Metal organic framework forming material as well as preparation method and application thereof

Abstract

The invention provides a metal organic framework forming material as well as a preparation method and application thereof. The preparation raw materials of the metal organic framework forming material comprise a base material and MOFs slurry loaded on the base material, the MOFs slurry contains an MOFs material and a composite binder, the composite binder comprises an inorganic binder and an organic binder, and the inorganic binder is dispersed in the organic binder. According to the metal organic framework forming material, the structure of MOFs can be well reserved, the performance of the formed material is not attenuated, the original performance of the MOFs material can be reserved to the maximum extent, and efficient utilization of the MOFs material is achieved; meanwhile, the defects of a traditional powder MOFs material can be avoided, and the application range of the MOFs material is widened. The invention further provides a preparation method and application of the metal organic framework forming material.

Description

Technical Field

[0001] The present invention belongs to the technical field of functional materials, and in particular relates to a metal organic framework molding material and a preparation method and application thereof. Background Art

[0002] Metal-organic frameworks (MOFs) materials refer to porous materials with topological structures formed by self-assembly of metal ions and organic ligands. As a new type of functional material, compared with traditional coordination polymers, it has the advantages of large specific surface area, variable structural composition, high porosity and large pore volume. Depending on the ligands and the bonding mode of metal ions, MOFs materials with various pore shapes and pore sizes can be prepared, and specific specific surface areas and porosities can be obtained. They have shown good application prospects in the fields of heterogeneous catalysis, molecular and ion exchange, gas adsorption and separation, drug delivery, proton conduction, optoelectronics and electromagnetics.

[0003] Although MOFs materials have rich application prospects, MOFs materials obtained by traditional synthesis methods are usually in powder form. In actual application, powders are prone to dust pollution and difficult to recycle, which limits their industrial application and makes it difficult to achieve large-scale industrial production and application. Therefore, for practical applications, especially industrial purposes, MOFs materials need to be structured into molding materials. In recent years, MOFs molding materials for application purposes have attracted great attention. At present, there are mainly two ways to structure MOFs materials: 1) in-situ synthesis (direct molding): that is, directly making the required shape during the formation of MOFs powder, such as hollow spheres, thin films, etc.; 2) indirect molding: the synthesized MOFs materials are reprocessed, such as through granulation, briquetting, sintering, etc., to prepare them into the required shape and size. Among them, indirect molding can be processed into various shapes as needed, so more related research focuses on the latter structuring method. However, the traditional indirect molding process mainly involves adding organic binders to MOFs materials, adjusting the ratio of organic binders to MOFs materials to control the structure and performance of MOFs molding materials, and then extruding them into a specific shape through a certain mold. After drying, they are calcined at high temperature to make the binder and MOFs materials tightly connected. When pure organic binders are used for molding, the organic binders are very easy to form films during the molding and drying process, wrapping on the surface of MOFs grains, blocking the MOFs pores, causing the performance of the MOFs material itself to not be fully utilized, and reducing the efficiency of the material.

[0004] Therefore, a new metal-organic framework forming material still needs to be developed. Summary of the invention

[0005] The present invention aims to solve at least one of the above technical problems existing in the prior art. To this end, the present invention provides a metal organic framework forming material, which will not form a whole film during the drying process and is not easy to block the pores of MOFs.

[0006] The invention also provides a method for preparing the metal organic framework molding material.

[0007] The invention also provides a use of the metal organic framework molding material.

[0008] The invention also provides a water collecting device.

[0009] The invention also provides a gas storage device.

[0010] The invention also provides an air purification device.

[0011] The invention also provides a household appliance.

[0012] The first aspect of the present invention provides a metal organic framework molding material, the preparation raw materials of the metal organic framework molding material include a substrate and a MOFs slurry loaded on the substrate, the MOFs slurry contains MOFs material and a composite binder, the composite binder includes an inorganic binder and an organic binder, and the inorganic binder is dispersed in the organic binder.

[0013] One of the technical solutions of the present invention regarding the metal organic framework molding material has at least the following beneficial effects:

[0014] In the metal organic framework molding material of the present invention, the inorganic binder is dispersed in the organic binder to prevent the organic binder from forming a whole film during the molding process, which can prevent the pore structure of the MOFs material itself from being blocked and avoid affecting the performance of the MOFs material. At the same time, it can achieve firm bonding and improve its use efficiency.

[0015] The metal organic framework molding material of the present invention can prevent the composite binder from forming a dense film structure during the drying process, and can effectively expose the active ingredients while playing a bonding role.

[0016] The metal organic framework molding material of the present invention contains an inorganic binder in the composite binder, so that the molding material has better compressive strength. In the related art, a briquetting process is required to improve the compressive strength. Although the material can have a greater crushing strength by increasing the extrusion pressure, it will cause the MOFs powders to be densely packed, the particles to agglomerate severely, and the pores between the MOFs single crystal particles are small, resulting in only the surface material working during use and a low utilization rate of the internal material.

[0017] The metal organic framework molding material of the present invention can better retain the structure of MOFs itself, and the performance of the material is not attenuated after molding. The original performance of the MOFs material can be retained to the maximum extent, and the efficient utilization of the MOFs material can be achieved; at the same time, the defects of traditional powder MOFs materials can be avoided, and the application range of MOFs materials can be broadened.

[0018] The metal organic framework molding material of the present invention, MOFs is loaded by a composite binder, has high loading efficiency, and has good application prospects in multiple fields such as adsorption, separation, and storage.

[0019] According to some embodiments of the present invention, the organic binder includes a binder with a molecular chain structure, and the inorganic binder is dispersed in the molecular chain structure of the organic binder.

[0020] According to some embodiments of the present invention, the particle size D50 of the raw material is 0.5 μm to 3 μm. Controlling the particle size of the raw material is beneficial to one-step molding and increasing the coating amount.

[0021] If the particle size is too small, the specific surface area of ​​the particle size will increase. When preparing the slurry, it is easy to absorb water and expand, resulting in low solid content of the slurry and reduced coating amount. In addition, if the particle size is too small, if the diameter of the substrate used is small, it is easy to cause agglomeration during the coating and drying process, and the material is easy to fall off after agglomeration. If the particle size is too large, the amount of binder will increase, otherwise it will not be easy to adhere. In addition, in the large particle size slurry, more slurry will agglomerate, and the utilization rate of the agglomerated slurry will be lower.

[0022] According to some embodiments of the present invention, in the MOFs slurry, the mass ratio of the composite binder to the MOFs material is 1 to 10: 100. By adding less binder, a molding material with good mechanical properties can be obtained, and the obtained molding material has high specific area and pore volume retention rate and low production cost.

[0023] According to some embodiments of the present invention, in the MOFs slurry, the mass percentage of MOFs material is 5% to 50%.

[0024] According to some embodiments of the present invention, the organic binder includes at least one of acrylic resin, polyurethane, epoxy resin, polyol, silicone, sodium hydroxymethyl cellulose, glycerol and starch.

[0025] According to some embodiments of the present invention, the inorganic binder includes at least one of silica sol, aluminum sol, aluminum phosphate sol, titanium dioxide sol, clay and kaolin.

[0026] According to some embodiments of the present invention, the aluminum phosphate-based sol includes at least one of aluminum phosphate sol and aluminum dihydrogen phosphate sol.

[0027] According to some embodiments of the present invention, the inorganic binder is a nanoscale inorganic binder, that is, the size of the inorganic binder in three-dimensional space is at least one dimension in the nanometer size of 1-100 nm.

[0028] According to some embodiments of the present invention, the particle size of the inorganic binder is below 50 nm.

[0029] According to some embodiments of the present invention, the particle size of the inorganic binder is below 5 nm.

[0030] According to some embodiments of the present invention, the inorganic binder accounts for 1% to 40% by weight of the organic binder.

[0031] When the proportion of inorganic binder is too low, the amount of organic binder will be too much, the film-forming property will be stronger, and the effective ingredients of the material will be partially covered, thus affecting the performance of the product; when the proportion of inorganic binder is too high, the amount of inorganic binder will be too much, the inorganic component will be too much, the adhesion ability will be reduced, and it will cause problems such as powdering and falling off.

