CN112958088A - Preparation method of biochar catalyst for synergistically purifying volatile organic pollutants - Google Patents
Preparation method of biochar catalyst for synergistically purifying volatile organic pollutants Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 29
- 239000002957 persistent organic pollutant Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 65
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims abstract description 56
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000001035 drying Methods 0.000 claims abstract description 23
- PAFZNILMFXTMIY-UHFFFAOYSA-N Cyclohexylamine Natural products NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 claims abstract description 19
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N N-phenyl amine Natural products NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000000243 solution Substances 0.000 claims abstract description 13
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- 238000000034 method Methods 0.000 claims abstract description 9
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical class [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000012266 salt solution Substances 0.000 claims abstract description 7
- 238000005470 impregnation Methods 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 34
- 239000007787 solid Substances 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 14
- 238000010531 catalytic reduction reaction Methods 0.000 claims description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims description 6
- 229940071125 manganese acetate Drugs 0.000 claims description 4
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 229940099596 manganese sulfate Drugs 0.000 claims description 3
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- 239000011702 manganese sulphate Substances 0.000 claims description 3
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 3
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 3
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 2
- 235000002867 manganese chloride Nutrition 0.000 claims description 2
- 239000011565 manganese chloride Substances 0.000 claims description 2
- 229940099607 manganese chloride Drugs 0.000 claims description 2
- 239000007789 gas Substances 0.000 abstract description 8
- 229910052751 metal Inorganic materials 0.000 abstract description 7
- 239000002184 metal Substances 0.000 abstract description 7
- 239000000126 substance Substances 0.000 abstract description 7
- 238000004056 waste incineration Methods 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 230000003647 oxidation Effects 0.000 abstract description 3
- 238000007254 oxidation reaction Methods 0.000 abstract description 3
- 150000002696 manganese Chemical class 0.000 abstract description 2
- 239000012018 catalyst precursor Substances 0.000 abstract 2
- 238000001354 calcination Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 19
- 239000000356 contaminant Substances 0.000 description 15
- 239000002253 acid Substances 0.000 description 10
- 239000003344 environmental pollutant Substances 0.000 description 7
- 231100000719 pollutant Toxicity 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 5
- 239000002912 waste gas Substances 0.000 description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 241000209140 Triticum Species 0.000 description 3
- 235000021307 Triticum Nutrition 0.000 description 3
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- 238000003306 harvesting Methods 0.000 description 3
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- 238000009776 industrial production Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 235000020234 walnut Nutrition 0.000 description 2
- 235000002566 Capsicum Nutrition 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000006002 Pepper Substances 0.000 description 1
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 1
- 235000011613 Pinus brutia Nutrition 0.000 description 1
- 241000018646 Pinus brutia Species 0.000 description 1
- 235000016761 Piper aduncum Nutrition 0.000 description 1
- 235000017804 Piper guineense Nutrition 0.000 description 1
- 244000203593 Piper nigrum Species 0.000 description 1
- 235000008184 Piper nigrum Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 235000014571 nuts Nutrition 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
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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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/656—Manganese, technetium or rhenium
- B01J23/6562—Manganese
-
- 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
- B01D53/8621—Removing nitrogen compounds
-
- 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
- B01D53/864—Removing carbon monoxide or hydrocarbons
-
- 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
-
- 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
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- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
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Abstract
The invention relates to a preparation method of a biochar catalyst for synergistically purifying volatile organic pollutants, which comprises the following steps: step one, putting a certain mass of agricultural waste biochar in a metal manganese salt solution with a certain concentration to obtain a manganese metal salt modified agricultural waste biochar catalyst precursor. And step two, performing ultrasonic impregnation on the manganese metal salt modified agricultural waste biochar catalyst precursor by using a chloropalladate solution with a certain concentration, drying the product, and calcining at high temperature to obtain the target catalyst. The catalyst is used for catalytic oxidation of benzene, cyclohexane and hexamethylene diamine three volatile organic pollution gases discharged by chemical enterprises. The method of the invention is reasonable and feasible, has low investment and operation cost, is easy to realize industrial application, reduces the secondary pollution of straw waste incineration to the atmosphere, has good social and economic benefits, and has good market prospect and development space for the prior art.
