A PROCESS FOR CARBONYLATING METHANOL TO ACETIC ACID AND/OR METHYL ACETATE

Abstract: A process for carbonylating methanol to acetic acid and/or methyl acetate characterized in that methanol is react­ ed with carbon monoxide in the presence of a catalyst com­ prising: a catalytically active amount of a homogeneous Group VIII metal compound, a promoter RZ wherein R is H or C₁-C₃-­ alkyl and Z is chlorine, bromine or iodine and a Group IA-, IIA- or transition metal iodide or carboxylate; and one or more li­ gands containing at least one electron-rich N atom.

Description: A PROCESS FOR CARBONYLRTING METHANOL TO ACETIC ACID AND/OR METHYL ACETATE Carbonylation processes for the preparation of carboxylic acids from alcohols particularly for the production of acetic acid from methanol are well known in the art. The prior art teaches the use of a nutter of catalysts for the synthesis of carboxylic acids from alcohols and carbon monoxide at elevated temperatures and pressures. Catalysts such as phosphoric acid, phosphates, heavy metal salts such as zinc and cuprous chlorides, silicates of various metals, and boron trifluoride in various hydration states have been reported to function for the production of acetic acid by the reaction of methanol and carbon monoxide at elevated temperatures and pressures of the order of 4000C and 700 bar, respectively. However, even under such severe conditions, the yields of acid were substantially poor, and, therefore, uneconomical. Other catalysts that have been reported under somewhat less severe conditions but still relatively high temperatures and pressures are liquid phosphoric acid containing copper phosphate, activated charcoal impregnated with phosphoric acid, and metal carbonyls, such as iron, cobalt and nickel, in conjunction with their halides or free halogens in liquid phase. Even with the use of these catalysts temperatures and pressures are more severe than would be desired in a commercial operation. A rhodium based catalyst system used in conjunction with a halide promoter has been disclosed in the prior art as allowing for the carbonylation of methanol to acetic acid to occur at relatively low pressures and temperatures. Rhodium, however, is a relatively expensive catalytic material. A catalytic material which would be much less exl?ensive than rhodium, but would carbonylate methanol to acetic acid at relatively low temperatures and pressures would be highly desirable. The present invention relates to a process for carbonylating methanol to acetic acid and/or methyl acetate characterized in that methanol is reacted with carbon monoxide in the presence of a catalyst comprising a catalytically active amount of a homogeneous Group VIII metal compound, a promoter RZ wherein R is H or C1-C3 alkyl and Z is chlorine, bromine or iodine and a Group IA-, IIA- or transition metal iodide or carboxylate, and one or more ligands containing at least one electron-rich N atom. Palladium is the preferred catalyst and is very active at relatively low temperatures and pressures. It is further more considerably less expensive than corresponding rhodium catalysts by a factor of about 6. The catalyst can be prepared in several ways. It can be prepared by combining the above components and then charging the resultant catalytic material to the reactor or it can be prepared by charging the individual components to the reactor and allowing the catalyst to form in situ. The catalytically active component is a homogeneous Group VIII metal having an atomic number of 26, 27, 28, 44, 45, 46, 76, 77 or 78. Two or more Group VIII metal compounds having differing anions, differing cations or both differing anions and cations may be utilized. Of the Group VIII metal compounds, palladium compounds are preferred. Concentrations of Group VIII metals will range from 10 to 10-1 moles per liter. The palladium is conveniently provided as a palladium salt which will be soluble in