Patent US5013329A successfully refreshed from Google Patents.
US5013329A
Expired / Lapsed
US
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Conversion of light hydrocarbons to ether rich gasoline
Assignee: Mobil Oil AS
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Filing: 1989-03-31
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Granted: 1991-05-07
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Expires: 2009-03-31
Abstract
Abstract A process is disclosed for converting a light hydrocarbon feedstock that contains a mixture of linear and branched olefins to ether-rich high octane gasoline streams that include tertiary alkyl and isoalkyl ethers such as MTBE, TAME, methyl isopropyl ether (MIPE), and methyl sec-butylether (MSBE). The conversion is achieved by utilizing the differing reactivity of tertiary olefins under selected conditions compared to linear olefins in the catalyzed etherification processes. The discovery has been made that unreacted olefins from the etherification reactions can be converted to gasoline boiling range hydrocarbons by contacting them with zeolite catalyst at elevated temperature. Further, it has been discovered that unreacted paraffins in the integrated process can be dehydrogenated to produce C3-C4 olefins which can be recycled to the etherification process.
Inventors
- 👤 Weldon K. Bell
- 👤 Werner O. Haag
- 👤 Mohsen N. Harandi
- 👤 Hartley Owen
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-08 13:31
CPC Classifications
C; C10; C10L; C10L1/00; C10L1/02; C10L1/023; C07; C07C; C07C41/00; C07C41/01; C07C41/05; C07C41/06; Y; Y02; Y02P; Y02P20/00; Y02P20/10; Y02P30/00; Y02P30/20
Claims Analysis
Total Claims: 24
Claim 1
Independent Claim
206 words
An integrated process for the production of ether-rich rich liquid fuels, comprising: (a) contacting a fresh mixture of lower alkanol and a light hydrocarbon feedstock containing linear olefins and C 4 + tertiary olefins with an acidic etherification catalyst in a first etherification zone under tertiary olefin etherification conditions whereby an etherification effluent stream containing lower alkyl tertiary alkyl ethers is produced; (b) separating said etherification effluent stream to provide a first stream comprising ether-rich C 5 + gasoline and a second stream comprising unreacted lower alkanol and linear olefins of C 5 - hydrocarbons; (c) contacting said second stream with an acidic catalyst in a second etherification zone under conditions effective to etherify said linear olefinic hydrocarbons; (d) recovering a first stream comprising C 5 + gasoline containing lower alkyl ethers of said C 5 - linear olefins and a second stream comprising unreacted olefins of C 4 - hydrocarbons from said second etherification zone; (e) passing said second stream to an olefins to higher molecular weight hydrocarbons conversion zone in contact with an acidic metallosilicate catalyst under olefins and oxygenates conversion conditions at elevated temperature whereby higher molecular C 5 + gasoline boiling range hydrocarbons are produced plus C 5 - paraffinic hydrocarbon by-product.
Claim 2
Dependent Claim
206 words
An integrated process for the production of ether-rich rich liquid fuels, comprising: (a) contacting a fresh mixture of lower alkanol and a light hydrocarbon feedstock containing linear olefins and C 4 + tertiary olefins with an acidic etherification catalyst in a first etherification zone under tertiary olefin etherification conditions whereby an etherification effluent stream containing lower alkyl tertiary alkyl ethers is produced; (b) separating said etherification effluent stream to provide a first stream comprising ether-rich C 5 + gasoline and a second stream comprising unreacted lower alkanol and linear olefins of C 5 - hydrocarbons; (c) contacting said second stream with an acidic catalyst in a second etherification zone under conditions effective to etherify said linear olefinic hydrocarbons; (d) recovering a first stream comprising C 5 + gasoline containing lower alkyl ethers of said C 5 - linear olefins and a second stream comprising unreacted olefins of C 4 - hydrocarbons from said second etherification zone; (e) passing said second stream to an olefins to higher molecular weight hydrocarbons conversion zone in contact with an acidic metallosilicate catalyst under olefins and oxygenates conversion conditions at elevated temperature whereby higher molecular C 5 + gasoline boiling range hydrocarbons are produced plus C 5 - paraffinic hydrocarbon by-product.
Claim 3
Dependent Claim
21 words
The process of claim 1 including the step of introducing a fresh stream of said alkanol to step (c) etherification zone.
Claim 4
Dependent Claim
28 words
The process of claim 1 including the further step of introducing a fresh stream of C 3 hydrocarbons to step (c) etherification zone and step (e) conversion zone.
Claim 5
Dependent Claim
39 words
The process of claim 1 wherein step (a) etherification conditions comprise a high excess of said alkanol over C 4 + tertiary olefins whereby the etherification reaction equilibrium is shifted substantially toward the formation of C 5 + ethers.
Claim 6
Dependent Claim
18 words
The process of claim 4 wherein said excess of said alkanol is between about 3 and 100 percent.
Claim 7
Dependent Claim
14 words
The process of claim 4 wherein said excess of alkanol is about 10 percent.
Claim 8
Dependent Claim
14 words
The process of claim 1 wherein said tertiary alkyl ethers comprise MTBE and TAME.
Claim 9
Dependent Claim
22 words
The process of claim 1 wherein step (c) catalyst comprises a shape-selective, acid aluminosilicate zeolite-type catalyst having the structure of zeolite Beta.
Claim 10
Dependent Claim
19 words
The process of claim 1 wherein step (c) etherified linear olefins comprise methyl isopropyl ether and methyl sec-butyl ether.
