CN104609596B - A kind of photovoltaic acidity washing waste water recycling technique - Google Patents
A kind of photovoltaic acidity washing waste water recycling technique Download PDFInfo
- Publication number
- CN104609596B CN104609596B CN201410846449.XA CN201410846449A CN104609596B CN 104609596 B CN104609596 B CN 104609596B CN 201410846449 A CN201410846449 A CN 201410846449A CN 104609596 B CN104609596 B CN 104609596B
- Authority
- CN
- China
- Prior art keywords
- water
- ultrafiltration
- type
- waste water
- photovoltaic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
Abstract
The present invention relates to waste water treatment process, particularly relate to a kind of photovoltaic acidity washing waste water recycling technique.It includes step successively: regulate pH value: collection photovoltaics acidity cleans waste water, and regulation pH value is to 78；Ultrafiltration: the waste water after being regulated by pH value squeezes into ultrafiltration apparatus, and ultrafiltration concentrated water drainage processes further to sewage plant；It is two parts that moisture is produced in ultrafiltration, and Part I is as follow-up Treatment for Reuse, and Part II is for the backwash of ultrafiltration apparatus；Circulation in first: the Part I ultrafiltration product water as follow-up Treatment for Reuse enters the first internal circulation system, and the first internal circulation system includes high-pressure pump and reverse osmosis desalination plant；Carry out repeatedly circular treatment in first by again squeezing into high pressure pump inlet through the water outlet of high-pressure pump and reverse osmosis desalination, make system recycled in its entirety rate >=85%；Pure water reuse: final reverse osmosis water outlet is back to production line as industrial tap water.Present invention process system salt rejection rate is high, recycled in its entirety rate is high, can realize waste water recycling.
Description
Technical field
The present invention relates to waste water treatment process, particularly relate to a kind of photovoltaic acidity washing waste water recycling technique.
Background technology
At present, under global energy faces the situation of sternness, solar photovoltaic industry gradually rises.Solar energy is a kind of ring
Protect, green, energy-conservation new forms of energy, it is utilized, can fully alleviate energy shortage trend.
As a kind of clean energy resource, itself there is not pollution, but it can produce many dirty in process of production in solar energy
Dye problem, wherein, photovoltaic cell production process can produce low concentration acidity clean waste water, the inside containing a small amount of HNO3, HCL,
HF, PH about 4.
For the waste water pollution problem of existing photovoltaic industry, technical staff proposes multiple solution, but still deposits
In the problem that many is to be solved:
1, major part photovoltaic enterprise wastewater is all not have reuse, processes rear directly discharge up to standard；
2, not regulating PH before the water inlet of existing reuse reverse osmosis unit, system salt rejection rate 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, work are disclosed
Acid waste water and alkaline waste water are collected by skill respectively, by regulation pH, fluorine removal and/or except COD, Aerobic biological process, reach row
Put and arrange outside the waste water of standard.The process technique of the waste water quality feature that produces for photovoltaic solar cell sheet that this invention provides,
Effectively eliminating fluorion, water outlet fluorinion concentration is reduced to below 10mg/L, below waste water COD Cr300mg/L, but at waste water
Only qualified discharge after reason.
CN202072558U(2011.12.14) disclose a kind of photovoltaic wastewater zero discharge system and relate to Treatment of Industrial Water dress
Put, connected by PLC control system and control two steps ro device, batch-type Fenton device, Multistage filtering device, ultrafiltration dress
Put and the equipment such as follow-up reverse osmosis unit, photovoltaic wastewater is carried out Treatment for Reuse, it is achieved recycling of water resource, but this dress
Putting system link many, complex process, operation easier is high.
Based on above present situation, consider that various places industrial tap water is expensive simultaneously, and the political affairs that response national energy-saving reduces discharging
Plan, we need a set of system for photovoltaic wastewater Treatment for Reuse badly, can reclaim again pure water while reducing total amount of pollutants discharged, real
The Treatment for Reuse of existing photovoltaic wastewater.
Summary of the invention
It is an object of the invention to provide a kind of system salt rejection rate height, recycled in its entirety rate is high, can realize the photovoltaic of waste water recycling
Acid washing waste water recycling technique.
