CN109126861A - A kind of preparation method for preparing propylene from methanol nanometer accumulation ZSM-5 molecular sieve - Google Patents
A kind of preparation method for preparing propylene from methanol nanometer accumulation ZSM-5 molecular sieve Download PDFInfo
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- CN109126861A CN109126861A CN201811006991.9A CN201811006991A CN109126861A CN 109126861 A CN109126861 A CN 109126861A CN 201811006991 A CN201811006991 A CN 201811006991A CN 109126861 A CN109126861 A CN 109126861A
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 96
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 48
- 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 48
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 title claims abstract description 28
- 238000009825 accumulation Methods 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000002425 crystallisation Methods 0.000 claims abstract description 30
- 230000008025 crystallization Effects 0.000 claims abstract description 30
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 25
- 239000010703 silicon Substances 0.000 claims abstract description 25
- 239000013078 crystal Substances 0.000 claims abstract description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000007788 liquid Substances 0.000 claims abstract description 12
- 239000003513 alkali Substances 0.000 claims abstract description 11
- 229910001868 water Inorganic materials 0.000 claims abstract description 11
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 9
- 238000000926 separation method Methods 0.000 claims abstract description 8
- 239000007787 solid Substances 0.000 claims abstract description 8
- -1 alcohol compound Chemical class 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 6
- 238000009415 formwork Methods 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims abstract description 6
- 239000000843 powder Substances 0.000 claims abstract description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 30
- 239000000377 silicon dioxide Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 12
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 8
- 235000019441 ethanol Nutrition 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 5
- 229910052681 coesite Inorganic materials 0.000 claims description 5
- 229910052593 corundum Inorganic materials 0.000 claims description 5
- 229910052906 cristobalite Inorganic materials 0.000 claims description 5
- 229910052682 stishovite Inorganic materials 0.000 claims description 5
- 229910052905 tridymite Inorganic materials 0.000 claims description 5
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 5
- 229910001593 boehmite Inorganic materials 0.000 claims description 4
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 4
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 4
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 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
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 239000005030 aluminium foil Substances 0.000 claims description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 2
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims description 2
- 239000006229 carbon black Substances 0.000 claims description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 2
- 229920001296 polysiloxane Polymers 0.000 claims description 2
- 235000019353 potassium silicate Nutrition 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 2
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 claims description 2
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 2
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims 2
- 239000005995 Aluminium silicate Substances 0.000 claims 1
- 125000005211 alkyl trimethyl ammonium group Chemical group 0.000 claims 1
- 235000012211 aluminium silicate Nutrition 0.000 claims 1
- 235000019241 carbon black Nutrition 0.000 claims 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims 1
- 235000012239 silicon dioxide Nutrition 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 35
- 238000006243 chemical reaction Methods 0.000 abstract description 18
- 239000003610 charcoal Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 12
- 238000011156 evaluation Methods 0.000 description 10
- 238000009792 diffusion process Methods 0.000 description 9
- 229910052799 carbon Inorganic materials 0.000 description 6
- 238000012512 characterization method Methods 0.000 description 6
- 150000001336 alkenes Chemical class 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- 239000005977 Ethylene Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000010189 synthetic method Methods 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000004939 coking Methods 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 229920000715 Mucilage Polymers 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- QCWMRAKRSCVYNJ-UHFFFAOYSA-N methanol;prop-1-ene Chemical group OC.CC=C QCWMRAKRSCVYNJ-UHFFFAOYSA-N 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- 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
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
-
- 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
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to a kind of preparation methods of nanometer accumulation ZSM-5 molecular sieve for preparing propylene from methanol to form uniform liquid gel by silicon source, alkali source, template, alcohol compound, water according to certain proportion stirring and dissolving；By gel in a kettle in 60-140 DEG C of progress crystallization, crystallization time 12-60h obtains crystal seed；By silicon source, silicon source, NaOH, organic formwork agent, water and crystal seed according to certain proportion stirring and dissolving, uniform gel is formed；By obtained gel in a kettle in 140-200 DEG C of progress crystallization, crystallization time 12-60h, crystallization product after the reaction was completed through separation of solid and liquid, washing, drying, exchange, roasting and etc. obtain molecular screen primary powder；Regulate and control the structure of nanometer accumulation ZSM-5 molecular sieve by changing crystal seed and consumption of template agent, molecular sieve catalyst obtained has the characteristics that high propylene yield and fabulous appearance charcoal ability and service life monocycle is long.
