WO2016000231A1 - 一种含氯氧化锌二次物料的处理方法 - Google Patents

一种含氯氧化锌二次物料的处理方法 Download PDF

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Publication number
WO2016000231A1
WO2016000231A1 PCT/CN2014/081557 CN2014081557W WO2016000231A1 WO 2016000231 A1 WO2016000231 A1 WO 2016000231A1 CN 2014081557 W CN2014081557 W CN 2014081557W WO 2016000231 A1 WO2016000231 A1 WO 2016000231A1
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zinc
chlorine
leaching
raffinate
solution
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PCT/CN2014/081557
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English (en)
French (fr)
Inventor
舒毓璋
张琦
杨桂芬
孙保华
韦林奎
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云南祥云飞龙再生科技股份有限公司
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Priority to PCT/CN2014/081557 priority Critical patent/WO2016000231A1/zh
Priority to MYPI2015703745A priority patent/MY174353A/en
Priority to EP14896593.2A priority patent/EP3165616B1/en
Priority to US14/907,579 priority patent/US9945008B2/en
Priority to CN201480033726.3A priority patent/CN106715729B/zh
Publication of WO2016000231A1 publication Critical patent/WO2016000231A1/zh

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    • 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
    • C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
    • C22B26/10—Obtaining alkali metals
    • 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
    • C22B19/00—Obtaining zinc or zinc oxide
    • C22B19/30—Obtaining zinc or zinc oxide from metallic residues or scraps
    • 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
    • C22B19/00—Obtaining zinc or zinc oxide
    • C22B19/20—Obtaining zinc otherwise than by distilling
    • C22B19/22—Obtaining zinc otherwise than by distilling with leaching with acids
    • 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
    • C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
    • C22B3/38—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds containing phosphorus
    • C22B3/381—Phosphines, e.g. compounds with the formula PRnH3-n, with n = 0-3
    • 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
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/006—Wet processes
    • C22B7/007—Wet processes by acid leaching
    • 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
    • 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 belongs to the field of comprehensive recycling of zinc-containing secondary resources, and particularly relates to a method for treating secondary materials containing chlorine and zinc oxide.
  • soot is associated with a variety of metal mineral resources. In the high-temperature smelting process of these metals, zinc enters the smelting dust; some zinc-containing wastes use high-temperature reduction and volatilization to volatilize lead and zinc into soot. These soots are the main source of secondary zinc resources.
  • the common point of such zinc-containing materials is that zinc exists in the form of oxides, and contains varying amounts of chlorine.
  • the chlorine content exceeds the maximum allowable amount of conventional wet zinc smelting. Up to several hundred times, including lead, calcium, magnesium, iron, sodium, potassium, silicon dioxide, etc. When treated by the existing wet zinc smelting technique, chlorine enters the solution, so that the electrolysis process of zinc cannot be performed normally.
  • the world's mineral zinc raw materials are becoming increasingly tense and facing depletion, while secondary zinc resources are increasing. Together with the accumulation of secondary zinc resources, the environment is under increasing pressure, forcing people to conduct extensive research on the use of secondary resources. .
  • the high chlorine content is the key factor that the secondary resources cannot be treated by the existing zinc smelting technology.
  • the removal of chlorine from the raw materials is the main research direction.
  • the current treatment idea is to remove the chlorine from such materials, and use the existing zinc smelting technology to reduce the chlorine content.
  • Dechlorination from chlorinated zinc oxide is carried out by desulfurization and wet dechlorination respectively.
  • Desulfurization by fire method is based on the fact that metal chloride has a high vapor pressure at high temperature and is easy to volatilize. At high temperature, chlorine is volatilized in the form of metal chloride.
  • Commonly used equipment for dechlorination is a multi-hearth furnace, a rotary kiln, and the like. It has also been studied to dechlorination by microwave, and the material is heated to 700-1100 ° C to volatilize chlorine.
  • the fire treatment of dechlorination has the disadvantages of high energy consumption, low metal recovery rate, generation of gas phase pollution sources, and production of higher chlorine-containing soot, which also causes pressure on the environment.
  • the zinc oxide is blended into the existing zinc smelting process.
  • Wet dechlorination is the conversion of chlorine into a solution based on the solubility of chloride in water.
  • the material is usually treated with sodium carbonate (or ammonium carbonate) to convert the lead-zinc chloride to a water-insoluble carbonate which enters the solution in the form of sodium chloride.
  • the disadvantages are incomplete dechlorination, large consumption of reagents, high cost, and large amount of dechlorination water.
  • the chlorine removal solution is a mixed solution of sodium chloride (potassium), sodium carbonate and sodium sulfate (potassium).
  • the dechlorination solution cannot be recycled, and it is not convenient to recover the chloride salt, which usually needs to be discharged. Therefore, the wet dechlorination process is accompanied by a large amount of chlorine-containing wastewater discharge.
  • the commonly used precipitant for precipitating chloride ions is monovalent copper ions, and chlorine is chlorinated.
  • the precipitation of cuprous copper can reduce the chlorine in the zinc sulfate solution to such an extent that the electrolysis proceeds normally.
