Catalyst and method for producing hydrocarbons and their oxygenated derivatives from synthesis gas

 

The invention relates to catalysts and methods for producing hydrocarbons and their oxygen-containing derivatives of a mixture of CO and hydrogen (synthesis gas). Proposed catalyst receiving hydrocarbons and/or oxygen-containing derivatives from synthesis gas, containing at least 0.4 g/cm3the aggregate phase representing a phase of a catalytically active metal, secured to the phase of the substrate of the oxide nature, exerting an active influence on the dispersion of the active metal phase or other of its physico-chemical properties, the catalyst body has a permeability of at least 510-15m2. Method for obtaining hydrocarbons and/or oxygen-containing derivatives, including passing the synthesis gas through one or more bodies of concentrated permeable catalyst. While it is preferable that one of the linear dimensions of the body of catalyst was comparable with the least linear in the size of the reactor. Technical result: the catalyst allows the synthesis of hydrocarbons and/or oxygen-containing derivatives from synthesis gas with high productivity per unit volume of reactor. 2 S. and 6 C.p. f-crystals, 1 tab., 3 Il.

Known methods for the conversion of synthesis gas into valuable chemical products for the reactions n CO+(2n+l)H2=CnH2n+2+n N2About; n CO+(2n)H2=CnH2n+mo2About; n CO+(2n)H2=CnH2n+1OH+(n-1)H2About; in the presence of a catalyst. These methods are combined under the name "Fischer-Tropsch synthesis". In the synthesis of Fischer Tropsch process 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 the content WITH:2determined by the method thereof, and m is the durability of the process in combination with high sensitivity, selectivity and activity of the process to the temperature. The increase in temperature leads to an increase in the rate of reaction, but shifts the selectivity towards formation of light hydrocarbons and methane, which is undesirable. Thus, a necessary condition for the optimal conduct of the Fischer-Tropsch synthesis is to maintain the set temperature and ensuring considered horizontally isothermal surface of the reactor.

Another feature of the Fischer-Tropsch synthesis is a relatively low speed of the process. Thus, the specific reaction rate when using Co-EN-TiO2containing catalysts at conditions close to industrial (20 ATM, 40% conversion), 220 kg of hydrocarbon per 1 m3of catalyst per hour (US Pat. 4670475, C 07 C 1/04, 06.02.1987). It follows that lowering the amount of catalyst per unit of reaction volume is very undesirable, as it leads to poor performance of the reactor and the average size of industrial units.

There are many types of reactors for Fischer-Tropsch synthesis. Among them traditional tubular type reactors, three-phase slurry reactors, fluidized bed of catalyst and others.

In tubular reactors typically use fixed Stacy can have different shapes (shamrocks, spheres, cylinders) and contain voids and pores, the volume of which is from 30 to 50% of the geometric volume of the particles. The flow of reactants through the catalyst bed, while flowing around each of the particles.

One of the drawbacks of the reactor with a fixed catalyst bed is low radial conductivity in the catalyst layer. To provide radial temperature difference at the 5oWith the diameter of the tubes may not be very large and usually does not exceed 6-10 see At the same time due to interdiffuse braking in the catalyst particles of high productivity and selectivity of the process can only be achieved when the particle size of the catalyst is less than 0.5 mm, the Hydrodynamic resistance of such a reactor is very high. Wetting of the catalyst particles to the reaction products inevitably leads to coalescence of the particles of the catalyst and formation of stagnant zones at the same time, with a fairly wide gas-filled channels. As a result, the efficiency of the catalytically active component is low. In the case of relatively large catalyst particles (>0.5 mm) process is characterized by a high yield of methane and low selectivity. This was the catalyst particles with hydrogen and promotes higher rate of formation of light hydrocarbons (primarily methane) compared with the target products.

Possible solution discussed the controversy is the use of large (>0.5 mm) particles of a catalyst comprising a porous carrier and a catalytically active component supported on a carrier in such a way that the bulk of the catalytically active component is concentrated in a thin surface layer of the device. In this case, the interior of the carrier catalytically active component is missing.