Description
Technical field
The present invention relates to Zeolite synthesis method and technology fields, and in particular to one kind is accumulated for preparing propylene from methanol nanometer
The preparation method of ZSM-5 molecular sieve.
Background technique
Propylene is to be only second to one of most important petrochemical industry base stock of ethylene, and application is extremely extensive.Methanol system third
The key technology of alkene (MTP) technique is MTP catalyst technology first, it is also the difficult point of research and the coke of industry concern simultaneously
Point, having grasped catalyst technology is exactly the core for having grasped technique.ZSM-5 is presently found to preparing propylene by methanol transformation reaction
The highest catalysis material of Propylene Selectivity, but traditional ZSM-5 molecular sieve is limited to pore size (aperture < 1nm), makes macromolecular
Into and diffusion escape that its duct is all relatively difficult, and diffusional resistance is also larger, the quick coking of catalyst, reduce it and use the longevity
Life, thus obviously constrain it and applied in bulky molecular catalysis conversion.
In order to overcome traditional ZSM-5 molecular sieve above shortcomings, people were new using the synthesis of all multi-methods in recent years
ZSM-5 molecular sieve, such as reduce molecular sieve crystallite dimension, exploitation multistage pore canal, but catalysis methanol propylene raising effect
Fruit is unsatisfactory.There are many report of catalyst used by preparing propylene from methanol at present, as United States Patent (USP) US 4440871,
US4079095, Chinese patent CN102380431A, CN101269340A etc., in these patents although the method improves third
Alkene is selective but often along with the increase of ethylene selectivity, does not achieve the effect that improve P/E ratio, not mention in patent
And another main problem of current this poor influence preparing propylene from methanol catalytic performance of catalyst appearance carbon ability, and patent
Although CN105253898A reports the synthetic method of a kind of nanometer of ZSM5 aggregation molecular sieve, but do not provide it in patent
Concrete application in methanol to propylene reaction, the present invention are combined by modulation amount of seed with organic formwork agent CTAB, are used
CTAB, Silicalite-1 crystal seed revulsion be synthesized nanometer accumulation ZSM-5 molecular sieve, with reach improve propene yield and
Catalyst holds carbon ability, extends service life catalyst monocycle.
Summary of the invention
The purpose of the present invention is to provide it is a kind of for preparing propylene from methanol nanometer accumulation ZSM-5 molecular sieve preparation method,
To overcome the problems, such as that it is short with catalyst life that propylene existing in the prior art selects yield low.
For achieving the above object, the invention adopts the following technical scheme:
A kind of preparation method for preparing propylene from methanol nanometer accumulation ZSM-5 molecular sieve, it is characterised in that: the method includes such as
Lower step:
(1) silicon source, alkali source, template, alcohol compound, water are formed into uniform liquid according to certain proportion stirring and dissolving
First gel；
(2) by gained the first gel of liquid in step (1) in a kettle in 60-140 DEG C of progress crystallization, crystallization time 12-
60h obtains crystal seed；
(3) by crystal seed obtained by silicon source, silicon source, alkali source, template, water and step (2) according to certain proportion stirring and dissolving, shape
At uniform second gel；
(4) the second gel for obtaining step (3) is in a kettle in 140-200 DEG C of progress crystallization, crystallization time 12-60h, instead
Crystallization product after the completion of answering obtains molecular screen primary powder through separation of solid and liquid, washing, drying, exchange, calcination steps.
Further, the silicon source in the step (1) and (3) selects solid silicone, silica solution, waterglass, white carbon black, height
One of ridge soil, silicate and ethyl orthosilicate are a variety of.
Further, the alkali source in the step (1) and (3) selects one of sodium hydroxide, potassium hydroxide or a variety of.
