CN104909508B - Electroplating chromium-containing wastewater treatment method and device - Google Patents
Electroplating chromium-containing wastewater treatment method and device Download PDFInfo
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- CN104909508B CN104909508B CN201510307762.0A CN201510307762A CN104909508B CN 104909508 B CN104909508 B CN 104909508B CN 201510307762 A CN201510307762 A CN 201510307762A CN 104909508 B CN104909508 B CN 104909508B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
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- Y02A20/124—Water desalination
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Abstract
The invention discloses an electroplating chromium-containing wastewater treatment method and device. The treatment method comprises the following steps: (A) pre-removing impurities in chromium-containing wastewater by virtue of a pretreatment device, so as to acquire primarily treated effluent; (B) sequentially carrying out primary desalination on effluent by virtue of a cation exchanger and an anion exchanger, carrying out secondary desalination on effluent by virtue of an advanced treatment cation bed and an advanced treatment anion bed again, so as to obtain desalted water which can be recycled for chromium plating rinsing; (C) regenerating by virtue of a cation bed regeneration device when the cation exchanger is saturated and penetrated, and regenerating by virtue of an anion bed regeneration device when the anion exchanger is saturated and penetrated; and (D) carrying out sodium removal on anion bed regenerated liquid, and concentrating to form recyclable high-concentration chromic acid or carrying out evaporative crystallization. According to the electroplating chromium-containing wastewater treatment method, by virtue of a two-stage cation-anion bed system, the environmental pollution of hexavalent chromium is eliminated, and meanwhile, high-quality desalted water can be obtained and can be applied to production, so that the consumption of tap water and desalted water is saved, and the good economic benefit is achieved.
Description
Technical field
The present invention relates to technical field of waste water processing, more particularly to a kind of processing method and process dress of waste electroplating liquor containing chromium
Put.
Technical background
Tin plate is commonly called as tinplate, is widely used in food, beverage, oil and fat chemical, coating, paint, spray, bottle cap etc.
The packaging of other commodity, shows according to the metal committee of Chinese packaging association statistics, China's tin plate consumption figure in 2006
Increased substantially than 2005：Inhalator jar increases by 11%, beverage built-up tin and increases the growth by 71%, crown plug of 33%, food built-up tin
Increase by 15%, chemical tank and increase by 30%, global tinplate demand reaches 20,000,000 tons within 2012,12 period China sackers
Rapid growth, tinplate container will be faced major opportunity by industry, and development space is huge, there is wide market.Electrotinning is thin
Board assembly line includes band charging workshop section, tin plating pre-treatment workshop section, electroplating bath workshop section, chemical treatment workshop section and finished product workshop section.Its
Middle chemical treatment workshop section：It is made up of passivation, flushing, drying and the part of Electrostatic greasing device four.The composition of passivating solution is sodium dichromate
And chromic acid.Tin plate after passivation enters finished product workshop section Jing after cleaning down, drying and Electrostatic greasing.
Substantial amounts of chromate waste water will be produced in passivation procedure and flushing operation, at present major part enterprise is straight by the effluent part
Run in and processed into workshop sewage plant, produce the danger containing chromium in a large number and give up, while wasting substantial amounts of water resource.12 planning
Period, the center of gravity of Chinese government's work starts to be inclined to energy-conserving and environment-protective field, and bringing forward will develop low-carbon economy and low-carbon (LC) energy
Source.The purpose of energy-saving and emission-reduction how is reached, is problem of the pendulum in face of all enterprises.
Cr VI is most serious in electroplating industry, is most difficult to process one of primary pollution source, Environmental Protection Agency USA (E P
A) Cr VI is defined as one of toxicant of 7 kinds of highly dangerous of l.Chromium exists in water with trivalent and hexavalent form, its
In chromic toxicity it is very big, it is about chromic 100 times, if concentration of the chromic content more than 0.1mg/L in water,
Toxic action will be produced to human body.Chromic waste water, waste are unable to natural degradation, and it is in biological and accumulated in creatures, energy
The harm of chronicity is enough caused, is a kind of extremely strong strong carcinogen of toxicity, be also serious corrosive medium.Chromium ion pollutes
Source in electroplating industry be mainly chromium plating carry-over loss, be plated on workpiece only less than 15% chromium ion, and 85% with
On chromium ion be all washed in sewage treatment tank, process and reuse to chromate waste water, and taking out of in chrome-plating process
Chromic acid is reclaimed will be with obvious economic benefit.
The main methods of current Domestic Plating chromate waste water are divided into：Chemical reduction method, electrolysis, membrane separation process, suction
Attached method, bioanalysis, ion-exchange etc..Chemical reduction method is to be reduced into the strong Cr of waste water Poisoning (VI) using reducing agent
The little Cr of toxicity low solubility (III), finally with chromium hydroxide precipitation removing, the method equipment is simple, processing ease, operating cost
It is low；But the substantial amounts of sediment sludge for being difficult to and processing is produced, secondary pollution can be produced.Electrolysis is using in electrode and waste water
The method that Cr (VI) occurs electrochemical reaction and eliminates its toxicity, the method electric energy consumption is big, and electrode metal consumption is big, and detached heavy
The not disposable utilization of starch, there is certain secondary pollution.Membrane separation process treatment of chromium containing wastewater is in exploration and develops rank
Section, additionally, the cost of film is of a relatively high, and need to be regenerated or be changed using a period of time for it, for high-volume
When wastewater treatment is produced, operating cost is larger.Absorption method is sent out with the Cr (VI) in waste water with the larger specific surface area of adsorbent
Life is adsorbed and removes method；The method can more rapidly process the chromium ion of waste water, and treatment effect is preferably, and operating cost is few, but
Adsorbent is consumed, equipment is huge；During actual production, the transport charging discharging of adsorbent is more difficult, and desorption is still suffered from necessarily
Technical difficulty.Bioanalysis is urged mainly by the function bacterium of artificial culture using the electrostatic adsorption of microorganism, enzyme
Cr (VI) in changing transformation, complexing, flocculation, co-precipitation to remove waste water, using less in Practical Project.
