EP0277824A2
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EP
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Process for acetic acid preparation and heterogeneous catalyst for same
Assignee: Vertellus Specialties Inc
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Filing: 1988-02-03
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Granted: —
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Expires: 2008-02-03
Abstract
Abstract An improved Monsanto-type process for acetic acid preparation and a heterogeneous-supported catalyst for accomplishing the same, comprising reacting methanol with carbon monoxide under pressure of about 65-80 Bar and temperature of about 170-200 DEG C in the presence of methyl iodide and a catalyst comprising an insoluble polymer having pendant free base, N-oxide or quaternized pyridine groups supporting a rhodium species loaded to less than about 10 weight percent (expressed as metal) of the polymer component.
Inventors
- 👤 Charles R. Marston
- 👤 Gerald L. Goe
Bibliographic Details
Application Number
—
Jurisdiction
EP
Data Source
google_patents
Last Synchronized
2026-11-08 19:35
CPC Classifications
B; B01; B01J; B01J31/00; B01J31/40; B01J31/4015; B01J31/4023; B01J31/4038; B01J31/4046; C; C07; C07C; C07C53/00; C07C53/08; B01J31/02; B01J31/06; B01J31/08; B01J31/16; B01J31/165; C07C51/00; C07C51/10; C07C51/12; B01J2231/00; B01J2231/30; B01J2231/34; B01J2531/00; B01J2531/80; B01J2531/82; B01J2531/822; B01J31/0231; B01J31/0234; B01J31/0235; B01J31/0239; B01J31/18; B01J31/1805; B01J31/181; Y; Y02; Y02P; Y02P20/00; Y02P20/50; Y02P20/584
Claims Analysis
Total Claims: 51
Claim 1
Independent Claim
81 words
In a Monsanto homogeneous carbonylation reaction of methanol to acetic acid under a pressure of carbon monoxide of about 65-80 Bars and a temperature of about 170-200°C in the presence of a rhodium species and an iodide promoter, the improvement comprising conducting the reaction in the presence of an insoluble polymer catalyst having pendant free base, N-oxide or quaternized pyridine groups or a combination thereof supporting the rhodium metal loaded to less than about 10 weight percent of the polymer component.
Claim 2
Dependent Claim
81 words
In a Monsanto homogeneous carbonylation reaction of methanol to acetic acid under a pressure of carbon monoxide of about 65-80 Bars and a temperature of about 170-200°C in the presence of a rhodium species and an iodide promoter, the improvement comprising conducting the reaction in the presence of an insoluble polymer catalyst having pendant free base, N-oxide or quaternized pyridine groups or a combination thereof supporting the rhodium metal loaded to less than about 10 weight percent of the polymer component.
Claim 3
Dependent Claim
18 words
The reaction of claim 1 wherein the polymer of said conducting is a copolymer derived from a vinylpyridine.
Claim 4
Dependent Claim
21 words
The reaction of claim 2 wherein said conducting achieves an enhanced reaction rate of at least four-fold over a homogeneous-catalyzed reaction.
Claim 5
Dependent Claim
26 words
The reaction of claim 2 wherein the improvement additionally comprises forming the insoluble polymer catalyst in situ by adding the polymer to the homogeneous reaction mixture.
Claim 6
Dependent Claim
30 words
The reaction of claim 4 wherein the improvement additionally comprises subsequently recovering the insoluble polymer catalyst after said forming and said conducting by filtering the catalyst from the reaction mixture.
Claim 7
Dependent Claim
49 words
The reaction of claim 4 wherein the improvement additionally comprises regenerating and recycling the insoluble polymer catalyst after said conducting by separating at least a portion of the liquid acetic acid product from the reaction mixture, recharging the mixture with additional amounts of reactants, and repeating said conducting step.
Claim 8
Dependent Claim
21 words
The reaction of claim 5 wherein said conducting achieves an enhanced reaction rate of at least four-fold over a homogeneous-catalyzed reaction.
