CN115475512B - Absorption oxidation method and device capable of simultaneously removing soluble and insoluble VOCs - Google Patents

Absorption oxidation method and device capable of simultaneously removing soluble and insoluble VOCs Download PDF

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CN115475512B
CN115475512B CN202210939118.5A CN202210939118A CN115475512B CN 115475512 B CN115475512 B CN 115475512B CN 202210939118 A CN202210939118 A CN 202210939118A CN 115475512 B CN115475512 B CN 115475512B
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absorption
activated carbon
vocs
absorption tower
soluble
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CN115475512A (en
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王亮亮
张忠国
吕丽荣
何沛然
刘月霞
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Beijing Science And Tech Research Inst
Institute Of Resources And Environment Beijing Academy Of Science And Technology
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Institute Of Resources And Environment Beijing Academy Of Science And Technology
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    • 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
    • B01D53/88—Handling or mounting catalysts
    • B01D53/885—Devices in general for catalytic purification of waste gases
    • 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
    • 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
    • B01D53/14—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 absorption
    • B01D53/1493—Selection of liquid materials for use as absorbents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8678—Removing components of undefined structure
    • B01D53/8687—Organic components
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/10—Oxidants
    • B01D2251/106—Peroxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10—Inorganic adsorbents
    • B01D2253/102—Carbon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/207—Transition metals
    • B01D2255/2073—Manganese
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/207—Transition metals
    • B01D2255/20761—Copper
    • 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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Abstract

The invention provides an absorption oxidation method and device capable of simultaneously removing soluble and insoluble VOCs, and belongs to the field of waste gas treatment. The method comprises the following steps: (1) Adding transition metal modified activated carbon into a Peroxymonosulfate (PMS) solution for catalytic activation treatment to obtain a mixed absorption liquid; (2) And (3) introducing the soluble and insoluble VOCs into the mixed absorption liquid obtained in the step (1) to perform absorption oxidation. The combined system of the transition metal modified activated carbon and the peroxide can play the dual roles of adsorption, catalysis and oxidation of the activated carbon, so that the absorption and degradation efficiency of VOCs molecules with different properties is improved.

Description

Absorption oxidation method and device capable of simultaneously removing soluble and insoluble VOCs
Technical Field
The invention belongs to the field of waste gas treatment, and particularly relates to an absorption oxidation method and device for simultaneously removing soluble and insoluble VOCs.
Background
VOCs have become one of the most important environmental problems of public concern as a pollution that seriously disturbs people and endangers human health. VOCs contaminants are generally perceived by humans at ppm levels and even below ppb levels, causing disorders, lesions, and even chronic, acute and death to the central nervous system of humans.
The current methods for treating VOCs pollutants mainly comprise an adsorption method, a combustion method, a biological method, an absorption method and the like. The chemical absorption advanced oxidation method oxidizes pollutant into non-toxic harmless micromolecular organic matters or inorganic matters by utilizing free radicals generated by an oxidant, so that the absorption mass transfer efficiency of insoluble VOCs can be improved, the treatment effect of the mixed VOCs is integrally improved, and the practical application effect is obvious.
Disclosure of Invention
The present invention has been made based on the findings and knowledge of the inventors regarding the following facts and problems:
the existing VOCs are mostly treated on researches on oxygen-containing VOCs such as acetone, methyl mercaptan and the like, and the researches on substances which are difficult to dissolve in water such as aromatic hydrocarbon, alkane and the like and have poor gas-liquid mass transfer effect are less.
In addition, the persulfate advanced oxidation technology is used as a research hot spot of an advanced oxidation method, and the reaction efficiency is higher through activating the generated sulfate radical. But the decomposition speed of the catalyst is slower at normal temperature, the treatment effect on organic pollutants is not obvious, the strong oxidizing property of the catalyst can be exerted under the catalysis of light, heat, transition metal ions and the like, the existing activation mode is complex in system, harsh in operation condition and high in cost, and the application of the persulfate advanced oxidation technology is hindered.
The present invention aims to solve at least one of the technical problems in the related art to some extent. To this end, embodiments of the present invention provide a method for simultaneously processing soluble and poorly soluble VOCs, which can stably process a variety of mixed VOCs for a long period of time.
