CA1253174A - Process for making monocarboxylic anhydrides - Google Patents
Process for making monocarboxylic anhydridesInfo
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- CA1253174A CA1253174A CA000493588A CA493588A CA1253174A CA 1253174 A CA1253174 A CA 1253174A CA 000493588 A CA000493588 A CA 000493588A CA 493588 A CA493588 A CA 493588A CA 1253174 A CA1253174 A CA 1253174A
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- carrier
- stands
- supported catalyst
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/54—Preparation of carboxylic acid anhydrides
- C07C51/56—Preparation of carboxylic acid anhydrides from organic acids, their salts, their esters or their halides, e.g. by carboxylation
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Furan Compounds (AREA)
Abstract
PROCESS FOR MAKING MONOCARROXYLIC ANHYDRIDES
ABSTRACT OF THE DISCLOSURE
Monocarboxylic anhydrides of the general formula (RCO)2O
are made by reacting a carboxylic acid ester or dialkylether of the general formulae RCOOR and ROR, respectively, in which R each stands for one and the same alkyl group having from 1 to 4 carbon atoms, with carbon monoxide in gas phase in the presence of iodine or bromine or their compounds as a reac-tion promoter and also in the presence of a carrier-support-ed catalyst, at temperatures of from 130 to 400°C and under pressures of from 1 to 150 bars. More particularly, a carrier-supported catalyst is used which has an organosilicon com-pound containing an alkoxy or halogen group and also an or-ganonitrogen, oryanophosphorus, organoarsenic, organosulfur, mercapto or thioether group as a polyfunctional adhesion promoter additively combined with the carrier material on the one hand, and with a nickel compound, on the other hand.
ABSTRACT OF THE DISCLOSURE
Monocarboxylic anhydrides of the general formula (RCO)2O
are made by reacting a carboxylic acid ester or dialkylether of the general formulae RCOOR and ROR, respectively, in which R each stands for one and the same alkyl group having from 1 to 4 carbon atoms, with carbon monoxide in gas phase in the presence of iodine or bromine or their compounds as a reac-tion promoter and also in the presence of a carrier-support-ed catalyst, at temperatures of from 130 to 400°C and under pressures of from 1 to 150 bars. More particularly, a carrier-supported catalyst is used which has an organosilicon com-pound containing an alkoxy or halogen group and also an or-ganonitrogen, oryanophosphorus, organoarsenic, organosulfur, mercapto or thioether group as a polyfunctional adhesion promoter additively combined with the carrier material on the one hand, and with a nickel compound, on the other hand.
Description
3~7~
This invention rela-tes to a process for making mono-carboxylic anhydrides of the general formula (RCO)2O by reacting a carboxylic acid ester or dialkylether of the general formulae RCOOR and ROR, respectively, in which R each stands for one and the same alkyl group having from 1 to 4 carbon atoms, with car-bon monoxide in gas phase in -the presence of iodine or bromine or their compounds as a reaction promoter and also in the pres-ence of a carrier-supported catalyst, at temperatures of from 130 to 400C and under pressures of from 1 to 150 bars, which comprises: using a carrier-supported catalys-t having an organo-silicon compound as a polyfunctional adhesion promoter bound to the carrier material on the one hand, and to a nickel compound on the other hand, the organosilicon compound corresponding to one of the following general Eormulae:
I. Rlx Si-(CR3) -Y or II. RnX3_nSi-(cR2)m-cHy2 or . 1 . 3 ILI. [Rnx3-nsl-(cR2)m]2 in which X stands for -Cl,-Br or -OR ;
Y stands for -NR2, -PR2, -~sR2, -SR or -SH;
Z stands for -NR -, -PR -, -~sR4- or -S-;
Rl stands for a Cl-C5-alkyl;
R stands for a Cl-C3-alkyl;
R stands for -H, a Cl-C5-alkyl or -C6H5;
R4 stands for a Cl-C6-alkyl, a C5-Cg-cycloalkyl or 6 5 6 5 2 ;
n stands for 0 or 1 or 2;
m stands for 0 -through 8.
~2~3~l~7~
23343-~00 A process of this kind carried out in gas phase with the use of a carrier-supported catalyst has already been dis-closed in German Specification DE-OS 24 50 965 and Japanese Specification JP-OS No. 47921/1975, which permits the disadvan-t-ages accompanying liquid-phase methods, namely the difficult separation and recycle of suspended and partially dissolved ca-talyst and optionally promoter, to be avoided.
The gas phase processes described in the two specific-ations use solid carrier-supported catalysts made by impregnat-ing the carrier with a catalyst solution containing noble metals.In this way, it is not possible, however, e.g. for organonitrog-en or organophosphorus compounds containing trivalent nitrogen and phosphorus, respectively, to be fixed in the carrier-support-ed catalyst, and this has been found generally to affect the activity of the catalyst and selectivity of the reaction.
