CN1515490A - Method for removing organic-inorganic composite porous material organic template agent - Google Patents

Method for removing organic-inorganic composite porous material organic template agent Download PDF

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CN1515490A
CN1515490A CNA031506119A CN03150611A CN1515490A CN 1515490 A CN1515490 A CN 1515490A CN A031506119 A CNA031506119 A CN A031506119A CN 03150611 A CN03150611 A CN 03150611A CN 1515490 A CN1515490 A CN 1515490A
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porous material
digestion
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inorganic composite
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CN1219701C (en
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田博之
刘晓英
屠波
赵东元
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复旦大学
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Abstract

The present invention relates to a method for removing organic template agent from organic-inorganic composite porous material. It adopts microwave heating counteracting system, and uses the cheap oxidizing inorganic acid and aqueous hydrogen peroxide as solvent, and utilize self-produced pressure in the system to remove the organic template agent. Said method is high-effective, quick and small in damage to inorganic skeleton, and the prepared ordered silicon oxide material has higher specific area, pore volume and structure ordered degree. Said invention can be used for removing organic material from various acid-resistant inorganic materials.

Description

一种有机-无机复合多孔材料有机模板剂的脱除方法 An organic - inorganic composite porous material removal process organic templating agent

技术领域 FIELD

本发明属无机多孔材料技术领域,具体涉及一种有机-无机复合多孔材料有机模板剂的脱除方法。 The present invention belongs to the technical field of inorganic porous materials, particularly relates to an organic - inorganic composite porous material of the organic templating agent removal process.

技术背景无机孔材料具有大的比表面积和孔体积、可调的孔径、可以修饰的表面性质以及可以控制的形貌等等,因而在分离、催化、传感以及作为合成其它材料的模板等各个领域都具有非常大的应用潜力。 BACKGROUND ART inorganic porous material having a large specific surface area and pore volume, pore size is adjustable, and may be modified surface properties like morphology can be controlled, thus separated, catalysis, sensing, and as a template the synthesis of various other materials, etc. It has a very large field of potential applications. 无机多孔材料这个家族包括以下几个主要成员:微孔材料、介孔材料、大孔材料以及多级孔材料。 The inorganic porous material of this family include the following main members: a microporous materials, mesoporous materials, macroporous materials and a multistage porous material. 在制备无机孔材料,尤其是具有有序的孔道结构的孔材料时,大多数条件下都需用到有机结构导向剂,即有机模板剂。 In the preparation of the inorganic porous material, especially porous materials having pore ordered structures, under most conditions are required to the organic structure directing agent, i.e., an organic templating agent. 对于微孔分子筛材料来说,合成时所采用的结构导向剂多为短链的小分子胺;对于介孔分子筛来说,人们采用的结构导向剂为两亲性的表面活性剂,包括阳离子型表面活性剂、阴离子型表面活性剂、非离子表面活性剂和双性表面活性剂。 For microporous molecular sieve materials, the structure directing agent employed in synthesis of small molecules, mostly short-chain amines; for mesoporous, the structure directing agent employed people amphiphilic surfactants, including cationic surfactants, anionic surfactants, nonionic surfactants and bis surfactant. 在反应过程中,得到无机物种在有机模板剂周围排列的有机-无机复合材料之后,只有将其含有的有机模板剂去除,才可以得到具有开放孔的孔洞结构。 During the reaction, to obtain an inorganic species in an organic templating agent arranged around an organic - inorganic composite material after only containing the organic templating agent is removed, it can be obtained a porous structure with open pores.

