CN106746113B - Process and system for recycling and reusing fluorine-containing wastewater in photovoltaic industry - Google Patents
Process and system for recycling and reusing fluorine-containing wastewater in photovoltaic industry Download PDFInfo
- Publication number
- CN106746113B CN106746113B CN201611172769.7A CN201611172769A CN106746113B CN 106746113 B CN106746113 B CN 106746113B CN 201611172769 A CN201611172769 A CN 201611172769A CN 106746113 B CN106746113 B CN 106746113B
- Authority
- CN
- China
- Prior art keywords
- wastewater
- tank
- pool
- concentrated
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- 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
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/08—Compounds containing halogen
- C01B33/10—Compounds containing silicon, fluorine, and other elements
- C01B33/103—Fluosilicic acid; Salts thereof
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/20—Halides
- C01F11/22—Fluorides
-
- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
-
- 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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
-
- 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
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
- C02F1/583—Treatment of water, waste water, or sewage by removing specified dissolved compounds by removing fluoride or fluorine compounds
-
- 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
- C02F2001/007—Processes including a sedimentation step
-
- 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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F2001/5218—Crystallization
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Engineering & Computer Science (AREA)
- Hydrology & Water Resources (AREA)
- Water Supply & Treatment (AREA)
- Geology (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Removal Of Specific Substances (AREA)
- Heat Treatment Of Water, Waste Water Or Sewage (AREA)
- Separation Of Suspended Particles By Flocculating Agents (AREA)
Abstract
The invention provides a process for recycling and reusing fluorine-containing wastewater in the photovoltaic industry, which is characterized by collecting concentrated acid wastewater, concentrated alkali wastewater, dilute acid wastewater and dilute alkali wastewater in a classified manner; adding sodium salt or potassium salt into the concentrated acid wastewater according to the concentration of fluosilicate ions in the concentrated acid wastewater to perform crystallization reaction to obtain fluosilicate, and adding calcium salt into the concentrated acid wastewater according to the concentration of the fluosilicate ions in the concentrated acid wastewater to perform crystallization reaction to obtain calcium fluoride; sending dilute alkali wastewater and dilute acid wastewater into a reaction tank for defluorination treatment, then sending into a sedimentation tank for sedimentation treatment, then carrying out chemical softening treatment, and sequentially passing through a sand filter, an activated carbon filter, a resin softener and a reverse osmosis device to obtain product water; the system effluent water and the concentrated alkali wastewater after the crystallization reaction of the concentrated acid wastewater are sent into a reaction tank for defluorination treatment, then sent into a sedimentation tank for sedimentation treatment, and then obtained through an evaporator to produce condensed water.
Description
Technical Field
The invention relates to the technical field of industrial wastewater treatment, in particular to a process and a system for recycling and reusing fluorine-containing wastewater in the photovoltaic industry.
Background
A large amount of hydrofluoric acid is used in the production process of the photovoltaic industry (monocrystalline silicon solar cells and polycrystalline silicon solar cells), so that industrial wastewater with high fluorine ion concentration is generated. The fluorine-containing wastewater is generated in the production links of acid washing, surface wool making, phosphorus-removed silicate glass and the like, and mainly comprises two parts of concentrated acid wastewater (with small water amount) and dilute acid wastewater. Wherein the content of fluorine ions in the polycrystalline silicon concentrated acid wastewater reaches 150000 mg/L, and the content of fluorine ions in the monocrystalline silicon concentrated acid wastewater reaches 10000 mg/L; the fluoride ion content of the polycrystalline silicon dilute acid wastewater is about 1000 mg/L, and the fluoride ion content of the monocrystalline silicon dilute acid wastewater is about 500 mg/L. Other pollutants contained in the concentrated acid wastewater and the dilute acid wastewater mainly comprise fluorine silicate, nitrate radical, chloride ion and the like. In addition, a large amount of concentrated alkali wastewater and dilute alkali wastewater can be discharged in the production process of polycrystalline silicon and monocrystalline silicon, the main pollutants are organic matters, sodium silicate and alkali, and the concentration of fluorine ions is more than 20 mg/L.
The conventional treatment process of fluorine-containing wastewater is to add calcium salts such as lime or calcium chloride to generate calcium fluoride precipitate. CaF in calcium fluoride sludge 2 The content of (A) is only about 60% or less (dry basis), and a large amount of silica, calcium carbonate and the like are contained, and the standard of direct utilization is not met, and the solid waste can only be landfilled and disposed. Meanwhile, the supernatant effluent after the calcium salt defluorination still contains at least 8mg/L of fluorinion and a large amount of calcium ions, so that reverse osmosis recycling cannot be directly carried out, and most of the supernatant effluent is discharged. Therefore, the calcium salt precipitation method not only causes a large amount of waste of reuse water resources and fluorine resources, but also causes the problem of secondary pollution of calcium fluoride sludge. The key for improving the wastewater process is to reduce the concentration of fluorine ions and calcium ions in the supernatant liquid after the calcium salt precipitation and the fluorine removal and recycle the fluorine.
The invention discloses a process for preparing sodium fluosilicate from fluorine-containing wastewater, and provides a process for producing sodium fluosilicate by adding silicon slag into fluorine-containing wastewater and then adding sodium chloride solution. The method can reduce the fluorine content in the water to 0.1-0.5 g/L, and solves the resource problem of the fluorine-containing wastewater with medium and low concentration (the concentration of fluorine ions is less than thousands of mg/L) to a certain extent; the patent does not provide a technical means for recycling high-concentration fluorine-containing wastewater and advanced treatment and reuse of the fluorine-containing wastewater.
