CN102745718A - Synthesis method of sub-micron ZSM-5 molecular sieve - Google Patents
Synthesis method of sub-micron ZSM-5 molecular sieve Download PDFInfo
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- CN102745718A CN102745718A CN2012102511286A CN201210251128A CN102745718A CN 102745718 A CN102745718 A CN 102745718A CN 2012102511286 A CN2012102511286 A CN 2012102511286A CN 201210251128 A CN201210251128 A CN 201210251128A CN 102745718 A CN102745718 A CN 102745718A
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Abstract
The invention relates to a synthesis method of a sub-micron ZSM-5 molecular sieve, belonging to the field of synthesis of molecular sieves. The method is characterized in that silica gel and water glass are used as a mixed silicon source, aluminum salt is used as an aluminum source, and crystallization is carried out in the presence of an organic template agent to obtain the ZSM-5 molecular sieve. The method is simple to operate, simplifies the synthesis steps of the ZSM-5 molecular sieve, and has the advantage of high synthesis efficiency; and the product has the advantages of high relative degree of crystallization, and complete crystal form, and the grain size ranges from 300nm to 500nm.
Description
Technical field
The present invention relates to a kind of compound method of submicron order ZSM-5 molecular sieve, belong to the synthetic field of molecular sieve.
Background technology
ZSM-5 molecular sieve with MFI crystalline structure, from 1972 by U.S. Mobil oil company open since, almost become except that Y zeolite, at field purposes such as petrochemical complex and fine chemistry industry molecular sieve catalytic material the most widely.The ZSM-5 molecular sieve can be used for petroleum cracking catalyzer and octane enhancing additive, is used for voluminous liquefied gas and propylene auxiliary agent, is used to select shape aromizing, isomerizing, alkylation catalyst, is used for the novel environment friendly catalyzer, or the like.
ZSM-5 molecular sieve synthetic with regard to its synthetic route, can be divided into amine method and non-amine method two big classes are arranged.
Non-amine method synthesizes the ZSM-5 molecular sieve, and its biggest advantage is that synthetic cost is lower, non-environmental-pollution, so its use range is wider.But its proportioning raw materials and product silica alumina ratio scope have certain limitation, and its crystalline structure or grain size still can not satisfy various request for utilizations fully.
Use template to have the amine method to synthesize the ZSM-5 molecular sieve, the product silica alumina ratio that can satisfy basically in a big way requires and the crystal grain requirement.
The characteristics of little crystal grain or submicron ZSM-5 molecular sieve are, zeolite crystal is little, and specific surface area is big, and the active site number is many, more helps improving the catalysis efficiency of sieve catalyst.
Synthetic ZSM-5 molecular sieve combined coefficient is low but the existing templates agent has the amine method, and the products obtained therefrom relative crystallinity is low, and crystal formation is imperfect.
Summary of the invention
According to the deficiency of prior art, the technical problem that the present invention will solve is: a kind of compound method of submicron order ZSM-5 molecular sieve is provided, has simplified the synthesis step of ZSM-5 molecular sieve, improve combined coefficient, the products obtained therefrom relative crystallinity is high, complete in crystal formation.
The technical solution adopted for the present invention to solve the technical problems is: the compound method that a kind of submicron order ZSM-5 molecular sieve is provided; It is characterized in that: with silica gel and water glass serves as to mix the silicon source; With aluminium salt is the aluminium source, the synthetic ZSM-5 molecular sieve of crystallization under the organic formwork agent existence condition.
Described silica gel is powder silicon-dioxide series products.
Add the molecular sieve crystal seed in the described mixing silicon source, the add-on of molecular sieve crystal seed is the 0-10% of total quality of material.
Described aluminium salt is one or more the mixture in Tai-Ace S 150, aluminum chloride or the aluminum nitrate, wherein is preferably Tai-Ace S 150.
Silica alumina ratio 20-100 in described mixing silicon source and the aluminium source.
Described organic formwork agent is an organic amine, and wherein organic amine is ethamine, propylamine or n-Butyl Amine 99.
