CN113548747A - Coal chemical industry salt-containing sewage treatment system and method - Google Patents
Coal chemical industry salt-containing sewage treatment system and method Download PDFInfo
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/22—Treatment of water, waste water, or sewage by freezing
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/469—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis
- C02F1/4693—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis electrodialysis
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2209/08—Chemical Oxygen Demand [COD]; Biological Oxygen Demand [BOD]
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- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/10—Solids, e.g. total solids [TS], total suspended solids [TSS] or volatile solids [VS]
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
Abstract
The application relates to a coal chemical industry salt-containing sewage treatment system and a treatment method. The processing system comprises: the pretreatment unit, the treatment unit, and crystallization salt production unit, wherein, the treatment unit includes the supercritical water oxidation unit, the treatment unit delivery port sets up on the supercritical water oxidation unit. The method can realize concentration of salt in the coal chemical industry sewage, removal of organic matters and utilization of separated salt in a synergistic manner, realizes harmless and recycling treatment of the coal chemical industry high-salt degradation-resistant sewage, and has the advantages of simple process, energy conservation, high efficiency and high quality of crystallized salt products.
Description
Technical Field
The invention relates to a sewage treatment technology, in particular to a coal chemical industry salt-containing degradation-resistant organic sewage treatment process system, and more particularly relates to a coal chemical industry salt-containing wastewater treatment system and method suitable for salt concentration of coal chemical industry salt-containing sewage, efficient removal of organic matters in cooperation and salt separation coupling.
Background
China has the energy characteristics of rich coal, less oil and poor gas, and the modern coal chemical industry needs to be continuously developed in the face of the current situation. The modern coal chemical industry conflicts with the shortage of water resources and the water environmental capacity in China. Therefore, the zero discharge of the wastewater is implemented for modern coal chemical engineering projects, so that the realization of wastewater recycling is an inevitable way to solve the contradiction.
The sewage in the modern coal chemical industry can be divided into two types according to the salt content: one type is organic wastewater which is mainly derived from coal gasification process wastewater and the like, has low salt content and high organic pollutant content and is generally treated by a biochemical process; the other type is strong-salt-containing wastewater which is mainly derived from chemical water station drainage, coal gasification washing wastewater, circulating water system drainage, desalted water system drainage, biochemically treated organic wastewater and the like in the production process, generally has high salt content, mainly contains total dissolved solid pollutants, and part of wastewater contains refractory organic matters. The treatment and resource utilization of the saline sewage in the coal chemical industry are the important difficulties of zero discharge in the coal chemical industry, wherein the treatment of high-concentration saline water and miscellaneous salt thereof is the core, and a high-concentration saline water treatment unit in the traditional wastewater zero discharge technology can generate crystallized miscellaneous salt which cannot be recycled. In 12 months in 2015, "environmental admission conditions (trial) for modern coal chemical engineering construction projects", which were issued by the environmental protection department, indicate that the salt mud which cannot be recycled belongs to hazardous waste. As the processing centers with the qualification in China are few, the processing capacity is limited, the processing cost is high (3000 yuan/ton), and the general enterprises are hard to bear. Therefore, in the zero-discharge treatment process of wastewater, the salt separation technology for purification and reuse is realized to obtain high-purity crystalline salt, so that the method is one of effective ways for realizing reduction, harmlessness and recycling of the miscellaneous salt and solving the miscellaneous salt, and is the last kilometer of environmental protection in coal chemical industry.
The traditional process for treating the coal chemical industry sewage can be summarized as pretreatment, membrane treatment and crystallization and salt separation. The pretreatment is to reduce COD in the wastewater to be below 100mg/L so as to avoid subsequent membrane blockage and membrane damage; the membrane treatment is to concentrate TDS in the brine to 50000-80000mg/L and recover 50-75% of wastewater; the crystallization salt separation is to perform evaporation salt extraction on the mixed salt solution or the single salt solution after nanofiltration. However, the conventional treatment process has several problems: (1) no process can realize the concentration of the salt in the coal chemical wastewater and the synchronous removal of COD, and the process is complex. (2) The method is a combined process treatment system, the process flow is long, and the later salt separation effect can be influenced by the occurrence of problems in any unit at the upstream. (3) For organic matters which are difficult to degrade in the wastewater, the traditional process is not thorough in treatment, and the quality of the crystallized salt is influenced. (4) TDS and COD in the high-concentration wastewater are high, the requirements on subsequent membrane treatment and concentration units are high, and energy consumption and cost are increased. (4) The obtained small amount of miscellaneous salt still contains high-concentration organic matters which are difficult to degrade and need further disposal.
Disclosure of Invention
The invention aims to provide a treatment system and a treatment method for coal chemical industry saline sewage, which can realize concentration of salt in the coal chemical industry sewage, removal of organic matters and utilization of separated salt in a synergistic manner, realize harmless and recycling treatment of high-salt refractory sewage in the coal chemical industry, and have the advantages of simple process, energy conservation, high efficiency and high quality of crystallized salt products.
The invention provides a coal chemical industry contains salt sewage treatment system, includes:
the pretreatment unit is used for preliminarily treating the coal chemical industry saline sewage to obtain pretreated sewage; the pretreatment unit is provided with a pretreatment unit feed inlet communicated with the coal chemical industry salt-containing sewage feed pipeline and a pretreatment unit discharge outlet used for discharging the pretreated sewage;
the treatment unit is used for treating the pretreated sewage to obtain strong brine and purified water; the treatment unit is provided with a treatment unit feed inlet communicated with the pretreatment unit discharge outlet, a treatment unit discharge outlet used for discharging the strong brine and a treatment unit water outlet used for discharging the purified water;
a crystallization salt production unit for crystallizing the strong brine from the treatment unit to obtain product salt; the crystallization salt production unit is provided with a crystallization salt production unit feeding port communicated with the treatment unit discharging port and a crystallization salt discharging port for discharging the product salt;
the treatment unit comprises a supercritical water oxidation unit, and the water outlet of the treatment unit is arranged on the supercritical water oxidation unit.
