U.S. patent application number 13/652681 was filed with the patent office on 2013-04-25 for phosphorus modified zeolite catalysts.
This patent application is currently assigned to ExxonMobil Research and Engineering Company. The applicant listed for this patent is ExxonMobil Research and Engineering Company. Invention is credited to TILMAN W. BEUTEL, MICHEL DAAGE, KARLTON J. HICKEY, STEPHEN J. McCARTHY, BEAU WALDRUP.
Application Number | 20130102824 13/652681 |
Document ID | / |
Family ID | 47089187 |
Filed Date | 2013-04-25 |
United States Patent
Application |
20130102824 |
Kind Code |
A1 |
BEUTEL; TILMAN W. ; et
al. |
April 25, 2013 |
PHOSPHORUS MODIFIED ZEOLITE CATALYSTS
Abstract
A bound phosphorus-modified catalyst composition comprises a
zeolite having a silica to alumina molar ratio of at least 40,
phosphorus in an amount between about 0.1 wt % and about 3 wt % of
the total catalyst composition, and a binder essentially free of
aluminum. The bound catalyst composition can advantageously exhibit
at least one of: (a) microporous surface area of at least 340
m.sup.2/g; (b) an alpha value after steaming in .about.100% steam
for .about.96 hours at .about.1000.degree. F. (.about.538.degree.
C.) of at least 40; and (c) a coke deactivation rate
constant<0.05 after steaming in .about.100% steam for .about.96
hours at .about.1000.degree. F. (.about.538.degree. C.). The bound
catalyst, as calcined, can advantageously also exhibit (i)
2,2-dimethylbutane diffusivity>.about.1.5.times.10.sup.-2
sec.sup.-1 measured at .about.120.degree. C. and .about.60 torr
(.about.8 kPa) and (ii) a coke deactivation rate
constant<.about.0.15.
Inventors: |
BEUTEL; TILMAN W.; (Neshanic
Station, NJ) ; McCARTHY; STEPHEN J.; (Center Valley,
PA) ; WALDRUP; BEAU; (Luberton, TX) ; DAAGE;
MICHEL; (Hellertown, PA) ; HICKEY; KARLTON J.;
(Boothwyn, PA) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
ExxonMobil Research and Engineering Company; |
Annandale |
NJ |
US |
|
|
Assignee: |
ExxonMobil Research and Engineering
Company
Annandale
NJ
|
Family ID: |
47089187 |
Appl. No.: |
13/652681 |
Filed: |
October 16, 2012 |
Related U.S. Patent Documents
|
|
|
|
|
|
Application
Number |
Filing Date |
Patent Number |
|
|
61548052 |
Oct 17, 2011 |
|
|
|
61548015 |
Oct 17, 2011 |
|
|
|
61548038 |
Oct 17, 2011 |
|
|
|
61548044 |
Oct 17, 2011 |
|
|
|
61548057 |
Oct 17, 2011 |
|
|
|
61548064 |
Oct 17, 2011 |
|
|
|
Current U.S.
Class: |
585/407 ; 502/60;
502/64; 502/77; 585/475; 585/899 |
Current CPC
Class: |
B01J 35/1014 20130101;
B01J 35/1061 20130101; C01B 39/54 20130101; B01J 21/04 20130101;
B01J 29/83 20130101; B01J 35/0026 20130101; B01J 35/1038 20130101;
Y02P 20/10 20151101; C10G 2400/04 20130101; B01J 2229/186 20130101;
B01J 35/002 20130101; B01J 37/06 20130101; B82Y 30/00 20130101;
B01J 29/40 20130101; B01J 35/1004 20130101; C07C 2/864 20130101;
C10G 3/49 20130101; B01J 37/28 20130101; B01J 2229/37 20130101;
C07C 1/22 20130101; B01J 2229/36 20130101; B82Y 40/00 20130101;
C07C 1/20 20130101; B01J 29/00 20130101; B01J 37/0009 20130101;
B01J 35/1019 20130101; B01J 2229/42 20130101; B01J 35/1085
20130101; Y02P 30/20 20151101; C07C 41/09 20130101; B01J 35/1042
20130101; B01J 37/0201 20130101; B01J 37/04 20130101; C07C 1/24
20130101; C10G 2400/02 20130101; C07C 41/09 20130101; C07C 43/043
20130101 |
Class at
Publication: |
585/407 ;
585/475; 585/899; 502/60; 502/77; 502/64 |
International
Class: |
B01J 29/83 20060101
B01J029/83; C07C 1/22 20060101 C07C001/22 |
Claims
1. A bound phosphorus-modified catalyst composition comprising a
zeolite having a silica to alumina molar ratio of at least 40,
phosphorus in an amount between about 0.1 wt % and about 3 wt % of
the total catalyst composition, and a binder that is essentially
free of aluminum, wherein the bound catalyst, as calcined at a
temperature of at least about 1000.degree. F. (about 538.degree.
C.) for at least about 3 hours, exhibits (i) a diffusivity for
2,2-dimethylbutane of greater than 1.5.times.10.sup.-2 sec.sup.-1
when measured at a temperature of about 120.degree. C. and a
2,2-dimethylbutane pressure of about 60 torr (about 8 kPa), and
(ii) a coke deactivation rate constant less than about 0.15, and
wherein the bound catalyst composition further exhibits at least
one of the following properties: (a) a microporous surface area of
at least 375 m.sup.2/g; (b) an alpha value after steaming in
approximately 100% steam for about 96 hours at about 1000.degree.
F. (about 538.degree. C.) of at least 40; and (c) a coke
deactivation rate constant less than 0.05 after steaming in
approximately 100% steam for about 96 hours at about 1000.degree.