Ion-exchange processes electroplating wastewater, and effluent quality is good, and recyclable utility facilitates implementation automation, and the shortcoming of the method is
Resin is easily oxidized and pollutes, higher to pre-processing requirements.
At present, the method for processing waste water containing chrome is a lot, but traditional electronation precipitation method, electrolysis there are secondary dirt
Dye, chromium ion is difficult to the shortcomings of recycling；Although bioanalysis, membrane separation process have a extensive future, but it is on probation to be also in research at present
Stage, extensive utilization needs time；And ion-exchange and absorption method are the preferable methods of current processing waste water containing chrome, have
Exchange adsorption capacity is big, and it is good to recycle effect, to environment non-secondary pollution, using wide, and the advantages of technology is more ripe, but
Have that pre-processing requirements are higher, resin is oxidized easily, the shortcomings of to reclaim chromic acid concentration relatively low.
In sum, the current waste electroplating liquor containing chromium discharge capacity of China is big, and hexavalent chromium polluted toxicity is big, is faced with the ring of sternness
Packing pressure, governs the development of industry.Environmental requirement can not have been met using traditional waste water treatment process, and economic benefit compared with
It is low.
Therefore, prior art has yet to be improved and developed.
The content of the invention
In view of above-mentioned the deficiencies in the prior art, it is an object of the invention to a kind of processing method of waste electroplating liquor containing chromium and place
Reason device, the processing method and processing meanss of the waste electroplating liquor containing chromium produce containing passivation technology suitable for processing tinplate
Chrome waste water and electroplating industry carry out the chromate waste water produced in chrome-plating process, it is intended to solve at present with regard to chromate waste water process side
There is secondary pollution in method, process that water is less to be back to electroplate rinsing technique, and chromic acid is the problems such as can not reclaim.
Technical scheme is as follows：
A kind of processing method of waste electroplating liquor containing chromium, for reclaiming electroplating process in chromic acid in chromate waste water, wherein, bag
Include following steps：
A, beforehand through preprocessor, the suspended impurity in chromate waste water, grease and iron ion are removed, obtain preliminary place
Water outlet after reason；Wherein, the preprocessor includes in settling vessel, grease trap, bag filter and fiber bundle filter
Plant or various；
B, water outlet passes sequentially through cation exchanger and anion exchanger carries out just one-step desalting and detects whether saturation
Penetrate；The pH value of water outlet is reduced, by the Cr in water outlet6+It is converted into Cr2O7 2-Form, and exchange the resin in anion exchanger
On；Again water outlet is passed sequentially through into advanced treating cation bed and advanced treating anion bed carries out desalination again, reduces the conductance of water outlet, obtains
Obtain the recyclable demineralized water for chromium plating rinsing；
C, after cation exchanger saturation is penetrated, regenerated by cation bed regenerating unit：To in cation exchanger
Being passed through HCl regenerated liquids carries out co-current regeneration, obtains cation bed regenerated liquid and enters in cation bed regenerated liquid collecting box；Work as anion exchange
After device saturation is penetrated, regenerated by anion bed regenerating unit：NaOH regenerated liquids are passed through in anion exchanger carries out following current
Regeneration, obtains anion bed regenerated liquid and enters in anion bed regenerated liquid collecting box；
The boosted pumping of anion bed regenerated liquid in D, anion bed regenerated liquid collecting box is delivered to and carried out at removing sodium in cation bed removing sodium device
Reason, obtains low concentration chromic acid and enters side by side in chromic acid recycling can；Again Jing chromic acid elevator pump pumps into vacuum evaporation device concentration
Into the recyclable high concentration chromic acid for chromium plating；The boosted pumping of regenerating cation exchanger liquid in cation bed regenerated liquid collecting box
Deliver to evaporative crystallization in vacuum evaporation device.
The processing method of the waste electroplating liquor containing chromium, wherein, in stepb, the resin filled in cation exchanger
For the strongly acidic styrene type cation exchange resin of H types 001 × 7；The height of the cationic ion-exchange resin be 1.0-3.0m, work
Operation flow velocity when making is 15-30m/h；The resin filled in anion exchanger is that D301 macroreticular weakly bases polystyrene is cloudy
Ion exchange resin；The height of the anion exchange resin is 2-3m, and operation flow velocity during work is 15-30m/h.
The processing method of the waste electroplating liquor containing chromium, wherein, in stepb, water outlet through the advanced treating cation bed and
After the desalination again of advanced treating anion bed, the demineralized water of the μ s/cm of electrical conductivity ＜ 10 is obtained；Filled in the advanced treating cation bed
Resin be the strongly acidic styrene type cation exchange resin of H types 001 × 7, its highly be 1-2m；In the advanced treating anion bed
The resin filled is 201 × 7 strong-basicity styrene series anion exchange resins, and it is highly 1-2m.
The processing method of the waste electroplating liquor containing chromium, wherein, in stepb, the water inlet pipe of the anion exchanger and
Outlet pipe is for monitoring the transparent pipe of water outlet color, while being additionally provided with one for detecting cation exchanger and anion
The exchanger ORP on-line detectors whether saturation is penetrated；The anion exchanger includes the first anion exchanger and second
Anion exchanger, wherein, one for work and another is standby, or to be sequentially communicated work.
The processing method of the waste electroplating liquor containing chromium, wherein, in step C, the cation bed regenerating unit and anion bed regenerate
Regeneration velocity in device is 5m/h；In the HCl regenerated liquids, the mass concentration of HCl is 5-7%；The NaOH regenerated liquids
In, the mass concentration of NaOH is 7-10%.
A kind of processing meanss of waste electroplating liquor containing chromium, wherein, the processing meanss include one for by chromate waste water
Suspended impurity, the preprocessor that removes of grease and iron ion, the preprocessor is connected with cation in turn and hands over by pipeline
Parallel operation, anion exchanger, advanced treating cation bed and advanced treating anion bed；
The cation exchanger is also associated with one is used for the cation bed regenerating unit of resin in cation regenerant exchanger；Institute
State anion exchanger be also associated with one for resin in anion regenerant exchanger anion bed regenerating unit.
The processing meanss of the waste electroplating liquor containing chromium, it is characterised in that the cation bed regenerating unit includes that the first regeneration is auxiliary
Tank, the first regeneration pump, acid batch meter and Acid injector are helped, wherein, the acid batch meter is sequentially connected to the acid by pipeline
Injector and cation exchanger, the first regeneration auxiliary tank is by pipeline successively in first regeneration pump and the acid spray
Emitter, the first regeneration auxiliary tank is also connected by pipeline with the evacuated tube of cation exchanger bottom, forms circulation line；
The acid batch meter is also connected with one by pipeline to be used to store the sour storage tank of HCl regenerated liquids；
The anion bed regenerating unit includes the second regeneration auxiliary tank, the second regeneration pump, alkali batch meter and alkali injector, its
In, the alkali batch meter is sequentially connected to the alkali injector and anion exchanger, the second regeneration auxiliary by pipeline
, by pipeline successively in second regeneration pump and the alkali injector, the second regeneration auxiliary tank is also by pipeline and the moon for tank
The evacuated tube connection of ion-exchanger bottom, forms circulation line；The alkali batch meter is also connected with one for depositing by pipeline
The alkali storage tank of storage NaOH regenerated liquids.
The processing meanss of the waste electroplating liquor containing chromium, wherein, the processing meanss are also included and are connected to the anion
The anion bed regenerated liquid collecting box of exchanger；In the anion bed regenerated liquid collecting box by pipeline be connected with turn cation bed removing sodium device,
Chromic acid recycling can and vacuum evaporation device；Also include the cation bed regenerated liquid collecting box for being connected to the cation exchanger；
The cation bed regenerated liquid collecting box is connected with the vacuum evaporation device.
The processing meanss of the waste electroplating liquor containing chromium, wherein, the processing meanss also include：After being connected to preprocessor
Chromate waste water case, the chromate waste water case be used to carrying out the chromate waste water after preprocessed device preliminary treatment and water quality and
Stabilizing water quantity；The reuse water tank being arranged between anion exchanger and advanced treating cation bed, the reuse water tank is used to store
Demineralized water after cation exchanger and the first one-step desalting of anion exchanger；One is additionally provided with for generation in processing procedure
The wastewater collection pond that waste water is reclaimed.
The processing meanss of the waste electroplating liquor containing chromium, wherein, the processing meanss also include：Be arranged on chromate waste water case and
The first bag filter between cation exchanger；Second bag be arranged between anion bed regeneration collection box and cation bed removing sodium device
Formula filter；And the 3rd bag filter being arranged between cation bed removing sodium device and chromic acid recycling can.
Beneficial effect：A kind of processing method and processing meanss of waste electroplating liquor containing chromium of the present invention, it is by by ion exchange
Method and evaporation concentration technique combine, and realize waste electroplating liquor containing chromium and administer reuse and the closed cycle of chromic acid utilization,
Zero-emission is substantially achieved, chromic environmental pollution is eliminated；The consumption of running water and demineralized water is reduced simultaneously, has saved chromium
The consumption of acid, reduces sewage water discharge expense and the handling containing chromium solid waste, and environmental benefit and economic benefit are obvious.
Description of the drawings
Fig. 1 is the process flow figure of waste electroplating liquor containing chromium of the present invention.
Fig. 2 is the structured flowchart of the processing meanss of waste electroplating liquor containing chromium of the present invention.
Fig. 3 be waste electroplating liquor containing chromium of the present invention processing meanss in anion exchanger and its anion bed regenerating unit set
Standby figure.
Specific embodiment
The present invention provides a kind of processing method and processing meanss of waste electroplating liquor containing chromium, to make the purpose of the present invention, technology
Scheme and effect are clearer, clear and definite, and below the present invention is described in more detail.It should be appreciated that described herein concrete
Embodiment only to explain the present invention, is not intended to limit the present invention.
Refer to Fig. 1, the present invention provides a kind of processing method of waste electroplating liquor containing chromium, for reclaiming electroplating process in contain chromium
Chromic acid in waste water, it specifically includes following steps：
S100, beforehand through preprocessor, the suspended impurity in chromate waste water, grease and iron ion are removed, obtain just
Water outlet after step process；Wherein, the preprocessor is included in settling vessel, grease trap, bag filter and fiber bundle filter
One or more；
S200, water outlet passes sequentially through cation exchanger and anion exchanger carries out just one-step desalting and detects whether to satisfy
With penetrate；The pH value of water outlet is reduced, by the Cr in water outlet6+It is converted into Cr2O7 2-Form, and exchange the tree in anion exchanger
On fat；Again water outlet is passed sequentially through into advanced treating cation bed and advanced treating anion bed carries out desalination again, reduces the conductance of water outlet,
Obtain the recyclable demineralized water for chromium plating rinsing；
S300, after cation exchanger saturation is penetrated, regenerated by cation bed regenerating unit：To cation exchanger
In be passed through HCl regenerated liquids and carry out co-current regeneration, obtain cation bed regenerated liquid and simultaneously enter in cation bed regenerated liquid collecting box；When anion is handed over
After parallel operation saturation is penetrated, regenerated by anion bed regenerating unit：Be passed through in anion exchanger NaOH regenerated liquids carry out it is suitable
Stream regeneration, obtains anion bed regenerated liquid and enters in anion bed regenerated liquid collecting box；
The boosted pumping of sodium chromate liquid in S400, anion bed regenerated liquid collecting box is delivered to and carried out at removing sodium in cation bed removing sodium device
Reason, obtains low concentration chromic acid and enters side by side in chromic acid recycling can；Again Jing chromic acid elevator pump pumps into vacuum evaporation device concentration
Into the recyclable high concentration chromic acid for chromium plating；The boosted pumping of regenerating cation exchanger liquid in cation bed regenerated liquid collecting box
Deliver to evaporative crystallization in vacuum evaporation device.
The processing method of waste electroplating liquor containing chromium of the present invention, is specifically applied to useless containing chromium in tinplate production passivation technology
Water and similar chromate waste water are processed, and it realizes electricity by the way that ion-exchange and evaporation concentration technique are combined
Plating route for treatment of chromium containing waste water reuse and the closed cycle of chromic acid are utilized, and eliminate chromic environmental pollution；Reduce originally simultaneously
The consumption of water and demineralized water, has saved the consumption of chromic acid.
Specifically, in the step s 100, in the chromate waste water, chromic concentration is generally 20-200mg/L, its electricity
Conductance is 500-2000 μ s/cm, and containing a small amount of impurity, iron ion content is low, pH value ＜ 5.Therefore preprocessor is first passed through
Granule foreign, grease and iron ion etc. are first removed, according to different water quality, different preprocessors is can select, such as settling vessel,
Grease trap, bag filter or fiber bundle filter etc..Chromate waste water is tentatively removed after impurity, is carried out in chromate waste water case
Uniform water quality and stabilizing water quantity, obtain the water outlet after preliminary treatment, are that the operation of next step is prepared.Subsequently, by elevator pump
The water outlet is promoted in the first bag filter, the filtering accuracy of first bag filter is 100 μm, and it can enter one
Walk to intercept the tiny suspended impurity in waste water and remove, it is to avoid the dirt of resin in follow-up cation exchanger and anion exchanger
Dye and blocking.
In subsequently entering step S200, i.e., just one-step desalting and again desalination are carried out to water outlet, reduce containing for poisonous hexavalent chromium
Amount.Specifically, just one-step desalting when the cation exchanger that adopted in, the resin that it is filled is the highly acid benzene of H types 001 × 7
Ethene cation exchanger resin, and the height of the cationic ion-exchange resin is 1.0-3.0m, operation flow velocity during work is
15-30m/h.Cr in the cationic exchange resin adsorption water outlet3+Deng cation, while discharging H+Ion, can make water outlet
PH value is reduced to≤4, and under this pH value, chromium is mainly with Cr in waste water2O7 2-Form is present.When water outlet is handed over through cation
When entering anion exchanger after parallel operation, because of pH value≤4 in waste water, Cr VI is mainly with the presence of dichromate ion form, weight chromium
Acid group form is beneficial to the exchange capacity of effectively utilizes resin, and principle is as follows：
2ROH + CrO4 2-=R2 CrO4 +2OH-
2ROH + Cr2O7 2-=R2Cr2 O7 +2OH-
From reaction equation, with same amount of resin treatment Cr VI, by Cr2O7 2-Exchange capacity be by CrO4 2-Exchange
2 times of capacity, and CrO4 2-It is difficult to replace by the SO of resin adsorption4 2-Fat, Cl-Deng anion, and Cr2O7 2-Then easily replace
By the SO of resin adsorption4 2-Fat, Cl-Deng anion.Therefore the resin filled in anion exchanger in the present embodiment adopts type
Number for D301 macroreticular weakly base polystyrenes anion exchange resin（Abbreviation D301 resins）；The anion exchange resin
Highly it is 2-3m, operation flow velocity during work is 15-30m/h.D301 resins has to dichromate ion preferably exchange selective power,
Cr2O7 2-Preferentially can be exchanged by D301 Choice of Resin, it can effectively improve Cr2O7 2-Adsorption rate.In addition, by the anion
The water inlet pipe and outlet pipe of exchanger is respectively provided with transparent pipe, can monitor water outlet color, while ORP on-line checking instrument is set,
Determine whether saturation is penetrated anion exchanger.Preferably, the anion exchanger includes the first anion exchanger and the
Two anion exchangers, wherein, it is a set of for work and another set of for standby, or to be sequentially communicated work.In the present embodiment
The anion exchanger method of operation is:The full saturation flow process of jack to jack adapter post series connection.As shown in figure 3, under normal circumstances, operation one
Set anion exchanger, when its close saturation is penetrated, that is, another set of anion exchanger of connecting is continued to run with；When first cloudy
When ion-exchanger water outlet is as water inlet hexavalent chromium concentration, first set anion exchanger out of service now, both can ensure
Total water outlet Cr VI is not exceeded, can make that the SO for exchanging may be adsorbed in the first anion exchanger again4 2-、Cl-Deng anion gradually
By Cr2O7 2-Replace, improve the concentration and purity of dichromate ion.Because D301 resins are to the exchange selectivity order of anion：
Cr2O7 2-＞ SO4 2-＞ NO3 -＞ CrO4 2-＞ Cl-＞ OH-, when in the first anion exchanger other anion completely by Cr2O7 2-
After replacement, its water inlet is as the content of 6-valence Cr ions in water outlet, you can the first anion exchanger out of service, and isolated operation
Second anion exchanger；Thus, Cr in anion exchanger can be improved2O7 2-Concentration and purity.
