CA1192576A - Production of an acylium anion product and carboxylic acids and esters therefrom - Google Patents
Production of an acylium anion product and carboxylic acids and esters therefromInfo
- Publication number
- CA1192576A CA1192576A CA000404491A CA404491A CA1192576A CA 1192576 A CA1192576 A CA 1192576A CA 000404491 A CA000404491 A CA 000404491A CA 404491 A CA404491 A CA 404491A CA 1192576 A CA1192576 A CA 1192576A
- Authority
- CA
- Canada
- Prior art keywords
- acid
- carbon monoxide
- psia
- bars
- recited
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/04—Preparation of carboxylic acids or their salts, halides or anhydrides from carboxylic acid halides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/10—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide
- C07C51/12—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide on an oxygen-containing group in organic compounds, e.g. alcohols
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/10—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide
- C07C51/14—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide on a carbon-to-carbon unsaturated bond in organic compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/58—Preparation of carboxylic acid halides
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
A carbonylation process for producing acylium anion addition product, e.g., acid fluorides, wherein the carbon monoxide and anhydrous acid such as hydrogen fluoride are premixed to form a single liquid phase which is reacted in a second reactor with the organic compound, e.g., propylene, to produce an organic carbon monoxide acid anion addition product, e.g., isobutyryl fluoride.
A carbonylation process for producing acylium anion addition product, e.g., acid fluorides, wherein the carbon monoxide and anhydrous acid such as hydrogen fluoride are premixed to form a single liquid phase which is reacted in a second reactor with the organic compound, e.g., propylene, to produce an organic carbon monoxide acid anion addition product, e.g., isobutyryl fluoride.
Description
5~
PRODUCTION OF AN ACYLIUM ANION PRODUCT AND
CARBOXYLIC ACIDS AND ESTERS TEIEREFROM
3ACKGROUN3 OF I~HE INVENTION
A. Fleld of the Invention The invention relates to the liquid phase produc-tion of an acylium anlon product, e.g., isobu~yryl fluorid2, by reacting a premi~ed carbon monoxide saturated anhydrous acid solution and an organic compound capable of adding carbon monoxide thereto.
B._ Description of the Prior ~rt The prio~ art such as GB 942,367 and DE - 2,750,719 as a whole stresses the requirement of gas-liquid phase systems and an aqueous acid catalys~ reac~.ion medium for p~oduction of carboxylic acid from compounds having one or more double bonds, or esters following by further hydrolysis of the reaction products to produGe carboxylic acids. In these processes, serious irreversible polymeriza-tion occurs and the aqueous acid medium is corrosive so that expensive equipment is required.
For example, in the prior ar~/ such as in Koch U.S. Patent No~ 2,831,877, acid fluorides can be formed by reacting an olefin with carbon monoxide and anhydrous hydrogen fluoride. This reaction is a dual phase reaction with the carbon monoxide in the gaseous state and the olefin and hydrogen fluoride remaining in the liquid state. As with most dual phase reactions,problems arise due to the requirement of additional mixing and replenishing the carbon monoxide into the liquid as it is used up. This is extremely significant in that the olefin dimerizes or polymerizes under ~hese conditions.
The problems of the prior art are overcome by the use of a liquid phase anhydrous system to form the acylium anion product by the process or reaction conditions described herei~, or the carboxylic acids bv the process described herein~
SUMMARY OF THE INV~NTION
.
Carbon monoxide and an anhydrous acid describe.d herein, e.~g., hydrogen fluoride are premixed in a first reac~or to form a liquid phase pre~erably saturated with car~on monoxide which is rapidly reacted in a second reactor with an organic compound described herein capable of adding carbon monoxide thexeto, e.g., propylene, under reaction conditions of a liquid phase whereby an acylium anion product forms, e.g., isobutyryl fluoride in substantial yields. The acylium anion product, e.g., isobutyryl fluoride, is further reacted with excess water to form carboxylic acid, e.g., isobuty~ic acid. The acid can be oxydehydrogena~ed to an unsaturated acid, e.g., metAacrylic acid as described herein.
DETAILED DESCRIPTION OF THE DR~WINGS
Fig. 1 is a di~agram of the solubility of carbon monoxide in anhydrous hydrogen fluoride.
Fig. 2 is a schematic diagram of a reactor for the process of the present invention.
DESCRIPTION OF TH~ INVENTION
The disclosed novel process ~or producing an acylium anion product and/or a carboxylic acid and/or ester therefrom comprises the following steps:
(a) Forming in a first reactor a liquid mixture comprlsed o~ carbon monoxide dissolved in an anhydrous acid described herein, eOg., hydrogen fluoride, preferably the anhydrous acid is saturated with carbon monoxide, (b) Reacting in the liquid phasP in a second reac~or under conditions whereby an acylium 57~
anion product forms the liquid mixture frorn the first reactox of CO di.ssolved in the anhydrous acid with a llquid mixture com-prised of an organic compo~md capable of addin~ carbon monoxide thereto, described herein, e.g., propylene, to form a produc~
m.ixture comprised of the acylium anion product, e.g., isobutyryl fluoride.
In one embodiment of the invention, the process fur~her comprises the s~ep of hvdrolyzing the acylium anion product, e.g.~ isobutyryl fluoride, ~o form the corres~onding carboxylic acid, e.g., isobutyric acid, under conditions whereby the carboxylic acid forms and the anhydrous acid is regenerated. Preferably the carboxylic acid is separated from the hydrolyzed mixture, and the remaining hydrolyzed mixture, absent o~ any deleterious amount of water and other deleterious materials comprised of anhydrous acid, e.g., hydrogen fluoride, and/or carbon monoxide, and/or unreacted acylium anion product, e.g., isobu~yryl fluoride, is recycled ~o the liquid mixture of anhydrous acid an~ carbon monoxide.
In another embodiment of the invention~ acrylic acid and/or methacrylic acid is produced from the propionic acid and/or isobutyric acid ~y oxydehydrogenation as described herein in the ~apor phase, in the presence of an oxygen-con~aining gas, air or oxygen itself, water, at a temperature from 30C to 500C, and at a pressure from 0.5 atmospheres to two (2) abmospheres in the presence of a catalyst described herein comprised of iron, ~hosphorous, and oxygen defined by the empirical formula FePxO~, where relative to one (1) atom of iron, x represents from 0.25 to 3.5 atoms of phosphorous and z represents the number of oxygen atoms required to satisfy the ~alence xequirements of the catalyst. Methyl or other alkyl esters or acrylic acid and/or me~hacrylic acid are foxmed by esterifying the acrylic and/or methacrylic acid.
REACTANTS
The carbon monoxide may be from any source, but must be substantially free from water; ~hat is, contain less than 1,000 ppm of water. The carbon monoxlde may be dlluted with other substances which do not interfere with the reac-tion. For example, dry synthesis gas may be used or dry coal con~ustion gases may be used. It is preferred that dry carbon monoxide itself be used.
~he organic compound ca~able o reacting with carbon monoxide and the anhydrous acid may contain other compounds and/or very small amounts of water, eOg., less than 1,000 ppm of water, which do not interfere with the liquid phase reaction and/or cause a dual phase to occur. The organic compounds may be organic esters or isopropanol described hereln which split to fo~m the acid and an acylium anion product or organic compounds having at least one unsaturated ~ond capable of adding carbon monoxide thereto as described herein.
Examples of these organic esters are represen~ed o by the general formula R - C - O - R'; wherein R is an alkyl of up to five carbon atoms; such as methyl, ethvl, pentyl.
Preferably -the alkyl is methyl, ethyl, propyl, isopropyl, with ethyl an~ isopropyl being highly preferred, and isopropyl being especially preerred. R' is an alkyl of from two to five carbon atoms, such as ethyl, propyl, pentyl.
Preferably R' is ethyl or isopropyl, with isopropyl being the most preferred.
Although any one of the esters mentioned herein may be used, it is ~referable if an ester is used to use isopropyl isobu~yrate (2-propanol 2-methylpro~ionate), ethyl isobutyrate (ethanol 2-methvlpropionate), isopropyl propionate (2-propanol propionate) or ethyl propionate (ethanol propionate). But isopropyl isobutyrate (2-propanol 3~
PRODUCTION OF AN ACYLIUM ANION PRODUCT AND
CARBOXYLIC ACIDS AND ESTERS TEIEREFROM
3ACKGROUN3 OF I~HE INVENTION
A. Fleld of the Invention The invention relates to the liquid phase produc-tion of an acylium anlon product, e.g., isobu~yryl fluorid2, by reacting a premi~ed carbon monoxide saturated anhydrous acid solution and an organic compound capable of adding carbon monoxide thereto.