The present invention also permits -the above deficien-cies to be obviated, however, by the use of so-called poly-functional adhesion promoters (spacers) which already have prom-oters of group, V, e.g. organylamines or phosphines, integrated therein, and permit nickel compounds to be fixed to the catalyst surface.
The invention is more specifically characterized by the fact that the carrier-supported catalyst has an organosilicon compound containing an alkoxy or halogen group and also an organonitrogen, organophosphorus, organoarsenic, organosulfur, mercapto or thioether group as a polyfunctional adhesion promoter bound to the carrier material on the one hand, and to a nickel compound, on -the other hand.
Further preferred and optional features of the process ~ `
~2~3~79~
of this invention provide:
a) for the carrier-supported catalyst additionally to con-tain as a promoter a metal compound seleeted from the 1st through 3rd principal groups or the 4th through 7th subgroups of the Periodic System of the elements;
b) for the organosilicon compound as the polyfunctional adhesion promoter in the carrier-supported catalyst to be bound to the carrier material on the one hand, and alternately to the nickel compound and to a metal compound selected from the 5th through 7th subgroups of the Periodic System of the elements on the other hand;
c) in the organosilicon compound of the formula III, R4 stands for a Cl- C6 -alkyl, a C5- C8-eycloalkyl or C6H5 or C6H5CH2- which may be substituted with a halogen, methoxy, ethoxy or a Cl- C3-alkyl;
m stands for 1 through 3;
d) for the earrler-supported eatalyst to eontain an inor-ganie oxidie earrier or an active carbon carrier the residual active hydroxy groups of which were inactivated by esterifica-0 tion or etherification;e) for the carrier-supported catalyst to contain from 0.01 -to 50 wg-t %, preferably 0.1 to 20 wgt %, nickel compound, adhesion promo-ter and further non noble metal compound, ii desir-ed;
f) Eor the carrier-supported catalyst to be used in form 1"',``
~5~7~
of particles with a size of from 1 to 20 mm.
The catalys-t carriers should preferably be selected from inorganic oxides, e.g. SiO2, Al203, MgO, TiO2, La203, ZrO2, zeoli-tes, clay, NiO, Cr203, W03 or corresponding mixed oxides but also active carbon having a BET-surface area of from 1 to 1000 m2/g, preferably 30 to 400 m2/g, and presenting OH-groups.
These OH-groups undergo reaction with the functi.onal group or groups X of the adhesion promoter with formation of oxygen bridges between carrier and adhesion promoter. The promoters of the 5th or 6th principal group are chemically combined with the adhesion promoter and are themselves one of its functional groups which have the nickel compounds linked thereto, if desired alternately with metal compounds from the 5th to 7th subgroups, especially vanadium, bromium or rhenium.
These nickel compound~s and further non-noble metal compounds, if any, may well form bridges between individual adhesion promoter molecules fixed to the carrier.
An advantage of the present process resides in the fact that the promoters increasing the catalyst activity and se-lectivity, which are selected from principal group V or VIof the Periodic System of the elements, form a functional group Y or Z in a polyfunctional adhesion promoter and can thus be fixed up to maximum concen-tration which is determined by the number of OH-groups on the carrier surface. This is the reason why it is not necessary for an organonitrogen or organophosphorus promoter, for example, to be separated and recycled. The process of this invention for making monocar-boxylic anhydrides compares favorably in catalyst activity and selectivity with the prior processes referred to herein-~2~3~7~
above carriea out in gas phase with the use of a carrier-supported catalyst. In addition to this, the carri.er-supported catalysts used in accordance with this invention are free from expensive noble metals of groups VIII of the Periodic System of the elements.
The process of this invention is more especially used for making acetic anhydride from methyl acetate or dimethyl-ether in the presence of methyl iodide or methyl bromide as a reaction promoter. HI, HBr or more generally RI or RBr, where R s~ands for an alkyl group having from 1 to 4 carbon atoms1 can also be used as a reaction promoter.
In the general formulae defining the organosilicon com-pounds which should conceniently be used as adhesion promo-ters (spacers), X preferably stands for -OR and more prefe-rably for methoxy and ethoxy. If n stands for 1 or 2, R1 preferably stands for an unbranched alkyl group, especially methyl, ethyl or propyl.
The useful carrier materials have already been specified hereinabove; useful mixed oxides are e.g. Cr203 - Al203, W03 -20 Al203, MgO - Al203, SiO2 - Al203 or ZrO2 - Al203. The carrler-supported catalyst preferably contains from 0.01 to 5 wgt %
nickel.
