CN102464327A - Method for modifying molecular sieve - Google Patents
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- CN102464327A CN102464327A CN201010536185XA CN201010536185A CN102464327A CN 102464327 A CN102464327 A CN 102464327A CN 201010536185X A CN201010536185X A CN 201010536185XA CN 201010536185 A CN201010536185 A CN 201010536185A CN 102464327 A CN102464327 A CN 102464327A
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Abstract
The invention relates to a method for modifying a molecular sieve, which comprises the steps of: firstly, extracting an organic template agent in molecular sieve raw powder containing the organic template agent on an extraction device by using an organic agent; and then carrying out ion exchange on the extraction device by using an acid solution, and translating into a hydrogen type molecular sieve, wherein no roasting step exists in the method of modifying the molecular sieve. The method provided by the invention has the advantages of high degree of crystallization, high modifying efficiency, no pollution and the like.
Description
Technical field
The present invention relates to a kind of method of modifying of molecular sieve.More particularly, the present invention relates to that a kind of former powder after synthetic removes organic formwork agent and the method that changes hydrogen type molecular sieve into molecular sieve.
Background technology
Molecular sieve is the important member in the crystalline material, has had been found that a variety of molecular sieves at present, zeolite A for example, ZSM series, β, X, Y, mesoporous molecular sieves such as micro porous molecular sieve such as SAPO series and MCM-41.
Molecular sieve is widely used in fields such as absorption, separation, catalysis, IX and Subjective and Objective assembling owing to having regular pore structure, bigger surface-area, a large amount of exchangable ion and abundant shape characteristics.In general; The building-up process of most molecular sieves will be introduced organism as template; Like organic amine, tensio-active agent etc.; Organic formwork agent has important effect in molecular sieve synthetic, many compositions are abundant, the existence of organic formwork agent is all given the credit in the successful exploitation of the porous material of novel structure, although the mechanism of action of organic formwork agent does not also obtain the understanding of unanimity; Have any to affirm, most exactly template finally all is to stay in the duct or cage of molecular sieve with the form bag of guest molecule.Before this type material being carried out application such as catalysis, absorption, separation and Subjective and Objective assembling, must organic formwork agent be removed from the duct of inorganic main body, to form regular, unobstructed duct.This shows that removing of organic formwork agent is the important step that molecular sieve is realized its application.
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 calcination under air, oxygen or inert atmosphere (400～800 ℃) that obtains, and make organic formwork agent resolve into small molecules or oxidized and from inorganic main body, remove out.But roasting method generally is suitable for the higher molecular sieve of some thermostabilitys; Skeleton contraction or avalanche phenomenon take place in the process of roasting in the molecular sieve easily relatively poor for thermostability; Even for the higher molecular sieve of thermostability; Because the long-time high temperature of roasting method also can cause the destruction in various degree of its structure, and then influence its use properties.CN1138007A discloses the promoted roasting method of a kind of oxygenant; Be earlier molecular sieve to be used oxygenant; Handle like hydrogen peroxide solution, then 200～500 ℃ of following roastings, this method is the improvement to the thermal bake-out method; But it is little that maturing temperature reduces amplitude, the shortcoming that still has common roasting method and had.CN200610038788.0 discloses a kind of preparation method of MCM-48 separatory membrane, and the technology of preparation MCM-48 separatory membrane is removed template with extracting process in the preparation process on cellular ceramic substrate.Adopt hydrothermal synthesis method on porous supporting body, to prepare the former film of MCM-48, adopt the organic solvent extraction template, improve molecular diffusion through heating and stirring extraction agent simultaneously, rapidly and efficiently remove the template in the former film of MCM-48.This method adopts the template in the common equipment extraction molecule sieve, and extraction efficiency needs further to improve.
The immense success of zeolite molecular sieve on using except the variation of the singularity of structure and kind, has confidential relation with the modifiability of their structures and performance.The study on the modification of zeolite molecular sieve and their the synthetic the same zeolite CHEMICAL DEVELOPMENT that promoted with application and development we can say the development that does not have modification technology, just do not have the widespread use of zeolite molecular sieve.
