Forming method of metal organic framework material for CO2 capture

Abstract

The invention belongs to the technical field of MOF (Metal Organic Framework) materials, and discloses a forming method of a metal organic framework material for CO2 capture, which comprises the following steps: S1, preparing a binder solution; s2, pretreating the waste paper pulp to obtain a structural aid; the pretreatment comprises impurity removal, pulping and drying treatment on the waste paper pulp; s3, carrying out mixing and granulation on the MOF material; a binder solution, a structural auxiliary agent, MOF powder and deionized water are mixed and stirred evenly to form a pasty material, then granulation is conducted, the total adding amount of the binder effective components and the structural auxiliary agent is not larger than 6% of the MOF powder, and the ratio of the binder effective components to the structural auxiliary agent is 1: 2-2: 1; and S4, carrying out gradient drying on the spherical wet particles. According to the invention, the particle strength and water resistance of the formed MOF material are improved, and multiple requirements of high strength, high adsorption retention and strong water resistance are synchronously realized.

Description

Technical Field

[0001] This invention belongs to the field of MOF material technology, specifically relating to a molding method for a metal-organic framework material for CO2 capture. Background Technology

[0002] Currently, the molding technology for traditional adsorbents such as molecular sieves and activated carbon is relatively mature: typically, a small amount of binder is used to form primary low-strength particles, and then high-temperature sintering (500~800℃) is used to further strengthen the interfacial bonding, ultimately obtaining industrial-grade particles with a compressive strength ≥50N. However, the crystal structure of MOF materials is extremely sensitive to high temperatures. Under high-temperature environments, framework decomposition and loss of adsorption active sites are prone to occur, making it impossible to improve strength using traditional high-temperature sintering processes. Instead, a stable structure can only be formed through the interfacial interaction between the binder and MOF particles, resulting in MOF material molding technology still being in the early exploratory stage.

[0003] The existing MOF molding methods generally have three major defects, which seriously restrict their large-scale application: (1) Insufficient particle mechanical strength. The compressive strength of particles prepared by most molding technologies is ≤40N, which is far from meeting the industrial equipment requirement of particle strength ≥50N. They are prone to breakage and dust generation under bed impact and airflow disturbance; (2) Severe degradation of adsorption performance. In order to improve strength, a large amount of functional additives such as binders (usually ≥8%) need to be added. Excessive additives can easily block the micropore channels of MOF and cover the adsorption active sites, resulting in a significant decrease in CO2 adsorption, which may exceed 20%; (3) Lack of water resistance. The existing technology has not optimized the formula for the 5~10% moisture content in industrial flue gas. The molded particles are prone to interface dissociation and sudden drop in strength in humid environments. The water resistance does not meet the needs of practical applications.

[0004] Specifically, the patent technology with application number 202110063750.3 uses a polyvinyl alcohol and methylcellulose composite bonding system to mold ZIF-7 powder for ethane / ethylene mixture separation. The molded particle strength is only slightly above 40N, and the binder content is as high as 8% or more, resulting in high molding costs and a risk of adsorption performance degradation. In the patent with application number 202410748345.9, a similar composite bonding system is used to mold other types of MOF materials (such as copper adamantane tetracarboxylate), but the particle strength can only reach below 15N. This further indicates that the composite bonding system has extremely poor universality for MOF material molding—it can achieve low-strength molding for some MOFs, but completely fails to meet the strength requirements for others, and none of them reach the ≥50N strength standard required for industrial applications. Furthermore, none of the above-mentioned existing technologies involve water resistance design and performance verification, making them unsuitable for the actual working conditions of industrial flue gas containing moisture. Therefore, in the existing technology, how to ensure that MOF materials used for CO2 capture meet the requirements of mechanical strength, adsorption performance retention and water resistance simultaneously after molding has become a technical problem that needs to be solved. Summary of the Invention

[0005] The purpose of this invention is to provide a molding method for metal-organic framework materials for CO2 capture, so as to solve the technical problem that existing MOF materials are difficult to simultaneously meet the requirements of mechanical strength, adsorption performance retention and water resistance.

