CN108441641A - A method of improving tannin germanium slag for comprehensive value - Google Patents
A method of improving tannin germanium slag for comprehensive value Download PDFInfo
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- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
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- C22B19/00—Obtaining zinc or zinc oxide
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Abstract
The invention belongs to technical field of wet metallurgy, provide a kind of method of raising tannin germanium slag for comprehensive value.This method includes：(1) alkaline leaching of tannin germanium slag：After the pH value and the temperature progress alkaline leaching that adjust tannin germanium slag, alkaline leaching liquid and alkaline leaching slag is obtained by filtration；Then the pH value of alkaline leaching liquid is adjusted, then adjusting evaporating temperature makes the volume concentration of alkaline leaching liquid obtain tanning solution；(2) villaumite of alkaline leaching slag leaches：Mixed liquor and alkaline leaching slag are mixed and add villaumite, after adjusting temperature progress villaumite leaching, chloride leaching solution and villaumite leached mud is obtained by filtration；(3) alkaline sedimentation of chloride leaching solution：Sodium hydroxide is added into chloride leaching solution, chlorine immersion liquid and lead cadmia is obtained by filtration after adjusting pH value and thermotonus.The method increase the tastes of the germanium of tannin germanium slag, reduce the tannin germanium slag quantity of slag, the rate of recovery of the lead zinc in tannin germanium slag is high, and the tannin rate of recovery is high in tannin germanium slag.
Description
Technical field
The invention belongs to technical field of wet metallurgy, specifically, being related to a kind of side of raising tannin germanium slag for comprehensive value
Method.
Background technology
Tannin germanium slag refers to：Germanium metallic element in wet zinc-making system in zinc calcine enters zinc hydrometallurgy leachate
Afterwards, organic matter tannin is added, under conditions of pH value is 2-3, reaction temperature is at 60 DEG C -70 DEG C, tannin is made to occur with germanium metal
Chemical reaction generates the solid slag formed after precipitation through filtering solid-liquor separation.
Tannin germanium is the byproduct of hydrometallurgy, at home in the production of present zinc hydrometallurgy, the zinc in tannin germanium slag
Content is 6%-10%, lead content 4%-6%, Ge content 0.5%-2%.Pb, Zn content in tannin germanium slag is higher.State
The technique of interior existing processing tannin germanium slag is generally：Tannin germanium slag is subjected to pyrogenic process roasting, product of roasting is leached through persalt
Effumability compound germanium chloride is generated, extraction temperature is 70 DEG C~80 DEG C, and germanium chloride steam volatilizees to be absorbed into condensing tube condensation
At purer germanium chloride.
Disadvantage of the existing technology：Ge content in tannin germanium slag is relatively low, and treating capacity is of high cost greatly；Lead zinc in tannin slag
Equal tenors are higher, and the rate of recovery is low；Organic matter tannin in tannin germanium cannot recycle.
Invention content
For deficiency above-mentioned in the prior art, the object of the present invention is to provide a kind of raising tannin germanium slag for comprehensive valences
The method of value；This method solve the valuable metals such as the lead zinc content height in tannin germanium slag, and germanium grade is low, and treating capacity is of high cost greatly
Etc. problems；And the germanium taste of tannin germanium slag is improved, the tannin germanium slag quantity of slag is reduced, the rate of recovery of the lead zinc in tannin germanium slag is high, single
The tannin rate of recovery is high in peaceful germanium slag.
In order to achieve the above object, the solution that the present invention uses is：
A method of tannin germanium slag for comprehensive value is improved, is included the following steps：(1) alkaline leaching of tannin germanium slag：It will
It is 4.5-5.5 that sodium hydroxide solution consolidates mass ratio with tannin germanium slag according to liquid:1 mixing keeps pH value to 9-10, adjusts and leach temperature
After degree carries out alkaline leaching 1.5h for 65 DEG C -75 DEG C, alkaline leaching liquid and alkaline leaching slag is obtained by filtration；Then to alkaline leaching
The sulfuric acid solution that mass concentration is 150g/L is added in liquid and adjusts alkaline leaching liquid pH value to 2-3, then adjust evaporating temperature to
85 DEG C -95 DEG C, makes the volume concentration of alkaline leaching liquid to the 1/20 of original volume, obtain tanning solution；(2) chlorine of alkaline leaching slag
Salt leaches：By in high lead material containing zinc zinc hydrometallurgy leaching process waste electrolyte and pneumatics leachate mix, be configured to
PH value is the mixed liquor of 2-3；According to mass ratio it is 4-7 by mixed liquor and alkaline leaching slag:1 is mixed, and it is dense to add quality
Degree is the villaumite of 280g/L-320g/L, is 65 DEG C -75 DEG C in temperature, and after carrying out villaumite leaching 1.5h, villaumite leaching is obtained by filtration
Liquid and villaumite leached mud；(3) alkaline sedimentation of chloride leaching solution：Be added sodium hydroxide into chloride leaching solution, adjust pH value to
8-9, and chlorine immersion liquid and lead cadmia is obtained by filtration after reacting 0.5h in 50-60 DEG C.