Claim 11
Dependent Claim
30 words
The process of claim 1 wherein said first zone etherification conditions comprise temperature between 37° and 93° C. and said second zone conditions comprise temperature between 50° and 300° C.
Claim 12
Dependent Claim
59 words
The process of claim 1 including the further steps of: passing the C 3 -C 5 fraction of step (e) C 5 - paraffinic hydrocarbon by-product to a dehydrogenation zone under paraffins dehydrogenation conditions whereby olefins are produced and hydrogen rich fuel gas; and passing said olefins to step (a) etherification zone in conjunction with said light hydrocarbon feedstock.
Claim 13
Dependent Claim
11 words
The process of claim 1 wherien said metallosilicate comprises zeolite ZSM-5.
Claim 14
Dependent Claim
22 words
The process of claim 1 including the further step of introducing ethene rich fuel gas as feedstock to step (e) conversion zone.
Claim 15
Dependent Claim
213 words
In the process for the production of methyl tertiary alkyl ethers comprising reacting a mixture comprising methanol and C 4 + hydrocarbons containing tertiary and linear olefins in contact with acid etherification catalyst under etherification conditions in an isoolefins etherification zone to produce a product stream comprising C 5 + methyl tertiary alkyl ethers, unreacted methanol and C 5 - hydrocarbons containing linear olefins; separating said product stream into unreacted methanol, unreacted C 5 - hydrocarbons and C 5 + ethers, recycling unreacted methanol and recovering a hydrocarbon stream rich in C 5 + methyl tertiary alkyl ethers, the improvement comprising: (a) contacting said C 5 - hydrocarbons with an acidic catalyst in a linear olefins etherification zone under conditions effective to etherify linear olefinic fraction of said hydrocarbons; (b) recovering a first stream comprising C 5 + gasoline containing methyl ethers of said C 5 - hydrocarbons and a second stream comprising unreacted olefins of said C 5 - hydrocarbons, methanol and dimethyl ether from said linear olefins etherification zone; (c) passing said second stream to an olefins to gasoline conversion zone in contact with an acidic metallosilicate catalyst under olefins and oxygenates conversion conditions at elevated temperature whereby C 5 + gasoline is produce dplus C 5 - paraffinic hydrocarbon by-product.
Claim 16
Dependent Claim
213 words
In the process for the production of methyl tertiary alkyl ethers comprising reacting a mixture comprising methanol and C 4 + hydrocarbons containing tertiary and linear olefins in contact with acid etherification catalyst under etherification conditions in an isoolefins etherification zone to produce a product stream comprising C 5 + methyl tertiary alkyl ethers, unreacted methanol and C 5 - hydrocarbons containing linear olefins; separating said product stream into unreacted methanol, unreacted C 5 - hydrocarbons and C 5 + ethers, recycling unreacted methanol and recovering a hydrocarbon stream rich in C 5 + methyl tertiary alkyl ethers, the improvement comprising: (a) contacting said C 5 - hydrocarbons with an acidic catalyst in a linear olefins etherification zone under conditions effective to etherify linear olefinic fraction of said hydrocarbons; (b) recovering a first stream comprising C 5 + gasoline containing methyl ethers of said C 5 - hydrocarbons and a second stream comprising unreacted olefins of said C 5 - hydrocarbons, methanol and dimethyl ether from said linear olefins etherification zone; (c) passing said second stream to an olefins to gasoline conversion zone in contact with an acidic metallosilicate catalyst under olefins and oxygenates conversion conditions at elevated temperature whereby C 5 + gasoline is produce dplus C 5 - paraffinic hydrocarbon by-product.
Claim 17
Dependent Claim
58 words
The process of claim 14 including the further steps of: passing the C 3 -C 5 fraction of said C 5 - paraffinic hydrocarbon by-product to a dehydrogenation zone under paraffins dehydrogenation conditions whereby olefins are produced and hydrogen rich fuel gas; and passing said olefins to said isoolefins etherification zone in conjunction with said light hydrocarbon feedstock.
Claim 18
Dependent Claim
21 words
The process of claim 14 including the step of introducing a fresh stream of methanol to said linear olefins etherification zone.
Claim 19
Dependent Claim
29 words
The process of claim 14 including the further step of introducing a fresh stream of C 3 hydrocarbons to said linear olefins etherification zone and step (c) conversion zone.
Claim 20
Dependent Claim
28 words
The process of claim 14 wherein isoolefins etherification conditions comprise temperature between 37° and 93° C. and linear olefins etherification conditions comprise temperature between 50° and 300° C.
Claim 21
Dependent Claim
20 words
The process of claim 1 wherein said lower alkanol is taken from the group comprising essentially methanol, ethanol and isopropanol.
Claim 22
Dependent Claim
27 words
The process of claim 1 wherein said olefins conversion conditions comprise olefin to gasoline conversion conditions and said higher molecular weight hydrocarbons comprise gasoline boiling range hydrocarbons.
Claim 23
Dependent Claim
31 words
The process of claim 1 wherein said olefins conversion conditions comprise olefin to gasoline and distillate conversion conditions and said higher molecular weight hydrocarbons comprise gasloine and distillate boiling range hydrocarbons.
Claim 24
Dependent Claim
24 words
The process of claim 1 wherein said olefins conversion conditions comprise olefin and paraffin conversion conditions and said higher molecular weight hydrocarbons comprise aromatics.
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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) | 1994-05-06 | 1994-11-05 | 1995-05-07 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1998-05-06 | 1998-11-05 | 1999-05-07 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 2002-05-06 | 2002-11-05 | 2003-05-07 | $7700.00 | Window Closed / Lapsed |