CN111960525A - Method and reaction device for catalytically oxidizing organic wastewater by using persulfate under assistance of ultrasound - Google Patents
Method and reaction device for catalytically oxidizing organic wastewater by using persulfate under assistance of ultrasound Download PDFInfo
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- 239000002351 wastewater Substances 0.000 title claims abstract description 51
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 title claims abstract description 44
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 23
- 230000001590 oxidative effect Effects 0.000 title claims abstract description 16
- 238000000034 method Methods 0.000 title claims description 12
- 238000002604 ultrasonography Methods 0.000 title abstract description 7
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 111
- 230000003647 oxidation Effects 0.000 claims abstract description 107
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 70
- 230000003197 catalytic effect Effects 0.000 claims abstract description 63
- 230000004913 activation Effects 0.000 claims abstract description 51
- 230000007704 transition Effects 0.000 claims abstract description 29
- -1 sulfate radicals Chemical class 0.000 claims description 17
- 239000002131 composite material Substances 0.000 claims description 13
- 238000004519 manufacturing process Methods 0.000 claims description 11
- 239000003054 catalyst Substances 0.000 claims description 10
- 239000003814 drug Substances 0.000 claims description 9
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 6
- 229910021645 metal ion Inorganic materials 0.000 claims description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 4
- 238000006356 dehydrogenation reaction Methods 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 230000027756 respiratory electron transport chain Effects 0.000 claims description 4
- FHHJDRFHHWUPDG-UHFFFAOYSA-L peroxysulfate(2-) Chemical compound [O-]OS([O-])(=O)=O FHHJDRFHHWUPDG-UHFFFAOYSA-L 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 3
- 230000009471 action Effects 0.000 claims description 2
- 239000001569 carbon dioxide Substances 0.000 claims description 2
- 239000003638 chemical reducing agent Substances 0.000 claims description 2
- 230000000977 initiatory effect Effects 0.000 claims description 2
- 239000010815 organic waste Substances 0.000 claims description 2
- 150000005839 radical cations Chemical class 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 238000006276 transfer reaction Methods 0.000 claims description 2
- 230000000593 degrading effect Effects 0.000 claims 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 229910052742 iron Inorganic materials 0.000 abstract description 3
- 239000007787 solid Substances 0.000 abstract description 2
- 238000001994 activation Methods 0.000 description 32
- 150000003254 radicals Chemical class 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 6
- 239000005416 organic matter Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 230000033558 biomineral tissue development Effects 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000009210 therapy by ultrasound Methods 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/34—Treatment of water, waste water, or sewage with mechanical oscillations
- C02F1/36—Treatment of water, waste water, or sewage with mechanical oscillations ultrasonic vibrations
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
Abstract
The invention relates to a reaction device for catalytically oxidizing organic wastewater by using persulfate under the assistance of ultrasound, which comprises the following components: the device comprises a water pump, a power supply, an ultrasonic source, an ultrasonic activation oxidation area, a transition area and a catalytic oxidation area; an outlet of the water pump is connected to an inlet of the ultrasonic activation oxidation area, a plurality of ultrasonic transducers are arranged in the ultrasonic activation oxidation area, and the plurality of ultrasonic transducers are electrically connected with an ultrasonic source; the outlet of the ultrasonic activation oxidation zone is connected with the inlet of the transition zone, and the transition zone is connected with the inlet of the catalytic oxidation zone; the water pump and the ultrasonic source are both connected with a power supply. The invention has the beneficial effects that: the reaction device provided by the invention does not need to adjust the pH value, the adopted persulfate is cheaper than hydrogen peroxide, the solid is easy to transport and store, and the iron mud subjected to Fenton treatment is not generated.
Description
Technical Field
The invention belongs to the field of ultrasonic-assisted heterogeneous catalytic degradation of organic wastewater, and particularly relates to a method and a reaction device for catalytically oxidizing organic wastewater by ultrasonic-assisted persulfate.
Background
The treatment of organic wastewater which is difficult to degrade and is generated in the chemical industry, the medicine industry and the printing and dyeing industry is always a big difficulty in wastewater treatment, the problem is completely solved by a single treatment technology with great difficulty, multiple technologies are required for coupling, the advanced oxidation technologies (AOPs) can assist the cooperation of an external energy field, and the catalytic oxidation treatment effect for the wastewater is very obvious.
