CN104609596A - Photovoltaic acid cleaning wastewater recycling process - Google Patents
Photovoltaic acid cleaning wastewater recycling process Download PDFInfo
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- CN104609596A CN104609596A CN201410846449.XA CN201410846449A CN104609596A CN 104609596 A CN104609596 A CN 104609596A CN 201410846449 A CN201410846449 A CN 201410846449A CN 104609596 A CN104609596 A CN 104609596A
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J39/00—Cation exchange; Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
- B01J39/08—Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
- B01J39/16—Organic material
- B01J39/18—Macromolecular 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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/24—Treatment of water, waste water, or sewage by flotation
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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
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
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- 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
- C02F1/66—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
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
- C02F2001/425—Treatment of water, waste water, or sewage by ion-exchange using cation exchangers
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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
- C02F2301/00—General aspects of water treatment
- C02F2301/04—Flow arrangements
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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
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
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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
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Abstract
The invention relates to a wastewater treatment technology, and particularly relates to a photovoltaic acid cleaning wastewater recycling process. The photovoltaic acid cleaning wastewater recycling process sequentially comprises the following steps: regulating the pH value: collecting photovoltaic acid cleaning wastewater, and regulating the pH value to be 7-8; performing ultrafiltration: sending the wastewater of which the pH value is regulated into an ultrafiltration device, and draining ultrafiltration concentrated water to a sewage station for further treatment, wherein ultrafiltration produced water is divided into two parts, a first part is used in subsequent recycle, and a second part is used for backwashing the ultrafiltration device; performing first inner circulation: enabling the first part of the ultrafiltration produced water for subsequent recycle to enter a first inner circulating system, wherein the first inner circulating system comprises a high-pressure pump and a reverse osmosis desalination device, and effluent water passing through the high-pressure pump and the reverse osmosis desalination device is sent into an inlet of the high-pressure pump for multiple first inner circulating treatments, so that the integral recycling rate of a system is greater than or equal to 85%; recycling pure water: using final reverse osmosis effluent water, as industrial running water, in a production line. The photovoltaic acid cleaning wastewater recycling process system is high in desalination rate and high in integral recycling rate and can achieve wastewater recycle.
Description
Technical field
The present invention relates to waste water treatment process, particularly relate to the acid washing waste water recycling technique of a kind of photovoltaic.
Background technology
At present, under global energy faces severe situation, solar photovoltaic industry rises gradually.Sun power is a kind of environmental protection, green, and energy-conservation new forms of energy utilize it, can fully alleviate energy shortage trend.
Sun power is as a kind of clean energy, and itself does not exist pollution, but it can produce many pollution problems in process of production, and wherein, can produce the acid Cleaning Wastewater of lower concentration in photovoltaic cell production process, the inside contains a small amount of HNO3, HCL, HF, PH about 4.
For the waste water pollution problem of existing photovoltaic industry, technician proposes multiple solution, but still there is many problems to be solved:
1, most of photovoltaic enterprise wastewater is all do not have reuse, processes rear direct discharge up to standard;
2, do not regulate PH before existing reuse reverse osmosis unit water inlet, system ratio of desalinization is low;
3, existing reclaiming system recycled in its entirety rate is low.
CN101973662A(2011.02.16) a kind of photovoltaic solar cell sheet production wastewater treatment technique is disclosed, technique is collected respectively to acid waste water and alkaline waste water, by regulating pH, except fluorine and/or except COD, Aerobic biological process, the waste water reaching emission standard is arranged outward.The treatment process for photovoltaic solar cell sheet factory effluent water quality characteristics that this invention provides, effectively eliminate fluorion, water outlet fluorinion concentration is reduced to below 10mg/L, below waste water COD Cr300mg/L, but only qualified discharge after wastewater treatment.
CN202072558U(2011.12.14) disclose a kind of photovoltaic wastewater zero discharge system and relate to Treatment of Industrial Water device, by equipment such as PLC control system connection control two steps ro device, sequence batch (Fenton device, Multistage filtering device, ultra-filtration equipment and follow-up reverse osmosis units, Treatment for Reuse is carried out to photovoltaic wastewater, realize the recycle of water resources, but this apparatus system link is many, complex process, operation easier is high.
