The method of preparation of palladium catalyst for selective hydrogenation of liquid and gaseous fractions of pyrolysis oil

 

(57) Abstract:

The invention relates to the production of palladium catalysts for selective hydrogenation of organic compounds. In accordance with the present invention of preparing a palladium-based catalyst for selective hydrogenation of liquid and gaseous fractions of pyrolysis oil by impregnation of the alumina carrier with an aqueous solution of salts of palladium and sodium and drying, and use alumina carrier with a total pore volume of 0.10-0.95 cm3/g and impregnation are an aqueous solution of palladium acetate and sodium, and saturated with a solution of palladium acetate and sodium alumina carrier before drying is maintained at atmospheric pressure and a temperature of 1-50oC for 0.5 to 24 hours additionally impregnated with a solution of palladium acetate and sodium alumina carrier is additionally subjected to acarnania sulfur-containing agent to the ratio, wt.h., palladium : sera from 20:1 to 3:1, and as the sulfur-containing agent use hydrogen sulfide, carbon sulfide or sodium sulfide. The technical result is to increase the specific activity of the catalyst. 2 C.p. f-crystals, 2 tab.

The present invention relates to the field of proizvodstvenyi

A method of obtaining palladium catalyst for selective hydrogenation of acetylene and/or diene hydrocarbons by impregnation of a pre-treated alcohol-containing component of the alumina carrier with a solution of palladium salt, followed by drying and activation [RF Patent 1677904, 01 J 37/02, 23/44].

The disadvantages of this method are the low specific activity of the catalyst and the use of organic solvents, which affects the environmental performance of the production.

Closest to the present invention to the technical essence and the achieved result is a method for preparing palladium catalyst for selective hydrogenation of organic compounds including the impregnated alumina carrier with an aqueous solution of salts of palladium and sodium, followed by drying [Process regulation N R-064 to the manufacture of palladium catalyst PC-50 "Angarsknefteorgsintez"]. In the known method as salts of palladium and use sodium chloride.

The disadvantage of the catalyst obtained by this method is low specific activity in the hydrogenation process due to the distribution of active componendo the process of hydrogenation.

Disclosure of the invention

The technical problem solved by the present invention is to improve the properties of the resulting palladium catalyst.

The technical result of the invention is the preparation of a palladium catalyst with high specific activity in the selective hydrogenation of liquid and gaseous fractions of pyrolysis oil. Additional technical result is the ability to control specific activity in the process of operation of palladium catalyst.

This technical problem with the achievement of the technical result is solved in the method of preparation of palladium catalyst for selective hydrogenation of liquid and gaseous fractions of pyrolysis oil comprising the impregnated alumina carrier with an aqueous solution of salts of palladium and sodium and drying, in which use alumina carrier with a total pore volume of 0.10-0.95 cm3/g and impregnation are an aqueous solution of palladium acetate and sodium, and saturated with a solution of palladium acetate and sodium alumina carrier before drying is maintained at atmospheric pressure and a temperature of 1-50oC for 0.5 to 24 hours in Addition, propeta the holding agent to the ratio, wt. 'clock, palladium : sera from 20:1 to 3: 1. In addition, as a sulfur-containing agent use hydrogen sulfide, carbon sulfide or sodium sulfide.

The main distinguishing features of the present invention is that the preparation of the catalyst as an aqueous solution of salts of palladium and sodium apply solutions of palladium acetate and sodium, use alumina carrier with a total pore volume of 0.10-0.95 cm3/g, and soaked in a solution of palladium acetate and sodium alumina carrier before drying is maintained at atmospheric pressure and a temperature of 1-50oC for 0.5-24 h

Additional distinctive features is that the preparation of the catalyst is impregnated with a solution of palladium acetate and sodium alumina carrier is subjected to acarnania sulfur-containing agent to the ratio, wt. 'clock, palladium : sera from 20:1 to 3:1, and as the sulfur-containing agent use hydrogen sulfide, carbon sulfide or sodium sulfide.

