CN109205829A - The method of film assisting crystallisation technique MAC selective removal and the copper in recycle-water - Google Patents
The method of film assisting crystallisation technique MAC selective removal and the copper in recycle-water Download PDFInfo
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- CN109205829A CN109205829A CN201811047096.1A CN201811047096A CN109205829A CN 109205829 A CN109205829 A CN 109205829A CN 201811047096 A CN201811047096 A CN 201811047096A CN 109205829 A CN109205829 A CN 109205829A
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or 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
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
- C02F1/62—Heavy metal compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F2001/5218—Crystallization
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2201/00—Apparatus for treatment of water, waste water or sewage
- C02F2201/002—Construction details of the apparatus
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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
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/005—Processes using a programmable logic controller [PLC]
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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
- C02F2303/00—Specific treatment goals
- C02F2303/14—Maintenance of water treatment installations
Abstract
The method that the present invention discloses a kind of film assisting crystallisation technique MAC selective removal and the copper in recycle-water, the technique are made of the crystallization reactor and membrane reactor of two series operations.In order to ensure precipitating purity and be convenient for Cu2+Recycling and reuse, respectively use Na2CO3And Cu2(OH)CO3As precipitating reagent and crystal seed (only needing once to add 0.1-0.5wt% when starting), Cu in water2+Nucleation and crystal growth occur mainly in crystallization reaction, the membrane module in membrane separator be mainly used for further crystallize and concentration solid phase, under optimum process condition, Cu in water2+Finally with Cu2(OH)CO3The form of crystal grain is recovered, and purity is up to 99%.Two key parameters of this process operation: supersaturated index (SI < 3.22) and excessive carbonate (35mg/L < CO3 2‑< 50mg/L), and can be required according to effluent quality, the dosage of precipitating reagent is adjusted, therefore there is the advantage for the cost that economizes on resources, reduces, there is positive meaning to promotion social sustainable development.
Description
Technical field
The present invention relates to the removal of copper ion in water and recycling, in particular to a kind of to go to remove water using film assisting crystallisation technique
The method of middle copper and recycling copper.
Background technique
Come in the past few decades, heavy metal (such as copper, zinc, nickel and cadmium etc.) is to environment, publilc health and economic potential impact
Main problem always concerned by people, wherein copper is the important component of untreated effluent[1-3].Although Cu2+It is closed in enzyme
At playing an important role in, tissue and skeleton development, but excessive Cu2+Many may be caused to have human body and organism
Harmful damage[4-6], such as cause in underground service line and home pipeline device copper and lead because of corruption due to lacking corrosion control processing
Lose Flintwater crisis caused by (caused by chlorine) leaching[7].The World Health Organization has determined that the Cu in drinking water2+Allow
Limit value is 2.0mg/L[8]；And for China, the limit value of permission is then 1.0mg/L[3].Therefore, earth's surface is discharged into Cu-W ore deposit waste water
Before water or sewerage, it is necessary to handle it, to protect the mankind and environment.
For removing Cu from aqueous solution2+Method, including chemical precipitation[9,10], condensation flocculation[11], UF membrane[12], inhale
It is attached[13-14], biological adsorption[15,16], electrochemistry[17], ion exchange[18]Deng.Wherein, chemical precipitation method is that a kind of suitable processing is big
The simple effective method of waste water is measured, and is widely used；As for other methods, due to the high cost limit built and runed
Its application and exploitation are made[19-21].Although chemical precipitation (being neutralized especially with highly basic or sulfide precipitation) has fortune
Row validity can be applied to heavy duty work unit, but can generate and largely be difficult to the sludge being separated from water；In addition, hydroxide is heavy
The optimal pH in shallow lake usually occurs in higher pH value range[22], therefore the corrosion of equipment is very serious, and final waste water row
It needs further to neutralize waste water with acid before putting[5,23]；For sulfide precipitation, although due to metal sulfide sediment
Solubility is lower[24], show quick reaction rate, the potentiality of selective removal metal and better settling property[24],
But it is difficult to control the formation of aqueous polysulfide, after metal removal, waste water needs further to aoxidize to remove before finally discharging
Sulfide in water[5,23].On the other hand, as one of metal most important and most widely used in many industries, copper consumption
It increases sharply, it is ensured that enough copper source supplies are to keep demand to be not easy to[23].Hence it is highly desirable to develop a kind of new
Method is able to maintain high metal removal and recovery efficiency in the low-down situation of concentration, and allows to go in metal
Except the rear reuse or discharge for directly carrying out water, without carry out it is any be further processed, such as alkali neutralization or the remaining vulcanization of oxidation
Object.
