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CA1264164A - Process for making monocarboxylic anhydrides - Google Patents

Process for making monocarboxylic anhydrides

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CA1264164A
CA1264164A CA000493586A CA493586A CA1264164A CA 1264164 A CA1264164 A CA 1264164A CA 000493586 A CA000493586 A CA 000493586A CA 493586 A CA493586 A CA 493586A CA 1264164 A CA1264164 A CA 1264164A
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carrier
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compound
catalyst
noble metal
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Gerhard Luft
Gebhard Ritter
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Hoechst AG
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Hoechst AG
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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
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
    • 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
    • B01J31/1616—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts
    • B01J31/1625—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts immobilised by covalent linkages, i.e. pendant complexes with optional linking groups
    • B01J31/1633—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts immobilised by covalent linkages, i.e. pendant complexes with optional linking groups covalent linkages via silicon containing groups
    • 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
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • 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
    • 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
    • B01J2531/60—Complexes comprising metals of Group VI (VIA or VIB) as the central metal
    • B01J2531/62—Chromium
    • 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
    • B01J2531/82—Metals of the platinum group
    • B01J2531/822—Rhodium
    • 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
    • B01J2531/82—Metals of the platinum group
    • B01J2531/827—Iridium

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Furan Compounds (AREA)

Abstract

PROCESS FOR MAKING MONOCARBOXYLIC 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-supported catalyst containing a compound of a noble metal belonging to group VIII of the Periodic System, 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 compound containing an alkoxy or halogen group and also an organonitrogen, organophosphorus, organo-arsenic, organosulfur, mercapto or thioether group as a poly-functional adhesion promoter additively combined with the carrier material on the one hand, and with the noble metal compound on the other hand.

Description

6~L

Th1s invention relates to a process for making mono-carboxylic anhydrides oF the general tormula (RCO)20 by re-acting a carboxylic acid ester or dialkylether of the gene-ral Formulae RCOOR and ROR, respectively, in which R 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 promoter and in the presence of a carrier-supported catalyst contain-ing a compound of a noble metal belonging to group 8 of the Periodic System, at temperatures of.from 130 to 400C under pressuresof from 1 - 150 bars.
A process of this kind carried out in gas phase with the use of a carrier-supported catalyst has already been disclosed in German Specification DE-OS 24 50 965 and Japa-nese Specification JP-OS No. 47921/1975, which p-ermits the disadvantages accompanying liquid-phase methods, namely the difficult separation and recycle of suspended and partially dissolved catalyst and optionally promoter, to be avoided.
The gas phase processes described i.n the two specifica-tions use solid carrier-supported catalysts made by impre-gnating the carrier with a catalyst solution. In this way, it is not possible, however, e.g. for organonitrogen or or-ganophosphorus compounds containing trivalent nitrogen and phosphorus, respectively, to be fixed in the carrier-sup-ported catalyst, and this has been found generally to adver-sely 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-6~L
- 2 - 23343-7g9 functional ad~.esion promoters (spacers) which already have promoters of group V, e,g. organylamines or phosphines, inte-yrated therein.
The invention provides a process for making mono-carboxylic anhydrides of the general formula (RC0)20 by react-ing a carboxylic acid ester or dialkylether of the general formulae RCOOR an~ ROR, respectively, in which R each stands for one and the same alkyl group having from l to 4 carbon atoms, with carbon monoxide in gas phase in the presence of iodine or bromine or their compounds as a reaction promoter and also in the presence of a carrier~supported catalyst containing a compound of a noble metal selected from the group consisting of Rh, Ir, Pd or Ru, at temperatures of from 130 to 400C and under pressures of from l 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 the noble metal compound on the other hand, the organosilicon compound corresponding to one o~ the following general formulae:
I. RnX3_nSi-(CR23)m-Y or II. RnX3-n(Si-(CR2)m-cHY2 or III. CRnx3-nsi-(cR2)m 72 ~
in which X stands for ~Cl, -Br or -oR2;
Y stands for -NR~, a nitrogen-containing aryl group, -PR24, -AsR~, -SR4 or -SH;
Z stands for -NR4-, PR4-, -AsR4- or -S-:
Rl stands for a Cl - Cs-alkyl;
R2 stands for a Cl - C3-alkyl;
R3 stands for -H, a Cl - Cs-alkyl or -C6Hs;