A kind of advantageous effect of method improving tannin germanium slag for comprehensive value provided by the invention is：
This kind provided by the invention improves the method that tannin germanium slag for comprehensive is worth：
Alkaline leaching first is carried out to tannin germanium slag；Using step of the present invention (1) provide alkaline leaching technological parameter (Gu
Liquor ratio, pH value, extraction temperature, extraction time) between coordinated synergy, make most of tannin in tannin germanium slag through hydrogen-oxygen
Change after sodium solution leaches filtering and leaches into alkaline leaching liquid；Alkaline leaching liquid is adjusted using pH and the techniques such as evaporation recycle
The rate of recovery to tannin can reach 65%~70%；
Then it uses in step (2) and villaumite leaching is carried out to alkaline leaching slag, the villaumite that step (2) provides through the invention
Collaboration between the technological parameter (solid-to-liquid ratio, the pH value of sodium chloride addition, extraction temperature, extraction time, mixed liquor) of leaching
Coordinate synergy, so that most of lead zinc metal in alkaline leaching slag is leached into chloride leaching solution after villaumite leaches filtering, obtain
To chloride leaching solution in lead zinc leaching rate can reach 90%-95%；
Then it uses in step (3) and alkaline sedimentation is carried out to chloride leaching solution, the alkalinity that step (3) provides through the invention
Coordinated synergy between the technological parameter (pH value, reaction temperature, time) of precipitation, makes most of lead in chloride leaching solution
Zinc metallic element is deposited in lead cadmia through alkaline sedimentation after refiltering, and the lead zinc leaching rate in obtained lead cadmia can reach
To 98%-99%；
Under above-mentioned technological process, the lead zinc recovery in tannin germanium slag can reach 88.2%-94.05%, and tannin returns
Yield can reach 65%-70%.The germanium taste that tannin germanium slag can be improved using this method, reduces the tannin germanium slag quantity of slag, single
The rate of recovery of lead zinc in peaceful germanium slag is high, and the tannin rate of recovery is high in tannin germanium slag.
Description of the drawings
Fig. 1 is the process flow chart for the method for improving tannin germanium slag for comprehensive value.
Specific implementation mode
It in order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below will be in the embodiment of the present invention
Technical solution be clearly and completely described.The person that is not specified actual conditions in embodiment, builds according to normal condition or manufacturer
The condition of view carries out.Reagents or instruments used without specified manufacturer is the conventional production that can be obtained by commercially available purchase
Product.
Below to it is provided in an embodiment of the present invention it is a kind of improve tannin germanium slag for comprehensive value method be specifically described.
A method of tannin germanium slag for comprehensive value is improved, is included the following steps：
(1) alkaline leaching of tannin germanium slag：It is 4.5- that sodium hydroxide solution and tannin germanium slag are consolidated mass ratio according to liquid
5.5:1 mixing, it should be noted that in the present embodiment, sodium hydroxide solution have alkalinity it is strong, it is cheap, be easy to storage and
The advantages that efficient；Further, it is 5 according to mass ratio by sodium hydroxide solution and institute's tannin germanium slag:1 is mixed；It keeps
For pH value to 9-10, it is 65 DEG C -75 DEG C to adjust extraction temperature, and further, control extraction temperature is 70 DEG C of progress alkaline leachings
After 1.5h, alkaline leaching liquid and alkaline leaching slag is obtained by filtration.
According to the coordinated between each technological parameter involved in the alkaline leaching of above-mentioned tannin germanium slag, make tannin
Lead zinc metallic element in germanium slag is leached into after alkaline leaching filters in alkaline leaching slag, and the tannin in tannin germanium slag is made to pass through
It is leached into alkaline leaching liquid after alkaline leaching filtering.
Then into alkaline leaching liquid be added mass concentration be 150g/L sulfuric acid solution adjust alkaline leaching liquid pH value to
2-3, it should be noted that in the present embodiment, due to being with dilute sulfuric acid in high lead material containing zinc zinc hydrometallurgy leaching process
Solution is as solvent, therefore, production cost can be saved using the pH to adjust alkaline leaching liquid of the sulfuric acid solution of 150g/L
And avoid the introducing of impurity；Then evaporating temperature is adjusted to 85 DEG C -95 DEG C, and further, it is 90 DEG C to adjust evaporating temperature, makes alkali
The volume concentration of property leachate obtains tanning solution to the 1/20 of original volume；Alkaline leaching liquid is adjusted and is evaporated by above-mentioned pH
Etc. techniques recycle to obtain the rate of recovery of tannin and can reach 65%~70%.
(2) villaumite of alkaline leaching slag leaches：By in high lead material containing zinc zinc hydrometallurgy leaching process waste electrolyte and
Pneumatics leachate is mixed, and the mixed liquor that pH value is 2-3 is configured to；According to mass ratio it is 4- by mixed liquor and alkaline leaching slag
7:1 is mixed, and the villaumite that mass concentration is 280g/L-320g/L is added, it should be noted that in the present embodiment, chlorine
Salt is more preferably sodium chloride, and compared to other villaumites, sodium chloride cost is lower and more stablizes, and the quality of sodium chloride is dense
Degree is further 300g/L；It is then 65 DEG C -75 DEG C in temperature, villaumite leaching is further carried out under the conditions of temperature is 70 DEG C
After going out 1.5h, chloride leaching solution and villaumite leached mud is obtained by filtration.
