CN101942560A - Method for directly leaching low-grade germanic lead oxide and zinc oxide ores - Google Patents

Method for directly leaching low-grade germanic lead oxide and zinc oxide ores Download PDF

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CN101942560A
CN101942560A CN2010105092779A CN201010509277A CN101942560A CN 101942560 A CN101942560 A CN 101942560A CN 2010105092779 A CN2010105092779 A CN 2010105092779A CN 201010509277 A CN201010509277 A CN 201010509277A CN 101942560 A CN101942560 A CN 101942560A
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ore
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梁杰
胡琼
周军
杨玉琼
鱼鹏涛
李�瑞
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BIJIE UNIVERSITY
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Abstract

The invention discloses a method for directly leaching low-grade germanic lead oxide and zinc oxide ores. The method comprises the following steps of: adding mineral sands into a leaching pool, adding diluted sulfuric acid into the leaching pool according to a liquid-solid ratio of 2:2-5:1 to perform leaching for the first time, and obtaining a leachate A after 30 to 90 days of the leaching which is performed at the natural environment temperature; removing leaching residues in the leaching pool, re-adding new mineral sands into the leaching pool, adding the leachate A into the leaching pool for leaching, adjusting the sulfuric acid concentration to be between 40 and 100 g/L, performing leaching on the second batch of the mineral sands, and obtaining a leachate B after 30 to 90 days of the leaching which is performed at the natural environment temperature; and repeating the second step until the zinc ion concentration in the obtained leachate accords with an extraction process requirement. The method adopts a heap leaching method to process the low-grade lead oxide and zinc oxide ores, uses a recycle leaching mode to leach metal zinc in the low-grade lead oxide and zinc oxide ores and has simple technical processes and low production cost; the obtained leachate can be processed conveniently; and other valuable metals such as germanium and the like in raw materials can be comprehensively recovered.

Description

Directly leach the method for low-grade germanic lead-zinc
Technical field
The present invention relates to a kind of METAL EXTRACTION method, the method for the low-grade germanic lead-zinc of particularly a kind of direct leaching.
Background technology
Zinc and compound thereof have purposes widely, and zinc has the good market requirement, and the metallurgical development of China's zinc rapidly.But because the metallurgical resource-constrained of zinc causes the zinc metallurgical raw material in short supply, for keeping the metallurgical sustainable and healthy development of zinc, must the various zinc raw materials of development and use.All the time, zinc sulfide ore is the main raw material that extracts metallic zinc.Along with the consumption of the zinc sulfide ore of easy choosing and the zinc oxide ore that can directly smelt, in, the problem of utilizing of low-grade lead-zinc day by day draws attention, the low-grade lead zinc resource is the important source material that zinc is smelted.By the comparative analysis of zinc metallurgical technology as can be known, adopting the pyrogenic process process of enriching for low-grade lead-zinc (containing zinc less than 15%) is feasible technically, but the cost height pollutes big.Low grade ore is one of developing direction of zinc metallurgical technology in the employing wet processing.
Guizhou Province contains the lead-zinc resource that relatively abundanter associated metal germanium is arranged, and mainly is distributed in rather area of Hezhang, prestige.Geologic information shows: only press in the sub-factories and miness district proven reserve in the sixth of the twelve Earthly Branches the Hezhang, and plumbous zinc 210kt, germanium 180t, silver-colored 120t are just arranged.The ore average grade is Zn4.26%, Pb2.36%, Ge56g/T.The plumbous zinc reserves of cat cat factories and miness are 6.901 ten thousand tons, and its average grade is Zn8.16%, Pbl.47%, Ge40～60g/T; The plumbous zinc reserves in cave ore deposit of dehiscing are 0.7013 ten thousand tons, and its grade is Zn 1.5%～10.54%, Pb0.12%～1.84%, Ge45～60g/T.The fuming process enrichment that this ore deposit industrial employing blast furnace melting mineral is equipped with the fuming furnace blowing obtains zinc oxide fumes, wherein contain Zn35～40%, Pb22～28%, Ge350～500g/T, Ag180～220g/T are to extract metallic zinc germanium, and the comprehensive important source material that reclaims plumbous silver.
