CN111151219A - Monolithic structure adsorbent, preparation method and application thereof - Google Patents

Monolithic structure adsorbent, preparation method and application thereof Download PDF

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Publication number
CN111151219A
CN111151219A CN201811325013.0A CN201811325013A CN111151219A CN 111151219 A CN111151219 A CN 111151219A CN 201811325013 A CN201811325013 A CN 201811325013A CN 111151219 A CN111151219 A CN 111151219A
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adsorbent
molecular sieve
clay
mud
wet
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王胜
王树东
林乐
袁中山
李德意
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Dalian Institute of Chemical Physics of CAS
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Dalian Institute of Chemical Physics of CAS
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • 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
    • 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
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    • 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
    • B01J20/12—Naturally occurring clays or bleaching earth
    • 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
    • B01J20/28042—Shaped bodies; Monolithic structures
    • 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
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3007—Moulding, shaping or extruding
    • 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
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3042—Use of binding agents; addition of materials ameliorating the mechanical properties of the produced sorbent
    • 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
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    • B01J20/3078—Thermal treatment, e.g. calcining or pyrolizing
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    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
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    • B01D2257/708—Volatile organic compounds V.O.C.'s
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Abstract

The application discloses a monolithic structure adsorbent, a preparation method and application thereof, wherein the monolithic structure adsorbent comprises mesoporous molecular sieve, clay and mullite fiber; the mass ratio of mesoporous molecular sieve, clay and mullite fiber in the monolithic adsorbent is 40-80: 5-20: 10 to 30. The monolithic structure adsorbent has the advantages of high adsorption capacity, good safety performance, high strength, difficult cracking, strong water resistance, long service life, simple preparation process and low preparation cost, and the preparation method thereof.

Description

Monolithic structure adsorbent, preparation method and application thereof
Technical Field
The application relates to an overall structure adsorbent for purifying VOCs gas, in particular to a preparation method of an overall extrusion type molecular sieve adsorbent for adsorbing VOCs gas, and belongs to the field of environmental protection.
Background
Volatile Organic Compounds (VOCs) are an important air pollutant, and generally refer to organic compounds with a boiling point of 50-260 ℃ and a saturated vapor pressure of over 133.132kpa at room temperature, and comprise hydrocarbons, halogenated hydrocarbons, aromatic hydrocarbons, polycyclic aromatic hydrocarbons and the like. The industrial exhaust such as the process tail gas discharged from chemical plants and the flue gas generated by burning wastes contains various VOCs, and the tail gas discharged from motor vehicles contains hydrocarbon substances which are not completely combusted. VOCs have complex components and great harm to human bodies, and have special odor which can cause the human bodies to have various discomforts and toxicity and irritation. Many VOCs are known to have neurotoxic, renal and hepatic toxicity, and even carcinogenic effects, which can damage blood components and cardiovascular system, cause gastrointestinal disorders, induce diseases of immune system, endocrine system and hematopoietic system, and cause metabolic defects. Thus, the discharge of VOCs has very serious consequences for human health, and has attracted widespread attention.
The pollution control method of VOCs mainly comprises an incineration method, an adsorption method, a condensation method, a corona method, a membrane separation method, a photocatalytic oxidation method, a biological method and the like. Among them, the adsorption method is one of the methods for effectively treating low-concentration VOCs. The level of removal of VOCs depends on the type of adsorbent, the composition and concentration of VOCs, the operating conditions (temperature, pressure, humidity), etc. Common adsorbents include activated carbon, activated carbon fibers, zeolites, molecular sieves, pillared clays, activated alumina, silica gel, and the like. The active carbon used as the adsorbent has the defects of low safety, poor adsorption efficiency, easy blockage of pore channels, short service cycle, difficult hazardous waste treatment and the like. The molecular sieve has a cage-like structure of faujasite, and has the advantages of good hydrothermal stability, large specific surface area, strong adsorption capacity, no flammability and the like.
