U.S. patent application number 11/661167 was filed with the patent office on 2008-12-04 for chemical production processes and systems.
Invention is credited to Janet Boggs, Stephan Brandstadter, Mitchel Cohn, Venkat Reddy Ghojala, Vicki Hedrick, P.V. Ramachandran.
Application Number | 20080300432 11/661167 |
Document ID | / |
Family ID | 36000391 |
Filed Date | 2008-12-04 |
United States Patent
Application |
20080300432 |
Kind Code |
A1 |
Hedrick; Vicki ; et
al. |
December 4, 2008 |
Chemical Production Processes and Systems
Abstract
Chemical production processes are provided that include reacting
a metal comprising olefin to form a conjugated olefin; reacting a
heterohalogenated olefin to form a conjugated olefin; reacting a
halogenated alkane to form a conjugated olefin; and/or reacting a
hydrohalogenated olefin to form a conjugated olefin. Chemical
production systems are also provided that can include: a first
reactant reservoir configured to house a perhalogenated olefin; a
second reactant reservoir configured to house a catalyst mixture; a
first reactor coupled to both the first and second reservoirs, the
first reactor configured to house a metal-comprising mixture and
receive both the perhalogenated olefin form the first reactant
reservoir and the reactant mixture from the second reactant
reservoir; and a product collection reservoir coupled to the first
reactor and configured to house a conjugated olefin.
Inventors: |
Hedrick; Vicki; (Brookston,
IN) ; Brandstadter; Stephan; (Indianapolis, IN)
; Boggs; Janet; (Crawfordsville, IN) ; Cohn;
Mitchel; (West Haven, CT) ; Ghojala; Venkat
Reddy; (Andhra Pradesh, IN) ; Ramachandran; P.V.;
(West Lafayette, IN) |
Correspondence
Address: |
Wells St. John, P.S.
601 W. First Avenue, Suite 1300
Spokane
WA
99201
US
|
Family ID: |
36000391 |
Appl. No.: |
11/661167 |
Filed: |
August 26, 2005 |
PCT Filed: |
August 26, 2005 |
PCT NO: |
PCT/US05/30350 |
371 Date: |
May 6, 2008 |
Related U.S. Patent Documents
|
|
|
|
|
|
Application
Number |
Filing Date |
Patent Number |
|
|
60605232 |
Aug 26, 2004 |
|
|
|
Current U.S.
Class: |
570/158 ;
422/219; 422/600 |
Current CPC
Class: |
B01J 2219/00006
20130101; C07C 17/21 20130101; C07C 17/263 20130101; C07C 17/25
20130101; C07C 17/25 20130101; C07C 19/12 20130101; C07C 21/18
20130101; C07C 21/20 20130101; C07C 19/14 20130101; C07C 17/04
20130101; C07C 21/18 20130101; C07C 17/21 20130101; C07C 17/04
20130101; C07C 17/23 20130101; C07C 17/263 20130101; C07C 21/20
20130101; C07C 17/23 20130101 |
Class at
Publication: |
570/158 ;
422/219; 422/190 |
International
Class: |
C07C 21/18 20060101
C07C021/18; B01J 19/00 20060101 B01J019/00 |
Claims
1. A chemical production process comprising reacting a metal
comprising olefin to form a conjugated olefin.
2. The chemical production process of claim 1 wherein the metal
comprising olefin comprises at least one element from groups 11 or
12 of the periodic table of elements.
3. The chemical production process of claim 2 wherein the one
element is Zn.
4. The chemical production process of claim 1 wherein the metal
comprising olefin comprises one or more of F, Cl, Br, and I.
5. The chemical production process of claim 4 wherein the metal
comprising olefin is heterohalogenated.
6. The chemical production process of claim 4 wherein the metal
comprising olefin is perhalogenated.
7. The chemical production process of claim 1 wherein the metal
comprising olefin is a C-2 olefin.
8. The chemical production process of claim 7 wherein the metal
comprising olefin comprises both F and Br.
9. The chemical production process of claim 7 wherein the metal
comprising olefin comprises F, Br, and Zn.
10. The chemical production process of claim 7 wherein the metal
comprising olefin is ##STR00017##
11. The chemical production process of claim 1 wherein the
conjugated olefin comprises one or more of F, Cl, Br, and I.
12. The chemical production process of claim 1 wherein the
conjugated olefin is perhalogenated.
13. The chemical production process of claim 1 wherein the
conjugated olefin is homohalogenated.
14. The chemical production process of claim 1 wherein the
conjugated olefin is a C-4 olefin.
15. The chemical production process of claim 14 wherein the C-4
olefin is perhalogenated with F.
16. The chemical production process of claim 1 wherein the
conjugated olefin is ##STR00018##
17. The chemical production process of claim 1 wherein the reacting
comprises exposing the metal-comprising olefin to a reactant
mixture to form the conjugated olefin.
18. The chemical production process of claim 17 wherein the
reactant mixture comprises one or more of Fe, Cu, Na, Mg, Ni, and
Ag.
19. The chemical production process of claim 17 wherein the
reactant mixture comprises a metal-halide composition.
20. The chemical production process of claim 19 wherein the metal
halide composition comprises one or more of Fe, Cu, Na, Mg, Ni, Ag,
F, Cl, Br, and I.
21. The chemical production process of claim 17 wherein the
reactant mixture comprises a polar aprotic solvent.
22. The chemical production process of claim 17 wherein the
reactant mixture comprises tetrahydrofuran.
23. The chemical production process of claim 17 wherein the
exposing comprises: providing the metal comprising olefin to within
a reactor; and providing the reactant mixture to within the
reactor, wherein a temperature of the contents of the reactor is
maintained during the providing of the catalyst mixture.
24. The chemical production process of claim 23 wherein: the metal
comprising olefin comprises ##STR00019## the reactant mixture
comprises FeCl.sub.3; and the temperature is less than about
70.degree. C.
25. The chemical production process of claim 23 further comprising
removing the conjugated olefin from the reactor.
26. The chemical production process of claim 25 wherein the
removing comprises increasing the maintained temperature of the
contents of the reactor.
27. The chemical production process of claim 26 wherein the
increasing comprises at least about a 15% increase in the
maintained temperature.
28. The chemical production process of claim 27 wherein the
maintained temperature is about 70.degree. C. and the increasing
comprises increasing the temperature to about 90.degree. C.
