JPS6048940A - Manufacture of ethanol from methanol and synthetic gas - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention]

The present invention uses a cobalt-containing compound and a glumani-containing compound as catalysts to react synthesis gas, i.e., a mixture of hydrogen and carbon monoxide, with methanol in the presence of an inert oxygen-containing solvent. Relating to a method of manufacturing. The potential market for using ethanol as a gasoline diluent is increasing. Due to fluctuations in oil supply equipment1, the field of syngas technology is gaining importance. A number of methods have previously been described in the art of reacting methanol with carbon monoxide* and hydrogen in the presence of catalyst systems to mill ethanol. A general drawback of the prior art, the methods of which have been described, is that all these techniques, in addition to the desired ethanol, produce polymeric alcohols, aldehydes, hydrocarbons, carboxylic acids and esters, etc. This means that it will stiffen the widespread Sen's Sakiki products. For example, US Pat. No. 3,285,948 discloses a method for the synthesis of alcohols using a cobalt catalyst system consisting of cobalt carbonyl-promoted scraping and ruthenium halide. U.S. Pat. A three-component catalyst system has been used: a first promoter consisting of a ruthenyl compound, a first promoter consisting of an iodine compound, and a second promoter consisting of a ruthenium t5 compound. Taylor U.S. Patent No. 4,1
No. 11,837 describes the use of cobalt carbonyl catalysts with novel heterogeneous cocatalyst systems such as rhenium metal to convert methanol to ethanol and hyethanol precursors (
- An improved method for achieving this is described. walker
ker ) U.S. Pat. No. 4,277.634 and Riley et al. U.S. Pat. No. 3,248.43.
No. 2 is a j! ! ! He teaches the method of making. Similarly, British Patent No. 1,546,428 discloses that methanol is reacted with carbon monoxide and hydrogen in the presence of a solvent such as a hydrocarbon solvent, a cobalt-containing catalyst such as cobalt iodide or bromide, and a tertiary phosphine. , teaches a method for producing ethanol. US patent for Slinkard @ 4
, 168,391 teaches a method for producing ethanol by reacting -carbon oxide, hydrogen, and methanol in the presence of cobalt carbonyl and an oxygen-containing solvent such as dioxane. All of the methods described above have one or more drawbacks. In most cases, methanol conversion is low and decomposition occurs.
The catalyst is found to be an insoluble and inert species, and various products other than heavy chain ethanol are formed, resulting in separation and processing problems. In the method of the invention, ethanol is produced in high yield by reacting methanol with a mixture of hydrogen and carbon monoxide. More specifically, the present invention produces ethanol by contacting methanol, hydrogen and carbon oxides with a catalyst system consisting of a cobalt-containing compound and a germanium-containing compound at high temperature and pressure in the presence of an oxygen-containing expanded hydrogen solvent. It is about the method. Separation of ethanol from the reacted product can be performed by any conventional or convenient method such as distillation, extraction, etc. High selectivity to ethanol is achieved by high conversion of methanol. Other advantages are that acetaldehyde is obtained as the main by-product and that a stable catalyst system is obtained that can be recycled. The present invention provides a catalyst system comprising a cobalt-containing compound and a germanium-containing compound.
, 6X 10" mHg) or more pressure and approx.
The present invention relates to a method for producing ethanol by reacting a mixture of hydrogen, carbon oxide, and methanol in the presence of an inert oxygen-containing hydrocarbon solvent at a temperature of 0 to about 350°C. Generally speaking, regarding the metal component of the catalyst system, the system contains about 20 to about 85 moles of cobalt compound and the remainder germanium-containing compound, based on the total number of moles of cobalt compound and the total number of moles of germanium compound in the system. It is included. Preferably, the catalyst system contains equimolar amounts of cobalt and germanium compounds;
The cobalt-containing compound and the germanium-containing compound are selected from a wide variety of organic or inorganic compounds, complexes, etc. as exemplified below. The catalyst precursors used may in fact be all metals in any ionization state. The species that is actually active as a catalyst is −
It is thought to consist of cobalt and armanium, which is a complex of one or more ligands, carbon monoxide, and hydrogen. The most effective catalysts are obtained when the cobalt and germanium species are soluble in the co-reactants methanol and oxygen-containing hydrocarbons. As mentioned above, the reaction in the method of the invention is carried out in the presence of a catalyst containing a cobalt-containing compound. The cobalt-containing compound used may be cobalt carbonyl or a compound in which cobalt carbonyl can form nyl during the reaction. The cobalt-containing catalyst precursor can take a variety of different forms. For example, cobalt is cobalt oxide (H) ((-
, o O) or cobalt oxide (■, ■) (co1o4)
etc., are added to the reaction mixture in the form of oxides. Alternatively, cobalt chloride (TI) (CoC4), cobalt chloride (11) hydrate (coClt・6■I20),
Cobalt bromide (IT) (CoBr, ) Cobalt nitride (TI) (COI! ) and Cobalt nitrate (1
1) as mineral acid salts such as hydrates (Co(NO,N,.6HtO), etc., or e.g. cobalt formate (IT),
Vinegar 9 Cobalt (TI), Cobalt Propionate (TI)
), cobalt naphthenate, cobalt acetylacetone, etc. may be added in combination with a suitable organic carboxylic acid salt. Cobalt may be added to the reaction zone as carbonyl or hydrocarbonyl derivatives. Here, as preferred specific examples, octacarbonyl dicobalt (Cot(CO)a), hydrocarbyl-?
