The method of preparation of the catalyst and a method of producing hydrocarbons and their oxygenated derivatives using it

 

(57) Abstract:

The invention relates to catalysts for obtaining hydrocarbons, including liquid synthetic fuels, olefins, solid hydrocarbons and their oxygenated derivatives, such as alcohols from a mixture of CO and hydrogen. The invention solves the problem of developing a method of making an effective catalyst and method of producing hydrocarbons and their oxygen-containing compounds using this catalyst. The catalyst is prepared from a powder of the catalytically active agent, heat-conductive agent and a pore-forming agent with a particle size less than 300 microns as follows: mix the powders heat-conductive and a pore-forming agents, the resulting powder was then mixed with a catalytically active agent, condense the mixture and give the body of catalyst required form, then carry out thermal treatment of the catalyst body. 2 C. and 13 C.p. f-crystals, 2 tab.

The invention relates to catalysts for obtaining hydrocarbons, including liquid synthetic fuels, olefins, solid hydrocarbons and their oxygenated derivatives, such as alcohols from a mixture of CO and hydrogen (synthesis gas). In further or to obtain useful chemical compounds for example hydrocarbons with a smaller number of carbon atoms per molecule, polymeric materials, higher alcohols, surfactants, etc.

Known methods for the conversion of synthesis gas into valuable chemical products by reactions

JI+(2n+1)H2=CnH2n+2+mo2O

JI+(2n)N2=CnH2n+mo2O

JI+(2n)N2=CnH2n+1HE+(n-1)H2O

in the presence of a catalyst. These methods are combined under the name "Fischer-Tropsch synthesis". As a result of the Fischer-Tropsch synthesis can be quantitatively obtained and allocated saturated and unsaturated hydrocarbons with any number of carbon atoms from 1 (methane) to more than 100, and alcohols. The catalyst typically contains one or more elements from the group of iron, cobalt, Nickel and ruthenium. The synthesis gas may have a different ratio of CO:H2determined by the method of its production, and can also be diluted with nitrogen.

The analysis of the characteristics of the Fischer-Tropsch synthesis, carried out in the overview A. A. hasin, V. A. Kirillov, Catalysis in industry, No. 2, 2002, pp. 26-37, helped to formulate the basic requirements for the organization katal is the following criteria to the layer of catalyst, necessary to ensure the effective conduct of the process of the Fischer-Tropsch synthesis:

1. high concentration of the catalytically active component in the reaction volume;

2. small characteristic size of the catalyst particles (less than 50 microns);

3. high effective thermal conductivity of the catalyst layer;

4. the developed surface of the partition phase gas - liquid;

5. securing and convective gas flow close to the ideal mode of displacement.

In the cited review also concludes the mismatch of process diagrams with traditional catalysts in the suspended layer, a fixed layer or fluidized bed set requirements. Therefore, improving the efficiency of the production of hydrocarbons from synthesis gas requires the development of a new method of preparation of the catalyst.

Closest to videoshablony tasks are solved with the invention of US Patent 5716899, B 01 J 21/04, 10.02.1998. This invention proposes a method of preparing a body of catalyst by placing the suspension containing particles of a catalytically active agent and other materials, including ceramics, metals, glass, etc. in a matrix of cellular materials liquid removed from the slurry. In this preferred relies on the use of a ceramic honeycomb matrix, as it provides a high porosity of the walls of the matrix.

The disadvantage of the proposed method is the low content of catalytically active component in a unit volume of the catalyst body, and the difficulty of reaching a wall thickness less than 50 microns, to provide intensive mass transfer within the porous structure of the wall matrix. It should also be noted the low thermal conductivity of ceramic materials proposed by the invention as a matrix.

The problem solved by this invention is to develop a method of making an effective catalyst for obtaining hydrocarbons and their oxygenated derivatives from synthesis gas that meets the following requirements:

1. High concentration of catalytically active agent is not less than 0.4 g/cm3;

2. High mechanical strength of the body of catalyst;

3. The high conductivity of the body of catalyst is not less than 1 W/(m·K);

4. The high permeability of the body of catalyst is not less than 5·10-15m2;

5. Developed porous structure with a predominance of pore size is let by successively carrying out the following operations:

- preparation of powders a, B and C, consisting respectively of granules catalytically active agent (powder A), heat-conductive agent (powder B) and a pore-forming agent (powder) with size less than 300 microns,

the mixture of powders B and C (powder D)

- compaction of the powder G, the preparation of the compacted powder mass fraction of less than 300 μm,

the mixture of powders a and G

seal the mixture and making the body of catalyst necessary forms

thermal treatment of the catalyst body.

