CN109502858A - A kind of photovoltaic industry fluorine-contained wastewater treatment system and its processing method - Google Patents
A kind of photovoltaic industry fluorine-contained wastewater treatment system and its processing method Download PDFInfo
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- CN109502858A CN109502858A CN201710830427.8A CN201710830427A CN109502858A CN 109502858 A CN109502858 A CN 109502858A CN 201710830427 A CN201710830427 A CN 201710830427A CN 109502858 A CN109502858 A CN 109502858A
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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
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/20—Nitrogen oxides; Oxyacids of nitrogen; Salts thereof
- C01B21/48—Methods for the preparation of nitrates in general
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
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- 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
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F1/24—Treatment of water, waste water, or sewage by flotation
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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/38—Treatment of water, waste water, or sewage by centrifugal separation
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- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—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
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- 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
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/447—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by membrane distillation
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
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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
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- 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
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- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/12—Halogens or halogen-containing compounds
- C02F2101/14—Fluorine or fluorine-containing compounds
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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
- C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
- C02F5/02—Softening water by precipitation of the hardness
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Abstract
The invention discloses a kind of photovoltaic industry fluorine-contained wastewater treatment system and its processing methods, including wastewater collection pond, precipitation process unit, micro-filtration processing unit, air-flotation process unit, sand carbon filter processing unit, ion exchange system, reverse osmosis treatment unit, membrane distillation processing unit, crystallization treatment unit and MVR evaporation process unit；Fluorine-contained wastewater treatment system of the present invention is stable, and failure rate is low, reduces the cleaning frequency and replacement number of film；Fluorine-contained wastewater treatment system of the present invention reduces operational management difficulty, and maintenance cost is low；Investment cost and operating cost is effectively reduced in fluorine-contained wastewater treatment system of the present invention, and fluorine-contained wastewater treatment system of the present invention can improve the economic benefit and social benefit of environmental protection with resource utilization nitrate.
Description
Technical field
The present invention relates to fluoride wastewater treatment technical field more particularly to a kind of photovoltaic industry fluorine-contained wastewater treatment system and
Using the processing method of the system.
Background technique
Using photovoltaic effect, sunlight is set to be mapped to the generation electric current direct generation of electricity on silicon materials, with the application and development of silicon materials
The industry chain (supply chain) of formation is referred to as " photovoltaic industry ", including the production of High Purity Polycrystalline silicon material, manufacture of solar cells, solar energy
Battery component production etc..Photovoltaic wastewater is mainly from polycrystalline silicon production line and diffusion furnace cleaning draining, soda acid exhaust gas scrubber
Draining, silicone hydride combustion tower-ammonia absorption device draining.The main polluted factors of photovoltaic industry waste water: F-、SiO3 2-、NO3 -、COD。
Photovoltaic wastewater water quality characteristics: the variation of Wastewater Pollutant concentration is greatly, property, the pH value of waste water are high, useless at times for discharge of wastewater flow
Water is big to the corrosivity of equipment.Since the content of sodium metasilicate in waste water is larger, in addition in waste water alcohols to the inhibiting effect of bacterium,
So the biodegradability of waste water is very poor.
The structural schematic diagram of existing country's conventional processing device is as shown in Figure 1.The photovoltaic waste water containing nitre being collected into first into
Enter pretreatment system a, be added calcium oxide or calcium hydroxide in pretreatment system a, calcium ion therein respectively with F-、SiO3 2-Instead
It answers.Reaction principle is as follows:
Ca2++ 2F?=CaF2
Ca2++SiO3 2-=CaSiO3, F- and SiO3 2-Respectively with CaF2And CaSiO3Form precipitate, by sludge dewatering
Machine b has the function that remove sludge.Sand carbon filter system c is continued through by the supernatant that pretreatment system a is obtained, is carried out secondary
Filtering, filtered clear liquid adjust back pH to 5.8-6.3 with acid, and the clear liquid after readjustment enters film separation system d, film separation system d
The concentrate of acquisition enters multi-effect evaporation system e, further condensing crystallizing, the waste water after multi-effect evaporation system e concentration by from
Scheming f carries out centrifugal treating.