F. (about 538.degree. C.).
2. The catalyst composition of claim 1, wherein the silica to
alumina molar ratio of the zeolite is from about 40 to about
200.
3. The catalyst composition of claim 1, wherein said zeolite has a
constraint index of about 1 to about 12.
4. The catalyst composition of claim 1, wherein said zeolite
comprises ZSM-5.
5. The catalyst composition of claim 1, wherein the bound catalyst
composition contains phosphorus in an amount between about 0.5 wt %
and about 2 wt % of the total catalyst composition.
6. The catalyst composition of claim 1, wherein the binder is
present in an amount between about 1 wt % and about 50 wt % of the
total catalyst composition.
7. The catalyst composition of claim 1, wherein the binder is
present in an amount between about 5 wt % and about 40 wt % of the
total catalyst composition.
8. The catalyst composition of claim 1, wherein the binder
comprises silica.
9. The catalyst composition of claim 1, wherein the alpha value
after steaming in approximately 100% steam for about 96 hours at
about 1000.degree. F. (about 538.degree. C.) is at least 60.
10. The catalyst composition of claim 1, wherein coke deactivation
rate constant after steaming in approximately 100% steam for about
96 hours at about 1000.degree. F. (about 538.degree. C.) is less
than 0.04.
11. The catalyst composition of claim 1, wherein the bound catalyst
composition exhibits at least two of the properties (a) to (c).
12. The catalyst composition of claim 1, wherein the bound catalyst
composition exhibits all of the properties (a) to (c).
13. A process for organic compound conversion employing contacting
a feedstock with the bound catalyst composition of claim 1 under
organic compound conversion conditions.
14. The process of claim 13, wherein said organic compound
conversion comprises the conversion of methanol to hydrocarbons
boiling in the gasoline boiling range.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application claims the benefit of U.S. Provisional
Application No. 61/548,052, filed on Oct. 17, 2011, the entire
contents of which are hereby incorporated by reference herein.
[0002] This application also claims the benefit of related U.S.
Provisional Application Nos. 61/548,015, 61/548,038, 61/548,044,
61/548,057, and 61/548,064, each filed on Oct. 17, 2011, the entire
contents of each of which are hereby also incorporated by reference
herein. This application is also related to five other co-pending
U.S. utility applications, each filed on even date herewith and
claiming the benefit to the aforementioned provisional patent
applications, and which are entitled "Process for Producing
Phosphorus Modified Zeolite Catalysts", "Process for Producing
Phosphorus Modified Zeolite Catalysts", "Phosphorus Modified
Zeolite Catalysts", "Phosphorus Modified Zeolite Catalysts", and
"Selective Dehydration of Alcohols to Dialkyl Ethers",
respectively, the entire contents of each of which utility patents
are hereby further incorporated by reference herein.
FIELD OF THE INVENTION
[0003] This disclosure relates to a phosphorus modified zeolite
catalyst and its use in organic conversion reactions, such as the
conversion of methanol to gasoline and diesel boiling range
hydrocarbons.
BACKGROUND OF THE INVENTION
[0004] Phosphorus modification is a known method of improving the
performance of zeolite catalysts for a variety of chemical
processes including, for example, the conversion of methanol to
hydrocarbons and the methylation of toluene to produce xylenes. For
example, U.S. Pat. Nos. 4,590,321 and 4,665,251 disclose a process
for producing aromatic hydrocarbons by contacting one or more
non-aromatic compounds, such as propane, propylene, or methanol,
with a catalyst containing a zeolite, such as ZSM-5. The zeolite is
modified with phosphorus oxide by impregnating the zeolite with a
source of phosphate ions, such as an aqueous solution of an
ammonium phosphate, followed by calcination. The phosphorus oxide
modification is said to render the zeolite more active and/or
benzene selective in the aromatization reaction.
[0005] In addition, U.S. Pat. No. 7,304,194 discloses a process for
the hydrothermal treatment of a phosphorus-modified ZSM-5 catalyst.
The ZSM-5 has a silica/alumina mole ratio of at least about 200, a
crystal particle size of at least 0.5 micron and may be used in
unbound form or combined with a binder selected from alumina, clay,
or silica. The phosphorus-modified zeolite contains from about 0.01
g P/g zeolite to about 0.15 g P/g zeolite and is calcined at a
temperature of at least 300.degree. C. to produce a catalyst having
a BET surface area of 150-200 m.sup.2/g determined by
N.sub.2adsorption techniques. The calcined catalyst is then treated
with steam at a temperature of from about 150.degree. C. to about
350.degree. C. The steamed, phosphorus modified zeolite is said to
exhibit improved para-selectivity and methanol selectivity when
used as a catalyst in toluene methylation reactions.
[0006] U.S. Patent Application Publication No. 2010/0168489
discloses a bound phosphorus-modified zeolite catalyst, in which
the binder material is treated with a mineral acid prior to being
bound with the phosphorus-modified zeolite. Suitable binder
materials are said to include inorganic oxides, such as alumina,
clay, aluminum phosphate and silica-alumina. After optional
extrusion, the zeolite-binder mixture is heated at a temperature of
about 400.degree. C. or higher to form a bound zeolite catalyst,
typically from 0.01 to about 0.15 gram of phosphorus per gram of
zeolite. The catalyst is particularly intended for use in the
alkylation of toluene with methanol to produce xylenes, but is also
said to be useful in MTG processes.
