技术领域technical field
本发明涉及无机有机杂化材料技术领域，具体一种微孔金属有机骨架材料及其制备方法与应用。The invention relates to the technical field of inorganic-organic hybrid materials, in particular to a microporous metal-organic framework material and its preparation method and application.
背景技术Background technique
近年来能源危机受到全世界的广泛关注，能源短缺问题亟待解决。虽然新能源技术被积极的研究并开发利用，但化石能源(如煤、石油和天然气)仍然是人类社会的主要能源，如何提高化石能源的使用效率成为解决问题的关键途径。甲烷是天然气的主要成分，不仅是生活常用的清洁燃料，还是一种重要的化工原料。然而甲烷中杂质(如其他烷烃、烯烃、炔烃和非烃气体)的存在会影响甲烷的使用和转化效率。另外，甲烷裂解制乙炔是工业上制备乙炔的一种常用方法，主要方程式如下：In recent years, the energy crisis has attracted worldwide attention, and the problem of energy shortage needs to be solved urgently. Although new energy technologies are actively researched, developed and utilized, fossil energy (such as coal, oil and natural gas) is still the main energy source of human society, how to improve the efficiency of fossil energy use has become a key way to solve the problem. Methane is the main component of natural gas. It is not only a clean fuel commonly used in daily life, but also an important chemical raw material. However, the presence of impurities in methane (such as other alkanes, alkenes, alkynes, and non-hydrocarbon gases) can affect methane use and conversion efficiency. In addition, methane cracking to acetylene is a common method for industrially producing acetylene, and the main equation is as follows:
该反应不仅需要纯度较高的甲烷作为原料(90％以上)，而且甲烷转化为乙炔的产率只有40％～50％，产生的裂解气为包含大量甲烷和乙炔的混合气。所以，从甲烷中分离乙炔是一种重要的工业生产流程，不仅能提高天然气的纯度，还能为化工生产提供纯化的乙炔原料。This reaction not only requires methane with higher purity (over 90%) as a raw material, but also the conversion rate of methane to acetylene is only 40% to 50%, and the cracked gas produced is a mixed gas containing a large amount of methane and acetylene. Therefore, the separation of acetylene from methane is an important industrial production process, which can not only improve the purity of natural gas, but also provide purified acetylene raw materials for chemical production.
传统的分离工艺是裂解气深冷分离技术，利用裂解气中各类烃相对挥发度的差异，在低温下将除氢气外的烃类全部冷凝，之后转入精馏塔进行多组分精馏分离，不仅能耗较大，而且设备造价较高[CN205774195U、CN205700034U、CN1292486A、CN104534812A]。另外工业上也常用溶剂吸附法对乙炔进行分离，例如美国专利US1960326用苯衍生物和硫酸作为吸收溶剂对乙炔进行吸附分离；美国专利US3647843则使用含有配位金属化合物CuAlCl4的甲苯溶液与乙炔发生络合反应，从而对乙炔甲烷混合气进行分离。但这类方法用到大量有机溶剂，成本较高，对环境有污染。The traditional separation process is cracked gas cryogenic separation technology, which uses the difference in relative volatility of various hydrocarbons in the cracked gas to condense all hydrocarbons except hydrogen at low temperature, and then transfers them to the rectification tower for multi-component rectification Separation not only consumes a lot of energy, but also has a high equipment cost [CN205774195U, CN205700034U, CN1292486A, CN104534812A]. In addition, the solvent adsorption method is commonly used in industry to separate acetylene. For example, U.S. PatentUS1960326 uses benzene derivatives and sulfuric acid as absorption solvents to adsorb and separate acetylene; Complexation reaction, so as to separate the mixed gas of acetylene methane. However, this method uses a large amount of organic solvents, which is costly and pollutes the environment.
