CN112619594A - 3DOM structure composite adsorbent and preparation method and application thereof - Google Patents

3DOM structure composite adsorbent and preparation method and application thereof Download PDF

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CN112619594A
CN112619594A CN202011607769.1A CN202011607769A CN112619594A CN 112619594 A CN112619594 A CN 112619594A CN 202011607769 A CN202011607769 A CN 202011607769A CN 112619594 A CN112619594 A CN 112619594A
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colloidal crystal
3dom
solution
microspheres
composite adsorbent
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李璐
段明哲
何炽
董瑞
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Xian Jiaotong University
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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
    • B01J20/02—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
    • B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
    • 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
    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
    • 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
    • B01D2257/30—Sulfur compounds
    • B01D2257/304—Hydrogen sulfide

Abstract

The invention provides ZnFe with a 3DOM structure2O4‑SiO2Preparation and application of composite adsorbent, belonging to the technical field of preparation of inorganic nano porous functional material, wherein ZnFe with 3DOM structure2O4‑SiO2The composite adsorbent has a stable ordered macroporous structure. The invention selects a plurality of template agent combinations to prepare a series of composite adsorbents with stable structures and high activity, and applies the composite adsorbents to a fine hydrogen sulfide removal process, thereby improving the removal precision, expanding the application range and effectively reducing the process cost.

Description

3DOM structure composite adsorbent and preparation method and application thereof
Technical Field
The invention belongs to the technical field of preparation of inorganic nano porous functional materials, and particularly relates to a 3DOM (three-dimensional object model) structure composite adsorbent, and a preparation method and application thereof, which are mainly used for H2The field of fine removal of S.
Background
Hydrogen sulfide (molecular formula H)2S) is colorless and has irritant odor under the standard condition, has the characteristics of toxicity, corrosivity, inflammability and the like, belongs to high-risk chemicals, and has a low threshold of H2S can cause serious harm to human health, ecological environment and industrial production. Currently, methods for removing hydrogen sulfide include absorption methods, membrane separation, cryogenic rectification, adsorption methods, and the like. The adsorption method is a technology with simple process, large sulfur adsorption capacity, high precision and low cost, is particularly suitable for the process with higher requirement on desulfurization precision, and has very important application prospect in the current and future industrial application fields. At present H2The S adsorbent has limited adsorption capacity and needs to be improved.
Disclosure of Invention
In order to solve the problems in the prior art, the invention aims to provide a 3DOM structure composite adsorbent, a preparation method and application thereof, and the 3DOM structure composite adsorbent is used for H2The adsorption effect of S is excellent.
The technical scheme adopted by the invention is as follows:
a composite adsorbent with 3DOM structure is prepared from ZnFe2O4And SiO2ZnFe in mass percent2O4Not less than 30 percent of SiO2The mass content of (A) is not more than 70%;
the pore size distribution range of the 3DOM structure composite adsorbent is 100-300nm, and the wall thickness is 10-30 nm.
The preparation method of the 3DOM structure composite adsorbent comprises the following steps:
obtaining the colloidal crystal microspheres with the diameter of 100-300 nm;
obtaining a metal salt solution chelated by citric acid, wherein the metal salt solution contains a Fe source, a Zn source and citric acid;
preparing a precursor solution: mixing a silicon precursor solution, a metal salt solution chelated by citric acid and an alcohol solution of a soft template agent to obtain the precursor solution;
preparing a complex by taking the colloidal crystal microspheres as a colloidal crystal template and using the colloidal crystal template and the precursor solution in a suction filtration manner; and drying and roasting the composite body to obtain the 3DOM structure composite adsorbent.
Preferably, the preparation process of the colloidal crystal microsphere comprises the following steps: and (3) carrying out polymerization inhibitor removal treatment on styrene or methyl methacrylate for 1-5 times by using a neutral or alkaline alumina chromatographic column, and preparing the colloidal crystal microspheres with different diameters by adopting a soap-free emulsion polymerization method after treatment.
