CN111186901B - Technology for feeding ozone into multistage ozone reaction tower by ejector - Google Patents
Technology for feeding ozone into multistage ozone reaction tower by ejector Download PDFInfo
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- CN111186901B CN111186901B CN202010099897.3A CN202010099897A CN111186901B CN 111186901 B CN111186901 B CN 111186901B CN 202010099897 A CN202010099897 A CN 202010099897A CN 111186901 B CN111186901 B CN 111186901B
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
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- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8671—Removing components of defined structure not provided for in B01D53/8603 - B01D53/8668
- B01D53/8675—Ozone
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Abstract
The utility model relates to the field of wastewater treatment, in particular to a technology of an ejector for feeding an ozone multistage ozone reaction tower; the concrete components include: a regulating tank, a lift pump, a water distributor, an anaerobic reaction tower and a methane collecting cover; the reaction tower disclosed by the utility model utilizes the jet technology to circulate jet wastewater and ozone, so that the contact time and the contact area of the wastewater and the ozone are greatly increased, and the ozone utilization rate is improved; the utility model also provides a hydrophobic ozonolysis catalyst, which has higher ozonolysis efficiency and better moisture resistance, the decomposition efficiency is not influenced by the environmental humidity, and the catalyst can be used for decomposing ozone under different humidity environments.
Description
Technical Field
The utility model relates to the field of wastewater treatment, in particular to a jet device ozone inlet multistage ozone reaction tower technology.
Background
Ozone is a strong oxidant which is unstable and easy to decompose. The treatment of wastewater with ozone is a very effective wastewater treatment technique.
201821943116.9 discloses an ozone oxidation reactor, which comprises a mixer, a gas phase balance pipe, a tower reactor and an ultrafine bubble distributor at the lower part in the tower reactor, the ultrafine bubble distributor comprises a gas cavity communicated with a gas inlet and a gas-liquid channel vertical to the gas cavity, the gas-liquid channel is a pipeline communicated with the gas cavity, the side wall of the pipeline is provided with a gas hole communicated with the gas cavity, the tower reactor comprises a gas outlet at the upper part of the tower reactor, a circulating liquid outlet, the liquid inlet is communicated with the bottom of the tower reactor, the circulating liquid outlet is communicated with the gas-liquid channel through the wall of the tower reactor through a liquid circulating pipeline, the liquid circulating pipeline is provided with a circulating pump and a mixer, and the inlet of the mixer is communicated with the upper part of the tower reactor through the gas phase balance pipe. The ozone oxidation reactor has the advantages of good catalyst fluidization performance, small gas pressure drop, large gas-liquid mass transfer reaction area, almost 100 percent utilization of gas, high reaction speed and the like.
201820012228.6A wastewater treatment mechanism, in particular to an ozone contact reaction mechanism. The method mainly solves the technical problems that in the prior art, a wastewater treatment mechanism is not completely contacted with wastewater, the wastewater is not uniformly distributed, and the wastewater cannot be completely blended with a catalyst filler, so that the treatment effect is poor, the treatment efficiency is low, and the like. The utility model relates to a reaction tower (1), wherein a plurality of packing supporting plates (2) are arranged in the reaction tower (1), packing layers (3) are arranged on the packing supporting plates, seasoning supporting plates are connected to a lifting rod (4), the top end of the lifting rod is connected with a hydraulic cylinder (5), a spiral stirring rod (6) is transversely introduced into the reaction tower, and the spiral stirring rod extends into the packing layers.
201621206721.9 discloses an ozone oxidation reactor, which comprises a reaction tower, wherein the reaction tower is connected with an ozone generator, a water and gas distribution layer, an ozone catalytic oxidation reaction zone and a clear water zone are sequentially arranged in the reaction tower from bottom to top, the ozone catalytic oxidation reaction zone is divided into two sections by a buffer zone, a water inlet is arranged on the water and gas distribution layer in the reaction tower, catalyst filler is filled in the ozone catalytic oxidation reaction zone, a water outlet and a circulating water outlet are arranged on the side part of the clear water zone, a residual ozone gas outlet is arranged in the clear water zone, and the circulating water outlet is connected to the water inlet through a pipeline, so that the contact efficiency of ozone and pollutants is improved, and the adding amount of ozone is reduced; the efficiency of removing the difficult degradation pollutant is improved, under the condition of the same ozone adding amount, the removal rate of the difficult degradation pollutant in water is further improved, and meanwhile, the biodegradability of the wastewater can be improved.
The technological equipment for water treatment by ozone oxidation method mainly consists of ozone generator and gas-water contact equipment. Above patent and prior art use ozone to exist ozone and waste water contact inadequately, and the shortcoming that ozone utilization ratio is low has restricted the efficiency of ozone treatment sewage, has increased the cost. The catalysts currently used in the heterogeneous catalytic ozonation process are mainly metal oxides (MnO2, TiO2, Al2O3 and the like) and metals or metal oxides (Cu/Al2O3, Ru/CeO2, V-O/silica gel, TiO2/Al2O3, Co3O4/Al2O3 and the like) supported on a carrier, the catalytic activity of the catalysts depends on the particle size and the morphology of the catalysts, and the smaller the particle size of the catalysts is, the better the activity of the catalysts is. These catalysts are prone to severe metal dissolution and tend to be ineffective under neutral pH conditions.
Disclosure of Invention
In order to solve the problems, the utility model provides a multi-stage ozone reaction tower technology for feeding ozone into an ejector.
