CN112108115B - Preparation method and testing device of carbon-based composite material for catalyzing and degrading various organic matters at room temperature - Google Patents
Preparation method and testing device of carbon-based composite material for catalyzing and degrading various organic matters at room temperature Download PDFInfo
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- CN112108115B CN112108115B CN202010994145.3A CN202010994145A CN112108115B CN 112108115 B CN112108115 B CN 112108115B CN 202010994145 A CN202010994145 A CN 202010994145A CN 112108115 B CN112108115 B CN 112108115B
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 132
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 72
- 239000002131 composite material Substances 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 230000000593 degrading effect Effects 0.000 title claims abstract description 12
- 238000012360 testing method Methods 0.000 title abstract description 14
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 101
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 101
- 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
- 230000003197 catalytic effect Effects 0.000 claims abstract description 36
- 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 26
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000004927 clay Substances 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
- 239000008096 xylene Substances 0.000 claims abstract description 15
- 239000012798 spherical particle Substances 0.000 claims abstract description 10
- 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 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 37
- 229910001868 water Inorganic materials 0.000 claims description 37
- 238000001816 cooling Methods 0.000 claims description 32
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 22
- 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
- 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
- 239000000463 material Substances 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- -1 salt silver nitrate Chemical class 0.000 claims description 12
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 11
- 229910052757 nitrogen 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
- 238000000034 method Methods 0.000 claims description 10
- 238000005303 weighing Methods 0.000 claims description 10
- 229960000892 attapulgite Drugs 0.000 claims description 9
- 238000001125 extrusion Methods 0.000 claims description 9
- 229910052625 palygorskite Inorganic materials 0.000 claims description 9
- 229910052786 argon Inorganic materials 0.000 claims description 8
- 239000000440 bentonite Substances 0.000 claims description 8
- 229910000278 bentonite Inorganic materials 0.000 claims description 8
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical group O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 8
- 239000003245 coal Substances 0.000 claims description 7
- 229920000742 Cotton Polymers 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
- 238000005469 granulation Methods 0.000 claims description 5
- 230000003179 granulation Effects 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 235000009827 Prunus armeniaca Nutrition 0.000 claims description 4
- 244000018633 Prunus armeniaca Species 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
- 235000013399 edible fruits Nutrition 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
- 239000002006 petroleum coke Substances 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 2
- 239000012855 volatile organic compound Substances 0.000 abstract description 35
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 abstract description 18
- 150000002894 organic compounds Chemical class 0.000 description 33
- 238000001179 sorption measurement Methods 0.000 description 17
- 239000007789 gas Substances 0.000 description 9
- 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
- 238000010438 heat treatment Methods 0.000 description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- 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
- 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
- 238000003795 desorption Methods 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
- 238000000746 purification Methods 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
- 238000001819 mass spectrum 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
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000003054 catalyst Substances 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
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 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
- 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
- 238000002336 sorption--desorption measurement Methods 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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- 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
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- 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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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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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- 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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- B01D2257/00—Components to be removed
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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, which takes modified activated carbon, clay, a first modified metal oxide 1 and a second modified metal oxide 2 as raw materials, and the raw materials are fully mixed, granulated or extruded to prepare columnar or spherical particles or honeycomb cubes, and then the columnar or spherical particles or honeycomb cubes are roasted in inert atmosphere, so that the formed carbon-based composite material with high specific surface area, high strength and long service life is obtained, and the obtained columnar or spherical or honeycomb carbon-based composite material is used for catalyzing and degrading various volatile organic compounds in gas phase at room temperature, such as formaldehyde, benzene, toluene, xylene, phenol, chlorophenol, benzaldehyde, chloroethane, cyclohexane or amyl acetate, and the results show that: for low concentration of 1-5mg/m 3 The catalytic degradation rate of volatile organic compounds such as toluene, benzene and formaldehyde in 24 hours is up to 95% or more, and the concentration is 5-10mg/m 3 The catalytic degradation rate of toluene, benzene, formaldehyde and the like in 24 hours is up to more than 90 percent.
