CN110294560A - A kind of thin-film solar cells producing wastewater treatment - Google Patents
A kind of thin-film solar cells producing wastewater treatment Download PDFInfo
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- CN110294560A CN110294560A CN201910206132.2A CN201910206132A CN110294560A CN 110294560 A CN110294560 A CN 110294560A CN 201910206132 A CN201910206132 A CN 201910206132A CN 110294560 A CN110294560 A CN 110294560A
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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
- C02F11/00—Treatment of sludge; Devices therefor
- C02F11/12—Treatment of sludge; Devices therefor by de-watering, drying or thickening
- C02F11/121—Treatment of sludge; Devices therefor by de-watering, drying or thickening by mechanical de-watering
- C02F11/122—Treatment of sludge; Devices therefor by de-watering, drying or thickening by mechanical de-watering using filter presses
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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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- 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
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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
- 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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- 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
- C02F1/20—Treatment of water, waste water, or sewage by degassing, i.e. liberation of dissolved gases
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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
- 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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- 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
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
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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
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/56—Macromolecular compounds
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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
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
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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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal 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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/40—Organic compounds containing sulfur
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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
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/023—Reactive oxygen species, singlet oxygen, OH radical
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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
- C02F7/00—Aeration of stretches of water
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- 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
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/20—Controlling water pollution; Waste water treatment
- Y02A20/208—Off-grid powered water treatment
- Y02A20/212—Solar-powered wastewater sewage treatment, e.g. spray evaporation
Abstract
The present invention provides a kind of thin-film solar cells producing wastewater treatments, handle by this method thin-film solar cells production waste water, the pharmaceutical quantities not being used only are few, and sludge yield is few, and recovery efficiency is high.Itself the following steps are included: one, remove cadmium；The alkaline hot waste water collected in conditioning tank is passed through high-temperature-resfilter filter system, it is filtered by the cadmium sulfide that filtration system generates cadmium salt and thiocarbamide under alkaline hot conditions, filter retentate matter obtains cadmium sulfide by drying, and filtering water outlet enters stripping ammonia steaming system；Two, ammonia still process is stripped；It adjusts except the wastewater pH after cadmium is 11 ~ 12, is passed through stripping ammonia still and carries out stripping ammonia still process, gas phase obtains ammonium hydroxide by condensation after stripping ammonia still process, and liquid phase is passed through except thiocarbamide reactor；Three, thiocarbamide is removed；To except hydrogen peroxide is added in thiocarbamide reactor, resolves into the hydroxyl radical free radical with strong oxidizing property at high temperature by hydrogen peroxide come thiocarbamide of degrading, be passed through aeration tank after reaction and be aerated.
Description
Technical field
The present invention relates to technical field of waste water processing, specially a kind of thin-film solar cells producing wastewater treatment.
Background technique
Thin-film solar cells has as a kind of novel solar battery compared to traditional crystal silicon solar batteries
Raw material sources are extensive, production cost is low, are convenient for the advantages that large-scale production, develop in recent years very rapidly.Thin film solar
Battery according to raw material and production technology can be divided into silicon-based film solar cells, copper indium gallium selenide (CIGS) thin-film solar cells and
Three kinds of cadmium telluride diaphragm solar battery.CIGS thin film solar battery is mesh because of high conversion efficiency, the advantages that stability is good
It is preceding to study the highest thin-film solar cells of temperature in the market.But CIGS thin film solar battery is in the processes meeting such as plated film, etching
A large amount of production waste water is generated, such waste water belongs to the difficult waste water containing heavy metal cadmium, high ammonia nitrogen and thiocarbamide, according to " battery
Emission of industrial pollutants standard " (GB 30484-2013) requirement, need to handle rear entirely to 3 kinds of pollutants in the waste water
It can discharge.
It makes a return journey removing heavy metals cadmium frequently with add-alkali concrete sedimentating technique at present, but since production waste discharge temperature is higher
(60 ~ 85 DEG C), and heavy metal cadmium can be complexed to form heavy metal complex with ammonia nitrogen, cause coagulating sedimentation effect poor, in water outlet
Heavy metal index is difficult to reach emission request.In addition, thiocarbamide belongs to bio-refractory organic matter, frequently with iron-carbon micro-electrolysis, sweet smell
Equal advanced oxidation processes processing, but exist and the problems such as need to adjust soda acid, sludge quantity big repeatedly, due to containing weight in sludge
Cadmium metal belongs to hazardous waste, further increases operating cost.