B._ Description of the Prior ~rt The prio~ art such as GB 942,367 and DE - 2,750,719 as a whole stresses the requirement of gas-liquid phase systems and an aqueous acid catalys~ reac~.ion medium for p~oduction of carboxylic acid from compounds having one or more double bonds, or esters following by further hydrolysis of the reaction products to produGe carboxylic acids. In these processes, serious irreversible polymeriza-tion occurs and the aqueous acid medium is corrosive so that expensive equipment is required.
For example, in the prior ar~/ such as in Koch U.S. Patent No~ 2,831,877, acid fluorides can be formed by reacting an olefin with carbon monoxide and anhydrous hydrogen fluoride. This reaction is a dual phase reaction with the carbon monoxide in the gaseous state and the olefin and hydrogen fluoride remaining in the liquid state. As with most dual phase reactions,problems arise due to the requirement of additional mixing and replenishing the carbon monoxide into the liquid as it is used up. This is extremely significant in that the olefin dimerizes or polymerizes under ~hese conditions.
The problems of the prior art are overcome by the use of a liquid phase anhydrous system to form the acylium anion product by the process or reaction conditions described herei~, or the carboxylic acids bv the process described herein~
SUMMARY OF THE INV~NTION
.
Carbon monoxide and an anhydrous acid describe.d herein, e.~g., hydrogen fluoride are premixed in a first reac~or to form a liquid phase pre~erably saturated with car~on monoxide which is rapidly reacted in a second reactor with an organic compound described herein capable of adding carbon monoxide thexeto, e.g., propylene, under reaction conditions of a liquid phase whereby an acylium anion product forms, e.g., isobutyryl fluoride in substantial yields. The acylium anion product, e.g., isobutyryl fluoride, is further reacted with excess water to form carboxylic acid, e.g., isobuty~ic acid. The acid can be oxydehydrogena~ed to an unsaturated acid, e.g., metAacrylic acid as described herein.
DETAILED DESCRIPTION OF THE DR~WINGS
Fig. 1 is a di~agram of the solubility of carbon monoxide in anhydrous hydrogen fluoride.
Fig. 2 is a schematic diagram of a reactor for the process of the present invention.
DESCRIPTION OF TH~ INVENTION
The disclosed novel process ~or producing an acylium anion product and/or a carboxylic acid and/or ester therefrom comprises the following steps:
(a) Forming in a first reactor a liquid mixture comprlsed o~ carbon monoxide dissolved in an anhydrous acid described herein, eOg., hydrogen fluoride, preferably the anhydrous acid is saturated with carbon monoxide, (b) Reacting in the liquid phasP in a second reac~or under conditions whereby an acylium 57~
anion product forms the liquid mixture frorn the first reactox of CO di.ssolved in the anhydrous acid with a llquid mixture com-prised of an organic compo~md capable of addin~ carbon monoxide thereto, described herein, e.g., propylene, to form a produc~
m.ixture comprised of the acylium anion product, e.g., isobutyryl fluoride.
In one embodiment of the invention, the process fur~her comprises the s~ep of hvdrolyzing the acylium anion product, e.g.~ isobutyryl fluoride, ~o form the corres~onding carboxylic acid, e.g., isobutyric acid, under conditions whereby the carboxylic acid forms and the anhydrous acid is regenerated. Preferably the carboxylic acid is separated from the hydrolyzed mixture, and the remaining hydrolyzed mixture, absent o~ any deleterious amount of water and other deleterious materials comprised of anhydrous acid, e.g., hydrogen fluoride, and/or carbon monoxide, and/or unreacted acylium anion product, e.g., isobu~yryl fluoride, is recycled ~o the liquid mixture of anhydrous acid an~ carbon monoxide.
In another embodiment of the invention~ acrylic acid and/or methacrylic acid is produced from the propionic acid and/or isobutyric acid ~y oxydehydrogenation as described herein in the ~apor phase, in the presence of an oxygen-con~aining gas, air or oxygen itself, water, at a temperature from 30C to 500C, and at a pressure from 0.5 atmospheres to two (2) abmospheres in the presence of a catalyst described herein comprised of iron, ~hosphorous, and oxygen defined by the empirical formula FePxO~, where relative to one (1) atom of iron, x represents from 0.25 to 3.5 atoms of phosphorous and z represents the number of oxygen atoms required to satisfy the ~alence xequirements of the catalyst. Methyl or other alkyl esters or acrylic acid and/or me~hacrylic acid are foxmed by esterifying the acrylic and/or methacrylic acid.
REACTANTS
The carbon monoxide may be from any source, but must be substantially free from water; ~hat is, contain less than 1,000 ppm of water. The carbon monoxlde may be dlluted with other substances which do not interfere with the reac-tion. For example, dry synthesis gas may be used or dry coal con~ustion gases may be used. It is preferred that dry carbon monoxide itself be used.
~he organic compound ca~able o reacting with carbon monoxide and the anhydrous acid may contain other compounds and/or very small amounts of water, eOg., less than 1,000 ppm of water, which do not interfere with the liquid phase reaction and/or cause a dual phase to occur. The organic compounds may be organic esters or isopropanol described hereln which split to fo~m the acid and an acylium anion product or organic compounds having at least one unsaturated ~ond capable of adding carbon monoxide thereto as described herein.
Examples of these organic esters are represen~ed o by the general formula R - C - O - R'; wherein R is an alkyl of up to five carbon atoms; such as methyl, ethvl, pentyl.
Preferably -the alkyl is methyl, ethyl, propyl, isopropyl, with ethyl an~ isopropyl being highly preferred, and isopropyl being especially preerred. R' is an alkyl of from two to five carbon atoms, such as ethyl, propyl, pentyl.
Preferably R' is ethyl or isopropyl, with isopropyl being the most preferred.
Although any one of the esters mentioned herein may be used, it is ~referable if an ester is used to use isopropyl isobu~yrate (2-propanol 2-methylpro~ionate), ethyl isobutyrate (ethanol 2-methvlpropionate), isopropyl propionate (2-propanol propionate) or ethyl propionate (ethanol propionate). But isopropyl isobutyrate (2-propanol 3~
2-methyl~ropionate) is es~ecially preferred when an ester is used in the process described herein.
Examples or organic compounds having at least one unsaturated bond capable of adding carbon monoxide thereto ~hich may be used in the process described herein are olefins oi up to twenty carbon atoms having at least one double bond capable o~ adding carbon monoxide there~o, such as: ethylene, propylene, butenes, dodecene, 1,3~butadiene, 1,4-pen~adiene, 1,5-hexadiene. Ethylene and propylene are preferred, and propylene is highly pre.~erred. The alkenes may be substituted with alky~ or aryl cycloalkyls, or other substitutes which do not interfere in ~he process described herein.
Although all of the organic compolmds described herein may be used in the process descri~ed herein, propylene, however, i5 especially preferred.
The acids used for the preferred process to the acylium ani~n described herein should be substantially free rom water; that is, anhydrous. The term "anhydrous'' as used herein and in the claims refers to acids which are substan-tially free from water, e.g., less than 1,000 ppm of water, or if water is present, it does not interfere with the reac-tion to form-the acylium anion, or the carboxvic ester therefrom.
~he anhydrous acids which may be used for the described process are:
hvdrogen fluoride (hydrofluoric acid) ~HF) hydroaen chloride (hydrochloric acid) (~Cl) hydrogen fluoride ~ boron trifluoride (HF-3F3) or mixtu~res thereof, but preferably the individual acids.
Preferably the anhydrous ac.id for the process described is selected from anhydrous hvdrogen fluoride and anhydrous hydrogen chloride. However, ~he most preferred anhydrous acid for the process described herei.n is hydro~e~
fluoride (hvdrofluoric acid).
