CN112551787A - Mine water deep treatment system and method for treating mine water - Google Patents
Mine water deep treatment system and method for treating mine water Download PDFInfo
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 262
- 238000000034 method Methods 0.000 title claims abstract description 48
- 150000003839 salts Chemical class 0.000 claims abstract description 93
- 238000002425 crystallisation Methods 0.000 claims abstract description 87
- 230000008025 crystallization Effects 0.000 claims abstract description 87
- 238000001471 micro-filtration Methods 0.000 claims abstract description 80
- 238000001223 reverse osmosis Methods 0.000 claims abstract description 56
- 238000000926 separation method Methods 0.000 claims abstract description 43
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 42
- 238000001704 evaporation Methods 0.000 claims abstract description 42
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- 238000011084 recovery Methods 0.000 claims description 13
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- 238000005273 aeration Methods 0.000 claims description 6
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- 241000282414 Homo sapiens Species 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
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- 230000009471 action Effects 0.000 description 1
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- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- 239000008394 flocculating agent Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229910001437 manganese ion Inorganic materials 0.000 description 1
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- RSIJVJUOQBWMIM-UHFFFAOYSA-L sodium sulfate decahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].[O-]S([O-])(=O)=O RSIJVJUOQBWMIM-UHFFFAOYSA-L 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 235000019722 synbiotics Nutrition 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Images
Classifications
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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
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/10—Nature of the water, waste water, sewage or sludge to be treated from quarries or from mining activities
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- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses a mine water deep treatment system and a treatment method thereof, which comprise an adjusting tank, a V-shaped filter tank, an ultrafiltration system, a primary reverse osmosis system, a secondary microfiltration softening system, a secondary reverse osmosis system, a tertiary microfiltration softening system, an ion exchange softening system, a DTRO system and an evaporative crystallization salt separation system which are connected in sequence. According to different water inlet conditions, the method is subjected to corresponding pretreatment procedures, including an ultrafiltration system, a secondary microfiltration softening system, a tertiary microfiltration softening system and a softener. Mixing the clear liquids produced by the primary reverse osmosis system, the secondary reverse osmosis system, the DTRO system and the evaporative crystallization salt separation system to obtain produced water, and discharging the produced water into a production water tank; and finally, taking concentrated water discharged by the DTRO system as strong brine, and entering an evaporation crystallization salt separation system to obtain industrial anhydrous sodium sulfate and sodium chloride crystal salt. The system and the method disclosed by the invention are simple in process, the produced water can be comprehensively utilized, the sodium sulfate and the sodium chloride crystal salt can be effectively separated, and the resource utilization of the crystal salt and the salt can be realized.
Description
Technical Field
The invention relates to a mine water advanced treatment method and a system, belonging to the technical field of environment-friendly water treatment.
Background
With the rapid development of the industry and the increasing demand of coal resources, the coal industry has been developed greatly, so that the related industries have been improved and advanced. However, a large amount of mine water is gushed during coal mining, and the gushed mine water far exceeds the self-consumption water of the coal mine. In the actual coal mining process, underground water is in contact with a coal bed and a rock stratum and is influenced by human activities, so that a series of physical and chemical synbiotic reactions are easy to occur, and the coal mining method has obvious characteristics in the coal industry. The mine water mainly has the advantages that the content of suspended matters in the mine water containing the suspended matters is far higher than that of surface water, and the sensory properties are poor; meanwhile, the particle size of the contained suspended matters is small, the specific gravity is light, the sedimentation speed is slow, and the coagulation effect is poor; the mine water contains much higher total ion content than the common surface water, the main ion components are sulfate ions and chloride ions, and most of the sulfate ions are sulfate ions; the mine water is often accompanied by a large amount of ferrous ions and bivalent manganese ions, so that the treatment difficulty is increased. If the waste water is directly discharged, not only is water resource waste caused, but also environmental pollution is easily caused, and the physical and mental health of human beings and the environment-friendly social construction are seriously influenced.
The mine water is used as high-salt-content wastewater, and has the characteristics of low COD (chemical oxygen demand) and ammonia nitrogen content, high mineralization degree, high suspended matter and TDS (total dissolved solids) content, large water yield and the like. The wastewater is comprehensively utilized after advanced treatment, so that water resource recycling and resource utilization of crystallized salt are realized. The membrane separation technology is an energy-saving and environment-friendly technology, can separate substances in a molecular level, belongs to typical physical separation in the separation process, and has the advantages of extremely low energy consumption, high automation degree, simple process and convenient operation. Therefore, aiming at the water quality condition of the mine water, the membrane separation technology is utilized to produce clean water meeting the water quality requirement of the outlet water by stage treatment, and the enrichment of the salt content in the mine water and the reduction are realized. The produced clean water is recycled as water resource. The concentrated mine water is used as strong brine, the main component of the mine water is mixed salt of sodium sulfate and sodium chloride, the sodium sulfate content accounts for the main part, and the mine water can be subjected to crystallization salt recycling treatment after further treatment.
