CA1173059A

CA1173059A - Manufacture of oxygenated compounds

Info

Publication number: CA1173059A
Application number: CA000374746A
Authority: CA
Inventors: David W. Smith
Original assignee: National Destillers and Chemical Corp
Current assignee: Millennium Petrochemicals Inc
Priority date: 1980-04-21
Filing date: 1981-04-06
Publication date: 1984-08-21
Also published as: DE3115854A1; NL8101956A; KR830005080A; GB2074164A; AU6962681A; NZ196857A; IT1137141B; BR8102398A; JPS56166133A; GB2074164B; ZA812443B; FR2480743A1; IT8121278A0; BE888462A

Abstract

ABSTRACT OF THE DISCLOSURE Process of reacting carbon monoxide and hydrogen in the presence of halogen-containing ruthenium catalysts to produce acetaldehyde and ethanol.

Description

~173059 .

This invention is concerned with the production of acetaldehyde and ethanol by reaction of carbon monoxide and hydrogen in the presence of a ruthenium catalyst.
Acetaldehyde is a very valuable commercial chemical with a wide variety of uses particularly as an intermediate for production of commercial chemicals. Ethyl alcohol is also an important valuable commercial chemical useful for a wide variety of purposes including as a chemical intermediate, as a solvent, 10 and perhaps more importantly as a component of gasohol.
The reaction of carbon monoxide and hydrogen has long been known and can result in a variety of products depending on reaction conditions and the type of catalyst employed. U.S.
Patent 3,833,634 describes the reaction of carbon monoxide and 15 hydrogen over rhodium catalyst to produc~ ethylene glycol, propylene glycol, glycerol, methanol, ethanol, methyl acetate and othex products. French Patent 2,259,077 discloses produc-ing ethanol from carbon monoxide and hydrogen usiny rhodium on silica gel as catalyst at 300-350C. and 1000-2500 psi pressure.
20 West German Specification 2,644,185 describes conversion of carbon monoxide and hydrogen to hydrocarbons employing Ru3(CO~12 in tetrahydrofuran as solvent. Use of the same ruthenium carbonyl catalyst on solid supports to produce hydrocarbon pro-~ ducts is described in J.A.C.S. 100, 2590 (1978). The conversion 25 of carbon monoxide and hydrogen over ruthenium carbonyl clustersto methanol and methyl formate has been described [ACS/CSJ
Chemical Congress Abstracts, INORG. 428 (1979)].
~ ~= .

It has now been found that the reaction of carbon 30 monoxide and hydrogen over certain selected ruthenium catalysts provides C2-oxygenated products, that is acetaldehyde and ethanol. The reaction apparently proceeds in several stages, 1 with acetaldehyde being the preclominant product in the early stages and ethanol predominating in later stages, so that the process can ~ive rise to one or the other product, or mixtures of these products, which can be readily separated as by frac-5 tionation. Thus~ by controlling reaction parameters, theprocess can be controlled to favor one or the other product, as desired. Methanol is the principal by-product obtained in the present process.
If desired, the overall process of the invention can 10 be conducted in separate stages, the initial stage re~ulting in production of acetaldehyde as the principal product, and the final stage resulting in production of ethanol as the principal product.
The very desirable results obtained in accordance with 15 the present process renders the process particularly amenable to commercial production of acetaldehyde and ethanol, not only from the viewpoint of the substantial yields of the products, but also the ease of recovery from the co-produced methanol, e.g., by fractional distillation. The ease of recovery is 20 extremely important since it permits separation of the products from the reaction mixture even in those process runs where methanol may be produced in substantial amount. Thus, for example, even where acetaldehyde is present in amounts corre-sponding to about 10 mole-percent, and even less, of the reac-25 tion product mixture, the ease of separation will permitrecovery of the aldehyde.
Acetaldehyde is also produced in a high order of purity. Usually, the initial stage reaction mixture can be used as such in the final stage reaction to produce ethanol by 30 reduction of acetaldehyde.
The results obtained with the present invention are indeed quite surprising and totally unexpected. In particular, 11~73(3S9 .

1 ruthenium carbonyl complcxcs have been known to catalyze the reaction of carbon monoxide and hydrogen to form only one carbon products such as methanol, methane and methyl formate.
Further, under the relatively mild reaction conditions 5 employed in the present process, particularly the moderate reaction temperatures, ruthenium ca~bonyl, Ru3(C0)12, forms little if any of the C2-oxygenated products of this invention.
Thus, the results obtained with the present catalysts are unobvious, particularly in view of the high conversions and 10 specificity of the process in producing two-carbon oxygenated products.