And in desalination again, the resin filled in the advanced treating cation bed for being adopted is the highly acid benzene of H types 001 × 7
Ethene cation exchanger resin（Abbreviation positive resin 001 × 7）, its resin height is 1-2m, and operation flow velocity is 15-30m/h.Separately
The resin filled in the outer advanced treating anion bed is 201 × 7 strong-basicity styrene series anion exchange resins（Referred to as cloudy tree
Fat 201 × 7）, its resin height 1-2m, operation flow velocity 15-30m/h.Advanced treating cation bed described in Jing and advanced treating anion bed
After deep desalting, make water outlet conductivity less than 10 μm, it is the demineralized water of high-quality, through bag filter impurity screening again
Afterwards, electroplate rinsing operation can be back to, the use water in electroplating process is saved, Sewage treatment utilization rate is improved.
After desalination, when observing that water outlet colour stable is constant by transparent pipe, and ORP on-line checking instrument detects cation
Exchanger and anion exchanger be when saturation is penetrated, into step S300, i.e., respectively by cation bed regenerating unit and anion bed
Regenerating unit is regenerated.For example, the Cr VI that anion exchanger absorption is exchanged, its time on resin can occur too long oxygen
Change reaction, become trivalent chromium, resin Jing alkali lye（The present invention is the NaOH in alkali storage tank）During regeneration, hydroxide three can be formed
Chromium sediment, invests resin surface, affects the exchange capacity of resin.Resin in anion exchanger is through alkali liquid regeneration for several times
Afterwards, operating capacity can be gradually reduced, and the regeneration period is gradually shortened, and when the regeneration period foreshortening to 1-2 days, need are active again
It is raw, with about 7% acid soak 8-10 hours so that sediment solution modeling, use alkali liquid regeneration after flushing again.
Specifically, the regenerating cation exchanger adopts co-current regeneration mode, and it adopts the mass concentration of HCl for 5-
7%, flow velocity is 3-5m/h, and the recovery time is 1-1.5h；After the completion of regeneration, obtain cation bed regenerated liquid and enter the cation bed again
In raw liquid collecting box.Then cleaning fluid is used（Such as clear water）Soak and repeatedly rinsed, for example, first time soaking flushing liquid continues
In entering cation bed regenerated liquid collecting box；Second and third, four soaking flushing liquid enter the first regeneration auxiliary in cation bed regenerating unit
In tank, the regenerated liquid as cation exchanger next time and cleaning fluid；Rinse being neutrality to flushing liquor pH value.It is preferred that
Ground, the cation exchanger bottom is provided with an inlet duct so that can in right amount enter gas agitating in soaking flushing, can strengthen
Developing result.Further, cation bed regenerated liquid collected in the cation bed regenerated liquid collecting box can enter into sewage collecting box
In focused on.
Similarly, the anion exchanger regeneration is also adopted by co-current regeneration mode, NaOH in its regenerated liquid for adopting
Mass concentration is 7-10%, and flow velocity is 3-5m/h, and the recovery time is 2-3h.Fig. 3 is specifically referred to, in the anion bed regenerating unit 1
Comprising the second regeneration auxiliary tank 14, the second regeneration pump 13, alkali batch meter 12, alkali injector 11（Cation bed regenerating unit structure is similar to,
Will not be described here）.Wherein, the water inlet of the second regeneration auxiliary tank 14 is provided with a pipe being connected with anion exchanger evacuation port
Road.During regeneration, work as regenerated liquid（That is NaOH solution）Just during dipped resin, start air stirrer, fully make regenerated liquid, sky
Gas is contacted with resin friction, it would be possible to which the sediment of the obstruction regeneration of generation is eluted by constantly flowing, is conducive to
Resin regeneration；Circular regeneration time about 1.5-2h.After the completion of regeneration, anion bed regenerated liquid is entered into the anion bed regenerated liquid and is collected
In case, clear water soaking flushing, first time flushing liquor is then used to enter anion bed regenerated liquid collecting box；Second and third, four times immersion punching
Washing lotion is entered in the second regeneration auxiliary tank, the regenerated liquid as anion exchanger next time and cleaning fluid；To flushing liquor pH value
When about 8, stop rinsing.Preferably, the anion exchanger bottom is provided with an inlet duct, can be appropriate during soaking flushing
Enter gas agitating, developing result can be strengthened.In addition, the top water distribution manner of the anion exchanger adopts spiral nozzle so that
Flushing liquor can be uniformly trickled down on resin face, in order to avoid form bias current so that relatively completely, washing water quantity is few and clean for regeneration.
