GB2036739A - The use of Group VIII metals as co-catalysts in the homologation of methanol - Google Patents

The use of Group VIII metals as co-catalysts in the homologation of methanol Download PDF

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GB2036739A
GB2036739A GB7939903A GB7939903A GB2036739A GB 2036739 A GB2036739 A GB 2036739A GB 7939903 A GB7939903 A GB 7939903A GB 7939903 A GB7939903 A GB 7939903A GB 2036739 A GB2036739 A GB 2036739A
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Abstract

Ethanol is produced by reacting methanol with carbon monoxide and hydrogen in the presence of a catalyst comprising (i) cobalt, (ii) one or more other metals of Group VIII of the Periodic Table of which ruthenium and osmium are preferred, (iii) an iodide or a bromide, typically iodine and (iv) a compound having the formula (A) (B) (C) X in which X is nitrogen, phosphorus, arsenic, antimony or bismuth and A, B and C are individually monovalent organic radicals or X is phosphorus, arsenic or antimony and any two of A, B and C together form an organic divalent cyclic ring system bonded to the X atom or X is nitrogen and all of A, B and C together form an organic trivalent cyclic ring system bonded to the X atom. Compounds which may be used as the component (iv) include triethylphosphine, tri-n-butylphosphine, tricyclohexylphosphine, tri-t- butylphosphine and triphenylphosphine. Other compounds may be added to further improve the molar yield of realisable ethanol.

Description

SPECIFICATION The use of group VIII metals as co-catalysts in the homologation of methanol The present invention relates to a process for the production of ethanol by reacting methanol with a mixture of carbon monoxide and hydrogen (hereinafter to be referred to as synthesis gas), in the presence of a promoted cobalt-containing catalyst and one, or more, of the other metals of Group VIII of the Periodic Table (viz iron, ruthenium, osmium, rhodium, iridium, nickel, palladium and platinum) as co-catalyst.
Ethanol is a valuable industrial product which is generally manufactured either by fermentation of natural products eg molasses or by hydration of ethylene in the presence of an acid catalyst, such as phosphoric acid. The rapidly dwindling reserves of crude oil from which ethylene is derived and the associated need to utilise fully the remaining natural resources such as coal and the vast amounts of gases, eg methane potentially available from the exploitation of North Sea oilfields has stimulated researches to investigate other routes to ethanol utilizing these materials as feedstocks. Both coal and methane gas can be converted into synthesis gas (CO + H2), which in turn can be reacted to form methanol, which methanol can be further reacted with carbon monoxide and hydrogen under appropriate conditions to form ethanol.
It has long been known that methanol can be hydrocarbonylated with hydrogen and carbon monoxide to ethanol in the presence of a water soluble cobalt catalyst at high temperatures and pressures. The course of this reaction can be represented by the following equation:
The problem with the majority of prior art processes is that they produce large amounts of by-products such as esters, and acids in addition to ethanol.
Recently it has been reported [19 July 1978 issue of CHEMICAL WEEK, page 41] that the molar selectivity to ethanol can be increased by adding small amounts of sodium iodide and ruthenium trichloride to the cobalt carbonyl catalyst. Another report in the April 1978 issue of CHEMTECH, page 256, suggests that the key to producing ethanol from methanol and synthesis gas is the use of ruthenium catalyst promoted by an iodine compound.
We have now found that the molar yield of realisable ethanol and/or the molar selectivity to realisable ethanol, both as hereinafter defined, may be improved by the addition of a metal or metals of Group VIII of the Periodic Table, such as ruthenium and osmium, as co-catalysts to a cobalt catalyst promoted with both an iodide or a bromide and a phosphorus, nitrogen, arsenic, antimony or bismuth-containing ligand, such as triphenyl phosphine and triphenyl-arsine.
By total realisable yield of ethanol within the context ofthe specification is meant the yield of free ethanol plus the yield of ethanol realisable by the hydrolysis of ethanol-yielding esters (eg ethyl acetate). In the same way, by realisable methanol is meant the free methanol plus the methanol realisable by the hydrolysis of methanol-yielding esters (eg methyl acetate).Thus, % Molar Yield of Realisable Ethanol Moles of realisable methanol converted into realisable ethanol x 100 Total moles of realisable methanol fed and, % Molar Selectivity to Realisable Ethanol Moles of realisable methanol converted into realisable ethanol = x100 Total moles of realisable methanol fed By the yield of realisable acetic acid is meant the yield of free acetic acid plus the yield of acetic acid realisable by the hydrolysis of acetic acid-yielding esters (eg methyl acetate). In calculating the yield it is assumed that all the acetic acid is derived from methanol and synthesis gas and no account is taken of acetic acid derived from cobalt acetate, when this is added as catalyst.Thus, % Molar Yield of Realisable Acetic Acid Moles of realisable methanol converted into realisable acetic acid x 100 Total moles of realisable methanol fed % Methanol conversion Total moles of methanol converted Total moles of methanol fed x 100 Thus according to the present invention there is provided a process for the production of ethanol which process comprises reacting at elevated temperature and pressure methanol with hydrogen and carbon monoxide in the presence of a catalyst comprising (i) cobalt, (ii) one or more other metals of Group VIII of the Periodic Table, (iii) an iodide or a bromide and (iv) a compound having the formula::
wherein X is nitrogen, phosphorus, arsenic, antimony or bismuth and A, B and C are individually monovalent organic radicals or X is phosphorus, arsenic or antimony and any two of A, B and C together form an organic divalent cyclic ring system bonded to the X atom or Xis nitrogen and all of A, B and C together form an organic trivalent cyclic ring system bonded to the X atom.
