CN104353484A - Preparation method of low-cost strong-acid hierarchical-pore Beta zeolite - Google Patents
Preparation method of low-cost strong-acid hierarchical-pore Beta zeolite Download PDFInfo
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Abstract
The invention discloses a preparation method of low-cost strong-acid hierarchical-pore Beta zeolite, and relates to a preparation method of hierarchical-pore Beta zeolite. The problem that the acidity of an existing desilicication post-treatment hierarchical-pore Beta zeolite molecular sieve is weakened is solved. The preparation method comprises the steps of 1. calcining Beta zeolite to obtain microporous hydrogen type Beta zeolite; 2. adding the microporous hydrogen type Beta zeolite into an alkaline solution, stirring, and washing and drying to obtain sodium type desilicication hierarchical-pore Beta zeolite; 3. adding the sodium type desilicication hierarchical-pore Beta zeolite into an ammonium nitrate aqueous solution for exchange, and calcining to obtain hydrogen type desilicication hierarchical-pore Beta zeolite; and 4. adding the hydrogen type desilicication hierarchical-pore Beta zeolite into an acidic solution, stirring, washing and drying, and repeating the step 3 to obtain the strong-acid hierarchical-pore Beta zeolite.
Description
Technical field
The present invention relates to a kind of preparation method of multi-stage porous Beta zeolite.
Background technology
Zeolitic material has peracidity and high-specific surface area, is a kind of outstanding acidic catalyst.Meanwhile, zeolitic material has very strong chemical stability and hydrothermal stability, is difficult to be destroyed by reactant corrosion dissolution.Relative to usual used homogeneous catalyst, zeolitic material catalyst directly can reuse and without the need to being separated, can not pollute environment and product simultaneously.
At present, zeolite catalyst is widely used in acidic catalyst reaction, as cracking reaction, in Friedel-Crafts reaction.Wherein, the pore passage structure of Beta zeolite is comparatively large, and is three-dimensional open-framework, and therefore reactivity worth is very excellent.Especially for Friedel-Crafts, Beta zeolite facies for other kind zeolite catalysts more excellence have high activity and high selectance simultaneously.But even if having larger pore passage structure, the application of Beta zeolite in large molecular acid reaction is still subject to the larger obstruction of pore size.
React for macromolecular acidic catalyst, except quantity and the intensity in acidity of catalyst site, what also need to consider acidity of catalyst site can contact, namely has how many acidic sites can be arrived by large molecule contacts.React for the Friedel-Crafts of trimethylbenzene and benzyl alcohol, benzyl alcohol can react in the duct of catalyst, generates intermediate.And be greater than the channel diameter of zeolite due to the size of trimethylbenzene so duct cannot be entered and intermediate continues to react, therefore, in the second stage of reaction, intermediate need to dissociate and trimethylbenzene outside to catalyst carries out reaction generation target product.In this process, intermediate micropore and mesoporous in mass transfer velocity be the key factor of reacting, on the one hand, can have influence on the speed of reaction, on the other hand, the intermediate that cannot touch trimethylbenzene immediately can generate methyl phenyl ethers anisole thus the productive rate of impact reaction.
The application of multi-stage porous Beta zeolite can address this problem.On the one hand multi-stage porous Beta zeolite has a large amount of mesopore surfaces, its size in several nanometer to tens nanometer, much larger than macromolecular size, the benzyl alcohol reacted at these mesopore surfaces can directly and trimethylbenzene react, raising reaction speed and selectance.On the other hand, these are mesoporous is connected to microcellular structure, by the pipe cutting of micropore, thus shortens the mass transfer distance of micropore.In addition, meso-hole structure is more difficult to be blocked by carbon distribution and reactant, and multi-stage porous Beta zeolite facies have stronger anti-deactivation for micropore Beta zeolite.Current research shows, porous zeotile can promote catalyst 10-15 anti-deactivation doubly.
But, the synthesis of multi-stage porous Beta zeolite molecular sieve at present mainly through adding the method preparation of mesoporous template or mesoporous directed agents in synthesis, this method due to the price of mesoporous template and directed agents very high, be only applicable to laboratory scope.And another kind of method, the multi-stage porous Beta zeolite molecular sieve obtained by desiliconization post processing, although cheap, simple to operate, be applicable to commercial Application, but because the special construction of Beta molecular sieve, post treatment method can cause acidity of catalyst decline and have a strong impact on its respond.
