WO2018161682A1 - 从硫酸体系电解液中选择性去除一价阴离子杂质的方法 - Google Patents

从硫酸体系电解液中选择性去除一价阴离子杂质的方法 Download PDF

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WO2018161682A1
WO2018161682A1 PCT/CN2017/117527 CN2017117527W WO2018161682A1 WO 2018161682 A1 WO2018161682 A1 WO 2018161682A1 CN 2017117527 W CN2017117527 W CN 2017117527W WO 2018161682 A1 WO2018161682 A1 WO 2018161682A1
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electrolyte
impurities
sulfuric acid
free
monovalent anion
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English (en)
French (fr)
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张伟明
陈庆
陈宝生
肖东
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温州大学
北京京润环保科技股份有限公司
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
    • C25C1/16—Electrolytic production, recovery or refining of metals by electrolysis of solutions of zinc, cadmium or mercury
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/42—Treatment or purification of solutions, e.g. obtained by leaching by ion-exchange extraction
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
    • C25C7/06—Operating or servicing
    • 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

Definitions

  • the invention relates to the field of hydrometallurgy, in particular to a method for selectively removing monovalent anion impurities from an electrolyte of a sulfuric acid system, in particular to a method for selectively removing fluorine and chlorine impurities from a zinc sulfate electrolyte solution, In this way, the content of fluorine and chlorine impurities in the electrolyte in the wet zinc smelting process cycle is always lower than or meets the process requirements.
  • the method is also suitable for selectively removing monovalent anion impurities (such as F - , Cl - , Br - , I - , NO 3 - , NO 2 ) from other sulfuric acid system electrolytes (such as Zn, Mn, Cu, Co, etc.). -etc .).
  • monovalent anion impurities such as F - , Cl - , Br - , I - , NO 3 - , NO 2
  • the main process is ZnS ore raw material roasting ⁇ sulfuric acid leaching ⁇ electrowinning zinc.
  • the electrolyte before electrowinning is near neutral, and some ZnSO 4 is converted to H 2 SO 4 during electrolytic zinc deposition.
  • the acidic electrolyte obtained after electrowinning zinc, whose main components are ZnSO 4 and H 2 SO 4 will be used to re-extract the calcined ore to regenerate the electrolyte to form an electrolyte cycle in the wet zinc smelting process.
  • the core of wet zinc smelting is to purify these zinc electrolytes in order to maintain the smooth progress of the process, while reducing the energy consumption of zinc hydride and finally obtaining high purity cathode metal zinc.
  • impurities such as iron, cobalt, nickel, gallium, antimony, arsenic, chlorine and fluorine are required to be maintained at a low concentration.
  • chlorine and fluorine impurities are often difficult to remove during actual operation, so their concentration tends to accumulate in the electrolyte.
  • Cl - can be AgCl (CN1936036A), BOCl ("Hydrometallurgy", Vol. 33, No. 6, pp. 480-482), Sn(OH)Cl (CN102851503A) and CuCl (CN101633982A, CN102796869A, CN102732725B) removing a precipitate; F - may be removed as precipitate CaF 2.
  • the same function can be achieved by means of the monovalent ion selectivity provided by the nanofiltration membrane, combined with ordinary electrodialysis (CN103572051A).
  • it is a monovalent ion-selective ion exchange membrane or a nanofiltration membrane material
  • its monovalent ion selectivity is directly related to the concentration of the salt solution it treats. As the salt concentration increases, its monovalent ion selectivity is also greatly reduced.
  • the concentration of zinc electrolyte used in the wet zinc industry is very high (the concentration of SO 4 2- ions is about 320g / L).
  • the present invention aims to solve at least one of the technical problems existing in the prior art.
  • the main chemical composition of the acidic zinc electrolyte is H 2 SO 4 and ZnSO 4 , and contains a small amount of impurities such as Cl - , F - and the like.
  • the current thinking mainly focuses on the selective precipitation and utilization of Zn resources in the waste electrolyte by using a base such as Ca(OH) 2 (CN101760632B, CN100450942C). Due to the presence of a large amount of free H 2 SO 4 , the amount of alkali and the amount of CaSO 4 slag produced during the precipitation of Zn resources are greatly increased.
  • the patent CN100450942C proposes a method of using diffusion dialysis technology to recover free H 2 SO 4 in the waste electrolyte, thereby reducing the amount of calcium and alkali used in the neutralization process, while reducing the reaction to some extent.
  • the slag amount, the processing flow is shown in Figure 1. First, a part of the acidic zinc electrolyte is taken out from the electrowinning zinc electrolyte circulating cycle into the waste acid chamber of the diffusion dialysis device, and the other water is used as a receiving liquid to pass into the diffusion dialysis recovery chamber in a countercurrent manner.
  • the free acid (including H 2 SO 4 , HCl and HF impurities) is transported from the spent acid chamber to the recovery chamber under concentration drive to obtain a recovered acid.
  • the purpose of the diffusion dialysis technique is to recover as much free acid or base as possible (Journal of Membrane Science 2011, 366: 1-16), in which more than 80% of the free H 2 SO 4 in the acid zinc electrolyte is recovered.
  • the concentration of free acid in the acidic electrolyte is greatly reduced, and the amount of alkali consumed when the alkali zinc is added can be greatly reduced, and the amount of CaSO 4 slag precipitated together with the basic zinc sulfate is also reduced.
  • the zinc-containing filter residue is reused, the filtrate is discharged, and the fluorine-chloride impurities contained in the supernatant are removed from the system.
  • the zinc-containing slag and the previously recovered H 2 SO 4 are reacted in an acid-dissolving step to obtain a zinc-containing electrolyte, which is reused in the main circulation of the electrolyte.
  • the acid-insoluble waste (mainly CaSO 4, etc.) must be discharged during this process.
  • the discharged waste residue and the filtrate contain a large amount of SO 4 2- , it is necessary to add a sufficient amount of concentrated H 2 SO 4 to maintain a constant sulfate content in the electrolyte system.
  • the patent CN100450942C reduces the comprehensive cost of acid zinc electrolyte treatment to a certain extent, reduces the consumption of alkali and the yield of residue, and has obvious economic benefits.
  • the amount of alkali consumed and the amount of slag produced are still large, resulting in a high overall cost, which the company cannot fully accept.
  • the large amount of filtrate and waste generated is still an environmental problem that cannot be solved for enterprises.
  • the present invention provides a method of selectively removing monovalent anion impurities from a sulfuric acid system electrolyte.
  • the method comprising: adjusting the electrolyte concentration of free H 4 2 SO, containing the free H 2 SO 4 electrolyte solution through dialysis spent acid into the diffuser chamber to receive the liquid water in the reverse
  • the flow mode is introduced into the diffusion dialysis recovery chamber to control the flow intensity of the electrolyte during the diffusion dialysis operation.
  • Part of the free H 2 SO 4 and anion impurities in the electrolyte inside the diffusion dialysis unit are transmitted through the membrane to the receiver under the concentration drive.
  • a dilute H 2 SO 4 enriched by monovalent anion impurities and a purified electrolyte are formed,
  • an anion exchange membrane is disposed in the diffusion dialysis device
  • sulfuric acid system electrolyte is at least one selected from the group consisting of Zn 2+ , Mn 2+ , Cu 2+ and Co 2+ sulfuric acid electrolytes;
  • the monovalent anion impurity is at least one selected from the group consisting of F - , Cl - , Br - , I - , NO 3 - , and NO 2 - .
  • the method for selectively removing monovalent anion impurities from an electrolyte of a sulfuric acid system breaks through separation of free acid and salt (or free base and salt) by diffusion dialysis, and recovers free acid (or alkali)
  • the thinking formula solves the problem that the traditional method such as the patent CN100450942C consumes a large amount of alkali, and at the same time produces waste residue discharge and long process flow.
  • Zn 2+ , Mn 2+ , Cu 2+ and Co 2+ sulfuric acid system electrolytes refers to ZnSO 4 , MnSO 4 , CuSO 4 and CoSO 4 electrolytes, and electrolysis of sulfuric acid systems.
  • the liquid may be selected from at least one of ZnSO 4 , MnSO 4 , CuSO 4 and CoSO 4 electrolytes.
  • the monovalent anion impurity-rich dilute H 2 SO 4 produced by diffusion dialysis is subjected to a regeneration purification treatment using a desalination apparatus to obtain purified water, and the purified water is reused.
  • a receiving liquid wherein the desalination device is one of a reverse osmosis, an electrodialysis, a thermal distillation, or a membrane distillation apparatus.
  • the dilute H 2 SO 4 enriched in the discarded monovalent anion impurities is removed by the purification treatment to form the purified water, and the purified water is reused as the receiving liquid to reduce the water consumption during the diffusion dialysis process, and at the same time Significantly reduce the volume of waste liquid discharge, industrial costs can be greatly reduced
  • the sulfuric acid system electrolyte may be a zinc sulfate electrolyte
  • the monovalent anion impurity may be a fluorine chlorine impurity.
  • the Cl - content in the electrolytic solution may be 200-10000 mg/L
  • the F - content may be 50-1000 mg/L.
