CN106807330A - The preparation and sorbing material and application of a kind of ordered structure sorbing material - Google Patents
The preparation and sorbing material and application of a kind of ordered structure sorbing material Download PDFInfo
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Abstract
Description
技术领域technical field
本发明涉及规整结构吸附材料设计制备、混合气体吸附分离技术领域，具体而言涉及一类新型吸附分离用的整体式吸附材料及其制备方法。The invention relates to the technical field of design and preparation of regular-structured adsorption materials and the adsorption and separation of mixed gases, in particular to a new type of monolithic adsorption material for adsorption and separation and a preparation method thereof.
背景技术Background technique
变压吸附气体分离技术是上世纪六十年代发展起来的，由美国联合碳化物公司(UCC)首次实现变压吸附四床工艺技术的工业化。该技术是依靠分子筛等吸附材料对特定气体的选择性吸附并随着压力变化实现吸附和脱附再生的。气体的变压吸附过程由于能耗低、可在常温下运行、自动化程度高、流程简单、在诸多领域得到广泛的应用，并随着吸附剂技术的发展近年来发展非常迅速。The pressure swing adsorption gas separation technology was developed in the 1960s, and the United States Union Carbide Corporation (UCC) first realized the industrialization of the pressure swing adsorption four-bed process technology. This technology relies on the selective adsorption of specific gases by adsorption materials such as molecular sieves, and realizes adsorption and desorption regeneration with pressure changes. The pressure swing adsorption process of gas has been widely used in many fields due to its low energy consumption, operation at room temperature, high degree of automation, and simple process, and has developed rapidly in recent years with the development of adsorbent technology.
变压吸附分离技术所用吸附剂的吸附分离性能直接决定了分离效果和装置操作能耗，所以有必要不断改进和研制性能更好的吸附剂。金属-有机骨架材料是由金属离子和有机配体通过配位键作用形成的一类多孔材料。在过去的十几年里，该类材料由于在气体存储、分离和催化等众多领域的潜在应用前景受到人们的广泛关注。The adsorption and separation performance of the adsorbent used in the pressure swing adsorption separation technology directly determines the separation effect and the energy consumption of the device operation, so it is necessary to continuously improve and develop an adsorbent with better performance. Metal-organic frameworks are a class of porous materials formed by coordination bonds between metal ions and organic ligands. In the past ten years, this type of material has attracted widespread attention due to its potential applications in many fields such as gas storage, separation, and catalysis.
目前工业变压吸附装置上使用的吸附剂大多为颗粒状吸附剂，吸附装置内吸附剂通常采用堆积装填方式，受吸附剂吸附容量和吸脱附速率的限制，吸附塔体积通常比较庞大。一般来讲，随吸附剂颗粒直径的减小，其气体吸附和脱附的扩散速率将快速增加，可以大幅提高变压吸附循环速率，从而大大减小吸附塔体积。但在成型吸附剂颗粒直径减小的同时，也将导致床层压降的大幅增加，阻碍易吸附气体的脱附，从而大大增加分离装置操作功耗。因此，采用一种有别于传统颗粒吸附剂的规整结构吸附材料，不仅可以大幅减小吸附剂颗粒尺寸，还可以解决吸附床的压降问题，对提高单位体积吸附剂的吸附效率具有重要意义。国外多家公司已采用蜂窝状分子筛吸附剂床层替代传统的颗粒吸附剂，研制了快速吸附分离氢气、空气等吸附分离工艺。然而，采用分子筛直接挤出整体结构吸附剂的工艺相对复杂，同时金属有机框架材料的后期可加工性能比传统分子筛差一些，导致规整结构挤出工艺很难直接用于金属有机框架材料的挤出。因此，开发适用于快速吸附分离过程的金属有机框架规整结构吸附剂制备技术，在维持金属有机框架材料优异性能的基础上，大幅提高气体在吸附材料上的吸脱附扩散速率，对提高变压装置的整体生产能力具有重要意义。At present, most of the adsorbents used in industrial pressure swing adsorption devices are granular adsorbents. The adsorbents in the adsorption device are usually packed in a stacked manner. Due to the limitation of the adsorption capacity and the adsorption and desorption rate of the adsorbent, the volume of the adsorption tower is usually relatively large. Generally speaking, as the diameter of adsorbent particles decreases, the diffusion rate of gas adsorption and desorption will increase rapidly, which can greatly increase the cycle rate of pressure swing adsorption, thereby greatly reducing the volume of the adsorption tower. However, when the particle diameter of the shaped adsorbent decreases, it will also lead to a substantial increase in the pressure drop of the bed layer, hindering the desorption of easily adsorbed gases, thereby greatly increasing the operating power consumption of the separation device. Therefore, the use of a structured adsorption material that is different from traditional granular adsorbents can not