CA1139789A - Process for the manufacture of ethanol from synthesis gas - Google Patents
Process for the manufacture of ethanol from synthesis gasInfo
- Publication number
- CA1139789A CA1139789A CA000354653A CA354653A CA1139789A CA 1139789 A CA1139789 A CA 1139789A CA 000354653 A CA000354653 A CA 000354653A CA 354653 A CA354653 A CA 354653A CA 1139789 A CA1139789 A CA 1139789A
- Authority
- CA
- Canada
- Prior art keywords
- cobalt
- catalyst
- ethanol
- gold
- reaction
- 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
Links
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
- C07C29/156—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 iron group metals, platinum group metals or compounds thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
PROCESS FOR THE MANUFACTURE OF ETHANOL FROM
SYNTHESIS GAS
Abstract of the Disclosure The invention relates to a process for the manufacture of ethanol from carbon monoxide and hydrogen on cobalt cata-lysts. According to the invention the catalyst contains, be-sides cobalt as metal or compound, at least one of the ele-ments gold, silver and rhenium als metal or compound. The catalysts are preferably supported on carriers.
SYNTHESIS GAS
Abstract of the Disclosure The invention relates to a process for the manufacture of ethanol from carbon monoxide and hydrogen on cobalt cata-lysts. According to the invention the catalyst contains, be-sides cobalt as metal or compound, at least one of the ele-ments gold, silver and rhenium als metal or compound. The catalysts are preferably supported on carriers.
Description
i39'~
- 2 - HOE 79/F 156 The present invention relates to a process for the ma-nufacture of ethanol by reacting carbon monoxide with hydro-gen on a cobalt catalyst, modified by gold andJor silver and/or rhenium.
Processes for the manufacture of alcohols from synthesis gas are already known.
It is known, for example, that the use of rhodium cata-lysts together with certain promotors in the synthesis gas reaction favour the formation of oxygen-containing compounds (DE-AS 25 03 204). The disadvantage is the relatively high price of rhodium. It is also known to use cheaper cobalt ca-talysts (Fischer Tropsch) in the synthesis gas reaction. He-reby, however, a variety of products is formed, preferably hydrocarbons, but only small amounts of oxygenated compounds.
The modification of cobalt catalysts by copper, chro-mium, zinc, alkali earth metals, alkali metals, aluminium, rare earths or iron provide a series of products from metha-nol to butanol, but the proportion of ethanol is only about 30 ~ by weight (DE-PS 857 799, DE-PS 5L14 665, FR-PS 660 678, FR-PS 1 074 0l~5, F~-PS 2 7Ll8 0g7). Besides this, these cata-lysts are very sensitive, concerning the manufacture, the initiation and the continuous operation. Therefore, in most cases they are not long-lived. Thus, the task was to produce ethanol from synthesis gas with high selectivity on resis-tant and long-lived catalysts.
Now it has been found that the selectivity of ethanol is considerably increased on cobalt catalysts by the addi-tion gold and/or silver and/or rhenium as promotors.
Subject of the invention is, therefore, a process for the manufacture of ethanol fro~ carbon monoxide and hydrogen on cobalt catalysts, which comprises using a catalyst contain-ing, besides cobalt as metal or compound, at least one of the elements gold, silver and rhenium as metal or compound.
Besides cobalt, the catalyst preferab]y contains gold, but even more preferably the combination gold/silver. The result that the selectivity of the synthesis gas reaction to etha-nol is increased to such a considerable degree by the addi-.", ~
Processes for the manufacture of alcohols from synthesis gas are already known.
It is known, for example, that the use of rhodium cata-lysts together with certain promotors in the synthesis gas reaction favour the formation of oxygen-containing compounds (DE-AS 25 03 204). The disadvantage is the relatively high price of rhodium. It is also known to use cheaper cobalt ca-talysts (Fischer Tropsch) in the synthesis gas reaction. He-reby, however, a variety of products is formed, preferably hydrocarbons, but only small amounts of oxygenated compounds.
The modification of cobalt catalysts by copper, chro-mium, zinc, alkali earth metals, alkali metals, aluminium, rare earths or iron provide a series of products from metha-nol to butanol, but the proportion of ethanol is only about 30 ~ by weight (DE-PS 857 799, DE-PS 5L14 665, FR-PS 660 678, FR-PS 1 074 0l~5, F~-PS 2 7Ll8 0g7). Besides this, these cata-lysts are very sensitive, concerning the manufacture, the initiation and the continuous operation. Therefore, in most cases they are not long-lived. Thus, the task was to produce ethanol from synthesis gas with high selectivity on resis-tant and long-lived catalysts.
