CN108033462A - A kind of multi-stage porous LTL molecular sieves and its synthetic method and application - Google Patents
A kind of multi-stage porous LTL molecular sieves and its synthetic method and application Download PDFInfo
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- CN108033462A CN108033462A CN201810023176.7A CN201810023176A CN108033462A CN 108033462 A CN108033462 A CN 108033462A CN 201810023176 A CN201810023176 A CN 201810023176A CN 108033462 A CN108033462 A CN 108033462A
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- ltl
- molecular sieves
- silicon source
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 58
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 238000010189 synthetic method Methods 0.000 title abstract description 5
- 239000003054 catalyst Substances 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 18
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 16
- 239000010703 silicon Substances 0.000 claims abstract description 16
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 15
- 238000005899 aromatization reaction Methods 0.000 claims abstract description 15
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 15
- 238000002360 preparation method Methods 0.000 claims abstract description 15
- 238000002425 crystallisation Methods 0.000 claims abstract description 14
- 230000008025 crystallization Effects 0.000 claims abstract description 14
- 239000007864 aqueous solution Substances 0.000 claims abstract description 11
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 9
- 239000011591 potassium Substances 0.000 claims abstract description 9
- 230000032683 aging Effects 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical group [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000004411 aluminium Substances 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 5
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 4
- 229920000604 Polyethylene Glycol 200 Polymers 0.000 claims description 3
- 229920002582 Polyethylene Glycol 600 Polymers 0.000 claims description 3
- 229920002593 Polyethylene Glycol 800 Polymers 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 2
- 239000004115 Sodium Silicate Substances 0.000 claims description 2
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical group [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 2
- 229910001593 boehmite Inorganic materials 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 2
- 229910052741 iridium Inorganic materials 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 235000019353 potassium silicate Nutrition 0.000 claims description 2
- 235000019795 sodium metasilicate Nutrition 0.000 claims description 2
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims 3
- 239000002184 metal Substances 0.000 claims 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 abstract description 8
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 239000012141 concentrate Substances 0.000 abstract description 2
- 231100000252 nontoxic Toxicity 0.000 abstract description 2
- 230000003000 nontoxic effect Effects 0.000 abstract description 2
- 238000001308 synthesis method Methods 0.000 abstract description 2
- 239000012467 final product Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 18
- 239000000047 product Substances 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000002441 X-ray diffraction Methods 0.000 description 8
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 8
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 7
- 229910052593 corundum Inorganic materials 0.000 description 7
- 239000011148 porous material Substances 0.000 description 7
- 239000003643 water by type Substances 0.000 description 7
- 229910001845 yogo sapphire Inorganic materials 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 238000009792 diffusion process Methods 0.000 description 5
- 239000000376 reactant Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000010457 zeolite Substances 0.000 description 5
- 244000205754 Colocasia esculenta Species 0.000 description 4
- 235000006481 Colocasia esculenta Nutrition 0.000 description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000005352 clarification Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000000634 powder X-ray diffraction Methods 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 229910052681 coesite Inorganic materials 0.000 description 3
- 229910052906 cristobalite Inorganic materials 0.000 description 3
- 238000001802 infusion Methods 0.000 description 3
- 238000012805 post-processing Methods 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 229910052682 stishovite Inorganic materials 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 229910052905 tridymite Inorganic materials 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 241001120493 Arene Species 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229960001484 edetic acid Drugs 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000007327 hydrogenolysis reaction Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/32—Type L
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/60—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the type L, as exemplified by patent document US3216789
- B01J29/61—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the type L, as exemplified by patent document US3216789 containing iron group metals, noble metals or copper
- B01J29/62—Noble metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
- C07C5/373—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen with simultaneous isomerisation