The present invention meets the condition of patentability "inventive step", because of the known prior art at the filing date of the application for the present invention it was not known that predlagaemaya palladium and sodium when the impregnated alumina carrier with a total pore volume of 0.10-0.95 cm3/g and cure it before drying at atmospheric pressure and a temperature of 1-50oC for 0.5-24 h ensures the application of palladium Korotkova layer thickness of 0.1 to 0.15 mm, Conducted by the authors showed that it is optimal to obtain a catalyst with high specific activity. But, as you know, the high specific activity of the catalyst is undesirable in the operation of its in-rush periods, because it leads to deactivation due to possible overheating. The proposed acarnania - introduction to the catalyst sulfur in certain quantities allows you to adjust the specific activity at the start, because in the process of operation, the sulfur is gradually removed and the activity is restored.

The invention is illustrated by the following examples.

Example 1.

999 alumina carrier with a total pore volume of 0.5 cm3/g is impregnated with 500 cm3an aqueous solution containing 4.3 g of sodium acetate and 2,11 g of palladium acetate, after which withstand the impregnated carrier at atmospheric pressure and a temperature of 20oC for 10 h, and then dried at 150oC.

The finished catalyst was tested in static conditions, the volumetric shall be as the amount of hydrogen, absorbed for 1 min, referred to 1 wt.% Pd.

The results of the tests and the conditions of preparation of the catalyst are given in table. 1.

Example 2.

The catalyst prepare and test as in example 1, but the impregnated carrier is maintained at a temperature of 50oC for 0.5 hours

Example 3.

The catalyst prepare and test as in example 1, but using alumina media with pore volume of 0.1 cm3/g and impregnate his 100 cm3an aqueous solution containing 4.3 g of sodium acetate and 4,22 g of palladium acetate.

Example 4 (limiting conditions on the total pore volume, temperature and time-keeping).

999 alumina carrier with a total pore volume of 0.95 cm3/g is impregnated with 950 cm3an aqueous solution containing 4.3 g of sodium acetate and 2,11 g of palladium acetate, then aged impregnated carrier at atmospheric pressure and a temperature of 1oC for 24 h the Finished catalyst was tested as in example 1.

Example 5 (nearest equivalent).

100 g of the alumina carrier with a total pore volume of 0.6 cm3/g is impregnated with 60 cm3an aqueous solution containing 0.9 g of palladium chloride and 0.6 g of sodium chloride, then 2">

Example 6.

The catalyst prepare and test as in example 1, but additionally sarnaut his 50 cm340% water-alcohol solution containing 0.12 g of carbon disulphide.

Example 7.

The catalyst prepare and test as in example 1, but the impregnated carrier is maintained at a temperature of 50oC for 0.5 h and optionally sarnaut his 50 cm3gas mixture containing 0.32 g of hydrogen sulfide.

Example 8 (limiting conditions on the total pore volume, temperature, time-keeping and the ratio of Pd:S).

999 alumina carrier with a total pore volume of 0.95 cm3/g is impregnated with 950 cm3an aqueous solution containing 4.3 g of sodium acetate and 2,11 g of palladium acetate, then aged impregnated carrier at atmospheric pressure and a temperature of 1oC for 24 h and optionally sarnaut 50 cm3an aqueous solution containing 0.12 g of sodium sulfide. The finished catalyst was tested as in example 1.

From the comparison of examples 1-4 (present invention) example 5 (the closest analogue) Fig. 1, it is seen that obtained in examples 1-4 catalyst has a significantly higher specific activity in comparison with the nearest and the activity is reduced by more than 100 times.

Example 9 (out-of-limit conditions on the total pore volume, temperature and time-keeping).

999 alumina carrier with a total pore volume of 0.05 cm3/g is impregnated with 50 cm3an aqueous solution containing 4.3 g of sodium acetate and 2,11 g of palladium acetate, after which withstand the impregnated carrier at atmospheric pressure and a temperature of 51oC for 0.25 h and then dried at 150oC. the Catalyst was tested as in example 1, the results are shown in table. 1.

