CN111960525B - Method and reaction device for catalyzing and oxidizing organic wastewater by using persulfate through ultrasonic assistance - Google Patents
Method and reaction device for catalyzing and oxidizing organic wastewater by using persulfate through ultrasonic assistance Download PDFInfo
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- 239000002351 wastewater Substances 0.000 title claims abstract description 50
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 title claims abstract description 42
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 22
- 230000001590 oxidative effect Effects 0.000 title claims abstract description 14
- 238000000034 method Methods 0.000 title claims description 16
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 114
- 230000003647 oxidation Effects 0.000 claims abstract description 111
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 73
- 230000003197 catalytic effect Effects 0.000 claims abstract description 64
- 230000004913 activation Effects 0.000 claims abstract description 52
- 230000007704 transition Effects 0.000 claims abstract description 31
- -1 sulfate radical Chemical class 0.000 claims description 18
- 239000002131 composite material Substances 0.000 claims description 13
- 239000003814 drug Substances 0.000 claims description 11
- 239000003054 catalyst Substances 0.000 claims description 8
- 238000004090 dissolution Methods 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 238000002604 ultrasonography Methods 0.000 claims description 6
- 238000006731 degradation reaction Methods 0.000 claims description 5
- 230000000694 effects Effects 0.000 claims description 5
- 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
- 230000009471 action Effects 0.000 claims description 4
- 230000015556 catabolic process Effects 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
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 239000005416 organic matter Substances 0.000 claims description 3
- 229910002092 carbon dioxide Inorganic materials 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
- 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
- FHHJDRFHHWUPDG-UHFFFAOYSA-L peroxysulfate(2-) Chemical compound [O-]OS([O-])(=O)=O FHHJDRFHHWUPDG-UHFFFAOYSA-L 0.000 claims 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 8
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052742 iron Inorganic materials 0.000 abstract description 4
- 230000009286 beneficial effect Effects 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 8
- 238000005516 engineering process Methods 0.000 description 7
- 125000005385 peroxodisulfate group Chemical group 0.000 description 5
- 238000009303 advanced oxidation process reaction Methods 0.000 description 4
- 238000009210 therapy by ultrasound Methods 0.000 description 4
- 230000007547 defect Effects 0.000 description 3
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 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
- 230000033558 biomineral tissue development Effects 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 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
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 230000006978 adaptation Effects 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
- 230000002498 deadly effect Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 239000010815 organic waste Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 238000001556 precipitation Methods 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
- 230000035939 shock Effects 0.000 description 1
- 239000010802 sludge Substances 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
Classifications
-
- 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
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- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physical Water Treatments (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
The invention relates to a reaction device for catalyzing and oxidizing organic wastewater by using ultrasonic-assisted persulfate, which comprises the following components: the device comprises a water pump, a power supply, an ultrasonic source, an ultrasonic activation oxidation zone, a transition zone and a catalytic oxidation zone; the outlet of the water pump is connected with the inlet of the ultrasonic activation oxidation zone, a plurality of ultrasonic transducers are arranged in the ultrasonic activation oxidation zone, and the 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 connected to the power supply. The beneficial effects of the invention are as follows: the reaction device provided by the invention does not need to adjust pH, the adopted persulfate is cheaper than hydrogen peroxide, the persulfate is solid and easy to transport and store, and Fenton-treated iron mud is not produced.
Description
Technical Field
The invention belongs to the field of ultrasound-assisted heterogeneous catalysis degradation of organic wastewater, and particularly relates to a method and a reaction device for catalyzing and oxidizing organic wastewater by using persulfate through ultrasound assistance.
Background
The treatment of organic waste water which is difficult to degrade and is produced in the chemical industry, the medicine industry and the printing and dyeing industry is always a great difficulty in waste water treatment, the difficulty in completely solving the problem is great by means of a single treatment technology, multiple technologies are needed for coupling, and an advanced oxidation technology (AOPs) can assist the cooperation of an external energy field, so that the catalytic oxidation treatment effect for the waste water is quite remarkable.
