CN101973662A - Method and system for treating industrial wastewater of photovoltaic solar cell plates - Google Patents
Method and system for treating industrial wastewater of photovoltaic solar cell plates Download PDFInfo
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- CN101973662A CN101973662A CN2010102860714A CN201010286071A CN101973662A CN 101973662 A CN101973662 A CN 101973662A CN 2010102860714 A CN2010102860714 A CN 2010102860714A CN 201010286071 A CN201010286071 A CN 201010286071A CN 101973662 A CN101973662 A CN 101973662A
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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
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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
- 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
Abstract
The invention discloses a process for treating industrial wastewater of photovoltaic solar cell plates. The process comprises the following steps of: collecting wastewater, namely collecting acid wastewater and alkaline wastewater respectively; regulating pH, namely adding strong acid or strong base into the acid wastewater, alkaline wastewater or acid-alkaline mixed wastewater mixed by the acid wastewater and the alkaline wastewater, and regulating the pH value to be between 8.0 and 8.5 to form conditioning fluid; defluorinating the conditioning fluid and/or removing chemical oxygen demand (COD) from the conditioning fluid, wherein the defluorinating step means throwing calcium salt into the conditioning fluid so as to remove fluorion from the wastewater, and the COD removing step means performing incomplete anaerobic reaction on the conditioning fluid; performing aerobic biological treatment; and sequentially completing the steps to discharge the wastewater meeting the discharge standard. The invention provides a treatment process aiming at the water quality characteristics of the industrial wastewater of the photovoltaic solar cell plates and main design operational parameters. By a treatment system, the fluorion can be effectively removed, the fluorion concentration of effluent can be reduced to be below 10mg/L, and the wastewater CODCr is below 300mg/L and meets the discharge standard. Meanwhile, the invention also provides a system for treating the industrial wastewater of the photovoltaic solar cell plates.
Description
Technical field
The present invention relates to waste water treatment process, relate to a kind of treatment process and applied Waste Water Treatment of this method of photovoltaic solar cell sheet factory effluent particularly.
Background technology
Under the pressure of global energy crisis and climate warming, the development of renewable new forms of energy industry more and more receives publicity.The inexhaustible clean energy that utilizes the Nature to give as development sun power, can not only solve the future source of energy problem of shortage, and can solve for a long time the environmental problem that fossil oil caused of mankind's dependence.
Under the promotion of policy, rules and the action plan of government, the production of solar cell is just with the looks rapid growth of a sunrise industry.In in the past 15 years, global photovoltaic industry is with 25% average annual rate increase, and the average annual compound rate of growth of global photovoltaic system installation was up to 49.1% in 2000～2009.In China, government also pays much attention to the development of solar energy industry.Hu Jintao secretary's once important written instructions in " about supporting the suggestion of China's sun power autonomous innovation gordian technique " report are pointed out: sun power is one of important renewable energy source, advance scientific and technical innovation, solving the expensive problem of solar electrical energy generation is the key that large-scale develops and utilizes sun power.From China's solar cell production high speed development in 2002, average growth rate per annum reached 180%.The solar product manufacturing enterprise of China has surpassed 500 families at present.
Yet as the sunrise industry of producing clean energy, the manufacture of solar cells process is also unclean.In the processes such as cutting, corrosion and rinsing that crystalline silicon is produced, can produce high pollution waste water.Also can produce waste water in the processes such as making herbs into wool, etching, rinsing and evaporation of the solar battery sheet course of processing, these manufacture of solar cells waste water have following characteristics:
1) the waste water acid-basicity is extremely strong;
2) fluorinion concentration height, fluorinion concentration are often at several thousand even several ten thousand ppm;
3) total dissolved solidss content is big, owing to adopt a large amount of strong acid and strong bases in the manufacture of solar cells, brings a large amount of mineral ions in the waste discharge into, causes total dissolved salt content height;
4) adopt organic solvent to cause the chemical oxygen demand (COD) that contains higher concentration in the waste discharge in the manufacture of solar cells.
At the These characteristics of the waste water that production process produced of following this solar cell, for the production wastewater treatment of photovoltaic solar cell has been brought following difficult point:
1) pH regulator consumption acids alkali number is big;
2) content of fluoride ion height needs to select reasonable medicament and treatment process just can reach the following emission standard of 10mg/L;
3) total dissolved salt height, and, cause the total salt amount of waste water height owing to add a large amount of medicaments in the removal fluorion process, and the hardness height, the traditional biological treatment system is caused inhibition, the COD removal effect is undesirable.
