JPS6245848B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention is a combination of zinc and chromium as one catalyst is capable of catalyzing the conversion of _H2 /CO mixtures to acyclic oxygen-containing hydrocarbons;
and from a mixture of carbon monoxide and hydrogen using a mixture of two catalysts, the other catalyst being a crystalline silicate capable of catalyzing the conversion of acyclic oxygen-containing hydrocarbons to aromatic hydrocarbons. The present invention relates to a method for producing an aromatic hydrocarbon mixture. The crystalline silicate, after calcination in air at 500°C for 1 hour, has the following properties: a) thermal stability at temperatures above 600°C, b) a powder X-ray diffraction pattern showing, inter alia, the reflections listed in Table A ; Radiation: Cu-Kα Wavelength 0.15418nm 2ΘRelative 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 S 24.2−24.8 M 29.7−30.1 M The symbols in the table have the following meanings: VS = very strong; S = strong; M = moderate; W = weak; Θ = angle according to Bragg'slaw, c 2 × 10 ^-9 Kg/cm ² , after evacuation at 400 °C for 16 hours, at 100 °C with a hydrocarbon pressure of 8 × 10 ^-2 Kg/cm ² n-hexane adsorption of at least 0.8 mmol/g, at least 0.5 mmol/g 2,
2-dimethylbutane adsorption amount, and at least
Ratio of 1.5 Adsorption amount of n-hexane/adsorption amount of 2,2-dimethylbutane, d Composition of the following formula expressed in moles of oxide; Y. (1.0±3). It is characterized by having M ₂ OYAl ₂ O ₃ .SiO ₂ , where M=H and alkali metal, 0<Y〓0.1. In the applicant's research on the above method,
It has been found that the catalyst mixture exhibits higher C ₅ ⁺ selectivity as the value of Y in the formula representing the composition of the silicate decreases. It has been found that Y must be at most 0.005 to reach an acceptable C ₅ ⁺ selectivity for industrial use of the process. This knowledge was published in Dutch patent application No. 7811735.
Japanese patent application corresponding to No.
issue). Studies by the Applicant regarding the above-mentioned process have further shown that even in catalyst mixtures in which silicates are present with a value of Y greater than 0.005, the silicates contain one or more elements selected from the group of manganese, calcium, magnesium and titanium. It was found that acceptable C ₅ ⁺ selectivity could be reached if The present invention is therefore a combination of zinc and chromium as having the ability to catalyze the conversion of a mixture of carbon monoxide and hydrogen, one of which is a _H2 /CO mixture, to an acyclic oxygen-containing hydrocarbon; And in the other equation giving the composition of the silicate, the value of Y is
Aromatic carbonization by contacting with a mixture of two catalysts, which are crystalline silicates as defined above, greater than 0.005 and containing one or more elements selected from the group of manganese, calcium, magnesium and titanium. The present invention relates to a method for producing a hydrogen mixture. The process according to the invention starts from a H ₂ /CO mixture. Such mixtures can be produced very conveniently by steam gasification of carbon-containing materials. Examples of such materials are lignite, anthracite, coke, crude mineral oil and its fractions, and oils recovered from tar sands and bituminous shales. Steam gasification is 900 or
Preferably it is carried out at a temperature of 1500° C. and a pressure of 10 to 51 kg/cm ² . Preferred starting materials in the process according to the invention are H ₂ /CO in a molar ratio of 0.25 to 1.0.
It is a mixture. The method according to the invention is preferably performed at a temperature of 200-500°C, especially 300-450°C, 1-153 Kg/ ^cm2, especially 5-102
It is carried out at a pressure of Kg/cm ² and a space velocity of 50-5000, especially 300-3000 Nl gas/catalyst/h. In the process according to the invention, a mixture of two catalysts is used, which for convenience are named catalysts X and Y. _Catalyst
or dimethyl ether), and catalyst Y is a crystalline silicate. Preferably, the X-catalyst is selected to have an atomic percentage of zinc of at least 60%, in particular 60-80%, based on the sum of zinc and chromium. The catalyst mixture used in the process according to the invention can be a macromixture or a micromixture. In the first case, the catalyst mixture consists of two types of macroparticles, one type consisting entirely of catalyst X and the other type consisting entirely of catalyst Y. In the latter case, the catalyst mixture consists of one type of macroparticles;
Each macroparticle is composed of a large number of fine particles of each of catalysts X and Y. Catalyst mixtures in the form of micromixtures can be produced, for example, by intimately mixing finely divided powders of catalyst X with finely divided powders of catalyst Y and shaping this mixture into larger particles, for example by extrusion or tabletting. In the process according to the invention, preference is given to using catalyst mixtures in the form of micromixtures. In view of the required activity of the catalyst mixture, preferred mixtures contain 1-5 parts by volume of catalyst X per 1 part by volume of catalyst Y. The crystalline silicate present as catalyst Y in the catalyst mixture is defined, inter alia, with respect to the powder X-ray diffraction pattern exhibited by the silicate after calcination at 500° C. for 1 hour in air. This powder X-ray diffraction pattern should contain, among other things, the reflections shown in Table A. Complete powder X-ray diffraction patterns of representative examples of silicates suitable for use in accordance with the present invention are shown in Table B (radiation: Cu-Kα, wavelength:
0.15418nm)

【table】

[Table] Intensity of the strongest single reflection.
The symbols in the notes column used to describe reflexes in Table B have the following meanings: SP = sharp; SR = shoulder; NL = normal; BD = wide; Θ = angle according to Bragg's law. The crystalline silicates used in the catalyst mixture may be prepared from an aqueous starting mixture containing a mixture of: 1 of the alkali metal (M);
species or more compounds, organic cations (R)
or generate such cations during silicate preparation, one or more silicon compounds and one or more aluminum compounds. The preparation is carried out by holding the mixture at elevated temperature until the silicate forms and then separating the silicate crystals from the mother liquor. In the aqueous mixture for silicate production, the various compounds should be present in the following molar ratios expressed in moles of oxide: _M2O :(R) _2/o O=0.1-20, ( R) _2O : _SiO2 = 0.01-0.5, and _SiO2 : _{Al2O3 <} 200, (n is the valence of R) In the production of silicates, M is a sodium compound and R is a tetrapropylammonium Preference is given to starting from the basic mixture present in the compound. Considering the required stability of the catalyst mixture in the process according to the invention, the average crystallite size is 3000 nm.
Smaller silicates, especially smaller than 1000 nm, are preferred. The average crystallite size of silicate is
It can be adjusted by the molar ratio of (R) _{2 /o} O to SiO 2 in the starting mixture, i.e. the larger the molar ratio of (R) _2/o O to SiO ₂ in the starting mixture is chosen, the more A silicate with a small average crystallite size is obtained. In the method according to the invention, silicates are preferred in which the value of Y in the formula giving the composition of the silicate is 0.01-0.02. In the formula giving the composition of the silicate, the value of Y can be adjusted by the molar ratio of SiO 2 to Al ₂ O ₃ in the starting mixture, i.e. the more _{SiO 2} to Al ₂ O ₃ in the starting mixture Depending on the selection, silicates with smaller Y values can be obtained. The silicates produced as described above contain alkali metal ions and organic cations.
By using appropriate exchange methods, alkali metal ions can be replaced by other cations such as hydrogen ions or ammonium ions. Organic cations can be very conveniently converted into hydrogen ions by calcination of the silicate. The crystalline silicates used in the catalyst mixture preferably have an alkali metal content of less than 1% by weight, in particular less than 0.05% by weight. If desired, binders such as bentonite or kaolin may be incorporated into the catalyst mixture. In the process according to the invention, catalyst mixtures should be used in which the crystalline silicate component contains one or more elements selected from the group of manganese, calcium, magnesium and titanium. Preferably catalyst mixtures are used in which the silicate component contains one or more of the above-mentioned elements in an amount of 0.1-10% by weight, in particular 0.5-5% by weight, based on the silicate component in the catalyst mixture. The addition of the element into the silicate component can be carried out in various ways, for example by ion exchange or impregnation. Addition of the element to the silicate component makes the component 1 of the element.
Preferably, a catalyst mixture is used in the process, which is made by impregnating with an aqueous solution of the species or salts, followed by drying and calcining the silicate. The process according to the invention can be carried out very advantageously by introducing the raw materials in an upward or downward direction into an uprightly mounted reactor, which is charged with a fixed or moving bed of the catalyst mixture. The process may be carried out, for example, by introducing the feedstock in an upward direction into a vertically loaded catalyst bed using a gas velocity such 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 or with an expanded catalyst bed or with a catalyst suspension, catalyst particles with a diameter of 1 to 5 mm, 0.5 to 2.5 mm and 20 to 150 μm, respectively, are preferred. The invention is further illustrated by the following examples. EXAMPLES A crystalline silicate (silicate A) was prepared as follows: a mixture of SiO ₂ , Na ₂ AlO ₂ , NaOH and [(C ₃ H ₇ ) ₄ N]OH in water (molar composition
1.5Na ₂ O.Al ₂ O ₃ .2.25
[(C ₃ H ₇ ) ₄ N] ₂ O.37.5SiO ₂ .675H ₂ O) was heated in an autoclave at 150° C. under autogenous pressure for 48 hours. After the reaction mixture had cooled down, the silicate produced was filtered, washed with water until the pH of the washing water was about 8, and dried at 120° C. for 2 hours. After calcination in air at 500°C for 1 hour, Silicate A had the following properties: a thermal stability up to temperatures above 800°C; b powder X substantially identical to that shown in Table B. Line diffraction pattern: c 2×10 ^-9 Kg/cm ² , after evacuation at 400°C for 16 hours, 8
x10 ^-2 Kg/cm ² hydrocarbon pressure and 100°C, n-hexane adsorption 1.2 mmol/g, 2,2-dimethylbutane adsorption 0.7 mmol/g and ratio n-hexane adsorption/ 2,2-dimethylbutane adsorption amount
1.7; d The composition expressed in moles of oxide is
0.025M ₂ O.0.025Al ₂ O ₃ .SiO ₂ (M=H and
Na). From silicate A with an average microcrystal size of 250 nm,
Boiling the calcined material at 500°C with a 1.0 molar NH ₄ NO ₃ solution, washing with water, boiling again with a 1.0 molar NH ₄ NO ₃ solution, washing, drying at 120°C for 2 hours, and calcining at 500°C for 1 hour. Silicate B (whose properties are essentially the same as those of silicate A) was prepared by: Starting from silicate B, seven silicates (silicate C-) containing 1-3% by weight of one of the following elements were prepared: magnesium, calcium, titanium, manganese, molybdenum, chromium and cerium. The production was carried out by impregnating a sample of silicate B with an aqueous solution of a salt of the element in question, then drying and calcining the impregnated material. Eight catalyst mixtures ₍ -) were prepared by mixing the ZnO- _Cr2O3 composition with each of the silicate B-. Zn in ZnO− _{Cr2O3 composition}
The atomic percentage was 70% based on the sum of Zn and Cr. All catalyst mixtures contained 4 parts by volume of ZnO- _Cr2O3 composition _per part by volume of silicate. The catalyst mixture was tested for the production of aromatic hydrocarbon mixtures in one stage from _H2 /CO mixtures. The test was loaded with a fixed catalyst bed with a volume of 7.5 ml.
It was carried out in a 50ml reactor. H ₂ /CO molar ratio is 0.5
The H ₂ /CO mixture was passed over the catalyst at a temperature of 375° C., a pressure of 61 Kg/cm ² and a space velocity of 1000· ^-1 ·h ⁻¹ for 48 hours. The experimental results are shown below: Experiments No. 1 and 6-8 are comparative examples outside the scope of the present invention, and Experiments No. 2-5 are examples of the present invention.

【table】

【table】

Claims (1)

[Claims] 1. A method for producing an aromatic hydrocarbon mixture,
contacting a mixture of carbon monoxide and hydrogen with a mixture of two catalysts, one containing zinc and chromium and the other a crystalline silicate, the silicate being heated at 500° C. in air for 1 hour After firing the following properties: a thermal stability at temperatures above 600°C, b powder X-ray diffraction pattern showing the reflections listed in Table A; Table A radiation: Cu-Kα wavelength 0.15418 nm 2θ 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 S 24.2− 24.8 M 29.7−30.1 M [The symbols used in the table have the following meanings: VS = very strong; S = strong; M = moderate; W = weak; θ = angle according to Bragg's law ] c After evacuation for 16 hours at 2×10 ^-9 Kg/cm ² and 400°C, hydrocarbon pressure of 8×10 ^-2 Kg/cm ² and 100°C
n of at least 0.8 mmol/g, measured at
- hexane adsorption amount, at least 0.5 mmol/
g of 2,2-dimethylbutane adsorption, and a ratio of at least 1.5 n-hexane adsorption/2,2-dimethylbutane adsorption, d composition of the following formula expressed in moles of oxide; 1.0±0.3)・M ₂ O・Y・Al ₂ O ₃・SiO ₂ (where M=H and alkali metal, Y>
0.005), and e the silicate contains one or more elements selected from the group of manganese, calcium, magnesium and titanium. 2. Process according to claim 1, characterized in that the catalyst mixture contains 1-5 parts by volume of catalyst containing zinc and chromium per part by volume of crystalline silicate catalyst. 3. Process according to claim 1 or 2, characterized in that the catalyst mixture comprises a crystalline silicate with an average crystallite size of less than 3000 nm. 4. Process according to any one of claims 1 to 3, characterized in that the catalyst mixture comprises a crystalline silicate in which the value of Y in the formula giving the composition of the silicate is 0.01-0.02. 5. The catalyst mixture contains one or more of the elements manganese, calcium, magnesium and titanium, based on the amount of silicate in the mixture.
5. Process according to any one of claims 1 to 4, characterized in that it contains crystalline silicates in an amount of 10% by weight. 6. Claims characterized in that the addition of the element into the silicate is carried out by impregnating the silicate with an aqueous solution of one or more salts of the element, then drying and calcining the silicate. The method described in Section 5. 7. Process according to any one of claims 1 to 6, characterized in that the catalyst mixture comprises a crystalline silicate with an alkali metal content of less than 0.05% by weight.