U.S. patent application number 15/550153 was filed with the patent office on 2018-02-01 for flexible chemical production platform.
This patent application is currently assigned to Novomer, Inc.. The applicant listed for this patent is Novomer, Inc.. Invention is credited to Sadesh H. SOOKRAJ.
Application Number | 20180029005 15/550153 |
Document ID | / |
Family ID | 56614807 |
Filed Date | 2018-02-01 |
United States Patent
Application |
20180029005 |
Kind Code |
A1 |
SOOKRAJ; Sadesh H. |
February 1, 2018 |
FLEXIBLE CHEMICAL PRODUCTION PLATFORM
Abstract
Disclosed are integrated systems and methods for the conversion
of epoxides to beta lactones and to multiple C.sub.3 products
and/or C.sub.4 products.
Inventors: |
SOOKRAJ; Sadesh H.;
(Cambridge, MA) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Novomer, Inc. |
Boston |
MA |
US |
|
|
Assignee: |
Novomer, Inc.
Boston
MA
|
Family ID: |
56614807 |
Appl. No.: |
15/550153 |
Filed: |
February 12, 2016 |
PCT Filed: |
February 12, 2016 |
PCT NO: |
PCT/US2016/017861 |
371 Date: |
August 10, 2017 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
62116234 |
Feb 13, 2015 |
|
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C07C 67/03 20130101;
C07C 29/132 20130101; C07C 29/147 20130101; B01J 19/245 20130101;
C07C 29/149 20130101; B01J 2219/00049 20130101; B01J 2219/24
20130101; C08G 63/78 20130101; C08J 11/12 20130101; C07D 307/33
20130101; C08G 63/08 20130101; C07C 51/09 20130101; C07D 305/12
20130101; C07D 307/08 20130101; C07D 307/60 20130101; C08G 63/785
20130101; B01J 19/2445 20130101; C07D 301/03 20130101; C08J 2367/04
20130101; B01J 19/0006 20130101; C07C 67/03 20130101; C07C 69/54
20130101; C07C 29/147 20130101; C07C 31/207 20130101; C07C 51/09
20130101; C07C 57/04 20130101; C07C 51/09 20130101; C07C 55/10
20130101 |
International
Class: |
B01J 19/24 20060101
B01J019/24; C07D 307/33 20060101 C07D307/33; C07D 307/08 20060101
C07D307/08; C07C 29/149 20060101 C07C029/149; B01J 19/00 20060101
B01J019/00; C08G 63/78 20060101 C08G063/78; C07D 307/60 20060101
C07D307/60; C08J 11/12 20060101 C08J011/12; C07C 51/09 20060101
C07C051/09; C07D 305/12 20060101 C07D305/12; C07C 67/03 20060101
C07C067/03; C08G 63/08 20060101 C08G063/08 |
Claims
1. A system for the production of C.sub.3 and C.sub.4 products,
comprising: an epoxide source; a carbon monoxide (CO) source; a
central reactor, comprising: an inlet configured to receive epoxide
from the epoxide source and CO from the CO source, a central
reaction zone configured to convert at least some of the epoxide to
a beta lactone, and an outlet configured to provide an outlet
stream comprising the beta lactone, two or more of (i)-(iii): (i) a
first C.sub.3 reactor, comprising: an inlet configured to receive
the outlet stream comprising beta lactone of the central reactor, a
first C.sub.3 reaction zone configured to convert at least some of
the beta lactone to a first C.sub.3 product, and an outlet
configured to provide an outlet stream comprising the first C.sub.3
product, (ii) a second C.sub.3 reactor, comprising: an inlet
configured to receive the outlet stream comprising beta lactone of
the central reactor, a second C.sub.3 reaction zone configured to
convert at least some of the beta lactone to a second C.sub.3
product, and an outlet configured to provide an outlet stream
comprising the second C.sub.3 product, and (iii) a first C.sub.4
reactor, comprising: an inlet configured to receive the outlet
stream comprising beta lactone of the central reactor, a first
C.sub.4 reaction zone configured to convert at least some of the
beta lactone to a first C.sub.4 product, and an outlet configured
to provide an outlet stream comprising the first C.sub.4 product,
and a controller to independently modulate production of the beta
lactone and each of the products, provided that the first C.sub.3
product differs from the second C.sub.3 product.
2. The system of claim 1, wherein the epoxide is ethylene oxide
(EO) and the beta lactone is beta propiolactone (BPL).
3. The system of claim 1, further comprising; an ethylene source;
an oxidative reactor comprising: an inlet configured to receive
ethylene, an oxidative reaction zone configured to convert at least
some of the ethylene to EO, and an outlet configured to provide an
outlet stream comprising the EO, and feed the outlet stream
comprising EO to the inlet of the central reactor.
4. The system of claim 1, wherein the first C.sub.3 product and the
second C.sub.3 product are independently selected from an
.alpha.,.beta.-unsaturated acid, an .alpha.,.beta.-unsaturated
ester, an .alpha.,.beta.-unsaturated amide, a polymer and
1,3-propanediol (PDO).
5. The system of claim 1, wherein the first C.sub.3 product is PPL,
and the system further comprises: a third C.sub.3 reactor
comprising: an inlet configured to receive the outlet stream
comprising PPL of the first C.sub.3 reactor, a third C.sub.3
reaction zone configured to convert at least some of the PPL to a
third C.sub.3 product, and an outlet configured to provide an
outlet stream comprising the third C.sub.3 product.
6. The system of claim 5, wherein the third C.sub.3 product is
acrylic acid (AA).
7. The system of claim 1, wherein the first C.sub.4 product is
succinic anhydride, and the system further comprises: a second
C.sub.4 reactor comprising: an inlet configured to receive the
outlet stream comprising succinic anhydride of the first C.sub.4
reactor, a second C.sub.4 reaction zone configured to convert at
least some of the succinic anhydride to a second C.sub.4 product,
and an outlet configured to provide an outlet stream comprising the
second C.sub.4 product.
8. The system of claim 7, wherein the second C.sub.4 product is
succinic acid, 1,4 butanediol (BDO), tetrahydrofuran (THF) or gamma
butyrolactone (GBL).
9. A system, comprising: an ethylene source; a carbon monoxide (CO)
source; an alcohol source; an oxidative reactor comprising: an
inlet configured to receive ethylene from the ethylene source, an
oxidative reaction zone configured to convert at least some of the
ethylene to ethylene oxide (EO), and an outlet configured to
provide an EO stream comprising the EO; a central reactor
comprising: an inlet configured to receive EO from the EO stream of
the oxidative reactor and CO from the CO source, a central reaction
zone configured to convert at least some of the EO to beta
propiolactone (BPL), and an outlet configured to provide a BPL
stream comprising the BPL; a first C3 reactor comprising: an inlet
configured to receive BPL from at least a portion of the BPL stream
of the central reactor, a first C3 reaction zone configured to
convert at least some of the BPL to a polypropiolactone (PPL), and
an outlet configured to provide a PPL stream comprising the PPL; a
second C3 reactor comprising; an inlet configured to receive PPL
from the PPL stream of the first C3 reactor, a second C3 reaction
zone configured to convert at least some of the PPL to AA, and an
outlet configured to provide an AA stream comprising the AA; a
third C3 reactor comprising: an inlet configured to receive BPL
from at least a portion of the BPL stream of the central reactor,
and an alcohol from the alcohol source, a third C3 reaction zone
configured to convert at least some of the BPL to acrylate esters,
and an outlet configured to provide an acrylate ester stream
comprising the acrylate esters; and a controller to independently
modulating production of the EO, BPL, PPL, AA, and acrylate
esters.
10. A system, comprising: an ethylene source; a carbon monoxide
(CO) source; an alcohol source; an oxidative reactor comprising: an
inlet configured to receive ethylene from the ethylene source, an
oxidative reaction zone configured to convert at least some of the
ethylene to ethylene oxide (EO), and an outlet configured to
provide an EO stream comprising the EO; a central reactor
comprising: an inlet configured to receive EO from the EO stream of
the oxidative reactor and CO from the CO source, a central reaction
zone configured to convert at least some of the EO to beta
propiolactone (BPL), and an outlet configured to provide a BPL
stream comprising the BPL; a first C3 reactor comprising: an inlet
configured to receive BPL from at least a portion of the BPL stream
of the central reactor, a first C3 reaction zone configured to
convert at least some of the BPL to a polypropiolactone (PPL), and
an outlet configured to provide a PPL stream comprising the PPL; a
second C3 reactor comprising; an inlet configured to receive BPL
from at least a portion of the BPL stream of the central reactor, a
second C3 reaction zone configured to convert at least some of the
BPL to AA, and an outlet configured to provide an AA stream
comprising the AA; a third C3 reactor comprising: an inlet
configured to receive BPL from at least a portion of the BPL stream
of the central reactor, and an alcohol from the alcohol source, a
third C3 reaction zone configured to convert at least some of the
BPL to acrylate esters, and an outlet configured to provide an
acrylate ester stream comprising the acrylate esters; and a
controller to independently modulating production of the EO, BPL,
PPL, AA, and acrylate esters.
11. A system, comprising: an ethylene source; a carbon monoxide
(CO) source; an oxidative reactor comprising: an inlet configured
to receive ethylene from the ethylene source, an oxidative reaction
zone configured to convert at least some of the ethylene to
ethylene oxide (EO), and an outlet configured to provide an EO
stream comprising the EO; a central reactor comprising: an inlet
configured to receive EO from the EO stream of the oxidative
reactor and CO from the CO source, a central reaction zone
configured to convert at least some of the EO to beta propiolactone
(BPL), and an outlet configured to provide a BPL stream comprising
the BPL; a first C3 reactor comprising: an inlet configured to
receive BPL from at least a portion of the BPL stream of the
central reactor, a first C3 reaction zone configured to convert at
least some of the BPL to a polypropiolactone (PPL), and an outlet
configured to provide a PPL stream comprising the PPL; a second C3
reactor comprising; an inlet configured to receive PPL from the PPL
stream of the first C3 reactor, a second C3 reaction zone
configured to convert at least some of the PPL to AA, and an outlet
configured to provide an AA stream comprising the AA; a first C4
reactor comprising: an inlet configured to receive BPL from at
least a portion of the BPL stream of the central reactor, and
carbon monoxide from the CO source, a first C4 reaction zone
configured to convert at least some of the BPL to succinic
anhydride (SA), and an outlet configured to provide a succinic
anhydride stream comprising the succinic anhydride; and a
controller to independently modulating production of the EO, BPL,
PPL, AA, and SA.
12. A system, comprising: an ethylene source; a carbon monoxide
(CO) source; an alcohol source; an oxidative reactor comprising: an
inlet configured to receive ethylene from the ethylene source, an
oxidative reaction zone configured to convert at least some of the
ethylene to ethylene oxide (EO), and an outlet configured to
provide an EO stream comprising the EO, a central reactor
comprising: an inlet configured to receive EO from the EO stream of
the oxidative reactor and at least a portion of CO from the CO
source, a central reaction zone configured to convert at least some
of the EO to beta propiolactone (BPL), and an outlet configured to
provide a BPL stream comprising the BPL; a first C3 reactor
comprising: an inlet configured to receive BPL from at least a
portion of the BPL stream of the central reactor, a first C3
reaction zone configured to convert at least some of the BPL to a
polypropiolactone (PPL), and an outlet configured to provide a PPL
stream comprising the PPL; a second C3 reactor comprising; an inlet
configured to receive BPL from the BPL stream of the central
reactor, a second C3 reaction zone configured to convert at least
some of the BPL to AA, and an outlet configured to provide an AA
stream comprising the AA; a third C3 reactor comprising: an inlet
configured to receive BPL from at least a portion of the BPL stream
of the central reactor, and an alcohol from the alcohol source, a
third C3 reaction zone configured to convert at least some of the
BPL to acrylate esters, and an outlet configured to provide an
acrylate ester stream comprising the acrylate esters; a first C4
reactor comprising: an inlet configured to receive BPL from at
least a portion of the BPL stream of the central reactor, and at
least a portion of CO from the CO source, a first C4 reaction zone
configured to convert at least some of the BPL to succinic
anhydride (SA), and an outlet configured to provide a SA stream
comprising the succinic anhydride; and a controller to
independently modulating production of the EO, BPL, PPL, AA,
acrylate esters, and SA.
13. The system of claim 11, further comprising: a hydrogen source;
and a second C4 reactor comprising: an inlet configured to receive
SA from the SA stream of the first C4 reactor, a hydrogen inlet fed
from the hydrogen source, a second C4 reaction zone configured to
hydrogenate at least a portion of the SA to provide a C4 product
stream comprising 1,4 butanediol (BDO), tetrahydrofuran (THF), or
gamma butyrolactone (GBL), or any combinations thereof.
14. The system of claim 13, wherein the controller is configured to
further modulate production of BDO, THF, and GBL.
15. A method for converting an epoxide to two or more of: a first
C.sub.3 product, a second C.sub.3 product, and a first C.sub.4
product within an integrated system, the method comprising:
providing an inlet stream comprising an epoxide and carbon monoxide
(CO) to a central reactor of the integrated system; contacting the
inlet stream with a carbonylation catalyst in a central reaction
zone; converting at least a portion of the epoxide to a beta
lactone to produce an outlet stream comprising beta lactone; (i)
directing the outlet stream comprising beta lactone from the
central reaction zone to a first C.sub.3 reactor, and converting at
least some of the beta lactone to a first C.sub.3 product in the
first C.sub.3 reactor to produce an outlet stream comprising the
first C.sub.3 product, or (ii) directing the outlet stream
comprising beta lactone from the central reaction zone to a second
C.sub.3 reactor, and converting at least some of the beta lactone
to a second C.sub.3 product in the second C.sub.3 reactor to
produce an outlet stream comprising the second C.sub.3 product, or
(iii) directing the outlet stream comprising beta lactone from the
central reaction zone to a first C.sub.4 reactor, and converting at
least some of the beta lactone to a first C.sub.4 product in the
first C.sub.4 reactor to produce an outlet stream comprising the
first C.sub.4 product, provided that at least two of (i)-(iii) are
selected; and obtaining two or more of the first C.sub.3 product,
the second C.sub.3 product, and the first C.sub.4 product.
16. A method for producing acrylic acid (AA) from ethylene in a
single integrated system, the method comprising: providing ethylene
to an oxidative reactor that converts at least some of the ethylene
to ethylene oxide (EO); providing EO to a central reactor that
converts at least some of the EO to beta propiolactone (BPL); and
at least one or both of (i) and (ii): (i) providing BPL to a first
reactor that converts at least some of the BPL to AA, and (ii)
providing BPL to a reactor that converts at least some of the BPL
to polypropiolactone (PPL).
17. The method of claim 16, wherein BPL is provided to a first
reactor that converts at least some of the BPL, and the method
further comprises isolating acrylic acid at a rate of about 200 to
about 800 kilotons per annum (kta).
18. A method, comprising: providing an EO stream and a CO stream to
a central reactor, wherein the EO stream comprises EO, and the CO
stream comprises CO; contacting the EO stream and the CO stream
with a carbonylation catalyst in the central reactor; converting at
least a portion of the EO to produce a beta propiolactone (BPL)
stream comprising BPL; directing at least a portion of the BPL
stream to a first C3 reactor; converting at least portion of the
BPL to polypropiolactone (PPL) in the first C3 reactor, to produce
a PPL stream comprising the PPL from the first C3 reactor;
directing the PPL stream to a second C3 reactor; converting at
least a portion of the PPL to acrylic acid (AA) in the second C3
reactor, to produce an AA stream comprising the AA from the second
C3 reactor; directing at least a portion of the BPL stream to a
third C3 reactor; contacting the BPL stream in the third C3 reactor
with an alcohol; and converting at least a portion of the BPL to
acrylate esters in the third C3 reactor, to produce an acrylate
ester stream comprising the acrylate esters.
19. A method, comprising: providing an EO stream and a CO stream to
a central reactor, wherein the EO stream comprises EO, and the CO
stream comprises CO; contacting the EO stream and the CO stream
with a carbonylation catalyst in the central reactor; converting at
least a portion of the EO to produce a beta propiolactone (BPL)
stream comprising BPL; directing at least a portion of the BPL
stream to a first C3 reactor; converting at least portion of the
BPL to polypropiolactone (PPL) in the first C3 reactor, to produce
a PPL stream comprising the PPL from the first C3 reactor;
directing at least a portion of the BPL stream to a second C3
reactor; converting at least a portion of the BPL to acrylic acid
(AA) in the second C3 reactor, to produce an AA stream comprising
the AA from the second C3 reactor; directing at least a portion of
the BPL stream to a third C3 reactor; contacting the BPL stream
with an alcohol in the third C3 reactor; and converting at least a
portion of the BPL to acrylate esters in the third C3 reactor, to
produce an acrylate ester stream comprising the acrylate
esters.
20. A method, comprising: providing an EO stream and a CO stream to
a central reactor, wherein the EO stream comprises EO, and the CO
stream comprises CO; contacting the EO stream and the CO stream
with a carbonylation catalyst in the central reactor; converting at
least a portion of the EO to produce a beta propiolactone (BPL)
stream comprising BPL; directing at least a portion of the BPL
stream to a first C3 reactor; converting at least portion of the
BPL to polypropiolactone (PPL) in the first C3 reactor, to produce
a PPL stream comprising the PPL from the first C3 reactor;
directing the PPL stream to a second C3 reactor; converting at
least some of the PPL to acrylic acid (AA) in the second C3
reactor, to produce an AA stream comprising the AA from the second
C3 reactor; directing at least a portion of the BPL stream to a
first C4 reactor; and converting at least some of the BPL to
succinic anhydride (SA) in the first C4 reactor, to produce a
succinic anhydride stream comprising the succinic anhydride from
the first C4 reactor.
21. A method, comprising: providing an EO stream and a CO stream to
a central reactor, wherein the EO stream comprises EO, and the CO
stream comprises CO; contacting the EO stream and at least a
portion of the CO stream with a carbonylation catalyst in the
central reactor; converting at least a portion of the EO to produce
a beta propiolactone (BPL) stream comprising BPL; directing at
least a portion of the BPL stream to a first C3 reactor; converting
at least portion of the BPL to polypropiolactone (PPL) in the first
C3 reactor, to produce a PPL stream comprising the PPL from the
first C3 reactor; directing at least a portion of the BPL stream to
a second C3 reactor; converting at least a portion of the BPL to
acrylic acid (AA) in the second C3 reactor, to produce an AA stream
comprising the AA from the second C3 reactor; directing at least a
portion of the BPL stream to a third C3 reactor; contacting the BPL
stream with an alcohol in the third C3 reactor; converting at least
a portion of the BPL to acrylate esters in the C3 reactor, to
produce an acrylate ester stream comprising the acrylate esters;
directing at least a portion of the BPL stream to a first C4
reactor; contacting the BPL stream and at least a portion of the CO
stream in the first C4 reactor; and converting at least a portion
of the BPL to succinic anhydride (SA) in the first C4 reactor, to
produce a SA stream comprising the SA.
22. The method claim 20, further comprising: directing the SA
stream to a second C4 reactor; contacting at the SA stream with
hydrogen in the second C4 reactor; and converting at least a
portion of the SA to 1,4 butanediol (BDO), tetrahydrofuran (THF),
or gamma butyrolactone (GBL), or any combinations thereof.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application claims priority to U.S. Provisional Patent
Application No. 62/116,234, filed Feb. 13, 2015, which is
incorporated herein by reference in its entirety.
FIELD
[0002] The present disclosure relates generally to the production
of chemicals, and more specifically to the conversion of epoxides
to various C.sub.3 products and/or C.sub.4 products, such as
acrylic acid and acid anhydrides.
BACKGROUND
[0003] Industrial-scale production of most chemicals generally
relies upon devoted synthetic precursors, chemical transformations
and production plants that cannot easily accommodate or integrate
the production of other chemicals. For example, production of
three-carbon-containing C.sub.3 chemicals, such as acrylic acid
(AA) and esters thereof, and that of four-carbon-containing C.sub.4
chemicals, such as succinic anhydride (SA), generally proceed from
distinct precursors via unrelated transformations that require
specialized plants and methods.
[0004] Acrylic acid (C.sub.3) is primarily produced via vapor phase
oxidation of C.sub.3 propylene, involving two reactors in series,
utilizing separate catalysts. In this arrangement, the first
reactor converts propylene to C.sub.3 acrolein and the second
reactor converts acrolein to AA. The production of acid anhydrides,
including C.sub.4 succinic anhydride, generally proceeds via
distinct synthetic transformations, such as dehydration of the
corresponding C.sub.4 acids or hydrogenation of C.sub.4 maleic
anhydride.
[0005] There is a need to develop flexible methods and centralized
systems for the production of distinct product trains from a common
synthetic precursor. Such methods and systems would be of
particular value if they could modulate relative production of
distinct product trains as needed.
BRIEF SUMMARY
[0006] Provided herein are methods and systems that consolidate
multiple product trains into a single facility that would allow
producers to respond quickly to changes in market demand for each
product and reduce their present reliance upon the transportation
of certain production intermediates, some of which like acrylic
acid are highly reactive and dangerous.
[0007] In one aspect, provided are integrated systems suitable for
effecting the conversion of epoxides to multiple C.sub.3 products
and/or C.sub.4 products. In certain embodiments, a system is
provided for the production of chemicals, comprising:
[0008] a central reactor, comprising an inlet fed by an epoxide
source and a carbon monoxide (CO) source, a central reaction zone
that converts at least some of the epoxide to a beta lactone, and
an outlet which provides an outlet stream comprising the beta
lactone,
[0009] two or more of: [0010] (i) a first C.sub.3 reactor,
comprising an inlet fed by the outlet stream comprising beta
lactone of the central reactor, a first C.sub.3 reaction zone that
converts at least some of the beta lactone to a first C.sub.3
product, and an outlet which provides an outlet stream comprising
the first C.sub.3 product, [0011] (ii) a second C.sub.3 reactor,
comprising an inlet fed by the outlet stream comprising beta
lactone of the central reactor, a second C.sub.3 reaction zone that
converts at least some of the beta lactone to a second C.sub.3
product, and an outlet which provides an outlet stream comprising
the second C.sub.3 product, and [0012] (iii) a first C.sub.4
reactor, comprising an inlet fed by the outlet stream comprising
beta lactone of the central reactor, a first C.sub.4 reaction zone
that converts at least some of the beta lactone to a first C.sub.4
product, and an outlet which provides an outlet stream comprising
the first C.sub.4 product, and
[0013] a controller for independently modulating production of the
beta lactone and each of the products,
[0014] with the provision that the first C.sub.3 product differs
from the second C.sub.3 product.
[0015] In some variations, provided is a system for the production
of C.sub.3 and C.sub.4 products, comprising:
[0016] an epoxide source;
[0017] a carbon monoxide (CO) source;
[0018] a central reactor, comprising: [0019] an inlet configured to
receive epoxide from the epoxide source and CO from the CO source,
[0020] a central reaction zone configured to convert at least some
of the epoxide to a beta lactone, and [0021] an outlet configured
to provide an outlet stream comprising the beta lactone,
[0022] two or more of (i)-(iii): [0023] (i) a first C.sub.3
reactor, comprising: [0024] an inlet configured to receive the
outlet stream comprising beta lactone of the central reactor,
[0025] a first C.sub.3 reaction zone configured to convert at least
some of the beta lactone to a first C.sub.3 product, and [0026] an
outlet configured to provide an outlet stream comprising the first
C.sub.3 product, [0027] (ii) a second C.sub.3 reactor, comprising:
[0028] an inlet configured to receive the outlet stream comprising
beta lactone of the central reactor, [0029] a second C.sub.3
reaction zone configured to convert at least some of the beta
lactone to a second C.sub.3 product, and [0030] an outlet
configured to provide an outlet stream comprising the second
C.sub.3 product, and [0031] (iii) a first C.sub.4 reactor,
comprising: [0032] an inlet configured to receive the outlet stream
comprising beta lactone of the central reactor, [0033] a first
C.sub.4 reaction zone configured to convert at least some of the
beta lactone to a first C.sub.4 product, and [0034] an outlet
configured to provide an outlet stream comprising the first C.sub.4
product, and
[0035] a controller to independently modulate production of the
beta lactone and each of the products,
[0036] provided that the first C.sub.3 product differs from the
second C.sub.3 product.
[0037] In another variation, provided is a system, comprising:
[0038] an ethylene source;
[0039] a carbon monoxide (CO) source;
[0040] an alcohol source;
[0041] an oxidative reactor comprising: [0042] an inlet configured
to receive ethylene from the ethylene source, [0043] an oxidative
reaction zone configured to convert at least some of the ethylene
to ethylene oxide (EO), and [0044] an outlet configured to provide
an EO stream comprising the EO;
[0045] a central reactor comprising: [0046] an inlet configured to
receive EO from the EO stream of the oxidative reactor and CO from
the CO source, [0047] a central reaction zone configured to convert
at least some of the EO to beta propiolactone (BPL), and [0048] an
outlet configured to provide a BPL stream comprising the BPL;
[0049] a first C3 reactor comprising: [0050] an inlet configured to
receive BPL from at least a portion of the BPL stream of the
central reactor, [0051] a first C3 reaction zone configured to
convert at least some of the BPL to a polypropiolactone (PPL), and
[0052] an outlet configured to provide a PPL stream comprising the
PPL;
[0053] a second C3 reactor comprising; [0054] an inlet configured
to receive PPL from the PPL stream of the first C3 reactor, [0055]
a second C3 reaction zone configured to convert at least some of
the PPL to AA, and [0056] an outlet configured to provide an AA
stream comprising the AA;
[0057] a third C3 reactor comprising: [0058] an inlet configured to
receive BPL from at least a portion of the BPL stream of the
central reactor, and an alcohol from the alcohol source, [0059] a
third C3 reaction zone configured to convert at least some of the
BPL to acrylate esters, and [0060] an outlet configured to provide
an acrylate ester stream comprising the acrylate esters; and
[0061] a controller to independently modulating production of the
EO, BPL, PPL, AA, and acrylate esters.
[0062] In another variation, provided is a system, comprising:
[0063] an ethylene source;
[0064] a carbon monoxide (CO) source;
[0065] an alcohol source;
[0066] an oxidative reactor comprising: [0067] an inlet configured
to receive ethylene from the ethylene source, [0068] an oxidative
reaction zone configured to convert at least some of the ethylene
to ethylene oxide (EO), and [0069] an outlet configured to provide
an EO stream comprising the EO;
[0070] a central reactor comprising: [0071] an inlet configured to
receive EO from the EO stream of the oxidative reactor and CO from
the CO source, [0072] a central reaction zone configured to convert
at least some of the EO to beta propiolactone (BPL), and [0073] an
outlet configured to provide a BPL stream comprising the BPL;
[0074] a first C3 reactor comprising: [0075] an inlet configured to
receive BPL from at least a portion of the BPL stream of the
central reactor, [0076] a first C3 reaction zone configured to
convert at least some of the BPL to a polypropiolactone (PPL), and
[0077] an outlet configured to provide a PPL stream comprising the
PPL;
[0078] a second C3 reactor comprising; [0079] an inlet configured
to receive BPL from at least a portion of the BPL stream of the
central reactor, [0080] a second C3 reaction zone configured to
convert at least some of the BPL to AA, and [0081] an outlet
configured to provide an AA stream comprising the AA;
[0082] a third C3 reactor comprising: [0083] an inlet configured to
receive BPL from at least a portion of the BPL stream of the
central reactor, and an alcohol from the alcohol source, [0084] a
third C3 reaction zone configured to convert at least some of the
BPL to acrylate esters, and [0085] an outlet configured to provide
an acrylate ester stream comprising the acrylate esters; and
[0086] a controller to independently modulating production of the
EO, BPL, PPL, AA, and acrylate esters.
[0087] In yet another variation, provided is a system,
comprising:
[0088] an ethylene source;
[0089] a carbon monoxide (CO) source;
[0090] an oxidative reactor comprising: [0091] an inlet configured
to receive ethylene from the ethylene source, [0092] an oxidative
reaction zone configured to convert at least some of the ethylene
to ethylene oxide (EO), and [0093] an outlet configured to provide
an EO stream comprising the EO;
[0094] a central reactor comprising: [0095] an inlet configured to
receive EO from the EO stream of the oxidative reactor and CO from
the CO source, [0096] a central reaction zone configured to convert
at least some of the EO to beta propiolactone (BPL), and [0097] an
outlet configured to provide a BPL stream comprising the BPL;
[0098] a first C3 reactor comprising: [0099] an inlet configured to
receive BPL from at least a portion of the BPL stream of the
central reactor, [0100] a first C3 reaction zone configured to
convert at least some of the BPL to a polypropiolactone (PPL), and
[0101] an outlet configured to provide a PPL stream comprising the
PPL;
[0102] a second C3 reactor comprising; [0103] an inlet configured
to receive PPL from the PPL stream of the first C3 reactor, [0104]
a second C3 reaction zone configured to convert at least some of
the PPL to AA, and [0105] an outlet configured to provide an AA
stream comprising the AA;
[0106] a first C4 reactor comprising: [0107] an inlet configured to
receive BPL from at least a portion of the BPL stream of the
central reactor, and carbon monoxide from the CO source, [0108] a
first C4 reaction zone configured to convert at least some of the
BPL to succinic anhydride (SA), and [0109] an outlet configured to
provide a succinic anhydride stream comprising the succinic
anhydride; and
[0110] a controller to independently modulating production of the
EO, BPL, PPL, AA, and SA.
[0111] In yet another variation, provided is a system,
comprising:
[0112] an ethylene source;
[0113] a carbon monoxide (CO) source;
[0114] an alcohol source;
[0115] an oxidative reactor comprising: [0116] an inlet configured
to receive ethylene from the ethylene source, [0117] an oxidative
reaction zone configured to convert at least some of the ethylene
to ethylene oxide (EO), and [0118] an outlet configured to provide
an EO stream comprising the EO,
[0119] a central reactor comprising: [0120] an inlet configured to
receive EO from the EO stream of the oxidative reactor and at least
a portion of CO from the CO source, [0121] a central reaction zone
configured to convert at least some of the EO to beta propiolactone
(BPL), and [0122] an outlet configured to provide a BPL stream
comprising the BPL;
[0123] a first C3 reactor comprising: [0124] an inlet configured to
receive BPL from at least a portion of the BPL stream of the
central reactor, [0125] a first C3 reaction zone configured to
convert at least some of the BPL to a polypropiolactone (PPL), and
[0126] an outlet configured to provide a PPL stream comprising the
PPL;
[0127] a second C3 reactor comprising; [0128] an inlet configured
to receive BPL from the BPL stream of the central reactor, [0129] a
second C3 reaction zone configured to convert at least some of the
BPL to AA, and [0130] an outlet configured to provide an AA stream
comprising the AA;
[0131] a third C3 reactor comprising: [0132] an inlet configured to
receive BPL from at least a portion of the BPL stream of the
central reactor, and an alcohol from the alcohol source, [0133] a
third C3 reaction zone configured to convert at least some of the
BPL to acrylate esters, and [0134] an outlet configured to provide
an acrylate ester stream comprising the acrylate esters;
[0135] a first C4 reactor comprising: [0136] an inlet configured to
receive BPL from at least a portion of the BPL stream of the
central reactor, and at least a portion of CO from the CO source,
[0137] a first C4 reaction zone configured to convert at least some
of the BPL to succinic anhydride (SA), and [0138] an outlet
configured to provide a SA stream comprising the succinic
anhydride; and
[0139] a controller to independently modulating production of the
EO, BPL, PPL, AA, acrylate esters, and SA.
[0140] In another aspect, related methods are disclosed for the
conversion of epoxides to multiple C.sub.3 products and/or C.sub.4
products. In one variation, provided is a method for converting an
epoxide to two or more of: a first C.sub.3 product, a second
C.sub.3 product, and a first C.sub.4 product within an integrated
system, the method comprising:
[0141] providing an inlet stream comprising an epoxide and carbon
monoxide (CO) to a central reactor of the integrated system;
[0142] contacting the inlet stream with a carbonylation catalyst in
a central reaction zone;
[0143] converting at least a portion of the epoxide to a beta
lactone to produce an outlet stream comprising beta lactone;
[0144] (i) directing the outlet stream comprising beta lactone from
the central reaction zone to a first C.sub.3 reactor, and
converting at least some of the beta lactone to a first C.sub.3
product in the first C.sub.3 reactor to produce an outlet stream
comprising the first C.sub.3 product, or
[0145] (ii) directing the outlet stream comprising beta lactone
from the central reaction zone to a second C.sub.3 reactor, and
converting at least some of the beta lactone to a second C.sub.3
product in the second C.sub.3 reactor to produce an outlet stream
comprising the second C.sub.3 product, or
[0146] (iii) directing the outlet stream comprising beta lactone
from the central reaction zone to a first C.sub.4 reactor, and
converting at least some of the beta lactone to a first C.sub.4
product in the first C.sub.4 reactor to produce an outlet stream
comprising the first C.sub.4 product,
[0147] provided that at least two of (i)-(iii) are selected;
and
[0148] obtaining two or more of the first C.sub.3 product, the
second C.sub.3 product, and the first C.sub.4 product.