为了提高分离效率、降低分离成本，开发新型选择性吸附材料是非常意义的。金属有机骨架材料(Metal-Organic Frameworks,MOF)具有比表面积大、孔结构可调节和孔道表面易于修饰等优点，可广泛的应用于气体吸附分离领域。由于MOFs材料对多种气体的捕获都有很好的效果，调节孔的功能性来选择性吸附某类气体从而进行分离成为研究的焦点。中国专利CN10505524083A公开了一种用于纯化天然气的锌金属有机骨架材料的制备方法，该方法以硝酸锌和双(3,5-二羧基苯基)次膦酸有机配体在N,N’-二甲基甲酰胺溶剂中反应制得一种金属有机骨架化合物，然后浸泡、真空干燥得到一种吸附材料，用于天然气的纯化。该制备方法用到有机溶剂N,N’-二甲基甲酰胺，非绿色环保，而且得到的多孔材料中缺少用于选择性分离的功能基团(如氨基、吡啶基等)。In order to improve separation efficiency and reduce separation cost, it is very meaningful to develop new selective adsorption materials. Metal-organic frameworks (Metal-Organic Frameworks, MOF) have the advantages of large specific surface area, adjustable pore structure and easy modification of pore surface, and can be widely used in the field of gas adsorption and separation. Since MOFs materials have a good effect on the capture of various gases, adjusting the functionality of the pores to selectively adsorb certain types of gases for separation has become the focus of research. Chinese patent CN10505524083A discloses a method for preparing a zinc metal organic framework material for purifying natural gas. The method uses zinc nitrate and bis(3,5-dicarboxyphenyl)phosphinic acid organic A metal-organic framework compound is prepared by reacting in a dimethylformamide solvent, and then soaked and vacuum-dried to obtain an adsorption material, which is used for the purification of natural gas. The preparation method uses the organic solvent N,N'-dimethylformamide, which is not environmentally friendly, and the obtained porous material lacks functional groups (such as amino, pyridyl, etc.) for selective separation.
发明内容Contents of the invention
本发明要解决的技术问题是，弥补上诉原有技术的不足，提出一种用于乙炔和甲烷吸附分离的金属有机骨架材料及其制备方法。The technical problem to be solved by the present invention is to make up for the deficiencies of the prior art and to propose a metal organic framework material for adsorption and separation of acetylene and methane and a preparation method thereof.
本发明的技术问题通过以下的技术方案予以解决:Technical problem of the present invention is solved by following technical scheme:
一种微孔金属有机骨架材料，分子式为Y(C30N10O12H15)，其结构式如下：A microporous metal organic framework material, the molecular formula is Y(C30 N10 O12 H15 ), and its structural formula is as follows:
该微孔金属有机骨架化合物属六方晶系，P31c空间群。The microporous metal organic framework compound belongs to the hexagonal crystal system and the space group P31c.
本发明提供了一种微孔金属有机骨架材料的制备方法：将硝酸钇与有机配体2,5,8-三(3,5-二羧基苯胺)-均草怕津(C30N10O10H18，H6TDPAH)溶于水中，于140～180℃反应24～48小时得到微孔金属有机骨架材料粗产品；用无水丙酮洗涤所述微孔金属有机骨架材料粗产品得到纯化的微孔金属有机骨架材料，于80℃～100℃烘干，得到无色块状晶体；有机配体H6TDPAH、硝酸钇、水的摩尔比为1:3～5:800～1200。The invention provides a preparation method of a microporous metal-organic framework material: combining yttrium nitrate with an organic ligand 2,5,8-tris(3,5-dicarboxyaniline)-sampazine (C30 N10 O10 H18 , H6 TDPAH) was dissolved in water, reacted at 140-180°C for 24-48 hours to obtain a crude microporous metal-organic framework material; washed the crude microporous metal-organic framework material with anhydrous acetone to obtain purified The microporous metal-organic framework material is dried at 80°C to 100°C to obtain colorless massive crystals; the molar ratio of organic ligand H6 TDPAH, yttrium nitrate, and water is 1:3 to 5:800 to 1200.
有益效果:Beneficial effect:
1.本发明制备的用于乙炔和甲烷吸附分离的一种微孔金属有机骨架材料是基于Y(III)金属离子与有机配体2,5,8-三(3,5-二羧基苯胺)-均草怕津(C30N10O10H18，H6TDPAH)水热条件下合成得到的金属有机骨架材料，由于有机配体中包含均草怕津与亚氨基官能团，该材料既保持金属有机材料比表面积大、物理吸附能力强的特点，又通过均草怕津与亚氨基官能团共同作用提高孔道与乙炔相互作用。1. A kind of microporous metal-organic framework material used for the adsorption and separation of acetylene and methane prepared by the present invention is based on Y(III) metal ion and organic ligand 2,5,8-three (3,5-dicarboxyaniline) - The metal-organic framework material synthesized under hydrothermal conditions of mesapazine (C30 N10 O10 H18 , H6 TDPAH), since the organic ligand contains mesopazine and imino functional groups, the material maintains both Metal-organic materials have the characteristics of large specific surface area and strong physical adsorption capacity, and the interaction between pores and acetylene is improved through the joint action of mesopazin and imino functional groups.
