CA1143713A - Process for the preparation of fischer-tropsch catalysts - Google Patents
Process for the preparation of fischer-tropsch catalystsInfo
- Publication number
- CA1143713A CA1143713A CA000350342A CA350342A CA1143713A CA 1143713 A CA1143713 A CA 1143713A CA 000350342 A CA000350342 A CA 000350342A CA 350342 A CA350342 A CA 350342A CA 1143713 A CA1143713 A CA 1143713A
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- pbw
- catalyst
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- 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
- C07C1/0435—Catalysts; their physical properties characterised by the composition containing a metal of group 8 or a compound thereof
- C07C1/044—Catalysts; their physical properties characterised by the composition containing a metal of group 8 or a compound thereof containing iron
-
- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- 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
- C07C1/0445—Preparation; Activation
-
- 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
- C07C2521/02—Boron or aluminium; Oxides or hydroxides thereof
- C07C2521/04—Alumina
-
- 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
- C07C2521/10—Magnesium; 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
- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/74—Iron group metals
- C07C2523/745—Iron
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A B S T R A C T
A process for the preparation of Fischer-Tropsch catalysts, co taining 30-75 pbw iron and 5-40 pbw magnesium per 100 pbw alumina by impregnating an alumina carrier with one or more aqueous solutions of salts of iron and of magnesium, followed by drying the composite, calcining it at a temperature of from 700 to 1200°C and reducing it.
A process for the preparation of Fischer-Tropsch catalysts, co taining 30-75 pbw iron and 5-40 pbw magnesium per 100 pbw alumina by impregnating an alumina carrier with one or more aqueous solutions of salts of iron and of magnesium, followed by drying the composite, calcining it at a temperature of from 700 to 1200°C and reducing it.
Description
1~37~3 A PROCESS FOR THE PREPARATIO~ OF
FISCXER-TROPSCX CATALYSTS
The invention relates to a process for the preparation of Fischer-Tropsch catalysts.
The preparation of hydrocarbons from a mixture of carbon monoxide and hydrogen by contacting this mixture at elevated temperature and pressure with a catalyst is referred to in the literature as the hydrocarbon synthesis according to Fischer-Tropsch. Catalysts which are often used for this purpose contain one or more metals from the iron group together with one or more promoters and sometimes a carrier material. The preparation of the Fischer-Tropsch catalysts can, in principle, be carried out in three ways, viz. by precipitation, by melting or by impregnation. The preparation of the catalysts by precipitation briefly consists in an aqueous solution of a salt of a metal from the iron group, to which, if desired, a salt of a promoter and a carrier material may have been added, being rendered alkaline, resulting in the precipitation of the catalyst.
One or more promoters and a carrier material may be added to this precipitate. The preparation of the catalysts by melting is effected, for instance, for iron catalysts by fusing iron oxide with one or more promoter oxides.
Both the precipitation route and the melting route are not very attractive procedures for the preparation of the Fischer-Tropsch catalysts, since their reproducibility is small. The nrecipitation route has the additional dis-advantage that it takes up a great deal of time, whilst the melting route requires much energy. ~loreover, the catalytic properties of the catalysts prepared by melting and by ' `~
1~3'7~3 precipitation, particularly the activit;y and stability, are often unsatisfactory. A much more attractive procedure for the preparation of the Fischer-TroE)sch catalysts is the impregnation route. It is easy to carry out, gives well reproducible results and, as a rule leads to catalysts with high activity and stability. The impregnation route briefly consists in a porous carrier being impregnated with one or more aqueous solution~ of salts of one or more metals from the iron group and of one ;r more promoters, followed by drying caIcining and reducing of the composite.
Many elements, ~uch as alkali metals, alkaline-earth metals, metals from Group VI B, Ti, Zr, Th, V, Mn and Cu, are eligible promoters for the catalysts prepared by impregnation.
A3 the carrier materials for the catalysts prepared by impregnation, amorphous as well as crystalline materials may be used. Suitable carriers are, inter alia, silica, alumina, zirconia, thoria, boria and combinations thereof, such as silica-alumina and silica-magnesia and further zeolites, such as mordenite, faujasite and zeolite-omega.
The Applicant has carried out an extensive investigation concerning the preparation of hydrocarbons from H2/C0 mixtures with an H2/C0 molar ratio smaller than 1.0, using Fischer-Tropsch catalysts prepared by impregnation. In the above-mentioned conversion the behaviour of these catalysts 25 was found to be greatly dependent on the following factors:
1) the nature of the metal from the iron group and the load used,
FISCXER-TROPSCX CATALYSTS
The invention relates to a process for the preparation of Fischer-Tropsch catalysts.
