CN101570372A - Method for purifying electroplating wastewater and comprehensively utilizing resources - Google Patents

Method for purifying electroplating wastewater and comprehensively utilizing resources Download PDF

Info

Publication number
CN101570372A
CN101570372A CNA2009100669058A CN200910066905A CN101570372A CN 101570372 A CN101570372 A CN 101570372A CN A2009100669058 A CNA2009100669058 A CN A2009100669058A CN 200910066905 A CN200910066905 A CN 200910066905A CN 101570372 A CN101570372 A CN 101570372A
Authority
CN
China
Prior art keywords
chromium
adsorption column
resin
exchange resin
acid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CNA2009100669058A
Other languages
Chinese (zh)
Other versions
CN101570372B (en
Inventor
陈继
邓岳锋
龙涛
祝丽荔
刘英辉
郭琳
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Changchun Institute of Applied Chemistry of CAS
Original Assignee
Changchun Institute of Applied Chemistry of CAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Changchun Institute of Applied Chemistry of CAS filed Critical Changchun Institute of Applied Chemistry of CAS
Priority to CN2009100669058A priority Critical patent/CN101570372B/en
Publication of CN101570372A publication Critical patent/CN101570372A/en
Application granted granted Critical
Publication of CN101570372B publication Critical patent/CN101570372B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Abstract

The invention relates to a method for purifying electroplating wastewater and comprehensively utilizing resources, which is to adopt low-cost strong basic anion-exchange resin containing macropores and imidazole structure to reclaim valuable resources in the electroplating wastewater by coupling technology based on a chemical oxidation-reduction method, a precipitation method and an ion exchange method. The method comprises the following steps: firstly, Cr(III) is oxidized into Cr(VI) under basic condition through a chemical reaction; then, Zn, Cu, Ni and other heavy metal elements in the wastewater are transformed into precipitation of hydroxide; and finally, the Cr(VI) in the wastewater is adsorbed by the strong basic anion-exchange resin, the purified water quality achieves the requirement of electroplating pollutant discharge standard and recycle, and the Cr and other heavy metal resources in the electroplating wastewater can be comprehensively reclaimed and utilized. The method overcomes the defects that the prior regenerating process of porous weak-basic resin requires acidification, and the method has the advantages of simple process, low treatment cost, large treatment quantity and acid and base consumption conservation, and is the electroplating wastewater treatment method with green environmental protection and efficient utilization of resources.