Preferably, the citric acid chelated metal salt solution is prepared as follows: weighing a preset amount of Fe source and Zn source according to the mass ratio, dissolving the Fe source and the Zn source in an alcohol solution to prepare a metal salt solution with the concentration of 0.5-2mol/L, adding citric acid according to the proportion of 1-2 times of the amount of the metal salt substance, heating to 50-80 ℃, mixing and stirring to obtain the metal salt solution chelated by the citric acid.
Preferably, the Fe source is Fe (NO)3)3、Fe2(SO4)3Or FeCl3(ii) a The Zn source is Zn (NO)3)2、ZnSO4Or ZnCl2(ii) a The alcohol solution is one or a mixture of methanol, ethanol, propanol, butanol, octanol and glycol.
Preferably, the silicon precursor solution is prepared by mixing and stirring tetraethoxysilane, concentrated hydrochloric acid (mass concentration is 37%), deionized water and ethanol according to the molar ratio of 10:39:3:18 for 0.5-3 h.
Preferably, when the complex is prepared by using the colloidal crystal template and the precursor solution in a suction filtration mode, under the condition of vacuum suction filtration, dropwise adding the precursor solution into the colloidal crystal template to enable the colloidal crystal template to be completely and uniformly soaked, removing the redundant precursor solution, drying for 6-12h at the temperature of 20-100 ℃, and repeating the steps of suction filtration, dropwise adding and drying for a plurality of times to enable the structure formed after the precursor solution is dried to reach the preset thickness, so as to obtain the complex.
Preferably, the composite is fired at N2Heating to 300 deg.C at a rate of 0.1-5 deg.C/min under atmosphere, maintaining for 3-12h, cooling to room temperature, switching to air atmosphere, heating to 300 deg.C at 0.1-5 deg.C/min, maintaining for 1-12h, heating to 500 deg.C at 0.1-5 deg.C/min, and maintaining for 3-1 hAnd 2h, obtaining the 3DOM structure composite adsorbent.
Preferably, when the complex is prepared, the colloidal crystal microspheres are subjected to heat treatment at 50-100 ℃ for 1-20min and then subjected to suction filtration;
the colloidal crystal microspheres are polystyrene microspheres or polymethyl methacrylate microspheres;
the soft template agent is polyether P123 or P127.
The invention also provides application of the 3 DOM-structured composite adsorbent, and the 3 DOM-structured composite adsorbent is used for H in gas-phase components2And (4) removing S.
The invention has the following beneficial effects:
the component of the 3DOM structure composite adsorbent comprises ZnFe2O4And SiO2ZnFe in mass percent2O4Not less than 30 percent of SiO2The mass content of (A) is not more than 70%; the pore size distribution range of the 3DOM structure composite adsorbent is 100-300nm, and the wall thickness is 10-30 nm. The composite adsorbent of the invention takes Zn and Fe as main active components and is used for H2And S removal efficiency is high. With SiO2Is a structural assistant, so the structure stability is good and the regeneration can be repeated. The 100-300nm macroporous structure promotes H2Adsorption efficiency of S.
According to the preparation method of the 3DOM structure composite adsorbent, the colloidal crystal microspheres are used as the colloidal crystal template during preparation, and the colloidal crystal template and the precursor solution are used for preparing a complex in a suction filtration mode; the invention adopts an in-situ coprecipitation process, can ensure that the active components are uniformly distributed, and the pore structure is regular and ordered by the template agent.
Furthermore, in the preparation process of the colloidal crystal microsphere, polymerization inhibitor removing treatment is carried out, and polymerization forming of the colloidal crystal microsphere can be promoted after the polymerization inhibitor is removed.
Furthermore, the metal salt solution chelated by the citric acid is prepared, so that the combination of the metal salt solution and the template agent can be promoted.