The drawback of such catalysts, called "korotkovym" (the English equivalent of "egg-shell"), is the complexity of their preparation. In addition, when using "Korotkevich" catalysts, the concentration of the catalytically active component in the reaction volume is low, which reduces the efficiency of the process and increases the dimensions of the reactor.

In suspension reactors are used, the suspension of catalyst particles with the size less than 100 microns. The flow of the reactants flowing through the suspension in the form of dispersed bubbles. In this case, the internal processes of diffusion does not have a significant impact on the flow velocity and selectivity of catalytic reactions. The advantages of suspension reactors need that because of the limited concentration of the catalytically active component in the suspension - not higher than 0.2 g/cm3(to provide the necessary dynamic viscosity of the suspension may not contain more than 20-25 wt.% catalyst particles). In addition, the rate of catalytic reaction can limit the processes of mass transfer at the phase boundary of gas-liquid.

An additional disadvantage of the suspension reactors is carried out in a suspension reactor mode close to the ideal mode mixing, which reduces the efficiency of the catalyst and reduces the selectivity of the process, when compared with the ideal displacement characteristic of the reactor with a fixed catalyst bed. Finally, the use of slurry reactors requires the introduction of the technological scheme of the process is technically difficult stage of separation of the reaction products from the catalyst particles.

In the invention (U.S. Pat. 5786393, C 07 C 27/00, 28.07.1998) proposed to use the recirculation of the liquid phase through a fixed bed of the catalyst to increase the efficiency of the process. This type of reactor has been called "the trickle-bed" (tricl) reactor, its distinctive feature is the simultaneous flow through the catalyst bed of the reaction gas mixture and the inert liquid (preferably in the form of voshodyaschih gnosti, and the selectivity of the process, due to better mass transfer at the phase boundary of gas-liquid, ensuring effective heat removal from the catalyst layer by the flow of inert fluid and lower longitudinal mixing.

However, tricl reactors have a number of disadvantages. First of all, it relates to the presence of hydrodynamic discontinuities in the layer, as well as a large pressure drop across the catalyst bed at high speed mass flow of gas and liquid, which is associated with low porosity (typically less than 45%) reactor with a fixed bed. In addition, as previously discussed types of reactors for Fischer-Tropsch synthesis with a fixed catalyst bed interdiffuse difficulties have a significant impact on the efficiency of the active component of the catalyst, reducing the efficiency of the process.

In the invention (U.S. Pat. 6211255, C 07 C 27/00, B 01 D 50/00, 03.04.2001) proposed to use a catalyst deposited on a monolithic carrier with parallel discrete channels. The invention is discussed and proposed the use of long monolithic media (e.g., longer than 10 cm) with an active component deposited on the surface of the channels. The authors ). During the flow of the gas stream through a liquid filled monolithic catalyst is Taylor mode (or "shell" gas flow), which according to the authors favored the high mass transfer at the phase boundary of gas-liquid. The advantage of this method is the high degree of utilization of the catalyst, as well as the relatively low hydrodynamic resistance of the monolithic catalyst. The disadvantages of the proposed method it is necessary to include a significant dilution of the catalytically active substance carrier and a minor proportion of the reaction volume occupied by the catalyst. Thus, in the invention examples, the content of the catalytically active component (Core/Al2O3) not more than 0.1 g per 1 cm3monolithic catalyst. Thus, as in the case of using a slurry reactor, the productivity per unit volume of the reactor with a solid catalyst essentially limited to a low concentration of the catalytically active component in the reaction volume. In addition, a significant drawback of the discussed invention is the need for fluid circulation to ensure effective heat dissipation, Viet-gas, the proposed patent [US Pat. 6262131, C 07 C 027/00, B 01 J 023/02, 17.07.2001] , using structured catalytic systems. The hallmark of the cited inventions is passing synthesis gas (or liquid-rich synthesis gas, or gas-liquid flow through a structured catalyst for Fischer-Tropsch synthesis, having a porosity of not less than 45% and providing a flow of gas (liquid or gas-liquid) flow mode, when Tayloresque thread cannot be formed. When this flow of gas through the fluid-filled channels occurs in a substantially turbulent regime of single gas bubbles. According to the text of the patents, for this length of transport channels to their diameter (L/D) should be less than 100 and preferably less than 10. The characteristic diameter of the channels in the patent text is specified to 1.5 mm at a length of less than 150 mm In the opinion of the authors of the cited inventions, it will provide better mass transfer inside the channels and reduce the possibility of formation of zones of laminar flow. To improve performance, amount of catalyst, the authors cited patents suggest the use of the content of the catalyst is not less Ob. % of the volume of the reactor. To nedostatki.

