Preparation of glyocol acetates

Claim 2

IN A PROCESS FOR PRODUCING GLYCOL ACETATES BY REACTING ACETIC ACID, ETHYLENE AND MOLECULAR OXYGEN IN AN OXIDATION ZONE IN THE PRESENCE OF A CATALYST SYSTEM COMPRISING A VARIABLE VALENT CATION SELECTED FROM AT LEAST ONE MEMBER OF THE GROUP CONSISTING OF TELLURIUM, CERIUM, ANTIMONY, MANGANESE, VANADIUM, GALLIUM, ARSENIC, COBALT, COPPER, CHROMIUM, AND SELENIUM AND AT LEAST ONE OF BROMINE, CHLORINE, A BROMINECONTANING COMPOUND YEILDING BROMIDE IONS DURING REACTION, OR A CHLORINE-CONTAINING COMPOUND YEILDING CHLORIDE IONS DURING REACTION TO PRODUCE A REACTION MIXTURE CONTANING SAID PRODUCT GLYCOL ACETATES, SAUD OXIDATION ZONE BEING SUPPLIED WITH A LIQUID FEED COMPRISING ACETIC ACID, THE IMPROVEMENT WHICH COMPRISES MAINTAINING IN SAID LIQUID FEED A LEVEL OF FORMIC MOIETIES OF 3 TO 10 WEIGHT PERCENT.

Claim 3

A process as defined in claim 1, wherein said formic moieties are maintained in the range of 4 to 8 weight percent in said liquid feed to said oxidation zone.

Claim 4

In a process for producing glycol acetates by reacting acetic acid, ethylene and molecular oxygen in an oxidation zone in the presence of a catalyst system comprising a variable valent cation selected from at least one member of the group consisting of tellurium, cerium, antimony, manganese, vanadium gallium, arsenic, cobalt, copper, chromium, and selenium and at least one of bromine, chlorine, a bromine-containing compound yielding bromide ions during reaction, or a chlorine-containg compound yielding chlorine ions during reaction to produce a reaction mixture comprising said product glycol acetates in combination with water, unreacted acetic acid, and higher boiling components of the reaction, the liquid feed to said oxidation zone comprising said acetic acid, components of said catalyst system and recycled higher boiling components, the improvement which comprises maintaining in said liquid feed a level of formic moieties of 3 to 10 weight percent.

Claim 5

In a process for producing glycol acetates by reacting acetic acid, ethylene and molecular oxygen in an oxidation zone in the presence of a catalyst system comprising a variable valent cation selected from at least one member of the group consisting of tellurium, cerium, antimony, manganese, vanadium gallium, arsenic, cobalt, copper, chromium, and selenium and at least one of bromine, chlorine, a bromine-containing compound yielding bromide ions during reaction, or a chlorine-containg compound yielding chlorine ions during reaction to produce a reaction mixture comprising said product glycol acetates in combination with water, unreacted acetic acid, and higher boiling components of the reaction, the liquid feed to said oxidation zone comprising said acetic acid, components of said catalyst system and recycled higher boiling components, the improvement which comprises maintaining in said liquid feed a level of formic moieties of 3 to 10 weight percent.

Claim 6

A process as defined in claim 3, wherein said formic moieties are maintained in the range of 4 to 8 weight percent in said liquid feed to said oxidation zone.

Claim 7

In a process for producing glycol acetates by reacting acetic acid, ethylene and molecular oxygen in an oxidation zone in the presence of a catalyst system comprising a variable valent cation selected from at least one member of the group consisting of tellurium, cerium, antimony, manganese, vanadium, gallium, arsenic, cobalt, copper, chromium, and selenium and at least one of bromine, chlorine, a bromine-containing compound yielding bromide ions during reaction, or a chlorine-containing compound yielding chloride ions during reaction to produce a liquid effluent comprising said product glycol acetates in combination with more volatile components and higher boiling components, including essentially non-volatile components, the improvement which comprises subjecting said liquid effluent to distillation to separate at least some of said product glycol acetates and more volatile components from said high boiling components, preparing a liquid feed to said oxidation zone comprising acetic acid, at least some of saId higher-boiling components and makeup catalyst components, together with 3 to 10 weight percent of formic moieties, and introducing said liquid feed into said oxidation zone for reaction with ethylene and molecular oxygen.

Claim 8

In a process for producing glycol acetates by reacting acetic acid, ethylene and molecular oxygen in an oxidation zone in the presence of a catalyst system comprising a variable valent cation selected from at least one member of the group consisting of tellurium, cerium, antimony, manganese, vanadium, gallium, arsenic, cobalt, copper, chromium, and selenium and at least one of bromine, chlorine, a bromine-containing compound yielding bromide ions during reaction, or a chlorine-containing compound yielding chloride ions during reaction to produce a liquid effluent comprising said product glycol acetates in combination with more volatile components and higher boiling components, including essentially non-volatile components, the improvement which comprises subjecting said liquid effluent to distillation to separate at least some of said product glycol acetates and more volatile components from said high boiling components, preparing a liquid feed to said oxidation zone comprising acetic acid, at least some of saId higher-boiling components and makeup catalyst components, together with 3 to 10 weight percent of formic moieties, and introducing said liquid feed into said oxidation zone for reaction with ethylene and molecular oxygen.

