Method for stepwise recovering iron, tin, indium, germanium and zinc from hard zinc hydrochloric acid leaching solution

Abstract

The invention discloses a method for stepwise recovering iron, tin, indium, germanium and zinc from a hard zinc hydrochloric acid leaching solution. The method comprises the steps of iron extraction, directional separation, indium extraction, germanium extraction and aftertreatment. Through technical innovation and process integration, comprehensive recovery of multiple metals such as indium, tin, germanium, iron and zinc in the complex solution system is realized. The main technical route is as follows: recycling of iron is realized by extracting and recovering iron; the separation of acid system tin is realized by adopting a directional separation technology; a novel extraction agent-sulfuric acid reverse extraction system is adopted for recovering indium, and green extraction of indium is achieved; germanium is extracted through extraction; preparing a zinc chloride product from the zinc-containing solution; through integration of the technologies, stepped recovery of multiple metals such as zinc, tin, indium, germanium and iron in the solution is realized.

Description

Technical Field

[0001] The invention belongs to the technical field of metallurgy, and further belongs to the technical field of comprehensive recycling and utilization, and specifically relates to a method for cascading recovery of iron, tin, indium, germanium and zinc from hard zinc hydrochloric acid leaching solution. Background Art

[0002] Pyrometallurgy is a classic zinc smelting process. Currently, about 10% of zinc production capacity comes from pyrometallurgy. Closed blast furnace zinc smelting (ISP) and electric furnace zinc smelting are the main pyrometallurgy methods. Among them, my country has built 4 ISP blast furnace zinc smelting production lines (Shaoguan, Huludao, Baiyin, Baoji Dongling); while electric furnace zinc smelting has relatively low investment, short process, simple operation, and no outstanding environmental protection problems. In the past ten years, it has been continuously developed in remote provinces and regions such as Yunnan, Guizhou, Sichuan, Shaanxi, Gansu, Ningxia, and Qinghai where there are zinc ore resources, sufficient electricity, and low costs. At present, more than 40 factories in the country have built and put into production 98 electric furnaces, with a total installed power of 232MW and an annual zinc output of 300,000 to 350,000 tons. The crude zinc obtained by pyrometallurgy is refined by the New Jersey process to obtain refined zinc. Hard zinc is an intermediate product of pyrometallurgy. It contains lead, iron, tin, and most of the rare and precious metals such as indium, germanium, and silver in the process. It is a secondary resource with high added value. Therefore, it is very necessary to develop a product that can solve the above-mentioned technical problems. Summary of the invention

[0003] The object of the present invention is to provide a method for stepwise recovery of iron, tin, indium, germanium and zinc from hard zinc hydrochloric acid leaching solution.

[0004] The object of the present invention is achieved in that the method for stepwise recovery of iron, tin, indium, germanium and zinc from hard zinc hydrochloric acid leachate comprises iron extraction, directional separation, indium extraction, germanium extraction and post-treatment steps, specifically comprising: A. Iron extraction: 1) The hard zinc hydrochloric acid leaching solution is extracted by using a TBP+n-octanol+sulfonated kerosene extraction system to obtain an organic phase a and an indium tin germanium zinc solution b; 2) The organic phase a is stripped of iron using an oxalic acid solution to obtain an organic phase c and a high-iron solution d; the organic phase c is returned to step 1) for recycling; the high-iron solution d is concentrated and crystallized to obtain a ferric oxalate product; B. Directional separation: Add separation reagent to indium tin germanium zinc solution b, react at a temperature of 40-80°C for 0.5-4h, filter the slurry to obtain tin-rich slag e and tin-removed liquid f; the tin-rich slag e is incorporated into lead pyrometallurgy to obtain lead-tin alloy, which can be further recovered to obtain metallic tin; C. Indium extraction: P204+Cyaner 923+TRPO+sulfonated kerosene novel extraction system is added to the tin-removed liquid f to obtain an organic phase g and an indium-extracted zinc-germanium solution h; the organic phase g is subjected to a stripping, neutralization-replacement-alkali fusion impurity removal process to obtain a crude indium product; D. Germanium extraction: adding modified isohydroxamic acid + N235 + sulfonated kerosene system to the zinc-germanium solution h after indium extraction to obtain a germanium-loaded organic phase i and a germanium-extracted zinc solution j; the germanium-loaded organic phase i is stripped and hydrolyzed to precipitate germanium to obtain a germanium dioxide product; E. Post-treatment: The zinc solution j after germanium extraction is evaporated and crystallized under reduced pressure to obtain zinc chloride product.

