CA1198451A - Process for the production of hydrocarbons - Google Patents
Process for the production of hydrocarbonsInfo
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- CA1198451A CA1198451A CA000406247A CA406247A CA1198451A CA 1198451 A CA1198451 A CA 1198451A CA 000406247 A CA000406247 A CA 000406247A CA 406247 A CA406247 A CA 406247A CA 1198451 A CA1198451 A CA 1198451A
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- catalyst
- hydrocarbons
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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
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
-
- 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
- C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
- C07C2523/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals of the platinum group metals
- C07C2523/46—Ruthenium, rhodium, osmium or iridium
-
- 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
-
- 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
- C07C2523/75—Cobalt
-
- 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
- C07C2523/755—Nickel
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/03—Catalysts comprising molecular sieves not having base-exchange properties
- C07C2529/035—Crystalline silica polymorphs, e.g. silicalites
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
A B S T R A C T
PROCESS FOR THE PRODUCTION OF HYDROCARBONS
Process for the production of hydrocarbons from a mixture of carbon monoxide and hydrogen, using a catalyst combination con-taining one or more metal components with catalytic activity for the conversion of an H2/CO mixture into acyclic hydrocarbons, e.g.
Ru, Co, Fe and Ni, and as carrier a crystalline zeolite having a ZSM-5 structure.
The catalyst is prepared by ion-exchange, followed by was-hing, drying and calcining. The reaction product predominantly consists of C5-C12 hydrocarbons.
PROCESS FOR THE PRODUCTION OF HYDROCARBONS
Process for the production of hydrocarbons from a mixture of carbon monoxide and hydrogen, using a catalyst combination con-taining one or more metal components with catalytic activity for the conversion of an H2/CO mixture into acyclic hydrocarbons, e.g.
Ru, Co, Fe and Ni, and as carrier a crystalline zeolite having a ZSM-5 structure.
The catalyst is prepared by ion-exchange, followed by was-hing, drying and calcining. The reaction product predominantly consists of C5-C12 hydrocarbons.
Description
- ~19~3451 PROCESS FOR THE PROD~CTION OF HYDROCARBO~S
The invention relates to a process for the production of hydrocarbons from a mixture of carbon monoxide and hydrogen, using a catalyst combination containing one or more metal components with catalytic activity for the conversion of an H2/CO mixture 5 into acyclic hydrocarbons and a carrier consisting of a crystalline silicate zeolite having, in dehydrated form, the following overall composition, expressed in moles of the oxides (l.O ' 0.3) (R)2/nO./a Me203/.y(d SiO2 + e GeO2), where R = one or more mono- or bivalent cations, Me = at leastone trivalent metal O ~ a ~ 1 y ~ 12 d 3 0.1, e 3 O, d + e = 1, and n = the valency of R, and having an ~-ray powder diffraction pattern showing, inter alia, the reflections given in Table A.
Table A
20 2~ Relative intensity 7.8 - 8.2 S
8.7 - 9.1 11.8 - 12.1 W
12.4 - 12.7 W
25 14.6 - 14.9 W
15.4 - 15.7 W
15.8 - 16.1 W
17.6 - 17.9 W
19.2 - 19.5 W
30 20.2 - 20.6 W
20.7 - 21.1 W
23.1 - 23.4 VS
~J
1198~5~
23.8 - 24.1 S
24.2 - 24.8 29.7 - 30.1 M
The values given in Table A have been determined according to 5 standard methods. Radiation: Cu-K, wavelength: 0.15418 nm. The letters in Table A used to indicate the relative intensities have the following meanings: VS = very strong; S = strong; M =
moderate; W = weak; 0 = angle according to Bragg's law.
The complete X-ray powder diffraction pattern of a silicate 10 to be used in the process according to the invention is given in Table B. (Radiation: Cu-K, wavelength: 0.15418 nm).
Table B
29 Relative intensity description of (100. I/Io) the reflection 8.00 55 SP
8.90 36 SP
9.10 20 SR
11.95 7 NL
12.55 3 NL
13.25 4 NL
13.95 10 NL
14.75 9 BD
15.55 7 BD
15.95 9 BD
17.?5 5 BD
19.35 6 NL
20.40 9 NL
20.90 10 NL
21.80 4 NL
22.25 8 NL
23.25 100* SP
23.95 45 SP
24.40 27 SP
~A
11984S~
25.90 11 BD
26.70 9 BD
27.50 4 NL
29.30 7 NL
29.90 11 BD
31.25 2 NL
32.75 4 NL
NL
36.05 5 BD
BD
* lo = intensity of the strongest separated reflection occurring in the pattern.
The letters in Table B used to describe the reflections have the following meanings: SP = sharp; SR = shoulder; NL = normal; BD
= broad; ~ = angle according to Bragg's law.
In an investigation by the Applicant concerning this process it was found that it has two drawbacks. In the first place, when using space velocities acceptable in actual practice, the conversion of the H2/C0 mixture is unsatisfactory. Further, the process yields a product substantially consisting of hydrocarbons with less than 5 carbon atoms in the molecule and too few hydrocarbons with 5-12 carbon atoms in the molecule.
Further investigation by the Applicant concerning this process has shown that the two above-mentioned drawbacks can be obviated by preparing the catalyst used by ion-exchange i.e. by contacting the feed with a catalyst containing one or more metal components with catalytic activity for the conversion of an H2/C0 mixture into acyclic hydrocarbons, which metal components are preferably chosen from the group formed by Fe, Ni, Co, and Ru, and which component(s) is/are deposited in the crystalline zeolite by ionexchange. In this manner it is not only achieved that, when using space velocities acceptable in actual practice, a higher conversion of the H2/C0 mixture is obtained, but moreover that the ~98~S~
reaction product consists predominantly of hydrocarbons with 5-12 carbon atoms in the molecule.