The method for simultaneously treating soluble and insoluble VOCs comprises the following steps:
(1) Adding transition metal modified activated carbon into a peroxymonosulfate solution for catalytic activation treatment to obtain a mixed absorption liquid;
(2) And (3) introducing the mixed VOCs into the mixed absorption liquid obtained in the step (1) to perform absorption oxidation.
The absorption oxidation method for simultaneously removing the soluble and insoluble VOCs provided by the embodiment of the invention has the advantages and technical effects that: 1. in the embodiment of the invention, the transition metal modified activated carbon is adopted to carry out catalytic activation treatment on the Peroxymonosulfate (PMS), and a combined system of the transition metal modified activated carbon and the Peroxymonosulfate (PMS) can play the dual roles of adsorption, catalysis and oxidation of the activated carbon, so that the absorption and degradation efficiency of VOCs molecules with different properties is improved; 2. in the embodiment of the invention, the transition metal modified activated carbon is used as a catalyst and an adsorbent, and the catalytic action of the transition metal can activate the Peroxymonosulfate (PMS) to generate a large amount of sulfate radicals, so that the VOCs can be stably removed for a long time; 3. in the embodiment of the invention, the transition metal modified activated carbon has an adsorption effect, and can effectively remove VOCs with poor gas-liquid mass transfer; 4. according to the method provided by the embodiment of the invention, the effect of stably removing various VOCs for a long time can be obtained without replacing any reagent.
In some embodiments of the invention, in the step (1), the pH of the peroxymonosulfate solution is adjusted to 9 to 10 using an alkaline solution.
In some embodiments of the invention, the peroxymonosulfate is selected from at least one of potassium monopersulfate or potassium peroxymonosulfonate; and/or the concentration of the peroxymonosulfate in the solution is 0.2-2g/L.
In some embodiments of the invention, the transition metal modified activated carbon is Cu/Mn loaded activated carbon particles having a particle size of 20 to 40 mesh.
In some embodiments of the present invention, the Cu/Mn-loaded activated carbon particles have a Cu mass content of 3-8%, a Mn mass content of 3-8%, and preferably a Cu to Mn mass ratio of 0.8-1.2:1.
In some embodiments of the invention, in step (1), the amount of transition metal modified activated carbon added per liter of the peroxymonosulfate solution is 500-1000mg.
In some embodiments of the invention, both step (1) and step (2) are performed in an absorber column.
The embodiment of the invention also provides an absorption oxidation device for simultaneously removing the soluble and insoluble VOCs, which comprises an exhaust gas collecting unit, a chemical absorption oxidation unit and a medicament supplementing unit which are sequentially connected, wherein transition metal modified activated carbon is put into the chemical absorption oxidation unit, and the medicament in the medicament supplementing unit is a peroxymonosulfate solution.
The adsorption oxidation device for simultaneously removing the soluble and insoluble VOCs has the advantages and technical effects that transition metal modified activated carbon is added in the chemical adsorption oxidation unit, a Persulfate (PMS) solution is added in the medicament supplementing unit, the PMS is catalyzed and activated by the transition metal modified activated carbon, and a combined system of the transition metal modified activated carbon and the PMS can play the dual roles of adsorption, catalysis and oxidation of peroxides of the activated carbon, so that the adsorption degradation efficiency of VOCs molecules with different properties is improved, and the stable removal of various VOCs for a long time is realized.
In some embodiments of the present invention, the exhaust gas collecting unit includes a gas collecting device, and a gas outlet is disposed on the gas collecting device; the chemical absorption oxidation unit comprises an absorption tower, a gas inlet and a liquid outlet are arranged at the lower part of the absorption tower, a gas discharge port and a liquid inlet are arranged at the upper part of the absorption tower, and the gas outlet on the gas collecting device is connected with the gas inlet on the absorption tower; the medicament supplementing unit comprises a medicament storage tank, wherein the medicament storage tank is provided with a liquid outlet, and the liquid outlet on the medicament storage tank is connected with a liquid inlet on the absorption tower; the liquid outlet at the lower part of the absorption tower is respectively connected with the liquid inlet at the upper part of the absorption tower and the subsequent treatment device through a three-way valve.