A jet aerator ozone-feeding multistage ozone reaction tower technology specifically comprises the following components: a wastewater inlet of a tower I, a wastewater outlet of the tower I, a wastewater inlet of a tower II, a wastewater outlet of the tower II, an ozone pipeline, an ozone aeration disc, a circulating pump, an ejector, a tail gas outlet of the tower II and a tail gas destructor; the waste water inlet of the tower I is positioned at the top end of the tower I, waste water flows in from the top end of the tower I, primary aeration is carried out on the waste water and ozone in the tower I, and generated waste gas flows out of a pipeline and enters the ejector; the wastewater flows out of a wastewater outlet of the tower I at the bottom end of the tower I, enters the tower II from a wastewater inlet of the tower II, and is subjected to secondary aeration with ozone discharged from an aeration disc of the tower II; the circulating pump and the ejector are arranged in the middle of the tower II to perform circulating jet reaction operation; the waste water outlet of the tower II is arranged at the top end of the tower II; and a tail gas outlet of the tower II is connected with a tail gas destructor, and the tail gas destructor is characterized in that a hydrophobic ozonolysis catalyst is adopted.
The preparation method of the hydrophobic ozonolysis catalyst comprises the following steps:
according to the mass parts, 20-35 parts of manganese nitrate are dissolved in 200-300 parts of deionized water and are uniformly stirred; then adding 20-40 parts of citric acid and 0.1-0.9 part of (ethylbenzyl) tetradecyldimethylammonium chloride into a reaction kettle, controlling the temperature to be 50-80 ℃, stirring for 20-30min, and then adjusting the pH value to 4-6 by using 0.01-0.05mol/L sodium hydroxide solution to form a colloidal solution; and then immersing the foam nickel net in the colloidal solution for 5-10min, taking out the foam nickel net, drying the foam nickel net for 40-80min at the temperature of 100-.
The copper-tin doped organic silicon modification liquid is prepared according to the following scheme:
according to the mass parts, 5-16 parts of copper acrylate and 18-38 parts of (1, 1-dimethyl-2-propenyl oxy) dimethylsilane, 0.6-3 parts of tetrakis (triphenylphosphine) palladium are added into 150 parts of tetrahydrofuran, stirred and mixed uniformly, then the temperature is controlled to be 60-80 ℃, reaction is carried out for 5-15h, 5-12 parts of ethyl orthosilicate, 0.1-0.8 part of tributyltin methacrylate, 1-6 parts of heptafluorobutyl acrylate and 1-4 parts of ammonium persulfate are added, stirring is carried out uniformly, then the temperature is controlled to be 80-100 ℃, reaction is carried out for 4-7h, then the pH value is adjusted to be neutral, and ethanol is added to dilute to the content of 0.1-0.5%, thus obtaining the copper-tin doped organic silicon modified liquid.
The circulating pump ejector enters ozone tail gas in the tower I and wastewater in the tower II.
The aeration disc adopts a micropore diffuser or a bubbler or an ejector.
The hydrosilylation reaction between copper acrylate and (1, 1-dimethyl-2-propenyl oxy) dimethyl silane is shown as the following reaction formula:
then residual double bonds and tributyltin methacrylate and heptafluorobutyl acrylate are polymerized to generate an organosilicon polymer containing fluorine ester, tin and alkene copper, and partial reaction is shown as the following schematic formula:
the utility model selects manganese nitrate as a precursor, takes copper-tin doped organosilicon modification liquid as a carrier, and highly disperses nanometer manganese oxide on the pore canal and the surface of the copper-tin doped organosilicon polymer by a dipping method to prepare the MnOX/organosilicon polymer catalyst containing fluorine ester, tin and alkene copper. Compared with the ozone oxidation of metal oxides (MnO2, TiO2, Al2O3 and the like) and metals or metal oxides loaded on a carrier, the catalyst has high ozone catalytic activity, stable property, less metal dissolution and good activity under neutral conditions, and is hopefully applied to the field of practical water treatment.
The reaction tower disclosed by the utility model utilizes the jet technology to circulate jet wastewater and ozone, so that the contact time and the contact area of the wastewater and the ozone are greatly increased, and the ozone utilization rate is improved; the utility model also provides a hydrophobic ozonolysis catalyst, which has higher ozonolysis efficiency and better moisture resistance, the decomposition efficiency is not influenced by the environmental humidity, and the catalyst can be used for decomposing ozone under different humidity environments.
Drawings
The utility model is further illustrated with reference to the following figures and examples:
FIG. 1 is a schematic view of an ejector-fed ozone multistage ozone reaction tower of the present invention.
In the figure, 1: a wastewater inlet of a tower I; 2: a wastewater outlet of the tower I; 3: a wastewater inlet of a tower II; 4: a wastewater outlet of a tower II; 5: an ozone pipe; 6: an ozone aeration disc; 7: a circulation pump; 8: an ejector; 9: a tail gas outlet of the tower II; 10: and a tail gas breaker.
Fig. 2 is a detection report of the environment detection limited company of the great company and the great company.
Detailed Description
The following example data comparison is provided by the Daliang public environmental testing, Inc.
The utility model is further illustrated by the following specific examples:
HJ828-2017 (for measuring chemical oxygen demand of water quality) for COD measurementAcid salt method) to determine the COD content in the wastewater. The untreated wastewater used in the following examples had a COD content of 1.44 beta 103mg/L。
Performance of the ozonolysis catalyst: controlling the relative humidity to be 70 percent and the ozone concentration to be about 500 micrograms/cubic so as to simulate high-concentration ozone gas which can be contacted in production; the space velocity of the catalyst reaction is 25000h-1。
Example 1
A jet aerator ozone-feeding multistage ozone reaction tower technology specifically comprises the following components: a wastewater inlet of a tower I, a wastewater outlet of the tower I, a wastewater inlet of a tower II, a wastewater outlet of the tower II, an ozone pipeline, an ozone aeration disc, a circulating pump, an ejector, a tail gas outlet of the tower II and a tail gas destructor; the waste water inlet of the tower I is positioned at the top end of the tower I, waste water flows in from the top end of the tower I, primary aeration is carried out on the waste water and ozone in the tower I, and generated waste gas flows out of a pipeline and enters the ejector; the wastewater flows out of a wastewater outlet of the tower I at the bottom end of the tower I, enters the tower II from a wastewater inlet of the tower II, and is subjected to secondary aeration with ozone discharged from an aeration disc of the tower II; the circulating pump and the ejector are arranged in the middle of the tower II to perform circulating jet reaction operation; the waste water outlet of the tower II is arranged at the top end of the tower II; and a tail gas outlet of the tower II is connected with a tail gas destructor, and the tail gas destructor is characterized in that a hydrophobic ozonolysis catalyst is adopted.
