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CN-122010129-A - Composite molecular sieve of MTT (methyl thiazolyl tetrazolium) configuration molecular sieve and beta configuration molecular sieve, and manufacturing method and application thereof

CN122010129ACN 122010129 ACN122010129 ACN 122010129ACN-122010129-A

Abstract

The invention relates to a composite molecular sieve with MTT configuration molecular sieve and beta configuration molecular sieve, a manufacturing method thereof and application thereof in hydroisomerization. The method for manufacturing the composite molecular sieve comprises the steps of providing a first molecular sieve containing a first template agent, and then manufacturing a second molecular sieve in the presence of a second template agent and the first molecular sieve containing the first template agent, so as to obtain the composite molecular sieve, wherein the first template agent and the second template agent are different in chemical structure and can form hydrogen bonds. And the first molecular sieve is an MTT-configured molecular sieve and the second molecular sieve is a beta-configured molecular sieve. The composite molecular sieve of the invention can improve the selectivity of isomerization reaction, thereby improving the content of monomethyl branched isomer and realizing the great improvement of the yield of target products.

Inventors

  • XU HUIQING
  • LIU QUANJIE
  • SONG ZHAOYANG
  • LI SIJIE
  • JIA LIMING
  • WANG YANG

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
20260512
Application Date
20241111

Claims (20)