The Periodic Table referred to throughout this specification is the Periodic Table of the Elements in the Handbook of Chemistry and.Physics, 44th Edition, published by the Chemical Rubber Publishing Company in 1963.
Methanol is a readily available industrial product It is generally manufactured on an industrial scale from synthesis gas. Whilst it is preferred that the methanol be substantially pure the presence of small amounts of certain impurities can be tolerated. The methanol may however contain up to 50% by weight of water.
Mixtures of the gases hydrogen and carbon monoxide are readily available in the form of synthesis gas.
Methods for preparing synthesis gas are well-known in the art and usually involve the partial oxidation of a carbonaceous substance, eg coal. Alternatively synthesis gas may be prepared, for example, by thermal steam reforming of methane. For the purpose of the present invention the molar ratio of carbon monoxide to hydrogen may suitably be in the range 2:1 to 1:3, preferably 1:1 to 2:5, even more preferably it is 1:2.
Methods for adjusting the molar ratio of carbon monoxide to hydrogen are well-known to those versed in the art. Although it is preferred to use substantially pure synthesis gas the presence of such impurities as carbon dioxide and nitrogen can be tolerated. On the other hand impurities having a deleterious effect on the reaction should be avoided. Thus it may be necessary in a continuously operated process to employ a gas purge to prevent the build-up of deleterious impurities.
The catalyst comprises (i) cobalt, (ii) one or more other metals of Group VIII of the Periodic Table, (iii) an iodide or bromide and (iv) a compound having the formula (I). With regard to component (i) any source of cobalt can be used in the process of the present invention. Cobalt is preferably employed in the ionic form, but the use of cobalt metal to react in situ to form ionic cobalt which then further reacts to form the desired cobalt complex is within the scope of the present invention. Typical sources of cobalt are, for example, compounds such as cobalt acetate, cobalt formate, cobalt propionate and the like, which under the reaction conditions form carbonyl or carbonyl/hydride complexes.
With regard to component (ii) suitable Group VIII metals include iron, ruthenium, osmium, rhodium, iridium, nickel, palladium and platinum, of which ruthenium and osmium are preferred. Particularly preferred is ruthenium. The metal may be added as the free metal but is preferably added in the form of a soluble compound thereof, for example a chloride or carbonyl.
With regard to component (iii) of the catalyst the iodide or bromide can be added either in ionic form, eg as cobalt iodide or cobalt bromide, or as molecular iodine (12) or bromine (Br2). Furthermore the iodide may be added as an alkyl or aryl iodide or bromide, preferably methyl iodide. However, the iodide or bromide may also be added in ionic form utilising cations which are inert with regard to the hydrocarbonylation reaction.
Typical of the inert form is potassium iodide or bromide, sodium iodide or bromide and lithium iodide or bromide. Of the iodide or bromide, the iodide is preferred.
With regard to component (iv) of the catalyst compounds having the formula (I) are tertiary phosphines, arsines, stibines, bismuthines, amines and nitrogen-containing heterocyclic systems, eg pyridine, of which compounds phosphines are preferred. A class of phosphines found to be particularly useful in the process of the present invention are those having the general formula: R3P (II) wherein R independently is an organo group contaning from 1 to 20 carbon atoms, is preferably free from aliphatic carbon-carbon unsaturation, and is bonded to the phosphorus atom by a carbon/phosphorus bond.
The organo group R in the phosphine of formula (II) is preferably a hydrocarbyl group which may be a saturated aliphatic, a saturated cycloaliphatic, an aromatic, a substituted saturated aliphatic, a substituted saturated cycloaliphatic or a substituted aromatic group of which the unsubstituted saturated and aromatic groups are preferred. The substituents are preferably free from aliphatic carbon-carbon unsaturation and may contain, besides atoms of carbon and hydrogen, other atoms, such as oxygen, sulphur and halogen, in particular halogen of atomic number from 9 to 35, provided that such atoms are not directly bonded to phosphorus.Illustrative of suitable saturated aliphatic R groups are hydrocarbyl R groups such as methyl, ethyl, propyl, isopropyl, butyl, isoctyl, decyl, dodecyl, octadecyl, cyclohexyl, cyclopentyl, 3,4-dimethyl cyclopentyl, cyclooctyl, benzyl and ss-phenylethyl. Aromatic R groups include hydrocarbyl aromatic groups such as phenyl, tolyl, xylyl, p-ethylphenyl, p-tert-butylphenyl, m-octyl-phenyl, 2,4-diethylphenyl, pphenylphenyl, m-benzylphenyl and 2,4,6-trimethylphenyl. In the compound of formula (II) the R moieties may be the same or different, although for economic reasons they are preferably identical. Exemplary compounds of formula (II) are triethyl phosphine, tributylphosphine, tricyclohexylphosphine, triphenylphosphine, tris (4-tolyl) phosphine, tris (3-chlorophenyl) phosphine, diphenylhexylphosphine, dibutyloctadecylphosphine, tribenzylphosphine, cyclohexyldibutylphosphine and the like. Preferred compounds are triethylphosphine, tri-n-butylphosphine, tricyclohexylphosphine, tri-t-butylphosphine and triphenylphosphine.
