CN110156040A - ZSM-5 molecular sieve and preparation method thereof - Google Patents
ZSM-5 molecular sieve and preparation method thereof Download PDFInfo
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- CN110156040A CN110156040A CN201810146999.9A CN201810146999A CN110156040A CN 110156040 A CN110156040 A CN 110156040A CN 201810146999 A CN201810146999 A CN 201810146999A CN 110156040 A CN110156040 A CN 110156040A
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 90
- 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 90
- 238000002360 preparation method Methods 0.000 title claims abstract description 49
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 65
- 239000011541 reaction mixture Substances 0.000 claims abstract description 36
- 239000000654 additive Substances 0.000 claims abstract description 29
- 230000000996 additive effect Effects 0.000 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 28
- 230000032683 aging Effects 0.000 claims abstract description 26
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 26
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000010703 silicon Substances 0.000 claims abstract description 24
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 24
- 238000003756 stirring Methods 0.000 claims abstract description 13
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 10
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 10
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 9
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 9
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 9
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 7
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000001914 filtration Methods 0.000 claims abstract description 3
- 239000000499 gel Substances 0.000 claims description 40
- 238000002425 crystallisation Methods 0.000 claims description 36
- 230000008025 crystallization Effects 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 14
- 229910001868 water Inorganic materials 0.000 claims description 13
- 239000000741 silica gel Substances 0.000 claims description 8
- 229910002027 silica gel Inorganic materials 0.000 claims description 8
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 7
- 235000013024 sodium fluoride Nutrition 0.000 claims description 7
- 239000011775 sodium fluoride Substances 0.000 claims description 7
- -1 template Substances 0.000 claims description 5
- 239000006229 carbon black Substances 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 239000004411 aluminium Substances 0.000 claims description 3
- 235000019353 potassium silicate Nutrition 0.000 claims description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims 1
- 239000011737 fluorine Substances 0.000 claims 1
- 125000001153 fluoro group Chemical group F* 0.000 claims 1
- WNEYXFDRCSFJCU-UHFFFAOYSA-N propan-1-amine;hydrate Chemical compound [OH-].CCC[NH3+] WNEYXFDRCSFJCU-UHFFFAOYSA-N 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 23
- 238000005406 washing Methods 0.000 abstract description 9
- 238000002156 mixing Methods 0.000 abstract description 8
- 239000007790 solid phase Substances 0.000 abstract description 7
- 239000003795 chemical substances by application Substances 0.000 abstract description 5
- 239000013078 crystal Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 9
- 229910021536 Zeolite Inorganic materials 0.000 description 7
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 7
- 239000010457 zeolite Substances 0.000 description 7
- 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 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 229960002050 hydrofluoric acid Drugs 0.000 description 3
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 241000446313 Lamella Species 0.000 description 2
- 230000029936 alkylation Effects 0.000 description 2
- 238000005804 alkylation reaction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000029087 digestion Effects 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- 229910016523 CuKa Inorganic materials 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 244000187656 Eucalyptus cornuta Species 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical group CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 238000005899 aromatization reaction Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- HRHBQGBPZWNGHV-UHFFFAOYSA-N azane;bromomethane Chemical compound N.BrC HRHBQGBPZWNGHV-UHFFFAOYSA-N 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- XJWSAJYUBXQQDR-UHFFFAOYSA-M dodecyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)C XJWSAJYUBXQQDR-UHFFFAOYSA-M 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229940009493 gel-one Drugs 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 239000004530 micro-emulsion Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000003053 piperidines Chemical class 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 230000002123 temporal effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- 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
- C01B39/36—Pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
- C01B39/38—Type ZSM-5
- C01B39/40—Type ZSM-5 using at least one organic template directing agent
-
- C—CHEMISTRY; METALLURGY
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The invention provides a preparation method of a thin plate type ZSM-5 molecular sieve. Mixing a silicon source, an aluminum source, a template agent and an additive in the process of preparing gel, and stirring for 1-20 h at 10-50 ℃; standing and aging for 10-30 h at 10-90 ℃; and (3) putting the prepared gel reaction mixture into a reaction kettle, putting the reaction kettle into an oven, crystallizing for 4-30 h at 100-220 ℃, taking out, filtering, washing and drying to obtain a ZSM-5 molecular sieve product. The ZSM-5 molecular sieve is synthesized under the condition of a similar solid phase, and the obtained ZSM-5 molecular sieve product is in a thin plate shape, has the relative crystallinity of 90-110 percent and is made of SiO2/Al2O3The molar ratio is ≦ 100.