Description
Technical Field
The invention relates to the technical field of a biochar catalyst, in particular to a preparation method of a biochar catalyst for synergistically purifying volatile organic pollutants.
Background
The waste gas discharged by chemical enterprises often contains a plurality of pollutants, and common organic gas pollutants such as benzene, cyclohexane, hexamethylene diamine and the like seriously pollute the environment. At present, benzene series, hydrocarbon VOCs and the like are commonly treated in industrial production, so that the method is particularly critical and is closer to the real situation of waste gas by adopting one catalyst to cooperatively treat a plurality of VOCs components in the actual waste gas purification process. Therefore, the development of a novel catalyst suitable for the synergistic treatment of benzene, cyclohexane and hexamethylene diamine under the low-temperature condition is the key for realizing the high-efficiency purification of the tail gas of the chemical enterprises.
The crop harvesting produces a large amount of byproducts such as corn straws, wheat straws and the like, and the byproducts are usually treated by adopting an incineration mode, so that serious atmospheric pollution is caused. Therefore, the prepared metal modified agricultural waste biochar composite catalyst is of great significance to environmental protection.
Benzene, cyclohexane and hexamethylene diamine are used as target products to prepare a manganese-based catalyst, noble metal palladium is introduced to improve the oxidation-reduction capability of the catalyst, and the low-temperature efficient synergistic removal of benzene, cyclohexane and hexamethylene diamine mixed polluted gas is realized. The catalytic activity of the catalyst is optimized by changing the use amounts of the manganese salt and the noble metal palladium, and a theoretical basis is provided for a tail gas purification technology discharged by chemical enterprises.
The problem to be solved at present is how to design a method which is reasonable and feasible, ingenious in design, low in investment and operation cost, easy to realize industrial application, capable of reducing secondary pollution to the atmosphere caused by straw waste incineration and good in social and economic benefits.
Disclosure of Invention
The invention provides a preparation method of a biochar catalyst for synergistically purifying volatile organic pollutants, which aims to solve the technical problems that waste gas discharged by the existing chemical enterprises often contains various pollutants, common organic gas pollutants such as benzene, cyclohexane, hexamethylene diamine and the like seriously pollute the environment, a large amount of byproducts such as corn straws, wheat straws and the like are produced during crop harvesting, and serious atmospheric pollution is caused due to the fact that the byproducts are usually treated in an incineration mode.
The technical scheme adopted by the invention for solving the technical problems is as follows: the preparation method of the biochar catalyst for synergistically purifying volatile organic pollutants comprises the following steps,
step one, putting 1-3 g of agricultural waste biochar into a manganese metal salt solution with the concentration of 0.5-5 mol/L, and stirring for 1 hour;
step two, performing ultrasonic treatment on the product obtained in the step one at the temperature of 60-70 ℃ for 1-2 hours, and then placing the product in a drying oven at the temperature of 105 ℃ for drying for 12 hours;
step three, placing 0.5-5 mL of chloropalladate solution with the concentration of 0.1-2 mmol/L into the dried product obtained in the step two, performing ultrasonic impregnation at 60-70 ℃ for 3-6 hours, placing the product into a 105 ℃ drying oven, and drying for 12 hours;
and step four, putting the solid dried in the step three into a muffle furnace, heating the solid to 350 ℃ from room temperature at a speed of 1-5 ℃/min, keeping the temperature for 1-3 hours, then continuously heating to 550 ℃ at a speed of 1-5 ℃/min, and keeping the temperature for 1-4 hours, thus finishing the preparation process.
The agricultural waste biochar in the first step is crop straw.
The manganese metal salt in the first step is manganese nitrate, manganese sulfate, manganese acetate or manganese chloride.
In the fourth step, the solid roasting after drying is divided into two stages: in the first stage, the temperature is raised from room temperature to 350 ℃ at a speed of 1-5 ℃/min, and the temperature is kept for 1-3 hours; and in the second stage, continuously heating to 550 ℃ at a speed of 1-5 ℃/min, and keeping the temperature for 1-4 hours.
