CN1307097C - Method of removing organic template agent from molecular sieve - Google Patents
Method of removing organic template agent from molecular sieve Download PDFInfo
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- CN1307097C CN1307097C CNB2005100611843A CN200510061184A CN1307097C CN 1307097 C CN1307097 C CN 1307097C CN B2005100611843 A CNB2005100611843 A CN B2005100611843A CN 200510061184 A CN200510061184 A CN 200510061184A CN 1307097 C CN1307097 C CN 1307097C
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- molecular sieve
- formwork agent
- organic formwork
- described method
- removes organic
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Abstract
The present invention provides a method for removing organic template agents from molecular sieves. The present invention comprises steps that the obtained molecular sieve with an organic template agent by synthesizing is arranged in a light reactor; a water solution of hydrogen peroxide with the amount of 1 to 10 wt % of the molecular sieve is added; the reaction system is agitated; the pH value is regulated between 1 and 10 by inorganic acid or inorganic hydroxide; the reaction system is radiated by an ultraviolet light source; after the reaction proceeds at room temperature for 0.5 to 5 hours, the reaction liquid is filtered and the molecular sieve is washed with deionized water. Compared with the existing methods for removing organic template agents, the present invention can effectively remove the organic template agent from the molecular sieve at room temperature, and have the advantages of moderate condition and simple operation.
Description
Technical field
Present technique belongs to the inorganic porous material field, is specifically related to a kind of method that removes organic formwork agent in the molecular sieve.
Technical background
Molecular screen material is owing to have the duct of rule, bigger surface-area and abundant pattern and be widely used in fields such as absorption, separation, catalysis, ion-exchange and Subjective and Objective assembling.As everyone knows, molecular sieve synthetic is to be feature to introduce organic formwork molecule (organic amine, tensio-active agent or block polymer), organic formwork agent plays a very important role in the building-up process of molecular sieve, many compositions are abundant, the synthetic existence that all should give the credit to organic formwork agent of the success of the porous material of novel structure, although the mechanism of action of organic formwork agent does not also obtain consistent understanding, have a bit and can affirm that but promptly Jue Daduoshuo template is finally all stayed in the duct or ridge of molecular sieve with the form bag of guest molecule.Before this class material being carried out application such as catalysis, absorption, separation and Subjective and Objective assembling, organic formwork agent must be removed from the duct of inorganic main body, to form regular, spacious duct.This shows that removing of organic formwork agent is that molecular sieve is realized its key in application step.
Removing the most frequently used and industrialized method of organic formwork agent is the thermal bake-out method.Promptly directly will synthesize the molecular sieve material that obtains and place retort furnace or tube furnace calcination under air, oxygen or inert atmosphere (400-600 ℃ usually), and make organic formwork agent resolve into small molecules and from inorganic main body, remove out.But roasting method only is suitable for some thermally-stabilised higher molecular sieves, and the relatively poor molecular sieve of thermostability skeleton takes place when thermal bake-out easily shrinks or the avalanche phenomenon.Report the novel method of some removed template methods in recent years in succession, as the promoted roasting method of oxygenant (CN 1138007A), solvent extration and Microwave Digestion etc.These methods have certain superiority, but also exist not enough.As the promoted roasting method of oxygenant be earlier with molecular sieve with aqueous hydrogen peroxide solution wetting after again 200-500 ℃ of following roasting, this method is the improvement to the thermal bake-out method, but the amplitude that maturing temperature reduces and little.Solvent extration is to use organic solvent that template is extracted from inorganic duct, the recyclable usefulness again of template, but this method not only needs a large amount of organic solvents, operates more consuming time, and organic formwork agent can not all remove, and needs follow-up roasting remove remaining organic formwork agent.Microwave Digestion adopts inorganic oxidising acid and hydrogen peroxide, makes organic formwork agent clear up and remove under microwave heating.This method biggest advantage is that the operating time is short, only need several minutes, but reaction conditions is too violent, and scale resistance and not acid proof molecular sieve are then not powerless to some.
Summary of the invention
The objective of the invention is to propose a kind of method that at room temperature can remove organic formwork agent in the molecular sieve effectively.
The removal methods of organic formwork agent in the molecular sieve that the present invention proposes is that the synthetic molecular sieve material that contains organic template that obtains is placed a kind of aqueous solution that contains oxygenant, in conjunction with ultraviolet radiation, at room temperature removes organic formwork agent.
The removal methods of organic formwork agent in the molecular sieve that the present invention proposes, the synthetic molecular sieve that obtains containing organic template is placed photoreactor, the consumption that adds hydrogen peroxide is the aqueous solution of 1～10% hydrogen peroxide of molecular sieve weight, the stirring reaction system, regulate the pH value between 1～10 with mineral acid or mineral alkali, ultraviolet source radioreaction system, reaction is carried out at ambient temperature, 0.5 after～5 hours, filtering reacting liquid also gets final product with deionized water wash.
Said molecular sieve is meant micro porous molecular sieve (as BEA etc.) and mesopore molecular sieve (as MCM-41, SBA15, SBA16, HMS etc.) in the method that the present invention proposes.
The hydrogen peroxide optimum amount scope of indication is in the method that the present invention proposes: the consumption of hydrogen peroxide is 1～4% of a molecular sieve weight.
The mineral acid of indication can be HCl, H in the method that the present invention proposes
2SO
4, mineral alkali can be NaOH, KOH, pH value scope is preferably between 3～7.
Can add catalyzer in the reaction system of the method that the present invention proposes is Fe
2+Or Fe
3+, its consumption is 0～1000ppm.
The indication UV-light is produced by low pressure or middle pressure Hg lamp in the method that the present invention proposes.
In the method that the present invention proposes, the ultraviolet radiation time is 1～4 hour.
The present invention compares with the method for existing stripper plate agent, condition as mild as a dove, can remove organic formwork agent in the molecular sieve under the room temperature effectively, simple to operate, adopt this method can improve the performance of molecular screen material, as structurally ordered Du Genggao, surface hydroxyl is abundanter, pore volume and the aperture is bigger and specific surface area is high more high.
Embodiment
Example 1:
The organic amine template removes among the micro porous molecular sieve BEA.The synthetic former powder of BEA that contains organic amine (tetraethyl ammonium hydroxide) that obtains of 0.6 gram is placed the glass reactor with chuck, and (reactor cools off with tap water all the time, guarantee to react and at room temperature carry out), add 60ml, concentration 0.1-10% superoxol, regulating pH with HCl is 1～7, with middle pressure Hg ultra violet lamp 1-5 hour, finish after-filtration and get final product of reaction with deionized water wash.The gained sample characterizes with means such as ultimate analysis, XRD, N2 absorption.The result shows that template 100% removes, and compares with roasting method, and the sample structure that this method obtains not have contraction substantially, and aperture, pore volume are bigger, and specific surface area is higher.
Example 2:
Removing of mesopore molecular sieve MCM-41 cats product template.The synthetic former powder of MCM-41 that contains cationic active agent (hexadecyl front three agent brometo de amonio) that obtains of 0.6 gram is placed glass reactor (reactor is cut to protect to react with the tap water cooling all the time and at room temperature carried out) with chuck, add 60ml, concentration 0.1～5% aqueous hydrogen peroxide solution is used H
2SO
4Regulate pH=1～7, ultra violet lamp 1～4 hour, finish after-filtration and get final product of reaction with deionized water wash.The ultimate analysis of gained sample, XRD, N
2Means such as absorption characterize.The result shows that template 100% removes, and compares with roasting method, and the sample skeleton degree of order that this method obtains improves greatly, and skeleton does not have to shrink substantially, and aperture/pore volume more greatly, and specific surface area is higher.
Example 3:
Removing of mesoporous molecular sieve SBA-15 nonionogenic tenside template.With 0.6 gram synthetic obtain contain nonionogenic tenside (block polymer P
123) the former powder of SBA-15 place glass reactor with chuck (reactor is cut with the tap water cooling all the time and protected reaction and at room temperature carry out), add 60ml, concentration 0.1～5% aqueous hydrogen peroxide solution and 1～500ppmFe
2+, regulate pH=1～10 with NaOH, ultra violet lamp 0.5～5 hour, finish after-filtration and get final product of reaction with deionized water wash.The ultimate analysis of gained sample, XRD, N
2Means such as absorption characterize.The result shows that template 100% removes, and compares with roasting method, and the sample skeleton degree of order that this method obtains improves greatly, and skeleton not have contraction substantially, and aperture, pore volume are bigger, and specific surface area is higher.
Example 4:
Removing of mesopore molecular sieve ZrSBA-15 nonionogenic tenside template.With 0.6 gram synthetic obtain contain nonionogenic tenside (block polymer P
123) the former powder of ZrSBA-15 place glass reactor with chuck (reactor is cut with the tap water cooling all the time and protected reaction and at room temperature carry out), add 60ml, concentration 0.1～5% aqueous hydrogen peroxide solution and 1～500ppmFe
2+, regulate pH=1～10 with KOH, ultra violet lamp 0.5～5 hour, finish after-filtration and get final product of reaction with deionized water wash.The ultimate analysis of gained sample, XRD, N
2Means such as absorption characterize.The result shows that template 100% removes, and compares with roasting method, and the sample skeleton degree of order that this method obtains improves greatly, and skeleton not have contraction substantially, and aperture, pore volume are bigger, and specific surface area is higher.
Example 5:
Removing of mesopore molecular sieve SBA-16 nonionogenic tenside template.With 0.6 gram synthetic obtain contain nonionogenic tenside (block polymer P
127) the former powder of SBA-16 place glass reactor with chuck (reactor is cut with the tap water cooling all the time and protected reaction and at room temperature carry out), add 60ml, concentration 0.1～5% aqueous hydrogen peroxide solution and 30～300ppmFe
3+, regulate pH=3～7 with NaOH, ultra violet lamp 0.5～4 hour, finish after-filtration and get final product of reaction with deionized water wash.The ultimate analysis of gained sample, XRD, N
2Means such as absorption characterize.The result shows that template 100% removes, and compares with roasting method, and the sample skeleton degree of order that this method obtains improves greatly, and skeleton not have contraction substantially, and aperture, pore volume are bigger, and specific surface area is higher.
Claims (8)
1, a kind of method that removes organic formwork agent in the molecular sieve, it is characterized in that this method is that the synthetic molecular sieve that obtains containing organic template is placed photoreactor, the consumption that adds hydrogen peroxide is the aqueous solution of 1～10% hydrogen peroxide of molecular sieve weight, the stirring reaction system, regulate between the pH value 1～10 with mineral acid or mineral alkali, the ultraviolet source irradiation reaction system, reaction is carried out at ambient temperature, 0.5 after～5 hours, filtering reacting liquid is also used deionized water wash.
2,, it is characterized in that said molecular sieve is meant that micro porous molecular sieve BEA or mesopore molecular sieve MCM-41, SBA15, SBA16, HMS's is a kind of according to the described method that removes organic formwork agent in the molecular sieve of claim 1.
3, according to the described method that removes organic formwork agent in the molecular sieve of claim 1, the consumption that it is characterized in that said hydrogen peroxide is 1～4% a scope of molecular sieve weight.
4,, it is characterized in that said ultraviolet source is meant low pressure or medium pressure mercury lamp according to the described method that removes organic formwork agent in the molecular sieve of claim 1.
5,, it is characterized in that said mineral acid is HCl or H according to the described method that removes organic formwork agent in the molecular sieve of claim 1
2SO
4
6,, it is characterized in that said mineral alkali is NaOH or KOH according to the described method that removes organic formwork agent in the molecular sieve of claim 1.
7,, it is characterized in that said pH value is between 1～7 according to the described method that removes organic formwork agent in the molecular sieve of claim 1.
8, according to the described method that removes organic formwork agent in the molecular sieve of claim 1, it is characterized in that in the said reaction system, add catalyst Fe
2+Or Fe
3+, its consumption is 0～1000ppm.
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| CNB2005100611843A CN1307097C (en) | 2005-10-20 | 2005-10-20 | Method of removing organic template agent from molecular sieve |
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| CNB2005100611843A CN1307097C (en) | 2005-10-20 | 2005-10-20 | Method of removing organic template agent from molecular sieve |
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| CN1307097C true CN1307097C (en) | 2007-03-28 |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101823728B (en) * | 2010-05-19 | 2012-06-20 | 上海化工研究院 | Method for preparing small-crystal-size SAPO-34 zeolite |
| JP6626103B2 (en) * | 2014-07-11 | 2019-12-25 | トタル リサーチ アンド テクノロジー フエリユイ | Method for producing a mesoporous microporous crystalline material containing a recoverable and recyclable mesopore-template agent |
| CN106145142B (en) * | 2015-04-13 | 2019-04-12 | 中国石油化工股份有限公司 | Remove molecular sieve organic formwork agent method |
| CN105271284A (en) * | 2015-06-09 | 2016-01-27 | 浙江师范大学 | Method for removing organic template agent in porous material through wet method |
| CN108529647B (en) * | 2018-06-05 | 2021-06-22 | 常州大学 | Synthesis method of nano ZSM-22 zeolite assembly containing mesoporous structure |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1138007A (en) * | 1995-06-14 | 1996-12-18 | 中国石油化工总公司 | Method for removing organic template agent in ultramacroporous molecular sieve |
| CN1515490A (en) * | 2003-08-26 | 2004-07-28 | 复旦大学 | Method for removing organic-inorganic composite porous material organic template agent |
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2005
- 2005-10-20 CN CNB2005100611843A patent/CN1307097C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1138007A (en) * | 1995-06-14 | 1996-12-18 | 中国石油化工总公司 | Method for removing organic template agent in ultramacroporous molecular sieve |
| CN1515490A (en) * | 2003-08-26 | 2004-07-28 | 复旦大学 | Method for removing organic-inorganic composite porous material organic template agent |
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