The method of preparation of the platinum source of catalyst for reforming of gasoline fractions

 

(57) Abstract:

Usage: oil refining, in particular the production of catalysts for reforming of gasoline fractions. The inventive catalyst is obtained by mixing the modified aluminum hydroxide, hot and cold deposition when the mass ratio (1.5 to 4):1. The mixture is washed, plastificator nitric acid. The resulting mass ekstragiruyut. The extrudates are dried. Raise the temperature to 550oWith and calcined. The resulting carrier is impregnated with a solution of active ingredients, including the platinum compound. The impregnated granules are dried, calcined in a stream of dry air and water vapor content of not more than 60 minutes at a temperature of 110 - 500oC. 1 table.

The invention relates to the refining, more particularly to a method of production of platinum-containing catalysts for refining gasoline fractions by reformirovania.

As a carrier of catalysts for reforming is widely used gamma-alumina, which is often produced by the method of precipitation of hydroxide from aqueous solutions of sodium aluminate and mineral acids, mainly nitric acid, with subsequent forming operations and heat treatment [1]-[8] However the/SUP>C and the pH of the suspension is close to neutral [1] [3] a slightly alkaline [4][6] or weakly acidic [7][8] and get pseudonymity (Amity) hydroxide.

Made from the latest media in the form of gamma alumina has acceptable mechanical and physico-chemical properties, however, the platinum reforming catalysts based on it not to be stable. Their selectivity, particularly in relation to flavoring (dehydrocyclization) paraffin hydrocarbons, also needs to increase.

A known method of producing pseudoboehmite method two-stream deposition [9] the method comprises the separate deposition of the so-called "cold" (X) and "hot" (G) modifications hydroxide obtained at a temperature of about 20aboutC and the pH of the pulp from 9.0 to 9.5 and at a temperature of 100-102aboutC and the pH of the pulp 8,5-8,9 respectively. The mixture of these two modifications in the ratio X:Y=1:1 gives ultimately granules gamma oxide suitable as a carrier of catalysts for reforming (carrier A-64).

However, the resulting media crack at drawing him active components and catalysts of rehoming on the basis of the media have low selectivity and stability catalyst for reforming of gasoline fractions, whereby conduct the separate precipitation of aluminum hydroxide from solutions of sodium aluminate and nitric acid in two stages: at room temperature and boiling; mix modification of aluminum hydroxide, hot and cold deposition at a mass ratio of 1:(1,5-4,0); washed aluminum hydroxide from impurities; conduct plasticization, molded; expose the media to heat treatment at 110-550aboutWith the current of air; impregnate the alumina with an aqueous solution of active ingredients; dried and calcined the catalyst when 110-500about[10]

The increase in the share of modifications of aluminum hydroxide hot deposition (boehmite) when mixed with a modification of aluminum hydroxide cold deposition (pseudoboehmite) leads to the development of large pores and the disappearance of cracking granules media impregnation. The stability of the catalysts prepared in this way exceeds the stability of the catalysts on the media And-64. However, the catalysts obtained as described, have a low selectivity.

The purpose of the invention to provide a method for preparing platinum source of catalyst for reforming of gasoline fractions, which would increase selectives is hydroxide aluminum, hot and cold deposition in a certain ratio.

We propose a method of preparing platinum source of catalyst for reforming of gasoline fractions by mixing the modified aluminum hydroxide, hot and cold deposition when the mass ratio (1.5 to 4):1, washing, plasticizing, forming, drying, calcination, impregnation of alumina with an aqueous solution of active components, including a platinum compound, drying and calcination of the obtained catalyst when 110-500aboutC.

A distinctive feature of the proposed method is a mixture of modified aluminum hydroxide, hot and cold deposition when the mass ratio (1.5 to 4):1.

Analysis of the known technical solutions in the field of production of platinum source of catalyst for reforming of gasoline fractions allows to make a conclusion about the absence of the characteristic, similar to the essential distinguishing feature of the proposed technical solution to the requirement of inventive step.

The effect of increasing the selectivity, discovered by chance, can be explained by the change of the porous structure and surface chemistry of media that should change the distribution of platinum on various pores and its status (electrondeficient leads to the increase of the values of bulk density, specific surface area, mechanical strength and lower values of pore volume as compared with catalysts based media A-64 and catalysts prepared according to the method, taken as a prototype. The increase in bulk density of the carrier reduces the content of platinum in catalysts without sacrificing performance. The transition from the catalyst with a bulk density of 0.65 g/cm3(a-64) to 0,77 g/cm3by reducing the concentration of platinum in the catalyst of 0.36 to 0.30 wt. because in both cases one and the same reactor will be loaded equal amounts of platinum. While catalysts with a lower content of platinum have a higher potential stability.

The proposed method can be used for the preparation of monometallic platinum, latinoreview and polymetallic catalysts reforming.

Testing of the catalysts is carried out in the reforming of gasoline fractions in the pilot unit. After loading the catalyst restore it in the following conditions; a step increase within 8 hours the temperature to 400aboutWith exposure at 400about2 h; pressure of 2.0 MPa, the ratio of the hydrogen circulation 1000 ml is a new faction with their boiling temperature 70-170aboutWith a sulfur content of 0.0001% and octane 45 research method (IOC).

Testing is carried out in soft mode at a temperature of 475aboutC, pressure of 2.0 MPa, speed feed 2,0 h-1and the frequency of circulation of the hydrogen-containing gas to 1500 nl/l of raw materials. The catalyst is characterized octane reforming, selectivity yield stable catalyzate. In severe conditions the test is carried out at a temperature of 515aboutC, a pressure of 1.0 MPa, the rate of feed of 1.8 h-1and circulation of hydrogen gas of 1000 nl/l of raw materials. The results of the experiment in hard mode are used to determine stability or, equivalently, the index of activity decline difference in the content of aromatic hydrocarbons in catalyzate between 20 and 100 hours of testing.

The industrial applicability of the proposed method and its advantages are confirmed by the following examples. The results of the tests of the catalysts shown in the table.

P R I m e R 1. Cold precipitation.

In a reactor with a stirrer and a coil pour 300 ml of distilled water, and then with continuous vigorous stirring for about 2 hours and drained at the same time, a solution of aluminate hydroxide is the support in the range of 15-25aboutC. the pH Value of the suspension in the reactor can withstand approximately constant (9,2-9,5), regulating the rate of discharge of nitric acid. The number of merged nitric acid 340 ml. After discharge solutions are stabilized hydroxide by boiling the suspension for 1 h at a constant pH value of 9.1 and 9.3.

The result is a suspension of aluminum hydroxide containing 125 g of pseudoboehmite that in terms of Al2O3is 100,0,

Hot deposition.

In the reactor pour 200 ml of distilled water, which is heated to boiling, with stirring, at the same time merge the solutions of sodium aluminate and nitric acid for 2 hours, the solution Flow rate of aluminate 138,9 ml, concentration of 180 g of Al2O3/l During deposition to produce boiling of the suspension, i.e. the temperature of the support in the range of 100-102aboutC. the Rate of discharge of nitric acid is adjusted to a pH of suspension shall not exceed the limits of 8.5-8.9 in. Acid consumption was 85 ml.

Receive a suspension of aluminum hydroxide containing of 31.6 g of boehmite, which is responsible 25,0 Al2O3.

Suspension of cold and hot mixed sediment, filtered water, and then sieges kneading machine, in which it is evaporated to a residual water content of 55% To one stripped off mass add 1.0 ml of nitric acid solution for plasticization.

Then, the resulting plastic mass ekstragiruyut on the screw-press. The extrudates are dried for 3 hours at a temperature of 110aboutWith, and then increase the temperature to 550aboutWith and produce calcination for 4 hours

The result is a media extruded gamma-alumina ratio of hot and cold modification 4:1 in the amount of 125 g

The media in the amount of 50.0 g load in a rotary evaporator, include a vacuum pump and produce evacuated to a residual pressure of 50 mm RT.article then the evaporator Inuktitut 35 ml of distilled water. Hydrated extrudates impregnated with 35 ml of an aqueous solution containing 0.27 g of hexachloroplatinic acid, 0.18 g of rhenium acid, 0,30 g Hcl, 0.12 g of sulfuric acid and 0.5 g of glacial acetic acid. Instead of acetic acid can be entered 0.27 g of formic acid and 7.2 g of N2ABOUT2.

The impregnation is carried out at a temperature below 20aboutC for 1 h, and then at a temperature of 75-105aboutTo completely remove excess water.

The impregnated granules are dried and procalim 500aboutC for 3 h

The composition of the obtained catalyst, wt. platinum 0,26, rhenium 0,26, chlorine 1,2, sulfur 0,1, alumina rest.