' ;
Reaction Conditions to Form the Acylium Anion Product The reaction of carbon monoxide, with an organic compound described herein and an anhydrous acid descrihed herein, can occur at temperatures of from zero degree Centi-grade (0C) to ninety degrees Centigrade (90C), the uppertemperature being determined bv side product formation. For the reaction between the preferred reactants described herein, the temperature can be from forty degrees Cen~igrade (40~C) to sixty degrees Centigrade (60CC), but preferably it is at about fifty degrees Centigrade (50C). The carbon monoxide pressure can varv from thirty-four (34) bars (500 psia) to three hundred for~y (340) bars (5,000 psia), and preferably it is from 2,500 psia to 2,000 psia. The pressure belng increased as required for the solubility o~ carbon monoxidP
in the anhydrous acid, as for example r shown in Figure l, which shows the increase in the amount of carbon monoxide dissol~ed in anhydrous hydrogen fluoride as the pressure and temperature increases.
The mole ratio of anhydrous acid to ~he organic compound described herein should be from l:l to 100:1, but generally it is from lQ:l to 20:1 and preferablv about 15:1.
The mole ratlo of carbon monoxi~e to the organic compound is from l:l to 5:1 or higher, but preferably it is from l.S:l to l:l, and the maximum corresponds to the saturation limit of carbon monoxide in the reaction mixture during and at the end of the reaction.
All of the carbon monoxide (CO) and anhydrous acid, e.g., anhydrous hydrogen fluoride, which is to be reacted with the orqanic campound, e.g., propylene, should be thoroughly mixed in the first reactor to form a liquid mixture in which the CO is dissolved therein, preferably the li~uid mixture is saturated with the CO prior to reacting with the organic compound described herein, e.g., propvlene, then the organic compound in the liquid phase is rapidly reacted, while mixing with the premixed carbon monoxide and acid in the second reactor. Generally, the reaction, depending upon ~he pressure and the temperature, will occur within mlnutes ~o form an acylium anion product, e.g., isobutyryl fluorideO The orqanic compound itself can be diluted with carbon monoxide or other inert diluents, eOg., methane, ethane, propanol, etc., in the li~uid phase to form a liquid mixture comprised of the organic compound, e.g., propylene, and CO, and/or inerts prior to reaction with the liquid mixture of anhydrous acid diluted with carbon monoxide.
The second reactor can be a semi-batch reactor, plug flow reactor, back mix reactor ~CSTX), or other reactor known to those skilled in the art; but the preferred reactor is a plug flow reactor.
After the reaction to form the acylium anion is complete, which depends upon the reaction conditions as known to those skilled in the art, from one (1) to one hundred (100) percent of the acylium anion product formed is separated from the product mixture. Preferably, from eighty 20 (80) to one hundred (100) percent of the acylium anion product is separated, and the remaining product mixture is recycled to the first or second reactor; that is, carbon monoxide, anhydrous acid, and the organic ccmpound described herein. Or, from one (1) to one hundred (100) percent 25 (preferably from eighty (80) to one hundred (100) percent), of the anhydrous acid is separated from the ~roduct mixture containing the acylium anion produc~ after the reaction to form the acylium anion is complete and the separated anhy-drous acid is recycled back to the first reactor for further mixing with carbon monoxide.
The separation can be by any of the known methods of separation, such as distillation.
The H drolvsis Process to Form the Corr~s ondin CarboxYlic Y , ~ P g Acid The hydrolysis reaction of the acylium anion addi-tion product, e.g., isobutyryl fluoride, with excess water can occur at temperatures from ~wenty degrees Centigrade (20C) to one hundred fifty degrees Centigrade (15CC) and at pressures from 14.7 psia to 5,000 psia, but normally it occurs at temperatures from forty degrees Centigrade (40C) to seventy degrees Cen-tigrade (70C) and pressures at 500 ~sia ~o 3,000 psia. The temperature and pressure being set to avoid the decomposition of the intended ~roducts.
The ~otal amount of water to be added, may be lnjected into the reaction mixture after the reaction to form acylium anion is complete. The hydrolysis step is exothermic; and, thus, cooling may be required.
The Esterlfication Process to Form_the Carboxylic Acid Esters The esterification reaction of the acylium anion product, e.g., isobutyryl fluoride, wlth an alcohol, particu-larlv, can occur at tem~eratures from twentv degrees Centi-qrade (20~C) to one hundred fifty degrees Centigrade (150C) and at pressures from 14.7 psia to 5,000 psia~ but normaily it occurs at temperatures from forty degrees Centigrade (40C) to seventy degrees Centigrade (70C) and pressures at 50 psia to lO0 psia. The temperature and pressure being set to avoid the decomposition of the intended products, and to facilit~te product separations.
It is preferred that the reactants be stirred during esterifica~ion. In many cases, when ra~id mixing is used, the esterification reaction with the concurrent regeneration of the anhydrous acid, e.g., HF, can be completed within seconds to minutes.
From one ~l) to one hundred (lO0) percent (prefer ably from eightv (80) to one hundred (lO0) percen-t) or the 7~
anhydrous acid is seoarated from the esterifica~ion product mixture and i5 recycled back for reac~ion to ~orm more acylium anion produc~. The recycle stream may contain small amounts of unseparated, unesterified acylium anion product 5 and/or carboxylic acid ester and/or unreacted organic compound .
The separation can be by any of the known methods of separation, such as distilla-tion or solvent extraction.
Preferably, distillation is used.
The carboxvlic acid of propionic acid or isobutyric acid formed from acylic anion product, e.g., propionyl fluoride or isobutyryl fluoride, after hydrolysis as described herein can be oxydehydrogenated by the ~rocess 15 described in U.S. patents 3,5~5,248; 3,585,24~; 3,585,250;
Examples or organic compounds having at least one unsaturated bond capable of adding carbon monoxide thereto ~hich may be used in the process described herein are olefins oi up to twenty carbon atoms having at least one double bond capable o~ adding carbon monoxide there~o, such as: ethylene, propylene, butenes, dodecene, 1,3~butadiene, 1,4-pen~adiene, 1,5-hexadiene. Ethylene and propylene are preferred, and propylene is highly pre.~erred. The alkenes may be substituted with alky~ or aryl cycloalkyls, or other substitutes which do not interfere in ~he process described herein.
Although all of the organic compolmds described herein may be used in the process descri~ed herein, propylene, however, i5 especially preferred.
The acids used for the preferred process to the acylium ani~n described herein should be substantially free rom water; that is, anhydrous. The term "anhydrous'' as used herein and in the claims refers to acids which are substan-tially free from water, e.g., less than 1,000 ppm of water, or if water is present, it does not interfere with the reac-tion to form-the acylium anion, or the carboxvic ester therefrom.
~he anhydrous acids which may be used for the described process are:
hvdrogen fluoride (hydrofluoric acid) ~HF) hydroaen chloride (hydrochloric acid) (~Cl) hydrogen fluoride ~ boron trifluoride (HF-3F3) or mixtu~res thereof, but preferably the individual acids.
Preferably the anhydrous ac.id for the process described is selected from anhydrous hvdrogen fluoride and anhydrous hydrogen chloride. However, ~he most preferred anhydrous acid for the process described herei.n is hydro~e~
fluoride (hvdrofluoric acid).
' ;
Reaction Conditions to Form the Acylium Anion Product The reaction of carbon monoxide, with an organic compound described herein and an anhydrous acid descrihed herein, can occur at temperatures of from zero degree Centi-grade (0C) to ninety degrees Centigrade (90C), the uppertemperature being determined bv side product formation. For the reaction between the preferred reactants described herein, the temperature can be from forty degrees Cen~igrade (40~C) to sixty degrees Centigrade (60CC), but preferably it is at about fifty degrees Centigrade (50C). The carbon monoxide pressure can varv from thirty-four (34) bars (500 psia) to three hundred for~y (340) bars (5,000 psia), and preferably it is from 2,500 psia to 2,000 psia. The pressure belng increased as required for the solubility o~ carbon monoxidP
in the anhydrous acid, as for example r shown in Figure l, which shows the increase in the amount of carbon monoxide dissol~ed in anhydrous hydrogen fluoride as the pressure and temperature increases.
The mole ratio of anhydrous acid to ~he organic compound described herein should be from l:l to 100:1, but generally it is from lQ:l to 20:1 and preferablv about 15:1.
