CA1128964A - Process for the preparation of hydrocarbons - Google Patents
Process for the preparation of hydrocarbonsInfo
- Publication number
- CA1128964A CA1128964A CA336,837A CA336837A CA1128964A CA 1128964 A CA1128964 A CA 1128964A CA 336837 A CA336837 A CA 336837A CA 1128964 A CA1128964 A CA 1128964A
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- CA
- Canada
- Prior art keywords
- catalyst
- silicate
- mixture
- process according
- composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides 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
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
- C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
- C07C1/0425—Catalysts; their physical properties
- C07C1/043—Catalysts; their physical properties characterised by the composition
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of zinc, cadmium or mercury
-
- 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
- C07C2523/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- C07C2523/24—Chromium, molybdenum or tungsten
- C07C2523/26—Chromium
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
ABSTRACT
PROCESS FOR THE PREPARATION OF HYDROCARBONS
In a single stage process for the production of aromatic gasoline from synthesis gas a mixture of a methanol synthesis catalyst and a specified crystal-line aluminosilicate zeolite is applied. The zeolite component has a SiO2/A1203 molar ratio below 200 and comprises an element selected from the group con-sisting of Mn, Ca, Mg and Ti.
PROCESS FOR THE PREPARATION OF HYDROCARBONS
In a single stage process for the production of aromatic gasoline from synthesis gas a mixture of a methanol synthesis catalyst and a specified crystal-line aluminosilicate zeolite is applied. The zeolite component has a SiO2/A1203 molar ratio below 200 and comprises an element selected from the group con-sisting of Mn, Ca, Mg and Ti.
Description
PROCESS FOR THE PREPARATION OF HYDROCAR~ONS
The invention relates to a prooess for the preparation of an aromatic hydrooarbon mixture ~rom a mixture of carbon monoxide and hydrogen using a mixture of two catalysts of which one haq the capability of catalysing the conversion of an H2/CO mixture into acyclic oxygen-containing hydro-carbons, and the other is a crystalline silicate which has the capability of catalysing the conversion of acyclic oxygen-containing hydrocarbons into aromatic hydrocarbons.
The said crystalline silicates are characterized by having the following properties after 1 hour's calcining in air at 500C:
a) thermally stable at a temperature above 600C, b) an X-ray powder diffraction pattern showing, inter alia, the reflections given in Table A.
~, , ,, .
~ , `
llZ8~
Table A
Radiation: Cu-K~ Wavelen~th 0.15418 nm _ relative intensity 7.8 - 8.2 S
8.7 - 9.1 M
11.8 - 12.1 W
12.4 - 12.7 W
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
20.2 - 20.6 W
20.7 - 21.1 W
23.1 - 23.4 VS
23.8 - 24.1 VS
24.2 - 24.8 S
29.7 - 30.1 M
where the letters used have the following meanings:
VS = very strong; S = strong; M = moderate; W = weak;
~ = angle according to Bragg's law.
c) after evacuation at 2 x 10 9 bar and 400C for 16 hours and measured at a hydrocarbon pressure of 8 x 10 2 bar and 100C, the adsorption of n-hexane is at least 0.8 mmol/g, the adsorption of 2,2-dimethylbutane at least 0.5 mmol/g, and the ratio o adsorption of n-hexane adsorption o~ 2,2-dimethylbutane at least 1-5 ~128964 d) the composition, expressed in moles of the oxides, is as follows:
y.(l.0 + 0.3). M20.y.A1203.Sio2, where M=H and alkali metal and O~ y~ 0.1, and e) the silicate contains one or more elements selected from the group of manganese, calcium, magnesium and titanium.
In an investigation by the Applicant concerning the above-mentioned process it was found that the catalyst mixtures show a higher C5+ selectivity according as, in the formula which shows the composition of the s licate, the value of y is lower.
It was found that to reach a C5+ selectivity which is acceptable for commercial use of the process, y should be at most 0.005.
This finding is the subject of Netherlands patent application No.
7811735*. Further investigation by the Applicant concerning the above-mentioned process has now revealed that also with catalyst mixtures in which a silicate is present whose value of y is greater than 0.005, an acceptable C5 selectivity can be reached, provided that the silicate contains one or more elements selected from the group of manganese, calcium, magnesium and titanium.