  • the concentration of fluorine and chlorine impurities is high, and is easily removed by osmosis, and when the Cl - content in the electrolyte is 200-10000 mg/L and the F - content is 50-1000 mg/L, the fluorine-chloride impurities are The removal rate remains stable.
  • the flow rate of the electrolyte during the diffusion dialysis operation is 1.6-20.0 L h -1 m -2 .
  • the flow rate of the electrolyte is usually controlled to be less than 1 L h -1 m -2 .
  • the recovery of free H 2 SO 4 is not an indicator of process efficiency.
  • the inventors have unexpectedly found that by reducing the contact time of the acidic electrolyte with water, i.e., by increasing the operating flow intensity of the diffusion dialysis process, the separation efficiency of the total SO 4 2- and F - , Cl - in the process can be significantly improved.
  • the removal efficiency of monovalent anion impurities (such as F - , Cl - etc.) in the acidic electrolyte can be significantly higher than the total SO 4 2- removal efficiency, which of Cl - sO 4 2- are removal rate of 2.5-2.8 times, F - removal of both sO 1.4-1.6 times 4 2-, thus, a monovalent anionic impurities removal Significantly increased.
  • the ratio of the flow rate of water and the zinc sulfate electrolyte containing free H 2 SO 4 is not particularly limited, and those skilled in the art can adjust according to specific conditions.
  • the ratio of the flow rate of water to the zinc sulfate electrolyte containing free H 2 SO 4 may be from 0.5 to 2.0:1. Thereby, the removal effect of the monovalent anion impurities in the electrolytic solution is good.
  • the ratio of the flow rate of water to the zinc sulfate electrolyte containing free H 2 SO 4 may be 1:1. Thereby, the pressure on both sides of the anion exchange membrane is equal, the ion exchange efficiency is high, and the removal rate of monovalent anion impurities is high.
  • the method for selectively removing monovalent anion impurities from the sulfuric acid system electrolyte can not only remove monovalent anion impurities from the acidic electrolyte, but also remove one price from the neutral electrolyte as shown in FIG. Anionic impurities.
  • the concentration of free H 2 SO 4 in the electrolyte can be adjusted to be 0.5 to 100 g/L by adding concentrated H 2 SO 4 or directly introducing SO 3 gas.
  • concentrated sulfuric acid refers to a sulfuric acid solution having a mass fraction greater than or equal to 70%.
  • electrolytic lean solution containing a high concentration of free acid it is also possible to add an electrolytic lean solution containing a high concentration of free acid to the electrolyte to adjust the concentration of free H 2 SO 4 in the electrolyte, and the amount of the electrolytic lean solution is 0.5% - 60%.
  • the electrolyte is a neutral electrolyte.
  • electrolytic lean liquid containing a high concentration of free acid means an electrolytic lean liquid having a free acid concentration (as H 2 SO 4 ) at 30-160 g/L.
  • the concentration of free H 2 SO 4 in the electrolyte can be adjusted by adding a material containing H 2 SO 4 or leaching the electrolyte of the process section.
  • a zinc electrolyte having a suitable acidity may be selected, that is, an electrolyte leaching section is selected.
  • At least one of the thermal acid leaching solution, the thermal acid leaching solution, the weak acid leaching solution and the neutral leaching solution adjusts the concentration of free H 2 SO 4 in the electrolyte, thereby controlling the suitable free acidity for the selection of fluorochloro impurities without external acid addition. Sexual removal.
  • the electrolyte selectively removes the fluorine chlorine process
  • the method can selectively remove the fluorine and chlorine impurities in the acid zinc electrolyte, so that the zinc electrolyte originally required to be discharged is returned to the electrolyte cycle.
  • a part of the acidic zinc electrolyte is taken out from the zinc electrolyte cycle in the form of a bypass circulation and passed into the waste acid chamber of the diffusion dialyzer, while another water is passed as a receiving liquid to the diffusion dialysis recovery chamber in a countercurrent manner.
  • the purpose of using diffusion dialysis in the present invention is to selectively remove fluorochloride impurities in the acidic zinc electrolyte, rather than separating and recovering free H 2 SO 4 . Therefore, in the present invention, the recovered H 2 SO 4 obtained after diffusion dialysis is waste, that is, the fluorine chlorine impurity outlet; and the diffusion dialysis residual liquid is the purified zinc electrolyte resource. Relative to the original acid zinc electrolyte, it lost some of the free H 2 SO 4 and HCl, HF after passing through the diffusion dialysis machine.
  • the loss of free H 2 SO 4 can be compensated by adding an equal mass of concentrated H 2 SO 4 or SO 3 gas, so that the removal of chlorochloride impurities in the electrolyte can be achieved.
  • the present invention can greatly enhance the selectivity of the diffusion dialysis process to monovalent anions (especially chlorofluoro impurities) in the sulfuric acid electrolyte system by controlling certain technical parameters.
  • the contact time of the spent acid solution (here, the acidic zinc electrolyte) with the receiver stream during the diffusion dialysis process can be measured by the operating flow intensity of the spent acid solution.
  • low operating flow intensity is often required, which means that the contact time of the spent acid solution with the receiving liquid is very high. long.
  • the recovery of free H 2 SO 4 is not an indicator of the efficiency of the process.
  • the removal efficiency of monovalent anion impurities (such as F - , Cl - etc.) in the acidic electrolyte can be significantly higher than the total SO 42- removal efficiency, wherein of Cl - SO 2.5-2.8 times the removal rate are 4 2-, F - removal of both SO 1.4-1.6 times 4 2-.
  • the process proposed in FIG. 2 can be further improved to improve the selectivity of removing Cl ⁇ , F ⁇ ion impurities during the separation process and reduce the loss of sulfate substances.
  • the concentration of free H 2 SO 4 in the acidic zinc electrolyte produced after the zinc electrowinning process is very high (typically 160 g/L), and the concentration of fluorine and chlorine impurities contained therein is very low (F - concentration is 50-300 mg /
  • the concentration of L,Cl - is 100-1000 mg / L), and the concentration of the substrate SO 4 2- ion can reach ⁇ 1000 times of the impurity ion concentration.
  • diffusion dialysis has a significant selective permeability to F - and Cl - relative to SO 4 2- , the loss of SO 4 2- species is still predominant and large.
  • the transmembrane transport of free H 2 SO 4 is completely meaningless (as opposed to acid recovery) and should be inhibited. Reducing the concentration of free H 2 SO 4 in the electrolyte is one of the powerful means to inhibit the transport of H 2 SO 4 across the membrane. After the free acid content is reduced, the transmembrane transport of H 2 SO 4 is greatly reduced, but the transport of F - and Cl - has little effect. Therefore, by reducing the free acid concentration in the electrolyte to regulate the transmembrane transport of different ions, the purpose of increasing the selectivity of chlorofluoro removal can be achieved.
  • the present invention therefore proposes a dechlorination process as shown in FIG.
  • the choice is to start with a neutral zinc electrolyte.
  • a small amount of concentrated sulfuric acid must be added to the neutral electrolyte to provide a driving force for diffusion dialysis (difference in the concentration of free acid on the left and right sides), and the concentration of H 2 SO 4 added is 0.5–100 g/L.
  • the addition of acid can also be added in the form of an acidic zinc electrolyte, as shown in Figure 4, wherein the acid zinc electrolyte is added in an amount of 0.5-60%.
  • the removal rate of chlorochloride impurities in Figures 3 and 4 remains basically the same, but the loss rate of sulfate is greatly reduced (down to 5%), which effectively improves the separation of the process. effectiveness.
  • the preparation of a neutral electrolyte from an acidic electrolyte is often done in multiple steps.
  • thermal acid leaching free H 2 SO 4 concentration is greater than 120g / L, temperature is higher than 90 ° C
  • hot acid leaching free H 2 SO 4 concentration is 30-80g / L, the temperature is higher than 90 ° C
  • weak acid leaching free H 2 SO 4 concentration of 10 g / L, temperature of about 60 ° C
  • neutral leaching pH 4.4-5.5, 60 ° C
  • the concentration of free sulfuric acid in the zinc electrolyte is gradually decreased as the degree of reaction with the zinc calcine increases, and the present invention can select a zinc electrolyte having a suitable acidity or mix the above-mentioned leachate, so that it is not necessary to pass External addition of acid can control the appropriate free acidity for selective removal of chlorochloride impurities.
  • the smelting process of Mn, Cu, and Co also uses a sulfuric acid electrolyte system, and also removes monovalent ion impurities such as F - , Cl - , Br - , I - , NO 3 - , NO 2 - Waiting for the demand.
  • monovalent ion impurities such as F - , Cl - , Br - , I - , NO 3 - , NO 2 - Waiting for the demand.
  • the sulfuric acid system electrolyte (including Zn 2+ , Mn 2 ) contaminated by monovalent ions X - impurities (such as F - , Cl - , Br - , I - , NO 3 - , NO 2 - etc.) + , Cu 2+ , Co 2+ and other systems), if necessary, can add a small amount of acidic substances (can be pure H 2 SO 4 , acidic electrolyte generated after electrolysis or other substances containing free acid, etc.) to adjust its free acidity Then, it is passed into the waste acid chamber of the diffusion dialysis unit. At the same time, the water enters the recovery chamber in a countercurrent manner. During this process, X - impurities and SO 4 2- enter the recovery chamber along with H + , leaving the electrolyte system to remove X - impurities.