Chinese patent CN101941752B is a method and apparatus for treating fluorine-containing waste water, which provides a process for extracting calcium fluoride from fluorine-containing waste water by using a solid-liquid two-phase fluidized bed as a crystallization reactor and calcium chloride as a seed crystalAn idea is provided. The method mainly aims at the fluorine-containing wastewater in the industries of chemical industry, nonferrous metallurgy, glass, electronics and the like, but does not consider that the silicate, the fluosilicate and the like which exist in the fluorine-containing wastewater in the photovoltaic industry can react with Ca 2+ And (3) reacting and pollutants influencing the purity of final product fluoride, so that the method cannot be directly used for fluorine resource utilization and water production advanced treatment and recycling of fluorine-containing wastewater in the photovoltaic industry.
The invention patent CN103011453B of China is a method for treating fluorine-containing wastewater in solar wafer production, which proposes to mix dilute alkali wastewater with calcium carbonate powder to prepare soluble calcium salt water solution, mix with concentrated acid wastewater and add into a stirring tank type reaction crystallizer to prepare calcium fluoride particles; the effluent is mixed with dilute acid waste water and alkaline waste water and then enters a fluidized bed crystallizer to prepare calcium fluoride particles. In the method, the fluorine concentration of the concentrated acid wastewater is more than 5000mg/L, and the fluorine concentration of the dilute acid wastewater is less than 100mg/L. The method does not fully consider the impurities such as fluosilicate contained in the fluorine-containing wastewater of the photovoltaic cell, and the effluent only meets the discharge standard.
The invention of Chinese patent CN102307816A fluorine and silicon-containing wastewater treatment method, calcium fluoride manufacturing method and fluorine-containing wastewater treatment equipment proposes adding sodium hydroxide to decompose fluosilicic acid in wastewater, so that silicon in wastewater is precipitated and discharged in the form of silicate; and adding water-soluble calcium salt into the separated mother liquor to recover calcium fluoride. The method does not need to dilute the wastewater of fluorine and silicon so as to reduce the silicon concentration to be below 500 mg/L. However, the strong alkali sodium hydroxide is directly added into the high-concentration fluorine-containing wastewater, so that the strong exothermic reaction is caused, local overheating is easily caused, and the requirements on equipment materials and safe operation are high; the silicate precipitate is discharged outside, which causes the waste of silicon resource.
The invention patent CN103936218B in China is a method for zero emission of wastewater from high-ammonia-content and nitrogen-containing cell production in photovoltaic industry, and provides a system process for adjusting homogenization, precipitation and fluorine removal, filtration, reverse osmosis, concentrated water crystallization, concentrated water reverse osmosis and evaporation. The key of the process is that the redundant calcium salt in the calcium salt defluorination supernatant is removed by adopting sodium carbonate, and the reverse osmosis concentrated water is used for inducing and accelerating crystallization, so that the aims of reducing membrane pollution and improving the recovery rate can be achieved. The calcium fluoride sludge in the method is discharged as sludge for disposal, and a corresponding fluorine recycling method is not provided.
Disclosure of Invention
Aiming at the problems in the fluorine-containing wastewater treatment method in the prior art, the invention provides a process for recycling and reusing the fluorine-containing wastewater in the photovoltaic industry, and further provides a system for recycling and reusing the fluorine-containing wastewater in the photovoltaic industry.
The technical scheme adopted by the invention is as follows: a process for recycling and reusing fluorine-containing wastewater in the photovoltaic industry is characterized in that concentrated acid wastewater, concentrated alkali wastewater, dilute acid wastewater and dilute alkali wastewater are collected in a classified manner; according to the concentration of fluorine ions and silicon ions in the concentrated acid wastewater, firstly adding sodium salt or potassium salt into the concentrated acid wastewater to carry out crystallization reaction to obtain fluosilicate, and then adding calcium salt into the concentrated acid wastewater to carry out crystallization reaction to obtain calcium fluoride; sending dilute alkali wastewater and dilute acid wastewater into a reaction tank for defluorination treatment, then sending into a sedimentation tank for sedimentation treatment, then carrying out chemical softening treatment, and sequentially passing through a sand filter, an activated carbon filter, a resin softener and a reverse osmosis device to obtain product water; and (3) feeding system effluent and concentrated alkali wastewater after the crystallization reaction of the concentrated acid wastewater into a reaction tank for defluorination treatment, then feeding the system effluent and the concentrated alkali wastewater into a sedimentation tank for sedimentation treatment, and then condensing the system effluent and the concentrated alkali wastewater through an evaporator to obtain water.
Furthermore, the reaction tank and the sedimentation tank are provided with one stage or two stages according to the concentration of the fluorine ions in the dilute alkali wastewater, the dilute acid wastewater and the concentrated alkali wastewater.
Further, a process for recycling and reusing fluorine-containing wastewater in photovoltaic industry is characterized by comprising the following steps:
step 1: collecting waste water: classifying and collecting concentrated acid wastewater, concentrated alkali wastewater, dilute acid wastewater and dilute alkali wastewater;
step 2: carrying out resource treatment on concentrated acid wastewater: feeding concentrated acid wastewater into a first regulating reservoir for homogenization, measuring the concentration of fluorine ions and silicon ions in the concentrated acid wastewater, pumping the concentrated acid wastewater into a first crystallization reactor, adding sodium salt or potassium salt into the first crystallization reactor for crystallization reaction, periodically discharging concentrated crystallization liquid at the bottom of the first reactor, and drying to obtain fluorosilicate; sending the supernatant in the first crystallization reactor into a second crystallization reactor, adding a calcium salt solution into the second crystallization reactor for crystallization reaction, periodically discharging a crystallization concentrated solution at the bottom of the second reactor, and drying to obtain calcium fluoride;
and 3, step 3: treating dilute alkali wastewater and dilute acid wastewater: discharging dilute alkali wastewater and dilute acid wastewater into a third regulating reservoir, homogenizing and homogenizing, pumping into a first reaction reservoir, adding calcium salt, a coagulant and a flocculant for reaction for defluorination treatment, feeding mixed liquor into a first sedimentation reservoir from the first reaction reservoir for sedimentation, feeding supernatant of the first sedimentation reservoir into a chemical softening reservoir, adding a softening agent for chemical softening treatment, feeding effluent of the chemical softening reservoir into a second sedimentation reservoir for sedimentation, feeding supernatant of the second sedimentation reservoir into a first intermediate water reservoir, sequentially passing through a sand filter, an active carbon filter and a resin softener by a pump for removing particles, organic matters and residual hardness in water, feeding produced water of the resin softener into a reverse osmosis device by a high-pressure pump, and discharging the produced water from a pure water outlet of the reverse osmosis device;
Further, partial sludge in the third sedimentation tank is filter-pressed and transported outwards, and partial sludge is returned to the second reaction tank; and part of sludge in the first sedimentation tank is filter-pressed and transported outwards, part of sludge is returned to the first reaction tank, and the sludge in the second sedimentation tank is filter-pressed and transported outwards.