A kind of alternative solution is will to precipitate to be converted into crystallization process.Crystallization is most ancient in chemistry and pharmaceuticals industry and application
One of widest separation process[25].Degree of supersaturation is the driving force of crystallization[26,27], usually can by change temperature and/
Or (solvent evaporation, add solvent resistant, crystal seed etc.) is formed to realize the saturation of solution.Wherein, it has been developed based on seeded crystallization
Two kinds of wastewater processing technologies, i.e. pellet reactor (PP) and film assisting crystallisation device (MAC), the former feature, that is, fluidized-bed reactor
(FBR), it is used for the processing of various water and sewage very early, such as the softening of drinking water[28], the recycling of calcirm-fluoride[29]In FBR
Phosphate removal[30], and the recycling for carrying out heavy metal by launching carbonate deposition agent etc. on sand grain surface[31], but
In the technique, only by the grain dissolution of recycling in acid after can just reuse.Alternative as pellet reactor (PR)
Case, MAC are developed by TNO first, this is the integrated of two well-known unit operations, i.e., continuous seeded crystallization and film filtering.
Due to the development of membrane technology, the research of MAC technique is in the past decade being increased always, Chabanon et al.[26]For so far
The present report about MAC difference research, give state-of-the-art technology comment, show reverse osmosis (RO), osmotic distillation (OD) and
Membrane distillation (MD) is the most common method of MAC technique[20,27].Currently, copper removal and removal process based on MAC technique do not appear in the newspapers
Road.
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friendly mechanochemical method:application for Cu(II)ions removal from water
and aquatic ecotoxicity.Sci.Total Environ.607-608,1479-1486.
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[17]Lambert,A.,Drogui,P.,Daghrir,R.,Zaviska,F.,Benzaazoua,M.,
2014.Removal of copper in leachate from mining residues using electrochemical
technology.J.Environ.Manage.133,78-85.
Lange and Adolph,N.,1999.Lange's handbook of chemistry.Mcgraw-Hill
Book Company.[18]Ntimbani,R.N.,Simate,G.S.,Ndlovu,S.,2016.Removal of copper
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Summary of the invention
It is an object of the invention to overcome the deficiencies in the prior art to provide a kind of film assisting crystallisation technique MAC selective removal
With the method for the copper in recycle-water.
The technical scheme is that the method for film assisting crystallisation technique MAC selective removal and the copper in recycle-water,
It is characterized in that, includes the following steps:
(1) effluent quality according to demand determines two key parameters of process operation: supersaturated index (SI) and excess
Carbonate (CO3 2-)；
(2) dosage of precipitating reagent is calculated:
If it is desired to be discharged Cu2+Concentration reaches the requirement of WHO effluent quality criterion, need to be by excessive CO3 2-Control is in 35-50mg/
Within the scope of L；
It, need to be by excess if effluent quality is needed to reach the requirement of China's " standards for drinking water quality " (GB 5749-2006)
CO3 2-Control is within the scope of 45-50mg/L；
(3) dosage for combining influent quality and precipitating reagent calculates SI value, and controls crystallization reaction by adjusting into dose
SI value in device is below 3.22；
(4) amount for adding crystal seed, 0.1-0.5wt% are determined, and MAC technique is only needed once to add when starting；
(5) after adding crystal seed, into crystallization reactor, water inlet adds required amount of sodium carbonate while simultaneously to design liquid level
Mechanical stirring is carried out, stirring intensity 120-180rpm, mixing time is no less than 5min, the sedimentation time is no less than 8min, in water
Copper ion just under the induction of basic copper carbonate crystal seed, reacts with sodium carbonate and generates big partial size compact grain object Cu2(OH)2CO3It is brilliant
Body, and it is deposited to the bottom of crystallization reactor, the supernatant in crystallization reactor goes successively to membrane reactor and further crystallizes, is solid
Liquid separation, to obtain more preferably effluent quality；After crystal runs up to certain volume, i.e. recoverable, crystallization reactor domestic demand
It stays a part of crystal to continue the crystal seed as subsequent reactions, and to keep a certain amount of residue CO in its reactor3 2-；
(6) due to the crystal formd in crystallization reactor, fouling membrane is effectively prevented, it is only i.e. desirable by washing
Obtain preferable membrane specific flux recovery rate.
