CN101613114A - A kind of preparation method of ZSM-23 molecular sieve - Google Patents
A kind of preparation method of ZSM-23 molecular sieve Download PDFInfo
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- CN101613114A CN101613114A CN200910056146A CN200910056146A CN101613114A CN 101613114 A CN101613114 A CN 101613114A CN 200910056146 A CN200910056146 A CN 200910056146A CN 200910056146 A CN200910056146 A CN 200910056146A CN 101613114 A CN101613114 A CN 101613114A
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Links
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 47
- 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 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000002425 crystallisation Methods 0.000 claims abstract description 39
- 230000008025 crystallization Effects 0.000 claims abstract description 39
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 36
- 239000007788 liquid Substances 0.000 claims abstract description 31
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 30
- 239000013078 crystal Substances 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000010703 silicon Substances 0.000 claims abstract description 16
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 14
- 238000000926 separation method Methods 0.000 claims abstract description 14
- 238000005406 washing Methods 0.000 claims abstract description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000002253 acid Substances 0.000 claims abstract description 6
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 6
- 239000004411 aluminium Substances 0.000 claims abstract description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 6
- 150000001412 amines Chemical class 0.000 claims abstract description 6
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 6
- 239000011707 mineral Substances 0.000 claims abstract description 6
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 5
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 5
- 229960001866 silicon dioxide Drugs 0.000 claims abstract description 5
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical group CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims description 20
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 16
- 239000011734 sodium Substances 0.000 claims description 15
- 235000019353 potassium silicate Nutrition 0.000 claims description 12
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 12
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical group CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 6
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical group CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 claims description 6
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 4
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 4
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- 229910052708 sodium Inorganic materials 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
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 14
- 238000010790 dilution Methods 0.000 description 13
- 239000012895 dilution Substances 0.000 description 13
- 238000013019 agitation Methods 0.000 description 10
- 229910001220 stainless steel Inorganic materials 0.000 description 9
- 239000010935 stainless steel Substances 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 238000004821 distillation Methods 0.000 description 8
- 239000003921 oil Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000006243 chemical reaction Methods 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
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910052728 basic metal Inorganic materials 0.000 description 1
- 150000003818 basic metals Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- XQMTUIZTZJXUFM-UHFFFAOYSA-N tetraethoxy silicate Chemical group CCOO[Si](OOCC)(OOCC)OOCC XQMTUIZTZJXUFM-UHFFFAOYSA-N 0.000 description 1
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- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The present invention relates to a kind of preparation method of ZSM-23 molecular sieve, this method is mixed with gel with mineral acid, aluminium source, organic amine template R, potassium hydroxide, silicon source, water and crystal seed, and the mol ratio of control gained gel moiety is SiO
2/ Al
2O
3=10.0～5000, R/SiO
2=0.2～10.0, Na
2O/SiO
2=0～0.3, K
2O/SiO
2=0.01～1.0 and H
2O/SiO
2=5～300.0, add the crystal seed quality be in the silicon source contained silicon-dioxide quality 0～5.0%.The gained gel 80～250 ℃ of following crystallization 1～150 hour, is obtained the ZSM-23 molecular sieve after reclaiming template, solid-liquid separation, washing, drying, roasting.Technical process of the present invention is short, is convenient to operation, helps suitability for industrialized production; Template used dose cheap, reduced production cost, and recyclable utilization, saves cost, reduces environmental pollution.
Description
Technical field
The invention belongs to the synthetic field of inorganic hydro-thermal, concrete Application Areas is aspects such as absorption and catalysis.