In some embodiments of the invention, a sprayer is arranged at the top of the absorption tower, a gas distributor is arranged at the bottom of the absorption tower, raschig rings are filled in the absorption tower, and the transition metal modified activated carbon is activated carbon particles loaded with Cu/Mn.
Drawings
FIG. 1 is a schematic diagram of an absorption oxidation apparatus for simultaneous removal of soluble and poorly soluble VOCs in accordance with an embodiment of the present invention.
Reference numerals: 1. the gas collecting device, the gas outlet of the collecting device, the stop valve, the fan, the absorption tower, the gas inlet of the absorption tower, the liquid outlet of the absorption tower, the three-way valve A, the pump, the three-way valve B and the pump are respectively arranged in the gas collecting device, the gas outlet of the collecting device, the stop valve, the fan, the absorption tower, the gas inlet of the absorption tower, the liquid outlet of the absorption tower, the three-way valve A, the three-way valve 9, the pump and the three-way valve B,11, an absorber liquid inlet, 12, a sprayer, 13, an absorber gas discharge port, 14, a medicine storage tank, 15, a medicine storage tank liquid outlet, 16, a Raschig ring, 17, activated carbon particles and 18, a gas distributor.
Detailed Description
The following detailed description of embodiments of the invention is exemplary and intended to be illustrative of the invention and not to be construed as limiting the invention.
The absorption oxidation method for simultaneously removing the soluble and insoluble VOCs comprises the following steps:
(1) Adding transition metal modified activated carbon into a peroxymonosulfate solution for catalytic activation treatment to obtain a mixed absorption liquid;
(2) And (3) introducing the mixed VOCs into the mixed absorption liquid obtained in the step (1) to perform absorption oxidation.
According to the adsorption oxidation method for simultaneously removing the soluble and insoluble VOCs, the transition metal modified activated carbon is adopted to catalyze and activate the Peroxymonosulfate (PMS), and the combined system of the transition metal modified activated carbon and the PMS can play the dual roles of adsorption, catalysis and oxidation of the activated carbon, so that the adsorption and degradation efficiency of VOCs molecules with different properties is improved. The transition metal modified activated carbon is used as a catalyst and an adsorbent, and the catalysis of the transition metal can activate PMS to generate a large amount of sulfate radical, so that mixed VOCs can be stably removed for a long time; the transition metal modified activated carbon has an adsorption effect, and can effectively remove the VOCs with poor gas-liquid mass transfer, such as benzene series, alkanes and other substances which are difficult to dissolve in water. The method can maintain a long-time and stable removal effect on various VOCs without replacing any reagent.
In some embodiments of the invention, in the step (1), the pH of the peroxymonosulfate solution is adjusted to 9 to 10 using an alkaline solution. PMS is ionized in water to generate persulfate ions, the standard oxidation-reduction potential of the persulfate ions reaches 2.01V, and the PMS contains peroxy-O-O-in molecules, so that the PMS is a strong oxidant. The sulfate radical is relatively stable in neutral and acidic aqueous solutions, when the pH is more than 8.5, the sulfate oxidation water or OH - generates hydroxyl radical, has a lone pair electron, has oxidation-reduction potential of 2.6V, is far higher than that of persulfate ions, and has stronger oxidation capability.
In some embodiments of the present invention, preferably, the peroxymonosulfate is selected from at least one of potassium monopersulfate (2 KHSO 5·KHSO4·K2SO4) or potassium peroxymonosulfonate (KHSO 5), and more preferably potassium monopersulfate; preferably, the concentration of the peroxomonosulphate in the solution is from 0.2 to 2g/L. In the embodiment of the invention, the dosage of the PMS solution can be converted and determined according to the concentration of the VOCs substances, the PMS solution is circularly operated in the chemical absorption oxidation device, and the PMS solution is periodically supplemented according to the exhaust gas quantity, so that the efficient oxidation process is maintained.