only greatly reduce the particle size of the adsorbent, but also solve the problem of pressure drop in the adsorption bed, which is of great significance for improving the adsorption efficiency of the adsorbent per unit volume. . Many foreign companies have used honeycomb molecular sieve adsorbent beds to replace traditional granular adsorbents, and have developed adsorption separation processes such as rapid adsorption and separation of hydrogen and air. However, the process of directly extruding monolithic adsorbents using molecular sieves is relatively complicated, and the post-processability of metal-organic framework materials is worse than that of traditional molecular sieves, making it difficult to directly apply the regular structure extrusion process to the extrusion of metal-organic framework materials. . Therefore, the development of metal-organic framework structured adsorbent preparation technology suitable for rapid adsorption and separation process can greatly improve the adsorption and desorption diffusion rate of gas on the adsorbent material on the basis of maintaining the excellent performance of metal-organic framework materials, which is very important for improving the pressure swing. The overall production capacity of the device is of great significance.
发明内容Contents of the invention
本发明的目的是针对当前变压吸附装置吸附床体积庞大、吸附剂装填量多、投资高、生产效率低、以及整体结构吸附剂成型复杂等系列问题，提出了一种能够用于快速吸附分离过程的规整结构吸附剂的制备方法，该方法所涉及的吸附材料制备工艺简单可靠，效率高，所制备的规整结构吸附剂能够用于循环周期较短的快速变压吸附分离过程，大幅提高单位体积装置的处理能力，特别适用于大气量气体混合物的分离净化与浓缩提纯等净化过程。The purpose of the present invention is to solve a series of problems such as the large volume of the adsorption bed of the current pressure swing adsorption device, the large amount of adsorbent loading, the high investment, the low production efficiency, and the complicated molding of the overall structure adsorbent, and propose a method that can be used for rapid adsorption and separation. The preparation method of the regular structure adsorbent in the process, the preparation process of the adsorption material involved in the method is simple and reliable, and the efficiency is high, and the prepared regular structure adsorbent can be used in the rapid pressure swing adsorption separation process with a short cycle period, greatly improving the unit The processing capacity of the volume device is especially suitable for purification processes such as separation, purification and concentration purification of large gas mixtures.
本发明提供了一类规整结构吸附材料的制备方法，该类吸附材料由金属有机框架材料、粘结剂和支撑基体构成。其制备方法的基本原理是将大吸附容量的金属-有机骨架材料粉体通过采用粘结剂直接涂覆在支撑基体上，通过喷涂、刷涂或浸渍等方式将基体与吸附材料粉体制成外扩散距离短的规整结构吸附材料。The invention provides a preparation method of a regular structure adsorption material, which is composed of a metal organic framework material, a binder and a support matrix. The basic principle of its preparation method is that the metal-organic framework material powder with large adsorption capacity is directly coated on the support substrate by using a binder, and the substrate and the adsorption material powder are made by spraying, brushing or dipping. Regular structure adsorption material with short out-diffusion distance.
本发明所采用的支撑基体为纤维布状，根据吸附材料所应用领域的不同和所担载的金属有机框架吸附材料的不同。本发明所采用的支撑基体主要为二氧化硅纤维布、氧化锆纤维布、氧化铝纤维布、聚酯纤维布、丙纶纤维布、芳纶纤维布、涤纶纤维布、维纶纤维布、氨纶纤维布、棉布和炭纤维布中的一种。所采用的基体材料应不溶于浆料制备时所选用的溶剂。The supporting matrix used in the present invention is in the form of fiber cloth, depending on the application field of the adsorbent material and the difference of the loaded metal organic framework adsorbent material. The supporting matrix used in the present invention is mainly silica fiber cloth, zirconia fiber cloth, alumina fiber cloth, polyester fiber cloth, polypropylene fiber cloth, aramid fiber cloth, polyester fiber cloth, vinylon fiber cloth, spandex fiber cloth , cotton cloth and carbon fiber cloth. The matrix material used should be insoluble in the solvent selected for slurry preparation.