Description

The method of a kind of purifying electroplating wastewater, comprehensive utilization of resources
Technical field
The present invention relates to the method for a kind of purifying electroplating wastewater, comprehensive utilization of resources.
Background technology
In recent years, plating of China and tanning industry development were very fast, and various places have been set up many medium and small sized enterprises in succession, but the environmental pollution that refuse caused that emits in the production process also is on the rise.According to incompletely statistics, the annual electroplating wastewater of discharging of China is about 40 * 10 8m 3, mainly contain Cr (III), Cr (VI), Zn (II), Cu (II), Ni (III), Fe heavy metal ion such as (III).Medical research shows that sexavalent chrome is a kind of carcinogenic substance, and the toxicity of Cr (VI) is bigger 100 times than Cr (III).Chromium in waste water (VI) with the difference of pH value respectively with CrO 3, CrO 4 2-, Cr 2O 7 2-Exist etc. form.Since the harmful substance contents height, complicated component, thereby cause the treatment technology difficulty bigger, surrounding environment is caused serious threat.
In order to protect the Sustainable development of environment and promotion electroplating industry, country has formulated plating pollutant emission standard (GB 21900-2008), and wherein discharging has strict regulation to chromate waste water: the highest permission quantity discharged that existing enterprise carries out Cr (VI) and total chromium from June 30,1 day to 2010 January in 2009 is respectively 0.5mg/L and 1.5mg/L; Newly-built enterprise is respectively 0.2mg/L and 1.0mg/L from August 1st, 2008 and existing enterprise from the execution Cr (VI) on July 1st, 2010 and the highest permission quantity discharged of total chromium; Higher in territorial development density, environmental bearing capacity weakens or water environment capacity is less, ecological environment frailty, easily serious water environment pollution problem takes place and need take the area of special protective measures carry out Cr (VI) and always the highest permission quantity discharged of chromium be respectively 0.1mg/L and 0.5mg/L.Discharging to huge sum of money elements such as other Zn, Cu, Ni simultaneously also has strict restriction.Along with the raising of Environmental Protection in China emission standard, the discharging of present many chromate waste waters all considerably beyond this regulation, has seriously been polluted environment.If can effectively reclaim chromium and other has the valency heavy metal resources, not only can reduce environmental pollution, can economize on resources again, turn waste into wealth, have important economic value and social effect.
Waste electroplating liquor containing chromium is handled method commonly used chemical precipitation method, electrolytic process, solvent extration and ion exchange method, and these methods respectively have relative merits.Though the chemical precipitation method cost is low, and is widely applicable, produce a large amount of waste residues, cause secondary pollution easily; Electrolytic reduction needs equipment simple, and floor space is few, but the electrolyzer big energy-consuming, treatment process is trouble, is difficult for promoting; Extraction process has higher efficient, uses more organic solvent, easily causes secondary pollution; Ion exchange method is current more advanced method, and it is fabulous to handle the back effluent quality, recyclable utilization chromium resource wherein, but one-time investment is big, the operational administrative complexity.(high concentration chrome wastewater purifies and reclaims Liu Zhigang, resource technology, CN 1810683A) chromium resource that utilizes in ion exchange resin and the resin and macroporous weak recovery chromate waste water is disclosed, sexavalent chrome in the resin and macroporous weak absorption electroplating wastewater reaches chromic resource recycling.The resin that tradition is used for treatment of chromium containing wastewater is macroporous weakly basic anion exchange resins such as D301, D371 and D370, since its alkalescence a little less than, effective absorption chromium under acid or nearly neutrallty condition only, make it reach high loading capacity, must carry out acidifying to resin earlier, in frequent resin regeneration process, have the problem of consumption acid than big and troublesome poeration.The strong anion-exchange resin that utilization contains glyoxaline structure can solve the above-mentioned defective that traditional anionite-exchange resin exists.Chinese invention patent (Chen Ji, Zhu Lili, Liu Yinghui, the method that a kind of strong anion-exchange resin that contains glyoxaline structure adsorbs hexavalent chromium in the waste water, number of patent application: 200810051262.5) prepared Cr (VI) in the strong anion-exchange resin absorption waste water that a kind of gel-type contains glyoxaline structure, do not need acidization in the regenerative process, solved the above-mentioned defective that traditional anionite-exchange resin exists.Yet this gel type resin has higher production cost, is restricting its extensive use on ion exchange technique.
Summary of the invention
Contain at gel-type on the research basis of strong anion-exchange resin of glyoxaline structure, the macropore that the present invention has prepared a kind of cheapness contains the strong anion-exchange resin of glyoxaline structure, the strong anion-exchange resin that adopts macropore to contain glyoxaline structure adsorbs the Cr (VI) in the electroplating wastewater, chemistry redox method, the precipitator method and ion exchange method are combined, make Cr (III) in the electroplating wastewater and Cr (VI) and other heavy metal resources obtain comprehensive reutilization.Fig. 1 has the valency heavy metal resources to reclaim process route view in the electroplating wastewater.
The method of a kind of purifying electroplating wastewater provided by the invention, comprehensive utilization of resources, its principle and correlated response are as follows:
(1) at first, make Cr (III) be oxidized to Cr (VI) under 13.0～14.0 the condition by chemical reaction, then waste water ph is recalled to 7.0～9.0, make Zn, Cu in the waste water, Ni, Fe, Al etc. have valency huge sum of money element to be converted into precipitation of hydroxide, the waste water that to remove at last behind the heavy metal adopts strongly basic anionic resin absorption Cr (VI), water quality requirement after the purification reaches electroplates pollutant emission standard and reuse requirement, simultaneously Cr in the waste water and heavy metal resources thereof is reclaimed.Cr (VI) in waste water mainly with HCrO 4 -, Cr 2O 4 2-, Cr 2O 7 2-Form exists, its existence form of pH value control of waste water.Utilize strongly basic anionic resin to anionic exchange characterization of adsorption, Cr (VI) is adsorbed on the anionite-exchange resin is removed, thereby make waste water reach purification.
Principle and the correlated response of strong anion-exchange resin absorption Cr (VI) are as follows:
RCl+HCrO 4 -＝RHCrO 4+Cl - (1)
2RCl+CrO 4 2-＝R 2CrO 4+2Cl - (2)
2RCl+Cr 2O 7 2-＝R 2Cr 2O 7+2Cl - (3)
2RCl+2HCrO 4 -＝R 2Cr 2O 7+2Cl -+H 2O (4)
After resin was saturated, available NaOH+NaCl mixing solutions regeneration recovered the resins exchange ability, and its principle and correlated response are as follows:
2RHCrO 4+2NaOH＝R 2CrO 4+Na 2CrO 4+2H 2O (5)
R 2Cr 2O 7+2NaOH＝R 2CrO 4+Na 2CrO 4+H 2O (6)
R 2CrO 4+2NaCl＝2RCl+Na 2CrO 4 (7)
The method of a kind of purifying electroplating wastewater of the present invention, comprehensive utilization of resources, its step and condition are as follows:
(1) chromium (III) is oxidized to chromium (VI): chromate waste water is imported in the pre-treatment pond, the pH value of at first using mineral alkali to regulate waste water is 13.0～14.0, add oxygenant then, Cr (III): the mol ratio of oxygenant is 1: l～3, and making chromium (III) complete oxidation in the waste water is chromium (VI);
Described mineral alkali is sodium hydroxide, potassium hydroxide or calcium hydroxide;
Described oxygenant is hydrogen peroxide or sodium peroxide;
(2) recovery has the valency heavy metal resources: the inorganic acid for adjusting pH value of water reuse that the process step (1) in step (1) the pre-treatment pond was handled is 7.0～9.0, make zinc in the waste water, copper, nickel, iron or aluminium huge sum of money element be converted into precipitation of hydroxide, filter then, filter residue is through dehydration, pulverize, grind, obtain the mixture-metal raw material, further prepare single heavy metal material by hydrometallurgical processes;
Described mineral acid is hydrochloric acid, sulfuric acid or nitric acid;
(3) strongly basic anion exchange resin absorption chromium (VI) and resin regeneration: the strongly basic anion exchange resin of packing in the adsorption column, is 4.0～6.0 with the filtrate in the step (2) with inorganic acid for adjusting pH value, import in the adsorption column from top to bottom then, after the absorption of the 1st adsorption column, chromium in the tail washings (VI) concentration is during greater than 0.1mg/L, and the 2nd adsorption column of contacting is when chromium (VI) concentration is greater than 0.1mg/L in the tail washings of the 2nd adsorption column, the 3rd adsorption column of contacting absorption, the 1st adsorption column leaching regeneration simultaneously; When chromium (VI) concentration is greater than 0.1mg/L in the tail washings of the 3rd adsorption column, the 1st adsorption column of contacting absorption, the 2nd adsorption column leaching regeneration simultaneously; When chromium (VI) concentration is greater than 0.1mg/L in the tail washings of the 1st adsorption column, the 2nd adsorption column of contacting absorption, the 3rd adsorption column leaching regeneration simultaneously; So above-mentioned absorption and renovation process are carried out in cyclical operation; Chromium in tail washings (VI) concentration stops less than 0.1mg/L;
Described mineral acid is hydrochloric acid, sulfuric acid or nitric acid;
Described adsorption column leaching regeneration condition is: leacheate is that mol ratio is 1: 1 sodium hydroxide and a sodium-chlor mixed aqueous solution, the volumetric molar concentration of sodium hydroxide and sodium-chlor is 0.1～1.0mol/L, leacheate imports in the adsorption column from top to bottom to the adsorption column leaching regeneration, be the regeneration terminal point when resin is converted into white by black or yellow, obtain chromium acid sodium solution;
Above-mentioned multicolumn polyphone uses, and adsorbs and the renovation process cyclical operation, and water quality chromium (VI) concentration after fully guaranteeing to adsorb also makes ion exchange resin reach maximum adsorptive capacity simultaneously less than 0.1mg/L.
(4) preparation chromium product: chromium acid sodium solution is adopted H +The type Zeo-karb takes off sodium, preparation chromic acid or chromic trioxide; Adopt soluble barium salt or lead salt precipitation to prepare baryta yellow or lead chromate product; The preferred bariumchloride of described soluble barium salt, barium carbonate or barium sulphide, the preferred plumbic acetate of solubility lead salt, lead nitrate or lead sulfate.
According to the demand of market, can prepare dissimilar chromium products to the chromium product.
The strongly basic anion exchange resin of described step (3) is a macropore glyoxaline structure anionite-exchange resin, and its structure is:
Figure A20091006690500101
In the formula, X -Be chlorion, sulfate ion or nitrate ion;
Preparation method's the step that described macropore contains glyoxaline structure anionite-exchange resin is as follows:
With the styrene tyle macroporous adsorption resin of chloromethylation at N, stirring at room 2h in the dinethylformamide solvent, add the N-Methylimidazole then, the styrene tyle macroporous adsorption resin of chloromethylation: the mol ratio of N-Methylimidazole is 1: 1～1.3, in 40～80 ℃ of reaction 24～72h, filter synthetic resins and use washing with alcohol, will wash back resin vacuum-drying, obtain the strong anion-exchange resin (being abbreviated as macropore RCl) that chlorine type macropore contains glyoxaline structure;
Chlorine type macropore is contained the strong anion-exchange resin of glyoxaline structure at deionized water for stirring 2h, add sodium sulfate then, chlorine type macropore contains the strong anion-exchange resin of glyoxaline structure: the sodium sulfate mol ratio is 1: 0.5～1, mix vibration 10～24h, until reacting completely, and filter resin, the resin after filtering with deionized water wash again, remove excessive sulfate ion, obtain the strong anion-exchange resin that sulfate radical type macropore contains glyoxaline structure and (be abbreviated as macropore R 2SO 4);
Chlorine type macropore is contained the strong anion-exchange resin of glyoxaline structure at deionized water for stirring 2h, the mol ratio that adds the SODIUMNITRATE chemical reactant then is 1: 1～1.5, mix vibration 10～24h, until reacting completely, and filtration resin, resin after filtering with deionized water wash is again removed excessive nitrate ion, obtains the strong anion-exchange resin that nitrate radical type macropore contains glyoxaline structure and (is abbreviated as macropore RNO 3).
Because gel-type contains the macropore of glyoxaline structure strong anion-exchange resin and the present invention preparation and contains the glyoxaline structure strong anion-exchange resin and have identical structure of functional groups, therefore the loading capacity of two kinds of resins, to adsorb top condition, work-ing life performance all very close.Fig. 2 is the influence of duration of oscillation to the different resins adsorptive capacity, and as can be seen from the figure macropore RCl resin has similar adsorption rate with the D301 resin, and the adsorption rate of RCl resin is the fastest, this granular relevant main and resin material.Therefore from the absorption property of resin, work-ing life aspect and regenerative process aspect relatively, the anionite-exchange resin that macropore contains glyoxaline structure has very large advantage, be expected in handling electroplating wastewater, substitute traditional weak anion resin among the Cr (VI), realize the technological innovation of ion exchange technique processing electroplating wastewater.
Beneficial effect: the method for (1) a kind of purifying electroplating wastewater provided by the invention, comprehensive utilization of resources, the strong anion-exchange resin that adopts macropore to contain glyoxaline structure adsorbs the Cr (VI) in the electroplating wastewater, having overcome in the macroporous weakly basic anion exchange resin regenerative processes such as commercialization D301, D371 and D370 needs to consume a large amount of acid, for chromium high efficiente callback in the electroplating wastewater provides a kind of new and effective sorbing material and isolation technique with utilizing.
(2) method of a kind of purifying electroplating wastewater provided by the invention, comprehensive utilization of resources, adopt coupling techniques such as chemical oxidation, ion-exchange and precipitation, make Cr, Ni in the electroplating wastewater, Cu etc. that valency heavy metal resources high efficiente callback utilization be arranged, have remarkable economic efficiency and social benefit.
(3) method of a kind of purifying electroplating wastewater provided by the invention, comprehensive utilization of resources, adopt the macropore of high thermal stability, physical strength and resistance of oxidation to contain Cr (VI) in the strong anion-exchange resin serialization absorption electroplating wastewater of glyoxaline structure, have advantages such as process stabilizing, processing cost are low.
Description of drawings
Fig. 1 has the valency heavy metal resources to reclaim process route view in the electroplating wastewater.
Fig. 2 is the influence figure of duration of oscillation to the different resins loading capacity.
Fig. 3 is the absorption and the desorption curve figure of adsorption resin column.
Embodiment
Embodiment 1
The styrene tyle macroporous adsorption resin of getting the 50g chloromethylation adds 300mL N in there-necked flask, dinethylformamide stirs 2h under the room temperature, adds 40 ℃ of reactions of 16.5g N-Methylimidazole 72h, filters synthetic resins and uses washing with alcohol.To wash back resin vacuum-drying, obtain the strong anion-exchange resin that chlorine type macropore contains glyoxaline structure.
1g chlorine type macropore is contained the strong anion-exchange resin of glyoxaline structure at deionized water for stirring 2h, adding the 20mL volumetric molar concentration then is the metabisulfite solution vibration 10h of 2mol/L, until reacting completely, and filtration resin, resin after filtering with deionized water wash again, remove excessive sulfate ion, obtain the strong anion-exchange resin that sulfate radical type macropore contains glyoxaline structure.
1g chlorine type macropore is contained the strong anion-exchange resin of glyoxaline structure at deionized water for stirring 2h, adding the 20mL volumetric molar concentration then is the sodium nitrate solution vibration 10h of 2mol/L, until reacting completely, and filtration resin, resin after filtering with deionized water wash again, remove excessive nitrate ion, obtain the strong anion-exchange resin that nitrate radical type macropore contains glyoxaline structure.
Embodiment 2
Waste water with certain Electroplate Factory is research object, main component test result such as table 1, contain a large amount of Cr (III), Cr (VI) as can be seen from the table in this waste water and other has the valency heavy metal element, directly discharging causes environmental pollution, and reclaiming has the valency heavy metal element can produce certain economic benefits.
The major ingredient of table 1 waste electroplating liquor containing chromium
The pollutent title Cr(V) Cr (always) Cu Zn Ni Fe Al
Concentration (mg/L) 250 344 28.92 16.61 8.589 134.6 5.063
Chromium (III) is oxidized to chromium (VI): get the 2L chromate waste water, the pH value of using NaOH to regulate waste water respectively is 13.00, adds the hydrogen peroxide of 10.8mmol then, makes the chromium (III) in the waste water be oxidized to chromium (VI).
Recovery has the valency heavy metal resources: it is 7.00 that water reuse sulfuric acid in step (1) the pre-treatment pond is regulated waste water ph, make zinc in the waste water, copper, nickel, iron, aluminium huge sum of money element be converted into precipitation of hydroxide, filter then, filter residue is through dehydration, pulverizing, grinding, be the mixture-metal raw material, can prepare single heavy metal material by hydrometallurgical processes.Zinc in the post precipitation filtrate, copper, nickel, iron, aluminium content are respectively 1.95mg/L, 0.28mg/L, 4.17mg/L, 1.02mg/L, 0.17mg/L.
Strongly basic anion exchange resin absorption chromium (VI) and resin regeneration: be 4.60 at first, import in the adsorption column from top to bottom then with the sharp sulphur acid for adjusting pH value of the filtrate in the step (2).After the 1st adsorption column absorption, chromium in the tail washings (VI) concentration is during greater than 0.1mg/L, the 2nd adsorption column of contacting, and when chromium (VI) concentration is greater than 0.1mg/L in the tail washings of the 2nd adsorption column, the 3rd adsorption column of contacting, the 1st adsorption column leaching regeneration simultaneously.Above-mentioned 2 posts polyphone uses, and water quality chromium (VI) concentration after fully guaranteeing to adsorb also makes ion exchange resin reach maximum adsorptive capacity simultaneously less than 0.1mg/L.The mixing leacheate of 0.3M sodium hydroxide and 0.3M sodium-chlor is imported in the 1st adsorption column from top to bottom, to adsorption column regeneration, is the regeneration terminal point when resin is converted into white by black or yellow, obtains chromium acid sodium solution.Above-mentioned absorption and renovation process cyclical operation.Fig. 3 is the curve of adsorption resin column absorption and desorption, and the internal diameter of adsorption column is 1cm, adds the 2.5g polymeric adsorbent, and the flow rate control of absorption and desorption is 3mL/min.
Preparation chromium product: chromium acid sodium solution is adopted H +The type Zeo-karb takes off sodium, prepares chromic acid or chromic trioxide product.Collect the elutriant in the above-mentioned desorption step, import H from top to bottom +Type cation seperation column, effluent liquid are rare bichromate solutions, when resin is become when orange to taking off the sodium terminal point by orange red, and H simultaneously +The type cation seperation column adopts 1%～10% sulphuric acid soln regeneration.Rare bichromate solutions obtains chromic acid or chromic trioxide product through evaporation concentration.
Embodiment 3
Method according to embodiment 2, have that to utilize the salt acid for adjusting pH value in the valency heavy metal resources step be 8.00 reclaiming copper, nickel etc., make huge sum of money elements such as zinc in the waste water, copper, nickel, iron be converted into precipitation of hydroxide, the zinc in the post precipitation filtrate, copper, nickel, iron, aluminium content are respectively 0.13mg/L, 0.22mg/L, 0.41mg/L, 0.69mg/L, 0.21mg/L.
It is 4.00 that filtrate in strongly basic anion exchange resin absorption chromium (VI) step is utilized the salt acid for adjusting pH value.Adopt secondary absorption posts polyphone to use according to embodiment 2, make after the ion exchange treatment in the waste water Cr (VI) content less than 0.1mg/L.
In the preparation chromium product step, adopt solubility chlorination precipitated barium method to prepare the baryta yellow product chromium acid sodium solution.Collect the elutriant 100mL in the above-mentioned desorption step, the concentration of measuring Cr (VI) in the elutriant is 3234mg/L, adds the stirring of 1.5g bariumchloride and makes Cr (VI) be converted into the baryta yellow precipitation, and filtration, drying obtain the baryta yellow product.
Embodiment 4
Method according to embodiment 2, have that to utilize the nitre acid for adjusting pH value in the valency heavy metal resources step be 9.00 reclaiming copper, nickel etc., make huge sum of money elements such as zinc in the waste water, copper, nickel, iron be converted into precipitation of hydroxide, the zinc in the post precipitation filtrate, copper, nickel, iron, aluminium content are respectively 0.06mg/L, 0.17mg/L, 0.32mg/L, 0.32mg/L, 0.19mg/L.
It is 6.00 that filtrate in strongly basic anion exchange resin absorption chromium (VI) step is utilized the nitre acid for adjusting pH value.Adopt secondary absorption posts polyphone to use according to embodiment 2, make after the ion exchange treatment in the waste water Cr (VI) content less than 0.1mg/L.
In the preparation chromium product step, adopt the solubility plumbic acetate precipitator method to prepare the lead chromate product chromium acid sodium solution.Collect the elutriant 100mL in the above-mentioned desorption step, the concentration of measuring Cr (VI) in the elutriant is 3234mg/L, adds the stirring of 2.8g plumbic acetate and makes Cr (VI) be converted into precipitation of lead chromate, and filtration, drying obtain the lead chromate product.

Claims (1)

1, the method for a kind of purifying electroplating wastewater, comprehensive utilization of resources is characterized in that, its step and condition are as follows: its step and condition are as follows:
(1) chromium (III) is oxidized to chromium (VI): chromate waste water is imported in the pre-treatment pond, the pH value of at first using mineral alkali to regulate waste water is 13.0～14.0, add oxygenant then, Cr (III): the chemical reaction mol ratio of oxygenant is 1: 1～3, and making chromium (III) complete oxidation in the waste water is chromium (VI);
Described mineral alkali is sodium hydroxide, potassium hydroxide or calcium hydroxide;
Described oxygenant is hydrogen peroxide or sodium peroxide;
(2) recovery has the valency heavy metal resources: the inorganic acid for adjusting pH value of water reuse that the process step (1) in step (1) the pre-treatment pond was handled is 7.0～9.0, make zinc in the waste water, copper, nickel, iron or aluminium huge sum of money element be converted into precipitation of hydroxide, filter then, filter residue is through dehydration, pulverize, grind, obtain the mixture-metal raw material, further prepare single heavy metal material by hydrometallurgical processes;
Described mineral acid is hydrochloric acid, sulfuric acid or nitric acid;
(3) strongly basic anion exchange resin absorption chromium (VI) and resin regeneration: the strongly basic anion exchange resin of packing in the adsorption column, is 4.0～6.0 with the filtrate in the step (2) with inorganic acid for adjusting pH value, import in the adsorption column from top to bottom then, after the absorption of the 1st adsorption column, chromium in the tail washings (VI) concentration is during greater than 0.1mg/L, and the 2nd adsorption column of contacting is when chromium (VI) concentration is greater than 0.1mg/L in the tail washings of the 2nd adsorption column, the 3rd adsorption column of contacting absorption, the 1st adsorption column leaching regeneration simultaneously; When chromium (VI) concentration is greater than 0.1mg/L in the tail washings of the 3rd adsorption column, the 1st adsorption column of contacting absorption, the 2nd adsorption column leaching regeneration simultaneously; When chromium (VI) concentration is greater than 0.1mg/L in the tail washings of the 1st adsorption column, the 2nd adsorption column of contacting absorption, the 3rd adsorption column leaching regeneration simultaneously; So above-mentioned absorption and renovation process are carried out in cyclical operation; Chromium in tail washings (VI) concentration stops less than 0.1mg/L;
Described mineral acid is hydrochloric acid, sulfuric acid or nitric acid;
Described adsorption column leaching regeneration condition is: leacheate is that mol ratio is 1: 1 sodium hydroxide and a sodium-chlor mixed aqueous solution, the concentration of sodium hydroxide and sodium-chlor is respectively 0.1～1.0mol/L, leacheate imports in the adsorption column from top to bottom to the adsorption column leaching regeneration, be the regeneration terminal point when resin is converted into white by black or yellow, obtain chromium acid sodium solution;
(4) preparation chromium product: chromium acid sodium solution is adopted H +The type Zeo-karb takes off sodium, preparation chromic acid or chromic trioxide; Adopt soluble barium salt or lead salt precipitation to prepare baryta yellow or lead chromate product; The preferred bariumchloride of described soluble barium salt, barium carbonate or barium sulphide, the preferred plumbic acetate of solubility lead salt, lead nitrate or lead sulfate;
The strongly basic anion exchange resin of described step (3) is a macropore glyoxaline structure anionite-exchange resin, and its structure is:
Figure A2009100669050003C1
In the formula, X -Be chlorion, sulfate ion or nitrate ion;
Preparation method's the step that described macropore contains glyoxaline structure anionite-exchange resin is as follows: with the styrene tyle macroporous adsorption resin of chloromethylation at N, stirring at room 2h in the dinethylformamide solvent, add the N-Methylimidazole then, the styrene tyle macroporous adsorption resin of chloromethylation: the mol ratio of N-Methylimidazole is 1: 1～1.3, in 40～80 ℃ of reaction 24～72h, filter synthetic resins and use washing with alcohol, to wash back resin vacuum-drying, obtain the strong anion-exchange resin that chlorine type macropore contains glyoxaline structure;
Chlorine type macropore is contained the strong anion-exchange resin of glyoxaline structure at deionized water for stirring 2h, add sodium sulfate then, chlorine type macropore contains the strong anion-exchange resin of glyoxaline structure: the mol ratio of sodium sulfate is 1: 0.5～1.0, mix vibration 10～24h, until reacting completely, and filter resin, the resin after filtering with deionized water wash again, remove excessive sulfate ion, obtain the strong anion-exchange resin that sulfate radical type macropore contains glyoxaline structure;
Chlorine type macropore is contained the strong anion-exchange resin of glyoxaline structure at deionized water for stirring 2h, add SODIUMNITRATE then, chlorine type macropore contains the strong anion-exchange resin of glyoxaline structure: the mol ratio of SODIUMNITRATE is 1: 1～1.5, mix vibration 10～24h, until reacting completely, and filter resin, the resin after filtering with deionized water wash again, remove excessive nitrate ion, obtain the strong anion-exchange resin that nitrate radical type macropore contains glyoxaline structure.
CN2009100669058A 2009-05-05 2009-05-05 Method for purifying electroplating wastewater and comprehensively utilizing resources Active CN101570372B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN2009100669058A CN101570372B (en) 2009-05-05 2009-05-05 Method for purifying electroplating wastewater and comprehensively utilizing resources

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN2009100669058A CN101570372B (en) 2009-05-05 2009-05-05 Method for purifying electroplating wastewater and comprehensively utilizing resources

Publications (2)

Publication Number Publication Date
CN101570372A true CN101570372A (en) 2009-11-04
CN101570372B CN101570372B (en) 2011-06-08

Family

ID=41229876

Family Applications (1)

Application Number Title Priority Date Filing Date
CN2009100669058A Active CN101570372B (en) 2009-05-05 2009-05-05 Method for purifying electroplating wastewater and comprehensively utilizing resources

Country Status (1)

Country Link
CN (1) CN101570372B (en)

Cited By (34)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101817560A (en) * 2010-04-07 2010-09-01 中国科学院过程工程研究所 Methods for removing calcium and magnesium alkaline-earth metal ions contained in chromate solution by adopting ion exchange resin
CN102001707A (en) * 2010-12-28 2011-04-06 南京源泉环保科技股份有限公司 Method for recycling chromic acid in electroplating waste water
CN102329030A (en) * 2011-09-06 2012-01-25 冯云香 Treatment method of chemical nickel-plating wastewater
CN102583620A (en) * 2012-02-16 2012-07-18 浙江工业大学 Method for removing heavy metal ions from waste water and solidifying and recycling
CN101723558B (en) * 2009-12-04 2012-08-15 南京大学 Integration method for electroplating acid pickle recycling and advanced waste treatment
CN102786171A (en) * 2012-08-28 2012-11-21 山东同大镍网有限公司 Comprehensive treatment process and device for electroplating wastewater containing heavy metal ions, Cr6+, Cu2+ and Ni2+
CN103011347A (en) * 2012-06-01 2013-04-03 浙江师范大学 Method for carrying out electrolytic treatment on copper-containing electroplating wastewater and recycling copper
CN103225131A (en) * 2013-05-06 2013-07-31 渤海大学 Al2O3, Cr2O3 composite nanofiber or nanosheet prepared from chromium-bearing aluminium sludge and preparation method thereof
CN103318934A (en) * 2013-07-12 2013-09-25 渤海大学 Preparation method for high-purity aluminate from mud containing chromium and aluminum
CN103318935A (en) * 2013-07-12 2013-09-25 渤海大学 Preparation method for high-purity aluminum hydroxide from mud containing chromium and aluminum
CN103496802A (en) * 2013-09-11 2014-01-08 洛阳鼎力环保科技有限公司 Chromium and manganese recovery method in electrolytic manganese chromium wastewater treatment process
CN103498050A (en) * 2013-09-11 2014-01-08 洛阳鼎力环保科技有限公司 Chromium recovery method in electrolytic manganese chromium wastewater treatment process
CN103572319A (en) * 2013-11-25 2014-02-12 南安市旭繁金属回收有限公司 Method for recovering nickel from electroplating centralized control wastewater
CN103880214A (en) * 2014-03-24 2014-06-25 河北钢铁股份有限公司承德分公司 Method for treating chromium-containing alkali solution
CN104451166A (en) * 2014-12-31 2015-03-25 北京清大国华环保科技有限公司 Method and device for recovering zinc and chrome in heavy metal sludge
CN104556476A (en) * 2014-12-23 2015-04-29 东莞市粤威环保科技有限公司 Method of treating reserve salt of sodium m-nitro-p-toluenesulfonate in electroplating wastewater harmlessly
CN105060584A (en) * 2015-07-18 2015-11-18 常州市鼎日环保科技有限公司 Method for removing heavy metals in plated plate etching wastewater
CN105800821A (en) * 2014-12-30 2016-07-27 上海轻工业研究所有限公司 Up-to-standard treatment method and device for zinc-nickel alloy waste water
CN106007040A (en) * 2016-07-23 2016-10-12 杭州真水流体技术有限公司 Heavy metal wastewater treatment system and method
CN106277427A (en) * 2016-04-28 2017-01-04 南京霖厚环保科技有限公司 Electroplating comprehensive waste water Intelligent processing device and control method thereof
CN106277456A (en) * 2016-08-30 2017-01-04 浙江奇彩环境科技股份有限公司 A kind of waste electroplating liquor containing chromium resource prepares the method that ferrochrome is black
CN106315676A (en) * 2016-08-29 2017-01-11 昆明理工大学 Method for using electrochromism slag to produce plumbous chromate
CN106745385A (en) * 2016-12-22 2017-05-31 郑州丽福爱生物技术有限公司 A kind of Industrial Waste Water Treatments medicament and preparation method thereof
CN106800352A (en) * 2017-03-27 2017-06-06 福建欣宇卫浴科技股份有限公司 System for processing chrome-containing wastewater
CN106830489A (en) * 2017-03-27 2017-06-13 福建欣宇卫浴科技股份有限公司 System for processing chrome-containing wastewater
CN109626443A (en) * 2018-12-17 2019-04-16 江苏永葆环保科技有限公司 A method of recycling sludge, which is washed, containing chromic acid utilizes
CN109722543A (en) * 2019-03-20 2019-05-07 东北大学 A kind of method that aluminium-nickel base contained high temperature alloy waste cut materials recycling prepares chromium oxide
CN110818198A (en) * 2019-11-26 2020-02-21 重庆龙健金属制造有限公司 High-salt heavy metal wastewater composite treatment method
CN111170503A (en) * 2020-01-03 2020-05-19 中南大学 Method for treating and recycling chromium and ammonia nitrogen in electroplating wastewater
CN111455185A (en) * 2020-06-08 2020-07-28 江苏美东环境科技有限公司 Harmless extraction treatment method for chromium-containing sludge
CN112777837A (en) * 2021-01-05 2021-05-11 广州大学 Method for removing aniline, chromium and antimony in wastewater
CN112919710A (en) * 2020-08-07 2021-06-08 江门市佰川环境科技有限公司 Hexavalent chromium cleaning wastewater recycling zero-discharge process
CN114057319A (en) * 2021-10-19 2022-02-18 浙江工业大学 Method for separating and recovering trace molybdenum element from molybdenum-containing wastewater
CN115259103A (en) * 2022-08-17 2022-11-01 四川省银河化学股份有限公司 Process for preparing acid-base from chromium-containing sodium sulfate solution

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN2050430U (en) * 1988-12-27 1990-01-03 张鹤鸣 Mixing treament apparatus for plating waste water
DE19502440A1 (en) * 1995-01-26 1997-01-02 Cwg Gmbh Purifying waste water esp. water from photographic industry, electroplating, eloxal process or neutralisation
CN1093180C (en) * 1996-12-30 2002-10-23 中国环境科学研究院 One-step process of resin regeneration and chromium reduction for reclaiming chromium from electroplating waste water
CN101037243A (en) * 2007-04-26 2007-09-19 陈启松 Heavy metal treatment method of electroplating wastewater
CN100572298C (en) * 2007-07-16 2009-12-23 赵文煜 Full recovery and treatment method of electroplating water and processing reclaiming system

