CN106884095B - A kind of integrated conduct method of the high germanium raw material of zinc hydrometallurgy and calcium sulfite waste residue - Google Patents
A kind of integrated conduct method of the high germanium raw material of zinc hydrometallurgy and calcium sulfite waste residue Download PDFInfo
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- CN106884095B CN106884095B CN201710148882.XA CN201710148882A CN106884095B CN 106884095 B CN106884095 B CN 106884095B CN 201710148882 A CN201710148882 A CN 201710148882A CN 106884095 B CN106884095 B CN 106884095B
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B19/00—Obtaining zinc or zinc oxide
- C22B19/30—Obtaining zinc or zinc oxide from metallic residues or scraps
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B11/00—Obtaining noble metals
- C22B11/04—Obtaining noble metals by wet processes
- C22B11/042—Recovery of noble metals from waste materials
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B13/00—Obtaining lead
- C22B13/04—Obtaining lead by wet processes
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
- C22B3/08—Sulfuric acid, other sulfurated acids or salts thereof
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B41/00—Obtaining germanium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B5/00—General methods of reducing to metals
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- 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
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
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Abstract
The invention discloses a kind of high germanium raw material of zinc hydrometallurgy and the integrated conduct methods of calcium sulfite waste residue, include the following steps：1）The pulp of zinc leaching residue；2）Pulp ore pulp leaches；3）It neutralizes and restores；4）Calcium slag mild acid wash；5）Tannin sinks germanium.The invention mainly includes while the directly Ti recovery from Zinc Hydrometallurgy Process, using easy method, the calcium sulfite waste residue that Dual alkali sulfur dioxide absorption when rotary kiln evaporation generates has been carried out integrated treatment, has obtained the calcium sulfate raw material of industry that can be sold；The recycling for realizing resource eliminates environmentally friendly risk, has saved production cost, while going on smoothly for directly from zinc hydrometallurgy high germanium raw material Ti recovery has been effectively ensured.
Description
Technical field
The invention belongs to technical field of wet metallurgy, and in particular to a kind of high germanium raw material of zinc hydrometallurgy and calcium sulfite waste residue
Integrated conduct method.
Background technique
The raw material of zinc hydrometallurgy is zinc roasted ore, and what is had is germanic higher, reaches 0.01wt% or more.Traditional germanium recovery method
It is that germanium is enriched in the leached mud of zinc hydrometallurgy, leached mud uses rotary kiln evaporation, and the valuable metals such as germanium is made to be volatized into oxidation
In Zn dust, then zinc oxide fumes are carried out with the recycling of the valuable metals such as zinc, germanium；This method is mainly adapted to directly to return
Germanium is received, it can only be using the low germanium raw material for being just able to achieve germanium recycling after rotary kiln evaporation enrichment.
For high germanium zinc metallurgy raw material, if recycling zinc, germanium after also waving enrichment using rotary kiln, not from economic and social benefit
Reality；Firstly, using rotary kiln evaporation, the volatility of germanium generally only has 65wt% ~ 75wt%, from zinc oxide fumes to output germanium essence
The rate of recovery of the process of mine, germanium only has 90wt% ~ 95wt%, that is to say, that rotary kiln evaporation Ti recovery is used, from zinc leaching residue
The rate of recovery to germanium concentrate, germanium only has 55wt% ~ 75wt%；Followed by, using rotary kiln evaporation, output largely needs separately
The Water Quenching Slag of processing, to cause the rising of production cost, environmentally friendly risk big.Directly zinc leaching residue is leached, is saved back
The process of rotary kiln volatilization, can reach save the cost, improve the effect of the germanium rate of recovery；Trivalent is only used when zinc hydrometallurgy leaches
The iron that a large amount of zinc ferrite also is leached out, and is leached out in the iron and slag of iron hydrolytic purification be almost ferric sulfate also
It is ferric iron, it is unfavorable that it recycles germanium, and the ferric iron back in solution is needed with reducing agent to be that ferrous iron is namely reduced to
Ferrous sulfate；Lead-in-dreg after leaching can reach 15wt% or more, can do lead concentrate sale, reach the innoxious recycling of germanium.
On the other hand, some utilising zinc containing waste residues produce zinc oxide fumes, output two in volatilization process using rotary kiln evaporation
Sulfur oxide flue gas absorbs ability qualified discharge using Dual alkali, and the calcium sulfite that thus output largely send slag library to store up is useless
Slag；This its main ingredient of calcium sulfite waste residue is calcium sulfite, secondly also contains the calcium hydroxide of about 10wt% ~ 15wt%, sub-
It is a kind of reducing agent again that calcium sulfate, which is a kind of oxidant, and property is unstable, is also easy to produce pollution, and its oxidation product calcium sulfate
Then a kind of good construction material, it is how economical, efficiently become the mixing slag of this calcium sulfite and calcium hydroxide can
The calcium sulfate utilized is a urgent problem.
In view of the above problems, we have invented a kind of from zinc hydrometallurgy high germanium raw material Ti recovery and calcium sulfite waste residue
Integrated conduct method, the ferric iron back in high germanium raw material leachate was not only achieved the purpose that Ti recovery at ferrous iron by it, but also was made
This calcium slag that gives up that mixes is converted into salable calcium sulfate.
Summary of the invention
The purpose of the present invention is to provide a kind of high germanium raw material of zinc hydrometallurgy and the integrated conduct methods of calcium sulfite waste residue.
The object of the present invention is achieved like this, includes the following steps：
1）The pulp of zinc leaching residue：Zinc leaching residue is pressed 4 ~ 5 with pulp liquid：1 liquid-solid ratio carries out pulp, slurry time 40
It is ~ 45 minutes, stand-by after stirring pulp uniformly；
2）Pulp ore pulp leaches：Ore pulp after uniform to stirring pulp adjusts the acid 140g/l ~ 150g/l that begins, control with the concentrated sulfuric acid
Process temperature processed is greater than 90 DEG C, extraction time 4.0 ~ 5.0 hours, up to being filtered 1 after 50g/l ~ 60g/l, filtering 1 produces acid eventually
No. 1 filter residue and No. 1 filtrate out, No. 1 filter residue can do the sale of lead silver preparation concentrate, and No. 1 filtrate is neutralized and restored；
3）It neutralizes and restores：Preceding liquid is done with No. 1 filtrate, is warming up to 60 DEG C ~ 65 DEG C, to be slowly stirred lower addition calcium sulfite useless
Slag, while the sulfur dioxide gas of releasing is sent to acid making system, mixing time 2.0 ~ 3.0 hours, to solution acidity to 20g/l
When ~ 30g/l, stops calcium sulfite waste residue and simultaneously continue stirring 1.0 ~ 1.5 hours, when solution acidity is in pH=1.5 ~ 2.0, and
It when no sulfur dioxide gas is released, neutralizes and reduction is completed and is filtered 2, filter No. 2 calcium slags of 2 output and No. 2 filtrates, No. 2
Calcium slag carries out mild acid wash, and No. 2 filtrates carry out the heavy germanium of tannin；
4）Tannin sinks germanium：With No. 2 filtrates, it is warming up to 80 DEG C ~ 85 DEG C, 30 ~ 40 times of tannic acid multiplying power of addition, stirring 15 ~ 20
Filter 23 is carried out after minute, filter 23 obtains liquid after No. 3 tannin germanium slags and No. 3 heavy germanium, and liquid power transmission Zn system recycles after No. 3 heavy germanium
Zinc produces No. 3 tannin germanium slags and germanium recovery workshop is sent to produce germanium concentrate；
5）Mild acid wash：3 ~ 4 are pressed to No. 2 calcium slags industrial water：1 liquid-solid ratio carries out pulp, then with the concentrated sulfuric acid to it
Adjustment begins acid to 30g/l ~ 35g/l, is warming up to 90 DEG C ~ 95 DEG C, stirs 2.5 ~ 3.0 hours, the purpose is to further aoxidize reconciliation
It analyses micro calcium sulfite and removes the objectionable impurities in calcium slag, when solution acidity is stablized in 15g/l ~ 20g/l, washed
Finish, is filtered 4, filtering 4 obtains No. 4 and washes rear calcium slag and No. 4 wash waters, and No. 4 wash waters do the pulp liquid of zinc leaching residue, produce No. 4
Wash the raw materials for production sale that rear calcium slag does gypsum.
Compared with prior art, the present invention has the following technical effects：
1, the present invention provides the integrated treatments of a kind of Ti recovery and calcium sulfite waste residue from zinc hydrometallurgy high germanium raw material
Method；The leaching of ore pulp after the pulp and pulp of the high germanium raw material zinc leaching residue of zinc hydrometallurgy, make a large amount of germanium in slag, zinc and
Iron is leached, and is laid the foundation for the direct recycling of germanium；The calcium sulfite of rotary kiln evaporation sulfur dioxide absorption flue gas output is used again
Waste residue neutralizes liquid after leaching, ferric reduction；In calcium sulfite waste residue and and it is ferric during, sulfurous
Sour calcium and calcium hydroxide, which then react, generates the calcium sulfate for being conducive to synthetical recovery i.e. gypsum；In this way, both having realized leaching
Ferric iron back also makes calcium sulfite waste residue be comprehensively utilized and handle at ferrous purpose in liquid, is allowed to turn waste into wealth
It is converted into salable calcium sulfate, not only having certain economic benefit also has very big environmental benefit.
2, the present invention is calculated from whole flow process, and the rate of recovery of germanium is in 90.00wt% or more, and the rate of recovery of zinc is in 90.50wt%
More than, the rate of recovery of lead is in 99.50wt% or more, the silver-colored rate of recovery in 95.50wt% or more.
3, the maximum feature of the present invention is to keep ferric reduction and calcium sulfite waste residue raw using easier method
It at the calcium sulfate i.e. gypsum that have interests synthetical recovery while carrying out, realizes ferric reduction without again plus other
Reducing agent, so that calcium sulfite waste residue has been obtained harmless treatment.
4, the present invention utilizes the part hydroxide in calcium sulfite waste residue during ferric iron back is at ferrous iron
Calcium, directly neutralize make solution terminal acid reach tannin sink germanium requirement i.e. pH=1.5 ~ 2.0, be not required to again to being carried out before heavy germanium
The adjustment of acidity.
5, the present invention is more environmentally friendly, more energy efficient compared with traditional recovery process, meets national resources comprehensive reutilization and can
The requirement of sustainable development.
Detailed description of the invention
Fig. 1 is process flow chart of the invention.
Specific embodiment
Below with reference to embodiment and attached drawing, the present invention is further illustrated, but is not subject in any way to the present invention
Limitation, based on present invention teach that it is made it is any transform or replace, all belong to the scope of protection of the present invention.