The invention therefore relates to a process for the preparation of an aromatic hydrocarbon mixture in which a mixture of carbon monoxide and hydrogen is contacted with a mixture of two catalystsof which one is capable of catalysing the conversion of an H2/CO mixture into acyclic oxygen-containing hydrocarbons, and the other is a crystalline silicate as defined above, of which, in the formula giving the composition of the silicate, the value * published May 30th, 1980 ~ ~ 1128964 of y is more than 0.005, and which contains one or more elements selected from the group of manganese, calcium, magnesium and titanium.
The process according to the invention starts from an H2/C0 mixture. Such a mixture can very conveniently 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 recovered from tar sand and bituminous shale.
The steam gasification is preferably carried out at a temperature between 900 and 1500C and a pressure between 10 and 50 bar. In the process according to the invention the preferred starting material is an H2/C0 mixture whose molar ratio iQ between 0.25 and 1Ø
The proce~s according to the invention is preferably carried out at a temperature of 200-500C and in particular of 300-450C, a pres~ure 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 a mixture of two catalysts is used, which, for the sake of convenience, will be designated catalysts X and Y. Catalyst X is the one which is capable of catalysing the conversion of an H2/C0 mixture into acyclic oxygen-containing hydrocarbons and ¢ataly9t Y is the crystalline silicate. Catalysts that are preferably used as X-catalysts are those which are capable of converting an H2/C0 mixture into substantially ~` 112896~
methanol and/or dimethyl ether. Very suitable for the present purpose are catalysts which contain zinc together with chromium. When using such a catalyst, it is preferred to choose one in which the atomic percentage of zinc, based on the sum of zinc and chromium, is at least 60%
and in particular 60-80S. The catalyst mixture that is used in the proces~ according to the invention may be a macromixture or a micromixture. In the first case the catalyst mixture consists of two kinds of macroparticles, of which one kind consists completely Or catalyst X, and the other kind completely of catalyst Y. In the second case the catalyst mixture consists of one kind of macroparticles, each macroparticle being built up of a great number of microparticles of each of the catalysts X and Y.
Catalyst mixtures in the form of micromixtures may be prepared, for instance, by thoroughly mixing a fine powder of catalyst X with a fine powder of catalyst Y and shaping the mixture into larger particles, for instance, by extru-ding or tabletting. In the process according to the inven-tion it is preferred to use catalyst mixtures in the form of micromixtures. In view of the required activity of the catalyst mixtures, preferred mixtures are those containing per part by volume of catalyst Y, 1-5 parts by volume of catalyst X.
The crystalline silicate that is present in the catalyst mixtures as catalyst Y, is defined, inter alia, with reference to the X-ray powder diffraction pattern shown by the silicate after 1 hour's calcining in air - - ~
,~ ' . .
~" ~ 1128964 at 500C. This X-ray powder diffraction pattern should contain, inter alia, the reflections shown in Table A.
The complete X-ray powder diffraction pattern of a typical example of a silicate eligible for use according to the invention is shown in Table B (Radiation: Cu-Kd; wave-length: 0.15418 nm).
Table B
The invention relates to a prooess for the preparation of an aromatic hydrooarbon mixture ~rom a mixture of carbon monoxide and hydrogen using a mixture of two catalysts of which one haq the capability of catalysing the conversion of an H2/CO mixture into acyclic oxygen-containing hydro-carbons, and the other is a crystalline silicate which has the capability of catalysing the conversion of acyclic oxygen-containing hydrocarbons into aromatic hydrocarbons.
The said crystalline silicates are characterized by having the following properties after 1 hour's calcining in air at 500C:
a) thermally stable at a temperature above 600C, b) an X-ray powder diffraction pattern showing, inter alia, the reflections given in Table A.
~, , ,, .
~ , `
llZ8~
Table A
Radiation: Cu-K~ Wavelen~th 0.15418 nm _ relative intensity 7.8 - 8.2 S
8.7 - 9.1 M
11.8 - 12.1 W
12.4 - 12.7 W
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
20.2 - 20.6 W
20.7 - 21.1 W
23.1 - 23.4 VS
23.8 - 24.1 VS
24.2 - 24.8 S
29.7 - 30.1 M
where the letters used have the following meanings:
VS = very strong; S = strong; M = moderate; W = weak;
~ = angle according to Bragg's law.
c) after evacuation at 2 x 10 9 bar and 400C for 16 hours and measured at a hydrocarbon pressure of 8 x 10 2 bar and 100C, the adsorption of n-hexane is at least 0.8 mmol/g, the adsorption of 2,2-dimethylbutane at least 0.5 mmol/g, and the ratio o adsorption of n-hexane adsorption o~ 2,2-dimethylbutane at least 1-5 ~128964 d) the composition, expressed in moles of the oxides, is as follows:
y.(l.0 + 0.3). M20.y.A1203.Sio2, where M=H and alkali metal and O~ y~ 0.1, and e) the silicate contains one or more elements selected from the group of manganese, calcium, magnesium and titanium.