The process of the present invention is accomplished by contacting carbon monoxide and hydxogen in the presence of 15 certain ruthenium-containing catalysts in a suitable solvent at elevated temperature and superatmospheric pressure. The major products of the reaction are acetaldehyde and ethanol, with the major by-product being methanol. The manner of contact is not critical since any of the various procedures normally 20 employed in this type of reaction can be used as long as efficient gas-li~uid contact is provided. Thus, the processes may be carried out by contacting the ruthenium catalyst in reaction solvent with a mixture of carbon monoxide and hydrogen at the selected conditions. Where convenient, trickle phase 25 operation can be used.
In view of the two-stage nature of the present process, the implementation can take several forms to produce ethanol.
The reaction can be accomplished by allowing both stages to proceed consecutively at suitable temperature and pressure, or 30 alternatively, the reaction can be stopped at the end of the first phase where the product is acetaldehyde and the second phase can be carried out under any applicable reduction process which will result in conversion of the aldehyde group of acetaldehyde to the primary alcohol group of ethanol. In most 35 cases, however, the production of ethanol occurs quite readily.

1:173~5S~

1 Usually, ethanol predominates as product when employing usual reaction conditions, the product mix being at least about 50/50 in most cases.
A wide variet~ of reduction processes can be employed 5 fox che second phase reaction including the well-known chemical reducing agents employed in reducin~ aldchydes to primary alcohols. For commercial processes, however, where possible, catalytic reductions employi~g hydrogen are usually preferred since they are more practical and efficient especially with 10 catalysts which can be regenerated and thus are re-usable. In the present process, catalytic hydrogenation is preferred for these same reasons, especially with catalysts which can be regenerated. Any hydrogenation catalyst can be employed.
Thus, typical hydrogenation catalysts include, for 15 example, Raney Nickel, cobalt, copper chromite, rhodium, palladium, platinum, and similar such metal catalysts, which can be used conveni~ntly on supports such as charcoal, silica, allmina, kieselguhr and the like. The conditions of catalytic hydrogenation are well-known and, in general, the reaction can 20 be conducted at temperatures ranging from about 30~ to about lSO~C., usually at pressures of from about 100 to about 5000 psig. The use of higher temperatures and pressures, though - operable, provides no special advantage and usually requires special equ pment which economically is disadvantageous and 25 therefore not preferred.
Particularly preferred hydrogenation catalysts are those which characteristically require short reaction times, e.g~, palladium and nic~el, which~is most desirable for commercial processes for economic reasons.
The active catalyst species of the catalyst system for the present process has not been fully identified but it is assumed to be comprised of ruthenium in complex combination with carbon monoxide together with a halide ligand. It is sufficient that the catalyst system initially comprise a 1~73~59 1 source of ruthenium and a source of halide and the active catalyst species then forms on initiation of the process, e.g., the complex ruthenium carbonyl will form on addition of the reactants, i.e., carbon monoxide and hydrogen. Alternatively, 5 the ruthenium source can be a preformed complex carbonyl.
Further, the sourc~ of both ruthenium, or ruthenium carbonyl complex, and halide can be the same compound, e.g., ruthenium carbonyl halides which are commercially available. The catalyst systems can be formed with ruthenium carbonyl halides 10 or alternatively by the combination of ruthenium carbonyl or hydrocarbonyl complexes with a separate source of halide.
The catalyst systems can be employed as such or deposited or affixed to a solid support such as molecular sieve zeolites, alumina, silica, ion exchange resin or a polymeric ligand.
15 The preferred halides are chloride and bromide. The ruthenium halocarbonyl catalysts may be represented by the formula Rua(CO)bXc wherein a, b and c are integers and X is halide.
Such catalysts may be prepared by reaction of ruthenium halides with carbon monoxide or by reaction of ruthenium 20 carbonyl complexes with halogen-containing compounds.
