CN102459096B - 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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- CN102459096B CN102459096B CN201080025924.7A CN201080025924A CN102459096B CN 102459096 B CN102459096 B CN 102459096B CN 201080025924 A CN201080025924 A CN 201080025924A CN 102459096 B CN102459096 B CN 102459096B
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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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
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 plating Cleaning Wastewater the method for 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 make it recycling and reduce the method for sludge creation amount by wastewater treatment.
Background technology
The plating Cleaning Wastewater of discharging from plating workshop, pH is 2～3 conventionally, and as a rule, also contains the valuable metals such as nickel, zinc, chromium, copper except containing ferrous iron, therefore, wishes to reclaim these metals to recycle.
As described in Patent Document 1, as the treatment process of plating Cleaning Wastewater, in conventionally adopting and coagulant sedimentation (hydroxide precipitation method) in the past.The method is using the pH regulator alkalize of waste water and by making metal ion precipitate to separate removal as oxyhydroxide.In the method, in the time reclaiming the valuable metal of so-called nickel or zinc, for by making them separate to reclaim with iron, can take to be undertaken by changing pH condition the method for coagulating sedimentation., following method: in pH3～6, under the existence of oxygenant etc., by Fe
2+be oxidized to Fe
3+after, make it precipitate removal as oxyhydroxide, then precipitate and separate nickel, zinc in pH7～10.Further, in the time of recycle-water, after precipitate and separate nickel, zinc, further implement solid-liquid separation or the processing of reverse osmosis (RO) film such as sand filtration, ultrafiltration in conjunction with the water quality requirement of recycle-water.
In addition,, as the facture of metallic waste water, there are sulphide precipitation, ion exchange method, resin method, membrane separation process etc.
Sulphide precipitation is to make metal that the method for precipitation occur as sulfide by adding sodium sulphite.In the method, because the solubility product constant of metallic sulfide compared with hydroxide precipitation method is low, so from the viewpoint of wastewater treatment, can process metal species under lower concentration.
As described in Patent Document 2, ion exchange method is by making the adsorption of metal ions method to remove on ion exchange resin in waste water, as long as use and just can remove reliably metal ion within the scope of the loading capacity of ion exchange resin.
Resin method be by use to special metal selectively resin carry out the method for Adsorption metal.Although can remove reliably metal ion same with ion exchange resin, resin is selective to metal implement, and metal that can Adsorption is by specialization.
Membrane separation process is that it can obtain good water quality treatment by using reverse osmosis membrane to remove the method for metal ion.
But, in above-mentioned any means, in the time of recycle-water from metallic waste water and valuable metal, there is respectively problem as described below.
I) in and coagulant sedimentation
The throw out separation property fine and in settling tank that hydroxides forms is unstable, therefore, for steady running, needs the precipitation auxiliarys such as high-molecular coagulant adopting.In addition, oxyhydroxide moisture percentage in sewage sludge is 70～80% left and right, can become problem to the processing of generated a large amount of mud.
And, in the method for iron and nickel or zinc are carried out to Separation and Recovery, need to by and time pH be set as two ranks, therefore need by settling tank be set as two ranks and needs large space is set.
And in the time that rear class is carried out the processing of RO (reverse osmosis) film with recycle-water, ion increases 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, and therefore precipitate and separate is poor.And sulfide produces hydrogen sulfide under acidic conditions, therefore there is safety issue.
Iii) ion exchange method
Ion exchange resin almost adsorbs all ions, therefore large to the ionic adsorption amount beyond metal ion in wastewater treatment, in inefficiency to remove metal ion as target in the situation that.And, in this case, also need the state of these ions contained in a large amount of regenerative agents and regenerated liquid in mixing, be therefore difficult to reclaim valuable metal.
Iv) resin method
With Ion Exchange Resin Phase ratio, resin method is high to the selectivity of metal ion, but should be noted that the trace variation of coexisting ion.In addition, conventionally using sulfuric acid, hydrochloric acid in the time of manipulation of regeneration, still, reach at the most 2～3 % by weight left and right if remain the concentration of metal ions of a large amount of acid and recovery liquid in regenerated liquid, is low for this concentration of recycling.