The high ammonia nitrogen of Chinese patent CN 106277513 contains cadmium photovoltaic wastewater containing thiocarbamide processing method and system, main technique
Process are as follows: oil removal and heavy metal cadmium are removed by adding the progress coagulating sedimentation such as NaOH, coagulant and flocculation aid, subsequently through
Stripping ammonia distillation process recycles to obtain 16 ~ 19% concentrated ammonia liquor, eventually passes through qualified discharge after Fenton technology processing.The technique into
Heavy metal cadmium is removed using coagulation-settlement process in the higher situation of coolant-temperature gage, treatment effect is bad, and water outlet cadmium ion is only capable of protecting
Card is in 0.1mg/L or less, it is difficult to meet higher emission request, furthermore except cadmium and Fenton technology need to add a large amount of medicines in the process
Agent, operating cost are higher.Meanwhile the invention can not recycle the portion in thin-film solar cells production waste water in addition to ammonium hydroxide
Point.
A kind of cadmium ammonia waste water technique of zero discharge of the thin-film solar cells production line of Chinese patent CN 107285545, mentions
Two-stage coagulation precipitation process cadmium is first used out, and after precipitating supernatant is using evaporation technology processing, condensate liquid is removed through ammonia degassing film
Ammonia nitrogen is discharged eventually by counter-infiltration system reuse.This method mainly for thin-film solar cells industry cadmium ammonia waste water, and
The processing of the organic matters such as thiocarbamide in waste water is not considered.
The high ammonia nitrogen of Chinese patent CN 108314242 contains the fluorine-containing photovoltaic wastewater processing method of arsenic and system, using " ammonia still process vapour
Mention+NaClO+ coagulating sedimentation " technique removal waste water in arsenic, ammonia nitrogen and part COD.The technique not only big problem of sludge output
It still remains, and add oxidant NaClO only to have preferable removal effect to ammonia nitrogen, to hardly degraded organic substances some in waste water
Removal effect it is bad, while NaClO dosage is larger, brings a large amount of salt, increases the load of rear end RO system；This
Outside, Pollutants in Wastewater type is more, due to not having to carry out sub-prime classification processing, can not achieve the recycling of heavy metal.
Summary of the invention
For existing processing photovoltaic wastewater mode dosing sludge quantity is big, problem that recovery efficiency is low, the present invention provides
A kind of thin-film solar cells producing wastewater treatment by this method produces at waste water thin-film solar cells
Reason, the pharmaceutical quantities not being used only are few, and sludge yield is few, and recovery efficiency is high.
Its technical solution is such that a kind of thin-film solar cells producing wastewater treatment, which is characterized in that it is wrapped
Include following steps:
One, cadmium is removed；Alkaline hot waste water in conditioning tank will be collected and be passed through high-temperature-resfilter filter system, by filtration system by cadmium
The cadmium sulfide filtering that salt and thiocarbamide generate under alkaline hot conditions, filter retentate matter obtain cadmium sulfide by drying, filter
Water outlet enters stripping ammonia steaming system；
Two, ammonia still process is stripped；It adjusts except the wastewater pH after cadmium is 11 ~ 12, is passed through stripping ammonia still and carries out stripping ammonia still process, strip ammonia still process
Gas phase obtains ammonium hydroxide by condensation afterwards, and liquid phase is passed through except thiocarbamide reactor；
Three, thiocarbamide is removed；To except hydrogen peroxide is added in thiocarbamide reactor, resolved at high temperature by hydrogen peroxide with strong oxygen
The hydroxyl radical free radical for the property changed is passed through aeration tank after reaction and is aerated come thiocarbamide of degrading.