The term “catalytically active agent” is understood here as a set of phases, including phase containing the active metal cations (for example, cobalt, iron, Nickel, ruthenium or their content). Essential is the ability of a catalytically active agent to become in the course of thermal treatment of the body of catalyst in a reducing environment in a set of phases, including phase active metal, secured to the phase of the substrate of the oxide nature have a decisive influence on the physico-chemical properties of the active metal phase, such as its dispersion. The content of active metal in the above-mentioned set of phases DG of the previously described methods of preparation by precipitation (US Patent 5397806, 07 With 001/04, 14.03.95), impregnation (US Patent 4960801, C 07 C 001/04, 02.10.90, US Patent 4613624, C 07 C 001/04, 23.09.86) or other known or original way. Preferably, the active metal phase formed during heat treatment, had a predominant particle size from 6-7 to 9-11 nm.

The term “heat transfer agent” refers to a phase or combination of phases of one or more metals, inert with respect to synthesis gas, such as copper, zinc, aluminum or their intermetallic compounds and alloys. Essential properties for the heat transfer agent is its high conductivity after stage heat treatment (not less than 50 W·m-1·K-1and stability under reaction conditions. An important property is the possibility of forming a solid contact between thermally conductive granules agent at the stage of heat treatment. This requires that the temperature of tammana for phase heat transfer agent does not exceed the temperature stage heat treatment. It should be noted that the heat-conducting agent performs in the catalyst function and strengthening (reinforcement) of the agent.

The term “pore-forming agent” refers to a phase or sovoobraznyh chemical compounds simultaneously with the formation of solid phases, the volume of which is substantially less than the volume of the original pore-forming agent. As a pore-forming agent is preferable to use salts and/or oxides and/or hydroxides and/or hydroxocobalamin one or more metals in the composition of the heat-conductive agent (such as basic copper carbonate (malachite) when using metallic copper as a heat transfer agent). As a pore-forming agent can also be used catalytically active agent in case of its transformation during heat treatment accompanied by a significant decrease in the volume of the solid phase.

To provide the required parameters of the porous structure of the body of catalyst granules comprising the powders a, B, C and D must have size less than 300 microns, and preferably less than 200 microns). While it is preferable that the prevailing size of the particles in the mixed powders were close.

The ratio of the content of the heat-conducting agent, the content of the pore-forming agent and the content of catalytically active agent determined the optimal value of the parameters the strength - permeability - performance and can vary widely the of the mass content of the powder In the mass content of powder B is not more than 4, and the mass ratio of the content of the powder And the mass content of the powder G is not less than 0.25.

It should be noted that the stage of compaction of the powder is optional, although its introduction in the proposed method improves the strength characteristics of the catalyst and the efficiency of the process of the Fischer-Tropsch synthesis using it.

Compaction of the mixture of powders a and G and form the body of the catalyst can be carried out using any known method tabletting, extrusion or rolled on a rolling mill, preferably at a pressure seal over 2000 kgs on cm2. The geometric shape of the body concentrated permeable catalyst may be any and is determined by the requirements of a particular reactor. Most preferred are presented in the form of plates (including disks) and hollow cylinders with multiple geometry sections (including hollow cylinder rotation). The thickness of the plate (or cylinder walls) can range from fractions of a millimeter to 1 m; the optimal size is determined from the technological parameters of the method of preparation and the conditions for achieving a reasonable pressure drop across the catalyst body.

The main advantages of the proposed method of preparation of the catalyst are the high content of catalytically active agent per unit volume of the catalyst body while ensuring a developed porous structure of the catalyst body, and the high conductivity of the obtained catalysts, thereby reducing the temperature gradient inside the body of the catalyst, i.e. to ensure flow exothermic process in a mode close to isothermal. An additional advantage of the proposed method is the ease of separation of the reaction products from the solid phase, which is relatively large dimensions of the body of catalyst and its high mechanical strength. Heat removal from tel concentrated Pronichev ncoi additional heat exchangers introduced in the reaction volume.

The task is also solved by a method of producing hydrocarbons and/or oxygen-containing derivatives from synthesis gas using the catalyst prepared as described above.

The invention is illustrated by the following examples.

Example 1. The catalyst is prepared on the basis of the following powders:

Powder And powder of gidroksicarbonata Co-Al (1:1) with the structure of hydrotalcite prepared according to the procedure described in A. A. Khassin, T. M. Yurieva, G. N. Kustova, I. Sh. Itenberg, M. P. Demeshkina, T. A. Kriger, L. M. Plyasova, G. K. Chermashentseva and V. N. Parmon. Cobalt-aluminum co-precipitated catalysts and their performance in the Fischer-Tropsch synthesis. J. Mol. Catal. A: Chem., 168 (1-2), 193-207 (2001). This gidroksicarbonat has the ability to turn into a course of rehabilitation treatment in a stream of hydrogen and the combination of the phases of the active metal (cobalt) and anionic-modified joint oxide Co-Al. According to the titration of the amount of active metal (cobalt) oxygen (control was performed according to the change of weight), according to photoelectron spectroscopy, and magnetic susceptibility data the content of the active metal in the above-mentioned set of phases is about 27 wt.% [A. A. Khassin, V. F. Anufrienko, V. N. Ikorskii, L. M. Plyasova, G. N. Kustova, T. V. Larina, I. Brosok B - the metallic copper powder with a particle size less than 50 microns.