Claim 9

A process as defined in claim 5, wherein said formic moieties are maintained in the range of 4 to 8 weight percent in said liquid feed to said oxidation zone.

Claim 10

In a process for producing glycol acetates by reacting acetic acid, ethylene and molecular oxygen in an oxidation zone in the presence of a catalyst system comprising a variable valent cation selected from at least one member of the group consisting of tellurium, cerium, antimony, manganese, vanadium, gallium, arsenic, cobalt, copper, chromium, and selenium and at least one of bromine, chlorine, a bromine-containing compound yielding bromide ions during reaction, or a chlorine-containing compound yielding chloride ions during reaction to produce a liquid effluent containing said glycol acetates in combination with water, unreacted acetic acid, liquid by-products of the reaction and non-volatile components, the improvement which comprises subjecting said liquid effluent to a plurality of distillation steps to separate therefrom a product stream composed primarily of said product glycol acetates, an aqueous stream, an acetic acid stream composed primarily of acetic acid and lower-boiling non-aqueous components of the liquid effluent, and a stream of components having higher-boiling points than said product glycol acetates and including non-volatile components, preparing a liquid feed to said oxidation zone from said acetic acid stream, said stream of higher-boiling components, makeup acetic acid, and makeup catalyst, said liquid feed being provided with 3 to 10 weight percent of formic moieties, and introducing said liquid feed into said oxidation zone for reaction with ethylene and molecular oxygen.

Claim 11

In a process for producing glycol acetates by reacting acetic acid, ethylene and molecular oxygen in an oxidation zone in the presence of a catalyst system comprising a variable valent cation selected from at least one member of the group consisting of tellurium, cerium, antimony, manganese, vanadium, gallium, arsenic, cobalt, copper, chromium, and selenium and at least one of bromine, chlorine, a bromine-containing compound yielding bromide ions during reaction, or a chlorine-containing compound yielding chloride ions during reaction to produce a liquid effluent containing said glycol acetates in combination with water, unreacted acetic acid, liquid by-products of the reaction and non-volatile components, the improvement which comprises subjecting said liquid effluent to a plurality of distillation steps to separate therefrom a product stream composed primarily of said product glycol acetates, an aqueous stream, an acetic acid stream composed primarily of acetic acid and lower-boiling non-aqueous components of the liquid effluent, and a stream of components having higher-boiling points than said product glycol acetates and including non-volatile components, preparing a liquid feed to said oxidation zone from said acetic acid stream, said stream of higher-boiling components, makeup acetic acid, and makeup catalyst, said liquid feed being provided with 3 to 10 weight percent of formic moieties, and introducing said liquid feed into said oxidation zone for reaction with ethylene and molecular oxygen.

Claim 12

A process as defined in claim 7, wherein said formic moieties are maintained in the range of 4 to 8 weight percent in said liquid feed to said oxidation zone.

Claim 13

A process for producing glycol acetates which comprises reacting acetic acid, ethylene and molecular oxygen in an oxidation zone in the presence of a catalyst system comprising a variable valent cation selected from at least one member of the group consisting of tellurium, cerium, antimony, manganese, vanadium, gallium, arsenic, cobalt, copper, chromium, and selenium and at least one of bromine, chlorine, a bromine-containing compound yielding bromide ions during reaction, or a chlorine-containing compound yielding chloride ions during reaction to produce a reaction mixture containing said product glycol acetates, continuously removing said reaction mixture from said oxidation zone, and continuously introducing said liquid feed into said oxidation zone, said liquid feed having maintained in it a level of formic moieties of 3 to 10 weight percent.

Claim 14

A process for producing glycol acetates which comprises reacting acetic acid, ethylene and molecular oxygen in an oxidation zone in the presence of a catalyst system comprising a variable valent cation selected from at least one member of the group consisting of tellurium, cerium, antimony, manganese, vanadium, gallium, arsenic, cobalt, copper, chromium, and selenium and at least one of bromine, chlorine, a bromine-containing compound yielding bromide ions during reaction, or a chlorine-containing compound yielding chloride ions during reaction to produce a reaction mixture containing said product glycol acetates, continuously removing said reaction mixture from said oxidation zone, and continuously introducing said liquid feed into said oxidation zone, said liquid feed having maintained in it a level of formic moieties of 3 to 10 weight percent.