The molecular sieve is usually prepared into a honeycomb shape by an extrusion method and a dip coating method. The dip coating method is to dip commercial honeycomb ceramics into slurry containing molecular sieve, and prepare a molecular sieve coating with the thickness of several microns to tens of microns after the processes of blowing, drying, roasting and the like. Patents CN1288781A and CN1269262A disclose in-situ synthesis of magnesium-base SiO on a bulk cordierite honeycomb ceramic carrier2A process for preparing a zeolite. Firstly, a certain proportion of Al is mixed2O3、SiO2、Na2Preparing O and water into gel slurry, then dip-coating the gel slurry on the honeycomb ceramic carrier, and finally adding organic amine solutionCrystallizing at a certain temperature for several days, and then washing, drying and roasting to obtain a finished product with a molecular sieve coating. The dip-coating method mainly has the defects of weak combination with the surface of the carrier, thin molecular sieve coating, complex process, high cost and the like. Patent CN101905145A discloses a honeycomb-shaped molecular sieve material prepared by extrusion method, which is simple in preparation process, but the crystal lattice of the molecular sieve is easily broken by high-strength extrusion, so that the adsorption capacity is lost. Patent CN103111322A reports a N2The preparation method of the monolithic honeycomb molecular sieve catalyst for O decomposition is characterized in that an active component, a binder, an extrusion aid and the like are directly molded by pressurization to prepare the monolithic honeycomb molecular sieve catalyst, but the method is only limited in a laboratory, the prepared size is small, a complete process route is not formed in industry, the problem of engineering amplification is to be solved, and the application field is narrow.
The molecular sieve is a porous material, has high heat sensitivity index, and is easy to crack in the drying process, so the molding preparation of the molecular sieve directly influences the industrial popularization and application of the molecular sieve catalyst. In the drying process, the control of temperature and humidity and the selection of the drying mode determine the dehydration rate of the green body, thereby influencing the shape and strength of the green body. In order to realize the large-scale industrial application, a complete process route and a preparation method are required to be formed, and each index is strictly controlled to obtain a qualified industrial application product.
Therefore, the invention aims to provide the adsorbent with the integral structure, which has the advantages of high adsorption capacity, high safety performance, high strength, difficult cracking, strong water resistance, long service life, simple preparation process and low preparation cost.
Disclosure of Invention
According to one aspect of the application, the monolithic adsorbent and the preparation method thereof are provided, and the monolithic adsorbent is high in adsorption capacity, good in safety performance, high in strength, not easy to crack, strong in water resistance, long in service life, simple in preparation process and low in preparation cost.
The monolithic structure adsorbent is characterized by comprising a mesoporous molecular sieve, clay and mullite fiber; the mass ratio of mesoporous molecular sieve, clay and mullite fiber in the monolithic adsorbent is 40-80: 5-20: 10 to 30.
Optionally, the mesoporous molecular sieve has an average pore diameter of 2 to 50 nm.
Optionally, the mass ratio of mesoporous molecular sieve, clay and mullite fiber in the monolithic adsorbent is 40: 5: 10. 50: 10: 15. 50: 12: 18. 50: 8: 12. 50: 6: 10. 80: 20: 30 and any two ratio ranges.
Optionally, the monolithic adsorbent is composed of mesoporous molecular sieve, clay and mullite fiber.
Optionally, the mesoporous molecular sieve is selected from at least one of MCM-41, MCM-48, MCM-50, SBA-15, SBA-3 and FDU-5.
Optionally, the adsorption temperature of the monolithic adsorbent for adsorbing the VOCs is 0-60 ℃, and the desorption temperature of the monolithic adsorbent is 120-300 ℃.
Optionally, the adsorption capacity of the monolithic adsorbent for adsorbing the VOCs gas is 0.1-0.3 g/g, and the desorption rate is greater than 95%.
Optionally, the monolithic adsorbent is a honeycomb monolithic adsorbent.
According to another aspect of the present application, there is provided a method for preparing the monolithic adsorbent, wherein the monolithic adsorbent is obtained by mixing mesoporous molecular sieve, clay, mullite fiber, binder, lubricant and water, kneading, vacuum pugging, aging, extrusion molding, microwave shaping and roasting.
The preparation method of the monolithic structure adsorbent is characterized by comprising the following steps of:
(1) pugging wet pug containing mesoporous molecular sieve, clay and mullite fiber to obtain pug;
(2) and sealing, aging and molding the pug to obtain a wet blank, and shaping and roasting to obtain the integral-structure adsorbent.
Optionally, the wet pug obtained in the step (1) further comprises a binder, a lubricant and deionized water.
Optionally, the binder is selected from at least one of phenolic resin emulsion, polyvinyl alcohol, sodium hydroxymethyl cellulose and acrylic resin emulsion.
Optionally, the mass ratio of the sum of the masses of the mesoporous molecular sieve, the clay and the mullite fiber in the step (1) to the mass of the binder, the lubricant and the deionized water is 100: 5-20: 3-10: 20 to 60.
Optionally, the mass ratio of the sum of the masses of the mesoporous molecular sieve, the clay and the mullite fiber in the step (1) to the mass of the binder, the lubricant and the deionized water is 100: 5: 3: 20. 100, and (2) a step of: 8: 5: 25. 100, and (2) a step of: 10: 5: 25. 100, and (2) a step of: 15: 8: 30. 100, and (2) a step of: 5: 10: 40. 100, and (2) a step of: 5: 10: 60. 100, and (2) a step of: 20: 10: 60 and ranges between any two of the ratios.
Optionally, the method of claim 3, wherein the forming in step (2) is extrusion;
the shaping in the step (2) is drying treatment, and the moisture content of the dried blank is less than 10%.
Optionally, the aging in step (2) is: aging for 8-24 h under the air condition with the humidity of 40-80%;
the setting conditions in the step (2) are as follows: heating by microwave at 90-120 ℃;
the roasting conditions in the step (2) are as follows: roasting at 500-800 ℃ for 3-10 h.
Optionally, the upper limit of the aging time in step (2) is selected from 10h, 12h, 15h, 18h, 20h, 22h or 24 h; the lower limit is selected from 8h, 10h, 12h, 15h, 18h, 20h or 22 h.
Optionally, the upper limit of the temperature for said shaping in step (2) is selected from 950 ℃, 100 ℃, 105 ℃, 110 ℃, 115 ℃ or 120 ℃; the upper limit is selected from 900 deg.C, 950 deg.C, 100 deg.C, 105 deg.C, 110 deg.C or 115 deg.C.
Optionally, the upper limit of the temperature of the roasting in step (2) is selected from 550 ℃, 600 ℃, 650 ℃, 700 ℃, 750 ℃ or 800 ℃; the lower limit is selected from 500 deg.C, 550 deg.C, 600 deg.C, 650 deg.C, 700 deg.C or 750 deg.C.
Optionally, the upper limit of the time for the calcination in step (2) is selected from 4h, 5h, 6h, 7h, 8h, 9h or 10 h; the lower limit is selected from 3h, 4h, 5h, 6h, 7h, 8h or 9 h.
Optionally, characterized by the steps of:
1) mixing mesoporous molecular sieve, clay and mullite fiber to obtain a mixed dry material;
2) adding a binder, a lubricant and deionized water into the mixed dry material obtained in the step 1), stirring and mixing mud to obtain wet mud material;
3) mixing and kneading the wet pug obtained in the step 2), and then performing vacuum pugging;
4) sealing the pug subjected to vacuum pugging in the step 3) by using a preservative film, standing and aging in air with the humidity of 40-80 at normal temperature and normal pressure;
5) extruding and molding the aged mud blank obtained in the step 4) at the extrusion pressure of xx-xxMPa, and cutting the mud blank into a wet blank body;
6) microwave heating the wet blank obtained in the step 5), and carrying out shaping and drying treatment at the temperature of 90-120 ℃;
7) and (3) roasting the blank dried in the step 6) to obtain the adsorbent with the integral structure.
According to yet another aspect of the present application, there is provided the monolithic adsorbent, and the use of the monolithic adsorbent for the purification of gas containing VOCs.
The beneficial effects that this application can produce include:
1) the adsorbent with the integral structure has high adsorption capacity and excellent heat regeneration performance;
2) the adsorbent with the integral structure has the advantages of high aperture ratio, low resistance and high strength;
3) the adsorbent with the integral structure has the advantages of good water resistance, strong safety performance and long service life;
4) the adsorbent with the integral structure is simple in preparation process and low in manufacturing cost.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
Unless otherwise stated, the raw materials in the examples of the present application are all industrial grade raw materials, and are readily available and cheap. In the examples, the mesoporous molecular sieve has an average pore diameter of 2 to 50 nm.
The application provides a monolithic adsorbent for purifying gas containing VOCs and a preparation method thereof, wherein the monolithic adsorbent comprises mesoporous molecular sieve, clay and mullite fiber; the mass ratio of mesoporous molecular sieve, clay and mullite fiber in the monolithic adsorbent is 40-80: 5-20: 10 to 30.
Optionally, the monolithic structure adsorbent is composed of a mesoporous molecular sieve, clay and mullite fiber, wherein the mesoporous molecular sieve is one or more of MCM-41, MCM-48, MCM-50, SBA-15, SBA-3 and FDU-5; the mass ratio of the mesoporous molecular sieve to the clay to the mullite fiber is as follows: 40-80: 5-20: 10 to 30.
The preparation of the adsorbent with the integral structure adopts the following technical scheme:
mixing mesoporous molecular sieve, clay, mullite fiber, binder, lubricant and water according to a certain proportion, and carrying out processes of pugging, vacuum pugging, aging, extrusion molding, low-temperature microwave shaping, roasting and the like.
The monolithic adsorbent for purifying the gas containing VOCs provided by the invention is prepared by the following specific steps:
1) mixing mesoporous molecular sieve, clay and mullite fiber according to a certain mass ratio (40-80/5-20/10-30);
2) adding a binder, a lubricant and deionized water into the dry material mixed in the step 1) according to a certain mass ratio, stirring and mixing mud, wherein the mass ratio of the dry material to the binder to the lubricant to the deionized water is as follows: 100/5-20/3-10/20-60;
3) putting the wet pug obtained in the step 2) into a pug mill for mixing and pugging, and putting the pug subjected to pugging into a vacuum pug mill for vacuum pugging;
4) sealing the pug subjected to vacuum pugging in the step 3) by using a preservative film, standing and aging in humid air at normal temperature and normal pressure for 8-24 hours;
5) putting the aged mud blank obtained in the step 4) into an extrusion forming machine for extrusion, wherein the extrusion pressure is 20MPa, and cutting the mud blank into a honeycomb ceramic wet blank body by using molybdenum wires;
6) microwave heating the wet blank obtained in the step 5), and carrying out shaping and drying treatment at the temperature of 90-120 ℃;
7) roasting the dried green body obtained in the step 6) at the roasting temperature of 500-.
The invention provides a monolithic adsorbent for purifying VOCs-containing gas, which is applied to purification of VOCs-containing industrial waste gas.
The monolithic adsorbent for purifying the gas containing the VOCs is applied to adsorption of the VOCs, the adsorption temperature is 0-60 ℃, the desorption temperature is 120-300 ℃, the adsorption capacity is 0.1-0.3 g/g, and the desorption rate is more than 95%.
In the examples of the present application, the parts by mass of each component indicates the ratio of each component, and the sum of the parts by mass of each component may be any positive number.
Example 1:
weighing 50 parts of MCM-41 molecular sieve, 10 parts of clay and 15 parts of mullite fiber according to the mass parts, mixing and stirring for 30min, adding 7 parts of sodium hydroxymethyl fiber, 5 parts of lubricant and 50 parts of deionized water into the mixed dry material according to the mass parts, stirring and mixing mud, putting wet mud into a mud mixer, mixing and kneading mud, pugging for 3 times, putting the pugging mud into a vacuum pug mill again for vacuum pugging for 3 times, sealing the pugging mud subjected to vacuum pugging with a preservative film, standing and aging for 15h in humid air (the relative humidity is 60%) at normal temperature and normal pressure; and (3) putting the aged mud blank into an extrusion forming machine for extrusion, wherein the extrusion pressure is 20MPa, cutting the mud blank into a honeycomb ceramic wet blank body by using a molybdenum wire, carrying out microwave heating on the wet blank body, carrying out shaping and drying treatment at the temperature of 110 ℃, carrying out microwave drying for 10min, roasting the dried blank body, and roasting for 6h at the roasting temperature of 600 ℃ to obtain the honeycomb type integral structure adsorbent.
Example 2:
weighing 50 parts of MCM-48 molecular sieve, 12 parts of clay and 18 parts of mullite fiber according to the mass parts, mixing and stirring for 30min, adding 7 parts of acrylic resin emulsion, 6 parts of lubricant and 50 parts of deionized water into the mixed dry material according to the mass parts, stirring and mixing mud, putting wet mud into a mud mixer, mixing and kneading mud, pugging for 3 times, putting the pugging mud into a vacuum pugging machine again for vacuum pugging for 3 times, sealing the pugging mud subjected to vacuum pugging with a preservative film, standing and aging for 10h in humid air (the relative humidity is 60%) at normal temperature and normal pressure; and (3) putting the aged mud blank into an extrusion forming machine for extrusion, wherein the extrusion pressure is 20MPa, cutting the mud blank into a honeycomb ceramic wet blank body by using a molybdenum wire, carrying out microwave heating on the wet blank body, carrying out shaping and drying treatment at the temperature of 110 ℃, carrying out microwave drying for 10min, roasting the dried blank body, and roasting for 6h at the roasting temperature of 600 ℃ to obtain the honeycomb type integral structure adsorbent.
Example 3:
weighing 50 parts of MCM-50 molecular sieve, 8 parts of clay and 12 parts of mullite fiber according to the mass parts, mixing and stirring for 30min, adding 7 parts of sodium hydroxymethyl fiber, 5 parts of lubricant and 50 parts of deionized water into the mixed dry material according to the mass parts, stirring and mixing mud, putting wet mud into a mud mixer, mixing and kneading mud, pugging for 3 times, putting the pugging mud into a vacuum pug mill again for vacuum pugging for 3 times, sealing the pugging mud subjected to vacuum pugging with a preservative film, standing and aging for 10h in humid air (the relative humidity is 75%) at normal temperature and normal pressure; and (3) putting the aged mud blank into an extrusion forming machine for extrusion, wherein the extrusion pressure is 20MPa, cutting the mud blank into a honeycomb ceramic wet blank body by using a molybdenum wire, carrying out microwave heating on the wet blank body, carrying out shaping and drying treatment at 100 ℃, carrying out microwave drying for 10min, roasting the dried blank body, and roasting for 6h at 600 ℃ to obtain the honeycomb type integral structure adsorbent.
Example 4:
weighing 50 parts of SBA-15 molecular sieve, 6 parts of clay and 10 parts of mullite fiber according to the mass parts, mixing and stirring for 30min, adding 7 parts of polyvinyl alcohol, 5 parts of lubricant and 50 parts of deionized water into the mixed dry material according to the mass parts, stirring and mixing mud, putting the wet mud into a mud mixer, mixing and kneading mud, pugging for 3 times, putting the pug subjected to pugging into a vacuum pug mill again, performing vacuum pugging for 3 times, sealing the pug subjected to vacuum pugging by using a preservative film, standing and aging for 10h in humid air (the relative humidity is 60%) at normal temperature and normal pressure; and (3) putting the aged mud blank into an extrusion forming machine for extrusion, wherein the extrusion pressure is 20MPa, cutting the mud blank into a honeycomb ceramic wet blank body by using a molybdenum wire, carrying out microwave heating on the wet blank body, carrying out shaping and drying treatment at 100 ℃, carrying out microwave drying for 10min, roasting the dried blank body, and roasting for 4h at the roasting temperature of 500 ℃ to obtain the honeycomb type integral structure adsorbent.
Example 5:
weighing 50 parts of SBA-3 molecular sieve, 8 parts of clay and 12 parts of mullite fiber according to the mass parts, mixing and stirring for 30min, adding 7 parts of polyvinyl alcohol, 5 parts of lubricant and 50 parts of deionized water into the mixed dry material according to the mass parts, stirring and mixing mud, putting the wet mud into a mud mixer, mixing and kneading mud, pugging for 3 times, putting the pug subjected to pugging into a vacuum pug mill again, performing vacuum pugging for 3 times, sealing the pug subjected to vacuum pugging by using a preservative film, standing and aging for 10h in humid air (the relative humidity is 70%) at normal temperature and normal pressure; and (3) putting the aged mud blank into an extrusion forming machine for extrusion, wherein the extrusion pressure is 20MPa, cutting the mud blank into a honeycomb ceramic wet blank body by using a molybdenum wire, carrying out microwave heating on the wet blank body, carrying out shaping and drying treatment at 100 ℃, carrying out microwave drying for 10min, roasting the dried blank body, and roasting for 4h at the roasting temperature of 500 ℃ to obtain the honeycomb type integral structure adsorbent.
Example 6:
the specific operation is the same as that in example 1, except that 50 parts by mass of MCM-41 molecular sieve, 6 parts by mass of clay and 12 parts by mass of mullite fiber are weighed.
The specific operation is the same as that in example 1, except that 50 parts by mass of MCM-41 molecular sieve, 8 parts by mass of clay and 17 parts by mass of mullite fiber are weighed.
The specific operation is the same as that in example 1, except that 3 parts by mass of sodium hydroxymethyl cellulose, 2 parts by mass of a lubricant and 15 parts by mass of deionized water are added to the mixed dry material, and stirring and mud mixing are performed.
The specific operation is the same as that in example 1, except that 15 parts by mass of sodium hydroxymethyl cellulose, 15 parts by mass of a lubricant and 45 parts by mass of deionized water are added to the mixed dry material, and the mixture is stirred and mixed with mud.
The specific operation is the same as that of example 1, except that the pug after vacuum pugging is sealed by a preservative film, and the pug is kept stand and aged for 8 hours in humid air at normal temperature and normal pressure.
The specific operation is the same as that of example 1, except that the pug after vacuum pugging is sealed by a preservative film, and the pug is kept stand and aged for 24 hours in humid air at normal temperature and normal pressure.
The specific operation is the same as that of example 1, except that the dried green body is roasted at 500 ℃ for 10 h.
The specific operation is the same as that of example 1, except that the dried green body is roasted at 800 ℃ for 3 h.
Example 7:
the adsorbent prepared in the embodiments 1 to 6 is subjected to VOCs adsorption and desorption performance test on a VOCs adsorption and desorption analyzer modified by Agilent 7890 chromatography at normal temperature and normal pressure at an adsorption airspeed of 6000h-1The adsorption performance test is carried out under the condition, the adsorption capacity of the prepared adsorbent is 0.1-0.3 g/g, and the desorption rate at 200 ℃ is more than 95%.
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.

Claims (10)

1. A monolithic structure adsorbent, comprising a mesoporous molecular sieve, clay, and mullite fibers; the mass ratio of the mesoporous molecular sieve to the clay to the mullite fiber is 40-80: 5-20: 10 to 30.
2. The monolithic structure adsorbent of claim 1, wherein the mesoporous molecular sieve is selected from at least one of MCM-41, MCM-48, MCM-50, SBA-15, SBA-3, FDU-5.
3. The monolithic structure adsorbent according to claim 1, wherein the adsorbent has an adsorption temperature of 0-60 ℃ and a desorption temperature of 120-300 ℃ for adsorbing VOCs gas;
preferably, the adsorbent has an adsorption capacity of 0.1-0.3 g/g for adsorbing VOCs gas, and a desorption rate of more than 95%.
4. A method of making a monolithic structure sorbent according to any of claims 1 to 3, comprising the steps of:
(1) pugging wet pug containing mesoporous molecular sieve, clay and mullite fiber to obtain pug;
(2) and sealing, aging and molding the pug to obtain a wet blank, and shaping and roasting to obtain the integral-structure adsorbent.
5. The method according to claim 4, wherein the wet pug in step (1) further comprises a binder, a lubricant and deionized water;
preferably, the binder is selected from at least one of phenolic resin emulsion, polyvinyl alcohol, sodium hydroxymethyl cellulose and acrylic resin emulsion.
6. The method of claim 5, wherein the mass ratio of the sum of the masses of the mesoporous molecular sieve, the clay and the mullite fiber to the mass of the binder, the lubricant and the deionized water in step (1) is 100: 5-20: 3-10: 20 to 60.
7. The method of claim 4, wherein the forming in step (2) is extrusion;
the shaping in the step (2) is drying treatment, and the moisture content of the dried blank is less than 10%.
8. The method according to claim 4, wherein the aging in step (2) is: aging for 8-24 h under the air condition with the relative humidity of 40-80%;
the setting conditions in the step (2) are as follows: heating by microwave at 90-120 ℃;
the roasting conditions in the step (2) are as follows: roasting at 500-800 ℃ for 3-10 h.
9. The method according to claim 4, characterized in that it comprises the following steps:
1) mixing mesoporous molecular sieve, clay and mullite fiber to obtain a mixed dry material;
2) adding a binder, a lubricant and deionized water into the mixed dry material obtained in the step 1), stirring and mixing mud to obtain wet mud material;
3) mixing and kneading the wet pug obtained in the step 2), and then performing vacuum pugging;
4) sealing the pug subjected to vacuum pugging in the step 3) by using a preservative film, standing and aging in air with the relative humidity of 40-80% at normal temperature and normal pressure;
5) extruding and molding the aged mud blank obtained in the step 4), wherein the extrusion pressure is 10-25 MPa, and cutting the mud blank into a wet blank body;
6) microwave heating the wet blank obtained in the step 5), and carrying out shaping and drying treatment at the temperature of 90-120 ℃;
7) and (3) roasting the blank dried in the step 6) to obtain the adsorbent with the integral structure.
10. At least one of the monolithic adsorbent according to any one of claims 1 to 3 and the monolithic adsorbent according to any one of claims 4 to 9 is used for purification of a gas containing VOCs.
CN201811325013.0A 2018-11-08 2018-11-08 Monolithic structure adsorbent, preparation method and application thereof Pending CN111151219A (en)

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Application publication date: 20200515