FR2480743A1 - PROCESS FOR THE PREPARATION OF OXYGEN COMPOUNDS - Google Patents

Abstract

THE INVENTION RELATES TO A PROCESS FOR PREPARING OXYGEN COMPOUNDS. THE PROCESS CONSISTS OF REACTING CARBON MONOXIDE AND HYDROGEN AT A TEMPERATURE OF APPROXIMATELY 150 TO 300C AND AT A SUPERATMOSPHERIC PRESSURE, IN THE PRESENCE OF A CATALYTIC SYSTEM INITIALLY FORMED BY A SOURCE OF RUTHENIUM AND A SOURCE D 'HALOGENIDE AND TO RECOVER ACETALDEHYDE AND OR ETHANOL.

Description

The invention relates to the preparation of acetaldehyde and ethanol by

  reaction of carbon monoxide and

  hydrogen, in the presence of a ruthenium catalyst.

  Acetaldehyde is a very useful commercial chemical with a wide variety of uses, especially as an intermediate for the manufacture of commercial chemicals. Ethyl alcohol is also a useful and important commercial chemical for a wide variety of uses, including chemical intermediates, solvents and, perhaps more

  important, that of constituent of "gazohol".

  The reaction of carbon monoxide and hydrogen has been known for a long time and can lead to various products, depending on the reaction conditions and the type of catalyst used. US Pat. No. 3,833,634 describes the reaction of carbon monoxide and hydrogen. in the presence of a rhodium catalyst for obtaining ethylene glycol, propylene glycol, methanol glyceryl, ethanol, methyl acetate and other products. FR 2,259,077 describes the preparation of ethanol from carbon monoxide and hydrochloride using rhodium on silica gel coaime catalyst, between 300 and 350 C and at a pressure of 6.9 to 17.2 MPa. DE 2,644,185 discloses the conversion of carbon monoxide and hydrogen to hydrocarbons using Ru 3 (CO) 12 in tetrahydrofuran as the solvent. The use of the same carbonylruthenium catalyst on solid supports for the production of hydrocarbons is described in J.AeC.S. 100, 2590 (1978). The conversion of carbon monoxide and hydrogen to methanol and methyl formate in the presence of carbonylruthenium clusters is described in ACS / CSJ Chemical Congress Abstracts,

Inorg. 428 (1979).

  It has now been established that the reaction of carbon monoxide and hydrogen in the presence of certain selected ruthenium catalysts results in C2-oxygenated products, namely acetaldehyde and ethanol. The reaction apparently takes place in several stages, acetaldehyde being the predominant product in the early stages, whereas ethanol predominates in the late stages, so that the process can give rise to one or the other product or mixtures of these products, which can be easily separated, for example by fractionation. Thus, by adjusting the reaction parameters, the process can be directed to favor one or the other product as desired. Methanol is the main by-product obtained in the present process. If desired, the overall process of the invention can be carried out in separate stages, the initial stage resulting in the formation of acetaldehyde as the main product and the final stage in the formation of ethanol.

as the main product.

  Given the very desirable results that we

  obtained according to the invention, the process is particularly suitable

  This is because of the commercial manufacture of acetaldehyde and ethanol, not only from the point of view of noticeable yields of products but also the ease with which they can be recovered by separating them, for example by fractional distillation, from the methanol formed together. The ease of recovery is extremely important since it allows the products to be separated from the reaction mixture even in operations where methanol can be formed as the main product. Thus, for example, even when acetaldehyde is present in amounts corresponding to about 10 mole% of the reaction product mixture and even less, the ease of

  separation allows recovery of the aldehyde.

  Acetaldehyde is also obtained with high purity. Usually the first stage reaction mixture can be used as it is in the second stage reaction to obtain ethanol by reduction.

acetaldehyde.

  The results obtained according to the invention are in fact quite surprising and totally unexpected. In

  particular, it is known that carbonylruthene complexes

  Nium catalyzes the reaction of carbon monoxide and hydrogen by forming only single-carbon products such as methanol, methane and methyl formate. In addition, under the relatively mild reaction conditions used in the present process, particularly at moderate reaction temperatures, the carbonyl ruthenium Ru 3 (CO) 12 forms little or no oxygenated C2-C products. 'invention. Also, the results obtained with the present catalysts are not obvious, given, in particular, the high conversions and the specificity of the process for the formation of 2-oxygenated products.

carbon atoms.

  The process of the invention is carried out by contacting carbon monoxide and hydrogen in the presence of certain ruthenium catalysts in a suitable solvent at elevated temperature and superatmospheric pressure. The main products of the reaction are acetaldehyde and ethanol, the main by-product being methanol. The mode of contact is not critical, since all the various procedures normally employed in this type of reaction can be used provided that effective gas-liquid contact is ensured. contacting the ruthenium catalyst in a reaction solvent with a mixture of carbon monoxide and hydrogen under the selected conditions. Where appropriate,

  a trickle phase operation can be used.

