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CN-122010133-A - Composite molecular sieve of AEL configuration molecular sieve and beta configuration molecular sieve, and manufacturing method and application thereof

CN122010133ACN 122010133 ACN122010133 ACN 122010133ACN-122010133-A

Abstract

The invention relates to a composite molecular sieve of an AEL configuration molecular sieve and a 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 to obtain the composite molecular sieve, wherein the first template agent and the second template agent are different in chemical structure, the first molecular sieve is an AEL configuration molecular sieve, and the second molecular sieve is a beta configuration molecular sieve. The composite molecular sieve of the invention is used as a catalyst, so that the content of single branched chain isomer can be increased, and the yield of target products can be effectively improved.

Inventors

  • SONG ZHAOYANG
  • LIU QUANJIE
  • XU HUIQING
  • LI SIJIE

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 AEL-configured molecular sieve (preferably a SAPO-11 molecular sieve) and the second molecular sieve is a beta-configured molecular sieve (preferably an all-silicon beta-configured molecular sieve).
  2. 2. The manufacturing method according to claim 1, wherein in step 1) there is also present an aluminum source, a silicon source, a phosphorus source and water, wherein the aluminum source (calculated as Al 2 O 3 ) is the phosphorus source (calculated as P 2 O 5 ) is the silicon source (calculated as SiO 2 ) is the water to the first templating agent molar ratio of 1:0.6-1.4:0.02-1.2:30-100:0.3-2.0, preferably 1:0.7-1.2:0.08-0.8:40-80:0.6-1.8; and/or in step 2), there is also present a silicon source, a fluorine source, an alkali source and water, wherein the silicon source (calculated as SiO 2 ) and the fluorine source (calculated as F -1 ) are in a molar ratio of 1:0.2-2.5:0-0.5:5-40:0.05-0.8, preferably 1:0.3-2.0:0-0.4:6-36:0.1-0.6, the alkali source (calculated as OH -1 ) and water; and/or the mass ratio of the first molecular sieve comprising the first templating agent to the silicon source of step 2) (in terms of SiO 2 ) is (59-99): 1, preferably (69-99): 1, further preferably (79-99): 1, and/or the average particle size of the first molecular sieve comprising the first templating agent is 85% or more, preferably 90% or more, through 60 mesh, preferably 100 mesh, and/or the free water content of the first molecular sieve comprising the first templating agent is not more than 10wt%, preferably not more than 5wt%, and/or the content of the first templating agent is 3wt% to 40wt%, preferably 6wt% to 35wt%, and/or the first template having a loss rate of less than 10wt% (preferably less than 5wt% or less than 2 wt%) after washing the first molecular sieve comprising the first template with deionized water 2 times at room temperature.
  3. 3. The method of manufacture of claim 1, wherein the first template and the second template are similar in polarity and are capable of forming hydrogen bonds with each other in the presence of water, and/or the first template is capable of being used for synthesizing the first molecular sieve, and/or the first template is selected from at least one of di-n-propylamine, diisopropylamine, diethylamine, triethylamine, n-butylamine, di-n-butylamine, diisobutylamine, preferably at least one of di-n-propylamine, diisopropylamine, and/or the second template is capable of being used for synthesizing the second molecular sieve, 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, preferably tetraethylammonium hydroxide.
  4. 4. 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, a phosphorus 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).
  5. 5. The production method according to claim 4, wherein in step 1-2), the crystallization conditions include a crystallization pressure of normal pressure to system autogenous pressure, the presence or absence of seed crystals, a crystallization temperature of 170 ℃ to 230 ℃ (preferably 180 ℃ to 220 ℃) and a crystallization time of 12h to 120h (preferably 24h to 100 h), and/or in step 1-3), the drying conditions include a drying temperature of 60 ℃ to 180 ℃, preferably 80 ℃ to 180 ℃, a drying time of 2h to 20h, preferably 4h to 15h, and/or in step 1-3), the spray drying conditions include a solid content of 35% -65%, an inlet air temperature of 150 ℃ to 250 ℃, an outlet air temperature of 80 ℃ to 150 ℃, an air velocity of 300m 3 /h-1500m 3 /h, and/or after the step 1-3), the first molecular sieve containing the first template agent is crushed (e.g., ground) to an average particle size of 85% or more, preferably 90% or more by passing through 60 mesh of 100 mesh.
  6. 6. 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.
  7. 7. 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, crystallizing said composite mixture to produce said composite molecular sieve, 2-4) Optionally washing and/or optionally filtering, and drying the composite molecular sieve.