It is further characterized by:
Its is further comprising the steps of:
Four, coagulating sedimentation；Adjusting aeration tank water outlet pH is 9 ~ 11, and aluminium polychloride is added and polyacrylamide progress coagulation is anti-
It answers；
Five, filtration treatment；Adjusting coagulating sedimentation water outlet pH is neutrality, by more medium filter and active carbon filter, to go
Suspended material and partial organic substances in water removal；
Six, reverse osmosis；Filtering water outlet enters RO system, produces water and flow to pure water tank reuse, concentrated water enters evaporation equipment processing；
Seven, evaporation process；Reverse osmosis concentrated water enters vapo(u)rization system evaporative crystallization, the recycling condensing water of generation, evaporation concentrated solution committee
Outer processing；
Eight, Treatment of Sludge；The sediment of step 4 coagulating sedimentation is imported filter press to be carried out dehydrating, squeeze water is passed through sulphur removal
Urea reactor water inlet end, the outer processing of mud cake committee of generation.
Conditioning tank is equipped with before the high-temperature-resfilter filter system of step 1, adjusting wastewater pH is 10 ~ 12, and inflow temperature is 60 ~ 85
℃；
The filtering accuracy of high-temperature-resfilter filter system in step 1 is 0.05 μm ~ 5 μm；
In step 2 after entering the waste water of stripping ammonia still and passing through heat exchanger and stripping ammonia still water outlet heat exchange, then it is passed through stripping
In ammonia still；
Step 3 except conditioning tank is equipped with before thiocarbamide reactor, adjusting wastewater pH is 9 ~ 12, and temperature is 40 ~ 60 DEG C；
Removing in step 3 is filled with catalyst, the catalyst preparation process are as follows: absorbent charcoal carrier is through 0.1 in thiocarbamide reactor
8 ~ 10 h are dried after mol/L chlorohydric acid pickling at 100 ~ 150 DEG C, the carrier after activation is in the copper nitrate solution of 0.5 mol/L
10 ~ 15 h are impregnated, 1 ~ 3 h of calcining, deionized water at 300 ~ 450 DEG C is dried to after solid in nitrogen atmosphere and rinses to neutrality
It is obtained by drying afterwards；
Step 3 is 1:1 ~ 1:0.6 except the mass ratio of thiocarbamide in the hydrogen peroxide and waste water added in thiocarbamide reactor, when reaction
Between 2 hours, be passed through after reaction aeration tank be aerated 0.5 hour.
After such method, is reacted at high temperature according to cadmium and thiocarbamide and generate cadmium sulfide inorganic particle, simultaneously life
Waste water is produced in alkalinity and the higher feature of temperature, is directly filtered using high-temperature-resfilter filter system, the higher vulcanization of purity can be recycled
Cadmium realizes that the resource utilization of heavy metal cadmium utilizes, cadmium concentration is discharged after filtering and is less than 0.01mg/L.Meanwhile the height in waste water
For concentration ammonia nitrogen after stripping ammonia steaming system processing, ammonia nitrogen aqueous concentration is less than 30mg/L, and the ammonium hydroxide that high concentration can be obtained carries out
Reuse or sale.The combination of technique back segment except thiocarbamide reactor removed by being added directly hydrogen peroxide heavy metal in waste water and
Organic matter, it can be achieved that whole additive amount of medicament reduces by 30 ~ 40% compared with conventional coagulating sedimentation+Fenton treatment process, sludge is produced
Amount reduces by 50% ~ 60%, and operating cost reduces by 30 ~ 40%, while can be realized the effective recycling of cadmium resource and ammonium hydroxide.
Detailed description of the invention
Fig. 1 is flow chart of the present invention.
Specific embodiment
A kind of thin-film solar cells producing wastewater treatment as shown in Figure 1 comprising following steps:
One, cadmium is removed；Alkaline hot waste water in conditioning tank will be collected and be passed through high-temperature-resfilter filter system, by filtration system by cadmium
The cadmium sulfide filtering that salt and thiocarbamide generate under alkaline hot conditions, filter retentate matter obtain cadmium sulfide by drying, filter
Water outlet enters stripping ammonia steaming system；
In the step, since the main component in waste water is cadmium sulfide, ammonium hydroxide and thiocarbamide, thiocarbamide is unstable under alkaline condition,
It can decompose when high temperature and generate sulphion, and the wastewater pH generated in thin-film solar cells production process is 10 ~ 12, inflow temperature
It is 60 ~ 85 DEG C, it is adjusted by conditioning tank if pH and inflow temperature are unsatisfactory for requiring, with this condition in waste water
Cadmium sulfate and thiocarbamide can directly react generate cadmium sulfide inorganic particle, by production line water outlet directly by filtering accuracy be 0.05
~ 5 μm of high-temperature-resfilter filter system can achieve the purpose that heavy metal is recovered by filtration, while remove part thiocarbamide, filter retentate
Matter obtains the CdS yellow crystals that purity is 90 ~ 95% after 60 DEG C of drying, and filtration system, can for ceramic membrane filter system,
Metal agglomeration filter core filter, filer element type high-temperature-resfilter filter system, accurate filter and meet above-mentioned filtering accuracy (0.05 ~ 5
μm) and temperature various types of filtration device for trapping.
