CN108314242A - High ammonia nitrogen contains the fluorine-containing photovoltaic wastewater processing method of arsenic and system - Google Patents
High ammonia nitrogen contains the fluorine-containing photovoltaic wastewater processing method of arsenic and system Download PDFInfo
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Abstract
The present invention provides a kind of high ammonia nitrogens to contain the fluorine-containing photovoltaic wastewater processing method of arsenic and system, the method includes：S1, waste water is subjected to pH adjusting processing after homogeneous, filtration treatment；S2, will treated that waste water carries out the processing of ammonia still process stripping, pH adjustings processing, advanced oxidation processing, coagulating kinetics, filtration treatment, RO processing, depth adsorption treatment and MVR processing successively through step S1.The system comprises the pH regulating reservoirs being sequentially connected, ammonia still process stripping system, pH regulating reservoirs, advanced oxidation system, coagulating sedimentation system, filtration system, RO systems, depth adsorption system, MVR systems.Ammonia nitrogen value in the water outlet of high ammonia nitrogen fluorine-containing photovoltaic wastewater containing arsenic, COD value, fluorine ion reach discharging standards and stable after the present invention is handled, and As can reach the instrument detection limit of ICP MS or less (about 10ng/L) after processing.The present invention has larger environmental benefit and direct economic benefit.
Description
Technical field
The present invention relates to a kind for the treatment of process of environmental technology field, specifically a kind of high ammonia nitrogen fluorine-containing photovoltaic wastewater containing arsenic
Processing method and system, be mainly used in GaAs thin-film solar cells production waste water the processing of substances such as ammonia nitrogen, As and F and
Recycling.
Background technology
With the development of solar-photovoltaic technology, GaAs thin-film solar cells due to high with conversion ratio, plasticity is strong,
The features such as temperature tolerance is good, dim light performance is good, more and more extensive promotion and application are achieved in photovoltaic industry." GaAs at present
Thin film solar cell technologies " maximum conversion can reach 31.6%, and this value is once by National Renewable Energy
(NREL) is confirmed as conversion ratio the first in the world in laboratory.One of huge advantage of GaAs is exactly theoretical efficiency height, almost
It doubles than crystal silicon, this belongs to the born superior properties of GaAs, and when the limitation of crystal silicon highlights, GaAs is one
Good direction.But in GaAs thin-film solar cells production processes, it need to discharge largely containing substances such as ammonia nitrogen, As and HF
Waste water, which has the characteristics that pollutant concentration is high, environment toxic is big.
GaAs thin-film solar cells production line is introduced by foreign countries, after production line enters the country, is wanted according to the regulation of China
It asks, photovoltaic enterprise can discharge after need to 3 kinds of polluters in the waste water be carried out with the processing of comprehensive high standard.
Invention content
For the defects in the prior art, useless it is an object of the invention to be directed to the GaAs thin-film solar cells project constructions
A kind of water quality characteristics offer high ammonia nitrogen of the water containing high ammonia nitrogen, As and F contains the fluorine-containing photovoltaic wastewater processing method of arsenic and system；Using this
Processing method, can effectively remove ammonia nitrogen, As and F, water outlet ammonia nitrogen concentration be reduced to 10mg/L hereinafter, waste water A s concentration 10ng/L with
Under, F concentration is in 5 μ g/L hereinafter, RO, DTRO fresh water and MVR distilled water meet pure water Zero-discharge reuse water quality standard, MVR outputs
Crystallization is not dangerous waste, and fixed-end forces cost is greatly reduced.Meanwhile ammonium hydroxide can be realized by the ammonia nitrogen that steam air lift system is handled
It recycles or sells.
The purpose of the present invention is achieved through the following technical solutions：
In a first aspect, the present invention provides a kind of high ammonia nitrogen fluorine-containing photovoltaic wastewater processing method containing arsenic, the method includes such as
Lower step：
S1, waste water is subjected to pH adjusting processing after homogeneous, filtration treatment；
S2, will be through step S1 treated waste water carries out successively ammonia still process stripping processing, pH adjustings processing, advanced oxidation at
Reason, coagulating kinetics, filtration treatment, RO processing, depth adsorption treatment and MVR processing.