Based on above present situation, consider that various places industrial tap water is expensive simultaneously, and the policy that response national energy-saving reduces discharging, we need a set of system for photovoltaic wastewater Treatment for Reuse badly, while minimizing total amount of pollutants discharged, can pure water be reclaimed again, realize the Treatment for Reuse of photovoltaic wastewater.
Summary of the invention
The object of this invention is to provide that a kind of system ratio of desalinization is high, recycled in its entirety rate is high, the acid washing waste water recycling technique of the photovoltaic of waste water recycling can be realized.
Above-mentioned technical purpose of the present invention is achieved by the following technical programs:
The acid washing waste water recycling technique of a kind of photovoltaic, it comprises step successively:
(1) adjust ph: the acid Cleaning Wastewater of collection photovoltaics, regulates the acid Cleaning Wastewater pH value of photovoltaic to 7-8;
(2) ultrafiltration: the waste water after pH value being regulated squeezes into ultra-filtration equipment under pressure 0.08-0.12MPa, obtain ultrafiltration after uf processing and produce water, ultrafiltration concentrated water drainage processes further to sewage plant; It is two portions that moisture is produced in described ultrafiltration, and first part is as follow-up Treatment for Reuse, and second section is used for the backwash of ultra-filtration equipment;
Described ultra-filtration equipment often runs and carries out an automatic back-washing half an hour; Rinsing flux controls at 100-120L/m2hr; Backwash pressure≤0.2MPa; Backwash time 20-40 second;
Described ultra-filtration equipment is external pressing type hollow fibrous membrane, and the ratio of its film silk internal-and external diameter is 1:1.5-2.5, ultrafiltration module packing density 800 ~ 1200m
2/ m
3;
(3) first internal recycle: the first part ultrafiltration as follow-up Treatment for Reuse is produced water and entered the first internal circulation system, described first internal circulation system comprises and is connected to high-pressure pump after described ultra-filtration equipment and reverse osmosis desalination plant; Water outlet through high-pressure pump and reverse osmosis desalination is squeezed into again high pressure pump inlet and carry out repeatedly the first internal recycle process, make the entire system rate of recovery >=85%;
(4) pure water reuse: final reverse osmosis water outlet is back to production line as industrial tap water.
Ultrafiltration utilizes to have selects the film through ability to do separating medium, membranous wall gathers micropore, and stoste is under a certain pressure by the side of film, and solvent and small organic molecule are filtrate through membranous wall, and more macromolecular organism tunicle retains, thus reach separating substances and concentrated object.Membrane separating process is dynamic filtration process, and larger molecular organics, solid substance are intercepted by membranous wall, and flow out membrane module with concentrated solution, film is not easily blocked, can life-time service continuously.Filtration procedure can run under normal temperature, low pressure, without phase-state change, energy-efficient;
Ultrafiltration is that a kind of fluid fed tangentially moves and pressure-actuated filtration procedure, as a kind of new separation method, has many incomparable advantages, as energy consumption is low, easy and simple to handle, and take up an area few, pollution-free etc., Ultra filtration membrane technology develops rapidly.But due in membrane separating process, there is various factors flux, flux is reduced.End is got up, and the principal element that flux is reduced is concentration polarization and fouling membrane, and concentration polarization can aggravate the pollution of film.Concentration polarization and fouling membrane not only make flux reduce, and shorten the work-ing life of film, become the important factor that restriction membrane separation technique is applied.The influence factor of fouling membrane mainly contains; The composition, film kind, cleaning situation etc. of the velocity of flow of temperature, working pressure, separated liquid, the flow state of separated liquid, separated liquid pH value, working time, separated liquid.Therefore solve and alleviate the effective ways of concentration polarization and fouling membrane, be select these influence factors desired value but due to the restriction of membrane sepn system, the intensity of film own and membrane technology efficiency etc., these influence factors can not arbitrarily change.Wherein alter flow state is relatively simple, and selects suitable condition also obvious to the effect alleviating concentration polarization and fouling membrane, and cost is also relatively low.
Ultrafiltration of the present invention adopts external pressing type hollow fibrous membrane (material is existing known conventional as polyvinylidene difluoride (PVDF) PVDF, polysulfones PS, PES polyethersulfone etc., and be preferably PVDF, anti-fouling performance is good, and chemistry, physical strength are good).Consider the filtration efficiency ensureing ultra-filtration process of the present invention to greatest extent, solve and alleviate concentration polarization and fouling membrane, by specific film operating parameter, film silk select and assembly packing density synergy run, simultaneously in conjunction with the first follow-up internal recycle, fully can to remove in water the materials such as HF, HN03, HCL, ultrafiltration be produced water by high-pressure pump and enter reverse osmosis desalination system, improve the ratio of desalinization of reverse osmosis system, pH adjusts to 7-8, makes reverse osmosis system ratio of desalinization >=90%; By the first internal circulation system, ensure the entire system rate of recovery >=85%, finally make reverse osmosis unit produce water effect industrial tap water and be applied to production line.
As preferably, acid for described photovoltaic Cleaning Wastewater is collected into former pond, then enters raw water pump, accurate filter and ultra-filtration equipment successively, regulate in accurate filter ingress the acid Cleaning Wastewater pH value of photovoltaic to 7-8.
As preferably, described ultra-filtration equipment produces the mouth of a river and is connected with ultrafiltration water tank, and described ultrafiltration water tank is connected to the recoil pump for cleaning described ultra-filtration equipment and the high-pressure pump for the first internal recycle.
As preferably, first part's ultrafiltration as follow-up Treatment for Reuse produces water before entering the first internal circulation system, first mix with pressure air-dissolving water, then gas-floating chamber is entered, gas-floating chamber operating pressure is 1-3N, the colloid formed in water and suspended substance are separated in gas-floating chamber, and scum silica frost enters described first internal circulation system by waterpower mode or mechanical system after water surface is removed.
Adopt the method can promote the efficiency of the first internal recycle process further, improve the ratio of desalinization of reverse osmosis system, improve the entire system rate of recovery.
As preferably, be re-used as industrial tap water after ionic adsorption is carried out in described reverse osmosis desalination plant water outlet and be back to production line, described ionic adsorption specifically by reverse osmosis desalination plant water outlet with the speed of 15-20cm/min by comprising by (0.1-2): the gel strong acid type Al-type ion exchange resin of (5-7) mixed in molar ratio and macropore weak-type Al-type ion exchange resin composition modified double resin ion-exchanger pillar.
Adopt and carry out ionic adsorption after reverse osmosis, the fluoride ion removing in waste water can be improved, reduce the fluorine content in pure water.
More preferably, the preparation method of described modified double resin ion-exchanger comprises the following steps successively:
A. the preparation of gel strong acid type Al-type ion exchange resin: the gel strong acid type H-type phenylethylene resin series of filling 1 parts by volume under normal temperature and pressure in fixed-bed reactor, the mass percent concentration injecting 10-12 times of parts by volume is alum liquor or the pyrosulfuric acid aluminum solutions of 1-5%, soak 1-3h, then washed with de-ionized water is used, for subsequent use;
B. the preparation of macropore weak-type Al-type ion exchange resin: the macropore weak-type H-type acrylic resin of filling 1 parts by volume under normal temperature and pressure in fixed-bed reactor, the mass percent concentration injecting 10-12 times of parts by volume is alum liquor or the pyrosulfuric acid aluminum solutions of 0.5-1.5%, soak 0.5-2.5h, then washed with de-ionized water is used, for subsequent use;
C. by (0.1-2): gel strong acid type Al-type ion exchange resin prepared by (5-7) mixed in molar ratio above-mentioned steps and macropore weak-type Al-type ion exchange resin.
Because aluminum ion has stronger avidity to fluorion, series of stable compound can be formed with fluorion, thus the fluorion in water can be removed:
Al
3++F
- = AlF
2+
AlF
2++F
- = AlF
+
…
AlF
5 2-+F
- = AlF
6 +
For a long time except some color of resin in exchange column after fluorine deepen, illustrate that resin is contaminated, need regeneration.Except the resin after fluorine can regenerate with alum liquor, regenerative response is as follows:
(R-SO
3)
2AlF+Al
3++（R-SO
3）
-=(R-SO
3)
3Al+AlF
2+
Regeneration frequency is controlled according to waste water fluorine content, on the downside of exchange column, ingress's importing alum liquor or pyrosulfuric acid aluminum solutions regenerate, after regenerative elution liquid flows out from exit on the upside of exchange column, then this regenerative elution liquid is imported in pending photovoltaic wastewater, due to AlF
2+still can react further with fluorion, therefore can improve technique fluoride removing rate, reduce the use except fluorine medicament.Modified double resin ion-exchanger of the present invention can repeatedly regenerate, and work-ing life is 3-5.