R4 stands for a Cl - C6-alkyl, a Cs - C8-cyclo-,;~ .
- 3 - 23343-759 alkyl or -C6H5 or C6H5CH2- which may be subs-ti-tuted with a halogen, methoxy, ethoxy or a Cl C3-alkyl;
n stands for 0 or 1 or 2;
m stands for 0 through 8, preferably 1 through 3;
Further preferred and optional features of the process of this invention provide:
a) for the carrier-supported catalyst additionally to contain as a promoter a compound of a non noble metal belonging to the 1st through 3rd principal groups or to the ~th through 6th or 8th subgroups of the Periodic System of the elements;
b) for the organosilicon compound as the polyfunctional ad-hesion promoter in the carrier-supported catalyst to be bound to the carrier materials on the one hand, and alternately with the noble metal compound and to a non noble metal compound selected from the 6th through 8th subgroups of the Periodic System of the elements;
0 c) for the carrier-supported catalyst to contain an inorganic oxidic carrier or an active carbon carrier the residual active hydroxy groups of which were inactivated by esterification or etherification;
d) for the carrier-supported catalyst to contain from 0.01 to 50 wgt %, preferably 0.1 to 20 wgt %, noble metal compound, adhesion promoter and non noble metal compound, if desired;
e) for the carrier-supported catalyst to be used in form , ~, .

6~

of particlss with a size of from 1 to 20 mm.
The catalyst carriers should preferably be selected from inorganic oxides, e.g. SiO2, A1203, MgO, TiO2, La203, ZrO2, zeolites, clay, NiO, Cr203, W03 or corresponding mixed oxides but also active carbon having a BET-surface area of from 1 to 1000 m /9, preferably 30 to 400 m /9, and present-ing OH-groups. These OH-groups undergo reaction with the functional group or groups 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 to which are linked the noble metal compounds from group VIII, especially Rh, Ir, Pd or Ru, if desired alternately with non noble metal compounds from the 6th or Bth subgroup, especially Cr or Ni, but also W, Fe, and Co. These noble metal compounds and non noble metal compounds, if any, may well give rise to the formation of bridges between individual adhesion promoter molecules fixed to the carrier.

20An advantage of the present process resides in the fact that the promoters increasing the catalyst activity and se-lectivity, which are selected from principal groups V or VI
- of 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 concentration which is determin-ed 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 mono carboxylic anhydrides compare favorably in catalyst activity and selectivity with the prior processes referred to herein-above carried out in gas phase with the use of a carrier-supported catalyst.
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 stands for an alkyl group having from 1 to 4 carbon atoms, can also be used as a reaction promoter.
In the general formulae defining the organosilicon com-pounds which should conveniently be used as adhesion promo-ters (spacers), X preferably stands for -ûR2 and more prefe-rably for methoxy and ethoxy. If n stands for 1 or 2, preferably stands for an unbranched alkyl group, especially methyl, ethyl or propyl.
The useful carrier materials have already been speci-fied hereinabove; useful mixed oxides are e.g. Cr203 2 3 3 23' MgO - A1203, SiO2 - Al 0 or Z 0 A1203. The carrier-supported catalyst preferably contains from 0.01 to 5 wgt O noble metal.
The noble metal compounds useful for making the car-rier-supported catalyst comprise e.g. -the following com-pounds:
Rhodium:

RhC13, RhC13 3 H20, RhBr3, RhI3, Rh(N03)3, Rh2(C0)4C12, Rh (cO)4Br2,~Rh(C0)4I2~ / P(C6H5)3-/3R ' - 6 5 3 2 6( )16' RH4(C)l2~ Rh2(2CCH3)4, / RhCl(C H ) / ;

~64~4 Iridium:

IrC13, ~ Ir(Cû)3Cl_72~ Ir ~ P(C6H5)3-/2(C ) ' 4 12 / IrCl(C8H12)_72, Cl(C0)2Irpyr (pyr = C6H5N);

Palladium:

PdC12' PdBr2' PdI2, (CH3C02)2Pd ~P(C6H5)3_72, PdCl rP(C H )3 72' Pd(û2CCH3)2, PdC12(C8H12), ( 6 5 2 2 Ruthenium:
3~ 3( )12~ RUcl2~p(c6H5)3-73~ RUC12(C)2 rP(C H ) 7 r Rucl2(co)3 72-Further useful non noble metal compounds from the 6th or 8th subgroup, especially Cr, Ni, but also W, Fe, Co,which can also be linked to a polyfunctional adhesion pro-moter, comprise Chromium:
Cr(C0)6 CrC13, C7H8Cr(C0)3 Nickel:

Ni(C0)4~ rp(c6Hs)3-72Ni(co)2~ Ni(C8H12)2, 2 The non noble metal compounds from the first to third principal groups or from the 4th through 6th or 8th subgroup of the Periodic System, preferably of Li, Na, Mg, Ca, Al, Ti, Zr, V, Cr, W, Fe, Co, Ni, should conveniently be select-ed from hydroxides, carbonates, carbonyls, hydrides, halides and further salts. The non noble metal compounds, e.g. sodi-um iodide, can be used in form of a solution for impregnat-ing the catalyst carrier therewith.