The catalyst restore and experience in the above conditions.

Test results: the activity of 93.3 IOC, selectivity 86,0 wt. stability 10 units.

P R I m m e R 2. 100 g of aluminum oxide, prepared according to example 1, impregnated with 150 ml of an aqueous solution containing 0,946 g of hexachloroplatinic acid, 0.7 g of hydrogen chloride and 0.11 g of sulfuric acid.

Conditions of impregnation, drying and calcination similar to example 1. The composition of the obtained catalyst, wt. platinum 0,45, chlorine 1,1, sulfur 0,1, alumina rest.

The catalyst restore and experience in these conditions.

Test results: activity 93,4 IOC, selectivity 84,9 wt. stability unit 19

P R I m e R 3. Get 100 g of aluminum oxide analogously to example 1, but modified aluminum hydroxide, hot and cold deposition mixed at a mass ratio of 3:1 (Al2O3). Prepare the catalyst, impregnating aluminum oxide 150 ml of an aqueous solution containing from 0.76 g of hexachloroplatinic acid, 0,49 g] is nelogichny example 1.

The composition of the obtained catalyst, wt. platinum 0,36, rhenium 0,36, chlorine 1,25, sulfur 0,1, alumina rest.

The catalyst restore and experience in the above conditions. Test results: the activity of the catalyst is 94,1 IOC, the selectivity of 84.8 wt. stability 10%

P R I m e R 4. Get 125 g of aluminum oxide analogously to example 1, for modification of aluminum hydroxide, hot and cold deposition mixed at a mass ratio of 2:1 (Al2O3). Prepare the catalyst, hydrates 50 g of the carrier 35 ml of distilled water, and then impregnating the alumina 35 ml of an aqueous solution containing 0.27 g of platinum-hydrochloric acid, 0.28 g of rhenium acid, 0.36 g Hcl, 0.12 g of sulfuric acid.

Conditions of impregnation, drying and calcination similar to example 1.

The composition of the obtained catalyst, wt. platinum 0,26, rhenium 0,40, chlorine 1,35, sulfur 0,1, alumina rest.

The catalyst restore and experience in the given conditions.

The test results of catalyst activity 94 IOC, selectivity 86,0 wt. stability 9 units

P R I m e R 5. Get 100 g of aluminum oxide analogously to example 1, by modifying gidrofilizatory prepared analogously to example 3.

The composition of the obtained catalyst, wt. platinum 0,36, rhenium 0,36, chlorine 1,25, sulfur 0,1, alumina rest. The catalyst restore and experience in the above conditions. Test results: activity 92,4 IOC, selectivity and 84.6 wt. the stability of the 11 units.

P R I m e R 6. On the media, prepared as in example 4, to prepare two samples of the catalyst containing 0.36 wt. platinum and rhenium and additional metals promoters.

In the first sample (A) enter 0.2 wt. zinc, which in the impregnating solution of the same composition as example 3 add to 0.29 g of zinc nitrate (50 g of alumina). To another portion of the carrier, taken in an amount of 50 g is applied impregnating solution composition similar to example 3, but with the addition of 0.06 g of zinc nitrate and 0,034 g of tungstic acid. The resulting catalyst is dried, calcined in accordance with the procedure described in example 1. Get the catalyst composition, wt.

Sample: platinum 0,36, rhenium 0,36, zinc 0,2, chlorine 1,25, sulfur 0,1, alumina rest.

Sample B: platinum 0,36, rhenium 0,36, zinc 0.05, the tungsten 0,05, chlorine 1,25, sulfur 0,1, alumina rest.

Catalysts restore and experience in the given conditions.

P R I m e R 7. Two portions of 50 g of the carrier prepared as in example 4, impregnated with solutions of active ingredients, but in a single impregnating solution further added 0.31 g of magnesium nitrate and 0.08 g of cobalt nitrate and receive the catalyst sample A. To obtain a catalyst (sample B) in the impregnation solution was added 0.20 g of magnesium chloride and 0.05 g of Nickel carbonate.

The resulting catalyst is dried, calcined in accordance with the procedure described in example 1. They have the following composition, wt.

Sample A: platinum 0,26, rhenium 0,40, magnesium 0,1, cobalt 0,05, chlorine 1,25, sulfur 0,1, alumina rest.

Sample B: platinum 0,26, rhenium 0,40, magnesium 0.05, the Nickel 0,05, chlorine 1,25, sulfur 0,1, alumina rest.