In some embodiments of the invention, the transition metal modified activated carbon is Cu/Mn loaded activated carbon particles having a particle size of 20-40 mesh; preferably, in the activated carbon particles loaded with Cu/Mn, the mass content of Cu is 3-8%, the mass content of Mn is 3-8%, further preferably, the mass ratio of Cu to Mn is 0.8-1.2:1, and further preferably, the mass ratio of Cu to Mn is 1:1. In the embodiment of the invention, the Cu/Mn-loaded activated carbon particles are preferably adopted as transition metal modified activated carbon, so that the catalytic activation treatment of the Peroxymonosulfate (PMS) is facilitated, the generation of more sulfate radicals is promoted, and the removal rate of mixed VOCs pollutants is further improved. The embodiment of the invention further optimizes the proportion of Cu and Mn in the activated carbon, if the Cu loading is too high, metal elements are accumulated, so that the surface active sites of the metal and the activated carbon are underexposed, and if the Cu loading is too low, the co-doping effect with Mn element is reduced, the active ingredients generated by catalyzing PMS are reduced, and the oxidation rate is reduced.
In some embodiments of the invention, in step (1), the amount of transition metal modified activated carbon added per liter of the peroxymonosulfate solution is 500-1000mg. In the embodiment of the invention, the addition of the transition metal modified activated carbon is further optimized, so that the catalytic activation of PMS is improved, if the addition of the transition metal modified activated carbon is too small, the activation of PMS is insufficient, more sulfate radicals are not formed, if the addition is too large, the gas-liquid contact opportunity is reduced, the absorption and mass transfer of insoluble VOCs are blocked, and the waste of catalysts is also caused.
In some embodiments of the invention, both step (1) and step (2) are performed in a chemical absorption oxidation unit, preferably an absorber column. In the embodiment of the invention, the activation and the absorption oxidation can be completed in one chemical absorption oxidation device, the requirement on equipment is low, and the industrial application is facilitated.
The absorption oxidation device for simultaneously removing the soluble and insoluble VOCs comprises an exhaust gas collecting unit, a chemical absorption oxidation unit and a medicament supplementing unit which are sequentially connected, wherein transition metal modified activated carbon is put into the chemical absorption oxidation unit, and the medicament in the medicament supplementing unit is a peroxymonosulfate solution.
According to the absorption oxidation device for simultaneously removing the soluble and insoluble VOCs, disclosed by the embodiment of the invention, the transition metal modified activated carbon is added into the chemical absorption oxidation unit, the PMS solution is added into the medicament supplementing unit, the transition metal modified activated carbon is adopted to catalyze and activate PMS, the combined system of the transition metal modified activated carbon and the PMS can play the dual roles of adsorption, catalysis and oxidation of the activated carbon, the absorption degradation efficiency of VOCs molecules with different properties is improved, and the stable removal of various mixed VOCs for a long time is realized.
As shown in fig. 1, in some embodiments of the present invention, the exhaust gas collecting unit includes a gas collecting device 1, where the gas collecting device 1 has a gas outlet 2; the chemical absorption oxidation unit comprises an absorption tower 5, a gas inlet 6 and a liquid outlet 7 are arranged at the lower part of the absorption tower 5, a gas discharge port 13 and a liquid inlet 11 are arranged at the upper part of the absorption tower 5, and a gas outlet 2 on the gas collecting device 1 is connected with the gas inlet 6 on the absorption tower 5; the medicament supplementing unit comprises a medicament storage tank 14, wherein a liquid outlet 15 is arranged on the medicament storage tank 14, and the liquid outlet 15 on the medicament storage tank 14 is connected with a liquid inlet 11 on the absorption tower; the liquid outlet 7 at the lower part of the absorption tower 5 is respectively connected with the liquid inlet 11 at the upper part of the absorption tower 5 and a subsequent treatment device through a three-way valve 8. Preferably, the top of the absorption tower 5 is provided with a sprayer 12, and the bottom of the absorption tower 5 is provided with a gas distributor 18. Further preferably, the absorption tower 5 is filled with a raschig ring 16, and a transition metal modified activated carbon 17 is fed.