In one embodiment, the treatment unit further comprises a salt separation unit connected in series with the supercritical water oxidation unit; wherein, according to the material flowing direction, the salt separation unit is arranged in front of the supercritical water oxidation unit;
the salt separation unit is provided with a feeding hole of the treatment unit and a discharging hole of the salt separation unit,
the supercritical water oxidation unit is provided with a treatment unit discharge hole and a supercritical water oxidation unit feed hole;
and the discharge hole of the salt separation unit is communicated with the feed inlet of the supercritical water oxidation unit through a pipeline.
In one embodiment, the treatment unit further comprises a salt separation unit connected in series with the supercritical water oxidation unit; wherein, according to the material flowing direction, the supercritical water oxidation unit is arranged in front of the salt separation unit;
the supercritical water oxidation unit is provided with a treatment unit feed inlet and a supercritical water oxidation unit discharge outlet;
the salt separation unit is provided with a discharge hole of the treatment unit and a feed hole of the salt separation unit,
the discharge hole of the supercritical water oxidation unit is communicated with the feed hole of the salt separation unit through a pipeline.
In one embodiment, the pretreatment unit comprises one or more of a softening treatment system, an ion exchange system, and a filtration treatment system.
In one embodiment, the filtration treatment system comprises an ultrafiltration treatment system.
In one embodiment, the salt separation unit comprises one or more of a membrane separation unit and an electrodialysis salt separation unit.
In one embodiment, the supercritical water oxidation unit is provided with a mixer of sewage and an oxidant, a combustion improver and a regulator, and is further provided with a tail gas collection and detection system.
In one embodiment, the crystallization salt-producing unit comprises an evaporative crystallization unit or a freeze crystallization unit.
On the other hand, the invention provides a method for treating the saline sewage in the coal chemical industry, which comprises the following steps:
enabling the coal chemical industry saline sewage to pass through a pretreatment unit to obtain pretreated sewage; the pretreatment unit is provided with a pretreatment unit feed inlet communicated with the coal chemical industry salt-containing sewage feed pipeline and a pretreatment unit discharge outlet used for discharging the pretreated sewage;
enabling the pretreated sewage to pass through a treatment unit to obtain strong brine and purified water; the treatment unit is provided with a treatment unit feed inlet communicated with the pretreatment unit discharge outlet, a treatment unit discharge outlet used for discharging the strong brine and a treatment unit water outlet used for discharging the purified water;
crystallizing the strong brine from the treatment unit in a crystallization salt production unit to obtain product salt; the crystallization salt production unit is provided with a crystallization salt production unit feeding port communicated with the treatment unit discharging port and a crystallization salt discharging port for discharging the product salt;
the treatment unit comprises a supercritical water oxidation unit, and the water outlet of the treatment unit is arranged on the supercritical water oxidation unit.
In one embodiment of the treatment process, the treatment unit further comprises a salt separation unit connected in series with the supercritical water oxidation unit; wherein, according to the material flowing direction, the salt separation unit is arranged in front of the supercritical water oxidation unit;
the salt separation unit is provided with a feeding hole of the treatment unit and a discharging hole of the salt separation unit,
the supercritical water oxidation unit is provided with a treatment unit discharge hole and a supercritical water oxidation unit feed hole;
the discharge hole of the salt separation unit is communicated with the feed hole of the supercritical water oxidation unit through a pipeline;
and the concentrated brine is discharged from a discharge hole of the treatment unit to the supercritical water oxidation unit.
In one embodiment of the treatment process, the treatment unit further comprises a salt separation unit connected in series with the supercritical water oxidation unit; wherein, according to the material flowing direction, the supercritical water oxidation unit is arranged in front of the salt separation unit;
the supercritical water oxidation unit is provided with a treatment unit feed inlet and a supercritical water oxidation unit discharge outlet;
the salt separation unit is provided with a discharge hole of the treatment unit and a feed hole of the salt separation unit,
the discharge hole of the supercritical water oxidation unit is communicated with the feed hole of the salt separation unit through a pipeline;
and the strong brine is discharged from the discharge hole of the processing unit to the salt separation unit.
In one embodiment of the treatment method, the pretreatment unit comprises one or more of a softening treatment system, an ion exchange system, and a filtration treatment system.
In one embodiment of the treatment method, the filtration treatment system comprises an ultrafiltration treatment system.
In one embodiment of the treatment method, the salt separation unit comprises one or more of a membrane separation unit and an electrodialysis salt separation unit.
In one embodiment of the treatment method, the reaction temperature of the supercritical water oxidation unit is 380-650 ℃, preferably 400-600 ℃, and the operation pressure is 20-35 MPa, preferably 23-30 MPa.
In one embodiment of the treatment process, the supercritical water oxidation unit is provided with a mixer of sewage with an oxidant, a combustion improver and a regulator, and is also provided with a tail gas collection and detection system.
In one embodiment of the treatment method, the oxidizing agent comprises one or more of hydrogen peroxide, oxygen, and air; the combustion improver comprises one or more flammable organic solvents; the conditioning agent comprises an alkaline solution.
In one embodiment of the treatment process, a catalyst is also added to the supercritical water oxidation unit, the catalyst being selected from the group consisting of homogeneous catalysts and heterogeneous catalysts.
In one embodiment of the treatment process, the homogeneous catalyst is selected from one or more of sodium hydroxide, soluble transition metal salts, alkaline salts.
In one embodiment of the treatment method, the soluble transition metal salt comprises a nitrate or sulfate of Cu, Fe, Mn, Ni, Co; the alkaline salt comprises one or more of sodium carbonate and sodium bicarbonate.
In one embodiment of the treatment process, the heterogeneous catalyst is selected from one or more of metal oxides and activated carbon.
In one embodiment of the treatment method, the metal oxide comprises CuO, MnO2、ZrO2、TiO2One or more of (a).
In one embodiment of the process, the crystallization salt-producing unit comprises an evaporative crystallization unit or a freeze crystallization unit.
The processing system and the processing method provided by the invention have the advantages that:
(1) the supercritical water oxidation unit can realize the synchronous removal of salt concentration and COD in the wastewater, has high concentration rate and thorough removal rate, can replace the traditional combined process coupling crystallization salt production unit, and simplifies the process flow.