The mole ratlo of carbon monoxi~e to the organic compound is from l:l to 5:1 or higher, but preferably it is from l.S:l to l:l, and the maximum corresponds to the saturation limit of carbon monoxide in the reaction mixture during and at the end of the reaction.
All of the carbon monoxide (CO) and anhydrous acid, e.g., anhydrous hydrogen fluoride, which is to be reacted with the orqanic campound, e.g., propylene, should be thoroughly mixed in the first reactor to form a liquid mixture in which the CO is dissolved therein, preferably the li~uid mixture is saturated with the CO prior to reacting with the organic compound described herein, e.g., propvlene, then the organic compound in the liquid phase is rapidly reacted, while mixing with the premixed carbon monoxide and acid in the second reactor. Generally, the reaction, depending upon ~he pressure and the temperature, will occur within mlnutes ~o form an acylium anion product, e.g., isobutyryl fluorideO The orqanic compound itself can be diluted with carbon monoxide or other inert diluents, eOg., methane, ethane, propanol, etc., in the li~uid phase to form a liquid mixture comprised of the organic compound, e.g., propylene, and CO, and/or inerts prior to reaction with the liquid mixture of anhydrous acid diluted with carbon monoxide.
The second reactor can be a semi-batch reactor, plug flow reactor, back mix reactor ~CSTX), or other reactor known to those skilled in the art; but the preferred reactor is a plug flow reactor.
After the reaction to form the acylium anion is complete, which depends upon the reaction conditions as known to those skilled in the art, from one (1) to one hundred (100) percent of the acylium anion product formed is separated from the product mixture. Preferably, from eighty 20 (80) to one hundred (100) percent of the acylium anion product is separated, and the remaining product mixture is recycled to the first or second reactor; that is, carbon monoxide, anhydrous acid, and the organic ccmpound described herein. Or, from one (1) to one hundred (100) percent 25 (preferably from eighty (80) to one hundred (100) percent), of the anhydrous acid is separated from the ~roduct mixture containing the acylium anion produc~ after the reaction to form the acylium anion is complete and the separated anhy-drous acid is recycled back to the first reactor for further mixing with carbon monoxide.
The separation can be by any of the known methods of separation, such as distillation.
The H drolvsis Process to Form the Corr~s ondin CarboxYlic Y , ~ P g Acid The hydrolysis reaction of the acylium anion addi-tion product, e.g., isobutyryl fluoride, with excess water can occur at temperatures from ~wenty degrees Centigrade (20C) to one hundred fifty degrees Centigrade (15CC) and at pressures from 14.7 psia to 5,000 psia, but normally it occurs at temperatures from forty degrees Centigrade (40C) to seventy degrees Cen-tigrade (70C) and pressures at 500 ~sia ~o 3,000 psia. The temperature and pressure being set to avoid the decomposition of the intended ~roducts.
The ~otal amount of water to be added, may be lnjected into the reaction mixture after the reaction to form acylium anion is complete. The hydrolysis step is exothermic; and, thus, cooling may be required.
The Esterlfication Process to Form_the Carboxylic Acid Esters The esterification reaction of the acylium anion product, e.g., isobutyryl fluoride, wlth an alcohol, particu-larlv, can occur at tem~eratures from twentv degrees Centi-qrade (20~C) to one hundred fifty degrees Centigrade (150C) and at pressures from 14.7 psia to 5,000 psia~ but normaily it occurs at temperatures from forty degrees Centigrade (40C) to seventy degrees Centigrade (70C) and pressures at 50 psia to lO0 psia. The temperature and pressure being set to avoid the decomposition of the intended products, and to facilit~te product separations.
It is preferred that the reactants be stirred during esterifica~ion. In many cases, when ra~id mixing is used, the esterification reaction with the concurrent regeneration of the anhydrous acid, e.g., HF, can be completed within seconds to minutes.
From one ~l) to one hundred (lO0) percent (prefer ably from eightv (80) to one hundred (lO0) percen-t) or the 7~
anhydrous acid is seoarated from the esterifica~ion product mixture and i5 recycled back for reac~ion to ~orm more acylium anion produc~. The recycle stream may contain small amounts of unseparated, unesterified acylium anion product 5 and/or carboxylic acid ester and/or unreacted organic compound .
The separation can be by any of the known methods of separation, such as distilla-tion or solvent extraction.
Preferably, distillation is used.
The carboxvlic acid of propionic acid or isobutyric acid formed from acylic anion product, e.g., propionyl fluoride or isobutyryl fluoride, after hydrolysis as described herein can be oxydehydrogenated by the ~rocess 15 described in U.S. patents 3,5~5,248; 3,585,24~; 3,585,250;
3,634,494; 3,652,65~; 3,660,514; 3,766,191; 3,781,336;
3,784,483; 3,8S5,279; 3,917,673; 3,948,959; 3,968,1~9;
3,975,301; 4,029,695; 4,061,673- 4,081,465- ~,088,602;
British Patent 1,447,593.
TEIE REP~CTOR TO FORM THE ACYLIUM ANIO~ PRODUCT
The reaction can be carried out in any reactor which has a means for forming a liquid phase mixture of carbon monoxide and anhydrous acid, e.g., a pressurized mixin~ tank, and a means for separately contacting the liquid phase mi.xture of carbon monoxide and anhvdrous acid with a liquid ohase comprised of an organic compound and reacting (e.g., a tubular reactor) so as to form a product mixture containing an acylium anion produc~. It can further comprise elther a means for separating the acylium anion product from the product mixture, e.g., a distillation column, or a means for separating the acylium anicn product from the product mixture, and separately hydrolyzing or 5~
esterifying the separated acylium anion produc-t rom the product mixture -to a carboxylic acid or ester (e.g., a distillation column connected to a reactor) or a means for separately hydrolyzing or esteri~ying -the acylium anion S product in ~he product mixture to a carboxylic acid or ester.
A means for separating the carboxylic acid or ester ca~ be attached to the reactor (e.g., distillation column). Means for introducinq the reactants -to reac~or (e.g., pumps) can be attached to the reactor.
Figure 2 shows a schematic diagram of a typical reaction system for use in the present invention. Such a syste~ should include sources of the ac d, e.g., hydrofluoric acid 10, a source o carbon monoxide 11 and a source of the organic compound, e.g., propylene 1.2. The carbon monoxide is metered by metering means such as a metering ~alve 13 through line 14 into a pressurized mixing tank 15 which is maintained under pressure. The acid, e.g., hydrofluoric acid, is injected into the mixing tank through line 16 by inserting means such as pump 17. The pressurized mi~ing tank 15 should also be equipped with agit~tion means such as a stirrer 18. The pressurized mixing tank may generally have a liquid phase 19 and a gaseous phase 20 wherein the carbon monoxide not dissolved in the acid, e.g., hydrogen fluoride, is maintained.
The Liquid phase comprises a mi~ture of carbon monoxide and hydrogen fluoride. This miYture is transferred through line 21 under pressure to the inlet of a reactor such as a plug flow or tubular reactor 22.
~he organic compound, such as propylene, is trans-ferred through a llne 23 into the reactor inlet via a liquid-llquld mlxing nozzle. A meterlng oump 24 should also be used to inject the organic compound at the desired rate and at the pressure of the reac~lon~
The reactor of the present in~ention must be capable of maintaining the hydraulic pressure of the system o ~
and must allow sufficient residence ~ime for the reaction to occur. The reac-tion time generally will vary based on the reac~ion temperature. Increased temperature increases the rate of reaction. Generally, the reactlon time should take no longer ~han approxima~.ely 120 seconds altnough it will be obvious to one of ordinary skill in the art ~o determine exactly what the preferred reaction time should be for partic-ular reagents, temperatures and ~ressures.
The reagent mixture comprising the acid, hydrogen ~luoride - car~on monoxide solution and the organic compound passes through the reactor and exits through a pressure release valve or let down ~alve 25.
This is a simple schematic diagram of a reaction svstem suitable for the present invention. Various types of reactors could be used for the present in~ention and one of ordinary skill in the ar~ would have no trouble in designing a particular reactor suitable or the particular intended purpose.
