CA1226875A - Process for the production of hydrocarbons - Google Patents
Process for the production of hydrocarbonsInfo
- Publication number
- CA1226875A CA1226875A CA000463446A CA463446A CA1226875A CA 1226875 A CA1226875 A CA 1226875A CA 000463446 A CA000463446 A CA 000463446A CA 463446 A CA463446 A CA 463446A CA 1226875 A CA1226875 A CA 1226875A
- Authority
- CA
- Canada
- Prior art keywords
- range
- metal compound
- catalyst
- synthesis gas
- hydrocarbons
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
- C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
- C07C1/0425—Catalysts; their physical properties
- C07C1/043—Catalysts; their physical properties characterised by the composition
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
- C07C2521/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the alkali- or alkaline earth metals or beryllium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of rare earths
Abstract
A B S T R A C T
PROCESS FOR THE PRODUCTION OF HYDROCARBONS
Process for the production of hydrocarbons from synthesis gas in which the gas is passed at elevated pressure and temper-ature over a catalyst consisting of zirconium oxide promoted with at least one alkaline earth metal compound and/or at least one Group III b metal compound. Preferably zirconium oxide has a specific surface area in the range from 20 to 500 m2/g, the alkaline earth metal compound is calcium and/or barium oxide and the Group III b metal compound is yttria. A major part of the product consists of iso-butene.
PROCESS FOR THE PRODUCTION OF HYDROCARBONS
Process for the production of hydrocarbons from synthesis gas in which the gas is passed at elevated pressure and temper-ature over a catalyst consisting of zirconium oxide promoted with at least one alkaline earth metal compound and/or at least one Group III b metal compound. Preferably zirconium oxide has a specific surface area in the range from 20 to 500 m2/g, the alkaline earth metal compound is calcium and/or barium oxide and the Group III b metal compound is yttria. A major part of the product consists of iso-butene.
Description
aye 37S
PROCESS FOR THE PRODUCTION OF HYDROCARBONS
The invention relates to a process for the production of hydrocarbons from synthesis gas, characterized in that the synthesis gas is passed at elevated pressure and temperature over a catalyst consisting of zirconium oxide promoted with at least one alkaline earth metal cc~Found and/or at least one Group III b metal cc~pound. The group III b metals of the Periodic Table of Elements are defined in the "Handbook of Chemistry and Physics", Thea edition (1962), page 448. The catalyst may be supported on a suitable carrier such as alumina or silica.
In the process according to the invention the starting material is synthesis gas, i.e. a gaseous mixture consisting substantially of Ho and CO. Such H2/CO mixtures can very suitably be prepared by steam gasification or partial cc~bustion of a carbon-containing material. Examples of such materials are wood, peat, brawn coal, bituminous coal, anthracite, coke, crude mineral oil and fractions thereof as well as tars and oils extracted from tar sand and bitterns shale. The steam gasify-cation or partial combustion is preferably carried out at a temperature of 900-1600C and a pressure of 10-100 bar. In the process according to the invention it is ac~van-tageolls to star-t from an H2/CO mixture with an HO molar ratio of ore than 0.25 and less -than 6.
The intention is to convert the largest possible quantity Of the CO present in the feed into hydrocarbons. To this end the H2/CO molar ratio in the feed is suitably about 1Ø
The process according to thy invention can very suitably be carried out by conducting the feed in upward or downward direction through a vertically mounted reactor containing a fixed bed of the catalyst or by passing the gaseous feeds upwardly through a fluid catalyst bed. The process can also be carried out using a suspension of the catalyst or catalyst combination in a hydrocarbon oil. The process is preferably carried out under the following conditions: a temperature in the range from 200 to 600C and in particular from 300 to 500C, a pressure in the range from 0.1 to 1000 bar and in particular from 5 to 200 bar and a space velocity in the range from 100 to lo 5000 No synthesis gas/l catalyst hour In order to improve the hydrocarbon yield of the process according to the invention a catalyst is applied having an extensive specific surface area, preferably in the range from 20 to 500 mug Such a ZrO2 catalyst is prepared in the following way: a zirconyl salt, e.g. a chloride or nitrate is solved in water. While stirring ammonia is gradually added to the solution until the pi of the solution is in the range from 7 to 10. The precipitated zirconium hydroxide is separated from the solution by filtration and washed. It is calcined during 1 to 24 hours in air at a temperature in the range from 300 to 1000C.