Further preferably, described gel strong acid type Al-type ion exchange resin bead footpath is 0.2-0.3mm, and water content is 48-52%, and wet true density is 1.28-1.32g/ml, rate of small round spheres >=98%.
Further preferably, described macropore weak-type Al-type ion exchange resin bead footpath is 0.6-1.1mm, and water content is 50-56%, and wet true density is 1.45-1.84g/ml, rate of small round spheres >=98%.
Again further preferably, add the regeneration that complexing agent promotes described modified double resin ion-exchanger after ionic adsorption completes, the mass ratio of described complexing agent and described modified double resin ion-exchanger is 1:70-90;
Described complexing agent is the citric acid and the mixture of edetate that form according to mass ratio 1-3:4-7.
As preferably, described ultra-filtration equipment, high-pressure pump and reverse osmosis unit form the second internal circulation system, ultrafiltration are produced water and squeeze into high-pressure pump and reverse osmosis unit carries out repeatedly the second internal recycle process, make the entire system rate of recovery >=85%.
In sum, the present invention has following beneficial effect:
1, reverse osmosis system ratio of desalinization >=90%;
2, the entire system rate of recovery >=85%.
Accompanying drawing explanation
Fig. 1 is the acid washing waste water recycling process flow sheet of photovoltaic of the present invention.
Embodiment
Below in conjunction with accompanying drawing, the present invention is described in further detail.
Embodiment one
As shown in Figure 1, the acid washing waste water recycling technique of photovoltaic comprises step:
(1) adjust ph: acid for photovoltaic Cleaning Wastewater is collected into former pond, then enters raw water pump, accurate filter successively, regulates the acid Cleaning Wastewater pH value to 7 of photovoltaic in accurate filter ingress;
(2) ultrafiltration: the waste water after pH value being regulated squeezes into ultra-filtration equipment under pressure 0.09MPa, obtain ultrafiltration after uf processing and produce water, ultrafiltration concentrated water drainage processes further to sewage plant; It is two portions that moisture is produced in ultrafiltration, and first part is as follow-up Treatment for Reuse, and second section is used for the backwash of ultra-filtration equipment;
Ultra-filtration equipment often runs and carries out an automatic back-washing half an hour; Rinsing flux controls at 110L/m2hr; Backwash pressure≤0.2MPa; 30 seconds backwash time;
Ultra-filtration equipment is external pressing type hollow fibrous membrane, and the ratio of film silk internal-and external diameter is 1:2, ultrafiltration module packing density 900m
2/ m
3;
(3) first internal recycle: the first part's ultrafiltration as follow-up Treatment for Reuse is produced water and entered the first internal circulation system, and the first internal circulation system comprises the high-pressure pump and reverse osmosis desalination plant that are connected successively with ultra-filtration equipment; Water outlet through high-pressure pump and reverse osmosis desalination is squeezed into again high pressure pump inlet and carry out repeatedly the first internal recycle process, make the entire system rate of recovery >=85%;
(4) pure water reuse: final reverse osmosis water outlet is back to production line as industrial tap water.
Economic benefit: most area industrial tap water price about 3 yuan/ton (Special section is as about 20 yuan/ton, Ningbo), this cover acid waste water reclaiming system can help the water of in reuse acid waste water 85% as production tap water, for user increases economic benefit.And the waste water of remaining 15% enters sewage plant, floor space and the chemical feeding quantity of whole sewage plant greatly reduce, and decrease the construction investment cost of user.
Table 1 Economic and Efficiency Analysis
Embodiment two
With embodiment one, under pressure 0.08MPa, squeeze into ultra-filtration equipment unlike the waste water after pH value specifically regulates by ultrafiltration, obtain ultrafiltration after uf processing and produce water, ultrafiltration concentrated water drainage processes further to sewage plant; It is two portions that moisture is produced in ultrafiltration, and first part is as follow-up Treatment for Reuse, and second section is used for the backwash of ultra-filtration equipment; Ultra-filtration equipment often runs and carries out an automatic back-washing half an hour; Rinsing flux controls at 100L/m2hr; Backwash pressure≤0.2MPa; 20 seconds backwash time; Ultra-filtration equipment is the ratio of external pressing type hollow fibrous membrane film silk internal-and external diameter is 1:1.5, ultrafiltration module packing density 800m
2/ m
3;
The acid Cleaning Wastewater pH value to 8 of photovoltaic is regulated in accurate filter ingress; Ultra-filtration equipment produces the mouth of a river and is connected with ultrafiltration water tank, and ultrafiltration water tank is connected to the recoil pump for cleaning ultra-filtration equipment and the high-pressure pump for the first internal recycle.
First part's ultrafiltration as follow-up Treatment for Reuse produces water before entering the first internal circulation system, first mix with pressure air-dissolving water, then gas-floating chamber is entered, gas-floating chamber operating pressure is 1N, the colloid formed in water and suspended substance are separated in gas-floating chamber, and scum silica frost enters the first internal circulation system by waterpower mode or mechanical system after water surface is removed.
Reverse osmosis desalination plant water outlet is re-used as industrial tap water after carrying out ionic adsorption and is back to production line, ionic adsorption specifically by reverse osmosis desalination plant water outlet with the speed of 15cm/min by comprising the modified double resin ion-exchanger pillar by the gel strong acid type Al-type ion exchange resin of 0.1:7 mixed in molar ratio and macropore weak-type Al-type ion exchange resin composition.
After ionic adsorption completes, add the regeneration that complexing agent promotes modified double resin ion-exchanger, the mass ratio of complexing agent and modified double resin ion-exchanger is 1:70; Complexing agent is the citric acid and the mixture of edetate that form according to mass ratio 1:7.
Ultra-filtration equipment, high-pressure pump and reverse osmosis unit form the second internal circulation system, ultrafiltration are produced water and squeeze into high-pressure pump and reverse osmosis unit carries out repeatedly the second internal recycle process, make the entire system rate of recovery 95%.
The preparation method of two resin ion exchanger comprises the following steps successively:
A. the preparation of gel strong acid type Al-type ion exchange resin: the gel strong acid type H-type phenylethylene resin series of filling 1 parts by volume under normal temperature and pressure in fixed-bed reactor, the mass percent concentration injecting 10 times of parts by volume is alum liquor or the pyrosulfuric acid aluminum solutions of 1%, soak 1-3h, then washed with de-ionized water is used, for subsequent use;
B. the preparation of macropore weak-type Al-type ion exchange resin: the macropore weak-type H-type acrylic resin of filling 1 parts by volume under normal temperature and pressure in fixed-bed reactor, the mass percent concentration injecting 10 times of parts by volume is alum liquor or the pyrosulfuric acid aluminum solutions of 0.5%, soak 0.5h, then washed with de-ionized water is used, for subsequent use;
C. the gel strong acid type Al-type ion exchange resin prepared of above-mentioned steps and macropore weak-type Al-type ion exchange resin is mixed in molar ratio.
Gel strong acid type Al-type ion exchange resin bead footpath is 0.2mm, and water content is 48%, and wet true density is 1.28g/ml, rate of small round spheres >=98%.
Macropore weak-type Al-type ion exchange resin bead footpath is 0. mm, and water content is 50%, and wet true density is 1.45g/ml, rate of small round spheres >=98%.
Comparative example two
With embodiment two, be adjusted to 6.5 unlike step (1) pH value, the first part's ultrafiltration product water as follow-up Treatment for Reuse does not enter high-pressure pump and carries out repeatedly the first internal recycle process, but directly enters reverse osmosis unit process.Experimental result is in table 2.As can be seen from Table 2, the photovoltaic wastewater within 2000ml reaches 4.58mg/L, much larger than the 0.02mg/L of embodiment by the filtrate fluorine content after exchange column.
Table 2 is tested except fluorine situation
Embodiment three
With embodiment two, squeeze into ultra-filtration equipment unlike the waste water after pH value being regulated under pressure 0.12MPa, obtain ultrafiltration after uf processing and produce water, ultrafiltration concentrated water drainage processes further to sewage plant; It is two portions that moisture is produced in ultrafiltration, and first part is as follow-up Treatment for Reuse, and second section is used for the backwash of ultra-filtration equipment; Ultra-filtration equipment often runs and carries out an automatic back-washing half an hour; Rinsing flux controls at 120L/m2hr; Backwash pressure≤0.2MPa; 40 seconds backwash time; Ultra-filtration equipment is the ratio of external pressing type hollow fibrous membrane film silk internal-and external diameter is 1:2.5, ultrafiltration module packing density 1200m
2/ m
3;
The acid Cleaning Wastewater pH value to 7.8 of photovoltaic is regulated in accurate filter ingress; First part's ultrafiltration as follow-up Treatment for Reuse produces water before entering the first internal circulation system, and first mix with pressure air-dissolving water, then enter gas-floating chamber, gas-floating chamber operating pressure is 1N.
Reverse osmosis desalination plant water outlet is re-used as industrial tap water after carrying out ionic adsorption and is back to production line, ionic adsorption specifically by reverse osmosis desalination plant water outlet with the speed of 20cm/min by comprising the modified double resin ion-exchanger pillar by the gel strong acid type Al-type ion exchange resin of 2:5 mixed in molar ratio and macropore weak-type Al-type ion exchange resin composition.
After ionic adsorption completes, add the regeneration that complexing agent promotes modified double resin ion-exchanger, the mass ratio of complexing agent and modified double resin ion-exchanger is 1:90; Complexing agent is the citric acid and the mixture of edetate that form according to mass ratio 3:4.
The preparation method of two resin ion exchanger comprises the following steps successively:
A. the preparation of gel strong acid type Al-type ion exchange resin: the gel strong acid type H-type phenylethylene resin series of filling 1 parts by volume under normal temperature and pressure in fixed-bed reactor, the mass percent concentration injecting 12 times of parts by volume is alum liquor or the pyrosulfuric acid aluminum solutions of 5%, soak 3h, then washed with de-ionized water is used, for subsequent use;
B. the preparation of macropore weak-type Al-type ion exchange resin: the macropore weak-type H-type acrylic resin of filling 1 parts by volume under normal temperature and pressure in fixed-bed reactor, the mass percent concentration injecting 12 times of parts by volume is alum liquor or the pyrosulfuric acid aluminum solutions of 1.5%, soak 2.5h, then washed with de-ionized water is used, for subsequent use;
C. the gel strong acid type Al-type ion exchange resin prepared by 1:6 mixed in molar ratio above-mentioned steps and macropore weak-type Al-type ion exchange resin.
Gel strong acid type Al-type ion exchange resin bead footpath is 0.3mm, and water content is 52%, and wet true density is 1.32g/ml, rate of small round spheres >=98%.
Macropore weak-type Al-type ion exchange resin bead footpath is 1.1mm, and water content is 56%, and wet true density is 1.84g/ml, rate of small round spheres >=98%.
Embodiment four
With embodiment three, produce water before entering the first internal circulation system unlike the first part's ultrafiltration as follow-up Treatment for Reuse, first mix with pressure air-dissolving water, then enter gas-floating chamber, gas-floating chamber operating pressure is 3N.
Reverse osmosis desalination plant water outlet is re-used as industrial tap water after carrying out ionic adsorption and is back to production line, ionic adsorption specifically by reverse osmosis desalination plant water outlet with the speed of 18cm/min by comprising the modified double resin ion-exchanger pillar by the gel strong acid type Al-type ion exchange resin of 2:5 mixed in molar ratio and macropore weak-type Al-type ion exchange resin composition.
After ionic adsorption completes, add the regeneration that complexing agent promotes modified double resin ion-exchanger, the mass ratio of complexing agent and modified double resin ion-exchanger is 1:70-90; Complexing agent is the citric acid and the mixture of edetate that form according to mass ratio 1-3:4-7.
The preparation method of two resin ion exchanger comprises the following steps successively:
A. the preparation of gel strong acid type Al-type ion exchange resin: the gel strong acid type H-type phenylethylene resin series of filling 1 parts by volume under normal temperature and pressure in fixed-bed reactor, the mass percent concentration injecting 11 times of parts by volume is alum liquor or the pyrosulfuric acid aluminum solutions of 4%, soak 2h, then washed with de-ionized water is used, for subsequent use;
B. the preparation of macropore weak-type Al-type ion exchange resin: the macropore weak-type H-type acrylic resin of filling 1 parts by volume under normal temperature and pressure in fixed-bed reactor, the mass percent concentration injecting 11 times of parts by volume is alum liquor or the pyrosulfuric acid aluminum solutions of 0.9%, soak 1.5h, then washed with de-ionized water is used, for subsequent use;
C. the gel strong acid type Al-type ion exchange resin prepared of above-mentioned steps and macropore weak-type Al-type ion exchange resin is mixed in molar ratio.
Gel strong acid type Al-type ion exchange resin bead footpath is 0.25mm, and water content is 50%, and wet true density is 1.29g/ml, rate of small round spheres >=98%.
Macropore weak-type Al-type ion exchange resin bead footpath is 0.9mm, and water content is 52%, and wet true density is 1.64g/ml, rate of small round spheres >=98%.
This specific embodiment is only explanation of the invention; it is not limitation of the present invention; those skilled in the art can make to the present embodiment the amendment not having creative contribution as required after reading this specification sheets, as long as but be all subject to the protection of patent law in right of the present invention.
Claims (10)
1. the acid washing waste water recycling technique of photovoltaic, is characterized in that comprising step successively:
(1) adjust ph: the acid Cleaning Wastewater of collection photovoltaics, regulates the acid Cleaning Wastewater pH value of photovoltaic to 7-8;
(2) ultrafiltration: the waste water after pH value being regulated squeezes into ultra-filtration equipment under pressure 0.08-0.12MPa, obtain ultrafiltration after uf processing and produce water, ultrafiltration concentrated water drainage processes further to sewage plant; It is two portions that moisture is produced in described ultrafiltration, and first part is as follow-up Treatment for Reuse, and second section is used for the backwash of ultra-filtration equipment;
Described ultra-filtration equipment often runs and carries out an automatic back-washing half an hour; Rinsing flux controls at 100-120L/m2hr; Backwash pressure≤0.2MPa; Backwash time 20-40 second;
Described ultra-filtration equipment is external pressing type hollow fibrous membrane, and the ratio of its film silk internal-and external diameter is 1:1.5-2.5, ultrafiltration module packing density 800 ~ 1200m
2/ m
3;
(3) first internal recycle: the first part ultrafiltration as follow-up Treatment for Reuse is produced water and entered the first internal circulation system, described first internal circulation system comprises and is connected to high-pressure pump after described ultra-filtration equipment and reverse osmosis desalination plant; Water outlet through high-pressure pump and reverse osmosis desalination is squeezed into again high pressure pump inlet and carry out repeatedly the first internal recycle process, make the entire system rate of recovery >=85%;
(4) pure water reuse: final reverse osmosis water outlet is back to production line as industrial tap water.
2. the acid washing waste water recycling technique of a kind of photovoltaic according to claim 1, it is characterized in that: acid for described photovoltaic Cleaning Wastewater is collected into former pond, then enter raw water pump, accurate filter and ultra-filtration equipment successively, regulate in accurate filter ingress the acid Cleaning Wastewater pH value of photovoltaic to 7-8.
3. the acid washing waste water recycling technique of a kind of photovoltaic according to claim 2, it is characterized in that: described ultra-filtration equipment produces the mouth of a river and is connected with ultrafiltration water tank, and described ultrafiltration water tank is connected to the recoil pump for cleaning described ultra-filtration equipment and the high-pressure pump for the first internal recycle.
4. the acid washing waste water recycling technique of a kind of photovoltaic according to claim 3, it is characterized in that: the first part's ultrafiltration as follow-up Treatment for Reuse produces water before entering the first internal circulation system, first mix with pressure air-dissolving water, then gas-floating chamber is entered, gas-floating chamber operating pressure is 1-3N, the colloid formed in water and suspended substance are separated in gas-floating chamber, and scum silica frost enters described first internal circulation system by waterpower mode or mechanical system after water surface is removed.
5. the acid washing waste water recycling technique of a kind of photovoltaic according to claim 4, it is characterized in that: be re-used as industrial tap water after ionic adsorption is carried out in described reverse osmosis desalination plant water outlet and be back to production line, described ionic adsorption specifically by reverse osmosis desalination plant water outlet with the speed of 15-20cm/min by comprising by (0.1-2): the gel strong acid type Al-type ion exchange resin of (5-7) mixed in molar ratio and macropore weak-type Al-type ion exchange resin composition modified double resin ion-exchanger pillar.