Advanced oxidation technologies (AOPs) mainly based on Fenton technology have been developed for many years, and although the treatment effect on organic wastewater is good, the method has fatal defects, such as the need of adjusting pH, additional addition of acid and alkali, increase of water salinity, and generation of a large amount of iron mud precipitate.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a reaction device and a method for catalytically oxidizing organic wastewater by persulfate under the assistance of ultrasound.
The reaction device for catalytically oxidizing organic wastewater by using the ultrasonic-assisted persulfate is an integrated ultrasonic composite catalytic oxidation reactor or a split type ultrasonic-assisted catalytic oxidation reactor:
the integrated ultrasonic composite catalytic oxidation reactor comprises: the device comprises a water pump, a power supply, an ultrasonic source, an ultrasonic activation oxidation area, a transition area and a catalytic oxidation area; an outlet of the water pump is connected to an inlet of the ultrasonic activation oxidation area, a plurality of ultrasonic transducers are arranged in the ultrasonic activation oxidation area, and the plurality of ultrasonic transducers are electrically connected with an ultrasonic source; the outlet of the ultrasonic activation oxidation zone is connected with the inlet of the transition zone, and the transition zone is connected with the inlet of the catalytic oxidation zone; the water pump and the ultrasonic source are both connected with a power supply;
the split type ultrasonic-assisted catalytic oxidation reactor comprises: the device comprises a dissolving box, two water pumps, an ultrasonic activation oxidation area, a power supply, an ultrasonic source, a transition area and a catalytic oxidation area; a stirrer is arranged in the dissolving tank, an outlet of the dissolving tank is connected to an inlet of one of the water pumps, and an outlet of the water pump is connected to an inlet of the ultrasonic activation oxidation zone; a plurality of ultrasonic transducers are arranged in the ultrasonic activation oxidation area, and are electrically connected with an ultrasonic source; the outlet of the ultrasonic activation oxidation zone is connected with the inlet of another water pump, the outlet of the water pump is connected with the inlet of a transition zone, and the outlet of the transition zone is connected with the inlet of a catalytic oxidation zone; the stirrer, the two water pumps and the ultrasonic source are all connected with a power supply.
Preferably, the integrated ultrasonic composite catalytic oxidation reactor further comprises: a dissolving tank, a solution tank and a water producing tank; an outlet of the medicine dissolving box is connected to an inlet of the solution box, a stirrer is arranged in the medicine dissolving box, and the stirrer is connected to a power supply; the outlet of the solution tank is connected to the inlet of the water pump; the inlet of the water production tank is connected to the outlet of the catalytic oxidation zone.
Preferably, a water distributor is arranged at an outlet of a transition zone in the integrated ultrasonic composite catalytic oxidation reactor.
Preferably, the split type ultrasonic-assisted catalytic oxidation reactor further comprises a water production tank, and an inlet of the water production tank is connected to an outlet of the catalytic oxidation zone.
The working method of the reaction device for catalytically oxidizing organic wastewater by using the persulfate under the assistance of the ultrasound comprises the following steps:
step 1, adding persulfate into the wastewater, and stirring and dissolving the persulfate through a stirrer;
step 2.1, enabling the wastewater with the persulfate fully dissolved to enter an ultrasonic activation oxidation area through a water pump, connecting an ultrasonic source with a plurality of ultrasonic transducers in the ultrasonic activation oxidation area, and performing ultrasonic activation oxidation on the persulfate (oxidant) in the wastewater in the ultrasonic activation oxidation area through the ultrasonic transducers by utilizing an ultrasonic external field (ultrasonic cavitation characteristic) generated by the ultrasonic source;
2.2, breaking peroxy bonds O-O in Peroxymonosulfate (PMS) or Peroxydisulfate (PDS) in the persulfate wastewater solution under the activation of ultrasonic cavitation energy in the ultrasonic activation oxidation process to generate sulfate radicals, initiating a series of chain reactions, and breaking chains of super-large molecular organic matters into organic matters with relatively low molecular weight:
S2O8 -2+us→2SO4 - (1)
SO4 -·standard electrode potential E of02.6V, which is second to hydroxyl radical (2.80), but the service life of the catalyst is longer than that of the hydroxyl radical, and the half-life period reaches about 4s, so that the reaction time of the catalyst and organic matters is longer;
step 2.3 sulfate radical SO in formula (1) above4 -·And carrying out electron transfer reaction with organic matters to generate organic radical cations:
SO4 -·+CH3CO2 -→SO4 2-+CH3CO2 · (2)
step 4.1, the wastewater enters a catalytic oxidation area, a metal ion catalyst is added into the wastewater, and the peroxygen bond in persulfate is activated and decomposed under the action of the metal ion catalyst by persulfate to generate free radical SO4 -·：
S2O8 -2+M+n→SO4 -·+M+n+1+SO4 -2 (3)
HSO5 -+M+n→SO4 -·+Mn+1+OH (4)
SO4 -·+H2O→·OH+HSO4 - (5)
Step 4.2 sulfate radical SO4 -·Degradation of the organic material by electron transfer, hydrogen abstraction or addition continues until the relatively low molecular weight organic material in this portion eventually oxidizes to carbon dioxide.