After the reactants have passed the let down valve 25, the addition step of hydrolysis or esterification of the acylium anion product, such as an acyl fluorlde, e.~., isobutyryl fluoride can be conducted in a second reactor 26 or in an extension of the tubular reactor 22. The hydrolysis is conducted simply by adding water to the stable organic carbon monoxide acid acion product, e.g., the acid fluoride, e.g., isobutyrvl fluoride. This produces the car~ox~lic acid, e.g., isobutyric acid, and acid, e~g., hydrogen fluoride, which then can be separated by means such as a distillation apparatus 27 and used again if desired to produce additional stable organic carbon monoxide acid anion addition product. The acid can also be reacted with other compounds such as an alcohol to form an ester.
It is extremely important in the present in~ention to maintain the proper amount of carbon monoxide in solution.
From the chart in Figure 1 the amount of carbon monoxide which can be dissolved in anhydrous hydrogen fluori~e can be determined. This data were empirically determlne~ and one of ordinary skill in the art should be able to likewise determi.ne the solubility of carbon monoxide in anv anhydrous or substantially anhydrous acid a~ a particular tem~erature and a particular pressure. Based on ~he mol~r amount of the organic compound whic~l is intended to be reacted, the amount of carbon monoxide needed for the reaction can ~e ~etexmined.
For example, as s~ated above, the desired range of molar lU ratios of organic compound to carbon monoxide to acid is ~ S:l-100 and the preferred ratio is 1~ 15, ~articularly for propylene, carbon monoxide, and anhydrous hydrogen fluoride.
Other informa~ion required are the reaction condi-tions desired, e.g., the pressure and the temperature of thereactor. From this the molar percentage o~ carbon monoxide dissolved in the acid, e.g., hydrogen fluoride, can be determined. From this, the amount of acid, e.g., hvdrogen fluorlde, solution required to supply sifficient carbon ~0 monoxide to react with the organic compound can also be de~ermined.
For example, if the intended reaction conditions are 5,000 psig and 80C, it is known from the Figure 1 or one could em2irically determine that under these conditions L4 pds. of carbon monoxicle will dissolve in 100 lbs. of anhydrous hydrogen fluoride.
More specifically, take for e~ample the formation of isobutyryl fluoride from propene where the intended flow rate of propene is 226 lb-moles/hr~ or 9,515 lb/hr. It is pxeferable to have about a 10 percent excess of carbon monoxide to insure sufficient carbon monoxide availability for the olefin~ Therefore, aoproximately 24~ lb-mole/hr.
(6,963 lb/hr.) of carbon monoY~ide is required. Since the solubility of carbon monoxide in hydrogen fluoride at the 35 reac~ion conditions is 14 lb. CO/100 pd. ~F it is kno~n tha~
- ~3 -49,736 pds/hr. of ~F is sufficient to dissolve the carbon monoxide needed to react with the propene. This equals 2,486 lb. mole/hr making a molar ratio of hydrogen fluorlde to propene of ll:l.
S At 3,000 psig and 80C~ 9 lbs. of carbon monoxide would be dissolved in 100 lbs. of hydrogen fluoride. There~
fore, the minimum mole ratio in this situation calculates to 17:1 HF to ~ropene.
Once the proper proportions of organic compound and acid carbon monoxide solutions are determined the carbon monoxide and acid solution is injected into the mixing vessel at the desired reaction conditions. The solution of carbon monoxide in acid, e.g., hydrogen fluoride, which is formed in the mixing vessel is metered into the reactor. The mixing vessel must be maintained at a high enough ~emperature and pressure to kee2 the carbon monoxide in solution. The desired amount of organic compound, e.g., propylene, is also metered into the reactor where it contacts and mixes with the solution of carbon monoxide in acid, e.g., hydrogen fluoride.
The reagents are passed through the reactor while maintaining the pressure and tem~erature. Since this reac-tion is generally exot~ermic, cooling jacke~s may be required for the reac~or. Thus, .~or carbon monoxide, hydrogen fluoride, propylene reactlon this is ~articularly important since this reaction should be conducted a-t less than 90C.
The reagents once having passed through the reactor are released through a let down valve and further purified and if requîred, further reacted. A typical reaction as described ~reviously would be the hydrolysis of the stable organic carbon monoxide and anion addition ~roduct, e.g., ~cid fluoride to form a carboxylic acid and the acid, e.g., hydrogen fluoride.
The following examples will illustrate the 2rocess and reactor scheme described herein.
Example 1 ..
The reactor in the presen-t example comprises a 1-liter Monel autoclave equipped with a turbine blade stirrer with two inlets and a bottom outlet connected to a reactor.
The reactor was a tubular reactor comprising a 1/2-inch diameter tube 40 feet in length connec-ted at one end to the outlet of the autoclave and at the exhaust end to a let down valve. The reaction temperature was maintained at approxi-mately 30C and ~he pressure was maintained at 3,000 psig.
In this reaction propene was reacted to form isobutyryl fluoride. The carbon monoxide was injected into the autoclave at a rate of 3.5 g. mole/hr. and the hy~rogen fluoride was injected at a rate of 55 g. mole/hrO and mixed therein to form a liquid phase of carbon monoxide in hydrogen fluoride which was injected into the tubular reactor. The flow rate of propene into the tubu~ar reactor was 2.6 g.
mole/hr. The total flow rate of reagents through the tubular reactor was 1,198 g. per hr. Using this method 2.05 g.
mole/hr. of isobutyryl fluoride was formed. Remaini~g in the efiluent w re 1.0 g. mole/hr. carbon monoxide, 52.4 g. mole/
hr. hydrogen Eluoride and a trace of propene. The remaining effluent comprised other undesixable organics. The selec-tivity of this reaction to isobutyryl fluoride was approxi-mately 75 percent.
2s While the invention has been described with refer-ence to specific de~ails of cextain illustrative embodiments, it is not intended that it shall be l.imited thereby except insofar as such details appear in the accompanying c]aims.
3,784,483; 3,8S5,279; 3,917,673; 3,948,959; 3,968,1~9;
3,975,301; 4,029,695; 4,061,673- 4,081,465- ~,088,602;
British Patent 1,447,593.
TEIE REP~CTOR TO FORM THE ACYLIUM ANIO~ PRODUCT
The reaction can be carried out in any reactor which has a means for forming a liquid phase mixture of carbon monoxide and anhydrous acid, e.g., a pressurized mixin~ tank, and a means for separately contacting the liquid phase mi.xture of carbon monoxide and anhvdrous acid with a liquid ohase comprised of an organic compound and reacting (e.g., a tubular reactor) so as to form a product mixture containing an acylium anion produc~. It can further comprise elther a means for separating the acylium anion product from the product mixture, e.g., a distillation column, or a means for separating the acylium anicn product from the product mixture, and separately hydrolyzing or 5~
esterifying the separated acylium anion produc-t rom the product mixture -to a carboxylic acid or ester (e.g., a distillation column connected to a reactor) or a means for separately hydrolyzing or esteri~ying -the acylium anion S product in ~he product mixture to a carboxylic acid or ester.
A means for separating the carboxylic acid or ester ca~ be attached to the reactor (e.g., distillation column). Means for introducinq the reactants -to reac~or (e.g., pumps) can be attached to the reactor.
Figure 2 shows a schematic diagram of a typical reaction system for use in the present invention. Such a syste~ should include sources of the ac d, e.g., hydrofluoric acid 10, a source o carbon monoxide 11 and a source of the organic compound, e.g., propylene 1.2. The carbon monoxide is metered by metering means such as a metering ~alve 13 through line 14 into a pressurized mixing tank 15 which is maintained under pressure. The acid, e.g., hydrofluoric acid, is injected into the mixing tank through line 16 by inserting means such as pump 17. The pressurized mi~ing tank 15 should also be equipped with agit~tion means such as a stirrer 18. The pressurized mixing tank may generally have a liquid phase 19 and a gaseous phase 20 wherein the carbon monoxide not dissolved in the acid, e.g., hydrogen fluoride, is maintained.
The Liquid phase comprises a mi~ture of carbon monoxide and hydrogen fluoride. This miYture is transferred through line 21 under pressure to the inlet of a reactor such as a plug flow or tubular reactor 22.