  • the problem of chlorine complicates the wet zinc smelting process, increases the consumption of expensive copper, and increases the emissions of large quantities of chlorine-containing wastewater.
  • the object of the present invention is to provide an environmentally-friendly and energy-saving process technology for secondary resources of zinc chloride-containing.
  • the inventors conducted extensive intensive research and completed the present invention after exerting creative labor.
  • a method for treating a secondary material containing chlorine and zinc oxide comprising the steps of:
  • the zinc-containing organic phase obtained in the step (2) is subjected to back extraction-electrolysis to recover zinc, and the organic phase after stripping the zinc is returned to the step (2) to extract zinc;
  • the raffinate obtained in the step (4) is opened, and the amount of the raffinate open circuit is controlled.
  • the chlorine content of the open-circuit raffinate is equal to the chlorine content of the raw material added in step (1) to maintain the chloride ion input and open circuit balance, and the open-circuit raffinate and the additional chlorine-containing zinc oxide secondary material II according to the liquid-solid ratio 1-3: 1 mixing, and then liquid-solid separation, the separated deposit is added to step (1) and leached with an acidic raffinate;
  • the separated solution contains chlorine ions up to 80-120 g/L, and when the total salt content reaches 160-240 g/L, the chlorine-containing aqueous phase is decontaminated to obtain a mixture of KCl and NaCl.
  • the KCl and NaCl mixed solution obtained in the step (6) is concentrated by evaporation, and respectively crystallized to produce KCl and NaCl products.
  • the leaching condition of the step (1) is: the liquid-solid ratio is controlled by the leaching solution containing Zn25-28 g/L, and the liquid-solid ratio is controlled at 20-40:1 according to the zinc content of the material, and the leaching is carried out in a mechanical stirring tank.
  • the leaching end point is pH 4.5-5.0.
  • the acidic solution used in the first leaching of step (1) is sulfuric acid, and sulfuric acid is added when the acid required for the leaching of step (1) is insufficient from the raffinate of step (4).
  • the P 204 -kerosene solvent in the step (2) is prepared by mixing the organic solvent P 204 with 260 # solvent kerosene in a volume ratio of 20-40%.
  • the stripping-electrolytic recovery of zinc in the step (3) is a zinc-containing organic phase stripped with a zinc electrolysis waste liquid, and the stripping solution contains Zn. 100-120g/L, H2SO4 60-100g/L, electrolytic zinc after degreasing.
  • step (5) is carried out in a mechanical agitation tank, or in the form of heap leaching, and the slurry is filtered for liquid-solid separation when carried out in a mechanical agitation tank.
  • the impurity removal of step (6) comprises the following steps:
  • Steps (1)-(7) of the present invention have no dechlorination process, thereby eliminating the chlorine removal process of the raw materials, simplifying the process flow, eliminating the gas phase and water phase pollution sources generated by the raw material dechlorination process, and saving the chlorine removal process.
  • the energy consumption and reagent consumption greatly reduce the production cost.
  • the step (2) of the present invention recovers zinc by organic solvent extraction, the step (6) removes impurities, and the step (7) recovers the chlorinated salt, thereby achieving zinc recovery, chloride recovery and impurity elimination simultaneously.
  • the present invention converts chlorine in the zinc chloride-containing zinc into a solution through steps (1), (2), (3), (4), (5) and enriches the solution into a high concentration chlorination solution, which is convenient for Recovery of sodium chloride and potassium chloride is carried out in the solution.
  • the step (7) of the present invention recovers the chlorinated salt, so that the chlorine in the raw material is recovered as a product, and in addition to having a certain economic value, the secondary pollution caused by the current dechlorination process is completely eliminated.
  • the invention has no process wastewater discharge, which creates conditions for zero discharge of enterprise wastewater.
  • the invention can directly treat different zinc oxide secondary materials with different chlorine content, and the raw material contains 1-20% chlorine.
  • the raw material having a slightly lower chlorine content is directly leached according to the step (1), and the raw material containing a higher chlorine content is used for the raffinate treatment according to the step (5), and then further leached according to the step (1).
  • Figure 1 is a process flow diagram of the present invention.
  • a method for treating a secondary material containing chlorine and zinc oxide includes the following steps:
  • the raffinate obtained in the step (4) is opened to a part and another The chlorine-containing zinc oxide secondary material II is mixed at a low liquid-solid ratio, and the precipitate is separated, and then the chlorine-containing zinc oxide secondary material of the step (1) is added.
  • the amount of the open circuit raffinate described in this step is equivalent to the chlorine content of the raw material input in step (1) to achieve the chloride ion input and open circuit balance;
  • the KCl and NaCl mixed solution obtained in the step (6) is concentrated by evaporation, and respectively crystallized to produce KCl and NaCl products.
  • the present invention is essentially an acid wet processing process of chlorine-containing zinc oxide (secondary material).
  • the process flow of the present invention is further explained:
  • the invention does not need pre-dechlorination treatment for the chlorine-containing zinc oxide (secondary material), but directly leaches zinc oxide with an acidic solution, and the soluble substances zinc, chlorine, potassium, sodium and magnesium in the zinc oxide are all leached into the solution.
  • Zinc is selectively extracted with a P 204 -kerosene solvent, and zinc is separated from Cl - , K + , Na + , Mg 2+ , etc. by extraction.