Coordinated in being leached according to the villaumite of above-mentioned alkaline leaching slag between involved each technological parameter, makes alkali
Property leached mud in most of lead zinc metallic element through villaumite leach filtering after leach into chloride leaching solution, and Germanium leach
To can extract in villaumite leached mud and by refining, the lead zinc leaching rate in the chloride leaching solution which obtains can reach
90%-95%.
(3) alkaline sedimentation of chloride leaching solution：Sodium hydroxide is added into chloride leaching solution, adjusts pH value to 8-9, and in
Chlorine immersion liquid and lead cadmia is obtained by filtration after 50-60 DEG C of reaction 0.5h；In this step, sodium hydroxide provide hydroxide ion with
Free lead or zinc ion combine the rate of recovery for obtaining lead zinc in lead cadmia for generating precipitation that can reach 98%-99%.It needs
Illustrate, the chlorine immersion liquid being obtained by filtration in this step can be applied to carry out the villaumite of alkaline leaching slag in step (2) again
It leaches, to further increase lead zinc leaching rate.
The feature and performance of the present invention are described in further detail with reference to embodiments.
Embodiment 1
A kind of method of raising tannin germanium slag for comprehensive value is present embodiments provided, is included the following steps：
(1) alkaline leaching of tannin germanium slag：It is 4.5 that sodium hydroxide solution and tannin germanium slag are consolidated mass ratio according to liquid:1 is mixed
It closes, keeps pH value to 9, after adjusting extraction temperature as 65 DEG C of progress alkaline leaching 1.5h, alkaline leaching liquid and alkalinity is obtained by filtration
Leached mud；Then the sulfuric acid solution that mass concentration is 150g/L is added into alkaline leaching liquid and adjusts alkaline leaching slag pH value to 2,
Then evaporating temperature is adjusted to 85 DEG C, is made the volume concentration of alkaline leaching liquid to the 1/20 of original volume, is obtained tanning solution；
(2) villaumite of alkaline leaching slag leaches：By in high lead material containing zinc zinc hydrometallurgy leaching process waste electrolyte and
Pneumatics leachate is mixed, and the mixed liquor that pH value is 2 is configured to；According to mass ratio it is 4 by mixed liquor and alkaline leaching slag:1
It is mixed, adds the villaumite that mass concentration is 280g/L, be 65 DEG C in temperature, after carrying out villaumite leaching 1.5h, filtered
To chloride leaching solution and villaumite leached mud；
(3) alkaline sedimentation of chloride leaching solution：Sodium hydroxide is added into chloride leaching solution, adjusts pH value to 8, and in 50
DEG C reaction 0.5h after chlorine immersion liquid and lead cadmia is obtained by filtration.
Embodiment 2
A kind of method of raising tannin germanium slag for comprehensive value is present embodiments provided, is included the following steps：
(1) alkaline leaching of tannin germanium slag：It is 5.5 that sodium hydroxide solution and tannin germanium slag are consolidated mass ratio according to liquid:1 is mixed
It closes, keeps pH value to 10, after adjusting extraction temperature as 75 DEG C of progress alkaline leaching 1.5h, alkaline leaching liquid and alkalinity is obtained by filtration
Leached mud；Then the sulfuric acid solution that mass concentration is 150g/L is added into alkaline leaching liquid and adjusts alkaline leaching slag pH value to 3,
Then evaporating temperature is adjusted to 95 DEG C, is made the volume concentration of alkaline leaching liquid to the 1/20 of original volume, is obtained tanning solution；
(2) villaumite of alkaline leaching slag leaches：By in high lead material containing zinc zinc hydrometallurgy leaching process waste electrolyte and
Pneumatics leachate is mixed, and the mixed liquor that pH value is 2 is configured to；According to mass ratio it is 4 by mixed liquor and alkaline leaching slag:1
It is mixed, adds the villaumite that mass concentration is 280g/L, be 65 DEG C in temperature, after carrying out villaumite leaching 1.5h, filtered
To chloride leaching solution and villaumite leached mud；
(3) alkaline sedimentation of chloride leaching solution：Sodium hydroxide is added into chloride leaching solution, adjusts pH value to 8, and in 50
DEG C reaction 0.5h after chlorine immersion liquid and lead cadmia is obtained by filtration.
