Heat-conducting composite catalyst and process of steam conversion of carbon monoxide

FIELD: disproportionation process catalysts.

SUBSTANCE: invention relates to generation of hydrogen through steam conversion of carbon monoxide and development of catalyst for indicated process. Invention provides carbon monoxide conversion catalyst showing high catalytic activity and heat-conductivity and a process of steam conversion of carbon monoxide using indicated catalyst. Catalyst is characterized by heat-conductivity at least 1 W(mK)-1, which enables performing process with low temperature gradient in direction transversal to gas stream direction.

EFFECT: increased catalytic activity and heat-conductivity.

7 cl, 4 dwg, 3 tbl, 10 ex

 

The invention relates to the field of hydrogen production steam conversion of carbon monoxide and development of catalysts for this process.

The steam reforming reaction WITH can be represented by the equation

CO+H2CO2+H2(ΔN°298K=-41.1 kJ/mol)

The process of conversion of carbon steam is widely used in large industrial plants producing hydrogen. The process is carried out in two stages, in which the transformation occurs consistently at high temperatures 320-450°on gelatobaby catalysts at low temperatures of 180-250°on Cu/Zn/Al(Cr) oxide catalysts. Steam reforming is carried out in the adiabatic reactors axial (shelf) or radial types with fixed bed catalysts. The design of such reactors are well known. Axial reactor is simpler in construction than the radial. However, the latter have a number of technological and operational advantages [Purification of process gases. Edited Caselnova and Illites. M, Chemistry, 1977, 488 S.]. In the radial reactor with a uniform distribution of gas in the catalyst bed hydraulic resistance is less than 0.01 MPa and practically does not change during operation. In axial reactor hydraulic resistance of the age of the et from 0.02-0.04 MPa to 0.2-0.4 MPa as operation, that can lead to the need for early discharge of the catalyst.

Two-stage process is quite cumbersome instrumentation in connection with the separation stage and large volumes of used catalysts. To improve mass-dimensional characteristics of the steam reforming process can be done WITH the organization of an optimal temperature profile in the catalyst bed operating in a wide temperature region. To carry out the reaction, it is expedient at high temperatures, at the same time, small concentrations (less than 1-1 .5%vol.) output can be achieved at temperatures of not more than 270-300°C. Consequently, the temperature in the catalyst bed should be changed approximately from 400 to 200°C. Such a change can be made by the organization of several isothermal catalyst or optimal temperature profile in a single layer of catalyst by continuous heat removal. In [D.Myers, .Krause, J.-M.Bae and Sreeja. Extending Abstracts. 2000 Fuel Cell Seminar, p.280-283, 2000] considered these variants for heat removal.

The implementation of the steam reforming reaction in the catalyst layer with an optimum temperature profile in a tubular reactor using a conventional catalyst, steadily working in the field to 350°discussed in the patent [US 5990040, B 01 J 023/00, 01 031/00, 28.07.1997]. For EF the objective of the heat of reaction are typically used tubular reactors with a diameter tubes 50-60 mm for a very high-heat processes. Traditional catalysts used in the steam reforming reactors, are oxides or metals on oxide carriers and have low ability to conduct heat. Heat transfer from the tablets of the catalyst to the wall of the reactor through the reaction gas. A small value of the coefficient of heat transfer from solid to gas and from gas to solid body determines the heating of the catalyst layer. Effective thermal conductivity of the catalyst layer in the transverse gas flow direction does not exceed 0.5-1 W(MK)-1therefore , the temperature difference in the radial direction in the layer of steam reforming catalyst for tubes with a diameter of 50-60 mm 20-30° [Beeskow S.D. Chemical calculations. Moscow Higher school" 1968; Boreskov G.K. Heterogeneous catalysis. Moscow, "Nauka" 1988].

In the present invention the problem of intense heat in the catalyst bed in a radial direction is addressed: (1) create a catalyst with high thermal conductivity of the catalyst body and (2) efficient catalyst layer, for example, by use of a catalyst body with lateral dimensions comparable to the size of the reactor, and/or provide direct contact with the wall of the reactor, through which the heat.

The problem which may be solved by using as catalysts for metal plates the foam materials or composite materials with good thermal properties and are easy to arrange direct contact with the reactor walls due to the fact that they are obtained by sintering of oxide and metal components at high temperatures, have a low specific surface and do not exhibit high catalytic activity [US 6517805, C 01 B 3/02, 02.10.1998; US 6432871, B 01 J 023/70, 18.10.1999]. Increasing the catalytic activity of these materials can be achieved by drawing on their surface a catalytically active component. However, in this case there is a problem of durability of fastening of the active substance. If not strong enough clamping possibly shedding and entrainment of catalyst in the process.

