CN114436443A - Energy-saving treatment method for high-salt organic wastewater generated in caustic soda preparation through ionic membrane - Google Patents
Energy-saving treatment method for high-salt organic wastewater generated in caustic soda preparation through ionic membrane Download PDFInfo
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Abstract
The invention relates to an energy-saving treatment method of high-salt organic wastewater for preparing caustic soda by using an ionic membrane, which comprises the steps of catalytic oxidation and the like. The treatment method can effectively save the energy consumption of organic wastewater treatment.
Description
Technical Field
The invention relates to a divisional application of a Chinese patent with application number of 201910597797.0 and application date of 2019.07.04, namely a method for treating high-salt organic wastewater generated in the production process of epoxy resin, and belongs to the technical field of wastewater treatment. More particularly, the invention relates to an energy-saving treatment method of high-salt organic wastewater for preparing caustic soda by using an ionic membrane.
Background
The epoxy resin is a generic name of a polymer having two or more epoxy groups in a molecule. It is a polycondensation product of epichlorohydrin and bisphenol A or a polyol. Because of the chemical activity of the epoxy group, the epoxy group can be opened by a plurality of compounds containing active hydrogen, and the epoxy group is cured and crosslinked to form a network structure, so that the epoxy group is a thermosetting resin. The bisphenol A epoxy resin has the largest yield and the most complete variety, and the new modified variety is continuously increased and the quality is continuously improved.
The epoxy resin is researched from 1958 in China, and is put into industrial production at a high speed, so that the epoxy resin is developed vigorously all over the country, and various types of novel epoxy resins are produced in addition to the common bisphenol A-epoxy chloropropane type epoxy resin so as to meet the urgent needs of national defense construction and national economic departments.
In the production process of the epoxy resin, a large amount of sodium chloride is produced as a byproduct, and in order to separate the sodium chloride from the resin, a water solution method is adopted for separation, so that a large amount of high-salt-content wastewater is formed. The part of wastewater belongs to a mixture of high-concentration organic wastewater and inorganic wastewater, has very complex components and can be mainly classified into 3 types: (1) the organic matter is mainly a macromolecular intermediate product, a small amount of incompletely reacted raw materials, organic solvent toluene, aging resin and the like in the production process of the epoxy resin; (2) ions such as Na, Cl-, OH-, etc., derived from production raw materials and by-products of the reaction; (3) water brought by raw material caustic soda in the water production process, generated water, washing water and the like.
The prior art has the following treatment methods for the wastewater: (1) concentration and incineration method. Because the epoxy resin wastewater contains a large amount of Na, Cl-and OH-in the incinerator, the epoxy resin wastewater can exist in a fused salt form, so that the incinerator is easy to block, the treatment cost is high, and the practicability and the economical efficiency are poor. (2) And (3) a dilution biochemical method. The method not only occupies large area, but also has high wastewater treatment cost. And because the wastewater contains more oily organic matters with larger molecular weight, alkali and salts, the conventional treatment method is difficult to completely remove, so the method is not suitable for being popularized in the epoxy resin industry.
The prior domestic effective treatment and salt recovery process is a closed cycle treatment process for epoxy resin high-salt wastewater. Firstly, separating oil phase and water phase of the epoxy resin high-salt-content wastewater to separate oily organic matters, concentrating, crystallizing and filtering the wastewater to obtain crystallized salt and crystallized mother liquor, and using condensed water as washing water of a resin finished product; and mixing the crystallization mother liquor with the next batch of epoxy resin wastewater, and returning to the first step for separation to form a closed circulation loop. The pretreatment (including removal of organic and inorganic substances) by this method is not ideal, resulting in poor evaporation efficiency and operational reliability, and is not suitable for long-term operation. Secondly, the obtained salt has poor quality, cannot obtain high-quality industrial salt, and has poor economic benefit and large steam consumption. In addition, water-soluble organic impurities are not discharged from a circulating system, and the stability of resin production and the quality of resin can be influenced along with the long-term recycling of crystallization mother liquor. Similar concentration and crystallization methods are adopted in Taizi and foreign capital epoxy resin production enterprises of more than ten thousand tons in China, namely, after salt-containing wastewater is separated by an organic phase, an inorganic phase is neutralized, concentrated and crystallized to obtain industrial salt for industrial production. However, the salt recovered by the method can only be used as a snow melting agent and a printing and dyeing auxiliary agent, the recycling level is low, the export sale of the recovered salt is easily restricted by external factors, and enterprises are very passive.
Therefore, in view of the drawbacks of the prior art, it is very desirable to explore a method for mineralizing and recycling organic pollutants in high-salt organic wastewater generated in the production process of epoxy resin, with low cost and energy consumption. The present inventors have completed the present invention through a large number of experiments and studies.
Disclosure of Invention
[ problem to be solved ]
The invention aims to provide an energy-saving treatment method of high-salt organic wastewater for preparing caustic soda by using an ionic membrane.
[ solution ]
The invention is realized by the following technical scheme.
The invention relates to an energy-saving treatment method of high-salinity organic wastewater for preparing caustic soda by using an ionic membrane.
The processing method comprises the following steps:
A. catalytic oxidation
High-salt organic wastewater, a catalyst and hydrochloric acid generated in the production process of epoxy resin are respectively conveyed into a storage tank 1 through a pipeline 11 and a pipeline 12, the pH of the high-salt organic wastewater is adjusted to 2-6 by adjusting the flow rates of the wastewater and the hydrochloric acid, then the adjusted high-salt wastewater is conveyed by a high-pressure pump 2, meanwhile, oxygen-containing gas is conveyed by a pipeline 31, the high-salt organic wastewater and the high-salt organic wastewater are conveyed into an oxidation tower 5 from the bottom of the tower through an oxidation tower feeding pipeline 51 through a heat exchanger 3 and a heater 4, and the high-salt organic wastewater and the oxygen-containing gas are subjected to oxidation treatment for 0.5-5 h under the conditions of the temperature of 150-300 ℃ and the pressure of 1.0-9.0 MPa; the oxidation wastewater and the oxidation tail gas are discharged from an oxidation tower discharge pipeline 52 positioned at the top of the oxidation tower 5, enter a gas-liquid separator 6 through a pipeline 61 after heat exchange by a heat exchanger 3 for gas-liquid separation, the separated gas phase is mainly a mixed gas containing CO2 and water vapor and is discharged from a gas-phase discharge pipeline 62 positioned at the top of the gas-liquid separator 6, and the separated liquid phase is discharged from a liquid-phase discharge pipeline 63 at the bottom of the gas-liquid separator 6 and is sent to a subsequent treatment step for treatment;
B. recovery of catalyst
Conveying oxidized wastewater discharged from a liquid-phase water outlet pipeline 63 at the bottom of the gas-liquid separator 6 into a pH adjusting tank 7 provided with a stirring paddle through an adjusting tank wastewater feeding pipeline 71, conveying alkali liquor into the pH adjusting tank 7 through an adjusting tank alkali liquor feeding pipeline 72, adjusting the pH of the oxidized wastewater to 6-9, then allowing the oxidized wastewater to enter a sludge dehydrator 8 for solid-liquid separation, discharging the obtained solid phase from the lower part of the sludge dehydrator 8 through a solid-phase discharging pipeline 81, and conveying the solid phase to the top of the storage tank 1 through a catalyst pipeline 12; the resulting aqueous phase is discharged from the side of the sludge dewatering machine 8, transferred to the resin tower 10 through the pipe 82 by the pump 9 to remove high-valence metal ions, and the clean brine is discharged from the resin tower discharge pipe 101 located at the bottom of the resin tower 10, and it is used for preparing caustic soda by ionic membrane.