Further, the template in the step (1) and (3) selects organic formwork agent, and organic formwork agent selects first
Amine, diethylamine, tetraethylammonium bromide, tetraethyl ammonium hydroxide, 4-propyl bromide, tetrapropylammonium hydroxide, 1,6- hexamethylene diamine,
One of n-butylamine, cetyl trimethylammonium bromide (CTAB) are a variety of.
Further, the alcohol compound in the step (1) selects one of methanol, ethyl alcohol, isopropanol, isobutanol
Or it is a variety of.
Further, the silicon source in the step (3) selects sodium metaaluminate, aluminium hydroxide, aluminum sulfate, aluminum nitrate, chlorination
One of aluminium, aluminium isopropoxide, aluminium foil, boehmite and boehmite are a variety of.
Further, in the step (2), crystallization temperature is 100 DEG C, and crystallization time is 36 h；In the step (4),
180 DEG C of crystallization temperature, crystallization time are 36 h.
Further, in the step (1) and (3), SiO in the template and silicon source of selection2Molar ratio be 1:0.05-
0.2。
Further, in the step (3), by the dosage of silicon source, silicon source and alkali source respectively in terms of its oxide, addition
The molar ratio SiO of each component2: Al2O3: Na2O=0.003-0.01:0.05-0.20:7-20.
Further, in the step (3), the Seed charge is SiO in the silicon source being added2The 1%- of mass fraction
10%。
Research is found: the acidity of molecular sieve affects the intrinsic kinetics process of methanol conversion process in MTP technique.This is
Since conversion of the methanol on ZSM-5 molecular sieve is carried out by cloth youth's acidic site on ZSM-5, Campbell etc. uses FTIR
It has studied methanol after the adsorbed state inside molecular sieve with C NMR to point out, the methanol being only adsorbed on skeleton Al can just be sent out
Raw further reaction.Therefore, when methanol converts on ZSM-5, the number and intensity of cloth youth's acidic site will be distributed product
Generate apparent influence.A large number of studies show that reducing acidity of catalyst site concentration, alkene wear rate can be reduced, so that
Low-carbon alkene overall selectivity increases.The diffusion of molecular sieve is mainly influenced by particle size.ZSM-5 molecular sieve granularity subtracts
It is small while increasing molecular sieve specific surface area, pore volume, produce more open hole, effectively shorten product molecule and urging
Diffusion path in agent duct reduces secondary response odds, so that the choosing of the Primary products such as propylene, butylene
Selecting property significantly improves, and the coking deactivation rate of catalyst substantially reduces.And ZSM-5 molecular sieve is a kind of with unique topological structure
Ten-ring molecular sieve, it includes two channel systems: being parallel to the straight hole road of b axis direction, (aperture is distributed in (010) crystal face
On) and be parallel to the sinusoidal duct of a axis direction (aperture is distributed on (100) crystal face).Molecule can in catalytic reaction process
Catalysis reaction and separation are realized inside molecular sieve crystal to pass in and out by straight hole road and sinusoidal duct.But by space configuration control
System, reactant molecule will be far longer than the diffusion velocity in sinusoidal duct in the diffusion velocity in straight hole road.And with the external world
The quantity in the straight hole road aperture communicated depends on the ratio of (010) crystal face of ZSM-5 molecular sieve plane of crystal exposure, and expose
(010) ratio of crystal face depends on the pattern of ZSM-5 molecular sieve.Therefore, the diffusion of ZSM-5 molecular sieve also has with its pattern
It closes.And nano molecular sieve is due to biggish external surface area, shorter micropore canals, the conversion capability for improving catalyst,
Diffusion, the enhancing catalyst anti-carbon deposit deactivation etc. for improving molecule show significant advantage.