29. The chemical production process of claim 25 wherein: the metal
comprising olefin comprises ##STR00020## the reactant mixture
comprises FeCl.sub.3; the temperature is less than about 70.degree.
C.; the conjugated olefin comprises and ##STR00021## and the
increased temperature is greater than about 80.degree. C.
30. The chemical production process of claim 25 further comprising
purifying the conjugated olefin.
31. The chemical production process of claim 30 wherein the
purifying comprises one or both of distilling and drying the
conjugated olefin.
32. The chemical production process of claim 31 wherein the
distilling comprises: providing a product mixture comprising the
conjugated olefin and by products to a distillation apparatus;
converting at least a portion of the mixture to the gas phase, the
portion of the mixture comprising at least a portion of the
conjugated olefin; and recovering a distillate comprising the
portion of the conjugated olefin, the distillate comprising less
by-products than the product mixture.
33. The chemical production process of claim 31 wherein the drying
comprises exposing a product mixture comprising the conjugated
olefin to one or both of a 3 .ANG. absorbent and a 13.times.
molecular sieve.
34. The chemical production process of claim 33 wherein the product
mixture is in the liquid phase during the exposing.
35. A chemical production process comprising reacting a
heterohalogenated olefin to form a conjugated olefin.
36. The chemical production process of claim 35 wherein the
heterohalogenated olefin is a C-2 olefin.
37. The chemical production process of claim 35 wherein the
heterohalogenated olefin comprises F and one or more of Cl, Br, and
I.
38. The chemical production process of claim 35 wherein the
heterohalogenated olefin is ##STR00022##
39. The chemical production process of claim 36 wherein the
reacting comprises: providing a reactor, the reactor being
configured to expose a metal comprising mixture to the
heterohalogenated olefin; providing the metal comprising mixture to
within the reactor; and exposing the metal-comprising mixture to
the heterohalogenated olefin to form a metal comprising olefin.
40. The chemical production process of claim 39 wherein the metal
comprising mixture comprises at least one or more elements from
groups 1, 2, 4, 8, 11, 12, and 14 of the periodic table of
elements.
41. The chemical production process of claim 39 wherein the metal
comprising mixture comprises Zn.
42. The chemical production process of claim 39 wherein the metal
comprising mixture comprises a polar aprotic solvent.
43. The chemical production process of claim 39 wherein the metal
comprising mixture comprises tetrahydrofuran.
44. The chemical production process of claim 39 wherein the
providing the metal comprising mixture to within the reactor
comprises: providing a composition comprising a polar aprotic
solvent and tetrahydrofuran to the reactor; providing a metal to
the reactor, the metal and composition forming the metal comprising
mixture; and heating the mixture to a temperature of from about
17.degree. C. to about 120.degree. C.
45. The chemical production process of claim 44 wherein the heating
further comprises maintaining the mixture at a temperature of from
about 60.degree. C. to about 110.degree. C.
46. The chemical production process of claim 39 further comprising
conjugating the metal comprising olefin to form the conjugated
olefin.
47. The chemical production process of claim 46 wherein: the
heterohalogenated olefin is ##STR00023## the reactant mixture is
Fe; the metal-comprising mixture is Zn; the metal comprising olefin
is ##STR00024## and the conjugated olefin is ##STR00025##
48. A chemical production process comprising reacting a halogenated
alkane to form a conjugated olefin.
49. The chemical production process of claim 48 wherein the
halogenated alkane comprises one or more of F, Cl, Br, and I.
50. The chemical production process of claim 48 wherein the
halogenated alkane is a C-2 alkane.
51. The chemical production process of claim 48 wherein the
halogenated alkane is heterohalogenated.
52. The chemical production process of claim 48 wherein the
halogenated alkane is C.sub.2HF.sub.3Br.sub.2.
53. The chemical production process of claim 52 wherein the
halogenated alkane is ##STR00026##
54. The chemical production process of claim 48 wherein the
reacting comprises: reacting the halogenated alkane to form a
heterohalogenated olefin; and reacting the heterohalogenated olefin
to from the conjugated olefin.
55. The chemical production process of claim 54 wherein the
reacting the halogenated alkane to form the heterohalogenated
olefin comprises: providing a reactor configured to expose the
halogenated olefin to a reducing reagent mixture; providing the
reducing reagent mixture to within the reactor; exposing the
halogenated olefin to the reducing regent mixture to form the
heterohalogenated olefin.
56. The chemical production process of claim 55 wherein the reactor
comprises a nickel alloy.
57. The chemical production process of claim 55 wherein the reactor
is glass lined.
58. The chemical production process of claim 55 wherein the
reducing-reagent mixture comprises a base.
59. The chemical production process of claim 55 wherein the
reducing reagent mixture comprises KOH and water.
60. The chemical production process of claim 55 wherein the
reducing reagent mixture comprises 40% (wt./wt.) KOH.
61. A chemical production process comprising reacting a
hydrohalogenated olefin to form a conjugated olefin.
62. The chemical production process of claim 61 wherein the
hydrohalogenated olefin comprises one or more of F, Cl, Br, and
I.
63. The chemical production process of claim 61 wherein the
hydrohalogenated olefin is a C-2 olefin.
64. The chemical production process of claim 61 wherein the
hydrohalogenated olefin is C.sub.2HF.sub.3.
65. The chemical production process of claim 61 wherein the
hydrohalogenated olefin is ##STR00027##
66. The chemical production process of claim 61 wherein the
reacting comprises: reacting the hydrohalogenated olefin to form a
halogenated alkane; and reacting the halogenated alkane to form the
conjugated olefin.
67. The chemical production process of claim 61 wherein the
reacting the hydrohalogenated olefin to form the halogenated alkane
comprises: providing a reactor configured to expose the
hydrohalogenated olefin to a halogenating reagent; providing the
hydrohalogenated olefin to within a reactor; and exposing the
hydrohalogenated olefin to the halogenating reagent to form the
halogenated alkane.
68. The chemical production process of claim 67 wherein
halogenating reagent comprises one or more of F, Cl, Br, and I.