The present application therefore relates to a process for the production of hydrocarbons, from a mixture of carbon monoxide and hydrogen, using a catalyst combination containing one or more metal components with catalytic activity for the conversion of an H2/C0 mixture into acyclic hydrocarbons and a carrier, consisting of a crystalline silicate zeolite having a dehydrated form, the following overall composition, expressed in moles of the oxides (1.0 ~ 0.3)(R)2/nO./ a Me203/.
y(d SiO2 + e GeO2), where R = one or more mono- or bivalent cations, Me = at least one trivalent metal l >a ~0, y ~12, d ~0.1, e 30, d + e - 1, and n = the valency of R
and having an X-ray powder diffraction pattern showing, inter alia, the reflections given in Table A, characterized in that, the metal component(s) has (have) been combined with the carrier by ion-exchange followed by washing, drying and calcining.
In the process according to the invention the starting material is an H2/C0 mixture. Such H2/C0 mixtures can very suit-ably be prepared by steam gasification or partial combustion of a carbon containing material. Examples of such materials are wood, peat, brown coal, bituminous coal, anthracite, coke, crude mineral oil and fractions thereof as well as tars and oils extracted from tar sand and bituminous shale. The steam gasification 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 preferred to start from an H2/CO mixture with an H2/C0 molar ratio of more than 0.25 and less than 6.
~984~1 The catalyst comblnations used in the process according to the inven~
tion contain~ ~n add~ti~on to metql comp~nents ~$th catalytic activity for hydro-carbon synthesis, at least one crystalline silicate, preferably belonging to the "Pentasil" group of crystalline silicates. These silicates are described in the "Atlas of zeolite structure Types" by W.M. Meier and D~H. 01son (1978), Polycrystal Book Service, Pittsburgh, Pa,, and by E M. Flaninger, J.M Bennet~
R.M. Grose, J.P, Cohen and J.V. Smith, Nature (London), 1978, 271, p 512 and by L.V.C, Rees, "Proceedings of the Fifth International Conference on Zeolites", (Naples), 2-6 June, 1980, p 562.
Particularly suitable silicates for the process according to the inven-tion is the crystalline "Silicalite" mentioned in U.S. patent specification No.
4,061,724 and the crystalline aluminosilicate ZSM-5, which is described in U.S
patent specification No. 3,702,886. Other preferred carriers for the catalyst to be used in the process according to the invention are a crystalline iron silicate (CIS) (which has been described in British patent specification No 1,555,928 and U.S. patent specification No. 4,208,305), a crystalline gallium silicate (Canadian patent No. 1,141,779), and a crystalline cobalt silicate (Canadian patent application No. 398,341).
In Canadian patent No. 1,142,159 a further crystalline silicate is described which is very suitable as a catalyst carrier in the process according to the invention. This silicate has the following composition expressed in moles of oxides:
p (0 9 + 0-3) M2~n-P (aX23 2 3 Si02 in which M = H and/or alkali and/or alkaline earth metal;
X = Rh, Cr and/or Sc;
Y = Al, Fe and/or Ga;
a ~ 0.5; b ~ 0; a + b = 1;
0 < p ~ 1; n = valency of M.
~ lL19~3~5~
The catalyst combinations used in the process according to the invention contain one or more metal com?onents with catalytic activity for the conversion of an H2/CO mixture into acyclic hydrocarbons.
Catalyst components capable of converting an H2/CO mixture into mainly acyclic hydrocarbons are known in the literature as Fischer- Tropsch catalyst. Such catalyst components comprise one or more metals of the iron group or ruthenium together, optionally with one or more promoters to increase the activity and/or selec-10 tivity. Suitable catalysts contain 0.1-10% by weight of ruthenium and/or 0.05-10~ by weight of one or more metals of the iron group together with one or more promoters in a quantity of 1-50% of the quantity of the iron group metals present on the catalyst. As promoters for the catalysts according to the invention a large 15 number of elements are suitable. The following may be mentioned as examples: alkali metals, alkaline earth metals, metals of group VIB (W, Mo, Cr), Ti, Zr, Al, Si, As, V, Mn, Cu, Ag, Zn, Cd, Bi, Pb, Sn, Ce, Th and U. One or more of these promoters are prefer-ably introduced into the carrier by ion-exchange. Very suitable 20 promoter combinations for the iron catalyst component used accor-ding to the invention consist of an alkali metal such as K, a readily reducible metal such as Cu or Ag and optionally a metal difficult to reduce, such as Al or Zn. An example of a very suitable iron catalyst co~ponent to be used according to the 25 invention is a catalyst component containing iron, potassium and copper in the crystalline silicate zeolite as carrier. If in the process according to the invention use is made of an iron catalyst component containing K as selectivity promoter, a catalyst con-taining not more than 0.15 g of K per g of Fe is preferred, since 30 it has been found that if higher K concentrations are applied the selectivity does not rise further while the stability substan-tially decreases as a result of carbon deposition on the catalyst.
Very suitable promoter combinations for cobalt catalyst components to be used according to the invention consist of an alkaline earth 35 metal and Th, U or Ce.
1~98~5~
An example of a very suitable cobalt catalyst component to be used according to the invention is a catalyst containing cobalt, mag-nesium and thorium in the crystalline silicate zeolite as carrier.
Other very suitable cobalt catalyst components to be used accor-ding to the invention are catalysts containing Co/Cr, Co/Zr, Co/Znor Co/Mg in the crystalline silicate zeolite as carrier. Very suitable promoters for nickel catalyst components to be used according to the invention are Al, Mn, Th, W and U.
If in the process according to the invention it is intended to use a catalyst combination of which the catalyst component having Fischer-Tropsch activity is iron, an iron catalyst compo-nent is preferably chosen containing a promoter combination consisting of an alkali metal, a readily reducible metal such as copper or silver and optionally a metal difficult to reduce, such as aluminium or zinc. A very suitable iron catalyst component for the present purpose is a catalyst prepared by ion-exchange con-taining iron, potassium and copper into the crystalline silicate zeolite as carrier. If in the catalyst combination iron is used as catalyst component having the required Fischer-Tropsch activity, the process according to the invention is preferably carried out at a temperature of 250-325C and a pressure of 20-100 bar.
