CA1154037A - Process for the preparation of hydrocarbons and hydrocarbons so prepared - Google Patents
Process for the preparation of hydrocarbons and hydrocarbons so preparedInfo
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- CA1154037A CA1154037A CA000369477A CA369477A CA1154037A CA 1154037 A CA1154037 A CA 1154037A CA 000369477 A CA000369477 A CA 000369477A CA 369477 A CA369477 A CA 369477A CA 1154037 A CA1154037 A CA 1154037A
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- 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
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- 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
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- 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
- B01J29/80—Mixtures of different zeolites
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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
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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
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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
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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
- C07C1/0455—Reaction conditions
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- 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
- C07C1/0485—Set-up of reactors or accessories; Multi-step processes
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- 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
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- 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
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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- 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
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- 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
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- C07C2529/87—Gallosilicates; Aluminogallosilicates; Galloborosilicates
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Abstract
A B S T R A C T
PROCESS FOR THE PREPARATION OF HYDROCARBONS AND
HYDROCARBONS SO PREPARED
Two-stage process for the preparation of hydrocarbons from syngas with an H2/CO mol. ratio between 1.0 and 2.0, in which the syngas is contacted in a first stage with a bi- or trifunctional catalyst com-prising a crystalline silicate with ZSM-5 structure followed by contacting at least the C2 - fraction of the first stage product in a second stage with a mono- or bifunctional catalyst comprising a Ni, Co or Ru Fischer-Tropsch function. In this way an economically very attractive process combination is achieved for the production of both aromatics and paraffins.
PROCESS FOR THE PREPARATION OF HYDROCARBONS AND
HYDROCARBONS SO PREPARED
Two-stage process for the preparation of hydrocarbons from syngas with an H2/CO mol. ratio between 1.0 and 2.0, in which the syngas is contacted in a first stage with a bi- or trifunctional catalyst com-prising a crystalline silicate with ZSM-5 structure followed by contacting at least the C2 - fraction of the first stage product in a second stage with a mono- or bifunctional catalyst comprising a Ni, Co or Ru Fischer-Tropsch function. In this way an economically very attractive process combination is achieved for the production of both aromatics and paraffins.
Description
llS~ '7 PROCESS FOR ~HE PREPARATIO~ OF HYDROCARBO~S A~D
HYDROCARBONS SO PREPARED
The invention relates to a process for the preparation of a hydrocarbon mixture from a mixture of carbon monoxide and hydrogen with an H2/CO molar ratio of less than 2.0, using a bifunctional catalyst combination (I) containing one or more metal components with catalytic activity for the conversion of an H2/CO mixture into acyclic hydrocarbons and/or acyclic oxygen-containing hydro-carbons and a crystalline silicate having the capability of catalyzing the conversion of acyclic hydrocarbons and acyclic oxygen-containing hydrocarbons into aromatic hydrocarbons, on the understanding that if the H2/CO mixture has an H2/CO molar ratio below 1.5, use is made of a trifunctional catalyst combination containine one or more metal components with catalytic activity for the conversion of an H2/CO mixture into acyclic hydrocarbons and/or acyclic oxygen-containing hydrocarbons, one or more metal components with catalytic activity for the conversion of an H2/CO mixture into an H2/C02 mixture and a crystalline silicate having the capability of catalyzing the conversion of acyclic ; hydrocarbons and acyclic oxygen-containing hydrocarbons into aromatic hydrocarbons. Said crystalline silicates are charac-terized in that they have the followine properties after one hour's calcination in air at 500C:
a) an X-ray powder diffraction pattern showing as strongest lines the 4 lines 3tated in ~able A:
TABLE A
d(~)Relative intensity 11.1 + 0.2 VS
10.0 + 0.2 VS
: 3.o4 + 0.07 S
3.72 + o.o6 s wherein the letters used have the following meaning:
VS = very strong, S = strong, and . .
. . .
~b~ in the formula which represents the composition of the silicate, ex-pressed in moles of the oxides, and in which, in addition to oxides of hydrogen, alkali metal and/or alkaline-earth metal and silicon, there is present one or more oxides of a trivalent metal A se]ected from the group formed by aluminium, iron, gallium, rhodium, chromium and scandium, the A2O3/SiO2 molar ratio (for ~he sake of brevity further designated m in this patent application) is less than 0.1.
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 H2/C0 mixture is found to be un-satisfactory. Further, the process yields a product substantially consisting of hydrocarbons with at most 12 carbon atoms in the molecule and only very few hydrocarbons with more than 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 giving the reaction product, or at least its C2 fraction, an after-treatment by contacting it 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 have been selected from the group formed by Ni, Co and Ru, on the understanding that if the feed for the second step has an H2/C0 molar ratio of less than 1.5, water is added to this feed and that in the second step a bifunctional catalyst combination ~II) is used, whic}l contaiTIs! in addition to metal components with catalytic activity for the convcrsion of an l12/C0 mixture into acyclic hydrocarbons, also one or more metal components with catalytic actiuity for the conversion of an H20/C0 mixture into an H2/C02 mixture. In this way it is achieved that .
~ - 2 -~1~4~3~ t when using space velocities acceptable in actual practice, not only a very high conversion of the ll2/C0 mixture is obtained, but also that the reaction product consists substantially of hydrocarbons with more than 12 carbon atoms in the molecule.
The present invention therefore relates to a process for the preparation of a hydrocarbon mixture, in which a mixture of carbon monoxide and hydrogen with an H2/C0 molar ratio of less than 2.0 is contacted in a first step with a bifunctional catalyst combination (I~ as defined above, on the under-standing that if the H2/C0 mixture has an H2/C0 molar ratio of less than 1.5, a trifunctional catalyst com~ination as defined above is used, at least the C2 fraction of the reaction product from the first step being contacted in a second step with a monofunctional catalyst as defined above, on the under-standing that, if the feed for the second step has- an H2/C0 molar ratio of less than 1.5, water is added to this feed and that in the second step a bifunctional catalyst combination (II) as defined above is used.
The Canadian patent application 354,626 filed on 6th August, 1979, relates to a process for the preparation of a hydrocarbon mixtureJ in which a mixture of carbon monoxide and hydrogen w~th an H2/C0 molar ratio of less than 1.0 i5 contacted in a first step with a trif~mctional catalyst combination as defined above and in which at least the C2 fraction of the reaction product from the first step i5 contacted in a second step with a monofunctional catalyst as defined a~ove, on the understand~ng that, if t}le feed For the second step has an H2/C0 molar ratio of less than 1.5, water is adcled to this feed and that in the second step a bifunctional catalyst com~ination (II) as defined above is used.
The present patent application thereore relates to a process for the preparation of a hydrocarbon mixture, in which a mixture of carbon monoxide and ' hydrogen with an H2/CO molar ratio of 1,0-2.0 is contacted in a first step with ~:15g~5)~7 a bifunctional catalyst combination ~I~ as defined above, on the understanding that, if the H2/C0 mixture has an H2/C0 molar ratio of less than 1.5, a tri-functional catalyst combination as defined above is used, and in which at least the C2 fraction of the reaction product from the first step is contacted in a second step with a monofunctional catalyst as defined above, on the understanding that, if the feed for the second step has an H2/C0 molar ratio of less than 1.5,water is added to this feed and that in the second step a bifunctional catalyst combination (II~ as defined above is used.
In the process according to the invention the starting material is an H2/C0 mixture with an H2/C0 molar ratio of less than 2Ø Such H2/C0 mixturescan very suitably be prepared by steam gasification of a carbon-containing material. Examples of such materials are brown coal, anthracite, coke, crude mineral oil and fractions thereof and oils~ extracted from tar sand and bituminous ; shale~ The steam gasification is preferably carried out at a temperature of 900 - 1500C and a pressure of 10 - 100 bar. In the process according to the invention it is preferred to start from an H2/C0 mixture with an H2/CO molar ratio of more than 0.25.
The bi- and trifunct~onal catalyst combinations used in the process according to the invention in the first step contain, in addition to the metal components with catalytic activity, a crystalline metal silicate characterized by the properties mentioned under (a~-~b). Although, in principle the silicates may contain several metals selected from the group formed by altmlinium, iron, gallium, rhodium, chromium and scandium, :it i5 pr0ferred or the process accord-ing to the invention to use catalysts in which the silicate contains only one ofthese metals and in particular silicates which contain as the metal aluminium, iron or gallium. As regards the presence of aluminium in the silicates, the follo~ing remarks shQuld be made. The silicon compounds, which from an economic point of vie~ are su~table for the preparation of crystalline silicates on a technical scale, contain as a rule a small amount of aluminium as contaminant.
' ~3 .
.' ~L~S4~
Usually, this aluminium is found, at least partly, in the silicate prepared~ This means that, if the aim is to prepare for use in the bi- and trifunctional catalyst combinations a crystalline silicate containing one or more of the metals iron, gallium, rhodium, chromium and scandium, whilst the starting material is a base mixture in which a silicon compound contaminated with aluminium has been incorporated, as a rule a crystalline silicate will be obtained containing a slight amount of aluminium.
