CN101774605A - Preparation method for mesoporous molecular sieve MCM-48 - Google Patents
Preparation method for mesoporous molecular sieve MCM-48 Download PDFInfo
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 26
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 19
- 239000000654 additive Substances 0.000 claims abstract description 17
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 15
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 230000000996 additive effect Effects 0.000 claims abstract description 12
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 12
- 239000010703 silicon Substances 0.000 claims abstract description 12
- -1 sodium fluorosilicate Chemical compound 0.000 claims abstract description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 8
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims abstract description 7
- 238000005216 hydrothermal crystallization Methods 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims description 5
- 238000002425 crystallisation Methods 0.000 claims description 4
- 230000008025 crystallization Effects 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- PVGBHEUCHKGFQP-UHFFFAOYSA-N sodium;n-[5-amino-2-(4-aminophenyl)sulfonylphenyl]sulfonylacetamide Chemical compound [Na+].CC(=O)NS(=O)(=O)C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 PVGBHEUCHKGFQP-UHFFFAOYSA-N 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 12
- 238000000034 method Methods 0.000 abstract description 11
- 239000011148 porous material Substances 0.000 abstract description 5
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052731 fluorine Inorganic materials 0.000 abstract description 4
- 239000011737 fluorine Substances 0.000 abstract description 4
- 231100001231 less toxic Toxicity 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000006116 polymerization reaction Methods 0.000 abstract description 2
- 238000003860 storage Methods 0.000 abstract description 2
- 230000002194 synthesizing effect Effects 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 10
- 230000005540 biological transmission Effects 0.000 description 6
- 235000019504 cigarettes Nutrition 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 239000000779 smoke Substances 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 238000009776 industrial production Methods 0.000 description 3
- 238000001988 small-angle X-ray diffraction Methods 0.000 description 3
- 239000011775 sodium fluoride Substances 0.000 description 3
- 235000013024 sodium fluoride Nutrition 0.000 description 3
- FMMWHPNWAFZXNH-UHFFFAOYSA-N Benz[a]pyrene Chemical compound C1=C2C3=CC=CC=C3C=C(C=C3)C2=C2C3=CC=CC2=C1 FMMWHPNWAFZXNH-UHFFFAOYSA-N 0.000 description 2
- 102220500397 Neutral and basic amino acid transport protein rBAT_M41T_mutation Human genes 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000001603 reducing effect Effects 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- TXVHTIQJNYSSKO-UHFFFAOYSA-N BeP Natural products C1=CC=C2C3=CC=CC=C3C3=CC=CC4=CC=C1C2=C34 TXVHTIQJNYSSKO-UHFFFAOYSA-N 0.000 description 1
- 241000208125 Nicotiana Species 0.000 description 1
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- MLUCVPSAIODCQM-NSCUHMNNSA-N crotonaldehyde Chemical compound C\C=C\C=O MLUCVPSAIODCQM-NSCUHMNNSA-N 0.000 description 1
- MLUCVPSAIODCQM-UHFFFAOYSA-N crotonaldehyde Natural products CC=CC=O MLUCVPSAIODCQM-UHFFFAOYSA-N 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 150000004005 nitrosamines Chemical class 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
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Abstract
本发明提供了一种合成高规整度的介孔分子筛MCM-48的方法，包括如下步骤：(1)将正硅酸四乙酯、十六烷基三甲基溴化铵、氢氧化钠、非水溶性添加剂及水组成的混合物加热到40至60℃搅拌反应2小时，用盐酸将其pH值调节到10至12之后转移到反应釜中；(2)在80至150℃水热晶化8至24小时，结晶产物经分离、洗涤、干燥、空气中灼烧6小时得高规整度纯硅MCM-48分子筛。本发明的特点在于所使用的含氟添加剂氟硅酸钠毒性较小，储存稳定，制备的纯硅分子筛MCM-48具有结晶度好、骨架聚合度高、孔径均匀规整，实验重现性好等特点，有利于实现工业化生产。
The invention provides a method for synthesizing high-regularity mesoporous molecular sieve MCM-48, comprising the steps of: (1) tetraethyl orthosilicate, cetyltrimethylammonium bromide, sodium hydroxide, The mixture composed of non-water-soluble additives and water is heated to 40 to 60 ° C and stirred for 2 hours, and the pH value is adjusted to 10 to 12 with hydrochloric acid, and then transferred to the reaction kettle; (2) hydrothermal crystallization at 80 to 150 ° C After 8 to 24 hours, the crystalline product was separated, washed, dried, and burned in air for 6 hours to obtain high regularity pure silicon MCM-48 molecular sieve. The present invention is characterized in that the fluorine-containing additive sodium fluorosilicate used is less toxic and stable in storage, and the prepared pure silicon molecular sieve MCM-48 has good crystallinity, high degree of skeleton polymerization, uniform and regular pore size, and good experimental reproducibility, etc. Features are conducive to the realization of industrialized production.