In addition, the sodium chromate containing higher concentration in anion bed regenerated liquid collected in anion bed regenerated liquid collecting box, therefore
Filtration can be pumped into the second bag filter by elevator pump, remove suspended impurity, enter back into is carried out in cation bed removing sodium device
Removing sodium process.Specifically, the resin of filling is the exchange of D001 macroporous type superacicd styrenes cation in the cation bed removing sodium device
Resin, its resin height is 2-3m, and operation flow velocity is 15-30m/h.Anion bed regenerated liquid（Containing chromium acid sodium solution）It is de- through cation bed
Dichromic acid is obtained after sodium device removing sodium, the fragment to prevent impurity and resin in equipment, pipeline pollutes, then through the 3rd pocket type mistake
Filter is filtered and gone after the removal of impurity and fragment, in being collected in chromic acid recycling can.And the chromic acid concentration in the chromic acid recycling can with
Practical application is compared, and its concentration is less, to reach technological requirement, chromic acid need to be concentrated to into respective concentration.Therefore carried by chromic acid again
Rise and be pumped into vacuum evaporation device, evaporation and concentration obtains the higher chromic acid of concentration, be back to plating production.
Fig. 2 and Fig. 3 is referred to, the present invention also provides a kind of processing meanss of waste electroplating liquor containing chromium, wherein, it is described to process dress
Put and include a preprocessor for the suspended impurity in chromate waste water, grease and iron ion to be removed, the preprocessor
By being connected with cation exchanger, anion exchanger, advanced treating cation bed and advanced treating anion bed in turn by pipeline；Institute
State cation exchanger be also associated with one for resin in cation regenerant exchanger cation bed regenerating unit；The anion is handed over
Parallel operation is also associated with one is used for the anion bed regenerating unit of resin in anion regenerant exchanger.
Further, the cation bed regenerating unit includes the first regeneration auxiliary tank, the first regeneration pump, acid batch meter and acid spray
Emitter, wherein, the acid batch meter is sequentially connected to the Acid injector and cation exchanger by pipeline, and described first again
, by pipeline successively in first regeneration pump and the Acid injector, the first regeneration auxiliary tank is also by pipe for raw auxiliary tank
Road is connected with the evacuated tube of cation exchanger bottom, forms circulation line；The acid batch meter is also connected with one by pipeline
For storing the sour storage tank of HCl regenerated liquids.
Similarly, the anion bed regenerating unit includes the second regeneration auxiliary tank, the second regeneration pump, alkali batch meter and alkali injection
Device, wherein, the alkali batch meter is sequentially connected to the alkali injector and anion exchanger, second regeneration by pipeline
By pipeline successively in second regeneration pump and the alkali injector, the second regeneration auxiliary tank also passes through pipeline to auxiliary tank
It is connected with the evacuated tube of anion exchanger bottom, forms circulation line；The alkali batch meter is also connected with a use by pipeline
In the alkali storage tank of storage NaOH regenerated liquids.
In preferred embodiment, the processing meanss also include the anion bed regenerated liquid for being all connected to the anion bed regenerating unit
Collecting box and anion cleaning liquid storage tank；In the anion bed regenerated liquid collecting box by pipeline be connected with turn cation bed removing sodium device,
Chromic acid recycling can and vacuum evaporation device；Also include the cation bed regenerated liquid collecting box for being all connected to the cation bed regenerating unit
Liquid storage tank is cleaned with cation；The cation bed regenerated liquid collecting box is connected with the vacuum evaporation device.
Preferably, the processing meanss also include：The chromate waste water case being connected to after preprocessor, the chromate waste water
Case is used to carry out the chromate waste water after preprocessed device preliminary treatment equal and water quality and stabilizing water quantity；It is arranged on anion exchange
Reuse water tank between device and advanced treating cation bed, the reuse water tank is used to store cation exchanger and anion exchanger
Demineralized water after first one-step desalting；It is additionally provided with a wastewater collection pond for being reclaimed to the waste water produced in processing procedure.
More specifically, the processing meanss also include：First be arranged between chromate waste water case and cation exchanger
Bag filter；The second bag filter being arranged between anion bed regeneration collection box and cation bed removing sodium device；And it is arranged on sun
The 3rd bag filter between bed removing sodium device and chromic acid recycling can.
The specific operation process of heretofore described device realizes that step is identical with said method flow process, and here is no longer gone to live in the household of one's in-laws on getting married
State.In addition it should be noted that accompanying drawing does not constitute the restriction to this programme in the present invention, accompanying drawing is only a kind of preferred embodiment
Enforcement figure.
In sum, the processing method and processing meanss of a kind of waste electroplating liquor containing chromium provided by the present invention, its with it is existing
Technology is compared, and is had the advantage that and treatment effect：
（1）The present invention combines ion-exchange and vacuum evaporation crystallisation, using General Office's science and engineering
Skill, can discharge waste water and be evaporated concentration cation bed etc., discharge Water circulation, and the crystal of generation can be reclaimed further；And
Sodium chromate in anion bed carries out concentration and recovery, reuses；The present invention is in energy-saving and emission-reduction, waste water recycling and resource reclaim, reduction
Secondary pollution aspect effect preferably, achieves certain economic benefit and social benefit；
（2）Using two grades of positive anion bed systems, chromic environmental pollution was both eliminated, while high-quality demineralized water is obtained,
Production is back to, running water, desalination water consumption is saved；Six in waste water are exchanged using the full saturation flow process method absorption of jack to jack adapter post series connection
Valency chromium, improves the concentration and purity for reclaiming chromate, improves the utilization rate of D301 resins, extends the cycle of operation；
（3）Improve the regeneration of ion-exchanger：The secondary utilization of circular regeneration, air bump rinse operation, cleaning fluid, reduces
The consumption of regenerated liquid and cleaning fluid, and improve regeneration solution concentration；After conventional regeneration for several times, using resurrection regeneration,
Regenerating agent consumption is reduced, delays the aging of resin；
（4）Ion exchanger top water distribution manner adopts spiral nozzle so that flushing liquor can be uniformly trickled down on resin face,
In order to avoid forming bias current so that relatively completely, washing water quantity is few and clean for regeneration；Ion-exchanger bottom arranges inlet duct, immersion
Enter gas agitating during flushing in right amount, developing result can be strengthened.
It should be appreciated that the application of the present invention is not limited to above-mentioned citing, and for those of ordinary skills, can
To be improved according to the above description or be converted, all these modifications and variations should all belong to the guarantor of claims of the present invention
Shield scope.
Claims (9)
1. a kind of processing method of waste electroplating liquor containing chromium, for reclaiming electroplating process in chromic acid in chromate waste water, its feature exists
In comprising the following steps：
A, beforehand through preprocessor, the suspended impurity in chromate waste water, grease and iron ion are removed, after obtaining preliminary treatment
Water outlet；Wherein, the preprocessor include settling vessel, grease trap, bag filter and fiber bundle filter in one kind or
It is various；
B, water outlet passes sequentially through cation exchanger and anion exchanger carries out just one-step desalting and detects whether that saturation is penetrated；
The pH value of water outlet is reduced, by the Cr in water outlet6+It is converted into Cr2O7 2-Form, and exchange on the resin of anion exchanger；Again
Water outlet is passed sequentially through into advanced treating cation bed and advanced treating anion bed carries out desalination again, reduces the conductance of water outlet, and acquisition can
Reclaim the demineralized water for chromium plating rinsing；
C, after cation exchanger saturation is penetrated, regenerated by cation bed regenerating unit：It is passed through in cation exchanger
HCl regenerated liquids carry out co-current regeneration, obtain cation bed regenerated liquid and enter in cation bed regenerated liquid collecting box；
After anion exchanger saturation is penetrated, regenerated by anion bed regenerating unit：It is passed through in anion exchanger
NaOH regenerated liquids carry out co-current regeneration, obtain anion bed regenerated liquid and enter in anion bed regenerated liquid collecting box；
The boosted pumping of anion bed regenerated liquid in D, anion bed regenerated liquid collecting box is delivered in cation bed removing sodium device and carries out removing sodium process, is obtained
Obtain low concentration chromic acid to enter side by side in chromic acid recycling can；Again Jing chromic acid elevator pump is pumped into vacuum evaporation device and is condensed into and can return
Receive the high concentration chromic acid for chromium plating；
The boosted pumping of cation bed regenerated liquid in cation bed regenerated liquid collecting box delivers to evaporative crystallization in vacuum evaporation device.
2. the processing method of waste electroplating liquor containing chromium according to claim 1, it is characterised in that in stepb, cation exchange
The resin filled in device is the strongly acidic styrene type cation exchange resin of H types 001 × 7；The height of the resin is 1.0-
3.0m, operation flow velocity during work is 15-30m/h；
The resin filled in anion exchanger is D301 macroreticular weakly base styrene series anion exchange resins；The resin
Highly it is 2-3m, operation flow velocity during work is 15-30m/h.
3. the processing method of waste electroplating liquor containing chromium according to claim 1, it is characterised in that in stepb, water outlet is through institute
After stating the desalination again of advanced treating cation bed and advanced treating anion bed, the demineralized water of the μ s/cm of electrical conductivity ＜ 10 is obtained；
Wherein, the resin filled in the advanced treating cation bed is that the strongly acidic styrene's cation of H types 001 × 7 exchanges tree
Fat, it is highly 1-2m；The resin filled in the advanced treating anion bed is the friendship of 201 × 7 strong-basicity styrene series anions
Resin is changed, it is highly 1-2m.
4. the processing method of waste electroplating liquor containing chromium according to claim 1, it is characterised in that in stepb, the anion
The water inlet pipe and outlet pipe of exchanger is for monitoring the transparent pipe of water outlet color, at the same be additionally provided with one for detect sun from
Sub- exchanger and the anion exchanger ORP on-line detectors whether saturation is penetrated；
The anion exchanger includes the first anion exchanger and the second anion exchanger, wherein, it is a set of for work
And it is another set of for standby, or to be sequentially communicated work.
5. the processing method of waste electroplating liquor containing chromium according to claim 1, it is characterised in that in step C, the cation bed is again
Regeneration velocity in generating apparatus and anion bed regenerating unit is 3-5m/h；In the HCl regenerated liquids, the mass concentration of HCl is 5-
7%；In the NaOH regenerated liquids, the mass concentration of NaOH is 7-10%.