Be regarded as green sunrise industry in China's manufacture of solar cells at present.And the environmental pollution that its factory effluent causes is not sufficiently paid attention to.Existing many enterprises only adopt simple flocculation sediment, add methods adjusting pH and removal part fluorine such as carbide slag or lime for this waste water, fluorine content still exceeds standard in its waste discharge, bring serious secondary pollution into, and the COD that large amount of organic causes does not remove; Simultaneously, also have part enterprise to adopt the traditional biological treatment system, but because manufacture of solar cells waste water acid-basicity is extremely strong, need to add a large amount of medicaments before entering biological treatment, cause in the waste water saltiness up to more than 2%, waste water hardness height, like this, the simple inhibition of adopting the traditional biological treatment system to tend to be subjected to high salt and high rigidity, the biological treatment effect extreme difference, COD removes undesirable, discharge of wastewater is not up to standard, directly discharging then causes the serious environmental pollution problem, enters city planting ductwork and then the downstream Sewage Plant is brought bigger impact load, even influence its normal operation.
Though the development trend of this sunrise industry of manufacture of solar cells is had an optimistic view of in the many areas of China at present, because the environmental protection pressure in the manufacture of solar cells forces many manufacture of solar cells projects to have to halt or shelve.
Therefore, be badly in need of the strong acid-base that is discharged at this photovoltaic solar cell production, high saliferous, high fluorine and the efficient cheap treatment technology of high COD trade effluent exploitation, satisfy qualified discharge or regeneration requirement.
Summary of the invention
The objective of the invention is provides a kind of treatment process and system of photovoltaic solar cell sheet factory effluent at above-mentioned photovoltaic solar cell sheet factory effluent characteristics and difficulty in treatment.This method flow is simple, and working cost is lower, and the level of automation height can solve a difficult problem that perplexs the wastewater treatment of current photovoltaic solar industry.
For this reason, the invention provides a kind of photovoltaic solar cell sheet production wastewater treatment technology, technology may further comprise the steps: wastewater collection, collect acid waste water and alkaline waste water respectively; PH regulator, oxytropism waste water, alkaline waste water or mixed in the soda acid composite waste that forms by acid waste water and alkaline waste water add strong acid or highly basic, regulate pH value to 8.0～8.5, the formation treatment solution; Treatment solution is carried out defluorination and/or removes the COD step; The defluorination step is to drop into calcium salt in treatment solution, to remove the fluorion in the waste water; Removing the COD step is that treatment solution is carried out incomplete anaerobic reaction; Carrying out aerobe again handles; Finish above-mentioned steps successively, the waste water that will reach emission standard effluxes.
According to further improvement of the present invention, the wastewater collection process further comprises: collect acid waste water and alkaline waste water respectively, hydraulic detention time is greater than 8h.
According to further improvement of the present invention, the defluorination process further comprises: the one-level defluorination, drop into calcium salt in the waste water that regulates the pH value, the input amount of calcium salt and the mass ratio of fluorion are 4: 1～5: 1, stirring reaction 20～30min, precipitation 1～2h, scavenger precipitation chemical sludge.
According to further improvement of the present invention, the defluorination process further comprises: the secondary defluorination, drop into calcium salt once more in the waste water through one-level defluorination process, the input amount of calcium salt is 500～1000mg/L, stirring reaction 20～30min, precipitation 2h, scavenger precipitation chemical sludge.
According to further improvement of the present invention, further comprise in the secondary defluorination process: when dropping into calcium salt, add 100～200mg/L flocculation agent, and the coagulant aids of 3～8mg/L.
According to further improvement of the present invention, the defluorination process further comprises: carry out concentration to precipitating the chemical sludge that is produced in the defluorination process, the advanced treatment that the resource recovery of fluorine was disposed or carried out to landfill is transported outward in thickened sludge dehydration back, concentrating filtrate turns back to the pH regulator step, continues to handle.
According to further improvement of the present invention, aerobe is handled and is further comprised: the biochemical sludge part of discharging in the aerobe treating processes is applied in the aerobe treating processes once more; Excess sludge is carried out concentration, and the biochemical sludge after concentrating is transported outward after processed or compost is disposed, and concentrating filtrate turns back to incomplete anaerobic reaction step, continues to handle.