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 endangers the body health and life quality of people, becomes a social problem of common people worry, leadership concern and media concern, and how to effectively control indoor organic compound (VOCs) pollution becomes a research hot spot in the indoor air field of China. The use of purification materials to remove organic compounds (VOCs) from indoor air is an important approach to solve this problem, where activated carbon adsorption is considered a relatively reliable and safe purification method, and is widely used in purification of organic compounds (VOCs) in indoor air, but activated carbon has limited adsorption capacity and does not have removal capacity when adsorption reaches saturation. In addition, toxic gases adsorbed in the pores of the activated carbon are at risk of desorption and release, and thus there is a possibility of secondary pollution. Thus, the activated carbon can only transiently enrich organic compounds (VOCs) and can not thoroughly convert the organic compounds (VOCs) into non-toxic 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 energy consumption is high, equipment investment is large, and the method is not suitable for removing low-concentration organic compounds (VOCs); the photocatalytic degradation performance is not ideal, toxic and harmful intermediate products are produced in the catalytic process, and organic matters are difficult to thoroughly mineralize. It is known that photocatalysis and thermocatalysis are not suitable for purifying organic compounds (VOCs) at low concentrations in the room of a general household. Therefore, developing a composite material integrating room temperature catalytic degradation and adsorption is significant 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 are converted into non-toxic and harmless carbon dioxide and water, so that the risk of secondary pollution caused by desorption and release does not exist. In addition, although powdered activated carbon has a relatively high specific surface area and a developed pore structure, it is one of the adsorbents that is preferable for adsorbing and removing organic compounds (VOCs). However, the powder material is limited in practical application, so that the preparation of the formed active carbon-based composite material has important practical significance for purifying indoor organic compounds (VOCs).
In order to solve the problems of the powdered activated carbon and the removal of indoor organic compounds (VOCs), the invention aims to prepare the formed activated carbon-based composite material, realizes the adsorption and catalytic degradation of the indoor organic compounds (VOCs), and performs catalytic degradation on Various Organic Compounds (VOCs) such as formaldehyde, benzene series and the like after adsorption, and mineralizes the activated carbon-based composite material 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 active carbon-based composite material, the active carbon is modified and a room-temperature catalytic material is added, so that the formed active carbon-based composite material with excellent adsorption and mineralization performance, high adsorption speed, long service life and high mechanical strength is obtained, and is used for simultaneously adsorbing and mineralizing formaldehyde, benzene, toluene, xylene, phenol, chlorophenol, benzaldehyde and other components.
Disclosure of Invention
The invention aims at overcoming the defects of the prior active carbon materials and provides a preparation method and a testing device of a carbon-based composite material for catalyzing and degrading various organic matters at room temperature, wherein the method takes modified active 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, granulating and extrusion molding, the adsorption capacity of the modified active carbon on organic compounds is improved by adding the modified active carbon, the catalytic degradation of the material on the organic compounds 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 realize the catalytic degradation of the material on the organic compounds with low concentration of 1-5mg/m 3 The catalytic degradation rate of volatile organic compounds such as toluene and formaldehyde in 24 hours is up to 95% or more, and the concentration is 5-10mg/m 3 The 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 raw materials 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. adding 0.01-1moL of metal salt silver nitrate and zinc nitrate and 1-100g of molybdenum oxide into water respectively, 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 first modified metal oxide 1;
preparing a second modified metal-free oxide 2:
b. adding 0.01-1moL of metal salt ferric nitrate, cupric nitrate, nickel nitrate or cobalt nitrate, 1-100g of zinc oxide, titanium dioxide and manganese dioxide into water respectively, fully stirring, transferring the mixture into a high-pressure reaction kettle, reacting for 12-48 hours at 200-300 ℃, cooling and washing to neutrality to obtain a second modified metal oxide 2;
preparing a carbon-based composite material:
c. b, respectively weighing raw material 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 1:0.1-0.5:0.1-0.5:0.1-0.1-0.5, adding 0.6kg of water into a mixing bin, 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 shell activated carbon, petroleum coke activated carbon and coal activated carbon; the clay is bentonite and 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 under the inert atmosphere of nitrogen or argon, wherein the roasting temperature is 300-800 ℃ for 1-8 hours, and cooling to room temperature to obtain the carbon-based composite material.