本发明所涉及的一类规整结构吸附材料的制备方法，制备中所使用的多孔状粉末吸附材料为金属有机框架吸附材料。该类吸附材料为不溶于浆料制备所使用的溶剂的粉末状多孔材料，其N2比表面积大于100m2/g，颗粒尺寸介于10nm-100μm。本发明优先使用的材料比表面积介于200-2000m2/g，其粉体颗粒尺寸优先使用0.2-30μm的颗粒材料。本发明所使用的金属有机框架吸附材料可以选用不同金属离子、不同结构的一种或多种材料的混合物，相关的工程技术人员可以根据应用领域的需求在上述范围内进行适当调整。The preparation method of a kind of regular structure adsorption material involved in the present invention, the porous powder adsorption material used in the preparation is metal organic framework adsorption material. This kind of adsorption material is a powdery porous material insoluble in the solvent used for slurry preparation, its N 2 specific surface area is greater than 100m 2 /g, and its particle size is between 10nm and 100μm. The specific surface area of the material preferably used in the present invention is between 200-2000m 2 /g, and the particle size of the powder is preferably 0.2-30μm. The metal-organic framework adsorption material used in the present invention can be a mixture of one or more materials with different metal ions and different structures, and relevant engineers and technicians can make appropriate adjustments within the above range according to the requirements of the application field.
本发明所涉及的一类规整结构吸附材料及其制备方法，所述金属有机框架材料是由金属离子、有机配体在溶剂中配位络合构成的多孔结构材料。金属-有机框架结构材料的构成部分包括：金属离子或金属簇合物节点、有机连接配体以及辅助共配体和溶剂分子。由于金属有机框架的拓扑结构主要由节点的配位数和几何构型来决定，尽管MOFs材料的种类非常多，但大多MOFs材料的合成条件比较苛刻，同时受其结构的性质限制，有很多MOFs材料很难实现大规模合成应用，所以本发明中优先推荐的、最具工业价值的多孔金属有机框架材料。优先选用的有机配体为甲酸、乙酸、吡啶、丁二酸、酒石酸、顺丁烯二酸、富马酸、异烟酸、对苯二甲酸、2,5-二羟基对苯二甲酸、1,3-苯二甲酸、4,4’-联吡啶、2-甲基咪唑、2-硝基咪唑、咪唑中的一种或多种；金属离子选自铝、铁、镁、钴、镍、铜、锌、锆、镧中的一种或多种。所采用的金属有机框架材料为多孔吸附材料，N2比表面积介于20-2000m2/g，平均孔径介于0.4-2nm之间，优先推荐使用平均孔径介于0.4-0.8nm的材料。The present invention relates to a class of regular structure adsorption materials and a preparation method thereof. The metal organic framework material is a porous structure material composed of metal ions and organic ligands coordinated and complexed in a solvent. The building blocks of metal-organic framework materials include: metal ions or metal cluster nodes, organic linking ligands, and auxiliary co-ligands and solvent molecules. Since the topological structure of metal-organic frameworks is mainly determined by the coordination number and geometric configuration of the nodes, although there are many types of MOFs materials, the synthesis conditions of most MOFs materials are relatively harsh. At the same time, limited by the properties of their structures, there are many MOFs Materials are difficult to achieve large-scale synthetic applications, so the porous metal-organic framework materials with the most industrial value are recommended in the present invention. Preferred organic ligands are formic acid, acetic acid, pyridine, succinic acid, tartaric acid, maleic acid, fumaric acid, isonicotinic acid, terephthalic acid, 2,5-dihydroxyterephthalic acid, 1 , one or more of 3-phthalic acid, 4,4'-bipyridine, 2-methylimidazole, 2-nitroimidazole, imidazole; the metal ion is selected from aluminum, iron, magnesium, cobalt, nickel, One or more of copper, zinc, zirconium, and lanthanum. The metal organic framework material used is a porous adsorption material, the specific surface area of N 2 is between 20-2000m 2 /g, and the average pore diameter is between 0.4-2nm, and the material with an average pore diameter between 0.4-0.8nm is preferably recommended.