The powder In the powder of the basic carbonate of copper si2(OH)2CO3(malachite).

The mixture of powders B and C to obtain a powder G is carried out in a ratio of 3:2 by weight. share. Compaction of the powder G is carried out by tableting at a pressure of 4000 kgf/cm2followed by crushing and Tsevaot fraction of particles with size less than 250 microns.

The mixture of powders a and G is carried out in a ratio of 9:11 wt. Seal the mixture of a and G and the shape of a disk with a diameter of 15 mm and a height of 6 mm is carried out by tableting at a pressure of 3000 kgf/cm2.

Heat treatment is carried out in two stages - in the current of argon at a temperature of 550°C in a stream of hydrogen at a temperature of 650°C. After the heat treatment, the catalyst body has the following phase composition: metallic copper + cobalt metal, fixed on the surface of the anionic-modified cobalt aluminate.

The main parameters of the obtained catalyst are shown in Table 1.

Catalytic test is carried out in a flow reactor with the reaction mixture WITH 30 vol.%, H260 vol.%, N210 vol.%, at pressures of 0.1 MPa and a temperature of C. Stream d is given by sealing the side surfaces of the disk. The catalytic properties of the catalyst are shown in Table 2.

Example 2. The catalyst is prepared analogously to example 1, but as a powder And use the powder gidroksicarbonata Co-Zn-Al structure hydrotalcite prepared according to the method described by A. A. Khassin, T. M. Yurieva, G. N. Kustova, I. Sh. Itenberg, M. P. Demeshkina, T. A. Kriger, L. M. Plyasova, G. K. Chermashentseva and V. N. Parmon. Cobalt-aluminum co-precipitated catalysts and their performance in the Fischer-Tropsch synthesis. J. Mol. Catal. A: Chem., 168 (1-2), 193-207 (2001), with a particle size less than 150 microns. This gidroksicarbonat has the ability to turn during processing in a stream of hydrogen and the combination of the phases of the active metal (cobalt) and anionic-modified joint oxide Zn-Al. According to the titration of the amount of active metal (cobalt) oxygen (control was performed according to the change of weight) concentration of active metal in the above-mentioned set of phases is about 24 wt.%. Powder G also contains particles smaller than 150 microns. After the heat treatment, the catalyst body has the following phase composition: metallic copper + cobalt metal, attached to the anionic surface-modified zinc aluminate.

The main parameters of the obtained catalyst are shown in Table 1.

The fractions obtained powder a and powder G are mixed in the ratio 2:3 wt.

Compaction of the mixture of powders a and G and the shape of a round plate with a diameter of 15 mm and a height of 6 mm is carried out by tableting at a pressure of 3000 kgf/cm2.

Heat treatment is carried out in one stage in a stream of hydrogen at a temperature of 650°C. After the heat treatment, the catalyst body has the following phase composition: metallic copper + Nickel metal attached to the surface of the joint of Nickel oxide-magnesium.

The main parameters obtained catalysis 2.

Example 4. The catalyst is prepared analogously to example 1, but as a powder B use powder tin bronze brand Pbro (SR 90 at.%, Sn 10 at.%) with a particle size less than 70 microns. The mixture of powders B and C to obtain a powder G is carried out in the ratio of 4:3 wt. share. The fractions obtained powder a and powder G are mixed in a ratio of 1:1 wt.

After the heat treatment, the catalyst body has the following phase composition: alloy of copper with tin + metal copper + cobalt metal, fixed on the surface of the anionic-modified cobalt aluminate.

The main parameters of the obtained catalyst are shown in Table 1.

The catalytic properties of the catalyst are shown in Table 2.

Example 5. The catalyst is prepared analogously to example 1, but as a powder using a powder of copper hydroxide cu(OH)2with a particle size less than 50 microns.

The mixture of powders B and C to obtain a powder G is carried out in a ratio of 3:2 by weight. share. The fractions obtained powder a and powder G are mixed in a ratio of 1:1 wt.

After the heat treatment, the catalyst body has the following phase composition: metallic copper + cobalt metal, secured the catalyst are shown in Table 1.

The catalytic properties of the catalyst are shown in Table 2.

Example 6. The catalyst is prepared analogously to example 1, but as a pore-forming agent powder In the use of catalytically active agent powder gidroksicarbonata Co-Zn-Al structure hydrotalcite. Compaction of the powder And is carried out by tableting at a pressure of 4000 kgf/cm2followed by grinding to obtain a powder fraction less than 250 microns. Stage mixing a pore-forming agent and a heat-conductive agent is not carried out. The fractions obtained powder A, powder B and powder are mixed in a ratio of 9:16 wt.