V) membrane separation process
By using reverse osmosis membrane can obtain good water quality treatment, can only reach 10 times of left and right in waste water but obtain concentrated metal ion (concentration) in RO condensed water, be therefore not suitable for single reverse osmosis membrane that relies on and carry out metal recovery.
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 object of the invention is to, provide a kind of from plating Cleaning Wastewater the method for efficient recovery water and metal to solve the above-mentioned problem existing in the past.
Solve the method for problem
The recycle-water from plating Cleaning Wastewater of first method and the method for metal, it is characterized in that, comprise following operation: under the existence of oxygenant, regulating plating Cleaning Wastewater is that pH3～6 make oxidation of divalent iron ion in liquid become ferric ion and the iron of separating out ironic hydroxide does not dissolve chemical industry order, the processing water that this iron is not dissolved to chemical industry order is by secondary filter film, ultra-filtration membrane or strainer carry out the solid-liquid separation process of solid-liquid separation, the Separation of Water separating in this solid-liquid separation process is carried out to reverse osmosis membrane separating treatment and will see through water as process the water reverse osmosis membrane separation circuit of discharging outside system, and, the crystallization operation that metal in liquid is separated out by add alkali and the powders using crystallization method using sour insoluble particle as crystal seed in the condensed water of this reverse osmosis membrane separation circuit as carbonate.
The recycle-water from plating Cleaning Wastewater of second method and the method for metal, it is characterized in that, in the aforementioned crystallization operation of first method, also comprise metal recovery operation, described metal recovery operation is dissolved in and in acid, is obtained metal salt solution by the metal carbonate that makes to separate out on crystal seed.
The recycle-water from plating Cleaning Wastewater of Third Way and the method for metal, is characterized in that, the metal salt solution obtaining in the aforementioned metal recovery process of second method is recycled as plating solution.
The recycle-water from plating Cleaning Wastewater of cubic formula and the method for metal, is characterized in that,, to the either type in Third Way, sends the processing water of aforementioned crystallization operation back to aforementioned iron and do not dissolve in chemical industry order and process first.
The effect of invention
Based on the present invention can be from plating Cleaning Wastewater efficient recovery water and metal.
, first do not dissolve in chemical industry order and make iron as ironic hydroxide (Fe (OH) at iron
3) separate out, this is separated in solid-liquid separation process to removal.This solid-liquid separation is undertaken by secondary filter (MF) film, ultrafiltration (UF) film or strainer, and therefore solid-liquid separation is good.Separate out in operation and be adjusted to pH3～6 at iron, therefore, although ironic hydroxide is separated out, the metal ions such as nickel, zinc are in dissolved state.Therefore,, from solid-liquid separation process, obtain the Separation of Water that contains above-mentioned dissolved metal ions.
In the present invention, first this solid-liquid separation water carried out to reverse osmosis membrane separating treatment, concentrate.Reverse osmosis membrane sees through glassware for drinking water the good water quality same with pure water, can be by discharging outside system and recycle as plating water for cleaning as processing water, or angle based on other application is set out and is used.
In RO condensed water, obtain the concentrated metal ion such as nickel, zinc, by proceeding crystallization processing, separate out on crystal seed as metal carbonate.If employing powders using crystallization method, metal carbonate particles that can be good using metal as dehydration property reclaims.In addition, in powders using crystallization method, need to be such as settling tank or the dehydration equipment in neutralization precipitation method etc.
In addition,, although can make nickel or zinc form undissolved oxyhydroxide, oxyhydroxide can produce the high throw out of water ratio that contains moisture, therefore inapplicable powders using crystallization method.
In second method, as the crystal seed of this powders using crystallization method, use sour insoluble particle, therefore, be dissolved in acid by the metal carbonate that makes to separate out on crystal seed, can be easy to reclaim as metal salt solution.Based on Third Way, this metal salt solution can be recycled as plating solution, and the crystal seed of recovery can be recycled in crystallization operation.