The range of application of zeolite molecular sieve has been expanded in the adjustable sex change of zeolite molecular sieve diversity structure, particularly structure and character widely.IX is the most classical, the most frequently used and the Zeolite modifying method of easy row, at present wide range of industrial applications.In processes such as absorption and catalysis; Generally all need the acid position to promote catalyzed reaction, and the positively charged ion on the molecular sieve that generally is synthesized surface is a basic metal, is not possess or very faint acidity; Can not satisfy the requirement of use; Will carry out IX like this, and be exchanged for the alkalimetal ion on surface to have the tart positively charged ion, what adopt at present generally is ammonium salt exchange and acid exchange.The ammonium salt exchange generally will just can reach requirement through repeatedly exchanging; There are shortcomings such as complex operation, time length and cost height; And the molecular sieve that obtains containing the ammonium radical ion will pass through roasting and be converted into hydrogen type molecular sieve, causes environmental pollution, cost to improve and to the shortcomings such as secondary destruction of molecular sieve.Problems such as the conventional method with the acid exchange exists still that above-mentioned periodical operation, labour intensity are big, serious waste of resources and environmental pollution.
Summary of the invention
To the deficiency of prior art, the invention provides a kind of method of modifying of molecular sieve, that the process that the present invention is used for modified molecular screen has is simple to operate, the time is short, temperature is low, molecular sieve is destroyed characteristics such as little.
The method of modifying process of molecular sieve of the present invention is following: the molecular screen primary powder that synthetic is contained organic formwork agent at first extracts organic formwork agent wherein with organic solvent on extraction plant; On this extraction plant, carry out IX with acid solution then; Change hydrogen type molecular sieve into, do not have calcination steps in the above-mentioned method of modifying of molecular sieve.
Organic solvent can for can with the interactional polar organic matter of organic formwork agent or/and nonpolar organic matter; Be preferably one or more that are selected from alkane, alkene, aromatic hydrocarbons and verivate thereof; More preferably be selected from sherwood oil, THF, furfural, acetate, benzene,toluene,xylene, methylene dichloride, trichloromethane, monochloroethane, the ethylene dichloride one or more; Most preferably be toluene or/and trichloromethane.Can preferably confirm according to the organic formwork agent kind described in the synthesis of molecular sieve.
The used acid of acid solution can be for organic acid or/and organic acid; Be preferably and be selected from hydrochloric acid, nitric acid, hydrofluoric acid, Hydrogen bromide, formic acid, acetate, the oxalic acid one or more; More preferably be selected from hydrochloric acid or/and nitric acid.The concentration of acid solution is generally 0.1～10mol/L.
The temperature of above-mentioned extraction organic formwork agent and acid solution IX can be the boiling temperature of room temperature to organic solvent or acid, and pressure can be normal pressure, and the time is confirmed according to the character needs of modified molecular screen, was generally 2～24 hours.
Continous way operation is preferably adopted in above-mentioned extraction organic formwork agent and acid solution IX, and the preferred recycling use of organic solvent and acid solution is as separating organic solvent or acid solution and recycle through distilling mode such as condensation.
The molecular sieve modified method of the present invention is under demulcent condition very, and modifying process does not carry out high-temperature roasting to be handled, and has reduced the molecular sieve pore passage structural damage.Specifically the inventive method has following advantage: 1. can keep the structure and the character of molecular sieve to greatest extent, avoid routine techniques to cause the destruction to molecular sieve structure and character; 2. operate continuously can be saved time significantly, improves processing efficiency; 3. can carry out recycling to treatment solution and the material that extracts, improve the utilization ratio of resource, avoid pollution again environment; 4. can be as required, the element that in the load simultaneously of a process, needs; 5. the sample after handling gets final product through super-dry, has avoided the multiple high temp of conventional treatment method to be burnt, and has avoided the destruction to molecular sieve structure, has reduced energy consumption.
Description of drawings
The molecular sieve modified schematic diagram of device of a kind of experiment that Fig. 1 the inventive method is adopted.
Wherein: 1-treatment solution, 2-distiller, 3-sample, 4-sample pool, 5-prolong.
Embodiment
For the ease of method of the present invention is expressed more specifically, in conjunction with the accompanying drawings, but realize that equipment of the present invention is not limited to the device of Fig. 1.
