PROCESS FOR PREPARING GLYCOL ETHERS

Abstract: Ethylene or propylene glycol ethers (the latter generally together with the corresponding alkoxy acetone) can be obtained in good yield and selectivity by reacting hydrogen. carbon monoxide and an aldehyde or acetal of the formula RCHO or RCH (OR′)₂ wherein R is hydrogen or methyl and R′ is C₁-₁₀ alkyl, in the presence of a cobalt-containing catalyst and an alcohol of the formula R′OH at a pressure of at least 35 bars and a temperature of 50 to 350 °C. The reaction is conducted in the presence of a tin-­ containing compound or a germanium-containing com­ pound as catalyst promoter. Formaldehyde or an acetal thereof or a formaldehyde-­ releasing compound is generally reacted at a temperature of from 50 to 300°C and a pressure from 70 to 350 bars to give a product containing ethylene glycol ethers, while acetal­ dehyde or an acetal thereof is reacted at a temperature of 50 to 350°C and a pressure of 70 to 700 bars to give a product containing propylene glycol ether of the formulae and an alkoxyacetone of the formula CH₃-CO-CH₂-OR′

Description: PROCESS FOR PREPARING GLYCOL ETHERS This invention relates to a process for preparing glycol ethers. More particularly this invention relates to a process for preparing monoalkyl ethers of ethylene glycol and propylene glycol by the reaction of synthesis gas (i.e. a mixture of hydrogen and carbon monoxide) with, (a) formaldehyde, acetaldehyde, or an acetal thereof, and (b) an alcohol. A cobalt catalyst, promoted by a compound of tin or germanium is employed. There is an ever increasing need for a wide variety of glycol monoalkyl ethers of different carbon numbers and structures which have become important articles of commerce. Such ethers are employed in a wide variety of application as solvents, reaction media, etc. In conventional processes, an olefin oxide such as ethylene oxide or propylene oxide, is first prepared from an olefin and reacted with suitable alcohol. Since the cost of materials derived from petroleum sources has been rising rapidly, research efforts are now being made to find a new process for producing these glycol ethers which does not utilize an olefin as a starting material. One of the newer methods for the preparation of glycol monoalkylethers, in which an acetal is reacted with carbon monoxide and hydrogen in the presence of a cobalt carbonyl catalyst, is described in German Patents 875,802 and 890,945. This process suffers from several disadvantages, including a low selectivity of the glycol ether, and decomposition of the carbonyl catalyst during recovery of the product from the reaction mixture. In the U.S. 4,071,568 a process for making glycol monoalkyl ethers is disclosed in which the catalyst utilized is cobalt carbonyl combined with a trivalent organic phosphorus compound such as tri-n-butylphosphine which is reported to give better selectivity. Other processes for preparing glycol monoalkyl ethers are described in U.S. 4,062,898 and in German-2,741,589. One of the objects of this invention is to provide a novel processes for preparing ethylene and propylene glycol monoalkyl ethers by means of a unique catalyst system in which the feedstock utilized comprises formaldehyde, acetaldehyde or an acetal thereof, an alcohol and synthesis gas. This invention provides a process for preparing ethylene or propylene glycol ethers by reacting hydrogen, carbon monoxide and an aldehyde or- acetal of the formula RCHO or RGH(ORl)2 wherein R is hydrogen or methyl and R' is -10 alkyl, in the presence of a cobalt-containing catalyst andanalcohol of the formula R'OH at a pressure of at least 35 bars and a temperature of -50 to 3500G, in -which process the reaction is conducted in the presence of a tin-containing compound or a germanium-containing compound as catalyst promoter. In one embodiment of the invention, formaldehyde or an acetal thereof or a formaldehyde-releasing compound is reacted at a temperature of from 50 to 3000C and a pressure from 70 to 350 bars to give a product containing ethylene glycol ethers. In this embodiment, formaldehyde or its acetal react as follows: EMI2.1 In another embodiment of the invention, acetaldehyde or an acetal thereof is reacted at a temperature of 50 to 3500C and a pressure of 70 to 700 bars to give a product containing propylene glycol ether of the formulae EMI3.1 generally an alkoxyacetone of the formula CH3-CO-CH20R' is obtained in association with the propylene glycol ethers. In these formulae R' has the meaning given above. In this latter embodiment, acetaldehyde and an alcohol react with synthesis gas as follows: EMI3.2 Under certain operating conditions, alkoxyacetones are formed as the major products in this embodiment of the process according to the reaction scheme of equation (iv) above. A high degree of selectivity is exhibited by the reaction of the process of this invention. For