the reaction medium. Suitable palladium salts, are for example, palladium dichloride, palladium acetate, palladium nitrate, palladium sulphate, palladium diiodide, palladium dibromide, and palladium acetylacetonate. The preferred palladium salt is palladium acetate. The palladium need only be present in the reaction medium in small concentrations. Preferred concentrations will range fom 10-5 to 10-1 molees per liter. A two-component promoter is utilized, the first component com- prising a halide of the general formula RZ wherein R is hydrogen or a lower alkyl having a carbon number ranging from 1 to 3 and Z is chlorine, bromine and/or iodine, and second component comprising a Group IA (alkali metal), IIA (alkaline eo-Wh metal) or transition metal iodide or carboxylate. In the absence of metal salts it is determined that the catalyst becomes inactive by plating out of the palladium. Large amounts of the salts, however, can procedure a lessening in rates. Molar ratios of promoter to Group VIII metal compound typically are greater than 1:1, preferably greater than about 10:1. Different metal iodide or carboxylate salts will require different optimum ratios of RZ to metal iodide or carboxylate salts. These optimum ratios can readily be determined by routine experi mentation. Preferably the first component will be comprised of an iodide component. Z thus is preferably iodine. Generally, it is preferred that the amount of iodine material present in the reaction medium will be in amounts such that the atomic ratio of iodine to the atomic ratio of Group VIII metal is above 2:1. Preferably, the atomic ratio of the iodine to the Group VIII metal will be in a range of 5:1 to 5000:1. A more preferred atomic ratio of the iodine to Group VIII metal is about 10:1 to about 2500:1. The multi-component catalytic system used in the process of the instant invention also utilizes one or more ligands containing at least one electron-rich nitrogen atom capable of forming coordina- tion compounds with the Group VIII metal moieties present in the catalytic system. Examples of ligands which can be used conveniently comprise pyrrole, alkyl substituted pyrroles, pyrrolidine, alkyl-sub- stituted pyrrolidines, pyridine, alkyl-substituted pyridines, piperidines, alkyl-substituted piperidines, pyrimidine, alkyl-substituted pyrimidines, pyraz ine, benz triazo le, tetra-ethy lenediamine, phenanthrolenes such as 1 ,10-phenanthroline, alkyl-substituted 1 ,l0-phenan- thrclines, morpholine and alkyl-substituted morpholines. The amount of organo-nitrogen ligand to be used in the process according to the present invention is generally related to the amount of Group VIII (and transition) metal compound(s) present in the reaction mixture. For example, when palladium is the sole "heavy metal" present, 2 or more mols of ligand per mol of palladium compound are sufficient. Generally, the molar amounts of ligand present will range from 2 to 10 or higher times the total molar amount of Group VIII metal compound present. The ligands listed in Table I below have been experimentally determined to exert ligand activity. Other ligands containing at least one electron-rich N atom would also be suitable. Table I: Ligands containing at least one electron-rich N atom: 2,2'-bipyridine (Bip) 2,2'-biquinoline pyridil (=di-2-pyridilglyoxal) phenanthroline picolinic acid 2,6-pyridine disulphonic acid (PDSA) pyrrole 2-quinolinol picolymethylamine N,N,N',N'-tetramethylethylenediamine (TMEDA) phenylenediamine pyrrolidinone ethylenediamine (EDA) 2-aminopyridine pyridine A particularly desirable ligand is 2,2'-bipyridine, particularly when palladium is the Group VIII metal utilized. The concentration of 2,2'-bipyridine is preferably maintained at 2 or more moles of bipyridine per mole of palladium compound. Lower concentrations of bipyridine lower the rates. Thus, the preferred molar ratio of bipyridine to palladium compound ranges from about 