The preparation method of the hydrophobic ozonolysis catalyst comprises the following steps:
dissolving 20kg of manganese nitrate in 200kg of deionized water, and uniformly stirring; then adding 20kg of citric acid and 0.1kg of (ethylbenzyl) tetradecyldimethylammonium chloride into a reaction kettle, controlling the temperature at 50 ℃, stirring for 20min, and then adjusting the pH value to 4 by using 0.01mol/L sodium hydroxide solution to form a colloidal solution; and then immersing the foam nickel net in the colloidal solution for 5min, taking out the foam nickel net, drying the foam nickel net for 40min at 100 ℃, placing the foam nickel net in a muffle furnace, calcining the foam nickel net for 1h at 400 ℃, cooling the foam nickel net to room temperature, immersing the foam nickel net in the copper-tin doped organic silicon modified solution, controlling the temperature to be 30 ℃ for treatment for 10h, taking out the foam nickel net and drying the foam nickel net at 80 ℃ to obtain the hydrophobic ozonolysis catalyst.
The copper-tin doped organic silicon modified liquid is prepared according to the following scheme:
adding 5Kg of copper acrylate and 18Kg of (1, 1-dimethyl-2-propenyl oxy) dimethylsilane and 0.6Kg of palladium tetrakis (triphenylphosphine) into 120Kg of tetrahydrofuran, stirring and mixing uniformly, then controlling the temperature to be 60 ℃, reacting for 5h, then adding 5Kg of ethyl orthosilicate and 0.1Kg of tributyltin methacrylate, 1Kg of heptafluorobutyl acrylate and 1Kg of ammonium persulfate, stirring uniformly, then controlling the temperature to be 80 ℃, reacting for 4h, then adjusting the pH value to be neutral, and adding ethanol to dilute to the content of 0.1%, thus obtaining the copper-tin doped organosilicon modified solution.
The circulating pump ejector enters ozone tail gas in the tower I and wastewater in the tower II.
The aeration disc adopts a micropore diffuser.
The COD removal rate in the wastewater of the experimental device is 97.1 percent, and the ozone purification and decomposition rate of the prepared hydrophobic ozonolysis catalyst is 97.7 percent.
Example 2
A jet aerator ozone-feeding multistage ozone reaction tower technology specifically comprises the following components: a wastewater inlet of a tower I, a wastewater outlet of the tower I, a wastewater inlet of a tower II, a wastewater outlet of the tower II, an ozone pipeline, an ozone aeration disc, a circulating pump, an ejector, a tail gas outlet of the tower II and a tail gas destructor; the waste water inlet of the tower I is positioned at the top end of the tower I, waste water flows in from the top end of the tower I, primary aeration is carried out on the waste water and ozone in the tower I, and generated waste gas flows out of a pipeline and enters the ejector; the wastewater flows out of a wastewater outlet of the tower I at the bottom end of the tower I, enters the tower II from a wastewater inlet of the tower II, and is subjected to secondary aeration with ozone discharged from an aeration disc of the tower II; the circulating pump and the ejector are arranged in the middle of the tower II to perform circulating jet reaction operation; the waste water outlet of the tower II is arranged at the top end of the tower II; and a tail gas outlet of the tower II is connected with a tail gas destructor, and the tail gas destructor is characterized in that a hydrophobic ozonolysis catalyst is adopted.
The preparation method of the hydrophobic ozonolysis catalyst comprises the following steps:
dissolving 25kg of manganese nitrate in 260kg of deionized water, and uniformly stirring; then adding 30kg of citric acid and 0.5kg of (ethylbenzyl) tetradecyldimethylammonium chloride into a reaction kettle, controlling the temperature at 60 ℃, stirring for 25min, and then adjusting the pH value to 5 by using 0.03mol/L sodium hydroxide solution to form a colloidal solution; and then immersing the foam nickel net in the colloidal solution for 8min, taking out the foam nickel net, drying the foam nickel net for 60min at 120 ℃, placing the foam nickel net in a muffle furnace, calcining the foam nickel net for 3h at 450 ℃, cooling the foam nickel net to room temperature, immersing the foam nickel net in the copper-tin doped organic silicon modified solution, controlling the temperature to be 35 ℃ for treatment for 16h, taking out the foam nickel net and drying the foam nickel net at 90 ℃ to obtain the hydrophobic ozonolysis catalyst.
The copper-tin doped organic silicon modified liquid is prepared according to the following scheme:
adding 11Kg of copper acrylate and 21Kg of (1, 1-dimethyl-2-propenyl oxy) dimethylsilane and 2.3Kg of tetrakis (triphenylphosphine) palladium into 132Kg of tetrahydrofuran, stirring and mixing uniformly, then controlling the temperature to be 66 ℃, reacting for 7h, then adding 5-12Kg of ethyl orthosilicate and 0.5Kg of tributyltin methacrylate, 2Kg of heptafluorobutyl acrylate and 1.3Kg of ammonium persulfate, stirring uniformly, then controlling the temperature to be 86 ℃, reacting for 5h, then adjusting the pH value to be neutral, and adding ethanol to dilute to the content of 0.2%, thereby obtaining the copper-tin doped organic silicon modified liquid.
The circulating pump ejector enters ozone tail gas in the tower I and wastewater in the tower II.
The aeration plate adopts a bubbler.
The COD removal rate in the wastewater of the experimental device is 97.6 percent, and the ozone purification and decomposition rate of the prepared hydrophobic ozonolysis catalyst is 98.4 percent.