Alternatively, ruthenium carbonyl halides are available commercially, (e.g., from Matthey-Bishop, Malverne, PA).
The catalysts of this invention may contain other ligands in addition to halide ligand which must be present 25 for the present process. As described in U.S. Patent 3,833,634, suitable ligands are compounds which contain at least one nitrogen and/or at least one oxygen atom, said atoms having a pair of electrons available for formation of coordinate bonds with ruthenium. Illustrative organic 30 ligands include various piperazines, dipyridyls, N-substituted diamines, aminopyridines, glycolic acid, alkoxy-substituted ~L173~59 1 acetic acids; tetrahydrofuran, dioxane, 1,2,-dimethoxybenzene, alkyl ethers of alkylene glycols, alkanolamines, iminodiacetic acid, nitrilo~riacetic acid, ethylenediaminetetraacetic acid and the like. In U.S. Patent 3,527,809 are described 5 phosphoruc-containing ligands such as trialkyl, triaryl and tricycloalkyl phosphites and phosphines, as well as the analogous antimony and arsenic compounds. Other ligands such as tin halides, e.g., SnC13 and SnBr3, or NO may be present.
The activity of the ruthenium catalyst systems of lO this invention is increased by the addition of alkali metal salts, particularly halide salts. In present experience, the most preferred are lithium halides, especially lithium chloride and lithium bromide. At 200C., a LiCl/Ru ratio of 15 resulted in reduction of 40 moles CO/mole Ru/hr. with a 15 44% selectivity to C2-oxygenated products. Comparative figures for lithium bromide activation were 13 moles CO and 44% selectivity.
For most purposes, the amount of halide employed can be varied considerably, with molar ratios of at least about 20 0.1 mole per mole of ruthenium being operable. The alkali metal halides may be present in large molar excess, e.g., about 115 moles/mole ruthenium, and even higher.
- In lieu of addition of alkali metal salts, preferably halides, the salts can be used with the selected catalyst to 25 produce ruthenium halocarbonyl anions which, for the purpose of this disclosure, are represented by the general formula MaRubXc(CO)d wherein a, b, c and d are integers, e.g.
NaRuBr3(CO)3 and NaRuC13(CO)3. Such compounds can be pre-formed and then added to the reaction in solvent as the 3O catalyst system.
The hydrohalic acids HCl and HBr also promote the activity of the ruthenium halocarbonyls of the present new ~ 30S9 1 process but to a lesser extent than alkali metal halides.
The addition of HCl increased the catalytic activity of ERuC12(CO)3]2 only to about 25% that of lithium chloride with a decrease of selectivity to ethanol and acetaldehyde, while 5 both HCl and HBr promoted the activity of Ru3(CO)12. Large excesses of hydrogen halides are of no advantage and are usually avoided since they may tend to decrease catalyst activity.
In addition, the catalyst systems for this invention 10 can also be formed by addition of halide to a suitable ruthenium compound in the selected solvent or in the reaction mixture, if preferred. For example, ruthenium acetylacetonate in combination with hydrogen halide in reaction solvents provides essentially the same results as preformed catalyst, 15 e.g. [Ru(CO)2Cl]2. It is noted that, in the absence of halide, e.g. chloride or bromide, the ruthenium catalysts, such as ruthenium carbonyl, form methanol as the principal product with negligible or trace amounts of ethanol or acetaldehyde. The amounts of halide added to the catalyst 20 need not be stoichiometric since even small amounts will result in the production of some ethanol. For most purposes, however, it is preferred to employ at least an equimolar - amount of halide which can be added as aqueous solution, e.g.
hydrohalic acid, or solution in organic solvents such as the 25 lower alkanols.
When lithium chloride was employed at equimolar ratios with Ru3(CO)12, at 200C., 13 moles CO/mole Ru/hr. were reduced with a selectivity to two-carbon products of 48%.
With excess lithium bromide (rV60 moles/mole Ru) at 250C., 30 enhanced productivity to two-carbon products was observed.
The determination of suitability of starting ruthenium compounds to be used for in situ formation of the halide-containing catalyst can be accomplished by a simple test procedure which involves running small scale reactions 35 with the selected ruthenium comPound, halide and reactants CO