Closest to the present invention is a patent [EP 1232790, B 01 J 23/722, 1.08.2002], which offers catalysts for endo - and exothermic reactions, in which the conductivity and the activity of the catalyst body can be achieved by using metal plates on the surface of which is synthesized active component.

The invention solves the problem of intense heat in the catalyst bed in a radial direction.

To solve this problem in the reaction of steam reforming WITH the proposed use as a catalyst composite having a high activity and heat conductivity is hodnotu not less than 1 W (m K) -1. The body of the catalyst is a composition of the catalytically active component of the oxide nature and metal particles with massoum ratio of not less than 0.25.

In the catalyst body of the catalytically active component is an oxide of nature is a catalyst based on copper and zinc promoted items III, IV, VI groups, preferably Zr.

In the catalyst body of the catalytically active component is an oxide of nature is a catalyst based on iron and chromium promoted items I, II, VII groups, preferably Cu.

In the composite metal particles are particles of metallic copper dendritic texture.

The catalyst used in the form of solids, the maximum overall size of which is not less than 0.8 times the minimum overall size of the reactor.

The inventive heat transfer catalyst consists of particles of the catalytically active component of the oxide nature and thermally conductive metal particles, employees and simultaneously reinforcing component. Such a composite can be obtained by a sequence of operations used in powder metallurgy comprising: 1) preparing a mixture of powders of the catalytically active component of the oxide nature of the metal and a pore-forming component, 2) the seal of the mixture and 3) sintering with ychenih temperatures, not lead to the deterioration of the properties of the catalytically active component.

Under the catalytically active component an oxide of nature is a set of phases, comprising an oxide phase containing the active metal cations, for example cations of Cu2+or iron cations. The catalytically active component can be prepared by precipitation [EN 2118910, B 01 J 23/84, 20.09.1998; US 5990040, B 01 J 023/00, 01 031/00, 28.07.1997] followed by calcining the obtained hydroxocobalamine, or any other known method. It is necessary that the oxide catalyst showed stable activity in the reaction of steam conversion of CO in the medium temperature (300-450° (C) region or in the low-temperature (180 to 250° (C) the area, preferably over the entire range of temperatures 450-180°C.

As a thermally conductive metal particles in the composite can be used particles of metallic copper dendritic structures with characteristic dimensions less than 50-100 microns. The ratio of the quantities of heat conducting substance, loosening substances and oxide catalyst determined by the requirements of thermal conductivity, strength and the developed surface of the heat conductive catalyst body.

Giving the desired shape of the heat conductive catalyst body can be carried out using any known method tabletting, preferably prizivlenie seal more than 1500 kgf/cm 2. Minimum working volume of the layer is achieved by an optimal placement of the tablets with dimensions comparable to the transverse dimensions of the tube reactor, and an optimal ratio of surface area to volume.

Heat treatment heat-conductive catalyst body carried in a stream of inert gas at temperatures above the temperature Tamanna (about 0.5 from the absolute melting temperature).

Prepared catalysts satisfy the requirements of high thermal conductivity and strength, and also show high activity in the reaction of steam reforming of carbon monoxide.

The invention is illustrated by the following examples, tables, and drawings.

Figure 1 (a) Data of scanning electron microscopy on the characteristic topology of the heat conductive catalyst body.

(b) Data on the distribution of the catalytically active component (areas in dark gray) and the heat-conducting component (areas of light gray color) optical micrograph.

Figure 2 Laboratory reactor rectangular cross-section as a variant of the optimal organization of the catalyst layer using a thermally conductive catalyst plates.

Figure 3 Comparison of temperature changes in the radial direction upon the reaction of steam reforming WITH body teploproizvoditelnosti diameter of 50 mm (circles, •) and on the catalyst in the form of tablets in traditional industries form in a tubular reactor with a diameter of 50 mm (triangles, ▴).

Table 1. Cooking parameters and values of thermal conductivity of the catalyst bodies of different shapes.

Table 2. Utilization of grain catalyst in heat-conductive catalyst body and in traditional tablet in a flow-circulation-ideal mixing reactor at different reaction temperatures.

Table 3. The results of catalytic tests thermally conductive catalyst plates in a laboratory reactor of rectangular cross-section when the velocity of the reaction gas mixture of 20 l/h 250 l/h.

Example 1A.

Heat transfer catalyst 1A was prepared as follows:

1) 38 wt.% powder joint copper oxide-zinc-aluminium-chromium obtained in accordance with the patent [EN 2118910, B 01 J 23/84, 20.09.1998], 52 wt.% powder heat-conductive substance and 10 wt.% powder loosening substances with a particle size less than 70 microns are thoroughly mixed,

2) the mixture of powders is compacted at a pressure of 2490 kg/cm2then crushed and Tsevaot fraction of particles with a size in the range of 100-200 microns,

3) the resulting fraction tabletirujut at a pressure of P=2490 kg/cm2in the form of a ring external diameter of 18 mm, an inner diameter of 7 mm, height 2.5 mm,

4) heat treatment, quenching the weave is carried out in a current of inert gas at a temperature T=380° C.