The problem solved by the present invention is to develop an efficient catalyst and a method of catalytic receiving hydrocarbons and their oxygenated derivatives from synthesis gas with high productivity per unit volume of reactor. For this catalyst and method must meet the following requirements: 1) high concentration of the catalytically active component in the reaction volume; 2) a high degree of use of a catalytically active component; 3) ensuring the homogeneity of the catalyst layer temperature.

In the present invention, the process of converting synthesis gas from hydrocarbons is suggested by passing carbon monoxide and hydrogen through one or more stationary particles (bodies) of concentrated permeable catalyst containing at least 0.4 g/cm3the aggregate phase representing a phase of a catalytically active metal, secured to the phase of the substrate of the oxide nature, with a significant impact on the dispersion of the active metal phase or other of its physico-chemical properties, the catalyst body has a permeability of at least 510-15m2.

As catalytically act is the actual content of the phase of catalytically active metal in the aggregate phases is not less than 5 wt.%. The volume of pores with a size less than 70 μm is not less than 90% of the total pore volume of the catalyst body.

The task is also solved by a method of producing hydrocarbons and/or oxygen-containing derivatives, including as one of the stages of passing a gas stream containing synthesis gas, through one or more bodies of concentrated permeable catalyst.

The term "concentrated" refers to a high concentration of the catalytically active component in the body of the catalyst, that is not less than 0.4 g/cm3body of catalyst, preferably above 0.8 g/cm3. The term "catalytically active component" here is a set of phases, including phase active metal (such as cobalt, iron, Nickel, ruthenium or intermetallic compounds with their contents) attached to the phase of the substrate of the oxide nature have a decisive influence on the physico-chemical properties of the active metal phase (e.g., dispersion). The content of active metal in the above-mentioned set of phases should be more than 5 wt.%, preferably 8-30 wt.%.

The term "permeable" means that the catalyst body has a permeability of at least 5

An important feature of the proposed method is that the flow of carbon monoxide and hydrogen is proposed to pass through (through) every body is concentrated permeable catalyst stochastically distributed transport pores with a characteristic size greater than 1 μm, preferably 10-50 μm. Wrap one or more bodies of concentrated permeable catalyst flow of reagents is undesirable because it reduces the utilization of the active component. While the geometric shape of the body concentrated permeable catalyst may be any and is determined by the method of preparation and 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). In the case of a cylindrical thread reage the Thickness of the plate (or cylinder walls) can range from fractions of a millimeter to 1 m; the optimum 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 microscopic size of the transport then concentrated permeable catalyst allows you to organize involuntary movement of the stream containing carbon monoxide and hydrogen, through the wet liquid (including the products of the Fischer-Tropsch synthesis) transport pores of the catalyst in the so-called "film" or "ring" (English synonym for "annular") mode, in which the surface boundary phase gas-liquid maximum and near-surface transport then. In this mode of mass transfer processes significantly intensifying due to the advanced interface. In addition, the longitudinal mass transfer in the direction opposite to the movement of the flow is negligible, which allows more efficient use of the catalytically active component. It is preferable that the volume of transport pores (pores larger than 1 µm) was more than 25% and not more than 70% of the geometric volume of a body of concentrated permeable catalyst.

The term "fixed" means that the bodies of the catalyst is not pareizticigie fluctuations ("vibrate"), due to the vibration of the reactor and the fluctuations of the flow velocity of the reactants.

The invention includes the possibility of the location in the reaction volume of several bodies of concentrated permeable catalyst installed in parallel or sequentially relative to the flow of CO and H2. While it is preferable that one of the linear dimensions of the bodies of the catalyst was comparable (i.e., was not less than 20%) with the least linear in the size of the reactor.

