CN104437606B - ZSM-12 molecular sieve of multilayer structure and preparation method thereof - Google Patents
ZSM-12 molecular sieve of multilayer structure and preparation method thereof Download PDFInfo
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Abstract
The invention relates a ZSM-12 molecular sieve of a multilayer structure and a preparation method thereof, mainly aiming at solving the technical problem that a multilayer ZSM-12 molecular sieve cannot be obtained in the prior art. The multilayer ZSM-12 molecular sieve comprises a nuclear phase and a shell for covering the nuclear phase, the nuclear phase and the shell are respectively of an MTW structure, the nuclear phase silicon-aluminum (Si/Al) atom ratio is equal to 10 to infinite, the shell silicon-aluminum atom ratio is equal to 10 to infinite, and the shell thickness is 0.2-3000nm. According to the technical scheme, the preparation method of the molecular sieve comprises the following steps: uniformly mixing a ZSM-12 molecular sieve nuclear, a silicon source, an aluminum source, a template R, water and an alkali metal raw material, and performing at least one synthesis under a hydrothermal condition to prepare the required multilayer ZSM-12 molecular sieve. The technical problem is well solved by adopting the technology, and the technology can be applied to the industrial production of the multilayer ZSM-12 molecular sieve.
Description
Technical field
The present invention relates to a kind of sandwich construction ZSM-12 molecular sieve and preparation method thereof.
Background technology
Zeolite molecular sieve is the crystalline microporous material that a class has skeleton structure, due to its have specific pore size,
Architectural feature, larger specific surface area, suitable mechanical strength, the applicability to chemical reaction and the selectivity to catalytic reaction
Controlled advantage, is often applied in many catalytic reactions, especially in petroleum refining and processing, Coal Chemical Industry, living beings industry with
And the aspect such as gas chemical industry has a wide range of applications.
ZSM-12 molecular sieve is a kind of molecular sieve with twelve-ring pore passage structure, and it has one-dimensional duct framework.Should
Molecular sieve is succeeded in developing by Mobil company of the U.S. earliest（USP 3832449）, and with being applied to catalytic cracking
（USP3970544）, catalytic dewaxing（USP4376036）, be hydrocracked（EP38140）, reformation, aromatisation, isomerization, alkylation
Deng（USP4112056、FR2374283）Important Industrial Catalysis field.
The molecular sieve catalyst that catalytic field uses at present mostly is sieve and silica-sesquioxide molecular sieve, and wherein Al atom is activity
Position, also has research to introduce tin, iron, titanium and gallium（CN101792153A）Deng element as catalytic active site.But in preparation process,
Active metal can cause side reaction to occur in molecular sieve surface in the distribution of catalyst surface, thus leading to catalyst to inactivate.
Once patent US4067920, US4011276, US5367099 and US5607888 was had to propose to carry out hole to molecular sieve
The modification of structure, that is, reduce port size and shielding outer surface acidity active sites preparing shape-selective catalyst, but it needs to urging
After agent carries out multiple modification, and modified catalysts selectively rise, conversion ratio declines more.
Have been reported that and by the method preparing core shell structure molecular sieve, molecular sieve surface active sites covered, to improve ZSM-5,
Modenite and the catalytic performance of Beta equimolecular sieve,（CN101723401B, CN101723402B and document D.J. Kong,
J.L. Zheng, X.H. Yuan, Y.D. Wang, D.Y. Fang, Fabrication of Core/shell
Structure via Overgrowth of ZSM-5 Layers on Mordenite Crystals, Microporous
And Mesoporous Materials 119 (2009) 91-96., Kong Dejin, Zheng Junlin, Qi Xiaolan, Xie Ku, room
Ancient cooking vessel industry, the synthesis of MFI@MOR core-shell type zeolite molecular sieve and sign, the 11st the youth of the nation is catalyzed academic meeting paper collection
（On））.
Though having patent to describe the synthetic method of ZSM-12 molecular sieve at present（CN1077400A and CN1774398A）.But
There is not been reported for ZSM-12 molecular sieve to sandwich construction and preparation method thereof.
Content of the invention
One of the technical problem to be solved is the ZSM-12 molecular sieve that prior art cannot prepare sandwich construction
Problem, a kind of new sandwich construction ZSM-12 molecular sieve is provided.Every layer of the sandwich construction ZSM-12 molecular sieve of the present invention all has
There is MTW structure, have on the premise of not blocking molecular sieve pipeline, ZSM-12 molecular sieve surface is modified, improve catalysis
The advantage of the performance of agent.