Substituted calcium such as nylcobalt (HCO (CO4)) and triphenylphosphine-tricarbonylcobalt dimer? Nil species can be mentioned. Preferred cobalt-containing compounds include cobalt oxides, cobalt mineral salts, cobalt organic carboxylates, and carbonyl cobalt or hydrocarbonyl derivatives. Among these, particularly preferred is cobal chloride)
(IIL cobalt acetylacetone (III), cobal acetate) (El), 7'ro'pionate) (
IF), and the more preferable one is octacal-? Cobalt cobalt and cobalt iodide. The germanium-containing compound used in conjunction with the cobalt-containing compound in the present method may also take a variety of different forms. For example, kermanium is a halogenide such as germanium trichloride, germanium trichloride, and germanium tetrachloride; ; Rugermanium compound; Also, diphenylkelmanium! tri-n-butyl germanium iodide, tri-n-butyl germanium iodide, tri-n-butyl germanium iodide, tri-n-butyl germanium iodide, triphenyl-r-rumaniginin AJI
IJ Organic halide compounds such as phenylgermanium chloride; or organic dalmanium compounds such as triphenyldarmanium hydride; or organic halmanium oxides such as triphenylgermanium acetate; or in the form of kalmanium alkoxides such as dallmanium butoxide, kalmanium ethoxide and dallmanium methoxide. Preferred germanium-containing promoter compounds are organic halide germanium compounds, hydrocarbyl glumaniyum compounds, and organic germanium hydrides. Particularly preferred among these are triphenylgermanium bromide, triethylgermanium chloride, triphenylgermanium chloride, triethylgermanium chloride,
Tetramethylglumane is preferred, and more preferred are tetraphenylglumane and triphenylgermanium phyllodes. The number of grams moles of germanium-containing compound per duram atom of cobalt can be varied within a wide range in the present process, but is usually in the range 0.01 to 100, preferably 0.1 to 100.
It is in the range of 5.0. The strength of the cobalt catalyst used in the present invention is not constant and can vary over a wide range. In general, the novel process is preferably carried out using a catalytically effective amount of one or more active cobalt species along with one or more germanium-containing promoters to produce the desired products in reasonable yields. . I7, about lXl0-6% by weight relative to the total weight of the reaction mixture
The reaction will proceed if a very small amount or an even smaller amount is used. The concentration limits are determined by various factors such as the cost of the catalyst, the partial pressures of carbon oxide and hydrogen, and the operating temperature. In the practice of this invention, it is desirable to use a cobalt catalyst at a concentration of about I x 10-' to 10% by weight, based on the total weight of the reaction mixture. The solvents used in the process of the invention are oxygen-containing hydrocarbons, in which, for example, only oxygen atoms are present in the ether groups, ester groups, ketone groups or hydroxyl groups of alcohols, carbon, hydrogen and FII groups. Examples include compounds consisting of: Typically, oxygen-containing hydrocarbons contain 3 to 12 carbon atoms. The solvent must be substantially inert during the reaction and must have a boiling point of at least 40°C at atmospheric pressure. Ethanol and other oxygen-containing reaction products J:
It is preferable that the solvent has a boiling point as high as possible. Preferred ester type solvents are aliphatic and non-circular calylyl 1v-F diesters exemplified by butyl acetate, methyl benzoate, isopropyl isobutyrate, and globyl propionate, as well as asobin dimethyl. Useful alcohol-type solvents include cyclohexanol, 1-
Examples include monohydric (hydroxy) alcohols such as hexanol, neopentanol, and 2-octatool. Suitable ketone type solvents include, for example, acyclic ketones such as 2-pentanone, butanone, and acetophenone, and cyclic ketones such as cyclohexanone and 2-methylcyclohexanone. The ethers used as solvents include cyclic, acyclic and heterocyclic substances. Preferred ethers and

