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CN105536738A - Composite adsorption material with MAR and MIL-53 (Al) combined and preparation method thereof - Google Patents

Composite adsorption material with MAR and MIL-53 (Al) combined and preparation method thereof Download PDF

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CN105536738A
CN105536738A CN201610056701.6A CN201610056701A CN105536738A CN 105536738 A CN105536738 A CN 105536738A CN 201610056701 A CN201610056701 A CN 201610056701A CN 105536738 A CN105536738 A CN 105536738A
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mar
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porous resin
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CN105536738B (en
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徐斌
龚宇
金诚妙
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Tongji University
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28078—Pore diameter
    • B01J20/2808—Pore diameter being less than 2 nm, i.e. micropores or nanopores
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
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Abstract

本发明涉及一种MAR与MIL-53（Al）组合的复合吸附材料的制备方法，所述复合吸？n？附材料是以多孔树脂（MAR）为晶体生长的载体，有机配体在多孔树脂孔内形成金属有机框架材料，复合材料的颗粒外径为3~6mm。本专利采用溶剂热法制备MAR与MIL-53（Al）组合的复合吸附材料，该复合材料不仅克服了单独MIL-53（Al）材料只能形成粉末状无法用于空气过滤的问题，而且克服了多孔树脂孔径过大、比表面积低的问题，能够突破实际应用中过滤超低浓度小分子气体污染物的现存技术瓶颈。

The invention relates to a preparation method of a composite adsorption material combined with MAR and MIL-53 (Al). The composite adsorption? n? The attached material uses porous resin (MAR) as the carrier for crystal growth, and the organic ligand forms a metal-organic framework material in the pores of the porous resin. The outer diameter of the particles of the composite material is 3-6mm. This patent uses a solvothermal method to prepare a composite adsorption material combined with MAR and MIL-53 (Al). This composite material not only overcomes the problem that MIL-53 (Al) alone can only form powder and cannot be used for air filtration, but also overcomes the The problem of too large pore size and low specific surface area of porous resin can be solved, and it can break through the existing technical bottleneck of filtering ultra-low concentration small molecular gas pollutants in practical applications.