. il730S~

1 and H2 in solvent. At the completion of the miniature reactions, gas~ uid chromatographic analyses of the reaction mixture will identify the products and, of course, will identify those ruthenium compounds which are suitable, through 5 in situ treatment, for production of ethanol and/or acetalde-hyde. ~sing this test procedure, suitable starting ruthenium compounds are easily identified.
When acetaldehyde is the desired product, of course, only the first stage reaction need be carried out. The 10 product can be separated fr~m the co-produced methanol, any ethanol formed and reaction solvent, if necessa~y, by fractional distillation.
As should be apparent, the ruthenium catalyst employed in the first stage reaction can also serve as the hydrogenation 15 catalyst for the second stage reaction to produce ethanol.
Thus, if the first phase reaction is allowed to continue, eventually the hydrogenation reaction will yield ethanol. In general, the ruthenium catalyst of the first stage reaction is an effective catalyst for the second stage hydrogenation, but 20 other hydrogenation catalysts can be used in lieu of the ruthe-nium catalyst. If desired, the ruthenium catalyst can be con-verted to a more effective hydrogenation catalyst by addition - of a phosphine ligand, particularly triaryl phosphines such as triphenyl phosphine, although other phosphine ligands as 25 described in U.S. Patent 3,527,809 can be used as well.
It is possible to effect the reduction step over metal catalysts such as palladium and nickel, or copper chromite and to effect the second stage reaction in a separate reactor.
Thus, the first stage reaction can be conducted in a first 30 reactor under selected conditions of temperature and pressure, and after completion the first stage product, with or without 1~73(~59 g . .

1 isolation from the reaction mixture, can then be transferred to a second reactor under selected conditions of temperature and pressure to eff~ct the hydrogenation reaction.
There of course is no criticality about stopping the 5 reaction exactly at the termination of the first stage, or holding the second stage reaction until all acetaldehyde is reduced to ethanol. The reaction can be stopped at any conven-ient point which will be dictated by the product desired, along with other considerations. Thus, after substantially maximum 10 yield of acetaldehyde is obtained, usually within about 2 hours, the reaction can be sto~ped and the aldehyde recovered.
However, the reaction mixture will undoubtedly contain quanti-ties of ethanol forMed through the second stage reaction. The products, however, are easily separable and are almost equally 15 commercially important. Obviously; where ethanol is desired, the reaction can be allowed to proceed, within economic consid-erations, until reasonably complete to obtain ethanol as the major product, and of course acetaldehyde the minor product.
The present invention, therefore, provides a simplified 20 process for production of acetaldehyde. In addition, this invention affords a simplified process for obtaining ethanol by either allowing the initial process for aldehyde - production to continue so that hydrogenation yields ethanol or, alternatively, the aldehyde product of the first stage reaction 25 is reduced employing art-recognized reduction processes to ethyl alcohol. In the latter process, the acetaldehyde product of the first stage reaction can be used in the form of the reaction mixture, or the product can be isolated, as by frac-tionation, and used in purified form.
The amount of catalyst employed in the present process does not seem to be critical and can vary considerably. At least a catalytically effective amount of catalyst should be used, of course. In general, an amount of catalyst which is effective to provide a reasonable reaction rate is sufficient.
35 As little as 0.001 gram atoms of ruthenium per liter of reaction ~173C~9 1 medium can suffice while amounts in excess of 0.1 gram ato~s do not appear to materially affect the rate of reaction. For most purposes, the ef~ective preferred amount of ruthenium is in the range of from about 0.002 to about 0.05 gram atoms per liter.
The reaction conditions are not overly critical in that wide ranges of elevated temperature and superatomspheric pressures are operable. The practical limitations of pxoduc-tion equipment will dictate to a great extent the selection of temperatures and pressure at which the reaction is to be 10 effected- Thus, using available production systems, the selected elevated temperature should be at least about 150C.
and can range up to about 300C. For most purposes, the preferred operating temperature ranges from about 175~ to about 275C. The superatmospheric pressure should be at 15 least about 10 atmospheres and can range up to almost any pressure attainable with production apparatus. Since extremely high pressure apparatus is quite expensive, pressures to about 700 atmospheres are suggested. Most desirably, the pressure should be in the range of from about 150 to about 400 atmos-20 pheres, particularly when employing the aforesaid preferredtemperature range. The reaction is preferably carried out in a solvent which ~ill dissol~e polar materials and which pre~erably is aprotic. The preferred solvents are N-substituted amides in 25 which each hydrogen of the amido nitrogen is substituted by a hydrocarbon group, e.g., l-methyl-pyrrolidin-2-one, N,N-dimethylacetamide, N,N-diethylacetamide, N-methylpiperidone, 1,5-dimethylpyrrolidin-2-one, l-benzyl-pyrrolidin-~-one, N,N-dimethylpropionamide, hexamethylphosphoric triamide and similar 30 such liquid amides. The amides are preferred solvents since their use results in the highest yields of product in present experience. Other solvents, usually aprotic, can be used but the yields are substantially less than obtained with the pre-f~rred amide solvents. Such solvents include, for example, 11~73(~S~