[0005] The specific operations are as follows: (1) Separation and recycling of iron. 1 , the iron was extracted using TBP + n-octanol + sulfonated kerosene extraction system, step I: extraction system O 1 The composition is TBP 10-50%, n-octanol 1-10%, sulfonated kerosene 89-40%, organic phase (O): aqueous phase (A) = 1:1-3, extraction stage 3-7, and iron-loaded organic phase O is obtained. 2 Indium tin germanium zinc solution after mining and extraction of iron 2 ; Step II: Loading iron organic phase O 2 The iron-loaded organic phase O was washed with water at a ratio of O:A = 1:1 to obtain the washed iron-loaded organic phase O 3 ; Step III: Loading iron organic phase O 3 Oxalic acid solution is used to strip iron, oxalic acid solution S 3 The concentration is 0.5~3mol / L, organic phase (O): aqueous phase (A) = 1~3:1, the stripping stage is 2~6, and the stripping organic phase O is obtained. 4 and high iron solution S 4 , O 4 Return to step Ⅰ for recycling; step Ⅳ: high iron solution S 4 The liquid was concentrated and crystallized to obtain the iron oxalate product P 1 .

[0006] (2) Directional separation and recovery of tin. Step V: Indium, tin, germanium and zinc solution S after iron extraction 2 The tin is selectively precipitated by directional separation. By adding separation reagent E (composed of sodium chlorate, high-purity zinc oxide powder, and polyacrylamide), the reaction temperature is 40-80°C and the amount of reagent E added is 0.5-10g / L. The slurry is filtered to obtain tin-rich slag Z 1 And the detinning liquid S 5 . Tin-rich slag Z 1 And incorporated into the lead pyrometallurgy smelting and washing to obtain lead-tin alloy, which can be further recovered to obtain metallic tin. 5 Hydrochloric acid concentration 5~30g / L.

[0007] (3) Green extraction of indium. Solution S after tin removal 5Mainly containing indium, germanium, and zinc, step VI: using a new extraction system of P204+Cyaner 923+TRPO+sulfonated kerosene to extract indium, the extraction system O 5 The composition is P204 20~50%, Cyaner 923 1~15%, TRPO 5~10%, sulfonated kerosene 74~25%, organic phase (O): aqueous phase (A) = 1:1~5, extraction stage 3~7, and indium-loaded organic phase O is obtained. 6 Zinc germanium solution S after mining and extraction of indium 6 ; Step VII: Loading indium organic phase O 6 Wash with water at a ratio of O:A = 1~1 to obtain the iron-loaded organic phase O after washing. 7 ; Step VIII: Loading indium organic phase O 7 Indium is stripped using sulfuric acid solution, sulfuric acid solution S 7 The concentration is 1~3mol / L, organic phase (O): aqueous phase (A) = 1:5~1, the stripping stage is 2~6, and the stripping organic phase O is obtained. 8 and indium-rich solution S 8 , O 8 After regeneration, return to step VI for recycling; Step IX: Indium-rich solution S 8 After the classic neutralization-replacement-alkali melting process, the crude indium product P is obtained. 2 .

[0008] (4) Recovery of germanium. Zinc-germanium solution S after indium extraction 6 Step X: Extracting germanium with a modified isohydroxamic acid + N235 + sulfonated kerosene system, wherein the extraction system O 9 The composition is modified isohydroxamic acid 10-30%, N235 5-15%, sulfonated kerosene 85-55%, and the germanium-loaded organic phase O 10 and zinc solution S after extraction of germanium 9 ; Step Ⅺ: Loading germanium organic phase O 10 Using ammonium chloride solution S 10 Stripping, ammonium chloride solution S 10 Concentration 0.5mol / L~2mol / L, organic phase (O): aqueous phase (A) = 1:5~1, stripping stage 2~5, obtain stripping organic phase O 11 and germanium chloride solution S 11 , O 1 After regeneration, return to step X for recycling; Step XII: germanium chloride solution S 11 , through the classic hydrolysis germanium precipitation technology to obtain the germanium dioxide product P 3 .

[0009] (5) Recovery of zinc. Zinc solution S after germanium extraction 9 It mainly contains zinc chloride, and other impurities are at a lower level. Zinc chloride product P is prepared by vacuum evaporation and crystallization.4 .

[0010] The technical solution provided by the present invention is a method for cascade recovery of iron, tin, indium, germanium and zinc from hard zinc hydrochloric acid leachate. Through technical innovation and process integration, the comprehensive recovery of multiple metals such as indium, tin, germanium, iron and zinc in the complex solution system is achieved. The main technical routes are as follows: using extraction to recover iron to realize the resource utilization of iron; using directional separation technology to achieve the separation of tin in the acidic system; using a new extractant-sulfuric acid stripping system to recover indium and realize the green extraction of indium; using extraction to achieve the extraction of germanium; preparing zinc chloride products with zinc-containing solutions; and realizing the cascade recovery of zinc, tin, indium, germanium and iron in the solution through the above-mentioned technical integration.

[0011] In the present invention, hard zinc is leached by hydrochloric acid oxidation, and the typical components of the leaching solution are: hydrochloric acid concentration 0.5mol / L~8mol / L, Zn30~200g / L, Fe5~80g / L, Sn1~15g / L, In1~10g / L, Ge0.5~10g / L.

[0012] Compared with the existing recovery technology of indium, iron, tin, germanium, zinc and the like in hydrochloric acid solution, the advantages of the present invention are: (1) A new extraction system of P204+Cyaner 923+TRPO+sulfonated kerosene was constructed - indium-loaded organic phase sulfuric acid stripping, which achieved efficient indium extraction and efficient stripping in the sulfuric acid system. This solved the problem of high chlorine wastewater in the traditional classic P204 extraction-6N hydrochloric acid stripping system and the problem of low indium stripping rate in the P204 extraction-sulfuric acid stripping system, thus achieving green and efficient extraction of indium.

[0013] (2) Through technological innovation and process integration, combined with extraction separation and chemical selective separation technology, multiple metals such as iron, tin, indium, germanium, and zinc are extracted step by step from the hard zinc hydrochloric acid leachate, realizing the cascade recycling of multiple metals, which has the advantages of high metal recovery rate and strong process adaptability. BRIEF DESCRIPTION OF THE DRAWINGS

[0014] Figure 1 It is a schematic diagram of the process flow of the present invention. DETAILED DESCRIPTION

[0015] The present invention is further described below in conjunction with the embodiments, but the present invention is not limited in any way. Any changes or substitutions made based on the teachings of the present invention belong to the protection scope of the present invention.

[0016] The method for stepwise recovery of iron, tin, indium, germanium and zinc from hard zinc hydrochloric acid leachate of the present invention comprises iron extraction, directional separation, indium extraction, germanium extraction and post-treatment steps, specifically comprising: A. Iron extraction: 1) The hard zinc hydrochloric acid leaching solution is extracted by using a TBP+n-octanol+sulfonated kerosene extraction system to obtain an organic phase a and an indium tin germanium zinc solution b; 2) The organic phase a is stripped of iron using an oxalic acid solution to obtain an organic phase c and a high-iron solution d; the organic phase c is returned to step 1) for recycling; the high-iron solution d is concentrated and crystallized to obtain a ferric oxalate product; B. Directional separation: Add separation reagent to indium tin germanium zinc solution b, react at a temperature of 40-80°C for 0.5-4h, filter the slurry to obtain tin-rich slag e and tin-removed liquid f; the tin-rich slag e is incorporated into lead pyrometallurgy to obtain lead-tin alloy, which can be further recovered to obtain metallic tin; C. Indium extraction: P204+Cyaner 923+TRPO+sulfonated kerosene novel extraction system is added to the tin-removed liquid f to obtain an organic phase g and an indium-extracted zinc-germanium solution h; the organic phase g is subjected to a stripping, neutralization-replacement-alkali fusion impurity removal process to obtain a crude indium product; D. Germanium extraction: adding modified isohydroxamic acid + N235 + sulfonated kerosene system to the zinc-germanium solution h after indium extraction to obtain a germanium-loaded organic phase i and a germanium-extracted zinc solution j; the germanium-loaded organic phase i is stripped and hydrolyzed to precipitate germanium to obtain a germanium dioxide product; E. Post-treatment: The zinc solution j after germanium extraction is evaporated and crystallized under reduced pressure to obtain zinc chloride product.

