CN106587102B - The synthetic method of ZSM-12 type zeolite molecular sieves - Google Patents
The synthetic method of ZSM-12 type zeolite molecular sieves Download PDFInfo
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Abstract
The present invention relates to a kind of synthetic method of 12 type zeolite molecular sieves of ZSM, mainly solve be in the prior art synthesize 12 type zeolite molecular sieves of ZSM template feasibility it is low, the more problem of the 12 type zeolite molecular sieve impurity of ZSM of acquisition.The present invention is by using according to 10SiO2:(0.5~4.5) Al2O3:(0.2~4.0) alkaline matter A:(0.5~5.0) template Q:(80~400) H2The initial molar of O matches, silicon source, silicon source, template Q and water are uniformly mixed to get mixture, then by the mixture at 95~180 DEG C hydrothermal crystallizing 20~200 hours, products therefrom is washed and is dried, the technical solution for obtaining 12 type zeolite molecular sieves of ZSM preferably solves the technical problem, can be used in Industrial Catalysis application.
Description
Technical field
The present invention relates to a kind of methods of synthesis ZSM-12 zeolite molecular sieves.
Background technology
Zeolite molecular sieve is due to unique duct shape selectivity, unique solid acid property and excellent ion exchange
Property, thus it is widely used general, it is adsorbing, detach and be catalyzed etc. has all shown their huge business application valences
Value.Such as in petroleum refining and chemical field, the application of Y zeolites brings the leather of a jumping to petroleum catalytic cracking technology
Life, and other molecular sieve catalysts, such as ZSM-5 zeolite, modenite, β zeolites, MCM-22 zeolites, SAPO-34 molecular sieves etc.
Using also give cracking, reformation, isomerization, aromatic disproportion and alkylation, methanol conversion etc. important petroleum refining and chemical industry skill
Art brings substantive breakthrough.Therefore important function in view of molecular sieve in many industrial circles is right in document and patent
It is all very abundant always in the research of recruit's sieve and the research of novel synthesis.
Mainly there are two aspects in the source of molecular sieve, first, being obtained from nature mineral, second is that by artificial synthesized
Method obtains, some molecular sieves can be obtained by both approach, but some molecular sieves can only be obtained by one of both.
But in petroleum refining and chemical field, most of molecular sieve catalyst is obtained by artificial synthesized method.
Common molecular sieve artificial synthesis is hydrothermal synthesis method, such as ZSM-5 (US 3702886), ZSM-11 (US 3709979),
ZSM-23(US 4076842),ZSM-35(US 4016245),Zeolite beta(US 3308069),SAPO-34(US
4440871),MCM-22(US 4954325).The use of hydro-thermal method synthesis zeolite is usually to first pass through silicon source compound, aluminium
Starting sol is obtained by the reaction in source compound, alkali, template and water etc., and then the colloidal sol is by the hydro-thermal reaction under enclosed system
Obtain the molecular sieve product of crystallization.Silicon source can generally use Ludox, silica gel, sodium metasilicate, White Carbon black and organosilicon etc., silicon source one
As use aluminum sulfate, aluminum nitrate, sodium metaaluminate, alumina sol, organo-aluminium and boehmite etc., alkali can be organic
Alkali, ammonium hydroxide, NaOH, KOH etc..Template is also referred to as structure directing agent, and mineralising, balance are primarily served in the building-up process of molecular sieve
The effect of charge and structure directing
It is the most effective approach of synthesizing new molecular screen material, the organic amine mould of special construction using new organic formwork agent
Plate agent plays an important role in Zeolite synthesis, synthesizes the silica-rich zeolite such as ITQ-4, ITQ-7, ITQ- of report in recent years
12, ITQ-13, ITQ-32, SSZ-26, SSZ-35, SSZ-74 etc. are synthesized as template using novel organic amine
's.