Technical effect obtained by the present invention are as follows:
The nanometer packed structures ZSM-5 molecular sieve that the present invention uses CTAB, Silicalite-1 crystal seed revulsion directly to prepare,
Have the characteristics that it is abundant it is transgranular it is mesoporous, relative crystallinity is high, specific surface area and external surface area are big, both had both conventional molecular
The acidity and hydrothermal stability of sieve, also improve the diffusion of molecular sieve, and the shortening of micropore canals distance increases molecule
Diffusion velocity reduces the generation of secondary response, substantially increases Propylene Selectivity, transgranular mesoporous increase to improve.Greatly
The appearance carbon ability for improving nano molecular sieve greatly improves the service life of catalyst to reduce the speed of catalyst carbon deposition.
Detailed description of the invention
Fig. 1 is the SEM result figure of sample in comparative example of the present invention；
Fig. 2 is the SEM result figure of sample in the embodiment of the present invention 1；
Fig. 3 is the SEM result figure of sample in the embodiment of the present invention 2；
Fig. 4 is the SEM result figure of sample in the embodiment of the present invention 3；
Fig. 5 is the SEM result figure of sample in the embodiment of the present invention 4；
Fig. 6 is the SEM result figure of sample in the embodiment of the present invention 5；
Fig. 7 is the life assessment figure of comparative example catalyst of the present invention；
Fig. 8 is the life assessment figure of 2 catalyst of the embodiment of the present invention.
Specific embodiment
Below with reference to specific example, invention is further explained, but the present invention is not limited to following examples.
It is raw materials used in embodiment to be described below:
Step (1) to (2) described crystal seed, synthetic method are as follows: 0.52g sodium hydroxide, 12g silica solution, 11gTPAOH are dissolved in
In 15g deionized water, 10g ethyl alcohol is added, gel is fitted into crystallizing kettle after mixing evenly, 36 h of crystallization at 100 DEG C, it is brilliant
Product natural cooling after change obtains crystal seed；
Step (3)-(4) described product, synthetic method are as follows: 0.52g sodium hydroxide, 12g silica solution, 0.06g aluminum sulfate is molten
In 15g deionized water, 0.5gCTAB and 3% step (2) obtained crystal seed (mass fraction) is then added, will coagulate after mixing evenly
Mucilage binding enters in crystallizing kettle, and 36 h of crystallization obtains molecular screen primary through separation of solid and liquid, washing, drying, exchange, roasting at 180 DEG C
Powder；
Evaluating catalyst: molecular sieve tabletting is sized to 20-40 mesh, and is checked and rated in fixed-bed micro-reactor, reaction condition
For first alcohol and water mixed feeding, the mass ratio of loaded catalyst 0.4g, water and methanol are 1:1,475 DEG C of reaction temperature, are adopted
Product is analyzed with gas-chromatography fid detector, chromatographic column selects Poraplot Q capillary column.
Comparative example: using 30% silica solution as silicon source, aluminum sulfate is silicon source, and sodium hydroxide is alkali source, and template selects 25%
TPAOH, according to Al2O3: SiO2: template: Na2O:H2The ratio of O=1:300:30:20:3000 prepares gel, is put into polytetrafluoro
In the reaction kettle of ethylene liner, crystallization 36h under the conditions of 180 DEG C, crystallization is handed over after completing through separation of solid and liquid, washing, drying, acid
It changes, roast the ZSM-5 sieve sample for obtaining silica alumina ratio as 1:200, the SEM the result is shown in Figure 1 of comparative example is catalyzed it
Agent performance evaluation, primary product distribution are shown in Table 1, and catalyst BET characterization result is shown in Table 2, and catalyst life evaluation result is shown in attached drawing
7。
Embodiment 1: using 30% silica solution as silicon source, aluminum sulfate is silicon source, and sodium hydroxide is alkali source, and template is selected
Crystal seed (mass fraction) obtained by step (2) is added according to Al in CTAB2O3: SiO2: template: Na2O:H2O=1:300:60:20:
3000 proportion prepares gel, is put into the reaction kettle of polytetrafluoroethyllining lining, crystallization 36h under the conditions of 180 DEG C, and crystallization is complete
Cheng Houjing is separated by solid-liquid separation, washing, dry, acid exchanges, roasting obtains the ZSM-5 sieve sample that silica alumina ratio is 200, embodiment 1
SEM result see Fig. 2, carry out catalyst performance evaluation to it, and keep evaluation condition identical with comparative example, primary product divides
Cloth is shown in Table 1, and catalyst BET characterization result is shown in Table 2.
