CA1269401A - Process of producing a mixture of methanol and higher alcohols - Google Patents
Process of producing a mixture of methanol and higher alcoholsInfo
- Publication number
- CA1269401A CA1269401A CA000472786A CA472786A CA1269401A CA 1269401 A CA1269401 A CA 1269401A CA 000472786 A CA000472786 A CA 000472786A CA 472786 A CA472786 A CA 472786A CA 1269401 A CA1269401 A CA 1269401A
- Authority
- CA
- Canada
- Prior art keywords
- methanol
- catalyst
- process according
- synthesis gas
- higher alcohols
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
- C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
- C07C29/153—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used
- C07C29/154—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing copper, silver, gold, or compounds thereof
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
ABSTRACT OF THE DISCLOSURE
A process of producing a mixture of methanol and higher alcohols having 2 to 7 carbon atoms per molecule.
The process comprises contacting a synthesis gas having a H2:CO mole ratio of 0.3 to 1.9 and a CO2 content not in excess of 2 vol. %, at a temperature in the range from 50 to 100 bars, with a copper-, zinc- and alumimum-containing catalyst. This catalyst is derived from a partly reduced catalyst precursor which contains 35 to 65 wt.% CuO, 15 to 45 wt.% ZnO and 5 to 20 wt.% Al2O3, and which has a total content of alkali metal and/or alkaline earth metal not in excess of 0.25 wt.%. The oxides of the catalyst precursor are reduced, at least in part, before the process begins.
The catalyst has a Cu:Zn weight ratio in the range from 1:1 to 2.4:1.
A process of producing a mixture of methanol and higher alcohols having 2 to 7 carbon atoms per molecule.
The process comprises contacting a synthesis gas having a H2:CO mole ratio of 0.3 to 1.9 and a CO2 content not in excess of 2 vol. %, at a temperature in the range from 50 to 100 bars, with a copper-, zinc- and alumimum-containing catalyst. This catalyst is derived from a partly reduced catalyst precursor which contains 35 to 65 wt.% CuO, 15 to 45 wt.% ZnO and 5 to 20 wt.% Al2O3, and which has a total content of alkali metal and/or alkaline earth metal not in excess of 0.25 wt.%. The oxides of the catalyst precursor are reduced, at least in part, before the process begins.
The catalyst has a Cu:Zn weight ratio in the range from 1:1 to 2.4:1.
Description
~6~
~ his invention relates to a process of producing a mixture of methanol and hiher alcohols having 2 to 7 carbon atoms per molecule from a synthesis gas containing hydrogen and carbon oxides by a reaction carried out at a temperature in the range from 200 to 320 C
and under a pressure in the range from 50 to 100 bars on a copper, zinc and aluminum con~aining catalyst.
~ aid-open German Application 33 10 540 discloses such a process in which the catalyst employed contains essentially copper, cobalt, aluminum and at least one alkali metal or alkaline earth metal. Zinc may also be contained in the known catalyst.
~ mith and Anderson have reported in the Canadian Journal of Chemical Engineering, Vol. 61 (February 1983), on pages 40 to 45 on investigations ~69~0~
concerning the synthesis of higher alcohols on a CuO-ZnO-Al2O3 catalyst which contains alkali metal. When the synthesis gas is caused to flow in contact with the catalyst, methanol and higher alcohols are formed and the content of higher alcohols in -the liquid product is distinctly dependent on the content of the K2CO3 activator in -the catalyst. The highest yield of higher alcohols has been obtained with a catalyst containing 0.5 wt.% K2CO3.
With catalysts having a lower content of K2CO3, the yield of higher alcohols dropped ~uickly.
It is an object of the invention to carry out the process described first hereinbefore in such a manner that the yields of methanol and higher alcohols are increased and a long life of the catalyst is achieved. Such methanol-alcohol mixtures are used in technology to improve the knock rating of fuels and as solubilizers for water in a mixture with natural fuels and as solubilizers for water in a mixture with natural fuels for Otto cycle engines.
Furthermore, it is desirable to minimize the water content of the product of the synthesis in order to avoid the need for a purifying distillation, which would be difficult because of the formation of an azeotropic mixture.
In meeting these and other objects, the present invention provides a process of producing a mixture of me-thanol and higher alcohols having 2 to 7 carbon atoms per molecule. The process comprises contac-ting a synthesis gas having a H2:CO mole ratio of 0.3 to 1.9 and a CO2 content not in excess of 2 vol. %, at a temperature in the range from 50 to 100 bars, with a copper-, zinc- and alumimum-containing catalyst. This catalyst is derived from a partly reduced catalyst precursor which contains 35 to 65 wt.% CuO, 15 to 45 wt.% ZnO and 5 to 20 wt.% Al2O3, and which has a total content of alkal~i metal and/or alkaline earth metal ~Z~4C~1 - 2a -not in excess of 0.25 wt.%. The oxides of the catalyst precursor are reduced, at least in part, before the process begins. The catalyst has a Cu:Zn weight ratio in the range from 1:1 to 2.4:1.
B
L26~
In accordance with the present invention the alcohols produced in contact with the catalyst may consist of about 50 to 99.8 % methanol and about 0.2 to 50 % C2 to C7 alcohols.
In accordance with the present invention, CO2 may be removed from the synthesis gas by means of methanol contained in the reaction product or by means of a methanol-alcoho~ mixture before the synthesis gas is used for the synthesis.
In accordance with the present invention a mix-ture of methanol and higher alcohols may be formed in a first reaction stage, the content of higher alcohols in the liquid product obtained from said mixture may be in excess of 10 wt.%, hydrogen is admixed to the residual gas to form a synthesis gas, and the latter is used in a succeeding second reaction stage to produce methanol, from which a liquid product may be derived which contains less than 0.5 wt.% higher alcohols.