According to a preferred embodiment of the present invention, in the step a, the high-salinity organic wastewater is wastewater with pH 8-12, wherein the sodium chloride content is 5-25% by weight, and the TOC content is 2000-20000 mg/L.
According to another preferred embodiment of the present invention, in the step a, the concentration of the hydrochloric acid is 1.0 to 4.0N.
According to another preferred embodiment of the present invention, in step a, the catalyst is one or more catalysts selected from metal oxides or metal salts of iron, cadmium, vanadium, nickel, copper, manganese, cobalt, molybdenum or cerium; the dosage of the catalyst is 0.1-2.0% of the weight of the wastewater.
According to another preferred embodiment of the present invention, in the step B, the high salinity organic wastewater and the oxygen-containing gas are oxidized for 0.5 to 5 hours at a temperature of 150 to 300 ℃ and a pressure of 1.0 to 9.0MPa, preferably at a temperature of 160 to 280 ℃ and a pressure of 1.2 to 7.5MPa for 1 to 4 hours, and more preferably at a temperature of 180 to 260 ℃ and a pressure of 1.5 to 5.0MPa for 2 to 3 hours.
According to another preferred embodiment of the present invention, in step A, the oxidation tower 5 is an oxidation reactor having a hollow tower structure.
According to another preferred embodiment of the present invention, in step A, the oxygen-containing gas is air, oxygen-enriched air or industrially pure oxygen.
According to another preferred embodiment of the invention, in step B, the alkaline solution is a sodium hydroxide solution having an alkali concentration of 2.0-10.0N.
According to another preferred embodiment of the present invention, in step B, the resin column 14 is a resin column having a filtering baffle structure and packed with a chelating ion exchange resin.
The present invention will be described in more detail below.
The invention relates to a method for treating high-salt organic wastewater generated in the production process of epoxy resin.
The processing method comprises the following steps:
A. catalytic oxidation
High-salt organic wastewater, a catalyst and hydrochloric acid generated in the production process of epoxy resin are respectively conveyed into a storage tank 1 through a pipeline 11 and a pipeline 12, the pH of the high-salt organic wastewater is adjusted to 2-6 by adjusting the flow rates of the wastewater and the hydrochloric acid, then the adjusted high-salt wastewater is conveyed by a high-pressure pump 2, meanwhile, oxygen-containing gas is conveyed by a pipeline 31, the high-salt organic wastewater and the high-salt organic wastewater are conveyed into an oxidation tower 5 from the bottom of the tower through an oxidation tower feeding pipeline 51 through a heat exchanger 3 and a heater 4, and the high-salt organic wastewater and the oxygen-containing gas are subjected to oxidation treatment for 0.5-5 h under the conditions of the temperature of 150-300 ℃ and the pressure of 1.0-9.0 MPa; the oxidation wastewater and the oxidation tail gas are discharged from an oxidation tower discharge pipeline 52 positioned at the top of the oxidation tower 5, enter a gas-liquid separator 6 through a pipeline 61 after heat exchange by a heat exchanger 3 for gas-liquid separation, the separated mixed gas containing CO2 and water vapor is discharged from a gas-phase discharge pipeline 62 positioned at the top of the gas-liquid separator 6, and the separated liquid phase is discharged from a liquid-phase discharge pipeline 63 at the bottom of the gas-liquid separator 6 and is sent to the subsequent treatment step for treatment;
in the present invention, the epoxy resin production method is specifically referred to documents CN105131252A, CN105153402A and the like.
In the invention, the high-salt organic wastewater generated in the epoxy resin production process is pH 8-12 wastewater with the sodium chloride content of 5-25% by weight and the TOC total organic carbon content of 2000-20000 mg/L.
In the invention, the pH value of the high-salt organic wastewater is adjusted to 2-6 by adjusting the flow rates of the high-salt organic wastewater and hydrochloric acid. If the pH of the high-salt organic wastewater used for the catalytic oxidation is not within the above range, it is disadvantageous to efficiently convert oxygen of the oxygen-containing gas into OH hydroxyl radicals during the catalytic oxidation, thus affecting the oxidation effect. Therefore, it is very important to adjust the pH of the high-salt organic wastewater to 2 to 6. The concentration of the hydrochloric acid used in the invention is 1.0-4.0N.
According to the invention, the catalyst is one or more catalysts selected from metal oxides or metal salts of iron, cadmium, vanadium, nickel, copper, manganese, cobalt, molybdenum or cerium; the catalysts used in the present invention are products currently marketed, for example, by Suzhou and chemical industries, Inc. under the trade names cupric chloride, nickel chloride; products sold under the trade names ferrous chloride, ferric chloride by Tianjin ShangZhi commercial products Co., Ltd; a product sold under the trade name vanadium pentoxide by Baichuan vanadium industries, Inc. in Jiangxi; products sold by Hubei Xin Rundchemical Limited under the tradenames cobalt oxide, nickel protoxide, cadmium oxide; products sold under the trade names cerium nitrate and cerium oxide by Qingda Fine chemical Co., Ltd, Yutai county; products sold under the trade names manganese oxide and manganese carbonate by Shanghai Syngnathus chemical Co., Ltd; a product sold under the trade name molybdenum pentachloride by shanghai advanced materials science and technology ltd.