Authorization Notice No. CN103373774B discloses " photovoltaic industry fluoride waste embrane method high power recycles dedicated system ", needle
Recovery process to the system is the following steps are included: first pre-process the fluoride waste being collected into, i.e., to being collected into
Fluoride waste carries out runoff investigation, keeps fluoride waste water quality uniform, and pH value will pass through containing for runoff investigation between 6-9
Fluorine waste water is filtered, and filtering removal SS, larger molecular organics and colloid are then passed through film pretreated fluoride waste is passed through
Separating treatment system carries out further purified treatment to fluoride waste and obtains producing water and concentrated water；Then obtained concentrated water is carried out
It is discharged after qualified discharge processing, the sludge generated in membrane separation system purification treatment process is finally subjected to desiccation outward transport.
Above two method is that waste water is passed through membrane separation system after filtration treatment, due to CaF2In pH value
It is first to increase to subtract afterwards for the solubility in this section 8-12, and CaF2With Ca (OH)2Total solution can be formed, leads to water outlet not
The requirement of subsequent UF membrane can be reached, the damage of film easily occur, need to be replaced frequently membrane component.
Summary of the invention
In order to solve the problems, such as that film is easy to damage in the prior art, it is fluorine-containing useless that the object of the present invention is to provide a kind of photovoltaic industries
Water treatment system and processing method.
To achieve the goals above, the present invention adopts the following technical scheme:
The first aspect of the present invention provides a kind of photovoltaic industry fluorine-contained wastewater treatment system, including wastewater collection pond, precipitation process
Unit, micro-filtration processing unit, air-flotation process unit, sand carbon filter processing unit, ion exchange system, reverse osmosis treatment unit, film
Processing unit, crystallization treatment unit and MVR evaporation process unit are distilled,
The water inlet of the water outlet connection precipitation process unit of the wastewater collection pond, the precipitation process unit are useless for settling
F in water collecting pit-And SiO3 2-；
The water inlet of the water outlet connection micro-filtration processing unit of the precipitation process unit, being used for will be after precipitation process cell processing
Waste water carry out micro-filtration processing；
The water inlet of the water outlet connection air-flotation process unit of the micro-filtration processing unit, for further removing SiO3 2-；
The water inlet of the water outlet connection sand carbon filter processing unit of the air-flotation process unit, in settlement air floatation processing unit
Suspended matter；
The water inlet of the water outlet connection ion exchange system of the sand carbon filter processing unit, at ion exchange system
Waste water total hardness after reason；
The water inlet of the water outlet connection reverse osmosis treatment unit of the ion exchange system is obtained for carrying out reverse osmosis treatment
To the first rich nitric acid salt water and the first fresh water；
The membrane distillation processing unit is used to the first rich nitric acid salt water carrying out membrane distillation processing, obtain third richness nitric acid salt water and
Third fresh water；
The membrane distillation processing unit water outlet connection crystallization treatment unit water inlet, for by third richness nitric acid salt water into
Row crystallization treatment obtains the 4th rich nitric acid salt water and the first crystal salt；
The water inlet of the water outlet connection MVR evaporation process unit of the crystallization treatment unit is used for the 4th rich nitric acid salt water
MVR evaporation process is carried out, the second crystal salt and the 4th fresh water are obtained.
Wherein, the micro-filtration processing unit connects sludge dewatering equipment.
Wherein, the reverse osmosis treatment unit includes the first reverse osmosis membrane and the second reverse osmosis membrane, and described first is reverse osmosis
Film is high pressure reverse osmosis membrane, and second reverse osmosis membrane is low-pressure reverse osmosis membrane, and the water outlet of the ion exchange system connects
The water inlet of first reverse osmosis membrane, obtains the first rich nitric acid salt water and the first fresh water, the first fresh water flow into the second reverse osmosis membrane, obtains
To the second rich nitric acid salt water and the second fresh water, the described second rich nitrate water flows into the first reverse osmosis membrane and carries out circulation concentration.
Wherein, first crystal salt and the second crystal salt are sodium nitrate.
The second aspect of the present invention provides a kind of photovoltaic industry fluorine-containing wastewater treatment method, using above-mentioned processing system,
Include the following steps:
Fluoride waste in sewage collecting box is passed through precipitation process unit, settles the F in sewage collecting box by S1-And SiO3 2-；
S2 will carry out sofening treatment in the supernatant obtained after settlement treatment, settle calcium and magnesium ion；
Fluoride waste after softening is carried out micro-filtration processing by S3；
Micro-filtration treated waste water is carried out air-flotation process, further removes SiO by S43 2-；
Waste water after air-flotation process is filtered processing, removes the suspended matter in air-flotation process unit by S5；
Waste water after filtration treatment is carried out ion exchange, reduces the total hardness of waste water by S6；
Waste water after ion-exchange treatment is carried out reverse osmosis treatment by S7, obtains the first rich nitric acid salt water and the first fresh water；
First rich nitric acid salt water is carried out membrane distillation processing, obtains third richness nitric acid salt water and third fresh water by S8；
Third richness nitric acid salt water is carried out crystallization treatment by S9, obtains the 4th rich nitric acid salt water and the first crystal salt；
4th rich nitric acid salt water is carried out MVR evaporation process, obtains the second crystal salt and the 4th fresh water by S10.
Wherein, the substance that the S2 sofening treatment is added is sodium carbonate.
Wherein, it carries out before air-flotation process further including the acid adding progress pH readjustment step into waste water in the S4.
Wherein, the filter of sand carbon is filtered into the S5.
Wherein, the ion-exchanger used in the S6 is sodium form strong acid positive resin.
Wherein, SiO in the described first rich nitric acid salt water3 2-The concentration of ion is 10-20mg/L.
Compared with prior art, the present invention realize the utility model has the advantages that
1) fluorine-contained wastewater treatment system of the present invention is stable, and failure rate is low, reduces the replacement number of film；
2) fluorine-contained wastewater treatment system of the present invention reduces operational management difficulty, and maintenance cost is low；
3) fluorine-contained wastewater treatment system of the present invention with resource utilization nitrate, can improve the economic benefit and society's effect of environmental protection
Benefit.
4) investment cost and operating cost is effectively reduced in fluorine-contained wastewater treatment system of the present invention.
Detailed description of the invention
Below in conjunction with the drawings and specific embodiments, present invention be described in more detail:
Fig. 1 is the structural schematic diagram of traditional fluoride wastewater treatment equipment；
Fig. 2 is the structural schematic diagram of fluorine-contained wastewater treatment system of the present invention.
Wherein: wastewater collection pond 1, precipitation process unit 2, micro-filtration processing unit 3, air-flotation process unit 4, sand carbon filter processing
Unit 5, ion exchange system 6, reverse osmosis treatment unit 7, membrane distillation processing unit 8, crystallization treatment unit 9, MVR evaporation process
Unit 10, the first reverse osmosis membrane 11, the second reverse osmosis membrane 12, sludge dewatering equipment 13, the first centrifuge 14, the second centrifuge 15,
Sofening treatment unit 16.
Specific embodiment
Such as Fig. 2, a kind of photovoltaic industry fluorine-contained wastewater treatment system, including wastewater collection pond 1, precipitation process unit 2, micro-filtration
Processing unit 3, air-flotation process unit 4, sand carbon filter processing unit 5, ion exchange system 6, reverse osmosis treatment unit 7, membrane distillation
Processing unit 8, sofening treatment unit 16, crystallization treatment unit 9 and MVR evaporation process unit 10.
Pollutant in wastewater collection pond 1 is mainly F-, SiO3 2-, NO3 -With COD etc..F-Concentration be 100-300mg/L,
SiO3 2-Concentration be 50-100mg/L, NO3 -Concentration be 1000-5000mg/L, COD 50-100mg/L, Mg2+Concentration be
50-200mg/L。
Precipitation process unit 2 includes sedimentation basin, and lime white, F is added in sedimentation basin-And SiO3 2-Respectively with CaF2And CaSiO3
Form precipitate, supernatant therein is passed through sofening treatment unit 16, sodium carbonate is added in sofening treatment unit 16, wherein
Ca2+、Mg2+Respectively with CaCO3With Mg (OH)2Form precipitate, the mixed liquor after reaction enters micro-filtration processing unit 3,
It is separated by solid-liquid separation.
There is no particular limitation for concrete configuration of the present invention to micro-filtration processing unit 3, can have micro-filtration using conventional
The micro-filtration of film.Treated that concentrate is discharged into sludge dewatering equipment 13 is carried out dehydrating for micro-filtration.Micro-filtration processing unit 3
F in treated supernatant-Concentration be 20-50mg/L, SiO3 2-Concentration be 10-30mg/L, NO3 -Concentration be 1000-
The concentration of 4000mg/L, COD are 30-50mg/L, Ca2+Concentration be 20-80mg/L (with CaCO3Meter), Mg2+Concentration be 2-
30mg/L is (with MgCO3Meter).
Treated the supernatant of micro-filtration processing unit 3 acid readjustment pH to 5.8-6.3, the waste water after readjustment enter at air bearing
Manage unit 4.There is no particular limitation for concrete configuration of the present invention to air-flotation process unit 4, can have air bearing using conventional
The air floatation machine of room.PAM is added into air-flotation process unit 4, the floccule formed in supernatant is separated in gas-floating chamber, is floated
Slag is mechanically removed from water surface, collects that treated that waste water is adsorbed in floccule while floccule is removed
In SiO3 2-Also it is removed, further decreases SiO in waste water3 2-Content.
Treated supernatant enters sand carbon filter processing unit 5, the further progress filtration treatment of air-flotation process unit 4.This
There is no particular limitation for concrete configuration of the invention to sand carbon filter processing unit 5, can filter processing equipment using conventional sand carbon.Sand
Carbon filters F in treated the supernatant of processing unit 5-Concentration be 15-30mg/L, SiO3 2-Concentration be 5-10mg/L, NO3 -'s
Concentration is 1000-4000mg/L, and the concentration of COD is 20-40mg/L, Ca2+Concentration be 10-70mg/L (with CaCO3Meter), Mg2+
Concentration be 2-25mg/L (with MgCO3Meter).
Sand carbon filters processing unit 5, and treated that supernatant enters ion exchange system 6, ion exchange system 6 of the invention
In ion-exchanger be sodium form strong acid positive resin, Ca in the supernatant after ion-exchange treatment2+Concentration be 0-20mg/L
(with CaCO3Meter), Mg2+Concentration be 0-5mg/L (with MgCO3Meter), total hardness is 0-20mg/L (with CaCO3And MgCO3Meter).
The total hardness handled by ion exchange system 6 is very low, small on film influence, can be passed through point that inorganic salts are carried out in reverse osmosis membrane
From processing.
Reverse osmosis treatment unit 7 includes the first reverse osmosis membrane 11 and the second reverse osmosis membrane 12, after the processing of ion exchange system 6
Waste water initially enter the first reverse osmosis membrane 11, the first reverse osmosis membrane 11 is high pressure reverse osmosis membrane, by the first reverse osmosis membrane 11
The first rich nitric acid salt water and the first fresh water, NO in the first rich nitrate are obtained after processing3 -Concentration be 10000-30000mg/L,
The conductivity of first fresh water is 1000us/cm, can not direct emission or reuse, the first fresh water flows into the second reverse osmosis membrane 12, the
Two reverse osmosis membranes 12 are low-pressure reverse osmosis membrane, obtain the second rich nitric acid salt water and the second fresh water, NO in the second rich nitric acid salt water3 -'s
Concentration is 100-500mg/L, and the second rich nitric acid salt water back flows back into the first reverse osmosis membrane 11, is further concentrated, second
The conductivity of fresh water is 50-200us/cm, reaches reuse standard, can be with recycling and reusing.High pressure reverse osmosis membrane operating pressure is big
In 50bar, the conductivity of handled sewage is 30000-40000us/cm, and low-pressure reverse osmosis membrane operating pressure is less than 10bar, institute
The conductivity of sewage is handled in 1000us/cm or less.
First rich nitric acid salt water enters membrane distillation processing unit 8, obtains third richness nitric acid salt water and third fresh water, third are light
The conductivity of water is 10-100us/cm, reaches standards for industrial water usage, can be with cycling and reutilization.What membrane distillation processing unit 8 obtained
Third richness nitric acid salt water enters crystallization treatment unit 9.
There is no particular limitation for concrete configuration of the present invention to membrane distillation processing unit 8, can be using conventional membrane distillation
Equipment.Preferably film layer number is 30-45 layers of membrane distillation equipment, and when film layer number is lower than 30 layers, the rejection of film is decreased obviously,
Water conductivity >=300us/cm is produced, and leakage scenarios easily occurs in stability difference；When film layer number is greater than 45 layers, flux depression is bright
It is aobvious, there is decline trend as film layer number rises, the manufacture difficulty and cost increase of film；Film layer numerical digit is in 30-45 layers of sexual valence
Than high, stability is good, membrane flux is big, rejection is good.
There is no particular limitation for concrete configuration of the present invention to crystallization treatment unit 9, can be using conventional with crystallization
The processing equipment of device, process conditions when crystallization are 60 DEG C, -0.085MPa.Third richness nitric acid salt water is in crystallization treatment unit 9
There are partial crystals to be precipitated, the first crystal salt and the 4th rich nitric acid salt water is obtained by the first centrifuge 14, the first crystal salt is pure
Degree is 98.5%, and industrial salt standard is fully achieved.Treated that supernatant enters MVR evaporation process unit for first centrifuge 14
10。
There is no particular limitation for concrete configuration of the present invention to MVR evaporation process unit 10, can be steamed using conventional MVR
Send out equipment.Treated the concentrate of MVR evaporation process unit 10 obtains the second crystal salt and the 4th light by the second centrifuge 15
Water, the second crystallization purity salt is 98.5%, industrial salt standard is fully achieved.
Third fresh water and the 4th fresh water reach standards for industrial water usage.
The present invention carries out at preheating respectively before waste water enters membrane distillation processing unit 8 and MVR evaporation process unit 10
The heat source of reason, preheating (is used from the waste heat of power plant for self-supply, plant area or low-quality Boiler Steam or other low-quality hot water etc.
Heat exchange or heat pump convert directly utilization or two times transfer and low-quality thermal energy are converted to high-quality heat energy), reduce operating cost.
Same amount of waste water is handled respectively with traditional desulfuration waste water treatment process and processing method of the invention, in waste water
Each parameter is as shown in table 1.
Table 1
| Ion | Content/(mg/L) |
| F- | 300 |
| SiO3 2- | 80 |
| NO3 - | 4000 |
| COD | 50 |
Treated that the results are shown in Table 2 for above two method.
Table 2
| Traditional handicraft | The method of the present invention | |
| Dosage kg/t | 4 | 3 |
| F before reverse osmosis treatment cell processing-Concentration mg/L | 40 | 20 |
| SiO before reverse osmosis treatment cell processing3 2-Concentration mg/L | 20 | 5 |
| Obtain the purity of crystal salt | 85 | > 98 |
| Direct processing cost member/t | 60 | 20 |
| Ten thousand yuan/t of system investments | 5~7 | 4~5 |
The above specific embodiments are only exemplary, is to preferably make skilled artisans appreciate that this is special
Benefit, be not to be construed as include to this patent range limitation；As long as any made by the spirit according to disclosed in this patent
Equivalent change or modification, each fall within the range that this patent includes.
Claims (10)
1. a kind of photovoltaic industry fluorine-contained wastewater treatment system, which is characterized in that including wastewater collection pond (1), precipitation process unit
(2), sofening treatment unit (16), micro-filtration processing unit (3), air-flotation process unit (4), sand carbon filter processing unit (5), and ion is handed over
It changes system (6), reverse osmosis treatment unit (7), membrane distillation processing unit (8), crystallization treatment unit (9) and MVR evaporation process list
First (10),
The water inlet of water outlet connection precipitation process unit (2) of the wastewater collection pond (1), the precipitation process unit (2)
For settling the F in wastewater collection pond (1)-And SiO3 2-；
The water inlet of water outlet connection sofening treatment unit (16) of the precipitation process unit (2), for removing precipitation process
Ca in unit (2) processed waste water2+、Mg2+；
The water inlet of water outlet connection micro-filtration processing unit (3) of the sofening treatment unit (16), is used for precipitation process list
First (2) treated, and waste water carries out micro-filtration processing；
The water inlet of water outlet connection air-flotation process unit (4) of the micro-filtration processing unit (3), for further removing
SiO3 2-；
The water inlet of water outlet connection sand carbon filter processing unit (5) of the air-flotation process unit (4), is handled for settlement air floatation
Suspended matter in unit (4)；
The water inlet of water outlet connection ion exchange system (6) of sand carbon filter processing unit (5), at sand carbon filter
Waste water total hardness of managing that unit (5) treated；
The water inlet of water outlet connection reverse osmosis treatment unit (7) of the ion exchange system (6), for carrying out reverse osmosis place
Reason obtains the first rich nitric acid salt water and the first fresh water；
The membrane distillation processing unit (8) is used to the first rich nitric acid salt water carrying out membrane distillation processing, obtains third richness nitrate
Water and third fresh water；
The water inlet of water outlet connection crystallization treatment unit (9) of the membrane distillation processing unit (8), is used for third richness nitric acid
Salt water carries out crystallization treatment, obtains the 4th rich nitric acid salt water and the first crystal salt；
The water inlet of water outlet connection MVR evaporation process unit (10) of the crystallization treatment unit (9) is used for the 4th rich nitre
Hydrochlorate water carries out MVR evaporation process, obtains the second crystal salt and the 4th fresh water.