The nickel compounds useful for making the carrier-suppor-t-ed catalyst comprise e.y. the following compounds:
25 Ni(C3)4, L-P (c6H5)3 72Ni(co)2~ Ni(c3Hl2)2l 2 The metal compounds from the first to third principal groups or from the 4th through 7th subgroups of the Periodic System, preferably of Li, Na, Mg, Ca, Al, Ti, Zr, V, Cr, W, Re, should conveniently be selcted from hydroxides, carbonates, ~2~3~
carbonyls, hydrides, halides and further salts. The metal compounds can be used in form of a solution for impregnat-ing the catalyst carrier therewith.
For preparation of the carrier-supported catalyst of this invention, it is necessary to have the polyfunctional adhesion promoter (organosilicon compound) which is a commercially available product or can be made by methods described in literature. Speaking generally, one of the nickel compounds speciEied and, if desired, one of the me-tal compounds of the 5th to 7th subgroups is linked to theadhesion promoter, namely to promoter group Y or Z contain-ing an element selected from the 5th or 6th principal group. Next, the nickel-containing intermediary product is reactively combined with the hydroxy groups of the carrier material with escape of a group X as a compound XH (e.g.
HCl, HBr, or R OH). This is achieved by heating the com-pounds suspended in an unpolar solvent (e.g. benzene, toluene, xylene) over a period of 24 to 100 hours until decolorized.
Alternatively, it is also possible first reactively to combine the polyfunctional adhesion promoter (organo-silicon compound) with the hydroxy groups of the carrier with escape of a group X as a compound XH, and then additi-vely to combine the nickel compound and, if desired, one of the metal compounds of the 5th to 7th subgroup wi-th the promoter group Y or Z of -the lntermediary product.
Details are indicated in tha catalyst description herainaEter.
In order to increase the selectivity and suppress - ~ ~r- ~
side reactions, it is good practice, especially for discon-tinuous operation but also for the initial phase in a con-tinuous process, to inactivate those residual 0~l-groups on the surface of the catalyst carrier which have not reacted with the functional yroups X of the adhesion promoter. This can be done e.g. by silylation with trimethylchlorosilane, methylation with methyl iodide or acetylation with acetic anhydride.
The quantitative ratio of carboxylic acid ester or di-alkylether and iodine(compound) or brominetcompound) in the reaction zone may vary within wide limits. Generally, howaver, 1 to 500 mols, preferably 1 to 100 mols, carboxy-lic acid ester and/or dialkylether is used per 1 mol iodine(compound) or bromine(compound). The temperature se-lected for the reaction zone should be high enough to al-ways have a gaseous reaction mixture therein, irrespective of the conversion rate, and preferably is between 170 and 250C. The preferred pressure is between 10 and 40 bars.
The reaction mixture should convaniently be contacted with the solid carrier-supported catalyst over a period of from 1 -to lûO0 seconds, preferably 1 to 180 seconds. The conversion should suitably be effected in a flow tube arranged in upright position, packed with the carrier-supported catalyst or in an autoclave provided with a stirrer or in a shaking autoclave, having the carrier-supported catalyst placed therein. While the carbonylation is generally effected under practically anhydrous con-ditions, lt is allowable for it to be carried out in the presence of minor amounts of water as normally found in 3~
commercial starting materials, which however should not exceed 1 mol %, based on the starting materials. In addition, the carbonylation remains substantially uneffected by the presence of minor amoun-ts of methanol in the starting mate-rials or of hydrogen in commercial carbon monoxida.
The reaction mixture coming from the carbonylation zoneis gaseous and contains carbon monoxide, methyL iodide, acetic anhydride, unreacted methyl acetate or dimethylether and, under circumstances, minor proportions of acetic acid.
lû The gaseous reaction mixture is cooled with condensation of acetic anhydride and, under circumstances, acetic acid. Un-condensed gases, such as C0, CH3I, methyl acetate or dimethyl-ether are recycled to the reaction zone, the reacted ester or ether and C0 portions being continuously renewed. The anhydrides are easy to separate, i.e. in uncomplicated fashion, by cooling the effluent reaction mixture and re-cycling the uncondensed gas. This is a particular advantage of the process of this invention. The carrier-supported catalyst is not con-taminated; it remains in the reac-tion zone. As a rasult, the entire process is rendered consider-ably simpler.
