CN104909508A - Electroplating chromium-containing wastewater treatment method and device - Google Patents
Electroplating chromium-containing wastewater treatment method and device Download PDFInfo
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- CN104909508A CN104909508A CN201510307762.0A CN201510307762A CN104909508A CN 104909508 A CN104909508 A CN 104909508A CN 201510307762 A CN201510307762 A CN 201510307762A CN 104909508 A CN104909508 A CN 104909508A
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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
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- Y02A20/124—Water desalination
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, particularly relate to a kind for the treatment of process and treatment unit of waste electroplating liquor containing chromium.
Technical background
Tin plate is commonly called as tinplate, be widely used in food, beverage, oil and fat chemical, coating, paint, sprays, the packaging of other daily necessities such as bottle cap, according to the statistic data display of the metal council of Chinese packaging association, China's tin plate consumption in 2006 increased substantially than 2005: inhalator jar increases by 11%, beverage Three piece Can increases by 33%, food Three piece Can increases by 71%, Metal Crown Lid increases by 15%, chemical tank increases by 30%, within 2012, global tinplate demand reaches 2,000 ten thousand tons, during 12, China's packaging industry will increase fast, tinplate container will face major opportunity, development space is huge, there is wide market.Electrolytic tin plate production line comprises band charging workshop section, zinc-plated pre-treatment workshop section, plating tank workshop section, chemical treatment workshop section and finished product workshop section.Wherein chemical treatment workshop section: be made up of passivation, flushing, oven dry and Electrostatic greasing device four part.The composition of passivating solution is sodium dichromate 99 and chromic acid.Tin plate after passivation enters finished product workshop section after cleaning down, oven dry and Electrostatic greasing.
To produce a large amount of chromate waste waters in passivation procedure and flushing operation, this effluent part is directly entered workshop sewage plant and processes by current most of enterprise, produces a large amount of chromium that contains and endangers useless, waste a large amount of water resourcess simultaneously.12 planning periods, the center of gravity of Chinese government's work starts to tilt to energy-conserving and environment-protective field, brings forward and will develop low-carbon economy and low-carbon energy.How reaching the object of energy-saving and emission-reduction, is the problem of pendulum in face of all enterprises.
Sexavalent chrome be in electroplating industry the most seriously, one of the most difficult primary pollution source, sexavalent chrome is defined as one of toxicant of l 7 kinds of highly dangerous by USEPA (E P A).Chromium exists with trivalent and hexavalent form in water, and wherein chromic toxicity is very large, is approximately chromic 100 times, if chromic content is more than the concentration of 0.1mg/L in water, will produces toxic action to human body.Chromic waste water, refuse can not natural degradations, and it, biological and accumulated in creatures, can cause the harm of chronicity, and being the extremely strong strong carcinogenic substance of a kind of toxicity, is also serious corrosive medium.The carry-over loss of chromium ion source of pollution mainly chromium plating in electroplating industry, only be plated on workpiece less than the chromium ion of 15%, and the chromium ion of more than 85% has all been washed in sewage treatment tank, to process and the reuse of chromate waste water, and the chromic acid taken out of in chrome-plating process recovery will be had obvious economic benefit.
The main methods of Present Domestic waste electroplating liquor containing chromium is divided into: chemical reduction method, electrolytic process, membrane separation process, absorption method, biological process, ion exchange method etc.Chemical reduction method utilizes reductive agent that Cr (VI) strong for waste water toxic is reduced into the little Cr of toxicity low solubility (III), and finally with chromium hydroxide precipitation removing, this method equipment is simple, processing ease, and working cost is low; But produce a large amount of sediment mud being difficult to process, can secondary pollution be produced.Electrolytic process utilizes Cr (VI) in electrode and waste water electrochemical reaction occurs and eliminates the method for its toxicity, and this method electric energy consumption is large, and electrode metal consumption is large, and the throw out not easily processing and utilizing be separated, there is certain secondary pollutant.Membrane separation process treatment of chromium containing wastewater is in exploration and developmental stage, and in addition, the cost of film is relatively high, and uses for some time need carry out regenerating or changing for it, and when producing for wastewater treatment in enormous quantities, process cost is larger.Absorption method occurs to adsorb with the Cr (VI) in the larger specific surface area of sorbent material and waste water and removes method; This method can process more rapidly the chromium ion of waste water, and treatment effect is better, and process cost is few, but consumes sorbent material, and equipment is huge; During actual production, the transport charging discharging of sorbent material is more difficult, and desorption still exists certain technical difficulty.Biological process mainly relies on the function yeast of artificial culture, utilizes the electrostatic adsorption of microorganism, the catalyzed conversion effect of enzyme, complexing action, throwing out, co-precipitation to remove Cr in waste water (VI), applies less in Practical Project.Ion exchange method process electroplating wastewater, effluent quality is good, recyclable useful matter, is convenient to realize automatization, and the shortcoming of this method is resin easily oxidized and pollution, higher to pre-processing requirements.