example, when acetaldehyde and ethanol are reacted with synthesis gas substantial yields of the propylene glycol monoethyl ethers and the ethoxyacetone are obtained. In carrying out the reaction of this invention selectively to produce high yields of the desired ethylene glycol ethers or the desired propylene glycol monoalkylethers and/or alkoxyacetones it is necessary to supply sufficient carbon monoxide, hydrogen, aldehyde' or acetal and alcohol to at least satisfy the stoichiometry of equations (i), (ii) (iii) and/or (iv) above although an excess of one or more of the reactants over the stoichiometric amounts may be present. Catalysts that are suitable for use in the practice of this invention contain cobalt The cobalt-containing compounds may be chosen from a wide variety of organic- or inorganic compounds, complexes, etc., as will be shown and illustrated below. It is only necessary that the catalyst precursor actually employed contain said metal in any of its ionic states. The actual catalytically active species is then believed to comprise cobalt in complex combination with one or more ligands and with carbon monoxide and hydrogen. The most effective catalyst is achieved where the cobalt hydrocarbonyl species is solubilized in the alcohol coreactant employed. The cobalt-containing catalyst precursors may take many different forms. For instance, the cobalt may be added to the reaction mixture in an oxide form, as in the case of, for example, cobalt(II) oxide (CoO) or cobalt(II, III) oxide (Co304). Alternatively, it may be added as the salt of a mineral acid, as in the case of cobalt(II) chloride (CoC12 ), cobaIt(II) chloride hydrate (CoC12 -6H2 O), cobalt(II) bromide (CoBr2 ), cobalt(II) iodide (CoI2) and cobalt(II) nitrate hydrate (Co(N03)2.6H20), etc., or as the salt of a suitable organic carboxylic acid, for example, cobalt(II) formate, cobalt(TI) acetate, cobalt(II) propionate, cobalt -naphthenate, cobalt acetylacetonate, etc. The cobalt may also be added to the reaction zone as a carbonyl or hydrocarbonyl derivative. Here, suitable examples include dicobalt octacarbonyl (Co (cho) ) cobalt hydrocarbonyl (HCo(CO) ) and substituted carbonyl 4 species such as the triphenylphosphine cobalt tricarbonyl dimer, etc. Preferred cobalt-containing compounds include oxides of cobalt, cobalt salts of a mineral acid, cobalt salts of organic- carboxylic acids and cobalt carbonyl or hydrocarbonyl derivatives. Among these, particularly preferred are cobalt(II) chloride, cobalt acetylacetonate, cobalt(II) ) acetate, cobalt(II) propionate, and dicobalt octacarbonyl. As previously pointed out in the process of this invention the reaction is conducted in the presence of a catalyst comprising a cobalt-containing compound and a tin- or germanium-containing promoter. The cobalt-containing compound employed may be a cobalt carbonyl or a compound capable of forming a cobalt carbonyl under reaction conditions. The tin-containing promoter compounds which may be utilized with the cobalt-containing compounds in this process may also take many different forms. For instance the tin may be added to the reaction mixture in elemental form, or in the form of a halide, such as stannic chloride, stannous iodide, stannic bromide, or a hydrocarbyl tin compound such as tetraphenyltin, tetra-n-butyltin, hexamethylditin, tetramethyltin, and dibutyl diphenyltin, or as organohalide tin compound such as trimethyltin chloride, di-t-butyltin dichloride, dimethyltin dichloride, methyltin trichloride, phenyltin trichloride, triethyltin bromide, trimethyltin bromide and tributyltin bromide, or an organotin hydride such as tributyltin hydride, or an organotin oxide such as dimethyltin oxide and diphenyltin oxide, or a carboxylate such as tin(II) caproate, tributyltin acetate, and trin-propyltin acetate, or an oxide such as stannous oxide and stannic oxide. The preferred tin-containing promoter compounds are the organo-halide tin compounds. Among these, particularly preferred are trimethyltin chloride, tributyltin hydride and tributyltin bromide. The germanium-containing promoter compounds which may be utilized with the cobalt-containing compounds in this- process may also take many different forms. For instance, the germanium may be added to the reaction mentioned in the form of a halide, such as germanium tetrachloride, germanium diiodide and germanium tetrabromide, or as a hydrocarbylgermanium compound such as tetra-n-butylgermane, tetraethylgermane, tetraphenylgermane and tetramethylgermane, or an organo-halide germanium compound such as diphenylgermanium chloride, methylgermanium trichloride, phenylgermanium trichloride, tri-n-butyigermanium iodide, triethylgermanium chloride, triethylgermanium iodide, trimethylgermanium chloride, triphenylgermanium bromide and triphenylgermanium chloride or an organogermanium hydride, such as triphenylgermanium hydride, or an