At present, the conventional treatment process for discharging the strong brine up to the standard is an evaporation crystallization technology, and mainly comprises single-effect evaporation, multi-effect evaporation and MVR evaporation. The mine water is treated to produce strong brine by a membrane separation technology, wherein inorganic salt exists in a mixed salt form, and if the crystalline salt produced by independently adopting the evaporative crystallization process is mixed salt, the crystalline salt can be regarded as dangerous solid waste in general and is not beneficial to resource utilization of the crystalline salt. If not properly treated, the crystalline salt forms secondary pollution under the leaching action. From the perspective of crystallization technology, the crystallization technology of single-component salt is mature, however, the solubility data and the rate constant of the single-component salt are not suitable for a complex system of mixed salt, even if the amount of other salts in the mixed salt is small, the crystallization process can be greatly influenced, and the discharge requirement of concentrated brine treatment is difficult to ensure. Therefore, aiming at the problems and the defects of the existing treatment technology, the mine water deep treatment process which is high in efficiency, energy saving and operability is developed, and the recycling of mine water resources and the salt separation recycling treatment are realized.
Disclosure of Invention
In order to solve the problems, the invention aims to provide a mine water deep treatment method and system. The main process is 'membrane separation technology + evaporative crystallization salt separation technology'. The treatment process has the characteristics of strong operability, simple process, high safety factor, low equipment investment and operation cost, cleanness and no pollution. The mine water advanced treatment technology is adopted to remove pollutants such as hardness, colloidal particles, sulfate ions, chloride ions and the like in water, the effluent quality meets the index requirements of three types of water quality (non-lake and reservoir) in table 1 and water quality index in table 2 of surface water environmental quality standard GB3838-2002, meanwhile, TDS is less than 500mg/L, sulfate is less than 250mg/L, and water resource recycling is realized. Meanwhile, an evaporative crystallization salt separation system creatively provides an evaporative crystallization technology, a freezing crystallization technology and a single-effect evaporation technology to realize the purpose of separating the sodium sulfate and the sodium chloride in the mine water, so that the problem of mixed salt hazardous waste is solved, and the crystallized salt can be recycled. The salt separation combination process has low energy consumption and simple operation, and the salt separation process of the sodium chloride and sodium sulfate binary system through evaporation and crystallization does not need to be accurately controlled, thereby reducing the operation cost.
In order to solve the problems, the invention adopts the following scheme: a mine water deep treatment system is characterized by comprising an adjusting tank, a V-shaped filter tank, an ultrafiltration system, a primary reverse osmosis system, a secondary microfiltration softening system, a secondary reverse osmosis system, a tertiary microfiltration softening system, an ion exchange softening system, a DTRO system and an evaporative crystallization salt separation system which are sequentially connected; the first-stage reverse osmosis system, the second-stage reverse osmosis system, the DTRO system and the evaporative crystallization salt separation system are all provided with clear liquid pipes and communicated with a water production pool, and the clear liquid pipes are used for discharging clear liquid into the water production pool.
Further, according to the design scheme, the mine water deep treatment system is characterized in that the secondary microfiltration softening system and the tertiary microfiltration softening system comprise a softening water tank and a microfiltration membrane unit; adding soda ash and caustic soda liquid into a softening water tank by adopting a chemical softening method to remove calcium, magnesium and silicon; the microfiltration membrane unit adopts a tubular microfiltration membrane, and after passing through a secondary microfiltration softening system and a tertiary microfiltration softening system, the calcium ion concentration is lower than 15mg/L, the magnesium ion concentration is lower than 20mg/L, and the silicon dioxide concentration is lower than 20 mg/L.
Further, according to the design scheme, the mine water advanced treatment system is characterized in that a pretreatment water production pool is arranged for water production of the secondary microfiltration softening system and the tertiary microfiltration softening system, acid is added into the pool to adjust the pH value to 6-9, and the alkalinity is removed by air stripping.
Further, according to the design scheme, the mine water deep treatment system is characterized in that the evaporative crystallization salt separation system comprises an evaporative crystallization unit, a freezing crystallization unit and a single-effect evaporative crystallization unit; the evaporative crystallization unit adopts MVR or multi-effect evaporation, and the evaporative crystallization unit and the freezing crystallization unit are jointly processed to obtain anhydrous sodium sulfate crystal salt with the purity of more than or equal to 97 percent; mother liquor produced by the freezing crystallization unit enters a single-effect evaporation crystallization unit; the single-effect evaporation crystallization unit adopts MVR or reduced pressure distillation to obtain sodium chloride crystal salt, the purity of the sodium chloride crystal salt is more than or equal to 97.5 percent, and the salt separation treatment of sodium sulfate and sodium chloride is realized; and the evaporation condensate discharged by the single-effect evaporation crystallization unit is used for preheating the liquid discharged by the freezing crystallizer.
