CN115501859A - Metal organic framework forming body, preparation method thereof, method for removing small molecule gas by using metal organic framework forming body and application of metal organic framework forming body - Google Patents

Metal organic framework forming body, preparation method thereof, method for removing small molecule gas by using metal organic framework forming body and application of metal organic framework forming body Download PDF

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CN115501859A
CN115501859A CN202110695815.6A CN202110695815A CN115501859A CN 115501859 A CN115501859 A CN 115501859A CN 202110695815 A CN202110695815 A CN 202110695815A CN 115501859 A CN115501859 A CN 115501859A
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cellulose
organic framework
mil
metal
organic
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李莹
文桂林
张红星
林雨
任悦萌
肖安山
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China Petroleum and Chemical Corp
Sinopec Qingdao Safety Engineering Institute
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China Petroleum and Chemical Corp
Sinopec Qingdao Safety Engineering Institute
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Priority to CN202110695815.6A priority Critical patent/CN115501859A/en
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
    • B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
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    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
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    • B01J20/28016—Particle form
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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    • B01J20/28069—Pore volume, e.g. total pore volume, mesopore volume, micropore volume
    • B01J20/28073—Pore volume, e.g. total pore volume, mesopore volume, micropore volume being in the range 0.5-1.0 ml/g
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    • B01J20/28078—Pore diameter
    • B01J20/2808—Pore diameter being less than 2 nm, i.e. micropores or nanopores
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    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
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    • Y02C20/40—Capture or disposal of greenhouse gases of CO2

Abstract

The invention relates to the technical field of metal organic framework material forming, and discloses a metal organic framework forming body, a preparation method thereof, a method for removing small molecule gas by using the metal organic framework forming body and application of the metal organic framework forming body. The formed body provided by the invention comprises a metal organic framework material and an organic binder; wherein the weight ratio of the organic binder to the metal-organic framework material is 1: (1-100); the shaped bodies contain no inorganic binders. The metal organic framework forming body provided by the invention has higher specific surface area, mechanical strength and adsorption capacity, and can be better used for gas molecule adsorption (such as adsorption of VOCs, adsorption of light hydrocarbon and adsorption of carbon dioxide and other small molecule gases) in the environment.

Description

Metal organic framework forming body, preparation method thereof, method for removing small molecule gas by using metal organic framework forming body and application of metal organic framework forming body
Technical Field
The invention relates to the technical field of metal organic framework material forming, in particular to a metal organic framework forming body, a preparation method thereof, a method for removing small molecule gas by using the metal organic framework forming body and application of the metal organic framework forming body.
Background
The Metal Organic Frameworks (MOFs) are three-dimensional network materials formed by self-assembling metal ions and organic ligands, have the advantages of large specific surface area, developed pore structures, good stability, adjustable pore channels, chemical modification of functional groups and the like, and have wide application prospects in the fields of gas storage, gas adsorption separation, selectivity and chiral catalysts, microreactors, molecular recognition, drug transmission, photoelectric property application and the like. During the last decades, the search for new structures of MOFs materials has been mainly focused, and the future research direction will turn to the real applications of MOFs materials. The MOFs material forming technology is one of the key steps for the industrial application of the porous material. In industrial applications, the shape and size of the target MOF material has a significant impact on the performance of the material during application. The formation of MOFs is essential for practical applications such as adsorption/separation and catalysis, which require the formation of fine nano/crystallite powders of MOFs into macroscopic bodies. In general, MOFs can be shaped into different types by post-synthesis processes (indirect means), i.e. secondary processing of pre-formed crystalline powders. The crystallinity, porosity and functionality of the molded MOFs material should remain intact while having sufficient mechanical and chemical stability and wear resistance to meet the requirements of a given process.
The extrusion method is one of the main methods for granulating and molding the traditional adsorbents and catalysts such as commercial activated carbon, molecular sieves and the like, and the research on the molding of MOFs materials is less. In the extrusion granulation process, a binder, a solvent, or the like is often added to the material. Common granulation binders include inorganic binders such as alumina, but the obtained product has poor performance (low specific surface area, mechanical strength and adsorption capacity).
Therefore, the existing technologies for preparing MOFs materials are in need of improvement.
Disclosure of Invention
The invention aims to overcome the technical problems in the prior art and provides a metal organic framework forming body and a preparation method and application thereof.
In order to achieve the above object, a first aspect of the present invention provides a metal-organic framework molded body comprising a metal-organic framework material (MOFs material) and an organic binder; wherein the weight ratio of the organic binder to the metal-organic framework material is 1: (1-100); the shaped bodies do not contain inorganic binders.
In a second aspect, the present invention provides a method of preparing a metal-organic framework shaped body, the method comprising: mixing organic agent binder and metal organic framework material, and molding;
wherein the weight ratio of the organic binder to the metal-organic framework material is 1: (1-100); the viscosity of the organic binder is more than or equal to 10000 mPas at 25 ℃.
In a third aspect, the present invention provides a method for removing small molecule gas, the method comprising: contacting a sample to be treated containing a small molecule gas with the molded body according to the first aspect;
alternatively, a molded body is prepared according to the method of the second aspect, and then a sample to be treated containing a small molecule gas is brought into contact with the obtained molded body.
In a fourth aspect, the present invention provides a use of the molded article of the first aspect or the molded article prepared by the method of the second aspect for small molecule gas adsorption.
