The preparation method of catalyst for the conversion of gasoline fractions

 

(57) Abstract:

Use: in the manufacture of catalysts, in particular catalysts for the conversion of gasoline fractions. The inventive aluminum hydroxide is prepared by mixing solutions of sodium silicate and aluminum sulfate followed by washing the precipitated aluminum hydroxide water, patsatsia hydrochloric acid to pH 3 to 4 with 85 150°C for 0.5 to 5 hours In the resulting paste is added ammonium molybdate, zeolite NH4Y silicate module 4.5 in the amount of 2 wt. Then add high-silica zeolite with structure pentasil with silicate module 32 70 in palladium shape with a palladium content of 0.6 to 2 wt. in the amount of 20 to 70% of the mixture is homogenized, evaporated to a moisture content of 42 to 47% formed into extrudates, which are dried and calcined at 500 520°C for 3 to 4 h 1 table.

The invention relates to methods for preparing catalysts for the petroleum industry, in particular catalysts for the conversion of light gasoline fractions, and can be used in the refining and petrochemical industry for producing high-octane gasoline.

A known catalyst for aromatization of gasoline palomine; possible deposition of platinum with the addition of rhenium [1] by the processing Conditions are: temperature 455-510aboutWith the pressure of 0.65-5 MPa, the volumetric rate of 1-3 h-1. The catalyst has a mechanical strength estimated by an index of the strength crush strength of 0.8 to 1.1 kgf/mm

The catalyst does not provide a high octane number gasoline, and its mechanical strength is insufficient for use in high-performance installations in reactors a considerable amount.

Known method of preparing zeolite-containing catalyst (CSK) in the form of spherical granules, in which the dispersed zeolite (type pajazit or pentasil) administered by mixing the aluminum hydroxide in an amount of 5-70% peptizer acetic acid and subsequent hydrocarbon-ammonia forming. After forming the balls of aluminum hydroxide with the zeolite is dried at room temperature for 16-18 h, and then in a drying Cabinet at 60, 80 and 120aboutWith 2 tsp Dried balls CSK was progulivali in air flow at 550aboutC for 3 hours, the Catalyst has a strength of 3.8-14.5 kg/balloon [2,3] However, activity in the conversion of light gasoline fractions in terms of the proposed method is very low. So parasitaemias (FGC) cat">

There is also known a method of preparation of the catalyst [4] for the conversion of hydrocarbons, which is prepared as follows. Clean granular aluminum metal dissolves in hydrochloric acid, and then mixed with an aqueous solution of hexamethylenetetramine to obtain sustainable Zola Al2O3. In the resulting solution is injected small dry crystalline aluminosilicate (e.g., pajazit or mordenite), weight is dispersed and Kapitsa in the oil, which forms a hydrogel in the form of spherical granules, which are subjected to aging in a layer of the same oil, then in an aqueous solution of ammonia (hydrocarbon-ammonia forming).

The prepared product is washed with water, dried, and then calcined and receive media, which is in turn a catalyst for conversion of hydrocarbons by deposition of at least one active metal (chromium, molybdenum, tungsten, or a metal of the iron group (0.5 to 4.0 wt.) or a metal from the platinum group in the amount of 0.05-5% by weight of the finished catalyst.

The catalyst used in the conversion of hydrocarbons, including, in the reforming process. When the processing gas, selected from the Kuwaiti oil content (about. paraffin 73-74; naphthenes 16-17; ar is-1, the molar ratio hydrogen:feedstock 6-7,6, get deputysecretary product with an octane rating 95-100 p. the Output of high-octane gasoline is 59,7-to 66.5 wt.

The disadvantage is the low yield of the target product. In addition, the use of a Sol of aluminum oxide, obtained from a mixture of aluminum metal, hydrochloric acid and hexamethylenetetramine, results in the ball of the catalyst with reduced mechanical strength (3,2-4 kg/table. when the content of zeolite 5-10 wt.).

The purpose of the proposed invention is to provide such a method of preparation of the catalyst, which would increase its mechanical strength while maintaining high activity.

The objective is achieved by using as bundles of aluminum hydroxide obtained by precipitation from solutions of aluminum sulfate and sodium aluminate, followed by patsatsia hydrochloric acid at 85-150aboutC for 0.5 to 2 hours until pH 3.0-4.0, and as crystalline aluminosilicate use zeolite with structure Pancasila in palladium form in the amount of 20-70 wt. when the palladium content of 0.6-2.0 wt.

The essence of the method consists in the following. Prepare the aluminum hydroxide PIO residual Na2About on the level of 0.02 to 0.08 wt. and peptizing hydrochloric acid to a pH of 3.0 to 4.0 at 85-150aboutC for 0.5 to 2 hours In the resulting paste is added sequentially ammonium molybdate, zeolite type A, high-silica zeolite (SiO2Al2O332-70) palladium form (Pd 0.6 to 2.0 wt.), the mixture was thoroughly homogenized, evaporated to a moisture content of 42 to 47 wt. formed into extrudates. The extrudates are dried and calcined at a temperature of 500-520aboutC for 3-4 h

P R I m e R 1. Take 309,4 g of aluminum hydroxide obtained by precipitation from solutions of aluminum sulfate and sodium aluminate at a pH of 7.9 with subsequent washing, containing a 49.5 g of absolutely dry matter alumina content of 0.02 wt. sodium oxide. To the pellet of aluminum hydroxide added 3.3 ml of hydrochloric acid concentration of 35% to a pH of 3.5 mass is thoroughly mixed and incubated in a water bath at 85aboutC for 2 h, while continuing the stirring. After 2 h the mass transfer in a laboratory mixer, add sequentially 10.6 g of salt ammonium molybdate, 2 g of zeolite NH4Y (SiO2: Al2O34,5), and then 40 g of high zeolite type pentasil (VCC) with SiO2/Al2O3(the moth) 48 in palladium (Pd 1,0%), stariway to a moisture content of 52 wt. formed into extrudates with a diameter of 3 mm, dried at 120about2 h and calcined at 500aboutC for 4 h the resulting catalyst has the following composition, wt. the molybdenum trioxide 8,5 high-silica zeolite in palladium form 40 zeolite NH4Y 2 alumina 49,5

A portion of the catalyst volume 25 cm3load in the flow reactor and passed through it sequentially hydrogen at a temperature of 320aboutC for 3 h (stage activation), and then the temperature was raised to 350aboutWith and served raw material: hydrotreated gasoline fraction with an octane number (mm) 73,3 p with a bulk velocity 5 h-1, at a pressure of 3 MPa, the flow of hydrogen to 1200 nl/l of raw materials. The results of the experiment are shown in the table.

P R I m m e R 2. The catalyst prepare and test as in example 1, but after deposition and leaching the aluminum hydroxide diluted with 90 ml of condensate to obtain a suspension concentration of 202 g/l was added to 4.4 ml of hydrochloric acid concentration of 35% to a pH of 3.0.

The mixture is placed in a reactor with a stirrer, which was heated to a temperature of 110aboutC and maintained under continuous stirring for 1 h After peptization mixture upload and add components in sequence and in quantities and m e R 3. The catalyst was prepared and feel of example 1, but the pH of the aluminum hydroxide after the addition of 2.2 ml of HCl withstand 4.0, and the temperature in the autoclave (reactor with stirrer) was raised to 150aboutOn time 0.5 hours the Results are shown in the table.

P R I m e R 4. The catalyst was prepared and feel in example 3, but the number of downloadable high zeolite with SiO2/Al2O332 (moth) in palladium form (Pd 2.0 wt.) equal to 20 g, 20 wt. on the catalyst and the aluminum hydroxide charge in the amount of 434,4 g in terms of dry substance of aluminum oxide is, 69,5

The catalyst has the following composition, wt. the molybdenum trioxide 8,5 high-silica zeolite in palladium and form 20 zeolite NH4Y 2 alumina 69,5

The test results are shown in the table.

P R I m e R 5. The catalyst was prepared and feel in example 2, but the number of downloaded vysokokremnezemnstogo zeolite (SiO2/Al2O370 (moth) in palladium form (Pd 0.6 wt.) equal to 70 g, 70 wt. on the catalyst and the aluminum hydroxide charge in the amount of the level of 121.8 g in terms of dry substance of aluminum oxide is 19.5,

The catalyst is e 70 zeolite NH4Y 2 alumina 19,5

The test results presented in the table.

As can be seen from the table, the catalyst has a high mechanical strength. Thus, the crushing strength is 8.1-12.3 kg/table. (TU 38.401-64-211-91), which is expressed by the figure of 2.7-4.1 kg/mm (OST 38.01130-77) in terms of the strength factor versus 3.2-4 kg/table. or 2-2,5 kg/mm, respectively, for the catalyst of the prototype.

At the same time in the same test conditions, the catalyst has higher compared with the reference output of gasoline 92,8-94,0 wt. which leads to a high level of octane-tons from 8004 up 8201 against 6650 for the prototype.

The PREPARATION METHOD of CATALYST FOR the conversion of GASOLINE FRACTIONS, including the dispersion of aluminum compounds with a crystalline aluminosilicate, the introduction of a hydrogenating component molybdenum, molding, drying and calcination, wherein, to improve the mechanical strength while maintaining high catalyst activity, as the aluminum compounds used aluminum hydroxide obtained by precipitation from solutions of aluminum sulfate and sodium aluminate, followed by patsatsia hydrochloric acid at 85 150oC for 0.5 to 2 h to pH 3, the ve 2 wt. and zeolite with structure pentasil with silicate module 32-70 in palladium shape with a palladium content of 0.6 to 2.0 wt. in the amount of 20 to 70 wt.

 

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