[0149] In another variation, provided is a method, comprising:
[0150] providing an EO stream and a CO stream to a central reactor,
wherein the EO stream comprises EO, and the CO stream comprises
CO;
[0151] contacting the EO stream and the CO stream with a
carbonylation catalyst in the central reactor;
[0152] converting at least a portion of the EO to produce a beta
propiolactone (BPL) stream comprising BPL;
[0153] directing at least a portion of the BPL stream to a first C3
reactor;
[0154] converting at least portion of the BPL to polypropiolactone
(PPL) in the first C3 reactor, to produce a PPL stream comprising
the PPL from the first C3 reactor;
[0155] directing the PPL stream to a second C3 reactor;
[0156] converting at least a portion of the PPL to acrylic acid
(AA) in the second C3 reactor, to produce an AA stream comprising
the AA from the second C3 reactor;
[0157] directing at least a portion of the BPL stream to a third C3
reactor;
[0158] contacting the BPL stream in the third C3 reactor with an
alcohol; and
[0159] converting at least a portion of the BPL to acrylate esters
in the third C3 reactor, to produce an acrylate ester stream
comprising the acrylate esters.
[0160] In yet another variation, provided is a method,
comprising:
[0161] providing an EO stream and a CO stream to a central reactor,
wherein the EO stream comprises EO, and the CO stream comprises
CO;
[0162] contacting the EO stream and the CO stream with a
carbonylation catalyst in the central reactor;
[0163] converting at least a portion of the EO to produce a beta
propiolactone (BPL) stream comprising BPL;
[0164] directing at least a portion of the BPL stream to a first C3
reactor;
[0165] converting at least portion of the BPL to polypropiolactone
(PPL) in the first C3 reactor, to produce a PPL stream comprising
the PPL from the first C3 reactor;
[0166] directing at least a portion of the BPL stream to a second
C3 reactor;
[0167] converting at least a portion of the BPL to acrylic acid
(AA) in the second C3 reactor, to produce an AA stream comprising
the AA from the second C3 reactor;
[0168] directing at least a portion of the BPL stream to a third C3
reactor;
[0169] contacting the BPL stream with an alcohol in the third C3
reactor; and
[0170] converting at least a portion of the BPL to acrylate esters
in the third C3 reactor, to produce an acrylate ester stream
comprising the acrylate esters.
[0171] In yet another variation, provided is a method,
comprising:
[0172] providing an EO stream and a CO stream to a central reactor,
wherein the EO stream comprises EO, and the CO stream comprises
CO;
[0173] contacting the EO stream and the CO stream with a
carbonylation catalyst in the central reactor;
[0174] converting at least a portion of the EO to produce a beta
propiolactone (BPL) stream comprising BPL;
[0175] directing at least a portion of the BPL stream to a first C3
reactor;
[0176] converting at least portion of the BPL to polypropiolactone
(PPL) in the first C3 reactor, to produce a PPL stream comprising
the PPL from the first C3 reactor;
[0177] directing the PPL stream to a second C3 reactor;
[0178] converting at least some of the PPL to acrylic acid (AA) in
the second C3 reactor, to produce an AA stream comprising the AA
from the second C3 reactor;
[0179] directing at least a portion of the BPL stream to a first C4
reactor; and
[0180] converting at least some of the BPL to succinic anhydride
(SA) in the first C4 reactor, to produce a succinic anhydride
stream comprising the succinic anhydride from the first C4
reactor.
[0181] In yet another variation, provided is a method,
comprising:
[0182] providing an EO stream and a CO stream to a central reactor,
wherein the EO stream comprises EO, and the CO stream comprises
CO;
[0183] contacting the EO stream and at least a portion of the CO
stream with a carbonylation catalyst in the central reactor;
[0184] converting at least a portion of the EO to produce a beta
propiolactone (BPL) stream comprising BPL;
[0185] directing at least a portion of the BPL stream to a first C3
reactor;
[0186] converting at least portion of the BPL to polypropiolactone
(PPL) in the first C3 reactor, to produce a PPL stream comprising
the PPL from the first C3 reactor;
[0187] directing at least a portion of the BPL stream to a second
C3 reactor;
[0188] converting at least a portion of the BPL to acrylic acid
(AA) in the second C3 reactor, to produce an AA stream comprising
the AA from the second C3 reactor;
[0189] directing at least a portion of the BPL stream to a third C3
reactor;
[0190] contacting the BPL stream with an alcohol in the third C3
reactor;
[0191] converting at least a portion of the BPL to acrylate esters
in the C3 reactor, to produce an acrylate ester stream comprising
the acrylate esters;
[0192] directing at least a portion of the BPL stream to a first C4
reactor;
[0193] contacting the BPL stream and at least a portion of the CO
stream in the first C4 reactor; and
[0194] converting at least a portion of the BPL to succinic
anhydride (SA) in the first C4 reactor, to produce a SA stream
comprising the SA.
[0195] The disclosed systems and methods are described in greater
detail below.
BRIEF DESCRIPTION OF THE FIGURES
[0196] The present application can be best understood by reference
to the following description taken in conjunction with the
accompanying figures, in which like parts may be referred to by
like numerals.
[0197] FIG. 1 shows, in one embodiment, a representative process
schematic for the disclosed systems.
DEFINITIONS
[0198] Definitions of specific functional groups and chemical terms
are described in more detail below. The chemical elements are
identified in accordance with the Periodic Table of the Elements,
CAS version, Handbook of Chemistry and Physics, 75.sup.th Ed.,
inside cover, and specific functional groups are generally defined
as described therein. Additionally, general principles of organic
chemistry, as well as specific functional moieties and reactivity,
are described in Organic Chemistry, Thomas Sorrell, University
Science Books, Sausalito, 1999; Smith and March March's Advanced
Organic Chemistry, 5.sup.th Edition, John Wiley & Sons, Inc.,
New York, 2001; Larock, Comprehensive Organic Transformations, VCH
Publishers, Inc., New York, 1989; Carruthers, Some Modern Methods
of Organic Synthesis, 3.sup.rd Edition, Cambridge University Press,
Cambridge, 1987.
[0199] The terms "halo" and "halogen" as used herein refer to an
atom selected from fluorine (fluoro, --F), chlorine (chloro, --Cl),
bromine (bromo, --Br), and iodine (iodo, --I).
[0200] The term "aliphatic" or "aliphatic group", as used herein,
denotes a hydrocarbon moiety that may be straight-chain (i.e.,
unbranched), branched, or cyclic (including fused, bridging, and
spiro-fused polycyclic) and may be completely saturated or may
contain one or more units of unsaturation, but which is not
aromatic. In some variations, the aliphatic group is unbranched or
branched. In other variations, the aliphatic group is cyclic.
Unless otherwise specified, in some variations, aliphatic groups
contain 1-30 carbon atoms. In certain embodiments, aliphatic groups
contain 1-12 carbon atoms. In certain embodiments, aliphatic groups
contain 1-8 carbon atoms. In certain embodiments, aliphatic groups
contain 1-6 carbon atoms. In certain embodiments, aliphatic groups
contain 1-5 carbon atoms, In certain embodiments, aliphatic groups
contain 1-4 carbon atoms, in yet other embodiments aliphatic groups
contain 1-3 carbon atoms, and in yet other embodiments aliphatic
groups contain 1-2 carbon atoms. Suitable aliphatic groups include,
for example, linear or branched, alkyl, alkenyl, and alkynyl
groups, and hybrids thereof such as (cycloalkyl)alkyl,
(cycloalkenyl)alkyl or (cycloalkyl)alkenyl.
[0201] The term "heteroaliphatic," as used herein, refers to
aliphatic groups wherein one or more carbon atoms are independently
replaced by one or more atoms selected from the group consisting of
oxygen, sulfur, nitrogen, phosphorus, or boron. In certain
embodiments, one or two carbon atoms are independently replaced by
one or more of oxygen, sulfur, nitrogen, or phosphorus.
Heteroaliphatic groups may be substituted or unsubstituted,
branched or unbranched, cyclic or acyclic, and include
"heterocycle," "hetercyclyl," "heterocycloaliphatic," or
"heterocyclic" groups. In some variations, the heteroaliphatic
group is branched or unbranched. In other variations, the
heteroaliphatic group is cyclic. In yet other variations, the
heteroaliphatic group is acyclic.
[0202] The term "unsaturated", as used herein, means that a moiety
has one or more double or triple bonds.
[0203] The terms "cycloaliphatic", "carbocycle", or "carbocyclic",
used alone or as part of a larger moiety, refer to a saturated or
partially unsaturated cyclic aliphatic monocyclic, bicyclic, or
polycyclic ring systems, as described herein, having from 3 to 12
members, wherein the aliphatic ring system is optionally
substituted as defined above and described herein. Cycloaliphatic
groups include, for example, cyclopropyl, cyclobutyl, cyclopentyl,
cyclopentenyl, cyclohexyl, cyclohexenyl, cycloheptyl,
cycloheptenyl, cyclooctyl, cyclooctenyl, and cyclooctadienyl. In
certain embodiments, the cycloalkyl has 3-6 carbons. The terms
"cycloaliphatic", "carbocycle" or "carbocyclic" also include
aliphatic rings that are fused to one or more aromatic or
nonaromatic rings, such as decahydronaphthyl or tetrahydronaphthyl,
where the radical or point of attachment is on the aliphatic ring.
In certain embodiments, a carbocyclic group is bicyclic. In certain
embodiments, a carbocyclic group is tricyclic. In certain
embodiments, a carbocyclic group is polycyclic.
[0204] The term "alkyl," as used herein, refers to a saturated
hydrocarbon radical. In some variations, the alkyl group is a
saturated, straight- or branched-chain hydrocarbon radicals derived
from an aliphatic moiety containing between one and six carbon
atoms by removal of a single hydrogen atom. Unless otherwise
specified, in some variations, alkyl groups contain 1-12 carbon
atoms. In certain embodiments, alkyl groups contain 1-8 carbon
atoms. In certain embodiments, alkyl groups contain 1-6 carbon
atoms. In certain embodiments, alkyl groups contain 1-5 carbon
atoms, In certain embodiments, alkyl groups contain 1-4 carbon
atoms, in yet other embodiments alkyl groups contain 1-3 carbon
atoms, and in yet other embodiments alkyl groups contain 1-2 carbon
atoms. Alkyl radicals may include, for example, methyl, ethyl,
n-propyl, isopropyl, n-butyl, iso-butyl, sec-butyl, sec-pentyl,
iso-pentyl, tert-butyl, n-pentyl, neopentyl, n-hexyl, sec-hexyl,
n-heptyl, n-octyl, n-decyl, n-undecyl, and dodecyl.
[0205] The terms "alkenyl," as used herein, denote a monovalent
group having at least one carbon-carbon double bond. In some
variations, the alkenyl group is a monovalent group derived from a
straight- or branched-chain aliphatic moiety having at least one
carbon-carbon double bond by the removal of a single hydrogen atom.
Unless otherwise specified, in some variations, alkenyl groups
contain 2-12 carbon atoms. In certain embodiments, alkenyl groups
contain 2-8 carbon atoms. In certain embodiments, alkenyl groups
contain 2-6 carbon atoms. In certain embodiments, alkenyl groups
contain 2-5 carbon atoms, In certain embodiments, alkenyl groups
contain 2-4 carbon atoms, in yet other embodiments alkenyl groups
contain 2-3 carbon atoms, and in yet other embodiments alkenyl
groups contain 2 carbon atoms. Alkenyl groups include, for example,
ethenyl, propenyl, butenyl, and 1-methyl-2-buten-1-yl.
[0206] The term "alkynyl," as used herein, refers to a monovalent
group having at least one carbon-carbon triple bond. In some
variations, the alkynyl group is a monovalent group derived from a
straight- or branched-chain aliphatic moiety having at least one
carbon-carbon triple bond by the removal of a single hydrogen atom.
Unless otherwise specified, in some variations, alkynyl groups
contain 2-12 carbon atoms. In certain embodiments, alkynyl groups
contain 2-8 carbon atoms. In certain embodiments, alkynyl groups
contain 2-6 carbon atoms. In certain embodiments, alkynyl groups
contain 2-5 carbon atoms, In certain embodiments, alkynyl groups
contain 2-4 carbon atoms, in yet other embodiments alkynyl groups
contain 2-3 carbon atoms, and in yet other embodiments alkynyl
groups contain 2 carbon atoms. Representative alkynyl groups
include, for example, ethynyl, 2-propynyl (propargyl), and
1-propynyl.
[0207] The term "carbocycle" and "carbocyclic ring" as used herein,
refers to monocyclic and polycyclic moieties wherein the rings
contain only carbon atoms. Unless otherwise specified, carbocycles
may be saturated, partially unsaturated or aromatic, and contain 3
to 20 carbon atoms. Representative carbocyles include, for example,
cyclopropane, cyclobutane, cyclopentane, cyclohexane,
bicyclo[2,2,1]heptane, norbornene, phenyl, cyclohexene,
naphthalene, and spiro[4.5]decane.
[0208] The term "aryl" used alone or as part of a larger moiety as
in "aralkyl", "aralkoxy", or "aryloxyalkyl", refers to monocyclic
and polycyclic ring systems having a total of five to 20 ring
members, wherein at least one ring in the system is aromatic and
wherein each ring in the system contains three to twelve ring
members. The term "aryl" may be used interchangeably with the term
"aryl ring". In certain embodiments, "aryl" refers to an aromatic
ring system which includes, for example, phenyl, naphthyl, and
anthracyl, which may bear one or more substituents. Also included
within the scope of the term "aryl", as it is used herein, is a
group in which an aromatic ring is fused to one or more additional
rings, such as benzofuranyl, indanyl, phthalimidyl, naphthimidyl,
phenanthridinyl, and tetrahydronaphthyl.
[0209] The terms "heteroaryl" and "heteroar-", used alone or as
part of a larger moiety, e.g., "heteroaralkyl", or
"heteroaralkoxy", refer to groups having 5 to 14 ring atoms,
preferably 5, 6, 9 or 10 ring atoms; having 6, 10, or 14 pi (.pi.)
electrons shared in a cyclic array; and having, in addition to
carbon atoms, from one to five heteroatoms. The term "heteroatom"
refers to nitrogen, oxygen, or sulfur, and includes any oxidized
form of nitrogen or sulfur, and any quaternized form of a basic
nitrogen. Heteroaryl groups include, for example, thienyl, furanyl,
pyrrolyl, imidazolyl, pyrazolyl, triazolyl, tetrazolyl, oxazolyl,
isoxazolyl, oxadiazolyl, thiazolyl, isothiazolyl, thiadiazolyl,
pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, indolizinyl, purinyl,
naphthyridinyl, benzofuranyl and pteridinyl. The terms "heteroaryl"
and "heteroar-" as used herein, also include groups in which a
heteroaromatic ring is fused to one or more aryl, cycloaliphatic,
or heterocyclyl rings, where the radical or point of attachment is
on the heteroaromatic ring. Examples include indolyl, isoindolyl,
benzothienyl, benzofuranyl, dibenzofuranyl, indazolyl,
benzimidazolyl, benzthiazolyl, quinolyl, isoquinolyl, cinnolinyl,
phthalazinyl, quinazolinyl, quinoxalinyl, 4H-quinolizinyl,
carbazolyl, acridinyl, phenazinyl, phenothiazinyl, phenoxazinyl,
tetrahydroquinolinyl, tetrahydroisoquinolinyl, and
pyrido[2,3-b]-1,4-oxazin-3(4H)-one. A heteroaryl group may be
monocyclic or bicyclic. The term "heteroaryl" may be used
interchangeably with the terms "heteroaryl ring", "heteroaryl
group", or "heteroaromatic", any of which terms include rings that
are optionally substituted. The term "heteroaralkyl" refers to an
alkyl group substituted by a heteroaryl, wherein the alkyl and
heteroaryl portions independently are optionally substituted.
[0210] As used herein, the terms "heterocycle", "heterocyclyl",
"heterocyclic radical", and "heterocyclic ring" are used
interchangeably and may be saturated or partially unsaturated, and
have, in addition to carbon atoms, one or more, preferably one to
four, heteroatoms, as defined above. In some variations, the
heterocyclic group is a stable 5- to 7-membered monocyclic or 7- to
14-membered bicyclic heterocyclic moiety that is either saturated
or partially unsaturated, and having, in addition to carbon atoms,
one or more, preferably one to four, heteroatoms, as defined above.
When used in reference to a ring atom of a heterocycle, the term
"nitrogen" includes a substituted nitrogen. As an example, in a
saturated or partially unsaturated ring having 0-3 heteroatoms
selected from oxygen, sulfur or nitrogen, the nitrogen may be N (as
in 3,4-dihydro-2H-pyrrolyl), NH (as in pyrrolidinyl), or +NR (as in
N-substituted pyrrolidinyl).
[0211] A heterocyclic ring can be attached to its pendant group at
any heteroatom or carbon atom that results in a stable structure
and any of the ring atoms can be optionally substituted. Examples
of such saturated or partially unsaturated heterocyclic radicals
include, for example, tetrahydrofuranyl, tetrahydrothienyl,
pyrrolidinyl, pyrrolidonyl, piperidinyl, pyrrolinyl,
tetrahydroquinolinyl, tetrahydroisoquinolinyl, decahydroquinolinyl,
oxazolidinyl, piperazinyl, dioxanyl, dioxolanyl, diazepinyl,
oxazepinyl, thiazepinyl, morpholinyl, and quinuclidinyl. The terms
"heterocycle", "heterocyclyl", "heterocyclyl ring", "heterocyclic
group", "heterocyclic moiety", and "heterocyclic radical", are used
interchangeably herein, and also include groups in which a
heterocyclyl ring is fused to one or more aryl, heteroaryl, or
cycloaliphatic rings, such as indolinyl, 3H-indolyl, chromanyl,
phenanthridinyl, or tetrahydroquinolinyl, where the radical or
point of attachment is on the heterocyclyl ring. A heterocyclyl
group may be mono- or bicyclic. The term "heterocyclylalkyl" refers
to an alkyl group substituted by a heterocyclyl, wherein the alkyl
and heterocyclyl portions independently are optionally
substituted.
[0212] As used herein, the term "partially unsaturated" refers to a
ring moiety that includes at least one double or triple bond. The
term "partially unsaturated" is intended to encompass rings having
multiple sites of unsaturation, but is not intended to include aryl
or heteroaryl moieties, as herein defined.
[0213] As described herein, compounds described herein may contain
"optionally substituted" moieties. In general, the term
"substituted", whether preceded by the term "optionally" or not,
means that one or more hydrogens of the designated moiety are
replaced with a suitable substituent. Unless otherwise indicated,
an "optionally substituted" group may have a suitable substituent
at each substitutable position of the group, and when more than one
position in any given structure may be substituted with more than
one substituent selected from a specified group, the substituent
may be either the same or different at every position. Combinations
of substituents envisioned are preferably those that result in the
formation of stable or chemically feasible compounds. The term
"stable", as used herein, refers to compounds that are not
substantially altered when subjected to conditions to allow for
their production, detection, and, in certain embodiments, their
recovery, purification, and use for one or more of the purposes
disclosed herein.
[0214] In some chemical structures herein, substituents are shown
attached to a bond which crosses a bond in a ring of the depicted
molecule. This means that one or more of the substituents may be
attached to the ring at any available position (usually in place of
a hydrogen atom of the parent structure). In cases where an atom of
a ring so substituted has two substitutable positions, two groups
may be present on the same ring atom. When more than one
substituent is present, each is defined independently of the
others, and each may have a different structure. In cases where the
substituent shown crossing a bond of the ring is --R, this has the
same meaning as if the ring were said to be "optionally
substituted" as described in the preceding paragraph.
[0215] Suitable monovalent substituents on a substitutable carbon
atom of an "optionally substituted" group are independently
halogen; --(CH.sub.2).sub.0-4R.sup..smallcircle.;
--(CH.sub.2).sub.0-4OR.sup..smallcircle.;
--O--(CH.sub.2).sub.0-4C(O)OR.sup..smallcircle.;
--(CH.sub.2).sub.0-4CH(OR.sup..smallcircle.).sub.2;
--(CH.sub.2).sub.0-4SR.sup..smallcircle.; --(CH.sub.2).sub.0-4Ph,
which may be substituted with R.sup..smallcircle.;
--(CH.sub.2).sub.0-4(CH.sub.2).sub.0-1Ph which may be substituted
with R.sup..smallcircle.; --CH.dbd.CHPh, which may be substituted
with R.sup..smallcircle.; --NO.sub.2; --CN; --N.sub.3;
--(CH.sub.2).sub.0-4N(R.sup..smallcircle.).sub.2;
--(CH.sub.2).sub.0-4N(R.sup..smallcircle.)C(O)R.sup..smallcircle.;
--N(R.sup..smallcircle.)C(S)R.sup..smallcircle.;
--(CH.sub.2).sub.0-4N(R.sup..smallcircle.)C(O)NR.sup..smallcircle..sub.2;
--N(R.sup..smallcircle.)C(S)NR.sup..smallcircle..sub.2;
--(CH.sub.2).sub.0-4N(R.sup..smallcircle.)C(O)OR.sup..smallcircle.;
--N(R.sup..smallcircle.)N(R.sup..smallcircle.)C(O)R.sup..smallcircle.;
--N(R.sup..smallcircle.)N(R.sup..smallcircle.)C(O)NR.sup..smallcircle..su-
b.2;
--N(R.sup..smallcircle.)N(R.sup..smallcircle.)C(O)OR.sup..smallcircle-
.; --(CH.sub.2).sub.0-4C(O)R.sup..smallcircle.;
--C(S)R.sup..smallcircle.;
--(CH.sub.2).sub.0-4C(O)OR.sup..smallcircle.;
--(CH.sub.2).sub.0-4C(O)N(R.sup..smallcircle.).sub.2;
--(CH.sub.2).sub.0-4C(O)SR.sup..smallcircle.;
--(CH.sub.2).sub.0-4C(O)OSiR.sup..smallcircle..sub.3;
--(CH.sub.2).sub.0-4OC(O)R.sup..smallcircle.;
--OC(O)(CH.sub.2).sub.0-4SR.sup..smallcircle.;
--SC(S)SR.sup..smallcircle.;
--(CH.sub.2).sub.0-4SC(O)R.sup..smallcircle.;
--(CH.sub.2).sub.0-4C(O)NR.sup..smallcircle..sub.2;
--C(S)NR.sup..smallcircle..sub.2; --C(S)SR.sup..smallcircle.;
--SC(S)SR.sup..smallcircle.;
--(CH.sub.2).sub.0-4OC(O)NR.sup..smallcircle..sub.2;
--C(O)N(OR.sup..smallcircle.)R.sup..smallcircle.;
--C(O)C(O)R.sup..smallcircle.;
--C(O)CH.sub.2C(O)R.sup..smallcircle.;
--C(NOR.sup..smallcircle.)R.sup..smallcircle.;
--(CH.sub.2).sub.0-4SSR.sup..smallcircle.;
--(CH.sub.2).sub.0-4S(O).sub.2R.sup..smallcircle.;
--(CH.sub.2).sub.0-4S(O).sub.2OR.sup..smallcircle.;
--(CH.sub.2).sub.0-4OS(O).sub.2R.sup..smallcircle.;
--S(O).sub.2NR.sup..smallcircle..sub.2;
--(CH.sub.2).sub.0-4S(O)R.sup..smallcircle.;
--N(R.sup..smallcircle.)S(O).sub.2NR.sup..smallcircle..sub.2;
--N(R.sup..smallcircle.)S(O).sub.2R.sup..smallcircle.;
--N(OR.sup..smallcircle.)R.sup..smallcircle.;
--C(NH)NR.sup..smallcircle..sub.2; --P(O).sub.2R.sup..smallcircle.;
--P(O)R.sup..smallcircle..sub.2; --OP(O)R.sup..smallcircle..sub.2;
--OP(O)(OR.sup..smallcircle.).sub.2; SiR.sup..smallcircle..sub.3;
--(C.sub.1-4 straight or branched
alkylene)O--N(R.sup..smallcircle.).sub.2; or --(C.sub.1-4 straight
or branched alkylene)C(O)O--N(R.sup..smallcircle.).sub.2, wherein
each R.sup..smallcircle. may be substituted as defined below and is
independently hydrogen, C.sub.1-8 aliphatic, --CH.sub.2Ph,
--O(CH.sub.2).sub.0-1Ph, or a 5-6-membered saturated, partially
unsaturated, or aryl ring having 0-4 heteroatoms independently
selected from nitrogen, oxygen, and sulfur, or, notwithstanding the
definition above, two independent occurrences of
R.sup..smallcircle., taken together with their intervening atom(s),
form a 3-12-membered saturated, partially unsaturated, or aryl
mono- or polycyclic ring having 0-4 heteroatoms independently
selected from nitrogen, oxygen, and sulfur, which may be
substituted as defined below.
[0216] Suitable monovalent substituents on R.sup..smallcircle. (or
the ring formed by taking two independent occurrences of
R.sup..smallcircle. together with their intervening atoms), are
independently halogen, --(CH.sub.2).sub.0-2R.sup. , -(haloR.sup. ),
--(CH.sub.2).sub.0-2OH, --(CH.sub.2).sub.0-2OR.sup. ,
--(CH.sub.2).sub.0-2CH(OR.sup. ).sub.2; --O(haloR.sup. ), --CN,
--N.sub.3, --(CH.sub.2).sub.0-2C(O)R.sup. ,
--(CH.sub.2).sub.0-2C(O)OH, --(CH.sub.2).sub.0-2C(O)OR.sup. ,
--(CH.sub.2).sub.0-4C(O)N(R.sup..smallcircle.).sub.2;
--(CH.sub.2).sub.0-2SR.sup. , --(CH.sub.2).sub.0-2SH,
--(CH.sub.2).sub.0-2NH.sub.2, --(CH.sub.2).sub.0-2NHR.sup. ,
--(CH.sub.2).sub.0-2NR.sup. .sub.2, --NO.sub.2, --SiR.sup. .sub.3,
--OSiR.sup. .sub.3, --C(O)SR.sup. , --(C.sub.1-4 straight or
branched alkylene)C(O)OR.sup. , or --SSR.sup. wherein each R.sup.
is unsubstituted or where preceded by "halo" is substituted only
with one or more halogens, and is independently selected from
C.sub.1-4 aliphatic, --CH.sub.2Ph, --O(CH.sub.2).sub.0-1Ph, or a
5-6-membered saturated, partially unsaturated, or aryl ring having
0-4 heteroatoms independently selected from nitrogen, oxygen, and
sulfur. Suitable divalent substituents on a saturated carbon atom
of R.sup..smallcircle. include .dbd.O and .dbd.S.
[0217] Suitable divalent substituents on a saturated carbon atom of
an "optionally substituted" group include the following: .dbd.O,
.dbd.S, .dbd.NNR*.sub.2, .dbd.NNHC(O)R*, .dbd.NNHC(O)OR*,
.dbd.NNHS(O).sub.2R*, .dbd.NR*, .dbd.NOR*,
--O(C(R*.sub.2)).sub.2-3O--, or --S(C(R*.sub.2)).sub.2-3S--,
wherein each independent occurrence of R* is selected from
hydrogen, C.sub.1-6 aliphatic which may be substituted as defined
below, or an unsubstituted 5-6-membered saturated, partially
unsaturated, or aryl ring having 0-4 heteroatoms independently
selected from nitrogen, oxygen, and sulfur. Suitable divalent
substituents that are bound to vicinal substitutable carbons of an
"optionally substituted" group include: --O(CR*.sub.2).sub.2-3O--,
wherein each independent occurrence of R* is selected from
hydrogen, C.sub.1-6 aliphatic which may be substituted as defined
below, or an unsubstituted 5-6-membered saturated, partially
unsaturated, or aryl ring having 0-4 heteroatoms independently
selected from nitrogen, oxygen, and sulfur.
[0218] Suitable substituents on the aliphatic group of R* include
halogen, --R.sup. , -(haloR.sup. ), --OH, --OR.sup. ,
--O(haloR.sup. ), --CN, --C(O)OH, --C(O)OR.sup. , --NH.sub.2,
--NHR.sup. , --NR.sup. .sub.2, or --NO.sub.2, wherein each R* is
unsubstituted or where preceded by "halo" is substituted only with
one or more halogens, and is independently C.sub.1-4 aliphatic,
--CH.sub.2Ph, --O(CH.sub.2).sub.0-1Ph, or a 5-6-membered saturated,
partially unsaturated, or aryl ring having 0-4 heteroatoms
independently selected from nitrogen, oxygen, and sulfur.
[0219] Suitable substituents on a substitutable nitrogen of an
"optionally substituted" group include --R.sup..dagger.,
--NR.sup..dagger..sub.2, --C(O)R.sup..dagger.,
--C(O)OR.sup..dagger., --C(O)C(O)R.sup..dagger.,
--C(O)CH.sub.2C(O)R.sup..dagger., --S(O).sub.2R.sup..dagger.,
--S(O).sub.2NR.sup..dagger..sub.2, --C(S)NR.sup..dagger..sub.2,
--C(NH)NR.sup..dagger..sub.2, or
--N(R.sup..dagger.)S(O).sub.2R.sup..dagger.; wherein each
R.sup..dagger. is independently hydrogen, C.sub.1-6 aliphatic which
may be substituted as defined below, unsubstituted --OPh, or an
unsubstituted 5-6-membered saturated, partially unsaturated, or
aryl ring having 0-4 heteroatoms independently selected from
nitrogen, oxygen, and sulfur, or, notwithstanding the definition
above, two independent occurrences of R.sup..dagger., taken
together with their intervening atom(s) form an unsubstituted
3-12-membered saturated, partially unsaturated, or aryl mono- or
bicyclic ring having 0-4 heteroatoms independently selected from
nitrogen, oxygen, and sulfur.
[0220] Suitable substituents on the aliphatic group of
R.sup..dagger. are independently halogen, --R.sup. , -(haloR.sup.
), --OH, --OR.sup. , --O(haloR.sup. ), --CN, --C(O)OH,
--C(O)OR.sup. , --NH.sub.2, --NHR.sup. , --NR.sup. .sub.2, or
--NO.sub.2, wherein each R.sup. is unsubstituted or where preceded
by "halo" is substituted only with one or more halogens, and is
independently C.sub.1-4 aliphatic, --CH.sub.2Ph,
--O(CH.sub.2).sub.0-1Ph, or a 5-6-membered saturated, partially
unsaturated, or aryl ring having 0-4 heteroatoms independently
selected from nitrogen, oxygen, and sulfur.
[0221] As used herein, the term "reaction zone" refers to a reactor
or portion thereof where a particular reaction occurs. A given
reaction may occur in multiple reaction zones, and different
reaction zones may comprise separate reactors or portions of the
same reactor. A "reactor" typically comprises one or more vessels
with one or more connections to other reactors or system
components.
[0222] As used herein, the terms "reaction stream" and "inlet
stream" refer to a solid, liquid or gas medium comprising a
reactant that enters a reaction zone. As used herein, the terms
"product stream" and "outlet stream" refer to a solid, liquid or
gas medium comprising a product that exits a reaction zone. Each
reaction and product (i.e., inlet or outlet) stream may be neat
with respect to reactant and product or they may include
co-reactants, co-products, catalysts, solvents, carrier gas and/or
impurities.
[0223] The term "polymer", as used herein, refers to a molecule
comprising multiple repeating units. In some variations, the
polymer is a molecule of high relative molecular mass, the
structure of which comprises the multiple repetition of units
derived, actually or conceptually, from molecules of low relative
molecular mass. In certain embodiments, a polymer is comprised of
only one monomer species (e.g., polyethylene oxide). In certain
embodiments, the polymer may be a copolymer, terpolymer,
heteropolymer, block copolymer, or tapered heteropolymer of one or
more epoxides. In one variation, the polymer may be a copolymer,
terpolymer, heteropolymer, block copolymer, or tapered
heteropolymer of two or more monomers.
[0224] In some variations, the term "epoxide", as used herein,
refers to a substituted or unsubstituted oxirane. No particular
constraints are placed on the identity of the epoxide used in the
carbonylation reactions described herein. In certain embodiments,
the epoxide is selected from the group consisting of ethylene
oxide, propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide,
epichlorohydrin, cyclohexene oxide, cyclopentene oxide,
3,3,3-trifluoro-1,2-epoxypropane, styrene oxide, a glycidyl ether,
and a glycidyl ester. In certain embodiments, the epoxide is
propylene oxide. In certain embodiments, the epoxide is EO. In
certain embodiments, the epoxide is prepared from an alkene such as
ethylene or propylene.