If in the process according to the invention it is intended to use a catalyst combination of which the catalyst component having the required Fischer-Tropsch activity is cobalt, a cobalt catalyst component is preferred containing a promoter combination consisting of an alkaline earth metal and chromium, thorium, uranium or cerium.
A very suitable cobalt catalyst for the present purpose is a catalyst prepared by ion-exchange and containing cobalt, magnesium and thorium in the crystalline silicate zeolite as carrier. Other very suitable cobalt catalysts prepared by ion-exchange are catalysts containing, in addition to cobalt, one of the elements chromium, titanium, zirconium and zinc in the crystalline silicate zeolite as carrier.
~98~
If in the catalyst combination cobalt is used as catalyst having the required Fischer-Tropsch activity, the process accor-ding to the invention is preferably carried out at a temperature of 220-300C and a pressure of 10-100 bar.
Very suitable catalysts for the process according to the invention are a) catalysts containing 0.05-10 parts by weight of iron and 0.025-5 parts by weight of magnesium per 100 parts by weight of crystalline silicate zeolite carrier and prepared by ion-exchange of the carrier with one or more solutions of salts of iron and of magnesium followed by washing and drying the composition, calci-ning it at a temperature of 300-600C and reducing it. Special preference is given to such catalysts containing, in addition to 0.1-5 parts by weight of iron and 0.05-2.5 parts by weight of magnesium, 0.05-2.5 parts by weight of copper as reduction promo-ter and 0.1-1.5 parts by weight of potassium as selectivity pro-moter per 100 parts by weight of carrier and calcined at 400-500C
and reduced at 250-450C.
b) catalysts containing 0.05-10 parts by weight of cobalt and 0.01-2.5 parts by weight of chromium per 100 parts by weight of crystalline silicate zeolite carrier and prepared by ion-exchange of the carrier with one or more solutions of salts of cobalt and of chromium followed by washing and drying the composition, calcining it and reducing it at a temperature of 300-750C.
~articular preference is given to such catalyst containing, in addition to 0.1-5 parts by weight of cobalt and 0.05-1 parts by weight of chromium, calcined at 300-700C and reduced at 300-700C;
c) catalysts containing 0.05-10 parts by weight of cobalt and 0.01-2.5 parts by weight of zirconium, titanium or chromium per 100 parts by weight of crystalline silicate zeolite carrier and prepared by ion-exchange of a silicate carrier with one or more solutions of salts of cobalt and zirconium, titanium or chromium, followed by washing and drying the composition, calcining at 350-700C and reducing it at 200-700C.
~198451 In the process according to the invention catalysts are used that are prepared by ion-exchange of the carrier, preferably with one or more aqueous solutions of salts of ruthenium or of metals of the iron group and salts of promoters, followed by washing with 5 washing water, drying and calc~ning the composition.
The ion-exchange ability of crystalline metal silicates is well known. In crystalline metal silicates, the electrovalence of the metal in the structure is balanced by the inclusion of a cation in the crystal. The cation is most commonly an alkali metal, such as sodium or potassium. The cations of either the synthetic or naturally occuring aluminosilicates can be exchanged for the mono- or polyvalent cations which are of a suitable physical size and configuration to diffuse into the intracrystal-line passages in the silicate structure~ The original cation can be replaced by another cation e.g. by a hydrogen ion or by an am~onium ion. In general, any suitable acid or salt solution such as a sulphate or nitrate can be used as a source of cations to be exchanged into the silicate.
The theoretical exchange capacity of the crystalline silicate is represented by the number of equivalents of cations, e.g.
sodium ions,,which balance the electroneutrality of the crystal-line silicate. The exchange capacity varies according to the particular type of sieve involved. In practice, not all of the cations in the silicate are readily replaced with the desired cations, so that the effective exchange capacity is often somewhat less than the theoretical exchange capacity. The extent of the exchange depends on such factors as the type of sieve, cations in the sieve, cations to be exchanged, type of solvent (water, alcohol) and temperature of exchange. Clearly, there is a limit to the amount of catalytically active metal which can be ion-exchanged into the crystalline silicate.
The ion-exchange is preferably carried out at a temperature in the range from 20 to 200C.
Following the ion-exchange step, the ion-exchange solution is removed from the zeolite con~aining the catalytically active metal 45~
exchanged therein, for example by filtration. The zeolite is then washed preferably with the ion-exchange solvent to remove any unreacted metal and the wash liquid is removed, for example by filtration. The zeolite cake from which the wash liquid has been removed usually contains about 50% solids. Either with or without further adjustment of the solvent content, the zeolite can be shaped to desired size. If desired one or more binders and/or extrusion aids can be added. The zeolite may then be dried, and the shaped catalyst is calcined, at a temperature of from about 10 300 to about 600C, to form the ~inished catalyst.
In the preparation of the catalysts the metals can be deposi-ted on the carrier in one or more steps. Between the separate ion-exchange steps the material may be dried. For the preparation of catalysts with a high metal content the use of a multi-step 15 technique may be necessary. The salts of the iron group metals and the salts of the promoters can be deposited on the carrier separate-ly from different solutions or together from one solution.
In the process according to the invention the intention is to convert the largest possible quartity of the C0 prese~t in the 20 feed into hydrocarbons over a catalyst containing one or more metal components with catalytic activity for the conversion of an H2/C0 mixture into hydrocarbons, which metal components are chosen from the group formed by iron, cobalt, nickel and ruthenium. To this end the H2/C0 molar ratio in the feed is suitably at least 25 1.0 and preferably 1.25-2.25.
The process according to the 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 30 catalyst bed. The process can also be carried out using a suspen-sion of the catalyst or catalyst combination in a hydrocarbon oil.
The process is preferably carried out under the following condi-tions: a temperature of 125-350C and in particular of 175-275C
34~
and a pressure of 1-150 bar and in particular of 5-100 bar.
The invention will now be explained with reference to the following Examples.
Example 1 The crystalline aluminosilicate ZSM-5 was prepared according to the recipe as described in U.S. patent specification No.
3,702,886. The silicate obtained was first transférred into the ammonium form by ion-exchange with a 2Normal NH4N03 solution. The ammonium form of the ZSM-5 was ion exchanged with an aqueous solution of RuC13 (5% wt.) during 48 hours. The catalyst was then washed with water, dried and subjected to a 2-hour calcination at 500C with air at atmospheric pressure and reduced for two hours at 280C with H2 at 4 bars. The resulting catalyst had the follo-wing composition:
1.7 Ru/66 SiO2/1 A12O3 (parts by weight). A gas mix~ure consisting of H2 and C0 (H2/CO = 1) was passed over this catalyst applying the following conditions:
gas hourly space velocity: 1000 1 (NTP)/lh pressure: 20 bar 20 temperature: 260C
The conversion of H2 + C0 into hydrocarbons was 20.0% wt. The space-time yield was 67 grams of hydrocarbons per litre of cata-lyst volume per hour.
The selectivity is given in the following table:
C 1 + C2 4% wt.
C 3 + C4 : 16% wt.
C 5 - C12: 78% wt.
C13 - C19: 1.5% wt.
C20 + : 0.5% wt. From this table it can be seen that the 30 yield of desired hydrocarbons boiling in the gasoline boiling range (C5-C12) is very high compared with those boiling below and above the preferred range.
The condensed liquid phase contained 40% wt aromatics, only trace amounts of durene being present.
S~
Comparative experiment 1 The ZSM-5 was prepared as shown in Example 1. It was impreg-nated with an aqueous solution of ruthenium chloride, dried, calcined during 2 hours at 500C in air and reduced for 2 hours at 280C with hydrogen at 4 bar pressure in order to obtain a cata-lyst having the composition: 1.7 Ru/66 SiO2/1 A1203 (parts by weight). Using this catalyst under the conditions described in Example 1 hydrocarbons were formed from a H2/C0 gas mixture (H2/C0 = 1). The conversion was 13% wt. The space-time yield was 26 grams 10 of hydrocarbons per litre of catalyst per hour.
The selectivity was:
C1 + C2 : 25% wt.
C3 + C4 : 40% wt.
C5 - C12: 35% wt.
15 C13 _ C19: 0% wt.
C20 + : 0% wt.
An inferior result as regards the yield of gasoline components (C5-C12) was thus obtained. Moreover no aromatics were present in the product.
20 Example 2 Crystalline silica was prepared according to the recipe of silicalite disclosed in column 6 of U.S. patent specification 4,061,724.
The crystalline silica obtained was first transferred to 25 ammonium form by ion-exchange with a 2N NH4 N03 solution. The a~monium form was ion-exchanged with an aqueous solution of Co (NH3)6(N03)2 (15% wt) during 24 hours.
The catalyst was then washed with water, dried, calcined two hours a~ 500C and subjected to a 24 hours' reduction with hydro-30 gen at 575C and 1 bar abs.
This catalyst had the following composition: 100 SiO2.2.5 Co (parts by weight).
A H2/C0 mixture (H2/C0 = 1) was passed over this catalyst applying the following conditions.
gas hourly space velocity: 1000 1 (NTP/1 h) 45~
pressure: 20 bar temperature: 260C
The conversion of H2 + C0 into hydrocarbons was 51% ~t. The space-time yield was 112 grams of hydrocarbons per litre of catalyst per hour.
The selectivity is given in the following table:
Cl + C2 16%
C3 + C4 15%
C5 C12: 58%
C 3 - Clg: 8%
C20 + : 3%
The invention relates to a process for the production of hydrocarbons from a mixture of carbon monoxide and hydrogen, using a catalyst combination containing one or more metal components with catalytic activity for the conversion of an H2/CO mixture 5 into acyclic hydrocarbons and a carrier consisting of a crystalline silicate zeolite having, in dehydrated form, the following overall composition, expressed in moles of the oxides (l.O ' 0.3) (R)2/nO./a Me203/.y(d SiO2 + e GeO2), where R = one or more mono- or bivalent cations, Me = at leastone trivalent metal O ~ a ~ 1 y ~ 12 d 3 0.1, e 3 O, d + e = 1, and n = the valency of R, and having an ~-ray powder diffraction pattern showing, inter alia, the reflections given in Table A.
Table A
20 2~ Relative intensity 7.8 - 8.2 S
8.7 - 9.1 11.8 - 12.1 W
12.4 - 12.7 W
25 14.6 - 14.9 W
15.4 - 15.7 W
15.8 - 16.1 W
17.6 - 17.9 W
19.2 - 19.5 W
30 20.2 - 20.6 W
20.7 - 21.1 W
23.1 - 23.4 VS
~J
1198~5~
23.8 - 24.1 S
24.2 - 24.8 29.7 - 30.1 M
The values given in Table A have been determined according to 5 standard methods. Radiation: Cu-K, wavelength: 0.15418 nm. The letters in Table A used to indicate the relative intensities have the following meanings: VS = very strong; S = strong; M =
moderate; W = weak; 0 = angle according to Bragg's law.
The complete X-ray powder diffraction pattern of a silicate 10 to be used in the process according to the invention is given in Table B. (Radiation: Cu-K, wavelength: 0.15418 nm).
Table B
29 Relative intensity description of (100. I/Io) the reflection 8.00 55 SP
8.90 36 SP
9.10 20 SR
11.95 7 NL
12.55 3 NL
13.25 4 NL
13.95 10 NL
14.75 9 BD
15.55 7 BD
15.95 9 BD
17.?5 5 BD
19.35 6 NL
20.40 9 NL
20.90 10 NL
21.80 4 NL
22.25 8 NL
23.25 100* SP
23.95 45 SP
24.40 27 SP
~A
11984S~
25.90 11 BD
26.70 9 BD
27.50 4 NL
29.30 7 NL
29.90 11 BD
31.25 2 NL
32.75 4 NL
NL
36.05 5 BD
BD
* lo = intensity of the strongest separated reflection occurring in the pattern.
The letters in Table B used to describe the reflections have the following meanings: SP = sharp; SR = shoulder; NL = normal; BD
= broad; ~ = angle according to Bragg's law.
In an investigation by the Applicant concerning this process it was found that it has two drawbacks. In the first place, when using space velocities acceptable in actual practice, the conversion of the H2/C0 mixture is unsatisfactory. Further, the process yields a product substantially consisting of hydrocarbons with less than 5 carbon atoms in the molecule and too few hydrocarbons with 5-12 carbon atoms in the molecule.
Further investigation by the Applicant concerning this process has shown that the two above-mentioned drawbacks can be obviated by preparing the catalyst used by ion-exchange i.e. by contacting the feed with a catalyst containing one or more metal components with catalytic activity for the conversion of an H2/C0 mixture into acyclic hydrocarbons, which metal components are preferably chosen from the group formed by Fe, Ni, Co, and Ru, and which component(s) is/are deposited in the crystalline zeolite by ionexchange. In this manner it is not only achieved that, when using space velocities acceptable in actual practice, a higher conversion of the H2/C0 mixture is obtained, but moreover that the ~98~S~
reaction product consists predominantly of hydrocarbons with 5-12 carbon atoms in the molecule.
The present application therefore relates to a process for the production of hydrocarbons, from a mixture of carbon monoxide and hydrogen, using a catalyst combination containing one or more metal components with catalytic activity for the conversion of an H2/C0 mixture into acyclic hydrocarbons and a carrier, consisting of a crystalline silicate zeolite having a dehydrated form, the following overall composition, expressed in moles of the oxides (1.0 ~ 0.3)(R)2/nO./ a Me203/.
y(d SiO2 + e GeO2), where R = one or more mono- or bivalent cations, Me = at least one trivalent metal l >a ~0, y ~12, d ~0.1, e 30, d + e - 1, and n = the valency of R
and having an X-ray powder diffraction pattern showing, inter alia, the reflections given in Table A, characterized in that, the metal component(s) has (have) been combined with the carrier by ion-exchange followed by washing, drying and calcining.
In the process according to the invention the starting material is an H2/C0 mixture. Such H2/C0 mixtures can very suit-ably be prepared by steam gasification or partial combustion of a carbon containing material. Examples of such materials are wood, peat, brown coal, bituminous coal, anthracite, coke, crude mineral oil and fractions thereof as well as tars and oils extracted from tar sand and bituminous shale. The steam gasification 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 preferred to start from an H2/CO mixture with an H2/C0 molar ratio of more than 0.25 and less than 6.
~984~1 The catalyst comblnations used in the process according to the inven~
tion contain~ ~n add~ti~on to metql comp~nents ~$th catalytic activity for hydro-carbon synthesis, at least one crystalline silicate, preferably belonging to the "Pentasil" group of crystalline silicates. These silicates are described in the "Atlas of zeolite structure Types" by W.M. Meier and D~H. 01son (1978), Polycrystal Book Service, Pittsburgh, Pa,, and by E M. Flaninger, J.M Bennet~
R.M. Grose, J.P, Cohen and J.V. Smith, Nature (London), 1978, 271, p 512 and by L.V.C, Rees, "Proceedings of the Fifth International Conference on Zeolites", (Naples), 2-6 June, 1980, p 562.
Particularly suitable silicates for the process according to the inven-tion is the crystalline "Silicalite" mentioned in U.S. patent specification No.
4,061,724 and the crystalline aluminosilicate ZSM-5, which is described in U.S
patent specification No. 3,702,886. Other preferred carriers for the catalyst to be used in the process according to the invention are a crystalline iron silicate (CIS) (which has been described in British patent specification No 1,555,928 and U.S. patent specification No. 4,208,305), a crystalline gallium silicate (Canadian patent No. 1,141,779), and a crystalline cobalt silicate (Canadian patent application No. 398,341).
In Canadian patent No. 1,142,159 a further crystalline silicate is described which is very suitable as a catalyst carrier in the process according to the invention. This silicate has the following composition expressed in moles of oxides:
p (0 9 + 0-3) M2~n-P (aX23 2 3 Si02 in which M = H and/or alkali and/or alkaline earth metal;
X = Rh, Cr and/or Sc;
Y = Al, Fe and/or Ga;
a ~ 0.5; b ~ 0; a + b = 1;
0 < p ~ 1; n = valency of M.
~ lL19~3~5~
The catalyst combinations used in the process according to the invention contain one or more metal com?onents with catalytic activity for the conversion of an H2/CO mixture into acyclic hydrocarbons.
Catalyst components capable of converting an H2/CO mixture into mainly acyclic hydrocarbons are known in the literature as Fischer- Tropsch catalyst. Such catalyst components comprise one or more metals of the iron group or ruthenium together, optionally with one or more promoters to increase the activity and/or selec-10 tivity. Suitable catalysts contain 0.1-10% by weight of ruthenium and/or 0.05-10~ by weight of one or more metals of the iron group together with one or more promoters in a quantity of 1-50% of the quantity of the iron group metals present on the catalyst. As promoters for the catalysts according to the invention a large 15 number of elements are suitable. The following may be mentioned as examples: alkali metals, alkaline earth metals, metals of group VIB (W, Mo, Cr), Ti, Zr, Al, Si, As, V, Mn, Cu, Ag, Zn, Cd, Bi, Pb, Sn, Ce, Th and U. One or more of these promoters are prefer-ably introduced into the carrier by ion-exchange. Very suitable 20 promoter combinations for the iron catalyst component used accor-ding to the invention consist of an alkali metal such as K, a readily reducible metal such as Cu or Ag and optionally a metal difficult to reduce, such as Al or Zn. An example of a very suitable iron catalyst co~ponent to be used according to the 25 invention is a catalyst component containing iron, potassium and copper in the crystalline silicate zeolite as carrier. If in the process according to the invention use is made of an iron catalyst component containing K as selectivity promoter, a catalyst con-taining not more than 0.15 g of K per g of Fe is preferred, since 30 it has been found that if higher K concentrations are applied the selectivity does not rise further while the stability substan-tially decreases as a result of carbon deposition on the catalyst.
Very suitable promoter combinations for cobalt catalyst components to be used according to the invention consist of an alkaline earth 35 metal and Th, U or Ce.
1~98~5~
An example of a very suitable cobalt catalyst component to be used according to the invention is a catalyst containing cobalt, mag-nesium and thorium in the crystalline silicate zeolite as carrier.
Other very suitable cobalt catalyst components to be used accor-ding to the invention are catalysts containing Co/Cr, Co/Zr, Co/Znor Co/Mg in the crystalline silicate zeolite as carrier. Very suitable promoters for nickel catalyst components to be used according to the invention are Al, Mn, Th, W and U.
If in the process according to the invention it is intended to use a catalyst combination of which the catalyst component having Fischer-Tropsch activity is iron, an iron catalyst compo-nent is preferably chosen containing a promoter combination consisting of an alkali metal, a readily reducible metal such as copper or silver and optionally a metal difficult to reduce, such as aluminium or zinc. A very suitable iron catalyst component for the present purpose is a catalyst prepared by ion-exchange con-taining iron, potassium and copper into the crystalline silicate zeolite as carrier. If in the catalyst combination iron is used as catalyst component having the required Fischer-Tropsch activity, the process according to the invention is preferably carried out at a temperature of 250-325C and a pressure of 20-100 bar.
If in the process according to the invention it is intended to use a catalyst combination of which the catalyst component having the required Fischer-Tropsch activity is cobalt, a cobalt catalyst component is preferred containing a promoter combination consisting of an alkaline earth metal and chromium, thorium, uranium or cerium.
A very suitable cobalt catalyst for the present purpose is a catalyst prepared by ion-exchange and containing cobalt, magnesium and thorium in the crystalline silicate zeolite as carrier. Other very suitable cobalt catalysts prepared by ion-exchange are catalysts containing, in addition to cobalt, one of the elements chromium, titanium, zirconium and zinc in the crystalline silicate zeolite as carrier.
~98~
If in the catalyst combination cobalt is used as catalyst having the required Fischer-Tropsch activity, the process accor-ding to the invention is preferably carried out at a temperature of 220-300C and a pressure of 10-100 bar.
Very suitable catalysts for the process according to the invention are a) catalysts containing 0.05-10 parts by weight of iron and 0.025-5 parts by weight of magnesium per 100 parts by weight of crystalline silicate zeolite carrier and prepared by ion-exchange of the carrier with one or more solutions of salts of iron and of magnesium followed by washing and drying the composition, calci-ning it at a temperature of 300-600C and reducing it. Special preference is given to such catalysts containing, in addition to 0.1-5 parts by weight of iron and 0.05-2.5 parts by weight of magnesium, 0.05-2.5 parts by weight of copper as reduction promo-ter and 0.1-1.5 parts by weight of potassium as selectivity pro-moter per 100 parts by weight of carrier and calcined at 400-500C
and reduced at 250-450C.
b) catalysts containing 0.05-10 parts by weight of cobalt and 0.01-2.5 parts by weight of chromium per 100 parts by weight of crystalline silicate zeolite carrier and prepared by ion-exchange of the carrier with one or more solutions of salts of cobalt and of chromium followed by washing and drying the composition, calcining it and reducing it at a temperature of 300-750C.
~articular preference is given to such catalyst containing, in addition to 0.1-5 parts by weight of cobalt and 0.05-1 parts by weight of chromium, calcined at 300-700C and reduced at 300-700C;
c) catalysts containing 0.05-10 parts by weight of cobalt and 0.01-2.5 parts by weight of zirconium, titanium or chromium per 100 parts by weight of crystalline silicate zeolite carrier and prepared by ion-exchange of a silicate carrier with one or more solutions of salts of cobalt and zirconium, titanium or chromium, followed by washing and drying the composition, calcining at 350-700C and reducing it at 200-700C.
~198451 In the process according to the invention catalysts are used that are prepared by ion-exchange of the carrier, preferably with one or more aqueous solutions of salts of ruthenium or of metals of the iron group and salts of promoters, followed by washing with 5 washing water, drying and calc~ning the composition.
The ion-exchange ability of crystalline metal silicates is well known. In crystalline metal silicates, the electrovalence of the metal in the structure is balanced by the inclusion of a cation in the crystal. The cation is most commonly an alkali metal, such as sodium or potassium. The cations of either the synthetic or naturally occuring aluminosilicates can be exchanged for the mono- or polyvalent cations which are of a suitable physical size and configuration to diffuse into the intracrystal-line passages in the silicate structure~ The original cation can be replaced by another cation e.g. by a hydrogen ion or by an am~onium ion. In general, any suitable acid or salt solution such as a sulphate or nitrate can be used as a source of cations to be exchanged into the silicate.
The theoretical exchange capacity of the crystalline silicate is represented by the number of equivalents of cations, e.g.
sodium ions,,which balance the electroneutrality of the crystal-line silicate. The exchange capacity varies according to the particular type of sieve involved. In practice, not all of the cations in the silicate are readily replaced with the desired cations, so that the effective exchange capacity is often somewhat less than the theoretical exchange capacity. The extent of the exchange depends on such factors as the type of sieve, cations in the sieve, cations to be exchanged, type of solvent (water, alcohol) and temperature of exchange. Clearly, there is a limit to the amount of catalytically active metal which can be ion-exchanged into the crystalline silicate.
The ion-exchange is preferably carried out at a temperature in the range from 20 to 200C.
Following the ion-exchange step, the ion-exchange solution is removed from the zeolite con~aining the catalytically active metal 45~
exchanged therein, for example by filtration. The zeolite is then washed preferably with the ion-exchange solvent to remove any unreacted metal and the wash liquid is removed, for example by filtration. The zeolite cake from which the wash liquid has been removed usually contains about 50% solids. Either with or without further adjustment of the solvent content, the zeolite can be shaped to desired size. If desired one or more binders and/or extrusion aids can be added. The zeolite may then be dried, and the shaped catalyst is calcined, at a temperature of from about 10 300 to about 600C, to form the ~inished catalyst.
In the preparation of the catalysts the metals can be deposi-ted on the carrier in one or more steps. Between the separate ion-exchange steps the material may be dried. For the preparation of catalysts with a high metal content the use of a multi-step 15 technique may be necessary. The salts of the iron group metals and the salts of the promoters can be deposited on the carrier separate-ly from different solutions or together from one solution.
In the process according to the invention the intention is to convert the largest possible quartity of the C0 prese~t in the 20 feed into hydrocarbons over a catalyst containing one or more metal components with catalytic activity for the conversion of an H2/C0 mixture into hydrocarbons, which metal components are chosen from the group formed by iron, cobalt, nickel and ruthenium. To this end the H2/C0 molar ratio in the feed is suitably at least 25 1.0 and preferably 1.25-2.25.
The process according to the 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 30 catalyst bed. The process can also be carried out using a suspen-sion of the catalyst or catalyst combination in a hydrocarbon oil.
The process is preferably carried out under the following condi-tions: a temperature of 125-350C and in particular of 175-275C
34~
and a pressure of 1-150 bar and in particular of 5-100 bar.
The invention will now be explained with reference to the following Examples.
Example 1 The crystalline aluminosilicate ZSM-5 was prepared according to the recipe as described in U.S. patent specification No.
3,702,886. The silicate obtained was first transférred into the ammonium form by ion-exchange with a 2Normal NH4N03 solution. The ammonium form of the ZSM-5 was ion exchanged with an aqueous solution of RuC13 (5% wt.) during 48 hours. The catalyst was then washed with water, dried and subjected to a 2-hour calcination at 500C with air at atmospheric pressure and reduced for two hours at 280C with H2 at 4 bars. The resulting catalyst had the follo-wing composition:
1.7 Ru/66 SiO2/1 A12O3 (parts by weight). A gas mix~ure consisting of H2 and C0 (H2/CO = 1) was passed over this catalyst applying the following conditions:
gas hourly space velocity: 1000 1 (NTP)/lh pressure: 20 bar 20 temperature: 260C
The conversion of H2 + C0 into hydrocarbons was 20.0% wt. The space-time yield was 67 grams of hydrocarbons per litre of cata-lyst volume per hour.
The selectivity is given in the following table:
C 1 + C2 4% wt.
C 3 + C4 : 16% wt.
C 5 - C12: 78% wt.
C13 - C19: 1.5% wt.
C20 + : 0.5% wt. From this table it can be seen that the 30 yield of desired hydrocarbons boiling in the gasoline boiling range (C5-C12) is very high compared with those boiling below and above the preferred range.
The condensed liquid phase contained 40% wt aromatics, only trace amounts of durene being present.
S~
Comparative experiment 1 The ZSM-5 was prepared as shown in Example 1. It was impreg-nated with an aqueous solution of ruthenium chloride, dried, calcined during 2 hours at 500C in air and reduced for 2 hours at 280C with hydrogen at 4 bar pressure in order to obtain a cata-lyst having the composition: 1.7 Ru/66 SiO2/1 A1203 (parts by weight). Using this catalyst under the conditions described in Example 1 hydrocarbons were formed from a H2/C0 gas mixture (H2/C0 = 1). The conversion was 13% wt. The space-time yield was 26 grams 10 of hydrocarbons per litre of catalyst per hour.
The selectivity was:
C1 + C2 : 25% wt.
C3 + C4 : 40% wt.
C5 - C12: 35% wt.
15 C13 _ C19: 0% wt.
C20 + : 0% wt.
An inferior result as regards the yield of gasoline components (C5-C12) was thus obtained. Moreover no aromatics were present in the product.
20 Example 2 Crystalline silica was prepared according to the recipe of silicalite disclosed in column 6 of U.S. patent specification 4,061,724.
The crystalline silica obtained was first transferred to 25 ammonium form by ion-exchange with a 2N NH4 N03 solution. The a~monium form was ion-exchanged with an aqueous solution of Co (NH3)6(N03)2 (15% wt) during 24 hours.
The catalyst was then washed with water, dried, calcined two hours a~ 500C and subjected to a 24 hours' reduction with hydro-30 gen at 575C and 1 bar abs.
This catalyst had the following composition: 100 SiO2.2.5 Co (parts by weight).
A H2/C0 mixture (H2/C0 = 1) was passed over this catalyst applying the following conditions.
gas hourly space velocity: 1000 1 (NTP/1 h) 45~
pressure: 20 bar temperature: 260C
The conversion of H2 + C0 into hydrocarbons was 51% ~t. The space-time yield was 112 grams of hydrocarbons per litre of catalyst per hour.
The selectivity is given in the following table:
Cl + C2 16%
C3 + C4 15%
C5 C12: 58%
C 3 - Clg: 8%
C20 + : 3%
Claims (7)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for the production of hydrocarbons, from a mixture of car-bon monoxide and hydrogen, using a catalyst combination containing one or more metal components with catalytic activity for the conversion of an H2/CO mixture into acyclic hydrocarbons and a carrier, consisting of a crystalline silicate zeolite having in dehydrated form, the following overall composition, expressed in moles of the oxides (1-0 ? 0.3)(R)2/nO./ a Me2 O3/ y(d SiO2 + e GeO2), where R = one or more mono- or bivalent cations, Me = at least one trivalent metal 0 ? a ? 1 y ? 12 d ? 0.1 e ? 0, d + e = 1, and n = the valency of R
and having an X-ray powder diffraction pattern showing, inter alia, the follow-ing reflections, using Cu-K radiation having a wavelength of 0.15418 nm:
Table A
characterized in that, the metal component(s) has (have) been combined with the carrier by ion-exchange followed by washing, drying and calcining.
and having an X-ray powder diffraction pattern showing, inter alia, the follow-ing reflections, using Cu-K radiation having a wavelength of 0.15418 nm:
Table A
characterized in that, the metal component(s) has (have) been combined with the carrier by ion-exchange followed by washing, drying and calcining.