The above-mentioned technical purpose of the present invention has the technical scheme that
A kind of photovoltaic acidity washing waste water recycling technique, it includes step successively:
(1) regulation pH value: collection photovoltaics acidity cleans waste water, regulation photovoltaic acidity cleaning pH value of waste water to 7-8；
(2) ultrafiltration: the waste water after being regulated by pH value squeezes into ultrafiltration apparatus, hyperfiltration treatment under pressure 0.08-0.12MPa
Water is produced in rear acquisition ultrafiltration, and ultrafiltration concentrated water drainage processes further to sewage plant；It is two parts that moisture is produced in described ultrafiltration, and Part I is made
For follow-up Treatment for Reuse, Part II is for the backwash of ultrafiltration apparatus；
Described ultrafiltration apparatus often runs and carries out an automatic back-washing half an hour；Rinse flux to control at 100-120L/m
hr；Backwash pressure≤0.2MPa；20-40 second backwash time；
Described ultrafiltration apparatus is external pressing type hollow fibrous membrane, and the ratio of its film silk internal-and external diameter is 1:1.5-2.5, and ultrafiltration module fills
Filling density 800 ~ 1200m2/m3；
Circulation in (3) first: the Part I ultrafiltration product water as follow-up Treatment for Reuse enters the first internal circulation system,
Described first internal circulation system includes being connected to the high-pressure pump after described ultrafiltration apparatus and reverse osmosis desalination plant；Will be through too high
The water outlet of press pump and reverse osmosis desalination is again squeezed into high pressure pump inlet and is carried out repeatedly circular treatment in first, makes system recycled in its entirety
Rate >=85%；
(4) pure water reuse: final reverse osmosis water outlet is back to production line as industrial tap water.
Ultrafiltration utilizes to have and selects to do separating medium through the thin film of ability, and membranous wall gathers micropore, and stock solution is at certain pressure
Under be filter liquor by the side of film, solvent and small organic molecule through membranous wall, and the Organic substance of relatively macromole is rejected by,
Thus reach the purpose that material separates and concentrates.Membrane separating process is dynamic filtration process, larger molecular organics, solid content tunicle
Wall intercepts, and flows out membrane module with concentrated solution, and film is difficult to blocked, can life-time service continuously.Filter process can be under room temperature, low pressure
Run, without phase-state change, energy-efficient；
Ultrafiltration is that a kind of fluid fed tangentially moves and pressure-actuated filter process, as a kind of new separation method, has
Many incomparable advantages, as energy consumption is low, easy and simple to handle, take up an area few, pollution-free etc., Ultra filtration membrane technology is sent out the most rapidly
Exhibition is got up.But owing to, in membrane separating process, having many factors to affect flux, make flux reduce.End is got up, and makes flux reduce
Principal element be concentration polarization and fouling membrane, and concentration polarization can aggravate the pollution of film.Concentration polarization and fouling membrane are not only
Make flux reduce, and shorten the service life of film, become the key factor of restriction membrane separation technique popularization and application.Fouling membrane
Influence factor mainly has；Temperature, operation pressure, by separate liquid flowing velocity, by separate liquid flow regime, by separate liquid pH
It is worth, runs the time, separated the composition of liquid, film kind, cleaning situation etc..Therefore solve and alleviate concentration polarization and fouling membrane
Effective ways, are to select the desired value of these influence factors but owing to membrance separation system, the intensity of film own and membrane technology are imitated
The restriction of rate etc., these influence factors can not arbitrarily change.Wherein change fluid flow state relatively simple easy, and
And select suitable condition the most obvious to the effect alleviating concentration polarization and fouling membrane, cost is relatively low.
Ultrafiltration of the present invention uses external pressing type hollow fibrous membrane, and (material is existing known conventional such as Kynoar
PVDF, polysulfones PS, PES polyether sulfone etc., preferably PVDF, anti-fouling performance is good, and chemistry, mechanical strength are good).In view of maximum limit
Degree ground ensures the filter efficiency of ultra-filtration process of the present invention, solves and alleviate concentration polarization and fouling membrane, by specific film
Operational factor, film silk select and the synergism of assembly loading density runs, and circulate in follow-up first, can be abundant
Remove in water the materials such as HF, HN03, HCL, ultrafiltration is produced water by high-pressure pump and enter reverse osmosis desalination system, improve reverse osmosis system
The salt rejection rate of system, pH is adjusted to 7-8, makes counter-infiltration system salt rejection rate >=90%；By the first internal circulation system, it is ensured that system is whole
The body response rate >=85%, finally makes reverse osmosis unit produce water effect industrial tap water and is applied to production line.