The low-grade germanic lead-zinc of industrial processing adopts the blast furnace slack melt that partly volatilizees, and its slag is in that blowing makes in the mineral plumbous zinc germanium volatilization and obtains enrichment through fuming furnace, and then extracts valuable metal with wet processing.Its pyrogenic process partly exists shortcomings such as the rate of recovery is low, pollution is big, energy consumption height.
Summary of the invention
The invention provides the method for the low-grade germanic lead-zinc of a kind of direct leaching, its production cost is low, and technological process is simple, can reach the purpose that leaches metallic zinc, can comprehensively reclaim other valuable metals such as germanium in the raw material again, to overcome the deficiencies in the prior art.
The present invention is achieved in that the method for the low-grade germanic lead-zinc of direct leaching, (1) in leaching the pond, adds ore in sand form, add dilute sulphuric acid according to liquid-solid ratio 2:1～5:1 and carry out the leaching first time, the leaching agent dilute sulphuric acid adds from leaching the top, pond, solution leaches from leaching the bottom, pond, filtrate is returned to add and is leached the pond, and after leaching 30～90 days under the physical environment temperature, obtains leach liquor A; (2) will leach that leached mud shifts out in the pond, add new ore in sand form again, and again will leach liquor A add to leach in the pond and soak, and adjust sulfuric acid concentration to 40～100 g/L, and carry out second batch of ore in sand form and leach, after leaching 30～90 days under the physical environment temperature, obtain leach liquor B; (3) zinc ion concentration of repeating step (2) in the leach liquor that obtains meets the extraction process requirement.
Vitriolic acidity is 40～100 g/L.Ore in sand form is an oxidized ore, and the ore in sand form zinc content is less than 10%, and germanic amount is 40-120 g/T.
In order to verify feasibility of the present invention, carry out following test according to processing condition of the present invention:
Experimental program:
Simultaneously also in order to utilize the useful component in the low-grade zinc oxide ore better, this experiment adopts the dump leaching method to handle low-grade lead-zinc at this situation.Good or bad for what determine that zinc leaches in the low-grade zinc oxide ore heap leaching process, just must know the leaching performance of zinc in the zinc oxide ore.For this reason, at first carry out the normal temperature leaching performance experimental study of low-grade zinc oxide ore, obtain the correlation technique parameter, to its leaching test research that circulates, consist predominantly of following content again:
1, the research of low-grade lead-zinc leaching process, the application heap leaching method directly leaches this ore deposit;
2, find out the optimum process condition that diafiltration is leached, i.e. vitriolic acidity, extraction time, how many liquid-solid ratioes is respectively, and leaches this ore deposit with this understanding and obtains first leach liquor;
3, the liquid-solid ratio scope be 5:1 to 2:1, circulate respectively with this leach liquor and to leach the next batch ore deposit, stable up to the leaching of zinc, change another batch ore deposit again;
4, investigate sulfuric acid and leach with hydrochloric acid and leach influence, analyze the behavior and the regularity of distribution of iron and silicon-dioxide etc. zinc leaching rate and useful component lead, silver, germanium.
Ore character: the test sample ore is taken from zinc oxide ore mining area, Hezhang County, Guizhou Province, and its main chemical analytical results is shown in table 1-1:
Table 1-1 zinc oxide ore main chemical analytical results
Ore grain size: account for more than 100 orders and account for 17.93%, 100 order below 4.74%, 200 order and have 77.33% between 200 orders.The zinc content of mineral is very low as can be seen from the above table, only is 6.84%, and the total content of plumbous zinc is less than 11%.And simultaneously Fe2O3, SiO2 content respectively up to 29.42% and 23.39%.
Low-grade germanic lead-zinc sulfuric acid leaches:
1, acidity of sulfuric acid is to the influence of test-results
Acidity is the important factor that influences leaching process, and it not only can control the effect of whole leaching process, simultaneously, because the acidity difference causes impurity concentration to vary in size.Thereby processes such as follow-up leach liquor filtration, extraction, electrodeposition are produced crucial influence.