The two of the technical problem to be solved are to provide a kind of multilayer corresponding with solving one of technical problem
The synthetic method of structure ZSM-12 molecular sieve.
The three of the technical problem to be solved are the catalyst choices that 2,6- dimethylnaphthalene is prepared in existing catalysis
The problem of difference, provides a kind of new preparation 2, the method for 6- dimethylnaphthalene.The method is used for methyl naphthalene, naphthalene, methyl alcohol, trimethylbenzene
When being converted into 2,6- dimethylnaphthalene etc. mixed material, there is the selectively high feature of 2,6- dimethylnaphthalene.
The four of the technical problem to be solved are the low problems of reaction conversion ratio that dimethylbenzene is prepared in existing catalysis,
A kind of new method preparing dimethylbenzene is provided.The method is used for benzene, toluene, methyl alcohol, trimethylbenzene, durene, penta-methyl benzene etc.
When mixed material is converted into dimethylbenzene, have the characteristics that feed stock conversion is high.
In order to solve one of above-mentioned technical problem, the technical solution used in the present invention is as follows：A kind of ZSM- of sandwich construction
12 molecular sieves, including nuclear phase ZSM-12 molecular sieve and the shell ZSM-12 molecular sieve being wrapped in outside nuclear phase, nuclear phase is equal with shell
There is MTW structure, described nuclear phase sial atomic ratio Si/Al=10～∞, described shell sial atomic ratio is 10～∞, shell
Thickness degree is 0.2～3000 nm.
For solving the two of above-mentioned technical problem, the technical solution used in the present invention is as follows：Described sandwich construction ZSM-12
The preparation method of molecular sieve, including several steps as follows：
（a）By silicon source Si, silicon source Al, with MxThe alkali source of O meter, water and template R mixing and stirring according to a certain percentage,
Obtain mixture I, the mol ratio of the various materials in gained mixture I is：MxO:Si=0.1 ~ 0.4, Si:Al=10～+
∞, R: MxO=0.25～19；x=1,2
（b）The ZSM-12 molecular sieve of any silica alumina ratio is put in said mixture I, and continues to stir, mixed
Compound II；
（c）Said mixture II is put in reactor, crystallization temperature is 80～180 C, and constant temperature keeps 12 h extremely
4320 h；
（d）By above-mentioned product cool down, and through filter, washing after be dried, after in 300 ~ 700 C roasting 3 ~ 10 hours, obtain final product
ZSM-12 molecular sieve to sandwich construction；
（e）Repeat the above steps（a）~（d）At least one times, that is, obtain the ZSM-12 molecular sieve of sandwich construction.
Wherein, silicon source is at least one in silica gel, white carbon, waterglass, tetraethyl orthosilicate etc.；Silicon source is meta-aluminic acid
At least one in sodium, aluminium chloride, aluminum sulfate, aluminum nitrate, aluminium hydroxide, AlOOH etc.；Alkali metal source is containing sodium, potassium, elemental lithium
In at least one element material；In template selection tetraethylammonium bromide, etamon chloride, tetraethyl ammonium hydroxide
At least one organic amine.
In technique scheme, in the described preparation method of sandwich construction ZSM-12 molecular sieve, in gained mixture I
The mol ratio of various materials is：MxO:Si=0.2 ~ 0.3, Si:Al=15～2000, R: MxIn the range of O=0.25～19.
Described crystallization time is 12 h to 6700 h, and crystallization temperature is 145～175 C
The preparation method of described sandwich construction ZSM-12 molecular sieve, middle repeat step（a）~（d）At least 2 times, obtain many
The ZSM-12 molecular sieve of Rotating fields.
For solving the three of above-mentioned technical problem, the technical solution used in the present invention is as follows：A kind of production 2,6- dimethylnaphthalene
Method, naphthalene, methyl naphthalene, methyl alcohol, trimethylbenzene be raw material, reaction temperature be 290 ~ 450 DEG C, reaction pressure 2.0 ~ 3.6 MPa,
Weight space velocity is 1.0 ~ 4.5h-1, by contacting with the bed containing above-mentioned catalyst, reaction generation comprises 2,6- dimethylnaphthalene to raw material
Product.
