CN101177282A - Method for synthesizing high-crystallinity ZSM-5 molecular sieve without organic template - Google Patents
Method for synthesizing high-crystallinity ZSM-5 molecular sieve without organic template Download PDFInfo
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- CN101177282A CN101177282A CNA2007101564798A CN200710156479A CN101177282A CN 101177282 A CN101177282 A CN 101177282A CN A2007101564798 A CNA2007101564798 A CN A2007101564798A CN 200710156479 A CN200710156479 A CN 200710156479A CN 101177282 A CN101177282 A CN 101177282A
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- 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 41
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 30
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000007787 solid Substances 0.000 claims abstract description 30
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 27
- 239000010703 silicon Substances 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 12
- 239000004809 Teflon Substances 0.000 claims abstract description 9
- 229920006362 Teflon® Polymers 0.000 claims abstract description 9
- 229910001220 stainless steel Inorganic materials 0.000 claims abstract description 9
- 239000010935 stainless steel Substances 0.000 claims abstract description 9
- 239000013078 crystal Substances 0.000 claims abstract description 7
- 150000004645 aluminates Chemical group 0.000 claims abstract description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 4
- 239000008367 deionised water Substances 0.000 claims abstract description 3
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 238000009415 formwork Methods 0.000 claims description 19
- 239000011734 sodium Substances 0.000 claims description 15
- 238000002425 crystallisation Methods 0.000 claims description 14
- 230000008025 crystallization Effects 0.000 claims description 14
- 239000011541 reaction mixture Substances 0.000 claims description 14
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 9
- 239000011707 mineral Substances 0.000 claims description 9
- 235000019353 potassium silicate Nutrition 0.000 claims description 9
- 238000000967 suction filtration Methods 0.000 claims description 9
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims description 8
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 6
- 159000000013 aluminium salts Chemical class 0.000 claims description 4
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- 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
- 239000004411 aluminium Substances 0.000 claims description 2
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 claims description 2
- 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 2
- 239000006229 carbon black Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 239000000741 silica gel Substances 0.000 claims description 2
- 229910002027 silica gel Inorganic materials 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- 238000005516 engineering process Methods 0.000 abstract description 4
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 abstract 1
- 230000007613 environmental effect Effects 0.000 abstract 1
- 238000005216 hydrothermal crystallization Methods 0.000 abstract 1
- 150000007529 inorganic bases Chemical class 0.000 abstract 1
- 150000007522 mineralic acids Chemical class 0.000 abstract 1
- 239000012265 solid product Substances 0.000 description 14
- 239000000499 gel Substances 0.000 description 12
- 238000002441 X-ray diffraction Methods 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 10
- 238000003756 stirring Methods 0.000 description 9
- 229910052708 sodium Inorganic materials 0.000 description 7
- 239000000243 solution Substances 0.000 description 6
- 238000010189 synthetic method Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000004090 dissolution Methods 0.000 description 5
- 229920001296 polysiloxane Polymers 0.000 description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 229960001866 silicon dioxide Drugs 0.000 description 3
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000007233 catalytic pyrolysis Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 1
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- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The invention discloses a synthesizing method of high crystallinity ZSM-5 molecular sieve without using organic template, comprising the following steps: mixing silicon source and aluminum source with de-ionized water and inorganic base (needless if two silicon source is used) according to a certain proportion, wherein, the silicon source is unbodied solid of silicon dioxide or the mixture of the unbodied solid of silicon dioxide and solid metasilicate, and the aluminum source is aluminate or aluminum compounds; placing the mixture in a stainless steel reaction kettle provided with a teflon lining and performing hydrothermal crystallization under certain condition. The invention is characterized in that the high crystallinity ZSM-5 molecular sieve can be obtained without adding crystal seed into the mixture; and the ratio of water to silicon is small and the solid content is high; the expensive and environment-unfriendly organic template and the corrosive inorganic acid are not used. The invention has the advantages of low production cost, high productivity of single kettle, simple technology and environmental protection.
Description
Technical field
The invention belongs to synthesis method of zeolite molecular sieve, especially relate to a kind of method without organic formwork synthesizing high-crystallinity ZSM-5 molecular sieve.
