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US4304871A Expired / Lapsed US ⏱️ 0.0 years remaining

Conversion of synthesis gas to hydrocarbon mixtures utilizing a dual catalyst bed

Assignee: Mobil Oil AS
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Filing: 1977-08-19
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Granted: 1981-12-08
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Expires: 1997-08-19
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Abstract

Abstract A gaseous mixture of carbon monoxide and hydrogen is passed in contact over a first catalyst bed comprising an iron or cobalt containing Fischer-Tropsch catalyst in combination with a crystalline aluminosilicate of the class of crystalline zeolite represented by ZSM-5 so as to obtain a liquid hydrocarbon product having a boiling range of less than 400 DEG F. at a 90% overhead and being a predominantly olefinic product. The total products from said contact including said liquid hydrocarbon product are then converted over a second catalyst bed containing HZSM-5 to obtain a highly aromatic product, i.e., greater than 20 weight percent.

Inventors

  • 👤 James A. Brennan
  • 👤 Philip D. Caesar
  • 👤 Julius Ciric
  • 👤 William E. Garwood

Bibliographic Details

Application Number —
Jurisdiction US
Data Source google_patents
Last Synchronized 2026-10-31 12:01
CPC Classifications
C; C07; C07C; C07C1/00; C07C1/02; C07C1/04; C07C1/0425; C07C1/043; C07C1/0435; C07C1/044; C07C1/0485; C07C2529/00; C07C2529/04; C07C2529/06; C07C2529/40; C07C2529/42; C07C2529/46