- C07C5/393—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen with simultaneous isomerisation with cyclisation to an aromatic six-membered ring, e.g. dehydrogenation of n-hexane to benzene
- C07C5/41—Catalytic processes
- C07C5/415—Catalytic processes with metals
- C07C5/417—Catalytic processes with metals of the platinum group
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C07C2529/00—Catalysts comprising molecular sieves
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- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/60—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the type L
- C07C2529/61—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the type L containing iron group metals, noble metals or copper
- C07C2529/62—Noble metals
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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- Y02P20/50—Improvements relating to the production of bulk chemicals
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Abstract
The invention discloses a kind of multi-stage porous LTL molecular sieves and its synthetic method and application.The preparation method of the LTL molecular sieves includes the following steps：(1) mixed aqueous solution of silicon source and potassium resource is prepared；(2) silicon source and Aqueous Solutions of Polyethylene Glycol are sequentially added into the mixed aqueous solution, sieve starting sol mixture is obtained through aging；(3) the sieve starting sol mixture through thermostatic crystallization and roasts successively to obtain the final product.Multi-stage porous LTL Zeolite synthesis methods of the present invention are simple, and building-up process is nontoxic；LTL molecular sieves of the present invention have hierarchical porous structure, its intermediary hole concentrates on 2~7nm；Multi-stage porous LTL molecular sieves of the present invention show excellent catalytic performance in normal octane aromatization, and compared with conventional microporous LTL catalyst, aromatics yield improves more than 20%, has good prospects for commercial application.
Description
Technical field
The present invention relates to a kind of multi-stage porous LTL molecular sieves and its synthetic method and application, belong to technical field of molecular sieve.
Background technology
Aromatic hydrocarbons occupies extremely important work as one of basic raw material of chemical industry in petrochemical industry system
With.LTL molecular sieves have unique shape selectivity, stronger basic center and good hydrothermal stability, in C6~C8 alkane virtue
Excellent catalytic performance is shown in structureization reaction.However, there is one-dimensional twelve-ring pore passage structure larger diffusion to limit, it is raw
Into higher carbon number aromatic hydrocarbons (such as dimethylbenzene) due to cannot be diffused into time outside duct may proceed to occur the secondary side reaction of hydrogenolysis,
Aromatization products are caused based on benzene and toluene, aromatics yield is reduced and liquid is received；Simultaneously because product is in one-dimensional channels
Diffusion limitation, easily causes carbon distribution and inactivates in catalytic reaction.Typically, introduced in micro porous molecular sieve system it is mesoporous can
To effectively improve the diffusion rate of reactant and product, and then the formation of carbon distribution is reduced, improve target product yield and catalysis
The service life of agent.Therefore, the synthesis of multi-stage porous LTL molecular sieves has important researching value.
In recent years, many synthetic method such as post treatment methods, hard template method and soft template method etc. have been successfully applied to make
Standby multistage porous molecular sieve.Wherein for LTL molecular sieves, the researcher such as Minkee Choi uses the pore forming method of post processing,
It is mesoporous to LTL molecular sieves construction intergranular i.e. first with ethylenediamine tetra-acetic acid dealuminzation again by the method for potassium hydroxide desiliconization
(J.Catal., 66-75 (2016) 340), and performance evaluation is carried out to the molecular sieve after processing by a variety of model compounds, it is real
Test it turns out that the method for continuous dealuminzation desiliconization can introduce secondary mesopore so as to improve diffusion of the product in molecular sieve pore passage
Performance, and then improve aromatics yield particularly C8 aronmatic yield.But use the method for post processing cumbersome while can produce
More acid-base waste fluid, limits its application in the industrial production.Thus seek a kind of simple, efficient and cheap method
Preparing multi-stage porous molecular sieve with high performance has great actual application value.
The content of the invention
The object of the present invention is to provide a kind of LTL molecular sieves with hierarchical porous structure and preparation method thereof, the LTL divides
Sub- sifter device has hierarchical porous structure, and average mean crystal size size is 1 μm or so, and mesopore size is concentrated mainly between 2~7nm, is situated between
Pore volume is 0.2cm3/ g, specific surface area are up to 350m2/g。
Hierarchical porous structure LTL molecular sieves of the present invention are conducive to improve the diffusion speed of reactant and product in molecular sieve pore passage
Rate, avoids the generation of secondary side reaction, so as to improve the yield of aromatic hydrocarbons.