The preparation of hydrocarbons from a mixture of carbon monoxide and hydrogen by contacting this mixture at elevated temperature and pressure with a catalyst is referred to in the literature as the hydrocarbon synthesis according to Fischer-Tropsch. Catalysts which are often used for this purpose contain one or more metals from the iron group together with one or more promoters and sometimes a carrier material. The preparation of the Fischer-Tropsch catalysts can, in principle, be carried out in three ways, viz. by precipitation, by melting or by impregnation. The preparation of the catalysts by precipitation briefly consists in an aqueous solution of a salt of a metal from the iron group, to which, if desired, a salt of a promoter and a carrier material may have been added, being rendered alkaline, resulting in the precipitation of the catalyst.
One or more promoters and a carrier material may be added to this precipitate. The preparation of the catalysts by melting is effected, for instance, for iron catalysts by fusing iron oxide with one or more promoter oxides.
Both the precipitation route and the melting route are not very attractive procedures for the preparation of the Fischer-Tropsch catalysts, since their reproducibility is small. The nrecipitation route has the additional dis-advantage that it takes up a great deal of time, whilst the melting route requires much energy. ~loreover, the catalytic properties of the catalysts prepared by melting and by ' `~
1~3'7~3 precipitation, particularly the activit;y and stability, are often unsatisfactory. A much more attractive procedure for the preparation of the Fischer-TroE)sch catalysts is the impregnation route. It is easy to carry out, gives well reproducible results and, as a rule leads to catalysts with high activity and stability. The impregnation route briefly consists in a porous carrier being impregnated with one or more aqueous solution~ of salts of one or more metals from the iron group and of one ;r more promoters, followed by drying caIcining and reducing of the composite.
Many elements, ~uch as alkali metals, alkaline-earth metals, metals from Group VI B, Ti, Zr, Th, V, Mn and Cu, are eligible promoters for the catalysts prepared by impregnation.
A3 the carrier materials for the catalysts prepared by impregnation, amorphous as well as crystalline materials may be used. Suitable carriers are, inter alia, silica, alumina, zirconia, thoria, boria and combinations thereof, such as silica-alumina and silica-magnesia and further zeolites, such as mordenite, faujasite and zeolite-omega.
The Applicant has carried out an extensive investigation concerning the preparation of hydrocarbons from H2/C0 mixtures with an H2/C0 molar ratio smaller than 1.0, using Fischer-Tropsch catalysts prepared by impregnation. In the above-mentioned conversion the behaviour of these catalysts 25 was found to be greatly dependent on the following factors:
1) the nature of the metal from the iron group and the load used,
2) the nature of the promoter and the load used,
3) the nature of the carrier, and
4) the temperature treatment used Catalysts prepared by impregnation were found to have a very high activity and a very high stability for the conversion of H2/C0 mixtures with an H2/C0 molar ratio smaller than 1.0, if they contain 30-75 pbw iron and ~37~3
5-40 pbw magnesium per 100 pbw alumina and have been calcined at a temperature of from 700 to 1200C. These are novel catalysts.
The present patent application therefore relates to a process for the preparation of novel catalysts, in which catalysts containing 30-75 pbw iron and 5-40 pbw magnesium per lO0 pbw alumina are prepared by impregnating an alumina carrier with one or more aqueous solutions of salts of iron and of magnesium, followed by drying the composite, calcining it at a temperature of from 700 to 1200C and reducing it. The patent application further relates to the use of these catalysts for the preparation of hydrocarbons from an H2/C0 mixture with an H2/CO molar ratio smaller than 1.0 as the starting material.
The hydrocarbons are prepared by contacting the H2/C0 mixture at elevated temperature and pressure with a novel catalyst as hereinbefore described.
When for the above-mentioned application use is made of catalysts prepared according to the invention, preferred catalysts are those containing 40-60 pbw iron and 7.5-30 pbw magnesium per 100 pbw alumina. Further, preferance is given to catalysts which contain, in addition to iron and magnesium, a reduction promoter and a selectivity promoter. A suitable reduction promoter is copper. Suitable selectivity promoters are the alkali metals, in particular potassium. In addition to iron and magnesium it is preferred in the catalyst preparation according to the invention to incorporate 0.5-5 pbw copper and 1-5 pbw potassium per 100 pbw alumina into the catalyst by impregnation.