Excessive CO in the step (2)3 2-Refer to and the Cu in pending water2+Concentration is compared, remaining carbonate
Amount, in terms of mg/L.
Water outlet pH meets GB 5749-2006 standard in the step (2), is discharged pH preferred scope between 7-8, avoids
The co-precipitation of the cation such as Ca, Mg, realizes the selective recovery of copper in water.
SI refers to the supersaturated index of the component in reactor before the reaction, i.e. crystallization driving force in the step (3).
The dosage of crystal seed in the step (4), in terms of the volume of period 1 pending water, i.e. 1.0-5.0g/L.
The step (5) realizes automatic running by PLC program.
The theory of MAC technique is used to handle and recycle copper-containing wastewater for the first time by the present invention, in order to obtain film and crystallization process
Inherent advantage and avoid its disadvantage, which is made of the crystallization reactor and membrane separator of series operation, nucleation and crystal
Growth occurs mainly in crystallizer, and the membrane module in membrane separator be used to further crystallize and concentration solid phase, i.e., for solid
Liquid separation, therefore the shortcomings that avoid fouling membrane.In order to ensure precipitating purity and be convenient for Cu2+Recycling and reuse, respectively
Use Na2CO3And Cu2(OH)CO3As precipitating reagent and crystal seed, following (the Lange and of the chemical reaction occurred in reactor
Adolph, 1999):
Cu2++CO3 2-=CuCO3；Ksp=1.4 × 10-9.9 (1)
2CuCO3+H2O=Cu2(OH)2CO3+CO2↑ (2)
CO3 2-+H2O=HCO3 -+OH- (3)
Cu2++2OH-=Cu (OH)2↓；Ksp=2.2 × 10-19.7 (4)
The key process parameter of MAC process operation is supersaturated index (Saturation index, SI) and excessive carbonic acid
Root (Excess CO3 2-, mg/L), wherein
SI=log ([Cu2+]·[CO3 2-]/ksp) (5)
Ksp Is is CuCO3Solubility product constant；[Cu2+]、It is Cu respectively2+And CO3 2-Molar concentration before reaction,
mol/L.Excessive carbonate refers to and the Cu in pending water2+Concentration is compared, the amount of remaining carbonate.
After process operation starts, pass through Cu in measurement membrane reactor water outlet2+Concentration, turbidity, pH value assess MAC process
Performance passes through the volume of calculation processing water and the volume ratio (concentration factor, CF) of sediment (copper of recycling)
The compression properties of MAC technique are measured, using the performance of measuring film than flux (Specific flux, SF), use granularity point
Cloth (Particle size distribution, PSD), scanning electron microscope (Scanning electron
Microscopy, SEM), X-ray diffraction (X-ray diffraction) and X-ray energy dispersion spectrum (Energy
Dispersive spectroscopy, EDS) characterize the feature for recycling crystal.
The present invention have compared with the existing technology it is following the utility model has the advantages that
1, the present invention takes full advantage of the advantage of crystallization reactor and membrane reactor respectively, realizes the selectivity of copper in water
It recycles；
2, the present invention can carry out the reuse or discharge of water after metal removal, without carry out it is any be further processed, such as
Alkali neutralization or the remaining sulfide of oxidation.
3, the present invention can determine the dosage of precipitating reagent, economize on resources, sustainable development according to effluent quality needs；
4, recovery product of the invention is closely knit Cu2(OH)2CO3Crystal grain, the shortcomings that effectively preventing fouling membrane；
5, the pH of Process for Effluent meets GB 5749-2006 standard in the present invention, avoids the cation such as Ca, Mg in water
Co-precipitation, realizes the selective recovery of copper；
6, recovery product Cu of the invention2(OH)2CO3Crystal purity is up to 99%, therefore, directly can recycle or continue
Crystal seed as MAC technique；
7, crystal seed of the invention only need to be added once, subsequent to reduce chemistry directly using recovery product as crystal seed
The dosage of reagent；
8, the present invention is at low cost, environment friendly, good in economic efficiency and economize on resources, to pushing social sustainable development tool
There is positive meaning.
