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CN-118183775-B - Molecular sieve composition, preparation method and application thereof

CN118183775BCN 118183775 BCN118183775 BCN 118183775BCN-118183775-B

Abstract

The invention relates to a molecular sieve composition, a preparation method and application thereof. The molecular sieve composition of the invention comprises a TON structure molecular sieve and a mosaic molecular sieve of a 5A type molecular sieve. The molecular sieve composition of the present invention has dual functions of adsorption and hydroisomerization.

Inventors

  • QUAN HUI
  • WANG XIAOSI
  • SONG ZHAOYANG
  • ZHANG ZHIYIN
  • ZHAO WEI
  • SUN GUOQUAN
  • LIU LINDONG
  • HU SHAOJIAN

Assignees

  • 中国石油化工股份有限公司
  • 中石化（大连）石油化工研究院有限公司

Dates

Publication Date
20260505
Application Date
20221213

Claims (20)

  1. 1. A molecular sieve composition comprising a TON structure molecular sieve and a mosaic molecular sieve of type 5A molecular sieve.
  2. 2. The molecular sieve composition of claim 1, wherein the TON structured molecular sieve is inlaid on at least a portion of a surface of the type 5A molecular sieve.
  3. 3. The molecular sieve composition of claim 1, wherein the calcined form of the mosaic molecular sieve has an XRD pattern as shown in Table I or Table II below, TABLE I 2θ D-spacing (nm) Relative intensity 7.184 1.204±0.020 W-S 8.229 1.090±0.020 M-VS 10.133 0.872±0.006 M 12.473 0.709±0.008 W-M 12.685 0.694±0.006 W-M 16.140 0.549±0.004 W 19.338 0.459±0.007 W 20.275 0.438±0.008 M-VS 21.699 0.409±0.008 W-S 24.098 0.369±0.005 VS 24.563 0.362±0.004 M-VS 25.680 0.347±0.005 W-M 26.148 0.341±0.003 W 27.152 0.328±0.002 W 29.997 0.298±0.003 W 34.237 0.262±0.005 W-M 35.537 0.252±0.006 W-M Table II 2θ D-spacing (nm) Relative intensity 7.184 1.204±0.020 W-S 8.229 1.090±0.020 M-VS 10.133 0.872±0.006 M 12.473 0.709±0.008 W-M 12.685 0.694±0.006 W-M 14.399 0.615±0.006 W 16.140 0.549±0.004 W 17.630 0.503±0.006 W 19.338 0.459±0.007 W 20.275 0.438±0.008 M-VS 21.699 0.409±0.008 W-S 24.098 0.369±0.005 VS 24.563 0.362±0.004 M-VS 25.680 0.347±0.005 W-M 26.148 0.341±0.003 W 26.675 0.334±0.004 W 27.152 0.328±0.002 W 29.997 0.298±0.003 W 30.725 0.290±0.004 W-M 32.624 0.274±0.005 W 34.237 0.262±0.005 W-M 35.537 0.252±0.006 W-M 36.835 0.244±0.004 W 38.038 0.236±0.004 W Wherein the intensity value of the strongest diffraction peak in the XRD pattern is set to 100, w=weak, i.e. relative intensity >0 to ∈20, m=medium, i.e. relative intensity >20 to ∈40, s=strong, i.e. relative intensity >40 to ∈60, and vs=very strong, i.e. relative intensity >60 to ∈100.
  4. 4. The molecular sieve composition of claim 1, wherein the mosaic molecular sieve has a specific surface area of 300m 2 /g-600m 2 /g, a pore volume of 0.15cm 3 /g-0.40cm 3 /g, or the molecular sieve composition has a specific surface area of 200m 2 /g-550m 2 /g, a pore volume of 0.25cm 3 /g-0.60cm 3 /g.
  5. 5. The molecular sieve composition of claim 1, wherein the weight ratio of the type 5A molecular sieve to the TON structured molecular sieve in the mosaic molecular sieve is from 1:80 to 3:1.
  6. 6. The molecular sieve composition of claim 1, wherein the weight ratio of the type 5A molecular sieve to the TON structured molecular sieve in the mosaic molecular sieve is from 1:30 to 1:1.
  7. 7. The molecular sieve composition of claim 1, wherein the TON structure molecular sieve is present in an amount of 10wt% to 80wt%, the type 5A molecular sieve is present in an amount of 1wt% to 50wt%, relative to the total weight of the molecular sieve composition, of 100wt%, or the mosaic molecular sieve is present in an amount of 10wt% to 90wt%, relative to the total weight of the molecular sieve composition, of 100 wt%.