1 cyclic ~thers such as tetrahydrofur~n, dioxane and tetrahydro-pyran; ethers such as diethyl ether, 1,2-dimethoxybenzene;
alkyl ethers of alkylene glycols and polyalkylene glycols, e.g., me~hyl e~hers of ethylene glycol, propyiene glycol and di-, tri-5 and ~etraethylene glycols; ketones such as acetone, methylisobutyl ketone, and cyclohexanone; esters, such as ethyl acetate, ethyl propionate and methyl laurate; and alkanols, such as methanol, ethanol, ~ropanol, 2-ethylhexanol and the like; tetramethylurea; ~-butyrolactone; and mixtures thereof.
10 The selected solvent should preferably be liquid under the reaction conditions.
The preferred solvents are aprotic organic amides.
The contemplated amides include cyclic amides, i.e., in which the amido group is part of a ring structure such as in pyrrol-15 idinones and piperidones; acylated cyclic amines, such as N--acyl piperidines, pyrroles, pyrrolidines, piperazines, morpho-lines, and the like, preferably in which the acyl group is derived from a lower alkanoic acid, e.g., acetic acid; as well as acyclic amides, i.e., wherein the amido group is not part of 20 a ring structure as in acetamides, formamides, propionamides, caproa~ides and the like. The most preferred of the amides are those in which the amido hydrogen atoms are fully replaced by - hydrocarbon groups preferably containing not more than 8 carbon atoms. Exemplary hydrocarbon groups are alkyl, preferably lower 25 alkyl such as methyl, ethyl and butyl; aralkyl, such as benzyl and phenethyl; cycloalkyl, such as cyclopentyl and cyclohexyl;
and alkenyl, such as allyl and pentenyl. The preferred amido nitrogen substituents are lower alkyl, especially methyl, ethyl and propyl groups and aralky~ groups, especially benzyl. The 30 most preferred amide solvents include 1-methylpyrrolidin-2-one, l-ethylpyrrolidin-2-one, and l-benzylpyrrolidin-2-one. Of course, mixtures of the solvents can be used, e.g. amide solvent with other solvents.
Water is not critical to the reaction and can be 35 present without serious adverse effect. It tends 1 to react with carbon monoxide to form C02 and hydrogen (water gas shi~t). Water can be e~cluded since it can reduce the selectivity of conversion of carbon monoxide, or the water-gas shif~ can be used advantageously to generate hydrogen.
The reaction pressures represent the total pressure of the gases contained in the reactor, i~e. carbon monoxide and H2, and, i~ present, any diluent gas such as nitrogen. As in any gaseous system, the total pressure is the sum of partial pressures of component gases. In the present reaction, the 10 molar ratio of hydrogen to carbon monoxide can range from about 1/10 to about 10/1, with the preferred ratio, from about 1/5 to about 5/1, and the reaction pressure can be achieved by - adjusting the pressure of these gases in the reactor.
Where the second phase reaction is carried out in a 15 separate reactor whether over the originally present ruthenium catalyst or a different metal hydrogenation catalyst, the reaction is normally conducted under hydrogen gas without diluent gas, as is usual in catalyzed hydrogenation reactions.
As with any process of this kind, the present process 20 can be conducted in batch, semi-continuous, and continuous operation. The reactor should be constructed of materials which will withstand the temperatures and pressures required, and the internal surfaces of the reactor are substantially ~ inert. The usual controls can be provided to permit control 25 of the reaction such as heat-exchangers and the like. The reactor should be provided with adequate means for gas-liquid contact such as shaking, stirring, oscillation, trickle column operation and like methods. Catalyst as well as reactants may be introduced into the first stage or the second stage reactor 30 at any time during the process for replenishment. Recovered catalyst, solvent and unreacted starting materials may be recycled.
The relative yields of ethyl alcohol, acetaldehyde and methanol are not overly critical since the product mixture can 35 be readily separated into the components by known techniques, l3l73(~59 1 especially by fractional distillation, regardless o~ the pro-portions contained in the mixture. Therefore, even where the desired product is 10-20~ of the reaction mixture, it can be readily separated from the mixture, especially under continuous 5 processing. Of course, the preferred processes yield mixtures in which acetaldehyde and ethanol predominate as the reaction product and methanol, as a by~product, is minimal.