[0225] In some variations, the term "glycidyl", as used herein,
refers to an oxirane substituted with a hydroxyl methyl group or a
derivative thereof. In other variations, the term glycidyl as used
herein is meant to include moieties having additional substitution
on one or more of the carbon atoms of the oxirane ring or on the
methylene group of the hydroxymethyl moiety, examples of such
substitution may include, for example, alkyl groups, halogen atoms,
and aryl groups. The terms glycidyl ester, glycidyl acrylate, and
glycidyl ether denote substitution at the oxygen atom of the
above-mentioned hydroxymethyl group. For example, the oxygen atom
is bonded to an acyl group, an acrylate group, or an alkyl group,
respectively.
[0226] The term "acrylate" or "acrylates" as used herein refer to
any acyl group having a vinyl group adjacent to the acyl carbonyl.
The terms encompass mono-, di- and tri-substituted vinyl groups.
Acrylates may include, for example, acrylate, methacrylate,
ethacrylate, cinnamate (3-phenylacrylate), crotonate, tiglate, and
senecioate.
[0227] As used herein, the terms "crude acrylic acid" and "glacial
acrylic acid" (GAA) describe AA of relatively low and high purity,
respectively. Crude AA (also called technical grade AA) has a
typical minimum overall purity level of 94%, by weight, and can be
used to make acrylic esters for paint, adhesive, textile, paper,
leather, fiber, and plastic additive applications. GAA has a
typical overall purity level ranging from 98% to 99.99% and can be
used to make polyacrylic acid (PAA), or a salt thereof, for
superabsorbent polymers (SAPs) in disposable diapers, training
pants, adult incontinence undergarments and sanitary napkins. PAA,
or a salt thereof, is also used in compositions for paper and water
treatment, and in detergent co-builder applications. In some
variations, acrylic acid has a purity of at least 98%, at least
98.5%, at least 99%, at least 99.1%, at least 99.2%, at least
99.3%, at least 99.4%, at least 99.5%, at least 99.6%, at least
99.7%, at least 99.8%, or at least 99.9%; or between 99% and
99.95%, between 99.5% and 99.95%, between 99.6% and 99.95%, between
99.7% and 99.95%, or between 99.8% and 99.95%.
[0228] Suitable salts of PAA include metal salts, such those of any
alkali (e.g., Na.sup.+, K.sup.+) cations, alkaline earth cations.
In certain embodiments, the PAA salt is the Na.sup.+ salt, i.e.,
sodium PAA. In certain embodiments, the salt is the K.sup.+ salt,
i.e., potassium PAA.
[0229] Impurities in GAA are reduced to an extent possible to
facilitate a high-degree of polymerization to PAA and avoid adverse
effects from side products in end applications. For example,
aldehyde impurities in AA hinder polymerization and may discolor
the PAA. Maleic anhydride impurities form undesirable copolymers
which may be detrimental to polymer properties. Carboxylic acids,
e.g., saturated carboxylic acids that do not participate in the
polymerization, can affect the final odor of PAA or SAP-containing
products and/or detract from their use. For example, foul odors may
emanate from SAP that contains acetic acid or propionic acid and
skin irritation may result from SAP that contains formic acid.
[0230] The reduction or removal of impurities from propylene-based
AA is costly, whether to produce propylene-based crude AA or
propylene-based glacial AA. Such costly multistage distillations
and/or extraction and/or crystallizations steps are generally
employed (e.g., as described in U.S. Pat. Nos. 5,705,688 and
6,541,665). Notable impurities from propylene-based AA that are
reduced and/or eliminated from the disclosed compositions include,
for example, aldehyde impurities and products or byproducts of
propylene oxidation.
[0231] As used herein, the term "product or byproduct of propylene
oxidation" or "compound that derives from the oxidation of
propylene" are used interchangeably to refer to products and
byproducts of propylene oxidation including, for example, C.sub.1
compounds such as formaldehyde, and formic acid; C.sub.2 compounds
such as acetaldehyde, acetic acid; C.sub.3 compounds such as
propylene, allyl alcohol, acrolein (i.e., propenal), propanol,
isopropyl alcohol, acetone, propionic acid; C.sub.4 compounds such
as maleic anhydride; and C.sub.5 compounds such as furfural,
etc.
[0232] As used herein, the term "aldehyde impurity" include any of
the aldehydes in the preceding paragraph.
[0233] As used herein, the term "substantially free" means less
than 5 wt %, 1 wt %, 0.1 wt %, 0.01 wt %, or a range including any
two of these values, or less than 10,000 ppm, 1,000 ppm, 500 ppm,
100 ppm, 50 ppm, 10 ppm, or a range including any two of these
values. In one variation, a composition that is substantially free
of Compound A has less than 5%, less than 4%, less than 3%, less
than 2%, less than 1%, less than 0.9%, less than 0.8%, less than
0.7%, less than 0.6%, less than 0.5%, less than 0.4%, less than
0.3%, less than 0.2%, less than 0.1%, less than 0.05%, less than
0.01%, or less than 0.001%, by weight, or a range including any two
of the aforementioned values, of Compound A.
[0234] Stabilizers are commonly used to preserve AA. As used
herein, the term "stabilizer" includes any radical polymerization
inhibitor or an anti-foaming agent. AA is susceptible to unwanted
Michael addition to itself and to unwanted free-radical
polymerization with itself, which may be counteracted by addition
of polymerization inhibitors to the AA. Suitable polymerization
inhibitors include, for example, hydroquinone monomethyl ether,
MEHQ, alkylphenols, such as o-, m- or p-cresol (methylphenol),
2-tert-butyl-4-methylphenol, 6-tert-butyl-2,4-dimethylphenol,
2,6-di-tert-butyl-4-methylphenol, 2-tert-butylphenol,
4-tert-butylphenol, 2,4-di-tert-butylphenol and
2-methyl-4-tert-butylphenol and hydroxyphenols such as
hydroquinone, catechol, resorcinol, 2-methylhydroquinone and
2,5-di-tert-butylhydroquinone. Examples of anti-foaming agents
include silicones (e.g., polydimethylsiloxanes), alcohols,
stearates, and glycols.
[0235] As used herein, the term "about" preceding one or more
numerical values means the numerical value .+-.5%. It should be
understood that reference to "about" a value or parameter herein
includes (and describes) embodiments that are directed to that
value or parameter per se. For example, description referring to
"about x" includes description of "x" per se.
DETAILED DESCRIPTION
[0236] Operators of existing chemical plants that produce a single
product are inevitably confronted with a reduction in demand for
that product. Generally, they must reduce or suspend production to
meet demand. Disclosed herein are chemical plants and production
methods that utilize ethylene-derived epoxides for the integrated
production of various C.sub.3 and/or C.sub.4 products that are
produced on-site. The disclosed plants are flexible because they
may direct epoxide, as needed, to any of the various C.sub.3 and/or
C.sub.4 products. A decrease in production of one product, due to a
drop in demand, can be offset by an increase in another product for
which demand is strong. Due in part to their versatility, the
disclosed chemical plants and production methods provide increased
efficiencies relative to existing chemical plants and methods.
Methods
[0237] In one aspect, provided are integrated methods for
converting epoxides to beta lactones and then to multiple C.sub.3
products and/or C.sub.4 products.
[0238] With reference to FIG. 1, an exemplary process schematic to
produce C.sub.3 and/or C.sub.4 products is depicted. The process
depicted involves ethylene oxidation in step 100, carbonylation
step 200 to produce BPL, and production of various C.sub.3 and/or
C.sub.4 products in step 300. In step 100, ethylene is fed into an
oxidative reactor to produce ethylene oxide by ethylene oxidation.
EO outlet stream 110 comprising EO exiting the oxidative reaction
zone is fed into a central reactor for the conversion of EO and CO
to BPL. In step 200, EO outlet stream 110 comprising EO, from the
oxidative reaction zone, enters the central reactor as an inlet
stream where it is combined with CO. BPL outlet streams 210 and/or
220 comprising BPL exit the central reactor. BPL outlet streams 210
and/or 220 are fed into the first, second, third and n.sup.th
C.sub.3 and/or C.sub.4 reactors. In step 300, BPL outlet streams
210 and/or 220 comprising BPL, from the central reactor, enters
each of the first, second, third and n.sup.th C.sub.3 and/or
C.sub.4 reactors as an inlet stream where each is converted to
first, second, third and n.sup.th C.sub.3 and/or C.sub.4 products.
In step 300, first, second, third and n.sup.th outlet streams
comprising first, second, third and n.sup.th C.sub.3 and/or C.sub.4
products exit the first, second, third and n.sup.th C.sub.3 and/or
C.sub.4 reactors. In step 400, the first, second, third and
n.sup.th outlet streams that exit are purified and/or isolated to
produce first, second, third and n.sup.th C.sub.3 and/or C.sub.4
products (depicted in FIG. 1 as "P1", "P2", "P3" and "Pn",
respectively).
[0239] It should generally be understood that, in other variations
of the process described in FIG. 1, one or more steps may be added
or omitted. For example, in one variation, step 100 may be omitted,
and ethylene oxide obtained from any commercially available source
may be fed into the central reactor in step 200.
[0240] Thus, in some aspects, provided is a method for converting
an epoxide to two or more of: a first C.sub.3 product, a second
C.sub.3 product, and a first C.sub.4 product within an integrated
system, the method comprising:
[0241] i) providing an inlet stream comprising an epoxide and
carbon monoxide (CO) to a central reactor of the integrated
system;
[0242] ii) contacting the inlet stream with a carbonylation
catalyst in a central reaction zone to effect conversion of at
least a portion of the provided epoxide to a beta lactone;
[0243] iii) directing the an outlet stream comprising beta lactone
from the central reaction zone to two or more of: [0244] (a) a
first C.sub.3 reactor, comprising an inlet fed by the outlet stream
comprising beta lactone of the central reactor, a first C.sub.3
reaction zone that converts at least some of the beta lactone to a
first C.sub.3 product, and an outlet from which an outlet stream
comprising the first C.sub.3 product is obtainable, [0245] (b) a
second C.sub.3 reactor, comprising an inlet fed by the outlet
stream comprising beta lactone of the central reactor, a second
C.sub.3 reaction zone that converts at least some of the beta
lactone to a second C.sub.3 product, and an outlet from which an
outlet stream comprising the second C.sub.3 product is obtainable,
and [0246] (c) a first C.sub.4 reactor, comprising an inlet fed by
the outlet stream comprising beta lactone of the central reactor, a
first C.sub.4 reaction zone that converts at least some of the beta
lactone to a first C.sub.4 product, and an outlet from which an
outlet stream comprising the first C.sub.4 product is obtainable,
and
[0247] iv) obtaining two or more of the first C.sub.3 product, the
second C.sub.3 product, and the first C.sub.4 product.
[0248] In certain embodiments, the method further comprises:
[0249] providing an inlet stream comprising ethylene to an inlet of
an oxidative reactor in which at least some of the ethylene is
converted to ethylene oxide (EO) and
[0250] providing an outlet stream comprising EO from the oxidative
reactor, to the inlet of the central reactor in which at least some
of the EO is converted to beta propiolactone (BPL).
[0251] In some variations, the method further comprises:
[0252] providing an inlet stream comprising ethylene to an inlet of
an oxidative reactor;
[0253] converting at least some of the ethylene to ethylene oxide
(EO) to produce an outlet stream comprising EO;
[0254] directing the outlet stream comprising EO from the oxidative
reactor to the inlet of the central reactor; and
[0255] converting at least some of the EO to BPL.
[0256] In certain embodiments, the method further comprises
directing the outlet stream comprising beta lactone from the
central reaction zone to the first C.sub.3 reactor and the second
C.sub.3 reactor.
[0257] In certain embodiments, the method further comprises
directing the outlet stream comprising beta lactone from the
central reaction zone to the first C.sub.3 reactor and the first
C.sub.4 reactor.
[0258] In certain embodiments, the epoxide is ethylene oxide (EO)
and the beta lactone is beta propiolactone (BPL).
[0259] In certain embodiments, the first C.sub.3 product and the
second C.sub.3 product are independently selected from an
.alpha.,.beta.-unsaturated acid, an .alpha.,.beta.-unsaturated
ester, an .alpha.,.beta.-unsaturated amide, a polymer and
1,3-propanediol (PDO).
[0260] In certain embodiments, the first C.sub.3 product is
polypropiolactone (PPL).
[0261] In certain embodiments, the first C.sub.3 product is acrylic
acid.
[0262] In certain embodiments, the first C.sub.3 product is
polyacrylic acid.
[0263] In certain embodiments, the first C.sub.3 product is an
acrylate ester. In certain embodiments, the acrylate ester is
selected from methyl acrylate, butyl acrylate and 2-ethylhexyl
acrylate.
[0264] In certain embodiments, the first C.sub.3 product is
PDO.
[0265] In certain embodiments, the method further comprises:
[0266] directing the outlet stream comprising PPL from the first
C.sub.3 reactor to a third C.sub.3 reactor, comprising an inlet fed
by the outlet stream comprising PPL of the first C.sub.3 reactor, a
third C.sub.3 reaction zone that converts at least some of the PPL
to a third C.sub.3 product, and an outlet from which an outlet
stream comprising the third C.sub.3 product is obtainable.
[0267] In some variations, the method further comprises:
[0268] directing the outlet stream comprising PPL from the first
C.sub.3 reactor to a third C.sub.3 reactor; and
[0269] converting at least some of the PPL to a third C.sub.3
product in the third C.sub.3 reactor to produce an outlet stream
comprising the third C.sub.3 product.
[0270] In certain embodiments, the first C.sub.3 product is
polypropiolactone (PPL).
[0271] In certain embodiments, the third C.sub.3 product is acrylic
acid.
[0272] In certain embodiments, the third C.sub.3 product is
polyacrylic acid.
[0273] In certain embodiments, the first C.sub.4 product is
succinic anhydride.
[0274] In certain embodiments, the first C.sub.4 product is
succinic anhydride, and the method further comprises a second
C.sub.4 reactor, comprising an inlet fed by the outlet stream
comprising succinic anhydride of the first C.sub.4 reactor, a
second C.sub.4 reaction zone that converts at least some of the
succinic anhydride to a second C.sub.4 product, and an outlet from
which an outlet stream comprising the second C.sub.4 product is
obtainable.
[0275] In some variations where the first C.sub.4 product is
succinic anhydride, the method further comprises:
[0276] directing the outlet stream comprising succinic anhydride
from the first C.sub.4 reactor to a second C.sub.4 reactor; and
[0277] converting at least some of the succinic anhydride to a
second C.sub.4 product in the second C.sub.4 reactor to produce an
outlet stream comprising the second C.sub.4 product.
[0278] In certain embodiments, the second C.sub.4 product is
succinic acid, 1,4 butanediol (BDO), tetrahydrofuran (THF) or gamma
butyrolactone (GBL).
[0279] In one embodiment, provided is an integrated method to
produce PPL, AA, and acrylate esters from an epoxide. Thus, in one
variation, provided is a method, comprising:
[0280] providing an EO stream and a CO stream to a central reactor,
wherein the EO stream comprises EO, and the CO stream comprises
CO;
[0281] contacting the EO stream and the CO stream with a
carbonylation catalyst in the central reactor;
[0282] converting at least a portion of the EO to produce a beta
propiolactone (BPL) stream comprising BPL;
[0283] directing at least a portion of the BPL stream to a first C3
reactor;
[0284] converting at least portion of the BPL to polypropiolactone
(PPL) in the first C3 reactor, to produce a PPL stream comprising
the PPL from the first C3 reactor;
[0285] directing the PPL stream to a second C3 reactor;
[0286] converting at least a portion of the PPL to acrylic acid
(AA) in the second C3 reactor, to produce an AA stream comprising
the AA from the second C3 reactor;
[0287] directing at least a portion of the BPL stream to a third C3
reactor;
[0288] contacting the BPL stream in the third C3 reactor with an
alcohol; and
[0289] converting at least a portion of the BPL to acrylate esters
in the third C3 reactor, to produce an acrylate ester stream
comprising the acrylate esters.
[0290] In some variations, the PPL stream, the AA stream, and the
acrylate ester stream are simultaneously produced. In certain
variations, the method further comprises modulating a ratio of
PPL:AA:acrylate ester produced in the PPL stream, the AA stream,
and the acrylate ester stream. In yet other variations, the method
further comprises modulating the fraction of the PPL stream that is
received by the second C3 reactor.
[0291] In another embodiment, provided is an integrated method to
produce PPL, AA, and acrylate esters from an epoxide. Thus, in
another variation, provided is a method, comprising:
[0292] providing an EO stream and a CO stream to a central reactor,
wherein the EO stream comprises EO, and the CO stream comprises
CO;
[0293] contacting the EO stream and the CO stream with a
carbonylation catalyst in the central reactor;
[0294] converting at least a portion of the EO to produce a beta
propiolactone (BPL) stream comprising BPL;
[0295] directing at least a portion of the BPL stream to a first C3
reactor;
[0296] converting at least portion of the BPL to polypropiolactone
(PPL) in the first C3 reactor, to produce a PPL stream comprising
the PPL from the first C3 reactor;
[0297] directing at least a portion of the BPL stream to a second
C3 reactor;
[0298] converting at least a portion of the BPL to acrylic acid
(AA) in the second C3 reactor, to produce an AA stream comprising
the AA from the second C3 reactor;
[0299] directing at least a portion of the BPL stream to a third C3
reactor;
[0300] contacting the BPL stream with an alcohol in the third C3
reactor; and
[0301] converting at least a portion of the BPL to acrylate esters
in the third C3 reactor, to produce an acrylate ester stream
comprising the acrylate esters.
[0302] In some variations, the PPL stream, the AA stream, and the
acrylate ester stream are simultaneously produced. In certain
variations, the method further comprises modulating a ratio of
PPL:AA:acrylate ester produced in the PPL stream, the AA stream,
and the acrylate ester stream. In yet other variations, the method
further comprises modulating the fraction of the BPL stream of the
first C3 reactor, and wherein the controller modulates the fraction
of the BPL stream that is received by the second C3 reactor.
[0303] In yet another embodiment, provided is an integrated method
to produce PPL, AA, and SA. Thus, in another variation, provided is
a method, comprising:
[0304] providing an EO stream and a CO stream to a central reactor,
wherein the EO stream comprises EO, and the CO stream comprises
CO;
[0305] contacting the EO stream and the CO stream with a
carbonylation catalyst in the central reactor;
[0306] converting at least a portion of the EO to produce a beta
propiolactone (BPL) stream comprising BPL;
[0307] directing at least a portion of the BPL stream to a first C3
reactor;
[0308] converting at least portion of the BPL to polypropiolactone
(PPL) in the first C3 reactor, to produce a PPL stream comprising
the PPL from the first C3 reactor;
[0309] directing the PPL stream to a second C3 reactor;
[0310] converting at least some of the PPL to acrylic acid (AA) in
the second C3 reactor, to produce an AA stream comprising the AA
from the second C3 reactor;
[0311] directing at least a portion of the BPL stream to a first C4
reactor; and
[0312] converting at least some of the BPL to succinic anhydride
(SA) in the first C4 reactor, to produce a succinic anhydride
stream comprising the succinic anhydride from the first C4
reactor.
[0313] In some variations, the PPL stream, the AA stream, and the
SA stream are simultaneously produced. In certain variations, the
method further comprises modulating a ratio of PPL:AA:SA from the
PPL stream, the AA stream, and the SA stream. In certain
variations, the method further comprises modulating the fraction of
the PPL stream that is received by the second C3 reactor. In yet
other variations, the method further comprises directing the SA
stream to a second C4 reactor; contacting at the SA stream with
hydrogen in the second C4 reactor; and converting at least a
portion of the SA to 1,4 butanediol (BDO), tetrahydrofuran (THF),
or gamma butyrolactone (GBL), or any combinations thereof. In
another variation, the method further comprises modulating a ratio
of BDO:THF:GBL produced in the second C4 reactor.
[0314] In yet another embodiment, provided is an integrated method
to produce PPL, AA and acrylate ester. Thus, in yet another
variation, provided is a method, comprising:
[0315] providing an EO stream and a CO stream to a central reactor,
wherein the EO stream comprises EO, and the CO stream comprises
CO;
[0316] contacting the EO stream and at least a portion of the CO
stream with a carbonylation catalyst in the central reactor;
[0317] converting at least a portion of the EO to produce a beta
propiolactone (BPL) stream comprising BPL;
[0318] directing at least a portion of the BPL stream to a first C3
reactor;
[0319] converting at least portion of the BPL to polypropiolactone
(PPL) in the first C3 reactor, to produce a PPL stream comprising
the PPL from the first C3 reactor;
[0320] directing at least a portion of the BPL stream to a second
C3 reactor;
[0321] converting at least a portion of the BPL to acrylic acid
(AA) in the second C3 reactor, to produce an AA stream comprising
the AA from the second C3 reactor;
[0322] directing at least a portion of the BPL stream to a third C3
reactor;
[0323] contacting the BPL stream with an alcohol in the third C3
reactor;
[0324] converting at least a portion of the BPL to acrylate esters
in the C3 reactor, to produce an acrylate ester stream comprising
the acrylate esters;
[0325] directing at least a portion of the BPL stream to a first C4
reactor;
[0326] contacting the BPL stream and at least a portion of the CO
stream in the first C4 reactor; and
[0327] converting at least a portion of the BPL to succinic
anhydride (SA) in the first C4 reactor, to produce a SA stream
comprising the SA.
[0328] In some variations, the PPL stream, the AA stream, and the
acrylate ester stream are simultaneously produced. In some
variations, the PPL stream, the AA stream, the acrylate ester
stream, and the SA stream are simultaneously produced. In certain
variations, the method further comprises modulating a ratio
PPL:AA:acrylate ester from the PPL stream, the AA stream, and the
acrylate ester stream. In other variations, the method further
comprises modulating a ratio PPL:AA:acrylate ester output:SA from
the PPL stream, the AA stream, the acrylate ester stream, and the
SA stream. In one variation, the method further comprises
modulating the fraction of the BPL stream that is received by the
second C3 reactor.
[0329] In some variations that may be combined with the foregoing
variations of the methods described herein, the method further
includes: directing the SA stream to a second C4 reactor;
contacting at the SA stream with hydrogen in the second C4 reactor;
and converting at least a portion of the SA to 1,4 butanediol
(BDO), tetrahydrofuran (THF), or gamma butyrolactone (GBL), or any
combinations thereof. In one variation, the method further
comprises modulating a ratio of BDO:THF:GBL produced in the second
C4 reactor.
[0330] In yet other variations that may be combined with the
foregoing variations of the methods described herein, the method
further comprises providing an ethylene stream to an oxidative
reactor, wherein the ethylene stream comprises ethylene; and
converting at least a portion of the ethylene to ethylene oxide
(EO), to produce the EO stream.
[0331] In yet other variations that may be combined with the
foregoing variations of the methods described herein where PPL is
produced, the method further comprises isolating PPL from the PPL
stream; and packaging the isolated PPL for distribution.
Systems
[0332] In one aspect, provided are integrated systems suitable for
effecting the conversion of epoxides to multiple C.sub.3 products
and/or C.sub.4 products. In certain embodiments, a system is
provided for the production of chemicals, comprising: [0333] a
central reactor, comprising an inlet fed by an epoxide source and a
carbon monoxide (CO) source, a central reaction zone that converts
at least some of the epoxide to a beta lactone, and an outlet which
provides an outlet stream comprising the beta lactone, [0334] two
or more of: [0335] (i) a first C.sub.3 reactor, comprising an inlet
fed by the outlet stream comprising beta lactone of the central
reactor, a first C.sub.3 reaction zone that converts at least some
of the beta lactone to a first C.sub.3 product, and an outlet which
provides an outlet stream comprising the first C.sub.3 product,
[0336] (ii) a second C.sub.3 reactor, comprising an inlet fed by
the outlet stream comprising beta lactone of the central reactor, a
second C.sub.3 reaction zone that converts at least some of the
beta lactone to a second C.sub.3 product, and an outlet which
provides an outlet stream comprising the second C.sub.3 product,
and [0337] (iii) a first C.sub.4 reactor, comprising an inlet fed
by the outlet stream comprising beta lactone of the central
reactor, a first C.sub.4 reaction zone that converts at least some
of the beta lactone to a first C.sub.4 product, and an outlet which
provides an outlet stream comprising the first C.sub.4 product, and
[0338] a controller for independently modulating production of the
beta lactone and each of the products, [0339] with the provision
that the first C.sub.3 product differs from the second C.sub.3
product.
[0340] In some variations, provided is a system for the production
of C.sub.3 and C.sub.4 products, comprising:
[0341] an epoxide source;
[0342] a carbon monoxide (CO) source;
[0343] a central reactor, comprising: [0344] an inlet configured to
receive epoxide from the epoxide source and CO from the CO source,
[0345] a central reaction zone configured to convert at least some
of the epoxide to a beta lactone, and [0346] an outlet configured
to provide an outlet stream comprising the beta lactone,
[0347] two or more of (i)-(iii): [0348] (i) a first C.sub.3
reactor, comprising: [0349] an inlet configured to receive the
outlet stream comprising beta lactone of the central reactor,
[0350] a first C.sub.3 reaction zone configured to convert at least
some of the beta lactone to a first C.sub.3 product, and [0351] an
outlet configured to provide an outlet stream comprising the first
C.sub.3 product, [0352] (ii) a second C.sub.3 reactor, comprising:
[0353] an inlet configured to receive the outlet stream comprising
beta lactone of the central reactor, [0354] a second C.sub.3
reaction zone configured to convert at least some of the beta
lactone to a second C.sub.3 product, and [0355] an outlet
configured to provide an outlet stream comprising the second
C.sub.3 product, and [0356] (iii) a first C.sub.4 reactor,
comprising: [0357] an inlet configured to receive the outlet stream
comprising beta lactone of the central reactor, [0358] a first
C.sub.4 reaction zone configured to convert at least some of the
beta lactone to a first C.sub.4 product, and [0359] an outlet
configured to provide an outlet stream comprising the first C.sub.4
product, and
[0360] a controller to independently modulate production of the
beta lactone and each of the products,
[0361] provided that the first C.sub.3 product differs from the
second C.sub.3 product.
[0362] In certain embodiments, the two or more of (i)-(iii) is (i)
the first C.sub.3 reactor and (ii) the second C.sub.3 reactor.
Thus, in certain variations, provided is a system for the
production of C.sub.3 products, comprising
[0363] an epoxide source;
[0364] a carbon monoxide (CO) source;
[0365] a central reactor, comprising: [0366] an inlet configured to
receive epoxide from the epoxide source and CO from the CO source,
[0367] a central reaction zone configured to convert at least some
of the epoxide to a beta lactone, and [0368] an outlet configured
to provide an outlet stream comprising the beta lactone,
[0369] a first C.sub.3 reactor, comprising: [0370] an inlet
configured to receive the outlet stream comprising beta lactone of
the central reactor, [0371] a first C.sub.3 reaction zone
configured to convert at least some of the beta lactone to a first
C.sub.3 product, and [0372] an outlet configured to provide an
outlet stream comprising the first C.sub.3 product;
[0373] a second C.sub.3 reactor, comprising: [0374] an inlet
configured to receive the outlet stream comprising beta lactone of
the central reactor, [0375] a second C.sub.3 reaction zone
configured to convert at least some of the beta lactone to a second
C.sub.3 product, and [0376] an outlet configured to provide an
outlet stream comprising the second C.sub.3 product; and
[0377] a controller to independently modulate production of the
beta lactone and each of the products,
provided that the first C.sub.3 product differs from the second
C.sub.3 product.
[0378] In certain embodiments, the two or more (i)-(iii) is (i) the
first C.sub.3 reactor and (iii) the first C.sub.4 reactor. Thus, in
certain variations, provided is a system for the production of
C.sub.3 and C.sub.4 products, comprising:
[0379] an epoxide source;
[0380] a carbon monoxide (CO) source;
[0381] a central reactor, comprising: [0382] an inlet configured to
receive epoxide from the epoxide source and CO from the CO source,
[0383] a central reaction zone configured to convert at least some
of the epoxide to a beta lactone, and [0384] an outlet configured
to provide an outlet stream comprising the beta lactone,
[0385] a C.sub.3 reactor, comprising: [0386] an inlet configured to
receive the outlet stream comprising beta lactone of the central
reactor, [0387] a C.sub.3 reaction zone configured to convert at
least some of the beta lactone to a C.sub.3 product, and [0388] an
outlet configured to provide an outlet stream comprising the
C.sub.3 product;
[0389] a C.sub.4 reactor, comprising: [0390] an inlet configured to
receive the outlet stream comprising beta lactone of the central
reactor, [0391] a C.sub.4 reaction zone configured to convert at
least some of the beta lactone to a C.sub.4 product, and [0392] an
outlet configured to provide an outlet stream comprising the
C.sub.4 product; and
[0393] a controller to independently modulate production of the
beta lactone and each of the products.
[0394] In certain embodiments, the two or more (i)-(iii) is (ii)
the second C.sub.3 reactor and (iii) the first C.sub.4 reactor.
Thus, in certain variations, provided is a system for the
production of C.sub.3 and C.sub.4 products, comprising:
[0395] an epoxide source;
[0396] a carbon monoxide (CO) source;
[0397] a central reactor, comprising: [0398] an inlet configured to
receive epoxide from the epoxide source and CO from the CO source,
[0399] a central reaction zone configured to convert at least some
of the epoxide to a beta lactone, and [0400] an outlet configured
to provide an outlet stream comprising the beta lactone,
[0401] a C.sub.3 reactor, comprising: [0402] an inlet configured to
receive the outlet stream comprising beta lactone of the central
reactor, [0403] a C.sub.3 reaction zone configured to convert at
least some of the beta lactone to a C.sub.3 product, and [0404] an
outlet configured to provide an outlet stream comprising the
C.sub.3 product;
[0405] a C.sub.4 reactor, comprising: [0406] an inlet configured to
receive the outlet stream comprising beta lactone of the central
reactor, [0407] a C.sub.4 reaction zone configured to convert at
least some of the beta lactone to a C.sub.4 product, and [0408] an
outlet configured to provide an outlet stream comprising the
C.sub.4 product; and
[0409] a controller to independently modulate production of the
beta lactone and each of the products,
[0410] In yet other embodiments, the two or more (i)-(iii) is (i) a
first C.sub.3 reactor, (ii) a second C.sub.3 reactor, and (iii) a
first C.sub.4 reactor. Thus, in other variations, provided is a
system for the production of C.sub.3 and C.sub.4 products,
comprising:
[0411] an epoxide source;
[0412] a carbon monoxide (CO) source;
[0413] a central reactor, comprising: [0414] an inlet configured to
receive epoxide from the epoxide source and CO from the CO source,
[0415] a central reaction zone configured to convert at least some
of the epoxide to a beta lactone, and [0416] an outlet configured
to provide an outlet stream comprising the beta lactone,
[0417] a first C.sub.3 reactor, comprising: [0418] an inlet
configured to receive the outlet stream comprising beta lactone of
the central reactor, [0419] a first C.sub.3 reaction zone
configured to convert at least some of the beta lactone to a first
C.sub.3 product, and [0420] an outlet configured to provide an
outlet stream comprising the first C.sub.3 product;
[0421] a second C.sub.3 reactor, comprising: [0422] an inlet
configured to receive the outlet stream comprising beta lactone of
the central reactor, [0423] a second C.sub.3 reaction zone
configured to convert at least some of the beta lactone to a second
C.sub.3 product, and [0424] an outlet configured to provide an
outlet stream comprising the second C.sub.3 product;
[0425] a first C.sub.4 reactor, comprising: [0426] an inlet
configured to receive the outlet stream comprising beta lactone of
the central reactor, [0427] a first C.sub.4 reaction zone
configured to convert at least some of the beta lactone to a first
C.sub.4 product, and [0428] an outlet configured to provide an
outlet stream comprising the first C.sub.4 product; and
[0429] a controller to independently modulate production of the
beta lactone and each of the products,
[0430] provided that the first C.sub.3 product differs from the
second C.sub.3 product.
[0431] It should generally be understood that, in other variations,
one or more components of the systems described above may be added
or omitted. For example, in one variation, the system further
comprises:
[0432] an ethylene source;
[0433] an oxidative reactor comprising: [0434] an inlet configured
to receive ethylene, [0435] an oxidative reaction zone configured
to convert at least some of the ethylene to EO, and [0436] an
outlet configured to provide an outlet stream comprising the EO,
and feed the outlet stream comprising EO to the inlet of the
central reactor.
[0437] In one variation where the first C.sub.3 product is PPL, the
system further comprises:
[0438] a third C.sub.3 reactor comprising: [0439] an inlet
configured to receive the outlet stream comprising PPL of the first
C.sub.3 reactor, [0440] a third C.sub.3 reaction zone configured to
convert at least some of the PPL to a third C.sub.3 product, and
[0441] an outlet configured to provide an outlet stream comprising
the third C.sub.3 product.