Claims Analysis

Total Claims: 12
Claim 1
Independent Claim 347 words
In a process for converting synthesis gas comprising carbon monoxide and hydrogen to gasoline boiling components wherein synthesis gas is contracted in a first stage under conditions of elevated temperatures and pressure with a Fischer-Tropsch catalyst and the total product from said first stage contact is passed to a second stage containing an acidic crystalline zeolite having a pore diameter greater than about five Angstroms, a silica-to-alumina ratio of at least 12, a crystal density substantially below 1.6 grams per cubic centimeter and a constraint index of from 1 to 12 the improvement which comprises: (a) carrying out said contact in said first stage at a temperature of 450°-750° F., a space velocity of 500-20,000 GHSV, and a pressure of from 50 to 1000 psig, with a catalyst composite comprising an intimate mixture of an iron or cobalt-containing Fischer-Tropsch component and a volume excess of a crystalline aluminosilicate zeolite having a pore size greater than 5 Angstroms, a silica-to-alumina ratio of at least 12 and a constraint index of from about 1 to 12, wherein the activity of said crystalline aluminosilicate zeolite in said first stage is balanced with said Fischer-Tropsch component so as to obtain products including a liquid olefinic naphtha having a boiling range of less than 400° F. at 90 percent overhead with an aromatic content of less than about 20 weight percent, an olefin plus aromatic content of at least 50 weight percent, wherein the olefins have predominantly branched chain double bonds; (b) operating said second stage at a temperature of from 550° F. to about 800° F., a pressure of from 50 to about 1000 psig and at a gas hourly space velocity of from 500 to 20,000; (c) recovering a C 5 + gasoline fraction in a yield of at least 40 weight percent based on the total hydrocarbons produced, said gasoline fraction having a boiling range of less than 400° F. at a 90 percent overhead and an aromatics content greater than 20 weight percent; and (d) producing methane plus ethane in an amount no greater than 30 weight percent.
Claim 2
Dependent Claim 347 words
In a process for converting synthesis gas comprising carbon monoxide and hydrogen to gasoline boiling components wherein synthesis gas is contracted in a first stage under conditions of elevated temperatures and pressure with a Fischer-Tropsch catalyst and the total product from said first stage contact is passed to a second stage containing an acidic crystalline zeolite having a pore diameter greater than about five Angstroms, a silica-to-alumina ratio of at least 12, a crystal density substantially below 1.6 grams per cubic centimeter and a constraint index of from 1 to 12 the improvement which comprises: (a) carrying out said contact in said first stage at a temperature of 450°-750° F., a space velocity of 500-20,000 GHSV, and a pressure of from 50 to 1000 psig, with a catalyst composite comprising an intimate mixture of an iron or cobalt-containing Fischer-Tropsch component and a volume excess of a crystalline aluminosilicate zeolite having a pore size greater than 5 Angstroms, a silica-to-alumina ratio of at least 12 and a constraint index of from about 1 to 12, wherein the activity of said crystalline aluminosilicate zeolite in said first stage is balanced with said Fischer-Tropsch component so as to obtain products including a liquid olefinic naphtha having a boiling range of less than 400° F. at 90 percent overhead with an aromatic content of less than about 20 weight percent, an olefin plus aromatic content of at least 50 weight percent, wherein the olefins have predominantly branched chain double bonds; (b) operating said second stage at a temperature of from 550° F. to about 800° F., a pressure of from 50 to about 1000 psig and at a gas hourly space velocity of from 500 to 20,000; (c) recovering a C 5 + gasoline fraction in a yield of at least 40 weight percent based on the total hydrocarbons produced, said gasoline fraction having a boiling range of less than 400° F. at a 90 percent overhead and an aromatics content greater than 20 weight percent; and (d) producing methane plus ethane in an amount no greater than 30 weight percent.
Claim 3
Dependent Claim 19 words
The process of claim 1 with a crystalline aluminosilicate zeolite in both the first and second stage is ZSM-5.
Claim 4
Dependent Claim 15 words
The process of claim 2 wherein the ZSM-5 zeolite in the first stage is KZSM-5.
Claim 5
Dependent Claim 24 words
The process of claim 3 wherein a cobalt containing Fischer-Tropsch catalyst is used in the first stage and the temperature is from 470°-540° F.
Claim 6
Dependent Claim 17 words
The process of claim 3 wherein an iron containing Fischer-Tropsch catalyst is used in the first stage.
Claim 7
Dependent Claim 343 words
In a process for converting synthesis gas comprising carbon monoxide and hydrogen to gasoline boiling components wherein synthesis gas is contacted in a first stage under conditions of elevated temperatures and pressure with a Fischer-Tropsch catalyst and the total product from said first stage contact is passed to a second stage containing an acidic crystalline zeolite having a pore diameter greater than about five Angstroms, a silica-to-alumina ratio of at least 12, a crystal density substantially below 1.6 grams per cubic centimeter and a constraint index of from 1 to 12 the improvement which comprises: (a) carrying out said contact in said first stage at a temperature of from 450°-750° F., a space velocity of 500-20,000 GHSV and a pressure from 50-1,000 psig with a catalyst composite comprising an intimate mixture of a potassium promoted iron Fischer-Tropsch component and a volume excess of a crystalline aluminosilicate zeolite having a pore size greater than five Angstroms, a silica-to-alumina ratio of at least 12 and a constraint index of from about 1 to 12, wherein the activity of said crystalline aluminosilicate zeolite in said first stage is balanced with said Fischer-Tropsch component so as to obtain products including a liquid olefinic naphtha having a boiling range of less than 400° F. at 90% overhead with an aromatic content of less than about 20 weight percent, an olefin plus aromatic content of at least 50 weight percent, wherein the olefins have predominantly branched chain double bonds; (b) operating said second stage at a temperature of from 550° F. to about 800° F. a pressure of from 50 to about 1000 psig and at a gas hourly space velocity of from 500 to 20,000; (c) recovering a C 5 + gasoline fraction in a yield of at least 40 weight percent based on the total hydrocarbons produced, said gasoline fraction having a boiling range of less than 400° F. at a 90% overhead and an aromatic content greater than 20 weight percent; and (d) producing methane plus ethane in an amount no greater than 30 weight percent.
Claim 8
Dependent Claim 343 words
In a process for converting synthesis gas comprising carbon monoxide and hydrogen to gasoline boiling components wherein synthesis gas is contacted in a first stage under conditions of elevated temperatures and pressure with a Fischer-Tropsch catalyst and the total product from said first stage contact is passed to a second stage containing an acidic crystalline zeolite having a pore diameter greater than about five Angstroms, a silica-to-alumina ratio of at least 12, a crystal density substantially below 1.6 grams per cubic centimeter and a constraint index of from 1 to 12 the improvement which comprises: (a) carrying out said contact in said first stage at a temperature of from 450°-750° F., a space velocity of 500-20,000 GHSV and a pressure from 50-1,000 psig with a catalyst composite comprising an intimate mixture of a potassium promoted iron Fischer-Tropsch component and a volume excess of a crystalline aluminosilicate zeolite having a pore size greater than five Angstroms, a silica-to-alumina ratio of at least 12 and a constraint index of from about 1 to 12, wherein the activity of said crystalline aluminosilicate zeolite in said first stage is balanced with said Fischer-Tropsch component so as to obtain products including a liquid olefinic naphtha having a boiling range of less than 400° F. at 90% overhead with an aromatic content of less than about 20 weight percent, an olefin plus aromatic content of at least 50 weight percent, wherein the olefins have predominantly branched chain double bonds; (b) operating said second stage at a temperature of from 550° F. to about 800° F. a pressure of from 50 to about 1000 psig and at a gas hourly space velocity of from 500 to 20,000; (c) recovering a C 5 + gasoline fraction in a yield of at least 40 weight percent based on the total hydrocarbons produced, said gasoline fraction having a boiling range of less than 400° F. at a 90% overhead and an aromatic content greater than 20 weight percent; and (d) producing methane plus ethane in an amount no greater than 30 weight percent.
Claim 9
Dependent Claim 24 words
The process of claim 6 wherein the catalyst in the first stage comprises an intimate mixture of potassium promoted iron and potassium ZSM-5 zeolite.
Claim 10
Dependent Claim 15 words
The process of claim 7 wherein the catalyst in the second stage is acid ZSM-5.
Claim 11
Dependent Claim 15 words
The process of claim 8 wherein the temperature of the first stage is 550°-700° F.
Claim 12
Dependent Claim 16 words
The process of claim 9 wherein the temperature of the second stage is from 550°-650° F.

References Cited (Backward Citations)

US3760024A Cited
US3756942A Cited
US3894106A Cited
US3894102A Cited
BE828228A Cited
US3960978A Cited
US3972958A Cited
US4041094A Cited
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USPTO Annuity & Maintenance Windows

Annuity Stage Window Opens Payment Deadline Surcharge Period Until Estimated Fee Status
3.5 Years (Year 4) 1984-12-07 1985-06-08 1985-12-08 $2000.00 Window Closed / Lapsed
7.5 Years (Year 8) 1988-12-07 1989-06-08 1989-12-08 $3760.00 Window Closed / Lapsed
11.5 Years (Year 12) 1992-12-07 1993-06-08 1993-12-08 $7700.00 Window Closed / Lapsed

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