  Since the present process is in two stages, the implementation can take many forms for obtaining ethanol. The reaction can be carried out by allowing both stages to proceed consecutively at an appropriate temperature and pressure, or the reaction can be stopped at the end of the first stage, where the reaction is complete. product is acetaldehyde, and conduct the second stage with any applicable reduction method, resulting in the conversion of the aldehyde group of acetaldehyde to primary alcohol group of ethanol. However, in most cases, ethanol formation occurs very easily. Usually, ethanol predominates as product, when the usual reaction conditions are applied, the product mixture being at least 50/50.

about in most cases.

  A wide variety of reduction processes can be used for the second stage reaction, including well-known chemical reducing agents for reducing aldehydes of primary alcohols. However, for commercial processes, where possible, catalytic reductions using hydrogen are usually preferred because they are more convenient and efficient, especially with regenerable catalysts. In the present process, catalytic hydrogenation is preferable for the same reasons, especially with catalysts that can be regenerated. Any hydrogenation catalyst can be used

  which is effective for the reduction of carbonyl groups.

  Thus, typical hydrogenation catalysts are, for example, Raney nickel, cobalt, copper chromite, rhodium, palladium, platinum and similar metal catalysts which can be conveniently used on supports such as charcoal, silica, alumina, kieselguhr, etc. The catalytic hydrogenation conditions are well known and, in general, the temperature reaction can be conducted ranging from about 30 to about 1500C, usually at relative pressures. from about 0.7 to 34.5 MPa. It is possible to use higher temperatures and pressures, but this provides no special advantage and usually special equipment is required which is economically disadvantageous and therefore not preferred. Particularly preferred catalysts are those which typically require short reaction times, for example palladium and nickel, which is most desirable in commercial processes.

for economic reasons.

  The catalytically active species of the catalyst system for the present process has not been fully identified, but is believed to be formed of ruthenium in complex combination with carbon monoxide and, at the same time, with a halide ligand. It is sufficient that the catalytic system initially comprises a source of ruthenium and a source of halide and the active catalyst space is then formed when the process is initiated, for example the carbonylruthenium complex is formed when the reagents are added. that is, carbon monoxide and hydrogen. Alternatively, the ruthenium source may be a preformed carbonyl complex. Further, the same compound may be both the source of ruthenium or carbonylruthium and halide complex, such as, for example, the carbonylruthenium halides found in the materials. Catalytic systems can be formed with carbonylruthenium halides or by combining carbonylruthenium or hydrocarbonylruthenium complexes with a separate halide source. The catalyst systems can be used as such or can be deposited or fixed on a solid support such as molecular sieve zeolites, alumina, silica, an ion exchange resin or a polymeric ligand. Preferred halides are chloride and bromide, especially

  chloride. Catalysts of the halocarbonyl-

  ruthenium can be represented by the formula Rua (CO) bX, in which a, _ and c are numbers - 6 -

  and X is a halogen atom, preferably chlorine.

  These catalysts can be prepared by reaction of ruthenium halides with carbon monoxide or by reaction

  of carbonylruthenium complexes on halogenated compounds.

  Or, carbonylruthenium halides are commercially available (eg Matthey-Bishop,

Malverne, Pennsylvania).

  The catalysts of the invention may contain other ligands, besides the halide ligand, which must be present for the process. As disclosed in US Pat. No. 3,833,634, suitable ligands are compounds which contain at least one nitrogen atom and / or at least one oxygen atom, these atoms having a pair of electrons available for bond formation. coordinated with ruthenium. Examples of organic ligands are various piperazines, bipyridyls, N-substituted diamines, aminopyridines, glycolic acid, substituted acetic acids

  alkoxyl, tetrahydrofuran, dioxane, 1,2-dimethoxy-

  benzene, alkyl alkylene glycol ethers,

  alkanolamines, iminodiacetic acid, nitrilotriacic acid,

  In US Pat. No. 3,527,809, phosphorus-containing ligands such as trialkyl, triaryl and tricycloalkyl phosphites and triarylphosphines, as well as antimony and arsenic-like compounds are described. . Other ligands such as tin halides, such as SnC13

  and SnBr3, or NO, may be present.

  The activity of the ruthenium catalyst systems of the invention is enhanced by the addition of alkaline salts, particularly halides. According to current experience, the most preferred are lithium halides, especially lithium chloride and bromide. At 200 ° C., a LiCl / Ru ratio of 15 results in the reduction of 40 moles of CO / mole Ru / h with

  selectivity of 44% for oxygenated C2 products.

  Comparative figures for lithium bromide activation are 13 moles of CO and a selectivity of 44% For most purposes, the amount of halide used and molar ratios of at least about 0.1 moles per mole of ruthenium are usable. The alkali halides can be present in large molar excess, for example about 115 moles / mole of ruthenium and even more. Instead of adding alkaline salts, preferably halides, the salts formed with

  the catalyst chosen to form halogenated anions

  carbonylruthenium, which, for the purposes of the description, are

  represented by the general formula M R X (CO) d, wherein a, b, ú and d are integers, for example NaRuBr 3 (CO) 3 and NaRuCl 3 (CO) 3. These compounds can be preformed and then added to the medium in the

  solvent, as catalytic system.