~26~

For preparation of the carrier~supported catalyst of this invention, i-t is necessary to have the polyfunctional adhesion promoter (organosilicon compound) which is ~ commercially available product or can be made by methods described in literature. Speaking generally, one of the noble metal com-pounds of group VIII and, if desired, one of the non noble metal compounds of the 6th or 8th subgroup is linked to the adhesion promoter, namely to promoter group Y or Z containing an element selected from the 5th or 6th principal group. Next, the noble metal-containing intermedia-ry product is reactively combined with the hydroxyl groups of the carrier material with escape of a group X as a compound XH (e.g. HCl, HBr or R20H).
This is achieved by heating the components 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 (organosilicon compound) with the hydroxy compounds of the carrier with escape of a group X as a compound XH and then additively to combine the noble metal compound of group VIII and, if desired, one of the non noble metal compounds of the 6th or 8th sub-group with the promoter group Y or Z of the intermediary product.
Details are indicated in the catalyst description here-inafter.
In order to increase the selectivity and suppress sidereactions, it is good practice, especially for discontinuous operation but also for the initial phase in a continuous process, to inactivate those residual OH-groups on the surface of -the catalyst carrier which have not reacted with the functional groups X of the adhesion promoter. This can be done e.g. by silylation with trimethylchlorosilane,.methyla-tion with methyl iodide or acetylation with acetic anhydride.
The quantitative ratio of carboxylic acid ester or di-alkylether and iodine(compound) or bromine(compound) in the reaction zone may vary within wide limits. Generally, ho~
ever, 1 to 500 mols, preferably 1 to 100 mols, carboxylic acid ester and/or dialkylether is used per 1 mol iodine(com-pound) or bromine(compound). The temperature selected for the reaction zone should be high enough to always ensure the -- presence of a gaseous reaction mixture, 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 conveniently be contacted with the solid carrier-supported catalyst over a period of from 1 to 1000 seconds, preferably 1 to 180 seconds. The conversion should suitably be effected in a flow tube packed with the carrier-supported catalyst or in an autoclave pro-vided with a stirrer or in a sha~ing autoclave, having the carrier-supported catalyst placed therein. While the carbony-lation is generally effected under practically anhydrous conditions, it is allowable for it to be carried out in the presence of minor amounts of water as normally found in commercial starting materials, which however should not exceed 1 mol %, based on the starting materials. In addition, the carbonylation remains substantially unaffected by the presence of minor amounts of methanol in the starting mate-rials or of hydrogen in commercial carbon monoxide.

~64~

The reaction mixture coming from the carbonylation zone is gaseous and contains carbon monoxide, methyl iodide, acetic anhydride, unreacted methyl acetate or dimethylether and, under circumstances, minor proportions of acetic acid 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 recycling the uncondensed gas. This is a particular advantaga of the process of this invention. The carrier-supported catalyst is not con-taminated; it remains in the reaction zone. As a result, the entire process is rendered considerably simpler.
Examples Autoclave experiments A stainless steel (Hastelloy~C) autoclave (0.25 1 capacity) provided with a stirrer, various inlets and outlets and with a turnable basket receiving the catalyst was used. The car-boxylic acid esters or dialkylethers were reacted in gas phase with Cû-gas in the presence of the massaged or prodded - solid carrier-supported catalyst. It was placed in the turn-able basket which simultaneously permitted the gases to be thoroughly intermixed. The autoclave was charged with 2.5 ml of a liquid mixture of 20 volume parts methyl iodide and 80 volume parts ester or ether and heated to reaction temperature.
The carbonylation was initiated by the injection of carbon monoxide. The C0-pressure was maintained constant by regular d~ f/~