In extraction time 30 days, liquid-solid ratio 5/1, carry out the experimental study of acidity of sulfuric acid under the normal temperature (25 ℃) to the influence of low-grade zinc oxide ore leaching yield.Leaching the results are shown in Table 1-2, Fig. 1, Fig. 2.
Table 1-2 acidity of sulfuric acid is to leaching result's influence
Figure 524331DEST_PATH_IMAGE002
We can see that the leaching yield along with the increase zinc of acidity of sulfuric acid is increasing gradually from table 1-2 and Fig. 1, and acidity is that zinc leaching rate increasess slowly after the 90g/L, zinc leaching rate slightly descend (66.45%) in 100g/L.Simultaneously we find that the highest leaching yield of zinc only is 66.50%, and this is mainly relevant with our extraction temperature and composition of ores.
Different with Zn as can be seen by table 1-2 and Fig. 2, the increase of acidity of sulfuric acid plays a role clearly to the leaching yield of silicon-dioxide, and along with the increase of acidity of sulfuric acid, the leaching yield of silicon-dioxide is more and more higher.This is owing to exist a large amount of SiO in the zinc oxide ore 2, and wherein a part of SiO 2Do not form compound and can generate H with the sulphuric acid soln reaction at normal temperatures with Zn 4SiO 4(silicic acid), but this to be us do not wish to obtain because silicone content is high more in the solution, the strainability of leach liquor is just poor more.
Simultaneously along with the increase germanium of acidity and the leaching yield of iron are also increasing gradually, germanium is that we wish that it enters the material of leach liquor in this experiment, germanium in the leach liquor will be reclaimed with method of extraction, and we can see that when acidity of sulfuric acid was 90g/L, the leaching yield of germanium had reached 75.98%.
2, liquid-solid ratio is to the influence of test-results
At acidity of sulfuric acid 70g/L, investigate different liquid-solid ratioes under 10 days the condition of extraction time to leaching result's influence, leach the result shown in table 1-3.
Table 1-3 liquid-solid ratio is to leaching result's influence
Figure 28124DEST_PATH_IMAGE003
By the result who shows 1-3 and Fig. 3 as can be known, along with the increase of liquid-solid ratio, zinc leaching rate has certain increase.This is that free material total amount is big in the leach liquor owing to increase liquid-solid ratio, and the total acid consumption that in fact leaches beginning increases; The consumption of acid is that liquid-solid ratio is half of 6/1 acid amount when liquid-solid ratio 3/1, and leaching in liquid-solid ratio 4/1 back increases liquid-solid ratio, and leaching yield increases little, but increase liquid-solid ratio simultaneously the residual acid of leach liquor is raise, and is unfavorable for the processing of subsequent technique.
From table 1-3 and Fig. 4 as can be seen, the leaching yield of iron, germanium and silicon-dioxide increases along with the increase of liquid-solid ratio, but owing to leach acidity of sulfuric acid lower (70g/L), make that the leaching yield of iron and silicon-dioxide is lower, and the leaching yield of germanium still remains on higher level, and liquid-solid ratio reaches 77.47% in 6/1.
, extraction time is to the influence of test-results
At liquid-solid ratio: L/S=5/1, carry out the experimental study of extraction time under acidity of sulfuric acid: the 70g/L, 25 ℃ of normal temperature to the influence of low-grade zinc oxide ore leaching yield, the results are shown in Table 1-4, Fig. 5, Fig. 6.
Table 1-4 extraction time is to the influence of test-results
Figure 752629DEST_PATH_IMAGE004
From showing 1-4 and result shown in Figure 5 as can be known, along with the increase of extraction time, the very fast raising of zinc leaching rate.After extraction time was greater than 30 days, the leaching yield of zinc increased little, and along with the passing of extraction time, the decline of solution acidity, and the zinc that has leached hydrolysis partly takes place enters and make the leaching yield of zinc slightly descend in the leached mud.