In the preparation of the catalysts the metal salts can be deposited on the carrier in one or more steps. Between the impregnation steps the material is dried and, optionally, calcined. Impregnation in more than one step may be necessary for the preparation of catalysts with a high meta] load.
The metal salts may be deposited on the , - 3 -~143~3 carrier separately or together from one solution. An attractive method of depositing the metal salts on the carrier i9 the dry impreenation technique, according to which a carrier is contacted with an aqueous solution of the salts concerned, which aqueous solution has a volume which is substantially the same as the pore volume of the carrier. Sorption of the aqueous solution by the carrier can be facilitated by heating the mixture. If this method is chosen for the preparation of catalysts with a high metal load, it may be neeessary to earry out more than one dry impregnation and to dry the material between the separate impregnation steps and, optionally, to ealeine it. The requirement of using a ca~eination temperature of 700-1200 C only applies to the ealeination immediately preceding the reduetion. If more calcinations are carried out in the eatalyst preparation, e.g. between several impregnation steps, these ealeinationq may, if desired, be carried out at a lower temperature. The ealcination immediately preceding the reduction i9 preferably carried 20 out at a temperature of 750-850 C. The eatalyst preparation is finished with a reduction. This reduetion is earried out at elevated temperature with a hydrogenous ga~, e.gt a mixture of hydrogen and nitrogen. The reduetion i9 preferably earried out at a temperature of 250-350 C.
The eatalysts prepared aeeording to the invention are pre-eminently suitable for the preparation of hydro-earbons from an H2/C0 mixture with an H2/CO molar ratio smaller than 1Ø Sueh H2/C0 mixtures ean very suitably be prepared by steam gasifieation of a carbon-containing material. Examples of such materials are brcwn coal, anthracite, eoke, erude mineral oil and fractions thereof and oils produced from tar sand and bituminous shale.
The steam gasification is preferably carried out at a temperature of from 900 to 1500C and a pressure of from ~143713 10 to 50 bar.
The preparation of hydrocarbons from an H2~C0 mixture with an H2/C0 molar ratio smaller than 1.0, using a Fischer-Tropsch catalyst according to the invention is preferably carried out at a temperature of from 200 to 350C and in particular of from 250 to 350C, a pressure of from 10 to 70 bar and in particular of from 20 to 50 bar and a space velocity of from 500 to 5000 and in particular of from 500 to 2500 Nl gas/l catalyst/h. The hydrocarbon preparation according to the invention can very suitably be carried out by contacting the feed in upward or downward direction through a vertically mounted reactor in which a fixed or a moving bed of the catalyst concerned is present.
The invention will now be explained with reference to the following example.
Example Eleven catalysts (A-H and 1-3) were prepared and tested for the hydrocarbon synthesis aceording to Fischer-Tropsch. The preparation of the catalysts was effectedby impregnating an alumina or silica earrier with aqueous solutions containing one or more of the following salts:
iron nitrate, magnesium nitrate, copper nitrate and potassium nitrate. In all impregnations the dry impregnation technique was used. The reduction of the catalysts was carried out at atmospheric pressure with an H2/N2 mixture in a volume ratio of 3:1 at a superficial gas rate of 1.6 m/s.
Further details about the preparation of the individual catalysts are given below.
Catalyst A
This eatalyst was prepared by impregnating an alumina carrier first with a solution of Mg(N03)2, followed by drying at 120 C and caleining for two hours at 400 C, and ~ 37~3
The present patent application therefore relates to a process for the preparation of novel catalysts, in which catalysts containing 30-75 pbw iron and 5-40 pbw magnesium per lO0 pbw alumina are prepared by impregnating an alumina carrier with one or more aqueous solutions of salts of iron and of magnesium, followed by drying the composite, calcining it at a temperature of from 700 to 1200C and reducing it. The patent application further relates to the use of these catalysts for the preparation of hydrocarbons from an H2/C0 mixture with an H2/CO molar ratio smaller than 1.0 as the starting material.
The hydrocarbons are prepared by contacting the H2/C0 mixture at elevated temperature and pressure with a novel catalyst as hereinbefore described.