迄今为止,国际上对于有机模板剂的去除多使用两种方法:直接焙烧法、离子交换法和溶剂萃取法。 To date, international for removal of the organic templating agent is often used in two ways: direct baking method, ion exchange and solvent extraction. 直接焙烧法是指将合成得到的有机-无机复合材料直接在特定的温度下在空气或氧气气氛中灼烧,使有机模板剂氧化成气体小分子而从体系中脱除;离子交换法是指使用一定的离子将孔道中的结构导向剂置换出来;溶剂萃取法是指将有机-无机复合物置于一定的溶剂(如乙醇、甲醇或者它们与盐酸的混合溶液)中,利用溶剂对有机模板剂的高的溶解度将其从复合物的孔道中萃取出来,从而得到开放的孔洞结构。 Method refers to the direct firing synthesized organic - inorganic composite material is calcined in air or an oxygen atmosphere at a specific temperature directly, the organic templating agent oxidized to small gas molecules removed from the system; ion exchange method is a method use of certain ions structure directing agent in the tunnels displaced; solvent extraction refers to an organic - inorganic composite was placed in a certain solvent (e.g., ethanol, methanol or a mixed solution thereof with hydrochloric acid) in a solvent of the organic templating agent the high solubility which was extracted from the bore of the composite, resulting in an open pore structure. 但是,这几种方法都存在着一定的缺点。 However, these methods have definite drawbacks. 对于直接焙烧法,形成的多孔材料与原来的复合材料相比,骨架有较大的收缩,使得孔径变小;而且由于改过程在较高的温度下进行,材料的表面基团(如羟基等)会受到一定程度的破坏,大大影响了材料本身的特殊性能。 For direct baking method, a porous material formed of a composite material compared to the original, the skeleton has large shrinkage, so the aperture becomes smaller; and because the change is carried out at a higher temperature, the material surface groups (e.g., hydroxyl group ) will be a certain degree of damage, greatly influenced the special properties of the material itself. 另外,焙烧法对于热稳定性较差的材料是不适用的,具有较大的局限性。 Further, calcination for poor thermal stability is not applicable, has great limitations. 对于离子交换法和溶剂萃取法,最后得到的材料虽然与复合材料相比,骨架并没有明显的收缩现象,但是操作比较费时,并且有机模板剂(结构导向剂)不可能全部被脱除,孔道达不到100%开放,孔材料孔道内表面也不可能有效地暴露出来。 For ion exchange and solvent extraction, the resulting composite material while compared with the skeleton and no significant shrinkage, but time consuming operation, and the organic template (structure directing agent) can not all be removed, bore reach 100% open, the inner surface of the pore porous material can not effectively be exposed.

发明内容 SUMMARY

本发明的目的在于提出一种可快速、简便、有效地脱除有机-无机复合多孔材料所含有机模板剂的方法。 Object of the present invention is to provide a quick, simple and effective removal of organic - an organic templating agent contained in the inorganic composite porous material. 从而使得最后所得的孔材料保留较多的表面羟基,具有较低的骨架收缩率以及高的比表面积、孔容、结构有序度和大的孔径,并且有机物种的去除率可以达到100%,以满足科学研究和工业应用的需要。 So that the resulting final porous material retain more surface hydroxyl groups, the skeleton has a lower shrinkage and high specific surface area, pore volume, and the structural order of the large aperture, and the removal of the organic species may reach 100%, to meet the needs of scientific research and industrial applications.

本发明提出的有机-无机复合多孔材料有机模板剂的脱除方法,是采用微波加热消解体系,结合以廉价的氧化性无机酸和双氧水为溶剂,利用体系中自生的压力,脱除有机模板剂。 The present invention is made of organic - inorganic composite porous material removal process, the organic templating agent, is heated by microwave digestion system, in conjunction with the pressure inexpensive oxidizing mineral acid and hydrogen peroxide as solvent, using autogenous system, removal of organic templating agent .

本发明提出的有机-无机复合多孔材料有机模板剂的脱除方法,其具体操作过程如下所述:首先将有机-无机复合多孔材料置于微波消解罐中,加入氧化性酸和双氧水,旋紧消解罐盖后置于微波炉腔内;选择消解压力和消解时间;消解完毕后使体系冷却,随即过滤除去消解液,并用蒸馏水洗涤;氧化性酸、双氧水与复合多孔材料的质量比为4-10∶1-20∶1;消解压力为5-20个大气压;消解温度为120-200℃;消解时间为1-20分钟。 The present invention is made of organic - inorganic composite porous material removal process, the organic templating agent, the specific operation is as follows: First, an organic - inorganic composite porous material is placed in a microwave digestion vessel, and hydrogen peroxide was added oxidizing acids, tighten after digestion can lids into a microwave oven cavity; selection pressure digestion and digestion time; the system was cooled after the completion of digestion, digestion was then removed by filtration, and washed with distilled water; oxidizing acid, hydrogen peroxide and the mass ratio of the composite porous material is 4-10 :1-20:1; digestion pressure 5-20 atm; digestion temperature of 120-200 deg.] C; digestion time of 1 to 20 minutes.

上述脱除方法中,去除有机模板剂时所用的氧化性酸可以是浓硝酸,也可以是浓硫酸或高氯酸等。 Removal of the above-described method, the oxidizing acid is removed organic templating agent may be used in concentrated nitric acid, concentrated sulfuric acid or may be perchloric acid and the like.