[0442] In another variation where the first C.sub.4 product is
succinic anhydride, the system further comprises:
[0443] a second C.sub.4 reactor comprising: [0444] an inlet
configured to receive the outlet stream comprising succinic
anhydride of the first C.sub.4 reactor, [0445] a second C.sub.4
reaction zone configured to convert at least some of the succinic
anhydride to a second C.sub.4 product, and [0446] an outlet
configured to provide an outlet stream comprising the second
C.sub.4 product.
[0447] In one variation of the foregoing methods, the epoxide is
ethylene oxide (EO) and the beta lactone is beta propiolactone
(BPL).
[0448] In one embodiment, provided is an integrated system to
produce PPL, AA, and acrylate esters from an epoxide. Thus, in one
variation, provided is a system, comprising:
[0449] an ethylene source;
[0450] a carbon monoxide (CO) source;
[0451] an alcohol source;
[0452] an oxidative reactor comprising: [0453] an inlet configured
to receive ethylene from the ethylene source, [0454] an oxidative
reaction zone configured to convert at least some of the ethylene
to ethylene oxide (EO), and [0455] an outlet configured to provide
an EO stream comprising the EO;
[0456] a central reactor comprising: [0457] an inlet configured to
receive EO from the EO stream of the oxidative reactor and CO from
the CO source, [0458] a central reaction zone configured to convert
at least some of the EO to beta propiolactone (BPL), and [0459] an
outlet configured to provide a BPL stream comprising the BPL;
[0460] a first C3 reactor comprising: [0461] an inlet configured to
receive BPL from at least a portion of the BPL stream of the
central reactor, [0462] a first C3 reaction zone configured to
convert at least some of the BPL to a polypropiolactone (PPL), and
[0463] an outlet configured to provide a PPL stream comprising the
PPL;
[0464] a second C3 reactor comprising; [0465] an inlet configured
to receive PPL from the PPL stream of the first C3 reactor, [0466]
a second C3 reaction zone configured to convert at least some of
the PPL to AA, and [0467] an outlet configured to provide an AA
stream comprising the AA;
[0468] a third C3 reactor comprising: [0469] an inlet configured to
receive BPL from at least a portion of the BPL stream of the
central reactor, and an alcohol from the alcohol source, [0470] a
third C3 reaction zone configured to convert at least some of the
BPL to acrylate esters, and [0471] an outlet configured to provide
an acrylate ester stream comprising the acrylate esters; and
[0472] a controller to independently modulating production of the
EO, BPL, PPL, AA, and acrylate esters.
[0473] In some variations, the system is configured to
simultaneously produce the PPL stream, the AA stream, and the
acrylate ester stream. In certain variations, the controller
modulates a ratio of PPL:AA:acrylate ester from the PPL stream, the
AA stream, and the acrylate ester stream. In one variation where
the inlet of the second C3 reactor is configured to receive PPL
from a fraction of the PPL stream of the first C3 reactor, the
controller modulates the fraction of the PPL output stream that is
received by the inlet of the second C3 reactor.
[0474] In another embodiment, provided is an integrated system to
produce PPL, AA, and acrylate esters from an epoxide. Thus, in
another variation, provided is a system, comprising:
[0475] an ethylene source;
[0476] a carbon monoxide (CO) source;
[0477] an alcohol source;
[0478] an oxidative reactor comprising: [0479] an inlet configured
to receive ethylene from the ethylene source, [0480] an oxidative
reaction zone configured to convert at least some of the ethylene
to ethylene oxide (EO), and [0481] an outlet configured to provide
an EO stream comprising the EO;
[0482] a central reactor comprising: [0483] an inlet configured to
receive EO from the EO stream of the oxidative reactor and CO from
the CO source, [0484] a central reaction zone configured to convert
at least some of the EO to beta propiolactone (BPL), and [0485] an
outlet configured to provide a BPL stream comprising the BPL;
[0486] a first C3 reactor comprising: [0487] an inlet configured to
receive BPL from at least a portion of the BPL stream of the
central reactor, [0488] a first C3 reaction zone configured to
convert at least some of the BPL to a polypropiolactone (PPL), and
[0489] an outlet configured to provide a PPL stream comprising the
PPL;
[0490] a second C3 reactor comprising; [0491] an inlet configured
to receive BPL from at least a portion of the BPL stream of the
central reactor, [0492] a second C3 reaction zone configured to
convert at least some of the BPL to AA, and [0493] an outlet
configured to provide an AA stream comprising the AA;
[0494] a third C3 reactor comprising: [0495] an inlet configured to
receive BPL from at least a portion of the BPL stream of the
central reactor, and an alcohol from the alcohol source, [0496] a
third C3 reaction zone configured to convert at least some of the
BPL to acrylate esters, and [0497] an outlet configured to provide
an acrylate ester stream comprising the acrylate esters; and
[0498] a controller to independently modulating production of the
EO, BPL, PPL, AA, and acrylate esters.
[0499] In one variation, the system is configured to simultaneously
produce the PPL stream, the AA stream, and the acrylate ester
stream. In certain variations, the controller modulates a ratio of
PPL:AA:acrylate ester from the PPL stream, the AA stream, and the
acrylate ester stream.
[0500] In yet another embodiment, provided is an integrated system
to produce PPL, AA, and SA. Thus, in another variation, provided is
a system, comprising:
[0501] an ethylene source;
[0502] a carbon monoxide (CO) source;
[0503] an oxidative reactor comprising: [0504] an inlet configured
to receive ethylene from the ethylene source, [0505] an oxidative
reaction zone configured to convert at least some of the ethylene
to ethylene oxide (EO), and [0506] an outlet configured to provide
an EO stream comprising the EO;
[0507] a central reactor comprising: [0508] an inlet configured to
receive EO from the EO stream of the oxidative reactor and CO from
the CO source, [0509] a central reaction zone configured to convert
at least some of the EO to beta propiolactone (BPL), and [0510] an
outlet configured to provide a BPL stream comprising the BPL;
[0511] a first C3 reactor comprising: [0512] an inlet configured to
receive BPL from at least a portion of the BPL stream of the
central reactor, [0513] a first C3 reaction zone configured to
convert at least some of the BPL to a polypropiolactone (PPL), and
[0514] an outlet configured to provide a PPL stream comprising the
PPL;
[0515] a second C3 reactor comprising; [0516] an inlet configured
to receive PPL from the PPL stream of the first C3 reactor, [0517]
a second C3 reaction zone configured to convert at least some of
the PPL to AA, and [0518] an outlet configured to provide an AA
stream comprising the AA;
[0519] a first C4 reactor comprising: [0520] an inlet configured to
receive BPL from at least a portion of the BPL stream of the
central reactor, and carbon monoxide from the CO source, [0521] a
first C4 reaction zone configured to convert at least some of the
BPL to succinic anhydride (SA), and [0522] an outlet configured to
provide a succinic anhydride stream comprising the succinic
anhydride; and
[0523] a controller to independently modulating production of the
EO, BPL, PPL, AA, and SA.
[0524] In some variations, the system is configured to
simultaneously produce the PPL stream, the AA stream, and the SA
stream. In certain variations, the controller modulates a ratio of
PPL:AA:SA from the PPL stream, the AA stream, and the SA stream. In
certain variations where the inlet of the second C3 reactor is
configured to receive PPL from a fraction of the PPL stream of the
first C3 reactor, the controller modulates the fraction of the PPL
stream that is received by the inlet of the second C3 reactor.
[0525] In some variations of the foregoing system, the system
further comprises:
[0526] a hydrogen source; and
[0527] a second C4 reactor comprising: [0528] an inlet configured
to receive SA from the SA stream of the first C4 reactor, [0529] a
hydrogen inlet fed from the hydrogen source, [0530] a second C4
reaction zone configured to hydrogenate at least a portion of the
SA to provide a C4 product stream comprising 1,4 butanediol (BDO),
tetrahydrofuran (THF), or gamma butyrolactone (GBL), or any
combinations thereof.
[0531] In some variations of the foregoing, the controller is
configured to further modulate production of BDO, THF, and GBL.
[0532] In yet another embodiment, provided is an integrated system
to produce PPL, AA and acrylate ester. Thus, in yet another
variation, provided is a system, comprising:
[0533] an ethylene source;
[0534] a carbon monoxide (CO) source;
[0535] an alcohol source;
[0536] an oxidative reactor comprising: [0537] an inlet configured
to receive ethylene from the ethylene source, [0538] an oxidative
reaction zone configured to convert at least some of the ethylene
to ethylene oxide (EO), and [0539] an outlet configured to provide
an EO stream comprising the EO,
[0540] a central reactor comprising: [0541] an inlet configured to
receive EO from the EO stream of the oxidative reactor and at least
a portion of CO from the CO source, [0542] a central reaction zone
configured to convert at least some of the EO to beta propiolactone
(BPL), and [0543] an outlet configured to provide a BPL stream
comprising the BPL;
[0544] a first C3 reactor comprising: [0545] an inlet configured to
receive BPL from at least a portion of the BPL stream of the
central reactor, [0546] a first C3 reaction zone configured to
convert at least some of the BPL to a polypropiolactone (PPL), and
[0547] an outlet configured to provide a PPL stream comprising the
PPL;
[0548] a second C3 reactor comprising; [0549] an inlet configured
to receive BPL from the BPL stream of the central reactor, [0550] a
second C3 reaction zone configured to convert at least some of the
BPL to AA, and [0551] an outlet configured to provide an AA stream
comprising the AA;
[0552] a third C3 reactor comprising: [0553] an inlet configured to
receive BPL from at least a portion of the BPL stream of the
central reactor, and an alcohol from the alcohol source, [0554] a
third C3 reaction zone configured to convert at least some of the
BPL to acrylate esters, and [0555] an outlet configured to provide
an acrylate ester stream comprising the acrylate esters;
[0556] a first C4 reactor comprising: [0557] an inlet configured to
receive BPL from at least a portion of the BPL stream of the
central reactor, and at least a portion of CO from the CO source,
[0558] a first C4 reaction zone configured to convert at least some
of the BPL to succinic anhydride (SA), and [0559] an outlet
configured to provide a SA stream comprising the succinic
anhydride; and
[0560] a controller to independently modulating production of the
EO, BPL, PPL, AA, acrylate esters, and SA.
[0561] In some variations, the system is configured to
simultaneously produce the PPL stream, the AA stream, and the
acrylate ester stream. In some variations, the system is configured
to simultaneously produce the PPL stream, the AA stream, the
acrylate ester stream, and the SA stream. In certain variations,
the controller modulates a ratio PPL:AA:acrylate ester from the PPL
stream, the AA stream, and the acrylate ester stream. In certain
variations, the controller modulates a ratio PPL:AA:acrylate
ester:SA from the PPL stream, the AA stream, the acrylate ester
stream, and the SA stream.
[0562] In some variations of the foregoing system, the system
further comprises:
[0563] a hydrogen source;
[0564] a second C4 reactor comprising: [0565] at least one inlet
configured to receive SA from the SA stream of the first C4
reactor, and hydrogen from the hydrogen source, [0566] a second C4
reaction zone configured to hydrogenate at least a portion of the
SA to provide a C4 product stream comprising 1,4 butanediol (BDO),
tetrahydrofuran (THF), or gamma butyrolactone (GBL), or any
combinations thereof.
[0567] In certain variations, the controller is configured to
further modulate production of BDO, THF, and GBL.
[0568] In some variations of the systems described herein wherein
PPL is produced, the system further comprises:
[0569] a PPL isolation unit comprising: [0570] a PPL processing
unit, [0571] a PPL packaging unit, and [0572] a PPL outlet
configured to provide packaged PPL for distribution.
[0573] It should generally be understood that reference to "a first
reaction zone" and "a second reaction zone", etc. or "a first
reactor" and "a second reactor", etc., or "a first stream" and "a
second stream", etc., or "a first product" and "a second product",
etc., does not necessarily imply an order of the reaction zones,
reactors, streams, or products. In some variations, the use of such
references denotes the number of reaction zones, reactors, streams,
or products present. In other variations, an order may be implied
by the context in which the reaction zones, reactors, streams, or
products are configured, used or present.
[0574] The sections below more fully describe elements of the
integrated systems and methods as well as some of the reactions and
conditions for effecting the conversion of epoxides to multiple
C.sub.3 and/or C.sub.4 products.
Controller
[0575] The controller can be any integrated means (e.g., a
computer-based network) to monitor, control and/or modulate (e.g.,
increase, decrease or maintain) all processes and components
related to the disclosed system, including all reaction zones (via
sensors, switches, valves, vacuum, pumps etc.). The controller can
independently modulate production of the beta lactone by the
central reactor, production of the epoxide in an oxidative reactor,
if present, and production for each of the products, in their
respective reactors, by, e.g., independently controlling
temperatures and pressures in each reaction zone and flow rates for
inlet and outlet streams.
[0576] In some embodiments, the controller is used to increase,
decrease or maintain production of the epoxide by the oxidative
reactor, and independently increase, decrease or maintain
production of the beta lactone by the central reactor, and
independently increase, decrease or maintain production of the
first C.sub.3 product by the first C.sub.3 reactor, and
independently increase, decrease or maintain production of the
second C.sub.3 product by the second C.sub.3 reactor, and
independently increase, decrease or maintain production of the
first C.sub.4 product by the first C.sub.4 reactor, etc. In some
embodiments, the controller is used to maintain production of the
epoxide and beta lactone, and independently increase and or
decrease production of the first C.sub.3 product, second C.sub.3
product and first C.sub.4 product, etc.
Alkene to Epoxide
[0577] In certain embodiments, ethylene oxide (EO) is the epoxide.
The disclosed system optionally further includes, at its upstream
end, an oxidative reactor that produces EO on-site and provides EO
to the central reactor. In certain embodiments, EO is obtained
directly from the gas phase oxidation of ethylene. This embodiment
is advantageous in that it avoids the need to isolate, store, and
transport ethylene oxide which is both toxic and explosive. In
certain embodiments, the ethylene oxide is maintained in the gas
phase as produced and fed to the central reactor without condensing
it to a liquid.
[0578] Another benefit of producing EO on-site includes a
considerable increase in the plant's capacity to produce greater
quantities of C.sub.3 and/or C.sub.4 products. In certain
embodiments, the system can produce any combination of C.sub.3
and/or C.sub.4 products at a rate of about 200, 250, 300, 350, 400,
450, 500, 550, 600, 650, 700, 750, 800, 850, 900, 950, 1,000
kilotons per annum (kta), or within a range including any two of
these values.
[0579] Thus, in certain embodiments, the system further comprises
an oxidative reactor, comprising an inlet fed by ethylene, an
oxidative reaction zone that converts at least some of the ethylene
to EO, and an outlet which provides an outlet stream comprising the
EO, which is fed to the inlet of the central reactor.
[0580] Alternatively, in other embodiments, EO is not produced
within the disclosed system. Rather, in such embodiments, an
upstream oxidative reactor is absent and the central reactor is fed
EO that was produced off-site.
Epoxide to Lactone
[0581] In certain embodiments, the disclosed system includes a
central reactor for carbonylation of an epoxide into beta lactone
via a "carbonylation reaction." The central reactor receives a
gaseous mixture containing the epoxide (e.g., from the epoxide
source) and CO (e.g., from the CO source), as well as the
carbonylation catalyst and solvents, etc. and carries out the
carbonylation reaction of the epoxide in the central reaction zone.
In certain embodiments, the epoxide is EO and the beta lactone is
BPL. In certain embodiments, the carbonylation reaction is
continuous. Such continuous carbonylation reactions can be
conducted in a continuous stirred tank reactor or a plug flow
reactor such that BPL solution is withdrawn at essentially the same
rate it is formed.
[0582] In certain embodiments, the carbonylation reaction proceeds
as shown below where the epoxide is EO and the carbonylation
product is BPL:
##STR00001##
[0583] In certain embodiments, the carbonylation reaction proceeds
as shown below where the epoxide is propylene oxide and the
carbonylation product is beta butyrolactone:
##STR00002##
[0584] In certain embodiments, the carbonylation reaction proceeds
as shown below:
##STR00003##
where, R.sup.1 is selected from the group consisting of --H and
C.sub.1-6 aliphatic.
[0585] Carbonylation Reaction Conditions
[0586] Methods of making BPL are known in the art and include those
described in WO2013/063191 and WO2014/004858. Suitable catalysts
and reaction conditions for effecting the above reactions are
described herein and also disclosed in published PCT applications:
WO2003/050154, WO2004/089923, WO2012/158573, WO2010/118128,
WO2013/063191, and WO2014/008232; in U.S. Pat. Nos. 5,359,081 and
5,310,948 and in the publication "Synthesis of beta-Lactones" J.
AM. CHEM. SOC., vol. 124, 2002, pages 1174-1175.
[0587] In certain embodiments, the central reactor, comprising an
inlet, is fed by a "reaction stream" comprising the epoxide and
carbon monoxide (CO). In certain embodiments, the reaction stream
fed into the carbonylation reaction comprises a gaseous mixture
containing epoxide and CO. In certain embodiments, the molar ratio
of CO to epoxide in the reaction stream ranges from about 1:1 to
about 10,000:1. In certain embodiments, the molar ratio of CO to
epoxide in the reaction stream is about 5000:1, is about 2500:1, is
about 2000:1, is about 1500:1, is about 1000:1, is about 500:1, is
about 1:500, is about 200:1, is about 100:1, is about 50:1, is
about 20:1, is about 10:1, is about 5:1 or is about 1:1, or within
a range including any two of these ratios.
[0588] In certain embodiments, the reaction stream further
comprises one or more additional components. In certain
embodiments, the additional components comprise diluents which do
not directly participate in the chemical reactions of the epoxide
or its derivatives. In certain embodiments, such diluents may
include one or more inert gases (e.g., nitrogen, argon, helium and
the like) or volatile organic molecules such as hydrocarbons,
ethers, and the like. In certain embodiments, the reaction stream
may comprise hydrogen, traces of carbon dioxide, methane, and other
compounds commonly found in industrial CO streams. In certain
embodiments, the feed stream may further comprise materials that
may have a direct or indirect chemical function in one or more of
the processes involved in the conversion of the epoxide to various
end products. Additional reactants can also include mixtures of CO
and another gas. For example, as noted above, In certain
embodiments, CO is provided in a mixture with hydrogen (e.g.,
Syngas).
[0589] In certain embodiments, the reaction stream is characterized
in that it is essentially free of oxygen. In certain embodiments,
the reaction stream is characterized in that it is essentially free
of water. In certain embodiments, the reaction stream is
characterized in that it is essentially free of oxygen and
water.
[0590] Carbonylation Solvents
[0591] In certain embodiments, the carbonylation reaction described
herein is performed in a solvent. In certain embodiments, the
solvent is fed to the central reaction zone as a separate stream.
In other embodiments, the solvent may be fed to the central
reaction zone along with the catalyst, the epoxide or another feed
stream entering the carbonylation reaction in the central reaction
zone. In certain embodiments, the solvent enters the central
reaction zone along with the carbonylation catalyst which is
provided as a catalyst solution in the solvent. In certain
embodiments, the solvent enters the central reaction zone in two or
more separate feed streams. In embodiments where solvent is present
in the central reaction zone, it is also present in the
carbonylation outlet stream.
[0592] The solvent may be selected from any solvent, and mixtures
of solvents. Additionally, beta lactone may be utilized as a
co-solvent. Solvents most suitable for the methods include ethers,
hydrocarbons and non protic polar solvents. Examples of suitable
solvents include, for example, tetrahydrofuran ("THF"), sulfolane,
N-methyl pyrrolidone, 1,3 dimethyl-2-imidazolidinone, diglyme,
triglyme, tetraglyme, diethylene glycol dibutyl ether, isosorbide
ethers, methyl tertbutyl ether, diethylether, diphenyl ether,
1,4-dioxane, ethylene carbonate, propylene carbonate, butylene
carbonate, dibasic esters, diethyl ether, acetonitrile, ethyl
acetate, dimethoxy ethane, acetone, and methylethyl ketone.
[0593] In certain embodiments, the carbonylation reaction further
includes a Lewis base additive to the carbonylation reaction in the
central reaction zone. In some embodiments such Lewis base
additives can stabilize or reduce deactivation of the catalysts. In
certain embodiments, the Lewis base additive is selected from the
group consisting of phosphines, amines, guanidines, amidines, and
nitrogen-containing heterocycles. In certain embodiments, the Lewis
base additive is a hindered amine base. In certain embodiments, the
Lewis base additive is a 2,6-lutidine; imidazole,
1-methylimidazole, 4-dimethylaminopyridine, trihexylamine or
triphenylphosphine.
[0594] Carbonylation Catalyst
[0595] Numerous carbonylation catalysts known in the art are
suitable for (or can be adapted to) methods described herein. For
example, in some embodiments, the carbonylation methods utilize a
metal carbonyl-Lewis acid catalyst such as those described in U.S.
Pat. No. 6,852,865. In other embodiments, the carbonylation is
performed with one or more of the carbonylation catalysts disclosed
in U.S. patent application Ser. No. 10/820,958; and Ser. No.
10/586,826. In other embodiments, the carbonylation is performed
with one or more of the catalysts disclosed in U.S. Pat. Nos.
5,310,948; 7,420,064; and 5,359,081. Additional catalysts for the
carbonylation of epoxides are discussed in a review in Chem.
Commun., 2007, 657-674.
[0596] In some embodiments, the carbonylation catalyst includes a
metal carbonyl compound. Typically, a single metal carbonyl
compound is provided, but in some embodiments, mixtures of two or
more metal carbonyl compounds are provided. Thus, when a provided
metal carbonyl compound "comprises", e.g., a neutral metal carbonyl
compound, it is understood that the provided metal carbonyl
compound can be a single neutral metal carbonyl compound, or a
neutral metal carbonyl compound in combination with one or more
metal carbonyl compounds. Preferably, the provided metal carbonyl
compound is capable of ring-opening an epoxide and facilitating the
insertion of CO into the resulting metal carbon bond. Metal
carbonyl compounds with this reactivity are well known in the art
and are used for laboratory experimentation as well as in
industrial processes such as hydroformylation.
[0597] In some embodiments, a provided metal carbonyl compound
comprises an anionic metal carbonyl moiety. In other embodiments, a
provided metal carbonyl compound comprises a neutral metal carbonyl
compound. In some embodiments, a provided metal carbonyl compound
comprises a metal carbonyl hydride or a hydrido metal carbonyl
compound. In some embodiments, a provided metal carbonyl compound
acts as a pre-catalyst which reacts in situ with one or more
reaction components to provide an active species different from the
compound initially provided. Such pre-catalysts are specifically
encompassed as it is recognized that the active species in a given
reaction may not be known with certainty; thus the identification
of such a reactive species in situ does not itself depart from the
spirit or teachings herein.
[0598] In certain embodiments, the hydrido metal carbonyl (either
as provided or generated in situ) comprises one or more of
HCo(CO).sub.4, HCoQ(CO).sub.3, HMn(CO).sub.5, HMn(CO).sub.4Q,
HW(CO).sub.3Q, HRe(CO).sub.5, HMo(CO).sub.3Q, HOs(CO).sub.2Q,
HMo(CO).sub.2Q.sub.2, HFe(CO.sub.2)Q, HW(CO).sub.2Q.sub.2,
HRuCOQ.sub.2, H.sub.2Fe(CO).sub.4 or H.sub.2Ru(CO).sub.4, where
each Q is independently as defined above and in the classes and
subclasses herein. In certain embodiments, the metal carbonyl
hydride (either as provided or generated in situ) comprises
HCo(CO).sub.4. In certain embodiments, the metal carbonyl hydride
(either as provided or generated in situ) comprises
HCo(CO).sub.3PR.sub.3, where each R is independently an optionally
substituted aryl group, an optionally substituted C.sub.1-20
aliphatic group, an optionally substituted C.sub.1-10 alkoxy group,
or an optionally substituted phenoxy group. In certain embodiments,
the metal carbonyl hydride (either as provided or generated in
situ) comprises HCo(CO).sub.3cp, where cp represents an optionally
substituted pentadienyl ligand. In certain embodiments, the metal
carbonyl hydride (either as provided or generated in situ)
comprises HMn(CO).sub.5. In certain embodiments, the metal carbonyl
hydride (either as provided or generated in situ) comprises
H.sub.2Fe(CO).sub.4.
[0599] In some embodiments, the metal carbonyl compound comprises
an anionic metal carbonyl species. In some embodiments, such
anionic metal carbonyl species have the general formula
[Q.sub.dM'.sub.e(CO).sub.w].sup.y-, where Q is any ligand and need
not be present, M' is a metal atom, d is an integer between 0 and 8
inclusive, e is an integer between 1 and 6 inclusive, w is a number
such as to provide the stable anionic metal carbonyl complex, and y
is the charge of the anionic metal carbonyl species. In some
embodiments, the anionic metal carbonyl has the general formula
[QM'(CO).sub.w].sup.y-, where Q is any ligand and need not be
present, M' is a metal atom, w is a number such as to provide the
stable anionic metal carbonyl, and y is the charge of the anionic
metal carbonyl.
[0600] In some embodiments, the anionic metal carbonyl species
include monoanionic carbonyl complexes of metals from groups 5, 7
or 9 of the periodic table or dianionic carbonyl complexes of
metals from groups 4 or 8 of the periodic table. In some
embodiments, the anionic metal carbonyl compound contains cobalt or
manganese. In some embodiments, the anionic metal carbonyl compound
contains rhodium. Suitable anionic metal carbonyl compounds
include, for example, [Co(CO).sub.4].sup.-, [Ti(CO).sub.6].sup.2-,
[V(CO).sub.6].sup.-, [Rh(CO).sub.4].sup.-, [Fe(CO).sub.4].sup.2-,
[Ru(CO).sub.4].sup.2-, [Os(CO).sub.4].sup.2-,
[Cr.sub.2(CO).sub.10].sup.2-, [Fe.sub.2(CO).sub.8].sup.2-,
[Tc(CO).sub.5].sup.-, [Re(CO).sub.5].sup.-, and
[Mn(CO).sub.5].sup.-. In some embodiments, the anionic metal
carbonyl comprises [Co(CO).sub.4].sup.-. In some embodiments, a
mixture of two or more anionic metal carbonyl complexes may be
present in the carbonylation catalysts used in the methods.
[0601] The term "such as to provide a stable anionic metal
carbonyl" for [Q.sub.dM'.sub.e(CO).sub.w].sup.y- is used herein to
mean that [Q.sub.dM'.sub.e(CO).sub.w].sup.y- is a species that may
be characterized by analytical means, e.g., NMR, IR, X-ray
crystallography, Raman spectroscopy and/or electron spin resonance
(EPR) and isolable in catalyst form in the presence of a suitable
cation or a species formed in situ. It is to be understood that
metals which can form stable metal carbonyl complexes have known
coordinative capacities and propensities to form polynuclear
complexes which, together with the number and character of optional
ligands Q that may be present and the charge on the complex will
determine the number of sites available for CO to coordinate and
therefore the value of w. Typically, such compounds conform to the
"18-electron rule". Such knowledge is within the grasp of one
having ordinary skill in the arts pertaining to the synthesis and
characterization of metal carbonyl compounds.
[0602] In embodiments where the provided metal carbonyl compound is
an anionic species, one or more cations must also necessarily be
present. The present disclosure places no particular constraints on
the identity of such cations. In some embodiments, the cation
associated with an anionic metal carbonyl compound comprises a
reaction component of another category described herein. For
example, in some embodiments, the metal carbonyl anion is
associated with a cationic Lewis acid. In other embodiments a
cation associated with a provided anionic metal carbonyl compound
is a simple metal cation such as those from Groups 1 or 2 of the
periodic table (e.g., Na.sup.+, Li.sup.+, K.sup.+, and Mg.sup.2+).
In other embodiments a cation associated with a provided anionic
metal carbonyl compound is a bulky non electrophilic cation such as
an `onium salt` (e.g., Bu.sub.4N.sup.+, PPN.sup.+, Ph.sub.4P.sup.+,
and Ph.sub.4As.sup.+). In other embodiments, a metal carbonyl anion
is associated with a protonated nitrogen compound (e.g., a cation
may comprise a compound such as MeTBD-H.sup.+, DMAP-H.sup.+,
DABCO-H.sup.+, and DBU-H.sup.+). In some embodiments, compounds
comprising such protonated nitrogen compounds are provided as the
reaction product between an acidic hydrido metal carbonyl compound
and a basic nitrogen-containing compound (e.g., a mixture of DBU
and HCo(CO).sub.4).
[0603] In some embodiments, a catalyst utilized in the methods
described herein comprises a neutral metal carbonyl compound. In
some embodiments, such neutral metal carbonyl compounds have the
general formula Q.sub.dM'.sub.e(CO).sub.w', where Q is any ligand
and need not be present, M' is a metal atom, d is an integer
between 0 and 8 inclusive, e is an integer between 1 and 6
inclusive, and w' is a number such as to provide the stable neutral
metal carbonyl complex. In some embodiments, the neutral metal
carbonyl has the general formula QM'(CO).sub.w'. In some
embodiments, the neutral metal carbonyl has the general formula
M'(CO).sub.w'. In some embodiments, the neutral metal carbonyl has
the general formula QM'.sub.2(CO).sub.w'. In some embodiments, the
neutral metal carbonyl has the general formula M'.sub.2(CO).sub.w'.
Suitable neutral metal carbonyl compounds include, for example,
Ti(CO).sub.7, V.sub.2(CO).sub.12, Cr(CO).sub.6, Mo(CO).sub.6,
W(CO).sub.6, Mn.sub.2(CO).sub.10, Tc.sub.2(CO).sub.10,
Re.sub.2(CO).sub.10, Fe(CO).sub.5, Ru(CO).sub.5, Os(CO).sub.5,
Ru.sub.3(CO).sub.12, Os.sub.3(CO).sub.12Fe.sub.3(CO).sub.12,
Fe.sub.2(CO).sub.9, Co.sub.4(CO).sub.12, Rh.sub.4(CO).sub.12,
Rh.sub.6(CO).sub.16, Ir.sub.4(CO).sub.12, Co.sub.2(CO).sub.8, and
Ni(CO).sub.4.
[0604] The term "such as to provide a stable neutral metal
carbonyl" for Q.sub.dM'.sub.e(CO).sub.w' is used herein to mean
that Q.sub.dM'.sub.e(CO).sub.w' is a species that may be
characterized by analytical means, e.g., NMR, IR, X-ray
crystallography, Raman spectroscopy and/or electron spin resonance
(EPR) and isolable in pure form or a species formed in situ. It is
to be understood that metals which can form stable metal carbonyl
complexes have known coordinative capacities and propensities to
form polynuclear complexes which, together with the number and
character of optional ligands Q that may be present will determine
the number of sites available for CO to coordinate and therefore
the value of w'. Typically, such compounds conform to
stoichiometries conforming to the "18-electron rule". Such
knowledge is within the grasp of one having ordinary skill in the
arts pertaining to the synthesis and characterization of metal
carbonyl compounds.
[0605] In some embodiments, no ligands Q are present on the metal
carbonyl compound. In other embodiments, one or more ligands Q are
present on the metal carbonyl compound. In some embodiments, where
Q is present, each occurrence of Q is selected from the group
consisting of phosphine ligands, amine ligands, cyclopentadienyl
ligands, heterocyclic ligands, nitriles, phenols, and combinations
of two or more of these. In some embodiments, one or more of the CO
ligands of any of the metal carbonyl compounds described above is
replaced with a ligand Q. In some embodiments, Q is a phosphine
ligand. In some embodiments, Q is a triaryl phosphine. In some
embodiments, Q is trialkyl phosphine. In some embodiments, Q is a
phosphite ligand. In some embodiments, Q is an optionally
substituted cyclopentadienyl ligand. In some embodiments, Q is cp.
In some embodiments, Q is cp*. In some embodiments, Q is an amine
or a heterocycle.
[0606] In some embodiments, the carbonylation catalyst utilized in
the methods described above further includes a Lewis acidic
component. In some embodiments, the carbonylation catalyst includes
an anionic metal carbonyl complex and a cationic Lewis acidic
component. In some embodiments, the metal carbonyl complex includes
a carbonyl cobaltate and the Lewis acidic co-catalyst includes a
metal-centered cationic Lewis acid. In some embodiments, an
included Lewis acid comprises a boron compound.
[0607] In certain embodiments, for any of the metal carbonyl
compounds described above, M' comprises a transition metal. In
certain embodiments, for any of the metal carbonyl compounds
described above, M' is selected from Groups 5 (Ti) to 10 (Ni) of
the periodic table. In certain embodiments, M' is a Group 9 metal.
In certain embodiments, M' is Co. In certain embodiments, M' is Rh.
In certain embodiments, M' is Ir. In certain embodiments, M' is Fe.