In the invention, the dosage of the catalyst is 0.1-2.0% of the weight of the wastewater. If the dosage of the catalyst is less than 0.1 percent, the catalytic effect is poor, and the requirement of treating the high-salt organic wastewater can not be met; if the amount of the catalyst is more than 2.0%, the catalyst is excessive, increasing the treatment cost; therefore, the amount of the catalyst is suitably 0.1 to 2.0%, preferably 0.6 to 1.6%, more preferably 0.9 to 1.2%.
In the invention, the high-salinity organic wastewater and the oxygen-containing gas are oxidized for 0.5 to 5 hours at the temperature of 150 to 300 ℃ and the pressure of 1.0 to 9.0 MPa.
The oxygen-containing gas used in the present invention is air, oxygen-enriched air or industrially pure oxygen.
In the invention, when the pressure and time of the oxidation treatment are in the range, if the temperature of the oxidation treatment is lower than 150 ℃, the oxidation effect of the pretreated wastewater is poor; if the oxidation treatment temperature is higher than 300 ℃, the oxidation effect is not obviously improved, but the energy consumption is overlarge and is not economical; therefore, the temperature of the oxidation treatment is preferably 150 to 300 ℃, more preferably 160 to 280 ℃, and most preferably 180 to 260 ℃.
Similarly, when the temperature and time of the oxidation treatment are within the above ranges, if the pressure of the oxidation treatment is less than 1.0MPa, the high-salinity wastewater is vaporized at the above temperature; if the oxidation treatment pressure is higher than 9.0MPa, the oxidation effect of the high-salinity wastewater is not greatly influenced; therefore, it is reasonable that the oxidation treatment pressure is 1.0 to 9.0MPa, preferably 1.2 to 7.5MPa, and more preferably 1.5 to 5.0 MPa.
When the temperature and pressure of the oxidation treatment are within the above ranges, if the time of the oxidation treatment is less than 0.5h, the oxidation reaction is not complete; if the oxidation treatment time is longer than 5.0h, the TOC removal rate is basically kept unchanged; therefore, the oxidation treatment time is suitably 0.5 to 5.0 hours, preferably 1.0 to 4.0 hours, more preferably 2.0 to 3.0 hours.
Preferably, the pretreated wastewater and the oxygen-containing gas are subjected to oxidation treatment for 1.0-4.0 h at the temperature of 160-280 ℃ and the pressure of 1.2-7.5 MPa.
More preferably, the pretreated wastewater and the oxygen-containing gas are oxidized for 2.0 to 3.0 hours at the temperature of 180 to 260 ℃ and under the pressure of 1.5 to 5.0 MPa.
In the invention, the heat exchanger 3 is used for recovering heat in the oxidized brine, and the oxidized brine is used as a heat source to heat the high-salinity organic wastewater which needs to enter the oxidation system, thereby saving resources; the heater 4 is used for supplementing heat so that the temperature of the high-salinity wastewater reaches the required oxidation reaction temperature, and the heater 4 is heated by adopting steam or heat conduction oil.
The heat exchanger 3 and the heater 4 used in the present invention are both heat exchangers, and are sold, for example, by Shandong Yian Heat exchanger Co., Ltd under the trade name of a shell-and-tube heat exchanger or a double-tube heat exchanger, and sold by Weike Heat exchanger Co., Ltd, New rural area under the trade name of a plate heat exchanger.
In the present invention, the oxidation tower 5 is an oxidation reactor having a hollow tower structure. The oxidation tower 5 used in the present invention is a nonstandard pressure vessel currently sold in the market, for example, a product manufactured and sold by Nanjing Huaxing pressure vessel manufacturing Co., Ltd., Dingzhou Dingsheng pressure vessel Co., Ltd., and the like.
According to the invention, oxidation wastewater and oxidation tail gas discharged from a discharge pipeline 52 positioned at the top of an oxidation tower 5 enter a gas-liquid separator 6 through a pipeline 61 after heat exchange by a heat exchanger 3 for gas-liquid separation, and the oxidation tail gas discharged from a tail gas pipeline 62 at the top of the gas-liquid separator 6 is a mixed gas containing 20-80% of CO2, 0.5-0.8% of water, 2.0-5.0% of oxygen and 14.2-75.0% of other gases. In the present invention, the contents of CO2 and O2 in the mixed gas were measured by analysis using a 1902-type austenite gas analyzer sold by shanghai ag ze instruments ltd, and the moisture content was measured using a dew point meter sold by shanghai toruli instruments ltd.
B. Recovery of catalyst
Conveying oxidized wastewater discharged from a liquid-phase water outlet pipeline 63 at the bottom of the gas-liquid separator 6 into a pH adjusting tank 7 provided with a stirring paddle through an adjusting tank wastewater feeding pipeline 71, conveying alkali liquor into the pH adjusting tank 7 through an adjusting tank alkali liquor feeding pipeline 72, adjusting the pH of the oxidized wastewater to 6-9, then allowing the oxidized wastewater to enter a sludge dehydrator 8 for solid-liquid separation, discharging the obtained solid phase from the lower part of the sludge dehydrator 8 through a solid-phase discharging pipeline 81, and conveying the solid phase to the top of the storage tank 1 through a catalyst pipeline 12; the resulting aqueous phase is discharged from the side of the sludge dewatering machine 8, transferred to the resin tower 10 through the pipe 82 by the pump 9 to remove high-valence metal ions, and the clean brine is discharged from the resin tower discharge pipe 101 located at the bottom of the resin tower 10, and it is used for preparing caustic soda by ionic membrane.
In the invention, the purpose of adjusting the pH value of the oxidation wastewater to 6-9 is to enable the catalyst to form a precipitate, which is beneficial to recovery. The pH value lower than 6 or higher than 9 is not favorable for the formation of precipitate of the catalyst, thereby affecting the recovery effect of the catalyst. Therefore, it is reasonable to adjust the pH of the oxidized wastewater to 6-9, preferably 6.5-7.5.
The sludge dewatering machine 8 used in the present invention is well known to those skilled in the art, and is a product currently marketed, for example, by Yixing Fengke environmental protection equipment Co., Ltd under the trade name of thailair sludge dewatering machine, and by Yuzhou Donglong chemical machinery Co., Ltd under the trade name of high pressure membrane filter press.
In the invention, the water phase discharged from the side of the sludge dewatering machine 8 is used for preparing caustic soda by ion membrane after high-valence metal ions are removed by the resin tower 10. According to the requirement of refined brine for preparing caustic soda by using a Wanhua chlor-alkali ionic membrane, the TOC is less than 10 mg/L.