  The hydrohalic acids HCl and HBr also promote the activity of the halocarbonylrutheniums of the present process, but to a lesser extent than the alkali halides. The addition of HCl increases the catalytic activity of [RuC12 (CO) 3] 2 by only one percent of the increase provided by lithium chloride, decreasing the selectivity for ethanol and acetaldehyde, while that HC1 and HBr promote the activity of Ru3 (CO) 12 Large excess hydrogen halides have no advantage and are usually avoided because they can

  tend to decrease the activity of the catalyst.

  In addition, the catalyst systems for the invention can also be formed by adding a halide to a suitable ruthenium compound, in the selected solvent or in the reaction mixture, if preferred. For example, ruthenium acetylacetonate combined with a hydrogen halide in reaction solvents gives substantially the same results as the preformed catalyst, for example [Ru (Co) 2c1] 2. it should be noted that in the absence of halide, for example chloride or bromide, ruthenium catalysts such as carbonylruthenium form methanol, as the main product, and negligible amounts or traces of ethanol or acetaldehyde . The amounts of halide added to the catalyst need not be stoichiometric because even small amounts result in some ethanol formation. However, in most cases it is preferable to use at least an equimolar amount of halide which can be added as an aqueous solution, for example as a hydrohalic acid, or a solution in solvents.

  organic compounds such as lower alkanols.

  When using lithium chloride and Ru 3 (CO) 12 in equimolar proportions, at 2000C, 13 moles of CO / mole Ru / h are reduced, the selectivity for products with 2 carbon atoms being 48%. With an excess of lithium bromide (about 60 moles / mole of Ru) at 250 ° C., an increased productivity in products with 2 atoms is observed.

of carbon.

  To determine whether any of the initial ruthenium compounds are suitable for the in situ formation of the halogenated catalyst, a simple test method can be applied, which consists in conducting small-scale reactions with the selected ruthenium compound, the halide and the CO and H2 reactants in the solvent. Upon completion of the small-scale reactions, the products are identified by analysis of the mixture by liquid chromatography and, of course, the appropriate ruthenium compounds are identified by in situ treatment for the production of ethanol. / or adetaldehyde. By this test method, suitable initial ruthenium compounds are readily identified. When the desired product is acetaldehyde, it is sufficient, of course, to conduct the first stage reaction. The product of the methanol formed together with all the ethanol formed and the reaction solvent can be separated if

  necessary, by fractional distillation.

  As is evident, the ruthenium catalyst used in the first stage reaction can also serve as a hydrogenation catalyst for obtaining ethanol in the second stage reaction. Thus, if the first stage reaction is allowed to proceed, the hydrogenation reaction yields ethanol. In general, the ruthenium catalyst of the first stage reaction is an effective catalyst for the second stage hydrogenation, but other hydrogenation catalysts may be used instead of the ruthenium catalyst. If desired, the ruthenium catalyst can be converted to a more efficient hydrogenation catalyst by the addition of a phosphene ligand, particularly triarylphosphines, such as triphenylphosphinep although other ligands can also be used.

  phosphines, as described in US Pat. No. 3,527,809.

  It is possible to carry out the reduction step using metal catalysts such as palladium and nickel or copper chromite and to perform the second stage reaction in a separate reactor. Thus, the first reaction can be carried out. in a first reactor, under selected conditions of temperature and pressure and, after completion, the product of the first stage can be transferred to a second reactor, by isolating it from the mixture or without isolating it, under selected conditions of temperature and pressure,

  to carry out the hydrogenation reaction.

  Of course, it is not essential to stop the reaction exactly at the completion of the first stage, nor to maintain the second stage reaction until all acetaldehyde is reduced to ethanol. The reaction can be stopped at any suitable point, dictated by the desired product as well as by other factors

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  Thus, once practically the maximum yield of acetaldehyde has been obtained, usually in about 2 hours,

  the reaction can be stopped and the aldehyde recovered.

  However, the reaction mixture will undoubtedly contain amounts of ethanol formed by the second stage reaction. However, the products are easily separable and have almost equal commercial importance. Obviously, when ethanol is desired, the reaction can be allowed to proceed, as long as it is economical, until it is reasonably complete, to obtain ethanol as the main product and of course of

  acetaldehyde as a byproduct.

  The invention thus provides a simplified process for the selective manufacture of acetaldehyde. In addition, the invention provides a simplified process for obtaining ethanol, either by allowing the initial aldehyde process to proceed so that the hydrogenation yields ethanol, but it can also be reduced. the aldehyde obtained in the first stage reaction, by applying known reduction processes to obtain ethyl alcohol. In this latter procedure, the acetaldehyde formed in the first stage can be used in the form of the reaction mixture or the product can be isolated, for example by fractionation, and used

in purified form.

  The amount of catalyst used in the first stage

  does not seem critical and can vary considerably.

  It is of course necessary to use at least a catalytically effective amount of catalyst. In general, a quantity of catalyst which makes it possible to obtain a reasonable reaction rate is sufficient. An amount as small as 0.001 gram atom of ruthenium per liter of reaction medium may suffice, while amounts greater than 0.1 gram atom do not seem to significantly influence the reaction rate. For most uses, the preferential and effective amount

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  The reaction conditions are not very critical, in that wide ranges of high temperatures and superatmospheric pressures can be used. manufacturing equipment will dictate to a large extent the choice of temperatures

  and pressures at which the reaction is to be conducted.