When for the above-mentioned application use is made of catalysts prepared according to the invention, preferred catalysts are those containing 40-60 pbw iron and 7.5-30 pbw magnesium per 100 pbw alumina. Further, preferance is given to catalysts which contain, in addition to iron and magnesium, a reduction promoter and a selectivity promoter. A suitable reduction promoter is copper. Suitable selectivity promoters are the alkali metals, in particular potassium. In addition to iron and magnesium it is preferred in the catalyst preparation according to the invention to incorporate 0.5-5 pbw copper and 1-5 pbw potassium per 100 pbw alumina into the catalyst by impregnation.
In the preparation of the catalysts the metal salts can be deposited on the carrier in one or more steps. Between the impregnation steps the material is dried and, optionally, calcined. Impregnation in more than one step may be necessary for the preparation of catalysts with a high meta] load.
The metal salts may be deposited on the , - 3 -~143~3 carrier separately or together from one solution. An attractive method of depositing the metal salts on the carrier i9 the dry impreenation technique, according to which a carrier is contacted with an aqueous solution of the salts concerned, which aqueous solution has a volume which is substantially the same as the pore volume of the carrier. Sorption of the aqueous solution by the carrier can be facilitated by heating the mixture. If this method is chosen for the preparation of catalysts with a high metal load, it may be neeessary to earry out more than one dry impregnation and to dry the material between the separate impregnation steps and, optionally, to ealeine it. The requirement of using a ca~eination temperature of 700-1200 C only applies to the ealeination immediately preceding the reduetion. If more calcinations are carried out in the eatalyst preparation, e.g. between several impregnation steps, these ealeinationq may, if desired, be carried out at a lower temperature. The ealcination immediately preceding the reduction i9 preferably carried 20 out at a temperature of 750-850 C. The eatalyst preparation is finished with a reduction. This reduetion is earried out at elevated temperature with a hydrogenous ga~, e.gt a mixture of hydrogen and nitrogen. The reduetion i9 preferably earried out at a temperature of 250-350 C.
The eatalysts prepared aeeording to the invention are pre-eminently suitable for the preparation of hydro-earbons from an H2/C0 mixture with an H2/CO molar ratio smaller than 1Ø Sueh H2/C0 mixtures ean very suitably be prepared by steam gasifieation of a carbon-containing material. Examples of such materials are brcwn coal, anthracite, eoke, erude mineral oil and fractions thereof and oils produced from tar sand and bituminous shale.
The steam gasification is preferably carried out at a temperature of from 900 to 1500C and a pressure of from ~143713 10 to 50 bar.
The preparation of hydrocarbons from an H2~C0 mixture with an H2/C0 molar ratio smaller than 1.0, using a Fischer-Tropsch catalyst according to the invention is preferably carried out at a temperature of from 200 to 350C and in particular of from 250 to 350C, a pressure of from 10 to 70 bar and in particular of from 20 to 50 bar and a space velocity of from 500 to 5000 and in particular of from 500 to 2500 Nl gas/l catalyst/h. The hydrocarbon preparation according to the invention can very suitably be carried out by contacting the feed in upward or downward direction through a vertically mounted reactor in which a fixed or a moving bed of the catalyst concerned is present.
The invention will now be explained with reference to the following example.
Example Eleven catalysts (A-H and 1-3) were prepared and tested for the hydrocarbon synthesis aceording to Fischer-Tropsch. The preparation of the catalysts was effectedby impregnating an alumina or silica earrier with aqueous solutions containing one or more of the following salts:
iron nitrate, magnesium nitrate, copper nitrate and potassium nitrate. In all impregnations the dry impregnation technique was used. The reduction of the catalysts was carried out at atmospheric pressure with an H2/N2 mixture in a volume ratio of 3:1 at a superficial gas rate of 1.6 m/s.
Further details about the preparation of the individual catalysts are given below.
Catalyst A
This eatalyst was prepared by impregnating an alumina carrier first with a solution of Mg(N03)2, followed by drying at 120 C and caleining for two hours at 400 C, and ~ 37~3
-6-then impregnating with a solution of Fe(N03)3, Cu(N03)2 and KN03, followed by drying at 120 C, calcining for two hours at 400C and reduction at 280C.
Catalyst B
The preparation of this catalyst was performed in substantially the same way as the preparation of catalyst A, the difference beine that after the second calcination at 400C another calcination was carried out at 800C.
Catalyst C
The preparation of this catalyst wa~ performed in sub~tantially the same way a~ the preparation of catalyst A, the differences being that in the second impregnation a ; solution was used with higher concentration~ of Fe, Cu and K and that the ~econd calcination was carried out for 16 hours at 650 C.