Described molecular sieve crystal seed joins fully making beating in the water glass solution under 50-100 ℃.
Pull an oar in the mixed serum of described silica gel adding water glass and molecular sieve crystal seed, add aluminium salt then, form the mixed serum of synthesis of molecular sieve, add organic formwork agent at last and continue making beating.
Described crystallization temperature is 100-200 ℃, and crystallization time is 10-100h.
Described silica gel and water glass mixed serum, wherein the pH value of the add-on hierarchy of control of water glass is 11-13.
The invention belongs to a kind of method of synthesizing submicron ZSM-5 molecular sieve under the template existence condition.Its zeolite crystal size is in the 300-500 nanometer range.
The method of synthetic ZSM-5 molecular sieve provided by the invention; Its principal feature is with solid silicone and the liquid soluble glass mixture silicon source as synthetic ZSM-5 molecular sieve; Improve the synthetic pulp fluid solid content thereby reach, realize having under the high density purpose of the synthetic ZSM-5 molecular sieve of amine.
The present invention utilizes the basicity of water glass solution self, satisfies the basicity requirement of synthetic system, has simplified the synthesis step of ZSM-5 molecular sieve.No longer add other alkaline matters or acidic substance regulation system potential of hydrogen in the synthetic system.
This compound method, simple to operate, combined coefficient is high, and the products obtained therefrom relative crystallinity is high, complete in crystal formation, grain colony is in the 300-500 nanometer.
Synthetic system no longer adds the potential of hydrogen of alkaline matter or acidic substance regulation system, only utilizes the basicity of water glass solution self, satisfies the basicity requirement of synthetic system, and raw material drops into the adjusting of ratio, must satisfy the pH value requirement of synthetic system.The additional proportion of the water glass solution in the system is the major components of regulation system basicity.Require synthetic slurry pH value in 11～13 scopes.
The adding of molecular sieve crystal seed in the mixed serum can improve crystallization rate.Crystal seed needs to dissolve in the water glass solution 50-100 ℃ of heating condition lower section, forms translucent emulsion.This emulsion play the guiding role to the molecular sieve crystallization.
The synthesis condition of ZSM-5 molecular sieve provided by the present invention, its crystallization temperature general requirement be 100～200 ℃ of scopes, crystallization time 10～100 hours.
ZSM-5 molecular sieve provided by the present invention, its BET specific surface area is greater than 350m
2/ g.
The invention has the beneficial effects as follows: present method is simple to operate, has simplified the synthesis step of ZSM-5 molecular sieve, and combined coefficient is high, and the products obtained therefrom relative crystallinity is high, complete in crystal formation, and grain colony is in the 300-500 nanometer.
Embodiment
Below in conjunction with embodiment the present invention is done and to further describe:
In an embodiment, said relative crystallinity is the ratio with the peak area sum of 5 characteristic peaks of 2 θ angles between 22.5～25.0 in the X-ray diffracting spectrum separately of product and standard specimen.The molecular sieve specific surface area adopts nitrogen adsorption BET method to measure.
Embodiment 1
In 25.2 gram deionized waters, add 235.3 gram water glass solutions and (contain SiO
219.9%, contain Na
2O 6.3%), add 3.8 gram crystal seeds, after the making beating evenly, be warming up to 90 ℃, continuously stirring 5 hours adds solid silicone 8.2 grams again and (contains SiO
289.3%), after the making beating evenly, adds alum liquor 43.5 grams and (contain Al
2O
37.2%), add n-Butyl Amine 99 10.6 grams at last, after the mixing making beating, in 180 ℃ of crystallization, finish crystallization after 20 hours, material is after 0.5N hydrochloric acid exchange washing, and 550 ℃ of retort furnace roastings obtain Hydrogen ZSM-5 molecular sieve.Product relative crystallinity 89%, silica alumina ratio 25, specific surface area 350m
2/ g, grain-size 400 nanometers.