Background technology
The ZSM-5 molecular sieve is a kind of supersiliceous zeolite (US3702886,1972) with three-dimensional open-framework of being developed the earliest by the U.S. Mobil company earlier 1970s.Because the unique texture of ZSM-5 molecular sieve, and good thermostability and hydrothermal stability, make its to alkylation, isomerization, disproportionation, select reactions such as type reaction, catalytic pyrolysis, preparing gasoline by methanol, heavy oil drastic cracking, methanol-to-olefins and have unique catalytic performance, thereby be widely used as catalystic material and support of the catalyst.
The synthetic method of ZSM-5 molecular sieve generally can be divided into organic method and inorganic method.So-called organic method is exactly a method of using organic formwork agents such as 4-propyl bromide or TPAOH in reaction system; Inorganic rule is without organic formwork agent in reaction system.Organic formwork agent price general charged costliness, poisonous; In addition, use the synthetic ZSM-5 molecular sieve that obtains of organic formwork agent to need high-temperature roasting, removing organic formwork agent contained in the molecular sieve pore passage, high-temperature roasting is not only during consumption energy consumption, and the gas that produced of organic formwork agent pyrolysis can polluted air; If pyrolysis is incomplete, thereby also can stopping up molecular sieve pore passage, solid residue reduces catalyst activity, therefore adopt organic method to synthesize the ZSM-5 molecular sieve, not only can increase production cost, and pollute the environment.
Therefore inorganic method the problems referred to above can not occur without organic formwork agent, is a kind of eco-friendly synthetic method.With the synthetic ZSM-5 molecular sieve of inorganic method, the selection in silicon source is very important.At present existing patent disclosure some methods without the synthetic ZSM-5 molecular sieve of organic formwork agent, from example, the silicon source of using mainly is water glass or silicon sol, as in the synthetic method of CN85100463 (1988) and CN1056818 patent disclosures such as (2000), with water glass as the silicon source; In the synthetic method of US4257885 (1981), US5240892 (1993), US5254327 (1993) and CN1318302 patent disclosures such as (2007), with silicon sol as the silicon source.With water glass or silicon sol as the silicon source, big (the general H of the mol ratio of water and silicon-dioxide in the reaction mixture (be called for short water silicon than) generally
2O/SiO
2〉=25), thus single-autoclave yield rate lower.
Replacing water glass or silicon sol with the soft silica solid is the silicon source, can improve the solid content of reaction system, thereby can improve single-autoclave yield rate.
In the disclosed synthetic method of US4257885 (1981) patent,, be the silicon source also with amorphous reactive silicon dioxide solid except being the silicon source with the silicon sol, but in the reaction system that is adopted water silicon than (H
2O/SiO
2=15-40) and solid content (8-15wt%) lower, and in reaction mixture, need to add crystal seed, to improve the degree of crystallinity and the productive rate of product as nucleator.
In the disclosed synthetic method of US5240892 (1993) patent, in the reaction system solid content higher (〉=35wt%), mainly be by using the higher silica suspension of solid content (granular size is the 1-500 micron) to realize as the silicon source, but the higher silica suspension of solid content is to be obtained through steps such as acidifying, filtration, washings by sodium silicate aqueous solution (water glass), therefore synthesis technique is comparatively complicated, and uses the mineral acid that equipment is had corrosive nature in the building-up process.In addition, need to use crystal seed in the building-up process, even like this, the molecular sieve crystallinity that obtains is still lower, has only 50-75%.
CN1056818 (2000) patent disclosure a kind of method that improves solid content in the reaction mixture, being about to raw water glass is heated to more than 40 ℃ in advance, and then mix with components such as acidifying aluminate solutions, allegedly can reduce the viscosity of reaction mixture so greatly, thereby can reduce the water yield that feeds intake, improve single still combined coefficient.The shortcoming of this patented method is that energy consumption is higher, needs to use the mineral acid that equipment is had corrosive nature simultaneously.
Summary of the invention
The object of the present invention is to provide a kind of method without organic formwork agent and the synthetic high-crystallinity ZSM-5 molecular sieve of crystal seed, this method has the high characteristics of single-autoclave yield rate.