As preferably, the cleaning wastewater collection of described photovoltaic acidity is entered former pond, then sequentially enter raw water pump, accurate mistake
Filter and ultrafiltration apparatus, at accurate filter porch regulation photovoltaic acidity cleaning pH value of waste water to 7-8.
As preferably, described ultrafiltration apparatus produce the mouth of a river connect have ultrafiltration water tank, described ultrafiltration water tank be connected to for
The recoil pump cleaning described ultrafiltration apparatus and the high-pressure pump circulated in first.
As preferably, produce water before entering the first internal circulation system as the Part I ultrafiltration of follow-up Treatment for Reuse, first
Mixing with pressure air-dissolving water, subsequently into gas-floating chamber, gas-floating chamber operating pressure is 1-3N, and the colloid and the float that are formed in water exist
Separating in gas-floating chamber, scum silica frost circulates in entering described first by waterpower mode or mechanical system after water surface is removed
System.
Use the method can promote the efficiency of circular treatment in first further, improve the salt rejection rate of counter-infiltration system,
Raising system recycled in its entirety rate.
As preferably, described reverse osmosis desalination plant water outlet is re-used as industrial tap water and is back to raw after carrying out ionic adsorption
Producing line, reverse osmosis desalination plant water outlet specifically is passed through to comprise by (0.1-by described ionic adsorption with the speed of 15-20cm/min
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
The modified double resin ion-exchanger pillar of composition.
Use and carry out ionic adsorption after reverse osmosis, the fluoride ion removing in waste water can be improved, reduce containing in pure water
Fluorine amount.
It is highly preferred 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: fill 1 under normal temperature and pressure in fixed bed reactors
The gel strong-acid type H-type phenylethylene resin series of parts by volume, the mass percent concentration injecting 10-12 times of parts by volume is 1-5%'s
Aluminum sulfate solution or pyrosulfuric acid aluminum solutions, soak 1-3h, then clean with deionized water, standby；
B. the preparation of macropore weak-type Al-type ion exchange resin: fill 1 under normal temperature and pressure in fixed bed reactors
The macropore weak-type H-type acrylic resin of parts by volume, the mass percent concentration injecting 10-12 times of parts by volume is 0.5-
The aluminum sulfate solution of 1.5% or pyrosulfuric acid aluminum solutions, soak 0.5-2.5h, then clean with deionized water, standby；
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
With macropore weak-type Al-type ion exchange resin.
Owing to aluminium ion has stronger affinity to fluorion, series of stable compound can be formed with fluorion, thus
Can remove the fluorion in water:
Al3++F- = AlF2+
AlF2++F- = AlF+
…
AlF5 2-+F- = AlF6 +
After long-time fluorine removal, some color of resin in exchange column deepen, and illustrate that resin is contaminated, need regeneration.After fluorine removal
Resin can regenerate with aluminum sulfate solution, regenerative response is as follows:
(R-SO3)2AlF+Al3++ (R-SO3)-=(R-SO3)3Al+AlF2+
Controlling regeneration frequency according to waste water fluorinated volume, on the downside of exchange column, import department imports aluminum sulfate solution or pyrosulfuric acid aluminum
Solution regenerates, regenerative elution liquid on the upside of exchange column exit flow out after, then by this regenerative elution liquid import pending
In photovoltaic wastewater, due to AlF2+Still can react further with fluorion, therefore can improve technique fluoride removing rate, reduce fluorine removal medicine
The use of agent.The modified double resin ion-exchanger of the present invention can repeatedly regenerate, and service life is 3-5.
It is further preferred that described gel strong-acid type Al-type ion exchange resin bead footpath is 0.2-0.3mm, water content
For 48-52%, wet true density is 1.28-1.32g/ml, rate of small round spheres >=98%.
It is further preferred that described macropore weak-type Al-type ion exchange resin bead footpath is 0.6-1.1mm, water content
For 50-56%, wet true density is 1.45-1.84g/ml, rate of small round spheres >=98%.