2:1 to about 6:1. The 2,2'-bipyridine can be readily made from pyridine by refluxing on Raney nickel with good yield. Crude bipyridine, containing mixtures of 2,2'-, 2,4'- and 4,4'-isomers, can be utilized in the instant invention as a source of 2,2'-bipyridine without separation of the respective isomers. The carbonylation reaction is carried out by intimately contact ing methanol with gaseous carbon monoxide in a liquid phase containing the catalyst system as prepared from the components described above under conditions of temperature and pressure suitable to form acetic z tic acrid and/or methyl acetate. The temperature accordingly will be in the range of 1250C to 2500C, preferably from 165"C to 2250C and most preferably from 1750C to 2050C. Partial pressures of carbon monoxide of the order of 1 bar to 360 bar are suitably employed, preferably, pressures ranging from 20 bar to 210 bar carbon monoxide partial pressure are generally preferred. Higher pressures may be used if desired under appropriate conditions. The carbon monoxide required for the reaction may be supplied in substantially pure form, or diluted with any inert gas, for example nitrogen. The presence of more than minor amounts of hydrogen in the gas stream has undesirable effects upon the activity of the catalyst. Generally, it is preferred that the amount of hydrogen in the gas stream should be less than about 5% by volume, preferably less than about 1% by volume. A separate solvent is not essential in the process according to the instant invention, and often a large excess of methanol, acetic acid or methyl acetate forms a convenient reaction medium. However, it may in some cases be desirable to use a separate solvent, and any suitable inert medium may be used. A suitable solvent may, for example, be selected from sulphones, for example dimethyl sulphone, diethyl sulphone or diisopropylsulphone or sulfolanes, either unsubstituted or alkyl substituted such as 2-methyl sulfolane or 3-methyl sulfolane. The addition of water to the reaction medium also appears to provide certain benefits when using certain Group VIII transition metal mixtures. For example, markedly higher rates and conversions are noted for the Ni/Pd system. It is generally desirable to have from 5 to 30% by weight of water present in the reaction medium. The following examples are provided to illustrate the invention and are not to be construed as limiting the invention. Examples In general, the following examples were carried out in a 300 ml stirred autoclave. The autoclave was charged with the appropriate reactant eJs indicated in Table II. The runs were conducted at constant pressure using a high-pressure regulator and a reservoir autoclave filled with CO. Both reaction vessel and reservoir were equipped with a pressure transducer enabling the measurement of the constant pressure in the reaction vessel and the pressure drop in the reservoir. This latter pressure drop is a measure for the rate of reaction. Before starting, the reservoir was pressured up to 270-360 bar and the reaction vessel was charged at room temperature with approximately half the carbon monoxide pressure desired at 1700-1000C. This procedure was followed in order to prevent plating out cf metals at low or zero carbon monoxide pressure. The space-time yields are calculated from yields as found by GLC analysis. In cases where certain variables were changed during a run a different procedure was followed. The space-time yield for a particular part of the reaction was calculated from the pressure drop per hour, the overall yield and the overall-pressure drop in the reservoir. The data for these experiments are shown in Table II below. The results are indicated as space-time yields in kilogram per liter per hour and the data also includes a percentage of the conversion over which the space-time yield has been calculated. TABLE II. CARBONYLATION OF METHANOL WITH Pd Space-Time