The Rosinski and Rubin in the laboratories Mobil of the U.S. in 1973 have synthesized ZSM-12 molecular sieves, structure class for the first time
Type is MTW types, and with the non-crossing duct of one-dimensional linear that twelve-ring is constituted, aperture is 0.57 × 0.61nm, belongs to high silicon class boiling
Stone.ZSM-12 molecular sieves can effectively realize the shape selective catalysis conversion of organic molecule, in reactions such as alkylating aromatic hydrocarbon, isomerization
In show excellent catalytic performance, application prospect is very wide.
The present invention, as template, provides one kind by using the quaternary ammonium salt and quaternary amine bases molecule of a kind of structure novel
It is efficiently synthesized the technical method of ZSM-12 molecular sieves.
Invention content
The technical problems to be solved by the invention are that the template of synthesis ZSM-12 type zeolite molecular sieves can in the prior art
Row is low, and the more problem of the ZSM-12 type zeolite molecular sieve impurity of acquisition provides one kind using quaternary ammonium salt or quaternary amine alkali as template
Agent, the method for synthesizing ZSM-12 type zeolite molecular sieves.The present invention is pressed by using organic quaternary ammonium salt or quaternary amine alkali for template
According to 10SiO2:(0.5~4.5) Al2O3:(2.0~4.0) alkaline matter:(0.5~5.0) template:(80~400) H2O's is first
Silicon source, silicon source, alkaline matter, template and water are uniformly mixed to get mixture, then the mixture exist by beginning mol ratio
20~200 hours technical solutions of hydrothermal crystallizing preferably solve the technical problem at 95~180 DEG C.
In order to solve the above technical problems, the technical solution adopted by the present invention is as follows：A kind of ZSM-12 types zeolite molecular sieve
Synthetic method includes the following steps：
A) according to 10SiO2:(0.01~4.5) Al2O3:(0.2~4.0) alkaline matter:(0.5~5.0) template:(80
~400) H2The initial molar of O matches, and silicon source, silicon source, alkaline matter, template and water are uniformly mixed to get mixture.
B) by the mixture, hydrothermal crystallizing 20~200 hours, products therefrom are washed and are dried at 95~180 DEG C,
Obtain ZSM-12 type zeolite molecular sieves.
Wherein, template is one kind in gemini quaternary ammonium salt or quaternary amine alkali, and structure is by following general molecular formula (A) or (B)
It is shown：
Wherein R1For C1~C10Alkyl, C6~C10Aryl in any one；R2For H, halogen atom and C1~C6
At least one of alkyl；X is any one in halide ion, hydroxyl.
In above-mentioned technical proposal, the X is any one in chlorine, bromine, iodine, hydroxyl.
In above-mentioned preparation ZSM-12 zeolite molecular sieve technical solutions, silicon source is selected from Ludox, solid silicone, gas phase hard charcoal
It is black, at least one of amorphous silica or organic silicone grease；Silicon source is selected from sodium metaaluminate, aluminum sulfate, aluminum nitrate, isopropyl
Aluminium alcoholates, at least one of boehmite；Alkaline matter is selected from lithia, sodium oxide molybdena, potassium oxide, cesium oxide, hydroxide
Lithium, sodium hydroxide, potassium hydroxide, at least one of rubidium hydroxide and cesium hydroxide.
In the above-mentioned technical solution for preparing ZSM-12 zeolite molecular sieves, the initial molar proportioning of preferred mixture is
10SiO2:(0.01~0.5) Al2O3:(0.2~3.6) alkaline matter:(0.5~2.0) template:(100~200) H2O, preferably
Crystallization temperature be 100~180 DEG C, preferred crystallization time is 30~150 hours.
In the above-mentioned technical solution for preparing ZSM-12 zeolite molecular sieves, the R1Preferably C1~C10Alkyl.
In the above-mentioned technical solution for preparing ZSM-12 zeolite molecular sieves, the R2Preferably it is H, halogen atom and C1~
C6At least one of alkyl.
The synthetic method feasibility of the ZSM-12 zeolite molecular sieves provided through the invention is high, can be readily available impurity and contain
The very low pure phase ZSM-12 structural zeolites for not finding impurity even of amount, and zeolite granular size is smaller.