The process conditions for the separate first stage reaction are essentially the same as employed in the first 10 stage of the combined two-stage reaction. Thus, the reaction is carried out at a temperature of at least about 150C. to obtain a reasonable reaction rate and up to about 300C. For best results, the temperature should be in the range of from about 175C. to about 275C. The total pressure of gas used 15 is generally maintained at from about 10 up to about 700 atmospheres, with from about 150 to about 600 atmospheres being preferred. Of course, high pressures and higher temperatures can be used but with no appreciable advàntage and, since they require the use of special high pressure 20 equipment, they are usually avoided.
The reaction conditfions employed in the second reaction stage, i.e. the hydrogenation, can be any of the standard reaction temperatures and pressures employed for such reactions since neither temperature nor pressure are critical for this 25 reaction. Preferably, the hydrogenation is conducted at a temperature of at least about 100C. in order to effect a reasonable reaction rate. Of course, lower temperatures can be used if longer reaction times can be tolerated. The pressure of hydrogen gas is not excessively critical as long as suffic-30 ient gas is available for the hydrogenation. For convenience, ~173~59 1 the pressure will range from about 500 psi to as much ~s 5000psi, ~lthough even higher pressures can ~e employed.
When the catalyst s$1ected for the hydrogenation step is other than ruthenium, it is preferred to remove the ruthenium 5 catalyst from the first stage reaction mixture. This preference is primarily predicated on the desirability of avoiding concomi-tant catalytic effects which may tend to reduce the yield of ethanol.
The following examples further illustrate the invention.
10 The equipment, synthetic procedure and analyses employed are as follows:
I. Equipment --- A Reactors Reactions were carried out in Parr 71 ml reactors con-15 structed of 310SS having one Type A 1/4" coned socket (Cat.$4740, Parr Instrument Co., Moline, IL). Glass liners with open tops were employed. Reactor seal was a modified ~ridgeman type, incorporating a special two piece gasket (Cat. ~61HD), comprising silver (exposed to process) with a nickel back-up ring. This 20 gasket arrangement was necessitated due to attack by carbon monoxide of the originally supplied one-piece nickel gasket.
The reactors were capped with 316SS Whitey severe - service valves with high temperature Grafoil packing (Cat.
~SS3NBS4-GTA-9K-3N, Whitey Co., Oakland, CA). The valves were 25 coupled to the reactors with 316SS Sno-Trik male high pressure to Swagelok adapters (Cat. ~SS-44M-A-400, Sno Trik Co., Solon, OH), and Swageiok port connectors (Cat. ~SS-401-PC, Crawford Fitting Co., Cleveland, OH).
B. Agitation and Heating 3 The arm of a Burrell wrist action shaker was projected into an oven comprising an insulated box and electrical strip-heaters. Reactors were clamped to the shaker arm. Oven ~1~73(~S9 1 temperature was measured by a thermocouple which connected to a con.roller ton-off type). A ti~er was used to contral reaction time by interrupting power to the temperature controller at the desired time. The temperature controller was used to activate 5a relay coilO A Variac was used to regulate the voltage going to the heater from the relay.
In cases where more vigorous agitation was required, the reactors (without glass liners) were bolted to a paint shaker by means of a special bracket which prevented whip loaction of the valve which would cause the port connector to sever.
C. Gas Compression and Delivery Custom carbon monoxide-hydrogen mixtures (Union Carbide CorpD, Linde Division, South Plainfield, NJ) were piped into an 15air driven, double-ended compressor (Cat. #46-14035, American Instrument Co., Silver Spring, MD), thence the reactor through a line containing shut-off and vent valves and a pressure gauge.
II. Synthesis Procedure Reactor charging and sealing generally were carried out 20in a nitrogen atmosphere (glove bag). Catalyst (about .02 gm) and additives were weighed into a glass liner which then was placed in the reactor. Solvent (5 ml) and liguid additives - (usually air free) were added by syringe or pipette. The reactor was sealed and capped with a valve.
The reactor was connected to the compressor discharge system and purged with the desired gas by pressurizing, then venting several times. Then gas was compressed into the reactor to the desired pressure (2000-~500 psig) as indicated on the system gauge. After gas feed-line venting, the reactor 3O was disconnected, and the valve plugged to prevent leakage through the seal.