The volatile organic pollutants for the reaction comprise benzene, cyclohexane or hexamethylene diamine, the concentration of the benzene is 100-1000 ppm, the concentration of the cyclohexane is 50-500 ppm, the concentration of the hexamethylene diamine is 50-500 ppm, and the reaction temperature of catalytic reduction is 150-350 ℃.
Compared with the prior art, the invention has the beneficial effects that:
1. the biomass raw material of the catalyst is derived from agricultural wastes, so that the secondary pollution of waste incineration to the atmosphere is reduced;
2. the catalyst is suitable for the cooperative catalytic oxidation of three volatile organic pollution gases, namely benzene, cyclohexane and hexamethylene diamine, discharged by chemical enterprises, and is suitable for actual industrial production;
3. the Mn-Pd-Ox/biochar catalyst prepared by the method has high catalytic oxidation performance, and can be used for efficiently catalytically oxidizing organic pollutants at a low reaction temperature.
Drawings
FIG. 1 is a schematic view of the conversion of volatile organic contaminants, respectively, removed in accordance with an embodiment of the present invention;
FIG. 2 is a graph showing the conversion of mixed volatile organic contaminants removed in accordance with an embodiment of the present invention;
FIG. 3 is a schematic representation of the conversion of two separately removed VOC's in an embodiment of the present invention;
FIG. 4 is a graph showing the conversion of mixed volatile organic contaminants removed in accordance with example two of the present invention;
FIG. 5 is a schematic representation of the conversion of three separate volatile organic contaminants removed in an example of the present invention;
FIG. 6 is a schematic representation of the conversion of a third mixture of volatile organic contaminants from an example of the present invention;
FIG. 7 is a graph showing the conversion of volatile organic contaminants separately removed in an example of the present invention;
FIG. 8 is a graph showing the conversion of four mixtures to remove volatile organic contaminants in accordance with an embodiment of the present invention.
Detailed Description
The following describes embodiments of the present invention in further detail with reference to the accompanying drawings.
In the first embodiment, the first step is,
the preparation method of the biochar catalyst for synergistically purifying volatile organic pollutants comprises the following steps,
step one, 1g of straw biochar is placed in a manganese sulfate metal salt solution with the concentration of 1 mol/L, and stirring is carried out for 1 hour;
step two, carrying out ultrasonic treatment on the product at 70 ℃ for 1-2 hours, placing the product in a 105 ℃ oven, and drying for 12 hours;
step three, placing 2mL of 1mmol/L chloropalladic acid solution into the dried product, performing ultrasonic impregnation at 70 ℃ for 3-6 hours, placing the product into a 105 ℃ drying oven, and drying for 12 hours;
and step four, putting the dried solid into a muffle furnace, heating the solid to 350 ℃ from room temperature at the speed of 2 ℃/min, keeping the temperature for 1 hour, then continuously heating the solid to 550 ℃ at the speed of 1 ℃/min, and keeping the temperature for 4 hours.
The volatile organic pollutants for the reaction comprise benzene, cyclohexane or hexamethylene diamine, the concentration of the benzene is 100-1000 ppm, the concentration of the cyclohexane is 50-500 ppm, the concentration of the hexamethylene diamine is 50-500 ppm, and the reaction temperature of catalytic reduction is 150-350 ℃.
FIG. 1 is a schematic diagram of the respective removal conversions of volatile organic contaminants, including 95, 90, and 75% for benzene, cyclohexane, and hexamethylene diamine, in accordance with an embodiment of the present invention.
FIG. 2 is a graph showing the conversion of mixed removal of volatile organic contaminants according to an embodiment of the present invention, wherein the conversion of mixed removal of benzene, cyclohexane and hexamethylene diamine is 80, 70 and 55%.
Example two
The preparation method of the biochar catalyst for synergistically purifying volatile organic pollutants comprises the following steps,
step one, 2g of corncob biochar is placed in a manganese nitrate metal salt solution with the concentration of 1 mol/L, and stirred for 1 hour;
step two, after the product is subjected to ultrasonic treatment for 2 hours at the temperature of 60 ℃, the product is placed in a drying oven at the temperature of 105 ℃ and dried for 12 hours;
step three, placing 4 mL of 1mmol/L chloropalladic acid solution into the dried product, ultrasonically dipping the chloropalladic acid solution for 3 hours at the temperature of 60 ℃, placing the chloropalladic acid solution into a drying oven at the temperature of 105 ℃, and drying the chloropalladic acid solution for 12 hours;
and step four, putting the dried solid into a muffle furnace, heating the solid to 350 ℃ from room temperature at the speed of 2 ℃/min, keeping the temperature for 1 hour, then continuously heating the solid to 550 ℃ at the speed of 1 ℃/min, and keeping the temperature for 4 hours.