Description

A kind of MAR and MIL-53(Al) composite adsorbing material that combines and preparation method thereof
Technical field
The invention belongs to air pollutants scavenging material preparation field, be specifically related to a kind of MAR and MIL-53(Al) composite adsorbing material that combines and preparation method thereof.
Background technology
At present, air pollution becomes the topic that people more and more pay close attention to, and surrounding air is to city atmospheric environment indoor, then pollutes to global atmosphere.According to the data display that the World Health Organization issues, the various diseases death toll that the whole world in 2012 causes because of air pollution is about 7,000,000.In order to the living environment of healthy high-quality, the improvement of new type purification material and equipment and invention, necessary.Particularly for the dusty gas of some molecular particle sizes very little (0.1-0.9nm), as formaldehyde (0.414nm), benzene (0.58nm), methane (0.414nm) etc., existing porous material (active carbon, macroreticular resin), not good to the adsorption effect of these micro-molecular gas pollutants, because molecular particle size is little, the time of staying in sorbing material is short, so affect its adsorption effect [1].MOFs is just developing rapidly as a kind of new type functional molecular material and is becoming the study hotspot of material, chemistry, environmental area.Its aperture is adjustable and the characteristic of bigger serface [2], make it in absorption, show abnormal advantage.Specific area as MIL-53 (Al) reaches 1086m 2/ g, pore volume reaches 0.58cm 3/ g, average pore size is 2.13nm, and average grain diameter, at 5.52nm, possesses stronger adsorption capacity.The MOFs reported now mostly is microcellular structure, has the characteristics such as specific area is large, thus achieves MOFs in the application of filtering the uniqueness on micro-molecular gas.But MOFs material is all Powdered, has the inferior position that can not form bulky grain product.In addition, although various NEW TYPE OF COMPOSITE MOFs material well solves the problem that large molecule is difficult to diffuse to internal active sites, as Lin-BingSun etc. [3]use CTAB as template, CA (citric acid) connects CTAB and Cu (II) as chelating agent, synthesis Cu 3(BTC) 2(HKUST-1).But cannot make granular product because its crystalline size is too small, its filtration application for super low concentration micro-molecular gas pollutant is still not good.On the whole, on the one hand, if the aperture in porous material is greater than more than 2 times of the dynamics equivalent diameter of gas molecule, molecule is easily through hole, and filter efficiency is low; Synthesis has the MOFs average crystal grain diameter of homogeneous microcellular structure all in micron level on the other hand, and this just causes and MOFs cannot be assembled into air cleaner in actual use.So also there is certain technical bottleneck for the filtration of super low concentration micro-molecular gas pollutant in present stage.
[1] Zhou Tianxiao. macroreticular resin absorbing method process carrene waste gas research [D]. Zhejiang University, 2014.
[2] Hao Xiangrong. based on MOF duct material [D] that rigid ligand and template effect are constructed. Northeast Normal University, 2012.
[3]SunLB,LiJR,ParkJ,etal.Cooperativetemplate-directedassemblyofmesoporousmetal–organicframeworks[J].JournaloftheAmericanChemicalSociety,2011,134(1):126-129。
Summary of the invention
The present invention is directed to the shortcoming and defect of above-mentioned current porous material and MOFs existence, a kind of MAR and MIL-53(Al is proposed) composite adsorbing material that combines and preparation method thereof, described composite adsorbing material has efficient adsorption effect to low concentration Small molecular dusty gas.
A kind of MAR and MIL-53(Al that the present invention proposes) composite adsorbing material that combines, this composite take porous resin as the complex carrier of crystal growth, organic ligand forms metal-organic framework material in porous resin hole, and the composite gauge made is 3 ~ 6mm.
A kind of MAR and MIL-53(Al that the present invention proposes) preparation method of composite adsorbing material that combines, concrete steps are as follows:
(1) terephthalic acid (TPA) and aluminum nitrate are joined in DMF solution, stir until terephthalic acid (TPA) and aluminum nitrate dissolve completely under the condition of 70 ~ 80 DEG C; The quality of terephthalic acid (TPA) is 1.2-1.5 times of the quality of aluminum nitrate;
(2) after porous resin absolute ethyl alcohol and massive laundering are washed, vacuum drying, is added in step (1) gained solution by dried porous resin, stirs 20 ~ 30h at the condition lower magnetic forces of 55 ~ 65 DEG C; Then mixed liquor is transferred in teflon-lined reactor, under 120 ~ 150 DEG C of conditions, heats 40 ~ 50h; Obtain white milkiness shape precipitation;
(3) after reaction terminates, the white milkiness shape pelleting centrifugation that step (2) is obtained, and wash away unreacted organic ligand with methyl alcohol and carrene; Finally, by obtained sample vacuum drying 20 ~ 30h, MAR and the MIL-53(Al obtained under vacuum drying chamber 75 ~ 80 DEG C of conditions) composite adsorbing material that combines.
In the present invention, the DMF liquor capacity mark selected is 60 ~ 65%, and the concentration of terephthalic acid (TPA) is 15 ~ 20g/L, and the concentration of aluminum nitrate is 50 ~ 60g/L.
In the present invention, the porous resin aperture in described step (1) is 100 ~ 200nm.
The present invention prepares scheme with existing MOFs sorbing material and compares with technology, has following innovation and advantage:
(1) a kind of MAR and the MIL-53(Al related in the present invention) in the composite adsorbing material that combines and preparation method thereof, with the carrier that porous resin (MAR) is crystal growth, organic ligand forms metal-organic framework material on porous resin surface, the size 3-6mm of composites, achieves the bulky grain sized products in practical application.