Catalyst D
This catalyst was prepared by impregnating an alumina carrier with a solution of Mg(N03)2-, Fe(N03)3, Cu(N03)2 and KN03, followed by drying at 120 C, calcining for two hours at 400 C and reduction at 280 C.
Catalyst E
The preparation of this catalyst was performed in substantially the qame way as the preparation of catalyst D, the differences being that a solution with higher concentrations of Fe, Cu and K and not containing Mg was used, and that the calcination was carried out for fourteen hour3 at 800C.
Catalyst F
The preparation of this catalyst was performed in substantially the same way as the preparation of catalyst D, the difference~ being that silica was used as the carrier, that a solution was used with higher concentrations of Fe, Cu and K3 and that the calcination was carried out for fourteen hours at 800 C.
Catalyst B
The preparation of this catalyst was performed in substantially the same way as the preparation of catalyst A, the difference beine that after the second calcination at 400C another calcination was carried out at 800C.
Catalyst C
The preparation of this catalyst wa~ performed in sub~tantially the same way a~ the preparation of catalyst A, the differences being that in the second impregnation a ; solution was used with higher concentration~ of Fe, Cu and K and that the ~econd calcination was carried out for 16 hours at 650 C.
Catalyst D
This catalyst was prepared by impregnating an alumina carrier with a solution of Mg(N03)2-, Fe(N03)3, Cu(N03)2 and KN03, followed by drying at 120 C, calcining for two hours at 400 C and reduction at 280 C.
Catalyst E
The preparation of this catalyst was performed in substantially the qame way as the preparation of catalyst D, the differences being that a solution with higher concentrations of Fe, Cu and K and not containing Mg was used, and that the calcination was carried out for fourteen hour3 at 800C.
Catalyst F
The preparation of this catalyst was performed in substantially the same way as the preparation of catalyst D, the difference~ being that silica was used as the carrier, that a solution was used with higher concentrations of Fe, Cu and K3 and that the calcination was carried out for fourteen hours at 800 C.
7~3 ~: C _ yst G
The preparation of thi~ catalyst was performed in substantially the same way as tbe preparation of cata-lyst D, the differences being that a so:Lution with higher concentrations of Mg, Fe, Cu and K was used, and that the calcination was carried out for fourteen hours at 800C.
_talyst H
The preparation of this catalyst was performed in substantially the same way a~ the preparation of cata-lyst A, the difference being that the reduction wascarried out at 400 C.
CataLyst 1 The preparation of this catalyst was performed in substantially the same way as the preparation of catalyst A, the differences being that in the second impregnation a solution with higher concentrations of Fe, Cu and K
was used, that the second calcination was carried out for sixteen hours at 300C, and that the reduction was carried out at 325C.
Catalyst 2 The preparation of this catalyst was performed in substantially the same way as the preparation of cata-lyst A, the differences being that in the first impregnation a solution with a higher concentration of Mg was used, that in the second impregnation a solution with higher concentrations of Fe, Cu and K was used, that the second calcination was carried out for sixteen hours at 800C, and that the reduction was carried out at 300C.
Catalyst 3 The preparation of this catalyst was performed in substantially the same way as the preparation of cata-lyst A, the differences being that calcination after the '7~3 first impregnation step was omitted, that in the second impregn2tion a solution with higher concentrations of Fe, Cu and K was used, that the calcination after the second impregnation was carried out for sixteen hours at 800 C, and that the reduction was carried out at 325C.
The composition of the catalysts is shown in Table A.
Table A
Cat. No. Composition expressed in pbw Fe Mg Cu 2 3 SiO2 .
A 25 20 1.25 2 100 ---B 25 20 1.25 2 100 ---C 50 20 2.5 4 100 ---D 25 20 1.25 2 100 ---E 50 -- 2.5 4 100 -__ F 50 20 2.5 4 --- 100 G 50 50 2.5 4 100 ---H 25 20 1.25 2 100 ---1 50 20 2.5 4 100 ---2 50 `10 2.5 4 100 ---3 60 20 3 4 100 ___ _ - The teating of the catalysta A-H and 2 and 3 for the hydrocarbon aynthesis according to Fiacher-Tropsch from aynthesis gas with an H2/C0 molar ratio of 0.5 as the starting material was performed in a 250-ml reactor which contained a catalyst bed with a volume of 50 ml. The expe-rimenta were carried out at a temperature of 280 C, a preasure of 30 bar and a space velocity of 1000 Nl.l 1.h The results of these experimenta are shown in Table B.
~L14~7~3 .
g Table B
Exp. No. Cat. No. conversion of the ~ynthesis gas, %
After 25 hAfter 500 h _
The preparation of thi~ catalyst was performed in substantially the same way as tbe preparation of cata-lyst D, the differences being that a so:Lution with higher concentrations of Mg, Fe, Cu and K was used, and that the calcination was carried out for fourteen hours at 800C.
_talyst H
The preparation of this catalyst was performed in substantially the same way a~ the preparation of cata-lyst A, the difference being that the reduction wascarried out at 400 C.
CataLyst 1 The preparation of this catalyst was performed in substantially the same way as the preparation of catalyst A, the differences being that in the second impregnation a solution with higher concentrations of Fe, Cu and K
was used, that the second calcination was carried out for sixteen hours at 300C, and that the reduction was carried out at 325C.
Catalyst 2 The preparation of this catalyst was performed in substantially the same way as the preparation of cata-lyst A, the differences being that in the first impregnation a solution with a higher concentration of Mg was used, that in the second impregnation a solution with higher concentrations of Fe, Cu and K was used, that the second calcination was carried out for sixteen hours at 800C, and that the reduction was carried out at 300C.
Catalyst 3 The preparation of this catalyst was performed in substantially the same way as the preparation of cata-lyst A, the differences being that calcination after the '7~3 first impregnation step was omitted, that in the second impregn2tion a solution with higher concentrations of Fe, Cu and K was used, that the calcination after the second impregnation was carried out for sixteen hours at 800 C, and that the reduction was carried out at 325C.
The composition of the catalysts is shown in Table A.
Table A
Cat. No. Composition expressed in pbw Fe Mg Cu 2 3 SiO2 .
A 25 20 1.25 2 100 ---B 25 20 1.25 2 100 ---C 50 20 2.5 4 100 ---D 25 20 1.25 2 100 ---E 50 -- 2.5 4 100 -__ F 50 20 2.5 4 --- 100 G 50 50 2.5 4 100 ---H 25 20 1.25 2 100 ---1 50 20 2.5 4 100 ---2 50 `10 2.5 4 100 ---3 60 20 3 4 100 ___ _ - The teating of the catalysta A-H and 2 and 3 for the hydrocarbon aynthesis according to Fiacher-Tropsch from aynthesis gas with an H2/C0 molar ratio of 0.5 as the starting material was performed in a 250-ml reactor which contained a catalyst bed with a volume of 50 ml. The expe-rimenta were carried out at a temperature of 280 C, a preasure of 30 bar and a space velocity of 1000 Nl.l 1.h The results of these experimenta are shown in Table B.
~L14~7~3 .
g Table B
Exp. No. Cat. No. conversion of the ~ynthesis gas, %
After 25 hAfter 500 h _
8 H 76
9 2 91 89 Catalyst l was tested for 3150 h for the hydrocarbon ~ynthesis accordine to Fischer-Tropsch from a synthesis gas with an H2/C0 molar ratio of 0.6 as the starting material.
The experiment (exp. 11) was carried out in substantially the same way as the experiments 1-10, the difference being that the experiment was continued over a longer period, during which temperature and space velocity were varied.
The results of experiment 11 and the reaction conditions used are shown in Table C.
11437~3
The experiment (exp. 11) was carried out in substantially the same way as the experiments 1-10, the difference being that the experiment was continued over a longer period, during which temperature and space velocity were varied.
The results of experiment 11 and the reaction conditions used are shown in Table C.
11437~3
-10 Table C
Conditions during the experiment Result __ __ Period in Temp., Space velocity At run Conversion of run hours C Nl.l .h 1 hourthe synthesis gas, -- -- -- .. . . .
1350-1850 280 500 1a50 80 _ _ . _ _ _ Of the experiments mentioned in Tables B and C only experiments 9-11 were carried out with catalysts prepared according to the invention. In these experiments the catalysts showed both a very high activity and a very high stability. The experiments 1-8 were carried out with catalysts which are outside the scope of the invention. They have been included in the patent application for comparison.
The iron content of the catalyst~ A, D and H was too low and the temperature at which these catalysts had been calcined was too low. The results of experiments 1, 4 and 8 show that these catalysts had a low activity.
The catalysts ~, E, F and G contained too little iron, no magnesium, no alumina and too much magnesium respectively. The results of experiments 2, 5, 6 and 7 show that these catalysts had a low activity.
The temperature at which catalyst C had been calcined was too low. The result3 of experiment 3 show that this catalyst indeed had a high activity, but a very low stability.