Further, according to the design scheme, the mine water deep treatment system is characterized in that a wastewater collecting tank, a high-efficiency clarification tank and a sludge concentration tank are arranged between the V-shaped filter tank and the regulating tank; the wastewater collection tank is arranged below the V-shaped filter tank; backwashing wastewater of the V-shaped filter tank enters a wastewater collecting tank through self-flow, and the outlet of the wastewater collecting tank is connected to a high-efficiency clarification tank; supernatant of the high-efficiency clarification tank enters a regulating tank, and a lower-layer sludge outlet is connected with an inlet of a sludge concentration tank; returning supernatant liquor of the sludge concentration tank to the wastewater collection tank, and feeding the concentrated sludge into a sludge treatment device.
Further, the mine water deep treatment system according to the design scheme is characterized in that a concentrated water reaction tank and a concentrated water concentration tank are respectively arranged in the secondary microfiltration softening system and the tertiary microfiltration softening system; the inlet of the concentrated water reaction tank of the secondary microfiltration softening system is connected with the concentrated water produced by the primary reverse osmosis system, and the water outlet of the concentrated water reaction tank overflows to the concentrated water concentration tank of the secondary microfiltration softening system; the inlet of the concentrated water reaction tank of the third-stage microfiltration softening system is connected with the concentrated water produced by the second-stage reverse osmosis system, and the water outlet of the concentrated water reaction tank overflows to a concentrated water concentration tank of the third-stage microfiltration softening system; sodium carbonate and sodium hydroxide are added into concentrated water reaction tanks of the second-stage microfiltration softening system and the third-stage microfiltration softening system. The outlet overflows to a concentrated water concentration tank, a stirring system is arranged in the tank, and the outlet is connected to the inlets of the second-stage microfiltration unit and the third-stage microfiltration unit.
The second-stage microfiltration softening system and the third-stage microfiltration softening system comprise a concentrated water reaction tank, a concentrated water concentration tank and a microfiltration membrane unit. Adding soda ash and liquid caustic soda into a concentrated water reaction tank by adopting a chemical softening method for softening treatment; the microfiltration membrane unit adopts a tubular microfiltration membrane, and after passing through a microfiltration softening system, the calcium ion concentration is lower than 15mg/L, the magnesium ion concentration is lower than 20mg/L, and the silicon dioxide concentration is lower than 20 mg/L.
And a pretreatment water producing tank is arranged in front of the second-stage reverse osmosis system and the ion exchange softener and is respectively used for pretreating the produced water of the second-stage microfiltration softening system and the third-stage microfiltration softening system, acid is added into the pretreatment water producing tank to adjust the pH value to 6-9, and the alkalinity is removed by air stripping.
Further, the method for treating the mine water by the mine water advanced treatment system according to the design scheme is characterized in that the mine water is adjusted and homogenized by the adjusting tank, then enters the V-shaped filter tank for filtration, and is taken as purified water, and then sequentially passes through an ultrafiltration system, a primary reverse osmosis system, a secondary microfiltration softening system, a secondary reverse osmosis system, a tertiary microfiltration softening system, an ion exchange softening system, a DTRO system and an evaporative crystallization salt separation system; clear liquid produced by the primary reverse osmosis system, the secondary reverse osmosis system and the DTRO system is mixed to be used as produced water and is discharged into a production water tank; the concentrated water produced by the first-stage reverse osmosis system enters a second-stage reverse osmosis system after passing through a second-stage microfiltration softening system; the concentrated water produced by the secondary reverse osmosis system sequentially passes through the three-stage microfiltration softening system, the ion exchange softening system and the DTRO system, and finally the concentrated water discharged by the DTRO system enters the evaporation crystallization salt separation system as concentrated brine to produce evaporation condensate, anhydrous sodium sulfate crystal salt and sodium chloride crystal salt.
Further, the method for treating the mine water by the mine water advanced treatment system according to the design scheme is characterized in that the adjusting tank is an aeration adjusting tank, and reducing substances in the wastewater are removed through aeration pre-oxidation treatment for homogeneous adjustment and maintaining the stability of the subsequent process.
Further, the method for treating the mine water by the mine water advanced treatment system according to the design scheme is characterized in that the V-shaped filter tank adopts quartz sand homogeneous filter materials for removing colloid and SS in water, and the turbidity of the outlet water is less than or equal to 3 NTU.
Further, the method for treating the mine water by the mine water advanced treatment system according to the design scheme is characterized in that the ultrafiltration system adopts a hollow fiber membrane element, removes bacteria, viruses and colloidal particles in a cross-flow filtration mode, and has a recovery rate of more than or equal to 95%.
Further, the method for treating the mine water by the mine water advanced treatment system according to the design scheme is characterized in that the primary reverse osmosis system adopts a roll-type membrane, the recovery rate is more than or equal to 70%, and clear water is discharged into a water producing pool; the second-stage reverse osmosis system adopts a roll-type membrane, the recovery rate is not lower than 80%, and clear water is discharged into a production water tank.