As can be seen from the test results, when going beyond the preparation conditions receive the catalyst with a specific activity at the level closest analogue.

Industrial applicability

The invention can be implemented using known means and used for production of palladium catalysts for selective hydrogenation of organic compounds.

1. The method of preparation of palladium catalyst for selective hydrogenation of liquid and gaseous fractions of pyrolysis oil comprising the impregnated alumina carrier with an aqueous solution of salts of palladium and sodium and drying, characterized in that use alumina carrier with a total pore volume of 0.10-0.95 cmalladia and sodium alumina carrier before drying is maintained at atmospheric pressure and a temperature of 1-50oC for 0.5-24 h

2. The method of preparation of palladium catalyst for selective hydrogenation of liquid and gaseous fractions of pyrolysis oil under item 1, characterized in that it is impregnated with a solution of palladium acetate and sodium alumina carrier is additionally subjected to acarnania sulfur-containing agent to the ratio, wt.h., palladium : sera from 20 : 1 to 3 : 1.

3. The method of preparation of palladium catalyst for selective hydrogenation of liquid and gaseous fractions of pyrolysis oil under item 2, characterized in that as the sulfur-containing agent use hydrogen sulfide, carbon sulfide or sodium sulfide.

 

Same patents:

The invention relates to a method for heterogeneous bimetallic palladium-gold catalyst to obtain a vinyl acetate from ethylene, acetic acid and oxygen

The invention relates to catalysts for (co)polymerization of ethylene containing chromium trioxide deposited on a solid inorganic oxide carrier of nature, i.e

The invention relates to a method for hydrogenation of aromatic ketones, which are intermediate compounds used in the production of dyes, varnishes, resins

The invention relates to the chemical industry, and in particular to methods of preparation of catalysts for the process of ethylene oxide gas-phase oxidation of ethylene with oxygen

The invention relates to the production of catalysts, in particular latinoreview catalyst for reforming of gasoline fractions

The invention relates to the catalytic substance and the method of its production

The invention relates to the production of catalysts and can be used for such catalytic processes such as the purification of olefins and their fractions from acetylene compounds

The invention relates to a method for producing a catalyst for the synthesis of unsaturated esters by gas-phase reactions, in particular for gas-phase formation of vinyl acetate in the reaction of ethylene, oxygen and acetic acid
The invention relates to the production of catalysts for the synthesis of tert-butyl methyl ether, used as an additive to gasoline

The invention relates to a method for heterogeneous bimetallic palladium-gold catalyst to obtain a vinyl acetate from ethylene, acetic acid and oxygen

The invention relates to a method for producing a catalyst for the synthesis of unsaturated esters by gas-phase reactions, in particular for gas-phase formation of vinyl acetate in the reaction of ethylene, oxygen and acetic acid

The invention relates to a catalyst and method of its preparation for the selective purification of gas mixtures containing nitrogen oxides, oxygen, and nitrogen dioxide

The invention relates to catalysts for the conversion of ammonia and can be used to produce oxides of nitrogen in nitric acid and has synthesis

The invention relates to the production of catalysts for heterogeneous processes, which are used in carrying out various chemical reactions, in particular catalysts for oxidation of SO2and SO3in the manufacture of sulfuric acid or purifying gases

The invention relates to the field of catalysts, in particular for the hydrogenation of vegetable oils and fats, and can be used in the food, perfume, petrochemical and refining industries

The invention relates to gas-phase purification of ethane-ethylene fraction of pyrogas from acetylene impurities, in particular to the purification catalysts by the method of selective hydrogenation

FIELD: inorganic synthesis catalysts.

SUBSTANCE: invention provides ammonia synthesis catalyst containing ruthenium as active ingredient supported by boron nitride and/or silicon nitride. Catalyst can be promoted by one ore more metals selected from alkali, alkali-earth metal, or rare-earth metals. Ammonia synthesis process in presence of claimed catalyst is also described.

EFFECT: increased temperature resistance of catalyst under industrial ammonia synthesis conditions.

4 cl, 6 ex

Up!