上述脱除方法中,去除有机模板剂时所用的双氧水可以是商品双氧水,也可以是由过氧化物如过氧化钾、过氧化钠与硝酸反应形成。 Removal of the above-described methods, when the removal of the organic templating agent used hydrogen peroxide may be hydrogen peroxide product, may be a peroxide such as potassium, sodium peroxide and nitric acid are formed.

上述脱除方法中,有机模板剂去除时采用高压密闭微波消解体系,消解压力为5-20个大气压。 Removal of the above-described method, the organic templating agent is removed using a high-pressure sealed microwave digestion system, a pressure of 5-20 atm digestion.

上述有机模板剂的脱除方法适用的有机-无机复合多孔材料,包括微孔分子筛材料(如ZSM-5等)、介孔分子筛材料(如MCM-41,MCM-48,SBA-2,SBA-12,SBA-15,SBA-16,MSU-X,HMS等)、大孔材料、大孔-介孔多级孔材料以及介孔-微孔多级孔材料。 The above-described method of removing an organic templating agent suitable organic - inorganic composite porous material comprises a microporous molecular sieve material (e.g. ZSM-5, etc.), mesoporous molecular sieve material (e.g., MCM-41, MCM-48, SBA-2, SBA- 12, SBA-15, SBA-16, MSU-X, HMS, etc.), macroporous materials, macroporous - multistage mesopores and pore mesoporous materials - micropores multistage porous material.

采用上述方法所得的材料较一般的经直接焙烧或溶剂萃取等方法得到的材料有更高的比表面积、孔容和结构有序度,更大的孔径,更多的表面硅羟基以及更低的骨架收缩率,有机物种的去除率可以达到100%。 The resulting material as the above-described method more general obtained by direct calcination or solvent extraction method has a higher specific surface area, pore volume, and the degree of structural order, larger pore size, more surface silanols and lower skeleton shrinkage, removal of the organic species may reach 100%. 这类具有优良性能的孔材料在催化、吸附以及作为合成纳米材料的硬模板等方面发挥特殊的作用。 Such porous materials having excellent properties play a special role in catalysis, adsorption as well as the synthesis of nanomaterials hard templates.

具体实施方式 detailed description

实施例1:微孔分子筛ZSM-5有机胺模板剂的脱除。 Removal of ZSM-5 zeolite pore templating agent an organic amine: Example 1. 将0.5g含有机胺的ZSM-5粉末加入聚四氟乙烯高压消解罐中,再分别加入3-5g浓硫酸和1-2g浓双氧水。 The 0.5g ZSM-5 powder was added an amine-containing PTFE high pressure digestion vessel, then added 3-5g 1-2g concentrated hydrogen peroxide and concentrated sulfuric acid, respectively. 密封消解罐后,将其置于MK-II型光纤压力自控微波炉中,设置压力为10个大气压。 After digestion vessel sealed, placed MK-II type fiber optic pressure-controlled microwave oven, the set pressure of 10 atm. 开启消解程序,在10个大气压下消解10分钟,消解温度为180℃。 Open digestion process, digestion at 10 atm for 10 minutes digestion temperature of 180 ℃. 消解完毕后体系冷却10分钟,随即过滤除去消解液,并用蒸馏水洗涤即可。 After digestion is complete the system was cooled for 10 minutes and then the digestion solution was removed by filtration, and washed with distilled water to.

实施例2:介孔分子筛SBA-15高分子模板剂的脱除。 Example 2: Removal of the polymer template mesoporous molecular sieve 15 SBA-. 将0.5g含高分子(P123)的SBA-15粉末加入聚四氟乙烯高压消解罐中,再分别加入3-5g浓硫酸和0.5-2g浓双氧水。 The polymer containing 0.5g (P123) of SBA-15 powder was added to the high-pressure digestion vessel polytetrafluoroethylene, 3-5g added concentrated sulfuric acid and concentrated hydrogen peroxide 0.5-2g respectively. 密封消解罐后,将其置于MK-II型光纤压力自控微波炉中,设置压力为5个大气压。 After digestion vessel sealed, placed MK-II type fiber optic pressure-controlled microwave oven, a pressure of 5 atm. 开启消解程序,在5个大气压下消解4分钟,消解温度为120℃。 Open digestion process, digested for 4 minutes at 5 atm, digestion temperature of 120 ℃. 消解完毕后体系冷却数分钟,随即过滤除去消解液,并用蒸馏水洗涤即可。 After digestion is complete the cooling system for several minutes, then digestion was removed by filtration, and washed with distilled water to.