The device provided by the invention has the advantages of simple system, convenient operation, lower cost and convenient popularization and application of PMS advanced oxidation technology. In addition, the liquid outlet at the lower part of the absorption tower is connected with the liquid inlet at the upper part of the absorption tower, so that the circulating flow of the absorption liquid in the absorption tower can be realized, the consumption of the absorption liquid can be saved, and the contact between gas and liquid can be more sufficient. The absorption tower is provided with the sprayer at the top and the gas distributor at the bottom, so that gas and liquid can be distributed more uniformly in the absorption tower, absorption liquid and VOCs molecules can be fully contacted, and mass transfer process between the gas and the liquid is facilitated. The absorption tower is filled with a certain amount of Raschig rings, the Raschig rings have the main functions of increasing distribution points of gas or liquid, and are used as supporting materials of metal modified activated carbon, so that the metal modified activated carbon can be supported and protected, and the overall treatment efficiency of soluble and insoluble VOCs is improved.
The present invention will be described in detail with reference to the following examples and drawings.
Example 1
The experimental engineering site is a refuse transfer station in a certain school in Beijing, the station is positioned at the north door of the station, one surface faces the road, the other three surfaces are all surrounded by residents, one side of a refuse channel is removed, and enclosing walls are arranged around the refuse station and are separated from the road and the residents. Because ventilation is not smooth and green belts are not isolated, peculiar smell is released when the garbage station is used, and the life of surrounding residents is influenced.
And collecting VOCs gas of the garbage station, and detecting the types and the concentrations of main VOCs substances, wherein specific data are shown in Table 1.
As shown in fig. 1, the device of the invention is used for treating the mixed VOCs gas, and the specific implementation process is as follows:
(1) Opening three-way valve A8-B and three-way valve B10-a to make potassium monopersulfate (2 KHSO 5·KHSO4·K2SO4) solution in medicine storage tank 14 enter liquid inlet 11 of absorption tower from liquid outlet 15 of medicine storage tank, and spray into absorption tower 5 by sprayer 12, wherein the concentration of potassium monopersulfate solution is 1g/L; the absorption tower is filled with a certain amount of Raschig rings 16 serving as supporting materials of transition metal modified activated carbon 17, the transition metal modified activated carbon is modified activated carbon particles with Cu and Mn loading amounts of 5%, and the addition amount of the transition metal modified activated carbon in each liter of potassium monopersulfate solution is 750mg/L. When the potassium monopersulfate solution rises to the height of 1/3 of the tower body, the stop valve 3 is opened, the gas outlet 2 of the collecting device is connected with the fan 4, gas is pumped into the gas inlet 6 of the absorption tower by the fan 4, and uniformly blown into the absorption tower 5 through the gas distributor 18;
(2) When the potassium monopersulfate solution rises to 1/2 of the height of the column, the three-way valve B10-B and the pump 9 are opened to circulate the potassium monopersulfate solution in the absorption column. After the mixed VOCs pollutants are treated by the potassium monopersulfate solution and the Cu/Mn activated carbon 17, the mixed VOCs pollutants are collected from the gas discharge port 13 of the absorption tower, and the residual main VOCs types and concentrations are detected.
After the mixed VOCs were treated by the method of this example, the treatment results are shown in table 1.
TABLE 1 effect of treatment of VOCs pollutants at refuse transfer station
Types of VOCs Pretreatment/. Mu.g/m 3 Post-treatment/. Mu.g/m 3 Removal rate/%
Ethanol 289.4 16.5 94.30
Carbon disulphide 320.3 10.4 96.75
N-hexane 41.2 10.68 74.08
Heptane (heptane) 44.7 13.4 70.02
Dimethyl disulfide 43.9 3.6 91.80
Benzene 36.6 8.3 77.32
Toluene (toluene) 72.1 10.5 85.44
Ethylbenzene (ethylbenzene) 11.9 3.14 73.61
M, p-xylene 40.1 9.73 75.74
Ortho-xylene 15.7 3.22 79.49
As can be seen from the test data in Table 1, the method and the device for treating VOCs pollutants in the garbage station have the efficiency of removing the main mixed VOCs pollutants in the garbage station above about 70%, particularly, the removal efficiency of removing the pollutants which are difficult to dissolve in water, such as benzene, toluene, xylene and the like, with poor gas-liquid mass transfer effect can reach 77.32%, 85.44% and 75.74-79.49%, respectively.