Example 3
A jet aerator ozone-feeding multistage ozone reaction tower technology specifically comprises the following components: the system comprises a tower I wastewater inlet, a tower I wastewater outlet, a tower II wastewater inlet, a tower II wastewater outlet, an ozone pipeline, an ozone aeration disc, a circulating pump, an ejector, a tower II tail gas outlet and a tail gas destructor; the waste water inlet of the tower I is positioned at the top end of the tower I, waste water flows in from the top end of the tower I, primary aeration is carried out on the waste water and ozone in the tower I, and generated waste gas flows out of a pipeline and enters the ejector; the wastewater flows out of a wastewater outlet of the tower I at the bottom end of the tower I, enters the tower II from a wastewater inlet of the tower II, and is subjected to secondary aeration with ozone discharged from an aeration disc of the tower II; the circulating pump and the ejector are arranged in the middle of the tower II to perform circulating jet reaction operation; the wastewater outlet of the tower II is arranged at the top end of the tower II; and a tail gas outlet of the tower II is connected with a tail gas destructor, and the tail gas destructor is characterized in that a hydrophobic ozonolysis catalyst is adopted.
The preparation method of the hydrophobic ozonolysis catalyst comprises the following steps:
dissolving 35kg of manganese nitrate in 300kg of deionized water, and uniformly stirring; then adding 40kg of citric acid and 0.9kg of (ethylbenzyl) tetradecyldimethylammonium chloride into a reaction kettle, controlling the temperature at 80 ℃, stirring for 30min, and then adjusting the pH value to 6 by using 0.05mol/L sodium hydroxide solution to form a colloidal solution; and then immersing the foam nickel net in the colloidal solution for 10min, taking out the foam nickel net, drying the foam nickel net for 80min at the temperature of 130 ℃, placing the foam nickel net in a muffle furnace, calcining the foam nickel net for 5h at the temperature of 500 ℃, cooling the foam nickel net to room temperature, immersing the foam nickel net in the copper-tin doped organic silicon modified solution, controlling the temperature to be 40 ℃, treating the foam nickel net for 18h, taking out the foam nickel net and drying the foam nickel net at the temperature of 100 ℃ to obtain the hydrophobic ozonolysis catalyst.
The copper-tin doped organic silicon modified liquid is prepared according to the following scheme:
adding 16Kg of copper acrylate and 38Kg of (1, 1-dimethyl-2-propenyl oxy) dimethylsilane and 3Kg of palladium tetrakis (triphenylphosphine) into 150Kg of tetrahydrofuran, stirring and mixing uniformly, then controlling the temperature to 80 ℃, reacting for 15h, then adding 12Kg of ethyl orthosilicate and 0.8Kg of tributyltin methacrylate, 6Kg of heptafluorobutyl acrylate and 4Kg of ammonium persulfate, stirring uniformly, then controlling the temperature to 100 ℃, reacting for 7h, then adjusting the pH value to be neutral, and adding ethanol to dilute to the content of 0.5%, thus obtaining the copper-tin doped organic silicon modified liquid.
The circulating pump ejector enters ozone tail gas in the tower I and wastewater in the tower II.
The aeration disc adopts an ejector.
The COD removal rate in the wastewater of the experimental device is 98.1 percent, and the ozone purification and decomposition rate of the prepared hydrophobic ozonolysis catalyst is 98.9 percent.
Comparative example 1
A jet aerator ozone-feeding multistage ozone reaction tower technology specifically comprises the following components: the system comprises a tower I wastewater inlet, a tower I wastewater outlet, a tower II wastewater inlet, a tower II wastewater outlet, an ozone pipeline, an ozone aeration disc, a circulating pump, an ejector, a tower II tail gas outlet and a tail gas destructor; the waste water inlet of the tower I is positioned at the top end of the tower I, waste water flows in from the top end of the tower I, primary aeration is carried out on the waste water and ozone in the tower I, and generated waste gas flows out of a pipeline and enters the ejector; the wastewater flows out of a wastewater outlet of the tower I at the bottom end of the tower I, enters the tower II from a wastewater inlet of the tower II, and is subjected to secondary aeration with ozone discharged from an aeration disc of the tower II; the circulating pump and the ejector are arranged in the middle of the tower II to perform circulating jet reaction operation; the waste water outlet of the tower II is arranged at the top end of the tower II; and a tail gas outlet of the tower II is connected with a tail gas destructor, and the tail gas destructor is characterized in that a hydrophobic ozonolysis catalyst is adopted.
The preparation method of the hydrophobic ozonolysis catalyst comprises the following steps:
dissolving 25kg of manganese nitrate in 260kg of deionized water, and uniformly stirring; then adding 30kg of citric acid and 0.5kg of (ethylbenzyl) tetradecyldimethylammonium chloride into a reaction kettle, controlling the temperature at 60 ℃, stirring for 25min, and then adjusting the pH value to 5 by using 0.03mol/L sodium hydroxide solution to form a colloidal solution; and then immersing the foam nickel net in the colloidal solution for 8min, taking out the foam nickel net, drying the foam nickel net for 60min at 120 ℃, placing the foam nickel net in a muffle furnace, calcining the foam nickel net for 3h at 450 ℃, cooling the foam nickel net to room temperature, immersing the foam nickel net in the copper-tin doped organic silicon modified solution, controlling the temperature to be 35 ℃ for treatment for 16h, taking out the foam nickel net and drying the foam nickel net at 90 ℃ to obtain the hydrophobic ozonolysis catalyst.