[0032] According to some embodiments of the present invention, the substrate is a porous substrate such as a corrugated substrate or a honeycomb substrate.

[0033] MOFs materials are formed on porous substrates and have many advantages, such as large specific surface area, low wind resistance, high material utilization, and continuous recycling.

[0034] In the related art, the substrate is first impregnated and then the substrate and MOFs slurry are wound together to form a rotating wheel. However, when the substrate impregnated with MOFs undergoes the winding process, the MOFs powder material is easily detached, thereby reducing the overall performance of the product. The present invention directly solidifies the substrate first to avoid the adverse effects of the substrate processing on the MOFs material. The corrugated paper with a certain flute height and flute width is pressed into a mold, and the corrugated paper and the flat paper are combined and formed by impregnating an inorganic or organic binder. After the sample is formed, it is calcined to obtain a finished corrugated substrate.

[0035] According to some embodiments of the present invention, the thickness of the substrate is above 5 mm.

[0036] If the substrate is too thin, its ability to withstand force during coating and other processes will be limited, and it will be prone to breakage.

[0037] According to some embodiments of the present invention, the thickness of the substrate is between 5 mm and 500 mm.

[0038] According to some embodiments of the present invention, the corrugated substrate has a flute height of 0.5 to 5 mm and a flute width of 1 to 5 mm.

[0039] According to some embodiments of the present invention, the honeycomb holes in the honeycomb substrate are hexagonal, the side length of the hexagon is 0.5 to 10 mm, and the hole wall thickness of the honeycomb hole is 0.1 to 5 mm. The substrate is directly solidified and formed by a die extrusion process, thereby avoiding the problem in the related art that adjacent honeycomb structures are easily misaligned and deformed during use due to no solidification treatment, which affects the service life of the product.

[0040] The parameters of the substrate can be selected according to the application requirements of the molding material. For example, if it is required to be applied in the field of air purification, a porous substrate structure parameter with smaller wind resistance and effective macroscopic specific surface area is selected so that the molding material has a better air purification effect.

[0041] According to some embodiments of the present invention, the material of the substrate includes at least one of glass, ceramic, paper, aluminum titanate, mullite and cordierite.

[0042] According to some embodiments of the present invention, the shape of the substrate includes at least one of a cylindrical shape, a cylindrical shape, a square shape and a rhombus shape.

[0043] It can be either a regular shape or an irregular shape, and can be prepared into any shape as needed.

[0044] According to some embodiments of the present invention, the MOFs material includes at least one of Al-Fum (Al), UiO-66 (Zr), MOFs-5 (Zn), ZIF-67 (Co), ZIF-7 (Zn), MIL-125 (Ti), MIL-88B (Fe), MIL-68 (Fe), MIL-47 (V), palladium-doped MOFs material, copper-containing MOFs material and chromium-containing MOFs material.

[0045] The scheme of the present invention can be applied to a variety of MOFs materials. All formable MOFs materials can be adapted to the present invention and can be purchased commercially or made at home.

[0046] According to some embodiments of the present invention, the MOFs slurry further contains an additive.

[0047] According to some embodiments of the present invention, in the MOFs slurry, the mass ratio of the additive to the MOFs material is 0.01 to 1:100.

[0048] According to some embodiments of the present invention, the auxiliary agent comprises at least one of a dispersant, a thickener, a wetting agent, a leveling agent and a defoaming agent.

[0049] The additives can be selected according to the needs, and the types of additives are not limited, and can be inorganic or organic.

[0050] A second aspect of the present invention provides a method for preparing a metal organic framework molding material, comprising the following steps:

[0051] S1, dispersing the inorganic binder in the organic binder to obtain a composite binder;

[0052] S2, preparing the composite binder and MOFs material into MOFs slurry;

[0053] S3, forming the MOFs slurry on a substrate, to obtain;

[0054] Wherein, the inorganic binder is dispersed in the organic binder.

[0055] A technical solution in the method for preparing a metal organic framework molding material of the present invention has at least the following beneficial effects:

[0056] First, prepare the composite binder, and then prepare it into a slurry with the MOFs material to form it. The operation is simple and the effective loading of the MOFs material can be achieved through simple operation. The production efficiency is high and it is easy to industrialize. The formed MOFs material has stable and reliable performance and can be reused and recycled. It does not require complicated processes or high-cost reagents, and the production cost is low and the economic benefits are high.

[0057] According to some embodiments of the present invention, the organic binder includes a binder with a molecular chain structure, and the inorganic binder is dispersed in the molecular chain structure of the organic binder.

[0058] According to some embodiments of the present invention, in step S1, the inorganic binder is dispersed in the organic binder by ultrasound to form a homogeneous emulsion.

[0059] The inorganic binder has a smaller molecular weight, while the organic binder has a larger molecular weight. When the organic binder acts as a binder, it usually forms a film and covers the surface of the active ingredient. The inorganic binder is effectively dispersed in the molecular chain structure of the organic binder by strong homogenization or dispersion means such as ultrasound. During the use of the composite binder, a dense film structure will not be formed, and the active ingredient can be effectively exposed while acting as a binder.

[0060] According to some embodiments of the present invention, in step S1, the ultrasonication time is more than 15 minutes.

[0061] According to some embodiments of the present invention, in step S1, the ultrasonication time is 15 to 30 minutes.

[0062] According to some embodiments of the present invention, the step S2 includes dissolving the composite binder and the MOFs material in a solvent to prepare a MOFs slurry.

[0063] According to some embodiments of the invention, the solvent is at least one of water, methanol or ethanol.

[0064] In the process of preparing the slurry, water, methanol or ethanol can be used as the solvent, which is easy to dry and will not cause harm to the human body.

[0065] According to some embodiments of the present invention, step S2 further includes a step of regulating the particle size of the MOFs slurry.

[0066] According to some embodiments of the present invention, the particle size control is to control the particle size to a D50 of 0.5 μm to 3 μm.

[0067] The particle size of the slurry can be adjusted by using tools such as a sand mill, a disperser or a colloid mill.

[0068] According to some embodiments of the present invention, in step S3, the forming includes the step of loading the MOFs slurry on a substrate.

[0069] The slurry is directly loaded on the substrate for processing and forming, avoiding the large resistance caused by filling and utilization and the difficulty in desorption and regeneration for recycling. The MOFs material solidified on the substrate has a high processing volume per unit time.

[0070] According to some embodiments of the present invention, step S3 further includes a step of preparing a substrate, specifically including first curing the substrate with a binder and then forming the substrate by calcination.

[0071] In the related art, the substrate is first impregnated and then the substrate and MOFs slurry are wound together to form a rotating wheel. However, when the substrate impregnated with MOFs undergoes the winding process, the MOFs powder material is easily lost, thereby reducing the overall performance of the product. The present invention directly solidifies the substrate first to avoid adverse effects of the substrate processing on the MOFs material.

[0072] A porous substrate such as corrugated paper with a certain flute height and flute width is pressed into a mold, and the corrugated paper and flat paper are combined and formed by impregnating an inorganic or organic binder. After the molding, the sample is calcined to obtain a finished corrugated substrate.

[0073] The present invention preferably uses a porous substrate as a mold, and the molded material has relatively large pores, extremely small wind resistance, and is easy to absorb fluid.

[0074] According to some embodiments of the present invention, in step S3, the MOFs slurry is loaded on a substrate by vacuum coating.

[0075] The vacuum one-time coating process is adopted, and the slurry can be directly and automatically poured onto the substrate in a continuous feeding vacuum coating device without dipping, which can realize fully automated production and reduce labor costs. At the same time, the coating is more uniform, does not block the holes, and the slurry is not easy to remain. There is no need for secondary purge with compressed air, which is more suitable for industrial production. The related technology adopts syringe extrusion molding, which is extremely inefficient and difficult to achieve mass production.

[0076] According to some embodiments of the present invention, the vacuum coating comprises the following steps: placing a substrate in a vacuum coating machine cavity, and pouring the MOFs slurry from one end of the substrate to cover the entire substrate.

[0077] Through vacuum coating, the slurry can flow to the entire substrate surface at one time, with uniform flow and good material uniformity. The excess slurry can be directly recycled by setting up a residual material recovery pool at the other end of the substrate. The residual material can be recycled, reducing waste and loss in the material coating process and reducing production costs.

[0078] According to some embodiments of the present invention, the relative vacuum degree during the vacuum coating process is controlled at -1 MPa to -0.01 MPa.

[0079] According to some embodiments of the present invention, the vacuum coating time is less than 30 seconds. Spraying and other coating processes usually take more than 5 minutes. The present invention uses vacuum coating, and the coating time does not exceed 30 seconds, which can shorten the time by more than 90% and has a high yield.

[0080] According to some embodiments of the present invention, the vacuum coating time is 10s to 30s.

[0081] The dip coating process usually involves first dipping the substrate into the slurry, then taking it out and placing it on a vacuum machine for vacuum filtration to remove excess slurry (or using air to blow away the remaining material). The process usually takes more than 3 minutes. Vacuum coating can greatly improve production efficiency.

[0082] According to some embodiments of the present invention, in step S3, the loading amount of the MOFs slurry on the substrate is 80 g / L to 200 g / L. 80 g / L to 200 g / L can be coated on the substrate as needed, the coating amount is high and controllable, and is suitable for industrial large-scale mass production.

[0083] According to some embodiments of the present invention, in step S3, the forming further includes the step of drying the coated slurry.

[0084] According to some embodiments of the present invention, in step S3, the drying is electromagnetic wave drying. No high-temperature drying is required, and the problem of MOFs material forming a plate on the substrate will not occur. In the molding process of the related art, the curing process adopts hot air high-temperature heating and curing molding. Since MOFs are organic framework structures, most MOFs materials have poor thermal stability. High-temperature heating and curing can easily cause the organic framework to deform, collapse or even carbonize, destroying the spatial structure of the material. Therefore, it is difficult to apply to most MOFs materials.

[0085] Traditional hot air drying evaporates water from the outside to the inside, and it takes a long time for the internal water to be discharged, and it is easy to cause multiple problems such as surface cracking and easy coating loss. The present invention adopts electromagnetic wave drying, and the drying process evaporates water from the inside to the outside, which shortens the drying time and improves production efficiency; the MOFs material after drying is not easy to agglomerate, the surface of the material is uniform and flat, without cracking or falling powder, the exposed surface of the material is large, and the adsorption performance is high.

[0086] According to some embodiments of the present invention, the electromagnetic wave drying is light wave drying. Light wave drying has no radiation, no fire, no smoke, and high drying efficiency.

[0087] According to some embodiments of the present invention, the wavelength of the light wave used in the light wave drying is 8 to 14 μm. Infrared light wave drying does not require excessively high temperatures and does not destroy the internal spatial structure of the material, and is applicable to most MOFs materials.

[0088] The third aspect of the present invention provides a metal-organic framework molding material for use as a catalyst, catalyst carrier, adsorbent, fluid storage agent, desiccant, ion exchange material, molecular sieve, separation material, material for selective molecular release, material for molecular uptake, molecular recognition, sensor, nanotube or nanoreactor, wherein the metal-organic framework molding material is the above-mentioned metal-organic framework molding material or is the metal-organic framework molding material prepared by the above-mentioned preparation method.

[0089] A technical solution in the use of the metal organic framework molding material of the present invention has at least the following beneficial effects:

[0090] The material of the present invention is suitable for various MOFs materials, and can retain the structure of the MOFs material itself to the maximum extent, so it has the same wide application as the MOFs material, and at the same time, it is easy to recycle and has low cost.

[0091] According to some embodiments of the invention, the separation material comprises a chromatographic material.

[0092] It can be prepared into chromatographic consumables such as chromatographic columns and solid phase extraction columns.

[0093] A fourth aspect of the present invention provides a water collection device, wherein the raw materials for preparing the water collection device include the metal organic framework forming material mentioned above or the metal organic framework forming material prepared by the above preparation method.

[0094] A technical solution of the water collecting device of the present invention has at least the following beneficial effects:

[0095] The raw material for preparing the water collection device of the present invention adopts the metal organic framework molding material of the present invention, thereby having the beneficial effects of the metal organic framework molding material. Specifically, the water collection device of the present invention has good water absorption. After the MOFs material in the metal organic framework molding material of the present invention is structured by a specific composite binder, the specific surface area and pore volume losses are small, the crystal structure of the MOFs material remains intact, and it has good adsorption separation and kinetic properties. At the same time, after structuring, it is easy to realize desorption and regeneration circulation, and has broad application prospects in the field of water collection devices.

[0096] A fifth aspect of the present invention provides a gas storage device, wherein the raw materials for preparing the gas storage device include the metal organic framework forming material mentioned above or the metal organic framework forming material prepared by the above preparation method.

[0097] A technical solution of the gas storage device of the present invention has at least the following beneficial effects:

[0098] The gas storage device of the present invention is prepared by using the metal organic framework molding material of the present invention as raw material, thereby having the beneficial effects of the metal organic framework molding material. Specifically, the gas storage device of the present invention has good gas adsorption. During the gas adsorption process, the morphology and size of the material have a significant influence on the adsorption effect. After the MOFs material in the metal organic framework molding material of the present invention is structured by a specific composite binder, the composite binder firmly solidifies the MOFs material, the performance is stable and reliable, the intrinsic pore structure of the MOFs material is retained to the maximum extent, and the MOFs pores are not blocked, the adsorption efficiency is high, and at the same time, the material is firmly solidified, so that it is easy to recycle and reuse, and has broad application prospects in the field of gas storage devices.

[0099] A sixth aspect of the present invention provides an air purification device, wherein the raw materials for preparing the air purification device include the metal organic framework molding material mentioned above or the metal organic framework molding material prepared by the above preparation method.

[0100] A technical solution of the air purification device of the present invention has at least the following beneficial effects:

[0101] The raw materials for preparing the air purification device of the present invention adopt the metal organic framework molding material of the present invention, thereby having the beneficial effects of the metal organic framework molding material. Specifically, the air purification device of the present invention has a good air purification effect. After the MOFs material in the metal organic framework molding material of the present invention is structured by a specific composite binder, the binder firmly solidifies the MOFs material, and the performance is stable and reliable. The intrinsic characteristics of the MOFs material are retained to the maximum extent, and the effective adsorption of harmful gases can be achieved, which can effectively prevent the harm of harmful gases to the human body.

[0102] A seventh aspect of the present invention provides a household appliance, wherein the raw materials for preparing the household appliance include the metal organic framework forming material or the metal organic framework forming material prepared by the above preparation method.

[0103] The present invention relates to a technical solution for household appliances, which has at least the following beneficial effects:

[0104] The raw material for preparing the household appliance of the present invention adopts the metal organic framework molding material of the present invention, thereby having the beneficial effects of the metal organic framework molding material. Specifically, the household appliance of the present invention has good fluid adsorption. After the MOFs material in the metal organic framework molding material of the present invention is structured by a specific composite binder, the binder firmly solidifies the MOFs material, the performance is stable and reliable, the intrinsic pore structure of the MOFs material is retained to the maximum extent, and the MOFs pores are not blocked, and the adsorption efficiency is high. The household appliance made using the metal organic framework molding material of the present invention has high working efficiency and stable performance, and has broad application prospects in the field of household appliances.

[0105] According to some embodiments of the present invention, the household appliance includes at least one of a fresh air fan, a dehumidifier, a fresh air air conditioner, an air purifier, a clothes dryer and a dishwasher. BRIEF DESCRIPTION OF THE DRAWINGS

[0106] Figure 1 It is a comparison diagram of water adsorption curves of the metal organic framework molding material in Example 1 of the present invention and the fresh MOFs material without coating treatment. In the figure, the Zr-based rotor MOF represents the metal organic framework molding material in Example 1, and the Zr-based fresh MOF represents the fresh MOFs material without coating treatment.