  • X - impurities such as F - , Cl - , Br - , I - , NO 3 -
  • the present invention can limit the transport of SO 4 2- in this process, the concentration of X - contaminated dilute H 2 SO 4 obtained in FIG. 5 is low, by a conventional desalting process (eg, electrodialysis, reverse osmosis, heat). Distillation, membrane distillation, etc.) can be effectively treated to obtain clean fresh water for reuse in the diffusion dialysis section, as shown in FIG.
  • the benefit of integrating the desalination unit into the electrolyte purification process is to reduce water consumption during diffusion dialysis while greatly reducing the volume of waste liquid discharge. In this way, the cost can be greatly reduced whether it is a subsequent recycling or a harmless disposal process.
  • a new way of using diffusion dialysis has been developed, from recovering free acids to selectively removing ionic impurities.
  • diffusion dialysis is used to recover the free acid in the acid zinc electrolyte, and the treated acid zinc electrolyte is still treated as alkali waste zinc as a waste liquid, and the treatment cycle is longer and the cost is higher. high.
  • the treated acidic zinc electrolyte in the present invention is a purified product, and the sulfuric acid can be returned to the main circulation of the electrolyte, and the treatment process is more concise and optimized.
  • the invention relies only on the spontaneous diffusion of ions for separation, does not involve a chemical reaction process, and the system can be continuously operated, stable and reliable.
  • the purification system inputs only water, does not input any additional impurities, and the outlet is a dilute H 2 SO 4 solution enriched in fluorine chlorine impurities, which is equivalent to the loss of a small amount of H 2 SO 4 .
  • Selective removal of chlorofluoro impurities Since H 2 SO 4 is a by-product of the electro-zinc industry, the cost here is basically negligible.
  • the dilute H 2 SO 4 obtained at the exit of the system is still relatively pure and can completely replace pure Water is used for SO 2 power wave washing (in this process, water will become dilute sulfuric acid with more pollutants, also known as fouling acid in the industry, and its final effluent H 2 SO 4 and chlorofluorocarbon impurity concentrations are higher than
  • the dilute H 2 SO 4 emission here is digested and used inside the plant, does not affect the existing process, does not generate additional wastewater discharge, and has no environmental pressure.
  • the invention solves two existing problems in the removal of fluorine and chlorine impurities and waste liquid in the zinc electrolyte at one time, and proposes a new method for realizing resource recycling in the hydrometallurgical industry.
  • FIG. 1 is a schematic view of a conventional technical route for removing fluorine and chlorine impurities in a zinc electrolyte by diffusion dialysis technology in the prior art
  • FIG. 2 is a schematic view showing a process flow for selectively removing fluorine and chlorine impurities from an acidic zinc electrolyte according to an embodiment of the present invention, wherein 101 is an anion exchange membrane and 102 is a diffusion dialyzer.
  • FIG 3 is a schematic view showing a process flow for selectively removing fluorine and chlorine impurities from a neutral zinc electrolyte by adding H 2 SO 4 according to an embodiment of the present invention.
  • FIG. 4 is a schematic view showing a process flow for selectively removing fluorine and chlorine impurities from a neutral zinc electrolyte by adding an acidic electrolyte according to an embodiment of the present invention.
  • FIG. 5 is a view showing selective removal of monovalent anion impurities X - (including F - , Cl - , Br - , I - from a sulfuric acid system electrolyte system (including Zn, Mn, Cu, Co, etc.) according to an embodiment of the present invention .
  • X - including F - , Cl - , Br - , I - from a sulfuric acid system electrolyte system (including Zn, Mn, Cu, Co, etc.) according to an embodiment of the present invention .
  • NO 3 -, NO 2 -, etc. is a schematic process flow schematic.
  • FIG. 6 is a schematic process flow diagram of selective removal of monovalent anion impurity X ⁇ integrated with a desalination apparatus, in accordance with one embodiment of the present invention.
  • an anion exchange membrane On both sides of an anion exchange membrane, the acidic electrolyte to be purified and the pure water as the free acid receiver are respectively filled. Since the solute concentration in the electrolyte on the left side of the membrane is larger than that on the right side, the solute in the left side tends to diffuse to the right. Because of the anion selectivity of the interlayer membrane, anions such as SO 4 2- , HSO 4 - and Cl - , F - are freely permeable, but such as Zn 2+ , Mg 2+ , Mn 2+ , Na + and K + , etc. The cation is impermeable.
  • the H + present in the solution is special, its hydration radius is small, and it can be rapidly transferred by hydrogen bond in the aqueous phase system, so it is more likely to leak through the anion exchange membrane. Therefore, in the process of diffusing the anion from left to right, in order to maintain the electrical neutrality of the solution on the left and right sides, H + will pass through, and a relatively pure free acid is obtained on the right side. This is the process by which diffusion dialysis is used to recover free acid. At the same time, since the water and radius of SO 4 2- and HSO 4 - are higher than those of Cl - , F - and so on, the former has a slightly higher transmission resistance during transmembrane, thereby causing an anionic membrane in the process.
  • the test diffusion dialysis device has an effective membrane area of 1.0 m 2 and a flow channel length of about 1.5 m, and completely simulates an industrial full-scale diffusion dialysis machine.
  • the circulation required for the main cycle of zinc electrolyte is about 8000 tons/day; in order to maintain the stability of chlorine impurities, the acid electrolyte to be discharged is 200 tons. /day. That is to say, in order to achieve chlorine balance, the total amount of chlorine impurities that the manufacturer needs to remove every day is about 200 tons of all chlorine impurities contained in the acidic electrolyte. If the Cl - removal rate is less than 100%, the same Cl - removal effect can be achieved by increasing the amount of bypass purification treatment.
  • the typical acidic electrolyte composition in the current process is Zn 2+ 58 g/L, SO 4 2- 365 g/L, H + 160 g/L in H 2 SO 4 , Cl - 540 mg/L, F - 120 mg/L.
  • the diffusion dialysis method of this embodiment uses the TWDDA anion exchange membrane of Shandong Tianwei Membrane Technology Co., Ltd. Take 50L of the acidic electrolyte, and pass the waste acid and pure water (or tap water) into the diffusion dialysis machine in reverse flow mode to control the flow ratio of electrolyte to water to 1:1, and the operating flow intensity is 5.0L h -1 m -2 , after the system reached steady state operation, it was found that the Cl - removal rate reached 51.5%, the F - removal rate reached 30.0%, the SO 4 2- loss rate was 20.1%, and the loss of Zn 2+ was only 0.74%. In the diffusion dialysis process the removal of Cl - SO 2.56 times the selectivity of 4 2-, removing F - SO 1.49 times the selectivity to 4 2-.
  • Example 1 With the method of Example 1, only the operating flow intensity of diffusion dialysis was changed, and other parameters were in agreement with Example 1. When the system reaches continuous and stable operation, its separation performance is shown in the following table:
  • diffusion dialysis can effectively remove the fluorine and chlorine impurities in the acidic zinc electrolyte, while ensuring an extremely low zinc loss rate.
  • the removal of Cl - SO 2.5-2.8 fold selectivity are 4 2-, removing F. - SO 1.4-1.6 fold selectivity are 4 2-.
  • Example 1 With the method of Example 1, only the flow ratio of water to electrolyte during the diffusion dialysis operation was changed, but the flow intensity of the acidic electrolyte was maintained at 5.0 L h -1 m -2 , which was in agreement with Example 1. Other conditions are also in agreement with Embodiment 1. When the system reaches continuous and stable operation, its separation performance is shown in the following table:
  • the diffusion dialysis can effectively remove the fluorine-chloride impurities in the acidic zinc electrolyte while ensuring a low zinc loss rate.
  • Example 2 Using the method of Example 1, only the initial fluorine chlorine content in the acidic electrolyte was changed, and other test conditions were in agreement with Example 1. When the system reaches continuous and stable operation, its separation performance is shown in the following table:
  • Example 1 With the method of Example 1, only the anion film type used for diffusion dialysis was changed, and other test conditions were the same as in Example 1. When the system reaches continuous and stable operation, its separation performance is shown in the following table:
  • the composition of the neutral zinc electrolyte is Zn 2+ 158g/L, SO 4 2- 365g/L, Cl - 540mg/L, F - 120mg/L, pH. It is 5.5 (free H + concentration is 0).
  • the diffusion dialysis test used the TWDDA anion exchange membrane of Shandong Tianwei Membrane Technology Co., Ltd. to simulate the purification process in Figure 3. 50 L of this acidic electrolyte was taken, and 98% of concentrated sulfuric acid was added thereto at a concentration of 5.0 g/L.
  • the electrolyte after adjusting the acidity is passed into the diffusion dialysis device in reverse flow mode to control the flow ratio of the electrolyte to the water to be 1:1, and the operating flow intensity is 5.0 L h -1 m -2
  • the Cl - removal rate reached 49.0%
  • the F - removal rate reached 30.4%
  • the SO 4 2- loss rate was 0.80%
  • the Zn 2+ loss was 0.84%.
  • the removal of Cl - SO 61 fold selectivity to 4 2- removing F - SO 38 fold selectivity to 4 2-.
  • Example 21 Using the method of Example 21, only the concentration of H 2 SO 4 added to the neutral electrolyte was changed.
  • the other test conditions were the same as in Example 21. After the system reached stable operation, the separation performance was as follows:
  • Example 21 The method of Example 21 was employed, except that the concentration of H 2 SO 4 in the neutral electrolyte was adjusted by a method of adding an acidic electrolyte (the detailed chemical composition thereof was as described in Example 1), the acidic zinc electrolyte used and examples The same test conditions are the same as those in the embodiment 21. After the system reaches stable operation, the separation performance is as shown in the following figure:
  • Example 21 The method of Example 21 was used, except that Zn 2+ in the electrolyte was replaced with other metal ions, a simulated electrolyte was prepared and 5.0 g/L of free H 2 SO 4 was added thereto, and Example 21 was repeated, and diffusion dialysis was performed. After achieving stable operation, the separation performance is shown in the following table:
  • Example 21 The method of Example 21 was adopted, except that the F - and Cl - impurities in the electrolyte were replaced with other monovalent anions at a concentration of 1000 mg / L, and a simulated zinc electrolyte was prepared and 5.0 g / L of free H was added thereto. 2 SO 4 , Example 21 was repeated. After the diffusion dialysis reached continuous stable operation, the separation performance is shown in the following table:
  • the method proposed in the present invention can effectively remove monovalent anion impurities in the electrolyte system of the sulfuric acid system, including F - , Cl - , Br - , I - , NO 3 - , NO 2 - and the like.
  • the conventional desalination method can achieve high rejection rate and high concentration multiple for the low concentration of dilute H 2 SO 4 discharged from the diffusion dialysis process, and can effectively recover fresh water therefrom, and greatly reduce the volume of the final discharge waste liquid.
  • these final concentrated raffinates can still be used as an SO 2 power wave water wash in an electro-zinc plant to achieve zero pollutant emissions during selective defluorination purification.

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Abstract

提供了从硫酸体系电解液中选择性去除一价阴离子杂质的方法。该方法包括：调节电解液中的游离H 2SO 4浓度，将含有游离H 2SO 4的电解液通入扩散渗析器废酸室，以水为接收液以反向流方式通入扩散渗析器回收室，控制扩散渗析操作过程中电解液的流量强度，在扩散渗析器内部电解液中部分游离H 2SO 4及阴离子杂质在浓差驱动下透过膜传输至接收液中，形成一价阴离子杂质富集的稀H 2SO 4和纯化的电解液，其中，扩散渗析器内设置有阴离子交换膜；其中，所述硫酸体系电解液为选自Zn 2+、Mn 2+、Cu 2+和Co 2+硫酸体系电解液中的至少一种；其中，所述一价阴离子杂质为F -、Cl -、Br -、I -、NO 3 -和NO 2 -中的至少一种。

Description

从硫酸体系电解液中选择性去除一价阴离子杂质的方法
优先权信息
本申请请求2017年3月6日向中国国家知识产权局提交的、专利申请号为201710127073.0的专利申请的优先权和权益，并且通过参照将其全文并入此处。
技术领域
本发明涉及湿法冶金领域，具体而言，涉及一种从硫酸体系电解液中选择性去除一价阴离子杂质的方法，特别涉及一种从硫酸锌电解液中选择性去除氟氯杂质的方法，以此保证湿法冶锌工艺循环中的电解液氟氯杂质的含量始终低于或达到工艺要求。该方法还适用于从其它硫酸体系电解液(如Zn、Mn、Cu、Co等)中选择性去除一价阴离子杂质(如F -、Cl -、Br -、I -、NO 3 -、NO 2 -等)。
背景技术
全世界约80％的金属锌均使用湿法冶锌技术生产得到，其主要工艺流程为ZnS矿原料焙烧→硫酸浸出→电积锌。电积锌之前的电解液接近中性，在电解沉锌过程中部分ZnSO 4会转化为H 2SO 4。电积锌后得到的酸性电解液，其主要组成是ZnSO 4和H 2SO 4，会被用来再次浸出焙烧矿来再生电解液，形成湿法冶锌工艺中的电解液循环过程。由于焙烧矿原料不可避免地存在一些杂质，因此在此过程中杂质就会在电解液中累积，危害整个冶锌过程。湿法冶锌的核心就在于纯化这些锌电解液，以维持工艺流程的顺利进行，同时降低电积锌的能耗并最终得到高纯度的阴极金属锌。电解液纯化过程中，绝大部分杂质如铁、钴、镍、镓、锑、砷、氯和氟均需要维持在低的浓度。但实际的操作过程中氯和氟杂质往往是较难去除的，因此其浓度往往会在电解液中进行累积。在此过程中Cl -离子的危害主要在于其腐蚀性，超标的Cl -离子除了会腐蚀管道和设备之外，往往还会腐蚀昂贵的Ag–Pb阳极板，造成电极损耗及电耗增加。更为糟糕的是，阳极板的腐蚀会引起电解液中Pb的含量增加，从而导致阴极金属锌产品中Pb含量超标，使产品不能达到应有的标准。F -的危害主要在于其会导致阴极金属锌牢牢粘附在Al阴极母板上无法剥离，从而使电积过程无法持续。