For solving the four of above-mentioned technical problem, the technical solution used in the present invention is as follows：A kind of method producing dimethylbenzene,
With benzene, toluene, methyl alcohol, trimethylbenzene, durene, penta-methyl benzene as raw material, it is 280 ~ 420 DEG C in reaction temperature, reaction pressure 0.1 ~
3.5MPa, weight space velocity is 1.0 ~ 4.5h-1, by contacting with the bed containing above-mentioned catalyst, reaction generation comprises diformazan to raw material
The product of benzene.
The present invention due to being nuclear phase using Si-Al molecular sieve, the shell prepared can containing only silica or
Compound containing silica or aluminum oxide.The innovative point of this technology is that the molecular sieve synthesizing is sandwich construction, by adjusting
The silica alumina ratio of each layer of the flexible modulation of the condition that is integrated into and thickness, and core is MTW structure with shell, can be used for 2,6- dimethylnaphthalene
Production field, improves the selectivity of 2,6- dimethylnaphthalene it can also be used to the production field of dimethylbenzene, improves the choosing of xylene products
Selecting property and Selectivity for paraxylene.
Brief description
Fig. 1：The XRD result of the ZSM-12 molecular sieve after growth shell
Fig. 2：The SEM characterization result of the ZSM-12 molecular sieve after growth shell
Below by instantiation, the present invention is further elaborated.
Specific embodiment
【Embodiment 1】
1st, by 38 g concentration be 40% silica gel, 0.3 g sodium metaaluminate, 0.65 g NaOH, 6.5 g tetraethyl brominations
Mixing and stirring under ammonium and 40 g deionized water room temperatures.
2nd, the ZSM-12 molecular sieve core of sodium form Si/Al=18 is poured in above-mentioned solution, and continue to stir.
3rd, sample is poured into in the little vexed tank of teflon-lined, seal, and be heated to 160 C constant temperature and keep
115 h.
4th, by above-mentioned product using cooling water quick cooling, and through filtering, washing, in 120 C baking ovens, 12h is dried.
5th, in 550 C roasting 4 hours after taking out, that is, Product samples are obtained.
This product core Si/Al=18, outer layer Si/Al=52, shell thickness 65 nm.Product X RD and SEM result are shown in
Bright book accompanying drawing 1,2, can be seen that nuclear phase ZSM-12 from XRD result and is MTW structure with the sample after growth shell.
【Embodiment 2】
1st, be 25% by 32 g white carbons, 0.05 g aluminium hydroxide, 0.75 g potassium hydroxide, 50 g mass concentrations four
Mixing and stirring under ethyl ammonium hydroxide solution and 110 g deionized water room temperatures.
2nd, Hydrogen ZSM-12 molecular sieve 10 g of Si/Al=150 is poured in above-mentioned solution, and continue to stir.
3rd, sample is poured into in the little vexed tank of teflon-lined, seal, and heat, keep the temperature at 155-
165 C keep 120 h.
4th, by above-mentioned product using cooling water quick cooling, and through filtering, washing, 12 hs are dried in 120 C baking ovens.
5th, in 550 C roasting 4 hours after taking out, on the ZSM-12 molecular sieve core of Si/Al=150, grow Si/Al
=550 MTW shell, shell thickness 1000 nm.
【Embodiment 3】
Using embodiment 2 products therefrom as nuclear phase molecular sieve, then the step through embodiment 1, you can obtain three layers
The different MTW structure molecular screen of silica alumina ratio, kernel Si/Al=150；Intermediate layer Si/Al=550, thickness 1000 nm；
Outer layer Si/Al=52, thick 65 nm.
【Embodiment 4-10】
By the ZSM-12 molecular sieve of any for 10g silica alumina ratio, according to material proportion and the synthesis condition of table 1, according to embodiment party
Step in case is operated, you can obtain the MTW structure molecular screen shell meeting silica alumina ratio in table.
Table 1
【Embodiment 11-18】
Sandwich construction ZSM-12 molecular sieve is used for the production of 2,6- dimethylnaphthalene.
With naphthalene, methyl naphthalene, trimethylbenzene, methyl alcohol etc. as raw material, it is catalyst using sandwich construction ZSM-12 molecular sieve, can obtain
To the product rich in 2,6- dimethylnaphthalene.The results are shown in Table 2.