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 advanced oxidation technologies (AOPs) have deadly defects, such as pH adjustment, additional addition of acid and alkali, water salinity increase, and a large amount of iron sludge precipitation are generated, and the single AOPs method cannot be flexibly adjusted to water quality fluctuation, so that the contradiction between efficiency and cost is caused.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a reaction device and a method for catalyzing and oxidizing organic wastewater by using persulfate through ultrasonic assistance.
The reaction device for catalyzing and oxidizing the organic wastewater by using the persulfate through the ultrasonic assistance is an integrated ultrasonic composite catalytic oxidation reactor or a split ultrasonic assistance 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 zone, a transition zone and a catalytic oxidation zone; the outlet of the water pump is connected with the inlet of the ultrasonic activation oxidation zone, a plurality of ultrasonic transducers are arranged in the ultrasonic activation oxidation zone, and the 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 connected to a power supply;
the split ultrasonic-assisted catalytic oxidation reactor comprises: the device comprises a dissolving box, two water pumps, an ultrasonic activation oxidation zone, a power supply, an ultrasonic source, a transition zone and a catalytic oxidation zone; a stirrer is arranged in the dissolution tank, the outlet of the dissolution tank is connected with the inlet of one water pump, and the outlet of the water pump is connected with the 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 the transition zone, and the outlet of the transition zone is connected with the inlet of the catalytic oxidation zone; the stirrer, the two water pumps and the ultrasonic source are all connected to a power supply.
Preferably, the integrated ultrasonic composite catalytic oxidation reactor further comprises: a medicine dissolving tank, a solution tank and a water producing tank; the outlet of the medicine dissolving box is connected with the inlet of the solution box, a stirrer is arranged in the medicine dissolving box, and the stirrer is connected with a power supply; the outlet of the solution tank is connected with the inlet of the water pump; the inlet of the water producing tank is connected with the outlet of the catalytic oxidation zone.
Preferably, a water distributor is arranged at the outlet of the transition zone in the integrated ultrasonic composite catalytic oxidation reactor.
Preferably, the split ultrasonic-assisted catalytic oxidation reactor further comprises a water production tank, wherein an inlet of the water production tank is connected with an outlet of the catalytic oxidation zone.
The working method of the reaction device for catalyzing and oxidizing the organic wastewater by using the ultrasonic-assisted persulfate comprises the following steps of:
step 1, adding persulfate into wastewater, and stirring and dissolving the persulfate by a stirrer;
step 2, performing ultrasonic activation oxidation on the wastewater containing persulfate (each water has a specific operation frequency, and performing catalytic oxidation on the persulfate by adopting a specific single frequency or frequency combination to accelerate activation):
step 2.1, enabling the wastewater after the persulfate is fully dissolved to enter an ultrasonic activation oxidation zone through a water pump, connecting an ultrasonic source with a plurality of ultrasonic transducers in the ultrasonic activation oxidation zone, and performing ultrasonic activation oxidation on the persulfate (oxidant) in the wastewater in the ultrasonic activation oxidation zone through the ultrasonic transducers by utilizing an ultrasonic external field (ultrasonic cavitation characteristic) generated by the ultrasonic source;
step 2.2, breaking peroxygen bond O-O in Peroxomonosulfate (PMS) or Peroxodisulfate (PDS) in the wastewater solution of persulfate under the activation action of ultrasonic cavitation energy in the ultrasonic activation oxidation process to generate sulfate radical, initiating a series of chain reactions, and breaking chains of super-large molecular organic matters into organic matters with relatively low molecular weight:
S 2 O 8 -2 +us→2SO 4 - (1)
SO 4 -· standard electrode potential E of (2) 0 2.6V, which is inferior to the hydroxyl radical (2.80), but has longer service life than the hydroxyl radical, and has a half-life of about 4s, so that the reaction time with organic matters is longer;
step 2.3 sulfate radical SO in formula (1) above 4 -· And organic matters undergo electron transfer reaction to generate organic radical cations:
SO 4 -· +CH 3 CO 2 - →SO 4 2- +CH 3 CO 2 · (2)
step 3, the wastewater enters a transition zone (directly entering a catalytic oxidation section) until sulfate radical SO generated by ultrasonic activation oxidation 4 -· Fully reacts with organic matters; the transition zone is arranged to allow enough time for oxidation reaction in the first stage reaction zone and the transition zone by utilizing sulfate radical generated by ultrasonic activation so as to prevent direct entry into the catalytic oxidation zone, and excessive metal ions quench R ·- The method comprises the steps of carrying out a first treatment on the surface of the Such as: m is M +n +SO 4 -· →M +n+1 +SO 4 -2 The method comprises the steps of carrying out a first treatment on the surface of the Free radicals generated by ultrasonic activation oxidation are wasted, and organic degradation reaction is inhibited;
step 4, carrying out catalytic oxidation on the wastewater containing persulfate;
step 4.1, the wastewater enters a catalytic oxidation zone, a metal ion catalyst is added into the wastewater, and the persulfate is activated and decomposed by the peroxide bond in the persulfate under the action of the metal ion catalyst to generate sulfuric acid free radical SO 4 -· ：
S 2 O 8 -2 +M +n →SO 4 -· +M +n+1 +SO 4 -2 (3)
HSO 5 - +M +n →SO 4 -· +M n+1 +OH (4)
SO 4 -· +H 2 O→·OH+HSO 4 - (5)
Step 4.2 sulfate radical SO 4 -· The degradation of the organic material continues by means of electron transfer, hydrogen abstraction or addition until this fraction of the relatively low molecular weight organic material eventually oxidizes completely to carbon dioxide.
Preferably, the sulfate radical SO in step 2.3 4 -· Also degrade most of organic matters in the wastewater by means of hydrogen abstraction or addition, and sulfate radical SO 4 -· Oxidizing the inorganic reducing substance; especially has application potential for oxidative degradation of toxic and harmful organic matters.
The beneficial effects of the invention are as follows: the sulfate radical has strong oxidizing property, can degrade most of persistent organic pollutants, and especially has a half-life of up to 4 seconds. Far longer than the hydroxyl radical, and is more beneficial to playing a role in the reaction mass transfer process. The invention has the advantages that the pH value is not required to be regulated, the persulfate is cheaper than hydrogen peroxide, the persulfate is solid and is easy to transport and store, the existing Fenton-treated iron mud is not generated, the iron mud can be regulated and controlled in real time according to the quality of the inlet water, the defect of a single treatment technology is avoided, and the catalytic oxidation treatment effect on the wastewater is quite remarkable.
Drawings
FIG. 1 is a schematic diagram of an integrated ultrasonic composite catalytic oxidation reactor;
fig. 2 is a schematic structural diagram of a split ultrasonic-assisted catalytic oxidation reactor.
Reference numerals illustrate: the device comprises a medicine dissolving tank 1, a solution tank 2, a stirrer 3, a water pump 4, an ultrasonic activation oxidation zone 5, an ultrasonic transducer 6, a power supply 7, an ultrasonic source 8, a catalytic oxidation zone 9, a transition zone 10, a water distributor 11, a dissolving tank 12, a catalytic filler 13 and a water producing tank 14.
Detailed Description
The invention is further described below with reference to examples. The following examples are presented only to aid in the understanding of the invention. It should be noted that it will be apparent to those skilled in the art that modifications can be made to the present invention without departing from the principles of the invention, and such modifications and adaptations are intended to be within the scope of the invention as defined in the following claims.
The ultrasonic wave is an external energy field which is convenient to control, and the ultrasonic wave with the ultrasonic frequency exceeding 20kHZ is the ultrasonic wave; ultrasonic cavitation is as follows: when the ultrasonic wave propagates in water, the ultrasonic wave propagates according to the sine wave intensity law, and the periodically generated micro bubbles burst and generate strong shock waves. 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 radical release is, but the mineralization rate is not high, and the energy generated in cavitation instant can strengthen mass transfer and accelerate the chemical reaction process.