The objective of the invention is to be achieved through the following technical solutions:
With the soft silica solid is the silicon source, is the aluminium source with aluminate or aluminium salt, mixes with deionized water, mineral alkali, and the mol ratio of each component is in the reaction mixture: Na
2O: SiO
2=0.05～0.2: 1, SiO
2: Al
2O
3=20～100: 1, H
2O: SiO
2=10～25: 1, then mixture is placed in the stainless steel crystallizing kettle of teflon lined hydrothermal crystallizing, 180～200 ℃ of crystallization temperatures, crystallization time 8～72 hours, the mixture after the crystallization get high-crystallinity ZSM-5 molecular sieve after suction filtration, washing, drying.
Mixture with soft silica solid and solid state si hydrochlorate is two silicon sources, without mineral alkali.
Described soft silica solid is silica gel or white carbon black.
Described solid state si hydrochlorate is the water glass crystal.
Described aluminium salt is a kind of in aluminum nitrate, Tai-Ace S 150, aluminum phosphate and the aluminum chloride, or two kinds of mixtures arbitrarily among them.
Described aluminate is a sodium aluminate.
Described mineral alkali is sodium hydroxide or potassium hydroxide.
The present invention compares the beneficial effect that has with background technology:
It is raw material that the present invention adopts low price, the abundant inorganics in source, does not use the mineral acid that equipment is had corrosive nature simultaneously.Adopting the soft silica solid in synthetic system is the silicon source, and water silicon is than little (H in the reaction mixture
2O/SiO
2=10-25), solid content height (13.6-38.6wt%), relative crystallinity height (102-172%).In reaction mixture, do not add under the prerequisite of crystal seed, can obtain the ZSM-5 molecular sieve of high-crystallinity.The present invention has that production cost is low, single-autoclave yield rate is high, technology is simple, advantages of environment protection.
Description of drawings
Fig. 1 is by embodiment 1 synthetic molecular sieve XRD spectra.
Fig. 2 is by Comparative Examples synthetic molecular sieve XRD spectra.
XRD determining all is to carry out on German Bruker axs type X-ray diffractometer, adopts CuK α diffraction, sweep limit 2 θ=5～40 °.By XRD spectra as can be known, the XRD diffraction peak of two samples is similar, in 2 θ=7.8 °, 8.8 °, 23.2 °, 23.8 °, 24.3 ° etc. locate to occur strong diffraction peak, illustrate that embodiment 1 and Comparative Examples synthetic molecular sieve all have typical ZSM-5 molecular sieve structure, i.e. the MFI structure.
The method of calculation of relative crystallinity (R%) are as follows:
Embodiment
Embodiment 1
0.480 gram dissolution of sodium hydroxide in 28.69 gram water, after stirring to clarify, is added 0.796 gram sodium aluminate (Al successively
2O
341.0wt%, Na
2O24.9wt%, H
2O34.1wt%) and 3.846 gram solid silicones (100-200 order), stirred 1 hour, must an even gel.Gel is transferred in the stainless steel crystallizing kettle of 100mL teflon lined, crystallization were stirred 12 hours in 190 ℃ in airtight back, after suction filtration, washing, drying solid product 6.72 grams.
Solid product is ZSM-5 molecular sieve (seeing accompanying drawing 1) through X-ray diffraction analysis, and relative crystallinity is 102%.
In the present embodiment, the mol ratio between each component of reaction mixture is as follows:
SiO
2∶Al
2O
3＝20∶1，Na
2O∶SiO
2＝0.14∶1，H
2O∶SiO
2＝25∶1。
Comparative Examples:
It is the method (reference literature: Cheng Yue of the synthetic ZSM-5 molecular sieve of organic formwork agent with the 4-propyl bromide that this Comparative Examples provides a kind of, Wang Lianjun, Li Jiansheng, Sun Xiuyun, Liu Xiaodong. with TPABr is the synthetic and sign of the ZSM-5 molecular screen membrane of template. Chinese pottery, 2005,41 (1): the method for 16-19), to compare with the ZSM-5 molecular sieve that synthesizes according to method of the present invention.The synthetic ZSM-5 molecular sieve that obtains of this Comparative Examples is considered as standard specimen, so its relative crystallinity is 100%.