Summary of the invention
The present invention is that the acidity that will solve existing desiliconization post processing multi-stage porous Beta zeolite molecular sieve weakens problem, provides a kind of preparation method of cheap highly acid multi-stage porous Beta zeolite.
The preparation method of the present invention's cheap highly acid multi-stage porous Beta zeolite, carries out according to the following steps:
One, Beta zeolite is calcined 3 ~ 10 hours at 500 ~ 600 DEG C, obtain micropore Hydrogen Beta zeolite;
Two, micropore Hydrogen Beta zeolite being joined concentration is in the aqueous slkali of 0.1 ~ 2mol/L, 0.5 ~ 2h is stirred at 0 ~ 100 DEG C, then deionized water micropore Hydrogen Beta zeolite is spent to filtrate in neutral, drier at 100 ~ 120 DEG C, obtain sodium form desiliconization multi-stage porous Beta zeolite;
Three, it is exchange 1 ~ 5 time in the aqueous ammonium nitrate solution of 1 ~ 2mol/L that sodium form desiliconization multi-stage porous Beta zeolite step 2 obtained joins concentration, exchanges 0.5 ~ 2h at every turn, obtains Hydrogen desiliconization multi-stage porous Beta zeolite at 500 ~ 600 DEG C after calcining 5h;
Four, the Hydrogen desiliconization multi-stage porous Beta zeolite obtained in step 3 being joined concentration is in the acid solution of 0.05 ~ 2mol/L, 0.5 ~ 10h is stirred at 0 ~ 100 DEG C, Hydrogen desiliconization multi-stage porous Beta zeolite is washed to filtrate in neutral again by deionized water, dry at 120 DEG C again, then repeat step 3, namely obtain highly acid multi-stage porous Beta zeolite.
The present invention recovers the acidity of desiliconization multi-stage porous Beta molecular sieve by the mode part continuing post processing, then promotes its reactivity.This multi-stage porous Beta zeolite molecular sieve, without the need to using mesoporous template or hole directed agents, can reduce costs to a great extent.Meanwhile, the parent Beta zeolite of use is existing business Beta zeolite, without the need to special synthesis, is easy to obtain and relative low price.Multi-stage porous Beta zeolite has larger reaction compartment and anti-deactivation, therefore, in macromolecular acid reaction, has the potentiality of application.
Accompanying drawing explanation
Fig. 1 is the XRD result of each zeolite prepared by experiment 1,2 and 3; Fig. 2 is sample nitrogen adsorption isotherm in experiment 1,2 and 3 preparation process; Conversion ratio curve over time on Fig. 3 various samples that to be trimethylbenzene and benzyl alcohol prepare in experiment 1,2 and 3; Productive rate curve over time on Fig. 4 various samples that to be trimethylbenzene and benzyl alcohol prepare in experiment 1,2 and 3.
Detailed description of the invention
Technical solution of the present invention is not limited to following cited detailed description of the invention, also comprises any combination between each detailed description of the invention.
Detailed description of the invention one: the preparation method of present embodiment cheap highly acid multi-stage porous Beta zeolite, carry out according to the following steps:
One, Beta zeolite is calcined 3 ~ 10 hours at 500 ~ 600 DEG C, obtain micropore Hydrogen Beta zeolite;
Two, micropore Hydrogen Beta zeolite being joined concentration is in the aqueous slkali of 0.1 ~ 2mol/L, 0.5 ~ 2h is stirred at 0 ~ 100 DEG C, then deionized water micropore Hydrogen Beta zeolite is spent to filtrate in neutral, drier at 100 ~ 120 DEG C, obtain sodium form desiliconization multi-stage porous Beta zeolite;
Three, it is exchange 1 ~ 5 time in the aqueous ammonium nitrate solution of 1 ~ 2mol/L that sodium form desiliconization multi-stage porous Beta zeolite step 2 obtained joins concentration, exchanges 0.5 ~ 2h at every turn, obtains Hydrogen desiliconization multi-stage porous Beta zeolite at 500 ~ 600 DEG C after calcining 5h;
Four, the Hydrogen desiliconization multi-stage porous Beta zeolite obtained in step 3 being joined concentration is in the acid solution of 0.05 ~ 2mol/L, 0.5 ~ 10h is stirred at 0 ~ 100 DEG C, Hydrogen desiliconization multi-stage porous Beta zeolite is washed to filtrate in neutral again by deionized water, dry at 120 DEG C again, then repeat step 3, namely obtain highly acid multi-stage porous Beta zeolite.
