Texaco Inc.

Texaco Chemical Company

Kenneth P Keating

Edward T Marquis

John R Sanderson

William A Smith

Robert A Meyer

John F Knifton

Robert M Gipson

Steven H Vanderpool

Mark A Mueller

Robert M Steinberg

Jonathan Lustri

An epoxidation reaction wherein: an olefin and an organic hydroperoxide, preferably, propylene and tertiary butyl hydroperoxide are reacted in a primary reaction zone in a liquid phase with an organic solvent, preferably tertiary butyl alcohol, in the presence of a soluble molybdenum catalyst at a ratio of propylene to tertiary butyl hydroperoxide of from about 0.9:1 to about 3:1, at a reaction temperature from about 100.degree. C. to about 140.degree. C. and a residence time sufficient to convert about 85 to 95% of the tertiary butyl hydroperoxide and form a primary epoxidation zone reaction product; fractionating, in a primary fractionation zone, the primary zone reaction product into a primary distillate fraction comprising unreacted propylene and propylene oxide and into a primary heavy liquid fraction, comprising molybdenum catalyst, unreacted tertiary butyl hydroperoxide, tertiary butyl alcohol and side reaction products; reacting, in a secondary epoxidation reaction zone, the primary heavy liquid fraction with propylene in the liquid phase, with substantially no back mixing, at a molar ratio of propylene to unreacted tertiary butyl hydroperoxide of about 5:1 to about 10:1, a reaction temperature of about 110.degree. C. to about 140.degree. C. and a residence time sufficient for conversion of substantially all the tertiary butyl hydroperoxide and production of a secondary reaction zone product; fractionating the secondary reaction zone product, in a secondary distillation zone, into a secondary distillate fraction comprising unreacted propylene, and propylene oxide, and into a secondary heavy liquid fraction comprising molybdenum catalyst, tertiary butyl alcohol, and side reaction products; recovering the secondary heavy liquid product for recovery and/or disposal of molybdenum; and fractional distillation of the first distillate fraction and the second distillate fraction for recovery of propylene, and propylene oxide product.

Epoxidation process for manufacture of olefin oxide and alcohol

Complexes made by reacting an ammonium-containing molybdenum compound with an alkylene glycol in the presence of water at an elevated temperature are described. Mild stripping of the water subsequent to complex formation is preferred. If some of the water is left in the complex, it may serve as an excellent olefin epoxidation catalyst. The ratio of moles of alkylene glycol to gram atoms of molybdenum in the complex forming reaction ranges from 7:1 to 20:1. Ethylene glycol and propylene glycol are the particularly preferred alkylene glycols.

Catalytic reaction of propyelne with tertiary butyl hydroperoxide

Tertiary butyl hydroperoxide and tertiary butyl alcohol are recovered from the reaction product formed by reacting excess propylene with tertiary butyl hydroperoxide in solution in tertiary butyl alcohol in the presence of a soluble molybdenum catalyst, by fractionating the reaction produce to provide distillate propylene, propylene oxide, and tertiary butyl alcohol fractions and a heavy distillation fraction comprising tertiary butyl hydroperoxide, tertiary butyl alcohol and impurities, including dissolved molybdenum catalyst, the tertiary butyl hydroperoxide and tertiary butyl alcohol being recovered from the heavy distillation fraction by vacuum evaporation under evaporation conditions including a temperature of about 25.degree. to about 160.degree. C. and a pressure of about 2 to about 200 mm Hg. in order to provide a lighter condensate fraction comprising about 60 to about 95 wt. % of the heavy distillation fraction and containing from about 70 to about 95 wt. % of tertiary butyl alcohol, about 1 to about 20 wt. % of the tertiary butyl hydroperoxide and from about 15 to about 3 wt. % of impurities and also into a clear liquid heavier residue fraction comprising tertiary butyl alcohol, tertiary butyl hydroperoxide and substantially all of the soluble molybdenum catalyst originally contained in the heavy liquid fraction.