The integrated conduct method of a kind of high germanium raw material of zinc hydrometallurgy of the present invention and calcium sulfite waste residue, including it is following
Step：
（1）The pulp of zinc leaching residue：Zinc leaching residue is pressed 4 ~ 5 with pulp liquid：1 liquid-solid ratio carries out pulp, slurry time
It is 40 ~ 45 minutes, stand-by after stirring pulp uniformly；
（2）Pulp ore pulp leaches：The ore pulp concentrated sulfuric acid after uniform to stirring pulp adjusts the acid 140g/l ~ 150g/l that begins,
Control process temperature is greater than 90 DEG C, extraction time 4.0 ~ 5.0 hours, acid is up to being filtered 1 after 50g/l ~ 60g/l eventually, filtering 1
No. 1 filter residue of output and No. 1 filtrate, No. 1 filter residue can do the sale of lead silver preparation concentrate, and No. 1 filtrate is neutralized and restored；
（3）It neutralizes and restores：Preceding liquid is done with No. 1 filtrate, 60 DEG C ~ 65 DEG C is warming up to, is slowly stirred lower addition calcium sulfite
Waste residue, while the sulfur dioxide gas of releasing is sent to acid making system, it mixing time 2.0 ~ 3.0 hours, is arrived to solution acidity
When 20g/l ~ 30g/l, stops calcium sulfite waste residue and simultaneously continue stirring 1.0 ~ 1.5 hours, when solution acidity is in pH=1.5 ~ 2.0, and
And when being released without sulfur dioxide gas, neutralizes and restores and complete and be filtered 2, filter No. 2 calcium slags of 2 output and No. 2 filtrates,
No. 2 calcium slags carry out mild acid wash, and No. 2 filtrates carry out the heavy germanium of tannin；
（4）Tannin sinks germanium：With No. 2 filtrates, it is warming up to 80 DEG C ~ 85 DEG C, 30 ~ 40 times of tannic acid multiplying power of addition, stirring 15 ~ 20
Filter 23 is carried out after minute, filter 23 obtains liquid after No. 3 tannin germanium slags and No. 3 heavy germanium, and liquid power transmission Zn system recycles after No. 3 heavy germanium
Zinc produces No. 3 tannin germanium slags and germanium recovery workshop is sent to produce germanium concentrate；
（5）Mild acid wash：3 ~ 4 are pressed to No. 2 calcium slags industrial water：1 liquid-solid ratio carries out pulp, then with the concentrated sulfuric acid to it
Adjustment begins acid to 30g/l ~ 35g/l, is warming up to 90 DEG C ~ 95 DEG C, stirs 2.5 ~ 3.0 hours, the purpose is to further aoxidize reconciliation
It analyses micro calcium sulfite and removes the objectionable impurities in calcium slag, when solution acidity is stablized in 15g/l ~ 20g/l, washed
Finish, is filtered 4, filtering 4 obtains No. 4 and washes rear calcium slag and No. 4 wash waters, and No. 4 wash waters do the pulp liquid of zinc leaching residue, produce No. 4
Wash the raw materials for production sale that rear calcium slag does gypsum.
Step（1）Described in the main ingredient of zinc leaching residue be：Zinc 9.5wt% ~ 15.0wt%, germanium 0.020wt% ~
0.030wt%, lead 3.0wt% ~ 5.0wtwt%, iron 13.0wt% ~ 18.0wt%, silver 0.002wt% ~ 0.005wt%.
Step（1）Described in pulp liquid be industrial water and/or No. 4 wash waters.
Step（2）Described in the concentrated sulfuric acid be the industrial concentrated sulfuric acid.
Step（2）Described in No. 1 filter residue i.e. lead silver preparation concentrate in leaded 15wt% ~ 22wt%, argentiferous 0.008wt% ~
0.020wt%。
Step（3）Described in calcium sulfite waste residue predominantly contain calcium sulfite 90 wt% ~ 85 wt%, containing calcium hydroxide
The mixture of 10wt% ~ 15wt%.
The zinc leaching residue and calcium sulfite waste residue crosses what 80 meshes obtained after drying division sample preparation.
Step（5）Described in No. 4 wash discovery two compared with rear calcium slag is scanned Electronic Speculum with analytically pure calcium sulphate crystal
The pattern similarity of person is very high, and the calcium sulfate that this method processing generates can be used as industrial materials dihydrate gypsum application.