Preferably, in step S1, the waste water is that the high ammonia nitrogen of GaAs thin-film solar cells production discharge is fluorine-containing containing arsenic
Photovoltaic wastewater.
Preferably, in step S1, the step of pH adjusts processing includes adjusting the pH value of waste water to meeting ammonia using alkali
Distill the process requirements of stripper.
Preferably, in step S2, the ammonia still process stripping processing is using the interior energy-efficient stripping rectifying deamination technology of coupling.
Preferably, in step S2, it includes that will strip the ammonia nitrogen being precipitated to absorb by ammonia that the ammonia still process, which strips the step of handling,
Tower is converted into the ammonium hydroxide of mass fraction 16%~19%, is stored in ammonia still process storage tank.
Preferably, in step S2, it includes that the pH value of waste water is adjusted to 9 that the pH, which adjusts the step of handling,.
Preferably, in step S2, the step of advanced oxidation processing includes that NaClO is added to the COD in waste water, trivalent
As and remaining ammonia nitrogen carry out oxygenolysis.
Preferably, in step S2, the step of coagulating kinetics includes level-one coagulating kinetics and two-stage coagulation
Precipitation process；
The step of level-one coagulating kinetics includes：Add the Fe of 8.5 times of raw water arsenic molal quantitys3+, 5 times of raw water fluorine rub
The Ca of your number2+And dilute sulfuric acid makes pH be stable at 6.25, and most F and As in water removal is removed by coagulating sedimentation；
The step of two-stage coagulation precipitation process includes：Supernatant is obtained to level-one coagulating kinetics and adds 0.85 times
The Fe of raw water arsenic molal quantity3+, 0.5 times of raw water fluorine molal quantity Ca2+And dilute sulfuric acid makes pH be stable at 6.25, it is heavy by coagulation
Remaining F and As in water removal is removed in shallow lake.
Preferably, in step S2, the RO processing includes level-one RO processing and two level DTRO processing；After RO processing
Obtain fresh water and concentrated water, wherein fresh water enters pure water system reuse, and concentrated water passes through depth adsorption treatment；It is adsorbed through the depth
For the supernatant obtained after processing after MVR is handled, distilled water enters pure water system reuse.
Preferably, in step S2, the step of depth adsorption treatment includes after nano adsorber removal concentration is added
Remaining As, F.
Preferably, the reagent dosage being added in each step should be according to specific water quality and quantity, and carries out pilot plant test
It determines.
Preferably, the waste liquid is added by two steps, wherein a part of waste liquid directly proceeds by place by step S1
Reason, another part waste liquid carry out obtained mixed liquor by the way that through ammonia still process stripping, treated that waste liquid mixes with step S2 again
PH processing.
Second aspect, the present invention provide a kind of high ammonia nitrogen fluorine-containing photovoltaic wastewater processing system containing arsenic, the system comprises according to
Secondary connected pH regulating reservoirs, ammonia still process stripping system, pH regulating reservoirs, advanced oxidation system, coagulating sedimentation system, filtration system, RO
System, depth adsorption system, MVR systems；The pH regulating reservoirs, ammonia still process stripping system, advanced oxidation system, coagulating sedimentation system
System, depth adsorption system are respectively equipped with adding of agent system.
Preferably, the coagulating sedimentation system includes sedimentation basin, intermediate pool, coarse filtration tank and precise filtering tank；It is described
In coagulating sedimentation system, the waste water gravity after flocculation reaction flows into the colloid and complex compound in removal waste water in sedimentation basin, so
Afterwards enter intermediate pool regulating water quality water, then sequentially enter coarse filtration tank, precise filtering tank be filtered processing to get.It adopts
With precise filtering tank to sand filtration water outlet (i.e. coarse filtration tank is discharged) further filtering clarification.
Preferably, the steam air lift system includes ammonia distillation stripper, ammonia absorber, the ammonia still process storage tank being sequentially connected.
The present invention uses " ammonia still process air lift+advanced oxidation+coagulating sedimentation " technique, has the advantages that：
(1) advanced：This technique equal beyond example in high ammonia nitrogen is containing the fluorine-containing photovoltaic wastewater processing of arsenic, is domestic initiation；Its
Water outlet ammonia nitrogen value, COD value, fluorine ion reach discharging standards and stable, and As can reach the instrument of ICP-MS after processing
(about 10ng/L) below device detection limit.The present invention has larger environmental benefit and direct economic benefit；
(2) stability：According to pilot plant test and Industrial Engineering achievement, the technique anti impulsion load is strong；
(3) economy：This technological process is short, in strict accordance with national design specification construction, reduces floor space, capital construction input
And the operating cost of daily management, meanwhile, ammonium hydroxide recycling can directly make industrial water, greatly reduce the operating cost of equipment.
Description of the drawings
Upon reading the detailed description of non-limiting embodiments with reference to the following drawings, other feature of the invention,
Objects and advantages will become more apparent upon：
Fig. 1 is the process flow chart of the high ammonia nitrogen of the present invention fluorine-containing photovoltaic wastewater processing containing arsenic；
Fig. 2 is the embodiment of the present invention 1, using present treatment process effect flow chart.
Specific implementation mode
With reference to specific embodiment, the present invention is described in detail.Following embodiment will be helpful to the technology of this field
Personnel further understand the present invention, but the invention is not limited in any way.It should be pointed out that the ordinary skill of this field
For personnel, without departing from the inventive concept of the premise, several changes and improvements can also be made.These belong to the present invention
Protection domain.
Embodiment 1
In actual application, process as shown in Figure 1, 2 can be used to realize in the present invention, high ammonia nitrogen of the present invention
The fluorine-containing photovoltaic wastewater processing system containing arsenic includes the ammonia-containing water regulating reservoir being sequentially connected, filtration system, pH regulating reservoirs, steam gas
Put forward system, composite waste regulating reservoir, advanced oxidation pond, two-stage coagulative precipitation tank, filtration system, two-stage RO systems, advanced treating
System, MVR systems；The pH regulating reservoirs, steam air lift system, advanced oxidation pond, two-stage coagulation sedimentation basin, advanced treatment system
It is respectively equipped with adding of agent system.The two-stage coagulating sedimentation system is additionally provided with sedimentation basin, intermediate pool, coarse filtration tank, precision
Filtering tank；The steam air lift system includes ammonia distillation stripper, ammonia absorber, the ammonia still process storage tank being sequentially connected.
Concrete processing procedure is：High arsenic alkalinity, low arsenic alkaline waste water regulating reservoir is arranged in high ammonia nitrogen fluorine-containing photovoltaic wastewater containing arsenic
1, waste water, balanced water quality and quantity are collected, water outlet is promoted to filtration system 1# through pump, carries out clarifying treatment to water outlet, is discharged into pH
Water inlet pH value is adjusted to distillation stripper demand is met, distills stripper by the ammonia nitrogen vapour in waste water by ammonia by regulating reservoir 1#
It carries and is precipitated and ammonium hydroxide is converted by ammonia absorber, be stored in ammonia still process storage tank, be discharged into composite waste regulating reservoir.Composite waste tune
Pond is saved, each stock waste water in the workshops 3#, balanced water quality and quantity are collected, water outlet is promoted to pH regulating reservoir 2# through pump, and it is left to adjust pH to 9
The right side, water outlet remove in waste water remaining ammonia nitrogen and carry out oxidation to arsenic and become arsenate from NaClO oxidative systems are flow to,
From two-stage coagulative precipitation tank is flow to, the first order adds the Fe of 8.5 times of raw water arsenic molal quantitys for water outlet3+And 5 times of raw water fluorine molal quantitys
Ca2+, the second level adds the Fe of 0.85 times of raw water arsenic molal quantity3+And the Ca of 0.5 times of raw water fluorine molal quantity2+, remove in waste water
Arsenic and fluorine, water outlet stores waste water, water outlet is promoted to level-one RO systems through pump, to waste water after filtering from intermediate pool is flow to
It is concentrated, removes organic matter, the salinity etc. in waste water, fresh water is recycled as pure water zero-emission, and concentrated water carries out two level
DTRO systems carry out concentration again, reduce the evaporation capacity of subsequent evaporation system.Fresh water is recycled as pure water zero-emission, dense
Water enters advanced treatment system, by adding heavy metal absorbent, removes the arsenic in waste water, it is danger to make the salinity being evaporated not
It is useless.Water outlet enters MVR vapo(u)rization systems, and crystallization is evaporated to salinity, and crystal is handled as general solid waste outward transport, water outlet recycling profit
With.
Embodiment 2
The present embodiment provides a kind of high ammonia nitrogen fluorine-containing photovoltaic wastewater processing methods containing arsenic, and described method includes following steps：
A, high ammonia nitrogen fluorine-containing photovoltaic wastewater containing arsenic enters wastewater equalization pond, balanced water quality and quantity, and water outlet was promoted to through pump
The 1# filterings of filter system；
B, filtration system 1# water outlets enter pH regulating reservoirs, and alkali, which is added, by adding of agent system adjusts pH value of waste water to satisfaction
Ammonia distills the process requirements of stripper；
C, the water outlet of pH regulating reservoirs is lifted into ammonia distillation stripper through pump, distills stripper by the ammonia nitrogen in waste water by ammonia
Stripping is precipitated；
D, ammonia distillation stripper water outlet gravity flow enters pH regulating reservoirs, and NaOH, which is added, by adding of agent system makes pH reach 9
To meet advanced oxidation reaction condition；
E, pH regulating reservoirs water outlet gravity flow enters advanced oxidation pond, NaClO is added by adding of agent system, in waste water
COD, trivalent As and remaining ammonia nitrogen carry out oxygenolysis；
F, advanced oxidation pond, which is discharged, enters two-stage coagulative precipitation tank, in the first order, is added successively by adding of agent system
The Fe of 8.5 times of raw water arsenic molal quantitys3+, 5 times of raw water fluorine molal quantitys Ca2+And dilute sulfuric acid makes pH be stable at 6.25, passes through coagulation
Precipitation removes most F and As in water removal.Supernatant water outlet gravity flow enters second level coagulative precipitation tank in the first order.The second level
In, add the Fe of 0.85 times of raw water arsenic molal quantity successively by adding of agent system3+, 0.5 times of raw water fluorine molal quantity Ca2+With
And dilute sulfuric acid makes pH be stable at 6.25, and remaining F and As in water removal is removed by coagulating sedimentation.Two-stage coagulation sedimentation basin supernatant goes out
Water enters filtration system 2# through pump, and the iron colloid that removing may contain in supernatant prevents fouling membrane；
G, filtration system 2# water outlets sequentially enter level-one RO systems through pump pressurization and two level DTRO systems concentrate, and mitigate
The burden of MVR systems；
H, membranous system water outlet fresh water enters pure water system Zero-discharge reuse, and concentrated water enters advanced treatment system, passes through medicament
Remaining As, F after nano adsorber removal concentration is added in dosing system；
I, advanced treatment system goes out supernatant and is evaporated into MVR systems through pump, and distilled water enters pure water system zero-emission
Reuse, salt are not dangerous waste, outer processing of entrusting.
Wherein, the high ammonia nitrogen is that GaAs thin-film solar cells produces waste discharge containing the fluorine-containing photovoltaic wastewater of arsenic.
In step C, it is using the energy-efficient stripping essence of interior coupling that ammonia, which distills stripper and the ammonia nitrogen stripping in waste water is precipitated,
Evaporate deamination technology.Step C further includes that the ammonia nitrogen of stripping precipitation is converted into the ammonia of mass fraction 16%~19% by ammonia absorber
Water, the step of being stored in ammonia still process storage tank.
In step G, the coagulative precipitation tank water outlet is discharged into intermediate pool using gravity after depth-type filtration.
20MWGaAs thin-film solar cells project construction wastewater treatment examples
The example device of high ammonia nitrogen fluorine-containing photovoltaic wastewater treatment process containing arsenic is set according to attached technological process shown in Fig. 2
Meter processing, wherein ammonia still process air lift system are using the interior energy-efficient stripping rectifying deamination technology of coupling.
Wastewater flow rate：49m3/ h, wherein 1. the water of nitrogen-containing wastewater containing arsenic is 27.75m3/ h, ammonia nitrogen：15000mg/L, As：
622mg/L, 2. remaining arsenic-containing waste water 21.25m3/ h, As：38.56mg/L F：508.24mg/L.
Using processing system water-in and water-out ammonia nitrogen, F concentration Csg,in、Cg,outAnd As concentration Csg,in、Cg,outTwo indices are to high ammonia
Nitrogen fluorine-containing photovoltaic wastewater treatment process containing arsenic is investigated.
It investigates result：After steam air lift system, ammonia nitrogen concentration is dropped to waste water by original 15000mg/L
102mg/L, As, F concentration remain unchanged；For waste water after advanced oxidation is handled, ammonia nitrogen concentration drops to 10mg/L by 102mg/L,
As, F concentration remain unchanged；Waste water is after the processing of coagulating sedimentation system, and ammonia nitrogen concentration remains unchanged, and As is dropped to by 375mg/L<
5 μ g/L, F drop to 10 μ g/L by 220mg/L；Waste water is after the processing of advanced treatment system system, and ammonia nitrogen concentration remains unchanged, As
By<5 μ g/L are dropped to<10ng/L, F are dropped to by 10 μ g/L<5μg/L.
It can be obtained by investigation result：High ammonia nitrogen contains containing arsenic when with 20MWGaAs thin-film solar cells project construction waste water
Fluorine photovoltaic wastewater treatment process has the characteristics that the treatment effect of ammonia nitrogen, As and F：
1, high ammonia nitrogen has very high treatment effeciency containing the fluorine-containing photovoltaic wastewater treatment process of arsenic to ammonia nitrogen, As and F, high respectively
Up to 99.93%, 99.999997%, 99.997% or more；
2, high ammonia nitrogen is containing the fluorine-containing photovoltaic wastewater treatment process technically reliable of arsenic, easy to operate, stable, effluent quality symbol
Close pure water Zero-discharge reuse standard.
Specific embodiments of the present invention are described above.It is to be appreciated that the invention is not limited in above-mentioned
Particular implementation, those skilled in the art can make a variety of changes or change within the scope of the claims, this not shadow
Ring the substantive content of the present invention.In the absence of conflict, the feature in embodiments herein and embodiment can arbitrary phase
Mutually combination.
Claims (10)
1. a kind of high ammonia nitrogen fluorine-containing photovoltaic wastewater processing method containing arsenic, which is characterized in that described method includes following steps：
S1, waste water is subjected to pH adjusting processing after homogeneous, filtration treatment；
S2, will be through step S1 treated waste water carries out successively ammonia still process stripping processing, pH adjustings processing, advanced oxidation processing, mixed
Solidifying precipitation process, filtration treatment, RO processing, depth adsorption treatment and MVR processing.
2. high ammonia nitrogen according to claim 1 fluorine-containing photovoltaic wastewater processing method containing arsenic, which is characterized in that in step S1,
The waste water is high ammonia nitrogen fluorine-containing photovoltaic wastewater containing arsenic of GaAs thin-film solar cells production discharge.
3. high ammonia nitrogen according to claim 1 fluorine-containing photovoltaic wastewater processing method containing arsenic, which is characterized in that in step S1,
It includes adjusting the pH value of waste water using alkali to arrive the process requirements for meeting ammonia distillation stripper that the pH, which adjusts the step of processing,.
