NL8101956A - PREPARATION OF OXYGENATED COMPOUNDS. - Google Patents

Description

-1-; ·: VO 1849

Preparation of oxygenated compounds

The invention relates to the preparation of acetaldehyde and ethanol by reacting carbon monoxide and ethanol in the presence of a ruthenium catalyst.

Acetaldehyde is a valuable commercial product with a wide variety of uses, particularly as an intermediate for the preparation of commercial chemicals. Ethyl alcohol is also an important commercial chemical useful for a wide variety of purposes, for example, as a chemical intermediate, solvent and optionally, most importantly as a component of glass alcohol.

The reaction of carbon monoxide and hydrogen has been known for a long time and results in a multitude of products depending on the reaction conditions and the type of catalyst used. U.S. Patent 3,833,63¼ describes the reaction of carbon monoxide and hydrogen with a rhodium catalyst to form ethylene glycol, propylene glycol, glycerol, methanol, ethanol, methyl acetate and other products.

French patent 2,259-07? describes the preparation of ethanol from carbon monoxide and hydrogen with rhodium-on-silica gel as a catalyst at 30 DEG-35 DEG C. at a pressure of 70-175 kg / cai. German Patent 2.6¼¼.185 describes the conversion of carbon monoxide and hydrogen 20 into hydrocarbons using Ru 2 (CO) 2 in tetrahydrofuran as a solvent. The use of the same ruthenium carbonyl catalyst on solid supports to prepare hydrocarbon products is described in J.A.C.S. 100, 2590 (1978). The reaction of carbon monoxide and hydrogen with ruthenium carbonyl clusters in methanol and methyl formate 25 is described in [ACS / CSJ Chemical Congress Abstracts, IH0RG k2Ö (1979)] · It has now been found that the reaction of carbon monoxide and hydrogen in the presence of certain selected ruthenium catalysts C yields oxygenated products, that is, acetaldehyde and ethanol.

The reaction appears to proceed in several stages, with acetaldehyde being the main product in earlier stages and ethanol predominating in later stages, so that the process can lead to one or the other, or mixtures thereof which are readily, such as by fractional can be separated. By setting the response parameters, 81 81 0 1 9 5 6 -2. the process is controlled to obtain one or the other product as desired. Methanol is the primary by-product of the process of the invention.

If desired, the total working method of the. The invention can be carried out in separate stages, the initial stage leading to the formation of acetaldehyde as the main product and the final stage to the ethanol as the main product.

The favorable results obtained according to the process of the invention make them particularly suitable for commercial production of acetaldehyde and ethanol, not only with a view to a considerable yield of the products but also to the easy recovery of them simultaneously methanol formed, for example, by fractional distillation. Easy recovery is particularly important as it allows the products of the reaction mixture to separate even TJ in those process operations, thereby forming methanol in a substantial amount. Even when acetaldehyde is present in amounts corresponding to about 10 moles or less of the reaction product mixture. the easy separation means the extraction of. aldehyde are possible.

Acetaldehyde is also formed with a high degree of purity. Usually, the initial stage reaction mixture as such can be used in the final stage reaction to form ethanol by reduction of acetaldehyde.

The results obtained with the invention are particularly surprising and totally unexpected. Ruthenium carbonyl complexes have long been known as catalysts of the reaction of carbon monoxide and hydrogen to form products with only one carbon atom, such as methanol. , methane and methyl formate Furthermore, under the relatively mild reaction conditions employed in the process of the invention, especially the moderate reaction temperature, by ruthenium carbonyl, Ru 2 CO 2 12, little or none of the The C 2 oxygenated products of the invention are formed, therefore, the results obtained with the catalysts of the invention are unexpected, especially in view of the high conversions and the selectivity of the process with respect to the production of oxygenated products. of two carbon atoms.

The process of the invention is accomplished by carbon monoxide and hydrogen in the presence of certain ruthenium-containing 8 f 0195 5 * 1 * 1; Contact catalysts in a suitable solvent at elevated temperatures and superatmospheric pressures. The main products of the reaction are acetaldehyde and ethanol, the main by-product of which is methanol. The mode of contact is not critical since various procedures commonly used for this type of reaction are useful. as long as an efficient gas-liquid contact is provided.

. Thus, the process can be carried out by contacting the ruthenium catalyst in a reaction solvent at selected conditions with a. mixture of carbon monoxide and hydrogen. If favorable, a drip phase can be used extensively.