In addition, in the present invention, the process of converting synthesis gas to hydrocarbons is suggested by passing carbon monoxide and hydrogen through a body of concentrated permeable catalyst with a thermal conductivity of not less than 1 wattm-1To-1.

The increased thermal conductivity of the solids of the catalyst can be achieved by introducing into the composition of the concentrated permeable catalyst phase metal inert under the reaction conditions of the Fischer-Tropsch synthesis (e.g., aluminum, zinc, copper, their alloys and other) or graphite-like phase (for example, porous carbon, catalytic filamentous carbon nanotubes). Thus between grains (metal or graphite-like phase) should be the sphere, wire, perforated plate, sawdust or other) and size, providing the possibility making bodies concentrated permeable catalyst with the stated parameters.

Increased conductivity tel concentrated permeable catalyst reduces the temperature gradient within the catalyst, that is, to ensure flow of process in a mode close to isothermal. Heat removal from tel concentrated permeable catalyst can be provided by thermal contact tel catalyst from the reactor wall or the wall of the additional heat exchange devices, introduced in the reaction volume.

It should be noted that the invention involves the possibility of a combination of concentrated permeable catalyst in conjunction with other catalysts that do not have the stated parameters. For example, the body of concentrated permeable catalyst may be used as the catalytically active valve gas flow, heat transfer devices, and other assistive devices. The hallmark of the present invention in this case is that at least part of the carbon monoxide in the of Aligator.

Another additional advantage of this method is the ease of separation of the reaction products from concentrated permeable catalyst and the absence of mechanical impurities (dust) in the composition of the products.

Another additional advantage of the proposed method is the possibility of the location of the reactor containing the body of concentrated permeable catalyst both vertically and horizontally, and at any required angle to the vertical. This makes possible the placement of the reactor at any mobile systems, including floating platforms.

Another additional advantage of the proposed method is the possibility of using one or more bodies of concentrated permeable catalyst as a compact module, with the arbitrary apparatus performance can be assembled from several modules. While it is preferable that one of the linear dimensions of the bodies of the catalyst was comparable (i.e., was not less than 20%) with the least linear in the size of the module. Additional modules can be added to the already existing apparatus without stopping the process.

The invention is illustrated by the following cheel concentrated permeable catalyst (represented by a schematic cross-section of the body of catalyst); Fig. 2 illustrates some of the possible variations of the geometry of solids concentrated permeable catalyst;
Fig. 3 illustrates some possible options for the location of tel concentrated permeable catalyst in the reactor and the flow of reactants and reaction products (white arrows denote the flow of reagents, black stream of reaction products).

Example 1
The process of catalytic conversion of synthesis gas to hydrocarbons is carried out by passing a gas stream containing 20% vol. of carbon monoxide, about 40. % hydrogen, 6% vol. nitrogen and saturated vapors N.-tetradecane (34%), sequentially through two bodies of concentrated permeable catalyst at T= 210oC. the First body has a disk shape with a thickness of 5.0 mm with a circular cross section with a diameter of 15.7 mm, the second body has a disk shape with a thickness of 4.4 mm with a circular cross section with a diameter of 15.8 mm, each body contains 0.9 g/cm3the aggregate phase representing a phase of cobalt metal, secured to the phase of aluminum oxide. The maintenance phase of cobalt metal in the above-mentioned set of phases is 24 wt.%. The dependence of pressure drop on the phone from a stream flowing through it gas at a temperature of conduct petstay average permeability K= 1,610-14m2. Study of the porous structure of concentrated permeable catalyst showed that the pore volume of the catalyst is 45% of the geometric volume of the body, 98% of the porous volume consists of pores with a size less than 70 μm, the characteristic size of the transport then is 6-7 μm.

The performance of the process is about 1.2 mmol WITH per hour per 1 cm3the geometric volume of the body of catalyst in R (CO+H2)=0.6 ATM, T= 210oWith, the degree of conversion FROM 8 to 22%. The value ofdistribution of the Anderson-Schulz-Flory is about 0.78 for products fraction of saturated hydrocarbons.