本发明提供了一类规整结构吸附材料的制备方法，其制备方法包括如下步骤：The invention provides a preparation method of a kind of regular structure adsorption material, and its preparation method comprises the following steps:
(1)将金属有机框架材料粉体在搅拌条件下加入到溶剂中，搅拌0.5-5小时形成混合浆料；(1) adding the metal-organic framework material powder into the solvent under stirring conditions, and stirring for 0.5-5 hours to form a mixed slurry;
(2)在混合浆料中加入粘结剂，搅拌均匀形成涂层用浆料；(2) Add binder in the mixed slurry, stir evenly to form coating slurry;
(3)将涂层用浆料通过喷涂、刷涂或浸渍方法在纤维布一侧或二侧表面形成涂层；(3) forming a coating on one side or two sides of the fiber cloth by spraying, brushing or dipping the coating slurry;
(4)纤维布卷制成柱状，经过干燥与活化制备规整结构吸附材料。(4) The fiber cloth is rolled into a columnar shape, and then dried and activated to prepare an adsorbent material with a regular structure.
本发明所涉及的规整结构吸附材料的制备方法，制备涂层用浆料时需使用大量溶剂分散吸附材料粉体，制备浆料时所用溶剂为水、甲醇、乙醇和其他低沸点有机溶剂中的一种或多种的混合物。本发明中优先推荐使用水作为分散溶剂，水价格低廉，易于操作，环保。对于一些在水溶剂中容易造成吸附材料孔结构破坏或可能吸附分离性能下降的吸附剂材料，则可能需要采用部分有机溶剂，上述有机溶剂可以为甲醇、乙醇和其他低沸点有机溶剂中的一种或多种的混合物，优先推荐使用无毒、价廉的乙醇作为有机溶剂。The preparation method of the regular structure adsorption material involved in the present invention needs to use a large amount of solvents to disperse the adsorption material powder when preparing the coating slurry, and the solvent used in the preparation of the slurry is water, methanol, ethanol and other organic solvents with low boiling points. A mixture of one or more. In the present invention, it is preferred to use water as the dispersion solvent, which is cheap, easy to operate, and environmentally friendly. For some adsorbent materials that are likely to cause damage to the pore structure of the adsorbent material or may reduce the adsorption and separation performance in water solvents, it may be necessary to use some organic solvents. The above-mentioned organic solvents can be one of methanol, ethanol and other low-boiling point organic solvents. or a mixture of several, it is preferred to use non-toxic and cheap ethanol as the organic solvent.
本发明所涉及的一类规整结构吸附材料的制备方法，制备涂层用浆料时需使用粘结剂，用于增强基体和吸附材料粉体相互之间的结合能力，粘结剂为可以分散于溶剂的无机粘结剂或者有机粘合剂。所述无机粘结剂可以为硅溶胶、铝溶胶、锆溶胶和钛溶胶中的一种或其混合溶胶粘结剂；本发明所述的有机粘结剂为可在水或有机溶剂中分散的环氧树脂、酚醛树脂、丙烯酸树脂、聚氨酯、聚碳酸酯、聚乙烯醇、聚乙二醇中的一种或二种以上的混合物。The preparation method of a class of regular structure adsorption materials involved in the present invention requires the use of a binder when preparing the coating slurry to enhance the bonding ability between the matrix and the adsorption material powder. The binder is dispersible Inorganic or organic binders in solvents. The inorganic binder can be one of silica sol, aluminum sol, zirconium sol and titanium sol or its mixed sol binder; the organic binder of the present invention is dispersible in water or organic solvent One or a mixture of two or more of epoxy resin, phenolic resin, acrylic resin, polyurethane, polycarbonate, polyvinyl alcohol, polyethylene glycol.
