A method for synergistic extraction of gallium and germanium concentrates

Abstract

The present application relates to a kind of methods for preparing gallium and germanium concentrate by synergistic extraction.The method comprises the following steps: S1: the high acid leaching solution containing gallium and germanium is extracted by complex organic phase liquid-liquid extraction I;The complex organic phase includes: the substance of formula (1), formula (21), formula (22) and formula (3) structure;S2: the loaded organic phase obtained in S1 is stripped I by solution of formula (4), and the stripping solution I containing gallium and iron is obtained;S3: S31: the loaded organic phase obtained in S2 is stripped II by solution of formula (5), and the stripping solution II of germanium is obtained;S32: ammonia is introduced into the stripping solution II of germanium in S31, and the reaction is carried out to the end point, and the germanium concentrate is obtained by filtering and drying calcining;S4: S41: the stripping solution I containing gallium and iron obtained in S2 is added with ion precipitant of formula (6), and the gallium and iron concentrate I is obtained by filtering;S42: sodium hydroxide solution is added to the gallium and iron concentrate I of S41, and the metal gallium is prepared by filtering, enriching filtrate and electrowinning.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of scattered gallium metal recovery, in particular to a method for preparing gallium and germanium concentrates by synergistic extraction. BACKGROUND

[0002] At present, gallium and germanium are important scattered metals, 90% of the gallium metal comes from aluminum smelting, and the rest comes from zinc smelting and coal; the recovery of germanium mainly comes from zinc smelting and coal, accounting for about 50% each.

[0003] In order to obtain a high gallium and germanium leaching rate, the gallium and germanium rich slag obtained in the zinc smelting process needs to be subjected to high acid leaching. The separation and enrichment of gallium and germanium from the high acid leaching solution containing gallium and germanium is the most critical core technology. At present, the main process routes for recovering gallium and germanium from the high acid leaching solution containing gallium and germanium are: (1) tannin precipitates germanium-acetamide extracts gallium; (2) P204+YW100 synergistic extraction of gallium and germanium; (3) hematite-tertiary carbon carboxylic acid extraction of gallium; (4) chlorination distillation of germanium-ethyl ether extraction of gallium; (5) chlorination distillation of germanium-TBP extraction of gallium; (6) LIX63 high acid extraction of germanium-low acid phosphoric acid ester extraction of gallium.

[0004] Although the above various process routes can realize the separation and enrichment of gallium and germanium, these processes still have many shortcomings: (1) tannin precipitates germanium and chlorination distillation germanium have a greater impact on the zinc smelting process, and tannin is expensive, resulting in high production cost; (2) in the P204+YW100 synergistic extraction, the gallium extraction rate is low under high acid, and an acid adjusting process is needed, which not only consumes a large amount of neutralizing agent, but also makes the acid in the leaching solution unable to be recycled, in addition, YW100 has high water solubility and needs to be constantly supplemented, and the soluble organic matter has a great impact on the zinc smelting process, resulting in high cost; (3) before extraction by tertiary carbon carboxylic acid, an iron reduction process is needed, which consumes a large amount of reducing agent, and the conditions are difficult to control, making it difficult to be applied in industry; (4) chlorination distillation germanium-extraction gallium both involve chlorine-containing solutions, and a large amount of chloride ions cause harm to the zinc smelting process, and the equipment is severely corroded, and the operating environment is poor; (5) LIX63 extracts germanium under high acid, and there are problems such as fast degradation of the extractant, high cost of the extractant, difficulty in procurement in China, and the need to add chloride ions when extracting gallium, which causes the raffinate to be difficult to return to the zinc system. In summary, the existing processes for extracting and recovering gallium and germanium from high acid gallium and germanium leaching solution generally have high production cost, introduce a large amount of harmful elements such as chloride ions or organic matter, and limit their application in the zinc smelting system. SUMMARY

[0005] Based on this, the purpose of the present application is to solve the above-mentioned shortcomings and deficiencies of the prior art, and to provide a method for preparing metal gallium and germanium concentrates by synergistic extraction from high-acid leaching solution containing gallium and germanium, which realizes one-step gallium-germanium extraction, step-by-step stripping separation and enrichment of gallium and germanium, does not introduce harmful impurities containing chlorine, has simple process method, low production cost and wide industrial application value.

