CN109467167B - Method for removing heavy metals in stainless steel pickling wastewater - Google Patents
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- 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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- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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- C02F2101/00—Nature of the contaminant
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Abstract
The invention relates to a method for removing heavy metals in stainless steel pickling wastewater. The method is characterized in that an anion exchange membrane and a cation exchange membrane are combined into a double-membrane three-chamber electrodialysis groove, an intermediate chamber is arranged between the anion membrane and the cation membrane, an anode chamber is arranged on one side of the cathode membrane, and a cathode chamber is arranged on one side of the anode membrane. Adding the stainless steel pickling wastewater into an intermediate chamber, adding dilute nitric acid into an anode chamber, and adding a complexing agent into a cathode chamber. Stainless steel is used as a cathode, graphite is used as an anode, and direct current is introduced. Under the action of an electric field, the selective permeability of an ion exchange membrane to anions and cations is utilized, so that heavy metal ions in the wastewater are enriched in a cathode chamber in the form of metal complex anions, and acid radical anions are enriched in an anode chamber. The method has the characteristics of simple and convenient operation and easy control of process parameters, and not only can remove heavy metal ions in the stainless steel pickling wastewater, but also can enrich and recover the heavy metal ions.
Description
Technical Field
The invention relates to a method for removing heavy metals in stainless steel pickling wastewater by an electrodialysis method.
Background
Stainless steel has excellent corrosion resistance and mechanical properties and a beautiful surface, and is a widely used metal material. During smelting, casting, rolling and heat treatment of stainless steel, a thin and compact oxide film is formed on the surface of the stainless steel, and the main components of the oxide film are iron oxide (FeO and Fe)2O3And Fe3O4) Chromium oxide (Cr)2O3) Nickel oxide (NiO) and insoluble FeO & Cr2O3、FeO·Cr2O3·Fe2O3、Ni·Fe2O3And the like. In order to eliminate adverse effects on subsequent processing of stainless steel and to maintain good appearance, it is necessary to pass through the surfaceThe oxide film is removed by physical processing. The surface treatment process of stainless steel is mainly acid pickling due to Cr2O3、FeO·Cr2O3And FeO. Cr2O3·Fe2O3Since it is difficult to dissolve in a single acid, a mixed acid of nitric acid, hydrofluoric acid, and the like is generally used for the acid cleaning.
Stainless steel mixed acid (HNO)3+ HF) the waste water from pickling can be divided into two main categories, one being spent acid raffinate from the pickling tank and the other being wash waste water from the rinse. The former has strong acidity and high concentration of heavy metal ions; the latter is weak in acidity and low in heavy metal ion concentration. In order to facilitate subsequent treatment and maintain the stability and reliability of treatment facilities, most enterprises mix waste acid residual liquid and washing wastewater for treatment, and the mixed wastewater is the so-called stainless steel pickling wastewater. The wastewater contains Cr3+、Ni2+The heavy metal ions are strictly prohibited from being discharged without treatment by the national regulations.
With the increasing use of stainless steel in industrial departments in China and daily life of people, the production capacity of stainless steel is rapidly increased, and the large amount of pickling wastewater generated therewith also brings great environmental protection pressure to enterprises. At present, the technical researches on the treatment of heavy metal ions in stainless steel pickling wastewater comprise an electrochemical reduction method, a solvent extraction method, an adsorption method, an ion exchange method and the like. However, in consideration of the comprehensive investment, operation cost and technical maturity, enterprises generally adopt a neutralization precipitation method to treat the stainless steel pickling wastewater.
Although the neutralization precipitation method can remove heavy metal ions in the wastewater in the form of hydroxide precipitation, the precipitate (commonly called stainless steel pickling sludge) contains heavy metal elements Cr and Ni, belongs to industrial dangerous solid wastes, and occupies a large amount of land and is easy to cause secondary pollution if the precipitate is not simply buried. From the viewpoint of resource utilization of sludge, researchers use the sludge as an additive material to produce building materials, but the building material products obtained by the method have low market acceptance, and particularly the environmental safety under natural conditions is still evaluated.
Disclosure of Invention
The invention aims to provide a method for removing heavy metal ions in stainless steel pickling wastewater.
According to the invention, by utilizing the principle of ion exchange membrane electrodialysis, wastewater is introduced into an intermediate chamber in an electrodialysis device, hydroxycarboxylic acid salt is added into a cathode chamber as a complexing agent, heavy metal ions penetrate through a cation exchange membrane and enter the cathode chamber under the action of a direct current electric field, and react with hydroxycarboxylic acid radicals in the cathode chamber to generate metal complex anions, so that the wastewater in the intermediate chamber can reach the standard and be discharged, acid in the anode chamber can be recovered, and heavy metals can be recovered in the cathode chamber, thus, the environmental pollution can be reduced, and the resource utilization of the heavy metals can be realized.