Preferably, the sulfate radical SO in step 2.3 is4 -·Most organic matters in the wastewater are also degraded by hydrogen abstraction or addition, and sulfate radicals SO4 -·Oxidizing the inorganic reducing substance; especially has application potential to the oxidative degradation of toxic and harmful organic matters.
The invention has the beneficial effects that: sulfate radical free radical has strong oxidizing property, can better degrade most of persistent organic pollutants, and particularly has a half-life period of 4 seconds. Is far longer than hydroxyl free radical, and is more beneficial to playing a role in the reaction mass transfer process. According to the invention, the pH value does not need to be adjusted, persulfate is cheaper than hydrogen peroxide, the solid is easy to transport and store, the existing Fenton-treated iron mud is not generated, the real-time regulation and control can be carried out according to the quality of inlet water, the defect of a single treatment technology is avoided, and the catalytic oxidation treatment effect on wastewater is very obvious.
Drawings
FIG. 1 is a schematic structural diagram of an integrated ultrasonic composite catalytic oxidation reactor;
fig. 2 is a structural schematic diagram of a split type ultrasonic-assisted catalytic oxidation reactor.
Description of reference numerals: the device comprises a dissolving tank 1, a solution tank 2, a stirrer 3, a water pump 4, an ultrasonic activation oxidation area 5, an ultrasonic transducer 6, a power supply 7, an ultrasonic source 8, a catalytic oxidation area 9, a transition area 10, a water distributor 11, a dissolving tank 12, a catalytic filler 13 and a water production tank 14.
Detailed Description
The present invention will be further described with reference to the following examples. The following examples are set forth merely to aid in the understanding of the invention. It should be noted that, for a person skilled in the art, several modifications can be made to the invention without departing from the principle of the invention, and these modifications and modifications also fall within the protection scope of the claims of the present invention.
The ultrasonic wave is an external energy field which is convenient to control, and the ultrasonic wave with the frequency exceeding 20kHZ is the ultrasonic wave; the ultrasonic cavitation is as follows: when the ultrasonic wave is transmitted in water, the ultrasonic wave is transmitted according to the sine wave intensity rule, and the periodically generated micro bubbles burst, so that strong shock waves are generated. The heat activation energy consumption of ultrasonic cavitation is 144kcal/mol, the higher the temperature is, the higher the degradation efficiency of organic matters is, the faster the free radicals are released, but the mineralization rate is not high, and the energy generated at the moment of cavitation can strengthen mass transfer and accelerate the chemical reaction process.
The radical speed that persulfate released in the twinkling of an eye is fast and many under the ultrasonic cavitation effect, and radical and aquatic organic pollutant can take place oxidation reaction mostly, with the organic matter of macromolecule organic oxidation to the organic matter of the low molecular weight of short chain, though some micromolecule organic matters obtain the mineralize mineralization, but still can't be completely with the direct oxidation of organic matter to the stage of mineralize mineralization, be suitable for the preoxidation process of handling the organic waste water of front end relative high concentration, only play the crushing effect. Then the wastewater with low molecular weight enters a catalytic oxidation reactor, and the generation speed of free radicals is relatively slow in catalytic oxidation, so that short-chain organic matter molecules broken by front-section molecular chains can be thoroughly mineralized. The two are combined with each other, so that the advantages can be exerted, the treatment efficiency is considered, and the organic matter can be treated more thoroughly.