In the processing water of crystallization operation, even if remain as the metal ion and the also fine metal of catching on crystal seed at large of dissolving not that reclaim target.In cubic formula, send iron back to and do not dissolve chemical industry order and again process by this crystallization being processed to water, can improve metal recovery rate and the water rate of recovery.
As mentioned above, based on the present invention, can be from plating Cleaning Wastewater efficient recovery water and valuable metal.And the series of processes combination of separating out operation, solid-liquid separation process, reverse osmosis membrane separation circuit and crystallization operation by iron, can reduce and process wastewater flow rate and discharge amount of metal, therefore can significantly reduce last sludge creation amount.
Accompanying drawing explanation
Fig. 1 be represent of the present invention from plating Cleaning Wastewater the system diagram of the embodiment of the method for recycle-water and metal.
Fig. 2 is the system diagram that represents the structure of crystallization device.
Fig. 3 is the system diagram that represents the structure of sour contact device.
Embodiment
Below, by with reference to accompanying drawing, describe in detail of the present invention from plating Cleaning Wastewater the embodiment of the method for recycle-water and metal.
Fig. 1 be represent of the present invention from plating Cleaning Wastewater the system diagram of the embodiment of the method for recycle-water and metal, Fig. 2 is the system diagram that represents the structure of crystallization device, Fig. 3 is the system diagram that represents the structure of sour contact device.
In the present invention, first will import in coagulation oxidation trough 1 as the plating Cleaning Wastewater of former water, interpolation oxygenant (in Fig. 1, being clorox (NaClO)), pH adjusting agent (in Fig. 1, being the caustic soda (NaOH) as alkaline agent), coagulating agent (are iron(ic) chloride (FeCl in Fig. 1
3)), by pH3～6 by the ferrous iron (Fe in liquid
2+) be oxidized to ferric iron (Fe
3+) separate out ironic hydroxide (Fe (OH)
3).
Do not dissolve in chemical industry order at above-mentioned iron, as oxygenant, except NaClO, can also use hydrogen peroxide or potassium permanganate, chlorine, ozone etc.The addition of oxygenant, as long as reach the Fe making in liquid
2+be oxidized to Fe
3+equivalent used above.
Plating Cleaning Wastewater is generally for example, acidity lower than pH3 (pH2 left and right), but in order to separate out Fe (OH)
3more than need to being adjusted to pH3, therefore by adding NaOH, the Ca (OH) as pH adjusting agent
2regulate pH in alkali.Wherein, although be to regulate according to the concentration situation in waste water, separate out if pH exceedes 7 nickel or zinc in liquid, therefore regulating pH is 3～7, is preferably adjusted to 5～6.
Do not dissolve in chemical industry order 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 add FeCl
3in coagulating agent.By adding FeCl
3in coagulating agent, improve the not precipitation threshold of dissolving particle, in the precipitate and separate efficiency promoting in the settling bath 2 of rear class, also increase throw out diameter, therefore, also can improve the filterableness in the UF film device 3 of rear class.And, thereby from make organism generation coagulation plating Cleaning Wastewater reduce rear class 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 conventionally made as 10～200mg/L, be preferably made as about 100～150mg/L.
In coagulation oxidation trough 1, make Fe (OH)
3the liquid that throw out is separated out, then (for example use MF film, UF film or strainer, sand filter) carry out solid-liquid separation, but in the method for Fig. 1, be then to use MF film device (MF membrane separation unit) 3 to carry out membrane filtration carrying out solid-liquid separation with settling bath 2 before this.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 rear class 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 to pump P
aimport in UF film device 3 and carry out membrane filtration.This UF film device 3 is carried out to regular backwash, by the Fe holding back (OH)
3mud is discharged outside system together with backwash waste.