It has surprisingly been found that a product having a very low water content will be obtained whenever the synthesis gas contacted with the catalyst has a low CO2 content and a H2:CO mole ratio which is distinctly lower than 2. The gas stream leaving the catalyst contains con-densible liquid products which usually consists of the following components:
Methanol 55 to 88 wt.%
Higher alcohols (C2 to C7) 10 to 45 wt.~
Water 0.1 to 1.5 wt.%
The process in accordance with the invention is preferably carried out at temperatures in the range from ~' 12~9~
- 3a -250 to 300C; in said process the catalyst obviously has a high importance. In the catalyst precursor and in the partly reduced catalyst used for the synthesis the weight ratio of Cu:Zn is suitably in the range from 0.7 to 4.8 and preferably in the range from 1.0 to 2.4.
In view of -the previously published investigations, such as that by Smith and Anderson, it was not to be pre-dicted that a Cu-Z~-A1 catalyst whic ~z~
stantially free of alkali would produce excellent results also in the simul-taneous synthesis of methanol and higher alcohols. It had previously been believed that additions of activating alkali metals or alkaline earth metals were required to accomplish that object.
Higher yields of higher alcohols will be particularly obtained if catalysts are used in which the total content of alkali metal and alkaline earth metal is not in excess of 0.1 wt. ~. The content of alkaline earth metal may be virtually zero. The alkali metals enter the catalyst in most cases as impurities during the production process and include lithium, sodium, potassium, rubidium and/or caesium. The corresponding alkaline earth metals are magnesium, calcium and/or barium.
The production of higher alcohols can be further increased in that the catalyst is contacted with a synthesis gas which contains methanol vapor, e.g., in a proportion of 3 to 15 vol. ~.
The preferred catalyst can be produced, e.g., in that the catalytically active copper oxide and zinc oxide components are precipitated from an aqueous solution of the corresponding salts, such as the nitrates or acetates, by an addition of alkaline substances in the presence of colloidal alumina or colloidal aluminum hydroxide (in the form of a gel or sol). The resulting mixture or precipitation product may be processed in known manner by drying, calcining, pressing to shapes and, if desired, reduction. The alkaline precipitants preferably consist of an alkali or ammonium carbonate or bicarbonate, preferably the carbonate or blcarbonate of potassium. It has been found that in the synthesis also of higher alcohols a low potassium content up to a certain limit will not be disturbing and will be much more favorable than a corresponding sodium content.
To improve the porous structure of the catalys-t ~r ~z~g~
the precipi-tation of the copper oxide and zinc oxide components is in the presence of the colloidal alumina or aluminum hydroxide is preferably carried out in the presence of a dilute solution of the alkaline substances, such as a solution of 10 to 20 wt. 96 alkali carbonate, and at low temperatures and at pH values in the neutral or slightly acid range. The precipitation is suitably affected at a temperature of 25 to 65C, preferably of 30 to 40C. The addition of the alkalies is usually terminated at a pH value in the range from 6.5 to 7.5.
A higher yield of higher alcohols can be achieved by the use of a catalyst which in its oxidic form has a void volume of 0.25 to 0.5 cm3/g. The distribution of the pores of that catalyst precursor is of great importance. 50 to 85% of the avoid volume may be constituted by pores which are 0.014 to 0.08 ~Im in diameter, 15 to 50% by pores which are less than 0.014 lum in diameter, and not in excess of 4g6 of the void volume by pores which are in excess of 0.08 Jum in diameter. That void volume is determined by mercury poroslmetry (Literature: R. Anderson, Experimental Methods in Catalytic Research, Academic Press, New York, 1968).
To a person skilled in the art it will be apparent that the catalysts of the type explained hereinbefore can be used also for the synthesis of methanol accompanied by very small ~[uantities of higher alcohols. This has been proved by experiments (see Example I). In that case a high-hydrogen synthesis gas is used.
Examples of the Preparation of the Catalyst Catalyst A
Two solutions are prepared for the precipitation of the catalyst precursor.
Solution 418 g copper nitrate and 50 g zinc oxide are 6~
dissolved in 1.6 liters water and 148 g 52% nitric acid.
Thereafter, a colloidal aluminum metahydrate gel is added.
Solution 2 535 g potassium carbonate are dissolved in 3317 g water.
The solutions are mixed at 40C with strong stirring in such a manner that the pH value during the precipitation is 6.9. The precipitation is terminated when the pH value is not in excess of 7.1. Thereafter the precipitate is filtered off and washed with water until alkali metal (potassium) can be no longer detected in the filtered effluent. The filter cake is dried at 120C and is subsequently calcined at 280C for 8 hours. The calcined product is reduced in size and is compacted after 2 wt. %
graphite have been added.
The calcined catalyst precursor is free of graphite and contains 65 wt. % CuO, 23 wt. % ZnO and 12 wt. % A12O3. The catalyst precursor A thus produced contains 0.06 wt. % potassium. The resulting tablets have a size of 5 mm x 5 mm and the following physical properties:
Bulk density of tablets: 1015 g/liter Void volume: 0.36 cm3/g Pore size distribution determined by Hg porosimetry Pores 0.08 to 0.014 lum 25in diameter 78% of void volume Pores less than 0.014 ~um in diameter 21% of void volume Pores in excess of 0.08 lum in diameter 1~ of void volume Catalyst B
Catalyst precursor B is made in a process which is similar to the preparation of catalyst precursor A with the single difference that the filter cake which has been filtered off is washed with water only twice so that the o~
filtered effluent is no-t free of alkali metal.
The calcined catalyst precursor is free of graphite and con-tains 65 wt. % CuO, 23 wt. % ZnO and 12 wt. % Al2O3 and has a residual alkali metal content of 0.31 wt. % potassium. As regards physical properties, catalyst B
does not exhibit detectable differences from catalyst A.