By adding an alkaline earth metal compound and/or a Group III b metal compound to the catalyst the selectivity for Kiwi-drocarbons and especially the selectivity for iso-butene is improved. Therefore, the process is carried out using a catalyst promoted with an alkaline earth metal compound and/or a Group III b metal compound, preferably a metal oxide.
In order to improve the activity and stability of the catalyst it is advantageously calcined before being used, suitably at a temperature in the range from 400 to 800C.
Although any alkaline earth metal compound may be used as catalyst promoter in the present process, preference is given to a calcium compound and/or barium compound because it is readily available, cheap and it gives good results as to selectivity improvement. Of the Group III b metals yttrium is particularly preferred.
The promoter metal content of the catalyst is advantageous-lye chosen between 0.05 and 50% by weight, and preferably button and 10~ by weight.
The invention will new be elucidated by means of the following Examples.
Employ 1 A gaseous mixture of hydrogen and carbon monoxide having a KIWI molar ratio of l was passed over a bed of zirconium oxide catalyst particles containing 1% by weight of calcium in the form of Coo and having a specific surface area of 97 mug which was the result of a previous calcination step carried out in air for 2 hours at 500C. The catalyst particles size was from 0.4-0.6 mm.
The reaction conditions were chosen as follows:
Temperature : 450C
Pros Æ e : 20 bar as.
Gas hourly space velocity: 1000 Nl/l.h me CO-conversion to hydrocarbons was 17%.
The hydrocarbon product had the following composition:
Hydrocarbons Paraffins Olefins Of 45'1 _ _ C2 7.6 3.3 4.3 C3 4.3 2.2 2.1 iso-C4 24.7 9.2 15.5 n-C4 3.8 not determined not determine C5 14.4 not determined not determine pi The C3-product consisted for 49% of propane.
me molar ratio between butane and butane in the product was 1.9.
Comparative e~Eeriment 1 The experiment of Example 1 was repeated using the same conditions with the exception of the catalyst not containing calcium.
me CO-conversion was 30~.
m e hydrocarbon product composition was:
Hydrocarbons Paraffins Olefins i White White White Of 6128 126 2 C3 8.1 6.5 1.6 iso-C4 7.3 2.3 5.0 n-C4 2.4 0.4 2.0 C5 2.2 not determine not determined _ By comparing the results given in the Example with those of the ccmparati~e experiment it can be concluded that by adding an alkaline earth metal compound to the catalyst the olefin content of the product is increased and especially the selectivity to iso-butene is markedly improved. 5 EXEMPT 2 m e experiment of Example 1 was repeated, using the same conditions, over a catalyst comprising White ZrO2 and White spa in the form of Boo, and having a surface area of 85 mug which was the result of a previous calcination step carried out in air for 2 hours at 500C. me catalyst particles size was from 0.4-0.6 mm. m e CO-conversion to hydrocarbons was 21.5%.
I
The hydrocarbon product had the following composition:
_ Hydrocarbons Paraffins Olefins White White White Clue 41.1 C213.0 6.9 6.1 C35.8 2.3 3.5 is C23.8 6.2 17.6 n-C 8.9 not determined not determined C57.4 not determined not determined .
A gaseous mixture of hydrogen and carbon monoxide having a KIWI molar ratio of 3 was passed over a bed of zirconium oxide catalyst particles containing 1% by weight of yttrium in the form of YO-YO and having a specific surface area of 85 mug which was the result of a previous calcination step carried out in air for 2 hours at 500C. The catalyst particles size was from 0.4-0.6 mm.
m e reaction conditions were chosen as follows:
Tem~rature : 450C
Pressure : 80 bar Gas hourly space velocity: 594 Nl/l.h The CO-conversion to hydrocarbons was 16~.
The hydrocarbon product had the following composition:
Hydrocarbons Paraffins Olefins White White White Of 27.0 27 C2 6.4 4.8 1.6 C3 6.8 5.5 1 1.3 iso-C4 27.4 5.4 122.0 n-C4 5.8 not determined not determine C5 26.5 not determined not determine
PROCESS FOR THE PRODUCTION OF HYDROCARBONS
The invention relates to a process for the production of hydrocarbons from synthesis gas, characterized in that the synthesis gas is passed at elevated pressure and temperature over a catalyst consisting of zirconium oxide promoted with at least one alkaline earth metal cc~Found and/or at least one Group III b metal cc~pound. The group III b metals of the Periodic Table of Elements are defined in the "Handbook of Chemistry and Physics", Thea edition (1962), page 448. The catalyst may be supported on a suitable carrier such as alumina or silica.