[0017] A. The volume ratio of TBP, n-octanol and sulfonated kerosene in the TBP+n-octanol+sulfonated kerosene extraction system described in step 1) is (10-50): (1-10): (40-89).

[0018] A. The concentration of the oxalic acid solution in step 2) is 0.5~3 mol / L.

[0019] The separation reagent described in step B is composed of sodium chlorate, high-purity zinc oxide powder and polyacrylamide.

[0020] The mass ratio of the sodium chlorate, high-purity zinc oxide powder and polyacrylamide is 5-15:83-94:1-2.

[0021] In the P204+Cyaner 923+TRPO+sulfonated kerosene system described in step C, the volume ratio of P204, Cyaner 923, TRPO and sulfonated kerosene is (20-50):(1-15):(5-10):(25-74).

[0022] In the modified isohydroxamic acid+N235+sulfonated kerosene system described in step D, the volume ratio of modified isohydroxamic acid, N235 and sulfonated kerosene is (10-30): (5-15): (55-85).

[0023] The present invention is further described below with specific implementation cases: Example 1 Composition of hard zinc hydrochloric acid leaching solution: hydrochloric acid concentration 89g / L, Zn 130.5g / L, Fe 58.6g / L, Sn 8.2g / L, In 3.6g / L, Ge 2.5g / L.

[0024] (1) Iron recovery. Using TBP 30% + n-octanol 10% + sulfonated kerosene 60%, the iron extraction rate reached 99.82% at a relative ratio of O / A = 1:1 and an extraction stage of 2; the iron-loaded organic phase was stripped with 1N oxalic acid, and under the conditions of a relative ratio of O:A = 3:1 and a stripping stage of 5, the iron ion concentration of the stripping solution was 110.2 g / L; the stripping solution was concentrated and crystallized to obtain a ferric oxalate product with a grade of 99.53%.

[0025] (2) Directional separation of tin. Add 6 g / L of separation reagent (sodium chlorate: high-purity zinc oxide powder: polyacrylamide = 6:94:1), under the conditions of 60°C and 2 h, the end point hydrochloric acid concentration is 55 g / L, the tin precipitation rate is 99.51%, and the tin grade in the tin enriched product reaches 42.17%.

[0026] (3) Recovery of indium. After tin removal, indium was extracted from the liquid using a new extraction system of P204 30% + Cyanex 923 5% + TRPO 5% + sulfonated kerosene 60%. Under the conditions of relative O:A=1:5 and extraction level 4, the indium extraction rate was 99.58%. The indium-loaded organic phase was stripped using 3 mol sulfuric acid solution. Under the conditions of relative O:A=15:1 and stripping level 7, the indium stripping rate reached 98.25%. After neutralization-replacement-alkali fusion and impurity removal, the indium-rich liquid was prepared to obtain a crude indium product with a content of 99.95%.

[0027] (4) Recovery of germanium. The indium raffinate was extracted with a modified isohydroxamic acid 25% + N235 15% + sulfonated kerosene 60% system. Under the conditions of phase ratio O:A=1:2 and extraction level 5, the germanium extraction rate reached 99.35%. The organic phase loaded with germanium was stripped with ammonium chloride solution. Under the conditions of ammonium chloride concentration of 1 mol, phase ratio O:A=2:1, and stripping level 3, the germanium stripping rate was 97.62%, and the germanium ion concentration of the stripping solution was 9.8 g / L. Germanium dioxide was prepared by precipitation with ammonia water, and the grade of germanium dioxide reached 98.78%.