From table 1-4 and Fig. 6 as can be seen, the leaching yield along with the increase iron of time does not enlarge markedly.This explanation leaching yield of iron under this test conditions has reached maximum leaching yield at preceding 10 days, also can great changes have taken place even leach for some time again; Begin the leaching yield of silicon-dioxide always in slow increase from reaction; Leach 30 days later on along with the carrying out of reaction, leach liquor acidity descends, and part unit molecule silicic acid generation polymerization generates oarse-grained γ form silicic acid precipitation, and its leaching yield descends to some extent; The leaching yield of germanium reached 78.13% in 30 days, after this As time goes on, the germanium leaching yield does not have large increase.
, sulfuric acid leaches orthogonal test
By above single factor experiment, the condition of each principal element is definite substantially, carries out the orthogonal regression test on this basis and leaches optimum process condition to determine sulfuric acid.It is acidity of sulfuric acid, liquid-solid ratio and extraction time that orthogonal test is chosen the investigation factor, and each factor is got three levels, therefore chooses L 9(3 4) orthogonal table arrangement test.Select for use level to see Table 1-5, testing program design and test-results thereof and see Table 1-6.
Table 1-5 experimental factor and level
Figure 378782DEST_PATH_IMAGE005
Table 1-6 L9(34) orthogonal experimental design
Figure 703584DEST_PATH_IMAGE006
The analysis of testing data and processing: experimental data adopts the range analysis method that data are handled.
1, range analysis
Table 1-7 range analysis table
Figure 150932DEST_PATH_IMAGE008
According to the aforementioned calculation result, relatively extreme difference value size as can be known: △ A ﹥ △ C ﹥ △ B explanation acidity of sulfuric acid is to influence the topmost factor of zinc leaching rate, and extraction time takes second place.So determine that zinc leaches optimum process condition and is: A 2C 3B 3Be acidity of sulfuric acid 90g/L, extraction time 40 days, liquid-solid ratio 5/1.
2, variance analysis
A, calculating total deviation sum of squares
The total deviation sum of squares
Figure 885670DEST_PATH_IMAGE009
Represented the change conditions of each testing data around population mean.By the test as can be known, the index of test-results fluctuates between 64.21～68.65, each test-results with
Figure 177062DEST_PATH_IMAGE010
Expression is used
Figure 350554DEST_PATH_IMAGE011
The mean value of representing them.
Figure 298919DEST_PATH_IMAGE012
Figure 266875DEST_PATH_IMAGE013
B, calculating factor change sum of squares
Factor A is placed on L 9(3 4) first the listing of orthogonal table, have three one levels, three two levels, three three levels.With the level of factor A average influence to intensity
Figure 995982DEST_PATH_IMAGE015
1/ 3 replace the influence of each level (totally three) to intensity.With two levels of factor A average influence to intensity
Figure 126749DEST_PATH_IMAGE016
1/ 3 replace the influence of each two level (totally three) to intensity.In like manner, use
Figure 203290DEST_PATH_IMAGE017
1/ 3 replace the influence of each three level to intensity.According to the comprehensive comparability of orthogonal table, 1/ 3,
Figure 36434DEST_PATH_IMAGE016
1/ 3,
Figure 710123DEST_PATH_IMAGE017
1/ 3 these three mean values can compare mutually, and they have reflected the difference between three levels of factor A.So sum of square of deviations S of factor A ACan be by calculating three
Figure 19881DEST_PATH_IMAGE015
1/ 3, three
Figure 90606DEST_PATH_IMAGE016
1/ 3, three
Figure 81695DEST_PATH_IMAGE017
1/ 3 obtain with the sum of square of deviations of Y.That is:
Figure 921475DEST_PATH_IMAGE018
Figure 402135DEST_PATH_IMAGE019
In multifactorial experiment, exist error without any exception.Do not arrange the blank column of factor to calculate at this moment in the sum of square of deviations available orthogonal table of miscalculation.Method of calculation and calculating S A, S BIdentical Deng the row method.In this test with the 4th row
Figure 881527DEST_PATH_IMAGE015
4,
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4,
Figure 370594DEST_PATH_IMAGE017
4Mean value respectively with Y 3 times of the difference sum of squares calculate S MistakeThat is:
Figure 22155DEST_PATH_IMAGE020
Because do not arrange factor in these row, so calculate S MistakeSum of square of deviations in do not have the difference between level of factor to cause yet deviation, these row have only reflected the testing error size.Therefore:
Figure 67472DEST_PATH_IMAGE021
The significance of d, check factor
Calculate S Cause, f Cause, S Mistake, f MistakePurpose be for the change of the caused test-results of variation of factor of judgment level whether remarkable.Therefore adopt the analysis of variance of single factor experiment to carry out test of significance.Promptly calculate V CauseWith V MistakeRatio, then the threshold value with the F-distribution table compares.