Cited By (49)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101723558B (en) * 2009-12-04 2012-08-15 南京大学 Integration method for electroplating acid pickle recycling and advanced waste treatment
CN101817560A (en) * 2010-04-07 2010-09-01 中国科学院过程工程研究所 Methods for removing calcium and magnesium alkaline-earth metal ions contained in chromate solution by adopting ion exchange resin
CN102001707A (en) * 2010-12-28 2011-04-06 南京源泉环保科技股份有限公司 Method for recycling chromic acid in electroplating waste water
CN102001707B (en) * 2010-12-28 2012-09-12 南京源泉环保科技股份有限公司 Method for recycling chromic acid in electroplating waste water
CN102329030B (en) * 2011-09-06 2013-03-27 冯云香 Treatment method of chemical nickel-plating wastewater
CN102329030A (en) * 2011-09-06 2012-01-25 冯云香 Treatment method of chemical nickel-plating wastewater
CN102583620B (en) * 2012-02-16 2013-11-13 浙江工业大学 Method for removing heavy metal ions from waste water and solidifying and recycling
CN102583620A (en) * 2012-02-16 2012-07-18 浙江工业大学 Method for removing heavy metal ions from waste water and solidifying and recycling
CN103011347A (en) * 2012-06-01 2013-04-03 浙江师范大学 Method for carrying out electrolytic treatment on copper-containing electroplating wastewater and recycling copper
CN103011347B (en) * 2012-06-01 2014-03-05 浙江师范大学 Method for carrying out electrolytic treatment on copper-containing electroplating wastewater and recycling copper
CN102786171A (en) * 2012-08-28 2012-11-21 山东同大镍网有限公司 Comprehensive treatment process and device for electroplating wastewater containing heavy metal ions, Cr6+, Cu2+ and Ni2+
CN102786171B (en) * 2012-08-28 2013-11-27 山东同大镍网有限公司 Comprehensive treatment process and device for electroplating wastewater containing heavy metal ions, Cr6+, Cu2+ and Ni2+
CN103225131A (en) * 2013-05-06 2013-07-31 渤海大学 Al2O3, Cr2O3 composite nanofiber or nanosheet prepared from chromium-bearing aluminium sludge and preparation method thereof
CN103318934A (en) * 2013-07-12 2013-09-25 渤海大学 Preparation method for high-purity aluminate from mud containing chromium and aluminum
CN103318935A (en) * 2013-07-12 2013-09-25 渤海大学 Preparation method for high-purity aluminum hydroxide from mud containing chromium and aluminum
CN103496802A (en) * 2013-09-11 2014-01-08 洛阳鼎力环保科技有限公司 Chromium and manganese recovery method in electrolytic manganese chromium wastewater treatment process
CN103498050A (en) * 2013-09-11 2014-01-08 洛阳鼎力环保科技有限公司 Chromium recovery method in electrolytic manganese chromium wastewater treatment process
CN103572319B (en) * 2013-11-25 2016-08-17 南安市旭繁金属回收有限公司 The method of electroplating concentrated control waste water reclamation nickel
CN103572319A (en) * 2013-11-25 2014-02-12 南安市旭繁金属回收有限公司 Method for recovering nickel from electroplating centralized control wastewater
CN103880214A (en) * 2014-03-24 2014-06-25 河北钢铁股份有限公司承德分公司 Method for treating chromium-containing alkali solution
CN103880214B (en) * 2014-03-24 2015-09-23 河北钢铁股份有限公司承德分公司 Process is containing the method for chromium alkaline aqueous solution
CN104556476A (en) * 2014-12-23 2015-04-29 东莞市粤威环保科技有限公司 Method of treating reserve salt of sodium m-nitro-p-toluenesulfonate in electroplating wastewater harmlessly
CN105800821A (en) * 2014-12-30 2016-07-27 上海轻工业研究所有限公司 Up-to-standard treatment method and device for zinc-nickel alloy waste water
CN104451166A (en) * 2014-12-31 2015-03-25 北京清大国华环保科技有限公司 Method and device for recovering zinc and chrome in heavy metal sludge
CN105060584A (en) * 2015-07-18 2015-11-18 常州市鼎日环保科技有限公司 Method for removing heavy metals in plated plate etching wastewater
CN106277427A (en) * 2016-04-28 2017-01-04 南京霖厚环保科技有限公司 Electroplating comprehensive waste water Intelligent processing device and control method thereof
CN106277427B (en) * 2016-04-28 2019-02-01 南京霖厚环保科技有限公司 Electroplating comprehensive waste water Intelligent processing device and its control method
CN106007040A (en) * 2016-07-23 2016-10-12 杭州真水流体技术有限公司 Heavy metal wastewater treatment system and method
CN106007040B (en) * 2016-07-23 2022-09-06 杭州真水流体技术有限公司 Heavy metal wastewater treatment system and method
CN106315676B (en) * 2016-08-29 2017-12-22 昆明理工大学 A kind of method that electrodeposited chromium slag prepares plumbous chromate
CN106315676A (en) * 2016-08-29 2017-01-11 昆明理工大学 Method for using electrochromism slag to produce plumbous chromate
CN106277456A (en) * 2016-08-30 2017-01-04 浙江奇彩环境科技股份有限公司 A kind of waste electroplating liquor containing chromium resource prepares the method that ferrochrome is black
CN106745385A (en) * 2016-12-22 2017-05-31 郑州丽福爱生物技术有限公司 A kind of Industrial Waste Water Treatments medicament and preparation method thereof
CN106830489A (en) * 2017-03-27 2017-06-13 福建欣宇卫浴科技股份有限公司 System for processing chrome-containing wastewater
WO2018177221A1 (en) * 2017-03-27 2018-10-04 福建欣宇卫浴科技股份有限公司 Treatment system for wastewater containing chromium
CN106800352A (en) * 2017-03-27 2017-06-06 福建欣宇卫浴科技股份有限公司 System for processing chrome-containing wastewater
CN109626443A (en) * 2018-12-17 2019-04-16 江苏永葆环保科技有限公司 A method of recycling sludge, which is washed, containing chromic acid utilizes
CN109722543A (en) * 2019-03-20 2019-05-07 东北大学 A kind of method that aluminium-nickel base contained high temperature alloy waste cut materials recycling prepares chromium oxide
CN109722543B (en) * 2019-03-20 2020-06-05 东北大学 Method for preparing chromium oxide by recycling aluminum-containing nickel-based superalloy cutting waste
CN110818198B (en) * 2019-11-26 2022-04-29 重庆龙健金属制造有限公司 High-salt heavy metal wastewater composite treatment method
CN110818198A (en) * 2019-11-26 2020-02-21 重庆龙健金属制造有限公司 High-salt heavy metal wastewater composite treatment method
CN111170503A (en) * 2020-01-03 2020-05-19 中南大学 Method for treating and recycling chromium and ammonia nitrogen in electroplating wastewater
CN111455185A (en) * 2020-06-08 2020-07-28 江苏美东环境科技有限公司 Harmless extraction treatment method for chromium-containing sludge
CN112919710A (en) * 2020-08-07 2021-06-08 江门市佰川环境科技有限公司 Hexavalent chromium cleaning wastewater recycling zero-discharge process
CN112777837A (en) * 2021-01-05 2021-05-11 广州大学 Method for removing aniline, chromium and antimony in wastewater
CN114057319A (en) * 2021-10-19 2022-02-18 浙江工业大学 Method for separating and recovering trace molybdenum element from molybdenum-containing wastewater
CN114057319B (en) * 2021-10-19 2023-09-08 浙江工业大学 Method for separating and recovering trace molybdenum element from molybdenum-containing wastewater
CN115259103A (en) * 2022-08-17 2022-11-01 四川省银河化学股份有限公司 Process for preparing acid-base from chromium-containing sodium sulfate solution
CN115259103B (en) * 2022-08-17 2023-11-10 四川省银河化学股份有限公司 Acid-base preparation process for chromium-containing sodium sulfate solution