(2) The supercritical water oxidation unit is flexible in application node, adjustable in salt concentration degree, capable of being applied to pretreatment before the salt separation unit, and capable of performing single salt concentration treatment after the salt separation unit.
(3) The advantage of the high-efficient treatment sewage of supercritical water oxidation unit can alleviate the pressure of salinity separation unit to a certain extent. Before the salt separation unit is applied, organic matters can be thoroughly removed, and the pollution of the organic matters to the separation unit is prevented; after the device is applied to the salt separation unit, the pressure of the upstream unit can be reduced, and the disadvantage that organic matters which are difficult to degrade in the earlier-stage sewage treatment unit are difficult to remove is made up.
(4) The process effectively couples the supercritical water oxidation technology with the traditional water treatment and salt separation technology, the produced crystal salt has high quality, and the reduction, harmlessness and resource utilization of the refractory high-concentration sewage in the coal chemical industry are realized.
(5) The supercritical water oxidation unit is efficient, thorough and rapid in sewage treatment, self-heating can be achieved to a certain extent, energy consumption is reduced, the device occupies a small area, skid-mounted equipment is easy to achieve, and investment cost is reduced.
Drawings
FIG. 1, FIG. 2 and FIG. 3 are schematic diagrams of the treatment process of saline wastewater in 3 different coal chemical industries provided by the invention.
The reference numbers illustrate:
in the figure 1, 1-coal chemical industry saline sewage, 2-pretreatment unit, 3-supercritical water oxidation unit, 4-crystallization salt production unit I, 5-crystallization salt production unit II, 6-oxidant inlet, 7-combustion improver inlet, 8-regulator inlet, 9-purified water outlet, 10-crystallization pure salt outlet, and 11-crystallization mixed salt.
In figure 2, 21-coal chemical industry saline sewage, 22-pretreatment unit, 23-supercritical water oxidation unit, 24-purified water outlet, 25-oxidant inlet, 26-combustion improver inlet, 27-regulator inlet, 28-salt separation unit, 29-crystallization salt production unit, 210-sodium chloride crystal salt, 211-crystallization salt production unit, 212-sodium sulfate crystal salt, 213-crystallization salt production unit, 214-sodium sulfate crystal salt, and 215-mother liquor drying miscellaneous salt.
In the figure 3, 31-coal chemical industry saline sewage, 32-pretreatment unit, 33-salt separation unit, 34-supercritical water oxidation unit, 35-supercritical water oxidation unit, 36-oxidant inlet, 37-combustion improver inlet, 38-regulator inlet, 39-purified water outlet, 310-crystallization salt production unit, 311-sodium chloride crystal salt, 312-crystallization salt production unit, 313-sodium sulfate crystal salt, 314-crystallization salt production unit, 315-sodium sulfate crystal salt, and 316-mother liquor drying miscellaneous salt.
Detailed Description
The technical solution of the present invention is further explained below according to specific embodiments. The scope of protection of the invention is not limited to the following examples, which are set forth for illustrative purposes only and are not intended to limit the invention in any way.
The application provides coal industry contains salt sewage treatment system includes:
the pretreatment unit is used for preliminarily treating the coal chemical industry saline sewage to obtain pretreated sewage; the pretreatment unit is provided with a pretreatment unit feed inlet communicated with the coal chemical industry salt-containing sewage feed pipeline and a pretreatment unit discharge outlet used for discharging the pretreated sewage;
the treatment unit is used for treating the pretreated sewage to obtain strong brine and purified water; the treatment unit is provided with a treatment unit feed inlet communicated with the pretreatment unit discharge outlet, a treatment unit discharge outlet used for discharging the strong brine and a treatment unit water outlet used for discharging the purified water;
a crystallization salt production unit for crystallizing the strong brine from the treatment unit to obtain product salt; the crystallization salt production unit is provided with a crystallization salt production unit feeding port communicated with the treatment unit discharging port and a crystallization salt discharging port for discharging the product salt;
the treatment unit comprises a supercritical water oxidation unit, and the water outlet of the treatment unit is arranged on the supercritical water oxidation unit.
FIG. 1 illustrates a processing system according to one embodiment of the present application. In the figure 1, 1-coal chemical industry saline sewage, 2-pretreatment unit, 3-supercritical water oxidation unit, 4-crystallization salt production unit I, 5-crystallization salt production unit II, 6-oxidant inlet, 7-combustion improver inlet, 8-regulator inlet, 9-purified water, 10-crystallization pure salt outlet and 11-crystallization mixed salt. When a certain salt content in the salt-containing sewage has a great advantage, the process can be used for separating and recovering the dominant salt component, as shown in figure 1. The method comprises the following steps that firstly, impurities in the salt-containing sewage 1 in the coal chemical industry are removed through a pretreatment unit 2, the obtained sewage is further concentrated through a supercritical water oxidation unit 3 and is subjected to synchronous organic matter removal treatment, the obtained sewage basically does not contain COD, a certain advantageous salt component is nearly saturated, and then the sewage enters a crystallization salt production unit I4 to produce most of sodium chloride or sodium sulfate pure salt 10. The supercritical water oxidation unit 3 is preferably provided with an oxidant inlet 6, a combustion improver inlet 7, a regulator inlet 8 and a purified water outlet 9. In the treatment of the crystallization salt-producing unit I4, the concentration ratio is controlled to be that the salt component with suboptimal potential is close to saturation, and the mother liquor discharged from the crystallization salt-producing unit I4 enters the mixed salt crystallization salt-producing unit II 5 to obtain a small amount of crystallized mixed salt 11 without COD. The crystallized mixed salt 11 belongs to general solid waste. In this embodiment, the treatment system mainly comprises a pretreatment unit, a supercritical water oxidation unit (treatment unit) and a crystallization salt production unit which are connected in sequence, so that the sewage passes through the pretreatment unit, the supercritical water oxidation unit (treatment unit) and the crystallization salt production unit in sequence for treatment, wherein purified water is discharged from the supercritical water oxidation unit (treatment unit), and corresponding salt is obtained in the crystallization salt production unit.
In the invention, the pretreatment unit comprises one or more of a softening treatment system, an ion exchange system and a filtering treatment system. Preferably, the filtration treatment system comprises an ultrafiltration treatment system.
The pretreatment unit is used for primarily treating the coal chemical industry saline sewage to remove impurities in the saline sewage, so as to obtain pretreated sewage. In a preferred embodiment of the present invention, the impurities are one or more of suspended substances and other insoluble substances contained in the wastewater. The impurity removal in the salt-containing sewage means that the water subjected to impurity removal treatment can be fed normally and smoothly circulates in a pipeline without deposition and blockage.
Fig. 2 and 3 each show a processing system according to another embodiment of the present application. In the treatment system, the treatment unit further comprises a salt separation unit connected in series with the supercritical water oxidation unit. The salt separation unit can be positioned before the supercritical water oxidation unit or positioned after the supercritical water oxidation unit.
Fig. 3 shows an embodiment in which the salt separation unit is located before the supercritical water oxidation unit. In the figure 3, 31-coal chemical industry saline sewage, 32-pretreatment unit, 33-salt separation unit, 34-supercritical water oxidation unit, 35-supercritical water oxidation unit, 36-oxidant inlet, 37-combustion improver inlet, 38-regulator inlet, 39-purified water outlet, 310-crystallization salt production unit, 311-sodium chloride crystal salt, 312-crystallization salt production unit, 313-sodium sulfate crystal salt, 314-crystallization salt production unit, 315-sodium sulfate crystal salt, and 316-mother liquor drying miscellaneous salt. In this treatment system, the treatment unit further comprises a salt separation unit 33 connected in series with the supercritical water oxidation units 34, 35; wherein, according to the material flowing direction, the salt separation unit 33 is arranged in front of the supercritical water oxidation units 34 and 35; the salt separation unit 33 is provided with a treatment unit feed port and a salt separation unit discharge port, and the supercritical water oxidation units 34 and 35 are provided with a treatment unit discharge port and a supercritical water oxidation unit feed port; and the discharge hole of the salt separation unit is communicated with the feed inlet of the supercritical water oxidation unit through a pipeline.
As shown in fig. 3, the saline wastewater 31 from coal chemical industry first passes through a pretreatment unit 32 to remove impurities, and the obtained wastewater further passes through a salt separation unit 33 (taking a nanofiltration membrane as an example) to separate monovalent salt and divalent salt, so as to obtain monovalent saline water and divalent saline water (generally sodium sulfate-rich solution or mixed saline water of sodium chloride and sodium sulfate) rich in sodium chloride. The nanofiltration permeate (monovalent brine rich in sodium chloride) mainly containing sodium chloride is concentrated and COD is synchronously removed through the supercritical water oxidation unit 34, and then the nanofiltration permeate enters the crystallization salt production unit 310 to obtain high-purity sodium chloride crystal salt 311. The supercritical water oxidation unit 34 is preferably provided with an oxidant inlet 6, a combustion improver inlet 7, a regulator inlet 8 and a purified water outlet 9. The divalent brine trapped by the salt separation unit 33 (taking a nanofiltration membrane as an example) is mainly divalent salt, the brine in the brine path is concentrated by the supercritical water oxidation unit 35 and COD is synchronously removed, and then different crystallization process units (an evaporation crystallization process unit 312 and a freezing crystallization process unit 314) are further selected to recover sodium sulfate enriched in the concentrated water, so as to respectively obtain crystalline salt sodium sulfate 313 and crystalline salt sodium sulfate decahydrate 315. The sodium sulfate decahydrate crystal salt 315 can be further processed by an evaporation crystallization process unit 312 to obtain a sodium sulfate crystal salt 313, and a very small amount of mother liquor is dried to obtain a miscellaneous salt without COD. The mother liquor dried miscellaneous salt 316 belongs to common solid waste.
Fig. 2 shows an embodiment in which the salt separation unit is located after the supercritical water oxidation unit. In figure 2, 21-coal chemical industry saline sewage, 22-pretreatment unit, 23-supercritical water oxidation unit, 24-purified water outlet, 25-oxidant inlet, 26-combustion improver inlet, 27-regulator inlet, 28-salt separation unit, 29-crystallization salt production unit, 210-sodium chloride crystal salt, 211-crystallization salt production unit, 212-sodium sulfate crystal salt, 213-crystallization salt production unit, 214-sodium sulfate crystal salt, and 215-mother liquor drying miscellaneous salt. In this treatment system, the treatment unit further includes a salt separation unit 28 connected in series with the supercritical water oxidation unit 23; wherein, according to the material flowing direction, the supercritical water oxidation unit 23 is arranged in front of the salt separation unit 28; the supercritical water oxidation unit 23 is provided with a treatment unit feeding hole and a supercritical water oxidation unit discharging hole; salt separation unit 28 is last to be provided with processing unit discharge gate and salt separation unit feed inlet, wherein, supercritical water oxidation unit discharge gate with salt separation unit feed inlet is linked together through the pipeline.
As shown in fig. 2, the salt-containing sewage 21 in the coal chemical industry is firstly subjected to impurity removal by the pretreatment unit 22, the obtained sewage is further concentrated by the supercritical water oxidation unit 23 and is subjected to synchronous organic matter removal treatment, so as to obtain concentrated brine which basically does not contain COD and meets the water quality requirement of the inlet of the subsequent salt separation unit 28, and then the concentrated brine enters the salt separation unit 28 (taking a nanofiltration membrane as an example) to realize the separation of monovalent salt and divalent salt, so as to obtain concentrated sodium chloride-rich water and concentrated sodium sulfate-rich water. The supercritical water oxidation unit 23 is preferably provided with a purified water outlet 24, an oxidant inlet 25, a combustion improver inlet 26 and a regulator inlet 27. The concentrated water rich in sodium chloride further enters a crystallization process unit 29 to obtain high-purity sodium chloride crystal salt 210. The sodium sulfate-rich concentrated water further passes through different crystallization process units (an evaporation crystallization process unit 211 and a freezing crystallization process unit 213) to respectively obtain a crystal salt sodium sulfate 212 and a crystal salt sodium sulfate decahydrate 214. The sodium sulfate decahydrate crystal salt 214 can be further processed by an evaporation crystallization process unit 211 to obtain a sodium sulfate crystal salt 212, and a very small amount of mother liquor is dried to obtain a mixed salt without COD. The mother liquor dried miscellaneous salt 215 belongs to common solid waste.