Description
Technical field
The present invention relates under a type solid phase conditions, using additive prepare high-crystallinity, ratio≤100 silica alumina ratio Mo Er,
The preparation method of sheet-type ZSM-5 molecular sieve, belongs to inorganic material and catalyst preparation technical field.
Background technique
ZSM-5 molecular sieve have unique pore structure, heat/hydrothermal stability, high solid it is acid and excellent select type,
It is widely used in the industrial process such as aromatisation, isomerization, alkylation.Modified high silicon is often used in catalytic cracking catalyst
ZSM-5 molecular sieve is aligned in some industrial reactions using the type of selecting of ZSM-5 as the propylene in auxiliary agent increasing production of liquid gas
Substituted alkylbenzene.ZSM-5 molecular sieve, which is also proved to be, acts on clearly effective material to MTP/MTO catalytic reaction.By
ZSM-5 molecular sieve is catalyzed in crystallite dimension and pattern and absorption property influence is very big, to adapt to industrial demand, to ZSM-
The pattern of 5 molecular sieves has done many modifications, and synthesis pattern is that the ZSM-5 molecular sieve of sheet-type comes into being.
Sheet-type ZSM-5 molecular sieve is that the direction growth of a kind of a axis and c-axis is advantageous, and b axis direction (straight hole road) direction is raw
A kind of crystal generated after length is limited.Its b axial thickness is limited in Nano grade, and a and c-axis still keep micron-scale.Such shape
The crystal grain straight hole road of shape is short, and micropore is not easy to plug, and inside diffusional resistance reduces, and activated centre is accessible, and its crystal grain is not easy to roll into a ball
It is poly-.
Lin and Yates synthesizes pure silicon coffin with a corpse in it type i.e. sheet-type ZSM-5 molecule in the microemulsion that CTAB and butanol form
Sieve, it is 20-100 microns a length of, it is 2-10 microns thick.CN 105523569A is described a kind of while being used piperidines, imidazoles, acetic acid
The nitrogenous compounds such as ammonium, ethylenediamine are used as template as additive, n-propylamine, tetrapropylammonium hydroxide, 4-propyl bromide etc.
Agent, fluoride is as mineralizer, under alkaline condition, by the additional proportion for controlling revolving speed, controlling template and additive, closes
At the method for sheet-type ZSM-5 molecular sieve.Obtained reaction gel mixture needs aging 0-120 hours at room temperature,
At a temperature of 60-300 DEG C, under 50-1000rpm stirring condition, crystallization 1-15 days.Gained ZSM-5 molecular sieve is used for butene cracking
Good catalytic effect has been obtained in reaction.But the substance classes added in the preparation of gel reaction mixture are more, and process
It controls finer.One kind is mentioned in CN 106006667A, and dodecyl trimethyl ammonium bromide, cetyl three are added in synthesis
Alkali source is first dissolved in water and matched by methyl bromide ammonium or Cetyltrimethylammonium bromide as amphiphilic cationic surfactant
At solution A, part solution A wiring solution-forming B is added in organic quaternary ammonium salt and silicon source, it is molten by being formed after silicon source addition part solution A
Liquid C, then solution D is formed after solution B and solution C are mixed, surfactant is added in part solution A after stirring and is added
Into solution D, stirring forms reaction mixture.Reaction mixture washs, dries, roasting to the end after hydrothermal crystallizing
ZSM-5 molecular sieve product.The SEM picture of products obtained therefrom is shown as the pattern of nanoscale twins accumulation, and is uniformly distributed, and size is equal
One.Although lamella crystal grain is relatively thick, single lamella is then smaller.Surfactant used in this preparation method is complicated, process
Also troublesome.
The present invention develops under a type solid phase conditions, using additive prepare high-crystallinity, silica alumina ratio Mo Er ratio≤
100, the preparation method of sheet-type ZSM-5 molecular sieve.The additive that the method uses is simple and cheap；It is easy to operate；It synthesized
Institute's water consumption is small in journey, improves the utilization rate of raw material；Not only relative crystallinity is high for the product of synthesis, silica alumina ratio≤100, and shape
Looks are sheet-type.
