CN102459096A - Method for recovering water and metals from plating wastewater resulting from washing - Google Patents
Method for recovering water and metals from plating wastewater resulting from washing Download PDFInfo
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- CN102459096A CN102459096A CN2010800259247A CN201080025924A CN102459096A CN 102459096 A CN102459096 A CN 102459096A CN 2010800259247 A CN2010800259247 A CN 2010800259247A CN 201080025924 A CN201080025924 A CN 201080025924A CN 102459096 A CN102459096 A CN 102459096A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D9/00—Crystallisation
- B01D9/0036—Crystallisation on to a bed of product crystals; Seeding
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/22—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D21/00—Processes for servicing or operating cells for electrolytic coating
- C25D21/16—Regeneration of process solutions
- C25D21/20—Regeneration of process solutions of rinse-solutions
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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
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/16—Nature of the water, waste water, sewage or sludge to be treated from metallurgical processes, i.e. from the production, refining or treatment of metals, e.g. galvanic wastes
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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
- C02F2209/06—Controlling or monitoring parameters in water treatment pH
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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Abstract
A method for water and metal recovery from a plating wastewater resulting from washing is disclosed with which water and metals are efficiently recovered from the plating wastewater, the method comprising an iron insolubilization step in which the pH of the plating wastewater is regulated to 3-6 in the presence of an oxidizing agent to oxidize divalent iron ions contained in the liquid to trivalent iron ions and precipitate an iron hydroxide, a solid-liquid separation step in which the water treated in the iron insolubilization step is subjected to solid-liquid separation by means of a microfiltration membrane, an ultrafiltration membrane, or a filter, a reverse osmosis membrane separation step in which the water separated in the solid-liquid separation step is treated with a reverse osmosis membrane and the filtrate water is taken as treated water out of the system, and a crystallization step in which an alkali is added to the high-concentration water resulting from the reverse osmosis membrane separation step and the metals contained in the liquid are precipitated as carbonates by a crystallization method in which acid-insoluble particles are used as seed crystals.
Description
Technical field
The present invention relates to a kind of from the plating Cleaning Wastewater method of efficient recovery water and valuable metal, particularly relate to a kind of valuable metal two sides such as efficient recovery water and nickel, zinc from the Cleaning Wastewater of electroplating work procedure and it can be utilized again and reduce the method for mud growing amount through wastewater treatment.
Background technology
The plating Cleaning Wastewater of being discharged from the plating workshop, pH is 2～3 usually, and as a rule, except that containing ferrous iron, also contains valuable metals such as nickel, zinc, chromium, copper, therefore, hopes to reclaim these metals to utilize again.
Such as in the patent documentation 1 record, as the treatment process of plating Cleaning Wastewater, in usually adopting and coagulant sedimentation (hydroxide precipitation method) in the past.This method is with the pH regulator alkalize of waste water and through metals ion is precipitated to separate removal as oxyhydroxide.In the method, when reclaiming the valuable metal of so-called nickel or zinc,, can take to carry out the method for coagulating sedimentation through changing the pH condition in order to reclaim through they are separated with iron.That is following method: in pH3～6, in the presence of oxygenant etc., with Fe
2+Be oxidized to Fe
3+After, make it precipitate removal, then precipitate and separate nickel, zinc in pH7～10 as oxyhydroxide.Further, when recycle-water, behind precipitate and separate nickel, zinc, in conjunction with solid-liquid separation or the processing of reverse osmosis (RO) film such as the filtration of the next further execution of the water quality requirement of recycle-water sand, ultrafiltration.
In addition, as the facture of metallic waste water, sulphide precipitation, ion exchange method, resin method, membrane separation process etc. are arranged.
Sulphide precipitation is to make metal as sulfide sedimentary method take place through adding sodium sulphite.In the method, because compare the solubility product constant of metallic sulfide with hydroxide precipitation method low, so, can under lower concentration, handle metal species from the viewpoint of wastewater treatment.