2.本发明制备的用于乙炔和甲烷吸附分离的一种微孔金属有机骨架材料预处理程序简单易操作。2. The pretreatment procedure of a microporous metal-organic framework material for the adsorption and separation of acetylene and methane prepared by the present invention is simple and easy to operate.
3.本发明制备的用于乙炔和甲烷吸附分离的一种微孔金属有机骨架材料可以实现常压下高效的选择性吸附。3. The microporous metal-organic framework material prepared by the present invention for the adsorption and separation of acetylene and methane can realize high-efficiency selective adsorption under normal pressure.
4.本发明制备的用于乙炔和甲烷吸附分离的一种微孔金属有机骨架在吸附小分子气体后，通过简单的再加热的方式可以将吸附的气体分子去除，有利于反复使用。4. The microporous metal-organic framework prepared by the present invention for the adsorption and separation of acetylene and methane can remove the adsorbed gas molecules by simple reheating after adsorbing small molecule gas, which is beneficial for repeated use.
5.反应用水做溶剂，环境友好。5. The reaction water is used as a solvent, which is environmentally friendly.
附图说明Description of drawings
图1本发明微孔金属有机骨架材料晶体样品图；Fig. 1 crystal sample diagram of microporous metal-organic framework material of the present invention;
图2本发明微孔金属有机骨架材料结构示意图；Fig. 2 is a schematic diagram of the structure of the microporous metal-organic framework material of the present invention;
图3本发明实施例1中制备的微孔金属有机骨架材料的XRD图谱；Fig. 3 is the XRD spectrum of the microporous metal-organic framework material prepared in Example 1 of the present invention;
图4本发明实施例1中制备的微孔金属有机骨架材料的红外图谱；The infrared spectrum of the microporous metal-organic framework material prepared in Example 1 of the present invention in Fig. 4;
图5 77K、0～101324Pa条件下本发明实施例1所制备的微孔金属有机骨架材料的氮气吸附等温线；Fig. 5 The nitrogen adsorption isotherm of the microporous metal-organic framework material prepared in Example 1 of the present invention under the conditions of 77K and 0-101324Pa;
图6在298K、0～101324Pa条件下本发明实施例1所制备的微孔金属有机骨架材料的乙炔和甲烷吸附等温线。Fig. 6 is the acetylene and methane adsorption isotherms of the microporous metal-organic framework material prepared in Example 1 of the present invention under the conditions of 298K and 0-101324Pa.
具体实施方式detailed description
以下结合附图与实施例对本发明作进一步详细描述，需要指出的是，其目的仅在于更好理解本发明的内容而非限制本发明的保护范围。The present invention will be further described in detail below in conjunction with the accompanying drawings and examples. It should be noted that the purpose is only to better understand the content of the present invention but not to limit the protection scope of the present invention.
实施例1：Example 1:
以下对本发明制备出的新型微孔金属有机骨架材料的合成具体条件做进一步详细说明。本实施例中，金属有机骨架微孔材料采用的合成条件如下：The specific conditions for the synthesis of the novel microporous metal-organic framework material prepared by the present invention will be further described in detail below. In this example, the synthesis conditions used for the metal-organic framework microporous material are as follows:
反应用有机配体为C30N10O10H18(0.07g)；The organic ligand used for the reaction is C30 N10 O10 H18 (0.07g);
金属钇盐为六水合硝酸钇Y(NO)3·6H2O(0.15g)；The metal yttrium salt is yttrium nitrate hexahydrate Y(NO)3 6H2 O (0.15g);
反应溶剂为水(7ml)。The reaction solvent was water (7ml).
具体合成步骤如下：Concrete synthetic steps are as follows:
顺序称量0.07g有机配体C30N10O10H18与0.15g六水合硝酸钇至10ml反应釜中，再加入1.8ml水，搅拌均匀，放入160℃烘箱中反应24小时后以3℃/小时降至室温过滤得到无色块状晶体，产率为90％(以有机配体H6TDPAH计算)。晶胞参数为15.0326，15.0326，13.4206，90，90，120。Sequentially weigh 0.07g of organic ligand C30 N10 O10 H18 and 0.15g of yttrium nitrate hexahydrate into a 10ml reaction kettle, then add 1.8ml of water, stir evenly, and put it in a 160°C oven for 24 hours to react with 3 The temperature/hour was lowered to room temperature and filtered to obtain colorless blocky crystals with a yield of 90% (calculated based on organic ligand H6 TDPAH ). The unit cell parameters are 15.0326, 15.0326, 13.4206, 90, 90, 120.
