Method for deep purification of high-salinity water total organic carbon

Abstract

The application provides a method for deep purification of high-salt water total organic carbon, and belongs to the technical field of fine chemical salt pollution resource utilization. The method comprises the following steps: S1, removing solid suspended matters and part of adsorbable total organic carbon in high-salt water by using an activated carbon adsorption system; S2, oxidizing organic matters in the high-salt water by using a nano-ozone catalysis system; and S3, separating residual total organic carbon in the high-salt water by using a targeted adsorption system after the high-salt water is oxidized by the nano-ozone catalysis system, so as to realize deep purification of the high-salt water total organic carbon. The application provides an economic, efficient and stable deep purification method for total organic carbon, solves the problem of total organic carbon treatment in the process of fine chemical salt pollution resource utilization, reduces the influence of total organic carbon on the process of salt pollution resource utilization, and provides engineering application guidance for salt pollution resource utilization.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of fine chemical salt resource, and particularly relates to a method for deep purification of total organic carbon in high-salt water. BACKGROUND

[0002] By recycling industrial waste salt for chemical production, soda ash, caustic soda and other high-value industrial products can be manufactured, which not only eliminates the problem of waste salt and reduces the cost of waste salt landfill, but also produces new products from waste salt resources, extends the product chain, and has good social and economic benefits.

[0003] The main factor restricting the large-scale development of waste salt resource is the removal of organic matter in waste salt. For example, too high content of organic pollutants in salt water feed will adversely affect the performance of electrodialysis, ion membrane and electrolytic cell. The composition of waste salt, especially waste salt in the chemical industry, is complex, and the types of organic pollutants are various. After treatment, the composition of residual impurities, especially total organic carbon, is uncertain, and it is difficult to completely apply the existing process of resource technology. SUMMARY

[0004] The purpose of the present application is to provide a method for deep purification of total organic carbon in high-salt water. The present application adopts a combined process technology of "activated carbon adsorption + nano catalytic ozone oxidation + targeted adsorption" to deeply purify the total organic carbon in high-salt water, and truly realizes the resource of waste salt.

[0005] The technical solution of the present application is as follows:

[0006] The present application provides a method for deep purification of total organic carbon in high-salt water, comprising the following steps:

[0007] S1. Using an activated carbon adsorption system to remove solid suspended matter and part of adsorbable total organic carbon in high-salt water;

[0008] S2. Oxidizing organic matter in high-salt water by a nano ozone catalytic system;

[0009] S3. The high-salt water oxidized by the nano ozone catalytic system enters a targeted adsorption system to separate the residual total organic carbon in the high-salt water, realizing deep purification of total organic carbon in high-salt water.

[0010] The activated carbon adsorption is mainly physical adsorption, and the aromatic hydrocarbon organic matters in the salt water can be adsorbed, so that the ozone dosage in the subsequent ozone catalysis can be reduced, thereby reducing the treatment cost (the aromatic hydrocarbon organic matters are difficult to be degraded by ozone, and the cost is high). After the adsorption, the high-salt water is subjected to the ozone catalytic oxidation, some long-chain and heterocyclic organic matters are oxidized into short-chain and alkane compounds and carbon dioxide; finally, the short-chain alkane compounds in the high-salt water are adsorbed by the targeted adsorption, so that the total organic carbon purification is realized. Through the combination of the above process, the deep purification of the saturated salt water can be realized.

[0011] As a further improvement of the present application, in the active adsorption system, the mass fraction of salt in the high-salt water is 10% to 26.5%, the adsorption temperature is 40 to 70℃, the pH is 9 to 12, the hydraulic retention time of the activated carbon in contact with the high-salt water is 30 to 180 min, the filling height of the activated carbon bed is 1.0 to 3.0 meters, when the pressure before and after the adsorption to the bed exceeds 0.06 Mpa, the backwashing is started, the intensity of the backwashing water is 5 to 10 L / (s·m 2 ), and the intensity of the backwashing gas is 10 to 15 L / (s·m 2 ).

[0012] As a further improvement of the present application, the activated carbon is coconut shell activated carbon, and the iodine value is 900 to 1200 mg / g; the activated carbon backwashing cycle is 1 to 3 days, and the backwashing time is 5 to 15 min.

[0013] As a further improvement of the present application, the nano ozone catalysis system comprises a nano ozone pre-oxidation system and a nano catalytic ozone oxidation system.

[0014] The nano ozone has higher solubility in water, which promotes the catalytic oxidation effect; in addition, the nano ozone has a larger contact area with the pollutants in water, and the reaction efficiency is higher; at the same time, the nano ozone also promotes the generation of hydroxyl radicals.

[0015] The core of the action mechanism of the ozone catalysis is that the dissolved ozone generates hydroxyl radicals under the action of the catalyst to oxidize the pollutants in the wastewater.

[0016] As a further improvement of the present application, in the nano ozone pre-oxidation system, air passes through an oxygen generator to generate oxygen, the generated oxygen enters an ozone generator to generate ozone, the ozone pressure generated by the ozone generator is 0.07 to 0.09 Mpa, the nano ozone gas bubbles in the nano ozone system are cut by a multi-stage cutter, the particle size of the nano ozone gas bubbles is 50 to 200 nm, the nano ozone is dissolved in the high-salt water to pre-oxidize the total organic carbon, the reaction time is 30 to 120 min, the reaction temperature is 40 to 60℃, and the reaction pH is 6 to 9.

[0017] As a further improvement of the present application, in the nano-catalytic ozone oxidation system, the gas-water mixture is pumped into the catalytic ozone tower by the jet pump, the speed of the jet outlet is 10-15 m / s, the filling height of the fixed bed catalyst is 1.5-4.5 m, the particle size of the catalyst is 3-5 mm, the contact reaction time of ozone and catalyst is 30-60 min, the reaction temperature is 40-50℃, the reaction pH is 7-8, the volume ratio of ozone and high-salt water mixture is 3 / 1-1 / 1, the mass ratio of total ozone dosage to total organic carbon is about 5 / 1-10 / 1, a pressure stabilizing valve is arranged at the top of the catalytic ozone tower, the pressure setting range is 0.09-0.12 MPa, part of the tail gas is returned to the nano-ozone system for continuous reaction, the remaining tail gas is collected and discharged after treatment by the tail gas destroyer, and the reflux ratio is 2 / 1-5 / 1.

[0018] As a further improvement of the present application, the catalytic ozone tower adopts a fixed bed form, and the catalyst is a heterogeneous catalyst, which is an alumina-based catalyst and mainly loaded with at least one of Mn, Cu, Ni and FeOOH.