Example 2
The process of catalytic conversion of synthesis gas to hydrocarbons is carried out by passing a gas stream containing 20% vol. of carbon monoxide, about 40. % hydrogen, 6% vol. nitrogen and saturated vapors N.-tetradecane (34%), through one body of concentrated permeable catalyst at T=210oC. the Body has a disk shape with a thickness 5.2 mm with a circular cross section with a diameter of 16 mm and contains 0.9 g/cm3the aggregate phase representing a phase Nickel metal secured to the phase of metasilicate magnesium. The content of phase metal is CA gas flowing through it at a temperature holding process (210o(C) is described by the equation P(ATM)= 9104V(m3/s), which corresponds to a permeability K=3,610-14m2. Study of the porous structure of the body concentrated permeable catalyst showed that the pore volume of the catalyst is 48% of the geometric volume of the body, 96% of the porous volume consists of pores with a size less than 70 μm, the characteristic size of the transport then is 6-7 μm.

The performance of the process is about 1.4 mmol WITH per hour per 1 cm3the geometric volume of the body of catalyst in R (CO+H2)=0.6 ATM, T= 210oWith, the degree of conversion FROM 8 to 22%. The value ofdistribution of the Anderson-Schulz-Flory is about 0.38 for products fraction of saturated hydrocarbons. (The catalyst may be used for the processes of conversion of synthesis gas to methane and light hydrocarbons).

Example 3 (for comparison to examples 4-6)
The process of catalytic conversion of synthesis gas to hydrocarbons is carried out by passing a gas stream containing 20% vol. of carbon monoxide, about 40. % hydrogen, 6% vol. nitrogen and saturated vapors N.-tetradecane (or.%), through a suspension of particles Co-Al catalyzer represents the phase of cobalt metal, secured to the phase aminomethylpropanol of cobalt aluminate. The maintenance phase of cobalt metal in the catalyst is 28 wt.%. The gas flow is arranged as a separate dispersed bubbles with size less than 0.2 mm, the contact Time of the bubble in suspension - more than 4 C. In such conditions, the mass transfer at the phase boundary of gas-liquid does not limit the speed of the process. The suspension is intensively mechanically stirred.

The results of catalytic tests carried out at the pressure of the reaction mixture of 1 ATM, T=210oWith that given in the table.

Example 4
The process of catalytic conversion of synthesis gas to hydrocarbons is carried out by passing a gas stream containing 20% vol. of carbon monoxide, about 40. % hydrogen, 6% vol. nitrogen and saturated vapors N.-tetradecane (34%), through one body of concentrated permeable catalyst at T=210oC. the Body has a disk shape with a thickness of 6.2 mm with a circular cross section with a diameter of 15 mm and contains 1.0 g/cm3the aggregate phases is identical to the catalyst used in example 3, i.e. representing a phase of cobalt metal, secured to the phase aminomethylpropanol of cobalt aluminate. The maintenance phase of cobalt metal in upominaemyh the catalyst also contains phase metallic copper. thermal conductivity of the body concentrated permeable catalyst experimentally determined about 5 W/m/K. the Dependence of pressure drop on the body from a stream flowing through it gas when the temperature of the process (210o(C) is described by the equation P(ATM)= 3,6104V(m3/s), which corresponds to a permeability K= 1,210-13m2. Study of the porous structure of the body concentrated permeable catalyst showed that the pore volume of the catalyst is 62% of the geometric volume of the body, 97% of the porous volume consists of pores with a size less than 70 μm, the characteristic size of the transport then is 10-12 microns.

The results of catalytic tests carried out at the pressure of the reaction mixture of 1 ATM, T=210oWith that given in the table. Comparison of experimental data with the data of the test particles of the catalytically active component in laboratory slurry reactor (see example 3) showed that the degree of use of the catalytically active component is 100%. Thus the value of the parameter Anderson-Schulz-Flory, reflecting the selectivity of the process in relation to heavy hydrocarbons, the same Dr. who and the active component, used in the catalyst. The selectivity to unsaturated hydrocarbons for the proposed process is significantly higher than the corresponding selectivity of the process with suspended catalytically active component, which reflects the more efficient transport of products from the catalyst surface into the gas phase.

