Catalyst and method of steam conversion of carbon monoxide

FIELD: alternate fuels.

SUBSTANCE: invention relates to a method for production of hydrogen via steam conversion of carbon monoxide and to relevant catalysts and can find used in different fields of national economy. Catalyst phase of copper-zinc-zirconium hydroxocarbonate of general formula (CuxZryZn1-x-2y)(CO3)2(OH)6 with hydrozinkite and/or aurichalcite structure, or of general formula (CuxZryZn1-x-2y)(CO3) (OH)2 with roasite structure, or containing heat treatment product thereof with general formula CuxZryZn1-x-2yO with vurcite structure, where x is number not higher than 0.7 and y number from 0.01 to 0.33. Also, method of conversion of O and H2O-containing gas mixture involving passage of reaction mixture through aforesaid catalyst bed at 150-400°C.

EFFECT: enabled preparation of heat-resistant catalyst efficiently functioning within temperature range 150 to 400°C.

4 cl, 3 dwg, 1 tbl, 7 ex

 

The invention relates to a method of producing hydrogen steam conversion of carbon monoxide and the catalyst for this process and may find application in various industries.

Hydrogen is an important component for many processes in the chemical industry. Recently also become very important processes for the production of pure hydrogen as an alternative gasoline fuel for the automotive industry and fuel for local power plants. The source of hydrogen is synthesis gas, which consists mainly of hydrogen and CO and is a product of natural gas processing. Depending on the method of processing natural gas to synthesis gas has a composition different ratio WITH/N2and CO/H2O. One of the ways to reduce the CO content and, consequently, increasing the total yield of hydrogen is the process of carrying out the reaction of steam reforming of carbon monoxide.

The reaction can be represented by the equation:

CO+H2O CO2+H2(ΔN0298=-41.1 kJ/mol)

Known and used in industry gelatobaby catalysts [D.S. Newsom, Catal. Rev., 21, R, 1980; Catalysts used in the nitrogen industry. Directory / Under the General editorship of A. M. Alekseeva. Cherkasy, Niitekhim. 1979. 23 C.], the advantage of which is high t is remotability, the disadvantage is the relatively low activity at temperatures below 300°C.

Also known and are widely used in industry copper oxide catalysts steam reforming WITH [reference catalysts for the production of ammonia and hydrogen. Ed. by V.P. Semenov. L.: Chemistry, 1973, 245 S.; Lloyd L., Twigg, M.V. - Nitrogen, 1979, No. 118, R-34], the advantage of which is the high activity at temperatures above 180°With, the disadvantage of low stability at temperatures above 280-340°With (depending on composition).

The most common way of carrying out the process of steam conversion of CO in the industry is a two-stage process, in which the transformation is conducted sequentially at high temperatures 320-450°on gelatobaby catalysts at low temperatures of 180-250°on Cu/Zn/Al(Cr) oxide catalysts [Purification of process gases. / Ed. by T.A. Semenova and IN the Leites. M.: Chemistry, 1977, 488 S.]. A two-stage process provides high speed conversion WITH the first stage due to the use of thermostable zhelezohromovyh catalyst at high temperatures and, at the same time, allows to achieve a large depth of the transformation FROM (0.1-0.6%) carrying out the process at low temperatures to highly active copper-containing catalysts is and the second stage.

Two-stage process implemented in the adiabatic reactors shelf or radial types with fixed bed catalysts. The process is quite cumbersome instrumentation used in connection with large amounts of catalysts and separation stage. To improve mass-dimensional characteristics of the process of steam reforming WITH features to carry out the process in one stage with a given change in the reaction temperature along the catalyst bed. The optimal temperature profile in the catalyst bed can be achieved by the organization of several isothermal layers or by using a single-stage variant of the process of steam reforming WITH a catalyst, working in a wide temperature region. In [D. Myers, T. Krause, J.-M. Bae and C. Pereira. Extending Abstracts. 2000 Fuel Cell Seminar, p.280-283, 2000] examples of optimal temperature profile in the catalyst bed of the mentioned ways.

The solution to the problem of improving the stability of copper-containing catalysts for steam reforming, including increasing the maximum allowable operating temperature of the catalyst is devoted to a large number of publications and patents, the most important of them are discussed below.