lZ~L6~

replacement of the quantities consumed. Details are indica-ted in the following Examples.
Example 1 2 ml (1.86 9) methyl acetate, 0.5 ml (1.14 9) methyl iodide and 1.69 9 catalyst No. 1 were reacted in the auto-clave with carbon monoxide under a C0-pressure of 20 bars at 200C. The space/time-yield after a reaction period of 1 h was 4 9 Ac20 per 9 Rh per hour. The yield of Ac20, based on the ester used, was 4 O for a selectivity of 9û O.
Example 2 2 ml (l.B6 9) methyl acetate, 0.5 ml (1.14 9) methyl iodide and 1.58 9 catalyst No. 2 were reacted in tne auto-clave with carbon monoxide under a Cû-pressure of 20 bars at 200C. The space/time-yield after a reaction period of 1 hour was 80 9 Ac20 per 9 Rh per hour. The yield of Ac20, based on the ester used, was 34,6 O for a selectivity of 96 ~O.
Example 3 2 ml (1.86 9) methyl acetate, 0.5 ml (1.14 9) methyl iodide and 1.92 9 catalyst No. 3 were reacted in the auto-clave with carbon monoxide under a C0-pressure of 20 bars at 200C. The space/time-yield after a reaction period of 1 h was 30 9 Ac20 per 9 Rh per hour. The yield of Ac20, based on the--~s~er used, was 18 O for a selectivity of 81 ~O.
Example 4 2 ml (1.86 9) methyl acetate, û.5 ml (1.14 9) methyl iodide and 1.95 9 catalyst No. 4 on an A1203/Cr203-carrier (ratio by weight 5:1) were reacted in the autoclave with carbon monoxide under a C0-pressure of 20 bars at 200C. The space/time-yield after a reaction period of 1 h was 140 9 ~26~4 AczO pel g Rh per hour. The yield of Ac20, based on the ester used, was 42.8 % for a selectivity of 97.5 %.
Example 5 2 ml (1.86 9) methyl acetate, 0.5 ml (1.14 9) methyl iodide and 1.9 9 catalyst No. 5 on an Al203/W03-carrier (ratio by weight 10 : 1) were reacted in the autoclave with carbon mono~ide under a C0-pressure of 20 bars at 200C. The space/
time-yield after a reaction period of 1 hour was 90 9 Ac20 per g Rh per hour. The yield of Ac20, based on the ester used, was 44.2 % for a selectivity of 94 %.
Exarnple 6 2 ml (1.86 9) methyl ace-tate, 0.5 ml (1.14 9) methyl-iodide and 1.66 9 catalyst No. 6, the aluminum oxide carrier of which had been impregnated with an aqueous NaI-solution and subsequently dried (ratio by weight Al203:NaI = 30 : 1) were reacted in the aut~oclave with carbon monoxide under a C0-pressure of 20 bars at 200C. The space/time-yield after a reaction period of 1 hour was 130 g Ac20 per g Rh per hour.
The yield of Ac20, based on the ester used, was 20.3 % for a selectivity of 99 %.
Example 7 2 ml (1.86 9) methyl acetate, 0.5 ml (1.14 9) methyl iodide and 2.65 9 catalyst No. 7 were reacted in the autoclave with carbon monoxide under a C0-pressure of 20 bars at 200C.
The space/time-yield after a reaction Deriod of 1 hour was 70 g Ac20 per 9 Rh Der hour. The vield of Ac20, based on the ester used, was 14.5 % for a selectivity of 88 %.
Example 8 A steel tube 20 mm wide and 450 mm long was arranged in 6~

uprignt position and used as a flow tube which was filled with 35 9 catalyst No. 8. 30 Nl C0 (Nl = liter measured at 1 013 bar and 0C) per hour and an evaporated mixture (10 ml liquid) of methyl acetate and methyl iodide (molar ratio 11 : 1) was passed through the flow tube under a pressure of 10 bars at 180C, The effluent reaction mixture was cooled to 0C at atmospheric pressure and analyzed gas-chromatographically.
A space/time-yield of 11.2 9 Ac20 per 9 Rh per hour was obtained. The yield of Ac20, based on the ester used, was 18.7 % for a selectivity of 98 %.
The carbonylation was effected over a period of 200 hours under these conditions after which the performance of the carrier-supported catalyst could not be found to have been impaired.
Example 9 2 ml (1.86 9) methyl acetate, 0~5 ml (1.14 9) methyl iodide and 1.93 9 catalyst No. 9 were reacted in the auto-clave with carbon monoxide under a C0-pressure of 20 bars at 200C. The space/time-yield after a reaction period of 1 h was 20 9 Ac2û per 9 Pd per hour. The yield of Ac20, based on the ester used, was 5.6 % for a selectivity of 99.5 %.
Example 10 2 ml (1.86 9) methyl acetate, 0.5 ml (1.14 9) methyl iodide and 1.92 9 catalyst No. 10 were reacted in the auto-clave with carbon monoxide under a C0-pressure of 20 bars at 200C. The space/time-yield after a reaction period of 1 hour was 10 9 Ac20 per 9 Ru per hour. The yield of Ac20, ~z~
-based on the ester used, was 3.61 % for a selectivity of 99.5 %.
Example 11 2 ml (1.86 9) methyl acetate, 0.5 ml (1.14 9) methyl iodide and 3.`5 9 catalyst No. 11 were reacted in the auto-clave with carbon monoxide under a C0-pressure of 20 bars at 200C. The space/time-yield after a reaction period of 1 hour was 20 9 Ac20 per 9 Ir per hour. The yield of Ac20, based on the ester used, was 11.4 % for a selectivity of 97.5 %.
Example 12 1.86 9 dimethylethbr, 0.5 ml (1.14 9) methyl iodide and 1.92 9 catalyst No. 12 were reacted in the autoclave with carbon monoxide under a C0-pressure of 20 bars at lS 200C. The space/time-yield was 30 9 Ac20 per 9 Rh per hour. The yield of Ac20 after 2 hours, based on the ether used, was 12.7 %.for a selectivity of 66 %.
The principal by-product was methyl acetate.
Example 13 2 ml (1.86 9) methyl acetate, 0.5 ml (1.14 9) methyl iodide and 1.6 9 catalyst No. 13 were reacted in the auto-clave with carbon monoxide under a C0-pressure of 20 bars at 200C. The space/time-yield after a reaction period of 1 h was 110 9 Ac20 per 9 Rh per hour. The yield of Ac20, based on the ester used, was 38 % for a selectivity of 93 %.
Example 14 2 ml (1.86 9) methyl acetate, 0.5 ml (1.14 9) methyl iodide and 1.6 9 catalyst No. 14 were reacted in the auto-clave with carbon monoxide under a C0-pressure of 20 bars ~2~6~