In the invention, the salt separation unit comprises one or more of a membrane separation unit and an electrodialysis salt separation unit. The salt separation unit can be used for separating different salt values of the salt-containing sewage entering the salt separation unit to obtain several salt water units with single components. As described above, in the preferred embodiment of the present invention, the salt separation unit may be disposed after the pretreatment unit and before the supercritical water oxidation unit, or may be disposed after the supercritical water oxidation unit and before the crystallization salt production unit. In a preferred embodiment of the present invention, the inlet of the salt separation unit may be connected to the outlet pipeline of the pretreatment unit, or may be connected to the outlet pipeline of the supercritical water oxidation unit, and the outlet of the salt separation unit may be connected to the inlet of the supercritical water oxidation unit, or may be connected to the inlet of the crystallization salt production unit.
As described above, in the preferred embodiment of the present invention, the supercritical water oxidation unit may be disposed after the pretreatment unit and before the salt separation unit, or may be disposed after the salt separation unit and before the crystallization salt production unit. In a preferred embodiment of the present invention, the inlet of the supercritical water oxidation unit may be connected to the outlet pipeline of the pretreatment unit, and may also be connected to the outlet pipeline of the salt separation unit, and the outlet of the supercritical water oxidation unit may be connected to the inlet of the salt separation unit, and may also be connected to the inlet of the crystallization salt production unit.
The supercritical water oxidation technology is a novel technology which can thoroughly, efficiently and quickly remove refractory organic matters, can be applied to the treatment of high-concentration organic sewage, sludge, oil sludge, refining tailings, hazardous wastes and the like in coal chemical industry and refineries, and the recovery of noble metals in catalysts or wastes, and has wide application prospect. The traditional supercritical water oxidation technology mainly focuses on the oxidation removal of organic matters in municipal sludge, printing and dyeing sludge and coal chemical industry organic wastewater, so that the final solid product can be used as general solid waste for landfill treatment, and the treated sewage can basically reach the discharge standard. Some researches have also mentioned that inorganic substances such as salts in the salt-containing wastewater are removed by using the property of water under the supercritical condition, but the researches mainly focus on research and development of special reactors or special materials for preventing salt deposition, blockage, corrosion and the like, or research on the influence of pre-removing salts before entering the supercritical reactor so as to reduce the degradation effect on organic substances in the wastewater and sludge. At present, no process application research for coupling the supercritical water oxidation desalination technology with the salt separation technology exists.
The supercritical water oxidation unit used in the present invention may be a supercritical water oxidation apparatus known in the art, which may be provided with a feed pump, a preheater, a mixer, a reactor, a gas-liquid separator, a tail gas collection detection unit, etc. The manner of connecting these components in a supercritical water oxidation unit is known to those skilled in the art. In one embodiment, the supercritical water oxidation unit comprises a mixer for mixing the wastewater with the oxidant, the oxidizer and the conditioner such that the saline organic wastewater, the oxidant, the oxidizer and the conditioner are mixed prior to entering the reactor. Therefore, the supercritical water oxidation unit is provided with an oxidant inlet, a combustion improver inlet and a regulator inlet, and is used for introducing the oxidant, the combustion improver and the regulator into the supercritical water oxidation unit and conveying the oxidant, the combustion improver and the regulator into the mixer. The supercritical water oxidation unit is provided with a purified water outlet for discharging the purified water passing through the supercritical water oxidation unit, and the purified water is the discharged water treated by the treatment system and can meet the emission standard. The TDS content in the purified water is less than 1000mg/L, and the chemical oxygen demand CODCrThe content is less than 50 mg/L.
The supercritical water oxidation unit is provided with a tail gas collecting and detecting system, can perform online detection and analysis on gas components generated by the device, guides optimization of process parameters, and can also recycle gas.
In a preferred embodiment of the invention, a supercritical water oxidation reactor is arranged in the supercritical water oxidation unit, organic matters in the fed sewage react with an oxidant quickly and thoroughly in the reactor, salt in the sewage and newly generated salt in the reaction process are crystallized and separated out quickly in a supercritical region and precipitate and descend, and the separated salt is dissolved into concentrated brine again after the bottom of the reactor is separated from the supercritical region, so that the concentration of the salt and the synchronous removal of the organic matters are realized. The concentrated high-concentration brine is discharged from the lower part of the reactor, enters the next treatment process link after being cooled and depressurized, desalted water vapor is discharged from the upper part of the reactor, the discharged water can be recycled as purified water after heat exchange, cooling, depressurization and gas-liquid separation, and the gas can be recycled after being analyzed and detected to be qualified.
The treatment system comprises a crystallization salt production unit, and can realize the recycling of salt. In a preferred embodiment of the present invention, the crystallization salt-producing unit comprises an evaporative crystallization unit or a freeze crystallization unit. The crystallization salt production unit is a unit for evaporating, crystallizing or freezing and crystallizing concentrated brine which is treated by the salt separation unit or the supercritical water oxidation unit and is basically free of organic matters to obtain product salt, and the crystallization salt production unit is provided with a crystallization single salt outlet. As described above, in the preferred embodiment of the present invention, the inlet of the crystallization salt-producing unit may be placed after the salt separation unit, or may be placed after the supercritical water oxidation unit. The inlet of the crystallization salt production unit can be connected with the outlet pipeline of the salt separation unit and also can be connected with the outlet of the supercritical water oxidation unit.
In the present invention, the treatment system of the present invention may include one or more sets of supercritical water oxidation units. When the supercritical water oxidation unit is arranged in front of the salt separation unit, the treatment system can comprise a group of supercritical water oxidation units, so that the mixed salt concentrated sewage treated by the supercritical water oxidation unit enters a subsequent salt separation unit for treatment to obtain several kinds of high concentrated single salt sewage which basically remove organic matters. And then, respectively processing in a crystallization salt production unit to obtain a crystal salt product.
When the supercritical water oxidation unit is disposed after the salt separation unit, the treatment system of the present invention may include one or more groups of supercritical water oxidation units. Mixing the single salt sewage subjected to pretreatment and separation by the salt separation unit with an oxidant, a combustion improver or a regulator respectively, then feeding the mixture into a supercritical water oxidation unit, and reacting together under a supercritical reaction condition to obtain several highly concentrated single salt sewage with organic matters basically removed. And then, respectively processing in a crystallization salt production unit to obtain a crystal salt product.