[2 means 1,
4-dioxane and ]. Examples include heterocyclic ethers exemplified by 3-dioxane. Other suitable ether solvents include di-n-propyl ether, diethylene glycol dibutyl ether, dibutyl ether, ethyl butyl gothyl, diphenyl ether, hephthylphenyl ether, anisole, tetrahydrofuran, and the like. Among all the above-mentioned groups, the most useful solvents include needles represented by monocyclic and heterocyclic ethers such as p-dioxane. Initial Ifr in the syngas mixture
2. - The relative amounts of carbon and hydrogen oxides can also be varied and these bodies can be varied over a wide range. Generally, the CO:H2 molar ratio ranges from about 20:1 to 1:20, preferably from about 5:1 to 1:5, although ratios outside these ranges are acceptable. In particular, when performing batch experiments in continuous operation (1), the -carbon oxide-hydrogen gas mixture may also be mixed with one or more inert gases such as nitrogen, argon, neon, etc. Alternatively, they may be used as a mixture under CO hydrogenation conditions, or gases that do not react, such as carbon dioxide; hydrocarbons such as methane, ethane, and propane; dimethyl ether, It may be mixed with gases such as ethers such as methyl ethyl ether and diethyl ether.The temperature range in which this synthesis can be effectively carried out can be further changed, but depending on the pressure and the concentration of cobalt-containing compounds and germanium compounds and their specificity. The preferred temperature range is from about 100 to about 250°C. Atmospheric pressures of about 500 psi (26.6 x 10" H, 9) or more provide high yields of the desired ethanol in the process of the present invention. At the end of the preferred working range, about 100 ~Approximately 10,000 nosai (53.3X10”~
533X1pi11IIHI), but 10, [3
The desired product can be obtained in good yield even at pressures above 0 psi. Here, pressure refers to the total pressure produced by all reactants, but in these examples is substantially based on the partial pressures of carbon oxide and hydrogen. As far as has been determined, the present invention is not limited to a single step process using the disclosed catalyst.
Primarily ethanol and acetaldehyde are formed. By-products such as water% n-gropanol, methyl acetate, ethyl acetate and acetic acid are also detected in the liquid product fraction. The novel process of the invention is carried out batchwise, semi-continuously or continuously. The catalyst may initially be introduced into the reaction zone batchwise or may be introduced into the zone continuously or intermittently during the course of the synthesis reaction. The operating conditions are adjusted to most effectively form the desired alcohol product. Also, distillation,
The material may be recovered by well known methods such as fractional extraction. Both the cobalt-containing compound and promoter-enriched adducts formed, if desired, on W may then be recycled into the reaction zone. In this study, the products formed by the method of the invention were
The following analytical method, namely gas-liquid gas chromatography (
GLC), infrared absorption (IR), mass spectrometry: nuclear magnetic resonance (
NMR) and elemental analysis or a combination thereof. Most analytes are expressed in parts by weight; all temperatures are in degrees Celsius and all pressures are expressed in units of 1 lb. per inch square.
It can be expressed as a number (1 psig). In order to explain the present invention blade #, an example is given in IJ-F. However, the examples are provided for illustrative purposes and should not be considered as limiting the invention in any way. Example 1 In a pressure reactor decorated with a glass lining, 0.341/(1rn
molle), triphenylgermanium hydride 0.