Also Published As

Publication number Publication date
CN101570372B (en) 2011-06-08

Similar Documents

Publication Publication Date Title
CN101570372B (en) Method for purifying electroplating wastewater and comprehensively utilizing resources
CN101269871B (en) Method for processing chrome wastewater
CN101337707B (en) Method for processing dimethylamine waste water by ion-exchange method
CN103553249B (en) In electroplating effluent, acid is separated and heavy metal collection method
CN104129831B (en) Method for simultaneous removal and recovery of heavy metal ions and organic acid by using chelating resin
CN104313348A (en) Method for extracting lithium from salt lake brine by using adsorption method
CN101172676A (en) Method for processing hexavalent chromium contained wastewater with ion exchange resin
CN102936070A (en) Method for treating mercury-containing wastewater during PVC (Polyvinyle Chloride) production through two-step process
CN103991924B (en) A kind of regeneration of ion-exchange resin method for the treatment of electrolytic manganese production technique tail end wastewater
CN105174556A (en) High-acidity high-iron heavy metal wastewater quality-divided resource recycling method
CN101838065A (en) Method for recycling hexavalent chromium in electrolytic manganese production tail end wastewater
CN108793493A (en) O-aminophenol recovery and treatment method in a kind of strong brine
CN105110544A (en) Method for treating wastewater with dilute alkali by aid of macroporous resin
CN103408102A (en) Ion exchange resin regeneration method reducing desorbed liquid
CN102120658B (en) Treatment and recycling method of ammonia nitrogen in electrolytic manganese production end wastewater
CN111003853A (en) Electroplating waste liquid treatment method
CN105289562A (en) Recovery utilization method for heavy metal wastewater
CN104150570B (en) A kind of method extracting chromium from chrome waste liquid
CN104005050B (en) In Electrolytic Manganese Wastewater, bivalent manganese is processed reuse method
CN103449623A (en) Method for preparing metal nanometer material by recovering from industrial waste water
CN101444716A (en) Heavy metal bioadsorbent and method for adsorbing heavy metal in electroplating wastewater by same
CN105152433A (en) Method for removing COD (chemical oxygen demand) from copper/molybdenum extraction raffinate mixed wastewater
CN110106356B (en) Method for separating lithium from salt lake brine by using powder type titanium ion exchanger
CN105502733A (en) Method for cooperatively removing and selectively recovering heavy metal cations and non-metal anions from wastewater
CN107473319B (en) Method for recovering cationic heavy metals in water through phase change regulation

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
ASS Succession or assignment of patent right

Owner name: CHANGZHOU INSTITUTE OF ENERGY STORAGE MATERIALS +

Free format text: FORMER OWNER: CHANGCHUN INST. OF APPLIED CHEMISTRY, CHINESE ACADEMY OF SCIENCES

Effective date: 20130916

C41 Transfer of patent application or patent right or utility model
COR Change of bibliographic data

Free format text: CORRECT: ADDRESS; FROM: 130022 CHANGCHUN, JILIN PROVINCE TO: 213000 CHANGZHOU, JIANGSU PROVINCE

TR01 Transfer of patent right

Effective date of registration: 20130916

Address after: Changzhou City, Jiangsu province Hehai road 213000 No. 9

Patentee after: CHANGZHOU INSTITUTE OF ENERGY STORAGE MATERIALS & DEVICES

Address before: 130022 Changchun people's street, Jilin, No. 5625

Patentee before: CHANGCHUN INSTITUTE OF APPLIED CHEMISTRY CHINESE ACADEMY OF SCIENCES

TR01 Transfer of patent right

Effective date of registration: 20230614

Address after: No. 5625 Renmin Street, Chaoyang District, Changchun City, Jilin Province, 130012

Patentee after: CHANGCHUN INSTITUTE OF APPLIED CHEMISTRY CHINESE ACADEMY OF SCIENCES

Address before: No. 9, river Hai Dong Road, Changzhou, Jiangsu Province

Patentee before: CHANGZHOU INSTITUTE OF ENERGY STORAGE MATERIALS & DEVICES

TR01 Transfer of patent right