  Thus, when using the manufacturing systems that are available, the high temperature chosen must be at least about 150 ° C. and may be up to about 300 ° C. For most uses, the preferred temperature ranges from approximately 100 to 1750 ° C. The superatmospheric pressure should be at least about 10 atmospheres and may be about any pressure achievable with the manufacturing apparatus. Since an apparatus for extremely high pressures is very expensive, pressures of up to about 700 atmospheres are suggested. Most desirable is that the pressure be about 150 to 600 bar, particularly when the preferred temperature range is used. The reaction is preferably carried out in a solvent which dissolves the polar bodies and which is preferably aprotic. The preferred solvents are N-substituted amides, in which each hydrogen atom of the amide group is replaced by a hydrocarbon group,

  for example 1-methylpyrrolidinone (2), NN-dimethyl-

  acetamide N, N-diethylacetamide, N-methylpiperidone, 1,5-dimethylpyrrolidinone (2), 1-benzylpyrrolidinone (2),

  N, N-dimethylpropionamide, hexamethyltriamide phosphori-

  as and similar bodies such as liquid amides.

  Amides are preferred solvents because their use results in the highest product yields based on current experience. Other solvents, usually aprotic, can be used, but the yields are significantly lower than those obtained with

2. & 7 3

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  amides, which are the preferred solvents. These solvents include, for example, cyclic ethers such as tetrahydrofuran, dioxane and tetrahydropyran,

  ethers such as diethyl ether, 1,2-dimethoxy-

  benzene, alkyl ethers of alkylene glycols and polyalkylene glycols, for example methyl ethers of ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol and tetraethylene glycol, ketones

  such as acetone, methyl isobutyl ketone and cyclo-

  hexanone, esters such as ethyl acetate, ethyl propionate and methyl laurate, alkanols such as methanol, ethanol, propanol, 2-ethylhexanol and the like, tetramethylurea, butyrolactone and mixtures of these bodies. The chosen solvent must

  Preferably, be liquid under the reaction conditions.

  Preferred solvents are aprotic organic amides. The amides envisaged include cyclic amides, that is to say in which the amide group is part of a ring structure such as in pyrrolidinones and piperidones, acylated cyclic amines such as N-acylpiperidines, pyrroles, pyrrolidines, piperazines, morpholines and the like, preferably those whose acyl group is derived from an alkanoic acid, for example acetic acid, as well as acyl amides, that is to say in which the amide group is not part of a cyclic structure

  such as acetamides, formamides, propionamides, capro-

  amides and the like. The especially preferred amides are those where the hydrogen atoms of the amide group are entirely replaced by hydrocarbon groups,

  preferably not containing more than 8 carbon atoms.

  Examples of hydrocarbon groups are alkyl groups, preferably lower such as methyl, ethyl and butyl, aralkyl, for example benzyl and phenethyl, cycloalkyl, for example cyclopentyl and cyclohexyl, and

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  alkenyl, for example allyl and pentenyl. Preferred substituents of the amide group are lower alkyl groups, especially methyl, ethyl and propyl, and aralkyl, especially benzyl. Especially preferred amide solvents include 1-methylpyrrolidinone (2), 1-ethylpyrrolidinone (2) and 1-benzylpyrrolidinone (2). Of course, it is possible to use solvent mixtures, for example

  amide solvents and other solvents.

  Water does not play a critical role in the reaction and may be present without serious deleterious effects. It tends to react on carbon monoxide by forming Co2 and hydrogen (transposition of gas to water) .We can exclude water because it can decrease the carbon monoxide conversion selectivity or can advantageously use the transposition of gas to water

to generate hydrogen.

  The reaction pressures represent the total pressure of the gases contained in the reactor, that is carbon monoxide and hydrogen and, if appropriate, an inert diluent gas such as nitrogen. in any gaseous system, the total pressure is the sum of the partial pressures of the constituents. In the present reaction, the hydrogen / carbon monoxide molar ratio can vary from about 1/10 to about 10/1, and preferably from about 1/5 to about 5/1, and the reaction pressure can be achieved by controlling the reaction rate. When the second stage reaction is conducted in a separate reactor, whether in the presence of the ruthenium catalyst originally present or a different metal hydrogenation catalyst, the reaction is normally carried out under hydrogen. without diluent gas, as well as

  is common in catalyzed hydrogenation reactions.

  As in any process of this kind, the present process can be carried out in discontinuous, semi-continuous form.

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  and carry on. The reactor must be made of materials

  able to withstand the temperatures and pressures required

  and the inner surfaces of the reactor are

  inert. The usual controls can be used to control the reaction, for example heat exchangers, etc. The reactor must be equipped with appropriate gas-liquid contact means, for example

  by vibration, agitation, oscillation, runoff etc ...

  The catalyst and reagents can be introduced into the first stage or second stage reactor at

  any time during the process, for renewal.