Embodiment 1
The high germanium raw material zinc leaching residue of Yunnan Luoping Zinc & Electricity Co., Ltd.'s zinc hydrometallurgy and rotary kiln titanium dioxide are taken respectively
The calcium sulfite waste residue of sulphur tail gas absorption Workshop Production, drying division sample preparation it is each 20000.00 grams and cross 80 mesh screens it is stand-by,
High germanium raw material zinc leaching residue main ingredient is：Zinc 9.66wt%, iron 13.12wt%, lead 3.25wt%, germanium 0.0216wt%, silver
0.0019wt%；
（1）The pulp of zinc leaching residue：Preceding liquid is done with industrial water, takes 60 liters, high germanium raw material zinc leaching residue 15000.0 is added
Gram carry out pulp, slurry time 40 minutes, stirring pulp uniformly afterwards carry out next step pulp ore pulp leach；
（2）Pulp ore pulp leaches：The ore pulp concentrated sulfuric acid after uniform to stirring pulp adjusts the acid 140g/l that begins, control process
Temperature be greater than 90 DEG C, process add water to keep volume, extraction time 4.0 hours, up to being filtered 1 after 50g/l, filtering 1 produces acid eventually
Out water content 26.35wt%, 2.69wt% containing zinc, germanium 0.0091wt%, lead 15.09wt%, silver 0.0088wt%, iron 22.65wt% 1
Number 4384.0 grams of wet filter residue does lead silver preparation concentrate and sells and 22.95g/l containing zinc, germanium 0.0496g/l, lead 0.001g/l, acid 49.85g/
L, silver 0.0002g/l, ferrous iron 2.54g/l, 59.40 liters of No. 1 filtrate of ferric iron 18.28g/l do in calcium sulfite waste residue
With and restore before liquid；
（3）It neutralizes and restores：Preceding liquid is done with No. 1 50 liters of filtrate, is warming up to 60 DEG C, to be slowly added to calcium sulfite under stirring useless
Slag, while the sulfur dioxide gas of releasing is sent to acid making system, it controls mixing time 2.0 hours, to solution acidity to 20g/l
When, stop that calcium sulfite waste residue is added, at this point, 15000.0 grams of calcium sulfite waste residue is added, process adds water to keep volume；And after
Continuous stirring 1.0 hours when solution acidity is stablized in pH=1.5, and releases without sulfur dioxide gas, neutralizes and reduction is completed
And 2 are filtered, 2 output water content 28.67wt% of filtering, 0.009wt% containing zinc, germanium 0.00010wt%, iron 0.007wt%, lead are micro-
The mild acid wash and 23.08g/l containing zinc of micro 20727.0 grams of No. 2 wet calcium slags progress next step of amount, silver, germanium 0.0497g/l,
Micro 49.65 liters of No. 2 filtrates of lead 0.001g/l, silver 0.0002g/l, ferrous iron 20.94g/l, ferric iron do liquid before heavy germanium；
（4）Tannin sinks germanium：With No. 2 35 liters of filtrates and be warmed to 80 DEG C, 52.18 grams of tannic acid are molten with the concentration of 15wt%
Solution is slowly added in 40 DEG C ~ 50 DEG C of water and in the case of stirring, add after continue stirring 15 minutes after be filtered
3, filter 23 obtains No. 3 tannin of water content 62.85wt%, germanic 3.25wt%, zinc 3.41wt%, iron 1.48wt%, lead 1.43wt%
143.77 grams of germanium slag weight in wet base and 23.13g/l containing zinc, germanic 0.0002g/l, ferrous iron 21.01g/l, ferric iron is micro, lead is micro
No. 3 heavy germanium after 34.85 liters of liquid；Liquid power transmission Zn system recycles zinc after No. 3 heavy germanium, produces No. 3 tannin germanium slags and send germanium recovery workshop
Produce germanium concentrate；
（5）Mild acid wash：Pulp is carried out with industrial 13.5 liters with No. 2 4500.0 grams of calcium slag dry weight, stirring pulp is uniform
It is adjusted afterwards acid to begin acid 30g/l, be warmed to 90 DEG C, stir 2.5 hours, process add water holding volume, when terminal acid is in 15g/l
When, washing finishes, be filtered 4, filtering 4 obtain water content 26.04wt%, < containing zinc 0.0001wt%, iron < 0.0001wt%,
Germanium is micro, lead is micro, silver is micro No. 4 wash 5980.0 grams of rear wet calcium slag and 0.03g/l containing zinc, germanium 0.00034g/l, ferrous iron
Micro 13.24 liters of No. 4 wash waters of 0.023g/l, ferric iron, No. 4 wash waters do the pulp liquid of zinc leaching residue, produce No. 4 and wash rear calcium slag
The raw materials for production for doing gypsum are sold.
It is by can be calculated each economic target：
1. the leaching process of the zinc leaching residue：The leaching of lead recovery 99.98wt%, silver raising recovery rate 95.83wt%, zinc
Rate is 94.01wt%, the leaching rate of germanium is 90.93wt%, the leaching rate of iron is 62.84wt%.
2. in the neutralization and reduction process of calcium sulfite waste residue, ferric reduction rate reaches 100wt%.
3. entire synthetical recovery process zinc loss 6.32wt%, i.e. zinc recovery 93.68wt%.
4. entire synthetical recovery process germanium rate of recovery 90.27wt%.