Description
技术领域technical field
本发明涉及一种介孔分子筛的制备方法，具体涉及降低卷烟烟气中有害成分的介孔分子筛MCM-48的制备方法。The invention relates to a preparation method of a mesoporous molecular sieve, in particular to a preparation method of a mesoporous molecular sieve MCM-48 which reduces harmful components in cigarette smoke.
背景技术Background technique
1992年美国Mobil公司首次报导了M41S系列介孔分子筛。这类材料具有均一可调的孔径、大的比表面和较高的热稳定性等优点，在催化、吸附、分离材料等领域有良好的应用前景。立方MCM-48是M41S系列的一员，含有两条具有2至7nm相互独立的三维孔道网络结构且镜面对称(空间群为Ia3d)，这种结构更有利于反应物质在其中传输，而对孔道堵塞不敏感。并且对某些大分子反应有择形作用，更有利于客体分子的输送、具有良好的长程有序性和较高的热稳定性，因此无论在选择性催化、吸附、还是纳米团簇的组装等方面都具有更加诱人的应用前景。但有关介孔MCM-48的合成、表征和应用等方面的研究报道要远远少于MCM-41。在2006年1月11日公告的，授权公告号为CN03116140.5，名称为“三元混合阳离子、非离子和阴离子表面活性剂为模板剂制备MCM-48中孔分子筛方法”中国专利中，公开了一种MCM-48中孔分子筛制备方法，但是该专利及现有技术用于制备MCM-48的条件比较苛刻、模板剂用量较大，晶化温度较高并且周期较长，并且实验室小量反应大多采用静态晶化过程，一旦放大反应易产生结块等现象使晶化不均匀，得到的材料结晶度和有序度较差，反应不易重复，很难实现工业化生产。In 1992, Mobil Corporation of the United States first reported the M41S series mesoporous molecular sieves. This type of material has the advantages of uniform and adjustable pore size, large specific surface area, and high thermal stability, and has good application prospects in the fields of catalysis, adsorption, and separation materials. Cubic MCM-48 is a member of the M41S series. It contains two independent three-dimensional pore network structures of 2 to 7 nm and mirror symmetry (space group Ia3d). Not clog sensitive. And it has a shape-selective effect on some macromolecular reactions, which is more conducive to the transportation of guest molecules, has good long-range order and high thermal stability, so whether it is in selective catalysis, adsorption, or the assembly of nanoclusters etc. have more attractive application prospects. However, the research reports on the synthesis, characterization and application of mesoporous MCM-48 are far less than those of MCM-41. Announced on January 11, 2006, the authorized announcement number is CN03116140.5, and the name is "Method for preparing MCM-48 mesoporous molecular sieve with ternary mixed cationic, non-ionic and anionic surfactants as templates" Chinese patent, disclosed A method for preparing MCM-48 mesoporous molecular sieves, but the conditions for preparing MCM-48 in this patent and the prior art are relatively harsh, the amount of template agent is large, the crystallization temperature is high and the cycle is long, and the laboratory is small. Quantitative reaction mostly adopts static crystallization process. Once the scale-up reaction is easy to produce agglomeration and other phenomena, the crystallization is uneven, and the crystallinity and order degree of the obtained material are poor. The reaction is not easy to repeat, and it is difficult to realize industrial production.
发明内容Contents of the invention
因此本发明要解决的问题是寻找一种能够在短周期内合成规整度高、结晶度好，并且便于重复的纯硅MCM-48分子筛的方法，使其更适合工业化生产，并将该材料应用于卷烟嘴棒中，初步评价其对卷烟烟气中主要有害成分的降低效果。Therefore the problem to be solved by the present invention is to find a method that can synthesize high regularity, good crystallinity and easy to repeat pure silicon MCM-48 molecular sieve in a short cycle, so that it is more suitable for industrial production, and this material is applied Preliminary evaluation of its reducing effect on the main harmful components in cigarette smoke in the cigarette mouthpiece.