Further, a complex is prepared by utilizing the colloidal crystal template and the precursor solution in a suction filtration mode, and the template agent and the precursor solution can be uniformly infiltrated through vacuum filtration.
Further, when the composite is baked, N is2The atmosphere protection can promote the forming of the active component, then the air atmosphere is introduced to further improve the strength, and finally the template agent is removed by high-temperature calcination. The combined process can prevent collapse of the structure caused by direct high temperature calcination.
Furthermore, when the composite is prepared, the colloidal crystal microspheres are subjected to heat treatment at 100 ℃ for 5min, so that the strength of the colloidal crystal microspheres can be enhanced, and the pore channel blockage caused by structural collapse in the pore-forming process can be prevented.
The 3DOM structure composite adsorbent is used for H in gas phase components2For removal of S, for H2The S removal effect is good, the adsorption efficiency can be effectively improved, the service life of the adsorbent is prolonged, the reuse of the adsorbent is promoted, and therefore the cost is reduced.
Drawings
FIG. 1(a) is an SEM image of PS (polystyrene) microspheres of about 280nm in diameter made in an example of the present invention;
FIG. 1(b) is an SEM image of PMMA (polymethyl methacrylate) microspheres with a diameter of about 250nm prepared in the examples of the present invention;
FIG. 1(c) is an SEM image of PS (polystyrene) microspheres of about 480nm diameter prepared in an example of the present invention;
FIG. 1(d) is an SEM image of a layered packing of the colloidal microspheres of the present invention;
FIG. 2(a) is an electron microscope image (30 wt% zinc ferrite) of the 3DOM structure composite adsorbent in the example of the present invention;
FIG. 2(b) is an electron microscope topographic map (50 wt% zinc ferrite) of the 3DOM structure composite adsorbent in the example of the present invention;
FIG. 2(c) is an electron microscope topographic map (70 wt% zinc ferrite) of the 3DOM structure composite adsorbent in the example of the present invention;
FIG. 2(d) is an electron microscope topographic map (100 wt% zinc ferrite) of the 3DOM structure composite adsorbent in the example of the present invention;
FIG. 3(a) is a TEM image of a 3DOM structured composite adsorbent of the present invention;
FIG. 3(b) is a TEM image of the 3DOM structured composite adsorbent of the present invention;
FIG. 4 is an XRD spectrum of the 3DOM structured composite adsorbent of the present invention, in which curve a is an XRD spectrum containing 30 wt% zinc ferrite, curve b is an XRD spectrum containing 50 wt% zinc ferrite, curve c is an XRD spectrum containing 70 wt% zinc ferrite, and curve d is an XRD spectrum containing 100 wt% zinc ferrite);
FIG. 5 is a material pair H of the present invention2S adsorption experiment result chart.
Detailed Description
The invention is further explained below with reference to the drawings and the specific implementation method. The following examples are intended to illustrate the invention, but are not to be construed as limiting the invention in any way
The technical scheme of the invention is as follows:
the 3DOM (three-dimensional ordered macroporous) structure composite adsorbent has an ordered macroporous structure, the pore size distribution range of the composite adsorbent is 100-300nm, the wall thickness is 10-30nm, and ZnFe is2O4The mass content of the components is as follows: 30% -100% of SiO2The mass content of (A) is not more than 70%.
The preparation method of the 3DOM structure composite adsorbent comprises the following steps:
(1) preparation of colloidal crystal template
Using a neutral/alkaline alumina chromatographic column to perform polymerization inhibitor removal treatment on styrene/methyl methacrylate for 1-5 times, and preparing the submicron colloidal crystal microspheres with different diameters (100- & ltSUB & gt and 300nm) by a soap-free emulsion polymerization method after the treatment.