Further, the method for treating the mine water by the mine water advanced treatment system according to the design scheme is characterized in that the ion exchange softener adopts chelating resin, and a 3-4% hydrochloric acid solution and a 4-5% sodium hydroxide solution are adopted for resin regeneration.
Further, the method for treating the mine water by the mine water advanced treatment system is characterized in that the recovery rate of the DTRO system is 50-55%, the operating pressure is less than or equal to 120bar, the concentrated water discharged by the DTRO system is used as the mother liquor of the evaporative crystallization salt separation system, and the clear water discharged by the DTRO system is discharged into a water production tank.
The invention discloses a mine water deep treatment method, which comprises the following steps:
after being regulated and homogenized by the regulating reservoir, the mine water enters the V-shaped filter tank for filtration, and filtrate is used as purified water and is subjected to step-by-step decrement treatment by a first-stage reverse osmosis system, a second-stage reverse osmosis system and a DTRO system. Wherein each stage of membrane system is subjected to corresponding pretreatment procedures according to different water inlet conditions, and comprises an ultrafiltration system, a secondary microfiltration softening system, a tertiary microfiltration softening system and an ion exchange softening system. Mixing the clear liquids output by the primary reverse osmosis system and the secondary reverse osmosis system and the DTRO system to be used as produced water, and discharging the produced water into a production water tank; and finally, taking concentrated water discharged by the DTRO system as strong brine, and entering an evaporation crystallization salt separation system to obtain industrial anhydrous sodium sulfate and sodium chloride crystal salt.
As a further scheme, the mixed salt mother liquor produced by the evaporative crystallization unit can be used for heating sodium sulfate decahydrate crystal slurry formed by freezing crystallization, and part of heat is recovered.
The invention also discloses a mine water deep treatment system which comprises an adjusting tank, a V-shaped filter tank, an ultrafiltration system, a primary reverse osmosis system, a secondary microfiltration softening system, a secondary reverse osmosis system, a tertiary microfiltration softening system, a DTRO system and an evaporative crystallization salt separation system which are sequentially connected.
Wherein a wastewater collecting tank, a high-efficiency clarifying tank and a sludge concentration tank are arranged between the V-shaped filtering tank and the adjusting tank. The waste water collecting tank sets up in V type filtering pond below, and V type filtering pond backwash waste water flows automatically and gets into the waste water collecting tank, and the waste water collecting tank goes out water connection to high-efficient depositing reservoir, and high-efficient depositing reservoir supernatant gets into the equalizing basin, and lower floor's sludge outlet and sludge thickening pond access connection, sludge thickening pond supernatant insert the waste water collecting tank, and sludge treatment device is arranged into to the mud after the concentration.
The invention has the following technical effects: (1) the mine water is treated by utilizing an adjusting tank and a V-shaped filter tank until the mine water meets the water inlet requirement of a membrane separation process, the stability of subsequent concentration treatment is maintained, and the mine water is further separated and purified by combining a membrane separation technology and an evaporative crystallization salt separation technology, so that the mine water outlet water meets the requirements of three types of water quality (non-lakes and reservoirs) in table 1 and the water quality index in table 2 of the 'surface water environmental quality standard GB 3838-2002'.
(2) The microfiltration softening device and the softening system can effectively remove calcium, magnesium and silicon in water, and the system is simple to operate and does not need to invest a large amount of medicaments and equipment cost.
(3) The quality of the effluent water is good and the system operation is stable after the mine water is deeply treated.
(4) The sodium sulfate and sodium chloride in the evaporative crystallization salt separation system have high salt yield purity, and the problems of mixed salt hazardous waste and the disadvantage of difficult evaporative crystallization salt separation of a sodium sulfate and sodium chloride binary system are solved.
(5) The whole process is simple and easy to implement, the safety coefficient is high, the salt separation operation is easy to control, and the cyclic utilization of mine water resources and the resource utilization of crystallized salt are realized.
Drawings
FIG. 1 is a schematic view of a mine water advanced treatment process flow disclosed by the invention;
FIG. 2 is a schematic process flow diagram of an evaporative crystallization salt separation system disclosed in the present invention.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings.