Embodiment 3
A kind of method of raising tannin germanium slag for comprehensive value is present embodiments provided, is included the following steps：
(1) alkaline leaching of tannin germanium slag：It is 5 that sodium hydroxide solution and tannin germanium slag are consolidated mass ratio according to liquid:1 is mixed
It closes, keeps pH value to 9, after adjusting extraction temperature as 70 DEG C of progress alkaline leaching 1.5h, alkaline leaching liquid and alkalinity is obtained by filtration
Leached mud；Then the sulfuric acid solution that mass concentration is 150g/L is added into alkaline leaching liquid and adjusts alkaline leaching slag pH value to 2,
Then evaporating temperature is adjusted to 90 DEG C, is made the volume concentration of alkaline leaching liquid to the 1/20 of original volume, is obtained tanning solution；
(2) villaumite of alkaline leaching slag leaches：By in high lead material containing zinc zinc hydrometallurgy leaching process waste electrolyte and
Pneumatics leachate is mixed, and the mixed liquor that pH value is 2 is configured to；According to mass ratio it is 4 by mixed liquor and alkaline leaching slag:1
It is mixed, adds the villaumite that mass concentration is 280g/L, be 65 DEG C in temperature, after carrying out villaumite leaching 1.5h, filtered
To chloride leaching solution and villaumite leached mud；
(3) alkaline sedimentation of chloride leaching solution：Sodium hydroxide is added into chloride leaching solution, adjusts pH value to 8, and in 50
DEG C reaction 0.5h after chlorine immersion liquid and lead cadmia is obtained by filtration.
Embodiment 4
A kind of method of raising tannin germanium slag for comprehensive value is present embodiments provided, is included the following steps：
(1) alkaline leaching of tannin germanium slag：It is 5 that sodium hydroxide solution and tannin germanium slag are consolidated mass ratio according to liquid:1 is mixed
It closes, keeps pH value to 9, after adjusting extraction temperature as 70 DEG C of progress alkaline leaching 1.5h, alkaline leaching liquid and alkalinity is obtained by filtration
Leached mud；Then the sulfuric acid solution that mass concentration is 150g/L is added into alkaline leaching liquid and adjusts alkaline leaching slag pH value to 2,
Then evaporating temperature is adjusted to 90 DEG C, is made the volume concentration of alkaline leaching liquid to the 1/20 of original volume, is obtained tanning solution；
(2) villaumite of alkaline leaching slag leaches：By in high lead material containing zinc zinc hydrometallurgy leaching process waste electrolyte and
Pneumatics leachate is mixed, and the mixed liquor that pH value is 3 is configured to；According to mass ratio it is 7 by mixed liquor and alkaline leaching slag:1
It is mixed, adds the villaumite that mass concentration is 320g/L, be 75 DEG C in temperature, after carrying out villaumite leaching 1.5h, filtered
To chloride leaching solution and villaumite leached mud；
(3) alkaline sedimentation of chloride leaching solution：Sodium hydroxide is added into chloride leaching solution, adjusts pH value to 8, and in 50
DEG C reaction 0.5h after chlorine immersion liquid and lead cadmia is obtained by filtration.
Embodiment 5
A kind of method of raising tannin germanium slag for comprehensive value is present embodiments provided, is included the following steps：
(1) alkaline leaching of tannin germanium slag：It is 5 that sodium hydroxide solution and tannin germanium slag are consolidated mass ratio according to liquid:1 is mixed
It closes, keeps pH value to 9, after adjusting extraction temperature as 70 DEG C of progress alkaline leaching 1.5h, alkaline leaching liquid and alkalinity is obtained by filtration
Leached mud；Then the sulfuric acid solution that mass concentration is 150g/L is added into alkaline leaching liquid and adjusts alkaline leaching slag pH value to 2,
Then evaporating temperature is adjusted to 90 DEG C, is made the volume concentration of alkaline leaching liquid to the 1/20 of original volume, is obtained tanning solution；
(2) villaumite of alkaline leaching slag leaches：By in high lead material containing zinc zinc hydrometallurgy leaching process waste electrolyte and
Pneumatics leachate is mixed, and the mixed liquor that pH value is 3 is configured to；According to mass ratio it is 5 by mixed liquor and alkaline leaching slag:1
It is mixed, adds the villaumite that mass concentration is 300g/L, be 70 DEG C in temperature, after carrying out villaumite leaching 1.5h, filtered
To chloride leaching solution and villaumite leached mud；
(3) alkaline sedimentation of chloride leaching solution：Sodium hydroxide is added into chloride leaching solution, adjusts pH value to 8, and in 50
DEG C reaction 0.5h after chlorine immersion liquid and lead cadmia is obtained by filtration.
Embodiment 6
A kind of method of raising tannin germanium slag for comprehensive value is present embodiments provided, is included the following steps：
(1) alkaline leaching of tannin germanium slag：It is 5 that sodium hydroxide solution and tannin germanium slag are consolidated mass ratio according to liquid:1 is mixed
It closes, keeps pH value to 9, after adjusting extraction temperature as 70 DEG C of progress alkaline leaching 1.5h, alkaline leaching liquid and alkalinity is obtained by filtration
Leached mud；Then the sulfuric acid solution that mass concentration is 150g/L is added into alkaline leaching liquid and adjusts alkaline leaching slag pH value to 2,
Then evaporating temperature is adjusted to 90 DEG C, is made the volume concentration of alkaline leaching liquid to the 1/20 of original volume, is obtained tanning solution；
(2) villaumite of alkaline leaching slag leaches：By in high lead material containing zinc zinc hydrometallurgy leaching process waste electrolyte and
Pneumatics leachate is mixed, and the mixed liquor that pH value is 2 is configured to；According to mass ratio it is 6 by mixed liquor and alkaline leaching slag:1
It is mixed, adds the villaumite that mass concentration is 300g/L, be 70 DEG C in temperature, after carrying out villaumite leaching 1.5h, filtered
To chloride leaching solution and villaumite leached mud；
(3) alkaline sedimentation of chloride leaching solution：Sodium hydroxide is added into chloride leaching solution, adjusts pH value to 8, and in 50
DEG C reaction 0.5h after chlorine immersion liquid and lead cadmia is obtained by filtration.
