CN112481505A - Method for preparing basic zinc chloride by using high-chlorine smelting soot - Google Patents
Method for preparing basic zinc chloride by using high-chlorine smelting soot Download PDFInfo
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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
- 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
- C22B7/02—Working-up flue dust
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/16—Halides of ammonium
- C01C1/164—Ammonium chloride
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- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G9/00—Compounds of zinc
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- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0084—Treating solutions
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- 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
- C22B19/26—Refining solutions containing zinc values, e.g. obtained by leaching zinc ores
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- 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
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- 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
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- 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
- C25C1/12—Electrolytic production, recovery or refining of metals by electrolysis of solutions of copper
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- 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 provides a method for preparing basic zinc chloride by using high-chlorine smelting soot, which takes the high-chlorine smelting soot and waste acidic liquid as raw materials, comprises neutral chlorine leaching, low leaching liquid and partial copper raffinate as bottom water, acidic chlorination leaching, copper extraction and electrolysis; the high-purity cathode copper is prepared by purifying and deironing leaching treatment and extraction-electrodeposition, the copper extraction raffinate is deironing, zinc extraction and back extraction to obtain a zinc chloride solution, and the zinc chloride solution is synthesized into basic zinc chloride under the action of ammonia water serving as a precipitator, so that the purposes of low cost, high comprehensive utilization rate, simple process and low production cost of high-chlorine smelting soot are achieved under the condition of no dechlorination, the purpose of recycling waste is achieved, and the production and preparation cost is reduced.
Description
Technical Field
The invention relates to the technical field of comprehensive utilization of metallurgical resources, in particular to a method for extracting valuable metal compounds from high-chlorine smelting soot, and particularly relates to a method for preparing basic zinc chloride from high-chlorine smelting soot.
Background
Basic zinc chloride (Zn)5(OH)8Cl2·H2O) is a flaky-structure basic chloride which is widely used as an important chemical raw material product. Meanwhile, as a new zinc source feed additive, compared with conventional zinc sources such as zinc oxide, zinc sulfate and the like, the zinc source feed additive has the advantages of low addition level, small using amount, good palatability, high biological value, good feeding effect and the like, is more favorable for protecting the environment, and is a novel feed additive which is safe, efficient, environment-friendly and comprehensive in effect. In the existing production and preparation processes of basic zinc chloride, waste zinc is generally used, zinc chloride is used for reacting with zinc oxide, hydrochloric acid and zinc oxide or hydrochloric acid and basic zinc carbonate are used for reacting, and in the preparation methods, the production cost is overhigh in some methods, the raw materials used in some methods are relatively expensive, and the by-products obtained in some preparation methods easily cause environmental pollution. Less smelting slag is used as raw material for production.
With the development of economic society, the domestic demand for non-ferrous metal resources is increasing day by day, but non-ferrous metal resources such as copper, zinc, lead and the like are scarce in China, and a large amount of mineral resources need to be imported every year. On the other hand, smelting of copper, lead and the like is mainly carried out by a pyrogenic process, and a large amount of smoke dust carrying valuable metals is generated in the smelting process. In addition, other dusts such as sinter dust, converter dust, electric furnace dust, etc. are generated during the steel smelting process. The smoke dust contains heavy metals such as copper, zinc, lead, tin and the like, and the content of the heavy metals is higher than that of the traditional ores, so that the smoke dust not only pollutes the water and soil environment but also causes huge resource waste if the smoke dust is not utilized. Therefore, it is necessary to develop a research for extracting valuable metals from smelting soot in terms of environmental protection and reducing the dependence of mineral resources on foreign imports.
The smelting soot often contains Cl-in addition to valuable metals such as copper, zinc, lead, tin and the like. The existing process for treating smelting soot mainly adopts wet acid leaching, a large amount of acid is consumed in the process, and most Cl & lt- & gt enters a leaching solution in the leaching process. If higher Cl & lt- & gt in the leachate is not treated, the Cl & lt- & gt is enriched in the zinc electrolysis process, so that the anode plate mainly containing lead and silver is dissolved to influence the quality of the electrolytic zinc, and the harm to the body of field operators is also caused. Therefore, dechlorination is generally required for smelting soot by wet treatment or pretreatment. The wet dechlorination mainly comprises the steps of leaching Cl < - >, removing chlorine by a cuprous chloride precipitation method, a bismuth oxychloride precipitation method, an extraction method and the like until the electrolytic zinc is required, and the pretreatment mainly comprises alkali washing or multi-hearth furnace treatment to reduce the chlorine content. However, each process has advantages, disadvantages and limitations, for example, the cuprous chloride precipitation method has good dechlorination effect and low cost, but the dechlorination copper slag treatment technology needs to be further improved and perfected; the alkaline washing operation is simple, but a large amount of water is needed, the dechlorination effect is limited, the Zn loss is easily caused, and the like. The method removes Cl without using, thereby causing resource waste.
The waste acidic etching solution is waste liquid generated in the PCB etching process, the main components of the waste acidic etching solution are CuCl2, HCl, NH4Cl and the like, and the treatment method mainly adopts alkali neutralization and then sulfuric acid neutralization to recover copper sulfate products. In the treatment process, a large amount of alkali is consumed, a large amount of sludge is generated, and secondary pollution is easily caused. Besides heavy metal elements, the free hydrochloric acid contained in the waste also has higher comprehensive utilization value, and larger economic and environmental benefits can be generated if the waste can be reasonably recycled. Therefore, how to utilize the comprehensive utilization and recovery of metallurgical resources and prepare basic zinc chloride from copper, zinc and the like so as to comprehensively utilize waste raw materials. And the cyclic utilization and development of resources are realized.
For example, Chinese patent publication No. CN 105399132A discloses a process for preparing basic copper chloride and basic zinc chloride from brass slag and zinc-containing flue ash. The process for preparing the basic copper chloride and the basic zinc chloride by using the brass slag and the zinc-containing flue ash. The process comprises the steps of S1, acid leaching, S2, basic copper chloride synthesis and S3, basic zinc chloride synthesis. The process realizes effective recovery of copper and zinc elements in the brass slag and the zinc-containing flue dust, and improves resource utilization compared with the prior process which only can treat the brass slag or the zinc-containing flue dust independently and can only recover the copper or the zinc in the brass slag or the zinc-containing flue dust, and the basic copper chloride and the basic zinc chloride prepared by the whole process meet feed-grade standards; and only one kind of production wastewater is produced, thereby reducing the wastewater treatment burden and conforming to the circulation. However, this method is expensive because the process flow is long and the treatment of waste acidity, particularly the treatment for dechlorination, i.e., the leaching of Cl "and the treatment of other metal elements are difficult.
Chinese patent publication No. CN 109576500A, "a process for extracting metallic zinc from high chlorine and zinc-containing soot". The process comprises the steps of zinc ash alkaline washing dechlorination, leaching, goethite-like ore purification and impurity removal, deep copper salt dechlorination, three-stage purification, electrodeposition and casting; the process adopts a wet alkali washing dechlorination process, realizes zero discharge of wastewater, and has the advantages of simplicity and high chlorine removal rate compared with the traditional fire dechlorination process; the recovery rate of zinc is effectively improved by the specific leaching process; the method adopts a goethite-like method to purify and remove impurities, and effectively improves the impurity removal rate and the removal rate by adding modified magnesium diboride and combining three-stage antimony salt continuous purification treatment.