69. The chemical production process of claim 67 wherein: the
hydrohalogenated olefin is ##STR00028## the halogenated reagent is
Br.sub.2; and the halogenated alkane is ##STR00029##
70. A chemical production process comprising: providing a
heterohalogenated olefin to within a reactor; providing a reducing
agent to within the reactor; and reacting the olefin with the
reducing agent within the reactor, at least the olefin being in the
liquid phase during the reacting.
71. The chemical production process of claim 70 further comprising
providing a catalyst composition to the reactor.
72. The chemical production process of claim 71 wherein the
catalyst composition comprises one or both of Pd and C.
73. The chemical production process of claim 70 further comprising
providing an organic media to the reactor.
74. The chemical production process of claim 73 wherein the organic
media comprises as solvent.
75. The chemical production process of claim 73 wherein the organic
media comprises methanol.
76. The chemical production process of claim 70 further comprising:
providing a catalyst composition to the reactor; and providing an
organic media to the reactor.
77. The chemical production process of claim 76 wherein:
heterohalogenated olefin is C.sub.2CIF.sub.3; the reducing agent
comprises H; the catalyst composition comprises one or both of Pd
and C; and the organic media comprises methanol.
78. A production system comprising: a first reactant reservoir
configured to house a perhalogenated olefin; a second reactant
reservoir configured to house a catalyst mixture; a first reactor
coupled to both the first and second reservoirs, the first reactor
configured to house a metal-comprising mixture and receive both the
perhalogenated olefin from the first reactant reservoir and the
reactant mixture from the second reactant reservoir; and a product
collection reservoir coupled to the first reactor and configured to
house a conjugated olefin.
79. The production system of claim 78 wherein: the perhalogenated
olefin is ##STR00030## the reactant mixture is Fe; the metal
comprising mixture is Zn; and the conjugated olefin is
##STR00031##
80. The production system of claim 78 further comprising a second
reactor coupled to both the product reservoir and the first
reactant reservoir, the second reactor configured to receive at
least one by-product from the product reservoir and react the
by-product to form the perhalogenated olefin.
81. The production system of claim 80 wherein second reactor
comprises both a third and a fourth reactor, the third reactor
being coupled to the fourth reactor, wherein: the third reactor is
configured to react a hydrohalogenated olefin to form a halogenated
alkane; and the fourth reactor is configured to react the
halogenated alkane to form a heterohalogenated olefin, wherein the
by-product is one or both of the hydrohalogenated olefin and the
halogenated alkane.
82. The production system of claim 81 wherein: the hydrohalogenated
olefin is ##STR00032## and the halogenated alkane is ##STR00033##
Description
CLAIM FOR PRIORITY
[0001] This application claims priority to U.S. Provisional Patent
Application Ser. No. 60/605,232, entitled "Chemical Preparation
Processes", filed Aug. 26, 2004; the entirety of which is
incorporated by reference herein.
TECHNICAL FIELD
[0002] The present invention relates to the field of chemical
production processes and systems and more specifically to the
production of conjugated olefins and systems for producing
conjugated olefins.
BACKGROUND
[0003] Time and efficiency have always played a role in the
development of chemical production processes and systems. There is
a constant need for the most efficient and reliable processes
thereby enabling the least expensive production costs. Recently
industries have required high purity specialized compounds for use
in manufacturing processes. Hexafluoro-1,3-butadiene
(C.sub.4F.sub.6) has been developed for dry etching and
semiconductor processing applications. C.sub.4F.sub.6 is just one
example of a conjugated olefin that can be prepared according to
the processes and systems described herein.
SUMMARY
[0004] Chemical production processes are provided that include
reacting a metal comprising olefin to form a conjugated olefin;
reacting a heterohalogenated olefin to form a conjugated olefin;
reacting a halogenated alkane to form a conjugated olefin; and/or
reacting a hydrohalogenated olefin to form a conjugated olefin.
[0005] Chemical production systems are also provided that can
include: a first reactant reservoir configured to house a
perhalogenated olefin; a second reactant reservoir configured to
house a catalyst mixture; a first reactor coupled to both the first
and second reservoirs with the first reactor configured to house a
metal-comprising mixture and receive both the perhalogenated olefin
from the first reactant reservoir and the reactant mixture from the
reservoir; and a product collection reservoir coupled to the first
reactor and configured to house a conjugated olefin.
BRIEF DESCRIPTION OF THE DRAWINGS
[0006] Embodiments are described with reference to the following
accompanying drawings:
[0007] FIG. 1 is an exemplary system for preparing compositions
according to an embodiment.
[0008] FIG. 2 is an exemplary system for preparing compositions
according to an embodiment.
[0009] FIG. 3 is an exemplary system for preparing compositions
according to an embodiment.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0010] Chemical production processes and systems are described with
reference to FIGS. 1-3. Referring first to FIG. 1, a system 10 is
disclosed that includes a reaction zone 11 coupled to a
heterohalogenated olefin reservoir 12, a metal-comprising mixture
reservoir 13 and a reactant mixture reservoir 14. System 10 also
includes a product recovery zone 16 and a recycle conduit 15
configured to return by-products separated from products in zone 16
to reaction zone 11. According to exemplary embodiments, reaction
zone 11 can include a single reactor or a plurality of reactors.
The reactor can be constructed of glass and/or a nickel-alloy such
as Inconel.RTM. 600 (Special Metals Corporation 3200 Riverside
Drive Huntington, W. Va. 25705-1771, USA). These reactors can be
configured to control the temperature within the reactor via
cooling coils and/or heat tape, for example, depending on the
requirements of the temperature within the reactor. The reactor can
also be configured to control the pressure within the reactor
during the combination of reactants.
[0011] According to exemplary embodiments, system 10 can be
configured to react a metal-comprising olefin to form a conjugated
olefin. The reacting can include exposing the metal-comprising
olefin to a reactant mixture to form the conjugated olefin, for
example. This exposing can include providing the metal-comprising
olefin to within the reactor and providing a reactant mixture to
within the reactor. Exemplary embodiments include maintaining the
temperature of the contents of the reactor during the providing of
the catalyst mixture.
[0012] The providing of the metal-comprising olefin can include
reacting a heterohalogenated olefin from heterohalogenated olefin
reservoir 12 to form the metal-comprising olefin. The
heterohalogenated olefin of heterohalogenated olefin reservoir 12
can include a C-2 olefin. The heterohalogenated olefin can also
include F and one or more of Cl, Br, and/or I. The
heterohalogenated olefin can be C.sub.2F.sub.3Br and/or
##STR00001##
for example.