~he organic compound, such as propylene, is trans-ferred through a llne 23 into the reactor inlet via a liquid-llquld mlxing nozzle. A meterlng oump 24 should also be used to inject the organic compound at the desired rate and at the pressure of the reac~lon~
The reactor of the present in~ention must be capable of maintaining the hydraulic pressure of the system o ~
and must allow sufficient residence ~ime for the reaction to occur. The reac-tion time generally will vary based on the reac~ion temperature. Increased temperature increases the rate of reaction. Generally, the reactlon time should take no longer ~han approxima~.ely 120 seconds altnough it will be obvious to one of ordinary skill in the art ~o determine exactly what the preferred reaction time should be for partic-ular reagents, temperatures and ~ressures.
The reagent mixture comprising the acid, hydrogen ~luoride - car~on monoxide solution and the organic compound passes through the reactor and exits through a pressure release valve or let down ~alve 25.
This is a simple schematic diagram of a reaction svstem suitable for the present invention. Various types of reactors could be used for the present in~ention and one of ordinary skill in the ar~ would have no trouble in designing a particular reactor suitable or the particular intended purpose.
After the reactants have passed the let down valve 25, the addition step of hydrolysis or esterification of the acylium anion product, such as an acyl fluorlde, e.~., isobutyryl fluoride can be conducted in a second reactor 26 or in an extension of the tubular reactor 22. The hydrolysis is conducted simply by adding water to the stable organic carbon monoxide acid acion product, e.g., the acid fluoride, e.g., isobutyrvl fluoride. This produces the car~ox~lic acid, e.g., isobutyric acid, and acid, e~g., hydrogen fluoride, which then can be separated by means such as a distillation apparatus 27 and used again if desired to produce additional stable organic carbon monoxide acid anion addition product. The acid can also be reacted with other compounds such as an alcohol to form an ester.
It is extremely important in the present in~ention to maintain the proper amount of carbon monoxide in solution.
From the chart in Figure 1 the amount of carbon monoxide which can be dissolved in anhydrous hydrogen fluori~e can be determined. This data were empirically determlne~ and one of ordinary skill in the art should be able to likewise determi.ne the solubility of carbon monoxide in anv anhydrous or substantially anhydrous acid a~ a particular tem~erature and a particular pressure. Based on ~he mol~r amount of the organic compound whic~l is intended to be reacted, the amount of carbon monoxide needed for the reaction can ~e ~etexmined.
For example, as s~ated above, the desired range of molar lU ratios of organic compound to carbon monoxide to acid is ~ S:l-100 and the preferred ratio is 1~ 15, ~articularly for propylene, carbon monoxide, and anhydrous hydrogen fluoride.
Other informa~ion required are the reaction condi-tions desired, e.g., the pressure and the temperature of thereactor. From this the molar percentage o~ carbon monoxide dissolved in the acid, e.g., hydrogen fluoride, can be determined. From this, the amount of acid, e.g., hvdrogen fluorlde, solution required to supply sifficient carbon ~0 monoxide to react with the organic compound can also be de~ermined.
For example, if the intended reaction conditions are 5,000 psig and 80C, it is known from the Figure 1 or one could em2irically determine that under these conditions L4 pds. of carbon monoxicle will dissolve in 100 lbs. of anhydrous hydrogen fluoride.
More specifically, take for e~ample the formation of isobutyryl fluoride from propene where the intended flow rate of propene is 226 lb-moles/hr~ or 9,515 lb/hr. It is pxeferable to have about a 10 percent excess of carbon monoxide to insure sufficient carbon monoxide availability for the olefin~ Therefore, aoproximately 24~ lb-mole/hr.
(6,963 lb/hr.) of carbon monoY~ide is required. Since the solubility of carbon monoxide in hydrogen fluoride at the 35 reac~ion conditions is 14 lb. CO/100 pd. ~F it is kno~n tha~
- ~3 -49,736 pds/hr. of ~F is sufficient to dissolve the carbon monoxide needed to react with the propene. This equals 2,486 lb. mole/hr making a molar ratio of hydrogen fluorlde to propene of ll:l.
S At 3,000 psig and 80C~ 9 lbs. of carbon monoxide would be dissolved in 100 lbs. of hydrogen fluoride. There~
fore, the minimum mole ratio in this situation calculates to 17:1 HF to ~ropene.
Once the proper proportions of organic compound and acid carbon monoxide solutions are determined the carbon monoxide and acid solution is injected into the mixing vessel at the desired reaction conditions. The solution of carbon monoxide in acid, e.g., hydrogen fluoride, which is formed in the mixing vessel is metered into the reactor. The mixing vessel must be maintained at a high enough ~emperature and pressure to kee2 the carbon monoxide in solution. The desired amount of organic compound, e.g., propylene, is also metered into the reactor where it contacts and mixes with the solution of carbon monoxide in acid, e.g., hydrogen fluoride.
The reagents are passed through the reactor while maintaining the pressure and tem~erature. Since this reac-tion is generally exot~ermic, cooling jacke~s may be required for the reac~or. Thus, .~or carbon monoxide, hydrogen fluoride, propylene reactlon this is ~articularly important since this reaction should be conducted a-t less than 90C.
The reagents once having passed through the reactor are released through a let down valve and further purified and if requîred, further reacted. A typical reaction as described ~reviously would be the hydrolysis of the stable organic carbon monoxide and anion addition ~roduct, e.g., ~cid fluoride to form a carboxylic acid and the acid, e.g., hydrogen fluoride.
The following examples will illustrate the 2rocess and reactor scheme described herein.
Example 1 ..
The reactor in the presen-t example comprises a 1-liter Monel autoclave equipped with a turbine blade stirrer with two inlets and a bottom outlet connected to a reactor.
The reactor was a tubular reactor comprising a 1/2-inch diameter tube 40 feet in length connec-ted at one end to the outlet of the autoclave and at the exhaust end to a let down valve. The reaction temperature was maintained at approxi-mately 30C and ~he pressure was maintained at 3,000 psig.
In this reaction propene was reacted to form isobutyryl fluoride. The carbon monoxide was injected into the autoclave at a rate of 3.5 g. mole/hr. and the hy~rogen fluoride was injected at a rate of 55 g. mole/hrO and mixed therein to form a liquid phase of carbon monoxide in hydrogen fluoride which was injected into the tubular reactor. The flow rate of propene into the tubu~ar reactor was 2.6 g.
mole/hr. The total flow rate of reagents through the tubular reactor was 1,198 g. per hr. Using this method 2.05 g.
mole/hr. of isobutyryl fluoride was formed. Remaini~g in the efiluent w re 1.0 g. mole/hr. carbon monoxide, 52.4 g. mole/
hr. hydrogen Eluoride and a trace of propene. The remaining effluent comprised other undesixable organics. The selec-tivity of this reaction to isobutyryl fluoride was approxi-mately 75 percent.
2s While the invention has been described with refer-ence to specific de~ails of cextain illustrative embodiments, it is not intended that it shall be l.imited thereby except insofar as such details appear in the accompanying c]aims.
Claims (15)
1. A process for carbonylation of olefins and organic esters which comprises:
(a) Forming in a first reactor at temperatures in the range of from zero (0) degree Centigrade to one hundred (100) degrees Centigrade and a pressure in the range from fourteen (14) bars (206 psia) to six hundred eighty-two (682) bars (10,000 psia) a liquid mixture of carbon monoxide in an anhydrous acid;
(b) Reacting in the liquid phase in a second reactor the liquid mixture of carbon monoxide in an anhy-drous acid and an organic compound for a time sufficient to form the corresponding acylium anion product at a temperature within the range of from zero (0) degree Centigrade to ninety (90) degrees Centigrade, and at pressures within the range of from thirty-four (34) bars (500 psia) to three hundred forty (340) bars (5,000 psia);
said anhydrous acid being selected from the group consisting of hydrogen fluoride (HF), hydrogen chloride (HC1), hydrogen fluoride - boron trifluoride, and mixtures thereof;
said organic compound being selected from the group consisting of an olefin of up to twenty (20) carbon atoms having at least one double bond capable of adding carbon monoxide thereto, and an organic ester represented by the formula , wherein R' is an alkyl of up to five (5) carbon atoms, and R' is an alkyl of from two (2) to five (5) carbon atoms;
the mole ratio of anhydrous acid to the organic compound being within the range of from one (1) mole to one hundred (100) moles of anhydrous acid to one (1) mole of organic com-pound; and the mole ratio of carbon monoxide to the organic compound is from one (1) mole to five (5 moles of carbon monoxide to one (1) mole of organic compound.