Chinese patent publication CN 105567983B discloses a process for comprehensively recovering and treating high fluorine chlorine zinc oxide soot and high fluorine chlorine waste acid. The invention provides a method for effectively removing fluorine and chlorine and utilizing waste acid and zinc oxide soot, wherein high fluorine chlorine zinc oxide is leached for the first time, the leaching solution for the first time uses the high fluorine chlorine waste acid, the liquid-solid separation is carried out by a filter press after the leaching for the first time, filter residue is filtered, the liquid is neutralized and then is separated by filter pressing by the high fluorine chlorine zinc oxide for the first time, the neutralized residue is returned to the first leaching to recover the metal therein, the neutralized liquid is added with zinc powder to purify and remove impurities, the filter pressing separation is carried out after the purification, the filter residue is filtered, the liquid is added with sodium carbonate for the second time to neutralize and precipitate zinc, the filter pressing separation is carried out after the second time neutralization, the liquid containing fluorine chlorine is taken as the sewage treatment process, the slag water containing alkali type zinc carbonate is washed and filter pressed, the water washing waste liquid is taken as the sewage treatment process, the slag is dried to obtain the basic zinc carbonate, the economic benefit is remarkable.
CN 107779606B discloses a method for wet processing of high fluorine chlorine zinc-copper containing soot, which comprises the following steps: the method comprises the steps of carrying out alkali elution twice on copper ash to remove fluorine and chlorine impurity elements in the copper ash, carrying out neutralization on secondary alkali washing slag of the copper ash after the secondary alkali washing to leach valuable metals such as zinc and copper in the copper ash, carrying out copper precipitation and chlorine removal on neutralized liquid, carrying out goethite process alum precipitation twice on the dechlorinated liquid, removing impurity ions such as iron, arsenic, antimony, fluorine, chlorine and the like in a solution and reducing COD (chemical oxygen demand) of the solution, feeding the alum-precipitated liquid into a concentration tank for subsequent purification treatment, finally feeding the alum-precipitated liquid into a zinc electrodeposition system, feeding neutralized slag into a pyrometallurgical lead smelting system after primary acid and primary high acid leaching, effectively recovering the valuable metals such as zinc and copper in the whole process, and achieving a fluorine and chlorine removal effect of more than 90%. The method realizes the effective treatment of the high fluorine chlorine zinc-copper containing soot with high efficiency and low cost, and simultaneously eliminates the influence of higher COD on zinc electrodeposition caused by the copper soot.
Also for example, chinese patent publication CN 110484730 a discloses a method for recovering feed-grade basic zinc chloride from zinc-containing sludge, which comprises the following steps: acidifying and removing impurities from sludge to obtain an iron removal solution containing zinc, nickel and cobalt, extracting the iron removal solution by using an extractant in a multistage manner to obtain a zinc-containing organic phase, washing and back-extracting the zinc-containing organic phase to obtain a zinc chloride solution, and preparing to obtain a basic zinc chloride product. The method adopts the electroplating sludge as the zinc raw material to recover the feed-grade basic zinc chloride, has more impurity content of the electroplating sludge, more complex components, more efficient and convenient one-step impurity removal, improves the recovery efficiency, realizes the separation and recovery of iron, cobalt, calcium, magnesium, nickel and zinc, and has good separation effect. The basic zinc chloride product recovered by the invention has low impurity content of feed hygiene indexes, completely meets the relevant standards of basic zinc chloride products of feed additives, has higher added value than zinc oxide and basic zinc carbonate, has simpler components of waste water, can recover the relevant products from the waste water for production, and has no waste water discharge in the whole process flow.
Furthermore, Chinese patent CN111453762A discloses a method for preparing basic zinc chloride by using hot galvanizing zinc smoke as a raw material; which is a method for preparing basic zinc chloride by taking hot galvanizing zinc smoke as a raw material, and belongs to the technical field of comprehensive utilization of resources. The method mainly comprises the following steps: mixing hot galvanizing zinc smoke with a zinc chloride aqueous solution, carrying out hydrolysis-hydration reaction, and carrying out suction filtration on the obtained product system to obtain the basic zinc chloride. The basic zinc chloride is prepared by taking the hot-dip galvanized smoke as a raw material, the raw material source is wide, the cost is low, the zinc resource utilization rate is improved, the environmental pollution is reduced, and the resource utilization of the hot-dip galvanized smoke is realized; the method can prepare basic zinc chloride products with higher added values while recycling the hot galvanizing zinc smoke. In addition, the filtered mother liquor can be used for preparing the hot galvanizing plating assistant solution again, so that the dual effects of economy and environment are achieved, and the comprehensive utilization of resources is realized. However, it can be seen from the above-mentioned embodiment that the hot dip galvanized smoke is used as a raw material. Meanwhile, the soot raw material in the smelting process cannot be well recycled in the preparation process.
As can be seen from the above-mentioned published patent and literature scope, the above-mentioned literature reports on the recovery of valuable metals by treating copper-containing soot by the all-wet process, and the literature reports on the combined treatment of copper soot and waste acid. However, the method is not a method for preparing high-alkali zinc chloride by treating copper-containing soot and acidic waste liquid, a multi-level medium circulation process is adopted, and the consumption of auxiliary materials in the processes of leaching, extraction and electrolysis is reduced, so that the same report is not found in the prior art documents.
Therefore, how to provide a technical process method for preparing basic zinc chloride by using high-chlorine smelting copper ash and acidic waste liquid aims at the problems that the conventional copper ash-containing process is high in auxiliary material consumption, low in leaching rate and low in quality of recovered products, and the conventional acidic waste liquid treatment technology is high in alkali liquor consumption and generates a large amount of sludge, so that secondary pollution is easily caused. Meanwhile, according to respective physicochemical properties of the copper-containing soot and the acidic waste liquid, the free acid in the acidic waste liquid is fully utilized to dissolve out heavy metals in the copper-containing soot, and the method for preparing the basic zinc chloride is realized by applying extraction-electrodeposition, so that the high-chlorine copper-containing soot and the acidic waste liquid are comprehensively utilized at low cost, and the method has the advantages of high metal recovery rate, small environmental pollution and simple process; has important practical significance.
Disclosure of Invention
In order to solve the defects in the prior art, the invention provides a method for preparing basic zinc chloride by using high-chlorine smelting soot, which takes the high-chlorine smelting soot and waste acidic liquid as raw materials, comprises neutral chlorine leaching, low leaching liquid and partial copper raffinate as bottom water, acidic chlorination leaching, copper extraction and electrolysis; the high-purity cathode copper is prepared by purifying and deironing leaching treatment and extraction-electrodeposition, the copper extraction raffinate is deironing, zinc extraction and back extraction to obtain a zinc chloride solution, and the zinc chloride solution is synthesized into basic zinc chloride under the action of ammonia water serving as a precipitator, so that the purposes of low cost, high comprehensive utilization rate, simple process and low production cost of high-chlorine smelting soot are achieved under the condition of no dechlorination, the purpose of recycling waste is achieved, and the production and preparation cost is reduced.