实施例2：Example 2:
将实施例1的溶液移至玻璃管中，将玻璃管抽真空，然后用酒精喷灯烧结封口，其他条件不变，得到与实施例1中所述相同材料。The solution in Example 1 was moved into a glass tube, the glass tube was evacuated, and then sealed with an alcohol torch. Other conditions remained unchanged, and the same material as described in Example 1 was obtained.
实施例3Example 3
顺序称量0.07g有机配体C30N10O10H18与0.12g六水合硝酸钇至10ml反应釜中，再加入1.4ml水，搅拌均匀，放入180℃烘箱中反应24小时后以3℃/小时降至室温过滤得到实施例1中所述的金属有机骨架材料，产率为80％(以有机配体H6TDPAH计算)。Sequentially weigh 0.07g of organic ligand C30 N10 O10 H18 and 0.12g of yttrium nitrate hexahydrate into a 10ml reaction kettle, then add 1.4ml of water, stir evenly, put it in a 180°C oven for 24 hours, and then use 3 The metal-organic framework material described in Example 1 was obtained by filtering at room temperature at °C/hour, with a yield of 80% (calculated based on the organic ligand H6 TDPAH).
实施例4Example 4
顺序称量0.07g有机配体C30N10O10H18与0.19g六水合硝酸钇至15ml反应釜中，再加入2.2ml水，搅拌均匀，放入140℃烘箱中反应48小时后以3℃/小时降至室温过滤得到实施例1中所述的金属有机骨架材料，产率为65％(以有机配体H6TDPAH计算)。Sequentially weigh 0.07g of organic ligand C30 N10 O10 H18 and 0.19g of yttrium nitrate hexahydrate into a 15ml reaction kettle, then add 2.2ml of water, stir evenly, and put it in a 140°C oven for 48 hours to react with 3 The metal-organic framework material described in Example 1 was obtained by filtering at room temperature at °C/hour, with a yield of 65% (calculated based on the organic ligand H6 TDPAH).
综上所述，本发明利用简单环保的方法，合成了一种以Y(III)为中心，含均草怕津和亚氨基功能基团的微孔金属有机骨架材料，该材料具有较大的比表面积(798m2g-1)，孔道直径为常温常压下具有良好乙炔和甲烷吸附分离能力，可在工业生产中捕获C2H2作为重要的化工原料。In summary, the present invention uses a simple and environmentally friendly method to synthesize a Y(III)-centered microporous metal-organic framework material containing homopyrazine and imino functional groups. The material has a relatively large Specific surface area (798m2 g-1 ), pore diameter is It has good adsorption and separation ability of acetylene and methane under normal temperature and pressure, and can capture C2 H2 in industrial production as an important chemical raw material.
以上内容是结合具体的优选实施方式对本发明所作的进一步详细说明，不能认定本发明的具体实施只局限于这些说明。对于本领域的普通技术人员来说，可以根据本发明的技术方案和发明构思，做出相应改变和替代，而且性能或用途相同，都应当视为本发明的保护范围。The above content is a further detailed description of the present invention in conjunction with specific preferred embodiments, and it cannot be assumed that the specific implementation of the present invention is limited to these descriptions. For those skilled in the art, corresponding changes and substitutions can be made according to the technical scheme and inventive concept of the present invention, and the same performance or use should be regarded as the protection scope of the present invention.
| Application Number | Priority Date | Filing Date | Title |
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| CN201710011593.5ACN106866985B (en) | 2017-01-07 | 2017-01-07 | A kind of metal-organic framework materials and preparation method thereof separated for acetylene and methane adsorption |
| Application Number | Priority Date | Filing Date | Title |
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| CN201710011593.5ACN106866985B (en) | 2017-01-07 | 2017-01-07 | A kind of metal-organic framework materials and preparation method thereof separated for acetylene and methane adsorption |
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| CN106866985Atrue CN106866985A (en) | 2017-06-20 |
| CN106866985B CN106866985B (en) | 2019-11-26 |
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| CN201710011593.5AExpired - Fee RelatedCN106866985B (en) | 2017-01-07 | 2017-01-07 | A kind of metal-organic framework materials and preparation method thereof separated for acetylene and methane adsorption |
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