At present, the method for processing waste water containing chrome is a lot, but traditional chemical reduction precipitator method, electrolytic process have secondary pollution, and chromium ion is difficult to the shortcomings such as recycling; Although biological process, membrane separation process have a extensive future, be also in the research trial period at present, extensive utilization needs time; And ion exchange method and absorption method are the good methods of current processing waste water containing chrome, there is exchange adsorption capacity large, recycle effective, to environment non-secondary pollution, apply more extensive, the advantages such as technology is more ripe, but have that pre-processing requirements is higher, resin easily oxidized, reclaim the shortcomings such as chromic acid concentration is lower.
In sum, the current waste electroplating liquor containing chromium quantity discharged of China is large, and hexavalent chromium polluted toxicity is large, is faced with severe environmental protection pressure, governs the development of industry.Adopt traditional waste water treatment process can not meet environmental requirement, and economic benefit is lower.
Therefore, prior art has yet to be improved and developed.
Summary of the invention
In view of above-mentioned the deficiencies in the prior art, the object of the invention is to a kind for the treatment of process and treatment unit of waste electroplating liquor containing chromium, the treatment process of described waste electroplating liquor containing chromium and treatment unit are applicable to process tinplate and produce the chromate waste water that chromate waste water in passivation technology and electroplating industry carry out producing in chrome-plating process, be intended to solve and there is secondary pollution about chromium containing waste water treatment method at present, water is less can be back to electroplate rinsing technique in process, and chromic acid such as can not to reclaim at the problem.
Technical scheme of the present invention is as follows:
A treatment process for waste electroplating liquor containing chromium, for reclaiming the chromic acid in electroplating process in chromate waste water, wherein, comprises the following steps:
A, in advance by pretreater, the suspended impurity in chromate waste water, grease and iron ion to be removed, obtain the water outlet after preliminary treatment; Wherein, described pretreater comprises one or more in settling vessel, grease trap, deep bed filter and fiber bundle filter;
B, water outlet is carried out just one-step desalting detect whether saturated penetrating by cation exchanger and anion exchanger successively; Reduce the pH value of water outlet, by the Cr in water outlet
6+be converted into Cr
2o
7 2-form, and exchange on the resin of anion exchanger; Again water outlet is carried out desalination again by advanced treatment cation bed and advanced treatment anion bed successively, reduce the electric conductivity of water outlet, obtain the recyclable de-mineralized water for chromium plating rinsing;
C, when cation exchanger is saturated penetrate after, regenerated by cation bed regenerating unit: in cation exchanger, pass into HCl regenerated liquid carry out co-current regeneration, obtain cation bed regenerated liquid and also enter in cation bed regenerated liquid collection box; When anion exchanger is saturated penetrate after, regenerated by anion bed regenerating unit: in anion exchanger, pass into NaOH regenerated liquid carry out co-current regeneration, obtain anion bed regenerated liquid and also enter in anion bed regenerated liquid collection box;
Anion bed regenerated liquid in D, anion bed regenerated liquid collection box is pumped to take off in sodium device to cation bed through lift pump and is carried out de-sodium process, obtains lower concentration chromic acid and enters in chromic acid withdrawing can side by side; Pump through chromic acid lift pump again and be condensed into the recyclable high density chromic acid for chromium plating to vacuum evaporation device; Regenerating cation exchanger liquid in cation bed regenerated liquid collection box pumps evaporative crystallization to vacuum evaporation device through lift pump.
The treatment process of described waste electroplating liquor containing chromium, wherein, in stepb, the resin of filling in cation exchanger is H type 001 × 7 strongly acidic styrene type cation exchange resin; The height of described Zeo-karb is 1.0-3.0m, and operation flow velocity during work is 15-30m/h; The resin of filling in anion exchanger is D301 macroreticular weakly base styrene series anion exchange resin; The height of described anionite-exchange resin is 2-3m, and operation flow velocity during work is 15-30m/h.
The treatment process of described waste electroplating liquor containing chromium, wherein, in stepb, water outlet, after the desalination again of described advanced treatment cation bed and advanced treatment anion bed, obtains the de-mineralized water of specific conductivity < 10 μ s/cm; The resin of filling in described advanced treatment cation bed is H type 001 × 7 strongly acidic styrene type cation exchange resin, and it is highly 1-2m; The resin of filling in described advanced treatment anion bed is 201 × 7 strong-basicity styrene series anion exchange resins, and it is highly 1-2m.
The treatment process of described waste electroplating liquor containing chromium, wherein, in stepb, the water inlet pipe of described anion exchanger and rising pipe are the transparent tube for monitoring water outlet color, are also provided with one for detecting cation exchanger and the whether saturated ORP on-line detector penetrated of anion exchanger simultaneously; Described anion exchanger comprises the first anion exchanger and the second anion exchanger, and wherein, one for work and another is for subsequent use, or for be communicated with work successively.
