CN104451172A - Method for comprehensively recovering valuable metals from zinc hydrometallurgy high-temperature purification slags - Google Patents
Method for comprehensively recovering valuable metals from zinc hydrometallurgy high-temperature purification slags Download PDFInfo
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Abstract
The invention discloses a method for comprehensively recovering valuable metals from zinc hydrometallurgy high-temperature purification slags. The method comprises the following steps: (1) drying and firing of the high-temperature purification slags; (2) first leaching; (3) second leaching; (4) purification and deposition of copper; (5) purification and deposition of cadmium; (6) deposition of tannin germanium; (7) deposition of cobalt; and (8) deposition of nickel and recovery of zinc by returning liquid obtained by deposition of nickel to a zinc hydrometallurgy system. The invention provides a method for leaching the zinc hydrometallurgy high-temperature purification slags twice after drying and firing to obtain the produced leaching slags, namely silver lead ore concentrate for sales, and comprehensively recovering copper, cadmium, germanium, cobalt, nickel and zinc from filtering liquid subjected to first leaching; the method is easy to carry out and simple in process; the recovery rate of the valuable metals is high, as the recovery rate of lead, silver, copper, cadmium, germanium, cobalt, nickel and zinc respectively reaches 98.50-99.50 percent, 99.10-99.70 percent, 94.40-97.80 percent, 95.10-96.90 percent, 93.50-96.70 percent, 94.70-95.70 percent, 94.80-96.80 percent, and 96.00-97.00 percent; moreover, the recovery of the valuable metals is more comprehensive, scientific and reasonable; waste water, waste gas and waste slags are avoided, and the requirement on national circular economy and sustainable development is met.
Description
Technical field
The present invention relates to a kind of method of comprehensively recovering valuable metal from zinc hydrometallurgy high temperature purification slag, particularly synthetical recovery zinc, copper, cadmium, germanium, cobalt, nickel, lead, silver-colored method from zinc hydrometallurgy high temperature purification slag, belong to hydrometallurgy field.
Background technology
Zinc hydrometallurgy process selects different production technique, though the scavenging process of centering supernatant has multiple technologies and method by its raw material and the unusual of impurity; But because zinc replacement itself has the incomparable advantage of other method to its solution, from but current one of major reason of adopting of most of zinc hydrometallurgy factories in the world.And to purify zinc powder used be generally all electric furnace zinc powder, because the production technology characteristic of electric furnace zinc powder determines, it contains certain lead and silver, adding electric furnace zinc powder at solution carries out in the process purified, its silver and lead almost enter purification slag, and zinc powder consumption is larger, the amount of the silver in purification slag and lead is more.
Zinc replacement is generally constituted jointly by low temperature purification and high temperature purification.Reclaim the process of purification slag, the maturation process technology of generally acknowledging at present is; One is by high and low temperature slag merging treatment, namely carries out carrying out cobalt, nickel purification again after cadmium is reclaimed in leaching to it; Lean cadmium solution after the purification of output cobalt, nickel returns electric zinc recovering zinc, and the copper ashes of output and purified cobalt, nickel slag muck are deposited or sold.Two is the separately process of high and low temperature slag, namely carries out reclaiming cadmium after routine leaches to low temperature slag, and output lean cadmium solution returns the copper ashes sale that electric Zn system reclaims zinc and output; Then carry out Selectively leaching under certain conditions to high temperature sludge, its objective is recovery zinc, the selective leaching fluid of output returns that electric Zn system reclaims the Selectively leaching cobalt of zinc and output, nickel slag muck is deposited or sold; Though high and low temperature slag separately processes the lean cadmium solution that produces and selective leaching fluid does not need purification can directly return electric Zn system, valuable metal comprehensive reutilization rate is low, and industrial chain is not long.
Known treatment technology, School of Materials & Metallurgy of Kunming University of Science and Technology Liu Chun is chivalrous, Xie Gang, Wang Jikun, Yang great Jin write articles the synthetical recovery describing zinc wet purification slag, report and adopt sulfuric acid leaching purification slag, the heavy cobalt of strong oxidizer Sodium Persulfate oxidation, obtains the rich cobalt slag containing cobalt about 18%; Zinc powder is adopted to add antimonous oxide, copper sulfate displacement nickel, obtains the rich nickel slag of nickeliferous about 5%, finally reaches the synthetical recovery of cobalt, nickel, zinc stays the object returning wet zinc-making system in the solution and reclaim, but does not reclaim the copper in slag, cadmium, germanium, lead, silver.
Hunan Research Institute of Non-ferrous Metals, the Chen Haiqing of Baiyin nonferrous metals companies, Liu Yaxiong write articles the research describing comprehensively recovering valuable metal from purification slag, article describes the technique of Call Provision and other valuable metal from purification slag, adopt dilute sulphuric acid selectively leaching, Call Provision, cadmium, nickel, zinc from leach liquor, copper, lead is reclaimed from leached mud, and copper, lead, cobalt, cadmium, zinc total yield reach 100%, 100%, 90.33%, 96.80%, 95.51% respectively, but do not relate to in purification slag silver, germanium recovery.
The patent of invention of patent No. ZL201110059299.4 " reclaiming the method for lead silver from purification slag of zinc hydrometallurgy ", report low temperature slag and adopt conventional leaching, lean cadmium solution power transmission zinc recovering zinc after recovery cadmium, copper ore concentrates is sold; High temperature sludge carries out leaching and Call Provision, output cobalt concentrate and plumbous silver preparation concentrate to its leached mud again after adopting Selectively leaching recovery zinc.And the copper, cadmium, germanium, nickel etc. in high temperature sludge is not recovered.