304.9 (]rnmole), methanol 5.6g
and p-dioxane 14.01/ml was added. The air in the reactor was replaced with a mixture of -carbon oxide and hydrogen (molar ratio 1:2) to increase the pressure to 10007'C (53,3
x 10' i+1I-IN >, and then the mixture was stirred with vibration and heated to 180°C. - Increased amount of oxidized carbonaceous hydrogen mixture to 40007' cider (2)
The pressure was increased to 3XIfF, 9). The reaction continued for 18 hours. 17) At the end of the reaction, the pressure bar was 30,007"tir (160×10"m1IW). Stop the reaction and cool the reactor to room temperature. When υ1 gas sample is taken out and excess gas is discharged from the reactor, 26
．． 1 g of dark brown liquid product was recovered. This brown liquid was analyzed by GLC. The carbon selectivity for the 4-components of ethanol (converted to methanol as feedstock), acetaldehyde, n-propanol, methyl acetate, and ethyl acetate was analyzed as follows: 56% heavy wound Ethanol 7 Acetaldehyde 7 n-Pronozonol 4 Methyl acetate 2 Ethyl acetate The methanol conversion rate was 61%. By Karl Fischer titration, the water content of the crude cylinder product was determined to be 7.
It was measured to be 67% by weight. A typical exhaust gas sample includes:
The following compounds were present: 53.9% hydrogen 41.1% carbon oxide 1.7% methane 0.58% carbon oxide Example 2 In a glass-lined pressure reactor, Octacarbonyl dicobalt 0.349 (Immode), triphenylgermanium hydrogen 4F, mono o, o8o y (
0.25 mmole), methanol 5.6f and p-
Dioxane 14. A mixture of Of was added. The air in the reactor was replaced with - a mixture of carbon oxide and hydrogen (molar ratio 1:2
) to increase the pressure to 1000 nosai (53.3X, 10"mm)
HP), then stir with vibration to 17
Heated to 5°C. The surge tank collar was further fed with a carbon-hydrogen oxide mixture to increase the pressure to 4200 near" sig (224.times.10" mmHf). The reaction continued for 18 hours. The pressure at the end of the reaction was 3800 zosaig (202 x 10" mm HP). The reaction was stopped and the reactor was cooled to room temperature. The exhaust gas sample was removed and the excess gas was vented from the reactor.
．． 1f of dark brown liquid product was collected. A sample of the liquid product was analyzed by GLC and the product selectivity was as follows: 54% solids ethanol 8 5 acetaldehyde 3 methyl acetate Ethyl acetate methanol conversion was 79%. Ta. The water content determined by Karl Fischer titration was 11.1% by weight. The recovery rate of cobalt in the solution was 54%. Example 3 In a pressure reactor, A phthalate was mixed with nyl dicobalt (1,3
411 (1,0 mmol 7e), tetraphenylgermanium 0.381 (1,0 mmolle 8 meta/-hel 5.6), P and p-dioxane 14.0.9 were charged.The air in the reactor was replaced. Then, the temperature was adjusted to 1000 psi with a mixture of carbon oxide and hydrogen (molar ratio 1:2), and then heated to 180'C with stirring without vibration.1: Surge tank filled with 2 moles of carbon monoxide and hydrogen mixture 75 f sipe (222X) O”ig
xH, 9). The reaction continued for 18 hours. The pressure at the end of the reaction was 3975 psig (212X10”i+wH
F) "'C" was there. The reaction was stopped and the reactor was cooled to room temperature. After venting and draining excess gas from the reactor, 21.4 # of dark brown liquid product was recovered. A liquid product sample was analyzed by GLC and the product selectivity was as follows: 53.0 wt% ethanol 7, Ott acetaldehyde 3.0 methyl acetate methanol conversion was 63 wt% . The moisture content determined by Karl Fischer titration was 5.18%. Example 4 Following the general procedure of Examples
．． 3411 (1 mmole), triphenyldarmanium hydride 0. :3011 (1mmoA!e)
, 5.6 g of methanol and 14.09 g of p-dioxane were added. The air in the reactor was replaced and the pressure was increased to 1000 psi (53
, 3x 1o" Tominokami HI), and then stirred and heated to 175°C while applying vibration.
) from the tank to the V VC supply 1 pressure/J7Y4 (100 sea IJ-Ik (:213X
10' Dragon H1) K-1-digit. The reaction continued for 18 hours. The reaction was stopped 1. and the reactor was cooled to room temperature in a trench. After draining the exhaust gas and venting excess gas from the reactor, 22.5 g of dark brown liquid product was recovered. Analyzing the liquid product sample by GLC1. The selectivity of the product was as follows: 44.0% by weight Ethanol 4, Ott n-propanol 10.0// Acetaldehyde 4.0 Ethyl acetate 8.0 The methanol acetate conversion was It was 60% by weight. The moisture content of the same crude liquid product by Karl Fischer titration was 8.54% by weight. The cobalt content of the same crude liquid product by atomic absorption spectroscopy is 4605 ppm;
It was found that 90% of the cobalt was recovered in solution. After the analytical test was completed, the liquid product remaining from the experiment was subjected to fractional distillation under atmospheric pressure, and the distilled fractions were collected. The remaining catalyst liquid (3,5II) was then dissolved in freshly prepared methanol (5,5II).