6. the acid washing waste water recycling technique of a kind of photovoltaic according to claim 5, is characterized in that: the preparation method of described modified double resin ion-exchanger comprises the following steps successively:
A. the preparation of gel strong acid type Al-type ion exchange resin: the gel strong acid type H-type phenylethylene resin series of filling 1 parts by volume under normal temperature and pressure in fixed-bed reactor, the mass percent concentration injecting 10-12 times of parts by volume is alum liquor or the pyrosulfuric acid aluminum solutions of 1-5%, soak 1-3h, then washed with de-ionized water is used, for subsequent use;
B. the preparation of macropore weak-type Al-type ion exchange resin: the macropore weak-type H-type acrylic resin of filling 1 parts by volume under normal temperature and pressure in fixed-bed reactor, the mass percent concentration injecting 10-12 times of parts by volume is alum liquor or the pyrosulfuric acid aluminum solutions of 0.5-1.5%, soak 0.5-2.5h, then washed with de-ionized water is used, for subsequent use;
C. by (0.1-2): gel strong acid type Al-type ion exchange resin prepared by (5-7) mixed in molar ratio above-mentioned steps and macropore weak-type Al-type ion exchange resin.
7. the acid washing waste water recycling technique of a kind of photovoltaic according to claim 6, it is characterized in that: described gel strong acid type Al-type ion exchange resin bead footpath is 0.2-0.3mm, water content is 48-52%, and wet true density is 1.28-1.32g/ml, rate of small round spheres >=98%.
8. the acid washing waste water recycling technique of a kind of photovoltaic according to claim 7, it is characterized in that: described macropore weak-type Al-type ion exchange resin bead footpath is 0.6-1.1mm, water content is 50-56%, and wet true density is 1.45-1.84g/ml, rate of small round spheres >=98%.
9. the acid washing waste water recycling technique of a kind of photovoltaic according to claim 8, it is characterized in that: after ionic adsorption completes, add the regeneration that complexing agent promotes described modified double resin ion-exchanger, the mass ratio of described complexing agent and described modified double resin ion-exchanger is 1:70-90;
Described complexing agent is the citric acid and the mixture of edetate that form according to mass ratio 1-3:4-7.
10. the acid washing waste water recycling technique of a kind of photovoltaic according to any one of claim 2-9, it is characterized in that: described ultra-filtration equipment, high-pressure pump and reverse osmosis unit form the second internal circulation system, ultrafiltration is produced water and squeeze into high-pressure pump and reverse osmosis unit carries out repeatedly the second internal recycle process.
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| CN110240319A (en) * | 2019-06-20 | 2019-09-17 | 一汽-大众汽车有限公司 | Waste water pretreatment system and method in a kind of automobile manufacturing process |
| CN112830621A (en) * | 2019-11-25 | 2021-05-25 | 福建杰达环保科技有限公司 | Beneficiation wastewater recycling system and method based on membrane chemical reactor |
| CN115557644A (en) * | 2022-10-19 | 2023-01-03 | 江苏道同环境科技有限公司 | Recycling treatment system and method for HF cleaning wastewater |
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| CN103172199A (en) * | 2013-03-21 | 2013-06-26 | 深圳市超纯环保科技有限公司 | Method for treating hydrofluoric acid wastewater |
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| US6338803B1 (en) * | 1999-08-30 | 2002-01-15 | Koch Microelectronic Service Co., Inc. | Process for treating waste water containing hydrofluoric acid and mixed acid etchant waste |
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| CN110240319A (en) * | 2019-06-20 | 2019-09-17 | 一汽-大众汽车有限公司 | Waste water pretreatment system and method in a kind of automobile manufacturing process |
| CN112830621A (en) * | 2019-11-25 | 2021-05-25 | 福建杰达环保科技有限公司 | Beneficiation wastewater recycling system and method based on membrane chemical reactor |
| CN115557644A (en) * | 2022-10-19 | 2023-01-03 | 江苏道同环境科技有限公司 | Recycling treatment system and method for HF cleaning wastewater |
| CN115557644B (en) * | 2022-10-19 | 2024-01-30 | 江苏道同环境科技有限公司 | Recycling treatment system and method for HF (high frequency) cleaning wastewater |
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| CN104609596B (en) | 2016-08-31 |
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Denomination of invention: A recycling process of photovoltaic acid cleaning wastewater Effective date of registration: 20211216 Granted publication date: 20160831 Pledgee: Nanxun Zhejiang rural commercial bank Limited by Share Ltd. and Fu sub branch Pledgor: ZHEJIANG DONGYANG ENVIRONMENTAL ENGINEERING Co.,Ltd. Registration number: Y2021330002548 |
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