Catalyst preparation method

FIELD: supported catalysts.

SUBSTANCE: invention claims a method for preparation of catalyst using precious or group VIII metal, which comprises treatment of carrier and impregnation thereof with salt of indicated metal performed at working pressure and temperature over a period of time equal to or longer than time corresponding most loss of catalyst metal. According to invention, treated carrier is first washed with steam condensate to entirely remove ions or particles of substances constituted reaction mixture, whereupon carrier is dried at 110-130oC to residual moisture no higher than 1%.

EFFECT: achieved additional chemical activation of catalyst, reduced loss of precious metal from surface of carrier, and considerably increased lifetime.

5 cl, 9 ex

 

The invention relates to catalytic chemistry, in particular to methods of producing metal-supported catalysts, for example, based activated carbons, mainly hydrogenation catalysts.

In catalytic chemistry are widely used in various metal-supported catalysts, in particular catalysts with precious metals such as silver or metals of group VIII of the Periodic system, such as palladium, using as the basis, for example, activated carbon. Due to the high cost of these metals, the challenge is to reduce their consumption in the production process. This problem is solved in modern catalytic chemistry in different ways. For example, in the copyright certificate of the Russian Federation No. 1538326, publ. 10.09.96,, bull. No. 25, the reduction of the palladium is achieved by increasing the activity and mechanical strength of the carbon media by getting media processing soot gaseous hydrocarbon mixture, then the processing vapor mixture with the subsequent further processing of the carbon material with gaseous hydrocarbons to increase its mass to 1-50%. The catalyst is prepared by impregnation of a granulated carbon media with a mixture of solutions paradichlorobenzene acid and sodium carbonate with the consequences of the decisions by reduction with hydrogen. The catalyst used in the process of hydrogenation of benzene to cyclohexane. In the patent of Russian Federation №1833204, publ. 07.08.93,, bull. No. 29, the reduction of the palladium is due to the fact that palladium catalyst based on alumina are impregnated alumina at the beginning of dimethylformamide and then acidified with oxalic acid solution of palladium salt, followed by reduction of palladium to the metal by heating, washing and drying. This method allows you to get on the surface of the palladium complex, well adsorbed by the media, having on the surface acid-base functional groups. In the copyright certificate of the Russian Federation No. 1796243, publ. G., bull. No. 7, reduced consumption of palladium is achieved by improving the chemical homogeneity of the surface of the media to create conditions for uniform distribution of the active metal on its surface, which palladium catalyst on charcoal is produced by impregnation of activated carbon with a solution of palladium compounds with methylformamide with subsequent recovery upon heating, washing and drying and impregnation of the coal gidroksilnuyu as palladium compounds use it dichlorobistriphenylphosphine complex and recovery of lead added to the reaction mixture of gersinhomala.

The disadvantage is the means of obtaining the catalyst on a solid support coated on the surface of the noble metal is that the processing of the carrier and the coating metal are using chemicals that differ in composition from the reaction media, which employ catalysts, which in the working conditions is the rapid destruction of the media reaction mass and thus increasing the losses of precious metals from the surface of the media.

The objective of the invention is to provide a method of producing catalyst, lowering losses of noble metals with the surface of the carrier and increase the service life of the catalyst.

The problem is solved in the proposed method of preparation of the catalyst noble metal, such as silver, or a metal of group VIII of the Periodic table, such as palladium, which includes treatment media such as activated carbon, and the subsequent impregnation of the support with a solution of salts of the mentioned metals, for example, a solution of palladium chloride, due to the fact that the processing of the media lead to reaction mass at operating temperature and pressure for a time equal to or greater time greatest losses of the metal catalyst.

After this processing the media prior to impregnation it is washed with steam condensate to the absence of ions or particles of substances in the reaction mass. Before the impregnated carrier is dried at temperature-130° C to a residual moisture content of not more than 1%.

The invention consists in that the catalyst carrier before applying the metal is placed in the working environment of the catalyst and maintained at a temperature holding process a certain time equal to the time of the greatest loss of catalyst. When this occurs the chemical and structural changes in the surface of the carrier caused by the influence of the reaction medium of the process and operating temperature. Therefore, after applying to the thus treated carrier noble metal of the finished catalyst is not already undergoing these changes and loss of metal from its surface is significantly reduced and the service life of the catalyst is increased.

The proposed method for the preparation of the catalyst is carried out as follows.

Example 1. Source media - charcoal active brand AG-3 according to GOST 20464-75, placed at 6 hours (while the greatest losses of metal catalyst) in a mixture of chlorinated derivatives of acetic acid with a content of dichloracetic acid from 4% to 9% (operating the reaction mixture in the hydrogenation process) and maintained at a temperature of 140°C (working temperature of the process) sparging the mixture with nitrogen. After that, the washed coal steam condensate to the absence of chlorine-ion, dried at a temperature of 110-130°and n is worn palladium in the form of a solution PdCl 2by impregnation of capacity, followed by drying at a temperature of 110-130°C to a residual moisture content of less than 1%. The loss of weight of coal in the process reaches 10%. After such loss treatment with palladium catalyst is reduced with 55.7 per cent (38 hours doing hydrogenation process) to 15.2% (over 74 hours of doing hydrogenation process, meaning that the loss has decreased more than three times.

Example 2. Source media - charcoal active brand AG-3 according to GOST 20464-75 placed for 12 hours in a mixture of chlorinated derivatives of acetic acid with a content of dichloracetic acid from 4% to 9%. Further processing of coal and the preparation of the catalyst is carried out as in example 1. After such loss treatment with palladium catalyst is reduced with 55,7% to 11% (39 hours doing hydrogenation process), i.e. the loss has decreased five times.