[0007] Current catalysts for the conversion of methanol to gasoline
(MTG) also generally employ a bound phosphorus-modified zeolite
catalyst. The MTG reaction is catalyzed by acid sites generated by
framework aluminum inside the micropores of the zeolite catalyst,
whereas the role of the phosphorus can be to stabilize the zeolite
framework aluminum against dealumination by the high temperature
steam generated as a by-product of the process. The role of the
binder material can be to assist in maintaining the integrity of
the catalyst particles in the catalyst bed but, with certain
binders, especially alumina-containing binders, the phosphorus can
preferentially migrate to the binder alumina and/or can increase
the coke selectivity of the catalyst. There is therefore a need for
an improved catalyst for use in the conversion of methanol to
gasoline.
SUMMARY OF THE INVENTION
[0008] In one aspect, the invention resides in a bound
phosphorus-modified catalyst composition comprising a zeolite
having a silica to alumina molar ratio of at least 40, phosphorus
in an amount between about 0.1 wt % and about 3 wt % of the total
catalyst composition, and a binder that is essentially tree of
aluminum, wherein the catalyst composition exhibits at least one,
and preferably at least two, of the following properties: (a) a
microporous surface area of at least 340 m.sup.2/g; (b) a
diffusivity for 2,2-dimethylbutane of greater than
1.2.times.10.sup.-2 sec.sup.-1, e.g., greater than
1.5.times.10.sup.-2 sec.sup.-1, when measured at a temperature of
.about.120.degree. C. and a 2,2-dimethylbutane pressure of
.about.60 torr (.about.8 kPa); (c) an alpha value after steaming in
.about.100% steam for .about.96 hours at .about.1000.degree. F.
(.about.538.degree. C.) of at least 20, e.g., of at least 40; and
(d) a coke deactivation rate constant less than or equal to 0.06
after steaming in .about.100% steam for .about.96 hours at
.about.900.degree. F. (.about.482.degree. C.).
[0009] Conveniently, the silica to alumina, molar ratio of the
zeolite can be from about 40 to about 200.
[0010] Conveniently, the zeolite can have a constraint index of
about 1 to about 12 and in one embodiment comprises ZSM-5.
[0011] Conveniently, the catalyst composition can contain
phosphorus in an amount between about 0.5 wt % and about 2 wt %, of
the total catalyst composition.
[0012] Conveniently, the binder can be present in an amount between
about 1 wt % and about 50 wt %, e.g., between about 5 wt % and
about 40 wt %, of the total catalyst composition. In one
embodiment, the binder can comprise or be silica.
[0013] In a further aspect, the invention can reside in use of
bound phosphorus-modified catalyst composition described herein in
organic conversion reactions, such as the conversion of methanol to
hydrocarbons boiling in the gasoline boiling range.
BRIEF DESCRIPTION OF THE DRAWINGS
[0014] FIG. 1 shows a graph comparing the normalized alpha values
of the catalysts of Examples 1-4 after steaming in .about.100%
steam for about 96 hours at .about.1000.degree. F.
(.about.538.degree. C.).
[0015] FIG. 2 shows a graph comparing the microporous surface area
of the catalysts of Examples 1-3, normalized by zeolite
content.
[0016] FIG. 3 shows a graph comparing the diffusivity for
2,2-dimethylbutane of the catalysts of Examples 1-3 at a
temperature of about 120.degree. C. and a 2,2-dimethylbutane
pressure of .about.60 torr (.about.8 kPa).
[0017] FIG. 4 shows a graph comparing the normalized alpha values
and the coke deactivation rate constants of the catalysts of
Example 6 after steaming in .about.100% steam for about 96 hours at
.about.900.degree. F. (.about.482.degree. C.).
DETAILED DESCRIPTION OF THE EMBODIMENTS
[0018] Described herein are bound phosphorus-stabilized zeolite
catalyst compositions and their use in a variety of organic
conversion reactions, particularly, but not exclusively, in the
conversion of methanol to hydrocarbons boiling in the gasoline
boiling range.
[0019] The zeolite employed in the present catalyst composition can
typically have a silica, to alumina molar ratio of at least 40, for
example from about 40 to about 200. Generally, the zeolite can
comprise at least one medium pore aluminosilicate zeolite, e.g.,
having a Constraint Index of 1-12 (as defined in U.S. Pat. No.
4,016,218). Suitable zeolites can include, but are not necessarily
limited to, ZSM-5, ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM-35, ZSM-48,
and the like, and combinations thereof. ZSM-5 is described in
detail in U.S. Pat. Nos. 3,702,886 and RE 29,948. ZSM-11 is
described in detail in U.S. Pat. No. 3,709,979. ZSM-12 is described
in U.S. Pat. No. 3,832,449. ZSM-22 is described in U.S. Pat. No.
4,556,477. ZSM-23 is described in U.S. Pat. No. 4,076,842. ZSM-35
is described in U.S. Pat. No. 4,016,245. ZSM-48 is more
particularly described in U.S. Pat. No. 4,234,231. In certain
preferred embodiments, the zeolite can comprise or be ZSM-5.
[0020] When used in the present catalyst composition, the zeolite
can advantageously be present at least partly in the hydrogen form.
Depending on the conditions used to synthesize the zeolite, getting
to the hydrogen form may involve converting the zeolite from, for
example, the alkali (sodium) form. This can readily be achieved,
e.g., by ion exchange to convert the zeolite to the ammonium form,
followed by calcination in air or an inert atmosphere, such as at a
temperature from about 400.degree. C. to about 700.degree. C. to
convert the ammonium form to the active hydrogen form. If an
organic structure directing agent is used in the synthesis of the
zeolite, calcination may be additionally desirable to remove the
organic structure directing agent.