[0028] (5) Recovery of zinc. The germanium extract contains 128 g / L of zinc. After concentration and crystallization, zinc chloride product is obtained, and the grade of zinc chloride reaches 99.44%.

[0029] Example 2 Composition of hard zinc hydrochloric acid leaching solution: hydrochloric acid concentration 89g / L, Zn 130.5g / L, Fe 58.6g / L, Sn 8.2g / L, In 3.6g / L, Ge 2.5g / L.

[0030] (1) Iron recovery. Using TBP45% + n-octanol 5% + sulfonated kerosene 50%, the iron extraction rate reached 99.82% at a relative ratio of O / A = 1:2 and an extraction stage of 2; the iron-loaded organic phase was stripped with 2N oxalic acid, and under the conditions of a relative ratio of O:A = 3:1 and a stripping stage of 5, the iron ion concentration of the stripping solution was 140.2 g / L; the stripping solution was concentrated and crystallized to obtain a ferric oxalate product with a grade of 99.73%.

[0031] (2) Directional separation of tin. Add 6 g / L of separation reagent (sodium chlorate: high-purity zinc oxide powder: polyacrylamide = 6:94:1), under the conditions of 60°C and 2 h, the end point hydrochloric acid concentration is 57 g / L, the tin precipitation rate is 99.27%, and the tin grade in the tin enriched product reaches 41.89%.

[0032] (3) Recovery of indium. After tin removal, indium was extracted from the liquid using a new extraction system of P204 35% + Cyanex 923 7% + TRPO 3% + sulfonated kerosene 50%. Under the conditions of relative O:A = 1:10 and extraction level 4, the indium extraction rate was 99.12%. The organic phase loaded with indium was stripped using 3 mol sulfuric acid solution. Under the conditions of relative O:A = 15:1 and stripping level 7, the indium stripping rate reached 98.31%. After neutralization-replacement-alkali fusion and impurity removal, the indium-rich liquid was prepared to obtain a crude indium product with a content of 99.95%.

[0033] (4) Recovery of germanium. The indium raffinate was extracted with a modified isohydroxamic acid 40% + N235 15% + sulfonated kerosene 45% system. Under the conditions of phase ratio O:A = 1:5 and stripping level 3, the germanium stripping rate reached 99.17%. The organic phase loaded with germanium was stripped with an ammonium chloride solution. Under the conditions of ammonium chloride concentration of 1 mol, phase ratio O:A = 1:1, and stripping level 5, the germanium stripping rate was 98.57%, and the germanium ion concentration of the stripping solution was 13.5 g / L. Germanium dioxide was prepared by precipitation with ammonia water, and the grade of germanium dioxide reached 98.75%.

[0034] (5) Recovery of zinc. The germanium extract contains 125 g / L of zinc. After concentration and crystallization, zinc chloride product is obtained, and the grade of zinc chloride reaches 99.15%.

[0035] Example 3 Composition of hard zinc hydrochloric acid leaching solution: hydrochloric acid concentration 160g / L, Zn 150g / L, Fe 76g / L, Sn 12g / L, In 5.2g / L, Ge 3.4g / L.

[0036] (1) Iron recovery. Using TBP 30% + n-octanol 10% + sulfonated kerosene 60%, the iron extraction rate reached 99.20% under the conditions of O / A = 1:1 and extraction level 3; the iron-loaded organic phase was stripped with 1N oxalic acid, and under the conditions of O:A = 3:1 and stripping level 5, the iron ion concentration of the stripping solution was 130.2 g / L; the stripping solution was concentrated and crystallized to obtain a ferric oxalate product with a grade of 99.67%.