1173~S9 1 After heating (80-250C.) and shaking the reactor for the desired time, it was cooled then vented through a wet test meter with a gas sample being taken. The liquid contents were discharged, and the reactor a`nd liner rinsed with solvent. The 5 combined liquid for analysis was 15 gm.
III GLC Anal sis Procedure Y
GLC analyses were performed on a Varian-Aerograph Series 1400 Chromatograph e~uipped with hydrogen flame detector.
A 6' x 1/8" O.D. 316SS column packed with 80-100 mesh Chromosorb 10 lOl*was utilized. The col~mn was operated at 100C. for 9 minutes then te~nperature was increased by 6C./min. to 200C.
This procedure provided reproducable isothermal analysis of lower boiling components and decreased retention times for higher boiling materials.¦
15 IV. Product Identification The components of the reaction mixtures employing Ru catalysts were identified by GLC-MS analysis. Besides the ma~or products - methanol, ethanol and acetaldehyde - several other components were found. These were formaldehyde, ethylene 20 glycol, propionaldehyde, n-propanol, acetic acid, methyl acetate, 1,3-dioxolane, 2-methyl-1,3-dioxolane, hydroxy-2-propanone and 1,2-propanediol. In a few cases, methane was _' observed.

2~

* Trade Mark 3o 1 EXP~LE 1 Using the described Synthesis Procedure, the catalysts produced with various alkali metal chlorides and Ru3(CO)12 were evaluated using the following materials and reaction 5 conditions:
0.093 mmole Ru 0.093 mmole salt 1.5:1 H2/CO at 4500 psig (20CC.) ml N-methylpyrrolidin-2-one 10 The reaction was conducted at 200C. for two hours. The results are given in TABLE I.

~173~5g ~_1 ~ _1 ~o ~ e~ CO
E ~ ~I
Z; U
s~ ~
~o I ~ o ~ o C`l o ~:

o I .
~ p~ ~1~ o ~ oo a~
-o ~I ~ . . . . I
~:

~ ~ U ~. V V

._' V l 1` U~ _l o ~ o J- ~1 ~ ~I
o ~ o ~ ... . . . U~
'1 -' ~

41 -- u~

I ~ Z ~

~ ~1730S9 Various catalysts formed ln situ from lithium salts and Ru3(C0)12 were evaluated using the same procedure as in EXAMPLE 1 excepting the salts were added at a level of 0.1 5 mmole.
The results are given in TABLE II.

3o ~L~73~5~ .

c~ 1 Q~ O C~ ~O C~l E \
Z;
S~
Q) o o _~ ~ ~, ~ O
C~ J~
o .

" o c~ ~ O _ o ~ ~ ~

~! 5~,o 0 ~
U) . ' ~ ~ I O O ~ o :~
o .
~ o u~ _l ~ O ~D o ~ ~ . . .
~:

~ _ -- t) 0~

305~3 ~ 2 1 r 1 EXA~LE 3 Various catalysts formed with hydrogen halides and Ru3(C0)12 were evaluated using the procedure of EXA~LE 2.
In addition~ the effect of hydrogenhalides on preformed 5 ruthenium chlorocarbonyls was also evaluated using the same procedure r The results are shown in TABLE III.

~173(~S9 O ~
O ~ ~I O . . . I . . I
E ~ t~
~?
~ o o ~ I o ~
c~ ~ o I . I
I ,~ , ~ o , , v~ I
o r --I
~, . . .. . . .
o ~ ~, .~ , ~ ,~
P~ o ~ I ~ o o o ~ ~ o Ul~ -- ~ ~ C`~
~ . .
~" . i H ¦ O ¦ ~ '` . .
~ ~ ~, ~ ~ ~ ~ ~

P~ ~
lo u~ ~ o o ~,~ ~D ~ O
C~

,, . ~, ~ ~, , ¢
H
Q) V ~ Oj a~ c~ ~ ~ O O O O

~d O O O O ~ c~

13~73(3S9 l F,XAMPLE 4 The effect of increasing lithium chloride molar ratio was evaluated using the procedure of EXAMæLE 2 with the results given in TABLE ~V, with IRu(C0)3Cl2~2 preformed catalyst.

11~3(1i59 h O ~1 ~I
O
E ~ ~) ~ a~
Z;~

O h ~ U~ r-l C~
~ ~) 'U ~
t~
O O~
C) a) ~ ~ ~ ~ N ~ , ~ C~
>1 ~ ~
~1 , .~ ~ I O 1~
~:
U C~

P~ ~

_~
Y 00~ 0 V~ .
~ ~ ~ I_ _~
~ O

-Various temperature, catalyst and additive effects on the reaction were evaluated using the procedure of EXAMPLE 1.
~ The results are given in TABLE V.