[0021] The zeolite can be combined with a binder, generally an
inorganic oxide, that is essentially free of aluminum. In the
present specification, a binder that is "essentially free of
aluminum" should be understood to mean a binder containing less
than 10 wt % aluminum, for example less than 7 wt %, less than 5 wt
%, less than 3 wt %, less than 1 wt %, less than 0.5 wt %, less
than 0.1 wt %, or no detectable aluminum, as measured by XRF/ICP. A
suitable binder is silica. Generally, the binder can be present in
an amount between about 1 wt % and about 50 wt %, for example
between about 5 wt % and about 40 wt %, of the total catalyst
composition. Combining the zeolite and the binder can generally be
achieved by mulling an aqueous mixture of the zeolite and binder
and then extruding the mixture into catalyst pellets. A process for
producing zeolite extrudates using a silica binder is disclosed in,
for example, U.S. Pat. No. 4,582,815, the entire contents of which
are incorporated herein by reference.
[0022] To enhance the steam stability of the zeolite without
excessive loss of its initial acid activity, the present catalyst
composition can contain phosphorus in an amount between about 0.01
wt % and about 3 wt % elemental phosphorus, for example between
about 0.05 wt % and about 2 wt %, of the total catalyst
composition. The phosphorus can be added to the catalyst
composition at any stage during synthesis of the zeolite or
formulation of the zeolite and binder into the bound catalyst
composition. Generally, phosphorus addition can be achieved by
spraying and/or impregnating the final catalyst composition (and/or
a precursor thereto) with a solution of a phosphorus compound.
Suitable phosphorus compounds can include, but are not limited to,
phosphinic [H.sub.2PO(OH)], phosphonic [HPO(OH).sub.2], and
phosphoric [PO(OH).sub.3] acids, salts and esters of such acids,
phosphorus halides, and the like, and combinations thereof. After
phosphorus treatment, the catalyst can generally be calcined, e.g.,
in air at a temperature from about 400.degree. C. to about
700.degree. C., to convert the phosphorus to an oxide form.
[0023] The bound phosphorus-stabilized zeolite catalyst composition
employed herein can advantageously exhibit both (i) a diffusivity
for 2,2-dimethylbutane of greater than 1.5.times.10.sup.-2
sec.sup.-1, for example at least 1.7.times.10.sup.-2 sec.sup.-1 or
at least 2.times.10.sup.-2 sec.sup.-1, when measured at a
temperature of about 120.degree. C. and a 2,2-dimethylbutane
pressure of about 60 torr (about 8 kPa) and (ii) a coke
deactivation rate constant, as calcined, of less than 0.2, e.g.,
less than about 0.15 or less than about 0.12. The bound
phosphorus-stabilized zeolite catalyst composition employed herein
can additionally or alternately be characterized by at least one,
and preferably at least two or in some embodiments all, of the
following properties: (a) a microporous surface area of at least
340 m.sup.2/g, for example of at least 375 m.sup.2/g; (b) an alpha
value after steaming in .about.100% steam for .about.96 hours at
.about.1000.degree. F. (.about.538.degree. C.) of at least 20, for
example of at least 40 or of at least 60; and (d) a coke
deactivation rate constant less than or equal to 0.06, for example
less than 0.05 or less than 0.04, after steaming in .about.100%
steam for .about.96 hours at .about.1000.degree. F.
(.about.538.degree. C.). It should be appreciated by one of
ordinary skill in the art that property (a) above, unlike
properties (b) and (c), are measured before any steaming of the
catalyst composition.
[0024] Of these properties, micoporosity and diffusivity for
2,2-dimethylbutane can be determined by a number of factors
including, but not limited to, the pore size and crystal size of
the zeolite and the accessibility of the zeolite pores at the
surfaces of the catalyst particles. Producing a zeolite catalyst
with the desired microporous surface area and 2,2-dimethylbutane
diffusivity should be well within the expertise of anyone of
ordinary skill in zeolite chemistry.
[0025] Alpha value is a measure of the acid activity of a zeolite
catalyst, as compared with a standard silica-alumina catalyst. The
alpha test is described in U.S. Pat. No. 3,354,078; in the Journal
of Catalysis, v. 4, p. 527 (1965); v. 6, p. 278 (1966); and v. 61,
p. 395 (1980), each incorporated herein by reference as to that
description. The experimental conditions of the test used herein
include a constant temperature of about 538.degree. C. and a
variable flow rate as described in detail in the Journal of
Catalysis, v. 61, p. 395. The higher alpha values can tend to
correspond to a more active cracking catalyst. Since the present
catalyst composition is intended for use in reactions such as MTG,
where the zeolite can be subject to hydro thermal dealumination of
the zeolite, it can be important for the bound catalyst composition
to retain a significant alpha value, namely at least 20, after
steaming in .about.100% steam for .about.96 hours at
.about.1000.degree. F. (.about.538.degree. C.).
[0026] The coke deactivation rate constant can be a measure of the
rate at which the catalyst deactivates and is explained in more
detail in the Examples.
[0027] The phosphorus-modified bound zeolite catalyst composition
described herein can be particularly useful in any organic
conversion process where the hydrothermal stability of the catalyst
is important. Examples of such processes can include, but are not
necessarily limited to, fluid catalytic cracking of heavy
hydrocarbons to gasoline and diesel boiling range hydrocarbons,
methylation and disproportionation of toluene to produce xylenes,
n-paraffin (e.g., C.sub.6 and higher) cyclization, conversion of
methanol to gasoline and diesel boiling range hydrocarbons, and the
like, and combinations and/or integrations thereof.
[0028] The invention can additionally or alternately include one or
more of the following embodiments.