Such as in the patent documentation 2 record, ion exchange method is through making the adsorption of metal ions method to remove on ion exchange resin in the waste water, just can remove metals ion reliably as long as in the loading capacity scope of ion exchange resin, use.
The resin method be through use to special metal selectively resin adsorb the method for removing metal.Though can remove metals ion reliably equally with ion exchange resin, resin has selectivity to metal, the metal that can adsorb removal is by specialization.
Membrane separation process is the method that removes metals ion through the use reverse osmosis membrane, and it can obtain good water quality treatment.
But, in the above-mentioned any means, when recycle-water and valuable metal from metallic waste water, have the problem that is described below respectively.
I) in and coagulant sedimentation
The formed throw out of oxyhydroxide is fine and the separation property in settling tank unstable, therefore, for steady running, needs deposition auxiliarys such as high-molecular coagulant adopting.In addition, the oxyhydroxide moisture percentage in sewage sludge is about 70～80%, can become problem to the processing of a large amount of mud of being generated.
And, in the method for iron and nickel or zinc are carried out Separation and Recovery, need will in the time pH be set as two ranks, therefore need settling tank be set as two ranks and need the big space that is provided with.
And when level was carried out the processing of RO (reverse osmosis) film with recycle-water in the back, ion increased along with neutralizing treatment, thereby the load of the ion on reverse osmosis membrane increases.
Ii) sulphide precipitation
The solubility product constant of sulfide is low, can reduce concentration of metal ions, but the throw out of sulfide is fine, so precipitate and separate property is poor.And sulfide produces hydrogen sulfide under acidic conditions, therefore has safety issue.
Iii) ion exchange method
Ion exchange resin almost adsorbs all ions, and is therefore big to the ionic adsorption amount beyond the metals ion in wastewater treatment, with remove metals ion as the situation of target under inefficiency.And in this case, also these contained ions are in the blended state in a large amount of regenerative agents of needs and the regenerated liquid, therefore are difficult to reclaim valuable metal.
Iv) resin method
Compare with ion exchange resin, the resin method is high to the selectivity of metals ion, but should be noted that the trace change of coexisting ion.In addition, when manipulation of regeneration, using sulfuric acid, hydrochloric acid usually, still, if residual in the regenerated liquid have the concentration of metal ions of a large amount of acid and recovery liquid to reach at the most about 2～3 weight %, is low as far as utilizing this concentration more then.
V) membrane separation process
Through using reverse osmosis membrane can obtain good water quality treatment, can only reach about 10 times in the waste water but in the RO condensed water, obtain spissated metals ion (concentration), therefore be not suitable for single reverse osmosis membrane that relies on and carry out metal recovery.
The prior art document
Patent documentation
Patent documentation 1: TOHKEMY 2002-192168 communique
Patent documentation 2: TOHKEMY 2004-107780 communique
Summary of the invention
The problem that invention will solve
The objective of the invention is to, provide a kind of from the plating Cleaning Wastewater method of efficient recovery water and metal to solve the above-mentioned problem that existed in the past.
Solve the method for problem
The recycle-water from the plating Cleaning Wastewater of first mode and the method for metal; It is characterized in that; Comprise following operation: in the presence of oxygenant, regulate the plating Cleaning Wastewater and be pH3～6 and make oxidation of divalent iron ion in the liquid become ferric ion and the iron of separating out ironic hydroxide does not dissolve the chemical industry preface; The treating water that this iron is not dissolved the chemical industry preface carries out the solid-liquid separation process of solid-liquid separation through secondary filter film, ultra-filtration membrane or strainer; With in this solid-liquid separation process the dried up reverse osmosis membrane separation circuit that carries out the reverse osmosis membrane separating treatment and permeate water is discharged outside system as treating water of isolating branch; And, through in the condensed water of this reverse osmosis membrane separation circuit, adding alkali and separating out operation as the crystallization that the crystallization liberation method of crystal seed makes the metal in the liquid separate out as carbonate with sour insoluble particle.
The recycle-water from the plating Cleaning Wastewater of second mode and the method for metal; It is characterized in that; Aforementioned crystallization in first mode is separated out in the operation; Also comprise the metal recovery operation, the metal carbonate that said metal recovery operation is separated out through making on the crystal seed is dissolved in and obtains metal salt solution in the acid.
The recycle-water from the plating Cleaning Wastewater of Third Way and the method for metal is characterized in that, resulting metal salt solution in the aforementioned metal recovery process of second mode is utilized as plating solution again.
The recycle-water from the plating Cleaning Wastewater of cubic formula and the method for metal is characterized in that, in first arbitrary mode to the Third Way, the treating water that operation is separated out in aforementioned crystallization is sent aforementioned iron back to and do not dissolved in the chemical industry preface and handle.
The effect of invention
Based on the present invention can be from the plating Cleaning Wastewater efficient recovery water and metal.
That is, at first do not dissolve and make iron in the chemical industry preface as ironic hydroxide (Fe (OH) at iron
3) separate out, this is separated removal in solid-liquid separation process.This solid-liquid separation is carried out through secondary filter (MF) film, ultrafiltration (UF) film or strainer, so solid-liquid separation property is good.Separate out at iron and to be adjusted to pH3～6 in the operation, therefore, though ironic hydroxide is separated out, metals ions such as nickel, zinc are in dissolved state.Therefore, from solid-liquid separation process, the branch that obtains to contain above-mentioned dissolved metal ions is dried up.
In the present invention, this solid-liquid separation water is at first carried out the reverse osmosis membrane separating treatment, concentrate.The reverse osmosis membrane permeate water has the good water quality same with pure water, can perhaps be used based on other point of view of application through discharging outside system as treating water and utilizing as the plating water for cleaning again.
In the RO condensed water, obtain metals ions such as spissated nickel, zinc, separate out processing, on crystal seed, separate out as metal carbonate through proceeding crystallization.If adopt the crystallization liberation method, then can metal be reclaimed as the good metal carbonate particles of dehydration property.In addition, in the crystallization liberation method, need be such as settling tank or the dehydration equipment in neutralization precipitation method etc.
In addition, though can make nickel or zinc form undissolved oxyhydroxide, oxyhydroxide can produce the high throw out of water ratio that contains moisture, therefore inapplicable crystallization liberation method.
In second mode, as the crystal seed of this crystallization liberation method, used sour insoluble particle, therefore, the metal carbonate of separating out through making on the crystal seed is dissolved in the acid, can be easy to reclaim as metal salt solution.Based on Third Way, can this metal salt solution be utilized as plating solution again, and can the crystal seed that reclaim be used in crystallization again and separate out in the operation.
Separate out in the treating water of operation in crystallization, even residual have as metals ion that reclaims target and the dissolving fine metal of catching on crystal seed also at large not.In cubic formula, send iron back to and do not dissolve the chemical industry preface and handle once more through this crystallization being separated out treating water, can improve the metal recovery rate and the water recovery.
As stated, based on the present invention, can be from the plating Cleaning Wastewater efficient recovery water and valuable metal.And, separate out the series of processes combination that operation is separated out in operation, solid-liquid separation process, reverse osmosis membrane separation circuit and crystallization through iron, can reduce and handle wastewater flow rate and discharge amount of metal, therefore can reduce last mud growing amount significantly.
Description of drawings
Fig. 1 be expression of the present invention from the plating Cleaning Wastewater system diagram of the embodiment of the method for recycle-water and metal.
Fig. 2 is the system diagram that the structure of device is separated out in the expression crystallization.
Fig. 3 is the system diagram of the structure of the sour contact device of expression.
Embodiment
Below, through with reference to accompanying drawing, specify of the present invention from the plating Cleaning Wastewater embodiment of the method for recycle-water and metal.
Fig. 1 be expression of the present invention from the plating Cleaning Wastewater system diagram of the embodiment of the method for recycle-water and metal, Fig. 2 is the system diagram that the structure of device is separated out in the expression crystallization, Fig. 3 is a system diagram of representing the structure of sour contact device.
In the present invention, at first will import as the plating Cleaning Wastewater of former water in the coagulation oxidation trough 1, interpolation oxygenant (being Youxiaolin (NaClO) among Fig. 1), pH regulator agent (being the caustic soda (NaOH) as alkaline agent among Fig. 1), coagulating agent (are iron(ic)chloride (FeCl among Fig. 1
3)), through in pH3～6 with the ferrous iron (Fe in the liquid
2+) be oxidized to ferric iron (Fe
3+) separate out ironic hydroxide (Fe (OH)
3).
Do not dissolve in the chemical industry preface at above-mentioned iron,, except that NaClO, can also use hydrogen peroxide or potassium permanganate, chlorine, ozone etc. as oxygenant.The addition of oxygenant is as long as reach the Fe that makes in the liquid
2+Be oxidized to Fe
3+Used equivalent is above to get final product.
The plating Cleaning Wastewater is generally the acidity that is lower than pH3 (for example about pH2), but in order to separate out Fe (OH)
3Need be adjusted to more than the pH3, therefore through adding NaOH, Ca (OH) as the pH regulator agent
2Regulate pH in alkali.Wherein, though be to regulate according to the concentration situation in the waste water, if nickel or zinc that pH surpasses in 7 liquid are separated out, therefore regulating pH is 3～7, preferably is adjusted to 5～6.
Do not dissolve in the chemical industry preface at above-mentioned iron, the interpolation of coagulating agent is not essential, but in order to improve Fe (OH)
3The precipitation threshold of throw out can be added FeCl
3In coagulating agent.Through adding FeCl
3In coagulating agent, improved not dissolving particulate precipitation threshold, in the precipitate and separate efficient after lifting in the settling bath 2 of level, also increased the throw out diameter, therefore, the filterableness after also can improving in the UF film device 3 of level.And, thereby the organism generation coagulation from make the plating Cleaning Wastewater reduce the back level reverse osmosis membrane device 6 load and prevent that the angle of the pollution of reverse osmosis membrane from considering, also preferably add coagulating agent.FeCl
3Addition be made as 10～200mg/L usually, preferably be made as about 100～150mg/L.
In coagulation oxidation trough 1, make Fe (OH)
3The liquid that throw out is separated out then carries out solid-liquid separation with MF film, UF film or strainer (for example, sand filter), but is to use MF film device (MF membrane separation unit) 3 to carry out membrane filtration then carrying out solid-liquid separation with settling bath 2 before this in the method for Fig. 1.This settling bath 2 is not essential, but passes through precipitate and separate Fe (OH) in settling bath 2 in advance
3Thick throw out, can alleviate the load of back level UF film device 3 grades, and can reduce backwash frequency, realize high-throughput.
The separated sludge of settling bath 2 is discharged outside system, parting liquid is passed through pump P
AImport in the UF film device 3 and carry out membrane filtration.This UF film device 3 is carried out regular backwash, with the Fe that holds back (OH)
3Mud is discharged outside system with backwash waste.
With the filtered water of UF film device 3, handle tank 4 through UF and import regulating tank 5, in regulating tank 5, regulate water quality.That is, in reverse osmosis membrane device (reverse osmosis membrane tripping device) 6, handle before the filtered water of UF film device 3,, in UF membrane filtration water, add sodium sulfite anhy 96 (NaHSO in order to protect reverse osmosis membrane
3), S-WAT (Na
2SO
4) wait reductive agent; Perhaps, remove residual oxygenant through the contact gac, and; So that the mode that the oxyhydroxide that concentrating in reverse osmosis membrane device 6 can not make metals such as nickel, zinc is separated out; Add the pH regulator agent as required, making the pH regulator of supplying with the water (RO supplies with water) in the reverse osmosis membrane device 6 thus is 4～6, preferably is adjusted to 4～5.
The amount of the reductive agent that in UF membrane filtration water, adds is made as more than the equivalent of residual oxygenant usually, sets excessive 5～20mg/L, preferably sets excessive 10～15mg/L.
Will be in regulating tank 5 the adjusted water of water quality, through pump P
BImport in the reverse osmosis membrane device 6, carry out membrane sepn and be treated to permeate water (RO permeate water) and condensed water (RO condensed water).A part of condensed water is flowed to RO concentrate in the tank 7, and remainder is carried out circular treatment.
Processing in this reverse osmosis membrane device 6 is that 5～10 times, the water recovery are that 80～90% mode is carried out according to concentration rate, but preferably in running, does not break down and carry out with the mode that height concentrating metals ion improves the water recovery.
The RO permeate water that is obtained in the reverse osmosis membrane device 6 has the good water quality with the pure water same degree, therefore, can it be utilized as the plating water for cleaning again.And this RO permeate water can also be used based on other point of view of application.
With the metals ion in the RO condensed water, be condensed into 5～10 times of concentration of metal ions in the plating Cleaning Wastewater, concentrate tank 7 through RO, this RO condensed water is imported crystallization separate out in the device 8 and separate out processing to carry out crystallization.
Separate out device 8 as crystallization; As long as can promote separating out of metal carbonate, not special restriction, but can preferably use tower reactor drum for example shown in Figure 2; Wherein, In crystallization evolution reaction tower 10, fill crystal seed,, in tower, form the fluidised bed of crystal seed from the bottom circulation RO condensed water of tower.
In the device of Fig. 2, former water is separated out in crystallization, pass through pump P through pipeline 11
1Circulate from the bottom of reaction tower 10, treating water is flowed out the back through pipeline 12 import in the processing tank 9.With a part of treating water, pass through circulating line 14 and recycle pump P from the top of tower
2Handle the bottom that is circulated to tower.
From the top of crystallization evolution reaction tower 13, inject yellow soda ash (Na
2CO
3) or sodium hydrogencarbonate (NaHCO
3) with the basic carbonates such as mixed solution of caustic soda (NaOH).In tower on the mobile crystal seed, through make yellow soda ash and metals ion react (for example following reaction) come the carbonate of precipitating metal.
Ni
2++ Na
2CO
3→ NiCO
3(separating out)+2Na
+
Zn
2++ Na
2CO
3→ ZnCO
3(separating out)+2Na
+
In addition,, be necessary to improve pH to 7～10 that former water is separated out in crystallization, preferably bring up to 8～9 and carry out separating out of this metal carbonate.Therefore, the amount of the basic carbonate that in crystallization evolution reaction tower 10, is injected is to form the necessary amount of metal carbonate, and is set at and makes crystallization separate out the amount that liquid pH in the tower becomes above-mentioned pH.If this pH is lower than 7 carbonate and does not produce and separate out, if this pH surpass 10 then zinc carbonate be easy to take place dissolving again.
Separating out in the operation in above-mentioned crystallization needs to improve pH, but in the present invention, before operation is separated out in crystallization, concentrates through the reverse osmosis membrane separating treatment, reduces and finishes the water yield that partial crystallization goes out process object, therefore can reduce and regulate the necessary amount of medicament of pH.
Among the present invention, used as crystal seed dissolved acid insoluble particle has not taken place under s.t. in the metal recovery operation of back level.As sour insoluble particle, can use sand (silica sand), hard coal etc.The particle diameter of crystal seed is 0.1～1mm, is preferably about 0.2～0.4mm especially.
The metals ion in the former water is separated out in crystallization, and separate out through crystallization and handle to form metal carbonate, thus dissolving and on seed surface, separating out not.Through separating out of metal carbonate, the seed particles growth, particle diameter increases to 0.3～1.5mm.The particle that increases separated out the device from crystallization take out, flow to the metal recovery operation.
Crystallization being separated out the treating water importing crystallization of device 8 separates out in the processing tank 9.
In the crystallization liberation method, according to the difference of operational condition, the recovery of metals ion is variant, but is 70～90% as a rule, is generally about 80%.Therefore, preferably treating water being separated out in this crystallization of a part sends iron back to and does not dissolve in the chemical industry preface and carry out circular treatment with the plating Cleaning Wastewater as former water.Thus, can handle the metals ion reclaim and carry out periodic crystallisation and separate out processing to separating out, thereby improve whole metal recovery rate through primary crystallization.