  8. 8. The molecular sieve composition of claim 1, wherein the TON structure molecular sieve is present in an amount of 20wt% to 60wt%, the type 5A molecular sieve is present in an amount of 2wt% to 20wt%, relative to the total weight of the molecular sieve composition, of 100wt%, or the mosaic molecular sieve is present in an amount of 20wt% to 70wt%, relative to the total weight of the molecular sieve composition, of 100 wt%.
  9. 9. The molecular sieve composition of claim 1, further comprising an inorganic refractory oxide and an active metal component, wherein the active metal component is present in an amount of 0.05wt% to 5.0wt% as elemental metal, relative to 100wt% of the total weight of the molecular sieve composition.
  10. 10. The molecular sieve composition of claim 1, further comprising an inorganic refractory oxide and an active metal component, wherein the active metal component is present in an amount of 0.1wt% to 1.0wt% as elemental metal, relative to 100wt% of the total weight of the molecular sieve composition.
  11. 11. The molecular sieve composition of claim 9 or 10, wherein the inorganic refractory oxide is selected from one or more of alumina, titania, boria, silica, zirconia and magnesia, and the active metal component is selected from at least one of the noble metals of group VIII of the periodic table of elements.
  12. 12. The molecular sieve composition of claim 9 or 10, wherein the inorganic refractory oxide is selected from alumina and the active metal component is selected from at least one of Pt and Pd.
  13. 13. The molecular sieve composition of claim 12, wherein the active metal component is selected from Pt.
  14. 14. The molecular sieve composition of claim 1, wherein the TON structured molecular sieve is selected from one or more of ZSM-22, theta-1, ISI-1, KZ-2, and NU-10, and the type 5A molecular sieve is selected from a type 5A molecular sieve.
  15. 15. The molecular sieve composition of claim 1, wherein the TON structured molecular sieve is selected from ZSM-22 and the type 5A molecular sieve is selected from a type 5A molecular sieve.
  16. 16. The molecular sieve composition of claim 1, having dual functions of adsorption and hydroisomerization.
  17. 17. A process for preparing the mosaic molecular sieve according to any one of claims 1 to 16, comprising the steps of: (1) Contacting a silicon source, an aluminum source, an alkali source in the presence of a templating agent, a TON structure molecular sieve, and water to obtain a gel mixture, and (2) And carrying out hydrothermal crystallization on the gel mixture, and then washing, drying and roasting to obtain the first mosaic molecular sieve.
  18. 18. The method of manufacturing of claim 17, further comprising the step of: (3) And (3) performing calcium exchange on the first mosaic molecular sieve, and then washing, drying and roasting to obtain the second mosaic molecular sieve.
  19. 19. The production method according to claim 17, wherein in the step (1), the silicon source is selected from at least one of water glass, sodium silicate, methyl orthosilicate, ethyl orthosilicate, propyl orthosilicate, butyl orthosilicate, the alkali source is selected from at least one of alkali metal hydroxide, the aluminum source is selected from at least one of sodium metaaluminate, aluminum isopropoxide, aluminum sulfate, aluminum hydroxide, aluminum oxide, pseudo-boehmite, the template agent is selected from at least one of polyethylene oxide triblock copolymer, dimethyloctadecyl [3- (trimethoxysilyl) propyl ] ammonium chloride, and the TON structure molecular sieve is selected from one or more of ZSM-22, theta-1, ISI-1, KZ-2, and NU-10.
  20. 20. The production process according to claim 17 or 19, wherein in step (1), the alkali source is selected from sodium hydroxide, and the TON-structured molecular sieve is selected from ZSM-22.