According to F A, F B, F CValue select corresponding F threshold value.To significance level α=0.05, look into F-distribution fractile table and get F 0.05(2,2)=19 are so it is as follows to get analysis of variance table.
Table 1-8 analysis of variance table
Figure 699890DEST_PATH_IMAGE023
Known by above The results of analysis of variance: under selected level, factor A is the most remarkable to test index influence, C secondly, B is the most weak, top condition is A2C3B3.
Drawn by range analysis and The results of analysis of variance, optimum process condition is A2C3B3, i.e. acidity of sulfuric acid 90g/L, extraction time 40 days, liquid-solid ratio 5/1.This group experiment does not appear in the orthogonal experiment, therefore need do for supplement and verify.With above-mentioned optimum process condition is the proof test condition, and the confirmatory experiment result is as follows:
Table 1-9 proof test result
Above proof test result has further proved the exactness of extreme difference variance analysis, and the leaching yield of zinc, germanium has all had further raising.
The vitriolic circulation is leached: the optimum process condition that records the sulfuric acid leaching by experiment is acidity of sulfuric acid 90g/L, extraction time 40 days, liquid-solid ratio 5:1.
Leach first ore deposit with sulfuric acid, claim ore deposit 1000g, sulfuric acid (95%～98%) 5L during the leaching 30 days, leaches at normal temperatures.Raw ore contains Zn6.84%, TFe2O3 29.42%, Pb3.72%, SiO2 23.39%, Al2O312.48%, Ge0.00595%, Ag33.8g/t.Leach the 2-1 that the results are shown in Table that analyzes.
Table 2-1 lead-zinc sulfuric acid leaches analytical results
Figure 992648DEST_PATH_IMAGE025
Zinc concentration is 9.8 g/l in the sulphuric leachate, and the concentration of iron is 4.28g/l, initial acidity 90g/L.Soak after rolling in first ore deposit, and the acidity of leach liquor is 79.08g/L, and slag is heavy: 889.67g.
With the sulphuric leachate of optimum process condition, leach the next batch ore deposit.When circulation was leached, we had leached three batches of ore deposits respectively with different liquid-solid ratioes from 2:1 to 5:1, examine or check the wherein leaching situation of zinc, germanium, lead, silver, iron, silicon-dioxide etc.
Liquid-solid ratio is that the circulation of 5:1 is leached
Claim ore deposit 200g, with the leach liquor 1L leaching that circulates.Leaching the results are shown in Table 2-2 and table 2-3.
Table 2-2 liquid-solid ratio is zinc in the leach liquor of 5:1, iron analysis
Figure 925969DEST_PATH_IMAGE026
After having circulated in every batch of ore deposit, leached mud heavily is respectively 210.92g, 202.39g, and 200.45g, the weight of slag has surpassed the weight of raw ore, and this is because circulation time has generated the cause of vitriol.The leaching yield of zinc is respectively 36.33%, 49.94%, 24.39%, and the ionic concn of valuable metal increases.The leaching yield of iron is respectively 0%, 2.16%, 2.0%.
Table 2-3 liquid-solid ratio is the leached mud chemical analysis of 5:1
Figure 781798DEST_PATH_IMAGE027
By table 2-3 as can be seen, be that circulation is leached under the situation of 5:1 in liquid-solid ratio, in the mineral leaching of each element more regular, wherein the leaching of SiO2, MgO, Pb, Ag reduces gradually, has been accumulated in the slag.The leaching yield of germanium is respectively 50.98%, 35.5%, 23.32%, and circulation is leached under the situation of initial leaching yield 75.98%, and the concentration of metal ions of germanium has also obtained significantly increasing.The leaching yield of silicon-dioxide is 0%, and in circulation was leached, they did not leach, but have been accumulated in the slag.