Embodiment 1
[0029] A bound phosphorus-modified catalyst composition comprising
a zeolite having a silica to alumina molar ratio of at least 40,
phosphorus in an amount between about 0.1 wt % and about 3 wt % of
the total catalyst composition, and a binder that is essentially
free of aluminum, wherein the bound catalyst, as calcined at a
temperature of at least about 1000.degree. F. (about 538.degree.
C.) for at least about 3 hours, exhibits (i) a diffusivity for
2,2-dimethylbutane of greater than 1.5.times.10.sup.-2 sec.sup.-1
when measured at a temperature of about 120.degree. C. and a
2,2-dimethylbutane pressure of about 60 torr (about 8 kPa), and
(ii) a coke deactivation rate constant less than about 0.15, and
wherein the bound catalyst composition further exhibits at least
one of the following properties: (a) a microporous surface area, of
at least 340 m.sup.2/g, e.g., at least 375 m.sup.2/g; (b) an alpha
value after steaming in approximately 100% steam for about 96 hours
at about 1000.degree. F. (about 538.degree. C.) of at least 20,
e.g., at least 40; and (c) a coke deactivation rate constant less
than or equal to 0.06, e.g., less than 0.05 or less than 0.04 after
steaming in approximately 100% steam for about 96 hours at about
1000.degree. F. (about 538.degree. C.).
Embodiment 2
[0030] The catalyst composition of embodiment 1, wherein the silica
to alumina molar ratio of the zeolite is from about 40 to about
200.
Embodiment 3
[0031] The catalyst composition of any one of the previous
embodiments, wherein said zeolite has a constraint index of about 1
to about 12.
Embodiment 4
[0032] The catalyst composition of any one of the previous
embodiments, wherein said zeolite comprises or is ZSM-5.
Embodiment 5
[0033] The catalyst composition of any one of the previous
embodiments, wherein the bound catalyst composition contains
phosphorus in an amount between about 0.5 wt % and about 2 wt % of
the total catalyst composition.
Embodiment 6
[0034] The catalyst composition of any one of the previous
embodiments, wherein the binder is present in an amount between
about 1 wt % and about 50 wt %, e.g., between about 5 wt % and
about 40 wt %, of the total catalyst composition.
Embodiment 7
[0035] The catalyst composition of any one of the previous
embodiments, wherein the binder comprises silica.
Embodiment 8
[0036] The catalyst composition of any one of the previous
embodiments, wherein the alpha value after steaming in
approximately 100% steam for about 96 hours at about 1000.degree.
F. (about 538.degree. C.) is at least 60.
Embodiment 9
[0037] The catalyst composition of any one of the previous
embodiments, wherein the bound catalyst composition exhibits at
least two of the properties (a) to (c).
Embodiment 10
[0038] The catalyst composition of any one of the previous
embodiments, wherein the bound catalyst composition exhibits ail of
the properties (a) to (c).
Embodiment 11
[0039] A process for organic compound conversion employing
contacting a feedstock with the bound catalyst composition of any
one of the previous embodiments under organic compound conversion
conditions.
Embodiment 12
[0040] The process of embodiment 12, wherein said organic compound
conversion comprises the conversion of methanol to hydrocarbons
boiling in the gasoline boiling range.
[0041] The invention will now be more particularly described with
reference to the Examples and the accompanying drawings.
EXAMPLES
Example 1
Preparation of P-Modified ZSM-5/Versal-300 Alumina Catalyst
[0042] A mixture of .about.80 wt % of as-synthesized NaZSM-5
zeolite (having a silica to alumina, molar ratio of about 50 and
containing the organic directing agent used in its synthesis) was
blended in a muller with .about.20 wt % of Versal.TM.-300 alumina
binder. The blend was extruded and the resultant extrudate sample
was calcined in nitrogen for .about.3 hours at .about.1000.degree.
F. (.about.538.degree. C.) to decompose the organic template into a
carbonaceous deposit. The calcined extrudate was then exchanged
with an ammonium nitrate solution to convert the zeolite from the
sodium to the ammonium form, whereafter the extrudate was calcined
in air for .about.3 hours at .about.1000.degree. F.
(.about.538.degree. C.) to convert the zeolite from the ammonium to
the hydrogen form. At the same time carbonaceous deposits were
removed by oxidation. The thus obtained H-ZSM-5-Al.sub.2O.sub.3
extrudate was then impregnated with phosphoric acid to a target
level of .about.0.96 wt % phosphorus via aqueous incipient wetness
impregnation. The sample was dried and then calcined in air for
.about.3 hours at .about.1000.degree. F. (.about.538.degree. C.).
The resultant product was labeled Catalyst A and had the properties
summarized in Table 1 below.
Example 2
Preparation of P-Modified Unbound ZSM-5 Catalyst
[0043] A sample of as-synthesized NaZSM-5 zeolite was extruded
without the use of binder. The sample was calcined in nitrogen for
.about.3 hours at .about.1000.degree. F. (.about.538.degree. C.),
exchanged with an ammonium nitrate solution, and calcined in air
for .about.3 hours at .about.1000.degree. F. (.about.538.degree.
C.). The extrudate was impregnated with phosphoric acid to a target
level of .about.1.2 wt % phosphorus via aqueous incipient wetness
impregnation. The sample was dried and then calcined for .about.3
hours at .about.1000.degree. F. (.about.538.degree. C.). The
resultant product was labeled Catalyst B and had the properties
summarized in Table 1 below.
Example 3
Preparation of P-Modified Unbound Small Crystal ZSM-5 Catalyst
[0044] A sample of as-synthesized small crystal NaZSM-5 zeolite was
extruded without the use of binder. The sample was calcined in
nitrogen for .about.3 hours at .about.1000.degree. F.