Typical topology of a thermally conductive catalyst body according to scanning electron microscopy is presented in figure 1(a). Optical micrograph (see Figure 1(b)) is clearly visible uniform distribution of the catalytically active component (areas in dark gray) and the heat-conducting component (areas of light gray color).

Examples 2A-6A.

The heat-conducting catalysts are prepared analogously to example 1A, but with different tabletting pressures and temperatures of heat treatment. Cooking parameters heat transfer catalysts 1A-6A are presented in Table 1.

Example 7A.

Heat transfer catalyst is prepared analogously to example 1A, but using the powder joint iron oxide-chromium-copper obtained in accordance with the patent [BG 32877, B 01 J 23/86, 15.11.1982]when the pressure tableting P=1720 kN/cm2and the temperature of heat treatment T=380°C.

Example 8.

Thermally conductive catalyst body Z1 is prepared analogously to example 1, but with the pelletizing shape of the plate is of square cross section with dimensions of 25×25×2.5 mm, the tabletting pressure is P=1720 kN/cm2.

Example 9.

Thermally conductive catalyst body prepared analogously to example 8, but the temperature of heat treatment is T=410°C.

Example 10 (comparative is th).

The catalyst prepared according to patent RU 2118910 in the form of tablets in the form of a cylinder with a diameter of 5 mm and a height of 5 mm, typical for use in traditional industrial reactors.

thermal conductivity of the body in the form of a ring with dimensions: outer diameter D=18 mm, inner diameter d=7 mm, ring height h=10 mm; determine if the change in heat flow through the sample at a purpose-built laboratory facility at the Institute SB RAS. To test the installation was measured conductivity of the sample, made of stainless steel 12X18H10T). From these measurements, it was shown that the conductivity of the test sample differs from the reference data is not more than 5%. The error of determination of thermal conductivity present in the patent sample is about 7%. Experimental values of thermal conductivity are presented in Table 1 in comparison with the magnitude of thermal conductivity of traditional tablets in the industry form a copper-zinc-aluminum catalyst promoted with chromium, prepared according to patent RU 2118910.

Catalytic tests of the heat-conducting catalysts is carried out in a flow-circulation reactor of ideal mixing in the composition of the reaction mixture WITH 16 vol.%, CO29 vol.%, H275% vol. at a pressure of 0.1 MPa in the temperature range 270-350°S. Raza is taty catalytic tests are presented in Table 2 as the degree of use of grain catalytically active component, that is, as the ratio of experimental values of the reaction constants for thermally conductive catalyst (or the traditional tablet form) to the experimental reaction rate constant in the kinetic region on the particles of the catalytically active component with a size of 0.25-0.5 mm, This value characterizes the real activity of the catalyst and allows us to quantitatively compare the activity of the catalysts proposed by the present invention and described in the examples with known catalysts in the form of cylindrical pellets of 5 mm ×5 mm

The results of catalytic tests the heat transfer catalysts according to examples 8 and 9 in a laboratory reactor of rectangular cross-section (Figure 2) when the velocity of the reaction gas mixture of 20 l/h 250 l/h are presented in Table 3.

Figure 3 represents the comparison of the temperature changes in the radial direction upon the reaction of steam reforming WITH body heat-conductive catalyst with a diameter of 50 mm (circles, •) and on the same catalyst in the form of tablets in traditional industries form in a tubular reactor with a diameter of 50 mm (triangles, ▴).

The presented examples show that the heat-conducting catalysts, claimed by the present invention, is not inferior to the famous catalysts with low heat conductivity in the utilization of grain is analiticheskii active component, however, provide a much smaller temperature gradient of the catalyst layer in the radial direction of the reactor.

Version of the proposed effective organization of the catalyst layer is provided comparable transverse dimensions of thermally conductive catalyst body and the reactor (Figure 2). While preferred, but optional, is the provision of direct contact heat transfer catalyst body with the wall of the reactor. From the outer wall of the reactor, the heat of reaction can be abstracted by means of known methods of heat exchange with the refrigerant.

Table 1.

Cooking parameters and values of thermal conductivity of the catalyst bodies of different shapes.
SampleR, kgf/cm2T °Thermal conductivity, W/m·
Example 1A29403802.8
Example 2A22003802.8
Example FOR17203802.8
Example 4A29404403.2
Example 5A22004403.2
Example 6A1720 4403.2
Example 7A17203802.6
Example 817203802.8
Example 917204103.0
Example 10 (comparative)the cylinder is d=5 mm, h=5 mm0.3

Table 2.