  Catalyst, solvent and materials can be recycled

  first unaltered that we recover.

  Relative yields of ethyl alcohol, acetal-

  Dehyde and methanol are not extremely critical since the product mixture can be readily separated into its components by known techniques, especially by fractional distillation, irrespective of the proportions contained in the mixture. Thus, even when the desired product represents 10 to 20% of the reaction mixture, it can be easily separated from the mixture, especially in the continuous treatment. Of course, the preferred processes give mixtures in which acetaldehyde and ethanol predominate as reaction products, while the amount of

  methanol as a by-product is minimal.

  The conditions of the separate first stage reaction are substantially the same as in the first stage of the two-stage reaction. Thus, the reaction is conducted at a temperature of at least about 1500 ° C to achieve a reasonable reaction rate, and up to about 300 ° C. To give the best results, the temperature should be about 175 to 2750C. The total gas pressure is generally maintained between about 10 and 700 bar, preferably between 150 and 600 bar. Of course, higher pressures and temperatures can be used,

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  but without appreciable advantage and, since they require the use of special high-pressure apparatus, they are usually avoided. The reaction conditions applied in the second-stage reaction, that is to say hydrogenation, can be avoided. all the temperatures and pressures used for these reactions, because neither the temperature nor the pressure is critical for this reaction. Preferably, the hydrogenation is conducted at a temperature of at least about 1000 ° C to effect a reasonable reaction rate. Of course, lower temperatures can be used if longer reaction times can be tolerated. The hydrogen pressure is not excessively critical as long as sufficient gas is available for the hydrogenation. For convenience, the pressure will vary from about 3p4 to 34.5 MPar although pressure can be applied

even higher.

  When the catalyst selected for the hydrogenation step is other than ruthenium, it is preferable to remove the ruthenium catalyst from the first stage reaction mixture. This preference results mainly from the fact that it is desirable to avoid concomitant catalytic effects, which may tend to diminish

the ethanol yield.

  The following examples further illustrate the invention.

  The equipment, the synthesis method and the analyzes used are as follows: 1. Equipment A. Reactors The reactions are carried out in 71 ml Parr reactors built in 310SS, having a 6.35 mm type A conical bushing <category No. 4740, By Coke Instrument Moline # Illinois). Open glass doublings are used at the top. The reactor gasket is of the modified Bridgeman type with a special L 'n743 gasket

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  two pieces (category No. 61HD) including silver

  (exposed to the process) with a nickel support ring.

  This packing arrangement is necessitated by the attack of carbon monoxide on the originally supplied single piece nickel packing. The reactors are closed with hard service 316SS Whitey valves with Grafoil High Temperature Gasket (# SS3NGS4-GTA-9K-3N, Whitey Co., Oakland, California). The valves are coupled to the reactors by means of 316SS Sno-Trik- (high-grade SS44M-A-400, Sno Trik Co., Solon, Ohio) high-pressure adapters and Swagelok fittings (SS-401 -PC, Crawford Fitting Co.g Cleveland,

Ohio).

  B. Stirring and Heating The arm of a Burrell wrist action stirrer is placed in a furnace comprising an insulated box and electric belt heaters. The reactors are tightened on the agitator arm. The oven temperature is measured by means of a thermocouple connected to a regulator (all or nothing). A timer is used to adjust the reaction time by cutting

  the current to the temperature controller at the desired time.

  The temperature controller is used to activate a relay coil. We use a Variac to adjust the

  voltage that goes from the relay to the heater.

  In cases where more vigorous agitation is required, the reactors (without glass lining) are bolted to a paint shaker by means of a special support to prevent whipping of the valve,

  which would cause the separation of the connection.

  C. Compression and Supply of Gas Usual mixtures of carbon monoxide and hydrogen (Union Carbide Corp., Linde Division, South Plainfield, New Jersey) are introduced into a compressor Zk8o743

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  air-driven two-end (grade 46-14035, American Instrument Co., Silver Spring, Maryland), then into the reactor through a pipe containing valves

  isolation and discharge and a pressure gauge.

  II. Synthesis Process The reactor is usually charged and capped in a nitrogen atmosphere (glove box). The catalyst (about 0.02 g) is weighed and the additives are introduced into a glass liner which is then placed in the reactor. 5 ml of solvent and liquid additives (usually free of air) are added by means of a syringe or pipette. The reactor is sealed and overfilled with a valve. The reactor is connected to the compressor discharge system and purged with the desired gas by pressurizing and releasing the pressure several times. Then gas is compressed in the reactor to the desired relative pressure (X 3.8 to 31 MPa) indicated by the manometer. After purging the gas supply pipe, the reactor is disconnected and

  plug the valve to prevent leakage through the seal.

  After heating the reactor (80-250 ° C) and stirring the desired time, it is cooled and then vented through a wet test instrument by taking a gas sample. The liquid contents are discharged and the reactor and the lining are rinsed with water.

  solvent. The liquid collected for the analysis represents 15 g.

