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Catalytic cracking catalyst

A catalytic cracking and catalyst technology, applied in catalytic cracking, physical/chemical process catalysts, molecular sieve catalysts, etc., can solve the problems of reduced catalytic performance, reduced pore volume and specific surface area, low phosphorus utilization efficiency, etc., and achieve high cracking conversion rate and the effect of high yield of low-carbon olefins and high yield of liquefied gas

Pending Publication Date: 2022-05-03
CHINA PETROLEUM & CHEM CORP +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Although ZSM-5 molecular sieve has good shape-selective properties and isomerization properties, its disadvantages are poor hydrothermal stability, and it is easy to deactivate under harsh high-temperature hydrothermal conditions, which reduces the catalytic performance.
[0007]Although the ZSM-5 molecular sieve is modified with an appropriate amount of inorganic phosphide, it can slow down the dealumination of the skeleton and improve the hydrothermal stability, and the phosphorus atoms will interact with the distorted The four-coordinated skeleton aluminum is combined to form a weak B acid center, so as to achieve a higher conversion rate of long-chain alkane cracking and a higher selectivity of light olefins, but excessive inorganic phosphides are used to modify ZSM-5 molecular sieves. It will block the pores of molecular sieves, reduce the pore volume and specific surface area, and occupy a large number of strong B acid centers
Moreover, in the prior art, during the roasting process, phosphoric acid or ammonium phosphate salts will self-polymerize to generate phosphorus species in different aggregation states, the coordination between phosphorus and skeleton aluminum is insufficient, the utilization efficiency of phosphorus is low, and phosphorus modification is not always satisfactory. Satisfactory hydrothermal stability improvement results

Method used

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preparation example Construction

[0040] The present invention also provides a preparation method of the catalyst, the method comprising: mixing Y-type molecular sieve, phosphorus-modified ZSM-5 molecular sieve and inorganic binder for beating and spray drying, and optionally performing roasting treatment , to obtain the catalytic cracking catalyst; wherein, the second clay is added or not added in the mixing; on a dry basis, the Y-type molecular sieve, the phosphorus-modified ZSM-5 molecular sieve, the inorganic binder The weight ratio with the second clay is (1-25): (5-50): (1-60): (0-60); the inorganic binder includes phosphorus aluminum inorganic binder and / or other inorganic binders; wherein the phosphorus-modified ZSM-5 molecular sieve is prepared by the following steps: the phosphorus-containing compound solution is contacted with the HZSM-5 molecular sieve, and after drying, external pressure and external It is obtained by carrying out hydrothermal roasting treatment and recovering the product under t...

Embodiment 1-1

[0079] Example 1-1 illustrates the phosphorus-modified ZSM-5 molecular sieve employed in the catalyst of the present invention.

[0080] Get 16.2g diammonium hydrogen phosphate (Tianjin Guangfu Science and Technology Development Co., Ltd., analytically pure, the same below) and dissolve it in 60g deionized water, stir for 0.5h to obtain a phosphorus-containing aqueous solution, add 113g HZSM-5 molecular sieve (Sinopec catalyst company Qilu Provided by the branch company, the relative crystallinity is 91.1%, the silica / alumina molar ratio is 24.1, and the Na 2 The O content is 0.039% by weight and the specific surface area is 353m 2 / g, the total pore volume is 0.177ml / g, the same below), modified by impregnation, impregnated at 20°C for 2 hours, dried in an oven at 110°C, applied external pressure and added water, at 500°C, The phosphorus-modified ZSM-5 molecular sieve sample obtained by treating under 0.5Mpa and 50% water vapor atmosphere for 0.5h is designated as PSZ1-1.

Embodiment 1-2

[0082] Examples 1-2 illustrate phosphorus-modified ZSM-5 molecular sieves employed in the catalysts of the present invention.

[0083] The materials, proportioning, drying and roasting are the same as those in Example 1-1, except that diammonium hydrogen phosphate, HZSM-5 molecular sieve and water are mixed and beaten into a slurry, and the temperature is raised to 100° C. for 2 hours. The obtained phosphorus-modified ZSM-5 molecular sieve sample is denoted as PSZ1-2.

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Abstract

The catalytic cracking catalyst is characterized by comprising a Y-type molecular sieve and a phosphorus-modified ZSM-5 molecular sieve, and in the phosphorus-modified ZSM-5 molecular sieve and 27Al MAS-NMR, the ratio of the resonance signal peak area with the chemical shift of 39 + / -3ppm to the resonance signal peak area with the chemical shift of 54 + / -3ppm is greater than or equal to 1.

Description

technical field [0001] The invention relates to a catalytic cracking catalyst, more specifically the invention relates to a catalytic cracking catalyst containing Y-type molecular sieve and ZSM-5 molecular sieve. Background technique [0002] Molecular sieves with MFI structure including ZSM-5 molecular sieves are a kind of widely used zeolite molecular sieve catalytic materials developed by Mobil Company of the United States in 1972. The molecular sieve has a three-dimensional intersecting channel structure. The channel along the a-axis is a straight hole with a cross-sectional size of 0.54×0.56 nm, which is approximately circular. The channel along the b-axis is a zigzag hole with a cross-sectional size of 0.51×0.56 nm, is an ellipse. Its orifice is composed of ten-membered rings, and its size is between small-pore zeolite and large-pore zeolite, so this type of molecular sieve has a unique shape-selective catalytic effect. It has a unique pore structure, good shape-sele...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J29/80B01J37/10B01J37/02C10G11/05
CPCB01J29/80B01J37/10B01J37/0009B01J37/0201B01J29/40B01J29/084B01J2229/18B01J2229/24
Inventor 王成强罗一斌欧阳颖邢恩会舒兴田
Owner CHINA PETROLEUM & CHEM CORP