Example 1
This invention rela-tes to a process for making mono-carboxylic anhydrides of the general formula (RCO)2O by reacting a carboxylic acid ester or dialkylether of the general formulae RCOOR and ROR, respectively, in which R each stands for one and the same alkyl group having from 1 to 4 carbon atoms, with car-bon monoxide in gas phase in -the presence of iodine or bromine or their compounds as a reaction promoter and also in the pres-ence of a carrier-supported catalyst, at temperatures of from 130 to 400C and under pressures of from 1 to 150 bars, which comprises: using a carrier-supported catalys-t having an organo-silicon compound as a polyfunctional adhesion promoter bound to the carrier material on the one hand, and to a nickel compound on the other hand, the organosilicon compound corresponding to one of the following general Eormulae:
I. Rlx Si-(CR3) -Y or II. RnX3_nSi-(cR2)m-cHy2 or . 1 . 3 ILI. [Rnx3-nsl-(cR2)m]2 in which X stands for -Cl,-Br or -OR ;
Y stands for -NR2, -PR2, -~sR2, -SR or -SH;
Z stands for -NR -, -PR -, -~sR4- or -S-;
Rl stands for a Cl-C5-alkyl;
R stands for a Cl-C3-alkyl;
R stands for -H, a Cl-C5-alkyl or -C6H5;
R4 stands for a Cl-C6-alkyl, a C5-Cg-cycloalkyl or 6 5 6 5 2 ;
n stands for 0 or 1 or 2;
m stands for 0 -through 8.
~2~3~l~7~
23343-~00 A process of this kind carried out in gas phase with the use of a carrier-supported catalyst has already been dis-closed in German Specification DE-OS 24 50 965 and Japanese Specification JP-OS No. 47921/1975, which permits the disadvan-t-ages accompanying liquid-phase methods, namely the difficult separation and recycle of suspended and partially dissolved ca-talyst and optionally promoter, to be avoided.
The gas phase processes described in the two specific-ations use solid carrier-supported catalysts made by impregnat-ing the carrier with a catalyst solution containing noble metals.In this way, it is not possible, however, e.g. for organonitrog-en or organophosphorus compounds containing trivalent nitrogen and phosphorus, respectively, to be fixed in the carrier-support-ed catalyst, and this has been found generally to affect the activity of the catalyst and selectivity of the reaction.
The present invention also permits -the above deficien-cies to be obviated, however, by the use of so-called poly-functional adhesion promoters (spacers) which already have prom-oters of group, V, e.g. organylamines or phosphines, integrated therein, and permit nickel compounds to be fixed to the catalyst surface.
The invention is more specifically characterized by the fact that the carrier-supported catalyst has an organosilicon compound containing an alkoxy or halogen group and also an organonitrogen, organophosphorus, organoarsenic, organosulfur, mercapto or thioether group as a polyfunctional adhesion promoter bound to the carrier material on the one hand, and to a nickel compound, on -the other hand.
Further preferred and optional features of the process ~ `
~2~3~79~
of this invention provide:
a) for the carrier-supported catalyst additionally to con-tain as a promoter a metal compound seleeted from the 1st through 3rd principal groups or the 4th through 7th subgroups of the Periodic System of the elements;
b) for the organosilicon compound as the polyfunctional adhesion promoter in the carrier-supported catalyst to be bound to the carrier material on the one hand, and alternately to the nickel compound and to a metal compound selected from the 5th through 7th subgroups of the Periodic System of the elements on the other hand;
c) in the organosilicon compound of the formula III, R4 stands for a Cl- C6 -alkyl, a C5- C8-eycloalkyl or C6H5 or C6H5CH2- which may be substituted with a halogen, methoxy, ethoxy or a Cl- C3-alkyl;
m stands for 1 through 3;
d) for the earrler-supported eatalyst to eontain an inor-ganie oxidie earrier or an active carbon carrier the residual active hydroxy groups of which were inactivated by esterifica-0 tion or etherification;e) for the carrier-supported catalyst to contain from 0.01 -to 50 wg-t %, preferably 0.1 to 20 wgt %, nickel compound, adhesion promo-ter and further non noble metal compound, ii desir-ed;
f) Eor the carrier-supported catalyst to be used in form 1"',``
~5~7~
of particles with a size of from 1 to 20 mm.
The catalys-t carriers should preferably be selected from inorganic oxides, e.g. SiO2, Al203, MgO, TiO2, La203, ZrO2, zeoli-tes, clay, NiO, Cr203, W03 or corresponding mixed oxides but also active carbon having a BET-surface area of from 1 to 1000 m2/g, preferably 30 to 400 m2/g, and presenting OH-groups.
These OH-groups undergo reaction with the functi.onal group or groups X of the adhesion promoter with formation of oxygen bridges between carrier and adhesion promoter. The promoters of the 5th or 6th principal group are chemically combined with the adhesion promoter and are themselves one of its functional groups which have the nickel compounds linked thereto, if desired alternately with metal compounds from the 5th to 7th subgroups, especially vanadium, bromium or rhenium.
These nickel compound~s and further non-noble metal compounds, if any, may well form bridges between individual adhesion promoter molecules fixed to the carrier.