(2) Preparation of precursor solution
Weighing a certain amount of Fe source and Zn source according to the mass ratio of metal oxide in the composite adsorbent accounting for 30-100% of the total adsorbent, and dissolving the Fe source and the Zn source in an alcohol mixed solution to prepare a 0.5-2mol/L metal salt solution. Adding citric acid into the solution according to the proportion of 1-2 times of the amount of the metal salt substance, heating, mixing and stirring to obtain the metal solution chelated by the citric acid. Weighing a certain amount of soft template agent (P123 or F127) to be dissolved in the mixed solution of alcohol, stirring uniformly, and then mixing with the metal solution chelated by the citric acid. And (3) dropwise adding corresponding ethyl orthosilicate into the mixed solution according to the mass ratio, and stirring at normal temperature for 1h to obtain a precursor solution.
(3) Glue crystal template filling
Before the colloidal crystal template is filled, the colloidal crystal template microspheres are subjected to heat treatment at 50-100 ℃ for 1-20min, so that the strength of the microspheres is enhanced. And then placing the microspheres in a Buchner funnel, and dropwise adding the precursor solution to the colloidal crystal template under the vacuum filtration condition to ensure that the colloidal crystal template is completely and uniformly soaked. Removing the redundant solution, drying in an oven at 20-100 ℃ for 6-12h, repeating the steps of suction filtration, dropwise addition and drying for 3-6 times, and drying at room temperature for 48 h.
(4) Removal of templating agent
The dried sample was placed in a tube furnace and 50ml/min N was passed through2After purging for 30min, at N2Slowly raising the temperature to 300-500 ℃ at the temperature raising rate of 0.1-5 ℃/min under the atmosphere and roasting for 1-12 h. After the temperature is reduced to room temperature, the air atmosphere is switched, the temperature is raised to 500 ℃ for 1 to 12 hours at the speed of 0.1 to 5 ℃/min, and then the temperature is raised to 700 ℃ at the same speed, and the temperature is maintained for 3 to 12 hours, so that 3DOM ZnFe is obtained2O4-SiO2A composite adsorbent.
In the invention, the colloidal crystal template microsphere monomer is styrene or methyl methacrylate. The alcohol mixed solution is one or more of methanol, ethanol, propanol, butanol, octanol and glycol. The Fe source adopts Fe (NO)3)3、Fe2(SO4)3Or FeCl3. The Zn source adopts Zn (NO)3)2、ZnSO4Or ZnCl2. The soft template agent is P123 or P127.
The 3DOM structure composite adsorbent can be used in the field of gas adsorption impurity removal and is used for H in gas phase components2And (4) fine removal of S.
Example 1
The preparation process of the DOM structure composite adsorbent of this example 3 includes the following processes:
preparing PS colloidal crystal template microspheres:
carrying out polymerization inhibitor removal treatment on the styrene solution, and drying at 105 ℃ for 12hThe sex alumina (special for chromatography) is used as a packed column, the styrene solution is dripped into the neutral alumina chromatographic column drop by drop, and the styrene monomer without the polymerization inhibitor is obtained after the treatment of the chromatographic column. Adding 300ml of deionized water into a 500ml three-neck flask, connecting a mechanical stirring device, a gas communication device and a condenser pipe, and introducing 50ml/minN into the system2While the temperature was raised to 70 ℃ stirring was continued for 1 h. 6ml of styrene monomer was poured into a three-necked flask. After 20min, the corresponding amount of initiator (K) was added dropwise2S2O8KPS) solution (azo-bis-isobutyronitrile AIBN is adopted as an initiator if large-size microspheres are prepared), and polymerization is initiated. After 28h of reaction, the polymerization reaction is finished to obtain milky PS (polystyrene) microsphere suspension, and the mixed solution is dissolved in 1000ml of deionized water for storage. And after cooling, centrifuging at the speed of 1000rpm for 4h, pouring off the supernatant, and drying at 40 ℃ for 48h to obtain the self-assembled PS colloidal crystal microspheres.
Preparing a precursor solution:
and (3) calculating the mass percentage of the metal oxide in the composite adsorbent to the total adsorbent by mass ratio to be 30%. 1.89g of Zn (NO) are weighed out3)2And 4.83g of Fe (NO)3)3Dissolved in a mixed solution of alcohol to prepare a metal salt solution having a total metal ion concentration of 1.5 mol/L. Adding a corresponding amount of citric acid into the solution according to the molar ratio of the citric acid to the total metal ions being 1:1, heating to 60 ℃, mixing and stirring for 2h to obtain the metal precursor solution chelated by the citric acid. The silicon precursor solution is prepared by mixing and stirring Tetraethoxysilane (TEOS), concentrated hydrochloric acid, deionized water and ethanol according to the molar ratio of 10:39:3:18 for 1 h.
Preparation of 3 DOM-structured renewable ZnFe by taking PS microspheres as template2O4-SiO2The process of compounding the adsorbent comprises the following steps:
weighing 2.0g F127 and dissolving in 10mL of glycol-methanol solution with the volume ratio of 3:2, mixing uniformly, mixing with 20mL of precursor solution, and stirring at normal temperature for 1 h. Before the colloidal crystal template is filled, the PS microspheres are firstly placed in an oven for heat treatment at 100 ℃ for 5min so as to enhance the strength of the microspheres. Then placing the colloidal crystal template in a Buchner funnel, under the condition of vacuum filtration,and dropwise adding the precursor solution into the colloidal crystal template to ensure that the colloidal crystal template is completely and uniformly soaked. After removing the excess solution, drying in an oven at 40 ℃ for 6h, repeating the above steps of suction filtration-dropwise addition-drying for 3 times. Finally drying at room temperature for 48 h. The dried sample was placed in a tube furnace and 50ml/min N was passed through2After purging for 30min, at N2Slowly raising the temperature to 300 ℃ at the temperature rising rate of 1 ℃/min under the atmosphere and roasting for 3 h. After the temperature is reduced to room temperature, the air atmosphere is switched, the temperature is raised to 300 ℃ at the speed of 1 ℃/min and maintained for 2h, and then the temperature is raised to 500 ℃ at the same speed and maintained for 4 h.
As shown in FIG. 5, an adsorbent in which zinc ferrite is present at a ratio of 30 wt% can adsorb 1000ppm of H in an atmosphere under relatively mild conditions2S is removed to be more than 0.1ppm and is stably kept for 45 hours.
Example 2
Preparing PMMA colloidal crystal template microspheres:
and (2) carrying out polymerization inhibitor removal treatment on the methyl methacrylate solution, filling alkaline alumina (special for chromatography) subjected to drying treatment at 105 ℃ for 12 hours into a packed column, and dropwise adding the methyl methacrylate solution into the chromatographic column to obtain the polymerization inhibitor-removed methyl methacrylate monomer. Adding 300ml of deionized water into a 500ml three-neck flask, connecting a mechanical stirring device, a gas communication device and a condenser pipe, and introducing 50ml/minN into the system2While the temperature was raised to 70 ℃ stirring was continued for 1 h. 22.5mL of MMA monomer containing 0.03 wt% of p-hydroxybenzoic acid was poured into a three-necked flask. After stirring was continued for 20min, 10mL of 100g/mL aqueous KPS solution was added dropwise to initiate polymerization. After 1h, the polymerization reaction is finished to obtain milky PMMA microsphere suspension, and the mixed solution is dissolved in 1000ml of deionized water for storage. And after cooling, centrifuging at the speed of 1000rpm for 4h, pouring off the supernatant, and drying at 40 ℃ for 48h to obtain the self-assembled PMMA colloidal crystal microspheres.
Preparing a precursor solution:
weighing 3.78g of Zn (NO) according to the mass ratio, wherein the mass percent of the metal oxide in the composite adsorbent accounts for 100 percent of the total adsorbent mass3)2And 9.66g of Fe (NO)3)3Dissolving in mixed alcohol solution to obtain concentrated metal ionA metal salt solution with the degree of 1.5 mol/L. Adding a corresponding amount of citric acid into the solution according to the molar ratio of the citric acid to the total metal ions being 1:2, heating to 60 ℃, mixing and stirring for 2h to obtain the metal precursor solution chelated by the citric acid.
Method for preparing 3DOM (three-dimensional ordered) structure renewable ZnFe by taking PMMA (polymethyl methacrylate) microspheres as template2O4-SiO2The process of compounding the adsorbent comprises the following steps:
weighing 2.0g P123 and dissolving in 10mL of glycol-methanol solution with the volume ratio of 3:2, mixing uniformly, mixing with 20mL of precursor solution, and stirring at normal temperature for 2 h. Before the colloidal crystal template is filled, the PMMA microspheres are firstly placed in an oven for heat treatment at 100 ℃ for 5min, so that the strength of the microspheres is enhanced. And then placing the colloidal crystal template in a Buchner funnel, and dropwise adding the precursor solution to the colloidal crystal template under the vacuum filtration condition to ensure that the colloidal crystal template is completely soaked and uniformly soaked. After removing the excess solution, drying in an oven at 50 ℃ for 6h, repeating the above steps of suction filtration-dropwise addition-drying for 3 times. Finally drying at room temperature for 48 h. The dried sample was placed in a tube furnace and 50ml/min N was passed through2After purging for 30min, at N2Slowly raising the temperature to 300 ℃ at the temperature raising rate of 2 ℃/min under the atmosphere and roasting for 3 h. After the temperature is reduced to room temperature, the air atmosphere is switched, the temperature is increased to 300 ℃ at the speed of 0.5 ℃/min and maintained for 2h, and then the temperature is increased to 500 ℃ at the same speed and maintained for 4 h.
As shown in FIG. 5, an adsorbent in which zinc ferrite is present in a proportion of 100 wt% can adsorb 1000ppm of H in an atmosphere under relatively mild conditions2S is removed to be more than 0.1ppm and kept for 55 h.
Example 3
The preparation process of the DOM structure composite adsorbent of this example 3 includes the following processes:
preparing PS colloidal crystal template microspheres:
and (3) carrying out polymerization inhibitor removal treatment on the styrene solution, adopting neutral alumina (special for chromatography) subjected to drying treatment at 105 ℃ for 12 hours as a packed column, dropwise adding the styrene solution into the neutral alumina chromatographic column, and carrying out treatment on the styrene solution through the chromatographic column to obtain the styrene monomer with the polymerization inhibitor removed. Adding 300ml of deionized water into a 500ml three-neck flask, connecting a mechanical stirring device, a gas communication device and a cold deviceCondensing the tube, and introducing 50ml/minN into the system2While the temperature was raised to 70 ℃ stirring was continued for 1 h. 6ml of styrene monomer was poured into a three-necked flask. After 20min, the corresponding amount of initiator (K) was added dropwise2S2O8KPS) solution (azo-bis-isobutyronitrile AIBN is adopted as an initiator if large-size microspheres are prepared), and polymerization is initiated. After 28h of reaction, the polymerization reaction is finished to obtain milky PS (polystyrene) microsphere suspension, and the mixed solution is dissolved in 1000ml of deionized water for storage. And after cooling, centrifuging at the speed of 1000rpm for about 4 hours, pouring off the supernatant, and drying at 60 ℃ for 48 hours to obtain the self-assembled PS colloidal crystal microspheres.
Preparing a precursor solution:
and calculating the mass ratio of the metal oxide in the composite adsorbent to the total adsorbent by 70%. 1.51g of Zn (NO) are weighed out3)2And 3.86g Fe (NO)3)3And dissolved in a mixed solution of alcohol to prepare a metal salt solution having a total metal ion concentration of 1.5 mol/L. Adding a corresponding amount of citric acid into the solution according to the molar ratio of the citric acid to the total metal ions being 1:1, heating to 60 ℃, mixing and stirring for 2h to obtain the metal precursor solution chelated by the citric acid. The silicon precursor solution is prepared by mixing and stirring Tetraethoxysilane (TEOS), hydrochloric acid, deionized water and ethanol according to the molar ratio of 10:39:3:18 for 1 h.
Preparation of 3 DOM-structured renewable ZnFe by taking PS microspheres as template2O4-SiO2The process of compounding the adsorbent comprises the following steps:
weighing 2.0g F127 and dissolving in 10mL of glycol-methanol solution with the volume ratio of 3:2, mixing uniformly, mixing with 20mL of precursor solution, and stirring at normal temperature for 1 h. Before the colloidal crystal template is filled, the PS microspheres are firstly placed in an oven for heat treatment at 100 ℃ for 5min so as to enhance the strength of the microspheres. And then placing the colloidal crystal template in a Buchner funnel, and dropwise adding the precursor solution to the colloidal crystal template under the vacuum filtration condition to ensure that the colloidal crystal template is completely soaked and uniformly soaked. After removing the excess solution, drying in an oven at 60 ℃ for 6h, and repeating the above steps of suction filtration, dropwise addition and drying for 3 times. Finally drying at room temperature for 48 h. The dried sample was placed in a tube furnace and 50ml of air was passed through/min N2After purging for 30min, at N2Slowly heating to 300 ℃ at the heating rate of 1.5 ℃/min under the atmosphere and roasting for 6 h. After the temperature is reduced to room temperature, the air atmosphere is switched, the temperature is raised to 300 ℃ at the speed of 1 ℃/min and maintained for 2h, and then the temperature is raised to 500 ℃ at the same speed and maintained for 6 h.
As shown in FIG. 5, an adsorbent in which zinc ferrite is present in a proportion of 70 wt% can adsorb 1000ppm of H in an atmosphere under relatively mild conditions2S is removed to be more than 0.1ppm and is stably maintained for 60 hours.
The invention selects a plurality of templates to prepare the series of composite adsorbents with 3DOM structures, and applies the series of composite adsorbents to the fine desulfurization process of hydrogen sulfide, thereby improving the removal precision, expanding the application range, and reducing the process cost because the developed desulfurizer can be repeatedly regenerated and used.
The preparation method of the 3DOM structure composite adsorbent is simple in process and good in product performance, and the product can be applied to the field of hydrogen sulfide fine removal.
The 3DOM composite material disclosed by the invention constructs the zinc ferrite composite oxide deep desulfurizing agent with high specific surface area, large pore volume and large pore diameter based on a 3DOM porous structure by using a colloidal crystal template for pore forming. The desulfurizer has high efficiency and strong mechanical stability, can be repeatedly regenerated without influencing the use, and can be used in H2The S adsorption purification field has good application prospect.
The 3DOM structure composite adsorbent has the characteristics of ordered periodicity, interconnected open pore channels and macroporous characteristics, and has great research value in the application fields of materials such as adsorption, separation, catalysis, electrodes and the like compared with the conventional microporous and mesoporous materials. In the preparation of the 3DOM structure composite adsorbent, a proper colloidal crystal template is selected, and a good macroporous structure is constructed, so that the adsorbent has a stable structure and a proper pore channel; proper active components are selected, so that the adsorbent has sufficient reaction activity; the influence of various auxiliaries on the physical and chemical properties of the material is considered, and the applicability and stability of the material under the actual working condition are ensured.

Claims (10)

1. 3DOM structureThe composite adsorbent is characterized in that the components comprise ZnFe2O4And SiO2ZnFe in mass percent2O4Not less than 30 percent of SiO2The mass content of (A) is not more than 70%;
the pore size distribution range of the 3DOM structure composite adsorbent is 100-300nm, and the wall thickness is 10-30 nm.