6. a kind of processing meanss of waste electroplating liquor containing chromium, it is characterised in that the processing meanss include and give up for containing chromium
The preprocessor that suspended impurity, grease in water and iron ion are removed, the preprocessor by pipeline be connected with turn sun from
Sub- exchanger, anion exchanger, advanced treating cation bed and advanced treating anion bed；
The cation exchanger is also associated with one is used for the cation bed regenerating unit of resin in cation regenerant exchanger；Described the moon
Ion-exchanger is also associated with one is used for the anion bed regenerating unit of resin in anion regenerant exchanger；
The cation bed regenerating unit includes the first regeneration auxiliary tank, the first regeneration pump, acid batch meter and Acid injector, wherein, institute
State acid batch meter and the Acid injector and cation exchanger are sequentially connected to by pipeline, the first regeneration auxiliary tank passes through
Pipeline successively in first regeneration pump and the Acid injector, also by pipeline with cation handed over by the first regeneration auxiliary tank
The evacuated tube connection of parallel operation bottom, forms circulation line；The acid batch meter is also connected with one for storing HCl again by pipeline
The sour storage tank of raw liquid；
The anion bed regenerating unit includes the second regeneration auxiliary tank, the second regeneration pump, alkali batch meter and alkali injector, wherein, institute
State alkali batch meter and the alkali injector and anion exchanger are sequentially connected to by pipeline, the second regeneration auxiliary tank passes through
Pipeline successively in second regeneration pump and the alkali injector, also by pipeline with anion handed over by the second regeneration auxiliary tank
The evacuated tube connection of parallel operation bottom, forms circulation line；The alkali batch meter is also connected with one for storing NaOH by pipeline
The alkali storage tank of regenerated liquid.
7. processing meanss of waste electroplating liquor containing chromium according to claim 6, it is characterised in that the processing meanss are also included
It is connected to the anion bed regenerated liquid collecting box of the anion exchanger；Connected successively by pipeline in the anion bed regenerated liquid collecting box
It is connected to cation bed removing sodium device, chromic acid recycling can and vacuum evaporation device；
Also include the cation bed regenerated liquid collecting box for being connected to the cation exchanger；The cation bed regenerated liquid collecting box and institute
State the connection of vacuum evaporation device.
8. processing meanss of waste electroplating liquor containing chromium according to claim 6, it is characterised in that the processing meanss also include：
The chromate waste water case being connected to after preprocessor, the chromate waste water case be used for preprocessed device preliminary treatment after containing chromium
Waste water carries out equal and water quality and stabilizing water quantity；The reuse water tank being arranged between anion exchanger and advanced treating cation bed, institute
Reuse water tank is stated for the demineralized water after storing cation exchanger and the first one-step desalting of anion exchanger；Being additionally provided with one is used for
The wastewater collection pond that the waste water produced in processing procedure is reclaimed.
9. processing meanss of waste electroplating liquor containing chromium according to claim 6, it is characterised in that the processing meanss also include：
The first bag filter being arranged between chromate waste water case and cation exchanger；It is arranged on anion bed regeneration collection box and cation bed
The second bag filter between removing sodium device；And the 3rd bag type filtering being arranged between cation bed removing sodium device and chromic acid recycling can
Device.
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| CN105130064A (en) * | 2015-09-25 | 2015-12-09 | 深圳前海中盛环保科技有限公司 | Novel method for treating chrome-containing wastewater and recycling chrome of chrome pigments |
| CN107522259A (en) * | 2016-06-22 | 2017-12-29 | 中山中粤马口铁工业有限公司 | A kind of chromic acid online recycling device and its application method |
| CN106241954A (en) * | 2016-08-22 | 2016-12-21 | 江苏辰盛环保科技有限公司 | A kind of ion exchange in solution device |
| CN106587433B (en) * | 2016-12-20 | 2020-04-10 | 无锡出新环保设备有限公司 | Chromium-containing wastewater treatment system adopting double anion exchange columns and treatment method thereof |
| CN107055898A (en) * | 2017-01-11 | 2017-08-18 | 广州奥科达水处理设备有限公司 | A kind of chromate waste water processing and recovery process |
| CN107828962A (en) * | 2017-10-19 | 2018-03-23 | 兰州城市学院 | The method that ferrochrome ion in industrial chromite is adsorbed using ion exchange resin |
| EP3715335A1 (en) * | 2018-07-26 | 2020-09-30 | Eisenmann SE | Surface treatment system, preconditioning device and method for preparing process medium and/or flushing medium |
| CN111036312B (en) * | 2020-01-04 | 2024-01-30 | 西安热工研究院有限公司 | Ion exchange resin regeneration monitoring control system and method |
| CN113044919B (en) * | 2021-04-28 | 2023-12-22 | 武汉恩孚水务有限公司 | Power plant condensate fine treatment process and device |
| CN116282163B (en) * | 2021-12-20 | 2024-03-22 | 重庆昌元化工集团有限公司 | Method for improving quality of chromic anhydride |
| CN115571948A (en) * | 2022-10-09 | 2023-01-06 | 泉州中节能水处理科技有限公司 | Method for treating and recycling electroplating chromium-containing wastewater through ion exchange |
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| US20030196962A1 (en) * | 2002-04-22 | 2003-10-23 | William Fries | Process for selective removal of toxic ions from water |
| CN1762830A (en) * | 2005-08-29 | 2006-04-26 | 陈秀恋 | Device for changing chromic acid waste water to high purity regenerated chromic acid liquid capable of circulated utilization |
| CN101746906A (en) * | 2008-12-03 | 2010-06-23 | 五邑大学 | Method for processing electroplating wastewater with heavy metal ions |
| CN104230035A (en) * | 2013-06-10 | 2014-12-24 | 天津市绿净源环保科技有限公司 | A chromium-containing water separation and purification method |
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