CN104098107B - Preparation method of the B-Al-ZSM-11 zeolite catalyst and application thereof - Google Patents
Preparation method of the B-Al-ZSM-11 zeolite catalyst and application thereof Download PDFInfo
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- CN104098107B CN104098107B CN201410322401.9A CN201410322401A CN104098107B CN 104098107 B CN104098107 B CN 104098107B CN 201410322401 A CN201410322401 A CN 201410322401A CN 104098107 B CN104098107 B CN 104098107B
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- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 28
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 239000010457 zeolite Substances 0.000 title claims abstract description 28
- 239000003054 catalyst Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 47
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 45
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 45
- 239000010703 silicon Substances 0.000 claims abstract description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 37
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 27
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 27
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052796 boron Inorganic materials 0.000 claims abstract description 26
- 239000003513 alkali Substances 0.000 claims abstract description 23
- 238000002425 crystallisation Methods 0.000 claims abstract description 22
- 230000008025 crystallization Effects 0.000 claims abstract description 22
- 229910017053 inorganic salt Inorganic materials 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 239000002253 acid Substances 0.000 claims abstract description 9
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 5
- 239000004411 aluminium Substances 0.000 claims abstract description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 65
- 238000003756 stirring Methods 0.000 claims description 36
- 239000004327 boric acid Substances 0.000 claims description 25
- 239000007864 aqueous solution Substances 0.000 claims description 23
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 15
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 13
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims description 11
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 9
- 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 8
- 238000003786 synthesis reaction Methods 0.000 claims description 7
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- 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 5
- 239000000243 solution Substances 0.000 claims description 5
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical group [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 125000005619 boric acid group Chemical group 0.000 claims description 4
- 238000006555 catalytic reaction Methods 0.000 claims description 4
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 3
- 239000004115 Sodium Silicate Substances 0.000 claims description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical group CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 3
- 229910021538 borax Inorganic materials 0.000 claims description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 3
- QCWMRAKRSCVYNJ-UHFFFAOYSA-N methanol;prop-1-ene Chemical group OC.CC=C QCWMRAKRSCVYNJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000011707 mineral Substances 0.000 claims description 3
- 238000000465 moulding Methods 0.000 claims description 3
- 150000003839 salts Chemical class 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
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 3
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 3
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 238000002242 deionisation method Methods 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 238000005554 pickling Methods 0.000 claims description 2
- 239000001117 sulphuric acid Substances 0.000 claims description 2
- 235000011149 sulphuric acid Nutrition 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 13
- 238000005406 washing Methods 0.000 abstract description 13
- 238000000034 method Methods 0.000 abstract description 6
- 239000002808 molecular sieve Substances 0.000 abstract description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 abstract description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract 1
- 239000005977 Ethylene Substances 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 238000001914 filtration Methods 0.000 abstract 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 23
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 21
- 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 description 7
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 7
- 239000011734 sodium Substances 0.000 description 7
- 229910052708 sodium Inorganic materials 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 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
- -1 silicon boron aluminum Chemical compound 0.000 description 3
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000004230 steam cracking Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- 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
-
- 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
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
-
- 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
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/40—Ethylene production
Landscapes
- Catalysts (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a B-Al-ZSM-11 zeolite catalyst in the methanol to propylene reaction and a preparation method of the B-Al-ZSM-11 zeolite catalyst. In the invention, the method includes the following steps: a boron source, an aluminium source, a silicon source, an alkali source, an inorganic salt, a template and water are used as raw materials; the raw materials are subjected to crystallization, filtration, washing, drying and roasting; the ZSM-11 zeolite simultaneously containing boron, aluminium and silicon in the skeleton is synthesized by one step. The synthetic process is simple, the degree of crystallinity of the product is high, the content of skeleton boron and aluminium can be adjusted, and the acid strength of a molecular sieve can be effectively controlled; the B-Al-ZSM-11 zeolite synthesized by the method can be used for catalyzing the methanol to propylene reaction, and is higher in propylene selectivity and product P/E ratio (molar ratio of propylene to ethylene in the product) compared with B-Al-ZSM-5 or ZSM-11.
