CN113663472B - Multistage treatment method for organic waste gas - Google Patents
Multistage treatment method for organic waste gas Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 30
- 239000007789 gas Substances 0.000 title claims abstract description 28
- 239000010815 organic waste Substances 0.000 title claims abstract description 20
- 238000001179 sorption measurement Methods 0.000 claims abstract description 39
- 230000003197 catalytic effect Effects 0.000 claims abstract description 38
- 239000000463 material Substances 0.000 claims abstract description 37
- 230000003647 oxidation Effects 0.000 claims abstract description 37
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 37
- 238000010438 heat treatment Methods 0.000 claims abstract description 34
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims abstract description 34
- 239000003463 adsorbent Substances 0.000 claims abstract description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910021417 amorphous silicon Inorganic materials 0.000 claims abstract description 18
- 239000010941 cobalt Substances 0.000 claims abstract description 17
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910000428 cobalt oxide Inorganic materials 0.000 claims abstract description 17
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 16
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 8
- 238000003795 desorption Methods 0.000 claims abstract description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 70
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 69
- 239000007787 solid Substances 0.000 claims description 64
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 60
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 46
- 238000001035 drying Methods 0.000 claims description 35
- 229910052757 nitrogen Inorganic materials 0.000 claims description 35
- 238000005406 washing Methods 0.000 claims description 35
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 33
- 238000006243 chemical reaction Methods 0.000 claims description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- 238000001354 calcination Methods 0.000 claims description 28
- 238000002156 mixing Methods 0.000 claims description 25
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 24
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 23
- 238000001914 filtration Methods 0.000 claims description 22
- 238000001816 cooling Methods 0.000 claims description 21
- 239000008367 deionised water Substances 0.000 claims description 21
- 229910021641 deionized water Inorganic materials 0.000 claims description 21
- 239000011521 glass Substances 0.000 claims description 21
- 239000013246 bimetallic metal–organic framework Substances 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 13
- 239000012295 chemical reaction liquid Substances 0.000 claims description 12
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 10
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 10
- 239000013110 organic ligand Substances 0.000 claims description 10
- GPNNOCMCNFXRAO-UHFFFAOYSA-N 2-aminoterephthalic acid Chemical compound NC1=CC(C(O)=O)=CC=C1C(O)=O GPNNOCMCNFXRAO-UHFFFAOYSA-N 0.000 claims description 9
- XNDZQQSKSQTQQD-UHFFFAOYSA-N 3-methylcyclohex-2-en-1-ol Chemical group CC1=CC(O)CCC1 XNDZQQSKSQTQQD-UHFFFAOYSA-N 0.000 claims description 9
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical group O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims description 9
- 238000006460 hydrolysis reaction Methods 0.000 claims description 9
- CNFDGXZLMLFIJV-UHFFFAOYSA-L manganese(II) chloride tetrahydrate Chemical group O.O.O.O.[Cl-].[Cl-].[Mn+2] CNFDGXZLMLFIJV-UHFFFAOYSA-L 0.000 claims description 9
- 238000002791 soaking Methods 0.000 claims description 9
- 238000003763 carbonization Methods 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 7
- 239000002244 precipitate Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 238000009210 therapy by ultrasound Methods 0.000 claims description 7
- OYFRNYNHAZOYNF-UHFFFAOYSA-N 2,5-dihydroxyterephthalic acid Chemical compound OC(=O)C1=CC(O)=C(C(O)=O)C=C1O OYFRNYNHAZOYNF-UHFFFAOYSA-N 0.000 claims description 4
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- 150000001868 cobalt Chemical class 0.000 claims description 4
- 150000002696 manganese Chemical class 0.000 claims description 4
- 239000012621 metal-organic framework Substances 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 230000003213 activating effect Effects 0.000 claims description 3
- 238000010000 carbonizing Methods 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 238000011049 filling Methods 0.000 claims description 3
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 2
- 230000007062 hydrolysis Effects 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 6
- 239000012855 volatile organic compound Substances 0.000 description 23
- 239000002912 waste gas Substances 0.000 description 18
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- 239000011572 manganese Substances 0.000 description 3
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- 230000008569 process Effects 0.000 description 3
- 239000005886 Chlorantraniliprole Substances 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- PSOVNZZNOMJUBI-UHFFFAOYSA-N chlorantraniliprole Chemical compound CNC(=O)C1=CC(Cl)=CC(C)=C1NC(=O)C1=CC(Br)=NN1C1=NC=CC=C1Cl PSOVNZZNOMJUBI-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
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- 230000007059 acute toxicity Effects 0.000 description 1
- 231100000403 acute toxicity Toxicity 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- -1 benzamide compound Chemical class 0.000 description 1
- KXDAEFPNCMNJSK-UHFFFAOYSA-N benzene carboxamide Natural products NC(=O)C1=CC=CC=C1 KXDAEFPNCMNJSK-UHFFFAOYSA-N 0.000 description 1
- 230000007665 chronic toxicity Effects 0.000 description 1
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- 238000011161 development Methods 0.000 description 1
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- ZGNITFSDLCMLGI-UHFFFAOYSA-N flubendiamide Chemical compound CC1=CC(C(F)(C(F)(F)F)C(F)(F)F)=CC=C1NC(=O)C1=CC=CC(I)=C1C(=O)NC(C)(C)CS(C)(=O)=O ZGNITFSDLCMLGI-UHFFFAOYSA-N 0.000 description 1
- 230000005484 gravity Effects 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
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
- B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
- B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
-
- 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
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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- B01J35/394—
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- B01J35/61—
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
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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 discloses a multistage treatment method of organic waste gas, which comprises the steps of carrying out adsorption treatment on the organic waste gas by adopting an adsorption assembly formed by serially connecting a plurality of adsorption columns filled with nitrogen-doped carbon adsorbents, then carrying out heating desorption treatment on the adsorption assembly, feeding gas desorbed by the adsorption assembly into a catalytic oxidation reactor, and carrying out catalytic oxidation treatment under the catalysis of a nitrogen-doped cobalt/manganese oxide material coated by amorphous silicon oxide. The method is simple to operate and has good treatment effect.