An embodiment of the process will now be explained with reference to the drawing~
A synthesis gas which contains hydrogen and carbon oxides is supplied by the compressor 1 and is mixed with residual gas from line 2. The resulting mixture is supplied in line 3 to a process stage 4 for removing CO2. In that stage, substantially all CO2 is removed from the mixed gases in known manner. The separated CO2 gas conducted in line 5 may desirably be used in the production of the synthesis gas if the latter is derived, e.g., from natural gas. CO2 may be removed by a scrubbing with methanol or with a mixture of methanol and higher alcohols and a product of the present process may be used for that purpose.
The gas which is substantially free of CO2 is supplied in line 6 to a heat exchanger 7, in which the gas is heated and from which the gas is conducted in line 8 to the synthesis reactor 9. The reactor 9 consists of a tubular heater, in which the tubes contain the catalyst consisting mainly of copper, zinc and aluminum. A liquid coolant, such as water, is disposed between the tubes.
The synthesis gas supplied to the reactor 9 consists mainly of H2 and CO in a mole ratio in the range from 0.3 to 1.9. the CO2 content is not in excess of 2 vol.
% in the catalyst in the catalyst-filled tubes of the reactor the temperatures are in the range from 200 to 320C, preferably at about 250 to 300C, and the pressure is 50 to 150 bars. In the reactor, the synthesis gas is reacted to form methanol and higher alcohols.
~26~
The product of the synthesis is withdrawn from the reactor 9 in line 10 and is first indirectly cooled in the heat exchanger 7 with the cold gas from line 6 and is cooled further by water in a cooler 11. The partly condensed product is conducted in line 12 to the separator 13, in which residual gases are separated and then withdrawn in line 20. Part of said residual gases is recycled through the circulating compressor 21 and the line 2. A branch stream of residual gases is withdrawn in line 22.
The liquid product obtained in the separator 13 is conducted in line 23 to a distilling stage 24, in which the low-boiling components, particularly dimethylether, methyl formate and acetone, are separated and withdrawn overhead in line 25. The sump product of the distillation column 24 consists of methanol and higher alcohols and contains water not in excess of about 2 wt. % and is withdrawn in line 26 and is suitable as a motor fuel, particularly as an additive to regular-grade or premium gasoline for Otto cycle engines.
The concentration of higher alcohols in the product withdrawn in line 26 may be increased, if desired, in that methanol is also distilled in the distilling stage 24 and is withdrawn either overhead in line 25 together with the low-boiling components or is separately withdrawn from the column 24 through a lateral outlet 27.
The yield of higher alcohols can also be increased in that the synthesis gas supplied to the catalyst of the reactor contains methanol vapor, e.g., in a proportion of 3 to 15 vol. %. That methanol may be produced in that the methanol contained in the product conducted in lines 10 and 12 is not completely condensed so that the residual gas in line 2 contains methanol vapor. Besides, methanol may be injected into the synthesis gas conducted in line 8.
The partial stream of residual gas in line 20 may be used entirely or in part for a second methanol synthesis, ,....
~Zi~314~
which is not shown. That second methanol synthesis may be carried out in known manner so that its product consists mainly of methanol and has only a low content of higher alcohols. The catalyst used for such methanol synthesis may consist of copper, zinc and aluminum, such as the catalyst used in the reactor 9. Because the residual gas in line 20 has substantial contents of CO and also of CO2, that residual gas must be enriched with hydrogen before entering the second methanol synthesis so that the H2:CO mole ratio is at least 2Ø
In the process illustrated in the drawing it is also possible to form in the synthesis reactor 9 a product consisting mainly of methanol without appreciable quantities of higher alcohols if the H2:CO mole ratio in the fresh synthesis gas is higher than 2. That fresh synthesis gas is sucked by the compressor 1 and its use has the result that a synthesis gas having a high H2 content is contacted with the catalyst.
100 cm3 of catalyst precursor A are placed into a tubular heater, which is cooled by a water jacket and in which the catalyst is reduced under normal pressure by a treatment with a mixture of 1 vol. % H2 and 99 vol. % N2.
The temperature in the reactor is raised in steps -to 240 C.
When a temperature of 240C has been reached, the reactor is supplied with a synthesis gas consisting of 4 vol. % CO2, 10 vol. % CO, 75 vol. % H2 and 11 vol. % inert gas. Under the selected experimental conditions, namely, a pressure of 50 30 bars, an hourly space velocity of 10,400 standard liters per liter of catalyst, a liquid product of 1,105 kg/h per liter of catalyst is obtained after an operation of about 100 to 150 hours. That product has the following composition:
~r 94~)~
Methanol 94~25 wt. %
Ethanol 0.08 wt. %
Propanols 0.04 wt. %
Butanols 0.03 wt. %
l~2O 5.6 wt. %
After an operation for 150 hours, the temperature is increased to 270C and the pressure to 100 bars~ If the catalyst is contacted at an hourly space velocity of 4,500 standard liters per liter of catalyst with a synthesis gas composed of 0.5 vol. % inert gas, the liquid product obtained after the 150th hour of operation at a rate of 1.02 kg/h per liter of catalyst has the following composition:
Methanol 84.7 wt. %
Ethanol 6.0 wt. %
Propanols 3.2 wt. %
Butanols 3.5 wt. %
Pentanols and other higher alcohols2.3 wt. %
Water 0.3 wt. %
It is apparent from this example that a catalyst which is almost free of alkali metal (0.06 wt. % potassium) and alkaline earth metal may be used to produce either a mixture of methanol and higher alcohols (e.g., 15 wt. %
higher alcohols) or methanol having a low content of higher alcohols (0.15 wt. %).
