CN112058217A - Silicon-based adsorption material capable of being rapidly regenerated and method for microwave in-situ degradation of organic pollutants - Google Patents
Silicon-based adsorption material capable of being rapidly regenerated and method for microwave in-situ degradation of organic pollutants Download PDFInfo
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Abstract
The invention particularly relates to a silicon-based adsorption material capable of being rapidly regenerated and a method for degrading organic pollutants in situ by microwaves. Aiming at organic pollutants, the invention provides a modified silicon-based adsorption material for treating the organic pollutants, wherein a molecular sieve is used as a carrier of the silicon-based adsorption material, and a metal oxide with catalysis and wave absorption characteristics is loaded on the surface of the silicon-based adsorption material. When the adsorption material loaded with the metal oxide is saturated to adsorb organic pollutants, the adsorption material is placed in a microwave field, and the reaction temperature is controlled by controlling the power. The microwave has a selective heating effect on the metal oxide, and local hot spots are shaped, so that the catalytic effect is started, and the microwave regeneration of the adsorption material and the in-situ catalytic oxidation of organic pollutants are achieved. The method can realize the regeneration of the adsorption material in a short time, and can carry out in-situ catalytic oxidation on the organic pollutants, thereby being energy-saving, efficient, safe and controllable, simple in device and convenient to operate.
Description
Technical Field
The invention belongs to the technical field of volatile organic pollutant treatment, and particularly relates to a modified silicon-based adsorption material and application of the silicon-based adsorption material in rapid microwave regeneration and in-situ catalytic organic pollutant oxidative degradation.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
Vocs (volatile organic compounds), which are a general term for a class of organic compounds, include halogenated hydrocarbons, aromatic compounds, polycyclic aromatic hydrocarbons, aldehydes, ketones, alcohols, ethers, alkanes, alkenes, and the like, and are widely used in the paint production, chemical fiber industry, metal coating, chemical coating, shoe making, leather making, plywood manufacturing, tire manufacturing, and other industries. Discharge of VOCs into the atmosphere destroys the ozone layer in the atmosphere, causes photochemical smog, and also promotes the formation of secondary organic aerosols and most VOCs are toxic and harmful, posing a serious threat to the environment and human health. Therefore, VOCs management is imminent.
The method for purifying and treating the waste gas with low cost, low energy consumption and no secondary pollution is preferably selected, and the realization of the recycling of resources is the main principle for treating the VOCs at present. The VOCs treatment technology at the present stage mainly comprises an adsorption method, a combustion method, a catalytic oxidation method, a biological method, a low-temperature plasma method, a photocatalytic oxidation method and the like. Among them, the adsorption method has the advantages of low cost and low energy consumption, and becomes a widely-used VOCs treatment technology. The adsorption method mostly adopts a solid adsorbent to adsorb volatile organic compounds in the waste gas, thereby achieving the purpose of removing. The adsorbent is used as the key of the adsorption technology, generally needs to have rich pore structure and specific surface area, and mainly comprises a molecular sieve and activated carbon, wherein the activated carbon adsorption material generally has larger adsorption capacity, but has larger potential safety hazard at higher regeneration temperature; in contrast, molecular sieve adsorption materials are used more because of their advantages of excellent thermal stability, safety and adsorption-desorption recycling performance. Although the adsorption technology can remove the VOCs in the exhaust gas to achieve the purpose of gas purification, it is essential to enrich the low-concentration VOCs, and the concentrated VOCs gas generated in the regeneration process of the adsorbent still needs to be carefully treated to avoid secondary pollution. The desorbed concentrated VOCs gas is introduced into catalytic oxidation equipment for complete degradation, so that the adsorption technology is often combined with the catalytic oxidation technology in industry for VOCs treatment, but the defects of low efficiency and complex equipment and process still exist, for example, the efficient regeneration of the adsorbent and the catalytic oxidation technology can be cooperated, so that the development of the VOCs treatment technology can be greatly promoted, and the technical economy can be improved.