[0037] (2) Directional separation of tin. Add 12 g / L of separation reagent (sodium chlorate: high-purity zinc oxide powder: polyacrylamide = 9:90:1), under the conditions of 60°C and 2 h, the end point hydrochloric acid concentration is 32 g / L, the tin precipitation rate is 99.78%, and the tin grade in the tin enriched product reaches 40.36%.

[0038] (3) Recovery of indium. After tin removal, indium was extracted from the liquid using a new extraction system of P204 30% + Cyanex 923 5% + TRPO 5% + sulfonated kerosene 60%. Under the conditions of relative O:A=1:5 and extraction level 5, the indium extraction rate was 99.35%. The indium-loaded organic phase was stripped using 3 mol sulfuric acid solution. Under the conditions of relative O:A=15:1 and stripping level 7, the indium stripping rate reached 98.25%. After neutralization-replacement-alkali fusion and impurity removal, the indium-rich liquid was prepared to obtain a crude indium product with a content of 99.95%.

[0039] (4) Recovery of germanium. The indium raffinate was extracted with a modified isohydroxamic acid 25% + N235 15% + sulfonated kerosene 60% system. Under the conditions of phase ratio O:A=1:2 and extraction level 5, the germanium extraction rate reached 98.87%. The organic phase loaded with germanium was stripped with ammonium chloride solution. Under the conditions of ammonium chloride concentration of 1 mol, phase ratio O:A=2:1, and stripping level 3, the germanium stripping rate was 98.25%, and the germanium ion concentration of the stripping solution was 12.5 g / L. Germanium dioxide was prepared by precipitation with ammonia water, and the grade of germanium dioxide reached 98.34%.

[0040] (5) Recovery of zinc. The germanium extract contains 146 g / L of zinc. After concentration and crystallization, zinc chloride product is obtained, and the grade of zinc chloride reaches 99.38%.

[0041] Example 4 Composition of hard zinc hydrochloric acid leaching solution: hydrochloric acid concentration 160g / L, Zn 150g / L, Fe 76g / L, Sn 12g / L, In 5.2g / L, Ge 3.4g / L.

[0042] (1) Iron recovery. Using TBP45% + n-octanol 5% + sulfonated kerosene 50%, the iron extraction rate reached 99.15% at a relative ratio of O / A = 1:2 and an extraction stage of 2; the iron-loaded organic phase was stripped with 2N oxalic acid, and the iron ion concentration of the stripping solution was 144.5 g / L at a relative ratio of O:A = 3:1 and a stripping stage of 5; the stripping solution was concentrated and crystallized to obtain a ferric oxalate product with a grade of 99.56%.

[0043] (2) Directional separation of tin. Add 12 g / L of separation reagent (sodium chlorate: high-purity zinc oxide powder: polyacrylamide = 9:90:1), under the conditions of 60°C and 2 h, the end point hydrochloric acid concentration is 35 g / L, the tin precipitation rate is 99.62%, and the tin grade in the tin enriched product reaches 40.55%.

[0044] (3) Recovery of indium. After tin removal, indium was extracted from the liquid using a new extraction system of P204 35% + Cyanex 923 7% + TRPO 3% + sulfonated kerosene 50%. Under the conditions of relative O:A = 1:10 and extraction level 4, the indium extraction rate was 98.61%. The indium-loaded organic phase was stripped using 3 mol sulfuric acid solution. Under the conditions of relative O:A = 15:1 and stripping level 7, the indium stripping rate reached 98.54%. After neutralization-replacement-alkali fusion and impurity removal, the indium-rich liquid was prepared to obtain a crude indium product with a content of 99.95%.

[0045] (4) Recovery of germanium. The indium raffinate was extracted with a modified isohydroxamic acid 40% + N235 15% + sulfonated kerosene 45% system. Under the conditions of phase ratio O:A = 1:5 and stripping level 3, the germanium stripping rate reached 98.77%. The organic phase loaded with germanium was stripped with an ammonium chloride solution. Under the conditions of ammonium chloride concentration of 1 mol, phase ratio O:A = 1:1, and stripping level 5, the germanium stripping rate was 98.52%, and the germanium ion concentration of the stripping solution was 15.8 g / L. Germanium dioxide was prepared by precipitation with ammonia water, and the grade of germanium dioxide reached 98.92%.