The present invention prepares multi-stage porous LTL molecular sieves using hydrothermal synthesis method, low by adding price using water as solvent
Honest and clean polyethylene glycol (PEG) polymer, modulation colloidal sol composition and concentration, are had in crystallization kettle by self-generated pressure
The LTL molecular sieves of hierarchical porous structure.
Specifically, the method for the present invention includes the following steps：
(1) mixed aqueous solution of silicon source and potassium resource is prepared；
(2) silicon source and Aqueous Solutions of Polyethylene Glycol are sequentially added into the mixed aqueous solution, starting sol is obtained through aging
Mixture；
(3) the starting sol mixture through thermostatic crystallization and is roasted up to the LTL with hierarchical porous structure successively
Molecular sieve.
In above-mentioned preparation method, source of aluminium can be aluminium isopropoxide, aluminum nitrate, aluminium hydroxide or boehmite；
The potassium resource can be potassium hydroxide；
The silicon source can be white carbon, waterglass, sodium metasilicate or Ludox.
In above-mentioned preparation method, the polyethylene glycol can be PEG-200, PEG-400, PEG-600 and PEG-800 in extremely
Few one kind；
The amount of the potassium resource, the silicon source and source of aluminium is with the gauge of its oxide, the polyethylene glycol, the potassium
Source, the silicon source, the molar ratio of source of aluminium and water can be 0.1~8：0.5~6：3~15：1：300~600, concretely 1
~2：2.56：11.30：1：375、1：2.56：11.30：1：375 or 2：2.56：11.30：1：375.
In above-mentioned preparation method, in step (1), the method is further included the mixed aqueous solution in 20~100 DEG C
Under the conditions of stir 1~20h the step of, such as under the conditions of 90~100 DEG C stirring 10~12h.
In above-mentioned preparation method, in step (2), the temperature of the aging can be 10~50 DEG C, and the time can be 1~10h,
When such as aging 1~5 is small at 20 DEG C.
In above-mentioned preparation method, in step (3), the temperature of the thermostatic crystallization can be 120~180 DEG C, and the time can be
20~48h, such as under conditions of 160~180 DEG C 24~48h of thermostatic crystallization, thermostatic crystallization 24h under conditions of 160 DEG C, 170 DEG C
Under conditions of thermostatic crystallization 48h under conditions of thermostatic crystallization 48h or 180 DEG C.
In above-mentioned preparation method, in step (3), the filtering carried out successively, washing, drying are further included before the roasting
The step of；
The washing step washs eluate to neutrality, preferably there is deionized water washing；
The temperature of the drying can be 80~130 DEG C, and the time can be 1~12h；
The temperature of the roasting can be 450~600 DEG C, and the time can be 4~10h, can carry out, pass through in oxygen or air
The roasting removes solvent contained in original powder, so as to obtain the LTL molecular sieves with hierarchical porous structure.
The preparation method that the present invention passes through is simple, and synthesis is of low cost, for post-processing approach, it is not necessary to follow-up
Soda acid processing, considerably reduces synthesis cost and caused waste liquor contamination.
Multi-stage porous LTL molecular sieves provided by the invention are widely used as the catalyst carrier of the various hydrocarbon conversions, especially may be used
Catalyst carrier as C6~C8 alkane aromatization reactions.
Multi-stage porous LTL molecular sieves of the present invention, can be by infusion process in institute when for C6~C8 structure alkane aromatization reactions
After stating the catalytic active component that suitable proportion is loaded on multi-stage porous LTL molecular sieves, that is, obtain alkane aromatization catalyst.
The catalytic active component can be the combination of any one or more in Pt, Pd, Ir etc..