Now it has been found that the selectivity of ethanol is considerably increased on cobalt catalysts by the addi-tion gold and/or silver and/or rhenium as promotors.
Subject of the invention is, therefore, a process for the manufacture of ethanol fro~ carbon monoxide and hydrogen on cobalt catalysts, which comprises using a catalyst contain-ing, besides cobalt as metal or compound, at least one of the elements gold, silver and rhenium as metal or compound.
Besides cobalt, the catalyst preferab]y contains gold, but even more preferably the combination gold/silver. The result that the selectivity of the synthesis gas reaction to etha-nol is increased to such a considerable degree by the addi-.", ~
3~
- 3 - _OE 79/F 156 tion of the abovementioned elements - with, at the same time, a good space-time yield - is extremely surprising and could not be foreseen, because gold and silver are known as cata-lyst poisons in hydrogenations, whilst hydrogenations with rhenium, ln general, yield hydrocarbons.
Besides ethanol which is formed according to the inven tion in high selectivity, there are formed small amounts of methanol, propanol and butanol and some acetaldehyde as by-products.
The catalysts for the process according to the inven-tion are preferably obtained by impregnating a catalyst car-rier with a solution of cobalt, gold and/or silver andJor rhenium salts and by subsequent drying, the salts being ap-plied together or one after the other. Suitable salts are all soluble cobalt, gold, silver and rhenium salts, such as the chlorides, bromides, nitrates, acetates, propionates, lactates, citrates of cobalt, the chlorides, acetates, pro-pionates of gold, as well as aurates (such as barium aceto-aurate or barium propionoaurate), furthermore the acetate, propionate, butyrate, lactate and nitrate of silver, as well as rhenium heptoxide, perrhenates and rhenates.
The salts mentioned are dissolved in suitable solvents.
Suitable solvents are, for example, water, aqueous carboxylic acids and anhydrous carboxylic acids, especially water and acetic acid.
Suitable supports are the common carrier materials with different specific surfaces and pore volumes. Carriers with a specific surface of from 50 - 1000 m2/g and a pore volu-~le of more than 0.3 ml/g are preferably used.
Suitable products are, for example, silicic acid, natu-ral or synthetic silicat.es of elements of the II. up to the VIII. group of the periodical system (for example the sili-cates of magnesium, aluminium or manganese, furthermore alu-minium oxide, thorium oxide and spinels.
It is also possible, however, to produce suitable cata-lysts by precipitation of cobalt oxide together with gold and/or silver and/or rhenium or by subsequent impregnation 7~
_ 4 _OE`, 79/F 156 of cobalt oxide with salts of gold and/or rhenium.
Preferably the catalyst is reduced prior to its use with a suitable reduction agent, such as hydrogen, carbon monoxide or methanol and this is expediently being done in the synthe-sis gas reactor itself. In general, the temperature duringthe reduction is lower than 400C, preferably between 200 and 300C. In many cases it is advisable not to carry out the reduction with the undiluted reducing gases, but with an additional portion of inert gases, such as nitrogen, carbon dioxide and noble gases.
The concentration of cobalt in the catalysts may vary within a very wide range; the cobalt compounds without car-riers, for example cobalt oxide, can be used as well as sup-ported catalysts with a minimum of 1 % by weight of cobalt.
The concentration of the promotors depends on the con-centration of the cobalt, per mole of cobalt from 0.001 to 0.5 mole, preferabiy from 0.02 to 0.2 mole of eaoh promotor being used.
For carrying out the process acording to the invention gas mixtures, which totally or predominantly consist of carbon monoxide and hydrogen and which optionally may also contain other components such as nitrogen, argon, carbon dioxide or methane, are passed over the catalyst. The ratio by volume of carbon monoxide to hydrogen may vary within a great range. Preferred ratios are from 5 : 1 and 1 : 5, especially from 3 : 1 to 1 : 3. The reaction temperaure in general is between 1~5 and 375C, preferably between 200 and 350C.
The reaction pressure lies between 1 and 30~ bar, pre-ferably between 20 and 200 bar.
For carrying out the reaction, the gaseous phase is preferred. The usual solid bed reactors may be used. Fur-thermore, there are suitable reactors with moved catalysts bed or fluidized bed reactors.
The reaction of the synthesis gas can also be performed in the presenc~ of the solid and finely divided catalyst suspended in inert solvents and/or reaction products.