at 200C. The space/time-yield after a reaction period of 1 h was 120 9 Ac20 per 9 Rh per hour. The yield of Ac20, based on the ester used, was 38 % for a selectivity of 96 %.
Description relating ta catalyst preparation In order to be activated, the catalyst carriers were in all cases dried for 10 h at 200C under a pressure of about 0.133 millibar. All syntheses were effected under nitrogen with exclusion of oxygen and water, and all reagents had previously been dried using molecular screen 4 A.
In oder to suppress side-reactions and improve the selectivity, the catalysts referred to hereinafter were finally treated with trimethylchlorosilane.

T-OH + Cl-Si(CH3)3 HCl > T-O-Sl (CH3)3 To this end, all the catalyst prepared were completely covered with trimethylchlorosilane at room temperature. The respective 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 at 85C over a period of 12 hours under a pressure of 1.33 millibars.
Thé symbol "0" used in the formulae hereinafter stands for the phenyl group (C6H5).
Catalyst No. 1 I

/ iO2~0 ISi-CH2CH2-P02 72RhCOCl ~Z~4~

20 9 activated silicon dioxide, which had a diameter of 3 mm, an inner BET-surface area of 300 mZ/g and a pore volume of 0.95 ml/g, was admixed wlth 30 ml benzene. Next, the sus-pension was admixed dropwise while stirring with 3.35 9 (37.5 mg Rh) of the compound of the formula / (C2H50)3SiCH2CH2P02_72 RhCOCl (prepared from (C2H50)35iCH2CH2P02 and L Rh(C)2Cl-/2~
cf. K.G. Allum, J. Organometallic Chem. 87 (1975), pages 203-21~; for preparation of (C2H50)3SiCH2CH2P02 f vinylsilane and diphenylphosphine with exposure to ultraviolet light, see H. Niebergall, Makromol. Chem. 52 (1962) page 218:
for preparation of L Rh(CO)2Cl 72 from RhCl3. 3 H20 and CO-gas, see J.A. McCleverty et al, Inorg. Synth. 8 (1966, page 211) which was dissolved in benzene, and the whole was heated to boiling. The yellow solution was completely decolorized after reflux over a period of 24 hours. The benzene solvent was drawn off by suction and the yellowish catalyst was given in-to a Soxhlet. After 12 h Soxhlet-extraction with benzene as the extractant, the catalyst was dried at 85C under 1.33 millibars and therearter subjected to further treatment with trimethylchlorosilane. The concentrated solutions were free from rhodium. The catalyst so made contained 1.5 wgt % rho-dium.
Catalyst No. 2 loc2H5 / 1203~0-1si-CH2CHi2P02 72RhCOCl 3 9 activated aluminum oxide balls, which had a diameter of 3 mm, an inner BET-surface area of 125 m2/g and a pore volume of 0.9 ml/g, were added, while stirring, to 200 mg 6~