In the patent [US 4308176, B 01 J 021/04, 29.08.1980] claimed low-temperature copper-containing catalysts based on oxides of zinc and aluminum what I consistently active at the reaction temperature 180-220°C.

The authors of the patent [EP 0296734 (B1), B 01 J 23/72, 28.12.1988] offer catalysts for the conversion of carbon monoxide formed from copper oxide, zinc oxide and/or magnesium oxide so that contain metallic copper surface is not less than 70 m2/, Catalysts also contain an oxide of at least one element selected from the group consisting of aluminum, vanadium, chromium, titanium, zirconium, thorium, uranium, molybdenum, tungsten, manganese, boron and rare earth elements, preferably Al2About3. The catalysts prepared by precipitation from solutions of metal-containing compounds and consistently active at temperatures above 250°C.

In the patent [US 4835132, B 01 J 021/04, 28.01.1987] presents Cu/Zn/Al catalysts, which is a product of the calcination of hydrotalcite copper-zinc-modified cations La3+CE4+, Zr4+. The General formula of such gidroksicarbonata is given by the expression (Cu+Zn)6AlxRy(CO3)(x+y)/2OH12+2(x+y)nH2O. Such catalysts can be prepared by coprecipitation or impregnation ∀-Al2About3and ceramic matrix solution mixture of different salts of the above metals. It is shown that the catalysts discussed in the patent have high activity in the interval pace is the atur 190-260° C. At the same time, the authors suggest that these catalysts for use in high-temperature CO conversion, indicating high thermal stability on the basis of the data on the change of the total surface area of the catalyst with increasing temperature of annealing from 360°to 600°C. While the surface area of the known Cu/Zn/Al catalyst is reduced by 87%, and the catalyst, modified La, under the same conditions of heat treatment lose only 17% of the surface.

As shown in the patent [EN 2046656, B 01 J 37/08, 27.10.1995] Cu/Zn and Cu/Zn/Al catalysts modified with chromium oxide obtained by termomaslyanym at 250-450°With mixed gidroksicarbonata copper-zinc-aluminum and/or chromium with structure type hydrotalcite-pyroaurite have healthy activity when 240°after overheating up to 300°C for 2 hours

A significant drawback of the above catalysts is their rapid deactivation at temperatures above 300°therefore, these catalysts cannot be used in the single-stage steam reforming process.

In the patent [EN 2118910, B 01 J 23/84, 20.09.1998] presents Cu/Zn/Al catalysts modified with Mn and/or Cr. The preparation of these catalysts was carried termomaslyanym mixed gidroksicarbonata copper-zinc-aluminum and manganese and/or chromium at temperatures of 250-450°C. ActiveState catalysts when 240° With no change after overheating up to 350°in the reaction medium during the 2 hours they are to be used in the temperature range 180-350°C. the disadvantages of these catalysts should include the use of chromium as a stabilizing additive, as there is a danger of poisoning people and the environment in the process of preparing, loading and disposal of spent catalyst. In addition, thermal stability of the obtained catalyst is not high enough for use in one-step process.

Closest to the present invention is a patent [US 5990040, B 01 J 023/00; 01 031/00, 28.07.1997], which describes catalysts for the conversion of carbon monoxide, comprising, in wt.%: 30-70 CuO, 20-50 ZnO, 5-40 Al2About3and 0.2-20 TiO2or ZrO2preferably TiO2as promoter and stabilizer. The authors claim that such catalysts can be consistently active to a temperature of 350°C. to demonstrate the change of activity as at 204° (10 ATM) after 104 hours of work it is shown that a catalyst composed of a titanium oxide, loses activity 14% less than non-modified. In the description of the invention indicates that the introduction of the catalyst of zirconium oxide does not increase thermal stability of the catalyst.

The disadvantage of this catalyst is weeks is quite a high level of thermal stability, therefore, the inability to use the single-stage process.

The present invention is to develop a thermostable catalyst for conversion of carbon monoxide, working effectively in the temperature range of 150-400°C.

To solve this problem is proposed catalyst of the process of conversion of carbon monoxide with water vapor containing copper and characterized in that it contains in its composition phase gidroksicarbonata copper-zinc-zirconium General formula (CuxZryZn1-x-2y)5(CO3)2(OH)6structure hydrozincite and/or aurichalcite, and/or gidroksicarbonata copper-zinc-zirconium General formula (CuxZryZn1-x-2y)2(CO3)(OH)2with the structure of rosasite, or consists of the product of their heat treatment of the General formula CuxZryZn1-x-2yO structure wurtzite, where: x is the number of not more than 0.7, y is a number from 0.01 to 0.33. The catalyst may further comprise a phase graphite, improves the rheological properties of the catalyst.