In an investigation by the Applicant concerning the above-mentioned process it was found that the catalyst mixtures show a higher C5+ selectivity according as, in the formula which shows the composition of the s licate, the value of y is lower.
It was found that to reach a C5+ selectivity which is acceptable for commercial use of the process, y should be at most 0.005.
This finding is the subject of Netherlands patent application No.
7811735*. Further investigation by the Applicant concerning the above-mentioned process has now revealed that also with catalyst mixtures in which a silicate is present whose value of y is greater than 0.005, an acceptable C5 selectivity can be reached, provided that the silicate contains one or more elements selected from the group of manganese, calcium, magnesium and titanium.
The invention therefore relates to a process for the preparation of an aromatic hydrocarbon mixture in which a mixture of carbon monoxide and hydrogen is contacted with a mixture of two catalystsof which one is capable of catalysing the conversion of an H2/CO mixture into acyclic oxygen-containing hydrocarbons, and the other is a crystalline silicate as defined above, of which, in the formula giving the composition of the silicate, the value * published May 30th, 1980 ~ ~ 1128964 of y is more than 0.005, and which contains one or more elements selected from the group of manganese, calcium, magnesium and titanium.
The process according to the invention starts from an H2/C0 mixture. Such a mixture can very conveniently 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 recovered from tar sand and bituminous shale.
The steam gasification is preferably carried out at a temperature between 900 and 1500C and a pressure between 10 and 50 bar. In the process according to the invention the preferred starting material is an H2/C0 mixture whose molar ratio iQ between 0.25 and 1Ø
The proce~s according to the invention is preferably carried out at a temperature of 200-500C and in particular of 300-450C, a pres~ure 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 a mixture of two catalysts is used, which, for the sake of convenience, will be designated catalysts X and Y. Catalyst X is the one which is capable of catalysing the conversion of an H2/C0 mixture into acyclic oxygen-containing hydrocarbons and ¢ataly9t Y is the crystalline silicate. Catalysts that are preferably used as X-catalysts are those which are capable of converting an H2/C0 mixture into substantially ~` 112896~
methanol and/or dimethyl ether. Very suitable for the present purpose are catalysts which contain zinc together with chromium. When using such a catalyst, it is preferred to choose one in which the atomic percentage of zinc, based on the sum of zinc and chromium, is at least 60%
and in particular 60-80S. The catalyst mixture that is used in the proces~ according to the invention may be a macromixture or a micromixture. In the first case the catalyst mixture consists of two kinds of macroparticles, of which one kind consists completely Or catalyst X, and the other kind completely of catalyst Y. In the second case the catalyst mixture consists of one kind of macroparticles, each macroparticle being built up of a great number of microparticles of each of the catalysts X and Y.
Catalyst mixtures in the form of micromixtures may be prepared, for instance, by thoroughly mixing a fine powder of catalyst X with a fine powder of catalyst Y and shaping the mixture into larger particles, for instance, by extru-ding or tabletting. In the process according to the inven-tion it is preferred to use catalyst mixtures in the form of micromixtures. In view of the required activity of the catalyst mixtures, preferred mixtures are those containing per part by volume of catalyst Y, 1-5 parts by volume of catalyst X.
The crystalline silicate that is present in the catalyst mixtures as catalyst Y, is defined, inter alia, with reference to the X-ray powder diffraction pattern shown by the silicate after 1 hour's calcining in air - - ~
,~ ' . .
~" ~ 1128964 at 500C. This X-ray powder diffraction pattern should contain, inter alia, the reflections shown in Table A.
The complete X-ray powder diffraction pattern of a typical example of a silicate eligible for use according to the invention is shown in Table B (Radiation: Cu-Kd; wave-length: 0.15418 nm).
Table B
2 ~ relative intensity de~cription (100. I/Io) 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
17.75 5 BD
19.35 6 NL
20.40 9 NL
20.90 10 NL
21.80 4 NL
22.25 8 NL
23.25 1oox) SP
23.95 45 SP
24.40 27 SP
2~964 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
34.40 4 NL
36.05 5 BD
37.50 4 BD
45.30 9 BD
x) Io - intensity of the strongest separate reflection preqent in the pattern.