Specifically, urged for example, 0.5wt.%Pt is loaded to obtained aromatisation on above-mentioned molecular sieve carrier by infusion process
Agent；Before use, it is necessary to need 120 DEG C of dry 12h in air atmosphere before the reaction, then 4h is roasted at 350 DEG C.
Above-mentioned catalyst is used to be catalyzed alkane aromatization reaction, when being such as catalyzed the aromatisation of C6~C8 alkane, aromatics yield
Significantly improve.
During using above-mentioned catalyst alkane aromatization reaction, can be carried out in fixed bed reactors, using normal octane as
Example, the reaction condition of the alkane aromatization reaction can be：Normal octane air speed can be 1~3h-1, hydrogen/normal octane molar ratio can
For 0.2~6.0, reaction pressure can be 0.1~2MPa, and reaction temperature can be 300~600 DEG C
The present invention has the following advantages：
1st, multi-stage porous LTL Zeolite synthesis methods of the present invention are simple, and building-up process is nontoxic；
2nd, LTL molecular sieves of the present invention have hierarchical porous structure, its intermediary hole concentrates on 2~7nm；
3rd, multi-stage porous LTL molecular sieves of the present invention show excellent catalytic performance in normal octane aromatization, with biography
System micropore LTL catalyst is compared, and aromatics yield improves more than 20%, has good prospects for commercial application.
Brief description of the drawings
Fig. 1 is the XRD spectra of LTL molecular sieves prepared by comparative example 1 of the present invention.
Fig. 2 is the SEM photograph of LTL molecular sieves prepared by comparative example 1 of the present invention.
Fig. 3 is the XRD spectra of LTL molecular sieves prepared by the embodiment of the present invention 1.
Fig. 4 is the SEM photograph of LTL molecular sieves prepared by the embodiment of the present invention 1.
Fig. 5 is the XRD spectra of LTL molecular sieves prepared by the embodiment of the present invention 2.
Fig. 6 is the SEM photograph of LTL molecular sieves prepared by the embodiment of the present invention 2.
Fig. 7 is the XRD spectra of LTL molecular sieves prepared by the embodiment of the present invention 3.
Fig. 8 is the SEM photograph of LTL molecular sieves prepared by the embodiment of the present invention 3.
Fig. 9 is the graph of pore diameter distribution of LTL molecular sieves prepared by the embodiment of the present invention 1,2,3.
Embodiment
Experimental method used in following embodiments is conventional method unless otherwise specified.
The materials, reagents and the like used in the following examples, is commercially available unless otherwise specified.
Comparative example 1,
Take 150.6g KOH, 45.2g aluminium hydroxides to be added in 1400g deionized waters, three mouthfuls are transferred to after stirring evenly
12h is reacted in 80 DEG C in flask, clarification KAlO is obtained after being cooled to room temperature2Solution, K in the silicon source solution2O:Al2O3Mole
Than for 3.85:1.It is slowly added to 305.4g Ludox (SiO while stirring into the solution2Content 30wt%), it is sufficiently mixed
To LTL molecular sieve colloidal sols, the crystallization 24h at 170 DEG C is transferred in static kettle after being aged 1h at 20 DEG C.Product is through deionized water
Then washing can obtain LTL molecular screen primary powders to neutrality in 120 DEG C of dry 12h, after 500 DEG C of roasting 4h.
Sample segment is taken to do X-ray powder diffraction measure, Fig. 1 is the XRD spectra of sample, the product as a result illustrated
For LTL molecular sieves；Fig. 2 is the SEM photograph of sample, and as a result sample prepared by explanation is cylindric, average mean crystal size size
It is typical LTL topological structures Molecular Sieve Morphology feature for 1 μm or so.Nitrogen adsorption test the result shows that the table of the sample
Area is 296m2/g。
Embodiment 1,
Take 100.3g KOH, 45.3g aluminium hydroxides to be added in 1300g deionized waters, three mouthfuls are transferred to after stirring evenly
12h is reacted in 90 DEG C in flask, clarification KAlO is obtained after being cooled to room temperature2Solution, K in the silicon source solution2O:Al2O3Mole
Than for 2.56:1.It is slowly added to 668g Ludox (SiO while stirring into the solution2Content 30wt%), strong stirring is uniform
After obtain starting sol.Take 59.52g PEG200 to be dissolved in 200g deionized waters and PEG solution is made.PEG solution is slowly added dropwise
Continue strong stirring into colloidal sol, be transferred to after being aged 1h at 20 DEG C in dynamic kettle, react 48h under the conditions of 170 DEG C.Crystallization
After, reactant is cooled to room temperature, filters, be washed with deionized water to neutrality and roasted in 85 DEG C of dry 11h, in 450 DEG C
Multi-stage porous LTL zeolites are obtained after 10h.