Two, ammonia still process is stripped；It adjusts except the wastewater pH after cadmium is 11 ~ 12, is passed through stripping ammonia still and carries out stripping ammonia still process, strip
Gas phase obtains ammonium hydroxide by condensation after ammonia still process, and liquid phase is passed through except thiocarbamide reactor；
In the step, after be discharged after exchanging heat to 80-95 DEG C into the waste water for stripping ammonia still by heat exchanger and stripping ammonia still,
It is passed through in stripping ammonia still, in ammonia still, is contacted with the steam counter-flow from tower reactor, steam containing ammonia is condensed into through condensing tower again
The concentrated ammonia liquor that concentration is 16 ~ 19%, ammonia still water outlet are directly entered except thiocarbamide reactor after heat exchanger cools down.
Three, thiocarbamide is removed；To except hydrogen peroxide is added in thiocarbamide reactor, there is strong oxygen by what hydrogen peroxide decomposition generated
The hydroxyl radical free radical of change effect is passed through aeration tank after reaction and is aerated come thiocarbamide of degrading；It is urged except being filled in thiocarbamide reactor
Agent, catalyst preparation process are as follows: absorbent charcoal carrier dries 8 ~ 10 after 0.1 mol/L chlorohydric acid pickling at 100 ~ 150 DEG C
H, the carrier after activation impregnate 10 ~ 15 h in the copper nitrate solution of 0.5 mol/L, be dried to after solid in nitrogen atmosphere in
1 ~ 3 h is calcined at 300 ~ 450 DEG C, deionized water is obtained by drying after rinsing to neutrality；Catalyst can increase reaction contact area
Catalyst surface loads heavy metal Cu simultaneously, has catalytic action to hydrogen peroxide, can increase decomposing hydrogen dioxide solution into hydroxyl radical free radical
Rate, while there is filtering crown_interception, reduce water outlet SS；
Waste water leaving water temperature after stripping ammonia still process processing is 40 ~ 60 DEG C, and pH is 9 ~ 12, if being unsatisfactory for through conditioning tank or changing
Hot device is adjusted to above range, is added directly hydroperoxidation 2 hours, (hydrogen peroxide is 1:1 ~ 1 with thiocarbamide mass ratio:
0.6), at the hydroxyl radical free radical with strong oxidizing property, can effectively degrade strips ammonia still and goes out accelerated decomposition H2O2 at high temperature
The thiocarbamide contained in water, achievees the purpose that remove COD, enters aeration tank after reaction and is aerated 0.5h.
Four, coagulating sedimentation；Adjusting aeration tank water outlet pH is 9 ~ 11, and aluminium polychloride is added and polyacrylamide carries out coagulation
Reaction 0.5 hour.
Five, filtration treatment；Adjusting coagulating sedimentation water outlet pH is neutrality, by more medium filter and active carbon filter,
To go suspended material and partial organic substances in water removal.
Six, reverse osmosis；Filtering water outlet enters RO system, and RO operating pressure is the MPa of 0.8 MPa ~ 1.5, produces water recycling
Rate is not less than 70%, produces water and flow to pure water tank reuse, concentrated water enters evaporation equipment processing.
Seven, evaporation process；Reverse osmosis concentrated water enters vapo(u)rization system evaporative crystallization, and the recycling condensing water of generation is concentrated by evaporation
The outer processing of liquid committee.
Eight, Treatment of Sludge；The sediment of step 4 coagulating sedimentation is imported filter press to be carried out dehydrating, squeeze water is passed through
Except thiocarbamide reactor water inlet end, the outer processing of mud cake committee of generation.