In certain embodiments, M' is Mn.
[0608] In some embodiments, where an included Lewis acid comprises
a boron compound, the boron compound comprises a trialkyl boron
compound or a triaryl boron compound. In some embodiments, an
included boron compound comprises one or more boron-halogen bonds.
In some embodiments, where an included boron compound comprises one
or more boron-halogen bonds, the compound is a dialkyl halo boron
compound (e.g., R.sub.2BX), a dihalo monoalkyl compound (e.g.,
RBX.sub.2), an aryl halo boron compound (e.g., Ar.sub.2BX or
ArBX.sub.2), or a trihalo boron compound (e.g., BCl.sub.3 or
BBr.sub.3), wherein each R is an alkyl group; each X is a halogen;
and each Ar is an aromatic group.
[0609] In some embodiments, where the included Lewis acid comprises
a metal-centered cationic Lewis acid, the Lewis acid is a cationic
metal complex. In some embodiments, the cationic metal complex has
its charge balanced either in part, or wholly by one or more
anionic metal carbonyl moieties. Suitable anionic metal carbonyl
compounds include those described above. In some embodiments, there
are 1 to 17 such anionic metal carbonyls balancing the charge of
the metal complex. In some embodiments, there are 1 to 9 such
anionic metal carbonyls balancing the charge of the metal complex.
In some embodiments, there are 1 to 5 such anionic metal carbonyls
balancing the charge of the metal complex. In some embodiments,
there are 1 to 3 such anionic metal carbonyls balancing the charge
of the metal complex.
[0610] In some embodiments, where carbonylation catalysts used in
methods described herein include a cationic metal complex, the
metal complex has the formula [(L.sup.c).sub.vM.sub.b].sup.z+,
wherein: [0611] L.sup.c is a ligand where, when two or more L.sup.c
are present, each may be the same or different; [0612] M is a metal
atom where, when two M are present, each may be the same or
different; [0613] v is an integer from 1 to 4 inclusive; [0614] b
is an integer from 1 to 2 inclusive; and [0615] z is an integer
greater than 0 that represents the cationic charge on the metal
complex.
[0616] In some embodiments, provided Lewis acids conform to
structure I:
##STR00004##
wherein:
##STR00005## [0617] is a multidentate ligand; [0618] M is a metal
atom coordinated to the multidentate ligand; and [0619] a is the
charge of the metal atom and ranges from 0 to 2.
[0620] In some embodiments, provided metal complexes conform to
structure II:
##STR00006##
wherein a is as defined above (each a may be the same or
different), and [0621] M.sup.1 is a first metal atom; [0622]
M.sup.2 is a second metal atom;
[0622] ##STR00007## [0623] comprises a multidentate ligand system
capable of coordinating both metal atoms.
[0624] For sake of clarity, and to avoid confusion between the net
and total charge of the metal atoms in complexes I and II and other
structures herein, the charge (a.sup.+) shown on the metal atom in
complexes I and II above represents the net charge on the metal
atom after it has satisfied any anionic sites of the multidentate
ligand. For example, if a metal atom in a complex of formula I were
Cr(III), and the ligand were porphyrin (a tetradentate ligand with
a charge of -2), then the chromium atom would have a net charge of
+1, and a would be 1.
[0625] Suitable multidentate ligands include, for example,
porphyrin derivatives 1, salen ligands 2,
dibenzotetramethyltetraaza[14]annulene (tmtaa) ligands 3,
phthalocyaninate ligands 4, the Trost ligand 5,
tetraphenylporphyrin ligands 6, and corrole ligands 7. In some
embodiments, the multidentate ligand is a salen ligand. In other
embodiments, the multidentate ligand is a porphyrin ligand. In
other embodiments, the multidentate ligand is a
tetraphenylporphyrin ligand. In other embodiments, the multidentate
ligand is a corrole ligand. Any of the foregoing ligands can be
unsubstituted or can be substituted. Numerous variously substituted
analogs of these ligands are known in the art and will be apparent
to the skilled artisan.
##STR00008## ##STR00009##
wherein each of R.sup.c, R.sup.d, R.sup.1a, R.sup.2a, R.sup.3a,
R.sup.4a, R.sup.1a', R.sup.2a', R.sup.3a', and M, is as defined and
described in the classes and subclasses herein.
[0626] In some embodiments, Lewis acids provided carbonylation
catalysts used in methods described herein comprise
metal-porphinato complexes. In some embodiments, the moiety
##STR00010##
has the structure:
##STR00011##
wherein:
[0627] each of M and a is as defined above and described in the
classes and subclasses herein, and
[0628] R.sup.d at each occurrence is independently hydrogen,
halogen, --OR.sup.4, --NR.sup.y.sub.2, --SR.sup.y, --CN,
--NO.sub.2, --SO.sub.2R.sup.y, --SOR.sup.y,
--SO.sub.2NR.sup.y.sub.2; --CNO, --NR.sup.ySO.sub.2R.sup.y, --NCO,
--N.sub.3, --SiR.sup.y.sub.3; or an optionally substituted group
selected from the group consisting of C.sub.1-20 aliphatic;
C.sub.1-20 heteroaliphatic having 1-4 heteroatoms independently
selected from the group consisting of nitrogen, oxygen, and sulfur;
6- to 10-membered aryl; 5- to 10-membered heteroaryl having 1-4
heteroatoms independently selected from nitrogen, oxygen, and
sulfur; and 4- to 7-membered heterocyclic having 1-2 heteroatoms
independently selected from the group consisting of nitrogen,
oxygen, and sulfur, where two or more R.sup.d groups may be taken
together to form one or more optionally substituted rings;
[0629] each R.sup.y is independently hydrogen, an optionally
substituted group selected the group consisting of acyl; carbamoyl,
arylalkyl; 6- to 10-membered aryl; C1-12 aliphatic; C.sub.1-12
heteroaliphatic having 1-2 heteroatoms independently selected from
the group consisting of nitrogen, oxygen, and sulfur; 5- to
10-membered heteroaryl having 1-4 heteroatoms independently
selected from the group consisting of nitrogen, oxygen, and sulfur;
4- to 7-membered heterocyclic having 1-2 heteroatoms independently
selected from the group consisting of nitrogen, oxygen, and sulfur;
an oxygen protecting group; and a nitrogen protecting group; two
R.sup.y on the same nitrogen atom are taken with the nitrogen atom
to form an optionally substituted 4- to 7-membered heterocyclic
ring having 0-2 additional heteroatoms independently selected from
the group consisting of nitrogen, oxygen, and sulfur; and
[0630] each R.sup.4 is independently is a hydroxyl protecting group
or R.sup.y.
[0631] In some embodiments, the moiety
##STR00012##
has the structure:
##STR00013##
where M, a and R.sup.d are as defined above and in the classes and
subclasses herein.
[0632] In some embodiments, the moiety
##STR00014##
has the structure:
##STR00015##
where M, a and R.sup.d are as defined above and in the classes and
subclasses herein.
[0633] In some embodiments, Lewis acids included in carbonylation
catalysts used in methods described herein comprise metallo
salenate complexes. In some embodiments, the moiety
##STR00016##
has the structure:
##STR00017##
wherein: [0634] M, and a are as defined above and in the classes
and subclasses herein. [0635] R.sup.1a, R.sup.1a', R.sup.2a,
R.sup.2a', R.sup.3a, and R.sup.3a' are independently hydrogen,
halogen, --OR.sup.4, --NR.sup.y.sub.2, --SR.sup.y, --CN,
--NO.sub.2, --SO.sub.2R, --SOR.sup.y, --SO.sub.2NR.sup.y.sub.2;
--CNO, --NR.sup.ySO.sub.2R, --NCO, --N.sub.3, --SiR.sup.y.sub.3; or
an optionally substituted group selected from the group consisting
of C.sub.1-20 aliphatic; C.sub.1-20 heteroaliphatic having 1-4
heteroatoms independently selected from the group consisting of
nitrogen, oxygen, and sulfur; 6- to 10-membered aryl; 5- to
10-membered heteroaryl having 1-4 heteroatoms independently
selected from nitrogen, oxygen, and sulfur; and 4- to 7-membered
heterocyclic having 1-2 heteroatoms independently selected from the
group consisting of nitrogen, oxygen, and sulfur; wherein each
R.sup.4, and R.sup.y is independently as defined above and
described in classes and subclasses herein, [0636] wherein any of
(R.sup.2a' and R.sup.3a'), (R.sup.2a and R.sup.3a), (R.sup.1a and
R.sup.2a), and (R.sup.1a' and R.sup.2a') may optionally be taken
together with the carbon atoms to which they are attached to form
one or more rings which may in turn be substituted with one or more
R.sup.y groups; and [0637] R.sup.4a is selected from the group
consisting of: [0638] e)
[0638] ##STR00018## [0639] f)
[0639] ##STR00019## [0640] g)
##STR00020##
[0640] and [0641] h)
##STR00021##
[0641] where [0642] R.sup.c at each occurrence is independently
hydrogen, halogen, --OR.sup.4, --NR.sup.y.sub.2, --SR.sup.y, --CN,
--NO.sub.2, --SO.sub.2R, --SOR.sup.y, --SO.sub.2NR.sup.y.sub.2;
--CNO, --NR.sup.ySO.sub.2R, --NCO, --N.sub.3, --SiR.sub.3; or an
optionally substituted group selected from the group consisting of
C.sub.1-20 aliphatic; C.sub.1-20 heteroaliphatic having 1-4
heteroatoms independently selected from the group consisting of
nitrogen, oxygen, and sulfur; 6- to 10-membered aryl; 5- to
10-membered heteroaryl having 1-4 heteroatoms independently
selected from nitrogen, oxygen, and sulfur; and 4- to 7-membered
heterocyclic having 1-2 heteroatoms independently selected from the
group consisting of nitrogen, oxygen, and sulfur; where: [0643] two
or more R.sup.c groups may be taken together with the carbon atoms
to which they are attached and any intervening atoms to form one or
more rings; [0644] when two R.sup.c groups are attached to the same
carbon atom, they may be taken together along with the carbon atom
to which they are attached to form a moiety selected from the group
consisting of: a 3- to 8-membered spirocyclic ring, a carbonyl, an
oxime, a hydrazone, an imine; and an optionally substituted alkene;
where R.sup.4 and R.sup.y are as defined above and in classes and
subclasses herein; [0645] Y is a divalent linker selected from the
group consisting of: --NR.sup.y--, --N(R.sup.y)C(O)--,
--C(O)NR.sup.y--, --O--, --C(O)--, --OC(O)--, --C(O)O--, --S--,
--SO--, --SO.sub.2--, --C(.dbd.S)--, --C(.dbd.NR.sup.y)--,
--N.dbd.N--; a polyether; a C.sub.3 to C.sub.8 substituted or
unsubstituted carbocycle; and a C.sub.1 to C.sub.8 substituted or
unsubstituted heterocycle; [0646] m' is 0 or an integer from 1 to
4, inclusive; [0647] q is 0 or an integer from 1 to 4, inclusive;
and [0648] x is 0, 1, or 2.
[0649] In some embodiments, a provided Lewis acid comprises a
metallo salen compound, as shown in formula Ia:
##STR00022##
[0650] wherein each of M, R.sup.d, and a, is as defined above and
in the classes and subclasses herein,
##STR00023##
represents is an optionally substituted moiety linking the two
nitrogen atoms of the diamine portion of the salen ligand,
where
##STR00024##
is selected from the group consisting of a C.sub.3-C.sub.14
carbocycle, a C.sub.6-C.sub.10 aryl group, a C.sub.3-C.sub.14
heterocycle, and a C.sub.5-C.sub.10 heteroaryl group; or an
optionally substituted C.sub.2-20 aliphatic group, wherein one or
more methylene units are optionally and independently replaced by
--NR.sup.y--, --N(R.sup.y)C(O)--, --C(O)N(R.sup.y)--,
--OC(O)N(R.sup.y)--, --N(R.sup.y)C(O)O--, --OC(O)O--, --O--,
--C(O)--, --OC(O)--, --C(O)O--, --S--, --SO--, --SO.sub.2--,
--C(.dbd.S)--, --C(.dbd.NR.sup.y)--, --C(.dbd.NOR.sup.y)-- or
--N.dbd.N--.
[0651] In some embodiments metal complexes having formula Ia above,
at least one of the phenyl rings comprising the
salicylaldehyde-derived portion of the metal complex is
independently selected from the group consisting of:
##STR00025## ##STR00026## ##STR00027## ##STR00028##
##STR00029##
[0652] In some embodiments, a provided Lewis acid comprises a
metallo salen compound, conforming to one of formulae Va or Vb:
##STR00030##
[0653] where M, a, R.sup.d, R.sup.1a, R.sup.3a, R.sup.1a',
R.sup.3a', and
##STR00031##
are as defined above and in the classes and subclasses herein.
[0654] In some embodiments of metal complexes having formulae Va or
Vb, each R.sup.1a and R.sup.3a is, independently, optionally
substituted C.sub.1-C.sub.20 aliphatic.
[0655] In some embodiments, the moiety
##STR00032##
comprises an optionally substituted 1,2-phenyl moiety.
[0656] In some embodiments, Lewis acids included in carbonylation
catalysts used in methods described herein comprise metal-tmtaa
complexes. In some embodiments, the moiety
##STR00033##
has the structure:
##STR00034##
where M, a and R.sup.d are as defined above and in the classes and
subclasses herein, and
[0657] R.sup.e at each occurrence is independently hydrogen,
halogen, --OR, --NR.sup.y.sub.2, --SR.sup.y, --CN, --NO.sub.2,
--SO.sub.2R.sup.y, --SOR.sup.y, --SO.sub.2NR.sup.y.sub.2; --CNO,
--NR.sup.ySO.sub.2R.sup.y, --NCO, --N.sub.3, --SiR.sup.y.sub.3; or
an optionally substituted group selected from the group consisting
of C.sub.1-20 aliphatic; C.sub.1-20 heteroaliphatic having 1-4
heteroatoms independently selected from the group consisting of
nitrogen, oxygen, and sulfur; 6- to 10-membered aryl; 5- to
10-membered heteroaryl having 1-4 heteroatoms independently
selected from nitrogen, oxygen, and sulfur; and 4- to 7-membered
heterocyclic having 1-2 heteroatoms independently selected from the
group consisting of nitrogen, oxygen, and sulfur.
[0658] In some embodiments, the moiety
##STR00035##
has the structure:
##STR00036##
where each of M, a, R.sup.c and R.sup.d is as defined above and in
the classes and subclasses herein.
[0659] In some embodiments, where carbonylation catalysts used in
methods described herein include a Lewis acidic metal complex, the
metal atom is selected from the periodic table groups 2-13,
inclusive. In some embodiments, M is a transition metal selected
from the periodic table groups 4, 6, 11, 12 and 13. In some
embodiments, M is aluminum, chromium, titanium, indium, gallium,
zinc cobalt, or copper. In some embodiments, M is aluminum. In
other embodiments, M is chromium.
[0660] In some embodiments, M has an oxidation state of +2. In some
embodiments, M is Zn(II), Cu(II), Mn(II), Co(II), Ru(II), Fe(II),
Co(II), Rh(II), Ni(II), Pd(II) or Mg(II). In some embodiments M is
Zn(II). In some embodiments M is Cu(II).
[0661] In some embodiments, M has an oxidation state of +3. In some
embodiments, M is Al(III), Cr(III), Fe(III), Co(III), Ti(III)
In(III), Ga(III) or Mn(III). In some embodiments M is Al(III). In
some embodiments M is Cr(III).
[0662] In some embodiments, M has an oxidation state of +4. In some
embodiments, M is Ti(IV) or Cr(IV).
[0663] In some embodiments, M.sup.1 and M.sup.2 are each
independently a metal atom selected from the periodic table groups
2-13, inclusive. In some embodiments, M is a transition metal
selected from the periodic table groups 4, 6, 11, 12 and 13. In
some embodiments, M is aluminum, chromium, titanium, indium,
gallium, zinc cobalt, or copper. In some embodiments, M is
aluminum. In other embodiments, M is chromium. In some embodiments,
M.sup.1 and M.sup.2 are the same. In some embodiments, M.sup.1 and
M.sup.2 are the same metal, but have different oxidation states. In
some embodiments, M.sup.1 and M.sup.2 are different metals.
[0664] In some embodiments, one or more of M.sup.1 and M.sup.2 has
an oxidation state of +2. In some embodiments, M.sup.1 is Zn(II),
Cu(II), Mn(II), Co(II), Ru(II), Fe(II), Co(II), Rh(II), Ni(II),
Pd(II) or Mg(II). In some embodiments M.sup.1 is Zn(II). In some
embodiments M.sup.1 is Cu(II). In some embodiments, M.sup.2 is
Zn(II), Cu(II), Mn(II), Co(II), Ru(II), Fe(II), Co(II), Rh(II),
Ni(II), Pd(II) or Mg(II). In some embodiments M.sup.2 is Zn(II). In
some embodiments M.sup.2 is Cu(II).
[0665] In some embodiments, one or more of M.sup.1 and M.sup.2 has
an oxidation state of +3. In some embodiments, M.sup.1 is Al(III),
Cr(III), Fe(III), Co(III), Ti(III) In(III), Ga(III) or Mn(III). In
some embodiments M.sup.1 is Al(III). In some embodiments M.sup.1 is
Cr(III). In some embodiments, M.sup.2 is Al(III), Cr(III), Fe(III),
Co(III), Ti(III) In(III), Ga(III) or Mn(III). In some embodiments
M.sup.2 is Al(III). In some embodiments M.sup.2 is Cr(III).
[0666] In some embodiments, one or more of M.sup.1 and M.sup.2 has
an oxidation state of +4. In some embodiments, M.sup.1 is Ti(IV) or
Cr(IV). In some embodiments, M.sup.2 is Ti(IV) or Cr(IV).
[0667] In some embodiments, the metal-centered Lewis-acidic
component of the carbonylation catalyst includes a dianionic
tetradentate ligand. In some embodiments, the dianionic
tetradentate ligand is selected from the group consisting of:
porphyrin ligands; salen ligands;
dibenzotetramethyltetraaza[14]annulene (tmtaa) ligands;
phthalocyaninate ligands; and the Trost ligand.
[0668] In some embodiments, the carbonylation catalyst includes a
carbonyl cobaltate in combination with an aluminum porphyrin
compound. In some embodiments, the carbonylation catalyst is
[(TPP)Al(THF).sub.2][Co(CO).sub.4], where TPP stands for
tetraphenylporphyrin and THF stands for tetrahydrofuran.
[0669] In some embodiments, the carbonylation catalyst includes a
carbonyl cobaltate in combination with a chromium porphyrin
compound.
[0670] In some embodiments, the carbonylation catalyst includes a
carbonyl cobaltate in combination with a chromium salen compound.
In some embodiments, the carbonylation catalyst includes a carbonyl
cobaltate in combination with a chromium salophen compound.
[0671] In some embodiments, the carbonylation catalyst includes a
carbonyl cobaltate in combination with an aluminum salen compound.
In some embodiments, the carbonylation catalyst includes a carbonyl
cobaltate in combination with an aluminum salophen compound.
[0672] In some embodiments, one or more neutral two electron donors
coordinate to M M.sup.1 or M.sup.2 and fill the coordination
valence of the metal atom. In some embodiments, the neutral two
electron donor is a solvent molecule. In some embodiments, the
neutral two electron donor is an ether. In some embodiments, the
neutral two electron donor is tetrahydrofuran, diethyl ether,
acetonitrile, carbon disulfide, or pyridine. In some embodiments,
the neutral two electron donor is tetrahydrofuran. In some
embodiments, the neutral two electron donor is an epoxide. In some
embodiments, the neutral two electron donor is an ester or a
lactone.
C.sub.3 and/or C.sub.4 Products
[0673] Once the beta lactone, such as BPL, is produced within the
central reactor, it can be distributed, e.g., fed into two or more
of a first C.sub.3 reactor, a second C.sub.3 reactor, and a first
C.sub.4 reactor, etc., where the beta lactone is subjected to
conditions that convert it to two or more of a first C.sub.3
product, a second C.sub.3 product, and a first C.sub.4 product.
This reaction stage is alternately referred to herein as the beta
lactone conversion stage.
[0674] As used herein the term "C.sub.3 reactor" refers to a
chemical reactor and related components that convert the beta
lactone, such as BPL, into the "C.sub.3 product" which means a
compound or polymer that includes a three-carbon chain.
Representative examples of C.sub.3 products include
polypropiolactone (PPL), polyacrylic acid, an
.alpha.,.beta.-unsaturated acid, such as acrylic acid, an
.alpha.,.beta.-unsaturated ester, an .alpha.,.beta.-unsaturated
amide or 1,3-propanediol (PDO).
[0675] As used herein the term "C.sub.4 reactor" refers to a
chemical reactor and its related components that convert the beta
lactone, e.g., BPL, into the "C.sub.4 product" which means a
compound or polymer that includes a four-carbon chain.
Representative examples of C.sub.4 products include succinic
anhydride, succinic acid, 1,4 butanediol (BDO), tetrahydrofuran
(THF) or gamma butyrolactone (GBL).
[0676] The disclosed systems may produce C.sub.3 and/or C.sub.4
products. In certain embodiments, the system comprises the first
C.sub.3 reactor and the first C.sub.4 reactor for the production of
at least one C.sub.3 product and at least one C.sub.4 product. In
some embodiments, the disclosed systems produce at least a first
C.sub.3 product and at least a first C.sub.4 product, each of which
is formed from the beta lactone (e.g., BPL).
[0677] In some embodiments, the disclosed systems produce at least
a first C.sub.3 selected from the group consisting of an
.alpha.,.beta.-unsaturated acid, such as AA, an
.alpha.,.beta.-unsaturated ester, an .alpha.,.beta.-unsaturated
amide, PPL, polyacrylic acid and PDO and at least a first C.sub.4
product, succinic anhydride, each of which is formed from BPL.
Lactone to C.sub.3 Products
[0678] In certain embodiments, the system comprises the first
C.sub.3 reactor and the second C.sub.3 reactor for the production
of at least two or more C.sub.3 products which differ from one
another. As such, at least two distinct C.sub.3 products are formed
from the beta lactone (e.g., BPL). For example, a first C.sub.3
product may be PPL, whereas a second C.sub.3 product may be AA.
Alternatively, a first C.sub.3 product may be AA, whereas a second
C.sub.3 product may be PAA, or a salt thereof. In the previous
embodiment, AA and PAA are produced in parallel from BPL: the first
C.sub.3 reactor converts BPL to AA, the first C.sub.3 product, and
the second C.sub.3 reactor converts BPL to an AA intermediate and
to PAA, the second C.sub.3 product. In certain embodiments, the
various .alpha.,.beta.-unsaturated esters, such as methyl and ethyl
acrylate, as well as the various .alpha.,.beta.-unsaturated amides,
are considered different from one another. Thus, the first C.sub.3
product may be methyl acrylate, and the second C.sub.3 product may
be ethyl acrylate, where these products are regarded as differing
from one another.
[0679] In other embodiments, the various .alpha.,.beta.-unsaturated
esters, such as methyl and ethyl acrylate are not considered
different from one another. Thus, the first C.sub.3 product may be
methyl acrylate, and the second C.sub.3 product may be ethyl
acrylate, where these products are not regarded as differing from
one another. Such embodiments necessarily include another, e.g.,
third C.sub.3 reaction zone and/or first C.sub.4 reaction zone for
making at least one product that is other than an
.alpha.,.beta.-unsaturated ester.
[0680] In certain embodiments, the disclosed systems include one or
more additional (third, fourth, fifth, sixth, seventh, eighth,
ninth, tenth, etc.) C.sub.3 reaction zones that produce
corresponding (third, fourth, fifth, sixth, seventh, eighth, ninth,
tenth, etc.) C.sub.3 products.
[0681] In certain embodiments, the first C.sub.3 product and the
second C.sub.3 product are independently selected from an
.alpha.,.beta.-unsaturated acid, an .alpha.,.beta.-unsaturated
ester, an .alpha.,.beta.-unsaturated amide, a C.sub.3 polymer and
1,3-propanediol (PDO).
[0682] In certain embodiments, the first C.sub.3 product is
polypropiolactone (PPL). In certain embodiments, the first C.sub.3
product is acrylic acid.
[0683] In certain embodiments, the first C.sub.3 product is PPL,
and the system further comprises a third C.sub.3 reactor,
comprising an inlet fed by the outlet stream comprising PPL of the
first C.sub.3 reactor, a third C.sub.3 reaction zone that converts
at least some of the PPL to a third C.sub.3 product, and an outlet
which provides an outlet stream comprising the third C.sub.3
product.
[0684] In certain embodiments, the third C.sub.3 product is acrylic
acid.
[0685] In certain embodiments, the first C.sub.3 reaction zone
converts BPL to PPL. In certain embodiments, the second C.sub.3
reaction zone converts BPL to PPL. In certain embodiments, the
third C.sub.3 reaction zone converts BPL to PPL. In certain
embodiments, the fourth C.sub.3 reaction zone converts BPL to PPL.
In certain embodiments, the fifth C.sub.3 reaction zone converts
BPL to PPL. In certain embodiments, the sixth, seventh, eighth,
ninth and/or tenth C.sub.3 reaction zone converts BPL to PPL.
[0686] In certain embodiments, the first C.sub.3 reaction zone
converts BPL to AA. In certain embodiments, the second C.sub.3
reaction zone converts BPL to AA. In certain embodiments, the third
C.sub.3 reaction zone converts BPL to AA. In certain embodiments,
the fourth C.sub.3 reaction zone converts BPL to AA. In certain
embodiments, the fifth C.sub.3 reaction zone converts BPL to AA. In
certain embodiments, the sixth, seventh, eighth, ninth and/or tenth
C.sub.3 reaction zone converts BPL to AA.
[0687] In certain embodiments, the first C.sub.3 reaction zone
converts BPL to an .alpha.,.beta.-unsaturated ester. In certain
embodiments, the second C.sub.3 reaction zone converts BPL to an
.alpha.,.beta.-unsaturated ester. In certain embodiments, the third
C.sub.3 reaction zone converts BPL to an .alpha.,.beta.-unsaturated
ester. In certain embodiments, the fourth C.sub.3 reaction zone
converts BPL to an .alpha.,.beta.-unsaturated ester. In certain
embodiments, the fifth C.sub.3 reaction zone converts BPL to an
.alpha.,.beta.-unsaturated ester. In certain embodiments, the
sixth, seventh, eighth, ninth and/or tenth C.sub.3 reaction zone
converts BPL to an .alpha.,.beta.-unsaturated ester.
[0688] In certain embodiments, the first C.sub.3 reaction zone
converts BPL to an .alpha.,.beta.-unsaturated amide. In certain
embodiments, the second C.sub.3 reaction zone converts BPL to an
.alpha.,.beta.-unsaturated amide. In certain embodiments, the third
C.sub.3 reaction zone converts BPL to an .alpha.,.beta.-unsaturated
amide. In certain embodiments, the fourth C.sub.3 reaction zone
converts BPL to an .alpha.,.beta.-unsaturated amide. In certain
embodiments, the fifth C.sub.3 reaction zone converts BPL to an
.alpha.,.beta.-unsaturated amide. In certain embodiments, the
sixth, seventh, eighth, ninth and/or tenth C.sub.3 reaction zone
converts BPL to an .alpha.,.beta.-unsaturated amide.
[0689] AA and .alpha.,.beta.-Unsaturated Esters
[0690] In certain embodiments, the product of the beta lactone
conversion stage is an .alpha.,.beta.-unsaturated carboxylic acid
or ester. There are a number of options possible for converting
beta lactones via thermolysis or alcoholoysis to a carboxylic acid
(e.g., AA) or an ester (e.g., acrylate esters), respectively. In
one embodiment, BPL is fed directly to a reactor containing heated
phosphoric acid, optionally including copper metal, a copper salt
or other catalyst, to produce AA vapors that are continuously
removed to avoid the formation of unwanted byproducts. The
formation of AA can be run at atmospheric, super-atmospheric or
sub-atmospheric pressures, at temperatures as high as 300.degree.
C. The AA produced is then condensed and purified by any of the
methods known to one skilled in the art. Additional compounds
useful in converting beta lactones to carboxylic acids include, for
example, sulfuric acid, zinc chloride, sodium bisulfate, boric
acid, boric anhydride, phosphorus pentoxide as well as metallic
catalysis such as, aluminum oxide, iron oxides, titanium oxides,
etc. Further, basic catalysis may be use including calcium
hydroxide, magnesium oxide, borax, disodium phosphate, etc.
[0691] In certain embodiments, water may be added to this process
to act as a catalyst. Without being bound by theory or limiting the
scope of the present invention, it is believed water can aid this
conversion by opening the beta lactone to form a beta hydroxy acid
intermediate which then dehydrates to provide the desired
a,P3-unsaturated acid and regenerate the water. The water may be
added to the beta lactone stream before entering the second
reaction zone, or it may be present in (or added independently to)
the second reaction zone. In certain embodiments, the conversion of
BPL to AA is performed using methods such as those disclosed in
U.S. Pat. Nos. 3,176,042, 2,485,510, 2,623,067, 2,361,036. In other
embodiments, the acrylate production may be base catalyzed, see for
example Journal of Organic Chemistry, 57(1), 389-91(1992).
[0692] Many catalysts known in the art can be used, or adapted for
this step. In certain embodiments, conditions include reaction with
dehydrating agents such as sulfuric acid, phosphoric acid or esters
thereof as described in U.S. Pat. Nos. 2,352,641; 2,376,704;
2,449,995; 2,510,423; 2,623,067; 3,176,042, and in British Patent
No. 994,091.
[0693] In other embodiments, the lactone can be reacted with a
halogenic compound to yield a beta halo acid, beta halo ester, or
beta halo acid halide, which may then undergo dehydrohalogenation
and/or solvolysis to afford the corresponding AA or
.alpha.,.beta.-unsaturated ester. In certain embodiments,
conditions disclosed in U.S. Pat. No. 2,422,728 are used in this
process.
[0694] Similarly, several methods can be employed to convert a beta
lactone to an .alpha.,.beta.-unsaturated ester. For example, most
methods use an alcohol in the beta lactone conversion stage (or
added to the beta lactone stream before it is fed to this stage) to
facilitate ring opening of the beta lactone to a beta hydroxy
ester, or beta alkoxy acid, both of which can convert to
.alpha.,.beta.-unsaturated esters. In certain embodiments, the
lactone conversion is performed in the presence of an alcohol. In
certain embodiments, the lactone conversion is performed in the
presence of a C.sub.1-20 alcohol. In certain embodiments, the
lactone conversion is performed in the presence of a C.sub.1-8
alcohol. In certain embodiments, the lactone conversion is
performed in the presence of an alcohol selected from the group
consisting of: methanol, ethanol, propanol, butanol, hexanol, and
2-ethyl-hexanol to make the corresponding acrylate ester. In
certain embodiments, the alcohol used is a heptyl alcohol, an octyl
alcohol, a nonyl alcohol, an n-decyl alcohol, an n-undecyl alcohol,
a cetyl alcohol, an n-dodecyl alcohol, an n-tetradecyl alcohol and
other primary alcohols. Further, other alcohols can be used in the
BPL conversion, for example, sec-butyl alcohol, tert-butyl alcohol,
allyl alcohol, beta-ethoxy-ethyl alcohol, diethylene glycol
monoethyl either, cyclohexanol, furfuryl alcohol benzyl alcohol,
and ethylene glycol among others as described above.
[0695] The beta lactone conversion is generally performed in the
presence of a catalyst. For example, in certain embodiments, the
beta lactone is reacted with an alcohol in the presence of a
dehydrating catalyst. Exemplary dehydrating catalysts include, for
example, metal oxides (e.g., aluminum oxides, titanium oxides),
zeolites, silica, and alumino-silicates, among others. Typically,
such a conversion is performed in the liquid phase, and the product
esters are isolated by distillation.
[0696] In certain embodiments, the beta lactone conversion can be
performed with activated carbon as a catalyst to produce
.alpha.,.beta.-unsaturated esters. In certain embodiments, the beta
lactone is reacted with an alcohol in the gas phase and over an
activated carbon catalyst to produce esters. The activated carbon
can be supplied in any form, for example, powdered, granulated,
extruded, beads, impregnated with other elements (e.g., iodine,
silver, metallic cations, etc.).
[0697] In certain embodiments, the reaction may include a
polymerization inhibitor to prevent the formation of polymers.
Exemplary polymerization inhibitors include copper, copper salts,
hydroquinone, manganese, manganese salts, chromium, and chromium
salts.