Embodiment 2: in addition to Seed charge increases to 5%, remaining condition is same as Example 1, the embodiment 2 of acquisition
The SEM result of ZSM-5 molecular sieve sample see Fig. 3, catalyst performance evaluation is carried out to it, and keep identical with comparative example and comment
Valence condition, primary product distribution are shown in Table 1, and catalyst BET characterization result is shown in Table 2, and catalyst life evaluation result is shown in attached drawing 8.
Embodiment 3: in addition to Seed charge increases to 8%, remaining condition is same as Example 1, the embodiment 3 of acquisition
The SEM result of ZSM-5 molecular sieve sample see Fig. 4, catalyst performance evaluation is carried out to it, and keep identical with comparative example and comment
Valence condition, primary product distribution are shown in Table 1, and catalyst BET characterization result is shown in Table 2.
Embodiment 4: modulation template CTAB dosage, according to Al2O3: SiO2: template: Na2O:H2O=1:300:45:20:
3000 proportions prepare gel, and crystal seed obtained by step (2) is added, is put into polytetrafluoro liner reaction kettle, brilliant under the conditions of 180 DEG C
Change 36h, crystallization exchanges through separation of solid and liquid, washing, drying, acid after completing, roasts the embodiment 4 for obtaining that silica alumina ratio is 300
The SEM result of ZSM-5 sieve sample is shown in Fig. 5, catalyst performance evaluation is carried out to it, and keep identical with comparative example and comment
Valence condition, primary product distribution are shown in Table 1, and catalyst BET characterization result is shown in Table 2.
Embodiment 5: modulation template CTAB dosage, according to Al2O3: SiO2: template: Na2O:H2O=1:300:30:20:
3000 proportions prepare gel, and other conditions are same as Example 4, and the SEM result for obtaining the sieve sample of embodiment 5 is shown in Fig. 6,
Catalyst performance evaluation is carried out to it, and keeps evaluation condition identical with comparative example, and primary product distribution is shown in Table 1, catalyst
BET characterization result is shown in Table 2.
From in Fig. 1-6 as can be seen that comparative example use conventional method to synthesize ZSM-5 molecular sieve for mono-crystalline structures,
Grain size is in 500-1000nm, and it is small for being can be seen that in Fig. 2-6 using the ZSM-5 molecular sieve that crystal seed revulsion synthesizes
Particle nanocrystal is accumulated, and granular size is in 500nm or so.
It can be seen that from the comparison of Fig. 7 and Fig. 8 and utilize present invention nanometer accumulation molecular sieve obtained for methanol system third
In alkene reaction, in 600h, conversion ratio still keeps 99 or more, and conversion ratio has the trend of being decreased obviously in comparative example.
Table 1 reacts primary product data (quality %)
| Sample | Comparative example | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 |
| Methanol conversion (%) | 99.1 | 99.6 | 99.9 | 99.9 | 99.9 | 99.9 |
| Propylene Selectivity | 38.3 | 44.6 | 45.8 | 44.3 | 45.3 | 43.2 |
| Ethylene selectivity | 8.4 | 6.3 | 5.8 | 5.7 | 6.1 | 6.4 |
| P/E ratio | 4.56 | 7.08 | 7.90 | 7.78 | 7.43 | 6.75 |
It can be seen from the data in Table 1 that the nanometer accumulation molecular sieve synthesized using the method for the present invention is anti-for preparing propylene from methanol
Ying Zhong has the characteristics of high Propylene Selectivity and high P/E ratio.
2 catalyst BET characterize data of table
It can be seen from the data in Table 2 that the nanometer accumulation molecular sieve using the synthesis of crystal seed revulsion all has transgranular Jie abundant
Hole, so as to shorten micropore canals, and mesoporous quantity increases the appearance charcoal ability for also substantially increasing catalyst, extends catalyst
Single pass life.