Analysis by chromatocrihi a-lcud

  Analyzes are carried out by gas chromatography

  liquid on a Varian-Aerograph 1400 series chromatograph equipped with a hydrogen flame detector. A column 316SS 1.8 m and 3.2 mm outside diameter packed with "Chromosorb 102" 149 to 177 pm was used. The column is operated at 1000 ° C. for 9 minutes, then the temperature is raised at a rate of 60 ° C./min to 200 ° C. This method gives a reproducible isothermal analysis.

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  low-boiling constituents and decreases the

  residence time of higher boiling bodies.

  IV. Identification of the products The constituents of the reaction mixtures using ruthenium catalysts are identified by multi-tasking liquid chromatography. In addition to the main products methanol, ethanol and acetaldehyde -

  finds several other constituents. These are formaldehyde

  hyde, ethylene glycol, propionaldehyde, propanol (n), acetic acid, methyl acetate, 1,3-dioxolane, 2-methyl-1,3-dioxolane, hydroxypropanone (2) and propanediol (l, 2). In some cases, methane is observed *

EXAMPLE 1

  Using the described synthesis method, the catalysts obtained with various alkali chlorides and Ru 3 (CO) 12 are evaluated using the following reaction bodies and conditions: 0.093 mmol Ru 0.093 mmol H2 / CO salt 1.5l1 at 31 MPa (200C) ml of N-methylpyrrolidinone (2). The reaction is carried out at 200 ° C. for 2 hours. The results are given in Table I.

TABLE I

Products, mmoles

CH30H CH3CHO C2H50H

  o 1.25 0.75 0.37 0.57 0.74 0.48 0.47 0.15 L0.11 0.10 tr 0.07 C1 / C2 molar ratio of the products

  ... 2.DTD: 0.10 tr0 2.2, 0 3.4 2.8 tro 6.8 Activity, moles of product / mole of Ru C1 o0 8.1 4w, 0 6.1 8.0 , 2 6.1 1.6 1.2 2.2 0.8

(1) 0.5 mimole of salt.

  ## STR2 ## LiCl NaCl Salt KCl RbCl RbCl (1) CsCl! i C2

L ^ 7 43

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EXAMPLE 2

  Various catalysts formed in situ from lithium and Ru 3 (CO) 12 salts were evaluated by the same method as in Example 1, except that salts were added at a rate of 0.1 mmol,

  The results are given in Table II.

TABLE II

Products, mmoles

CH3OH CH3CHO C2H50H

0 0 0

tr. O 0

1.25 0.47 0.10

0.51 0.27 0

1.59 tr. 0.06

0.30 0.05 0

0.16 tr. O

0 0 0

  C1 / C2 molar ratio of products i, 2.2 1.9 6.0 Activity, moles of product / mole of Ru C1 o tr. , O C2 o 6.1 2.9 0.6 0.5 (1) 0.15 mmol (2) 0.6 mmol LiF salt (1) LiCl LiBr LiBr (2) LiI LiOAc Li2CO3 r%) (of> 1J td FI

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EXAMPLE 3

  Various catalysts formed with hydrogen halides and Ru 3 (CO) 12 were evaluated by the method of Example 2. In addition, the effect of hydrogen halides on

  preformed chlorocarbonylruthenium.

  The results are shown in Table III.

TABLE III

  Catalyst Ru3 (CO) 12 Ru3 (CO) 12 Ru3 (CO) 12

RU3 (CO) 12

  [uC12 (CO) 3] 2 [Ruc 2 (CO) 2 [Ruc 2 (CO) 3] 2 [RU 1 Cl 2 (CO) 3] 2 Acid HCI HBr HI (1) HCI HBr HI Products, mmol H3n CH3CHO C2H5OR 3 300 25o

0 0 0

0.65 0.16 0.12

0.66 0.32 0.20

0 O O

1,2 0.20 0.20

2.0 tr0 0.26 1.4 tr. 0.23

0 0 0

  C1 / C2 molar ratio of the products 2,3 1,3 3,0 7,7 6,1 Activity, moles of product / mole of Ru

C1 C

O 0

7.0 3.0

7.1 5.6

  2.6 2.3 (1) 8 mmoles HI r ') t'O. I t you I

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EXAMPLE 4

  The effect obtained when increasing the molar proportion of lithium chloride with the results given in Table IV when using a [Ru (CO) 3 Cl 2] catalyst is evaluated by the method of Example 2. préforméo

TABLE IV

  Moles of LiCl / mole of Ru o 0.9 2.0 7.7 Products, mmols

CH3OH CH3CHO C2H5OH

1,18 0,20 0,20

2.44 0.37 0.43

3.05 0.51 0.55

4.08 0.62 0.88

4.41 0.62 1.1

  C1 / C2 molar ratio of products 2.9 3.0 2.9 2.7 2.6 Activity, moles of product / mole of Ru

C1 C2

12 4.1

8.2

31 11

42 15

17

u I Ln (o <M

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EXAMPLE 5

  The effects of various temperatures, various catalysts and various additives are evaluated by the method of Example 1. The results are given in Table V.