The copper-tin doped organic silicon modification liquid is prepared according to the following scheme:
adding 11Kg of copper acrylate and 21Kg of (1, 1-dimethyl-2-propenyl oxy) dimethylsilane and 2.3Kg of tetrakis (triphenylphosphine) palladium into 132Kg of tetrahydrofuran, stirring and mixing uniformly, then controlling the temperature to be 66 ℃, reacting for 7h, then adding 5-12Kg of ethyl orthosilicate and 0.5Kg of tributyltin methacrylate, 2Kg of heptafluorobutyl acrylate and 1.3Kg of ammonium persulfate, stirring uniformly, then controlling the temperature to be 86 ℃, reacting for 5h, then adjusting the pH value to be neutral, and adding ethanol to dilute to the content of 0.2%, thereby obtaining the copper-tin doped organic silicon modified liquid.
The circulating pump ejector enters ozone tail gas in the tower I and wastewater in the tower II.
The aeration plate adopts a bubbler.
The ejector in this comparative example was not opened.
The COD removal rate in the wastewater of the experimental device is 81.5 percent, and the ozone purification and decomposition rate of the prepared hydrophobic ozonolysis catalyst is 97.7 percent.
Comparative example 2
A jet aerator ozone-feeding multistage ozone reaction tower technology specifically comprises the following components: a wastewater inlet of a tower I, a wastewater outlet of the tower I, a wastewater inlet of a tower II, a wastewater outlet of the tower II, an ozone pipeline, an ozone aeration disc, a circulating pump, an ejector, a tail gas outlet of the tower II and a tail gas destructor; the waste water inlet of the tower I is positioned at the top end of the tower I, waste water flows in from the top end of the tower I, primary aeration is carried out on the waste water and ozone in the tower I, and generated waste gas flows out of a pipeline and enters the ejector; the wastewater flows out of a wastewater outlet of the tower I at the bottom end of the tower I, enters the tower II from a wastewater inlet of the tower II, and is subjected to secondary aeration with ozone discharged from an aeration disc of the tower II; the circulating pump and the ejector are arranged in the middle of the tower II to perform circulating jet reaction operation; the waste water outlet of the tower II is arranged at the top end of the tower II; and a tail gas outlet of the tower II is connected with a tail gas destructor, and the tail gas destructor is characterized in that a hydrophobic ozonolysis catalyst is adopted.
The preparation method of the hydrophobic ozonolysis catalyst comprises the following steps:
dissolving 25kg of manganese nitrate in 260kg of deionized water, and uniformly stirring; then adding 30kg of citric acid and 0.5kg of (ethylbenzyl) tetradecyldimethylammonium chloride into a reaction kettle, controlling the temperature at 60 ℃, stirring for 25min, and then adjusting the pH value to 5 by using 0.03mol/L sodium hydroxide solution to form a colloidal solution; and then immersing the foam nickel net in the colloidal solution for 8min, taking out the foam nickel net, drying the foam nickel net for 60min at 120 ℃, placing the foam nickel net in a muffle furnace, calcining the foam nickel net for 3h at 450 ℃, cooling the foam nickel net to room temperature, and taking out the foam nickel net to obtain the hydrophobic ozonolysis catalyst.
The circulating pump ejector enters ozone tail gas in the tower I and wastewater in the tower II.
The aeration plate adopts a bubbler.
The COD removal rate in the wastewater of the experimental device is 85.1 percent, and the ozone purification and decomposition rate of the prepared hydrophobic ozonolysis catalyst is 86.2 percent.
Comparative example 3
A jet aerator ozone-feeding multistage ozone reaction tower technology specifically comprises the following components: a wastewater inlet of a tower I, a wastewater outlet of the tower I, a wastewater inlet of a tower II, a wastewater outlet of the tower II, an ozone pipeline, an ozone aeration disc, a circulating pump, an ejector, a tail gas outlet of the tower II and a tail gas destructor; the waste water inlet of the tower I is positioned at the top end of the tower I, waste water flows in from the top end of the tower I, primary aeration is carried out on the waste water and ozone in the tower I, and generated waste gas flows out of a pipeline and enters the ejector; the wastewater flows out of a wastewater outlet of the tower I at the bottom end of the tower I, enters the tower II from a wastewater inlet of the tower II, and is subjected to secondary aeration with ozone discharged from an aeration disc of the tower II; the circulating pump and the ejector are arranged in the middle of the tower II to perform circulating jet reaction operation; the waste water outlet of the tower II is arranged at the top end of the tower II; and a tail gas outlet of the tower II is connected with a tail gas destructor, and the tail gas destructor is characterized in that a hydrophobic ozonolysis catalyst is adopted.
The preparation method of the hydrophobic ozonolysis catalyst comprises the following steps:
dissolving 25kg of manganese nitrate in 260kg of deionized water, and uniformly stirring; then adding 30kg of citric acid and 0.5kg of (ethylbenzyl) tetradecyldimethylammonium chloride into a reaction kettle, controlling the temperature at 60 ℃, stirring for 25min, and then adjusting the pH value to 5 by using 0.03mol/L sodium hydroxide solution to form a colloidal solution; and then immersing the foam nickel net in the colloidal solution for 8min, taking out the foam nickel net, drying the foam nickel net for 60min at 120 ℃, placing the foam nickel net in a muffle furnace, calcining the foam nickel net for 3h at 450 ℃, cooling the foam nickel net to room temperature, immersing the foam nickel net in the copper-tin doped organic silicon modified solution, controlling the temperature to be 35 ℃ for treatment for 16h, taking out the foam nickel net and drying the foam nickel net at 90 ℃ to obtain the hydrophobic ozonolysis catalyst.
The copper-tin doped organic silicon modified liquid is prepared according to the following scheme:
adding 11Kg of copper acrylate and 21Kg of (1, 1-dimethyl-2-propenyl oxy) dimethylsilane and 2.3Kg of tetrakis (triphenylphosphine) palladium into 132Kg of tetrahydrofuran, stirring and mixing uniformly, then controlling the temperature at 66 ℃, reacting for 7h, then adjusting the pH value to be neutral, and adding ethanol to dilute to the content of 0.2%, thus obtaining the copper-tin doped organic silicon modified solution.