实施例3:介孔分子筛薄膜高分子模板剂的脱除。 Removal of the polymer film mesoporous templating agent: Example 3. 将0.5g含高分子(F127)的介孔分子筛薄膜加入聚四氟乙烯高压消解罐中,再分别加入2-4g浓硝酸和5-8g浓双氧水。 Mesoporous film containing 0.5g of polymer (F127) added to the high-pressure Teflon digestion vessel, then added 2-4g 5-8g concentrated hydrogen peroxide and concentrated nitric acid respectively. 密封消解罐后,将其置于MK-II型光纤压力自控微波炉中,设置压力为20个大气压。 After digestion vessel sealed, placed MK-II type fiber optic pressure-controlled microwave oven, a pressure of 20 atmospheres. 开启消解程序,在20个大气压下消解3分钟,消解温度为200℃,消解完毕后体系冷却数分钟,随即过滤除去消解液,并用蒸馏水洗涤即可。 Open digestion process, digestion at 20 atmospheres for 3 minutes, digestion temperature of 200 ℃, digestion cooling system is completed after a few minutes, then digestion was removed by filtration, and washed with distilled water to.

实施例4:大孔材料高分子模板剂的脱除。 Removal of macroporous polymer material templating agent: Example 4. 将0.4g含高分子(聚苯乙烯)的大孔材料加入聚四氟乙烯高压消解罐中,再分别加入3-4g高氯酸和1-2g浓双氧水。 0.4g of macroporous polymer containing material (polystyrene) in the high-pressure digestion tank polytetrafluoroethylene was added, followed by addition 3-4g 1-2g concentrated perchloric acid and hydrogen peroxide, respectively. 密封消解罐后,将其置于MK-II型光纤压力自控微波炉中,设置压力为10个大气压。 After digestion vessel sealed, placed MK-II type fiber optic pressure-controlled microwave oven, the set pressure of 10 atm. 开启消解程序,在10个大气压下消解20分钟,消解温度为180℃。 Open digestion process, digestion at 10 atm for 20 minutes digestion temperature of 180 ℃. 消解完毕后体系冷却数分钟,随即过滤除去消解液,并用蒸馏水洗涤即可。 After digestion is complete the cooling system for several minutes, then digestion was removed by filtration, and washed with distilled water to.

实施例5:大孔一介孔多级孔材料高分子模板剂的脱除。 Example 5: macroporous pore ordinary multistage polymer porous material removed templating agent. 将0.2g含高分子(聚苯乙烯和P123)的大孔-介孔多级孔材料加入聚四氟乙烯高压消解罐中,再分别加入0.8-1g浓硝酸和3-4g浓双氧水。 Containing 0.2g of polymer (polystyrene and P123) macroporous - mesopores multistage polytetrafluoroethylene porous material added to the high-pressure digestion vessel, 0.8-1g added concentrated nitric acid and concentrated hydrogen peroxide are 3-4g. 密封消解罐后,将其置于MK-II型光纤压力自控微波炉中,设置压力为5个大气压。 After digestion vessel sealed, placed MK-II type fiber optic pressure-controlled microwave oven, a pressure of 5 atm. 开启消解程序,在5个大气压下消解5分钟,消解温度为120℃。 Open digestion process, digestion at 5 atm for 5 minutes, digestion temperature of 120 ℃. 消解完毕后体系冷却数分钟,随即过滤除去消解液,并用蒸馏水洗涤即可。 After digestion is complete the cooling system for several minutes, then digestion was removed by filtration, and washed with distilled water to.

由上述实施例获得的有机-无机复合多孔材料,其有机模板剂的去除率均达到100%,且材料性能优良。 The organic obtained by the above-described embodiment - inorganic composite porous material, an organic templating agent removal rate reached 100%, and the excellent material properties.

