Catalyst for hydrogenation of unsaturated hydrocarbons

 

(57) Abstract:

Catalyst for hydrogenation of unsaturated hydrocarbons containing palladium on the carrier of alumalite composition x B2O3y Al2O3where x 0,07 0,22 and y 0,83 0,93, with the following ratio of components, wt. Pd 0,2 0,5; media else. The catalyst contains palladium in the oxide or sulfide form. 1 C.p. f-crystals, 1 table.

The invention relates to catalysts for hydrogenation of unsaturated hydrocarbons and can be used for hydrofining of liquid pyrolysis products.

A known catalyst for the hydrogenation of olefins, which represents a palladium and/or ruthenium on alumina promoted with the addition of nitrates Cr, La, Ba in mass ratio of Pd and/or ruthenium and the promoter equal to 0.005 to 1: 1 [1] the Disadvantages of this catalyst are low mechanical strength and hydrogenating activity. Thus, the hydrogenation of 1-hexene (10% solution in toluene) at a pressure of 5 MPa, flow rate 3 h-1, the ratio of hydrogen to the raw material, 100 nm3/m3the degree of hydrogenation at 50aboutWith 49% of the Mechanical strength of the catalyst 1.8 kg/mm

A known catalyst for the hydrogenation of unsaturated who uminia [2] the Disadvantage of this catalyst is its low hydrogenation activity and mechanical strength. Thus, the hydrogenation of 1-hexene (10% solution in toluene, a pressure of 5 MPa, a space velocity of 3 h-1) if 50aboutWith the degree of hydrogenation of this catalyst is 47,19% of the Mechanical strength of the catalyst 1.9 kg/mm

Closest to the invention is an aluminum-palladium catalyst containing 0.5% of Pd on AL2O3[2] the Disadvantages of the catalyst are not high hydrogenating activity at low temperatures and low mechanical strength. Thus, the hydrogenation of 1-hexene (10% solution of hexene-1 in toluene, a pressure of 5 MPa, a space velocity of 3 h-1N2:raw 100 m3/m3) at a temperature of 50aboutWith the degree of hydrogenation of hexane-1 is 91.3% of the Mechanical strength is 1.4 kg/mm

The aim of the invention is to increase the mechanical strength and hydrogenating activity of the catalyst.

This goal is achieved by using as the carrier palladium catalyst bismuth composition xB2O3yAl2O3when the next value of molar ratios:

X 0,07-0,22

Y 0,83-0,93 and the following composition of the catalyst, wt. palladium and 0.2-0.5; medium up to 100.

The goal to is a symptom of the invention is the composition of the media. A variation of the molar ratios of B2O3and Al2O3(i.e., the coefficients X and Y) optimizes the characteristics of medium strength, rastreskivaetsja the sudden change in temperature and a high hydrogenating activity of the catalyst.

The catalyst is prepared as follows: fresh pasta aluminium hydroxide contribute oxide of boron (as boric acid) and nitric acid peptization. The resulting mass is formed into extrudates, dried at a temperature of 100-120aboutWith 4-5 hours and calcined 3 h at 500aboutC.

The resulting carrier is impregnated with a solution of palladium chloride in a 0.25% solution of hydrochloric acid at a temperature of 20-25aboutC for 1 h After impregnation, the excess solution is drained and the catalyst is subjected to drying at a temperature of 100-150aboutWith the current of air within 4-6 hours (drying may precede acarnania in a stream of hydrogen sulfide at a temperature of 110aboutC for 2-10 h).

P R I m e R 1. 316 g of paste of aluminum hydroxide is mixed with 5.5 g boric acid (H3IN3) and 0.4 DM357% nitric acid, formed into extrudates, dried at a temperature of 120aboutWith 4 hrs and calcined at a temperature of 500aboutWith a 3 hour 100 g of the extrudates wear palladium chloride. The catalyst is dried in a current of air at a temperature of 120aboutAt 6 a.m. the Composition and properties of the obtained catalyst are shown in table.

P R I m m e R 2. The catalyst prepared according to example 1 with the difference that the carrier extrudates at 110aboutWith dried 5 h, and the impregnating solution contains 0,83 g of palladium chloride. Drying of the catalyst is carried out in a current of air at 130aboutWith 4 hours Composition and properties of the obtained catalyst are shown in table.

P R I m e R 3. The catalyst prepared in example 1, except that the impregnating solution contains 0.5 g of palladium chloride. Before drying, the catalyst is treated with hydrogen sulfide at 110aboutWith 2 hours Composition and properties of the obtained catalyst are shown in table.