Finally, it should be noted that above embodiments are only to illustrate the present invention and not limit technology described in the invention
Scheme, therefore, although this specification is referring to above-mentioned each embodiment, the present invention has been described in detail, this
Field it is to be appreciated by one skilled in the art that still can modify to the present invention or equivalent replacement, and all do not depart from this
The technical solution and its improvement of the spirit and scope of invention, should all cover within the scope of the claims of the present invention.
Claims (10)
1. a kind of preparation method for preparing propylene from methanol nanometer accumulation ZSM-5 molecular sieve, it is characterised in that: the method includes
Following steps:
(1) silicon source, alkali source, template, alcohol compound, water are formed into uniform liquid according to certain proportion stirring and dissolving
First gel；
(2) by gained the first gel of liquid in step (1) in a kettle in 60-140 DEG C of progress crystallization, crystallization time 12-
60h obtains crystal seed；
(3) by crystal seed obtained by silicon source, silicon source, alkali source, template, water and step (2) according to certain proportion stirring and dissolving, shape
At uniform second gel；
(4) the second gel for obtaining step (3) is in a kettle in 140-200 DEG C of progress crystallization, crystallization time 12-60h, instead
Crystallization product after the completion of answering obtains molecular screen primary powder through separation of solid and liquid, washing, drying, exchange, calcination steps.
2. a kind of preparation method for preparing propylene from methanol nanometer accumulation ZSM-5 molecular sieve according to claim 1, special
Sign is: the silicon source in the step (1) and (3) selects solid silicone, silica solution, waterglass, white carbon black, kaolin, silicic acid
One of salt and ethyl orthosilicate are a variety of.
3. a kind of preparation method for preparing propylene from methanol nanometer accumulation ZSM-5 molecular sieve according to claim 1, special
Sign is: the alkali source in the step (1) and (3) selects one of sodium hydroxide, potassium hydroxide or a variety of.
4. a kind of preparation method for preparing propylene from methanol nanometer accumulation ZSM-5 molecular sieve according to claim 1, special
Sign is: template in the step (1) and (3) selects organic formwork agent, and organic formwork agent select methylamine, diethylamine,
Tetraethylammonium bromide, tetraethyl ammonium hydroxide, 4-propyl bromide, tetrapropylammonium hydroxide, 1,6- hexamethylene diamine, n-butylamine, ten
One of six alkyl trimethyl ammonium bromides (CTAB) are a variety of.
5. a kind of preparation method for preparing propylene from methanol nanometer accumulation ZSM-5 molecular sieve according to claim 1, special
Sign is: the alcohol compound in the step (1) selects one of methanol, ethyl alcohol, isopropanol, isobutanol or a variety of.
6. a kind of preparation method for preparing propylene from methanol nanometer accumulation ZSM-5 molecular sieve according to claim 1, special
Sign is: the silicon source in the step (3) selects sodium metaaluminate, aluminium hydroxide, aluminum sulfate, aluminum nitrate, aluminium chloride, isopropanol
One of aluminium, aluminium foil, boehmite and boehmite are a variety of.
7. a kind of preparation method for preparing propylene from methanol nanometer accumulation ZSM-5 molecular sieve according to claim 1, special
Sign is: in the step (2), crystallization temperature is 100 DEG C, and crystallization time is 36 h；In the step (4), crystallization temperature
180 DEG C, crystallization time be 36 h.
8. a kind of preparation method for preparing propylene from methanol nanometer accumulation ZSM-5 molecular sieve according to claim 1, special
Sign is: in the step (1) and (3), SiO in the template and silicon source of selection2Molar ratio be 1:0.05-0.2.
9. a kind of preparation method for preparing propylene from methanol nanometer accumulation ZSM-5 molecular sieve according to claim 1, special
Sign is: in the step (3), by the dosage of silicon source, silicon source and alkali source respectively in terms of its oxide, each component of addition rubs
You compare SiO2: Al2O3: Na2O=0.003-0.01:0.05-0.20:7-20.
10. a kind of preparation method for preparing propylene from methanol nanometer accumulation ZSM-5 molecular sieve according to claim 1,
Be characterized in that: in the step (3), the Seed charge is SiO in the silicon source being added2The 1%-10% of mass fraction.
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