Report is had no at present about synthetical recovery zinc, copper, cadmium, cobalt, germanium, nickel and lead, silver from high temperature purification slag.
Summary of the invention
The object of this invention is to provide a kind of method of comprehensively recovering valuable metal from zinc hydrometallurgy high temperature purification slag, it is mainly for the characteristic of purification slag, and Conventional cryogenic purification slag is generally directly carry out routine to leach recovery zinc, cadmium, copper; The present invention carries out calcination, leaching to high temperature purification slag, and from leach liquor synthetical recovery zinc, copper, cadmium, cobalt, germanium, nickel, plumbous and silver is then stayed in leached mud and is recycled with plumbous silver preparation concentrate.
The present invention's method of comprehensively recovering valuable metal from zinc hydrometallurgy high temperature purification slag completes according to the following steps:
(1) oven dry of high temperature purification slag and calcination: first to containing zinc 30wt%-40wt%, cupric 1.5wt%-3.5wt%, containing cadmium 1.0wt%-2.0wt%, dry containing the high temperature purification slag of cobalt 0.06wt%-0.08wt%, nickeliferous 0.04wt%-0.09wt%, germanic 0.05wt%-0.08wt%, leaded 3.0wt%-4.0wt%, argentiferous 0.01wt%-0.02wt%, then the high temperature purification slag of drying calcination 2.5-3.0 hour when natural ventilation, calcination temperature is 350 DEG C-450 DEG C, makes each valuable metal in slag fully oxidized;
(2) once leach: with process water, the high temperature purification slag after calcination is carried out pulp by the liquid-solid ratio of 5-6:1, slurry time 0.2-0.4 hour, with vitriol oil adjustment beginning sour 90-100g/l, control process temperature 70 C-80 DEG C, extraction time 1.5-2.0 hour, filtration 1 is carried out, output No. 1 leached mud and No. 1 leach liquor after terminal pH=4.5-5.0; No. 1 leached mud carries out secondary leaching, and No. 1 leach liquor carries out next step valuable metal recovery;
(3) secondary leaches: carry out pulp to No. 1 leached mud by the liquid-solid ratio of 3-4:1, with vitriol oil adjustment beginning sour 80-90g/l, control process temperature 80 DEG C-90 DEG C, extraction time 3.0-4.0 hour, carry out filtration 2 after terminal acid 50-60g/l, output No. 2 leached muds can return once to leach as plumbous silver preparation concentrate sale and No. 2 leach liquors and do pulp liquid;
(4) the heavy copper of purification: the heavy copper of purification is according to copper, cadmium, germanium, cobalt, the current potential of nickel is different, the metal zinc No. 1 leach liquor being added at normal temperatures to the 98wt%-99wt% of copper theoretical amount carries out copper displacement, metal zinc joining day 45-55 minute, after 70-90 minute replacement(metathesis)reaction time, filter 23 is carried out to it, filter 23 obtains water content 10.00wt%-12.50wt%, copper 64wt%-70wt%, cadmium 0.05wt%-0.09wt%, zinc 3.50wt%-8.00wt%, germanium 0.004wt%-0.006wt%, cobalt 0.004wt%-0.006wt%, liquid after the copper powder of nickel 0.004wt%-0.005wt% and heavy copper, after heavy copper, liquid carries out next step heavy cadmium, and copper powder then can be sold,
(5) the heavy cadmium of purification: the heavy cadmium of purification is different according to the current potential of cadmium, germanium, cobalt, nickel, metal zinc liquid after heavy copper being added at 45 DEG C-50 DEG C to the 97wt%-99wt% of cadmium theoretical amount carries out cadmium displacement, metal zinc joining day 30-40 minute, after 60-70 minute replacement(metathesis)reaction time, filtration 4 is carried out to it, filter 4 and obtain liquid after water content 20.00wt%-25.00wt%, cadmium 75.00wt%-80.00wt%, zinc 6.50wt%-8.00wt%, germanium 0.006wt%-0.009wt%, cobalt 0.005wt%-0.009wt%, the sponge cadmium of nickel 0.006wt%-0.009wt% and heavy cadmium; After sponge cadmium send cake of press workshop cake of press, founding becomes thick cadmium ingot and produces pure cadmium, and the tannin that after heavy cadmium, liquid carries out next step sinks germanium;
(6) tannin sinks germanium: because the chemical property of germanium, cobalt, nickel determines, is difficult to separately germanium be separated from containing the high solution of cobalt, nickel with zinc powder.Therefore adopt tannin to sink the method for germanium here to precipitate germanium, cobalt, nickel then retain in the solution.Actual conditions is the pH=2.5-3.5 of liquid after first adjusting heavy cadmium, temperature 65 DEG C-75 DEG C, add Weibull amount be the 25-30 of germanium total amount in solution doubly, carry out filtration 5 after reaction times 20-30 minute, filter 5 and obtain liquid after tannin germanium slag and heavy germanium; After heavy germanium, liquid carries out next step heavy cobalt, and tannin germanium slag carries out filtration 7 after needing to wash 30-40 minute at liquid-solid ratio 3-4:1, temperature 65 DEG C-75 DEG C; Filter 7 obtain water content 55.00wt%-65.00wt%, germanium 3.20wt%-3.60wt%, zinc 4.00wt%-4.50wt%, cobalt 0.006wt%-0.009wt%, nickel 0.005wt%-0.008wt% wash rear tannin germanium slag and germanium wash heat water.Washing rear tannin germanium slag send the calcination of calcination workshop to become germanium concentrate to sell, and germanium wash heat water returns once to leach and sizes mixing;
(7) heavy cobalt: be that liquid after heavy germanium is warming up to 65 DEG C-75 DEG C, then Sodium Nitrite and β-Nai phenol is added, Sodium Nitrite add-on is 0.4-0.5 times of cobalt total amount in solution, β-Nai phenol add-on is 8-12 times of cobalt total amount in solution, carry out filtration 6 after reaction times 40-60 minute, filter 6 and obtain liquid after water content 40wt%-50wt%, cobalt 15.00wt%-16.00wt%, nickel 0.005wt%-0.008wt%, the cobalt concentrate of zinc 5.00wt%-6.00wt% and heavy cobalt; After heavy cobalt, liquid carries out next step heavy nickel, and cobalt concentrate then can be sold;
(8) heavy nickel: be that liquid after heavy cobalt is warming up to 75-85 DEG C, the pH=5.0-5.2 of liquid after the heavy cobalt of adjustment, then metal zinc is added, antimonous oxide and copper sulfate, metal zinc add-on is 1.3-1.5 times of nickel total amount in solution, antimonous oxide add-on is the 0.5wt%-1.0wt% of added metal zinc amount, copper sulfate add-on is the 1.0wt%-1.5wt% of added metal zinc amount, filtration 8 is carried out after reaction times 45-55 minute, filter 8 and obtain water content 14.00wt%-15.00wt%, nickel 15.00wt%-16.00wt%, liquid after the nickel ore concentrate of zinc 8.50 wt%-9.50wt% and heavy nickel, after heavy nickel, liquid returns electric Zn system and reclaims zinc, and nickel ore concentrate then can be sold.