(2) a kind of MAR and the MIL-53(Al related in the present invention) in the composite adsorbing material that combines and preparation method thereof, MAR and the MIL-53(Al made) specific area of composite adsorbing material that combines reaches 1746m 2/ g, pore volume reaches 1.58cm 3/ g, average pore size is 0.5 ~ 1nm, has higher adsorption effect to small size gas molecule, possesses stronger adsorption applications potentiality to the purification of low concentration Small molecular air pollutants;
(3) a kind of MAR and the MIL-53(Al related in the present invention) in the composite adsorbing material that combines and preparation method thereof, can according to the monitoring result of reality gas molecule size to be clean, and select suitable porous resin size, and prepare MAR and the MIL-53(Al of high efficiency filter) composite adsorbing material that combines.
(4) a kind of MAR and the MIL-53(Al related in the present invention) in the composite adsorbing material that combines and preparation method thereof, adopt hydrothermal synthesis method, technique is simple, and repeatability is better.
Accompanying drawing explanation
Fig. 1 MAR and MIL-53(Al) the composite synthetic schemes that combines.
Detailed description of the invention
Be below by reference to the accompanying drawings 1 and the instantiation that completes according to technical scheme of the present invention of inventor, the present invention is described in further detail.
Embodiment 1
1.245g terephthalic acid (TPA) and 4.220g aluminum nitrate being joined volume fraction is in the DMF solution of 60%, stirs until terephthalic acid (TPA) and aluminum nitrate dissolve completely under the condition of 80 DEG C.Then, the aperture selecting porous resin is 120nm, and after washing by absolute ethyl alcohol and massive laundering, vacuum drying, is added to dried macroporous absorbent resin in above-mentioned solution, stirs 25h at the condition lower magnetic forces of 65 DEG C.Mixed solution is transferred in teflon-lined reactor, under 130 DEG C of conditions, heats 48h.After reaction terminates, obtained milkiness shape pelleting centrifugation is also washed away unreacted organic ligand with methyl alcohol and carrene.Finally, by obtained sample vacuum drying 24h under vacuum drying chamber 80 DEG C of conditions, MAR and MIL-53(Al is obtained) composite adsorbing material that combines.
Get obtained composite 1, pass into the mist of benzene, formaldehyde and nitrogen composition, carry out Static Adsorption test, to test its clean-up effect.In mist, the gas concentration of benzene and formaldehyde is 400ppb, and adsorption column is of a size of 10mm × 200mm, and experimental temperature is 27 DEG C, and after purification, the concentration of benzene and formaldehyde is respectively 6ppb and 21ppb.
Embodiment 2
1.245g terephthalic acid (TPA) and 4.220g aluminum nitrate being joined volume fraction is in the DMF solution of 60%, stirs until terephthalic acid (TPA) and aluminum nitrate dissolve completely under the condition of 80 DEG C.Then, the aperture selecting porous resin is 200nm, and after washing by absolute ethyl alcohol and massive laundering, vacuum drying, is added to dried macroporous absorbent resin in above-mentioned solution, stirs 25h at the condition lower magnetic forces of 65 DEG C.Mixed solution is transferred in teflon-lined reactor, under 130 DEG C of conditions, heats 48h.After reaction terminates, obtained milkiness shape pelleting centrifugation is also washed away unreacted organic ligand with methyl alcohol and carrene.Finally, by obtained sample vacuum drying 24h under vacuum drying chamber 80 DEG C of conditions, MAR and MIL-53(Al is obtained) composite adsorbing material that combines.
Get obtained composite 2, pass into the mist of benzene, formaldehyde and nitrogen composition, carry out Static Adsorption test, to test its clean-up effect.In mist, the gas concentration of benzene and formaldehyde is 400ppb, and adsorption column is of a size of 10mm × 200mm, and experimental temperature is 27 DEG C, and after purification, the concentration of benzene and formaldehyde is respectively 3ppb and 14ppb.
Embodiment 3
1.245g terephthalic acid (TPA) and 4.220g aluminum nitrate being joined volume fraction is in the DMF solution of 60%, stirs until terephthalic acid (TPA) and aluminum nitrate dissolve completely under the condition of 80 DEG C.Then, the aperture selecting porous resin is 300nm, and after washing by absolute ethyl alcohol and massive laundering, vacuum drying, is added to dried macroporous absorbent resin in above-mentioned solution, stirs 25h at the condition lower magnetic forces of 65 DEG C.Mixed solution is transferred in teflon-lined reactor, under 130 DEG C of conditions, heats 48h.After reaction terminates, obtained milkiness shape pelleting centrifugation is also washed away unreacted organic ligand with methyl alcohol and carrene.Finally, by obtained sample vacuum drying 24h under vacuum drying chamber 80 DEG C of conditions, MAR and MIL-53(Al is obtained) composite adsorbing material that combines.
Get obtained composite 3, pass into the mist of benzene, formaldehyde and nitrogen composition, carry out Static Adsorption test, to test its clean-up effect.In mist, the gas concentration of benzene and formaldehyde is 400ppb, and adsorption column is of a size of 10mm × 200mm, and experimental temperature is 27 DEG C, and after purification, the concentration of benzene and formaldehyde is respectively 28ppb and 46ppb.
Comparative example
Get undressed MIL-53 (Al), pass into the mist of benzene, formaldehyde and nitrogen composition, carry out Static Adsorption test, to test its clean-up effect.In mist, the gas concentration of benzene and formaldehyde is 400ppb, and adsorption column is of a size of 10mm × 200mm, and experimental temperature is 27 DEG C, and after purification, the concentration of benzene and formaldehyde is respectively 106ppb and 114ppb.
Table the effect contrast table of each embodiment
Above-mentioned is can understand and use invention for ease of those skilled in the art to the description of embodiment.Person skilled in the art obviously easily can make various amendment to these embodiments, and General Principle described herein is applied in other embodiments and need not through performing creative labour.Therefore, the invention is not restricted to above-described embodiment, those skilled in the art, according to announcement of the present invention, do not depart from improvement that scope makes and amendment all should within protection scope of the present invention.

