Preparation method of high-medium oil selective hydrocracking catalyst

A technology of catalytic materials and composite catalytic materials, which is applied in the field of preparation of composite catalytic materials and selective hydrogenation catalysts, can solve the problems of poor balance between cracking activity and medium oil selectivity, unfavorable activity and stability of hydrocracking catalysts, Uniform distribution of acid centers and other adverse effects, to solve the problems of agglomeration and filtration, improve accessibility, and reduce the cost of preparation

Inactive Publication Date: 2010-09-29
BC P INC CHINA NAT PETROLEUM CORP +1
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  • Description
  • Claims
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Problems solved by technology

The characteristics of these methods are that the preparation process is complicated. Although the problem of agglomeration of small-particle molecular sieves has been solved, microwave or ultrasonic dispersion methods are used in the preparation process, and the industrial production cost is high, and it is difficult to realize. At the same time, the technical solutions disclosed in these two applications The removal of sodium ions is not raised either, and sodium residues have a very adverse effect on the activity and stability of hydrocracking catalysts
[0005] Chinese patent application 200710010390.0 describes a preparation method of a layered clay / molecular sieve composite material. The prepared composite material has both layered clay and molecular sieve channel structure, but the preparation method is time-consuming and the acidity of the carrier is not easy to control
[0006] US4738767 discloses a hydrocracking catalyst. Since the acidic silica-alumina cannot provide the pores required by the catalyst carrier at the same time, it needs to be dispersed on a macroporous alumina matrix, which limits the adjustment of the carrier formula and also affects the acidity. Uniform distribution of centers in the channels adversely affects catalyst performance
[0007] US5536687 discloses a catalyst, which specifically uses a composite carrier obtained by combining β molecular sieve and Y molecular sieve. This carrier is suitable for preparing light fraction hydrocracking catalyst, but it cannot balance cracking activity and medium oil selectivity paradox

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  • Preparation method of high-medium oil selective hydrocracking catalyst

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Embodiment 1

[0037] Example 1 Preparation of Small Particle Y Molecular Sieve

[0038] This embodiment provides a method for preparing a small particle Y molecular sieve, and the specific synthesis steps are as follows:

[0039] Mix sodium metaaluminate, silicate solution (water glass), sodium hydroxide and deionized water in a molar ratio of Na 2 O:Al 2 o 3 : SiO 2 :H 2 O=18:1:16:336 ratio mixing, stirring evenly, standing and aging for 20-50h to obtain the directing agent;

[0040] In an ice-water bath (0°C), mix a certain amount of sodium metaaluminate, sodium hydroxide and deionized water, stir evenly, then add a certain amount of silicate solution, so that the molar ratio of the system is Na 2 O:Al 2 o 3 : SiO 2 :H 2 O=8: 1: 3.2: 300, after high-speed stirring for 30min, the synthetic mother liquor was obtained;

[0041] Add the above-mentioned directing agent in the synthesis mother liquor, wherein the directing agent / (directing agent+mother liquor) is 5-20% by weight, so t...

Embodiment 2

[0046] This embodiment provides a method for preparing a Y molecular sieve / amorphous silicon aluminum oxide composite carrier, which uses the remaining crystallization liquid as the silicon source and aluminum nitrate as the aluminum source, and includes the following specific steps:

[0047] Get 40g of the small particle Y molecular sieve precipitate prepared by Example 1, place it in a constant temperature reactor at 90°C, add 50mL of deionized water and 33mL of ammonium nitrate solution (NH 4 + ion concentration is 6.0mol / L), after stirring for 3 hours, the temperature was lowered to 60°C, and at the same time, 21mL of aluminum nitrate solution (as Al 2 o 3 The concentration of the meter is 1.27mol / L) and dilute ammonia solution (the volume ratio of concentrated ammonia water to deionized water is 5:7), so that the pH value of the mixed solution is between 7-8, after stirring for 20min, add 164mL of Crystallization residual liquid (that is, all the crystallization residua...

Embodiment 3

[0051] This example provides a method for preparing a Y molecular sieve / amorphous silicon-aluminum oxide composite carrier, which is based on sodium silicate and crystallization residual liquid with SiO 2 A mass ratio of 0.5 is mixed as a silicon source, and aluminum nitrate is an aluminum source, including the following specific steps:

[0052] Take 50g of the precipitated small particle Y molecular sieve prepared in Example 1, place it in a constant temperature reactor at 90°C, add 50mL of deionized water, stir evenly, and then add 42.5mL of ammonium nitrate solution (NH 4 + ion concentration is 6.0mol / L), after stirring for 3 hours, the temperature of the reactor was lowered to 60°C, and at the same time, 43.5mL of aluminum nitrate solution was added dropwise (in the form of Al 2 o 3 The concentration of the meter is 1.27mol / L) and dilute ammonia solution (the volume ratio of concentrated ammonia water to deionized water is 5:7), so that the pH value of the mixed solution...

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Abstract

The invention relates to a preparation method of a high-medium oil selective hydrocracking catalyst. The invention firstly provides a preparation method of a Y-molecular sieve/ Si-Al oxide composite catalytic material, comprising the steps of: synthesizing a Y-molecular sieve by a guide agent method, controlling the synthesis temperature of mother solution to be below 0 DEG C, the ageing time to be 4-8h, the crystallization temperature to be 90-95 DEG C and the crystallization time to be 9-18h, and obtaining slurry formed by the Y-molecular sieve and the rest crystallization liquid; carrying out ammonium exchange treatment on the Y-molecular sieve, and obtaining the mixed solution; and adding an Al source and a Si source into the mixed solution, adjusting the pH value to be 6-10 to form gel, drying the gel, and obtaining the composite catalytic material. The invention also provides the preparation method of the high-medium oil selective hydrocracking catalyst, comprising the following steps of: preparing the Y-molecular sieve/Si-Al oxide composite catalytic material according to the method; taking the composite catalytic material as a carrier for carrying active components; and obtaining the high-medium oil selective hydrocracking catalyst by drying and calcining.

Description

technical field [0001] The invention relates to a composite catalytic material and a method for preparing a selective hydrogenation catalyst, in particular to a Y molecular sieve / silicon aluminum oxide composite catalytic material, and a selective hydrocracking of medium oil for improving the selectivity of medium oil in hydrocracking Catalyst preparation method. Background technique [0002] Hydrocracking is an important processing method for the production of heavy oil to light and clean oil products. The middle distillate type (referred to as medium oil type) hydrocracking for the purpose of producing more kerosene and diesel has developed rapidly. The development of medium oil selective catalysts is The key to improving the technical level of hydrocracking process. High-medium oil selectivity (that is, high medium oil selectivity) hydrocracking catalyst should have: moderate acid activity, providing acid centers required for macromolecular cracking, and avoiding excessi...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J29/16B01J29/08C10G47/20
Inventor 周亚松魏强张涛由慧玲王燕
Owner BC P INC CHINA NAT PETROLEUM CORP
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