  1. 1. A method of making a composite molecular sieve comprising the steps of: 1) Providing a first molecular sieve comprising a first template (such as making the first molecular sieve comprising a first template in the presence of the first template), and then 2) Producing a second molecular sieve in the presence of a second template and the first molecular sieve comprising the first template to obtain the composite molecular sieve, Wherein the first template is chemically different from the second template and the first molecular sieve is an MTT-configured molecular sieve (such as at least one selected from the group consisting of a ZSM-23 molecular sieve, an EU-13 molecular sieve, a KZ-1 molecular sieve, and an ISI-4 molecular sieve, preferably a ZSM-23 molecular sieve), and the second molecular sieve is a beta-configured molecular sieve (preferably an all-silica beta-configured molecular sieve).
  2. 2. The production method according to claim 1, wherein in step 1) there is also present a silicon source, an aluminum source, an alkali source and water, wherein the silicon source (calculated as SiO 2 ) is such that the molar ratio of the aluminum source (calculated as Al 2 O 3 ) to the alkali source (calculated as OH -1 ) is SiO 2 :Al 2 O 3 :OH - :R:H 2 O = 1:0.002-0.02:0.02-0.30:0.1-2.0:15-90, preferably SiO 2 :Al 2 O 3 :OH - :R:H 2 O=1:0.005-0.015:0.05-0.20:0.15-1.5:20-80, and/or in step 2) there is also present a silicon source, a fluorine source, an alkali source and water, wherein the molar ratio of the fluorine source (calculated as SiO 2 ) to the alkali source (calculated as F -1 ) to the second template D and the water is such that SiO 2 :F - : OH - :D:H 2 O = 1:0.2-2.5:0.25-3.0:0.45-3.0.0:0.0:0.9, preferably SiO 84 = 1.0.0.99-0.5, preferably SiO 99.0.99-0.5:0.99 and/or the molar ratio of the alkali source (calculated as SiO -1 ) to the second template D and the water is such that the molar ratio of SiO 2 :F - : OH - :D:H 2 O = 1:0.2-2.5:0.25-3.0.25-0:0.0.0:0.5:0.9-0.5, preferably SiO 99.99-0.9 and/or the molecular sieve (step 1-99.20) is further comprising the molecular weight ratio of the first template (calculated as SiO 35.35) to the alkali source).
  3. 3. The production process according to claim 1, wherein in step 2), the average particle size of the first molecular sieve containing the first template is 85% or more, preferably 90% or more, passing through 60 mesh, preferably 100 mesh, and/or the free water content of the first molecular sieve containing the first template is not more than 10%, preferably not more than 5%.
  4. 4. The manufacturing process according to claim 1, wherein in step 2) the first template is present in an amount of 3-40wt%, preferably 6-35wt%, based on 100wt% of the total weight of the first molecular sieve comprising the first template, and/or the loss rate of the first template is less than 10% (preferably less than 5% or less than 2%) after washing the first molecular sieve comprising the first template with deionized water 2 times at room temperature.
  5. 5. The method of manufacture of claim 1, wherein the first template and the second template are similar in polarity and capable of forming hydrogen bonds with each other in the presence of water, and/or the first template is capable of being used to synthesize the first molecular sieve, and/or the second template is capable of being used to synthesize the second molecular sieve.
  6. 6. The manufacturing method according to claim 1, wherein the first template is selected from at least one of pyrrolidine, isopropylamine or diisopropylamine, preferably pyrrolidine, and/or the second template is selected from at least one of tetraethylammonium hydroxide, tetraethylammonium fluoride, triethylamine, tetrapropylammonium hydroxide, tetraethylammonium chloride, tetraethylammonium bromide, tetraethylammonium iodide, triethanolamine, polyvinyl alcohol, sodium carboxymethyl cellulose, preferably from at least one of tetraethylammonium hydroxide, tetraethylammonium fluoride and triethylamine.
  7. 7. The manufacturing method of claim 1, wherein in step 1), the step 1) comprises the steps of: 1-1) mixing a silicon source, an aluminum source, an alkali source, a first templating agent, and water to form a first mixture, 1-2) Crystallizing said first mixture to produce said first molecular sieve comprising a first templating agent, 1-3) Isolating the first molecular sieve comprising the first template, preferably, after optional washing and/or optional filtration, drying (in particular spray drying) the first molecular sieve comprising the first template.
  8. 8. The production method according to claim 7, wherein in step 1-2), the crystallization conditions include a crystallization pressure of normal pressure to system autogenous pressure, presence or absence of seed crystal, a crystallization temperature of 100 to 200 ℃, preferably 140 to 180 ℃, a crystallization time of 20 to 96 hours, preferably 24 to 84 hours.
  9. 9. The production method according to claim 7, wherein in step 1-3), the drying conditions include a drying temperature of 60-150 ℃, preferably 80-120 ℃, a drying time of 5-20 hours, preferably 8-15 hours.
  10. 10. The method according to claim 7, wherein in the step 1-3), the spray-drying conditions include a solid content of 35-65%, an inlet air temperature of 150-250 ℃, an outlet air temperature of 80-150 ℃ and a wind speed of 300-1500m 3 /h.
  11. 11. The method of claim 7, further comprising the step of pulverizing (e.g., grinding) the first molecular sieve containing the first template to an average particle size of 85% or more passing through 60 mesh, preferably 90% or more passing through 100 mesh after the step 1-3).
  12. 12. The method of manufacture of claim 1, excluding a step capable of removing a portion or all of the first template from the first molecular sieve comprising the first template, and/or, wherein the step 1) does not include a calcination step.
  13. 13. The manufacturing method of claim 1, wherein the step 2) comprises the steps of: 2-1) mixing a silicon source, a fluorine source, an alkali source, a second templating agent, and water to form a second mixture, 2-2) Mixing said first molecular sieve comprising a first templating agent with said second mixture to obtain a composite mixture, 2-3) Optionally drying said composite mixture, thereafter crystallizing said composite mixture to produce said composite molecular sieve, 2-4) Optionally washing and/or optionally filtering, drying and calcining to obtain the composite molecular sieve.
  14. 14. The manufacturing method of claim 13, wherein in said step 2-2) said second mixture is finely divided (e.g. sprayed) onto said first molecular sieve comprising the first template and/or the morphological integrity (in particular the bulk structure or the pore structure) of said first molecular sieve comprising the first template is substantially maintained after said mixing.
  15. 15. The production method according to claim 13, wherein in the step 2-3), the crystallization conditions include a crystallization pressure of normal pressure to system autogenous pressure, a water vapor concentration of 20% to 70%, preferably a water vapor concentration of 30% to 50%, a crystallization temperature of 100 to 200 ℃, preferably a crystallization temperature of 120 to 180 ℃, a crystallization time of 24 to 96 hours, preferably a crystallization time of 24 to 72 hours.
  16. 16. The production method according to claim 13, wherein in the step 2-4), the drying conditions include a drying temperature of 60 to 150 ℃, preferably 80 to 130 ℃, a drying time of 4 to 20 hours, preferably 6 to 15 hours.
  17. 17. The production method according to claim 13, wherein in the step 2-4), the conditions of the calcination include a calcination temperature of 400-650 ℃, preferably 450-600 ℃, a calcination time of 5-20 hours, preferably 8-15 hours under an oxygen-containing atmosphere.
  18. 18. The method of manufacture of claim 1, wherein in step 1), the first molecular sieve comprising a first templating agent is not substantially removed after manufacture.
  19. 19. The production process according to claim 1, wherein in step 2) the morphological integrity (in particular the bulk structure or the pore structure) of the first molecular sieve comprising the first template is substantially maintained under the production conditions of the second molecular sieve and/or in step 2) the second molecular sieve is grown in situ on the first molecular sieve comprising the first template.
  20. 20. A composite molecular sieve comprising a first molecular sieve and a second molecular sieve covering the surface of the first molecular sieve, wherein the first molecular sieve is an MTT-configured molecular sieve (such as at least one selected from the group consisting of ZSM-23 molecular sieve, EU-13 molecular sieve, KZ-1 molecular sieve, and ISI-4 molecular sieve, preferably ZSM-23 molecular sieve), the second molecular sieve is a beta-configured molecular sieve (preferably an all-silica beta-configured molecular sieve), the mass ratio of the first molecular sieve to the second molecular sieve is (60-99): 1, preferably (70-99): 1, more preferably (80-99): 1, and the composite molecular sieve has an external surface acid weight of 0.001 mmol/g to 0.025mmol/g (preferably 0.003mmol/g to 0.02 mmol/g).