[0013] According to exemplary aspects a metal-comprising mixture
from metal-comprising mixture reservoir 13 can be provided to
reaction zone 11. This mixture can be in the form of a slurry and
can include one or more elements from groups 1, 2, 4, 8, 11, 12,
and/or 14 of the periodic table of elements and in specific
embodiments zinc, as well as, a composition including
tetrahydrofuran and/or a polar aprotic solvent such as one or more
of acetonitrile, methyl-ethyl-ketone, dimethylformamide, and/or
dimethylsulfoxide. The elements may be activated and/or
unactivated, for example, unactivated Zn may be utilized. The
compositions may be anhydrous and/or contain small amounts of
water, such as amounts as high as 0.15% (wt./wt.). For example, a
composition of one or more acetonitrile, tetrahydrofuran,
methyl-ethyl-ketone, dimethylformamide, and dimethylsulfoxide may
be provided to reaction zone 11 followed by providing a metal to
zone 11 with the metal and the composition forming the
metal-comprising mixture. Within zone 11, the metal-comprising
mixture may be heated to a temperature of from about room
temperature to about 120.degree. C. According to exemplary
embodiments, the temperature of the metal-comprising mixture can be
maintained at from about 60.degree. C. to about 70.degree. C.,
and/or greater than 70.degree. C. The heterohalogenated olefin can
be added from heterohalogenated olefin reservoir 12 to form the
metal-comprising olefin. In exemplary embodiments, the addition of
the heterohalogenated olefin can be performed under atmospheric
pressures and in other embodiments, system 10 can be closed and the
addition can be performed under a vacuum such as 15 mm Hg.
[0014] According to other embodiments the metal-comprising mixture
may be heated to about 70.degree. C. and a portion of the molar
charge of the heterohalogenated olefin may be added to the mixture.
In exemplary embodiments, adding less than molar charge can
initiate the production of the metal-comprising olefin. For
example, the portion can be at least about 15% to 25% of the molar
charge and combined with the metal-comprising mixture within zone
11 to produce the metal-comprising olefin. Upon addition of the
portion of the molar charge of the heterohalogenated olefin,
production of the metal-comprising olefin can initiate and a
remainder of the heterohalogenated olefin may then be added to zone
11 and consumed upon addition. According to exemplary embodiments,
adding the portion of the heterohalogenated olefin to initiate the
production followed by adding the remainder of the olefin can
facilitate temperature and/or pressure control of zone 11 which can
also facilitate purification of the conjugated olefin where system
10 is a closed system.
[0015] According to other embodiments, a complete charge of the
heterohalogenated olefin may be added to the metal-comprising
mixture. Upon addition of the complete charge the system can be
cooled to control exotherms.
[0016] Where system 10 is a closed system, the pressure may be
controlled to regulate production and control reaction rates, as
well as, efficiency. For example the system may be maintained under
vacuum. In other instances the pressure of system 10 may be
maintained below about 300 mm Hg and in other instances the
pressure can be greater than 20 mm Hg.
[0017] The metal-comprising olefin can contain at least one element
from groups 1, 2, 4, 8, 11, 12, and/or 14 of the periodic table of
elements. The element can be Zn, for example. The metal-comprising
olefin also can include one or more of F, Cl, Br, and/or I. The
metal-comprising olefin can be heterohalogenated in exemplary
embodiments and/or perhalogenated. The metal-comprising olefin can
be a C-2 olefin and/or, according to exemplary embodiments, the
metal-comprising olefin can include both F and Br. According to
other embodiments, the metal-comprising olefin can include F, Br,
and/or Zn. In exemplary embodiments, the metal-comprising olefin
is
##STR00002##
The metal-comprising olefin can be prepared and, in exemplary
embodiments, is stable for up to 4 days. As such, according to
exemplary embodiments, the reactions can be performed in stages, at
separate facilities and/or locations.
[0018] The metal-comprising olefin can be reacted to form a
conjugated olefin by providing a reactant mixture from reactant
mixture reservoir 14 to reactor zone 11. The reactant mixture can
include one or more of Fe, Cu, Ni, and/or Mn. The reactant mixture
can also include a metal-halide composition and the metal-halide
composition can comprise one or more of Fe, Cu, Ni, Mn, F, Cl, Br,
and/or I. The reactant mixture can also include one or both of
polar aprotic solvents and/or non-polar solvents. Exemplary
compositions that can be a component of the reactant mixture can
include one or more of acetonitrile, tetrahydrofuran,
methyl-ethyl-ketone, dimethylformamide, and dimethylsulfoxide. In
exemplary embodiments, the reactant mixture includes FeCl.sub.3.
Exemplary reactant mixtures can be stable for use for up to 4
days.
[0019] A product mixture including the conjugated olefin can be
formed while providing the reactant mixture to zone 11 while
maintaining the contents of the reaction zone at less than about
70.degree. C., for example. According to still other embodiments,
heating zone 11 to temperatures as high and or greater than
70.degree. C. can facilitate efficient production of the conjugated
olefin. For example, the product mixture can include approximately
60% conjugated olefin when zone 11 is maintained below 70.degree.
C., however when zone 11 is maintained above 70.degree. C. product
mixtures including as high as 90% conjugated olefin can be
obtained.
[0020] The conjugated olefin formed can include one or more of F,
Cl, Br, and/or I. The conjugated olefin can be perhalogenated
and/or homohalogenated. The olefin can be perhalogenated with F,
for example. In exemplary embodiments, the conjugated olefin is a
C-4 olefin. The conjugated olefins can be
##STR00003##
for example. The conjugated olefin can be removed from reaction
zone 11 and transferred to product recovery zone 16. The conjugated
olefin can be removed by increasing the maintained temperature of
the contents of the reaction zone 11, for example. In exemplary
embodiments, this can include increasing the temperature at least
15% above the maintained temperature; and/or from about 15% to
about 30% above the maintained temperature. For example, where the
maintained temperature is about 70.degree. C. the conjugated olefin
can be removed by increasing the temperature within reaction zone
11 to about 120.degree. C.