Embodiment 2
In 56.5 gram deionized waters, add 217.5 gram water glass solutions and (contain SiO
220.5%, contain Na
2O 6.8%), add 3.0 gram crystal seeds, after the making beating evenly, be warming up to 80 ℃, continuously stirring 6 hours adds solid silicone 18.8 grams again and (contains SiO
290.7%), after the making beating evenly, adds alum liquor 36.2 grams and (contain Al
2O
37.5%), add n-Butyl Amine 99 11.6 grams at last, after the mixing making beating, in 170 ℃ of crystallization, finish crystallization after 24 hours, material is after 0.5N hydrochloric acid exchange washing, and 550 ℃ of retort furnace roastings obtain Hydrogen ZSM-5 molecular sieve.Product relative crystallinity 88%, silica alumina ratio 33, specific surface area 340m
2/ g, grain-size 300 nanometers.
Embodiment 3
In 97.3 gram deionized waters, add 276.4 gram water glass solutions and (contain SiO
218.5%, contain Na
2O 5.8%), add 4.5 gram crystal seeds, after the making beating evenly, be warming up to 100 ℃, continuously stirring 4 hours adds solid silicone 23.2 grams again and (contains SiO
289.3%), after the making beating evenly, adds alum liquor 40.6 grams and (contain Al
2O
37.7%), add n-Butyl Amine 99 15.6 grams at last, after the mixing making beating, in 180 ℃ of crystallization, finish crystallization after 22 hours, material is after 0.5N hydrochloric acid exchange washing, and 550 ℃ of retort furnace roastings obtain Hydrogen ZSM-5 molecular sieve.Product relative crystallinity 86, silica alumina ratio 41, specific surface area 342m
2/ g, grain-size 400 nanometers.
Embodiment 4
In 157.4 gram deionized waters, add 261.3 gram water glass solutions and (contain SiO
219.9%, contain Na
2O 6.3%), add 5.6 gram crystal seeds, after the making beating evenly, be warming up to 80 ℃, continuously stirring 6 hours adds solid silicone 32.6 grams again and (contains SiO
289.3%), after the making beating evenly, adds aluminum nitrate solution 39.1 grams and (contain Al
2O
37.2%), add n-Butyl Amine 99 18.9 grams at last, after the mixing making beating, in 175 ℃ of crystallization, finish crystallization after 24 hours, material is after 0.5N hydrochloric acid exchange washing, and 550 ℃ of retort furnace roastings obtain Hydrogen ZSM-5 molecular sieve.Product relative crystallinity 89%, silica alumina ratio 45, specific surface area 345m
2/ g, grain-size 300 nanometers.
Embodiment 5
In 134.5 gram deionized waters, add 285.3 gram water glass solutions and (contain SiO
218.5%, contain Na
2O 5.8%), add 5.5 gram crystal seeds, after the making beating evenly, be warming up to 90 ℃, continuously stirring 6 hours adds solid silicone 24.8 grams again and (contains SiO
289.3%), after the making beating evenly, adding aluminum chloride and alum liquor 34.7 grams (contain Al
2O
37.7%), add n-Butyl Amine 99 19.5 grams at last, after the mixing making beating, in 180 ℃ of crystallization, finish crystallization after 20 hours, material is after 0.5N hydrochloric acid exchange washing, and 550 ℃ of retort furnace roastings obtain Hydrogen ZSM-5 molecular sieve.Product relative crystallinity 85%, silica alumina ratio 45, specific surface area 335m
2/ g, grain-size 400 nanometers.
Embodiment 6
In 167.3 gram deionized waters, add 331.2 gram water glass solutions and (contain SiO
219.9%, contain Na
2O 6.3%), after the making beating evenly, be warming up to 100 ℃, continuously stirring 5 hours adds solid silicone 31.2 grams again and (contains SiO
289.3%), after the making beating evenly, adds alum liquor 37.7 grams and (contain Al
2O
37.2%), add n-Butyl Amine 99 23.1 grams at last, after the mixing making beating, in 160 ℃ of crystallization, finish crystallization after 100 hours, material is after 0.5N hydrochloric acid exchange washing, and 550 ℃ of retort furnace roastings obtain Hydrogen ZSM-5 molecular sieve.Product relative crystallinity 82%, silica alumina ratio 48, specific surface area 335m
2/ g, grain-size 500 nanometers.