[0046] (5) Recovery of zinc. The germanium extract contains 126 g / L of zinc. After concentration and crystallization, zinc chloride product is obtained, and the grade of zinc chloride reaches 99.48%.

Claims

1. A method for stepwise recovery of iron, tin, indium, germanium and zinc from hard zinc hydrochloric acid leaching solution, characterized in that: The method for stepwise recovery of iron, tin, indium, germanium and zinc from hard zinc hydrochloric acid leachate comprises iron extraction, directional separation, indium extraction, germanium extraction and post-treatment steps, specifically comprising: A. Iron extraction: 1) The hard zinc hydrochloric acid leaching solution is extracted by using a TBP+n-octanol+sulfonated kerosene extraction system to obtain an organic phase a and an indium tin germanium zinc solution b; 2) The organic phase a is stripped of iron using an oxalic acid solution to obtain an organic phase c and a high-iron solution d; the organic phase c is returned to step 1) for recycling; the high-iron solution d is concentrated and crystallized to obtain a ferric oxalate product; B. Directional separation: Add separation reagent to indium tin germanium zinc solution b, react at a temperature of 40-80°C for 0.5-4h, filter the slurry to obtain tin-rich slag e and tin-removed liquid f; the tin-rich slag e is incorporated into lead pyrometallurgy to obtain lead-tin alloy, which can be further recovered to obtain metallic tin; C. Indium extraction: P204+Cyaner 923+TRPO+sulfonated kerosene novel extraction system is added to the tin-removed liquid f to obtain an organic phase g and an indium-extracted zinc-germanium solution h; the organic phase g is subjected to a stripping, neutralization-replacement-alkali fusion impurity removal process to obtain a crude indium product; D. Germanium extraction: adding modified isohydroxamic acid + N235 + sulfonated kerosene system to the zinc-germanium solution h after indium extraction to obtain a germanium-loaded organic phase i and a germanium-extracted zinc solution j; the germanium-loaded organic phase i is stripped and hydrolyzed to precipitate germanium to obtain a germanium dioxide product; E. Post-treatment: The zinc solution j after germanium extraction is evaporated and crystallized under reduced pressure to obtain zinc chloride product.

2. The method for stepwise recovery of iron, tin, indium, germanium and zinc from hard zinc hydrochloric acid leachate according to claim 1, characterized in that: A. The volume ratio of TBP, n-octanol and sulfonated kerosene in the TBP+n-octanol+sulfonated kerosene extraction system described in step 1) is (10-50): (1-10): (40-89).

3. The method for stepwise recovery of iron, tin, indium, germanium and zinc from hard zinc hydrochloric acid leachate according to claim 1, characterized in that: A. The concentration of the oxalic acid solution in step 2) is 0.5~3 mol / L.

4. The method for stepwise recovery of iron, tin, indium, germanium and zinc from hard zinc hydrochloric acid leachate according to claim 1, characterized in that: The separation reagent described in step B is composed of sodium chlorate, high-purity zinc oxide powder and polyacrylamide.

5. The method for stepwise recovery of iron, tin, indium, germanium and zinc from hard zinc hydrochloric acid leachate according to claim 4, characterized in that: The mass ratio of the sodium chlorate, high-purity zinc oxide powder and polyacrylamide is 5-15:83-94:1-2.

6. The method for stepwise recovery of iron, tin, indium, germanium and zinc from hard zinc hydrochloric acid leachate according to claim 1, characterized in that: In the P204+Cyaner 923+TRPO+sulfonated kerosene system described in step C, the volume ratio of P204, Cyaner 923, TRPO and sulfonated kerosene is (20-50):(1-15):(5-10):(25-74).

7. The method for stepwise recovery of iron, tin, indium, germanium and zinc from hard zinc hydrochloric acid leaching solution according to claim 1, characterized in that: In the modified isohydroxamic acid+N235+sulfonated kerosene system described in step D, the volume ratio of modified isohydroxamic acid, N235 and sulfonated kerosene is (10-30): (5-15): (55-85).

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