(22.4 mg Rh) of the compound of the formula / (C2H50)3SiCH2CH2P02 72RhCOCl, which was dissolved in 20 ml xylene. The suspension was heated to boiling. The yellow solu-tion was completely decolorized after having been refluxed over a period of 48 hours. The xylene solvent was removed by suction and the yellowish catalyst was given into a Soxhlet.
After 12 h Soxhlet-extraction with benzene, the catalyst was dried at 85C over a period of 8 hours under 1.33 millibars, and then subjected to further treatment with trimethylchloro-silane. The concentrated solutions were free from rhodium.
The catalyst so prepared contained 0.7 wgt % rhodium.
Catalyst No. 3 l A12U3~0-li-CH2CH2CH2S 72Rh2(Co)4 3.2 9 driedaluminum oxide pellets, which had a diameter of 3 mm, an inner BET-surface area of 125 m2/g and a pore volume of 0.9 ml were admixed with 3 ml (û.016 mol) of ths commercially available compound of the formula (CH30)3SiCH2CH2CH2SH, which was dissulved in 20 ml toluene, and the whola was heated to boiling. After having been re-fluxed over a period of 24 hours, the solution was distilled off under reduced pressure and the residue was glven into the Soxhlet. After 12 h Soxhlet-extraction with benzene, the pellets were dried overnight at 85C and under a pressure of 1 mm of mercury. 3.1 9 pellets were admixed at room tempera-ture with 50 mg of the compound of the formula Rh2(CO)4Cl2 in benzene and hydrogen chloride was found to escape at once.
After 20 hours, the supernatant solution was completely de-colorlzed while the pellets were found to have assumed thereddish coloration of the solution. The reddish-brown pellets were filtered off and glven into the Soxhlet, extracted for 12 hours with benzene, dried at 85C under 1.33 mlllibars and subjected to further treatment with trimethylchlorosilane.
The catalyst so made contained 0.8 wgt % Rh.
Catalyst No. 4 l Cr2o330~5iCH2CH2P02 72RhCOCl C2~5 285 mg (31.9 mg Rh) of the compound of the formula L (C2H5o)3sicH2cH2p02-72Rhcocl~ dissolved in 20 ml xylene was added, while stirring, to a mixture of 7 9 activated aluminum oxide and 19 wgt % chromium(III)oxide which had an inner BET-surface area of 60 m2/g and consisted substantially of par-ticles with a size of 2 mm, and the resulting suspension was heated to boiling. After having been refluxed for 48 h, the solution was found to have been completely decolorized. The xylene solvent was distilled off ùnder reduced pressure and the greenish catalyst was given into the Soxhlet. After 12 h Soxhlet-extraction with benzene, the catalyst was dried for-8 h at 85C under 1.33 millibars and then subjected to further treatment with trimethylchlorosilane. The concentrated solu-tionswere free from rhodium. The catalyst so made contained 0.4 wgt % rhodium.
Catalyst No. 5 W03 3~sicH2cH2P02 72Rh ~6~

125 mg (14 mg Rh) of the compound of the formula/ (C2H50)3SiCH2CH2P02 72RhCûCl, dissolved in 20 ml xylene, was added, while stirring, to a mixture of 2 9 activated aluminum oxide and lO wgt % -tungsten oxide which had an inner BET-sur-face area of 140 m2/g and consisted substantially of particleswith a size of 2 mm, and the suspension was heated to boiling.
After having been refluxed over a period of 48 h, the yellow solution was ~ound to have been completely decolorized. The xylene solvent was distilled off under reduced pressure and the catalyst was given into the Soxhlet. After 12 h Soxhlet-extraction with benzene, the catalyst was dried for a period of 8 h at 85C under l.33 millibars and then subjected to further treatment with trimethylchlorosilane. The catalyst so made contained 0.66 wgt % rhodium.
Catalyst No. 6 /~l23~-l~_CH2c~12_P02_72RhcOCl ~ NaI
ûC2H5 O.l g sodium iodide, dissolved in 30 ml acetone, was added, while stirring, to 3.l 9 activated aluminum oxide (99 % Al203) which consisted substan~ially of particles with a size of 3 mm, had an inner BET-surface area of 125 m2/g and a pore volume of 0.9 ml/g, and the whole was heated to boiling. After having been refluxed over a period of 48 hours, the solvent was re-moved by suction and the catalyst pellets were dried for 4 hours at 85C under 1.33 millibars. They contained 2.55 wgt %
_ iodide. The solvent was free from iodide.
3.2 9 of this catalyst mass was admixed, while stirring, with 70 mg (7.8 mg Rh) of the compound of the formula L (C2~5o)3sicHzcH2p~2-72Rhcocl which was dissolved in 20 ml xylene, and the suspension was heated to boiling. After hav-ing been refluxed for 36 hours, the yellow solution was found to have been completely decolorized. The xylene solvent was removed by suction under reduced pressure and the yellowish catalyst was given into the Soxhlet. After 12 h Soxhlet-ex-traction with benzene, the catalyst was dried over a period of 8 hours at 85C under 1.33 milliba-rs, and then subjected to further treatment with trimethylchlorosilane. The catalyst û so made contained 0.24 wgt % rhodium.
Catalyst No. 7 l C2H5 - NaX ~U-si-CH2-CH2P02 7 RhCOCl 1.07 9 (112 mg Rh) of the compound of the formula l (C2H5o)3sicH2cH2p02-72Rhcocl~ dissolved in 100 ml xylene, was added, while stirring, to 25 9 activated NaX-zeolite which consisted substantially of particles with a size of 2 mm in diameter and had a BET-surface area of 800 m2/g, and the 0 whole was heated to boiling. After having been refluxed for 72 hours, the solution was found to have been completely decolo-rized. The solvent was removed by suction and the catalyst was given into the Soxhlet. After 12 h Soxhlet-extraction with benzene, the catalyst was dried over a period of 8 hours at 85C under 1.33 millibars, and then subjected to further treatment with trimethylchlorosilane. The catalyst so made contained 0.26 wgt % rhodium.
Catalyst No. 8 ~L~64~