4. high ammonia nitrogen according to claim 1 fluorine-containing photovoltaic wastewater processing method containing arsenic, which is characterized in that in step S2,
The step of pH adjustings processing includes that the pH value of waste water is adjusted to 9.
5. high ammonia nitrogen according to claim 1 fluorine-containing photovoltaic wastewater processing method containing arsenic, which is characterized in that in step S2,
The step of advanced oxidation processing include be added NaClO in waste water COD, trivalent As and remaining ammonia nitrogen carry out oxidation point
Solution.
6. high ammonia nitrogen according to claim 1 fluorine-containing photovoltaic wastewater processing method containing arsenic, which is characterized in that in step S2,
The step of coagulating kinetics includes level-one coagulating kinetics and two-stage coagulation precipitation process；
The step of level-one coagulating kinetics includes：Add the Fe of 8.5 times of raw water arsenic molal quantitys3+, 5 times of raw water fluorine molal quantitys
Ca2+And dilute sulfuric acid makes pH be stable at 6.25, and most F and As in water removal is removed by coagulating sedimentation；
The step of two-stage coagulation precipitation process includes：Supernatant is obtained to level-one coagulating kinetics and adds 0.85 times of raw water
The Fe of arsenic molal quantity3+, 0.5 times of raw water fluorine molal quantity Ca2+And dilute sulfuric acid makes pH be stable at 6.25, is gone by coagulating sedimentation
Remaining F and As in water removal.
7. high ammonia nitrogen according to claim 1 fluorine-containing photovoltaic wastewater processing method containing arsenic, which is characterized in that in step S2,
The RO processing includes level-one RO processing and two level DTRO processing；Fresh water and concentrated water are obtained after RO processing, wherein fresh water
Into pure water system reuse, concentrated water passes through depth adsorption treatment；The supernatant obtained after the depth adsorption treatment passes through MVR
After processing, distilled water enters pure water system reuse.
8. high ammonia nitrogen according to claim 1 or claim 7 fluorine-containing photovoltaic wastewater processing method containing arsenic, which is characterized in that step S2
In, the step of depth adsorption treatment includes remaining As, the F being added after nano adsorber removal concentration.
9. a kind of high ammonia nitrogen fluorine-containing photovoltaic wastewater processing system containing arsenic, which is characterized in that the system comprises the pH being sequentially connected
Regulating reservoir, ammonia still process stripping system, pH regulating reservoirs, advanced oxidation system, coagulating sedimentation system, filtration system, RO systems, depth are inhaled
Attached system, MVR systems；The pH regulating reservoirs, ammonia still process stripping system, advanced oxidation system, coagulating sedimentation system, depth absorption system
System is respectively equipped with adding of agent system.
10. high ammonia nitrogen according to claim 9 fluorine-containing photovoltaic wastewater processing system containing arsenic, which is characterized in that the coagulation
Settling system includes sedimentation basin, intermediate pool, coarse filtration tank and precise filtering tank；It is anti-through flocculating in the coagulating sedimentation system
Waste water gravity after answering flows into the colloid and complex compound in removal waste water in sedimentation basin, subsequently into intermediate pool regulating water quality water
Amount, then sequentially enter coarse filtration tank, precise filtering tank be filtered processing to get.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109052785A (en) * | 2018-09-06 | 2018-12-21 | 四川恒泰环境技术有限责任公司 | A kind of Zero-discharge treating process of thin-film solar cells production waste water |
| CN109867415A (en) * | 2019-03-27 | 2019-06-11 | 四川恒泰环境技术有限责任公司 | A kind of energy-saving semiconductor new material GaAs production wastewater treatment process |
| CN113716775A (en) * | 2021-08-31 | 2021-11-30 | 四川恒泰环境技术有限责任公司 | Comprehensive treatment method for high-arsenic high-salt wastewater and arsenic-containing grinding wastewater of gallium arsenide chip |
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