The invention discloses a method for preparing basic zinc chloride by using high-chlorine smelting soot, which takes the high-chlorine smelting soot and waste acidic liquid as raw materials and comprises the following steps:
1) neutral chlorination leaching:
adding the high-chlorine smelting soot into a reaction device under the negative pressure state of the reaction device, sequentially adding a residual copper extraction solution containing hydrogen chloride, hydrochloric acid and a corresponding sulfuric acid solution for neutral chlorination leaching, and performing filter pressing to obtain neutral chlorination leaching filter residue and a neutral chlorination leaching solution;
2) the acid chlorination leaching is carried out to obtain the acid chlorination leaching,
placing neutral chlorination leaching filter residues in an acidic chlorination leaching reaction device, then sequentially adding a hydrogen chloride-containing solution zinc extraction raffinate, a waste acidic etching solution and a corresponding sulfuric acid solution, simultaneously adding ground washing water, high-chlorine smelting ash packaging bag washing water and initial rainwater, carrying out acidic chlorination leaching, and filtering to obtain acidic chlorination leaching residues which are sent to a lead-tin smelting system and an acidic chlorination leaching solution which enters a copper extraction process system;
3) copper extraction and copper electrolysis
Copper extraction, namely performing precision filtration on the acidic chlorination leaching solution to obtain precision filtrate, controlling the solid content in the precision filtrate to be less than 0.03g/L, conveying the precision filtrate to an extraction section for Cu extraction, taking M5640 or LiX984 as an extracting agent, mixing the extracting agent with No. 260 kerosene to obtain an organic phase, and taking the precision filtrate as a water phase; fully stirring and mixing the organic phase and the water phase, and then carrying out Cu extraction, wherein the flow ratio of the water phase to the organic phase is controlled to be 1: 40-50, obtaining raffinate and a copper-containing organic phase, sending the copper-containing organic phase to a washing section for washing, controlling the concentration of washing acid to be 0.1N, sending the washed copper-containing organic phase to a back extraction section, and performing back extraction treatment to obtain a copper-rich solution;
copper electrolysis, namely pumping the copper-rich solution obtained by the back extraction treatment into an electrolytic cell after removing oil, and electrolyzing by taking insoluble Pb-Ca-Sn alloy as an anode and a copper plate as a cathode to prepare cathode copper; the solution after copper electrodeposition is used for the copper extraction and back extraction process; controlling electrolysis parameters: cell voltage is 1.75V-2.0V, and current density is 160A/m2-190 A/m2The copper pole pitch is 75mm-85 mm.
4) Neutral chlorination leaching purification iron removal
Adding an oxidant into the neutral chlorination leachate obtained in the step 1) for oxidation treatment to obtain an oxidation treatment solution, adjusting the pH value of the oxidation treatment solution to 4.5-5.0 by using calcium oxide or calcium hydroxide, then performing iron removal treatment to obtain an iron-removed solution, filtering and separating the iron-removed solution to obtain an iron-removed filtering separation solution, adding zinc powder into the iron-removed filtering separation solution for reduction treatment, and then performing further replacement impurity removal to obtain a post-replacement solution;
5) zinc extraction
Performing multi-stage countercurrent extraction on the liquid obtained after the replacement in the step 4) by using a zinc extractant to ensure that Zn is obtained2+An extract compound is generated with a zinc extracting agent and enters an organic phase, the organic phase after clarification and layering is a zinc extracting organic phase, and a water phase is a zinc extracting residual liquid; carrying out back extraction treatment on the loaded organic phase by adopting hydrochloric acid to obtain a zinc chloride solution;
6) preparing basic zinc chloride
And (3) pumping the zinc chloride solution obtained in the step 5) into a reaction device after oil removal, adding an ammonia water solution under the condition of no stirring, carrying out synthetic reaction, carrying out filter pressing after the reaction is finished to obtain filter pressing residues and filter pressing liquid, rinsing and drying the filter pressing residues to obtain a basic zinc chloride product, and recovering zinc from the filter pressing liquid through resin and recovering ammonium chloride by-products through MVR (mechanical vapor recompression) concentration and crystallization.
In the method for preparing basic zinc chloride by using high-chlorine smelting soot, the neutral chlorination leaching condition in the step 1) is to control the pH value at the end point of leaching to be 4.0-4.5 under the normal temperature condition; the leaching time is 1-2 h; controlling zinc content in the neutral chlorination leachate: 80-85g/L, copper: 2-1.5 g/L.
The method for preparing basic zinc chloride by using high-chlorine smelting soot comprises the following steps of 2) acid chlorination leaching, wherein the pH value at the end point of the acid chlorination leaching is controlled to be 2.0-2.5 under the normal temperature condition; controlling leaching time: 1-2 h; copper in acidic chlorination leachate: 20-25g/L, zinc: 50-60 g/L.
The method for preparing basic zinc chloride by using high-chlorine smelting soot comprises the following steps of 3) copper extraction and copper electrolysis, wherein an extracting agent is controlled: 30-35 of No. 260 kerosene: 65-70, controlling the extraction organic phase: controlling Cu in the raffinate to be less than or equal to 1.0g/L when the water phase is 2: 1; during the back extraction treatment, sulfuric acid-copper sulfate solution is used as back extraction acid, the Cu concentration during the back extraction is controlled to be 20-30g/L, and H is controlled+The sulfuric acid-copper sulfate electrobarren solution with the concentration of 3.0-3.5N is used as a back extraction acid, and the copper-containing organic phase is controlled to be a back extraction organic phase: the back extraction acid is water phase 5:1, and Cu concentration is 50-60g/L, H+Is a copper-rich solution of 1.0-1.5N.
The method for preparing the basic zinc chloride by using the high-chlorine smelting soot comprises the step 4) of neutral chlorination leaching, purification and iron removal, wherein the oxidant is H2O2Controlling Fe2 after iron removal+8-12 mg/L; the filtrate obtained after the solid-liquid separation of the iron-removed liquid is iron-removing filtering separation liquid, zinc powder is added into the iron-removing filtering separation liquid, and the adding amount of the zinc powder is controlled to be 1.2-2 times of the amount of Cu and Cd metals; carrying out two-stage displacement reduction impurity removal reaction, removing other heavy metal impurities, and filtering; stirring with one-section displacement controlStirring time: filtering for 35-50min to obtain first-stage replacement solution, and controlling Cu in the first-stage replacement solution2+<30 mg/L; then, carrying out second-stage replacement control, and controlling the stirring second-stage replacement time for 35-50 min; controlling the pH value of the solution after the second-stage replacement to be 4.8-5.2.
The method for preparing the basic zinc chloride by using the high-chlorine smelting soot comprises the step 5) of zinc extraction, wherein a zinc extracting agent is a mixture of P204 and% sulfonated kerosene, and the volume ratio of the P204 to the% sulfonated kerosene is controlled to be 25-35: 75-65 parts; controlling the extraction conditions during zinc extraction, namely a zinc extraction organic phase: water phase 2: 1; back extraction of organic phase: water phase 3: 1.