According to further improvement of the present invention, employed calcium salt is CaCl in the above-mentioned technology
2Flocculation agent is Al
2(SO
4)
3, polyaluminium sulfate; Coagulant aids is a polyacrylamide.
According to further improvement of the present invention, remove in the COD step, not exclusively the time of anaerobic reaction is 8～12h.
According to further improvement of the present invention, remove in the COD step, the hydraulic detention time of aerobe treating processes is greater than 20h, and sludge concentration is 3000～4000mg/L, reaction postprecipitation 1～2h.
Simultaneously, a kind of Waste Water Treatment also is provided in the present invention, has been used for handling the waste water that photovoltaic solar cell sheet production process is produced, having comprised: the wastewater collection pond, comprise acid waste water pond and alkaline waste water pond, be used for collecting respectively acid waste water and alkaline waste water; The pH regulator pond is connected respectively with acid waste water pond and alkaline waste water pond, and the pH regulator pond is provided with the soda acid dog-house, is used to add strong acid or the highly basic of regulating waste water ph; The defluorination unit, in order to remove the fluorion in the waste water, the defluorination unit comprises reaction tank and settling tank, and pH regulator pond, reaction tank and settling tank connect in regular turn, and reaction tank is provided with dog-house; Settling tank is provided with chemical sludge relief outlet and water outlet; Not exclusively anaerobic reation pool links to each other with the water outlet and the pH regulator pond of settling tank in the defluorination unit respectively, is used to carry out incomplete anaerobic reaction; The aerobe reaction member, being used to carry out aerobe handles, comprise aerobe reaction tank and biochemical settling tank, not exclusively anaerobic reation pool, aerobe reaction tank and biochemical settling tank connect in regular turn, and biochemical settling tank is provided with waste water and effluxes mouth and biochemical sludge relief outlet.
According to the present invention, comprise two defluorination unit that connect in regular turn, the first defluorination unit: comprise first reaction tank and first settling tank, be used to finish the one-level defluorination; The second defluorination unit: comprise second reaction tank and second settling tank; Finish the secondary defluorination; Second reaction tank is connected with the water outlet of first settling tank; First reaction tank in the first defluorination unit is connected with the pH regulator pond, and the water outlet of second settling tank in the second defluorination unit is connected with incomplete anaerobic reation pool.
According to further improvement of the present invention, also comprise sludge thickener, sludge thickener comprises: the chemical sludge concentration basin, be used for the chemical sludge that the defluorination unit is produced is carried out concentration, and the chemical sludge concentration basin is connected with the chemical sludge relief outlet of each settling tank in the defluorination unit.The biochemical sludge concentration basin, the biochemical sludge that is used for the aerobe treating processes is discharged carries out concentration, and the biochemical sludge concentration basin links to each other with the biochemical sludge relief outlet of biochemical settling tank.
According to further improvement of the present invention, all be provided with whipping appts in each reaction tank in pH regulator pond and the defluorination unit.
According to further improvement of the present invention, be provided with online pH monitor in the pH regulator pond, be used for pH value in the measuring cell.
Beneficial effect of the present invention is: the invention provides treatment process and main design and operation parameter at photovoltaic solar factory effluent water quality characteristics, adopt this treatment system, can effectively remove fluorion, the water outlet fluorinion concentration is reduced to below the 10mg/L, simultaneity factor has been eliminated the restraining effect of high saliferous and hardly degraded organic substance, guarantee that biochemical system can normally move, handle waste discharge COD
Cr(chemical oxygen demand that adopts potassium bichromate to determine as oxygenant) is below the 300mg/L.Waste water can directly discharge or reach and receive pipe standards and enter downstream sewage centralized treatment plant after treatment.
Description of drawings
Accompanying drawing constitute this specification sheets a part, be used for further understanding the present invention, accompanying drawing shows the preferred embodiments of the present invention, and is used for illustrating principle of the present invention with specification sheets.Among the figure:
Fig. 1 shows the schema of a kind of treatment process of photovoltaic solar cell sheet factory effluent according to the present invention.
Embodiment
Be noted that following detailed description all is exemplary, is intended to the invention provides further instruction.Unless otherwise, all technology used herein and scientific terminology have the identical meanings with general technical staff of the technical field of the invention's common sense.