The instantaneous persulfate releases fast and many free radicals under the action of ultrasonic cavitation, most of the free radicals and organic pollutants in water can be subjected to oxidation reaction, macromolecular organic matters are oxidized into short-chain low-molecular-weight organic matters, and although some small-molecular organic matters are mineralized, the organic matters cannot be completely oxidized to a mineralized stage, so that the method is suitable for the preoxidation process of treating the organic wastewater with relatively high concentration at the front end, and only has the crushing effect. Then the wastewater with low molecular weight enters a catalytic oxidation reactor, the generation speed of free radicals is relatively slow during catalytic oxidation, and short-chain organic molecules broken by the front molecular chain can be thoroughly mineralized. The two are combined with each other, so that the advantages are brought into play, the treatment efficiency is both considered, and the organic matters can be thoroughly treated.
Example 1:
the reaction device for catalyzing and oxidizing the organic wastewater by using the persulfate through the ultrasonic assistance is an integrated ultrasonic composite catalytic oxidation reactor or a split ultrasonic assistance catalytic oxidation reactor:
as shown in fig. 1, the integrated ultrasonic composite catalytic oxidation reactor includes: the ultrasonic oxidation device comprises a water pump 4, a power supply 7, an ultrasonic source 8, an ultrasonic activation oxidation zone 5, a transition zone 10 and a catalytic oxidation zone 9; the outlet of the water pump 4 is connected with the inlet of the ultrasonic activation oxidation zone 5, a plurality of ultrasonic transducers 6 are arranged in the ultrasonic activation oxidation zone 5, and the 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 the transition zone 10, and the transition zone 10 is connected with the inlet of the catalytic oxidation zone 9; the water pump 4 and the ultrasonic source 8 are connected to the power supply 7; the integrated ultrasonic composite catalytic oxidation reactor further comprises: a medicine dissolving tank 1, a solution tank 2 and a water producing tank 14; the outlet of the medicine dissolving box 1 is connected to the inlet of the solution box 2, a stirrer 3 is arranged in the medicine dissolving box 1, and the stirrer 3 is connected to a power supply 7; the outlet of the solution tank 2 is connected with the inlet of the water pump 4; the inlet of the water producing tank 14 is connected with the outlet of the catalytic oxidation zone 9. The outlet of a transition zone 10 in the integrated ultrasonic composite catalytic oxidation reactor is provided with a water distributor 11.
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 zone 5, a power supply 7, an ultrasonic source 8, a transition zone 10 and a catalytic oxidation zone 9; the dissolution box 12 is internally provided with a stirrer 3, the outlet of the dissolution box 12 is connected with the inlet of one water pump 4, and the outlet of the water pump 4 is connected with the inlet of the ultrasonic activation oxidation zone 5; a plurality of ultrasonic transducers 6 are arranged in the ultrasonic activation oxidation zone 5, and the 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 the other water pump 4, the outlet of the water pump 4 is connected with the inlet of the transition zone 10, and the outlet of the transition zone 10 is connected with the inlet of the catalytic oxidation zone 9; the stirrer 3, the two water pumps 4 and the ultrasonic source 8 are connected to a power supply 7. The split ultrasonic-assisted catalytic oxidation reactor also comprises a water production tank 14, wherein the inlet of the water production tank 14 is connected with the outlet of the catalytic oxidation zone 9.
Example 2:
experimental environment: coal chemical wastewater (high COD is 500-600 mgL) is used as experimental water quality, and the experimental device is as follows: the experimental setup in fig. 1 or fig. 2 was used.