人们已经开发了许多方法来去除锌电解液循环中的Cl -和F -离子杂质。(1)化学沉淀方法。通过向电解液中加入合适的化学药剂，Cl -可以以AgCl(CN1936036A)，BOCl(《湿法冶金》2014年第33卷第6期480-482页)，Sn(OH)Cl(CN102851503A)以及CuCl(CN101633982A,CN102796869A,CN102732725B)沉淀的形式去除；F -可以以CaF 2沉淀的形式加以去除。AgCl，BOCl和Sn(OH)Cl沉淀法除氯的效率均很高，但操作成本也很高，不适用于工业化生产。主要是由于这些沉淀需要繁复的多步化学处理才能被重新利用，在此过程中不可避免的会造成昂贵的Ag，B及Sn物质的损失。目前在湿法冶锌工业中CuCl沉淀法除氯被广泛采用，但该方法也存在一些不足。首先，该方 法除氯效率有限，更适合处理一些Cl -杂质含量较高的电解液；第二，由于Cu在水溶液中容易生成稳定的Cu 2+而失去除氯能力，造成Cu的利用率不高，因此过程中工艺参数控制十分严格，不易掌握；第三，由于大量Cu 2+残留，除氯完成后必须向电解液中加入足量Zn粉将其置换出来，进一步增加了操作成本。(2)化学氧化法除氯。Cl -可被一些强氧化剂如O 3(US4379037；Hydrometallurgy 2016,160:147-151)或PbO 2(CN103668324B)氧化成气体形式的Cl 2，从而从电解液溶液中被分离出来。然而在此过程中，由于氧化剂的利用率往往较低，造成其消耗量太大，成本较高。另外，锌电解液中往往还存在浓度较高的Mn 2+杂质，浓度较Cl -杂质高出10–20倍，因同样具有还原性，还会额外消耗大量的氧化剂，造成操作成本的进一步增加。(3)离子交换及萃取法。离子交换法(CN101492772A)也可用来去除电解液中的Cl -杂质，但由于Cl -杂质浓度较低，且与高浓度的SO 4 2-离子(～1000倍)共存，因此树脂的选择性较低，需要使用的树脂量较大，成本较高。另外，树脂的再生需要使用大量高浓度的硫酸，产生大量的含氯高酸性废水，处理十分困难。液相萃取法(CN103451449B,CN103060561A,CN101886170B)用于Cl -去除也面临同样的问题，即操作成本高、存在废水废液排放问题。(4)热蒸发方法。热蒸发及结晶纯化工艺是另一种从锌电解液中去除氟氯杂质的可靠技术。与ZnSO 4和H 2SO 4相比较，HCl及HF挥发性均要强得多，因此可以利用蒸馏的方法将其去除(US4698139)。然而，高温条件下电解液的腐蚀性明显增加，其设备材质防腐要求更高，成本也更为高昂。另外，蒸发操作能耗也太高，工业上一般较少采用。(5)膜分离方法。由于氯氟杂质离子与电解液中主要的阴离子SO 4 2-和HSO 4 -物理化学性质存在明显不同，可以利用膜分离方法进行分离和纯化。利用一价离子选择性电渗析技术，氟氯等一价离子杂质可从电解液中被分离去除(US4715939,CN87102881A)。同时，借助纳滤膜提供的一价离子选择性，再结合普通电渗析也可以实现同样的功能(CN103572051A)。然而，无论是一价离子选择性离子交换膜，还是纳滤膜材料，其一价离子选择性均与其处理的盐溶液浓度直接相关。随着盐浓度的增加，其一价离子选择性也大大减弱。湿法冶锌工业中使用的锌电解液浓度很高(其中SO 4 2-离子浓度约为320g/L)，在如此之高的浓度下，这些膜的一价离子选择性均大大减弱，造成氟氯等杂质脱除效率较低，电渗析能耗很高，综合处理成本仍然居高不下。
到目前为止，湿法冶金行业还没有找到一种低成本，稳定可靠，操作简单的氟氯去除方法。因此，尽管存在前文所述的诸多不足，工业界仍采用CuCl沉淀法为主要处理手段。然而，即使使用了该方法，由于操作条件要求严格难以保证，系统的可靠程度并不高，国内许多电锌厂家仍需要定时排放一部分电解液来解决氟氯累积的问题，使电锌生产得以持续。这样一来，不但白白浪费了大量的Zn资源，同时产生了含有高浓度硫酸和锌盐的酸性锌电解废液，处置十分困难。目前如何纯化处理这一部分排放的电解液，使其能重新回到锌电解液循环之中，是摆在电锌企业面前的一道行业难题，亟待解决。
发明内容
本发明旨在至少解决现有技术中存在的技术问题之一。
本发明是基于以下考虑完成的：
酸性锌电解液的主要化学组成是H 2SO 4和ZnSO 4，同时含有少量杂质如Cl -，F -等。目前的思路主要集中在利用Ca(OH) 2等碱将废电解液中的Zn资源选择性沉淀出来并加以利用(CN101760632B，CN100450942C)。由于大量游离H 2SO 4的存在，在沉淀Zn资源时碱的用量及产生的CaSO 4渣量均会大大增加。为了缓解这一难题，专利CN100450942C提出了一种方法，使用扩散渗析技术来回收废电解液中的游离H 2SO 4，从而减少中和过程中钙碱的用量，同时一定程度上减少反应产生的渣量，其处理流程如图1所示。首先从电积锌电解液循环中以旁路循环形式取出一部分酸性锌电解液通入扩散渗析器废酸室，同时另一股水作为接受液以逆流方式通入扩散渗析器回收室。在扩散渗析器中，游离酸(包括H 2SO 4，HCl及HF杂质)在浓差驱动下从废酸室迁移至回收室，得到回收酸。扩散渗析技术的目的是回收尽可能多的游离酸或碱(Journal of Membrane Science 2011,366:1-16)，在该过程中酸性锌电解液中超过80％的游离H 2SO 4得到回收。这样一来该酸性电解液中的游离酸浓度大大下降，在加碱沉锌时消耗的碱量可以大大减小，同时与碱式硫酸锌一起沉淀下来的CaSO 4渣量也会减小。经过滤后，含锌滤渣回用，滤清液排放，清液中所含的氟氯杂质离开体系得到去除。紧接着，将含锌渣和前面得到的回收H 2SO 4在酸溶工序中进行反应重新得到含锌电解液，并回用至电解液主循环。在此过程中不溶于酸的废渣(主要是CaSO 4等)必须排放。同时，由于排放的废渣和滤液含有大量的SO 4 2-，此时必须补加足量浓H 2SO 4以维持电解液体系硫酸根含量恒定。专利CN100450942C在一定程度上降低了酸性锌电解液处理的综合成本，减少了碱的消耗量和残渣的产量，经济效益明显。然而由于锌电解液中锌和硫酸根浓度均很高，因此消耗的碱量和产生的渣量仍然很大，导致其综合成本仍然较高，企业无法完全接受。另外，产生的大量滤液及废渣排放，对企业来讲仍然是无法解决的环境难题。
一直以来，扩散渗析被认为仅仅是用来进行游离酸和盐(或者是游离碱和盐)的分离，回收游离酸(或碱)已成为扩散渗析技术应用的思维定式。同样的，在之前详细提到的专利CN100450942C中，回收的H 2SO 4被视为有用的“洁净”资源被重新回用(用于溶解含锌滤渣)，其中含有的Cl -杂质会被重新带入锌电解液循环。Cl -杂质是从扩散渗析残液中去除的(含锌沉渣回用，滤清液排放)。
因此，根据本发明的一个方面，本发明提出了一种从硫酸体系电解液中选择性去除一价阴离子杂质的方法。根据本发明的实施例，该方法包括：调节电解液中的游离H 2SO 4浓度，将含有游离H 2SO 4的电解液通入扩散渗析器废酸室，以水为接收液以反向流方式通入扩散渗析器回收室，控制扩散渗析操作过程中电解液的流量强度，在扩散渗析器内部电解液中部分游离H 2SO 4及阴离子杂质在浓差驱动下透过膜传输至接收液中，形成一价阴离子杂质富集的稀H 2SO 4和纯化的电解液，
其中，扩散渗析器内设置有阴离子交换膜；
其中，硫酸体系电解液为选自Zn 2+、Mn 2+、Cu 2+和Co 2+硫酸体系电解液中的至少一种；
其中，一价阴离子杂质为选自F -、Cl -、Br -、I -、NO 3 -、NO 2 -中的至少一种。
根据本发明实施例的从硫酸体系电解液中选择性去除一价阴离子杂质的方法，突破了利用扩散渗析来进行游离酸和盐(或者是游离碱和盐)的分离，回收游离酸(或碱)的思维定式，解决了专利CN100450942C等传统方法需要消耗大量碱，同时产生废渣排放，工艺流程长等问题。
在此，需要说明的是，本文中“Zn 2+、Mn 2+、Cu 2+和Co 2+硫酸体系电解液”是指ZnSO 4、MnSO 4、CuSO 4和CoSO 4电解液，硫酸体系电解液可以选自ZnSO 4、MnSO 4、CuSO 4和CoSO 4电解液中的至少一种。
参考图6，根据本发明的实施例，利用脱盐装置对扩散渗析产生的所述一价阴离子杂质富集的稀H 2SO 4进行再生净化处理，以便得到净水，所述净水重新用作接收液；其中，脱盐装置是反渗透、电渗析、热蒸馏或膜蒸馏装置中的一种。由此，通过净化处理，使废弃的一价阴离子杂质富集的稀H 2SO 4去除杂质离子，形成净水，该净水，重新用作接收液，减少扩散渗析过程中的水耗，同时大大减小废液排放的体积，工业成本可大大下降
根据本发明的实施例，硫酸体系电解液可以为硫酸锌电解液，一价阴离子杂质可以为氟氯杂质。由此，一价阴离子杂质的去除效果好。根据本发明的具体实施例，电解液中Cl -含量可以为200-10000mg/L，F -含量可以为50-1000mg/L。由此，氟和氯杂质的浓度高，易于通过渗透作用选择性去除，并且，当电解液中Cl -含量为200-10000mg/L，F -含量为50-1000mg/L时，氟氯杂质的去除率保持稳定。