The circulating pump ejector enters ozone tail gas in the tower I and wastewater in the tower II.
The aeration plate adopts a bubbler.
The COD removal rate in the wastewater of the experimental device is 93.2 percent, and the ozone purification and decomposition rate of the prepared hydrophobic ozonolysis catalyst is 91.7 percent.
Comparative example 4
A jet aerator ozone-feeding multistage ozone reaction tower technology specifically comprises the following components: a wastewater inlet of a tower I, a wastewater outlet of the tower I, a wastewater inlet of a tower II, a wastewater outlet of the tower II, an ozone pipeline, an ozone aeration disc, a circulating pump, an ejector, a tail gas outlet of the tower II and a tail gas destructor; the waste water inlet of the tower I is positioned at the top end of the tower I, waste water flows in from the top end of the tower I, primary aeration is carried out on the waste water and ozone in the tower I, and generated waste gas flows out of a pipeline and enters the ejector; the wastewater flows out of a wastewater outlet of the tower I at the bottom end of the tower I, enters the tower II from a wastewater inlet of the tower II, and is subjected to secondary aeration with ozone discharged from an aeration disc of the tower II; the circulating pump and the ejector are arranged in the middle of the tower II to perform circulating jet reaction operation; the waste water outlet of the tower II is arranged at the top end of the tower II; and a tail gas outlet of the tower II is connected with a tail gas destructor, and the tail gas destructor is characterized in that a hydrophobic ozonolysis catalyst is adopted.
The preparation method of the hydrophobic ozonolysis catalyst comprises the following steps:
dissolving 25kg of manganese nitrate in 260kg of deionized water, and uniformly stirring; then adding 30kg of citric acid and 0.5kg of (ethylbenzyl) tetradecyldimethylammonium chloride into a reaction kettle, controlling the temperature at 60 ℃, stirring for 25min, and then adjusting the pH value to 5 by using 0.03mol/L sodium hydroxide solution to form a colloidal solution; and then immersing the foam nickel net in the colloidal solution for 8min, taking out the foam nickel net, drying the foam nickel net for 60min at 120 ℃, placing the foam nickel net in a muffle furnace, calcining the foam nickel net for 3h at 450 ℃, cooling the foam nickel net to room temperature, immersing the foam nickel net in the copper-tin doped organic silicon modified solution, controlling the temperature to be 35 ℃ for treatment for 16h, taking out the foam nickel net and drying the foam nickel net at 90 ℃ to obtain the hydrophobic ozonolysis catalyst.
The copper-tin doped organic silicon modified liquid is prepared according to the following scheme:
adding 11Kg of copper acrylate and 21Kg of (1, 1-dimethyl-2-propenyl oxy) dimethylsilane and 2.3Kg of tetrakis (triphenylphosphine) palladium into 132Kg of tetrahydrofuran, stirring and mixing uniformly, then controlling the temperature at 66 ℃, reacting for 7h, then adding 5-12Kg of ethyl orthosilicate and 2Kg of heptafluorobutyl acrylate, and stirring uniformly, then controlling the temperature at 86 ℃, reacting for 5h, then adjusting the pH value to be neutral, and adding ethanol to dilute to the content of 0.2%, thus obtaining the copper-tin doped organic silicon modified liquid.
And the circulating pump ejector enters ozone tail gas in the tower I and wastewater in the tower II.
The aeration plate adopts a bubbler.
The COD removal rate in the wastewater of the experimental device is 94.5 percent, and the ozone purification and decomposition rate of the prepared hydrophobic ozonolysis catalyst is 90.8 percent.
Comparative example 5
A jet aerator ozone-feeding multistage ozone reaction tower technology specifically comprises the following components: a wastewater inlet of a tower I, a wastewater outlet of the tower I, a wastewater inlet of a tower II, a wastewater outlet of the tower II, an ozone pipeline, an ozone aeration disc, a circulating pump, an ejector, a tail gas outlet of the tower II and a tail gas destructor; the waste water inlet of the tower I is positioned at the top end of the tower I, waste water flows in from the top end of the tower I, primary aeration is carried out on the waste water and ozone in the tower I, and generated waste gas flows out of a pipeline and enters the ejector; the wastewater flows out of a wastewater outlet of the tower I at the bottom end of the tower I, enters the tower II from a wastewater inlet of the tower II, and is subjected to secondary aeration with ozone discharged from an aeration disc of the tower II; the circulating pump and the ejector are arranged in the middle of the tower II to perform circulating jet reaction operation; the waste water outlet of the tower II is arranged at the top end of the tower II; and a tail gas outlet of the tower II is connected with a tail gas destructor, and the tail gas destructor is characterized in that a hydrophobic ozonolysis catalyst is adopted.
The preparation method of the hydrophobic ozonolysis catalyst comprises the following steps:
dissolving 25kg of manganese nitrate in 260kg of deionized water, and uniformly stirring; then adding 30kg of citric acid and 0.5kg of (ethylbenzyl) tetradecyldimethylammonium chloride into a reaction kettle, controlling the temperature at 60 ℃, stirring for 25min, and then adjusting the pH value to 5 by using 0.03mol/L sodium hydroxide solution to form a colloidal solution; and then immersing the foam nickel net in the colloidal solution for 8min, taking out the foam nickel net, drying the foam nickel net for 60min at 120 ℃, placing the foam nickel net in a muffle furnace, calcining the foam nickel net for 3h at 450 ℃, cooling the foam nickel net to room temperature, immersing the foam nickel net in the copper-tin doped organic silicon modified solution, controlling the temperature to be 35 ℃ for treatment for 16h, taking out the foam nickel net and drying the foam nickel net at 90 ℃ to obtain the hydrophobic ozonolysis catalyst.