The treatment process of described waste electroplating liquor containing chromium, wherein, in step C, the regeneration velocity in described cation bed regenerating unit and anion bed regenerating unit is 5m/h; In described HCl regenerated liquid, the mass concentration of HCl is 5-7%; In described NaOH regenerated liquid, the mass concentration of NaOH is 7-10%.
A kind for the treatment of unit of waste electroplating liquor containing chromium, wherein, described treatment unit includes a pretreater for the suspended impurity in chromate waste water, grease and iron ion being removed, and described pretreater is connected with cation exchanger, anion exchanger, advanced treatment cation bed and advanced treatment anion bed in turn by pipeline;
Described cation exchanger is also connected with one for the cation bed regenerating unit of resin in cation regenerant interchanger; Described anion exchanger is also connected with one for the anion bed regenerating unit of resin in anion regenerant interchanger.
The treatment unit of described waste electroplating liquor containing chromium, it is characterized in that, described cation bed regenerating unit comprises the first regeneration auxiliary tank, the first regenerative pump, sour batch meter and Acid injector, wherein, described sour batch meter is connected to described Acid injector and cation exchanger successively by pipeline, described first regeneration auxiliary tank passes through pipeline successively in described first regenerative pump and described Acid injector, described first regeneration auxiliary tank is also connected with the evacuated tube bottom cation exchanger by pipeline, forms circulation line; Described sour batch meter is also connected with one for storing the sour storage tank of HCl regenerated liquid by pipeline;
Described anion bed regenerating unit comprises the second regeneration auxiliary tank, the second regenerative pump, alkali batch meter and alkali injector, wherein, described alkali batch meter is connected to described alkali injector and anion exchanger successively by pipeline, described second regeneration auxiliary tank passes through pipeline successively in described second regenerative pump and described alkali injector, described second regeneration auxiliary tank is also connected with the evacuated tube bottom anion exchanger by pipeline, forms circulation line; Described alkali batch meter is also connected with one for storing the alkali storage tank of NaOH regenerated liquid by pipeline.
The treatment unit of described waste electroplating liquor containing chromium, wherein, described treatment unit also includes the anion bed regenerated liquid collection box being connected to described anion exchanger; Be connected with cation bed in turn by pipeline in described anion bed regenerated liquid collection box and take off sodium device, chromic acid withdrawing can and vacuum evaporation device; Also include the cation bed regenerated liquid collection box being connected to described cation exchanger; Described cation bed regenerated liquid collection box is connected with described vacuum evaporation device.
The treatment unit of described waste electroplating liquor containing chromium, wherein, described treatment unit also comprises: the chromate waste water case after being connected to pretreater, and described chromate waste water case is used for carrying out all the chromate waste water after pretreater preliminary treatment and water quality and stabilizing water quantity; Be arranged on the reuse water tank between anion exchanger and advanced treatment cation bed, described reuse water tank is for storing the de-mineralized water after cation exchanger and the first one-step desalting of anion exchanger; Also be provided with a wastewater collection pond for reclaiming the waste water produced in treating processes.
The treatment unit of described waste electroplating liquor containing chromium, wherein, described treatment unit also comprises: be arranged on the first deep bed filter between chromate waste water case and cation exchanger; Be arranged on anion bed regeneration collection box and cation bed takes off the second deep bed filter between sodium device; And be arranged on cation bed and take off the 3rd deep bed filter between sodium device and chromic acid withdrawing can.
Beneficial effect: the treatment process of a kind of waste electroplating liquor containing chromium of the present invention and treatment unit, it is by combining ion exchange method and evaporation concentration technique, achieve the closed cycle utilization that waste electroplating liquor containing chromium administers reuse and chromic acid, substantially obtain zero release, eliminate chromic environmental pollution; Decrease the consumption of tap water and de-mineralized water simultaneously, saved the consumption of chromic acid, decrease sewage water discharge expense and containing the handling of chromium solid waste, environmental benefit and economic benefit obvious.
Accompanying drawing explanation
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 treatment unit of waste electroplating liquor containing chromium of the present invention.
Fig. 3 is anion exchanger and anion bed regenerating unit equipment drawing thereof in the treatment unit of waste electroplating liquor containing chromium of the present invention.
Embodiment
The invention provides a kind for the treatment of process and treatment unit of waste electroplating liquor containing chromium, for making object of the present invention, technical scheme and effect clearly, clearly, the present invention is described in more detail below.Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not intended to limit the present invention.