Wherein, the amount of aluminium hydroxide is with Al2O3Meter, the amount of KOH is with K2O is counted, and the amount of Ludox is with SiO2Meter, rate of charge (rub
That ratio) be：11.30SiO2：2.56K2O：1Al2O3：1PEG200：375H2O。
Sample segment is taken to do X-ray powder diffraction measure, Fig. 3 is the XRD spectra of sample, the product as a result illustrated
For LTL molecular sieves；Fig. 4 is the SEM photograph of sample, and as a result sample prepared by explanation is cylindric, and granular size is on 1 μm of left side
The right side, is typical LTL topological structures Molecular Sieve Morphology feature.Nitrogen adsorption test the result shows that the sample have higher table
Area, up to 320m2/g。
Embodiment 2,
Take 100.3gKOH, 45.3g aluminium hydroxide to be added in 1200g deionized waters, three mouthfuls of burnings are transferred to after stirring evenly
12h is reacted in 100 DEG C in bottle, clarification KAlO is obtained after being cooled to room temperature2Solution, K in the silicon source solution2O:Al2O3Molar ratio
For 2.56:1.It is slowly added to 668g Ludox (SiO while stirring into the solution2Content 30wt%), after strong stirring is uniform
Obtain starting sol.Take 357.12g PEG600 to be dissolved in 300g deionized waters and PEG solution is made.PEG solution is slowly added dropwise
Continue strong stirring into colloidal sol, be transferred to after being aged 1h at 20 DEG C in dynamic kettle, react 48h under the conditions of 180 DEG C.Crystallization
After, reactant is cooled to room temperature, filters, be washed with deionized water to neutrality and roasted in 130 DEG C of dry 3h, in 450 DEG C
Multi-stage porous LTL zeolites are obtained after 6h.
Wherein, the amount of aluminium hydroxide is with Al2O3Meter, the amount of KOH is with K2O is counted, and the amount of Ludox is with SiO2Meter, rate of charge (rub
That ratio) be：11.30SiO2：2.56K2O：1Al2O3：2PEG600：375H2O。
Sample segment is taken to do X-ray powder diffraction measure, Fig. 5 is the XRD spectra of sample, and the product shown is LTL
Molecular sieve；And compared with comparative example 1, there is widthization in the peak of sample XRD, shows that zeolite crystal size has reduced.Fig. 6
For the SEM photograph of sample, as a result sample prepared by explanation is fusiform, is a kind of special LTL topological structure molecular sieve shapes
Looks.Nitrogen adsorption test the result shows that the surface area of the sample is 337m2/g。
Embodiment 3,
Take 100.3gKOH, 45.3g aluminium hydroxide to be added in 1100g deionized waters, three mouthfuls of burnings are transferred to after stirring evenly
10h is reacted in 90 DEG C in bottle, clarification KAlO is obtained after being cooled to room temperature2Solution, K in the silicon source solution2O:Al2O3Molar ratio
For 2.56:1.It is slowly added to 668g Ludox (SiO while stirring into the solution2Content 30wt%), after strong stirring is uniform
Obtain starting sol.Take 476.16g PEG800 to be dissolved in 400g deionized waters and PEG solution is made.PEG solution is slowly added dropwise
Continue strong stirring into colloidal sol, be transferred to after being aged 5h at 20 DEG C in dynamic kettle, react 24h under the conditions of 160 DEG C.Crystallization
After, reactant is cooled to room temperature, filters, be washed with deionized water to neutrality and roasted in 110 DEG C of dry 12h, in 600 DEG C
Multi-stage porous LTL zeolites are obtained after 4h.