In view of the two-stage aspect of the process of the invention, the preparation of ethanol can be carried out in various ways. The reaction can be effected by both stages in succession at suitable temperatures and pressures. or optionally, the reaction may be stopped at the end of the first phase where the product acetaldehyde is and the second phase may be carried out with any applicable reduction process, which will eventually lead to the conversion of the aldehyde group of acetaldehyde into the primary alcohol group of ethanol. In most cases, however, the voiming of ethanol takes place very smoothly. Usually ethanol as a product when used for conventional reaction conditions predominates, in which case the product mixture is usually about 50/50.

A wide variety of reduction processes can be used for the second phase reaction, including the known chemical reducing agents used for the reduction of aldehydes of primary alcohols. Where possible, catalytic reductions using hydrogen are chosen for commercial processes since they are more practical and efficient, especially with catalysts that can be regenerated and thus reused. In the process of the invention, catalytic hydrogenation is preferred for the same reasons, especially with catalysts that can be regenerated. Any hydrogenation catalyst can be used.

Thus, typical hydrogenation catalysts include, for example, Eaney nickel, cobalt, copper heatite, rhodium, palladium, platinum, and the like with catalysts suitable for use on supports such as charcoal, silica, alumina, kieselguhr, and the like.

8101956 * * - -: - -b- "1" I I {, The circumstances of. the catalytic hydrogenation are known and in; generally, the reaction can be carried out at temperatures of about 30-150 ° C, usually at pressures of about 7-350 kg / cm.

The use of higher temperatures and pressures, although possible, does not offer any special advantages and usually requires special equipment which is economically disadvantageous and therefore not preferred.

Particularly preferred hydrogenation catalysts are. those which "usually require short reaction times, for example palladium and. nickel, which are most desirable for commercial processes for economic reasons.

The active catalyst component of the catalyst system for the process of the invention has not yet been fully identified, but is believed to consist of ruthenium in complex combination with. carbon monoxide together with. a halide ligand. It is sufficient that the catalyst system initially contains a ruthehium source and a halide source, after which the active catalyst component is formed at the start of the process, for example, the addition of the catalyst. reactants, i.e. carbon monoxide and hydrogen, ruthenium carbonyl complex are flashed. Optionally, the ruthenium source may be a preformed carbonyl complex. Furthermore, the source. of both ruthenium or ruthanium carbonyl complexes and halide are the same compound, for example ruthenium carbonyl halides which are commercially available. The catalyst systems can be formed with ruthenium carbonyl halides or optionally by the combination of ruthenium carbonyl or hydrocarbonyl complexes with a separate halide source. The catalyst systems may be used as such or may be precipitated or attached to a solid support such as molecular sieve zeolites, alumina, silica. ion exchange resins or a polymeric ligand. The preferred halides are chloride and bromide.

The ruthenium halocarbonyl catalysts can be represented by the formula Ru (CO). X, where a, b and c are integers and

3 »DC

X is halide. Such catalysts can be prepared by the reaction of ruthenium halide with carbon monoxide or by the reaction of ruthenium carbonyl complexes with halogen-containing compounds.

Optionally, ruthenium carbonyl halides are commercially available (for example, from Matthey-Bishop, Malveme, PA).

The catalysts of the invention can be used in addition to the halide

*. a

ligand to be present in the method contain other ligands.

As described in U.S. Patent 3,833,634, suitable ligands are compounds containing at least one nitrogen atom and / or at least one. oxygen atom, which atoms have an electron pair 5 available to form coordinate bonds with ruthenium. Examples of organic ligands include various piperazines, dipyridyls, N-substituted diamines. aminopyridines, glyoleic acid, alkoxy-substituted acetic acids; tetrahydrofuran, dioxane, 1,2-dimethaxybenzene, alkyl ethers of alkylene glycols, alkanolamines, imino diacetic acid, nitrilotriacetic acid, ethyl diamine tetraacetic acid and the like. In U.S. Patent 3,527,809. Phosphorus-containing ligands such as trialkyl, triaryl and tricycloalilyl phosphites and phosphines, as well as the analogous antimony and arsenic compounds are disclosed. Other ligands, such as tin halides, for example SnCl 4, SnBr 3, or NO, may also be present.

The activity of the ruthenium catalyst system of the invention is enhanced by the addition of alkali metal salts, for example, halide salts. According to experience, lithium halides, in particular lithium chloride and lithium bromide; the preference.