Embodiment 7
A kind of method of raising tannin germanium slag for comprehensive value is present embodiments provided, is included the following steps：
(1) alkaline leaching of tannin germanium slag：It is 5 that sodium hydroxide solution and tannin germanium slag are consolidated mass ratio according to liquid:1 is mixed
It closes, keeps pH value to 9, after adjusting extraction temperature as 70 DEG C of progress alkaline leaching 1.5h, alkaline leaching liquid and alkalinity is obtained by filtration
Leached mud；Then the sulfuric acid solution that mass concentration is 150g/L is added into alkaline leaching liquid and adjusts alkaline leaching slag pH value to 2,
Then evaporating temperature is adjusted to 90 DEG C, is made the volume concentration of alkaline leaching liquid to the 1/20 of original volume, is obtained tanning solution；
(2) villaumite of alkaline leaching slag leaches：By in high lead material containing zinc zinc hydrometallurgy leaching process waste electrolyte and
Pneumatics leachate is mixed, and the mixed liquor that pH value is 2 is configured to；According to mass ratio it is 6 by mixed liquor and alkaline leaching slag:1
It is mixed, adds the villaumite that mass concentration is 300g/L, be 70 DEG C in temperature, after carrying out villaumite leaching 1.5h, filtered
To chloride leaching solution and villaumite leached mud；
(3) alkaline sedimentation of chloride leaching solution：Sodium hydroxide is added into chloride leaching solution, adjusts pH value to 9, and in 60
DEG C reaction 0.5h after chlorine immersion liquid and lead cadmia is obtained by filtration.
Embodiment 8
A kind of method of raising tannin germanium slag for comprehensive value is present embodiments provided, is included the following steps：
(1) alkaline leaching of tannin germanium slag：It is 5 that sodium hydroxide solution and tannin germanium slag are consolidated mass ratio according to liquid:1 is mixed
It closes, keeps pH value to 9, after adjusting extraction temperature as 70 DEG C of progress alkaline leaching 1.5h, alkaline leaching liquid and alkalinity is obtained by filtration
Leached mud；Then the sulfuric acid solution that mass concentration is 150g/L is added into alkaline leaching liquid and adjusts alkaline leaching slag pH value to 2,
Then evaporating temperature is adjusted to 90 DEG C, is made the volume concentration of alkaline leaching liquid to the 1/20 of original volume, is obtained tanning solution；
(2) villaumite of alkaline leaching slag leaches：By in high lead material containing zinc zinc hydrometallurgy leaching process waste electrolyte and
Pneumatics leachate is mixed, and the mixed liquor that pH value is 2 is configured to；According to mass ratio it is 6 by mixed liquor and alkaline leaching slag:1
It is mixed, adds the villaumite that mass concentration is 300g/L, be 70 DEG C in temperature, after carrying out villaumite leaching 1.5h, filtered
To chloride leaching solution and villaumite leached mud；
(3) alkaline sedimentation of chloride leaching solution：Sodium hydroxide is added into chloride leaching solution, adjusts pH value to 9, and in 55
DEG C reaction 0.5h after chlorine immersion liquid and lead cadmia is obtained by filtration.
Comparative example 1
This comparative example provides a kind of method of raising tannin germanium slag for comprehensive value, includes the following steps：
(1) alkaline leaching of tannin germanium slag：It is 4 that sodium hydroxide solution and tannin germanium slag are consolidated mass ratio according to liquid:1 is mixed
It closes, keeps pH value to 11, after adjusting extraction temperature as 60 DEG C of progress alkaline leaching 1.5h, alkaline leaching liquid and alkalinity is obtained by filtration
Leached mud；Then the sulfuric acid solution that mass concentration is 150g/L is added into alkaline leaching liquid and adjusts alkaline leaching slag pH value to 1,
Then evaporating temperature is adjusted to 100 DEG C, is made the volume concentration of alkaline leaching liquid to the 1/20 of original volume, is obtained tanning solution；
(2) villaumite of alkaline leaching slag leaches：By in high lead material containing zinc zinc hydrometallurgy leaching process waste electrolyte and
Pneumatics leachate is mixed, and the mixed liquor that pH value is 2 is configured to；According to mass ratio it is 6 by mixed liquor and alkaline leaching slag:1
It is mixed, adds the villaumite that mass concentration is 300g/L, be 70 DEG C in temperature, after carrying out villaumite leaching 1.5h, filtered
To chloride leaching solution and villaumite leached mud；
(3) alkaline sedimentation of chloride leaching solution：Sodium hydroxide is added into chloride leaching solution, adjusts pH value to 9, and in 55
DEG C reaction 0.5h after chlorine immersion liquid and lead cadmia is obtained by filtration.
Comparative example 2
This comparative example provides a kind of method of raising tannin germanium slag for comprehensive value, includes the following steps：
(1) alkaline leaching of tannin germanium slag：It is 6 that sodium hydroxide solution and tannin germanium slag are consolidated mass ratio according to liquid:1 is mixed
It closes, keeps pH value to 8, after adjusting extraction temperature as 80 DEG C of progress alkaline leaching 1.5h, alkaline leaching liquid and alkalinity is obtained by filtration
Leached mud；Then the sulfuric acid solution that mass concentration is 150g/L is added into alkaline leaching liquid and adjusts alkaline leaching slag pH value to 4,
Then evaporating temperature is adjusted to 80 DEG C, is made the volume concentration of alkaline leaching liquid to the 1/20 of original volume, is obtained tanning solution；
(2) villaumite of alkaline leaching slag leaches：By in high lead material containing zinc zinc hydrometallurgy leaching process waste electrolyte and
Pneumatics leachate is mixed, and the mixed liquor that pH value is 2 is configured to；According to mass ratio it is 6 by mixed liquor and alkaline leaching slag:1
It is mixed, adds the villaumite that mass concentration is 300g/L, be 70 DEG C in temperature, after carrying out villaumite leaching 1.5h, filtered
To chloride leaching solution and villaumite leached mud；
(3) alkaline sedimentation of chloride leaching solution：Sodium hydroxide is added into chloride leaching solution, adjusts pH value to 9, and in 55
DEG C reaction 0.5h after chlorine immersion liquid and lead cadmia is obtained by filtration.
Comparative example 3
This comparative example provides a kind of method of raising tannin germanium slag for comprehensive value, includes the following steps：
(1) alkaline leaching of tannin germanium slag：It is 5 that sodium hydroxide solution and tannin germanium slag are consolidated mass ratio according to liquid:1 is mixed
It closes, keeps pH value to 9, after adjusting extraction temperature as 70 DEG C of progress alkaline leaching 1.5h, alkaline leaching liquid and alkalinity is obtained by filtration
Leached mud；Then the sulfuric acid solution that mass concentration is 150g/L is added into alkaline leaching liquid and adjusts alkaline leaching slag pH value to 2,
Then evaporating temperature is adjusted to 90 DEG C, is made the volume concentration of alkaline leaching liquid to the 1/20 of original volume, is obtained tanning solution；
(2) villaumite of alkaline leaching slag leaches：By in high lead material containing zinc zinc hydrometallurgy leaching process waste electrolyte and
Pneumatics leachate is mixed, and the mixed liquor that pH value is 1 is configured to；According to mass ratio it is 8 by mixed liquor and alkaline leaching slag:1
It is mixed, adds the villaumite that mass concentration is 330g/L, be 60 DEG C in temperature, after carrying out villaumite leaching 1.5h, filtered
To chloride leaching solution and villaumite leached mud；
(3) alkaline sedimentation of chloride leaching solution：Sodium hydroxide is added into chloride leaching solution, adjusts pH value to 9, and in 55
DEG C reaction 0.5h after chlorine immersion liquid and lead cadmia is obtained by filtration.
Comparative example 4
This comparative example provides a kind of method of raising tannin germanium slag for comprehensive value, includes the following steps：
(1) alkaline leaching of tannin germanium slag：It is 5 that sodium hydroxide solution and tannin germanium slag are consolidated mass ratio according to liquid:1 is mixed
It closes, keeps pH value to 9, after adjusting extraction temperature as 70 DEG C of progress alkaline leaching 1.5h, alkaline leaching liquid and alkalinity is obtained by filtration
Leached mud；Then the sulfuric acid solution that mass concentration is 150g/L is added into alkaline leaching liquid and adjusts alkaline leaching slag pH value to 2,
Then evaporating temperature is adjusted to 90 DEG C, is made the volume concentration of alkaline leaching liquid to the 1/20 of original volume, is obtained tanning solution；
(2) villaumite of alkaline leaching slag leaches：By in high lead material containing zinc zinc hydrometallurgy leaching process waste electrolyte and
Pneumatics leachate is mixed, and the mixed liquor that pH value is 4 is configured to；According to mass ratio it is 3 by mixed liquor and alkaline leaching slag:1
It is mixed, adds the villaumite that mass concentration is 270g/L, be 80 DEG C in temperature, after carrying out villaumite leaching 1.5h, filtered
To chloride leaching solution and villaumite leached mud；
(3) alkaline sedimentation of chloride leaching solution：Sodium hydroxide is added into chloride leaching solution, adjusts pH value to 9, and in 55
DEG C reaction 0.5h after chlorine immersion liquid and lead cadmia is obtained by filtration.
