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CN-117816235-B - Catalyst composition containing modified Beta molecular sieve and application thereof

CN117816235BCN 117816235 BCN117816235 BCN 117816235BCN-117816235-B

Abstract

The application provides a catalyst composition and application thereof, wherein the catalyst composition comprises 5-20wt% of modified Beta molecular sieve, the particle size of the modified Beta molecular sieve is 100-300nm, the volume of meso-macropores is 0.15-0.40cm 3 /g, the volume of the meso-macropores accounts for 40-60% of the total pore volume, the crystallinity is 80-160%, the SiO 2 /Al 2 O 3 is 20-200%, 20-40wt% of USY type molecular sieve, 40-50wt% of catalyst carrier, 10-20wt% of binder and 0-20wt% of ZSM-5 molecular sieve. The catalyst composition can be used for catalytic cracking of heavy oil, can improve the total yield of ethylene, propylene and butylene, increase the yield of gasoline, increase the yield of diesel oil and reduce the yield of coke.

Inventors

  • LI JIANGCHENG
  • YANG XIAOBO
  • ZHANG JUNLIANG
  • HAN DEZHI
  • WANG JINGHAN

Assignees

  • 泛恩(北京)新材料有限公司

Dates

Publication Date
20260512
Application Date
20231229

Claims (9)

  1. 1. A catalyst composition comprising: 5-20wt% of modified Beta molecular sieve, wherein the modified Beta molecular sieve does not contain a template agent, the particle size of the modified Beta molecular sieve is 100-300 nm, the volume of meso-macropores of the modified Beta molecular sieve is 0.15-0.40cm 3 /g, the volume of the meso-macropores accounts for 40-60% of the total pore volume, the crystallinity of the modified Beta molecular sieve is 80-160%, and the SiO 2 /Al 2 O 3 of the modified Beta molecular sieve is 20-200; 20-40wt% of USY type molecular sieve; 40-50wt% of a catalyst support comprising kaolin clay; 10-20wt% of a binder, and 0 To 20 weight percent of ZSM-5 molecular sieve, Wherein the total mass of the catalyst composition is 100wt%, The modified Beta molecular sieve is prepared as follows: completely removing the template agent from the template agent-containing raw material Beta molecular sieve to obtain the template agent-removed raw material Beta molecular sieve; Performing at least two steps of circulation on the template agent-removed raw material Beta molecular sieve to obtain the modified Beta molecular sieve, namely performing ammonium ion exchange or hydrogen ion exchange, and then performing high-temperature roasting or high-temperature hydrothermal treatment, wherein the temperature of the high-temperature hydrothermal treatment is 400-800 ℃, and the temperature of the high-temperature roasting treatment is 500-800 ℃; the template agent-containing raw material Beta molecular sieve is prepared as follows: Sequentially adding an aluminum source, an alkali source and a template agent into a solvent, stirring the mixture into a solution, and then continuously aging the solution to obtain an intermediate product A; Step two, adding a silicon source, a seed crystal and an additive into another solvent, stirring until the silicon source, the seed crystal and the additive are completely dissolved, adding the intermediate product A in the step one, and then adding an aluminum source to obtain alkaline gel B, wherein the additive is a surfactant; Step three, crystallizing the alkaline gel B in the step two to obtain a Beta molecular sieve which is a raw material containing a template agent, wherein the Beta molecular sieve is in a rod shape, and the crystallization is dynamic crystallization or sectional crystallization; The template agent is used in an amount of 2 to 10 percent of the aluminum source by mol, the grain diameter of the template agent-containing raw material Beta molecular sieve is 100 to 300 nanometers, the utilization rate of the aluminum source is more than or equal to 90 percent, the utilization rate of the silicon source is more than or equal to 83 percent, the crystallinity of the raw material Beta molecular sieve is more than or equal to 93 percent, The catalyst composition is prepared by the following steps: step one, uniformly mixing the components, molding, and aging in water vapor to obtain an aged composition; And step two, sieving the aged composition, and roasting to obtain the catalyst composition, wherein the volume value of the meso-macropores of the catalyst composition is greater than or equal to 25% of that of the modified Beta molecular sieve, and the ratio of the volume of the meso-macropores of the catalyst composition to the total pore volume is greater than or equal to 110% of that of the modified Beta molecular sieve.
  2. 2. The catalyst composition of claim 1 comprising 10 to 15wt% of the modified Beta molecular sieve.
  3. 3. The catalyst composition of claim 1 wherein the USY molecular sieve has a silica to alumina ratio of 10 to 100.
  4. 4. The catalyst composition of claim 1 wherein the USY molecular sieve has a silica to alumina ratio of 20 to 80.
  5. 5. The catalyst composition of claim 1 wherein the USY molecular sieve has a silica to alumina ratio of 30 to 40.
  6. 6. The catalyst composition of claim 2, wherein the catalyst composition has a meso-macroporous volume value of 33% or greater than the meso-macroporous volume value of the modified Beta molecular sieve, and wherein the catalyst composition has a meso-macroporous volume of about 120% or greater than the modified Beta molecular sieve.
  7. 7. The catalyst composition of claim 1 wherein the binder is an alumina sol and the catalyst support is kaolin clay.
  8. 8. A process for carrying out catalytic cracking reactions, characterized in that a catalyst composition according to any one of claims 1 to 6 is used as catalyst.
  9. 9. The method of claim 8, wherein the method is used to perform a catalytic cracking reaction on heavy oil.