Description

Molecular sieve composition, preparation method and application thereof Technical Field The invention belongs to the technical field of catalytic materials, and relates to a molecular sieve composition, a preparation method and application thereof. Background With the increasing strictness of environmental regulations and the rapid development of the mechanical industry, higher and higher demands are being placed on the properties of lubricating base oils. The traditional production of the base oil of the lubricating oil adopts a solvent refining process, and the main two steps are that the solvent refining is adopted to remove non-ideal components such as aromatic hydrocarbon and the like and the solvent dewaxing is adopted to ensure the low-temperature flow property of the base oil. In addition, clay or hydrofinishing is generally performed. At present, the whole crude oil worldwide shows a development trend of poor quality, so that the quantity of crude oil suitable for producing lubricating oil is gradually reduced, and the development and application of the traditional process are restricted due to high energy consumption, heavy pollution and other factors. In recent years, the hydrogenation process for producing lubricating oil has been developed very rapidly. The hydrogenation process is a method for producing the lubricating oil base oil by adopting a hydrocracking process or a hydrotreating-isomerization dewaxing-hydrofining combined process, and has the advantages of high raw material flexibility, high base oil yield, high economic value of byproducts and the like. Currently, the technical problem with hydroisomerization dewaxing processes is that it is difficult to simultaneously make both the light and heavy lubricant oil components meet the pour point and viscosity index requirements when using full or wide cut feeds. Typically, to qualify the pour point of a heavy lubricant component, excessive isomerization of the light lubricant component will result in a loss of viscosity index of the light lubricant component, making it difficult to produce an API group III light base oil product having a viscosity index of greater than 120. In the prior art, in order to prepare the high-viscosity index lubricating oil base oil product, some methods adopt cutting raw materials into narrow components, and then respectively taking the narrow fractions as feeding materials for hydroisomerization dewaxing, so as to solve the problem of producing the high-viscosity index light lubricating oil base oil. There are also lubricating base oils of high viscosity index produced by a step-wise isomerization dewaxing-product separation process using full or wide cut feeds. US7,198,710 discloses a method for producing a high viscosity index lubricant base oil from a fischer-tropsch wax, which comprises the steps of first fractionating the fischer-tropsch wax to obtain light and heavy components, then respectively hydroisomerizing and dewaxing to reduce the pour point of the raw material, thereby obtaining the light lubricant base oil with pour point meeting the requirements, further reducing the pour point of the heavy component by a solvent dewaxing method due to unqualified pour point of the heavy component, and finally obtaining the heavy lubricant base oil product with pour point meeting the requirements. CN102911726a discloses a method for producing a high viscosity index lubricating oil base oil, which uses wax-containing oil without prefractionation as a feed for hydroisomerization dewaxing, and firstly enters a first hydroisomerization dewaxing reaction zone to complete hydroisomerization reaction at a proper depth, and the reaction product is fractionated to obtain a light lubricating oil base oil product with pour point meeting the requirement and high viscosity index and a heavy base oil component with higher pour point. The heavy base oil component continues to enter a second hydroisomerization dewaxing reaction zone, and the reaction product is fractionated to obtain a heavy lubricating oil base oil product with pour point meeting the requirements and high viscosity index. Disclosure of Invention The inventors of the present invention have found during the course of research that long chain isoparaffins and long side chain monocyclic naphthenes are desirable components for making up high viscosity index lubricating oil base oils. Besides synthetic products such as Fischer-Tropsch synthetic oil (F-T oil) and polyester, raw materials for producing lubricating oil base oil in natural petroleum products such as hydrocracking tail oil, hydrotreating wax oil, hydrofined wax grease and other waxy raw materials generally contain non-ideal components such as long-chain isoparaffin, long-side-chain monocyclic naphthene and long-chain monocyclic aromatic hydrocarbon, and contain a certain content of more than two rings of naphthene and aromatic hydrocarbon, and the non-ideal components cannot be converted into high-vis