Background technology
The ZSM-23 molecular sieve is a kind of mesoporous molecular sieve, has the MTT topological framework.Comprise five-ring, six-ring and ten-ring in the skeleton structure of ZSM-23 molecular sieve simultaneously, its one-dimensional channels of being made up of ten-ring is mutual not crosslinked parallel duct, and diameter is 0.56 * 0.45nm.The pore passage structure of ZSM-23 molecular sieve uniqueness and stronger surface acidity, make it in the isomerization of butene reaction, show very high catalytic activity and selectivity of product, in the reaction of catalysis C4 olefin cracking system ethene and propylene, also show splendid performance, this will alleviate that present petroleum resources face exhaustion and circumstances that the demand of ethene and propylene increases year by year to the requirement of catalyzer.It is the method for the synthetic ZSM-23 of template with the tetramethyleneimine that US4076482 discloses a kind of, and the preferable material molar ratio of this method is (0.7～2.8) R
2O: (0.08～0.25) M
2O: Al
2O
3: (50～220) SiO
2, wherein R represents tetramethyleneimine, and M represents basic metal, and its crystallization temperature is 150～190 ℃, and crystallization time is 24～264 hours.US 4490342 is with (CH
3)
3N
+-(CH
2)
7-N
+(CH
3)
3Being template, is that 150～190 ℃, crystallization time are to have synthesized the ZSM-23 molecular sieve under 24～168 hours the condition at crystallization temperature.US 5405596 is with (CH
3)
3N
+-(CH
2)
12-N
+(CH
3)
3Being template, is that 170～190 ℃, crystallization time are to have synthesized the ZSM-23 molecular sieve under 96～192 hours the condition at crystallization temperature.CN 10214971A discloses a kind of synthetic method of ZSM-23 molecular sieve, and this method is template with the Isopropylamine, is that 150～180 ℃, crystallization time are to have obtained the ZSM-23 molecular sieve under 18～72 hours the condition at crystallization temperature.But on the whole, above-mentioned patent or template used dose are comparatively expensive, and perhaps crystallization time is longer, all is unfavorable for industrial production.So must seek a suitable route and come low cost, synthesize the ZSM-23 molecular sieve expeditiously, with of the requirement of reply international energy new situations to catalyzer.
Summary of the invention
The object of the present invention is to provide a kind of ZSM-23 molecular sieve that can be used for adsorbing with aspects such as catalysis.Another object of the present invention is to provide a kind of method of the ZSM-23 of preparation molecular sieve.
ZSM-23 molecular sieve of the present invention is a synthetic by the following method: mineral acid, aluminium source, organic amine template R, potassium hydroxide, silicon source, water and crystal seed are mixed with gel, and the mol ratio of control gained gel moiety is SiO
2/ Al
2O
3=10.0～5000, R/SiO
2=0.2～10.0, Na
2O/SiO
2=0～0.3, K
2O/SiO
2=0.01～1.0 and H
2O/SiO
2=5.0～300.0; To add crystal seed be one or both mixtures in ZSM-23 and the ZSM-22 molecular sieve, add the crystal seed quality be in the silicon source contained silicon-dioxide quality 0～5.0%, under the above-mentioned crystallization condition, institute adds ZSM-23 or the ZSM-22 crystal seed all can guide generation ZSM-23 molecular sieve of the present invention; The gained gel 80～250 ℃ of following crystallization 1～150 hour, is obtained the ZSM-23 molecular sieve after reclaiming template, solid-liquid separation, washing, drying, roasting.Wherein, the synthetic described mineral acid of ZSM-23 molecular sieve is one or more mixtures in sulfuric acid, hydrochloric acid, phosphoric acid and the nitric acid, preferably sulfuric acid.Described aluminium source is one or more mixtures in aluminum oxide, aluminium hydroxide, sodium metaaluminate, Tai-Ace S 150, aluminum nitrate, aluminum chloride and the aluminum isopropylate,, one or more mixtures in preferred aluminium hydroxide, sodium metaaluminate, Tai-Ace S 150 and the aluminum isopropylate; Described organic amine template R is ethamine, Tri N-Propyl Amine, n-Butyl Amine 99 and 1, one or more mixtures in the 6-hexanediamine, one or more mixtures in preferred ethamine, Tri N-Propyl Amine and the n-Butyl Amine 99; Described silicon source is one or more mixtures of water glass, silicon sol, water glass, tetraethoxy and butyl silicate, one or more mixtures in preferably water glass or the silicon sol; The mol ratio of described ZSM-23 molecular sieve gel moiety is preferably SiO
2/ Al
2O
3=20.0～200.0, R/SiO
2=0.5～2.0, Na
2O/SiO
2=0.05～0.2, K
2O/SiO
2=0.1～0.5 and H
2O/SiO
2=10.0～100.0; Add the crystal seed quality optimization be in the silicon source contained silicon-dioxide quality 0.1～1.0%; Preferred 130～170 ℃ of the crystallization temperature of described synthetic ZSM-23 molecular sieve; Preferred 10～60 hours of described crystallization time; Described maturing temperature is 300～850 ℃, preferred 450～650 ℃; Used roasting time is 1～80 hour, preferred 3～20 hours.
Compared with prior art, the present invention has following remarkable advantage: (1) technical process is short, is convenient to operation, is beneficial to suitability for industrialized production; (2) template used dose is cheap ethamine, Tri N-Propyl Amine or n-Butyl Amine 99, and can recycle, and not only saves cost, also can reduce environmental pollution.