TABLE V

Catalyst Ru3 (CO) 12

RU3 (CO) 12

Ru3 (C0) 12

RU3 (CO) 12

  Ru 3 (CO) 12 Ru 3 (CO) 12 Ru 3 (CO) 12 Ru 3 (CO) 12 Ru 3 (CO) 12 LuCl 2 (CO) 2 [Rucl 2 (co) 3 2 [RuC 12 (Co) 3] 2 Ru 3 Cl (CO) 3> 2 RuC12 (C0> 31 2 [RuC12 (CO) 3] 2 [RuC12 (CO) 31 2 [Ruc12 (CO) 3] 2 [RuC 2 (CO) 31 2 LRuC 2 (CO)> 31 2 CO) 3 2 [RuC 2 (CO) 31 2 [Ruc 2 (CO) 3] 2

promotional

  P: LiCl LiCl LiCl HBr HBr HBr LiCl LiCl LiCl LiCl LiCl LiBr LiBr LiBr Moles P / mole Ru 7.5 7.7

tempera-

ture, C O0 O Products, mmoles

CH3 OH

  o 0.05 0.47 0.38 1.25 0.24 0.66 11.0 tr. 0.26 1.20 7.6 1.4 4.1 4.4 23.2 1, 47 11.7

CH3CHO C2H5OR

0 0

* 0 0

O O

0.29 O

0.47 0.10

0 0.24

0.11 0.16

0.32 0.20

O 0.44

  tr. tr. 0.20 tr. 0.32 0.62 0.62 0.30 0.27 tr. 0, 10 0.20 0.32 0.47 0.88 1, 1 1.32 O, 27 1.96

14.5 0.35 3.96

Moderate report

  Ci / C products om 1.3 2.2 0.9 1.3 2.6 3.0 1.7 2.8 2.6 2.6, 2 3, 4 Activity, moles of product / mole of Ru Ci O 0.5, 0 4.1 13.4 2.6 7.1 tr. 2.6 12.2 C2 o 3.1 3.1 2.5 2.9, 6 4.7 tr. 1, O 4,1 3,3 8,1l Z> Co w! -4! TABLE V (cont.) Catalyst [RuCl2 (CO) 312 RuCl2 (CO) 2 (Ph3P) 2 RuCl2 (CO) 2 (Ph3P) 2 (SnCl3) Ru2Cl3 (CO) 5 (SnCl3) Ru2Cl3 (CO)

Promo- Moles P / Tempera-

  P, Molecule, C LiBr LiCl LiCl LiCl

mmOles, Modal Report

  Products, mmol / lar CH / CH OHCH3CHO CAH OH products 8.0 1.02, 8 0.89 4.36 0.47 tr. tr. 0.08 0.81 4.99 0.03 0.09 0.16 1.71 1.5 3.7 1.7 Activity, moles of product / mole of Ru

C1 C2

  , 4 59.2 9.1 0.31 0.92 2.4 I OD l -'I

2 80743

- 29 -

  It can be seen from Table V that the use of a high reaction temperature above 2000C and preferably above 225C results in significant increases in methanol formation and, in some cases, extreme selectivities. large for methanol, as shown by the Cl / C2 molar ratios of products and activities. This increase in methanol formation is further enhanced by the addition of halides, especially chlorides, which appear to be generally more active than others

halides from this point of view.

  The combination of a higher reaction temperature and the addition of halide, i.e. metal halide and / or hydrogen halide, according to current experience, gives the methanol productivities and is thus a particularly preferential embodiment of this aspect.

of the new process.

EXAMPLE 6

  Chlorocarbonylruthenesider chlorocarbonyl rhodiums, with and without lithium chloride promoters, are compared as promoters in the process of Example 1 and

  the results are given in Table VI.

  From these data, it is clear that lithium chloride does not activate the rhodium catalyst, but

inhibits it rather.

TABLE VI

  mmol of Metal Catalyst [Rh (CO) 2 Cl] 2 0.129 [RuCl 2 (CO) 3] 2 0.098 Rh (CO) 2 Cl 2 0.129 [RuCl 2 (CO 3) 2 0.098 [Rh (CO) 2 Cl 2] 0.129 [RuCl 2 (CO) 0.098 [Rh (CO) 2 Cl] 2 0.129 [Rh (CO) 2 Cl] 2 0.098 [RuCl 2 (CO 3) 2 0.098 Additive, mmol LiCl LiCl LiCl LiCl 0.129 0.098 0.75 0.75 LiCl 0.77

tempera-

  re, oC Product yields, mmoles

CH3 OH

0.066 0.26 0.023 2.44 0.24 1.18 o

CH3 CHO

C3 0.012 tr. 0.013 0.37 tr. 0.20 o0

4.08 0.62

C2H50H '

  0.046 0.10 o 0.43 0.056 0.20 o 0.88 Activity, moles of product / mole of metal C1 0.5 2.6 0.2 1.9 oo C2 0.4 1.0 0, 1 8.2 0.4 4.1 o0 o I o I king IN> co 0- - 'LW

- 31 -

EXAMPLE 7

  Various preformed halocarbonylruthenium anions were evaluated using the method of Example 1 with the results given in Table VII. The alkaline salt and carbonylruthenium halide of Example 1 were

  replaced by the indicated anionic complex.