E~AMPLE 2 100 cm3 of catalyst precursor B having an alkali metal content of 0.31 wt. % potassium are placed into the reactor used in Example 1 and are reduced therein as described in Example 1.
Operating at 270C and 100 bars, the reactor is contacted at an hourly space velocity of 4500 standard liters per liter of catalyst with a synthesis gas consisting ~L26940~
of 0.5 vol. % CO2, 48 vol. % CO, 50 vol. % H2 and 1.5 vol. %
inert gas. Between the 150th and 200th hours of operation, the liquid product obtained in the reactor at a rate of 0.98 kg/h per liter of ca-talyst has the following composition:
Methanol 90.9 wt. %
Ethanol 3.5 wt. %
Propanols 1.8 wt. %
Butanols 1.9 wt. %
Hexanols and other higher alcohols1.7 wt. %
Water 0.2 wt. %
It is apparent from this experiment that the use of catalyst precursor B which contains 0.31 wt. % potassium under the same conditions results almost in the same yield of liquid product as the use of the catalyst precursor A, from which alkali metal has been removed to the practical limit (residual potassium content 0.06 wt. %).
The decisive difference resides in that use of the product obtained by the use of catalyst A having a low content of alkali metal and/or alkaline earth metal has much higher contents of C2 to C7 alcohols (15.0 wt. %) the product obtained by the use of catalyst B, which has a high alkali metal content and results in a liquid product which contains 8.9 wt. % C2 to C7 alcohols.
Catalyst precursor A is placed in-to the reactor used also in Example 1. When the catalyst has been reduced, it is supplied first with a synthesis gas having a low CO2 content (gas I) and subsequently with a synthesis gas having a high CO2 content (gas II). The experimental conditions and the results obtained are listed hereinafter:
~6~
Gas IGas II
.
Synthesis gas CO2, vol. % 1.4 11.4 CO, vol. % 61.0 60.1 H2, vol. % 30.0 26.1 Inert gas, vol. % 7,6 2.4 Pressure, bar 50 50 Temperature, C 75 75 Hourly space velocity, standard liters per liter2650 2700 Rate of liquld product kg/1-h 0.21 0.16 Composition of liquid product Methanol, wt. % 80.0 86.4 Higher alcohols, wt. % 19.8 12.1 Water, wt. % 0.2 1.5 It is apparent from the above table that the contacting of the catalyst with a synthesis gas having a higher CO2 content results in a distinct decrease of the yield of higher alcohols and in a higher water content of the liquid product so that the highest permissible water content in the mixed fuel may be exceeded.
~`~
1.
~ his invention relates to a process of producing a mixture of methanol and hiher alcohols having 2 to 7 carbon atoms per molecule from a synthesis gas containing hydrogen and carbon oxides by a reaction carried out at a temperature in the range from 200 to 320 C
and under a pressure in the range from 50 to 100 bars on a copper, zinc and aluminum con~aining catalyst.
~ aid-open German Application 33 10 540 discloses such a process in which the catalyst employed contains essentially copper, cobalt, aluminum and at least one alkali metal or alkaline earth metal. Zinc may also be contained in the known catalyst.
~ mith and Anderson have reported in the Canadian Journal of Chemical Engineering, Vol. 61 (February 1983), on pages 40 to 45 on investigations ~69~0~
concerning the synthesis of higher alcohols on a CuO-ZnO-Al2O3 catalyst which contains alkali metal. When the synthesis gas is caused to flow in contact with the catalyst, methanol and higher alcohols are formed and the content of higher alcohols in -the liquid product is distinctly dependent on the content of the K2CO3 activator in -the catalyst. The highest yield of higher alcohols has been obtained with a catalyst containing 0.5 wt.% K2CO3.
With catalysts having a lower content of K2CO3, the yield of higher alcohols dropped ~uickly.
It is an object of the invention to carry out the process described first hereinbefore in such a manner that the yields of methanol and higher alcohols are increased and a long life of the catalyst is achieved. Such methanol-alcohol mixtures are used in technology to improve the knock rating of fuels and as solubilizers for water in a mixture with natural fuels and as solubilizers for water in a mixture with natural fuels for Otto cycle engines.
Furthermore, it is desirable to minimize the water content of the product of the synthesis in order to avoid the need for a purifying distillation, which would be difficult because of the formation of an azeotropic mixture.
In meeting these and other objects, the present invention provides a process of producing a mixture of me-thanol and higher alcohols having 2 to 7 carbon atoms per molecule. The process comprises contac-ting a synthesis gas having a H2:CO mole ratio of 0.3 to 1.9 and a CO2 content not in excess of 2 vol. %, at a temperature in the range from 50 to 100 bars, with a copper-, zinc- and alumimum-containing catalyst. This catalyst is derived from a partly reduced catalyst precursor which contains 35 to 65 wt.% CuO, 15 to 45 wt.% ZnO and 5 to 20 wt.% Al2O3, and which has a total content of alkal~i metal and/or alkaline earth metal ~Z~4C~1 - 2a -not in excess of 0.25 wt.%. The oxides of the catalyst precursor are reduced, at least in part, before the process begins. The catalyst has a Cu:Zn weight ratio in the range from 1:1 to 2.4:1.
B
L26~
In accordance with the present invention the alcohols produced in contact with the catalyst may consist of about 50 to 99.8 % methanol and about 0.2 to 50 % C2 to C7 alcohols.
In accordance with the present invention, CO2 may be removed from the synthesis gas by means of methanol contained in the reaction product or by means of a methanol-alcoho~ mixture before the synthesis gas is used for the synthesis.
In accordance with the present invention a mix-ture of methanol and higher alcohols may be formed in a first reaction stage, the content of higher alcohols in the liquid product obtained from said mixture may be in excess of 10 wt.%, hydrogen is admixed to the residual gas to form a synthesis gas, and the latter is used in a succeeding second reaction stage to produce methanol, from which a liquid product may be derived which contains less than 0.5 wt.% higher alcohols.