In the present invention; Preferably handle with following condition: the ratio that treating water is separated out in the crystallization of this circular treatment is set at crystallization and separates out and handle 10～80% of the water that imported in the tank 9; Make the water recovery on the whole become 70～90%, and metal recovery rate become about 80～95%.
Separate out in the device 8 in crystallization; Make with the insoluble crystal seed of acid and contact with acid such as sulfuric acid, hydrochloric acid as the particle that nuclear is attached with the metal carbonate of nickel, zinc etc.; Then dissolving again takes place in the metal carbonate of nickel, zinc etc., obtains the vitriol of these metals or the highly concentrated solution of chloride salt.In the processing of electroplating Cleaning Wastewater, can be with directly in bath, utilizing again through the high density metal sulfate aqueous solution that operation like this obtained.And the particle through making above-mentioned recovery contacts with acid and behind the dissolution of metals carbonate, and residual have a sour insoluble seed particles, and this seed particles can be separated out device through crystallization and utilize as crystal seed once more.Particle diameter management through utilizing seed particles, crystallization to separate out in the device so again becomes easy.
Therefore, preferably regularly separate out to take out the device 8 and separate out the seed particles that metal carbonate is arranged from the teeth outwards, handle with acid then and reclaim metal salt solution and crystal seed more respectively from crystallization.
The device that contacts as the particle (particle that metal carbonate is separated out on seed surface) that crystallization is separated out taken out in the device 8 and acid; As long as can both be contacted; Not special restriction for example, can be used sour contact device as shown in Figure 3.
This acid contact device has sour contact tower 20; In said sour contact tower 20, pack into and separate out the taking-up particle of device 8 from crystallization; Bottom in this tower is provided with water collection sheet (porous plate or mesh), and said water collection sheet has only moisture to see through and particle can not see through.When processing is separated out the taking-up particle of device 8 from crystallization, open valve V
1, V
2And close other valve, and will take out then in particle packs sour contact tower 20 into from pipeline 21, moisture is taken out from pipeline 23,24.Sending this moisture back to crystallization separates out in the processing tank 9.Then, open valve V
3, V
4And close other valve, then, use pump P
3Through the acid such as bottom circulation sulfuric acid of piping 25,23 by sour contact tower 20, come in contact through making acid and particle, make the metal carbonate dissolving of seed surface.Contain metal carbonate dissolved metal ion solution through pipeline 26 taking-ups.As this metal salt solution, can obtain metals ion usually is the highly concentrated solution about 5～15 weight %, and therefore preferably this metal salt solution utilizes as plating solution again.
After the metal carbonate that makes seed surface dissolves, open valve V
2, V
5And close other valve, use then pump (not shown) with the high flow rate mode through pipeline 24,23 and from the bottom of sour contact tower 20 circulation water, with crystal seed through valve V
5Sending crystallization back to separates out device 8 and utilizes.
In addition, as the acid that is used to dissolve the metal carbonate on the crystal seed, be preferably the high-concentration sulfuric acid aqueous solution about 50～98 weight %, perhaps the aqueous hydrochloric acid of 20～35 weight %.
In hydroxide precipitation method in the past, also can make not dissolving of metals ion, and be used in the bath again after it is dissolved again, but separate out processing through as the present invention, carrying out crystallization, need not settling tank or water extracter.And, can obtain particle diameter bigger remove the good particle of water-based, therefore, can use such as sour contact device shown in Figure 3, through easily dewater, dissolved operation again, can reclaim the metal salt solution of high density.
Through carrying out aforesaid operations, reduced wastewater flow rate, discharged amount of metal and reduced the mud growing amount of system in its entirety significantly based on the present invention, thus recycle-water and valuable metal from the plating Cleaning Wastewater effectively.
Embodiment
Below, through combining embodiment the present invention is described more specifically.