Example 2
The same procedure as in example 1 was followed except that the pH of the PMS was adjusted to 9.5 with lye.
After the mixed VOCs gas was treated by the method of this example, the treatment results are shown in table 2.
TABLE 2 effect of treatment of VOCs pollutants at refuse transfer station
Types of VOCs Pretreatment/. Mu.g/m 3 Post-treatment/. Mu.g/m 3 Removal rate/%
Ethanol 289.4 8.12 97.19
Carbon disulphide 320.3 7.58 97.63
N-hexane 41.2 7.61 81.53
Heptane (heptane) 44.7 11.4 74.50
Dimethyl disulfide 43.9 1.87 95.74
Benzene 36.6 6.87 81.23
Toluene (toluene) 72.1 8.22 88.60
Ethylbenzene (ethylbenzene) 11.9 2.06 82.69
M, p-xylene 40.1 6.24 84.44
Ortho-xylene 15.7 2.53 83.89
Example 3
The same procedure as in example 1 was followed except that potassium peroxymonosulphate (KHSO 5) was used as peroxomonosulphate.
After the mixed VOCs gas was treated by the method of this example, the treatment results are shown in table 3.
TABLE 3 effect of treatment of VOCs pollutants at refuse transfer station
Types of VOCs Pretreatment/. Mu.g/m 3 Post-treatment/. Mu.g/m 3 Removal rate/%
Ethanol 289.4 18.9 93.47
Carbon disulphide 320.3 17.4 94.57
N-hexane 41.2 13.7 66.75
Heptane (heptane) 44.7 14.8 66.89
Dimethyl disulfide 43.9 7.2 83.60
Benzene 36.6 10.5 71.31
Toluene (toluene) 72.1 10.5 85.44
Ethylbenzene (ethylbenzene) 11.9 3.14 73.61
M, p-xylene 40.1 10.35 74.19
Ortho-xylene 15.7 4.36 72.23
Comparative example 1
The same procedure as in example 1 was conducted except that activated carbon not loaded with Cu/Mn was fed into the absorption column 5.
The treatment results of the mixed VOCs gas after the treatment by the method of comparative example 1 are shown in table 4.
TABLE 4 effect of VOCs pollutant treatment at refuse transfer station
Types of VOCs Pretreatment/. Mu.g/m 3 Post-treatment/. Mu.g/m 3 Removal rate/%
Ethanol 289.4 27.31 90.56
Carbon disulphide 320.3 34.7 89.17
N-hexane 41.2 22.3 45.87
Heptane (heptane) 44.7 23.5 47.43
Dimethyl disulfide 43.9 12.14 72.35
Benzene 36.6 16.28 55.52
Toluene (toluene) 72.1 27.64 61.66
Ethylbenzene (ethylbenzene) 11.9 5.65 52.52
M, p-xylene 40.1 17.3 56.86
Ortho-xylene 15.7 7.52 52.10
Comparative example 2
The same procedure as in example 1 was followed except that Mn-loaded activated carbon was fed into the absorption column 5.
The treatment results of the mixed VOCs gas after the treatment by the method of comparative example 2 are shown in table 5.
TABLE 5 effect of treatment of VOCs pollutants at refuse transfer station
Types of VOCs Pretreatment/. Mu.g/m 3 Post-treatment/. Mu.g/m 3 Removal rate/%
Ethanol 289.4 21.36 92.62
Carbon disulphide 320.3 19.25 93.99
N-hexane 41.2 14.57 64.64
Heptane (heptane) 44.7 17.48 60.89
Dimethyl disulfide 43.9 7.23 83.53
Benzene 36.6 11.04 69.84
Toluene (toluene) 72.1 18.71 74.05
Ethylbenzene (ethylbenzene) 11.9 4.36 63.36
M, p-xylene 40.1 12.62 68.53
Ortho-xylene 15.7 5.64 64.08
Comparative example 3
The same procedure as in example 1 was followed except that sodium peroxodisulfate (Na 2S2O8), a peroxodisulfate salt (PDS), was used in the reservoir 14.