[0019] The preparation method of the catalyst is as follows:

[0020] T1. Preparation of mesoporous alumina: dissolve the pore former in ethanol, adjust the pH value of the solution, add aluminum isopropylate, stir and mix uniformly, heat and stir to react, calcine, ball mill, and prepare mesoporous alumina;

[0021] T2. Preparation of N / C-doped mesoporous alumina: dissolve glucose and urea in water, immerse the mesoporous alumina in the solution, evaporate the solvent, and calcine to prepare N / C-doped mesoporous alumina;

[0022] T3. MnO2 loading: dissolve manganese salt in water, add N / C-doped mesoporous alumina, stir and mix uniformly, add potassium permanganate, transfer the solution to a stainless steel reaction kettle with a polytetrafluoroethylene liner, seal, heat and stir to react, cool to room temperature, filter the product, wash and dry to prepare MnO2-loaded N / C-doped mesoporous alumina;

[0023] T4. Cu / Ni element doping: dissolve copper salt and nickel salt in water, add MnO2-loaded N / C-doped mesoporous alumina, immerse, filter, wash, dry, calcine, and prepare a catalyst precursor;

[0024] T5. FeOOH loading: add the catalyst precursor to water, add ferrous salt and ammonium bicarbonate, heat and stir to react, filter, wash, dry, calcine, and prepare a catalyst.

[0025] Preferably, in step T1, the mass ratio of the pore-forming agent, aluminum isopropoxide is 1-2:15-20, the pH value of the adjusting solution is 5-6, the temperature of the heated stirring reaction is 70-80℃, the time is 24-36h, the temperature of the calcination is 400-600℃, the time is 1-3h, and the time of the ball milling is 1-2h.

[0026] Preferably, in step T2, the mass ratio of the glucose, urea, mesoporous aluminum oxide is 2-4:1-2:12-15, the temperature of the calcination is 550-650℃, and the time is 90-150min.

[0027] Preferably, in step T3, the mass ratio of the manganese salt, N / C-doped mesoporous aluminum oxide, potassium permanganate is 2-4:10:2.5-3, the temperature of the heated stirring reaction is 150-170℃, and the time is 10-14h.

[0028] Preferably, in step T4, the mass ratio of the copper salt, nickel salt, MnO2-loaded N / C-doped mesoporous aluminum oxide is 1-2:0.8-1.2:20-30, the temperature of the calcination is 500-600℃, and the time is 1-2h.

[0029] Preferably, in step T5, the mass ratio of the catalyst precursor, ferrous salt, and ammonium bicarbonate is 10:2-3:7-10, the temperature of the heated stirring reaction is 60-70℃, the time is 1-3h, the temperature of the calcination is 300-400℃, and the time is 60-90min.

[0030] Preferably, the pore-forming agent is at least one selected from oxyethylene-oxypropylene triblock copolymer PEO20-PPO70-PEO20 (P123), PEO106-PPO70-PEO106 (F127).

[0031] Preferably, the manganese salt is at least one selected from manganese chloride, manganese sulfate, manganese nitrate.

[0032] Preferably, the copper salt is at least one selected from copper chloride, copper sulfate, copper nitrate.

[0033] Preferably, the nickel salt is at least one selected from nickel chloride, nickel sulfate, nickel nitrate.

[0034] Preferably, the ferrous salt is ferrous chloride or ferrous sulfate.

[0035] As a further improvement of the present application, the targeted adsorption system selects a targeted adsorbent for adsorption according to the molecular structure and corresponding functional groups of the organic pollutants, the filling height of the adsorbent is 1.0-5.0 m, the hydraulic retention time of the adsorbent and the high-salt water is 30-90 min, the adsorption temperature is 30-40℃, the adsorption pH is 4-6, the eluent is 2-8% sodium hydroxide solution, the eluent amount is 2-4 times the volume of the adsorbent, the high-salt water upward flow rate is 1.0-5.0 m / h, and the eluent flow rate is 1.0-5.0 m / h.

[0036] The targeted adsorption is achieved by changing the structure of the resin surface to selectively adsorb alkane organic matter. Therefore, in this case, different resins are selected as the targeted adsorbent for adsorption according to the molecular structure and corresponding functional groups of the organic pollutants. The adsorbent uses ultrahigh cross-linked polystyrene as a substrate, introduces acrylamide groups, cyano groups, ester groups and other targeted groups, and performs targeted adsorption on the organic pollutants in the high-salt water according to the structure and polarity of the groups. When the organic pollutants contain strong polar functional groups such as carboxylic acids and phenols, an adsorbent containing acrylamide groups and cyano groups is selected for targeted adsorption. When the organic pollutants contain medium polar functional groups such as nitro groups, dimethylamine and ethers, an adsorbent containing ester groups is selected for targeted adsorption. Otherwise, an adsorbent without functional groups is selected for adsorption.

[0037] As a further improvement of the present application, the adsorbent uses ultrahigh cross-linked polystyrene as a substrate, introduces at least one of acrylamide groups, cyano groups and ester groups as a targeted group, and the diameter of the adsorbent ranges from 0.2 mm to 2.0 mm.

[0038] As a further improvement of the present application, the activated carbon tower, the ozone catalytic oxidation tower and the targeted adsorption tower all adopt a carbon steel lining structure, the lining material includes PP, PO and PE, and the thickness of the lining is 8-16 mm.

[0039] Specifically, a method for deep purification of total organic carbon in high-salt water includes the following steps:

[0040] S1. An activated carbon adsorption system is used to remove solid suspended matter and part of the adsorbable total organic carbon in the high-salt water. The activated carbon adsorption system adopts a fixed bed tower structure, the activated carbon uses coconut shell activated carbon with an iodine value ranging from 900 mg / g to 1200 mg / g, the filling height of the activated carbon bed is 1.0-3.0 meters, the hydraulic retention time of the activated carbon and the high-salt water is 30-180 min, aromatic hydrocarbon organic matter is adsorbed in the contact process, the adsorption temperature is 40-70℃, the pH is 9-12, and solid suspended matter (ss) in the high-salt water is intercepted at the same time; when the pressure before and after the bed layer exceeds 0.06 MPa, backwashing is started, the backwashing water intensity is 5-10 L / (s·m 2), the intensity of backwashing gas is 10-15 L / (s·m 2 After adsorption, the high-salinity water enters the next nanometer ozone catalytic oxidation unit for further treatment.