Refer to Fig. 1, the invention provides a kind for the treatment of process of waste electroplating liquor containing chromium, for reclaiming the chromic acid in electroplating process in chromate waste water, it specifically comprises the following steps:
S100, in advance by pretreater, the suspended impurity in chromate waste water, grease and iron ion to be removed, obtain the water outlet after preliminary treatment; Wherein, described pretreater comprises one or more in settling vessel, grease trap, deep bed filter and fiber bundle filter;
S200, water outlet is carried out just one-step desalting detect whether saturated penetrating by cation exchanger and anion exchanger successively; Reduce the pH value of water outlet, by the Cr in water outlet
6+be converted into Cr
2o
7 2-form, and exchange on the resin of anion exchanger; Again water outlet is carried out desalination again by advanced treatment cation bed and advanced treatment anion bed successively, reduce the electric conductivity of water outlet, obtain the recyclable de-mineralized water for chromium plating rinsing;
S300, when cation exchanger is saturated penetrate after, regenerated by cation bed regenerating unit: in cation exchanger, pass into HCl regenerated liquid carry out co-current regeneration, obtain cation bed regenerated liquid and also enter in cation bed regenerated liquid collection box; When anion exchanger is saturated penetrate after, regenerated by anion bed regenerating unit: in anion exchanger, pass into NaOH regenerated liquid carry out co-current regeneration, obtain anion bed regenerated liquid and also enter in anion bed regenerated liquid collection box;
Sodium chromate liquid in S400, anion bed regenerated liquid collection box is pumped to take off in sodium device to cation bed through lift pump and is carried out de-sodium process, obtains lower concentration chromic acid and enters in chromic acid withdrawing can side by side; Pump through chromic acid lift pump again and be condensed into the recyclable high density chromic acid for chromium plating to vacuum evaporation device; Regenerating cation exchanger liquid in cation bed regenerated liquid collection box pumps evaporative crystallization to vacuum evaporation device through lift pump.
The treatment process of waste electroplating liquor containing chromium of the present invention, be specifically applied to tinplate and produce chromate waste water and similar chromate waste water process in passivation technology, it is by combining ion exchange method and evaporation concentration technique, achieve the closed cycle utilization that waste electroplating liquor containing chromium administers reuse and chromic acid, eliminate chromic environmental pollution; Decrease the consumption of tap water and de-mineralized water simultaneously, save the consumption of chromic acid.
Particularly, in the step s 100, in described chromate waste water, chromic concentration is generally 20-200mg/L, and its specific conductivity is 500-2000 μ s/cm, and containing a small amount of impurity, iron ion content is low, pH value < 5.Therefore first by pretreater, granule foreign, grease and iron ion etc. are first removed, according to different water quality, different pretreaters can be selected, as settling vessel, grease trap, deep bed filter or fiber bundle filter etc.After chromate waste water tentatively removes impurity, enter in chromate waste water case and carry out even water quality and stabilizing water quantity, obtain the water outlet after preliminary treatment, for next step operation is prepared.Subsequently, by lift pump, described water outlet is promoted in the first deep bed filter, the filtering accuracy of described first deep bed filter is 100 μm, tiny suspended impurity interception in waste water can be removed by further, avoids pollution and the blocking of resin in follow-up cation exchanger and anion exchanger.
Enter subsequently in step S200, namely just one-step desalting and again desalination are carried out to water outlet, reduce the content of poisonous hexavalent chromium.Particularly, in the cation exchanger adopted during first one-step desalting, its resin of filling is H type 001 × 7 strongly acidic styrene type cation exchange resin, and the height of described Zeo-karb is 1.0-3.0m, and operation flow velocity during work is 15-30m/h.Cr in described cationic exchange resin adsorption water outlet
3+deng positively charged ion, discharge H simultaneously
+ion, can make water outlet pH value be reduced to≤4, under this pH value, in waste water, chromium element is mainly with Cr
2o
7 2-form exists.When water outlet enters anion exchanger after cation exchanger, because of pH value≤4 in waste water, sexavalent chrome mainly exists with dichromate ion form, and dichromate ion form is beneficial to the exchange capacity effectively utilizing resin, and principle is as follows:
2ROH + CrO
4 2-= R
2CrO
4+2OH
-
2ROH + Cr
2O
7 2- =R
2Cr
2O
7+2OH
-
From reaction formula, with the plastic resin treatment sexavalent chrome of identical amount, by Cr
2o
7 2-exchange capacity for press CrO
4 2-2 times of exchange capacity, and CrO
4 2-very difficult replacement is by the SO of resin absorption
4 2-fat, Cl
-deng negatively charged ion, and Cr
2o
7 2-then easily replace by the SO of resin absorption
4 2-fat, Cl
-deng negatively charged ion.The resin employing model of therefore filling in anion exchanger in the present embodiment is the anionite-exchange resin (being called for short D301 resin) of D301 macroreticular weakly base polystyrene; The height of described anionite-exchange resin is 2-3m, and operation flow velocity during work is 15-30m/h.D301 resin has dichromate ion and exchanges selective power preferably, Cr
2o
7 2-can preferentially be exchanged by D301 Choice of Resin, it effectively can improve Cr
2o
7 2-adsorption rate.In addition, the water inlet pipe of described anion exchanger and rising pipe are all arranged transparent tube, water outlet color can be monitored, ORP on-line checkingi instrument is set simultaneously, determine that whether anion exchanger is saturated and penetrate.Preferably, described anion exchanger comprises the first anion exchanger and the second anion exchanger, wherein, a set of for work and another set of be for subsequent use, or for be communicated with work successively.The operation scheme of anion exchanger described in the present embodiment is: the complete saturated flow process of jack to jack adapter post series connection.As shown in Figure 3, under normal circumstances, run a set of anion exchanger, when it is close to saturated penetrating, another set of anion exchanger of namely connecting, continues to run; When the first anion exchanger water outlet is the same with water inlet hexavalent chromium concentration, first set anion exchanger out of service, now, both can ensure that total water outlet sexavalent chrome did not exceed standard, can make again the SO that may adsorb exchange in the first anion exchanger
4 2-, Cl
-deng negatively charged ion gradually by Cr
2o
7 2-replace, improve concentration and the purity of dichromate ion.Because the exchange selectivity order of D301 resin to negatively charged ion is: Cr
2o
7 2-> SO
4 2-> NO
3 -> CrO
4 2-> Cl
-> OH
-, when other negatively charged ion in the first anion exchanger are completely by Cr
2o
7 2-after replacement, its water inlet is the same with the content of 6-valence Cr ions in water outlet, gets final product the first anion exchanger out of service, and isolated operation second anion exchanger; So, Cr in anion exchanger can be improved
2o
7 2-concentration and purity.