An advantage of the present process resides in the fact that the promoters increasing the catalyst activity and se-lectivity, which are selected from principal group V or VIof the Periodic System of the elements, form a functional group Y or Z in a polyfunctional adhesion promoter and can thus be fixed up to maximum concen-tration which is determined by the number of OH-groups on the carrier surface. This is the reason why it is not necessary for an organonitrogen or organophosphorus promoter, for example, to be separated and recycled. The process of this invention for making monocar-boxylic anhydrides compares favorably in catalyst activity and selectivity with the prior processes referred to herein-~2~3~7~
above carriea out in gas phase with the use of a carrier-supported catalyst. In addition to this, the carri.er-supported catalysts used in accordance with this invention are free from expensive noble metals of groups VIII of the Periodic System of the elements.
The process of this invention is more especially used for making acetic anhydride from methyl acetate or dimethyl-ether in the presence of methyl iodide or methyl bromide as a reaction promoter. HI, HBr or more generally RI or RBr, where R s~ands for an alkyl group having from 1 to 4 carbon atoms1 can also be used as a reaction promoter.
In the general formulae defining the organosilicon com-pounds which should conceniently be used as adhesion promo-ters (spacers), X preferably stands for -OR and more prefe-rably for methoxy and ethoxy. If n stands for 1 or 2, R1 preferably stands for an unbranched alkyl group, especially methyl, ethyl or propyl.
The useful carrier materials have already been specified hereinabove; useful mixed oxides are e.g. Cr203 - Al203, W03 -20 Al203, MgO - Al203, SiO2 - Al203 or ZrO2 - Al203. The carrler-supported catalyst preferably contains from 0.01 to 5 wgt %
nickel.
The nickel compounds useful for making the carrier-suppor-t-ed catalyst comprise e.y. the following compounds:
25 Ni(C3)4, L-P (c6H5)3 72Ni(co)2~ Ni(c3Hl2)2l 2 The metal compounds from the first to third principal groups or from the 4th through 7th subgroups of the Periodic System, preferably of Li, Na, Mg, Ca, Al, Ti, Zr, V, Cr, W, Re, should conveniently be selcted from hydroxides, carbonates, ~2~3~
carbonyls, hydrides, halides and further salts. The metal compounds can be used in form of a solution for impregnat-ing the catalyst carrier therewith.
For preparation of the carrier-supported catalyst of this invention, it is necessary to have the polyfunctional adhesion promoter (organosilicon compound) which is a commercially available product or can be made by methods described in literature. Speaking generally, one of the nickel compounds speciEied and, if desired, one of the me-tal compounds of the 5th to 7th subgroups is linked to theadhesion promoter, namely to promoter group Y or Z contain-ing an element selected from the 5th or 6th principal group. Next, the nickel-containing intermediary product is reactively combined with the hydroxy groups of the carrier material with escape of a group X as a compound XH (e.g.
HCl, HBr, or R OH). This is achieved by heating the com-pounds suspended in an unpolar solvent (e.g. benzene, toluene, xylene) over a period of 24 to 100 hours until decolorized.
Alternatively, it is also possible first reactively to combine the polyfunctional adhesion promoter (organo-silicon compound) with the hydroxy groups of the carrier with escape of a group X as a compound XH, and then additi-vely to combine the nickel compound and, if desired, one of the metal compounds of the 5th to 7th subgroup wi-th the promoter group Y or Z of -the lntermediary product.
Details are indicated in tha catalyst description herainaEter.
In order to increase the selectivity and suppress - ~ ~r- ~
side reactions, it is good practice, especially for discon-tinuous operation but also for the initial phase in a con-tinuous process, to inactivate those residual 0~l-groups on the surface of the catalyst carrier which have not reacted with the functional yroups X of the adhesion promoter. This can be done e.g. by silylation with trimethylchlorosilane, methylation with methyl iodide or acetylation with acetic anhydride.
The quantitative ratio of carboxylic acid ester or di-alkylether and iodine(compound) or brominetcompound) in the reaction zone may vary within wide limits. Generally, howaver, 1 to 500 mols, preferably 1 to 100 mols, carboxy-lic acid ester and/or dialkylether is used per 1 mol iodine(compound) or bromine(compound). The temperature se-lected for the reaction zone should be high enough to al-ways have a gaseous reaction mixture therein, irrespective of the conversion rate, and preferably is between 170 and 250C. The preferred pressure is between 10 and 40 bars.
The reaction mixture should convaniently be contacted with the solid carrier-supported catalyst over a period of from 1 -to lûO0 seconds, preferably 1 to 180 seconds. The conversion should suitably be effected in a flow tube arranged in upright position, packed with the carrier-supported catalyst or in an autoclave provided with a stirrer or in a shaking autoclave, having the carrier-supported catalyst placed therein. While the carbonylation is generally effected under practically anhydrous con-ditions, lt is allowable for it to be carried out in the presence of minor amounts of water as normally found in 3~
commercial starting materials, which however should not exceed 1 mol %, based on the starting materials. In addition, the carbonylation remains substantially uneffected by the presence of minor amoun-ts of methanol in the starting mate-rials or of hydrogen in commercial carbon monoxida.