1 2 0 3 ~ 0 - 1S l - C H 2 C H 2 P 0 2 7 2 R h C
OC2~5 The catalyst was made ln the same manner as catalyst No. 2, but it contained 0.6 wgt % rhodium.
Catalyst No. 9 1203~0-1SiCH2CH2P02 72PdC12 140 mg ~15.8 mg Pd) of the compound of the ~ormula / (C2H50)3SiCH2CH2P02_72PdC12 (prepared from 2 5 3 2 2P~2 and Pd(CH3C02)2 or (C6H5CNPdC1 or PdCl2(C8H12), cf. J. Chem. Soc. (London) Chem. Com 1977, page 510) which was dissolved in a mixture of 10 ml benzene and 10 ml dichloromethane, was added while stirring to 3.1 9 acti-vated aluminum oxide (99 % Al203) which consisted substan-tially of particles with a size 3 mm in diameter, had an inner BET-surface area of 125 m2/g and a pore volume of 0.9 ml/g, and the suspension was heated to boiling. After having been refluxed over a period of 56 hours, the yellow solution was found to have been completely decolorized. The solvent mixture was removed by suction and the yellowish catalyst was given into the Soxhlet. After 12 h Soxhlet-extraction with benzene, the catalyst was dried for 8 hours at 85C under 1.33 millibars and then subjected to further treatment with trimethylchlorosilane. The concentrated solutions were free from palladium. The catalyst so made contained 0.37 wgt %
palladium.

6~

Catalyst No. 10 A1203~0~ CH2-CH2P02 72Ru(C.û)2Cl 140 mg (15.5 mg Ru) of the compound of the formula L ( czH5n) 3SicH2c~2P02 72RU (co) 2C12 (prepared from (C2H50)3SiCH2CH2P~2 and (P03)2RuC12(C0)2, cf. Pittman JACS
(1975), page 1749) which was dissolved in a mixture of 15 ml dichloromethane and 15 ml benzene was added, while stirring, to 3.2 g activated aluminum oxide (99 % Al2û3) which consist-ed substantially of particles with a size of 3 mm in dia-meter, had an inner BET-surface area of 125 m2/g and a pore volume of 0.9 ml/g, and the suspension was heated to boil-ing. After having been refluxed for 72 hours, the solution was found to have been decolorized. After separation of the solvent mixture, the catalyst was gi.ven into the Soxhlet.
After 12 h Soxhlet-extraction with benzene, the catalyst was dried for 8 hours at 85C under 1.33 millibars and then subjected to further treatment with trimethylchlorosilane.
The concentrated solutions were free from ruthenium. The catalyst so made cbntained 0.48 wgt % ruthenium.
Catalyst No. 11 12O3~0-1Si-CH2CH2P02 72Ir 125 mg (23.8 mg Ir) of the compound of the formula (C2H50)3SiCH2CH2P02_72Ir COCl (prepared from (C2H50)3sicH2cH2p~2 and / IrCl(C8H12) 72 or Cl(Cû)2Irpyr or ( ~3)2~ cf. Pittman, JACS 97 (1975), page 4774) which was dissolved in 100 ml toluene was addded to 5.6 9 activated aluminum oxide (99 % Al203) which consisted substantially of particles with a diameter of 3 mm, had an inner 8ET-surface area of 125 m2/g and a pore volume of 0.9 ml/g, and the whole was heated to boiling. After having been refluxed for 100 hours, the solution was found to have been decolorized. After separation of the solvent, the catalyst was givsn into the Soxhlet. After 12 h Soxhlet-extraction with benzene, the catalyst was dried for 8 hours at 85C under 1.33 millibars.
The concentrated solutions were free from iridium. The cata-lyst so made contained 0.41 wgt % iridium.
Catalyst No. 12 ~OC2H5 L Al23~U-lsic~l2cH2-p~2 72RhCOCl The catalyst was made in the same manner as catalyst No.

2, but it contained 0.9 wgt % rhodium.