And in desalination again, the resin of filling in the advanced treatment cation bed adopted is H type 001 × 7 strongly acidic styrene type cation exchange resin (being called for short positive resin 001 × 7), its resin height is 1-2m, and operation flow velocity is 15-30m/h.The resin of filling in described advanced treatment anion bed is in addition 201 × 7 strong-basicity styrene series anion exchange resins (being called for short negative resin 201 × 7), and its resin height 1-2m, runs flow velocity 15-30m/h.After the deep desalting of described advanced treatment cation bed and advanced treatment anion bed, make water outlet conductivity lower than 10 μm, it is the de-mineralized water of high-quality, after deep bed filter again impurity screening, electroplate rinsing operation can be back to, save the use water in electroplating process, improve waste water reclamation utilization ratio.
After desalination, constant when being observed water outlet colour stable by transparent tube, and ORP on-line checkingi instrument detects that cation exchanger and anion exchanger are saturated when penetrating, and enters step S300, namely regenerates respectively by cation bed regenerating unit and anion bed regenerating unit.Such as, the sexavalent chrome that anion exchanger absorption exchanges, its on resin the time after oxidizing reaction occurring for a long time, become trivalent chromium, resin is when alkali lye (the present invention is the NaOH being arranged in alkali storage tank) regenerates, hydroxide three chromium throw out can be formed, invest resin surface, affect the exchange capacity of resin.Resin in anion exchanger is after several alkali liquid regeneration, operating capacity can decline gradually, regeneration period shortens gradually, when the regeneration period foreshortens to 1-2 days, need active regeneration, with the acid soak 8-10 hour of about 7%, precipitate dissolves is separated out, again with alkali liquid regeneration after flushing.
Particularly, described regenerating cation exchanger adopts co-current regeneration mode, and it adopts the mass concentration of HCl to be 5-7%, and flow velocity is 3-5m/h, and the recovery time is 1-1.5h; After regeneration completes, obtain cation bed regenerated liquid and enter in described cation bed regenerated liquid collection box.Then use scavenging solution (as clear water) soak and repeatedly rinse, such as, soaking flushing liquid continues to enter in cation bed regenerated liquid collection box for the first time; Second and third, four soaking flushing liquid enter in the first regeneration auxiliary tank in cation bed regenerating unit, are used as regenerated liquid and the scavenging solution of cation exchanger next time; Rinse to washing fluid pH value is neutrality.Preferably, bottom described cation exchanger, be provided with a diffuser, make appropriate air inlet to stir when soaking flushing, can developing result be strengthened.Further, collected in described cation bed regenerated liquid collection box cation bed regenerated liquid can enter into sewage collecting box and focus on.
Similarly, described anion exchanger regeneration also adopts co-current regeneration mode, and in its regenerated liquid adopted, the mass concentration of NaOH is 7-10%, and flow velocity is 3-5m/h, and the recovery time is 2-3h.Specifically refer to Fig. 3, comprise the second regeneration auxiliary tank 14, second regenerative pump 13, alkali batch meter 12, alkali injector 11(cation bed regenerating unit similar in described anion bed regenerating unit 1, be not repeated herein).Wherein, the water-in of the second regeneration auxiliary tank 14 is provided with a pipeline be connected with anion exchanger evacuation port.During regeneration, when regenerated liquid (i.e. NaOH solution) just dipped resin time, start air stirrer, fully make regenerated liquid, air contacts with resin friction, the issuable throw out of regeneration that hinders being eluted by constantly flowing, being conducive to resin regeneration; The cyclic regeneration time is about 1.5-2h.After regeneration completes, entered by anion bed regenerated liquid in described anion bed regenerated liquid collection box, then use clear water soaking flushing, washing fluid, enters anion bed regenerated liquid collection box for the first time; Second and third, four soaking flushing liquid enter in the second regeneration auxiliary tank, are used as regenerated liquid and the scavenging solution of anion exchanger next time; When being about 8 to washing fluid pH value, stop rinsing.Preferably, bottom described anion exchanger, be provided with a diffuser, air inlet can stir in right amount during soaking flushing, can developing result be strengthened.In addition, the top water distribution manner of described anion exchanger adopts spiral nozzle, and washing fluid can evenly be trickled down on resin face, in order to avoid form bias current, make regeneration comparatively complete, washing water quantity is few and clean.