organogermanium oxide or carboxylate such as triphenylgermanium acetate, or a germanium alkoxide such as germanium butoxide, germanium ethoxide and germanium methoxide. The preferred germanium-containing promoter compounds are the organo-halide germanium compounds, the hydrocarbylgermanium compounds and the organogermanium hydrides. Among these, particularly preferred are triphenylgermanium bromide, triphenylgermanium hydride, trimethylgermanium chloride, triphenylgermanium chloride, trimethylgermanium bromide, triethylgermanium chloride, tetraphenylgermane and tetramethylgermane. The amount of the tin-containing or germaniumcontaining compound employed can be varied widely in this process and is generally in the range of 0.01 to 100 and preferably from 0.1 to 5 gram moles per gram atom of cobalt The quantity of cobalt catalyst employed in the instant invention is not critical and may vary over a wide range. In general, the novel process is desirably conducted in the presence of a catalytically effective quantity of one or more of the active cobalt - species together with one or more of the tin- or germanium-containing promoters which gives the desired products in reasonable yields.. The reaction proceeds when employing as little as 1 x 10 6 weight percent and even lesser amount of cobalt, basis the total weight of the reaction mixture. The upper concentration is dictated by a variety of factors including catalyst cost, partial pressures of carbon monoxide and hydrogen, operating temperature, etc. A cobalt catalyst concentration of from 1 x 10 5 to 10 weight percent cobalt, based on the total weight of reaction mixture, is generally desirable in the practice of this invention. Alcohols useful as starting materials in the process of this invention (see equations (i) to (iv) above) have the formula: R'OH where R' is an alkyl radical of from 1 to 10 carbon atoms. Suitable alcohols include methanol, ethanol, propanol, butanol, heptanol, decanol, etc., and isomers thereof. Formaldehyde acetals which may be utilized in the process of this invention include compounds of formula: (R'O)2CH2, where R' is alkyl of from 1 to 10 carbon atoms as exemplified by methyl, ethyl, butyl, hexyl, nonyl, etc., and isomers thereof. The preferred acetals include dimethoxymethane, di-n-butoxymethane, diethoxymethane, and dipropoxymethane. Acetals of acetaldehyde which may be utilized in the process of this invention include compounds of the formula: (R'O)2CH2CH3 where R' has the meaning given above. The preferred acetals include 1,1-dimethoxyethane, 1, l-diethoxyethane (commonly known as acetal) and l,l-di-n-propyloxyethane. The acetal or aldehyde are used in combination with an alcohol. The ratio of alcohol to aldehyde is not critical but is usually in the range of 0.01 to 100 moles of alcohol per mole of aldehyde (or acetal). The relative amounts of carbon monoxide and hydrogen which may be initially present in the syngas mixture are also variable, and these amounts may be varied over a wide range. In general, the mole ratio of CO:H2 is in the range from 20:1 up to 1:20, preferably from 5:1 to 1:5, although ratios outside these ranges may also be employed. Particularly in continuous operations, but also in batch experiments, the carbon monoxide-hydrogen gaseous mixtures may also be used in conjunction with up to 50% by volume of one or more other gases. These other gases may include one or more inert gases such as nitrogen, argon, neon and the like, or they may include gases that may, or may not, undergo reaction under CO hydrogenation conditions, such as carbon dioxide, hydrocarbons such as methane, ethane, propane and the like, ethers such as dimethyl ether, methylethyl ether and diethyl ether. The temperature range which can usefully be employed in these syntheses is a further variable, dependent upon other experimental factors, including the choice bf the alcohol, the pressure, and the concentration and choice of particular species of the cobalt-containing compound and the promoter compounds among other things. The range of operability is from 50- to 35O0C, although with formaldehyde or an acetal thereof, the preferred maximum temperature is 3000C. A narrower range of 100 to 2500C represents the most preferred temperature range. Superatmospheric pressures of 35 bars or greater leads to substantial yields of desirable glycol ethers by the process of this invention. Preferred operating ranges are from 70 to 350 bars when using formaldehyde (or its acetal), and 70 to 700 bars when using acetaldehyde (or its acetal), although pressures above 700 bars also provide useful yields of the desired products. The pressures referred to here represent the total pressure generated by all the reactants, although they are substantially due to the carbon monoxide and hydrogen fractions in these examples. As far as can be determined, without limiting the invention thereby, the one-step process disclosed herein leads primarily to the formation of ethylene glycol monoalkyl ethers or propylene glycol monoalkyl ethers and alkoxyacetone products. Ethylene glycol dialkyl ether products are also formed, and in the case, for example, where formaldehyde and n-butanol are the co-reactants, the principal products are ethylene glycol monobutyl ether and ethylene glycol dibutyl ether. Diethylene glycol monobutyl ether, methanol, butyl formate and water are also detected in the liquid product fraction. The propylene monoalkyl ethers may be generated in this process in two isomeric forms, i.e., the propylene glycol OC-monoalkyl ethers and propylene glycol p-monoalkyl ethers which have the general structures I and TI respectively, where in this case R' is an alkyl radical of from 1 to 10 carbon atoms. EMI9.1 In the case where acetaldehyde and ethanol are the coreactants, the principal products are the propylene glycol monoethyl ethers and ethoxyacetone. By-products such as water, ethanol and diethyl ether are also detected in the liquid product fraction. The novel process of this invention can be conducted in a batch, semicontinuous or continuous fashion. The catalyst may be initially introduced into the reaction zone batchwise, or it may be continuously or intermittently introduced into such a zone during the course of the synthesis reaction. Operating conditions can be adjusted to optimize the formation of the desired ether products, and said material may be recovered by methods well known in the art, such as distillation, fractionation, extraction and the like. A fraction rich in the cobalt-containing compound and the promoter compound may then be recycled to the reaction zone, if desired, andsadditional products generated. The products formed by the process of this invention have been identified in this work by one or more of the following analytical procedure, viz, gas-liquid phase chromatograph (glc), infrared (ir), mass spectrometry, nuclear magnetic resonance (nmr) and elemental analysis, or a combination of these techniques Analyses have, for the most part, been by parts in weight; all temperatures are in degrees centigrade and all pressures in bars. The following Examples which illustrate various embodiments of the invention are to be considered not limitative. EXAMPLE 1 To a 450 ml glass-lined, pressure reactor was charged a mixture of dicobalt octacarbonyl (2 mmole Co), triphenylgermanium bromide (2 mmole) and paraformaldehyde (0.1 mole) in 37.1 g of n-butanol (0.5 mole). The mixture was flushed with nitrogen, the reactor sealed, flushed with CO/H2 (1:1 molar ratio), pressured to 187.2 bars with 2:1 molar ratio syngas (H2/CO) and then heated to 16O0C with agitation. After four hours, the reactor was allowed to cool, the gas pressure (173.4 bars) noted, the excess gas sampled and vented, and the deep red liquid product (44.5 g) recovered. Analysis (glc and Karl Fischer titration) of the liquid product showed it to contain: 12.2 wt. % ethylene glycol monobutyl ether 1.4 wt. % ethylene glycol dibutyl ether 1.2 wt. % water 71.4 wt. % unreacted n-butanol. Estimated yield of ethylene glycol monobutyl ether (basis formaldehyde charged) was 46 mole percent. Total glycol monobutyl plus dibutyl ether yield was 50 mole percent. Analysis of the liquid product by atomic adsorption showed it to contain =-98 % of the cobalt originally charged. There was no solid product phase. Typical off-gas samples showed the presence of: 58 % hydrogen 37 % carbon monoxide 3.5 % carbon dioxide The glycol monobutyl ethers were recovered from the crude liquid product by fractional distillation in vacuo. EXAMPLE 2 To a 450 ml glass-lined pressure reactor was charged a mixture of dicobalt octacarbonyl (2 mmole Co), triphenylgermanium bromide (2.0 mmoles), dibutoxymethane (0.1 mole) in 22.2 g of n-butanol (0.3 mole). The mixture was flushed with nitrogen, the reactor sealed, flushed with CO/H2 (1:2 molar), was pressured to 187.2 bars with 1:2 molar syngas (CO/H2 ) and then heated to 160 C with agitation. After four hours, the reactor was allowed to cool, the gas pressure (159.6 bars) was noted, the excess gas sampled and vented, and the deep reddish- brown liquid product (43.0 g) recovered. Analysis (glc and Karl Fisher titration) of the liquid product showed it to contain: II.6 wt % ethylene glycol monobutyl ether 3.5 wt. % ethylene glycol dibutyl ether 1.7 wt % water 69.2 wt. % butanol Estimated yield of ethylene glycol monobutyl ether (basis dibutoxymethane charged) was 41 mole percent Total glycol monobutyl plus dibutyl ether yield was 50 mole percent Analysis of the liquid product by atomic adsorption showed it to contain 97% of the cobalt originally charged. There was no solid product phase. Typical of f-gas samples showed the presence of 58 % hydrogen 34 on carbon monoxide 1.9 % carbon dioxide. EXAMPLE 3 Following the procedure of Example 1 and 2, the resctor was charged with a mixture of dicobalt octacarbonyl (2 mmole Co), triphenylgermanium bromide (2 mmole), dimethoxymethane (0.1 mole) in 9.6 g of methanol (0.3 mole). The mixture was flushed with nitrogen, the reactor sealed, flushed with CO/H2 (1:2 molar), pressured to 187.2 bars with 1:2 molar syngas (CO/H2) and then heated with agitation to 200 OC. After four hours, the reactor was allowed to cool, the gas pressure (169.9 bars) noted, the excess gas sampled and vented, and the black liquid product (18.3 g) recovered. Analysis of the liquid product showed it to contain: 9.8 wt. % ethylene glycol monomethyl ether 3.2 wt. % ethylene glycol dimethyl ether 8.9 wt. % water 9.1 wt. % dimethoxymethane 60.5 wt. % methanol. Typical off-gas samples showed the presence of: 54 % hydrogen 32 % carbon monoxide 1.1 % carbon dioxide 0.5 % methane. EXAMPLES 4-18 A number of additional Examples were carried out using the procedure of Example I in which a variety of tin- and germanium-containing promoters were employed along with cobalt octacarbonyl catalyst. Data relating to these Examples are shown in Tables 1 and 2 which follows. Specifically: a) Examples 4 to 9 illustrate the effectiveness of dicobalt octacarbonyl coupled with various germanium promoters, including triphenylgermanium hydride, tetraphenylgermane, tetraethylgermane, triphenylgermanium chloride, trimethylgermanium bromide and triethylgermanium chloride. b) Examples 10 to 18 demonstrate the effective use of dicobalt octacarbonyl coupled with various tin-containing promoters, including tributyltin bromide, tributyltin chloride and trimethyltin chloride. TABLE 1 a,b Liquid Product Composition (wt. %) EGMBEd Example Catalyst Composition H2O MeOH BuOH EGMBE EGDBE EG Yield (Mole %) 4 Co2(CO)8-Ph3GeCl 4.9 0.3 72.4 12.2 1.4 0.2 45 5 Co2(CO)8-Me3GeBr 5.1 0.3 73.8 11.3 1.5 0.2 42 6 Co2(CO)8-Et3GeCl 4.9 0.3 72.9 12.3 1.4 0.2 46 7 Co2(CO)8-Ph4Ge 4.5 0.4 74.2 14.0 1.0 0.5 53 8 Co2(CO)8-Et4Ge 5.1 0.3 70.9 13.2 1.6 0.3 50 9 Co2(CO)8-Ph3GeH 4.7 0.4 72.6 13.0 1.4 0.3 47 aRun Change: Co, 2 mmoles; Co/Ge = 1/1; BuOH, 0.5 mole; HCHO, 0.1 mole. aRun Condition: 160 C., initial 187.2 bars of CO/H2 (1:2 molar), 4 hours. cDesingnation: EGMBE, Ethylene glycol monobutyl ether; EGDBe, ethylene glycol dibutyl ether; dEGMBE yield basis formaldehyde charged. TABLE 2 a,b Liquid Product Composition (wt. %)c EGMBEd Example Catalyst Composition H2O MeOH BuOH EGMBE EGDBE EG Yield (Mole %) 10 Co2(CO)8-Bu3SnBr 4.9 0.4 76.3 8.2 1.1 0.2 29 11 Co2(CO)8-Bu3SnH 1.7 0.9 93.0 < 0.1 0.3 0.4 < 2 12 Co2(CO)8-Bu3SnOAc 2.4 0.8 87.4 0.3 0.6 0.2 < 2 13 Co2(CO)8-Bu3SnCl 4.8 0.3 76.4 9.9 0.7 1.5 37 14 Co2(CO)8-Me3SnCl 4.6 0.3 73.1 8.8 0.9 0.2 33 15 Co2(CO)8-Ph3SnCl 3.8 0.6 85.2 0.9 0.3 0.3 3 16 Co2(CO)8-Ph4Sn 3.8 0.3 83.1 1.3 0.3 0.3 5 17 Co2(CO)8-SnCl4 4.4 0.4 82.4 1.4 0.8 0.2 5 18 Co2(CO)8-SnCl2 4.4 0.4 87.7 1.8 0.8 0.1 6 aRun Change: Co, 2 mmoles; Co/Sn = 1/1; BuOH, 0.5 mole; HCHO, 0.1 mole. aRun Condition: 160 C., initial 187.2 bars of CO/H2 (1:2 molar), 4 hours. cDesingnation as per Table 1 dEGMBE yield basis formaldehyde charged. EXAMPLE 19 Following the procedure of Example 1, the reactor was charged with a mixture of dicobalt octacarbonyl (2 mmole Co), triphenylgermanium bromide (2 mmole) and paraformaldehyde (0.1 mole) in 16.0 g of methanol (0.5 mole). The mixture was flushed with CO/H2 , the reactor sealed, pressured to 187.2 bars with CO/H2 (1:2 molar) and heated with agitation to 1800C. After four hours, the reactor was allowed to cool, the excess gas vented and the liquid product (23.4 g) recovered. Analysis of the liquid product showed it to contain 8.4 wt. % of ethylene- glycol monomethyl ether and 0.7 wt. % of ethylene glycol dimethyl ether. Cobalt recovery in solution was 298 % of that originally charged, there was no solid product phase. EXAMPLE 20 Following the general procedure of Example 1, the 450 ml glass-lined pressure reactor was charged with 0.1 mole of paraformaldehyde, dicobalt octacarbonyl (2.0 mmole Co), triphenylgermanium bromide (2.0 mmole) and 0.5 mole of n-butanol. After flushing with syngas (CO/H2 mixture), the reactor was pressured to 187.2 bars with a gaseous mixture containing 2 moles of hydrogen per mole of carbon monoxide, and heated to 1600C -with agitation. After 4 hours at temperature, the reactor was cooled and vented and the clear red liquid product (44.5 g) recovered and analyzed by glc and Karl Fischer titration. There were no residual solids at this state. The product liquid was distilled in vacuo, and ethylene glycol monobutyl ether was recovered as a distillate fraction at- 48-520C (1 mm Hg pressure). The residual catalyst remained behind as a -deep red colored liquid (3.6 'g) and this residual catalyst liquid was returned to the 450 ml glass-lined reactor by washing with additional n-butanol (0.5 mole). Fresh paraformaldehyde (0.1 mole) was also added at this stage, the reactor sealed, flushed with syngas, pressured to 187.2 bars with CO/H2 (1:2 molar) and heated to 1600C with agitation for 4 hours. In this manner the synthesis of ethylene glycol monobutyl ether was repeated successfully, and the later recovered from the crude liquid product (44.6 g) by vacuum distillation as outlined above. The residual catalyst solution (5.1 g) from this second cycle was again returned to the reactor for further glycol ether synthesis. The yields of glycol monobutyl ether (basis paraformaldehyde charged) for this three cycle experiment are shown in Table 3. TABLE 3 Ethylene Glycol Butyl Ethers From Syngas Catalyst Recycling Number of Yield of Example Catalyst Cycles BuOCH2CH2OH(%)a 20 1 46 2 47 3 45 a Yield basis paraformaldehyde charged (0.1 mole) at the start of each catalyst cycle. EXAMPLE 21 A 450 ml glass-lined pressure reactor was charged with a mixture of dicobalt octacarbonyl (20 mmole Co), triphenylgermanium hydride (2.0 mmole) and l,l-diethoxylethane, i.e., acetal (0.1 mole) in 23.0 g of ethanol (0.5 mole). The mixture was charged under a nitrogen atmosphere, the reactor sealed, flushed with CO/H2 (1:2 molar), pressured to 311.3 bars with 1:2 molar syngas (CO/H2 ) and then heated to 1800C with agitation. After carbonylation the reactor was cooled, the gas pressure noted (277.9 bars), the excess gas sampled and vented, and the dark brown liquid product (40.5 g) recovered. Analysis of the liquid product by glc and Karl Fischer titration showed it to contain: 4.9 % propylene glycol X-monoethyl ether 3.0 % propylene glycol -monoethyl ether 0.7 % l-ethoxyacetone -4.5 % water 7.8 % diethylether 66.6 % ethanol 1.4 % unreacted acetal Estimated yield of propylene glycol monoethyl ethers (Basis acetal charged) = 31 mole %. Yield of propylene glycol monoethyl ethers + l-ethoxyacetone (basis acetal converted) = 35 mole %. Typical off-gas samples showed the presence of: 66 % hydrogen 27 % carbon monoxide 3.4 % carbon dioxide The propylene glycol monoethyl ethers were recovered from the crude liquid product by fractional distillation in vacuo. EXAMPLE 22 Following the operating procedures of Example 21, the reactor was charged with a mixture of dicobalt octacarbonyl (2 mmole Co), triethylgermanium chloride (2.0 mmole Co), acetal (0.05 mole) and 13.80 g of ethanol (0.3 mole). After pressuring to 311.3 bars with 1:2 molar syngas (CO/H2), the reactor was heated to 180C with agitation. After 8 hours, the reactor was cooled, the gas pressure noted (256.1 bars), the excess gas sampled and vented and the red liquid product (22.3 g) recovered. Analysis of the liquid product by glc and Karl Fischer titration showed it to contain: 6.2 % propylene glycol oGmonoethyl ether 4.0 % propylene glycol p-monoethyl ether 0.2 % ethoxyacetone 4.9 % water 1.5 % diethyl ether 69.8 % ethanol 0.2 % unreacted acetal Estimated yield of propylene glycol monoethyl ethers (basis acetal charged) = 44 mole % Yield of propylene glycol monoethylethers + ethoxyacetone (basis acetal converted) = 45 mole % Typical off-gas samples showed the presence of: 55 % hydrogen 40 % carbon monoxide 37 % carbon dioxide Analysis of the liquid product by atomic absorption showed it to contain 98% of the cobalt originally charged. There was no solid product phase. EXAMPLE 23 Following the operating procedures of Example 21, the reactor was charged with a mixture of dicobalt octacarbonyl (2 mmole Co), triphenylgermanium hydride (2.0 mmole), acetaldehyde (0.1 mole) and 37.1 g of n-butanol (0.5 mole). After pressuring to 187.2 bars with 1:2 molar syngas (CO/H2 ), the reactor was heated to 160 C with agitation. After four hours, the reactor was cooled, the gas pressure (177.9 bars) noted, the excess gas sampled and vented and the deep-red liquid product (44.2 g) recovered. There was no solid phase. Analysis of the liquid product by glc and Karl Fischer titration showed it to contain: 6.6 * n-butoxypropanone 3.1 % propylene glycol monobutyl ethers 5.3 % water 79.3 % n-butanol 0.2 % unreacted acetaldehyde Typical off-gas samples show the presence of 56.5 % hydrogen 31.6 % carbon monoxide 2.2 % carbon dioxide EXAMPLE 24 Following the operating-procedures of Example 21, the reactor was charged with a mixture of dicobalt octacarbonyl (2 mmole Co), triphenylgermanium hydride (2.0 mmole), acetaldehyde (0.1 mole) and 18.0 g of n-propanol (0.3 mole). After pressuring to 311.3 bars with 2:1 molar syngas (CO/H2), the reactor was heated to 180 C with agitation. After four hours, the reactor was cooled, the gas pressure noted (273.4 bars) the excess gas sampled and vented and the liquid product (24.9 g) recovered. Analysis of the liquid product by glc and Karl Fischer titration showed it to contain: 4.8 % propylene glycol monopropyl ethers 4.2 % n-propoxyacetone 4.5 % water 66.9 % n-propanol 7.7 % ethanol 0.5 % unreacted acetaldehyde Typical off-gas samples showed the presence of: 2.9 % hydrogen 7.0 % carbon monoxide 0.1 % carbon dioxide Analysis of the liquid product showed it to contain > 98% of the cobalt originally charged. There was no solid product phase. EXAMPLE 25 Following the operating procedure of Example 23, the reactor was charged with a mixture of dicobalt octacarbonyl (2 mmole Co), triphenylgermanium hydride (2.0 mmole), acetaldehyde (0.1 mole) and 37.1 g of n-butanol. After pressuring to 311.3 bars with 1:2 molar syngas (CO/H 2 the reactor was heated to 1800C with agitation. After four hours, the reactor was cooled, the gas pressure noted (287.2 bars), the excess gas sampled and vented and the liquid product (44.1 g) recovered. Analysis of the liquid product by glc and Karl Fischer titration showed it to contain: 5.6 % propylene glycol monobutyl ethers 1.8 % n-butoxypropanone 2.8 % water 76.9 % n-butanol 5.2 % ethanol cO.l % unreacted acetaldehyde Typical off-gas samples showed the presence of: 5.6 % hydrogen 4.1 % carbon monoxide 2.0 % carbon dioxide Analysis of the liquid product showed it to contain > 98% of the cobalt originally charged. There was no solid process phase. EXAMPLES 26-39 Using the same procedure as in Example 21, a number of additional Examples were carried out in which acetal was reacted with carbon monoxide and hydrogen in the presence of a variety of tin and germanium promoters. Data relating to these Examples are included in Tables 4 and 5 which follow. It may be noted that: 1) Propylene glycol monoethyl ethers may be generated from synthesis gas, acetal (l,l-diethoxyethane) and ethanol using solubilized cobalt octacarbonyl coupled with a variety of tin and germanium promoters. Suitable promoters include triphenylgermanium bromide, triphenylgermanium hydride, triethylgermanium chloride, tetraethylgermane, trimethylgermanium bromide and tetraphenylgermane. 2) Cobalt recovery in solution was )98% for many of these cobalt catalyst combinations. 3) Syntheses were conducted over the temperature range 160-1800C when employing reaction times of 4 to 18 hours. TABLE 4 Propylene Glycol Monoalkyl Ethers By Reaction of Synthesis Gas, Ethanol and Acetala Aldehyde Liquid Product Composition (Wt. %)b Catalyst Co- Time 1-Et, 2-Et, Cobalt Example Composition Reactant Hour 2-Pro 1-Pro 1-EtAcet Acetal H2O EtOH Recovered (%) 26 Co2(CO98-Ph3GeBr Acetal 4 1.4 1.5 8.8 1.4 2.6 70.0 > 98 27 Co2(CO98-Ph3GeH Acetal 4 1.0 1.6 8.6 1.5 3.0 73.5 28 Co2(CO98-Me3GeBr Acetal 4 1.7 1.6 8.4 0.7 3.5 70.6 > 98 29 Co2(CO98-Bu3SnH Acetal 4 0.1 6.7 17.6 1.4 64.6 > 98 30 Co2(CO98-Bu3SnCl Acetal 4 0.6 7.5 3.0 2.1 78.2 31 Co2(CO98-Et4Gec Acetal 4 5.8 5.0 4.2 2.6 4.2 65.2 32 Co2(CO98-Ph4Gec Acetal 4 4.2 3.5 4.1 2.2 3.3 73.3 33 Co2(CO98-Et3GeClc Acetal 4 4.7 4.8 5.7 2.2 3.6 66.4 > 98 aRun Conditions: Co, 2 mmole; Ge/Sn, 2 mmole; Acetal, 0.1 mole; EtOH, 0.3 mole; 160 C; 187.2 bars (Co/H2, 1:2 Molar). bAbbrev: 1-Et, 2-Pro, EMI24.1 c Run Conditions: 180 C, 311.3 bars (CO/H2, 1:2 molar). TABLE 5 Propylene Glycol Monoalkyl Ethers from Synthesis Gas, Ethanol and Acetal a Aldehyde Liquid Product Composition (Wt. %)b Catalyst Co- Time 1-Et, 2-Et, Cobalt Example Composition Reactant Hour 2-Pro 1-Pro 1-EtAcet Acetal H2O EtOH Et2O Recovered (%) 34 Co2(CO)8-Et3GeCl Acetal d 8 6.2 4.0 0.2 0.2 4.9 69.8 1.5 > 98 35 Co2(CO)8-Ph3GeH c Acetal 18 5.8 4.9 Trace 1.5 2.6 54.7 9.0 36 Co2(CO)8-Ph3GeH c Acetal d 8 4.2 4.0 0.2 2.8 5.0 72.6 5.9 37 Co2(CO)8-Ph3GeBr c Acetal d 8 5.6 3.1 0.2 2.3 5.0 68.4 5.8 38 Co2(CO)8-Ph3GeBr c Acetal d 8 3.9 3.3 0.2 2.5 4.0 69.6 6.9 39 Co2(CO)8-Ph3GeBr Acetal d,e 4 0.4 7.1 6.2 2.7 77.5 1.6 > 98 a Run conditions: Co, 2mmole; Ge/Sn, 2 mmole; Acetal, 0.1 mole; EtOH, 0.3 mole; 160 C, 187.2 bars (CO/H2, 1:2 molar) b Abbrev. 1-Et, 2-Pro, EMI25.1 2-Et, 1-Pro, EMI25.2 c Run conditions: 180 C, 311.3 bars (CO/H2, 1:2 molar) d 0.05 mole, Acetal e 207.9 bars CO/H2, 2:1 molar EXAMPLE 40 A 450 ml glass-lined pressure reactor was charged with a mixture of dicobalt octacarbonyl (2.0 mmole Co) and tetraethylgermane (2.0 mmole) in l,l-dimethoxyethane (0.1 mole, 9.01 g) and methanol (0.3 mole, 9.60 g). The mixture was charged under a nitrogen atmosphere, the reactor sealed, flushed with CO/H2 (1:1 molar), pressured to 187.2 bars with 1:1 molar syngas (H2 /CO) and then heated to 130 0 C with agitation. After 4 hours at temperature the reactor was cooled, the gas pressure noted (173.4 bars), the excess gas sampled and vented, and the red liquid product (19.6 g, 23 ml) recovered. There was no solid precipitate at this stage. Analysis of the liquid product by glc and Karl Fischer titration shows it to contain: 9.0 % methoxyacetone 3.9 % water 0.8 % propylene glycol monomethyl ether 24.3 % unreacted l,l-dimethoxyethane 5.8 % unreacted acetaldehyde 46.1 % unreacted methanol 0.1 % ethanol Estimated conversion of l,l-dimethoxyethane + acetaldehyde = 24 %. Estimated yield of methoxyacetone (basis aldehyde + acetal