Wherein, the amount of aluminium hydroxide is with Al2O3Meter, the amount of KOH is with K2O is counted, and the amount of Ludox is with SiO2Meter, rate of charge (rub
That ratio) be：11.30SiO2：2.56K2O：1Al2O3：2PEG800：375H2O。
Sample segment is taken to do X-ray powder diffraction measure, Fig. 7 is the XRD spectra of sample, the product as a result illustrated
For LTL molecular sieves, the widthization at XRD peaks shows that zeolite crystal size has reduced；Fig. 8 is the SEM photograph of sample, is as a result illustrated
Prepared sample is spherical, is a kind of LTL molecular sieves of special appearance.Nitrogen adsorption test the result shows that the sample has
The surface area of higher, up to 354m2/g。
Fig. 9 is the pore size distribution curve of sample prepared by the embodiment of the present invention 1,2 and 3, wherein positioned at the hole of 0.7nm or so
Road belongs to the twelve-ring duct of LTL molecular sieves, and belongs to mesopore orbit positioned at the duct of 2.0~7.0nm or so.
Embodiment 4, reactivity worth evaluation
LTL molecular sieves in the embodiment 1-3 hetero-atom molecular-sieves prepared and comparative example 1 are loaded by infusion process
The Pt of 0.5wt.%, then in 120 DEG C of dry 12h in air atmosphere, then roasts 4h at 350 DEG C and prepares corresponding catalyst.So
Afterwards using normal octane as raw material, its Aromatization Activity is evaluated in fixed bed reactors.
Wherein, mass space velocity (WHSV) is 2h-1, hydrogen-hydrocarbon ratio is 7 (molar ratios), reaction pressure 0.7MPa, reaction temperature
For 500 degrees Celsius.The wherein condensed rear off-line analysis of liquid product, gas-phase product on-line analysis.
Evaluating catalyst result is as follows：
Excellent catalytic performance is shown in normal octane aromatization with catalyst prepared by the carrier, such as the institute of table 1
Showing, it can be seen that for catalyst prepared by embodiment 3 in the case of 91.35% conversion ratio, total arenes yield reaches 66.58%,
Wherein C8 aromatics yields reach 34.76%.And conventional molecular sieve (comparative example 1) catalyst is in the case of similar in conversion ratio, always
Aromatics yield is 44.21%, and C8 aromatics yields are only 6.23%, and the catalyst standby well below system with molecular sieve for preparing of the present invention turns
Change effect.
The catalytic performance test of 1 each catalyst of table
It is anti-in normal octane aromatisation that the standby catalyst of multi-stage porous system with molecular sieve for preparing of the present invention is can be seen that from the data in table 1
There is higher aromatics yield and liquid to receive, particularly C8 aromatics yields are significantly improved in answering.
Claims (10)
1. a kind of preparation method of the LTL molecular sieves with hierarchical porous structure, includes the following steps：
(1) mixed aqueous solution of silicon source and potassium resource is prepared；
(2) silicon source and Aqueous Solutions of Polyethylene Glycol are sequentially added into the mixed aqueous solution, obtaining sieve starting sol through aging mixes
Compound；
(3) the sieve starting sol mixture through thermostatic crystallization and is roasted up to described the LTL with hierarchical porous structure points successively
Son sieve.
2. preparation method according to claim 1, it is characterised in that：Source of aluminium is aluminium isopropoxide, aluminum nitrate, hydroxide
Aluminium or boehmite；
The potassium resource is potassium hydroxide；
The silicon source is white carbon, waterglass, sodium metasilicate or Ludox.