The reaction mixture coming from the carbonylation zoneis gaseous and contains carbon monoxide, methyL iodide, acetic anhydride, unreacted methyl acetate or dimethylether and, under circumstances, minor proportions of acetic acid.
lû The gaseous reaction mixture is cooled with condensation of acetic anhydride and, under circumstances, acetic acid. Un-condensed gases, such as C0, CH3I, methyl acetate or dimethyl-ether are recycled to the reaction zone, the reacted ester or ether and C0 portions being continuously renewed. The anhydrides are easy to separate, i.e. in uncomplicated fashion, by cooling the effluent reaction mixture and re-cycling the uncondensed gas. This is a particular advantage of the process of this invention. The carrier-supported catalyst is not con-taminated; it remains in the reac-tion zone. As a rasult, the entire process is rendered consider-ably simpler.
Example 1
2 ml (1.86 9) methyl acetate, 0.5 ml (1.14 9) rnethyl iodide and 3.15 9 catalyst of the formula L-A12o3~o-Si-CH2-CH2-P(C6H5)2 72Ni( )2 ~3~
were reacted with carbon monoxide in a stainless steel (Hastelloy C) autoclave having a capacity of 0.25 liter, at 200C under a C0-pressure of 20 bars. The space/time-yield after a reaction period of 1 h was 140 9 Ac20/g Ni per hour The yield of Ac20, based on the ester used,was 22 %
for a selectivity of 92 %.
Example 2 1.86 ml dimethylether, 0,5 ml (1.14 9) methyl iodide 10 and 3.15 9 of the catalyst of Example 1 were reacted in the autoclave of Example 1 at 200C under a C0-pressure of 20 bars. Acetic anhydride was obtained in a space/time-yield of 30 9 Ac20 per 9 Ni per hour. The experiment was run over a period of 5 hours.
The yield of Ac20, based on the ether used, was 6 %
for a selectivlty of 19 %.
Preparation of the catalyst of the formula:
/-Al2o3~o-si-cH2-cH2-p(c6~ls)2-72Ni( )2 OC2~l5 Aluminum oxide was activated by drying it over a period of 10 hours at 200C under a préssure of 0.1 to 0.2 mi].li-bar.
The catalyst was prepared in the presence of nitrogen with exclusion of oxygen and water, all of the reactants having been dried previously using a molecular screen 4 A.
65 mg (~.4 mg Ni.) of the compound of the formula (C2H50)36i-cH2cH2p(c6H5)2 /2Ni(C0)2, dissolved in 40 ml ~ ~J~de ~a~
~L~S3~'7~
xylene, was added whila stirring to 3.2 9 activated aluminum oxide (99 % Al203) which consisted substantially of particles with a diameter of 3 mm, had an inner BET-surface area of 125 m2/g and a pore volume of 0.9 ml per 9, and the mixture was brought to boiling. After having been refluxed over a period of 72 hours, the solution was found to have been com-pletely decolorized. The solvent was separated and the catalyst was given into a Soxhlet. After 12 h Soxhlet-extrac-tion with benzene, the catalyst was dried over a period of 8 hours at 85C under a pressure of 1.33 millibar.
To suppress side-reactions and improve the selectivity, the catalyst was ultimately treated with trimethylchloro-silane.
Al203~0H ~ Cl-Si(CH3)3 ) Al203~U-si(cH3)3 r To this end, the catalyst was completely covered at room temperature with trimethylchlorosilane. The suspension was heated to boiling and boiled under reflux until gas ceased to be evolved. Next, the suspension was allowed to cool, the catalyst was separated from the liquid and dried over a period of 12 hours at 85C under 1.33 millibar.
The concentrated solvents were free from nickel. The catalyst so made contained 0.13 wgt % nickel.
The intermediate compound of the formula
were reacted with carbon monoxide in a stainless steel (Hastelloy C) autoclave having a capacity of 0.25 liter, at 200C under a C0-pressure of 20 bars. The space/time-yield after a reaction period of 1 h was 140 9 Ac20/g Ni per hour The yield of Ac20, based on the ester used,was 22 %
for a selectivity of 92 %.
Example 2 1.86 ml dimethylether, 0,5 ml (1.14 9) methyl iodide 10 and 3.15 9 of the catalyst of Example 1 were reacted in the autoclave of Example 1 at 200C under a C0-pressure of 20 bars. Acetic anhydride was obtained in a space/time-yield of 30 9 Ac20 per 9 Ni per hour. The experiment was run over a period of 5 hours.
The yield of Ac20, based on the ether used, was 6 %
for a selectivlty of 19 %.