The letters used in Table B for describing the reflections have the following meanings:
SP = sharp; SR = ~houlder; NL = normal; BD = broad;
~ angle according to Bragg's law.
The crystalline silicates which are used in the catalyst mixtures can be prepared from an aqueous mixture as the starting material which contains the following compoundq:
one or more compounds of an alkali metal (M), one or more compounds containing an organic cation ~R) or from which such a cation is formed during the preparation of the sllicate, one or more silicon compound~ and one or more aluminium compounds. The preparation takes place by maintaining the mixture at elevated temperature until the silicate has been formed and subsequently separating ` 11~8964 the crystals of the silicate from the mother liquor.
In the aqueous mixture from which the silicates are pre-pared, the various compounds should be present in the following molar ratio, expressed in moles of the oxides:
M20 : (R)2/nO 0.1 20, (R)20 : SiO2 = 0.01-0.5, and SiO2 : Al203 ~ 200; n is the valency of R.
In the preparation of the silicates it is preferred to start from a basic mixture in which M is present in a sodium compound and R in a tetrapropylammonium compound.
In view of the required stability of the catalyst mixtures in the process according to the invention preference is given to silicates having an average crystallite size of less than 3000 nm and in particular of less than 1000 nm.
The average crystallite size of the silicates can be adjusted with the aid of the molar ratio of (R)2~nO to SiO2 in the starting mixture, in the sense that silicates with a lower average crystallite size are obtained accor-ding as the molar ratio of (R)2/nO to SiO2 in the starting mixture is cho~en higher.
In the process according to the invention preference is given to silicates of which, in the formula giving the composition of the silicate, the value of y is 0.01-0.02.
In the formula which gives the composition of the silicates, the value of y can be adjusted with the aid of the molar ratio of SiO2 to Al203 in the starting mixture, in the sense that silicates with a lower value for y are obtained according Z8g64 as the molar ratio Or SiO2 to Al203 in the starting mixture is chosen higher.
The silicate~ prepared in the way de~cribed above contain alkali metal ions and organic cations. By using suitable exchange methods the alkali metal ions can be replaced by other cations, such as hydrogen ions or ammonium ions. Organic cations can be very suitably converted into hydrogen ions by calcining the silicates.
The crystalline silicates which are u3ed in the catalyst mixtures preferably have an alkali metal content of less than 1 Sw and in particular less than 0.05 %w. If desired, a binder material such as bentonite or kaolin may be incor-porated into the catalyst mixtures.
In the process according to the invention a catalyst mixture should be used whose crystalline silicate component contains one or more elements selected from the group of manganese, calcium, magnesium and titanium. Preférably a catalyst mixture is used whose silicate component contains one or more of the above elements in an amount of 0.1-10 %w and in particular of 0.5-5 Sw, based on the silicate compo-nent in the mixture. Incorporation of the elements into the silicate component may take place in various ways, - for instance by ion exchange or by impregnation. It is preferred to use in the process a catalyst mixture in which incorporation of the elements into the silicate component has taken place by impregnating this component with an aqueous solution of one or more salts of the elements ," ~
:, , .', ' '' ~lZ~964 concerned, followed by drying and calcining of the silicate.
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, in which a fixed or a moving bed of the catalyst mixture concerned is present. The process may, for instance, be carried out by conducting a feed in upward direction through a vertically mounted catalyst bed, using ~uch a gas rate that expansion of the catalyst bed occurs.
If desired, the process can also be carried out using a suspension of the catalyst mixture in a hydrocarbon oil. Depending on whether the process is carried out with a fixed catalyst bed, an expanded catalyst bed or a catalyst suspension, preference is given to catalyst particles with a diameter between 1 and 5 mm, 0.5 and 2.5 mm and 20 and 150~ m, respectively.
The invention will now be explained with reference to the following example.
Example A crystalline silicate(silicate A) was prepared as follows: A mixture of SiO2, Na2AlO2, NaOH and /~C3H7)4N 70H in water with the molar composition 2 .Al2O3- 2.25/~3H7)4N72o- 37-5 sio2. 675 H2O was heated for 48 hours in an autoclave at 150C under auto-genous pressure. After the reaction mixture had cooled down, the silicate formed was filtered off 9 washed with water until the pH of the wash water was about 8 and dried ` llZ~3964 for two hours at 120C. After 1 hour's calcining in air at 500C silicate A had the following properties:
(a) thermally stable up to a temperature above 800C;
(b) an X-ray powder diffraction pattern substantially equal to the one given in Table B;
(c) after evacuation for 16 hours at 2 x 10 9 bar and 400C and measured at a hydrocarbon pressure of 8 x 10 2 bar and 100C, the adsorption of n-hexane is 1.2 mmol/g, the adsorption of 2,2-dimethylbutane 0.7 ~mol/g, ti adsorption of 2n 2-dimethylbutane (d) the composition, expressed in moles of the oxides, is 0.025 M20. 0.025 Al203.SiO2, where M - H and Na.