[0041] S2. Further oxidizing the organic matter in the high-salinity water through a nanometer ozone catalytic system. The nanometer catalytic ozone oxidation system includes two parts, nanometer ozone pre-oxidation and catalytic ozone oxidation: first, air passes through an oxygen generator to generate oxygen, the generated oxygen enters an ozone generator to generate ozone, the ozone is cut into nanometer ozone bubbles with a particle size range of 50-200 nm in the nanometer ozone system, and is dissolved in the high-salinity water to pre-oxidize the total organic carbon therein, the volume ratio of ozone to high-salinity water is 3 / 1-1 / 1, the reaction time is 30-120 min, the reaction temperature is 40-60℃, and the reaction pH is 6-9. The gas-water mixture after pre-oxidation is injected into a catalytic ozone oxidation tower through a jet device, the speed of the jet outlet is 10-15 m / s, the catalytic ozone oxidation tower adopts a fixed bed form, the catalyst adopts a heterogeneous catalyst, the total organic carbon in the high-salinity water that is not adsorbed by the activated carbon is oxidized by the hydroxyl radical (·OH) generated by the catalytic ozone, the filling height of the fixed bed catalyst is 1.5-4.5 m, the particle size range of the catalyst is 3-5 mm, the ozone and the catalyst contact for a reaction time of 30-60 min, the reaction temperature is 40-50℃, the reaction pH is 7-8, part of the tail gas after the reaction is returned to the nanometer ozone system for continuous reaction, the remaining tail gas is collected and treated in a tail gas destroyer before being discharged, the reflux ratio is 2 / 1-5 / 1, and the oxidized high-salinity water enters a targeted adsorption system.

[0042] S3. According to the different molecular structures and corresponding functional groups of the organic pollutants, a targeted adsorbent is selected for adsorption, a tower structure is adopted, the filling height of the adsorbent is 1.0-5.0 m, the diameter range of the adsorbent is 0.2-1.5 mm, the upward flow rate of the high-salinity water in the adsorption tower is 1.0-5.0 m / h, the hydraulic retention time is 30-90 min, the adsorption temperature is 30-40℃, and the adsorption pH is 4-6. After saturation, an eluent is used for elution and activation to ensure the adsorption reuse effect of the targeted adsorbent, the eluent is a 2-8% sodium hydroxide solution, the amount of the eluent is 2-4 times the volume of the adsorbent, and the flow rate of the eluent is 1.0-5.0 m / h. The total organic carbon in the high-salinity water is separated through targeted adsorption, the index requirements for entering the salt recovery system are achieved, and the purpose of resource utilization of the contaminated salt is achieved.

[0043] The application has the following beneficial effects:

[0044] The main purpose of the present application is to provide an economic, efficient and stable total organic carbon deep purification method, solve the total organic carbon treatment problem in the current fine chemical salt pollution resourceization process, reduce the influence of total organic carbon on the salt pollution resourceization process, and provide engineering application guidance for salt pollution resourceization.

[0045] The process of the present application adopts the combination process technology of "activated carbon adsorption + nano catalytic ozone oxidation + targeted adsorption" to deeply purify the total organic carbon in high-salt water, and truly realizes the resourceization of salt pollution. First, the activated carbon adsorption system is used to remove the solid suspended matter and part of the adsorbable total organic carbon in the high-salt water; then, oxygen is generated by an oxygen generator, the generated oxygen is used to generate ozone by an ozone generator, and the ozone is pumped into a nano ozone generator by a booster pump to fully mix and react with the high-salt water. In the nano ozone catalytic system, the ozone is cut into nanoscale particles and dissolved in water to pre-oxidize the organic pollutants in the high-salt water. The gas-water mixture after reaction is injected into a catalytic ozone oxidation tower through a jet device. The catalytic ozone oxidation tower adopts a fixed bed form, and the catalyst adopts a heterogeneous catalyst. The catalyst catalyzes the ozone to generate hydroxyl radicals (·OH) to continue to degrade the total organic carbon in the high-salt water. The oxidized high-salt water is further separated from the total organic carbon that cannot be oxidized and degraded in the targeted adsorption system, realizing the deep purification of the total organic carbon in the high-salt water. The total organic carbon in the treated high-salt water is less than 10 mg / L. The treated high-salt water is introduced into a salt recovery system to recover the salt therein, thereby achieving the purpose of salt pollution resourceization. The present application fully combines the characteristics of organic pollutants in salt water, and the combination process has good total organic carbon degradation effect, is economic, efficient and stable, and has a guiding role for engineering application.

[0046] The present application prepares a catalytic oxidation catalyst. Mesoporous alumina is used as a carrier. The carrier has a large specific surface area formed by a pore-forming agent, which greatly improves the loading capacity of the catalytic metal. Then, a solution containing urea and glucose is impregnated, and calcination is performed, so that the carrier is doped with C / N. By introducing non-metallic elements (such as carbon and nitrogen) into the carrier, non-metallic active sites are formed, the binding capacity of the carrier and the loaded metal oxide is improved, the affinity of the carrier for ozone molecules is enhanced, which is beneficial to the rapid conversion of ozone molecules into active radicals, and further improves the degradation capacity of the catalyst for organic pollutants.

[0047] Then, the prepared doped N / C mesoporous alumina loaded with MnO2 is subjected to oxidation reaction. Compared with noble metal supported catalysts, transition metal oxides such as MnO2 catalysts have the characteristics of wide raw material sources, low price and good resistance to toxicity. Then, Cu / Ni is loaded by impregnation and calcination, which greatly improves the catalytic performance of the catalyst under synergistic action. Finally, hydroxyl ferric oxide (FeOOH) is formed in situ, which further improves the catalytic performance.

[0048] The catalyst prepared by the method has good synergistic catalytic effect among various metal elements, and has strong catalytic oxidation under the help of non-metal elements, and has large specific surface area, high loading capacity, good catalytic performance and wide application prospect. BRIEF DESCRIPTION OF DRAWINGS

[0049] In order to more clearly illustrate the technical solutions in the embodiments of the present application or the prior art, the drawings needed to be used in the embodiments or the prior art description will be briefly introduced below. Obviously, the drawings in the following description are only some embodiments of the present application, and other drawings can be obtained by those skilled in the art without creative labor.

[0050] Figure 1 The process flow chart of the method for high-salinity water total organic carbon deep purification. DETAILED DESCRIPTION

[0051] The technical solutions in the embodiments of the present application will be described clearly and completely below. Obviously, the described embodiments are only some embodiments of the present application, not all embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor are within the scope of protection of the present application.