  • Zinc-containing organic reverse extraction-electrolytic recovery of zinc, and the raffinate is returned to leach the zinc-containing zinc oxide.
  • the cycle is repeated such that the Cl - , K + , Na + , Mg 2+ ions in the solution are continuously circulated and enriched, and finally the solution is formed by Cl - ions and contains K + , Na + , Mg 2+ , Zn 2+ . And a complex mixture of a small amount of sulfuric acid chloride-sulfate.
  • the open zinc extract contains an equimolar amount of free acid and unextracted zinc, and the open raffinate is mixed with excess chlorine-containing zinc oxide raw material under low liquid-solid ratio conditions. Neutralization, zinc and sulfate decreased, and chloride ion concentration increased further.
  • the solution is neutralized with lime to remove Mg 2+ and trace heavy metal ions. After the treatment, the solution is a mixed solution of KCl and NaCl, and the solution is concentrated and crystallized to produce potassium chloride and sodium chloride products, respectively.
  • High-chlorine zinc oxide raw materials do not require prior fire method or wet method to remove chlorine, but directly carry out acid leaching.
  • the Cl - , Zn 2+ , Mg 2+ , K + , Na + in the raw material enters the leachate, and the acid required for leaching comes from the zinc extraction residual liquid used for recycling, and the insufficient portion is supplemented with sulfuric acid.
  • Pb and Ca in the raw materials enter the leaching slag in the form of sulfate and SiO 2 respectively, and the sulfate does not accumulate and accumulate in the solution, and the leaching slag is a resource for recovering lead.
  • a preferred leaching condition is that the liquid-solid ratio is controlled by the leaching solution containing Zn25-28 g/L, and the leaching is carried out in a mechanical stirring tank, and the leaching end point is pH 4.5-5.0.
  • M is Zn, Mg, etc., and the chlorides of KCl, NaCl, and Zn, Mg are directly dissolved into the solution.
  • the leachate is filtered to obtain a clear solution, which is mixed with P 204 organic solvent to selectively extract zinc.
  • extracting zinc it generates an equimolar amount of free acid with the extracted zinc ions.
  • Other ions Cl - , SO 4 2- , K + , Na + , Mg 2+, etc. remain in the solution, and the remaining zinc solution is returned to leaching, so that Cl - , K + , Na + , Mg 2+ ions are accumulated in the process of leaching - extracting zinc - re-leaching.
  • the reaction to extract zinc is:
  • the organic solvent P 204 is used in a volume ratio of 20-40% by using 260# solvent kerosene, and may be, for example, 20%, 25%, 30%, 35% or 40%.
  • the organic phase for extracting zinc is back-extracted with zinc electrolysis waste liquid, and the stripping solution contains Zn100-120g/L, H 2 SO 4 60-100g/L, and electrolytic zinc after degreasing.
  • the solution is repeatedly used, and once per cycle, zinc is extracted by an organic solvent, and other soluble ions are accumulated in the circulating liquid, and finally the circulating solution forms a chlorine ion-containing SO 4 2- and Zn 2+ , K + , A complex mixture of chlorine salts and sulfates such as Na + and Mg 2+ .
  • the zinc extraction system is significantly different from the current common sulfate zinc extraction system and belongs to two different dissolution systems.
  • Feed Cl - in by - SX - After a further leaching cycle, rising in the circulating solution content, after a certain concentration (e.g. 50-80g / L), in accordance of Cl - input-output balance, fluid from the circulation Open the part of the chlorine-containing solution for treatment.
  • a certain concentration e.g. 50-80g / L
  • the specific treatment process is: using the residual liquid after partial extraction of zinc, the remaining liquid is an acidic solution, the acid content and the extracted zinc ions are equimolar, and contain different amounts of SO 4 2- and Zn 2+ , K + , Na + , Mg 2+, etc.
  • the open solution is mixed with the chlorine-containing zinc oxide raw material at a low liquid-solid ratio. During this process, the acid in the solution is neutralized, and part of the Zn 2+ is precipitated by the basic zinc sulfate.
  • the neutralizing acid reaction is:
  • the chloride in the raw material is dissolved into the solution, the chloride ion of the solution is increased, the chlorine in the raw material is lowered, and the secondary zinc material after the chlorine content is lowered is leached together with other chlorine-containing zinc oxide.
  • the treatment process of the open circuit raffinate may be carried out in a mechanical agitation tank or in the form of heap leaching.
  • the slurry In the mechanical agitation tank, the slurry must be filtered to perform liquid-solid separation.
  • the solution after the above treatment usually contains chlorine up to 80-120 g/L, and the total salt content is 160-240 g/L, which is a high-concentration solution, which is a raw material for recovering KCl and NaCl, and is also a condition for recovery.
  • the solution passes through the impurity removal to become a mixed solution of KCl and NaCl, and is concentrated by evaporation to separately crystallize the KCl and NaCl products.