3o 1 3L 7 3~59 a~
h ~
a) o E --~1 O o ~ o ~ ~ ~ ~
~Z I ....... ~........... . ..
h ~ ~1 ~ ~1 ~ ~t ~
a) I
h O l C U~
E~ ' ',1 u~ o ~ ~ ~D ~ ~D ~ ~ ~ ,1 ~ N~ C~l 1~ D O 1~ 00 ~
~0 ~--O I I . I
h o C~ O C`1 ~NI ~J ~ ~D
P.l ;~ ~1 O O ~t ~D O ~ O O ~ r. o~ ~ I~ ~ ~ ~ C~) cr~
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1 Referring to TA~LE V, it is noted that the use of higher reaction temperature over 200C. and preferably above 225~C., results in significant increases in methanol production and, in some cases, in extremely high selectivities 5 to methanol, as evidenced by the Product Mole Ratio Cl/C2 values, and the Turnover Number values. This increase in methanol production is further enhanced by added halide, especially chlorides which generally appear to be more effective than other halides in this regard.
The combination of increased reaction temperature and addition of halide, i.e., metal halide and/or hydrogen halide, in present experience gives the best productivities to methanol and therefore comprises a particularly preferred embodiment of-this aspect of the present new process.

3o ~1'73059 1 EXAMPI.E 6 Ruthenium and rhodium chlorocarbonyls are compared with and without lithium chloride as a promoter in the procedure of EXAMPLE 1 with the results given in T~BLE VI.
From these data, it is apparent that lithium chloride does not promote but rather inhibits the rhodium catalyst.

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1 EX~PLE 7 Various preformed ruthenium halocarbonyl anions were evaluated using the procedure of E4YAMPLE 1 with the results given in TABLE VII. The alkali metal salt and ruthenium 5 ca.:bo.nyl halide of EXAMPLE 1.are re~laced by the indicated anionic complex~

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3 ~73~59 1 EXP~LE 8 The procedure of the preceding examples was repeated employin~ HBr or HCl with Ru3(C0)12 (at 0.093 mmole Ru) and with H4Ru~(CO)12 (at 0.1 mmole Ru) at H2/CO of 1.5:1 and initial pressure of 4500 psig for two hours at the indicated temperatures. The results are given in TABLE VIII.

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Claims

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A process for producing acetaldehyde in a first stage reaction and then reducing said acetaldehyde to produce ethanol in a second stage reaction with methanol as the prin-cipal-by-product which comprises reacting carbon monoxide and hydrogen at a temperature of from about 150° to about 300°C.
and superatmospheric pressure in the presence of a catalyst system consisting essentially of a member selected from a ruthenium carbonyl halide complex, and a combination of ruth-enium carbonyl complex and a separate source of halide and re-covering acetaldehyde and/or ethanol from said reaction.

2. A process according to claim 1, wherein the catalyst system is present at least during said first reaction stage.

3. A process according to claim 2, wherein said ruthenium complex is present during said second reaction stage.

4. A process according to claim 2, wherein a further hydrogenation catalyst is present during said second reaction stage.

5. A process according to claim 4, wherein said ruthenium complex is removed from product of the first reac-tion stage prior to said second stage reaction.

6. A process according to claim 4, wherein said further hydrogenation catalyst comprises palladium.

7. A process according to claim 1, 4 or 6, wherein said temperature is in the range of from about 175° to about 275°C.

8. A process according to claim 1, 4 or 6, wherein said pressure is in the range of from about 150 to about 600 atmospheres.

9. A process according to claim 1, 4 or 6, wherein the molar ratio of hydrogen to carbon monoxide is from about 1/10 to about 10/1.

10. A process according to claim 1, wherein the ruthenium complex catalyst system further comprises an alkali metal chloride or bromide.

11. A process according to claim 1, wherein the ruthenium complex catalyst system further comprises hydrogen chloride or hydrogen bromide.

12. A process according to claim 10, wherein the alkali metal is lithium.

13. A process according to claim 1, wherein the reaction is carried out in the presence of a solvent compris-ing an aprotic organic amide.

14. A process according to claim 13, wherein the solvent comprises an N-lower alkyl pyrrolidin-2-one.

15. A process according to claim 13 wherein the solvent comprises an N,N-di(lower alkyl) acetamide.

16. A process according to claim 13 wherein the solvent comprises N-methyl pyrrolidin-2-one.

17. A process according to claim 13, wherein the solvent comprises N-N-diethyl acetamide.

18. A process according to claim 13, wherein the solvent comprises N,N-diethyl propionamide.