In the present invention, the chelating resin filled in the resin tower 10 mainly functions to remove high-valence metal ions, such as calcium and magnesium ions or residual catalyst metal ions, present in the water phase, so as to meet the process requirements of preparing caustic soda by using an ionic membrane. The chelating resin is a cross-linked functional polymer material capable of forming a multi-coordination complex with metal ions, and the mechanism of metal ion adsorption is that functional atoms on the resin and the metal ions perform a coordination reaction to form a stable structure similar to a micromolecular chelate, so that the chelating resin has higher selectivity and stability compared with the traditional ion exchange resin. The chelate resins used according to the invention are products which are well known to the skilled engineer and are widely marketed at present, for example the product sold under the name D401 chelate resin by Shanghai Kaiping resins Co., Ltd or the product sold under the name D463 chelate resin by Zibodong Dainippon Chemicals Co., Ltd.
The resin column 14 is a chelating ion exchange resin packed resin column having a filtering baffle structure, is a non-standard vessel well known to those skilled in the art, and is easily designed and manufactured, for example, by Haoyang Huanwang glass fiber reinforced Plastic, Inc., and Haoyko plant installation, Inc., of Laoyu.
In the invention, TOC (Total organic carbon, abbreviated as English) takes platinum as a catalyst to oxidize and burn a water sample to be measured at 900 ℃, and the increment of CO2 in gas is measured, so that the total carbon content in the water sample is determined to represent the total organic matter content in the water sample to be measured. As the TOC is measured by high-temperature combustion, all organic matters in a water sample to be measured can be oxidized, and the total amount of the organic matters can be objectively expressed more than BOD or COD.
[ advantageous effects ]
The invention has the beneficial effects that: the method has the advantages of simple and convenient process flow, simple operation, high automation degree and environmental protection, and can realize the harmless treatment and resource utilization of the high-salinity organic wastewater generated in the production process of the epoxy resin.
Drawings
FIG. 1 is a schematic flow diagram of the catalytic oxidation step of the high-salt organic wastewater treatment method of the invention;
FIG. 2 is a schematic flow diagram of the catalyst recovery step of the high-salt organic wastewater treatment method of the invention;
in the figure:
1-a storage tank; 11-a waste water line; 12-catalyst, hydrochloric acid line; 2-a high pressure pump; 3-a heat exchanger; 31-an oxygen-containing gas feed conduit; 4-a heater; 5-an oxidation tower; 51-an oxidation column feed line; 52-an oxidation tower discharge pipeline; 6-gas-liquid separator; 61-a gas-liquid separator feed line; 62-a gas phase discharge pipeline; 63-a liquid phase discharge conduit; 7-pH adjusting tank; 71-a conditioning tank wastewater feed line; 72-adjusting tank alkali liquor feeding pipeline; 8-sludge dewatering machine; 81-solid phase discharge line; 82-aqueous phase discharge line; 9-aqueous phase transfer pump; 10-a resin column; 101-resin column discharge line.
Detailed Description
The invention will be better understood from the following examples.
Example 1: treatment of high-salt organic wastewater generated in epoxy resin production process
The implementation steps of this example are as follows:
A. catalytic oxidation
The high-salt organic wastewater treated in this example was a wastewater having a sodium chloride content of 5% by weight, a TOC of 2000mg/L and a pH of 8.0.
High-salt organic wastewater generated in the production process of epoxy resin, a ferrous chloride catalyst with the weight of 0.1 percent of the wastewater and hydrochloric acid with the acid concentration of 0.1N are respectively conveyed into a storage tank 1 through a pipeline 11 and a pipeline 12, the pH of the high-salt organic wastewater is adjusted to 2 by adjusting the flow of the wastewater and the hydrochloric acid, then the adjusted high-salt wastewater is conveyed by a high-pressure pump 2, meanwhile, compressed air is conveyed by a pipeline 31, the high-salt organic wastewater and the high-salt organic wastewater are conveyed into an oxidation tower 5 from the bottom of the tower through a heat exchanger 3 and a heater 4 through an oxidation tower feeding pipeline 51, and the high-salt organic wastewater and the compressed air are subjected to oxidation treatment for 5 hours under the conditions of the temperature of 150 ℃ and the pressure of 1.0 MPa; the oxidation wastewater and the oxidation tail gas are discharged from an oxidation tower discharge pipeline 52 positioned at the top of the oxidation tower 5, enter a gas-liquid separator 6 through a pipeline 61 after heat exchange by a heat exchanger 3 for gas-liquid separation, the separated gas phase is mainly a mixed gas containing CO2 and water vapor and is discharged from a gas-phase discharge pipeline 62 positioned at the top of the gas-liquid separator 6, and the separated liquid phase is discharged from a liquid-phase discharge pipeline 63 at the bottom of the gas-liquid separator 6 and is sent to a subsequent treatment step for treatment;
B. recovery of catalyst
Conveying oxidized wastewater discharged from a liquid-phase discharge pipeline 63 at the bottom of a gas-liquid separator 6 into a pH adjusting tank 7 provided with a stirring paddle through an adjusting tank wastewater feed pipeline 71, simultaneously conveying sodium hydroxide with the alkali concentration of 2.0N into the pH adjusting tank 7 through an adjusting tank alkali liquor feed pipeline 72, adjusting the pH of the oxidized wastewater to 9, then feeding the oxidized wastewater into a sludge dewatering machine 8 for solid-liquid separation, discharging the obtained solid phase from the lower part of the sludge dewatering machine 8 through a solid-phase discharge pipeline 81, and conveying the solid phase to the top of a storage tank 1 through a catalyst pipeline 12; the resulting aqueous phase is discharged from the side of the sludge dewatering machine 8, transferred to the resin tower 10 through the pipe 82 by the pump 9 to remove high-valence metal ions, and the clean brine is discharged from the resin tower discharge pipe 101 located at the bottom of the resin tower 10, and it is used for preparing caustic soda by ionic membrane.
The TOC contents of the raw wastewater and the treated effluent of this example were measured using a Multi N/C instrument sold by Jena, Germany under the conditions described in the instruction manual, and the results are shown in Table 1.
Table 1: TOC test results of this example
Example 2: treatment of high-salt organic wastewater generated in epoxy resin production process
The implementation steps of this embodiment are as follows:
A. pretreatment of
The high-salt organic wastewater treated in this example was a pH9.0 wastewater having a sodium chloride content of 8% by weight and a TOC of 6000 mg/L.
