CN105645428A - Preparation method of SSZ-32 molecular sieve adopting mesoporous-microporous grading structure - Google Patents
Preparation method of SSZ-32 molecular sieve adopting mesoporous-microporous grading structure Download PDFInfo
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- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/04—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof using at least one organic template directing agent, e.g. an ionic quaternary ammonium compound or an aminated compound
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2006/12—Surface area
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
Abstract
The invention provides a preparation method of an SSZ-32 molecular sieve adopting a mesoporous-microporous grading structure. An aluminum source, sodium hydroxide and deionized water are homogenized and mixed, a template agent and a silicon source are added, and the mixture is homogenized and mixed; starch is added, an initial gel mixture is obtained, aged and crystallized, a crystallized solid product is separated, washed and dried, and SSZ-32 molecular sieve raw powder is obtained; the SSZ-32 molecular sieve raw powder is calcined, and the SSZ-32 molecular sieve adopting the mesoporous-microporous grading structure is obtained. The preparation method has the advantages of simplicity in preparation, good catalytic performance and low price.
Description
Art
The preparation method that the present invention relates to a kind of SSZ-32 Si-Al molecular sieve with mesoporous-micropore graded structure.
Technical background
SSZ-32 molecular sieve is that same ZSM-23 Si-Al molecular sieve is similar, and topological structure is the molecular sieve of medium pore size of MTT. United States Patent (USP) 5252527 and 5053373 discloses a kind of method that N-low alkyl group-N '-isopropyl-imidazolium hydroxide prepares SSZ-32 molecular sieve as template. SSZ-32 molecular sieve, because having suitable acidity and unique pore passage structure, is demonstrated by superior performance in n-alkane skeletal isomerization, thus at petrochemical industry, and especially the aspect such as lube base oil isomerization dewaxing gets the attention.
In lube base oil, the main component of wax is high-melting-point long-chain normal paraffin, and its pour point is high, and low temperature flowability is poor. By hydroisomerization reaction, n-alkane is converted into branched paraffin, it is possible to improve these performances. Owing to the molecular dimension of wax is relatively large, its isomerization reaction on a catalyst occurs mainly in the aperture place of catalyst, and being only positioned at the active center near molecular sieve aperture could really be utilized. Therefore highly active long-chain normal paraffin isomerization catalyst requires that molecular sieve used has more exposure aperture number.
Chinese patent application CN1942560A discloses a kind of method of little crystal grain SSZ-32 molecular sieve. With alkali metal oxide or hydroxide, alkylamine, N-low alkyl group-N '-isopropyl-imidazoles, (aluminum oxide is dispersed in silicon oxide with covalency form aluminum oxide, use a kind of aluminising silica sol), Si oxide be raw material, the SSZ-32 of little crystal grain can be generated. Chinese patent application CN103153860A discloses a kind of method of SSZ-32 preparing little crystal grain when being absent from amine component, the reaction raw materials of the method includes: at least one Si oxide activated source, at least one aluminum oxide activated source (alumina source provides the aluminium oxide that can be scattered on silicon dioxide with covalency form), at least one alkali metal active source, hydroxide ion and organic formwork agent, the molecular sieve average length of the SSZ-32 synthesized is about 10��40nm.
Except reducing the crystallite dimension of molecular sieve, zeolite crystal manufactures larger-size mesopore orbit (2��50nm), form graded structure, it is also possible to improve and expose aperture number.Although little crystal grain SSZ-32 molecular sieve improves exposure aperture number, the big non-confinement external surface area produced therewith can make non-selective isomerization reaction aggravate, and then cause that cracked product increases, reduce the yield of lube base oil, the viscosity index (VI) of deterioration base oil and volatilizable performance.
Summary of the invention
For solving above-mentioned technical problem, it is an object of the invention to provide one and prepare simply, catalytic performance is good, cheap mesoporous-preparation method of micropore graded structure SSZ-32 molecular sieve.
The present invention, by adding the synthesis path of starch regulation and control SSZ-32 molecular sieve, has synthesized a class graded structure molecular sieve. Starch, rich in hydroxyl, self forms spongiosis under aging temperature, and simultaneously hydroxyl and molecular sieve silicon-aluminum structure effect, ultimately form mesoporous-micropore graduation composite construction. Roasting produces mesopore orbit structure after removing starch. The SSZ-32 molecular sieve of the method synthesis gained has based on MTT microcellular structure and in crystal grain and intercrystalline contains abundant mesoporous, has bigger mesoporous confinement specific surface area and mesoporous pore volume.