Claims (10)
1. the compound method of a submicron order ZSM-5 molecular sieve is characterized in that: with silica gel and water glass serves as to mix the silicon source, is the aluminium source with aluminium salt, is crystal seed with the ZSM-5 molecular sieve, the synthetic ZSM-5 molecular sieve of crystallization under the organic formwork agent existence condition.
2. according to the compound method of the said submicron order ZSM-5 of claim 1 molecular sieve, it is characterized in that described silica gel is powder silicon-dioxide series products.
3. according to the compound method of the said submicron order ZSM-5 of claim 1 molecular sieve, it is characterized in that adding the molecular sieve crystal seed in the described mixing silicon source, the add-on of molecular sieve crystal seed is the 0-10% of total quality of material.
4. according to the compound method of the said submicron order ZSM-5 of claim 1 molecular sieve, it is characterized in that described aluminium salt is one or more the mixture in Tai-Ace S 150, aluminum chloride or the aluminum nitrate, wherein is preferably Tai-Ace S 150.
5. according to the compound method of the said submicron order ZSM-5 of claim 1 molecular sieve, it is characterized in that silica alumina ratio is 20-100 in described mixing silicon source and the aluminium source.
6. according to the compound method of the said submicron order ZSM-5 of claim 1 molecular sieve, it is characterized in that described organic formwork agent is an organic amine, wherein organic amine is ethamine, propylamine or n-Butyl Amine 99.
7. according to the compound method of the said submicron order ZSM-5 of claim 3 molecular sieve, it is characterized in that described molecular sieve crystal seed joins fully making beating in the water glass solution under 50-100 ℃.
8. according to the compound method of the said submicron order ZSM-5 of claim 1 molecular sieve; It is characterized in that described silica gel adds in the mixed serum of water glass and molecular sieve crystal seed pulls an oar; Add aluminium salt then, form the mixed serum of synthesis of molecular sieve, add organic formwork agent at last and continue making beating.
9. according to the compound method of the said submicron order ZSM-5 of claim 1 molecular sieve, it is characterized in that described crystallization temperature is 100-200 ℃, crystallization time is 10-100h.
10. according to the compound method of the said submicron order ZSM-5 of claim 1 molecular sieve, wherein the pH value of the add-on hierarchy of control of water glass is 11-13.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103495378A (en) * | 2013-09-27 | 2014-01-08 | 上海绿强新材料有限公司 | Olefin purification adsorbent and method thereof for olefin purification technology |
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| CN102442686A (en) * | 2010-09-30 | 2012-05-09 | 中国石油化工股份有限公司 | Preparation method of ZSM-5 molecular sieve |
| CN102502696A (en) * | 2011-11-16 | 2012-06-20 | 大连理工大学 | Synthetic method of ZSM-5 zeolites |
| CN102530986A (en) * | 2012-01-10 | 2012-07-04 | 复旦大学 | Method for producing MFI type zeolites |
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2012
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102442686A (en) * | 2010-09-30 | 2012-05-09 | 中国石油化工股份有限公司 | Preparation method of ZSM-5 molecular sieve |
| CN102502696A (en) * | 2011-11-16 | 2012-06-20 | 大连理工大学 | Synthetic method of ZSM-5 zeolites |
| CN102530986A (en) * | 2012-01-10 | 2012-07-04 | 复旦大学 | Method for producing MFI type zeolites |
Non-Patent Citations (2)
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| 张领辉等: "不同晶粒大小ZSM-5的合成和表征", 《催化学报》 * |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103495378A (en) * | 2013-09-27 | 2014-01-08 | 上海绿强新材料有限公司 | Olefin purification adsorbent and method thereof for olefin purification technology |
| CN103495378B (en) * | 2013-09-27 | 2015-08-05 | 上海绿强新材料有限公司 | A kind of alkene purifying adsorbent and the method for alkene process for purifying thereof |
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