The volatile organic pollutants for the reaction comprise benzene, cyclohexane or hexamethylene diamine, the concentration of the benzene is 100-1000 ppm, the concentration of the cyclohexane is 50-500 ppm, the concentration of the hexamethylene diamine is 50-500 ppm, and the reaction temperature of catalytic reduction is 150-350 ℃.
FIG. 3 is a graph showing the respective conversions of the volatile organic contaminants to benzene, cyclohexane and hexamethylenediamine in the examples of the present invention, respectively, as 92, 91 and 76%.
FIG. 4 is a graph showing the conversion of mixed removal of volatile organic contaminants according to example two of the present invention, wherein the conversion of mixed removal of benzene, cyclohexane and hexamethylene diamine is 84, 66 and 54%.
EXAMPLE III
The preparation method of the biochar catalyst for synergistically purifying volatile organic pollutants comprises the following steps,
step one, 2g of walnut shell biochar is placed in a manganese acetate metal salt solution with the concentration of 1 mol/L, and stirred for 1 hour;
step two, after the product is subjected to ultrasonic treatment for 2 hours at the temperature of 60 ℃, the product is placed in a drying oven at the temperature of 105 ℃ and dried for 12 hours;
step three, placing 4 mL of 1mmol/L chloropalladic acid solution into the dried product, ultrasonically dipping the chloropalladic acid solution for 3 hours at the temperature of 60 ℃, placing the chloropalladic acid solution into a drying oven at the temperature of 105 ℃, and drying the chloropalladic acid solution for 12 hours;
and step four, putting the dried solid into a muffle furnace, heating the solid to 350 ℃ from room temperature at the speed of 2 ℃/min, keeping the temperature for 1 hour, then continuously heating the solid to 550 ℃ at the speed of 1 ℃/min, and keeping the temperature for 4 hours.
The volatile organic pollutants for the reaction comprise benzene, cyclohexane or hexamethylene diamine, the concentration of the benzene is 100-1000 ppm, the concentration of the cyclohexane is 50-500 ppm, the concentration of the hexamethylene diamine is 50-500 ppm, and the reaction temperature of catalytic reduction is 150-350 ℃.
FIG. 5 is a graph showing the respective removal conversions of the volatile organic contaminants, namely, the removal conversions of benzene, cyclohexane and hexamethylene diamine, of 93, 92 and 78%, respectively, in the example of the present invention.
FIG. 6 is a graph showing the conversion of mixed removal of volatile organic contaminants according to example three of the present invention, wherein the conversion of mixed removal of benzene, cyclohexane and hexamethylene diamine is 86, 70 and 60%.
Example four
The preparation method of the biochar catalyst for synergistically purifying volatile organic pollutants comprises the following steps,
step one, putting 1g of bagasse biochar into a manganese acetate metal salt solution with the concentration of 1 mol/L, and stirring for 1 hour;
step two, after the product is subjected to ultrasonic treatment for 2 hours at the temperature of 60 ℃, the product is placed in a drying oven at the temperature of 105 ℃ and dried for 12 hours;
step three, placing 2mL of 1mmol/L chloropalladic acid solution into the dried product, performing ultrasonic immersion for 3 hours at 60 ℃, placing the product into a 105 ℃ drying oven, and drying for 12 hours;
and step four, heating the dried solid in a muffle furnace from room temperature to 350 ℃ at the speed of 2 ℃/min, keeping the temperature for 1 hour, then continuously heating to 550 ℃ at the speed of 1 ℃/min, and keeping the temperature for 4 hours.
