Huntsman Specialty Chemicals Corporation

Texaco Chemical Inc.

Texaco Inc.

Texaco Chemical Company

Texaco Development Corporation

Huntsman International LLC

Huntsman Ici Chemicals LLC

Kyle Lee Preston

Charles J Kruse

Rei-Yu Judy Hwan

Brian L Benac

Pei-Shing E Dai

Laurence D Neff

Mark E Taylor

Mark A Mueller

John F Knifton

William K Culbreth, Iii

Rei-Yu J Hwan

Chung-Nan T Wu

Karen A Thomas

Lawrence E Tillotson

Feng-Ran Sheu

A method for the preparation of methyl tertiary butyl ether is provided wherein a mixture of methanol and substantially peroxides-free tertiary butyl alcohol are catalytically reacted to form a reaction product comprising unreacted methanol, unreacted tertiary butyl alcohol, water, isobutylene and methyl tertiary butyl ether, that is separated into a substantially anhydrous first lighter distillation fraction comprising isobutylene, methanol and methyl tertiary butyl ether and a second heavier distillation fraction comprising methanol, tertiary butyl alcohol and water, and wherein the isobutylene and methanol in the first distillation fraction are reacted to form an isobutylene conversion product that contains additional methyl tertiary butyl ether that is substantially free from tertiary butyl alcohol.

Method for the reduced formation of tertiary butyl alcohol in a finishing reactor in the manufacture of methyl tertiary butyl ether

Peroxides are prepared from organic compounds and oxygen in a reaction vessel by introducing organic compound and oxygen to the reaction vessel and by simultaneously withdrawing a first liquid product stream from adjacent the top of the reactor and a second liquid product stream from adjacent the bottom of the reaction vessel. Suitable organic compounds include, but are not limited to, alkanes and all aryl compounds.

Peroxide production

A tertiary butyl alcohol charge stock contaminated with from about 0.5 to about 2 wt. % of corrosive oxygen-containing impurities, including peroxides and formates, is passed through an oxygenates decomposition reactor containing a bed of a basic zeolite catalyst to decompose the peroxides and oxygen-containing impurities, including peroxides and formates, and to dehydrate a portion of the tertiary butyl alcohol to form isobutylene and water to form a substantially less-corrosive tertiary butyl alcohol feedstock that is substantially free from oxygen-containing impurities, including formates that is suitable for reaction with methanol in a methyl tertiary butyl ether etherification reactor to form a methyl tertiary butyl ether etherification reaction product from which methyl tertiary butyl ether can be recovered.

Method for the purification of tertiary butyl alcohol for use in the

Methyl tertiary butyl ether is prepared from contaminated tertiary butyl alcohol and methanol by decomposing peroxides in a peroxides decomposition reactor, by dehydrating the tertiary butyl alcohol to form isobutylene and also decomposing acidic contaminants in a tertiary butyl alcohol dehydration reactor to form a feedstock that is distilled to provide a first lower boiling fraction comprising isobutylene and water; from which isobutylene is recovered for reaction with methanol in an etherification reactor containing a bed of an etherification catalyst to form methyl tertiary butyl ether.

Method for the purification of tertiary butyl alcohol and to its use in

MTBE is prepared from TBA and MeOH by passing a feed mixture comprising TBA and MeOH through a primary MTBE reaction zone to form a primary reaction product containing MTBE, unreacted TBA, unreacted MeOH, isobutylene and water; the primary reaction product is fractionated to provide a first lighter distillation fraction comprising isobutylene, MeOH and MTBE and a first higher boiling distillation fraction comprising MeOH, TBA and water and the first higher boiling distillation fraction is charged to a second stage MTBE reaction zone to form a second stage reaction product comprising unreacted MeOH, unreacted TBA water, isobutylene and MTBE.

Use of a second stage reactor in the manufacture and recovery of methyl

Methyl tertiary butyl ether is prepared from TBA contaminated with oxygen-containing impurities by decomposing the impurities to gaseous products, by charging the thus-treated tertiary butyl alcohol and methanol to an etherification reactor to form an etherification reaction product, by distilling the etherification reaction product to provide a lower boiling fraction containing isobutylene, methanol and methyl tertiary butyl ether by charging the lower boiling fraction to a finishing reactor to react the isobutylene and methanol contained therein to from additional MTBE and by recovering MTBE from the etherification reaction product and the isobutylene conversion product.

Method for the manufacture of methyl tertiary butyl ether from tertiary

Methyl tertiary butyl ether and diisobutylene are prepared by reacting methanol with tertiary butyl alcohol to provide an etherification reaction product containing methyl tertiary butyl ether, tertiary butyl alcohol, methanol, isobutylene, and water. A methyl tertiary butyl ether product fraction and an isobutylene fraction are recovered from the etherification reaction product; the isobutylene fraction is charged to an isobutylene conversion reaction zone to form a diisobutylene conversion product, and the diisobutylene conversion product is charged to a diisobutylene distillation zone and separated therein into a lower boiling distillation fraction comprising isobutylene, and diisobutylene and a higher boiling distillation fraction consisting essentially of diisobutylene.

Conjoint manufacture of MTBE and diisobutylene

An aqueous methanol feed stream contaminated with tertiary butyl alcohol is charged to a reactive distillation column having a reaction distillation section in the upper portion thereof containing an acid cation exchange resin and separated therein into a substantially anhydrous lower boiling methanol fraction contaminated with isobutylene and a higher boiling water fraction by charging the feed stream to the lower portion of the reactive distillation column to separate the feed stream into a higher boiling water fraction and a lower boiling methanol fraction containing a tertiary butyl alcohol-water azeotrope for upward flow into the reactive distillation section for reaction of the tertiary butyl alcohol to form isobutylene, MTBE and water and recovery of a substantially anhydrous lower boiling methanol fraction contaminated with isobutylene and MTBE.

Use of reactive distillation in the manufacture of methyl tertiary butyl

Disclosed is a method for decomposing formate esters, free acids and peroxides in a tertiary butyl alcohol stream to produce noncondensible gas products which comprises reacting said tertiary butyl alcohol stream or a methyl tertiary butyl alcohol stream containing formate esters over a catalyst comprising a non-noble Group VIII metal and a metal of Group IB on a support comprising an inert composition mixed with a hydrotalcite-like composition.

Catalytic decomposition of formate impurities in tertiary butyl alcohol

Tertiary butyl alcohol and methanol are reacted in a primary reactor in the presence of an acid cation exchange resin to provide a primary reaction product comprising methyl tertiary butyl ether, unreacted tertiary butyl alcohol, unreacted methanol, isobutylene, water and oxygen-containing by-products, and the primary reaction product is charged to a reactive distillation column where additional methyl tertiary butyl ether is prepared from the methanol, tertiary butyl alcohol and isobutylene present in the primary reaction product.

Manufacture of methyl tertiary butyl ether in reactive distillation

Methanol and isobutylene are reacted to form a methyl tertiary butyl ether product stream containing contaminating quantities of dimethyl ether, methanol and isobutylene that is separated into a first fraction comprising isobutylene and methyl tertiary butyl ether and a second fraction comprising residual methyl tertiary butyl ether, methanol, dimethyl ether and water. The second fraction is separated into a first lower boiling distillation fraction comprising methyl tertiary butyl ether, methanol, isobutylene, dimethyl ether, and water and a first higher boiling distillation fraction comprising methanol and water. Dimethyl ether and isobutylene are recovered from the first lower boiling distillation fraction and charged to a second distillation column for separation into a second lower boiling distillation fraction consisting essentially of dimethyl ether and a second higher boiling distillation fraction comprising dimethyl ether and isobutylene.

Method for the manufacture and purification of methyl tertiary butyl

An improved method of recovering methyl tertiary butyl ether from an etherification reaction product containing acidic by-products wherein the reaction product is charged to an MTBE distillation zone and fractionated therein to provide a lower boiling distillation fraction comprising isobutylene, methyl tertiary butyl ether, methanol and acidic by-products, wherein the lower boiling distillation fraction is counter-currently washed with alkaline water in a methanol extraction tower, and wherein an aqueous solution of an alkali is injected into the tower below the charge point for the wash water to substantially completely neutralize the acidic by-products and to provide an overhead extract substantially free from acidic by-products comprising isobutylene, methyl tertiary butyl ether and a minor amount of water, and a bottoms raffinate comprising methanol, water, alkaline by-products and a minor amount of methyl tertiary butyl ether.

Method for the water washing and recovery of methyl tertiary butyl ether

MTBE, prepared by reacting MeOH with TBA to form a primary etherification reaction product, is distilled in a first distillation column to provide a first lower boiling distillation fraction comprising methyl tertiary butyl ether, isobutylene, methanol, dimethyl ether, and the first lower boiling fraction is water washed to provide an overhead extract that is distilled in a second distillation column to provide a second lower boiling distillation fraction comprising isobutylene, dimethyl ether and water, which is dewatered to provide a feed fraction comprising isobutylene and dimethyl ether that is reacted with less than an equivalent amount of MeOH to provide a secondary reaction product comprising MTBE, less than 0.5 wt. % of MeOH, isobutylene and contaminants including TBA and dimethyl ether, and the secondary reaction product is recycled to the second distillation column.

Removal of methanol from methyl tertiary butyl ether

Methyl tertiary butyl ether is sequentially prepared from tertiary butyl alcohol and methanol by: passing tertiary butyl alcohol and methanol through a primary reaction zone to form a primary etherification reaction product comprising unreacted methanol, unreacted tertiary butyl alcohol, water, dimethyl ether, isobutylene and methyl tertiary butyl ether; separating the primary etherification reaction product into a methanol recycle fraction, a tertiary butyl alcohol recycle fraction, an isobutylene fraction and a methyl tertiary butyl ether product fraction; recycling the methanol recycle fraction and the tertiary butyl alcohol recycle fraction to the methyl tertiary butyl ether etherification reaction zone; passing at least a portion of said isobutylene fraction together with added methanol through a secondary reaction zone to form a secondary etherification reaction product comprising water, methanol, isobutylene, DME, methyl tertiary butyl ether and tertiary butyl alcohol; and recovering the methyl tertiary butyl ether from said secondary etherification reaction product.

Sequential reaction of TBA and isobutylene with methanol

Tertiary butyl hydroperoxide and tertiary butyl alcohol are prepared from isobutane and oxygen in a vertical reactor by sparging a mixture of isobutane with oxygen to the bottom of the reactor, by charging a reaction mixture recycle stream to the reactor above the sparge point, by centrally charging a downwardly flowing stream of cooled fresh isobutane to the top of the reactor to induce central downflow of the fresh isobutane annular and upflow of the sparged mixture and the recycle stream, by withdrawing a liquid product stream adjacent the top of the reactor, by withdrawing a vapor product stream from the top of the reactor, by condensing entrained liquids in the vapor product, by recycling the condensed liquids and by recovering the liquid product stream.

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Port Arthur, TX, United States of America

Kyle Lee Preston