It has surprisingly been found that a product having a very low water content will be obtained whenever the synthesis gas contacted with the catalyst has a low CO2 content and a H2:CO mole ratio which is distinctly lower than 2. The gas stream leaving the catalyst contains con-densible liquid products which usually consists of the following components:
Methanol 55 to 88 wt.%
Higher alcohols (C2 to C7) 10 to 45 wt.~
Water 0.1 to 1.5 wt.%
The process in accordance with the invention is preferably carried out at temperatures in the range from ~' 12~9~
- 3a -250 to 300C; in said process the catalyst obviously has a high importance. In the catalyst precursor and in the partly reduced catalyst used for the synthesis the weight ratio of Cu:Zn is suitably in the range from 0.7 to 4.8 and preferably in the range from 1.0 to 2.4.
In view of -the previously published investigations, such as that by Smith and Anderson, it was not to be pre-dicted that a Cu-Z~-A1 catalyst whic ~z~
stantially free of alkali would produce excellent results also in the simul-taneous synthesis of methanol and higher alcohols. It had previously been believed that additions of activating alkali metals or alkaline earth metals were required to accomplish that object.
Higher yields of higher alcohols will be particularly obtained if catalysts are used in which the total content of alkali metal and alkaline earth metal is not in excess of 0.1 wt. ~. The content of alkaline earth metal may be virtually zero. The alkali metals enter the catalyst in most cases as impurities during the production process and include lithium, sodium, potassium, rubidium and/or caesium. The corresponding alkaline earth metals are magnesium, calcium and/or barium.
The production of higher alcohols can be further increased in that the catalyst is contacted with a synthesis gas which contains methanol vapor, e.g., in a proportion of 3 to 15 vol. ~.
The preferred catalyst can be produced, e.g., in that the catalytically active copper oxide and zinc oxide components are precipitated from an aqueous solution of the corresponding salts, such as the nitrates or acetates, by an addition of alkaline substances in the presence of colloidal alumina or colloidal aluminum hydroxide (in the form of a gel or sol). The resulting mixture or precipitation product may be processed in known manner by drying, calcining, pressing to shapes and, if desired, reduction. The alkaline precipitants preferably consist of an alkali or ammonium carbonate or bicarbonate, preferably the carbonate or blcarbonate of potassium. It has been found that in the synthesis also of higher alcohols a low potassium content up to a certain limit will not be disturbing and will be much more favorable than a corresponding sodium content.
To improve the porous structure of the catalys-t ~r ~z~g~
the precipi-tation of the copper oxide and zinc oxide components is in the presence of the colloidal alumina or aluminum hydroxide is preferably carried out in the presence of a dilute solution of the alkaline substances, such as a solution of 10 to 20 wt. 96 alkali carbonate, and at low temperatures and at pH values in the neutral or slightly acid range. The precipitation is suitably affected at a temperature of 25 to 65C, preferably of 30 to 40C. The addition of the alkalies is usually terminated at a pH value in the range from 6.5 to 7.5.
A higher yield of higher alcohols can be achieved by the use of a catalyst which in its oxidic form has a void volume of 0.25 to 0.5 cm3/g. The distribution of the pores of that catalyst precursor is of great importance. 50 to 85% of the avoid volume may be constituted by pores which are 0.014 to 0.08 ~Im in diameter, 15 to 50% by pores which are less than 0.014 lum in diameter, and not in excess of 4g6 of the void volume by pores which are in excess of 0.08 Jum in diameter. That void volume is determined by mercury poroslmetry (Literature: R. Anderson, Experimental Methods in Catalytic Research, Academic Press, New York, 1968).
To a person skilled in the art it will be apparent that the catalysts of the type explained hereinbefore can be used also for the synthesis of methanol accompanied by very small ~[uantities of higher alcohols. This has been proved by experiments (see Example I). In that case a high-hydrogen synthesis gas is used.
Examples of the Preparation of the Catalyst Catalyst A
Two solutions are prepared for the precipitation of the catalyst precursor.
Solution 418 g copper nitrate and 50 g zinc oxide are 6~
dissolved in 1.6 liters water and 148 g 52% nitric acid.
Thereafter, a colloidal aluminum metahydrate gel is added.
Solution 2 535 g potassium carbonate are dissolved in 3317 g water.
The solutions are mixed at 40C with strong stirring in such a manner that the pH value during the precipitation is 6.9. The precipitation is terminated when the pH value is not in excess of 7.1. Thereafter the precipitate is filtered off and washed with water until alkali metal (potassium) can be no longer detected in the filtered effluent. The filter cake is dried at 120C and is subsequently calcined at 280C for 8 hours. The calcined product is reduced in size and is compacted after 2 wt. %
graphite have been added.
The calcined catalyst precursor is free of graphite and contains 65 wt. % CuO, 23 wt. % ZnO and 12 wt. % A12O3. The catalyst precursor A thus produced contains 0.06 wt. % potassium. The resulting tablets have a size of 5 mm x 5 mm and the following physical properties:
Bulk density of tablets: 1015 g/liter Void volume: 0.36 cm3/g Pore size distribution determined by Hg porosimetry Pores 0.08 to 0.014 lum 25in diameter 78% of void volume Pores less than 0.014 ~um in diameter 21% of void volume Pores in excess of 0.08 lum in diameter 1~ of void volume Catalyst B
Catalyst precursor B is made in a process which is similar to the preparation of catalyst precursor A with the single difference that the filter cake which has been filtered off is washed with water only twice so that the o~
filtered effluent is no-t free of alkali metal.