In another aspect, the invention provides a method for treating saline sewage in coal chemical industry, comprising the following steps:
enabling the coal chemical industry saline sewage to pass through a pretreatment unit to obtain pretreated sewage; the pretreatment unit is provided with a pretreatment unit feed inlet communicated with the coal chemical industry salt-containing sewage feed pipeline and a pretreatment unit discharge outlet used for discharging the pretreated sewage;
enabling the pretreated sewage to pass through a treatment unit to obtain strong brine and purified water; the treatment unit is provided with a treatment unit feed inlet communicated with the pretreatment unit discharge outlet, a treatment unit discharge outlet used for discharging the strong brine and a treatment unit water outlet used for discharging the purified water;
crystallizing the strong brine from the treatment unit in a crystallization salt production unit to obtain product salt; the crystallization salt production unit is provided with a crystallization salt production unit feeding port communicated with the treatment unit discharging port and a crystallization salt discharging port for discharging the product salt;
the treatment unit comprises a supercritical water oxidation unit, and the water outlet of the treatment unit is arranged on the supercritical water oxidation unit.
The processing method of the present invention can be performed in the processing system of the present invention, and for the description of the processing system, reference may be made to the above description, which is not repeated herein.
As described above, the supercritical water oxidation unit is internally provided with the supercritical water oxidation reactor, in the reactor, organic matters in the fed sewage react with the oxidant quickly and thoroughly, salt in the sewage and newly generated salt in the reaction process are crystallized, separated out and precipitated rapidly in the supercritical region and descend in a precipitation mode, and the separated salt is dissolved into the concentrated brine again after the bottom of the reactor is separated from the supercritical region, so that the concentration of the salt and the synchronous removal of the organic matters are realized. The concentrated high-concentration brine is discharged from the lower part of the reactor, enters the next treatment process link after being cooled and depressurized, desalted water vapor is discharged from the upper part of the reactor, the discharged water can be recycled as purified water after heat exchange, cooling, depressurization and gas-liquid separation, and the gas can be recycled after being analyzed and detected to be qualified.
In one embodiment, the reaction temperature of the supercritical water oxidation unit is 380-650 ℃, preferably 400-600 ℃, and the operation pressure is 20-35 MPa, preferably 23-30 MPa.
As described above, the supercritical water oxidation unit is provided with a mixer of the sewage and the oxidant, the combustion improver and the regulator, so that the salt-containing organic sewage, the oxidant, the combustion improver and the regulator are mixed before entering the reactor. The oxidant generally refers to one or more of hydrogen peroxide, oxygen and air. The combustion improver generally refers to one or more of flammable organic solvents (ethanol, isopropanol and the like). The modifier is generally an alkaline solution (such as an alkaline solution or an alkaline salt solution) for adjusting some acidic substances generated in the reaction process, so that the pH value of the obtained high-concentrated-salt wastewater is about 7. The mass fraction of the organic matter content in the sewage after mixing in the mixer is kept at 2-3%, so that the heat released by combustion can realize self-heating of the system.
The supercritical water oxidation unit may be added with a catalyst capable of improving the degradation effect of organic substances and reducing the operating conditions, as the case may be, the catalyst being selected from homogeneous catalysts such as sodium hydroxide, soluble transition metal salts (nitrates, sulfates, etc. of Cu, Fe, Mn, Ni, Co, etc.), alkaline salts (sodium carbonate, sodium bicarbonate, etc.), etc., and heterogeneous catalysts such as metal saltsOxides (CuO, MnO)2、ZrO2、TiO2Etc.) and activated carbon, etc.
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The saline wastewater treatment system in coal chemical industry provided by the invention is further described with reference to the accompanying drawings, but the invention is not limited thereby.
Example 1
As shown in figure 1, when a certain salt content in the salt-containing sewage has a great advantage, the process is adopted to separate and recover the dominant salt component. The method comprises the following steps that firstly, impurities in the salt-containing sewage 1 in the coal chemical industry are removed through a pretreatment unit 2, the obtained sewage is further concentrated through a supercritical water oxidation unit 3 and is subjected to synchronous organic matter removal treatment, the obtained concentrated solution basically does not contain COD (chemical oxygen demand) and has a certain dominant salt component close to saturation enters a unit 4 of a pure salt crystallization process I, and most of sodium chloride or sodium sulfate pure salt 10 is produced. The supercritical water oxidation unit 3 is provided with an oxidant inlet 6, a combustion improver inlet 7, a regulator inlet 8 and a purified water outlet 9. In the treatment of the unit 4 of the pure salt crystallization process I, the concentration ratio is controlled to be that the suboptimal salt component is close to saturation, and the mother liquor discharged from the unit 4 of the pure salt crystallization process I enters the unit 5 of the mixed salt crystallization process II to obtain a small amount of crystallized miscellaneous salt 11 without COD. The crystallized mixed salt 11 belongs to general solid waste.
In the embodiment, the saline wastewater 1 in the coal chemical industry is characterized in that TDS is more than or equal to 3000mg/L, and COD is more than or equal to 100 mg/L;
the final treatment effects are that the TDS content of the water in the purified water outlet 9 is less than 30mg/L, and the chemical oxygen demand CODCrThe content is basically 0mg/L, the TDS of the concentrated solution entering the unit 4 of the pure salt crystallization process I is more than or equal to 150000mg/L, and the COD isCrThe content is basically 0 mg/L; compared with the raw coal chemical salt-containing sewage 1, the concentration rate of the salt in the concentrated solution is more than 98%.