Embodiment 2
The high germanium raw material zinc leaching residue of Yunnan Luoping Zinc & Electricity Co., Ltd.'s zinc hydrometallurgy and rotary kiln titanium dioxide are taken respectively
The calcium sulfite waste residue of sulphur tail gas absorption Workshop Production, drying division sample preparation it is each 20000.00 grams and cross 80 mesh screens it is stand-by,
High germanium raw material zinc leaching residue main ingredient is：Zinc 14.86wt%, iron 17.89wt%, lead 4.88wt%, germanium 0.028wt%, silver
0.0047wt%；
（1）The pulp of zinc leaching residue：Preceding liquid is done with industrial water, takes 65 liters, high germanium raw material zinc leaching residue 13000.0 is added
Gram carry out pulp, slurry time 45 minutes, stirring pulp uniformly afterwards carry out next step pulp ore pulp leach；
（2）Pulp ore pulp leaches：The ore pulp concentrated sulfuric acid after uniform to stirring pulp adjusts the acid 150g/l that begins, control process
Temperature be greater than 90 DEG C, process add water to keep volume, extraction time 5.0 hours, up to being filtered 1 after 60g/l, filtering 1 produces acid eventually
Water content 23.04wt%, 4.41wt% containing zinc, germanium 0.012wt%, lead 21.39wt%, silver 0.02wt%, No. 1 of iron 29.68wt% out
3853.0 grams of wet filter residue do lead silver preparation concentrate sell and 27.76g/l containing zinc, germanium 0.0506g/l, lead 0.001g/l, acid 59.67g/l,
Silver-colored 0.0003g/l, ferrous iron 2.63g/l, 64.88 liters of No. 1 filtrate of the ferric iron 19.65g/l neutralizations for doing calcium sulfite waste residue
And liquid before restoring；
（3）It neutralizes and restores：Preceding liquid is done with No. 1 60 liters of filtrate, is warming up to 65 DEG C, to be slowly added to calcium sulfite under stirring useless
Slag, while the sulfur dioxide gas of releasing is sent to acid making system, it controls mixing time 3.0 hours, to solution acidity to 30g/l
When, stop that calcium sulfite waste residue is added, at this point, 18000.0 grams of calcium sulfite waste residue is added, process adds water to keep volume；And after
Continuous stirring 1.5 hours when solution acidity is stablized in pH=2.0, and releases without sulfur dioxide gas, neutralizes and reduction is completed
And 2 are filtered, 2 output water content 29.05wt% of filtering, 0.008wt% containing zinc, germanium 0.00012wt%, iron 0.006wt%, lead are micro-
The mild acid wash and 28.23g/l containing zinc of micro 25000.0 grams of No. 2 wet calcium slags progress next step of amount, silver, germanium 0.0512g/l,
Micro 58.95 liters of No. 2 filtrates of lead 0.001g/l, silver 0.0002g/l, ferrous iron 22.49g/l, ferric iron do liquid before heavy germanium；
（4）Tannin sinks germanium：With No. 2 40 liters of filtrates and be warmed to 85 DEG C, 71.68 grams of tannic acid are molten with the concentration of 15wt%
Solution is slowly added in 40 DEG C ~ 50 DEG C of water and in the case of stirring, add after continue stirring and be filtered after twenty minutes
3, filter 23 obtains No. 3 lists of water content 62.43wt%, germanic 3.46wt%, zinc 3.22wtwt%, iron 1.32wt%, lead 1.24wt%
157.31 grams of peaceful germanium slag weight in wet base and 28.44g/l containing zinc, germanic 0.0001g/l, ferrous iron 22.47g/l, ferric iron is micro, lead is micro-
39.64 liters of liquid after No. 3 heavy germanium of amount；Liquid power transmission Zn system recycles zinc after No. 3 heavy germanium, produces No. 3 tannin germanium slags and send germanium recovery vehicle
Between produce germanium concentrate；
（5）Mild acid wash：Pulp is carried out with industrial 20.0 liters with No. 2 5000.0 grams of calcium slag dry weight, stirring pulp is uniform
It is adjusted afterwards acid to begin acid 35g/l, be warmed to 95 DEG C, stir 3.0 hours, process add water holding volume, when terminal acid is in 20g/l
When, washing finishes, be filtered 4, filtering 4 obtain water content 25.48wt%, < containing zinc 0.0002wt%, iron < 0.0001wt%,
Germanium is micro, lead is micro, silver is micro No. 4 wash 6602.0 grams of rear wet calcium slag and 0.020g/l containing zinc, germanium 0.00030g/l, ferrous iron
Micro 19.65 liters of No. 4 wash waters of 0.015g/l, ferric iron, No. 4 wash waters do the pulp liquid of zinc leaching residue, produce No. 4 and wash rear calcium slag
The raw materials for production for doing gypsum are sold.
It is by can be calculated each economic target：
1. the leaching process of the zinc leaching residue：The leaching of lead recovery 99.98wt%, silver raising recovery rate 96.82wt%, zinc
Rate is 93.23wt%, the leaching rate of germanium is 90.19wt%, the leaching rate of iron is 62.15 wt%.
2. in the neutralization and reduction process of calcium sulfite waste residue, ferric reduction rate reaches 100wt%.
3. entire synthetical recovery process zinc loss 7.01wt%, i.e. zinc recovery 92.99wt%.
4. entire synthetical recovery process germanium rate of recovery 89.53wt%.