Disclosure of Invention
Aiming at the defects of low efficiency and complex equipment and process of the prior molecular sieve adsorption, hot air desorption and catalytic oxidation process. The invention aims to overcome the defects of the VOCs treatment technology, integrates the two processes of adsorbent regeneration and VOCs catalytic oxidation, and provides the VOCs treatment technology for simultaneously carrying out adsorbent adsorption and microwave regeneration and in-situ catalytic organic matter degradation by utilizing the characteristic advantages of microwave selectivity and rapid heating. The key point of the technology lies in the modification of the adsorption material, so that the invention provides a silicon-based adsorption material which can be rapidly regenerated and can simultaneously catalyze the degradation of organic matters in situ.
Based on the technical purpose, the invention provides the following technical scheme:
the invention provides a silicon-based adsorption material capable of being rapidly regenerated, which takes a porous silicon material as a carrier, and metal oxide with wave-absorbing and catalyzing dual-function characteristics is loaded on the surface of the silicon-based adsorption material;
the porous silicon material molecular sieve comprises one or a mixture of USY, NaY and 13X, ZSM molecular sieves;
the metal oxide is selected from the group consisting of, but not limited to, CuO, MnO, Mn3O4、Co3O4、NiO、CeO2One or more of them.
The invention provides a modification method for a silicon-based adsorption material, which loads metal oxide with catalytic activity and wave-absorbing property on an adsorbent: on one hand, the adsorbent can provide an effective surface and a proper pore structure, reduce the agglomeration of active components, improve the dispersity and catalytic activity of the active components and enhance the mechanical strength of the catalyst. On the other hand, the integration of adsorbent regeneration and VOCs catalytic oxidation can be realized by utilizing a microwave heating characteristic mechanism, and the rapid desorption of adsorbates and the rapid regeneration of adsorption materials can be realized by microwave rapid and integral heating; the selective heating characteristic of the microwave can quickly heat up the metal oxide to start the catalytic action of the metal oxide, thereby achieving the in-situ catalytic oxidation of the organic pollutants. The modified silicon-based adsorption material has a good adsorption effect on VOCs, and particularly can realize a good adsorption effect on organic pollutants of formaldehyde, ether, acetone, benzene and benzene series, and organic pollutants with a concentration of 10ppm to 1000 ppm. The modified silicon-based adsorption material can realize in-situ catalytic oxidation degradation of organic pollutants and quick regeneration of the adsorption material through microwave heating.
Particularly, the research of the invention also proves that the silicon-based adsorption material obtained based on the modification mode has good degradation effect on organic pollutants after being heated by microwaves, and the silicon-based adsorption material also has good cyclic regeneration performance, and the efficiency is not reduced after being heated for many times.
In a second aspect of the present invention, a method for microwave in-situ catalytic degradation of organic pollutants is provided, wherein the method comprises adsorbing organic pollutants with the silicon-based adsorbing material of the first aspect, and heating the adsorbed material in a microwave environment to degrade the adsorbed organic pollutants.
The microwave has a selective heating effect on the metal oxide. The capacity of the substance for absorbing the microwave is related to the characteristics of the substance, the metal oxide with the wave absorbing characteristic has stronger coupling effect with the microwave, the microwave is strongly absorbed, and the microwave energy is converted into heat energy to quickly increase the temperature. The adsorption material takes a silicon-based adsorption material as a carrier and loads metal oxide with wave-absorbing characteristics, so that the metal oxide forms local hot spots in a microwave field, and the catalytic action of the adsorption material is started.
When the adsorption material loaded with the metal oxide is saturated in adsorbing organic pollutants, the adsorption material is placed in a microwave field, and the temperature is controlled by controlling certain power. The microwave accurately heats the metal oxide, local hot spots are formed on the surface of the adsorption material, the in-situ catalytic oxidation effect on organic pollutants is achieved, and meanwhile, the silicon-based adsorption material is quickly regenerated.
Based on the principle, the silicon-based adsorption material provided by the invention can effectively shorten the treatment time and improve the treatment efficiency of organic pollutants by degrading the organic pollutants in situ through microwaves. And because the silicon-based adsorption material has good regeneration performance, the use times in industrial production application can be effectively increased, and the cost is reduced.
In a third aspect of the invention, there is provided the use of the silica-based adsorbent material of the first aspect in the preparation of a decontamination product.
The beneficial effects of one or more technical schemes are as follows:
1. the method for degrading organic pollutants in situ provided by the invention is simple, low in equipment cost, high in degradation efficiency, short in catalytic oxidation time and high in reliability, and can be carried out under normal pressure.
2. The invention fully utilizes the characteristics of microwave integral and high-efficiency heating of the wave-absorbing medium, breaks through the limitation of low efficiency of the traditional heating mode, realizes the rapid regeneration of the adsorbent, selectively acts on the strong wave-absorbing medium based on the microwave to shape high-temperature hot spots, and realizes the synergy of the regeneration of the adsorbent and the degradation of organic matters. Compared with the traditional adsorbent regeneration technology, the method realizes the synergy of adsorbent regeneration and organic matter degradation elimination.
3. The adsorbent is quickly regenerated based on the characteristic of microwave quick heating wave-absorbing medium, and the in-situ degradation of VOCs in the desorption process is realized by utilizing a mechanism of microwave induction high-temperature hot spot effect.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the invention and together with the description serve to explain the invention and not to limit the invention.
FIG. 1 shows a silicon-based adsorbing material Co described in example 13O4XRD pattern of/USY.
FIG. 2 shows a silicon-based adsorbing material Co as described in example 13O4Scanning electron microscope picture of/USY.
FIG. 3 shows a silicon-based adsorbing material Co as described in example 13O4Adsorption curve of/USY on toluene.
FIG. 4 shows a silicon-based adsorbing material Co as described in example 13O4The catalytic degradation effect curve of USY to toluene.
FIG. 5 shows the silicon-based adsorbing material Co of example 13O4The effect curve of USY catalyzing the degradation of toluene in a dry and wet state.
FIG. 6 shows a silicon-based adsorbing material Co as described in example 13O4Temperature rise characteristic of USY under the action of microwave.
FIG. 7 shows a silicon-based adsorbing material Co as described in example 13O4The degradation effect curve of the catalytic toluene under the microwave action of the USY.
Detailed Description
It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the invention. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
The invention aims to provide a method for degrading organic pollutants by microwave rapid regeneration coupling in-situ catalytic oxidation, which is a process technology with short treatment time, high efficiency, low cost and high reliability.
In order to achieve the purpose, the invention provides a method for degrading organic pollutants by microwave rapid regeneration coupling in-situ catalytic oxidation, wherein an adsorption material is loaded with a metal oxide with wave-absorbing property. When the adsorption material adsorbs organic pollutants to reach saturation, the adsorption material is regenerated in a microwave heating mode, the adsorbent is quickly regenerated based on the characteristic of a microwave quick heating wave-absorbing medium, and meanwhile, the metal oxide is selectively heated by microwaves, the catalytic effect of the metal oxide is started, and the in-situ degradation of the organic pollutants in the desorption process is realized.
The invention provides a silicon-based adsorption material capable of being quickly regenerated, wherein the silicon-based adsorption material takes a porous silicon material as a carrier, and a metal oxide with wave-absorbing and catalyzing dual-function characteristics is loaded on the surface of the silicon-based adsorption material;
the porous silicon material molecular sieve comprises one or a mixture of USY, NaY and 13X molecular sieves;
the metal oxide is selected from the group consisting of, but not limited to, CuO, MnO, Mn3O4、Co3O4、NiO、CeO2One or more of them.
Preferably, the metal oxide is uniformly attached to the surface of the porous silicon material.
Further preferably, the metal oxide is partially or completely bound to the surface of the molecular sieve material by physical adsorption.
Further preferably, the metal oxide is partially or completely bonded to the surface of the molecular sieve by a chemical bond.
Preferably, the preparation method of the silicon-based adsorption material comprises the following steps: adding a metal oxide synthesis raw material and a molecular sieve into a solvent, uniformly mixing to obtain a mixed solution, placing the mixed solution into a reaction kettle, and obtaining a solid sample through a hydrothermal synthesis method, wherein the solid sample is calcined to obtain the silicon-based adsorption material.
Further preferably, the metal oxide synthesis raw materials are mixed uniformly and then added with a molecular sieve for further mixing to obtain a uniform mixed solution.
Further preferably, the solid sample obtained by the hydrothermal synthesis further comprises a washing step.
Further preferably, the modification of the silicon-based adsorption material further comprises a step of performing surface modification by using a noble metal, wherein the noble metal modification includes but is not limited to one or more of platinum modification, palladium modification and rubidium modification.
The invention provides a silicon-based adsorption material which has good adsorption effect on VOCs (volatile organic compounds), particularly organic pollutants of formaldehyde, ether, acetone, benzene and benzene series, and can realize good adsorption effect on the organic pollutants with the concentration of 10ppm-1000 ppm. The silicon-based adsorption material can realize in-situ catalytic oxidation degradation of organic pollutants and regeneration of the adsorption material by heating. Particularly, the research of the invention proves that the silicon-based adsorbing material has good degradation effect on organic pollutants and good cyclic regeneration performance after being heated by microwave.
In a second aspect of the present invention, a method for microwave in-situ catalytic degradation of organic pollutants is provided, wherein the method comprises adsorbing organic pollutants with the silicon-based adsorbing material of the first aspect, and heating the adsorbed material in a microwave environment to degrade the adsorbed organic pollutants.
Preferably, the organic contaminants are organic contaminants including, but not limited to, formaldehyde, diethyl ether, acetone, benzene, toluene, benzene series, and the like.
Preferably, the power of the microwave field is 100W-3000W.
Preferably, the microwave heating time is 2min-30 min.
In some embodiments of the above preferred technical solution, the power of the microwave field is adjusted in the range of 100W-1000W, and the silica-based adsorbent material has a mass of 0.1-1g and a particle size of 20-40 mesh. The microwave power is set according to the mass of the silicon-based adsorption material and the height of the bed layer, when the mass of the silicon-based adsorption material is larger and the particle size is larger, a microwave field with higher power needs to be used, and the heating time is properly prolonged.
Preferably, the method further comprises the steps of collecting the degraded gas by using the gas bag, and testing and analyzing the gas in the gas bag by using a gas chromatograph.
In some specific embodiments of the above preferred technical solutions, the method for in situ catalytic degradation of organic pollutants by microwaves specifically operates as follows: firstly, setting the power of a microwave oven, placing a silicon-based adsorption material in a fixed bed reactor, and carrying out catalytic oxidation decomposition on pollutants on the surface of the silicon-based adsorption material in the microwave oven when carrier gas passes through the fixed bed reactor at a constant speed, thereby achieving the degradation effect and regeneration of the silicon-based adsorption material.
The carrier gas contains organic pollutant components such as formaldehyde, diethyl ether, acetone, benzene, toluene, benzene series, etc. with air as carrier gas.
The mass space velocity is 60L g-1·h-1-600L·g-1·h-1。
In a third aspect of the invention, there is provided the use of the silica-based adsorbent material of the first aspect in the preparation of a decontamination product.
Preferably, the organic pollutant degradation product is applied to removal of organic pollutants in gas and water body environments;
further preferably, the gas environment includes an open and closed gas environment, and also includes a visible light gas environment or a humid gas environment.
Preferably, the organic pollutant degradation product also comprises other types of organic pollutant catalytic degradation materials.
In some embodiments of the above preferred embodiments, the organic contaminant adsorbent is used in combination with other substances having an organic contaminant degradation effect, such as composite metal oxides, activated carbon-supported metal oxides, iron-based magnetic metal oxides, or organometallic framework-type materials.
In still other embodiments of the above preferred embodiments, the silica-based adsorbent material is used in combination with other carriers or auxiliary materials, such as biochar, nanomaterials, algae, gels, bentonite, diatomaceous earth, and the like.
In order to make the technical solutions of the present invention more clearly understood by those skilled in the art, the technical solutions of the present invention will be described in detail below with reference to specific embodiments.
Example 1
In this embodiment, a silicon-based adsorbing material is provided, where the silicon-based adsorbing material uses USY as a carrier of the silicon-based adsorbing material, and the metal oxide is Co3O4。
A method for degrading organic pollutants by coupling microwave rapid regeneration and in-situ catalytic oxidation of a silicon-based adsorption material is disclosed, wherein the adsorbent is a granular silicon-based adsorption material.
The adsorbent Co degraded by microwave rapid regeneration coupling in-situ catalytic oxidation3O4The USY is prepared by a hydrothermal synthesis method, and comprises the following steps:
(1) 3.36g of Co (CH) are weighed out3COO)2·4H2O in a 250mL beaker, 60mL of deionized water was added and stirred uniformly, 1.62g of urea was added to a small beaker, and 60mL of deionized water was added and stirred uniformly. The prepared urea solution is dripped into the cobalt acetate solution. Adding 3g of molecular sieve USY, stirring uniformly, and performing ultrasonic treatment for 30min to form a uniform mixed solution.
(2) And transferring the mixed solution into a reaction kettle, and controlling the hydrothermal temperature at 110 ℃ and the hydrothermal time at 6 h. After the reaction is finishedFiltering, washing with deionized water and anhydrous ethanol repeatedly, vacuum drying at 80 deg.C for 12 hr, and grinding. Raising the temperature of the obtained sample to 350 ℃ at the heating rate of 1 ℃/min and keeping the temperature for 3 hours to obtain Co3O4the/USY material.
As can be seen from FIG. 1, the prepared adsorbing material is Co3O4/USY。
As can be seen from FIG. 2, Co produced3O4The USY adsorbing material is in a flower-shaped structure, the surface of the USY adsorbing material is provided with a larger pore structure, and the contact area of the adsorbing material and organic pollutant gas is increased.
FIG. 3 is Co3O4The flow rate of carrier gas air is 36 L.g-1·h-1The mass of the adsorbing material is 1.0g, the particle size is 20-40 meshes, and the concentration of the organic pollutants is 350 ppm. As can be seen from FIG. 3, Co produced3O4The toluene adsorption of the/USY adsorption material started to penetrate at 36min, and the Co adsorption time was 170min3O4The toluene adsorption of the 1: 1/USY adsorbent was saturated and the toluene adsorption capacity was 84.56m3In terms of/g, it can be seen that Co is produced3O4The USY adsorbing material has better adsorption property to toluene.
FIG. 4 shows the prepared Co3O4The catalytic oxidation characteristic of toluene by using USY adsorbing material. The air flow rate of the carrier gas is 600mL/min, the inlet concentration of the toluene is 320ppm, the mass of the adsorbent is 0.2g, and the adsorbent is uniformly mixed with 1g of quartz sand to be used as a catalyst bed layer, so that the prepared Co can be seen3O4The toluene conversion rate of the USY adsorbing material is more than 90 percent at 300 ℃; the degradation rate and the mineralization rate of toluene at 325 ℃ are both high, which shows that the regeneration of the adsorbent and the catalytic degradation of organic matters can be realized by adopting hot air at 325 ℃ to regenerate the adsorbent saturated in adsorption.
FIG. 5 preparation of Co3O4The comparison of the catalytic oxidative degradation results of toluene in dry and wet states of the USY adsorbing material is shown in FIG. 6. The air flow rate of the carrier gas is 600mL/min, the inlet concentration of the toluene is 330ppm, the mass of the adsorbent is 0.2g, and the adsorbent is uniformly mixed with 1g of quartz sandThen the catalyst is used as a catalyst bed layer; the relative humidity in wet condition was 75%. As can be seen, Co produced3O4The USY adsorbing material also has excellent catalytic oxidation performance in a wet state, and the toluene degradation rate and the mineralization rate are both good at 325 ℃, which shows that the prepared adsorbing material can be applied to the catalytic conversion of high-humidity flue gas organic matters.
As can be seen from FIG. 6, Co produced3O4the/USY has excellent wave absorbing property, the temperature rises to 445 ℃ in a microwave field with the microwave power of 1000W for 2min and is kept unchanged, and the reaction temperature can be quickly adjusted by adjusting the microwave power, so that the potential of quickly regenerating and degrading VOCs in situ is realized.
FIG. 7 Co prepared under microwave conditions3O4The USY is used for catalyzing toluene to be oxidized and degraded, the reaction temperature is controlled to be 400 ℃ in the experimental process, the mass of the adsorbent is 1g, the flow rate of carrier gas is 600mL/min, the concentration of a toluene inlet is 300ppm, and the relative humidity is 75%. As can be seen, the toluene degradation rate and the carbon dioxide selectivity can both reach 90%, and the prepared material is proved to have the function of catalyzing the degradation of VOCs in situ under the microwave action.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A silicon-based adsorption material capable of being rapidly regenerated is characterized in that a porous silicon material is used as a carrier of the silicon-based adsorption material, and a metal oxide with wave-absorbing property is loaded on the surface of the silicon-based adsorption material;
the porous silicon material molecular sieve comprises one or a mixture of USY, NaY and 13X molecular sieves;
the metal oxide is selected from the group consisting of, but not limited to, CuO, MnO, Mn3O4、Co3O4、NiO、CeO2One or more of them.
2. The fast regenerating silicon-based adsorbent material according to claim 1, wherein said metal oxide is uniformly attached to the surface of the porous silicon material; the load capacity of the metal oxide is 1 mmol-0.05 mol/g of the silicon-based adsorption material;
preferably, the metal oxide is partially or completely bound on the surface of the molecular sieve material through physical adsorption;
preferably, the metal oxide is partially or completely bonded to the surface of the molecular sieve by a chemical bond.
3. The fast regenerating silicon-based adsorbent material according to claim 1, wherein said silicon-based adsorbent material is prepared by a method comprising the steps of: adding a metal oxide synthesis raw material and a molecular sieve into a solvent, uniformly mixing to obtain a mixed solution, placing the mixed solution into a reaction kettle, and obtaining a solid sample through a hydrothermal synthesis method, wherein the solid sample is calcined to obtain the silicon-based adsorption material.
4. The rapidly regenerating silicon-based adsorbent material of claim 3, wherein the metal oxide synthesis feedstock is mixed uniformly and then added to a molecular sieve for one-step mixing to obtain a homogeneous mixed solution;
or the solid sample obtained by the hydrothermal synthesis further comprises a washing step;
or the silicon-based adsorption material further comprises a step of performing surface modification by using noble metal, wherein the noble metal modification comprises one or more of platinum modification, palladium modification and rubidium modification.
5. A method for degrading organic pollutants by microwave in-situ catalysis, which is characterized by comprising the steps of adsorbing the organic pollutants by using the rapidly-regenerated silicon-based adsorbing material as claimed in any one of claims 1 to 4, and heating the adsorbing material in a microwave environment for degradation.
6. The microwave in-situ catalytic degradation method for organic pollutants according to claim 5, wherein the organic pollutants are organic pollutants including but not limited to formaldehyde, diethyl ether, acetone, benzene, toluene, benzene series, and the like;
or the power of the microwave field is 100W-3000W;
or the microwave heating time is 2min-30 min.
7. The microwave in-situ catalytic degradation method for organic pollutants according to claim 6, wherein the power of the microwave field is adjusted within a range from 100W to 3000W, the mass space velocity of the silicon-based adsorption material is 60-600L/(g.h), and the particle size is 20-40 meshes.
8. The method for microwave in-situ catalytic degradation of organic pollutants as claimed in claim 5, further comprising collecting the degraded gas by using an air bag.
9. Use of a fast regenerating silicon-based adsorption material according to any one of claims 1 to 4 for the preparation of a decontamination product.
10. Use of a rapidly regenerating silicon-based adsorbent material according to claim 9 in the preparation of a decontamination product, wherein said organic contaminant degradation product is used for the removal of organic contaminants from a gaseous, aqueous environment; preferably, the gas environment includes an open and closed gas environment, and also includes a visible light gas environment or a humid gas environment;
or, the organic pollutant degradation product also comprises other types of organic pollutant catalytic degradation materials;
preferably, the organic pollutant absorbent is used in combination with other substances having an organic pollutant degradation effect, such as a composite metal oxide, an activated carbon-supported metal oxide, an iron-based magnetic metal oxide, or an organic metal framework type material; further, the silica-based adsorbent material is used in combination with other carriers or auxiliary materials.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114797763A (en) * | 2022-04-28 | 2022-07-29 | 中国城市建设研究院有限公司 | Molecular sieve composite material for adsorbing organic matters in water, preparation method and application thereof |
| CN115722070A (en) * | 2021-08-25 | 2023-03-03 | 中国科学院城市环境研究所 | Electromagnetic induction heating material, preparation method and application thereof in VOCs purification |
Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011094456A1 (en) * | 2010-01-27 | 2011-08-04 | The Regents Of The University Of California | Nanostructed transition metal oxides useful for water oxidation catalysis |
| CN102814191A (en) * | 2012-09-03 | 2012-12-12 | 上海电力学院 | Low-temperature denitrated CeO2-NaX molecular sieve catalyst and preparation method thereof |
| CN103224258A (en) * | 2013-04-26 | 2013-07-31 | 吉林化工学院 | Simple method for preparing Co3O4 nano-spheres and beta-Co(OH)2 micron-flowers |
| CN105854887A (en) * | 2016-03-25 | 2016-08-17 | 武汉工程大学 | Cobalt-cerium double-metal oxide nanosphere and preparation method thereof |
| CN106268814A (en) * | 2015-05-20 | 2017-01-04 | 中国科学院大连化学物理研究所 | A kind of flower-shaped Cobalto-cobaltic oxide catalyst and its preparation method and application |
| CN106475130A (en) * | 2016-11-10 | 2017-03-08 | 上海纳米技术及应用国家工程研究中心有限公司 | Low-temperature SCR integral catalyzer and its preparation and application in a kind of manganese base |
| CN106582651A (en) * | 2017-01-10 | 2017-04-26 | 武汉大学 | Preparation method for porous carrier-loaded nano-cobalt catalyst |
| CN107789941A (en) * | 2016-08-31 | 2018-03-13 | 姜兴茂 | The method of microwave induced absorption in-situ catalytic oxidation degradable organic pollutant |
| CN108722472A (en) * | 2017-04-19 | 2018-11-02 | 北京化工大学 | A kind of preparation method and application of rare earth modified NaY molecular sieve |
| CN109289901A (en) * | 2018-11-02 | 2019-02-01 | 张浩然 | A kind of Oxidation at room temperature eliminates the Y type molecular sieve carried noble metal Pt catalyst of formaldehyde |
| CN109817929A (en) * | 2019-01-25 | 2019-05-28 | 安徽师范大学 | A kind of helical form silica/cobaltosic oxide composite nano materials and preparation method thereof and the application in lithium ion battery |
| CN111013590A (en) * | 2019-11-21 | 2020-04-17 | 南京理工大学 | Preparation method of biocarbon-loaded cobaltosic oxide catalytic material |
| CN111420697A (en) * | 2020-04-07 | 2020-07-17 | 浙江大学 | Pt/Ce-USY catalyst for oxidative degradation of chlorine-containing VOCs and preparation method thereof |
| CN111479630A (en) * | 2017-12-22 | 2020-07-31 | 亮锐控股有限公司 | Manganese catalyst for catalyzing formaldehyde oxidation and preparation and application thereof |
-
2020
- 2020-09-04 CN CN202010922450.1A patent/CN112058217A/en active Pending
Patent Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011094456A1 (en) * | 2010-01-27 | 2011-08-04 | The Regents Of The University Of California | Nanostructed transition metal oxides useful for water oxidation catalysis |
| CN102814191A (en) * | 2012-09-03 | 2012-12-12 | 上海电力学院 | Low-temperature denitrated CeO2-NaX molecular sieve catalyst and preparation method thereof |
| CN103224258A (en) * | 2013-04-26 | 2013-07-31 | 吉林化工学院 | Simple method for preparing Co3O4 nano-spheres and beta-Co(OH)2 micron-flowers |
| CN106268814A (en) * | 2015-05-20 | 2017-01-04 | 中国科学院大连化学物理研究所 | A kind of flower-shaped Cobalto-cobaltic oxide catalyst and its preparation method and application |
| CN105854887A (en) * | 2016-03-25 | 2016-08-17 | 武汉工程大学 | Cobalt-cerium double-metal oxide nanosphere and preparation method thereof |
| CN107789941A (en) * | 2016-08-31 | 2018-03-13 | 姜兴茂 | The method of microwave induced absorption in-situ catalytic oxidation degradable organic pollutant |
| CN106475130A (en) * | 2016-11-10 | 2017-03-08 | 上海纳米技术及应用国家工程研究中心有限公司 | Low-temperature SCR integral catalyzer and its preparation and application in a kind of manganese base |
| CN106582651A (en) * | 2017-01-10 | 2017-04-26 | 武汉大学 | Preparation method for porous carrier-loaded nano-cobalt catalyst |
| CN108722472A (en) * | 2017-04-19 | 2018-11-02 | 北京化工大学 | A kind of preparation method and application of rare earth modified NaY molecular sieve |
| CN111479630A (en) * | 2017-12-22 | 2020-07-31 | 亮锐控股有限公司 | Manganese catalyst for catalyzing formaldehyde oxidation and preparation and application thereof |
| CN109289901A (en) * | 2018-11-02 | 2019-02-01 | 张浩然 | A kind of Oxidation at room temperature eliminates the Y type molecular sieve carried noble metal Pt catalyst of formaldehyde |
| CN109817929A (en) * | 2019-01-25 | 2019-05-28 | 安徽师范大学 | A kind of helical form silica/cobaltosic oxide composite nano materials and preparation method thereof and the application in lithium ion battery |
| CN111013590A (en) * | 2019-11-21 | 2020-04-17 | 南京理工大学 | Preparation method of biocarbon-loaded cobaltosic oxide catalytic material |
| CN111420697A (en) * | 2020-04-07 | 2020-07-17 | 浙江大学 | Pt/Ce-USY catalyst for oxidative degradation of chlorine-containing VOCs and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| JINGRONG LI ET AL.: ""Preparation and high performance of rare earth modified Co/USY for benzene catalytic combustion"", 《CATALYSIS COMMUNICATIONS》 * |
| QINQIN HUANG ET AL.: ""Catalytic behavior and durability of CeO2 or/and CuO modified USY zeolite catalysts for decomposition of chlorinated volatile organic compounds"", 《JOURNAL OF MOLECULAR CATALYSIS A: CHEMICAL》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115722070A (en) * | 2021-08-25 | 2023-03-03 | 中国科学院城市环境研究所 | Electromagnetic induction heating material, preparation method and application thereof in VOCs purification |
| CN114797763A (en) * | 2022-04-28 | 2022-07-29 | 中国城市建设研究院有限公司 | Molecular sieve composite material for adsorbing organic matters in water, preparation method and application thereof |
| CN114797763B (en) * | 2022-04-28 | 2023-10-31 | 中国城市建设研究院有限公司 | Molecular sieve composite material for adsorbing organic matters in water, preparation method and application thereof |
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