  • a preferred impurity removal process is: 1) neutralization of heavy metals: addition of lime, control of pH 7.0-7.5, formation of hydroxide precipitates of heavy metals such as Zn 2+ in solution. 2) Neutralization and removal of Mg: Lime is added, pH 10 is controlled, and Mg forms a hydroxide precipitate. 3) Calcium removal: The solution contains a small amount of Ca 2+ , which is Ca 2 3 precipitated by Na 2 CO 3 . The precipitated solution was separated by pH 10-11, and concentrated by crystallization to yield KCl and NaCl, respectively.
  • the chemical composition (% by weight) is:
  • composition of the zinc raffinate after repeated cycles to reach equilibrium is as follows: (unit: g/L)
  • Implementation step (2) filtering the clear leachate, extracting the zinc with 30% P 204 -260 # solvent oil, compared with 1:1, the extraction grade is 4, to obtain the raffinate, Zn13g / L, H + 0.4mol / L.
  • Implementation step (3) the organic phase for extracting zinc is back-extracted with zinc by electrolysis of zinc electrolysis, and the liquid after stripping contains Zn110g/L, H 2 SO 4 85g/L, and electrolytic zinc after degreasing.
  • Step (4) According to the step (1), the amount of chlorine is 34g, and the zinc raffinate of step (2) is taken out, 500mL (containing 34g of chlorine) is opened, and the remaining 20.5L is added to the 21L return step (1) to be leached. cycle.
  • Step (5) Open 500 mL open-circuit raffinate, mix with 200 g of zinc chloride-containing secondary material II at a liquid-solid ratio of 2.5:1, mix for 30 min with stirring, and filter to obtain 500 mL of a solution.
  • the ingredients are as follows: (Unit: g/L)
  • the Cl - , K + and Na + ions in the solution increased, Zn 2+ and SO 4 2- decreased, and the total salt content of the solution was 235.7 g/L.
  • the sediment weighed 190 g, containing 31.5% of Zn, and the Cl content decreased from 20.02% to 4.6%, and proceeded to step (1) for leaching.