Detailed description of the invention two: present embodiment and detailed description of the invention one unlike: in step 2, aqueous slkali is the NaOH aqueous solution.Other is identical with detailed description of the invention one.
Detailed description of the invention three: present embodiment and detailed description of the invention one or two unlike: the solid-to-liquid ratio of the Hydrogen of micropore described in step 2 Beta zeolite and aqueous slkali is 1g:10 ~ 50mL.Other is identical with detailed description of the invention one or two.
Detailed description of the invention four: one of present embodiment and detailed description of the invention one to three unlike: in step 3, the solid-to-liquid ratio of sodium form desiliconization multi-stage porous Beta zeolite and aqueous ammonium nitrate solution is 1g:30 ~ 200mL.Other is identical with one of detailed description of the invention one to three.
Detailed description of the invention five: one of present embodiment and detailed description of the invention one to three unlike: in step 3, the solid-to-liquid ratio of sodium form desiliconization multi-stage porous Beta zeolite and aqueous ammonium nitrate solution is 1g:100mL.Other is identical with one of detailed description of the invention one to three.
Detailed description of the invention six: one of present embodiment and detailed description of the invention one to five unlike: in step 4, the solid-to-liquid ratio of Hydrogen desiliconization multi-stage porous Beta zeolite and acid solution is 1g:10 ~ 100mL.Other is identical with one of detailed description of the invention one to five.
Detailed description of the invention seven: one of present embodiment and detailed description of the invention one to five unlike: in step 4, the solid-to-liquid ratio of Hydrogen desiliconization multi-stage porous Beta zeolite and acid solution is 1g:30mL.Other is identical with one of detailed description of the invention one to five.
Detailed description of the invention eight: one of present embodiment and detailed description of the invention one to seven unlike: in step 4, acid solution is HNO
3solution or hydrochloric acid.Other is identical with one of detailed description of the invention one to seven.
Detailed description of the invention nine: one of present embodiment and detailed description of the invention one to eight unlike: in step 4, the concentration of acid solution is 0.1 ~ 0.5mol/L.Other is identical with one of detailed description of the invention one to eight.
Detailed description of the invention ten: one of present embodiment and detailed description of the invention one to nine unlike: in step 4 stir 2 ~ 8h.Other is identical with one of detailed description of the invention one to nine.
Experiment 1:
Beta zeolite is calcined 5 hours at 550 DEG C, obtains micropore Hydrogen Beta zeolite (HB); This tests Beta zeolite used is that commercial sources purchase obtains.
Experiment 2:
One, Beta zeolite is calcined 5 hours at 550 DEG C, obtain micropore Hydrogen Beta zeolite;
Two, it is in the NaOH aqueous solution of 0.2mol/L that micropore Hydrogen Beta zeolite step one obtained joins concentration, 0.5h is stirred at 60 ~ 70 DEG C, spend deionized water to filtrate in neutral, drier at 120 DEG C, obtain sodium form desiliconization multi-stage porous Beta zeolite;
The solid-to-liquid ratio of the Hydrogen of micropore described in step 2 Beta zeolite and the NaOH aqueous solution is 1g:30mL,
Three, it is exchange 2 times in the aqueous ammonium nitrate solution of 2mol/L that sodium form desiliconization multi-stage porous Beta zeolite step 2 obtained joins concentration, exchanges 2h at every turn, obtains traditional Hydrogen desiliconization multi-stage porous Beta zeolite (HB-B) at 550 DEG C after calcining 5h;
Experiment 3:
One, Beta zeolite is calcined 5 hours at 550 DEG C, obtain micropore Hydrogen Beta zeolite;
Two, it is in the NaOH aqueous solution of 0.2mol/L that micropore Hydrogen Beta zeolite step one obtained joins concentration, 0.5h is stirred at 60 ~ 70 DEG C, spend deionized water to filtrate in neutral, drier at 120 DEG C, obtain sodium form desiliconization multi-stage porous Beta zeolite;
The solid-to-liquid ratio of the Hydrogen of micropore described in step 2 Beta zeolite and the NaOH aqueous solution is 1g:30mL,
Three, it is exchange 2 times in the aqueous ammonium nitrate solution of 2mol/L that sodium form desiliconization multi-stage porous Beta zeolite step 2 obtained joins concentration, exchanges 2h at every turn, obtains Hydrogen desiliconization multi-stage porous Beta zeolite at 550 DEG C after calcining 5h;
In step 3, the solid-to-liquid ratio of sodium form desiliconization multi-stage porous Beta zeolite and aqueous ammonium nitrate solution is 1g:100mL
Four, the Hydrogen desiliconization multi-stage porous Beta zeolite obtained in step 3 is joined the HNO that concentration is 0.1mol/L
3in the aqueous solution, 6h is stirred at 60 ~ 70 DEG C, Hydrogen desiliconization multi-stage porous Beta zeolite is washed to filtrate in neutral again by deionized water, dry at 120 DEG C again, then dried Hydrogen desiliconization multi-stage porous Beta zeolite being joined concentration is exchange 2 times in the aqueous ammonium nitrate solution of 2mol/L, each exchange 2h, calcines 5h at 550 DEG C, namely obtains highly acid multi-stage porous Beta zeolite (HB-BA).
