The method of preparation of the zeolite catalyst for reforming of gasoline fractions

 

(57) Abstract:

Usage: in the catalytic petrochemical industries, in particular in the production method of reforming catalysts. The inventive method provides for the impregnation of the support with a solution containing complex compounds chloride first base of the Raise with the sodium salt of the promoter group: [Pt(NH3]4Cl2] (0,2 - 1,35) Na2EA4where e is tungsten or molybdenum. The impregnated carrier is dried and calcined. The specified connection is prepared by mixing hexachloroplatinic acid or hexachloroplatinate ammonium, sodium salt promoter and 25% ammonia solution with constant stirring for 20 to 30 h, 40 ° - 55oC and a pressure of 0.05 to 0.2 MPa, and the ratio of ammonia solution to platinum is 30 - 70 DM3solution to 1 g of platinum, and as a carrier, a mixture of 65% zeolite ZSM-5, ZSM-8, ZSM-11 in the sodium form and aluminum oxide. 1 C.p. f-crystals, 1 table.

The invention relates to the preparation of reforming catalysts and can be used over the oil refining and petrochemical industries.

There is a method of preparation of the catalyst renovatory ammonium, either chloride tetraamine platinum II, and are impregnated with a pH of 3.1 to 6.7 for 2 hours, the Excess solution is drained and the catalyst is dried (Kozlov N. C. Pavement L. J. Yanchuk, A. F. and other Vesti Academy of Sciences of the Byelorussian SSR N 1, 1984 ) the Disadvantage of this method is the high coking ability of the catalyst. So, when reforming a gasoline fraction 85 - 180oC at a pressure of 1 MPa, a temperature of 500oC, space velocity of the raw material 3h-1, a molar ratio of hydrogen feedstock 5:1, the content of the coke on the catalyst is increased from 1.5% wt. after 24 h up to 16% wt. after 240 hours

A known method for preparation of the reforming catalyst by double impregnation, in which the glued carrier (aluminum oxide) impregnated with aqueous solution of tin tetrachloride and hydrochloric acid at pH 1 to 3, the excess solution is drained, the catalyst is dried and calcined in air flow (patent USSR N 470972, MKI C 10 g 35/08, 1972). The disadvantage of this method is the high coking ability of the catalyst. So, when reforming a gasoline fraction 85 180oC at a pressure of 1 MPa, a temperature of 500oC, space velocity of the raw material 3h-1, a molar ratio of hydrogen feedstock 5:1, the content of the coke on the catalyst was increased from 0.5% wt. after 24 h to 8.2 wt.%. h the teachings of the reforming catalyst, which comprises calcining the zeolite ZSM-5, ZSM-8 or ZSM-11 at a temperature of 200 600oC for 1 to 48 hours, the impregnated zeolite carrier with an aqueous solution of chloride tetraammineplatinum (II) within 4 h, washing with water, the impregnation compound promoter, drying, impregnation, and the primary exchange with the cation of an alkali metal (U.S. patent N 46523690, C 10 G 35/06, 1986). The disadvantage of the catalyst, obtained in a known manner, is its high coking ability. So, when reforming a gasoline fraction 85 180oC at a pressure of 1 MPa, a temperature of 500oC, the speed of feeding raw 3h-1, the molar ratio of hydrogen - raw 5:1 the content of the coke on the catalyst is increased from 0.2 wt.%. after 24 h of work to 3.4 wt.%. after 240 hours of work.

The aim of the invention is to reduce maksuameti catalyst.

This objective is achieved in that the carrier is impregnated with an impregnating solution containing separately synthesized complex compounds of platinum and sodium salt promoter (tungsten or molybdenum) and a salt of an alkali metal. Moreover, the complex compound of platinum and a promoter having the composition [Pt(NH3)4]Cl2(0,2 1,35)Na2EA4where e tungsten or molybdenum is prepared by mixing platinite 25% ammonia solution (30 70 DM3/g Pt) at a temperature of 40 - 55oC for 20 to 30 h and a pressure of 0.05 to 0.2 MPa.

This goal is achieved by the fact that the media contains 65 wt.%. zeolite ZSM-5, ZS M-8 or ZS M-11 in the sodium form and the aluminum oxide, and a salt of an alkali metal (sodium, potassium or lithium) in the impregnating solution corresponds to an atomic ratio of alkali metal to PT (1 - 50) 1.

The hallmark of the invention is the composition and conditions of formation of complex compounds of platinum and a promoter and simultaneous impregnation and treatment of the zeolite is the alkali metal.

The method is as follows.

For the synthesis of complex compounds of platinum and a promoter in a solvent is poured 25% aqueous ammonia solution, heated to a temperature of 40oC, include the stirrer and add hexachloroplatinic acid or hexachloroplatinate ammonium. The dissolution is carried out for 10 hours at a temperature of 40 - 55oC, then download wolframates or sodium molybdate and a fresh portion of 25% aqueous ammonia. Mixing continued for another 10 to 20 h with periodic introduction of ammonia solution. The total number of 25% aqueous ammonia required for dissolution, is in mesilat with the solution of complex compounds of platinum and a promoter. The atomic ratio of platinum and of an alkali metal 1 (1 50).

Zeolite ZS M-5 or ZSM-8 or ZSM-11 in the sodium form is made from 35% wt. aluminium oxide is dried at 110oC 6 h and calcined in air flow at a temperature of 450oC for two hours and immersed in the impregnating solution. Impregnation are 2 hours at a temperature of 80oC, pH 10.

After impregnation, the excess solution is drained, the catalyst is dried at a temperature of 110oC for 6 h and calcined at a temperature of 450oC for 2 h in a current of air.

Below are examples of the preparation of the catalyst is known and the proposed method.

Example 1. In laboratory solvent was placed 5 ml of 25% aqueous ammonia solution, is heated to a temperature of 40oC, include a mixer and load 0,7457 g of crystalline platinochloride acid (37,25% wt. Pt), the temperature of the solvent to the 50oC and hold dissolving 10 h with constant stirring. Then the solvent load 0,0472 g wolframalpha sodium and add another 5 ml of 25% aqueous ammonia. Dissolution continue for another 8 h, after which the solvent contribute an additional 2.5 ml of NH4OH and continue dissolving 6 o'clock the Process of dissolution is carried out at amerivault with a solution 2,4993 g of sodium chloride in 200 ml of distilled water and heated obtained impregnating solution to a temperature of 80 90oC.

an 81.25 g of Zeolite ZSM-5 in an alkaline form is mixed with 175 g of paste of aluminum hydroxide and 2.8 ml of 57% nitric acid peptization, formed into extrudates, dried at a temperature of 110oC 6 h and calcined at a temperature of 450oC 2 h

100 g of the carrier Extrudates are immersed in the impregnating solution and carry out the impregnation of 2 hours at a temperature of 80 90oC pH 10. Then the excess solution is drained, the catalyst is dried at 110oC 6 h and calcined at 450oC for 2 hours the Finished catalyst has a composition, by weight. platinum 0,25; tungsten 0,03; media up to 100.

Example 2. The catalyst prepared according to example 1, with the difference that in the preparation of complex compounds of platinum and a promoter take 0,3196 g Na2WO42H2O, and the impregnating solution contains 2,87 g KCl. Get the catalyst composition, wt. platinum 0,25; tungsten 0,2; media up to 100.

Example 3. The catalyst prepared according to example 1, with the difference that in the preparation of complex compounds of platinum and a promoter take 0,6943 g hexachloroplatinate ammonium (content of platinum 40% wt.) and 0,3196 g Na2WO42H2O, and the dissolution of lead 20 hours Receive the catalyst composition, wt. platinum 0,25; tungsten 0,12; media up to 100.

Primerahora take 0,2113 g Na2MoO42H2O and the dissolution is carried out for 30 h, and the impregnating solution contains 6,79 g of sodium carbonate. Get the catalyst composition, wt. platinum 0,25; molybdenum 0.1; media up to 100.

Example 5. The catalyst prepared according to example 1, with the difference that for the production of complex compounds of platinum and a promoter take 0,1651 g Na2WO42H2O and 7.5 ml of 25% ammonia solution (portions of 2.5 ml 3 times), and the impregnating solution contains 5.34 g of lithium chloride. The finished catalyst has a composition, by weight. platinum 0,25; tungsten 0.1; media up to 100.

Example 6. The catalyst prepared according to example 5, with the difference that for the production of complex compounds of platinum and a promoter take 17,5 ml of 25% ammonia solution (6 ml + 6 ml + 4.5 ml), and the medium contains 65% ZSM-8 in the sodium form.

Get the catalyst composition, wt. platinum 0,25; tungsten 0.1; media up to 100.

Example 7. The catalyst prepared according to example 4, with the difference that the process of dissolution is carried out at a pressure of 0.05 MPa for 24 h, the medium contains 65% ZSM-11 in Na form. Get the catalyst composition, wt. platinum 0,25; molybdenum 0.1; media up to 100.

Example 8. The catalyst prepared according to example 4, with the difference that the process of dissolution Provo ሺ/P> Example 9. The catalyst prepared according to example 5, with the difference that the amount of 25% ammonia solution take 12.5 ml (as in example 1), and the dissolution is conducted at a temperature of 40oC. Get the catalyst composition, wt. platinum 0,25; tungsten 0.1; media up to 100.

Example 10. The catalyst prepared according to example 9, with the difference that the dissolution is conducted at a temperature of 55oC, and the impregnating solution contains 1.63 g of lithium chloride. The finished catalyst has a composition, by weight. platinum 0,25; tungsten 0.1; media up to 100.

Example 11(comparative). The catalyst prepared according to example 1, with the difference that for the preparation of complex compounds of platinum and a promoter take 0,0236 g Na2WO42 H2. Get a catalyst of the following composition, wt. platinum 0,25; tungsten 0,015; media up to 100.

Example 12 (comparative). The catalyst prepared according to example 1, with the difference that for the preparation of complex compounds of platinum and a promoter take 0,3538 g Na2WO42H2O and obtain a catalyst of the following composition, wt. platinum 0,25; tungsten 0,22; media up to 100.

Example 13 (comparative). The catalyst prepared according to example 5, with the difference that for the preparation of complex compounds of platinum and a promoter be the tel to 100.

Example 14 (comparative). The catalyst prepared according to example 6, with the difference that for the preparation of complex compounds of platinum and a promoter take 20 ml (10 ml + 6 ml + 4 ml) 25-ammonia solution. Get the catalyst composition, wt. platinum 0,25; tungsten 0.1; media up to 100.

Example 15(comparative). The catalyst prepared according to example 4, with the difference that the duration of the dissolution 16 hours Receive a catalyst of the following composition, wt. platinum 0,25; molybdenum 0.1; media up to 100.

Example 16 (comparative). The catalyst prepared according to example 4, with the difference that the duration of the dissolution 35 am Finished catalyst has a composition, by weight. platinum 0,25; molybdenum 0.1; media up to 100.

Example 17 (comparative). The catalyst prepared according to example 7, with the difference that the dissolution of lead under pressure of 0.02 MPa. The finished catalyst has a composition, by weight. platinum 0,25; molybdenum 0.1; media up to 100.

Example 18(comparative). The catalyst prepared according to example 7, with the difference that the dissolution of lead under pressure of 0.3 MPa. The finished catalyst has a composition, by weight. platinum 0,25; molybdenum 0.1; media up to 100.

Example 19 (comparative). The catalyst prepared according to example 10, with the difference, is 1; media 100.

Example 20 (comparative). The catalyst prepared according to example 10, with the difference that the dissolution is conducted at a temperature of 60oC. the Finished catalyst has a composition, by weight. platinum 0,25; tungsten 0.1; media up to 100.

Example 21(prototype). 100 g of Zeolite ZSM-5 in an alkaline form calcined at a temperature of 538oC 10 h, impregnated with a solution of 0.5 g of Pt(NH3)4Cl2H2O 482 ml of distilled water for 4 h at room temperature, washed with 200 ml of distilled water and filtered. Then the zeolite is impregnated with a solution containing 0,61 g H2/rCl4in 482 ml of distilled water for 4 h at room temperature. The excess solution is drained, the catalyst was calcined in air at 500oC and treated with 160 ml of 3% sodium carbonate solution, filtered and dried at 110oC 2 h

Get the catalyst composition, wt. platinum 0,25; iridium 0,35; zeolite ZSM-5 in an alkaline form to 100.

The catalysts prepared according to examples 1 to 21 were tested at pilot plant in the process of reforming a gasoline fraction 85 180oC under the following conditions: a pressure of 1 MPa, a temperature of 500oC, the feed rate 3h-1, the molar ratio of hydrogen raw material 5 1. who. After stopping delivery of raw materials / 24 and 240 h/ catalysts was otdovali hydrogen for 10 h, cooled in a circulating stream of hydrogen and analyzed for the content of coke (chromatographic method). The resulting produce was debutanizer and determined its octane number by the research method.

The test results presented in the table.

Analysis of the data presented in the table shows that the preliminary synthesis of complex compounds of platinum and a promoter and carrying out impregnation from a solution containing both this compound and a salt of an alkali metal in an amount to provide a reduction in the acidity of the zeolite plays an important role in reducing maksuameti catalyst. So in the catalysts prepared by the proposed method (examples 1 to 10) the content of the coke on the catalyst is 1.4 to 1.8 wt. 3,4% wt. coke on the catalyst, prepared in a known manner.

While the importance of the conditions of preparation and composition of complex compounds. So, by reducing the molar content of the sodium salt of the promoter (example 11) below 0.2 coking ability of the catalyst is increased, increasing the molar content of sodium salt of p is alistor.

In the synthesis of complex compounds of platinum and a promoter consumption reduction of 25% ammonia solution below 30 DM31 g of platinum (example 13), reducing the duration of dissolution below 20 h (example 15), the reduction of pressure below 0.05 MPa (example 17), the process temperature is below 40oC (example 19) or rise above 55oC leads to the formation of the unstable solution of complex compounds and, consequently, increasing maksuameti catalyst.

Increased consumption of ammonia over 70 DM31 g of platinum (example 14), the duration of the dissolution of more than 30 hours (example 16), pressures in excess of 0.02 MPa (example 18) does not entail changes in the quality of the catalyst and its maksuameti and is uneconomical.

1. The method of preparation of the zeolite catalyst for reforming of gasoline fractions by impregnation of the carrier with a solution containing platinum, the promoter and alkaline metal, drying and calcining the obtained catalyst, characterized in that the impregnation are the solution containing the complex compound of chloride of 1st Foundation Raise with the sodium salt promoter composition

[PT(NH3)4]CL2(0,2 1,35)NA2EA4,

where e tungsten or molybdenum,

obtained by smeester ammonia under stirring for 20 to 30 h, the temperature of 40 - 55oC and a pressure of 0.05 to 0.2 MPa, and the ratio of ammonia solution to platinum is 30 to 70 DM3solution to 1 g Pt.

2. The method according to p. 1, characterized in that the use of media containing, by weight.

The zeolite ZSM-5, ZSM-8, ZSM-11 in the sodium form 65

The aluminum oxide To 100

and impregnating solution contains a salt of alkaline metal is sodium, potassium or lithium with atomic ratio of alkali metal to platinum 1 50 1.

 

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