2. photovoltaic industry fluorine-contained wastewater treatment system as described in claim 1, which is characterized in that the micro-filtration processing unit
(3) sludge dewatering equipment (13) are connected.
3. photovoltaic industry fluorine-contained wastewater treatment system as described in claim 1, which is characterized in that the reverse osmosis treatment unit
It (7) include the first reverse osmosis membrane (11) and the second reverse osmosis membrane (12), first reverse osmosis membrane (11) is high pressure reverse osmosis membrane,
Second reverse osmosis membrane (12) is low-pressure reverse osmosis membrane, and the water outlet connection first of the ion exchange system (6) is reverse osmosis
The water inlet of film (11), obtains the first rich nitric acid salt water and the first fresh water, the first fresh water flow into the second reverse osmosis membrane (12), obtains
Second rich nitric acid salt water and the second fresh water, the described second rich nitrate water flow into the first reverse osmosis membrane (11) and carry out circulation concentration.
4. photovoltaic industry fluorine-contained wastewater treatment system as described in claim 1, which is characterized in that first crystal salt and
Two crystal salts are sodium nitrate.
5. a kind of photovoltaic industry fluorine-containing wastewater treatment method, using the described in any item processing systems of claim 1-4, feature
It is, includes the following steps:
Fluoride waste in wastewater collection pond (1) is passed through precipitation process unit (2) by S1, the F in sedimentation wastewater collection pond (1)-
And SiO3 2-；
S2 will carry out sofening treatment in the supernatant obtained after settlement treatment, settle calcium and magnesium ion；
Fluoride waste after softening is carried out micro-filtration processing by S3；
Micro-filtration treated waste water is carried out air-flotation process, further removes SiO by S43 2-；
Waste water after air-flotation process is filtered processing, removes the suspended matter in air-flotation process unit by S5；
Waste water after filtration treatment is carried out ion exchange, reduces the total hardness of waste water by S6；
Waste water after ion-exchange treatment is carried out reverse osmosis treatment by S7, obtains the first rich nitric acid salt water and the first fresh water；
First rich nitric acid salt water is carried out membrane distillation processing, obtains third richness nitric acid salt water and third fresh water by S8；
Third richness nitric acid salt water is carried out crystallization treatment by S9, obtains the 4th rich nitric acid salt water and the first crystal salt；
4th rich nitric acid salt water is carried out MVR evaporation process, obtains the second crystal salt and the 4th fresh water by S10.
6. photovoltaic industry fluorine-containing wastewater treatment method as claimed in claim 5, which is characterized in that the S2 sofening treatment is added
Substance be sodium carbonate.
7. photovoltaic industry fluorine-containing wastewater treatment method as claimed in claim 5, which is characterized in that carried out at air bearing in the S4
It further include the acid adding progress pH readjustment step into waste water before reason.
8. photovoltaic industry fluorine-containing wastewater treatment method as claimed in claim 5, which is characterized in that be filtered into sand in the S5
Carbon filter.
9. photovoltaic industry fluorine-containing wastewater treatment method as claimed in claim 5, which is characterized in that the ion used in the S6
Exchanger is sodium form strong acid positive resin.
10. photovoltaic industry fluorine-containing wastewater treatment method as claimed in claim 5, which is characterized in that the described first rich nitrate
SiO in water3 2-The concentration of ion is 10-20mg/L.
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| 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 |
| CN114195241A (en) * | 2021-12-17 | 2022-03-18 | 陕西长武亭南煤业有限责任公司 | Fluorine-containing mine water deep treatment system and process |
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