Comparative example 5
A kind of method of raising tannin germanium slag for comprehensive value is present embodiments provided, is included the following steps：
(1) alkaline leaching of tannin germanium slag：It is 5 that sodium hydroxide solution and tannin germanium slag are consolidated mass ratio according to liquid:1 is mixed
It closes, keeps pH value to 9, after adjusting extraction temperature as 70 DEG C of progress alkaline leaching 1.5h, alkaline leaching liquid and alkalinity is obtained by filtration
Leached mud；Then the sulfuric acid solution that mass concentration is 150g/L is added into alkaline leaching liquid and adjusts alkaline leaching slag pH value to 2,
Then evaporating temperature is adjusted to 90 DEG C, is made the volume concentration of alkaline leaching liquid to the 1/20 of original volume, is obtained tanning solution；
(2) villaumite of alkaline leaching slag leaches：By in high lead material containing zinc zinc hydrometallurgy leaching process waste electrolyte and
Pneumatics leachate is mixed, and the mixed liquor that pH value is 2 is configured to；According to mass ratio it is 6 by mixed liquor and alkaline leaching slag:1
It is mixed, adds the villaumite that mass concentration is 300g/L, be 70 DEG C in temperature, after carrying out villaumite leaching 1.5h, filtered
To chloride leaching solution and villaumite leached mud；
(3) alkaline sedimentation of chloride leaching solution：Sodium hydroxide is added into chloride leaching solution, adjusts pH value to 7, and in 45
DEG C reaction 0.5h after chlorine immersion liquid and lead cadmia is obtained by filtration.
Comparative example 6
This comparative example provides a kind of method of raising tannin germanium slag for comprehensive value, includes the following steps：
(1) alkaline leaching of tannin germanium slag：It is 5 that sodium hydroxide solution and tannin germanium slag are consolidated mass ratio according to liquid:1 is mixed
It closes, keeps pH value to 9, after adjusting extraction temperature as 70 DEG C of progress alkaline leaching 1.5h, alkaline leaching liquid and alkalinity is obtained by filtration
Leached mud；Then the sulfuric acid solution that mass concentration is 150g/L is added into alkaline leaching liquid and adjusts alkaline leaching slag pH value to 2,
Then evaporating temperature is adjusted to 90 DEG C, is made the volume concentration of alkaline leaching liquid to the 1/20 of original volume, is obtained tanning solution；
(2) villaumite of alkaline leaching slag leaches：By in high lead material containing zinc zinc hydrometallurgy leaching process waste electrolyte and
Pneumatics leachate is mixed, and the mixed liquor that pH value is 2 is configured to；According to mass ratio it is 6 by mixed liquor and alkaline leaching slag:1
It is mixed, adds the villaumite that mass concentration is 300g/L, be 70 DEG C in temperature, after carrying out villaumite leaching 1.5h, filtered
To chloride leaching solution and villaumite leached mud；
(3) alkaline sedimentation of chloride leaching solution：Sodium hydroxide is added into chloride leaching solution, adjusts pH value to 10, and in
Chlorine immersion liquid and lead cadmia is obtained by filtration after 65 DEG C of reaction 0.5h.
Experimental example 1
Experimental method：It is surveyed respectively by permanganimetric method in the tannin germanium slag that embodiment 1-3 and ratio 1-2 are provided
Tannin content M1 and tanning solution in tannin content M2, calculate tannin leaching rate=V (%)=M2/M1, the results are shown in Table
Shown in 1：
The tannin leaching rate of table 1 embodiment 1-8 and comparative example 1-6
| Group number | Tannin leaching rate V (%) |
| Embodiment 1 | 65 |
| Embodiment 2 | 65 |
| Embodiment 3 | 70 |
| Comparative example 1 | 45 |
| Comparative example 2 | 52 |
From the data in table 1, it can be seen that compared to comparative example 1-2, it is worth using the raising tannin germanium slag for comprehensive that embodiment 1-3 is provided
The obtained tanning solution leaching rate higher of method；Each process parameters range involved by the step of comparative example 1-2 is provided (1) is equal
Not in range provided in an embodiment of the present invention, should the result shows that, using the alkalinity of tannin germanium slag provided in an embodiment of the present invention
It being capable of coordinated between involved each technological parameter (solid-to-liquid ratio, pH value, extraction temperature, extraction time) in leaching step
Synergy makes most of tannin in tannin germanium slag be leached into alkaline leaching liquid after sodium hydroxide solution leaches filtering, alkalinity
The pH ranges that leachate is improved using the embodiment of the present invention are adjusted and the techniques such as evaporating temperature range recycle to obtain returning for tannin
High income.
Experimental example 2
Experimental method：It is measured by AA7050 atomic absorption spectrophotometers and measures embodiment Isosorbide-5-Nitrae -6 and comparative example respectively
Pb, Zn content M1 in the alkaline leaching slag that 3-4 is provided, the Pb, Zn content M2 in villaumite leached mud calculate lead zinc leaching rate V
(%)=(M1-M2)/M1, the results are shown in Table shown in 2：
The lead zinc leaching rate of table 2 embodiment Isosorbide-5-Nitrae -6 and comparative example 3-4
From the data in table 2, it can be seen that compared to comparative example 3-4, using the raising tannin of embodiment Isosorbide-5-Nitrae -6 and comparative example 3-4 confessions
The lead zinc leaching rate higher that the method and step (2) of germanium slag for comprehensive value obtains；Involved by the step of comparative example 3-4 is provided (2)
Each process parameters range not in range provided in an embodiment of the present invention, should the result shows that, provided using the embodiment of the present invention
Alkaline leaching slag villaumite leaching step in involved each technological parameter (solid-to-liquid ratio, leaches temperature at sodium chloride addition
The pH value of degree, extraction time, mixed liquor) between can coordinated synergy, make most of lead zinc metal in alkaline leaching slag
It is leached into chloride leaching solution after villaumite leaches filtering, the lead zinc leaching rate in obtained chloride leaching solution is high.