In addition, the Sodium chromate containing higher concentration in anion bed regenerated liquid collected in anion bed regenerated liquid collection box, therefore can be pumped by lift pump and filter to the second deep bed filter, removing suspended impurity, then enters cation bed and take off in sodium device and carry out de-sodium process.Particularly, it is D001 macroporous type superacicd styrene cation exchange resin that described cation bed takes off the resin of filling in sodium device, and its resin height is 2-3m, and operation flow velocity is 15-30m/h.Anion bed regenerated liquid (containing chromium acid sodium solution) takes off after sodium device takes off sodium through cation bed and obtains dichromic acid, pollute for preventing the broken thing of impurity and resin in equipment, pipeline, filter after removal impurity and broken thing through the 3rd deep bed filter again, be collected in chromic acid withdrawing can.And the chromic acid concentration in described chromic acid withdrawing can is compared with practical application, its concentration is less, for reaching processing requirement, chromic acid need be concentrated to respective concentration.Therefore send into vacuum evaporation device by chromic acid lift pump again, evaporation concentration obtains the higher chromic acid of concentration, is back to Electroplating Production.
Refer to Fig. 2 and Fig. 3, the present invention also provides a kind for the treatment of unit of waste electroplating liquor containing chromium, wherein, described treatment unit includes a pretreater for the suspended impurity in chromate waste water, grease and iron ion being removed, and described pretreater is by being connected with cation exchanger, anion exchanger, advanced treatment cation bed and advanced treatment anion bed in turn by pipeline; Described cation exchanger is also connected with one for the cation bed regenerating unit of resin in cation regenerant interchanger; Described anion exchanger is also connected with one for the anion bed regenerating unit of resin in anion regenerant interchanger.
Further, described cation bed regenerating unit comprises the first regeneration auxiliary tank, the first regenerative pump, sour batch meter and Acid injector, wherein, described sour batch meter is connected to described Acid injector and cation exchanger successively by pipeline, described first regeneration auxiliary tank passes through pipeline successively in described first regenerative pump and described Acid injector, described first regeneration auxiliary tank is also connected with the evacuated tube bottom cation exchanger by pipeline, forms circulation line; Described sour batch meter is also connected with one for storing the sour storage tank of HCl regenerated liquid by pipeline.
Similarly, described anion bed regenerating unit comprises the second regeneration auxiliary tank, the second regenerative pump, alkali batch meter and alkali injector, wherein, described alkali batch meter is connected to described alkali injector and anion exchanger successively by pipeline, described second regeneration auxiliary tank passes through pipeline successively in described second regenerative pump and described alkali injector, described second regeneration auxiliary tank is also connected with the evacuated tube bottom anion exchanger by pipeline, forms circulation line; Described alkali batch meter is also connected with one for storing the alkali storage tank of NaOH regenerated liquid by pipeline.
In preferred embodiment, described treatment unit also includes the anion bed regenerated liquid collection box and negatively charged ion scavenging solution storage tank that are all connected to described anion bed regenerating unit; Be connected with cation bed in turn by pipeline in described anion bed regenerated liquid collection box and take off sodium device, chromic acid withdrawing can and vacuum evaporation device; Also include the cation bed regenerated liquid collection box and positively charged ion scavenging solution storage tank that are all connected to described cation bed regenerating unit; Described cation bed regenerated liquid collection box is connected with described vacuum evaporation device.
Preferably, described treatment unit also comprises: the chromate waste water case after being connected to pretreater, and described chromate waste water case is used for carrying out all the chromate waste water after pretreater preliminary treatment and water quality and stabilizing water quantity; Be arranged on the reuse water tank between anion exchanger and advanced treatment cation bed, described reuse water tank is for storing the de-mineralized water after cation exchanger and the first one-step desalting of anion exchanger; Also be provided with a wastewater collection pond for reclaiming the waste water produced in treating processes.
More specifically, described treatment unit also comprises: be arranged on the first deep bed filter between chromate waste water case and cation exchanger; Be arranged on anion bed regeneration collection box and cation bed takes off the second deep bed filter between sodium device; And be arranged on cation bed and take off the 3rd deep bed filter between sodium device and chromic acid withdrawing can.