Utilization of grain catalyst in heat-conductive catalyst body and in traditional tablet in a flow-circulation-ideal mixing reactor at different reaction temperatures.
SampleThe utilization of the grain of the catalyst in the form of a traditional tablet and thermally conductive catalyst body at the temperature of reaction:
270°300°330°350°
Example 10 (comparative)0.410.370.360.34
Example 1A0.500.440.350.27
Example 2A0.470.440.350.29
Example 3A0.530.46 0.360.39
Example 4A0.310.280.230.20
Example 5A0.390.380.280.24
Example 6A0.510.400.330.33
Example 7A0.470.450.38
Example 80.550.460.370.37
Example 90.600.480.400.40

Table 3.

The results of catalytic tests thermally conductive catalyst plates in a laboratory reactor of rectangular cross-section when the velocity of the reaction gas mixture of 20 l/h 250 l/h.
SampleThe degree of grain usage of catalyst heat-conductive catalyst body at various speeds the reaction gas mixture and the temperature of the reaction:
20 l/h250 l/h
270°300°330°350°270°300 330°350°
Example 80.480.400.340.330.500.430.350.35
Example 90.550.420.360.360.570.460.380.38

1. The catalyst for steam reforming of carbon monoxide, which is the composition of the catalytically active component an oxide of nature and the metallic component, wherein as the metal component it contains particles of metallic copper with a size less than 100 μm at a mass ratio of the catalytically active component to the metal particles of copper not less than 0.25 and the catalyst is a composite having a thermal conductivity of not less than 1 W/(m·).

2. The catalyst according to claim 1, characterized in that the catalytically active composite oxide component of nature is a catalyst based on copper and zinc promoted items III, IV, VI groups, preferably Zr.

3. The catalyst according to claim 1, characterized in that the catalytically active composite oxide component of nature is a catalyst based on iron and chromium promoted items I, II, VII groups, before occhialino Cu.

4. The way steam conversion of carbon monoxide, characterized in that it is carried out by using the catalyst according to any one of claims 1 to 3.

5. The method according to claim 4, characterized in that the catalyst used in the form of plates, the area of which is not less than 0.65 from the cross-sectional area of the reactor.



 

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1 tbl

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FIELD: inorganic synthesis.

SUBSTANCE: iron-chromium-nickel spinels are prepared by homogenization of original oxides of nickel(II), iron(III), and chromium(III) in presence of 0.5-1.5% of potassium halides as mineralizing agent followed by briquetting and heat treatment of oxides at 800-1000°C.

EFFECT: enabled preparation of spinels at lowered temperatures and in shorter time.

2 tbl, 2 ex

FIELD: hydrogenation-dehydrogenation catalysts.

SUBSTANCE: invention relates to catalysts used in isoamylenes-into-isoprene dehydrogenation process and contains, wt %: iron oxide 62-75.4, potassium carbonate 12-21.5, chromium oxide 1-3, potassium hydroxide 0.5-2.5, sulfur 0.1-2.0, ammonium nitrate 0.1-2.0, silicon dioxide 1-5, calcium carbonate 1-5, and cerium nitrate 1-3.

EFFECT: increased mechanical strength, resistance to saturated steam and moisture, and stability during long-time operation.

3 ex

The invention relates to an improved method for the oxidation of cyclic hydrocarbons, alcohols and/or ketones to carboxylic acids with oxygen or oxygen-containing gas

FIELD: various-destination catalysts.

SUBSTANCE: invention relates to production of copper-zinc-aluminum catalysts appropriate for low-temperature steam conversion of carbon monoxide, low-temperature methanol synthesis, and hydrogenation-dehydrogenation of various organic compounds. Catalyst preparation process comprises preparing ammonia-carbonate solutions of copper and zinc, treating aluminum-containing raw material with ammonia-carbonate solution of zinc, mixing thus treated or its mixture with untreated aluminum-containing raw material with copper and zinc compounds, holding resulting suspension in reactor at elevated temperature and stirring, separating formed catalyst mass from solution, drying, calcination, and granulation. Specifically, treatment of aluminum-containing raw material with ammonia-carbonate solution of zinc is carried out at 75-90°C and is followed by ageing at stirring until ammonia-carbonate solution of zinc is decomposed and mixing of copper, zinc, and aluminum-containing raw material is conducted in dosed manner while maintaining reactor temperature 75-90°C and specified copper-to-zinc ratio in liquid phase of suspension. Moreover, zinc compounds are introduced into reactor in the form of ammonia-carbonate solution or oxide, or basic carbonate and copper compound in the form of ammonia-carbonate solution so that copper-to-zinc atomic ratio in finished catalyst is (0.55-2.2):1 and atomic content of aluminum ranges from 2.6 to 10.6.

EFFECT: simplified catalyst preparation technology, avoided noxious effluents and gas emissions, and assured preparation of high-activity, stable, and strong catalysts.

3 cl, 1 tbl, 16 ex

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