Catalyst No. 13 20_ -o-sicH2cH2-p02-72Rh l C2H5 _ -o-sicH2cH2-p02-72Ni(co)2 25100 mg (11.2 mg Rh) of the compound of the formula (C2H50)3SiCH2CH2P02_72RhCOCl and 100 mg (6.7 mg Ni) of the compound of the formula / (C2H50)3SiCH2CH2P02 72Ni(Co)2 (prepared from (C2H50)3SiCH2CH2P02 and / Rh(C0)2Cl 72~ and ~i4~

Ni~CO)4, cf. A.K. Smith et al. J. mol. Catal. 2 (1977), page 223) which were dissolved in 40 ml xylene, were added, while stirring, to 3.2 9 activated aluminum oxide (99 % A1203) which consisted substantially of particles 3 mmin diameter, had an inner BET~surface area of 125 m2/g and a pore volume of 0.9 ml/g, and the suspension was heated to boiling. After having been refluxed over a period of 72 hours, the yellow solution was found to have been decolorized. After separa-tion of the solvent, the catalyst was given into the Soxhlet.
After 12 h Soxhlet-extraction with benzene, the catalyst was dried for 8 hours at 95C under 1.33 millibars and subjected to further treatment with trimethylchlorosilane. The concen-trated solutions were free from rhodium and nickel. The catalyst so made contained 0.33 wgt % rhodium and û.l9 wgt %
nickel promoter.
Catalyst No. 14 --O-si-CH2CH2-P02 72RhCOCl A1203 _ OCz15 0-Si-CH2CH2-P02 7Cr(c0)5 .. OC2H5 100 mg (11.2 mg Rh) of the compound of the formula 25 / (C2H50)3SiCHZcH2P02_72RhCOCl and 125 mg (11.4 mg Cr) of the compound of the formula L (C2H5O)3SiCH2CH2P02 7Cr(CO)5 (prepared fram (C2H50)3SiCH2CH2P02 and L Rh(CO)2~1_72, Cr(CO)6, res,aectively, cf. JACS 81 (1959), page 2273) which were dissolved in 40 ml xylene, were added, while stirring ~26~

to 3.2 9 activated aluminum oxide (99 ,' Al203) which consisted substantially of particles 3 mm in diameter, had an inner BET-surface area of 125 m2/g and a pore volume of 0.9 ml/g, and-the suspension was heated to boiling. After having bean re-fluxed for 72 hours, the yellow solution was found to havebeen completely decolorized. The solvent was separated and the catalyst was given into the Soxhlet. After 12 h Soxhlet-extraction with benzene, the catalyst was dried for 8 hours at 85C under 1.33 millibars and then subjected to further treatment with -trimethylchlorosilane. The concentrated solu-tions were free from rhodium and nickel. The catalyst so made contained û.33 wgt % rhodium and 0.3 wgt % chromium promoter.

Claims (7)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
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 containing a compound of a noble metal selected from the group consisting of Rh, Ir, Pd or Ru, at tempe-ratures of from 130 to 400°C and under pressures of from 1 to 150 bars, which comprises: using a carrier-suppor-ted catalyst having an organosilicon compound as a poly-functional adhesion promoter bound to the carrier mate-rial on the one hand, and to the noble metal compound on the other hand, the organosilicon compound corresponding to one of the following general formulae:
I. or II. or III. in which X stands for -Cl, -Cr 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-cy-cloalkyl or -C6H5 or C6H5CH2- which may be substituted with a halo-gen, methoxy, ethoxy or a C1-C3-alkyl;
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 of a non noble metal selected from the group consisting of Li, Na, Mg, Ca, Al, Ti, Zr, V, Cr, W, Fe, Co or Ni.
3. A process as claimed in claim 1, 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 noble metal compound and to a compound of a non noble metal selected from Cr, W, Fe, Co or Ni, on the other hand.
4. 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.
5. A process as claimed in claim 1, wherein the carrier-supported catalyst contains from 0.01 to 50 wgt %
noble metal compound and adhesion promoter.
6. A process as claimed in claim 2, wherein the carrier-supported catalyst contains from 0.01 to 50 wgt %
noble metal compound, adhesion promoter and non noble metal compound.
7. 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.
CA000493586A 1984-11-07 1985-10-22 Process for making monocarboxylic anhydrides Expired - Fee Related CA1264164A (en)

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EP0203286B1 (en) * 1985-03-27 1988-09-14 Hoechst Aktiengesellschaft Supported catalyst and procedure for the production of monocarboxylic acid anhydrides
DE3544765C2 (en) * 1985-12-18 1994-04-07 Roehm Gmbh Process for the production of unsaturated aliphatic carboxylic anhydrides
DE3808867A1 (en) * 1988-03-17 1989-09-28 Hoechst Ag METHOD FOR PRODUCING MONOCARBONIC ACID ANHYDRIDES
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US2722504A (en) * 1950-12-04 1955-11-01 Union Oil Co Silicone coated catalyst and use thereof
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US4007130A (en) * 1975-12-29 1977-02-08 Monsanto Company Catalyst regeneration method
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