~3~
An especially preferred embodiment of the invention consist in carrying out the reaction in a cycle gas appara-tus in the gaseous phase, in which, after the separation of the condensable reaction products, the non-reacted gas mixture is recycled into the reactor.
This embodiment is especially economical and by dilu-tion of the fresh gas with the rest gas poorer in hydro-gen which is recycled, it allows higher reaction temperatu-res and thus higher space-time yields without~ change of se-lectivity. Suitable cycle gas apparatus are those with in-terior or exterior gas circulation.
The following examples illustrate the invention.
E X A M P L E S
A) General test description The apparatus consists of a heated reaction tube of 20 cm length and 14 mm inner diameter of corrosion resis~
tent steel and a centrally installed shell for measuring the temperature with a thermocouple.
This reactor is in a heating bath of Wood's metal in which the synthesis gas is also preheated. The tempera~
ture in the reactor as well as the temperature of the me-tal bath may be followed on a recorder. In the case of an overheating of the catalyst, N2 is passed through.
The reduction of the catalyst freshly filled into the reactor, is carried out with a mixture of H2/N2 in a ratio of 1 : 4 at atmospheric pressure and at 300C.
The synthesis gas mixture ~CO : H2 ~ 1 : 1) is taken from a compressed gas cylinder, the amount being measured by the fall of pressure with a sensitive gas manometer.
Pressure adjustment and pressure maintenance are provided by a pressure controller. Prior for the pressure controller the condensable proportions of the reaction mixture are condensed in a separator and passed to the GC-analysis.
.
,: ~
. :
'7~
- 6 ~ H0~ 79/F 156 According to thls method the catalysts described below are examined. The following table shows the tes-t conditions as well as the space~time-yields of oxygenated C2 products per liter of catalyst and hour as well as the selectivities to ethanol.
Description of the catalyst The following percentages are given by weight.
E mple 1 40 g of a commercial silica gel carrier with a specific surface of 400 m2~g, a pore volume of 1.2 ml/g and an appa-rent density of 0.4 g/ml are soaked ~ith a solution of 16.3 g of cobalt acetate, 3.5 g of barium acetoaurate and 0.5 g sil-ver acetate in a mixture of 35 ml of water and 5 ml of acetic acid and dried at 60C under 250 mbar. The catalyst con-tains 8.4 % Co, 2.8 % Au, 0.7 % AG and 1 % Ba in the form of the acetates.
Example 2 35 g of the carriers mentioned in Example 1 are soaked with a solition of 16.3 g cobalt acetate, 1.7 g of barium acetoaurate and 2.0 g of rhenium heptoxide in 43 ml of a 7%
acetic acid and dried at 110C under atmospheric pressure.
The finished catalyst contains 9.4 % Co, 1.5 % Au, 3.7 g Re t and 0.6 % Ba.
Example 3 35 g of the carrier mentioned in Example 1 are soaked with a solution of 16.3 g cobalt acetate and 2 g rheniumhept-oxide in 43 ml of 7% acetic acid and dried at 80 in a ni-trogen flow. The finished catalyst contains 9.5 % Co and 3.8 % Re.
Example 4 ,~
40 g of` a commercial silicic acid carrier (250 m'/g surface, o.8 ml/g pore volume, 0.7 ml/g apparent density) are soaked with a solution of 16.3 g cobalt acetate and 1.9 g gold acetate in 40 ml of 12.5 % acetic acid in two stages, after each soaking the product is dried until it has reached a constant weight. The finished catalyst contains 8.3 ~ Co and 2 % Au.
3~317~
Test results The following table shows the test results:
Ex. Pres- tempe- space space-tlme-yield (g/l.h) sure rature velo-(bar) (C) city metha- etha- propa- buta- acet- selec-(Nl/ nol nol nol nol alde- tivity l.h) hyde * to etha-nol _ 100 280 1200 7.2 16.5 4.5 0 0.05 60 2 80 ~75 6000 9.9 33 9.9 1.6 o 6Z
3 100 260 8050 8.5 27.5 6.7 0.7 0 65
- 3 - _OE 79/F 156 tion of the abovementioned elements - with, at the same time, a good space-time yield - is extremely surprising and could not be foreseen, because gold and silver are known as cata-lyst poisons in hydrogenations, whilst hydrogenations with rhenium, ln general, yield hydrocarbons.
Besides ethanol which is formed according to the inven tion in high selectivity, there are formed small amounts of methanol, propanol and butanol and some acetaldehyde as by-products.