[0698] As described above, the beta lactone conversion can be
operated within a variety of temperature and pressure ranges when
.alpha.,.beta.-unsaturated carboxylic acid or ester are the desired
products. In certain embodiments, the temperature can range from
about 0.degree. C. to about 300.degree. C. In certain embodiments,
the temperature ranges from about 0.degree. C. to 50.degree. C. In
certain embodiments, the temperature ranges from about 0.degree. C.
to 100.degree. C. In certain embodiments, the temperature ranges
from about 0.degree. C. to 150.degree. C. In certain embodiments,
the temperature ranges from about 0.degree. C. to 200.degree. C. In
certain embodiments, the temperature ranges from about 50.degree.
C. to 100.degree. C. In certain embodiments, the temperature ranges
from about 50.degree. C. to 150.degree. C. In certain embodiments,
the temperature ranges from about 50.degree. C. to 200.degree. C.
In certain embodiments, the temperature ranges from about
100.degree. C. to 150.degree. C. In certain embodiments, the
temperature ranges from about 100.degree. C. to 200.degree. C. In
certain embodiments, the temperature ranges from about 100.degree.
C. to 250.degree. C. In certain embodiments, the temperature ranges
from about 150.degree. C. to 250.degree. C. In certain embodiments,
the temperature ranges from about 150.degree. C. to 300.degree. C.
In certain embodiments, the temperature ranges from about
200.degree. C. to 300.degree. C.
[0699] In certain embodiments, the pressure can range from about
0.01 atmospheres to about 500 atmospheres (absolute). In certain
embodiments, the pressure can range from about 0.01 atmospheres to
about 10 atmospheres (absolute). In certain embodiments, the
pressure can range from about 0.01 atmospheres to about 50
atmospheres (absolute). In certain embodiments, the pressure can
range from about 1 atmosphere to about 10 atmospheres (absolute).
In certain embodiments, the pressure can range from about 1
atmosphere to about 50 atmospheres (absolute). In certain
embodiments, the pressure can range from about 1 atmosphere to
about 100 atmospheres (absolute). In certain embodiments, the
pressure can range from about 10 atmospheres to about 50
atmospheres (absolute). In certain embodiments, the pressure can
range from about 10 atmospheres to about 100 atmospheres
(absolute). In certain embodiments, the pressure can range from
about 50 atmospheres to about 100 atmospheres (absolute). In
certain embodiments, the pressure can range from about 50
atmospheres to about 200 atmospheres (absolute). In certain
embodiments, the pressure can range from about 100 atmospheres to
about 200 atmospheres (absolute). In certain embodiments, the
pressure can range from about 100 atmospheres to about 250
atmospheres (absolute). In certain embodiments, the pressure can
range from about 200 atmospheres to about 300 atmospheres
(absolute). In certain embodiments, the pressure can range from
about 200 atmospheres to about 500 atmospheres (absolute). In
certain embodiments, the pressure can range from about 250
atmospheres to about 500 atmospheres (absolute).
[0700] In some embodiments, the pressure used in provided methods
and systems for converting beta lactones to alpha beta unsaturated
acids or esters is less than about 5 atmospheres (absolute). In
some embodiments, the pressure used in provided methods and systems
is less than about 1 atmosphere (absolute). In some embodiments,
the pressure can range from about 0.01 atmospheres to about 1
atmosphere (absolute). In some embodiments, the pressure can range
from about 0.1 atmospheres to about 0.8 atmospheres (absolute). In
some embodiments, the pressure can range from about 0.1 atmospheres
to about 0.5 atmospheres (absolute). In some embodiments, the
pressure can range from about 0.01 atmospheres to about 0.1
atmospheres (absolute). In some embodiments, the pressure can range
from about 0.4 atmospheres to about 1 atmosphere (absolute). In
some embodiments, the pressure can range from about 0.05
atmospheres to about 0.1 atmospheres (absolute).
[0701] Methods of producing .alpha.,.beta.-unsaturated esters from
beta lactones are described in U.S. Pat. Nos. 2,466,501,
2,376,704.
[0702] AA Via Celanese Process
[0703] In certain embodiments, AA and its esters are prepared
according to the process developed by the Celanese Corporation for
the thermolysis of BPL, formed from the product of the reaction of
formaldehyde with ketene, to produce AA and its esters. In such
embodiments, the central reactor receives formaldehyde and ketene
that are converted to BPL. In certain embodiments, thermolysis of
BPL proceeds with phosphoric acid using a copper powder catalyst at
140-180.degree. C. and 25-250 bar to quantitatively form AA. In
some embodiments, this reaction may be catalyzed by adding water.
If the same reaction is run in the presence of an alcohol, the
corresponding acrylate ester is formed directly.
[0704] .alpha.,.beta.-Unsaturated Amides
[0705] Alternatively, ammonia or an organic amine may be present in
this stage to facilitate ring opening of the beta lactone to a beta
hydroxy amide, which can be converted to .alpha.,.beta.-unsaturated
amides. In certain embodiments, the lactone conversion is performed
in the presence of ammonia to produce acrylamide. In certain
embodiments, the lactone conversion is performed in the presence of
a C.sub.1-20 amine to produce N-substituted acrylamide derivatives
(e.g., .alpha.,.beta.-unsaturated amide). Exemplary amines include
for example methyl amine, ethyl amine, propyl amines, butyl amines,
amyl amines, and dialkyl amines. In certain embodiments, the amine
and the beta lactone are both soluble in water.
[0706] As described above, the beta lactone conversion can be
operated within a variety of temperature and pressure ranges when
.alpha.,.beta.-unsaturated amides are the desired products. Some of
the reactions are exothermic and therefore lower temperatures may
be useful, as well as sufficient heat transfer to control reaction
temperature. As described above, the beta lactone conversion can be
operated within a variety of temperature and pressure ranges when
.alpha.,.beta.-unsaturated amides are the desired products. In
certain embodiments, the temperature can range from about 0.degree.
C. to about 300.degree. C. In certain embodiments, the temperature
ranges from about 0.degree. C. to 50.degree. C. In certain
embodiments, the temperature ranges from about 0.degree. C. to
100.degree. C. In certain embodiments, the temperature ranges from
about 0.degree. C. to 150.degree. C. In certain embodiments, the
temperature ranges from about 0.degree. C. to 200.degree. C. In
certain embodiments, the temperature ranges from about 50.degree.
C. to 100.degree. C. In certain embodiments, the temperature ranges
from about 50.degree. C. to 150.degree. C. In certain embodiments,
the temperature ranges from about 50.degree. C. to 200.degree. C.
In certain embodiments, the temperature ranges from about
100.degree. C. to 150.degree. C. In certain embodiments, the
temperature ranges from about 100.degree. C. to 200.degree. C. In
certain embodiments, the temperature ranges from about 100.degree.
C. to 250.degree. C. In certain embodiments, the temperature ranges
from about 150.degree. C. to 250.degree. C. In certain embodiments,
the temperature ranges from about 150.degree. C. to 300.degree. C.
In certain embodiments, the temperature ranges from about
200.degree. C. to 300.degree. C.
[0707] In certain embodiments, the pressure can range from about
0.01 atmospheres to about 500 atmospheres (absolute). In certain
embodiments, the pressure can range from about 0.01 atmospheres to
about 10 atmospheres (absolute). In certain embodiments, the
pressure can range from about 0.01 atmospheres to about 50
atmospheres (absolute). In certain embodiments, the pressure can
range from about 1 atmosphere to about 10 atmospheres (absolute).
In certain embodiments, the pressure can range from about 1
atmosphere to about 50 atmospheres (absolute). In certain
embodiments, the pressure can range from about 1 atmosphere to
about 100 atmospheres (absolute). In certain embodiments, the
pressure can range from about 10 atmospheres to about 50
atmospheres (absolute). In certain embodiments, the pressure can
range from about 10 atmospheres to about 100 atmospheres
(absolute). In certain embodiments, the pressure can range from
about 50 atmospheres to about 100 atmospheres (absolute). In
certain embodiments, the pressure can range from about 50
atmospheres to about 200 atmospheres (absolute). In certain
embodiments, the pressure can range from about 100 atmospheres to
about 200 atmospheres (absolute). In certain embodiments, the
pressure can range from about 100 atmospheres to about 250
atmospheres (absolute). In certain embodiments, the pressure can
range from about 200 atmospheres to about 300 atmospheres
(absolute). In certain embodiments, the pressure can range from
about 200 atmospheres to about 500 atmospheres (absolute). In
certain embodiments, the pressure can range from about 250
atmospheres to about 500 atmospheres (absolute).
[0708] In some embodiments, the pressure used in provided methods
and systems for converting beta lactones to alpha beta unsaturated
amides is less than about 5 atmospheres (absolute). In some
embodiments, the pressure used in provided methods and systems is
less than about 1 atmosphere (absolute). In some embodiments, the
pressure can range from about 0.01 atmospheres to about 1
atmosphere (absolute). In some embodiments, the pressure can range
from about 0.1 atmospheres to about 0.8 atmospheres (absolute). In
some embodiments, the pressure can range from about 0.1 atmospheres
to about 0.5 atmospheres (absolute). In some embodiments, the
pressure can range from about 0.01 atmospheres to about 0.1
atmospheres (absolute). In some embodiments, the pressure can range
from about 0.4 atmospheres to about 1 atmosphere (absolute). In
some embodiments, the pressure can range from about 0.05
atmospheres to about 0.1 atmospheres (absolute).
[0709] Methods of producing .alpha.,.beta.-unsaturated amides from
beta lactones are described in U.S. Pat. No. 2,548,155.
Lactone to Polymers
[0710] In certain embodiments, the beta lactone from the
carbonylation is fed into a subsequent stage comprising a
polymerization catalyst, described in more detail below. This
provides the opportunity to produce biodegradable polyesters such
as poly(3-hydroxy butyrate) (P-3HB), and polypropiolactone (PPL)
without the need to handle and transport beta lactones.
[0711] In certain embodiments where the beta lactone conversion
comprises polymerizing the beta lactone, the step includes
contacting the beta lactone with a polymerization catalyst,
optionally in the presence of one or more solvents. Suitable
solvents can include, for example, hydrocarbons, ethers, esters,
ketones, nitriles, amides, sulfones, halogenated hydrocarbons, and
the like. In certain embodiments, the solvent is selected such that
the polymer formed is soluble in the reaction medium.
[0712] In certain embodiments where the beta lactone conversion
comprises polymerizing the beta lactone to form a polyester, the
step comprises a continuous polymerization. Such continuous
polymerizations can be conducted in a continuous stirred tank
reactor or a plug flow reactor such that polymer or polymer
solution is withdrawn at essentially the same rate it is formed.
Polymerization of lactones to polyester can be performed with a
number of polymerization initiators including, for example,
alcohols, amines, polyols, polyamines, and diols, amongst others.
Further a variety of catalysts may be used in the polymerization
reaction, including by not limited to metals (e.g., lithium,
sodium, potassium, magnesium, calcium, zinc, aluminum, titanium,
cobalt, etc.) metal oxides, carbonates of alkali- and alkaline
earth metals, borates, silicates, of various metals. In some
variations, catalysts that may be used in the polymerization
reaction, include for example metals (e.g., lithium, sodium,
potassium, magnesium, calcium, zinc, aluminum, titanium, cobalt,
etc.) metal oxides, salts of alkali and alkaline earth metals (such
as carbonates, borates, hydroxides, alkoxides, and carboxylates),
and borates, silicates, or salts of other metals.
[0713] U.S. Pat. Nos. 3,169,945 and 3,678,069 describe methods of
producing polyesters from beta lactones.
[0714] Polymerization Catalysts
[0715] Many catalysts are known for the ring-opening polymerization
of lactones (such as caprolactone and beta lactones). Any such
catalyst can be employed.
[0716] Catalysts suitable for the ring-opening polymerization of
the methods disclosed herein are disclosed, for example, in:
Journal of the American Chemical Society (2002), 124(51),
15239-15248 Macromolecules, vol. 24, No. 20, pp. 5732-5733, Journal
of Polymer Science, Part A-1, vol. 9, No. 10, pp. 2775-2787; Inoue,
S., Y. Tomoi, T. Tsuruta & J. Furukawa; Macromolecules, vol.
26, No. 20, pp. 5533-5534; Macromolecules, vol. 23, No. 13, pp.
3206-3212; Polymer Preprints (1999), 40(1), 508-509;
Macromolecules, vol. 21, No. 9, pp. 2657-2668; and Journal of
Organometallic Chemistry, vol. 341, No. 1-3, pp. 83-9; and in U.S.
Pat. Nos. 3,678,069, 3,169,945, 6,133,402; 5,648,452; 6,316,590;
6,538,101; and 6,608,170.
[0717] In certain embodiments, suitable catalysts include
carboxylate salts of metal ions or organic cations. In certain
embodiments, a carboxylate salt is other than a carbonate.
[0718] In certain embodiments, the polymerization catalyst is
combined with BPL in a molar ratio up to about 1:100,000
polymerization catalyst:BPL. In certain embodiments, the ratio is
from about 1:100,000 to about 25:100 polymerization catalyst:BPL.
In certain embodiments, the polymerization catalyst is combined
with BPL in a molar ratio of about 1:50,000 polymerization
catalyst:BPL to about 1:25,000 polymerization catalyst:BPL. In
certain embodiments, the polymerization catalyst is combined with
BPL in a molar ratio of about 1:25,000 polymerization catalyst:BPL
to about 1:10,000 polymerization catalyst:BPL. In certain
embodiments, the polymerization catalyst is combined with BPL in a
molar ratio of about 1:20,000 polymerization catalyst:BPL to about
1:10,000 polymerization catalyst:BPL. In certain embodiments, the
polymerization catalyst is combined with BPL in a molar ratio of
about 1:15,000 polymerization catalyst:BPL to about 1:5,000
polymerization catalyst:BPL. In certain embodiments, the
polymerization catalyst is combined with BPL in a molar ratio of
about 1:5,000 polymerization catalyst:BPL to about 1:1,000
polymerization catalyst:BPL. In certain embodiments, the
polymerization catalyst is combined with BPL in a molar ratio of
about 1:2,000 polymerization catalyst:BPL to about 1:500
polymerization catalyst:BPL. In certain embodiments, the
polymerization catalyst is combined with BPL in a molar ratio of
about 1:1,000 polymerization catalyst:BPL to about 1:200
polymerization catalyst:BPL. In certain embodiments, the
polymerization catalyst is combined with BPL in a molar ratio of
about 1:500 polymerization catalyst:BPL to about 1:100
polymerization catalyst:BPL. In certain embodiments the molar ratio
of polymerization catalyst:BPL is about 1:50,000, 1:25,000,
1:15,000, 1:10,000, 1:5,000, 1:1,000, 1:500, 1:250 or a range
including any two of these values. In certain embodiments, the
polymerization catalyst is combined with BPL in a molar ratio of
about 1:100 polymerization catalyst:BPL to about 25:100
polymerization catalyst:BPL. In certain embodiments the molar ratio
of polymerization catalyst:BPL is about 1:100, 5:100, 10:100,
15:100, 20:100, 25:100 or a range including any two of these
values.
[0719] In certain embodiments, where the polymerization catalyst
comprises a carboxylate salt, the carboxylate has a structure such
that upon initiating polymerization of BPL, the polymer chains
produced have an acrylate chain end. In certain embodiments, the
carboxylate ion on a polymerization catalyst is the anionic form of
a chain transfer agent (CTA) used in the polymerization
process.
[0720] In certain embodiments, the carboxylate salt of the
polymerization catalyst is an acrylate salt (i.e., the anionic
form) of a compound
##STR00037##
or a mixture of any two or more of these, where p is from 0 to 9.
In certain embodiments, p is from 0 to 5. In certain embodiments,
the carboxylate salt of the polymerization catalyst is an acrylate
salt (i.e., of compound above where p=0).
[0721] In certain embodiments, the carboxylate salt of the
polymerization catalyst is a salt of an acrylic acid dimer,
##STR00038##
In certain embodiments, the carboxylate salt of the polymerization
catalyst is a salt of an acrylic acid trimer,
##STR00039##
[0722] In certain embodiments, where the polymerization catalyst
comprises a carboxylate salt, the carboxylate is the anionic form
of a C.sub.1-40 carboxylic acid. In certain embodiments, the
carboxylate salt can be a salt of a polycarboxylic acid (e.g. a
compound having two or more carboxylic acid groups). In certain
embodiments, the carboxylate comprises the anion of a C.sub.1-20
carboxylic acid. In certain embodiments, the carboxylate comprises
the anion of a C.sub.1-12 carboxylic acid. In certain embodiments,
the carboxylate comprises the anion of a C.sub.1-8 carboxylic acid.
In certain embodiments, the carboxylate comprises the anion of a
C.sub.1-4 carboxylic acid. In certain embodiments, the carboxylate
comprises the anion of an optionally substituted benzoic acid. In
certain embodiments, the carboxylate is selected from the group
consisting of: formate, acetate, propionate, valerate, butyrate,
C.sub.5-10 aliphatic carboxylate, and C.sub.10-20 aliphatic
carboxylate.
[0723] As noted, in certain embodiments, the polymerization
catalyst comprises a carboxylate salt of an organic cation. In
certain embodiments, the polymerization catalyst comprises a
carboxylate salt of a cation wherein the positive charge is located
at least partially on a nitrogen, sulfur, or phosphorus atom. In
certain embodiments, the polymerization catalyst comprises a
carboxylate salt of a nitrogen cation. In certain embodiments, the
polymerization catalyst comprises a carboxylate salt of a cation
selected from the group consisting of: ammonium, amidinium,
guanidinium, a cationic form of a nitrogen heterocycle, and any
combination of two or more of these. In certain embodiments, the
polymerization catalyst comprises a carboxylate salt of a
phosphorus cation. In certain embodiments, the polymerization
catalyst comprises a carboxylate salt of a cation selected from the
group consisting of: phosphonium and phosphazenium. In certain
embodiments, the polymerization catalyst comprises a carboxylate
salt of a sulfur-containing cation. In certain embodiments, the
polymerization catalyst comprises a sulfonium salt.
[0724] In certain embodiments, the polymerization catalyst
comprises a carboxylate salt of a metal. In certain embodiments,
the polymerization catalyst comprises a carboxylate salt of a
alkali or alkaline earth metal. In certain embodiments, the
polymerization catalyst comprises a carboxylate salt of an alkali
metal. In certain embodiments, the polymerization catalyst
comprises a carboxylate salt of sodium or potassium. In certain
embodiments, the polymerization catalyst comprises a carboxylate
salt of sodium.
[0725] In certain embodiments, the polymerization catalyst
comprises a carboxylate salt of a protonated amine:
##STR00040##
where:
[0726] each R.sup.1 and R.sup.2 is independently hydrogen or an
optionally substituted radical selected from the group consisting
of C.sub.1-20 aliphatic; C.sub.1-20 heteroaliphatic; a 3- to
8-membered saturated or partially unsaturated monocyclic
carbocycle; a 7- to 14-membered saturated or partially unsaturated
polycyclic carbocycle; a 5- to 6-membered monocyclic heteroaryl
ring having 1-4 heteroatoms independently selected from nitrogen,
oxygen, or sulfur; an 8- to 14-membered polycyclic heteroaryl ring
having 1-5 heteroatoms independently selected from nitrogen,
oxygen, or sulfur; a 3- to 8-membered saturated or partially
unsaturated monocyclic heterocyclic ring having 1-3 heteroatoms
independently selected from nitrogen, oxygen, or sulfur; a 6- to
14-membered saturated or partially unsaturated polycyclic
heterocycle having 1-5 heteroatoms independently selected from
nitrogen, oxygen, or sulfur; phenyl; or an 8- to 14-membered
polycyclic aryl ring; wherein R.sup.1 and R.sup.2 can be taken
together with intervening atoms to form one or more optionally
substituted rings optionally containing one or more additional
heteroatoms;
[0727] each R.sup.3 is independently hydrogen or an optionally
substituted radical selected from the group consisting of
C.sub.1-20 aliphatic; C.sub.1-20 heteroaliphatic; a 3- to
8-membered saturated or partially unsaturated monocyclic
carbocycle; a 7- to 14-membered saturated or partially unsaturated
polycyclic carbocycle; a 5- to 6-membered monocyclic heteroaryl
ring having 1-4 heteroatoms independently selected from nitrogen,
oxygen, or sulfur; an 8- to 14-membered polycyclic heteroaryl ring
having 1-5 heteroatoms independently selected from nitrogen,
oxygen, or sulfur; a 3- to 8-membered saturated or partially
unsaturated monocyclic heterocyclic ring having 1-3 heteroatoms
independently selected from nitrogen, oxygen, or sulfur; a 6- to
14-membered saturated or partially unsaturated polycyclic
heterocycle having 1-5 heteroatoms independently selected from
nitrogen, oxygen, or sulfur; phenyl; or an 8- to 14-membered
polycyclic aryl ring; wherein an R.sup.3 group can be taken with an
R.sup.1 or R.sup.2 group to form one or more optionally substituted
rings.
[0728] In certain embodiments where the polymerization catalyst
comprises a carboxylate salt of a protonated amine, the protonated
amine is selected from the group consisting of:
##STR00041## ##STR00042##
[0729] In certain embodiments, the polymerization catalyst
comprises a carboxylate salt of a quaternary ammonium salt:
##STR00043##
where: [0730] each R.sup.1, R.sup.2 and R.sup.3 is described above;
and [0731] each R.sup.4 is independently hydrogen or an optionally
substituted radical selected from the group consisting of
C.sub.1-20 aliphatic; C.sub.1-20 heteroaliphatic; a 3- to
8-membered saturated or partially unsaturated monocyclic
carbocycle; a 7- to 14-membered saturated or partially unsaturated
polycyclic carbocycle; a 5- to 6-membered monocyclic heteroaryl
ring having 1-4 heteroatoms independently selected from nitrogen,
oxygen, or sulfur; an 8- to 14-membered polycyclic heteroaryl ring
having 1-5 heteroatoms independently selected from nitrogen,
oxygen, or sulfur; a 3- to 8-membered saturated or partially
unsaturated monocyclic heterocyclic ring having 1-3 heteroatoms
independently selected from nitrogen, oxygen, or sulfur; a 6- to
14-membered saturated or partially unsaturated polycyclic
heterocycle having 1-5 heteroatoms independently selected from
nitrogen, oxygen, or sulfur; phenyl; or an 8- to 14-membered
polycyclic aryl ring; wherein an R.sup.4 group can be taken with an
R.sup.1, R.sup.2 or R.sup.3 group to form one or more optionally
substituted rings.
[0732] In certain embodiments, a polymerization catalyst comprises
a carboxylate salt of a guanidinium group:
##STR00044##
wherein each R.sup.1 and R.sup.2 is independently as defined above
and described in classes and subclasses herein. In certain
embodiments, each R.sup.1 and R.sup.2 is independently hydrogen or
C.sub.1-20 aliphatic. In certain embodiments, each R.sup.1 and
R.sup.2 is independently hydrogen or C.sub.1-12 aliphatic. In
certain embodiments, each R.sup.1 and R.sup.2 is independently
hydrogen or C.sub.1-20 heteroaliphatic. In certain embodiments,
each R.sup.1 and R.sup.2 is independently hydrogen or phenyl. In
certain embodiments, each R.sup.1 and R.sup.2 is independently
hydrogen or 8- to 10-membered aryl. In certain embodiments, each
R.sup.1 and R.sup.2 is independently hydrogen or 5- to 10-membered
heteroaryl. In certain embodiments, each R.sup.1 and R.sup.2 is
independently hydrogen or 3- to 7-membered heterocyclic. In certain
embodiments, one or more of R.sup.1 and R.sup.2 is optionally
substituted C.sub.1-12 aliphatic.
[0733] In certain embodiments, any two or more R.sup.1 or R.sup.2
groups are taken together with intervening atoms to form one or
more optionally substituted carbocyclic, heterocyclic, aryl, or
heteroaryl rings. In certain embodiments, R.sup.1 and R.sup.2
groups are taken together to form an optionally substituted 5- or
6-membered ring. In certain embodiments, three or more R.sup.1
and/or R.sup.2 groups are taken together to form an optionally
substituted fused ring system.
[0734] In certain embodiments, an R.sup.1 and R.sup.2 group are
taken together with intervening atoms to form a compound selected
from:
##STR00045##
wherein each R and R is independently as defined above and
described in classes and subclasses herein, and Ring G is an
optionally substituted 5- to 7-membered saturated or partially
unsaturated heterocyclic ring.
[0735] It will be appreciated that when a guanidinium cation is
depicted as
##STR00046##
all such resonance forms are contemplated and encompassed by the
present disclosure. For example, such groups can also be depicted
as
##STR00047##
[0736] In specific embodiments, a guanidinium cation is selected
from the group consisting of:
##STR00048##
[0737] In certain embodiments, a polymerization catalyst comprises
a carboxylate salt of a sulfonium group or an arsonium group, such
as
##STR00049##
wherein each of R.sup.1, R.sup.2, and R.sup.3 are as defined above
and described in classes and subclasses herein.
[0738] In specific embodiments, an arsonium cation is selected from
the group consisting of:
##STR00050##
[0739] In certain embodiments, a polymerization catalyst comprises
a carboxylate salt of an optionally substituted nitrogen-containing
heterocycle. In certain embodiments, the nitrogen-containing
heterocycle is an aromatic heterocycle. In certain embodiments, the
optionally substituted nitrogen-containing heterocycle is selected
from the group consisting of: pyridine, imidazole, pyrrolidine,
pyrazole, quinoline, thiazole, dithiazole, oxazole, triazole,
pyrazole, isoxazole, isothiazole, tetrazole, pyrazine, thiazine,
and triazine.
[0740] In certain embodiments, a nitrogen-containing heterocycle
includes a quaternarized nitrogen atom. In certain embodiments, a
nitrogen-containing heterocycle includes an iminium moiety such
as
##STR00051##
In certain embodiments, the optionally substituted
nitrogen-containing heterocycle is selected from the group
consisting of pyridinium, imidazolium, pyrrolidinium, pyrazolium,
quinolinium, thiazolium, dithiazolium, oxazolium, triazolium,
isoxazolium, isothiazolium, tetrazolium, pyrazinium, thiazinium,
and triazinium.
[0741] In certain embodiments, a nitrogen-containing heterocycle is
linked to a metal complex via a ring nitrogen atom. In certain
embodiments, a ring nitrogen to which the attachment is made is
thereby quaternized, and In certain embodiments, linkage to a metal
complex takes the place of an N--H bond and the nitrogen atom
thereby remains neutral. In certain embodiments, an optionally
substituted N-linked nitrogen-containing heterocycle is a
pyridinium derivative. In certain embodiments, optionally
substituted N-linked nitrogen-containing heterocycle is an
imidazolium derivative. In certain embodiments, optionally
substituted N-linked nitrogen-containing heterocycle is a
thiazolium derivative. In certain embodiments, optionally
substituted N-linked nitrogen-containing heterocycle is a
pyridinium derivative.
[0742] In certain embodiments, a polymerization catalyst comprises
a carboxylate salt of
##STR00052##
In certain embodiments, ring A is an optionally substituted, 5- to
10-membered heteroaryl group. In certain embodiments, Ring A is an
optionally substituted, 6-membered heteroaryl group. In certain
embodiments, Ring A is a ring of a fused heterocycle. In certain
embodiments, Ring A is an optionally substituted pyridyl group.
[0743] In specific embodiments, a nitrogen-containing heterocyclic
cation is selected from the group consisting of:
##STR00053## ##STR00054##
[0744] In certain embodiments, a polymerization catalyst comprises
a carboxylate salt of
##STR00055##
where each R.sup.1, R.sup.2, and R.sup.3 is independently as
defined above and described in classes and subclasses herein.
[0745] In certain embodiments, a polymerization catalyst comprises
a carboxylate salt of
##STR00056##
wherein each R.sup.1 and R.sup.2 is independently as defined above
and described in classes and subclasses herein.
[0746] In certain embodiments, a polymerization catalyst comprises
a carboxylate salt of
##STR00057##
wherein each R.sup.1, R.sup.2, and R.sup.3 is independently as
defined above and described in classes and subclasses herein.
[0747] In certain embodiments, a polymerization catalyst comprises
a carboxylate salt of
##STR00058##
wherein each of R.sup.1, R.sup.2, R.sup.6, and R.sup.7 is as
defined above and described in classes and subclasses herein.
[0748] In certain embodiments, R.sup.6 and R.sup.7 are each
independently an optionally substituted group selected from the
group consisting of C.sub.1-20 aliphatic; C.sub.1-20
heteroaliphatic; phenyl, and 8-10-membered aryl. In certain
embodiments, R.sup.6 and R.sup.7 are each independently an
optionally substituted C.sub.1-20 aliphatic. In certain
embodiments, R.sup.6 and R.sup.7 are each independently an
optionally substituted C.sub.1-20 heteroaliphatic having. In
certain embodiments, R.sup.6 and R.sup.7 are each independently an
optionally substituted phenyl or 8-10-membered aryl. In certain
embodiments, R.sup.6 and R.sup.7 are each independently an
optionally substituted 5- to 10-membered heteroaryl. In certain
embodiments, R.sup.6 and R.sup.7 can be taken together with
intervening atoms to form one or more rings selected from the group
consisting of: optionally substituted C.sub.3-C.sub.14 carbocycle,
optionally substituted C.sub.3-C.sub.14 heterocycle, optionally
substituted C.sub.6-C.sub.10 aryl, and optionally substituted 5- to
10-membered heteroaryl. In certain embodiments, R.sup.6 and R.sup.7
are each independently an optionally substituted C.sub.1-6
aliphatic. In certain embodiments, each occurrence of R.sup.6 and
R.sup.7 is independently methyl, ethyl, propyl, butyl, pentyl,
hexyl, heptyl, octyl, or benzyl. In certain embodiments, each
occurrence of R.sup.6 and R.sup.7 is independently perfluoro. In
certain embodiments, each occurrence of R.sup.6 and R.sup.7 is
independently --CF.sub.2CF.sub.3.
[0749] In certain embodiments, a polymerization catalyst comprises
a carboxylate salt of
##STR00059##
wherein each R.sup.1 and R.sup.2 is independently as defined above
and described in classes and subclasses herein.
[0750] In certain embodiments, a polymerization catalyst comprises
a carboxylate salt of
##STR00060##
wherein each R.sup.1, R.sup.2, and R.sup.3 is independently as
defined above and described in classes and subclasses herein.
[0751] In certain embodiments, a cation is
##STR00061##
wherein each R.sup.1 and R.sup.2 is independently as defined above
and described in classes and subclasses herein.
[0752] In certain embodiments, a polymerization catalyst comprises
a carboxylate salt of
##STR00062##
wherein each R.sup.1 and R.sup.2 is independently as defined above
and described in classes and subclasses herein.
[0753] In certain embodiments, a polymerization catalyst comprises
a carboxylate salt of
##STR00063##
wherein each R.sup.1, R.sup.2, and R.sup.3 is independently as
defined above and described in classes and subclasses herein.
[0754] In certain embodiments, a polymerization catalyst comprises
a carboxylate salt of
##STR00064##
wherein each R.sup.1 and R.sup.2 is independently as defined above
and described in classes and subclasses herein. In certain
embodiments, suitable catalysts include transition metal compounds.
In certain embodiments, suitable catalysts include acid catalysts.
In certain embodiments, the catalyst is a heterogeneous
catalyst.
[0755] In certain embodiments, any of the foregoing cationic
functional groups are attached to a solid support. Examples of
suitable solid supports include polymeric solids (e.g. polymer
beads, films, fibers, fabrics, particles and the like) as well as
inorganic solids (e.g. clays, silicas, aluminas, diatomaceous
earth, ceramics, metal oxides, mineral fibers beads or particles,
and the like). Specific examples of such supported cationic
functional groups include polystyrene resin beads functionalized
with ammonium groups, polystyrene resin beads functionalized with
phosphonium groups, and polystyrene resin beads functionalized with
guanidinium groups. Specific examples of such supported cationic
functional groups include silica particles functionalized with
ammonium groups, alumina particles functionalized with phosphonium
groups, and ceramic beads functionalized with guanidinium groups.
In certain embodiments, polymerization catalysts comprise
carboxylate salts of any of the foregoing supported solid cationic
functional groups. In certain embodiments, polymerization catalysts
comprise acrylate salts of any of the foregoing solid supported
cationic functional groups.
[0756] In certain embodiments, polymerization catalysts comprise
cationic solids wherein the cations comprise metal atoms. In
certain embodiments, polymerization catalysts comprise carboxylate
salts of any of the foregoing supported solid cationic metal atoms.
In certain embodiments, polymerization catalysts comprise acrylate
salts of any of the foregoing supported solid cationic metal
atoms.