Experimental data:
wastewater water sample: coal chemical industry waste water: 200ml, COD 1200-1600 mg/L, aluminum-based metal oxide catalyst: 60g; persulfates: 1.4g; ultrasonic frequency: 20kHZ; ultrasonic power: 500-800W; adding the same amount of catalyst into raw water;
two batches were run:
1) Firstly, measuring COD of a wastewater sample in the first batch, adding 1.4g of potassium Peroxodisulfate (PDS) into four groups of 200ml wastewater samples, then measuring the COD, respectively carrying out ultrasonic treatment for 20min, 25min, 35min and 45min on the four groups of water samples (all carried out according to the frequency of 90s and 60s of ultrasonic treatment), and after the completion, respectively measuring the COD for the four groups of water samples at normal temperature; then 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 the COD; 200ml of wastewater sample was simultaneously added to 1.4g PDS, 60 catalyst was directly added without ultrasound, and the reaction was carried out for 1 hour and sampling was carried out after 24 hours to determine COD.
2) In the second batch of experiments, three 200ml wastewater samples are taken, firstly, the COD of raw water is measured, secondly, 1.4g of potassium Peroxodisulfate (PDS) is respectively added into the three groups of water samples, and after the three water samples are fully dissolved, the COD of the three water samples is measured again. And respectively carrying out ultrasonic treatment on the three water samples for 20min, 25min and 30min, measuring the COD of the water sample again after the completion of ultrasonic treatment, and measuring the COD again after 48 hours.
TABLE 1 Experimental data for first batch and second batch
Incomplete data for the molecular weight of one set of samples (set 2 of table 1) is the following table 2:
table 2 molecular weight data for samples
From the above experimental data, it can be seen that the use of the wastewater after the pretreatment by ultrasonic activation shows that in the ultrasonic activation process of pretreatment, despite the limited decrease of COD, the molecular weight of the organic matter is significantly decreased, which creates conditions for the subsequent catalytic oxidation of the wastewater by sulfuric acid until mineralization, so that there is a larger rate of decrease of COD in the effluent of the subsequent catalytic oxidation of persulfate. However, the activation pretreatment time is not longer and better, the optimal time is 25min, the molecules cannot be completely broken, the generated free radicals are not enough to remove the oxidized organic matters, and quenching occurs when the ultrasonic time is too long, so that the optimal time is only when the free radical generation rate is matched with the rate of the free radical oxidized organic matters.
Claims (6)
1. A reaction device for catalyzing and oxidizing organic wastewater by using persulfate under the assistance of ultrasound is characterized in that: the reaction device for catalyzing and oxidizing the organic wastewater by using the ultrasonic-assisted persulfate is an integrated ultrasonic composite catalytic oxidation reactor or a split 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 zone (5), a transition zone (10) and a catalytic oxidation zone (9); an outlet of the water pump (4) is connected with an inlet of the ultrasonic activation oxidation zone (5), a plurality of ultrasonic transducers (6) are arranged in the ultrasonic activation oxidation zone (5), and the 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 the transition zone (10), and the transition zone (10) is connected with the inlet of the catalytic oxidation zone (9); the water pump (4) and the ultrasonic source (8) are connected to the power supply (7);
the split ultrasonic-assisted catalytic oxidation reactor comprises: the device comprises a dissolving box (12), two water pumps (4), an ultrasonic activation oxidation zone (5), a power supply (7), an ultrasonic source (8), a transition zone (10) and a catalytic oxidation zone (9); a stirrer (3) is arranged in the dissolution tank (12), the outlet of the dissolution tank (12) is connected with the inlet of one water pump (4), and the outlet of the water pump (4) is connected with the inlet of the ultrasonic activation oxidation zone (5); a plurality of ultrasonic transducers (6) are arranged in the ultrasonic activation oxidation zone (5), and the 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 the transition zone (10), and the outlet of the transition zone (10) is connected with the inlet of the catalytic oxidation zone (9); the stirrer (3), the two water pumps (4) and the ultrasonic source (8) are connected to a power supply (7);
the transition zone (10) is used for allowing enough time for oxidation reaction in the first stage reaction zone and the transition zone (10) by utilizing sulfate radical generated by ultrasonic activation to prevent the sulfate radical from directly entering the catalytic oxidation zone.