[0021] As a more specific example, the metal-comprising olefin can
include
##STR00004##
the reactant mixture can include FeCl.sub.3, and the temperature
within the reaction zone upon addition of the reactant mixture to
the metal-comprising olefin can be less than about 70.degree. C.
The conjugated olefin can include
##STR00005##
and the temperature of the reactor can be increased to a
temperature greater than about 80.degree. C. to remove the
conjugated olefin from the reactor.
[0022] According to an exemplary embodiment, within the product
recovery zone 16, the conjugated olefin can be purified. This
purification can include distilling and drying the conjugated
olefin, for example.
[0023] The distilling can include providing a product mixture that
includes the conjugated olefin and by-products to a distillation
apparatus. At least a portion of the mixture can be converted to
the gas phase with the portion being converted to the gas phase
including at least a portion of the conjugated olefin within the
product mixture. A distillate can be recovered comprising the
portion of the conjugated olefin with the distillate comprising
less by-products than the product mixture.
[0024] Either before or after distillation, the conjugated olefin
can be dried by exposing a product mixture including the conjugated
olefin to one or both of a 3 .ANG. absorbent and/or a 13.times.
molecular sieve, for example. During this exposing to the 3 .ANG.
absorbent and/or the 13.times. molecular sieve, the product mixture
can be in a liquid phase, for example.
[0025] Further examples of the reactions that can be performed with
reference to system 10 are given below with reference to Schemes
1-5.
##STR00006##
[0026] According to scheme (1) above, in a reaction flask that can
be equipped with an agitator, jacketing, a thermocouple, reflux
condenser, a product collecting container, a vacuum pump, and a
feeding tube which can be slidably coupled to a flask neck member,
600 grams (9.18 moles) of zinc and 3000 grams of
N,N-dimethylformamide (DMF) can be added to form a slurry. The
slurry can be agitated at from about 0 rpm to 220 rpm and heated to
about 70.degree. C. To the slurry, from about 92.4 grams (0.57
mole) to about 231 grams (1.44 moles) of bromotrifluoroethylene can
be added subsurface relative to the slurry through the feeding tube
to form a mixture. The mixture can be observed to have an exotherm,
thereby bringing the mixture temperature to from about 90.degree.
to about 120.degree. C. The mixture can then be cooled to about
70.degree. C. whereupon from about 693 grams (4.31 moles) to about
831.6 grams (5.17 moles) of bromotrifluoroethylene can be added
through said feeding tube over a period of about 2-664 minutes to
form an organometallic mixture. The organometallic mixture can be
held, while agitating, at temperature for about one hour. In a
separate flask that can be coupled with the reaction flask and
equipped with a supplying tube having a needle valve (Teflon), an
agitator, and a reflux condenser, 1038 grams (6.4 moles) of ferric
chloride (FeCl.sub.3) and 1971 grams of DMF can be added to form an
addition mixture. An exotherm can be observed when the DMF and
FeCl.sub.3 are combined. The addition mixture can be added dropwise
through the feeding tube to the surface of the organometallic
mixture to form a reaction mixture. A vacuum of about 10 cm Hg can
be applied to the entire reaction system to assist in the
delivering of the addition mixture to the organometallic mixture
and subsequent removal of the product dimer. The reaction mixture
temperature can be held at about 70.degree. C. by using an ice
water bath. Near the end of the addition, the reaction mixture can
be allowed to warm to from about 80.degree. C. to about 85.degree.
C. (feed time range from 9-582 minutes) to facilitate removal of
hexafluoro-1,3-butadiene product from reaction mixture into the
product collecting container chilled by a dry ice and acetone bath.
In the product collecting container, 384 grams (2.37 moles) of
hexafluoro-1,3-butadiene product can be collected having a purity
by gas chromatography of about 93 percent.
[0027] According to scheme (1) above, in a reaction flask that can
be equipped with an agitator, jacketing, a thermocouple, reflux
condenser, a product collecting container, a vacuum pump, and a
feeding tube which can be slidably coupled to a neck of the flask,
100 grams of acetonitrile and 20 grams (0.31 mole) of zinc can be
placed to form a mixture. The mixture can be heated to from about
47.degree. C. to about 78.degree. C. and bromotrifluoroethylene can
be fed into the reactor over a period of about 95 minutes to form a
reaction mixture. During the bromotrifluoroethylene feeding period,
the reaction mixture can be observed to change from having a grey
color to having a greenish color. The reaction mixture can be
heated to about 60.degree. C. and held for from about 15 hours to
about 21 hours, and/or about 18 hours whereupon a color change can
be observed from greenish to brownish. The flask can be equipped
with an addition funnel containing a reactant mixture. The reactant
mixture can be prepared by mixing 26.7 grams (0.165 mole) of ferric
chloride and 48.1 grams of acetonitrile whereupon an exotherm can
be observed. The reactant mixture can be added dropwise to the
reaction mixture over a period of about 20 minutes to form a
product mixture. The product mixture can contain
hexafluoro-1,3-butadiene, which can be collected in the product
collecting container. The reactant mixture can be added to the
reaction mixture while removing the hexafluoro-1,3-butadiene
product from the product mixture, for example. The remainder of
product can be driven out of the product mixture by heating to
about 80.degree. C. until no more gas evolution can be observed. A
total of 4.6 grams of the product can be collected. The product
structure as well as reaction efficiency can be confirmed by GC/MS
analysis.
[0028] In accordance with scheme (1) above, in a reaction flask
that can be equipped with an agitator, jacketing, a thermocouple,
reflux condenser, a product collecting container, a vacuum pump,
and a feeding tube which can be slidably coupled to a neck of the
flask, 101 grams of tetrahydrofuran (THF) and 20 grams (0.31 mole)
of zinc can be placed to form a mixture. The mixture can be heated
to from about 60.degree. C. to about 70.degree. C. and a total of
23.37 grams (0.145 mole) of bromotrifluoroethylene can be fed into
the reactor over a period of about 90 minutes to form a reaction
mixture. During the bromotrifluoroethylene feeding period, the
reaction mixture can be observed to change from having a grey color
to having a greenish color. The reaction mixture can be heated to
about 60.degree. C. and held for from about 15 hours to about 21
hours, and/or about 18 hours. The flask can be equipped with an
addition funnel containing a reactant mixture. The reactant mixture
can be prepared by mixing 27.6 grams (0.17 mole) of ferric chloride
and 68 grams of tetrahydrofuran (THF). The reactant mixture can be
added dropwise to the reaction mixture over a period of about 20
minutes to form a product mixture. The product,
hexafluoro-1,3-butadiene, can be collected from the product mixture
in the product collecting container. While adding the reactant
mixture to the reaction mixture product can be recovered from the
product mixture. The remainder of product can be driven out of the
product mixture by heating to about 60.degree. C. until no more gas
evolution can be observed affording about 6 grams total. The
product structure, as well as, reaction efficiency can be confirmed
by GC/MS analysis.