Description
Technical field
The invention belongs to inorganic chemical synthesis technical field, it is related to a kind of silicon boron aluminum zeolite catalyst and preparation method thereof,
A kind of specifically related to b-al-zsm-11 zeolite catalyst for preparing propylene from methanol reaction and preparation method thereof.
Background technology
Propylene, as a kind of important industrial chemicals, is widely used in the chemical products such as polypropylene, expoxy propane, acrylonitrile
Production process in.Propylene is mainly obtained through steam cracking or catalytic cracking by petroleum at present, and its price is subject to oil price
Impact.The continuous minimizing of petroleum resources reserves and the growing propylene market demand make to develop the propylene life being independent of oil
Production. art becomes required.Preparing propylene from methanol (mtp) technology because the coal of its available rich reserves or natural gas are through preparing propylene from methanol,
Receive more and more attention.
The dominant catalyst of preparing propylene from methanol reaction at present is zsm-5 zeolite molecular sieve.Research shows, weaker acid strength
Favourable with prolongation catalyst life to improving Propylene Selectivity with preferable duct diffusivity.Xu Hualong et al. is using having relatively
The boracic zsm-5 zeolite of weak acid intensity, as catalyst, makes the medium acid strength of molecular sieve surface and the ratio of strong acidic site obtain
Effectively control, the life-span of catalyst is greatly improved.Francesca bleken et al. compares zsm-5 and zsm-11 etc.
Catalytic performance in methanol hydrocarbon reaction for the catalyst, result shows, compared with zsm-5, comprises only straight hole road in crystal
Zsm-11 shows preferable catalyst stability.
In sum, synthesize b-al-zsm-11, adjust acid strength and the pore passage structure of catalyst simultaneously, and be allowed to produce
Synergism, creates the more preferable catalytic effect than common zsm-11 or b-al-zsm-5, and it is anti-to use it for preparing propylene from methanol
Should, will have very important significance.However, the document of synthesis b-al-zsm-11 is less at present, use it for preparing propylene from methanol
There is not been reported for reaction.
Content of the invention
In place of solving the deficiencies in the prior art, the technical solution used in the present invention is:
A kind of preparation method of b-al-zsm-11 zeolite catalyst, comprises the steps:
Under room temperature, alkali source is added in the mixed solution of template, silicon source and water, stirs 1-3h, add silicon source, boron source
With the mixed aqueous solution of inorganic salt, load after continuing stirring 1-3h in crystallizing kettle, crystallization 3 days at 160 DEG C, filter, deionization
Water washing, after 6-12 hour being dried in 100-120 DEG C, in 540-580 DEG C of roasting 1-6 hour, obtains b-al-zsm-11 zeolite；
Described, alkali source is selected from TBAH or sodium hydroxide；
Described silicon source is tetraethyl orthosilicate or Ludox or sodium silicate or white carbon；
Source of aluminium is aluminum isopropylate. or aluminum sulfate or sodium aluminate；
Described boron source is boric acid or sodium borate；
Described template is TBAH or tetrabutyl ammonium bromide；
With the molar ratio computing of pure material, sio in silicon source2: the b in boron source2o3: al in silicon source2o3: the tba in template+∶
Oh in alkali source-: inorganic salt: h2O=1: 0.005-0.2: 0.0005-0.01: 0.05-0.6: 0.05-0.6: 0-0.6: 10-
100；
Described, crystallization temperature is 80-170 DEG C, and crystallization time is 1-5d.
Preferably alkali source is sodium hydroxide, and sodium hydroxide is cheap and easy to get.
Preferably silicon source is Ludox, and the plastic process of Ludox is easier to control.
Preferably silicon source is aluminum sulfate, and aluminum sulfate is cheap and easy to get, and dissolubility is good.
Preferably boron source is boric acid, and boric acid is cheap and easy to get, easily hydrolyzes.
Preferably template is tetrabutyl ammonium bromide, will not change the ph value of solution, cheap and easy to get, and the ph value of system can shadow
Ring the crystallization process to zeolite, for certain zeolite, beyond suitable ph value, product will be cannot get.
Preferably, sio in silicon source2: the b in boron source2o3: al in silicon source2o3: the tba in template+: the oh in alkali source-∶
Inorganic salt: 1: 0.2: 0.00083: 0.18: 0.19: 0: 30.6, under this material ratio, most useful for sol-gel process, and
Crystallization afterwards.