Detailed description of the invention
Fig. 1 is Cu in the removal of MAC technique and recycle-water2+Flow chart；
Fig. 2 is embodiment 1 and two groups of group check experiment recovery product XRD analysis；
Fig. 3 is embodiment 1 and two groups of group check experiment recovery product grain size analyses；
Fig. 4 is electromicroscopic photograph: (a) crystal seed；(b) embodiment 1；(c) control group A；(d) control group B.
Specific embodiment
Below by specific embodiments and the drawings, the present invention is further illustrated.The embodiment of the present invention is in order to more
So that those skilled in the art is more fully understood the present invention well, any limitation is not made to the present invention.
MAC removal and recycling Cu2+The composition of technique, it includes crystallization reactors and membrane separator, in order to make into water
Cu2+It is sufficiently mixed with precipitating reagent, crystal seed, a blender is matched in crystallization reactor, and divided into crystallization in two reactors and produce
Object discharge port, the removal of MAC technique and recycling Cu2+Process flow chart see Fig. 1.
Process unit size can carry out flexible design according to water to be processed.
The continuous operation of technique can be automatically controlled by PLC program, and operational process is as follows:
MAC technique starting before, crystal seed (only needing once to add) is added into reactor first, backward crystallization reactor in
After water inlet to design liquid level, adds required amount of sodium carbonate and carry out mechanical stirring simultaneously (stirring intensity 120-180rpm, is stirred
Mix that the time is no less than 5min, the sedimentation time is no less than 8min), the copper ion in water just under the induction of basic copper carbonate crystal seed,
It is reacted with sodium carbonate and generates big partial size compact grain object Cu2(OH)2CO3Crystal, and it is deposited to the bottom of crystallization reactor, it crystallizes
Supernatant in reactor goes successively to membrane reactor and further crystallizes, is separated by solid-liquid separation, to obtain more preferably effluent quality；Crystal
After running up to certain volume, i.e., recoverable, crystallization reactor domestic demand stay a part of crystal to continue the crystalline substance as subsequent reactions
Kind, and a certain amount of residue CO is kept in its reactor3 2-。
Design and operation method of the invention is carried out using following examples, but is not limited to:
The plant bulk of present example is as follows: it is cylindrical body, Φ × H=240 × 347mm that device is answered in crystallization；Membrane separator
Φ × H=120 × 1500mm is equipped with 1 hollow fiber microfiltration membrane component, and nominal pore size is 0.22 μm, and effective area is
0.5m2, intake pump and water outlet pump are elevator pump, and dosing pump and film water outlet pump are peristaltic pump, and water flow is calculated as spinner flowmeter.
Device is programmed using PLC (programmable controller) control, fully automatic operation, PLC using general technology.
Device is daily continuous operation for 24 hours, and wherein crystallization reactor is batch-type Inlet and outlet water, and membrane separator is that interval goes out
Water.
Embodiment 1: using the copper-containing wastewater of above-mentioned apparatus processing 18.9mg/L, which is configured by tap water, wherein
Ca2+: 26.3mg/L；Mg2+: 9.0/L；K+: 3.4mg/L；Na+: 12.4mg/L.The processing water of device is 12.9L/h, and crystallization is anti-
The residence time for answering device is 13 minutes (stir 5 minutes, precipitate 8 minutes), and the hydraulic detention time of membrane separator is 30 minutes.It is real
Before testing starting, 0.1wt% basic copper carbonate crystal seed is added into crystallization reactor, is computed the control of sodium carbonate dosage and is existed
When 104mg/L, SI value is 2.76, and remaining carbon acid ion concentration is 41.1mg/L, and the copper concentration of MAC Process for Effluent is stablized at this time
Stablize in 0.8mg/L or less, turbidity in 0.1NTU, being discharged pH is 7.62 ± 0.1.After handling 1800L water, the product recycled is
0.24ml, i.e., the cycles of concentration of the technique is 7500 with this condition, through SEM and EDS analysis it is found that reaction product is Cu2
(OH)2CO3Crystal (as shown in Figure 2,3, 4), and its Ca, Mg content < 0.4% (table 1), i.e., purity is very high.Membrane specific flux is from initial
57L/ (m2Hm) it is down to 35L/ (m2Hm), can restore after washing to 53L/ (m2Hm), membrane flux restores
92%.