CN107098358A disclose it is a kind of reduce ZSM-5 molecular sieve aperture method, be by silicon source, additive (A) and
Template (T) wiring solution-forming, is added silicon source after mixing, makes the molar ratio SiO of each component2:Al2O3: T:A:H2O=(40~
400): 1:(10~70): (1~10): (100~1500), be stirred at room temperature uniformly after under the conditions of 100~180 DEG C crystallization 6~
72 hours, crystallization was cooling after the completion, is centrifugated, is drying to obtain product after washing.Method described in this method is that A class is added to add
After adding agent, the ZSM-5 molecular sieve with small crystal grains that controllable aperture reduces can be directly synthesized, it is modified after saving to reduce ZSM-5 molecule
The processing step of mesh size shortens the technical process of catalyst preparation, improves the selective activization of ZSM-5 molecular sieve, is used for first
The fields such as the preparing propylene transformed, benzene alkylation of alcohol optimize ZSM-5 molecular sieve with small crystal grains in the catalytic performance in above-mentioned field.
The present invention plays facilitation to subsequent crystallization process by increasing ageing process.Ensuring product grains pattern
Under the premise of for sheet-type, the stability of synthesis and the crystallization degree of product are improved.
Summary of the invention
The purpose of the present invention is to provide under a type solid phase conditions, high-crystallinity is prepared using additive, silica alumina ratio rubs
The preparation method of Er Bi≤100, sheet-type ZSM-5 molecular sieve.
The present invention provides a kind of preparation method of ZSM-5 molecular sieve, includes the following steps:
(1) gel reaction mixture is prepared:
Additive, silicon source, template are added to the water, is uniformly mixed, adds silicon source, and be uniformly mixed, is stirred；Then
It is still aging, obtain gel reaction mixture；
Al element in above-mentioned material is with Al2O3Meter, Si element is with SiO2Meter, source of aluminium, the silicon source, the template
The dosage of agent, the additive and water makes Al2O3、SiO2, template, additive and H2The molar ratio of O is 0.01~1:1:
0.01~0.06:0.05~0.5:4~10；
(2) ZSM-5 molecular sieve is prepared
The gel reaction mixture is put into reaction kettle, then reaction kettle is put into baking oven, crystallization, using mistake
ZSM-5 molecular sieve product is made in filter, washing, drying steps.
The preparation method of ZSM-5 molecular sieve of the present invention, wherein silicon source described in step (1) preferably be selected from silica solution,
One or more of silica gel, white carbon black and waterglass.
The preparation method of ZSM-5 molecular sieve of the present invention, wherein template is preferably tetrapropyl hydrogen in step (1)
Amine-oxides and/or 4-propyl bromide.
The preparation method of ZSM-5 molecular sieve of the present invention, wherein additive is preferably ammonium fluoride, hydrogen in step (1)
One or more of fluoric acid and sodium fluoride.
The preparation method of ZSM-5 molecular sieve of the present invention, wherein the condition of ageing described in step (1) is preferred are as follows:
At 10~90 DEG C, still aging 10~30h.
The preparation method of ZSM-5 molecular sieve of the present invention, wherein the time of stirring described in step (1) is preferably 1
~20h.
The preparation method of ZSM-5 molecular sieve of the present invention, wherein the condition of crystallization described in step (2) is preferred are as follows:
100~220 DEG C of 4~30h of crystallization.
The preparation method of ZSM-5 molecular sieve of the present invention, wherein by additive, silicon source, template in step (1)
It is added to the water, is uniformly mixed and is preferably carried out under the conditions of 10~50 DEG C.
It is as made from the preparation method of above-mentioned ZSM-5 molecular sieve the present invention also provides a kind of ZSM-5 molecular sieve.
ZSM-5 molecular sieve of the present invention, wherein the pattern of the ZSM-5 molecular sieve is sheet-type, relative crystallinity
90~110%, SiO2/Al2O3Mole Zhi≤100 Bi.