  8. 8. The manufacturing process of claim 7, wherein in step 2-2) the first molecular sieve comprising the first template is finely divided (e.g., sprayed) with the second mixture, and/or in step 2-2) the morphological integrity (particularly the bulk structure or the pore structure) of the first molecular sieve comprising the first template is substantially maintained after the mixing.
  9. 9. The production process according to claim 7, wherein in step 2-3) the composite mixture is dried, the crystallization conditions include a crystallization pressure of from atmospheric pressure to system autogenous pressure, a water vapor concentration of 20% to 70%, preferably 30% to 50%, a crystallization temperature of 120 ℃ to 200 ℃, preferably 140 ℃ to 180 ℃, a crystallization time of 24h to 180h, preferably 30h to 150h, and/or, in step 2-3), the crystallization conditions include a crystallization pressure of from atmospheric pressure to system autogenous pressure, a crystallization temperature of 100 ℃ to 200 ℃, preferably 120 ℃ to 180 ℃, a crystallization time of 20h to 150h, preferably 24h to 80h, and/or, in step 2-3), the drying conditions include a drying temperature of 60 ℃ to 250 ℃, preferably 80 ℃ to 200 ℃, a drying time of 0.1h to 20h, preferably 4h to 12h, and/or, in step 2-4), the drying conditions include a drying temperature of 60 ℃ to 80 ℃ and/or, preferably, the drying time of 0.1h to 20h to 12h.
  10. 10. The method of claim 7, further comprising the step of calcining the composite molecular sieve after the step 2-4), wherein the conditions of the calcining include a calcining temperature of 400 ℃ to 650 ℃ (preferably 450 ℃ to 600 ℃) and a calcining time of 3h to 18h (preferably 4h to 12 h) under an oxygen-containing atmosphere.
  11. 11. The manufacturing process of claim 1, wherein in step 1) the first molecular sieve comprising the first template is substantially not removed after manufacture and/or 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 manufacturing 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.
  12. 12. 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 AEL-configured molecular sieve (preferably a SAPO-11 molecular sieve), the second molecular sieve is a beta-configured molecular sieve (preferably an all-silica beta-configured molecular sieve), and 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 amount of 0.001mmol/g to 0.018mmol/g (preferably 0.002mmol/g to 0.014 mmol/g).
  13. 13. The composite molecular sieve of claim 12, wherein the first molecular sieve has an average particle size of 85% or more passing 60 mesh (preferably 90% or more passing 100 mesh).
  14. 14. The composite molecular sieve of claim 12, wherein the first molecular sieve and the second molecular sieve are substantially interpenetrated, and/or the XRD spectrum of the composite molecular sieve is substantially the same as that of the first molecular sieve, and/or the composite molecular sieve has a bimodal pore distribution, and/or the pore distribution of the composite molecular sieve has a most probable pore size of 0.60nm to 0.66nm (preferably about 0.62 nm) and 0.67nm to 0.72nm (preferably about 0.69 nm), respectively, and/or the pore of the most probable pore size of 0.60nm to 0.66nm accounts for more than 80% (preferably about 90%) of the total pore volume, and/or the BET specific surface area of the composite molecular sieve is 160m 2 /g-450m 2 /g (preferably 200m 2 /g-400m 2 /g), and the pore volume is 0.10ml/g to 0.45ml/g (preferably 0.15ml/g to 0.40 ml/g).
  15. 15. The composite molecular sieve of claim 12, producible according to the production method of any one of claims 1 to 11.
  16. 16. A hydroisomerization catalyst, preferably an n-alkane hydroisomerization catalyst, comprising the composite molecular sieve of claim 12 and an active metal component.
  17. 17. The hydroisomerization catalyst of claim 16, wherein the composite molecular sieve is present in an amount (dry basis) of from 1 wt.% to 80 wt.% (preferably from 10 wt.% to 70 wt.%, further preferably from 20 wt.% to 60 wt.%) and the active metal component is present in an amount (calculated as metal element) of from 0.01 wt.% to 10 wt.% (preferably from 0.05 wt.% to 8.0 wt.%, further preferably from 0.1 wt.% to 5.0 wt.%) based on the total weight of the hydroisomerization catalyst taken as 100 wt.%.
  18. 18. The hydroisomerization catalyst according to claim 16, wherein the active metal component is selected from at least one of the noble metal elements of group VIII of the periodic table of the elements, preferably from at least one of Pt and Pd, in particular Pt.
  19. 19. A hydroisomerization process, such as a process for the isomerization dewaxing of a lube fraction, comprising the step of hydroisomerizing an n-alkane, such as a paraffinic hydrocarbon, in the presence of the hydroisomerization catalyst of claim 16.
  20. 20. The hydroisomerization process of claim 19, wherein the hydroisomerization reaction conditions comprise a reaction temperature of 250 ℃ to 420 ℃, a reaction pressure of 1.0MPa to 20MPa, a volume space velocity of 0.5h -1 -4.0h -1 , and a hydrogen-to-oil volume ratio of 500:1 to 1400:1.