Example Pd(OAc)2 Bip MeOH MeOH H2O CH3I NaI Temp Pressure Conv. Yield, Remarks g g g g g g g C bar % kg/1 h EMI7.1 1 <SEP> 0,75 <SEP> 1,1 <SEP> 24 <SEP> 12 <SEP> 8 <SEP> 7,5 <SEP> 3 <SEP> 195-225 <SEP> 110-140 <SEP> 0-123b) <SEP> 0,18a) <SEP> Glass-lining. <SEP> Temperature <tb> <SEP> # <SEP> overshot. <SEP> Conversion <SEP> too <tb> 2 <SEP> 0,075 <SEP> 0,22 <SEP> 24 <SEP> 12 <SEP> 8 <SEP> 7,5 <SEP> 3 <SEP> 190-200 <SEP> 200-140 <SEP> 0-117 <SEP> 0,19a) <SEP> high. <SEP> 3 <SEP> runs. <tb> 3 0,10 0,14 80 40 30 29 7 178 110 0-72 0,14 2,5 h/run 4 0,10 0,07 80 40 30 29 7 180 110 0-44 0,07 3 h 5 0,10 0,14 80 40 30 22 14 180 110 0-54 0,12 2 h 6 0,20 0,28 80 40 30 50 20 182 110 0-53 0,26 1 h/run 7 0,25 0,035 80 40 30 25 13 192 140 0-8 0,12 8-15 0,16 Added 0,025 g Pd acetate, 0.035 g Bip 15-30 0,18 Added 0,050 g Pd acetate, 0.070 g Bip 0-30 0,16 Average 8 0,10 0,14 80 40 30 25 13 192 140 0-12 0,34 12-25 0,35 Added 0.10 g Pd acetate, 0.14 g Bip 35-78 0,08 Added 0.20 g Pd acetate, 0.28 g Bip 0-78 0,15 Average a) Based on an assumed 60-70% liquid volume in autoclave. b) Yields of greater than 100% refer to cenversion of solvent methyl acetate in addition to reactant methanol. Using a general procedure similar to that described above, the carbonylation of methanol was carried out in an 80 ml autoclave using different organo-nitrogen ligands. The autoclave was initially charged with 50 bar CO pressure at 250C. The reaction was carried out at 3000C for 3 hours. The results are shown in Table III. Table III Carbonylation of methanol using various ligands Pd(OAc)2 Ligand Methanol CH3 I Sulfo- Salt Carbonylation catalyst lane (g) (g) (g) (g) (g) (g) 0,005 TMEDAa) 4 1,5 14 NiI2 75 0,17 0,17 0,005 PDSAb) 4 1,5 14 NiBr2 58 0,20 0,10 0,005 BIPc) ) 2 0,75 7 FeI2 38 0,10 0,10 0,005 2-amino- 4 1,5 14 Ni(OAc)2.4H2O 62 pyridine 0,2 0,10 a) N,N,N',N'-tetramethylethylenediamine b) 2,6-pyridine disulphonic acid c) 2,2'-bipyridine

Claims: CLAIMS 1. A process for carbonylating methanol to acetic acid and/or methyl acetate characterized in that methanol is reacted with carbon monoxide in the presence of a catalyst comprising a catalytically active amount of a homogeneous Group VIII metal compound, a promoter RZ wherein R is H or C1-C3- alkyl and Z is chlorine, bromine or iodine and a Group IA-, IIA- or transition metal iodide or carboxylate; and one or more ligands containing at least one electron-rich N atom. 2. A process according to claim 1 characterized in that the Group VIII metal is palladium. 3. A process according to claim 1 or 2 characterized in that the ligand is 2,2'-bipyridine, 2,2'-biquinoline, di-2-pyridilglyoxal, phenanthroline, picolinic acid, 2,6-pyridine disulphonic acid, pyrrole, 2quinolinol, picolylmethylamine, N,N,N' ,N'-tetramethyl- ethylenediamine, pheny lenediamine, pyrrolidinone, ethylenediamine, 2-aminopyridine, or pyridine. 4. A process according to claims 1 to 3 characterized in that the Group VIII metal compound concentration ranges from 10-5 to 10-1 moles per liter, the molar ratio of ligand to Group VIII metal compound is 2:1 or more, the atomic ratio of Z to Group VIII metal ranges from 5:1 to 5000:1, the molar ratio of promoter to Group VIII metal compound is greater than 1:1. 5. A process according to claims 1 to 4 characterized in that the temperature ranges from 125 C to 2500C. 6. A process according to claim 5 characterized in that the terry perature ranges from 165 C to 2250C. 7. A process according to claims 1 to 6 characterized in that the partial pressure of carbon monoxide ranges fran 1 bar to 360 bar. 8. A process according to claims 5-7 characterized in that the temperature ranges from 1750C to 2050C and the pressure ranges fra 20 bar to 210 bar.

Inventors: VAN LEEUWEN, PETRUS WILHELMUS N.
Applicants: SHELL INTERNATIONALE RESEARCH MAATSCHAPPIJ B.V.
Application year: 1983
Main classification: C07C51
IPC codes: C07C69, C07C53, C07C27, C07B61, B01J31, C07C51, C07C67