At 200 ° C, a LiCl / Ru ratio of 15 led to the reduction of 40 moles of C0 / mole Hu / hr at a 44 # Ts selectivity to C18 oxygenated products. Comparative figures for lithium brcmide activation were 13 moles CO and 44 # selectivity.

For most purposes, the amount of halide used will vary considerably, with molar ratios of at least 0.1 mole per mole of ruthenium being useful. The alkali halides can be present in a large molar excess, for example about 115 mol / mol ruthenium or even higher.

Instead of the addition of alkali salt and, preferably halides, the salts with the selected catalyst can be used to form ruthenium halocarbonyl anions which, for the purposes of the invention, are represented by the general formula M ^ Hu ^ X ^ iCO) ^, where a, b, c and d are integers, for example NaEuBr ^ iCO) ^ and NaEuCl ^ iCO) ^. Such compounds can be preformed and then added to the reaction in a solvent as the catalyst system.

The hydrogen halogen acids, HCl and HBr, also promote the 8101956 *: t. 1.

i. activity of the ruthenium halocarbonyls of the process of the invention, but to a lesser extent than the alkali metal halides. Addition of HCl increased the catalytic activity of [RuClgCCO3g by only about 25% of that of lithium chloride while decreasing the selectivity to ethanol and acetaldehyde, while both HCl and EBr promoted the activity of Eu2CO3]. . A large excess of hydrogen halide is of no benefit and is usually avoided since it may lower catalyst activity.

Also can. the catalyst systems of the invention are formed by adding halides to a suitable ruthenium compound either in the selected solvent or in the reaction mixture. Ruthenium acetacetonate in combination with hydrogen halide in reaction solvents, for example, provides essentially the same results as a preformed catalyst, . for example [Ru (CO) 2Cl] 2 · Noted. that in the absence of a halide, for example chloride or chloride, the ruthenium catalysts such as ruthenium carbonyl form methanol as the main product with negligible or trace amounts of ethanol or acetaldehyde. The amount of halide to be added to the catalyst need not be stoichiometric since even small amounts will lead to the formation of some ethanol. For most purposes, however, it is preferable to use an equimolar amount of halide which can be added as an aqueous solution, for example hydrogen halide or a solution in an organic solvent such as the lower alkanols.

25 When lithium chloride at equimolar ratios with o

Ru ^ 10CO) at 200 ° C, 13 moles were used. CO / mol Ru / hour reduced with a selectivity to producers with two carbon atoms of k8%. With excess lithium bromide (about 60 mol / moi Ru) at 250 ° C, increased productivity to products with 2 carbon atoms was observed.

The suitability of the starting ruthenium compounds for the in situ formation of the halide-containing catalyst can be determined by a simple test procedure involving small scale reactions with the selected ruthenium compound, halide and reactants CO and Hg 35 in a solvent. Upon completion of these miniature reactions, gas-liquid chromatographic analyzes of the reaction mixture allow the products to be identified and will, of course, "81 0 1 9 5 6 ........

* c * -τ- those ruthenium compounds are identified which are suitable via the in situ treatment for the preparation of ethanol and / or acetaldehyde. With this test procedure, the suitable starting rhenium compounds can be easily identified.

5 When acetaldehyde is the desired product. is. only the first stage reaction needs to be carried out. If necessary, the product can be separated from the co-formed methyl alcohol, optionally formed ethanol and reaction solvent by fractional distillation.

As is clear, the ruthenium catalyst used in the first stage reaction can also function as a hydrogenation catalyst for the second stage reaction to prepare ethanol. If the first phase reaction is allowed to proceed. finally ethanol was formed by the hydrogenation reaction. Generally, the first stage reaction ruthenium catalyst is an effective catalyst for the second stage hydrogenation, but other hydrogenation catalysts may also be used in place of the ruthenium catalyst. If desired, you can. the. ruthenium catalyst can be converted into a more effective hydrogenation catalyst by addition of a phosphine ligand, especially triarylphosphines or triphenylphosphines, although other phosphine ligands as described in U.S. Patent No. 3, 27, 809 may also be used. .

It is possible to carry out the reduction stage in the presence of metal catalysts, such as palladium, nickel or copper chromite, and the second stage reaction in a separate reactor. Thus, the first stage reaction can be conducted in a first reactor under selected temperature and pressure conditions, upon completion of which the first stage can be transferred, with or without isolation from the reaction mixture, to a second reactor under selected temperature and pressure conditions. carry out hydrogenation reaction.