Description

Catalyst composition containing modified Beta molecular sieve and application thereof Technical Field The invention relates to a preparation method and application of a raw material Beta molecular sieve modification and a catalyst thereof, in particular to a preparation method and application of a raw material Beta molecular sieve modification and a catalyst thereof with rod-shaped and small grains, belonging to the technical field of molecular sieve materials and preparation thereof. Background The zeolite molecular sieve is a material featuring micropores, and plays a role in the fields of adsorption separation, ion exchange, heterogeneous catalysis and the like. The zeolite molecular sieve has pore size smaller than 1nm and different sizes, so that different size molecules may be sieved, and especially, the zeolite molecular sieve has unique shape selecting function and is especially important in heterogeneous catalysis. However, the diffusion limitations of the microporous channels to large size molecules therein severely impact the use of zeolite molecular sieves in catalytic reactions. The China is a large country for consuming fuel oil, and how to effectively improve the processing capacity of the catalyst on heavy oil macromolecules is the core of the problem of improving the yield of the fuel oil produced by catalytic cracking of the heavy oil macromolecules. The zeolite molecular sieve is used as a main active component in the heavy oil conversion catalyst, the diffusion performance of the zeolite molecular sieve plays a crucial role in cracking heavy oil macromolecules, and the problem of heavy raw oil conversion can be better solved by improving the diffusion capability of the zeolite molecular sieve. The preparation of zeolite molecular sieves with meso-microporous composite pore channels is one of the research hotspots. In the method for preparing the hierarchical pore zeolite molecular sieve, dealumination, desilication or structural rearrangement of the zeolite molecular sieve is more commonly performed in a post-treatment mode. The skeleton of the raw material Beta molecular sieve has high silicon-aluminum ratio, low hydrogen transfer reaction activity, average pore diameter between the Y-type molecular sieve and the ZSM-5 molecular sieve, and excellent carbon tetraolefin selectivity. Therefore, the modified Beta molecular sieve is developed, and the catalyst is prepared by adopting the existing process, so that the performance of the oil refining catalyst is greatly improved, the technical progress of the oil refining catalyst is driven, and simultaneously, great social benefit and economic benefit are brought. Disclosure of Invention In view of the above, in order to solve one of the problems, a raw material molecular sieve modified catalyst, a catalyst composition, a method and an application thereof have an effect of improving the total yield of ethylene, propylene and butylene, or increasing the gasoline yield, or increasing the diesel yield, or decreasing the coke yield. In addition, the application also provides a preparation method of the modified Beta molecular sieve, various application modes of the modified Beta molecular sieve are used in a single catalysis way, the modified Beta molecular sieve is used after being combined, and the effect of the Beta molecular sieve catalyst in catalytic cracking application is obvious. The invention comprises the following contents: embodiment 1, a catalyst composition comprising: 5-20wt% of modified Beta molecular sieve, wherein the modified Beta molecular sieve does not contain a template agent, the particle size of the modified Beta molecular sieve is 100-300nm, the volume of meso-macropores of the modified Beta molecular sieve is 0.15-0.40cm 3/g, the volume of the meso-macropores accounts for 40-60% of the total pore volume, the crystallinity of the modified Beta molecular sieve is 80-160%, and the SiO 2/Al2O3 of the modified Beta molecular sieve is 20-200; 20-40wt% of USY type molecular sieve; 40-50wt% of a catalyst support; 10-20wt% of a binder, and 0 To 20 weight percent of ZSM-5 molecular sieve, Wherein the total mass of the catalyst composition is 100wt%. Embodiment 2. The catalyst composition according to embodiment 1 is prepared by the steps of: step one, uniformly mixing the components, molding, and aging in water vapor to obtain an aged composition; And step two, sieving the aged composition and roasting to obtain the catalyst composition, wherein the mesoporous volume value of the catalyst composition is greater than or equal to 25%, preferably 33%, of the mesoporous volume value of the modified Beta molecular sieve, and the ratio of the volume of meso-macropores of the catalyst composition to the total pore volume is greater than or equal to 110%, preferably 120%, of the ratio of the volume of meso-macropores of the modified Beta molecular sieve to the total pore volume. Embodiment 3. The catalyst composition of embodiment 2, th