Another type of phosphine which may be used in the operation of the invention is that disclosed by Mason et al in US Patent No 3,400,163. These compounds are bicyclic heterocyclic tertiary phosphines, and are generally hydrocarbyl-substituted or unsubstituted monophosphabicyclo-alkanes of 8 to 9 atoms in which the smallest phosphorus-containing ring contains at least 5 atoms and the phosphorus atom therein is a member of a bridge linkage but is not a bridgehead atom.
Exemplary compounds of formula (I) wherein Xis nitrogen, arsenic, antimony or bismuth are pyridine, diphenylamine, triphenylamine, triphenylarsine, triphenylstibine, triphenylbismuth and tri-n-butylarsine.
We have found that, whereas acetaldehyde is produced as the main product in the presence of cobalt catalysts promoted with an iodide or bromide and an arsenic, antimony or bismuth-containing ligand, the molar yield of realisable ethanol is greatly increased and the molar yield of acetaldehyde and its derivatives is decreased when a Group VIII metal eg ruthenium, is added as co-catalyst.
The term "hydrocarbyl" has been used throughout the foregoing in its accepted meaning as representing a radical formed from a hydrocarbon by removal of a hydrogen atom.
The exact nature of the catalysts of this invention under the reaction conditions is not known but they are thought to be phosphine, arsine, stibine, bismuthine or nitrogen-containing ligand/metal carbonyl/hydride/ halide complexes. The metals are thought to be in a reduced state but their exact valency is not known. It is also possible that under the conditions of the reaction, in addition to mononuclear metallic complexes, polynuclear cluster compounds may be formed, which contain a number of atoms of either the same metal or any combination of the different metals present in the initial reaction mixture. The catalyst may be prepared by first reacting the individual components together and then adding the mixture to the reaction vessel, or by adding the individual components to the reaction vessel and allowing the catalyst to form under the reaction conditions.During formation of the catalyst under the reaction conditions it may be advantageous to employ pressures higher than those used in the subsequent hydrocarbonylation reaction, particularly when reaction pressures of about 100 bar, or below, are used.
In our Belgian Patent No 867,548, our published European application No 78300608.3 are our unpublished European application No 79300174.4 (BP Case No 4516) improvements to the hydrocarbonylation of methanol with synthesis gas are disclosed, these improvements being consequent upon the deliberate addition of certain additives and solvents, such as organic acids and/or derivatives thereof, inert immiscible liquids and various oxygen-containing organic liquids. We have now found that when such additives are used in the presence of the catalysts of the present invention the molar yield of realisable ethanol may be improved still further.
Thus there may be added to the initial reaction mixture an acid and/or an acid derivative having the formula:
wherein in the formula (III) R is a hydrocarbyl group or an oxygen containing hydrocarbyl group and the substituent X is the group -OR1 in which R1 is independently a hydrogen atom, a hydrocarbyl group or an oxygen-containing hydrocarbyl group or Xis the group - 0 - CO - R2 wherein R2 is independently a hydrocarbyl group or an oxygen-containing hydrocarbyl group, as described in our Belgian Patent specification No 867548. Suitable compounds having the structural formula (III) include acetic acid, pcetic anhydride, propionic acid, phenylacetic acid, benzoic acid, methyl acetate and butyl acetate. Preferred compounds having the structural formula (III) are acetic acid and methyl acetate.The acid and/or acid derivative of structural formula (III) may be added in an amount such that the molar ratio of acid and/or acid derivative to free methanol can be as high as 1.5:1, more usually in the range of from 0.1:1 to 0.7:1.
Alternatively, or in addition, the additive may be an inert liquid which is an aryl halide, an ether, a thiophene, a long chain acid, an aromatic acid or a silicone oil. An example of a suitable aryl halide is chlorobenzene. A suitable example of a long chain acid is decanoic acid. Typical of the silicone oils which may be used are polydimethylsiloxane fluids and methyl phenyl silicone fluids. Specific silicone fluids which have been found useful in the process are the DC 200 series of fluids supplied by Dow Corning. The molar ratio of methanol to inert liquid can be varied within wide limits, eg from 30:1 to 1 :10, preferably from 25:1 to 1:2. In the case of silicone oils for which the molecular weight is not known with any degree of certainty the volume added/volume of methanol may be in the range 0.05 to 50, preferably from 0.1 to 5 v/v.
Alternatively, or in addition, there may be added an oxygen-containing organic compound comprising compounds containing at least one of the groups:
which compound preferably exists mainly in the form of a liquid under the reaction conditions employed.