From silicate A, which had an average crystallite size of 250 nm, a silicate B was prepared by boiling the material calcined at 500C with 1.0 molar NH4N03 solution, washing with water, boiling again with 1.0 molar NH4N03 solution and washing, drying for 2 hours at 120C and calcining for 1 hour at 500C.
With silicate B as the starting material seven ~ilicates (silicateq C-I) were prepared, which contained 1-3 %w of one of the following elements: magnesium, calcium, titanium, manganese, molybdenum, chromium and cerium. The preparation was effected by impregnating samples of sili-cate B with an aqueous solution of a salt of the element concerned, followed by drying and calcining of the impregnated material.
Eight catalyst mixtures (I-VIII) were prepared by mixing ~12~3~164 a ZnO-Cr203 composition with each of the silicate~ B-I.
The atomic Zn percentage of the ZnO-Cr203 composition based on the sum of Zn and Cr was 70Z. The catalyst mixtures all contained per part by volume of silicate, 4 parts by volume of the ZnO-Cr203 composition.
Catalyst mixtures I-VIII were tested for the one-step preparation of an aromatic hydrocarbon mixture from an H2/C0 mixture. The testing was carried out in a 50-ml reactor in which a fixed catalyst bed with a volume of 7.5 ml was present. An H2/C0 mixture with an H2/C0 molar ratio of 0.5 was conducted for 48 hours at a temperature of 375C, a presqure of 60 bar and a space velocity of 1000 1.1 1.h 1 over the catalyst. The results of these experiments are given below:
-- -~ llZ896~
Exp. No. 1 2 3 4 5 6 7 8 Catalyst mixture No. I II III IV V VI VII VIII
Element deposited on the silicate - Mg Ca Ti Mn Mo Cr Ce Average composition of the C +
product, %w c4 16 15 6 7 12 13 13 17 c5+ 53 64 71 67 68 50 52 56 Average composition of the C5 pro-duct, Sw acyclic hydro-carbon~ 12 21 19 13 27 10 9 13 naphthenes 3 8 7 3 13 2 2 4 aromatics 85 71 74 84 59 88 89 83
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
17.75 5 BD
19.35 6 NL
20.40 9 NL
20.90 10 NL
21.80 4 NL
22.25 8 NL
23.25 1oox) SP
23.95 45 SP
24.40 27 SP
2~964 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
34.40 4 NL
36.05 5 BD
37.50 4 BD
45.30 9 BD
x) Io - intensity of the strongest separate reflection preqent in the pattern.
The letters used in Table B for describing the reflections have the following meanings:
SP = sharp; SR = ~houlder; NL = normal; BD = broad;
~ angle according to Bragg's law.
The crystalline silicates which are used in the catalyst mixtures can be prepared from an aqueous mixture as the starting material which contains the following compoundq:
one or more compounds of an alkali metal (M), one or more compounds containing an organic cation ~R) or from which such a cation is formed during the preparation of the sllicate, one or more silicon compound~ and one or more aluminium compounds. The preparation takes place by maintaining the mixture at elevated temperature until the silicate has been formed and subsequently separating ` 11~8964 the crystals of the silicate from the mother liquor.
In the aqueous mixture from which the silicates are pre-pared, the various compounds should be present in the following molar ratio, expressed in moles of the oxides:
M20 : (R)2/nO 0.1 20, (R)20 : SiO2 = 0.01-0.5, and SiO2 : Al203 ~ 200; n is the valency of R.
In the preparation of the silicates it is preferred to start from a basic mixture in which M is present in a sodium compound and R in a tetrapropylammonium compound.
In view of the required stability of the catalyst mixtures in the process according to the invention preference is given to silicates having an average crystallite size of less than 3000 nm and in particular of less than 1000 nm.
The average crystallite size of the silicates can be adjusted with the aid of the molar ratio of (R)2~nO to SiO2 in the starting mixture, in the sense that silicates with a lower average crystallite size are obtained accor-ding as the molar ratio of (R)2/nO to SiO2 in the starting mixture is cho~en higher.