[0006] A method for preparing metal gallium and germanium concentrates by synergistic extraction, comprising the following steps:

[0007] Step S1: the high-acid leaching solution containing gallium and germanium is subjected to liquid-liquid extraction I with a complex organic phase; the complex organic phase comprises the following components: 2 vol% to 30 vol% of hydroxamic chelate extractant of formula (1), 20 vol% to 30 vol% of alkyl phenoxy phosphate extractant, 5 vol% to 10 vol% of alcohol modifier of formula (3), and the balance is kerosene diluent; wherein,

[0008] Formula (1):

[0009]

[0010] Wherein, R1 is one of C9-C18 alkyl;

[0011] The alkyl phenoxy phosphate extractant comprises 88-90 mol% of monophosphate ester of formula (21) and 12-10 mol% of bisphosphate ester of formula (22);

[0012] Formula (21):

[0013]

[0014] Formula (22):

[0015]

[0016] Wherein, in formula (21) and formula (22), R2 is one of C8-C12 alkyl;

[0017] Formula (3):

[0018]

[0019] Step S2: the loaded organic phase obtained in step S1 is subjected to stripping I with a solution of formula (4) to obtain a loaded organic phase and a stripping solution I of gallium and iron;

[0020] Formula (4):

[0021]

[0022] Wherein, M4 is H +, Na + , K + , NH4 + ;

[0023] Step S3 comprises:

[0024] Step S31: stripping solution II of germanium is obtained by stripping II of the loaded organic phase obtained in step S2 with a solution of formula (5);

[0025] Formula (5):

[0026]

[0027] wherein M5 is NH4 + ;

[0028] Step S32: liquid ammonia is introduced into the stripping solution II of germanium obtained in step S3, and the reaction is neutralized to a final pH value of 8.5-10, and germanium concentrate II is obtained by filtration, and germanium concentrate II is dried and calcined to obtain germanium concentrate;

[0029] Step S4 comprises

[0030] Step S41: an ionic precipitant of formula (6) is added to the stripping solution I containing gallium and iron obtained in step S2, and gallium and iron concentrate I is obtained by filtration;

[0031] Formula (6):

[0032]

[0033] wherein M3 is H + , Na + , K + , NH4 + ;

[0034] Step S42: sodium hydroxide solution is added to the gallium and iron concentrate I obtained in step S4, and the gallium concentration in the filtrate is measured or the gallium concentration is recycled to 20-80 g / L before electrodeposition to prepare metallic gallium.

[0035] The method for preparing gallium and germanium concentrates by synergistic extraction according to the application is characterized in that: in step S1, the high-gallium-and-germanium-containing acid leaching solution is subjected to liquid-liquid extraction I by using a complex organic phase containing 2vol%-30vol% hydroxamic chelate extractant with the structure of formula (1), 20vol%-30vol% alkyl phenoxy phosphonate extractant mixed with 12-10mol% bisphosphonate ester with the structure of formula (22) and 5vol%-10vol% alcohol modifier with the structure of formula (3), so that the gallium and germanium in the high-gallium-and-germanium-containing acid leaching solution are enriched into the loaded organic phase in one step by liquid-liquid extraction I. Then, the gallium and germanium are extracted and separated from the loaded organic phase by stepwise stripping: first, in step S2, the loaded organic phase after the liquid-liquid extraction I in step S1 is subjected to stripping I by using a solution containing a substance with the structure of formula (4), to obtain a gallium and iron stripping solution I, so that the germanium remains in the loaded organic phase obtained after the stripping I, and the gallium and germanium are separated.

[0036] In step S3, in step S31, the loaded organic phase obtained after the stripping I in step S2 is subjected to stripping II by using a solution containing a substance with the structure of formula (5), to obtain a germanium stripping solution II. In step S32, the germanium stripping solution II obtained in step S31 is subjected to stripping II by passing liquid ammonia into the stripping solution II, to obtain a germanium enrichment II. The germanium enrichment II is dried and calcined to obtain a germanium concentrate.

[0037] In step S4, in step S41, the gallium and iron stripping solution I obtained after the stripping I in step S2 is added with an ionic precipitant with the structure of formula (6), so that the gallium and iron are precipitated, and a gallium and iron enrichment I is obtained by filtration. In step S6, the gallium and iron enrichment I is added with a high-concentration sodium hydroxide solution to precipitate the gallium and iron in the gallium and iron enrichment I, and the generated gallium hydroxide is dissolved, and a sodium gallate solution and iron residue are obtained by filtration. The gallium concentration in the sodium gallate solution is measured, or a high-concentration sodium gallate solution is obtained by cyclic enrichment, and then metal gallium is prepared by electrodeposition.

[0038] The method for preparing gallium and germanium concentrates by synergistic extraction according to the application realizes the extraction and separation and enrichment of gallium and germanium from high-acid leaching solution by one-step extraction and stepwise stripping, and the extraction rate of gallium and germanium is greater than 98%. The method for preparing gallium and germanium concentrates by synergistic extraction according to the application has the advantages of simple and efficient process flow and high product metal recovery rate.

[0039] Further, in step S1, the high-acid leaching solution containing gallium and germanium contains 0.1-3 g / L of gallium and 0.1-3 g / L of germanium, and the main impurities include Fe, Cu, Zn, Sb, As, Co and Ni, wherein the concentration of Cu is less than 40 g / L, the concentration of Zn is less than 200 g / L, and the concentration of the remaining main impurities is less than 5 g / L; the high-acid leaching solution containing gallium and germanium is a gallium and germanium-containing sulfuric acid leaching solution, and the concentration of sulfuric acid is in the range of 10-130 g / L.

[0040] Further, in step S1, the extraction temperature of liquid-liquid extraction I is 20-60°C, and the phase ratio O / A is 1:1-5:1; the extraction time is 2-30 min, and the extraction stage is 2-5 stages.

[0041] Further, in step S2, the stripping temperature in stripping I is 20-60°C, the phase ratio O / A is 1:1-1:10, the stripping time is 10-30 min, and the stripping stage is 2-5 stages.

[0042] Further, in step S2, the structure substance of formula (4) is a gallium and iron stripping agent, which is an organic acid or an organic salt; in step S2, the concentration of the solution of formula (4) used in stripping I is 1.0-2.0 mol / L.

[0043] Further, in step S31, the structure substance of formula (5) is a germanium stripping agent, which is an organic salt, and the concentration of the solution of formula (5) used in stripping II is 1.0-3.0 mol / L.

[0044] Further, in step S31, the stripping temperature in stripping II is 30-65°C, the phase ratio O / A is 1:1-1:10; the stripping time is 15-30 min, and the stripping stage is 2-5 stages. The loaded organic phase after stripping II can be regenerated and recycled for liquid-liquid extraction I in step S2.

[0045] Further, in step S32, the germanium stripping solution II is introduced into liquid ammonia, the reaction time is 60-120 min, and the reaction temperature is 40-80°C; the filtered germanium concentrate II is dried and calcined, the calcination temperature is 450-650°C, and the calcination time is greater than 2 h to obtain germanium concentrate; and the filtered filtrate can be used for recycling stripping I.

[0046] Further, in step S41, the addition amount of the ion precipitating agent of formula (6) is in the molar ratio of 1.5:1-3:1 to the sum of the total amount of gallium and iron ions in the gallium and iron stripping solution I, the reaction time is 10 min-60 min, and the reaction temperature is 10-80°C. The ion precipitating agent of formula (6) is used for ion precipitation in the gallium and iron stripping solution I, the solid effective component is 95%, or the aqueous effective component is greater than 50%. After filtering to obtain the gallium and iron concentrate I, the filtrate is returned to stripping I for recycling stripping.

[0047] Further, in step S42, the concentration of the sodium hydroxide solution added to the gallium and iron concentrate I is 120-200 g / L, the liquid-solid ratio of the sodium hydroxide solution to the gallium and iron concentrate I is 4-8, the reaction temperature is 30-80℃, the reaction time is 1-4 h, the gallium concentration of the filtrate is measured, and the gallium is enriched and recycled to a gallium concentration of 20-80 g / L before being electro-deposited to prepare metallic gallium.

[0048] The present application adopts the above technical solution, and has the following advantages compared with the prior art.

[0049] (1) The method of the present application realizes the extraction and separation of gallium and germanium from the gallium and germanium-containing sulfuric acid leaching solution through one-step extraction (i.e. liquid-liquid extraction I) and stepwise stripping (i.e. stripping I and stripping II), and the extraction rates of gallium and germanium are both greater than 98%; the gallium and iron stripping solution I obtained after stripping I is subjected to precipitation enrichment of gallium and iron, and the precipitation rate is greater than 70%; the gallium and iron concentrate I obtained after neutralization and precipitation of the gallium and iron is recycled to an alkali solution, so that gallium and iron are separated, and the gallium is enriched and then electro-deposited to prepare metallic gallium, and the gallium grade is greater than 99.9%; the germanium stripping solution II obtained after stripping II is subjected to neutralization and precipitation in liquid ammonia to enrich germanium, and the germanium concentrate is prepared by drying and calcining, and the germanium grade is greater than 50%; both of the two stripping solutions are recycled after removing gallium and germanium, the consumption of stripping agent is low, the recovery rates of gallium and germanium are greater than 96%, the overall technology does not introduce other harmful impurities such as chlorine, the process is simple, the production cost is low, and the method has wide industrial application value.

[0050] (2) In the complex organic phase used in liquid-liquid extraction I, the hydroxamic chelating extractant with the structure of formula (1) has a long carbon chain and small water solubility, which meets the requirements of recycling; the alkyl phenoxy phosphate ester with the structures of formula (21) and formula (22) has strong acidity due to the electron-withdrawing effect of the benzene ring, can undergo hydrogen ionization in a high-acid system, and can exchange ions with gallium to achieve high-acid extraction without adjusting the acid.

[0051] (3) The gallium and iron stripping agent organic acid or organic salt solution with the structure of formula (4) is used for stripping I to obtain the gallium and iron stripping solution I, which solves the problem of stripping of alkyl phenoxy phosphate ester and avoids the problem of decomposition of hydroxamic acid extractant caused by high-acid stripping in the P204+YW100 system of the prior art.

[0052] (4) The gallium and iron stripping solution I is added with the ion precipitant with the structure of formula (6) to obtain the gallium and iron concentrate I, and the organic acid or organic salt in the gallium and iron stripping solution I is released so as to be recycled, thereby saving the operation cost.