The volatile organic pollutants for the reaction comprise benzene, cyclohexane or hexamethylene diamine, the concentration of the benzene is 100-1000 ppm, the concentration of the cyclohexane is 50-500 ppm, the concentration of the hexamethylene diamine is 50-500 ppm, and the reaction temperature of catalytic reduction is 150-350 ℃.
FIG. 7 is a graph showing the respective conversions of the example of the present invention to remove volatile organic contaminants, such as benzene, cyclohexane, and hexamethylenediamine, respectively, at 96, 94, and 80%.
FIG. 8 is a graph showing the conversion of mixed removal of volatile organic contaminants according to example four of the present invention, wherein the conversion of mixed removal of benzene, cyclohexane, and hexamethylene diamine is 85, 80, and 55%.
In practical application, the agricultural waste biochar adopted by the invention is straw, walnut shells, bagasse, corncobs, pine nut shells, pepper stalks and the like can be selected, the biomass raw material of the catalyst is derived from agricultural waste, the secondary pollution of waste incineration to the atmosphere is reduced, and the prepared metal modified agricultural waste biochar composite catalyst is used for treating environmental pollutants and has important significance for the environmental protection industry.
The method is reasonable and feasible, has low investment and operation cost, is easy to realize industrial application, reduces secondary pollution to the atmosphere caused by straw waste incineration, has good social and economic benefits, solves the technical problems that the waste gas discharged by the existing chemical enterprises often contains various pollutants, common organic gas pollutants such as benzene, cyclohexane, hexamethylene diamine and the like seriously pollute the environment, a large amount of byproducts such as corn straws, wheat straws and the like are produced during crop harvesting, and the serious atmosphere pollution is caused by adopting an incineration mode for treatment, and has good market prospect and development space for the prior art.
The preferred embodiments and examples of the present invention have been described in detail with reference to the accompanying drawings, but the present invention is not limited to the embodiments and examples described above, and various changes can be made within the knowledge of those skilled in the art without departing from the concept of the present invention.
Claims (5)
1. The preparation method of the biochar catalyst for synergistically purifying volatile organic pollutants is characterized by comprising the following steps of: comprises the following steps of (a) carrying out,
step one, putting 1-3 g of agricultural waste biochar into a manganese metal salt solution with the concentration of 0.5-5 mol/L, and stirring for 1 hour;
step two, performing ultrasonic treatment on the product obtained in the step one at the temperature of 60-70 ℃ for 1-2 hours, and then placing the product in a drying oven at the temperature of 105 ℃ for drying for 12 hours;
step three, placing 0.5-5 mL of chloropalladate solution with the concentration of 0.1-2 mmol/L into the dried product obtained in the step two, performing ultrasonic impregnation at 60-70 ℃ for 3-6 hours, placing the product into a 105 ℃ drying oven, and drying for 12 hours;
and step four, putting the solid dried in the step three into a muffle furnace, heating the solid to 350 ℃ from room temperature at a speed of 1-5 ℃/min, keeping the temperature for 1-3 hours, then continuously heating to 550 ℃ at a speed of 1-5 ℃/min, and keeping the temperature for 1-4 hours, thus finishing the preparation process.
2. The method for preparing the biochar catalyst for synergistically purifying volatile organic pollutants according to claim 1, which is characterized in that: the agricultural waste biochar in the first step is crop straw.
3. The method for preparing the biochar catalyst for synergistically purifying volatile organic pollutants according to claim 1, which is characterized in that: the manganese metal salt in the first step is manganese nitrate, manganese sulfate, manganese acetate or manganese chloride.
4. The method for preparing the biochar catalyst for synergistically purifying volatile organic pollutants according to claim 1, which is characterized in that: in the fourth step, the solid roasting after drying is divided into two stages: in the first stage, the temperature is raised from room temperature to 350 ℃ at a speed of 1-5 ℃/min, and the temperature is kept for 1-3 hours; and in the second stage, continuously heating to 550 ℃ at a speed of 1-5 ℃/min, and keeping the temperature for 1-4 hours.
5. The method for preparing the biochar catalyst for synergistically purifying volatile organic pollutants according to claim 1, which is characterized in that: the volatile organic pollutants for the reaction comprise benzene, cyclohexane or hexamethylene diamine, the concentration of the benzene is 100-1000 ppm, the concentration of the cyclohexane is 50-500 ppm, the concentration of the hexamethylene diamine is 50-500 ppm, and the reaction temperature of catalytic reduction is 150-350 ℃.