In the process according to the invention preference is given to silicates of which, in the formula giving the composition of the silicate, the value of y is 0.01-0.02.
In the formula which gives the composition of the silicates, the value of y can be adjusted with the aid of the molar ratio of SiO2 to Al203 in the starting mixture, in the sense that silicates with a lower value for y are obtained according Z8g64 as the molar ratio Or SiO2 to Al203 in the starting mixture is chosen higher.
The silicate~ prepared in the way de~cribed above contain alkali metal ions and organic cations. By using suitable exchange methods the alkali metal ions can be replaced by other cations, such as hydrogen ions or ammonium ions. Organic cations can be very suitably converted into hydrogen ions by calcining the silicates.
The crystalline silicates which are u3ed in the catalyst mixtures preferably have an alkali metal content of less than 1 Sw and in particular less than 0.05 %w. If desired, a binder material such as bentonite or kaolin may be incor-porated into the catalyst mixtures.
In the process according to the invention a catalyst mixture should be used whose crystalline silicate component contains one or more elements selected from the group of manganese, calcium, magnesium and titanium. Preférably a catalyst mixture is used whose silicate component contains one or more of the above elements in an amount of 0.1-10 %w and in particular of 0.5-5 Sw, based on the silicate compo-nent in the mixture. Incorporation of the elements into the silicate component may take place in various ways, - for instance by ion exchange or by impregnation. It is preferred to use in the process a catalyst mixture in which incorporation of the elements into the silicate component has taken place by impregnating this component with an aqueous solution of one or more salts of the elements ," ~
:, , .', ' '' ~lZ~964 concerned, followed by drying and calcining of the silicate.
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, in which a fixed or a moving bed of the catalyst mixture concerned is present. The process may, for instance, be carried out by conducting a feed in upward direction through a vertically mounted catalyst bed, using ~uch a gas rate that expansion of the catalyst bed occurs.
If desired, the process can also be carried out using a suspension of the catalyst mixture in a hydrocarbon oil. Depending on whether the process is carried out with a fixed catalyst bed, an expanded catalyst bed or a catalyst suspension, preference is given to catalyst particles with a diameter between 1 and 5 mm, 0.5 and 2.5 mm and 20 and 150~ m, respectively.
The invention will now be explained with reference to the following example.
Example A crystalline silicate(silicate A) was prepared as follows: A mixture of SiO2, Na2AlO2, NaOH and /~C3H7)4N 70H in water with the molar composition 2 .Al2O3- 2.25/~3H7)4N72o- 37-5 sio2. 675 H2O was heated for 48 hours in an autoclave at 150C under auto-genous pressure. After the reaction mixture had cooled down, the silicate formed was filtered off 9 washed with water until the pH of the wash water was about 8 and dried ` llZ~3964 for two hours at 120C. After 1 hour's calcining in air at 500C silicate A had the following properties:
(a) thermally stable up to a temperature above 800C;
(b) an X-ray powder diffraction pattern substantially equal to the one given in Table B;
(c) after evacuation for 16 hours at 2 x 10 9 bar and 400C and measured at a hydrocarbon pressure of 8 x 10 2 bar and 100C, the adsorption of n-hexane is 1.2 mmol/g, the adsorption of 2,2-dimethylbutane 0.7 ~mol/g, ti adsorption of 2n 2-dimethylbutane (d) the composition, expressed in moles of the oxides, is 0.025 M20. 0.025 Al203.SiO2, where M - H and Na.
From silicate A, which had an average crystallite size of 250 nm, a silicate B was prepared by boiling the material calcined at 500C with 1.0 molar NH4N03 solution, washing with water, boiling again with 1.0 molar NH4N03 solution and washing, drying for 2 hours at 120C and calcining for 1 hour at 500C.
With silicate B as the starting material seven ~ilicates (silicateq C-I) were prepared, which contained 1-3 %w of one of the following elements: magnesium, calcium, titanium, manganese, molybdenum, chromium and cerium. The preparation was effected by impregnating samples of sili-cate B with an aqueous solution of a salt of the element concerned, followed by drying and calcining of the impregnated material.
Eight catalyst mixtures (I-VIII) were prepared by mixing ~12~3~164 a ZnO-Cr203 composition with each of the silicate~ B-I.
The atomic Zn percentage of the ZnO-Cr203 composition based on the sum of Zn and Cr was 70Z. The catalyst mixtures all contained per part by volume of silicate, 4 parts by volume of the ZnO-Cr203 composition.