The catalysts for the process according to the inven-tion are preferably obtained by impregnating a catalyst car-rier with a solution of cobalt, gold and/or silver andJor rhenium salts and by subsequent drying, the salts being ap-plied together or one after the other. Suitable salts are all soluble cobalt, gold, silver and rhenium salts, such as the chlorides, bromides, nitrates, acetates, propionates, lactates, citrates of cobalt, the chlorides, acetates, pro-pionates of gold, as well as aurates (such as barium aceto-aurate or barium propionoaurate), furthermore the acetate, propionate, butyrate, lactate and nitrate of silver, as well as rhenium heptoxide, perrhenates and rhenates.
The salts mentioned are dissolved in suitable solvents.
Suitable solvents are, for example, water, aqueous carboxylic acids and anhydrous carboxylic acids, especially water and acetic acid.
Suitable supports are the common carrier materials with different specific surfaces and pore volumes. Carriers with a specific surface of from 50 - 1000 m2/g and a pore volu-~le of more than 0.3 ml/g are preferably used.
Suitable products are, for example, silicic acid, natu-ral or synthetic silicat.es of elements of the II. up to the VIII. group of the periodical system (for example the sili-cates of magnesium, aluminium or manganese, furthermore alu-minium oxide, thorium oxide and spinels.
It is also possible, however, to produce suitable cata-lysts by precipitation of cobalt oxide together with gold and/or silver and/or rhenium or by subsequent impregnation 7~
_ 4 _OE`, 79/F 156 of cobalt oxide with salts of gold and/or rhenium.
Preferably the catalyst is reduced prior to its use with a suitable reduction agent, such as hydrogen, carbon monoxide or methanol and this is expediently being done in the synthe-sis gas reactor itself. In general, the temperature duringthe reduction is lower than 400C, preferably between 200 and 300C. In many cases it is advisable not to carry out the reduction with the undiluted reducing gases, but with an additional portion of inert gases, such as nitrogen, carbon dioxide and noble gases.
The concentration of cobalt in the catalysts may vary within a very wide range; the cobalt compounds without car-riers, for example cobalt oxide, can be used as well as sup-ported catalysts with a minimum of 1 % by weight of cobalt.
The concentration of the promotors depends on the con-centration of the cobalt, per mole of cobalt from 0.001 to 0.5 mole, preferabiy from 0.02 to 0.2 mole of eaoh promotor being used.
For carrying out the process acording to the invention gas mixtures, which totally or predominantly consist of carbon monoxide and hydrogen and which optionally may also contain other components such as nitrogen, argon, carbon dioxide or methane, are passed over the catalyst. The ratio by volume of carbon monoxide to hydrogen may vary within a great range. Preferred ratios are from 5 : 1 and 1 : 5, especially from 3 : 1 to 1 : 3. The reaction temperaure in general is between 1~5 and 375C, preferably between 200 and 350C.
The reaction pressure lies between 1 and 30~ bar, pre-ferably between 20 and 200 bar.
For carrying out the reaction, the gaseous phase is preferred. The usual solid bed reactors may be used. Fur-thermore, there are suitable reactors with moved catalysts bed or fluidized bed reactors.
The reaction of the synthesis gas can also be performed in the presenc~ of the solid and finely divided catalyst suspended in inert solvents and/or reaction products.
~3~
An especially preferred embodiment of the invention consist in carrying out the reaction in a cycle gas appara-tus in the gaseous phase, in which, after the separation of the condensable reaction products, the non-reacted gas mixture is recycled into the reactor.
This embodiment is especially economical and by dilu-tion of the fresh gas with the rest gas poorer in hydro-gen which is recycled, it allows higher reaction temperatu-res and thus higher space-time yields without~ change of se-lectivity. Suitable cycle gas apparatus are those with in-terior or exterior gas circulation.
The following examples illustrate the invention.
E X A M P L E S
A) General test description The apparatus consists of a heated reaction tube of 20 cm length and 14 mm inner diameter of corrosion resis~
tent steel and a centrally installed shell for measuring the temperature with a thermocouple.
This reactor is in a heating bath of Wood's metal in which the synthesis gas is also preheated. The tempera~
ture in the reactor as well as the temperature of the me-tal bath may be followed on a recorder. In the case of an overheating of the catalyst, N2 is passed through.
The reduction of the catalyst freshly filled into the reactor, is carried out with a mixture of H2/N2 in a ratio of 1 : 4 at atmospheric pressure and at 300C.
