CN113941319A - Block adsorbent and forming method and application thereof - Google Patents

Block adsorbent and forming method and application thereof Download PDF

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CN113941319A
CN113941319A CN202111217845.2A CN202111217845A CN113941319A CN 113941319 A CN113941319 A CN 113941319A CN 202111217845 A CN202111217845 A CN 202111217845A CN 113941319 A CN113941319 A CN 113941319A
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adsorbent
forming
block
powder
reaction system
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CN113941319B (en
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刘丽影
王哲
李茁
其他发明人请求不公开姓名
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Northeastern University China
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • 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
    • B01J20/26—Synthetic macromolecular compounds
    • B01J20/262—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon to carbon unsaturated bonds, e.g. obtained by polycondensation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/16—Alumino-silicates
    • B01J20/165—Natural alumino-silicates, e.g. zeolites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • 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]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/50—Carbon oxides
    • B01D2257/504—Carbon dioxide
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
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    • Y02C20/40—Capture or disposal of greenhouse gases of CO2

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  • Engineering & Computer Science (AREA)
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Abstract

The invention relates to a method for forming a block adsorbent, which comprises the following steps: adding pyrrole monomer into the acid solution, and taking an oxidant as an initiator to perform polymerization reaction on the pyrrole monomer to generate polypyrrole; adding the adsorption material powder into the reaction system before, during or immediately after the polymerization reaction, and uniformly stirring; after the reaction is finished, filtering the reaction system to obtain a filter cake, and forming the filter cake into a blocky adsorbent; or centrifugally depositing the reaction system to obtain the blocky adsorbent. The method adopts pyrrole monomer polymerization to generate polypyrrole, and before the polypyrrole is tightly stacked, the powder adsorption material is wrapped together by utilizing the network structure of the polypyrrole, and the polypyrrole is formed into a block-shaped adsorbent after sedimentation and stacking. He-ShiCompared with the prior art, the block-shaped adsorbent has water resistance and better adsorbability, can not disintegrate in the presence of moisture, and can adsorb CO in a humid environment2The structure of the MOFs can not be damaged, and the energy is saved.

Description

Block adsorbent and forming method and application thereof
Technical Field
The invention relates to the technical field of adsorbent preparation, in particular to a block adsorbent and a forming method and application thereof.
Background
Carbon emissions are considered to be a major cause of global warming, and the problem of the continuing rise in atmospheric greenhouse gas concentrations is of public concern. Carbon capture technology can reduce carbon emissions. Carbon capture technology relies primarily on CO2Adsorbing the material. CO 22The adsorbing material generally has large specific surface area, proper pore structure and surface structure, strong adsorption capacity to the adsorbate, stable chemical property, difficult chemical reaction with the adsorbate, easy manufacture and regeneration and better mechanical property.
Commonly used solid adsorbents include zeolite molecular sieves, porous metal oxides, Metal Organic Frameworks (MOFs), mesoporous silica, porous polymer materials, porous carbon materials, and the like. Zeolite molecular sieves are microporous crystalline materials with excellent hydrothermal stability, and are widely used in the fields of acid catalysis, selective oxidation, adsorption and desorption and the like due to adjustable acidity and unique pore channel structures. MOFs (Metal Organic Framework) are crystalline porous materials with periodic network structures formed by the mutual connection of inorganic Metal centers (Metal ions or Metal clusters) and bridged Organic ligands through self-assembly.
Generally, when zeolite molecular sieve powder and MOFs powder are used as the adsorption material, a binder such as alumina or clay is added to perform molding so as to ensure the mechanical strength of the molded product. However, alumina and clay have no catalytic activity and adsorbability, so the addition of such a binder reduces the content of effective adsorption components in the adsorbent, and reduces the adsorption performance. At present, the development of the MOFs powder forming process mainly includes mechanical forming under pressure and blending forming. Mechanical forming means that the MOFs powder is processed into massive MOFs with certain shape and density under the action of mechanical load with or without adding a binder. For example, MOFs powders are press molded using a tablet press. Mechanical forming methods can deform and collapse the MOFs structure itself. The blending molding is to mix and stir the polymer, the solvent and the MOFs powder, and to prepare the film or the particle after the solvent is volatilized. However, the viscosity of most polymers is relatively high, which easily causes the aggregation of the particles of the MOFs, and in addition, the molecular chains of the polymers also easily block the pore structure of the MOFs, which causes the problem of the reduction of the specific surface area of the adsorbent product. Therefore, the development of a new forming method of the adsorbent is of great significance for improving the adsorption performance of the adsorbent.