根据本发明的实施例，扩散渗析操作过程中电解液的流量强度为1.6-20.0L h -1m -2。现有技术中，为了提供硫酸的回收率，通常控制电解液的流量小于1L h -1m -2。游离H 2SO 4的回收率不是考量过程效率的指标。发明人意外发现，通过减小酸性电解液与水的接触时间，即通过提高扩散渗析过程的操作流量强度，可以显著提高该过程中总的SO 4 2-与F -、Cl -的分离效率。当酸性电解液的流量强度在1.6–20.0L h -1m -2范围内时，酸性电解液中的一价阴离子杂质(如F -、Cl -等)的去除效率可显著高于总SO 4 2-的去除效率，其中Cl -的去除率均为SO 4 2-的2.5-2.8倍，F -的去除率均为SO 4 2-的1.4-1.6倍，从而，一价阴离子杂质的去除率显著提高。
根据本发明的实施例，水和含有游离H 2SO 4的硫酸锌电解液的流量之比不受特别的限制，本领域技术人员可以根据具体情况进行调节。根据本发明的实施例，水和含有游离H 2SO 4的硫酸锌电解液的流量之比可以为0.5–2.0:1。由此，电解液中的一价阴离子杂质的去除效果好。根据本发明的优选实施例，水和含有游离H 2SO 4的硫酸锌电解液的流量之比可以为1:1。由此，阴离子交换膜两侧的压力相等，离子交换效率高，一价阴离子杂质的去除率高。
本发明实施例的从硫酸体系电解液中选择性去除一价阴离子杂质的方法，不仅能从酸性电解液中去除一价阴离子杂质，如图3所示，还可以从中性电解液中去除一价阴离子杂质。这就需要在进入扩散渗析器之前必须向中性电解液添加少量的浓硫酸以提供扩散渗析的驱动力，即阴离子交换膜两侧游离酸的浓度差。根据本发明的实施例，可以通过加入浓H 2SO 4或直接通入SO 3气体，调节电解液中游离H 2SO 4浓度在0.5–100g/L。其中，浓 硫酸是指质量分数大于或等于70％的硫酸溶液。
根据本发明的又一些实施例，还可以向电解液中加入含高浓度游离酸的电解贫液调节电解液中游离H 2SO 4浓度，电解贫液的加入量为0.5％–60％。其中，电解液是中性电解液。本文中“含高浓度游离酸的电解贫液”是指游离酸浓度(以H 2SO 4计)在30–160g/L的电解贫液。进一步地，根据本发明的实施例，可以通过添加含有H 2SO 4的物料，或者浸出工艺段电解液，调节电解液中的游离H 2SO 4浓度。由此，实现了工业生产的废弃物的合理利用。在湿法冶锌工业中，从酸性电解液制备得到中性电解液往往也是要分多步才能完成的。在实际工业生产中往往分为热强酸浸出(游离H 2SO 4浓度大于120g/L，温度高于90℃)，热酸浸出(游离H 2SO 4浓度为30-80g/L，温度高于90℃)，弱酸性浸出(游离H 2SO 4浓度为10g/L，温度约为60℃)和中性浸出(pH 4.4-5.5，60℃)几个步骤。因此，锌电解液中游离硫酸的浓度是随着与锌焙砂的反应程度增加而逐渐降低的，根据本发明的实施例，可以选择具有合适酸度的锌电解液，即选取电解液浸出工段的热强酸性浸出液、热酸浸出液、弱酸浸出液和中性浸出液中的至少一种调节电解液中游离H 2SO 4浓度，从而，无需通过外部加酸即可控制合适游离酸度进行氟氯杂质的选择性去除。
为了便于理解本发明的从硫酸体系电解液中选择性去除一价阴离子杂质的方法，在此对其原理进行详细解释说明：
如图2所示的电解液选择性除氟氯工艺流程，该方法可以选择性地去除酸性锌电解液中的氟氯杂质，使原本需要排放的锌电解液回到电解液循环之中。首先从锌电解液循环中以旁路循环形式取出一部分酸性锌电解液通入扩散渗析器废酸室，同时另一股水作为接收液以逆流方式通入扩散渗析器回收室。与专利CN100450942C截然不同之处在于，本发明中使用扩散渗析的目的在于选择性地去除酸性锌电解液中的氟氯杂质，而不在于分离和回收游离H 2SO 4。因此本发明视扩散渗析后得到的回收H 2SO 4为废弃物，即氟氯杂质出口；同时视扩散渗析残液为纯化后的锌电解液资源。相对于原始酸性锌电解液而言，其经过扩散渗析器后损失了部分游离H 2SO 4及HCl、HF。损失的游离H 2SO 4可通过添加等物质量浓H 2SO 4或SO 3气体的方式实现补偿，这样一来就可以实现电解液中氟氯杂质的去除。同时，本发明通过控制某些技术参数，可大大增强扩散渗析过程对硫酸电解液体系中一价阴离子(特别是氟氯杂质)的选择性。
1、减小酸性电解液与接收液(水)在扩散渗析器中的接触时间。
扩散渗析过程中废酸液(此处为酸性锌电解液)与接收液流的接触时间可用废酸液的操作流量强度来衡量。其操作流量强度越大，意味着废酸液和接收液在扩散渗析器中接触的时间越短，二者存在严格的反比例关系。在利用扩散渗析回收酸性电解液中游离H 2SO 4的过程中，为了提高游离H 2SO 4的回收率，往往需要低的操作流量强度，这意味着废酸液与接收液的接触时间很长。特别地，在回收H 2SO 4过程中，为了使游离酸回收率高于80％，其废酸的操作流量强度一般需要低至0.8L h -1m -2。在该操作模式下，绝大部分游离H 2SO 4与F -、Cl -杂质一起从废酸液中透过膜扩散传输至接收液中，该传输过程观察不到明显的阴离子选择性(即总的SO 4 2-与F -、Cl -杂质跨膜传输的几率几乎 相同)。例如在专利CN100450942C中，回收得到的游离H 2SO 4(再生酸，从废酸液中去除的部分)含有原液中80％以上的H 2SO 4，50％左右的F -和60％左右的Cl -杂质。
在本发明中，游离H 2SO 4的回收率不是考量过程效率的指标。通过减小酸性电解液与水的接触时间，即通过提高扩散渗析过程的操作流量强度，可以显著提高该过程中总的SO 4 2-与F -、Cl -的分离效率。通过将酸性电解液的流量强度控制在1.6–20.0L h -1m -2范围内，酸性电解液中的一价阴离子杂质(如F -、Cl -等)的去除效率可显著高于总SO 4 2-的去除效率，其中Cl -的去除率均为SO 4 2-的2.5-2.8倍，F -的去除率均为SO 4 2-的1.4-1.6倍。同时，其选择性随着流量强度的减小而逐渐减小，这与专利CN100450942C中提供的数据吻合，在极低的操作流量强度下(例如0.4-0.8L h -1m -2)，虽然游离H 2SO 4的去除率(或称为回收率)可以显著提高，但其一价离子选择性远低于本发明中的数据。2、降低欲纯化电解液体系的游离酸度以抑制H 2SO 4的损失。
由于本发明中使用扩散渗析单元操作的思路从回收游离酸的限制中被解放出来，其主要目的在于选择性去除Cl -，F -离子杂质。因此图2中提出的工艺还可以进一步改进，提高分离过程中去除Cl -，F -离子杂质的选择性，减少硫酸根物质的损失。由于电积锌工序后产生的酸性锌电解液中游离H 2SO 4浓度很高(其典型值为160g/L)，而其中含有的氟氯杂质浓度很低(F -浓度为50-300mg/L，Cl -浓度为100-1000mg/L)，基体SO 4 2-离子浓度可达杂质离子浓度的～1000倍。虽然相对于SO 4 2-，扩散渗析对F -和Cl -存在明显的选择透过性，但SO 4 2-物质的损失仍然是主要和大量的。从选择性去除氟氯的角度来看，游离H 2SO 4的跨膜传输是完全没有意义的(与酸回收完全相反)，应该被抑制。减小电解液中的游离H 2SO 4浓度是抑制H 2SO 4跨膜传输的有力手段之一。游离酸含量减小后，H 2SO 4的跨膜传输大大下降，但F -和Cl -的传输却影响不大。因此，通过减小电解液中的游离酸浓度调控不同离子的跨膜传输，最终可达到增加氟氯去除选择性的目的。
因此本发明提出了如图3所示的除氯流程。不同于从酸性锌电解液中进行氟氯杂质的去除，这里选择从中性锌电解液开始着手。在进入扩散渗析器之前必须向中性电解液添加少量的浓硫酸以提供扩散渗析的驱动力(左右两侧游离酸的浓度差)，添加H 2SO 4的浓度为0.5–100g/L。同样的，酸的补加也可以以酸性锌电解液的形式加入，如图4所示，其中酸性锌电解液加入量为0.5-60％。与图2中的流程相比较，图3和4中氟氯杂质的去除率基本保持不变，但硫酸根的损失率大大降低(可低至原来的5％)，有效提高了该过程的分离效率。
在湿法冶锌工业中，从酸性电解液制备得到中性电解液往往也是要分多步才能完成的。在实际工业生产中往往分为热强酸浸出(游离H 2SO 4浓度大于120g/L，温度高于90℃)，热酸浸出(游离H 2SO 4浓度为30-80g/L，温度高于90℃)，弱酸性浸出(游离H 2SO 4浓度为10g/L，温度约为60℃)和中性浸出(pH 4.4-5.5，60℃)几个步骤。因此，锌电解液中游离硫酸的浓度是随着与锌焙砂的反应程度增加而逐渐降低的，本发明可以选择具有合适酸度的锌电解液，或将上述浸出液进行混合，这样一来无需通过外 部加酸即可控制合适游离酸度进行氟氯杂质的选择性去除。
除了湿法冶锌以外，Mn、Cu、Co的冶炼过程也使用硫酸电解液体系，同时也存在去除一价离子杂质如F -、Cl -、Br -、I -、NO 3 -、NO 2 -等的需求。本发明提出的去除方法灵感虽然来源于冶锌过程，但对上述体系仍然是完全适用的。如图5所示，被一价离子X -杂质(如F -、Cl -、Br -、I -、NO 3 -、NO 2 -等)污染的硫酸体系电解液(包括Zn 2+、Mn 2+、Cu 2+、Co 2+等体系)，如有需要可以添加少量酸性物质(可以是纯净H 2SO 4，电解后产生的酸性电解液或其它含有游离酸的物质等)调节其游离酸度，然后通入扩散渗析器废酸室。同时水以逆流方式进入回收室，在此过程中X -杂质和SO 4 2-随H +一起进入回收室，离开电解液体系，实现X -杂质的去除。