[0053] In order to better understand and implement the present application, the present application will be described in detail below with reference to the accompanying drawings. BRIEF DESCRIPTION OF DRAWINGS

[0054] Figure 1 Process flow chart of the method for preparing metal gallium and germanium concentrate from high-acid gallium and germanium leaching solution by synergistic extraction according to the present application. DETAILED DESCRIPTION

[0055] The present application is further described below in conjunction with specific examples, but the scope of protection of the present application is not limited thereto.

[0056] The high-acid leaching solution containing gallium and germanium is industrially produced from zinc smelting process, and the main impurity elements in the leaching solution are Fe, Zn, Co, Ni, Cu, As, Cd, etc.

[0057] A method for preparing metal gallium and germanium concentrate from high-acid leaching solution containing gallium and germanium by synergistic extraction, please refer to the process flow chart of Figure 1 , including the following steps:

[0058] Step S1: The high-acid leaching solution containing gallium and germanium is subjected to liquid-liquid extraction I with a compounded organic phase, the extraction temperature is 20-60℃, the phase ratio O / A is 1:1-5:1; the extraction time is 2-30min, and the extraction stage is 2-5 stages; the compounded organic phase consists of the following components: 2%-30% of hydroxamic acid chelating extractant with structure of formula (1); 20%-30% of alkyl phenoxy phosphate extractant; 5%-10% of alcohol modifier with structure of formula (3), and the rest is kerosene diluent.

[0059] Formula (1):

[0060]

[0061] In the formula, R1 is one of C9-C18 alkyl;

[0062] The alkyl phenoxy phosphate extractant includes 88-90mol% of monophosphate ester of formula (21) and 12-10mol% of diphenyl phosphate of formula (22);

[0063] Formula (21):

[0064]

[0065] Formula (22):

[0066]

[0067] In the formula (21) and formula (22), R2 is one of C8-C12 alkyl;

[0068] Formula (3):

[0069]

[0070] The high-acid leaching solution containing gallium and germanium has a gallium concentration of 0.1-3 g / L and a germanium concentration of 0.1-3 g / L, and the main impurities in the high-acid leaching solution containing gallium and germanium include Fe, Cu, Zn, Sb, As, Co and Ni, wherein the Cu is less than 40 g / L, the Zn is less than 200 g / L, and the rest is less than 5 g / L.

[0071] In step S1, the high-acid leaching solution containing gallium and germanium is a sulfuric acid leaching solution containing gallium and germanium, and the sulfuric acid concentration is 10-130 g / L.

[0072] Step S2: The loaded organic phase after the liquid-liquid extraction I is subjected to stripping I using a solution containing a substance with the structure of formula (4) to obtain a loaded organic phase and a gallium and iron stripping solution I; the loaded organic phase after the stripping I is subjected to step S3, and the gallium and iron stripping solution I is subjected to step S4.

[0073] Formula (4):

[0074]

[0075] wherein M4 is H + , Na + , K + , NH4 + .

[0076] In step S2, the temperature of the stripping I is 20-60°C, the phase ratio O / A is 1:1-1:10, the stripping time is 10-30 min, and the stripping stages are 2-5 stages; the substance with the structure of formula (4) is a gallium and iron stripping agent, which is an organic acid or an organic salt, and the solution of formula (4) has a concentration of 1.0-2.0 mol / L.

[0077] Step S3:

[0078] In step S31, the loaded organic phase obtained in step S2 is subjected to stripping II using a solution containing a substance with the structure of formula (5) to obtain a germanium stripping solution II, and the organic phase after the stripping II is subjected to recycling extraction, and the germanium stripping solution II is subjected to step S32.

[0079] Formula (5):

[0080]

[0081] wherein M5 is NH4 + .

[0082] In step S31, the temperature of the stripping II is 30-65°C, the phase ratio O / A is 1:1-1:10, the stripping time is 15-30 min, and the stripping stages are 2-5 stages; the substance with the structure of formula (5) is a germanium stripping agent, which is an organic salt, and the solution of formula (5) has a concentration of 1.0-3.0 mol / L.

[0083] Step S32: passing liquid ammonia into the stripping solution II of germanium obtained in step S31, and reacting to neutralize to a final pH value of 8.5-10.

[0084] The reaction time is 60-120 min, the reaction temperature is 40-80°C, the filtrate is filtered and returned to step 3 for recycling stripping; the filtered germanium concentrate II is dried and calcined, the calcination temperature is 450-650°C, and the calcination time is greater than 2 h to obtain germanium concentrate.

[0085] Step S4:

[0086] Step S41: adding an ionic precipitant of formula (6) to the gallium and iron stripping solution I obtained in step S2, the amount of the ionic precipitant added is: the ionic molar ratio of the effective component to the sum of the amounts of gallium and iron ions in the gallium and iron stripping solution I is 1.5:1-3:1, the reaction time is 10 min-60 min, and the reaction temperature is 10-80°C; filtering to obtain the gallium and iron concentrate I which enters step S42, and the filtrate is returned to step S2 for recycling stripping.

[0087] Formula (6):

[0088]

[0089] wherein M3 is one of H + , Na + , K + , NH4 + .