Compared with the prior art, the metal organic framework forming body provided by the invention has higher specific surface area, mechanical strength and adsorption capacity, and can be better used for gas molecule adsorption in the environment (such as adsorption of VOCs, adsorption of light hydrocarbon and adsorption of carbon dioxide and other small molecule gases). In addition, the invention also provides a method for preparing the metal organic framework forming body and application thereof. According to the preparation method provided by the invention, MOFs materials and the organic binder are uniformly mixed, and a proper amount of solvent is added in the forming process to fully mix the MOFs materials and the organic binder, so that columnar particles with different sizes can be obtained, and the columnar particles can be filled in a fixed bed, and the technical defects of process equipment blockage, difficult mass and heat transfer, obvious pressure drop and the like caused by powder materials can be avoided.
Drawings
FIG. 1 is a nitrogen adsorption isotherm (77K) of a Cu-BTC material prepared in accordance with one embodiment of the present invention;
FIG. 2 is a nitrogen adsorption isotherm (77K) of the molded article prepared in example 3.
FIG. 3 is an ethane sorption isotherm diagram of the shaped bodies prepared in example 1.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides in a first aspect a metal-organic framework shaped body comprising a metal-organic framework material and an organic binder; wherein the weight ratio of the organic binder to the metal-organic framework material is 1: (1-100); the shaped bodies contain no inorganic binders.
In the invention, the test method of the viscosity refers to GB/T1632-93 determination of viscosity number and intrinsic viscosity number of polymer dilute solution.
According to some embodiments of the invention, the weight ratio of the organic binder to the metal-organic framework material is 1: (5-50).
According to some embodiments of the invention, the organic binder has a viscosity of more than or equal to 10000 mPas, preferably from 10000 to 200000 mPas, more preferably from 50000 to 150000 mPas at 25 ℃.
According to some embodiments of the invention, the shaped bodies are columnar particles; preferably, the diameter of the columnar particles is 1-6mm, and the length is 1-8mm; more preferably, the columnar particles have a diameter of 2 to 4mm and a length of 2 to 4mm.
According to some embodiments of the invention, the shaped body has a specific surface area of 700 to 3000m 2 A/g, preferably of 800 to 2000m 2 /g。
According to some embodiments of the invention, the average pore diameter of the shaped bodies is between 0.5 and 0.9nm, preferably between 0.6 and 0.8nm.
According to some embodiments of the invention, the pore volume is 0.3-0.9cm 3 Per g, preferably 0.65-0.9cm 3 (ii) in terms of/g. Wherein pore volume refers to micropore volume.
According to some embodiments of the invention, the mechanical strength of the shaped body is between 20 and 200N/Pc, preferably between 50 and 150N/Pc.
According to some embodiments of the invention, the organic binder is a polysaccharide.
Preferably, the molecular weight of the polysaccharide is 100000-1000000, preferably 150000-300000.
Preferably, the polysaccharide is a cellulosic polysaccharide.
According to some embodiments of the present invention, the organic binder may be selected from at least one of methyl cellulose, ethyl cellulose, propyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl methyl cellulose, cellulose triacetate, cyanomethyl cellulose, cyanoethyl cellulose, and cyanopropyl cellulose, preferably from at least one of methyl cellulose, ethyl cellulose, and propyl cellulose.
According to some embodiments of the invention, the metal-organic framework material may have a specific surface area of 1000 to 5000m 2 A/g, preferably from 1200 to 2000m 2 /g。
In the present invention, the metal-organic framework material is at least one selected from the group consisting of Cu-BTC, uiO-66, uiO-67, uiO-68, MIL-53 (Al), MIL-53 (Fe), MIL-53 (Cr), MIL-101 (Al), MIL-101 (Fe), MIL-101 (Cr), MIL-100 (Al), MIL-100 (Fe), and MIL-100 (Cr), and is preferably Cu-BTC.
In the present invention, the source of the metal-organic framework material is not particularly limited, and it can be obtained commercially or prepared by itself by using a conventional technique.
In the present invention, preferably, taking Cu-BTC as an example of the metal-organic framework material, the metal-organic framework material can be prepared by itself according to the following steps: in a solvent, a copper source is contacted with trimesic acid for reaction, and the solid obtained after the reaction is washed and dried in sequence. Preferably, the copper source is dissolved in a solvent, which may be water (preferably deionized water) and ethanol, in advance before the contact reaction is performed. Wherein, the molar ratio of the copper source, the trimesic acid, the water and the ethanol in terms of Cu is 1.5-3. The copper source may be a common substance capable of providing copper ions, preferably copper hydroxide. The conditions of the contacting may include: the temperature is 20-40 deg.C, and the time is 15-30h. The washing conditions may include: the temperature is 50-70 ℃. The drying conditions may include: the temperature is 70-90 ℃. More specifically, the process for the self-preparation of HKUST-1 is as follows: uniformly stirring a copper source, trimesic acid, water and ethanol in a molar ratio of 1.5-3 at room temperature. Washing with absolute ethyl alcohol at 50-70 deg.c, and drying at 70-90 deg.c to obtain HKUST-1 material. Wherein, the copper source can be mixed with water in advance to obtain a mixed solution A, the trimesic acid can be mixed with ethanol in advance to obtain a mixed solution B, and the mixed solution A is slowly introduced into the mixed solution B when the copper source is contacted with the ethanol.