  • Step (6) After the step (5), the chlorine ion in the chlorine-containing aqueous phase reaches 132 g/L, and the chlorine-containing aqueous phase is decontaminated to obtain a mixed solution of KCl and NaCl; wherein the impurity removal process is: 1) And removal of heavy metals: adding lime, controlling pH 7.0-7.5, forming a hydroxide precipitate of heavy metals such as Zn 2+ in the solution. 2) Neutralization and removal of Mg: Lime is added, pH 10 is controlled, and Mg forms a hydroxide precipitate. 3) Calcium removal: The solution contains a small amount of Ca 2+ , which is Ca 2 3 precipitated by Na 2 CO 3 .
  • step (7) mixing the KCl and NaCl mixed solution obtained in the step (6) at pH 10-11, and concentrating by evaporation to separately crystallize the KCl and NaCl products.

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Abstract

一种含氯氧化锌二次物料的处理方法，包括如下步骤:1)将含氯氧化锌二次物料I用酸性溶液浸出; 2)用P 204-煤油溶剂选择性萃取锌; 3)进行反萃-电解回收锌； 4)循环操作1) -4)，使氯、钾、钠、镁等富集，形成氯盐-硫酸盐混合体系；5)将步骤 4)得到的萃余液开路，当氯离子投入和开路平衡，将开路萃余液与含氧氧化锌二次物料II混合，再进行液固分离，分离的沉积物加入步骤1)用酸性萃余液浸出；6)当分离出的溶液达到预定条件时，将含氯水相进行除杂；7)蒸发浓缩，分别结晶产出KCl和NaCl产品。该处理方法环保节能，无工艺废水排放，大幅度降低生产成本，彻底消除日前脱氯工艺带来的次生污染。

Description

一种含氯氧化锌二次物料的处理方法 技术领域
本发明属于含锌二次资源综合回收领域，具体涉及一种含氯氧化锌二次物料的处理方法。
 背景技术
目前世界每年消费的锌锭在1400万吨左右，其中50%用于钢材的表面保护，在回收镀锌钢材时，锌在高温下挥发进入炼钢烟尘，这类烟尘简称EAFD。另外，锌又伴生在多种金属矿产资源中，在这些金属的高温冶炼过程中，锌又进入冶炼烟尘；有的含锌废料采用高温还原挥发方式将铅锌挥发进入烟尘。这些烟尘是二次锌资源的主要来源，这类含锌物料的共同点是锌以氧化物形态存在，同时含有数量不等的氯，含氯量超过常规湿法炼锌最高允许量的数十至数百倍，同时含有铅、钙、镁、铁、钠、钾、二氧化硅等。用现有湿法炼锌技术处理时，氯进入溶液，使锌的电解过程不能正常进行。世界矿产锌原料日趋紧张，面临枯竭，而二次锌资源却越来越多，加上二次锌资源存积给环境造成日益增大的压力，迫使人们对二次资源的利用进行大量的研究。
氯含量高是二次资源不能用现有锌冶炼技术处理的关键因素，为了使原料能适应湿法炼锌工艺要求，脱除原料中的氯是目前研究的主要方向。现在的处理思路都是将这类物料的氯脱除，氯含量降低后利用现有炼锌技术搭配处理。
从含氯氧化锌中脱氯分别用火法脱氯和湿法脱氯工艺。火法脱氯的依据是金属氯化物在高温下有较高的蒸汽压，易于挥发的特性，在高温下将氯以金属氯化物的形态挥发脱除。通常用于脱氯的设备有多膛炉、回转窑等。也有人研究用微波脱氯，将物料加温至700-1100℃，将氯挥发。火法处理脱氯存在能耗高、金属回收率低、产生气相污染源、产出含氯更高的烟尘对环境同样造成压力等缺点，但仍为目前各企业采用的常用方法，脱除氯后的氧化锌搭配到现有锌冶炼流程中处理。
湿法脱氯是依据氯化物溶于水的特性，将氯转入溶液。通常用碳酸钠（或碳酸铵）对物料进行处理，将铅锌氯化物转化为不溶于水的碳酸盐，氯则以氯化钠形态进入溶液。缺点是脱氯不彻底、试剂消耗量大、成本高、脱氯用水量大，除氯后液为氯化钠（钾）、碳酸钠、硫酸钠（钾）混合稀溶液。脱氯溶液不能循环使用，也不便于回收氯化盐，通常需排放。因此，湿法脱氯方法伴随大量含氯废水排放。
从原料中脱除氯的工艺尽管存在各种缺点，但仍然是目前处理含氯氧化锌二次资源的选择。含氯氧化锌脱氯后，可以搭配入现有锌冶炼工艺处理，由于从原料脱氯不彻底，仍然会有一定数量的氯，在湿法冶炼锌过程中不断在浸出—电解循环过程中积累。因此，又必须从循环的硫酸锌溶液中除氯。硫酸锌溶液中除氯依据某些氧化物在硫酸锌溶液中的溶解度低，生成氯化物沉淀将氯从溶液中除去，通常用的沉淀氯离子的沉淀剂是一价铜离子，氯生成氯化亚铜沉淀，可以使硫酸锌溶液中的氯降低至使电解正常进行的程度。也有采用离子交换或有机溶剂萃取氯等方法，将硫酸锌溶液中的氯转移到另外的溶液中，以废水形式排放。氯的问题使湿法炼锌流程变得复杂，昂贵的铜消耗增加，同时增加大量含氯废水的排放。
因此，二次锌氧化物含氯高的问题仍然是锌循环利用领域的难题。由于含氯高问题不能彻底解决，二次锌氧化物资源长期不能有效利用，造成锌二次资源利用率远远低于其它有色金属。
 技术问题
鉴于此，为解决上述难题，本发明的目的是为含氯氧化锌二次资源提供一种环保节能的工艺技术。本发明人进行了大量的深入研究，在付出了创造性劳动后，从而完成了本发明。