The copper-tin doped organic silicon modified liquid is prepared according to the following scheme:
adding 11Kg of copper acrylate and 21Kg of (1, 1-dimethyl-2-propenyl oxy) dimethylsilane and 2.3Kg of tetrakis (triphenylphosphine) palladium into 132Kg of tetrahydrofuran, stirring and mixing uniformly, then controlling the temperature at 66 ℃, reacting for 7h, then adding 5-12Kg of ethyl orthosilicate and 0.5Kg of tributyltin methacrylate, and 1.3Kg of ammonium persulfate, stirring uniformly, then controlling the temperature at 86 ℃, reacting for 5h, then regulating the pH value to be neutral, and adding ethanol to dilute to the content of 0.2%, thus obtaining the copper-tin doped organic silicon modified liquid.
The circulating pump ejector enters ozone tail gas in the tower I and wastewater in the tower II.
The aeration plate adopts a bubbler.
The COD removal rate in the wastewater of the experimental device is 93.1 percent, and the ozone purification and decomposition rate of the prepared hydrophobic ozonolysis catalyst is 91.6 percent.
Comparative example 6
A jet aerator ozone-feeding multistage ozone reaction tower technology specifically comprises the following components: a wastewater inlet of a tower I, a wastewater outlet of the tower I, a wastewater inlet of a tower II, a wastewater outlet of the tower II, an ozone pipeline, an ozone aeration disc, a circulating pump, an ejector, a tail gas outlet of the tower II and a tail gas destructor; the waste water inlet of the tower I is positioned at the top end of the tower I, waste water flows in from the top end of the tower I, primary aeration is carried out on the waste water and ozone in the tower I, and generated waste gas flows out of a pipeline and enters the ejector; the wastewater flows out of a wastewater outlet of the tower I at the bottom end of the tower I, enters the tower II from a wastewater inlet of the tower II, and is subjected to secondary aeration with ozone discharged from an aeration disc of the tower II; the circulating pump and the ejector are arranged in the middle of the tower II to perform circulating jet reaction operation; the wastewater outlet of the tower II is arranged at the top end of the tower II; and a tail gas outlet of the tower II is connected with a tail gas destructor, and the tail gas destructor is characterized in that a hydrophobic ozonolysis catalyst is adopted.
The preparation method of the hydrophobic ozonolysis catalyst comprises the following steps:
dissolving 25kg of manganese nitrate in 260kg of deionized water, and uniformly stirring; then adding 30kg of citric acid and 0.5kg of (ethylbenzyl) tetradecyldimethylammonium chloride into a reaction kettle, controlling the temperature at 60 ℃, stirring for 25min, and then adjusting the pH value to 5 by using 0.03mol/L sodium hydroxide solution to form a colloidal solution; and then immersing the foam nickel net in the colloidal solution for 8min, taking out the foam nickel net, drying the foam nickel net for 60min at 120 ℃, placing the foam nickel net in a muffle furnace, calcining the foam nickel net for 3h at 450 ℃, cooling the foam nickel net to room temperature, immersing the foam nickel net in the copper-tin doped organic silicon modified solution, controlling the temperature to be 35 ℃ for treatment for 16h, taking out the foam nickel net and drying the foam nickel net at 90 ℃ to obtain the hydrophobic ozonolysis catalyst.
The copper-tin doped organic silicon modified liquid is prepared according to the following scheme:
adding 21Kg of (1, 1-dimethyl-2-propenyl oxy) dimethylsilane and 2.3Kg of tetrakis (triphenylphosphine) palladium into 132Kg of tetrahydrofuran, stirring and mixing uniformly, then controlling the temperature to be 66 ℃, reacting for 7h, then adding 5-12Kg of ethyl orthosilicate and 0.5Kg of tributyltin methacrylate, 2Kg of heptafluorobutyl acrylate and 1.3Kg of ammonium persulfate, stirring uniformly, then controlling the temperature to be 86 ℃, reacting for 5h, then adjusting the pH value to be neutral, and adding ethanol to dilute to the content of 0.2%, thereby obtaining the copper-tin doped organic silicon modified liquid.
The circulating pump ejector enters ozone tail gas in the tower I and wastewater in the tower II.
The aeration disc adopts a bubbler.
The COD removal rate in the wastewater of the experimental device is 92.5 percent, and the ozone purification and decomposition rate of the prepared hydrophobic ozonolysis catalyst is 90.6 percent.
Comparative example 7
A jet aerator ozone-feeding multistage ozone reaction tower technology specifically comprises the following components: a wastewater inlet of a tower I, a wastewater outlet of the tower I, a wastewater inlet of a tower II, a wastewater outlet of the tower II, an ozone pipeline, an ozone aeration disc, a circulating pump, an ejector, a tail gas outlet of the tower II and a tail gas destructor; the waste water inlet of the tower I is positioned at the top end of the tower I, waste water flows in from the top end of the tower I, primary aeration is carried out on the waste water and ozone in the tower I, and generated waste gas flows out of a pipeline and enters the ejector; the wastewater flows out of a wastewater outlet of the tower I at the bottom end of the tower I, enters the tower II from a wastewater inlet of the tower II, and is subjected to secondary aeration with ozone discharged from an aeration disc of the tower II; the circulating pump and the ejector are arranged in the middle of the tower II to perform circulating jet reaction operation; the waste water outlet of the tower II is arranged at the top end of the tower II; and a tail gas outlet of the tower II is connected with a tail gas destructor, and the tail gas destructor is characterized in that a hydrophobic ozonolysis catalyst is adopted.
The preparation method of the hydrophobic ozonolysis catalyst comprises the following steps:
dissolving 25kg of manganese nitrate in 260kg of deionized water, and uniformly stirring; then adding 30kg of citric acid and 0.5kg of (ethylbenzyl) tetradecyldimethylammonium chloride into a reaction kettle, controlling the temperature at 60 ℃, stirring for 25min, and then adjusting the pH value to 5 by using 0.03mol/L sodium hydroxide solution to form a colloidal solution; and then immersing the foam nickel net in the colloidal solution for 8min, taking out the foam nickel net, drying the foam nickel net for 60min at 120 ℃, placing the foam nickel net in a muffle furnace, calcining the foam nickel net for 3h at 450 ℃, cooling the foam nickel net to room temperature, immersing the foam nickel net in the copper-tin doped organic silicon modified solution, controlling the temperature to be 35 ℃ for treatment for 16h, taking out the foam nickel net and drying the foam nickel net at 90 ℃ to obtain the hydrophobic ozonolysis catalyst.