Table 2
| Real Apply Example | Raw material | Raw material rubs That proportioning | Reaction pressure Power （MPa） | When weight empty Speed（h-1） | Reaction temperature Degree（℃） | Hydrogen Hydrocarbon Than | How to be former Material conversion Rate | Dimethyl Naphthalene yield | 2,6- dimethyl Naphthalene/dimethyl Naphthalene |
| 11 | Naphthalene:Front three Benzene:Methyl alcohol | 1:5:9 | 2.2 | 1.0 | 360 | 1. 5 | >96% | >75% | 14.14% |
| 12 | Naphthalene:Front three Benzene:Methyl alcohol | 1:1:3 | 3.5 | 4.0 | 400 | 4. 5 | >73% | >61% | 12.32% |
| 13 | Naphthalene:Front three Benzene:Methyl alcohol | 1:3:6 | 3.0 | 2.5 | 350 | 2. 5 | >84% | >72% | 12.64% |
| 14 | Methyl naphthalene:Three Toluene:Methyl alcohol | 1:4:8 | 2.5 | 1.5 | 300 | 1. 5 | >93% | >79% | 14.65% |
| 15 | Methyl naphthalene:Three Toluene:Methyl alcohol | 1:1:2 | 3.5 | 4.5 | 290 | 4. 5 | >69% | >68% | 13.31% |
| 16 | Methyl naphthalene:Three Toluene:Methyl alcohol | 1:3:5 | 3.0 | 2.5 | 450 | 2. 5 | >82% | >76% | 14.24% |
| 17 | Naphthalene:Methyl Naphthalene:Trimethylbenzene | 1:2:5 | 2.5 | 2.0 | 420 | 4. 0 | >40% | >30% | 14.14% |
| 18 | Naphthalene:Methyl Naphthalene:Trimethylbenzene | 2:1:11 | 3.5 | 3.5 | 330 | 2. 0 | >87% | >80% | 14.23% |
【Embodiment 18-23】
Sandwich construction ZSM-12 molecular sieve is used for the production of dimethylbenzene.The results are shown in Table 3
Table 3
| Real Apply Example | Raw material | Raw material rubs That proportioning | Reaction pressure （MPa） | When weight air speed （h-1） | Reaction temperature Degree（℃） | Hydrogen Hydrocarbon Than | Dimethylbenzene Selectively | Paraxylene/ Dimethylbenzene |
| 19 | Benzene:Toluene:First Alcohol:Water | 2:1:9:1 | 2.5 | 2.5 | 420 | 0 | 51% | 35.14 |
| 20 | Benzene:Toluene:First Alcohol:Water | 1:2:6:0 | 0.1 | 4.0 | 310 | 1 | 42% | 34.32 |
| 21 | Benzene:Toluene:Three Toluene | 2:1:7 | 2.0 | 1.0 | 350 | 0 | 72% | 35.64 |
| 22 | Toluene:Front three Benzene:Durene | 2:1:4:1 | 3.5 | 2.5 | 360 | 3.0 | 73% | 36.65 |
| 23 | Toluene:Front three Benzene:Penta-methyl benzene | 5:3:1 | 3.0 | 4.5 | 280 | 4.0 | 61% | 35.41 |
Claims (7)
1. the ZSM-12 molecular sieve of a kind of sandwich construction, including nuclear phase ZSM-12 molecular sieve and the shell being wrapped in outside nuclear phase
ZSM-12 molecular sieve, nuclear phase and shell are respectively provided with MTW structure, described nuclear phase sial atomic ratio Si/Al=15～1000, described
Shell sial atomic ratio be 15～1000, shell thickness be 0.5～2000nm；Described sandwich construction ZSM-12 molecular sieve
Preparation method, including several steps as follows：(a) by silicon source Si, silicon source Al, with MxThe alkali source of O meter, water and template R are according to one
Certainty ratio mixing and stirring, obtains mixture I, and the mol ratio of the various materials in gained mixture I is：MxO:Si=0.1
～0.4, Si:Al=15～1000, R:MxO=0.25～19；X=1,2；B ZSM-12 molecular sieve is put into said mixture I by ()
In, and continue to stir, obtain mixture II；C said mixture II is put in reactor by (), crystallization temperature be 80～
180 DEG C, and constant temperature keeps 12h to 4320h；D above-mentioned product is cooled down by (), and be dried through filtering, after washing, after 300～700
DEG C roasting 3～10 hours, that is, obtain the ZSM-12 molecular sieve of sandwich construction；(e) repeat the above steps (a)～(d) at least one times,
Obtain the ZSM-12 molecular sieve of sandwich construction.