Description

Composite molecular sieve of MTT (methyl thiazolyl tetrazolium) configuration molecular sieve and beta configuration molecular sieve, and manufacturing method and application thereof Technical Field The invention relates to a preparation method and application of a composite molecular sieve, in particular to a composite molecular sieve with an MTT (methyl thiazolyl tetrazolium) configuration molecular sieve and a beta configuration molecular sieve, a preparation method and application thereof in hydroisomerization. Background The normal alkane hydroisomerization reaction typically employs a dual-function solid catalyst comprising a metal component (transition metal or noble metal) that provides the addition/dehydrogenation and an acidic component (amorphous oxide, superacid, molecular sieve, etc.) that undergoes skeletal isomerization, the molecular sieve exhibiting superior performance in terms of shape selectivity, stability, resistance to poisoning, and resistance to carbon deposition compared to amorphous oxides and superacids. Therefore, the isomerization catalyst using molecular sieve as a carrier is widely used. Many reports are made about the preparation of alkane isomerization catalysts at present, for example, patent documents such as CN2004138051, CN2005077209, CN1792451 and the like describe in detail the preparation method of alkane hydroisomerization catalysts taking molecular sieves as carriers. U.S. patent US5990371、US5833837、US5817907、US5149421、US5882505、US5135638、US5110445、US4919788、US4419420、US4601993、US4599162、US4518485, et al, also relates to isomerization dewaxing techniques wherein acidic components used are predominantly mordenite, SAPO-11, SAPO-31, SAPO-41, ZSM-23, SSZ-32, ZSM-48 type molecular sieves, etc. which are suitable for different applications due to their unique pore structure and physicochemical properties. CN201010539097.5 discloses an MF I molecular sieve with core-shell structure and its preparation method. The MF I molecular sieve takes a micron-sized SI L ICA L ITE-1 molecular sieve as a nuclear phase, takes a nano ZSM-5 molecular sieve as a shell phase, and has the thickness of 10-50nm, and the preparation method of the molecular sieve comprises the steps of firstly loading active metal on the SI L I CA L ITE-1 molecular sieve by dipping, and then placing a pure silicon molecular sieve loaded with the active metal in a ZSM-5 molecular sieve growth mother solution for hydrothermal crystallization. The composite molecular sieve can be applied to the fields of petrochemical industry and the like, is a good catalytic material, and has good catalytic performance in the aspects of aromatic hydrocarbon alkylation, aromatic hydrocarbon isomerization, methane aromatization, alkane hydroisomerization and the like. CN10311000399a discloses a preparation method of a mesoporous-microporous composite molecular sieve. The microporous molecular sieve after the hydrothermal treatment is added into a mixed system of a silicon source, an acid solution and a surfactant, and is crystallized, filtered, washed, dried and roasted to obtain the mesoporous-microporous composite molecular sieve, so that non-framework aluminum removed by the microporous molecular sieve is fully utilized, the hydrothermal stability and the thermal stability of the composite molecular sieve are improved, and the composite molecular sieve is applied to catalytic cracking reaction for producing middle distillate oil by taking heavy oil as a raw material, and the conversion rate and the selectivity of the reaction are improved. Beta zeolite has BEA structure, higher silicon-aluminum ratio and special three-dimensional twelve-membered ring pore canal structure, and has excellent properties in hydrocarbon cracking, isomerization, cyclization, alkylation, hydrocracking and other aspects due to the unique structure and good thermal stability. The MTT molecular sieve is a molecular sieve with one-dimensional ten-membered ring linear pore canal, the pore diameter is 0.45 multiplied by 0.52nm, and the molecular sieve has good catalyst activity and selectivity in paraffin dewaxing reaction due to proper acidity and excellent shape selective effect, thereby attracting extensive attention of researchers in the field. In the process that the molecular sieve acts on long-chain alkane hydroisomerization, the pore structure and acidity determine the performance of the catalyst, and according to the theory of orifice-key shape-selective isomerization catalysis, the linear alkane hydroisomerization reaction is mainly carried out at the orifice of a micropore of the molecular sieve, although the molecular sieves of one-dimensional ten-membered ring pore canals such as ZSM-23, SAPO-11 and the like have uniform and developed pore structure and high constraint index, have better shape-selective effect on the reaction occurring in the pore, and are widely used in the field of small molecule conversion. However, the pore canal has a sin