The most preferably, after ionic adsorption completes, add chelating agent and promote described modified double resin ion-exchanger
Regeneration, the mass ratio of described chelating agent and described modified double resin ion-exchanger is 1:70-90；
Described chelating agent is the citric acid according to mass ratio 1-3:4-7 composition and the mixture of edetate.
As preferably, described ultrafiltration apparatus, high-pressure pump and reverse osmosis unit form the second internal circulation system, and ultrafiltration is produced water
Squeeze into high-pressure pump and reverse osmosis unit carries out repeatedly circular treatment in second, make system recycled in its entirety rate >=85%.
In sum, the method have the advantages that
1, counter-infiltration system salt rejection rate >=90%；
2, system recycled in its entirety rate >=85%.
Accompanying drawing explanation
Fig. 1 is photovoltaic acidity washing waste water recycling process chart of the present invention.
Detailed description of the invention
Below in conjunction with accompanying drawing, the present invention is described in further detail.
Embodiment one
As it is shown in figure 1, photovoltaic acidity washing waste water recycling technique includes step:
(1) regulation pH value: the cleaning wastewater collection of photovoltaic acidity is entered former pond, then sequentially enters raw water pump, accurate mistake
Filter, in accurate filter porch, regulation photovoltaic acidity cleans pH value of waste water to 7；
(2) ultrafiltration: the waste water after being regulated by pH value squeezes into ultrafiltration apparatus under pressure 0.09MPa, obtains after hyperfiltration treatment
Water is produced in ultrafiltration, and ultrafiltration concentrated water drainage processes further to sewage plant；It is two parts that moisture is produced in ultrafiltration, and Part I is as follow-up reuse
Processing, Part II is for the backwash of ultrafiltration apparatus；
Ultrafiltration apparatus often runs and carries out an automatic back-washing half an hour；Rinse flux to control at 110L/m hr；Backwash pressure
Power≤0.2MPa；30 seconds backwash time；
Ultrafiltration apparatus is external pressing type hollow fibrous membrane, and the ratio of film silk internal-and external diameter is 1:2, ultrafiltration module loading density 900m2/
m3；
Circulation in (3) first: the Part I ultrafiltration product water as follow-up Treatment for Reuse enters the first internal circulation system, the
One internal circulation system includes high-pressure pump and the reverse osmosis desalination plant being sequentially connected with ultrafiltration apparatus；Will be through high-pressure pump and reverse osmosis
Thoroughly the water outlet of desalination is again squeezed into high pressure pump inlet and is carried out repeatedly circular treatment in first, makes system recycled in its entirety rate >=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 (about 20 yuan/ton of Special section such as Ningbo), this
Set acid waste water reclaiming system can help the water of 85% in reuse acid waste water as production tap water, to increase economic effect for user
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 use
The construction investment cost at family.
Table 1 Economic and Efficiency Analysis
Embodiment two
With embodiment one, the waste water after except for the difference that pH value is specifically regulated by ultrafiltration is squeezed into super under pressure 0.08MPa
Filter device, obtains ultrafiltration and produces water after hyperfiltration treatment, ultrafiltration concentrated water drainage processes further to sewage plant；It is two that moisture is produced in ultrafiltration
Point, Part I is as follow-up Treatment for Reuse, and Part II is for the backwash of ultrafiltration apparatus；Ultrafiltration apparatus often runs and enters half an hour
Automatic back-washing of row；Rinse flux to control at 100L/m hr；Backwash pressure≤0.2MPa；20 seconds backwash time；Ultrafiltration fills
The ratio being set to external pressing type hollow fibrous membrane film silk internal-and external diameter is 1:1.5, ultrafiltration module loading density 800m2/m3；
In accurate filter porch, regulation photovoltaic acidity cleans pH value of waste water to 8；Ultrafiltration apparatus produces mouth of a river connection to be had super
Water filtering tank, ultrafiltration water tank is connected to the recoil pump for cleaning ultrafiltration apparatus and the high-pressure pump circulated in first.