The calcined catalyst precursor is free of graphite and con-tains 65 wt. % CuO, 23 wt. % ZnO and 12 wt. % Al2O3 and has a residual alkali metal content of 0.31 wt. % potassium. As regards physical properties, catalyst B
does not exhibit detectable differences from catalyst A.
An embodiment of the process will now be explained with reference to the drawing~
A synthesis gas which contains hydrogen and carbon oxides is supplied by the compressor 1 and is mixed with residual gas from line 2. The resulting mixture is supplied in line 3 to a process stage 4 for removing CO2. In that stage, substantially all CO2 is removed from the mixed gases in known manner. The separated CO2 gas conducted in line 5 may desirably be used in the production of the synthesis gas if the latter is derived, e.g., from natural gas. CO2 may be removed by a scrubbing with methanol or with a mixture of methanol and higher alcohols and a product of the present process may be used for that purpose.
The gas which is substantially free of CO2 is supplied in line 6 to a heat exchanger 7, in which the gas is heated and from which the gas is conducted in line 8 to the synthesis reactor 9. The reactor 9 consists of a tubular heater, in which the tubes contain the catalyst consisting mainly of copper, zinc and aluminum. A liquid coolant, such as water, is disposed between the tubes.
The synthesis gas supplied to the reactor 9 consists mainly of H2 and CO in a mole ratio in the range from 0.3 to 1.9. the CO2 content is not in excess of 2 vol.
% in the catalyst in the catalyst-filled tubes of the reactor the temperatures are in the range from 200 to 320C, preferably at about 250 to 300C, and the pressure is 50 to 150 bars. In the reactor, the synthesis gas is reacted to form methanol and higher alcohols.
~26~
The product of the synthesis is withdrawn from the reactor 9 in line 10 and is first indirectly cooled in the heat exchanger 7 with the cold gas from line 6 and is cooled further by water in a cooler 11. The partly condensed product is conducted in line 12 to the separator 13, in which residual gases are separated and then withdrawn in line 20. Part of said residual gases is recycled through the circulating compressor 21 and the line 2. A branch stream of residual gases is withdrawn in line 22.
The liquid product obtained in the separator 13 is conducted in line 23 to a distilling stage 24, in which the low-boiling components, particularly dimethylether, methyl formate and acetone, are separated and withdrawn overhead in line 25. The sump product of the distillation column 24 consists of methanol and higher alcohols and contains water not in excess of about 2 wt. % and is withdrawn in line 26 and is suitable as a motor fuel, particularly as an additive to regular-grade or premium gasoline for Otto cycle engines.
The concentration of higher alcohols in the product withdrawn in line 26 may be increased, if desired, in that methanol is also distilled in the distilling stage 24 and is withdrawn either overhead in line 25 together with the low-boiling components or is separately withdrawn from the column 24 through a lateral outlet 27.
The yield of higher alcohols can also be increased in that the synthesis gas supplied to the catalyst of the reactor contains methanol vapor, e.g., in a proportion of 3 to 15 vol. %. That methanol may be produced in that the methanol contained in the product conducted in lines 10 and 12 is not completely condensed so that the residual gas in line 2 contains methanol vapor. Besides, methanol may be injected into the synthesis gas conducted in line 8.
The partial stream of residual gas in line 20 may be used entirely or in part for a second methanol synthesis, ,....
~Zi~314~
which is not shown. That second methanol synthesis may be carried out in known manner so that its product consists mainly of methanol and has only a low content of higher alcohols. The catalyst used for such methanol synthesis may consist of copper, zinc and aluminum, such as the catalyst used in the reactor 9. Because the residual gas in line 20 has substantial contents of CO and also of CO2, that residual gas must be enriched with hydrogen before entering the second methanol synthesis so that the H2:CO mole ratio is at least 2Ø
In the process illustrated in the drawing it is also possible to form in the synthesis reactor 9 a product consisting mainly of methanol without appreciable quantities of higher alcohols if the H2:CO mole ratio in the fresh synthesis gas is higher than 2. That fresh synthesis gas is sucked by the compressor 1 and its use has the result that a synthesis gas having a high H2 content is contacted with the catalyst.
100 cm3 of catalyst precursor A are placed into a tubular heater, which is cooled by a water jacket and in which the catalyst is reduced under normal pressure by a treatment with a mixture of 1 vol. % H2 and 99 vol. % N2.
The temperature in the reactor is raised in steps -to 240 C.
When a temperature of 240C has been reached, the reactor is supplied with a synthesis gas consisting of 4 vol. % CO2, 10 vol. % CO, 75 vol. % H2 and 11 vol. % inert gas. Under the selected experimental conditions, namely, a pressure of 50 30 bars, an hourly space velocity of 10,400 standard liters per liter of catalyst, a liquid product of 1,105 kg/h per liter of catalyst is obtained after an operation of about 100 to 150 hours. That product has the following composition:
~r 94~)~
Methanol 94~25 wt. %
Ethanol 0.08 wt. %
Propanols 0.04 wt. %
Butanols 0.03 wt. %
l~2O 5.6 wt. %
After an operation for 150 hours, the temperature is increased to 270C and the pressure to 100 bars~ If the catalyst is contacted at an hourly space velocity of 4,500 standard liters per liter of catalyst with a synthesis gas composed of 0.5 vol. % inert gas, the liquid product obtained after the 150th hour of operation at a rate of 1.02 kg/h per liter of catalyst has the following composition:
Methanol 84.7 wt. %
Ethanol 6.0 wt. %
Propanols 3.2 wt. %
Butanols 3.5 wt. %
Pentanols and other higher alcohols2.3 wt. %
Water 0.3 wt. %
It is apparent from this example that a catalyst which is almost free of alkali metal (0.06 wt. % potassium) and alkaline earth metal may be used to produce either a mixture of methanol and higher alcohols (e.g., 15 wt. %
higher alcohols) or methanol having a low content of higher alcohols (0.15 wt. %).