 技术解决方案
所采用的技术方案为：
一种含氯氧化锌二次物料的处理方法，其特征在于，包括如下步骤：
（1）将含氯氧化锌二次物料Ⅰ用酸性溶液浸出，得到浸出液和浸出渣；
（2）将步骤（1）得到的浸出液用P204-煤油溶剂选择性萃取锌，得到含锌有机相和含氯含酸的萃余液；
（3）将步骤（2）得到的含锌有机相进行反萃-电解回收锌，反萃锌后的有机相返回步骤（2）萃取锌；
（4）将步骤（2）得到的萃余液作为步骤（1）所述的酸性溶液，返回步骤（1）循环操作（1）-（4）；
（5）当步骤（2）中含氯水相的氯离子在循环操作多次后氯离子达到50—80g/L，将步骤（4）得到的萃余液开路，萃余液开路数量控制在开路萃余液含氯量等于步骤（1）加入的原料含氯量维持氯离子投入和开路平衡，将开路萃余液与另外的含氯氧化锌二次物料Ⅱ按液固比1-3:1混合，再进行液固分离，分离的沉积物加入步骤（1）用酸性萃余液浸出；
（6）当步骤（5）完成，分离出的溶液含氯离子达80-120g/L，含盐总量达160-240g/L时，将含氯水相进行除杂，得到KCl和NaCl混合溶液；
（7）将步骤（6）得到的KCl和NaCl混合溶液，通过蒸发浓缩，分别结晶产出KCl和NaCl产品。
优选地，步骤（1）浸出的条件为：液固比按浸出液含Zn25-28g/L控制，根据物料含锌量不同，液固比控制在20-40:1，浸出在机械搅拌槽内进行，浸出终点pH4.5-5.0。
优选地，步骤（1）第一次浸出所用的酸性溶液为硫酸，当步骤（1）浸出需要的酸来自步骤（4）的萃余液不足时，补入硫酸。
优选地，步骤（2）中P204-煤油溶剂通过将有机溶剂P204用260#溶剂煤油配为体积比为20-40%制备。
优选地，步骤（3）中反萃-电解回收锌是含锌有机相用锌电解废液进行反萃，反萃液含Zn 100-120g/L、H2SO4 60-100g/L，除油后电解锌。
优选地，步骤（5）的混合在机械搅拌槽内进行，或者堆浸的形式进行，在机械搅拌槽内进行时需将矿浆过滤进行液固分离。
优选地，步骤（6）的除杂包括如下步骤：
1）中和除重金属：加入石灰，控制pH7.0-7.5；
2）中和除Mg：加入石灰，控制pH10;
3）除钙：加入Na2CO3。
 有益效果
本发明的优点在于：
1、本发明步骤（1）-（7）没有除氯过程，从而省去了原料除氯过程，简化了工艺流程，消除了原料除氯过程产生的气相和水相污染源，节省了除氯过程的能源消耗和试剂消耗，大幅度降低了生产成本。
2、本发明步骤（2）通过有机溶剂萃取回收锌，步骤（6）除杂，步骤（7）回收氯化盐，从而达到锌回收，氯化盐回收及杂质的排除同时进行。
3、本发明将含氯氧化锌中的氯通过步骤（1）、（2）、（3）、（4）、（5）转化到溶液中并富集为高浓度的氯化溶液，便于从溶液中进行氯化钠和氯化钾的回收。
4、本发明步骤（7）回收氯化盐，从而使原料中的氯作为产品回收，除具有一定经济价值外，还彻底消除了目前脱氯工艺带来的次生污染。
5、本发明无工艺废水排放，为企业废水零排放创造了条件。
6、本发明可以直接处理不同含氯量的氧化锌二次物料，原料含氯量1－20%。含氯稍低的原料按步骤（1）直接浸出，含氯更高的原料按步骤（5）用于萃余液处理，再按步骤（1）再浸出。
 附图说明
为了更清楚地说明本发明实施例或现有技术中的技术方案，下面将对实施例使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本发明的实施例，对于本领域普通技术人员来讲，在不付出创造性劳动性的前提下，还可以根据这些附图获得其他的附图。
图1为本发明的工艺流程图。
 本发明的实施方式
下面将结合本发明实施例中的附图，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明优选的实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
参见图1所示的工艺流程图，一种含氯氧化锌二次物料的处理方法，包括如下步骤：
（1）将含氯氧化锌二次物料Ⅰ用酸性溶液浸出，得到浸出液和浸出渣；
（2）将步骤（1）得到的浸出液用P204-煤油溶剂选择性萃取锌，得到含锌有机相和含氯含酸萃余液；
（3）将步骤（2）得到的含锌有机相进行反萃-电解回收锌，反萃后的贫有机相再返回步骤（2）萃取锌；
（4）将步骤（2）得到的萃余液作为步骤（1）所述的酸性溶液，返回步骤（1）循环操作（1）-（4）；
（5）当步骤（2）中含氯含酸萃余液的氯离子在循环操作多次后达到50——80g/L时，将步骤（4）得到的萃余液开路出一部分与另外的含氯氧化锌二次物料Ⅱ按低的液固比混合，分离出沉淀物，然后加入步骤（1）的含氯氧化锌二次物料。本步骤所述的开路萃余液的数量相当于步骤（1）投入的原料含氯量，以实现氯离子的投入和开路平衡；
（6）当步骤（5）中含氯水相的氯离子达80-120g/L以及含盐总量达160-240g/L时，将含氯水相进行除杂，得到KCl和NaCl混合溶液；
（7）将步骤（6）得到的KCl和NaCl混合溶液，通过蒸发浓缩，分别结晶产出KCl和NaCl产品。
因此，从本工艺流程可知，本发明实质是一种含氯氧化锌（二次物料）酸性湿法处理工艺。现对本发明的工艺流程做进一步说明：