After such method, is reacted at high temperature according to cadmium and thiocarbamide and generate cadmium sulfide inorganic particle, simultaneously life
Waste water is produced in alkalinity and the higher feature of temperature, is directly filtered using high-temperature-resfilter filter system, the higher vulcanization of purity can be recycled
Cadmium realizes that the resource utilization of heavy metal cadmium utilizes, cadmium concentration is discharged after filtering and is less than 0.01mg/L.Meanwhile the height in waste water
For concentration ammonia nitrogen after stripping ammonia steaming system processing, ammonia nitrogen aqueous concentration is less than 30mg/L, and the ammonium hydroxide that high concentration can be obtained carries out
Reuse or sale.The combination of technique back segment except thiocarbamide reactor removed by being added directly hydrogen peroxide heavy metal in waste water and
Organic matter mixes on the basis of meeting relevant criterion " battery industry pollutant emission standard " (GB 30484-2013) with conventional
Retrogradation shallow lake+Fenton treatment process is compared, it can be achieved that whole additive amount of medicament reduces by 30 ~ 40%, and sludge yield reduces by 50% ~ 60%,
Operating cost reduces by 30 ~ 40%, while can be realized the effective recycling of cadmium resource and ammonium hydroxide.
Meanwhile as another of the invention beneficial effect, using " recycling is except cadmium filtration system+stripping ammonia still process+remove thiocarbamide
Reactor " pretreating process handles waste water, and effluent quality is improved significantly, compared with the method for conventionally employed Fenton technology,
The influent load for greatly reducing RO reclaiming system, compared with traditional reclamation set, recycle-water rate can be improved 20% or more；Together
When reverse osmosis concentrated water enter vapo(u)rization system condensing crystallizing, the condensed water of generation can reuse to workshop.Entire technique removes part solid waste
Need to entrust outer processing, without the generation of outer draining, realizes the near-zero release of film photovoltaic waste water substantially.
It is proved by the following examples:
Certain thin-film solar cells factory CBD plated film waste water quality of embodiment 1-3: concentration of cadmium ions is 80 ~ 100mg/L, ammonia nitrogen
It is 400 ~ 500mg/L for 11000 ~ 12000mg/L, COD, wherein thiocarbamide is 400 ~ 450mg/L.Wastewater flow is 5t/h, daily
Run 20h.
Implement 1 the following steps are included:
Step 1: adjusting pH is 11, into high-temperature-resfilter filter system, device material is 316L, and filter core aperture is 5 μm, inlet-pressure
Power is 0.3MPa, and inflow temperature is 70 DEG C, flow of inlet water 5t/h, and it is higher that filter retentate matter obtains purity after 60 DEG C of drying
CdS crystal, the cadmium concentration of filtering water outlet at this time are less than 0.01mg/L.
Step 2: filtering water outlet enters stripping ammonia steaming system, adjusting pH is 12, and inflow temperature is 85 DEG C, into stripper,
It is passed through steam (steam pressure is about 0.25MPa), steam containing ammonia is condensed into the concentrated ammonia liquor that concentration is 16 ~ 19%, tower bottom through condensing tower
Ammonia nitrogen water outlet is 18-23mg/L.
Step 3: stripping ammonia still water outlet, which enters, removes thiocarbamide reactor, inlet flow-patterm is 10 at this time, and inflow temperature is 50 DEG C,
H2O2(30% dosage) is 15L/h, enters aeration tank aeration 0.5h after reacting 2h.
Step 4: adjusting pH is 10, aluminium polychloride (10%) is added and polyacrylamide (1 ‰) is 15L/h and 17L/h,
React 0.5h.
Step 5: coagulating sedimentation goes out dilutional hyponatremia medium filter and active carbon filter, adjusting pH is 7, when inlet and outlet are pressed
Backwash is carried out using tap water when poor > 0.2kg/cm2.
Step 6: filtering water outlet enters RO system, final producing water ratio is that the concentrated water that 73 ~ 75%, RO is generated enters evaporation equipment
Processing.
Step 7: reverse osmosis concentrated water enters vapo(u)rization system evaporative crystallization, the outer processing of evaporation concentrated solution committee of generation, condensed water
Reuse is to workshop.
Embodiment 2 is the following steps are included: step 1: adjusting pH is 12, and into high-temperature-resfilter filter system, device material is
316L, filter core aperture are 0.05 μm, inlet pressure 0.3MPa, and inflow temperature is 60 DEG C, flow of inlet water 5t/h, filter retentate
Matter obtains the higher CdS crystal of purity after 60 DEG C of drying, and the cadmium concentration of filtering water outlet at this time is less than 0.01mg/L.