[0107] Figure 2 It is a comparison diagram of water adsorption curves of the metal organic framework forming material in comparative example 1 of the present invention and the fresh MOFs material without coating treatment. In the figure, the dip-coated rotor MOF represents the metal organic framework forming material in comparative example 1, and the Zr-based fresh MOF represents the fresh MOFs material without coating treatment. DETAILED DESCRIPTION

[0108] The following are specific embodiments of the present invention, and the technical solutions of the present invention are further described in conjunction with the embodiments, but the present invention is not limited to these embodiments.

[0109] In the description of the present invention, it is to be understood that above, below, etc. are understood to include the number itself, while greater than, less than, etc. are understood to exclude the number itself.

[0110] In some embodiments of the present invention, the present invention provides a metal organic framework molding material, wherein the raw materials for preparing the metal organic framework molding material include a substrate and a MOFs slurry loaded on the substrate, the MOFs slurry contains MOFs material and a composite binder, the composite binder includes an inorganic binder and an organic binder, and the inorganic binder is dispersed in the organic binder.

[0111] It can be understood that in the metal organic framework molding material of the present invention, the inorganic binder is dispersed in the organic binder to prevent the organic binder from forming a whole film during the molding process, which can prevent the pore structure of the MOFs material itself from being blocked and avoid affecting the performance of the MOFs material. At the same time, it can achieve strong bonding and improve its use efficiency.

[0112] It can also be understood that in the metal organic framework molding material of the present invention, the composite binder can form a spider web-like structure during the drying process to avoid forming a dense film structure, and can effectively expose the active ingredients while playing a bonding role.

[0113] It can also be understood that the metal organic framework molding material of the present invention contains an inorganic binder in the composite binder, so that the molding material has better compressive strength; in the related art, a briquetting process is required to improve the compressive strength. Although the material can have a greater crushing strength by increasing the extrusion pressure, it will cause the MOFs powders to be tightly packed, the particles to agglomerate severely, and the pores between the MOFs single crystal particles are small, resulting in only the surface material working during use and the internal material utilization rate is low.

[0114] It can also be understood that the metal organic framework molding material of the present invention can better retain the structure of MOFs itself, and the performance of the material is not attenuated after molding. The original performance of the MOFs material can be retained to the maximum extent. At the same time, it can avoid the defects of traditional powder MOFs materials and broaden the application range of MOFs materials.

[0115] It can be understood that the metal organic framework molding material of the present invention, MOFs, is loaded by a composite binder with high loading efficiency and has good application prospects in multiple fields such as adsorption, separation, and storage.

[0116] In some embodiments of the present invention, the organic binder includes a binder with a molecular chain structure, and the inorganic binder is dispersed in the molecular chain structure of the organic binder.

[0117] In some embodiments of the present invention, the particle size D50 of the raw material is 0.5-3 μm. Controlling the particle size of the raw material is beneficial to one-step molding and increasing the coating amount.

[0118] If the particle size is too small, the specific surface area of ​​the particle size will increase. When preparing the slurry, it is easy to absorb water and expand, resulting in low solid content of the slurry and reduced coating amount. In addition, if the particle size is too small, if the diameter of the substrate used is small, it is easy to cause agglomeration during the coating and drying process, and the material is easy to fall off after agglomeration. If the particle size is too large, the amount of binder will increase, otherwise it will not be easy to adhere. In addition, in the large particle size slurry, more slurry will agglomerate, and the utilization rate of the agglomerated slurry will be lower.

[0119] For example, the particle size D50 is 1.8μm, 2.0μm, and 2.5μm.

[0120] In some embodiments of the present invention, in the MOFs slurry, the mass ratio of the composite binder to the MOFs material is 1 to 10: 100. By adding less binder, a molding material with better mechanical properties can be obtained, and the obtained molding material has high specific area and pore volume retention rate and low production cost.

[0121] Such as the mass ratio is 2:100, 3:100, 3.5:100, 5:100, 7:100, 8:100, 9:100, etc.

[0122] In some embodiments of the present invention, in the MOFs slurry, the mass percentage of MOFs material is 5% to 50%.

[0123] For example, the mass percentage is 7%, 8%, 10%, 11%, 11.7%, 12%, 14%, 15%, 16%, 16.5%, 17%, 19%, 19.9%, 20%, 22%, 25%, 28%, 30%, 32%, 35%, 38%, 40%, 42%, 45%, 48%, etc.

[0124] In some embodiments of the present invention, the organic binder includes at least one of acrylic resin, polyurethane, epoxy resin, polyol, silicone, sodium hydroxymethyl cellulose, glycerin and starch.

[0125] In some embodiments of the present invention, the inorganic binder includes at least one of silica sol, aluminum sol, aluminum phosphate sol, titanium dioxide sol, clay and kaolin.

[0126] In some embodiments of the present invention, the aluminum phosphate sol includes at least one of aluminum phosphate sol and aluminum dihydrogen phosphate sol.

[0127] In some embodiments of the present invention, the inorganic binder is a nanoscale inorganic binder, that is, the size of the inorganic binder in three-dimensional space has at least one dimension in the nanometer size of 1-100 nm.

[0128] Such as 7nm, 18nm, 28nm, 38nm, 48nm, 55nm, 60nm, 70nm, 80nm, 90nm, etc.

[0129] In some embodiments of the present invention, the particle size of the inorganic binder is below 50 nm.

[0130] Such as 6nm, 8nm, 10nm, 15nm, 20nm, 25nm, 30nm, 35nm, 40nm, 45nm, etc.

[0131] In some embodiments of the present invention, the particle size of the inorganic binder is less than 5 nm.

[0132] Such as 1nm, 1.5nm, 2nm, 2.5nm, 3nm, 3.5nm, 4nm, 4.5nm, etc.

[0133] In some embodiments of the present invention, the inorganic binder accounts for 1% to 40% by weight of the organic binder.

[0134] For example, the mass percentage is 2%, 5%, 8%, 10%, 12%, 14%, 15%, 16%, 17%, 19%, 20%, 22%, 25%, 28%, 30%, 32%, 35%, 38%, 40%, 42%, 45%, 48%, etc.

[0135] When the proportion of inorganic binder is too low, the amount of organic binder will be too much, the film-forming property will be stronger, and the effective ingredients of the material will be partially covered, thus affecting the performance of the product; when the proportion of inorganic binder is too high, the amount of inorganic binder will be too much, the inorganic component will be too much, the adhesion ability will be reduced, and it will cause problems such as powdering and falling off.

[0136] In some embodiments of the present invention, the substrate is a porous substrate such as a corrugated substrate or a honeycomb substrate.

[0137] MOFs materials are formed on porous substrates and have many advantages, such as large specific surface area, low wind resistance, high material utilization, and continuous recycling.

[0138] In some embodiments of the present invention, the thickness of the substrate is above 5 mm.

[0139] If the substrate is too thin, its ability to withstand force during coating and other processes will be limited, and it will be prone to breakage.

[0140] In some embodiments of the present invention, the thickness of the substrate is between 5 mm and 500 mm.

[0141] In some embodiments of the present invention, the corrugated substrate has a corrugation height of 0.5 to 5 mm and a corrugation width of 1 to 5 mm.

[0142] In some embodiments of the present invention, the honeycomb holes in the honeycomb substrate are hexagonal, the side length of the hexagon is 0.5-10 mm, and the hole wall thickness of the honeycomb holes is 0.1-5 mm.

[0143] The substrate is directly solidified and formed through a die extrusion process, thus avoiding the problem in related technologies that there is no solidification treatment, which causes adjacent honeycomb structures to be easily misaligned and deformed during use, thus affecting the service life of the product.

[0144] The parameters of the substrate can be selected according to the application requirements of the molding material. For example, if it is required to be applied in the field of air purification, a porous substrate structure parameter with smaller wind resistance and effective macroscopic specific surface area is selected so that the molding material has a better air purification effect.