Disclosure of Invention
Technical problem to be solved
In view of the above disadvantages and shortcomings of the prior art, the present invention provides a method for forming an adsorbent and an application thereof, which solves the problems of low content of effective adsorption components, reduced specific surface area, poor performance, etc. existing in the existing method for forming a molecular sieve adsorbent or a MOFs adsorbent.
(II) technical scheme
In order to achieve the purpose, the invention adopts the main technical scheme that:
in a first aspect, the present invention provides a method for forming a bulk adsorbent, comprising:
adding pyrrole monomer into the acid solution, and taking an oxidant as an initiator to perform polymerization reaction on the pyrrole monomer to generate polypyrrole; adding the adsorption material powder into the reaction system before, during or just after the polymerization reaction, and uniformly stirring;
after the reaction is finished, filtering the reaction system to obtain a filter cake, and forming the filter cake into a blocky adsorbent; or, centrifugally depositing the reaction system, and forming solid slag obtained by centrifugation into a blocky adsorbent.
According to a preferred embodiment of the present invention, the adsorption material powder is MOFs powder or zeolite molecular sieve powder.
According to a preferred embodiment of the present invention, the acidic solution is a concentrated hydrochloric acid solution, and the pH value is 0-2.
According to a preferred embodiment of the present invention, the oxidizing agent is a mixture of hydrogen peroxide and a ferric salt. Preferably, the amount of the oxidizing agent is added in the following ratio: the molar ratio of the hydrogen peroxide to the pyrrole monomer is 4.6:1, and the molar ratio of the iron ions in the ferric iron salt to the pyrrole monomer is 0.03: 1. Preferably, the iron salt is ferric chloride. The bi-component catalyst, which reacts as follows:
H2O2+2Fe3+＝2Fe2++O2↑+2H+，H2O2+2Fe2++2H+＝2Fe3++2H2the O phases are combined to obtain the total reaction formula 2H2O2═O2↑+2H2O，Fe3+It can be used as oxidation catalyst to accelerate reaction speed.
The Fenton reagent formed by hydrogen peroxide and ferric iron salt has high oxidability, a system and a product are green and non-toxic, good oxidation performance can be achieved only by a small amount of iron ions, and other common oxidants such as sodium persulfate, ammonium persulfate and the like have certain toxicity and are not beneficial to long-term use.
According to the preferred embodiment of the invention, after filtering to obtain a filter cake or centrifugally depositing to obtain solid slag, washing with deionized water until the washing liquid is clear, and then drying to obtain the block adsorbent, wherein the drying condition is 80-90 ℃ and the drying time is 12-24 hours.
According to the preferred embodiment of the present invention, the device used for filtering is a mold with filtering function; after the reaction system is added to the mould, the filtrate is filtered off and a filter cake is formed in the mould, so that the filter cake has a shape matching the inner cavity of the mould. Preferably, the device is connected with a vacuum pump for suction filtration.
According to a preferred embodiment of the present invention, when the adsorbing material powder is MOFs powder, the forming method comprises the following steps:
step 1: adding pyrrole monomer into the acid solution, and uniformly stirring;
step 2: adding MOFs powder into the solution obtained in the step 1, and uniformly stirring;
and step 3: adding an oxidant into the solution obtained in the step (2), stirring at normal temperature, and initiating a pyrrole monomer polymerization reaction by the oxidant to generate polypyrrole;
and 4, step 4: filtering the reaction system obtained in the step 3 to obtain a filter cake, and forming the filter cake into a blocky MOFs adsorbent; or centrifugally depositing the reaction system to obtain the massive MOFs adsorbent.
According to a preferred embodiment of the present invention, the stirring reaction time in step 3 is 3-9 h.
According to the preferred embodiment of the present invention, the stirring time in step 2 is 0.5-1 h; the stirring time in the step 1 is 5-15 min.
According to a preferred embodiment of the present invention, when the adsorption material powder is zeolite molecular sieve powder, the forming method comprises the following steps:
s1, adding pyrrole monomer into the acidic solution, and stirring uniformly;
s2, adding an oxidant into the solution of S1, stirring at normal temperature, and initiating polymerization reaction of pyrrole monomers by the oxidant to generate polypyrrole;
s3, washing the reaction system obtained in the step S2 with water until the reaction system is neutral, adding zeolite molecular sieve powder, and fully stirring at normal temperature;
s4, filtering the reaction system obtained in the step S3 to obtain a filter cake, and forming the filter cake into a blocky zeolite molecular sieve adsorbent; or, centrifugally depositing the reaction system to obtain the blocky zeolite molecular sieve adsorbent.
According to the preferred embodiment of the present invention, in S2, the stirring reaction time is 3-9 h.
According to the preferred embodiment of the present invention, in S3, the stirring time is 5-15 min; and the stirring time in the S1 is 5-15 min.
In a second aspect, the present invention also provides a bulk adsorbent, which is prepared by the preparation method of any one of the above embodiments.
In a third aspect, the invention also provides the use of the bulk adsorbent; the block adsorbent is used as a gas adsorbent.
Preferably, the bulk adsorbent adsorbs gas in a humid environment. For example, it can be packed in wet flue gas to adsorb CO directly2And the like. The existing mass production adsorbent can not directly adsorb CO2The flue gas is pretreated for removing moisture to adsorb CO2(ii) a Therefore, the block-shaped sucker prepared by the inventionThe advantages of the additive are obvious.
In addition, the block-shaped adsorbent prepared by the invention can adsorb and desorb CO under the conditions of temperature change and pressure change2、CH4Or N2And the gas is adsorbed and separated. For example, the gas can be effectively adsorbed at high pressure (low temperature), and the adsorbed gas can be released at low pressure (high temperature) to achieve the purpose of adsorption separation.
(III) advantageous effects
The forming method of the block-shaped adsorbent provided by the invention comprises the steps of adding pyrrole monomers into an acid solution, and providing conditions for polymerization of the pyrrole monomers; and adding MOFs or zeolite molecular sieve powder and the like (or other adsorbent materials) into a reaction system before, during or just after polymerization to form polypyrrole, and filtering (preferably suction filtering) or centrifugally depositing the liquid-phase reaction system to respectively obtain a filter cake or solid slag, wherein the filter cake or the solid slag is the blocky adsorbent. The adsorbent material powder and polypyrrole in the block adsorbent have adsorption effect, and compared with the existing binder-doped forming method, the block adsorbent formed by the invention has water resistance and better adsorbability, can not disintegrate in case of moisture, and can adsorb CO in a humid environment2And the moisture in the flue gas is not required to be removed in advance, so that the environment-friendly and energy-saving effects are achieved. The forming method of the block-shaped adsorbent is simple, convenient and quick, does not damage the structure of MOFs, and is suitable for industrial application.
Drawings
Fig. 1 is a schematic view of a mold having a filtering function for preparing a bulk adsorbent.
FIG. 2 is a graph of CO at 0 ℃ for a bulk MOFs adsorbent containing 20% PPy2Adsorption isotherm of (1).
FIG. 3 is a diagram of a 15% PPy block-shaped MOFs adsorbent with CO at 0 ℃2Adsorption isotherm of (1).
FIG. 4 is a graph of CO at 0 ℃ for a bulk MOFs adsorbent containing 10% PPy2Adsorption isotherm of (1).
FIG. 5 is a graph of CO at 0 ℃ for a bulk MOFs adsorbent containing 5% PPy2Adsorption isotherm of (1).
Detailed Description
The main conception of the invention is as follows: when the adsorbent powder is molded into a block (large granular) adsorbent, the powdered adsorbent is aggregated into a monolith form using polypyrrole. Specifically, before, during or immediately after polymerization of pyrrole monomers to generate polypyrrole, adding adsorption material powder into a reaction system, and uniformly stirring to enable the generated polypyrrole to integrate the powdery adsorption material into blocks in the forms of wrapping, winding and the like. It should be noted that, in the present invention, polypyrrole and the adsorbent powder are not simply stirred and mixed, but the powder adsorbent is wrapped and wound together in a loose network structure before the polypyrrole is tightly stacked, and the adsorbent powder is formed into a block adsorbent after sedimentation and stacking. On the contrary, if the finished polypyrrole product and the adsorption material powder are directly mixed and stirred, or the adsorption material powder is added into the reaction system after the polypyrrole monomer is polymerized to generate polypyrrole for a certain period of time, the polypyrrole can not be fully subjected to polycondensation reaction and has settled/stacked to be in a more compact state, and the adsorption material powder cannot be wrapped in the polypyrrole, and meanwhile, the gaps of the polypyrrole per se are reduced, and the adsorbability of the polypyrrole per se is also deteriorated.
In the formed block-shaped adsorbent, polypyrrole plays a role in wrapping and winding to enable powdered adsorption materials (MOFs or molecular sieve powder) to be aggregated into a block, and the powdered adsorption materials (MOFs or molecular sieve powder) are supported between a polypyrrole molecular chain and a membrane layer, so that the polypyrrole has a large specific surface area and porosity, and the polypyrrole has certain adsorbability.
In particular, based on the different characteristics of the MOFs and zeolite molecules, when the bulk adsorbent is shaped using the method of the present invention, it can be operated as follows.
When the block MOFs adsorbent is formed, the method comprises the following steps: adding pyrrole monomer into an acidic solution, adding MOFs powder into the solution, fully and uniformly stirring, adding an oxidant (hydrogen peroxide and ferric chloride) into the solution, fully stirring until the polymerization reaction is complete to generate polypyrrole, filtering and washing a reaction system, pouring the washed mixed solution into a mold with a filtering function, filtering, washing and drying to obtain the blocky MOFs adsorbent.
When the block zeolite molecular sieve adsorbent is formed, the forming method comprises the following steps: adding pyrrole monomer into an acid solution, adding an oxidant (hydrogen peroxide and ferric chloride) into the solution, fully stirring until the polymerization reaction is complete to generate polypyrrole, washing to be neutral, then adding zeolite molecular sieve powder into the solution, fully stirring uniformly, pouring the mixed solution into a mold with a filtering function, and filtering, washing and drying to obtain a massive zeolite molecular sieve solid. Since zeolite molecular sieve cannot exist under strong acid environment, when the block zeolite molecular sieve adsorbent is formed, the zeolite molecular sieve is added into polypyrrole after polypyrrole reaction is finished and acid is washed and removed.
The method of the invention has the advantages of rapid reaction, mild reaction conditions such as temperature and pressure and no secondary pollution. The filtrate obtained by filtering is collected, an acidic environment and an oxidant can be provided for the next forming, the filtrate can be recycled for multiple times, and the cost is reduced; the final product of the molding is solid hard block-shaped and can be directly put into an adsorption column for use.
For a better explanation of the invention, reference will now be made in detail to the embodiments illustrated in the drawings.
Example 1 (20% PPy)
Adding 1mL of HCl into 55mL of deionized water, uniformly stirring on a magnetic stirrer, then dropwise and slowly adding 0.5mL of pyrrole monomer into a prepared acidic environment, stirring for 10min until uniform mixing is realized, adding 2.4g of UiO-66 powder (the weight ratio is PPy: UiO-66 is 1: 4, and the weight ratio of UiO-66 is 80 wt%), stirring for 30min until uniform mixing is realized, and adding an oxidant (2.5mL of H)2O2And 0.08g FeCl3) Stirring for 6h at normal temperature until the polymerization reaction is complete, then filtering with a device shown in figure 1 (polypyrrole is settled and stacked, and UiO-66 powder is wrapped and formed into a block) to obtain a filter cake, and placing the filter cake in a drying oven at 90 ℃ to remove water, so as to obtain the cylindrical UiO-66 block. Wherein, the polypyrrole accounts for 20 percent of the mass of the cylindrical UiO-66 block body.
The filter device 10 shown in fig. 1 comprises a mould 1 provided with a plurality of cells 11. The bottom of the die 1 is provided with a filter material 12, and the hole groove 11 penetrates through the bottom of the die 1. A joint 13 connected with a suction pump is arranged below the filter material 12.
In order to prevent the solids in the reaction mixture from flowing out of the bottom of the well 11, a plastic gasket 14 may be provided, which is provided with a groove of a certain depth (0.5cm) into which the bottom of the mould 1 is inserted. The filtering material 12 is arranged below the plastic gasket 14, and the bottom of each hole groove 11 is contacted with the filtering material 12.
After the reaction mixture is poured into each hole groove 11 of the mould 1, the suction pump starts to work, the filtrate is pumped to be dry, and a filter cake is formed in the hole groove 11, wherein the filter cake is the formed block-shaped adsorbent, and the shape of the filter cake is matched with the shape of the hole groove 11. According to the shape and size requirements of the block-shaped adsorbent, the hole grooves 11 with different shapes and sizes can be arranged, or the formed block-shaped adsorbent can be cut or crushed for use.
Example 2 (15% PPy)
Adding 1mL of HCl into 55mL of deionized water, stirring uniformly on a magnetic stirrer, then dropwise and slowly adding 0.5mL of pyrrole monomer into a prepared acidic environment, stirring for 5-15min until the mixture is uniform, adding 3.4g of UiO-66 powder (UiO-66 is a metal organic framework material), stirring for 30min until the mixture is uniform, adding an oxidant (2.5mL of H)2O2And 0.08g FeCl3) Stirring for 6h at normal temperature until the polymerization reaction is complete, then filtering by using a device shown in figure 1 (polypyrrole is settled and stacked, and UiO-66 powder is wrapped and formed into a block) to obtain a filter cake, and placing the filter cake in a drying oven at 90 ℃ to remove water, so as to obtain the cylindrical UiO-66 block. Wherein the polypyrrole accounts for 15 percent of the mass of the cylindrical UiO-66 block body.
Example 3 (10% PPy)
Adding 1mL of HCl into 55mL of deionized water, stirring uniformly on a magnetic stirrer, then dropwise and slowly adding 0.5mL of pyrrole monomer into the prepared acidic environment, stirring for 5-15min until the mixture is uniform, adding 5.4g of UiO-66 powder (the weight ratio of UiO-66 is 90 wt%), stirring for 30min until the mixture is uniform, and adding an oxidant (2.5mL of H)2O2And 0.08g FeCl3) Stirring for 6h at normal temperature until the polymerization reaction is complete, then filtering by using a device shown in figure 1 (polypyrrole is settled and stacked, and UiO-66 powder is wrapped and formed into a block) to obtain a filter cake, and placing the filter cake in a drying oven at 90 ℃ to remove water, so as to obtain the cylindrical UiO-66 block. Wherein, the polypyrrole accounts for 10 percent of the mass of the cylindrical UiO-66 block body.
Example 4 (5% PPy)
Adding 1mL of HCl into 55mL of deionized water, uniformly stirring on a magnetic stirrer, then dropwise and slowly adding 0.5mL of pyrrole monomer into a prepared acidic environment, stirring for 5-15min until the mixture is uniform, adding 11.4g of UiO-66 powder (the weight ratio of UiO-66 is 95 wt%, the metal organic framework material), stirring for 30min until the mixture is uniform, and adding an oxidant (2.5mL of H)2O2And 0.08g FeCl3) Stirring for 6h at normal temperature until the polymerization reaction is complete, then filtering by using a device shown in figure 1 (polypyrrole is settled and stacked, and UiO-66 powder is wrapped and formed into a block) to obtain a filter cake, and placing the filter cake in a drying oven at 90 ℃ to remove water, so as to obtain the cylindrical UiO-66 block. Wherein, the polypyrrole accounts for 5 percent of the mass of the cylindrical UiO-66 block body.
The cylindrical UiO-66 adsorbent of examples 1-4 above, in which polypyrrole was present in 20%, 15%, 10%, and 5% by mass, respectively.
For the bulk MOFs adsorbents formed in examples 1 to 4, the individual component CO was measured at 0 ℃ using a physical adsorption apparatus2And (3) carrying out an adsorption experiment on the gas, and drawing an adsorption curve graph by taking absolute pressure as a horizontal coordinate and adsorption quantity as a vertical coordinate. As shown in fig. 2-5. The results show that when the UiO-66 weight ratio is 95 wt%, the sample has CO at 0 deg.C2The adsorption amount of (2) is obviously larger than that when the weight ratio of UiO-66 is 100 wt% (as shown in figure 5), not only the adsorption amount is improved, but also the purpose of saving cost is achieved. As shown in FIGS. 3-4, when the UiO-66 weight ratio was 90 wt% and 85 wt%, the samples were CO at 0 deg.C2The adsorption amount of the catalyst is basically equal to that when the weight ratio of UiO-66 is 100 wt%, and the aim of saving the cost is also fulfilled. As shown in FIG. 2, when the UiO-66 weight ratio was 80 wt%, the sample was CO at 0 deg.C2The adsorption amount of the catalyst is slightly lower than that of UiO-66The adsorbent has the adsorption capacity of 100 wt%, but the invention forms the powder adsorbent into blocks, improves the practical occasion of the adsorbent, prevents the powder adsorbent from being taken away in an airflow environment (flue or air passage) to cause loss, and is washed away when meeting water, saves a large amount of cost, and has high neutral price ratio in practical application.
Likewise, the method of the present invention is also applicable to the preparation of zeolite molecular sieve powder into a bulk adsorbent. As in the following examples.
Example 5
Adding 1mL of HCl into 55mL of deionized water, stirring uniformly on a magnetic stirrer with pH of 0, adding 0.5mL of pyrrole monomer, stirring for 10min until uniform mixing is achieved, (generating 0.6g of polypyrrole), and adding an oxidant (2.5mL of H)2O2And 0.08g FeCl3) Stirring for 6h at normal temperature until the polymerization reaction is complete, washing the obtained PPy with ultrapure water to remove an acid solution, then adding 2.4g of NaY molecular sieve powder (the weight ratio of NaY is 80 wt%), uniformly mixing, filtering by using a device shown in figure 1 (polypyrrole is settled and stacked, and the molecular sieve powder is wrapped and formed into a block) to obtain a filter cake, and placing the filter cake in a drying box at 90 ℃ to remove water to obtain the cylindrical NaY block adsorbent. Wherein the content of polypyrrole is 20%.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.

Claims (10)

1. A method of forming a block adsorbent, comprising:
adding pyrrole monomer into the acid solution, and taking an oxidant as an initiator to perform polymerization reaction on the pyrrole monomer to generate polypyrrole; adding the adsorption material powder into the reaction system before, during or immediately after the polymerization reaction, and uniformly stirring;
after the reaction is finished, filtering the reaction system to obtain a filter cake, and forming the filter cake into a blocky adsorbent; or centrifugally depositing and forming the reaction system into a block adsorbent.
2. The method for forming a bulk adsorbent according to claim 1, wherein the adsorbent powder is a MOFs powder or a zeolite molecular sieve powder.
3. The method for forming a block adsorbent according to claim 1, wherein the acidic solution is a concentrated hydrochloric acid solution and has a pH of 0 to 2.
4. The method for forming a block-shaped adsorbent according to claim 1, wherein the oxidant is a mixture of hydrogen peroxide and a ferric salt.
5. The method for forming a block adsorbent according to claim 4, wherein the oxidizing agent is added in the following ratio: the molar ratio of the hydrogen peroxide to the pyrrole monomer is 4.6:1, and the molar ratio of the iron ions in the ferric iron salt to the pyrrole monomer is 0.03: 1.
6. The method for forming a block-shaped adsorbent according to claim 1, wherein the device for filtration is a mold having a filtration function; after the reaction system is added to the mould, the filtrate is filtered off and a filter cake is formed in the mould, so that the filter cake has a shape matching the inner cavity of the mould.
7. The method for forming a bulk adsorbent according to claim 2, wherein when the adsorbent material powder is a MOFs powder, the method comprises the steps of:
step 1: adding pyrrole monomer into the acid solution, and uniformly stirring;
step 2: adding MOFs powder into the solution obtained in the step 1, and uniformly stirring;
and step 3: adding an oxidant into the solution obtained in the step (2), stirring at normal temperature, and initiating a pyrrole monomer polymerization reaction by the oxidant to generate polypyrrole;
and 4, step 4: filtering the reaction system obtained in the step 3 to obtain a filter cake, and forming the filter cake into a blocky MOFs adsorbent; or centrifugally depositing the reaction system to obtain solid slag, and forming the solid slag into the blocky MOFs adsorbent.
8. The method for forming a block adsorbent according to claim 2, wherein when the adsorbent powder is zeolite molecular sieve powder, the method comprises the steps of:
s1, adding pyrrole monomer into the acidic solution, and stirring uniformly;
s2, adding an oxidant into the solution of S1, stirring at normal temperature, and initiating polymerization reaction of pyrrole monomers by the oxidant to generate polypyrrole;
s3, washing the reaction system obtained in the step S2 with water until the reaction system is neutral, adding zeolite molecular sieve powder, and fully stirring at normal temperature;
s4, filtering the reaction system obtained in the step S3 to obtain a filter cake, and forming the filter cake into a blocky zeolite molecular sieve adsorbent; or, centrifugally depositing the reaction system and forming to obtain the block zeolite molecular sieve adsorbent.
9. A bulk adsorbent produced by the production method according to any one of claims 1 to 8.
10. Use of the block adsorbent according to claim 9 as a gas adsorbent.
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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010115320A1 (en) * 2009-04-10 2010-10-14 北京化工大学 Integral porous adsorbent and preparation method therefor
US20140378563A1 (en) * 2013-06-24 2014-12-25 Gwangju Institute Of Science And Technology Solid state vapor phase polymerization method for nanoporous polypyrrole and nanoporous polypyrrole prepared therefrom
CN106925235A (en) * 2017-03-27 2017-07-07 东北大学 One kind can efficiently separate CO in moisture2Adsorbent and preparation method thereof
CN110229330A (en) * 2019-06-27 2019-09-13 东北大学 A kind of environmentally protective synthetic method and its application of polypyrrole
CN110479221A (en) * 2019-08-30 2019-11-22 天津大学 A kind of preparation method and application of red mud/polypyrrole composite adsorbing material
CN110581027A (en) * 2019-09-30 2019-12-17 长江勘测规划设计研究有限责任公司 Preparation method of composite pseudo capacitor electrode material
CN110639481A (en) * 2019-09-20 2020-01-03 桂林理工大学 Method for preparing polypyrrole and mesoporous molecular sieve composite material

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010115320A1 (en) * 2009-04-10 2010-10-14 北京化工大学 Integral porous adsorbent and preparation method therefor
US20140378563A1 (en) * 2013-06-24 2014-12-25 Gwangju Institute Of Science And Technology Solid state vapor phase polymerization method for nanoporous polypyrrole and nanoporous polypyrrole prepared therefrom
CN106925235A (en) * 2017-03-27 2017-07-07 东北大学 One kind can efficiently separate CO in moisture2Adsorbent and preparation method thereof
CN110229330A (en) * 2019-06-27 2019-09-13 东北大学 A kind of environmentally protective synthetic method and its application of polypyrrole
CN110479221A (en) * 2019-08-30 2019-11-22 天津大学 A kind of preparation method and application of red mud/polypyrrole composite adsorbing material
CN110639481A (en) * 2019-09-20 2020-01-03 桂林理工大学 Method for preparing polypyrrole and mesoporous molecular sieve composite material
CN110581027A (en) * 2019-09-30 2019-12-17 长江勘测规划设计研究有限责任公司 Preparation method of composite pseudo capacitor electrode material

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