The embodiment discloses a mine water deep treatment method, which comprises the following technical scheme:
the mine water is primarily treated and then enters an adjusting tank for homogeneous adjustment to maintain the stability of the subsequent process. And carrying out preoxidation by aeration to remove iron, manganese and other reducing substances in the wastewater, and then entering a V-shaped filter tank to further remove colloid and SS (suspended solid) so as to reduce the effluent turbidity which is less than or equal to 3 NTU. The filter tank adopts quartz sand homogeneous filter materials, and the inlet water quality requirement meeting the follow-up process is obtained after screening, filtering, intercepting and adhering. The V-shaped filter chamber backwashing wastewater automatically flows to the wastewater collecting tank, and the wastewater collecting tank can be arranged below the V-shaped filter chamber, so that the backwashing wastewater can automatically flow conveniently. And (4) conveying the wastewater in the wastewater collection tank into a high-efficiency clarification tank through a lifting pump, and adding a flocculating agent for reaction and precipitation. Discharging the supernatant into an adjusting tank; and discharging the sludge to a sludge concentration tank. After the sludge entering the sludge concentration tank is subjected to gravity precipitation, supernatant liquid returns to the V-filter backwashing wastewater collection tank, and the sludge enters the sludge treatment system.
The effluent from the V-shaped filter tank enters a purified water tank and is used as the inlet water of an ultrafiltration system. The ultrafiltration system adopts a hollow fiber membrane element, removes bacteria, viruses and colloidal particles in a cross flow filtration mode, and improves the recovery rate of the system through a circulating pump. The ultrafiltration water enters an ultrafiltration pool. The ultrafiltration is used as a pretreatment unit of a first-stage reverse osmosis system, produced water directly enters the first-stage reverse osmosis system, the first-stage reverse osmosis system adopts a roll type reverse osmosis membrane, the scale formation of membrane elements is slowed down by adding a scale inhibitor, clear water automatically flows to a water producing tank after treatment, and concentrated water is used as raw water of the next stage for subsequent treatment. The first-stage reverse osmosis concentrated water enters a second-stage microfiltration softening system, is pumped into a concentrated water reaction tank by a lift pump, is added with soda ash and liquid caustic soda in the reaction tank, and is subjected to chemical reaction to convert the hardness of calcium and magnesium into chemical precipitates, and then passes through Mg (OH)2Reduction of SiO by adsorption2Concentration, retained by tubular microfiltration membranes. And adjusting the pH value to 6-9 by adding acid, entering a pretreatment water production tank, and removing the alkalinity. The softened water in the pretreatment water producing pool is pumped into a secondary reverse osmosis system by a booster pump and a high pressure pump, the system adopts a roll-type membrane, and the inlet water is provided with a scale inhibitor adding deviceAnd (4) automatically flowing the produced water to a water producing pool, and softening the concentrated water by a three-stage microfiltration softening system. The composition mode and the technological process of the three-stage microfiltration softening system are basically the same as those of the two-stage microfiltration softening system. In order to further remove hardness in water, an ion exchange softening system is arranged on the outlet water of the three-stage microfiltration softening system, chelating resin is adopted in the softening system, a 3-4% hydrochloric acid solution and a 4-5% sodium hydroxide solution are adopted in the regeneration process, and the produced water enters the DTRO system. The inlet water enters the DTRO membrane column through the high-pressure pump and the circulating pump, and the produced water is collected and then is pumped to a water producing pool; part of the concentrated water entering the concentrated water pipeline is connected to the inlet of the circulating pump, and the other part of the concentrated water is taken as concentrated solution to be extracted and collected and is taken as concentrated brine to be sent to an evaporation crystallization salt separation system.
The evaporative crystallization salt separation system comprises an evaporative crystallization unit, a freezing crystallization unit and a single-effect evaporative crystallization unit. The strong brine from DTRO enters an evaporation crystallization unit, wherein MVR or multi-effect evaporation can be adopted, sodium sulfate crystal slurry is produced from a salt leg, and sodium sulfate crystal salt is obtained through subsequent centrifugal drying. And the mixed salt mother liquor discharged from the evaporation unit enters a freezing crystallization unit, most of sodium sulfate crystal slurry in the mixed salt is separated out through freezing crystallization, and the mixed salt mother liquor returns to the evaporation unit. The return line can adopt a heat exchange device to exchange heat between the mixed salt mother liquor and the sodium sulfate crystal slurry discharged by the freezing crystallization, on one hand, part of heat is recovered, and on the other hand, the temperature of the mixed salt mother liquor entering the freezing crystallization unit is reduced. After the treatment of the freezing crystallization unit, the discharged mother liquor mainly comprises sodium chloride and a very small amount of sodium sulfate, the mother liquor enters a single-effect evaporation crystallization unit, and the sodium chloride crystal salt is obtained after MVR or reduced pressure distillation concentration and centrifugal drying.
The present invention will be described in further detail with reference to specific examples.
Example 1
In the embodiment of the invention, a schematic diagram of a process flow of deep treatment of mine water and a schematic diagram of a process flow of an evaporative crystallization salt separation system are shown in fig. 1 and fig. 2. The water quality conditions of the mine water from a mining area and the water source are shown in the table 1.
Table 1 mine water effluent quality conditions in a certain mining area:
| serial number | Name (R) | Unit of | Numerical value |
| 1 | Flow rate | m3/h | 2000 |
| 2 | pH | 7.91 | |
| 3 | COD | mg/L | 20 |
| 4 | Suspended matter | 20 | |
| 5 | Suspended particles | mm | 0.3 |
| 6 | NH4 + | mg/L | 0.37 |
| 7 | K+ | mg/L | 5.76 |
| 8 | Na+ | mg/L | 709.5 |
| 9 | Mg2+ | mg/L | 34.15 |
| 10 | Ca2+ | mg/L | 233 |
| 11 | HCO3 - | mg/L | 306.7 |
| 12 | Cl- | mg/L | 96.94 |
| 13 | F- | mg/L | 0.73 |
| 14 | SO4 2- | mg/L | 1927 |
| 15 | SiO2 | mg/L | 14.37 |
| 16 | Mn | mg/L | 0.29 |
| 17 | TDS | mg/L | 3330 |
The mine water enters a V-shaped filter tank for filtering after passing through a regulating tank, aeration pre-oxidation and homogenization regulation, the filter tank adopts quartz sand homogeneous filter materials, the turbidity of the outlet water is reduced to 1NTU after screening, filtering, interception and adhesion, and the outlet water enters a purified water tank and is used as the inlet water of an ultrafiltration system. The ultrafiltration system adopts a PVDF hollow fiber membrane element, removes bacteria, viruses and colloidal particles in a cross-flow filtration mode, has the recovery rate of about 96 percent and the operating pressure of 0.2MPa, and leads the ultrafiltration water to enter an ultrafiltration pool. The ultrafiltration is used as a pretreatment unit of a first-stage reverse osmosis system, produced water directly enters the first-stage reverse osmosis system, the first-stage reverse osmosis system adopts a roll type reverse osmosis membrane, the scale formation of a membrane element is slowed down by adding a scale inhibitor, the recovery rate can reach 73% after treatment, clear water TDS is about 18mg/L and automatically flows to a water producing pool, concentrated water TDS is about 6500mg/L and is used as raw water of the next stage for subsequent treatment. And the first-stage reverse osmosis concentrated water enters a second-stage microfiltration softening system, is pumped into a concentrated water reaction tank by a lift pump, soda ash and liquid caustic soda are added into the reaction tank, and are intercepted by a tubular microfiltration membrane, wherein the concentration of calcium ions in effluent is about 12mg/L, the concentration of magnesium ions is about 15mg/L, and the concentration of silicon dioxide is about 16 mg/L. Adjusting pH to 6.8 by adding sulfuric acid, feeding into a pretreatment water producing tank, and removing alkalinity by blowing. Softened water in the pretreatment production pool is pumped into a secondary reverse osmosis system through a booster pump and a high-pressure pump, the system adopts a roll-type membrane, the inlet water is provided with a scale inhibitor dosing device, the recovery rate reaches 85%, the TDS of the produced water is about 150mg/L, the produced water flows to the production pool automatically, the TDS of the concentrated water is about 27000mg/L, and the softened water is softened by a tertiary microfiltration softening system. The composition mode and the technological process of the three-stage microfiltration softening system are basically the same as those of the two-stage microfiltration softening system. In order to further remove the hardness in water, the water discharged from the three-stage microfiltration softening system is provided with an ion exchange softening system, the softening system adopts chelating resin, and the calcium ion concentration, the magnesium ion concentration and the silicon dioxide concentration of the discharged water after passing through the softening system are respectively about 14mg/L, 16mg/L and 18 mg/L. When the effluent water does not meet the requirement, 4 percent hydrochloric acid solution and 5 percent sodium hydroxide solution are adopted for regeneration. The produced water enters the DTRO system. The inlet water enters a DTRO membrane column through a high-pressure pump and a circulating pump, the operating pressure is about 3.0MPa, the recovery rate is about 52 percent, the TDS of the produced water is about 495mg/L, and the collected water is pumped to a water producing pool; the TDS of the concentrated water is about 45000mg/L, one part of the TDS enters a circulating pump inlet when entering a concentrated water pipeline, and the other part of the TDS is extracted as concentrated solution and collected as concentrated brine to be sent to an evaporation crystallization salt separation system.
And (3) enabling the strong brine from the DTRO to enter an evaporation crystallization unit, wherein the evaporation crystallization unit preferably adopts countercurrent triple-effect evaporation, controlling a sodium sulfate crystallization tank to be in a high-temperature section as shown in figure 2, wherein the single-effect evaporation temperature is about 90 ℃, the double-effect evaporation temperature is about 77 ℃, the triple-effect evaporation temperature is 60 ℃, producing sodium sulfate crystal slurry from a single-effect salt leg, and obtaining the sodium sulfate crystal salt with the purity of 98% through subsequent centrifugal drying. And (3) the mixed salt mother liquor discharged from the evaporation crystallization unit enters a freezing crystallization unit, most of sodium sulfate crystal slurry in the mixed salt is separated out through freezing crystallization, and the mixed salt mother liquor returns to the evaporation crystallization unit. The return line can adopt a heat exchange device to exchange heat between the mixed salt mother liquor and the sodium sulfate crystal slurry discharged by the freezing and crystallizing unit, so that on one hand, partial heat is recovered, and on the other hand, the temperature of the mixed salt mother liquor entering the freezing and crystallizing unit is reduced. After being processed by the freezing crystallization unit, the discharged mother liquor mainly comprises sodium chloride and a very small amount of sodium sulfate, the mother liquor enters a single-effect evaporation crystallization unit, reduced pressure evaporation crystallization is adopted, the evaporation temperature is 60 ℃, and sodium chloride crystal salt with the purity of 98% is obtained after centrifugal drying. The TDS of the produced water of the evaporation salt separation system is about 28mg/L and is discharged into a water producing pool.
The mine water is treated by the method, the produced water is formed by mixing a primary reverse osmosis system, a secondary reverse osmosis system, a DTRO system and triple effect evaporation condensate water, the comprehensive TDS is lower than 500mg/L, and the recycling standard of a local industrial park is met; the produced sodium sulfate with the purity of 98 percent and the sodium chloride crystal salt with the purity of 98 percent can be recycled as industrial salt products, thereby meeting the requirements of water resource recycling and salt separation recycling.
In the embodiments of the present invention, unless otherwise specifically defined and limited by the skilled in the art, the above embodiments should be regarded as describing, explaining and guiding the treatment process related to the present invention, and not as limiting, and are not limited to the above-mentioned embodiments. It will be apparent to those skilled in the art that various changes and modifications can be made in the embodiments without departing from the scope of the invention as defined in the appended claims.
Claims (15)
1. A mine water deep treatment system is characterized by comprising an adjusting tank, a V-shaped filter tank, an ultrafiltration system, a primary reverse osmosis system, a secondary microfiltration softening system, a secondary reverse osmosis system, a tertiary microfiltration softening system, an ion exchange softening system, a DTRO system and an evaporative crystallization salt separation system which are sequentially connected; the first-stage reverse osmosis system, the second-stage reverse osmosis system, the DTRO system and the evaporative crystallization salt separation system are all provided with clear liquid pipes and communicated with a water production pool, and the clear liquid pipes are used for discharging clear liquid into the water production pool.
2. The mine water deep treatment system of claim 1, wherein the secondary and tertiary microfiltration softening systems comprise a softening water tank and a microfiltration membrane unit; adding soda ash and caustic soda liquid into a softening water tank by adopting a chemical softening method to remove calcium, magnesium and silicon; the microfiltration membrane unit adopts a tubular microfiltration membrane, and after passing through a secondary microfiltration softening system and a tertiary microfiltration softening system, the calcium ion concentration is lower than 15mg/L, the magnesium ion concentration is lower than 20mg/L, and the silicon dioxide concentration is lower than 20 mg/L.
3. The mine water deep treatment system of claim 1, wherein the water produced by the secondary and tertiary microfiltration softening systems is provided with a pretreatment water producing tank, acid is added into the tank to adjust the pH value to 6-9, and the alkalinity is removed by air stripping.
4. The mine water deep treatment system of claim 1, wherein the evaporative crystallization salt separation system comprises an evaporative crystallization unit, a freezing crystallization unit, a single-effect evaporative crystallization unit; the evaporative crystallization unit adopts MVR or multi-effect evaporation, strong brine coming to a DTRO system is treated by the evaporative crystallization unit, discharged mixed salt mother liquor enters the freezing crystallization unit, most of sodium sulfate crystal slurry in the mixed salt mother liquor is separated out through freezing crystallization, the crystal slurry is returned to the evaporative crystallization unit, the evaporative crystallization unit and the freezing crystallization unit are jointly treated to obtain anhydrous sodium sulfate crystal salt, and the purity is more than or equal to 97%; mother liquor produced by the freezing crystallization unit enters a single-effect evaporation crystallization unit; the single-effect evaporation crystallization unit adopts MVR or reduced pressure distillation to obtain sodium chloride crystal salt, the purity of the sodium chloride crystal salt is more than or equal to 97.5 percent, and the salt separation treatment of sodium sulfate and sodium chloride is realized; the evaporation condensate produced by the single-effect evaporation crystallization unit enters the water producing tank through the clear liquid pipe.
5. The mine water deep treatment system of claim 1, wherein a wastewater collecting tank, a high-efficiency clarification tank and a sludge concentration tank are arranged between the V-shaped filter tank and the regulating tank; the wastewater collection tank is arranged below the V-shaped filter tank; backwashing wastewater of the V-shaped filter tank enters a wastewater collecting tank through self-flow, and the outlet of the wastewater collecting tank is connected to a high-efficiency clarification tank; supernatant of the high-efficiency clarification tank enters a regulating tank, and a lower-layer sludge outlet is connected with an inlet of a sludge concentration tank; returning supernatant liquor of the sludge concentration tank to the wastewater collection tank, and feeding the concentrated sludge into a sludge treatment device.