[0145] In some embodiments of the present invention, the material of the substrate includes at least one of glass, ceramic, paper, aluminum titanate, mullite and cordierite.

[0146] In some embodiments of the present invention, the shape of the substrate includes at least one of a cylindrical shape, a cylindrical shape, a square shape and a rhombus shape.

[0147] It can be either a regular shape or an irregular shape, and can be prepared into any shape as needed.

[0148] In some embodiments of the present invention, the MOFs material includes at least one of Al-Fum (Al), UiO-66 (Zr), MOFs-5 (Zn), ZIF-67 (Co), ZIF-7 (Zn), MIL-125 (Ti), MIL-88B (Fe), MIL-68 (Fe), MIL-47 (V), palladium-doped MOFs material, copper-containing MOFs material and chromium-containing MOFs material.

[0149] The scheme of the present invention can be applied to a variety of MOFs materials. All formable MOFs materials can be adapted to the present invention and can be purchased commercially or made at home.

[0150] In some embodiments of the present invention, the MOFs slurry further contains an additive.

[0151] In some embodiments of the present invention, in the MOFs slurry, the mass ratio of the additive to the MOFs material is 0.01 to 1:100.

[0152] In some embodiments of the present invention, the auxiliary agent comprises at least one of a dispersant, a thickener, a wetting agent, a leveling agent and a defoaming agent.

[0153] The additives can be selected according to the needs, and the types of additives are not limited, and can be inorganic or organic.

[0154] In some other embodiments of the present invention, a method for preparing a metal organic framework molding material is provided, comprising the following steps:

[0155] S1, dispersing the inorganic binder in the organic binder to obtain a composite binder;

[0156] S2, preparing the composite binder and MOFs material into MOFs slurry;

[0157] S3, forming the MOFs slurry on a substrate, to obtain;

[0158] Wherein, the inorganic binder is dispersed in the organic binder.

[0159] It can be understood that the preparation method of the metal organic framework molding material of the present invention is to first prepare a composite binder, then prepare it and the MOFs material into a slurry to form it, which is simple to operate, has high production efficiency, and is easy to industrialize; the molded MOFs material has stable and reliable performance and can be reused and recycled; no complicated process or high-cost reagents are required, the production cost is low, and the economic benefit is high.

[0160] In some embodiments of the present invention, the organic binder includes a binder with a molecular chain structure, and the inorganic binder is dispersed in the molecular chain structure of the organic binder.

[0161] In some embodiments of the present invention, in step S1, the inorganic binder is dispersed in the organic binder by ultrasound to form a homogeneous emulsion.

[0162] The inorganic binder has a smaller molecular weight, while the organic binder has a larger molecular weight. When the organic binder acts as a binder, it usually forms a film and covers the surface of the active ingredient. The inorganic binder is effectively dispersed in the molecular chain structure of the organic binder by strong homogenization or dispersion means such as ultrasound. During the use of the composite binder, a dense film structure will not be formed, and the active ingredient can be effectively exposed while acting as a binder.

[0163] According to some embodiments of the present invention, in step S1, the ultrasonication time is more than 15 minutes.

[0164] In some embodiments of the present invention, in step S1, the ultrasonic treatment time is 15 to 30 minutes.

[0165] Such as 18min, 20min, 22min, 25min, 28min.

[0166] The ultrasonic power can be set as required, such as 500 W, 550 W, 600 W, 650 W, 700 W, 750 W, and 800 W. In some embodiments of the present invention, the step S2 includes dissolving the composite binder and the MOFs material in a solvent to prepare a MOFs slurry.

[0167] In some embodiments of the present invention, the solvent may be at least one of water, methanol or ethanol.

[0168] In the process of preparing the slurry, water, methanol or ethanol can be used as the solvent, which is easy to dry and will not cause harm to the human body.

[0169] In some embodiments of the present invention, step S2 further includes a step of regulating the particle size of the MOFs slurry.

[0170] In some embodiments of the present invention, the particle size control is to control the particle size to a D50 of 0.5 μm to 3 μm.

[0171] The particle size of the slurry can be adjusted by using tools such as a sand mill, a disperser or a colloid mill.

[0172] In some embodiments of the present invention, in step S3, the forming includes the step of loading the MOFs slurry on a substrate.

[0173] The slurry is directly loaded on the substrate for processing and forming, avoiding the large resistance caused by filling and utilization and the difficulty in desorption and regeneration for recycling. The MOFs material solidified on the substrate has a high processing volume per unit time.

[0174] In some embodiments of the present invention, step S3 further includes a step of preparing a substrate, specifically including first curing the substrate with a binder and then forming the substrate by calcination.

[0175] In the related art, the substrate is first impregnated and then the substrate and MOFs slurry are wound together to form a rotating wheel. However, when the substrate impregnated with MOFs undergoes the winding process, the MOFs powder material is easily lost, thereby reducing the overall performance of the product. The present invention directly solidifies the substrate first to avoid adverse effects of the substrate processing on the MOFs material.

[0176] A porous substrate such as corrugated paper with a certain flute height and flute width is pressed into a mold, and the corrugated paper and flat paper are combined and formed by impregnating an inorganic or organic binder. After the molding, the sample is calcined to obtain a finished corrugated substrate.

[0177] The present invention preferably uses a porous substrate as a mold, and the molded material has relatively large pores, extremely small wind resistance, and is easy to absorb fluid.

[0178] In some embodiments of the present invention, in step S3, the MOFs slurry is loaded on the substrate by vacuum coating.

[0179] The vacuum one-time coating process is adopted, and the slurry can be directly and automatically poured onto the substrate in a continuous feeding vacuum coating device without dipping, which can realize fully automated production and reduce labor costs. At the same time, the coating is more uniform, the molding is done in one time, there is no hole blocking, the slurry is not easy to remain, and there is no need for secondary purge with compressed air, which is more suitable for industrial production. The related technology adopts syringe extrusion molding, which is extremely inefficient and difficult to achieve mass production.

[0180] In some embodiments of the present invention, the vacuum coating comprises the following steps: placing the substrate in a vacuum coating machine cavity, and pouring the MOFs slurry from one end of the substrate to cover the entire substrate.

[0181] Through vacuum coating, the slurry can flow to the entire substrate surface at one time, with uniform flow and good material uniformity. The excess slurry can be directly recycled by setting up a residual material recovery pool at the other end of the substrate. The residual material can be recycled, reducing waste and loss in the material coating process and reducing production costs.

[0182] In some embodiments of the present invention, the relative vacuum degree during the vacuum coating process is controlled at -1 MPa to -0.01 MPa.

[0183] In some embodiments of the present invention, the vacuum coating time is less than 30 seconds, such as 1 second, 2 seconds, 3 seconds, 5 seconds, 10 seconds, 13 seconds, 15 seconds, 20 seconds, 25 seconds, etc. Spraying and other coating processes usually require more than 5 minutes. The present invention adopts vacuum coating, and the coating time does not exceed 30 seconds, which can shorten the time by more than 90% and has a high yield.

[0184] In some embodiments of the present invention, the vacuum coating time is 10s to 30s.

[0185] In some embodiments of the present invention, in step S3, the loading amount of the MOFs slurry on the substrate is 80 g / L to 200 g / L. 80 g / L to 200 g / L can be coated on the substrate as needed, the coating amount is high and controllable, and is suitable for industrial large-scale mass production.

[0186] In some embodiments of the present invention, in step S3, the forming further includes the step of drying the coated slurry.

[0187] In some embodiments of the present invention, in step S3, the drying is electromagnetic wave drying. No high-temperature drying is required, and the problem of MOFs material forming a plate on the substrate will not be formed. In the molding process of the related art, the curing process adopts hot air high-temperature heating and curing molding. Since MOFs are organic framework structures, most MOFs materials have poor thermal stability. High-temperature heating and curing can easily cause the organic framework to deform, collapse or even carbonize, destroying the spatial structure of the material. Therefore, it is difficult to apply to most MOFs materials.

[0188] Traditional hot air drying evaporates water from the outside to the inside, and it takes a long time for the internal water to be discharged, and it is easy to cause multiple problems such as surface cracking and easy coating loss. The present invention adopts electromagnetic wave drying, and the drying process evaporates water from the inside to the outside, which shortens the drying time and improves production efficiency; the MOFs material after drying is not easy to agglomerate, the surface of the material is uniform and flat, without cracking or falling powder, the exposed surface of the material is large, and the adsorption performance is high.

[0189] In some embodiments of the present invention, the electromagnetic wave drying is light wave drying. Light wave drying has no radiation, no fire, no smoke, and high drying efficiency.

[0190] In some embodiments of the present invention, the wavelength of the light wave used in the light wave drying is 8 to 14 μm. Infrared light wave drying does not require excessively high temperatures and does not destroy the internal spatial structure of the material, and is applicable to most MOFs materials.

[0191] In some other embodiments of the present invention, there is provided a metal-organic framework forming material for use as a catalyst, a catalyst carrier, an adsorbent, a fluid storage agent, a desiccant, an ion exchange material, a molecular sieve, a separation material, a material for selective molecular release, a material for molecular uptake, molecular recognition, a sensor, a nanotube or a nanoreactor, wherein the metal-organic framework forming material is the above-mentioned metal-organic framework forming material or is a metal-organic framework forming material prepared by the above-mentioned preparation method.

[0192] It can be understood that the metal organic framework molding material of the present invention is suitable for reprocessing various MOFs materials. It can retain the structure of the MOFs material itself to the maximum extent, so it has the same wide application as MOFs material. At the same time, it is easy to recycle and low cost.

[0193] In some embodiments of the invention, the separation material comprises a chromatographic material.

[0194] It can be prepared into chromatographic consumables such as chromatographic columns and solid phase extraction columns.

[0195] In some other embodiments of the present invention, a water collection device is provided, wherein the raw materials for preparing the water collection device include the metal organic framework forming material mentioned above or the metal organic framework forming material prepared by the above preparation method.

[0196] It can be understood that the raw material for preparing the water collection device of the present invention adopts the metal organic framework molding material of the present invention, thereby having the beneficial effects of the metal organic framework molding material. Specifically, the water collection device of the present invention has good water absorption. After the MOFs material in the metal organic framework molding material of the present invention is structured by a specific composite binder, the specific surface area and pore volume losses are small, the crystal structure of the MOFs material remains intact, and it has good adsorption separation and kinetic properties. At the same time, after structuring, it is easy to realize desorption and regeneration circulation, and has broad application prospects in the field of water collection devices.

[0197] In some other embodiments of the present invention, a gas storage device is provided, wherein the raw materials for preparing the gas storage device include the metal organic framework forming material mentioned above or the metal organic framework forming material prepared by the above preparation method.

[0198] It can be understood that the raw material for preparing the gas storage device of the present invention adopts the metal-organic framework molding material of the present invention, thereby having the beneficial effects of the metal-organic framework molding material. Specifically, the gas storage device of the present invention has good gas adsorption. During the gas adsorption process, the morphology and size of the material have a significant influence on the adsorption effect. After the MOFs material in the metal-organic framework molding material of the present invention is structured by a specific composite binder, the composite binder firmly solidifies the MOFs material, and the performance is stable and reliable. The intrinsic pore structure of the MOFs material is retained to the maximum extent without blocking the MOFs pores, and the adsorption efficiency is high. At the same time, the material is firmly solidified, which makes it easy to recycle and reuse, and has broad application prospects in the field of gas storage devices.

[0199] In some other embodiments of the present invention, an air purification device is provided, wherein the raw materials for preparing the air purification device include the metal organic framework forming material mentioned above or the metal organic framework forming material prepared by the above preparation method.

[0200] It can be understood that the raw materials for preparing the air purification device of the present invention adopt the metal organic framework molding material of the present invention, thereby having the beneficial effects of the metal organic framework molding material. Specifically, the air purification device of the present invention has a good air purification effect. After the MOFs material in the metal organic framework molding material of the present invention is structured by a specific composite binder, the binder firmly solidifies the MOFs material, and the performance is stable and reliable. The intrinsic characteristics of the MOFs material are retained to the maximum extent, and the effective adsorption of harmful gases can be achieved, which can effectively avoid the harm of harmful gases to the human body.

[0201] In some other embodiments of the present invention, a household appliance is provided, wherein the raw materials for preparing the household appliance include the metal organic framework forming material or the metal organic framework forming material prepared by the above preparation method.

[0202] It can be understood that the raw materials for preparing the household appliances of the present invention adopt the metal-organic framework molding material of the present invention, thereby having the beneficial effects of the metal-organic framework molding material. Specifically, the household appliances of the present invention have good fluid adsorption. After the MOFs material in the metal-organic framework molding material of the present invention is structured by a specific composite binder, the binder firmly solidifies the MOFs material, and the performance is stable and reliable. The intrinsic pore structure of the MOFs material is retained to the maximum extent without blocking the MOFs pores, and the adsorption efficiency is high. The household appliances made using the metal-organic framework molding material of the present invention have high working efficiency and stable performance, and have broad application prospects in the field of household appliances.

[0203] In some embodiments of the present invention, the household appliance includes at least one of a fresh air fan, a dehumidifier, a fresh air air conditioner, an air purifier, a clothes dryer and a dishwasher.

[0204] The metal organic framework molding material of the present invention can be applied to various household appliances requiring purification and dehumidification.

[0205] The technical solution of the present invention will be better understood with reference to specific embodiments below.

[0206] It should be noted that in the following examples and comparative examples, the additives are composed of a dispersant and a leveling agent in a mass ratio of 1:1. Among them, the dispersant: Guangzhou Lanxi Chemical Technology Co., Ltd., item number W100; the leveling agent: Foshan Kening New Materials Co., Ltd., item number KMT-5510S.

[0207] It should also be noted that in the following examples and comparative examples, Zr-based MOFs and Cr-based MOFs are homemade and can also be directly purchased from the market.

[0208] The specific process of Zr-based MOFs is as follows:

[0209] 200 g of zirconium oxychloride octahydrate, 180 g of fumaric acid and 0.7 L of acetic acid were added to 15 L of water, reacted in a water bath at 80 °C for 6 h, taken out, washed with ethanol, filtered and dried in an oven at 150 °C to obtain Zr-based MOFs.

[0210] The specific process of Cr-based MOFs is:

[0211] 19 g of sodium hydroxide, 150 g of terephthalic acid and 300 g of chromium nitrate nonahydrate were added to 1.2 L of water, reacted at 200 ° C in a high-pressure reactor for 4 hours, taken out and washed with N, N-dimethylformamide (DMF), centrifuged and dried in an oven at 100 ° C to obtain Cr-based-MOFs.

[0212] Example 1

[0213] In this embodiment, a metal organic framework molding material is first prepared. The raw materials for preparing the molding material include a substrate and a MOFs slurry loaded on the substrate. The MOFs slurry contains MOFs material and a composite binder. The composite binder is composed of an inorganic binder and an organic binder with a molecular chain structure.

[0214] The specific preparation method is:

[0215] An inorganic binder silica sol (particle size 30-50 nm, MacLean reagent, item number S888350) and an organic binder polyurethane (McLean reagent, item number A909856) in a mass ratio of 0.2:1 were ultrasonically treated at a power of 600 W for 20 minutes to obtain a composite binder for later use.

[0216] 500 g of Zr-based MOFs for humidity control, 10 g of composite binder and 1 g of additive were dispersed in 2 kg of deionized water to obtain MOFs slurry; the MOFs slurry was passed through a colloid mill for 10 cycles to adjust the particle size, and the D50 of the slurry after adjustment was 1.8 μm.

[0217] A cylindrical glass fiber corrugated board calcined at 550°C was selected as the substrate, with a cylindrical glass fiber diameter of 300 mm, a substrate thickness of 30 mm, a corrugated corrugation height of 1.5 mm, and a corrugation width of 3 mm. The substrate was placed in the mold of the vacuum coating equipment, and the relative vacuum degree was adjusted to -0.1 MPa. The prepared MOFs slurry was poured on the upper end of the substrate to evenly cover (flow) the entire substrate surface. The one-time coating of the MOFs slurry was completed within 13 seconds.

[0218] The coated MOFs sample was placed in an infrared light wave dryer (power 900 W) and dried for 15 minutes to obtain a MOFs wheel sample (i.e., metal organic framework molding material).

[0219] Example 2

[0220] The difference between this embodiment and embodiment 1 is that the diameter of the cylindrical glass fiber in the preparation process of the metal organic framework molding material is 400 mm. In addition, this embodiment also provides the application of the prepared metal organic framework molding material in a dehumidifier. The MOFs wheel is divided into 3:1, of which 1 / 4 is the heating desorption zone and 3 / 4 is the adsorption zone, and the wheel speed is 2 min / r.

[0221] The wheel adsorption area absorbs moisture to achieve the purpose of dehumidification. The wheel after moisture absorption is rotated to the coating area for regeneration through 70℃ hot air. The regenerated wheel returns to the adsorption area by rotation. In this cycle, the wheel adsorbs and desorbs at the same time, achieving the purpose of adsorption-desorption cycle regeneration.

[0222] Example 3

[0223] In this embodiment, a metal organic framework molding material is first prepared. The raw materials for preparing the molding material include a substrate and a MOFs slurry loaded on the substrate. The MOFs slurry contains MOFs material and a composite binder. The composite binder is composed of an inorganic binder and an organic binder with a molecular chain structure.

[0224] The specific preparation method is:

[0225] An inorganic binder silica sol (particle size 30-50 nm, MacLean reagent, product number S888350) and an organic binder polyacrylic acid (McLean reagent, CAS: 9003-01-4) with a mass ratio of 0.3:1 were ultrasonically treated at a power of 600 W for 20 minutes to obtain a composite binder for later use.

[0226] 200 g of Zr-based MOFs for humidity control, 7 g of composite binder and 0.7 g of additives were dispersed in 1.5 kg of deionized water to obtain MOFs slurry; the MOFs slurry was passed through a colloid mill for 10 cycles to adjust the particle size, and the D50 of the slurry after adjustment was 1.8 μm.

[0227] A cylindrical glass fiber corrugated board calcined at 550°C was selected as the substrate, with a cylindrical glass fiber diameter of 200 mm, a substrate thickness of 20 mm, a corrugated corrugation height of 1.5 mm, and a corrugation width of 3 mm. The substrate was placed in the mold of the vacuum coating equipment, and the relative vacuum degree was adjusted to -0.1 MPa. The prepared MOFs slurry was poured on the upper end of the substrate to evenly cover (flow) the entire substrate surface. The one-time coating of the MOFs slurry was completed within 13 seconds.

[0228] The coated MOFs sample was placed in an infrared light wave dryer (power 900 W) and dried for 15 minutes to obtain a MOFs wheel sample (i.e., metal organic framework molding material).

[0229] In addition, this embodiment also provides the application of the prepared metal organic framework molding material in fresh air air conditioning for latent heat treatment. The rotor speed is 3min / r, the ratio of the rotor adsorption zone to the regeneration zone is 1:1, the rotor regeneration temperature is 50°C, and under the conditions of 250CMH air volume, 21°C and 90%RH, the rotor processes 1300g of water per unit time. In this cycle, the rotor adsorbs and desorbs at the same time, and continuously rotates and regenerates, achieving the purpose of adsorption-desorption cycle regeneration.

[0230] Example 4

[0231] The difference between this embodiment and embodiment 3 is that the vacuum coating process is replaced by an immersion process, specifically, the substrate is placed in the prepared slurry and immersed for 120 seconds, and the residual material is removed by air blowing after being taken out. The rotor speed is 3min / r, the ratio of the rotor adsorption zone to the regeneration zone is 1:1, the rotor regeneration temperature is 50°C, and under the conditions of 250CMH air volume, 21°C and 90%RH, the rotor processes 610g of water per unit time. In this cycle, the rotor adsorbs and desorbs at the same time, and continuously rotates and regenerates, achieving the purpose of adsorption-desorption cyclic regeneration.

[0232] Example 5

[0233] In this embodiment, a metal organic framework molding material is first prepared. The raw materials for preparing the molding material include a substrate and a MOFs slurry loaded on the substrate. The MOFs slurry contains MOFs material and a composite binder. The composite binder is composed of an inorganic binder and an organic binder with a molecular chain structure.

[0234] The specific preparation method is:

[0235] An inorganic binder aluminum sol (particle size of about 3 nm, Ningbo Jiwei Nano New Material Technology Co., Ltd., product number: JWN-AS15) and sodium hydroxymethyl cellulose (McLean reagent, CAS: 9085-26-1) with a mass ratio of 0.3:1 were ultrasonically treated at a power of 600 W for 20 minutes to obtain a composite binder for use.

[0236] 100 g of Cr-based MOFs for humidity control, 5 g of composite binder and 0.5 g of additives were dispersed in 0.5 kg of deionized water to obtain MOFs slurry; the MOFs slurry was ball milled for 10 minutes to adjust the particle size, and the D50 of the slurry after adjustment was 2 μm.

[0237] A honeycomb ceramic with hexagonal honeycomb holes, a side length of 2 mm, and a wall thickness of 2 mm is selected as the substrate. The overall thickness of the substrate is 15 mm. The substrate is placed in the mold of the vacuum coating equipment, the relative vacuum degree is adjusted to -0.05 MPa, and the prepared MOFs slurry is poured on the upper end of the substrate to evenly cover (flow) the entire substrate surface. The one-time coating of the MOFs slurry can be completed within 13 seconds.

[0238] The coated MOFs sample was placed in an infrared light wave dryer (power 900 W) and dried for 15 minutes to obtain a MOFs sample (ie, metal organic framework molding material).

[0239] Comparative Example 1

[0240] The difference between this comparative example and Example 1 is that the composite adhesive is replaced with 10 g of polyurethane.

[0241] Comparative Example 2

[0242] The difference between this comparative example and Example 2 is that the preparation raw material does not include a substrate, and Zr-MOF is directly prepared into a slurry and then formed by extrusion.

[0243] The obtained MOFs molding material has a particle size of 2.5mm*10mm. The MOFs molding material particles are filled in a dehumidifier, and the MOFs molding material is adsorbed. After the adsorption is completed, it is dried and regenerated by an external heating power supply (it can also be taken out). It is found that it cannot achieve the purpose of adsorption-desorption cycle regeneration.

[0244] Comparative Example 3

[0245] The difference between this comparative example and Example 5 is that the composite binder is replaced by 5 g of sodium hydroxymethyl cellulose.

[0246] Comparative Example 4

[0247] The difference between this comparative example and Example 5 is that the two are directly mixed to obtain the product.

[0248] Test example

[0249] The coating effects and properties of the metal organic framework molding materials prepared in the above Examples 1 to 5 and Comparative Examples 1 to 4 were tested. The coating effects are shown in Table 1 below:

[0250] Table 1

[0251]

[0252]

[0253] According to the results in Table 1, the metal organic framework molding material prepared by the composite binder has a higher coating amount and a good coating effect. The coating process also has a certain influence on the coating amount and the coating effect. The vacuum coating process has a high coating amount and a better effect. The immersion coating process has a good coating amount, but the coating uniformity is weaker than the vacuum coating process.

[0254] In the metal organic framework molding materials in Comparative Examples 1 and 2, since the organic binder forms a whole film during the drying process, the MOFs material has weak adhesion and is prone to powdering.

[0255] The molding material in Comparative Example 4 cannot be fully dispersed in the organic binder due to the simple mixing of the inorganic binder, so the coating amount is significantly reduced and the effect is greatly reduced. However, the composite binders in Examples 1 to 5 are prepared by strong homogenization or dispersion means, so that the inorganic binder is dispersed in the molecular chain structure of the organic binder, so that it forms a spider web-like structure during the drying process.

[0256] Since the MOFs materials in Examples 1 to 4 and Comparative Example 1 are usually used for dehumidification, the water adsorption effect of the molding materials obtained in Examples 1 to 4 and Comparative Example 1 was tested. The water adsorption test program was tested at 25°C using Bel's fully automatic specific surface area, pore analysis and vapor adsorption instrument. The results showed that the molding materials obtained in Comparative Examples 1 to 4 had a water adsorption capacity comparable to that of fresh MOFs materials without coating treatment. The water adsorption curve comparison diagrams of the molding materials in Example 1 and Comparative Example 1 and the fresh MOFs materials without coating treatment are shown in the figure below. Figure 1 and 2 shown.

[0257] from Figure 1 It can be seen that the water adsorption performance of the molded material in Example 1 is not significantly reduced compared with the fresh MOFs material.

[0258] from Figure 2 It can be seen that the water adsorption performance of the molding material using pure organic binder in Comparative Example 1 is significantly reduced compared with the fresh MOFs material.

[0259] Since the MOFs materials in Example 5 and Comparative Example 3 are used for air purification, the toluene adsorption effect of the molding materials prepared in Example 5 and Comparative Example 3 was tested. The prepared molding materials were placed in a VOC treatment tooling to test the toluene adsorption capacity, and the toluene detection was analyzed by GC-MS, and the initial concentration of toluene was 100 ppm.

[0260] The test results show that the mass adsorption capacity of the molding material in Example 5 for toluene is 96.5%; the mass adsorption capacity of the molding material in Comparative Example 3 for toluene is 67.3%, which shows that the molding material of the present invention can effectively remove toluene and has good application prospects in the field of air purification.

[0261] Evaluation standard of toluene removal capacity: The toluene removal capacity is limited to 90%, that is, greater than 90% is considered effective, and less than 90% is considered ineffective.

[0262] For the molding material in Example 5, after toluene is adsorbed, the adsorbed toluene can be desorbed by heat treating the material, and the material can be regenerated and reused.

[0263] It can be seen from the above results that the metal organic framework molding material of the embodiment of the present invention can better retain the intrinsic structure of the MOFs material and has an adsorption performance comparable to that of the original MOFs material.

[0264] In addition, for the coating process, when the thickness of the substrate is relatively thin, such as only 3mm, the force bearing capacity during the coating process is limited due to the thin thickness. Therefore, after one coating, the substrate is damaged and cannot be used. If other molding processes are used, there is no such requirement for the substrate.

[0265] It can be understood that the household appliances of the present invention, such as fresh air blowers, dehumidifiers, fresh air air conditioners, air purifiers, clothes dryers and dishwashers, etc., have good moisture absorption or air purification effects because the metal organic framework molding material of the present invention is used in the preparation materials. For dehumidifiers, clothes dryers and dishwashers, they can quickly absorb moisture in the air and quickly dehumidify or dry; for fresh air blowers and fresh air air conditioners, they can reduce the humidity in the air and have a good latent heat treatment effect; for air purifiers, they can effectively adsorb and degrade harmful gases in the air to purify the air. The user's experience of household appliances using the metal organic framework molding material of the present invention can be further improved.

[0266] It should be noted that the "load amount" or "coating amount" referred to in the present invention refers to the mass of the slurry loaded (or coated) on the surface of the substrate per unit volume.

[0267] The present invention has been described in detail above in conjunction with the embodiments, but the present invention is not limited to the above embodiments, and various changes can be made within the knowledge scope of ordinary technicians in the relevant technical field without departing from the purpose of the present invention.

Claims

1. A metal organic framework molding material, characterized in that: The raw materials for preparing the metal organic framework molding material include a substrate and a MOFs slurry loaded on the substrate. The MOFs slurry contains MOFs material and a composite binder. The composite binder includes an inorganic binder and an organic binder. The inorganic binder is dispersed in the organic binder.

2. The metal organic framework molding material according to claim 1, characterized in that: The organic binder includes a binder with a molecular chain structure, and the inorganic binder is dispersed in the molecular chain structure of the organic binder.

3. The metal organic framework molding material according to claim 1 or 2, characterized in that: The particle size D50 of the MOFs slurry is 0.5-3 μm.

4. The metal organic framework molding material according to claim 1, characterized in that: The organic binder includes at least one of acrylic resin, polyurethane, epoxy resin, polyol, silicone, sodium hydroxymethyl cellulose, glycerin and starch.

5. The metal organic framework molding material according to claim 1, characterized in that: The inorganic binder includes at least one of silica sol, aluminum sol, aluminum phosphate sol, titanium dioxide sol, clay and kaolin.

6. The metal organic framework molding material according to claim 1, 4 or 5, characterized in that: The inorganic binder accounts for 1% to 40% of the weight of the organic binder.

7. The metal organic framework molding material according to claim 1, characterized in that: The substrate is a porous substrate.

8. The metal organic framework molding material according to claim 1 or 7, characterized in that: The thickness of the substrate is above 5 mm.

9. The metal organic framework molding material according to claim 1 or 7, characterized in that: The substrate is a corrugated substrate, and the corrugated substrate has a corrugation height of 0.5 to 5 mm and a corrugation width of 1 to 5 mm.

10. The metal organic framework molding material according to claim 1 or 7, characterized in that: The substrate is a honeycomb substrate, the honeycomb holes in the honeycomb substrate are hexagonal, the side length of the hexagon is 0.5-10 mm, and the hole wall thickness of the honeycomb holes is 0.1-5 mm.

11. The metal organic framework molding material according to claim 1, characterized in that: The MOFs slurry further contains an auxiliary agent, which includes at least one of a dispersant, a thickener, a leveling agent and a defoamer.

12. A method for preparing a metal organic framework molding material, characterized in that: The steps include: S1, dispersing the inorganic binder in the organic binder to form a homogeneous emulsion to obtain a composite binder; S2, preparing the composite binder and MOFs material into MOFs slurry; S3, forming the MOFs slurry on a substrate, to obtain; Wherein, the inorganic binder is dispersed in the organic binder.

13. The method for preparing a metal organic framework molding material according to claim 12, characterized in that: In the step S1, the inorganic binder is dispersed in the organic binder by ultrasound to form a homogeneous emulsion.

14. The method for preparing a metal organic framework molding material according to claim 12 or 13, characterized in that: In the step S3, the forming includes the step of loading the MOFs slurry on a substrate by vacuum coating.

15. The method for preparing a metal organic framework molding material according to claim 14, characterized in that: In the step S3, the molding further includes the step of drying the coated slurry, and the drying is electromagnetic wave drying.

16. Use of a metal organic framework forming material as a catalyst, catalyst carrier, adsorbent, fluid storage agent, desiccant, ion exchange material, molecular sieve, separation material, material for selective molecular release, material for selective molecular uptake, molecular recognition, sensor, nanotube or nanoreactor, characterized in that: The metal organic framework molding material is the metal organic framework molding material as claimed in any one of claims 1 to 11 or is the metal organic framework molding material prepared by the preparation method as claimed in any one of claims 12 to 15.

17. A water collection device, characterized in that: The raw material for preparing the water collection device includes the metal organic framework forming material as described in any one of claims 1 to 11 or the metal organic framework forming material prepared by the preparation method as described in any one of claims 12 to 15.

18. A gas storage device, characterized in that: The raw material for preparing the gas storage device includes the metal organic framework forming material as described in any one of claims 1 to 11 or the metal organic framework forming material prepared by the preparation method as described in any one of claims 12 to 15.

19. An air purification device, characterized in that: The raw material for preparing the air purification device includes the metal organic framework molding material as described in any one of claims 1 to 11 or the metal organic framework molding material prepared by the preparation method as described in any one of claims 12 to 15.

20. A household appliance, characterized in that: The raw materials for preparing the household appliance include the metal organic framework forming material as described in any one of claims 1 to 11 or the metal organic framework forming material prepared by the preparation method as described in any one of claims 12 to 15.

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