The method for preparing the basic zinc chloride by using the high-chlorine smelting soot comprises the step 6) of preparing the basic zinc chloride by controlling the synthetic reaction to be at 70-80 ℃ and stirring for 2-3h, and controlling the pH value of a solution in the reaction process to be 6.0-7.0; the filter press residue is rinsed, and secondary rinsing is carried out to remove soluble chlorine salt and excessive alkali; the primary rinsing water is reused for the synthesis process, and the secondary rinsing water is reused for the primary rinsing.
The invention discloses a method for preparing basic zinc chloride by using high-chlorine smelting soot, which mainly comprises the following production process steps: copper soot and waste acidic liquid → neutral chlorination leaching → oxidative iron removal → conversion and impurity removal → purified liquid → zinc extraction → back extraction → basic zinc chloride precipitation → filtration → preparation of basic zinc chloride.
Middle leaching residue + waste acidic etching solution → acidic chlorination leaching → acid leaching solution → copper extraction → back extraction → electrodeposition or electrolysis → cathode copper.
Compared with the prior art, the method for preparing the basic zinc chloride by using the high-chlorine smelting soot has the following characteristics:
compared with the traditional method for preparing the basic zinc chloride, the method has the following advantages:
firstly, the waste acidic etching solution is used as a leaching reagent, and the raffinate is used for multi-level medium circulation, so that the leaching cost is reduced; the respective physicochemical properties of the high-chlorine smelting soot and the waste acidic etching solution are utilized, so that high-value utilization of solid waste resources is realized, and the aim of preparing waste from waste is fulfilled; under the condition of no dechlorination, the low-cost high-value utilization of the high-chlorine smelting soot is realized, cathode copper and basic zinc chloride products with high additional values are prepared, the production cost is reduced, and the economic benefit is improved;
secondly, the cathode copper and the basic zinc chloride products recovered by the method have low impurity content and stable product quality, wherein the basic zinc chloride reaches the feed-grade national standard feed additive basic zinc chloride (GB/T22546-2008) of the basic zinc chloride products by detecting each index;
thirdly, the invention has the advantages of simple process, high recovery rate of valuable metals, high purity of the prepared basic zinc chloride product, low production cost, low labor intensity of workers and the like, and is easy for industrialized popularization.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments.
The invention discloses a method for preparing basic zinc chloride by using high-chlorine smelting soot, which mainly adopts the following technical scheme:
1) neutral chlorination leaching is carried out to obtain the final product,
adding high-chlorine smelting soot into a reaction device under the negative pressure state of the reaction device, sequentially adding raffinate containing hydrogen chloride, hydrochloric acid and corresponding sulfuric acid solution for neutral chlorination leaching, and performing filter pressing to obtain neutral chlorination leaching filter residue and neutral chlorination leaching liquid; the method comprises the following steps of packaging high-chlorine smelting soot by using a woven bag, arranging a discharge hole at the bottom of the high-chlorine smelting soot, opening the discharge hole completely and placing the discharge hole into a reaction kettle during production, keeping a micro negative pressure state in the reaction kettle, then opening the discharge hole, enabling materials to enter the reaction kettle through a funnel formed by a slender discharge hole, sequentially adding copper extraction raffinate mainly comprising a hydrogen chloride solution, hydrochloric acid, a small amount of sulfuric acid and the like for neutral chlorination leaching, wherein the solubility product of calcium and lead is low, and most of calcium and lead and sulfuric acid preferentially react and enter slag during leaching; carrying out neutral chlorination leaching and then carrying out filter pressing to obtain neutral chlorination leaching filter residues or a neutral leaching cake and a neutral chlorination leaching liquid, wherein the neutral leaching cake enters an acid chlorination leaching process, and the filtrate is the neutral chlorination leaching liquid and enters an oxidation iron removal process; the technical conditions of neutral chlorination leaching are as follows: the reaction is carried out under the condition of normal temperature; controlling the pH value of the leaching end point to be 4.0-4.5; the leaching time is 1-2 h; the neutral chlorination leachate or leachate contains zinc: 80-85g/L, copper: 2-1.5 g/L;
2) and the acid chlorination leaching is carried out,
putting a neutral chlorination leaching filter cake, namely neutral chlorination leaching filter residue, into an acidic chlorination leaching reaction kettle, sequentially adding a zinc extraction residual liquid, wherein the zinc extraction residual liquid mainly comprises a hydrogen chloride solution, a waste acidic etching solution and a small amount of sulfuric acid solution, performing acidic chlorination leaching, and simultaneously adding ground washing water, packaging bag washing water, initial rainwater and the like, controlling the pH value to be 1.5-2.0 during acidic chlorination leaching, and ensuring that the solubility product of calcium and lead is low, and during leaching, most of calcium and lead in raw materials preferentially react with sulfuric acid to enter acidic chlorination leaching residues; carrying out pressure filtration after acidic chlorination leaching, washing filter residues, namely filter cakes, by using a zinc extraction residual liquid, returning a washing liquid to the acidic chlorination leaching, allowing a leaching liquid, namely an acidic chlorination leaching liquid to enter a copper extraction process, and conveying acidic chlorination leaching residues to a lead-tin smelting system; the technical conditions of the acidic chlorination leaching are as follows: normal temperature; the pH value of the leaching end point is 2.0-2.5; time: 1-2 h; leaching liquor copper: 20-25g/L, zinc: 50-60 g/L;
3) and then the copper is extracted,
copper extraction, namely performing precise filtration on the acidic chlorination leaching solution to obtain a precise filtrate, controlling the solid content in the precise filtrate to be less than 0.03g/L, then conveying the precise filtrate to an extraction section for Cu extraction, mixing an extracting agent with No. 260 kerosene by taking M5640 or LiX984 as an extracting agent to obtain an organic phase, namely a copper extraction organic phase, and taking the precise filtrate as an aqueous phase, namely a dissolution liquid, namely a copper extraction aqueous phase; controlling an extracting agent: and (2) adding No. 260 kerosene 30-35:65-70, fully stirring and mixing the organic phase and the aqueous phase, and then carrying out Cu extraction, wherein the flow ratio of the aqueous phase to the organic phase is controlled to be 1: 40-50, obtaining raffinate and a copper-containing organic phase, controlling Cu in the raffinate to be less than or equal to 1.0g/L, sending the copper-containing organic phase to a washing section for washing, controlling the concentration of washing acid to be 0.1N, sending the copper-containing organic phase subjected to washing to a stripping section, and performing stripping treatment to obtain a copper-rich solution;
the concentration of Cu is 20-30g/L, H+Sulfuric acid-copper sulfate electrobarren solution with 3.0-3.5N is used as back extraction acid,taking a copper-containing organic phase as a back extraction organic phase, taking back extraction acid as a water phase or a back extraction water phase, and controlling the back extraction organic phase: water phase 5:1, Cu concentration 50-60g/L, H+Is a copper-rich solution of 1.0-1.5N.
4) Copper electrodeposition or copper electrolysis,
deoiling the copper-rich solution after back extraction to be used as electrolyte or electro-deposition liquid, pumping the electrolyte or electro-deposition liquid into an electrolytic bath, and depositing copper in the electrolyte or the electro-deposition liquid to a cathode under the action of direct current by using insoluble Pb-Ca-Sn alloy as an anode and a copper plate as a cathode during electrolysis to obtain cathode copper; the solution after copper electrodeposition is returned to be used for a copper extraction stripping process, namely a stripping section of copper extraction; controlling electrolysis parameters during copper electrolysis: cell voltage is 1.7V-2.1V, and current density is 150A/m2-200 A/m2The same polar distance is 70mm-90 mm.