6. The mine water deep treatment system of claim 1, wherein a concentrated water reaction tank and a concentrated water concentration tank are respectively arranged in the secondary microfiltration softening system and the tertiary microfiltration softening system; the inlet of the concentrated water reaction tank of the secondary microfiltration softening system is connected with the concentrated water produced by the primary reverse osmosis system, and the water outlet of the concentrated water reaction tank overflows to the concentrated water concentration tank of the secondary microfiltration softening system; the inlet of the concentrated water reaction tank of the third-stage microfiltration softening system is connected with the concentrated water produced by the second-stage reverse osmosis system, and the water outlet of the concentrated water reaction tank overflows to a concentrated water concentration tank of the third-stage microfiltration softening system; sodium carbonate and sodium hydroxide are added into concentrated water reaction tanks of the second-stage microfiltration softening system and the third-stage microfiltration softening system for water softening treatment; stirring systems are arranged in concentrated water concentration tanks of the second-stage microfiltration softening system and the third-stage microfiltration softening system; and the concentrated water produced by the three-stage microfiltration softening system enters an ion exchange softening system.
7. The mine water advanced treatment system according to claim 1, wherein a pretreatment water production tank is arranged in front of the second-stage reverse osmosis system and the ion exchange softener, and is used for respectively pretreating water produced by the second-stage microfiltration softening system and the third-stage microfiltration softening system, adding acid into the pretreatment water production tank to adjust the pH value to 6-9, and removing alkalinity by air stripping.
8. The mine water deep treatment system as claimed in claim 4, wherein the mixed salt mother liquor produced by the evaporative crystallization unit exchanges heat with the sodium sulfate crystal slurry produced by the freezing crystallization unit, and is used for increasing the temperature of the sodium sulfate crystal slurry and reducing the temperature of the mixed salt mother liquor; the evaporative condensate discharged by the single-effect evaporative crystallization unit exchanges heat with the mother liquor produced by the freezing crystallization unit, and the temperature of the mother liquor produced by the freezing crystallization unit is increased.
9. The mine water deep treatment system for treating mine water according to claims 1-8, characterized in that the mine water is adjusted and homogenized by a regulating reservoir, then enters a V-shaped filter tank for filtration, and the filtrate is used as purified water and then sequentially passes through an ultrafiltration system, a primary reverse osmosis system, a secondary microfiltration softening system, a secondary reverse osmosis system, a tertiary microfiltration softening system, an ion exchange softening system, a DTRO system and an evaporative crystallization salt separation system; clear liquid produced by the primary reverse osmosis system, the secondary reverse osmosis system and the DTRO system is mixed to be used as produced water and is discharged into a production water tank; the concentrated water produced by the first-stage reverse osmosis system enters a second-stage reverse osmosis system after passing through a second-stage microfiltration softening system; the concentrated water produced by the secondary reverse osmosis system sequentially passes through the three-stage microfiltration softening system, the ion exchange softening system and the DTRO system, and finally the concentrated water discharged by the DTRO system enters the evaporation crystallization salt separation system as concentrated brine to produce evaporation condensate, anhydrous sodium sulfate crystal salt and sodium chloride crystal salt.
10. The mine water deep treatment system for treating mine water according to claim 9, wherein the adjusting tank is an aeration adjusting tank, and through aeration pre-oxidation treatment, reducing substances in wastewater are removed for homogenization adjustment and stability of subsequent processes is maintained.
11. The method for treating mine water by using the mine water advanced treatment system as claimed in claim 9, wherein the V-shaped filter chamber adopts a quartz sand homogeneous filter material for removing colloids and SS in water, and the turbidity of the effluent is less than or equal to 3 NTU.
12. The mine water deep treatment system of claim 9, wherein the ultrafiltration system employs a hollow fiber membrane element to remove bacteria, viruses and colloidal particles in a cross-flow filtration manner with a recovery rate of 95% or more.
13. The mine water advanced treatment system of claim 9, wherein the primary reverse osmosis system adopts a roll-type membrane, the recovery rate is greater than or equal to 70%, and clean water is discharged into a water producing pool; the second-stage reverse osmosis system adopts a roll-type membrane, the recovery rate is not lower than 80%, and clear water is discharged into a production water tank.
14. The mine water deep treatment system for treating mine water according to claim 9, wherein the ion exchange softener adopts chelating resin, and adopts 3-4% hydrochloric acid solution and 4-5% sodium hydroxide solution for resin regeneration.
15. The mine water advanced treatment system of claim 9, wherein the recovery rate of the DTRO system is 50-55%, the operating pressure is less than or equal to 120bar, the concentrated water discharged from the DTRO system is used as the mother liquor of the evaporative crystallization salt separation system, and the clear water discharged from the DTRO system is discharged into a water production tank.
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