Embodiment 1
Adopt method shown in Figure 1 from the plating Cleaning Wastewater, to reclaim water and metal.
At first, in coagulation oxidation trough 1, the plating Cleaning Wastewater is added the 5mg/L Youxiaolin, make contained Fe in the waste liquid
2+Be oxidized to Fe
3+, and use caustic soda to be adjusted to pH5, make Fe
3+Form the not ironic hydroxide Fe (OH) of dissolving
3, and change Fe (OH) in order to increase not dissolve
3Particle diameter, add 100mg/L iron(ic)chloride (FeCl
3) carry out coagulating treatment.
The treatment solution of coagulation oxidation trough 1 is imported in the settling bath 2, more than half part of the throw out that generates is carried out precipitate and separate, the parting liquid with 3 pairs of settling baths 2 of UF film device carries out membrane filtration then.This UF film device 3 is carried out regular backwash.
Filtered water with UF film device 3; Handle tank 4 through UF and import in the regulating tank 5, and add the 15mg/L sodium sulfite anhy 96 to remove residual chlorine, then; Supply with reverse osmosis membrane device 6 (RO supplies with water); Reclaim the RO permeate water, and, the RO condensed water is concentrated tank 7 through RO flow to crystallization and separate out device 8 and separate out processing to carry out crystallization.The water recovery of this reverse osmosis membrane device 6 is 80%.
It is to be that sand about 0.2mm is processed through being filled with particle diameter in the crystallization evolution reaction tower 10 as shown in Figure 2 that device 8 is separated out in crystallization; Circulation RO condensed water to be forming the thermopnore of sand from the bottom of crystallization evolution reaction tower 10, and in thermopnore, adds yellow soda ash (Na
2CO
3) be 9 with the pH that regulates in the thermopnore.Separate out in the processing tank 9 in crystallization, treating water is separated out in the crystallization that reception is separated out device 8 from this crystallization.
The water quality of each operation in this processing is shown in Table 1.
Table 1
Can be clearly as follows according to table 1.
Through not dissolving processing of iron, make iron that not dissolving reaction take place and be removed, and reach RO supply with the detection of water stage less than level.In addition, before reverse osmosis membrane device 6, nickel, zinc nearly all are in dissolved state and not dissolving do not take place.In RO condensed water one side directly with dissolved state by spissated nickel, zinc, separate out to handle through crystallization and be removed about 80% (metal recovery rate is 80%).At this moment, on the surface of the sand of packing into, there are nickel, zinc to separate out as crystal seed, and the increase of visible crystal seed particle diameter.
UF backwash waste, crystallization are separated out treating water and are used as the waste water discharge, and therefore, the water recovery that goes up as a whole reaches 75%.
Embodiment 2
In embodiment 1, particle diameter increases to the crystal seed about 0.3～0.4mm to separate out processing through crystallization, imports in the sour contact tower 20 shown in Figure 3, and after dewatering 10 minutes, injects 50 weight % aqueous sulfuric acids from the tower bottom.The particulate water ratio that removed the stage of water is 10 weight %.Through inject sulfuric acid from the tower bottom, the nickel, the zinc that on seed surface, adhere to dissolve, and obtain the sulfate liquor of nickel, zinc from tower top.The nickel of this solution, zinc concentration are respectively 1.5 weight %, 17 weight %.This result is that nickel, the zinc of the plating Cleaning Wastewater in the former water is concentrated into 600 times, 577 times respectively.
Except 90% crystallization being separated out inlet side that treating water sends coagulation oxidation trough 1 back to the plating Cleaning Wastewater is handled, likewise operate with embodiment 1.In the present embodiment; Metal recovery rate after processing is once separated out in crystallization does not change, and is 80%, but sends back to handle once more through crystallization being separated out treating water; Make thus to obtain crystallization repeatedly and separate out processing, metal recovery rate has on the whole been brought up to 98%.And, the water recovery has been brought up to 92%.
Through using specific mode to specify the present invention, but to those skilled in the art, can clearly in not exceeding aim of the present invention and scope, can carry out various changes.