Furthermore the compound is preferably one which is miscible with methanol containing up to 20% w/w water under normal conditions of temnerature and nressure. Whilst the oxvoen-containina nmanic compound containing
a C-O-C group may be an aliphatic, containing N C-OH, > C=O and alicyclic or aromatic ether it is preferred that those compounds
groups are, respectively, aliphatic alcohols, aliphatic ketones and aliphatic aldehydes. Oxygen-containing organic compounds which may be added include, for example, 1 ,4-dioxane, tetrahydrofuran, di-n propylether, diphenylether, acetone, acetaldehyde, n-propanol n-butanol and crown ethers.The oxygen containing organic compound may be added in an amount such that the molar ratio of methanol to the oxygen-containing organic compound is in the range from 20:1 to 1:3, preferably from 10:1 to 1:1.
Alternatively, or in addition, the additive may be a non-polar solvent. Suitable non-polar solvents include alkanes, benzene and alkyl-substituted benzenes as disclosed in the complete specification of UK PATENT No 1,546,428. The molar ratio of methanol to non-polar solvent may suitably be in the range of from 30:1 to 1:10, preferably from 25:1 to 1:2.
Alternatively, or in addition, the solvent may be a co-ordinating solvent, such as sulpholane in the proportions as described hereinbefore for inert and polar-solvents addition.
Whilst it is appreciated that both acids and acid derivatives having the formula (III) and oxygen-containing organic compounds may be formed as by-products during the course of the reaction one aspect of the present invention resides in the addition of one or other or both to the reaction. By so-doing the amount of undesirable side-reaction is reduced, with the attendant consequence that the yield and selectivity to ethanol and/or acetaldehyde is increased.
Methanol may suitably be reacted with carbon monoxide and hydrogen at any temperature in the range 150 to 250, preferably 180 to 230"C and a pressure greater than 50 bars, preferably in the range 50 to 300 bars.
The process may be carried out batchwise or continuously, operation in a continuous manner being preferred. The process may be carried out continuously for example by continuously feeding methanol and synthesis gas to a reactor containing the catalyst, removing from the reactor a liquid product containing ethanol, by-products, unchanged methanol, catalyst and unreacted synthesis gas, separating the synthesis gas which may be recycled to the reactor, removing light ends including ethers, separating the product containing ethanol and by-products from the catalyst and thereafter recovering ethanol from the by-products, there being recycled to the reactor the catalyst and methanol.Other reaction by-products particularly those which can act as precursors for the formation of ethanol such as acetaldehyde and 1 ,1-dimethyloxyethane may also be recycled to the reactor with advantage. It may be necessary to feed from time to time further catalyst.
The residence time may suitably be up to 8 hours, but is preferably in the range of from 10 to 180 minutes.
Within the context of the specification the residence time for batchwise operation is that time during which the reactor is at the specified reaction temperature. When the process is operated continuously the residence time is calculated as follows: Residence Time (Hours) = Volume of the reactor occupied by the liquid phase at STP (litres) Total flow of liquid into the reactor (litres/hour at STP) With regard to the various ratios of reactants to be employed in the process of the invention it has already been stated that the methanol may contain up to 50% by weight of water. In both continuous and batch operations the molar ratio of methanol to synthesis gas fed may be in the range of from 10:1 to 1:20, preferably from 2:1 to 1:5.
In the catalyst the molar ratio of cobalt to iodine or bromide may be in the range from 1:3 to 10:1, preferably from 1:1 to 5:1. The molar ratio of cobalt to compound of formula (I) may be in the range of from 2:1 to 1:10, preferably from 1:1 to 1:5. The molar ratio of iodine or bromine to compound offormula (I) may be in the range of from 2:1 to 1:10 preferably from 1:1 to 1 The molar ratio of the other Group VIII metal or the ratio of the total of these metals to cobalt, where more than one is employed, may suitably be in the I range from 2:1 to 1:100, preferably from 1:1 to 1:20. The molar ratio of cobalt to methanol may be in the rangeoffrom 1:10to 1:1,000 preferablyfrom 1:20 to 1:800.
The invention will now be illustrated by reference to the following Examples and Comparison Tests.
Comparison Test A A stainless steel, magnetically-stirred autoclave equipped for pressurised reactions was charged with methanol (8 moles) containing cobalt acetatetetrahydrate Co(OAc)24H20 (100 x 10-3 moles). The system was purged with nitrogen, then pressurised to 200 bars with a mixture of carbon monoxide and hydrogen (1:1 molar). The reactor temperature was raised to 185"C and maintained at this temperature for 2 hours. When heating was started the pressure in the reactor rose above 200 bars and then began to decrease as the reaction commenced. During the course of the reaction, whenever the pressure in the autoclave fell to 140 bars a fresh charge of carbon monoxide and hydrogen (1:1 molar mixture) was added thereby increasing the reactor pressure to 200 bars.After two hours at 185"C the autoclave was allowed to cool and the reaction product was found to contain realisable ethanol (1.15 moles), realisable acetic acid (0.47 moles) together with other by-products such as dimethyl ether, methyl ethyl ether, acetaldehyde, 1,1-dimethoxy ethane, n-propanol and n-butanol. The amounts of reactants are given in Table 1A and the results in Table 1 B. This test is not an example according to the invention because the catalyst was deficient in components (ii), (iii) and (iv) and is included for the purpose of comparison only.