High-salt organic wastewater generated in the production process of epoxy resin, a nickel protoxide catalyst with 0.6 percent of the weight of the wastewater and hydrochloric acid with the acid concentration of 0.5N are respectively conveyed into a storage tank 1 through a pipeline 11 and a pipeline 12, the pH of the high-salt organic wastewater is adjusted to 3 by adjusting the flow of the wastewater and the hydrochloric acid, then the adjusted high-salt wastewater is conveyed by a high-pressure pump 2, meanwhile, compressed air is conveyed by a pipeline 31 and is conveyed into a high-salt organic wastewater together with the high-salt organic wastewater from the bottom of an oxidation tower 5 through a heat exchanger 3 and a heater 4 through an oxidation tower feeding pipeline 51, and the high-salt organic wastewater and the compressed air are subjected to oxidation treatment for 4 hours under the conditions of 160 ℃ and 1.2 MPa; the oxidation wastewater and the oxidation tail gas are discharged from an oxidation tower discharge pipeline 52 positioned at the top of the oxidation tower 5, enter a gas-liquid separator 6 through a pipeline 61 after heat exchange by a heat exchanger 3 for gas-liquid separation, the separated gas phase is mainly a mixed gas containing CO2 and water vapor and is discharged from a gas-phase discharge pipeline 62 positioned at the top of the gas-liquid separator 6, and the separated liquid phase is discharged from a liquid-phase discharge pipeline 63 at the bottom of the gas-liquid separator 6 and is sent to a subsequent treatment step for treatment;
B. recovery of catalyst
Conveying oxidized wastewater discharged from a liquid-phase discharge pipeline 63 at the bottom of a gas-liquid separator 6 into a pH adjusting tank 7 provided with a stirring paddle through an adjusting tank wastewater feed pipeline 71, conveying sodium hydroxide with the alkali concentration of 4.0N into the pH adjusting tank 7 through an adjusting tank alkali liquor feed pipeline 72, adjusting the pH of the oxidized wastewater to 8, then feeding the oxidized wastewater into a sludge dehydrator 8 for solid-liquid separation, discharging the obtained solid phase from the lower part of the sludge dehydrator 8 through a solid-phase discharge pipeline 81, and conveying the solid phase to the top of a storage tank 1 through a catalyst pipeline 12; the resulting aqueous phase is discharged from the side of the sludge dewatering machine 8, transferred to the resin tower 10 through the pipe 82 by the pump 9 to remove high-valence metal ions, and the clean brine is discharged from the resin tower discharge pipe 101 located at the bottom of the resin tower 10, and it is used for preparing caustic soda by ionic membrane.
The TOC contents of the raw wastewater used in this example and the treated effluent of this example were measured according to the method described in example 1, and the results are shown in Table 2.
Table 2: TOC test results of this example
Example 3: treatment of high-salt organic wastewater generated in epoxy resin production process
The implementation steps of this embodiment are as follows:
A. pretreatment of
The high-salt organic wastewater treated in this example was a wastewater of pH9.5 having a sodium chloride concentration of 12% by weight and a TOC of 10000 mg/L.
High-salt organic wastewater generated in the production process of epoxy resin, cerium oxide catalyst with the weight of 0.9 percent of the wastewater and hydrochloric acid with the acid concentration of 1.0N are respectively conveyed into a storage tank 1 through a pipeline 11 and a pipeline 12, the pH of the high-salt organic wastewater is adjusted to 4 by adjusting the flow of the wastewater and the hydrochloric acid, then the adjusted high-salt wastewater is conveyed by a high-pressure pump 2, meanwhile, compressed air is conveyed by a pipeline 31, the high-salt organic wastewater and the high-salt organic wastewater are conveyed into an oxidation tower 5 from the bottom of the tower through an oxidation tower feeding pipeline 51 through a heat exchanger 3 and a heater 4, and the high-salt organic wastewater and the compressed air are subjected to oxidation treatment for 3 hours under the conditions of the temperature of 180 ℃ and the pressure of 1.5 MPa; the oxidation wastewater and the oxidation tail gas are discharged from an oxidation tower discharge pipeline 52 positioned at the top of the oxidation tower 5, enter a gas-liquid separator 6 through a pipeline 61 after heat exchange by a heat exchanger 3 for gas-liquid separation, the separated gas phase is mainly a mixed gas containing CO2 and water vapor and is discharged from a gas-phase discharge pipeline 62 positioned at the top of the gas-liquid separator 6, and the separated liquid phase is discharged from a liquid-phase discharge pipeline 63 at the bottom of the gas-liquid separator 6 and is sent to a subsequent treatment step for treatment;
B. recovery of catalyst
The oxidized waste water discharged from a liquid phase discharge pipeline 63 at the bottom of the gas-liquid separator 6 is conveyed into a pH adjusting tank 7 provided with a stirring paddle through an adjusting tank waste water feeding pipeline 71, meanwhile, sodium hydroxide with the alkali concentration of 6.0N is conveyed into the pH adjusting tank 7 through an adjusting tank alkali liquor feeding pipeline 72, the pH of the oxidized waste water is adjusted to 7.5, then the oxidized waste water enters a sludge dewatering machine 8 for solid-liquid separation, and the obtained solid phase is discharged from the lower part of the sludge dewatering machine 8 through a solid phase discharge pipeline 81 and is conveyed to the top of a storage tank 1 through a catalyst pipeline 12; the resulting aqueous phase is discharged from the side of the sludge dewatering machine 8, transferred to the resin tower 10 through the pipe 82 by the pump 9 to remove high-valence metal ions, and the clean brine is discharged from the resin tower discharge pipe 101 located at the bottom of the resin tower 10, and it is used for preparing caustic soda by ionic membrane.
The TOC contents of the raw wastewater used in this example and the treated effluent of this example were measured according to the method described in example 1, and the results are shown in Table 3.
Table 3: TOC test results of this example
Example 4: treatment of high-salt organic wastewater generated in epoxy resin production process
The implementation steps of this example are as follows:
A. pretreatment of
The high-salt organic wastewater treated in this example was a wastewater of pH10.0 having a calcium chloride concentration of 15% by weight and a TOC of 12000 mg/L.