The organic matter is formaldehyde, benzene, toluene, xylene, phenol, chlorophenol, benzaldehyde, chloroethane, cyclohexane or amyl acetate.
The testing device comprises an air 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 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.
The columnar or honeycomb carbon-based composite material is adopted to catalyze and degrade various volatile organic compounds in the gas phase.
The carbon-based composite material is catalytically degraded at room temperature, and an external heat source or a light source is not needed.
The invention relates to a preparation method of a carbon-based composite material for catalyzing and degrading various organic matters at room temperature, which comprises the following specific operations: adding water into different metal salts and different oxides respectively, stirring thoroughly, transferring the mixture into a high-pressure reaction kettle, reacting for 12-48 hours at 200-300 ℃, cooling, and washing to neutrality to obtain a first modified metal oxide 1 and a second modified metal oxide 2 respectively. 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 insoluble in water, wherein the nitrate comprises ferric nitrate, cupric nitrate, nickel nitrate or cobalt nitrate.
The invention relates to a preparation method and a testing device of a carbon-based composite material for catalyzing and degrading various organic matters at room temperature, which are compared with the prior art: the preparation method is simple, environment-friendly, safe and free of extra pollutants, the obtained formed active 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 of the invention adopts a testing device to absorb and desorb nitrogenThe test shows that: has rich pore structure and large specific surface area, and the surface area is up to 600-800m 2 And/g, through XRD, infrared and Raman spectrum tests, the active carbon, clay, first modified metal oxide 1 and second modified metal oxide 2 have obvious characteristic peaks. The catalyst has strong adsorption and catalytic degradation capability on VOC, low cost and rich resources. Therefore, the carbon-based composite material obtained by the method is applied to the field of indoor organic compound (VOC) control as a purifying agent. Carbon-based composite material with low concentration of 1-5mg/m 3 The 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 concentration is 5-10mg/m 3 The catalytic degradation rate of toluene, formaldehyde and the like in 24 hours is up to more than 90 percent, and the catalytic degradation rate is shown in table 1; tables 1-4 illustrate that the first modified metal oxide 1 and the second modified metal oxide 2 are the main components of the composite material for degrading organic compounds (VOCs), and that the synergistic effect among the modified activated carbon, clay, the first modified metal oxide 1 and the second modified metal oxide 2 can significantly improve the degradation performance of the composite material, and that other materials are replaced by the modified activated carbon, the clay and the first modified metal oxide 1, and the second modified metal oxide 2 have no good degradation performance, thus indicating that the other materials have no 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;
FIG. 2 is a high resolution scanning electron microscope image of the molded carbon-based composite material of the present invention;
FIG. 3 is a graph of nitrogen adsorption and desorption for a molded carbon-based composite material of the present invention, wherein (a) the nitrogen adsorption curve; (b) a pore size distribution curve;
FIG. 4 is a schematic illustration of a test apparatus for the catalytic degradation of organic compounds by a shaped carbon-based composite material in accordance with the present invention.
Detailed Description
The present invention will be described in detail with reference to examples, but is not limited to the examples.
Example 1
Preparation of first modified metal oxide 1:
a. adding 0.01mol of silver nitrate, 0.01mol of zinc nitrate and 20g of molybdenum oxide into water respectively, fully stirring, transferring the mixture into a high-pressure reaction kettle, reacting for 12 hours at 200 ℃, cooling, and washing to neutrality to obtain a first modified metal oxide 1;
preparation of modified metal oxide 2:
b. adding 0.05mol of copper 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 neutrality to obtain a second modified metal oxide 2;
preparing a carbon-based composite material:
c. c, respectively weighing raw material 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 1:0.1:0.1:0.1:0.1, adding the raw material modified cotton stalk activated carbon, bentonite and the second modified metal oxide 2 into a mixing bin, stirring for 1h, adding 0.6kg of water, and continuing stirring for 1h 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 time is 1h, and cooling to room temperature to obtain the carbon-based composite material.
Example 2
Preparation of first modified metal oxide 1:
a. adding 0.01mol of silver nitrate, 0.01mol of zinc nitrate and 20g of molybdenum oxide into water respectively, fully stirring, transferring the mixture into a high-pressure reaction kettle, reacting for 12 hours at 200 ℃, cooling, and washing to neutrality to obtain a first modified metal oxide 1;
preparing a second modified metal oxide 2:
b. adding 0.05mol of ferric 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 neutrality to obtain a second modified metal oxide 2;
preparing a carbon-based composite material:
c. c, respectively weighing raw material modified fruit tree active 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 material modified fruit tree active carbon, the attapulgite and the second modified metal oxide 2 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, wherein the roasting temperature is 600 ℃, the time is 3 hours, and cooling to room temperature to obtain the carbon-based composite material.
Example 3
Preparation of first modified metal oxide 1:
a. adding 0.01mol of silver nitrate, 0.01mol of zinc nitrate and 20g of molybdenum oxide into water respectively, fully stirring, transferring the mixture into a high-pressure reaction kettle, reacting for 12 hours at 200 ℃, cooling, and washing to neutrality to obtain a first modified metal oxide 1;
preparing a 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 neutrality to obtain a second modified metal oxide 2;
preparing a carbon-based composite material:
c. c, respectively weighing raw material 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 material modified apricot shell active carbon, bentonite and the second modified metal oxide 2 into a mixing bin, stirring for 5 hours, adding 0.3kg of water, and continuing 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 under the inert atmosphere of nitrogen, wherein the roasting temperature is 800 ℃, the time is 6 hours, and cooling to room temperature to obtain the carbon-based composite material.
Example 4
Preparation of first modified metal oxide 1:
a. adding 0.01mol of silver nitrate, 0.01mol of zinc nitrate and 20g of molybdenum oxide into water respectively, fully stirring, transferring the mixture into a high-pressure reaction kettle, reacting for 12 hours at 200 ℃, cooling, and washing to neutrality to obtain a first modified metal oxide 1;
preparing a second modified metal oxide 2:
b. adding 0.05mol of cobalt nitrate, 50g of titanium dioxide and 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 neutrality to obtain a second modified metal oxide 2;
preparing a carbon-based composite material:
c. b, 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 1:0.4:0.4:0.4:0.4, adding the raw materials into a mixing bin, stirring for 1h, adding 0.3kg of water, and continuing stirring for 1h 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 at the roasting temperature of 300 ℃ for 1h, and cooling to room temperature to obtain the carbon-based composite material.
Example 5
Preparation of first modified metal oxide 1:
a. adding 0.03mol of silver nitrate, 0.03mol of zinc nitrate and 20g of molybdenum oxide into water respectively, fully stirring, transferring the mixture into a high-pressure reaction kettle, reacting for 12 hours at 200 ℃, cooling, and washing to neutrality to obtain a first modified metal oxide 1;
preparing a second modified metal oxide 2:
b. adding 0.05mol of copper 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 neutrality to obtain a second modified metal oxide 2;
preparing a carbon-based composite material:
c. c, respectively weighing raw material coal active 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 active carbon, the attapulgite and the second modified metal oxide 2 into a mixing bin, stirring for 5h, adding 0.5kg of water, and continuing stirring for 2h 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. roasting the honeycomb cube obtained in the step d under the inert atmosphere of nitrogen or argon, wherein the roasting temperature is 500 ℃, the time is 8 hours, and cooling to room temperature to obtain the carbon-based composite material, and the degradation rate of organic matters is shown in table 1:
table 1 shows the degradation rate of the carbon composite material of example 5 of the present invention to organic compounds
| Component (A) | Formaldehyde | Toluene (toluene) | Benzene | Xylene (P) | Phenol (P) | 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 for 24 hours | 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. adding 0.05mol of silver nitrate, 0.05mol of zinc nitrate and 20g of molybdenum oxide into water respectively, fully stirring, transferring the mixture into a high-pressure reaction kettle, reacting for 12 hours at 200 ℃, cooling, and washing to neutrality to obtain a first modified metal oxide 1;
preparing a second modified metal oxide 2:
b. adding 0.05mol of copper 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 neutrality to obtain a second modified metal oxide 2;
preparing a carbon-based composite material:
c. b, respectively weighing raw material modified cotton stalk 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 1:0.5:0.4:0.5, adding the raw material modified cotton stalk active carbon, bentonite and the second modified metal oxide 2 into a mixing bin, stirring for 4 hours, adding 0.4kg of water, and continuing 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, wherein the roasting temperature is 800 ℃, the time is 8 hours, and cooling to room temperature to obtain the carbon-based composite material.
Example 7
The molded carbon-based composite material of any one of examples 1 to 3 was subjected to a study on catalytic degradation performance of an organic compound (VOC) by using a fixed bed adsorption/desorption device:
the related testing device is shown in fig. 4, and consists of 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;
the columnar formed carbon-based composite material 6100g is weighed and put into a sealed cabin 3, mixed gas of organic compounds formaldehyde, benzene, toluene, xylene, phenol, chlorophenol and benzaldehyde enters the sealed cabin 3 through an air inlet 1 and a first valve 2, after adsorption is finished in different time periods of 0.5h, 1h, 3h, 5h, 7h, 9h, 12h, 15h, 18h, 24h, 30h, 36h and 48h, a heating element 4 is started, the sealed cabin is heated, the heating temperature is controlled to be 100-150 ℃ through a temperature controller 5, the organic gas adsorbed in the composite material is desorbed, the organic gas in the sealed cabin 3 is extracted through a second valve 7 and an air outlet 8, the components and the content of the organic gas are measured through gas chromatography and mass spectrum, the influence of VOC concentration on catalytic degradation performance is inspected, and the concentration of formaldehyde, benzene, toluene, xylene, phenol, chlorophenol and benzaldehyde is respectively set to be 0.1mg/m 3 、0.5mg/m 3 、1mg/m 3 、3mg/m 3 、5mg/m 3 、7mg/m 3 、10mg/m 3 The effect of initial concentration on degradation performance was examined and shown in table 1.
Example 8
The honeycomb shaped carbon-based composite material of any one of examples 4 to 6 is subjected to research on catalytic degradation performance of the shaped composite material on organic compounds VOC by adopting a fixed bed adsorption device:
the test apparatus involved is according to example 7;
400g of honeycomb-shaped formed carbon-based composite material 6 is weighed and put into a sealed cabin 3, mixed gas of organic compounds formaldehyde, benzene, toluene, xylene, phenol, chlorophenol and benzaldehyde is introduced into the sealed cabin 3 through an air inlet 1 and a first valve 2, after adsorption is finished in different time periods of 0.5h, 1h, 3h, 5h, 7h, 9h, 12h, 15h, 18h, 24h, 30h, 36h and 48h, a heating element 4 is started, the sealed cabin is heated, the temperature in the sealed cabin is controlled to be 100-150 ℃ through a temperature controller 5, the organic gas adsorbed in the composite material is desorbed, the organic gas in the sealed cabin 3 is extracted through a second valve 7 and an air outlet 8, the components and the content of the organic gas are measured through gas chromatography and mass spectrum, and the influence of VOC concentration on catalytic degradation performance is respectively inspected, and the formaldehyde, benzene, toluene, xylene, phenol, chlorophenol and benzaldehyde concentration are respectively set to be 0.1mg/m 3 、0.5mg/m 3 、1mg/m 3 、3mg/m 3 、5mg/m 3 、7mg/m 3 、10mg/m 3 The effect of initial concentration on degradation performance was examined and shown in table 1.
Example 9 (comparative)
The difference on the basis of example 5 is that the first modified metal oxide 1 and the second modified metal oxide 2 are not added, and the degradation rate (removal rate) of the organic compound is shown in table 2:
preparing a carbon-based composite material:
raw material coal active carbon and attapulgite are respectively weighed according to the mass ratio of 1:0.3:0.5:0.5 and are added into a mixing bin to be stirred for 5 hours, 0.5kg of water is added, and the stirring is continued for 2 hours, so as 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 under the inert atmosphere of nitrogen or argon, wherein the roasting temperature is 500 ℃, the time is 8 hours, and cooling to room temperature to obtain the carbon-based composite material, and the degradation rate of organic matters is shown in table 2:
table 2 degradation ratio (removal ratio) of organic compound by the first modified metal oxide 1 and the second modified metal oxide 2 were not added
| Component (A) | Formaldehyde | Toluene (toluene) | Benzene | Xylene (P) | Phenol (P) | 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 for 24 hours | 11％ | 10％ | 10％ | 9％ | 8％ | 7％ | 8％ |
| 48h catalytic degradation rate | 12％ | 11％ | 11％ | 10％ | 9％ | 8％ | 9％ |
| Component (A) | Formaldehyde | Toluene (toluene) | Benzene | Xylene (P) | Phenol (P) | 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 for 24 |
6％ | 5％ | 6％ | 5％ | 4％ | 3％ | 4％ |
| 48h |
7％ | 6％ | 5％ | 5％ | 5％ | 4％ | 5％ |
Example 10 (comparative)
Based on example 5, the modified activated carbon was replaced with a commercially available common molecular sieve;
preparation of first modified metal oxide 1:
a. adding 0.03mol of silver nitrate, 0.03mol of zinc nitrate and 20g of molybdenum oxide into water respectively, fully stirring, transferring the mixture into a high-pressure reaction kettle, reacting for 12 hours at 200 ℃, cooling, and washing to neutrality to obtain a first modified metal oxide 1;
preparing a second modified metal oxide 2:
b. adding 0.05mol of copper 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 neutrality to obtain a second modified metal oxide 2;
preparing a carbon-based composite material:
c. c, respectively weighing a commercial 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 first modified metal oxide and the second modified metal oxide into a mixing bin, stirring for 5 hours, adding 0.5kg of water, and continuing 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. roasting the honeycomb cube obtained in the step d under the inert atmosphere of nitrogen or argon, wherein the roasting temperature is 500 ℃, the time is 8 hours, and cooling to room temperature to obtain the carbon-based composite material, and the degradation rate of organic matters is shown in table 3:
table 3 shows the degradation rate (removal rate) of organic compounds by the molecular sieve used as the common molecular sieve in the market instead of the modified activated carbon
| Component (A) | Formaldehyde | Toluene (toluene) | Benzene | Xylene (P) | Phenol (P) | 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 for 24 hours | 50％ | 50％ | 50％ | 52％ | 52％ | 53％ | 55％ |
| 48h catalytic degradation rate | 62％ | 61％ | 61％ | 60％ | 69％ | 68％ | 69％ |
| Component (A) | Formaldehyde | Toluene (toluene) | Benzene | Xylene (P) | Phenol (P) | 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 for 24 hours | 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 clay was replaced by sodium carboxymethylcellulose;
preparation of first modified metal oxide 1:
a. adding 0.03mol of silver nitrate, 0.03mol of zinc nitrate and 20g of molybdenum oxide into water respectively, fully stirring, transferring the mixture into a high-pressure reaction kettle, reacting for 12 hours at 200 ℃, cooling, and washing to neutrality to obtain a first modified metal oxide 1;
preparing a second modified metal oxide 2:
b. adding 0.05mol of copper 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 neutrality to obtain a second modified metal oxide 2;
preparing a carbon-based composite material:
c. c, respectively weighing raw material coal active 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 active carbon, sodium carboxymethyl cellulose and the second modified metal oxide 2 into a mixing bin, stirring for 5h, adding 0.5kg of water, and continuously stirring for 2h 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. roasting the honeycomb cube obtained in the step d under the inert atmosphere of nitrogen or argon, wherein the roasting temperature is 500 ℃, the time is 8 hours, and cooling to room temperature to obtain the carbon-based composite material, and the degradation rate of organic matters is shown in table 4:
table 4 shows the degradation rate (removal rate) of organic compounds by replacing clay with sodium carboxymethylcellulose
| Component (A) | Formaldehyde | Toluene (toluene) | Benzene | Xylene (P) | Phenol (P) | 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 for 24 hours | 61％ | 60％ | 60％ | 63％ | 64％ | 65％ | 66％ |
| 48h catalytic degradation rate | 72％ | 71％ | 71％ | 70％ | 69％ | 68％ | 69％ |
| Component (A) | Formaldehyde | Toluene (toluene) | Benzene | Xylene (P) | Phenol (P) | 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 for 24 hours | 56％ | 55％ | 56％ | 55％ | 54％ | 53％ | 54％ |
| 48h catalytic degradation rate | 67％ | 66％ | 65％ | 65％ | 65％ | 64％ | 65％ |
Tables 1-4 illustrate that the first modified metal oxide 1 and the second modified metal oxide 2 are the main components of the composite material for degrading organic compounds (VOCs), and that the synergistic effect among the modified activated carbon, clay, the first modified metal oxide 1 and the second modified metal oxide 2 can significantly improve the degradation performance of the composite material, and that other materials are replaced by the modified activated carbon, the clay and the first modified metal oxide 1, and the second modified metal oxide 2 have no good degradation performance, thus indicating that the other materials have no efficient degradation capability on the organic compounds (VOCs).
Claims (2)
1. The preparation method of the carbon-based composite material for catalyzing and degrading various organic matters at room temperature is characterized by taking 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 roasting the materials in an inert atmosphere, wherein the preparation method comprises the following specific operations:
preparation of first modified metal oxide 1:
a. 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 for 12-48 hours at the temperature of 200-300 ℃, cooling, and washing to be neutral to obtain a first modified metal oxide 1;
preparing a second modified metal oxide 2:
b. adding 0.01-1moL of metal salt ferric nitrate, cupric nitrate, nickel nitrate or cobalt nitrate, 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 200-300 ℃, cooling and washing to neutrality to obtain a second modified metal oxide 2;
preparing a carbon-based composite material:
c. the method comprises the steps of weighing raw material modified activated carbon, clay, a first modified metal oxide 1 in the step a and a second modified metal oxide 2 in the step b according to the mass ratio of 1:0.1-0.5:0.1-0.5:0.1-0.1-0.5, respectively, adding the raw material modified activated carbon, clay, the first modified metal oxide 1 and the second modified metal oxide 2 in the step b into a mixing bin, stirring for 1-5h, adding 0.3-0.6kg of water, and continuing stirring for 1-2h to obtain a mixture, wherein the modified activated carbon is modified cotton stalk activated carbon, fruit tree activated carbon, apricot shell activated carbon, petroleum coke activated carbon and coal activated carbon; the clay is bentonite and attapulgite;
d. c, transferring the mixture obtained in the step c into a granulator for granulation to obtain columnar or spherical particles with the diameters 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 100X (50-100) mm;
e. and d, roasting the columnar or spherical particles or the honeycomb cubes obtained in the step d under the inert atmosphere of nitrogen or argon, wherein the roasting temperature is 300-800 ℃, the time is 1-8h, and cooling to room temperature to obtain the carbon-based composite material.
2. The method for preparing the carbon-based composite material for the catalytic degradation of various organic matters at room temperature according to claim 1, wherein the organic matters are formaldehyde, benzene, toluene, xylene, phenol, chlorophenol, benzaldehyde, chloroethane, cyclohexane or amyl acetate.
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