The specific operation process of device described in the present invention is identical with the performing step of aforesaid method flow process, does not repeat them here.It should be noted that in the present invention, accompanying drawing does not form the restriction to this programme in addition, accompanying drawing is only a kind of enforcement figure of preferred embodiment.
In sum, the treatment process of a kind of waste electroplating liquor containing chromium provided by the present invention and treatment unit, its compared with prior art, tool has the following advantages and treatment effect:
(1) the present invention combines ion exchange method and vacuum evaporation crystallization process, adopts comprehensive processing technique, and cation bed etc. can be discharged waste water and carry out evaporation concentration, discharge water reuse, the crystal of generation can reclaim further; And the Sodium chromate in anion bed is carried out concentration and recovery, again utilizes; The present invention's effect in energy-saving and emission-reduction, waste water recycling and resource reclaim, minimizing secondary pollution is better, achieves certain economic benefit and social benefit;
(2) adopt secondary sun anion bed system, both eliminated chromic environmental pollution, and high-quality de-mineralized water can have been obtained simultaneously, be back to production, and saved tap water, de-mineralized water consumption; Adopt the sexavalent chrome in the complete saturated flow process method absorption exchange waste water of jack to jack adapter post series connection, improve the concentration and purity that reclaim chromate, improve the utilization ratio of D301 resin, extend the cycle of operation;
(3) regeneration of ion-exchanger is improved: cyclic regeneration, air bump rinse operation, scavenging solution second stage employ, decrease the consumption of regenerated liquid and scavenging solution, and improve regeneration solution concentration; After several conventional regeneration, adopt and bring back to life regeneration, decrease regenerating agent consumption, delay the aging of resin;
(4) ion exchanger top water distribution manner adopts spiral nozzle, and washing fluid can evenly be trickled down on resin face, in order to avoid form bias current, make regeneration comparatively complete, washing water quantity is few and clean; Arrange diffuser bottom ion-exchanger, during soaking flushing, appropriate air inlet is stirred, and can strengthen developing result.
Should be understood that, application of the present invention is not limited to above-mentioned citing, for those of ordinary skills, can be improved according to the above description or convert, and all these improve and convert the protection domain that all should belong to claims of the present invention.
Claims (10)
1. a treatment process for waste electroplating liquor containing chromium, for reclaiming the chromic acid in electroplating process in chromate waste water, is characterized in that, comprising the following steps:
A, in advance by pretreater, the suspended impurity in chromate waste water, grease and iron ion to be removed, obtain the water outlet after preliminary treatment; Wherein, described pretreater comprises one or more in settling vessel, grease trap, deep bed filter and fiber bundle filter;
B, water outlet is carried out just one-step desalting detect whether saturated penetrating by cation exchanger and anion exchanger successively; Reduce the pH value of water outlet, by the Cr in water outlet
6+be converted into Cr
2o
7 2-form, and exchange on the resin of anion exchanger; Again water outlet is carried out desalination again by advanced treatment cation bed and advanced treatment anion bed successively, reduce the electric conductivity of water outlet, obtain the recyclable de-mineralized water for chromium plating rinsing;
C, when cation exchanger is saturated penetrate after, regenerated by cation bed regenerating unit: in cation exchanger, pass into HCl regenerated liquid carry out co-current regeneration, obtain cation bed regenerated liquid and also enter in cation bed regenerated liquid collection box;
When anion exchanger is saturated penetrate after, regenerated by anion bed regenerating unit: in anion exchanger, pass into NaOH regenerated liquid carry out co-current regeneration, obtain anion bed regenerated liquid and also enter in anion bed regenerated liquid collection box;
Anion bed regenerated liquid in D, anion bed regenerated liquid collection box is pumped to take off in sodium device to cation bed through lift pump and is carried out de-sodium process, obtains lower concentration chromic acid and enters in chromic acid withdrawing can side by side; Pump through chromic acid lift pump again and be condensed into the recyclable high density chromic acid for chromium plating to vacuum evaporation device;
Regenerating cation exchanger liquid in cation bed regenerated liquid collection box pumps evaporative crystallization to vacuum evaporation device through lift pump.
2. the treatment process of waste electroplating liquor containing chromium according to claim 1, it is characterized in that, in stepb, the resin of filling in cation exchanger is H type 001 × 7 strongly acidic styrene type cation exchange resin; The height of this resin is 1.0-3.0m, and operation flow velocity during work is 15-30m/h;
The resin of filling in anion exchanger is D301 macroreticular weakly base styrene series anion exchange resin; The height of this resin is 2-3m, and operation flow velocity during work is 15-30m/h.
3. the treatment process of waste electroplating liquor containing chromium according to claim 1, is characterized in that, in stepb, water outlet, after the desalination again of described advanced treatment cation bed and advanced treatment anion bed, obtains the de-mineralized water of specific conductivity < 10 μ s/cm;
Wherein, the resin of filling in described advanced treatment cation bed is H type 001 × 7 strongly acidic styrene type cation exchange resin, and it is highly 1-2m; The resin of filling in described advanced treatment anion bed is 201 × 7 strong-basicity styrene series anion exchange resins, and it is highly 1-2m.