本发明的技术方案为：将正硅酸四乙酯、十六烷基三甲基溴化铵、氢氧化钠、非水溶性添加剂及水组成的混合物加热到40至60℃搅拌反应2小时，用盐酸将其PH值调节到10至12之后转移到反应釜中，在80至150℃水热晶化8至24小时，结晶产物经分离、洗涤、干燥、空气中灼烧6小时得高规整度纯硅MCM-48分子筛；其中各物质之间的摩尔比为：十六烷基三甲基溴化铵/正硅酸四乙酯＝0.15至0.4，氢氧化钠/正硅酸四乙酯＝0.56至0.76，H2O/正硅酸四乙酯＝65至100，非水溶性添加剂/正硅酸四乙酯＝0.02至0.07。The technical scheme of the present invention is: heating the mixture composed of tetraethyl orthosilicate, cetyltrimethylammonium bromide, sodium hydroxide, non-water-soluble additives and water to 40 to 60°C and stirring for 2 hours, Adjust its pH value to 10 to 12 with hydrochloric acid, then transfer it to a reaction kettle, and conduct hydrothermal crystallization at 80 to 150°C for 8 to 24 hours. Pure silicon MCM-48 molecular sieve; wherein the molar ratio between each substance is: hexadecyltrimethylammonium bromide/tetraethyl orthosilicate=0.15 to 0.4, sodium hydroxide/tetraethyl orthosilicate =0.56 to 0.76, H 2 O/tetraethyl orthosilicate=65 to 100, water-insoluble additive/tetraethyl orthosilicate=0.02 to 0.07.
其中，非水溶性添加剂为氟硅酸钠。Among them, the water-insoluble additive is sodium fluorosilicate.
本发明提供一种短周期内合成介孔分子筛MCM-48的方法，该方法在合成工艺中添加一种非水溶性含氟化合物氟硅酸钠，该添加剂常温、常压下稳定；遇热和氧化、还原性物质不会发生燃烧、爆炸，不溶于水，反应中与碱作用生成F-和硅酸盐，与一般水溶性含氟添加剂相比，该添加剂毒性较小，安全性较高，与碱作用生成的硅酸盐还可作为硅源，将降低原料成本。该方法能够在短周期内制备出规整度高、结晶度好的纯硅介孔分子筛MCM-48，与传统的合成方法相比，可以较大程度地节省时间，降低能耗及成本，更有利于实现纯硅介孔分子筛MCM-48的工业化生产。将该分子筛用于降低卷烟烟气中主要有害成分，取得了较好的效果。The invention provides a method for synthesizing mesoporous molecular sieve MCM-48 in a short period. In the method, a water-insoluble fluorine-containing compound sodium fluorosilicate is added in the synthesis process. The additive is stable at normal temperature and pressure; Oxidizing and reducing substances will not burn or explode, and are insoluble in water. During the reaction, they react with alkali to form F- and silicate. Compared with general water-soluble fluorine-containing additives, this additive is less toxic and safer. The silicate formed by the action of alkali can also be used as a silicon source, which will reduce the cost of raw materials. This method can prepare pure silicon mesoporous molecular sieve MCM-48 with high regularity and good crystallinity in a short period. Compared with the traditional synthesis method, it can save time, reduce energy consumption and cost to a large extent, and is more It is beneficial to realize the industrialized production of pure silicon mesoporous molecular sieve MCM-48. The molecular sieve is used to reduce the main harmful components in cigarette smoke, and a good effect is obtained.
本发明的特点在于所使用的含氟添加剂氟硅酸钠毒性较小，储存较稳定，置于反应中与碱作用才释放出有效成分F-，使反应周期缩短。该法所制备的纯硅分子筛MCM-48结晶度好、骨架聚合度高、热稳定性和水热稳定性好，可重复性高，与碱作用释放出的硅酸盐作为硅源可节约原料成本，有利于纯硅分子筛MCM-48实现工业化生产。The present invention is characterized in that the used fluorine-containing additive, sodium fluorosilicate, has less toxicity and is more stable in storage, and the active ingredient F - is released only when it is reacted with alkali, so that the reaction cycle is shortened. The pure silicon molecular sieve MCM-48 prepared by this method has good crystallinity, high degree of skeleton polymerization, good thermal stability and hydrothermal stability, and high repeatability. The silicate released by the action of alkali can be used as a silicon source to save raw materials. The cost is conducive to the industrial production of pure silicon molecular sieve MCM-48.