Control group A: it is identical as 1 experimental condition of embodiment, but SI and excess CO3 2-Not in the scope of the invention (SI=
3.39, excessive CO3 2-: 53.3mg/L), concentration for the treatment of is the copper-containing wastewater of 52.2mg/L, at this time the copper concentration of MAC Process for Effluent
Stablize in 0.5mg/L or less, turbidity in 0.1NTU although stablizing, being discharged pH is 8.52 ± 0.1, its recovery product is cotton-shaped heavy
Form sediment rather than crystal (as shown in Figure 2,3, 4), the cycles of concentration of technique are only 148, and its Ca, Mg content be 1.32%, height
In embodiment 1 (table 1).
Control group B: it is identical as 1 experimental condition of embodiment, but SI is not excessive in condition and range of the present invention (SI=3.28)
CO3 2-(35.3mg/L) meets minimum requirements, and concentration for the treatment of is the copper-containing wastewater of 46.8mg/L, and the copper of MAC Process for Effluent is dense at this time
Degree stablize in 1.3mg/L hereinafter, and as the extension of runing time is gradually decrease to 0.80mg/L or so, turbidity, which is stablized, to exist
0.1NTU, water outlet pH are 8.05 ± 0.1, but its recovery product is the mixture (as shown in Figure 2,3, 4) of crystal and flocculent deposit,
It is 2030 that the cycles of concentration of its technique, which is slightly better than control group A, and Ca, Mg content are 0.81%, are higher than embodiment 1 (table 1), slightly good
In control group B.
Embodiment 2: using the copper-containing wastewater of above-mentioned apparatus processing 29.5mg/L, which is configured by tap water, wherein
Ca2+: 33.0mg/L；Mg2+: 8.9mg/L；K+: 3.4mg/L；Na+: 19..4mg/L.The processing water of device is 15L/h, crystallization
The residence time of reactor is 15 minutes (stir 8 minutes, precipitate 15 minutes), and the hydraulic detention time of membrane separator is 40 points
Clock.Before experiment starting, 0.2wt% basic copper carbonate crystal seed is added into crystallization reactor, is computed the control of sodium carbonate dosage
In 115mg/L, SI value is 3.17, and remaining carbon acid ion concentration is 37.8mg/L, and the copper concentration of MAC Process for Effluent is steady at this time
1.295mg/L or less, turbidity stabilization are scheduled in 0.1NTU, being discharged pH is 7.42 ± 0.1, and recovery product is closely knit Cu2(OH)2CO3Crystal grain.
Embodiment 3: using the copper-containing wastewater of above-mentioned apparatus processing 29.5mg/L, which is configured by tap water, wherein
Ca2+: 33.0mg/L；Mg2+: 8.9mg/L；K+: 3.4mg/L；Na+: 19..4mg/L.The processing water of device is 15L/h, crystallization
The residence time of reactor is 15 minutes (stir 8 minutes, precipitate 15 minutes), and the hydraulic detention time of membrane separator is 40 points
Clock.Before experiment starting, 0.2wt% basic copper carbonate crystal seed is added into crystallization reactor, is computed the control of sodium carbonate dosage
In 95mg/L, SI value is 3.12, and remaining carbon acid ion concentration is 31.1mg/L, and the copper concentration of MAC Process for Effluent is steady at this time
1.895mg/L or less, turbidity stabilization are scheduled in 0.1NTU, being discharged pH is 7.32 ± 0.1, and recovery product is closely knit Cu2(OH)2CO3Crystal grain.