Step 2: filtering water outlet enters stripping ammonia steaming system, adjusting pH is 11.5, and inflow temperature is 80 DEG C, into stripping
Tower is passed through steam (steam pressure is about 0.25MPa), and steam containing ammonia is condensed into the concentrated ammonia liquor that concentration is 16 ~ 19% through condensing tower,
The water outlet of tower bottom ammonia nitrogen is 13-16mg/L.
Step 3: stripping ammonia still water outlet, which enters, removes thiocarbamide reactor, inlet flow-patterm is 12 at this time, and inflow temperature is 40 DEG C,
H2O2(30% dosage) is 15L/h, enters aeration tank aeration 0.5h after reacting 2h.
Step 4: adjusting pH is 11, aluminium polychloride (10%) is added and polyacrylamide (1 ‰) is 15L/h and 17L/h,
React 0.5h.
Step 5: coagulating sedimentation goes out dilutional hyponatremia medium filter and active carbon filter, adjusting pH is 7, when inlet and outlet are pressed
Backwash is carried out using tap water when poor > 0.2kg/cm2.
Step 6: filtering water outlet enters RO system, final producing water ratio is that the concentrated water that 73 ~ 75%, RO is generated enters evaporation equipment
Processing.
Step 7: reverse osmosis concentrated water enters vapo(u)rization system evaporative crystallization, the outer processing of evaporation concentrated solution committee of generation, condensed water
Reuse is to workshop.
Embodiment 3 is the following steps are included: step 1: adjusting pH is 10, and into high-temperature-resfilter filter system, device material is
316L, filter core aperture are 0.5 μm, inlet pressure 0.3MPa, and inflow temperature is 85 DEG C, flow of inlet water 5t/h, filter retentate
Matter obtains the higher CdS crystal of purity after 60 DEG C of drying, and the cadmium concentration of filtering water outlet at this time is less than 0.01mg/L.
Step 2: filtering water outlet enters stripping ammonia steaming system, adjusting pH is 11, and inflow temperature is 95 DEG C, into stripper,
It is passed through steam (steam pressure is about 0.25MPa), steam containing ammonia is condensed into the concentrated ammonia liquor that concentration is 16 ~ 19%, tower bottom through condensing tower
Ammonia nitrogen water outlet is 22-27mg/L.
Step 3: stripping ammonia still water outlet, which enters, removes thiocarbamide reactor, inlet flow-patterm is 9 at this time, and inflow temperature is 60 DEG C,
H2O2(30% dosage) is 15L/h, enters aeration tank aeration 0.5h after reacting 2h.
Step 4: adjusting pH is 9, aluminium polychloride (10%) is added and polyacrylamide (1 ‰) is 15L/h and 17L/h,
React 0.5h.
Step 5: coagulating sedimentation goes out dilutional hyponatremia medium filter and active carbon filter, adjusting pH is 7, when inlet and outlet are pressed
Backwash is carried out using tap water when poor > 0.2kg/cm2.
Step 6: filtering water outlet enters RO system, final producing water ratio is that the concentrated water that 73 ~ 75%, RO is generated enters evaporation equipment
Processing.
Step 7: reverse osmosis concentrated water enters vapo(u)rization system evaporative crystallization, the outer processing of evaporation concentrated solution committee of generation, condensed water
Reuse is to workshop.
Embodiment 4: certain thin-film solar cells factory clean waste water quality: Cd2+ be 40 ~ 50mg/L, ammonia nitrogen be 9000 ~
10000mg/L, COD are 250 ~ 300mg/L, and wherein thiocarbamide is 200 ~ 300mg/L.Wastewater flow is 10t/h, runs 12h daily.
Present case implement the following steps are included:
Step 1: adjusting pH is 11.5, into high-temperature-resfilter filter system, filter core aperture is 0.5 μm, inlet pressure 0.2MPa, into
Coolant-temperature gage is 85 DEG C, flow of inlet water 5t/h, and filter retentate matter obtains the higher CdS crystal of purity after 60 DEG C of drying, at this time
Filtering water outlet cadmium concentration is less than 0.01mg/L.