Example 2
As shown in fig. 2, the salt-containing sewage 21 in the coal chemical industry is firstly subjected to impurity removal by the pretreatment unit 22, the obtained sewage is further concentrated by the supercritical water oxidation unit 23 and is subjected to synchronous organic matter removal treatment, so as to obtain concentrated brine which basically does not contain COD and meets the water quality requirement of the inlet of the subsequent salt separation unit 28, and then the concentrated brine enters the salt separation unit 28 (taking a nanofiltration membrane as an example) to realize the separation of monovalent salt and divalent salt, so as to obtain concentrated sodium chloride-rich water and concentrated sodium sulfate-rich water. The supercritical water oxidation unit 3 is provided with a purified water outlet 24, an oxidant inlet 25, a combustion improver inlet 26 and a regulator inlet 27. The concentrated water rich in sodium chloride further enters a crystallization process unit 29 to obtain high-purity sodium chloride crystal salt 210. The sodium sulfate-rich concentrated water further passes through different crystallization process units (an evaporation crystallization process unit 211 and a freezing crystallization process unit 213) to respectively obtain a crystal salt sodium sulfate 212 and a crystal salt sodium sulfate decahydrate 214. The sodium sulfate decahydrate crystal salt 214 can be further processed by an evaporation crystallization process unit 211 to obtain a sodium sulfate crystal salt 212, and a very small amount of mother liquor is dried to obtain a mixed salt without COD. The mother liquor dried miscellaneous salt 215 belongs to common solid waste.
In the embodiment, the saline wastewater 21 of coal chemical industry is characterized in that TDS is more than or equal to 5000mg/L, and COD is more than or equal to 100 mg/L;
the final treatment effects are that the TDS content of the water in the purified water outlet 24 is less than 100mg/L, and the Chemical Oxygen Demand (COD)CrThe content is basically 0mg/L, the TDS of the concentrated solution entering the salt separation unit 28 is more than or equal to 100000mg/L, and the COD isCrThe content is basically 0 mg/L; compared with the raw coal chemical salt-containing sewage 21, the concentration rate of the salt in the concentrated solution is more than 95%.
Example 3
As shown in fig. 3, the saline wastewater 31 from coal chemical industry first passes through a pretreatment unit 32 to remove impurities, and the obtained wastewater further passes through a salt separation unit 33 (taking a nanofiltration membrane as an example) to separate monovalent salt and divalent salt, so as to obtain a saline water rich in sodium chloride and a saline water containing sodium sulfate and sodium chloride. The nanofiltration permeate mainly containing sodium chloride is concentrated and COD is synchronously removed through the supercritical water oxidation unit 34, and then the nanofiltration permeate enters the crystallization salt production unit 310 to obtain high-purity sodium chloride crystal salt 11. The supercritical water oxidation unit 34 is provided with an oxidant inlet 36, a combustion improver inlet 37, a regulator inlet 38 and a purified water outlet 39. The brine intercepted by the salt separation unit 33 (taking a nanofiltration membrane as an example) is mainly divalent salt, generally a sodium sulfate-rich solution or a mixed brine of sodium chloride and sodium sulfate, and the brine is concentrated by the supercritical water oxidation unit 35 and COD is synchronously removed, and then different crystallization process units (an evaporation crystallization process unit 312 and a freezing crystallization process unit 314) are further selected to recover sodium sulfate enriched in the concentrated water, so as to obtain a crystalline salt sodium sulfate 313 and a sodium sulfate decahydrate crystalline salt 315 respectively. The sodium sulfate decahydrate crystal salt 315 can be further processed by an evaporation crystallization process unit 312 to obtain a sodium sulfate crystal salt 313, and a very small amount of mother liquor is dried to obtain a miscellaneous salt without COD. The mother liquor dried miscellaneous salt 316 belongs to common solid waste.
In the embodiment, the saline wastewater 31 of coal chemical industry is characterized in that TDS is more than or equal to 20000mg/L, and COD is more than or equal to 1000 mg/L;
the final treatment effect is that the TDS content of the water in the purified water outlet 39 is less than 100mg/L and the chemical oxygen demand CODCrThe content is basically 0mg/L, the TDS of the concentrated solution entering the crystallization salt production unit 310 (or entering the evaporation crystallization process unit 312 or the freezing crystallization process unit 314) is more than or equal to 200000mg/L, and the COD isCrThe content is less than 50 mg/L; compared with the raw coal chemical salt-containing sewage 31, the concentration rate of the salt in the concentrated solution is over 90 percent.
It should be noted by those skilled in the art that the described embodiments of the present invention are merely exemplary and that various other substitutions, alterations, and modifications may be made within the scope of the present invention. Accordingly, the present invention is not limited to the above-described embodiments, but is only limited by the claims.
Claims (23)
1. A coal industry contains salt sewage treatment system includes:
the pretreatment unit is used for preliminarily treating the coal chemical industry saline sewage to obtain pretreated sewage; the pretreatment unit is provided with a pretreatment unit feed inlet communicated with the coal chemical industry salt-containing sewage feed pipeline and a pretreatment unit discharge outlet used for discharging the pretreated sewage;
the treatment unit is used for treating the pretreated sewage to obtain strong brine and purified water; the treatment unit is provided with a treatment unit feed inlet communicated with the pretreatment unit discharge outlet, a treatment unit discharge outlet used for discharging the strong brine and a treatment unit water outlet used for discharging the purified water;
a crystallization salt production unit for crystallizing the strong brine from the treatment unit to obtain product salt; the crystallization salt production unit is provided with a crystallization salt production unit feeding port communicated with the treatment unit discharging port and a crystallization salt discharging port for discharging the product salt;
the treatment unit comprises a supercritical water oxidation unit, and the water outlet of the treatment unit is arranged on the supercritical water oxidation unit.
2. The coal chemical industry saline sewage treatment system according to claim 1, wherein the treatment unit further comprises a salt separation unit connected in series with the supercritical water oxidation unit; wherein, according to the material flowing direction, the salt separation unit is arranged in front of the supercritical water oxidation unit;
the salt separation unit is provided with a feeding hole of the treatment unit and a discharging hole of the salt separation unit,
the supercritical water oxidation unit is provided with a treatment unit discharge hole and a supercritical water oxidation unit feed hole;
and the discharge hole of the salt separation unit is communicated with the feed inlet of the supercritical water oxidation unit through a pipeline.