By the filtered water of UF film device 3, process tank 4 through UF and import regulating tank 5, at the interior regulating water quality of regulating tank 5.,, process the filtered water of UF film device 3 in reverse osmosis membrane device (reverse osmosis membrane tripping device) 6 before, in order to protect reverse osmosis membrane, in UF membrane filtration water, add sodium bisulfite (NaHSO
3), S-WAT (Na
2sO
4) etc. reductive agent, or, remove residual oxygenant by contact gac, and, so that the concentrated mode that can not make the oxyhydroxide of the metal such as nickel, zinc separate out in reverse osmosis membrane device 6, add as required pH adjusting agent, the pH regulator that makes thus to supply with the water (RO is for feedwater) in reverse osmosis membrane device 6 is 4～6, is preferably adjusted to 4～5.
To the amount of the reductive agent adding in UF membrane filtration water, more than being conventionally made as the equivalent of residual oxygenant, set excessive 5～20mg/L, preferably set excessive 10～15mg/L.
By the adjusted water of water quality in regulating tank 5, by pump P
bimport in reverse osmosis membrane device 6, carry out membrane separation for seeing through water (RO sees through water) and condensed water (RO condensed water).A part of condensed water is flowed in the concentrated tank 7 of RO, and remainder is carried out to circular treatment.
Processing in this reverse osmosis membrane device 6, is that the mode that 5～10 times, the water rate of recovery are 80～90% is carried out according to concentration rate, but preferably in running, does not break down and carry out in the mode that height concentrating metals ion improves the water rate of recovery.
The RO obtaining in reverse osmosis membrane device 6 sees through water, has and the good water quality of pure water same degree, therefore, can set it as plating water for cleaning and recycle.And this RO sees through water and can also the angle based on other application sets out and be used.
By the metal ion in RO condensed water, be condensed into 5～10 times of concentration of metal ions in plating Cleaning Wastewater, through the concentrated tank 7 of RO, this RO condensed water is imported in crystallization device 8 to carry out crystallization processing.
As crystallization device 8, as long as can promote separating out of metal carbonate, be not particularly limited, but preferably example tower reactor as shown in Figure 2, wherein, at the interior filling crystal seed of crystallization reaction tower 10, from the bottom circulation RO condensed water of tower, in tower, form the fluidised bed of crystal seed.
In the device of Fig. 2, by former crystallization water, pass through pump P through pipeline 11
1circulate from the bottom of reaction tower 10, will process water and flow out in rear importing processing tank 9 by pipeline 12.A part is processed to water, pass through circulating line 14 and recycle pump P from the top of tower
2process the bottom that is circulated to tower.
From the top of crystallization reaction tower 13, inject sodium carbonate (Na
2cO
3) or sodium bicarbonate (NaHCO
3) with the basic carbonate such as the mixed solution of caustic soda (NaOH).In tower on mobile crystal seed, by make sodium carbonate react with metal ion (for example following reaction) carry out 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, for separating out of this metal carbonate, be necessary to improve pH to 7～10 of the former water of crystallization, preferably bring up to 8～9 and carry out.Therefore, to the amount of the basic carbonate injecting in crystallization reaction tower 10, be to form the necessary amount of metal carbonate, and be set as making liquid pH in crystallization tower to become the amount of above-mentioned pH.If this pH does not produce and separates out lower than 7 carbonate, if this pH exceed 10 zinc carbonate be easy to occur dissolve again.
In above-mentioned crystallization operation, need to improve pH, but in the present invention, before crystallization operation, concentrate by reverse osmosis membrane separating treatment, reduce the water yield of finishing partial crystallization and go out handling object, therefore can reduce and regulate the necessary amount of medicament of pH.
In the present invention, use the sour insoluble particle that dissolving does not occur in the metal recovery operation of rear class under acid treatment as crystal seed.As sour insoluble particle, can use sand (silica sand), hard coal etc.The particle diameter of crystal seed is 0.1～1mm, is particularly preferably 0.2～0.4mm left and right.
Metal ion in the former water of crystallization, is processed and is formed metal carbonate by crystallization, thus dissolving separating out on seed surface not.By separating out of metal carbonate, seed particles growth, particle diameter increases to 0.3～1.5mm.The particle of increase is taken out from crystallization device, flow to metal recovery operation.