The task of increasing thermal stability of the catalyst is solved by the introduction of zirconium cations in the structure of the phase copper-zinc gidroksicarbonata or phases of copper oxide-zinc in the catalyst. It is preferable that this phase was a guide is oxocarbon copper-zinc-zirconium structure type hydrozincite or aurichalcite, decompose under the reaction conditions or during the heat treatment with the formation of the oxide phase copper-zinc-zirconium structure type wurtzite. Under the reaction conditions, there is also the recovery of copper cations from the structure of the ternary oxide with the formation phase metallic copper and preservation of the oxide phase with structure type wurtzite containing cations of zirconium. The structural definition of the type discussed phases is performed on the basis of the data of x-ray diffraction (see Figure 1).

It is important to note that the present invention does not apply to catalysts in which the Zr cations are included in the composition of the catalyst only in the form of phase ZrO2as such the presence of zirconium oxide leads to a slight increase of thermal stability of the catalyst. At the same time, the catalyst of the present invention may contain a phase of zirconium oxide, ZrO2.

The dry catalyst or subjected to termoobrabotke at temperatures above 250°in a stream of air or inert gas is formed into or tabletirujut into pellets of any shape.

The following examples illustrate the advantage of the catalysts according to this invention is the possibility of sustainable process steam conversion of CO in a wide temperature range of 150-400°C.

An additional advantage of the invention is the possibility of replacing t is adicionado industrial two-stage steam reforming process WITH one-step conversion process with water vapor when using the catalyst of this invention.

Another advantage of the invention is the absence in the proposed catalyst components that are harmful to the environment.

Characterization of activity and temperature limits of use of the catalyst is determined by comparing its properties with the properties of known CuZnAl catalyst, the catalyst on the basis of CuZnAl-modified Zirconia, and the catalyst prepared in accordance with the patent [EN 2118910, B 01 J 23/84, 20.09.1998].

Mapping carried out in two ways:

1) coefficient of thermal resistance (TMF), which is calculated as the ratio of the rate constants of the reaction, measured at a temperature of 300°before and after overheating in the reaction medium at temperatures of 350, 380 and 400°With over 5 hours of Tests carried out in bigradient (flow-circulation) reactor at atmospheric pressure. Use the reaction mixture composition, vol.%: 18, 10 CO2, 72 H2when steam:gas ratio equal to 0.4;

2) biggest change of the reaction rate constants are in the process of long-term operation observed in the interval after 100 h 150 h of operation. Tests are conducted in flow-through mode under a pressure of 20 ATM and a reaction temperature of 380°C.

The invention is illustrated by the following drawings and examples.

Figure 1. Data on x-ray phase analysis XRD pattern of the catalyst PR is a measure 1 after testing in the reaction medium at a temperature of 380° C.

Figure 2. Data on x-ray phase analysis XRD pattern of the catalyst of example 6 (comparative, zirconium oxide in a separate phase) after testing in the reaction medium at a temperature of 380°C.

Figure 3. Experimental data on the change in catalytic activity with long-term testing of catalysts (◆ - Cu/Zn/Al, ▴Cu/Zn/Al/Cr, • - example 1, o - example 2 x example 6 (comparative, zirconium oxide in a separate phase)in the reaction medium in a flow reactor under a pressure of 20 ATM and a temperature of 380°C.

Example 1.

The catalyst was prepared by coprecipitation of a mixture of 10 wt.% aqueous solutions of nitrate salts of copper, zinc and zirconium 5 wt.% aqueous solution of sodium carbonate at pH 6.8-7.1 and a temperature of 70°C, washing the precipitate with distilled water and drying under an infrared lamp for 24 hours of Cationic composition of the obtained catalyst according to the atomic-absorption spectroscopy is expressed by the formula Cu0.4Zn0.5Zr0.1(hereinafter atomic fraction). According to x-ray phase analysis XRD catalyst represents one phase of gidroksicarbonata with the structure type of aurichalcite and formula (Cu0,36Zr0,09Zn0,46)5(CO3)2(OH)6. In the diffraction pattern of the catalyst has a characteristic set of peaks corresponding to the following interplanar distances patterns and is of raulzito [JCPDS 17-0743]:

d Å6.825.013.722.912.722.642.331.61
IntensityOCScf.S.S.S.S.cf.cf.
where: intensity OCS - very strong, s - strong, Ms. the average. Depending on the cationic composition of the mixed hydroxocobalamine d values can deviate from the above.