2. The method for preparing 3DOM structured composite adsorbent of claim 1, comprising the following steps:
obtaining the colloidal crystal microspheres with the diameter of 100-300 nm;
obtaining a metal salt solution chelated by citric acid, wherein the metal salt solution contains a Fe source, a Zn source and citric acid;
preparing a precursor solution: mixing a silicon precursor solution, a metal salt solution chelated by citric acid and an alcohol solution of a soft template agent to obtain the precursor solution;
preparing a complex by taking the colloidal crystal microspheres as a colloidal crystal template and using the colloidal crystal template and the precursor solution in a suction filtration manner; and drying and roasting the composite body to obtain the 3DOM structure composite adsorbent.
3. The preparation method according to claim 2, wherein the preparation process of the colloidal crystal microsphere comprises the following steps: and (3) carrying out polymerization inhibitor removal treatment on styrene or methyl methacrylate for 1-5 times by using a neutral or alkaline alumina chromatographic column, and preparing the colloidal crystal microspheres with different diameters by adopting a soap-free emulsion polymerization method after treatment.
4. The method of claim 2, wherein the citric acid chelated metal salt solution is prepared as follows: weighing a preset amount of Fe source and Zn source according to the mass ratio, dissolving the Fe source and the Zn source in an alcohol solution to prepare a metal salt solution with the concentration of 0.5-2mol/L, adding citric acid according to the proportion of 1-2 times of the amount of the metal salt substance, heating to 50-80 ℃, mixing and stirring to obtain the metal salt solution chelated by the citric acid.
5. The method according to claim 2 or 4, wherein the Fe source is Fe (NO)3)3、Fe2(SO4)3Or FeCl3(ii) a The Zn source is Zn (NO)3)2、ZnSO4Or ZnCl2(ii) a The alcohol solution is one or a mixture of methanol, ethanol, propanol, butanol, octanol and glycol.
6. The preparation method of claim 2, wherein the silicon precursor solution is prepared by mixing and stirring tetraethoxysilane, concentrated hydrochloric acid, deionized water and ethanol according to a molar ratio of 10:39:3:18 for 0.5-3 h.
7. The preparation method according to claim 2, wherein when the complex is prepared by suction filtration of the colloidal crystal template and the precursor solution, the precursor solution is dropwise added to the colloidal crystal template under vacuum suction filtration to completely and uniformly infiltrate the colloidal crystal template, the excess precursor solution is removed, the colloidal crystal template is dried at 20-100 ℃ for 6-12h, and the steps of suction filtration, dropwise addition and drying are repeated for several times to ensure that the structure formed after the precursor solution is dried reaches a preset thickness to obtain the complex.
8. The method according to claim 2, wherein the composite is fired under N2Heating to 300 ℃ at a heating rate of 0.1-5 ℃/min under the atmosphere, preserving heat for 3-12h, cooling to the greenhouse temperature along with the furnace, switching to the air atmosphere, heating to 300 ℃ at 0.1-5 ℃/min, preserving heat for 1-12h, heating to 500 ℃ at 0.1-5 ℃/min, preserving heat for 3-12h, and obtaining the 3DOM structure composite adsorbent.
9. The preparation method according to claim 2, wherein in the preparation of the complex, the colloidal crystal microspheres are subjected to heat treatment at 50-100 ℃ for 1-20min and then subjected to suction filtration;
the colloidal crystal microspheres are polystyrene microspheres or polymethyl methacrylate microspheres;
the soft template agent is polyether P123 or P127.
10. Use of the 3DOM structured composite adsorbent of claim 1, wherein the 3DOM structured composite adsorbent is used for H in a gas phase component2And (4) removing S.
CN202011607769.1A 2020-12-29 2020-12-29 3DOM structure composite adsorbent and preparation method and application thereof Pending CN112619594A (en)

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