2. the preparation method of the sandwich construction ZSM-12 molecular sieve described in a kind of claim 1, including several steps as follows：
(a) by silicon source Si, silicon source Al, with MxThe alkali source of O meter, water and template R mixing and stirring according to a certain percentage, obtain
Mixture I, the mol ratio of the various materials in gained mixture I is：MxO:Si=0.1～0.4, Si:Al=15～1000, R:
MxO=0.25～19；X=1,2；
B () puts into ZSM-12 molecular sieve in said mixture I, and continue to stir, and obtains mixture II；
C said mixture II is put in reactor by (), crystallization temperature is 80～180 DEG C, and constant temperature keeps 12h to 4320h；
D above-mentioned product is cooled down by (), and through filter, washing after be dried, after in 300～700 DEG C of roastings 3～10 hours, that is, obtain
The ZSM-12 molecular sieve of sandwich construction；
E () repeat the above steps (a)～(d) at least one times, that is, obtains the ZSM-12 molecular sieve of sandwich construction.
3. sandwich construction ZSM-12 molecular sieve according to claim 2 preparation method it is characterised in that：Silicon source is silicon
At least one in glue, white carbon, waterglass, tetraethyl orthosilicate；Silicon source be sodium metaaluminate, aluminium chloride, aluminum sulfate, aluminum nitrate,
At least one in aluminium hydroxide, AlOOH；Alkali metal source is the material containing at least one element in sodium, potassium, elemental lithium；Mould
At least one organic amine in plate agent selection tetraethylammonium bromide, etamon chloride, tetraethyl ammonium hydroxide.
4. sandwich construction ZSM-12 molecular sieve according to claim 2 preparation method it is characterised in that：Gained mixture
The mol ratio of the various materials in I is：MxO:Si=0.1～0.4, Si:Al=15～900, R:MxO=0.25～19；X=1,
2.
5. sandwich construction ZSM-12 molecular sieve according to claim 2 preparation method it is characterised in that：Crystallization temperature is
140～170 DEG C, and constant temperature keeps 48h to 240h.
6. sandwich construction ZSM-12 molecular sieve according to claim 2 preparation method it is characterised in that：350～650
DEG C roasting 3～5 hours.
7. sandwich construction ZSM-12 molecular sieve according to claim 2 preparation method it is characterised in that：Repeat step
A ()～(d) is at least twice.
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| CN106698465B (en) * | 2015-11-12 | 2018-08-14 | 中国石油化工股份有限公司 | A method of preparing a nanometer ZSM-12 molecular sieves |
| CN106517240B (en) * | 2016-10-25 | 2018-07-24 | 浙江大学 | The method for synthesizing flakes ZSM-12 zeolite molecular sieves with single small molecule organic formwork agent |
| CN112939009B (en) * | 2019-12-11 | 2022-11-15 | 中国科学院大连化学物理研究所 | Solid-phase synthesis method of MTW type molecular sieve |
| CN113860323B (en) * | 2020-06-30 | 2023-06-09 | 中国石油化工股份有限公司 | Synthesis method of molecular sieve |
| CN114805000B (en) * | 2022-05-23 | 2023-09-26 | 煤炭科学技术研究院有限公司 | Method for preparing 2-methylnaphthalene by decalin |
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| EP0118632A1 (en) * | 1983-03-14 | 1984-09-19 | Mobil Oil Corporation | Crystalline materials and process for their manufacture |
| CN101723401A (en) * | 2008-10-28 | 2010-06-09 | 中国石油化工股份有限公司 | ZSM-5/ZSM-5 core-shell type zeolite molecular sieve |
| CN102648158A (en) * | 2009-08-07 | 2012-08-22 | 埃克森美孚研究工程公司 | Synthesis and use of ZSM-12 |
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|---|---|---|---|---|
| EP0118632A1 (en) * | 1983-03-14 | 1984-09-19 | Mobil Oil Corporation | Crystalline materials and process for their manufacture |
| CN101723401A (en) * | 2008-10-28 | 2010-06-09 | 中国石油化工股份有限公司 | ZSM-5/ZSM-5 core-shell type zeolite molecular sieve |
| CN102648158A (en) * | 2009-08-07 | 2012-08-22 | 埃克森美孚研究工程公司 | Synthesis and use of ZSM-12 |
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