In the process according to the invention the starting material is synthesis gas, i.e. a gaseous mixture consisting substantially of Ho and CO. Such H2/CO mixtures can very suitably be prepared by steam gasification or partial cc~bustion of a carbon-containing material. Examples of such materials are wood, peat, brawn coal, bituminous coal, anthracite, coke, crude mineral oil and fractions thereof as well as tars and oils extracted from tar sand and bitterns shale. The steam gasify-cation or partial combustion is preferably carried out at a temperature of 900-1600C and a pressure of 10-100 bar. In the process according to the invention it is ac~van-tageolls to star-t from an H2/CO mixture with an HO molar ratio of ore than 0.25 and less -than 6.
The intention is to convert the largest possible quantity Of the CO present in the feed into hydrocarbons. To this end the H2/CO molar ratio in the feed is suitably about 1Ø
The process according to thy invention can very suitably be carried out by conducting the feed in upward or downward direction through a vertically mounted reactor containing a fixed bed of the catalyst or by passing the gaseous feeds upwardly through a fluid catalyst bed. The process can also be carried out using a suspension of the catalyst or catalyst combination in a hydrocarbon oil. The process is preferably carried out under the following conditions: a temperature in the range from 200 to 600C and in particular from 300 to 500C, a pressure in the range from 0.1 to 1000 bar and in particular from 5 to 200 bar and a space velocity in the range from 100 to lo 5000 No synthesis gas/l catalyst hour In order to improve the hydrocarbon yield of the process according to the invention a catalyst is applied having an extensive specific surface area, preferably in the range from 20 to 500 mug Such a ZrO2 catalyst is prepared in the following way: a zirconyl salt, e.g. a chloride or nitrate is solved in water. While stirring ammonia is gradually added to the solution until the pi of the solution is in the range from 7 to 10. The precipitated zirconium hydroxide is separated from the solution by filtration and washed. It is calcined during 1 to 24 hours in air at a temperature in the range from 300 to 1000C.
By adding an alkaline earth metal compound and/or a Group III b metal compound to the catalyst the selectivity for Kiwi-drocarbons and especially the selectivity for iso-butene is improved. Therefore, the process is carried out using a catalyst promoted with an alkaline earth metal compound and/or a Group III b metal compound, preferably a metal oxide.
In order to improve the activity and stability of the catalyst it is advantageously calcined before being used, suitably at a temperature in the range from 400 to 800C.
Although any alkaline earth metal compound may be used as catalyst promoter in the present process, preference is given to a calcium compound and/or barium compound because it is readily available, cheap and it gives good results as to selectivity improvement. Of the Group III b metals yttrium is particularly preferred.
The promoter metal content of the catalyst is advantageous-lye chosen between 0.05 and 50% by weight, and preferably button and 10~ by weight.
The invention will new be elucidated by means of the following Examples.
Employ 1 A gaseous mixture of hydrogen and carbon monoxide having a KIWI molar ratio of l was passed over a bed of zirconium oxide catalyst particles containing 1% by weight of calcium in the form of Coo and having a specific surface area of 97 mug which was the result of a previous calcination step carried out in air for 2 hours at 500C. The catalyst particles size was from 0.4-0.6 mm.
The reaction conditions were chosen as follows:
Temperature : 450C
Pros Æ e : 20 bar as.
Gas hourly space velocity: 1000 Nl/l.h me CO-conversion to hydrocarbons was 17%.
The hydrocarbon product had the following composition:
Hydrocarbons Paraffins Olefins Of 45'1 _ _ C2 7.6 3.3 4.3 C3 4.3 2.2 2.1 iso-C4 24.7 9.2 15.5 n-C4 3.8 not determined not determine C5 14.4 not determined not determine pi The C3-product consisted for 49% of propane.
me molar ratio between butane and butane in the product was 1.9.