Device mainly is made up of three parts among Fig. 1, is respectively distiller 2, sample pool 4 and prolong 5.Sieve sample 3 is positioned in the sample pool 4, and treatment solution 1 (can be the organic solvent of extraction template, also can be the acid solution of IX) is positioned in the distiller 2; After solution in the distiller is heated and seethes with excitement, flow in the sample pool 4 after 5 condensations of steam process prolong, aperture is arranged at the sample pool bottom; Chuck outside the liquid that refluxes enters into through sample layer, the chuck upper end highly is lower than the upper end height of sample pool, along with the increase of liquid; When liquid level is higher than the edge of chuck, will overflow, be back in the distiller; The sample that can keep like this handling in treatment solution, improves processing efficiency all the time.In addition,, so just can accelerate extraction (IX) speed, reach better treatment effect because the liquid that refluxes is the treatment solution than comparatively fresh all the time.
The method of handling of molecular sieve disclosed by the invention can be divided into for two steps: the first step is with organic solvent molecular sieve to be handled, and purpose is under than the demulcent condition, to extract the template in the molecular sieve pore passage; Second step was to be replaced by acid solution to treatment solution, and the backflow through after a while just can become hydrogen ion to the alkali metal cation-exchanged in the molecular sieve, changes molecular sieve into hydrogen type molecular sieve.The another one benefit of present method is exactly can be as required, the element that introducing needs in IX, for example halogen etc.
Through embodiment scheme of the present invention is further explained below.
Among below the embodiment and Comparative Examples, the relative crystallinity of molecular screen primary powder and sample is used XRD analysis, and wherein the relative crystallinity of molecular screen primary powder is defined as 100%, and the percent crystallinity of sample obtains relative crystallinity by comparison.
The preparation of modified zsm-5 zeolite (E-1)
The process of this method is following:
(1) gets the former powder of 100 gram ZSM-5 (nitrogen content 0.8 quality %; Sodium content 2.8 quality %) be positioned in the sample pool 4, in distiller 2, add 500 milliliters of toluene, heating makes the toluene boiling; Refluxed 6 hours; Sample calculates denitrification percent (template is a nitrogenous compound) through drying treatment post analysis nitrogen content wherein, and the result sees table 1.
(2) sample that step (1) obtains of learning from else's experience is positioned in the sample pool 4, in distiller 2, adds the hydrochloric acid of 500 milliliter of 3.0 quality %, and heating makes the hydrochloric acid boiling; Refluxed 8 hours; Sample calculates and takes off the sodium rate through drying treatment its relative crystallinity of post analysis and sodium content, and the result sees table 1.
The preparation of modified beta molecular sieve (E-2)
The process of this method is following:
(1) gets the former powder of 100 gram beta-molecular sieves (nitrogen content 1.1 quality %; Sodium content 3.2 quality %) be positioned in the sample pool 4, in distiller 2, add 500 milliliters of trichloromethanes, heating makes the trichloromethane boiling; Refluxed 12 hours; Sample calculates denitrification percent through drying treatment post analysis nitrogen content wherein, and the result sees table 1.
(2) sample that step (1) obtains of learning from else's experience is positioned in the sample pool 4, in distiller 2, adds 500 milliliter 3.0% hydrochloric acid, and heating makes the hydrochloric acid boiling; Refluxed 8 hours; Sample calculates and takes off the sodium rate through the relative crystallinity and the sodium content of drying treatment post analysis sample, and the result sees table 1.
The preparation of modified ZSM-5-22 molecular sieve (E-3)
Treating processes is at the beginning of the difference that with embodiment 1 ZSM-22 molecular sieve (nitrogen content 0.6 quality %, sodium content 1.6 quality %) replaces the ZSM-5 molecular sieve, and the result sees table 1.
The preparation of modified ZSM-5-23 molecular sieve (E-4)
Treating processes is at the beginning of the difference that with embodiment 1 ZSM-23 molecular sieve (nitrogen content 0.7 quality %, sodium content 1.9 quality %) replaces the ZSM-5 molecular sieve, and organic solvent is the mixture (volume ratio 1: 1) of toluene and THF, and the sample analysis result sees table 1.
The preparation of modification EU-1 molecular sieve (E-5)
Treating processes is at the beginning of the difference that with embodiment 1 EU-1 molecular sieve (nitrogen content 0.9 quality %, sodium content 2.1 quality %) replaces the ZSM-5 molecular sieve, and the result sees table 1.
Embodiment 6
The preparation of modified MC M-22 molecular sieve (E-6)
Treating processes is at the beginning of the difference that with embodiment 1 MCM-22 molecular sieve (nitrogen content 1.2 quality %, sodium content 2.3 quality %) replaces the ZSM-5 molecular sieve, and the result sees table 1.
Comparative Examples 1
The preparation of modified zsm-5 zeolite (C-1)
(1) get the 100 gram former powder of ZSM-5 (nitrogen content 0.8 quality %, sodium content 2.8 quality %), in 500 ℃ of air atmospheres, burnt 6 hours, the nitrogen content of analytic sample calculates denitrification percent, and the result sees table 1.
(2) get in the hydrochloric acid that sample 50 grams that step (1) obtains join 500 milliliter 3.0%, exchange is 1 hour under 80 ℃ of stirring condition, repeats 3 times; The sample that obtains is through drying treatment; The relative crystallinity of analytic sample and sodium content calculate and take off the sodium rate, and the result sees table 1.
The character of the various samples of table 1
| Sample | Denitrification percent, % | Take off the sodium rate, % | Relative crystallinity, % |
| E-1 | 98.6 | 96.0 | 93.3 |
| E-2 | 98.9 | 95.5 | 91.7 |
| E-3 | 97.3 | 95.8 | 92.5 |
| E-4 | 98.4 | 95.1 | 94.8 |
| E-5 | 99.1 | 96.7 | 93.2 |
| E-6 | 97.4 | 97.3 | 92.4 |
| C-1 | 98.8 | 92.9 | 86.4 |
Can find out from the result of table 1; The sample that the inventive method obtains is under the situation suitable with the sample denitrification percent of control methods preparation; Compare with comparative example, the sample of the inventive method preparation takes off the rate of receiving and improves more than 2 percentage points, and relative crystallinity improves more than 5 percentage points.
Claims (8)
1. the method for modifying of a molecular sieve; It is characterized in that: the molecular screen primary powder that synthetic is contained organic formwork agent at first extracts organic formwork agent wherein with organic solvent on extraction plant; On this extraction plant, carry out IX with acid solution then; Change hydrogen type molecular sieve into, do not have calcination steps in the above-mentioned method of modifying of molecular sieve.
2. according to the described method of claim 1, it is characterized in that: organic solvent for can with the interactional polar organic matter of organic formwork agent or/and nonpolar organic matter.
3. according to the described method of claim 2, it is characterized in that: organic solvent is selected from one or more in sherwood oil, THF, furfural, acetate, benzene,toluene,xylene, methylene dichloride, trichloromethane, monochloroethane, the ethylene dichloride.
4. according to the described method of claim 1, it is characterized in that: the used acid of acid solution is that organic acid is or/and organic acid.
5. according to the described method of claim 4, it is characterized in that: the used acid of acid solution is selected from one or more in hydrochloric acid, nitric acid, hydrofluoric acid, Hydrogen bromide, formic acid, acetate, the oxalic acid.
6. according to the described method of claim 1, it is characterized in that: the temperature of extraction organic formwork agent and acid solution IX is from the boiling temperature of room temperature to organic solvent or acid, and pressure is normal pressure, and the time is 2～24 hours.
7. according to the described method of claim 1, it is characterized in that: the continous way operation is adopted in extraction organic formwork agent and acid solution IX.
8. according to the described method of claim 7, it is characterized in that: organic solvent and acid solution recycling use.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114105167A (en) * | 2020-08-28 | 2022-03-01 | 中国石油化工股份有限公司 | Sulfydryl functionalized MCM-41 molecular sieve and preparation method and application thereof |
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| US20010044372A1 (en) * | 1998-10-09 | 2001-11-22 | Vaughan David E.W. | Soft chemistry resynthesis route to faujasitic and related FCC catalyst promoters (LAW529) |
| CN1608992A (en) * | 2003-10-24 | 2005-04-27 | 中国石油化工股份有限公司 | Modified molecular sieve and its prepn process |
| CN101161343A (en) * | 2007-11-22 | 2008-04-16 | 天津大学 | A novel catalyst for synthesizing pyridine base as well as its preparing and using method |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114105167A (en) * | 2020-08-28 | 2022-03-01 | 中国石油化工股份有限公司 | Sulfydryl functionalized MCM-41 molecular sieve and preparation method and application thereof |
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Application publication date: 20120523 |