[0052] Preparation of the catalyst in Preparation Example 1

[0053] The method is as follows:

[0054] T1. Preparation of mesoporous alumina: 1g of oxyethylene-oxypropylene triblock copolymer PEO20-PPO70-PEO20 (P123) was dissolved in 200mL of ethanol, the pH value of the solution was adjusted to 5, 15g of aluminum isopropoxide was added, stirring and mixing for 15min, heating to 70℃, stirring and reacting for 24h, calcining at 400℃ for 1h, and ball milling for 1h to obtain mesoporous alumina;

[0055] T2. Preparation of N / C-doped mesoporous alumina: 2g of glucose and 1g of urea were dissolved in 200mL of water, 12g of mesoporous alumina was immersed in the solution, the solvent was evaporated, and the N / C-doped mesoporous alumina was obtained by calcining at 550℃ for 90min;

[0056] T3. MnO2 loading: 2g of manganese chloride was dissolved in 200mL of water, 10g of N / C-doped mesoporous alumina was added and stirred and mixed uniformly, then 2.5g of potassium permanganate was added, the solution was transferred to a stainless steel reaction kettle with a polytetrafluoroethylene liner, sealed, heated to 150℃, stirred and reacted for 10h, cooled to room temperature, the product was filtered, washed and dried to obtain MnO2-loaded N / C-doped mesoporous alumina;

[0057] T4. Cu / Ni element doping: 1 g of copper chloride and 0.8 g of nickel chloride were dissolved in 200 mL of water, 20 g of MnO2-loaded doping N / C mesoporous alumina was added, impregnated for 1 h, filtered, washed, dried, calcined at 500°C for 1 h, and a catalyst precursor was prepared;

[0058] T5. FeOOH loading: 10 g of the catalyst precursor was added to 200 mL of water, 2 g of ferrous chloride and 7 g of ammonium bicarbonate were added, heated to 60°C, stirred for 1 h, filtered, washed, dried, calcined at 300°C for 60 min, and a catalyst was prepared.

[0059] Preparation of the catalyst of Preparation Example 2

[0060] The method is as follows:

[0061] T1. Preparation of mesoporous alumina: 2 g of PEO106-PPO70-PEO106(F127) was dissolved in 200 mL of ethanol, the pH value of the solution was adjusted to 6, 20 g of aluminum isopropoxide was added, the mixture was stirred for 15 min, heated to 80°C, and stirred for 36 h, calcined at 600°C for 3 h, and ball milled for 2 h to obtain mesoporous alumina;

[0062] T2. Preparation of N / C-doped mesoporous alumina: 4 g of glucose and 2 g of urea were dissolved in 200 mL of water, 15 g of mesoporous alumina was impregnated in the solution, the solvent was evaporated, and calcination was performed at 650°C for 150 min to obtain N / C-doped mesoporous alumina;

[0063] T3. MnO2 loading: 4 g of manganese sulfate was dissolved in 200 mL of water, 10 g of N / C-doped mesoporous alumina was added and stirred until uniform, 3 g of potassium permanganate was added, the solution was transferred to a stainless steel reaction kettle with a polytetrafluoroethylene liner, sealed, heated to 170°C, stirred for 14 h, cooled to room temperature, the product was filtered, washed, and dried to obtain MnO2-loaded N / C-doped mesoporous alumina;

[0064] T4. Cu / Ni element doping: 2 g of copper sulfate and 1.2 g of nickel sulfate were dissolved in 200 mL of water, 30 g of MnO2-loaded doping N / C mesoporous alumina was added, impregnated for 1 h, filtered, washed, dried, calcined at 600°C for 2 h, and a catalyst precursor was prepared;

[0065] T5. FeOOH loading: 10 g of the catalyst precursor was added to 200 mL of water, 3 g of ferrous sulfate and 10 g of ammonium bicarbonate were added, heated to 70°C, stirred for 3 h, filtered, washed, dried, calcined at 400°C for 90 min, and a catalyst was prepared.

[0066] Preparation of the catalyst of Preparation Example 3

[0067] The method is as follows:

[0068] T1. Preparation of mesoporous alumina: 1.5 g of oxyethylene-oxypropylene triblock copolymer PEO20-PPO70-PEO20 (P123) was dissolved in 200 mL of ethanol, the pH value of the solution was adjusted to 5.5, 17 g of aluminum isopropoxide was added, the mixture was stirred for 15 min, heated to 75°C, and stirred for 30 h, calcined at 500°C for 2 h, and ball-milled for 1.5 h to obtain mesoporous alumina;

[0069] T2. Preparation of N / C-doped mesoporous alumina: 3 g of glucose and 1.5 g of urea were dissolved in 200 mL of water, 13.5 g of mesoporous alumina was immersed in the solution, the solvent was evaporated, and calcination was performed at 600°C for 120 min to obtain N / C-doped mesoporous alumina;

[0070] T3. MnO2 loading: 3 g of manganese sulfate was dissolved in 200 mL of water, 10 g of N / C-doped mesoporous alumina was added and stirred until uniform, 2.7 g of potassium permanganate was added, the solution was transferred to a stainless steel reaction kettle with a polytetrafluoroethylene liner, sealed, heated to 160°C, and stirred for 12 h, and then cooled to room temperature, the product was filtered, washed, and dried to obtain MnO2-loaded N / C-doped mesoporous alumina;

[0071] T4. Cu / Ni element doping: 1.5 g of copper nitrate and 1 g of nickel nitrate were dissolved in 200 mL of water, 25 g of MnO2-loaded N / C-doped mesoporous alumina was added and immersed for 1 h, filtered, washed, and dried, and then calcination was performed at 550°C for 1.5 h to obtain a catalyst precursor;

[0072] T5. FeOOH loading: 10 g of the catalyst precursor was added to 200 mL of water, 2.5 g of ferrous chloride and 8 g of ammonium bicarbonate were added, heated to 65°C, and stirred for 2 h, and then filtered, washed, and dried, and calcination was performed at 350°C for 75 min to obtain a catalyst.

[0073] Comparative Preparation Example 1

[0074] The difference compared with Preparation Example 3 is that no oxyethylene-oxypropylene triblock copolymer PEO20-PPO70-PEO20 (P123) was added in step T1.