Example 3. Source media - charcoal active brand AG-3 according to GOST 20464-75 placed for 6 hours in a mixture of chlorinated derivatives of propionic acid content dichloropropionic acid 9%. Further processing of the media and the preparation of the catalyst are as in example 1. After this treatment, the loss of palladium on the surface of the catalyst is reduced with 40,83% (after 6 hours of doing hydrogenation process on the raw catalyst) to 25.2% (after 6 hours of doing process gidrirovanie is). Losses decreased by more than 1.5 times.

Example 4. Source media - charcoal active brand art And according to GOST 8703-74 placed for 6 hours in a mixture of chlorinated derivatives of acetic acid with a content of dichloracetic acid from 4% to 9%. Further processing of the media and the preparation of the catalyst are as in example 1. Loss with palladium catalyst is: without additional processing - 34,78%, with additional processing was 15.19%. The loss has decreased more than twice.

Example 5. Source media - charcoal active brand AG-2 according to GOST 23998-80 placed for 6 hours in a mixture of chlorinated derivatives of acetic acid with a content of dichloracetic acid from 4% to 9%. Further processing is as in example 1. Loss with palladium catalyst is: without additional processing - 36,88%, with additional processing - 15,85%. The loss has decreased more than twice.

Example 6. Manufacture of palladium catalyst by a known method. Source media - charcoal active brand AG-3 according to GOST 20464-75. Production of Dzerzhinsk or Perm. The coal is dried at a temperature of 110-130°and his cause palladium in the form of a solution PdCl2by impregnation of capacity, followed by drying at a temperature of 110-130°C to a residual moisture content of less than 1%. Loss of palladium on Dzerzhinsky coal is on average about 40% for 4-24 hours selective the project. Loss on the Permian coal was 41,25% for the first 6 hours of hydrogenation and 55.7% for 38 hours hydrogenation. After treatment of the catalyst loss palladium Dzerzhinsk coal was 17-2%, Perm and 19.4% (6 hours) and 28.7% (38 hours), i.e. the loss of palladium declined by about 2 times.

Example 7. Source media - charcoal active AG-3 according to GOST 20464-75 placed for 6 hours in a mixture of chlorinated derivatives of acetic acid with a content of dichloracetic acid from 4% to 9%. Further processing of the media and the preparation of the catalyst are as in example 1, except that instead of palladium chloride impregnation of coal is the solution platinochloride acid. Losses platinum catalyst is: without additional processing - 61,54% (after 6 hours of doing hydrogenation process), with additional processing to 15.4 (after 6 hours of doing hydrogenation process). The loss dropped 4 times.

Example 8. Source media - charcoal active AG-3 PAST 20464-75 placed for 12 hours in a mixture of propionovoi (50%) and propionic (50%) of the acid and maintained at a temperature of 50-80°C (working temperature of the process) by sparging with nitrogen. After that, the washed coal steam condensate to a neutral environment and is dried at a temperature of 110-130°C to a residual moisture content of not more than 1% and it is applied cobalt in the form of a solution l2method prop the TCI on capacity, followed by drying at 110-130° C to a residual moisture content of less than 1%. After this treatment in the process of getting propionic acid from propionovoi (hydrogenation of the triple bond) loss of cobalt from the media reduced from 34.7% in 48 hours to process) to 16.8 (after 48 hours of operation). That is, the loss has decreased more than 2 times.

Example 9. Source media - silicon oxide (SiO2) granulated we will lay 12 hours in benzene and maintained at a temperature of 70-80°C (working temperature of the process) by sparging with nitrogen. After that, the silica was washed with 96%ethanol to remove benzene, dried at a temperature of 110-130°and covered with palladium in the form of a solution PdCl2and gold in the form of AuCl3by impregnation of capacity, followed by drying at a temperature of 110-130°C to a residual moisture content of less than 1%. The original palladium content is not more than 0.2%, the original gold content is not more than 5%. After this treatment, the loss of palladium decreased from 12% (after 72 hours of conducting the process of hydrogenation of benzene in cyclohexane) to 5% (after 72 hours of operation). Loss of gold decreased from 15.4% (after 48 hours) to 6.8% (after 48 hours). That is, losses on palladium and gold fell by more than twice.

The present invention allows to provide additional chemical activation of the carrier, to reduce the loss of blagoroden the first metal with the surface of the carrier and substantially increase the service life of the catalyst.

1. The method of producing catalyst with precious metal or a metal of group VIII of the Periodic table, including handling the media and the subsequent impregnation of the support with a solution of salts of the specified metal, characterized in that the processing of the media lead to reaction mass at operating temperature and pressure for a time equal to or greater time greatest losses of the metal catalyst, after processing the media prior to impregnation it is washed with steam condensate for removal of ions or particles of substances in the reaction mass, and drying the carrier before the impregnation is carried out at a temperature of 110-130°C to a residual moisture content of not more than 1%.

2. The method according to claim 1, characterized in that the noble metal is used, for example, silver.

3. The method according to claim 1, characterized in that as the metal of group VIII of the Periodic table are used, for example, palladium.

4. The method according to items 1 to 3, characterized in that as the carrier is used, for example, activated carbon.

5. The method according to claim 1, characterized in that as the metal salt catalyst is used, for example, a solution of palladium chloride.



 

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