Liquid-solid ratio is that the circulation of 4:1 is leached
Claim ore deposit 200g, with the leach liquor 800mL leaching that circulates.Leaching the results are shown in Table 2-4 and table 2-5.
Table 2-4 liquid-solid ratio is zinc in the leach liquor of 4:1, iron analysis
Figure 40741DEST_PATH_IMAGE028
After having circulated in every batch of ore deposit, leached mud heavily is respectively 207.08g, 200.31g, and 205.57g, the weight of slag has also surpassed the weight of raw ore, is because circulation time has generated the cause of vitriol equally.
From table 2-4 as can be seen, be comparing of 5:1 with liquid-solid ratio, the leaching of zinc increases to some extent, and the leaching of iron reduces to some extent.The leaching yield of zinc is respectively 52.44%, 36.85%, 24.32%, and same, the concentration of zine ion increases gradually.The leaching yield of iron is respectively 0%, 2.15%, 0.81%.
Table 2-5 liquid-solid ratio is the leached mud chemical analysis of 4:1
Figure 467174DEST_PATH_IMAGE029
The leaching yield of germanium is respectively 52.25%, 37.79%, 20.49%, and the leaching yield of silicon-dioxide all is 0%, and silicon-dioxide does not still leach, and has been accumulated in the slag.The leaching of other elements becomes irregular when the 3rd batch of ore deposit, continue to reduce liquid-solid ratio and observe the leaching situation.
Liquid-solid ratio is that the circulation of 3:1 is leached
Claim ore deposit 100g, with the leach liquor 300mL leaching that circulates.Leaching the results are shown in Table 2-6 and table 2-7.
Table 2-6 liquid-solid ratio is zinc in the leach liquor of 3:1, iron analysis
Figure 469765DEST_PATH_IMAGE030
Table 2-7 liquid-solid ratio is the leached mud chemical analysis of 3:1
Figure 681566DEST_PATH_IMAGE031
Soak after rolling in every batch of ore deposit, and the weight of leached mud is respectively 106.37g, 105.20g, 108.91g.
Is respectively 34.11%, 24.13%, 6.68% from table 2-6 with the leaching yield that table 2-7 can calculate zinc.The leaching yield of iron is respectively 0%, 0.42%, 0.41%, and the leaching of iron remains on a lower level.The leaching yield of germanium is respectively 54.59%, 36.66%, 20.06%.The leaching yield of silicon-dioxide all is 0%.4:1 compares with liquid-solid ratio, and the leaching of zinc reduces, and the leaching of germanium increases.The reduction of liquid-solid ratio makes that free material total amount reduces in the leach liquor, so the leaching of zinc reduces.According to the analysis of chapter 3, the solubleness of germanium dioxide in sulfuric acid is to reduce along with the increase of acidity, and at circulation time, along with liquid-solid ratio reduces, whole acid concentration also reduces, so the leaching of germanium increases.
Liquid-solid ratio is that the circulation of 2:1 is leached
Claim ore deposit 200g, with the leach liquor 400mL leaching that circulates.Leaching the results are shown in Table 2-8 and table 2-9.
Table 2-8 liquid-solid ratio is zinc in the leach liquor of 2:1, iron analysis
Figure 845831DEST_PATH_IMAGE032
Soak after rolling in every batch of ore deposit, and the weight of leached mud is respectively 198.81g, 205.84g, 204.84g.
The leaching yield of zinc is respectively 23.81%, 19.65%, 13.40%.The leaching yield of iron is respectively 0%, 0.03%, 0.04%, and iron keeps lower level in the circulation time leaching yield always.The leaching yield of germanium is respectively 67.72%, 52.00%, 35.29%.Circulate in three batches of ore deposits, silicon-dioxide does not all have to leach, and leaching yield is 0%.