Embodiment 3
The high germanium raw material zinc leaching residue of Yunnan Luoping Zinc & Electricity Co., Ltd.'s zinc hydrometallurgy and rotary kiln titanium dioxide are taken respectively
The calcium sulfite waste residue of sulphur tail gas absorption Workshop Production, dries division sample preparation and 80 mesh screens excessively are stand-by, high germanium raw material zinc leaching
Main ingredient of slagging tap is：Zinc 9.5wt%, germanium 0.020wt%, lead 3.0wt%, iron 13.0wt%, silver 0.002wt%；
（1）The pulp of zinc leaching residue：Zinc leaching residue is pressed 4 with pulp liquid：1 liquid-solid ratio carries out pulp, slurry time 40
Minute, it is stand-by after stirring pulp uniformly；
（2）Pulp ore pulp leaches：The ore pulp concentrated sulfuric acid after uniform to stirring pulp adjusts the acid 140g/l that begins, control process
93 DEG C of temperature, extraction time 4.0 hours, acid is up to being filtered 1 after 50g/l eventually, filters No. 1 filter residue of 1 output and No. 1 filtrate, and No. 1
Filter residue can do the sale of lead silver preparation concentrate, and No. 1 filtrate is neutralized and restored；The leaded 15wt% of lead silver preparation concentrate, argentiferous
0.008wt%；
（3）It neutralizes and restores：Do preceding liquid with No. 1 filtrate, be warming up to 60 DEG C, slowly and to be added with stirring calcium sulfite useless
Slag, while the sulfur dioxide gas of releasing is sent to acid making system, mixing time 2.0 hours, when solution acidity is to 20g/l,
Stop calcium sulfite waste residue and simultaneously continue stirring 1.0 hours, is released when solution acidity is in pH=1.5, and without sulfur dioxide gas
When, it neutralizing and reduction is completed and is filtered 2, filter No. 2 calcium slags of 2 output and No. 2 filtrates, No. 2 calcium slags carry out mild acid wash, and 2
Number filtrate carries out tannin and sinks germanium；
（4）Tannin sinks germanium：With No. 2 filtrates, be warming up to 80 DEG C, be added 30 times of tannic acid multiplying power, stirring 15 minutes after carry out
Filter 23, filter 23 obtain liquid after No. 3 tannin germanium slags and No. 3 heavy germanium, and liquid power transmission Zn system recycles zinc after No. 3 heavy germanium, produce No. 3 lists
Peaceful germanium slag send germanium recovery workshop to produce germanium concentrate；
（5）Mild acid wash：3 are pressed to No. 2 calcium slags industrial water：1 liquid-solid ratio carries out pulp, then is adjusted with the concentrated sulfuric acid to it
Whole beginning acid arrives 30g/l, is warming up to 90 DEG C, stirs 2.5 hours, the purpose is to further aoxidize and parse micro calcium sulfite and
The objectionable impurities in calcium slag is removed, when solution acidity is stablized in 15g/l, washing is finished, and is filtered 4, filtering 4 obtains No. 4
Rear calcium slag and No. 4 wash waters are washed, No. 4 wash waters do the pulp liquid of zinc leaching residue, produce No. 4 and wash rear calcium slag and analytically pure calcium sulfate crystalline substance
Body is scanned Electronic Speculum and compares, and the pattern similarity of the two is very high, and the calcium sulfate that this method processing generates can be used as industry
Material dihydrate gypsum, that is, the raw materials for production for doing gypsum are sold.
Step（1）Described in pulp liquid when starting device for the first time carries out first time pulp the pulp liquid that uses be industry
With water, when there is No. 4 wash waters to generate, the pulp liquid is No. 4 wash waters.
It is by can be calculated each economic target：
1. the leaching process of the zinc leaching residue：The leaching of lead recovery 99.55wt%, silver raising recovery rate 95.60wt%, zinc
Rate is 92.33wt%, the leaching rate of germanium is 92.10wt%, the leaching rate of iron is 63.20 wt%.
2. in the neutralization and reduction process of calcium sulfite waste residue, ferric reduction rate reaches 100wt%.
3. entire synthetical recovery process zinc loss 8.60wt%, i.e. zinc recovery 91.40wt%.
4. entire synthetical recovery process germanium rate of recovery 91.55wt%.
Embodiment 4
The high germanium raw material zinc leaching residue of Yunnan Luoping Zinc & Electricity Co., Ltd.'s zinc hydrometallurgy and rotary kiln titanium dioxide are taken respectively
The calcium sulfite waste residue of sulphur tail gas absorption Workshop Production, dries division sample preparation and 80 mesh screens excessively are stand-by, high germanium raw material zinc leaching
Main ingredient of slagging tap is：Zinc 15.0wt%, germanium 0.030wt%, lead 5.0wtwt%, iron 18.0wt%, silver 0.005wt%；
（1）The pulp of zinc leaching residue：Zinc leaching residue is pressed 5 with pulp liquid：1 liquid-solid ratio carries out pulp, slurry time 45
Minute, it is stand-by after stirring pulp uniformly；
（2）Pulp ore pulp leaches：The ore pulp concentrated sulfuric acid after uniform to stirring pulp adjusts the acid 150g/l that begins, control process
95 DEG C of temperature, extraction time 5.0 hours, acid is up to being filtered 1 after 60g/l eventually, filters No. 1 filter residue of 1 output and No. 1 filtrate, and No. 1
Filter residue can do the sale of lead silver preparation concentrate, and No. 1 filtrate is neutralized and restored；The leaded 22wt% of lead silver preparation concentrate, argentiferous
0.020wt%；
（3）It neutralizes and restores：Do preceding liquid with No. 1 filtrate, be warming up to 65 DEG C, slowly and to be added with stirring calcium sulfite useless
Slag, while the sulfur dioxide gas of releasing is sent to acid making system, mixing time 3.0 hours, when solution acidity is to 30g/l,
Stop calcium sulfite waste residue and simultaneously continue stirring 1.5 hours, is released when solution acidity is in pH=2.0, and without sulfur dioxide gas
When, it neutralizing and reduction is completed and is filtered 2, filter No. 2 calcium slags of 2 output and No. 2 filtrates, No. 2 calcium slags carry out mild acid wash, and 2
Number filtrate carries out tannin and sinks germanium；
（4）Tannin sinks germanium：With No. 2 filtrates, be warming up to 85 DEG C, be added 40 times of tannic acid multiplying power, stirring carry out after twenty minutes
Filter 23, filter 23 obtain liquid after No. 3 tannin germanium slags and No. 3 heavy germanium, and liquid power transmission Zn system recycles zinc after No. 3 heavy germanium, produce No. 3 lists
Peaceful germanium slag send germanium recovery workshop to produce germanium concentrate；
（5）Mild acid wash：4 are pressed to No. 2 calcium slags industrial water：1 liquid-solid ratio carries out pulp, then is adjusted with the concentrated sulfuric acid to it
Whole beginning acid arrives 35g/l, is warming up to 95 DEG C, stirs 3.0 hours, the purpose is to further aoxidize and parse micro calcium sulfite and
The objectionable impurities in calcium slag is removed, when solution acidity is stablized in 20g/l, washing is finished, and is filtered 4, filtering 4 obtains No. 4
Rear calcium slag and No. 4 wash waters are washed, No. 4 wash waters do the pulp liquid of zinc leaching residue, produce No. 4 and wash rear calcium slag and analytically pure calcium sulfate crystalline substance
Body is scanned Electronic Speculum and compares, and the pattern similarity of the two is very high, and the calcium sulfate that this method processing generates can be used as industry
Material dihydrate gypsum, that is, the raw materials for production for doing gypsum are sold.