Example 1:
the reaction device for catalytically oxidizing organic wastewater by using the ultrasonic-assisted persulfate is an integrated ultrasonic composite catalytic oxidation reactor or a split type ultrasonic-assisted catalytic oxidation reactor:
as shown in fig. 1, the integrated ultrasonic composite catalytic oxidation reactor comprises: the device comprises a water pump 4, a power supply 7, an ultrasonic source 8, an ultrasonic activation oxidation area 5, a transition area 10 and a catalytic oxidation area 9; an outlet of the water pump 4 is connected with an inlet of the ultrasonic activation oxidation area 5, a plurality of ultrasonic transducers 6 are arranged in the ultrasonic activation oxidation area 5, and the plurality of ultrasonic transducers 6 are electrically connected with an ultrasonic source 8; the outlet of the ultrasonic activation oxidation zone 5 is connected with the inlet of a transition zone 10, and the transition zone 10 is connected with the inlet of a catalytic oxidation zone 9; the water pump 4 and the ultrasonic source 8 are both connected to the power supply 7; the integrated ultrasonic composite catalytic oxidation reactor further comprises: a dissolving medicine box 1, a solution box 2 and a water production box 14; an outlet of the dissolving medicine box 1 is connected to an inlet of the solution box 2, a stirrer 3 is arranged in the dissolving medicine box 1, and the stirrer 3 is connected to a power supply 7; an outlet of the solution tank 2 is connected to an inlet of a water pump 4; the inlet of the water production tank 14 is connected to the outlet of the catalytic oxidation zone 9. A water distributor 11 is arranged at the outlet of a transition zone 10 in the integrated ultrasonic composite catalytic oxidation reactor.
As shown in fig. 2, the split-type ultrasonic-assisted catalytic oxidation reactor includes: the device comprises a dissolving tank 12, two water pumps 4, an ultrasonic activation oxidation area 5, a power supply 7, an ultrasonic source 8, a transition area 10 and a catalytic oxidation area 9; a stirrer 3 is arranged in the dissolving tank 12, an outlet of the dissolving tank 12 is connected to an inlet of one water pump 4, and an outlet of the water pump 4 is connected to an inlet of the ultrasonic activation oxidation zone 5; a plurality of ultrasonic transducers 6 are arranged in the ultrasonic activation oxidation area 5, and the plurality of ultrasonic transducers 6 are all electrically connected with an ultrasonic source 8; the outlet of the ultrasonic activation oxidation zone 5 is connected with the inlet of another water pump 4, the outlet of the water pump 4 is connected with the inlet of a transition zone 10, and the outlet of the transition zone 10 is connected with the inlet of a catalytic oxidation zone 9; the stirrer 3, the two water pumps 4 and the ultrasonic source 8 are all connected to a power supply 7. The split type ultrasonic-assisted catalytic oxidation reactor also comprises a water production tank 14, and an inlet of the water production tank 14 is connected to an outlet of the catalytic oxidation zone 9.
Example 2:
the experimental environment is as follows: coal chemical industry waste water (high COD is at 500 ~ 600mgL) is used as experimental water quality, experimental apparatus: the experimental set-up of fig. 1 or fig. 2 was used.
Experimental data:
wastewater sample: coal chemical wastewater: 200ml, COD 1200-1600 mg/L, aluminum-based metal oxide catalyst: 60g of the total weight of the mixture; persulfate: 1.4 g; ultrasonic frequency: 20 kHZ; ultrasonic power: 500-800W; adding the same amount of catalyst into raw water;
the experiment was performed in two batches:
1) the COD of the wastewater samples is firstly determined in the first batch, 1.4g of potassium Peroxodisulfate (PDS) is added into four groups of 200ml wastewater samples, then the COD is determined, then the four groups of water samples are respectively subjected to 20min, 25min, 35min and 45min of ultrasound (all performed according to the frequency of ultrasound stopping for 60s for 90 s), and after the completion, the COD is respectively determined for the four groups of water samples at normal temperature; respectively adding 60g of aluminum-based metal oxide catalyst into the four groups of water samples, respectively measuring COD after reacting for 20min, standing the four groups of water samples for 24 hours, and then sampling to measure COD; 200ml of wastewater sample is synchronously added into 1.4g of PDS, 60 catalysts are directly added without ultrasonic treatment, and the wastewater sample is sampled to determine COD after 1 hour of reaction and 24 hours of reaction.