[0757] In certain embodiments, the carboxylate salt of the
polymerization catalyst is a compound:
##STR00065##
where p is from 0 to 9 and R.sup.a is a non-volatile moiety. The
term "non-volatile moiety," as used herein, refers to a moiety or
material to which a carboxylate can be attached, and that renders
the carboxylate (e.g., when p=0) non-volatile to pyrolysis
conditions. In certain embodiments, a non-volatile moiety is
selected from the group consisting of glass surfaces, silica
surfaces, plastic surfaces, metal surfaces including zeolites,
surfaces containing a metallic or chemical coating, membranes
(e.g., nylon, polysulfone, silica), micro-beads (e.g., latex,
polystyrene, or other polymer), and porous polymer matrices (e.g.,
polyacrylamide, polysaccharide, polymethacrylate). In certain
embodiments, a non-volatile moiety has a molecular weight above
100, 200, 500, or 1000 g/mol. In certain embodiments, a
non-volatile moiety is part of a fixed or packed bed system. In
certain embodiments, a non-volatile moiety is part of a fixed or
packed bed system comprising pellets (e.g., zeolite).
[0758] In certain embodiments, p is from 0 to 5. In certain
embodiments, the carboxylate salt of the polymerization catalyst is
an acrylate salt (i.e., of the above compound where p=0).
[0759] In certain embodiments, a suitable carboxylate catalyst is
heterogeneous. In certain embodiments, a suitable carboxylate
catalyst will remain in a reaction zone as a salt or melt after
removal of all other products, intermediates, starting materials,
byproducts, and other reaction components. In certain embodiments,
a suitable carboxylate catalyst (i.e., the above compound where p
is from 0 to 9) will remain in a reaction zone as a salt or melt
after removal of all AA product stream.
[0760] In certain embodiments, a catalyst is recycled for further
use in a reaction zone. In certain embodiments, a salt or melt
catalyst is recycled to a reaction zone. In certain embodiments,
provided methods further comprise withdrawing a recycling stream of
homogeneous catalyst to a reaction zone. In certain embodiments,
such a recycling stream comprises a high boiling solvent, wherein
the solvent's boiling point is above the pyrolysis temperature of
PPL and the catalyst remains in the high boiling solvent during
pyrolysis while the withdrawn product stream is gaseous.
BPL to AA
[0761] In some embodiments, BPL is converted to AA (including, for
example, GAA) without isolation of the intermediate PPL, wherein
the PPL formed by polymerization of BPL is concurrently converted
to AA (including, for example, GAA) via pyrolysis in the same
reaction zone (e.g., a "one-pot" method). In certain embodiments,
the reaction zone containing the reaction of BPL to PPL is
maintained at a temperature at or above the pyrolysis temperature
of PPL such that the thermal decomposition of PPL produces AA.
Without wishing to be bound by any particular theory, it is
believed that in such embodiments as BPL reacts with AA to start
polymer chains, thermal decomposition will degrade the polymer to
AA.
[0762] A one-pot BPL conversion to AA can be operated within a
variety of temperature and pressure ranges. In certain embodiments,
the temperature can range from about 150.degree. C. to about
300.degree. C. In certain embodiments, the temperature ranges from
about 150.degree. C. to about 200.degree. C. In certain
embodiments, the temperature ranges from about 150.degree. C. to
about 250.degree. C. In certain embodiments, the temperature ranges
from about 175.degree. C. to about 300.degree. C. In some
embodiments, the temperature ranges from about 200.degree. C. to
about 250.degree. C. In certain embodiments, the temperature ranges
from about 225.degree. C. to about 275.degree. C. In certain
embodiments, the temperature ranges from about 250.degree. C. to
about 300.degree. C. In certain embodiments, the temperature ranges
from about 200.degree. C. to about 300.degree. C.
[0763] In certain embodiments, the pressure used in provided
methods and systems can range from about 0.01 atmospheres to about
500 atmospheres (absolute). In certain embodiments, the pressure
can range from about 0.01 atmospheres to about 10 atmospheres
(absolute). In certain embodiments, the pressure can range from
about 0.01 atmospheres to about 50 atmospheres (absolute). In
certain embodiments, the pressure can range from about 1 atmosphere
to about 10 atmospheres (absolute). In certain embodiments, the
pressure can range from about 1 atmosphere to about 50 atmospheres
(absolute). In certain embodiments, the pressure can range from
about 1 atmosphere to about 100 atmospheres (absolute). In certain
embodiments, the pressure can range from about 10 atmospheres to
about 50 atmospheres (absolute). In certain embodiments, the
pressure can range from about 10 atmospheres to about 100
atmospheres (absolute). In certain embodiments, the pressure can
range from about 50 atmospheres to about 100 atmospheres
(absolute). In certain embodiments, the pressure can range from
about 50 atmospheres to about 200 atmospheres (absolute). In
certain embodiments, the pressure can range from about 100
atmospheres to about 200 atmospheres (absolute). In certain
embodiments, the pressure can range from about 100 atmospheres to
about 250 atmospheres (absolute). In certain embodiments, the
pressure can range from about 200 atmospheres to about 300
atmospheres (absolute). In certain embodiments, the pressure can
range from about 200 atmospheres to about 500 atmospheres
(absolute). In certain embodiments, the pressure can range from
about 250 atmospheres to about 500 atmospheres (absolute).
[0764] In some embodiments, the pressure used in provided methods
and systems for converting BPL to AA is less than about 5
atmospheres (absolute). In some embodiments, the pressure used in
provided methods and systems is less than about 1 atmosphere
(absolute). In some embodiments, the pressure can range from about
0.01 atmospheres to about 1 atmosphere (absolute). In some
embodiments, the pressure can range from about 0.1 atmospheres to
about 0.8 atmospheres (absolute). In some embodiments, the pressure
can range from about 0.1 atmospheres to about 0.5 atmospheres
(absolute). In some embodiments, the pressure can range from about
0.01 atmospheres to about 0.1 atmospheres (absolute). In some
embodiments, the pressure can range from about 0.4 atmospheres to
about 1 atmosphere (absolute). In some embodiments, the pressure
can range from about 0.05 atmospheres to about 0.1 atmospheres
(absolute).
PPL to AA
[0765] In some embodiments where at least one of the C3 reactors
produces PPL, at least a portion of the resulting PPL stream is fed
to another C3 where it is converted to AA (including, for example,
GAA). In certain embodiments, the reaction zone converting the PPL
to AA is maintained at a temperature at or above the pyrolysis
temperature of PPL such that the thermal decomposition of PPL
produces AA.
[0766] PPL conversion to AA can be operated within a variety of
temperature and pressure ranges. In certain embodiments, the
temperature can range from about 150.degree. C. to about
300.degree. C. In certain embodiments, the temperature ranges from
about 150.degree. C. to about 200.degree. C. In certain
embodiments, the temperature ranges from about 150.degree. C. to
about 250.degree. C. In certain embodiments, the temperature ranges
from about 175.degree. C. to about 300.degree. C. In some
embodiments, the temperature ranges from about 200.degree. C. to
about 250.degree. C. In certain embodiments, the temperature ranges
from about 225.degree. C. to about 275.degree. C. In certain
embodiments, the temperature ranges from about 250.degree. C. to
about 300.degree. C. In certain embodiments, the temperature ranges
from about 200.degree. C. to about 300.degree. C.
[0767] In certain embodiments, the pressure used in provided
methods and systems to convert PPL to AA can range from about 0.01
atmospheres to about 500 atmospheres (absolute). In certain
embodiments, the pressure can range from about 0.01 atmospheres to
about 10 atmospheres (absolute). In certain embodiments, the
pressure can range from about 0.01 atmospheres to about 50
atmospheres (absolute). In certain embodiments, the pressure can
range from about 1 atmosphere to about 10 atmospheres (absolute).
In certain embodiments, the pressure can range from about 1
atmosphere to about 50 atmospheres (absolute). In certain
embodiments, the pressure can range from about 1 atmosphere to
about 100 atmospheres (absolute). In certain embodiments, the
pressure can range from about 10 atmospheres to about 50
atmospheres (absolute). In certain embodiments, the pressure can
range from about 10 atmospheres to about 100 atmospheres
(absolute). In certain embodiments, the pressure can range from
about 50 atmospheres to about 100 atmospheres (absolute). In
certain embodiments, the pressure can range from about 50
atmospheres to about 200 atmospheres (absolute). In certain
embodiments, the pressure can range from about 100 atmospheres to
about 200 atmospheres (absolute). In certain embodiments, the
pressure can range from about 100 atmospheres to about 250
atmospheres (absolute). In certain embodiments, the pressure can
range from about 200 atmospheres to about 300 atmospheres
(absolute). In certain embodiments, the pressure can range from
about 200 atmospheres to about 500 atmospheres (absolute). In
certain embodiments, the pressure can range from about 250
atmospheres to about 500 atmospheres (absolute).
[0768] In some embodiments, the pressure used in provided methods
and systems for converting PPL to AA is less than about 5
atmospheres (absolute). In some embodiments, the pressure used in
provided methods and systems is less than about 1 atmosphere
(absolute). In some embodiments, the pressure can range from about
0.01 atmospheres to about 1 atmosphere (absolute). In some
embodiments, the pressure can range from about 0.1 atmospheres to
about 0.8 atmospheres (absolute). In some embodiments, the pressure
can range from about 0.1 atmospheres to about 0.5 atmospheres
(absolute). In some embodiments, the pressure can range from about
0.01 atmospheres to about 0.1 atmospheres (absolute). In some
embodiments, the pressure can range from about 0.4 atmospheres to
about 1 atmosphere (absolute). In some embodiments, the pressure
can range from about 0.05 atmospheres to about 0.1 atmospheres
(absolute).
Lactone to C.sub.4 Products
[0769] In certain embodiments, the disclosed systems comprise a
first C.sub.4 reactor comprising an inlet fed by the outlet stream
comprising beta lactone from the central reactor. The first C.sub.4
reactor converts the beta lactone, such as BPL, into a first
C.sub.4 product. In certain embodiments, the first C.sub.4 product
is succinic anhydride (SA).
[0770] In certain embodiments, the first C.sub.4 product is SA, and
the system further comprises a second C.sub.4 reactor, comprising
an inlet fed by the outlet stream comprising SA of the first
C.sub.4 reactor, a second C.sub.4 reaction zone that converts at
least some of the SA to a second C.sub.4 product, and an outlet
which provides an outlet stream comprising the second C.sub.4
product.
[0771] In certain embodiments, the second C.sub.4 product is
succinic acid, 1,4 butanediol (BDO), tetrahydrofuran (THF) or gamma
butyrolactone (GBL).
[0772] In certain embodiments, the first C.sub.4 product is the
result of a second carbonylation reaction as shown below where the
epoxide is EO and the two-step carbonylation C.sub.4 product is
SA:
##STR00066##
[0773] This is a stepwise sequence by which two equivalents of CO
are added to the EO to first produce the C.sub.3 BPL followed by a
second insertion of CO to produce C.sub.4 SA. In certain
embodiments, the two-step sequence is carried out step-wise in
different reactors, wherein the central reactor receives a reaction
stream comprising EO and CO and converts them into the BPL, and the
first C.sub.4 reactor is a different reaction vessel from the
central reactor; it receives a reaction stream comprising the BPL
and additional CO and converts them into the first C.sub.4 product,
SA.
[0774] In other embodiments, the two-step sequence is carried out
in a one-pot sequence in a single reaction vessel, wherein the
central reactor receives an inlet stream comprising EO and CO and
converts them into BPL. In this instance, the central reactor
becomes the first C.sub.4 reaction zone when it receives additional
CO and converts BPL into a first C.sub.4 product, SA.
[0775] In certain embodiments, the two-step carbonylation reaction
produces the following overall reaction:
##STR00067##
[0776] where, R.sup.1 is selected from the group consisting of --H
and C.sub.1-6 aliphatic.
[0777] In certain embodiments, the two-step carbonylation reaction
produces the following overall reaction where the epoxide is
propylene oxide and the carbonylation product is methylsuccinic
anhydride:
##STR00068##
[0778] Suitable catalysts and reaction conditions for effecting the
above reactions are described herein and also disclosed in
published PCT applications WO2012/030619 and WO2013/122905, and
U.S. Pat. No. 8,481,756.
Succinic Anhydride to THF, GBL and BDO
[0779] Likewise, in certain embodiments, the system may include a
first C.sub.4 reactor for converting BPL to SA, where the system
further comprises a second C.sub.4 reaction zone that receives an
inlet stream comprising the succinic anhydride from the first
C.sub.4 reaction zone and converts it to a second C.sub.4 product
such as 1,4 butanediol (BDO), tetrahydrofuran (THF) or gamma
butyrolactone (GBL).
[0780] In some embodiments of the system, C.sub.3 and/or C.sub.4
reaction zones, producing an initial C.sub.3 and/or C.sub.4
product, can be configured in parallel with subsequent downstream
C.sub.3 and/or C.sub.4 reaction zones to convert the initial
C.sub.3 and/or C.sub.4 product into a subsequent C.sub.3 and/or
C.sub.4 product. For example, in certain embodiments, the system
may include a first C.sub.3 reaction zone for converting BPL to
PPL, where the system further comprises a third C.sub.3 reaction
zone that receives a reaction stream comprising the PPL from the
first C.sub.3 reaction zone and converts it to a third C.sub.3
product such as AA.
Large Scale AA Production
[0781] In another aspect, a system is provided for the production
of AA, e.g., an AA production plant, wherein the system produces AA
at a rate of about 200 to about 1,000 kilotons per annum (kta).
Presently, chemical plants generate approximately 160 kta AA from
propylene-based feedstock. Without being bound by theory, the
disclosed systems are capable of producing greater output of AA
from ethylene-based feedstock. In certain embodiments, the system
produces the AA from ethylene. In certain embodiments, the AA is
crude AA. In certain embodiments, the AA is glacial AA. In some
embodiments, the AA is substantially free of a product or by
product of propylene oxidation. In some embodiments, the AA is
substantially free of an aldehyde impurity. In some embodiments,
the AA is substantially free of stabilizers. In some embodiments,
the AA is substantially free of radical polymerization inhibitors.
In some embodiments, the AA is substantially free of anti-foam
agents.
[0782] Specifically, the disclosed systems include a reactor for
the oxidation of ethylene to EO, a reactor for carbonylating EO
with CO to produce BPL, and reactors for converting BPL to AA,
optionally via PPL.
[0783] In certain embodiments, the system produces AA at a rate of
about 200, 250, 300, 350, 400, 450, 500, 550, 600, 650, 700, 750,
800, 850, 900, 950, 1,000 kta, or within a range including any two
of these values.
[0784] In certain embodiments, the system comprises
[0785] an oxidative reactor, comprising an inlet fed by ethylene,
an oxidative reaction zone that converts at least some of the
ethylene to ethylene oxide (EO), and an outlet which provides an
outlet stream comprising the EO, which is fed to an inlet of a
central reactor,
[0786] the central reactor, comprising the inlet fed by the outlet
stream comprising the EO from the oxidative reactor and a carbon
monoxide (CO) source, a central reaction zone that converts at
least some of the EO to beta propiolactone (BPL), and an outlet
which provides an outlet stream comprising the BPL,
[0787] one or more of: [0788] (i) a first C.sub.3 reactor,
comprising an inlet fed by the outlet stream comprising BPL of the
central reactor, a first C.sub.3 reaction zone that converts at
least some of the BPL to a polypropiolactone (PPL), and an outlet
which provides an outlet stream comprising the PPL, and a second
C.sub.3 reactor, comprising an inlet fed by the outlet stream
comprising PPL of the first C.sub.3 reactor, a second C.sub.3
reaction zone that converts at least some of the PPL to AA, and an
outlet which provides an outlet stream comprising the AA, and
[0789] (ii) a third C.sub.3 reactor, comprising an inlet fed by the
outlet stream comprising BPL of the central reactor, a third
C.sub.3 reaction zone that converts at least some of the BPL to a
second C.sub.3 product that is other than PPL or AA, and an outlet
which provides an outlet stream comprising the second C.sub.3
product, and
[0790] a controller for independently modulating production of the
EO, BPL, AA and, optionally, PPL and any other C.sub.3
products.
[0791] In some variations, provided is a system for producing AA
from ethylene, comprising:
[0792] an ethylene source;
[0793] a carbon monoxide (CO) source;
[0794] an oxidative reactor comprising: [0795] an inlet configured
to receive ethylene from the ethylene source, [0796] an oxidative
reaction zone configured to convert at least some of the ethylene
to ethylene oxide (EO), and [0797] an outlet configured to provide
an outlet stream comprising the EO, and feed the outlet stream
comprising the EO to an inlet of a central reactor;
[0798] the central reactor comprising: [0799] an inlet configured
to receive EO from the outlet stream of the oxidative reactor and
CO from the CO source, [0800] a central reaction zone configured to
convert at least some of the EO to beta propiolactone (BPL), and
[0801] an outlet configured to provide an outlet stream comprising
the BPL;
[0802] one of (i) or (ii), or both: [0803] (i) a first C.sub.3
reactor comprising: [0804] an inlet configured to receive the
outlet stream comprising BPL of the central reactor, [0805] a first
C.sub.3 reaction zone configured to convert at least some of the
BPL to a polypropiolactone (PPL), and [0806] an outlet configured
to provide an outlet stream comprising the PPL, and [0807] a second
C.sub.3 reactor comprising; [0808] an inlet configured to receive
the outlet stream comprising PPL of the first C.sub.3 reactor,
[0809] a second C.sub.3 reaction zone configured to convert at
least some of the PPL to AA, and [0810] an outlet configured to
provide an outlet stream comprising the AA, and [0811] (ii) a third
C.sub.3 reactor comprising: [0812] an inlet configured to receive
the outlet stream comprising BPL of the central reactor, [0813] a
third C.sub.3 reaction zone configured to convert at least some of
the BPL to AA, and [0814] an outlet configured to provide an outlet
stream comprising the AA; and
[0815] a controller to independently modulating production of the
EO, BPL, AA and, optionally, PPL and any products.
[0816] In one embodiment, one of (i) or (ii), or both is (i). Thus,
in one variation, provided is a system for producing AA from
ethylene, comprising:
[0817] an ethylene source;
[0818] a carbon monoxide (CO) source;
[0819] an oxidative reactor comprising: [0820] an inlet configured
to receive ethylene from the ethylene source, [0821] an oxidative
reaction zone configured to convert at least some of the ethylene
to ethylene oxide (EO), and [0822] an outlet configured to provide
an outlet stream comprising the EO, and feed the outlet stream
comprising the EO to an inlet of a central reactor;
[0823] the central reactor comprising: [0824] an inlet configured
to receive the outlet stream comprising the EO from the oxidative
reactor and the CO source, [0825] a central reaction zone
configured to convert at least some of the EO to beta propiolactone
(BPL), and [0826] an outlet configured to provide an outlet stream
comprising the BPL;
[0827] a first C.sub.3 reactor comprising: [0828] an inlet
configured to receive the outlet stream comprising BPL of the
central reactor, [0829] a first C.sub.3 reaction zone configured to
convert at least some of the BPL to polypropiolactone (PPL), and
[0830] an outlet configured to provide an outlet stream comprising
the PPL, and
[0831] a second C.sub.3 reactor comprising; [0832] an inlet
configured to receive the outlet stream comprising PPL of the first
C.sub.3 reactor, [0833] a second C.sub.3 reaction zone configured
to convert at least some of the PPL to AA, and [0834] an outlet
configured to provide an outlet stream comprising the AA, and
[0835] a controller to independently modulating production of the
EO, BPL, PPL and AA.
[0836] In one embodiment, one of (i) or (ii), or both is (ii).
Thus, in one variation, provided is a system for producing AA from
ethylene, comprising:
[0837] an ethylene source;
[0838] a carbon monoxide (CO) source;
[0839] an oxidative reactor comprising: [0840] an inlet configured
to receive ethylene from the ethylene source, [0841] an oxidative
reaction zone configured to convert at least some of the ethylene
to ethylene oxide (EO), and [0842] an outlet configured to provide
an outlet stream comprising the EO, and feed the outlet stream
comprising the EO to an inlet of a central reactor;
[0843] the central reactor comprising: [0844] an inlet configured
to receive the outlet stream comprising the EO from the oxidative
reactor and the CO source, [0845] a central reaction zone
configured to convert at least some of the EO to beta propiolactone
(BPL), and [0846] an outlet configured to provide an outlet stream
comprising the BPL;
[0847] a C.sub.3 reactor comprising: [0848] an inlet configured to
receive the outlet stream comprising BPL of the central reactor,
[0849] a C.sub.3 reaction zone configured to convert at least some
of the BPL to AA, and [0850] an outlet configured to provide an
outlet stream comprising the AA; and
[0851] a controller to independently modulating production of the
EO, BPL and AA.
[0852] In certain embodiments, the system further comprises one or
more of:
[0853] (iv) a fourth C.sub.3 reactor, comprising an inlet fed by
the outlet stream comprising BPL of the central reactor, a fourth
C.sub.3 reaction zone that converts at least some of the BPL to a
C.sub.3 product other than acrylic acid, and an outlet which
provides an outlet stream comprising the C.sub.3 product other than
acrylic acid, and
[0854] (v) a first C.sub.4 reactor, comprising an inlet fed by the
outlet stream comprising BPL of the central reactor, a first
C.sub.4 reaction zone that converts at least some of the BPL to a
first C.sub.4 product, and an outlet which provides an outlet
stream comprising the first C.sub.4 product.
[0855] In some embodiments, the system further comprises one of
(iv) or (v), or both:
[0856] (iv) a fourth C.sub.3 reactor comprising: [0857] an inlet
configured to receive the outlet stream comprising BPL of the
central reactor, [0858] a fourth C.sub.3 reaction zone configured
to convert at least some of the BPL to a C.sub.3 product other than
acrylic acid, and [0859] an outlet configured to provide an outlet
stream comprising the C.sub.3 product other than acrylic acid,
and
[0860] (v) a first C.sub.4 reactor comprising: [0861] an inlet
configured to receive the outlet stream comprising BPL of the
central reactor, [0862] a first C.sub.4 reaction zone configured to
convert at least some of the BPL to a first C.sub.4 product, and
[0863] an outlet configured to provide an outlet stream comprising
the first C.sub.4 product.
[0864] In certain embodiments, one of (iv) or (v), or both is (iv).
Thus, in certain variations, the system further comprises:
[0865] another C.sub.3 reactor comprising: [0866] an inlet
configured to receive the outlet stream comprising BPL of the
central reactor, [0867] another C.sub.3 reaction zone configured to
convert at least some of the BPL to a C.sub.3 product other than
acrylic acid, and [0868] an outlet configured to provide an outlet
stream comprising the C.sub.3 product other than acrylic acid.
[0869] In certain embodiments, one of (iv) or (v), or both is (v).
Thus, in certain variations, the system further comprises:
[0870] a C.sub.4 reactor comprising: [0871] an inlet configured to
receive the outlet stream comprising BPL of the central reactor,
[0872] a C.sub.4 reaction zone configured to convert at least some
of the BPL to a first C.sub.4 product, and [0873] an outlet
configured to provide an outlet stream comprising the first C.sub.4
product.
[0874] In another aspect, a method is provided for producing
acrylic acid (AA) from ethylene in a single integrated system, the
method comprising:
[0875] providing ethylene to an oxidative reactor that converts at
least some of the ethylene to ethylene oxide (EO),
[0876] providing EO to a central reactor that converts at least
some of the EO to beta propiolactone (BPL),
[0877] and at least one of the following providing steps:
[0878] providing BPL to a first reactor that converts at least some
of the BPL to AA, and
[0879] providing BPL to a reactor that converts at least some of
the BPL to polypropiolactone (PPL), and
[0880] isolating acrylic acid at a rate of about 200 to about 800
kilotons per annum (kta).
[0881] In some variations, provided is a method for producing
acrylic acid (AA) from ethylene in a single integrated system, the
method comprising:
[0882] providing ethylene to an oxidative reactor that converts at
least some of the ethylene to ethylene oxide (EO);
[0883] providing EO to a central reactor that converts at least
some of the EO to beta propiolactone (BPL);
[0884] and at least one or both of (i) and (ii):
[0885] (i) providing BPL to a first reactor that converts at least
some of the BPL to AA, and
[0886] (ii) providing BPL to a reactor that converts at least some
of the BPL to polypropiolactone (PPL).
[0887] In certain variations of the foregoing method, BPL is
provided to a first reactor that converts at least some of the BPL,
and the method further comprises isolating acrylic acid at a rate
of about 200 to about 800 kilotons per annum (kta).
[0888] In one embodiment, the at least one or both of (i) and (ii)
is (i). Thus, in one variation, provided is a method for producing
acrylic acid (AA) from ethylene in a single integrated system, the
method comprising:
[0889] providing ethylene to an oxidative reactor that converts at
least some of the ethylene to ethylene oxide (EO);
[0890] providing EO to a central reactor that converts at least
some of the EO to beta propiolactone (BPL); and
[0891] providing BPL to a first reactor that converts at least some
of the BPL to AA; and optionally isolating acrylic acid at a rate
of about 200 to about 800 kilotons per annum (kta).
[0892] In another embodiment, the at least one or both of (i) and
(ii) is (ii). Thus, in one variation, provided is a method for
producing acrylic acid (AA) from ethylene in a single integrated
system, the method comprising:
[0893] providing ethylene to an oxidative reactor that converts at
least some of the ethylene to ethylene oxide (EO);
[0894] providing EO to a central reactor that converts at least
some of the EO to beta propiolactone (BPL); and
[0895] providing BPL to a reactor that converts at least some of
the BPL to polypropiolactone (PPL).
[0896] In yet another embodiment, the at least one or both of (i)
and (ii) is both (i) and (ii). Thus, in yet another variation,
provided is a method for producing acrylic acid (AA) from ethylene
in a single integrated system, the method comprising:
[0897] providing ethylene to an oxidative reactor that converts at
least some of the ethylene to ethylene oxide (EO);
[0898] providing EO to a central reactor that converts at least
some of the EO to beta propiolactone (BPL);
[0899] providing BPL to a first reactor that converts at least some
of the BPL to AA; and
[0900] providing BPL to a reactor that converts at least some of
the BPL to polypropiolactone (PPL); and
optionally isolating acrylic acid at a rate of about 200 to about
800 kilotons per annum (kta).
[0901] The term "integrated system" as used herein means a single
system such as a chemical plant, confined to a single geographic
location, and comprising an abutting series of reactors or system
components. The integrated system can produce multiple products
from a single precursor such as an epoxide or lactone.
Enumerated Embodiments
[0902] The following enumerated embodiments are representative of
some aspects of the invention.
1. A system for the production of chemicals, comprising: [0903] a
central reactor, comprising an inlet fed by an epoxide source and a
carbon monoxide (CO) source, a central reaction zone that converts
at least some of the epoxide to a beta lactone, and an outlet which
provides an outlet stream comprising the beta lactone, [0904] two
or more of: [0905] (i) a first C.sub.3 reactor, comprising an inlet
fed by the outlet stream comprising beta lactone of the central
reactor, a first C.sub.3 reaction zone that converts at least some
of the beta lactone to a first C.sub.3 product, and an outlet which
provides an outlet stream comprising the first C.sub.3 product,
[0906] (ii) a second C.sub.3 reactor, comprising an inlet fed by
the outlet stream comprising beta lactone of the central reactor, a
second C.sub.3 reaction zone that converts at least some of the
beta lactone to a second C.sub.3 product, and an outlet which
provides an outlet stream comprising the second C.sub.3 product,
and [0907] (iii) a first C.sub.4 reactor, comprising an inlet fed
by the outlet stream comprising beta lactone of the central
reactor, a first C.sub.4 reaction zone that converts at least some
of the beta lactone to a first C.sub.4 product, and an outlet which
provides an outlet stream comprising the first C.sub.4 product, and
[0908] a controller for independently modulating production of the
beta lactone and each of the products, [0909] with the provision
that the first C.sub.3 product differs from the second C.sub.3
product. 2. The system of embodiment 1, comprising the first
C.sub.3 reactor and the second C.sub.3 reactor. 3. The system of
embodiment 1, comprising the first C.sub.3 reactor and the first
C.sub.4 reactor. 4. The system of embodiment 1, wherein the epoxide
is ethylene oxide (EO) and the beta lactone is beta propiolactone
(BPL). 5. The system of embodiment 4, further comprising an
oxidative reactor, comprising an inlet fed by ethylene, an
oxidative reaction zone that converts at least some of the ethylene
to EO, and an outlet which provides an outlet stream comprising the
EO, which is fed to the inlet of the central reactor. 6. The system
of embodiment 1, wherein the first C.sub.3 product and the second
C.sub.3 product are independently selected from an
.alpha.,.beta.-unsaturated acid, an .alpha.,.beta.-unsaturated
ester, an .alpha.,.beta.-unsaturated amide, a polymer and
1,3-propanediol (PDO). 7. The system of embodiment 6, wherein the
first C.sub.3 product is polypropiolactone (PPL). 8. The system of
embodiment 6, wherein the first C.sub.3 product is acrylic acid. 9.