Claims (3)

1.一种有机-无机复合多孔材料有机模板剂的脱除方法,其特征在于具体步骤如下:首先将有机-无机复合多孔材料置于微波消解罐中,加入氧化性酸和双氧水,旋紧消解罐盖后置于微波炉腔内;选择消解压力为5-20个大气压,消解温度为120-200℃,消解时间为1-20分钟;消解完毕后将体系冷却,随即过滤除去消解液,并用蒸馏水洗涤;氧化性酸、双氧水与复合多孔材料的质量比为4-10∶1-20∶1。 An organic - inorganic composite porous material removal process organic templating agent, wherein the following steps: First, an organic - inorganic composite porous material is placed in a microwave digestion vessel, and hydrogen peroxide was added oxidizing acids, tighten digestion after the can lids into a microwave oven cavity; digestion selected pressure of 5-20 atm, digestion temperature of 120-200 deg.] C, digestion time of 1 to 20 min; cooled after completed digestion, digestion was then removed by filtration, and washed with distilled water washed; oxidizing acid, hydrogen peroxide and the mass ratio of the composite porous material is 4-10:1-20:1.
2.根据权利要求1所述的一种有机-无机复合多孔材料有机模板剂的脱除方法,其特征在于所用的氧化性酸为浓硝酸,或浓硫酸,或高氯酸。 2. An organic according to claim 1 - Method for removing inorganic composite porous material of an organic templating agent, wherein the oxidizing acid is used in concentrated nitric acid, or sulfuric acid, or perchloric acid.
3.根据权利要求1所述的一种有机-无机复合多孔材料有机模板剂的脱除方法,其特征在于有机-无机复合多孔材料为抗酸性的材料,包括各种微孔分子筛材料、各种介孔分子筛材料、大孔材料、大孔-介孔多级孔材料以及大孔-微孔多级孔材料。 According to the claim 1, an organic - inorganic composite porous material removal process, the organic templating agent, wherein the organic - inorganic composite porous material of acid resistant materials, including microporous molecular sieve materials, various mesoporous materials, macroporous materials, macroporous - multistage mesopores and macropores porous material - micropores multistage porous material.
CN 03150611 2003-08-26 2003-08-26 Method for removing organic-inorganic composite porous material organic template agent CN1219701C (en)

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CN1307097C (en) * 2005-10-20 2007-03-28 浙江大学 Method of removing organic template agent from molecular sieve
WO2007091828A1 (en) * 2006-02-07 2007-08-16 Korea Research Institute Of Chemical Technology A preparation method of porous hybrid inorganic-organic materials
CN102180479A (en) * 2011-03-21 2011-09-14 复旦大学 Method for digesting organic template agent of nano zeolite in situ with assistance of microwave
CN102583529A (en) * 2012-02-28 2012-07-18 南京大学 Method for preparing mesoporous titanium dioxide by template method and application of mesoporous titanium dioxide to preparation of dye-sensitized solar cells
CN104556100A (en) * 2013-10-24 2015-04-29 中国石油化工股份有限公司 Method for removing organic amine template in borosilicate beta molecular sieve
CN105271284A (en) * 2015-06-09 2016-01-27 浙江师范大学 Method for removing organic template agent in porous material through wet method
CN106745026A (en) * 2016-12-16 2017-05-31 南京工业大学 A kind of preparation method of zero defect DDR molecular screen membranes

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1307097C (en) * 2005-10-20 2007-03-28 浙江大学 Method of removing organic template agent from molecular sieve
WO2007091828A1 (en) * 2006-02-07 2007-08-16 Korea Research Institute Of Chemical Technology A preparation method of porous hybrid inorganic-organic materials
US7855299B2 (en) 2006-02-07 2010-12-21 Korea Research Institute Of Chemical Technology Preparation method of porous organic inorganic hybrid materials
CN102180479A (en) * 2011-03-21 2011-09-14 复旦大学 Method for digesting organic template agent of nano zeolite in situ with assistance of microwave
CN102583529A (en) * 2012-02-28 2012-07-18 南京大学 Method for preparing mesoporous titanium dioxide by template method and application of mesoporous titanium dioxide to preparation of dye-sensitized solar cells
CN102583529B (en) * 2012-02-28 2014-12-10 南京大学 Method for preparing mesoporous titanium dioxide by template method and application of mesoporous titanium dioxide to preparation of dye-sensitized solar cells
CN104556100A (en) * 2013-10-24 2015-04-29 中国石油化工股份有限公司 Method for removing organic amine template in borosilicate beta molecular sieve
CN105271284A (en) * 2015-06-09 2016-01-27 浙江师范大学 Method for removing organic template agent in porous material through wet method
CN106745026A (en) * 2016-12-16 2017-05-31 南京工业大学 A kind of preparation method of zero defect DDR molecular screen membranes
CN106745026B (en) * 2016-12-16 2019-01-11 南京工业大学 A kind of preparation method of zero defect DDR molecular screen membrane

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