According to XRD after heat treatment at 400°the catalyst contains a single phase structure type wurtzite [JCPDS 36-1451] and can be considered as a solid solution of copper ions and zirconium in the structure of defective zinc oxide, after the reaction at a temperature of 380°the catalyst contains two phases: phase structure type wurtzite and phase of Cu0phase on the basis of zirconium oxide is missing (see Figure 1).

The results of catalytic tests are presented in table and figure 3.

Example 2.

The catalyst was prepared under conditions analogous to example 1, but contains cations of copper, zinc and zirconium in an atomic ratio of Cu0.4Zn0.45Zr0.15. According to the XRD phase composition of the catalyst after heat treatment at 400°and conducting reacts and at a temperature of 380° With identical to those given in example 1. Phase characteristic of oxides of zirconium, the sample is not observed.

The results of catalytic tests are presented in table and figure 3.

Example 3.

The catalyst was prepared under conditions analogous to example 1, but the cation composition of the obtained catalyst according to the atomic-absorption spectroscopy is expressed by the formula Cu0.2Zn0.6Zr0.2(hereinafter atomic fraction). According to x-ray phase analysis XRD catalyst represents one phase of gidroksicarbonata structure type hydrozincite and formula (Cu0.22Zr0.22Zn0.67)5(CO3)2(OH)6. In the diffraction pattern of the catalyst has a characteristic set of peaks corresponding to the following interplanar distances patterns of hydrozincite [JCPDS 19-1458]:

d Å6.773.663.142.922.722.482.301.69
IntensityOCSS.S.cf.S.S.cf.S.
where: intensity OCS - very strong, s - strong, Ms. the average. Depending on the cationic composition of the mixed hydroxocobalamine C is achene d can deviate from the above.

The results of catalytic tests are presented in the table.

Example 4.

The catalyst obtained by the coprecipitation of a mixture of aqueous solutions of salts of copper, zinc and zirconium. The cation composition of the obtained catalyst according to the atomic-absorption spectroscopy is expressed by the formula Cu0.59Zn0.23Zr0.18(hereinafter atomic fraction). According to x-ray phase analysis XRD catalyst represents one phase of gidroksicarbonata with the structure of rosasite and formula (Cu0,50Zrof 0.15Zn0,20)5(CO3)2(OH)6. In the diffraction pattern of the catalyst has a characteristic set of peaks corresponding to the following interplanar distances patterns rosasite [JCPDS 36-1475]:

d Å6.045.073.692.962.5992.4992.3392.141.696
IntensityOCSOCSOCSS.OCScf.cf.cf.cf.
where: intensity OCS - very strong, s - strong, Ms. the average. Depending on the cationic composition of the mixed hydroxocobalamine d values can deviate from the websites is the R above.

The results of catalytic tests are presented in the table.

Example 5.

Similar to example 1, but the catalyst contains a separate phase of graphite, improving its formation, and is a tablet size 5×2.5 mm After working in the reaction medium at a temperature of 380°the catalyst contains according to x-ray fluorescence analysis in two phases: phase structure type wurtzite and phase of Cu0. Phase characteristic of oxides of zirconium, the sample is not observed. The results of catalytic tests the extent of use of grain in the temperature range 250-380°was 0.30-0.14, respectively. The coefficient of thermal resistance does not differ from KTU defined in example 1.

The results of catalytic tests are presented in the table.

Example 6 (comparative, zirconium oxide in a separate phase).

The catalyst obtained by mechanical stirring, including the state seal, the two catalyst components, representing a solid solution of copper in the zinc oxide and zirconium oxide. The cation composition of the obtained catalyst is expressed by the formula Cu0.4Zn0.5Zr0.1and close, thus, the composition of the catalyst of example 1. However, according to x-ray phase analysis XRD catalyst contains a phase type wurtzite and separate phase of zirconium oxide ZrO2(see figure 2)and after the reaction is arawai conversion - phase metallic copper phase type wurtzite and separate phase of zirconium oxide ZrO2.