Furthermore, the proportion of partial sludge returned to the reaction tank is 20 to 50 percent of the total sludge amount of the sedimentation tank.
Furthermore, the sand filter and the activated carbon filter in the step 3 are respectively provided with a backwashing device, and backwashing water of the backwashing devices of the sand filter and the activated carbon filter, regenerated water of the resin softener and concentrated water discharged by the reverse osmosis device, and supernatant and concentrated alkali wastewater of the second crystallization reactor in the step 2 are discharged into a second regulating tank for homogenizing and equalizing.
Further, the sodium salt comprises at least one of sodium chloride, sodium nitrate and sodium silicate, and the adding amount of the sodium salt is kept in a manner that the total molar concentration ratio of sodium and silicon in the first crystallization reactor in the sodium in the first crystallization reactor is kept in a ratio of Na: si = (2-3.5) 1; the potassium salt comprises at least one of potassium chloride and potassium nitrate; the amount of potassium salt added was such that the total molar concentration ratio of potassium and silicon in the first crystallization reactor was maintained at K: si = (2-3): 1.
Further, the calcium salt solution includes at least one of a calcium chloride solution and a calcium hydroxide solution, and the calcium salt solution is added in an amount to maintain the total molar concentration ratio of calcium and fluorine in the second crystallization reactor at (0.6-0.75): 1.
The utility model provides a system for fluoride waste water resource and retrieval and utilization of photovoltaic trade which characterized in that: comprises a dilute alkali wastewater pool connected with dilute alkali wastewater incoming water through a pipeline, a dilute acid wastewater pool connected with dilute acid wastewater incoming water, a concentrated alkali wastewater pool connected with concentrated alkali wastewater incoming water, and a concentrated acid wastewater pool connected with concentrated acid wastewater incoming water;
the concentrated acid wastewater pool is sequentially connected with a first regulating pool, a first crystallization reactor, a second crystallization reactor and a second regulating pool; the first crystallization reactor is provided with a feed port for adding sodium salt or potassium salt, the second crystallization reactor is provided with a feed port for adding calcium salt solution, and a lift pump is arranged between the concentrated acid wastewater pool and the first regulating pool;
the concentrated alkali wastewater pool is connected with a second regulating pool, the water outlet of the second regulating pool is connected with a second reaction pool through a lifting pump, the second reaction pool is provided with a feed inlet for adding a defluorinating agent, the second reaction pool is sequentially connected with a third sedimentation pool, a second intermediate pool and an evaporator, and produced water is discharged from a condensate water outlet of the evaporator;
the dilute alkali wastewater pool and the dilute acid wastewater pool are respectively connected to a third regulating pool, the third regulating pool is connected with a first reaction pool through a lifting pump, the first reaction pool is provided with a feed port for adding a defluorination agent, the first reaction pool is sequentially connected with a first sedimentation pool, a chemical softening pool, a second sedimentation pool and a first intermediate pool, the chemical softening pool is provided with a feed port for adding a chemical softening agent, the first intermediate pool is sequentially connected with a sand filter, a carbon filter and a resin softener through the lifting pump, a water outlet of the resin softener is connected with a reverse osmosis device, and produced water is discharged from a pure water outlet of the reverse osmosis device;
furthermore, the sand filter and the carbon filter are respectively connected with a backwashing device, backwashing water outlets of the sand filter and the carbon filter are respectively connected with a second regulating reservoir, and a regenerated water outlet of the resin softener and a concentrated water outlet of the reverse osmosis device are respectively connected with the second regulating reservoir;
further, a sludge conveying device is arranged between the second reaction tank and the third sedimentation tank, sludge in the third sedimentation tank is conveyed to the second reaction tank through the sludge conveying device, a sludge conveying device is arranged between the first reaction tank and the first sedimentation tank, and sludge in the first sedimentation tank is conveyed to the first reaction tank through the sludge conveying device;
furthermore, the first sedimentation tank, the second sedimentation tank, the third sedimentation tank and the evaporator are respectively provided with a slag discharge port.
The invention has the beneficial effects that:
1) Concentrated acid wastewater, concentrated alkali wastewater, dilute acid wastewater and dilute alkali wastewater are classified, collected and treated, the set process is strong in pertinence, and the overall treatment difficulty and the operation cost are reduced;
2) Carrying out secondary crystallization recycling treatment on the concentrated acid wastewater: the first-stage crystallization can prepare fluosilicate, and the second-stage crystallization can prepare calcium fluoride with higher purity;
3) The lime is adopted to remove fluorine from the dilute acid wastewater and the dilute alkali wastewater, so that the salt content of the wastewater is reduced, and the later reverse osmosis desalination treatment is facilitated;
4) Part of sludge in the defluorination sedimentation tank flows back, and excess lime in the sludge can be further utilized, so that the lime consumption is reduced by 5-10%;
5) The chemical softening method and the resin softening method are adopted to carry out secondary softening treatment on calcium in the supernatant of the defluorination sedimentation tank, so that the low hardness of reverse osmosis inlet water is ensured, and membrane pollution is slowed down.