[0090] Step S42: adding a sodium hydroxide solution to the gallium and iron concentrate I obtained in step S41, the concentration is 120-200 g / L, the liquid-solid ratio is 4-8, the reaction temperature is 30-80°C, the reaction time is 1-4 h, filtering, measuring the gallium concentration in the filtrate, and recycling enrichment to a gallium concentration of 20-80 g / L to prepare metal gallium by electrodeposition.

[0091] Example 1

[0092] A method for cooperatively extracting and preparing metal gallium and germanium concentrate from a high-acid leaching solution containing gallium and germanium, please refer to the process flow of Figure 1 , including the following steps:

[0093] Step S1: liquid-liquid extraction I of the high-acid leaching solution containing gallium and germanium with a complex organic phase.

[0094] In this embodiment, the high-acid leaching solution containing gallium and germanium is an industrial gallium and germanium-containing sulfuric acid leaching solution, wherein the sulfuric acid concentration is 25 g / L, and the concentrations of Ga, Ge, Fe, As, Zn, Co, Ni, Cd, and Cu are shown in Table 1.

[0095] In this embodiment, the composition of the complex organic phase is: 10 vol% hydroxamic chelating extractant + 20 vol% alkyl phenoxy phosphate extractant + 10 vol% alcohol modifier + 60 vol% 260# sulfonated kerosene.

[0096] Wherein:

[0097] The hydroxamic chelating extractant of this embodiment has the following structure:

[0098]

[0099] The alkyl phenoxy phosphate extractant of this embodiment includes 88 mol% mono-phosphate ester and 12 mol% di-phosphate ester.

[0100] The mono-phosphate ester has the following structure:

[0101]

[0102] The di-phosphate ester has the following structure:

[0103]

[0104] The alcohol modifier of this embodiment has the following structure:

[0105]

[0106] In this embodiment, two-stage extraction is carried out using a separatory funnel, the extraction temperature is 35°C, the extraction phase ratio O / A is 1:1, and the extraction time is 10 min.

[0107] Table 1 shows the separation results of the liquid-liquid extraction I process of Example 1.

[0108]

[0109]

[0110] The results in Table 1 show that the single-stage extraction rates of gallium and germanium in the liquid-liquid extraction I process are 98.86% and 100%, respectively, and iron is co-extracted, with an extraction rate of 96.88%, and other impurities are extracted in trace amounts.

[0111] Step S2: The loaded organic phase after liquid-liquid extraction I is subjected to two-stage 1.5 mol oxalic acid solution stripping I using a separatory funnel to obtain a loaded organic phase and a gallium and iron stripping solution I (referred to as gallium stripping solution in Table 2), and the gallium stripping rates of the two stripping solutions I are calculated after mixing. The results are shown in Table 2 below. The stripping temperature in stripping I is 45°C, the phase ratio O / A is 1:1, and the stripping time is 15 min.

[0112] The oxalic acid used in the embodiment has the following structure:

[0113]

[0114] wherein M4 is H + .

[0115] Step S3:

[0116] Step S31: The loaded organic phase after step S2 stripping I is subjected to two-stage 2 mol 2,3-dihydroxy-succinic acid diammonium salt solution stripping II using a separatory funnel to obtain a germanium stripping solution II (indicated as germanium stripping solution in Table 2), and the stripping rate of germanium is calculated after mixing the stripping solutions II of the two stripping processes, and the results are shown in Table 2. The stripping temperature in stripping II is 45°C, and the O / A ratio is 1:1; the stripping time is 15 min.

[0117] The 2,3-dihydroxy-succinic acid diammonium salt used in the embodiment has the following structure:

[0118]

[0119] wherein M5 is NH4 + .

[0120] Table 2 Process separation results of stripping I and stripping II in Example 1

[0121]

[0122]

[0123] As can be seen from Table 2, after two-stage stripping of gallium and germanium, the gallium stripping rate can reach 96.55%, and the germanium stripping rate can reach 98.36%, wherein the impurity Fe is stripped together with gallium in the gallium stripping process, and the iron stripping rate reaches 96.77%, and the remaining iron is completely stripped out in the germanium stripping process.

[0124] Step S32: The germanium stripping solution II in S31 is subjected to cyclic enrichment to obtain a high-concentration germanium stripping solution II (see Table 3, which is indicated as germanium stripping solution in Table 3), and liquid ammonia is introduced into the high-concentration germanium stripping solution II (2L) for neutralization, and when the pH is 9.0, the reaction is carried out for 2 hours to obtain a wet germanium concentrate, which is calcined in a muffle furnace at a temperature of 550°C for 4h, and then crushed to obtain a germanium concentrate of 31.8g. The results are shown in Table 3.