[0029] Referring to scheme (1) above, in a reaction flask that can
be equipped with an agitator, jacketing, a thermocouple, reflux
condenser, a product collecting container, a vacuum pump, and a
feeding tube which can be slidably coupled to a neck of the flask,
100 grams of methyl-ethyl-ketone (MEK) and 20 grams (0.31 mole) of
zinc can be placed to form a mixture. The mixture can be heated to
from about 50.degree. C. to about 70.degree. C. and a total of
20.42 grams (0.13 mole) of bromotrifluoroethylene can be fed into
the reactor over a period of about 90 minutes to form a reaction
mixture. The reaction mixture can be heated to about 60.degree. C.
and held for from about 15 hours to about 21 hours, and/or about 18
hours. The flask can be equipped with an addition funnel containing
a reactant mixture. The reactant mixture can be prepared by mixing
27.8 grams (0.171 mole) of ferric chloride and 48.4 grams of MEK
whereupon an exotherm can be observed. The reactant mixture can be
added dropwise to the reaction mixture over a period of about 5
minutes to form a product mixture. The product,
hexafluoro-1,3-butadiene, can be collected from the product mixture
in the product collecting container. While adding the reactant
mixture, the product can collected from the product mixture. A
remainder of product can be driven out of the product mixture by
heating the mixture to about 80.degree. C. until no more gas
evolution can be observed. A total of 2.0 grams of the product can
be collected. The product structure, as well as, reaction
efficiency can be confirmed by GC/MS analysis.
[0030] In reference to scheme (1) above, in a reaction flask that
can be equipped with an agitator, jacketing, a thermocouple, reflux
condenser, a product collecting container, a vacuum pump, and a
feeding tube which can be slidably coupled to a neck of the flask,
107 grams of dimethyl sulfoxide (DMSO) and 20 grams (0.31 mole) of
zinc can be placed to form a mixture. The mixture can be heated to
from about 57.degree. C. to about 85.degree. C. and a total of 20.2
grams (0.125 mole) of bromotrifluoroethylene can be fed into the
reactor over a period of about 45 minutes to form a reaction
mixture. During the bromotrifluoroethylene feeding period, the
reaction mixture can be observed to change from having a grey color
to having a greenish color. The reaction mixture can be heated to
about 60.degree. C. and held for from about 15 hours to about 21
hours, and/or about 18 hours. The flask can be equipped with an
addition funnel containing a reactant mixture. The reactant mixture
can be prepared by mixing 28 grams (0.174 mole) of ferric chloride
and 52 grams of DMSO. The reactant mixture can be added dropwise to
the reaction mixture over a period of about 10 minutes to form a
product mixture. The product, hexafluoro-1,3-butadiene, can be
collected from the product mixture in the product collecting
container. While adding the reactant mixture, the product can be
removed from the product mixture. The remainder of product can be
driven out of the product mixture by heating the product mixture to
about 80.degree. C. until no more gas evolution can be observed. A
total of 1.7 grams of the product can be collected. The product
structure, as well as, reaction efficiency can be confirmed by
GC/MS analysis.
##STR00007##
[0031] In accordance with scheme (2) above, 2 grams (0.03 mole) of
activated zinc and 30 mL of dry dimethylformamide (DMF) can be
added to a 3-necked 100 mL round bottom flask fitted with a dry ice
condenser to form a slurry. To the slurry, 5.3 grams (0.033 mole)
of bromotrifluoroethylene can be added to form an initial mixture.
The initial mixture can be warmed slightly to about room
temperature, whereupon about 15 minutes later, the reaction can
initiate and an exotherm can occur with the temperature rising to
about 70.degree. C. To control the exotherm the round bottom flask
can be at least partially submerged in ice-water. The initial
mixture can be observed to turn brown and can be stirred further
for 1 hour at room temperature to form the trifluorovinylzinc
bromide. The flask can be fitted with an addition funnel containing
a reactant mixture. The initial mixture can be cooled to
0-5.degree. C., a vacuum of approximately 100 mm Hg can be applied,
and 0.033 mole of the reactant mixture including, for example
ferric salt [FeCl.sub.3 (in some embodiments, added as a solution
in dimethylformamide), FeBr.sub.3, Fe(OAc).sub.3] and/or cupric
salt [Copper triflate, CuBr.sub.2, Cu(OAc).sub.2] can be added
slowly to the initial mixture while maintaining the reaction
temperature at less than about 5.degree. C. to form a reaction
mixture containing the hexafluoro-1,3-butadiene product. Most of
the product can be collected in the cold (dry ice-acetone) trap. A
remainder of the product can be collected by warming the product
mixture to about 40.degree. C. and stirring for 2 hours while
maintaining the vacuum. A yield of the reactions can range from
about 60-68% as confirmed by GC/MS. Yields can be correlated with
the catalysts utilized in accordance with Table 1, below.