Obviously, it is not critical to accurately stop the reaction at the termination of the first stage or allow the second stage to proceed until all the acetaldehyde has been reduced to ethanol.

The reaction can be stopped at any convenient time dictated by the product desired and by other considerations.

Thus, after a substantially maximum yield of acetaldehyde, usually within about 2 hours, the reaction can be stopped and the aldehyde recovered. The reaction mixture will undoubtedly contain quantities of ethanol, 81 0 1 9 5 6 .......

»« ·! . ; ::: "" Formed by the second stage reaction. However, the products are easy to isolate and are of almost equal commercial importance. Obviously, if ethanol is desired, the reaction can be continued within economic considerations until it is reasonably complete and ethanol as the main product and, of course, acetaldehyde as. minor product is obtained.

The invention therefore provides a simplified method for the formation of acetaldehyde. The invention also provides a simplified method for the. obtain ethanol by. or 10 continuing the initial reaction to the aldehyde products to yield hydrogenation to give ethanol, or optionally reducing the aldehyde product of the first stage reaction to known ethyl alcohol by known reduction processes. In the latter, the acetaldehyde product of the first step reaction can be used in the form of the reaction mixture or the product can be isolated, such as by fractionation, and used in purified form. The amount of catalyst to be used in the process of the invention is not critical and can vary considerably. Of course, at least a catalytically effective amount of catalyst should be used.

Generally, an amount of catalyst which effectively gives a reasonable reaction rate is sufficient. A small amount of 0.001 g of ruthenium per liter of reaction medium will suffice, while amounts greater than 0.1 g of atoan appear not to contribute substantially to the reaction rate. For most purposes, the effective preferred amount of ruthenium is in the range from about 0.002 to about 0.05 g atom per liter.

The reaction conditions are not extremely critical because wide ranges of elevated temperatures and superatmospheric pressures are useful. The practical limitations of production equipment 30 will largely dictate the choice of temperatures and pressures at which the reaction is to be conducted. Thus, when using available production systems, the selected elevated temperature should be at least about 150 ° C and can rise to about 300 ° C. For most purposes, the preferred operating temperature is in the range of 175-275 ° C. The superatmospheric pressure should be at least about 10 atmospheres and can rise to almost any pressure achievable with the production equipment. Since equipment ....... 81 0 19 5 6.-9- t * is extremely expensive for extremely high pressures, pressures up to approximately TOO atmosphere are suggested. It is most desirable that the pressure be in the range of about 150-100 atmospheres, especially when using the aforementioned preferred temperature range.

The reaction is preferably carried out in a solvent which will dissolve the polar materials and is preferably aprotic.

; Preferred solvents are H-substituted amides in which each hydrogen of the amido nitrogen is substituted with a hydrocarbon group, for example 1-methylpyrrolidin-2-one, ΕΓ, Η-dimethylacet-10 amide, IT, N-ciethylacetamide, N, II methylpiperidone, 1,5-dimethylpyrrolidin-2-one, 1-benzyl-pyrrolidin-2-one, N, Η-dimethylpropionamide, methylphosphoric triamide and similar liquid amides. The amides are preferred solvents since their use has been found to lead to the highest product yield. Other solvents, usually aprotic, can be used, but the yields are considerably less than those obtained with the preferred amide solvents. Such solvents include, for example, cyclic ethers such as tetrahydrofuraa, dicocan and tetrahydropyram; ethers such as diethyl ether 1,2-dimethoxybenzene; alkyl ethers of alkylene glycols and polyalkylene glycols, for example methyl ethers of ethylene glycol, propylene glycol and di-, tri- and tetraethylene glycols; ketones such as acetone, methyl isobutyl ketone and cyclohexanone; esters, such as ethyl acetate, ethyl propionate and ethyl laurate; and alkanols, such as methanol, ethanol, propanol, 2-ethylhexanol and the like; tetramethyl urea; X-butyrolactone; and mixtures thereof. The selected solvent should preferably be liquid under the reaction conditions.

The preferred solvents are aprotic organic amides.

The intended amides include cyclic amides, ie, wherein the amide group is part of a ring structure, such as in pyrrolidinones and piperidones; acylated cyclic amides such as H-acylpiperidines, pyrroles, pyrrolidines, piperazines, morpholines and the like, preferably those in which the acyl group is derived from a lower alkanoic acid, for example acetic acid; as well as acyclic amides, ie, in which the amido group is not part of the ring structure, such as in acetamides, formamides, propionaiden, caproamides and the like. The most preferred amides are those in which the amido hydrogen atoms. ... have been completely replaced by hydrocarbon groups, which preferably should not be 8101956 f -10- .....

ί (; i contain more than 8 carbon atoms. Examples of hydrocarbon

"I

! groups are alkyl, preferably lower alkyl such as methyl, ethyl, 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 aralkyl groups, especially benzyl. The most preferred arnide solvents include 1-methyl-pyrrolidin-2-one-methylpyrrolidin-2-one and. 1-benzylpyrrolidin-2-one.

. Of course, mixtures of. the solvents are used, at; Example amide solvent with other solvents.

Water is not critical to the reaction and can. are present without serious adverse effects. It tends to react with carbon monoxide to form CO 2 and hydrogen (water gas shift). Water can be excluded since it can reduce the selectivity of carbon monoxide conversion or the water gas shift. are advantageously used to form hydrogen.

The reaction pressure represents the total pressure. of the gases present in the reactor, ie carbon monoxide and H 2 and, if present, optionally diluent gas, such as nitrogen. As in any gaseous system, the total pressure is the sum of the partial pressures of the component gases. In the. reaction according to the invention, the molar ratio of hydrogen and carbon monoxide can range from about 1/10 to about 10 / f, with the preferred ratio being about 1/5 to about.

25 is spring 5/1, while the reaction pressure. can be achieved by adjusting the pressure of these gases in the reactor.

When the second phase reaction is conducted in a separate reactor, whether or not in the presence of the original ruthenium catalyst or other metal hydrogenation catalyst present, the reaction is normally conducted under hydrogen gas without dilution gas, as is usually the case in catalyzed hydrogenation reactions.

As with any method of this type, the method of the invention can be carried out batchwise, semi-continuously or continuously.

The reactor should be constructed of materials that can withstand the required temperatures and pressures, while the interior surfaces of the reactor should be substantially inert. Conventional controllers can be provided to control the reaction, such as heat exchangers and the like. The reaction must be carried out by effective methods of promoting gas-liquid contact, such as freezing, shaking, stirring, oscillation, dropper and the like. Catalysts and reactants can be introduced into the first stage or second stage reactor at any time during the replenishment process. Recovered catalyst, solvents and unreacted starting materials can be recycled.

The relative yields of ethyl alcohol, acetaldehyde and methanol are not particularly critical since the product mixture can be easily separated into the components by known techniques, especially by fractional distillation, regardless of the amounts contained in the mixture. Therefore, even if the desired product constitutes 10-20% of the reaction mixture, it can be easily separated from the mixture, in particular through continuous processing.

Of course, the preferred methods yield mixtures in which acetaldehyde and ethanol predominate as reaction product and methanol as by-product is minimal.

The process conditions for the individual first stage reaction are essentially the same as those used in the first stage of the combined two stage reaction. Thus, the reaction is carried out at. o ...

a temperature of at least about 150 ° C to achieve a reasonable reaction rate and the temperature may be up to about 300 ° C. For best results, the temperature should be in the range of about 175-2.75 ° C. The total gas pressure used is generally maintained at about 10-700 atmospheres, with about 150-600 atmospheres being preferred. Higher pressures and higher temperatures can of course be used, but no particular advantages are attained thereby, since they require the use of special high pressure equipment, so that they are usually avoided.

The reaction conditions used in the second stage, ie the hydrogenation, can be any standard reaction temperature and pressure used in such a reaction since neither the temperature nor the pressure are critical to this reaction. Preferably, the hydrogenation is carried out at a temperature of at least about 100 ° C to achieve a reasonable reaction rate. Lower temperatures can of course be used if long reaction times can be tolerated. The hydrogen gas pressure is not 81 0 1 9 5 6 ....................................

: -12- overly critical as long as sufficient gas is "available" for hydrogenation. Thus, the pressure can vary up to about 35 to 350 kg / crn although even higher pressures are possible.

When the catalyst selected for the hydrogenation stage is other than ruthenium, it is preferable to remove the ruthenium catalyst from the first stage reaction mixture. This preference is primarily determined by the desirability of the accompanying catalytic effects that the ». ·" ". Avoid reducing ethanol yield.

The following examples provide a further illustration of the; 10 invention.