本发明所涉及的一类规整结构吸附材料的制备方法，制备涂层用浆料必须通过采用适当的机械手段在基体表面形成一定厚度的涂层，所述浆料涂覆用方法为机械喷涂、刷涂或浸渍等多种方法中的一种，技术人员可以根据需要调整涂层浆料浓度和涂覆时间和涂覆次数来调整涂层厚度。In the preparation method of a class of regular structure adsorption materials involved in the present invention, a coating with a certain thickness must be formed on the surface of the substrate by adopting appropriate mechanical means to prepare the coating slurry, and the coating method of the slurry is mechanical spraying, One of many methods such as brushing or dipping, technicians can adjust the coating thickness by adjusting the coating slurry concentration and coating time and number of coatings according to needs.
本发明所涉及的一类规整结构吸附材料的制备方法，所述浆料涂覆时，涂层厚度一般可控制在50～300微米，本发明推荐的较佳涂层厚度为100～200微米，该涂层厚度既能保证较大的吸附容量，又能保证较快的吸附和脱附速率。The preparation method of a class of regular structure adsorption materials involved in the present invention, when the slurry is coated, the coating thickness can generally be controlled at 50-300 microns, and the preferred coating thickness recommended by the present invention is 100-200 microns. The coating thickness can not only ensure a large adsorption capacity, but also ensure a faster adsorption and desorption rate.
本发明所涉及的一类规整结构吸附材料的制备方法，所述涂覆浆料中金属有机框架材料、粘结剂和溶剂组分的重量比例为：金属有机框架材料粉体20-50％，粘结剂5-30％，溶剂40-75％。上述三种材料中金属有机框架材料粉体决定着规整结构吸附材料的吸附容量，粘结剂用量控制着吸附粉体材料和规整结构吸附材料基体的结合牢固程度，溶剂用量决定了涂层浆料的粘度和单次涂覆的涂层厚度。需要注意的是浆料中的粘结剂组分本身不具有吸附和分离性能，其用量可能会导致最终规整结构吸附材料吸附容量的降低，因此本发明中推荐在规整结构牢固度许可的条件下，尽可能减少粘结剂的使用量。在实际的整体吸附材料制备过程中相关工程技术人员可以根据实际需要在上述用量范围内，调整各组分的使用量。The preparation method of a class of regular structure adsorption materials involved in the present invention, the weight ratio of metal organic framework material, binder and solvent components in the coating slurry is: metal organic framework material powder 20-50%, Binder 5-30%, solvent 40-75%. Among the above three materials, the metal-organic framework material powder determines the adsorption capacity of the structured adsorption material, the amount of binder controls the bonding firmness of the adsorption powder material and the structured adsorption material matrix, and the amount of solvent determines the coating slurry. Viscosity and coating thickness in a single application. It should be noted that the binder component in the slurry itself does not have adsorption and separation properties, and its dosage may lead to a reduction in the adsorption capacity of the final structured adsorption material. Therefore, it is recommended in the present invention that the regular structure firmness permits , reduce the amount of binder used as much as possible. In the actual preparation process of the overall adsorption material, relevant engineering and technical personnel can adjust the usage amount of each component within the above dosage range according to actual needs.
本发明所涉及的一类规整结构吸附材料及其制备方法，其特征在于所述吸附材料中金属有机框架材料粉体、粘结剂和基体组分的重量比例为：金属有机框架材料粉体30-92％，粘结剂5-30％，基体3-40％。The present invention relates to a class of regular structure adsorption material and its preparation method, which is characterized in that the weight ratio of metal organic framework material powder, binder and matrix component in the adsorption material is: metal organic framework material powder 30 -92%, binder 5-30%, matrix 3-40%.
本发明所涉及的一类规整结构吸附材料及其制备方法，涂覆后基体材料在室温下适当晾干后即可卷制成型，本发明推荐室温条件下干燥0.1-4小时，优选0.5-2小时。The present invention relates to a class of regular structure adsorption material and its preparation method. After coating, the base material can be rolled and molded after being properly dried at room temperature. The present invention recommends drying at room temperature for 0.1-4 hours, preferably 0.5- 2 hours.