Step（1）Described in pulp liquid when starting device for the first time carries out first time pulp the pulp liquid that uses be industry
With water, when there is No. 4 wash waters to generate, the pulp liquid is industrial water and No. 4 wash waters.
It is by can be calculated each economic target：
1. the leaching process of the zinc leaching residue：The leaching of lead recovery 99.96wt%, silver raising recovery rate 97.75wt%, zinc
Rate is 95.30wt%, the leaching rate of germanium is 93.25wt%, the leaching rate of iron is 62.68wt%.
2. in the neutralization and reduction process of calcium sulfite waste residue, ferric reduction rate reaches 100wt%.
3. entire synthetical recovery process zinc loss 6.52wt%, i.e. zinc recovery 93.48wt%.
4. entire synthetical recovery process germanium rate of recovery 91.99wt%.
Embodiment 5
The high germanium raw material zinc leaching residue of Yunnan Luoping Zinc & Electricity Co., Ltd.'s zinc hydrometallurgy and rotary kiln titanium dioxide are taken respectively
The calcium sulfite waste residue of sulphur tail gas absorption Workshop Production, dries division sample preparation and 80 mesh screens excessively are stand-by, high germanium raw material zinc leaching
Main ingredient of slagging tap is：Zinc 13.0wt%, germanium 0.025wt%, lead 4.0wt%, iron 15.0wt%, silver 0.004wt%；
（1）The pulp of zinc leaching residue：Zinc leaching residue is pressed 4.5 with pulp liquid：1 liquid-solid ratio carries out pulp, slurry time
It is 42 minutes, stand-by after stirring pulp uniformly；
（2）Pulp ore pulp leaches：The ore pulp concentrated sulfuric acid after uniform to stirring pulp adjusts the acid 145g/l that begins, control process
95 DEG C of temperature, extraction time 4.5 hours, acid is up to being filtered 1 after 55g/l eventually, filters No. 1 filter residue of 1 output and No. 1 filtrate, and No. 1
Filter residue can do the sale of lead silver preparation concentrate, and No. 1 filtrate is neutralized and restored；The leaded 18wt% of lead silver preparation concentrate, argentiferous
0.012wt%；
（3）It neutralizes and restores：Do preceding liquid with No. 1 filtrate, be warming up to 62 DEG C, slowly and to be added with stirring calcium sulfite useless
Slag, while the sulfur dioxide gas of releasing is sent to acid making system, mixing time 2.5 hours, when solution acidity is to 25g/l,
Stop calcium sulfite waste residue and simultaneously continue stirring 1.2 hours, is released when solution acidity is in pH=1.7, and without sulfur dioxide gas
When, it neutralizing and reduction is completed and is filtered 2, filter No. 2 calcium slags of 2 output and No. 2 filtrates, No. 2 calcium slags carry out mild acid wash, and 2
Number filtrate carries out tannin and sinks germanium；
（4）Tannin sinks germanium：With No. 2 filtrates, be warming up to 82 DEG C, be added 35 times of tannic acid multiplying power, stirring 17 minutes after carry out
Filter 23, filter 23 obtain liquid after No. 3 tannin germanium slags and No. 3 heavy germanium, and liquid power transmission Zn system recycles zinc after No. 3 heavy germanium, produce No. 3 lists
Peaceful germanium slag send germanium recovery workshop to produce germanium concentrate；
（5）Mild acid wash：3 ~ 4 are pressed to No. 2 calcium slags industrial water：1 liquid-solid ratio carries out pulp, then with the concentrated sulfuric acid to it
Adjustment begins acid to 32g/l, is warming up to 92 DEG C, stirs 2.8 hours, the purpose is to further aoxidize and parse micro calcium sulfite
With the objectionable impurities in washout calcium slag, when solution acidity is stablized in 18g/l, washing is finished, and is filtered 4, filtering 4 obtains 4
Number rear calcium slag and No. 4 wash waters are washed, No. 4 wash waters do the pulp liquid of zinc leaching residue, produce No. 4 and wash rear calcium slag and analytically pure calcium sulfate
Crystal is scanned Electronic Speculum and compares, and the pattern similarity of the two is very high, and the calcium sulfate that this method processing generates can be used as work
Industry material dihydrate gypsum, that is, the raw materials for production for doing gypsum are sold.