Comparative e~Eeriment 1 The experiment of Example 1 was repeated using the same conditions with the exception of the catalyst not containing calcium.
me CO-conversion was 30~.
m e hydrocarbon product composition was:
Hydrocarbons Paraffins Olefins i White White White Of 6128 126 2 C3 8.1 6.5 1.6 iso-C4 7.3 2.3 5.0 n-C4 2.4 0.4 2.0 C5 2.2 not determine not determined _ By comparing the results given in the Example with those of the ccmparati~e experiment it can be concluded that by adding an alkaline earth metal compound to the catalyst the olefin content of the product is increased and especially the selectivity to iso-butene is markedly improved. 5 EXEMPT 2 m e experiment of Example 1 was repeated, using the same conditions, over a catalyst comprising White ZrO2 and White spa in the form of Boo, and having a surface area of 85 mug which was the result of a previous calcination step carried out in air for 2 hours at 500C. me catalyst particles size was from 0.4-0.6 mm. m e CO-conversion to hydrocarbons was 21.5%.
I
The hydrocarbon product had the following composition:
_ Hydrocarbons Paraffins Olefins White White White Clue 41.1 C213.0 6.9 6.1 C35.8 2.3 3.5 is C23.8 6.2 17.6 n-C 8.9 not determined not determined C57.4 not determined not determined .
A gaseous mixture of hydrogen and carbon monoxide having a KIWI molar ratio of 3 was passed over a bed of zirconium oxide catalyst particles containing 1% by weight of yttrium in the form of YO-YO and having a specific surface area of 85 mug which was the result of a previous calcination step carried out in air for 2 hours at 500C. The catalyst particles size was from 0.4-0.6 mm.
m e reaction conditions were chosen as follows:
Tem~rature : 450C
Pressure : 80 bar Gas hourly space velocity: 594 Nl/l.h The CO-conversion to hydrocarbons was 16~.
The hydrocarbon product had the following composition:
Hydrocarbons Paraffins Olefins White White White Of 27.0 27 C2 6.4 4.8 1.6 C3 6.8 5.5 1 1.3 iso-C4 27.4 5.4 122.0 n-C4 5.8 not determined not determine C5 26.5 not determined not determine
Claims (7)
1. Process for the production of hydrocarbons from synthesis gas, characterized in that the synthesis gas is passed at elevated pressure and temperature over a catalyst consisting of zirconium oxide promoted with at least one alkaline earth metal compound and/or at least one Group III b metal compound.
2. Process as claimed in claim 1, characterized in that the zirconium oxide has a specific surface area in the range from 20 to 500 m2/g.
3. Process as claimed in claim 1 or 2, characterized in that the promoter metal compound is a metal oxide.
4. Process as claimed in claim 1 or 2, characterized in that the promoter metal compound is a calcium compound, a barium compound and/or an yttrium compound.
5. Process as claimed in claim 1 or 2, characterized in that the catalyst contains a promoter metal content in the range from 0.05 to 50% by weight.
6. Process as claimed in claim 1 or 2, characterized in that it is carried out at a pressure in the range form 0.1 to 1000 bar abs., a temperature in the range from 200 to 600°C and a space velocity in the range from 100 to 5000 normal litres synthesis gas per litre of catalyst per hour.
7. Process as claimed in claim 1 or 2, characterized in that the synthesis gas consists substantially of H2 and CO, the H2/CO
molar ratio being in the range from 0.25 to 6Ø
molar ratio being in the range from 0.25 to 6Ø
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR8316375A FR2553406A1 (en) | 1983-10-14 | 1983-10-14 | Process for the production of hydrocarbons. |
| FR8316375 | 1983-10-14 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1226875A true CA1226875A (en) | 1987-09-15 |
Family
ID=9293140
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000463446A Expired CA1226875A (en) | 1983-10-14 | 1984-09-18 | Process for the production of hydrocarbons |
Country Status (2)
| Country | Link |
|---|---|
| CA (1) | CA1226875A (en) |
| FR (1) | FR2553406A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0380937A (en) * | 1989-08-25 | 1991-04-05 | Tonen Corp | Steam reforming catalyst of hydrocarbon and preparation thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1223311A (en) * | 1957-09-27 | 1960-06-16 | Improvements in processes for preparing gaseous hydrocarbon mixtures consisting almost entirely of ethylene | |
| FR2513625A1 (en) * | 1981-09-28 | 1983-04-01 | Shell Int Research | PROCESS FOR THE PRODUCTION OF HYDROCARBONS FROM SYNTHESIS GAS |
-
1983
- 1983-10-14 FR FR8316375A patent/FR2553406A1/en active Pending
-
1984
- 1984-09-18 CA CA000463446A patent/CA1226875A/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| FR2553406A1 (en) | 1985-04-19 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |