CN112108115A - Preparation method and testing device of carbon-based composite material for catalyzing and degrading multiple organic matters at room temperature - Google Patents
Preparation method and testing device of carbon-based composite material for catalyzing and degrading multiple organic matters at room temperature Download PDFInfo
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- CN112108115A CN112108115A CN202010994145.3A CN202010994145A CN112108115A CN 112108115 A CN112108115 A CN 112108115A CN 202010994145 A CN202010994145 A CN 202010994145A CN 112108115 A CN112108115 A CN 112108115A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 143
- 239000002131 composite material Substances 0.000 title claims abstract description 68
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- 230000000593 degrading effect Effects 0.000 title claims abstract description 14
- 238000012360 testing method Methods 0.000 title claims abstract description 14
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 95
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 95
- 230000015556 catabolic process Effects 0.000 claims abstract description 51
- 238000006731 degradation reaction Methods 0.000 claims abstract description 51
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000012855 volatile organic compound Substances 0.000 claims abstract description 37
- 230000003197 catalytic effect Effects 0.000 claims abstract description 35
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000002994 raw material Substances 0.000 claims abstract description 27
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims abstract description 16
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims abstract description 15
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000004927 clay Substances 0.000 claims abstract description 15
- 239000008096 xylene Substances 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 14
- 239000012798 spherical particle Substances 0.000 claims abstract description 12
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 claims abstract description 8
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims abstract description 8
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims abstract description 8
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229940072049 amyl acetate Drugs 0.000 claims abstract description 3
- PGMYKACGEOXYJE-UHFFFAOYSA-N anhydrous amyl acetate Natural products CCCCCOC(C)=O PGMYKACGEOXYJE-UHFFFAOYSA-N 0.000 claims abstract description 3
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229960003750 ethyl chloride Drugs 0.000 claims abstract description 3
- MNWFXJYAOYHMED-UHFFFAOYSA-M heptanoate Chemical compound CCCCCCC([O-])=O MNWFXJYAOYHMED-UHFFFAOYSA-M 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims description 45
- 238000003756 stirring Methods 0.000 claims description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 37
- 229910001868 water Inorganic materials 0.000 claims description 37
- 150000002894 organic compounds Chemical class 0.000 claims description 35
- 238000001816 cooling Methods 0.000 claims description 32
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- 239000007789 gas Substances 0.000 claims description 23
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 22
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 22
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 22
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 22
- 230000007935 neutral effect Effects 0.000 claims description 21
- 238000005406 washing Methods 0.000 claims description 21
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver nitrate Substances [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 20
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 16
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 14
- 238000005303 weighing Methods 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 11
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 11
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims description 11
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 11
- 239000004408 titanium dioxide Substances 0.000 claims description 11
- 239000011787 zinc oxide Substances 0.000 claims description 11
- 238000001125 extrusion Methods 0.000 claims description 9
- 229910052786 argon Inorganic materials 0.000 claims description 8
- 229960000892 attapulgite Drugs 0.000 claims description 8
- 229910052625 palygorskite Inorganic materials 0.000 claims description 8
- 239000003245 coal Substances 0.000 claims description 7
- 238000005469 granulation Methods 0.000 claims description 6
- 230000003179 granulation Effects 0.000 claims description 6
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(III) nitrate Inorganic materials [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 6
- 239000000440 bentonite Substances 0.000 claims description 5
- 229910000278 bentonite Inorganic materials 0.000 claims description 5
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical group O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- -1 salt silver nitrate Chemical class 0.000 claims description 5
- 229920000742 Cotton Polymers 0.000 claims description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 4
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 4
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 4
- 235000009827 Prunus armeniaca Nutrition 0.000 claims description 3
- 244000018633 Prunus armeniaca Species 0.000 claims description 3
- 235000013399 edible fruits Nutrition 0.000 claims description 3
- 239000002006 petroleum coke Substances 0.000 claims description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 abstract description 39
- 238000001179 sorption measurement Methods 0.000 description 18
- 239000000463 material Substances 0.000 description 12
- SESBRVCBFPABHX-UHFFFAOYSA-N C(C1=CC=CC=C1)=O.ClC1=C(C=CC=C1)O Chemical compound C(C1=CC=CC=C1)=O.ClC1=C(C=CC=C1)O SESBRVCBFPABHX-UHFFFAOYSA-N 0.000 description 7
- DALDUXIBIKGWTK-UHFFFAOYSA-N benzene;toluene Chemical compound C1=CC=CC=C1.CC1=CC=CC=C1 DALDUXIBIKGWTK-UHFFFAOYSA-N 0.000 description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- 238000003795 desorption Methods 0.000 description 5
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 4
- 239000001768 carboxy methyl cellulose Substances 0.000 description 4
- 239000002808 molecular sieve Substances 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 4
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 4
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 4
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 3
- 231100000252 nontoxic Toxicity 0.000 description 3
- 230000003000 nontoxic effect Effects 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 238000004949 mass spectrometry Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000001237 Raman spectrum Methods 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 230000033558 biomineral tissue development Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000003905 indoor air pollution Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 230000001089 mineralizing effect Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000012629 purifying agent Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- IPCXNCATNBAPKW-UHFFFAOYSA-N zinc;hydrate Chemical compound O.[Zn] IPCXNCATNBAPKW-UHFFFAOYSA-N 0.000 description 1
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Classifications
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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
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
-
- 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
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8678—Removing components of undefined structure
- B01D53/8687—Organic components
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8993—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with chromium, molybdenum or tungsten
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/88—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/80—Type of catalytic reaction
- B01D2255/802—Photocatalytic
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/708—Volatile organic compounds V.O.C.'s
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
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- B01D2258/06—Polluted air
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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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- B01J35/617—
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/88—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86
- G01N2030/8809—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86 analysis specially adapted for the sample
- G01N2030/884—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86 analysis specially adapted for the sample organic compounds
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Abstract
The invention relates to a preparation method and a testing device of a carbon-based composite material for catalyzing and degrading volatile organic compounds at room temperature, the method takes modified activated carbon, clay, a first modified metal oxide 1 and a second modified metal oxide 2 as raw materials, the raw materials are fully mixed, granulated or extruded and molded to prepare columnar or spherical particles or honeycomb cubes, and then the columnar or spherical particles or the honeycomb cubes are roasted in inert atmosphere, so that the molded carbon with high specific surface area, high strength and long service life is obtainedThe obtained columnar or spherical or honeycomb carbon-based composite material is used for catalyzing and degrading a plurality of volatile organic compounds in a gas phase at room temperature, such as formaldehyde, benzene, toluene, xylene, phenol, chlorophenol, benzaldehyde, ethyl chloride, cyclohexane or amyl acetate, and the result shows that: for low concentration 1-5mg/m3The catalytic degradation rate of volatile organic compounds such as toluene, benzene and formaldehyde in 24 hours is up to more than 95 percent, and the catalytic degradation rate is 5-10mg/m for high concentration3The catalytic degradation rate of toluene, benzene, formaldehyde and the like in 24 hours is up to more than 90%.
Description
Technical Field
The invention relates to a preparation method and a testing device of a carbon-based composite material for catalyzing and degrading volatile organic compounds at room temperature.
Background
Indoor air pollution caused by various Volatile Organic Compounds (VOCs) emitted by building decoration and furniture harms the health and life quality of people, and the method becomes a social problem for people to worry about, lead about and pay media attention to, and a research hotspot for effectively controlling indoor organic compound (VOCs) pollution in the indoor air field of China is formed accordingly. The method for removing organic compounds (VOCs) in indoor air by adopting the purification material is an important way for solving the problem, wherein activated carbon adsorption is considered as a reliable and safe purification mode, and the method is widely applied to the purification of the organic compounds (VOCs) in the indoor air, but the adsorption capacity of the activated carbon is limited, and the removal capacity is not realized when the adsorption is saturated. In addition, toxic gases adsorbed in the pores of activated carbon run the risk of desorption and release, and thus there is a possibility of secondary pollution. Therefore, the activated carbon can only temporarily enrich organic compounds (VOCs) and cannot radically and thoroughly convert the organic compounds (VOCs) into nontoxic and harmless carbon dioxide and water. In addition, although photocatalytic degradation and thermocatalytic combustion are common means for industrially removing high concentration organic compounds (VOCs), thermocatalytic has high energy consumption and large equipment investment, and is not suitable for removing low concentration organic compounds (VOCs); the photocatalytic degradation performance is not ideal, toxic and harmful intermediate products are generated in the catalytic process, and organic matters are difficult to mineralize completely. From this, it is known that photocatalysis and thermocatalysis are not suitable for indoor purification of low concentration organic compounds (VOCs) in general households. Therefore, the development of the composite material integrating room temperature catalytic degradation and adsorption is of great significance for removing indoor VOC. The room temperature catalytic degradation material is combined with the activated carbon, so that on one hand, the enrichment of organic compounds (VOCs) can be realized through the ultrahigh adsorption capacity of the activated carbon, and on the other hand, the enriched organic compounds (VOCs) can be catalytically degraded in a certain time and converted into nontoxic and harmless carbon dioxide and water, and the risk of secondary pollution caused by desorption and release does not exist. In addition, powdered activated carbon is one of the more desirable adsorbents for adsorbing and removing organic compounds (VOCs) due to its high specific surface area and developed pore structure. However, the powder material is limited in practical application, so that the preparation of the formed activated carbon-based composite material has important practical significance for purifying indoor organic compounds (VOCs).
In order to solve the problems of powdered activated carbon and removal of indoor organic compounds (VOCs), the invention aims to prepare a molded activated carbon-based composite material, realize adsorption and catalytic degradation of the indoor organic compounds (VOCs), perform catalytic degradation after adsorption of Various Organic Compounds (VOCs) such as formaldehyde, benzene series and the like, and mineralize the organic compounds into nontoxic and harmless carbon dioxide and water. Starting from the aspects of improving the adsorption capacity, conversion efficiency, service life, mechanical strength and the like of the activated carbon-based composite material, the formed activated carbon-based composite material with excellent adsorption and mineralization performance, high adsorption speed, long service life and high mechanical strength is obtained by modifying the activated carbon and adding a room-temperature catalytic material, and is used for simultaneously adsorbing and mineralizing components such as formaldehyde, benzene, toluene, xylene, phenol, chlorophenol, benzaldehyde and the like.
Disclosure of Invention
The invention aims to provide a preparation method and a testing device of a carbon-based composite material for catalyzing and degrading various organic matters at room temperature, aiming at the defects of the existing activated carbon material, the method takes modified activated carbon, clay, a first modified metal oxide 1 and a second modified metal oxide 2 as raw materials, the carbon-based composite material is prepared by mixing, granulation molding and extrusion molding, the adsorption capacity of the modified activated carbon on organic compounds is improved by adding the modified activated carbon, the catalytic degradation of the organic compounds by the material is realized by adding the first modified metal oxide 1 and the second modified metal oxide 2, and the carbon-based composite material obtained by the method adopts the testing device to catalyze the low concentration of 1-5mg/m3The catalytic degradation rate of volatile organic compounds such as toluene and formaldehyde in 24 hours is up to more than 95 percent, and 5-fold organic acid with high concentration is used10mg/m3The catalytic degradation rate of toluene and formaldehyde in 24 hours is up to more than 90%.
The invention relates to a preparation method of a carbon-based composite material for catalyzing and degrading various organic matters at room temperature, which takes modified activated carbon, clay, a first modified metal oxide 1 and a second modified metal oxide 2 as raw materials to prepare columnar or spherical particles or honeycomb cubes, and then the columnar or spherical particles or the honeycomb cubes are roasted in inert atmosphere, and the specific operation is carried out according to the following steps:
preparation of first modified metal oxide 1:
a. respectively adding 0.01-1moL of metal salt silver nitrate and zinc nitrate and 1-100g of molybdenum oxide into water, fully stirring, transferring the mixture into a high-pressure reaction kettle, reacting at the temperature of 200-300 ℃ for 12-48 hours, cooling, and washing to be neutral to obtain a first modified metal oxide 1;
preparation of second modified metal-free oxide 2:
b. respectively adding 0.01-1moL of metal salt ferric nitrate, cupric nitrate, nickel nitrate or cobalt nitrate and 1-100g of zinc oxide, titanium dioxide and manganese dioxide into water, fully stirring, transferring the mixture into a high-pressure reaction kettle, reacting for 12-48 hours at the temperature of 200-300 ℃, cooling and washing to be neutral to obtain a second modified metal oxide 2;
preparing a carbon-based composite material:
c. respectively weighing raw materials of modified activated carbon, clay, the first modified metal oxide 1 in the step a and the second modified metal oxide 2 in the step b according to the mass ratio of 1:0.1-0.5:0.1-0.5:0.1-0.5, adding the raw materials into a mixing bin, stirring for 1-5 hours, adding 0.3-0.6kg of water, and continuously stirring for 1-2 hours to obtain a mixture, wherein the modified activated carbon is modified cotton stalk activated carbon, fruit tree activated carbon, apricot hull activated carbon, petroleum coke activated carbon and coal activated carbon; the clay is bentonite or attapulgite;
d. c, transferring the mixture obtained in the step c into a granulator for granulation to obtain columnar or spherical particles with the diameter of 1-4 mm;
or transferring the mixture obtained in the step c into an extruder for extrusion molding to obtain a honeycomb cube with the specification of 100 multiplied by 50-100 mm;
e. and d, roasting the columnar or spherical particles or the honeycomb cubes obtained in the step d in an inert atmosphere of nitrogen or argon at the roasting temperature of 300-800 ℃ for 1-8h, and cooling to room temperature to obtain the carbon-based composite material.
The organic matter is formaldehyde, benzene, toluene, xylene, phenol, chlorophenol, benzaldehyde, ethyl chloride, cyclohexane or amyl acetate.
The testing device for the carbon-based composite material obtained by the method is used for preparing and simultaneously catalyzing and degrading various volatile organic compounds in gas phase, and comprises a gas inlet (1), a first valve (2), a sealed cabin (3), a heating element (4), a temperature controller (5), a carbon-based composite material (6), a second valve (7) and a gas outlet (8), wherein the gas inlet (1) is arranged on one side of the sealed cabin (3), the first valve (2) is arranged between the sealed cabin (3) and the gas inlet (1), the gas outlet (8) is arranged on the other side of the sealed cabin (3), the second valve (7) is arranged between the sealed cabin (3) and the gas outlet (8), and the heating element (4) and the temperature controller (5) are arranged in the sealed cabin.
The columnar or honeycomb carbon-based composite material is adopted to catalyze and degrade a plurality of volatile organic compounds in a gas phase.
The carbon-based composite material is catalytically degraded at room temperature without an external heat source or light source.
The preparation method of the carbon-based composite material for catalyzing and degrading various organic matters at room temperature, which is disclosed by the invention, comprises the following specific operations: respectively adding different metal salts and different oxides into water, fully stirring, transferring the mixture into a high-pressure reaction kettle, reacting at the temperature of 200-300 ℃ for 12-48 hours, cooling, and washing to be neutral to respectively obtain a first modified metal oxide 1 and a second modified metal oxide 2. Wherein the raw materials of the first modified metal oxide 1 are water-soluble silver nitrate, zinc nitrate and water-insoluble molybdenum oxide; the raw materials of the second modified metal oxide 2 are nitrate dissolved in water and zinc oxide, titanium dioxide and manganese dioxide which are not dissolved in water, wherein the nitrate comprises ferric nitrate, cupric nitrate, nickel nitrate or cobalt nitrate.
Compared with the prior art, the method for preparing the carbon-based composite material for catalyzing and degrading various organic matters at room temperature and the testing device thereof have the advantages that: the preparation method is simple, environment-friendly and safe, no extra pollutant exists, the obtained molded activated carbon-based composite material has high mechanical strength, good removal performance, recyclable material, long service life, convenient operation and low energy consumption, and is suitable for large-scale industrial production.
The carbon-based composite material obtained by the method adopts a testing device and a nitrogen adsorption and desorption test, and the result shows that: has rich pore structure and larger specific surface area which is as high as 600-800m2The specific surface area of the modified metal oxide is/g, and the specific surface area is measured by XRD, infrared and Raman spectrums, and the specific surface area has obvious characteristic peaks of activated carbon, clay, the first modified metal oxide 1 and the second modified metal oxide 2. Has strong capability of adsorbing VOC and catalyzing degradation, and has lower cost and abundant resources. Therefore, the carbon-based composite material obtained by the method is applied as a purifying agent in the field of indoor organic compound (VOC) control. Carbon-based composite material with low concentration of 1-5mg/m3The catalytic degradation rate of volatile organic compounds such as toluene, formaldehyde and the like in 24 hours is up to more than 95 percent, and the catalytic degradation rate is 5-10mg/m for high concentration3The catalytic degradation rate of toluene, formaldehyde and the like in 24 hours is up to more than 90 percent, which is shown in table 1; tables 1 to 4 show that the first modified metal oxide 1 and the second modified metal oxide 2 are main components for degrading organic compounds (VOCs) in the composite material, and the synergistic effect between the modified activated carbon, the clay, the first modified metal oxide 1 and the second modified metal oxide 2 can significantly improve the degradation performance of the composite material, while the modified activated carbon, the clay, the first modified metal oxide 1 and the second modified metal oxide 2 are replaced by other materials without good degradation performance, which indicates that the other materials do not have efficient degradation capability on the organic compounds (VOCs).
Drawings
FIG. 1 is a process flow diagram of the present invention for forming a carbon-based composite material;
FIG. 2 is a high-resolution scanning electron microscope image of the formed carbon-based composite material of the present invention;
FIG. 3 is a nitrogen adsorption and desorption graph of the formed carbon-based composite material of the present invention, wherein (a) the nitrogen adsorption curve; (b) pore size distribution curve;
FIG. 4 is a testing apparatus for the catalytic degradation of organic compounds by the formed carbon-based composite material of the present invention.
Detailed Description
For further understanding of the present invention, the present invention will be described in detail with reference to the following examples, but the present invention is not limited to the examples.
Example 1
Preparation of first modified metal oxide 1:
a. respectively adding 0.01mol of silver nitrate, 0.01mol of zinc nitrate and 20g of molybdenum oxide into water, fully stirring, transferring the mixture into a high-pressure reaction kettle, reacting for 12 hours at 200 ℃, cooling and washing to be neutral to obtain a first modified metal oxide 1;
preparation of modified Metal oxide 2:
b. respectively adding 0.05mol of copper nitrate, 50g of titanium dioxide, 50g of manganese dioxide and 50g of zinc oxide into water, fully stirring, transferring the mixture into a high-pressure reaction kettle, reacting for 24 hours at 300 ℃, cooling, and washing to be neutral to obtain a second modified metal oxide 2;
preparing a carbon-based composite material:
c. respectively weighing raw materials of modified cotton stalk activated carbon, bentonite, the first modified metal oxide 1 obtained in the step a and the second modified metal oxide 2 obtained in the step b according to the mass ratio of 1:0.1:0.1:0.1, adding the raw materials into a mixing bin, stirring for 1 hour, adding 0.6kg of water, and continuously stirring for 1 hour to obtain a mixture;
d. c, transferring the mixture obtained in the step c into a granulator for granulation to obtain spherical particles with the diameter of 1 mm;
e. and d, roasting the spherical particles obtained in the step d under the inert atmosphere of nitrogen, wherein the roasting temperature is 300 ℃, the roasting time is 1 hour, and cooling to room temperature to obtain the carbon-based composite material.
Example 2
Preparation of first modified metal oxide 1:
a. respectively adding 0.01mol of silver nitrate, 0.01mol of zinc nitrate and 20g of molybdenum oxide into water, fully stirring, transferring the mixture into a high-pressure reaction kettle, reacting for 12 hours at 200 ℃, cooling and washing to be neutral to obtain a first modified metal oxide 1;
preparation of second modified metal oxide 2:
b. respectively adding 0.05mol of ferric nitrate, 50g of titanium dioxide, 50g of manganese dioxide and 50g of zinc oxide into water, fully stirring, transferring the mixture into a high-pressure reaction kettle, reacting for 24 hours at 300 ℃, cooling and washing to be neutral to obtain a second modified metal oxide 2;
preparing a carbon-based composite material:
c. respectively weighing raw materials of modified fruit tree activated carbon, attapulgite, the first modified metal oxide 1 obtained in the step a and the second modified metal oxide 2 obtained in the step b according to the mass ratio of 1:0.2:0.3:0.3, adding the raw materials into a mixing bin, stirring for 2 hours, adding 0.6kg of water, and continuing stirring for 2 hours to obtain a mixture;
d. c, transferring the mixture obtained in the step c into a granulator for granulation to obtain columnar granules with the diameter of 2 mm;
e. and d, roasting the columnar particles obtained in the step d under the inert atmosphere of argon at the roasting temperature of 600 ℃ for 3 hours, and cooling to room temperature to obtain the carbon-based composite material.
Example 3
Preparation of first modified metal oxide 1:
a. respectively adding 0.01mol of silver nitrate, 0.01mol of zinc nitrate and 20g of molybdenum oxide into water, fully stirring, transferring the mixture into a high-pressure reaction kettle, reacting for 12 hours at 200 ℃, cooling and washing to be neutral to obtain a first modified metal oxide 1;
preparation of second modified metal oxide 2:
b. adding 0.05mol of nickel nitrate, 50g of titanium dioxide, 50g of manganese dioxide and 50g of zinc oxide into water respectively, fully stirring, transferring the mixture into a high-pressure reaction kettle, reacting for 24 hours at 300 ℃, cooling and washing to be neutral to obtain a second modified metal oxide 2;
preparing a carbon-based composite material:
c. respectively weighing raw materials of modified apricot shell active carbon, bentonite, the first modified metal oxide 1 obtained in the step a and the second modified metal oxide 2 obtained in the step b according to the mass ratio of 1:0.3:0.4:0.4, adding the raw materials into a mixing bin, stirring for 5 hours, adding 0.3kg of water, and continuously stirring for 1 hour to obtain a mixture;
d. c, transferring the mixture obtained in the step c into a granulator for granulation to obtain columnar granules with the diameter of 4 mm;
e. and d, roasting the columnar particles obtained in the step d in an inert atmosphere of nitrogen at the roasting temperature of 800 ℃ for 6 hours, and cooling to room temperature to obtain the carbon-based composite material.
Example 4
Preparation of first modified metal oxide 1:
a. respectively adding 0.01mol of silver nitrate, 0.01mol of zinc nitrate and 20g of molybdenum oxide into water, fully stirring, transferring the mixture into a high-pressure reaction kettle, reacting for 12 hours at 200 ℃, cooling and washing to be neutral to obtain a first modified metal oxide 1;
preparation of second modified metal oxide 2:
b. respectively adding 0.05mol of cobalt nitrate, 50g of titanium dioxide and 50g of manganese dioxide and 50g of zinc oxide into water, fully stirring, transferring the mixture into a high-pressure reaction kettle, reacting for 24 hours at 300 ℃, cooling and washing to be neutral to obtain a second modified metal oxide 2;
preparing a carbon-based composite material:
c. respectively weighing raw materials of petroleum coke activated carbon, attapulgite, the first modified metal oxide 1 obtained in the step a and the second modified metal oxide 2 obtained in the step b according to the mass ratio of 1:0.4:0.4:0.4, adding the raw materials into a mixing bin, stirring for 1 hour, adding 0.3kg of water, and continuously stirring for 1 hour to obtain a mixture;
d. c, transferring the mixture obtained in the step c into an extruder for extrusion molding to obtain a honeycomb cube with the specification of 100 multiplied by 50-100 mm;
e. and d, roasting the honeycomb cube obtained in the step d under the inert atmosphere of nitrogen, wherein the roasting temperature is 300 ℃, the roasting time is 1 hour, and cooling to room temperature to obtain the carbon-based composite material.
Example 5
Preparation of first modified metal oxide 1:
a. respectively adding 0.03mol of silver nitrate, 0.03mol of zinc nitrate and 20g of molybdenum oxide into water, fully stirring, transferring the mixture into a high-pressure reaction kettle, reacting for 12 hours at 200 ℃, cooling and washing to be neutral to obtain a first modified metal oxide 1;
preparation of second modified metal oxide 2:
b. respectively adding 0.05mol of copper nitrate, 50g of titanium dioxide, 50g of manganese dioxide and 50g of zinc oxide into water, fully stirring, transferring the mixture into a high-pressure reaction kettle, reacting for 24 hours at 300 ℃, cooling, and washing to be neutral to obtain a second modified metal oxide 2;
preparing a carbon-based composite material:
c. respectively weighing raw material coal-based activated carbon, attapulgite, the first modified metal oxide 1 obtained in the step a and the second modified metal oxide 2 obtained in the step b according to the mass ratio of 1:0.3:0.5:0.5, adding the raw material coal-based activated carbon, the attapulgite, the first modified metal oxide 1 obtained in the step a and the second modified metal oxide 2 obtained in the step b into a mixing bin, stirring for 5 hours, adding 0.5kg of water, and continuously stirring for 2 hours to obtain a mixture;
d. c, transferring the mixture obtained in the step c into an extruder for extrusion molding to obtain a honeycomb cube with the specification of 100 multiplied by 50-100 mm;
e. and d, roasting the honeycomb cube obtained in the step d under the inert atmosphere of nitrogen or argon at the roasting temperature of 500 ℃ for 8 hours, and cooling to room temperature to obtain the carbon-based composite material, wherein the degradation rate of the organic matters is shown in table 1:
table 1 shows the degradation rate of the carbon composite material for organic compounds in example 5 of the present invention
| Components | Formaldehyde (I) | Toluene | Benzene and its derivatives | Xylene | Phenol and its preparation | Chlorophenol | Benzaldehyde |
| Initial concentration/(mg/m)3) | 8 | 8 | 8 | 8 | 8 | 8 | 8 |
| 24h concentration/(mg/m)3) | 0.72 | 0.80 | 0.72 | 0.80 | 0.56 | 0.64 | 0.80 |
| 48h concentration/(mg/m)3) | 0.4 | 0.48 | 0.56 | 0.64 | 0.48 | 0.56 | 0.72 |
| Catalytic degradation rate of 24h | 91％ | 90％ | 91％ | 90％ | 93％ | 92％ | 90％ |
| 48h catalytic degradation rate | 95％ | 94％ | 93％ | 92％ | 94％ | 93％ | 91％ |
Example 6
Preparation of first modified metal oxide 1:
a. respectively adding 0.05mol of silver nitrate, 0.05mol of zinc nitrate and 20g of molybdenum oxide into water, fully stirring, transferring the mixture into a high-pressure reaction kettle, reacting for 12 hours at 200 ℃, cooling and washing to be neutral to obtain a first modified metal oxide 1;
preparation of second modified metal oxide 2:
b. respectively adding 0.05mol of copper nitrate, 50g of titanium dioxide, 50g of manganese dioxide and 50g of zinc oxide into water, fully stirring, transferring the mixture into a high-pressure reaction kettle, reacting for 24 hours at 300 ℃, cooling, and washing to be neutral to obtain a second modified metal oxide 2;
preparing a carbon-based composite material:
c. respectively weighing raw materials of modified cotton stalk activated carbon, bentonite, the first modified metal oxide 1 obtained in the step a and the second modified metal oxide 2 obtained in the step b according to the mass ratio of 1:0.5:0.4:0.5, adding the raw materials into a mixing bin, stirring for 4 hours, adding 0.4kg of water, and continuously stirring for 1 hour to obtain a mixture;
d. c, transferring the mixture obtained in the step c into an extruder for extrusion molding to obtain a honeycomb cube with the specification of 100 multiplied by 50-100 mm;
e. and d, roasting the honeycomb cube obtained in the step d under the inert atmosphere of argon at the roasting temperature of 800 ℃ for 8 hours, and cooling to room temperature to obtain the carbon-based composite material.
Example 7
The molded carbon-based composite material prepared in any one of the embodiments 1 to 3 is used for researching the catalytic degradation performance of organic compounds (VOC) by adopting a fixed bed adsorption and desorption device:
the related testing device is shown in figure 4 and comprises an air inlet 1, a first valve 2, a sealed cabin 3, a heating element 4, a temperature controller 5, a columnar or spherical carbon-based composite material 6, a second valve 7 and an air outlet 8, wherein the air inlet 1 is arranged on one side of the sealed cabin 3, the first valve 2 is arranged between the sealed cabin 3 and the air inlet 1, the air outlet 8 is arranged on the other side of the sealed cabin 3, the second valve 7 is arranged between the sealed cabin 3 and the air outlet 8, and the heating element 4 and the temperature controller 5 are arranged in the sealed cabin;
weighing 6100g of columnar forming carbon-based composite material, filling into a sealed cabin 3, introducing mixed gas of organic compounds of formaldehyde, benzene, toluene, xylene, phenol, chlorophenol and benzaldehyde into the sealed cabin 3 through an air inlet 1 and a first valve 2, starting a heating element 4 after adsorption of 0.5h, 1h, 3h, 5h, 7h, 9h, 12h, 15h, 18h, 24h, 30h, 36h and 48h is finished in different time periods, heating the sealed cabin, controlling the heating temperature to be 100-150 ℃ through a temperature controller 5 to desorb the organic gas adsorbed in the composite material, extracting the organic gas in the sealed cabin 3 through a second valve 7 and an air outlet 8, measuring the components and the content of the organic gas by adopting gas chromatography and mass spectrometry, and respectively inspecting the influence of VOC concentration on the catalytic degradation performanceThe concentrations of formaldehyde, benzene, toluene, xylene, phenol, chlorophenol and benzaldehyde were set to 0.1mg/m, respectively3、0.5mg/m3、1mg/m3、3mg/m3、5mg/m3、7mg/m3、10mg/m3The effect of the initial concentration on the degradation performance was examined and is shown in table 1.
Example 8
The honeycomb-shaped formed carbon-based composite material prepared in any one of the embodiments 4 to 6 is subjected to the catalytic degradation performance of the formed composite material on organic compounds VOC by adopting a fixed bed adsorption device:
the test apparatus concerned is according to example 7;
weighing 400g of honeycomb-shaped formed carbon-based composite material 6, putting the honeycomb-shaped formed carbon-based composite material into a sealed cabin 3, introducing mixed gas of organic compounds of formaldehyde, benzene, toluene, xylene, phenol, chlorophenol and benzaldehyde into the sealed cabin 3 through an air inlet 1 and a first valve 2, starting a heating element 4 after adsorption is finished in different time periods of 0.5h, 1h, 3h, 5h, 7h, 9h, 12h, 15h, 18h, 24h, 30h, 36h and 48h, heating the sealed cabin, controlling the temperature in the sealed cabin to be 100-150 ℃ through a temperature controller 5 to desorb the organic gas adsorbed in the composite material, extracting the organic gas in the sealed cabin 3 through a second valve 7 and an air outlet 8, measuring the components and the content of the organic gas by adopting gas chromatography and mass spectrometry, respectively inspecting the influence of VOC concentration on catalytic degradation performance, formaldehyde, benzene, toluene, xylene, phenol and chlorophenol, The concentrations of benzaldehyde were set to 0.1mg/m, respectively3、0.5mg/m3、1mg/m3、3mg/m3、5mg/m3、7mg/m3、10mg/m3The effect of the initial concentration on the degradation performance was examined and is shown in table 1.
Example 9 (comparative)
The difference from example 5 is that, without adding the first modified metal oxide 1 and the second modified metal oxide 2, the degradation rate (removal rate) of the organic compound is shown in table 2:
preparing a carbon-based composite material:
respectively weighing raw materials of coal-based activated carbon and attapulgite according to the mass ratio of 1:0.3:0.5:0.5, adding the raw materials into a mixing bin, stirring for 5 hours, adding 0.5kg of water, and continuously stirring for 2 hours to obtain a mixture;
transferring the obtained mixture into an extruder for extrusion molding to obtain a honeycomb cube with the specification of 100 multiplied by 50-100 mm;
roasting the obtained honeycomb cube in an inert atmosphere of nitrogen or argon at 500 ℃ for 8 hours, and cooling to room temperature to obtain the carbon-based composite material, wherein the degradation rate of organic matters is shown in table 2:
TABLE 2 degradation rates (removal rates) of organic compounds without addition of the first modified metal oxide 1 and the second modified metal oxide 2
| Components | Formaldehyde (I) | Toluene | Benzene and its derivatives | Xylene | Phenol and its preparation | Chlorophenol | Benzaldehyde |
| Initial concentration/(mg/m)3) | 4 | 4 | 4 | 4 | 4 | 4 | 4 |
| 24h concentration/(mg/m)3) | 3.56 | 3.60 | 3.60 | 3.64 | 3.68 | 3.72 | 3.68 |
| 48h concentration/(mg/m)3) | 3.52 | 3.52 | 3.52 | 3.60 | 3.64 | 3.68 | 3.64 |
| Catalytic degradation rate of 24h | 11％ | 10％ | 10％ | 9％ | 8％ | 7％ | 8％ |
| 48h catalytic degradation rate | 12％ | 11％ | 11％ | 10％ | 9％ | 8％ | 9％ |
| Components | Formaldehyde (I) | Toluene | Benzene and its derivatives | Xylene | Phenol and its preparation | Chlorophenol | Benzaldehyde |
| Initial concentration/(mg/m)3) | 8 | 8 | 8 | 8 | 8 | 8 | 8 |
| 24h concentration/(mg/m)3) | 7.52 | 7.60 | 7.52 | 7.60 | 7.68 | 7.76 | 7.68 |
| 48h concentration/(mg/m)3) | 7.44 | 7.52 | 7.60 | 7.60 | 7.60 | 7.68 | 7.60 |
| Catalytic degradation rate of |
6％ | 5％ | 6％ | 5％ | 4％ | 3％ | 4％ |
| 48h |
7％ | 6％ | 5％ | 5％ | 5％ | 4％ | 5％ |
Example 10 (comparative)
Based on the embodiment 5, the difference is that the modified activated carbon is replaced by a common molecular sieve sold in the market;
preparation of first modified metal oxide 1:
a. respectively adding 0.03mol of silver nitrate, 0.03mol of zinc nitrate and 20g of molybdenum oxide into water, fully stirring, transferring the mixture into a high-pressure reaction kettle, reacting for 12 hours at 200 ℃, cooling and washing to be neutral to obtain a first modified metal oxide 1;
preparation of second modified metal oxide 2:
b. respectively adding 0.05mol of copper nitrate, 50g of titanium dioxide, 50g of manganese dioxide and 50g of zinc oxide into water, fully stirring, transferring the mixture into a high-pressure reaction kettle, reacting for 24 hours at 300 ℃, cooling, and washing to be neutral to obtain a second modified metal oxide 2;
preparing a carbon-based composite material:
c. respectively weighing a commercially available common molecular sieve, attapulgite, the first modified metal oxide 1 obtained in the step a and the second modified metal oxide 2 obtained in the step b according to the mass ratio of 1:0.3:0.5:0.5, adding the weighed materials into a mixing bin, stirring for 5 hours, adding 0.5kg of water, and continuously stirring for 2 hours to obtain a mixture;
d. c, transferring the mixture obtained in the step c into an extruder for extrusion molding to obtain a honeycomb cube with the specification of 100 multiplied by 50-100 mm;
e. and d, roasting the honeycomb cube obtained in the step d under the inert atmosphere of nitrogen or argon at the roasting temperature of 500 ℃ for 8 hours, and cooling to room temperature to obtain the carbon-based composite material, wherein the degradation rate of organic matters is shown in Table 3:
table 3 shows the degradation rate (removal rate) of organic compounds by replacing modified activated carbon with a conventional molecular sieve commercially available as a molecular sieve
| Components | Formaldehyde (I) | Toluene | Benzene and its derivatives | Xylene | Phenol and its preparation | Chlorophenol | Benzaldehyde |
| Initial concentration/(mg/m)3) | 4 | 4 | 4 | 4 | 4 | 4 | 4 |
| 24h concentration/(mg/m)3) | 2 | 2 | 2 | 1.92 | 1.92 | 1.88 | 1.8 |
| 48h concentration/(mg/m)3) | 1.52 | 1.56 | 1.56 | 1.6 | 1.24 | 1.28 | 1.24 |
| Catalytic degradation rate of 24h | 50％ | 50％ | 50％ | 52％ | 52％ | 53％ | 55％ |
| 48h catalytic degradation rate | 62％ | 61％ | 61％ | 60％ | 69％ | 68％ | 69％ |
| Components | Formaldehyde (I) | Toluene | Benzene and its derivatives | Xylene | Phenol and its preparation | Chlorophenol | Benzaldehyde |
| Initial concentration/(mg/m)3) | 8 | 8 | 8 | 8 | 8 | 8 | 8 |
| 24h concentration/(mg/m)3) | 4.8 | 4.4 | 4.64 | 4.4 | 4.48 | 4.56 | 4.48 |
| 48h concentration/(mg/m)3) | 4 | 3.92 | 3.84 | 3.92 | 4 | 3.76 | 3.6 |
| Catalytic degradation rate of 24h | 40％ | 45％ | 42％ | 45％ | 44％ | 43％ | 44％ |
| 48h catalytic degradation rate | 50％ | 51％ | 52％ | 51％ | 50％ | 53％ | 55％ |
Example 11 (comparative)
On the basis of example 5, the difference is that the clay is replaced by sodium carboxymethyl cellulose;
preparation of first modified metal oxide 1:
a. respectively adding 0.03mol of silver nitrate, 0.03mol of zinc nitrate and 20g of molybdenum oxide into water, fully stirring, transferring the mixture into a high-pressure reaction kettle, reacting for 12 hours at 200 ℃, cooling and washing to be neutral to obtain a first modified metal oxide 1;
preparation of second modified metal oxide 2:
b. respectively adding 0.05mol of copper nitrate, 50g of titanium dioxide, 50g of manganese dioxide and 50g of zinc oxide into water, fully stirring, transferring the mixture into a high-pressure reaction kettle, reacting for 24 hours at 300 ℃, cooling, and washing to be neutral to obtain a second modified metal oxide 2;
preparing a carbon-based composite material:
c. respectively weighing raw material coal-based activated carbon, sodium carboxymethyl cellulose, the first modified metal oxide 1 obtained in the step a and the second modified metal oxide 2 obtained in the step b according to the mass ratio of 1:0.3:0.5:0.5, adding the raw material coal-based activated carbon, the sodium carboxymethyl cellulose, the first modified metal oxide 1 obtained in the step a and the second modified metal oxide 2 obtained in the step b into a mixing bin, stirring for 5 hours, adding 0.5kg of water, and continuously stirring for 2 hours to obtain a mixture;
d. c, transferring the mixture obtained in the step c into an extruder for extrusion molding to obtain a honeycomb cube with the specification of 100 multiplied by 50-100 mm;
e. and d, roasting the honeycomb cube obtained in the step d under the inert atmosphere of nitrogen or argon at the roasting temperature of 500 ℃ for 8 hours, and cooling to room temperature to obtain the carbon-based composite material, wherein the degradation rate of organic matters is shown in Table 4:
TABLE 4 degradation rate (removal rate) of organic compounds by replacing clay with sodium carboxymethylcellulose
| Components | Formaldehyde (I) | Toluene | Benzene and its derivatives | Xylene | Phenol and its preparation | Chlorophenol | Benzaldehyde |
| Initial concentration/(mg/m)3) | 4 | 4 | 4 | 4 | 4 | 4 | 4 |
| 24h concentration/(mg/m)3) | 1.56 | 1.6 | 1.6 | 1.48 | 1.44 | 1.4 | 1.36 |
| 48h concentration/(mg/m)3) | 1.12 | 1.16 | 1.16 | 1.2 | 1.24 | 1.28 | 1.24 |
| Catalytic degradation rate of 24h | 61％ | 60％ | 60％ | 63％ | 64％ | 65％ | 66％ |
| 48h catalytic degradation rate | 72％ | 71％ | 71％ | 70％ | 69％ | 68％ | 69％ |
| Components | Formaldehyde (I) | Toluene | Benzene and its derivatives | Xylene | Phenol and its preparation | Chlorophenol | Benzaldehyde |
| Initial concentration/(mg/m)3) | 8 | 8 | 8 | 8 | 8 | 8 | 8 |
| 24h concentration/(mg/m)3) | 3.52 | 3.6 | 3.52 | 3.6 | 3.68 | 3.76 | 3.68 |
| 48h concentration/(mg/m)3) | 2.64 | 2.72 | 2.8 | 2.8 | 2.8 | 2.88 | 2.8 |
| Catalytic degradation rate of 24h | 56％ | 55％ | 56％ | 55％ | 54％ | 53％ | 54％ |
| 48h catalytic degradation rate | 67％ | 66％ | 65％ | 65％ | 65％ | 64％ | 65％ |
Tables 1 to 4 show that the first modified metal oxide 1 and the second modified metal oxide 2 are main components for degrading organic compounds (VOCs) in the composite material, and the synergistic effect between the modified activated carbon, the clay, the first modified metal oxide 1 and the second modified metal oxide 2 can significantly improve the degradation performance of the composite material, while the modified activated carbon, the clay, the first modified metal oxide 1 and the second modified metal oxide 2 are replaced by other materials without good degradation performance, which indicates that the other materials do not have efficient degradation capability on the organic compounds (VOCs).
Claims (3)
1. The preparation method of the carbon-based composite material for catalyzing and degrading various organic matters at room temperature is characterized in that modified activated carbon, clay, a first modified metal oxide 1 and a second modified metal oxide 2 are used as raw materials to prepare columnar or spherical particles or honeycomb cubes, and then the columnar or spherical particles or the honeycomb cubes are roasted in an inert atmosphere, and the specific operation is carried out according to the following steps:
preparation of first modified metal oxide 1:
a. respectively adding 0.01-1moL of metal salt silver nitrate and zinc nitrate and 1-100g of molybdenum oxide into water, fully stirring, transferring the mixture into a high-pressure reaction kettle, reacting at the temperature of 200-300 ℃ for 12-48 hours, cooling, and washing to be neutral to obtain a first modified metal oxide 1;
preparation of second modified metal-free oxide 2:
b. respectively adding 0.01-1moL of metal salt ferric nitrate, cupric nitrate, nickel nitrate or cobalt nitrate and 1-100g of zinc oxide, titanium dioxide and manganese dioxide into water, fully stirring, transferring the mixture into a high-pressure reaction kettle, reacting for 12-48 hours at the temperature of 200-300 ℃, cooling and washing to be neutral to obtain a second modified metal oxide 2;
preparing a carbon-based composite material:
c. respectively weighing raw materials of modified activated carbon, clay, the first modified metal oxide 1 in the step a and the second modified metal oxide 2 in the step b according to the mass ratio of 1:0.1-0.5:0.1-0.5:0.1-0.5, adding the raw materials into a mixing bin, stirring for 1-5 hours, adding 0.3-0.6kg of water, and continuously stirring for 1-2 hours to obtain a mixture, wherein the modified activated carbon is modified cotton stalk activated carbon, fruit tree activated carbon, apricot hull activated carbon, petroleum coke activated carbon and coal activated carbon; the clay is bentonite or attapulgite;
d. c, transferring the mixture obtained in the step c into a granulator for granulation to obtain columnar or spherical particles with the diameter of 1-4 mm;
or transferring the mixture obtained in the step c into an extruder for extrusion molding to obtain a honeycomb cube with the specification of 100 multiplied by 50-100 mm;
e. and d, roasting the columnar or spherical particles or the honeycomb cubes obtained in the step d in an inert atmosphere of nitrogen or argon at the roasting temperature of 300-800 ℃ for 1-8h, and cooling to room temperature to obtain the carbon-based composite material.
2. A method for preparing a carbon-based composite material for catalytic degradation of organic compounds at room temperature as claimed in claim 1, wherein the organic compound is formaldehyde, benzene, toluene, xylene, phenol, chlorophenol, benzaldehyde, ethyl chloride, cyclohexane or amyl acetate.
3. The device for testing the carbon-based composite material obtained by the method according to claim 1 in preparing and catalytically degrading a plurality of volatile organic compounds in a gas phase simultaneously is characterized by comprising a gas inlet (1), a first valve (2), a sealed cabin (3), a heating element (4), a temperature controller (5), the carbon-based composite material (6), a second valve (7) and a gas outlet (8), wherein the gas inlet (1) is arranged on one side of the sealed cabin (3), the first valve (2) is arranged between the sealed cabin (3) and the gas inlet (1), the gas outlet (8) is arranged on the other side of the sealed cabin (3), the second valve (7) is arranged between the sealed cabin (3) and the gas outlet (8), and the heating element (4) and the temperature controller (5) are arranged in the sealed cabin.
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