Preparation of the catalyst of the formula:
/-Al2o3~o-si-cH2-cH2-p(c6~ls)2-72Ni( )2 OC2~l5 Aluminum oxide was activated by drying it over a period of 10 hours at 200C under a préssure of 0.1 to 0.2 mi].li-bar.
The catalyst was prepared in the presence of nitrogen with exclusion of oxygen and water, all of the reactants having been dried previously using a molecular screen 4 A.
65 mg (~.4 mg Ni.) of the compound of the formula (C2H50)36i-cH2cH2p(c6H5)2 /2Ni(C0)2, dissolved in 40 ml ~ ~J~de ~a~
~L~S3~'7~
xylene, was added whila stirring to 3.2 9 activated aluminum oxide (99 % Al203) which consisted substantially of particles with a diameter of 3 mm, had an inner BET-surface area of 125 m2/g and a pore volume of 0.9 ml per 9, and the mixture was brought to boiling. After having been refluxed over a period of 72 hours, the solution was found to have been com-pletely decolorized. The solvent was separated and the catalyst was given into a Soxhlet. After 12 h Soxhlet-extrac-tion with benzene, the catalyst was dried over a period of 8 hours at 85C under a pressure of 1.33 millibar.
To suppress side-reactions and improve the selectivity, the catalyst was ultimately treated with trimethylchloro-silane.
Al203~0H ~ Cl-Si(CH3)3 ) Al203~U-si(cH3)3 r To this end, the catalyst was completely covered at room temperature with trimethylchlorosilane. The suspension was heated to boiling and boiled under reflux until gas ceased to be evolved. Next, the suspension was allowed to cool, the catalyst was separated from the liquid and dried over a period of 12 hours at 85C under 1.33 millibar.
The concentrated solvents were free from nickel. The catalyst so made contained 0.13 wgt % nickel.
The intermediate compound of the formula
3 2 2 ( 6 5)2_/2Ni(C)2 from (C2H5o)3sicH CH P(C H ) and Ni(C0)4 with escape of C0-gas was prepared as described by A.K. Smith e-t al.. J. mol. Catal. 2 (1977), page 223. The 3~t7~
compound of the formula (C2H50)3SiCH2CH2P(C6H5)2 from tri-ethoxyvinylsilane and diphenylphosphine with exposure to ultraviolet light was made as described by H. Nieberyall, Makromol Chem. 52 (19~2), page 21S.
compound of the formula (C2H50)3SiCH2CH2P(C6H5)2 from tri-ethoxyvinylsilane and diphenylphosphine with exposure to ultraviolet light was made as described by H. Nieberyall, Makromol Chem. 52 (19~2), page 21S.
Claims (9)
1. A process for making monocarboxylic anhydrides of the general formula (RCO)2O by reacting a carboxylic acid ester or dialkylether of the general formulae RCOOR and ROR, respectively, in which R each stands for one and the same alkyl group having from 1 to 4 carbon atoms, with carbon monoxide in gas phase in the presence of iodine or bromine or their compounds as a reaction pro-moter and also in the presence of a carrier-supported catalyst, at temperatures of from 130 to 400°C and under pressures of from 1 to 150 bars, which comprises: using a carrier-supported catalyst having an organosilicon compound as a polyfunctional adhesion promoter bound to the carrier material on the one hand, and to a nickel compound on the other hand, the organosilicon compound corresponding to one of the following general formulae:
I. R?X3-nSi-(CR?)m-Y or II. R?X3-nSi-(CR?)m-CHY2 or III. [R?X3-nSi-(CR?)m]2Z
in which X stands for -C1,-Br or -OR2;
Y stands for -NR?, -PR?, -AsR?, -SR4 or -SH;
Z stands for -NR4-, -PR4-, -AsR4- or -S-;
R1 stands for a C1-C5-alkyl;
R2 stands for a C1-C3-alkyl;
R3 stands for -H, a C1-C5-alkyl or -C6H5;
R4 stands for a C1-C6-alkyl, a C5-C8-cyclo-alkyl or -C6H5 or C6H5CH2;
n stands for 0 or 1 or 2;
m stands for 0 through 8.
I. R?X3-nSi-(CR?)m-Y or II. R?X3-nSi-(CR?)m-CHY2 or III. [R?X3-nSi-(CR?)m]2Z
in which X stands for -C1,-Br or -OR2;
Y stands for -NR?, -PR?, -AsR?, -SR4 or -SH;
Z stands for -NR4-, -PR4-, -AsR4- or -S-;
R1 stands for a C1-C5-alkyl;
R2 stands for a C1-C3-alkyl;
R3 stands for -H, a C1-C5-alkyl or -C6H5;
R4 stands for a C1-C6-alkyl, a C5-C8-cyclo-alkyl or -C6H5 or C6H5CH2;
n stands for 0 or 1 or 2;
m stands for 0 through 8.