E~AMPLE 2 100 cm3 of catalyst precursor B having an alkali metal content of 0.31 wt. % potassium are placed into the reactor used in Example 1 and are reduced therein as described in Example 1.
Operating at 270C and 100 bars, the reactor is contacted at an hourly space velocity of 4500 standard liters per liter of catalyst with a synthesis gas consisting ~L26940~
of 0.5 vol. % CO2, 48 vol. % CO, 50 vol. % H2 and 1.5 vol. %
inert gas. Between the 150th and 200th hours of operation, the liquid product obtained in the reactor at a rate of 0.98 kg/h per liter of ca-talyst has the following composition:
Methanol 90.9 wt. %
Ethanol 3.5 wt. %
Propanols 1.8 wt. %
Butanols 1.9 wt. %
Hexanols and other higher alcohols1.7 wt. %
Water 0.2 wt. %
It is apparent from this experiment that the use of catalyst precursor B which contains 0.31 wt. % potassium under the same conditions results almost in the same yield of liquid product as the use of the catalyst precursor A, from which alkali metal has been removed to the practical limit (residual potassium content 0.06 wt. %).
The decisive difference resides in that use of the product obtained by the use of catalyst A having a low content of alkali metal and/or alkaline earth metal has much higher contents of C2 to C7 alcohols (15.0 wt. %) the product obtained by the use of catalyst B, which has a high alkali metal content and results in a liquid product which contains 8.9 wt. % C2 to C7 alcohols.
Catalyst precursor A is placed in-to the reactor used also in Example 1. When the catalyst has been reduced, it is supplied first with a synthesis gas having a low CO2 content (gas I) and subsequently with a synthesis gas having a high CO2 content (gas II). The experimental conditions and the results obtained are listed hereinafter:
~6~
Gas IGas II
.
Synthesis gas CO2, vol. % 1.4 11.4 CO, vol. % 61.0 60.1 H2, vol. % 30.0 26.1 Inert gas, vol. % 7,6 2.4 Pressure, bar 50 50 Temperature, C 75 75 Hourly space velocity, standard liters per liter2650 2700 Rate of liquld product kg/1-h 0.21 0.16 Composition of liquid product Methanol, wt. % 80.0 86.4 Higher alcohols, wt. % 19.8 12.1 Water, wt. % 0.2 1.5 It is apparent from the above table that the contacting of the catalyst with a synthesis gas having a higher CO2 content results in a distinct decrease of the yield of higher alcohols and in a higher water content of the liquid product so that the highest permissible water content in the mixed fuel may be exceeded.
~`~
1.
Claims (14)
1. A process of producing a mixture of methanol and higher alcohols having 2 to 7 carbon atoms per molecule comprising contacting a synthesis gas having a H2:CO mole ratio of 0.3 to 1.9 and a CO2 content not in excess of 2 vol.%, at a temperature in the range from 200 to 320°C and under a pressure in the range from 50 to 100 bars, with a copper-, zinc- and aluminum-containing catalyst derived from a partly reduced catalyst precursor which contains 35 to 65 wt.% CuO, 15 to 45 wt.% ZnO and 5 to 20 wt.% Al2O3, said precursor having a total content of alkali metal and/or alkaline earth metal not in excess of 0.25 wt.%, the oxides of said catalyst precursor being reduced at least in part before said process begins, and the catalyst having a Cu:Zn weight ratio in the range from 1:1 to 2.4:1.
2. A process according to claim 1, wherein the synthesis is carried out at a temperature in the range from 250 to 300°C.
3. A process according to claim 1, wherein the catalyst precursor has a void volume of 0.25 to 0.5 cm3/g.
4. A process according to claim 2, wherein the catalyst precursor has a void volume of 0.25 to 0.5 cm3/g.
5. A process according to claim 1 or 2, wherein, in the catalyst precursor, 50 to 85% of the void volume are constituted by pores which are 0.014 to 0.08 µm in diameter, 15 to 50% by pores which are less than 0.014 µm in diameter, and not in excess of 4% of the void volume by pores which are in excess of 0.08 µm in diameter.
6. A process according to claim 1, wherein the alcohols produced in contact with the catalyst consist of about 50 to 99.8% methanol and about 0.2 to 50% C2 to C7 alcohols.
7. A process according to claim 5, wherein the alcohols produced in contact with the catalyst consist of about 50 to 99.8% methanol and about 0.2 to 50% C2 to C7 alcohols.
8. A process according to claim 1, wherein the condensible fraction of the product withdrawn from the catalyst contains water not in excess of 2 wt.%.
9. A process according to claim 1, wherein CO2 is removed from the synthesis gas by means of methanol contained in the reaction product or by means of a methanol-alcohol mixture before the synthesis gas is used for the synthesis.
10. A process according to claim 7, wherein CO2 is removed from the synthesis gas by means of methanol contained in the reaction product or by means of a methanol-alcohol mixture before the synthesis gas is used for the synthesis.
11. A process according to claim 1, wherein a mixture of methanol and higher alcohols is formed in a first reaction stage, the content of higher alcohols in the liquid product obtained from said mixture is in excess of 10 wt.%, hydrogen is admixed to the residual gas to form a synthesis gas, and the latter is used in a succeeding second reaction stage to produce methanol, from which a liquid product is derived which contains less than 0.5 wt.% higher alcohols.
12. A process according to claim 5, wherein a mixture of methanol and higher alcohols is formed in a first reaction stage, the content of higher alcohols in the liquid product obtained from said mixture is in excess of 10 wt.%, hydrogen is admixed to the residual gas to form a synthesis gas, and the latter is used in a succeeding second reaction stage to produce methanol, from which a liquid product is derived which contains less than 0.5 wt.% higher alcohols.