[0075] The details are as follows:

[0076] T1. Preparation of alumina: 200 mL of ethanol was adjusted to a pH value of 5.5, 17 g of aluminum isopropoxide was added, the mixture was stirred for 15 min, heated to 75°C, and stirred for 30 h, calcined at 500°C for 2 h, and ball-milled for 1.5 h to obtain alumina;

[0077] T2. Preparation of N / C doped alumina: 3 g of glucose and 1.5 g of urea were dissolved in 200 mL of water, 13.5 g of mesoporous alumina was immersed in the solution, the solvent was evaporated, and calcination was performed at 600 °C for 120 min to obtain N / C doped alumina;

[0078] T3. MnO2 loading: 3 g of manganese sulfate was dissolved in 200 mL of water, 10 g of N / C doped alumina was added and stirred until mixed uniformly, 2.7 g of potassium permanganate was added, the solution was transferred to a stainless steel reaction kettle with a polytetrafluoroethylene liner, sealed, heated to 160 °C, and stirred for 12 h, then cooled to room temperature, the product was filtered, washed, and dried to obtain MnO2 loaded N / C doped alumina;

[0079] T4. Cu / Ni element doping: 1.5 g of copper nitrate and 1 g of nickel nitrate were dissolved in 200 mL of water, 25 g of MnO2 loaded N / C doped alumina was added and immersed for 1 h, then filtered, washed, and dried, and calcination was performed at 550 °C for 1.5 h to obtain a catalyst precursor;

[0080] T5. FeOOH loading: 10 g of the catalyst precursor was added to 200 mL of water, 2.5 g of ferrous chloride and 8 g of ammonium bicarbonate were added, heated to 65 °C, and stirred for 2 h, then filtered, washed, and dried, and calcination was performed at 350 °C for 75 min to obtain a catalyst.

[0081] Comparative Preparation Example 2

[0082] Compared with Preparation Example 3, the difference is that step T2 is not performed.

[0083] The details are as follows:

[0084] T1. Preparation of mesoporous alumina: 1.5 g of ethylene oxide-propylene oxide triblock copolymer PEO20-PPO70-PEO20 (P123) was dissolved in 200 mL of ethanol, the pH value of the solution was adjusted to 5.5, 17 g of aluminum isopropoxide was added, stirred for 15 min, heated to 75 °C, and stirred for 30 h, then calcination was performed at 500 °C for 2 h and ball milling was performed for 1.5 h to obtain mesoporous alumina;

[0085] T2. MnO2 loading: 3 g of manganese sulfate was dissolved in 200 mL of water, 10 g of mesoporous alumina was added and stirred until mixed uniformly, 2.7 g of potassium permanganate was added, the solution was transferred to a stainless steel reaction kettle with a polytetrafluoroethylene liner, sealed, heated to 160 °C, and stirred for 12 h, then cooled to room temperature, the product was filtered, washed, and dried to obtain MnO2 loaded mesoporous alumina;

[0086] T3. Cu / Ni element doping: 1.5 g of copper nitrate and 1 g of nickel nitrate were dissolved in 200 mL of water, 25 g of the mesoporous alumina supported MnO2 was added, impregnated for 1 h, filtered, washed, dried, calcined at 550 °C for 1.5 h, and a catalyst precursor was prepared;

[0087] T4. FeOOH loading: 10 g of the catalyst precursor was added to 200 mL of water, 2.5 g of ferrous chloride and 8 g of ammonium bicarbonate were added, heated to 65 °C, stirred for 2 h, filtered, washed, dried, calcined at 350 °C for 75 min, and a catalyst was prepared.

[0088] Comparative Preparation Example 3

[0089] Compared with Preparation Example 3, the difference is that step T3 is not performed.

[0090] Specifically as follows:

[0091] T1. Preparation of mesoporous alumina: 1.5 g of ethylene-oxide-propylene-oxide triblock copolymer PEO20-PPO70-PEO20 (P123) was dissolved in 200 mL of ethanol, the pH value of the solution was adjusted to 5.5, 17 g of aluminum isopropoxide was added, the mixture was stirred for 15 min, heated to 75 °C, and stirred for 30 h, calcined at 500 °C for 2 h, and ball-milled for 1.5 h, and mesoporous alumina was prepared;

[0092] T2. Preparation of N / C-doped mesoporous alumina: 3 g of glucose and 1.5 g of urea were dissolved in 200 mL of water, 13.5 g of mesoporous alumina was impregnated in the solution, the solvent was evaporated, and calcination was performed at 600 °C for 120 min, and N / C-doped mesoporous alumina was prepared;

[0093] T3. Cu / Ni element doping: 1.5 g of copper nitrate and 1 g of nickel nitrate were dissolved in 200 mL of water, 25 g of the mesoporous alumina supported MnO2 was added, impregnated for 1 h, filtered, washed, dried, calcined at 550 °C for 1.5 h, and a catalyst precursor was prepared;

[0094] T4. FeOOH loading: 10 g of the catalyst precursor was added to 200 mL of water, 2.5 g of ferrous chloride and 8 g of ammonium bicarbonate were added, heated to 65 °C, stirred for 2 h, filtered, washed, dried, calcined at 350 °C for 75 min, and a catalyst was prepared.

[0095] Comparative Preparation Example 4

[0096] Compared with Preparation Example 3, the difference is that step T4 is not performed.

[0097] Specifically as follows:

[0098] T1. Preparation of mesoporous alumina: 1.5 g of ethylene-oxide-propylene-oxide triblock copolymer PEO20-PPO70-PEO20 (P123) was dissolved in 200 mL of ethanol, the pH value of the solution was adjusted to 5.5, 17 g of aluminum isopropoxide was added, the mixture was stirred for 15 min, heated to 75 °C, and stirred for 30 h, calcined at 500 °C for 2 h, and ball-milled for 1.5 h to obtain mesoporous alumina;

[0099] T2. Preparation of N / C-doped mesoporous alumina: 3 g of glucose and 1.5 g of urea were dissolved in 200 mL of water, 13.5 g of mesoporous alumina was immersed in the solution, the solvent was evaporated, and the mixture was calcined at 600 °C for 120 min to obtain N / C-doped mesoporous alumina;

[0100] T3. MnO2 loading: 3 g of manganese sulfate was dissolved in 200 mL of water, 10 g of N / C-doped mesoporous alumina was added and stirred until uniform, 2.7 g of potassium permanganate was added, the solution was transferred to a stainless steel reaction kettle with a polytetrafluoroethylene liner, sealed, heated to 160 °C, and stirred for 12 h, and then cooled to room temperature, the product was filtered, washed, and dried to obtain MnO2-loaded N / C-doped mesoporous alumina;

[0101] T4. FeOOH loading: 10 g of MnO2-loaded N / C-doped mesoporous alumina was added to 200 mL of water, 2.5 g of ferrous chloride and 8 g of ammonium bicarbonate were added, heated to 65 °C, and stirred for 2 h, then filtered, washed, and dried, and calcined at 350 °C for 75 min to obtain the catalyst.