The synthesis gas mixture ~CO : H2 ~ 1 : 1) is taken from a compressed gas cylinder, the amount being measured by the fall of pressure with a sensitive gas manometer.
Pressure adjustment and pressure maintenance are provided by a pressure controller. Prior for the pressure controller the condensable proportions of the reaction mixture are condensed in a separator and passed to the GC-analysis.
.
,: ~
. :
'7~
- 6 ~ H0~ 79/F 156 According to thls method the catalysts described below are examined. The following table shows the tes-t conditions as well as the space~time-yields of oxygenated C2 products per liter of catalyst and hour as well as the selectivities to ethanol.
Description of the catalyst The following percentages are given by weight.
E mple 1 40 g of a commercial silica gel carrier with a specific surface of 400 m2~g, a pore volume of 1.2 ml/g and an appa-rent density of 0.4 g/ml are soaked ~ith a solution of 16.3 g of cobalt acetate, 3.5 g of barium acetoaurate and 0.5 g sil-ver acetate in a mixture of 35 ml of water and 5 ml of acetic acid and dried at 60C under 250 mbar. The catalyst con-tains 8.4 % Co, 2.8 % Au, 0.7 % AG and 1 % Ba in the form of the acetates.
Example 2 35 g of the carriers mentioned in Example 1 are soaked with a solition of 16.3 g cobalt acetate, 1.7 g of barium acetoaurate and 2.0 g of rhenium heptoxide in 43 ml of a 7%
acetic acid and dried at 110C under atmospheric pressure.
The finished catalyst contains 9.4 % Co, 1.5 % Au, 3.7 g Re t and 0.6 % Ba.
Example 3 35 g of the carrier mentioned in Example 1 are soaked with a solution of 16.3 g cobalt acetate and 2 g rheniumhept-oxide in 43 ml of 7% acetic acid and dried at 80 in a ni-trogen flow. The finished catalyst contains 9.5 % Co and 3.8 % Re.
Example 4 ,~
40 g of` a commercial silicic acid carrier (250 m'/g surface, o.8 ml/g pore volume, 0.7 ml/g apparent density) are soaked with a solution of 16.3 g cobalt acetate and 1.9 g gold acetate in 40 ml of 12.5 % acetic acid in two stages, after each soaking the product is dried until it has reached a constant weight. The finished catalyst contains 8.3 ~ Co and 2 % Au.
3~317~
Test results The following table shows the test results:
Ex. Pres- tempe- space space-tlme-yield (g/l.h) sure rature velo-(bar) (C) city metha- etha- propa- buta- acet- selec-(Nl/ nol nol nol nol alde- tivity l.h) hyde * to etha-nol _ 100 280 1200 7.2 16.5 4.5 0 0.05 60 2 80 ~75 6000 9.9 33 9.9 1.6 o 6Z
3 100 260 8050 8.5 27.5 6.7 0.7 0 65
4 150 280 7000 14.6 19.7 5.6 1.3 1.0 52 comp.100 280 6500 0.5 0.04 0.030.01 0.03 7~**
ex .
**
* Definition of the seleCtivitY: Mol CO totally reacted ** Comparative example with cobalt alone; catalyst manufactured in other respects as in Example 1.
*** The other reaction products consist of saturated and unsatu-rated hydrocarbons.
. , .
ex .
**
* Definition of the seleCtivitY: Mol CO totally reacted ** Comparative example with cobalt alone; catalyst manufactured in other respects as in Example 1.
*** The other reaction products consist of saturated and unsatu-rated hydrocarbons.
. , .
Claims (9)
OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for the preparation of ethanol in which carbon monoxide is reacted with hydrogen in the gaseous phase and at a pressure of 2 to 200 bar in the presence of a cobalt catalyst containing at least one of the elements gold, silver, rhenium and mixtures thereof, in the form of a metal or a compound thereof, the catalyst being supported on a carrier by impregnation of the carrier with the catalyst.
2. A process as claimed in claim 1 in which the carrier has a specific surface of from 50 to 1000 m2/g and a pore volume of more than 0.3 ml/g.
3. A process as claimed in claim 1 in which the cobalt catalyst contains gold.
4. A process as claimed in claim 1, claim 2 or claim 3 in which the cobalt catalyst contains gold and silver.
5. A process as claimed in claim 1, claim 2 or claim 3 in which the catalyst is reduced prior to its use.
6. A process as claimed in claim 1, claim 2 or claim 3 in which the reaction is carried out at a temperature of from 175 to 375°C.