The crystalline silicates used in the bi- and trifunctional catalyst combinations should have a value for m which is less than 0.~. It is preferred to use crystalline silicates for which m is greater than 0.001 and in particular greater than 0.002 and silicates ~or which m is smaller than 0.05. If in the process according to the invention use is made of a bi- or trifunctional catalyst combination in which a crystalline aluminium silicate is present for which m is greater than 0.005, it is preferred to choose for this purpose an aluminium silicate which contains 0.1-10 %w of one of the elements selected from the group formed by manganese, calcium, magnesium and titanium, in particular manganese.
The crystalline silicate used in the bi- and trifunctional catalyst combinations has been defined, inter alia, with reference to the X-ray powder diffraction pattern. This X-ray powder diffraction pattern should contain, as strongest lines, the four lines shown in Table A. The complete X-ray powder diffraction pattern of a typical example of a silicate suitable for use accord-ing to the invention is shown in Table B:
3L~ 4~7 Table B
d(~) Relative intensity d(~)Relative intensity . . . _ 11.1 loo 4.oo 3 .o 70 3.8457 8.93 1 3.7231 7.99 ~ 3.64lo 7.42 1 3.41~ 5 6.68 7 3.34 3 6.35 11 3.30 5 5.97 ~8 3.25 2 5.70 ? 3.05 5 5.56 10 2.9812 5.35 2 2.96 3 4.98 6 2.86 2 4.60 4 2.73 2 4-35 5 2.60 2 4.25 7 2.48 3 4.o7 2 2.40 2 ~' ~: ~he crystalline silicates used in the bi- and trifunctional catalyst combinations can be prepared starting from an aqueous mixture containing the following compounds: one or more compounds of an alkali metal or alkaline-earth metal (M), one or more com-5 pounds containing an organic cation (R) or from which such a cation is formed during the preparation of the silicate, one or more silicon compounds and one or more compounds in which a tri~alent metal A selected from the group ~ormed by alumlnium, iron, gallium, rhodium, chromium and scandium is present,. The preparation is 10 performed by maintaining the mixture at elevated temperature until the silicate has been formed and subsequently separating the crystals of the silicate from the mother liquor and calcining them. In the aqueous mixture from which the silicates are prepared the various compounds should be present in the ~ollowing ratio, expressed in `j 15 moles of the oxides:
-, ~ .
1~5~
M2/nO : R20 = 0.1 - 20, R20 : SiO2 = 0.01 - 0.5, SiO2 : A203 10, and H20 : SiO2 = 5 - 50; (n is the valency of M) In the preparation of the silicates it is preferred to start from a base mixture in which M is present in an alkali metal compound and R in a tetra-alkylammonium compound and in particular from a base mixture in which ~ is present in a sodium compound and R in a tetrapropylammonium compound. The crystalline silicates prepared as described above contain alkali metal ions and/or alkaline-earth metal ions. They can be replaced By other cations such as hydrogen ions or ammonium ions by using suitable exchange methods. The crystalline silicates used in the bi~ and trifunctional catalyst combinations preferably have an alkali metal content of less than 0.1 ~Ow and in particular less than 0.05 ~OW.
Although the trifunctional catalyst combinations are described in this patent application as catalyst combinations containing one or more metal components with catalytic activity for the conversion of an H2/C0 mixture into acyclic hydrocarbons and/or acyclic oxygen-containing hydrocarbons and one or more metal components ~ith catalytic activity for the conversion of an H20/C0 mixture into an H2/C02 mixture, this does not mean at all that separate metal components that each have one of the two catalytic functions should always be present in the trifunctional catalyst combinations. For, it has been found that metal components and combinations of metal compon0nts with catalytic activity for the conversion of an H2/C0 mixture into substantially acyclic oxygen-contain-ing hydrocarbons often also have sufficient catalytic activity for the conversion of an H20/CO mixture into an H2/CO2 mixture, so that incorpor~tion of one metal component or one combination of metal components into the trifunctional catalyst ,.~ .
, ~54t)3~
combinations will then usually suffice. Metal components and combinations of metal components with catalytic activity for the conversion of an H2/CO
mixture into substantially acyclic hydrocarbons) usually have no or insufficient activity for the conversion of an H20/CO mixture into an H2/C02 mixture. When using such metal components or `` ~l1~4~J~'7 combinations of metal components in the trifunctional catalyst com-binations, one or more separate metal components with catalytic activity for the conversion of an H20/C0 mixture into an H2/C02 - mixture should therefore in most cases be incorporated into these 5 metal components.
The bi- and trif mctional catalyst combinations used in the first step of the process according to the invention are preferably composed of two or three separate catalysts, which will, for con-venience, be designated catalysts X, Y and Z. Catalyst X is the one 10 containing the metal components having catalytic activity for the conversion of an H2/C0 mixture into acyclic hydrocarbons and/or acyclic oxygen-containing hydrocarbons. Catalyst Y is the crystalline silicate. Catalyst Z is the one containing the metal components having catalytic activity for the conversion of an 15 H20/C0 mixture into an H2/C02 mixture. As has been explained here-inbefore the use of a Z-catalyst may in some cases be omitted for the trifunctional catalyst combinations.
If as the X-catalyst a catalyst is used which is capable of converting an H2/C0 mixture into substantially acyclic oxygen-20 containing hydrocarbons, preference is given to a catalyst whichis capable of converting an H2/C0 mixture into substantially `- methanol and/or dimethyl ether. Very suitable catalysts for this purpose are ZnO-Cr203 compositions, in particular such compoæitions in which the atomic percentage of zinc, based on the sum of zinc 25 and chromium, is at least 60% - 80~. When using a ZnO-Cr203 composition as X-catalyst, the use of a Z-catalyst may be omitted for the trifunctional catalyst combinations.
X-catalysts which are capable of converting an H2/C0 mixture into substantially acyclic hydrocarbons are referred to in the 30 literature as Fischer-Tropach catalysts. ~uch catalysts contain one or more metals from the iron group or ruthenium together with one or more promotera to increase the activity and/or selectivity and sometimes a carrier material such as kieselguhr. If in the .
~, ,,~, '7 first step of the process according to the invention use is made of a bi- or trifunctional catalyst combination in which the X-catalyst is a Fischer-Tropsch catalyst, it is preferred to choose ~or this purpose an iron or cobalt cat~yst~ in particular such a catalyst which has been prepared by impregnation. Very sui-table catalysts for this purpose are:
(a~ Catalysts that contain 30-75 pbw iron and 5-40 pbw magnesiumfor 100 pbw alumina and which have been prepared by impregnating an alumina carrier with one or more ~ueouss~utions of salts of iron and of magnesium followed by drying the compostion, calcining it at a temperature of 700-~ 200 C and reducing it.
: Particular preference is given to such catalysts that contain, in addition to 40-60 pbw iron and 7.5-30 pbw magnesium, 0.5-5 pbw copper as the reduction promoter and ~-5 pbw potassium as the selectivity promoter per 100 pbw alumina, and which have been calcined at 750-850 C and reduced at 250 -350 C.
(b~ Catalysts that contain ~0-40 pbw iron and 0.25-10 pbw chromium per 100 pbw silica and which have been prepared by impregnating a silica carrier with one or more aqueous solutions of salts of iron and of chromium, followed by drying the composition, calcining it and reducing it at a temperature of 350-750C. Particular preference is given to such catalysts which contain, in addition to 20-35 pbw iron and o.5-5 pbw chromium, 1-5 pbw potassium as the selectivity promoter and which have been calcined at 350-700 C and reduced at 350-500C.
(c~ Catalysts that contain 10-40 pbw cobalt and 0. 25-5 pbw zirconium, titanium or chromium per 100 pbw silica and which have been prepared by impregnatin~ a silica carrier with one or more aqueous solutions of salts of cobalt and zirconium, titanium or chromium followed by drying the CQmpOsition~ calcining it at 350-700 C and reducing it at 200-350C .
When using the iron catalysts mentioned under (a~ and (b) 35 as X-catalyst, the use of a Z-catalyst can be omitted. When using the cobalt catalysts mentioned under ~c~ as X-catalyst, a 1~540;~
-- ~o Z-catal~st should also be incorporated into the trifunctional catalyst combinations. If in the first step of the process accord;ng to the invention use is made of a bi- or trifunctional catalyst combination in which catalyst X is a Fischer-Tropsch catalyst, it is preferred to choose for this purpose an iron catalyst as described under (a~ and (b).
Z-catalysts which are capable of converting an H20/CO ~ixture into H2/C02 mixture are referred to in ~he literature as C0-shift catalysts.
In the bi- and trifunctional catalyst combinations the catalysts X,Y and, optionally, Z are preferably present as a physical mixture. When carrying out the first step of the process, using a fixed catalyst bed, this bed may also be built up of alternate layers of particles of the catalysts X, Y and, optionally, Z.
The first step of the process according to the invention can very suitably be carried out by conducting the feed in upward or in downward direction through a vertically mounted reactor in which a fixed or moving bed of the bi- or trifunction-al catalyst combination is present. ~he first step may, for instance, be carried out in the so-called fixed-bed operation, in bunker-flow operation, in ebullated-bed operation or fluidi~ed-bed operation. ~he first step of the process is preferably carried out under the following conditions: a temperature of ; 25 200-500C and in particular 250-450C, a pressure of 1-150 bar and in particular of 5-100 bar and a space velocity of 50~5000 and in particular of 300-3000 Nl gas/l catalyst/h.