2. The reaction device for the ultrasonic-assisted persulfate catalytic oxidation of organic wastewater according to claim 1, wherein the integrated ultrasonic composite catalytic oxidation reactor further comprises: a medicine dissolving box (1), a solution box (2) and a water producing box (14); an outlet of the medicine dissolving box (1) is connected with an inlet of the solution box (2), a stirrer (3) is arranged in the medicine dissolving box (1), and the stirrer (3) is connected with a power supply (7); the outlet of the solution tank (2) is connected with the inlet of the water pump (4); the inlet of the water producing tank (14) is connected with the outlet of the catalytic oxidation zone (9).
3. The reaction device for the ultrasonic-assisted persulfate catalytic oxidation of organic wastewater according to claim 1, wherein: the outlet of a transition zone (10) in the integrated ultrasonic composite catalytic oxidation reactor is provided with a water distributor (11).
4. The reaction device for the ultrasonic-assisted persulfate catalytic oxidation of organic wastewater according to claim 1, wherein: the split ultrasonic-assisted catalytic oxidation reactor further comprises a water production tank (14), and an inlet of the water production tank (14) is connected with an outlet of the catalytic oxidation zone (9).
5. A method of operating the reaction apparatus for the ultrasound-assisted persulfate catalytic oxidation of organic wastewater as set forth in claim 1, comprising the steps of:
step 1, adding persulfate into wastewater, and stirring and dissolving the persulfate through a stirrer (3);
step 2, carrying out ultrasonic activation oxidation on the wastewater containing persulfate:
step 2.1, enabling the wastewater after the persulfate is fully dissolved to enter an ultrasonic activation oxidation zone (5) through a water pump (4), connecting an ultrasonic source (8) with a plurality of ultrasonic transducers (6) in the ultrasonic activation oxidation zone (5), and performing ultrasonic activation oxidation on the persulfate in the wastewater through the ultrasonic transducers (6) in the ultrasonic activation oxidation zone (5) by utilizing an ultrasonic external field generated by the ultrasonic source (8);
step 2.2, breaking peroxygen bond O-O in the peroxymonosulfate or peroxydisulfate in the wastewater solution of the persulfates under the activation effect of ultrasonic cavitation energy in the ultrasonic activation oxidation process to generate sulfate radical, and initiating chain reaction:
S 2 O 8 -2 +us→2SO 4 - (1)
step 2.3 sulfate radical SO in formula (1) above 4 -· And organic matters undergo electron transfer reaction to generate organic radical cations:
SO 4 -· +CH 3 CO 2 - →SO 4 2- +CH 3 CO 2 · (2)
step 3, the wastewater enters a transition zone (10) until sulfate radical SO generated by ultrasonic activation oxidation 4 -· Fully reacts with organic matters;
step 4, carrying out catalytic oxidation on the wastewater containing persulfate;
step 4.1, the wastewater enters a catalytic oxidation zone (9), a metal ion catalyst is added into the wastewater, and the persulfate is activated and decomposed by the peroxide bond in the persulfate under the action of the metal ion catalyst to generate sulfuric acid free radical SO 4 -· ：
S 2 O 8 -2 +M +n →SO 4 -· +M +n+1 +SO 4 -2 (3)
HSO 5 - +M +n →SO 4 -· +M n+1 +OH (4)
SO 4 -· +H 2 O→·OH+HSO 4 - (5)
Step 4.2 sulfate radical SO 4 -· The degradation of the organic matter is continued by means of electron transfer, hydrogen abstraction or addition until the organic matter is finally completely oxidized to carbon dioxide.
6. The method for operating an apparatus for the ultrasound-assisted persulfate catalytic oxidation of organic wastewater according to claim 5The method is characterized in that: sulfate radical SO in step 2.3 4 -· Also degrade most of organic matters in the wastewater by means of hydrogen abstraction or addition, and sulfate radical SO 4 -· Oxidizing the inorganic reducing substance.
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| CN202010924187.XA CN111960525B (en) | 2020-09-04 | 2020-09-04 | Method and reaction device for catalyzing and oxidizing organic wastewater by using persulfate through ultrasonic assistance |
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