P R I m e R 4. The catalyst prepared according to the techniques of example 1, with the difference that for the preparation of media 282,1 g of paste of aluminum hydroxide is mixed with 17.3 g of N3IN3and 0.33 DM357% nitric acid. The resulting extrudates are dried at 100aboutWith 6 hours Impregnating solution contains 0.5 h of palladium chloride. The catalyst was dried at 150aboutWith 4 hours Composition and properties of the obtained catalyst are shown in table.

P R I m e R 5. The catalyst prepared according to the techniques of example 1, with the m357% nitric acid, and the impregnating solution contains 0.5 g of palladium chloride. The catalyst was dried at 100aboutAt 6 a.m. the Composition and properties of the obtained catalyst are shown in table.

P R I m e R 6. The catalyst prepared according to example 3, with the difference that the treatment with hydrogen sulfide is carried out at a temperature of 110aboutC for 6 hours Composition and properties of the obtained catalyst are shown in table.

P R I m e R 7. The catalyst prepared according to example 3, with the difference that the treatment with hydrogen sulfide is carried out at 110aboutWith over 10 hours Composition and properties of the obtained catalyst are presented in the table.

P R I m e R 8 (comparative). The catalyst prepared according to the techniques of example 1, except that the impregnating solution contains 0.25 g of Pd. The composition and properties of the finished catalyst shown in the table.

P R I m e R 9 (comparative). The catalyst prepared according to the techniques of example 1, except that the impregnating solution contains 1.0 g of Pd. The composition and properties of the obtained catalyst are shown in table.

P R I m e R 10 (comparative). The catalyst prepared according to example 3, with the difference that for the preparation of media 313,7 g of aluminum hydroxide is mixed with 3.9 g of boric acid and 0.4 DM3retelny). The catalyst prepared according to example 3, with the difference that for the preparation of media 285,5 g of aluminum hydroxide is mixed with 19.6 g of boric acid and 0.3 DM3nitric acid. Get the catalyst. The composition and properties of the obtained catalyst are shown in table.

P R I m e R 12. The catalyst prepared according to example 1, with the difference that for the preparation of media 271,9 g of aluminum hydroxide is mixed with 11 g of boric acid and 0.30 DM3nitric acid. The composition and properties of the obtained catalyst are shown in table.

P R I m e p 13. The catalyst prepared according to example 1, with the difference that for the preparation of media 321,1 g of aluminum hydroxide is mixed with 11 g of boric acid and 0.42 DM3nitric acid. The composition and properties of the obtained catalyst are shown in table.

P R I m e R 14 (prototype). 100 g of preformed aluminum oxide impregnated with a solution of palladium chloride 0.25% hydrochloric acid containing 0.8 g of palladium chloride, dried at 120aboutWith 6 h and calcined in the presence of air at 500aboutWith 4 hours Composition and properties of the catalyst are shown in table.

The mechanical strength of the catalysts prepared according to examples 1-10, determine on a standard install of PPK-1.

3at a temperature of 50aboutWith the entrance into the reactor. Loaded in the reactor, the catalyst is activated with hydrogen at 100aboutC and a pressure of 5.0 MPa for 2 hours Then cooled reactor 50aboutWith and begin testing.

Test conditions: a pressure of 5 MPa, a space velocity of 3 h-1N2/sire nm3/m3temperature at the inlet of the reactor 50aboutC.

Analysis of the obtained hydrogenated feed is separated carried out on the chromatograph with a flame ionization detector, the results are given in the table.

Data analysis shows that the proposed catalyst is superior to the prototype by hydrogenating activity and mechanical strength even at a lower palladium content. While the importance of the ratio of the components. Thus, the catalyst on alumalite with molar amount of IN2ABOUT2< 0,07 and a molar ratio of Al2O3< 0.83 (example 10,12), characterized by a low mechanical strength and hydrogenating activity. The increase in alumalite of boron oxide above 0.22 mol2ABOUT3(example 11) was not feasible due to deterioration of formemost mass media and the fall of the strength factor of the catalyst. The increase of PR. When the content of palladium in the catalyst is less than 0.2 wt. (example 8) a catalyst lowers the hydrogenating activity. The increase in the number of palladium over 0.5. (example 9) leads to the appreciation of the catalyst without substantial increase in activity.

1. CATALYST FOR hydrogenation of UNSATURATED HYDROCARBONS containing palladium on a carrier, characterized in that as the media it contains alumbra composition x B2O3y Al2O3when the value of molar ratios: x 0,07 0,22, y 0,83 0,93, and the following ratio, wt.

Pd 0,2 0,5

Media 100

2. The catalyst p. 1, characterized in that the catalyst contains palladium in the oxide or sulfide form.

 

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