The equipment, the synthetic procedure and the analyzes are as follows.

I. Equipment A. Reactors. Reactions were performed in a Parr 71 ml reactor constructed of 310 SS with one type A 0.6 cm cone pedestal (Cat. ^ 7 ^ 0, Parr Instruments Co, Moline IL). Glass vessel and open top vessel were used. The reactor seal was of a modified Bridgeman type incorporating a special two-piece packing ring (Cat. 61 HD) cm silver containing (in contact with the reaction mixture) with a nickel backing ring. This packing arrangement was necessary because the originally used one-piece nickel packing was attacked by carbon monoxide. ... ...

The reactors were sealed with 316 SS Whitey valves 25 'resistant to severe operating conditions with a high temperature Grafoil packing Cat. SS 3NBSU-GTA-9K-3U, Whitey Co., Oakland, CH). The valves were coupled to the reactors with 316 SS Sno-Trik high pressure adapters - for Swagelok (Cat SS-UU MA-UOO, Sno Trik Co, Solon OH) and Swagelok port fittings (Cat. SS- ^ 01 PC Crawford Fitting Co Cleveland OH).

30 B. Stirring and heating

The arm of a Burrell shaker was "inserted into an oven comprising an insulated box and electric strip heaters.

The reactors were clamped to the schudaim. The oven temperature was eaten by a thermocouple connected to a controller (on-35 off type). Time control was used to control the reaction time by interrupting the energy supply to the temperature controller at the desired time. The temperature controller was used to control a relay 81 0 1 9 5 6 ..........

! I13I

coil. A Variac was used to regulate the voltage going from the relay to the afterhitter.

In numbers that more vigorous agitation was required, the reactors (without glass cladding) were screwed to a paint shaker 5 by means of a special clamp which prevents impact of the valve, thus causing the port coupler. can break off.

C. Gas compression and delivery

Conventional carbon monoxide-hydrogen mixtures (Union Carbide Corp. Linde Division, South Plainfield, NJ) were piped into an air-powered, double-ended compressor (Car 1 * 6-1 ^ 035, American Instrument Co. Silver Spring, MD ), and from there it was fed to the reactor through a conduit containing shutoff and air valves and a pressure gauge.

II Synthesis Procedure 15 The loading and sealing of the reactor was generally carried out in a nitrogen atmosphere (glove bag). Catalyst (about 0.02g) paraformaldehyde (usually 0.5g) or other substrate and additive were weighed into a glass container which was then placed in the reactor. Solvent (5 ml) and liquid additives (usually 20 air-free) were added through a syringe or pipette. The reactor was spun off and closed from above with a valve.

The reactor was connected to the compressor discharge system and purged with the desired pressurized gas and then vented several times. Thereafter, the gas in the reactor was compressed to the desired gauge pressure (1kQ / 315 kg / cm) as indicated on the pressure measurement systems.

After draining the gas supply line, the reactor was disconnected and the valve blocked to prevent leakage through the seal.

After the reactor had been heated (80-250 ° C) and shaken for the desired time, it was cooled and the contents passed through a wet test. 30 meters were dropped and a gas sample was taken. The liquid contents were discharged and the reactor and internal glass container rinsed with solvent. The combined liquid for analysis was 15 g.

III. GLC Analysis Procedure GLC analyzes were performed on a Varian-Aerograph Series 35 1 ^ 00 chromatograph equipped with a hydrogen flame detector. A 316 SS column of 1.8 m x 0.3 cm outer diameter packed with Chramosorb 102 with a size of 0.15-0.18 mm was used. The column was put into operation 8101 956 -1U-! At 100 ° C for 9 minutes after which the temperature was raised to 200 ° G at 6 ° C per minute. This procedure provided a reproducible isothermal analysis of lower boiling components and a reduced retention time for higher boiling materials.

5 IV. Product identification

The components of the reaction mixture using Ru catalysts were identified by GLC-MS analysis. In addition to the main products - methanol and acetaldehyde - several other components were found. These were formaldehyde, ethylene glycol, propionaldehyde, n-propanol, acetic acid, methyl acetate, 1,3-dioxolan, 2-methyl-1,3-dioxolan, hydroxy-2-propanol and 1,2-propanediol. In some cases, methane was observed.

Example I

Using the described synthesis procedure, the catalysts prepared with various alkali chlorides and Ru (CCO) were evaluated using the following materials and reaction conditions: 0.093 mmol Ru 0.093 mmol salt 1.5: 1 Hg / CO at an overpressure of 315 kg / cm 2 (20 ° C) 5 ml N-methylpyrrolidin-2-one.