In addition, please be to make in this according to the japanese application that proposed on June 11st, 2009 (the special 2009-140335 of hope of Japan), here cite its whole content.
Claims (6)
1. the method for recycle-water and metal from a plating Cleaning Wastewater is characterized in that, comprises following operation:
In the presence of oxygenant, regulate the plating Cleaning Wastewater and be pH3～6 and make oxidation of divalent iron ion in the liquid become ferric ion and the iron of separating out ironic hydroxide does not dissolve the chemical industry preface,
The treating water that this iron is not dissolved the chemical industry preface carries out the solid-liquid separation process of solid-liquid separation through secondary filter film, ultra-filtration membrane or strainer,
With in this solid-liquid separation process the dried up reverse osmosis membrane separation circuit that carries out the reverse osmosis membrane separating treatment and permeate water is discharged outside system as treating water of isolating branch, and
Through in the condensed water of reverse osmosis membrane separation circuit, adding alkali and separating out operation as the crystallization that the crystallization liberation method of crystal seed makes the metal in the liquid separate out as carbonate with sour insoluble particle.
2. as claimed in claim 1 from the plating Cleaning Wastewater method of recycle-water and metal; It is characterized in that; Separate out in said crystallization and also to comprise the metal recovery operation in the operation, the metal carbonate that said metal recovery operation is separated out through making on the crystal seed is dissolved in and obtains metal salt solution in the acid.
3. as claimed in claim 2 from the plating Cleaning Wastewater method of recycle-water and metal, it is characterized in that, resulting metal salt solution in the said metal recovery operation is utilized as plating solution again.
4. as claimed in claim 2 from the plating Cleaning Wastewater method of recycle-water and metal, it is characterized in that, from said metal recovery operation, reclaim crystal seed and separate out in the operation and utilize again in crystallization.
5. as claimed in claim 2 from the plating Cleaning Wastewater method of recycle-water and metal, it is characterized in that said acid is aqueous sulfuric acid or aqueous hydrochloric acid.
As in the claim 1 to 5 each described from the plating Cleaning Wastewater method of recycle-water and metal, it is characterized in that the partially disposed water that operation is separated out in said crystallization is sent said iron back to and do not dissolved in the chemical industry preface and handle.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2009140335A JP5471054B2 (en) | 2009-06-11 | 2009-06-11 | Methods for recovering water and metals from plating cleaning wastewater |
| JP2009-140335 | 2009-06-11 | ||
| PCT/JP2010/059680 WO2010143623A1 (en) | 2009-06-11 | 2010-06-08 | Method for recovering water and metals from plating wastewater resulting from washing |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102459096A true CN102459096A (en) | 2012-05-16 |
| CN102459096B CN102459096B (en) | 2014-06-18 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201080025924.7A Expired - Fee Related CN102459096B (en) | 2009-06-11 | 2010-06-08 | Method for recovering water and metals from plating wastewater resulting from washing |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP5471054B2 (en) |
| CN (1) | CN102459096B (en) |
| WO (1) | WO2010143623A1 (en) |
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Also Published As
| Publication number | Publication date |
|---|---|
| CN102459096B (en) | 2014-06-18 |
| WO2010143623A1 (en) | 2010-12-16 |
| JP2010284593A (en) | 2010-12-24 |
| JP5471054B2 (en) | 2014-04-16 |
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Address after: Tokyo, Japan Co-patentee after: NIPPON STEEL & SUMITOMO METAL Corp. Patentee after: KURITA WATER INDUSTRIES Ltd. Address before: Tokyo, Japan Co-patentee before: NIPPON STEEL & SUMITOMO METAL Corp. Patentee before: KURITA WATER INDUSTRIES Ltd. Address after: Tokyo, Japan Co-patentee after: NIPPON STEEL & SUMITOMO METAL Corp. Patentee after: KURITA WATER INDUSTRIES Ltd. Address before: Tokyo, Japan Co-patentee before: NIPPON STEEL Corp. Patentee before: KURITA WATER INDUSTRIES Ltd. |
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