The preparation method of the present invention specifically comprises the following steps that
(1) homogenize mixing by aluminum source, sodium hydroxide, deionized water;
(2) adding template and silicon source in step (1) mixture, homogenize mixing again;
(3) in (2) mixture, add starch, obtain initial gel mixture;
(4) step (3) initial gel mixture is carried out burin-in process, then carry out crystallization, crystallization solid product is separated, wash, dry, obtain SSZ-32 molecular screen primary powder;
(5) by SSZ-32 molecular screen primary powder roasting, the SSZ-32 molecular sieve of mesoporous-micropore graded structure is obtained;
Wherein in building-up process, silicon source is with SiO2Meter, aluminum source is with Al2O3Meter, sodium hydroxide is with OH-Meter, starch is with C6H10O5Meter, the mol ratio control of each admixture is:
SiO2: Al2O3: template: OH-: C6H10O5: deionized water=1.0:0.01-0.05:0.01-0.5:0.05-1.5:0.1-0.6:5-150.
The chemical formula of starch described above is [(C6H10O5)n]. Adopted starch can be one or more in cereal starch and potato starch
As above the aluminum source adopted can be one or more in sodium aluminate, aluminum sulfate, aluminum isopropylate., isobutanol aluminum, the silicon source adopted can be one or more in Ludox, white carbon, tetraethyl orthosilicate, the template adopted can be isobutyl amine, di-iso-butylmanice, diisopropylamine, N, one or more in N '-diisopropyl imidazolium hydroxide.
Step as above (1), (2), (3) mixed process carry out in 20-50 DEG C.
Step as above (4) aging temperature may be controlled to 90-140 DEG C, and ageing time may be controlled to 1-8 hour, and crystallization temperature may be controlled to 160-260 DEG C, and crystallization time may be controlled to 0.5-6 days.
Step as above (5) sintering temperature may be controlled to 500-600 DEG C, and roasting time may be controlled to 5-12 hour.
It is specific surface area is 200-360m that the present invention prepares the technical specification of mesoporous-micropore graded structure SSZ-32 molecular sieve2/ g, micropore area is 120-190m2/ g, mesoporous area is 110-180m2/ g, mesoporous average pore size is 12-20nm.
In the hydroisomerization reaction of straight chain C 20-C30 alkane, compared with tradition SSZ-32 molecular sieve, having graded structure SSZ-32 molecular sieve when isomerization product yield is similar, the ratio of highly branched chain product and single branched product greatly increases, and contributes to the reduction of product pour point.
Present invention advantage compared with prior art is as follows:
1, this synthetic method adopts low cost starch to achieve the synthesis of mesoporous-micropore graded structure SSZ-32, is conducive to increasing the mesoporous area of SSZ-32 molecular sieve, is beneficial to the large-scale application of graded structure SSZ-32 molecular sieve.
2, by selecting different types of starch, type and the ratio of branched chain molecule and straight chain molecule in starch is regulated, it is possible to be relatively easy to the structure of graded structure SSZ-32 intermediary hole.
Detailed description of the invention
Embodiment 1
Under 30 DEG C of stirrings, 0.64g sodium aluminate and 1.2g sodium hydroxide being added the mixing that homogenizes in 50ml deionized water, adds isobutyl amine 1.97g, be subsequently adding white carbon 5.6g, homogenize mixing one hour again. In gained mixture, add cereal starch 2.5g, system is warmed up to 90 DEG C, stirs aging 8 hours. Finally the mixture that obtains is loaded in band teflon-lined stainless steel cauldron, 160 DEG C of static crystallizations 144 hours, take out, cooling, filter, 80 DEG C of drying, obtain molecular screen primary powder. 500 DEG C of roastings 12 hours in air atmosphere, (total BET specific surface area is 269m to obtain the SSZ-32 molecular sieve of last graded structure2/ g, micropore area is 145m2/ g, mesoporous area is 124m2/ g, mesoporous average pore size is 12nm).