6) Fully recovering the produced water, evaporating the concentrated acid wastewater subjected to resource treatment and the wastewater discharged in the treatment process of the dilute acid wastewater and the dilute alkali wastewater together with the concentrated alkali wastewater, and having high wastewater regeneration recovery rate.
The invention fully considers the characteristics of various waste water in the photovoltaic industry: recycling dilute acid dilute alkali wastewater with low salt content; carrying out secondary resource recovery on concentrated acid wastewater with high fluoride ion concentration; and (4) evaporating the concentrated alkali wastewater with high organic matter concentration and other backwashing water. The process can achieve nearly 100% of wastewater regeneration recovery rate; the calcium fluoride sludge is reduced by more than 85 percent; the recovered fluosilicate and calcium fluoride have obvious economic benefit.
Drawings
FIG. 1 is a process flow diagram for the recycling and reusing of fluorine-containing wastewater in the photovoltaic industry according to the present invention;
FIG. 2 is a block diagram of a system for recycling and reusing fluorine-containing wastewater in the photovoltaic industry.
Detailed Description
The following examples are given for illustrative purposes and to help further understand the nature of the present invention, but the details of the examples are only for the purpose of illustrating the present invention and do not represent all the technical solutions under the inventive concept, therefore, should not be construed as limiting the present invention, and some insubstantial additions and/or modifications, such as simple changes or substitutions with technical features having the same or similar technical effects, which do not depart from the inventive concept, are considered to be within the scope of the present invention.
Referring to fig. 1, a process for recycling and reusing fluorine-containing wastewater in photovoltaic industry comprises the following steps:
step 1: collecting waste water: classifying and collecting concentrated acid wastewater, concentrated alkali wastewater, dilute acid wastewater and dilute alkali wastewater;
step 2: resource treatment of concentrated acid wastewater: feeding the concentrated acid wastewater into a first regulating reservoir for homogenizing, measuring the concentration of fluorine ions and silicon ions in the concentrated acid wastewater, pumping the concentrated acid wastewater into a first crystallization reactor, adding sodium salt or potassium salt into the first crystallization reactor for crystallization reaction, wherein the sodium salt comprises at least one of sodium chloride, sodium nitrate and sodium silicate, and the adding amount of the sodium salt keeps the total molar concentration ratio of sodium to silicon in the first crystallization reactor to be Na: si = (2-3.5) 1; the potassium salt comprises at least one of potassium chloride and potassium nitrate; the amount of potassium salt added is such that the total molar concentration ratio of potassium and silicon in the first crystallization reactor is maintained at K: si = (2-3): 1, and periodically discharging the concentrated crystallization solution at the bottom of the first reactor, and drying to obtain fluorosilicate; feeding the supernatant in the first crystallization reactor into a second crystallization reactor, adding a calcium salt solution into the second crystallization reactor for crystallization reaction, wherein the calcium salt solution comprises at least one of a calcium chloride solution and a calcium hydroxide solution, the adding amount of the calcium salt solution keeps the total molar concentration ratio of calcium to fluorine in the second crystallization reactor at (0.6-0.75): 1, periodically discharging a crystallization concentrated solution at the bottom of the second reactor, and drying to obtain calcium fluoride;
and step 3: treating dilute alkali wastewater and dilute acid wastewater: discharging dilute alkali wastewater and dilute acid wastewater into a third regulating tank, homogenizing and homogenizing, pumping into a first reaction tank, adding calcium salt, a coagulant and a flocculant for reaction for defluorination, feeding mixed liquor into a first sedimentation tank from the first reaction tank for sedimentation, carrying out filter pressing and outward transportation on part of sludge in the first sedimentation tank, returning part of sludge to the first reaction tank, carrying out filter pressing and outward transportation on part of sludge in a second sedimentation tank, feeding supernatant of the first sedimentation tank into a chemical softening tank, adding a softening agent for chemical softening treatment, feeding effluent of the chemical softening tank into the second sedimentation tank for sedimentation, feeding part of sludge returned to the reaction tank into a reverse osmosis device by a high-pressure pump, wherein the proportion of the part of sludge is 20-50% of the total sludge of the sedimentation tank, feeding supernatant of the second sedimentation tank into a first intermediate water tank, and then sequentially passing through a sand filter, an activated carbon filter and a resin softener by a pump for removing particles, organic matters and residual hardness in water, and feeding softened produced water into a reverse osmosis device by the high-pressure pump, and discharging the produced water from a pure water outlet of the reverse osmosis device;
Referring to fig. 2, the system for recycling and reusing fluorine-containing wastewater in the photovoltaic industry comprises a dilute alkali wastewater pool 1 connected with dilute alkali wastewater incoming water through a pipeline, a dilute acid wastewater pool 2 connected with dilute acid wastewater incoming water, a concentrated alkali wastewater pool 3 connected with concentrated alkali wastewater incoming water, and a concentrated acid wastewater pool 4 connected with concentrated acid wastewater incoming water;
the concentrated acid wastewater tank 4 is connected with a first regulating tank 5, a first crystallization reactor 6, a second crystallization reactor 7 and a second regulating tank 8 in sequence; the first crystallization reactor 6 is provided with a feed port for adding sodium salt or potassium salt, the second crystallization reactor 7 is provided with a feed port for adding calcium salt solution, and a lift pump is arranged between the concentrated acid wastewater pool 4 and the first regulating pool 5; the concentrated alkali wastewater tank 3 is connected with a second regulating tank 8, the water outlet of the second regulating tank 8 is connected with a second reaction tank 10 through a lifting pump 9, the second reaction tank 10 is provided with a feed inlet for adding a defluorination agent, the second reaction tank 10 is sequentially connected with a third sedimentation tank 11, a second intermediate water tank 12 and an evaporator 13, produced water is discharged from a condensed water outlet of the evaporator 13, a sludge conveying device is arranged between the second reaction tank 10 and the third sedimentation tank 11, and sludge in the third sedimentation tank 11 is conveyed to the second reaction tank 10 through the sludge conveying device;