The XRD result of each zeolite of experiment 1,2 and 3 preparation as shown in Figure 1, in Fig. 1, HB is micropore Hydrogen Beta zeolite prepared by experiment 1, HB-B is traditional Hydrogen desiliconization multi-stage porous Beta zeolite prepared by experiment 2, and HB-BA is desiliconization acid treatment multi-stage porous Beta zeolite prepared by experiment 3.As seen from Figure 1, three samples all have the characteristic diffraction peak of Beta zeolite, illustrate that the process of each step of preparation process does not all destroy the skeleton structure of Beta zeolite.
In experiment 1,2 and 3 preparation process, the situation of change of sample nitrogen adsorption isotherm as shown in Figure 2, in Fig. 2, HB is micropore Hydrogen Beta zeolite prepared by experiment 1, HB-B is traditional Hydrogen desiliconization multi-stage porous Beta zeolite prepared by experiment 2, and HB-BA is desiliconization acid treatment multi-stage porous Beta zeolite prepared by experiment 3.As seen from Figure 2, the micro-pore zeolite prepared by step one, with certain meso-hole structure, and along with step 2, three, four constantly carry out, absorption equipotential line, by I type transposition IV type, defines multi-stage porous.Associative list 1, the sample obtained after can seeing the inventive method process has larger specific area and mesoporous surface area, mesopore volume.Table 1 is the adsorption of nitrogen gas data of various material.
Table 1 adsorption of nitrogen gas data
Trimethylbenzene and the conversion ratio of benzyl alcohol on various sample over time curve as shown in Figure 3, in Fig. 3-■-expression HB ,-●-represent HB-B ,-▲-represent HB-BA.Trimethylbenzene and the productive rate of benzyl alcohol on various sample over time curve as shown in Figure 4, in Fig. 4-■-expression HB ,-●-represent HB-B ,-▲-represent HB-BA.
As can be seen from Fig. 3 and 4, its catalytic activity of material of experiment 2 and 3 preparation is better than the material of experiment 1 preparation.This is the existence due to meso-hole structure, provides more reaction compartment.And its catalytic activity of material of testing 3 preparations will further higher than the catalyst of experiment 2 gained.Associative list 2, can know that this is due to acidic site quantity, the especially lifting of B acid number amount, embodies the superiority of the condition involved by experiment 3.Table 2 is the acidic site quantity of various material.
Table 2 acidic site quantity
Claims (10)
1. the preparation method of cheap highly acid multi-stage porous Beta zeolite, is characterized in that the method is carried out according to the following steps:
One, Beta zeolite is calcined 3 ~ 10 hours at 500 ~ 600 DEG C, obtain micropore Hydrogen Beta zeolite;
Two, micropore Hydrogen Beta zeolite being joined concentration is in the aqueous slkali of 0.1 ~ 2mol/L, 0.5 ~ 2h is stirred at 0 ~ 100 DEG C, then deionized water micropore Hydrogen Beta zeolite is spent to filtrate in neutral, drier at 100 ~ 120 DEG C, obtain sodium form desiliconization multi-stage porous Beta zeolite;
Three, it is exchange 1 ~ 5 time in the aqueous ammonium nitrate solution of 1 ~ 2mol/L that sodium form desiliconization multi-stage porous Beta zeolite step 2 obtained joins concentration, exchanges 0.5 ~ 2h at every turn, obtains Hydrogen desiliconization multi-stage porous Beta zeolite at 500 ~ 600 DEG C after calcining 5h;
Four, the Hydrogen desiliconization multi-stage porous Beta zeolite obtained in step 3 being joined concentration is in the acid solution of 0.05 ~ 2mol/L, 0.5 ~ 10h is stirred at 0 ~ 100 DEG C, Hydrogen desiliconization multi-stage porous Beta zeolite is washed to filtrate in neutral again by deionized water, dry at 120 DEG C again, then repeat step 3, namely obtain highly acid multi-stage porous Beta zeolite.