(.about.538.degree. C.), exchanged with an ammonium nitrate
solution, and calcined in air for .about.3 hours at
.about.1000.degree. F. (.about.538.degree. C.). The extrudate was
impregnated with phosphoric acid to a target level of .about.1.2 wt
% phosphorus via aqueous incipient wetness impregnation. The sample
was dried and then calcined for .about.3 hours at
.about.1000.degree. F. (.about.538.degree. C.). The resultant
product was labeled Catalyst C and had the properties summarized in
Table 1 below.
Example 4
Preparation of P-Modified Silica-Bound ZSM-5 Catalyst
[0045] A mixture of .about.80 wt % as-synthesized small crystal
NaZSM-5 zeolite was extruded with .about.20 wt % Ultrasil.TM.
silica. The sample was calcined in nitrogen for .about.3 hours at
.about.1000.degree. F. (.about.538.degree. C.), exchanged with an
ammonium nitrate solution, and calcined in air for .about.3 hours
at .about.1000.degree. F. (.infin.538.degree. C.). The extrudate
was impregnated with phosphoric acid to a target level of
.about.0.96 wt % phosphorus via aqueous incipient wetness
impregnation. The sample was dried and then calcined for .about.3
hours at .about.1000.degree. F. (.about.538.degree. C.). The
resultant product was labeled Catalyst D and had the properties
summarized in Table 1 below.
TABLE-US-00001 TABLE 1 Binder Binder content, P (wt % based Cat
Si/Al.sub.2 type wt % on zeolite) A ~50 Al.sub.2O.sub.3 ~20 ~1.0 B
~50 N/A 0 ~1.2 C ~50 N/A 0 ~1.2 D ~50 SiO.sub.2 ~20 ~1.0
Example 5
Alpha Testing
[0046] Samples of the Catalysts A-D were tested for their n-hexane
cracking activity (alpha test) after steaming in .about.100%
H.sub.2O atmosphere for .about.96 hours at .about.1000.degree. F.
(.about.538.degree. C.). The n-hexane cracking activity, expressed
as alpha value, can be a measure of the acidity of the catalyst.
Alpha value is defined as the ratio of the first order rate
constant for n-hexane cracking, relative to a silica-alumina
standard, and can be determined using the following formula:
.alpha.=A*ln(1-X)/.tau.
where: [0047] A: includes the reference rate constant & unit
conversion.apprxeq.-1.043 [0048] X: fractional conversion [0049]
.tau.: Residence time=wt/(.rho.*F) [0050] .rho.: Packing density
[g/cm.sup.3] [0051] F: gas flow rate [cm.sup.3/min] [0052] wt:
Catalyst weight [g]
[0053] The flow rate was adjusted to maintain a conversion between
about 5% and about 25%. Four data points were measured at .about.4,
.about.11, .about.18, and .about.25 minutes. The alpha value was
the relative first order rate constant at .about.18 minutes.
[0054] FIG. 1 shows the alpha values, normalized by the nominal
amounts of zeolite that went into the extrudate formulation. The
alumina-containing reference Catalyst A exhibited a relatively low
alpha value, while the alumina-free catalysts B, C, and D exhibited
a significantly higher alpha value. In particular, Catalysts, B, C,
and D exhibited an alpha value greater than 40 in the n-hexane
cracking test after treatment in .about.100% H.sub.2O atmosphere
for .about.96 hours at .about.1000.degree. F. (.about.538.degree.
C.). It was surprising that the elimination of the alumina binder
in catalyst formulations B and C, and the replacement of the
alumina binder with a silica binder in catalyst formulation D,
resulted in a dramatic increase in alpha value after steaming.
Example 6
Microporous Surface Area
[0055] The MTG reaction generally takes place inside the zeolite
micropores. It can, therefore, be beneficial to improve/maximize
the zeolitic micropore volume in order to achieve maximum MTG
activity. Samples of Catalysts A-D were calcined for .about.6 hours
at .about.1000.degree. F. (.about.538.degree. C.) in air prior to
measurement of the micropore surface are by N.sub.2-BET. The
micropore surface areas were normalized by the zeolite content
present in the extrudates, and the results are shown in FIG. 2. The
formulation without added binder presented a higher microporosity,
compared with the reference formulation A containing the alumina
binder. Since the acid sites responsible for MTG activity are
believed to be located inside the zeolite micropores, this result
indicated an advantage of catalyst formulations B and C in an MTG
application, relative to the alumina-containing formulation A. The
results were surprising, because binder particles are typically
larger than the opening of the microchannels of the zeolite and
hence penetration of binder into the zeolite micropores was
therefore not anticipated. Moreover, blockage of zeolite micropores
by binder located at the pore mouth of the microchannels was not
expected to occlude zeolite micropore volume in a zeolite with
three-dimensional pore structure, as in MFI. The preferred catalyst
extrudate had a micropore surface area of at least 375 m.sup.2/g
zeolite.
Example 7
Diffusivity for 2,2-Dimethylbutane
[0056] The porosity of a zeolite can play a role in product
selectivity and coke formation in reactions involving the zeolite.
Fast diffusion of reactants into and of products out of zeolite
micropores can be advantageous, or even necessary, to obtain the
desired product composition and/or to prevent coke formation.