本发明所涉及的一类规整结构吸附材料及其制备方法，其特征在于所述吸附材料具有丰富的孔结构，均匀的孔径分布，较快的吸附和脱附速率；Langmuir法N2比表面积大于100m2/g，孔径分布介于0.4-2nm之间，特别适用于大气量气体混合物的分离净化与浓缩提纯等净化过程，可优先用于快速变压或变温的气体吸附分离过程。The present invention relates to a class of regular structure adsorption material and preparation method thereof, it is characterized in that described adsorption material has rich pore structure, uniform pore size distribution, faster adsorption and desorption rate; Langmuir method N The specific surface area is greater than 100m 2 /g, pore size distribution between 0.4-2nm, especially suitable for purification processes such as separation, purification and concentration purification of large gas mixtures, and can be preferentially used in gas adsorption separation processes with rapid pressure change or temperature change.
本发明所述规整结构吸附材料与现有吸附技术使用的吸附材料相比具有如下的显著优势：Compared with the adsorption materials used in the existing adsorption technology, the regular structure adsorption material of the present invention has the following significant advantages:
(1)吸附材料制备工艺简单方便，重复性容易控制，制备成本低。(1) The preparation process of the adsorption material is simple and convenient, the repeatability is easy to control, and the preparation cost is low.
(2)吸附材料适应范围广，可根据应用需要成型各种形状的整体结构吸附材料组件，材料易于装填。(2) The adsorption material has a wide range of applications, and various shapes of integral structure adsorption material components can be formed according to application requirements, and the material is easy to load.
(3)本发明所制备的规整结构吸附剂组件床层阻力低，生产效率高，降低吸附操作了生产成本，节省功耗。(3) The regular structure adsorbent module prepared by the present invention has low bed resistance and high production efficiency, reduces the production cost of adsorption operation, and saves power consumption.
(4)本发明所制备的规整结构吸附剂材料，适用于大气量快速吸附分离和提纯过程，适合于每分钟可以完成多次循环周期的吸附分离过程，尤其适用于切换频率高达每分钟数次规模以上的变压吸附过程，在诸多领域具有广阔的应用前景。(4) The regular structure adsorbent material prepared by the present invention is suitable for rapid adsorption separation and purification process of air volume, suitable for the adsorption separation process that can complete multiple cycles per minute, especially suitable for switching frequency up to several times per minute The pressure swing adsorption process above the scale has broad application prospects in many fields.
该规整结构吸附材料制备工艺简单，重复性好，吸附材料具有丰富的多孔结构，用于气体吸附分离时吸附、脱附速率快，特别适用于大气量气体混合物的分离净化与浓缩提纯等净化过程。The regular structure adsorption material has a simple preparation process and good repeatability. The adsorption material has a rich porous structure, and the adsorption and desorption rate is fast when used for gas adsorption and separation. .
具体实施方式detailed description
下面结合实施例对本发明给予进一步说明，但并不因此而限制本发明。Below in conjunction with embodiment the present invention is given further description, but does not limit the present invention thereby.
实施例1：Example 1:
金属有机框架吸附材料ZIF-8：BET比表面积1350m2/g，粒径2-5μm，平均孔径0.9nm。Metal organic framework adsorption material ZIF-8: BET specific surface area 1350m 2 /g, particle size 2-5μm, average pore size 0.9nm.
量取200ml水做溶剂，称取100g金属有机框架吸附材料粉体，将粉体在搅拌条件下分批加入到溶剂中，搅拌2小时形成混合浆料。在混合浆料中加入30g聚氨酯胶黏剂，高速搅拌3小时形成均匀的涂覆用浆料。浆料中各组分重量比例为：吸附材料粉体30.3％，溶剂60.6％，胶粘剂9.1％。选用二氧化硅纤维布作基体，采用机械喷涂方式将浆料均匀涂覆在基体表面，涂层厚度140μm。将涂覆好的基体在室温下自然干燥，时间2小时，然后卷制成圆柱状整体规整结构吸附材料。Measure 200ml of water as a solvent, weigh 100g of metal-organic framework adsorption material powder, add the powder into the solvent in batches while stirring, and stir for 2 hours to form a mixed slurry. Add 30 g of polyurethane adhesive to the mixed slurry, and stir at high speed for 3 hours to form a uniform slurry for coating. The weight ratio of each component in the slurry is: 30.3% of the adsorption material powder, 60.6% of the solvent, and 9.1% of the adhesive. The silica fiber cloth is selected as the substrate, and the slurry is uniformly coated on the surface of the substrate by mechanical spraying, and the coating thickness is 140 μm. The coated substrate was naturally dried at room temperature for 2 hours, and then rolled into a cylindrical overall regular structure adsorption material.