Example 5
Analogously to example 4, but the porous structure of the body of catalyst in the absence of gas flow (before test) liquid filled - ad-tetradecanol. The body has a disk shape with a thickness of 4.6 mm with a circular cross section with a diameter of 15 mm Concentrated permeable catalyst contains 0.8 g/cm aggregate phases is identical to the catalyst used in example 3, i.e. representing a phase of cobalt metal, secured to the phase aminomethylpropanol of cobalt aluminate. The maintenance phase of cobalt metal in the above-mentioned population is 28 wt.%. To ensure high thermal conductivity concentrated permeable catalyst also contains phase metallic copper. thermal conductivity of the body concentrated permeable catalyst experimentally determined about 5 W/m/K. Research PORTFLEET 58% of the geometric volume of the body, 99% of the porous volume consists of pores with a size less than 70 microns. The dependence of pressure drop on the body from a stream flowing through it gas when the temperature of the process (210o(C) is described by the equation P(ATM)= 0,141 + 4,5104V(m3/c), which corresponds to a permeability K= 0,7210-13m2and characteristic pore size of 7.6 μm.

The results of catalytic tests carried out at 1 ATM, T=210oWith that given in the table. Comparison of experimental data with the data of the test particles of the catalytically active component in laboratory slurry reactor (see example 3) showed that the degree of use of the catalytically active component is 70%. Thus the value of the parameter Anderson-Schulz-Flory, reflecting the selectivity of the process in relation to heavy hydrocarbons, the same process concentrated on permeable catalyst and for tests on suspended catalytically active component used in the catalyst. The selectivity to unsaturated hydrocarbons for the proposed process is significantly higher than the corresponding selectivity of the process using scoverglossy catalyst in the gas phase.

Example 6
Analogously to example 5, but spotno the flow of gas through the body of the concentrated catalyst is a stream of fluid - present-tetradecane. The ratio of volumetric flow rates Vgas/Vfluid=50.

The results of catalytic tests carried out at 1 ATM, T=210oWith that given in the table. Comparison of experimental data with the data of the test particles of the catalytically active component in laboratory slurry reactor (see example 3) showed that the degree of use of the catalytically active component is 68%. Thus the value of the parameter Anderson-Schulz-Flory, reflecting the selectivity of the process in relation to heavy hydrocarbons, the same process concentrated on permeable catalyst and for tests on suspended catalytically active component used in the catalyst. The selectivity to unsaturated hydrocarbons for the proposed process is significantly higher than the corresponding selectivity of the process with suspended catalytically active component, which reflects the more efficient transport of products from the catalyst surface into the gas phase.

The above paragraph is Nizamova catalyst can reach 10-16 kg hydrocarbon per 1 m3reactor at a partial pressure of synthesis gas 0.6 ATM (examples 4-6), which significantly exceeds the performance of the suspension reactor (example 3).

Example 7
Analogously to example 5, concentrated permeable catalyst containing 0.6 g/cm3the aggregate phase representing a phase of cobalt metal, secured to the phase aminomethylpropanol of zinc aluminate. The maintenance phase of cobalt metal in the catalytically active component is 14 wt.%. To ensure high thermal conductivity concentrated permeable catalyst also contains a phase of aluminum metal. thermal conductivity of the body concentrated permeable catalyst experimentally determined about 3 W/m/K. the Dependence of pressure drop on the body from a stream flowing through it gas when the temperature of the process (210o(C) is described by the equation P(ATM)=0,076+1,6104V(m3/s), which corresponds to a permeability of K=210-13m2. Study of the porous structure of the body concentrated permeable catalyst showed that the pore volume of the catalyst is 58% of the geometric volume is yet 15-20 microns.