A kind of purposes of b-al-zsm-11 zeolite, uses it for the reaction of catalysis methanol propylene, wherein, by the b- of synthesis
Al-zsm-11 zeolite uses aluminium oxide extruded moulding, exchanges 3 times through 0.4m aqueous ammonium nitrate solution room temperature, using 2m mineral acid
It is used for preparing propylene from methanol after washing to react, described mineral acid is hydrochloric acid or sulphuric acid or nitric acid or phosphoric acid.
The preparation method of the present invention, with the molar ratio computing of pure material, sio in silicon source2: the b in boron source2o3: al in silicon source2o3
: the tba in template+: the oh in alkali source-: inorganic salt: h2O=1: 0.005-0.2: 0.0005-0.01: 0.05-0.6: 0.05-
0.6∶0-0.6∶10-100；Why limit above-mentioned mol ratio, be because that material molar ratio both can ensure that conjunction within this range
Become out b-al-zsm-11 zeolite, do not result in waste again.
In above-mentioned preparation process, crystallization temperature is 80-170 DEG C, and crystallization time is 1-5d.Too high or too low for temperature, the time
The long or too short degree of crystallinity that all will affect sample.
In sum, advantages of the present invention is: compared with prior art, the present invention has taken into full account acidity of catalyst and hole
The impact to reactivity worth for the road structure, while controlling acid site, improves the diffusion in duct, makes propylene faster from hole
Diffuse out in road, slow down propylene and side reaction is occurred further on strong acid center, there is higher Propylene Selectivity and product
Thing p/e ratio.
In addition, the present invention also has synthesis technique simply, reaction system is simultaneously introduced boron source and silicon source, effectively adjusts
Save catalyst strong acid center and the content at weak acid center, while ensureing that reaction is carried out, slow down propylene and enter in duct
There is side reaction in one step, have higher Propylene Selectivity and product p/e ratio.By the b-al-zsm-11 boiling synthesized by the present invention
Stone is used for catalysis methanol synthesis propylene reaction, compared with b-al-zsm-5 or zsm-11, has higher Propylene Selectivity and product
Thing p/e ratio.
Brief description
Fig. 1 is the xrd collection of illustrative plates of the b-al-zsm-11 zeolite of embodiment 1 synthesis；
Fig. 2 is the sem picture of embodiment 1 sample；
Fig. 3 is embodiment 1, the result of comparative example 1 and the reaction of comparative example 2 sample catalysis methanol propylene, its reaction condition
For: reaction temperature: 500 DEG C, reaction pressure: normal pressure, methanol quality air speed: 1h-1, the mol ratio of water and methanol in reactant: 1:
1.
Specific embodiment
Embodiment 1
Under room temperature, 126.2g tetrabutyl ammonium bromide and 439.2g Ludox (30wt%) are dissolved in 100ml water；Stirring feelings
Under condition, Deca sodium hydrate aqueous solution (16.4g sodium hydroxide+200ml water) thereto, stirs 1 hour, adds boric acid and aluminic acid
The aqueous solution (54.4g boric acid+0.3g sodium aluminate+602ml water) of sodium continues to stir 1 hour afterwards, dress kettle, crystallization 3 days at 160 DEG C,
Filter, washing, 100 DEG C are dried overnight, and obtain b-al-zsm-11 after 540 DEG C of roasting 6h.Raw materials used, with pure material mole
Ratio meter, sio in silicon source2: the b in boron source2o3: al in silicon source2o3: the tba in template+: the oh in alkali source-: inorganic salt: h2O=
1∶0.2∶0.00083∶0.18∶0.19∶0∶30.6.
Fig. 1 is the xrd collection of illustrative plates of sample, and as can be seen from the figure sample has mel structure；
Fig. 2 is the sem picture of sample, and as can be seen from the figure sample is little crystal grain aggregate.