Conditions during the experiment Result __ __ Period in Temp., Space velocity At run Conversion of run hours C Nl.l .h 1 hourthe synthesis gas, -- -- -- .. . . .
1350-1850 280 500 1a50 80 _ _ . _ _ _ Of the experiments mentioned in Tables B and C only experiments 9-11 were carried out with catalysts prepared according to the invention. In these experiments the catalysts showed both a very high activity and a very high stability. The experiments 1-8 were carried out with catalysts which are outside the scope of the invention. They have been included in the patent application for comparison.
The iron content of the catalyst~ A, D and H was too low and the temperature at which these catalysts had been calcined was too low. The results of experiments 1, 4 and 8 show that these catalysts had a low activity.
The catalysts ~, E, F and G contained too little iron, no magnesium, no alumina and too much magnesium respectively. The results of experiments 2, 5, 6 and 7 show that these catalysts had a low activity.
The temperature at which catalyst C had been calcined was too low. The result3 of experiment 3 show that this catalyst indeed had a high activity, but a very low stability.
Claims (6)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for the preparation of Fischer-Tropsch catalysts, char-acterized in that catalysts containing 30-75 pbw iron and 5-40 pbw magnesium per 100 pbw alumina are prepared by impregnating an alumina carrier with one or more aqueous solutions of salts of iron and of magnesium, followed by drying the composite, calcining it at a temperature of from 700 to l200°C
and reducing it.
and reducing it.
2. A process according to claim 1, characterized in that a catalyst is prepared containing 40-60 pbw iron per 100 pbw alumina and 7.5-30 pbw magnesium per 100 pbw alumina.
3. A process according to claim 1 or 2, characterized in that a catalyst is prepared containing 0.5-5 pbw copper per 100 pbw alumina.
4. A process according to claim 1 or 2, chatacterized in that a catalyst is prepared containing 1-5 pbw potassium per 100 pbw alumina.
5. A process for the preparation of hydrocarbons from an H2/CO mixture, characterized in that an H2/CO mixture with an H2/CO molar ratio smaller than 1.0 is contacted at elevated temperature and pressure with a catalyst containing 30-75 pbw iron and 5-40 pbw magnesium per 100 pbw alumina, said catalyst being prepared by impregnating an alumina carrier with one or more aqueous solutions of salts of iron and of magnesium, followed by drying the composite, calcining it at a temperature of from 700 to 1200°C and reducing it.
6. A process according to claim 5, characterized in that the preparation of hydrocarbons from the H2/CO mixture is carried out at a temperature of from 200 to 350°C, a pressure of from 10 to 70 bar and a space velocity of from 500 to 5000 Nl gas/l catalyst/h.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| NL7905480A NL190574C (en) | 1979-07-13 | 1979-07-13 | Process for the preparation of iron magnesium catalysts and their use in the preparation of hydrocarbons. |
| NL7905480 | 1979-07-13 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1143713A true CA1143713A (en) | 1983-03-29 |
Family
ID=19833538
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000350342A Expired CA1143713A (en) | 1979-07-13 | 1980-04-22 | Process for the preparation of fischer-tropsch catalysts |
Country Status (10)
| Country | Link |
|---|---|
| JP (1) | JPS5621647A (en) |
| AU (1) | AU535352B2 (en) |
| BE (1) | BE884143A (en) |
| CA (1) | CA1143713A (en) |
| DE (1) | DE3026390A1 (en) |
| FR (1) | FR2460711B1 (en) |
| GB (1) | GB2053713B (en) |
| IT (1) | IT1148709B (en) |
| NL (1) | NL190574C (en) |
| ZA (1) | ZA804187B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7815413B2 (en) | 2006-02-03 | 2010-10-19 | Ricon Corp. | Method of stowing wheelchair lift |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59146089U (en) * | 1983-03-17 | 1984-09-29 | オムロン株式会社 | envelope storage device |