In the process according to the invention at least the C2 fraction of the reaction product from the first step i8 3 used as the feed for the second step. Instead of the C2 fraction of the reaction product from the first step, a different fraction of this product, e.g. the C4 fraction, or even the whole product from the first step, ma~ be used -if desired - as the feed for the second step. In the second step of the process according to the invention it is intended to convert as much as possible of the C0 present in the feed for the second step into acyclic hydrocarbons over a monofunction-al catalyst containing one or more metal components with catalytic activity for the conversion of an H2/C0 mixture into acyclic hydro-carbons, which metal components have been selected from the group 5 formed by cobalt, nickel and ruthenium. To this end the H2/C0 molar ratio in the feed for the second step should be at least 1.5 and preferably 1.75-2.25. When using an H2/C0 mixture with a high H2/C0 molar ratio as the feed for the first step, the process according to the invention can yield a reaction product from the first step, lO which has an H2/C0 molar ratio of at least 1.5, which is suitable, as such, to be converted in the second step over the said catalyst.
An attractive way of ensuring in the process according to the invention that the reaction product from the first step has an H2/C0 molar ratio of at least 1.5 is adding water to the feed for the 15 first step and the use of a trifunctional catalyst combination in the first step. Under the influence of the catalyst combination present in the first step this water reacts with C0 from the feed to form an H2/C02 mixture. A further advantage of the addition of water to the feed of the first step in the process according to 20 thè invention is that it increases the stability of the trifunctional catalyst combination. Water addition to the feed for the first step, and a trifunctional catalyst combination can be applied in the process according to the invention both in cases where withou-t water addition the first step would have given a reaction 25 product with an H2/C0 molar ratio of less than 1.5, and in cases where, also without water addition, the first step would have given a reaction product with an H2/C0 molar ratio of at least 1.5, but where it is desirable tha-t the feed which is contacted with the catalyst in the second step has a higher H2/C0 molar ratio. If in the 30 process accordin~ to the invention an embodiment is chosen in which water i6 added to the ~eed ~or the first step, and a tri~unctional catalyst combination is used , the amount of water required is substantially determined by the H2~C0 molar ratio of the feed for the first step, the activity of the trifunctional catalyst 35 combination in the first step for converting an H23/C0 mixture into an H2fC02mixture and the desired H2/C0 molar ratio of the ~15~7 reaction product of the first step.
If in the process according vo the invention a reaction roduct is obtained from the first step with an H2~C0 molar ratio of less than 1.5, after water addition to the feed for the f;rst step or not and using a trifunctional catalyst combination, water should be added to the feed for the second step and in the second step a bifunctional catalyst combination (II) should be incorporated, which contains, in addition to the metal components with catalytic activity for the conversion of an ~2/C0 mixture into acyclic hydro-10 carbons~ also one or more metal components with catalytic activityfor the conversion of an H20/C0 mixture into an ~2/C02 mixture.
The bifunctional catalyst combinations which are optionally used in the second step of the process according to the invention, are preferably composed of two separate catalysts, which will, for con-15 venience, be designated catalyst A and catalyst B. Catalyst A is theone containing the metal components having catalytic activity for the conversion of an X2/C0 mixture in~o acyclic hydrocarbons, and which metal components have been selected from the group formed by cobalt, nickel and ruthenium. Catalyst B is the one containing the metal 20 components having catalytic activity for the conversion of an H2Q/
C0 mixture into an H2/C02 mixture. Both when using a monofunctional ; catalyst and when using a bifunctional catalyst combination in the second step of the process according to the invention, preference is given to a cobalt catalyst as the A-catalyst and in particular 25 to a cobalt catalyst prepared by impregnation. Very suitable catalysts for this purpose are the cobalt catalysts described hereinbefore under (c~. Suitable B-catalysts are the usual C0-shift catalysts. In the bifunctional catalyst combinations (II) catalysts A and B may be present as a physical mixture. When the second step of the process 30 is carried out using a fixed catalyst bed~ this bed is pre~erably built up of two or more alternate layers of particles of, success-ively, catalyst B and catalyst A. Water addition to the feed for the second step together with the use of a bifunctional catalyst com-bination in tke second step can be used in the process according ~G
35 the invention both in cases where the reaction product from the first step has an H2/C0 molar ratio of less than 1.5, and in cases where . .
- ~3 -the reaction product f`rom the ~irst step already has an ~2/CO molar ratio o~ at least ~.5, but where it is desirable that the feed which is contacted with catal~st A in the second step should have a higher H2/CO molar ratio. If in the process according to the invention an 5 embodiment is chosen in which water is added to the feed for the second step together with the use of a bifunctional catal~st com-bination in the second step, the amount of water required is sub-stantially determined by the ~2/CO molar ratio of the feed for the second step, the activity of the catalyst combination for the con-lO version of an H20/CO mixture into an H2/C02 mixture and the desiredH2/CO molar ratio of the product that is contacted with catalyst A.
The second step of the process according to the invention can very eonveniently be carried out by conducting the feed in upward or in downward direction through a vertieally mounted reactor in which 15 a fixed bed of the monofunctional catalyst or of the bifunctional catalyst combination is present. The second step of the process can also be carried out using a suspension of the catalyst or catalyst combination in a hydrocarbon oil. The second step of the process is preferably earried out under the f`ollowing conditions: a temperature 20 of 125-350C and in partie~lar of 175-275C 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 example:
Exam~le The following catalysts were used in the investigation:
Catalyst 1 A Co/Zr/SiOz catalyst that contained 25 pbw cobalt and 1.8 pbw zirconium per ~00 pbw silica and which had been prepared ~y impregnating a siliea earrier with an aqueous solution containing 30 a eobalt and a zireonium salt, rollowed by drying the eomposition, calcining it at 500 C and reducing it at 280C.
Catalyst 2 An Fe/Mg/Cu/K/Al~03 catalyst that contained 50 pbw iron,20 pbw magnesium, 2.5 pbw copper and 4 pbw potassium per 100 pbw alumina 35 and which had been prepared by impregnating an alumina carrier with an aqueous solution containing an iron, a magnesium, a copper and a _ ~4 -potassium salt, follo~ed by dr~ing the composition, calcining it at 800 C and reducing it at 325 C.
Catal~st 3 An Fe/Cu/K/SiO2 catalyst that contained 25 pbw iron, 1.25 pbw copper and 2 pbw potassium per 100 pbw silica and which had been prepared by impregnating a silica carrier with an aqueous solution containing an iron, a copper and a potassium salt, ~ollowed by drying the composition, calcining it at 400C and reducing it at 280C.
Catalyst 4 lO A Cu/Zn/A1203 catalyst with a Cu/Zn atomic ratio of 0.55.
Catalyst 5 A ZnO-Cr203 catalyst in which the atomic percentage of zinc based on the sum of zinc and chromium was 70%.
CatPlysts 6-8 Three crystalline silicates (silicates A-C) were prepared by heating mixtures of SiO2, NaOH, CC3H7)4~ OH and either NaAlO2, or Fe(N03)3, or Ga(N03)3 in water for six hours at 150 C in an autoclaue under autogenous pressure. After the reaction mixtures had cooled down, the silicates formed were filtered off, washed with water until the 20 pH of the wash water was about 8, dried at 120 C and calcined at 500C.
The silicates A-C had the following properties:
(a) thermally stable up to a temperature above 800C, (b) an X-ray powder diffraction pattern substantially equ~l to the one given in Table B, (c) a value for m as mentioned below:
silicate A: A1203/SiO2 molar ratio = 0.0133, silicate B: Fe203/SiO2 molar ratio = 0.0050, silicate C: Ga203/SiO2 mol~r ratio 5 o.oo83.
The molar composition of the a~ueous mixtures from which the silicates A-C were prepared can be represented as follows:
Silicate A:
1 Na20 .4.5 ~C3H7)4N120. 0.33 Al203. 25 SiO2 .450 H20 Silicate B:
HYDROCARBONS SO PREPARED
The invention relates to a process for the preparation of a hydrocarbon mixture from a mixture of carbon monoxide and hydrogen with an H2/CO molar ratio of less than 2.0, using a bifunctional catalyst combination (I) containing one or more metal components with catalytic activity for the conversion of an H2/CO mixture into acyclic hydrocarbons and/or acyclic oxygen-containing hydro-carbons and a crystalline silicate having the capability of catalyzing the conversion of acyclic hydrocarbons and acyclic oxygen-containing hydrocarbons into aromatic hydrocarbons, on the understanding that if the H2/CO mixture has an H2/CO molar ratio below 1.5, use is made of a trifunctional catalyst combination containine one or more metal components with catalytic activity for the conversion of an H2/CO mixture into acyclic hydrocarbons and/or acyclic oxygen-containing hydrocarbons, one or more metal components with catalytic activity for the conversion of an H2/CO mixture into an H2/C02 mixture and a crystalline silicate having the capability of catalyzing the conversion of acyclic ; hydrocarbons and acyclic oxygen-containing hydrocarbons into aromatic hydrocarbons. Said crystalline silicates are charac-terized in that they have the followine properties after one hour's calcination in air at 500C:
a) an X-ray powder diffraction pattern showing as strongest lines the 4 lines 3tated in ~able A:
TABLE A
d(~)Relative intensity 11.1 + 0.2 VS
10.0 + 0.2 VS
: 3.o4 + 0.07 S
3.72 + o.o6 s wherein the letters used have the following meaning:
VS = very strong, S = strong, and . .