Water is produced entering before the first internal circulation system, elder generation and pressure air-dissolving as the Part I ultrafiltration of follow-up Treatment for Reuse
Water mixes, and subsequently into gas-floating chamber, gas-floating chamber operating pressure is 1N, and the colloid and the float that are formed in water are carried out in gas-floating chamber
Separating, 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 and is back to production line, ionic adsorption after carrying out ionic adsorption
Specifically that reverse osmosis desalination plant water outlet is strong by comprising by the gel of 0.1:7 mixed in molar ratio with the speed of 15cm/min
Acid type Al-type ion exchange resin and the modified double resin ion-exchanger of macropore weak-type Al-type ion exchange resin composition
Pillar.
Adding chelating agent after ionic adsorption completes and promote the regeneration of modified double resin ion-exchanger, chelating agent is with modified
The mass ratio of double resin ion exchangers is 1:70；Chelating agent is the citric acid according to mass ratio 1:7 composition and ethylenediamine tetrem
The mixture of hydrochlorate.
Ultrafiltration apparatus, high-pressure pump and reverse osmosis unit form the second internal circulation system, ultrafiltration is produced water squeeze into high-pressure pump and
Reverse osmosis unit carries out repeatedly circular treatment in second, makes system recycled in its entirety rate 95%.
The preparation method of double resin ion exchangers comprises the following steps successively:
A. the preparation of gel strong-acid type Al-type ion exchange resin: fill 1 under normal temperature and pressure in fixed bed reactors
The gel strong-acid type H-type phenylethylene resin series of parts by volume, injects the aluminum sulfate that mass percent concentration is 1% of 10 times of parts by volume
Solution or pyrosulfuric acid aluminum solutions, soak 1-3h, then clean with deionized water, standby；
B. the preparation of macropore weak-type Al-type ion exchange resin: fill 1 under normal temperature and pressure in fixed bed reactors
The macropore weak-type H-type acrylic resin of parts by volume, injects the sulphuric acid that mass percent concentration is 0.5% of 10 times of parts by volume
Aluminum solutions or pyrosulfuric acid aluminum solutions, soak 0.5h, then clean with deionized water, standby；
Mix gel strong-acid type Al-type ion exchange resin and macropore weak-type prepared by above-mentioned steps the most in molar ratio
Al-type ion exchange resin.
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, except for the difference that step (1) pH value regulates to 6.5, and the Part I as follow-up Treatment for Reuse surpasses
Filter is produced water and is introduced into high-pressure pump and carries out repeatedly circular treatment in first, but is directly entered reverse osmosis unit and processes.Experimental result
It is shown in Table 2.As can be seen from Table 2, the photovoltaic wastewater within 2000ml reaches 4.58mg/L, far by the filtrate fluorinated volume after exchange column
0.02mg/L more than embodiment.
Fluorine removal situation tested by table 2
Embodiment three
With embodiment two, the waste water after except for the difference that being regulated by pH value squeezes into ultrafiltration apparatus, ultrafiltration under pressure 0.12MPa
Obtaining ultrafiltration after process and produce water, ultrafiltration concentrated water drainage processes further to sewage plant；It is two parts that moisture is produced in ultrafiltration, and Part I is made
For follow-up Treatment for Reuse, Part II is for the backwash of ultrafiltration apparatus；Ultrafiltration apparatus often runs and carries out half an hour once the most instead
Wash；Rinse flux to control at 120L/m hr；Backwash pressure≤0.2MPa；40 seconds backwash time；Ultrafiltration apparatus is in external-compression type
The ratio of hollow fiber film film silk internal-and external diameter is 1:2.5, ultrafiltration module loading density 1200m2/m3；
In accurate filter porch, regulation photovoltaic acidity cleans pH value of waste water to 7.8；As follow-up Treatment for Reuse
A part of ultrafiltration product water, before entering the first internal circulation system, first mixes with pressure air-dissolving water, subsequently into gas-floating chamber, gas-floating chamber
Operating pressure is 1N.
Reverse osmosis desalination plant water outlet is re-used as industrial tap water and is back to production line, ionic adsorption after carrying out ionic adsorption
Specifically pass through to comprise by the gel strong acid of 2:5 mixed in molar ratio with the speed of 20cm/min by reverse osmosis desalination plant water outlet
Type Al-type ion exchange resin and the modified double resin ion-exchanger post of macropore weak-type Al-type ion exchange resin composition
Son.
