CN109467167A - A kind of method of heavy metal in removal stainless steel acid cleaning waste water - Google Patents
A kind of method of heavy metal in removal stainless steel acid cleaning waste water Download PDFInfo
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- CN109467167A CN109467167A CN201811272159.3A CN201811272159A CN109467167A CN 109467167 A CN109467167 A CN 109467167A CN 201811272159 A CN201811272159 A CN 201811272159A CN 109467167 A CN109467167 A CN 109467167A
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- waste water
- stainless steel
- heavy metal
- acid cleaning
- cleaning waste
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/469—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis
- C02F1/4693—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis electrodialysis
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/203—Iron or iron compound
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
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- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Water Supply & Treatment (AREA)
- Environmental & Geological Engineering (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
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- Health & Medical Sciences (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
Abstract
The present invention relates to a kind of methods of heavy metal in removal stainless steel acid cleaning waste water.This method is that anion-exchange membrane and cation-exchange membrane are combined into dual membranes and three chambers electrodialysis cell, is medial compartment between yin-yang film, and cavity block side is anode chamber, and anode membrane side is cathode chamber.Medial compartment is added in stainless steel acid cleaning waste water, dust technology is added in anode chamber, and complexing agent is added in cathode chamber.Using stainless steel as cathode, graphite is anode, is passed through direct current.Under electric field action, using amberplex to the selective penetrated property of zwitterion, in this way, then the heavy metal ion in waste water is enriched in the form of metal complex anion in cathode chamber, acid radical anion is enriched in anode chamber.This method has the characteristics of easy to operate, technological parameter is easy to control, can not only remove the heavy metal ion in stainless steel acid cleaning waste water, moreover it is possible to enriching and recovering heavy metal ion.
Description
Technical field
The present invention relates to a kind of methods with heavy metal in electroosmose process removal stainless steel acid cleaning waste water.
Background technique
Stainless steel has the surface of excellent corrosion resistance and mechanical property and beauty, a kind of to be widely used
Metal material.Stainless steel will form one layer of thin and dense oxidation in smelting, founding, rolling and heat treatment process, on surface
Film, main component are iron oxide (FeO, Fe2O3And Fe3O4), chromium oxide (Cr2O3), the FeO of nickel oxide (NiO) and indissoluble
Cr2O3、FeO·Cr2O3·Fe2O3、Ni·Fe2O3Equal substances.Have an adverse effect and protect to stainless steel following process to eliminate
Good appearance is held, therefore needs to remove this layer of oxidation film by process of surface treatment.Surface treatment technique for stainless steel is with pickling
Based on, due to Cr2O3、FeO·Cr2O3And FeOCr2O3·Fe2O3It is insoluble in single acid, therefore pickling generallys use nitric acid
With the mixed acid of the compositions such as hydrofluoric acid.
Stainless steel nitration mixture (HNO3+ HF) waste water that generates of pickling can be divided into two major classes, and one kind is giving up from descaling bath
Sour raffinate, another kind of is by rinsing the washes generated.The former is acid strong, and concentration of heavy metal ion is high；The latter's acidity is weak, weight
Concentration of metal ions is low.In order to facilitate subsequent processing, treatment facility is made to keep stability and reliability, most enterprises that can will give up
It is handled together after sour raffinate and washes mixing, mixed waste water is exactly so-called stainless steel acid cleaning waste water.This waste water
Because containing Cr3+、Ni2+Etc. heavy metal ion and forbidded strictly unprocessed and arbitrarily discharged by country.
As Industry Branch and people's daily life use more and more stainless steels, stainless steel output increases rapidly
Add, a large amount of pickling waste waters generated therewith also bring great environmental protection pressure to enterprise.At present in stainless steel acid cleaning waste water
The Study on treatment technology of heavy metal ion includes electrochemical reducing, solvent extraction, absorption method and ion-exchange etc..But from
Investment, operating cost and technical maturity comprehensively consider, and enterprise generallys use neutralization precipitation method processing stainless steel acid cleaning waste water.
Although neutralization precipitation method can remove the heavy metal ion in waste water in the form that hydroxide precipitates, because of precipitating
(being commonly called as acid-washing stainless steel sludge) Cr containing heavy metal element and Ni, belongs to industrial hazard solid waste, if untreated simple
Landfill, can occupy a large amount of soils and be easy to cause secondary pollution.From the resource utilization angle of sludge consider, have researcher by its
Construction material is produced as adding raw materials, however thus obtained building material product, traction is lower, especially in natural item
Environmental safety under part is still to be assessed.
Summary of the invention
The purpose of the present invention is to provide a kind of methods of heavy metal ion in removal stainless steel acid cleaning waste water.
The present invention utilizes ion-exchange membrane electrodialysis principle, and waste water is introduced into the medial compartment in electrodialysis plant, cathode chamber
Hydroxycarboxylate is added as complexing agent, under DC electric field effect, heavy metal ion enters cathode through cation-exchange membrane
Room and and hydroxycarboxylic acid root therein reaction generate metal complex anion, enable the waste water qualified discharge of medial compartment, and
Acid therein can be recycled in anode chamber, heavy metal can be recycled in cathode chamber, can not only be reduced environmental pollution in this way, but also can be with
Realize the resource utilization of heavy metal.
Insight of the invention is that by the method for the removal of heavy metal ions in stainless steel acid cleaning waste water, using dual membranes and three chambers
Electrodialysis cell, as shown in Figure 1, electrodialysis cell is divided into anode chamber, centre by anion-exchange membrane and cation-exchange membrane
Room and cathode chamber.Medial compartment is added in stainless steel acid cleaning waste water, anode chamber is added in dust technology, and cathode chamber is added in complexing agent X, uses
Direct current carries out electrodialysis.Fe using the selective penetrated property of amberplex, under electric field action, in medial compartment waste water3+、
Cr3+And Ni2+Cathode chamber is entered by cation-exchange membrane Deng cationic, is chemically reacted with complexing agent X, metal network is formed
Anion and medial compartment cannot be returned；NO3 -And F-Equal acid radical anions enter anode chamber by anion-exchange membrane, acid ion
It is enriched in the anode compartment.Under the continuous action of electric field, the concentration of medial compartment heavy metal ions in wastewater is gradually reduced, until reaching
To discharge standard, metal ion is enriched in the cathodic compartment in the form of complex anion.
Conceived according to foregoing invention, the present invention adopts the following technical solutions:
A kind of method of heavy metal in removal stainless steel acid cleaning waste water, it is characterised in that the specific steps of this method are as follows:
It a. is 0~2.0 by pH value, the concentration of total iron, total chromium and total nickel is respectively 1500~1800 mg/L, 140~200 mg/
The stainless steel acid cleaning waste water of L and 100~160 mg/L are added to the medial compartment of dual membranes and three chambers electrodialysis cell；
B. the complexing agent X solution that concentration is 0.12~0.36 mol/L, pH value is 7.0~9.0 is added to dual membranes and three chambers electric osmose
Analyse the cathode chamber of slot；
C. 0.1 mol/L HNO is added in the anode chamber of dual membranes and three chambers electrodialysis cell3Solution；
D. using stainless steel as cathode, graphite is anode, is passed through direct current, and cathode-current density control is 250~300 A/m2；
With the progress of electrodialytic process, the acid radical anion in medial compartment waste water moves to anode chamber, metal ion transport to cathode
Room is simultaneously and complexing agent reacts to form metal complex anion；
E. reach national emission standard to the reduction of heavy metal ions in wastewater concentration, medial compartment waste water is discharged.
Above-mentioned complexing agent X is hydroxycarboxylate.
Above-mentioned hydroxycarboxylate are as follows: sodium citrate or sulfosalicylic acid sodium salt.
The features and advantages of the invention are as described below:
1, by the way that complexing agent X is added in the cathode chamber of electrolyzer with dual membranes and three chambers, make itself and Fe3+、Cr3+And Ni2+Equal metal ions
Generate complex anion, promote in medial compartment pickling waste waters metal ion and penetrate cation-exchange membrane, at the same avoid metal from
Hydrolysis of the son in cathode chamber solution, enables electrodialytic process to be persistently normally carried out.
2, through the invention, the concentration of heavy metal ion can achieve " integrated wastewater discharge mark in stainless steel acid cleaning waste water
It is quasi- " requirement of (GB 8978-1996) (calling " discharge standard " in the following text).Continuous 10 electrodialysis, the stainless steel acid cleaning waste water of medial compartment
The requirement that " discharge standard " can be reached realizes the innoxious of stainless steel acid cleaning waste water.
3, the iron in pickling waste waters is mainly deposited on cathode plate, and chromium and nickel are mainly enriched in cathode chamber solution, thus
Greatly reduce the volume of the solution containing heavy metal ion.Acid group in pickling waste waters is enriched in anode chamber's solution, so that acid solution
It is recycled.Realize the recycling of stainless steel acid cleaning waste water.
4, the complexing agent X used is environmentally friendly, nontoxic and pollution-free, and pregnant solution extracts a huge sum of money through proper method in cathode chamber
After category, complexing agent X can be used with regeneration cycle.
Method of the invention removes simple process, and removal efficiency is high, while avoiding existing neutralisation processing stainless steel acid
Wash the shortcomings that waste water generates acid-washing stainless steel sludge and causes secondary pollution.The present invention not only realizes reaching for stainless steel acid cleaning waste water
Mark discharge, and the recycling for metallic element (Fe, Cr and Ni) provides effective way.
The present invention penetrates characteristic according to the selectivity of amberplex, i.e. cation-exchange membrane only allows cation permeable,
Anion-exchange membrane only allows anion-permeable, and pickling waste waters is therein in the electrodialysis cell that anions and canons exchange membrane forms
Heavy metal ion passes through cation-exchange membrane and reaches the other side and occur to be coordinated with anion ligand anti-under DC electric field effect
It answers, generates metal complex anion.With the progress of electrodialytic process, the heavy metal ions in wastewater of cation-exchange membrane side is dense
Degree constantly reduces, until reaching discharge standard.And other side heavy metal ion is then enriched in the form of complex anion.
The present invention with ion-exchange membrane electrodialysis method handle stainless steel acid cleaning waste water, enable wherein heavy metal concentration reach
To discharge standard, and valuable metal and acid therein can be recycled, can not only reduced environmental pollution, but also heavy metal may be implemented
Resource utilization.
Detailed description of the invention
Fig. 1 dual membranes and three chambers electrodialysis cell schematic diagram.
Specific embodiment
After now specific embodiments of the present invention are described in.
Embodiment 1
The ingredient of 1 stainless steel acid cleaning waste water of table
Electrodialysis cell is divided into anode chamber, medial compartment and cathode chamber by anion-exchange membrane and cation-exchange membrane, it will not
The medial compartment of dual membranes and three chambers electrodialysis cell is added in the steel pickling waste waters that becomes rusty, and anode chamber, complexing agent is added in 0.1 mol/L dilute nitric acid solution
Sulfosalicylic acid na concn is that cathode chamber is added in the solution that 0.12 mol/L, pH is 7.2, carries out electrodialysis using direct current.Sun
Extremely graphite plate, cathode are stainless steel plate, and cathode-current density is 278 A/m2.After 10 h of electrodialysis, total Chromium in Waste concentration
0.872 mg/L is dropped to, total nickel concentration drops to 0.747 mg/L, meets the requirement of " discharge standard ".
Embodiment 2
Stainless steel acid cleaning waste water is added to the medial compartment of dual membranes and three chambers electrodialysis cell, anode is added in 0.1 mol/L dilute nitric acid solution
Room, complexing agent X sodium citrate concentration are that cathode chamber is added in the solution that 0.24 mol/L, pH is 8.8, carry out electric osmose using direct current
Analysis.Anode is graphite plate, and cathode is stainless steel plate, and cathode-current density is 253 A/m2.After 12 h of electrodialysis, total Chromium in Waste
Concentration drops to 0.910 mg/L, and total nickel concentration drops to 0.326 mg/L, meets the requirement of " discharge standard ", realizes stainless
The qualified discharge of steel pickling waste waters.
Claims (3)
1. a kind of method of heavy metal in removal stainless steel acid cleaning waste water, it is characterised in that the specific steps of this method are as follows:
It a. is 0~2.0 by pH value, the concentration of total iron, total chromium and total nickel is respectively 1500~1800 mg/L, 140~200 mg/
The stainless steel acid cleaning waste water of L and 100~160 mg/L are added to the medial compartment of dual membranes and three chambers electrodialysis cell；
B. the complexing agent X solution that concentration is 0.12~0.36 mol/L, pH value is 7.0~9.0 is added to dual membranes and three chambers electric osmose
Analyse the cathode chamber of slot；
C. 0.1 mol/L HNO is added in the anode chamber of dual membranes and three chambers electrodialysis cell3Solution；
D. using stainless steel as cathode, graphite is anode, is passed through direct current, and cathode-current density control is 250~300 A/m2；With
The progress of electrodialytic process, the acid radical anion in medial compartment waste water move to anode chamber, metal ion transport to cathode chamber
And it reacts to form metal complex anion with complexing agent；
E. reach national emission standard to the reduction of heavy metal ions in wastewater concentration, medial compartment waste water is discharged.
2. the method for heavy metal in removal stainless steel acid cleaning waste water according to claim 1, it is characterised in that complexing agent X is
Hydroxycarboxylate.
3. the method for heavy metal in removal stainless steel acid cleaning waste water according to claim 1, it is characterised in that the hydroxyl
Yl carboxylic acid salt are as follows: sodium citrate or sulfosalicylic acid sodium salt.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201811272159.3A CN109467167B (en) | 2018-10-30 | 2018-10-30 | Method for removing heavy metals in stainless steel pickling wastewater |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201811272159.3A CN109467167B (en) | 2018-10-30 | 2018-10-30 | Method for removing heavy metals in stainless steel pickling wastewater |
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| CN109467167A true CN109467167A (en) | 2019-03-15 |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110550707A (en) * | 2019-09-06 | 2019-12-10 | 温州捷朴环保科技有限公司 | Electrodialysis water treatment facilities with middle electrode |
| CN110963619A (en) * | 2019-12-02 | 2020-04-07 | 常州大学 | Integrated treatment device for steel pickling waste liquid |
| CN111003843A (en) * | 2019-12-26 | 2020-04-14 | 泰州市科源水处理有限公司 | Reduction treatment method for pickling sewage |
| CN113072233A (en) * | 2021-04-12 | 2021-07-06 | 大同氢都驰拓新能源有限公司 | Treatment method for treating acid wastewater for graphite purification |
| CN113578916A (en) * | 2021-06-23 | 2021-11-02 | 常熟理工学院 | Method for realizing resource utilization of phosphogypsum by utilizing waste incineration fly ash |
| CN115415304A (en) * | 2022-08-24 | 2022-12-02 | 昆明理工大学 | Method for high-value separation of valuable components in bulk solid waste soil |
| CN115849524A (en) * | 2023-02-23 | 2023-03-28 | 西安泰瑞环保技术有限公司 | Method, device and equipment for recovering heavy metals in wastewater based on improved electrodialysis method |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110550707A (en) * | 2019-09-06 | 2019-12-10 | 温州捷朴环保科技有限公司 | Electrodialysis water treatment facilities with middle electrode |
| CN110963619A (en) * | 2019-12-02 | 2020-04-07 | 常州大学 | Integrated treatment device for steel pickling waste liquid |
| CN111003843A (en) * | 2019-12-26 | 2020-04-14 | 泰州市科源水处理有限公司 | Reduction treatment method for pickling sewage |
| CN113072233A (en) * | 2021-04-12 | 2021-07-06 | 大同氢都驰拓新能源有限公司 | Treatment method for treating acid wastewater for graphite purification |
| CN113578916A (en) * | 2021-06-23 | 2021-11-02 | 常熟理工学院 | Method for realizing resource utilization of phosphogypsum by utilizing waste incineration fly ash |
| CN115415304A (en) * | 2022-08-24 | 2022-12-02 | 昆明理工大学 | Method for high-value separation of valuable components in bulk solid waste soil |
| CN115849524A (en) * | 2023-02-23 | 2023-03-28 | 西安泰瑞环保技术有限公司 | Method, device and equipment for recovering heavy metals in wastewater based on improved electrodialysis method |
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