The results of catalytic tests carried out at the pressure of the reaction mixture of 1 ATM, T=210oWith that given in the table. Comparison of experimental data with the data of the test particles of the catalytically active component in laboratory slurry reactor (see example 3) showed that the degree of use of the catalytically active component is 75%. Thus the value of the parameter Anderson-Schulz-Flory, reflecting the selectivity of the process in relation to heavy hydrocarbons, the same process concentrated on permeable catalyst and for tests on suspended catalytically active component used in the catalyst. The selectivity to unsaturated hydrocarbons for the proposed process is significantly higher than the corresponding selectivity of the process with suspended catalytically active component, which reflects the more efficient transport of products from the catalyst surface into the gas phase.

Example 8
Analogously to example 5, concentrated permeable catalyst contains 0.9 g/cm3the aggregate phase representing a phase of cobalt metal, secured to the phase Aninat what those amounts to 22 wt.%. The catalyst body has the shape of a hollow cylinder of revolution with an inner diameter of 8 mm, an outer diameter of 17 mm and a height of 12 mm, the Flow of reagents is served inside the cavity of the cylinder with one of its ends, the opposite end of the cylinder bore is plugged. Further, the flow of reactants passes radially through the cylinder wall in the direction of the outer geometric surface (see Fig.3b). To ensure high thermal conductivity concentrated permeable catalyst also contains graphite-like carbon phase, representing a three-dimensional carbon matrix formed by the belt layers of carbon with a thickness of 0.01-1 μm and radius of curvature of 0.01-1 microns, characterized by a porous structure with a pore distribution with a maximum in the range of 0.02-0.2 μm (US Patent 4978649, From 01 To 31/10, 1990; RF Patent 1706690, From 01 To 31/10, 1992). The conductivity of the concentrated permeable catalyst experimentally determined about 1.2 W/m/K. the Dependence of pressure drop on the body from a stream flowing through it gas when the temperature of the process (210o(C) is described by the equation P(ATM)=0,07+1,9104V(m3/s), which corresponds to a permeability K= 1,2and, that the pore volume of the catalyst is 57% of the geometric volume of the body, 92% of the porous volume consists of pores with a size less than 70 μm, the characteristic size of the transport is then 17-22 ám.

Process productivity is about 0.7 mmol WITH per hour per 1 cm3the geometric volume of the body of catalyst at P=(CO+H2)=0.6 ATM, T= 210oWith, the degree of conversion WITH 7-20%. In terms of per unit of reaction volume (i.e., considering the volume of the internal cavity of the cylinder) the performance of the process is about 0.55 mmol WITH 1 cm3the reaction volume per hour.


Claims

1. The catalyst receiving hydrocarbons and/or oxygen-containing derivatives from synthesis gas, containing at least 0.4 g/cm3the aggregate phase representing a phase of active metal, which is used as one of the metals of group VIII or intermetallic compound with their contents, fixed on the phase of the substrate of the oxide nature, with a significant impact on the dispersion of the active metal phase or other of its physico-chemical properties, the content phase of catalytically active metal in the aggregate phases is not the volume of pores with a size less than 70 μm is not less than 90% of the total pore volume of the catalyst body.

2. The catalyst p. 1, which includes phase inert with respect to the synthesis-gas metal and/or graphite-like phase.

3. The catalyst p. 2, in which the inert towards the synthesis gas metal using copper and/or zinc and/or aluminum, and/or their alloys.

4. The catalyst PP. 1-3, in which his body has a thermal conductivity of not less than 1 W m-1To-1.

5. The catalyst PP. 1-4, in which at least part of the volume of its pores filled with hydrocarbons and/or oxygen-containing derivatives in liquid or solid state of aggregation.

6. A method of producing hydrocarbons and/or oxygen-containing derivatives, including as one of the stages of passing a gas stream containing synthesis gas, through one or more bodies of concentrated permeable catalyst according to any one of paragraphs. 1-5.

7. The method according to p. 6, in which a body of concentrated permeable catalyst saputo bypass gas stream flow stream of the liquid phase, forming with it a single gas-liquid flow.

8. The method according to PP. 6 and 7, in which the stage of passing of gas or gas-liquid flow through a body of concentrated permeable catalyst repeat a lot

 

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1 tbl, 3 ex

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