US5313006A
Expired / Lapsed
US
⏱️ 0.0 years remaining
Cogeneration of isobutylene plus MTBE from crude t-butanol/methanol feedstocks
Assignee: TEXACO PETROCHEMICAL Inc A CORP OF DELAWARE
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Filing: 1992-12-21
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Granted: 1994-05-17
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Expires: 2012-12-21
Abstract
Abstract Disclosed is an improvement in a method for cogeneration of isobutylene and MTBE by etherification of tBA/MeOH over an ion-exchange resin which allows for more complete conversion of the remaining tBA fraction and comprises a second step consisting essentially of recovering the MTBE from the primary fractionator as an overhead fraction and etherifying the bottoms from the primary fractionator over an inorganic acid catalyst comprising a crystalline aluminosilicate faujasite-type Y-zeolite modified with a compound selected from a fluoride-containing compound including hydrofluoric acid, ammonium fluoride, fluorosulfonic acids and their cogeners and triflic anhydride at a temperature of greater than 120 DEG C.
Inventors
- 👤 John F. Knifton
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-04 17:26
CPC Classifications
C; C07; C07C; C07C41/00; C07C41/01; C07C41/09; C07C1/00; C07C1/20; C07C1/24; C07C2529/00; C07C2529/04; C07C2529/06; C07C2529/08
Claims Analysis
Total Claims: 10
Claim 1
Independent Claim
155 words
In a method for the etherification of tert-butanol/methanol to methyl tertiary butyl ether over an ion exchange resin etherification catalyst and recovery of the product and bottoms in a primary fractionator, the improvement, allowing more complete conversion of the remaining tertiary butyl alcohol (tBA) fraction in the bottoms to MTBE plus isobutylene, which comprises: a) recovering the methyl tertiary butyl ether (MTBE) from the etherification as an overhead fraction in the primary fractionator, b) recovering tertiary butyl alcohol, isopropanol and methanol from the etherification as bottoms in the primary fractionator, c) removing the bottoms from the primary fractionator, and d) reacting said bottoms in a second step over a catalyst comprising an acidic type Y-zeolite having a silica:alumina ratio in the range of 100:1 to 1:1, modified with a fluorine-containing compound selected from the group consisting of hydrogen fluoride, hydrofluoric acid, ammonium fluoride and triflic anhydride, at a temperature from 180° C. to 220° C.
Claim 2
Dependent Claim
155 words
In a method for the etherification of tert-butanol/methanol to methyl tertiary butyl ether over an ion exchange resin etherification catalyst and recovery of the product and bottoms in a primary fractionator, the improvement, allowing more complete conversion of the remaining tertiary butyl alcohol (tBA) fraction in the bottoms to MTBE plus isobutylene, which comprises: a) recovering the methyl tertiary butyl ether (MTBE) from the etherification as an overhead fraction in the primary fractionator, b) recovering tertiary butyl alcohol, isopropanol and methanol from the etherification as bottoms in the primary fractionator, c) removing the bottoms from the primary fractionator, and d) reacting said bottoms in a second step over a catalyst comprising an acidic type Y-zeolite having a silica:alumina ratio in the range of 100:1 to 1:1, modified with a fluorine-containing compound selected from the group consisting of hydrogen fluoride, hydrofluoric acid, ammonium fluoride and triflic anhydride, at a temperature from 180° C. to 220° C.
Claim 3
Dependent Claim
16 words
The method of claim 1 wherein said Y-zeolite has a Si:Al ratio of 1.5 to 2.
Claim 4
Dependent Claim
15 words
The method of claim 1 wherein said Y-zeolite has a silica:alumina ratio of about 8:1.
Claim 5
Dependent Claim
15 words
The method of claim 1 wherein said Y-zeolite has a silica:alumina ratio of about 46:1.
Claim 6
Dependent Claim
24 words
The method of claim 1 wherein the fluoride-treated Y-zeolite consists essentially of a Y-zeolite having a Si:Al ratio of 1.5-2:1 modified with hydrofluoric acid.
Claim 7
Dependent Claim
25 words
The method of claim 1 wherein the fluoride-treated Y-zeolite consists essentially of a Y-zeolite having a silica:alumina ratio of about 46:1 modified with hydrofluoric acid.
Claim 8
Dependent Claim
25 words
The method of claim 1 wherein the fluoride-treated Y-zeolite consists essentially of a Y-zeolite having a silica:alumina ratio of about 8:1, modified with ammonium fluoride.
Claim 9
Dependent Claim
23 words
The method of claim 1 wherein the modified Y-zeolite catalyst has a residual acidity in the range of 0.1 to 100 mg KOH/gm.
Claim 10
Dependent Claim
20 words
The method of claim 1 wherein the hydrogen fluoride or ammonium fluoride are added to the Y-zeolite as aqueous solutions.
References Cited (Backward Citations)
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1997-05-16 | 1997-11-15 | 1998-05-17 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 2001-05-16 | 2001-11-15 | 2002-05-17 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 2005-05-16 | 2005-11-15 | 2006-05-17 | $7700.00 | Window Closed / Lapsed |