The results of catalytic tests are presented in figure 3.

Example 7 (comparative, aluminum).

The catalyst, similar in structure and composition of the catalyst of the patent [US 5990040, B 01 J 023/00; 01, 031/00, 28.07.1997], obtained by coprecipitation of a mixture of aqueous solutions of salts of copper, zinc, aluminum and zirconium. The cation composition of the obtained catalyst according to the atomic-absorption spectroscopy is expressed by the formula Cu0.4Zn0.17Al0.33Zr0.1. According to x-ray phase analysis XRD catalyst is a phase gidroksicarbonata structure type hydrotalcite. In the diffraction pattern of this compound with the structure of hydrotalcite has a characteristic set of peaks corresponding to the following interplanar distances [JCPDS 41-1428]:

d Å5.544.042.532.331.86
Intensitycf.cf.OCSS.cf.
where: intensity OCS - very strong, s - strong, Ms. the average.

Depending on the composition of the mixed hydroxocobalamine d values may have little to deviate from those listed in the above. The results of catalytic tests are presented in the table. The results of catalytic tests using overheating when 350-380-400°it is seen that the known low-temperature Cu/Zn/Al catalyst, as expected, quickly deactivated under these conditions.

The data in table 1 and Figure 3 confirm that the catalysts of examples 1, 2 and 5, in which the cations of zinc and zirconium are included in a single chemical compound, thermally more resistant to overheating than previously known catalysts.

The catalyst prepared in accordance with the patent Cu/Zn/Al/Cr [EN 2118910, B 01 J 23/84, 20.09.1998] and have a sustainable activity at temperatures up to 350°With less thermostable than the catalysts of examples 1, 2 and 5. After overheating at temperatures of 380°400°With this catalyst loses catalytic activity.

The catalyst of example 7 (comparative, aluminum), which is a phase of gidroksicarbonata structure hydrotalcite, about 2.5-3 times less active and is approximately 1.5 times less resistant to overheating in comparison with the catalysts of examples 1 and 2.

According to long-term tests in the reaction medium under a pressure of 20 ATM and a reaction temperature of 380°it is seen that the known Cu/Zn/Al catalyst is rapidly deactivated during the first 90 hours. Catalyst Cu/Zn/Al/Cr prepared according to the following patent [EN 2118910, B 01 J 23/84, 20.09.1998], under these conditions deactivated at a constant speed. The catalyst of example 6 (comparative, zirconium oxide in a separate phase) also loses activity during the trial, which is due to the fact that the zirconium cations in its structure mainly form a separate phase of zirconium oxide, ZrO2. In contrast to these catalysts, the catalysts of examples 1, 2 and 5 after 100 hours of operation and up to 150 hours at a sufficiently high constant activity.

0.52
Table.

Experimental data on the change in the value of catalytic activity and thermal stability (KTU), determined at a temperature of 300°before and after overheating at 350, 380 and 400°in a flow-circulation reactor.
Catalystk, 1/sk, 1/ck, 1/ck, 1/c
300°350°KTU380°KTU400°KTU
Cu/Zn/Al18.611.40.616.90.373.80.20
Cu/Zn/Al/Cr36.125.60.7118.915.30.42
Example 12519.50.7818.70.7515.70.63
Example 220.620.40.9918.30.8913.80.67
Example 3128.10.675.50.464.00.33
Example 430150.50100.3070.23
Example 57.55.850.785.60.754.70.63
Example 7 (comparative, Al)10.670.665.80.555.40.51

1. The catalyst of the process of conversion of carbon monoxide with water vapor containing copper, characterized in that it contains in its composition phase gidroksicarbonata copper-zinc-zirconium General formula (CuxZryZn1-x-2U)5(CO3)2(OH)6structure hydrozincite and/or aurichalcite and/or gidroksicarbonata copper-zinc-zirconium General formula (CuxZryZn1-x-2 )2(CO3)(OH)2with the structure of rosasite or consists of the product of thermal treatment of General formula CuxZryZn1-x-2yO structure wurtzite, where x is the number of not more than 0.7, y is a number from 0.01 to 0.33.

2. The catalyst according to claim 1, characterized in that it further comprises a phase graphite, improves the rheological properties of the catalyst.