The present invention can also details are as follows:
In order to achieve the above object, this method mainly includes step the present invention provides a kind of preparation method of ZSM-5 molecular sieve
It is rapid:
(1) gel reaction mixture is prepared:
At 10~50 DEG C, additive, silicon source, template are added to the water, are uniformly mixed, silicon source is added, is uniformly mixed,
Stir 1~20h.At 10~90 DEG C, by the still aging 10~30h of gel reaction mixture of preparation；
Al element in above-mentioned material is with Al2O3Meter, Si element is with SiO2Meter, source of aluminium, the silicon source, the template
The dosage of agent, the additive and water makes Al2O3、SiO2, template, additive and H2The molar ratio of O is 0.01~1:1:
0.01~0.06:0.05~0.5:4~10；
(2) ZSM-5 molecular sieve is prepared
The gel reaction mixture of preparation is put into reaction kettle, then reaction kettle is put into baking oven, it is warming up to 100~
220 DEG C of 4~30h of crystallization, using be filtered, washed, drying steps be made ZSM-5 molecular sieve product.
Method of the present invention, wherein the silicon source is preferably selected from silica solution, silica gel, white carbon black, one in waterglass
Kind is a variety of.
Method of the present invention, wherein the template is one of tetrapropylammonium hydroxide, 4-propyl bromide
Or it is a variety of.
Method of the present invention, wherein the additive is ammonium fluoride, ammonium fluoroborate, hydrofluoric acid, one in sodium fluoride
Kind is a variety of.
Method of the present invention, wherein preferred mole of the dosage of silicon source, the additive and water described in step (1)
Ratio is 1:0.05~0.5:4~10.
Method of the present invention, wherein be aged 10~30h after the completion of the preparation of gel reaction mixture in step (1).
In the preparation method of Y molecular sieve of the present invention, the step of not referring in detail such as crystallization temperature, crystallization time and
Being filtered, washed of crystallization product, drying and other steps can be carried out according to the routine operation of fields.Crystallization product in the present invention
Preferably it is dried at 60 DEG C~160 DEG C.
In the preparation method of ZSM-5 molecular sieve provided by the present invention, add mainly in reactant gel preparation process
Enter additive, to inhibit the speed of growth in zeolite crystal a direction.By uniformly mixed reaction mixture gel one
Ageing a period of time is fixed, additive and silicon source, silicon source, template is made to act on forming enough crystallites, to form molecular sieve
Crystal seed is provided.After obtained reaction mixture gel is put into reaction kettle later, then reaction kettle is put into crystallization in baking oven, obtained
Pattern is sheet-type, the ZSM-5 molecular sieve product that crystallization degree is higher, silica alumina ratio is medium.In addition, in synthetic method of the invention
In, reaction mixture gel is prepared under the system of a class solid phase, reduces water, improves the utilization rate of raw material.
Additive uses the crystal morphology for making ZSM-5 molecular sieve product that sheet-type is presented, and does not impact to crystallization degree.
Sheet-type crystal grain has straight hole road short, and micropore is not easy to plug, and inside diffusional resistance reduces, and activated centre is accessible, and its crystal grain
Feature not easy to reunite.Method of the invention can prepare high-crystallinity, silica alumina ratio mole using additive under class solid phase conditions
Bi≤100, sheet-type ZSM-5 molecular sieve.
In the preparation method of ZSM-5 molecular sieve of the present invention, the step of not referring in detail such as crystallization product filtering, wash
It washs, drying and other steps can be carried out according to the routine operation of fields.In the present invention crystallization product preferably 100 DEG C~
160 DEG C are dried.
In conclusion the preparation method of ZSM-5 molecular sieve of the invention has the advantage that
(1) ZSM-5 molecular sieve is prepared under conditions of class solid phase.
(2) additive is used in preparation process, is controlled the speed of growth in some direction of ZSM-5 molecular sieve, is made
ZSM-5 molecular sieve product grains pattern is sheet-type, and does not influence its crystallization degree.
Detailed description of the invention
Fig. 1 is the XRD diagram for the ZSM-5 molecular sieve that embodiment 1 is prepared；
Fig. 2 is the SEM figure for the ZSM-5 molecular sieve that embodiment 1 is prepared；
Fig. 3 is the XRD diagram for the ZSM-5 molecular sieve that comparative example 1 is prepared；
Fig. 4 is the SEM figure for the ZSM-5 molecular sieve that comparative example 1 is prepared；
Fig. 5 is the XRD diagram for the ZSM-5 molecular sieve that comparative example 2 is prepared.
Specific embodiment
Elaborate below to the embodiment of the present invention: the present embodiment carries out under the premise of the technical scheme of the present invention
Implement, gives detailed embodiment and process, but protection scope of the present invention is not limited to following embodiments, following implementation
Test method without specific conditions in example, usually according to normal condition.