另外，由于在此过程中本发明可以限制SO 4 2-的传输，因此图5中得到的X -污染的稀H 2SO 4浓度较低，通过常规脱盐过程(如电渗析，反渗透，热蒸馏，膜蒸馏等)可以对其进行有效处理，得到洁净淡水以重用至扩散渗析工段，如图6所示。将脱盐装置集成至电解液纯化过程的益处在于减少扩散渗析过程中的水耗，同时大大减小废液排放的体积。这样一来，无论是后续的回用还是无害化处置过程，其成本均可大大下降。
本发明实施例的从硫酸体系电解液中选择性去除一价阴离子杂质的方法至少具有下列优点之一：
(1)发展了扩散渗析新的使用方式，即从回收游离酸到选择性去除离子杂质。在之前的技术方案中(如CN100450942C)，扩散渗析用于回收酸性锌电解液中的游离酸，处理后的酸性锌电解液仍作为废液进行加碱沉锌处理，处理周期较长，成本较高。而本发明中处理后的酸性锌电解液即为纯化后产品，补充硫酸即可回到电解液主循环，处理流程更为简洁和优化。
(2)在锌电解液体系中，相对于主要阴离子SO 4 2-和HSO 4 -而言，Cl -和F -离子透过膜从废酸室迁移至回收室的倾向明显更高，存在明显的选择性。也就是说Cl -和F -杂质在此过程中更倾向于在回收室中富集，从回收酸中去除Cl -和F -杂质的效率较以前的过程(如CN100450942C)要高得多。在之前的专利中几乎没有观察到这种选择性，其原因主要在于H 2SO 4回收率过高。在扩散渗析过程中SO 4 2-与Cl -是竞争透过AEM的，但Cl -由于水合半径小，带电荷也相对较少，透过膜要相对容易，倾向于优先透过。但随着渗析时间延长，左右两侧Cl -的浓度差迅速减小，Cl -的传输迅速减慢；但此时SO 4 2-的浓差依然较大，传输速率变化不大，因此SO 4 2-的透过也迅速跟上，减弱了其Cl -选择透过性。因此，要实现高的游离H 2SO 4回收率，必然会损失Cl -等的选择性。传统扩散渗析回收游离酸的思维禁锢限制了其Cl -和F -离子的选择透过性。
(3)由于此过程中扩散渗析的主要用途是选择性去除氟氯杂质，对游离酸的回收率不做追求(回收率大大低于常规80-90％水平)，因此其操作流量强度也远远高于传统的扩散渗析操作(～5倍，常规扩散渗析操作的流量强度约为0.5-1.0L h -1m -2)。这样一来纯化过程中需要的离子膜面积大大减小，设备等固定资产投入极大降低。同时，扩散渗析操作是自发过程，无需电能等外部能量输入，系统运行成本也实现了最小化。
(4)本发明仅仅依赖离子的自发扩散进行分离，不涉及化学反应过程，系统可连续运行，稳定可靠。
(5)本发明涉及的纯化过程中，纯化系统输入仅仅为水，不输入任何额外杂质，出口为氟氯杂质富集的稀H 2SO 4溶液，相当于以损失少量H 2SO 4为代价选择性去除了氟氯杂质。由于H 2SO 4为电锌行业副产品，在此处成本基本上可以忽略。另外，由于锌电解液循环中对氟氯等杂质要求非常严格(其最高允许浓度约为10 2ppm量级)，系统出口处得到的稀H 2SO 4仍是比较纯净的，完全可以替代纯水用于SO 2动力波水洗(在此过程中水会变为含污染物较多的稀硫酸，行业内也称为污酸，其最终排放液H 2SO 4及氟氯杂质浓度均高于此处的稀H 2SO 4排放)在厂区内部实现消化使用，不影响现有工艺流程，不会产生额外的废水排放，无环保压力。
(6)本发明一次性解决了锌电解液中去除氟氯杂质和废液处置的两个现存难题，为实现湿法冶金行业的资源循环利用提出了新的方法。
本发明的附加方面和优点将在下面的描述中部分给出，部分将从下面的描述中变得明显，或通过本发明的实践了解到。
附图说明
本发明的上述和/或附加的方面和优点从结合下面附图对实施例的描述中将变得明显和容易理解，其中：
图1为现有技术中利用扩散渗析技术去除锌电解液中氟氯杂质的传统技术路线示意图；
图2为根据本发明一个实施例的从酸性锌电解液中选择性去除氟氯杂质的工艺流程示意图，其中，101为阴离子交换膜，102为扩散渗析器。
图3为根据本发明一个实施例的通过补加H 2SO 4从中性锌电解液中选择性去除氟氯杂质的工艺流程示意图。
图4为根据本发明一个实施例的通过补加酸性电解液从中性锌电解液中选择性去除氟氯杂质的工艺流程示意图。
图5为根据本发明一个实施例的从硫酸体系电解液体系(包括Zn、Mn、Cu、Co等)中选择性去除一价阴离子杂质X -(包括F -、Cl -、Br -、I -、NO 3 -、NO 2 -等)的简要工艺流程示意图。
图6为根据本发明一个实施例的集成了脱盐装置的选择性去除一价阴离子杂质X -的简要工艺流程示意图。
发明详细描述
下面详细描述本发明的实施例，所述实施例的示例在附图中示出，其中自始至终相同或类似的标号表示相同或类似的元件或具有相同或类似功能的元件。下面通过参考附图描述的实施例是示例性的，仅用于解释本发明，而不能理解为对本发明的限制。
下面结合附图和实施例对本发明的从硫酸体系电解液中选择性去除一价阴离子杂质的方法的原理和离子的扩散过程做进一步说明：
在一张阴离子交换膜两侧分别充满需要纯化的酸性电解液，以及作为游离酸接收液的纯水。由于膜左侧电解液中溶质浓度大于右侧接收液，因此左侧中的溶质有向右扩散的趋势。又因为中间膜的阴离子选择性，SO 4 2-，HSO 4 -及Cl -，F -等阴离子可以自由透过，但如Zn 2+，Mg 2+，Mn 2+，Na +及K +等阳离子无法透过。溶液中存在的H +比较特殊，其水合半径很小，并可以在水相体系中通过氢键翻转快速传递，因而在阴离子交换膜中比较容易渗漏透过。于是在阴离子从左向右扩散的过程中，为了维持左右两侧溶液的电中性，H +会随之透过，在右侧得到比较纯净的游离酸。这正是扩散渗析用来回收游离酸的过程。同时，由于SO 4 2-和HSO 4 -的水和半径要高于Cl -，F -等卤素阴离子，因此前者在跨膜时受到的传输阻力稍大一些，由此造成阴离子膜在此过程中的Cl -，F -离子选择性，最终Cl -，F -等阴离子透过阴离子交换膜的倾向要明显高于电解液中的基体阴离子SO 4 2-和HSO 4 -。换而言之在此过程中Cl -，F -等阴离子杂质会倾向于在回收的游离酸中富集，而在酸性电解液中被选择性去除。这样一来，从回收酸一侧去除氟氯杂质就更加高效。本发明中测试扩散渗析器有效膜面积为1.0m 2，流道长度约为1.5m，完全模拟工业全规模扩散渗析器。
下面将结合实施例对本发明的方案进行解释。本领域技术人员将会理解，下面的实施例仅用于说明本发明，而不应视为限定本发明的范围。实施例中未注明具体技术或条件的，按照本领域内的文献所描述的技术或条件(或者按照产品说明书进行)。所用试剂或仪器未注明生产厂商者，均为可以通过市购获得的常规产品。
实施例1
以年生产规模为24万吨金属锌的典型电锌工艺为例，其锌电解液主循环需要的循环量约为8000吨/天；为了维持氯杂质稳定，需要排放的酸性电解液为200吨/天。也就是说为了实现氯平衡，生产企业每天需要去除的氯杂质的总量约为200吨酸性电解液中所含有的全部氯杂质。如果Cl -去除率低于100％，可以通过增加旁路纯化处理量的方式来达到同样的Cl -去除效果。现行工艺中典型的酸性电解液组成为Zn 2+58g/L，SO 4 2-365g/L，H +以H 2SO 4计160g/L，Cl -540mg/L，F -120mg/L。
本实施的扩散渗析方法使用山东天维膜技术有限公司的TWDDA阴离子交换膜。取50L该酸性电解液，将废酸与纯水(或自来水)以反向流方式通入扩散渗析器，控制电解液与水的流量比为1：1，操作流量强度为5.0L h -1m -2，系统达到稳态运行之后发现酸性锌电解中Cl -去除率达到了51.5％，F -去除率达到30.0％，SO 4 2-损失率为20.1％，而Zn 2+的损失仅为0.74％。在此过程中扩散渗析去除Cl -的选择性为SO 4 2-的2.56倍，去除F -的选择性为SO 4 2-的1.49倍。
实施例2-10
采用实施例1的方法，只改变扩散渗析的操作流量强度，其它参数与实施例1一致。 当系统达到持续稳定运行之后，其分离性能如下表所示：
Figure PCTCN2017117527-appb-000001
在1.6-20.0L h -1m -2操作流量强度范围内，扩散渗析均可以有效去除酸性锌电解液中的氟氯杂质，同时保证极低的锌损失率。在此过程中去除Cl -的选择性均为SO 4 2-的2.5-2.8倍，去除F -的选择性均为SO 4 2-的1.4-1.6倍。
实施例11-12
采用实施例1的方法，只改变扩散渗析操作过程中水与电解液的流量比，但维持酸性电解液的流量强度为5.0L h -1m -2，与实施例1一致。其它条件也与实施例1一致。当系统达到持续稳定运行之后，其分离性能如下表所示：
Figure PCTCN2017117527-appb-000002