Comparison Test B The procedure of Comparison Test A was followed except that ruthenium trichloride was added to the reaction mixture. The amounts of reactants are given in Table 1A and the results in Table 1 B.
This is not an example according to the present invention because the catalyst was deficient in components (iii) and (iv). It is included for the purpose of comparison only.
Comparison Test C The procedure of Comparison Test A was followed except that iodine was added to the reaction mixture and it was carried out on a smaller scale. The amounts of reactants are given in Table 1A and the results in Table 1B.
This is not an example according to the present invention because the catalyst was deficient in components (ii) and (iv). It is included for the purpose of comparison only.
Comparison TestD The procedure of Comparison Test A was followed except that both iodine and ruthenium chioride trihydrate were added to the reaction mixture. The amounts of reactants are given in Table 1A and the results in Table 1B.
This is not an example according to the present invention becuase the catalyst was deficient in component (iv). It is included for the purpose of comparison only.
Comparison Test E The procedure for Comparison Test A was followed except that iodine and triphenylphosphine were added to the initial reaction mixture and the reaction time was only 1 hour. The amounts of reactants are given in Table 1A and the results in Table 1 B.
This is not an example according to the present invention because the catalyst was deficient in component (ii). It is included for the purpose of comparison only.
Example 1 The procedure of Comparison Test A was followed except that iodine, ruthenium chloride tri hydrate and triphenyl phosphine were added to the initial reaction mixture and the reaction time was only 1 hour. The amounts of reactants are given in Table 1A and the results in Table 1 B.
Comparison Test F A stainless steel, magnetically-stirred autoclave equipped for pressurised reactions was charged under nitrogen with methanol (1.8 moles) containing cobalt acetate tetrahydrate (0.0225 moles), triphenyl phosphine (0.0393 mole) and iodine (0.0113 mole). The system was purged with nitrogen, then pressurised to 120 bars (roughly equivalent to a pressure of 200 bars at 1 900C) with a mixture of carbon monoxide and hydrogen (1 mole carbon monoxide to 2 moles hydrogen). The reactor temperature was then raised to 1 900C and maintained at this value for 2 hours. When heating was started the pressure in the reactor rose above 120 bars. As soon as the reaction commenced the rate of increase in the pressure began to decrease.It was therefore necessary to make periodic injections of the carbon monoxide/hydrogen mixture to compensate for the gas consumed by the reaction and maintain the rate of pressure increase in accord with achieving a pressure of 200 bars at 190"C. When this objective was achieved the pressure was maintained at a value of 200 bars throughout the reaction by continuously feeding fresh carbon monoxide and hydrogen (1:2 molar mixture) to the autoclave. After 2 hours at 1 90"C the autoclave was allowed to cool and the reaction product was analysed. The amounts of reactants are given in Table 2A and the results in Table 2B.
This is not an example according to the present invention because of the absence of the essential component (ii) of the catalyst. It is included only for the purpose of comparison.
Example 2 The procedure of Comparison Test F was followed except that ruthenium trichloride trihydrate was added to the initial reactants and it was carried out on a larger scale. The amount of reactants are given in Table 2A and the results in Table 28.
Example 3 The procedure of Comparison Test F was followed except that ruthenium trichloride trihydrate and acetone were added to the initial reactants. The amounts of reactants are given in Table 2A and the results in Table 2B.
Example 4 The procedure of Comparison Test F was followed except that ruthenium trichloride trihydrate and acetone were added to the initial reactants. The amounts of reactants are given in Table 2A and the results in Table 2B.
Example 5 The procedure of Comparison Test F was followed except that acetone and osmium trichloride were added to the initial reactants. The amounts of reactants are given in Table 2A and the results in Table 2B.
Comparison Test G The procedure of Comparison Test F was followed except that acetone was added to the initial reactants.
The amounts of reactants are given in Table 2A and the results in Table 2B.
This is not an example according to the present invention because of the absence from the catalyst of the essential component (ii). It is included for the purpose of comparison only.
Comparison Test H The procedure of Comparison Test F was followed except that the carbon monoxide to hydrogen ratio of the synthesis gas fed was 1:1 and the initial pressure was 60 bars increasing to 100 bars at 195"C. In addition acetone was added to the initial reactants. The amounts of reactants are given in Table 2A and the results in Table 2B.
This is not an example according to the present invention because component (ii) was absent from the catalyst system. It is included for the purpose of comparison only.
Example 6 The procedure of Comparison Test H was followed except that ruthenium trichloride trihydrate was added to the initial reaction mixture. The amounts of reactants are given in Table 2A and the results in Table 2B.
Example 7 The procedure of Comparison Test H was followed except that acetone was replaced by sulpholane and ruthenium trichloride trihydrate was added to the initial reaction mixture. The amounts of reactants are given in Table 2A and the results in Table 2B.
Example 8 The procedure of Comparison Test A was followed except for the addition of acetone, iodine, ruthenium trichloride trihydrate and triphenylarsine to the reaction mixture and a reduction in the reaction time to 1 hour. The amounts of reactants are given in Table 3A and the results in Table 3B.