The processing water of crystallization device 8 is imported to crystallization to be processed in tank 9.
In powders using crystallization method, according to the difference of operational condition, the rate of recovery of metal ion is variant, but is 70～90% as a rule, is generally 80% left and right.Therefore, preferably this crystallization of a part being processed to water sends iron back to and does not dissolve in chemical industry order with together with the plating Cleaning Wastewater of former water and carry out circular treatment.Thus, can be for separating out and process the metal ion that reclaims and carry out periodic crystallisation and separate out processing by primary crystallization, thus improve overall metal recovery rate.
In the present invention, preferably process with following condition: the ratio of the crystallization of this circular treatment being processed to water is set as 10～80% of the water being imported in crystallization processing tank 9, make the water rate of recovery on the whole become 70～90%, and metal recovery rate become 80～95% left and right.
In crystallization device 8, the particle that is attached with the metal carbonate of nickel, zinc etc. using the insoluble crystal seed of acid as core is contacted with the acid such as sulfuric acid, hydrochloric acid, the metal carbonate of nickel, zinc etc. occurs to dissolve again, obtains the vitriol of these metals or the highly concentrated solution of chloride salt.In the processing of electroplating cleaning waste water, the high density metal sulfate aqueous solution obtaining directly in bathing, plating can be recycled by operation like this.And, contact with acid and after dissolution of metals carbonate, remain sour insoluble seed particles by the particle that makes above-mentioned recovery, this seed particles can be utilized as crystal seed again by crystallization device.By so recycling seed particles, the particle diameter management in crystallization device becomes easy.
Therefore, preferably regularly from crystallization device 8, take out and separate out from the teeth outwards the seed particles that has metal carbonate, then process and reclaim respectively again metal salt solution and crystal seed with acid.
The device contacting with acid as the particle that makes to take out in crystallization device 8 (particle that metal carbonate is separated out on seed surface), as long as can effectively make both contact, be not particularly limited, for example, can use sour contact device as shown in Figure 3.
This acid contact device has sour contact tower 20, in described sour contact tower 20, pack the taking-up particle from crystallization device 8 into, bottom in this tower, is provided with water collection sheet (porous plate or mesh), described water collection sheet only have moisture can see through and particle can not see through.In the time processing from the taking-up particle of crystallization device 8, open valve V
1, V
2and close other valve, and then taking-up particle is packed in sour contact tower 20 from pipeline 21, moisture is taken out from pipeline 23,24.Sending this moisture back to crystallization processes in tank 9.Then, open valve V
3, V
4and close other valve, then, use pump P
3through acid such as piping 25,23 circulation of the bottom by sour contact tower 20 sulfuric acid, by acid and particle are come in contact, the metal carbonate of seed surface is dissolved.Take out the solution of the metal ion that contains metal carbonate dissolving through pipeline 26.As this metal salt solution, conventionally can obtain metal ion is the highly concentrated solution of 5～15 % by weight left and right, and therefore preferably this metal salt solution recycles as plating solution.
After the metal carbonate of seed surface is dissolved, open valve V
2, V
5and close other valve, then use pump (not shown) in high flow rate mode through pipeline 24,23 and from the bottom circulation water of sour contact tower 20, by crystal seed through valve V
5sending crystallization device 8 back to recycles.
In addition, as the acid for dissolving the metal carbonate on crystal seed, be preferably the high-concentration sulfuric acid aqueous solution of 50～98 % by weight left and right, or the aqueous hydrochloric acid of 20～35 % by weight.
In hydroxide precipitation method in the past, also can make not dissolving of metal ion, and after making it dissolve again under sour effect, recycle in plating is bathed, but by carry out crystallization processing as the present invention, without settling tank or water extracter.And, can obtain particle diameter larger except the good particle of water-based, therefore, can use all sour contact devices as shown in Figure 3, by the operation that easily dewaters, dissolves again, can reclaim the metal salt solution of high density.
By carrying out aforesaid operations, reduce wastewater flow rate, discharged amount of metal and significantly reduced the sludge creation amount in entire system based on the present invention, thus recycle-water and valuable metal from plating Cleaning Wastewater effectively.
Embodiment
Below, by be described more specifically the present invention in conjunction with the embodiments.
Embodiment 1
Adopt the method shown in Fig. 1 from plating Cleaning Wastewater, to reclaim water and metal.
First, in coagulation oxidation trough 1, plating Cleaning Wastewater is added to 5mg/L clorox, make contained Fe in 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 settling bath 2, more than half part of the throw out generating is carried out to precipitate and separate, then with UF film device 3, the parting liquid of settling bath 2 is carried out to membrane filtration.This UF film device 3 is carried out to regular backwash.
By the filtered water of UF film device 3, processing tank 4 through UF imports in regulating tank 5, and add 15mg/L sodium bisulfite to remove residual chlorine, then, supply with reverse osmosis membrane device 6 (RO is for feedwater), reclaim RO and see through water, and, RO condensed water is flowed to crystallization device 8 to carry out crystallization processing through the concentrated tank 7 of RO.The water rate of recovery of this reverse osmosis membrane device 6 is 80%.
The water quality of each operation in this processing is shown in Table 1.
Table 1
Can specify as follows according to table 1.
By not dissolving processing of iron, make iron that not dissolving occur and react and be removed, and reach the level can't detect for the feedwater stage at RO.In addition, before reverse osmosis membrane device 6, nearly all there is not dissolving in nickel, zinc in dissolved state.The nickel, the zinc that are directly concentrated with dissolved state in RO condensed water one side, be removed approximately 80% (metal recovery rate is 80%) by crystallization processing.Now, on the surface of the sand packing into as crystal seed, there are nickel, zinc to separate out, and the increase of visible crystal seed particle diameter.
UF backwash waste, crystallization are processed water and are used as waste water discharge, and therefore, the water rate of recovery going up as a whole reaches 75%.
Embodiment 2
In embodiment 1, to processing by crystallization, particle diameter increases to the crystal seed of 0.3～0.4mm left and right, imports in the sour contact tower 20 shown in Fig. 3, and is dewatering after 10 minutes, injects 50 % by weight aqueous sulfuric acids from tower bottom.The water ratio that removed the particle in the stage of water is 10 % by weight.By inject sulfuric acid from 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, be respectively 1.5 % by weight, 17 % by weight.This result is that nickel, the zinc of the plating Cleaning Wastewater in former water is concentrated into respectively 600 times, 577 times.
Embodiment 3
Send back to the inlet side of coagulation oxidation trough 1 processes together with plating Cleaning Wastewater except 90% crystallization being processed to water, operate similarly to Example 1.In the present embodiment, metal recovery rate after crystallization is processed once does not change, and is 80%, but sends back to again to process by crystallization being processed to water, make thus repeatedly to obtain crystallization processing, metal recovery rate has on the whole been brought up to 98%.And, the water rate of recovery has been brought up to 92%.
By using specific mode to describe the present invention in detail, but to those skilled in the art, can, clearly not exceeding in aim of the present invention and scope, can carry out various changes.
In addition, in this, please be to make according to the Japanese Patent application (Japanese Patent Application 2009-140335) that on June 11st, 2009 proposes, here cite its whole content.
Claims (6)
1. a method for recycle-water and metal from plating Cleaning Wastewater, is characterized in that, comprises following operation:
Under the existence of oxygenant, regulating plating Cleaning Wastewater is that pH3～6 make oxidation of divalent iron ion in liquid become ferric ion and the iron of separating out ironic hydroxide does not dissolve chemical industry order,
The processing water that this iron is not dissolved to chemical industry order carries out the solid-liquid separation process of solid-liquid separation by secondary filter film, ultra-filtration membrane or sand filter,
The Separation of Water separating in this solid-liquid separation process is carried out to reverse osmosis membrane separating treatment and will see through water as process the water reverse osmosis membrane separation circuit of discharging outside system, and
The crystallization operation that metal in liquid is separated out by add the mixed solution of sodium carbonate or sodium bicarbonate and sodium hydroxide and the powders using crystallization method using sour insoluble particle as crystal seed in the condensed water of reverse osmosis membrane separation circuit as carbonate,
And in above-mentioned reverse osmosis membrane separation circuit, the pH that supplies with the water in reverse osmosis membrane device is 4～6.
As claimed in claim 1 from plating Cleaning Wastewater the method for recycle-water and metal, it is characterized in that, in described crystallization operation, also comprise metal recovery operation, described metal recovery operation is dissolved in and in acid, is obtained metal salt solution by the metal carbonate that makes to separate out on crystal seed.
As claimed in claim 2 from plating Cleaning Wastewater the method for recycle-water and metal, it is characterized in that, the metal salt solution obtaining in described metal recovery operation is recycled as plating solution.
As claimed in claim 2 from plating Cleaning Wastewater the method for recycle-water and metal, it is characterized in that, from described metal recovery operation, reclaim crystal seed and recycle in crystallization operation.
As claimed in claim 2 from plating Cleaning Wastewater the method for recycle-water and metal, it is characterized in that, described acid is aqueous sulfuric acid or aqueous hydrochloric acid.
6. the recycle-water from plating Cleaning Wastewater as described in any one in claim 1 to 5 and the method for metal, is characterized in that, sends the partially disposed water of described crystallization operation back to described iron and do not dissolve in chemical industry order and process.
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 CN102459096A (en) | 2012-05-16 |
| CN102459096B true 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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| JP5445777B2 (en) * | 2010-07-28 | 2014-03-19 | 住友金属鉱山株式会社 | Method for producing ferronickel smelting raw material from low-grade nickel oxide ore |
| WO2012098924A1 (en) * | 2011-01-20 | 2012-07-26 | 三菱レイヨン株式会社 | Wastewater treatment apparatus, wastewater treatment method, and wastewater treatment system |
| JP5719320B2 (en) * | 2012-01-27 | 2015-05-13 | Ｊｆｅエンジニアリング株式会社 | Zinc recovery method from galvanizing waste liquid |
| CN103539276A (en) * | 2013-06-03 | 2014-01-29 | 广州凯膜过滤设备有限公司 | System and technology for realizing electroplating washing zero discharge and electroplating solution recovery |
| JP6189205B2 (en) * | 2013-12-18 | 2017-08-30 | 三菱重工業株式会社 | Concentrator scale detection device and method, water regeneration treatment system |
| WO2015129541A1 (en) * | 2014-02-27 | 2015-09-03 | 三菱レイヨン株式会社 | Treatment method and treatment device for waste water containing heavy metal |
| CN104724857B (en) * | 2015-03-27 | 2016-08-24 | 天津大学 | The recycling processing method of rinsing liquid during Production of bleaching powder concentrate |
| EP3156508A1 (en) * | 2015-10-16 | 2017-04-19 | Vito NV | Recovery process for metal-containing byproducts of metal production and processing |
| JP6709036B2 (en) * | 2015-11-12 | 2020-06-10 | 岩井ファルマテック株式会社 | Hot water recovery system |
| US20180029907A1 (en) * | 2015-12-22 | 2018-02-01 | Sumitomo Electric Industries, Ltd. | Water treatment method and water treatment system |
| JP6216856B1 (en) * | 2016-10-06 | 2017-10-18 | 川村 彰彦 | Useful resource recovery apparatus and method for recovering useful resources from an eluate from which useful resources are eluted |
| CN106587478A (en) * | 2017-01-22 | 2017-04-26 | 青岛北方节能环保有限公司 | Hot-dip galvanizing waste acid resource treatment method |
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| CN102459096A (en) | 2012-05-16 |
| JP2010284593A (en) | 2010-12-24 |
| JP5471054B2 (en) | 2014-04-16 |
| WO2010143623A1 (en) | 2010-12-16 |
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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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Granted publication date: 20140618 Termination date: 20210608 |