本发明对含氯氧化锌（二次物料）无需预先脱氯处理，而是用酸性溶液直接浸出氧化锌，氧化锌中的可溶物锌、氯、钾、钠、镁都被浸出进入溶液，用P204-煤油溶剂选择性萃取锌，通过萃取，将锌与Cl- 、K+、Na+、Mg2+等分离。含锌有机相反萃—电解回收锌，萃余液再返回浸出含氯氧化锌。如此反复循环，使溶液中的Cl-、K+、Na+、Mg2+等离子不断循环富集，最终溶液形成以Cl-离子为主同时含有K+、Na+、Mg2+、Zn2+和少量硫酸的氯盐-硫酸盐的复杂混合体系。
溶液中Cl-、K+、Na+、Mg2+达到一定浓度后，开路出部分萃锌溶液回收氯化盐，实现Cl-、K+、Na+、Mg2+等离子的投入产出平衡。
开路的部分锌萃余液中含有被萃锌离子等摩尔的游离酸和未被萃取的锌，将开路萃余液在低液固比条件下与过量含氯氧化锌原料混合，溶液的酸被中和，锌和硫酸根下降，氯离子浓度进一步升高。该溶液用石灰中和除去Mg2+和微量重金属离子，处理后，溶液为KCl和NaCl混合高浓度溶液，将溶液浓缩结晶分别产出氯化钾和氯化钠产品。
进一步地，以下将叙述本发明工艺流程的原理和特点，其中包含了优选的上述步骤(1)-(7)的工艺条件。本领域技术人员通过以下的原理和特点所做的等效的或等同的工艺条件，均应包含在本发明的内容包含范围和保护范围之内。
本发明具有以下特点：
1、高氯氧化锌原料不需预先的火法或湿法除氯，而是直接进行酸性浸出。
原料中的Cl-、Zn2+、Mg2+、K+、Na+进入浸出液，浸出需要的酸来自循环使用的锌萃取余液，不足部分补入硫酸。原料中的Pb、Ca分别以硫酸盐形态与SiO2等进入浸出渣，溶液中硫酸根不会积累、富集，浸出渣是回收铅的资源。
一个较佳的浸出条件为：液固比按浸出液含Zn25-28g/L控制，浸出在机械搅拌槽内进行，浸出终点pH4.5-5.0。
为了提高锌的浸出率，可采用湿法炼锌工艺通常采用的多段逆流浸出。
浸出反应：
MO+H2SO4→MSO4+H2O
MO+2HCl→MCl2+H2O
PbO+H2SO4→PbSO4↓+H2O
PbCl2+H2SO4→PbSO4↓+2HCl
CaO+H2SO4+H2O→CaSO4•2H2O↓
M为Zn、Mg等，KCl、NaCl及Zn、Mg的氯化物直接溶解进入溶液。
2、锌回收及氯的循环富集
浸出液过滤后得到清亮溶液，用P204有机溶剂与其混合，将锌选择性萃取，萃取锌时生成与被萃锌离子等摩尔的游离酸，其它离子Cl-、SO4 2-、K+、Na+、Mg2+等仍然留在溶液中，萃锌余液返回浸出，使Cl-、K+、Na+、Mg2+等离子在浸出—萃取锌—再浸出的过程中循环积累。萃取锌的反应为：
ZnCl2+3HR→ZnR2•HR+2HCl
ZnSO4+3HR→ZnR2•HR+H2SO4
萃取锌时，有机溶剂P204用260#溶剂煤油配为体积比为20-40%，例如可以是20%、25%、30%、35%或40%。
萃取锌的有机相用锌电解废液进行反萃，反萃液含Zn100-120g/L、H2SO460-100g/L，除油后电解锌。
溶液反复循环使用，每循环一次，通过有机溶剂提取锌，而其他可溶离子则在循环液中积累，最终循环溶液形成以氯离子为主的含有SO4 2-和Zn2+、K+、Na+、Mg2+等氯盐-硫酸盐复杂混合体系。锌的萃取体系与目前通用的硫酸盐萃锌体系有明显的区别，属于两种不同的溶解体系。
3、氯离子的控制
原料中的Cl-通过浸出—萃取—再浸出循环后，在循环溶液中含量不断升高，到一定浓度后（例如50-80g/L），按照Cl-的投入产出平衡，从循环液中开路出部分含氯溶液进行处理。
具体处理过程为，用部分萃取锌后的余液，余液为酸性溶液，含酸量与被萃锌离子等摩尔数，同时含有不同量的SO4 2-及Zn2+、K+、Na+、Mg2+等。用该开路溶液与含氯的氧化锌原料按低的液固比混合，在此过程中，溶液中的酸被中和，部分Zn2+生成碱式硫酸锌沉淀。
中和酸反应为：
ZnO+2HCl→ZnCl2+H2O
ZnO+H2SO4→ZnSO4+H2O
过量的ZnO再继续反应，生产碱式锌盐沉淀：
ZnSO4+ZnO+H2O→2Zn•SO4•(OH)2↓
同时原料中的氯化物被溶解进入溶液，溶液氯离子升高，原料中的氯降低，氯含量降低后的二次锌物料再与其它含氯氧化锌一起进行浸出。
开路萃余液的处理过程可以在机械搅拌槽内进行，也可以以堆浸的形式进行，在机械搅拌槽内进行则必须矿浆过滤，进行液固分离。
4、含氯溶液回收KCl、NaCl
经过上述处理后的溶液通常含氯可达80-120g/L，含盐总量160-240g/L，为高浓度溶液，是回收KCl和NaCl的原料，也是可以进行回收的判断条件。
溶液通过除杂，成为KCl和NaCl混合溶液，通过蒸发浓缩，分别结晶产出KCl和NaCl产品。
一种优选的除杂过程为：1）中和除重金属：加入石灰，控制pH7.0-7.5，将溶液中Zn2+等重金属形成氢氧化物沉淀。2）中和除Mg：加入石灰，控制pH10，Mg形成氢氧化物沉淀。3）除钙：溶液中含有少量的Ca2+，用Na2CO3使其生成CaCO3沉淀。分离沉淀后的溶液pH10-11，通过浓缩结晶，分别产出KCl和NaCl。
下面用实施例进一步说明本发明:
实施例：
以某含氯氧化锌二次物料为试料，化学成分（重量百分含量%）为：
Zn Pb CaO SiO2 Cl MgO K Na
含氯氧化锌二次物料Ⅰ% 55 5 3 2 6.8 1.2 1.2 1.6