6,9) and p-dioxane (14,0,P) and placed in a glass-lined reactor. The reactor was sealed, purged with air, and brought to a pressure of 1000 psi (53,3X I
O” + u H, 9) at 175°C with stirring.
heated to. Pressure to 4000 psi (213X10”
llH,9) and the reaction continued for 18 hours. - In the second cycle, the selectivity of the liquid product recovered for GLC analysis of this product was as follows: 50 FFF 1% Ethanol 6, Ott n-propertool 10.0 // Acetaldehyde 5 .0 Ethyl acetate 9.0 Methanol acetate conversion was 60% by weight. The crude liquid product from the second catalyst cycle was then subjected to the same fractional distillation as above. The remaining catalyst solution (2, ON
) is returned to the reactor together with freshly prepared methanol (5,6,9) and p-dioxane (14,0,9)17,
A third cobalt-r-rumanium catalyst cycle was placed under the same reaction conditions. - The liquid products recovered in the second and second circulations were analyzed by GLC and the following results were found: 48.0% heavy needles ethanol 5, Ott n-propertool 11.0 // acetaldehyde 4, O〃Ethyl acetate methanol conversion rate was 60% by weight. The data obtained in these three cycle experiments using the same sample of octacarbnyldicobalt-triphenyldarmanium hydride catalyst are summarized in Table 1. The methanol conversion rate and ethanol selectivity from this ball circulation experiment are shown in Table 1. Table 1 Number of cycles of ethanol synthesis catalyst from methanol and synthesis gas Methanol conversion rate (support) Ethanol selectivity (weight 1%) 1 60 44 2 60 50 3 60 48 From these data, octacarbonyl dicobalt-tri A phenyldalmanium hydride catalyst system was found to retain its activity in converting methanol to its congener ethanol even after recycling the same catalyst sample. Example 5 In this comparative example, the same experimental operations as in Example 1 were performed except that no kermanium-containing compound was added to the reaction system. In a glass-lined reactor, 0.341 (1,(1 mmole)) of octacarbonyl dicobalt,
5.6 g of methanol and 14. p-dioxane. A mixture of OF was added. The air in the reactor was replaced with a mixture of carbon oxide and hydrogen (molar ratio l:2) at a pressure of 1000 f'.
#I(53,3
2] 01 with pressure increased to 2X10”5n) IIi)
The reaction continued for 8 hours. The pressure at the end of the reaction is 22007″
cider (117 x 10105 lNH).The reaction was stopped and the reactor was cooled to room temperature.The exhaust gas was taken out and the excess gas was discharged from the reactor.22.
A green solution of 2.9 was collected. Analysis of the liquid product by GLCK gave the following product selectivity: 64 % solids ethanol 9 n-propatool 4 acetaldehyde 3 methyl formate methanol conversion was 78% by weight. The cobalt content in the sum liquid product by ring absorption spectroscopy is 1
It was 22 pprn. This value indicates that the recovery rate of cobalt in the solution is 3% relative to the amount of octacarbonyl dicobalt initially added. Example 6 In another embodiment of the process of the invention, cobal iodide (IT) was added in a glass-lined pressure reactor.
0.681 (2mmoJe), tetraphenyl curmano, 741 (2mmo/e), methanol 5.6y and p-dioxane 14. A mixture of OII was charged. The air in the reactor is replaced with - a mixture of carbon oxide and hydrogen (
molar ratio 1:2) at a pressure of 1000 psig (53,3X
The mixture was heated to 180° C. with stirring under 1/i vibration. The pressure was increased to 20° C. from a surge tank filled with a 1:2 molar carbon monoxide and hydrogen mixture.
00 psi (107 x 10” HF) K raised. 18
Continuing the reaction for an hour, cooling and discharging the reactor, 24.