[0125] Table 3 Separation results of the process of introducing liquid ammonia into the germanium stripping solution of Example 1

[0126] Composition Ga Ge Fe As Zn Cu Gallium stripping solution (g / L) 0.5 10.15 0.9 0.01 0.1 0.1 After precipitation liquid (g / L) 0 1.8 0 0.005 0.05 0.05 Precipitation rate (%) 100 82.27 100 50 50 50 Gallium concentrate (%) 3.14 52.52 5.66 0.03 0.3 0.3

[0127] Step S4:

[0128] Step S41: The stripping solution I of gallium and iron obtained in step S2 is subjected to cyclic enrichment to obtain a high-concentration stripping solution I of gallium and iron (see Table 4, which is referred to as gallium stripping solution I in Table 4). To the high-concentration stripping solution I (1 L) of gallium and iron, 252 g of amino-tris-methyl-phosphonic acid ion precipitant with an effective content of 95% (the molar ratio of the total effective content to the total amount of gallium and iron ions in the stripping solution I of gallium and iron is 3:1) is added. The reaction is carried out at 45°C for 30 min, and white precipitate 385 g containing water is obtained by suction filtration. After dehydration by high-temperature drying, 98 g of enrichment I containing 9.18% of gallium and 5.10% of iron is obtained.

[0129] The amino-tris-methyl-phosphonic acid of the present embodiment has the following structure:

[0130]

[0131] wherein M3 is H + .

[0132] Step S42: The enrichment I of gallium and iron obtained in step S41 is dissolved by using 400 mL of 200 g / L sodium hydroxide (the enrichment I of 98 g containing 9.18% of gallium and 5.10% of iron is dissolved by the above-mentioned sodium hydroxide). The reaction is carried out at 80°C for 120 min, and brown-red precipitate (iron residue) appears. The alkali-soluble filtrate is obtained by filtration (see Table 4).

[0133] Table 4: Separation results of the precipitation and alkali-soluble process of the cyclic enrichment solution of the gallium stripping solution of Example 1

[0134] Composition Ga Ge Fe As Zn Cu Gallium stripping solution (g / L) 11.5 0.15 6.5 0 0.5 0.1 Precipitation rate (%) 78.26 80.00 76.92 0 10.00 50 After precipitation liquid (g / L) 2.5 0.12 1.5 0 0.45 0.05 Alkaline solution liquid (g / L) 21.5 0.3 0.001 0 0.10 0.01

[0135] As shown in Table 4, the gallium precipitation rate is 78.26%. After the precipitation, the solid is dissolved by using a high-concentration alkali solution, so that the gallium is transferred into the alkali solution. The gallium dissolution rate is 95.56%, and the separation of gallium and iron can be realized. The metal gallium containing 99.9% of gallium is obtained by electrodepositing the alkali-soluble solution.

[0136] Example 2

[0137] A method for preparing metal gallium and germanium concentrates by synergistic extraction from high-acid gallium and germanium leaching solution, please refer to the process flow of Figure 1 , including the following steps:

[0138] Step S1: The high-acid leaching solution containing gallium and germanium is subjected to liquid-liquid extraction I with a complex organic phase.

[0139] In the present embodiment, the high-acid leaching solution containing gallium and germanium is an industrial gallium and germanium-containing sulfuric acid leaching solution, wherein the concentration of sulfuric acid is 45 g / L, and the concentrations of Ga, Ge, Fe, As, Zn, Co, Ni, Cd, and Cu are shown in Table 5.

[0140] In this embodiment, the composition of the complex organic phase is: 15 vol% hydroxamic chelating extractant + 25% alkyl phenoxy phosphate extractant + 10 vol% alcohol modifier + 50 vol% 260# sulfonated kerosene.

[0141] wherein:

[0142] The hydroxamic chelating extractant of this embodiment has the following structure:

[0143]

[0144] The alkyl phenoxy phosphate extractant of this embodiment includes 90 mol% mono-phosphate ester and 10 mol% di-phosphate ester.

[0145] The mono-phosphate ester has the following structure:

[0146]

[0147] The di-phosphate ester has the following structure:

[0148]

[0149] The alcohol modifier of this embodiment has the following structure:

[0150]

[0151] This embodiment uses a separatory funnel to perform 3-stage extraction, with an extraction temperature of 35°C, an extraction phase ratio of O / A = 1:1, and an extraction time of 10 min. The results are shown in Table 5.

[0152] Table 5 Separation results of liquid-liquid extraction I process of Example 2

[0153]

[0154] The results in Table 5 show that the single-stage extraction rates of gallium and germanium in the liquid-liquid extraction I process are 98.43% and 100%, respectively, and iron is co-extracted, with an extraction rate of 78.61%, of which the extraction is trace.

[0155] Step S2: The loaded organic phase after liquid-liquid extraction I is used to perform 4-stage 1.5 mol oxalic acid solution gallium stripping I using a separatory funnel, to obtain a loaded organic phase, a gallium and iron stripping solution I (referred to as gallium stripping solution in Table 6), and the gallium stripping rate is calculated after mixing the gallium and iron stripping solutions I from 4 times of stripping. The results are shown in Table 6 below. The stripping temperature in stripping I is 45°C, the phase ratio O / A = 1:1, and the stripping time is 15 min.

[0156] The oxalic acid used in this embodiment has the following structure:

[0157]

[0158] wherein M4 is H + .