2.45 gram dissolution of sodium hydroxide in 45.0 gram water, after stirring to clarify, are added 3.32 gram 4-propyl bromides (TPABr), 0.304 gram sodium aluminate (Al successively
2O
341.0wt%, Na
2O24.9wt%, H
2O34.1wt%) and 36.7 gram silicon sol (40wt%), stirred 1 hour, must an even gel.Gel is transferred in the stainless steel crystallizing kettle of 100mL teflon lined, airtight back is in 180 ℃ of crystallization 24 hours, after suction filtration, washing, drying solid product 5.35 grams.
Solid product is ZSM-5 molecular sieve (seeing accompanying drawing 2) through X-ray diffraction analysis.
With 5.457 gram water glass (SiO
221.15wt%, Na
2O21.82wt%, H
2O57.03wt%) be dissolved in the 34.30 gram water, stir to clarify, get solution A; In another beaker, with 0.796 gram sodium aluminate (Al
2O
341.0wt%, Na
2O24.9wt%, H
2O34.1wt%) be dissolved in the 34.30 gram water, stir to clarify, get solution B.Under the room temperature solution B is added in the solution A fast, adds 8.462 gram solid silicones (100-200 order) then while stirring, add the back and continue to stir 1 hour, get an even gel.Gel is transferred in the stainless steel crystallizing kettle of 100mL teflon lined, crystallization were stirred 72 hours in 180 ℃ in airtight back, after suction filtration, washing, drying solid product 5.44 grams.
Solid product is the ZSM-5 molecular sieve through X-ray diffraction analysis, and relative crystallinity is 114%.
In the present embodiment, the mol ratio between each component of reaction mixture is as follows:
SiO
2∶Al
2O
3＝50∶1，Na
2O∶SiO
2＝0.14∶1，H
2O∶SiO
2＝25∶1。
Embodiment 3
4.608 gram dissolution of sodium hydroxide in 71.46 gram water, after stirring to clarify, are added 1.592 gram sodium aluminate (Al successively
2O
341.0wt%, Na
2O24.9wt%, H
2O34.1wt%) and 19.23 gram solid silicones (100-200 order), stirred 1 hour, must an even gel.Gel is transferred in the stainless steel crystallizing kettle of 100mL teflon lined, crystallization were stirred 24 hours in 190 ℃ in airtight back, after suction filtration, washing, drying solid product 9.08 grams.
Solid product is the ZSM-5 molecular sieve through X-ray diffraction analysis, and relative crystallinity is 172%.
In the present embodiment, the mol ratio between each component of reaction mixture is as follows:
SiO
2∶Al
2O
3＝50∶1，Na
2O∶SiO
2＝0.2∶1，H
2O∶SiO
2＝12.5∶1。
Embodiment 4
1.024 gram dissolution of sodium hydroxide in 71.46 gram water, after stirring to clarify, are added 1.592 gram sodium aluminate (Al successively
2O
341.0wt%, Na
2O24.9wt%, H
2O34.1wt%) and 19.23 gram solid silicones (100-200 order), stirred 1 hour, must an even gel.Gel is transferred in the stainless steel crystallizing kettle of 100mL teflon lined, crystallization were stirred 24 hours in 190 ℃ in airtight back, after suction filtration, washing, drying solid product 8.96 grams.
Solid product is the ZSM-5 molecular sieve through X-ray diffraction analysis, and relative crystallinity is 159%.
In the present embodiment, the mol ratio between each component of reaction mixture is as follows:
SiO
2∶Al
2O
3＝50∶1，Na
2O∶SiO
2＝0.06∶1，H
2O∶SiO
2＝12.5∶1。
Embodiment 5
1.024 gram dissolution of sodium hydroxide in 71.46 gram water, after stirring to clarify, are added 0.796 gram sodium aluminate (Al successively
2O
341.0wt%, Na
2O24.9wt%, H
2O34.1wt%) and 19.23 gram solid silicones (100-200 order), stirred 1 hour, must an even gel.Gel is transferred in the stainless steel crystallizing kettle of 100mL teflon lined, crystallization were stirred 24 hours in 190 ℃ in airtight back, after suction filtration, washing, drying solid product 9.54 grams.