Description of drawings
Fig. 1 is the X-ray diffraction spectrogram of product ZSM-23 molecular sieve of the present invention.
Embodiment
Below by embodiment in detail the present invention is described in detail, but the present invention is not limited to these embodiment.
Raw material consumption " part " number average described in following examples is " weight part " number.
[embodiment 1]
Under agitation condition, be 98.7% the vitriol oil with 38.2 parts of weight concentrations of 88 parts of water dilution, obtain dilution heat of sulfuric acid, be 65.8% ethamine to wherein dripping 96 parts of weight concentrations, make solution A.Stir then down solution A is slowly splashed into 357 parts of water glass (SiO
2Weight concentration be 24.93%; Na
2The weight concentration of O is 7.33%) in obtain mixed liquid B.20 parts of water that will be dissolved with 9 parts of potassium hydroxide (weight concentration is 90%) again splash in the mixed liquid B, add 1.2 parts of ZSM-22 molecular sieves as crystal seed at last, and the back that stirs forms gel.Above-mentioned gel transferred to have in the teflon-lined stainless steel cauldron, in 155 ℃ of following crystallization 24 hours.After crystallization finishes, obtain the ZSM-23 molecular sieve after ethamine, solid-liquid separation, washing, drying, roasting are reclaimed in distillation, its X-ray diffraction spectrogram as shown in Figure 1.
[embodiment 2]
With gained gel among the embodiment 1 in 165 ℃ of following crystallization 15 hours.After crystallization finishes, after reclaiming ethamine, solid-liquid separation, washing, drying, roasting, distillation obtains the ZSM-23 molecular sieve,
[embodiment 3]
In embodiment 1, after obtaining mixed liquid B, 20 parts of water that will be dissolved with 6 parts of potassium hydroxide (weight concentration is 90%) splash in the mixed liquid B, add 1.2 parts of ZSM-22 molecular sieves as crystal seed at last, and the back that stirs forms gel.Above-mentioned gel transferred to have in the teflon-lined stainless steel cauldron, in 155 ℃ of following crystallization 30 hours.After crystallization finishes, after reclaiming ethamine, solid-liquid separation, washing, drying, roasting, distillation obtains the ZSM-23 molecular sieve.
[embodiment 4]
In embodiment 2, after obtaining mixed liquid B, 20 parts of water that will be dissolved with 3 parts of potassium hydroxide (weight concentration is 90%) splash in the mixed liquid B, add 2 parts of ZSM-23 molecular sieves as crystal seed at last, and the back that stirs forms gel.Above-mentioned gel transferred to have in the teflon-lined stainless steel cauldron, in 150 ℃ of following crystallization 30 hours.After crystallization finishes, after reclaiming ethamine, solid-liquid separation, washing, drying, roasting, distillation obtains the ZSM-23 molecular sieve.
[embodiment 5]
Under agitation condition, be 98.7% the vitriol oil with 38.2 parts of weight concentrations of 40 parts of water dilution, obtain dilution heat of sulfuric acid, be 41.48% recovery ethamine to wherein dripping 144 parts of weight concentrations, make solution A.Stir then down solution A is slowly splashed into 357 parts of water glass (SiO
2Weight concentration be 24.93%; Na
2The weight concentration of O is 7.33%) in obtain mixed liquid B.20 parts of water that will be dissolved with 9 parts of potassium hydroxide (weight concentration is 90%) again splash in the mixed liquid B, add 1.2 parts of ZSM-22 molecular sieves as crystal seed at last, and the back that stirs forms gel.Above-mentioned gel transferred to have in the teflon-lined stainless steel cauldron, in 155 ℃ of following crystallization 24 hours.After crystallization finishes, after reclaiming ethamine, solid-liquid separation, washing, drying, roasting, distillation obtains the ZSM-23 molecular sieve.
[embodiment 6]
Under agitation condition, be 98.7% the vitriol oil with 30 parts of weight concentrations of 60 parts of water dilution, obtain dilution heat of sulfuric acid, be 41.48% recovery ethamine to wherein dripping 144 parts of weight concentrations, make solution A.Stir then down solution A is slowly splashed into 357 parts of water glass (SiO
2Weight concentration be 24.93%; Na
2The weight concentration of O is 7.33%) in obtain mixed liquid B.20 parts of water that will be dissolved with 9 parts of potassium hydroxide (weight concentration is 90%) again splash in the mixed liquid B, add 1.2 parts of ZSM-22 molecular sieves as crystal seed at last, and the back that stirs forms gel.Above-mentioned gel transferred to have in the teflon-lined stainless steel cauldron, in 155 ℃ of following crystallization 24 hours.After crystallization finishes, after reclaiming ethamine, solid-liquid separation, washing, drying, roasting, obtain the ZSM-23 molecular sieve.