. . .
~b~ in the formula which represents the composition of the silicate, ex-pressed in moles of the oxides, and in which, in addition to oxides of hydrogen, alkali metal and/or alkaline-earth metal and silicon, there is present one or more oxides of a trivalent metal A se]ected from the group formed by aluminium, iron, gallium, rhodium, chromium and scandium, the A2O3/SiO2 molar ratio (for ~he sake of brevity further designated m in this patent application) is less than 0.1.
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 H2/C0 mixture is found to be un-satisfactory. Further, the process yields a product substantially consisting of hydrocarbons with at most 12 carbon atoms in the molecule and only very few hydrocarbons with more than 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 giving the reaction product, or at least its C2 fraction, an after-treatment by contacting it 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 have been selected from the group formed by Ni, Co and Ru, on the understanding that if the feed for the second step has an H2/C0 molar ratio of less than 1.5, water is added to this feed and that in the second step a bifunctional catalyst combination ~II) is used, whic}l contaiTIs! in addition to metal components with catalytic activity for the convcrsion of an l12/C0 mixture into acyclic hydrocarbons, also one or more metal components with catalytic actiuity for the conversion of an H20/C0 mixture into an H2/C02 mixture. In this way it is achieved that .
~ - 2 -~1~4~3~ t when using space velocities acceptable in actual practice, not only a very high conversion of the ll2/C0 mixture is obtained, but also that the reaction product consists substantially of hydrocarbons with more than 12 carbon atoms in the molecule.
The present invention therefore relates to a process for the preparation of a hydrocarbon mixture, in which a mixture of carbon monoxide and hydrogen with an H2/C0 molar ratio of less than 2.0 is contacted in a first step with a bifunctional catalyst combination (I~ as defined above, on the under-standing that if the H2/C0 mixture has an H2/C0 molar ratio of less than 1.5, a trifunctional catalyst com~ination as defined above is used, at least the C2 fraction of the reaction product from the first step being contacted in a second step with a monofunctional catalyst as defined above, on the under-standing that, if the feed for the second step has- an H2/C0 molar ratio of less than 1.5, water is added to this feed and that in the second step a bifunctional catalyst combination (II) as defined above is used.
The Canadian patent application 354,626 filed on 6th August, 1979, relates to a process for the preparation of a hydrocarbon mixtureJ in which a mixture of carbon monoxide and hydrogen w~th an H2/C0 molar ratio of less than 1.0 i5 contacted in a first step with a trif~mctional catalyst combination as defined above and in which at least the C2 fraction of the reaction product from the first step i5 contacted in a second step with a monofunctional catalyst as defined a~ove, on the understand~ng that, if t}le feed For the second step has an H2/C0 molar ratio of less than 1.5, water is adcled to this feed and that in the second step a bifunctional catalyst com~ination (II) as defined above is used.
The present patent application thereore relates to a process for the preparation of a hydrocarbon mixture, in which a mixture of carbon monoxide and ' hydrogen with an H2/CO molar ratio of 1,0-2.0 is contacted in a first step with ~:15g~5)~7 a bifunctional catalyst combination ~I~ as defined above, on the understanding that, if the H2/C0 mixture has an H2/C0 molar ratio of less than 1.5, a tri-functional catalyst combination as defined above is used, and in which at least the C2 fraction of the reaction product from the first step is contacted in a second step with a monofunctional catalyst as defined above, on the understanding that, if the feed for the second step has an H2/C0 molar ratio of less than 1.5,water is added to this feed and that in the second step a bifunctional catalyst combination (II~ as defined above is used.
In the process according to the invention the starting material is an H2/C0 mixture with an H2/C0 molar ratio of less than 2Ø Such H2/C0 mixturescan very suitably be prepared by steam gasification of a carbon-containing material. Examples of such materials are brown coal, anthracite, coke, crude mineral oil and fractions thereof and oils~ extracted from tar sand and bituminous ; shale~ The steam gasification is preferably carried out at a temperature of 900 - 1500C and a pressure of 10 - 100 bar. In the process according to the invention it is preferred to start from an H2/C0 mixture with an H2/CO molar ratio of more than 0.25.
The bi- and trifunct~onal catalyst combinations used in the process according to the invention in the first step contain, in addition to the metal components with catalytic activity, a crystalline metal silicate characterized by the properties mentioned under (a~-~b). Although, in principle the silicates may contain several metals selected from the group formed by altmlinium, iron, gallium, rhodium, chromium and scandium, :it i5 pr0ferred or the process accord-ing to the invention to use catalysts in which the silicate contains only one ofthese metals and in particular silicates which contain as the metal aluminium, iron or gallium. As regards the presence of aluminium in the silicates, the follo~ing remarks shQuld be made. The silicon compounds, which from an economic point of vie~ are su~table for the preparation of crystalline silicates on a technical scale, contain as a rule a small amount of aluminium as contaminant.
' ~3 .
.' ~L~S4~
Usually, this aluminium is found, at least partly, in the silicate prepared~ This means that, if the aim is to prepare for use in the bi- and trifunctional catalyst combinations a crystalline silicate containing one or more of the metals iron, gallium, rhodium, chromium and scandium, whilst the starting material is a base mixture in which a silicon compound contaminated with aluminium has been incorporated, as a rule a crystalline silicate will be obtained containing a slight amount of aluminium.
The crystalline silicates used in the bi- and trifunctional catalyst combinations should have a value for m which is less than 0.~. It is preferred to use crystalline silicates for which m is greater than 0.001 and in particular greater than 0.002 and silicates ~or which m is smaller than 0.05. If in the process according to the invention use is made of a bi- or trifunctional catalyst combination in which a crystalline aluminium silicate is present for which m is greater than 0.005, it is preferred to choose for this purpose an aluminium silicate which contains 0.1-10 %w of one of the elements selected from the group formed by manganese, calcium, magnesium and titanium, in particular manganese.
The crystalline silicate used in the bi- and trifunctional catalyst combinations has been defined, inter alia, with reference to the X-ray powder diffraction pattern. This X-ray powder diffraction pattern should contain, as strongest lines, the four lines shown in Table A. The complete X-ray powder diffraction pattern of a typical example of a silicate suitable for use accord-ing to the invention is shown in Table B:
3L~ 4~7 Table B
d(~) Relative intensity d(~)Relative intensity . . . _ 11.1 loo 4.oo 3 .o 70 3.8457 8.93 1 3.7231 7.99 ~ 3.64lo 7.42 1 3.41~ 5 6.68 7 3.34 3 6.35 11 3.30 5 5.97 ~8 3.25 2 5.70 ? 3.05 5 5.56 10 2.9812 5.35 2 2.96 3 4.98 6 2.86 2 4.60 4 2.73 2 4-35 5 2.60 2 4.25 7 2.48 3 4.o7 2 2.40 2 ~' ~: ~he crystalline silicates used in the bi- and trifunctional catalyst combinations can be prepared starting from an aqueous mixture containing the following compounds: one or more compounds of an alkali metal or alkaline-earth metal (M), one or more com-5 pounds containing an organic cation (R) or from which such a cation is formed during the preparation of the silicate, one or more silicon compounds and one or more compounds in which a tri~alent metal A selected from the group ~ormed by alumlnium, iron, gallium, rhodium, chromium and scandium is present,. The preparation is 10 performed by maintaining the mixture at elevated temperature until the silicate has been formed and subsequently separating the crystals of the silicate from the mother liquor and calcining them. In the aqueous mixture from which the silicates are prepared the various compounds should be present in the ~ollowing ratio, expressed in `j 15 moles of the oxides:
-, ~ .
1~5~
M2/nO : R20 = 0.1 - 20, R20 : SiO2 = 0.01 - 0.5, SiO2 : A203 10, and H20 : SiO2 = 5 - 50; (n is the valency of M) In the preparation of the silicates it is preferred to start from a base mixture in which M is present in an alkali metal compound and R in a tetra-alkylammonium compound and in particular from a base mixture in which ~ is present in a sodium compound and R in a tetrapropylammonium compound. The crystalline silicates prepared as described above contain alkali metal ions and/or alkaline-earth metal ions. They can be replaced By other cations such as hydrogen ions or ammonium ions by using suitable exchange methods. The crystalline silicates used in the bi~ and trifunctional catalyst combinations preferably have an alkali metal content of less than 0.1 ~Ow and in particular less than 0.05 ~OW.