Solid product is the ZSM-5 molecular sieve through X-ray diffraction analysis, and relative crystallinity is 165%.
In the present embodiment, the mol ratio between each component of reaction mixture is as follows:
SiO
2∶Al
2O
3＝100∶1，Na
2O∶SiO
2＝0.05∶1，H
2O∶SiO
2＝12.5∶1。
Embodiment 6
Repeat the operation steps of embodiment 2, its difference is that crystallization condition changes 200 ℃ into and stirred crystallization 12 hours down, and all the other are all identical with embodiment 2.After suction filtration, washing, drying, get solid product 6.30 grams.
Solid product is the ZSM-5 molecular sieve through X-ray diffraction analysis, and relative crystallinity is 126%.
In the present embodiment, the mol ratio between each component of reaction mixture is as follows:
SiO
2∶Al
2O
3＝50∶1，Na
2O∶SiO
2＝0.14∶1，H
2O∶SiO
2＝25∶1。
Embodiment in the above-mentioned embodiment is used for the present invention that explains, rather than limits the invention, and in the protection domain of spirit of the present invention and claim, any modification and change to the present invention makes all fall into protection scope of the present invention.
Claims (7)
1. method without organic formwork synthesizing high-crystallinity ZSM-5 molecular sieve, it is characterized in that: with the soft silica solid is the silicon source, with aluminate or aluminium salt is the aluminium source, mixes with deionized water, mineral alkali, and the mol ratio of each component is in the reaction mixture: Na
2O: SiO
2=0.05～0.2: 1, SiO
2: Al
2O
3=20～100: 1, H
2O: SiO
2=10～25: 1, then mixture is placed in the stainless steel crystallizing kettle of teflon lined hydrothermal crystallizing, 180～200 ℃ of crystallization temperatures, crystallization time 8～72 hours, the mixture after the crystallization get high-crystallinity ZSM-5 molecular sieve after suction filtration, washing, drying.
2. a kind of method without organic formwork synthesizing high-crystallinity ZSM-5 molecular sieve according to claim 1 is characterized in that: the mixture with soft silica solid and solid state si hydrochlorate is two silicon sources, without mineral alkali.
3. a kind of method without organic formwork synthesizing high-crystallinity ZSM-5 molecular sieve according to claim 1, it is characterized in that: described soft silica solid is silica gel or white carbon black.
4. according to the described a kind of method without organic formwork synthesizing high-crystallinity ZSM-5 molecular sieve of claim 1, it is characterized in that: described solid state si hydrochlorate is the water glass crystal.
5. a kind of method according to claim 1 without organic formwork synthesizing high-crystallinity ZSM-5 molecular sieve, it is characterized in that: described aluminium salt is a kind of in aluminum nitrate, Tai-Ace S 150, aluminum phosphate and the aluminum chloride, or two kinds of mixtures arbitrarily among them.
6. a kind of method without organic formwork synthesizing high-crystallinity ZSM-5 molecular sieve according to claim 1, it is characterized in that: described aluminate is a sodium aluminate.
7. a kind of method without organic formwork synthesizing high-crystallinity ZSM-5 molecular sieve according to claim 1, it is characterized in that: described mineral alkali is sodium hydroxide or potassium hydroxide.
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| CN101993091B (en) * | 2009-08-27 | 2012-07-18 | 中国石油化工股份有限公司 | Method for synthesizing ZSM-5 zeolite |
| CN102757068A (en) * | 2011-04-29 | 2012-10-31 | 山东齐鲁华信高科有限公司 | Method for synthesizing amine-free ZSM (zeolite socony mobil)-5 molecular sieve |
| CN102757069A (en) * | 2011-04-29 | 2012-10-31 | 山东齐鲁华信高科有限公司 | Method for reusing mother liquor generated in ZSM (zeolite socony mobil)-5 molecular sieve preparation |
| CN102962091A (en) * | 2012-11-23 | 2013-03-13 | 中国天辰工程有限公司 | Preparation method of ZSM-5 (zeolites synthesized by mobil-5) molecular sieve catalyst with small grain diameter |
| CN101993092B (en) * | 2009-08-27 | 2014-04-30 | 中国石油化工股份有限公司 | Method for synthesizing ZSM-5 zeolite |
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