2. A process as claimed in claim 1, characterized in that it is carried out at a temperature of 125-400°C and a pressure of 1-150 bar.
3. A process as claimed in claim 1, characterized in that the catalyst contains iron, nickel, cobalt, and/or ruthenium as the metal component(s).
4. A process as claimed in claim 1, characterized in that the catalyst contains ZSM-5 and/or silicalite.
5. A process as claimed in claim 3, characterized in that the catalyst contains from 0.05 up to 10% by weight of one or more metals of the iron group, which have been introduced by ion-exchange.
6. A process as claimed in claim 5, characterized in that the catalyst contains one or more promoters in a quantity of 1-50% by weight of the quantity of the metals of the iron group.
7. A process as claimed in claim 3, characterized in that the catalyst contains from 0.1 up to 10% by weight of ruthenium.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR8114008A FR2509719A1 (en) | 1981-07-17 | 1981-07-17 | PROCESS FOR PRODUCING HYDROCARBONS |
| FR8114008 | 1981-07-17 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1198451A true CA1198451A (en) | 1985-12-24 |
Family
ID=9260632
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000406247A Expired CA1198451A (en) | 1981-07-17 | 1982-06-29 | Process for the production of hydrocarbons |
Country Status (11)
| Country | Link |
|---|---|
| JP (1) | JPS5819386A (en) |
| AU (1) | AU8605282A (en) |
| BE (1) | BE893843A (en) |
| CA (1) | CA1198451A (en) |
| DE (1) | DE3226616A1 (en) |
| FR (1) | FR2509719A1 (en) |
| GB (1) | GB2102022B (en) |
| IT (1) | IT8222443A0 (en) |
| NL (1) | NL8202690A (en) |
| NZ (1) | NZ201295A (en) |
| ZA (1) | ZA825084B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4477595A (en) * | 1982-03-31 | 1984-10-16 | Exxon Research And Engineering Co. | Liquid hydrocarbon synthesis using supported ruthenium catalysts |
| CA1196617A (en) * | 1982-07-14 | 1985-11-12 | George E. Morris | Catalyst composition, method for its production and its use in the production of hydrocarbons from synthesis gas |
| JPS6023330A (en) * | 1983-07-15 | 1985-02-05 | Daido Sanso Kk | Production of hydrocarbon |
| CA1240708A (en) * | 1983-11-15 | 1988-08-16 | Johannes K. Minderhoud | Process for the preparation of hydrocarbons |
| CA1234158A (en) * | 1983-11-15 | 1988-03-15 | Johannes K. Minderhoud | Process for the preparation of hydrocarbons |
| AU615698B2 (en) * | 1987-12-17 | 1991-10-10 | Broken Hill Proprietary Company Limited, The | Hydrocarbon processing |
| US7943674B1 (en) * | 2009-11-20 | 2011-05-17 | Chevron U.S.A. Inc. | Zeolite supported cobalt hybrid fischer-tropsch catalyst |
| US8461220B2 (en) * | 2010-06-10 | 2013-06-11 | Chevron U.S.A. Inc. | Process and system for reducing the olefin content of a fischer-tropsch product stream |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4180516A (en) * | 1977-08-18 | 1979-12-25 | Mobil Oil Corporation | Conversion of synthesis gas to aromatic hydrocarbons |
| NL7711719A (en) * | 1977-10-26 | 1979-05-01 | Shell Int Research | PROCESS FOR THE PREPARATION OF HYDROCARBONS. |
| US4172843A (en) * | 1978-07-21 | 1979-10-30 | Mobil Oil Corporation | Conversion of synthesis gas to high octane predominantly olefinic naphtha |
| NL179576C (en) * | 1979-06-06 | 1986-10-01 | Shell Int Research | CRYSTALLINE SILICATES; PROCESS FOR PREPARING CRYSTALLINE SILICATES; PROCESS FOR PREPARING AROMATIC HYDROCARBONS. |
| US4294725A (en) * | 1979-11-20 | 1981-10-13 | University Of Delaware | Catalyst, method for catalyst manufacture and use |
-
1981
- 1981-07-17 FR FR8114008A patent/FR2509719A1/en active Granted
-
1982
- 1982-06-29 CA CA000406247A patent/CA1198451A/en not_active Expired
- 1982-07-05 NL NL8202690A patent/NL8202690A/en not_active Application Discontinuation
- 1982-07-15 BE BE0/208593A patent/BE893843A/en not_active IP Right Cessation
- 1982-07-15 AU AU86052/82A patent/AU8605282A/en not_active Abandoned
- 1982-07-16 DE DE19823226616 patent/DE3226616A1/en not_active Withdrawn
- 1982-07-16 GB GB08220660A patent/GB2102022B/en not_active Expired
- 1982-07-16 NZ NZ201295A patent/NZ201295A/en unknown
- 1982-07-16 ZA ZA825084A patent/ZA825084B/en unknown
- 1982-07-16 JP JP57123037A patent/JPS5819386A/en active Pending
- 1982-07-16 IT IT8222443A patent/IT8222443A0/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| NZ201295A (en) | 1985-04-30 |
| JPS5819386A (en) | 1983-02-04 |
| DE3226616A1 (en) | 1983-02-17 |
| BE893843A (en) | 1983-01-17 |
| FR2509719A1 (en) | 1983-01-21 |
| GB2102022A (en) | 1983-01-26 |
| ZA825084B (en) | 1983-05-25 |
| GB2102022B (en) | 1984-08-15 |
| FR2509719B1 (en) | 1984-01-06 |
| NL8202690A (en) | 1983-02-16 |
| AU8605282A (en) | 1983-01-20 |
| IT8222443A0 (en) | 1982-07-16 |
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