Table 2-9 liquid-solid ratio is the leached mud chemical analysis of 2:1
Figure 87457DEST_PATH_IMAGE033
From above form as can be seen, at circulation time, along with the reduction of liquid-solid ratio, the leaching yield of zinc reduces gradually, and the leaching of iron reduces gradually, and the leaching of germanium increases gradually, and leaching yield has reached 67.72%, and this is relevant with the liquid-solid acidity of leach liquor when.
The zinc leaching performance is good in the low-grade lead-zinc, and it is feasible adopting heap leaching method, and its dump leaching speed is mainly determined by the physicochemical property of low-grade lead-zinc.Circulation is leached and have been improved the ionic concn of valuable metal in the leach liquor, and this is for the crucial effects that played of the recovery of valuable metal in the raw material and next step operation.Therefore, the selection of liquid-solid ratio need be considered according to the character of ore itself, also needs to consider the efficiency of actual production simultaneously.
Beneficial effect of the present invention: adopt the dump leaching method to handle low-grade lead-zinc, the mode of utilizing circulation to leach leaches the metallic zinc in the low-grade lead-zinc, its technological process is simple, low production cost, the leach liquor that obtains is handled convenient, also can comprehensively reclaim other valuable metals such as germanium in the raw material.The inventive method is simple, and is applied widely, the result of use ideal.
Description of drawings
Accompanying drawing 1 is the influence of acidity of sulfuric acid to zinc leaching rate;
Accompanying drawing 2 is the influence of acidity of sulfuric acid to iron, silicon-dioxide, germanium leaching yield;
Accompanying drawing 3 is the influence of liquid-solid ratio to zinc leaching rate;
Accompanying drawing 4 is the influence of liquid-solid ratio to iron, silicon-dioxide, germanium leaching yield;
Accompanying drawing 5 is the influence of extraction time to zinc leaching rate;
Accompanying drawing 6 is the influence of extraction time to iron, silicon-dioxide, germanium leaching yield.
Below in conjunction with embodiment the present invention is further detailed.
Embodiment
Embodiments of the invention 1: the technology that directly leaches low-grade germanic lead-zinc, be 8% with zinc ion content earlier, germanic amount is that the ore in sand form of 80 g/T adds in the leaching pond, adding concentration according to the liquid-solid ratio of 5:1 is that the dilute sulphuric acid of 90g/L carries out leaching first time, the leaching agent dilute sulphuric acid adds from leaching the top, pond, solution leaches from leaching the bottom, pond, by the Flux Valve Control flow of filtrate, filtrate is returned to add and is leached the pond, and after (determining envrionment temperature) under the physical environment temperature and leaching 40 days according to concrete weather and place, leach leached mud, obtain leach liquor A; In leach liquor A, add the raw ore that contains zine ion once more, and additional sulfuric acid, carry out the second time and leach, after leaching 40 days under the physical environment temperature, leach leached mud again, obtain leach liquor B; Add the raw ore that contains zine ion once more, and additional sulfuric acid, leach for the third time, after leaching 40 days under the physical environment temperature, leach leached mud again, obtain leach liquor C, promptly obtain the product of this operation.
Directly leach the technology of low-grade germanic lead-zinc, it is characterized in that: (1) adds ore in sand form in leaching the pond, carrying out the first time according to liquid-solid ratio 2:1～5:1 leaches, the leaching agent dilute sulphuric acid adds from leaching the top, pond, solution leaches from leaching the bottom, pond, and by the Flux Valve Control flow of filtrate, filtrate is returned to add and leached the pond, and after leaching 30～90 days under the physical environment temperature, obtain leach liquor A; (2) will leach that leached mud shifts out in the pond, add new ore in sand form again, and again will leach liquor A add to leach in the pond and soak, and adjust sulfuric acid concentration to 40～100 g/L, and carry out second batch of ore in sand form and leach, after leaching 30～90 days under the physical environment temperature, obtain leach liquor B; (3) zinc ion concentration of repeating step (2) in the leach liquor that obtains meets the extraction process requirement.
