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CN-122010130-A - Composite molecular sieve of TON or MRE configuration molecular sieve and MWW configuration molecular sieve, manufacturing method and application thereof

CN122010130ACN 122010130 ACN122010130 ACN 122010130ACN-122010130-A

Abstract

The method for manufacturing a composite molecular sieve according to the present invention comprises the steps of providing a first molecular sieve comprising a first template (such as manufacturing the first molecular sieve comprising the first template in the presence of the first template), and then manufacturing a second molecular sieve in the presence of a second template and the first molecular sieve comprising the first template, whereby the composite molecular sieve is obtained, wherein the first template is chemically different from the second template and the first molecular sieve is selected from at least one of TON-configured molecular sieves and MRE-configured molecular sieves (preferably selected from at least one of ZSM-22 molecular sieves and ZSM-48 molecular sieves), and the second molecular sieve is an MWW-configured molecular sieve (preferably an all-silicon MWW-configured molecular sieve, in particular an all-silicon MWW-configured molecular sieve). The composite molecular sieve can realize the goal of directionally generating monomethyl branched isomer products, and remarkably improve the quality of the isomer products.

Inventors

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

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 selected from at least one of TON-configured molecular sieves and MRE-configured molecular sieves (preferably at least one selected from ZSM-22 molecular sieves and ZSM-48 molecular sieves), and the second molecular sieve is an MWW-configured molecular sieve (preferably an all-silica MWW-configured molecular sieve, in particular an all-silica MCM-22 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 alkali source (calculated as Al 2 O 3 ) to the first template R and the water is SiO 2 :Al 2 O 3 :OH - :R:H 2 O=1:0.01-0.05: 0.01-0.35: 0.15-1.0: 5-50,, preferably SiO 2 :Al 2 O 3 :OH - :R:H 2 O=1: 0.02-0.04: 0.05-0.25: 0.25-0.7: 10-40, and/or in step 2) there is also present a silicon source, an alkali source and water, wherein the molar ratio of the alkali source (calculated as SiO 2 ) to the second template D and the water is SiO 2 :OH - :D:H 2 o=1:0.1-1.0:0.02-0.5:6-100, preferably SiO 2 :OH - :D:H 2 o=1:0.1-0.5:0.05-10-100, and/or the molar ratio of the first molecular sieve comprising the first template to the silicon source (calculated as SiO 2 ) of step 2) is preferably 99-99 (99) and preferably 99-99 (99) is further preferred.
  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 of claim 1, wherein in step 2) the first template is present in an amount of 2-50wt%, preferably 3-40wt%, based on the total weight of the first molecular sieve comprising the first template being 100wt%, 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 production method according to claim 1, wherein the first template agent is selected from at least one of 1-butylamine, diethylamine, ethylenediamine, 1, 6-hexamethylenediamine, 1-ethylbromopyridine, 1, 5-bis (N-methylimidazole) pentane, 1, 6-bis (N-methylimidazole) -hexane, tetramethylammonium chloride, 1, 8-octanediamine, hexamethylammonium bromide, hexamethylammonium hydroxide, diethylenetriamine, triethyltetramine, tetraethyltetramine and allyltrimethylammonium chloride, preferably 1, 6-hexamethylenediamine, and/or the second template agent is selected from at least one of hexamethyleneimine, ethylenediamine, piperidine, homopiperazine, N, N, N-trimethyl-1-adamantylammonium hydroxide, cyclohexylamine, N ' -hexamethyl-1, 5-pentanediamine salt, N, N, N ', N ' -tetraisopropyl-1, 5-pentanediamine salt, preferably ethylenediamine.
  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) Separating the first molecular sieve comprising the first template, preferably, after optional washing and/or optional filtration, drying (in particular, heat-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 145 to 200 ℃, preferably 155 to 190 ℃, a crystallization time of 20 to 150 hours, preferably 25 to 120 hours.
  9. 9. The production method according to claim 7, wherein in step 1-3), the drying conditions include a drying temperature of 60-120 ℃, preferably 65-110 ℃, a drying time of 5-20 hours, preferably 8-15 hours.
  10. 10. The production method according to claim 7, wherein in step 1-3), the heat-drying is oil bath heat-drying.
  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, 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 the step 2-2) the first molecular sieve comprising the first template is finely divided (e.g. sprayed) over the second mixture and/or the morphological integrity (in particular the bulk structure or the pore structure) of the first molecular sieve comprising the first template is substantially maintained after the mixing.
  15. 15. The production process according to claim 13, wherein in the step 2-3), the crystallization conditions include a crystallization pressure of from normal pressure to system autogenous pressure, a water vapor concentration of 20% to 70%, preferably 30% to 50%, a crystallization temperature of 130 to 220 ℃, preferably 140 to 200 ℃, a crystallization time of 24 to 120 hours, preferably 36 to 96 hours.
  16. 16. The production method according to claim 13, wherein in the step 2-4), the drying conditions include a drying temperature of 80-150 ℃, preferably 85-130 ℃, a drying time of 5-20 hours, preferably 8-15 hours.
  17. 17. The production method according to claim 13, wherein in the step 2-4), the firing conditions include a firing temperature of 400 to 650 ℃, preferably a firing temperature of 450 to 600 ℃, a firing time of 5 to 20 hours, preferably a firing time of 8 to 15 hours under an oxygen-containing atmosphere.
  18. 18. The method of manufacture of claim 1, wherein in the step 1), the first molecular sieve comprising a first templating agent is substantially not removed after manufacture.
  19. 19. The production process of 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 selected from at least one of a TON-configured molecular sieve and an MRE-configured molecular sieve (preferably selected from at least one of a ZSM-22 molecular sieve and a ZSM-48 molecular sieve), the second molecular sieve is a MWW-configured molecular sieve (preferably an all-silica MWW-configured molecular sieve, in particular an all-silica MCM-22 molecular sieve), the mass ratio of the first molecular sieve to the second molecular sieve is (60-99): 1, preferably (70-99): 1, further preferably (80-99): 1, and the amount of external surface acid of the composite molecular sieve is 0.001 mmol/g to 0.030mmol/g (preferably 0.002mmol/g to 0.025 mmol/g).

Description

Composite molecular sieve of TON or MRE configuration molecular sieve and MWW configuration molecular sieve, manufacturing method and application thereof Technical Field The invention relates to a preparation method and application of a double microporous composite molecular sieve, in particular to a composite molecular sieve with TON or MRE configuration molecular sieve and MWW 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 ICA 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. CN202110070904.1 discloses an MCM-41 and SSZ-32 composite molecular sieve catalyst, which is prepared by loading noble metal on an MCM-41 and SSZ-32 composite molecular sieve, wherein the MCM-41 and SSZ-32 composite molecular sieve is of a core-shell structure, a core is an SSZ-32 molecular sieve, a shell is an MCM-41 molecular sieve, micropores are formed in the SSZ-32 molecular sieve, the aperture is 0.45 multiplied by 0.52nm, mesopores are formed in the MCM-41 molecular sieve, and the aperture is 2-10nm. The invention also discloses a preparation method of the composite molecular sieve catalyst and application of the composite molecular sieve catalyst in the hydroisomerization reaction of normal paraffins to improve the ratio of single branched products. 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-22, 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.