Although the trifunctional catalyst combinations are described in this patent application as catalyst combinations containing one or more metal components with catalytic activity for the conversion of an H2/C0 mixture into acyclic hydrocarbons and/or acyclic oxygen-containing hydrocarbons and one or more metal components ~ith catalytic activity for the conversion of an H20/C0 mixture into an H2/C02 mixture, this does not mean at all that separate metal components that each have one of the two catalytic functions should always be present in the trifunctional catalyst combinations. For, it has been found that metal components and combinations of metal compon0nts with catalytic activity for the conversion of an H2/C0 mixture into substantially acyclic oxygen-contain-ing hydrocarbons often also have sufficient catalytic activity for the conversion of an H20/CO mixture into an H2/CO2 mixture, so that incorpor~tion of one metal component or one combination of metal components into the trifunctional catalyst ,.~ .
, ~54t)3~
combinations will then usually suffice. Metal components and combinations of metal components with catalytic activity for the conversion of an H2/CO
mixture into substantially acyclic hydrocarbons) usually have no or insufficient activity for the conversion of an H20/CO mixture into an H2/C02 mixture. When using such metal components or `` ~l1~4~J~'7 combinations of metal components in the trifunctional catalyst com-binations, one or more separate metal components with catalytic activity for the conversion of an H20/C0 mixture into an H2/C02 - mixture should therefore in most cases be incorporated into these 5 metal components.
The bi- and trif mctional catalyst combinations used in the first step of the process according to the invention are preferably composed of two or three separate catalysts, which will, for con-venience, be designated catalysts X, Y and Z. Catalyst X is the one 10 containing the metal components having catalytic activity for the conversion of an H2/C0 mixture into acyclic hydrocarbons and/or acyclic oxygen-containing hydrocarbons. Catalyst Y is the crystalline silicate. Catalyst Z is the one containing the metal components having catalytic activity for the conversion of an 15 H20/C0 mixture into an H2/C02 mixture. As has been explained here-inbefore the use of a Z-catalyst may in some cases be omitted for the trifunctional catalyst combinations.
If as the X-catalyst a catalyst is used which is capable of converting an H2/C0 mixture into substantially acyclic oxygen-20 containing hydrocarbons, preference is given to a catalyst whichis capable of converting an H2/C0 mixture into substantially `- methanol and/or dimethyl ether. Very suitable catalysts for this purpose are ZnO-Cr203 compositions, in particular such compoæitions in which the atomic percentage of zinc, based on the sum of zinc 25 and chromium, is at least 60% - 80~. When using a ZnO-Cr203 composition as X-catalyst, the use of a Z-catalyst may be omitted for the trifunctional catalyst combinations.
X-catalysts which are capable of converting an H2/C0 mixture into substantially acyclic hydrocarbons are referred to in the 30 literature as Fischer-Tropach catalysts. ~uch catalysts contain one or more metals from the iron group or ruthenium together with one or more promotera to increase the activity and/or selectivity and sometimes a carrier material such as kieselguhr. If in the .
~, ,,~, '7 first step of the process according to the invention use is made of a bi- or trifunctional catalyst combination in which the X-catalyst is a Fischer-Tropsch catalyst, it is preferred to choose ~or this purpose an iron or cobalt cat~yst~ in particular such a catalyst which has been prepared by impregnation. Very sui-table catalysts for this purpose are:
(a~ Catalysts that contain 30-75 pbw iron and 5-40 pbw magnesiumfor 100 pbw alumina and which have been prepared by impregnating an alumina carrier with one or more ~ueouss~utions of salts of iron and of magnesium followed by drying the compostion, calcining it at a temperature of 700-~ 200 C and reducing it.
: Particular preference is given to such catalysts that contain, in addition to 40-60 pbw iron and 7.5-30 pbw magnesium, 0.5-5 pbw copper as the reduction promoter and ~-5 pbw potassium as the selectivity promoter per 100 pbw alumina, and which have been calcined at 750-850 C and reduced at 250 -350 C.
(b~ Catalysts that contain ~0-40 pbw iron and 0.25-10 pbw chromium per 100 pbw silica and which have been prepared by impregnating a silica carrier with one or more aqueous solutions of salts of iron and of chromium, followed by drying the composition, calcining it and reducing it at a temperature of 350-750C. Particular preference is given to such catalysts which contain, in addition to 20-35 pbw iron and o.5-5 pbw chromium, 1-5 pbw potassium as the selectivity promoter and which have been calcined at 350-700 C and reduced at 350-500C.
(c~ Catalysts that contain 10-40 pbw cobalt and 0. 25-5 pbw zirconium, titanium or chromium per 100 pbw silica and which have been prepared by impregnatin~ a silica carrier with one or more aqueous solutions of salts of cobalt and zirconium, titanium or chromium followed by drying the CQmpOsition~ calcining it at 350-700 C and reducing it at 200-350C .
When using the iron catalysts mentioned under (a~ and (b) 35 as X-catalyst, the use of a Z-catalyst can be omitted. When using the cobalt catalysts mentioned under ~c~ as X-catalyst, a 1~540;~
-- ~o Z-catal~st should also be incorporated into the trifunctional catalyst combinations. If in the first step of the process accord;ng to the invention use is made of a bi- or trifunctional catalyst combination in which catalyst X is a Fischer-Tropsch catalyst, it is preferred to choose for this purpose an iron catalyst as described under (a~ and (b).
Z-catalysts which are capable of converting an H20/CO ~ixture into H2/C02 mixture are referred to in ~he literature as C0-shift catalysts.
In the bi- and trifunctional catalyst combinations the catalysts X,Y and, optionally, Z are preferably present as a physical mixture. When carrying out the first step of the process, using a fixed catalyst bed, this bed may also be built up of alternate layers of particles of the catalysts X, Y and, optionally, Z.
The first step of the process according to the invention can very suitably be carried out by conducting the feed in upward or in downward direction through a vertically mounted reactor in which a fixed or moving bed of the bi- or trifunction-al catalyst combination is present. ~he first step may, for instance, be carried out in the so-called fixed-bed operation, in bunker-flow operation, in ebullated-bed operation or fluidi~ed-bed operation. ~he first step of the process is preferably carried out under the following conditions: a temperature of ; 25 200-500C and in particular 250-450C, a pressure of 1-150 bar and in particular of 5-100 bar and a space velocity of 50~5000 and in particular of 300-3000 Nl gas/l catalyst/h.
In the process according to the invention at least the C2 fraction of the reaction product from the first step i8 3 used as the feed for the second step. Instead of the C2 fraction of the reaction product from the first step, a different fraction of this product, e.g. the C4 fraction, or even the whole product from the first step, ma~ be used -if desired - as the feed for the second step. In the second step of the process according to the invention it is intended to convert as much as possible of the C0 present in the feed for the second step into acyclic hydrocarbons over a monofunction-al catalyst containing one or more metal components with catalytic activity for the conversion of an H2/C0 mixture into acyclic hydro-carbons, which metal components have been selected from the group 5 formed by cobalt, nickel and ruthenium. To this end the H2/C0 molar ratio in the feed for the second step should be at least 1.5 and preferably 1.75-2.25. When using an H2/C0 mixture with a high H2/C0 molar ratio as the feed for the first step, the process according to the invention can yield a reaction product from the first step, lO which has an H2/C0 molar ratio of at least 1.5, which is suitable, as such, to be converted in the second step over the said catalyst.
An attractive way of ensuring in the process according to the invention that the reaction product from the first step has an H2/C0 molar ratio of at least 1.5 is adding water to the feed for the 15 first step and the use of a trifunctional catalyst combination in the first step. Under the influence of the catalyst combination present in the first step this water reacts with C0 from the feed to form an H2/C02 mixture. A further advantage of the addition of water to the feed of the first step in the process according to 20 thè invention is that it increases the stability of the trifunctional catalyst combination. Water addition to the feed for the first step, and a trifunctional catalyst combination can be applied in the process according to the invention both in cases where withou-t water addition the first step would have given a reaction 25 product with an H2/C0 molar ratio of less than 1.5, and in cases where, also without water addition, the first step would have given a reaction product with an H2/C0 molar ratio of at least 1.5, but where it is desirable tha-t the feed which is contacted with the catalyst in the second step has a higher H2/C0 molar ratio. If in the 30 process accordin~ to the invention an embodiment is chosen in which water i6 added to the ~eed ~or the first step, and a tri~unctional catalyst combination is used , the amount of water required is substantially determined by the H2~C0 molar ratio of the feed for the first step, the activity of the trifunctional catalyst 35 combination in the first step for converting an H23/C0 mixture into an H2fC02mixture and the desired H2/C0 molar ratio of the ~15~7 reaction product of the first step.
If in the process according vo the invention a reaction roduct is obtained from the first step with an H2~C0 molar ratio of less than 1.5, after water addition to the feed for the f;rst step or not and using a trifunctional catalyst combination, water should be added to the feed for the second step and in the second step a bifunctional catalyst combination (II) should be incorporated, which contains, in addition to the metal components with catalytic activity for the conversion of an ~2/C0 mixture into acyclic hydro-10 carbons~ also one or more metal components with catalytic activityfor the conversion of an H20/C0 mixture into an ~2/C02 mixture.