Embodiment 2
Under room temperature, 86g tetrabutyl ammonium bromide and 330.4g Ludox (30wt%) are dissolved in 400ml water；Stirring state
Under, Deca sodium hydrate aqueous solution (10.6g sodium hydroxide+200ml water) thereto, stirs 3 hours, adds boric acid and sodium aluminate
Aqueous solution (41.6g boric acid+0.48g aluminum sulfate+58g sodium chloride+500ml water) afterwards continue stirring 3 hours, fill kettle, at 160 DEG C
Crystallization 3 days, filters, washing, and 100 DEG C are dried overnight, and obtain b-al-zsm-11 after 580 DEG C of roasting 1h.Raw materials used, with pure thing
The molar ratio computing of matter, sio in silicon source2: the b in boron source2o3: al in silicon source2o3: the tba in template+: the oh in alkali source-: no
Machine salt: h2O=1: 0.2: 0.00083: 0.16: 0.16: 0.6: 44.8.
Embodiment 3
Under room temperature, 35.1g tetrabutyl ammonium bromide and 131.8g white carbon are dissolved in 200ml water；Under stirring state, Xiang Qi
Middle Deca sodium hydrate aqueous solution (8.6g sodium hydroxide+100ml water), stirs 2 hours, adds the aqueous solution of boric acid and sodium aluminate
(2.1g sodium borate+0.18g sodium aluminate+95ml water) continues stirring 2 hours afterwards, fills kettle, crystallization 3 days at 160 DEG C, filters, washing,
100 DEG C are dried overnight, and obtain b-al-zsm-11 after 560 DEG C of roasting 3h.Raw materials used, with the molar ratio computing of pure material, in silicon source
sio2: the b in boron source2o3: al in silicon source2o3: the tba in template+: the oh in alkali source-: inorganic salt: h2O=1: 0.005:
0.0005∶0.05∶0.1∶0∶10.
Embodiment 4
Under room temperature, 420.7g tetrabutyl ammonium bromide and 268g sodium silicate are dissolved in 1753ml water；Under stirring state, Xiang Qi
Middle Deca sodium hydrate aqueous solution (4.3g sodium hydroxide+200ml water), stirs 2 hours, adds the aqueous solution of boric acid and sodium aluminate
(54.4g boric acid+2.84g aluminum sulfate+48.8g ammonium fluoride+2000ml water) continues stirring 2 hours afterwards, fills kettle, crystallization 3 at 160 DEG C
My god, filter, washing, 100 DEG C are dried overnight, and obtain b-al-zsm-11 after 540 DEG C of roasting 6h.Raw materials used, rubbing with pure material
You count ratio, sio in silicon source2: the b in boron source2o3: al in silicon source2o3: the tba in template+: the oh in alkali source-: inorganic salt: h2o
=1: 0.2: 0.01: 0.6: 0.05: 0.6: 100.
Embodiment 5
Under room temperature, 126.2g tetrabutyl ammonium bromide and 439.2g Ludox (30wt%) are dissolved in 100ml water；Stirring feelings
Under condition, Deca sodium hydrate aqueous solution (51.8g sodium hydroxide+464ml water) thereto, stirs 2 hours, adds boric acid and aluminic acid
The aqueous solution (54.4g boric acid+2.84g aluminum sulfate+48.8g ammonium fluoride+1500ml water) of sodium continues stirring 2 hours afterwards, fills kettle,
Crystallization 3 days at 160 DEG C, filter, washing, and 100 DEG C are dried overnight, and obtain b-al-zsm-11 after 540 DEG C of roasting 6h.It is raw materials used,
With the molar ratio computing of pure material, sio in silicon source2: the b in boron source2o3: al in silicon source2o3: the tba in template+: in alkali source
oh-: inorganic salt: h2O=1: 0.2: 0.01: 0.18: 0.6: 0.6: 60.
Embodiment 6
Under room temperature, 126.2g tetrabutyl ammonium bromide and 439.2g Ludox (30wt%) are dissolved in 100ml water；Stirring feelings
Under condition, Deca sodium hydrate aqueous solution (16.4g sodium hydroxide+200ml water) thereto, stirs 2 hours, adds boric acid and aluminic acid
The aqueous solution (54.4g boric acid+0.3g sodium aluminate+602ml water) of sodium continues to stir 2 hours afterwards, dress kettle, crystallization 3 days at 160 DEG C,
Filter, washing, 100 DEG C are dried overnight, and obtain b-al-zsm-11 after 540 DEG C of roasting 6h.Raw materials used, with pure material mole
Ratio meter, sio in silicon source2: the b in boron source2o3: al in silicon source2o3: the tba in template+: the oh in alkali source-: inorganic salt: h2O=
1∶0.2∶0.00083∶0.18∶0.19∶0∶30.6.