2. the preparation method of cheap highly acid multi-stage porous Beta zeolite according to claim 1, is characterized in that in step 2, aqueous slkali is the NaOH aqueous solution.
3. the preparation method of cheap highly acid multi-stage porous Beta zeolite according to claim 1 and 2, is characterized in that the solid-to-liquid ratio of the Hydrogen of micropore described in step 2 Beta zeolite and aqueous slkali is 1g:10 ~ 50mL.
4. the preparation method of cheap highly acid multi-stage porous Beta zeolite according to claim 3, is characterized in that the solid-to-liquid ratio of sodium form desiliconization multi-stage porous Beta zeolite and aqueous ammonium nitrate solution in step 3 is 1g:30 ~ 200mL.
5. the preparation method of cheap highly acid multi-stage porous Beta zeolite according to claim 3, is characterized in that the solid-to-liquid ratio of sodium form desiliconization multi-stage porous Beta zeolite and aqueous ammonium nitrate solution in step 3 is 1g:100mL.
6. the preparation method of cheap highly acid multi-stage porous Beta zeolite according to claim 4, is characterized in that the solid-to-liquid ratio of Hydrogen desiliconization multi-stage porous Beta zeolite and acid solution in step 4 is 1g:10 ~ 100mL.
7. the preparation method of cheap highly acid multi-stage porous Beta zeolite according to claim 4, is characterized in that the solid-to-liquid ratio of Hydrogen desiliconization multi-stage porous Beta zeolite and acid solution in step 4 is 1g:30mL.
8. the preparation method of cheap highly acid multi-stage porous Beta zeolite according to claim 6, is characterized in that in step 4, acid solution is HNO
3solution or hydrochloric acid.
9. the preparation method of cheap highly acid multi-stage porous Beta zeolite according to claim 8, is characterized in that the concentration of acid solution in step 4 is 0.1 ~ 0.5mol/L.
10. the preparation method of cheap highly acid multi-stage porous Beta zeolite according to claim 9, is characterized in that stirring 2 ~ 8h in step 4.
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| CN107028218A (en) * | 2017-05-25 | 2017-08-11 | 云南中烟工业有限责任公司 | A kind of method for preparing geranyl acetone slow-release material |
| CN109502607A (en) * | 2018-11-30 | 2019-03-22 | 中国科学院山西煤炭化学研究所 | A kind of synthetic method of nanometer of ZSM-22 molecular sieve |
| CN111097493A (en) * | 2018-10-25 | 2020-05-05 | 中国石油化工股份有限公司 | Preparation method of mesoporous molecular sieve |
| CN111097367A (en) * | 2018-10-29 | 2020-05-05 | 中国石油化工股份有限公司 | Adsorbent for adsorbing normal alkane and preparation method and application thereof |
| US11572283B2 (en) | 2017-10-26 | 2023-02-07 | China Petroleum & Chemical Corporation | Molecular sieve having mesopores, preparation method therefor, and application thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107028218A (en) * | 2017-05-25 | 2017-08-11 | 云南中烟工业有限责任公司 | A kind of method for preparing geranyl acetone slow-release material |
| US11572283B2 (en) | 2017-10-26 | 2023-02-07 | China Petroleum & Chemical Corporation | Molecular sieve having mesopores, preparation method therefor, and application thereof |
| CN111097493A (en) * | 2018-10-25 | 2020-05-05 | 中国石油化工股份有限公司 | Preparation method of mesoporous molecular sieve |
| CN111097493B (en) * | 2018-10-25 | 2023-05-02 | 中国石油化工股份有限公司 | Preparation method of mesoporous molecular sieve |
| CN111097367A (en) * | 2018-10-29 | 2020-05-05 | 中国石油化工股份有限公司 | Adsorbent for adsorbing normal alkane and preparation method and application thereof |
| CN109502607A (en) * | 2018-11-30 | 2019-03-22 | 中国科学院山西煤炭化学研究所 | A kind of synthetic method of nanometer of ZSM-22 molecular sieve |
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Application publication date: 20150218 |