High-salt organic wastewater generated in the production process of epoxy resin, a vanadium pentoxide catalyst with the weight of 1.2 percent of the wastewater and hydrochloric acid with the acid concentration of 2.0N are respectively conveyed into a storage tank 1 through a pipeline 11 and a pipeline 12, the pH of the high-salt organic wastewater is adjusted to 5 by adjusting the flow of the wastewater and the hydrochloric acid, then the adjusted high-salt wastewater is conveyed by a high-pressure pump 2, meanwhile, oxygen-enriched air is conveyed by a pipeline 31 and is conveyed into the high-salt organic wastewater from the bottom of an oxidation tower 5 through an oxidation tower feeding pipeline 51 together with a heat exchanger 3 and a heater 4, and the high-salt organic wastewater and the oxygen-enriched air are subjected to oxidation treatment for 2 hours under the conditions of the temperature of 260 ℃ and the pressure of 5.0 MPa; the oxidation wastewater and the oxidation tail gas are discharged from an oxidation tower discharge pipeline 52 positioned at the top of the oxidation tower 5, enter a gas-liquid separator 6 through a pipeline 61 after heat exchange by a heat exchanger 3 for gas-liquid separation, the separated gas phase is mainly a mixed gas containing CO2 and water vapor and is discharged from a gas-phase discharge pipeline 62 positioned at the top of the gas-liquid separator 6, and the separated liquid phase is discharged from a liquid-phase discharge pipeline 63 at the bottom of the gas-liquid separator 6 and is sent to a subsequent treatment step for treatment;
B. recovery of catalyst
The oxidized waste water discharged from a liquid phase discharge pipeline 63 at the bottom of the gas-liquid separator 6 is conveyed into a pH adjusting tank 7 provided with a stirring paddle through an adjusting tank waste water feeding pipeline 71, meanwhile, sodium hydroxide with the alkali concentration of 8.0N is conveyed into the pH adjusting tank 7 through an adjusting tank alkali liquor feeding pipeline 72, the pH of the oxidized waste water is adjusted to 6.5, then the oxidized waste water enters a sludge dewatering machine 8 for solid-liquid separation, and the obtained solid phase is discharged from the lower part of the sludge dewatering machine 8 through a solid phase discharge pipeline 81 and is conveyed to the top of a storage tank 1 through a catalyst pipeline 12; the resulting aqueous phase is discharged from the side of the sludge dewatering machine 8, transferred to the resin tower 10 through the pipe 82 by the pump 9 to remove high-valence metal ions, and the clean brine is discharged from the resin tower discharge pipe 101 located at the bottom of the resin tower 10, and it is used for preparing caustic soda by ionic membrane.
The TOC contents of the raw wastewater used in this example and the treated effluent of this example were measured according to the measurement method described in example 1, and the measurement results are shown in Table 4.
Table 4: TOC test results of this example
Example 5: treatment of high-salt organic wastewater generated in epoxy resin production process
The implementation steps of this example are as follows:
A. pretreatment of
The high-salt organic wastewater treated in this example was a pH12.0 wastewater having a sodium chloride concentration of 16% by weight and a TOC of 15000 mg/L.
A. Pretreatment of
The high-salt organic wastewater treated in this example was a wastewater of pH10.0 having a calcium chloride concentration of 15% by weight and a TOC of 12000 mg/L.
High-salt organic wastewater generated in the production process of epoxy resin, a copper chloride catalyst with the weight of 1.6 percent of the wastewater and hydrochloric acid with the acid concentration of 3.0N are respectively conveyed into a storage tank 1 through a pipeline 11 and a pipeline 12, the pH of the high-salt organic wastewater is adjusted to 6 by adjusting the flow of the wastewater and the hydrochloric acid, then the adjusted high-salt wastewater is conveyed by a high-pressure pump 2, meanwhile, oxygen-enriched air is conveyed by a pipeline 31, the high-salt organic wastewater and the high-salt organic wastewater are conveyed into an oxidation tower 5 from the bottom of the tower through an oxidation tower feeding pipeline 51 through a heat exchanger 3 and a heater 4, and the high-salt organic wastewater and the oxygen-enriched air are subjected to oxidation treatment for 1 hour under the conditions of the temperature of 280 ℃ and the pressure of 7.5 MPa; the oxidation wastewater and the oxidation tail gas are discharged from an oxidation tower discharge pipeline 52 positioned at the top of the oxidation tower 5, enter a gas-liquid separator 6 through a pipeline 61 after heat exchange by a heat exchanger 3 for gas-liquid separation, the separated gas phase is mainly a mixed gas containing CO2 and water vapor and is discharged from a gas-phase discharge pipeline 62 positioned at the top of the gas-liquid separator 6, and the separated liquid phase is discharged from a liquid-phase discharge pipeline 63 at the bottom of the gas-liquid separator 6 and is sent to a subsequent treatment step for treatment;
B. recovery of catalyst
Conveying oxidized wastewater discharged from a liquid-phase discharge pipeline 63 at the bottom of a gas-liquid separator 6 into a pH adjusting tank 7 provided with a stirring paddle through an adjusting tank wastewater feed pipeline 71, conveying sodium hydroxide with the alkali concentration of 10.0N into the pH adjusting tank 7 through an adjusting tank alkali liquor feed pipeline 72, adjusting the pH of the oxidized wastewater to 6, then feeding the wastewater into a sludge dewatering machine 8 for solid-liquid separation, discharging the obtained solid phase from the lower part of the sludge dewatering machine 8 through a solid-phase discharge pipeline 81, and conveying the solid phase to the top of a storage tank 1 through a catalyst pipeline 12; the resulting aqueous phase is discharged from the side of the sludge dewatering machine 8, transferred to the resin tower 10 through the pipe 82 by the pump 9 to remove high-valence metal ions, and the clean brine is discharged from the resin tower discharge pipe 101 located at the bottom of the resin tower 10, and it is used for preparing caustic soda by ionic membrane.
The TOC contents of the raw wastewater used in this example and the treated effluent of this example were measured according to the method described in example 1, and the results are shown in Table 5.
Table 5: TOC test results of this example
Example 6: treatment of high-salt organic wastewater generated in epoxy resin production process
The implementation steps of this example are as follows:
A. pretreatment of
The high-salt organic wastewater treated in this example was a wastewater of pH11.0 having a sodium chloride concentration of 18% by weight and a TOC of 17000 mg/L.