the dilute alkali wastewater pool 1 and the dilute acid wastewater pool 2 are respectively connected to a third regulating pool 14, the third regulating pool 14 is connected with a first reaction pool 15 through a lifting pump 9, the first reaction pool 15 is provided with a feed inlet for adding a fluorine removal medicament, the first reaction pool 15 is sequentially connected with a first sedimentation pool 16, a chemical softening pool 17, a second sedimentation pool 18 and a first intermediate pool 19, a sludge conveying device is further arranged between the first reaction pool 15 and the first sedimentation pool 16, sludge in the first sedimentation pool 16 is conveyed to the first reaction pool 15 through the sludge conveying device, the chemical softening pool is provided with a feed inlet for adding a chemical softener, the first intermediate pool 19 is sequentially connected with a sand filter 20, a carbon filter 21 and a resin softener 22 through the lifting pump 9, a water outlet of the resin softener 22 is connected with the reverse osmosis device 23, produced water is discharged from a pure water outlet of the reverse osmosis device 23, a regenerated water outlet of the resin softener 22 and a concentrated water outlet of the reverse osmosis device 23 are respectively connected with a second regulating pool 8, the carbon filter 20 and the reverse osmosis filter device 21 are respectively connected with a reverse osmosis filter device, and a reverse osmosis device, and a backwash water outlet of the sand filter 21 are respectively connected with a reverse osmosis regulating pool 8;
further, the first sedimentation tank 15, the second sedimentation tank 18, the third sedimentation tank 11 and the evaporator 14 are respectively provided with a slag discharge port.
Specific example 1: the water quality and the water quantity of the production wastewater in a certain photovoltaic industry are shown in table 1:
TABLE 1 quality and quantity of wastewater from photovoltaic industry
The implementation steps of the invention are as follows:
(1) Classifying and collecting concentrated acid wastewater, concentrated alkali wastewater, dilute acid wastewater and dilute alkali wastewater;
(2) Recycling concentrated acid wastewater: the concentrated acid wastewater enters a first regulating reservoir for homogenization; measuring the concentration of fluorine ions and silicon ions in the concentrated acid wastewater (the average concentration of the fluorine ions is 66000mg/L, and the concentration of the silicon ions is 6000 mg/L), and pumping the concentrated acid wastewater into a first crystallization reactor for reaction; adding NaCl in an amount of 25g/L into the first crystallization reactor to perform crystallization reaction; and (3) periodically discharging the concentrated crystallization liquid at the bottom of the first crystallization reactor, and drying to obtain the sodium fluosilicate with high purity (2.5 t/d). And (3) conveying the clear liquid of the first crystallization reactor into a second crystallization reactor, adding a calcium chloride solution (the addition amount is 23g/L, carrying out crystallization reaction, periodically discharging a crystallization concentrated solution at the bottom of the second crystallization reactor, drying to obtain a high-purity calcium fluoride product (6.8 t/d), and conveying the clear liquid of the second crystallization reactor into a second regulating reservoir.
(3) And discharging the dilute alkali wastewater and the dilute acid wastewater into a third regulating reservoir for homogenizing and equalizing the volume. Then pumping into a first reaction tank, and sequentially adding 30% of calcium hydroxide, PAC (polyaluminium chloride) and PAM (polyacrylamide) for reaction; the mixed liquid enters a first sedimentation tank, 60 percent of sludge in the first sedimentation tank is subjected to filter pressing and outward transportation, and 40 percent of sludge is returned to a third reaction tank. And sending the supernatant of the first sedimentation tank into a chemical softening tank.
(4) Adding sodium carbonate into the chemical softening tank to primarily remove excessive calcium in the supernatant of the first sedimentation tank; the effluent enters a second sedimentation tank; and discharging the sludge in the second sedimentation tank, and feeding the supernatant in the second sedimentation tank into a first intermediate water tank, and then pumping into a sand filter, an activated carbon filter and a resin softener to remove particles, organic matters and residual hardness in water. The water discharged from the resin softener is sent to a reverse osmosis device through a high-pressure pump; the reverse osmosis effluent is reused for supplementing water to a pure water system, and the recovery rate is 75 percent.
(5) Sending the concentrated alkali wastewater, the supernatant of the second crystallization reactor, the sand filter backwashing water, the activated carbon filter backwashing water, the resin softener regenerated water and the reverse osmosis concentrated water into a second regulating tank for homogenizing and equalizing; then pumping into a second reaction tank and a third sedimentation tank for defluorination treatment. Carrying out filter pressing on the sludge in the third sedimentation tank and then carrying out outward; the supernatant from the third settling tank is sent to a second intermediate water tank and then to the evaporator. The condensate of the evaporator is discharged from the condensation outlet and can be reused for water supplement of a pure water system, and the residue is transported outside.
Comparative example:
which is a method for treating fluorine-containing wastewater in photovoltaic industry in the prior art
(1) The water quality and the water quantity are the same as those of the embodiment; collecting concentrated acid wastewater, concentrated alkali wastewater, dilute acid wastewater and dilute alkali wastewater to an adjusting tank;
(2) Pumping the mixed wastewater into a reaction tank, and sequentially adding 30% of calcium hydroxide, PAC and PAM for reaction; the mixed liquid enters a sedimentation tank. The reaction tank and the sedimentation tank are arranged in 2 stages. Sludge in the sedimentation tank is pressed and filtered for outward transportation, and supernatant is sent into a chemical softening tank.