The treatment results of the mixed VOCs gas after the treatment by the method of comparative example 3 are shown in table 6.
TABLE 6 effect of VOCs pollutant treatment at refuse transfer station
Types of VOCs Pretreatment/. Mu.g/m 3 Post-treatment/. Mu.g/m 3 Removal rate/%
Ethanol 289.4 19.07 93.41
Carbon disulphide 320.3 18.38 94.26
N-hexane 41.2 14.67 64.39
Heptane (heptane) 44.7 16.02 64.16
Dimethyl disulfide 43.9 8.23 81.25
Benzene 36.6 10.65 70.90
Toluene (toluene) 72.1 18.71 74.05
Ethylbenzene (ethylbenzene) 11.9 5.32 55.29
M, p-xylene 40.1 11.24 71.97
Ortho-xylene 15.7 5.37 65.80
As can be seen from tables 1 to 3, examples 1 to 3 enable the removal rate of mixed VOCs to be substantially 70% or more. In example 2, the pH value of the Peroxymonosulfate (PMS) is adjusted by adopting alkali liquor, so that the removal rate of the mixed VOCs is further improved, and besides the removal rate of the heptane is 74.50%, the removal rate of other pollutants is more than 80%, because the alkane has the lowest water solubility and the longest heptane carbon chain, and the alkane is difficult to be adsorbed by the activated carbon. After the pH is regulated, the PMS can be catalyzed to generate singlet oxygen free radicals 1O2, compared with the free radicals in other pH ranges, the method has the advantages that the types of the free radicals are more abundant, and the degradation of VOCs can be further accelerated. In the comparative example 1, the activated carbon which is not loaded with Cu/Mn is put in, and the removal rate of pollutants is obviously reduced, because the activated carbon not only improves the mass transfer rate of VOCs at a gas-liquid interface through adsorption, but also can activate PMS to generate a certain amount of SO 4 - & and OH, and has higher removal rate for most of VOCs; however, the removal rate of the substances of the comparative example 1 on partial alkanes and aromatic hydrocarbons is only about 40-50%, and the substances are difficult to degrade efficiently mainly because of the low yield of free radicals of the unmodified activated carbon activated PMS. In comparative example 2, the activated carbon loaded with Mn alone was dosed, and the removal rate of contaminants was reduced compared with example 1, because multicomponent VOCs produced competitive adsorption on the activated carbon surface, and in the experiment, it was found that ethyl acetate was replaced with toluene, so that the penetration curve of ethyl acetate reached a peak at a certain time in the adsorption process, and the activated carbon was more easily combined with toluene after the bimetal element modification. By adding Cu and Mn elements, the coupling adsorption effect of benzene series on the activated carbon can be improved, and the absorption process of insoluble VOCs in the solution is further improved. Meanwhile, cu/Mn coupling can catalyze PMS to generate more free radicals, so that the degradation rate of VOCs absorbed in a liquid phase is improved, and therefore, the modified activated carbon only loaded with Mn element is poorer than that of the embodiment 1. In comparative example 3, peroxodisulfate (PDS) was used as the oxidant, and the effect was worse than that of Peroxomonosulfate (PMS), mainly because the PDS system was activated to mainly produce SO 4 -. The small amount of OH was formed by direct oxidation of adsorbed H 2 O or-OH, and for the mixed VOCs adsorption oxidation system, the abundant free radical species were more susceptible to catalytic oxidation of VOCs. The modified activated carbon material can directly transfer electrons to PMS to generate a large amount of SO 4 -.and OH, and the asymmetric structure of the modified activated carbon material can also generate strong interaction with VOCs, SO that activated PMS molecules directly oxidize the VOCs, and the removal effect of the mixed VOCs by adopting the peroxymonosulfate is better.
In the description of the present invention, it should be understood that the terms "center", "longitudinal", "lateral", "length", "width", "thickness", "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", "clockwise", "counterclockwise", "axial", "radial", "circumferential", etc. indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings are merely for convenience in describing the present invention and simplifying the description, and do not indicate or imply that the device or element being referred to must have a specific orientation, be configured and operated in a specific orientation, and therefore should not be construed as limiting the present invention.