Embodiment 2: the technology that directly leaches low-grade germanic lead-zinc, the ore in sand form that earlier with zinc ion content be 5%, germanic amount is 40 g/T adds and leaches in the pond, adding concentration according to the liquid-solid ratio of 4:1 is that the dilute sulphuric acid of 75g/L carries out leaching first time, the leaching agent dilute sulphuric acid adds from leaching the top, pond, solution leaches from leaching the bottom, pond, by the Flux Valve Control flow of filtrate, filtrate is returned to add and is leached the pond, and after (determining envrionment temperature) under the physical environment temperature and leaching 60 days according to concrete weather and place, leach leached mud, obtain leach liquor A; In leach liquor A, add the raw ore that contains zine ion once more, and additional sulfuric acid, carry out the second time and leach, after leaching 60 days under the physical environment temperature, leach leached mud again, obtain leach liquor B; Add the raw ore that contains zine ion once more, and additional sulfuric acid, leach for the third time, after leaching 60 days under the physical environment temperature, leach leached mud again, obtain leach liquor C, promptly obtain the product of this operation.
Embodiment 3: the technology that directly leaches low-grade germanic lead-zinc, the ore in sand form that earlier with zinc ion content be 10%, germanic amount is 120g/T adds and leaches in the pond, adding concentration according to the liquid-solid ratio of 3:1 is that the dilute sulphuric acid of 80g/L carries out leaching first time, the leaching agent dilute sulphuric acid adds from leaching the top, pond, solution leaches from leaching the bottom, pond, by the Flux Valve Control flow of filtrate, filtrate is returned to add and is leached the pond, and after leaching 30 days under the physical environment temperature, leach leached mud again, obtain leach liquor B; Add the raw ore that contains zine ion once more, and additional sulfuric acid, leach for the third time, after leaching 30 days under the physical environment temperature, leach leached mud again, obtain leach liquor C, promptly obtain the product of this operation.

Claims (2)

1. method that directly leaches low-grade germanic lead-zinc, it is characterized in that: (1) adds ore in sand form in leaching the pond, add dilute sulphuric acid according to liquid-solid ratio 2:1～5:1 and carry out the leaching first time, the leaching agent dilute sulphuric acid adds from leaching the top, pond, solution leaches from leaching the bottom, pond, filtrate is returned to add and is leached the pond, and after leaching 30～90 days under the physical environment temperature, obtains leach liquor A; (2) will leach that leached mud shifts out in the pond, add new ore in sand form again, and again will leach liquor A add to leach in the pond and soak, and adjust sulfuric acid concentration to 40～100 g/L, and carry out second batch of ore in sand form and leach, after leaching 30～90 days under the physical environment temperature, obtain leach liquor B; (3) zinc ion concentration of repeating step (2) in the leach liquor that obtains meets the extraction process requirement.
2. the method for the low-grade germanic lead-zinc of direct leaching according to claim 1 is characterized in that: vitriolic acidity is 40～100 g/L; Ore in sand form is an oxidized ore, and zinc content is less than 10% in the ore in sand form, and germanic amount is 40～120 g/T.
CN2010105092779A 2010-10-15 2010-10-15 Method for directly leaching low-grade germanic lead oxide and zinc oxide ores Pending CN101942560A (en)

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CN110055430A (en) * 2019-04-17 2019-07-26 中国恩菲工程技术有限公司 The extracting method of low-grade zinc oxide
CN114921664A (en) * 2022-06-01 2022-08-19 云南临沧鑫圆锗业股份有限公司 Method for extracting germanium from low-grade germanium concentrate

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Publication number Priority date Publication date Assignee Title
CN110055430A (en) * 2019-04-17 2019-07-26 中国恩菲工程技术有限公司 The extracting method of low-grade zinc oxide
CN110055430B (en) * 2019-04-17 2021-08-03 中国恩菲工程技术有限公司 Extraction method of low-grade zinc oxide
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CN114921664B (en) * 2022-06-01 2024-02-02 云南临沧鑫圆锗业股份有限公司 Method for extracting germanium from low-grade germanium concentrate

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