[embodiment 7]
In embodiment 6, change the crystal seed that adds into 3 parts of ZSM-23 molecular sieves, with the gained gel in 155 ℃ of following crystallization 24 hours.After crystallization finishes, after reclaiming ethamine, solid-liquid separation, washing, drying, roasting, obtain the ZSM-23 molecular sieve.
[embodiment 8]
Under agitation condition, be 90% the vitriol oil with 38.2 parts of weight concentrations of 80 parts of water dilution, be 41.48% recovery ethamine to wherein dripping 144 parts of weight concentrations, make solution A.Stir then down solution A is slowly splashed into 357 parts of water glass (SiO
2Weight concentration be 24.93%; Na
2The weight concentration of O is 7.33%) in obtain mixed liquid B.20 parts of water that will be dissolved with 9 parts of potassium hydroxide (weight concentration is 90%) and 7 parts of Tai-Ace S 150 again splash in the mixed liquid B, add 4 parts of ZSM-23 molecular sieves as crystal seed at last, and the back that stirs forms gel.Above-mentioned gel transferred to have in the teflon-lined stainless steel cauldron, in 155 ℃ of following crystallization 24 hours.After crystallization finishes, after reclaiming ethamine, solid-liquid separation, washing, drying, roasting, obtain the ZSM-23 molecular sieve.
[embodiment 9]
Under agitation condition, be 98.7% the vitriol oil with 38.2 parts of weight concentrations of 70 parts of water dilution, obtain dilution heat of sulfuric acid, be 98% Tri N-Propyl Amine to wherein splashing into 83 parts of weight concentrations, make solution A.Under agitation solution A is slowly splashed into 357 parts of water glass (SiO then
2Weight concentration be 24.93%; Na
2The weight concentration of O is 7.33%) in obtain mixed liquid B.Splash into 50 parts of water that are dissolved with 9 parts of potassium hydroxide (weight concentration is 90%) in B, add 1.2 parts of ZSM-22 molecular sieves as crystal seed at last, the back that stirs forms gel.Above-mentioned gel transferred to have in the teflon-lined stainless steel cauldron, in 155 ℃ of following crystallization 28 hours.After crystallization finishes, after reclaiming ethamine, solid-liquid separation, washing, drying, roasting, distillation obtains the ZSM-23 molecular sieve.
[embodiment 10]
Under agitation condition, be 98.7% the vitriol oil with 38.2 parts of weight concentrations of 90 parts of water dilution, obtain dilution heat of sulfuric acid, to wherein adding 40 parts of water that are dissolved with 9 parts of potassium hydroxide and 1 part of sodium hydroxide, make solution A.Under agitation condition, be that 98% n-Butyl Amine 99 slowly splashes into 316 parts of silicon sol (SiO with 102 parts of weight concentrations
2Weight concentration be 29.3%; Na
2The weight concentration of O is 0.31%) in obtain mixed liquid B.Solution A is slowly splashed in the mixed liquid B, add 1.2 parts of ZSM-22 molecular sieves as crystal seed at last, the back that stirs forms gel.Above-mentioned gel transferred to have in the teflon-lined stainless steel cauldron, in 155 ℃ of following crystallization 50 hours.After crystallization finishes, after reclaiming ethamine, solid-liquid separation, washing, drying, roasting, distillation obtains the ZSM-23 molecular sieve.
[embodiment 11]
Under agitation condition, be 98.7% the vitriol oil with 38.2 parts of weight concentrations of 90 parts of water dilution, obtain dilution heat of sulfuric acid, to wherein drip 166 parts of weight concentrations be 98% 1, the 6-hexanediamine is made solution A.Under agitation solution A is slowly splashed into 357 parts of water glass (SiO then
2Weight concentration be 24.93%; Na
2The weight concentration of O is 7.33%) in, mixed liquid B obtained.50 parts of water that will be dissolved with 9 parts of potassium hydroxide (weight concentration is 90%) again splash in the mixed liquid B, add 1.2 parts of ZSM-22 molecular sieves as crystal seed at last, and the back that stirs forms gel.Above-mentioned gel transferred to have in the teflon-lined stainless steel cauldron, in 155 ℃ of following crystallization 12 hours.After crystallization finishes, after reclaiming ethamine, solid-liquid separation, washing, drying, roasting, distillation obtains the ZSM-23 molecular sieve.
Claims (8)
1, a kind of preparation method of ZSM-23 molecular sieve is characterized in that preparation process comprises the steps:
1) mineral acid, aluminium source, organic amine template R, potassium hydroxide, silicon source, water and crystal seed are mixed with gel, the mol ratio of control gained gel moiety is SiO
2/ Al
2O
3=10.0～5000, R/SiO
2=0.2～10.0, Na
2O/SiO
2=0～0.3, K
2O/SiO
2=0.01～1.0 and H
2O/SiO
2=5.0～300.0;
2) in above-mentioned gel, add crystal seed, make add the crystal seed quality be in the silicon source contained silicon-dioxide quality 0～5.0%;
3) with step 2) in the gained gel 80～250 ℃ of following crystallization 1～150 hour;
4) with product in the step 3) after reclaiming template, solid-liquid separation, washing, drying, in 300～850 ℃ of following roastings 1～80 hour, obtain the ZSM-23 molecular sieve again.
2, preparation method according to claim 1 is characterized in that the mineral acid described in the step 1) is one or more mixtures in sulfuric acid, hydrochloric acid, phosphoric acid and the nitric acid; Described aluminium source is one or more mixtures in aluminum oxide, aluminium hydroxide, sodium metaaluminate, Tai-Ace S 150, aluminum nitrate, aluminum chloride and the aluminum isopropylate; Described organic amine template R is ethamine, Tri N-Propyl Amine, n-Butyl Amine 99 and 1, one or more mixtures in the 6-hexanediamine; Described silicon source is one or more mixtures in water glass, silicon sol, water glass, tetraethoxy and the butyl silicate.
3, preparation method according to claim 2 is characterized in that the mineral acid described in the step 1) is a sulfuric acid; Described aluminium source is one or more mixtures in aluminium hydroxide, sodium metaaluminate, Tai-Ace S 150 and the aluminum isopropylate; Described organic amine template R is one or more mixtures in ethamine, Tri N-Propyl Amine and the n-Butyl Amine 99; Described silicon source is one or both mixtures in water glass and the silicon sol.
4, preparation method according to claim 1, the mol ratio that it is characterized in that gained gel moiety in the step 1) is SiO
2/ Al
2O
3=20.0～200.0, R/SiO
2=0.5～2.0, Na
2O/SiO
2=0.05～0.2, K
2O/SiO
2=0.1～0.5 and H
2O/SiO
2=10.0～100.0.
5, preparation method according to claim 1 is characterized in that step 2) in, to add crystal seed be one or both mixtures in ZSM-23 and the ZSM-22 molecular sieve.
6, preparation method according to claim 1 is characterized in that step 2) in, add the crystal seed quality be in the silicon source contained silicon-dioxide quality 0.1～1.0%.
7,1 described preparation method as requested is characterized in that in the step 3) that described crystallization temperature is 130～170 ℃; Described crystallization time is 10～60 hours.
8, preparation method according to claim 1 is characterized in that in the step 4), and described maturing temperature is 450～650 ℃; Described roasting time is 3～20 hours.
Priority Applications (1)
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| CN102897785A (en) * | 2011-07-29 | 2013-01-30 | 中国石油化工股份有限公司 | Synthesis method for ZSM-23 molecular sieve |
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| CN111233000A (en) * | 2018-11-28 | 2020-06-05 | 中国科学院大连化学物理研究所 | Synthesis method of MTT type molecular sieve with low silicon-aluminum ratio |
| WO2022148416A1 (en) | 2021-01-07 | 2022-07-14 | 中国石油化工股份有限公司 | Zsm-23 molecular sieve and preparation method therefor |
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| CN102992346A (en) * | 2012-12-09 | 2013-03-27 | 浙江大学 | Seed crystal synthesis method for preparing ZSM-23 molecular sieve |
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| WO2022148416A1 (en) | 2021-01-07 | 2022-07-14 | 中国石油化工股份有限公司 | Zsm-23 molecular sieve and preparation method therefor |
| CN114988430A (en) * | 2022-06-06 | 2022-09-02 | 山西大学 | Synthesis method of nanorod-shaped ZSM-23 molecular sieve |
| CN114988430B (en) * | 2022-06-06 | 2024-03-12 | 山西大学 | Synthesis method of nanorod ZSM-23 molecular sieve |
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