US3025322A - Acrylic monomers and the preparation thereof - Google Patents

Acrylic monomers and the preparation thereof Download PDF

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US3025322A
US3025322A US776403A US77640358A US3025322A US 3025322 A US3025322 A US 3025322A US 776403 A US776403 A US 776403A US 77640358 A US77640358 A US 77640358A US 3025322 A US3025322 A US 3025322A
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copper
nickel
weight
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Smolin Edwin Marvin
Anderson Richard Dean
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Wyeth Holdings LLC
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American Cyanamid Co
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
    • B01J31/2208—Oxygen, e.g. acetylacetonates
    • B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
    • B01J31/2252—Sulfonate ligands
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
    • B01J31/30—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
    • C07C51/14—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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
    • B01J2231/32—Addition reactions to C=C or C-C triple bonds
    • B01J2231/321—Hydroformylation, metalformylation, carbonylation or hydroaminomethylation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
    • B01J2531/0213—Complexes without C-metal linkages
    • B01J2531/0216—Bi- or polynuclear complexes, i.e. comprising two or more metal coordination centres, without metal-metal bonds, e.g. Cp(Lx)Zr-imidazole-Zr(Lx)Cp
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
    • B01J2531/16—Copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/84—Metals of the iron group
    • B01J2531/847—Nickel

Definitions

  • This invention relates to a novel method for preparing acrylic acid. More particularly, the invention relates to an improvement in nickel salt-catalyzed, liquid-phase reactions at elevated temperatures and pressures of equivalent amounts of acetylene, carbon monoxide and Water.
  • alkyl substituent having 1 to 8 carbon atoms an unsubstituted aryl group, such as mono- -;;nuclear and po-lynuclear aryl groups; an alkyl-substituted aryl group, said alkyl substituent having from 1 to 18 carbon atoms, preferably C to C an alkyl-substituted aryl group of the type just mentioned in which the alkyl substituent having 1 to 18 carbon atoms is, in turn, substituted with a member selected from the group consisting of C to C alkyl groups, anaryl group, an aralkyl group having 1 to 18 carbon atoms in the alkyl moiety,
  • nickel chloride copper chloride, nickel bromide, copper bromide, nickel iodide, copper iodide, and mixtures thereof.
  • metal hydrocarbon sulfonate and the metal halide have different metal cations.
  • a copper halide such as copper bromide
  • a nickel halide such as nickel bromide
  • the catalysts are present in sufiicient quantity to provide from 0.1 to 8.0 percent by weight nickel salt, preferably 0.2 to 5.0 percent by weight, basis the total weight of the non-gaseous mixture.
  • cient quantity of catalyst is generally present to provide from 0.02 to 5.0 percent by weight copper salt, preferably from 0.5 to 1.0 percent by weight, basis the total weight of the non-gaseous reaction mixture.
  • non-gaseous reaction mixture i.e., the solvent, water and catalyst, are intended.
  • the nickelcontaining catalyst is present in a molar excess with respect to the copper catalyst, usually in the mole ratio range of 2:1 to 4:1; however, a range of 1:1 to 6:1 is suitable.
  • the solvents are not irreversibly changed by the presence of Water and are not able to react with acetylene or carbon monoxide.
  • the solvents therefore, should not contain free hydroxy, mercapto, or carboxy groups, olefinic or acetylenic linkages, or primary or secondary amino groups.
  • the boiling points of the solvents are preferably below that of acrylic-acid.
  • Preferred solvents are cyclic 'ethers, such as tetrahydrofuran, dioxane, and saturated aliphatic ketones, such as acetone, methyl ethyl ketone and diethyl ketone.
  • the reactions contemplated herein advantageously may be conducted attemperatures as low as C. and as high as 220 C. Preferably, reaction temperatures in the range of about C. to about 205 C are employed. On the other hand, pressures 'as low as 300 pounds per square inch gauge and as high as about 900 pounds per square inch gauge are suitable, yet pressures in the range of about 450 pounds per square inch gauge to 840 pounds per square inch gauge are preferred.
  • the process of the instant invention may be conducted in a batch, semi-continuous and continuous manner.
  • the water component utilized in the instant discovery may be present in an equivalent amount, basis the acetylene and carbon monoxide reactants. More commonly, however, these gaseous components are used in excess over the water. An excess of acetylene and/orcarbon monoxide over water of 10 to 20 molar percent orv more, for example, is often desirable.