Experimental example 3
Experimental method：It is measured by AA7050 atomic absorption spectrophotometers and measures embodiment 1,7-8 and comparative example respectively
Pb, Zn content M1 in the chloride leaching solution that 5-6 is provided, the Pb, Zn content M2 in lead cadmia, calculate lead zinc leaching rate V (%)=
(M1-M2)/M1, the results are shown in Table shown in 3：
3 embodiment 1 of table, the lead zinc leaching rate of 7-8 and comparative example 5-6
From the data in table 3, it can be seen that compared to comparative example 5-6, using embodiment 1, the raising list of 7-8 and comparative example 5-6 offers
The lead zinc leaching rate higher that the method and step (3) of peaceful germanium slag for comprehensive value obtains；The step of comparative example 5-6 is provided (3) is involved
Each process parameters range not in range provided in an embodiment of the present invention, should the result shows that, carried using the embodiment of the present invention
Energy between involved each technological parameter (pH value, reaction temperature, time) in the alkaline sedimentation step of the chloride leaching solution of confession
Enough coordinated synergy, makes most of lead zinc metallic element in chloride leaching solution through alkaline sedimentation, lead is deposited to after refiltering
In cadmia, the lead zinc leaching rate in obtained lead cadmia is high.
In conclusion using the method for raising tannin germanium slag for comprehensive value provided by the invention；This method solve in list
The valuable metals content such as lead zinc is high in peaceful germanium slag, and germanium grade is low, the problems such as big cost height for the treatment of capacity；And improve the germanium of tannin germanium slag
Taste reduces the tannin germanium slag quantity of slag, and the rate of recovery of the lead zinc in tannin germanium slag is high, and the tannin rate of recovery is high in tannin germanium slag.
The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, for the skill of this field
For art personnel, the invention may be variously modified and varied.All within the spirits and principles of the present invention, any made by repair
Change, equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (8)
1. a kind of method improving tannin germanium slag for comprehensive value, it is characterised in that：Include the following steps：
(1) alkaline leaching of tannin germanium slag：It is 4.5-5.5 that sodium hydroxide solution and tannin germanium slag are consolidated mass ratio according to liquid:1 is mixed
It closes, keeps pH value that alkaline leaching is obtained by filtration after adjusting extraction temperature as 65 DEG C of -75 DEG C of progress alkaline leaching 1.5h to 9-10
Liquid and alkaline leaching slag；Then the sulfuric acid solution that mass concentration is 150g/L is added into the alkaline leaching liquid and adjusts the alkali
Property pH of leaching solution to 2-3, then adjust evaporating temperature to 85 DEG C -95 DEG C, make the volume concentration of the alkaline leaching liquid to original
The 1/20 of volume, obtains tanning solution；
(2) villaumite of alkaline leaching slag leaches：By the waste electrolyte and pneumatics in high lead material containing zinc zinc hydrometallurgy leaching process
Leachate is mixed, and the mixed liquor that pH value is 2-3 is configured to；By the mixed liquor and the alkaline leaching slag according to mass ratio
For 4-7:1 is mixed, and the villaumite that mass concentration is 280g/L-320g/L is added, and is 65 DEG C -75 DEG C in temperature, is carried out chlorine
After salt leaches 1.5h, chloride leaching solution and villaumite leached mud is obtained by filtration；
(3) alkaline sedimentation of chloride leaching solution：Sodium hydroxide is added into the chloride leaching solution, adjusts pH value to 8-9, and in
Chlorine immersion liquid and lead cadmia is obtained by filtration after 50-60 DEG C of reaction 0.5h.
2. the method according to claim 1 for improving tannin germanium slag for comprehensive value, it is characterised in that：In step (1), by institute
It is 5 that sodium hydroxide solution and the tannin germanium slag, which are stated, according to mass ratio:1 is mixed.
3. the method according to claim 1 for improving tannin germanium slag for comprehensive value, it is characterised in that：In step (1), control
Extraction temperature is 70 DEG C.
4. the method according to claim 1 for improving tannin germanium slag for comprehensive value, it is characterised in that：In step (1), adjust
The evaporating temperature is 90 DEG C.
5. the method according to claim 1 for improving tannin germanium slag for comprehensive value, it is characterised in that：It is described in step (2)
Villaumite includes sodium chloride.
6. the method according to claim 5 for improving tannin germanium slag for comprehensive value, it is characterised in that：It is described in step (2)
The mass concentration of sodium chloride is 300g/L.
7. the method according to claim 1 for improving tannin germanium slag for comprehensive value, it is characterised in that：In step (2), by institute
It is 5-6 that mixed liquor and the high lead material containing zinc leached mud, which are stated, according to mass ratio:1 is mixed.
8. the method according to claim 1 for improving tannin germanium slag for comprehensive value, it is characterised in that：In step (2), villaumite
Extraction temperature is 70 DEG C.
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