Examination of Table 1 B shows that the use of cobalt acetate tetrahydrate as the sole catalytic entity gives a low molar yield of, and selectivity to, realisable ethanol (Comparison Test A). Although the addition of ruthenium trichloride trihydrate appears to increase the molar selectivity to realisable ethanol, the conversion is low and the molar realisable ethanol yield is decreased slightly (Comparison Test B).
Promoting the cobalt acetate tetrahydrate catalyst with iodine marginally improves the ethanol yield but lowers the selectivity to ethanol (Comparison Test C). Addition of both iodine as promoter and ruthenium trichloride trihydrate as co-catalyst to the cobalt acetate tetrahydrate catalyst reduces both the ethanol yield and selectivity to ethanol markedly (Comparison Test D). However the further addition of triphenyl phosphine as co-promoter dramatically increased both the ethanol yield and selectivity to ethanol (Example 1).
It is seen from Table 2B that the addition of ruthenium trichloride trihydrate as co-catalyst increases significantly both the ethanol yield and selectivity to ethanol (Example 2) of the cobalt acetate tetrahydrate, iodine/triphenyl phosphine-promoted reaction (Comparison Test F) when carried out at a pressure of 200 bars. The addition of acetone (oxygen-containing organic solvent) further improves the ethanol yield (Examples 3 and 4). Example 5 shows that the addition of osmium trichloride as co-catalyst also increases both the ethanol yield and selectivity.
Comparison Test H shows that poor ethanol yields are obtained with a cobalt acetate tetrahydrate, iodine/triphenylphosphine-promoted reaction when carried out at a pressure of 100 bars. The addition of ruthenium trichloride trihydrate, however, greatly improved both the ethanol yield and selectivity (Examples 6 and 7).
TABLE 1A Reactor Feed Additive Catalyst componenets Example/ CH3OH Test (moles) No of (i) Co(OAc)24H2O (ii) Co-catalyst (iii)I2 (iv)Compound Nature moles (moles x 10-3) (moles x 10-3) (moles x 10-3) of formula (I) (moles x 10-3) (a) (b) (c) (d) (e) (f) (g) (h) Comparison 8.0 None - 100 None None None Test A Comparison 8.0 None - 100 RuCl3.3H2O(12.5) None None Test B Comparison 2.0 None - 24.9 None 12.5 None Test C Comparison 8.0 None - 100 RuCl3.3H2O(12.5) 50.0 None Test D Comparison 2.0 None - 25.0 None 12.5 P(C6H5)3(43.7) Test E 1 8.0 None - 100 RuCl3.3H2O(12.5) 50.0 P(C6H5)3(175.2) TABLE 2A (a) (b) (c) (d) (e) (f) (g) (h) Comparison 1.8 None - 22.5 None 11.3 P(C6H5)3(39.3) Test F 2 8.0 None - 100.0 RuCI3.3H2O(12.5) 50.0 P(C6H5)3(175.2) Comparison 1.8 Acetone 0.145 22.5 None 11.3 P(C6H5)3(39.3) Test G 3 1.8 Acetone 0.145 22.5 RuCI3.3H20(5.6) 11.3 P(C6H5)3(39.3) 4 1.8 Acetone 0.145 22.5 RuCI3.3H2O(2.8) 11.3 P(C6H5)3(39.3) 5 1.6 Acetone 0.130 20.2 OsCI3(3.4) 10.1 P(C6H5)3(35.4) Comparison 1.8 Acetone 0.148 22.5 None 11.3 P(C6H5)3(39.3) Test H 6 1.8 Acetone 0.145 22.5 RuCI3.3H2O(5.6) 11.3 P(C6H5)3(39.3) 7 1.6 Sulpho- 0.128 20.0 RuCl3.3H2O(5.0) 10.0 P(C6H5)3(35.0) lane TABLE 3A (a) (b) (c) (d) (e) (f) (g) (h) 8 1.8 Acetone 0.145 22.5 RuCI3.3H20(5.6) 11.3 As(C6H5)3(34.7) TABLE 1B %Molar yields on methanol fed %Molar Example/ Temp Pressure %CH3OH %Molar selectivity Test ( C) (bars) Realis- Realis- n-C3H7OH conver- yield to able able Dimethyl CH3CHO sion CH4+CO2 realisable C2H5OH CH3COOH acetal* n-C4H9OH ** C2H5OH (i) (j) (k) (l) (m) (n) (o) (p) (q) (r) (s) Comparison 185 200 14.4 5.9 3.3 < 1 1.3 36.8 5.9 39.1 Test A Comparison 185 200 13.7 4.7 5.3 < 1 1.7 25.2 11.5 54.4 Test B Comparison 185 200 16.6 10.5 4.9 1.1 < 1 45.0 6.8 36.9 Test C Comparison 185 200 9.9 4.3 9.1 < 1 < 1 39.3 48.4 25.2 Test D Comparison 185 200 9.9 9.6 14.2 5.9 < 1 53.6 8.8 18.5 Test E 1 185 200 27.7 8.5 3.9 < 1 < 1 43.0 7.1 64.4 * Dimethyl acetal is 1,1-dimethoxyethane ** The % molar yield of methane + carbon dioxide (ie CH4+CO2) is calculated on the carbon monoxide fed to the reaction TABLE 2B (i) (j) (k) (I) (m) (n) (o) (p) (q) (r) (s) Comparison 190 200 18.9 3.3 8.9 2.0 1.8 45.1 7.0 41.9 Test F 2 190 200 34.6 2.9 1.2 < 1 1.2 47.2 14.6 73.3 Comparison 190 200 24.7 3.8 9.0 2.2 1.5 53.5 8.9 46.2 Test G 3 190 200 35.4 3.2 < 1 < 1 < 1 52.6 18.1 67.3 4 190 200 36.4 3.8 1.8 < 1 1.4 53.2 8.7 68.4 5 190 200 26.9 2.8 8.0 < 1 1.2 46.0 9.1 58.5 Comparison 195 100 5.2 2.6 10.3 1.3 < 1 27.7 5.9 18.8 Test H 6 190 100 16.4 3.5 < 1 < 1 < 1 31.3 25.1 52.4 7 190 100 15.6 4.7 < 1 < 1 < 1 25.8 24.7 60.5 TABLE 3B (i) (j) (k) (I) (m) (n) (o) (p) (q) (r) (s) 8 185 200 16.4 9.6 13.0 4.7 < 1 55.5 3.5 29.5