[0159] Step S3:

[0160] Step S31: The loaded organic phase after stripping I in step S2 is subjected to 4-stage 2.5 mol 2,3-dihydroxy-succinic acid diammonium salt solution stripping II using a separatory funnel to obtain a germanium stripping solution II (indicated as germanium stripping solution in Table 6), and the stripping rate of germanium is calculated after mixing the stripping solution II of 4-stage stripping. The results are shown in Table 6 below. The stripping temperature in stripping II is 45°C, and the O / A ratio is 1:1; the stripping time is 15 min.

[0161] The 2,3-dihydroxy-succinic acid diammonium salt in this embodiment has the following structure:

[0162]

[0163] wherein M5 is NH4 + .

[0164] Table 6 Process separation results of stripping I and stripping II in Example 2

[0165]

[0166] As can be seen from the results in Table 6, after 4-stage stripping of gallium and germanium, the gallium stripping rate reaches 98.41%, and the impurity iron is co-extracted in the extraction process, and is stripped together with gallium in the gallium stripping process, and the iron stripping rate reaches 96.55%, and the remaining iron is completely stripped out in the germanium stripping process.

[0167] S32: The germanium stripping solution II in S31 is subjected to cyclic enrichment, and high-concentration germanium stripping solution II is obtained by cyclic enrichment (see Table 7, indicated as germanium stripping solution in Table 7), and liquid ammonia is introduced into the high-concentration germanium stripping solution II (2L) for neutralization, and when the neutralization pH is 9.0, the reaction is carried out for 2 hours to obtain wet germanium concentrate, and the wet germanium concentrate is calcined in a muffle furnace at a set temperature of 550°C for 4 hours, and then broken to obtain germanium concentrate 31.65g. The results are shown in Table 7.

[0168] Table 7 Separation results of the process of introducing liquid ammonia into the germanium stripping solution in Example 2

[0169] Composition Ga Ge Fe As Zn Cu Gallium stripping solution (g / L) 0 10.15 0.5 0.01 0.1 0.1 After precipitation liquid (g / L) 0 1.8 0 0.005 0 0 Precipitation rate (%) 0 82.27 100 50 100 100 Gallium concentrate (%) 0 52.76 3.16 0.03 0.63 0.63

[0170] Step S4:

[0171] Step S41: The gallium and iron stripping solution I obtained in step S2 is subjected to cyclic enrichment to obtain a high-concentration gallium-containing solution (see Table 8, which is referred to as gallium stripping solution in Table 8). 1 L of the gallium and iron stripping solution I is taken, 370 g of an amino-trimethylene phosphonic acid ion precipitant with an effective content of 95% (the total effective amount is in a molar ratio of 3:1 to the total amount of gallium and iron ions in the gallium and iron stripping solution I) is added, and the reaction is carried out at 45°C for 30 min. White precipitate 310 g containing water is obtained by suction filtration, and 148 g of enrichment I containing 6.43% of gallium and 10.47% of iron is obtained after dehydration by high-temperature drying.

[0172] The amino-trimethylene phosphonic acid of the present embodiment has the following structure:

[0173]

[0174] wherein M3 is HH + .

[0175] Step S42: The gallium and iron enrichment I obtained in step S41 is dissolved using 180 g / L of sodium hydroxide 600 mL to dissolve the enrichment I (148 g of enrichment I containing 6.43% of gallium and 10.47% of iron), and the reaction is carried out at 80°C for 120 min. Brown-red precipitate (iron slag) appears, and the gallium-containing filtrate is obtained by filtration, as shown in Table 3.

[0176] Table 8: Separation results of the precipitation and alkaline dissolution process of the gallium stripping solution cyclic enrichment solution of Example 2

[0177] Composition Ga Ge Fe As Zn Cu Gallium stripping solution (g / L) 12.5 0.05 20.15 0 0.3 0 Precipitation rate (%) 76.16 60.00 76.92 0 50.00 0 After precipitation liquid (g / L) 2.98 0.02 4.65 0 0.15 0 Alkaline solution liquid (g / L) 15.5 0.05 0.1 0 0.25 0

[0178] As shown in Table 8, the gallium precipitation rate is 76.16%, the gallium is transferred into the alkaline solution after the solid obtained after precipitation is dissolved using a high-concentration alkaline solution, the gallium dissolution rate is 97.67%, the separation of gallium and iron can be achieved, and the metal gallium containing 99.9% of gallium is obtained by electrowinning after the alkaline solution after dissolution is cyclically enriched when the gallium concentration is greater than 20 g / L.

[0179] The above-described embodiments only express several embodiments of the present application, which are described in a more specific and detailed manner, but should not be understood as limiting the scope of the patent. It should be noted that for ordinary skilled persons in the art, several modifications and improvements can be made without departing from the concept of the present application, and the present application is intended to include these modifications and improvements.