The condition of ageing described in step (1):
In the present invention, the condition of ageing described in step (1) is not particularly limited, it is old described in usual step (1)
The condition of change is preferred are as follows: at 10~90 DEG C, still aging 10~30h；
If Aging Temperature is less than 10~90 DEG C, since Aging Temperature is too low, it be easy to cause gel nucleation rate excessively slow, after
Continuous crystallization process slows down；And Aging Temperature is higher than 10~90 DEG C, since Aging Temperature is excessively high, is not much different with crystallization temperature, institute
The crystal grain for obtaining product is larger, and it is excessive to consume energy, and has no other beneficial effects；
If digestion time is less than 10~30h, since digestion time is not enough, it be easy to cause the opposite knot of products obtained therefrom
Brilliant degree is lower；And Aging Temperature is more than 10~30h, due to overlong time, causes temporal waste, reduces combined coefficient, and
The crystallization degree raising of product is not obvious, and has no other beneficial effects.
In each embodiment and comparative example, the measurement of the relative crystallinity of the ZSM-5 zeolite synthesized uses BRUKER D8
ADVANCE (German Bruker) type X-ray diffractometer, experiment condition are as follows: CuKa radiates (0.1541nm), tube voltage 40kV, pipe
Electric current 40mA.The measurement of the silica alumina ratio of the ZSM-5 zeolite synthesized uses Rigaku ZSM100 type Xray fluorescence spectrometer
(XRF).The measurement of the grain morphology of the ZSM-5 zeolite synthesized accelerates electricity using in JSM-6380 type scanning electron microscope
Pressure is 15kV.
And thus calculate silica alumina ratio relative crystallinity measurement be with sample (2 θ) 22.5 °~25 ° diffraction peak areas with
What the percent value of reference (2 θ) 22.5 °~25 ° of diffraction peak areas was calculated.
As the zeolite standard specimen of crystallinity standard from industrial ZSM-5 reference used in embodiment and comparative example
Its crystallinity is set as 100% by sample.
Embodiment 1
The present embodiment provides a kind of preparation methods of ZSM-5 molecular sieve comprising following steps:
Take 1.45g ammonium fluoride (Han Liang≤96.0wt%), it is added in 40.10g deionized water, after to be dissolved, 2.45g is added
Aluminum sulfate (Han Liang≤99.0wt%), 14.61g tetrapropylammonium hydroxide (content 25.0wt%), after mixing, be added
23.67g silica gel (content 94.0wt%), stirs evenly, and gel reaction mixture is made；
By gel reaction mixture under the conditions of 80 DEG C still aging 16h；
Above-mentioned gel reaction mixture is packed into reaction kettle, then reaction kettle is put into baking oven, the crystallization 28h at 140 DEG C
After filter, washing be dried to obtain ZSM-5 molecular sieve.
Resulting ZSM-5 molecular sieve is characterized with XRD technology, obtained XRD diagram is as shown in Figure 1, carry out table with SEM
Sign obtains SEM picture as shown in Fig. 2, the silica alumina ratio for measuring above-mentioned ZSM-5 is 96.7, and relative crystallinity 99%, pattern is thin
Template.
Embodiment 2
The present embodiment provides a kind of preparation methods of ZSM-5 molecular sieve comprising following steps:
Take 9.72g sodium fluoride (Han Liang≤99.0wt%), it is added in 81.00g deionized water, after to be dissolved, 5.01g is added
Aluminum sulfate (Han Liang≤99.0wt%), 9.57g 4-propyl bromide (Han Liang≤99.0wt%), after mixing, be added
47.34g silica gel (content 94.0wt%), stirs evenly, and gel reaction mixture is made；
By gel reaction mixture under the conditions of 50 DEG C it is still aging for 24 hours；
Above-mentioned gel reaction mixture is packed into reaction kettle, then reaction kettle is put into baking oven, the crystallization 20h at 180 DEG C
After filter, washing be dried to obtain ZSM-5 molecular sieve.
Resulting ZSM-5 molecular sieve is characterized with XRD technology, obtained XRD diagram is as shown in figure 3, carry out table with SEM
Sign obtains SEM picture as shown in figure 4, the silica alumina ratio for measuring above-mentioned ZSM-5 is 97.0, and relative crystallinity 104%, pattern is
Sheet-type.