[0006] The method for molding a metal-organic framework material for CO2 capture includes the following steps: S1. Prepare the adhesive solution; S2. Pre-treat waste paper pulp to obtain structural additives; the pre-treatment includes removing impurities, beating and drying the waste paper pulp; S3. Mix and granulate the MOF material; mix the binder solution, structural aid, MOF powder and deionized water and stir evenly to form a paste, then granulate. The total amount of binder active ingredients and structural aids added together should not exceed 6% of the MOF powder, and the ratio between binder active ingredients and structural aids should be 1:2 to 2:1. S4. Gradient drying of spherical wet particles.

[0007] Preferably, in step S2, the impurity removal treatment of waste paper pulp includes: adding waste paper pulp to a mixing tank, adding deionized water at a solid-liquid ratio of 1:10 to 1:15, and then adding 0.5 to 1 wt% of alkaline substance by weight of waste paper pulp, stirring at 50 to 60°C for 30 to 60 minutes; filtering through a sieve to remove large particulate impurities, and then centrifuging at 3000 to 5000 r / min for 10 to 15 minutes to remove fine filler impurities.

[0008] Preferably, in step S2, the pulping process for waste paper pulp includes: adding the purified pulp after impurity removal to a double-disc refiner, refining to a fiber length of 150~400μm, and controlling the freeness to 30~45°SR to obtain pulp.

[0009] Preferably, in step S2, the drying treatment of waste paper pulp includes: placing the pulped material in a forced-air drying oven at 80~95℃ for 4~8 hours until the moisture content is ≤1wt%, thereby obtaining pretreated waste paper pulp.

[0010] Preferably, in step S1, PVA powder with a molecular weight of not less than 170,000 is mixed with deionized water, and the mass concentration of the resulting solution is 5-10%. The solution is placed in a constant temperature water bath at 90-95°C and stirred at a rate of 300-500 r / min for 30-60 min until the solution is clear and transparent. After cooling to 25-50°C, a PVA adhesive solution is obtained.

[0011] Preferably, in step S3, a PVA binder solution consisting of 100 parts MOF powder, 2-4 parts pretreated waste paper pulp, and 2-4 parts PVA active ingredient is mixed with added deionized water, so that the total amount of deionized water in the mixture is 40-90 parts after adding deionized water.

[0012] Preferably, in step S3, the mixture is stirred for 30 to 120 minutes at a temperature of 25 to 90°C and a rotation speed of 50 to 1000 r / min to form a uniform and plastic paste, and the resulting spherical wet particles are granulated.

[0013] Preferably, in step S4, the spherical wet particles obtained in step S3 are first dried at 60~80℃ for 2~4h, and then the temperature is raised to 110~150℃ for 4~24h.

[0014] Preferably, the MOF powder is made of any one of Cu-BTC, calf-20, or Co-MOF-74.

[0015] Preferably, the waste paper pulp is recycled plant fiber pulp, and the source includes one or more of office waste paper, packaging waste paper, and cultural waste paper.

[0016] The technical advantages of this invention are as follows: This invention employs a targeted treatment process on waste paper pulp, resulting in abundant hydroxyl groups on the surface of the fiber structure. The fibers further form a 150-400 μm three-dimensional interwoven network, providing structural support. While ensuring structural strength, an appropriate amount of binding agent is incorporated, creating a synergistic effect of bonding and support, simultaneously improving the strength and water resistance of the molded MOF material particles. This material, combined with a gradient drying process, slowly removes the solvent, protecting the crystal structure and adsorption active sites of the MOF material. This method simultaneously achieves multiple requirements for high strength, high adsorption retention, and strong water resistance, addressing the core pain points of existing technologies from a mechanistic perspective and better supporting the industrial application of MOF materials. Attached Figure Description

[0017] Figure 1 This is a basic flowchart of a molding method for a metal-organic framework material for CO2 capture according to the present invention.

[0018] Figure 2 The physical adsorption curves of CO2 for Cu-BTC powder at room temperature (pressure range 0-800 Torr).

[0019] Figure 3 The physical adsorption curves of CO2 for Co-MOF-74 powder at room temperature (pressure range 0-800 Torr).

[0020] Figure 4 The physical adsorption curves of CO2 for calf-20 powder at room temperature (pressure range 0-800 Torr).

[0021] Figure 5 The CO2 physical adsorption curve of the product in Example 1 of this invention at room temperature (pressure range 0-800 Torr).

[0022] Figure 6 The CO2 physical adsorption curve of the product in Example 3 of this invention at room temperature (pressure range 0-800 Torr).

[0023] Figure 7 The CO2 physical adsorption curve of the product in Example 5 of this invention at room temperature (pressure range 0-800 Torr).

[0024] Figure 8 The CO2 physical adsorption curve of the product of Comparative Example 1 of this invention at room temperature (pressure range 0-800 Torr).

[0025] Figure 9 The CO2 physical adsorption curve of the product of Comparative Example 2 of this invention at room temperature (pressure range 0-800 Torr).

[0026] Figure 10The CO2 physical adsorption curve of the product of Comparative Example 3 of this invention at room temperature (pressure range 0-800 Torr).

[0027] Figure 11 The CO2 physical adsorption curve of the product of Comparative Example 4 of this invention at room temperature (pressure range 0-800 Torr).

[0028] Figure 12 This is a breakthrough curve of the product of Example 1 of the present invention in the CO2 / N2 selectivity test.

[0029] Figure 13 This is a breakthrough curve of the product of Example 3 of the present invention in the CO2 / N2 selectivity test.

[0030] Figure 14 This is the breakthrough curve of the product of Example 5 of the present invention in the CO2 / N2 selectivity test. Detailed Implementation

[0031] The following detailed description of the embodiments, with reference to the accompanying drawings, will further illustrate the specific implementation of the present invention, in order to help those skilled in the art to have a more complete, accurate, and in-depth understanding of the inventive concept and technical solution of the present invention.

[0032] like Figure 1 As shown, the present invention provides a method for molding a metal-organic framework material for CO2 capture, comprising the following steps.

[0033] S1. Prepare the adhesive solution.

[0034] Mix PVA powder with a molecular weight of not less than 170,000 with deionized water to obtain a solution with a mass concentration of 5-10%. Place the solution in a constant temperature water bath at 90-95℃ and stir at a rate of 300-500 r / min for 30-60 min until the solution is clear and transparent. Cool the solution to 25-50℃ to obtain a PVA adhesive solution (the effective adhesive component content is 5-10% of the solution mass). Seal and store for later use.

[0035] S2. Pretreatment of waste paper pulp yields structural additives.

[0036] This step involves the preparation of structural additives, specifically including the following sub-steps.

[0037] S2.1. Remove impurities from waste paper pulp.

[0038] Add waste paper pulp to a mixing tank, add deionized water at a solid-liquid ratio of 1:10 to 1:15, and then add 0.5 to 1 wt% of an alkaline substance, such as sodium hydroxide or potassium hydroxide, from the waste paper pulp. Stir the resulting mixture at 200 to 300 rpm for 30 to 60 minutes at 50 to 60°C to achieve deinking and loosening of impurities. Then filter through a 200-mesh sieve to remove large particles of impurities such as plastic and metal. Finally, place the filtrate in a centrifuge and centrifuge at 3000 to 5000 rpm for 10 to 15 minutes to remove fine filler impurities.

[0039] S2.2, The waste paper pulp after impurity removal is pulped.

[0040] The purified pulp after impurity removal is added to a double-disc refiner and pulped to a fiber length of 150~400μm. During this process, the fiber length is monitored in real time by a fiber length meter, and the pulping degree is controlled at 30~45°SR to obtain the pulp.

[0041] S2.3. The obtained slurry is dried.

[0042] The pulp after beating is placed in a forced-air drying oven at 80~95℃ and dried for 4~8 hours until the moisture content is ≤1wt%, thus obtaining pretreated waste paper pulp, which is then sealed for later use.

[0043] Among them, waste paper pulp is recycled plant fiber pulp, and its sources include one or more of the following: office waste paper (printing paper, copy paper), packaging waste paper (corrugated paper, kraft paper), and cultural waste paper (book paper, magazine paper), with office waste paper pulp being the preferred choice.

[0044] S3. Mix and granulate the MOF material.

[0045] In the materials used for molding, the total amount of binder active ingredients and structural aids added together, by mass, shall not exceed 6% of the MOF powder, and the ratio between binder active ingredients and structural aids shall be 1:2 to 2:1.

[0046] Weigh out the following by weight: 100 parts MOF powder, 2-4 parts pretreated waste paper pulp (structural additive), and 2-4 parts PVA binder solution with PVA active ingredient, and add them all to a high-speed mixer; then add an appropriate amount of deionized water so that the total amount of deionized water in the mixture is 40-90 parts; stir the mixture at a temperature of 25-90℃ and a speed of 50-1000r / min for 30-120min to form a uniform and plastic paste; feed the paste into a granulator, adjust the mold parameters, and obtain spherical wet granules with a particle size of 2-5mm.

[0047] The MOF powder material can be any one of Cu-BTC, calf-20, or Co-MOF-74.

[0048] S4. Gradient drying of spherical wet particles: The spherical wet particles are placed in a forced-air drying oven for segmented drying. First, they are dried at 60~80℃ for 2~4 hours, and then the temperature is raised to 110~150℃ for 4~24 hours to completely remove the solvent, thus obtaining MOF shaped particles for CO2 capture.

[0049] Thus, this solution simultaneously achieves the performance goals of "high strength (≥50N), high adsorption retention (CO2 adsorption decrease ≤15%), and strong water resistance (strength still ≥50N after immersion in water)", and improves resource utilization by turning waste paper pulp into a valuable resource, significantly reducing molding costs, and providing key technical support for the large-scale and industrial application of MOF materials.

[0050] The specific implementation of this solution is as follows.

[0051] Example 1.

[0052] S1. Prepare the adhesive solution.

[0053] Take a certain amount of PVA powder with a molecular weight of 200,000 and mix it with deionized water. The resulting solution has a mass concentration of 7%. Place the solution in a constant temperature water bath at 90~95℃ and stir at a rate of 300~500r / min for 30~60min until the solution is clear and transparent. Cool it to 25~50℃ to obtain the PVA adhesive solution, and seal it for later use.

[0054] S2. Pretreatment of waste paper pulp yields structural additives.

[0055] In this step, waste paper pulp is added to a mixing tank, and deionized water is added at a solid-liquid ratio of 1:10 to 1:15. Then, 0.5 to 1 wt% sodium hydroxide is added by weight of the waste paper pulp. The resulting mixture is stirred at 200 to 300 r / min at 50 to 60°C for 30 to 60 minutes to achieve deinking and loosening of impurities. The mixture is then filtered through a 200-mesh sieve to remove large particles of impurities such as plastic and metal. The filtrate is then placed in a centrifuge and centrifuged at 3000 to 5000 r / min for 10 to 15 minutes to separate and remove fine filler impurities.

[0056] The purified pulp after centrifugation is added to a double-disc refiner and refined to a fiber length of 150~400μm. During this process, the fiber length is monitored in real time by a fiber length meter, and the beating degree is controlled at 30~45°SR to obtain the pulp.

[0057] The pulp after beating is placed in a forced-air drying oven at 80~95℃ and dried for 4~8 hours until the moisture content is ≤1wt%, thus obtaining pretreated waste paper pulp, which is then sealed for later use.

[0058] Among them, waste paper pulp is recycled plant fiber pulp, specifically office waste paper pulp.

[0059] S3. Mix and granulate the MOF material.

[0060] Weigh out the following by weight: 100g Cu-BTC powder, 2.5g pretreated waste paper pulp, and 3g PVA binder solution (PVA active ingredient). Add all of these to a high-speed mixer. Add an appropriate amount of deionized water to make the total amount of deionized water 50g. Mix at 25-90℃ and 50-1000r / min for 30-120min to form a uniform and plastic paste. Feed the paste into a granulator, adjust the mold parameters, and obtain spherical wet granules with a particle size of 2-5mm.

[0061] S4. Gradient drying of spherical wet particles.

[0062] The spherical wet particles were placed in a forced-air drying oven and dried in stages. The first stage was dried at 60°C for 3 hours, and the second stage was dried at 120°C for 8 hours to completely remove the solvent, thus obtaining MOF shaped particles for CO2 capture.

[0063] Example 2.

[0064] The scheme is basically the same as that in Example 1, with the following differences: In step S1, the molecular weight of the PVA powder is 180,000; in step S3, the amount of pretreated waste paper pulp is 3g, and the total amount of deionized water after adding an appropriate amount of deionized water is 70g; in step S4, the drying temperature of the first stage of the gradient drying is 70℃ and the drying time is 2h; the drying temperature of the second stage is 140℃ and the drying time is 10h.

[0065] Example 3.

[0066] The scheme is basically the same as that in Example 1, with the following differences: In step S1, the molecular weight of the PVA powder is 210,000, and the mass concentration of the solution obtained by mixing the PVA powder with deionized water is 10%. In step S3, the material of the MOF powder is Co-MOF-74, the effective PVA component in the PVA binder solution is 3.5g, the amount of pretreated waste paper pulp is 2g, and the total amount of deionized water after adding an appropriate amount of deionized water is 40g. In step S4, the drying temperature of the first stage of the gradient drying is 80℃ and the drying time is 2h; the drying temperature of the second stage is 150℃ and the drying time is 10h.

[0067] Example 4.

[0068] The scheme is basically the same as that in Example 1, with the following differences: In step S1, the molecular weight of the PVA powder is 180,000, and the mass concentration of the solution obtained by mixing the PVA powder with deionized water is 5%. In step S3, the material of the MOF powder is Co-MOF-74, the effective PVA component in the PVA binder solution is 2.5g, the amount of pretreated waste paper pulp is 3.2g, and the total amount of deionized water after adding an appropriate amount of deionized water is 90g.

[0069] Example 5.

[0070] The scheme is basically the same as that in Example 1, with the following differences: In step S3, the MOF powder material is Calf-20, the effective PVA component in the PVA binder solution is 3.1g, the amount of pretreated waste paper pulp is 2.8g, and the total amount of deionized water after adding an appropriate amount of deionized water is 70g; in step S4, the drying temperature of the second stage in the gradient drying is 140℃.

[0071] Example 6.

[0072] The scheme is basically the same as that in Example 1, with the following differences: In step S1, the molecular weight of the PVA powder is 170,000. In step S3, the material of the MOF powder is Calf-20. The amount of pretreated waste paper pulp is 2.2g. After adding an appropriate amount of deionized water, the total amount of deionized water is 70g. In step S4, the drying temperature of the first stage of the gradient drying is 70℃ and the drying time is 2h. The drying temperature of the second stage is 120℃ and the drying time is 12h.

[0073] As a comparative example, the applicant also conducted the following experiments.

[0074] Comparative Example 1.

[0075] The scheme is basically the same as that in Example 1, with the following differences: This comparative example did not use structural additives and did not include step S2 in the corresponding embodiment.

[0076] In step S3, the effective PVA component in the PVA adhesive solution is 6g; in step S4, the drying time of the second stage in the gradient drying is 12h.

[0077] Comparative Example 2.

[0078] The scheme is basically the same as that in Example 1, with the following differences: In step S2, the waste paper pulp is directly crushed and used as a structural aid; in step S3, the MOF powder material is Co-MOF-74, the amount of structural aid is 3g, and the total amount of deionized water after adding an appropriate amount of deionized water is 60g; in step S4, the drying temperature of the second stage of the gradient drying is 130℃, and the drying time is 10h.

[0079] Comparative Example 3.

[0080] The scheme is basically the same as that in Example 1, with the following differences: In step S1, the molecular weight of the PVA powder is 30,000. In step S3, the material of the MOF powder is Calf-20, and the amount of structural additive is 3g. In step S4, the drying temperature of the first stage of the gradient drying is 70℃ and the drying time is 2h. The drying temperature of the second stage is 140℃.

[0081] Comparative Example 4.

[0082] The scheme is basically the same as that in Example 1, with the following differences: In step S3, the MOF powder material is Calf-20, and the amount of structural additive is 3g; in step S4, a one-step drying method is used, the drying temperature is 130℃, and the drying time is 12h.

[0083] Comparative Example 5.

[0084] The scheme is basically the same as that in Example 1, with the following differences: This comparative example uses bentonite as a structural additive and does not include step S2 in the corresponding embodiment.

[0085] In step S1, the molecular weight of the PVA powder is 190,000. In step S3, the effective PVA component in the PVA binder solution is 3.5g, the amount of bentonite is 2.5g, and the total amount of deionized water after adding an appropriate amount of deionized water is 55g. In step S4, the drying temperature of the second stage of the gradient drying is 130℃, and the drying time is 10 hours.

[0086] Comparative Example 6.

[0087] The scheme is basically the same as that in Example 1, with the following differences: This comparative example uses talc as a structural additive and does not include step S2 in the corresponding embodiment.

[0088] In step S1, the molecular weight of the PVA powder is 170,000. In step S3, the material of the MOF powder is Co-MOF-74, and the amount of talc is 2.5g. In step S4, the drying temperature of the first stage of the gradient drying is 70℃ and the drying time is 2 hours. The drying temperature of the second stage is 140℃ and the drying time is 8 hours.

[0089] The following performance tests were performed on the MOF molded particles produced in the above specific embodiments and comparative examples.

[0090] (1) CO2 adsorption capacity test: The CO2 adsorption capacity of the molded particles was tested by static volumetric method under the conditions of 25℃ and 1 bar using a physical adsorption instrument, and the decrease in adsorption capacity relative to the raw material MOF powder was calculated.

[0091] (2) Compressive strength test: Using a particle compressive strength tester, 10 molded particles were randomly selected and their axial compressive strength was tested respectively, and the average value was taken; another 10 identical particles were soaked in deionized water at 25℃ for 24h, and then dried at 100~120℃ for 4~6h, and the compressive strength was tested again, and the average value was taken.

[0092] (3) CO2 / N2 selectivity test: A multi-component competitive gas breakthrough curve analyzer was used to simulate the industrial flue gas composition (20 vol% CO2 + 80 vol% N2). Under the conditions of 25℃, 1 bar and gas flow rate of 50 mL / min, the CO2 / N2 separation coefficient was calculated by breakthrough curve.

[0093] Based on the above performance test results, and combined with the key parameters of the relevant embodiments and comparative examples, the specific details are shown in Table 1.

[0094] Table 1: Key parameters and performance test results of the examples and comparative examples

[0095] As shown in Table 1, this invention addresses the core technical pain points of existing MOF molding technology, namely "insufficient strength, adsorption attenuation, lack of water resistance, and excessive cost." Through innovative design of a "binder-structural aid" composite formula and appropriate process, the MOF molded particles prepared meet the following performance indicators: (1) Compressive strength ≥ 50 N; under conditions of 25℃ and 1 bar, the decrease in CO2 adsorption relative to the raw material MOF powder does not exceed 15%; under conditions of 25℃ and 1 bar, the CO2 / N2 separation coefficient is not less than 20; after soaking in water at 25℃ for 24 h and drying at 100~120℃ for 4~6 h, the compressive strength of the particles is still ≥ 50 N. The MOF particles prepared by the above molding method have good CO2 adsorption capacity, selectivity, and high compressive strength; in addition, the amount of binder and structural aid is small, and the structural aid is waste pulp, turning waste into treasure.

[0096] According to Table 1, in Comparative Example 1, without the addition of pretreated waste paper pulp, the CO2 adsorption of the molded product was reduced by more than 15%, and the particle strength after molding was less than 50N. The molded particles turned into powder and failed to form after being soaked in water, indicating that without the addition of structural additives, the performance requirements could not be met at all.

[0097] In Comparative Example 2, the waste paper pulp that was directly crushed was added. The waste paper pulp was not pretreated. The CO2 adsorption of the product after molding was reduced by more than 15%, and the particle strength after molding was less than 50N. The molded particles turned into powder and failed to form after being soaked in water. This shows that simply crushing the waste paper pulp without undergoing the pretreatment step S2 of this invention cannot effectively achieve the performance requirements of this invention. Comparative Example 3 uses PVA with a molecular weight of 30,000. Although the CO2 adsorption of the product after molding is reduced by less than 15%, the particle strength after molding is less than 50N. The molded particles turn into powder and fail to form after being soaked in water. This indicates that the molecular weight of the added PVA binder cannot be too small, otherwise the requirements for structural strength and water resistance cannot be met.

[0098] Comparative Example 4 uses a one-step drying method. Although the granules do not turn into powder after soaking in water after molding, and the CO2 adsorption of the product after molding decreases by no more than 15%, the strength of the granules after molding and after soaking in water and drying is less than 50N. This indicates that one-step drying will damage the structure of the molded MOF material granules, highlighting the necessity of segmented and stepped drying. Comparative Examples 5 and 6 used bentonite and talc as structural additives to replace the pretreated pulp, respectively. The CO2 adsorption of the products after molding was reduced by more than 15%, and the particle strength after molding was less than 50N. The molded particles pulverized or expanded after being soaked in water. This shows that the pretreated waste paper pulp has a significant advantage in meeting performance requirements compared with the structural additives such as bentonite and talc commonly used in the existing technology.

[0099] And combined with the appendix Figure 2-14 look, Figure 2-4 The CO2 adsorption capacity of three MOF materials, Cu-BTC, Co-MOF-74, and calf-20, in powder form and their trend with pressure are shown in turn. Figure 5-7 This demonstrates the CO2 adsorption capacity of the products obtained in Examples 1, 3, and 5 of this invention, and its trend with pressure. Compared with the powders of Cu-BTC, Co-MOF-74, and calf-20, the adsorption capacity loss is smaller, not exceeding 15%. Figure 8-11 This demonstrates the CO2 adsorption capacity of the products obtained in Comparative Examples 1-4 and its trend with pressure. Compared with the powders of Cu-BTC, Co-MOF-74, and calf-20, the adsorption capacity loss is significant, exceeding 15% in all three cases. Figure 12-14 This demonstrates the selectivity of the products obtained in Examples 1, 3, and 5 in CO2 / N2 separation, showing that the products obtained by the present invention have superior selectivity and meet the performance requirements for the production of corresponding MOF molded particles.

[0100] The present invention has been described above by way of example with reference to the accompanying drawings. Obviously, the specific implementation of the present invention is not limited to the above-described manner. Any non-substantial improvements made using the inventive concept and technical solution of the present invention, or the direct application of the inventive concept and technical solution of the present invention to other occasions without modification, are all within the protection scope of the present invention.

Claims

1. A method for shaping a metal organic framework material for CO2 capture, characterized in that, The method comprises the following steps: S1, preparing a binder solution; S2, pretreating waste paper pulp to obtain a structure aid; the pretreatment comprises removing impurities, beating and drying the waste paper pulp; S3, mixing and granulating MOF material; the binder solution, the structure aid, the MOF powder and deionized water are mixed and stirred uniformly to form a paste material, and then granulation is performed; the total amount of the binder effective component and the structure aid together is not more than 6% of the MOF powder, and the ratio between the binder effective component and the structure aid is 1:2 to 2:1; S4, gradient drying the spherical wet granules.

2. A method of forming a metal organic framework material for CO2 capture according to claim 1, wherein, In step S2, the removing impurities treatment of the waste paper pulp comprises: adding the waste paper pulp into a stirring tank, adding deionized water at a solid-liquid ratio of 1:10 to 1:15, adding an alkaline substance at 0.5 to 1 wt% of the mass of the waste paper pulp, and stirring at 50 to 60 DEG C for 30 to 60 min; filtering through a screen to remove large-particle impurities, and centrifuging at 3000 to 5000 r / min for 10 to 15 min to remove fine filler impurities.

3. A method of forming a metal organic framework material for CO2 capture according to claim 1, wherein, In step S2, the beating treatment of the waste paper pulp comprises: adding the purified pulp after removing impurities into a double-disc beater, beating to a fiber length of 150 to 400 mu m, and controlling the beating degree to be 30 to 45 SR to obtain the pulp.

4. A method of forming a metal organic framework material for CO2 capture according to claim 1, wherein, In step S2, the drying treatment of the waste paper pulp comprises: placing the pulp after beating in a 80 to 95 DEG C air-drying oven for 4 to 8 h until the water content is less than or equal to 1 wt%, to obtain the waste paper pulp after pretreatment.

5. A method of forming a metal organic framework material for CO2 capture according to claim 1, wherein, In step S1, PVA powder with a molecular weight of not less than 170,000 is mixed with deionized water to obtain a solution with a mass concentration of 5 to 10%, the solution is placed in a 90 to 95 DEG C constant-temperature water bath, and stirred at a rate of 300 to 500 r / min for 30 to 60 min until the solution is clear and transparent, and then cooled to 25 to 50 DEG C to obtain the PVA binder solution.

6. A method of forming a metal organic framework material for CO2 capture according to claim 1, wherein, In step S3, the MOF powder is 100 parts, the waste paper pulp after pretreatment is 2 to 4 parts, the PVA binder solution is 2 to 4 parts of PVA effective component, and deionized water is additionally added; after the deionized water is added, the total amount of deionized water in the mixture is 40 to 90 parts.

7. A method of forming a metal organic framework material for CO2 capture according to claim 6, wherein, In step S3, the mixture is stirred at a temperature of 25 to 90 DEG C and a rotation speed of 50 to 1000 r / min for 30 to 120 min to form a uniform and plastic paste material, and the spherical wet granules are obtained by granulation.

8. A method of forming a metal organic framework material for CO2 capture according to claim 1, wherein, In step S4, the spherical wet granules obtained in step S3 are first dried at 60 to 80 DEG C for 2 to 4 h, and then dried at 110 to 150 DEG C for 4 to 24 h.

9. The method of claim 1, wherein the metal organic framework material is a MOF-808 material. The material of the MOF powder is any one of Cu-BTC, calf-20 and Co-MOF-74.

10. A method of forming a metal organic framework material for CO2 capture according to claim 1, wherein, The waste paper pulp is a regenerated plant fiber pulp, and the source comprises one or more of office waste paper, packaging waste paper and cultural waste paper.

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