[0102] Comparative Preparation Example 5

[0103] The difference compared with Preparation Example 3 is that step T5 is not performed.

[0104] The details are as follows:

[0105] T1. Preparation of mesoporous alumina: 1.5 g of ethylene-oxide-propylene-oxide triblock copolymer PEO20-PPO70-PEO20 (P123) was dissolved in 200 mL of ethanol, the pH value of the solution was adjusted to 5.5, 17 g of aluminum isopropoxide was added, the mixture was stirred for 15 min, heated to 75 °C, and stirred for 30 h, calcined at 500 °C for 2 h, and ball-milled for 1.5 h to obtain mesoporous alumina;

[0106] T2. Preparation of N / C-doped mesoporous alumina: 3 g of glucose and 1.5 g of urea were dissolved in 200 mL of water, 13.5 g of mesoporous alumina was immersed in the solution, the solvent was evaporated, and the mixture was calcined at 600 °C for 120 min to obtain N / C-doped mesoporous alumina;

[0107] T3. MnO2 loading: 3 g of manganese sulfate was dissolved in 200 mL of water, 10 g of N / C doped mesoporous alumina was added and stirred until mixed uniformly, 2.7 g of potassium permanganate was added, the solution was transferred into a stainless steel reaction kettle with a polytetrafluoroethylene liner, sealed, heated to 160°C, stirred for 12 h, cooled to room temperature, the product was filtered, washed, and dried to obtain MnO2 loaded N / C doped mesoporous alumina;

[0108] T4. Cu / Ni element doping: 1.5 g of copper nitrate and 1 g of nickel nitrate were dissolved in 200 mL of water, 25 g of MnO2 loaded N / C doped mesoporous alumina was added and soaked for 1 h, filtered, washed, dried, and calcined at 550°C for 1.5 h to obtain the catalyst.

[0109] Test Example 1

[0110] The specific surface area and pore volume of the catalysts prepared in Preparation Examples 1-3 and Comparative Preparation Examples 1-5 of the present application were determined by using an ASAP2460 full-automatic specific surface and porosity analyzer produced by Micromeritics Instrument Company, USA, and the results are shown in Table 1.

[0111] Table 1

[0112]

[0113] As shown in the above table, the catalysts prepared in Preparation Examples 1-3 of the present application have a larger specific surface area and a larger pore volume.

[0114] Test Example 2

[0115] The catalyst prepared in Preparation Example 1-3 or Comparative Preparation Example 1-5 was added to a catalytic ozone system, the initial dosage was 150 g / L, the ozone inlet mass concentration was set to 9 mg / L, and the reaction time was set to 40 min. The initial simulated wastewater had a tetracycline mass concentration of 100 mg / L and a pH of 7. After 40 min of continuous treatment, 5 mL of simulated wastewater was taken, the simulated wastewater was filtered through a water system filter membrane with a pore size of 0.45 μm, the absorbance was determined by using a UV spectrophotometer, and the mass concentration of tetracycline was calculated. The results are shown in Table 2.

[0116] Table 2

[0117]

[0118] As shown in the above table, the catalysts prepared in Preparation Examples 1-3 of the present application have a better catalytic ozone oxidation degradation effect on organic matter.

[0119] Example 1

[0120] In combination Figure 1 with the process flow, the method described in the present embodiment comprises the following steps:

[0121] S1. For the chemical high-salinity wastewater system with a mass fraction of 15%, an activated carbon adsorption system is used to remove solid suspended substances and part of the adsorbable total organic carbon in the high-salinity water. The activated carbon adsorption system adopts a fixed bed tower structure, the activated carbon is coconut activated carbon with an iodine value range of 1000 mg / g, the filling height of the activated carbon bed is 1.5 meters, the hydraulic retention time of the activated carbon in contact with the high-salinity water is 30 minutes, aromatic hydrocarbon organic matters in the high-salinity water are adsorbed in the contact process, the adsorption temperature is 55℃, the pH is 10, and the ss in the high-salinity water is intercepted at the same time. When the pressure before and after the bed layer exceeds 0.06 Mpa, backwashing starts, the intensity of backwashing water is 5.0 L / (s·m 2 ), the intensity of backwashing gas is 10 L / (s·m 2 ), and backwashing lasts for 5 minutes.

[0122] The high-salinity water after the bed layer pressure drop adsorption enters the next nanometer ozone catalytic oxidation unit for further treatment.

[0123] S2. The nanometer ozone catalytic system is used to further oxidize the organic matters in the high-salinity water. The nanometer catalytic ozone oxidation system includes two parts of nanometer ozone pre-oxidation and catalytic ozone oxidation. First, oxygen is generated by an oxygen generator, the generated oxygen enters an ozone generator to generate ozone, the ozone concentration is 120-140 mg / L, the ozone is cut into nanometer ozone bubbles with a particle size range of 100-200 nm by multiple stages in the nanometer ozone system, and is dissolved in the high-salinity water to pre-oxidize the total organic carbon. The volume ratio of ozone to high-salinity water is 1 / 1, the reaction time is 30 minutes, the reaction temperature is 45℃, and the reaction pH is 7.5. The gas-water mixture after pre-oxidation is injected into a catalytic ozone oxidation tower by a jetifier, the jet outlet speed is 10 m / s, the catalytic ozone oxidation tower adopts a fixed bed form, the catalyst is a heterogeneous catalyst, the catalyst catalyzes the ozone to generate hydroxyl radicals (·OH) to oxidize the total organic carbon in the high-salinity water that is not adsorbed by the activated carbon, the filling height of the fixed bed catalyst is 2.5 m, the particle size range of the catalyst is 3-5 mm, the ozone contact reaction time with the catalyst is 30 minutes, the reaction temperature is 45℃, the reaction pH is 7.5, part of the tail gas after the reaction is returned to the nanometer ozone system for continuous reaction, the remaining tail gas is collected and treated by a tail gas destroyer before being discharged, the reflux ratio is 2 / 1, and the high-salinity water after oxidation enters a targeted adsorption system.

[0124] S3. According to the molecular structure of organic pollutants and the corresponding functional groups, select the adsorbent without functional groups for adsorption, adopt tower structure, the filling height of adsorbent is 1.5 m, the diameter of adsorbent ranges from 0.2 to 1.5 mm, the upward flow rate of high-salinity water in the adsorption tower is 3.0 m / h, the hydraulic retention time is 45 min, the adsorption temperature is 35℃, and the adsorption pH is 5.5. After adsorption saturation, desorption and activation are carried out using a desorption agent, the desorption agent is 8% sodium hydroxide solution, the amount of desorption agent is 3 times the volume of adsorbent, the flow rate of desorption agent is 3.0 m / h, the total organic carbon in high-salinity water is separated by targeted adsorption, and after meeting the requirements, it enters the salt recovery system.