Step 2: filtering water outlet enters stripping ammonia steaming system, adjusting pH is 11, and inflow temperature is 80 DEG C, into stripper,
It is passed through steam (steam pressure is about 0.25MPa), steam containing ammonia is condensed into the concentrated ammonia liquor that concentration is 16 ~ 19%, tower bottom through condensing tower
Ammonia nitrogen water outlet is 12-17mg/L.
Step 3: stripping ammonia still water outlet, which enters, removes thiocarbamide reactor, inlet flow-patterm is 9 at this time, and inflow temperature is 60 DEG C,
H2O2(30% dosage) is 17L/h, enters aeration tank aeration 0.5h after reacting 2h.
Step 4: adjusting pH is 10, aluminium polychloride (10%) is added and polyacrylamide (1 ‰) is 30L/h and 35L/h,
React 0.5h.
Step 5: coagulating sedimentation goes out dilutional hyponatremia medium filter and active carbon filter, adjusting pH is 7, when inlet and outlet are pressed
Backwash is carried out using tap water when poor > 0.2kg/cm2.
Step 6:: filtering water outlet enters RO system, and final producing water ratio enters evaporation for 78 ~ 80%, the RO concentrated water generated and sets
Standby processing.
Step 7: reverse osmosis concentrated water enters vapo(u)rization system evaporative crystallization, the outer processing of solid waste committee of generation, condensed water is returned
With to workshop.
Comparative example: certain thin-film solar cells factory clean waste water quality: Cd2+ be 40 ~ 50mg/L, ammonia nitrogen be 9000 ~
10000mg/L, COD are 250 ~ 300mg/L, and wherein thiocarbamide is 200 ~ 300mg/L.Wastewater flow is 10t/h, runs 12h daily.
Present case implement the following steps are included:
Step 1: adjusting pH is 12, adds aluminium polychloride (10%) and polyacrylamide (1 ‰) carries out coagulating sedimentation, dosage
Respectively 30L/h and 40L/h, reaction time 0.5h.
Step 2: precipitating water outlet enters stripping ammonia steaming system, adjusting pH is 12, and inflow temperature is 90 DEG C, into stripper,
It is passed through steam (steam pressure >=0.4MPa), steam containing ammonia is condensed into the concentrated ammonia liquor that concentration is 16 ~ 19%, tower bottom ammonia through condensing tower
Nitrogen water outlet is 68-73mg/L.
Step 3: adjusting water outlet pH is 3, H2O2(30%) and dosage FeSO4(10%) be respectively 20L/h and 25L/h.
Adjusting pH later is 10, and heavy metal chelating agent (15%) 6L/h is added, and reacts 0.5h, adds aluminium polychloride (10%) and poly- third
Acrylamide (1 ‰) is 30L/h and 35L/h, reacts 0.5h.
Step 4: precipitating water outlet, which is adjusted, enters RO system after sand filtration, carbon filter after pH is 7, water reuse is produced, concentrated water enters
MVR evaporator, the recycling condensing water of generation, the outer processing of concentrate committee.
Using the process flow of " coagulating sedimentation+ammonia still process+Fenton+RO+MVR ", final sludge output is 240kg/d, is put down
Equal producing water ratio is 62%, and operating cost is about 32.26 yuan/ton of water (not including ammonium hydroxide income).Compared with the technique, this patent is most
Whole sludge output is 130kg/d, reduces by 45.8%；This patent Chinese medicine addition link is less simultaneously, and adding of agent expense reduces
30% or more；Average producing water ratio is 78%, increases by 20.5%；Operating cost is about 18.87 yuan/ton of water (not including ammonium hydroxide income).
More than, it is merely preferred embodiments of the present invention, but scope of protection of the present invention is not limited thereto, it is any
It is familiar with the people of the technology within the technical scope disclosed by the invention, any changes or substitutions that can be easily thought of, should all cover at this
Within the protection scope of invention.Therefore, protection scope of the present invention should be subject to the protection scope in claims.