Adding chelating agent after ionic adsorption completes and promote the regeneration of modified double resin ion-exchanger, chelating agent is with modified
The mass ratio of double resin ion exchangers is 1:90；Chelating agent is the citric acid according to mass ratio 3:4 composition and ethylenediamine tetrem
The mixture of hydrochlorate.
The preparation method of double resin ion exchangers comprises the following steps successively:
A. the preparation of gel strong-acid type Al-type ion exchange resin: fill 1 under normal temperature and pressure in fixed bed reactors
The gel strong-acid type H-type phenylethylene resin series of parts by volume, injects the aluminum sulfate that mass percent concentration is 5% of 12 times of parts by volume
Solution or pyrosulfuric acid aluminum solutions, soak 3h, then clean with deionized water, standby；
B. the preparation of macropore weak-type Al-type ion exchange resin: fill 1 under normal temperature and pressure in fixed bed reactors
The macropore weak-type H-type acrylic resin of parts by volume, injects the sulphuric acid that mass percent concentration is 1.5% of 12 times of parts by volume
Aluminum solutions or pyrosulfuric acid aluminum solutions, soak 2.5h, then clean with deionized water, standby；
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 acid
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, except for the difference that water circulation in entering first is produced in the Part I ultrafiltration as follow-up Treatment for Reuse
Before system, first mixing with pressure air-dissolving water, subsequently into gas-floating chamber, gas-floating chamber operating pressure is 3N.
Reverse osmosis desalination plant water outlet is re-used as industrial tap water and is back to production line, ionic adsorption after carrying out ionic adsorption
Specifically pass through to comprise by the gel strong acid of 2:5 mixed in molar ratio with the speed of 18cm/min by reverse osmosis desalination plant water outlet
Type Al-type ion exchange resin and the modified double resin ion-exchanger post of macropore weak-type Al-type ion exchange resin composition
Son.
Adding chelating agent after ionic adsorption completes and promote the regeneration of modified double resin ion-exchanger, chelating agent is with modified
The mass ratio of double resin ion exchangers is 1:70-90；Chelating agent is the citric acid according to mass ratio 1-3:4-7 composition and second two
The mixture of amine tetraacetate.
The preparation method of double resin ion exchangers comprises the following steps successively:
A. the preparation of gel strong-acid type Al-type ion exchange resin: fill 1 under normal temperature and pressure in fixed bed reactors
The gel strong-acid type H-type phenylethylene resin series of parts by volume, injects the aluminum sulfate that mass percent concentration is 4% of 11 times of parts by volume
Solution or pyrosulfuric acid aluminum solutions, soak 2h, then clean with deionized water, standby；
B. the preparation of macropore weak-type Al-type ion exchange resin: fill 1 under normal temperature and pressure in fixed bed reactors
The macropore weak-type H-type acrylic resin of parts by volume, injects the sulphuric acid that mass percent concentration is 0.9% of 11 times of parts by volume
Aluminum solutions or pyrosulfuric acid aluminum solutions, soak 1.5h, then clean with deionized water, standby；
Mix gel strong-acid type Al-type ion exchange resin and macropore weak-type prepared by above-mentioned steps the most in molar ratio
Al-type ion exchange resin.
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, and it is not limitation of the present invention, people in the art
The present embodiment can be made after reading this specification by member as required does not has the amendment of creative contribution, but as long as at this
All protected by Patent Law in the right of invention.
