Search

CN-122010132-A - Composite molecular sieve of beta-configuration molecular sieve and MOR-configuration molecular sieve, and manufacturing method and application thereof

CN122010132ACN 122010132 ACN122010132 ACN 122010132ACN-122010132-A

Abstract

The invention relates to a preparation method of a beta configuration molecular sieve and MOR configuration molecular sieve composite microporous material with a double microporous structure and application of the beta configuration molecular sieve and MOR configuration molecular sieve composite microporous material in light alkane isomerization. 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 a beta configuration molecular sieve, and the second molecular sieve is a MOR configuration molecular sieve. The composite molecular sieve of the invention can effectively improve the selectivity of the high-octane component multi-branched alkane, thereby improving the product quality.

Inventors

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

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 a beta configuration molecular sieve and the second molecular sieve is a MOR configuration molecular sieve.
  2. 2. The production method according to claim 1, wherein in step 1), a silicon source, an aluminum source, an alkali source and water are also present, wherein the silicon source (calculated as SiO 2 ) is the aluminum source (calculated as Al 2 O 3 ) and the alkali source (calculated as OH -1 ) is the water in a molar ratio of 1:0.01-0.05:0.01-0.5:5-25:0.05-0.6, preferably 1:0.012-0.04:0.02-0.4:7.5-20:0.1-0.5; and/or, in step 2), there is also a silicon source, an aluminum source, an alkali source and water, wherein the mass ratio of the first molecular sieve comprising the first template to the silicon source (calculated as SiO 2 ) of step 2) is (59-99): 1, preferably (69-99): 1, more preferably (79-99): 1, and/or the first molecular sieve comprising the first template has an average particle size of 85% or more, preferably 90% or more, of 60 mesh, preferably 90% or more, of 1:0.0167-0.125:0.01-0.8, preferably 1:0.02-0.1:0.06-0.6:10-50:0.05-0.6, and/or the mass ratio of the first molecular sieve comprising the first template to the silicon source (calculated as SiO 2 ) of step 2) is (59-99): 1, preferably (69-99): 1, more preferably (79-99): 1, and/or the first molecular sieve comprising the first template has an average particle size of 85% or more, preferably 90% or more, 100% or more, and/or more than 100% by weight of the first molecular sieve comprising the first template and more preferably no water, and no weight of the first template is present in the total weight of 5% or more than 48%, preferably 7wt% to 40wt%, 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 manufacturing method of claim 1, wherein the first template agent and the second template agent are similar in polarity and are capable of forming hydrogen bonds with each other in the presence of water, and/or the first template agent is capable of being used for synthesizing the first molecular sieve, and/or the first template agent is selected from at least one of tetraethylammonium hydroxide, tetraethylammonium fluoride, triethylamine, tetrapropylammonium hydroxide, tetraethylammonium chloride, tetraethylammonium bromide, tetraethylammonium iodide, preferably from tetraethylammonium hydroxide, and/or the second template agent is capable of being used for synthesizing the second molecular sieve, and/or the second template agent is selected from at least one of benzyltrimethylamine, tetraethylammonium bromide, tributylamine, triethylamine, diisopropylamine, isobutylamine, diisobutylamine, tert-octylamine, neopentylamine, cyclohexylamine, cycloheptylamine, 1, 2-diaminocyclohexane, 2-or 4-methylcyclohexylamine, tetramethylethylenediamine, hexamethyleneimine, preferably hexamethyleneimine.
  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, 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).
  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, presence or absence of seed crystals, a crystallization temperature of 100 ℃ to 200 ℃ (preferably 120 ℃ to 180 ℃) and a crystallization time of 20h to 150h (preferably 24h to 80 h), and/or in step 1-3), the drying conditions include a drying temperature of 60 ℃ to 250 ℃ (preferably 80 ℃ to 200 ℃) and a drying time of 0.1h to 20h (preferably 4h to 12 h), 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 speed of 300m 3 /h-1500m 3 /h, and/or further including a step of passing (grinding) the first molecular sieve containing the first template through an average particle size of preferably more than 60% (preferably more than 90 mesh) after the step 1-3).
  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, an aluminum 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 method according to claim 7, wherein in step 2-3), the composite mixture is dried, the crystallization conditions include a crystallization pressure of normal pressure to system autogenous pressure, a water vapor concentration of 20% -70% (preferably 30% -50%), a crystallization temperature of 120 ℃ to 200 ℃ (preferably 140 ℃ to 180 ℃) and a crystallization time of 24h to 150h (preferably 30h to 130 h), and/or, in step 2-3), the crystallization conditions include a crystallization pressure of normal pressure to system autogenous pressure, a crystallization temperature of 120 ℃ to 200 ℃ (preferably 150 ℃ to 180 ℃) and a crystallization time of 18h to 150h (preferably 24h to 120 h), and/or, in step 2-3), the drying conditions include a drying temperature of 60 ℃ to 250 ℃ (preferably 80 ℃ to 200 ℃) and a drying time of 0.1h to 20h (preferably 4h to 12 h), and/or, in step 2-4), the drying conditions include a drying temperature of 60 ℃ to 150 ℃ (preferably 24 ℃ to 150 h).
  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 a beta configuration molecular sieve, the second molecular sieve is a MOR configuration 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.
  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 0.67nm to 0.72nm (preferably about 0.69 nm) and 0.61nm to 0.66nm (preferably about 0.64 nm), respectively, and/or the pore of the most probable pore size of 0.67nm to 0.72nm 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 200m 2 /g-650m 2 /g (preferably 250m 2 /g-600m 2 /g), and the pore volume is 0.15ml/g to 0.60ml/g (preferably 0.22ml/g to 0.55 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 a lower 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 comprising the step of hydroisomerizing a lower alkane 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 200 ℃ to 350 ℃, a reaction pressure of 1MPa to 10MPa, and a volume space velocity of 0.5h -1 -4.0h -1 .

Description

Composite molecular sieve of beta-configuration molecular sieve and MOR-configuration molecular sieve, and manufacturing method and application thereof Technical Field The invention relates to a molecular sieve, in particular to a preparation method of a beta configuration molecular sieve and MOR configuration molecular sieve composite microporous material with a double microporous structure and application of the beta configuration molecular sieve and MOR configuration molecular sieve composite microporous material in light alkane isomerization. Background With the increasingly strict environmental protection requirements, the upgrading frequency of the gasoline quality standard is accelerated, and the demand for the clean gasoline with high octane number is also increasing. Light alkane isomerization technology is receiving increasing attention as one of the most economical and effective methods for producing high octane clean gasoline. Light alkane isomerization catalysts are used as the core of the isomerization technology and are of great importance to the development of the isomerization technology. The light alkane isomerization catalysts currently used in industry mainly comprise low-temperature type and medium-temperature type isomerization catalysts. The low-temperature isomerization catalyst is prepared by taking noble metal Pt or Pd as a metal active component and loading the noble metal Pt or Pd on halogen-containing alumina, and the catalyst has the advantages of low reaction temperature, high catalytic activity, small cracking reaction, high liquid phase yield and the like, and the technology is mature, but the catalyst is very sensitive to sulfur, water and other impurities, the halogen is easy to run off in the production process, chlorine supplementing is needed, and the problems of corrosion and the like of production devices are caused. The reaction temperature of the medium-temperature isomerization catalyst is higher, usually 250-300 ℃, and the isomerization reaction is a micro exothermic reaction, so that the reaction is more favorable at low temperature, but the medium-temperature isomerization catalyst mainly adopts a molecular sieve loaded with noble metal or non-noble metal as a main component, and the catalyst has the advantages of high impurity resistance, strong tolerance and the like, and has the advantages of complete reproducibility, repeated use and better industrialized application value. Chinese patent CN108993575A discloses a noble metal-loaded n-alkane isomerization noble metal catalyst using ZSM-5 and SAPO-11 composite molecular sieve as carrier and cerium as carrier structure auxiliary agent, and its preparation method and application. The catalyst adopts a composite molecular sieve carrier, has proper acid center and acid strength distribution, and improves the mass transfer efficiency of the catalyst and reactants. Chinese patent CN105521811B discloses a hydrocarbon isomerization catalyst with two pore systems of different pore diameters prepared by using a macroporous pore-forming agent and small-grain mordenite. The mordenite pore structure provides a smaller pore system, and the pore-forming agent provides a macroporous pore system, so that the diffusion speed of reactants and products is improved, and the deep reaction of the reactants is avoided. The alkane isomerization catalyst of the molecular sieve has the advantages that the catalyst is designed and modified in terms of acidity and pore canal structure respectively, the reactivity is improved to a certain extent, the side reaction degree is inhibited, the distribution of target products is not optimized further, and particularly, the content of the high-octane component multi-branched isomer is low. Disclosure of Invention Aiming at the defects existing in the prior art, the invention provides a preparation method of a beta configuration molecular sieve and MOR configuration molecular sieve composite microporous material with a double microporous structure, which is applied to light alkane isomerization reaction, has high isoparaffin yield and obviously improves the selectivity of high-octane component multi-branched alkane. The present invention relates in a first aspect to a process for the manufacture of a composite molecular sieve comprising the steps of providing a first molecular sieve comprising a first template (such as the manufacture of 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 to obtain the composite molecular sieve, wherein the first template is chemically different from the second template and the first molecular sieve is a beta configuration molecular sieve and the second molecular sieve is a MOR configuration molecular sieve. The inventor of the present invention found that, in a preferred embodim