3. The coal chemical industry saline sewage treatment system according to claim 1, wherein the treatment unit further comprises a salt separation unit connected in series with the supercritical water oxidation unit; wherein, according to the material flowing direction, the supercritical water oxidation unit is arranged in front of the salt separation unit;
the supercritical water oxidation unit is provided with a treatment unit feed inlet and a supercritical water oxidation unit discharge outlet;
the salt separation unit is provided with a discharge hole of the treatment unit and a feed hole of the salt separation unit,
the discharge hole of the supercritical water oxidation unit is communicated with the feed hole of the salt separation unit through a pipeline.
4. The coal chemical industry saline sewage treatment system according to any one of claims 1 to 3, wherein the pretreatment unit comprises one or more of a softening treatment system, an ion exchange system and a filtering treatment system.
5. The coal chemical industry saline sewage treatment system according to claim 4, wherein the filtration treatment system comprises an ultrafiltration treatment system.
6. The coal chemical industry saline sewage treatment system according to any one of claims 1 to 3, wherein the salt separation unit comprises one or more of a membrane separation unit and an electrodialysis salt separation unit.
7. The coal chemical industry saline sewage treatment system according to any one of claims 1 to 3,
the supercritical water oxidation unit is provided with a mixer of sewage, an oxidant, a combustion improver and a regulator, and is also provided with a tail gas collection and detection system.
8. The coal chemical industry saline sewage treatment system according to any one of claims 1 to 3, wherein the crystallization salt production unit comprises an evaporative crystallization unit or a freeze crystallization unit.
9. A method for treating saline sewage in coal chemical industry comprises the following steps:
enabling the coal chemical industry saline sewage to pass through a pretreatment unit to obtain pretreated sewage; the pretreatment unit is provided with a pretreatment unit feed inlet communicated with the coal chemical industry salt-containing sewage feed pipeline and a pretreatment unit discharge outlet used for discharging the pretreated sewage;
enabling the pretreated sewage to pass through a treatment unit to obtain strong brine and purified water; the treatment unit is provided with a treatment unit feed inlet communicated with the pretreatment unit discharge outlet, a treatment unit discharge outlet used for discharging the strong brine and a treatment unit water outlet used for discharging the purified water;
crystallizing the strong brine from the treatment unit in a crystallization salt production unit to obtain product salt; the crystallization salt production unit is provided with a crystallization salt production unit feeding port communicated with the treatment unit discharging port and a crystallization salt discharging port for discharging the product salt;
the treatment unit comprises a supercritical water oxidation unit, and the water outlet of the treatment unit is arranged on the supercritical water oxidation unit.
10. The process of claim 9, wherein the process unit further comprises a salt separation unit connected in series with the supercritical water oxidation unit; wherein, according to the material flowing direction, the salt separation unit is arranged in front of the supercritical water oxidation unit;
the salt separation unit is provided with a feeding hole of the treatment unit and a discharging hole of the salt separation unit,
the supercritical water oxidation unit is provided with a treatment unit discharge hole and a supercritical water oxidation unit feed hole;
the discharge hole of the salt separation unit is communicated with the feed hole of the supercritical water oxidation unit through a pipeline;
and the concentrated brine is discharged from a discharge hole of the treatment unit to the supercritical water oxidation unit.
11. The process of claim 9, wherein the process unit further comprises a salt separation unit connected in series with the supercritical water oxidation unit; wherein, according to the material flowing direction, the supercritical water oxidation unit is arranged in front of the salt separation unit;
the supercritical water oxidation unit is provided with a treatment unit feed inlet and a supercritical water oxidation unit discharge outlet;
the salt separation unit is provided with a discharge hole of the treatment unit and a feed hole of the salt separation unit,
the discharge hole of the supercritical water oxidation unit is communicated with the feed hole of the salt separation unit through a pipeline;
and the strong brine is discharged from the discharge hole of the processing unit to the salt separation unit.
12. The process of any one of claims 9 to 11, wherein the pre-treatment unit comprises one or more of a softening treatment system, an ion exchange system, a filtration treatment system.
13. The process of claim 12, wherein the filtration process system comprises an ultrafiltration process system.
14. The treatment method according to any one of claims 9 to 11, wherein the salt separation unit comprises one or more of a membrane separation unit and an electrodialysis salt separation unit.
15. The processing method according to any one of claims 9 to 11,
the reaction temperature of the supercritical water oxidation unit is 380-650 ℃, preferably 400-600 ℃, and the operation pressure is 20-35 MPa, preferably 23-30 MPa.
16. The processing method according to any one of claims 9 to 11,
the supercritical water oxidation unit is provided with a mixer of sewage, an oxidant, a combustion improver and a regulator, and is also provided with a tail gas collection and detection system.
17. The processing method according to claim 16,
the oxidant comprises one or more of hydrogen peroxide, oxygen and air;
the combustion improver comprises one or more flammable organic solvents;
the conditioning agent comprises an alkaline solution.
18. The process of claim 16, wherein a catalyst is also added to the supercritical water oxidation unit, the catalyst being selected from the group consisting of homogeneous catalysts and heterogeneous catalysts.
19. The process of claim 18, wherein the homogeneous catalyst is selected from one or more of sodium hydroxide, soluble transition metal salts, alkaline salts.
20. The treatment method of claim 19, wherein the soluble transition metal salt comprises a nitrate or sulfate of Cu, Fe, Mn, Ni, Co; the alkaline salt comprises one or more of sodium carbonate and sodium bicarbonate.
21. The process of claim 18, wherein the heterogeneous catalyst is selected from one or more of a metal oxide and activated carbon.
22. The process of claim 21, wherein said metal oxide comprises CuO, MnO2、ZrO2、TiO2One or more of (a).
23. The process of any one of claims 9 to 11, wherein the crystallization salt-producing unit comprises an evaporative crystallization unit or a freeze crystallization unit.
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| CN110963595A (en) * | 2018-09-28 | 2020-04-07 | 中国石油化工股份有限公司 | Coal chemical industry salt-containing wastewater treatment system and treatment method |
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| CN117105492A (en) * | 2023-10-25 | 2023-11-24 | 常熟理工学院 | Method for purifying high-concentration landfill leachate by utilizing supercritical water generator and product thereof |
| CN117105492B (en) * | 2023-10-25 | 2024-02-23 | 常熟理工学院 | Method for purifying high-concentration landfill leachate by utilizing supercritical water generator and product thereof |
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