Claims (4)

1.一种MAR与 MIL-53（Al）组合的复合吸附材料，其特征在于复合材料是以多孔树脂为晶体生长的复合载体，有机配体在多孔树脂孔内形成金属有机框架材料，所制出的复合材料尺寸为3~6mm。1. A composite adsorption material combined with MAR and MIL-53 (Al), which is characterized in that the composite material is a composite carrier for crystal growth with porous resin, and organic ligands form a metal-organic framework material in the pores of the porous resin. The size of the composite material produced is 3~6mm. 2.一种如权利要求1所述的MAR与 MIL-53（Al）组合的复合吸附材料的制备方法，其特征在于具体步骤如下：2. A preparation method of a composite adsorbent material combined with MAR and MIL-53 (Al) as claimed in claim 1, characterized in that the specific steps are as follows: （1）将对苯二甲酸和硝酸铝加入到DMF溶液中，在70~80℃的条件下搅拌直至对苯二甲酸和硝酸铝完全溶解；对苯二甲酸的质量是硝酸铝的质量的1.2-1.5倍；(1) Add terephthalic acid and aluminum nitrate to the DMF solution and stir at 70~80°C until the terephthalic acid and aluminum nitrate are completely dissolved; the mass of terephthalic acid is 1.2 times the mass of aluminum nitrate -1.5 times; （2）多孔树脂用无水乙醇和大量水洗涤后，真空干燥，将干燥后的多孔树脂加到步骤（1）所得溶液中，在55~65℃的条件下磁力搅拌20~30h；然后将混合液转移至聚四氟乙烯内衬的反应釜中，120~150℃条件下加热40~50h；得到白色乳浊状沉淀；(2) After washing the porous resin with absolute ethanol and a large amount of water, dry it in vacuum, add the dried porous resin to the solution obtained in step (1), and stir magnetically at 55-65°C for 20-30 hours; then The mixed solution was transferred to a polytetrafluoroethylene-lined reaction kettle, and heated at 120-150°C for 40-50 hours; a white milky precipitate was obtained; （3）反应结束后，将步骤（2）所得到的白色乳浊状沉淀离心，并用甲醇和二氯甲烷洗去未反应的有机配体；最终，将所得到的样品在真空干燥箱75~80℃条件下真空干燥20~30h，得到的MAR与 MIL-53（Al）组合的复合吸附材料。(3) After the reaction, centrifuge the white milky precipitate obtained in step (2), and wash away unreacted organic ligands with methanol and dichloromethane; finally, put the obtained sample in a vacuum drying oven for 75~ Vacuum drying at 80°C for 20-30 hours to obtain a composite adsorption material combining MAR and MIL-53 (Al). 3.根据权利要求1所述的MAR与 MIL-53（Al）组合的复合吸附材料的制备方法，其特征在于选用的DMF溶液体积分数为60~65%，对苯二甲酸的浓度为15~20g/L，硝酸铝的浓度为50~60g/L。3. according to the preparation method of the composite adsorption material of MAR and MIL-53 (Al) combination according to claim 1, it is characterized in that the selected DMF solution volume fraction is 60 ~ 65%, and the concentration of terephthalic acid is 15 ~ 20g/L, the concentration of aluminum nitrate is 50~60g/L. 4.根据权利要求1所述的MAR与 MIL-53（Al）组合的复合吸附材料的制备方法，其特征在于所述步骤（1）中的多孔树脂孔径为100~200nm。4. The preparation method of the composite adsorption material combining MAR and MIL-53 (Al) according to claim 1, characterized in that the pore diameter of the porous resin in the step (1) is 100-200nm.
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Cited By (2)

* Cited by examiner, † Cited by third party
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CN106732459A (en) * 2016-12-26 2017-05-31 南京师范大学 A kind of porous resin metal organic frame composite pellets adsorbent and its preparation method and application
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