2) The second batch of experiments was performed by taking three 200ml wastewater samples, first determining the COD of the raw water, then adding 1.4g of potassium Peroxodisulfate (PDS) to each of the three groups of water samples, and determining the COD of the three water samples again after fully dissolving. Then, the three water samples are subjected to ultrasonic treatment for 20min, 25min and 30min respectively, the COD of the water samples is measured again after the ultrasonic treatment is finished, and the COD is measured again after 48 hours.
TABLE 1 Experimental data for the first and second batches
Incomplete data for molecular weights for one set of samples (table 1, set 2 samples) is given in table 2 below:
table 2 molecular weight data for samples
From the experimental data, the wastewater after the ultrasonic activation pretreatment is adopted, which shows that in the ultrasonic activation process of the pretreatment, although the COD is reduced to a limited extent, the molecular weight of the organic matters is obviously reduced, which creates conditions for the subsequent catalytic oxidation of the wastewater by sulfuric acid until mineralization, so that the COD of the effluent of the subsequent catalytic oxidation of persulfate is reduced at a larger rate. However, the activation pretreatment time is not as long as possible, and the optimum time is 25min, molecules cannot be completely broken if the time is too short, and the generated radicals are not ready to deoxidize organic substances if the ultrasonic time is too long, and quenching occurs, so that the optimum time is the optimum time when the generation rate of the radicals is matched with the rate of oxidizing the organic substances by the radicals.
Claims (6)
1. The utility model provides a reaction unit of supplementary persulfate catalytic oxidation organic waste water of supersound which characterized in that: the reaction device for catalytically oxidizing the organic wastewater by using the ultrasonic-assisted persulfate is an integrated ultrasonic composite catalytic oxidation reactor or a split type ultrasonic-assisted catalytic oxidation reactor;
the integrated ultrasonic composite catalytic oxidation reactor comprises: the device comprises a water pump (4), a power supply (7), an ultrasonic source (8), an ultrasonic activation oxidation area (5), a transition area (10) and a catalytic oxidation area (9); an outlet of the water pump (4) is connected to an inlet of the ultrasonic activation oxidation area (5), a plurality of ultrasonic transducers (6) are arranged in the ultrasonic activation oxidation area (5), and the plurality of ultrasonic transducers (6) are all electrically connected with an ultrasonic source (8); the outlet of the ultrasonic activation oxidation zone (5) is connected to the inlet of a transition zone (10), and the transition zone (10) is connected to the inlet of a catalytic oxidation zone (9); the water pump (4) and the ultrasonic source (8) are both connected to the power supply (7);
the split type ultrasonic-assisted catalytic oxidation reactor comprises: a dissolving box (12), two water pumps (4), an ultrasonic activation oxidation area (5), a power supply (7), an ultrasonic source (8), a transition area (10) and a catalytic oxidation area (9); a stirrer (3) is arranged in the dissolving tank (12), the outlet of the dissolving tank (12) is connected to the inlet of one water pump (4), and the outlet of the water pump (4) is connected to the inlet of the ultrasonic activation oxidation zone (5); a plurality of ultrasonic transducers (6) are arranged in the ultrasonic activation oxidation area (5), and the plurality of ultrasonic transducers (6) are electrically connected with an ultrasonic source (8); the outlet of the ultrasonic activation oxidation zone (5) is connected with the inlet of another water pump (4), the outlet of the water pump (4) is connected with the inlet of a transition zone (10), and the outlet of the transition zone (10) is connected with the inlet of a catalytic oxidation zone (9); the stirrer (3), the two water pumps (4) and the ultrasonic source (8) are all connected to a power supply (7).