The reaction was performed at 20 ° C for 3 hours. The results are summarized in Table A.

81 0 1 9 5 6 "" ", ——" -15- »

ft CV1 i- VO CU CU .CO

¢ 3 Η O

+> O Vfl r · r- OJ O

0) Ö

0? -P

3%

• H

-PO

ί) & T- O -r- O CU

Nj r * * Λ Λ Λ ft g H ü Ο cn CO 4 · \ ο Ο 1Λ Ο ο <“η << · γ1 ** -Ρ <d (Μ Αί30 W Ο af Ο co J 3 Ο I" "Λ "I« * Μ> - oiiTicncvi να Η Ο U Ο UV Ρ3 Ρη ί> <$ & <U ¾ «ο ο ο. 1— 0 ο

'in o' * ft 'I I ft I

scj ο to (a

CU

ο

0 N

SO

SW t— ΙΓνι-OOt— H

”8 if 1— 1— CVI Ο Ο o« cno ** "** '> ft" § öW ooootao g £ ° 1 i ο dJtEi in 1A t- f- af oD' O oj f- m in t- af 00 Ο Λ Λ Λ Λ Λ λ 5} ι-ΟΟΟΟΟ Ο +3 ι — J γ — ϊ ri Η Η 3 Ο ο ft Ο Ο Ο σ ι · Η ai Ο, Ω fQ 03 ta jsw «« ο 8101956 «K ·

, "-"! Example II

Several catalysts in situ formed from lithium salts and Ru 2 (CO 2) were evaluated using the same procedure as in Example 1, except that the salts were added in an amount of 0.1 mmol. The results are summarized in Table B .

81 0 1 9 5 6 ......

; ! -1 ° -1 ° -1 ° ° ^ CM O * O 1 °

.p o VO "CM O O

<u «• ar> o -p st -

+3 O

g ft O IA

N t— O * «HO O Pi fl IA N tn t- O O O tO * -

S

e Ij

+3 T (CM

, ¾ 3 ü CM ON O

J Ö O ^ II * * "II

14 CM- CM'-t-O

pq Ö tl O CM

! 4 IU P5 P +> <

§ O - CO

in t— o H oo «* o« o o o

CM O O

O

H

O

H O H H

”W t— m Pi O O

«O J-CMOOO g g

ö cn o o "« o «oo SS

(UK O O ft O Pi +3 0 on 5 vo ê o o o Λ

(¾ <- CM

M kU \ i-0 \ OV0 w w O o cm m m on t— cn o o «·>« "« o K ft o ^ o o o o

Λ CM

r- ^ on q o

43 H 5+ P «5 O

3 ΙΧ, ΟΡΡΡΡΗΟ CM

O I · γ + · γ + · <+ · Η Ή · η · η Ν Η J ft ft ft> -Ρ Η 8101956 ** *,! 1 '^:: ":' ~ * I!

Example III

Various catalysts filled with vessel or halides and were evaluated according to the procedure of Example II.

Also, the effect of hydrogen halides on preformed ruthenium-5 'chlorocarbonyls was evaluated using the same procedure.

The results are shown in Table C.

i.

t? • 0 810195 6 "" ~ ^ - d (§ o vo vo co +5 cu o * Λ 1. "1« ho η ιλ - = f cu cu bO o ra g '• p * 3 p' d <1) O «ft ^ '- O» - ° ^' CU O ^ 'g t- CU r-rf

-H

P'0 CU _.

Ai ^ o co co. o t— r- 3 O V. I "fi I» * «|» i ^ r · CU · - co t- vo O hO ft <D (ft> a cu o o vo m

O 1— CU CU CU CU

Λ Λ Λ Λ Λ a oooooooo o cu o t4

H

a h s-ι s- <

OOVOCUOOO

<S g a r ™ CO cu o o gO "" · ft Pi

C4 oOOOOOO M DIO

* a ΰ o

<D

μ, Μ,. - g: - - 0

Sn a la vo a 5 vo vo cu o j- (V) Λ Λ Λ Λ Λ a 0000 ^ - cu · "- θ ο Η a Η ο 3 I Η ft * - rJ, ¾ ϋ 3 ο ρρ - 'ο η μ αο ta aa η aa Λ a Λ Τ "