3. preparation method according to claim 1 or 2, it is characterised in that：The polyethylene glycol is PEG-200, PEG-
400th, at least one of PEG-600 and PEG-800；
The amount of the potassium resource, the silicon source and source of aluminium is with the gauge of its oxide, the polyethylene glycol, the potassium resource, institute
The molar ratio for stating silicon source, source of aluminium and water is 0.1~8：0.5~6：3~15：1：300~600.
4. preparation method according to any one of claim 1-3, it is characterised in that：In step (1), the method is also wrapped
Include by the mixed aqueous solution under the conditions of 20~100 DEG C stir 1~20h the step of.
5. according to the preparation method any one of claim 1-4, it is characterised in that：In step (2), the temperature of the aging
Spend for 10~50 DEG C, the time is 1~10h.
6. according to the preparation method any one of claim 1-5, it is characterised in that：In step (3), the thermostatic crystallization
Temperature be 120~180 DEG C, the time is 20~48h.
The temperature of the roasting is 450~600 DEG C, and the time is 4~10h；
Further include before the roasting carry out successively the step of being filtered, washed and dried；
The washing step washs eluate to neutrality；
The temperature of the drying is 80~130 DEG C, and the time is 1~12h.
7. the LTL molecular sieves with hierarchical porous structure prepared by method any one of claim 1-6.
It is 8. a kind of to have catalyst of the LTL molecular sieves of hierarchical porous structure as carrier described in claim 7.
9. catalyst according to claim 8, it is characterised in that：Born on the LTL molecular sieves with hierarchical porous structure
Carry active metal；
The active metal is selected from following at least one：Pt, Pd and Ir；
The load capacity of the active metal is 0.1~2.0%.
10. application of the catalyst described in claim 8 in alkane aromatization reaction is catalyzed.
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| CN113753911A (en) * | 2021-09-03 | 2021-12-07 | 化学与精细化工广东省实验室 | KL molecular sieve and morphology regulation and synthesis method thereof |
| CN113830783A (en) * | 2021-09-03 | 2021-12-24 | 化学与精细化工广东省实验室 | KL molecular sieve dynamically synthesized by structureless directing agent and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3216789A (en) * | 1962-08-03 | 1965-11-09 | Union Carbide Corp | Crystalline zeolite l |
| CN1669925A (en) * | 2004-03-16 | 2005-09-21 | 中国石油化工股份有限公司 | Preparation method of L zeolite with high silicon aluminum ratio |
| CN103011189A (en) * | 2012-12-17 | 2013-04-03 | 吉林大学 | Microporous-mesoporous molecular sieve containing noble metal, preparation method and application to catalytic reduction of p-nitrophenol |
| CN106395851A (en) * | 2016-08-30 | 2017-02-15 | 中科合成油技术有限公司 | Ba hetero atom-containing LTL molecular sieve as well as preparation method and application thereof |
-
2018
- 2018-01-10 CN CN201810023176.7A patent/CN108033462B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3216789A (en) * | 1962-08-03 | 1965-11-09 | Union Carbide Corp | Crystalline zeolite l |
| CN1669925A (en) * | 2004-03-16 | 2005-09-21 | 中国石油化工股份有限公司 | Preparation method of L zeolite with high silicon aluminum ratio |
| CN103011189A (en) * | 2012-12-17 | 2013-04-03 | 吉林大学 | Microporous-mesoporous molecular sieve containing noble metal, preparation method and application to catalytic reduction of p-nitrophenol |
| CN106395851A (en) * | 2016-08-30 | 2017-02-15 | 中科合成油技术有限公司 | Ba hetero atom-containing LTL molecular sieve as well as preparation method and application thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113753911A (en) * | 2021-09-03 | 2021-12-07 | 化学与精细化工广东省实验室 | KL molecular sieve and morphology regulation and synthesis method thereof |
| CN113830783A (en) * | 2021-09-03 | 2021-12-24 | 化学与精细化工广东省实验室 | KL molecular sieve dynamically synthesized by structureless directing agent and preparation method thereof |
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