TABLE VII

  Yields, mmoles Catalyst CsRu (CO) 3Cl3 CsRu (CO) 3Cl3 Cs2Ru (CO) 3Cl4 Cs2Ru (CO) 3C14 K2Ru (NO) C15 K2Ru (NO) C15 LiRu (CO) 3Cl3 LiRu (CO) 3Cl3 LiRu (CO) 3Br3 LiRu (CO) 3Br3 CsRu (CO) 3CI3 Cs2Ru (CO) 2C14 Additive ---- CsBr (1.5 mmol) CsBr (1.5 mmol) Temperature, Oc MeOH 8.4 6.5 9.1 9, 0 1.2 7.1 2, 7 7.7 1.4 1.0 0.93 CH4 o0 0.5 0.8 1.2

CH 3 CHO

  0.22 0.28 0.2 tro 0.31 tr. 0.77 tr. 0.25 0.37 0.22 0.14! (I) EtOH 0, 54 0, 54 0.56 0.97 0.37 4.3 0.71 0.58 0.5 1.5. 0.21 0.26 0.4 6.8 o o O 1.9 O o ri t., -.9. f- The

- 33 -

EXAMPLE 8

  The procedure of the preceding examples is repeated using HBr or HCl with Ru3 (CO) 12 (at 0.093 mmol Ru) and with H4Ru (CO) 12 (at 0.001 mmol Ru), the ratio H2 / CO being 1.5 : 1 and the initial relative pressure

  of 31 MPa, for 2 hours at the indicated temperatures.

  The results are given in Table VIII, where the results are shown in Table VIII.

9T '0 TT' 0

O * 1% 4

ZiO Zú O

ET '0 9T' 0

0 0

ST "O LT 'O

O 0

  ## EQU1 ## OOt OOZ OOZ aO0 OO 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 O o '0 TS' 0 HOON (totu T'0) -SH ('[Oum = T') (Totux T 'O) TDT'I (o TUO) (TOMu T'O) EBH (TOtU = T'O1) XEIH (ToU & Tt'O) 211H aflH (ToU <UT'O) TEH (ToUrr TO) XER

(TOWU T '0)

  SH ZBH ii iY Zl (00) Enu Z1 (OD) Enu Z (00) únu ZT (O;)) ne AND (00) Enu AND (OD) Cflu ZT (oo) Cr1u E 0 (0D) null T (OD) ) nu (0nT) n H

IIIA EMMENI

  C:> c / i tt!

T'9 6T '80'0

  O t''O 6 'tT 9s' 0 HO HO: H HOO HO HOHH DO DO IT ((ToMu T'O) 1 H (Touu 8'S)

T; TPPV

  (ta; Tn) IIIA nvogvë: r) (S, -e; u Ln om! saToum 'sueueapueu * (On) mt (OD) únu i C743

- 36 -

Claims (13)

  Process for the preparation of acetaldehyde and / or ethanol, characterized in that carbon monoxide and hydrogen are reacted at a temperature of about 150 to 300 ° C and at superatmospheric pressure in the presence of a catalytic system initially formed of a ruthenium source and a halide source   and recovering acetaldehyde and / or ethanol.   2. Process according to claim 1, characterized in that acetaldehyde is formed in a first reaction stage and, subsequently, ethanol in a second reaction stage, the catalytic system being present.   at least during the first reaction stage.   3. A process according to claim 2, characterized in that the ruthenium is present during the second stage of reaction.   4. Process according to claim 2, characterized in that a hydrogenation catalyst is present   during the second stage reaction.   5. A process according to claim 4, characterized in that the ruthenium is removed from the product of the first stage of reaction before the reaction of the second stage. 6. A process according to claim 4, characterized in that the hydrogenation catalyst comprises palladium.   7. A process according to one of claims 1 to 6,   characterized by the fact that the temperature is about at 2750C.   8. Process according to one of claims 1 to 7,   characterized by the fact that the pressure is about at 600 bar.   9. A process according to one of claims 1 to 8,   characterized in that the molar ratio of hydrogen to   carbon monoxide is between 1/10 and 10/1 approximately. Z C 743 - 37 -   10.- Method according to one of claims 1 to 9,   characterized by the fact that the catalytic system comprises   in addition an alkaline chloride or bromide.   11. A process according to one of claims 1 to 9,   characterized by the fact that the catalytic system comprises   in addition, hydrogen chloride or hydrogen bromide.   12. Process according to claim 10, characterized   in that the alkali metal is lithium.   13.- Method according to one of claims 1 to 12,   characterized in that the reaction is carried out in the presence of a solvent comprising an organic amide aprotic 14.- Method according to the fact that the solvent laughing) -pyrrolidinone (2).   15.- Method according to the fact that the lower solvent) -acetamide 16. - Method according to the fact that the solvent dinone (2). 17.- Method according to the fact that the solvent acetamide. 18.- Method according to the fact that the solvent propionamide. claim 13, characterized comprises an N- (lower alkyl)   Claim 13, characterized comprises an N, N-bis- (alkyl claim 13, characterized includes N-methylpyrrolidine claim 13, characterized comprises N, N-diethyl- claim 13, characterized comprises N, N-diethyl-