Technical solution using the present invention, obtained gemini quaternary ammonium salt or quaternary amine alkali cpd are used to prepare molecular sieve,
Purity is high, and crystal grain is thin, achieves preferable technique effect.
Description of the drawings
Fig. 1 is the ZSM-12 molecular sieve SEM electron microscopic pictures that embodiment 7 obtains.
The present invention will be further described below by way of examples, but the protection domain being not intended to limit the present invention.
Specific implementation mode
【Embodiment 1】
By 0.021 gram of sodium metaaluminate, 0.29 gram of sodium hydroxide, 1.46 grams of template Q1,7.21 gram 40% of Ludox with
And 10.8 grams of water are uniformly mixed, and said mixture is moved into reaction kettle in 170 DEG C of crystallization 100 hours, is passed through after reaction
After washing, drying, the molecular sieve with ZSM-12 structures is accredited as through XRD.Template Q1 dependency structures are shown in Table 1.
【Embodiment 2】
By 0.041 gram of sodium metaaluminate, 0.58 gram of sodium hydroxide, 2.91 grams of template Q2,14.42 gram 40% of Ludox with
And 3.6 grams of water are uniformly mixed, and said mixture is moved into 170 DEG C of crystallization 120 hours in reaction kettle, after reaction by washing
After washing, drying, identify that product is the molecular sieve with ZSM-12 structures through XRD.Template Q2 dependency structures are shown in Table 1.
【Embodiment 3】
By 0.041 gram of sodium metaaluminate, 1.18 grams of sodium hydroxides, 2.91 grams of template Q2,14.42 gram 40% of Ludox with
And 3.6 grams of water are uniformly mixed, and said mixture is moved into 160 DEG C of crystallization 120 hours in reaction kettle, after reaction by washing
After washing, drying, it is accredited as the molecular sieve with ZSM-12 structures through XRD, with a small amount of stratified material Kenyaite.Template Q2
Dependency structure is shown in Table 1.
【Embodiment 4】
By 0.021 gram of sodium metaaluminate, 0.36 gram of sodium hydroxide, 1.82 grams of template Q3,7.21 gram 40% of Ludox with
And 10.8 grams of water are uniformly mixed, and said mixture is moved into 170 DEG C of crystallization 96 hours in reaction kettle, after reaction by washing
After washing, drying, the molecular sieve with ZSM-12 structures is accredited as through XRD.Template Q3 dependency structures are shown in Table 1.
【Embodiment 5】
By 0.041 gram of sodium metaaluminate, 1.08 grams of sodium hydroxides, 3.06 grams of template Q4,14.42 gram 40% of Ludox with
And 3.6 grams of water are uniformly mixed, and said mixture is moved into 150 DEG C of crystallization 96 hours in reaction kettle, after reaction by washing
After washing, drying, it is accredited as the molecular sieve with ZSM-12 structures through XRD, is associated with quartz.Template Q4 dependency structures are shown in Table 1.
【Embodiment 6】
By 0.041 gram of sodium metaaluminate, 0.58 gram of sodium hydroxide, 14.55 grams of 19%wt template Q5 solution, 14.42 grams
40% Ludox is uniformly mixed, and said mixture is moved into reaction kettle in 160 DEG C of crystallization 100 hours, is passed through after reaction
After crossing washing, drying, identify that product is the molecular sieve with ZSM-12 structures through XRD.Template Q5 dependency structures are shown in Table 1.
【Embodiment 7】
By 0.041 gram of sodium metaaluminate, 0.58 gram of sodium hydroxide, 9.54 grams of 15%wt template Q6 solution, 14.42 gram 40%
Ludox be uniformly mixed, said mixture is moved into 160 DEG C of crystallization 120 hours in reaction kettle, after reaction by washing
After washing, drying, identify that product is the molecular sieve with ZSM-12 structures through XRD.Template Q6 dependency structures are shown in Table 1.SEM Electronic Speculum
Picture shows that preparation-obtained ZSM-12 sieve particles are smaller, has reached nano-scale.