High-salt organic wastewater generated in the production process of epoxy resin, a manganese oxide catalyst with the weight of 2.0 percent of the wastewater and hydrochloric acid with the acid concentration of 4.0N are respectively conveyed into a storage tank 1 through a pipeline 11 and a pipeline 12, the pH of the high-salt organic wastewater is adjusted to 2.5 by adjusting the flow of the wastewater and the hydrochloric acid, then the adjusted high-salt wastewater is conveyed by a high-pressure pump 2, meanwhile, industrial pure oxygen is conveyed by a pipeline 31 and is conveyed into a high-salt organic wastewater together with the high-salt organic wastewater from the bottom of an oxidation tower 5 through an oxidation tower feeding pipeline 51 through a heat exchanger 3 and a heater 4, and the high-salt organic wastewater and the industrial pure oxygen are subjected to oxidation treatment for 0.5h at the temperature of 300 ℃ and the pressure of 9.0 MPa; the oxidation wastewater and the oxidation tail gas are discharged from an oxidation tower discharge pipeline 52 positioned at the top of the oxidation tower 5, enter a gas-liquid separator 6 through a pipeline 61 after heat exchange by a heat exchanger 3 for gas-liquid separation, the separated gas phase is mainly a mixed gas containing CO2 and water vapor and is discharged from a gas-phase discharge pipeline 62 positioned at the top of the gas-liquid separator 6, and the separated liquid phase is discharged from a liquid-phase discharge pipeline 63 at the bottom of the gas-liquid separator 6 and is sent to a subsequent treatment step for treatment;
B. recovery of catalyst
Conveying oxidized wastewater discharged from a liquid-phase discharge pipeline 63 at the bottom of a gas-liquid separator 6 into a pH adjusting tank 7 provided with a stirring paddle through an adjusting tank wastewater feed pipeline 71, conveying sodium hydroxide with the alkali concentration of 6.5N into the pH adjusting tank 7 through an adjusting tank alkali liquor feed pipeline 72, adjusting the pH of the oxidized wastewater to 7, then feeding the oxidized wastewater into a sludge dehydrator 8 for solid-liquid separation, discharging the obtained solid phase from the lower part of the sludge dehydrator 8 through a solid-phase discharge pipeline 81, and conveying the solid phase to the top of a storage tank 1 through a catalyst pipeline 12; the resulting aqueous phase is discharged from the side of the sludge dewatering machine 8, transferred to the resin tower 10 through the pipe 82 by the pump 9 to remove high-valence metal ions, and the clean brine is discharged from the resin tower discharge pipe 101 located at the bottom of the resin tower 10, and it is used for preparing caustic soda by ionic membrane.
The TOC contents of the raw wastewater used in this example and the effluent treated in this example were measured according to the measurement method described in example 1, and the measurement results are shown in Table 6.
Table 6: TOC test results of this example
Example 7: treatment of high-salt organic wastewater generated in epoxy resin production process
The implementation steps of this example are as follows:
A. pretreatment of
The high-salt organic wastewater treated in this example was a wastewater having a pH of 10.6 and a sodium chloride concentration of 20% by weight and a TOC of 19000 mg/L.
Conveying high-salt organic wastewater generated in an epoxy resin production process, 0.5% of cadmium oxide and 0.6% of cobalt oxide catalyst based on the weight of the wastewater, and hydrochloric acid with the acid concentration of 2.5N into a storage tank 1 through a pipeline 11 and a pipeline 12 respectively, adjusting the pH of the high-salt organic wastewater to 4.2 by adjusting the flow rates of the wastewater and the hydrochloric acid, conveying the adjusted high-salt wastewater through a high-pressure pump 2, conveying industrial pure oxygen through a pipeline 31, conveying the industrial pure oxygen and the high-salt organic wastewater into a high-salt organic wastewater through a heat exchanger 3 and a heater 4 and an oxidation tower 5 bottom through an oxidation tower feeding pipeline 51, and carrying out oxidation treatment on the high-salt organic wastewater and the industrial pure oxygen for 1.5h at the temperature of 220 ℃ and the pressure of 3.5 MPa; the oxidation wastewater and the oxidation tail gas are discharged from an oxidation tower discharge pipeline 52 positioned at the top of the oxidation tower 5, enter a gas-liquid separator 6 through a pipeline 61 after heat exchange by a heat exchanger 3 for gas-liquid separation, the separated gas phase is mainly a mixed gas containing CO2 and water vapor and is discharged from a gas-phase discharge pipeline 62 positioned at the top of the gas-liquid separator 6, and the separated liquid phase is discharged from a liquid-phase discharge pipeline 63 at the bottom of the gas-liquid separator 6 and is sent to a subsequent treatment step for treatment;
B. recovery of catalyst
The oxidized waste water discharged from a liquid phase discharge pipeline 63 at the bottom of the gas-liquid separator 6 is conveyed into a pH adjusting tank 7 provided with a stirring paddle through an adjusting tank waste water feeding pipeline 71, meanwhile, sodium hydroxide with the alkali concentration of 4.5N is conveyed into the pH adjusting tank 7 through an adjusting tank alkali liquor feeding pipeline 72, the pH of the oxidized waste water is adjusted to 8.2, then the oxidized waste water enters a sludge dewatering machine 8 for solid-liquid separation, and the obtained solid phase is discharged from the lower part of the sludge dewatering machine 8 through a solid phase discharge pipeline 81 and is conveyed to the top of a storage tank 1 through a catalyst pipeline 12; the resulting aqueous phase is discharged from the side of the sludge dewatering machine 8, transferred to the resin tower 10 through the pipe 82 by the pump 9 to remove high-valence metal ions, and the clean brine is discharged from the resin tower discharge pipe 101 located at the bottom of the resin tower 10, and it is used for preparing caustic soda by ionic membrane.
The TOC contents of the raw wastewater used in this example and the effluent treated in this example were measured according to the measurement method described in example 1, and the measurement results are shown in Table 7.
Table 7: TOC test results of this example
Example 8: treatment of high-salt organic wastewater generated in epichlorohydrin production process
The implementation steps of this example are as follows:
A. pretreatment of
The high-salt organic wastewater treated in this example was a wastewater of pH12.0 having a calcium chloride concentration of 25% by weight and a TOC of 20000 mg/L.