Claims (9)
1. a photovoltaic acidity washing waste water recycling technique, it is characterised in that include step successively:
(1) regulation pH value: collection photovoltaics acidity cleans waste water, regulation photovoltaic acidity cleaning pH value of waste water to 7-8；
(2) ultrafiltration: the waste water after being regulated by pH value squeezes into ultrafiltration apparatus under pressure 0.08-0.12MPa, obtains after hyperfiltration treatment
Water is produced in ultrafiltration, and ultrafiltration concentrated water drainage processes further to sewage plant；It is two parts that moisture is produced in described ultrafiltration, and Part I is as follow-up
Treatment for Reuse, Part II is for the backwash of ultrafiltration apparatus；
Described ultrafiltration apparatus often runs and carries out an automatic back-washing half an hour；Rinse flux to control at 100-120L/m hr；Instead
Wash pressure≤0.2MPa；20-40 second backwash time；
Described ultrafiltration apparatus is external pressing type hollow fibrous membrane, and the ratio of its film silk internal-and external diameter is 1:1.5-2.5, and ultrafiltration module filling is close
Degree 800 ~ 1200m2/m3；
Circulation in (3) first: produce water as the Part I ultrafiltration of follow-up Treatment for Reuse and enter the first internal circulation system, described the
One internal circulation system includes being connected to the high-pressure pump after described ultrafiltration apparatus and reverse osmosis desalination plant；Will through high-pressure pump and
The water outlet of reverse osmosis desalination is again squeezed into high pressure pump inlet and is carried out repeatedly circular treatment in first, make system recycled in its entirety rate >=
85%；
Produce water entering before the first internal circulation system as the Part I ultrafiltration of follow-up Treatment for Reuse, first mix with pressure air-dissolving water
Closing, subsequently into gas-floating chamber, gas-floating chamber operating pressure is 1-3N, and the colloid and the float that are formed in water are carried out point in gas-floating chamber
From, scum silica frost enters described first internal circulation system by waterpower mode or mechanical system after water surface is removed；
(4) pure water reuse: final reverse osmosis water outlet is back to production line as industrial tap water.
A kind of photovoltaic acidity washing waste water recycling technique the most according to claim 1, it is characterised in that: by the acid of described photovoltaic
Property clean wastewater collection enter former pond, then sequentially enter raw water pump, accurate filter and ultrafiltration apparatus, enter at accurate filter
Regulate photovoltaic acidity at Kou and clean pH value of waste water to 7-8.
A kind of photovoltaic acidity washing waste water recycling technique the most according to claim 2, it is characterised in that: described ultrafiltration apparatus
Produce the mouth of a river connect have ultrafiltration water tank, described ultrafiltration water tank be connected to the recoil pump for cleaning described ultrafiltration apparatus and for
The high-pressure pump of circulation in first.
A kind of photovoltaic acidity washing waste water recycling technique the most according to claim 3, it is characterised in that: described reverse osmosis removes
Salt device water outlet is re-used as industrial tap water and is back to production line after carrying out ionic adsorption, described ionic adsorption is specifically by reverse osmosis
Demineralizer water outlet is passed through to comprise by (0.1-2) with the speed of 15-20cm/min thoroughly: the gel strong acid of (5-7) mixed in molar ratio
Type Al-type ion exchange resin and the modified double resin ion-exchanger post of macropore weak-type Al-type ion exchange resin composition
Son.
A kind of photovoltaic acidity washing waste water recycling technique the most according to claim 4, it is characterised in that: the double tree of described modification
The preparation method of fat ion-exchanger comprises the following steps successively:
A. the preparation of gel strong-acid type Al-type ion exchange resin: fill 1 volume under normal temperature and pressure in fixed bed reactors
The gel strong-acid type H-type phenylethylene resin series of part, injects the sulphuric acid that mass percent concentration is 1-5% of 10-12 times of parts by volume
Aluminum solutions or pyrosulfuric acid aluminum solutions, soak 1-3h, then clean with deionized water, standby；
B. the preparation of macropore weak-type Al-type ion exchange resin: fill 1 volume under normal temperature and pressure in fixed bed reactors
The macropore weak-type H-type acrylic resin of part, the mass percent concentration injecting 10-12 times of parts by volume is 0.5-1.5%'s
Aluminum sulfate solution or pyrosulfuric acid aluminum solutions, soak 0.5-2.5h, then clean with deionized water, standby；
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 is with big
Hole weak-type Al-type ion exchange resin.
A kind of photovoltaic acidity washing waste water recycling technique the most according to claim 5, it is characterised in that: described gel is 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%.
A kind of photovoltaic acidity washing waste water recycling technique the most according to claim 6, it is characterised in that: described macropore is weak
Acid 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%.
A kind of photovoltaic acidity washing waste water recycling technique the most according to claim 7, it is characterised in that: complete in ionic adsorption
Add chelating agent after one-tenth and promote the regeneration of described modified double resin ion-exchanger, described chelating agent and described modified double resin from
The mass ratio of sub-exchanger is 1:70-90；
Described chelating agent is the citric acid according to mass ratio 1-3:4-7 composition and the mixture of edetate.