(3) Adding sodium carbonate into the chemical softening tank to remove excessive calcium in the supernatant of the sedimentation tank; the effluent enters a sedimentation tank; and discharging the sludge in the sedimentation tank, and pumping the supernatant into an intermediate water tank, and then pumping into a sand filter and an activated carbon filter to remove particles and organic matters in water. The effluent of the activated carbon filter is sent into a reverse osmosis device through a high-pressure pump; the reverse osmosis effluent is reused for water supplement of a pure water system, and the recovery rate is 50%.
(4) And feeding the sand filter backwashing water, the activated carbon filter backwashing water and the reverse osmosis concentrated water into the evaporator. The condensate of the evaporator can be reused for greening and transporting the residue outside.
The main operating parameter pairs for the specific example 1 of the invention and the comparative example are shown in table 2:
TABLE 2 comparison of the Main operating parameters
As can be seen from table 2: aiming at the fluorine-containing wastewater in the photovoltaic industry, the invention carries out classified collection treatment on concentrated acid wastewater, concentrated alkali wastewater, dilute acid wastewater and dilute alkali wastewater, the set process has strong pertinence, reduces the overall treatment difficulty and the operation cost, improves the recovery rate of a reverse osmosis system, and can reach 75 percent. A large amount of byproducts, specifically 2.5t/d of sodium fluosilicate and 6.8t/d of calcium fluoride, can be recycled from the concentrated acid wastewater, and the annual income reaches 330 ten thousand yuan per year. Meanwhile, the sludge production is only 1.5t/d which is far less than 14.2t/d of the comparative case, and the annual sludge disposal cost is reduced by 89%. The secondary softening treatment is carried out on calcium in the supernatant of the defluorination sedimentation tank by adopting a chemical softening method and a resin softening method, so that the low hardness of reverse osmosis inlet water is ensured, and the reverse osmosis recovery rate reaches 75 percent and is far higher than 50 percent of that of a comparative case.
In general, the implementation case of the invention fully considers the characteristics of each strand of wastewater in the photovoltaic industry: recycling dilute acid dilute alkali wastewater with low salt content; carrying out secondary resource recovery on concentrated acid wastewater with high fluoride ion concentration; and (4) evaporating the concentrated alkali wastewater with high organic matter concentration and other backwash water. The process can achieve nearly 100% of wastewater regeneration recovery rate; the calcium fluoride sludge is reduced by more than 85 percent; the recovered fluosilicate and calcium fluoride have obvious economic benefit.
Claims (4)
1. A process for recycling and reusing fluorine-containing wastewater in photovoltaic industry is characterized by comprising the following steps: the method comprises the following steps:
step 1: collecting waste water: classifying and collecting concentrated acid wastewater, concentrated alkali wastewater, dilute acid wastewater and dilute alkali wastewater;
step 2: resource treatment of concentrated acid wastewater: feeding the concentrated acid wastewater into a first regulating reservoir for homogenizing, measuring the concentration of fluorine ions and silicon ions in the concentrated acid wastewater, pumping the concentrated acid wastewater into a first crystallization reactor, adding sodium salt or potassium salt into the first crystallization reactor for crystallization reaction, wherein the sodium salt comprises at least one of sodium chloride, sodium nitrate and sodium silicate, and the adding amount of the sodium salt keeps the total molar concentration ratio of sodium to silicon in the first crystallization reactor to be Na: si = (2-3.5) 1; the potassium salt comprises at least one of potassium chloride and potassium nitrate; the amount of potassium salt added was such that the total molar concentration ratio of potassium and silicon in the first crystallization reactor was maintained at K: si = (2-3): 1, and periodically discharging the concentrated crystallization solution at the bottom of the first reactor, and drying to obtain fluorosilicate; feeding the supernatant in the first crystallization reactor into a second crystallization reactor, adding a calcium salt solution into the second crystallization reactor for crystallization reaction, wherein the calcium salt solution comprises at least one of a calcium chloride solution and a calcium hydroxide solution, the adding amount of the calcium salt solution keeps the total molar concentration ratio of calcium to fluorine in the second crystallization reactor at (0.6-0.75): 1, periodically discharging a crystallization concentrated solution at the bottom of the second reactor, and drying to obtain calcium fluoride;
and step 3: treating dilute alkali wastewater and dilute acid wastewater: discharging dilute alkali wastewater and dilute acid wastewater into a third regulating tank, homogenizing and homogenizing, pumping into a first reaction tank, adding calcium salt, a coagulant and a flocculant for reaction for defluorination, feeding mixed liquor into a first sedimentation tank from the first reaction tank for sedimentation, carrying out filter pressing and outward transportation on part of sludge in the first sedimentation tank, returning part of sludge to the first reaction tank, carrying out filter pressing and outward transportation on part of sludge in a second sedimentation tank, feeding supernatant of the first sedimentation tank into a chemical softening tank, adding a softening agent for chemical softening treatment, feeding effluent of the chemical softening tank into the second sedimentation tank for sedimentation, feeding part of sludge returned to the reaction tank into a reverse osmosis device by a high-pressure pump, wherein the proportion of the part of sludge is 20-50% of the total sludge of the sedimentation tank, feeding supernatant of the second sedimentation tank into a first intermediate water tank, and then sequentially passing through a sand filter, an activated carbon filter and a resin softener by a pump for removing particles, organic matters and residual hardness in water, and feeding softened produced water into a reverse osmosis device by the high-pressure pump, and discharging the produced water from a pure water outlet of the reverse osmosis device;
step 4, treating concentrated alkali wastewater: and 3, respectively arranging backwashing devices on the sand filter and the activated carbon filter in the step 3, discharging backwashing water of the backwashing devices of the sand filter and the activated carbon filter, regenerated water of the resin softener and concentrated water discharged by the reverse osmosis device into a second regulating tank together with supernatant and concentrated alkali wastewater of the second crystallization reactor in the step 2 for homogenizing and equalizing, pumping into a second reaction tank, adding calcium salt, a coagulant and a flocculating agent for reaction for defluorination, allowing the mixed solution to enter a third sedimentation tank from the second reaction tank for sedimentation, carrying out filter pressing on part of sludge in the third sedimentation tank, returning part of sludge to the second reaction tank, allowing part of sludge returned to the reaction tank to be 20-50% of the total sludge amount of the sedimentation tank, allowing supernatant in the third sedimentation tank to enter a second intermediate tank and then enter an evaporator, and discharging produced water from a condensed water outlet of the evaporator.