7. A process as claimed in claim 1, claim 2 or claim 3 in which the reaction is carried out at a temperature of from 200 to 350°C.
8. A process as claimed in claim 1, claim 2 or claim 3 in which the ratio by volume of carbon monoxide to hydrogen is in the range of from 5:1 to 1:5.
9. A process as claimed in claim 1, claim 2 or claim 3 in which the ratio by volume of carbon monoxide to hydrogen is in the range of from 3:1 to 1:3.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP2925571.8 | 1979-06-25 | ||
| DE19792925571 DE2925571A1 (en) | 1979-06-25 | 1979-06-25 | METHOD FOR PRODUCING ETHANOL FROM SYNTHESIS GAS |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1139789A true CA1139789A (en) | 1983-01-18 |
Family
ID=6074088
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000354653A Expired CA1139789A (en) | 1979-06-25 | 1980-06-24 | Process for the manufacture of ethanol from synthesis gas |
Country Status (8)
| Country | Link |
|---|---|
| EP (1) | EP0021330B1 (en) |
| JP (1) | JPS5625124A (en) |
| AU (1) | AU5956380A (en) |
| CA (1) | CA1139789A (en) |
| DD (1) | DD151741A5 (en) |
| DE (2) | DE2925571A1 (en) |
| PL (1) | PL225177A1 (en) |
| ZA (1) | ZA803763B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4670475A (en) * | 1984-06-29 | 1987-06-02 | Exxon Research And Engineering Company | Improved cobalt catalysts, and use thereof for Fischer-Tropsch synthesis |
| US4752622A (en) * | 1984-07-30 | 1988-06-21 | The Dow Chemical Company | Process for producing alcohols from synthesis gas |
| US4762858A (en) * | 1985-09-16 | 1988-08-09 | The Dow Chemical Company | Syngas conversion to oxygenates by reduced yttrium/lanthanide/actinide-modified catalyst |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ZA814841B (en) * | 1980-07-23 | 1983-02-23 | British Petroleum Co | Process for the production of lower hydrocarbons and oxygenated derivatives thereof by the catalytic conversion of carbon monoxide and hydrogen |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR660678A (en) * | 1927-06-07 | 1929-07-16 | Ig Farbenindustrie Ag | Process for the production of ethyl alcohol and other organic compounds |
| US3947563A (en) * | 1974-10-07 | 1976-03-30 | Celanese Corporation | Hydrogenolysis of formates |
| US4150246A (en) * | 1976-08-30 | 1979-04-17 | Celanese Corporation | Homologation of alkanols |
-
1979
- 1979-06-25 DE DE19792925571 patent/DE2925571A1/en not_active Withdrawn
-
1980
- 1980-06-18 EP EP80103378A patent/EP0021330B1/en not_active Expired
- 1980-06-18 DE DE8080103378T patent/DE3063458D1/en not_active Expired
- 1980-06-23 DD DD80222088A patent/DD151741A5/en unknown
- 1980-06-24 PL PL22517780A patent/PL225177A1/xx unknown
- 1980-06-24 AU AU59563/80A patent/AU5956380A/en not_active Abandoned
- 1980-06-24 CA CA000354653A patent/CA1139789A/en not_active Expired
- 1980-06-24 JP JP8467880A patent/JPS5625124A/en active Pending
- 1980-06-24 ZA ZA00803763A patent/ZA803763B/en unknown
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4670475A (en) * | 1984-06-29 | 1987-06-02 | Exxon Research And Engineering Company | Improved cobalt catalysts, and use thereof for Fischer-Tropsch synthesis |
| US4752622A (en) * | 1984-07-30 | 1988-06-21 | The Dow Chemical Company | Process for producing alcohols from synthesis gas |
| US4762858A (en) * | 1985-09-16 | 1988-08-09 | The Dow Chemical Company | Syngas conversion to oxygenates by reduced yttrium/lanthanide/actinide-modified catalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0021330B1 (en) | 1983-05-25 |
| DE3063458D1 (en) | 1983-07-07 |
| EP0021330A1 (en) | 1981-01-07 |
| DE2925571A1 (en) | 1981-01-22 |
| DD151741A5 (en) | 1981-11-04 |
| PL225177A1 (en) | 1981-03-27 |
| ZA803763B (en) | 1981-07-29 |
| JPS5625124A (en) | 1981-03-10 |
| AU5956380A (en) | 1981-01-08 |
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