A second aspect of the present invention provides a method for preparing a metal-organic framework shaped body according to the first aspect, comprising: mixing organic agent binder and metal organic framework material, and molding;
wherein the weight ratio of the organic binder to the metal-organic framework material is 1: (1-100); the viscosity of the organic binder is more than or equal to 10000 mPas at 25 ℃.
According to some embodiments of the invention, the method does not comprise the use of an inorganic binder.
According to some embodiments of the invention, the conditions of the mixing may comprise: the temperature is 15-35 deg.C, preferably 20-30 deg.C, and the time is 0.5-6 hr, preferably 1-2 hr.
According to some embodiments of the invention, the mixing is performed under stirring, preferably at a speed of 10-100rpm, more preferably 30-60rpm.
According to some embodiments of the invention, the weight ratio of the organic binder to the metal-organic framework material is 1: (5-50).
According to some embodiments of the invention, the mixing is performed in the presence of a solvent.
According to some embodiments of the present invention, the solvent is used in an amount of 0.5 to 3mL/g, preferably 1 to 2mL/g, based on the total weight of the organic binder and the metal-organic framework material.
Preferably, the solvent is selected from water and/or organic solvents.
More preferably, the volume ratio of water to solvent is (0.1-10): 1, more preferably (0.25-4): 1;
more preferably, the organic solvent is selected from at least one of methanol, ethanol, N-propanol, isopropanol, N-pentanol, benzyl alcohol, butanol, diacetone alcohol, propylene glycol ethyl ether, propylene glycol methyl ether, propylene glycol propyl ether, acetone, methyl ethyl ketone, cyclohexanone, dichloromethane, chloroform, N-dimethylformamide, N-diethylformamide, and is preferably selected from methanol and/or ethanol.
According to some embodiments of the invention, the shaping is by extrusion.
Preferably, the molding is carried out to obtain the molded body as columnar particles, wherein the diameter of the columnar particles is 1-6mm, and the length of the columnar particles is 1-8mm; more preferably, the columnar particles have a diameter of 2 to 4mm and a length of 2 to 4mm.
And/or the shaping conditions are such that the shaped body has a specific surface area of 700 to 3000m 2 A/g, preferably of 800 to 2000m 2 /g。
And/or the shaping conditions are such that the pore size of the shaped bodies is from 0.5 to 0.9nm, preferably from 0.6 to 0.8nm.
And/or the molding conditions are such that the mechanical strength of the molded body is 20-200N/Pc, preferably 50-150N/Pc.
In the present invention, the forming further includes a drying step, wherein the drying manner is not particularly limited, and may be a manner of natural airing and/or drying in a drying device, and preferably, the drying conditions include: the temperature is 60-150 ℃, preferably 80-120 ℃; the time is 5-30h, preferably 12-24h.
According to a most preferred embodiment of the invention, the process for the preparation of the shaped body comprises: mixing 8-12 parts by weight of a Cu-BTC material and 1 part by weight of methylcellulose (viscosity 100000-150000mPa · s) under stirring, and slowly dropwise adding a solvent thereto until the mixture becomes a paste; then extruding the mixture into 2-4mm columnar particles, airing, and drying at 100-120 ℃ for 12-16h to obtain a forming body; wherein the solvent is used in an amount of 1.5-2.5mL relative to 1g of the sum of the Cu-BTC material and the methylcellulose, and the solvent is selected from water and ethanol; volume ratio of water to ethanol (1.5-3): 1.
in a third aspect, the present invention provides a method for removing small molecule gases, the method comprising: contacting a sample to be treated containing a small molecule gas with the shaped body according to the first aspect;
alternatively, a molded body is prepared according to the method described in the foregoing second aspect, and then a sample to be treated containing a small molecule gas is brought into contact with the resulting molded body.
In the present invention, the amount of the molded article is not particularly limited, and it is preferable that the molded article is used in an amount of 0.5 to 2g per gram of the sample to be treated in terms of the small molecule gas.
Preferably, the conditions of the contacting include: the temperature is 15-40 ℃.
In the present invention, in order to sufficiently remove the solvent or water vapor adsorbed in the gaps of the molded body and maximize the adsorption property of the material, the method further comprises activating the molded body before contacting with the sample to be treated, wherein the activating condition can comprise that the temperature is 140-160 ℃, and the activating time can be 2-5h.
In a fourth aspect, the present invention provides the use of a shaped body according to the first aspect or a shaped body prepared according to the method of the second aspect for adsorption of small gas molecules.
According to some embodiments of the invention, the small molecule gas may be selected from light hydrocarbons (e.g., C1-C6 light hydrocarbons), CO 2 And CO, preferably selected from methane, ethane, propane, CO 2 And CO. The sample to be treated containing light hydrocarbon can be oil gas produced by refining industry and/or oil storage.
The present invention will be described in detail below by way of examples.
Preparation example 1
Mixing Cu (OH) 2 (19.5g, 0.2mol) is added into deionized water and stirred evenly; trimesic acid (42g, 0.2mol) was added to ethanol and stirred well. Cu (OH) 2 The molar ratio/trimesic acid/deionized water/ethanol was 1. Mixing Cu (OH) 2 The aqueous solution of (2) was slowly introduced into an ethanol solution of trimesic acid, and stirred at room temperature for 24 hours. The solid was separated by centrifugation (3500rpm, 20min), and the solid was washed twice with anhydrous ethanol at 60 ℃. And drying the solid in an oven at 80 ℃ to obtain the Cu-BTC material. The product obtained is the Cu-BTC material used in the examples proved by X-ray powder diffraction detection. The X-ray powder diffraction test conditions are as follows: the German Bruker-AXS D8 type X-ray full-automatic diffractometer is adopted, a light source adopts a radiation source Cu target Kalpha radiation, the tube pressure is 30kV, the tube flow is 30mA, the scanning is continuously carried out, the scanning speed is 2 degrees/min, and the scanning range is 2 degrees to 20 degrees.
The specific surface area of the Cu-BTC material prepared by the preparation example is 1750m 2 /g。
Example 1
9.9g of Cu-BTC material and 0.1g of methylcellulose (with the viscosity of 50000mPa & s) are weighed into a beaker respectively, are stirred sufficiently for 1 hour by a glass rod and are mixed uniformly, and then solvent water/ethanol (with the volume ratio of 1:0, 10 mL) is slowly added dropwise under stirring until the mixture becomes pasty. Then placing the mixture into a miniature single-screw extruder (Tianjin North ocean chemical plant, inc., model TBL-3), extruding into long 2-4mm columnar particles, air drying, and drying in a vacuum oven at 80 deg.C for 24h to obtain the molded body.
Example 2
9.5g of the Cu-BTC material and 0.1g of methylcellulose (viscosity 100000mPa & s) are weighed into a beaker respectively, are stirred sufficiently for 1.5h by a glass rod and are mixed uniformly, and then the solvent water/ethanol (4:1, 10 mL) is slowly added dropwise under stirring until the mixture is pasty. And then placing the mixture into a miniature single-screw extruder, extruding the mixture into long 3-5mm columnar granules, airing the granules, and placing the granules into a vacuum oven to dry the granules for 18 hours at the temperature of 100 ℃ to obtain a formed body.
Example 3
9g of Cu-BTC material and 1g of methylcellulose (viscosity 150000 mPas) are weighed into a beaker respectively, stirred well with a glass rod for 2h and mixed uniformly, and then the solvent water/ethanol (2:1, 10 mL) is slowly added dropwise with stirring until the mixture becomes pasty. And then placing the mixture into a miniature single-screw extruder, extruding the mixture into long 2-4mm columnar granules, airing the granules, and placing the granules in a vacuum oven to dry the granules for 12 hours at 120 ℃ to obtain a formed body.
Example 4
Weighing 8g of Cu-BTC material and 2g of methylcellulose (with the viscosity of 50000mPa & s) into a beaker, fully stirring with a glass rod for 1h, uniformly mixing, and then slowly dropwise adding solvent water/ethanol (1:1, 10 mL) under stirring until the mixture is pasty. And then placing the mixture into a miniature single-screw extruder, extruding the mixture into long 3-5mm columnar granules, airing the granules, and placing the granules in a vacuum oven to dry the granules for 24 hours at the temperature of 80 ℃ to obtain a formed body.
Example 5
7g of the Cu-BTC material and 3g of methylcellulose (with the viscosity of 100000mPa & s) are weighed into a beaker respectively, are stirred sufficiently for 1.5h by a glass rod and are mixed uniformly, and then the solvent water/ethanol (1:2, 10 mL) is slowly added dropwise under stirring until the mixture becomes pasty. And then placing the mixture into a miniature single-screw extruder, extruding the mixture into long 2-4mm columnar granules, airing the granules, and placing the granules in a vacuum oven to dry the granules for 18 hours at the temperature of 100 ℃ to obtain a formed body.
Example 6
5g of Cu-BTC material and 5g of methylcellulose (viscosity 150000 mPas) are weighed into a beaker respectively, stirred well with a glass rod for 2h and mixed uniformly, and then the solvent water/ethanol (1:4, 10 mL) is slowly added dropwise with stirring until the mixture becomes pasty. And then placing the mixture into a miniature single-screw extruder, extruding the mixture into long 3-5mm columnar granules, airing the granules, and placing the granules in a vacuum oven to dry the granules for 12 hours at 120 ℃ to obtain a formed body.
Example 7
9.9g of Cu-BTC material and 0.1g of methylcellulose (viscosity 50000mPa & s) are weighed into a beaker respectively, are stirred sufficiently for 1 hour by a glass rod and are mixed uniformly, and then solvent water/ethanol (1:0, 15 mL) is slowly added dropwise under stirring until the mixture becomes pasty. And then placing the mixture into a miniature single-screw extruder, extruding the mixture into long 2-4mm columnar granules, airing the granules, and placing the granules in a vacuum oven to dry the granules for 24 hours at the temperature of 80 ℃ to obtain a formed body.
Example 8
9.5g of the Cu-BTC material and 0.5g of methylcellulose (viscosity 100000mPa & s) are weighed into a beaker respectively, are stirred sufficiently for 1.5h by a glass rod and are mixed uniformly, and then the solvent water/ethanol (4:1, 15 mL) is slowly added dropwise under stirring until the mixture is pasty. And then placing the mixture into a miniature single-screw extruder, extruding the mixture into long 3-5mm columnar granules, airing the granules, and placing the granules in a vacuum oven to dry the granules for 18 hours at the temperature of 100 ℃ to obtain a formed body.
Example 9
9g of the Cu-BTC material and 1g of methylcellulose (viscosity 150000mPa · s) are weighed into a beaker respectively, mixed uniformly with a glass rod under thorough stirring for 2h, and then the solvent water/ethanol (2:1, 15 mL) is slowly added dropwise with stirring until the mixture is pasty. And then placing the mixture into a miniature single-screw extruder, extruding the mixture into long 2-4mm columnar granules, airing the granules, and placing the granules in a vacuum oven to dry the granules for 12 hours at 120 ℃ to obtain a formed body.
Example 10
Weighing 8g of Cu-BTC material and 2g of methylcellulose (with the viscosity of 50000mPa & s) into a beaker, fully stirring with a glass rod for 1h, uniformly mixing, and then slowly dropwise adding solvent water/ethanol (1:1, 15 mL) under stirring until the mixture is pasty. And then placing the mixture into a miniature single-screw extruder, extruding the mixture into long 3-5mm columnar granules, airing the granules, and placing the granules into a vacuum oven to dry the granules for 24 hours at the temperature of 80 ℃ to obtain a formed body.
Example 11
7g of the Cu-BTC material and 3g of methylcellulose (with the viscosity of 100000mPa & s) are weighed into a beaker respectively, are stirred sufficiently for 1.5h by a glass rod and are mixed uniformly, and then solvent water/ethanol (1:2, 15 mL) is slowly added dropwise under stirring until the mixture becomes pasty. And then placing the mixture into a miniature single-screw extruder, extruding the mixture into long 2-4mm columnar particles, airing the particles, and placing the particles in a vacuum oven to dry the particles for 18 hours at the temperature of 100 ℃ to obtain a formed body.
Example 12
5g of Cu-BTC material and 5g of methylcellulose (viscosity 150000mPa · s) are weighed into a beaker respectively, mixed uniformly with a glass rod under thorough stirring for 2h, and then the solvent water/ethanol (1:4, 15 mL) is slowly added dropwise with stirring until the mixture is pasty. And then placing the mixture into a miniature single-screw extruder, extruding the mixture into long 3-5mm columnar granules, airing the granules, and placing the granules in a vacuum oven to dry the granules for 12 hours at 120 ℃ to obtain a formed body.
Example 13
9.9g of Cu-BTC material and 0.1g of methylcellulose (viscosity 50000mPa & s) are weighed into a beaker respectively, are stirred sufficiently for 1 hour by a glass rod and are mixed uniformly, and then solvent water/ethanol (1:0, 20 mL) is slowly added dropwise under stirring until the mixture becomes pasty. And then placing the mixture into a miniature single-screw extruder, extruding the mixture into long 2-4mm columnar granules, airing the granules, and placing the granules in a vacuum oven to dry the granules for 24 hours at the temperature of 80 ℃ to obtain a formed body.
Example 14
9.5g of the Cu-BTC material and 0.5g of methylcellulose (viscosity 100000mPa & s) are weighed into a beaker respectively, are stirred sufficiently for 1.5h by a glass rod and are mixed uniformly, and then the solvent water/ethanol (4:1, 20 mL) is slowly added dropwise under stirring until the mixture is pasty. And then placing the mixture into a miniature single-screw extruder, extruding the mixture into long 3-5mm columnar granules, airing the granules, and placing the granules in a vacuum oven to dry the granules for 18 hours at the temperature of 100 ℃ to obtain a formed body.
Example 15
9g of the Cu-BTC material and 1g of methylcellulose (viscosity 150000mPa · s) are weighed into a beaker respectively, mixed uniformly with a glass rod under thorough stirring for 2h, and then the solvent water/ethanol (2:1, 20 mL) is slowly added dropwise with stirring until the mixture is pasty. And then placing the mixture into a miniature single-screw extruder, extruding the mixture into long 2-4mm columnar granules, airing the granules, and placing the granules in a vacuum oven to dry the granules for 12 hours at 120 ℃ to obtain a formed body.
Example 16
Weighing 8g of Cu-BTC material and 2g of methylcellulose (with the viscosity of 50000mPa & s) into a beaker, fully stirring with a glass rod for 1h, uniformly mixing, and then slowly dropwise adding solvent water/ethanol (1:1, 20 mL) under stirring until the mixture is pasty. And then placing the mixture into a miniature single-screw extruder, extruding the mixture into long 3-5mm columnar granules, airing the granules, and placing the granules into a vacuum oven to dry the granules for 24 hours at the temperature of 80 ℃ to obtain a formed body.
Example 17
7g of the Cu-BTC material and 3g of methylcellulose (with the viscosity of 100000mPa & s) are weighed into a beaker respectively, are stirred sufficiently for 1.5h by a glass rod and are mixed uniformly, and then solvent water/ethanol (1:2, 20 mL) is slowly added dropwise under stirring until the mixture becomes pasty. And then placing the mixture into a miniature single-screw extruder, extruding the mixture into long 2-4mm columnar granules, airing the granules, and placing the granules in a vacuum oven to dry the granules for 18 hours at the temperature of 100 ℃ to obtain a formed body.
Example 18
5g of Cu-BTC material and 5g of methylcellulose (viscosity 150000mPa · s) are weighed into a beaker respectively, mixed uniformly with a glass rod under thorough stirring for 2h, and then the solvent water/ethanol (1:4, 20 mL) is slowly added dropwise with stirring until the mixture is pasty. And then placing the mixture into a miniature single-screw extruder, extruding the mixture into long 3-5mm columnar granules, airing the granules, and placing the granules in a vacuum oven to dry the granules for 12 hours at 120 ℃ to obtain a formed body.
Example 19
The procedure is as in example 15, except that methylcellulose having a viscosity of 10000 mPas is used.
Example 20
The procedure is as in example 15, except that methylcellulose having a viscosity of 200000 mPas is used.
Example 21
The procedure is as in example 15, except that the Cu-BTC material is replaced by an equal amount of MIL-100 (Fe) material.
Example 22
The procedure is as in example 15, except that 0.5g of methylcellulose (viscosity 150000 mPas) and 0.5g of the inorganic binder alumina are used instead of the methylcellulose (viscosity 150000 mPas) in example 15.
Comparative example 1
9.9g of Cu-BTC material and 0.1g of inorganic binder aluminum oxide are respectively weighed into a beaker, fully stirred for 1 hour by a glass rod and uniformly mixed, and then the solvent water/ethanol (1:0, 15 mL) is slowly added dropwise under stirring until the mixture becomes pasty. And then placing the mixture into a miniature single-screw extruder, extruding the mixture into long 2-4mm columnar granules, airing the granules, and placing the granules in a vacuum oven to dry the granules for 24 hours at the temperature of 80 ℃ to obtain a formed body.
Comparative example 2
9.5g of Cu-BTC material and 0.1g of inorganic binder alumina are respectively weighed in a beaker, fully stirred by a glass rod for 1.5h and uniformly mixed, and then the solvent water/ethanol (4:1, 15 mL) is slowly added dropwise under stirring until the mixture is pasty. And then placing the mixture into a miniature single-screw extruder, extruding the mixture into long 3-5mm columnar granules, airing the granules, and placing the granules in a vacuum oven to dry the granules for 18 hours at the temperature of 100 ℃ to obtain a formed body.
Comparative example 3
9g of Cu-BTC material and 1g of inorganic binder alumina are respectively weighed in a beaker, fully stirred for 2 hours by a glass rod and uniformly mixed, and then the solvent water/ethanol (2:1, 15 mL) is slowly added dropwise under stirring until the mixture becomes pasty. And then placing the mixture into a miniature single-screw extruder, extruding the mixture into long 2-4mm columnar granules, airing the granules, and placing the granules in a vacuum oven to dry the granules for 12 hours at 120 ℃ to obtain a formed body.
Comparative example 4
Respectively weighing 8g of Cu-BTC material and 2g of inorganic binder alumina in a beaker, fully stirring for 1h by using a glass rod, uniformly mixing, and then slowly dropwise adding solvent water/ethanol (1:1, 15 mL) under stirring until the mixture becomes paste. And then placing the mixture into a miniature single-screw extruder, extruding the mixture into long 3-5mm columnar granules, airing the granules, and placing the granules in a vacuum oven to dry the granules for 24 hours at the temperature of 80 ℃ to obtain a formed body.
Comparative example 5
7g of Cu-BTC material and 3g of inorganic binder alumina are respectively weighed into a beaker, fully stirred for 1.5h by a glass rod and uniformly mixed, and then the solvent water/ethanol (1:2, 15 mL) is slowly added dropwise under stirring until the mixture becomes pasty. And then placing the mixture into a miniature single-screw extruder, extruding the mixture into long 2-4mm columnar granules, airing the granules, and placing the granules in a vacuum oven to dry the granules for 18 hours at the temperature of 100 ℃ to obtain a formed body.
Comparative example 6
5g of Cu-BTC material and 5g of inorganic binder alumina are respectively weighed in a beaker, fully stirred for 2 hours by a glass rod and uniformly mixed, and then the solvent water/ethanol (1:4, 15 mL) is slowly dripped under stirring until the mixture becomes pasty. And then placing the mixture into a miniature single-screw extruder, extruding the mixture into long 3-5mm columnar granules, airing the granules, and placing the granules in a vacuum oven to dry the granules for 12 hours at 120 ℃ to obtain a formed body.
Comparative example 7
The procedure is as in example 15, except that methylcellulose having a viscosity of 5000 mPas is used.
Test example 1
The samples obtained in the examples and comparative examples were subjected to the performance test in the following manner, and the results are shown in table 1:
(1) Examples and comparative examples N of samples was obtained 2 The adsorption-desorption curve was measured on a specific surface apparatus of model ASAP2020, mcMack USA, evacuated and degassed at 150 ℃ for 12h, weighed and transferred to an analysis station, subjected to N at 77K 2 Determining an adsorption-desorption isotherm; calculating the specific surface area of the sample by Brunauer-Emett-Teller (BET) method; the pore size distribution of the sample was calculated by the Barrett-Joyner-Halenda (BJH) method; the pore volume (micropore volume) of the sample was calculated by the H-K (Original) method.
(2) The volume (crush) strength of the samples obtained in the examples and comparative examples was determined by a frictionless piston test: a shaped body pellet was placed in a cylindrical container (inner diameter 3 cm). The piston then exerts a mechanical force by gravity, which is increased by increasing the weight on the piston until the particles collapse. The compressive strength of the individual particles is expressed as the weight they can bear before comminution and the average of 10 measurements is calculated.
(3) Examples and comparative examples the absorption-desorption curves of the light hydrocarbons (ethane) of the samples obtained were tested on a specific surface instrument, model ASAP2020, mck usa, degassed under vacuum at 150 ℃ for 12h, weighed and transferred to an analysis station, and the absorption-desorption curves were measured at 298K at a pressure range of 0-2bar for ethane and propane, from which the static maximum absorption of the sample in this pressure range was obtained.
TABLE 1
Figure BDA0003128316140000161
Figure BDA0003128316140000171
As can be seen from the results in Table 1, examples 1-6,7-12,13-18 are all formed Cu-BTC with different organic binder specific gravities. From the results in Table 1, it is understood that as the specific gravity of the binder increases, the specific surface area of the molded article decreases, the pore diameter becomes smaller, and the ethane adsorption amount decreases, but the mechanical strength increases. In comparative examples 1 to 6,7 to 12,13 to 18, the specific surface area of the molded article did not change much with an increase in the amount of solvent added, but the mechanical strength decreased. Comparative examples 1 to 6 are Cu-BTC molded bodies prepared by using an inorganic alumina binder, and compared with examples 1 to 6,7 to 12,13 to 18, the molded bodies have smaller specific surface area, smaller pore size distribution and relatively smaller ethane adsorption amount, because the inorganic binder has small size and blocks partial pore channels of Cu-BTC in the preparation process of the molded bodies. Example 19 produced a shaped material having a specific surface area equivalent to that of example 15, but having a mechanical strength and an ethane-adsorbing amount lower than those of example 15. Example 20 used an organic binder having a higher viscosity than that of example 15, produced a shaped material having a specific surface area equivalent to that of example 15 and a mechanical strength higher than that of example 15, but having a lower ethane adsorption amount than that of example 15. Although the specific surface area and mechanical strength of the shaped material prepared in example 21 are similar to those of example 15, the adsorption amount of ethane is lower than that of example 15 because MIL-100 (Fe) is selected as a mesoporous material. The material prepared in comparative example 7 has a specific surface area and a pore size distribution similar to those of example 15, but has a mechanical strength and an ethane adsorption amount significantly lower than those of example 15. Comparing example 15 with example 22, it can be seen that the method of the present invention can further improve the specific surface area, pore size and ethane adsorption amount without using an inorganic binder.
Test example 2
The same test method as in test example 1 was used to test the adsorption performance of the molding material prepared in example 15 on benzene vapor, and the adsorption amount of benzene-saturated vapor was 180mg/g, and the adsorption amount of benzene was 576mg/g for the mesoporous MIL-100 (Fe) molding material prepared in example 21.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.

Claims (16)

1. A metal-organic framework molded body, characterized in that the molded body comprises a metal-organic framework material and an organic binder; wherein the weight ratio of the organic binder to the metal-organic framework material is 1: (1-100); the shaped bodies contain no inorganic binders.
2. Shaped body according to claim 1, wherein the weight ratio of the organic binder to the metal-organic framework material is 1: (5-50);
and/or the viscosity of the organic binder at 25 ℃ is not less than 10000 mPas, preferably 10000 to 200000 mPas, more preferably 50000 to 150000 mPas.
3. Shaped body according to claim 1 or 2, wherein the shaped body is a columnar particle; preferably, the diameter of the columnar particles is 1-6mm, and the length is 1-8mm; more preferably, the columnar particles have a diameter of 2-4mm and a length of 2-4mm;
and/or the specific surface area of the molded body is 700-3000m 2 A/g, preferably of 800 to 2000m 2 /g；
And/or the average pore diameter of the shaped bodies is from 0.5 to 0.9nm, preferably from 0.6 to 0.8nm; pore volume is 0.3-0.9cm 3 (ii)/g; preferably 0.65-0.9cm 3 /g；
And/or the mechanical strength of the molded body is 20-200N/Pc, preferably 50-150N/Pc.
4. Shaped body according to any one of claims 1 to 3, wherein the organic binder is a polysaccharide;
preferably, the polysaccharide has a molecular weight of 100000-1000000, preferably 150000-300000;
preferably, the polysaccharide is a cellulosic polysaccharide.
5. Shaped body according to any one of claims 1 to 4, wherein the organic binder is selected from at least one of methyl cellulose, ethyl cellulose, propyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl methyl cellulose, cellulose triacetate, cyanomethyl cellulose, cyanoethyl cellulose and cyanopropyl cellulose, preferably from at least one of methyl cellulose, ethyl cellulose and propyl cellulose.
6. Shaped body according to any one of claims 1 to 5, wherein the metal-organic framework material has a specific surface area of 1000 to 5000m 2 A/g, preferably of 1200 to 2000m 2 /g。
7. Shaped body according to any one of claims 1 to 6, wherein the metal-organic framework material is selected from at least one of Cu-BTC, uiO-66, uiO-67, uiO-68, MIL-53 (Al), MIL-53 (Fe), MIL-53 (Cr), MIL-101 (Al), MIL-101 (Fe), MIL-101 (Cr), MIL-100 (Al), MIL-100 (Fe) and MIL-100 (Cr), preferably Cu-BTC.
8. A method of preparing a metal-organic framework shaped body, characterized in that the method comprises: mixing organic agent binder and metal organic framework material, and molding;
wherein the weight ratio of the organic binder to the metal-organic framework material is 1: (1-100); the viscosity of the organic binder is more than or equal to 10000 mPas at 25 ℃.
9. The method of claim 8, wherein the method does not include the use of an inorganic binder.
10. The method of claim 8 or 9, wherein the conditions of mixing comprise: the temperature is 15-35 ℃, preferably 20-30 ℃, and the time is 0.5-6h, preferably 1-2h;
and/or, the mixing is carried out under stirring, preferably, the rotation speed of the stirring is 10-100rpm, more preferably 30-60rpm;
and/or the weight ratio of the organic binder to the metal-organic framework material is 1: (5-50);
and/or the viscosity of the organic binder at 25 ℃ is 10000 to 200000 mPas, preferably 50000 to 150000 mPas.
11. The method of any one of claims 8-10, wherein the mixing is performed in the presence of a solvent;
and/or, the dosage of the solvent is 0.5-3mL/g, preferably 1-2mL/g, based on the total weight of the organic binder and the metal-organic framework material;
preferably, the solvent is selected from water and/or organic solvents;
preferably, the volume ratio of water to solvent is (0.1-10): 1, more preferably (0.25-4): 1;
preferably, the organic solvent is selected from at least one of methanol, ethanol, N-propanol, isopropanol, N-pentanol, benzyl alcohol, butanol, diacetone alcohol, propylene glycol ethyl ether, propylene glycol methyl ether, propylene glycol propyl ether, acetone, methyl ethyl ketone, cyclohexanone, dichloromethane, chloroform, N-dimethylformamide, N-diethylformamide, and is preferably selected from methanol and/or ethanol.
12. The method according to any one of claims 8-11, wherein the forming is by extrusion;
preferably, the molding is carried out so that the obtained molded body is columnar particles, wherein the diameter of the columnar particles is 1-6mm, and the length of the columnar particles is 1-8mm; more preferably, the columnar particles have a diameter of 2-4mm and a length of 2-4mm;
and/or the shaping conditions are such that the shaped body has a specific surface area of 700 to 3000m 2 A/g, preferably of 800 to 2000m 2 /g；
And/or the shaping conditions are such that the pore size of the shaped body is from 0.5 to 0.9nm, preferably from 0.6 to 0.8nm;
and/or the molding conditions are such that the mechanical strength of the molded body is 20-200N/Pc, preferably 50-150N/Pc.
13. The method of any one of claims 8-12, wherein the organic binder is a polysaccharide;
preferably, the polysaccharide has a molecular weight of 100000-1000000, preferably 150000-300000;
preferably, the polysaccharide is a cellulosic polysaccharide;
and/or the organic binder is selected from at least one of methyl cellulose, ethyl cellulose, propyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl methyl cellulose, cellulose triacetate, cyanomethyl cellulose, cyanoethyl cellulose and cyanopropyl cellulose, preferably from at least one of methyl cellulose, ethyl cellulose and propyl cellulose;
and/or the specific surface area of the metal organic framework material is 1000-5000m 2 A/g, preferably of 1200 to 2000m 2 /g；
And/or the metal organic framework material is selected from at least one of Cu-BTC, uiO-66, uiO-67, uiO-68, MIL-53 (Al), MIL-53 (Fe), MIL-53 (Cr), MIL-101 (Al), MIL-101 (Fe), MIL-101 (Cr), MIL-100 (Al), MIL-100 (Fe) and MIL-100 (Cr), preferably Cu-BTC.
14. A method for removing small molecule gases, the method comprising: contacting a sample to be treated containing a small molecule gas with the shaped body according to any one of claims 1 to 7;
alternatively, a shaped body is produced according to the method of any one of claims 8 to 13, and the sample to be treated containing a small molecule gas is then brought into contact with the shaped body obtained.
15. Use of the shaped bodies according to any of claims 1 to 7 or the shaped bodies produced by the process according to any of claims 8 to 13 for the adsorption of small molecule gases.
16. The use of claim 15, wherein the small molecule gas is selected from the group consisting of light hydrocarbons, CO 2 And CO, preferably selected from methane, ethane, propane, CO 2 And CO.
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CN107774233A (en) * 2016-08-29 2018-03-09 中国石油化工股份有限公司 A kind of formed body of metal-organic framework materials and preparation method and application
CN108620023A (en) * 2017-03-23 2018-10-09 中国石油化工股份有限公司 A kind of enhanced thermal conduction type metal organic framework formed body and preparation method thereof
CN107029670A (en) * 2017-04-20 2017-08-11 华中科技大学 A kind of metal organic framework moulding material and its forming method
CN109486208A (en) * 2017-09-09 2019-03-19 中国石油化工股份有限公司 A kind of metal organic framework formed body and preparation method thereof
CN112679965A (en) * 2019-10-17 2021-04-20 中国石油化工股份有限公司 Metal organic framework forming body and preparation method and application thereof
CN112705168A (en) * 2021-01-18 2021-04-27 太原理工大学 Forming method of ultra-microporous MOF adsorbent material
CN112717888A (en) * 2021-01-18 2021-04-30 太原理工大学 Application of ultra-microporous MOF adsorbent material in hydrocarbon gas separation

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