Description
Technical Field
The invention relates to the technical field of waste gas treatment, in particular to a multistage treatment method of organic waste gas.
Background
The big problems influencing the existence and development of the cattle of the human beings at present comprise population, environment, food, energy and the like, pesticides are closely and indiscriminately connected with the problems, the improvement of the pesticides can promote the income increase and yield increase of the food so as to improve the living conditions of people, but the unreasonable use of the pesticides also brings about little harm to the environment, and further the health of people is influenced by the enrichment of a food chain. Therefore, some pesticides with high toxicity, poor selectivity and large residual quantity must be abandoned, and novel pesticides with low toxicity, small residual quantity and small environmental pollution are sought. China is a big agricultural country, and 22% of the population of the world is cultivated by 7% of cultivated land area of the world. The pesticide is also in a relatively important position in China, but the unreasonable use of the pesticide in China pollutes the environment, so the research and development of the pesticide with low toxicity is urgent.
Chlorantraniliprole is a novel o-formamido benzamide compound developed by DuPont corporation in 2000, is formed by structural optimization and transformation on the basis of flubendiamide, has a good insecticidal effect, is low in toxicity, has extremely small acute, sub-chronic and chronic toxicity on mammals, has little influence on non-target organisms and a plurality of non-target arthropods, and is widely applied. At present, the synthesis process of chlorantraniliprole is mature, but a large amount of waste gas is generated in the synthesis process, and if the waste gas is not treated in time, the waste gas pollutes the atmosphere.
The patent with the application number of CN201711292252.6 provides a catalytic purification treatment method for VOC-containing waste gas, the VOC-containing waste gas enters a heat exchanger after passing through a fan, the heated VOC-containing waste gas enters a catalytic oxidation reactor, a low-temperature catalytic oxidation reactor is arranged in parallel with the catalytic oxidation reactor, and the outlet material flows of the catalytic oxidation reactor and the low-temperature catalytic oxidation reactor are cooled by the heat exchanger and then reach the standard to be discharged. CN201610983548.1 provides a method for treating VOC waste gas, comprising the following steps: selecting a compound microorganism; domesticating the composite microorganism by using a domestication nutrient solution; carrying out centrifugal resuspension operation to improve the concentration of microorganisms; soaking the activated carbon particles in the composite microbial liquid to obtain a microbial activated carbon filler; selecting a skeleton filler, and mixing the skeleton filler with a microbial activated carbon filler to obtain a biological carrier filler; filling a biological carrier filler into the biological trickling filter; spraying the spray liquid to the top of the biological carrier filler, wherein the spray liquid can flow through the biological carrier filler and drip to the bottom of the biological trickling filter based on the self gravity of the spray liquid; introducing VOC waste gas to the bottom of the biological carrier filler for enabling the VOC waste gas to permeate the biological carrier filler; the spray liquid at the bottom of the biological trickling filter is collected and discharged, so that the VOC waste gas treatment efficiency can be improved. As can be seen from the above prior art, although the existing methods for treating organic waste gas are mature, the treatment effect needs to be further improved in specific applications. Since how to optimize the organic waste gas treatment process to improve the treatment effect becomes an important objective of research.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: aiming at the defects in the prior art, the method for treating the organic waste gas in multiple stages is simple to operate and good in treatment effect.
In order to solve the technical problem, the technical scheme of the invention is as follows:
a multi-stage treatment method for organic waste gas includes such steps as adsorbing the organic waste gas by serially connected adsorption modules with multiple adsorption columns containing N-doped carbon adsorbent, heating for desorption, introducing the desorbed gas into catalytic oxidation reactor, and catalytic oxidizing under the catalysis of nitrogen-doped Co/Mn oxide coated by amorphous silicon oxide.
As a preferred aspect of the above technical solution, the preparation method of the nitrogen-doped carbon adsorbent comprises:
mixing aluminum salt, organic ligand, sodium hydroxide solution and methanol at 500-600W, performing ultrasonic treatment for 30-50min, placing the obtained mixture in an autoclave at 120-130 ℃ for performing constant temperature reaction for 2.5-3.5h, cooling to room temperature after the reaction is finished, performing centrifugal treatment, washing the obtained precipitate with methanol, and drying to obtain metal-organogel powder; placing the mixture in a muffle furnace under nitrogen atmosphere for primary calcination treatment, washing calcined solids by using a hydrochloric acid solution and deionized water in sequence, and then mixing the calcined solids with a 2mol/L ethanol solution of potassium hydroxide in a mass ratio of 1: (4-5) mixing and activating for 30min, drying, then carrying out secondary calcination, and finally washing the calcined solid with a hydrochloric acid solution and deionized water in sequence, and drying to obtain the adsorbent;
preferably, in the above aspect, the aluminum salt is aluminum nitrate nonahydrate, the organic ligand is 2-aminoterephthalic acid, the concentration of the sodium hydroxide solution is 2mol/L, and the ratio of the amount of aluminum nitrate nonahydrate, 2-aminoterephthalic acid, sodium hydroxide solution and methanol is (1.5-1.7) g: (0.1-0.15) g: (2-2.5) ml:50ml.
Preferably, the nitrogen flow rate is 100ml/min, the temperature rise rate is 3-5 ℃/min, the calcination temperature is 700 ℃, the time of the first calcination treatment is 4.5-5.5h, and the time of the second calcination treatment is 0.5-1.5h.
Preferably, the preparation method of the amorphous silicon oxide coated nitrogen-doped cobalt/manganese oxide material comprises the following steps:
(1) Mixing manganese salt, cobalt salt and an organic ligand, adding a solvent mixed by DMF (dimethyl formamide), water and ethanol, stirring until a solid is dissolved, reacting at 115-125 ℃ for 22-25h, cooling to room temperature after the reaction is finished, filtering a reaction solution, washing the obtained solid by deionized water and ethanol in sequence, and drying to obtain the bimetallic MOF material;
(2) Soaking the prepared bimetallic MOF material in ethyl orthosilicate at 55-65 ℃ for 10-15h, filtering, washing the filtered solid by adopting methanol, putting the washed solid in a glass tube, adding a hydrochloric acid solution into the glass tube, introducing nitrogen into the glass tube, carrying out hydrolysis reaction at constant temperature of 45-55 ℃ for 28-32h, stopping introducing the nitrogen after the reaction is finished, cooling to room temperature, filtering the reaction liquid, drying, carbonizing in nitrogen atmosphere, and finally calcining the carbonized solid to prepare the amorphous silicon oxide coated nitrogen-doped cobalt/manganese oxide material.
Preferably, in the step (1), the manganese salt is manganese chloride tetrahydrate, the cobalt salt is cobalt nitrate hexahydrate, and the organic ligand is one of 2-methylimidazole, 2, 5-dihydroxyterephthalic acid and 1,3, 5-trimesic acid; the dosage ratio of the manganese chloride tetrahydrate, the cobalt nitrate hexahydrate, the organic ligand, the DMF, the water and the ethanol is (5-5.5) mmol: (1.5-2) mmol: (2-2.5) mmol:150ml: (5-10) ml: (5-10) ml.
Preferably, the dosage ratio of the bimetallic MOF material to the tetraethoxysilane is (0.5-1) g: (8-10) ml.
Preferably, in the above technical scheme, the concentration of the hydrochloric acid solution is 0.1mol/L, and the dosage ratio of the hydrochloric acid solution to the solid is 5-8ml:1g of a compound; the nitrogen flow rate during hydrolysis is 10-15ml/min.
Preferably, in the carbonization treatment, the flow rate of nitrogen is 145-155ml/min, the temperature is firstly increased to 400 ℃ at the speed of 5 ℃/min, the temperature is kept for 1h, then the temperature is increased to 600 ℃ at the speed of 3 ℃/min, and the constant temperature is kept for 3-4h; the calcination treatment is to heat up to 500 ℃ at the speed of 1 ℃/min and keep the temperature for 1-3h.
As a preferable aspect of the above-mentioned technical means,the air input during adsorption is 0.5-1m3The desorption temperature is 95-105 ℃, the desorption time is 1-1.5h, the reaction temperature in the catalytic oxidation reactor is 300-450 ℃, and the air speed ratio during catalytic oxidation is 30000-50000h-1The catalytic oxidation reactor is a fixed bed with the outer diameter of 20mm, the inner diameter of 10mm and the height of 20mm, and the filling amount of the catalyst is 0.2-0.3m3。
Due to the adoption of the technical scheme, the invention has the beneficial effects that:
the invention adopts the adsorption method and the catalytic oxidation method to jointly treat the organic waste gas, and has simple operation and good effect. The method comprises the steps of firstly preparing a Co and manganese-based bimetallic MOF material, then taking the Co and manganese-based bimetallic MOF material as a template, adding the template into tetraethoxysilane for soaking by adopting a nano-casting method, then hydrolyzing, then carbonizing in a nitrogen atmosphere, and finally calcining, wherein a nitrogen-doped cobalt/manganese oxide is coated in an amorphous silicon oxide nanotube, so that the catalytic activity site of a catalyst is effectively protected, and the catalyst has higher catalytic activity; in addition, the method adopts the bimetal MOF material as the template, and the nano-casting method is more favorable for dispersing the catalytic active sites, so that the prepared material has high catalytic efficiency.
According to the invention, the self-made nitrogen-doped porous carbon is used as the adsorbent, the metal-organic gel is firstly prepared as the precursor, after the precursor is calcined, the porosity of the precursor is increased by adopting the calcination treatment after the activation of potassium hydroxide, and the prepared adsorbent has high porosity, large specific surface area and irregular multistage pore channel structure, and can effectively improve the collision probability of waste gas and pore channels, thereby improving the adsorption efficiency of the waste gas.
Detailed Description
The invention is further illustrated by the following examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention.
In the following examples the content of VOCs in the organic waste gas is 8000-10000mg/m3。
Example 1
Mixing 15g of aluminum nitrate nonahydrate, 1g of 2-aminoterephthalic acid, 20ml of 2mol/L sodium hydroxide solution and 500ml of methanol under 500W, carrying out ultrasonic treatment for 30min, placing the obtained mixture in an autoclave for carrying out constant temperature reaction at 120 ℃ for 2.5h, cooling to room temperature after the reaction is finished, carrying out centrifugal treatment, washing the obtained precipitate with methanol, and drying to obtain metal-organic gel powder; placing the mixture into a muffle furnace, controlling the flow of nitrogen to be 100ml/min, heating to 700 ℃ at the speed of 3 ℃/min to perform primary calcination treatment for 4.5 hours, then washing calcined solids by sequentially adopting 1mol/L hydrochloric acid solution and deionized water, and then mixing the washed calcined solids with 2mol/L ethanol solution of potassium hydroxide in a mass ratio of 1:4, mixing and activating for 30min, drying, heating to 700 ℃ at the speed of 3 ℃/min, controlling the flow of nitrogen to be 100ml/min, carrying out secondary calcination for 1h, and finally washing the calcined solid by sequentially adopting 1mol/L hydrochloric acid solution and deionized water, and drying to obtain the adsorbent;
mixing 5mmol of manganese chloride tetrahydrate, 1.5mmol of cobalt nitrate hexahydrate and 2mmol of 1,3 and 5-trimesic acid, adding 150ml of DMF, 5ml of water and 5ml of ethanol mixed solvent, stirring until the solid is dissolved, reacting for 22 hours at 115 ℃, cooling to room temperature after the reaction is finished, filtering the reaction liquid, washing the obtained solid with deionized water and ethanol in sequence, and drying to obtain the MOF bimetallic material;
soaking 5g of prepared bimetallic MOF material in 80ml of ethyl orthosilicate at 55 ℃ for 10h, then filtering, washing the filtered solid by adopting methanol, then placing the washed solid in a glass tube, adding a hydrochloric acid solution with the concentration of 0.1mol/L into the glass tube, wherein the dosage ratio of the hydrochloric acid solution to the solid is 5ml:1g, introducing nitrogen into a glass tube, wherein the flow rate of the nitrogen is 145ml/min, carrying out hydrolysis reaction at constant temperature of 45 ℃ for 28h, stopping introducing the nitrogen after the reaction is finished, cooling to room temperature, filtering and drying the reaction liquid, heating to 400 ℃ at the speed of 5 ℃/min in the nitrogen atmosphere, keeping the temperature for 1h, heating to 600 ℃ at the speed of 3 ℃/min, keeping the temperature for 3h, heating the solid obtained by carbonization to 500 ℃ at the speed of 1 ℃/min in the air atmosphere, and keeping the temperature for 1h to obtain the amorphous silicon oxide-coated nitrogen-doped cobalt/manganese oxide material;
the content of VOCs is 8000mg/m3Organic waste gas ofAt 1m3Pumping the nitrogen-doped carbon adsorbent into an adsorption assembly formed by serially connecting 3 adsorption columns filled with the nitrogen-doped carbon adsorbent at a flow rate of/h for adsorption treatment, then heating and desorbing the adsorption assembly at the temperature of 95 ℃ for 1h, introducing the gas desorbed from the adsorption assembly into a catalytic oxidation reactor, and controlling the air speed ratio during catalytic oxidation to be 30000h-1Catalytic oxidation treatment is carried out at 300 ℃ under the catalysis of amorphous silicon oxide coated nitrogen-doped cobalt/manganese oxide material, and the content of VOCs in the waste gas at the outlet of a catalytic oxidation reactor is 5mg/m3The removal rate of VOCs was 99.94%.
Example 2
Mixing 17g of aluminum nitrate nonahydrate, 1.5g of 2-amino terephthalic acid, 25ml of sodium hydroxide solution with the concentration of 2mol/L and 500ml of methanol under 600W, carrying out ultrasonic treatment for 50min, placing the obtained mixture in a high-pressure kettle, carrying out constant-temperature reaction for 3.5h at 130 ℃, cooling to room temperature after the reaction is finished, carrying out centrifugal treatment, washing the obtained precipitate with methanol, and drying to obtain metal-organic gel powder; placing the mixture into a muffle furnace, controlling the flow of nitrogen to be 100ml/min, heating to 700 ℃ at the speed of 5 ℃/min to perform primary calcination treatment for 5.5h, then washing calcined solids by sequentially adopting 1mol/L hydrochloric acid solution and deionized water, and then mixing the washed calcined solids with 2mol/L ethanol solution of potassium hydroxide in a mass ratio of 1:5 for 30min, drying, heating to 700 ℃ at the speed of 5 ℃/min, controlling the flow of nitrogen to be 100ml/min, carrying out secondary calcination for 1.5h, washing calcined solids by adopting 1mol/L hydrochloric acid solution and deionized water in sequence, and drying to obtain an adsorbent;
mixing 5.5mmol of manganese chloride tetrahydrate, 2mmol of cobalt nitrate hexahydrate and 2.5mmol of 1,3 and 5-trimesic acid, adding 150ml of DMF, 10ml of water and 10ml of ethanol mixed solvent, stirring until the solid is dissolved, reacting for 25 hours at 125 ℃, cooling to room temperature after the reaction is finished, filtering the reaction liquid, washing the obtained solid with deionized water and ethanol in sequence, and drying to obtain the bimetallic MOF material;
soaking 10g of prepared bimetallic MOF material in 100ml of ethyl orthosilicate at 65 ℃ for 15h, then filtering, washing the filtered solid by adopting methanol, then placing the washed solid in a glass tube, adding a hydrochloric acid solution with the concentration of 0.1mol/L into the glass tube, wherein the dosage ratio of the hydrochloric acid solution to the solid is 8ml:1g, introducing nitrogen into a glass tube, wherein the flow rate of the nitrogen is 155ml/min, carrying out hydrolysis reaction at constant temperature of 55 ℃ for 32h, stopping introducing the nitrogen after the reaction is finished, cooling to room temperature, filtering and drying the reaction liquid, heating to 400 ℃ at the speed of 5 ℃/min in the nitrogen atmosphere, keeping the temperature for 1h, heating to 600 ℃ at the speed of 3 ℃/min, keeping the temperature for 4h, heating the solid obtained by carbonization to 500 ℃ at the speed of 1 ℃/min in the air atmosphere, and keeping the temperature for 3h to obtain the amorphous silicon oxide-coated nitrogen-doped cobalt/manganese oxide material;
the content of VOCs is 10000mg/m3In the organic waste gas of 1m3Pumping the nitrogen-doped carbon adsorbent into an adsorption component formed by serially connecting 3 adsorption columns filled with the nitrogen-doped carbon adsorbent at a flow rate of/h for adsorption treatment, then heating and desorbing the adsorption component at the temperature of 105 ℃ for 1.5h, feeding the gas desorbed by the adsorption component into a catalytic oxidation reactor, and controlling the air speed ratio during catalytic oxidation to 50000h-1Catalytic oxidation treatment is carried out at 450 ℃ under the catalysis of nitrogen-doped cobalt/manganese oxide materials coated by amorphous silicon oxide, and the content of VOCs in the waste gas at the outlet of a catalytic oxidation reactor is 20mg/m3The removal rate of VOCs was 99.8%.
Example 3
Mixing 15.5g of aluminum nitrate nonahydrate, 1g of 2-amino terephthalic acid, 22ml of sodium hydroxide solution with the concentration of 2mol/L and 500ml of methanol under 500W, carrying out ultrasonic treatment for 35min, placing the obtained mixture in an autoclave for carrying out constant temperature reaction at 120 ℃ for 3h, cooling to room temperature after the reaction is finished, carrying out centrifugal treatment, washing the obtained precipitate with methanol, and then drying to obtain metal-organic gel powder; placing the mixture into a muffle furnace, controlling the flow of nitrogen to be 100ml/min, heating to 700 ℃ at the speed of 3.5 ℃/min to perform primary calcination treatment for 5h, washing calcined solids by sequentially adopting 1mol/L hydrochloric acid solution and deionized water, and then mixing the washed calcined solids with 2mol/L ethanol solution of potassium hydroxide in a mass ratio of 1:4 for 30min, drying, heating to 700 ℃ at the speed of 3 ℃/min, controlling the nitrogen flow to be 100ml/min, carrying out secondary calcination treatment for 1h, and finally washing the calcined solid by sequentially adopting 1mol/L hydrochloric acid solution and deionized water, and drying to obtain the adsorbent;
mixing 5mmol of manganese chloride tetrahydrate, 2mmol of cobalt nitrate hexahydrate and 2.5mmol of 1,3, 5-trimesic acid, adding 150ml of DMF, 8ml of water and 8ml of ethanol mixed solvent, stirring until the solid is dissolved, reacting for 23 hours at 120 ℃, cooling to room temperature after the reaction is finished, filtering the reaction liquid, washing the obtained solid with deionized water and ethanol in sequence, and drying to obtain the MOF bimetallic material;
soaking 6g of prepared bimetallic MOF material in 90ml of 60 ℃ ethyl orthosilicate for 11h, then filtering, washing the filtered solid by adopting methanol, then placing the washed solid in a glass tube, adding a hydrochloric acid solution with the concentration of 0.1mol/L into the glass tube, wherein the dosage ratio of the hydrochloric acid solution to the solid is 5ml:1g, introducing nitrogen into a glass tube, wherein the flow rate of the nitrogen is 150ml/min, carrying out hydrolysis reaction at constant temperature of 50 ℃ for 29h, stopping introducing the nitrogen after the reaction is finished, cooling to room temperature, filtering and drying the reaction liquid, heating to 400 ℃ at the speed of 5 ℃/min in the nitrogen atmosphere, keeping the temperature for 1h, heating to 600 ℃ at the speed of 3 ℃/min, keeping the temperature for 3h, heating the solid obtained by carbonization to 500 ℃ at the speed of 1 ℃/min in the air atmosphere, and keeping the temperature for 2h to obtain the amorphous silicon oxide-coated nitrogen-doped cobalt/manganese oxide material;
the content of VOCs is 9000mg/m3At a rate of 1m3Pumping the nitrogen-doped carbon adsorbent into an adsorption assembly formed by serially connecting 3 adsorption columns filled with the nitrogen-doped carbon adsorbent at a flow rate, heating and desorbing the adsorption assembly at the temperature of 100 ℃ for 1 hour, introducing the gas desorbed from the adsorption assembly into a catalytic oxidation reactor, and performing catalytic oxidation at an air speed ratio of 40000 hours-1Catalytic oxidation treatment is carried out at 450 ℃ under the catalysis of nitrogen-doped cobalt/manganese oxide materials coated by amorphous silicon oxide, and the content of VOCs in the waste gas at the outlet of a catalytic oxidation reactor is 10mg/m3The removal rate of VOCs was 99.89%.
Example 4
Mixing 16g of aluminum nitrate nonahydrate, 1.5g of 2-amino terephthalic acid, 25ml of sodium hydroxide solution with the concentration of 2mol/L and 500ml of methanol at 5600W, carrying out ultrasonic treatment for 50min, placing the obtained mixture in a high-pressure kettle, carrying out constant-temperature reaction at 120 ℃ for 3.5h, cooling to room temperature after the reaction is finished, carrying out centrifugal treatment, washing the obtained precipitate with methanol, and drying to obtain metal-organic gel powder; placing the mixture into a muffle furnace, controlling the flow of nitrogen to be 100ml/min, heating to 700 ℃ at the speed of 4 ℃/min to perform primary calcination treatment for 5 hours, washing calcined solids by sequentially adopting 1mol/L hydrochloric acid solution and deionized water, and then mixing the washed solids with 2mol/L ethanol solution of potassium hydroxide in a mass ratio of 1:5 for 30min, drying, heating to 700 ℃ at a speed of 4 ℃/min, controlling the nitrogen flow to be 100ml/min, carrying out secondary calcination treatment for 1h, and finally washing the calcined solid by sequentially adopting 1mol/L hydrochloric acid solution and deionized water, and drying to obtain the adsorbent;
mixing 5.5mmol of manganese chloride tetrahydrate, 2mmol of cobalt nitrate hexahydrate and 2.5mmol of 1,3, 5-trimesic acid, adding 150ml of DMF, 10ml of water and 10ml of ethanol mixed solvent, stirring until the solid is dissolved, reacting for 25h at 120 ℃, cooling to room temperature after the reaction is finished, filtering the reaction liquid, washing the obtained solid by deionized water and ethanol in sequence, and drying to obtain the bimetallic MOF material;
soaking 8g of prepared bimetallic MOF material in 90ml of 60 ℃ ethyl orthosilicate for 12h, then filtering, washing the filtered solid by adopting methanol, then placing the washed solid in a glass tube, adding a hydrochloric acid solution with the concentration of 0.1mol/L into the glass tube, wherein the dosage ratio of the hydrochloric acid solution to the solid is 8ml:1g, introducing nitrogen into a glass tube, wherein the flow rate of the nitrogen is 150ml/min, carrying out hydrolysis reaction at a constant temperature of 50 ℃ for 30h, stopping introducing the nitrogen after the reaction is finished, cooling to room temperature, filtering and drying the reaction liquid, heating to 400 ℃ at a speed of 5 ℃/min in the nitrogen atmosphere, keeping the temperature for 1h, heating to 600 ℃ at a speed of 3 ℃/min, keeping the temperature for 3.5h, heating the solid obtained by carbonization to 500 ℃ at a speed of 1 ℃/min in the air atmosphere, and keeping the temperature for 2h to obtain the amorphous silicon oxide coated nitrogen-doped cobalt/manganese oxide material;
the content of VOCs is 9500mg/m3At a rate of 1m3Pumping the nitrogen-doped carbon adsorbent into an adsorption assembly formed by serially connecting 3 adsorption columns filled with the nitrogen-doped carbon adsorbent at a flow rate of/h for adsorption treatment, then heating and desorbing the adsorption assembly at the temperature of 100 ℃ for 1.5h, introducing the gas desorbed by the adsorption assembly into a catalytic oxidation reactor, and leading the space velocity ratio during catalytic oxidation to be 40000h-1Catalytic oxidation treatment is carried out at 400 ℃ under the catalysis of amorphous silicon oxide coated nitrogen-doped cobalt/manganese oxide material, and the content of VOCs in the waste gas at the outlet of a catalytic oxidation reactor is 20mg/m3The removal rate of VOCs was 99.79%.