Claim 15

A process as defined in claim 9 wherein said formic moieties are maintained in the range of 4 to 8 weight percent in said liquid feed to said oxidation zone.

Claim 16

A process for producing glycol acetates by reacting acetic acid, ethylene and molecular oxygen in an oxidation zone in the presence of a catalyst system comprising a variable valent cation selected from at least one member of the group consisting of tellurium, cerium, antimony, manganese, vanadium, gallium, arsenic, cobalt, copper, chromium, and selenium and at least one of bromine, chlorine, a bromine-containing compound yielding bromide ions during reaction, or a chlorine-containing compound yielding chloride ions during reaction to produce a liquid effluent comprising said product glycol acetates in combination with more volatile components and higher boiling components, including essentially non-volatile components, subjecting said liquid effluent to distillation to separate at least some of said product glycol acetatEs and more volatile components from said higher boiling components, preparing a liquid feed to said oxidation zone comprising acetic acid, at least some of said higher-boiling components and makeup catalyst components, together with 3 to 10 weight percent of formic moieties, and introducing said liquid feed into said oxidation zone for reaction with ethylene and molecular oxygen.

Claim 17

A process for producing glycol acetates by reacting acetic acid, ethylene and molecular oxygen in an oxidation zone in the presence of a catalyst system comprising a variable valent cation selected from at least one member of the group consisting of tellurium, cerium, antimony, manganese, vanadium, gallium, arsenic, cobalt, copper, chromium, and selenium and at least one of bromine, chlorine, a bromine-containing compound yielding bromide ions during reaction, or a chlorine-containing compound yielding chloride ions during reaction to produce a liquid effluent comprising said product glycol acetates in combination with more volatile components and higher boiling components, including essentially non-volatile components, subjecting said liquid effluent to distillation to separate at least some of said product glycol acetatEs and more volatile components from said higher boiling components, preparing a liquid feed to said oxidation zone comprising acetic acid, at least some of said higher-boiling components and makeup catalyst components, together with 3 to 10 weight percent of formic moieties, and introducing said liquid feed into said oxidation zone for reaction with ethylene and molecular oxygen.

Claim 18

A process as defined in claim 11, wherein said formic moieties are maintained in the range of 4 to 8 weight percent in said liquid feed to said oxidation zone.

Claim 19

A process for producing glycol acetates by reacting acetic acid, ethylene and molecular oxygen in an oxidation zone in the presence of a catalyst system comprising a variable valent cation selected from at least one member of the group consisting of tellurium, cerium, antimony, manganese, vanadium, gallium, arsenic, cobalt, copper, chromium, and selenium and at least one of bromine, chlorine, a bromine-containing compound yielding bromide ions during reaction, or a chlorine-containing compound yielding chloride ions during reaction to produce a liquid effluent containing said glycol acetates in combination with water, unreacted acetic acid, liquid by-products of the reaction and non-volatile components, subjecting said effluent to a plurality of distillation steps to separate therefrom a product stream composed primarily of said product glycol acetates, an aqueous stream, an acetic acid stream composed primarily of acetic acid and lower-boiling non-aqueous components of the liquid effluent, and a stream of components having higher boiling points than said product glycol acetates and including non-volatile components, preparing a liquid feed to said oxidation zone from said acetic acid stream, said stream of higher-boiling components, makeup acetic acid, and makeup catalyst, said liquid feed being provided with 3 to 10 weight percent of formic moieties, and introducing said liquid feed into said oxidation zone for reaction with ethylene and molecular oxygen.

Claim 20

A process for producing glycol acetates by reacting acetic acid, ethylene and molecular oxygen in an oxidation zone in the presence of a catalyst system comprising a variable valent cation selected from at least one member of the group consisting of tellurium, cerium, antimony, manganese, vanadium, gallium, arsenic, cobalt, copper, chromium, and selenium and at least one of bromine, chlorine, a bromine-containing compound yielding bromide ions during reaction, or a chlorine-containing compound yielding chloride ions during reaction to produce a liquid effluent containing said glycol acetates in combination with water, unreacted acetic acid, liquid by-products of the reaction and non-volatile components, subjecting said effluent to a plurality of distillation steps to separate therefrom a product stream composed primarily of said product glycol acetates, an aqueous stream, an acetic acid stream composed primarily of acetic acid and lower-boiling non-aqueous components of the liquid effluent, and a stream of components having higher boiling points than said product glycol acetates and including non-volatile components, preparing a liquid feed to said oxidation zone from said acetic acid stream, said stream of higher-boiling components, makeup acetic acid, and makeup catalyst, said liquid feed being provided with 3 to 10 weight percent of formic moieties, and introducing said liquid feed into said oxidation zone for reaction with ethylene and molecular oxygen.

Claim 21

A process as defined in claim 13, wherein said formic moieties are maintained in the range of 4 to 8 weight percent in said liquid feed to said oxidation zone.