Conveying high-salt organic wastewater generated in an epoxy resin production process, cerium nitrate accounting for 0.3 percent of the weight of the wastewater, a ferric chloride catalyst accounting for 0.9 percent of the weight of the wastewater and hydrochloric acid with the acid concentration of 1.5N into a storage tank 1 through a pipeline 11 and a pipeline 12 respectively, adjusting the pH value of the high-salt organic wastewater to 3.8 by adjusting the flow rate of the wastewater and the hydrochloric acid, conveying the adjusted high-salt wastewater through a high-pressure pump 2, conveying industrial pure oxygen through a pipeline 31, conveying the industrial pure oxygen and the high-salt organic wastewater into a high-salt organic wastewater through a heat exchanger 3 and a heater 4 and an oxidation tower 5 bottom through an oxidation tower feeding pipeline 51, and carrying out oxidation treatment on the high-salt organic wastewater and the industrial pure oxygen for 2.0h at the temperature of 250 ℃ and the pressure of 4.5 MPa; the oxidation wastewater and the oxidation tail gas are discharged from an oxidation tower discharge pipeline 52 positioned at the top of the oxidation tower 5, enter a gas-liquid separator 6 through a pipeline 61 after heat exchange by a heat exchanger 3 for gas-liquid separation, the separated gas phase is mainly a mixed gas containing CO2 and water vapor and is discharged from a gas-phase discharge pipeline 62 positioned at the top of the gas-liquid separator 6, and the separated liquid phase is discharged from a liquid-phase discharge pipeline 63 at the bottom of the gas-liquid separator 6 and is sent to a subsequent treatment step for treatment;
B. recovery of catalyst
The oxidized waste water discharged from a liquid phase discharge pipeline 63 at the bottom of the gas-liquid separator 6 is conveyed into a pH adjusting tank 7 provided with a stirring paddle through an adjusting tank waste water feeding pipeline 71, meanwhile, sodium hydroxide with the alkali concentration of 2.5N is conveyed into the pH adjusting tank 7 through an adjusting tank alkali liquor feeding pipeline 72, the pH of the oxidized waste water is adjusted to 7.7, then the oxidized waste water enters a sludge dewatering machine 8 for solid-liquid separation, and the obtained solid phase is discharged from the lower part of the sludge dewatering machine 8 through a solid phase discharge pipeline 81 and is conveyed to the top of a storage tank 1 through a catalyst pipeline 12; the resulting aqueous phase is discharged from the side of the sludge dewatering machine 8, transferred to the resin tower 10 through the pipe 82 by the pump 9 to remove high-valence metal ions, and the clean brine is discharged from the resin tower discharge pipe 101 located at the bottom of the resin tower 10, and it is used for preparing caustic soda by ionic membrane.
The TOC contents of the raw wastewater and the treated effluent of this example were measured according to the method described in example 1, and the results are shown in Table 8.
Table 8: TOC test results of this example
The results of examples 1-8 clearly show that the high-salt organic wastewater treated by the examples can meet the index requirement that TOC is less than or equal to 20mg/L specified in GB 31571-2015 petrochemical industry pollutant discharge Standard, and can also meet the requirement that TOC of ion membrane caustic soda is less than or equal to 10mg/L, thereby well explaining the beneficial effects of the high-salt organic wastewater treatment of the invention.
The embodiments of examples 1-3, 4-5, 6-8 demonstrate the beneficial effects of air, oxygen-enriched air, and commercially pure oxygen, respectively, as oxygen-containing gases for oxidation.
Claims (10)
1. An energy-saving treatment method of high-salt organic wastewater for preparing caustic soda by using an ionic membrane is characterized by comprising the following steps of:
the processing method comprises the following steps:
A. catalytic oxidation
The organic wastewater, a catalyst and an oxygen-containing gas are subjected to catalytic oxidation treatment in an oxidation tower (5), the oxidation wastewater and oxidation tail gas are discharged from an oxidation tower discharge pipeline (52) of the oxidation tower (5), are subjected to heat exchange by a heat exchanger (3) and then enter a gas-liquid separator (6) for gas-liquid separation, a gas phase is discharged from a gas phase discharge pipeline (62) of the gas-liquid separator (6), and a liquid phase is discharged from a liquid phase discharge pipeline (63) of the gas-liquid separator (6) and is sent to a subsequent treatment step for treatment.
2. The energy-saving treatment method of the high-salt organic wastewater for preparing the caustic soda by the ionic membrane according to claim 1, characterized in that:
the treatment method is used for treating organic wastewater generated in the production process of epoxy resin.
3. The energy-saving treatment method of the high-salinity organic wastewater for preparing caustic soda by using the ionic membrane according to claim 2, is characterized in that:
in the organic wastewater generated in the production process of the epoxy resin: the sodium chloride content is 5-25% by weight, and the TOC content is 2000-20000 mg/L, pH is 8-12.
4. The energy-saving treatment method of the high-salinity organic wastewater for preparing caustic soda by using the ionic membrane according to claim 2, is characterized in that:
in step A, the catalyst is one or more catalysts selected from metal oxides or metal salts of iron, cadmium, vanadium, nickel, copper, manganese, cobalt, cadmium, molybdenum or cerium; the dosage of the catalyst is 0.1-2.0% of the weight of the wastewater.
5. The energy-saving treatment method of the high-salt organic wastewater for preparing the caustic soda by the ionic membrane according to any one of claims 1 to 4, characterized by comprising the following steps:
also comprises a step B of recovering the catalyst
Adjusting the pH value of the liquid phase to 6-9, then carrying out solid-liquid separation, and conveying the obtained solid phase to the top of the storage tank (1); the resulting aqueous phase is transferred to a resin column (10) to remove high-valence metal ions, and the resin column (10) discharges clean brine.
6. The energy-saving treatment method of the high-salinity organic wastewater for preparing caustic soda by using the ionic membrane according to claim 2, is characterized in that:
in the step A, the organic wastewater and the oxygen-containing gas are oxidized for 0.5 to 5 hours at the temperature of 150 to 300 ℃ and under the pressure of 1.0 to 9.0 MPa.
7. The energy-saving treatment method of the high-salinity organic wastewater for preparing caustic soda by using the ionic membrane according to claim 6, is characterized in that:
in the step A, the organic wastewater and the oxygen-containing gas are oxidized for 1-4 hours at the temperature of 160-280 ℃ and under the pressure of 1.2-7.5 MPa.
8. The energy-saving treatment method of the high-salinity organic wastewater for preparing caustic soda by using the ionic membrane according to claim 7, is characterized in that:
in the step A, the organic wastewater and the oxygen-containing gas are oxidized for 2-3 hours at the temperature of 180-260 ℃ and under the pressure of 1.5-5.0 MPa.
9. The energy-saving treatment method of the high-salinity organic wastewater for preparing caustic soda by using the ionic membrane according to claim 1, is characterized in that:
the oxygen-containing gas and the organic wastewater enter an oxidation tower (5) through a heat exchanger (3) and a heater (4).
10. The energy-saving treatment method of the high-salinity organic wastewater for preparing caustic soda by using the ionic membrane according to claim 9, is characterized in that:
the oxygen-containing gas is air, oxygen-enriched air or industrial pure oxygen.
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| CN111470677A (en) * | 2020-05-14 | 2020-07-31 | 浙江德强科技有限公司 | Method for producing ionic membrane caustic soda by using high-salt organic wastewater generated in epoxy chloropropane production process |
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