The copper-tin doped organic silicon modification liquid is prepared according to the following scheme:
adding 11Kg of copper acrylate and 2.3Kg of palladium tetrakis (triphenylphosphine) into 132Kg of tetrahydrofuran, stirring and mixing uniformly, then controlling the temperature at 66 ℃ and reacting for 7h, then adding 5-12Kg of ethyl orthosilicate and 0.5Kg of tributyltin methacrylate, 2Kg of heptafluorobutyl acrylate and 1.3Kg of ammonium persulfate, stirring uniformly, then controlling the temperature at 86 ℃ and reacting for 5h, then adjusting the pH value to be neutral, and adding ethanol to dilute to the content of 0.2%, thus obtaining the copper-tin doped organic silicon modified liquid.
The circulating pump ejector enters ozone tail gas in the tower I and wastewater in the tower II.
The aeration plate adopts a bubbler.
The COD removal rate in the wastewater of the experimental device is 91.6 percent, and the ozone purification and decomposition rate of the prepared hydrophobic ozonolysis catalyst is 89.7 percent.
Claims (6)
1. A method for feeding ozone into a multistage ozone reaction tower by an ejector specifically comprises the following steps: a wastewater inlet (1) of a tower I, a wastewater outlet (2) of the tower I, a wastewater inlet (3) of a tower II, a wastewater outlet (4) of the tower II, an ozone pipeline (5), an ozone aeration disc (6), a circulating pump (7), an ejector (8), a tail gas outlet (9) of the tower II and a tail gas destructor (10); the waste water inlet (1) of the tower I is positioned at the top end of the tower I, waste water flows in from the top end of the tower I, primary aeration is carried out on the waste water and ozone in the tower I, and generated waste gas flows out of a pipeline and enters the ejector (8); wastewater flows out of a wastewater outlet (2) of the tower I at the bottom end of the tower I, enters the tower II from a wastewater inlet (3) of the tower II, and is subjected to secondary aeration with ozone discharged from an aeration disc of the tower II; the circulating pump (7) and the ejector (8) are arranged in the middle of the tower II to perform circulating jet reaction operation; the wastewater outlet (4) of the tower II is arranged at the top end of the tower II; the tail gas outlet (9) of the tower II is connected with a tail gas destructor (10), and the tail gas destructor (10) is characterized in that a hydrophobic ozonolysis catalyst is adopted;
a preparation method of the hydrophobic ozonolysis catalyst comprises the following steps:
according to the mass parts, 20-35 parts of manganese nitrate are dissolved in 200-300 parts of deionized water and are uniformly stirred; then adding 20-40 parts of citric acid and 0.1-0.9 part of (ethylbenzyl) tetradecyldimethylammonium chloride into a reaction kettle, controlling the temperature at 50-80 ℃, stirring for 20-30min, and then adjusting the pH value to 4-6 by using 0.01-0.05mol/L sodium hydroxide solution to form a colloidal solution; then immersing the foam nickel net in the colloidal solution for 5-10min, taking out the foam nickel net and drying the foam nickel net for 40-80min at the temperature of 100-130 ℃, placing the foam nickel net in a muffle furnace and calcining the foam nickel net for 1-5h at the temperature of 400-500 ℃, cooling the foam nickel net to room temperature, immersing the foam nickel net in the copper-tin doped organic silicon modified solution, controlling the temperature to be 30-40 ℃ and treating the foam nickel net for 10-18h, taking out the foam nickel net and drying the foam nickel net at the temperature of 80-100 ℃ to obtain the hydrophobic ozonolysis catalyst;
the copper-tin doped organic silicon modified liquid is prepared according to the following scheme:
according to the mass parts, 5-16 parts of copper acrylate and 18-38 parts of (1, 1-dimethyl-2-propenyl oxy) dimethylsilane, 0.6-3 parts of tetrakis (triphenylphosphine) palladium are added into 150 parts of tetrahydrofuran, stirred and mixed uniformly, then the temperature is controlled to be 60-80 ℃, reaction is carried out for 5-15h, 5-12 parts of ethyl orthosilicate, 0.1-0.8 part of tributyltin methacrylate, 1-6 parts of heptafluorobutyl acrylate and 1-4 parts of ammonium persulfate are added, stirring is carried out uniformly, then the temperature is controlled to be 80-100 ℃, reaction is carried out for 4-7h, then the pH value is adjusted to be neutral, and ethanol is added to dilute to the content of 0.1-0.5%, thus obtaining the copper-tin doped organic silicon modified liquid.
2. The ejector-feed ozone multistage ozone reaction tower method according to claim 1, characterized in that: and the circulating pump (7) and the ejector (8) enter ozone tail gas in the tower I and wastewater in the tower II.
3. The ejector-feed ozone multistage ozone reaction tower method according to claim 1, characterized in that: the aeration disc adopts a micropore diffuser or a bubbler or an ejector.
4. The ejector-feed ozone multistage ozone reaction tower method according to claim 1, characterized in that: the hydrophobic ozonolysis catalyst adopts manganese nitrate as a precursor.
5. The ejector-feed ozone multistage ozone reaction tower method according to claim 1, characterized in that: the hydrophobic ozonolysis catalyst adopts copper-tin doped organic silicon modified liquid as a carrier.
6. The ejector-feed ozone multistage ozone reaction tower method according to claim 1, characterized in that: the reaction tower utilizes a jet technology to circulate jet wastewater and ozone.
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