Step（1）Described in pulp liquid when starting device for the first time carries out first time pulp the pulp liquid that uses be industry
With water, when there is No. 4 wash waters to generate, the pulp liquid is industrial water.
It is by can be calculated each economic target：
1. the leaching process of the zinc leaching residue：The leaching of lead recovery 99.99wt%, silver raising recovery rate 96.88wt%, zinc
Rate is 95.66wt%, the leaching rate of germanium is 95.10wt%, the leaching rate of iron is 63.85 wt%.
2. in the neutralization and reduction process of calcium sulfite waste residue, ferric reduction rate reaches 100wt%.
3. entire synthetical recovery process zinc loss 5.50wt%, i.e. zinc recovery 94.50wt%.
4. entire synthetical recovery process germanium rate of recovery 93.77wt%.
Claims (5)
1. the integrated conduct method of a kind of high germanium raw material of zinc hydrometallurgy and calcium sulfite waste residue, it is characterised in that the method packet
Include following steps：
1）The pulp of zinc leaching residue：Zinc leaching residue 9.5wt% containing zinc ~ 15.0wt%, germanium 0.020wt% ~ 0.030wt%, lead 3.0wt% ~
5.0wtwt%, iron 13.0wt% ~ 18.0wt%, silver 0.002wt% ~ 0.005wt%；Zinc leaching residue is pressed 4 ~ 5 with pulp liquid:1 liquid
Gu slurry time 40 ~ 45 minutes, stand-by after stirring pulp uniformly than carrying out pulp；
2）Pulp ore pulp leaches：The ore pulp concentrated sulfuric acid after uniform to stirring pulp adjusts the acid 140g/l ~ 150g/l that begins, and controls
Cheng Wendu is greater than 90 DEG C, extraction time 4.0 ~ 5.0 hours, acid filters 1 output 1 up to being filtered 1 after 50g/l ~ 60g/l eventually
Filter residue and No. 1 filtrate, No. 1 filter residue can do the sale of lead silver preparation concentrate, and No. 1 filtrate is neutralized and restored；
3）It neutralizes and restores：Calcium sulfite waste residue is 90wt% containing calcium sulfite ~ 85wt%, 10wt% containing calcium hydroxide ~ 15wt%
Mixture does preceding liquid with No. 1 filtrate, is warming up to 60 DEG C ~ 65 DEG C, is slowly stirred lower addition calcium sulfite waste residue, while releasing
Sulfur dioxide gas send to acid making system, mixing time 2.0 ~ 3.0 hours, when solution acidity is to 20g/l ~ 30g/l, stop
The addition of calcium sulfite waste residue simultaneously continues stirring 1.0 ~ 1.5 hours, when solution acidity is in pH=1.5 ~ 2.0, and without titanium dioxide
It when sulphur gas is released, neutralizes and restores and complete and be filtered 2, filter No. 2 calcium slags of 2 output and No. 2 filtrates, No. 2 calcium slags carry out
Mild acid wash, No. 2 filtrates carry out the heavy germanium of tannin；
4）Tannin sinks germanium：With No. 2 filtrates, it is warming up to 80 DEG C ~ 85 DEG C, 30 ~ 40 times of tannic acid multiplying power of addition, stirring 15 ~ 20 minutes
After carry out filter 23, filter 23 obtains liquid after No. 3 tannin germanium slags and No. 3 heavy germanium, after No. 3 heavy germanium liquid power transmission Zn system recycle zinc, institute
Producing No. 3 tannin germanium slags send germanium recovery workshop to produce germanium concentrate；
5）Mild acid wash：3 ~ 4 are pressed to No. 2 calcium slags industrial water:1 liquid-solid ratio carries out pulp, then is adjusted with the concentrated sulfuric acid to it
Acid begin to 30g/l ~ 35g/l, is warming up to 90 DEG C ~ 95 DEG C, stirs 2.5 ~ 3.0 hours, when solution acidity is stablized in 15g/l ~ 20g/l
When, washing finishes, and is filtered 4, filtering 4 obtains No. 4 and washes rear calcium slag and No. 4 wash waters, and No. 4 wash waters do the pulp of zinc leaching residue
Liquid produces No. 4 and washes the raw materials for production sale that rear calcium slag does gypsum.
2. integrated conduct method according to claim 1, it is characterised in that step（1）Described in pulp liquid be it is industrial
Water and/or No. 4 wash waters.
3. integrated conduct method according to claim 1, it is characterised in that step（2）Described in the concentrated sulfuric acid be industry it is dense
Sulfuric acid.
4. integrated conduct method according to claim 1, it is characterised in that step（2）Described in No. 1 filter residue it is leaded
15wt% ~ 22wt%, argentiferous 0.008wt% ~ 0.020wt%.
5. integrated conduct method according to claim 1, it is characterised in that the zinc leaching residue and calcium sulfite waste residue
Cross what 80 meshes obtained after drying division sample preparation.
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| CN113832346B (en) * | 2021-09-16 | 2023-07-21 | 云南驰宏资源综合利用有限公司 | Method for efficiently and simply treating germanium-containing zinc leaching residues |
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