TABLE-US-00001 TABLE 1 Production Run Reactant Component Yield 1
FeCl.sub.3 68 2 FeBr.sub.3 67 3 Cu(OAc).sub.2 63 4 CuBr.sub.2 68 5
Cu(OTf).sub.2 62 (3) ##STR00008##
[0032] In accordance with scheme (3) above, under nitrogen, to a
100 mL round bottom flask having a side-arm and fitted with a
reflux condenser, 4.2 grams (0.032 mole) of anhydrous zinc
chloride, and 30 mL of dry tetrahydrofuran can be added to form an
initial mixture. The initial mixture can be cooled to 10.degree. C.
and tetrafluoroethane (HFC-134a, 0.036 mole) can be added slowly to
form a slurry. Lithium diisopropyl amine (1.8 M solution in
heptane/tetrahydrofuran (THF), 0.064 mole) can be added slowly via
a syringe to the slurry, while maintaining the temperature at less
than about 15.degree. C. to form a reaction mixture. (The tip of
the needle of the syringe can be dipped into the slurry to avoid
decomposition of trifluorovinyllithium formed by a reaction of
HFC-134a with lithium diisopropyl amine). The reaction mixture can
be stirred for 1 hour and allowed to warm to room temperature. The
reaction mixture can then be cooled to from about 0.degree. C. to
about 5.degree. C. while applying vacuum (100 mm Hg). Ferric salt
(FeCl.sub.3, FeBr.sub.3, 0.033 mole)] or cupric salt [Copper
triflate, Cu(OAc).sub.2] can be added slowly while maintaining the
vacuum and the reaction temperature below about 5.degree. C. to
form a final mixture. The final mixture can then be stirred while
maintaining the temperature at about 40.degree. C. for two hours
and the product can be collected in -78.degree. C. (dry
ice-acetone) trap. Yields can be from about 65-70%.
##STR00009##
According to scheme (4) above, 18 grams (0.26 mole) of activated
zinc and 150 mL of dry dimethylformamide (DMF) can be added to a
250 mL round bottom flask having a side-arm and fitted with a
reflux condenser to form a slurry. Zinc dust can be activated by
stirring a mixture of 100 grams of zinc powder with 50 mL of 10%
dilute hydrochloric acid for 2-4 minutes, filtering and washing the
mixture with 100 mL of water followed by 50 mL of acetone and
drying the filtrate in an oven at about 130-140.degree. C. for one
hour. To the slurry, 42.5 grams (0.26 mole) of
bromotrifluoroethylene can be added slowly to the round bottom
flask while stirring at room temperature to form a mixture. After
1.5 hours, the reaction can initiate and an exotherm can occur
(temperature raises to 50-60.degree. C., for example), which can be
controlled by submerging a portion of the reaction flask in an ice
water bath. The mixture can turn a brownish color and can be
stirred for an additional 3 hours at room temperature. After this
stirring, the mixture can be cooled to 0-5.degree. C. and iodine
(101 g, 400 mmol) can be added slowly while maintaining the
reaction temperature at <15.degree. C. to form a reaction
mixture. The reaction mixture can be stirred at room temperature
for over night. The product can be distilled at 30-42.degree. C.
under nitrogen to obtain 34 grains (62%) of the trifluorovinyl
iodide product. Similar reaction chemistries can be used to prepare
compounds such as trifluorovinyl chloride and trifluorovinyl
bromide as well.
##STR00010##
[0033] According to scheme (5) above, 8.5 grams (0.132 mole) of
activated copper powder and 50 mL of dry dimethylformamide can be
added to a 100 mL round bottom flask having a side arm and fitted
with a reflux condenser to form a slurry. The activated copper
powder can be prepared according to A. I. Vogel, Textbook of
Practical Organic Chemistry, 5th Ed. Page No. 426, herein
incorporated by reference. According to an exemplary embodiment, 20
grams of copper powder can be exposed to 200 mL of 2% solution of
iodine in acetone for 10 minutes to form a grayish colored mixture.
The mixture can be filtered and washed with 100 mL of a 1:1
solution of concentrated HCl in acetone. The filtrate of the
filtered mixture can be dried under vacuum at 40-50.degree. C.
[0034] To the round bottom flask containing the activated copper
powder and dimethylformamide, trifluorovinyl iodide 25 grams (0.120
mole) can be added slowly and kept stirring at room temperature to
form a reaction mixture. The reaction mixture can be stirred at
room temperature for one hour and the product can be collected in a
cold trap (-78.degree. C.) with the following results: yield: 6.5 g
(67%); conversion 77%; selectivity 74%; mass balance >99%; crude
reaction mixture can contain 57% C.sub.4F.sub.6, 23%
iodotrifluoroethylene (starting material), and 20%
trifluoroethylene (by-product). Qualitative and quantitative
analyses can be determined by gas chromatography mass spectrometry
utilizing total area counts.
[0035] Referring to FIG. 2, a system 20 for reacting a halogenated
alkane to form a conjugated olefin is depicted according to an
exemplary embodiment. System 20 includes at least two reaction
zones, reaction zone 11 as previously described and coupled to
reaction zone 21. System 20 also includes a heterohalogenated
alkane reservoir 12 which also can be considered a portion of the
product recovery zone of reaction zone 21. System 20 also includes
a recycling conduit 15 that can be coupled between reactors 11 and
21, as well as, product recovery zone 16. The halogenated alkane
within halogenated alkane reservoir 22 can include one or more of
F, Cl, Br, and I. The halogenated alkane can be a C-2 alkane and/or
the halogenated alkane can be heterohalogenated. The halogenated
alkane can have the general formula C.sub.2HF.sub.3Br.sub.2 and in
specific embodiments can be
##STR00011##
[0036] System 20 further includes a reducing-reagent mixture
reservoir 23 coupled to reaction zone 21. The reducing-reagent
mixture can include a base. The base can be NaOH and/or KOH, for
example. According to exemplary embodiments, that base can be KOH
and water. Other mixtures can include NaOH and/or KOH and methanol.
More particularly, the reducing-reagent mixture can include a 40%
(wt./wt.) mixture of KOH and water.
[0037] Reaction zone 21 can be configured to expose the halogenated
olefin from halogenated olefin reservoir 22 to the reducing-reagent
mixture from reducing-reagent mixture reservoir 23. In exemplary
embodiments the reducing-reagent mixture can be provided from
reservoir 23 to the reaction zone and then the halogenated olefin
exposed to the reducing reagent mixture within the reaction zone to
form a heterohalogenated olefin. Accordingly, the halogenated
alkane can be reacted to form a heterohalogenated olefin and the
heterohalogenated olefin can be reacted to form a conjugated
olefin, for example, by transferring the heterohalogenated olefin
produced in reaction zone 21 to reaction zone 11 and reacting the
olefin as described above. The heterohalogenated olefin can be
prepared from the halogenated alkane in accordance with scheme 6
below, for example.
##STR00012##
[0038] In accordance with scheme (6) above, a mixture including 40
(wt/wt) % KOH in water can be provided to a glass-lined reactor
equipped with an agitating apparatus. Dibromodifluoroethane can be
added to the reactor above the surface of the mixture at about
76.degree. C., ambient pressure, and flow rates of from about 1.3
grams per minute to about 5.1 grams per minute.