[0125] Example 2

[0126] In combination Figure 1 with the process flow, the method described in the present embodiment includes the following steps:

[0127] S1. For a chemical high-salinity wastewater system with a mass fraction of 20%, an activated carbon adsorption system is used to remove solid suspended matter and part of the adsorbable total organic carbon in high-salinity water. The activated carbon adsorption system adopts a fixed bed tower structure, the activated carbon uses coconut shell activated carbon with an iodine value ranging from 1000 mg / g, the activated carbon bed layer filling height is 2.0 meters, the hydraulic retention time of activated carbon contact with high-salinity water is 60 min, aromatic hydrocarbon organic matter is adsorbed during the contact process, the adsorption temperature is 55℃, the pH is 10, and ss in high-salinity water is intercepted at the same time. When the pressure before and after the adsorption bed layer exceeds 0.06 Mpa, backwashing begins, the intensity of backwashing water is 7.0 L / (s·m 2 ),the intensity of backwashing gas is 12 L / (s·m 2 ),and backwashing lasts for 10 min.

[0128] When the bed layer pressure drop adsorbed high-salinity water enters the next nanometer ozone catalytic oxidation unit for further treatment.

[0129] S2. Further oxidize the organic matter in the high-salinity water through a nano-ozone catalytic system. The nano-catalytic ozone oxidation system includes two parts, nano-ozone pre-oxidation and catalytic ozone oxidation: first, air passes through an oxygen generator to generate oxygen, the generated oxygen enters an ozone generator to generate ozone, the ozone concentration is 120-140 mg / L, the ozone is cut into nano-ozone bubbles with a particle size range of 100-200 nm in a multi-stage nano-ozone system, and is dissolved in the high-salinity water to pre-oxidize the total organic carbon therein. The volume ratio of ozone to high-salinity water is 2 / 1, the reaction time is 45 min, the reaction temperature is 45°C, and the reaction pH is 7.5. The gas-water mixture after pre-oxidation is injected into a catalytic ozone oxidation tower through a jetifier, the jet outlet speed is 15 m / s, the catalytic ozone oxidation tower adopts a fixed bed form, the catalyst is a heterogeneous catalyst, the catalyst catalyzes the ozone to generate hydroxyl radicals (·OH) to oxidize the total organic carbon in the high-salinity water that is not adsorbed by the activated carbon, the filling height of the fixed bed catalyst is 3.0 m, the particle size range of the catalyst is 3-5 mm, the ozone and the catalyst contact for a reaction time of 45 min, the reaction temperature is 45°C, the reaction pH is 7.5, part of the tail gas after the reaction is returned to the nano-ozone system for continuous reaction, the remaining tail gas is collected and treated in a tail gas destroyer before being discharged, the reflux ratio is 3 / 1, and the oxidized high-salinity water enters the targeted adsorption system.

[0130] S3. According to the different molecular structures and corresponding functional groups of the organic pollutants, an adsorbent containing an ester group is selected for targeted adsorption, a tower structure is adopted, the filling height of the adsorbent is 2.0 m, the diameter range of the adsorbent is 0.2-1.5 mm, the upward flow rate of the high-salinity water in the adsorption tower is 2.0 m / h, the hydraulic retention time is 60 min, the adsorption temperature is 35°C, and the adsorption pH is 4.0. After saturation, an eluent is used for elution and activation, the eluent is a 6% sodium hydroxide solution, the eluent amount is 2.5 times the volume of the adsorbent, and the eluent flow rate is 2.0 m / h. The total organic carbon in the high-salinity water is separated by targeted adsorption, and after meeting the requirements, the high-salinity water enters the salt recovery system.

[0131] Example 3

[0132] In combination Figure 1 with the process flow, the method described in the present embodiment includes the following steps:

[0133] S1. For the chemical industry high-salinity sewage system with a mass fraction of 25%, an activated carbon adsorption system is used to remove solid suspended matter and part of the adsorbable total organic carbon in high-salinity water. The activated carbon adsorption system adopts a fixed bed tower structure, the activated carbon uses coconut activated carbon, the iodine value range is 1100 mg / g, the filling height of the activated carbon bed is 2.5 meters, the hydraulic retention time of the activated carbon in contact with high-salinity water is 60 minutes, the aromatic hydrocarbon organic matter in the contact process is adsorbed, the adsorption temperature is 55℃, the pH is 10, and the ss in the high-salinity water is intercepted. When the pressure before and after the bed layer exceeds 0.06 Mpa, backwashing starts, the intensity of the backwashing water is 10.0 L / (s·m 2 ), the intensity of the backwashing gas is 15 L / (s·m 2 ), and the backwashing time is 15 minutes.

[0134] When the bed layer pressure drop adsorbed high-salinity water enters the next nanometer ozone catalytic oxidation unit for further treatment.

[0135] S2. The nanometer ozone catalytic system is used to further oxidize the organic matter in the high-salinity water. The nanometer catalytic ozone oxidation system includes two parts: nanometer ozone pre-oxidation and catalytic ozone oxidation. First, air passes through an oxygen generator to produce oxygen, the generated oxygen enters an ozone generator to generate ozone, the ozone concentration is 120-140 mg / L, the ozone is cut into nanometer ozone bubbles with a particle size range of 50-100 nm in the nanometer ozone system by multiple stages, and is dissolved in high-salinity water to pre-oxidize the total organic carbon. The volume ratio of ozone to high-salinity water is 3 / 1, the reaction time is 60 minutes, the reaction temperature is 45℃, and the reaction pH is 7.5. The pre-oxidized gas-water mixture is injected into the catalytic ozone oxidation tower through a jet device, the jet outlet speed is 12 m / s, the catalytic ozone oxidation tower adopts a fixed bed form, the catalyst uses a heterogeneous catalyst, the catalyst catalyzes the ozone to generate hydroxyl radicals (·OH) to oxidize the total organic carbon in the high-salinity water that is not adsorbed by the activated carbon, the filling height of the fixed bed catalyst is 4.0 m, the particle size range of the catalyst is 3-5 mm, the ozone contact reaction time with the catalyst is 60 minutes, the reaction temperature is 45℃, the reaction pH is 7.5, part of the tail gas after the reaction is returned to the nanometer ozone system for continuous reaction, the remaining is collected and treated by the tail gas destroyer before being discharged, the reflux ratio is 4 / 1, and the oxidized high-salinity water enters the targeted adsorption system.