Embodiment 2
Under 30 DEG C of stirrings, 0.64g sodium aluminate and 1.2g sodium hydroxide being added the mixing that homogenizes in 50ml deionized water, adds di-iso-butylmanice 3.48g, be subsequently adding white carbon 5.6g, homogenize mixing one hour again. In gained mixture, add cereal starch 4.5g, system is warmed up to 120 DEG C, stirs aging 4 hours. Finally the mixture that obtains is loaded in band teflon-lined stainless steel cauldron, 200 DEG C of static crystallizations 24 hours, take out, cooling, filter, 80 DEG C of drying, obtain molecular screen primary powder. 550 DEG C of roastings 5 hours in air atmosphere, (total BET specific surface area is 336m to obtain the SSZ-32 molecular sieve of last graded structure2/ g, micropore area is 163m2/ g, mesoporous area is 173m2/ g, mesoporous average pore size is 14nm).
Embodiment 3
Under 20 DEG C of stirrings, the aluminum isopropylate. of 1.10g and 1.8g sodium hydroxide are added the mixing that homogenizes in 50ml deionized water, adds diisopropylamine 1.97g, be subsequently adding Ludox (SiO225wt%) 22.2g, homogenize mixing one hour again. Add cereal starch 5.5g, system is warmed up to 140 DEG C, stirs aging 1 hour. Finally the mixture that obtains is loaded in band teflon-lined stainless steel cauldron, 200 DEG C of static crystallizations 24 hours, take out, cooling, filter, 80 DEG C of drying, obtain molecular screen primary powder. 600 DEG C of roastings 5 hours in air atmosphere, (total BET specific surface area is 355m to obtain the SSZ-32 molecular sieve of last graded structure2/ g, micropore area is 188m2/ g, mesoporous area is 167m2/ g, mesoporous average pore size is 14nm).
Embodiment 4
Under 50 DEG C of stirrings, the isobutanol aluminum of 1.20g and 1.8g sodium hydroxide are added in 50ml deionized water. It is subsequently adding solution, after solution homogenizes, adds N, N '-diisopropyl imidazolium hydroxide 2.87g, be subsequently adding tetraethyl orthosilicate 18.7g, again homogenize one hour. Add cereal starch 4.5g, mixture is warmed up to 100 DEG C, stirs aging 4 hours. Finally the mixture that obtains is loaded in band teflon-lined stainless steel cauldron, 190 DEG C of static crystallizations 96 hours, take out, cooling, filter, 80 DEG C of drying, obtain molecular screen primary powder.600 DEG C of roastings 8 hours in air atmosphere, (total BET specific surface area is 234m to obtain the SSZ-32 molecular sieve of last graded structure2/ g, micropore area is 124m2/ g, mesoporous area is 110m2/ g, mesoporous average pore size is 15nm).
Embodiment 5
Adopting the preparation process of above-described embodiment 4, ageing time is 1 hour, and aging temperature is 140 DEG C, and crystallization time is 24 hours, and crystallization temperature is 260 DEG C (without teflon-lined stainless steel cauldrons). The total BET specific surface area of SSZ-32 molecular sieve of last graded structure is 272m2/ g, micropore area is 163m2/ g, mesoporous area is 109m2/ g, mesoporous average pore size is 20nm.
Embodiment 6
Adopting the preparation process of above-described embodiment 1, template is the mixture of isobutyl amine and diisopropylamine, and wherein isobutyl amine is 1.2g, and diisopropylamine is 0.77g. The total BET specific surface area of SSZ-32 molecular sieve of last graded structure is 313m2/ g, micropore area is 190m2/ g, mesoporous area is 123m2/ g, mesoporous average pore size is 14nm.
Embodiment 7
Adopting the preparation process of above-described embodiment 6, cereal starch addition is 5.5g. The total BET specific surface area of SSZ-32 molecular sieve of last graded structure is 309m2/ g, micropore area is 165m2/ g, mesoporous area is 144m2/ g, mesoporous average pore size is 18nm.
Embodiment 8
Under 50 DEG C of stirrings, the aluminum sulfate of 0.29g and 2.2g sodium hydroxide being added in 50ml deionized water and homogenize, add isobutyl amine 1.2g and diisopropylamine 0.77g, be subsequently adding white carbon 5.6g, homogenize mixing one hour again. Add potato starch 4.5g, mixture is warmed up to 140 DEG C, stirs aging 1 hour. Finally the mixture that obtains is loaded in band teflon-lined stainless steel cauldron, 200 DEG C of static crystallizations 12 hours, take out, cooling, filter, 80 DEG C of drying, obtain molecular screen primary powder. 650 DEG C of roastings 4 hours in air atmosphere, (total BET specific surface area is 217m to obtain the SSZ-32 molecular sieve of last graded structure2/ g, micropore area is 105m2/ g, mesoporous area is 112m2/ g, mesoporous average pore size is 13nm).