Example 5
Mixing 16.5g of aluminum nitrate nonahydrate, 1.5g of 2-amino terephthalic acid, 25ml of sodium hydroxide solution with the concentration of 2mol/L and 500ml of methanol under 600W, carrying out ultrasonic treatment for 50min, placing the obtained mixture in an autoclave for carrying out constant-temperature reaction for 3h at 130 ℃, cooling to room temperature after the reaction is finished, carrying out centrifugal treatment, washing the obtained precipitate with methanol, and then drying to obtain metal-organogel powder; placing the mixture into a muffle furnace, controlling the flow of nitrogen to be 100ml/min, heating to 700 ℃ at the speed of 5 ℃/min, carrying out primary calcination treatment for 5.5h, then washing calcined solids by sequentially adopting 1mol/L hydrochloric acid solution and deionized water, and then mixing the calcined solids with 2mol/L ethanol solution of potassium hydroxide in a mass ratio of 1:4 for 30min, drying, heating to 700 ℃ at the speed of 5 ℃/min, controlling the flow of nitrogen to be 100ml/min, carrying out secondary calcination for 1.5h, and finally washing the calcined solid by sequentially adopting 1mol/L hydrochloric acid solution and deionized water, and drying to prepare the adsorbent;
mixing 5mmol of manganese chloride tetrahydrate, 1.5mmol of cobalt nitrate hexahydrate and 2.5mmol of 1,3, 5-trimesic acid, adding 150ml of DMF, 10ml of water and 10ml of ethanol mixed solvent, stirring until the solid is dissolved, reacting for 22h at 120 ℃, cooling to room temperature after the reaction is finished, filtering the reaction liquid, washing the obtained solid by deionized water and ethanol in sequence, and drying to obtain the bimetallic MOF material;
soaking 10g of prepared bimetallic MOF material in 80ml of 60 ℃ ethyl orthosilicate for 15h, then filtering, washing the filtered solid by adopting methanol, then placing the washed solid in a glass tube, adding a hydrochloric acid solution with the concentration of 0.1mol/L into the glass tube, wherein the dosage ratio of the hydrochloric acid solution to the solid is 8ml:1g, introducing nitrogen into a glass tube, wherein the flow rate of the nitrogen is 150ml/min, carrying out hydrolysis reaction at constant temperature of 50 ℃ for 32h, stopping introducing the nitrogen after the reaction is finished, cooling to room temperature, filtering and drying the reaction liquid, heating to 400 ℃ at the speed of 5 ℃/min in the nitrogen atmosphere, keeping the temperature for 1h, heating to 600 ℃ at the speed of 3 ℃/min, keeping the temperature for 4h, heating the solid obtained by carbonization to 500 ℃ at the speed of 1 ℃/min in the air atmosphere, and keeping the temperature for 2h to obtain the amorphous silicon oxide-coated nitrogen-doped cobalt/manganese oxide material;
the content of VOCs is 9500mg/m3At a rate of 1m3Pumping the nitrogen-doped carbon adsorbent into an adsorption component formed by serially connecting 3 adsorption columns filled with the nitrogen-doped carbon adsorbent at a flow rate of/h for adsorption treatment, then heating and desorbing the adsorption component at the temperature of 100 ℃ for 1.5h, feeding the gas desorbed by the adsorption component into a catalytic oxidation reactor, and controlling the air speed ratio during catalytic oxidation to 50000h-1Catalytic oxidation treatment is carried out at 450 ℃ under the catalysis of amorphous silicon oxide coated nitrogen-doped cobalt/manganese oxide material, and the content of VOCs in the waste gas at the outlet of a catalytic oxidation reactor is 20mg/m3The removal rate of VOCs was 99.79%.
The embodiment shows that the method provided by the invention has the advantages that the removal rate of volatile organic pollutants is up to more than 99% and the effect is good when the method is used for treating high-concentration organic waste gas.
Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Claims (8)
1. A multistage treatment method of organic waste gas is characterized in that: the method comprises the steps of adsorbing organic waste gas by adopting an adsorption assembly formed by serially connecting a plurality of adsorption columns filled with nitrogen-doped carbon adsorbents, heating and desorbing the adsorption assembly, feeding gas desorbed by the adsorption assembly into a catalytic oxidation reactor, and carrying out catalytic oxidation treatment under the catalysis of a nitrogen-doped cobalt/manganese oxide material coated by amorphous silicon oxide;
the preparation method of the nitrogen-doped carbon adsorbent comprises the following steps:
mixing aluminum salt, organic ligand, sodium hydroxide solution and methanol under 500-600W, performing ultrasonic treatment for 30-50min, placing the obtained mixture in a high-pressure kettle, performing constant-temperature reaction for 2.5-3.5h at 120-130 ℃, cooling to room temperature after the reaction is finished, performing centrifugal treatment, washing the obtained precipitate with methanol, and drying to obtain metal-organic gel powder; placing the calcined solid in a muffle furnace under a nitrogen atmosphere for primary calcination treatment, washing the calcined solid by using a hydrochloric acid solution and deionized water in sequence, and then mixing the washed solid with a 2mol/L ethanol solution of potassium hydroxide in a mass ratio of 1: (4-5) mixing and activating for 30min, drying, then carrying out secondary calcination, and finally washing the calcined solid with a hydrochloric acid solution and deionized water in sequence, and drying to obtain the adsorbent;
the preparation method of the amorphous silicon oxide coated nitrogen-doped cobalt/manganese oxide material comprises the following steps:
(1) Mixing manganese salt, cobalt salt and an organic ligand, adding a solvent mixed by DMF (dimethyl formamide), water and ethanol, stirring until a solid is dissolved, reacting at 115-125 ℃ for 22-25h, cooling to room temperature after the reaction is finished, filtering a reaction solution, washing the obtained solid by deionized water and ethanol in sequence, and drying to obtain the bimetallic MOF material;
(2) Soaking the prepared bimetal MOF material in ethyl orthosilicate at the temperature of 55-65 ℃ for 10-15h, filtering, washing the solid obtained by filtering with methanol, then placing the washed solid in a glass tube, adding a hydrochloric acid solution into the glass tube, introducing nitrogen into the glass tube, carrying out hydrolysis reaction at the constant temperature of 45-55 ℃ for 28-32h, stopping introducing the nitrogen after the reaction is finished, cooling to room temperature, filtering the reaction liquid, drying, carbonizing in the nitrogen atmosphere, and finally calcining the solid obtained by carbonization to obtain the amorphous silicon oxide coated nitrogen-doped cobalt/manganese oxide material.
2. The method of claim 1, further comprising the step of: the aluminum salt is aluminum nitrate nonahydrate, the organic ligand is 2-amino terephthalic acid, the concentration of a sodium hydroxide solution is 2mol/L, and the dosage ratio of the aluminum nitrate nonahydrate, the 2-amino terephthalic acid, the sodium hydroxide solution and the methanol is (1.5-1.7) g: (0.1-0.15) g: (2-2.5) ml:50ml.
3. The multi-stage treatment method of an organic waste gas according to claim 1, wherein: the nitrogen flow during the first calcination treatment and the second calcination treatment is 100ml/min, the heating rate is 3-5 ℃/min, the calcination temperature is 700 ℃, the time of the first calcination treatment is 4.5-5.5h, and the time of the second calcination treatment is 0.5-1.5h.
4. The method of claim 1, further comprising the step of: in the step (1), the manganese salt is manganese chloride tetrahydrate, the cobalt salt is cobalt nitrate hexahydrate, and the organic ligand is one of 2-methylimidazole, 2, 5-dihydroxyterephthalic acid and 1,3, 5-trimesic acid; the dosage ratio of the manganese chloride tetrahydrate, the cobalt nitrate hexahydrate, the organic ligand, the DMF, the water and the ethanol is (5-5.5) mmol: (1.5-2) mmol: (2-2.5) mmol:150ml: (5-10) ml: (5-10) ml.
5. The method of claim 1, further comprising the step of: in the step (2), the dosage ratio of the bimetallic MOF material to the tetraethoxysilane is (0.5-1) g: (8-10) ml.
6. The method of claim 1, further comprising the step of: in the step (2), the concentration of the hydrochloric acid solution is 0.1mol/L, and the dosage ratio of the hydrochloric acid solution to the solid is 5-8ml:1g of a compound; the nitrogen flow rate during hydrolysis is 10-15ml/min.
7. The multi-stage treatment method of an organic waste gas according to claim 1, wherein: in the step (2), during carbonization treatment, the flow rate of nitrogen is 145-155ml/min, the temperature is firstly increased to 400 ℃ at the speed of 5 ℃/min, the temperature is kept for 1h, then the temperature is increased to 600 ℃ at the speed of 3 ℃/min, and the temperature is kept for 3-4h; the calcining treatment is to heat up to 500 ℃ at the speed of 1 ℃/min and keep the temperature for 1-3h.
8. The multi-stage treatment method of an organic waste gas according to claim 1, wherein: the air inflow during adsorption is 0.5-1m3The desorption temperature is 95-105 ℃, the desorption time is 1-1.5h, the reaction temperature in the catalytic oxidation reactor is 300-450 ℃, and the air speed ratio during catalytic oxidation is 30000-50000h-1The catalytic oxidation reactor is a fixed bed with the outer diameter of 20mm, the inner diameter of 10mm and the height of 20mm, and the filling amount of the catalyst is 0.2-0.3m3。
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