In the present invention, unless explicitly specified and limited otherwise, the terms "mounted," "connected," "secured," and the like are to be construed broadly, and may be, for example, fixedly connected, detachably connected, or integrally formed; may be mechanically connected, may be electrically connected or may be in communication with each other; either directly or indirectly, through intermediaries, or both, may be in communication with each other or in interaction with each other, unless expressly defined otherwise. The specific meaning of the above terms in the present invention can be understood by those of ordinary skill in the art according to the specific circumstances.
While the above embodiments have been shown and described, it should be understood that the above embodiments are illustrative and not to be construed as limiting the invention, and that variations, modifications, alternatives, and variations of the above embodiments may be made by those of ordinary skill in the art without departing from the scope of the invention.

Claims (10)

1. An absorption oxidation method capable of simultaneously removing soluble and insoluble VOCs, which is characterized by comprising the following steps:
(1) Adding transition metal modified activated carbon into a peroxymonosulfate solution for catalytic activation treatment to obtain a mixed absorption liquid, wherein the transition metal modified activated carbon is Cu/Mn loaded activated carbon particles, and an alkaline solution is used for adjusting the pH value of the peroxymonosulfate solution to 9.5-10;
(2) And (3) introducing the mixed VOCs into the mixed absorption liquid obtained in the step (1) to perform absorption oxidation.
2. The method for the simultaneous removal of soluble and poorly soluble VOCs according to claim 1, wherein said peroxymonosulfate is selected from at least one of potassium monopersulfate or potassium peroxymonosulfonate; and/or the concentration of the peroxymonosulfate in the solution is 0.2-2g/L.
3. The method for the absorption oxidation of simultaneously removing soluble and insoluble VOCs according to claim 1, wherein the particle size of the activated carbon particles is 20 to 40 mesh.
4. The method for absorption oxidation for simultaneously removing soluble and insoluble VOCs according to claim 1 or 3, wherein the Cu/Mn-loaded activated carbon particles have a Cu mass content of 3 to 8% and a Mn mass content of 3 to 8%.
5. The method for absorption oxidation for simultaneously removing soluble and insoluble VOCs according to claim 1, wherein the mass ratio of Cu to Mn is 0.8-1.2:1.
6. The method for simultaneous removal of soluble and insoluble VOCs according to claim 1, wherein in said step (1), the amount of transition metal modified activated carbon added per liter of the peroxymonosulfate solution is 500-1000mg.
7. The method for simultaneous removal of soluble and poorly soluble VOCs according to claim 1, wherein both step (1) and step (2) are performed in an absorber column.
8. The method for absorbing and oxidizing while removing soluble and insoluble VOCs according to claim 1, wherein the absorbing and oxidizing device adopted by the method comprises an exhaust gas collecting unit, a chemical absorbing and oxidizing unit and a chemical supplementing unit which are connected in sequence, transition metal modified activated carbon is put into the chemical absorbing and oxidizing unit, and the chemical in the chemical supplementing unit is a peroxymonosulfate solution.
9. The method for simultaneous removal of soluble and insoluble VOCs according to claim 8, wherein said waste gas collecting unit comprises a gas collecting means provided with a gas outlet; the chemical absorption oxidation unit comprises an absorption tower, a gas inlet and a liquid outlet are arranged at the lower part of the absorption tower, a gas discharge port and a liquid inlet are arranged at the upper part of the absorption tower, and the gas outlet on the gas collecting device is connected with the gas inlet on the absorption tower; the medicament supplementing unit comprises a medicament storage tank, wherein the medicament storage tank is provided with a liquid outlet, and the liquid outlet on the medicament storage tank is connected with a liquid inlet on the absorption tower; the liquid outlet at the lower part of the absorption tower is respectively connected with the liquid inlet at the upper part of the absorption tower and the subsequent treatment device through a three-way valve.
10. The method for absorbing and oxidizing while removing soluble and insoluble VOCs according to claim 9, wherein a sprayer is installed at the top of the absorption tower, a gas distributor is installed at the bottom of the absorption tower, and raschig rings are installed in the absorption tower.
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