含氯氧化锌二次物料Ⅱ% 28.7 15.50 - - 20.2 - 9.55 7.39
反复循环达到平衡后的锌萃余液成分如下：（单位：g/L）
Cl- K+ Na+ Mg2+ Zn2+ H+(mol/L) SO4 2-
67.2 10 15.6 10.1 13 0.40 32
实施步骤（1）：用上述锌萃余液浸出含氯氧化锌Ⅰ500g，控制浸出后液含锌26g/L，采用液：固=42，加入锌萃余液21L，缓慢加入H2SO4控制浸出终点pH5.0，得到浸出液成分如下：（单位：g/L）
Zn2+ Cl- K+ Na+ Mg2+ SO4 2-
26 68.8 10.2 15.8 10.3 32.5
实施步骤（2）：过滤清亮的浸出液，用30%P204-260#溶剂油萃取锌，相比1:1，萃取级数4级，得到萃余液，Zn13g/L、H+0.4mol/L。
实施步骤（3）：萃取锌的有机相用锌电解废液反萃锌，反萃后液含Zn110g/L、H2SO485g/L，除油后电解锌。
实施步骤（4）：按步骤（1）投入氯量34g，取出步骤（2）的锌萃余液500mL（含氯34g）开路，其余20.5L，体积补充到21L返回步骤（1）浸出，进行循环。
实施步骤（5）：开路的500mL开路萃余液，按液固比2.5:1用含氯氧化锌二次物料Ⅱ200g与其混合，在搅拌下混合30min，进行过滤，得到溶液500mL。成分如下：（单位：g/L）
Zn2+ Cl- K+ Na+ Mg2+ SO4 2- pH
8 132.8 40.7 39.2 10.5 5.3 6.0
溶液Cl-、K+、Na+离子升高，Zn2+和SO4 2-下降，溶液含盐总量235.7g/L。过滤分离后沉积物重190g，含Zn31.5%，含Cl由20.02%降至4.6%，进入步骤（1）进行浸出。
实施步骤（6）：经过步骤（5）处理后含氯水相的氯离子达132g/L，将含氯水相进行除杂，得到KCl和NaCl混合溶液；其中除杂过程为：1）中和除重金属：加入石灰，控制pH7.0-7.5，将溶液中Zn2+等重金属形成氢氧化物沉淀。2）中和除Mg：加入石灰，控制pH10，Mg形成氢氧化物沉淀。3）除钙：溶液中含有少量的Ca2+，用Na2CO3使其生成CaCO3沉淀。
实施步骤（7）：将步骤（6）得到的KCl和NaCl混合溶液pH10-11，通过蒸发浓缩，分别结晶产出KCl和NaCl产品。
上所述仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。

Claims (7)

  1. 一种含氯氧化锌二次物料的处理方法，其特征在于，包括如下步骤：
    （1）将含氯氧化锌二次物料Ⅰ用酸性溶液浸出，得到浸出液和浸出渣；
    （2）将步骤（1）得到的浸出液用P204-煤油溶剂选择性萃取锌，得到含锌有机相和含氯含酸的萃余液；
    （3）将步骤（2）得到的含锌有机相进行反萃-电解回收锌，反萃锌后的有机相返回步骤（2）萃取锌；
    （4）将步骤（2）得到的萃余液作为步骤（1）所述的酸性溶液，返回步骤（1）循环操作（1）-（4）；
    （5）当步骤（2）中含氯水相的氯离子在循环操作多次后氯离子达到50—80g/L，将步骤（4）得到的萃余液开路，萃余液开路数量控制在开路萃余液含氯量等于步骤（1）加入的原料含氯量维持氯离子投入和开路平衡，将开路萃余液与另外的含氯氧化锌二次物料Ⅱ按液固比1-3:1混合，再进行液固分离，分离的沉积物加入步骤（1）用酸性萃余液浸出；
    （6）当步骤（5）完成，分离出的溶液含氯离子达80-120g/L，含盐总量达160-240g/L时，将含氯水相进行除杂，得到KCl和NaCl混合溶液；
    （7）将步骤（6）得到的KCl和NaCl混合溶液，通过蒸发浓缩，分别结晶产出KCl和NaCl产品。
  2. 如权利要求1所述的含氯氧化锌二次物料的处理方法，其特征在于，步骤（1）浸出的条件为：液固比按浸出液含Zn25-28g/L控制，根据物料含锌量不同，液固比控制在20-40:1，浸出在机械搅拌槽内进行，浸出终点pH4.5-5.0。
  3. 如权利要求1所述的含氯氧化锌二次物料的处理方法，其特征在于，步骤（1）第一次浸出所用的酸性溶液为硫酸，当步骤（1）浸出需要的酸来自步骤（4）的萃余液不足时，补入硫酸。
  4. 如权利要求1所述的含氯氧化锌二次物料的处理方法，其特征在于，步骤（2）中P204-煤油溶剂通过将有机溶剂P204用260#溶剂煤油配为体积比为20-40%制备。
  5. 如权利要求1所述的含氯氧化锌二次物料的处理方法，其特征在于，步骤（3）中反萃-电解回收锌是含锌有机相用锌电解废液进行反萃，反萃液含Zn100-120g/L、H2SO460-100g/L，除油后电解锌。
  6. 如权利要求1所述的含氯氧化锌二次物料的处理方法，其特征在于，步骤（5）的混合在机械搅拌槽内进行，或者堆浸的形式进行，在机械搅拌槽内进行时需将矿浆过滤进行液固分离。
  7. 如权利要求1所述的含氯氧化锌二次物料的处理方法，其特征在于，步骤（6）的除杂包括如下步骤：
    1）中和除重金属：加入石灰，控制pH7.0-7.5；
    2）中和除Mg：加入石灰，控制pH10；
    3）除钙：加入Na2CO3。
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