实施例2：Example 2:
金属有机框架吸附材料CuBTC：BET比表面积1550m2/g，平均粒径5μm，平均孔径0.75nm。Metal organic framework adsorption material CuBTC: BET specific surface area 1550m 2 /g, average particle diameter 5μm, average pore diameter 0.75nm.
量取200ml水与200mL乙醇做溶剂，称取100g金属有机框架吸附材料粉体，将粉体在搅拌条件下分批加入到溶剂中，搅拌1小时形成混合浆料。在混合浆料中加入：70g硅溶胶，高速搅拌1小时形成均匀的涂覆用浆料。浆料中各组分重量比例为：吸附材料粉体23.8％，溶剂59.5％，胶粘剂16.7％。选用二氧化硅纤维布作基体，采用刷涂方式将浆料均匀涂覆在基体表面，涂层厚度130μm。将涂覆好的基体在室温下自然干燥，时间0.5小时，然后卷制成圆柱状整体规整结构吸附材料。Measure 200ml of water and 200mL of ethanol as a solvent, weigh 100g of metal-organic framework adsorption material powder, add the powder to the solvent in batches under stirring, and stir for 1 hour to form a mixed slurry. Add: 70g of silica sol to the mixed slurry, stir at high speed for 1 hour to form a uniform slurry for coating. The weight ratio of each component in the slurry is: 23.8% of the adsorption material powder, 59.5% of the solvent, and 16.7% of the adhesive. The silica fiber cloth is selected as the substrate, and the slurry is evenly coated on the surface of the substrate by brushing, with a coating thickness of 130 μm. The coated substrate was naturally dried at room temperature for 0.5 hours, and then rolled into a cylindrical overall regular structure adsorption material.
实施例3：Example 3:
金属有机框架吸附材料Al-BDC：BET比表面积1250m2/g，粒径2-5μm，平均孔径0.75nm。Metal organic framework adsorption material Al-BDC: BET specific surface area 1250m 2 /g, particle size 2-5μm, average pore size 0.75nm.
量取200ml乙醇做溶剂，称取100g金属有机框架吸附材料粉体，将粉体在搅拌条件下分批加入到溶剂中，搅拌0.5小时形成混合浆料。在混合浆料中加入：50g环氧树脂胶黏剂，高速搅拌2小时形成均匀的涂覆用浆料。浆料中各组分重量比例为：吸附材料粉体28.6％，溶剂57.1％，胶粘剂14.3％。选用氧化锆纤维布作基体，采用机械喷涂方式将浆料均匀涂覆在基体表面，涂层厚度150μm。将涂覆好的基体在室温下自然干燥，时间0.5小时，然后卷制成圆柱状整体规整结构吸附材料。Measure 200ml of ethanol as a solvent, weigh 100g of MOF adsorption material powder, add the powder into the solvent in batches under stirring, and stir for 0.5 hours to form a mixed slurry. Add: 50g of epoxy resin adhesive to the mixed slurry, stir at high speed for 2 hours to form a uniform slurry for coating. The weight ratio of each component in the slurry is: 28.6% of the adsorption material powder, 57.1% of the solvent, and 14.3% of the adhesive. Zirconia fiber cloth is selected as the substrate, and the slurry is evenly coated on the surface of the substrate by mechanical spraying, with a coating thickness of 150 μm. The coated substrate was naturally dried at room temperature for 0.5 hours, and then rolled into a cylindrical overall regular structure adsorption material.
以上实施例仅用于对本发明的发明内容作进一步的详细描述，但不应将此理解为本发明上述主题的范围仅限于上述实施例。在不脱离本发明上述技术思想情况下，根据本领域普通的技术知识和常用手段，做出的各种替换和变更，均应包括在本发明应保护的范围内。The above embodiments are only used to further describe the content of the present invention in detail, but it should not be understood that the scope of the above subject matter of the present invention is limited to the above embodiments. Without departing from the above-mentioned technical idea of the present invention, various replacements and changes made according to ordinary technical knowledge and common means in this field shall be included in the protection scope of the present invention.
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| CN106048778A (en) * | 2016-06-28 | 2016-10-26 | 武汉纺织大学 | Porous adsorptive fibers and preparation method thereof |
| CN107759801A (en) * | 2017-09-27 | 2018-03-06 | 华南理工大学 | The method of the materials of micro-diplopore MOF 74 in being synthesized using crystal defect method |
| CN107970884A (en) * | 2017-12-08 | 2018-05-01 | 苏州思美特表面材料科技有限公司 | The preparation method of the low si molecular sieves load filler of lithium type |
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| CN116622074A (en) * | 2023-07-25 | 2023-08-22 | 齐河力厚化工有限公司 | Modified MOFs and preparation method and application thereof |
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| CN108499534A (en) * | 2018-03-30 | 2018-09-07 | 南宁学院 | A kind of graphene-containing metal organic framework dense gas separation hybrid material and preparation method |
| CN108499534B (en) * | 2018-03-30 | 2021-03-16 | 南宁学院 | A kind of graphene-containing metal organic framework dense gas separation hybrid material and preparation method |
| CN110075782A (en) * | 2019-04-19 | 2019-08-02 | 中国科学院大学 | A kind of novel arsenic adsorbent material and preparation method thereof |
| CN110075782B (en) * | 2019-04-19 | 2022-04-08 | 中国科学院大学 | A new type of arsenic adsorption material and preparation method thereof |
| CN110559999B (en) * | 2019-08-21 | 2022-09-27 | 中山大学 | Preparation method of structured adsorbent based on metal organic framework material |
| CN110559999A (en) * | 2019-08-21 | 2019-12-13 | 中山大学 | preparation method of structured adsorbent based on metal organic framework material |
| CN110982087A (en) * | 2019-12-18 | 2020-04-10 | 中国农业科学院农业质量标准与检测技术研究所 | Metal-organic framework material and preparation method and application thereof |
| CN110982087B (en) * | 2019-12-18 | 2022-05-24 | 中国农业科学院农业质量标准与检测技术研究所 | Metal-organic framework material and preparation method and application thereof |
| CN113117647B (en) * | 2019-12-31 | 2023-07-28 | 中国石油化工股份有限公司 | Foam metal supporting adsorption material and preparation method thereof |
| CN113117647A (en) * | 2019-12-31 | 2021-07-16 | 中国石油化工股份有限公司 | Foam metal supporting adsorption material and preparation method thereof |
| JP7611928B2 (en) | 2020-03-04 | 2025-01-10 | エクソンモービル テクノロジー アンド エンジニアリング カンパニー | Method for producing metal-organic framework composites |
| CN115209986A (en) * | 2020-03-04 | 2022-10-18 | 埃克森美孚技术与工程公司 | Method for preparing metal-organic framework composite material |
| CN112755955A (en) * | 2020-12-24 | 2021-05-07 | 赣南师范大学 | Preparation method of light honeycomb molecular sieve purification module |
| CN113521880A (en) * | 2021-06-30 | 2021-10-22 | 武汉理工大学 | Photothermal regeneration mask core layer material and preparation method thereof |
| CN113521880B (en) * | 2021-06-30 | 2024-07-02 | 武汉理工大学 | Photothermal regeneration mask core layer material and preparation method thereof |
| CN114659701A (en) * | 2022-03-04 | 2022-06-24 | 武汉理工大学 | High-sensitivity gas pressure sensor for rapidly desorbing gas and preparation method thereof |
| CN114659701B (en) * | 2022-03-04 | 2023-09-26 | 武汉理工大学 | Highly sensitive air pressure sensor for rapid desorption of gas and preparation method thereof |
| CN115193396B (en) * | 2022-05-12 | 2023-06-09 | 北京科技大学 | A kind of monolithic adsorbent and preparation method thereof |
| CN115193396A (en) * | 2022-05-12 | 2022-10-18 | 北京科技大学 | Integral adsorbent and preparation method thereof |
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