4. the treatment process of waste electroplating liquor containing chromium according to claim 1, it is characterized in that, in stepb, the water inlet pipe of described anion exchanger and rising pipe are the transparent tube for monitoring water outlet color, are also provided with one for detecting cation exchanger and the whether saturated ORP on-line detector penetrated of anion exchanger simultaneously;
Described anion exchanger comprises the first anion exchanger and the second anion exchanger, wherein, a set of for work and another set of be for subsequent use, or for be communicated with work successively.
5. the treatment process of waste electroplating liquor containing chromium according to claim 1, is characterized in that, in step C, the regeneration velocity in described cation bed regenerating unit and anion bed regenerating unit is 3-5m/h; In described HCl regenerated liquid, the mass concentration of HCl is 5-7%; In described NaOH regenerated liquid, the mass concentration of NaOH is 7-10%.
6. the treatment unit of a waste electroplating liquor containing chromium, it is characterized in that, described treatment unit includes a pretreater for the suspended impurity in chromate waste water, grease and iron ion being removed, and described pretreater is connected with cation exchanger, anion exchanger, advanced treatment cation bed and advanced treatment anion bed in turn by pipeline;
Described cation exchanger is also connected with one for the cation bed regenerating unit of resin in cation regenerant interchanger; Described anion exchanger is also connected with one for the anion bed regenerating unit of resin in anion regenerant interchanger.
7. the treatment unit of waste electroplating liquor containing chromium according to claim 6, it is characterized in that, described cation bed regenerating unit comprises the first regeneration auxiliary tank, the first regenerative pump, sour batch meter and Acid injector, wherein, described sour batch meter is connected to described Acid injector and cation exchanger successively by pipeline, described first regeneration auxiliary tank passes through pipeline successively in described first regenerative pump and described Acid injector, described first regeneration auxiliary tank is also connected with the evacuated tube bottom cation exchanger by pipeline, forms circulation line; Described sour batch meter is also connected with one for storing the sour storage tank of HCl regenerated liquid by pipeline;
Described anion bed regenerating unit comprises the second regeneration auxiliary tank, the second regenerative pump, alkali batch meter and alkali injector, wherein, described alkali batch meter is connected to described alkali injector and anion exchanger successively by pipeline, described second regeneration auxiliary tank passes through pipeline successively in described second regenerative pump and described alkali injector, described second regeneration auxiliary tank is also connected with the evacuated tube bottom anion exchanger by pipeline, forms circulation line; Described alkali batch meter is also connected with one for storing the alkali storage tank of NaOH regenerated liquid by pipeline.
8. the treatment unit of waste electroplating liquor containing chromium according to claim 6, it is characterized in that, described treatment unit also includes the anion bed regenerated liquid collection box being connected to described anion exchanger; Be connected with cation bed in turn by pipeline in described anion bed regenerated liquid collection box and take off sodium device, chromic acid withdrawing can and vacuum evaporation device;
Also include the cation bed regenerated liquid collection box being connected to described cation exchanger; Described cation bed regenerated liquid collection box is connected with described vacuum evaporation device.
9. the treatment unit of waste electroplating liquor containing chromium according to claim 6, it is characterized in that, described treatment unit also comprises: the chromate waste water case after being connected to pretreater, and described chromate waste water case is used for carrying out all the chromate waste water after pretreater preliminary treatment and water quality and stabilizing water quantity; Be arranged on the reuse water tank between anion exchanger and advanced treatment cation bed, described reuse water tank is for storing the de-mineralized water after cation exchanger and the first one-step desalting of anion exchanger; Also be provided with a wastewater collection pond for reclaiming the waste water produced in treating processes.
10. the treatment unit of waste electroplating liquor containing chromium according to claim 6, it is characterized in that, described treatment unit also comprises: be arranged on the first deep bed filter between chromate waste water case and cation exchanger; Be arranged on anion bed regeneration collection box and cation bed takes off the second deep bed filter between sodium device; And be arranged on cation bed and take off the 3rd deep bed filter between sodium device and chromic acid withdrawing can.
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| CN106587433A (en) * | 2016-12-20 | 2017-04-26 | 无锡出新环保设备有限公司 | Chromium-containing waste water treatment system adopting double anion exchange columns and treatment method of system |
| 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 |
| CN110777371A (en) * | 2018-07-26 | 2020-02-11 | 艾森曼欧洲公司 | Surface treatment device, pretreatment device and method for treating a working and/or rinsing medium |
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| CN113044919A (en) * | 2021-04-28 | 2021-06-29 | 武汉恩孚水务有限公司 | Fine treatment process and device for condensed water in power plant |
| 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 |
| CN116282163A (en) * | 2021-12-20 | 2023-06-23 | 重庆昌元化工集团有限公司 | Method for improving quality of chromic anhydride |
| 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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