[0039] Referring to FIG. 3, a system 30 is shown that includes two
reaction zones, reaction zone 31 coupled to reaction zone 32.
Reaction zone 31 can be configured to be a plurality of reactors
and in exemplary embodiments reaction zone 31 can be configured as
system 20 previously described or as system 10 previously
described. In such configurations, reaction zone 31 can be coupled
to a halogenated alkane reservoir 33, which can form a portion of
the product recovery reservoir of reaction zone 32. The halogenated
alkane can be produced within reaction zone 32 by reacting a
hydrohalogenated olefin from a hydrohalogenated olefin reservoir 34
to form the halogenated alkane. The hydrohalogenated olefin within
hydrohalogenated olefin reservoir 34 can comprise one or more of F,
Cl, Br, and/or I. The hydrohalogenated olefin can be a C-2 olefin
such as C.sub.2HF.sub.3 and in exemplary embodiments can be
##STR00013##
System 30 also includes a halogenating reagent reservoir 35 coupled
to reaction zone 32. The halogenating reagent of the halogenating
reagent reservoir can comprise one or more of F, Cl, Br, and/or I.
In exemplary embodiments, the halogenating reagent can include
Br.sub.2. Utilizing system 30, for example, a hydrohalogenated
olefin can be reacted to form a halogenated alkane and the
halogenated alkane can be reacted to form a conjugated olefin. As
such, the hydrohalogenated olefin can be reacted to form a
conjugated olefin.
[0040] In exemplary embodiments, the reacting of the
hydrohalogenated olefin to form the halogenated alkane can include
configuring reaction zone 32 to expose the hydrohalogenated olefin
to the halogenating reagent from halogenating reagent reservoir 35.
The hydrohalogenated olefin from hydrohalogenated olefin reservoir
34 can be provided to within reaction zone 32 and the
hydrohalogenated olefin provided therein can be exposed to the
halogenating reagent to form the halogenated alkane. System 30 can
also include recycle conduit 15 that can be coupled to reaction
zone 31 and 32 as well as halogenated product recovery zone 16.
According to exemplary embodiments, the recycled conduits of
systems 10, 20, and 30 can be configured to receive at least one
by-product from product reservoirs of those systems and convey
those by-products to previous points in the systems for conversion
of those by-products to the sought after products such as the
conjugated olefin. Exemplary aspects of system 30 are described
with reference to scheme (7) below.
##STR00014##
[0041] In accordance with scheme (7) above, to a flask that can be
equipped with a magnetic stirrer, reflux condenser, and a gas
bubbler, about 10 grams (0.125 mole) of elemental bromine can be
placed. The elemental bromine can be exposed to an incandescent
lamp, and about 9.24 grams (0.113 mole) of gaseous
1,1,2-trifluoroethene (TFE) can be fed though a rotometer at a rate
such that no reflux of TFE can be observed on the condenser, to
form a mixture. The mixture can be observed to turn from deep red
to semi-clear in color whereupon the incandescent light can be
removed and the crude mixture can be charged to a separation funnel
where it can be washed sequentially with saturated sodium
bicarbonate solution and water. The resulting clear oil can be
dried over magnesium sulfate, filtered, and distilled to afford the
1,2-dibromo-1,1,2-trifluoroethane product.
[0042] A metal (Inconel.RTM. or Hastelloy.RTM.) tube reactor can be
charged with the appropriate amount of activated carbon and heated
by a furnace to about 150.degree. C. To this tube, equal molar
amounts of 1,1,2-trifluoroethene and elemental bromine can be fed
at such a rate that they are consumed resulting in a semi-clear
(reddish) liquid which can be collected in a flask cooled with dry
ice. The liquid can be charged to a separation funnel where it can
be washed sequentially with saturated sodium bicarbonate solution
and water. The resulting clear oil can be dried over magnesium
sulfate, filtered, and distilled to afford the
1,2-dibromo-1,1,2-trifluoroethane product.
[0043] Chemical production processes are also provided that can
include providing a heterohalogenated olefin and a reducing reagent
to within a reactor and reacting the olefin with the reducing agent
within the reactor with at least the olefin being in the liquid
phase during the reacting. The heterohalogenated olefin can include
C.sub.2CIF.sub.3 and the reducing reagent can include H, such as
H.sub.2. A catalyst composition may also be provided to the
reactor, the catalyst composition can include one or both of Pd
and/or C, such as activated carbon. An organic media may be
provided to the reactor as well. The media can include methanol,
for example.
##STR00015##
[0044] According to scheme (8) above, to a reactor equipped with an
agitator, methanol can be added and cooled to about -10.degree. C.
To the methanol can be added a sufficient amount of a 10% (wt./wt.)
palladium on activated carbon (Pd/AC) composition. At least about
1% (wt./wt.) of the amount of chlorotrifluoroethylene (CTFE) to be
fed to the reactor can be a sufficient amount of the composition.
The reactor can then be sealed, evacuated, and purged with hydrogen
(H.sub.2) twice. The reactor can then be heated to from about 30 to
about 40.degree. C. and then pressurized to 6 Kg/cm.sup.2 of
H.sub.2. CTFE and H.sub.2 can then be fed simultaneously to the
reactor using a 20% molar ratio excess of H.sub.2 to CTFE. The
reactor pressure may increase, and when the pressure within the
reactor reaches the desired operating pressure (1-12 Kg/cm.sup.2),
the product trifluoroethylene (TriFE), CTFE, and H.sub.2 can be
removed which can result in a 50% conversion of CTFE to TriFE. A
crude reaction mixture can assay as high as 70% TriFE by GC.
[0045] The crude reaction mixture can then be fed into another
reactor (equipped with an agitator), and the reactor can be charged
with elemental bromine (Br.sub.2) at 50.degree. C. while H.sub.2
can be removed via a column connected to the reactor and fitted
with a cooled condenser. Another crude reaction mixture can then be
separated by distillation giving the desired
1,2-dibromo-1,1,2-trifluoroethylene (DBTFE) as a overhead
condensate.
[0046] According to another embodiment, the perhalogenated olefin
can be produced according to scheme (9) below from the starting
material perchloroethene.
##STR00016##
* * * * *