Comparative example
Under 50 DEG C of stirrings, the isobutanol aluminum of 1.20g and 1.8g sodium hydroxide are added in 50ml deionized water. It is subsequently adding solution, after solution homogenizes, adds N, N '-diisopropyl imidazolium hydroxide 2.87g, be subsequently adding tetraethyl orthosilicate 18.7g, again homogenize one hour. Mixture is warmed up to 100 DEG C, stirs aging 4 hours. Finally the mixture that obtains is loaded in band teflon-lined stainless steel cauldron, 190 DEG C of static crystallizations 96 hours, take out, cooling, filter, 80 DEG C of drying, obtain molecular screen primary powder. 600 DEG C of roastings 8 hours in air atmosphere, (total BET specific surface area is 146m to obtain the SSZ-32 molecular sieve of last graded structure2/ g, micropore area is 135m2/ g, mesoporous area is 11m2/g��
Comparative example is as follows with embodiment 4 reaction condition and catalytic result in straight chain C 20-C30 alkane hydroisomerization reaction:
Reaction condition: reaction temperature 280 DEG C; Liquid air speed 1.1h-1; Hydrogen-oil ratio 750; Reaction hydrogen pressure 4.0Mpa
Comparative example: liquid receives (C5+): 96%; C20-C30 isomerisation degree: 100%; C20-C30 isomerization product yield: 51%; The ratio of highly branched chain product and single branched product in C20-C30 isomerization product: 0.6
Embodiment 4: liquid receives (C5+): 95%; C20-C30 isomerisation degree: 100%;C20-C30 isomerization product yield: 55%; The ratio of highly branched chain product and single branched product in C20-C30 isomerization product: 2.2.
Claims (10)
1. the preparation method of a SSZ-32 molecular sieve with mesoporous-micropore graded structure, it is characterised in that comprise the steps:
(1) homogenize mixing by aluminum source, sodium hydroxide, deionized water;
(2) adding template and silicon source in step (1) mixture, homogenize mixing again;
(3) in (2) mixture, add starch, obtain initial gel mixture;
(4) step (3) initial gel mixture is carried out burin-in process, then carry out crystallization, crystallization solid product is separated, wash, dry, obtain SSZ-32 molecular screen primary powder;
(5) by SSZ-32 molecular screen primary powder roasting, the SSZ-32 molecular sieve of mesoporous-micropore graded structure is obtained;
Wherein in building-up process, silicon source is with SiO2Meter, aluminum source is with Al2O3Meter, sodium hydroxide is with OH-Meter, starch is with C6H10O5Meter, the mol ratio control of each addition material is:
SiO2: Al2O3: template: OH-: C6H10O5: deionized water=1.0:0.01-0.05:0.01-0.5:0.05-1.5:0.1-0.6:5-150.
2. the preparation method of a kind of SSZ-32 molecular sieve with mesoporous-micropore graded structure as claimed in claim 1, it is characterised in that described starch is one or more in cereal starch and potato starch.
3. the preparation method of a kind of SSZ-32 molecular sieve with mesoporous-micropore graded structure as claimed in claim 1, it is characterised in that described aluminum source is one or more in sodium aluminate, aluminum sulfate, aluminum isopropylate., isobutanol aluminum.
4. the preparation method of a kind of SSZ-32 molecular sieve with mesoporous-micropore graded structure as claimed in claim 1, it is characterised in that described silicon source is one or more in Ludox, white carbon, tetraethyl orthosilicate.
5. the preparation method of a kind of SSZ-32 molecular sieve with mesoporous-micropore graded structure as claimed in claim 1, it is characterized in that described template is one or more in isobutyl amine, di-iso-butylmanice, diisopropylamine, N, N '-diisopropyl imidazolium hydroxide.
6. the preparation method of a kind of SSZ-32 molecular sieve with mesoporous-micropore graded structure as claimed in claim 1, it is characterised in that described step (1), (2), (3) mixed process are at 20-50oC carries out.