Claims (16)

1. A process for the production of ethanol which process comprises reacting at elevated temperature and pressure methanol with hydrogen and carbon monoxide in the presence of a catalyst comprising: (i) cobalt, (ii) one or more other metals of Group VIII of the Periodic Table, (iii) an iodide or a bromide, and (iv) a compound having the formula:
wherein X is nitrogen, phoshorus, arsenic, antimony or bismuth and A, B and C are individually monovalent organic radicals or X is phosphorus, arsenic or antimony and any two of A, B and C together form an organic divalent cyclic ring system bonded to the X atom or X is nitrogen and all of A, B and C together form an organic trivalent cyclic ring system bonded to the X atom.
2. A process according to claim 1 wherein the cobalt constituting component (i) of the catalyst is in the form of cobalt acetate, cobalt formate or cobalt propionate.
3. A process according to either one of the preceding claims wherein the other Group VIII metal constituting component (ii) of the catalyst is either iron, ruthenium, osmium, rhodium, iridium, nickel, palladium or platinum.
4. A process according to claim 3 wherein the Group VIII metal is ruthenium.
5. A process according to any one of the preceding claims wherein component (iii) of the catalyst is the iodide.
6. A process according to any one of the preceding claims wherein the compound constituting component (iv) of the catalyst has the formula: R3P (II) wherein R independently is an organo group containing from 1 to 20 carbon atoms, is free from carbon-carbon unsaturation and is bonded to the phosphorus atom by a carbon/phosphorus bond.
7. A process according to claim 7 wherein R in the compound of formula (II) is a hydrocarbyl group.
8. A process according to either one of claims 6 or 7 wherein the compound of formula (II) is triethylphosphine, tri-n-butylphosphine, tricyclohexylphosphine, tri-t-butylphosphine or triphenylphos- phine.
9. A process according to any one of claims 1 to 5 wherein the compound constituting component (iv) of the catalyst is pyridine, diphenylamine, triphenylamine, triphenylarsine, triphenylstibine, triphenylbismuth or tri-n-butylarsine.
10. A process according to any one of the preceding claims wherein there is deliberately added either acetic acid or methyl acetate in an amount such that the molar ratio of the additive to free methanol is in the range from 0.1:1 to 0.7:1.
11. A process according to any one of the preceding claims wherein there is deliberately added either chlorobenzene, decanoic acid, a poly-dimethylsiloxane fluid, or a methyl phenyl silicone fluid in an amount such that the molar ratio of methanol to additive is in the range from 25:1 to 1:2.
12. A process according to any one of the preceding claims wherein there is deliberately added either 1,4-dioxane, tetrahydrofuran, di-n-propylether, diphenylether, acetone, acetaldehyde, n-propanol, nbutanol, sulpholane or a crown ether in an amount such that the molar ratio of methanol to the additive is in the range from 10:1 to 1:1
13. A process according to any one of the preceding claims wherein there is deliberately added an alkane, benzene or an alkyl-substituted benzene in an amount such that the molar ratio of methanol to the additive is in the range from 25:1 to 1:2.
14. A process according to any one of the preceding claims wherein the elevated temperature is in the range from 150 to 250"C, the elevated pressure is greater than 50 bars and the residence time is up to 8 hours.
15. A process according to claim 14 wherein the elevated temperature is in the range from 180 to 2300C, the elevated pressure is in the range from 50 to 300 bars and the residence time is from 10 to 180 minutes.
16. A process according to any one of the preceding claims wherein the molar ratio of carbon monoxide to hydrogen is in the range from 2:1 to 1 :3, the molar ratio of methanol to synthesis gas fed is in the range from 10:1 to 1 :20, in the catalyst the molar ratio of component (i) to component (iii) is in the range from 1:3 to 10:1,the molar ratio of component (i) to component (iv) is in the range from 2:1 to 1:10, the molar ratio of component (iii) to component (iv) is in the range from 1:1 to 1 :8, the molar ratio of component (ii) to component (i) is in the range from 2:1 to 1:100 and the molar ratio of component (i) to methanol is in the range from 1:10to 1:1000.