Embodiment 7
Under room temperature, 126.2g tetrabutyl ammonium bromide and 439.2g Ludox (30wt%) are dissolved in 100ml water；Stirring feelings
Under condition, Deca sodium hydrate aqueous solution (16.4g sodium hydroxide+200ml water) thereto, stirs 2 hours, adds boric acid and aluminic acid
The aqueous solution (27.2g boric acid+0.3g sodium aluminate+16.4g potassium chloride+602ml water) of sodium continues to stir 2 hours afterwards, dress kettle, and 170
Crystallization 1 day at DEG C, filters, washing, and 100 DEG C are dried overnight, and obtain b-al-zsm-11 after 540 DEG C of roasting 6h.Raw materials used, with
The molar ratio computing of pure material, sio in silicon source2: the b in boron source2o3: al in silicon source2o3: the tba in template+: the oh in alkali source-
: inorganic salt: h2O=1: 0.1: 0.00083: 0.18: 0.19: 0.1: 30.6.
Embodiment 8
Under room temperature, 126.2g tetrabutyl ammonium bromide and 439.2g Ludox (30wt%) are dissolved in 100ml water；Stirring feelings
Under condition, Deca sodium hydrate aqueous solution (16.4g sodium hydroxide+200ml water) thereto, stirs 2 hours, adds boric acid and aluminic acid
The aqueous solution (54.4g boric acid+0.3g sodium aluminate+9.22g ammonium fluoride+602ml water) of sodium continues to stir 2 hours afterwards, dress kettle, 80 DEG C
Lower crystallization 5 days, filters, washing, and 100 DEG C are dried overnight, and obtain b-al-zsm-11 after 540 DEG C of roasting 6h.Raw materials used, with pure
The molar ratio computing of material, sio in silicon source2: the b in boron source2o3: al in silicon source2o3: the tba in template+: the oh in alkali source-∶
Inorganic salt: h2O=1: 0.2: 0.00083: 0.18: 0.19: 0.1: 30.6.
Embodiment 9
Under room temperature, 456g TBAH (25wt%) and 457g tetraethyl orthosilicate are mixed with 81ml water, stir 3
Hour, add boric acid and the aqueous solution (2.72g boric acid+0.45g aluminum isopropylate .+1000ml water) of aluminum isopropylate. to continue stirring 2 afterwards
Hour, fill kettle, crystallization 3 days at 160 DEG C, filter, washing, 100 DEG C are dried overnight, and obtain b-al-zsm- after 540 DEG C of roasting 6h
11.Raw materials used, with the molar ratio computing of pure material, sio in silicon source2: the b in boron source2o3: al in silicon source2o3: in template
tba+: the oh in alkali source-: inorganic salt: h2O=1: 0.01: 0.0005: 0.2: 0.2: 0: 36.
Comparative example 1
Under room temperature, 104.2g 4-propyl bromide and 439.2g Ludox (30wt%) are dissolved in 100ml water；Stirring feelings
Under condition, Deca sodium hydrate aqueous solution (16.4g sodium hydroxide+200ml water) thereto, stirs 2 hours, adds boric acid and aluminic acid
The aqueous solution (54.4g boric acid+0.3g sodium aluminate+602ml water) of sodium continues to stir 2 hours afterwards, dress kettle, crystallization 3 days at 160 DEG C,
Filter, washing, 100 DEG C are dried overnight, and obtain b-al-zsm-5 after 540 DEG C of roasting 6h.Raw materials used, with the mol ratio of pure material
Meter, sio in silicon source2: the b in boron source2o3: al in silicon source2o3: the tba in template+: the oh in alkali source-: inorganic salt: h2O=1:
0.2∶0.00083∶0.18∶0.19∶0∶30.6.