Quaternary ammonium salt or quaternary amine alkali structure used in 1 embodiment of table
Claims (7)
1. a kind of method of synthesis ZSM-12 type zeolite molecular sieves, includes the following steps：
A) according to 10SiO2:(0.01~4.5) Al2O3:(0.2~4.0) alkaline matter:(0.5~5.0) template:(80~
400)H2The initial molar of O matches, and silicon source, silicon source, alkaline matter, template and water are uniformly mixed to get mixture；
B) by the mixture, hydrothermal crystallizing 20~200 hours, products therefrom are washed and are dried, obtained at 95~180 DEG C
To ZSM-12 type zeolite molecular sieves；
Wherein, template is one kind in gemini quaternary ammonium salt or quaternary amine alkali, and structure is shown in following general molecular formula (A) or (B)：
Wherein R1For C1~C10Alkyl, C6~C10Aryl in any one；R2For H, halogen atom and C1~C6Hydrocarbon
At least one of base；X is any one in halide ion, hydroxyl.
2. the method for synthesis ZSM-12 type zeolite molecular sieves according to claim 1, it is characterised in that the silicon source is selected from
Ludox, solid silicone, gas-phase silica, at least one of amorphous silica or organic silicone grease.
3. the method for synthesis ZSM-12 type zeolite molecular sieves according to claim 1, it is characterised in that source of aluminium is choosing
From sodium metaaluminate, aluminum sulfate, aluminum nitrate, aluminium isopropoxide, at least one of boehmite.
4. the method for synthesis ZSM-12 type zeolite molecular sieves according to claim 1, it is characterised in that the alkaline matter
To be selected from lithia, sodium oxide molybdena, potassium oxide, cesium oxide, lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide and hydroxide
At least one of caesium.
5. the method for synthesis ZSM-12 type zeolite molecular sieves according to claim 1, it is characterised in that the mixture
Initial molar proportioning is 10SiO2:(0.01~0.5) Al2O3:(0.2~3.6) alkaline matter:(0.5~2.0) template:(100
~200) H2O。
6. the method for synthesis ZSM-12 type zeolite molecular sieves according to claim 1, it is characterised in that the mixture exists
At 100~180 DEG C, hydrothermal crystallizing 30~150 hours.
7. the method for synthesis ZSM-12 type zeolite molecular sieves according to claim 1, it is characterised in that the R1For C1~C10
Alkyl.
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| CN109665542B (en) * | 2017-10-17 | 2022-07-12 | 中国石油化工股份有限公司 | Layered molecular sieve and preparation method thereof |
| CN109665541B (en) * | 2017-10-17 | 2022-04-01 | 中国石油化工股份有限公司 | Synthesis method of ZSM-12 type zeolite molecular sieve with low silica-alumina ratio |
| CN109665543B (en) * | 2017-10-17 | 2022-04-05 | 中国石油化工股份有限公司 | Layered molecular sieve and preparation method thereof |
| CN109665544B (en) * | 2017-10-17 | 2022-05-27 | 中国石油化工股份有限公司 | Layered molecular sieve and preparation method thereof |
| CN108997146A (en) * | 2018-06-27 | 2018-12-14 | 运城市泓翔建材有限公司 | A kind of anti-mud agent of novel gemini quaternary ammonium salt and preparation method and application |
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| CN102910644A (en) * | 2011-08-01 | 2013-02-06 | 中国石油化工股份有限公司 | Multistage pore ZSM-5 molecular sieve and preparation method thereof |
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Non-Patent Citations (2)
| Title |
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| "Diquaternary structure-directing agents built upon charged imidazolium ring centers and their use in synthesis of one-dimensional pore zeolites";Stacey I. Zones et al.;《J. Mater. Chem.》;20050817;第15卷;第4217页第4段以及表2 * |
| "新型双子季胺碱模板剂的合成及纳米ZSM-5分子筛的制备";沈少春等;《工业催化》;20151015(第10期);第763-766页 * |
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