CU CU CU CU

i — i i — i i — i i — i CO 00 CO 00 O λ λ ^

4-3 cucucucuoopo dj r-t-t-t-OOOO

t O O O O CU CU CU CU

fSSSÏÏÖÖÖÖ s ί ’/’ / 'ίί a s i a (Baaa1 — ji — i 8101956 I 1 "' -20-!" · i 1

Example IV

The effect of increasing the molar ratio of lithium chloride was evaluated by the procedure of Example II, the results of which are shown in Table D, with a [Ru (CO)? Clg] 2. 5 preformed catalyst.

i. . ^ 81 0 1 9 5 6 "" "':" "-21- -SS' '' · '·'

bQ t— CJ

mH CVJ * "_ MOO Λ CO r 1Λ t— 51 • rf -P -P -P .¾ 0 3 1! P- H r (il 1Λ r W U} OO i— ΟΙ Π 4 4 s ° Λ

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Example V

The effect of different temperatures, catalysts and additives on the reaction was evaluated using the procedure of Example I. The results are shown in Table E.

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It follows from Table E that the use of higher reaction temperatures above 200 ° C and preferably above 225 ° C leads to a significant increase in the production of methanol and in some cases gives extremely high selectivity to methanol as can be seen from the product molar ratio C Cg values and the conversion number values. This increase in methanol production is further promoted by the addition of halide, especially chlorides, which, in general, are found to be more effective in this respect than other halides.

The. combination of an elevated reaction temperature and addition. 10 of halide, for example metal halide and / or hydrogen halide, gives the best productivity over methanol and therefore comprises a particularly preferred embodiment of this aspect of the process of the invention.

-Example VI

Ruthenium and rhodium chlorocarbonyls were compared with and without premotor lithium chloride in the procedure of Example I, the results of which are shown in Table F.

From this data, it is clear that lithium chloride does not activate the rhodium catalyst but rather inhibits it.

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Several preformed rut henium halocarbonyl anions were evaluated using the procedure of Example I, the results of which are shown in Table G. The alkali salt and ruthenium-5 carbonyl halide of Example I were replaced by the indicated anionic complex.

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The results are shown in Table II.

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Claims (9)

1. Process for the preparation of acetaldehyde and / or ethanol by reacting carbon monoxide and hydrogen at a temperature of about 150 to about 300 ° C and superatmospheric pressures in the presence of a catalyst system composed in the beginning 5. from a ruthenium source and a balogenide source, after which the acetaide hyde and / or the ethanol is recovered from said reaction mixture. 2. Process according to claim 1, characterized in that acetaide hyde is formed in a first reaction stage and then ethanol in a second reaction stage 10, wherein the catalyst system is present during at least the first reaction stage. 3. A method according to claim 2, characterized in that the ruthenium during the second reaction step. is present. 1+. Method according to claim 2, characterized in that during 15. second stage reaction a hydrogenation catalyst is present. Method according to claim U, characterized in that the ruthenium. is removed from the product of the first reaction stage prior to the second stage reaction. 6. Process according to claim U, characterized in that the hydrogenation catalyst comprises palladium. .7 *. Method according to claims 1-6, characterized in that the temperature is in the range from about 175 to about 275 ° C. A method according to claims 1-7, characterized in that the pressure is in the range from about 150 to about 600 atmospheres. 9. Process according to claims 1-8, characterized in that the molar ratio of hydrogen to carbon monoxide is about 1/10 to about 10/1. 10. Process according to claims 1-9, characterized in that the catalyst system further comprises an alkali chloride or chloride. Process according to claims 1-9, characterized in that the catalyst system further comprises hydrogen chloride or hydrogen bromide. A method according to claim 10, characterized in that the alkali metal is lithium. 13. Process according to claims 1-12, characterized in that the reaction 35_ is carried out in the presence of a solvent comprising an aprotonic organic ground. 1¾. Process according to claim 13, characterized in that the solvent comprises an H-lower alkylpyrrolidin-2-one. 15 * Process according to claim 13, characterized in that the solvent comprises an N, N-di- (lower alkyl) acetamide. 16 * Process according to claim 13, characterized in that the solvent comprises W-methylpyrrolidin-2-one. .17 ·. Process according to claim 13, characterized in that the solvent comprises ΪΓ, N-diet hylacine amide. TO 18. A process according to claim 13, characterized in that the solvent comprises Ν, Ν-diethylpropionamide. 8101956