Compared with known technology, the following advantages that the present invention has and positively effect:
(1) the invention provides and a kind of carry out two-stage leaching by after zinc hydrometallurgy high temperature purification slag drying, calcination, the leached mud of output is plumbous silver preparation concentrate and sells, and from a leach liquor method of Recovering Copper, cadmium, germanium, cobalt, nickel, zinc.
(2) the invention provides a kind of use metal zinc, by controlling different condition, from the solution containing zinc, copper, cadmium, germanium, cobalt, nickel, the method for copper, cadmium, nickel can be separated preferably smoothly, and processing ease, flow process is simple.
(3) the present invention is compared with known technology, recovery rate of valuable metals is high, reaches plumbous 98.50-99.50%, silver-colored 99.10-99.70%, copper 94.40-97.80%, cadmium 95.10-96.90%, germanium 93.50-96.70%, cobalt 94.70-95.70%, nickel 94.80-96.80%, zinc 96.00-97.00% respectively; And valuable metal recovery more comprehensively, more scientific, more reasonable.
(4) the present invention is compared with known technology, does not produce waste water,waste gas and industrial residue, meets the requirement of national recycling economy and Sustainable development.
Accompanying drawing explanation
Fig. 1 is the process flow sheet that high temperature purification slag for comprehensive of the present invention is recycled.
Embodiment
Below in conjunction with accompanying drawing 1, the present invention is further illustrated, but limited the present invention never in any form, and according to the teachings of the present invention done any change or replacement, all belong to protection scope of the present invention.
(1) oven dry of high temperature purification slag and calcination: first to containing zinc 30wt%-40wt%, cupric 1.5wt%-3.5wt%, containing cadmium 1.0wt%-2.0wt%, dry containing the high temperature purification slag of cobalt 0.06wt%-0.08wt%, nickeliferous 0.04wt%-0.09wt%, germanic 0.05wt%-0.08wt%, leaded 3.0wt%-4.0wt%, argentiferous 0.01wt%-0.02wt%, then the high temperature purification slag of drying calcination 2.5-3.0 hour when natural ventilation, calcination temperature is 350 DEG C-450 DEG C, makes the valuable metal in slag fully oxidized.
(2) once leach: with process water, the high temperature purification slag after calcination is carried out pulp by the liquid-solid ratio of 5-6:1, slurry time 0.2-0.4 hour, with vitriol oil adjustment beginning sour 90-100g/l, control process temperature 70 C-80 DEG C, extraction time 1.5-2.0 hour, carries out filtration 1 after terminal pH=4.5-5.0.Output No. 1 leached mud carries out secondary leaching and carries out No. 1 leach liquor of valuable metal recovery.
(3) secondary leaches: carry out pulp to No. 1 leached mud by the liquid-solid ratio of 3-4:1, and with vitriol oil adjustment beginning sour 80-90g/l, control process temperature 80 DEG C-90 DEG C, extraction time 3.0-4.0 hour, carries out filtration 2 after terminal acid 50-60g/l.Output No. 2 leached muds do plumbous silver preparation concentrate and to sell and No. 2 leach liquors return once leaching and do pulp liquid.
(4) the heavy copper of purification: the heavy copper of purification is according to copper, cadmium, germanium, cobalt, the current potential of nickel is different, the metal zinc No. 1 leach liquor being added at normal temperatures to the 98wt%-99wt% of copper theoretical amount carries out copper displacement, metal zinc joining day 45-55 minute, after 70-90 minute replacement(metathesis)reaction time, filter 23 is carried out to it, filter 23 obtains water content 10.00wt%-12.50wt%, copper 64wt%-70wt%, cadmium 0.05wt%-0.09wt%, zinc 3.50wt%-8.00wt%, germanium 0.004wt%-0.006wt%, cobalt 0.004wt%-0.006wt%, liquid after the copper powder of nickel 0.004wt%-0.005wt% and heavy copper.After heavy copper, liquid carries out next step heavy cadmium, and copper powder is then sold.