Recovery of tertiary butyl hydroperoxide and tertiary butyl alcohol

A heavy distillation fraction comprising tertiary butyl hydroperoxide, tertiary butyl alcohol, impurities and dissolved molybdenum catalyst resulting from the removel of propylene, propylene oxide and tertiary butyl alcohol from an epoxidation reaction product is mixed with about 5 to about 10 wt. %, based on the weight of the heavy liquid distilation fraction, of a lower aliphatic alcohol containing from 1 to 3 carbon atoms to provide a charge mixture, and the charge mixture is:

An impure propylene oxide feedstock contaminated with from about 50 to about 1000 ppm of methanol and from about 0 to about 1 wt. % of acetone is charged to the lower half of an extractive distillation column containing at least about 25 theoretical plates and an extractive distillation agent consisting essentially of a blend of acetone and water (acetone/water blend) containing about 20 to about 30 wt. % of acetone and, correspondingly, about 80 to about 70 wt. % of water is charged to the tower at a point 4 to 7 theoretical stages above the impure propylene oxide feed point; the extractive distillation agent being introduced into the extractive distillation column in the ratio of said feedstock to said extractive distillation agent of from about 5:1 to about 20:1, whereby an overhead distillate fraction is obtained consisting essentially of propylene oxide contaminated with not more than about 60 ppm of methanol, not more than about 0.02 wt. % of acetone and not more than about 0.3 wt. % of water.

Purification of propylene oxide using an aqueous acetone extractive

A process for substantially completely removing a minor amount of molybdenum dissolved in a substantially anhydrous organic solution, such as a heavy distillation fraction resulting from the removal of unreacted propylene, propylene oxide and tertiary butyl alcohol from an epoxidation reaction mixture:

Method for recovering solid molybdenum compounds

A hydroperoxide charge stock (t-butyl hydroperoxide or t-amyl hydroperoxide) is reacted with a C.sub.3 to C.sub.20 olefin charge stock in liquid phase in a reaction zone in the presence of a catalytically effective amount of a soluble molybdenum catalyst to form a product olefin epoxide corresponding to the olefin charge stock and a product alcohol corresponding to the hydroperoxide charge (t-butyl alcohol or t-amyl alcohol), which process is improved in accordance with the present invention by maintaining a reaction medium composed of more than 60 wt % of polar components (hydroperoxide charge stock, product alcohol and product epoxide) in the reaction zone by charging to the reaction zone at least about a 30 wt % solution of the hydroperoxide charge stock in the corresponding product alcohol and charging said olefin charge stock to said reaction zone in an amount relative to the amount of said charged solution of charged hydroperoxide in product alcohol sufficient to provide a ratio of from about 0.5 to about 2 moles of charged olefin per mole of charged hydroperoxide. The preferred olefin charge stock is propylene and the preferred hydroperoxide charge stock is t-butyl hydroperoxide. The corresponding epoxide in this situation is propylene oxide and the corresponding product alcohol is t-butyl alcohol.

Olefin epoxidation of olefins in a polar medium

Complexes are made by reacting a solid ammoniummolybdate and a solid alkali metal molybdate with ethylene -glycol. Stripping of water of reaction subsequent to complex formation is preferred. The ratio of moles of alkylene glycol to total gram atoms of molybdenum should be in the range from about 7:1 to about 20:1 and the ratio of gram atoms of molybdenum in the ammonium molybdate to gram atoms of molybdenum in the alkali metal molybdenum should be in the range of about 1:1 to about 20:1. Solutions of the complexes are excellent catalysts for the reaction of propylene with an organic hydroperoxide such as tertiary butyl hydroperoxide to form propylene oxide and tertiary butyl alcohol.

Epoxidation in the presence of molybdenum/alkali metal/ethylene glycol

Motor-fuel grade tertiary butyl alcohol contaminated with residual amounts of tertiary butyl hydroperoxide and ditertiary butyl peroxide (which is prepared, for example, by reacting propylene with tertiary butyl hydroperoxide to form propylene oxide and a motor fuel grade tertiary butyl alcohol reaction product) can be effectively catalytically treated under mild conversion conditions including a temperature of about 80.degree. to 180.degree. C. with a base-treated hydrogenation catalyst from groups VIB or VIIIB of the Periodic Table in order to substantially selectively convert the two peroxide contaminants to tertiary butyl alcohol and to thereby provide a treated tertiary butyl alcohol product substantially free from contaminating quantities of such peroxides.