Claim 9
Dependent Claim
20 words
The reaction of claim 7 wherein said conducting achieves a reaction rate in excess of about 5 mol AcOH/L, hr.
Claim 10
Dependent Claim
25 words
The reaction of claim 7 wherein said conducting achieves about a 50% conversion to acetic acid in a period of about 4 horus or less.
Claim 11
Dependent Claim
26 words
The reaction of claim 5 wherein said conducting achieves an average reaction rate from about 0-35% conversion of at leaast about 10.0 mol AcOH/mol Rh, hr.
Claim 12
Dependent Claim
14 words
The reaction of claim 5 wherein the vinylpyridine polymer of said conducting is 2-vinylpyridine.
Claim 13
Dependent Claim
19 words
The reaction of claim 11 wherein the vinylpyridine polymer of said conducting is poly(2-vinylpyridine) cross-linked with 25 % divinylbenzene.
Claim 14
Dependent Claim
13 words
The reaction of claim 12 wherein the polymer is in its N-oxide form.
Claim 15
Dependent Claim
14 words
The reaction of claim 5 wherein the vinylpyridine polymer of said conducting is 4-vinylpyridine.
Claim 16
Dependent Claim
18 words
The reaction of claim 14 wherein the 4-vinylpyridine polymer of said conducting is poly(4-vinylpyridine) cross-linked with 2% divinlybenzene.
Claim 17
Dependent Claim
17 words
The reaction of claim 14 wherein the 4-vinylpyridine polymer of said conducting poly(4-vinylpyridine) cross-linked with 25% divinlybenzene.
Claim 18
Dependent Claim
15 words
The reaction of claim 15 or 16 wherein the polymer is in its N-oxide form.
Claim 19
Dependent Claim
69 words
A commercial process for preparing acetic acid, comprising the step of reacting methanol with carbon monoxide under pressures of about 65-80 Bar and temperature of about 170-200°C in the presence of an iodide promoter and a catalyst comprising an insoluble polymer having pendant free base, N-oxide or quaternized pyridine groups supporting a rhodium species loaded to less than about 10 weight percent (expressed as metal) of the polymer component.
Claim 20
Dependent Claim
69 words
A commercial process for preparing acetic acid, comprising the step of reacting methanol with carbon monoxide under pressures of about 65-80 Bar and temperature of about 170-200°C in the presence of an iodide promoter and a catalyst comprising an insoluble polymer having pendant free base, N-oxide or quaternized pyridine groups supporting a rhodium species loaded to less than about 10 weight percent (expressed as metal) of the polymer component.
Claim 21
Dependent Claim
18 words
The process of claim 18 wherein the polymer of said reacting is a copolymer derived from a vinylpyridine.
Claim 22
Dependent Claim
14 words
The process of claim 19 wherein the vinylpyridine polymer of said reacting is 4-vinylpyridine.
Claim 23
Dependent Claim
14 words
The process of claim 19 wherein the vinylpyridine polymer of said reacitng is 2-vinylpyridine.
Claim 24
Dependent Claim
17 words
The process of claim 20 wherein the polymer of said reacting is poly(4-vinylpyridine) cross-linked with 2% divinylbenzene.
Claim 25
Dependent Claim
17 words
The process of claim 20 wherein the polymer of said reacting is poly(4-vinylpyridine) cross-linked with 25% divinylbenzene.
Claim 26
Dependent Claim
17 words
The process of claim 21 wherein the polymer of said reacting is poly(2-vinylpyridine) cross-linked with 25% divinylbenzene.
Claim 27
Dependent Claim
16 words
The process of claim 19 wherein the rhodium species of said reacting is rhodium chloride trihydrate.
Claim 28
Dependent Claim
22 words
The process of claim 19 wherein the polymer of said reacting contains at least about 50% by weight of pendant pyridine groups.
Claim 29
Dependent Claim
30 words
The process of claim 19 wherein said reacting additionally comprises: charging a pressure vessel with the liquid reaction components; pressurizing the mixture to about 65-80 Bars with carbon monoxide; and
Claim 30
Dependent Claim
20 words
The process of claim 27 additionally comprising replenishing the vessel with carbon monoxide to about 65-80 Bar during said heating.