Embodiment 3
The present embodiment provides a kind of preparation methods of ZSM-5 molecular sieve comprising following steps:
Take 7.73g hydrofluoric acid (Han Liang≤40.0wt%), it is added in 79.89g deionized water, after to be dissolved, 4.98g is added
Aluminum sulfate (Han Liang≤99.0wt%), 9.60g 4-propyl bromide (Han Liang≤99.0wt%), after mixing, be added
47.42g white carbon black (content 94.0wt%), stirs evenly, and gel reaction mixture is made；
By gel reaction mixture under the conditions of 60 DEG C still aging 22h；
Above-mentioned gel reaction mixture is packed into reaction kettle, then reaction kettle is put into baking oven, the crystallization 18h at 190 DEG C
After filter, washing be dried to obtain ZSM-5 molecular sieve.
By resulting ZSM-5 molecular sieve with characterizing, the silica alumina ratio for measuring above-mentioned ZSM-5 is 97.4, relative crystallinity
It is 98%, pattern is sheet-type.
Embodiment 4
The present embodiment provides a kind of preparation methods of ZSM-5 molecular sieve comprising following steps:
Take 3.24g sodium fluoride (Han Liang≤99.0wt%), it is added in 34.02g deionized water, after to be dissolved, 1.68g is added
Aluminum sulfate (Han Liang≤99.0wt%), 14.59g tetrapropylammonium hydroxide (content 25.0wt%), after mixing, be added
23.68g silica gel (content 94.0wt%), stirs evenly, and gel reaction mixture is made；
By gel reaction mixture under the conditions of 70 DEG C still aging 20h；
Above-mentioned gel reaction mixture is packed into reaction kettle, then reaction kettle is put into baking oven, the crystallization 14h at 205 DEG C
After filter, washing be dried to obtain ZSM-5 molecular sieve.
By resulting ZSM-5 molecular sieve with characterizing, the silica alumina ratio for measuring above-mentioned ZSM-5 is 96.0, relative crystallinity
It is 101%, pattern is sheet-type.
Embodiment 5
The present embodiment provides a kind of preparation methods of ZSM-5 molecular sieve comprising following steps:
Take 6.49g sodium fluoride (Han Liang≤99.0wt%), it is added in 81.02g deionized water, after to be dissolved, 4.97g is added
Aluminum sulfate (Han Liang≤99.0wt%), 9.57g 4-propyl bromide (Han Liang≤99.0wt%), after mixing, be added
47.35g silica gel (content 94.0wt%), stirs evenly, and gel reaction mixture is made；
By gel reaction mixture under the conditions of 70 DEG C still aging 20h；
Above-mentioned gel reaction mixture is packed into reaction kettle, then reaction kettle is put into baking oven, the crystallization 10h at 220 DEG C
After filter, washing be dried to obtain ZSM-5 molecular sieve.
By resulting ZSM-5 molecular sieve with characterizing, the silica alumina ratio for measuring above-mentioned ZSM-5 is 96.9, relative crystallinity
It is 96%, pattern is sheet-type.
Embodiment 6
The present embodiment provides a kind of preparation methods of ZSM-5 molecular sieve comprising following steps:
Take 2.89g sodium fluoride (Han Liang≤99.0wt%), it is added in 33.77g deionized water, after to be dissolved, 1.68g is added
Aluminum sulfate (Han Liang≤99.0wt%), 9.75g tetrapropylammonium hydroxide (Han Liang≤99.0wt%), after mixing, be added
15.98g silica gel (content 94.0wt%), stirs evenly, and gel reaction mixture is made；
By gel reaction mixture under the conditions of 80 DEG C still aging 20h；
Above-mentioned gel reaction mixture is packed into reaction kettle, then reaction kettle is put into baking oven, crystallization is for 24 hours at 175 DEG C
After filter, washing be dried to obtain ZSM-5 molecular sieve.
By resulting ZSM-5 molecular sieve with characterizing, the silica alumina ratio for measuring above-mentioned ZSM-5 is 97.3, relative crystallinity
It is 100%, pattern is sheet-type.
Comparative example 1
This comparative example provides a kind of method of synthetic ZSM-5 zeolite comprising following steps:
The preparation of reaction gel mixture and used various raw materials and consumptions are the same as embodiment 1.
The difference is that: the additive is not added in gel mixture preparation process.
Aging condition, crystal pattern, crystallization temperature and crystallization time after the completion of reaction gel mixture preparation are the same as real
Apply example 1.