5) Neutral chlorination leaching, purifying and iron removing,
h is adopted in the neutral chlorination leaching solution in the step 1)2O2Oxidizing with oxidant to obtain oxidation liquid, regulating pH to 4.5-5.0 with lime (calcium oxide or calcium hydroxide), and removing iron; obtaining iron-removed liquid, and controlling Fe in the iron-removed liquid2+8-12 mg/L; adding zinc powder into the iron-removing filtering separation liquid to perform two-stage reduction reaction, namely two-stage replacement, removing other heavy metal impurities, and then filtering, wherein the adding amount of the zinc powder is controlled to be 1.2-2 times of the amount of metals such as Cu, Cd and the like; one-stage replacement control: stirring time: 45min, one-stage replacement of Cu2+<30 mg/L; and (3) second-stage replacement control: carrying out second-stage replacement under the condition of continuous stirring, and controlling the stirring time: controlling the pH value of the second-stage replacement solution to be 5.0 after 45min to obtain the replacement solution;
6) zinc extraction
Performing multi-stage countercurrent extraction on the displaced liquid obtained in the previous step by adopting a zinc extractant of 30 percent P204 and 70 percent sulfonated kerosene to ensure that Zn is obtained2+An extract compound is generated with a zinc extractant and enters an organic phase, the clarified and layered organic phase is an extract liquid which is a zinc extraction organic phase, and the water phase is a zinc extraction residual liquid; the zinc extraction organic phase is also called as the loading organic phase and adopts saltCarrying out back extraction treatment on the acid to obtain a zinc chloride solution; controlling extraction conditions: zinc extraction organic phase: 2:1 of water phase; back extraction of organic phase: water phase 3: 1;
7) basic zinc chloride synthesis
Deoiling the zinc chloride solution, pumping into a synthesis reaction kettle, adding ammonia water under the condition of continuous stirring, controlling the pH value in the process to be 6.0-7.0, stirring and reacting at 70-80 ℃ for 2-3h, and then performing filter pressing to obtain filter pressing residues, namely filter cakes, and performing secondary rinsing treatment to remove soluble chlorine salt and excessive alkali; reusing the primary rinsing water in the synthesis process, and reusing the secondary rinsing water in the primary rinsing; drying the filter cake to obtain a basic zinc chloride product;
and after zinc is recovered from the synthesized filtrate through resin, ammonium chloride byproduct is recovered through MVR concentration and crystallization, water generated by evaporation is recycled after condensation, no wastewater is generated in the whole process, and clean production is realized.
The following examples are the same as the above-described embodiments except for the following descriptions.
Example 1
The ingredients of the raw materials used in this example are shown in the following table;
the main components of the high-chlorine smelting soot in the table are as follows: is based on
The table is a table unit of main components of the waste acidic etching solution: g/L
| Cu2+ | Cl- | NH3-N | Fe | H+ |
| 115.20g/L | 254.16g/L | 0.62g/L | 0.013g/L | 3.89mol/L |
The waste acid is the waste sulfuric acid solution as the main component.
The invention discloses a method for preparing basic zinc chloride by using high-chlorine smelting soot, which comprises the following steps of:
1) neutral chlorination leaching is carried out to obtain the final product,
packaging about 100Kg of high-chlorine smelting ash by adopting a woven bag, arranging a discharge hole at the bottom of the high-chlorine smelting ash, completely placing the discharge hole into a reaction kettle during production, keeping a micro negative pressure state in the reaction kettle, opening the discharge hole, enabling the materials to enter the reaction kettle through a funnel formed by a slender discharge hole, sequentially adding raffinate containing hydrogen chloride, hydrochloric acid and corresponding sulfuric acid solution for neutral chlorination leaching, and performing pressure filtration to obtain neutral chlorination leaching filter residue and neutral chlorination leaching liquid; the method comprises the following steps of packaging high-chlorine smelting soot by using a woven bag, arranging a discharge hole at the bottom of the high-chlorine smelting soot, opening the discharge hole completely and placing the discharge hole into a reaction kettle during production, keeping a micro negative pressure state in the reaction kettle, then opening the discharge hole, enabling materials to enter the reaction kettle through a funnel formed by a slender discharge hole, sequentially adding copper extraction raffinate mainly comprising a hydrogen chloride solution, hydrochloric acid, a small amount of sulfuric acid and the like for neutral chlorination leaching, wherein the solubility product of calcium and lead is low, and most of calcium and lead and sulfuric acid preferentially react and enter slag during leaching; carrying out neutral chlorination leaching and then carrying out filter pressing to obtain neutral chlorination leaching filter residues or a neutral leaching cake and a neutral chlorination leaching liquid, wherein the neutral leaching cake enters an acid chlorination leaching process, and the filtrate is the neutral chlorination leaching liquid and enters an oxidation iron removal process; the technical conditions of neutral chlorination leaching are as follows: the reaction is carried out under the condition of normal temperature; controlling the pH value of the leaching end point to be 4.0-4.5; the leaching time is 1.5 h; the neutral chlorination leachate or leachate contains zinc: 80g/L, about: 2 g/L;
2) and the acid chlorination leaching is carried out,
putting a neutral chlorination leaching filter cake, namely neutral chlorination leaching filter residue, into an acidic chlorination leaching reaction kettle, sequentially adding a zinc extraction residual liquid which mainly comprises a hydrogen chloride solution, a waste acidic etching solution, a small amount of sulfuric acid and other solutions, performing acidic chlorination leaching, simultaneously adding ground washing water, packaging bag washing water, initial rainwater and the like, controlling the pH value to be 1.5-2.0 during acidic chlorination leaching, and ensuring that the solubility product of calcium and lead is low, and during leaching, most of calcium and lead in raw materials preferentially react with sulfuric acid and enter acidic chlorination leaching residues; carrying out pressure filtration after acidic chlorination leaching, washing filter residues, namely filter cakes, by using a zinc extraction residual liquid, returning a washing liquid to the acidic chlorination leaching, allowing a leaching liquid, namely an acidic chlorination leaching liquid to enter a copper extraction process, and conveying acidic chlorination leaching residues to a lead-tin smelting system; the technical conditions of the acidic chlorination leaching are as follows: normal temperature; the leaching end point pH is 2.5; time: 2 h; leaching liquor copper: 25g/L, zinc: 55 g/L;
3) and then the copper is extracted,
copper extraction, namely performing precise filtration on the acidic chlorination leaching solution to obtain a precise filtrate, controlling the solid content in the precise filtrate to be less than 0.03g/L, then conveying the precise filtrate to an extraction section for Cu extraction, mixing an extracting agent with No. 260 kerosene by taking M5640 or LiX984 as an extracting agent to obtain an organic phase, namely a copper extraction organic phase, and taking the precise filtrate as an aqueous phase, namely a dissolution liquid, namely a copper extraction aqueous phase; controlling an extracting agent: 260# kerosene 30: and 70, fully stirring and mixing the organic phase and the aqueous phase, and then carrying out Cu extraction, wherein the flow ratio of the aqueous phase to the organic phase is controlled to be 1: 40-50, obtaining raffinate and a copper-containing organic phase, controlling Cu in the raffinate to be less than or equal to 1.0g/L, sending the copper-containing organic phase to a washing section for washing, controlling the concentration of washing acid to be 0.1N, sending the copper-containing organic phase subjected to washing to a stripping section, and performing stripping treatment to obtain a copper-rich solution;
the Cu concentration is 25g/L, H+The sulfuric acid-copper sulfate electrobarren solution with the concentration of 3.5N is used as a back extraction acid, a copper-containing organic phase is used as a back extraction organic phase, the back extraction acid is a water phase or a back extraction water phase, and the back extraction organic phase is controlled: water phase 5:1, Cu concentration 60g/L, H+Is a 1.5N copper rich solution.