(a) Forming in a first reactor at temperatures in the range of from zero (0) degree Centigrade to one hundred (100) degrees Centigrade and a pressure in the range from fourteen (14) bars (206 psia) to six hundred eighty-two (682) bars (10,000 psia) a liquid mixture of carbon monoxide in an anhydrous acid;
(b) Reacting in the liquid phase in a second reactor the liquid mixture of carbon monoxide in an anhy-drous acid and an organic compound for a time sufficient to form the corresponding acylium anion product at a temperature within the range of from zero (0) degree Centigrade to ninety (90) degrees Centigrade, and at pressures within the range of from thirty-four (34) bars (500 psia) to three hundred forty (340) bars (5,000 psia);
said anhydrous acid being selected from the group consisting of hydrogen fluoride (HF), hydrogen chloride (HC1), hydrogen fluoride - boron trifluoride, and mixtures thereof;
said organic compound being selected from the group consisting of an olefin of up to twenty (20) carbon atoms having at least one double bond capable of adding carbon monoxide thereto, and an organic ester represented by the formula , wherein R' is an alkyl of up to five (5) carbon atoms, and R' is an alkyl of from two (2) to five (5) carbon atoms;
the mole ratio of anhydrous acid to the organic compound being within the range of from one (1) mole to one hundred (100) moles of anhydrous acid to one (1) mole of organic com-pound; and the mole ratio of carbon monoxide to the organic compound is from one (1) mole to five (5 moles of carbon monoxide to one (1) mole of organic compound.
2. The process as recited in Claim 1 wherein the organic compound is an organic ester selected from the group consisting of isopropyl isobutyrate, ethyl isobutyrate, isopropyl propionate, and ethyl propionate.
3. The process as recited in Claim 1 wherein the organic compound is isopropyl isobutyrate.
4. The process as recited in Claim 1 wherein the organic compound is an olefin of up to twenty carbon atoms having at least one double bond capable of adding carbon monoxide thereto.
5. The process as recited in Claim 1 wherein the organic compound is an olefin selected from the group consisting of ethylene and propylene.
6. The process as recited in Claim 1 wherein the organic compound is an olefin, propylene.
7. The process as recited in claim 1 wherein the anhydrous acid is hydrogen fluoride,
8. The process as recited in Claim 7 wherein the anion formed is substantially separated from the reac-tion mixture.
9. The process as recited in claim 8 wherein the acylium anion is further reacted with water at temperatures of from twenty (20) degrees Centigrade to one hundred fifty (150) degrees Centigrade and at pressures from one (1) bar (14.7 psia) to three hundred forty (340) bars (5,000 psia).
A process for producing acids selected from the group consisting of acrylic acid and methacrylic acid which comprises:
(a) Forming in a first reactor at temperatures in the range of from zero (0) degree Centigrade to one hundred (100) degrees Centigrade and a pressure in the range from fourteen (14) bars (206 psia) to six hundred eighty-two (682) bars (10,000 psia) a liquid mixture of carbon monoxide in an anhydrous acid;
(b) Reacting in the liquid phase in a second reactor under conditions whereby the acylium anion product forms the liquid mixture of carbon monoxide dissolved in the anhydrous acid and a liquid mixture comprised of an olefin anhydrous acid being selected from the group consisting of hydrogen fluoride (HF), hydrogen chloride (HCL), hydrogen fluoride - boron trifluoride (HF-BF3), and mixtures thereof;
hydrolyzing the acylium anion product under conditions whereby a carboxylic acid forms;
separating the carboxylic acid from the hydrolyzed mixture;
oxydehydrogenating in the vapor phase a mixture comprised of the carboxylic acid, water, and oxygen at a temperature from 300 to 500°C, at a pressure from 0.5 atmospheres to two (2) atmospheres, in the presence of a catalyst comprised of iron, phosphorous, and oxygen, defined by the empirical formula Fe Px Oz, where relative to atom of Fe, x represents from 0.25 to 3.5 atoms of phosphorous, and z represents the number of oxygen atoms required to satisfy the valence requirements of the catalyst for time sufficient to produce the corresponding unsaturated carboxylic acid of acrylic acid or methacrylic acid.
(a) Forming in a first reactor at temperatures in the range of from zero (0) degree Centigrade to one hundred (100) degrees Centigrade and a pressure in the range from fourteen (14) bars (206 psia) to six hundred eighty-two (682) bars (10,000 psia) a liquid mixture of carbon monoxide in an anhydrous acid;
(b) Reacting in the liquid phase in a second reactor under conditions whereby the acylium anion product forms the liquid mixture of carbon monoxide dissolved in the anhydrous acid and a liquid mixture comprised of an olefin anhydrous acid being selected from the group consisting of hydrogen fluoride (HF), hydrogen chloride (HCL), hydrogen fluoride - boron trifluoride (HF-BF3), and mixtures thereof;
hydrolyzing the acylium anion product under conditions whereby a carboxylic acid forms;
separating the carboxylic acid from the hydrolyzed mixture;
oxydehydrogenating in the vapor phase a mixture comprised of the carboxylic acid, water, and oxygen at a temperature from 300 to 500°C, at a pressure from 0.5 atmospheres to two (2) atmospheres, in the presence of a catalyst comprised of iron, phosphorous, and oxygen, defined by the empirical formula Fe Px Oz, where relative to atom of Fe, x represents from 0.25 to 3.5 atoms of phosphorous, and z represents the number of oxygen atoms required to satisfy the valence requirements of the catalyst for time sufficient to produce the corresponding unsaturated carboxylic acid of acrylic acid or methacrylic acid.
11. The process as recited in claim 10 wherein the catalyst further comprises a promoter represented by Mey wherein Me represents the promoter and y represents the number of promoter atoms relative to one atom of iron and is from 0.01 to 2.0, said promoter Me being selected from the group comprised of Le, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, and mixtures thereof.
12. The process as recited in any of claims 10 or 11 wherein the anhydrous acid is hydrogen fluoride, and the olefin is propylene.
13. A process for forming isobutyryl fluoride by the carbonylation of propylene with carbon monoxide in anhydrous hydrogen fluoride, which comprises:
(a) Forming in a first reactor at temperatures in the range of from zero (0) degree Centigrade to one hundred (100) degrees Centigrade and a pressure in the range from fourteen (14) bars (206 psia) to six hundred eighty-two (682) bars (10,000 psia) a liquid mixture of carbon monoxide in substantially anhydrous hydrogen flouride, and (b) Reacting together in a liquid phase reaction the first liquid mixture and propylene in a reactor under conditions whereby isobutyryl fluoride forms forty (40) to sixty (60) degrees Centigrade, and at pressures within the range of 500 psia (39 bars) to 5000 psia (340 bars), the mole ratio of carbon monoxide to propylene being from 1.1 to 5, the mole ratio of hydrogen fluoride to propylene being from 10 to 20 at a residence time from 0.2 to 310 minutes.
(a) Forming in a first reactor at temperatures in the range of from zero (0) degree Centigrade to one hundred (100) degrees Centigrade and a pressure in the range from fourteen (14) bars (206 psia) to six hundred eighty-two (682) bars (10,000 psia) a liquid mixture of carbon monoxide in substantially anhydrous hydrogen flouride, and (b) Reacting together in a liquid phase reaction the first liquid mixture and propylene in a reactor under conditions whereby isobutyryl fluoride forms forty (40) to sixty (60) degrees Centigrade, and at pressures within the range of 500 psia (39 bars) to 5000 psia (340 bars), the mole ratio of carbon monoxide to propylene being from 1.1 to 5, the mole ratio of hydrogen fluoride to propylene being from 10 to 20 at a residence time from 0.2 to 310 minutes.