The bifunctional catalyst combinations which are optionally used in the second step of the process according to the invention, are preferably composed of two separate catalysts, which will, for con-15 venience, be designated catalyst A and catalyst B. Catalyst A is theone containing the metal components having catalytic activity for the conversion of an X2/C0 mixture in~o acyclic hydrocarbons, and which metal components have been selected from the group formed by cobalt, nickel and ruthenium. Catalyst B is the one containing the metal 20 components having catalytic activity for the conversion of an H2Q/
C0 mixture into an H2/C02 mixture. Both when using a monofunctional ; catalyst and when using a bifunctional catalyst combination in the second step of the process according to the invention, preference is given to a cobalt catalyst as the A-catalyst and in particular 25 to a cobalt catalyst prepared by impregnation. Very suitable catalysts for this purpose are the cobalt catalysts described hereinbefore under (c~. Suitable B-catalysts are the usual C0-shift catalysts. In the bifunctional catalyst combinations (II) catalysts A and B may be present as a physical mixture. When the second step of the process 30 is carried out using a fixed catalyst bed~ this bed is pre~erably built up of two or more alternate layers of particles of, success-ively, catalyst B and catalyst A. Water addition to the feed for the second step together with the use of a bifunctional catalyst com-bination in tke second step can be used in the process according ~G
35 the invention both in cases where the reaction product from the first step has an H2/C0 molar ratio of less than 1.5, and in cases where . .
- ~3 -the reaction product f`rom the ~irst step already has an ~2/CO molar ratio o~ at least ~.5, but where it is desirable that the feed which is contacted with catal~st A in the second step should have a higher H2/CO molar ratio. If in the process according to the invention an 5 embodiment is chosen in which water is added to the feed for the second step together with the use of a bifunctional catal~st com-bination in the second step, the amount of water required is sub-stantially determined by the ~2/CO molar ratio of the feed for the second step, the activity of the catalyst combination for the con-lO version of an H20/CO mixture into an H2/C02 mixture and the desiredH2/CO molar ratio of the product that is contacted with catalyst A.
The second step of the process according to the invention can very eonveniently be carried out by conducting the feed in upward or in downward direction through a vertieally mounted reactor in which 15 a fixed bed of the monofunctional catalyst or of the bifunctional catalyst combination is present. The second step of the process can also be carried out using a suspension of the catalyst or catalyst combination in a hydrocarbon oil. The second step of the process is preferably earried out under the f`ollowing conditions: a temperature 20 of 125-350C and in partie~lar of 175-275C 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 example:
Exam~le The following catalysts were used in the investigation:
Catalyst 1 A Co/Zr/SiOz catalyst that contained 25 pbw cobalt and 1.8 pbw zirconium per ~00 pbw silica and which had been prepared ~y impregnating a siliea earrier with an aqueous solution containing 30 a eobalt and a zireonium salt, rollowed by drying the eomposition, calcining it at 500 C and reducing it at 280C.
Catalyst 2 An Fe/Mg/Cu/K/Al~03 catalyst that contained 50 pbw iron,20 pbw magnesium, 2.5 pbw copper and 4 pbw potassium per 100 pbw alumina 35 and which had been prepared by impregnating an alumina carrier with an aqueous solution containing an iron, a magnesium, a copper and a _ ~4 -potassium salt, follo~ed by dr~ing the composition, calcining it at 800 C and reducing it at 325 C.
Catal~st 3 An Fe/Cu/K/SiO2 catalyst that contained 25 pbw iron, 1.25 pbw copper and 2 pbw potassium per 100 pbw silica and which had been prepared by impregnating a silica carrier with an aqueous solution containing an iron, a copper and a potassium salt, ~ollowed by drying the composition, calcining it at 400C and reducing it at 280C.
Catalyst 4 lO A Cu/Zn/A1203 catalyst with a Cu/Zn atomic ratio of 0.55.
Catalyst 5 A ZnO-Cr203 catalyst in which the atomic percentage of zinc based on the sum of zinc and chromium was 70%.
CatPlysts 6-8 Three crystalline silicates (silicates A-C) were prepared by heating mixtures of SiO2, NaOH, CC3H7)4~ OH and either NaAlO2, or Fe(N03)3, or Ga(N03)3 in water for six hours at 150 C in an autoclaue under autogenous pressure. After the reaction mixtures had cooled down, the silicates formed were filtered off, washed with water until the 20 pH of the wash water was about 8, dried at 120 C and calcined at 500C.
The silicates A-C had the following properties:
(a) thermally stable up to a temperature above 800C, (b) an X-ray powder diffraction pattern substantially equ~l to the one given in Table B, (c) a value for m as mentioned below:
silicate A: A1203/SiO2 molar ratio = 0.0133, silicate B: Fe203/SiO2 molar ratio = 0.0050, silicate C: Ga203/SiO2 mol~r ratio 5 o.oo83.
The molar composition of the a~ueous mixtures from which the silicates A-C were prepared can be represented as follows:
Silicate A:
1 Na20 .4.5 ~C3H7)4N120. 0.33 Al203. 25 SiO2 .450 H20 Silicate B:
2 ~ 3 7) 4~ 2 o 125 Fe203 .25 ~iO2~ 468 EI O
.
J
Silicate C:
2 4-5 [(C3x7)4~ 2Q 0-22 Ga2o3 25 Sio2.450 H20.
The silicates D-F were prepared from the silicates A-C, respectively, by boiling the silicates A-C with ~.0 molar NH4~03 solution, washing with water, boiling again with ~.0 molar NH4N03 solution and washing, drying and calcining. A catalyst 6 was pre-pared from silicate D by impregnating silicate D with an aqueous solution of a manganese salt followed by drying the composition and calcining it. Catalyst 6 contained 3%w manganese.
Silicates E and F were used as such as catalyst 7 and catalyst 8, respectively.
Cata yst mixtures I-VI
- Six catalyst mixtures were prepared. The catalyst mixtures I-V
consisted each of a physical mixture of two of the above-mentioned catalysts in the following ratio:
Cat. mixture I = 2 pbv of cat. 5 + 1 pbv of cat. 6, Cat. mixture II = 2 pbv of cat. 5 + 1 pbv of cat. 7, Cat. mixture III= 2 pbv of cat. 5 + 1 pbv of cat. 8, Cat. mixture IV = 2.5 pbv of cat. 2 + 1 pbv of cat. 6, 20 Cat. mixture V = 2 pbv of cat. 3 + 1 pbv of cat. 7.
Catalyst mixture VI consisted of a layer of catalyst 4 ; and a layer of catalyst 1 in a volume ratio of 1:2.
The catalyst mixtures I-VI and catalyst 1 were tested for the preparation in one or two steps of a hydrocarbon mixture from an H2/C0 mixture. The test was carried out in ~e.or two reactors of 50 ml each, in which a fixed catalyst bed was present.
Twenty-three experiments were carried out. The experiments 1,4,7,10,15,17,19 and 22 were carried out in one step; the other experiments in two steps. In all the exEeriments, with the exception o~ experiments 14,22 and 23, a temperature of 375C was used in the ~irst step. In experiment 14 the temperature in the first step was 280C and in the experiments 22 and 23 the temperature in the first step was 250C.
:
'7 - ~6 -In all the experiments carried out in two steps the temperature in the second step was 220 C. In all the experiments, with the exception o~ experiments 14,22 and 23, a pressure of 60 bar was used. In OEperi~ents ~4,22 and 23 the pressure was 30 bar.
In the experi~ents 1,4,7 and 10 the space velocity was ~OOQ Nl.l h . In the experiments ~5,~7,~9 and 22 the space velocity was 50Q
Nl.l -1.h . In all the experiments carrîed out in two steps the space velocity, based on the sum of the total catalyst system (in the first & second step~ was 500 Nl.l. .h . In the experiments 6,9, and 12 the C4 fraction of the product from the first step was used as the feed for the second step. In the remainine experiments which were carried out in two steps, the total reaction product ~rom the first step was used as the feed for the second step. The results of the experiments are stated in Table C.
~ .
, ' , , '~ .
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Il~ ~ Il~ G~ Ir~ ~ $
~ O ' ' ~
~ ; ,_ ~
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H
H ~ O
Lr~
~ H U~ ~ ~ o ,,~ 0 U~
~ ~ N O Ir\ 0 U~ H Il~ H I ~D
- ~ O N t--O ~r ,~ H t-- O ~ N
H ~ o U~ 0 ~ 0 N H I H I
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'-- H I I I I
a~
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~ O~ C\J ~ H
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.
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~, I i ~ Ctl ~ I
u~
~0 N t-- cO
~,,1 U~ C~ O
--,. E~
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~ U~ O CO O~ O~ O C~
-- O O~
--aJ
,tn O
rl d $ ~ ~ ~J
vd O a~ ~
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~ & ~ a~ v~
.. . .. .
~154~3'7 Of the experiments listed in the table, only the two-step experiments 3, 6, 9, 12, 13, 14, 16, 18, 20, 21 and 23 are experiments according to the invention.
The one-step experiments 1, 4, 7, 10, 15, 17, 19 and 22 and the two-step experiments 2, 5, 8 and 11 are outside the scope of the invention. They have been included in the patent application for comparison. Of the two-step experiments 3, 6, 9, 12, 13, 14, 16, 18, 20, 21 and 23 only the experiments 16, 18, 20, 21 and 23 are experiments according to the present patent application.
The two-step experiments 3, 6, 9, 12, 13 and 14 are experiments according to the Canadian patent application 354,626, 10 The advantages of the two-step process according to the invention as regards the conversion of the H2/C0 mixture and the composition of the reaction product are evident when the results of the following experiments are compared Experiments 3 with experiments 1 and 2 " 6 " " 4 and 5 " 9 " " 7 and 8 " 12 and 13 " " 10 and 11 " 16 " " 15 " 18 " " 17 " 20 and 21 " " 19 ; " 23 " " 22 ~ - 20 -.~
.
J
Silicate C:
2 4-5 [(C3x7)4~ 2Q 0-22 Ga2o3 25 Sio2.450 H20.
The silicates D-F were prepared from the silicates A-C, respectively, by boiling the silicates A-C with ~.0 molar NH4~03 solution, washing with water, boiling again with ~.0 molar NH4N03 solution and washing, drying and calcining. A catalyst 6 was pre-pared from silicate D by impregnating silicate D with an aqueous solution of a manganese salt followed by drying the composition and calcining it. Catalyst 6 contained 3%w manganese.
Silicates E and F were used as such as catalyst 7 and catalyst 8, respectively.
Cata yst mixtures I-VI
- Six catalyst mixtures were prepared. The catalyst mixtures I-V
consisted each of a physical mixture of two of the above-mentioned catalysts in the following ratio:
Cat. mixture I = 2 pbv of cat. 5 + 1 pbv of cat. 6, Cat. mixture II = 2 pbv of cat. 5 + 1 pbv of cat. 7, Cat. mixture III= 2 pbv of cat. 5 + 1 pbv of cat. 8, Cat. mixture IV = 2.5 pbv of cat. 2 + 1 pbv of cat. 6, 20 Cat. mixture V = 2 pbv of cat. 3 + 1 pbv of cat. 7.
Catalyst mixture VI consisted of a layer of catalyst 4 ; and a layer of catalyst 1 in a volume ratio of 1:2.
The catalyst mixtures I-VI and catalyst 1 were tested for the preparation in one or two steps of a hydrocarbon mixture from an H2/C0 mixture. The test was carried out in ~e.or two reactors of 50 ml each, in which a fixed catalyst bed was present.
Twenty-three experiments were carried out. The experiments 1,4,7,10,15,17,19 and 22 were carried out in one step; the other experiments in two steps. In all the exEeriments, with the exception o~ experiments 14,22 and 23, a temperature of 375C was used in the ~irst step. In experiment 14 the temperature in the first step was 280C and in the experiments 22 and 23 the temperature in the first step was 250C.
:
'7 - ~6 -In all the experiments carried out in two steps the temperature in the second step was 220 C. In all the experiments, with the exception o~ experiments 14,22 and 23, a pressure of 60 bar was used. In OEperi~ents ~4,22 and 23 the pressure was 30 bar.
In the experi~ents 1,4,7 and 10 the space velocity was ~OOQ Nl.l h . In the experiments ~5,~7,~9 and 22 the space velocity was 50Q
Nl.l -1.h . In all the experiments carrîed out in two steps the space velocity, based on the sum of the total catalyst system (in the first & second step~ was 500 Nl.l. .h . In the experiments 6,9, and 12 the C4 fraction of the product from the first step was used as the feed for the second step. In the remainine experiments which were carried out in two steps, the total reaction product ~rom the first step was used as the feed for the second step. The results of the experiments are stated in Table C.
~ .
, ' , , '~ .
~L154~'7 H Ir~ 0 N H ~ ~ I
H ~ O ~ N ;--L
H Lr~ ~t N ~ 1~
H ~ N H I ~o H
U~
H u \ ~ Lr~ ~-- I U\ O
O H ~ N I I Ll~ C~
Il~ ~ Il~ G~ Ir~ ~ $
~ O ' ' ~
~ ; ,_ ~
CO H u~ . H I ~O
H
H ~ O
Lr~
~ H U~ ~ ~ o ,,~ 0 U~
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'-- H I I I I
a~
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~ ~ æ ~ , O ~ ~ ~ ~ o c~ ~ ~R ~ ~~ ~ . ~
~ $ ~ ~ --NhO ~ a) ~ s , .
~L1540;~7 ~ ~ ~ o N (rl ~ ~ N
,_ U~
~0 O ~ N Lf~ 1~ co O N C-- I N ~ ~ I I
~ . .
Lr~ N tr) O '- H Lr~ O
(:~ ~ ~ ~ N N H N
N ~ N
O CO N O H11~ ~ ~ H ,c~
CO ~ ~0 I N H I ~
N ~ O
~ O~ C\J ~ H
C-- N ~D I ~ H ~ I
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1~ 0 U~ t-- H
U~ ~ ~ I H I ~ I
O ~ CO ~ ~O ~ ~ O
~ C~
a) a u~ 0 ~ o ~1 u~
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N U~ ~t I ` H I .
i . ;
O t-- ~1 ~ U`\ :~ Lr~ Lr~ H
\ I -- H ~
-- O O
~ O
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h0~ ,~ I + ah~ ^ ~ ~ O q~ o . o 1~ C) Pl ~ . N ~ ~ p N~ 3 :
.
:
3L~s~
r~
c\J o L~
u~ ~o o ~ ~ o O ~ ~ ~ ~ CO
C~J
o~ o Lr~
Lr~
cO C~l C-- -- ~ ~D
~, I i ~ Ctl ~ I
u~
~0 N t-- cO
~,,1 U~ C~ O
--,. E~
:, ~
O U~
~ U~ O CO O~ O~ O C~
-- O O~
--aJ
,tn O
rl d $ ~ ~ ~J
vd O a~ ~
O C~ ~ ~1 O
æ n ~ o g R ~ ~ qo h ~ ~r/ ~ c~.
-- h ~ ~ ~ ~
R g ~ p ~ I +
1~ ~ o O 0 ~ R tR ~3 0 I Ir) O
~ & ~ a~ v~
.. . .. .
~154~3'7 Of the experiments listed in the table, only the two-step experiments 3, 6, 9, 12, 13, 14, 16, 18, 20, 21 and 23 are experiments according to the invention.
The one-step experiments 1, 4, 7, 10, 15, 17, 19 and 22 and the two-step experiments 2, 5, 8 and 11 are outside the scope of the invention. They have been included in the patent application for comparison. Of the two-step experiments 3, 6, 9, 12, 13, 14, 16, 18, 20, 21 and 23 only the experiments 16, 18, 20, 21 and 23 are experiments according to the present patent application.
The two-step experiments 3, 6, 9, 12, 13 and 14 are experiments according to the Canadian patent application 354,626, 10 The advantages of the two-step process according to the invention as regards the conversion of the H2/C0 mixture and the composition of the reaction product are evident when the results of the following experiments are compared Experiments 3 with experiments 1 and 2 " 6 " " 4 and 5 " 9 " " 7 and 8 " 12 and 13 " " 10 and 11 " 16 " " 15 " 18 " " 17 " 20 and 21 " " 19 ; " 23 " " 22 ~ - 20 -.~
Claims (8)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for the preparation of a hydrocarbon mixture, characterized in that a mixture of carbon monoxide and hydrogen with an H2/CO molar ratio of 1.0 - 2.0 is contacted in a first step with a bifunctional catalyst combination containing one or more metal components with catalytic activity for the con-version of an H2/CO mixture into acyclic hydrocarbons and/or acyclic oxygen-containing hydrocarbons, and a crystalline silicate which has the following properties after one hour's calcination in air at 500°C:
a) an X-ray powder diffraction pattern showing as strongest lines the 4 lines stated in Table A:
TABLE A
wherein the letters used have the following meanings:
VS = very strong; S = strong;
b) in the formula which represents the composition of the silicate, expressed in moles of the oxides, and in which, in addition to oxides of hydrogen, alkali metal and/or alkaline-earth metal and silicon, there is present one or more oxides of a trivalent metal A selected from the group formed by aluminium, iron, gallium, rhodium, chromium and scandium, the A2O3/SiO2 molar ratio (m) is less than 0.1, on the understanding that, if the H2/CO mixture has an H2CO molar ratio of less than 1.5, a trifunctional catalyst combination is used containing one or more metal components with catalytic activity for the conversion of an H2/CO
mixture into acyclic hydrocarbons, and/or acyclic oxygen-containing hydrocarbons, one or more metal components with catalytic activity for the conversion of an H2O/CO mixture into an H2/CO2 mixture and the crystalline silicate and that at least the C2- fraction of the reaction product from the first step is contacted in a second step with a catalyst containing one or more metal components with catalytic activity for the conversion of an H2/CO mixture into acyclic hydro-carbons, which metal components have been selected from the group formed by cobalt, nickel and ruthenium, on the understanding that if the feed for the second step has an H2/CO molar ratio of less than 1.5, water is added to this feed and that in the second step a bifunctional catalyst combination is used, which contains, in addition to the metal components with catalytic activity for the conversion of an H2/CO mixture into acyclic hydrocarbons, also one or more metal components with catalytic activity for the conversion of an H2O/CO mixture into an H2/CO2 mixture.
a) an X-ray powder diffraction pattern showing as strongest lines the 4 lines stated in Table A:
TABLE A
wherein the letters used have the following meanings:
VS = very strong; S = strong;
b) in the formula which represents the composition of the silicate, expressed in moles of the oxides, and in which, in addition to oxides of hydrogen, alkali metal and/or alkaline-earth metal and silicon, there is present one or more oxides of a trivalent metal A selected from the group formed by aluminium, iron, gallium, rhodium, chromium and scandium, the A2O3/SiO2 molar ratio (m) is less than 0.1, on the understanding that, if the H2/CO mixture has an H2CO molar ratio of less than 1.5, a trifunctional catalyst combination is used containing one or more metal components with catalytic activity for the conversion of an H2/CO
mixture into acyclic hydrocarbons, and/or acyclic oxygen-containing hydrocarbons, one or more metal components with catalytic activity for the conversion of an H2O/CO mixture into an H2/CO2 mixture and the crystalline silicate and that at least the C2- fraction of the reaction product from the first step is contacted in a second step with a catalyst containing one or more metal components with catalytic activity for the conversion of an H2/CO mixture into acyclic hydro-carbons, which metal components have been selected from the group formed by cobalt, nickel and ruthenium, on the understanding that if the feed for the second step has an H2/CO molar ratio of less than 1.5, water is added to this feed and that in the second step a bifunctional catalyst combination is used, which contains, in addition to the metal components with catalytic activity for the conversion of an H2/CO mixture into acyclic hydrocarbons, also one or more metal components with catalytic activity for the conversion of an H2O/CO mixture into an H2/CO2 mixture.
2. A process as claimed in claim 1, characterized in that the crystal-line silicate is an aluminium, iron or gallium silicate.
3. A process as claimed in claim 1, characterized in that the crystal-line silicate has a value form which is greater than 0.002 but smaller than 0.05.
4. A process as claimed in claim 2 or 3, characterized in that the crystalline silicate is an aluminum silicate which has a value for m which is greater than 0.005 and in that the silicate contains 0.1 - 10%w of an element selected from the group formed by manganese, calcium, magnesium and titanium.
5. A process as claimed in claim 1, 2 or 3, characterized in that the crystalline silicate has an alkali metal content of less than 0.1%w.
6. A process as claimed in claim 1, 2 or 3, characterized in that the first step is carried out at a temperature of 200 - 500°C, a pressure of 1 - 150 bar and a space velocity of 50 - 5000 Nl gas/l catalyst/h.
7. A process as claimed in claim 1, 2 or 3, characterized in that water is added to the feed for the first step and that a trifunctional catalyst combination is used in the first step.
8. A process as claimed in claim 1, 2 or 3, characterized in that the second step is carried out at a temperature of 125 - 350°C and a pressure of 1 - 150 bar.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| NL8001935 | 1980-04-02 | ||
| NL8001935A NL8001935A (en) | 1980-04-02 | 1980-04-02 | PROCESS FOR PREPARING HYDROCARBONS. |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1154037A true CA1154037A (en) | 1983-09-20 |
Family
ID=19835101
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000369477A Expired CA1154037A (en) | 1980-04-02 | 1981-01-28 | Process for the preparation of hydrocarbons and hydrocarbons so prepared |
Country Status (14)
| Country | Link |
|---|---|
| JP (1) | JPS56151786A (en) |
| AT (1) | AT371429B (en) |
| AU (1) | AU542307B2 (en) |
| BE (1) | BE887907A (en) |
| BR (1) | BR8101943A (en) |
| CA (1) | CA1154037A (en) |
| DE (1) | DE3112855A1 (en) |
| ES (1) | ES8203070A1 (en) |
| GB (1) | GB2073237B (en) |
| IN (1) | IN153737B (en) |
| IT (1) | IT1137551B (en) |
| NL (1) | NL8001935A (en) |
| NZ (1) | NZ196687A (en) |
| ZA (1) | ZA812143B (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3725018A (en) * | 1971-04-19 | 1973-04-03 | Fmc Corp | Form coke coated with glanz carbon and methods of production |
| NL8006484A (en) * | 1980-11-28 | 1982-06-16 | Shell Int Research | PROCESS FOR PREPARING HYDROCARBONS. |
| US4477595A (en) * | 1982-03-31 | 1984-10-16 | Exxon Research And Engineering Co. | Liquid hydrocarbon synthesis using supported ruthenium catalysts |
| IN161735B (en) * | 1983-09-12 | 1988-01-30 | Shell Int Research | |
| US4579986A (en) * | 1984-04-18 | 1986-04-01 | Shell Oil Company | Process for the preparation of hydrocarbons |
| US4568663A (en) * | 1984-06-29 | 1986-02-04 | Exxon Research And Engineering Co. | Cobalt catalysts for the conversion of methanol to hydrocarbons and for Fischer-Tropsch synthesis |
| US4579995A (en) * | 1984-06-29 | 1986-04-01 | Exxon Research And Engineering Co. | Process for the conversion of methanol to hydrocarbons |
| US4542122A (en) * | 1984-06-29 | 1985-09-17 | Exxon Research And Engineering Co. | Cobalt catalysts for the preparation of hydrocarbons from synthesis gas and from methanol |
| US4595703A (en) * | 1984-06-29 | 1986-06-17 | Exxon Research And Engineering Co. | Preparation of hydrocarbons from synthesis gas |
| US4513161A (en) * | 1984-06-29 | 1985-04-23 | Exxon Research And Engineering Co. | Conversion of methanol to hydrocarbons |
| US4556752A (en) * | 1984-06-29 | 1985-12-03 | Exxon Research And Engineering Co. | Preparation of liquid hydrocarbons from methanol |
| GB9009392D0 (en) * | 1990-04-26 | 1990-06-20 | Shell Int Research | Process for the preparation of an olefins-containing mixture of hydrocarbons |
| CN108816275B (en) * | 2018-04-19 | 2021-02-05 | 南京红太阳生物化学有限责任公司 | Catalyst for preparing pyridine base from synthesis gas, preparation method and application |
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| NL7811735A (en) * | 1978-11-30 | 1980-06-03 | Shell Int Research | PROCESS FOR PREPARING HYDROCARBONS. |
| NL7811736A (en) * | 1978-11-30 | 1980-06-03 | Shell Int Research | PROCESS FOR PREPARING HYDROCARBONS. |
| NL184214C (en) * | 1979-08-06 | 1989-05-16 | Shell Int Research | PROCESS FOR THE PREPARATION OF A HYDROCARBON MIXTURE FROM A MIXTURE CONTAINING CARBON MONOXIDE AND HYDROGEN WITH ONE HŸ2/CO MOL. CONTAINS LESS THAN 1.0 RATIO. |
-
1980
- 1980-04-02 NL NL8001935A patent/NL8001935A/en active Search and Examination
-
1981
- 1981-01-27 IN IN84/CAL/81A patent/IN153737B/en unknown
- 1981-01-28 CA CA000369477A patent/CA1154037A/en not_active Expired
- 1981-03-12 BE BE1/10169A patent/BE887907A/en not_active IP Right Cessation
- 1981-03-31 ZA ZA00812143A patent/ZA812143B/en unknown
- 1981-03-31 GB GB8110061A patent/GB2073237B/en not_active Expired
- 1981-03-31 JP JP4662181A patent/JPS56151786A/en active Pending
- 1981-03-31 AU AU68946/81A patent/AU542307B2/en not_active Ceased
- 1981-03-31 IT IT20840/81A patent/IT1137551B/en active
- 1981-03-31 ES ES500897A patent/ES8203070A1/en not_active Expired
- 1981-03-31 NZ NZ196687A patent/NZ196687A/en unknown
- 1981-03-31 AT AT0149781A patent/AT371429B/en not_active IP Right Cessation
- 1981-03-31 DE DE19813112855 patent/DE3112855A1/en active Granted
- 1981-03-31 BR BR8101943A patent/BR8101943A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| ZA812143B (en) | 1982-04-28 |
| GB2073237B (en) | 1983-08-24 |
| AU6894681A (en) | 1981-10-08 |
| NZ196687A (en) | 1983-04-12 |
| IN153737B (en) | 1984-08-18 |
| DE3112855C2 (en) | 1989-01-12 |
| AU542307B2 (en) | 1985-02-14 |
| GB2073237A (en) | 1981-10-14 |
| JPS56151786A (en) | 1981-11-24 |
| IT8120840A0 (en) | 1981-03-31 |
| IT1137551B (en) | 1986-09-10 |
| BR8101943A (en) | 1981-10-06 |
| BE887907A (en) | 1981-09-14 |
| DE3112855A1 (en) | 1982-01-07 |
| ES500897A0 (en) | 1982-02-16 |
| ATA149781A (en) | 1982-11-15 |
| NL8001935A (en) | 1981-11-02 |
| ES8203070A1 (en) | 1982-02-16 |
| AT371429B (en) | 1983-06-27 |
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