[0136] S3. According to the molecular structure and corresponding functional groups of the organic pollutants, an adsorbent containing acrylamide group is selected for targeted adsorption, a tower structure is adopted, the filling height of the adsorbent is 3.5 m, the diameter of the adsorbent ranges from 0.2 to 1.5 mm, the upward flow rate of the high-salt water in the adsorption tower is 1.0 m / h, the hydraulic retention time is 60 min, the adsorption temperature is 35℃, and the adsorption pH is 4.0. After adsorption saturation, a desorption agent is used for desorption and activation, the desorption agent is 4% sodium hydroxide solution, the amount of the desorption agent is 4.0 times the volume of the adsorbent, the flow rate of the desorption agent is 1.0 m / h, the total organic carbon in the high-salt water is separated by targeted adsorption, and after meeting the requirements, the high-salt water enters a salt recovery system.

[0137] After the above treatment, the main treatment effects are summarized in Table 3 as follows:

[0138] Table 3 Summary of treatment effects

[0139]

[0140] As can be seen from the above table, after the combined process of the present application, the total organic carbon removal rate can reach 97.6%, and the removal effect is very good.

[0141] The above description is only the preferred embodiment of the present application, and is not intended to limit the present application. Any modification, equivalent replacement, improvement, etc. made within the spirit and principles of the present application shall be included in the protection scope of the present application.

Claims

1. A method for high-salinity water total organic carbon polishing, characterized in that, It comprises the following steps: S1. Removing solid suspended matters and part of total organic carbon in high-salinity water by using activated carbon adsorption system; S2. Oxidizing organic matters in high-salinity water by using nano-ozone catalysis system; S3. High-salinity water after oxidation by nano-ozone catalysis system enters targeted adsorption system to separate residual total organic carbon in high-salinity water, realizing deep purification of total organic carbon in high-salinity water; The nano-ozone catalysis system comprises a nano-ozone pre-oxidation system and a nano-catalytic ozone oxidation system; The catalytic ozone tower in the nano-catalytic ozone oxidation system adopts a fixed bed form, and the catalyst is a heterogeneous catalyst; The preparation method of the catalyst is as follows: T1. Preparation of mesoporous alumina: dissolving a pore former in ethanol, adjusting the pH value of the solution, adding aluminum isopropoxide, stirring and uniformly mixing, heating and stirring for reaction, calcining, and ball milling to prepare mesoporous alumina; T2. Preparation of N / C-doped mesoporous alumina: dissolving glucose and urea in water to obtain a solution, immersing mesoporous alumina in the solution, volatilizing dry solvents, and calcining to prepare N / C-doped mesoporous alumina; T3. MnO2 loading: dissolving a manganese salt in water, adding potassium permanganate after uniformly mixing the N / C-doped mesoporous alumina, transferring to a stainless steel reaction kettle with a polytetrafluoroethylene liner, sealing, heating and stirring for reaction, cooling to room temperature, filtering the product, washing, and drying to prepare MnO2-loaded N / C-doped mesoporous alumina; T4. Cu / Ni element doping: dissolving copper and nickel salts in water, adding MnO2-loaded N / C-doped mesoporous alumina, immersing, filtering, washing, drying, calcining to prepare a catalyst precursor; T5. FeOOH loading: adding the catalyst precursor to water, adding ferrous salt and ammonium bicarbonate, heating and stirring for reaction, filtering, washing, drying, and calcining to prepare a catalyst.

2. The method of claim 1, wherein, The mass fraction of salt in the high-salt water is 10% to 26.5%, the adsorption temperature is 40 to 70 DEG C, the pH is 9 to 12, the hydraulic residence time of the activated carbon and the high-salt water is 30 to 180 min, the filling height of the activated carbon bed is 1.0 to 3.0 m, the intensity of the backwashing water for backwashing the activated carbon bed is 5 to 10 L / (s·m 2 ), and the intensity of the backwashing gas is 10 to 15 L / (s·m 2 ).

3. The method of claim 2, wherein, The activated carbon is coconut shell activated carbon, and the iodine value range is 900-1200 mg / g; the activated carbon backwashing cycle is 1-3 days, and the backwashing time is 5-15 min.

4. The method of claim 1, wherein, In the nano-ozone pre-oxidation system, air passes through an oxygen generator to generate oxygen, the generated oxygen enters an ozone generator to generate ozone, the ozone pressure generated by the ozone generator is 0.07-0.09 Mpa, the nano-ozone bubbles are cut by multiple stages in the nano-ozone system, the particle size of the formed nano-ozone bubbles ranges from 50 to 200 nm, the nano-ozone bubbles are dissolved in high-salinity water to pre-oxidize total organic carbon, the reaction time is 30-120 min, the reaction temperature is 40-60℃, and the reaction pH is 6-9.

5. The method of claim 1, wherein, In the nano-catalytic ozone oxidation system, the gas-water mixture is pumped into the catalytic ozone tower by the jet pump, the speed of the jet outlet is 10-15 m / s, the filling height of the catalyst in the fixed bed is 1.5-4.5 m, the particle size of the catalyst is 3-5 mm, the contact reaction time of ozone and catalyst is 30-60 min, the reaction temperature is 40-50℃, the reaction pH is 7-8, the volume ratio of ozone and high-salt water mixture is 3 / 1-1 / 1, the mass ratio of total ozone dosage and total organic carbon is 5 / 1-10 / 1, a pressure stabilizing valve is arranged at the top of the catalytic ozone tower, the pressure setting range is 0.09-0.12 MPa, part of the tail gas is backflowed into the nano-ozone catalytic system for continuous reaction, and the remaining part is collected to the tail gas destroyer for treatment and then exhausted.

6. The method of claim 1, wherein, The target adsorption system selects a target adsorbent for adsorption according to the molecular structure and functional groups of the organic pollutants, the filling height of the target adsorbent is 1.0-5.0 m, the hydraulic retention time of the target adsorbent and high-salt water is 30-90 min, the adsorption temperature is 30-40℃, and the adsorption pH is 4-6.

7. The method of claim 6, wherein, The target adsorbent takes super-high cross-linked polystyrene as a substrate, introduces at least one kind of targeting group of acrylamide group, cyano group and ester group, and the diameter of the target adsorbent ranges from 0.2 mm to 2.0 mm.

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