Catalysts restore and experience in the above conditions.

When testing both catalysts show the same results: activity 94,0 IOC, the selectivity of 85.7% stability 10%

P R I m e R 8. Two portions of 50 g of the carrier prepared as in example 4, impregnated with solutions of the active components. In General, the conditions of impregnation are the same as those in example 1, however, the amount of rhenium acid increase the catalyst sample A: 0,038 g of barium chloride and 0,034 g tungstic acid, and in the case of catalyst sample B 0,038 g of barium chloride and 0.11 g of tin tetrachloride.

The resulting catalyst is dried, calcined in accordance with the procedure described in example 1. They have the following composition, wt.

Sample: platinum 0,26, rhenium 0,60, barium 0.05, the tungsten 0,05, chlorine 1,25, sulfur 0,1, alumina rest.

Sample B: platinum 0,26, rhenium 0,60,barium 0.05, the tin 0,1, chlorine 1,25, sulfur 0,1, alumina rest.

Catalysts restore and experience in the above conditions.

When tested catalysts obtained the following results:

Sample A: activity 94,3 IOC, selectivity 96,0 wt. stability 10%

Sample B: activity 94,1 IOC, the selectivity of 85.7 wt. stability 11%

P R I m e R 9 (known way). Get 300 g of aluminum oxide analogously to example 1, for modification of aluminum hydroxide, hot and cold deposition mixed at a mass ratio of 1:1 (Al2O3).

100 g of the carrier used for the preparation of monometallic platinum catalyst. For this purpose, the aluminum oxide is impregnated with an aqueous solution of active ingredients as in example 2.

Other 100 g of the carrier is of Italia put impregnating solution analogously to example 3 composition, but with the addition of zinc and tungsten, as in example 6.

The resulting catalyst is dried, calcined in accordance with the procedure described in example 1.

The composition of the obtained catalyst, wt.

monometallic: platinum 0,45, chlorine 1,2, sulfur 0,1, alumina rest;

latinoreview: platinum 0,36, rhenium 0,36, chlorine 1,25, sulfur 0,1, alumina rest;

polymetallic: platinum 0,36, rhenium 0,36, zinc 0.05, the tungsten 0,05, chlorine 1,25, sulfur 0,1, alumina rest.

Catalysts restore and experience in the above conditions.

When tested catalysts obtained the following results: monometallic platinum: activity 89,9 IOC, the selectivity of 80.6 wt. the stability of the 22 units; latinoreview: activity 91,0 IOC, selectivity 81,0 wt. stability 16 unit complex: activity 91,8 IOC, selectivity to 83.2 wt. stability 13%

P R I m e R 10 (the prototype). Get 300 g of aluminum oxide analogously to example 1, for modification of aluminum hydroxide, hot and cold deposition mixed at a mass ratio of 1:2 (Al2O3).

100 g of the carrier charge for the preparation of monometallic platinum catalyst.e 100 g of aluminum oxide impregnated with a solution of the active components as in example 3.

The remaining portion of the carrier is applied impregnating solution similar to example 3, but with the addition of zinc and tungsten, as in example 6. The resulting catalyst is dried, calcined in accordance with the procedure described in example 1.

The composition of the catalyst, wt.

monometallic platinum 0,45, chlorine 1,0, sulfur 0,1, alumina rest:

latinoreview platinum 0,36, rhenium 0,36, chlorine 1,2, sulfur 0,1, alumina rest;

polymetallic platinum 0,36, rhenium 0,36, zinc 0.05, the tungsten 0.05, the alumina rest.

Catalysts restore and experience in the above conditions.

When tested catalysts obtained the following results:

monometallic platinum: activity 93,3 IOC, the selectivity of 80.9 wt. stability 19 ed;

latinoreview: activity 92,4 IOC, selectivity 82,7 wt. stability 13 ed;

polymetallic activity 92,0 IOC, the selectivity of 82.9 wt. stability 12 units

As follows from the data presented in the table, the catalysts prepared by the proposed method have the highest selectivity while maintaining high activity and stability.

The WAY Prepared aluminum hot and cold deposition, washing, plasticizing, forming, drying, calcination, impregnation of alumina with an aqueous solution of active components, including a platinum compound, drying and calcination of the obtained catalyst at 110 - 500o, Characterized in that the mixture of modified aluminum hydroxide, hot and cold deposition is carried out in a mass ratio (1.5 to 4) 1.

 

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