2. A process as claimed in claim 1, wherein the carrier-supported catalyst additionally contains as a promoter a compound containing a metal selected from the 1st through 3rd principal groups or the 4th through 7th subgroups of the Periodic System of the elements.
3. A process as claimed in claim 2, wherein the organosili-con compound as the polyfunctional adhesion promoter in the carrier-supported catalyst is bound to the carrier material on the one hand and alternately to the nickel compound and to a metal compound selected from the 5th through 7th subgroups of the Periodic System of the ele-ments on the other hand.
4. A process as claimed in claim 1, wherein R4 stands for -C6H5 or C6H5CH2 substituted with a halogen, methoxy, ethoxy or C1-C3-alkyl.
5. A process as claimed in claim 1, wherein m stands for 1 or 2 or 3.
6. A process as claimed in claim 1, wherein the carrier-supported catalyst contains an inorganic oxidic carrier or an active carbon carrier, the residual active hydroxy groups of which were inactivated by esterification or etherification.
7. A process as claimed in claim 1, wherein the carrier-supported catalyst contains from 0.01 to 50 wgt % nickel compound and adhesion promoter.
8. A process as claimed in claim 2, wherein the carrier-supported catalyst contains a total quantity of from 0.01 to 50 wgt % nickel compound, adhesion promoter and further non noble metal compounds.
9. A process as claimed in claim 1, wherein the carrier-supported catalyst is used in form of particles with a size of from 1 to 20 mm.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP3440644.1 | 1984-11-07 | ||
| DE19843440644 DE3440644A1 (en) | 1984-11-07 | 1984-11-07 | METHOD FOR PRODUCING MONOCARBONIC ACID ANHYDRIDES |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1253174A true CA1253174A (en) | 1989-04-25 |
Family
ID=6249704
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000493588A Expired CA1253174A (en) | 1984-11-07 | 1985-10-22 | Process for making monocarboxylic anhydrides |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0181502B1 (en) |
| JP (1) | JPH0710788B2 (en) |
| AT (1) | ATE32059T1 (en) |
| CA (1) | CA1253174A (en) |
| DE (2) | DE3440644A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0203286B1 (en) * | 1985-03-27 | 1988-09-14 | Hoechst Aktiengesellschaft | Supported catalyst and procedure for the production of monocarboxylic acid anhydrides |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3907852A (en) * | 1972-06-23 | 1975-09-23 | Exxon Research Engineering Co | Silylhydrocarbyl phosphines and related compounds |
| JPS5926611B2 (en) * | 1973-08-24 | 1984-06-29 | 昭和電工株式会社 | Method for producing acetic anhydride |
| DE2450965C2 (en) * | 1974-10-26 | 1983-06-09 | Hoechst Ag, 6230 Frankfurt | Process for the production of acetic anhydride |
| US4007130A (en) * | 1975-12-29 | 1977-02-08 | Monsanto Company | Catalyst regeneration method |
| JPS5459214A (en) * | 1977-10-11 | 1979-05-12 | Mitsubishi Gas Chem Co Inc | Preparation of carboxylic acid anhydride |
| DE2834691C2 (en) * | 1978-08-08 | 1983-11-10 | Degussa Ag, 6000 Frankfurt | MONOMERS, POLYMERS AND CARRIER-FIXED RHODIUM COMPLEX COMPOUNDS, METHOD FOR THEIR PRODUCTION AND USE AS CATALYSTS |
| US4284586A (en) * | 1979-12-26 | 1981-08-18 | Halcon Research And Development Corp. | Process for the preparation of acetic anhydride |
| DE3266549D1 (en) * | 1981-07-13 | 1985-10-31 | Mitsubishi Gas Chemical Co | Process for producing acetic anhydride |
| JPS5940377A (en) * | 1982-08-30 | 1984-03-06 | Hitachi Ltd | Pickup servo circuit |
-
1984
- 1984-11-07 DE DE19843440644 patent/DE3440644A1/en not_active Withdrawn
-
1985
- 1985-10-11 AT AT85112887T patent/ATE32059T1/en not_active IP Right Cessation
- 1985-10-11 DE DE8585112887T patent/DE3561457D1/en not_active Expired
- 1985-10-11 EP EP85112887A patent/EP0181502B1/en not_active Expired
- 1985-10-22 CA CA000493588A patent/CA1253174A/en not_active Expired
- 1985-11-07 JP JP60248155A patent/JPH0710788B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| DE3561457D1 (en) | 1988-02-25 |
| JPH0710788B2 (en) | 1995-02-08 |
| EP0181502B1 (en) | 1988-01-20 |
| EP0181502A1 (en) | 1986-05-21 |
| JPS61118341A (en) | 1986-06-05 |
| ATE32059T1 (en) | 1988-02-15 |
| DE3440644A1 (en) | 1986-05-07 |
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