(5) the heavy cadmium of purification: the heavy cadmium of purification is different according to the current potential of cadmium, germanium, cobalt, nickel, metal zinc liquid after heavy copper being added at 45 DEG C-50 DEG C to the 97wt%-99wt% of cadmium theoretical amount carries out cadmium displacement, metal zinc joining day 30-40 minute, after 60-70 minute replacement(metathesis)reaction time, filtration 4 is carried out to it, filter 4 and obtain liquid after water content 20.00wt%-25.00wt%, cadmium 75.00wt%-80.00wt%, zinc 6.50wt%-8.00wt%, germanium 0.006wt%-0.009wt%, cobalt 0.005wt%-0.009wt%, the sponge cadmium of nickel 0.006wt%-0.009wt% and heavy cadmium.After sponge cadmium send cake of press workshop cake of press, founding becomes thick cadmium ingot and produces pure cadmium, and the tannin that after heavy cadmium, liquid carries out next step sinks germanium.
(6) tannin sinks germanium: because the chemical property of germanium, cobalt, nickel determines, is difficult to separately germanium be separated from containing the high solution of cobalt, nickel with zinc powder.Therefore adopt tannin to sink the method for germanium here to precipitate germanium, cobalt, nickel then retain in the solution.Actual conditions is the pH=2.5-3.5 of liquid after first adjusting heavy cadmium, temperature 65 DEG C-75 DEG C, add Weibull amount be the 25-30 of germanium total amount in solution doubly, carry out filtration 5 after reaction times 20-30 minute, filter 5 and obtain liquid after tannin germanium slag and heavy germanium.After heavy germanium, liquid carries out next step heavy cobalt, and tannin germanium slag carries out filtration 7 after will washing 30-40 minute at liquid-solid ratio 3-4:1, temperature 65 DEG C-75 DEG C, filter 7 obtain water content 55.00wt%-65.00wt%, germanium 3.20wt%-3.60wt%, zinc 4.00wt%-4.50wt%, cobalt 0.006wt%-0.009wt%, nickel 0.005wt%-0.008wt% wash rear tannin germanium slag and germanium wash heat water.Washing rear tannin germanium slag send the calcination of calcination workshop to become germanium concentrate to sell, and germanium wash heat water returns once to leach and sizes mixing.
(7) heavy cobalt: be that liquid after heavy germanium is warming up to 65 DEG C-75 DEG C, then Sodium Nitrite and β-Nai phenol is added, Sodium Nitrite add-on is 0.4-0.5 times of cobalt total amount in solution, β-Nai phenol add-on is 8-12 times of cobalt total amount in solution, carry out filtration 6 after reaction times 40-60 minute, filter 6 and obtain liquid after water content 40wt%-50wt%, cobalt 15.00wt%-16.00wt%, nickel 0.005wt%-0.008wt%, the cobalt concentrate of zinc 5.00wt%-6.00wt% and heavy cobalt; After heavy cobalt, liquid carries out next step heavy nickel, and cobalt concentrate is then sold.
(8) heavy nickel: be that liquid after heavy cobalt is warming up to 75-85 DEG C, the pH=5.0-5.2 of liquid after the heavy cobalt of adjustment, then metal zinc is added, antimonous oxide and copper sulfate, metal zinc add-on is 1.3-1.5 times of nickel total amount in solution, antimonous oxide add-on is the 0.5wt%-1.0wt% of added metal zinc amount, copper sulfate add-on is the 1.0wt%-1.5wt% of added metal zinc amount, filtration 8 is carried out after reaction times 45-55 minute, filter 8 and obtain water content 14.00wt%-15.00wt%, nickel 15.00wt%-16.00wt%, liquid after the nickel ore concentrate of zinc 8.50 wt%-9.50wt% and heavy nickel, after heavy nickel, liquid returns electric Zn system and reclaims zinc, nickel ore concentrate is then sold.
embodiment 1: the zinc hydrometallurgy high temperature purification slag adopting Yunnan Luoping Zinc & Electricity Co., Ltd. is raw material, after drying, division sample preparation 20000.00 grams is stand-by, and its composition is: zinc 31.15wt%, copper 1.47wt%, cadmium 1.05wt%, cobalt 0.06wt%, nickel 0.04wt%, germanium 0.04wt%, plumbous 3.41wt%, silver-colored 0.0119wt%.
(1) high temperature purification slag calcination: be the high temperature purification slag 15000.00 grams after getting oven dry, the calcination 2.5 hours when 350 DEG C of natural ventilations, obtain containing zinc 32.63wt%, copper 1.54wt%, cadmium 1.10wt%, cobalt 0.063wt%, nickel 0.042wt%, germanium 0.042wt%, plumbous 3.56wt%, silver-colored 0.0125wt% burning after high temperature purification slag 14250.00 grams.
(2) once leach: be do front liquid with process water, get 72 liters, add the high temperature purification slag 13000.00 grams after calcination and carry out pulp; Then with vitriol oil adjustment beginning sour 90g/l, be warmed up to 70 DEG C-80 DEG C and leach, extraction time 1.5 hours, carries out filtration 1 after terminal pH=4.5-5.0.Filter 1 and obtain No. 1 leached mud and No. 1 leach liquor 45.00 liters containing zinc 89.47g/l, copper 3.88 g/l, cadmium 2.80 g/l, cobalt 0.1600 g/l, nickel 0.1100 g/l, germanium 0.1030 g/l, plumbous 0.0028 g/l, silver-colored 0.0002 g/l.No. 1 leached mud carries out secondary leaching, and No. 1 leach liquor carries out next step valuable metal recovery.
(3) secondary leaches: carry out pulp to No. 1 leached mud by the liquid-solid ratio of 3:1, and with vitriol oil adjustment beginning sour 80g/l, control process temperature 80 DEG C-90 DEG C, extraction time 3.0 hours, carries out filtration 2 after terminal acid 50g/l.Filter 2 and obtain water content 14.85wt%, zinc 6.82wt%, copper 0.59wt%, cadmium 0.28wt%, cobalt 0.0240wt%, nickel 0.0160wt%, germanium 0.0150wt%, plumbous 45.17wt%, No. 2 leached mud weight in wet bases 1203 grams of silver-colored 0.1585wt% and No. 2 filtered liquids 14.85 liters containing zinc 9.82g/l, copper 1.32g/l, cadmium 0.95g/l, cobalt 0.0500g/l, nickel 0.0230g/l, germanium 0.0450 g/l, plumbous 0.006 g/l, silver-colored 0.00006 g/l.No. 2 leached muds do plumbous silver preparation concentrate and sell, and No. 2 filtered liquids return once to leach sizes mixing.
(4) the heavy copper of purification: the heavy copper of purification gets No. 1 leach liquor 44 liters, add metal zinc 177 grams, 45 minutes metal zinc joining days, process temperature is normal temperature, after 70 minutes replacement(metathesis)reaction time, filter 23 is carried out to it, filter 23 obtain water content 12.24wt%, copper 63.77wt%, cadmium 0.084wt%, zinc 7.84 wt%, germanium 0.0043wt%, cobalt 0.0048wt%, nickel 0.0041wt% copper powder weight in wet base 299 grams and containing zinc 95.52g/l, copper 0.085g/l, cadmium 2.87g/l, cobalt 0.1640g/l, nickel 0.1127g/l, germanium 0.1055g/l heavy copper after liquid 42.85 liters.After heavy copper, liquid carries out next step heavy cadmium, and copper powder is then sold.
(5) the heavy cadmium of purification: the heavy cadmium of purification gets liquid 41 liters after heavy copper, add metal zinc 69 grams, 30 minutes metal zinc joining days, process temperature is 45 DEG C, after 60 minutes replacement(metathesis)reaction time, filtration 4 is carried out to it, filter 4 obtain water content 20.35wt%, cadmium 75.16wt%, zinc 6.78wt%, germanium 0.0060wt%, cobalt 0.0090wt%, nickel 0.0060wt% sponge cadmium weight in wet base 192 grams and containing zinc 99.83g/l, cadmium 0.067g/l, cobalt 0.1685g/l, nickel 0.1158g/l, germanium 0.1084g/l heavy cadmium after liquid 39.82 liters.After heavy cadmium, liquid carries out next step heavy germanium, and the cotton cadmium of Mare Humorum send cake of press workshop cake of press after founding become thick cadmium ingot and produce pure cadmium.
(6) tannin sinks germanium: get liquid after 38 heave cadmiums, after the heavy cadmium of adjustment liquid pH=2.5-3.5, temperature 65 DEG C-75 DEG C, add 103 grams, Weibull, 20 minutes reaction times after carry out filtration 5, filter liquid 38.00 liters and tannin germanium slag after the 5 heavy germanium obtaining containing zinc 103.38g/l, cobalt 0.1744g/l, nickel 0.1198g/l, germanium 0.0035g/l.After heavy germanium, liquid carries out next step heavy cobalt, and tannin germanium slag washs after 30 minutes and carries out filtration 7 at liquid-solid ratio 3:1, temperature 65 DEG C-75 DEG C, filter 7 obtain water content 61.24wt%, germanium 3.51wt%, zinc 4.08wt%, cobalt 0.009wt%, nickel 0.008wt% wash rear tannin germanium slag weight in wet base 294 grams and 1.20 liters, the tannin germanium wash heat water containing zinc 17.23g/l, cobalt 0.0291g/l, nickel 0.0200g/l, germanium 0.00058g/l.Washing rear tannin germanium slag send germanium concentrate calcination workshop calcination to become germanium concentrate, and germanium wash heat water returns once to leach and sizes mixing.
(7) heavy cobalt: get liquid after 35 heave germanium, temperature 65 DEG C-75 DEG C, add Sodium Nitrite 2.56 grams, 51.22 grams, β-Nai phenol, filtration 6 is carried out after 40 minutes reaction times, filter 6 obtain water content 40.58wt%, cobalt 15.01wt%, nickel 0.005wt%, zinc 5.16wt% cobalt concentrate weight in wet base 68 grams and containing zinc 106.93g/l, cobalt 0.0012g/l, nickel 0.1239g/l heavy cobalt after liquid 33.82 liters, after heavy cobalt, liquid carries out next step heavy nickel, and cobalt concentrate is then sold.
(8) heavy nickel: get liquid after 30.00 heave cobalts, after the heavy cobalt of adjustment liquid pH=5.0-5.2, temperature 75 DEG C-85 DEG C, add metal zinc 5.53 grams, antimonous oxide 0.03 gram, 0.5 gram, copper sulfate, react and carry out filtration 8 after 45 minutes, filter 8 obtain water content 14.35wt%, nickel 15.31wt%, zinc 8.52wt% nickel ore concentrate weight in wet base 28 grams and containing zinc 111.51g/l, nickel 0.0015g/l heavy nickel after liquid 28.80 liters; After heavy nickel, liquid returns electric Zn system and reclaims zinc, and nickel ore concentrate is then sold.
By can be calculated each economic target be:
1. from high temperature purification slag to product; Lead recovery 98.99%, silver raising recovery rate are 99.68%, copper recovery 94.48%, the cadmium rate of recovery are 95.12%, the germanium rate of recovery is 93.68%, the cobalt rate of recovery 95.54%, nickel recovery are 94.89%.
2. whole valuable metal recovery process zinc loss 3.06%, i.e. zinc recovery 96.94%.
3. high temperature purification slag calcination under 350 DEG C of conditions, the evaporation rate of zinc, lead, silver, copper, cadmium, germanium, cobalt, nickel is all less than 1.0%.
4. after calcination, the leaching yield of high temperature sludge each valuable metal element in leaching process is zinc 98.35%, copper 97.00%, cadmium 97.98%, cobalt 96.97%, nickel 96.91%, germanium 97.13%, plumbous 0.14%, silver-colored 0.11% respectively.
5. the plumbous silver preparation concentrate major ingredient of output is: plumbous 45.17wt%, silver-colored 0.1585wt%, copper 0.59wt%, zinc 6.82wt%, arsenic 0.22wt%, magnesium oxide 0.98wt% meet the requirement of lead ore concentrate industry quality standard level Four product.The cobalt concentrate major ingredient of output is: cobalt 15.01wt%, manganese 0.008wt%, plumbous 0.76wt%, arsenic 0.08wt%, cadmium 0.01wt%, mercury 0.0006wt% meet the requirement of mixing cobalt concentrate industry quality standard first grade.The nickel ore concentrate major ingredient of output is: nickel 15.31wt%, magnesium oxide 5.68wt% meet the requirement of nickel ore concentrate industry quality standard select quality.
embodiment 2:
The zinc hydrometallurgy high temperature purification slag adopting Yunnan Luoping Zinc & Electricity Co., Ltd. is raw material, after drying, division sample preparation 18000.00 grams is stand-by, and its composition is: zinc 39.08wt%, copper 3.49wt%, cadmium 1.98wt%, cobalt 0.076wt%, nickel 0.088wt%, germanium 0.076wt%, plumbous 3.96wt%, silver-colored 0.0180wt%.
(1) high temperature purification slag calcination: be the high temperature purification slag 14000.00 grams after getting oven dry, the calcination 3.5 hours when 450 DEG C of natural ventilations, obtain containing zinc 41.76wt%, copper 3.74wt%, cadmium 2.11wt%, cobalt 0.081wt%, nickel 0.094wt%, germanium 0.081wt%, plumbous 4.23wt%, silver-colored 0.0192wt% burning after high temperature purification slag 13020.00 grams.
(2) once leach: be do front liquid with process water, get 66 liters, add the high temperature purification slag 11000.00 grams after calcination and carry out pulp; With vitriol oil adjustment beginning sour 100 g/l, be warmed up to 70 DEG C-80 DEG C and leach, extraction time 2.0 hours, carries out filtration 1 after terminal pH=4.5-5.0.Filter 1 and obtain No. 1 leached mud and No. 1 leach liquor 44.50 liters containing zinc 98.64g/l, copper 8.70 g/l, cadmium 4.83 g/l, cobalt 0.1800 g/l, nickel 0.2190 g/l, germanium 0.1820 g/l, plumbous 0.0026 g/l, silver-colored 0.0021 g/l.No. 1 leached mud carries out secondary leaching, and No. 1 leach liquor carries out next step valuable metal recovery.
(3) secondary leaches: carry out pulp to No. 1 leached mud by the liquid-solid ratio of 4:1, and with vitriol oil adjustment beginning sour 90g/l, control process temperature 80 DEG C-90 DEG C, extraction time 4.0 hours, carries out filtration 2 after terminal acid 60g/l.Filter 2 and obtain water content 14.53wt%, zinc 6.88wt%, copper 0.56wt%, cadmium 0.31wt%, cobalt 0.0220wt%, nickel 0.0150wt%, germanium 0.0140wt%, plumbous 46.05wt%, No. 2 leached mud weight in wet bases 1182 grams of silver-colored 0.1990wt% and No. 2 filtered liquids 13.15 liters containing zinc 10.25g/l, copper 1.42g/l, cadmium 1.05g/l, cobalt 0.0510g/l, nickel 0.0320g/l, germanium 0.0510 g/l, plumbous 0.005 g/l, silver-colored 0.0008 g/l.No. 2 leached muds do plumbous silver preparation concentrate and sell, and No. 2 filtered liquids return once to leach sizes mixing;
(4) the heavy copper of purification: get No. 1 leach liquor 43 liters, add metal zinc 391 grams, 55 minutes metal zinc joining days, process temperature is normal temperature, after 90 minutes replacement(metathesis)reaction time, filter 23 is carried out to it, filter 23 obtains water content 10.13wt%, copper 69.94wt%, cadmium 0.051wt%, zinc 3.92 wt%, germanium 0.0059wt%, cobalt 0.0058wt%, the copper powder weight in wet base 592 grams of nickel 0.0049wt% and containing zinc 108.51g/l, copper 0.048g/l, cadmium 4.88g/l, cobalt 0.1810g/l, nickel 0.2210g/l, liquid 42.50 liters after the heavy copper of germanium 0.1830g/l, after heavy copper, liquid carries out next step heavy cadmium, copper powder is then sold,
(5) the heavy cadmium of purification: the heavy cadmium of purification gets liquid 41.5 liters after heavy copper, add metal zinc 119 grams, 40 minutes metal zinc joining days, process temperature is 50 DEG C, after 70 minutes replacement(metathesis)reaction time, filtration 4 is carried out to it, filter 4 obtain water content 24.85wt%, cadmium 79.80wt%, zinc 7.68wt%, germanium 0.0090wt%, cobalt 0.0050wt%, nickel 0.0090wt% sponge cadmium weight in wet base 335.4 grams and containing zinc 113.64g/l, cadmium 0.035g/l, cobalt 0.1850g/l, nickel 0.2260g/l, germanium 0.1870g/l heavy cadmium after liquid 40.50 liters.After heavy cadmium, liquid carries out next step heavy germanium, and the cotton cadmium of Mare Humorum send cake of press workshop cake of press after founding become thick cadmium ingot and produce pure cadmium;
(6) tannin sinks germanium: get liquid after 39 heave cadmiums, after the heavy cadmium of adjustment liquid pH=2.5-3.5, temperature 65 DEG C-75 DEG C, add 218 grams, Weibull, 30 minutes reaction times after carry out filtration 5, filter liquid 37.52 liters and tannin germanium slag after the 5 heavy germanium obtaining containing zinc 117.18g/l, cobalt 0.1900g/l, nickel 0.2340g/l, germanium 0.005g/l.After heavy germanium, liquid carries out next step heavy cobalt, and tannin germanium slag washs after 40 minutes and carries out filtration 7 at liquid-solid ratio 4:1, temperature 65 DEG C-75 DEG C, filter 7 obtain water content 55.48wt%, germanium 3.20wt%, zinc 4.49wt%, cobalt 0.006wt%, nickel 0.005wt% wash rear tannin germanium slag weight in wet base 499 grams and 1.53 liters, the tannin germanium wash heat water containing zinc 16.54g/l, cobalt 0.0320g/l, nickel 0.0210g/l, germanium 0.00061g/l.Washing rear tannin germanium slag send germanium concentrate calcination workshop calcination to become germanium concentrate, and tannin germanium wash heat water returns once to leach and sizes mixing;
(7) heavy cobalt: get liquid after 36 heave germanium, temperature 65 DEG C-75 DEG C, add Sodium Nitrite 3.42 grams, 82.00 grams, β-Nai phenol, filtration 6 is carried out after 60 minutes reaction times, filter 6 obtain water content 44.82wt%, cobalt 15.83wt%, nickel 0.008wt%, zinc 5.94wt% cobalt concentrate weight in wet base 78 grams and containing zinc 123.42g/l, cobalt 0.0010g/l, nickel 0.2465g/l heavy cobalt after liquid 34.16 liters, after heavy cobalt, liquid carries out next step heavy nickel, and cobalt concentrate is then sold;
(8) heavy nickel: get liquid after 31.00 heave cobalts, after the heavy cobalt of adjustment liquid pH=5.0-5.2, temperature 75 DEG C-85 DEG C, add metal zinc 11.50 grams, antimonous oxide 0.12 gram, 0.17 gram, copper sulfate, react and carry out filtration 8 after 55 minutes, filter 8 obtain water content 14.95wt%, nickel 15.85wt%, zinc 9.48wt% nickel ore concentrate weight in wet base 56.50 grams and containing zinc 130.60g/l, nickel 0.0012g/l heavy nickel after liquid 29.26 liters; After heavy nickel, liquid returns electric Zn system and reclaims zinc, and nickel ore concentrate is then sold.
By can be calculated each economic target be:
1. from high temperature purification slag to product; Lead recovery 99.30%, silver raising recovery rate are 99.15%, copper recovery 97.77%, the cadmium rate of recovery are 96.84%, the germanium rate of recovery is 96.68%, the cobalt rate of recovery 94.77%, nickel recovery are 96.71%;
2. whole valuable metal recovery process zinc loss 3.38%, i.e. zinc recovery 96.62%.
3. high temperature purification slag calcination under 450 DEG C of conditions, the evaporation rate of zinc, lead, silver, copper, cadmium, germanium, cobalt, nickel is all less than 1.0%.
4. after calcination, the leaching yield of high temperature sludge each valuable metal element in leaching process is zinc 98.49%, copper 98.64%, cadmium 98.55%, cobalt 97.43%, nickel 98.32%, germanium 98.42%, plumbous 0.039%, silver-colored 0.05% respectively.
5. the plumbous silver preparation concentrate major ingredient of output is: plumbous 46.05wt%, silver-colored 0.1990wt%, copper 0.56wt%, zinc 6.88wt%, arsenic 0.23wt%, magnesium oxide 0.96wt% meet the requirement of lead ore concentrate industry quality standard level Four product.The cobalt concentrate major ingredient of output is: cobalt 15.83wt%, manganese 0.006wt%, plumbous 0.74wt%, arsenic 0.06wt%, cadmium 0.01wt%, mercury 0.0007wt% meet the requirement of mixing cobalt concentrate industry quality standard first grade.The nickel ore concentrate major ingredient of output is: nickel 15.85wt%, magnesium oxide 5.69wt% meet the requirement of nickel ore concentrate industry quality standard select quality.
Claims (1)
1. the method for comprehensively recovering valuable metal from zinc hydrometallurgy high temperature purification slag, is characterized in that completing according to the following steps:
1) oven dry of high temperature purification slag and calcination: first to containing zinc 30wt%-40wt%, cupric 1.5wt%-3.5wt%, containing cadmium 1.0wt%-2.0wt%, dry containing the high temperature purification slag of cobalt 0.06wt%-0.08wt%, nickeliferous 0.04wt%-0.09wt%, germanic 0.05wt%-0.08wt%, leaded 3.0wt%-4.0wt%, argentiferous 0.01wt%-0.02wt%, then the high temperature purification slag of drying calcination 2.5-3.0 hour when natural ventilation, calcination temperature is 350 DEG C-450 DEG C, makes each valuable metal in slag fully oxidized;
2) once leach: with process water, the high temperature purification slag after calcination is carried out pulp by the liquid-solid ratio of 5-6:1, slurry time 0.2-0.4 hour, with vitriol oil adjustment beginning sour 90-100g/l, control process temperature 70 C-80 DEG C, extraction time 1.5-2.0 hour, filtration 1 is carried out, output No. 1 leached mud and No. 1 leach liquor after terminal pH=4.5-5.0; No. 1 leached mud carries out secondary leaching, and No. 1 leach liquor carries out next step valuable metal recovery;
3) secondary leaches: carry out pulp to No. 1 leached mud by the liquid-solid ratio of 3-4:1, with vitriol oil adjustment beginning sour 80-90g/l, control process temperature 80 DEG C-90 DEG C, extraction time 3.0-4.0 hour, carry out filtration 2 after terminal acid 50-60g/l, output No. 2 leached muds can return once to leach as plumbous silver preparation concentrate sale and No. 2 leach liquors and do pulp liquid;
4) the heavy copper of purification: the heavy copper of purification is according to copper, cadmium, germanium, cobalt, the current potential of nickel is different, the metal zinc No. 1 leach liquor being added at normal temperatures to the 98wt%-99wt% of copper theoretical amount carries out copper displacement, metal zinc joining day 45-55 minute, after 70-90 minute replacement(metathesis)reaction time, filter 23 is carried out to it, filter 23 obtains water content 10.00wt%-12.50wt%, copper 64wt%-70wt%, cadmium 0.05wt%-0.09wt%, zinc 3.50wt%-8.00wt%, germanium 0.004wt%-0.006wt%, cobalt 0.004wt%-0.006wt%, liquid after the copper powder of nickel 0.004wt%-0.005wt% and heavy copper, after heavy copper, liquid carries out next step heavy cadmium, and copper powder then can be sold,
5) the heavy cadmium of purification: the heavy cadmium of purification is different according to the current potential of cadmium, germanium, cobalt, nickel, metal zinc liquid after heavy copper being added at 45 DEG C-50 DEG C to the 97wt%-99wt% of cadmium theoretical amount carries out cadmium displacement, metal zinc joining day 30-40 minute, after 60-70 minute replacement(metathesis)reaction time, filtration 4 is carried out to it, filter 4 and obtain liquid after water content 20.00wt%-25.00wt%, cadmium 75.00wt%-80.00wt%, zinc 6.50wt%-8.00wt%, germanium 0.006wt%-0.009wt%, cobalt 0.005wt%-0.009wt%, the sponge cadmium of nickel 0.006wt%-0.009wt% and heavy cadmium; After sponge cadmium send cake of press workshop cake of press, founding becomes thick cadmium ingot and produces pure cadmium, and the tannin that after heavy cadmium, liquid carries out next step sinks germanium;
6) tannin sinks germanium: because the chemical property of germanium, cobalt, nickel determines, is difficult to separately germanium be separated from containing the high solution of cobalt, nickel with zinc powder.Therefore adopt tannin to sink the method for germanium here to precipitate germanium, cobalt, nickel then retain in the solution.Actual conditions is the pH=2.5-3.5 of liquid after first adjusting heavy cadmium, temperature 65 DEG C-75 DEG C, add Weibull amount be the 25-30 of germanium total amount in solution doubly, carry out filtration 5 after reaction times 20-30 minute, filter 5 and obtain liquid after tannin germanium slag and heavy germanium; After heavy germanium, liquid carries out next step heavy cobalt, and tannin germanium slag carries out filtration 7 after needing to wash 30-40 minute at liquid-solid ratio 3-4:1, temperature 65 DEG C-75 DEG C; Filter 7 obtain water content 55.00wt%-65.00wt%, germanium 3.20wt%-3.60wt%, zinc 4.00wt%-4.50wt%, cobalt 0.006wt%-0.009wt%, nickel 0.005wt%-0.008wt% wash rear tannin germanium slag and germanium wash heat water.Washing rear tannin germanium slag send the calcination of calcination workshop to become germanium concentrate to sell, and germanium wash heat water returns once to leach and sizes mixing;
7) heavy cobalt: be that liquid after heavy germanium is warming up to 65 DEG C-75 DEG C, then Sodium Nitrite and β-Nai phenol is added, Sodium Nitrite add-on is 0.4-0.5 times of cobalt total amount in solution, β-Nai phenol add-on is 8-12 times of cobalt total amount in solution, carry out filtration 6 after reaction times 40-60 minute, filter 6 and obtain liquid after water content 40wt%-50wt%, cobalt 15.00wt%-16.00wt%, nickel 0.005wt%-0.008wt%, the cobalt concentrate of zinc 5.00wt%-6.00wt% and heavy cobalt; After heavy cobalt, liquid carries out next step heavy nickel, and cobalt concentrate then can be sold;
8) heavy nickel: be that liquid after heavy cobalt is warming up to 75-85 DEG C, the pH=5.0-5.2 of liquid after the heavy cobalt of adjustment, then metal zinc is added, antimonous oxide and copper sulfate, metal zinc add-on is 1.3-1.5 times of nickel total amount in solution, antimonous oxide add-on is the 0.5wt%-1.0wt% of added metal zinc amount, copper sulfate add-on is the 1.0wt%-1.5wt% of added metal zinc amount, filtration 8 is carried out after reaction times 45-55 minute, filter 8 and obtain water content 14.00wt%-15.00wt%, nickel 15.00wt%-16.00wt%, liquid after the nickel ore concentrate of zinc 8.50 wt%-9.50wt% and heavy nickel, after heavy nickel, liquid returns electric Zn system and reclaims zinc, and nickel ore concentrate then can be sold.
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