14. The process as recited in claim 13 wherein the pressure is from 2500 to 5000 psia (170 to 340 bars).
15. The process as recited in claim 13 (wherein the pressure is from 2500 to 3000 psia (170 to 204 bars).
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US28213081A | 1981-07-10 | 1981-07-10 | |
| US282,130 | 1981-07-10 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1192576A true CA1192576A (en) | 1985-08-27 |
Family
ID=23080232
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000404491A Expired CA1192576A (en) | 1981-07-10 | 1982-06-04 | Production of an acylium anion product and carboxylic acids and esters therefrom |
Country Status (19)
| Country | Link |
|---|---|
| JP (1) | JPS6024089B2 (en) |
| KR (1) | KR850001912B1 (en) |
| AT (1) | AT392066B (en) |
| AU (1) | AU532911B1 (en) |
| BE (1) | BE893415A (en) |
| BR (1) | BR8203330A (en) |
| CA (1) | CA1192576A (en) |
| CH (1) | CH656608A5 (en) |
| DD (1) | DD207900A5 (en) |
| DE (1) | DE3221173C2 (en) |
| ES (2) | ES513956A0 (en) |
| FR (1) | FR2512811B1 (en) |
| GB (1) | GB2101591B (en) |
| IT (1) | IT1195931B (en) |
| NL (1) | NL187626C (en) |
| PL (1) | PL140231B1 (en) |
| RO (1) | RO83931B (en) |
| SE (1) | SE452609B (en) |
| ZA (1) | ZA823929B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0759531B2 (en) * | 1986-11-04 | 1995-06-28 | 三菱瓦斯化学株式会社 | Method for synthesizing isobutyryl fluoride |
| US5463095A (en) * | 1993-06-15 | 1995-10-31 | Mitsubishi Gas Chemical Company, Inc. | Process for the production of esters |
| BR102012020205A2 (en) * | 2012-08-13 | 2014-08-19 | Cesar Roque Ecker | MORTAR APPLICATOR |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE972291C (en) * | 1954-05-16 | 1959-07-02 | Studiengesellschaft Kohle Mbh | Process for the production of monocarboxylic acids from olefins, carbon monoxide and water |
| DE973077C (en) * | 1954-07-30 | 1959-11-26 | Studiengesellschaft Kohle Mbh | Process for the production of carboxylic acids from olefins and carbon oxide |
| DE1064941B (en) * | 1957-04-24 | 1959-09-10 | Studiengesellschaft Kohle Mbh | Process for the preparation of mixtures of saturated aliphatic or cycloaliphatic monocarboxylic acid alkyl esters |
| US3065242A (en) * | 1960-02-23 | 1962-11-20 | Du Pont | Production of acyl halides, carboxylic acids and lactones |
| GB942367A (en) * | 1961-04-29 | 1963-11-20 | Basf Ag | Continuous production of carboxylic acids from olefines, carbon monoxide and water |
| NL6816940A (en) * | 1967-11-28 | 1969-05-30 | ||
| BE755997A (en) * | 1969-09-11 | 1971-03-10 | Bp Chem Int Ltd | PRODUCTION OF DICARBOXYLIC ACIDS |
| DE2750719A1 (en) * | 1977-11-12 | 1979-05-17 | Roehm Gmbh | Isobutyric acid prepn. by boron tri:fluoride-catalysed carbonylation - of propylene, isopropanol, ether and/or ester deriv. in aliphatic carboxylic acid medium |
-
1982
- 1982-06-04 KR KR8202508A patent/KR850001912B1/en active
- 1982-06-04 DD DD82240468A patent/DD207900A5/en not_active IP Right Cessation
- 1982-06-04 CH CH3477/82A patent/CH656608A5/en not_active IP Right Cessation
- 1982-06-04 JP JP57096066A patent/JPS6024089B2/en not_active Expired
- 1982-06-04 AU AU84608/82A patent/AU532911B1/en not_active Ceased
- 1982-06-04 IT IT21709/82A patent/IT1195931B/en active
- 1982-06-04 RO RO107796A patent/RO83931B/en unknown
- 1982-06-04 DE DE3221173A patent/DE3221173C2/en not_active Expired
- 1982-06-04 GB GB08216302A patent/GB2101591B/en not_active Expired
- 1982-06-04 BE BE0/208267A patent/BE893415A/en not_active IP Right Cessation
- 1982-06-04 ZA ZA823929A patent/ZA823929B/en unknown
- 1982-06-04 ES ES513956A patent/ES513956A0/en active Granted
- 1982-06-04 NL NLAANVRAGE8202269,A patent/NL187626C/en not_active IP Right Cessation
- 1982-06-04 AT AT0217782A patent/AT392066B/en not_active IP Right Cessation
- 1982-06-04 CA CA000404491A patent/CA1192576A/en not_active Expired
- 1982-06-04 FR FR8209811A patent/FR2512811B1/en not_active Expired
- 1982-06-04 SE SE8203478A patent/SE452609B/en not_active IP Right Cessation
- 1982-06-04 PL PL1982236785A patent/PL140231B1/en unknown
- 1982-06-07 BR BR8203330A patent/BR8203330A/en not_active IP Right Cessation
-
1983
- 1983-06-01 ES ES523258A patent/ES523258A0/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| AT392066B (en) | 1991-01-25 |
| JPS5810535A (en) | 1983-01-21 |
| BR8203330A (en) | 1983-05-24 |
| DD207900A5 (en) | 1984-03-21 |
| PL140231B1 (en) | 1987-04-30 |
| FR2512811A1 (en) | 1983-03-18 |
| ATA217782A (en) | 1990-07-15 |
| FR2512811B1 (en) | 1985-07-05 |
| KR840000464A (en) | 1984-02-22 |
| SE452609B (en) | 1987-12-07 |
| PL236785A1 (en) | 1983-02-14 |
| ES8500208A1 (en) | 1984-10-01 |
| KR850001912B1 (en) | 1985-12-31 |
| RO83931A (en) | 1984-04-12 |
| IT8221709A0 (en) | 1982-06-04 |
| SE8203478L (en) | 1983-01-11 |
| CH656608A5 (en) | 1986-07-15 |
| ES523258A0 (en) | 1984-10-01 |
| JPS6024089B2 (en) | 1985-06-11 |
| GB2101591A (en) | 1983-01-19 |
| NL187626B (en) | 1991-07-01 |
| IT1195931B (en) | 1988-11-03 |
| ZA823929B (en) | 1983-11-30 |
| RO83931B (en) | 1984-05-30 |
| ES8400376A1 (en) | 1983-10-16 |
| DE3221173A1 (en) | 1983-01-27 |
| NL187626C (en) | 1991-12-02 |
| BE893415A (en) | 1982-10-01 |
| NL8202269A (en) | 1983-02-01 |
| GB2101591B (en) | 1985-11-27 |
| ES513956A0 (en) | 1983-10-16 |
| DE3221173C2 (en) | 1984-07-26 |
| AU532911B1 (en) | 1983-10-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US3769329A (en) | Production of carboxylic acids and esters | |
| KR100220824B1 (en) | Carbonylation of olefins | |
| US20080269459A1 (en) | Process for the Preparation of a Dicarboxylic Acid | |
| EP0665210B1 (en) | Process for producing acetic anhydride alone or both of acetic anhydride and acetic acid | |
| US3725534A (en) | Method of forming complex cobalt carbonyl compounds | |
| EP0283586B1 (en) | Homologation process | |
| US4256913A (en) | Preparation of carboxylic acids using a BF3 catalyst complex | |
| JP3656030B2 (en) | Method for producing tertiary butyl alcohol | |
| EP0580735A1 (en) | Preparation of trialkylacetic acids, particularly of pivalic acid, using solid acid catalysis | |
| CA1192576A (en) | Production of an acylium anion product and carboxylic acids and esters therefrom | |
| KR102397805B1 (en) | Acetic acid production method | |
| KR890003785B1 (en) | Production of carboxylic acids from alcohols | |
| US3778468A (en) | Process for preparing ethylene glycol esters | |
| US4111982A (en) | Coproduction of acetic and propionic acids | |
| EP0042633B1 (en) | Process for the carbonylation of alkanols and/or ethers | |
| JPH0148889B2 (en) | ||
| KR850001914B1 (en) | Process for the preparation of isobutyryl fluoride | |
| US5117046A (en) | Preparation of alkylidene diesters | |
| US4810821A (en) | Preparation of alkylidene diesters | |
| JPS63192738A (en) | Carbonylation | |
| US5227521A (en) | Preparation of trialkylacetic acids, particularly of pivalic acid, using lewis acid catalysts | |
| EP0077116A1 (en) | Preparation of alkylidene diesters | |
| EP0101719B1 (en) | Formation of isobutyric acid or methyl isobutyrate | |
| US20230150908A1 (en) | Process for Producing Acetic Acid | |
| CA1156256A (en) | Production of carboxylic esters from acylium anions formed by carbonylation |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |