CN115490306A - Treatment method of waste acid containing arsenic - Google Patents
Treatment method of waste acid containing arsenic Download PDFInfo
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- CN115490306A CN115490306A CN202210960881.6A CN202210960881A CN115490306A CN 115490306 A CN115490306 A CN 115490306A CN 202210960881 A CN202210960881 A CN 202210960881A CN 115490306 A CN115490306 A CN 115490306A
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- 150000002739 metals Chemical class 0.000 description 11
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Images
Classifications
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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
- C02F1/4695—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis electrodialysis electrodeionisation
-
- 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
- C02F2101/103—Arsenic compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/16—Nature of the water, waste water, sewage or sludge to be treated from metallurgical processes, i.e. from the production, refining or treatment of metals, e.g. galvanic wastes
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2201/00—Apparatus for treatment of water, waste water or sewage
- C02F2201/46—Apparatus for electrochemical processes
- C02F2201/461—Electrolysis apparatus
- C02F2201/46105—Details relating to the electrolytic devices
- C02F2201/46115—Electrolytic cell with membranes or diaphragms
-
- 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 discloses a method for treating waste acid containing arsenic, which comprises the following steps: (1) Carrying out electrodialysis treatment on the arsenic-containing waste acid by using common electrodialysis equipment to obtain an arsenic-rich solution and an acid-rich solution; (2) And carrying out electrodialysis treatment on the acid-rich solution by using bipolar membrane electrodialysis equipment to obtain an acid solution and a metal salt solution, so as to realize the separation of acid, metal elements and arsenic. The method for treating the waste acid containing arsenic has the characteristics of simple process operation, good quality separation effect, high quality separation efficiency, high effective utilization rate of resources and capability of realizing the open circuit of inorganic salt in acid, realizes the effective separation of arsenic, valuable metal and waste acid in the waste acid under the condition of no addition of an external medicament, realizes the effective open circuit of metal cations easy to scale in the arsenic and the waste acid, and lays a solid foundation for the concentration and recycling of the waste acid.
Description
Technical Field
The invention relates to the field of metallurgical environmental protection, in particular to a method for treating waste acid containing arsenic.
Background
The non-ferrous smelting process can generate a large amount of sulfur dioxide flue gas containing heavy metals such as arsenic and the like, the flue gas absorption process can generate a large amount of acidic wastewater, the concentration of arsenic in pollutants is highest, and the pollutants simultaneously contain heavy metal ions such as lead, cadmium, zinc, copper and the like and anions such as fluorine, chlorine and the like. The non-ferrous smelting waste acid has the characteristics of complex components, high arsenic concentration, large concentration fluctuation, high acidity and the like, and is also a difficult point for treating the smelting waste acid. In order to implement the concept of 'green development', meet the requirements of valuable metal and acid recovery and resource recycling, and reduce environmental pollution caused by wastewater discharge, a process for separating arsenic and recovering valuable metal and acid with environmental protection and high efficiency is urgently needed to be developed.
At present, domestic high-arsenic waste acid treatment methods mainly comprise a neutralization method, a vulcanization method, an adsorption method, a precipitation method, a membrane method and other treatment methods, but all have various problems and have not ideal treatment effects. Although the treatment process of the neutralization method is simple, a large amount of arsenic-alkali hazardous waste residues can be generated, the stacking and disposal of the residues have high risk and high cost, and a large amount of valuable metals and acid resources in the wastewater are wasted; although the amount of slag is reduced in the vulcanization method compared with the neutralization method, valuable metals such as copper, zinc and the like and arsenic are precipitated simultaneously in the vulcanization process, so that the effective recovery of the valuable metals cannot be realized, and in the concentration and recycling processes of the recovered acid, inorganic salts in the recovered acid are accumulated continuously to cause equipment scaling and finally cause the collapse of an acid recycling system; the membrane method treatment is a recent research hotspot and has a better effect on the quality-based treatment of the wastewater. Patent 202021364220.X (a concentrated brine resource utilization device in non-ferrous metal smelting industry) discloses a method for carrying out resource utilization on concentrated brine by adopting a defluorinating agent, a decalcifying agent, electrodialysis, a dechlorinating agent and a bipolar membrane acid and alkali production process, belonging to the resource utilization direction of the concentrated brine, and having small resource relevance with high arsenic-containing waste acid generated in smelting industry; patent 201510995648 (method for purifying and recycling high-arsenic waste acid wastewater) discloses a technology for treating arsenic-containing waste acid by membrane distillation, reduction crystallization, vulcanization precipitation and ion exchange, which can realize the removal of fluorine, chlorine and heavy metals in waste acid and the recycling of acid, but the arsenic and valuable metals are co-precipitated, so that the valuable metals cannot be effectively recovered, and the resource waste is caused, and the inorganic salt in the acid cannot be opened, so that the accumulation of the inorganic salt is caused.
Disclosure of Invention
The invention provides a method for treating waste acid containing arsenic, which is used for solving the technical problems that the existing treatment method is low in recovery efficiency, inorganic salt in equipment is easy to accumulate and scale, and the like.
In order to solve the technical problem, the invention adopts the following technical scheme:
a treatment method of waste acid containing arsenic comprises the following steps:
(1) Performing electrodialysis treatment on the arsenic-containing waste acid by using common electrodialysis equipment to obtain an arsenic-rich solution and an acid-rich solution;
(2) And carrying out electrodialysis treatment on the acid-rich solution by using bipolar membrane electrodialysis equipment to obtain an acid solution and a metal salt solution, so as to realize the separation of acid, metal elements and arsenic.
The design idea of the technical scheme is that the electrodialysis-bipolar membrane electrodialysis process is adopted to treat the waste acid with high arsenic content, so that a new solution and idea are provided for the problems of difficulty in recycling valuable metal resources in the waste acid with high arsenic content, accumulation of inorganic salts in acid and the like, the electrodialysis technology is applied to arsenic separation, and due to the valence state characteristic of trivalent arsenic, the trivalent arsenic is difficult to permeate through an anion-cation exchange membrane and is trapped in a light chamber of electrodialysis so as to separate arsenic and provide a basis for further step-by-step recovery of acid and valuable metals; the bipolar membrane electrodialysis can effectively separate acid and valuable metals, acid solution is recovered in an acid chamber, salt solution containing valuable metal ions such as copper and zinc is recovered in a salt chamber, and the purpose of efficiently recovering the valuable metals and the acid in waste acid can be achieved. Meanwhile, the common technical route of the existing waste acid treatment and recycling technology is 'precipitation for removing heavy metals, evaporation for removing fluorine and chlorine, acid concentration and recycling', inorganic salts of the waste acid enter recycled acids, and the inorganic salts are continuously accumulated along with the increase of the acid concentration of the recycled acids in the evaporation and concentration process to cause equipment scaling and finally cause the collapse of an acid concentration system. The invention can well solve the problem, and separates more than 95 percent of metal ions such as Mg, ca, fe, mn, cd, pb and the like and more than 90 percent of ions such as Na, K and the like in the waste acid, thereby realizing the open circuit of the metal ions which are easy to form scale in Ca, mg and the like in the recycled acid and providing a good basis for the concentration and recycling of the acid.
As a further preferable mode of the above technical solution, the metal salt solution in the step (2) is recycled for electrolysis after precipitation and acid dissolution, so as to realize effective recovery of valuable metal resources such as copper and zinc.
As a further optimization of the technical scheme, the acid solution is concentrated and then recycled, so that the resource utilization of the acid is realized.
As a further preferred aspect of the above technical solution, the common electrodialysis apparatus comprises a plurality of electrodialysis units connected in series; the electrodialysis unit comprises an anion exchange membrane, a cation exchange membrane and an anion exchange membrane which are assembled in sequence; the bipolar membrane electrodialysis equipment comprises a plurality of bipolar membrane electrodialysis units connected in series; the bipolar membrane electrodialysis unit comprises a bipolar membrane, an anion exchange membrane, a cation exchange membrane, an anion exchange membrane and a bipolar membrane which are assembled in sequence. Compared with the conventional electrodialysis membrane stack, the membrane stack structure of the electrodialysis equipment has the advantages that the bipolar membranes are additionally arranged at the two ends, valuable metals and other ions in the grid chambers at the two ends can be effectively prevented from entering the cathode chamber and the anode chamber through the bipolar membranes, the recovery rate of the valuable metals can be effectively improved, and meanwhile, the pollution of polar liquid is avoided.
As a further preferable mode of the above technical solution, bipolar membranes are provided at both ends of a cathode and an anode of the electrodialysis unit. The bipolar membrane is used for replacing the cathode membrane and the anode membrane at the cathode and the anode of the electrodialysis equipment, so that the anions and the cations in the waste acid can be prevented from entering the polar liquid, and the electrode corrosion and the valuable metal ion loss are avoided. In a further preferred aspect of the above technical solution, the anion exchange membrane is one or a combination of two of an amine-based amino exchange membrane and an aromatic amino exchange membrane; the cation exchange membrane is one or the combination of two of a sulfonic acid exchange membrane, a carboxylic acid group exchange membrane and a phosphate group exchange membrane.
As a further preferred aspect of the above technical means, in the electrodialysis unit, the total effective area of the anion exchange membrane and the cation exchange membrane is 550cm 2 。
In a further preferred embodiment of the present invention, adjacent ion exchange membranes in the electrodialysis unit are separated by a separator.
As a further preferable mode of the above technical means, in the step (2), the acid-rich solution is treated by a bipolar membrane electrodialysis treatment operation under a constant current condition, and the density of the constant current is 1.0 to 2.0mA/cm 2 . The current density limited by the optimal scheme can give consideration to both current efficiency and production energy consumption.
As a further preferred aspect of the above technical solution, the arsenic-containing waste acid is treated by a multi-stage electrodialysis in step (1). In the preferred scheme, the high-arsenic waste acid treated by two or more stages of electrodialysis in series can remove more than 99% of high-concentration arsenic, improve the recovery efficiency of arsenic and reduce impurity ions in subsequent acid solution.
As a further preferable mode of the above technical solution, before the arsenic-containing waste acid is subjected to electrodialysis treatment in step (1), an operation of subjecting the arsenic-containing waste acid to filtration treatment with a filter membrane is further included.
As a further preferable mode of the above technical means, the pore diameter of the filtration membrane is 0.2 to 0.8 μm; the material of the filtering membrane is an organic porous material, and the organic porous material comprises one or more of PP, PE, PVDF and PTFE.
As a further optimization of the technical proposal, in the waste acid containing arsenic, the concentration of copper ions is 0 to 5.0g/L, the concentration of zinc ions is 0 to 5.0g/L, the concentration of acid is 0.1 to 1.0mol/L, and the concentration of arsenic is 0 to 15g/L.
Compared with the prior art, the invention has the advantages that:
the method for treating the arsenic-containing waste acid has the characteristics of simple process operation, good quality separation effect, high quality separation efficiency, high effective utilization rate of resources and capability of realizing the open circuit of inorganic salt in acid, realizes the effective separation of arsenic, valuable metals (including metal cations) and waste acid in the waste acid under the condition of no addition of exogenous medicament, realizes the effective open circuit of the arsenic and the metal cations easy to scale in the waste acid, and lays a solid foundation for the concentration and recycling of the waste acid.
Drawings
FIG. 1 is a process flow diagram of the treatment process of spent acid containing arsenic according to example 1;
FIG. 2 is a schematic diagram of the structure and operation principle of an electrodialysis unit in example 1;
FIG. 3 is a schematic diagram of the construction and operation of the electrodialysis unit in example 2;
fig. 4 is a schematic diagram of the structure and the operation principle of the bipolar membrane electrodialysis unit in example 1.
Detailed Description
The present invention will be described in further detail with reference to specific examples.
Example 1:
the process flow diagram of the treatment method of waste acid containing arsenic of the embodiment is shown in fig. 1, the copper ions in the waste acid containing arsenic treated by the treatment method are 518mg/L, the zinc ions are 260mg/L, the acid concentration is 0.34mol/L, and the arsenic concentration is 510mg/L, and the treatment method comprises the following steps:
(1) Filtering the arsenic-containing waste acid by adopting a vacuum filtration method to obtain filtrate; wherein the aperture of the used filtering membrane is 0.45 μm; the filter membrane material is an organic porous material and is PP;
(2) Carrying out two-stage electrodialysis series treatment on the filtrate obtained in the step (1), recovering an arsenic-rich solution from a light chamber, and recovering an acid-rich solution from a thick chamber; the membrane stack configuration of the electrodialysis device used in the step is formed by connecting a plurality of electrodialysis units in series, the structure and the operation principle of each electrodialysis unit are shown in figure 2, the assembly sequence from the cathode to the anode is an anion exchange membrane, a cation exchange membrane and an anion exchange membrane, two adjacent membranes are separated by a partition plate, the cathode of the electrodialysis is connected with the cathode of a direct current power supply, and the anode is connected with the anode of the direct current power supply.The electrodialysis fresh room is connected with a desalting tank, which is called an S room for short; the electrodialysis concentration chamber is connected with a concentration tank, referred to as a chamber B for short; the current density is adjusted to be 1.5mA/cm in the electrodialysis process 2 The experimental time is 120min, and tests show that the separation rate of arsenic in a dilute chamber is 92%, the recovery rate of copper ions in a dense chamber is 74%, the recovery rate of zinc ions is 70%, and the recovery rate of acid is 80%;
(3) Carrying out electrodialysis treatment on the acid-rich solution in the step (2) by adopting a two-compartment bipolar membrane, recovering a metal salt solution containing valuable metal ions such as copper and zinc from a salt chamber, and recovering an acid solution from an acid chamber; the two-compartment bipolar membrane electrodialysis membrane stack structure is formed by connecting a plurality of bipolar membrane electrodialysis units in series, the structure and the operation principle of the bipolar membrane electrodialysis units are shown in figure 4, the assembly sequence of each bipolar membrane electrodialysis unit from the cathode to the anode is a bipolar membrane, an anion exchange membrane and a bipolar membrane, and two adjacent membranes are separated by a partition plate; the current density is adjusted to be 1.5mA/cm in the electrodialysis process 2 The experimental time is 90min, the test shows that the recovery rate of acid in an acid chamber is 99%, and the recovery rate of valuable metal ions such as copper, zinc and the like in a salt chamber is 99%.
And (4) obtaining an acid solution and a metal salt solution from the high-arsenic-content waste acid treated in the step (3), wherein the obtained acid concentration is 0.27mol/L, the comprehensive recovery rate is 80%, the comprehensive recovery rates of copper and zinc ions in the metal salt solution are 74% and 73%, and the comprehensive separation rate of arsenic is 92%.
And (4) concentrating the acid obtained in the step (3) to the purity of 96%, and realizing the recycling of the acid.
The concentration of copper-containing zinc ions in the metal salt solution obtained in the step (3) is 344.5mg/L, 176.9mg/L (recovery rate is 74% and 69%) and the concentration of arsenic is 40mg/L (arsenic separation rate is more than 92%), and the metal salt solution is recycled for electrolysis after precipitation and acid dissolution, so that the effective recovery of valuable metal resources such as copper, zinc and the like is realized.
Example 2:
in the treatment method of the arsenic-containing waste acid of the embodiment, the treated arsenic-containing waste acid contains 423.5mg/L of copper ions, 233.4mg/L of zinc ions, 0.34mol/L of acid and 6620mg/L of arsenic ions, and the method comprises the following steps:
(1) Filtering the arsenic-containing waste acid by adopting a vacuum filtration method to obtain filtrate; wherein the aperture of the used filter membrane is 0.45 μm; the filter membrane material is an organic porous material and is PP;
(2) Carrying out two-stage electrodialysis series treatment on the filtrate obtained in the step (1), recovering an arsenic-rich solution from a light chamber, and recovering an acid-rich solution from a thick chamber; the membrane stack configuration of the electrodialysis device used in the step is formed by connecting a plurality of electrodialysis units in series, the structure and the operation principle of each electrodialysis unit are shown in figure 3, the assembly sequence from the cathode to the anode is an anion exchange membrane, a cation exchange membrane and an anion exchange membrane, two bipolar membranes respectively replace a cathode membrane and an anode membrane at two ends of the cathode and the anode, the two adjacent membranes are separated by a partition plate, the cathode of the electrodialysis is connected with the cathode of a direct current power supply, and the anode is connected with the anode of the direct current power supply. The electrodialysis fresh room is connected with a desalting tank, which is called an S room for short; the electrodialysis concentration chamber is connected with a concentration tank, referred to as a chamber B for short; the current density is adjusted to be 4mA/cm in the electrodialysis process 2 The experimental time is 60min, and tests show that the separation rate of arsenic in the dilute chamber is 99.3%, the recovery rate of copper ions in the concentrate chamber is 94.4%, the recovery rate of zinc ions is 94.00%, and the recovery rate of acid is 96.2%.
(3) Performing electrodialysis treatment on the acid-rich solution in the step (2) by adopting a two-compartment bipolar membrane, recovering a metal salt solution containing valuable metal ions such as copper and zinc from a salt chamber, and recovering an acid solution from an acid chamber; the two-compartment bipolar membrane electrodialysis membrane stack structure is formed by connecting a plurality of bipolar membrane electrodialysis units in series, the bipolar membrane, the anion exchange membrane and the bipolar membrane are assembled in sequence from the cathode to the anode of each bipolar membrane electrodialysis unit, and two adjacent membranes are separated by a partition plate; the current density is adjusted to be 1.5mA/cm in the electrodialysis process 2 The experimental time is 90min, the recovery rate of acid in an acid chamber is 99.1% through testing, and the recovery rate of valuable metal ions such as copper, zinc and the like in a salt chamber is 99.0%.
And (4) obtaining an acid solution and a metal salt solution from the high-arsenic-content waste acid treated in the step (3), wherein the obtained acid concentration is 0.30mol/L, the comprehensive recovery rate is 95.1%, the comprehensive recovery rates of copper and zinc ions in the metal salt solution are 93.6% and 93.1%, and the comprehensive separation rate of arsenic is 99.4%.
The acid obtained in the step (3) can be concentrated to the purity of 94.5%, so that the recycling of the acid is realized. Metal ions such as Mg, ca, fe, mn, cd, pb and the like in the waste acid are less than 5 percent, na and K are less than 10 percent and enter the recovered acid, so that the open circuit of the scale-forming metal ions which are easily formed by Ca, mg and the like in the waste acid is realized.
The concentrations of copper and zinc ions in the metal salt solution obtained in the step (3) are 393.4mg/L, 215.7mg/L (the comprehensive recovery rates are 93.6% and 93.1% respectively) and the arsenic concentration is 40mg/L (the arsenic separation rate is more than 92%), and the metal salt solution is recycled for electrolysis after precipitation and acid dissolution, so that the effective recovery of valuable metal resources such as copper, zinc and the like is realized.
The above description is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above-described embodiments. Modifications and variations that may occur to those skilled in the art without departing from the spirit and scope of the invention are to be considered as within the scope of the invention.
Claims (9)
1. The method for treating the waste acid containing arsenic is characterized by comprising the following steps of:
(1) Performing electrodialysis treatment on the arsenic-containing waste acid by using common electrodialysis equipment to obtain an arsenic-rich solution and an acid-rich solution;
(2) And performing electrodialysis treatment on the acid-rich solution by using a bipolar membrane electrodialysis device to obtain an acid solution and a metal salt solution, so as to realize the separation of acid, metal elements and arsenic.
2. A method for treating waste acid containing arsenic as claimed in claim 1, wherein the common electrodialysis unit comprises several electrodialysis units connected in series; the electrodialysis unit comprises an anion exchange membrane, a cation exchange membrane and an anion exchange membrane which are assembled in sequence; the bipolar membrane electrodialysis equipment comprises a plurality of bipolar membrane electrodialysis units connected in series; the bipolar membrane electrodialysis unit comprises a bipolar membrane, an anion exchange membrane and a bipolar membrane which are assembled in sequence.
3. The method for treating waste acid containing arsenic as claimed in claim 2, wherein bipolar membranes are arranged at both ends of the cathode and the anode of the electrodialysis unit.
4. The method for treating waste acid containing arsenic of claim 2, wherein the anion exchange membrane is one or a combination of an amine amino exchange membrane and an aromatic amino exchange membrane; the cation exchange membrane is one or the combination of two of a sulfonic acid exchange membrane, a carboxylic acid group exchange membrane and a phosphate group exchange membrane.
5. The method for treating waste acid containing arsenic as claimed in claim 2, wherein the acid-rich solution in step (2) is treated by bipolar membrane electrodialysis under constant current with density of 1.0-2.0 mA/cm 2 。
6. The method for treating waste acid containing arsenic as claimed in claim 1, wherein step (1) comprises treating the waste acid containing arsenic by multi-stage electrodialysis.
7. The method for treating waste acid containing arsenic as claimed in claim 1, wherein step (1) further comprises the step of subjecting the waste acid containing arsenic to filtration treatment with a filter membrane before subjecting the waste acid containing arsenic to electrodialysis treatment.
8. The treatment method of waste acid containing arsenic according to claim 7, wherein the aperture of the filter membrane is 0.2-0.8 μm; the material of the filtering membrane is an organic porous material, and the organic porous material comprises one or more of PP, PE, PVDF and PTFE.
9. The treatment method of waste acid containing arsenic as claimed in any one of claims 1 to 8, wherein the concentration of copper ions in the waste acid containing arsenic is 0-5.0 g/L, the concentration of zinc ions is 0-5.0 g/L, the concentration of acid is 0.1-1.0 mol/L, and the concentration of arsenic is 0-15 g/L.
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