Compaction of the mixture of powders a and B and the shape of a round plate with a diameter of 15 mm and a height of 6 mm is carried out by tableting at a pressure of 3000 kgf/cm2.

After the heat treatment, the catalyst body has the following phase composition: metallic copper + cobalt metal, fixed on the surface of the anionic-modified cobalt aluminate.

The main parameters of the obtained catalyst are shown in Table 1.

The catalytic properties of the catalyst are shown in Table 2.

Example 7. The catalyst is prepared analogichnogo and G is carried out in a ratio of 2:3 by weight.share.

After the heat treatment, the catalyst body has the following phase composition: metallic copper + cobalt metal, fixed on the surface of the anionic-modified cobalt aluminate.

The main parameters of the obtained catalyst are shown in Table 1.

The catalytic properties of the catalyst are shown in Table 2.

Example 8. The catalyst is prepared analogously to example 1, but the mixture of powders a and G is carried out in a ratio of 1:2 by weight.share.

The main parameters of the obtained catalyst are shown in Table 1.

The catalytic properties of the catalyst are shown in Table 2.

Example 9. The catalyst is prepared analogously to example 2, but the shape of the body concentrated permeable catalyst is a hollow cylinder of revolution with an outer diameter of 45 mm, an inner diameter of 10 mm and a height of 30 mm and compacting a mixture of a and G and the shape of a hollow cylinder rotation is carried out by tabletting pressure of 2300 kgf/cm2.

The main parameters of the obtained catalyst are shown in Table 1.

The catalytic properties of the catalyst are shown in Table 2.

Example 10. It is made by a plate thickness of 1 mm, and compaction and shaping of the body is concentrated permeable catalyst is carried out by rolling a mixture of powders a and G on rollers with a diameter of 35 cm with an estimated pressure seal around 3500 kgf/cm2.

The main parameters of the obtained catalyst are shown in Table 1.

1. The method of preparation of the catalyst receiving hydrocarbons and/or oxygen-containing derivatives from synthesis gas, wherein the catalyst is prepared from a powder of the catalytically active agent, heat-conductive agent and a pore-forming agent with a particle size less than 300 microns as follows: mix the powders heat-conductive and a pore-forming agents, the resulting powder was then mixed with a catalytically active agent, condense the mixture and give the body of catalyst required form, then carry out thermal treatment of the catalyst body.

2. The method according to p. 1, characterized in that after the stage of mixing powders thermal conductivity and pore-forming agents hold the seal obtained powder is prepared from a compacted mass of powder consisting of grains smaller than 300 microns.

3. The method according to any of paragraphs.1 and 2, atricauda agent does not exceed 4.

4. The method according to any of paragraphs.1-3, characterized in that the ratio of the mass content of catalytically active agent to the mass content of the heat-conducting and a pore-forming agent is not less than 0.25.

5. The method according to any of paragraphs.1-4, characterized in that the catalytically active agent contains one of the metals of group VIII.

6. The method according to any of paragraphs.1-5, characterized in that the content of the phase of catalytically active metal in the catalytically active agent is at least 2 wt.%.

7. The method according to any of paragraphs.1-6, characterized in that as the heat transfer agent is used metallic copper and/or zinc and/or aluminum and/or tin and/or their mixtures or alloys.

8. The method according to any of paragraphs.1-7, characterized in that as a pore-forming agent is used, the oxide and/or hydroxide and/or carbonate and/or gidroksicarbonat, and/or salt of one or more metals in the composition of the heat transfer agent.

9. The method according to any of paragraphs.1, 3-7, characterized in that as a pore-forming agent is used, the powder of the catalytically active agent.

10. The method according to any of paragraphs.1-9, characterized in that the compaction of the mix and form the body of the catalyst is cu, and the shaping of the body of the catalyst is carried out by rolling the mixture in the rolling mill with the introduction of additional stages of the cutting plate of the desired shape.

12. The method according to any of paragraphs.1-11, characterized in that the catalyst body is formed into the shape of a cylinder or a perforated cylinder or plate, or a profiled plate.

13. The method according to any of paragraphs.1-12, characterized in that the heat treatment is carried out in a stream of hydrogen containing gas at temperatures above 400C.

14. The method according to any of paragraphs.1-12, characterized in that the heat treatment is carried out in two stages in a stream of inert gas at temperatures above 400C and in the current of hydrogen containing gas at temperatures above 300C.

15. A method of producing hydrocarbons and/or oxygen-containing derivatives from synthesis gas, characterized in that it is carried out using the catalyst prepared according to any one of paragraphs.1-14.

 

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