The conception of the invention is as follows: a method for removing heavy metal ions in stainless steel pickling wastewater adopts a double-membrane three-chamber electrodialysis tank, and as shown in figure 1, the electrodialysis tank is divided into an anode chamber, a middle chamber and a cathode chamber through an anion exchange membrane and a cation exchange membrane. Adding stainless steel pickling wastewater into an intermediate chamber, adding dilute nitric acid into an anode chamber, adding a complexing agent X into a cathode chamber, and performing electrodialysis by adopting direct current. Fe in the wastewater of the middle chamber under the action of an electric field by utilizing the selective permeability of an ion exchange membrane3+、Cr3+And Ni2+Enabling cations to enter the cathode chamber through the cation exchange membrane and to perform chemical reaction with the complexing agent X to form metal complex anions which cannot return to the intermediate chamber; NO3 -And F-The acid radical anions enter the anode chamber through an anion exchange membrane, and the acid radical ions are enriched in the anode chamber. Under the continuous action of the electric field, the concentration of heavy metal ions in the wastewater in the intermediate chamber is gradually reduced until the discharge standard is reached, and the metal ions are enriched in the cathode chamber in the form of complex anions.
According to the inventive concept, the invention adopts the following technical scheme:
a method for removing heavy metals in stainless steel pickling wastewater is characterized by comprising the following specific steps:
a. adding stainless steel pickling wastewater with the pH value of 0-2.0 and the concentrations of total iron, total chromium and total nickel of 1500-1800 mg/L, 140-200 mg/L and 100-160 mg/L into a middle chamber of a double-membrane three-chamber electrodialysis tank;
b. adding a complexing agent X solution with the concentration of 0.12-0.36 mol/L, pH value of 7.0-9.0 into a cathode chamber of a double-membrane three-chamber electrodialysis tank;
c. adding 0.1 mol/L HNO into the anode chamber of the double-membrane three-chamber electrodialysis tank3A solution;
d. stainless steel is used as a cathode, graphite is used as an anode, direct current is introduced, and the current density of the cathode is controlled to be 250-300A/m2(ii) a Along with the proceeding of the electrodialysis process, acid radical anions in the wastewater in the middle chamber are transferred to the anode chamber, and metal ions are transferred to the cathode chamber and react with a complexing agent to form metal complex anions;
e. and discharging the wastewater of the intermediate chamber when the concentration of the heavy metal ions in the wastewater is reduced to reach the national discharge standard.
The complexing agent X is a hydroxycarboxylic acid salt.
The above-mentioned hydroxycarboxylic acid salt is: sodium citrate or sodium sulfosalicylate.
The features and advantages of the present invention are as follows:
1. adding complexing agent X into cathode chamber of double-membrane three-chamber electrolytic tank to make it and Fe3+、Cr3+And Ni2+And the metal ions generate complex anions, so that the metal ions in the acid washing wastewater of the intermediate chamber can be promoted to permeate through the cation exchange membrane, and meanwhile, the metal ions are prevented from being hydrolyzed in the solution of the cathode chamber, so that the electrodialysis process can be continuously and normally carried out.
2. By the method, the concentration of the heavy metal ions in the stainless steel pickling wastewater can meet the requirements of Integrated wastewater discharge Standard (GB 8978 & 1996) (hereinafter referred to as discharge Standard). The electrodialysis is continuously carried out for 10 times, the stainless steel pickling wastewater in the middle chamber can meet the requirement of 'discharge standard', and the harmlessness of the stainless steel pickling wastewater is realized.
3. Iron in the pickling wastewater is mainly deposited on the cathode plate, and chromium and nickel are mainly enriched in the cathode chamber solution, so that the volume of the heavy metal ion-containing solution is greatly reduced. Acid radicals in the acid washing wastewater are enriched in the anode chamber solution, so that the acid liquor is recovered. Realizes the recycling of the stainless steel pickling wastewater.
4. The used complexing agent X is environment-friendly, nontoxic and pollution-free, and can be regenerated and recycled after heavy metals are extracted from the concentrated solution in the cathode chamber by a proper method.
The method has simple removal process and high removal efficiency, and simultaneously avoids the defect of secondary pollution caused by stainless steel pickling sludge generated by the treatment of stainless steel pickling wastewater by the traditional neutralization method. The invention not only realizes the standard discharge of the stainless steel pickling wastewater, but also provides an effective way for the recycling of metal elements (Fe, Cr and Ni).
According to the selective permeation characteristic of the ion exchange membrane, namely, the cation exchange membrane only allows cations to permeate, the anion exchange membrane only allows anions to permeate, the acid washing wastewater passes through the cation exchange membrane to the other side under the action of a direct current electric field and is subjected to coordination reaction with anion ligands in an electrodialysis tank consisting of the anion exchange membrane and the cation exchange membrane to generate metal complex anions. Along with the proceeding of the electrodialysis process, the concentration of heavy metal ions in the wastewater at one side of the cation exchange membrane is continuously reduced until the discharge standard is reached. While the heavy metal ions on the other side are enriched in the form of a complex anion.
The method treats the stainless steel pickling wastewater by using the ion exchange membrane electrodialysis method, so that the concentration of heavy metal in the stainless steel pickling wastewater can reach the discharge standard, and valuable metal and acid in the stainless steel pickling wastewater can be recovered, thereby not only reducing the environmental pollution, but also realizing the resource utilization of the heavy metal.
Drawings
Figure 1 schematic diagram of a two-membrane three-compartment electrodialysis cell.
Detailed Description
Specific embodiments of the present invention will now be described.
Example 1
TABLE 1 composition of stainless Steel Pickling waste Water
By means of anion-exchange membranesAnd a cation exchange membrane divides the electrodialysis groove into an anode chamber, an intermediate chamber and a cathode chamber, stainless steel pickling wastewater is added into the intermediate chamber of the double-membrane three-chamber electrodialysis groove, 0.1 mol/L dilute nitric acid solution is added into the anode chamber, and a solution with complexing agent sodium sulfosalicylate concentration of 0.12 mol/L, pH of 7.2 is added into the cathode chamber, and direct current is adopted for electrodialysis. The anode is a graphite plate, the cathode is a stainless steel plate, and the current density of the cathode is 278A/m2. After electrodialysis for 10 h, the total chromium concentration in the wastewater is reduced to 0.872 mg/L, and the total nickel concentration is reduced to 0.747 mg/L, which meets the requirement of 'discharge standard'.
Example 2
Adding the stainless steel pickling wastewater into an intermediate chamber of a double-membrane three-chamber electrodialysis tank, adding 0.1 mol/L dilute nitric acid solution into an anode chamber, adding a solution with a complexing agent X sodium citrate concentration of 0.24 mol/L, pH of 8.8 into a cathode chamber, and performing electrodialysis by adopting direct current. The anode is a graphite plate, the cathode is a stainless steel plate, and the current density of the cathode is 253A/m2. After electrodialysis is carried out for 12 hours, the total chromium concentration in the wastewater is reduced to 0.910 mg/L, the total nickel concentration is reduced to 0.326 mg/L, the requirement of discharge standard is met, and the standard discharge of the stainless steel pickling wastewater is realized.
Claims (1)
1. A method for removing heavy metals in stainless steel pickling wastewater is characterized by comprising the following specific steps:
a. adding stainless steel pickling wastewater with the pH value of 0-2.0 and the concentrations of total iron, total chromium and total nickel of 1500-1800 mg/L, 140-200 mg/L and 100-160 mg/L into a middle chamber of a double-membrane three-chamber electrodialysis tank;
b. adding a complexing agent X solution with the concentration of 0.12-0.36 mol/L, pH value of 7.0-9.0 into a cathode chamber of a double-membrane three-chamber electrodialysis tank; the complexing agent X is a hydroxycarboxylic acid salt which is: sodium citrate or sodium sulfosalicylate;
c. adding 0.1 mol/L HNO into the anode chamber of the double-membrane three-chamber electrodialysis tank3A solution;
d. stainless steel is used as a cathode, graphite is used as an anode, direct current is introduced, and the current density of the cathode is controlled to be 250-300A/m2(ii) a With electricityCarrying out a dialysis process, wherein acid radical anions in the wastewater in the intermediate chamber are transferred to the anode chamber, and metal ions are transferred to the cathode chamber and react with a complexing agent to form metal complex anions;
e. and discharging the wastewater in the intermediate room when the concentration of the heavy metal ions in the wastewater is reduced to reach the national discharge standard GB 8978-1996.
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| 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 |
| CN113072233B (en) * | 2021-04-12 | 2023-03-17 | 大同氢都驰拓新能源有限公司 | Treatment method for treating acidic wastewater generated in graphite purification |
| CN113578916B (en) * | 2021-06-23 | 2022-05-10 | 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 |
| CN115849524B (en) * | 2023-02-23 | 2023-05-05 | 西安泰瑞环保技术有限公司 | Wastewater heavy metal recovery method, device and equipment based on improved electrodialysis method |
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| CA2236393C (en) * | 1997-05-07 | 2004-01-20 | Ulrich Reiter | Method and device for regenerating tin-plating solutions |
| CN106608696A (en) * | 2015-10-26 | 2017-05-03 | 天津工业大学 | Method for selectively separating heavy metal ions based on EDI and complexing agent |
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| CA2236393C (en) * | 1997-05-07 | 2004-01-20 | Ulrich Reiter | Method and device for regenerating tin-plating solutions |
| CN106608696A (en) * | 2015-10-26 | 2017-05-03 | 天津工业大学 | Method for selectively separating heavy metal ions based on EDI and complexing agent |
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| 电渗析法分离医疗垃圾焚烧飞灰浸出液中重金属;魏国侠等;《过程工程学报》;20141031;第776-781页 * |
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