4) Copper electrodeposition or copper electrolysis,
deoiling the copper-rich solution after back extraction to be used as electrolyte or electro-deposition liquid, pumping the electrolyte or electro-deposition liquid into an electrolytic bath, and depositing copper in the electrolyte or the electro-deposition liquid to a cathode under the action of direct current by using insoluble Pb-Ca-Sn alloy as an anode and a copper plate as a cathode during electrolysis to obtain cathode copper; the solution after copper electrodeposition is returned to be used for a copper extraction stripping process, namely a stripping section of copper extraction; controlling electrolysis parameters during copper electrolysis: cell voltage is 1.7V-2.1V, and current density is 180A/m2The same polar distance is 80 mm.
5) Neutral chlorination leaching, purifying and iron removing,
h is adopted in the neutral chlorination leaching solution in the step 1)2O2Oxidizing with oxidant to obtain oxidation liquid, regulating pH to 4.8 with lime (calcium oxide or calcium hydroxide), and removing iron; obtaining iron-removed liquid, and controlling Fe in the iron-removed liquid2+10 mg/L; adding zinc powder into the iron-removing filtering separation liquid to perform two-stage reduction reaction, namely two-stage replacement, removing other heavy metal impurities, and then filtering, wherein the adding amount of the zinc powder is controlled to be 1.2-2 times of the amount of metals such as Cu, Cd and the like; one-stage replacement control: stirring time: 45min, one-stage replacement of Cu2+<30 mg/L; and (3) second-stage replacement control: carrying out second-stage replacement under the condition of continuous stirring, and controlling the stirring time: controlling the pH value of the second-stage replacement solution to be 5.0 after 45min to obtain the replacement solution;
6) zinc extraction
The replacement liquid obtained in the previous step is subjected to zinc extraction by adopting a zinc extraction agent with the composition ratio of 30 percent of P204 and 70 percent of sulfonated keroseneMulti-stage countercurrent extraction of Zn2+An extract compound is generated with a zinc extractant and enters an organic phase, the clarified and layered organic phase is an extract liquid which is a zinc extraction organic phase, and the water phase is a zinc extraction residual liquid; the zinc extraction organic phase is also called as a loaded organic phase, and hydrochloric acid is adopted for carrying out back extraction treatment to obtain a zinc chloride solution; controlling extraction conditions: zinc extraction organic phase: 2:1 of water phase; back extraction of organic phase: water phase 3: 1;
7) basic zinc chloride synthesis
Deoiling the zinc chloride solution, pumping into a synthesis reaction kettle, adding ammonia water under the condition of continuous stirring, controlling the pH value of the process to be 6.5, stirring and reacting at 70-80 ℃ for 3 hours, and then performing filter pressing to obtain filter pressing residues, namely filter cakes, and performing secondary rinsing treatment to remove soluble chlorine salt and excessive alkali; reusing the primary rinsing water in the synthesis process, and reusing the secondary rinsing water in the primary rinsing; drying the filter cake to obtain a basic zinc chloride product with the weight of about 104.2 Kg; the quality requirement of the feed additive is met through detection.
In conclusion, the invention utilizes the high-chlorine smelting soot to carry out dechlorination and recover valuable metals of zinc and copper, the high-fluorine chlorine zinc oxide soot and the high-fluorine chlorine waste acid for comprehensive recovery treatment, and utilizes the zinc-containing sludge to recover feed-grade basic zinc chloride.
Example 2
The ingredients of the raw materials used in this example are shown in the following table;
the main components of the high-chlorine smelting soot in the table are as follows: is based on
| Zn | Pb | Cu | Sn | Cd | Fe | Cl | F | S |
| 36.18 | 9.31 | 4.23 | 0.96 | 0.14 | 0.91 | 7.94 | 0.16 | 2.28 |
The table is a table unit of main components of the waste acidic etching solution: g/L
| Cu2+ | Cl- | NH3-N | Fe | H+ |
| 114.60g/L | 255.08g/L | 0.66g/L | 0.015g/L | 3.83mol/L |
The components of the high-chlorine smelting soot and the sexual etching solution are used as raw materials, and the waste acid is a waste sulfuric acid solution as a main component.
This example was prepared using the above starting materials in the following process steps,
1) neutral chlorination leaching is carried out to obtain the final product,
adding about 100Kg of high-chlorine smelting soot into a reaction device under the negative pressure state of the reaction device, sequentially adding a residual copper extraction solution containing hydrogen chloride, hydrochloric acid and a corresponding sulfuric acid solution for neutral chlorination leaching, and performing pressure filtration to obtain neutral chlorination leaching filter residue and a neutral chlorination leaching solution; the method comprises the following steps of packaging high-chlorine smelting soot by using a woven bag, arranging a discharge hole at the bottom of the high-chlorine smelting soot, opening the discharge hole completely and placing the discharge hole into a reaction kettle during production, keeping a micro negative pressure state in the reaction kettle, then opening the discharge hole, enabling materials to enter the reaction kettle through a funnel formed by a slender discharge hole, sequentially adding copper extraction raffinate mainly comprising a hydrogen chloride solution, hydrochloric acid, a small amount of sulfuric acid and the like for neutral chlorination leaching, wherein the solubility product of calcium and lead is low, and most of calcium and lead and sulfuric acid preferentially react and enter slag during leaching; carrying out neutral chlorination leaching and then carrying out filter pressing to obtain neutral chlorination leaching filter residues or a neutral leaching cake and a neutral chlorination leaching liquid, wherein the neutral leaching cake enters an acid chlorination leaching process, and the filtrate is the neutral chlorination leaching liquid and enters an oxidation iron removal process; the technical conditions of neutral chlorination leaching are as follows: the reaction is carried out under the condition of normal temperature; controlling the pH value of the leaching end point to be 4.5; the leaching time is 2 h; the neutral chlorination leachate or leachate contains zinc: 85g/L, copper: 1.8 g/L;
2) and the acid chlorination leaching is carried out,
putting a neutral chlorination leaching filter cake, namely neutral chlorination leaching filter residue, into an acidic chlorination leaching reaction kettle, sequentially adding a zinc extraction residual liquid which mainly comprises a hydrogen chloride solution, a waste acidic etching solution, a small amount of sulfuric acid and the like for acidic chlorination leaching, and simultaneously adding ground washing water, packaging bag washing water, initial rainwater and the like, wherein the pH value is controlled to be 1.50 during acidic chlorination leaching, the solubility product of calcium and lead is low, and most of calcium and lead in raw materials and sulfuric acid preferentially react and enter acidic chlorination leaching residues during leaching; carrying out pressure filtration after acidic chlorination leaching, washing filter residues, namely filter cakes, by using a zinc extraction residual liquid, returning a washing liquid to the acidic chlorination leaching, allowing a leaching liquid, namely an acidic chlorination leaching liquid to enter a copper extraction process, and conveying acidic chlorination leaching residues to a lead-tin smelting system; the technical conditions of the acidic chlorination leaching are as follows: normal temperature; the leaching end point pH is 2.5; time: 2 h; leaching liquor copper: 25g/L, zinc: 60 g/L;