Embodiment 4: using the copper-containing wastewater of above-mentioned apparatus processing 23.4mg/L, which is configured by tap water, wherein
Ca2+: 39.3mg/L；Mg2+: 8.1mg/L；K+: 3.9mg/L；Na+: 17.0mg/L.The processing water of device is 15.0L/h, crystallization
The residence time of reactor is 15 minutes (stir 6 minutes, precipitate 10 minutes), and the hydraulic detention time of membrane separator is 35 points
Clock.Before experiment starting, 0.15wt% basic copper carbonate crystal seed is added into crystallization reactor, is computed the control of sodium carbonate dosage
In 115mg/L, SI value is 3.17, and remaining carbon acid ion concentration is 49.5mg/L, and the copper concentration of MAC Process for Effluent is steady at this time
0.5mg/L or less, turbidity stabilization are scheduled in 0.1NTU, being discharged pH is 7.89 ± 0.1, and recovery product is closely knit Cu2(OH)2CO3
Crystal grain.
The pellet fraction of above-described embodiment 1 and two groups of control groups analysis result is as follows:
1 embodiment 1 of table and two groups of group check experiment recovery product element compositions
As Fig. 2,3,4 it is found that using technical parameter defined by the present invention, the recovery product of MAC technique is Cu2(OH)2CO3Crystal (Fig. 4 b), crystal grain grows up to biggish rule particle on the basis of crystal seed (Fig. 4 a), and its purity is greater than
99% (table 1) directly can recycle or continue to serve as the crystal seed of MAC technique.And control group A, control group B, it is especially right
According to group A, due to inappropriate Process operating parameters, its recovery product does not almost increase (Fig. 4 c)；Its sediment of control group B is averaged ruler
Although very little increase, the mixture of crystal and wadding body is presented, if undoubtedly the SI value during its operation is preferably controlled,
It is beneficial to the growth of its crystal.
Claims (6)
1. the method for film assisting crystallisation technique MAC selective removal and the copper in recycle-water, which is characterized in that including walking as follows
It is rapid:
(1) effluent quality according to demand determines two key parameters of process operation: supersaturated index (SI) and excessive carbon
Acid group (CO3 2-)；
(2) dosage of precipitating reagent is calculated:
If it is desired to be discharged Cu2+Concentration reaches the requirement of WHO effluent quality criterion, need to be by excessive CO3 2-Control is in 35-50mg/L model
In enclosing；
It, need to be by excessive CO if effluent quality is needed to reach the requirement of China's " standards for drinking water quality " (GB 5749-2006)3 2-
Control is within the scope of 45-50mg/L；
(3) dosage for combining influent quality and precipitating reagent calculates SI value, and is controlled in crystallization reactor by adjusting into dose
SI value below 3.22；
(4) amount for adding crystal seed, 0.1-0.5wt% are determined, and MAC technique is only needed once to add when starting；
(5) after adding crystal seed, into crystallization reactor, water inlet adds required amount of sodium carbonate simultaneously and carries out to design liquid level
Mechanical stirring, stirring intensity 120-180rpm, mixing time is no less than 5min, the sedimentation time is no less than 8min, the copper in water from
Son just under the induction of basic copper carbonate crystal seed, reacts with sodium carbonate and generates big partial size compact grain object Cu2(OH)2CO3Crystal,
And be deposited to the bottom of crystallization reactor, the supernatant in crystallization reactor go successively to membrane reactor further crystallize, solid-liquid
Separation, to obtain more preferably effluent quality；After crystal runs up to certain volume, i.e., recoverable, crystallization reactor domestic demand are stayed
A part of crystal continues the crystal seed as subsequent reactions, and a certain amount of residue CO is kept in its reactor3 2-。
2. the method according to claim 1, wherein the excessive CO in the step (2)3 2-Refer to it is to be processed
Cu in water2+Concentration is compared, the amount of remaining carbonate, in terms of mg/L.
3. the method according to claim 1, wherein water outlet pH meets GB 5749-2006 in the step (2)
Standard is discharged pH preferred scope between 7-8.
4. the method according to claim 1, wherein SI refers to the component in reactor anti-in the step (3)
Supersaturated index before answering, i.e. crystallization driving force.
5. the method according to claim 1, wherein in the step (4) crystal seed dosage, with the period 1
The stereometer of pending water, i.e. 1.0-5.0g/L.
6. the method according to claim 1, wherein the step (5) realizes automatic running by PLC program.
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