9. according to a kind of photovoltaic acidity washing waste water recycling technique described in any one of claim 2-8, it is characterised in that: described
Ultrafiltration apparatus, high-pressure pump and reverse osmosis unit form the second internal circulation system, ultrafiltration is produced water and squeezes into high-pressure pump and reverse osmosis dress
Put and carry out repeatedly circular treatment in second.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410846449.XA CN104609596B (en) | 2014-12-31 | 2014-12-31 | A kind of photovoltaic acidity washing waste water recycling technique |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410846449.XA CN104609596B (en) | 2014-12-31 | 2014-12-31 | A kind of photovoltaic acidity washing waste water recycling technique |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104609596A CN104609596A (en) | 2015-05-13 |
| CN104609596B true CN104609596B (en) | 2016-08-31 |
Family
ID=53144294
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410846449.XA Active CN104609596B (en) | 2014-12-31 | 2014-12-31 | A kind of photovoltaic acidity washing waste water recycling technique |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104609596B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN112830621B (en) * | 2019-11-25 | 2022-07-29 | 福建杰达环保科技有限公司 | Beneficiation wastewater recycling system and method based on membrane chemical reactor |
| 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 |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN1931746A (en) * | 2006-09-29 | 2007-03-21 | 上海科程水处理技术有限公司 | Industrial effluent reusing zero-drainage process |
| CN103172199B (en) * | 2013-03-21 | 2015-03-25 | 深圳市超纯环保股份有限公司 | Method for treating hydrofluoric acid wastewater |
-
2014
- 2014-12-31 CN CN201410846449.XA patent/CN104609596B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN104609596A (en) | 2015-05-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106045035B (en) | A kind of ternary sewage water treatment method for coupling anaerobic acid-production, positive infiltration and microbiological fuel cell | |
| WO2022143014A1 (en) | Resourceful treatment system and method for sodium nitrate wastewater | |
| CN104609596B (en) | A kind of photovoltaic acidity washing waste water recycling technique | |
| CN106350614B (en) | Comprehensive recycling method for preparing ion exchange water and acid and alkali from maltose syrup | |
| CN109987739A (en) | A kind of container-type seawater desalination system | |
| CN105399249B (en) | A kind of device and method of municipal wastewater advanced treating | |
| CN203602414U (en) | System for recovering silvering wastewater and silver | |
| CN105439347B (en) | A kind of mother liquor treatment process and system for the concentration of clopyralid feed separation | |
| CN103848422B (en) | Activated carbon purging system and method thereof | |
| CN102351336A (en) | Electroplating wastewater treatment process | |
| CN106830451A (en) | The deionization integral treatment method and device of a kind of desalination water | |
| CN212864458U (en) | Boiler makeup water deep desalination treatment system | |
| CN204824274U (en) | Waste water recycling equipment | |
| CN211847452U (en) | Ion exchange water treatment device | |
| CN210419589U (en) | Novel acid wastewater recovery equipment for semiconductor factory | |
| CN208594058U (en) | A kind of integration microkinetic low-pressure membrane filtration device | |
| CN102874804B (en) | Cleaning method in activated carbon for super capacitors production | |
| CN207361986U (en) | A kind of polyamide -6 produces sewage recovering system | |
| CN207775032U (en) | Electroplating wastewater zero processing unit | |
| CN205347001U (en) | Wastewater recycling device | |
| CN206529343U (en) | A kind of reverse osmosis purification device | |
| CN204803125U (en) | Desalt and categorised use equipment | |
| CN205953609U (en) | Device that lower valency salt solution back flush alleviating milipore filter pollutes | |
| CN206359357U (en) | A kind of Catalyst sewage zero-discharge treatment system | |
| CN2211319Y (en) | Ultra filtering reverse osmosis unified water treating apparatus |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
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 |
|
| PE01 | Entry into force of the registration of the contract for pledge of patent right | ||
| PC01 | Cancellation of the registration of the contract for pledge of patent right |
Date of cancellation: 20230531 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 |
|
| PC01 | Cancellation of the registration of the contract for pledge of patent right |