附图说明Description of drawings
图1为本发明实施例一产品的小角X射线衍射谱图；Fig. 1 is the small-angle X-ray diffraction spectrogram of the product of embodiment one of the present invention;
图2、3为本发明实施例一产品的高分辨透射电镜谱图；Fig. 2, 3 are the high-resolution transmission electron microscope spectrograms of the product of embodiment one of the present invention;
图4为实施例一、对比例1、对比例2的产品的高分辨透射电镜谱图；Fig. 4 is the high-resolution transmission electron microscope spectrogram of the product of embodiment one, comparative example 1, comparative example 2;
其中，图4中A为实施例一的高分辨透射电镜谱图，B为对比例一的高分辨透射电镜谱图；C为对比例二的高分辨透射电镜谱图。Wherein, A in Fig. 4 is the high-resolution transmission electron microscope spectrum of embodiment one, B is the high-resolution transmission electron microscope spectrum of comparative example one; C is the high-resolution transmission electron microscope spectrum of comparative example two.
具体实施方式Detailed ways
实施例一Embodiment one
先将十六烷基三甲基溴化铵加入水中，搅拌使其溶解，然后依次加入氢氧化钠、氟硅酸钠和正硅酸四乙酯，将上述反应混合物加热到50℃搅拌反应2小时，然后用盐酸将混合液的PH值调节到11-12之间后转移到反应釜中，在110℃水热晶化16小时，结晶产物经分离、洗涤、干燥、空气中灼烧6小时得高规整度有序纯硅MCM-48分子筛。First add cetyltrimethylammonium bromide into water, stir to dissolve it, then add sodium hydroxide, sodium fluorosilicate and tetraethyl orthosilicate in sequence, heat the above reaction mixture to 50°C and stir for 2 hours , and then use hydrochloric acid to adjust the pH value of the mixed solution to between 11-12, then transfer it to the reaction kettle, hydrothermally crystallize it at 110°C for 16 hours, and separate, wash, dry and ignite the crystallized product in the air for 6 hours to obtain High regularity ordered pure silicon MCM-48 molecular sieve.
其中各物质之间的摩尔比为：十六烷基三甲基溴化铵/正硅酸四乙酯＝0.25，氢氧化钠/正硅酸四乙酯＝0.60，H2O/正硅酸四乙酯＝80，Na2SiF6/正硅酸四乙酯＝0.03。Wherein the molar ratio between each substance is: hexadecyltrimethylammonium bromide/tetraethyl orthosilicate=0.25, sodium hydroxide/tetraethyl orthosilicate=0.60, H 2 O/orthosilicate Tetraethyl ester=80, Na 2 SiF 6 /tetraethyl orthosilicate=0.03.
如附图1所示，从小角X射线衍射谱图来看，用氟硅酸钠作为添加剂合成的材料具备MCM-48的特征峰；如附图2、3所示，从高分辨透射电镜谱图来看，该材料孔径均一，约为3nm左右，并且具有很高的规整度。As shown in Figure 1, from the small angle X-ray diffraction spectrum, the material synthesized with sodium fluorosilicate as an additive has the characteristic peak of MCM-48; as shown in Figure 2 and 3, from the high-resolution transmission electron microscope From the picture, the pore size of the material is uniform, about 3nm, and has a high degree of regularity.
对比例一Comparative example one
用氟化钠作为添加剂合成MCM-48分子筛：Synthesis of MCM-48 molecular sieve with sodium fluoride as additive:
除用氟化钠替代氟硅酸钠，F-/Si比不变外，其他合成条件与实施例1相同。Except that sodium fluoride was used instead of sodium fluorosilicate, and the F − /Si ratio remained unchanged, other synthesis conditions were the same as in Example 1.