By resulting ZSM-5 molecular sieve with characterizing, the silica alumina ratio for measuring above-mentioned ZSM-5 is 96.8, relative crystallinity
It is 101%, pattern is hexagon.
Comparative example 2
This comparative example provides a kind of method of synthetic ZSM-5 zeolite comprising following steps:
The preparation of reaction gel mixture and used various raw materials and consumptions are the same as embodiment 1.
The difference is that: the not aged direct carry out crystallization of reaction mixture of gel is made.
Crystal pattern, crystallization temperature and crystallization time are the same as embodiment 1 after the completion of reaction gel mixture preparation.
By resulting ZSM-5 molecular sieve with characterizing, the silica alumina ratio for measuring above-mentioned ZSM-5 is 96.2, relative crystallinity
It is 80%, pattern is sheet-type.
Claims (10)
1. a kind of preparation method of ZSM-5 molecular sieve, includes the following steps:
(1) gel reaction mixture is prepared:
Additive, silicon source, template are added to the water, is uniformly mixed, adds silicon source, and be uniformly mixed, is stirred；Then it stands
Ageing, obtains gel reaction mixture；
Al element in above-mentioned material is with Al2O3Meter, Si element is with SiO2Meter, source of aluminium, the silicon source, the template, institute
The dosage for stating additive and water makes Al2O3、SiO2, template, additive and H2The molar ratio of O is 0.01~1:1:0.01
~0.06:0.05~0.5:4~10；
(2) ZSM-5 molecular sieve is prepared
The gel reaction mixture is put into reaction kettle, then reaction kettle is put into baking oven, crystallization, using filtering, wash
It washs, ZSM-5 molecular sieve product is made in drying steps.
2. the preparation method of ZSM-5 molecular sieve according to claim 1, which is characterized in that the choosing of silicon source described in step (1)
From one or more of silica solution, silica gel, white carbon black and waterglass.
3. the preparation method of ZSM-5 molecular sieve according to claim 1, which is characterized in that template is four in step (1)
Propyl ammonium hydroxide and/or 4-propyl bromide.
4. the preparation method of ZSM-5 molecular sieve according to claim 1, which is characterized in that additive is fluorine in step (1)
Change one or more of ammonium, hydrofluoric acid and sodium fluoride.
5. the preparation method of ZSM-5 molecular sieve according to claim 1, which is characterized in that ageing described in step (1)
Condition are as follows: at 10~90 DEG C, still aging 10~30h.
6. the preparation method of ZSM-5 molecular sieve according to claim 1, which is characterized in that stirring described in step (1)
Time is 1~20h.
7. the preparation method of ZSM-5 molecular sieve according to claim 1, which is characterized in that crystallization described in step (2)
Condition are as follows: 100~220 DEG C of 4~30h of crystallization.
8. the preparation method of ZSM-5 molecular sieve according to claim 1, which is characterized in that in step (1) by additive,
Silicon source, template are added to the water, and being uniformly mixed is carried out under the conditions of 10~50 DEG C.
9. a kind of ZSM-5 molecular sieve is made by the preparation method of ZSM-5 molecular sieve according to any one of claims 1 to 8
's.
10. ZSM-5 molecular sieve as claimed in claim 9, which is characterized in that the pattern of the ZSM-5 molecular sieve is sheet-type,
Relative crystallinity 90~110%, SiO2/Al2O3Mole Zhi≤100 Bi.
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| CN114160183A (en) * | 2021-12-20 | 2022-03-11 | 西北师范大学 | Preparation of flaky HZSM-5 molecular sieve catalyst and application of catalyst in preparation of aromatic hydrocarbon by hydrogenation of carbon dioxide |
| CN114426288A (en) * | 2020-10-10 | 2022-05-03 | 中国石油化工股份有限公司 | Low-silicon strip-shaped ZSM-5 molecular sieve and preparation method and application thereof |
| CN114643041A (en) * | 2022-03-11 | 2022-06-21 | 山东大学 | Adsorption catalytic oxidation dual-function material and preparation method and application thereof |
| CN115490243A (en) * | 2022-09-27 | 2022-12-20 | 厦门大学 | Short b-axis HZSM-5 zeolite molecular sieve and preparation method and application thereof |
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| CN115490243A (en) * | 2022-09-27 | 2022-12-20 | 厦门大学 | Short b-axis HZSM-5 zeolite molecular sieve and preparation method and application thereof |
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