Samples of Catalysts A-C were calcined in air for .about.6 hours at
.about.1000.degree. F. (.about.538.degree. C.) prior to measurement
of the diffusivity of 2,2-dimethyl-butane (2,2-DMB). The
diffusivity was calculated from the rate of 2,2-DMB uptake and the
amount of hexane uptake using the following equation:
D/r.sup.2=k*(2,2-DMB uptake rate/hexane uptake)
where [0057] D/r.sup.2: Diffusivity [10.sup.-6 sec.sup.-1] [0058]
2,2-DMB uptake rate: [mg/g/min.sup.0.5] [0059] Hexane uptake:
[mg/g] [0060] k: Proportionality constant
[0061] Hexane and 2,2-DMB uptakes were measured in two separate
experiments using a microbalance. Prior to hydrocarbon adsorption,
about 50 mg catalyst sample was heated in air for .about.30 minutes
to .about.500.degree. C., in order to remove moisture and
hydrocarbon/coke impurities. For hexane adsorption, the sample was
cooled to .about.90.degree. C. and subsequently exposed to a flow
of .about.100 mbar hexane in nitrogen at .about.90.degree. C. for
.about.40 minutes. For 2,2-DMB adsorption, the sample was cooled to
.about.120.degree. C. after the air calcination step and exposed to
a 2,2-dimethylbutane pressure of .about.60 torr (.about.8 kPa) for
.about.30 minutes. The results are shown in FIG. 3, from which it
can be seen that Catalysts B and C exhibited a higher 2,2-DMB
diffusivity than Catalyst A. Preferred catalysts can advantageously
exhibit a hydrocarbon diffusivity greater than 1.2.times.10.sup.-2
sec.sup.-1, for example greater than 1.5.times.10.sup.-2 sec.sup.-1
or greater than 2.times.10.sup.-2 sec.sup.-1, using 2,2-dimethyl
butane (22-DMB) as hydrocarbon.
Example 8
Coke Resistance
[0062] Coke resistance can be an important property of a catalyst
intended for the application in the MTG reaction. The acid sites in
the catalyst are generally believed not only to catalyze the MTG
reaction but also to catalyze the formation of coke, which can
eventually deactivate the catalyst. In order to ensure a continuous
process, the catalyst should typically be regenerated periodically
from coke. The ability to maintain n-hexane cracking activity in
the alpha test was used as a measure for the coking stability of
the catalyst.
[0063] The catalysts used in the test were produced in the same way
as Examples 1 and 2, but with higher nominal P loadings of
.about.1.8 wt % and .about.1.6 wt %, respectively, on the
extrudate. The resultant catalysts were designated Catalysts A1 and
B1 and had the properties shown in Table 2 below.
TABLE-US-00002 TABLE 2 P content in Binder Binder content, Catalyst
extrudate, wt % type wt % A1 1.8 Al.sub.2O.sub.3 20 B1 1.6 none
0
[0064] The samples A1 and B1 listed in Table 2 were analyzed for
their coke resistance. Samples in Table 2 were steamed for
.about.96 hours at .about.900.degree. F. (.about.482.degree. C.)
and subsequently evaluated for their coke resistance in the alpha
test described above. For the evaluation of the coke resistance of
the catalyst in the n-hexane cracking reaction, the alpha values
measured at .about.4, .about.11, .about.18, and .about.25 minutes
were plotted as a function of time, and fitted by an exponential
function given in the following equation:
.alpha.=.alpha..sub.0*e.sup.-ct.sup.1/3
where .alpha..sub.0 is the alpha value at time 0, and c is the coke
deactivation rate constant.
[0065] Since the coke deactivation rate constant, c, can be
sensitive to flow rates, it can be important to keep the flow
constant during the four points of measurement. The results are
shown in FIG. 4.
[0066] The alpha values for the catalysts, A1 and B1, were 51 and
99, respectively. Evaluation of the coke deactivation rate constant
revealed that the initial alpha values, .alpha..sub.0, were 64 and
106, respectively. The corresponding coke deactivation rate
constants were 0.08 and 0.03, respectively. It was surprising that
the sample B1, exhibiting a higher alpha and initial alpha value,
was characterized by a lower coke deactivation constant than A1.
The preferred catalyst, B1 had a higher coke resistance and was
characterized by a coke deactivation rate constant smaller than
0.05, or smaller than 0.04, in the alpha test.
Example 9
Preparation of P-Modified ZSM-5/Versal-300 Alumina Catalyst
[0067] A mixture of .about.80 wt % of as-synthesized NaZSM-5
zeolite (having a silica to alumina molar ratio of about 50 and
containing the organic directing agent used in its synthesis) was
blended in a muller with .about.20 wt % of Versal.TM.-300 alumina
binder. The blend was extruded and the resultant extrudate sample
was calcined in nitrogen for .about.3 hours at .about.1000.degree.
F. (.about.538.degree. C.) to decompose the organic template. The
calcined extrudate was then exchanged with an ammonium nitrate
solution to convert the zeolite from the sodium to the ammonium
form, whereafter the extrudate was calcined in air for another
.about.3 hours at .about.1000.degree. F. (.about.538.degree. C.) to
convert the zeolite from the ammonium to the hydrogen form. At the
same time, any carbonaceous deposits (e.g., from the decomposition
of the organic template and/or from the ammonium nitrate exchange)
were removed by oxidation. The thus obtained
H-ZSM-5-Al.sub.2O.sub.3 extrudate was then impregnated with
phosphoric acid to a target level of .about.0.96 wt % phosphorus
via aqueous incipient wetness impregnation. The sample was dried
and then calcined in air for another .about.3 hours at
.about.1000.degree. F. (.about.538.degree. C.). The resultant
product was labeled Catalyst A'' and had the properties summarized
in Table 3 below.
Example 10
Preparation of P-Modified Unbound ZSM-5 Catalyst
[0068] A sample of as-synthesized NaZSM-5 zeolite was extruded
without the use of binder. The sample was calcined in nitrogen for
.about.3 hours at .about.1000.degree. F. (.about.538.degree. C.),
exchanged with an ammonium nitrate solution, and calcined in air
for another .about.3 hours at .about.1000.degree. F.