Catalyst mixtures I-VIII were tested for the one-step preparation of an aromatic hydrocarbon mixture from an H2/C0 mixture. The testing was carried out in a 50-ml reactor in which a fixed catalyst bed with a volume of 7.5 ml was present. An H2/C0 mixture with an H2/C0 molar ratio of 0.5 was conducted for 48 hours at a temperature of 375C, a presqure of 60 bar and a space velocity of 1000 1.1 1.h 1 over the catalyst. The results of these experiments are given below:
-- -~ llZ896~
Exp. No. 1 2 3 4 5 6 7 8 Catalyst mixture No. I II III IV V VI VII VIII
Element deposited on the silicate - Mg Ca Ti Mn Mo Cr Ce Average composition of the C +
product, %w c4 16 15 6 7 12 13 13 17 c5+ 53 64 71 67 68 50 52 56 Average composition of the C5 pro-duct, Sw acyclic hydro-carbon~ 12 21 19 13 27 10 9 13 naphthenes 3 8 7 3 13 2 2 4 aromatics 85 71 74 84 59 88 89 83
Claims (9)
1. A process for the preparation of an aromatic hydrocarbon mixture, characterized in that a mixture of carbon monoxide and hydrogen is contacted with a mixture of two catalysts of which one is capable of catalysing the conversion of an H2/C0 mixture into acyclic oxygen-containing hydrocarbons, and the other is a crystalline silicate, which silicate is characterized by having the following properties after 1 hour's calcining in air at 500°C:
(a) thermally stable at a temperature above 600°C, (b) an X-ray powder diffraction pattern showing, inter alia, the reflectionq given in Table A.
Table A
where the letters used have the following meanings:
VS = very strong; S = strong; M = moderate; W - weak;
.THETA. = angle according to Bragg's law.
(c) after evacuation at 2 x 10 9 bar and 400°C for 16 hours and measured at a hydrocarbon pressure of 8x10 2 bar and 100°C, the adsorption of n-hexane is at least 0.8 mmol/g, the adsorption of 2,2-dimethylbutane at least 0.5 mmol/g, and the ratio at least 1.5 (d) the composition, expressed in moles of the oxides, is as follows:
y.(1.0+0.3). M20.y.A1203.SiO2, where M = H and alkali metal and y >0.005, and (e) the silicate contains one or more elements selected from the group of manganese, calcium, magnesium and titanium.
(a) thermally stable at a temperature above 600°C, (b) an X-ray powder diffraction pattern showing, inter alia, the reflectionq given in Table A.
Table A
where the letters used have the following meanings:
VS = very strong; S = strong; M = moderate; W - weak;
.THETA. = angle according to Bragg's law.
(c) after evacuation at 2 x 10 9 bar and 400°C for 16 hours and measured at a hydrocarbon pressure of 8x10 2 bar and 100°C, the adsorption of n-hexane is at least 0.8 mmol/g, the adsorption of 2,2-dimethylbutane at least 0.5 mmol/g, and the ratio at least 1.5 (d) the composition, expressed in moles of the oxides, is as follows:
y.(1.0+0.3). M20.y.A1203.SiO2, where M = H and alkali metal and y >0.005, and (e) the silicate contains one or more elements selected from the group of manganese, calcium, magnesium and titanium.
2. A process according to claim 1, characterized in that the catalyst mixture is built up of a catalyst X and a catalyst Y, catalyst X being capable of converting an H2/CO mixture into substantially methanol and/or dimethyl ether, and catalyst Y being the crystalline silicate.
3. A process according to claim 2, characterized in that as the X-catalyst a composition is used which contains zinc to-gether with chromium.
4. A process according to any one of claims 2 and 3, char-acterized in that the catalyst mixture contains per part by volume of catalyst Y, 1-5 parts by volume of catalyst X.
5. A process according to claim 1, characterized in that the catalyst mixture contains a crystalline silicate whose average crystallite size is less than 3000 nm.
6. A process according to claim 1, characterized in that the catalyst mixture contains a crystalline silicate of which, in the formula which gives the composition of the silicate, the value of y is 0.01-0.02.
7. A process according to claim 1, characterized in that the catalyst mixture contains a crystalline silicate containing one or more of the elements manganese, calcium,magnesium and titanium in an amount of 0.1-10 %w based on the amount of silicate in the mixture.
8. A process according to claim 7, characterized in that the incorporation of the elements into the silicate has been effec-ted by impregnating the silicate with an aqueous solution of one or more salts of the elements concerned followed by drying and calcining the silicate.