7. the preparation method of a kind of SSZ-32 molecular sieve with mesoporous-micropore graded structure as claimed in claim 1, it is characterised in that described step (4) aging temperature controls as 90-140oC, ageing time controlled as 1-8 hour.
8. the preparation method of a kind of SSZ-32 molecular sieve with mesoporous-micropore graded structure as claimed in claim 1, it is characterised in that described crystallization temperature controls as 160-260oC, crystallization time controlled as 0.5-6 days.
9. the preparation method of a kind of SSZ-32 molecular sieve with mesoporous-micropore graded structure as claimed in claim 1, it is characterised in that described step (5) sintering temperature controls as 500-600oC, roasting time controlled as 5-12 hour.
10. the SSZ-32 molecular sieve of prepared by preparation method as described in any one of claim 1-9 mesoporous-micropore graded structure, it is characterised in that the specific surface area of mesoporous-micropore graded structure SSZ-32 molecular sieve is 200-360m2/ g, micropore area is 120-190m2/ g, mesoporous area is 110-180m2/ g, mesoporous average pore size is 12-20nm.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10160657B2 (en) * | 2016-11-17 | 2018-12-25 | Chevron U.S.A. Inc. | High-silica SSZ-32x zeolite |
| CN109704361A (en) * | 2017-10-26 | 2019-05-03 | 中国石油化工股份有限公司 | A kind of TON structure molecular screen and its preparation method and application |
| WO2019154071A1 (en) * | 2018-02-06 | 2019-08-15 | Basf Se | A process for preparing a zeolitic material having a framework structure type RTH |
| WO2019200989A1 (en) * | 2018-04-20 | 2019-10-24 | Basf Se | A process for preparing a porous oxidic material which comprises micropores and mesopores and which comprises a zeolitic material having a framework type aei |
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| US5053373A (en) * | 1988-03-23 | 1991-10-01 | Chevron Research Company | Zeolite SSZ-32 |
| CN1942560A (en) * | 2003-10-31 | 2007-04-04 | 切夫里昂美国公司 | Preparing small crystal SSZ-32 and its use in a hydrocarbon conversion process |
| CN103153860A (en) * | 2010-11-05 | 2013-06-12 | 雪佛龙美国公司 | Method for preparing small crystal SSZ-32 |
| CN103663493A (en) * | 2013-12-04 | 2014-03-26 | 中国科学院山西煤炭化学研究所 | Preparation method of silicoaluminophosphate molecular sieve with mesoporous-microporous hierarchical structure |
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| US5053373A (en) * | 1988-03-23 | 1991-10-01 | Chevron Research Company | Zeolite SSZ-32 |
| CN1942560A (en) * | 2003-10-31 | 2007-04-04 | 切夫里昂美国公司 | Preparing small crystal SSZ-32 and its use in a hydrocarbon conversion process |
| CN103153860A (en) * | 2010-11-05 | 2013-06-12 | 雪佛龙美国公司 | Method for preparing small crystal SSZ-32 |
| CN103663493A (en) * | 2013-12-04 | 2014-03-26 | 中国科学院山西煤炭化学研究所 | Preparation method of silicoaluminophosphate molecular sieve with mesoporous-microporous hierarchical structure |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10160657B2 (en) * | 2016-11-17 | 2018-12-25 | Chevron U.S.A. Inc. | High-silica SSZ-32x zeolite |
| JP2020504698A (en) * | 2016-11-17 | 2020-02-13 | シェブロン ユー．エス．エー． インコーポレイテッド | High silica SSZ-32X zeolite |
| JP7138102B2 (en) | 2016-11-17 | 2022-09-15 | シェブロン ユー．エス．エー． インコーポレイテッド | High Silica SSZ-32X Zeolite |
| CN109704361A (en) * | 2017-10-26 | 2019-05-03 | 中国石油化工股份有限公司 | A kind of TON structure molecular screen and its preparation method and application |
| CN109704361B (en) * | 2017-10-26 | 2021-02-09 | 中国石油化工股份有限公司 | TON structure molecular sieve and preparation method and application thereof |
| WO2019154071A1 (en) * | 2018-02-06 | 2019-08-15 | Basf Se | A process for preparing a zeolitic material having a framework structure type RTH |
| WO2019200989A1 (en) * | 2018-04-20 | 2019-10-24 | Basf Se | A process for preparing a porous oxidic material which comprises micropores and mesopores and which comprises a zeolitic material having a framework type aei |
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