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5145657A (en) * | 1987-01-21 | 1992-09-08 | Nippon Shokubai Kagaku Kogyo Co., Ltd. | Method for purification of gas |
| CN101204654A (en) * | 2006-12-20 | 2008-06-25 | 中国科学院生态环境研究中心 | A kind of supported precious metal catalyst and preparation method thereof for catalytic oxidation of benzene series at low temperature |
| CN101780952A (en) * | 2010-03-26 | 2010-07-21 | 上海交通大学 | Method for preparing loading functional oxide porous carbon |
| CN101961653A (en) * | 2010-09-30 | 2011-02-02 | 浙江工业大学 | Composite oxide catalytic combustion catalyst as well as preparation method and application thereof |
| CN102240557A (en) * | 2011-05-12 | 2011-11-16 | 南京工业大学 | A nickel-iron-manganese composite oxide catalyst for treating industrial waste gas and its preparation method |
| CN104874396A (en) * | 2015-04-03 | 2015-09-02 | 上海华峰新材料研发科技有限公司 | Catalytic combustion-based catalyst for removing low-concentration and volatile organic compounds and preparation method thereof |
| CN106582266A (en) * | 2016-11-16 | 2017-04-26 | 中山大学 | Device and method for purifying combined air pollutants |
| CN107159202A (en) * | 2017-04-01 | 2017-09-15 | 浙江工业大学 | A kind of supported palladium catalyst of additive Mn and preparation method and application |
| CN107261830A (en) * | 2017-08-01 | 2017-10-20 | 中国科学院过程工程研究所 | A kind of system and method for ira situ degradation dioxin in flue gas class material |
-
2021
- 2021-03-23 CN CN202110305519.0A patent/CN112958088A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5145657A (en) * | 1987-01-21 | 1992-09-08 | Nippon Shokubai Kagaku Kogyo Co., Ltd. | Method for purification of gas |
| CN101204654A (en) * | 2006-12-20 | 2008-06-25 | 中国科学院生态环境研究中心 | A kind of supported precious metal catalyst and preparation method thereof for catalytic oxidation of benzene series at low temperature |
| CN101780952A (en) * | 2010-03-26 | 2010-07-21 | 上海交通大学 | Method for preparing loading functional oxide porous carbon |
| CN101961653A (en) * | 2010-09-30 | 2011-02-02 | 浙江工业大学 | Composite oxide catalytic combustion catalyst as well as preparation method and application thereof |
| CN102240557A (en) * | 2011-05-12 | 2011-11-16 | 南京工业大学 | A nickel-iron-manganese composite oxide catalyst for treating industrial waste gas and its preparation method |
| CN104874396A (en) * | 2015-04-03 | 2015-09-02 | 上海华峰新材料研发科技有限公司 | Catalytic combustion-based catalyst for removing low-concentration and volatile organic compounds and preparation method thereof |
| CN106582266A (en) * | 2016-11-16 | 2017-04-26 | 中山大学 | Device and method for purifying combined air pollutants |
| CN107159202A (en) * | 2017-04-01 | 2017-09-15 | 浙江工业大学 | A kind of supported palladium catalyst of additive Mn and preparation method and application |
| CN107261830A (en) * | 2017-08-01 | 2017-10-20 | 中国科学院过程工程研究所 | A kind of system and method for ira situ degradation dioxin in flue gas class material |
Non-Patent Citations (4)
| Title |
|---|
| MOHAMMAD ZABIHI ET AL.,: "Supported copper and cobalt oxides on activated carbon for simultaneous oxidation of toluene and cyclohexane in air", 《RSC ADVANCES》 * |
| 刘希涛: "《活化过硫酸盐在环境污染控制中的应用》", 30 April 2018, 中国环境科学出版社 * |
| 卢英等: "整体式锰铈复合氧化物催化剂的二乙胺催化燃烧性能", 《环境化学》 * |
| 王建成著: "《超临界水介质制备能源和环境材料》", 31 December 2013, 国防工业出版社 * |
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