2. The reaction unit for catalytic oxidation of organic wastewater by using ultrasonic assisted persulfate as claimed in claim 1, wherein the integrated ultrasonic composite catalytic oxidation reactor further comprises: a dissolving medicine box (1), a solution box (2) and a water producing box (14); an outlet of the dissolving medicine box (1) is connected to an inlet of the solution box (2), a stirrer (3) is arranged in the dissolving medicine box (1), and the stirrer (3) is connected to a power supply (7); the outlet of the solution tank (2) is connected to the inlet of a water pump (4); the inlet of the water production tank (14) is connected to the outlet of the catalytic oxidation zone (9).
3. The reaction device for catalytically oxidizing organic wastewater by using the persulfate under the assistance of the ultrasonic waves as claimed in claim 1, is characterized in that: and a water distributor (11) is arranged at an outlet of a transition region (10) in the integrated ultrasonic composite catalytic oxidation reactor.
4. The reaction device for catalytically oxidizing organic wastewater by using the persulfate under the assistance of the ultrasonic waves as claimed in claim 1, is characterized in that: the split type ultrasonic-assisted catalytic oxidation reactor further comprises a water production tank (14), and an inlet of the water production tank (14) is connected to an outlet of the catalytic oxidation zone (9).
5. The working method of the reaction device for the ultrasonic-assisted persulfate catalytic oxidation of the organic wastewater according to claim 1 is characterized by comprising the following steps:
step 1, adding persulfate into the wastewater, and stirring and dissolving the persulfate through a stirrer (3);
step 2, carrying out ultrasonic activation oxidation on the waste water containing persulfate:
2.1, enabling the wastewater with the persulfate fully dissolved to enter an ultrasonic activation oxidation area (5) through a water pump (4), connecting an ultrasonic source (8) with a plurality of ultrasonic transducers (6) in the ultrasonic activation oxidation area (5), and performing ultrasonic activation oxidation on the persulfate in the wastewater in the ultrasonic activation oxidation area (5) through the ultrasonic transducers (6) by utilizing an ultrasonic external field generated by the ultrasonic source (8);
2.2, breaking peroxy bonds O-O in peroxymonosulfate or peroxydisulfate in the persulfate wastewater solution under the activation of ultrasonic cavitation energy in the ultrasonic activation oxidation process to generate sulfate radicals, and initiating a chain reaction:
S2O8 -2+us→2SO4 - (1)
step 2.3 sulfate radical SO in formula (1) above4 -·And carrying out electron transfer reaction with organic matters to generate organic radical cations:
SO4 -·+CH3CO2 -→SO4 2-+CH3CO2 · (2)
step 3, the wastewater enters a transition region (10) until sulfate radicals SO generated by ultrasonic activation and oxidation4 -·Fully reacting with organic matters;
step 4, carrying out catalytic oxidation on the waste water containing persulfate;
step 4.1, the wastewater enters a catalytic oxidation area (9), a metal ion catalyst is added into the wastewater, and the peroxygen bond in persulfate is activated and decomposed to generate sulfuric acid free radical SO under the action of the metal ion catalyst4 -·：
S2O8 -2+M+n→SO4 -·+M+n+1+SO4 -2 (3)
HSO5 -+M+n→SO4 -·+Mn+1+OH (4)
SO4 -·+H2O→·OH+HSO4 - (5)
Step 4.2 sulfate radical SO4 -·And continuously degrading the organic matters by means of electron transfer, hydrogen abstraction or addition until the organic matters are finally and completely oxidized into carbon dioxide.
6. The working method of the reaction device for the ultrasonic-assisted persulfate catalytic oxidation of the organic wastewater according to claim 5, is characterized in that: sulfate radical SO in step 2.34 -·Most organic matters in the wastewater are also degraded by hydrogen abstraction or addition, and sulfate radicals SO4 -·Oxidizing the inorganic reducing substance.
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| CN114132991A (en) * | 2021-11-29 | 2022-03-04 | 哈尔滨工业大学 | Equipment for activating persulfate by using acoustic-gas coupling driving iron-like carbon packed bed and method for treating wastewater by using equipment |
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| CN102500376A (en) * | 2011-10-24 | 2012-06-20 | 武汉大学 | Activated carbon loaded iron-cobalt oxide catalyst and application thereof in degrading organic pollutants |
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| CN114132991A (en) * | 2021-11-29 | 2022-03-04 | 哈尔滨工业大学 | Equipment for activating persulfate by using acoustic-gas coupling driving iron-like carbon packed bed and method for treating wastewater by using equipment |
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