converted) = 82%. Cobalt recovery in the product solution was > 98%. Analysis of a typical gas sample showed the presence of: 58 % carbon monoxide 41 % hydrogen 0.2 % carbon dioxide The methoxyacetone was recovered from the crude liquid product by fractional distillation in vacuo. Identification of the product fractions was confirmed by glc trapping and nmr analyses. EXAMPLES 41-52 Following the same procedure as in Example 40, a number of additional Examples were carried out in which l,l-dimethoxyethane and methanol were reacted with synthesis gas in the presence of a variety of germanium and tin promoters. Data relating to these Examples are included in Tables 6 and 7 which follow. TABLE 6 MEthoxyacetone From Synthesis Gas Plus 1,1-Dimethoxyethane a Liquid Product Composition (%) b Catalyst Example Composition MeAcet EMI28.1 Cobalt Acetal MeAcet c Recov. Acetal CH3CHO MeOH H2O EtOH Conv(%) Yield (%) (%) 40 Co2(CO)8-Et4Ge 9.0 0.8 24.3 5.8 46.1 3.9 0.1 24 82 > 98 41 Co2(CO)8-Ph3GeCl 6.4 0.2 29.1 6.0 47.0 3.6 0.1 17 78 > 98 42 Co2(CO)8-Ph3GeBr 4.7 0.2 30.6 6.7 46.3 4.5 0.1 10 > 95 27 43 Co2(CO)8-CsGeCl3 1.1 0.2 28.8 3.2 57.5 1.9 --- 22 11 > 98 44 Co2(CO)8-Ph4Ge 7.2 0.2 24.4 4.7 46.7 4.4 0.3 24 70 > 98 45 Co2(CO)8-Me3GeI 2.4 0.2 32.3 17.7 20.3 12.6 0.5 < 10 N.D. d > 98 46 Co2(CO)8-Me3GeBr 5.0 0.2 31.2 4.5 40.3 4.6 0.1 11.8 > 95 > 98 47 Co2(CO)8-Et3GeCl 7.2 0.3 27.7 5.4 45.2 3.9 0.3 17 93 > 98 48 Co2(CO)8-Bu3SnH 1.3 0.1 34.6 2.9 48.2 1.2 1.2 20 13 > 98 a Reaction charge: CO2(CO)8, 2.0 mmole Co; Ge/Sn, 2.0 mmole; MeOH, 0.3 mole; 1,1-dimethoxyethane, 0.1 mole. Reaction conditions: 130 C, 187.2 bars CO/H2 (1:1) initial pressure, 4 hours b Abbreviations: MeAcet, EMI28.2 Acetal, (MeO)2 CHCH3. c Methoxyacetone yield basis acetaldehyde + acetal converted d N.D., Not Determined TABLE 7 Methoxyacetone From Synthesis Gas Plus 1,1-Dimethoxyethane a Liquid Product Composition (%) b Catalyst Operating Example Composition Temp.( C) MeAcet EMI29.1 Acetal MeAcet c Acetal CH3CHO MeOH EtOH Conv(%) Yield(%) 49 Co2(CO)8-Et3GeCl 130 7.2 0.3 27.7 5.4 45.2 0.3 17 93 50 Co2(CO)8-Et3GeCl 145 7.9 0.4 19.1 5.5 46.6 1.0 30 62 51 Co2(CO)8-Et3GeCl 160 8.3 0.7 10.1 5.1 46.7 4.6 48 45 52 Co2(CO)8-Et3GeCl 180 4.1 6.0 4.6 3.8 39.3 8.2 69 15 a Reaction charge: CO2(CO)8, 2.0 mmole Co; Ge, 2.0 mmole; MeOH, 0.3 mole; 1,1-dimethoxyethane, 0.1 mole Reaction conditions: 187.2 bars CO/H2 (1:1) initial pressure, 4 hours b Abbreviations: MeAcet, EMI29.2 Acetal, (MeO)2CHCH3. c Methoxyacetone yield basis acetaldehyde + acetal converted

Claims: SET A CLAIMS: 1. A process for preparing ethylene or propylene glycol ethers by reacting hydrogen, carbon monoxide and an aldehyde or acetal of the formula RCHO or RCH(OR')2 wherein R is hydrogen or methyl and R' is C1 10 alkyl, in the presence - of a cobalt-containing catalyst and an alcohol of the formula R'OH at a pressure of at least 35 bars and a temperature of 50 to 3500C, characterized in that the reaction is conducted in the presence of a tin-containing compound or a germanium-containing compound as catalyst promoter. 2. A process according to Claim 1 characterized in that formaldehyde or an acetal thereof or a formaldehyde-releasing compound is reacted at a temperature of from 50 to 3000C and a pressure from 70 to 350 bars to give a product containing ethylene glycol ethers. 3. A process according to Claim 1 characterized in that acetaldehyde or an acetal thereof is reacted at a temperature of 50 to 3500C and a pressure of 70 to 700 bars to give a product containing propylene glycol ether of the formulae EMI30.1 and an alkoxyacetone of the formula CH3-CO-CH2OR' wherein R' has the meaning given in Claim 1. 4. A process according to any of Claims 1 to 3 characterized in that the cobalt-containing catalyst is one or more oxides of cobalt, a cobalt salt of a mineral acid, a cobalt salt of an organic carboxylic acid or a cobalt carbonyl or hydrocarbonyl derivative. 5. A process according to Claim 4 characterized in that the cobalt-containing catalyst is cobalt oxide, cobalt chloride, cobalt iodide, cobalt nitrate, cobalt sulfate, cobalt acetate, cobalt propionate, cobalt acetylacetonate, or dicobalt octacarbonyl. 6. A process according to any of Claims 1 to 5 characterized in that the catalyst promoter is trimethyltin chloride, tributyltin chloride, tributyltin hydride, or tributyltin bromide. 7. A process according to any of Claims 1 to 5 characterized in that the catalyst promoter is triphenylgermanium chloride, triphenylgermanium bromide, triphenylgermanium hydride, triethylgermanium chloride, tetraethylgermane, tetraphenylgermane or trimethylgermanium bromide. 8. A process according to any of Claims 1 to 7 characterized in that the temperature is from 100 to 2500C.

Inventors: KNIFTON, JOHN FREDERICK
Applicants: TEXACO DEVELOPMENT CORPORATION
Application year: 1982
Main classification: C07C43
IPC codes: C07C45, C07C41, C07C43