Claims (8)
1. a kind of thin-film solar cells producing wastewater treatment, which is characterized in that itself the following steps are included:
One, cadmium is removed；Alkaline hot waste water in conditioning tank will be collected and be passed through high-temperature-resfilter filter system, by filtration system by cadmium
The cadmium sulfide filtering that salt and thiocarbamide generate under alkaline hot conditions, filter retentate matter obtain cadmium sulfide by drying, filter
Water outlet enters stripping ammonia steaming system；
Two, ammonia still process is stripped；It adjusts except the wastewater pH after cadmium is 11 ~ 12, is passed through stripping ammonia still and carries out stripping ammonia still process, strip ammonia still process
Gas phase obtains ammonium hydroxide by condensation afterwards, and liquid phase is passed through except thiocarbamide reactor；
Three, thiocarbamide is removed；To except hydrogen peroxide is added in thiocarbamide reactor, resolved at high temperature by hydrogen peroxide with strong oxygen
The hydroxyl radical free radical for the property changed is passed through aeration tank after reaction and is aerated come thiocarbamide of degrading.
2. one kind according to claim 1, it is characterised in that: its is further comprising the steps of:
Four, coagulating sedimentation；Adjusting aeration tank water outlet pH is 9 ~ 11, and aluminium polychloride is added and polyacrylamide progress coagulation is anti-
It answers；
Five, filtration treatment；Adjusting coagulating sedimentation water outlet pH is neutrality, by more medium filter and active carbon filter, to go
Suspended material and partial organic substances in water removal；
Six, reverse osmosis；Filtering water outlet enters RO system, produces water and flow to pure water tank reuse, concentrated water enters evaporation equipment processing；
Seven, evaporation process；Reverse osmosis concentrated water enters vapo(u)rization system evaporative crystallization, the recycling condensing water of generation, evaporation concentrated solution committee
Outer processing；
Eight, Treatment of Sludge；The sediment of step 4 coagulating sedimentation is imported filter press to be carried out dehydrating, squeeze water is passed through sulphur removal
Urea reactor water inlet end, the outer processing of mud cake committee of generation.
3. a kind of thin-film solar cells producing wastewater treatment according to claim 1, it is characterised in that: step 1
High-temperature-resfilter filter system before be equipped with conditioning tank, adjust wastewater pH be 10 ~ 12, inflow temperature be 60 ~ 85 DEG C.
4. a kind of thin-film solar cells producing wastewater treatment according to claim 1 or 3, it is characterised in that: step
The filtering accuracy of high-temperature-resfilter filter system in rapid one is 0.05 μm ~ 5 μm.
5. a kind of thin-film solar cells producing wastewater treatment according to claim 1, it is characterised in that: step 2
In wait enter stripping ammonia still waste water by heat exchanger and stripping ammonia still water outlet heat exchange after, then be passed through stripping ammonia still in.
6. a kind of thin-film solar cells producing wastewater treatment according to claim 1, it is characterised in that: step 3
Except conditioning tank is equipped with before thiocarbamide reactor, adjusting wastewater pH is 9 ~ 12, and temperature is 40 ~ 60 DEG C.
7. a kind of thin-film solar cells producing wastewater treatment according to claim 1, it is characterised in that: step 3
In except being filled with catalyst, the catalyst preparation process are as follows: absorbent charcoal carrier is through 0.1 mol/L hydrochloric acid in thiocarbamide reactor
8 ~ 10 h are dried after pickling at 100 ~ 150 DEG C, the carrier after activation impregnates 10 ~ 15 in the copper nitrate solution of 0.5 mol/L
H, is dried to after solid in nitrogen atmosphere 1 ~ 3 h of calcining at 300 ~ 450 DEG C, and deionized water is dried i.e. after rinsing to neutrality
?.
8. a kind of thin-film solar cells producing wastewater treatment described according to claim 1 or 6 or 7, it is characterised in that:
Step 3 is 1:1 ~ 1:0.6 except the mass ratio of thiocarbamide in the hydrogen peroxide and waste water added in thiocarbamide reactor, and the reaction time 2 is small
When, it is passed through aeration tank after reaction and is aerated 0.5 hour.
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| CN114314921A (en) * | 2021-12-30 | 2022-04-12 | 广东先导微电子科技有限公司 | Comprehensive recovery treatment method for tellurium-zinc-cadmium processing wastewater |
| CN115043541A (en) * | 2022-06-14 | 2022-09-13 | 尚越光电科技股份有限公司 | Treatment process and treatment system for flexible solar film roll-to-roll copper indium gallium selenide (CSD) production wastewater |
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