9. A process according to claim 1, characterized in that the catalyst mixture contains a crystalline silicate having an alkali metal content of less than 0.05 %w.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| NL7811736A NL7811736A (en) | 1978-11-30 | 1978-11-30 | PROCESS FOR PREPARING HYDROCARBONS. |
| NL7811736 | 1978-11-30 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1128964A true CA1128964A (en) | 1982-08-03 |
Family
ID=19831974
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA336,837A Expired CA1128964A (en) | 1978-11-30 | 1979-10-02 | Process for the preparation of hydrocarbons |
Country Status (9)
| Country | Link |
|---|---|
| JP (1) | JPS5589234A (en) |
| AU (1) | AU529719B2 (en) |
| CA (1) | CA1128964A (en) |
| DE (1) | DE2947930A1 (en) |
| FR (1) | FR2442818A1 (en) |
| GB (1) | GB2037808B (en) |
| IT (1) | IT1126414B (en) |
| NL (1) | NL7811736A (en) |
| ZA (1) | ZA796468B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9938217B2 (en) | 2016-07-01 | 2018-04-10 | Res Usa, Llc | Fluidized bed membrane reactor |
| US9981896B2 (en) | 2016-07-01 | 2018-05-29 | Res Usa, Llc | Conversion of methane to dimethyl ether |
| US10189763B2 (en) | 2016-07-01 | 2019-01-29 | Res Usa, Llc | Reduction of greenhouse gas emission |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL176551C (en) * | 1979-04-25 | 1985-05-01 | Shell Int Research | PROCESS FOR PREPARING AN AROMATIC HYDROCARBON MIXTURE BY CATALYTIC CONVERSION OF A MIXTURE OF CARBON MONOXIDE AND HYDROGEN. |
| 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. |
| NL8001935A (en) * | 1980-04-02 | 1981-11-02 | Shell Int Research | PROCESS FOR PREPARING HYDROCARBONS. |
| NL8103397A (en) * | 1981-07-17 | 1983-02-16 | Shell Int Research | METHOD FOR PREPARING ORGANIC COMPOUNDS. |
| JPH0330442U (en) * | 1989-07-31 | 1991-03-26 |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1062285A (en) * | 1974-04-24 | 1979-09-11 | Mobil Oil Corporation | Conversion of synthesis gas to hydrocarbon mixtures |
| GB1489357A (en) * | 1975-06-02 | 1977-10-19 | Mobil Oil Corp | Conversion of synthesis gas to hydrocarbon mixtures |
-
1978
- 1978-11-30 NL NL7811736A patent/NL7811736A/en not_active Application Discontinuation
-
1979
- 1979-10-02 CA CA336,837A patent/CA1128964A/en not_active Expired
- 1979-11-28 JP JP15306079A patent/JPS5589234A/en active Granted
- 1979-11-28 IT IT27659/79A patent/IT1126414B/en active
- 1979-11-28 ZA ZA00796468A patent/ZA796468B/en unknown
- 1979-11-28 DE DE19792947930 patent/DE2947930A1/en active Granted
- 1979-11-28 FR FR7929273A patent/FR2442818A1/en active Granted
- 1979-11-28 AU AU53271/79A patent/AU529719B2/en not_active Ceased
- 1979-11-28 GB GB7941074A patent/GB2037808B/en not_active Expired
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9938217B2 (en) | 2016-07-01 | 2018-04-10 | Res Usa, Llc | Fluidized bed membrane reactor |
| US9981896B2 (en) | 2016-07-01 | 2018-05-29 | Res Usa, Llc | Conversion of methane to dimethyl ether |
| US10189763B2 (en) | 2016-07-01 | 2019-01-29 | Res Usa, Llc | Reduction of greenhouse gas emission |
Also Published As
| Publication number | Publication date |
|---|---|
| IT1126414B (en) | 1986-05-21 |
| FR2442818B1 (en) | 1984-01-27 |
| AU529719B2 (en) | 1983-06-16 |
| DE2947930A1 (en) | 1980-06-12 |
| IT7927659A0 (en) | 1979-11-28 |
| JPS6245848B2 (en) | 1987-09-29 |
| AU5327179A (en) | 1980-06-05 |
| GB2037808A (en) | 1980-07-16 |
| FR2442818A1 (en) | 1980-06-27 |
| DE2947930C2 (en) | 1987-08-20 |
| JPS5589234A (en) | 1980-07-05 |
| ZA796468B (en) | 1980-11-26 |
| NL7811736A (en) | 1980-06-03 |
| GB2037808B (en) | 1982-09-22 |
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