As shown in Figure 1, a kind of schema of treatment process of photovoltaic solar cell sheet factory effluent has been shown according to the present invention among Fig. 1.Wherein the solid line step of connecting is explained the sewage disposal step, and the dotted line step of connecting is represented the sludge treatment step.
In a kind of typical embodiment of the present invention, a kind of photovoltaic solar cell sheet production wastewater treatment technology may further comprise the steps: collect acid waste water and alkaline waste water respectively in acid waste water pond and alkaline waste water pond; Oxytropism waste water, alkaline waste water or mixed in the soda acid composite waste that forms by acid waste water and alkaline waste water add strong acid or highly basic, regulate pH value to 8.0～8.5, the formation treatment solution.Treatment solution is carried out defluorination and/or removes the COD step; Wherein, the defluorination step is to drop into calcium salt in treatment solution, to remove the fluorion in the waste water; Removing the COD step is that treatment solution is carried out incomplete anaerobic reaction; Carrying out aerobe again handles; Finish above-mentioned steps successively, the waste water that will reach emission standard effluxes.
In the photovoltaic solar cell sheet production wastewater treatment technology of the present invention, acid waste water and alkaline waste water can individual curing, also can mix aftertreatment.According to the kind of handled waste water in the pH regulator process, those skilled in the art are easy to judge in the subsequent processes and should carry out defluorination and/or remove the COD step treatment solution; Regulate pH to 8.0～8.5 as in the acid waste water of collecting, add highly basic for being treated to of separate acid wastewater, form treatment solution, treatment solution is transported to the defluorination unit, in treatment solution, drop into calcium salt, to remove the fluorion in the treatment solution in the defluorination unit; Make fluorinion concentration less than 10mg/L, satisfy outwards discharging after the emission standard.In the alkaline waste water of collecting, add strong acid for being treated to of alkaline waste water and regulate pH to 8.0～8.5, form treatment solution, treatment solution is carried out incomplete anaerobic reaction; Carrying out aerobe again handles; Make treatment solution COD
CrLess than 300mg/L, satisfy outwards discharging after the emission standard.For the soda acid composite waste, can utilize the spent acid salkali waste to regulate pH mutually, part realizes the treatment of wastes with processes of wastes against one another, reduces the input amount of strong acid and strong base.The soda acid composite waste is regulated pH to 8.0～8.5 in the pH regulator pond by adding strong acid or highly basic, forms treatment solution, and treatment solution is transported to the defluorination unit, drops into calcium salt in the defluorination unit in treatment solution, to remove the fluorion in the treatment solution; The treatment solution of finishing the defluorination step is carried out incomplete anaerobic reaction; Carry out aerobe again and handle removal COD.After finishing above-mentioned steps successively, the waste water that will reach emission standard effluxes.
Preferably, in the above-mentioned waste water treatment process, acid waste water and alkaline waste water respectively the hydraulic detention time in acid waste water pond and alkaline waste water pond all greater than 8h.
Preferably, in the pH regulator pond, carry out the pH regulator hydraulic detention time in the above-mentioned waste water treatment process and be not less than 30min.
Preferably, in a kind of preferred implementation of the present invention, the defluorination process of above-mentioned waste water treatment process further comprises: the one-level defluorination, in the waste water that regulates the pH value, drop into calcium salt, the input amount of calcium salt and the mass ratio of fluorion are 4: 1～5: 1, stirring reaction 20～30min, precipitation 1～2h regularly discharges precipitating sludge to the chemical sludge concentration basin.More preferably, above-mentioned defluorination process further comprises: the secondary defluorination, drop into calcium salt once more in the waste water through one-level defluorination process, the input amount of calcium salt is 500～1000mg/L, stirring reaction 20～30min, precipitation 2h regularly discharges precipitating sludge to the chemical sludge concentration basin.More preferably further comprise in the secondary defluorination process: when dropping into calcium salt, add 100～200mg/L flocculation agent, and the coagulant aids of 3～8mg/L.Operable in the present invention calcium salt includes but not limited to CaCl
2Operable in the present invention flocculation agent includes but not limited to Al
2(SO
4)
3, polyaluminium sulfate; Operable in the present invention coagulant aids includes but not limited to polyacrylamide; Step through secondary defluorination among the present invention can be reduced to the fluorinion concentration in the waste water below the 10mg/L, but reaches the emission standard of fluorion in the waste water.