| JPS6023330A (en) * | 1983-07-15 | 1985-02-05 | Daido Sanso Kk | Production of hydrocarbon |
| US4621162A (en) * | 1985-07-25 | 1986-11-04 | Phillips Petroleum Company | Method for conversion of C3 and C4 hydrocarbons to olefinic products |
| TW316852B (en) * | 1994-08-02 | 1997-10-01 | Mitsui Toatsu Chemicals | |
| DE69817777T2 (en) * | 1998-06-10 | 2004-07-29 | Lion Corp. | Process for the preparation of alkylene oxide adducts |
| US6504061B1 (en) | 1998-06-10 | 2003-01-07 | Lion Corporation | Alkoxylation catalyst and method for producing the same, and method for producing alkylene oxide adduct using the catalyst |
| JP5136831B2 (en) * | 2007-08-17 | 2013-02-06 | バイオマスエナジー株式会社 | Equipment for producing hydrocarbons from biomass |
| ITMI20092288A1 (en) * | 2009-12-23 | 2011-06-24 | Eni Spa | POROUS OXIDE WITH IMPROVED HYDROTHERMAL RESISTANCE SUITABLE FOR SUPPORT FOR FISCHER-TROPSCH CATALYSTS |
| CN102452878B (en) * | 2010-10-21 | 2014-03-05 | 中国石油化工股份有限公司 | Method for preparing low-carbon olefin by synthetic gas one-step technology |
| CN103551207B (en) * | 2013-11-01 | 2015-11-18 | 神华集团有限责任公司 | A kind of fixed fluidized bed or gas-solid bubbling bed fischer-tropsch catalysts reduction activation system and technique |
| CN105709742B (en) * | 2014-12-04 | 2019-04-09 | 神华集团有限责任公司 | A kind of iron-base fischer-tropsch catalyst and its preparation method and application and a kind of Fischer-Tropsch synthesis method |
| CN105214663B (en) * | 2015-09-02 | 2018-05-25 | 中国科学院上海高等研究院 | A kind of ferrum-based catalyst synthesized for low temperature syrup state bed Fischer Tropsch and its preparation method and application |
| CN105597776A (en) * | 2016-02-22 | 2016-05-25 | 神华集团有限责任公司 | Catalyst for Fischer-Tropsch synthesis and preparing method thereof |
| CN106040257B (en) * | 2016-05-06 | 2018-12-11 | 神华集团有限责任公司 | Fischer-tropsch synthetic catalyst and preparation method thereof and catalyst and Fischer-Tropsch synthesis method |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE888589C (en) * | 1944-03-15 | 1953-09-03 | Koppers Gmbh Heinrich | Process for increasing the calorific value of fuel gases through methanation |
| NL127928C (en) * | 1945-12-22 | |||
| NL7612460A (en) * | 1976-11-10 | 1978-05-12 | Shell Int Research | PROCESS FOR THE PREPARATION OF HYDROCARBONS. |
-
1979
- 1979-07-13 NL NL7905480A patent/NL190574C/en not_active IP Right Cessation
-
1980
- 1980-04-22 CA CA000350342A patent/CA1143713A/en not_active Expired
- 1980-07-03 BE BE1/9878A patent/BE884143A/en not_active IP Right Cessation
- 1980-07-11 FR FR8015466A patent/FR2460711B1/en not_active Expired
- 1980-07-11 DE DE19803026390 patent/DE3026390A1/en active Granted
- 1980-07-11 JP JP9405480A patent/JPS5621647A/en active Granted
- 1980-07-11 GB GB8022790A patent/GB2053713B/en not_active Expired
- 1980-07-11 IT IT23409/80A patent/IT1148709B/en active
- 1980-07-11 AU AU60343/80A patent/AU535352B2/en not_active Ceased
- 1980-07-11 ZA ZA00804187A patent/ZA804187B/en unknown
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7815413B2 (en) | 2006-02-03 | 2010-10-19 | Ricon Corp. | Method of stowing wheelchair lift |
Also Published As
| Publication number | Publication date |
|---|---|
| IT8023409A0 (en) | 1980-07-11 |
| NL190574B (en) | 1993-12-01 |
| FR2460711A1 (en) | 1981-01-30 |
| NL7905480A (en) | 1981-01-15 |
| GB2053713B (en) | 1983-04-20 |
| NL190574C (en) | 1994-05-02 |
| AU6034380A (en) | 1981-01-15 |
| AU535352B2 (en) | 1984-03-15 |
| ZA804187B (en) | 1981-07-29 |
| DE3026390A1 (en) | 1981-01-29 |
| JPS6352936B2 (en) | 1988-10-20 |
| DE3026390C2 (en) | 1989-11-02 |
| IT1148709B (en) | 1986-12-03 |
| BE884143A (en) | 1981-01-05 |
| FR2460711B1 (en) | 1986-08-01 |
| GB2053713A (en) | 1981-02-11 |
| JPS5621647A (en) | 1981-02-28 |
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