  • the acrylic acid produced by the novel process of the present invention is avery desirable material of commerce.
  • its use in prosthetic surgery, electrical insulation, etc. is very extensive. Consequently, preparation of this material by a suitable economical and trouble-free process'has been the object of research for many years.
  • loss of catalyst has been a source of great anxiety and heretofore a wholly satisfactory solution to the problem has not been found.
  • the metal hydrocarbon sulfonate catalysts of the present invention may be prepared as shown by the following typical process:
  • EXAMPLE A To 13.5 parts of para-toluene sulfonic acid dissolved in water is added suflicient aqueous barium hydroxide solution to exactly neutralize the acid. To the resulting solution 9.3 parts of NiSO -6H O dissolved in water is added. Barium sulfate precipitates and is removed by filtration, the filtrate being then dried by heating to a temperature of about 100 C. on a steam bath for a period of about 16 hours.
  • a yield of 16.2 parts of the hydrated nickel salt of para-toluene sulfonic acid (90 percent by Weight of theory) is recovered, the salt having the formula EXAMPLE I 1
  • a solution containing 12 parts by weight of water, 88 parts by weight of acetone, 0.4 part by weight of NiBr -BH O, 0.2 part copper decylbenzene sulfonate and 0.15 part by weight of hydroquinone inhibitor is continuously pumped into a suitable high pressure reactor at the rate of 19 milliliters .per minute and maintained at about 720 pounds per square inch gauge throughout the reaction.
  • A- product solution containing 24.2 percent by weight acrylic acid is recovered.
  • the recovery of nickel catalyst in the eflluent stream amounts to 30.9 percent by 3 weight; similarly, .the recovery of copper catalyst at the end of 15 hours is 51.5 percent by weight, basis the copper catalyst charged.
  • EXAMPLE II A solutionv containing 12 parts of water, 88 parts of acetone, 0.05 part of cupric bromide, 0.15 part of hydro- .quinone inhibitor and 0.3 part by weight of nickel do- 1 .decylbenzene sulfonate is passed into a high-pressure continuous reactor at the rate of 16 milliliters per minute, thus providing a residence time of 119 minutes, computed as described in Example I, supra. While heating the reactor to 200 C., equal volumes of acetylene and carbon monoxide are introduced therein at a rate sufiicient to provide a 20 mole percent carbon monoxide excess over the water and a 20 mole percent acetylene excess over the carbon monoxide. The pressure on the reacting mixture is maintained at 710 pounds per square inch gauge throughout the reaction.
  • Comparative data disclose that Examples I and II, when repeated using similar amounts of CuBr and NiBr respectively, for the hydrocarbon sulfonates in the examples, show recovery of less than one-third of the catalyst recovered in these examples.
  • EXAMPLE III One hundred and fifty parts of a solution consisting of 120 parts of water, 880 parts of acetone, 1.5 parts of cupric bromide, 1 part of hydroquinone inhibitor and 6 parts of nickel methane sulfonate trihydrate is charged to a suitable stainless steel rocking autoclave. The autoclave is then evacuated with a water aspirator and purged with nitrogen 3 times. After charging the vessel with sufiicient acetylene to produce a pressure of 50 pounds per square inch gauge, the vessel is heated to 200 C., and the pressure therein raised to 750 pounds per square inch gauge by introducing equal amounts by volume of acetylene and carbon monoxide. Rocking of the autoclave is then started and the pressure drop is observed.
  • Example III is repeated with the exception that the nickel methane sulfonate trihydrate catalyst is replaced by the nickel salt'of xylene sulfonic acid (trihydrate). As in Example III the pressure on the system is raised to 750 pounds per square inch gauge.
  • the repressuring cycles may be represented by the following table:
  • Example III is repeated with the exception that the nickel methane sulfonate trihydrate is replaced by the nickel salt of 2-tolyl-2-(tolyl sulfonic acid) butane (SI-I 0). As in Example III the pressure on the system is raised to 750 pounds per square inch gauge.
  • the system is repressured several times, also as in Example III, above, the autoclave is cooled to ambient temperature (21 C. to 23 C.), and the product solution removed therefrom.
  • a desirable yield of acrylic acid is realized and over 75 percent by weight of the catalyst charged is recovered in substantially unchanged form.
  • Example III is repeated with the exception that the nickel methane sulfonate trihydrate catalyst is replaced by mixed nickel dodecyl sulfonates (C H hydrocarbon fraction having a boiling point of 200 C.-214 C.) prepared in the manner shown in Example A, above, from a commercial mixture of the corresponding sulfonic acids.
  • the system is represented several times, also as in Example III, above, the autoclave is cooled to ambient temperature (21 C. to 23 C.), and the product solution removed therefrom. A desirable yield of acrylic acid is realized and over 75 percent by weight of the catalyst charged is recovered in substantially unchanged form.
  • the catalyst combination is the hydrated nickel salts of methane sulfonic acid having less than about 6 moles of combined water and a copper halide selected from the group consisting of copper chloride, copper bromide and copper iodide.
  • the catalyst combination is the hydrated nickel salt of naphthalene-2-sulfonic acid having less than about 6 moles of combined water and a copper halide selected from the group consisting of copper chloride, copper bromide and copper iodide.
  • the catalyst combination is the hydrated nickel salt of 2-tolyl-2-(tolyl sulfonic acid) butane having less than about 6 moles of combined water and a copper halide selected from the group consisting of copper chloride, copper bromide and copper iodide.
  • the catalyst combination is the hydrated copper salt of decylbenzene sulfonic acid having less than about 6 moles of combined water and a nickel halide selected from the group consisting of nickel chloride, nickel bromide and nickel iodide.
  • the catalyst combination is the hydrated nickel salt of xylene sulfonic acid having less than about 6 moles of combined water and a copper halide selected from the group consisting of copper chloride, copper bromide and copper iodide.

Description

3,025,322 ACRYLIC MONOMERS AND THE PREPARATION THEREGF Edwin Marvin Smolin, Springdale, and Richard Dean Anderson, Greenwich, Conn., assignors to American Cyanamid Company, New York, N.Y., a corporation of Maine No Drawing. Filed Nov. 26, 1958, Ser. No. 776,403 8 Claims. (Cl. 260533) This invention relates to a novel method for preparing acrylic acid. More particularly, the invention relates to an improvement in nickel salt-catalyzed, liquid-phase reactions at elevated temperatures and pressures of equivalent amounts of acetylene, carbon monoxide and Water. It has been the experience in reaction systems of this type that the catalysts heretofore employed occasioned a number of side reactions which resulted in lowering spacetime yields of acrylic acid product. For example, precipitates were formed and accumulated in the reaction system causing mechanical difficulties. Also, the metal ions of the catalysts heretofore employed were usurped by t ese side reactions, thus rapidly removing them from solution and causing the reaction rate to fall off.
According to the present invention, however, the difficulties encountered in the prior art have been overcome to a very considerable extent, thus greatly enhancing the product yield and catalyst recovery. Pursuant to the instant discovery, equivalent amounts of acetylene, carbon monoxide and water are reacted in the liquid phase at elevated temperatures and pressures in the presence of a combination of catalysts corresponding to the formulae wherein n is a value from to 1; x represents a value from 0 to 20; X is a halogen atom, including bromine, chlorine and iodine; and A represents an alkyl group having 1 to 18 carbon atoms, preferably C to C an alkylsubstituted alkyl group having 1 to 18 carbon atoms, pref-,
erably C to C said alkyl substituent having 1 to 8 carbon atoms; an unsubstituted aryl group, such as mono- -;;nuclear and po-lynuclear aryl groups; an alkyl-substituted aryl group, said alkyl substituent having from 1 to 18 carbon atoms, preferably C to C an alkyl-substituted aryl group of the type just mentioned in which the alkyl substituent having 1 to 18 carbon atoms is, in turn, substituted with a member selected from the group consisting of C to C alkyl groups, anaryl group, an aralkyl group having 1 to 18 carbon atoms in the alkyl moiety,
copper para-toluene sulfonate, nickel decylbenzene sul-' fonate, copper decylbenzene sulfonate, nickel Z-napthalene sulfonate, copper Z-naphthalene -su1fonate,- nickel dodecylbenzene sulfonate, copper dodecylbenz'ene sulfonate, nickel bis(2,2-ditolylbutane)sulfonate, copper bis(2,2 tolylbutane)sulfonate, nickel bis(2 ,2 diphenylbutane) sulfonate, copper bis(2,2-diphenylbutane)sulfonate, nickel bis(1,1-dixylyleth-ane)sulfonate, copper bis- (1,1-dixylethane)sulfonate, and the like, and mixtures thereof.
Among'the nickel halides-and copper halides contem- Uni ted States Patent 0 3,025,322 Patented Mar. 13, 1962 ice plated herein are nickel chloride, copper chloride, nickel bromide, copper bromide, nickel iodide, copper iodide, and mixtures thereof.
It has been found, pursuant to the present discovery and as indicated by the above general formulae, that best results are achieved when the metal hydrocarbon sulfonate and the metal halide have different metal cations. For instance, when nickel para-toluene sulfonate is the metal sulfonate, a copper halide, such as copper bromide, is paired with it. Similarly, When copper para-toluene sulfonate is the metal sulfonate, a nickel halide, such as nickel bromide, is used.
Generally, the catalysts are present in sufiicient quantity to provide from 0.1 to 8.0 percent by weight nickel salt, preferably 0.2 to 5.0 percent by weight, basis the total weight of the non-gaseous mixture. cient quantity of catalyst is generally present to provide from 0.02 to 5.0 percent by weight copper salt, preferably from 0.5 to 1.0 percent by weight, basis the total weight of the non-gaseous reaction mixture.
By the expression non-gaseous reaction mixture used herein, the non-gaseous components charged to the reactor, i.e., the solvent, water and catalyst, are intended.
Very desirable results are obtained when the nickelcontaining catalyst is present in a molar excess with respect to the copper catalyst, usually in the mole ratio range of 2:1 to 4:1; however, a range of 1:1 to 6:1 is suitable.
In carrying out the reaction of acetylene, carbon monoxide and water in the presence. of the catalyst combination contemplated herein, it is very advantageous to use an excess by volume of an inert oxygen-containing organicsolvent which is inert to the reactants under the reaction conditions and miscible with Water. In other words, the solvents are not irreversibly changed by the presence of Water and are not able to react with acetylene or carbon monoxide. The solvents, therefore, should not contain free hydroxy, mercapto, or carboxy groups, olefinic or acetylenic linkages, or primary or secondary amino groups. The boiling points of the solvents are preferably below that of acrylic-acid.
Preferred solvents are cyclic 'ethers, such as tetrahydrofuran, dioxane, and saturated aliphatic ketones, such as acetone, methyl ethyl ketone and diethyl ketone.
While a slight excess of the solvent with respect to the water employed is suitable for example, parts by volume of solvent for 40 parts by volume of water, much greater excesses of the liquid organic solvent are preferred. 'For instance, a volume ratio of solvent to water in the range'of about :25 to about :5 is desirable.
While an equimolar ratio of acetylene to carbon monoxide is generally used, the instant invention contemplates the use of an excess of either of these reactants up to about molar percent or more. i The reactions contemplated herein advantageously may be conducted attemperatures as low as C. and as high as 220 C. Preferably, reaction temperatures in the range of about C. to about 205 C are employed. On the other hand, pressures 'as low as 300 pounds per square inch gauge and as high as about 900 pounds per square inch gauge are suitable, yet pressures in the range of about 450 pounds per square inch gauge to 840 pounds per square inch gauge are preferred.
. The process of the instant invention may be conducted in a batch, semi-continuous and continuous manner.
The water component utilized in the instant discovery may be present in an equivalent amount, basis the acetylene and carbon monoxide reactants. More commonly, however, these gaseous components are used in excess over the water. An excess of acetylene and/orcarbon monoxide over water of 10 to 20 molar percent orv more, for example, is often desirable.
As is well known, the acrylic acid produced by the novel process of the present invention is avery desirable material of commerce. For example, its use in prosthetic surgery, electrical insulation, etc. is very extensive. Consequently, preparation of this material by a suitable economical and trouble-free process'has been the object of research for many years. Peculianly enough, as indicated above, loss of catalyst has been a source of great anxiety and heretofore a wholly satisfactory solution to the problem has not been found.
The metal hydrocarbon sulfonate catalysts of the present invention may be prepared as shown by the following typical process:
EXAMPLE A To 13.5 parts of para-toluene sulfonic acid dissolved in water is added suflicient aqueous barium hydroxide solution to exactly neutralize the acid. To the resulting solution 9.3 parts of NiSO -6H O dissolved in water is added. Barium sulfate precipitates and is removed by filtration, the filtrate being then dried by heating to a temperature of about 100 C. on a steam bath for a period of about 16 hours. A yield of 16.2 parts of the hydrated nickel salt of para-toluene sulfonic acid (90 percent by Weight of theory) is recovered, the salt having the formula EXAMPLE I 1 A solution containing 12 parts by weight of water, 88 parts by weight of acetone, 0.4 part by weight of NiBr -BH O, 0.2 part copper decylbenzene sulfonate and 0.15 part by weight of hydroquinone inhibitor is continuously pumped into a suitable high pressure reactor at the rate of 19 milliliters .per minute and maintained at about 720 pounds per square inch gauge throughout the reaction. Concurrently a mixture of equal volumes of carbon monoxide and acetylene is continuously fed to the reactor in approximately stoichiometric amounts, basis the water charged. The reaction is continued for a period of 15 hours at a temperature of 190 C. to 195 C. andreactor residence time of 200 minutes, computed by dividing the reactor volume by the feed rate, both in equivalent units.
A- product solution containing 24.2 percent by weight acrylic acid is recovered. The recovery of nickel catalyst in the eflluent stream amounts to 30.9 percent by 3 weight; similarly, .the recovery of copper catalyst at the end of 15 hours is 51.5 percent by weight, basis the copper catalyst charged.
EXAMPLE II A solutionv containing 12 parts of water, 88 parts of acetone, 0.05 part of cupric bromide, 0.15 part of hydro- .quinone inhibitor and 0.3 part by weight of nickel do- 1 .decylbenzene sulfonate is passed into a high-pressure continuous reactor at the rate of 16 milliliters per minute, thus providing a residence time of 119 minutes, computed as described in Example I, supra. While heating the reactor to 200 C., equal volumes of acetylene and carbon monoxide are introduced therein at a rate sufiicient to provide a 20 mole percent carbon monoxide excess over the water and a 20 mole percent acetylene excess over the carbon monoxide. The pressure on the reacting mixture is maintained at 710 pounds per square inch gauge throughout the reaction.
After 280 minutes of operation, a sample of the product of reaction is taken, titrated, and analyzed to determine the double bond content thereof. Analysis shows an acrylic acid content of 15.5 parts by weight of the product. Higher boiling tarry materials are present only to the extent of 0.8 part by weight of the product. Further analysis of the product solution shows the presence of 83.10 percent by weight of the nickel catalyst charged, which catalyst is still in soluble form.
Comparative data disclose that Examples I and II, when repeated using similar amounts of CuBr and NiBr respectively, for the hydrocarbon sulfonates in the examples, show recovery of less than one-third of the catalyst recovered in these examples.
EXAMPLE III One hundred and fifty parts of a solution consisting of 120 parts of water, 880 parts of acetone, 1.5 parts of cupric bromide, 1 part of hydroquinone inhibitor and 6 parts of nickel methane sulfonate trihydrate is charged to a suitable stainless steel rocking autoclave. The autoclave is then evacuated with a water aspirator and purged with nitrogen 3 times. After charging the vessel with sufiicient acetylene to produce a pressure of 50 pounds per square inch gauge, the vessel is heated to 200 C., and the pressure therein raised to 750 pounds per square inch gauge by introducing equal amounts by volume of acetylene and carbon monoxide. Rocking of the autoclave is then started and the pressure drop is observed. After 23 minutes the pressure drops to 560 pounds per square inch gauge and the reaction mixture is immediately repressed by the addition of equal amounts by volume of acetylene and carbon monoxide to create a pressure of 750 pounds per square inch gauge. Twenty-one minutes later the pressure is down to 560 pounds per square inch gauge. The autoclave is then cooled to ambient temperature (21 C. to 23 C.) and the prodtezt solution removed therefrom. This solution contains 4.2 percent by weight acrylic acid. Over 75 percent by weight of the catalyst charged is recovered in unchanged form.
EXAMPLE IV Example III is repeated with the exception that the nickel methane sulfonate trihydrate catalyst is replaced by the nickel salt'of xylene sulfonic acid (trihydrate). As in Example III the pressure on the system is raised to 750 pounds per square inch gauge. The repressuring cycles may be represented by the following table:
Table I Pressure Drops Repressurcd to Tune (minutes) to (pounds per (pounds per square inch square inch gauge) gauge) At the end of this period the autoclave is cooled to ambient temperature (21 C. to 23 C.) and the product solution removed therefrom. This solution contains 4.5 percent by weight acrylic acid and over 75 percent by weight of the catalyst charged to the autoclave, the catalyst being substantially in unchanged form.
EXAMPLE V Table 11 Pressure Drops to (pounds per square inch gauge) Repressured to (pounds per square inch gauge) Time (minutes) At the end of this period the autoclave is cooled to ambient temperature (21 C. to 23 C.) and the product solution removed therefrom. This solution contains 3.5 percent by weight acrylic acid and over 75 percent by weight of the catalyst charged to the autoclave, the catalyst being substantially in unchanged form.
EXAMPLE VI Example III is repeated with the exception that the nickel methane sulfonate trihydrate is replaced by the nickel salt of 2-tolyl-2-(tolyl sulfonic acid) butane (SI-I 0). As in Example III the pressure on the system is raised to 750 pounds per square inch gauge.
In addition, the system is repressured several times, also as in Example III, above, the autoclave is cooled to ambient temperature (21 C. to 23 C.), and the product solution removed therefrom. A desirable yield of acrylic acid is realized and over 75 percent by weight of the catalyst charged is recovered in substantially unchanged form.
EXAMPLE VII Example III is repeated with the exception that the nickel methane sulfonate trihydrate catalyst is replaced by mixed nickel dodecyl sulfonates (C H hydrocarbon fraction having a boiling point of 200 C.-214 C.) prepared in the manner shown in Example A, above, from a commercial mixture of the corresponding sulfonic acids. In addition, the system is represented several times, also as in Example III, above, the autoclave is cooled to ambient temperature (21 C. to 23 C.), and the product solution removed therefrom. A desirable yield of acrylic acid is realized and over 75 percent by weight of the catalyst charged is recovered in substantially unchanged form.
While the present invention has been described in detail as to specific embodiments thereof, it is not intended that these details constitute undue limitations upon the scope of the invention, excepting, of course, insofar as these limitations appear in the appended claims.
We claim:
1. In a process for preparing acrylic acid by the reaction of equivalent amounts of acetylene, carbon monoxide and water in the liquid phase at an elevated temperature and pressure in the presence of a catalyst, the improvement of carrying out said reaction in the presence of a combination of catalysts corresponding to the formulae Nil-n Gun wherein n is a value from 0 to 1; x represents a value from 0 to 20; X is a halogen atom selected from the group consisting of bromine, chlorine and iodine; and A represents a radical selected from the group consisting of an alkyl group having 1 to 18 carbon atoms, said alkyl substituent having 1 to 8 carbon atoms; an unsubstituted aryl group selected from the group consisting of phenyl and naphthyl; an alkyl substituted aryl group, said alkyl substituent having from 1 to 18 carbon atoms and said aryl group being selected from the group consisting of phenyl and naphthyl; and an aryl substituted alkyl group having 1 to 18 carbon atoms, said aryl substituent being selected from the group consisting of phenyl, tolyl, xylyl and naphthyl.
2. The process of claim 1 wherein the catalyst combination is the hydrated nickel salts of methane sulfonic acid having less than about 6 moles of combined water and a copper halide selected from the group consisting of copper chloride, copper bromide and copper iodide.
3. The process of claim 1 wherein the catalyst combination is the hydrated nickel salt of naphthalene-2-sulfonic acid having less than about 6 moles of combined water and a copper halide selected from the group consisting of copper chloride, copper bromide and copper iodide.
4. The process of claim 1 wherein the catalyst combination is the hydrated nickel salt of 2-tolyl-2-(tolyl sulfonic acid) butane having less than about 6 moles of combined water and a copper halide selected from the group consisting of copper chloride, copper bromide and copper iodide.
5. The process of claim 1 wherein the catalyst combination is the hydrated copper salt of decylbenzene sulfonic acid having less than about 6 moles of combined water and a nickel halide selected from the group consisting of nickel chloride, nickel bromide and nickel iodide.
6. The process of claim 1 wherein the catalyst combination is the hydrated nickel salt of xylene sulfonic acid having less than about 6 moles of combined water and a copper halide selected from the group consisting of copper chloride, copper bromide and copper iodide.
7. The process of claim 1 wherein the catalysts are present in sufi'icient amounts to provide from 0.1 to 8.0 percent by weight nickel salt, basis the total Weight of the non-gaseous reaction mixture, and from 0.02 to 5 percent by weight copper salt, basis the total weight of the non-gaseous reaction mixture.
8. The process of claim 1 wherein the catalysts are present in sufficient amounts to provide from 0.2 to 5.0 percent by weight nickel salt, basis the total weight of the non-gaseous reaction mixture, and from 0.5 to 1.0 percent by weight copper salt, basis the total weight of the non-gaseous reaction mixture.
References Cited in the file of this patent UNITED STATES PATENTS 2,806,040 Reppe et al. Sept. 10, 1957 FOREIGN PATENTS 750,538 Great Britain June 20, 1956 805,641 Germany May 25, 1951 863,194 Germany Ian. 15, 1953 OTHER REFERENCES Berkman et al.: Catalysis, p. 515 (1940). German application Serial No. B29,113, printed Dec. 27, 1956.

Claims (1)

1. IN A PROCESS FOR PREPARING ACRYLLIC ACID BY THE REACTION OF EQUIVALENT AMOUNTS OF ACETYLENE, CARBON MONOXIDE AND WATER IN THE LIQUID PHASE AT AN ELEVATED TEMPERTURE AND PRESSURE IN THE PRESENCE OF A CATALYST, THE IMPROVEMENT OF CARRYING OUT SAID REACTION IN THE PRESENCE OF A COMBINATION OF CATALYSTS CORESPONDING TO THE FORMULAE
US776403A 1958-11-26 1958-11-26 Acrylic monomers and the preparation thereof Expired - Lifetime US3025322A (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3210417A (en) * 1961-12-29 1965-10-05 American Cyanamid Co Preparation of acrylic monomers
US3247234A (en) * 1961-10-03 1966-04-19 Dow Chemical Co Cupric catalyst
US3268579A (en) * 1961-12-29 1966-08-23 American Cyanamid Co Preparation of acrylic acid
US3340296A (en) * 1966-06-06 1967-09-05 American Cyanamid Co Preparation of acrylic acid
US5364957A (en) * 1992-04-08 1994-11-15 Shell Oil Company Carbonylation process using palladium phosphine catalyst

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE29113C (en) * 1900-01-01 R. FLOSKY in Sagan Gas burner with preheating of the gas
DE805641C (en) * 1948-10-02 1951-05-25 Basf Ag Process for the production of ª ‡, ª ‰ -unsaturated carboxylic acids and their derivatives
DE863194C (en) * 1943-04-01 1953-01-15 Basf Ag Process for the preparation of carboxylic acids and carboxylic anhydrides
GB750538A (en) * 1953-02-17 1956-06-20 Basf Ag Improvements in the production of acrylic acid
US2806040A (en) * 1954-10-26 1957-09-10 Basf Ag Production of acrylic acid or its derivatives using a nickel halide catalyst in the presence of an activator containing sulfur or selenium

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE29113C (en) * 1900-01-01 R. FLOSKY in Sagan Gas burner with preheating of the gas
DE863194C (en) * 1943-04-01 1953-01-15 Basf Ag Process for the preparation of carboxylic acids and carboxylic anhydrides
DE805641C (en) * 1948-10-02 1951-05-25 Basf Ag Process for the production of ª ‡, ª ‰ -unsaturated carboxylic acids and their derivatives
GB750538A (en) * 1953-02-17 1956-06-20 Basf Ag Improvements in the production of acrylic acid
US2806040A (en) * 1954-10-26 1957-09-10 Basf Ag Production of acrylic acid or its derivatives using a nickel halide catalyst in the presence of an activator containing sulfur or selenium

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3247234A (en) * 1961-10-03 1966-04-19 Dow Chemical Co Cupric catalyst
US3210417A (en) * 1961-12-29 1965-10-05 American Cyanamid Co Preparation of acrylic monomers
US3268579A (en) * 1961-12-29 1966-08-23 American Cyanamid Co Preparation of acrylic acid
US3340296A (en) * 1966-06-06 1967-09-05 American Cyanamid Co Preparation of acrylic acid
US5364957A (en) * 1992-04-08 1994-11-15 Shell Oil Company Carbonylation process using palladium phosphine catalyst

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