3) and then the copper is extracted,
copper extraction, namely performing precise filtration on the acidic chlorination leaching solution to obtain a precise filtrate, controlling the solid content in the precise filtrate to be less than 0.03g/L, then conveying the precise filtrate to an extraction section for Cu extraction, mixing an extracting agent with No. 260 kerosene by taking M5640 or LiX984 as an extracting agent to obtain an organic phase, namely a copper extraction organic phase, and taking the precise filtrate as an aqueous phase, namely a dissolution liquid, namely a copper extraction aqueous phase; controlling an extracting agent: and (2) adding No. 260 kerosene 35:65, fully stirring and mixing the organic phase and the aqueous phase, and then carrying out Cu extraction, wherein the flow ratio of the aqueous phase to the organic phase is controlled to be 1: 40-50, obtaining raffinate and a copper-containing organic phase, controlling Cu in the raffinate to be less than or equal to 1.0g/L, sending the copper-containing organic phase to a washing section for washing, controlling the concentration of washing acid to be 0.1N, sending the copper-containing organic phase subjected to washing to a stripping section, and performing stripping treatment to obtain a copper-rich solution;
the Cu concentration is 30g/L, H+The sulfuric acid-copper sulfate electrobarren solution with the concentration of 3.5N is used as a back extraction acid, a copper-containing organic phase is used as a back extraction organic phase, the back extraction acid is a water phase or a back extraction water phase, and the back extraction organic phase is controlled: water phase 5:1, Cu concentration 60g/L, H+Is a copper-rich solution of 1.0-1.5N.
4) Copper electrodeposition or copper electrolysis,
deoiling the copper-rich solution after back extraction to be used as electrolyte or electro-deposition liquid, pumping the electrolyte or electro-deposition liquid into an electrolytic bath, and depositing copper in the electrolyte or the electro-deposition liquid to a cathode under the action of direct current by using insoluble Pb-Ca-Sn alloy as an anode and a copper plate as a cathode during electrolysis to obtain cathode copper; the solution after copper electrodeposition is returned to be used for a copper extraction stripping process, namely a stripping section of copper extraction; controlling electrolysis parameters during copper electrolysis: cell voltage is 1.7V-2.1V, and current density is 200A/m2And the same polar distance is 90 mm.
5) Neutral chlorination leaching, purifying and iron removing,
h is adopted in the neutral chlorination leaching solution in the step 1)2O2Using calcium peroxide as oxidant, or using calcium peroxide as oxidant, making oxidation treatment to obtain oxidation treatment liquor, utilizing lime calcium oxide or calcium hydroxide to regulate pH value of oxidation treatment liquor to 5.0, then making iron-removing treatment; obtaining iron-removed liquid, and controlling Fe in the iron-removed liquid2+10 mg/L; adding zinc powder into the iron-removing filtering separation liquid to perform two-stage reduction reaction, namely two-stage replacement, removing other heavy metal impurities, and then filtering, wherein the addition amount of the zinc powder is controlled to be 2 times of the amount of metals such as Cu, Cd and the like; one-stage replacement control: stirring time: 45min, one-stage replacement of Cu2+<30 mg/L; and (3) second-stage replacement control: carrying out second-stage replacement under the condition of continuous stirring, and controlling the stirring time: controlling the pH value of the second-stage replacement solution to be 5.0 after 45min to obtain the replacement solution;
6) zinc extraction
Performing multi-stage countercurrent extraction on the displaced liquid obtained in the previous step by adopting a zinc extractant of 30 percent P204 and 70 percent sulfonated kerosene to ensure that Zn is obtained2+An extract compound is generated with a zinc extractant and enters an organic phase, the clarified and layered organic phase is an extract liquid which is a zinc extraction organic phase, and the water phase is a zinc extraction residual liquid; the zinc extraction organic phase is also called as a loaded organic phase, and hydrochloric acid is adopted for carrying out back extraction treatment to obtain a zinc chloride solution; controlling extraction conditions: zinc extraction organic phase: 2:1 of water phase; back extraction of organic phase: water phase 3: 1;
7) basic zinc chloride synthesis
Deoiling the zinc chloride solution, pumping into a synthesis reaction kettle, adding ammonia water under the condition of continuous stirring, controlling the pH value in the process to be 6.0-7.0, stirring and reacting at 70-80 ℃ for 2-3h, and then performing filter pressing to obtain filter pressing residues, namely filter cakes, and performing secondary rinsing treatment to remove soluble chlorine salt and excessive alkali; reusing the primary rinsing water in the synthesis process, and reusing the secondary rinsing water in the primary rinsing; and drying the filter cake to obtain the basic zinc chloride product. And the comprehensive leaching rates of copper and zinc are 98.5 percent and 98.2 percent.
Comparative examples
The main components of the high-chlorine smelting soot in the table are as follows: is based on
| Zn | Pb | Cu | Sn | Cd | Fe | Cl | F | S |
| 35.12 | 9.31 | 4.23 | 0.96 | 0.14 | 0.91 | 7.94 | 0.16 | 2.28 |
The description is the same as example 1 except for the above description, except that the prior art process is adopted:
adding 100kg of high-chlorine smelting soot into a reaction device under the negative pressure state of the reaction device, adding a proper amount of impurity removing agent, reacting for 1 hour, removing toxic metals such as lead, arsenic and chromium, and obtaining copper and zinc solution containing 1.33g/L of copper and 66.2g/L of zinc after impurity removal; reacting the copper and zinc solution after impurity removal with copper containing 20g/L after impurity removal, controlling the temperature at 40 ℃, preparing the rest according to the prior art method, rinsing, filtering and drying the solid to obtain 986.4g of basic zinc chloride product; the acid leaching uses hydrochloric acid as a main raw material. The water washing and the bottom water are both carried out by using tap water as raw materials, the specific steps are carried out according to the prior art method, and meanwhile, the high-chlorine smelting soot and the waste acid liquid are not used as raw materials.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents. Are within the scope of the patent protection.