The system of embodiment 1, wherein the first C.sub.3 product is
PPL, and the system further comprises a third C.sub.3 reactor,
comprising an inlet fed by the outlet stream comprising PPL of the
first C.sub.3 reactor, a third C.sub.3 reaction zone that converts
at least some of the PPL to a third C.sub.3 product, and an outlet
which provides an outlet stream comprising the third C.sub.3
product. 10. The system of embodiment 1, wherein the third C.sub.3
product is acrylic acid. 11. The system of embodiment 1, wherein
the first C.sub.4 product is succinic anhydride. 12. The system of
embodiment 1, wherein the first C.sub.4 product is succinic
anhydride, and the system further comprises a second C.sub.4
reactor, comprising an inlet fed by the outlet stream comprising
succinic anhydride of the first C.sub.4 reactor, a second C.sub.4
reaction zone that converts at least some of the succinic anhydride
to a second C.sub.4 product, and an outlet which provides an outlet
stream comprising the second C.sub.4 product. 13. The system of
embodiment 12, wherein the second C.sub.4 product is succinic acid,
1,4 butanediol (BDO), tetrahydrofuran (THF) or gamma butyrolactone
(GBL). 14. A system for the production of acrylic acid (AA),
wherein the system produces AA at about 200 to about 800 kilotons
per annum (kta). 15. The system of embodiment 14, wherein the
system produces the AA from ethylene. 16. The system of embodiment
15, comprising: [0910] an oxidative reactor, comprising an inlet
fed by ethylene, an oxidative reaction zone that converts at least
some of the ethylene to ethylene oxide (EO), and an outlet which
provides an outlet stream comprising the EO, which is fed to an
inlet of a central reactor, [0911] the central reactor, comprising
the inlet fed by the outlet stream comprising the EO from the
oxidative reactor and a carbon monoxide (CO) source, a central
reaction zone that converts at least some of the EO to beta
propiolactone (BPL), and an outlet which provides an outlet stream
comprising the BPL, [0912] one or more of: [0913] (i) a first
C.sub.3 reactor, comprising an inlet fed by the outlet stream
comprising BPL of the central reactor, a first C.sub.3 reaction
zone that converts at least some of the BPL to a polypropiolactone
(PPL), and an outlet which provides an outlet stream comprising the
PPL, and a third C.sub.3 reactor, comprising an inlet fed by the
outlet stream comprising PPL of the first C.sub.3 reactor, a third
C.sub.3 reaction zone that converts at least some of the PPL to AA,
and an outlet which provides an outlet stream comprising the AA,
and [0914] (iii) a second C.sub.3 reactor, comprising an inlet fed
by the outlet stream comprising BPL of the central reactor, a
second C.sub.3 reaction zone that converts at least some of the BPL
to AA, and an outlet which provides an outlet stream comprising the
AA, and [0915] a controller for independently modulating production
of the EO, BPL, AA and, optionally, PPL and any products. 17. The
system of embodiment 16, further comprising one or more of: [0916]
(iv) a fourth C.sub.3 reactor, comprising an inlet fed by the
outlet stream comprising BPL of the central reactor, a fourth
C.sub.3 reaction zone that converts at least some of the BPL to a
C.sub.3 product other than acrylic acid, and an outlet which
provides an outlet stream comprising the C.sub.3 product other than
acrylic acid, and [0917] (v) a first C.sub.4 reactor, comprising an
inlet fed by the outlet stream comprising BPL of the central
reactor, a first C.sub.4 reaction zone that converts at least some
of the BPL to a first C.sub.4 product, and an outlet which provides
an outlet stream comprising the first C.sub.4 product. 18. A
method, wherein the method is for the conversion of an epoxide to
two or more of: a first C.sub.3 product, a second C.sub.3 product,
and a first C.sub.4 product within an integrated system, the method
comprising: [0918] providing an inlet stream comprising an epoxide
and carbon monoxide (CO) to a central reactor of the integrated
system; [0919] contacting the inlet stream with a carbonylation
catalyst in a central reaction zone to effect conversion of at
least a portion of the provided epoxide to a beta lactone;
directing an outlet stream comprising beta lactone from the central
reaction zone to two or more of: [0920] (i) a first C.sub.3
reactor, comprising an inlet fed by the outlet stream comprising
beta lactone of the central reactor, a first C.sub.3 reaction zone
that converts at least some of the beta lactone to a first C.sub.3
product, and an outlet from which an outlet stream comprising the
first C.sub.3 product is obtainable, [0921] (ii) a second C.sub.3
reactor, comprising an inlet fed by the outlet stream comprising
beta lactone of the central reactor, a second C.sub.3 reaction zone
that converts at least some of the beta lactone to a second C.sub.3
product, and an outlet from which an outlet stream comprising the
second C.sub.3 product is obtainable, and [0922] (iii) a first
C.sub.4 reactor, comprising an inlet fed by the outlet stream
comprising beta lactone of the central reactor, a first C.sub.4
reaction zone that converts at least some of the beta lactone to a
first C.sub.4 product, and an outlet from which an outlet stream
comprising the first C.sub.4 product is obtainable, and [0923]
obtaining two or more of the first C.sub.3 product, the second
C.sub.3 product, and the first C.sub.4 product. 19. The method of
embodiment 18, further comprising: [0924] providing an inlet stream
comprising ethylene to an inlet of an oxidative reactor in which at
least some of the ethylene is converted to ethylene oxide (EO), and
[0925] providing an outlet stream comprising EO from the oxidative
reactor, to the inlet of the central reactor in which at least some
of the EO is converted to BPL. 20. The method of embodiment 18,
comprising directing the outlet stream comprising beta lactone from
the central reaction zone to the first C.sub.3 reactor and the
second C.sub.3 reactor. 21. The method of embodiment 18, comprising
directing the outlet stream comprising beta lactone from the
central reaction zone to the first C.sub.3 reactor and the first
C.sub.4 reactor. 22. The method of embodiment 18, wherein the
epoxide is ethylene oxide (EO) and the beta lactone is beta
propiolactone (BPL). 23. The method of embodiment 18, wherein the
first C.sub.3 product and the second C.sub.3 product are
independently selected from an .alpha.,.beta.-unsaturated acid, an
.alpha.,.beta.-unsaturated ester, an .alpha.,.beta.-unsaturated
amide, a C.sub.3 polymer and 1,3-propanediol (PDO). 24. The method
of embodiment 18, wherein the first C.sub.3 product is
polypropiolactone (PPL). 25. The method of embodiment 18, wherein
the first C.sub.3 product is acrylic acid. 26. The method of
embodiment 24, further comprising: [0926] directing the an outlet
stream comprising PPL from the first C.sub.3 reactor to a third
C.sub.3 reactor, comprising an inlet fed by the outlet stream
comprising PPL of the first C.sub.3 reactor, a third C.sub.3
reaction zone that converts at least some of the PPL to a third
C.sub.3 product, and an outlet from which an outlet stream
comprising the third C.sub.3 product is obtainable. 27. The method
of enumerated 26, wherein the third C.sub.3 product is acrylic
acid. 28. The method of embodiment 18, wherein the first C.sub.4
product is succinic anhydride. 29. The method of embodiment 18,
wherein the first C.sub.4 product is succinic anhydride, and the
system further comprises a second C.sub.4 reactor, comprising an
inlet fed by the outlet stream comprising succinic anhydride of the
first C.sub.4 reactor, a second C.sub.4 reaction zone that converts
at least some of the succinic anhydride to a second C.sub.4
product, and an outlet from which an outlet stream comprising the
second C.sub.4 product is obtainable. 30. The method of embodiment
29, wherein the second C.sub.4 product is succinic acid, 1,4
butanediol (BDO), tetrahydrofuran (THF) or gamma butyrolactone
(GBL). 31. A method, wherein the method is for the production of
acrylic acid (AA) from ethylene in a single integrated system, the
method comprising: [0927] providing ethylene to an oxidative
reactor that converts at least some of the ethylene to ethylene
oxide (EO), [0928] providing EO to a central reactor that converts
at least some of the EO to beta propiolactone (BPL), and at least
one of: [0929] providing BPL to a first reactor that converts at
least some of the BPL to AA, and [0930] providing BPL to a reactor
that converts at least some of the BPL to polypropiolactone (PPL),
and [0931] isolating acrylic acid at a rate of about 200 to about
800 kilotons per annum (kta). 32. A system for the production of
C.sub.3 and C.sub.4 products, comprising: [0932] an epoxide source;
[0933] a carbon monoxide (CO) source; [0934] a central reactor,
comprising: [0935] an inlet configured to receive epoxide from the
epoxide source and CO from the CO source, [0936] a central reaction
zone configured to convert at least some of the epoxide to a beta
lactone, and [0937] an outlet configured to provide an outlet
stream comprising the beta lactone, [0938] two or more of
(i)-(iii): [0939] (i) a first C.sub.3 reactor, comprising: [0940]
an inlet configured to receive the outlet stream comprising beta
lactone of the central reactor, [0941] a first C.sub.3 reaction
zone configured to convert at least some of the beta lactone to a
first C.sub.3 product, and [0942] an outlet configured to provide
an outlet stream comprising the first C.sub.3 product, [0943] (ii)
a second C.sub.3 reactor, comprising: [0944] an inlet configured to
receive the outlet stream comprising beta lactone of the central
reactor, [0945] a second C.sub.3 reaction zone configured to
convert at least some of the beta lactone to a second C.sub.3
product, and [0946] an outlet configured to provide an outlet
stream comprising the second C.sub.3 product, and [0947] (iii) a
first C.sub.4 reactor, comprising: [0948] an inlet configured to
receive the outlet stream comprising beta lactone of the central
reactor, [0949] a first C.sub.4 reaction zone configured to convert
at least some of the beta lactone to a first C.sub.4 product, and
[0950] an outlet configured to provide an outlet stream comprising
the first C.sub.4 product, and [0951] a controller to independently
modulate production of the beta lactone and each of the products,
[0952] provided that the first C.sub.3 product differs from the
second C.sub.3 product. 33. The system of embodiment 32, wherein
the two or more of (i)-(iii) is (i) the first C.sub.3 reactor and
(ii) the second C.sub.3 reactor. 34. The system of embodiment 32,
wherein the two or more (i)-(iii) is (i) the first C.sub.3 reactor
and (iii) the first C.sub.4 reactor. 35. The system of any one of
embodiments 32 to 34, wherein the epoxide is ethylene oxide (EO)
and the beta lactone is beta propiolactone (BPL). 36. The system of
embodiment 35, further comprising; [0953] an ethylene source;
[0954] an oxidative reactor comprising: [0955] an inlet configured
to receive ethylene, [0956] an oxidative reaction zone configured
to convert at least some of the ethylene to EO, and [0957] an
outlet configured to provide an outlet stream comprising the EO,
and feed the outlet stream comprising EO to the inlet of the
central reactor. 37. The system of any one of embodiments 32 to 36,
wherein the first C.sub.3 product and the second C.sub.3 product
are independently selected from an .alpha.,.beta.-unsaturated acid,
an .alpha.,.beta.-unsaturated ester, an .alpha.,.beta.-unsaturated
amide, a polymer and 1,3-propanediol (PDO). 38. The system of
embodiment 37, wherein the first C.sub.3 product is
polypropiolactone (PPL). 39. The system of embodiment 37, wherein
the first C.sub.3 product is acrylic acid. 40. The system of any
one of embodiments 32 to 38, wherein the first C.sub.3 product is
PPL, and the system further comprises: [0958] a third C.sub.3
reactor comprising: [0959] an inlet configured to receive the
outlet stream comprising PPL of the first C.sub.3 reactor, [0960] a
third C.sub.3 reaction zone configured to convert at least some of
the PPL to a third C.sub.3 product, and [0961] an outlet configured
to provide an outlet stream comprising the third C.sub.3 product.
41. The system of embodiment 40, wherein the third C
.sub.3 product is acrylic acid (AA). 42. The system of embodiment
41, wherein the system is configured to produce AA at about 200 to
about 800 kilotons per annum (kta). 43. The system of any one of
embodiments 32 to 42, wherein the first C.sub.4 product is succinic
anhydride. 44. The system of any one of embodiments 32 to 42,
wherein the first C.sub.4 product is succinic anhydride, and the
system further comprises: [0962] a second C.sub.4 reactor
comprising: [0963] an inlet configured to receive the outlet stream
comprising succinic anhydride of the first C.sub.4 reactor, [0964]
a second C.sub.4 reaction zone configured to convert at least some
of the succinic anhydride to a second C.sub.4 product, and [0965]
an outlet configured to provide an outlet stream comprising the
second C.sub.4 product. 45. The system of embodiment 44, wherein
the second C.sub.4 product is succinic acid, 1,4 butanediol (BDO),
tetrahydrofuran (THF) or gamma butyrolactone (GBL). 46. A system,
comprising: [0966] an ethylene source; [0967] a carbon monoxide
(CO) source; [0968] an alcohol source; [0969] an oxidative reactor
comprising: [0970] an inlet configured to receive ethylene from the
ethylene source, [0971] an oxidative reaction zone configured to
convert at least some of the ethylene to ethylene oxide (EO), and
[0972] an outlet configured to provide an EO stream comprising the
EO; [0973] a central reactor comprising: [0974] an inlet configured
to receive EO from the EO stream of the oxidative reactor and CO
from the CO source, [0975] a central reaction zone configured to
convert at least some of the EO to beta propiolactone (BPL), and
[0976] an outlet configured to provide a BPL stream comprising the
BPL; [0977] a first C3 reactor comprising: [0978] an inlet
configured to receive BPL from at least a portion of the BPL stream
of the central reactor, [0979] a first C3 reaction zone configured
to convert at least some of the BPL to a polypropiolactone (PPL),
and [0980] an outlet configured to provide a PPL stream comprising
the PPL; [0981] a second C3 reactor comprising; [0982] an inlet
configured to receive PPL from the PPL stream of the first C3
reactor, [0983] a second C3 reaction zone configured to convert at
least some of the PPL to AA, and [0984] an outlet configured to
provide an AA stream comprising the AA; [0985] a third C3 reactor
comprising: [0986] an inlet configured to receive BPL from at least
a portion of the BPL stream of the central reactor, and an alcohol
from the alcohol source, [0987] a third C3 reaction zone configured
to convert at least some of the BPL to acrylate esters, and [0988]
an outlet configured to provide an acrylate ester stream comprising
the acrylate esters; and [0989] a controller to independently
modulating production of the EO, BPL, PPL, AA, and acrylate esters.
47. The system of embodiment 46, wherein the system simultaneously
produces the PPL stream, the AA stream, and the acrylate ester
stream. 48. The system embodiment 46 or 47, wherein the controller
modulates a ratio of PPL:AA:acrylate ester from the PPL stream, the
AA stream, and the acrylate ester stream. 49. The system of any one
of embodiments 46 to 47, wherein the inlet of the second C3 reactor
is configured to receive PPL from a fraction of the PPL stream of
the first C3 reactor, and wherein the controller modulates the
fraction of the PPL output stream that is received by the inlet of
the second C3 reactor. 50. The system of any one of embodiments 46
to 49, further comprising: [0990] a PPL isolation unit comprising:
[0991] a PPL processing unit; [0992] a PPL packaging unit; and
[0993] a PPL outlet configured to provide packaged PPL for
distribution. 51. A system, comprising: [0994] an ethylene source;
[0995] a carbon monoxide (CO) source; [0996] an alcohol source;
[0997] an oxidative reactor comprising: [0998] an inlet configured
to receive ethylene from the ethylene source, [0999] an oxidative
reaction zone configured to convert at least some of the ethylene
to ethylene oxide (EO), and [1000] an outlet configured to provide
an EO stream comprising the EO; [1001] a central reactor
comprising: [1002] an inlet configured to receive EO from the EO
stream of the oxidative reactor and CO from the CO source, [1003] a
central reaction zone configured to convert at least some of the EO
to beta propiolactone (BPL), and [1004] an outlet configured to
provide a BPL stream comprising the BPL; [1005] a first C3 reactor
comprising: [1006] an inlet configured to receive BPL from at least
a portion of the BPL stream of the central reactor, [1007] a first
C3 reaction zone configured to convert at least some of the BPL to
a polypropiolactone (PPL), and [1008] an outlet configured to
provide a PPL stream comprising the PPL; [1009] a second C3 reactor
comprising; [1010] an inlet configured to receive BPL from at least
a portion of the BPL stream of the central reactor, [1011] a second
C3 reaction zone configured to convert at least some of the BPL to
AA, and [1012] an outlet configured to provide an AA stream
comprising the AA; [1013] a third C3 reactor comprising: [1014] an
inlet configured to receive BPL from at least a portion of the BPL
stream of the central reactor, and an alcohol from the alcohol
source, [1015] a third C3 reaction zone configured to convert at
least some of the BPL to acrylate esters, and [1016] an outlet
configured to provide an acrylate ester stream comprising the
acrylate esters; and [1017] a controller to independently
modulating production of the EO, BPL, PPL, AA, and acrylate esters.
52. The system of embodiment 51, wherein the system simultaneously
produces two or more of the PPL stream, the AA stream, and the
acrylate ester stream 53. The system of embodiment 51, wherein the
system simultaneously produces the PPL stream, the AA stream, and
the acrylate ester stream. 54. The system of any one of embodiments
51 to 53, wherein the controller modulates a ratio of
PPL:AA:acrylate ester from the PPL stream, the AA stream, and the
acrylate ester stream. 55. A system, comprising: [1018] an ethylene
source; [1019] a carbon monoxide (CO) source; [1020] an oxidative
reactor comprising: [1021] an inlet configured to receive ethylene
from the ethylene source, [1022] an oxidative reaction zone
configured to convert at least some of the ethylene to ethylene
oxide (EO), and [1023] an outlet configured to provide an EO stream
comprising the EO; [1024] a central reactor comprising: [1025] an
inlet configured to receive EO from the EO stream of the oxidative
reactor and CO from the CO source, [1026] a central reaction zone
configured to convert at least some of the EO to beta propiolactone
(BPL), and [1027] an outlet configured to provide a BPL stream
comprising the BPL; [1028] a first C3 reactor comprising: [1029] an
inlet configured to receive BPL from at least a portion of the BPL
stream of the central reactor, [1030] a first C3 reaction zone
configured to convert at least some of the BPL to a
polypropiolactone (PPL), and [1031] an outlet configured to provide
a PPL stream comprising the PPL; [1032] a second C3 reactor
comprising; [1033] an inlet configured to receive PPL from the PPL
stream of the first C3 reactor, [1034] a second C3 reaction zone
configured to convert at least some of the PPL to AA, and [1035] an
outlet configured to provide an AA stream comprising the AA; [1036]
a first C4 reactor comprising: [1037] an inlet configured to
receive BPL from at least a portion of the BPL stream of the
central reactor, and carbon monoxide from the CO source, [1038] a
first C4 reaction zone configured to convert at least some of the
BPL to succinic anhydride (SA), and [1039] an outlet configured to
provide a succinic anhydride stream comprising the succinic
anhydride; and [1040] a controller to independently modulating
production of the EO, BPL, PPL, AA, and SA. 56. The system
embodiment 55, wherein the system simultaneously produces the PPL
stream, the AA stream, and the SA stream. 57. The system of
embodiment 55 or 56, wherein the controller modulates a ratio of
PPL:AA:SA from the PPL stream, the AA stream, and the SA stream.
58. The system of any one of embodiments 55 to 57, wherein the
inlet of the second C3 reactor is configured to receive PPL from a
fraction of the PPL stream of the first C3 reactor, and wherein the
controller modulates the fraction of the PPL stream that is
received by the inlet of the second C3 reactor. 59. The system of
any one of embodiments 55 to 58, further comprising: [1041] a PPL
isolation unit comprising: [1042] a PPL processing unit, [1043] a
PPL packaging unit, and [1044] a PPL outlet configured to provide
packaged PPL for distribution. 60. The system of any one of
embodiments 55 to 59, further comprising: [1045] a hydrogen source;
and [1046] a second C4 reactor comprising: [1047] an inlet
configured to receive SA from the SA stream of the first C4
reactor, [1048] a hydrogen inlet fed from the hydrogen source,
[1049] a second C4 reaction zone configured to hydrogenate at least
a portion of the SA to provide a C4 product stream comprising 1,4
butanediol (BDO), tetrahydrofuran (THF), or gamma butyrolactone
(GBL), or any combinations thereof. 61. The system of embodiment
60, wherein the controller is configured to further modulate
production of BDO, THF, and GBL. 62. A system, comprising: [1050]
an ethylene source; [1051] a carbon monoxide (CO) source; [1052] an
alcohol source; [1053] an oxidative reactor comprising: [1054] an
inlet configured to receive ethylene from the ethylene source,
[1055] an oxidative reaction zone configured to convert at least
some of the ethylene to ethylene oxide (EO), and [1056] an outlet
configured to provide an EO stream comprising the EO, [1057] a
central reactor comprising: [1058] an inlet configured to receive
EO from the EO stream of the oxidative reactor and at least a
portion of CO from the CO source, [1059] a central reaction zone
configured to convert at least some of the EO to beta propiolactone
(BPL), and [1060] an outlet configured to provide a BPL stream
comprising the BPL; [1061] a first C3 reactor comprising: [1062] an
inlet configured to receive BPL from at least a portion of the BPL
stream of the central reactor, [1063] a first C3 reaction zone
configured to convert at least some of the BPL to a
polypropiolactone (PPL), and [1064] an outlet configured to provide
a PPL stream comprising the PPL; [1065] a second C3 reactor
comprising; [1066] an inlet configured to receive BPL from the BPL
stream of the central reactor, [1067] a second C3 reaction zone
configured to convert at least some of the BPL to AA, and [1068] an
outlet configured to provide an AA stream comprising the AA; [1069]
a third C3 reactor comprising: [1070] an inlet configured to
receive BPL from at least a portion of the BPL stream of the
central reactor, and an alcohol from the alcohol source, [1071] a
third C3 reaction zone configured to convert at least some of the
BPL to acrylate esters, and [1072] an outlet configured to provide
an acrylate ester stream comprising the acrylate esters; [1073] a
first C4 reactor comprising: [1074] an inlet configured to receive
BPL from at least a portion of the BPL stream of the central
reactor, and at least a portion of CO from the CO source, [1075] a
first C4 reaction zone configured to convert at least some of the
BPL to succinic anhydride (SA), and [1076] an outlet configured to
provide a SA stream comprising the succinic anhydride; and [1077] a
controller to independently modulating production of the EO, BPL,
PPL, AA, acrylate esters, and SA. 63. The system of embodiment 62,
wherein the system simultaneously produces the PPL stream, the AA
stream, and the acrylate ester stream. 64. The system of embodiment
62, wherein the system simultaneously produces the PPL stream, the
AA stream, the acrylate ester stream, and the SA stream. 65. The
system of any one of embodiments 62 to 64, wherein the controller
modulates a ratio PPL:AA:acrylate ester from the PPL stream, the AA
stream, and the acrylate ester stream. 66. The system of any one of
embodiments 62 to 65, wherein the controller modulates a ratio
PPL:AA:acrylate ester:SA from the PPL stream, the AA stream, the
acrylate ester stream, and the SA stream. 67. The system of any one
of embodiments 62 to 66, wherein the inlet of the second C3 reactor
is configured to receive PPL from a fraction of the PPL stream of
the first C3 reactor, and wherein the controller modulates the
fraction of the PPL stream that is fed to the second C3 reactor.
68. The system of any one of embodiments 62 to 67, further
comprising: [1078] a hydrogen source; [1079] a second C4 reactor
comprising: [1080] at least one inlet configured to receive SA from
the SA stream of the first C4 reactor, and hydrogen from the
hydrogen source, [1081] a second C4 reaction zone configured to
hydrogenate at least a portion of the SA to provide a C4 product
stream comprising 1,4 butanediol (BDO), tetrahydrofuran (THF), or
gamma butyrolactone (GBL), or any combinations thereof. 69. The
system of embodiment 68, wherein the controller is configured to
further modulate production of BDO, THF, and GBL. 70. A method for
converting an epoxide to two or more of: a first C.sub.3 product, a
second C.sub.3 product, and a first C.sub.4 product within an
integrated system, the method comprising: [1082] providing an inlet
stream comprising an epoxide and carbon monoxide (CO) to a central
reactor of the integrated system; [1083] contacting the inlet
stream with a carbonylation catalyst in a central reaction zone;
[1084] converting at least a portion of the epoxide to a beta
lactone to produce an outlet stream comprising beta lactone; [1085]
(i) directing the outlet stream comprising beta lactone from the
central reaction zone to a first C.sub.3 reactor, and converting at
least some of the beta lactone to a first C.sub.3 product in the
first C.sub.3 reactor to produce an outlet stream comprising the
first C.sub.3 product, or [1086] (ii) directing the outlet stream
comprising beta lactone from the central reaction zone to a second
C.sub.3 reactor, and converting at least some of the beta lactone
to a second C.sub.3 product in the second C.sub.3 reactor to
produce an outlet stream comprising the second C.sub.3 product, or
[1087] (iii) directing the outlet stream comprising beta lactone
from the central reaction zone to a first C.sub.4 reactor, and
converting at least some of the beta lactone to a first C.sub.4
product in the first C.sub.4 reactor to produce an outlet stream
comprising the first C.sub.4 product, [1088] provided that at least
two of (i)-(iii) are selected; and [1089] obtaining two or more of
the first C.sub.3 product, the second C.sub.3 product, and the
first C.sub.4 product. 71. The method of embodiment 70, further
comprising: [1090] providing an inlet stream comprising ethylene to
an inlet of an oxidative reactor;
[1091] converting at least some of the ethylene to ethylene oxide
(EO) to produce an outlet stream comprising EO; [1092] directing
the outlet stream comprising EO from the oxidative reactor to the
inlet of the central reactor; and [1093] converting at least some
of the EO to BPL. 72. The method of embodiment 70 or 71, wherein
the outlet stream comprising beta lactone is directed from the
central reaction zone to the first C.sub.3 reactor and the second
C.sub.3 reactor. 73. The method of embodiment 70 or 71, wherein the
outlet stream comprising beta lactone is directed from the central
reaction zone to the first C.sub.3 reactor and the first C.sub.4
reactor. 74. The method of any one of embodiments 70 to 73, wherein
the epoxide is ethylene oxide (EO) and the beta lactone is beta
propiolactone (BPL). 75. The method of any one of embodiments 70 to
74, wherein the first C.sub.3 product and the second C.sub.3
product are independently selected from an
.alpha.,.beta.-unsaturated acid, an .alpha.,.beta.-unsaturated
ester, an .alpha.,.beta.-unsaturated amide, a C.sub.3 polymer and
1,3-propanediol (PDO). 76. The method of any one of embodiments 70
to 74, wherein the first C.sub.3 product is polypropiolactone
(PPL). 77. The method of any one of embodiments 70 to 74, wherein
the first C.sub.3 product is acrylic acid. 78. The method of
embodiment 77, further comprising: [1094] directing the outlet
stream comprising PPL from the first C.sub.3 reactor to a third
C.sub.3 reactor; [1095] converting at least some of the PPL to a
third C.sub.3 product in the third C.sub.3 reactor to produce an
outlet stream comprising the third C.sub.3 product. 79. The method
of embodiment 78, wherein the third C.sub.3 product is acrylic
acid. 80. The method of any one of embodiments 70 to 79, wherein
the first C.sub.4 product is succinic anhydride. 81. The method of
any one of embodiments 70 to 79, wherein the first C.sub.4 product
is succinic anhydride, and the method further comprises: [1096]
directing the outlet stream comprising succinic anhydride from the
first C.sub.4 reactor to a second C.sub.4 reactor; [1097]
converting at least some of the succinic anhydride to a second
C.sub.4 product in the second C.sub.4 reactor to produce an outlet
stream comprising the second C.sub.4 product. 82. The method of
embodiment 81, wherein the second C.sub.4 product is succinic acid,
1,4 butanediol (BDO), tetrahydrofuran (THF) or gamma butyrolactone
(GBL). 83. A method for producing acrylic acid (AA) from ethylene
in a single integrated system, the method comprising: [1098]
providing ethylene to an oxidative reactor that converts at least
some of the ethylene to ethylene oxide (EO); [1099] providing EO to
a central reactor that converts at least some of the EO to beta
propiolactone (BPL); [1100] and at least one or both of (i) and
(ii): [1101] (i) providing BPL to a first reactor that converts at
least some of the BPL to AA, and [1102] (ii) providing BPL to a
reactor that converts at least some of the BPL to polypropiolactone
(PPL). 84. The method of embodiment 83, wherein BPL is provided to
a first reactor that converts at least some of the BPL, and the
method further comprises isolating acrylic acid at a rate of about
200 to about 800 kilotons per annum (kta). 85. A method,
comprising: [1103] providing an EO stream and a CO stream to a
central reactor, wherein the EO stream comprises EO, and the CO
stream comprises CO; [1104] contacting the EO stream and the CO
stream with a carbonylation catalyst in the central reactor; [1105]
converting at least a portion of the EO to produce a beta
propiolactone (BPL) stream comprising BPL; [1106] directing at
least a portion of the BPL stream to a first C3 reactor; [1107]
converting at least portion of the BPL to polypropiolactone (PPL)
in the first C3 reactor, to produce a PPL stream comprising the PPL
from the first C3 reactor; [1108] directing the PPL stream to a
second C3 reactor; [1109] converting at least a portion of the PPL
to acrylic acid (AA) in the second C3 reactor, to produce an AA
stream comprising the AA from the second C3 reactor; [1110]
directing at least a portion of the BPL stream to a third C3
reactor; [1111] contacting the BPL stream in the third C3 reactor
with an alcohol; and [1112] converting at least a portion of the
BPL to acrylate esters in the third C3 reactor, to produce an
acrylate ester stream comprising the acrylate esters. 86. The
method of embodiment 85, the PPL stream, the AA stream, and the
acrylate ester stream are simultaneously produced. 87. The method
embodiment 85 or 86, further comprising modulating a ratio of
PPL:AA:acrylate ester produced in the PPL stream, the AA stream,
and the acrylate ester stream. 88. The method of any one of
embodiments 85 to 87, further comprising modulating the fraction of
the PPL stream that is received by the second C3 reactor. 89. A
method, comprising: [1113] providing an EO stream and a CO stream
to a central reactor, wherein the EO stream comprises EO, and the
CO stream comprises CO; [1114] contacting the EO stream and the CO
stream with a carbonylation catalyst in the central reactor; [1115]
converting at least a portion of the EO to produce a beta
propiolactone (BPL) stream comprising BPL; [1116] directing at
least a portion of the BPL stream to a first C3 reactor; [1117]
converting at least portion of the BPL to polypropiolactone (PPL)
in the first C3 reactor, to produce a PPL stream comprising the PPL
from the first C3 reactor; [1118] directing at least a portion of
the BPL stream to a second C3 reactor; [1119] converting at least a
portion of the BPL to acrylic acid (AA) in the second C3 reactor,
to produce an AA stream comprising the AA from the second C3
reactor; [1120] directing at least a portion of the BPL stream to a
third C3 reactor; [1121] contacting the BPL stream with an alcohol
in the third C3 reactor; and [1122] converting at least a portion
of the BPL to acrylate esters in the third C3 reactor, to produce
an acrylate ester stream comprising the acrylate esters. 90. The
method of embodiment 89, wherein two or more of the PPL stream, the
AA stream, and the acrylate ester stream are simultaneously
produced. 91. The method of embodiment 89, wherein the PPL stream,
the AA stream, and the acrylate ester stream are simultaneously
produced. 92. The method of any one of embodiments 89 to 91,
further comprising modulating a ratio of PPL:AA:acrylate ester
produced in the PPL stream, the AA stream, and the acrylate ester
stream. 93. A method, comprising: [1123] providing an EO stream and
a CO stream to a central reactor, wherein the EO stream comprises
EO, and the CO stream comprises CO; [1124] contacting the EO stream
and the CO stream with a carbonylation catalyst in the central
reactor; [1125] converting at least a portion of the EO to produce
a beta propiolactone (BPL) stream comprising BPL; [1126] directing
at least a portion of the BPL stream to a first C3 reactor; [1127]
converting at least portion of the BPL to polypropiolactone (PPL)
in the first C3 reactor, to produce a PPL stream comprising the PPL
from the first C3 reactor; [1128] directing the PPL stream to a
second C3 reactor; [1129] converting at least some of the PPL to
acrylic acid (AA) in the second C3 reactor, to produce an AA stream
comprising the AA from the second C3 reactor; [1130] directing at
least a portion of the BPL stream to a first C4 reactor; and [1131]
converting at least some of the BPL to succinic anhydride (SA) in
the first C4 reactor, to produce a succinic anhydride stream
comprising the succinic anhydride from the first C4 reactor. 94.
The method of embodiment 93, wherein the PPL stream, the AA stream,
and the SA stream are simultaneously produced. 95. The method of
embodiment 93 or 94, further comprising modulating a ratio of
PPL:AA:SA from the PPL stream, the AA stream, and the SA stream.
96. The method of any one of embodiments 93 to 95, further
comprising modulating the fraction of the PPL stream that is
received by the second C3 reactor. 97. The method of any one of
embodiments 93 to 96, further comprising: [1132] directing the SA
stream to a second C4 reactor; [1133] contacting at the SA stream
with hydrogen in the second C4 reactor; and [1134] converting at
least a portion of the SA to 1,4 butanediol (BDO), tetrahydrofuran
(THF), or gamma butyrolactone (GBL), or any combinations thereof.
98. The method of embodiment 97, further comprising modulating a
ratio of BDO:THF:GBL produced in the second C4 reactor. 99. A
method, comprising: [1135] providing an EO stream and a CO stream
to a central reactor, wherein the EO stream comprises EO, and the
CO stream comprises CO; [1136] contacting the EO stream and at
least a portion of the CO stream with a carbonylation catalyst in
the central reactor; [1137] converting at least a portion of the EO
to produce a beta propiolactone (BPL) stream comprising BPL; [1138]
directing at least a portion of the BPL stream to a first C3
reactor; [1139] converting at least portion of the BPL to
polypropiolactone (PPL) in the first C3 reactor, to produce a PPL
stream comprising the PPL from the first C3 reactor; [1140]
directing at least a portion of the BPL stream to a second C3
reactor; [1141] converting at least a portion of the BPL to acrylic
acid (AA) in the second C3 reactor, to produce an AA stream
comprising the AA from the second C3 reactor; [1142] directing at
least a portion of the BPL stream to a third C3 reactor; [1143]
contacting the BPL stream with an alcohol in the third C3 reactor;
[1144] converting at least a portion of the BPL to acrylate esters
in the C3 reactor, to produce an acrylate ester stream comprising
the acrylate esters; [1145] directing at least a portion of the BPL
stream to a first C4 reactor; [1146] contacting the BPL stream and
at least a portion of the CO stream in the first C4 reactor; and
[1147] converting at least a portion of the BPL to succinic
anhydride (SA) in the first C4 reactor, to produce a SA stream
comprising the SA. 100. The method of embodiment 99, wherein the
PPL stream, the AA stream, and the acrylate ester stream are
simultaneously produced. 101. The method of embodiment 99, wherein
the PPL stream, the AA stream, the acrylate ester stream, and the
SA stream are simultaneously produced. 102. The method of any one
of embodiments 99 to 101, further comprising modulating a ratio
PPL:AA:acrylate ester from the PPL stream, the AA stream, and the
acrylate ester stream. 103. The method of any one of embodiments 99
to 102, further comprising modulating a ratio PPL:AA:acrylate ester
output:SA from the PPL stream, the AA stream, the acrylate ester
stream, and the SA stream. 104. The method of any one of
embodiments 99 to 103, further comprising modulating the fraction
of the BPL stream that is received by the second C3 reactor. 105.
The method of any one of embodiments 99 to 104, further comprising:
[1148] directing the SA stream to a second C4 reactor; [1149]
contacting at the SA stream with hydrogen in the second C4 reactor;
and [1150] converting at least a portion of the SA to 1,4
butanediol (BDO), tetrahydrofuran (THF), or gamma butyrolactone
(GBL), or any combinations thereof. 106. The method of embodiment
105, further comprising modulating a ratio of BDO:THF:GBL produced
in the second C4 reactor. 107. The method of any one of embodiments
85 to 106, further comprising: [1151] providing an ethylene stream
to an oxidative reactor, wherein the ethylene stream comprises
ethylene; and [1152] converting at least a portion of the ethylene
to ethylene oxide (EO), and providing the EO stream. 108. The
method of any one of embodiments 85 to 107, further comprising:
[1153] isolating PPL from the PPL stream; and [1154] packaging the
isolated PPL for distribution.
[1155] The foregoing has been a description of certain non-limiting
embodiments of the invention. Accordingly, it is to be understood
that the embodiments of the invention herein described are merely
illustrative of the application of the principles of the invention.
Reference herein to details of the illustrated embodiments is not
intended to limit the scope of the claims, which themselves recite
those features regarded as essential to the invention.
* * * * *