Claims

1. A process for the synergistic extraction of gallium and germanium concentrates, characterised in that: Comprise the following steps: Step S1: the high acid leaching solution containing gallium and germanium is subjected to liquid-liquid extraction I with a compounded organic phase; the compounded organic phase comprises the following components: 2 vol%-30 vol% of hydroxamic acid chelating extractant of formula (1), 20 vol%-30 vol% of alkyl phenoxy phosphate extractant, 5 vol%-10 vol% of alcohol modifier of formula (3), and the balance of kerosene diluent; wherein, Formula (1): In the formula, R1 is one of C9-C18 alkyl; The alkyl phenoxy phosphate extractant comprises 88-90 mol% of monophosphate ester of formula (21) and 12-10 mol% of dipolyphosphate ester of formula (22); Formula (21): Formula (22): In the formula (21) and formula (22), R2 is one of C8-C12 alkyl; Formula (3): or Step S2: The loaded organic phase obtained in the liquid-liquid extraction I in step S1 is subjected to stripping I with a solution of formula (4) to obtain a loaded organic phase and a stripping solution I of gallium and iron; Formula (4): wherein M4is H + , Na + , K + , NH4 + ; Step S3, comprising: Step S31: the loaded organic phase obtained in the stripping I in step S2 is subjected to stripping II with a solution of formula (5) to obtain a stripping solution II of germanium; Formula (5): wherein M5is NH4 + ; Step S32: liquid ammonia is introduced into the stripping solution II of germanium obtained in step S31, and the reaction is neutralized to a final pH value of 8.5-10, and a germanium concentrate II is obtained by filtration, and the germanium concentrate II is dried and calcined to obtain germanium concentrate; Step S4, comprising: Step S41: an ionic precipitant of formula (6) is added to the stripping solution I of gallium and iron obtained in step S2, and a gallium and iron concentrate I is obtained by filtration; Formula (6): wherein M3is H + , Na + , K + , NH4 + ; Step S42: sodium hydroxide solution is added to the gallium and iron concentrate I obtained in step S42, and filtration is performed, and the gallium concentration in the filtrate is measured, or after the gallium concentration is enriched to 20-80 g / L, metal gallium is prepared by electrodeposition.

2. The process for the synergistic extraction of gallium and germanium concentrates according to claim 1, characterized in that: In step S1, the high acid leaching solution containing gallium and germanium contains 0.1-3 g / L of gallium and 0.1-3 g / L of germanium, and the main impurities include Fe, Cu, Zn, Sb, As, Co and Ni, wherein the concentration of Cu is less than 40 g / L, the concentration of Zn is less than 200 g / L, and the concentrations of the remaining main impurity components are less than 5 g / L; the high acid leaching solution containing gallium and germanium is a sulfuric acid leaching solution containing gallium and germanium, and the concentration of sulfuric acid is in the range of 10-130 g / L.

3. The process for the synergistic extraction of gallium and germanium concentrates according to claim 1, characterized in that: In step S1, the extraction temperature of liquid-liquid extraction I is 20-60 ℃, and the phase ratio O / A is 1:1-5:1; the extraction time is 2-30 min.

4. The process for the synergistic extraction of gallium and germanium concentrates according to claim 1, characterized in that: In step S2, the stripping temperature of stripping I is 20-60 ℃, the phase ratio O / A is 1:1-1:10, and the stripping time is 10-30 min.

5. The process for synergistic extraction of gallium and germanium concentrates as claimed in claim 1 wherein: In step S2, the concentration of the solution of formula (4) is 1.0-2.0 mol / L.

6. The process for synergistic extraction of gallium and germanium concentrates as claimed in claim 1 wherein: In step S31, the concentration of the solution of formula (5) used in stripping II is 1.0-3.0 mol / L.

7. The process for the synergistic extraction of gallium and germanium concentrates according to claim 1, characterized in that: In step S31, the stripping temperature of stripping II is 30-65 ℃, the phase ratio O / A is 1:1-1:10; the stripping time is 15-30 min, and the stripping stages are 2-5 stages.

8. The process for the synergistic extraction of gallium and germanium concentrates according to claim 1, characterized by: In step S32, the reaction of passing liquid ammonia into the stripping solution II of germanium is carried out, the reaction time is 60-120 min, and the reaction temperature is 40-80℃; the filtered germanium enrichment II is dried and calcined, the calcination temperature is 450-650℃, and the calcination time is greater than 2h.

9. The process for the synergistic extraction of gallium and germanium concentrates according to claim 1, characterized in that: In step S41, the adding amount of the ion precipitant of formula (6) is 1.5-3:1 of the molar ratio of the sum of the effective components and the total amount of the ions of gallium and iron in the stripping solution I, the reaction time is 10 min-60 min, and the reaction temperature is 10-80℃.

10. The process for synergistic extraction of gallium and germanium concentrates as claimed in claim 1 wherein: In step S42, the concentration of the sodium hydroxide solution is 120-200 g / L, the liquid-solid ratio of the sodium hydroxide solution and the gallium and iron enrichment I is 4-8, the reaction temperature is 30-80℃, and the reaction time is 1-4h.

Images