Description

Composite molecular sieve of AEL configuration molecular sieve and beta configuration molecular sieve, and manufacturing method and application thereof Technical Field The invention relates to a molecular sieve, in particular to a composite molecular sieve of an AEL configuration molecular sieve and a beta configuration molecular sieve, a manufacturing method thereof and application thereof in hydroisomerization. Background With rapid development of the automobile industry and increasingly strict environmental protection requirements, the demand for high-end lubricating oil is increasing, and high-quality III and III + lubricating oil base oils are required to be used as basic blending components for producing high-end lubricating oil, and the isomerization dewaxing technology is attracting more and more attention as a main technology for producing high-end lubricating oil base oils. At the heart of the isomerization dewaxing technology is the development of isomerization dewaxing catalysts, which typically employ a dual function catalyst having a combination of a metal active component having a hydrodeoxygenation function and an acidic component having a skeletal isomerization function. Wherein, the metal active component is usually noble metal of group VIII, and the acid component is mainly molecular sieve with one-dimensional pore structure and proper acid property, wherein the molecular sieve acid component is the key of the isomerization dewaxing catalyst. The molecular sieve suitable for the isomerization dewaxing reaction is usually a one-dimensional straight-pore molecular sieve, common molecular sieves suitable for the isomerization dewaxing reaction are AEL type molecular sieves, MTT type molecular sieves, TON type molecular sieves, MRE type molecular sieves and the like, the pore channel structure size can realize shape selection according to the size of alkane molecules, the acidity of the molecular sieves cannot be too strong, the quick desorption of products is facilitated, and the occurrence of secondary isomerization, cracking and other side reactions caused by the fact that the adsorption capacity of the molecular sieves is too strong to enable the products to be unable to be separated from active centers is avoided. Although the pore canal structure of the molecular sieve can meet the shape-selective requirement that normal alkane can freely enter and exit, isoparaffin with larger molecular size can not enter, and has better shape-selective effect on the reaction occurring in the pore canal, the single-molecular sieve pore canal structure system has certain limitation in the aspects of molecular adsorption and product diffusion, has single structure, can not effectively restrict the product at the orifice, and easily generates non-target product multi-branched isomer, thereby leading to lower yield of the isomerized product, low product liquid yield and further improving the product quality. The composite molecular sieve can enhance the constraint on the reaction by coupling pore channels and acidity of molecular sieves with different characteristics, thereby being more beneficial to generating a single branched chain isomer product of a target product. Chinese patent CN107512725B discloses a composite molecular sieve having a core-shell structure TON-MF I and a preparation method thereof, wherein the composite molecular sieve uses MF I molecular sieve as a core and TON molecular sieve as a shell to form a core-shell molecular sieve. The composite molecular sieve has high crystallinity, regular particle dispersion and morphology, simple synthesis method, no complicated preparation steps, ten-membered ring one-dimensional pore canal and Z-shaped pore canal, more exposed pore opening active sites due to the combination mode, and potential application value in the fields of fine chemical industry, petrochemical industry and the like, and can be used for various shape-selective catalytic reactions. Chinese patent CN112717995B discloses a MCM-41 and SSZ-32 composite molecular sieve catalyst, wherein the composite molecular sieve comprises a microporous molecular sieve SSZ-32 molecular sieve as a core and a mesoporous molecular sieve MCM-41 molecular sieve as a shell, the composite molecular sieve has obvious acid gradient distribution, the acidity of the internal micropores is stronger, the acidity of the external mesopores is weaker, and the two have synergistic effects, so that excellent performance is shown in hydroisomerization catalytic reaction, the isomerism rate of normal paraffins and the yield of target products are improved, the occurrence of secondary reaction-cracking reaction is reduced, the yield of single branched chain isomerism products is improved, the catalytic activity is improved, the generation of carbon deposition is reduced, and the service life of the catalyst is prolonged. The inventor of the invention discovers that when a single molecular sieve is applied to long-pa