Claim 31
Dependent Claim
17 words
The process of claim 27 additionally comprising recovering the polymer-supported rhodium catalyst after said pressurizing and heating.
Claim 32
Dependent Claim
38 words
The process of claim 29 wherein said recovering additionally comprises decanting the acetic acid product from the reaction mixture after the vessel has been cooled and vented; and filtering the insoluble polymer-supported rhodium catalyst from the reaction mixture.
Claim 33
Dependent Claim
60 words
The process of claim 27 additionally comprising regenerating and recycling the catalyst after said reacting, including the steps of: separating at least a portion of the liquid acetic acid product from the reaction mixture after the vessel has been cooled and vented; recharging the vessel with additional amounts of the liquid reactants; and repeating said pressurizing and said heating steps.
Claim 34
Dependent Claim
16 words
The process of claim 27 wherein said separating, recharging and repeating steps are carried out continuously.
Claim 35
Dependent Claim
21 words
The process of claim 19 wherein said reacting achieves about 100% conversion from methanol at about 99% selectivity to acetic acid.
Claim 36
Dependent Claim
21 words
The process of claim 19 wherein said reacting achieves an enhanced reaction rate in excess of about 5 mol AcOH/L, hr.
Claim 37
Dependent Claim
21 words
The process of claim 19 wherein said reacting achieves an enhanced reaction rate of at least four-fold over a homogeneous-catalyzed reaction.
Claim 38
Dependent Claim
23 words
The process of claim 19 wherein said reacting achieves about 50% conversion of methanol to acetic acid in less than about one hour.
Claim 39
Dependent Claim
25 words
The process of claim 18 wherein said reacting achieves an average reaction rate from about 0-35% conversion of at least about 10 ml AcOH/mol Rh,min.
Claim 40
Dependent Claim
46 words
A heterogeneous catalyst for use in the carbonylation of methanol to acetic acid, comprising an insoluble polymer having pendant free base, N-oxide or quaternized pyridine groups supporting a rhodium species loaded to less than about 10 weight percent (expressed as of metal) of the polymer component.
Claim 41
Dependent Claim
46 words
A heterogeneous catalyst for use in the carbonylation of methanol to acetic acid, comprising an insoluble polymer having pendant free base, N-oxide or quaternized pyridine groups supporting a rhodium species loaded to less than about 10 weight percent (expressed as of metal) of the polymer component.
Claim 42
Dependent Claim
15 words
The catalyst of claim 38 wherein the polymer is a copolymer derived from a vinylpyridine.
Claim 43
Dependent Claim
10 words
The catalyst of claim 39 wherein the vinylpyridine is 4-vinylpyridine.
Claim 44
Dependent Claim
10 words
The catalyst of claim 39 wherein the vinylpyridine is 2-vinylpyridine.
Claim 45
Dependent Claim
14 words
The catalyst of claim 40 wherein the polymer is poly(4-vinylpyridine) cross-linked with 2% divinylbenzene.
Claim 46
Dependent Claim
14 words
The catalyst of claim 40 wherein the polymer is poly(4-vinylpyridine) cross-linked with 25% divinylbenzene.
Claim 47
Dependent Claim
14 words
The catalyst of claim 41 wherein the polymer is poly(2-vinylpyridine) cross-linked with 25% divinlybenzene.
Claim 48
Dependent Claim
13 words
The catalyst of claim 39 wherein the rhodium compound is rhodium chloride trihydrate.
Claim 49
Dependent Claim
19 words
The catalyst of claim 39 wherein the polymer contains at least about 50% by weight of pendant pyridine groups.
Claim 50
Dependent Claim
21 words
The catalyst of claim 39 wherein the polymer is loaded to about 2 weight percent (of metal) of the polymer present.
Claim 51
Dependent Claim
16 words
The catalyst of claim 42, 43 or 44 wherein the polymer is in its N-oxide form.
References Cited (Backward Citations)
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