Preferably, in the above-mentioned waste water treatment process, the hydraulic detention time of waste water in incomplete anaerobic reation pool is controlled at 8～12h in the process of removal COD.
Preferably, in the above-mentioned waste water treatment process, remove in the process of COD, the hydraulic detention time of waste water in the aerobe reaction tank is greater than 20h, and sludge concentration is 3000～4000mg/L, reaction postprecipitation 1～2h.
In a kind of preferably embodiment of the present invention, in order to improve resource utilization, also in order to reduce pollution, defluorination process in waste water treatment process of the present invention further comprises: the chemical sludge that is produced in the defluorination process is carried out concentration, chemical sludge after concentrating can be transported outward the resource recovery that fluorine was disposed or carried out to landfill after dewatering, concentrating filtrate turns back to the pH regulator step, continues to handle.Simultaneously, further comprise in the aerobe treating processes: the sludge part of discharging in the aerobe treating processes is applied in the aerobe treating processes once more, excess sludge is carried out concentration, biochemical sludge after concentrating is transported outward after processed or compost is disposed, concentrating filtrate turns back to incomplete anaerobic reaction step, continues to handle.
Simultaneously, in order to realize above-mentioned waste water treatment process by efficiently and effectively, a kind of Waste Water Treatment also is provided in the present invention, be used for handling the waste water that photovoltaic solar cell sheet production process is produced, this system comprises: wastewater collection pond, pH regulator pond, defluorination unit, incomplete anaerobic reation pool, aerobe reaction member.The wastewater collection pond comprises acid waste water pond and alkaline waste water pond, is used for collecting respectively acid waste water and alkaline waste water.The pH regulator pond is connected respectively with acid waste water pond and alkaline waste water pond, and the pH regulator pond is provided with the soda acid dog-house, is used to add strong acid or the highly basic of regulating waste water ph.The defluorination unit, in order to remove the fluorion in the waste water, this defluorination unit comprises reaction tank and settling tank, wherein pH regulator pond, reaction tank and settling tank connect in regular turn.On reaction tank, be provided with dog-house, be used for dropping into calcium salt and the flocculation agent that to remove the waste water fluorion, coagulant aids etc.First settling tank is provided with chemical sludge relief outlet and water outlet.Finishing the liquid of separate acid wastewater treating processes can directly get rid of by water outlet.Not exclusively the water port and the pH regulator pond of settling tank links to each other respectively in anaerobic reation pool and the defluorination unit, is used to carry out incomplete anaerobic reaction; The aerobe reaction member is used to carry out aerobe to be handled, comprise aerobe reaction tank and biochemical settling tank, not exclusively anaerobic reation pool, aerobe reaction tank and biochemical settling tank connect in regular turn, and wherein, biochemical settling tank is provided with waste water and effluxes mouth and biochemical sludge relief outlet.
Preferably, this Waste Water Treatment, comprise two defluorination unit that connect successively, the first defluorination unit comprises first reaction tank and first settling tank, be used to finish the one-level defluorination, the second defluorination unit comprises, second reaction tank and second settling tank, be used to finish the secondary defluorination, second reaction tank is connected with the first sedimentary water outlet.First reaction tank in the first defluorination unit is connected with the pH regulator pond, and the water outlet of second settling tank in the second defluorination unit is connected with incomplete anaerobic reation pool.
Preferably, all be provided with whipping appts, be used for the liquid in the reaction process stirred vessel, more preferably, be provided with online pH monitor in the pH pond, be used for pH value in the measuring cell in the pH regulator pond and in unitary each reaction tank of defluorination.
Preferably, the chemical sludge and the biochemical sludge that are produced in order to handle well in the wastewater treatment process better at this Waste Water Treatment, also comprise sludge thickener, and this sludge thickener comprises chemical sludge concentration basin and biochemical sludge concentration basin.The chemical sludge concentration basin is used for the chemical sludge that the defluorination unit is produced is carried out concentration, and this chemical sludge concentration basin is connected with the chemical sludge relief outlet of each settling tank in the defluorination unit.Subsequent disposal at the chemical sludge concentration basin partly connects dewatering system, and dewatering system carries out processed to chemical sludge, and the chemical sludge concentrating filtrate that produces need turn back to the pH regulator pond and handle.The biochemical sludge concentration basin, the biochemical sludge that is used for the aerobe treating processes is discharged carries out concentration, and the biochemical sludge concentration basin links to each other with the biochemical sludge relief outlet of biochemical settling tank.Subsequent disposal at the biochemical sludge concentration basin partly connects the outlet dewatering system, and dewatering system carries out processed to biochemical sludge, and the biochemical sludge concentrating filtrate that is produced turns back to incomplete anaerobic reation pool and handles.
Preferably, the problem that in the practical application of this Waste Water Treatment, may have elevation, at this moment, can in this Waste Water Treatment, add an intermediate pool, and sewage pump is set in intermediate pool, so that lay according to the engineering real system, lifting sewage satisfies waterpower elevation demand to the subsequent reactions pond.
The invention provides a kind of treatment process of photovoltaic solar cell sheet factory effluent, adopt the thing treatment technology of delivering a child behind the multistage defluorination to handle photovoltaic solar cell sheet factory effluent, processed waste water reaches direct emission standard or enters downstream sewage work receives pipe standards.
Embodiment one
In a tame photovoltaic solar cell sheet manufacturer, acid waste water and the alkaline waste water collecting in the production process respectively to be produced are tested acid waste water and alkaline waste water, and wherein the pH value of acid waste water is 1.5, and content of fluoride ion is 4700mg/L; The pH value of alkaline waste water is 13.1, COD
CrConcentration value is 5800mg/L.
About respectively 8h of the acid waste water pond and the alkaline waste water tank waterpower residence time, being promoted to the pH regulator pond through lift pump mixes, the built-in stirrer in pH regulator pond, the rotating speed of stirrer is 160 rev/mins (RPM) in the mixing process, the pH value was 4.9 after the online pH instrument demonstration that is provided with in the pond mixed, utilize online pH instrument control to add alkali pump, utilize volume pump to add NaOH solution and regulate between composite waste pH to 8.0～8.5 pH regulator tank waterpower residence time 30min.
The composite waste gravity flow enters unitary first reaction tank removal of follow-up first defluorination fluorion after regulating pH, utilizes volume pump to add CaCl
2About 8.84g/L, stirring reaction time 20min under the built-in stirrer effect of reaction tank, the rotating speed of stirrer is 160RPM, the waste water gravity flow of reaction back enters first settling tank precipitation, settling tank hydraulic detention time 1.5h.The waste water gravity flow enters unitary second reaction tank of second defluorination behind the one-level defluorination, carries out the reaction of secondary defluorination, utilizes volume pump to add CaCl
2About 500mg/L, reaction tank is provided with stirrer, and rotating speed 88RPM utilizes volume pump to add Al simultaneously
2(SO4)
3Flocculation agent 150mg/L and PAM coagulant aids 5mg/L, reaction times 30min, the gravity flow of reaction back enters second settling tank, hydraulic detention time 2h.Precipitated outlet water is from flowing into intermediate pool, hydraulic detention time 1h.
Intermediate pool waste water is promoted to incomplete anaerobic reation pool through lift pump, hydraulic detention time 8h, and reaction tank adopts pulse water distribution.Not exclusively anaerobic reaction water outlet gravity flow enters follow-up aerobic biochemical pond, hydraulic detention time 20h.Gas-water ratio 30: 1 adopts the microporous diaphragm aeration tube.Sludge concentration 3000mg/L, the biochemistry pool water outlet flows into follow-up biochemical settling tank, settling tank residence time 2h.
The priority pollutant index is as shown in table 1 in the biochemical settling tank water outlet.
Table 1 is handled the principal pollutant index of back water outlet
These parameters all adopts this area method test gained commonly used.By data in the table 1 as can be known, the waste water of discharging through waste water treatment process of the present invention meets China's discharge of wastewater respective standard, can enter the downstream and concentrate sewage work.
The precipitation discharging contains CaF in above-mentioned one-level and secondary defluorination process
2Chemical sludge, gravitational discharge is collected in the chemical sludge concentration basin, mud discharging is manually controlled, concentrating chemical mud is promoted to plate-and-frame filter press dehydration back through the mud spiral pump and transports outward landfill, the sludge dewatering filtrate turns back to the pH regulator pond.Biochemical settling tank precipitating sludge is partly refluxed to the aerobic biochemical pond, reflux ratio 50%, all the other excess sludge gravitational discharges are collected in the biochemical sludge concentration basin, mud discharging is manually controlled, spissated biological sludge is transported outward disposal after processed, biochemical sludge dehydration filtrate turns back to incomplete anaerobic reation pool.
In this actual case history, this system is provided with programmable logic controller (PLC) system, is used for according to liquid level control lift pump start and stop in the pond, according to control dosing volume pump start and stop such as pH and fluorinion concentrations, also regulating being used for the unitary fan operation of biochemical treatment time and air quantity.
Embodiment two
Discharging alkaline waste water COD in the solar battery sheet production process
Cr5000mg/L, pH12.3, acid waste water pH 1.2, fluorinion concentration 5800mg/L.Adopt acid waste water, alkaline waste water shunting to handle.Acid waste water tank waterpower residence time 10h, alkaline waste water tank waterpower residence time 8h.
Acid waste water is promoted to the pH regulator pond, adds NaOH solution and regulates pH to 8.0～8.5, and the water outlet gravity flow enters unitary first reaction tank of first defluorination, adds CaCl
2About 29g/L, reaction 30min, the waste water gravity flow of reaction back enters first settling tank, hydraulic detention time 2h.The water outlet gravity flow enters second reaction tank, adds CaCl
21000mg/L adds Al simultaneously
2(SO
4)
3Flocculation agent 200mg/L and PAM coagulant aids 8mg/L, reaction times 30min, the gravity flow of reaction back enters second settling region, hydraulic detention time 2h.Precipitated outlet water pH is about about 8.0, fluorinion concentration 8mg/L, directly standard discharge.Defluorination settling tank discharging chemical sludge concentrates the back at the chemical sludge concentration basin and regularly beats to the mud and sewage unit, and the dehydrated sludge outward transport is as reclaiming purification fluorite raw material.
Alkaline waste water is promoted to another pH regulator pond, adds sulfuric acid and regulates pH to 8.0～8.5.Regulate back water outlet gravity flow and enter incomplete anaerobic reation pool, hydraulic detention time 12h, water outlet enters follow-up aerobic biochemical reaction tank, hydraulic detention time 28h, the about 4000mg/L of sludge concentration is through biochemical post precipitation water outlet COD
CrAbout 280mg/L, pH 7.5～8.0, can standard discharge.Biochemical settling tank mud dewaters after concentration and transports outward landfill.
The above is the preferred embodiments of the present invention only, is not limited to the present invention, and for a person skilled in the art, the present invention can have various changes and variation.Within the spirit and principles in the present invention all, any modification of being done, be equal to replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (15)
1. photovoltaic solar cell sheet production wastewater treatment technology is characterized in that described technology may further comprise the steps:
Acid waste water and alkaline waste water are collected in wastewater collection respectively;
PH regulator, oxytropism waste water, alkaline waste water or mixed in the soda acid composite waste that forms by described acid waste water and alkaline waste water add strong acid or highly basic, regulate pH value to 8.0～8.5, the formation treatment solution;
Described treatment solution is carried out defluorination and/or removes the COD step;
Described defluorination step is to drop into calcium salt in described treatment solution, to remove the fluorion in the waste water;
The described COD step of removing is that treatment solution is carried out incomplete anaerobic reaction; Carrying out aerobe again handles;
Finish above-mentioned steps successively, the waste water that will reach emission standard effluxes.
2. waste water treatment process according to claim 1 is characterized in that, described wastewater collection process further comprises:
Collect acid waste water and alkaline waste water respectively, hydraulic detention time is greater than 8h.
3. waste water treatment process according to claim 1 is characterized in that, described defluorination process further comprises:
The one-level defluorination drops into calcium salt in the waste water that regulates the pH value, the input amount of described calcium salt and the mass ratio of fluorion are 4: 1～5: 1, stirring reaction 20～30min, precipitation 1～2h, scavenger precipitation chemical sludge.
4. waste water treatment process according to claim 3 is characterized in that, described defluorination process further comprises:
The secondary defluorination drops into calcium salt once more in the waste water through one-level defluorination process, the input amount of described calcium salt is 500～1000mg/L, stirring reaction 20～30min, precipitation 2h, scavenger precipitation chemical sludge.
5. waste water treatment process according to claim 4 is characterized in that, further comprises in the described secondary defluorination process:
When dropping into calcium salt, add 100～200mg/L flocculation agent, and the coagulant aids of 3～8mg/L.
6. according to each described waste water treatment process of claim 1-5, it is characterized in that described defluorination process further comprises:
Carry out concentration to precipitating the chemical sludge that is produced in the defluorination process, with the advanced treatment that the resource recovery of fluorine was disposed or carried out to thickened sludge dehydration back outward transport landfill, concentrating filtrate turns back to the pH regulator step, continues to handle.
7. waste water treatment process according to claim 1 is characterized in that, described aerobe is handled and further comprised:
The biochemical sludge part of discharging in the aerobe treating processes is applied in the described aerobe treating processes once more; Excess sludge is carried out concentration, and the biochemical sludge after concentrating is transported outward after processed or compost is disposed, and concentrating filtrate turns back to incomplete anaerobic reaction step, continues to handle.
8. waste water treatment process according to claim 5 is characterized in that,
Described calcium salt is CaCl
2
Described flocculation agent is Al
2(SO
4)
3, polyaluminium sulfate;
Described coagulant aids is a polyacrylamide.
9. waste water treatment process according to claim 1 is characterized in that, removes in the COD step, and not exclusively the time of anaerobic reaction is 8～12h.
10. waste water treatment process according to claim 1 is characterized in that, removes in the COD step, and the hydraulic detention time of aerobe treating processes is greater than 20h, and sludge concentration is 3000～4000mg/L, reaction postprecipitation 1～2h.
11. a Waste Water Treatment is used for handling the waste water that photovoltaic solar cell sheet production process is produced, and it is characterized in that described system comprises:
The wastewater collection pond comprises acid waste water pond and alkaline waste water pond, is used for collecting respectively acid waste water and alkaline waste water;
The pH regulator pond is connected respectively with acid waste water pond and alkaline waste water pond, and described pH regulator pond is provided with the soda acid dog-house, is used to add strong acid or the highly basic of regulating waste water ph;
The defluorination unit, in order to remove the fluorion in the waste water, described defluorination unit comprises reaction tank and settling tank, and described pH regulator pond, reaction tank and settling tank connect in regular turn, and described reaction tank is provided with a dog-house; Described settling tank is provided with chemical sludge relief outlet and water outlet;
Not exclusively anaerobic reation pool links to each other respectively with the water outlet and the pH regulator pond of settling tank in the described defluorination unit, is used to carry out incomplete anaerobic reaction;
The aerobe reaction member, being used to carry out aerobe handles, comprise aerobe reaction tank and biochemical settling tank, described incomplete anaerobic reation pool, described aerobe reaction tank and described biochemical settling tank connect in regular turn, and described biochemical settling tank is provided with waste water and effluxes mouth and biochemical sludge relief outlet.
12. Waste Water Treatment according to claim 11 is characterized in that, comprises two defluorination unit that connect in regular turn,
The first defluorination unit: comprise first reaction tank and first settling tank, be used to finish the one-level defluorination;
The second defluorination unit: comprise second reaction tank and second settling tank; Finish the secondary defluorination; Described second reaction tank is connected with the water outlet of described first settling tank;
First reaction tank in the first defluorination unit is connected with described pH regulator pond, and the water outlet of second settling tank in the second defluorination unit is connected with described incomplete anaerobic reation pool.
13., it is characterized in that also comprise sludge thickener, described sludge thickener comprises according to claim 11 or 12 described Waste Water Treatments:
The chemical sludge concentration basin is used for the chemical sludge that the defluorination unit is produced is carried out concentration, and described chemical sludge concentration basin is connected with the chemical sludge relief outlet of each settling tank in the described defluorination unit;
The biochemical sludge concentration basin, the biochemical sludge that is used for the aerobe treating processes is discharged carries out concentration, and described biochemical sludge concentration basin links to each other with the biochemical sludge relief outlet of described biochemical settling tank.
14. Waste Water Treatment according to claim 11 is characterized in that, all is provided with whipping appts in each reaction tank in described pH regulator pond and the described defluorination unit.
15. Waste Water Treatment according to claim 11 is characterized in that, is provided with online pH monitor in the described pH regulator pond, is used for pH value in the measuring cell.
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