Catalytic removal of peroxide contaminants from tertiary butyl alcohol

Complexes are made by reacting a solid ammonium molybdate and a solid alkali metal molybdate with ethylene glycol. Stripping of water of reaction subsequent to complex formation is preferred. The ratio of moles of alkylene glycol to total gram atoms of molybdenum should be in the range from about 7:1 to about 20:1 and the ratio of gram atoms of molybdenum in the ammonium molybdate to gram atoms of molybenum in the alkali metal molybdenum should be in the range of about 1:1 to about 20:1. Solutions of the complexes are excellent catalysts for the reaction of propylene with an organic hydroperoxide such as tertiary butyl hydroperoxide to form proplyene oxide and tertiary butyl alcohol.

Molybdenum/alkali metal/ethylene glycol complexes useful as epoxidation

Methyl formate is removed from propylene oxide by treatment with a selected base such as sodium hydroxide in water and glycerol. Selected inert salts may be added. The rate of methyl formate hydrolysis by selected bases was increased to commercially acceptable levels by addition of the glycerol. The glycerol and inert salts reduced the amount of residual water in the propylene oxide.

Purification of propylene oxide by treatment with a selected base and

Methyl formate is removed from propylene oxide by treatment with aqueous calcium hydroxide slurry. Calcium hydroxide solubility is increased by adding a solubilizer selected from the group consisting of sucrose, fructose, maltose, glycerol and mixtures thereof. Methyl formate hydrolysis rate is improved by propylene oxide/water ratio control. Addition of an aldehyde scavenger improves propylene oxide purity.

Purification of propylene oxide by treatment with calcium hydroxide in

Storage stable solutions of molybdenum/alkanol complexes in the alkanol are prepared by reacting a molybdenum oxide and ammonium hydroxide and an amount of a straight chain or branched chain C.sub.6 -C.sub.13 alkanol, within the range of about 10 to about 55 moles of alkanol per gram atom of molybdenum sufficient to form a storage stable molybdenum/alkanol complex. The complex-forming reaction is initiated in the presence of about 1 to about 4 moles of water per gram atom of molybdenum and about 0.5 to about 10 moles of ammonia per gram atom of molybdenum, the water and ammonia preferably being added in the form of concentrated ammonium hydroxide. The reaction is conducted at a temperature of about 120.degree. to about 190.degree. C. for a period of time, normally about 3 to about 8 hours, sufficient to substantially completely remove ammonia and water to provide a liquid reaction product comprising said solution of molybdenum/alkanol complex dissolved in unreacted alkanol and containing about 0.001 to about 0.1 wt. % of water. The reaction product is filtered to provide a clarified storage stable solution of the molybdenum/alkanol complex having a dissolved molybdenum content of about 3 to about 10.5 wt. %.

Synthesis of molybdenum oxide/alkanol complexes

Storage stable solutions of molybdenum/alkanol complexes in the alkanol are prepared by reacting an ammonium molybdate with an amount of a straight chain or branched chain C.sub.6 -C.sub.13 alkanol, within the range of about 7 to about 20 moles of alkanol per gram atom of molybdenum sufficient to form a storage stable molybdenum/alkanol complex. The complex-forming reaction is initiated in the presence of about 1 to about 4 moles of added water per gram atom of molybdenum and is conducted at a temperature of about 120.degree. to about 190.degree. C. for a period of time, normally about 3 to about 8 hours, sufficient to substantially completely remove ammonia and water to provide a liquid reaction product comprising said solution of molybdenum/alkanol complex dissolved in unreacted alkanol and containing about 0.001 to about 0.1 wt. % of water. The reaction product is filtered to provide a clarified storage stable solution of the molybdenum/alkanol complex.

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Georgetown, TX, United States of America

Kenneth P Keating