(.about.538.degree. C.). The extrudate was impregnated with
phosphoric acid to a target level of .about.1.2 wt % phosphorus via
aqueous incipient wetness impregnation. The sample was dried and
then calcined for another .about.3 hours at .about.1000.degree. F.
(.about.538.degree. C.). The resultant product was labeled Catalyst
B'' and had the properties summarized in Table 3 below.
Example 11
Preparation of P-Modified Unbound Small Crystal ZSM-5 Catalyst
[0069] A sample of as-synthesized small crystal NaZSM-5 zeolite was
extruded without the use of binder. The sample was calcined in
nitrogen for .about.3 hours at .about.1000.degree. F.
(.about.538.degree. C.), exchanged with an ammonium nitrate
solution, and calcined in air for another .about.3 hours at
.about.1000.degree. F. (.about.538.degree. C.). The extrudate was
impregnated with phosphoric acid to a target level of .about.1.2 wt
% phosphorus via aqueous incipient wetness impregnation. The sample
was dried and then calcined for another .about.3 hours at
.about.1000.degree. F. (.about.538.degree. C.). The resultant
product was labeled Catalyst C'' and had the properties summarized
in Table 3 below.
Example 12
Preparation of P-Modified Silica-Bound ZSM-5 Catalyst
[0070] A mixture of .about.80 wt % as-synthesized small crystal
NaZSM-5 zeolite was extruded with .about.20 wt % Ultrasil.TM.
silica. The sample was calcined in nitrogen for -3 hours at
.about.1000.degree. F. (.about.538.degree. C.), exchanged with an
ammonium nitrate solution, and calcined in air for another .about.3
hours at .about.1000.degree. F. (.about.538.degree. C.). The
extrudate was impregnated with phosphoric acid to a target level of
.about.0.96 wt % phosphorus via aqueous incipient wetness
impregnation. The sample was dried and then calcined for another
.about.3 hours at .about.1000.degree. F. (.about.538.degree. C.).
The resultant product was labeled Catalyst D'' and had the
properties summarized in Table 3 below.
Comparative Example 13
Preparation of P-Modified Silica-Bound ZSM-5 Catalyst
[0071] A mixture of .about.80 wt % of as-synthesized NaZSM-5
zeolite (having a silica to alumina molar ratio of about 28 and
containing the organic directing agent used in its synthesis) was
blended in a muller with .about.20 wt % of Ultrasil.TM. silica
binder. The blend was extruded and the resultant extrudate sample
was calcined in nitrogen for .about.3 hours at .about.1000.degree.
F. (.about.538.degree. C.). The calcined extrudate was then
exchanged with an ammonium nitrate solution, and then calcined in
air for another .about.3 hours at .about.1000.degree. F.
(.about.538.degree. C.). The extrudate was then impregnated with
phosphoric acid to a target level of .about.0.96 wt % phosphorus
via aqueous incipient wetness impregnation. The sample was dried
and then calcined in air for another .about.3 hours at
.about.1000.degree. F. (.about.538.degree. C.). The resultant
product was labeled Catalyst E and had the properties summarized in
Table 3 below.
TABLE-US-00003 TABLE 3 Binder content, P (wt % based Cat
Si/Al.sub.2 Binder type wt % on zeolite) A'' ~50 Al.sub.2O.sub.3
~20 ~1.0 B'' ~50 N/A 0 ~1.2 C'' ~50 N/A 0 ~1.2 D'' ~50 SiO.sub.2
~20 ~1.0 E ~28 SiO.sub.2 ~20 ~1.0
Example 14
Characterizations of Samples from Examples 9-13
[0072] For the samples made according to Examples 9-13 and detailed
in Table 3 above (A'', B'', C'', D'', and E, respectively), the
following tests were conducted. Alpha testing was done according to
Example 5, on samples that were treated by steaming in .about.100%
H.sub.2O atmosphere for .about.96 hours at .about.1000.degree. F.
(.about.538.degree. C.). Microporous surface area testing was done
according to Example 6, on as calcined samples. Diffusivity testing
for 2,2-dimethylbutane was done according to Example 7, on samples
that were calcined in air for .about.6 hours at .about.1000.degree.
F. (.about.538.degree. C.) prior to measurement. Coke resistance
testing, however, in order to measure coke deactivation rate
constants, was done similarly to, but slightly different than,
Example 8--coke resistance testing for these samples was done after
the samples were steamed for .about.96 hours at .about.1000.degree.
F. (.about.538.degree. C.), not at .about.900.degree. F.
(.about.482.degree. C.). Coke resistance testing was additionally
done for these samples on as calcined samples. The results of these
characterizations are shown in Table 4 below.
TABLE-US-00004 TABLE 4 Alpha value Surface area 2,2-DMB Diffus.
Coke Deact. Rate Coke Deact. Rate Catalyst (as steamed) (m.sup.2/g)
(*10.sup.-2 sec.sup.-1) Const. (steamed) Const. (as calcined) A''
33 385 1.42 0.43 0.30 B'' 103 429 2.14 0.01 0.10 C'' 81 385 2.51
0.02 0.02 D'' 100 409 1.76 0.01 0.03 E 128 386 0.03 0.05 0.22
[0073] While the present invention has been described and
illustrated by reference to particular embodiments, those of
ordinary skill in the art will appreciate that the invention lends
itself to variations not necessarily illustrated herein. For this
reason, then, reference should be made solely to the appended
claims for purposes of determining the true scope of the present
invention.
* * * * *