5 # of dark brown liquid product was collected. The liquid product was analyzed by GLC and the product selectivity was as follows: 59% by weight ethanol 15% acetaldehyde 3% sodium bicarbonate n-propanol 4 methyl acetate 3 ethyl acetate methanol conversion was 94 %Met. The moisture content determined by Karl Fischer titration was 13.6%. The cobalt content in the crude liquid product is 4985 ppm and t
) ivy. This figure indicates a 99% recovery in the cobalt solution initially added as cobalt iodide. Example 7 Copal iodide (IT) 0.681 was added to a glass-lined pressure reactor according to the procedure of Example 1.
1 (2 mmole),) Riphenylgermanium hydride 0.3041 (1 mmole), meta/-
5.611 and p-dioxane x4. I put oy. The air in the reactor was replaced and a mixture of - oxidized hydrogen and hydrogen (
The pressure was increased to 1000f cider (53,3×
The mixture was heated to 180° C. for 10 s, and then stirred with vibration. The pressure was raised to 2000 psi (107 x 10" mHg) by feeding CO/H, (2:2) from a surge tank. The reaction continued for 18 hours, the reactor was cooled, and the gas was released. Upon draining, a dark brown liquid product was collected. The liquid product was analyzed by GLC and the product selectivity was as follows: 60% by weight Ethanol 15 Acetaldehyde 2 N-Glonoryl 3 〃 Methyl acetate 2 〃 Ethyl acetate The methanol conversion rate was 88%.The water content by Karl Fischer titration was 13.2%.The soluble cobalt recovered was 99%.Example 8 In a glass-lined pressure reactor, 0.341 (1 mmole) of cobalt iodide, trif
Nilgermanium hydride 0.381 (1rnmol
e), methanol 5.6 g and p-diocane 14.
0.9 of the mixture was added. Replace the air in the reactor and -
A mixture of sulfur oxide and hydrogen (molar ratio 1:2) was used to reduce the pressure to 10
(53,3X10"llH,!i') and then stirred with vibration and heated to 180°C. Pressure was removed from a surge tank filled with a 1:2 molar carbon monoxide and hydrogen mixture. 4250 psi (226X10
``yx*)L!/ ).The reaction was continued for 18 hours.The pressure at the end of the reaction was 4 (] (10 zosaig(
2] Stop the 0 reaction that was 3X10” Tomiyuki H, 9),
The reactor was cooled to room temperature. Take out the exhaust gas,
Excess gas was vented from the reactor car and a dark brown product of 20.0.9 was recovered. The liquid product was analyzed by GLC and the selectivity of the product was as follows: 58% ethanol, 14% acetaldehyde (1//8.0% acetaldehyde)
n-propanol 3.0 // methyl acetate 3.0 Ethyl acetate methanol conversion rate was 93.0%. The moisture content determined by Karl Fischer titration was 15.1%. Example 9 As a comparative example, the same experimental operation as in Example 6 was performed, but
No germanium compound was added during the operation. Cobalt iodide (TI) 0.681 (2.0 mmo/e),
Methanol 5.6I and p-dioxane (14°0.1
Added a mixture of The air in the reactor was replaced, and the pressure was increased to 1000 psi (53.3 x 10 sIIH!) with a mixture of carbon oxide and hydrogen (molar ratio 1:2).Then, the mixture was stirred with vibration and heated to 180°C. The pressure was increased to 2.
000 psi (107 X 10" mm H#) and the pressure was maintained by a surge tank. The reaction was continued for 18 hours and cooled to room temperature (pressure was 1500 psi).
(79,9 x 10" tonnage wHI).) When the excess gas was vented from the reactor, a slightly purplish brown solution (23,41) was recovered. The liquid product was analyzed by GLC. The selectivity of the product was as follows: 29% by weight ethanol 3 tt n-grono(nol 29 acetaldehyde 0 methyl acetate 8 ethyl acetate Unreacted methanol was 92%. Crude liquid production The cobalt content of the product was 3717 ppm, which indicates a 74% recovery in the cobalt solution initially added as cobalt iodide. It was found that this example using a cobalt catalyst had significantly lower ethanol selectivity (29%) and cobalt recovery rate (74%) than Example 6 using a cobalt iodide-tetraphenylglumane catalyst. did.

Claims (1)

[Claims] 500 prig (35,5 bar; 26,6 X) in the presence of an inert oxygen-containing hydrocarbon solvent
1 (18II HII) or more and about 50
A process for the production of ethanol, characterized in that carbon oxide, hydrogen and methanol are brought into contact with a catalyst system consisting of a cobalt-containing compound and a germanium-containing compound at a temperature of -350C.