13. A process according to claim 1, wherein the synthesis gas contacted with the catalyst contains 3 to 15 vol.% methanol vapor.
14. A process according to claim 5, wherein the synthesis gas contacted with the catalyst contains 3 to 15 vol.% methanol vapor.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP3403492.7 | 1984-02-02 | ||
| DE19843403492 DE3403492A1 (en) | 1984-02-02 | 1984-02-02 | METHOD FOR PRODUCING A MIXTURE OF METHANOL AND HIGHER ALCOHOLS |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1269401A true CA1269401A (en) | 1990-05-22 |
Family
ID=6226485
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000472786A Expired - Lifetime CA1269401A (en) | 1984-02-02 | 1985-01-24 | Process of producing a mixture of methanol and higher alcohols |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0152648B1 (en) |
| JP (1) | JPS60181038A (en) |
| AU (1) | AU566455B2 (en) |
| CA (1) | CA1269401A (en) |
| DE (2) | DE3403492A1 (en) |
| ZA (1) | ZA85691B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB8521650D0 (en) * | 1985-08-30 | 1985-10-02 | Ici Plc | Catalyst |
| DE3641774C2 (en) * | 1986-12-06 | 1996-05-15 | Metallgesellschaft Ag | Process for the preparation of a mixture of methanol and higher alcohols |
| ATE80328T1 (en) * | 1987-06-29 | 1992-09-15 | Unisearch Ltd | CATALYST FOR METANOL SYNTHESIS. |
| US4751248A (en) * | 1987-07-02 | 1988-06-14 | Phillips Petroleum Company | Preparation of alcohols from synthesis gas |
| DE3805397A1 (en) * | 1988-02-20 | 1989-08-24 | Ruhrkohle Ag | Process for producing fuel methanol (motor fuel) from coke oven gas and metallurgical plant gas |
| US4886651A (en) * | 1988-05-18 | 1989-12-12 | Air Products And Chemicals, Inc. | Process for co-production of higher alcohols, methanol and ammonia |
| DE102008049622B4 (en) * | 2008-09-30 | 2012-10-31 | Lurgi Gmbh | Process and plant for the production of methanol |
| CN103480378B (en) * | 2012-06-15 | 2016-08-10 | 中国石油化工股份有限公司 | The preparation method of Modified Copper-based Catalysts for Methanol |
Family Cites Families (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1159035A (en) * | 1965-08-18 | 1969-07-23 | Ici Ltd | Methanol Synthesis. |
| DE2056612C3 (en) * | 1970-11-18 | 1979-09-13 | Basf Ag, 6700 Ludwigshafen | Process for the production of methanol |
| CA1021354A (en) * | 1972-04-20 | 1977-11-22 | Alvin B. Stiles | Methanol synthesis catalyst |
| DE2846614C3 (en) * | 1978-10-26 | 1982-05-19 | Basf Ag, 6700 Ludwigshafen | Process for the production of methanol |
| AU535073B2 (en) * | 1979-12-17 | 1984-03-01 | Unisearch Limited | Methanol synthesis catalyst and use thereof |
| DE3005551A1 (en) * | 1980-02-14 | 1981-08-20 | Süd-Chemie AG, 8000 München | CATALYST FOR THE SYNTHESIS OF METHANOL AND ALCOHOL MIXTURES CONTAINING HIGHER ALCOHOLS |
| DE3005550A1 (en) * | 1980-02-14 | 1981-08-20 | Süd-Chemie AG, 8000 München | METHOD FOR PRODUCING OLEFINS |
| AU534460B2 (en) * | 1980-08-25 | 1984-02-02 | Theodore Oscar Wentworth | Process |
| JPS57130547A (en) * | 1981-02-06 | 1982-08-13 | Mitsubishi Gas Chem Co Inc | Catalyst for methanol synthesis |
| US4376721A (en) * | 1981-07-22 | 1983-03-15 | Electric Power Research Institute, Inc. | Methanol synthesis catalyst and method for its preparation |
| FR2523957A1 (en) * | 1982-03-26 | 1983-09-30 | Inst Francais Du Petrole | PROCESS FOR PRODUCING A MIXTURE OF METHANOL AND HIGHER ALCOHOLS FROM SYNTHESIS GAS |
| DE3317725A1 (en) * | 1983-05-16 | 1984-11-22 | Süd-Chemie AG, 8000 München | CATALYST FOR METHANOL SYNTHESIS |
| FR2558738B1 (en) * | 1984-01-27 | 1987-11-13 | Inst Francais Du Petrole | PROCESS FOR THE MANUFACTURE OF CATALYSTS CONTAINING COPPER, ZINC AND ALUMINUM FOR USE IN THE PRODUCTION OF METHANOL FROM SYNTHESIS GAS |
-
1984
- 1984-02-02 DE DE19843403492 patent/DE3403492A1/en not_active Withdrawn
- 1984-12-19 DE DE8484201907T patent/DE3465292D1/en not_active Expired
- 1984-12-19 EP EP84201907A patent/EP0152648B1/en not_active Expired
-
1985
- 1985-01-24 CA CA000472786A patent/CA1269401A/en not_active Expired - Lifetime
- 1985-01-29 ZA ZA85691A patent/ZA85691B/en unknown
- 1985-02-01 AU AU38288/85A patent/AU566455B2/en not_active Ceased
- 1985-02-02 JP JP60019177A patent/JPS60181038A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| EP0152648A1 (en) | 1985-08-28 |
| DE3465292D1 (en) | 1987-09-17 |
| DE3403492A1 (en) | 1985-08-08 |
| AU3828885A (en) | 1985-08-08 |
| AU566455B2 (en) | 1987-10-22 |
| JPS60181038A (en) | 1985-09-14 |
| ZA85691B (en) | 1986-09-24 |
| EP0152648B1 (en) | 1987-08-12 |
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