2. The process for recycling and reusing the fluorine-containing wastewater in the photovoltaic industry according to claim 1, which is characterized in that: the softening medicament comprises sodium carbonate and sodium bicarbonate; the reverse osmosis device comprises a cartridge filter, a reverse osmosis membrane assembly and a bracket; the calcium salt in the defluorination treatment is calcium hydroxide.
3. The utility model provides a system for fluoride waste water resource and retrieval and utilization of photovoltaic trade which characterized in that: the process for recycling and reusing the fluorine-containing wastewater in the photovoltaic industry comprises a dilute alkali wastewater pool, a dilute acid wastewater pool, a concentrated alkali wastewater pool and a concentrated acid wastewater pool, wherein the dilute alkali wastewater pool is connected with the dilute alkali wastewater incoming water through a pipeline;
the concentrated acid wastewater tank is sequentially connected with a first regulating tank, a first crystallization reactor, a second crystallization reactor and a second regulating tank; the first crystallization reactor is provided with a feed port for adding sodium salt or potassium salt, the second crystallization reactor is provided with a feed port for adding calcium salt solution, and a lift pump is arranged between the concentrated acid wastewater pool and the first regulating pool; the concentrated alkali wastewater tank is connected with a second regulating tank, a water outlet of the second regulating tank is connected with a second reaction tank through a lifting pump, the second reaction tank is provided with a feed inlet for adding a defluorination agent, the second reaction tank is sequentially connected with a third sedimentation tank, a second intermediate water tank and an evaporator, produced water is discharged from a condensate water outlet of the evaporator, a sludge conveying device is arranged between the second reaction tank and the third sedimentation tank, and sludge in the third sedimentation tank is conveyed to the second reaction tank through the sludge conveying device;
the dilute alkali wastewater pool and the dilute acid wastewater pool are respectively connected to a third regulating pool, the third regulating pool is connected with a first reaction pool through a lifting pump, a feed inlet is formed in the first reaction pool and used for adding a defluorination agent, the first reaction pool is sequentially connected with a first sedimentation pool, a chemical softening pool, a second sedimentation pool and a first intermediate pool, a sludge conveying device is further arranged between the first reaction pool and the first sedimentation pool, sludge in the first sedimentation pool is conveyed to the first reaction pool through the sludge conveying device, the chemical softening pool is provided with a feed inlet and used for adding a chemical softening agent, the first intermediate pool is sequentially connected with a sand filter, an activated carbon filter and a resin softener through the lifting pump, a water outlet of the resin softener is connected with a reverse osmosis device, produced water is discharged from a pure water outlet of the reverse osmosis device, a regenerated water outlet of the resin softener and a concentrated water outlet of the reverse osmosis device are respectively connected with the second regulating pool, the sand filter and the activated carbon filter are respectively connected with the reverse osmosis device, and a reverse washing water outlet of the activated carbon filter is respectively connected with the second regulating pool.
4. The photovoltaic industry fluoride waste water recycling and reusing system according to claim 3, characterized in that: the first sedimentation tank, the second sedimentation tank, the third sedimentation tank and the evaporator are respectively provided with a slag discharge port.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611172769.7A CN106746113B (en) | 2016-12-18 | 2016-12-18 | Process and system for recycling and reusing fluorine-containing wastewater in photovoltaic industry |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611172769.7A CN106746113B (en) | 2016-12-18 | 2016-12-18 | Process and system for recycling and reusing fluorine-containing wastewater in photovoltaic industry |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106746113A CN106746113A (en) | 2017-05-31 |
| CN106746113B true CN106746113B (en) | 2023-04-07 |
Family
ID=58889557
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611172769.7A Active CN106746113B (en) | 2016-12-18 | 2016-12-18 | Process and system for recycling and reusing fluorine-containing wastewater in photovoltaic industry |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106746113B (en) |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109502858A (en) * | 2017-09-15 | 2019-03-22 | 上海江柘环境工程技术有限公司 | A kind of photovoltaic industry fluorine-contained wastewater treatment system and its processing method |
| CN107651774A (en) * | 2017-09-26 | 2018-02-02 | 上海晶宇环境工程股份有限公司 | Coal chemical industry strong brine silicon removing process and its special purpose device |
| CN107973467A (en) * | 2017-10-16 | 2018-05-01 | 杭州绿色环保技术开发有限公司 | A kind of manufacture of solar cells waste water zero discharge treatment process |
| CN109437438B (en) * | 2018-12-15 | 2024-05-10 | 深圳凯盛科技工程有限公司 | TFT-LCD glass thinning wastewater treatment system |
| CN110078261B (en) * | 2019-05-20 | 2024-02-09 | 中国恩菲工程技术有限公司 | Method and system for treating wastewater |