Comparative example 2
Under room temperature, 126.2g tetrabutyl ammonium bromide and 439.2g Ludox (30wt%) are dissolved in 100ml water；Stirring feelings
Under condition, Deca sodium hydrate aqueous solution (16.4g sodium hydroxide+200ml water) thereto, stirs 2 hours, adds boric acid and aluminic acid
The aqueous solution (4.5g aluminum isopropylate .+602ml water) of sodium continues stirring 2 hours afterwards, fills kettle, crystallization 3 days at 160 DEG C, filters, wash
Wash, 100 DEG C are dried overnight, after 540 DEG C of roasting 6h, obtain zsm-11.Raw materials used, with the molar ratio computing of pure material, in silicon source
sio2: the b in boron source2o3: al in silicon source2o3: the tba in template+: the oh in alkali source-: inorganic salt: h2O=1: 0.005:
0.18∶0.19∶0∶30.6.
Experimental example 1
Respectively by embodiment 1, comparative example 1 and b-al-zsm-11, b-al-zsm-5, zsm-11 synthesized by comparative example 2 boiling
Stone use aluminium oxide extruded moulding, through 0.4m aqueous ammonium nitrate solution room temperature exchange 3 times, using after 2m salt pickling be used for methanol system
Propylene reacts.
The result that Fig. 3 reacts for catalyst preparing propylene from methanol, result shows compared with b-al-zsm-5 or zsm-11,
B-al-zsm-11 has higher Propylene Selectivity and product p/e ratio.
Claims (7)
1. a kind of preparation method of b-al-zsm-11 zeolite catalyst is it is characterised in that comprise the steps:
Under room temperature, alkali source is added in the mixed solution of template, silicon source and water, stirs 1-3h, add silicon source, boron source and nothing
The mixed aqueous solution of machine salt, loads after continuing stirring 1-3h in crystallizing kettle, crystallization 3 days at 160 DEG C, filters, deionization is washed
Wash, after 6-12 hour being dried in 100-120 DEG C, in 540-580 DEG C of roasting 1-6 hour, obtain b-al-zsm-11 zeolite；
Described, alkali source is selected from TBAH or sodium hydroxide；
Described silicon source is tetraethyl orthosilicate or Ludox or sodium silicate or white carbon；
Source of aluminium is aluminum isopropylate. or aluminum sulfate or sodium aluminate；
Described boron source is boric acid or sodium borate；
Described template is TBAH or tetrabutyl ammonium bromide；
With the molar ratio computing of pure material, sio in silicon source2: the b in boron source2o3: al in silicon source2o3: the tba in template+: alkali source
In oh-: inorganic salt: h2O=1:0.005-0.2:0.0005-0.01:0.05-0.6:0.05-0.6:0-0.6:10-100；
Described, crystallization temperature is 80-170 DEG C, and crystallization time is 1-5d；
The purposes of described b-al-zsm-11 zeolite, uses it for the reaction of catalysis methanol propylene, wherein, by the b-al- of synthesis
Zsm-11 zeolite uses aluminium oxide extruded moulding, exchanges 3 times through 0.4m aqueous ammonium nitrate solution room temperature, after the inorganic pickling of 2m
For preparing propylene from methanol reaction, described mineral acid is hydrochloric acid or sulphuric acid or nitric acid or phosphoric acid.
2. as claimed in claim 1 a kind of preparation method of b-al-zsm-11 zeolite catalyst it is characterised in that described
Alkali source is sodium hydroxide.
3. as claimed in claim 1 or 2 a kind of preparation method of b-al-zsm-11 zeolite catalyst it is characterised in that described
Silicon source be Ludox.
4. as claimed in claim 1 or 2 a kind of preparation method of b-al-zsm-11 zeolite catalyst it is characterised in that described
Silicon source be aluminum sulfate.
5. as claimed in claim 1 a kind of preparation method of b-al-zsm-11 zeolite catalyst it is characterised in that described
Boron source is boric acid.
6. as claimed in claim 1 a kind of preparation method of b-al-zsm-11 zeolite catalyst it is characterised in that described mould
Plate agent is tetrabutyl ammonium bromide.
7. as claimed in claim 1 a kind of preparation method of b-al-zsm-11 zeolite catalyst it is characterised in that in silicon source
sio2: the b in boron source2o3: al in silicon source2o3: the tba in template+: the oh in alkali source-: inorganic salt: 1:0.2:0.00083:
0.18:0.19:0:30.6.
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