3. A method of converting a gas mixture containing CO and H2Oh, characterized in that it comprises passing the reaction gas mixture through the catalyst bed according to claim 1 or 2.

4. The method according to claim 3, characterized in that it is carried out at a temperature of from 150 to 400°C.



 

Same patents:

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12 cl

FIELD: production of catalysts on base of compounds of copper, zinc and aluminum for low-temperature conversion of carbon oxide with water steam; chemical, and petrochemical industries; production of ammonia and hydrogen.

SUBSTANCE: proposed method consists in mixing the solution of ammonia-carbonate complex of copper with solution of ammonia-carbonate complex of zinc and with oxide or hydroxide of aluminum; suspension thus obtained is heated to 40-50°C, then it is subjected to stirring continued for 1-2 h, after which temperature is raised to 85-97°C and purge gas is introduced, for example nitrogen or carbon dioxide and suspension is mixed at solid-to-liquid ratio of 1:(2.0-4.0); sediment is removed; mixture is dried, calcined and liquid stabilizing additives are introduced into calcined mass at solid-to-liquid ratio of 1: (0.2-1.0) and 1-1.5 mass-% of graphite is added; mixture is stirred, granulated and pelletized. Used as stabilizing additives are chromic, nitric or oxalic acids, or their salts, or carbamide.

EFFECT: enhanced activity and thermal stability.

2 cl, 1 tbl, 20 ex

FIELD: industrial organic synthesis catalysts.

SUBSTANCE: invention relates to copper-containing catalysts for low-temperature synthesis of methanol in fluidized bed at high pressure and provides catalyst, whose preparation involves impregnation and which contains oxides of copper, zinc, chromium, magnesium, aluminum, boron, and barium and has following molar ratio: CuO:ZnO:Cr2O3, MgO:Al2O3:B2O3:BaO = 1:(0.7-1.1):(0.086-0.157):(0.05-0.15):(0.125-0.2):(0.018-0.029):(0.04-0.075).

EFFECT: increased mechanical strength and wear resistance of catalyst.

1 tbl

FIELD: industrial organic synthesis catalysts.

SUBSTANCE: invention relates to copper-containing catalysts for low-temperature synthesis of methanol in fluidized bed at low pressure and provides a wear-resistant catalyst, whose preparation involves impregnation and which contains oxides of copper, zinc, chromium, magnesium, aluminum, and boron and has following molar ratio: CuO:ZnO:Cr2O3, MgO:Al2O3:B2O3 = 1:0.3:(0.15-0.2):(0.1-0.025):(0.25-0.3):(0.08-0.1).

EFFECT: increased mechanical strength and wear resistance of catalyst.

1 tbl

FIELD: industrial organic synthesis catalysts.

SUBSTANCE: invention relates to copper-containing catalysts for low-temperature synthesis of methanol in fluidized bed at median pressure and provides catalyst, whose preparation involves impregnation and which contains oxides of copper, zinc, chromium, magnesium, aluminum, boron, and barium and has following molar ratio: CuO:ZnO:Cr2O3, MgO:Al2O3:B2O3:BaO = 1:0.3:(0.014-0.038):(0.047-0.119):(0.05-0.1):(0.007-0.014):(0.0292-0.054).

EFFECT: increased mechanical strength and wear resistance of catalyst.

1 tbl

The invention relates to a process for the preparation of catalysts based on copper compounds and zinc for low-temperature conversion of carbon monoxide with water vapor and can be used in the chemical and petrochemical industry, for example, in the production of ammonia and hydrogen, the synthesis of methanol and other industries

The invention relates to a method for preparing CdS photocatalyst for hydrogen production and to a method of obtaining hydrogen from water by photochemical reaction with its application

The invention relates to a method for producing ester of formic acid or methanol and the catalyst of this method

The invention relates to catalysts and methods for selective hydrogenation of acetylene hydrocarbons, in particular ethylene by selective hydrogenation of acetylene in the gas phase, and may find application in processes for purifying gas mixtures from impurities acetylene

FIELD: organic synthesis catalysts.

SUBSTANCE: catalyst for modifying colophony contains, as carrier, high-porosity cellular α-alumina-based block material and, as active catalyst fraction, sulfated group IV metal oxide and metallic palladium.

EFFECT: increased modification rate due to developed catalyst surface and eliminated disintegration and carry-over of catalyst.

5 ex

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