当进入扩散渗析的水与电解液流量比在0.6-1.6范围内变化时，扩散渗析均可以有效去除酸性锌电解液中的氟氯杂质，同时保证低的锌损失率。
实施例13-14
采用实施例1的方法，只改变酸性电解液中的初始氟氯含量，其他测试条件与实施例1一致。当系统达到持续稳定运行之后，其分离性能如下表所示：
Figure PCTCN2017117527-appb-000003
Figure PCTCN2017117527-appb-000004
由此可见，当Cl -浓度在200-10000mg/L，F -浓度在50-1000mg/L范围内时，系统的氟氯去除效率及选择性基本维持不变。
实施例15-20
采用实施例1的方法，只改变扩散渗析所使用的阴离子膜型号，其它测试条件与实施例1相同。当系统达到持续稳定运行之后，其分离性能如下表所示：
Figure PCTCN2017117527-appb-000005
商业可获得的阴离子交换膜普遍可用于选择性去除酸性锌电解液中的氟氯杂质，但其分离性能也略有差异。从上述结果来看具有一价阴离子选择性的Selemion ASV膜对氟氯杂质的选择性去除效率较高。
实施例21
以实施例1中电锌厂中性电解液为例，其中性锌电解液组成为Zn 2+158g/L，SO 4 2-365g/L，Cl -540mg/L，F -120mg/L，pH为5.5(游离H +浓度为0)。扩散渗析测试使用山东天维膜技术有限公司的TWDDA阴离子交换膜，模拟图3中的纯化过程。取50L该酸性电解液，向其中加入98％的浓硫酸，浓度为5.0g/L。将调节酸度后的电解液与纯水(或自来水)以反向流方式通入扩散渗析器，控制电解液与水的流量比为1：1，操作流量强度为5.0L h -1m -2，系统达到稳态运行之后发现酸性锌电解中Cl -去除率达到了49.0％，F -去除率达到30.4％，SO 4 2-损失率为0.80％，而Zn 2+的损失为0.84％。在此过程中扩散渗析去除Cl -的选择性为SO 4 2-的61倍，去除F -的选择性为SO 4 2-的38倍。
实施例22-25
采用实施例21的方法，只改变加入中性电解液中H 2SO 4的浓度，其它测试条件均与实施例21相同，系统达到稳定运行之后，其分离性能如下图所示：
Figure PCTCN2017117527-appb-000006
Figure PCTCN2017117527-appb-000007
由此可见，当添加的H 2SO 4浓度在0.5-100g/L范围内变化时，电解液中的氟氯杂质均能被有效去除，选择性很高(可达120倍)。
实施例26-29
采用实施例21的方法，区别在于通过加入酸性电解液的方法(其详细化学组成如实施例1中所述)调节中性电解液中H 2SO 4的浓度，所用酸性锌电解液与实施例1相同，其它测试条件均与实施例21相同，系统达到稳定运行之后，其分离性能如下图所示：
Figure PCTCN2017117527-appb-000008
由此可见，利用酸性电解液调节游离酸度时，电解液中的氟氯杂质均能被有效去除，选择性很高。
实施例30-33
采用实施例21的方法，区别在于将电解液中的Zn 2+换成其他金属离子，配制模拟电解液并向其中加入5.0g/L的游离H 2SO 4，重复实施例21，待扩散渗析达到持续稳定运行之后，其分离性能如下表所示：
Figure PCTCN2017117527-appb-000009
由此可见，电解液体系中的金属阳离子对氟氯阴离子的选择性去除基本没有影响，Mn、Cu、Co、Na及其它硫酸体系金属电解液中的氟氯杂质均能被有效去除，选择性很高。
实施例34-37
采用实施例21的方法，区别在于将电解液中的F -、Cl -杂质换成其它一价阴离子，浓度均为1000mg/L，配制模拟锌电解液并向其中加入5.0g/L的游离H 2SO 4，重复实施例21， 待扩散渗析达到持续稳定运行之后，其分离性能如下表所示：
Figure PCTCN2017117527-appb-000010
由此可见，本发明中提出的方法可有效去除硫酸体系电解液体系中的一价阴离子杂质，包括F -、Cl -、Br -、I -、NO 3 -、NO 2 -等。
实施例38-41
采用实施例21的方法，其扩散渗析达到稳态操作之后，Cl -去除率达到了49.0％，F -去除率达到30.4％，SO 4 2-损失率为0.80％。此时得到的F -，Cl -富集的稀H 2SO 4杂质组成为：Cl -271mg/L，F -40mg/L，SO 4 2-2.90g/L，Zn 2+1.28g/L，H +0.020mol/L。采用如图6中所示的脱盐系统来处理回用扩散渗析排出的稀H 2SO 4废液，以回收重用水资源，减小废液体积。我们测试了如下几种常规脱盐方法对该稀H 2SO 4进行净化处理，其最终测试性能如下表所示：
Figure PCTCN2017117527-appb-000011
常规的脱盐方法对扩散渗析过程排出的低浓度稀H 2SO 4均可实现较高的截留率和高的浓缩倍数，可有效从其中回收淡水，大大减少最终排出废液的体积。特别地，这些最终的浓缩残液仍然可以作为电锌厂SO 2动力波水洗之用，实现选择性除氟氯纯化过程中的零污染物排放。
尽管本发明的具体实施方式已经得到详细的描述，本领域技术人员将会理解。根据已经公开的所有教导，可以对那些细节进行各种修改和替换，这些改变均在本发明的保护范围之内。本发明的全部范围由所附权利要求及其任何等同物给出。
在本说明书的描述中，参考术语“一个实施例”、“一些实施例”、“示意性实施例”、“示例”、“具体示例”、或“一些示例”等的描述意指结合该实施例或示例描述的具体特征、结构、材料或者特点包含于本发明的至少一个实施例或示例中。在本说明书中，对上述术语的示意性表述不一定指的是相同的实施例或示例。而且，描述的具体特征、结构、材料或者特点可以在任何的一个或多个实施例或示例中以合适的方式结合。

Claims (10)

  1. 一种从硫酸体系电解液中选择性去除一价阴离子杂质的方法，其特征在于，包括：调节电解液中的游离H 2SO 4浓度，将含有游离H 2SO 4的电解液通入扩散渗析器废酸室，以水为接收液以反向流方式通入扩散渗析器回收室，控制扩散渗析操作过程中电解液的流量强度，在扩散渗析器内部电解液中部分游离H 2SO 4及阴离子杂质在浓差驱动下透过膜传输至接收液中，形成一价阴离子杂质富集的稀H 2SO 4和纯化的电解液，
    其中，扩散渗析器内设置有阴离子交换膜；
    其中，所述硫酸体系电解液为选自Zn 2+、Mn 2+、Cu 2+和Co 2+硫酸体系电解液中的至少一种；
    其中，所述一价阴离子杂质为F -、Cl -、Br -、I -、NO 3 -和NO 2 -中的至少一种。
  2. 根据权利要求1所述的从硫酸体系电解液中选择性去除一价阴离子杂质的方法，其特征在于，利用脱盐装置对扩散渗析产生的所述一价阴离子杂质富集的稀H 2SO 4进行再生净化处理，以便得到净水，所述净水重新用作接收液；
    其中，所述脱盐装置是反渗透、电渗析、热蒸馏或膜蒸馏装置中的一种。
  3. 根据权利要求1或2所述的从硫酸体系电解液中选择性去除一价阴离子杂质的方法，所述硫酸体系电解液为硫酸锌电解液，一价阴离子杂质为氟氯杂质。
  4. 根据权利要求1-3任一项所述的从硫酸体系电解液中选择性去除一价阴离子杂质的方法，其特征在于，所述电解液中Cl -含量为200–10000mg/L，F -含量为50–1000mg/L。
  5. 根据权利要求1-4任一项所述的从硫酸体系电解液中选择性去除一价阴离子杂质的方法，其特征在于，所述扩散渗析操作过程中所述电解液的流量强度为1.6–20.0L h -1m -2。
  6. 根据权利要求1-5任一项所述的从硫酸体系电解液中选择性去除一价阴离子杂质的方法，其特征在于，所述水和所述含有游离H 2SO 4的硫酸锌电解液的流量之比为0.5–2.0:1。
  7. 根据权利要求1-6任一项所述的从硫酸体系电解液中选择性去除一价阴离子杂质的方法，其特征在于，通过添加含有H 2SO 4的物料，或者浸出工艺段电解液，调节电解液中的游离H 2SO 4浓度。
  8. 根据权利要求1-7任一项所述的一种从硫酸体系电解液中选择性去除一价阴离子杂质的方法，其特征在于，通过加入浓H 2SO 4或直接通入SO 3气体，调节所述电解液中所述游离H 2SO 4浓度在0.5–100g/L。
  9. 根据权利要求1-8任一项所述的一种从硫酸体系电解液中选择性去除一价阴离子杂质的方法，其特征在于，通过向所述电解液中加入含高浓度游离酸的电解贫液调节所述电解液中游离H 2SO 4浓度，所述电解贫液的加入量为0.5％–60％。
  10. 根据权利要求1-9任一项所述的从硫酸体系电解液中选择性去除一价阴离子杂质的方法，其特征在于，利用电解液浸出工段的热强酸性浸出液、热酸浸出液、弱酸浸出液和中性浸出液中的至少一种调节电解液中游离H 2SO 4浓度。
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