对比例二Comparative example two
不加添加剂合成MCM-48分子筛：Synthesis of MCM-48 molecular sieve without additives:
除不用任何添加剂外，其他合成条件与实施例1相同。Except without any additive, other synthetic conditions are identical with
如附图4所示，将实施例一、对比例一、对比例二生产的产品，进行小角X射线衍射谱图分析，特征峰越强孔道结构越好，有序度越高。从图上的特征峰的强弱可以看出，采用本发明实施例一制备的产品，结构更好、有序度更高，而对比例一和对比例二则没有明显差异。从附图4还可看出，同是水热晶化反应16小时，添加氟硅酸钠的反应已生成有序的MCM-48，而添加氟化钠和无添加剂的反应还未大量形成有序的MCM-48。As shown in Figure 4, the products produced in Example 1, Comparative Example 1, and Comparative Example 2 were subjected to small-angle X-ray diffraction spectrum analysis. The stronger the characteristic peak, the better the pore structure and the higher the degree of order. It can be seen from the intensity of the characteristic peaks in the figure that the product prepared by Example 1 of the present invention has a better structure and a higher degree of order, while there is no obvious difference between Comparative Example 1 and Comparative Example 2. Can also find out from accompanying
实施例二Embodiment two
取实施例一制备的介孔材料5mg添加于卷烟嘴棒中制成复合滤嘴，用于降低卷烟烟气中主要有害成分，取得了较好的效果，其中苯并(a)芘可降低15％，巴豆醛可降低16％，烟草特有亚硝胺(NNK)可降低18％。Get 5 mg of the mesoporous material prepared in Example 1 and add it to the cigarette tip rod to make a composite filter, which is used to reduce the main harmful components in cigarette smoke, and has achieved good results, wherein benzo(a)pyrene can reduce 15 %, crotonaldehyde can be reduced by 16%, and tobacco-specific nitrosamines (NNK) can be reduced by 18%.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102259886A (en) * | 2011-06-01 | 2011-11-30 | 华东师范大学 | Preparation method of MCM-48 mesoporous molecular sieve |
| CN103172080A (en) * | 2013-03-27 | 2013-06-26 | 南京理工大学 | Method for preparing mesoporous molecular sieve |
| WO2014000247A1 (en) * | 2012-06-29 | 2014-01-03 | 海洋王照明科技股份有限公司 | Method for preparing polyacrylonitrile-methyl methacrylate gel electrolyte film, corresponding electrolyte and preparation method thereof |
| CN103855427A (en) * | 2012-12-07 | 2014-06-11 | 海洋王照明科技股份有限公司 | Modified polymethyl methacrylate electrolyte as well as preparation method, lithium ion battery and application thereof |
| CN103855424A (en) * | 2012-12-07 | 2014-06-11 | 海洋王照明科技股份有限公司 | Modified polyvinyl chloride electrolyte as well as preparation method thereof, lithium ion battery and application lithium ion battery |
| CN104803827A (en) * | 2015-03-17 | 2015-07-29 | 南京钟腾化工有限公司 | Method for preparing 2,6-dichlorotoluene by catalyzing o-chlorotoluene with ionic liquid |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1594085A (en) * | 2004-07-05 | 2005-03-16 | 华东理工大学 | Synthesis method of molecular sieve |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102259886A (en) * | 2011-06-01 | 2011-11-30 | 华东师范大学 | Preparation method of MCM-48 mesoporous molecular sieve |
| WO2014000247A1 (en) * | 2012-06-29 | 2014-01-03 | 海洋王照明科技股份有限公司 | Method for preparing polyacrylonitrile-methyl methacrylate gel electrolyte film, corresponding electrolyte and preparation method thereof |
| CN104271648A (en) * | 2012-06-29 | 2015-01-07 | 海洋王照明科技股份有限公司 | Method for preparing polyacrylonitrile-methyl methacrylate gel electrolyte film, corresponding electrolyte and preparation method thereof |
| CN103855427A (en) * | 2012-12-07 | 2014-06-11 | 海洋王照明科技股份有限公司 | Modified polymethyl methacrylate electrolyte as well as preparation method, lithium ion battery and application thereof |
| CN103855424A (en) * | 2012-12-07 | 2014-06-11 | 海洋王照明科技股份有限公司 | Modified polyvinyl chloride electrolyte as well as preparation method thereof, lithium ion battery and application lithium ion battery |
| CN103172080A (en) * | 2013-03-27 | 2013-06-26 | 南京理工大学 | Method for preparing mesoporous molecular sieve |
| CN104803827A (en) * | 2015-03-17 | 2015-07-29 | 南京钟腾化工有限公司 | Method for preparing 2,6-dichlorotoluene by catalyzing o-chlorotoluene with ionic liquid |
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| CN101774605B (en) | 2011-09-07 |
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