Claims (7)
1. A method for preparing basic zinc chloride by using high-chlorine smelting soot, which takes the high-chlorine smelting soot and waste acidic liquid as raw materials, comprises the following steps:
1) neutral chlorination leaching:
adding the high-chlorine smelting soot into a reaction device under the negative pressure state of the reaction device, sequentially adding a residual copper extraction solution containing hydrogen chloride, hydrochloric acid and a corresponding sulfuric acid solution for neutral chlorination leaching, and performing filter pressing to obtain neutral chlorination leaching filter residue and a neutral chlorination leaching solution;
2) the acid chlorination leaching is carried out to obtain the acid chlorination leaching,
placing neutral chlorination leaching filter residues in an acidic chlorination leaching reaction device, then sequentially adding a hydrogen chloride-containing solution zinc extraction raffinate, a waste acidic etching solution and a corresponding sulfuric acid solution, simultaneously adding ground washing water, high-chlorine smelting ash packaging bag washing water and initial rainwater, carrying out acidic chlorination leaching, and filtering to obtain acidic chlorination leaching residues which are sent to a lead-tin smelting system and an acidic chlorination leaching solution which enters a copper extraction process system;
3) copper extraction and copper electrolysis
Copper extraction, namely performing precision filtration on the acidic chlorination leaching solution to obtain precision filtrate, controlling the solid content in the precision filtrate to be less than 0.03g/L, conveying the precision filtrate to an extraction section for Cu extraction, taking M5640 or LiX984 as an extracting agent, mixing the extracting agent with No. 260 kerosene to obtain an organic phase, and taking the precision filtrate as a water phase; fully stirring and mixing the organic phase and the water phase, and then carrying out Cu extraction, wherein the flow ratio of the water phase to the organic phase is controlled to be 1: 40-50, obtaining raffinate and a copper-containing organic phase, sending the copper-containing organic phase to a washing section for washing, controlling the concentration of washing acid to be 0.1N, sending the washed copper-containing organic phase to a back extraction section, and performing back extraction treatment to obtain a copper-rich solution;
copper electrolysis, namely pumping the copper-rich solution obtained by the back extraction treatment into an electrolytic cell after removing oil, and electrolyzing by taking insoluble Pb-Ca-Sn alloy as an anode and a copper plate as a cathode to prepare cathode copper; the solution after copper electrodeposition is used for the copper extraction and back extraction process; controlling electrolysis parameters: cell voltage is 1.75V-2.0V, and current density is 160A/m2-190 A/m2The copper pole distance is 75mm-85 mm;
4) neutral chlorination leaching purification iron removal
Adding an oxidant into the neutral chlorination leachate obtained in the step 1) for oxidation treatment to obtain an oxidation treatment solution, adjusting the pH =4.5-5.0 of the oxidation treatment solution by using calcium oxide or calcium hydroxide, then performing iron removal treatment to obtain an iron-removed solution, filtering and separating the iron-removed solution to obtain an iron-removed filtering separation solution, adding zinc powder into the iron-removed filtering separation solution for reduction treatment, and then further performing replacement impurity removal to obtain a post-replacement solution;
5) zinc extraction
Performing multi-stage countercurrent extraction on the liquid obtained after the replacement in the step 4) by using a zinc extractant to ensure that Zn is obtained2+An extract compound is generated with a zinc extracting agent and enters an organic phase, the organic phase after clarification and layering is a zinc extracting organic phase, and a water phase is a zinc extracting residual liquid; carrying out back extraction treatment on the loaded organic phase by adopting hydrochloric acid to obtain a zinc chloride solution;
6) preparing basic zinc chloride
And (3) pumping the zinc chloride solution obtained in the step 5) into a reaction device after oil removal, adding an ammonia water solution under the condition of no stirring, carrying out synthetic reaction, carrying out filter pressing after the reaction is finished to obtain filter pressing residues and filter pressing liquid, rinsing and drying the filter pressing residues to obtain a basic zinc chloride product, and recovering zinc from the filter pressing liquid through resin and recovering ammonium chloride by-products through MVR (mechanical vapor recompression) concentration and crystallization.
2. The method for preparing basic zinc chloride by using high-chlorine smelting soot according to claim 1, wherein the conditions of the neutral chlorination leaching in the step 1) are that the pH =4.0-4.5 of the leaching end point is controlled under normal temperature conditions; the leaching time is 1-2 h; controlling zinc content in the neutral chlorination leachate: 80-85g/L, copper: 2-1.5 g/L.
3. The method for preparing basic zinc chloride by using high-chlorine smelting soot according to claim 1, wherein the step 2) of acidic chlorination leaching is performed under the condition of normal temperature, and the leaching time is controlled as follows: 1-2 h; controlling the pH =2.0-2.5 at the end of the acidic chlorination leaching; copper in acidic chlorination leachate: 20-25g/L, zinc: 50-60 g/L.
4. The method for preparing basic zinc chloride by using high-chlorine smelting soot according to claim 1, which is characterized in that in the step 3), copper extraction and copper electrolysis are carried out, and the extracting agents are controlled to be as follows: 260# kerosene = 30-35:65-70, controlling the extraction organic phase: the water phase =2:1, and Cu in the raffinate is controlled to be less than or equal to 1.0 g/L; during the back extraction treatment, sulfuric acid-copper sulfate solution is used as back extraction acid, the Cu concentration during the back extraction is controlled to be 20-30g/L, and H is controlled+Sulfuric acid-copper sulfate with concentration of 3.0-3.5NThe electrobarren solution is a strip acid, and the copper-containing organic phase is controlled to be a strip organic phase: the back extraction acid is water phase =5:1, and Cu concentration is 50-60g/L, H+Is a copper-rich solution of 1.0-1.5N.
5. The method for preparing basic zinc chloride by using high-chlorine smelting soot according to claim 1, wherein step 4) neutral chlorination leaching is used for purifying and removing iron, and the oxidant is H2O2Controlling Fe2 after iron removal+8-12 mg/L; the filtrate obtained after the solid-liquid separation of the iron-removed liquid is iron-removing filtering separation liquid, zinc powder is added into the iron-removing filtering separation liquid, and the adding amount of the zinc powder is controlled to be 1.2-2 times of the amount of Cu and Cd metals; carrying out two-stage displacement reduction impurity removal reaction, removing other heavy metal impurities, and filtering; controlling the stirring time of a displacement: filtering for 35-50min to obtain first-stage replacement solution, and controlling Cu in the first-stage replacement solution2+<30 mg/L; then, carrying out second-stage replacement control, and controlling the stirring second-stage replacement time for 35-50 min; controlling the pH of the solution after the second-stage replacement to be 4.8-5.2.
6. The method for preparing basic zinc chloride by using high-chlorine smelting soot according to claim 1, wherein in the step 5), the zinc extraction is carried out by controlling the zinc extraction agent to be a mixture of P204 and% sulfonated kerosene, and controlling the volume ratio of the P204 to the% sulfonated kerosene to be 25-35: 75-65 parts; controlling the extraction conditions during zinc extraction, namely a zinc extraction organic phase: water phase =2: 1; back extraction of organic phase: water phase =3: 1.
7. The method for preparing basic zinc chloride by using high-chlorine smelting soot according to claim 1, wherein the step 6) is used for preparing the basic zinc chloride by controlling the synthesis reaction to be at 70-80 ℃ and stirring for 2-3h, and controlling the pH =6.0-7.0 of the solution during the reaction; the filter press residue is rinsed, and secondary rinsing is carried out to remove soluble chlorine salt and excessive alkali; the primary rinsing water is reused for the synthesis process, and the secondary rinsing water is reused for the primary rinsing.
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| CN115652103A (en) * | 2022-11-03 | 2023-01-31 | 中冶南方都市环保工程技术股份有限公司 | Method for extracting zinc element from blast furnace dust by wet process |
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