GB7939903A 1978-11-21 1979-11-19 Use of group viii metals as co-cata-lysts in the homologation of methanol Expired GB2036739B (en)

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Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2493835A2 (en) * 1980-11-12 1982-05-14 Union Rheinische Braunkohlen PROCESS FOR PREPARING DIMETHYLACETAL OF ACETALDEHYDE
EP0053132A1 (en) * 1980-05-21 1982-06-09 Us Energy Method and system for ethanol production.
DE3045891A1 (en) * 1980-12-05 1982-06-09 Union Rheinische Braunkohlen Kraftstoff AG, 5000 Köln METHOD FOR PRODUCING ACETALDEHYDE AND ETHANOL
EP0053792A1 (en) * 1980-12-10 1982-06-16 Ruhrchemie Aktiengesellschaft Process for synthesizing ethanol and n-propanol from methanol
EP0055887A2 (en) * 1980-12-29 1982-07-14 Gulf Research & Development Company Novel catalyst system and process for producing ethanol using said novel catalyst system
EP0136499A1 (en) * 1983-08-24 1985-04-10 Ruhrchemie Aktiengesellschaft Process for the production of ethanol
EP0141535A2 (en) * 1983-10-08 1985-05-15 The British Petroleum Company p.l.c. Process for the production of ethanol and/or acetaldehyde by the metal catalysed liquid phase reaction of methanol, carbon monoxide and hydrogen in the presence of a solvent
US4605796A (en) * 1983-12-26 1986-08-12 Agency Of Industrial Science And Technology Process for producing ethanol
US4650911A (en) * 1982-06-16 1987-03-17 S. Ishizaka, President Of Agency Of Industrial Science And Technology Process for producing ethanol
US4670473A (en) * 1985-08-09 1987-06-02 Amoco Corporation Syn gas conversion
US4727200A (en) * 1987-03-27 1988-02-23 Union Carbide Corporation Alcohol homologation
US4760171A (en) * 1986-12-10 1988-07-26 Agency Of Industrial Science And Technology Process for producing ethanol
EP0287728A1 (en) * 1987-04-24 1988-10-26 Amoco Corporation Syn gas conversion

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0053132A1 (en) * 1980-05-21 1982-06-09 Us Energy Method and system for ethanol production.
EP0053132B1 (en) * 1980-05-21 1984-09-19 United States Department Of Energy Method and system for ethanol production
FR2493835A2 (en) * 1980-11-12 1982-05-14 Union Rheinische Braunkohlen PROCESS FOR PREPARING DIMETHYLACETAL OF ACETALDEHYDE
DE3045891A1 (en) * 1980-12-05 1982-06-09 Union Rheinische Braunkohlen Kraftstoff AG, 5000 Köln METHOD FOR PRODUCING ACETALDEHYDE AND ETHANOL
FR2495607A1 (en) * 1980-12-05 1982-06-11 Union Rheinische Braunkohlen PROCESS FOR THE PREPARATION OF ACETALDEHYDE AND ETHANOL
EP0053792A1 (en) * 1980-12-10 1982-06-16 Ruhrchemie Aktiengesellschaft Process for synthesizing ethanol and n-propanol from methanol
EP0055887A2 (en) * 1980-12-29 1982-07-14 Gulf Research & Development Company Novel catalyst system and process for producing ethanol using said novel catalyst system
EP0055887A3 (en) * 1980-12-29 1982-08-25 Gulf Research & Development Company Novel catalyst system and process for producing ethanol using said novel catalyst system
US4650911A (en) * 1982-06-16 1987-03-17 S. Ishizaka, President Of Agency Of Industrial Science And Technology Process for producing ethanol
EP0136499A1 (en) * 1983-08-24 1985-04-10 Ruhrchemie Aktiengesellschaft Process for the production of ethanol
EP0141535A2 (en) * 1983-10-08 1985-05-15 The British Petroleum Company p.l.c. Process for the production of ethanol and/or acetaldehyde by the metal catalysed liquid phase reaction of methanol, carbon monoxide and hydrogen in the presence of a solvent
EP0141535A3 (en) * 1983-10-08 1985-06-26 The British Petroleum Company p.l.c. Process for the production of ethanol and/or acetaldehyde by the metal catalysed liquid phase reaction of methanol, carbon monoxide and hydrogen in the presence of a solvent
US4605796A (en) * 1983-12-26 1986-08-12 Agency Of Industrial Science And Technology Process for producing ethanol
US4670473A (en) * 1985-08-09 1987-06-02 Amoco Corporation Syn gas conversion
US4760171A (en) * 1986-12-10 1988-07-26 Agency Of Industrial Science And Technology Process for producing ethanol
US4727200A (en) * 1987-03-27 1988-02-23 Union Carbide Corporation Alcohol homologation
EP0287728A1 (en) * 1987-04-24 1988-10-26 Amoco Corporation Syn gas conversion

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