| CN110304765A (en) * | 2019-07-25 | 2019-10-08 | 鞍钢贝克吉利尼水处理有限公司 | Rapid subsidence defluorinating agent and the preparation, application method of fluorine-containing turbid circulating water are made steel in processing |
| CN111153531A (en) * | 2020-03-06 | 2020-05-15 | 上海东振环保工程技术有限公司 | Liquid crystal display panel production plant fluorine-containing wastewater treatment device and process |
| CN111268830A (en) * | 2020-04-01 | 2020-06-12 | 江苏中电创新环境科技有限公司 | System and process for advanced treatment and recycling of fluorine-containing wastewater in electronic industry |
| CN114105365A (en) * | 2021-12-02 | 2022-03-01 | 苏州新能环境技术股份有限公司 | Photovoltaic production wastewater recycling treatment process |
| CN114605018B (en) * | 2022-02-04 | 2024-02-02 | 重庆大学 | Method for treating phosphorus-containing fluorine-containing high-salt organic wastewater and recovering salt |
| CN114988612A (en) * | 2022-06-22 | 2022-09-02 | 氟恩泰克株式会社 | Method for producing high-purity calcium fluoride wet mud by using fluorine-containing waste acid as raw material |
| CN115340221A (en) * | 2022-09-14 | 2022-11-15 | 深圳市环境科学研究院 | Deep defluorination treatment process and recycling system |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102730871A (en) * | 2011-04-01 | 2012-10-17 | 深圳恒通源水处理科技有限公司 | Recycling process of fluorine-containing wastewater |
| WO2013040716A1 (en) * | 2011-09-21 | 2013-03-28 | Ostara Nutrient Recovery Technologies Inc. | Treatment of phosphate-containing wastewater with fluorosilicate and phosphate recovery |
| CN103011453A (en) * | 2012-12-08 | 2013-04-03 | 北京国环清华环境工程设计研究院有限公司 | Processing method for fluoride waste water in production of solar cells |
| CN105753211A (en) * | 2016-03-24 | 2016-07-13 | 北京国环清华环境工程设计研究院有限公司 | Method and system for recovering fluorine from waste acid produced in thinning production of solar cells or glass |
| CN205442751U (en) * | 2016-03-08 | 2016-08-10 | 温州市赛拉弗能源有限公司 | Fluoride waste water treatment system |
-
2016
- 2016-12-18 CN CN201611172769.7A patent/CN106746113B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102730871A (en) * | 2011-04-01 | 2012-10-17 | 深圳恒通源水处理科技有限公司 | Recycling process of fluorine-containing wastewater |
| WO2013040716A1 (en) * | 2011-09-21 | 2013-03-28 | Ostara Nutrient Recovery Technologies Inc. | Treatment of phosphate-containing wastewater with fluorosilicate and phosphate recovery |
| CN103011453A (en) * | 2012-12-08 | 2013-04-03 | 北京国环清华环境工程设计研究院有限公司 | Processing method for fluoride waste water in production of solar cells |
| CN205442751U (en) * | 2016-03-08 | 2016-08-10 | 温州市赛拉弗能源有限公司 | Fluoride waste water treatment system |
| CN105753211A (en) * | 2016-03-24 | 2016-07-13 | 北京国环清华环境工程设计研究院有限公司 | Method and system for recovering fluorine from waste acid produced in thinning production of solar cells or glass |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106746113A (en) | 2017-05-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106746113B (en) | Process and system for recycling and reusing fluorine-containing wastewater in photovoltaic industry | |
| CN108249646B (en) | Power plant desulfurization wastewater zero-emission treatment process and device capable of recycling resources | |
| US10662075B2 (en) | Method and apparatus for the recovery and deep treatment of polluted acid | |
| CN108689522B (en) | Method for treating and recycling mixed acid wastewater in photovoltaic industry | |
| WO2010092946A1 (en) | Method for processing waste water containing fluorine and silicon, method for producing calcium fluoride, and facility for processing fluorine-containing waste water | |
| CN111547885B (en) | Process for removing fluorine, controlling salt and recovering fluorine from silicon solar cell production wastewater | |
| CN107915354A (en) | A kind of desulfurization wastewater zero-emission and resource utilization device and method | |
| CN112142249B (en) | SO (SO)4·HCO3Method and system for treating and recycling-Na-type high-salt mine water | |
| CN112759165A (en) | Mine strong brine zero-discharge treatment method and system | |
| CN110950474A (en) | Phenol-cyanogen wastewater resource zero-discharge method and process | |
| CN109205876B (en) | Method and device for treating desulfurization wastewater | |
| CN205442916U (en) | Contain salt effluent disposal system | |
| CN111170340A (en) | Method for recovering salt and nitrate from salt and nitrate waste brine | |
| CN111099773A (en) | Desulfurization wastewater treatment method and system | |
| WO2015198438A1 (en) | Method and device for treating fluoride-containing water | |
| CN111170516A (en) | Treatment process and treatment system for desulfurization wastewater | |
| CN111170519A (en) | Treatment process and treatment system for desulfurization wastewater | |
| CN106145498A (en) | A kind of thermal power plant high slat-containing wastewater zero-emission recovery and treatment method | |
| CN111606487A (en) | Method for continuously treating and recycling manganese and ammonia nitrogen resources from electrolytic manganese wastewater | |
| CN214611993U (en) | Mine strong brine zero release processing system | |
| CN215089715U (en) | Fly ash water washing system and fly ash treatment system containing same | |
| CN113698002A (en) | Novel reverse osmosis strong brine recovery treatment process | |
| CN206580692U (en) | A kind of photovoltaic industry fluoride waste recycling and the system of reuse | |
| CN106698790A (en) | Comprehensive recycling method for graphite production wastewater | |
| CN113248040B (en) | Process for removing fluorine and recycling solar cell production wastewater |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |