CN102676833A - High grade cobalt sulfonate slag and production process thereof - Google Patents
High grade cobalt sulfonate slag and production process thereof Download PDFInfo
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- CN102676833A CN102676833A CN2012101888124A CN201210188812A CN102676833A CN 102676833 A CN102676833 A CN 102676833A CN 2012101888124 A CN2012101888124 A CN 2012101888124A CN 201210188812 A CN201210188812 A CN 201210188812A CN 102676833 A CN102676833 A CN 102676833A
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Abstract
The invention relates to high grade cobalt sulfonate slag produced by using ammonium sulfate instead of copper sulfate as an oxidant. The high grade cobalt sulfonate slag comprises 15 to 21 percent of cobalt. The method comprises the following steps: preparing an agent from sodium isethionate, ammonium persulfate and cobalt in a ratio of (9-12):(4-5):(0.5-2); preparing the sodium isethionate into a 10 percent solution, and preparing the ammonium persulfate into a solution for later use; introducing 40 to 45 m<3> of two-stage cadmium removing solution into a cobalt removing tank, controlling the pH of initial acid to be more than 5.0, adding sodium hydroxide to regulate the pH to the required range when the acidity is high, and controlling the temperature to be less than or equal to 45DEG C; and adding the ammonium persulfate, slowly and uniformly adding the sodium isethionate, controlling the dosing time to be 20-30 minutes, reacting for 0.5 to 1.5 hours, discharging a solution into a middle tank by opening a bottom current valve, pumping into a cobalt removing filter press by using a pump for filter pressing, unloading the cobalt slag into a cobalt slag primary rinsing bath, and conveying filtrate into a leaching workshop.
Description
Technical field
The present invention relates to a kind of ammonium persulphate that utilizes and replace conventional oxidant (copper sulfate) to do oxidant production higher-grade wbolt sulfonate slag and production technique thereof, relate more specifically to a kind of Zinc hydrometallurgy process, it has utilized above-mentioned recovery cobalt technology to remove cobalt.
Background technology
The recovery of cobalt mainly contains three kinds of technologies in the zinc hydrometallurgy process, is respectively that antimonic salt removes cobalt technology, β-Nai Fen removes cobalt technology and ethylsulfonic acid sodium removes cobalt technology.At present antimonic salt removes cobalt technology and is mainly used in the clean liquid operation of zinc hydrometallurgy, and the cobalt in the zinc ore concentrate gets in clean liquid process and purifies the slag open circuit, and the recovery technology that purifies cobalt metal in the slag mainly contains β-Nai Fen and removes cobalt technology and ethylsulfonic acid sodium except that cobalt technology.β-Nai Fen commonly used at present removes cobalt technology and has following shortcoming, and β-Nai Fen costs an arm and a leg, and reaction process produces a large amount of nitrogen oxides pollution things, and oxynitride is difficult to handle, and causes huge environmental problem.The recovery that purifies cobalt metal in the slag adopts ethylsulfonic acid sodium to remove cobalt technology, because ethylsulfonic acid sodium market price is far below β-Nai Fen, thereby significantly improves the economic benefit of cobalt metal recovery.
Cobalt is brought into the leach liquor from zinc ore concentrate.Its content in leach liquor can not carry out electrolyting precipitation process when reaching certain concentration, for this reason, must remove it and be lower than below the 1mg/L.Clean liquid removes cobalt one convenient assurance electrolytic process to carry out smoothly, also from solution, extracts utmost point metal values cobalt on the other hand most possibly.
It is a kind of sulphonate that ethylsulfonic acid sodium removes the used ethylsulfonic acid sodium reagent of cobalt, is a kind of organic substance, and its molecular formula has C1H
9OCSSK, C
2H
5OCSSE, C
4H
9OCSSNa, C
2H
5OCSSNa etc.If contain CoSO in the solution of zinc sulfate
4And when directly adding sodium sulfonate or potassium xanthate and removing cobalt, then only generate white yellow acid zinc to separate out, and cobalt does not precipitate.For wanting precipitate cobalt, must at first from solution, remove almost all zinc.If form the trivalent cobalt xanthate, then situation significantly changes, because trivalent sulfonic acid cobalt is a kind of stable and salt of indissoluble.Cobalt xanthate precipitated before yellow acid zinc and separates out in this case, even yellow acid zinc has formed and also can dissolve and separate out cobalt xanthate.Therefore we can say that the basic chemical process of removing cobalt with ethylsulfonic acid sodium is to utilize oxygenant that the divalence cobalt oxidation in the solution of zinc sulfate is become the trivalent cobalt, forms cobaltic xanthate then.Cu
2+, Fe
3+, KMnO
4Deng all can be as oxygenant.
The basic chemical process that ethylsulfonic acid sodium removes cobalt is to utilize oxygenant that the divalence cobalt oxidation in the solution of zinc sulfate is become the trivalent cobalt, forms cobaltic xanthate then.Generally adopt copper sulfate to make oxygenant at present and carry out ethylsulfonic acid sodium except that cobalt.When copper sulfate exists, just can make the divalence cobalt be oxidized to the trivalent cobalt in the solution, and well deposition is removed.But the cobalt technology of removing that adopts copper sulfate to make oxygenant exists oxygenant to cost an arm and a leg, and contains shortcomings such as copper oxidation of impurities agent autophage ethylsulfonic acid sodium in the sulfonic acid cobalt slag, and this arts demand further improves.
One Chinese patent application CN1172859A and CN101440431A disclose the method for utilizing wbolt sulfonate slag to reclaim cobalt respectively; Yet its wbolt sulfonate slag is and utilizes copper sulfate to remove that cobalt obtains; The technology of this preparation wbolt sulfonate slag has following defective: traditional ethylsulfonic acid sodium that oxygenant is made with copper sulfate in (1) removes cobalt technology; Copper sulfate costs an arm and a leg, and it is high to cause removing the cobalt cost, the objective of the invention is to adopt cheap oxygenant to replace copper sulfate to make oxygenant.
(2) traditional ethylsulfonic acid sodium removes cobalt technology; Contain the copper impurity that copper sulfate is brought in the sulfonic acid cobalt slag of its generation; The subsequent disposal of sulfonic acid cobalt slag needs copper removal; The objective of the invention is to select for use a kind of novel oxygenant, this oxygenant can become the trivalent cobalt with the divalence cobalt oxidation, and self component does not get in the sulfonic acid cobalt slag.
(3) traditional ethylsulfonic acid sodium removes cobalt technology; Oxygenant copper sulfate and the reaction of ethylsulfonic acid sodium; Additive decrementation ethylsulfonic acid sodium has further increased and has removed the cobalt cost, the objective of the invention is to select a kind of ethylsulfonic acid sodium to remove the oxygenant of cobalt; This oxygenant does not react with ethylsulfonic acid sodium, reduces ethylsulfonic acid sodium consumption to greatest extent.
(4) traditional ethylsulfonic acid sodium is low except that the cobalt salt efficient that cobalt technology makes, and it is low to contain the cobalt amount.
Summary of the invention
In order to overcome the deficiency of above-mentioned prior art.The invention provides a kind of higher-grade wbolt sulfonate slag, contain the cobalt of 15-21%.
A kind of aforesaid wbolt sulfonate slag, it contains 20% the cobalt of having an appointment.
A kind of aforesaid wbolt sulfonate slag, it also contains Zn, the 0.3-1.5%Fe of 0.1-5.0%Cu, 0.1-10%Cd, 5-45%, the impurity of surplus.
A kind of ethylsulfonic acid sodium that utilizes ammonium persulphate to make oxygenant reclaims cobalt technology, and its step comprises:
1) removes cobalt dosing, the configuration proportion of medicament according to solution cobalt total;
2) ethylsulfonic acid sodium is configured to solution, ammonium persulphate is configured to solution for later use;
3) squeeze into except that liquid behind the cadmium except that in the cobalt groove, control beginning sour PH＞5.0 when acidity is higher, adds sodium hydroxide and regulate PH to claimed range, controlled temperature;
4) add ammonium persulphate, after ammonium persulphate adds, slowly and equably add ethylsulfonic acid sodium, after adding, reaction;
5) after reaction finishes, open the underflow valve solution is put into medial launder, to removing the press filtration of cobalt pressure filter, the cobalt slag is discharged into the washing trough of cobalt slag primary water through the pump pump, and filtrating is sent and leached the workshop, and gained cobalt slag is above-mentioned higher-grade wbolt sulfonate slag.
A kind of above-mentioned ethylsulfonic acid sodium that utilizes ammonium persulphate to make oxygenant reclaims cobalt technology, and it comprises:
Reaction conditions is: temperature 35-40 ℃; Initial p H5.0-5.2; Ethylsulfonic acid sodium: ammonium persulphate: cobalt=(9-12): (4-5): (0.5-2); 20-30 minute adding medicine time; Reaction times 0.5-1.5 hour,
Step comprises:
1) remove the cobalt dosing according to solution cobalt total, the configuration proportion of medicament: ethylsulfonic acid sodium: ammonium persulphate: cobalt=(9-12): (4-5): (0.5-2),
2) ethylsulfonic acid sodium is configured to 10% solution, ammonium persulphate is configured to solution for later use,
3) squeeze into 40-45m except that in the cobalt groove
3Two sections are removed liquid behind the cadmium, and control beginning sour PH＞5.0 when acidity is higher, adds sodium hydroxide and regulate PH to claimed range, controlled temperature≤45 ℃,
4) add ammonium persulphate rapidly, after ammonium persulphate adds, slowly and equably add ethylsulfonic acid sodium, control administration timing of drug 20-30 minute after medicament adds, reacted 0.5-1.5 hour,
5) after reaction finishes, open the underflow valve solution is put into medial launder, to removing the press filtration of cobalt pressure filter, the cobalt slag is discharged into the washing trough of cobalt slag primary water through the pump pump, and filtrating is sent and leached the workshop.
A kind of above-mentioned ethylsulfonic acid sodium that utilizes ammonium persulphate to make oxygenant reclaims cobalt technology, and it comprises: wherein, reaction conditions is: 38 ℃ of temperature; Initial p H5.1; Ethylsulfonic acid sodium: ammonium persulphate: cobalt=10: 4.5: 1; 25 minutes adding medicine time; 1 hour reaction times.
A kind of Zinc hydrometallurgy process further, comprises that utilizing the above-mentioned ethylsulfonic acid sodium that utilizes ammonium persulphate to make oxygenant to reclaim cobalt technology removes cobalt.
Principle of the present invention is different from prior art; Principle of the present invention is: ammonium persulphate is a kind of strong oxidizer, and ethylsulfonic acid sodium removes cobalt and makees oxygenant with ammonium persulphate, compares traditional technology and makees oxygenant with copper sulfate; The impurity that the oxygen-free agent is brought in the sulfonic acid cobalt slag of its generation; Alleviated cobalt slag extraction burden, ammonium persulphate itself does not react with ethylsulfonic acid sodium, has reduced dosing; Thereby in purifying slag cobalt metals recovery processes, it is the at present optimal cobalt technology of removing except that cobalt technology that ammonium persulphate is done oxygenant ethylsulfonic acid sodium.
Ethylsulfonic acid sodium removes cobalt, and cobalt is often brought into the leach liquor from zinc ore concentrate.Its content in leach liquor often reaches later normal electrolyting precipitation process can not be carried out, and for this reason, must remove it.Clean liquid removes cobalt one convenient assurance electrolytic process to carry out smoothly, also from solution, extracts utmost point metal values cobalt on the other hand most possibly.
It is that the oxidisability of utilizing ammonium persulphate is with the Co in the solution that ammonium persulphate is done the mechanism that oxygenant ethylsulfonic acid sodium removes cobalt
2+Be oxidized to Co
3+, because (C
2H
5OCSS)
3The solubility product of Co is than (C
2H
5OCSS)
2Zn is little, the preferential and Co of ethylsulfonic acid sodium
3+Reaction generates blackish green complex salt deposition.
Reaction formula is following:
(NH
4)
2S
2O
8+2CoSO
4→Co
2(SO
4)
3+(NH
4)
2SO
4 (1)
6C
2H
5OCSSNa+Co
2(SO
4)
3→2(C
2H
5OCSS)
3Co↓+3Na
2SO
4 (2)
By this mechanism, ammonium persulphate only plays the effect of oxygenant in removing the cobalt process, can additive decrementation ethylsulfonic acid sodium.And copper sulfate is made oxygenant because himself and ethylsulfonic acid sodium reaction, not only can additive decrementation ethylsulfonic acid sodium, and can bring copper impurity into in the wbolt sulfonate slag.
It is following except that the reaction formula of cobalt that copper sulfate is done oxygenant ethylsulfonic acid sodium:
CuSO
4+2C
4H
9OCSSK＝K
2SO
4+(C
4H
9OCSS)
2Cu (1)
CuSO
4+2C
4H
9OCSSK+(C
4H
9OCSS)
2Cu＝K
2SO
4+C
4H
9OCSSCu+(C
4H
9OCSS)
2Co (2)
Removing the cobalt process is in mechanical agitating tank, to carry out.Remove in the cobalt groove and squeeze into 40-45m
3Two sections are removed liquid behind the cadmium, and control beginning sour PH＞5.0 when acidity is higher, adds sodium hydroxide and regulate PH to claimed range, controlled temperature≤45 ℃.Add ammonium persulphate rapidly, after ammonium persulphate adds, slowly and equably add ethylsulfonic acid sodium, control administration timing of drug 20-30 minute after medicament adds, reacted 1 hour.Reaction is opened the underflow valve solution is put into medial launder after finishing, and to removing the press filtration of cobalt pressure filter, the cobalt slag is discharged into the washing trough of cobalt slag primary water through the pump pump, and filtrating is sent and leached the workshop.
Ethylsulfonic acid sodium is flow to except that in the cobalt groove by the stream pipe power of relying on for support with tap water melt into solution again.Should be noted that the ethylsulfonic acid sodium that dissolves can not use hot water, can not shelve too of a specified duration after dissolving with tap water.This is because ethylsulfonic acid sodium has time enough or enough temperature just to carry out following decomposition reaction in water, loses the effect of ethylsulfonic acid sodium:
Remove the most outstanding in the technological operation of cobalt with ethylsulfonic acid sodium is ethylsulfonic acid sodium waste and the problem that concerns of removing the cobalt rate.The ethylsulfonic acid sodium waste with remove the cobalt rate and influenced by following factors:
(1) pH value of solution.Because ethylsulfonic acid sodium has the characteristic of being decomposed by acid, when pH value is low, promptly removes cobalt liquid and contain sourly when high, the ethylsulfonic acid sodium waste increases, and reduces operation efficiency.It is as shown in table 1 that the contriver removes the cobalt situation in different PH tests.Tabular data explanation, only pH value differs from 2.5 on the identical basis of ethylsulfonic acid sodium waste amount and other conditions, then removes cobalt rate variance 72.8%.This shows that fully pH value is to removing the influence of cobalt efficient.Rule of thumb, removing the cobalt pH value is advisable with 5.5-6.5.
Table 1
(2) remove the temperature of cobalt liquid.
Remove the temperature of cobalt liquid.The temperature of solution is advisable with 35-45 ℃ when removing the cobalt operation.Make ethylsulfonic acid sodium decomposition increasing ethylsulfonic acid sodium waste remove the cobalt rate thereby temperature is crossed the higher position, also cause bigger vaporization losses simultaneously, hinder workers'health with reducing.Cross low can the reduction like temperature and remove the due chemical response speed of cobalt, thereby influence removes cobalt efficient.Temperature with remove the cobalt rate concern free list 2 data declarations:
Temperature and the relation of removing the cobalt rate
Table 2
| Temperature ℃ | 28-30 | 38-40 | 48-50 |
| Remove cobalt rate % | 70 | 96 | 68 |
(3) amount of cupric ion.A certain amount of cupric ion can play the divalence cobalt oxidation in the solution is become cobaltic effect.The copper amount increases can increase the ethylsulfonic acid sodium waste.
(4) existence of reductive agent.Reductive agent mainly contains in the ethylsulfonic acid sodium and is mingled with, like Na
2S
2O
3, Na
2S, Na
2SO
3Deng.Their content should not surpass 2%.These materials also possibly form H except that influencing except that the oxidizing condition of cobalt under oxidizing atmosphere
2SO
4, the normal operation that is unfavorable for removing cobalt.
The invention has the advantages that, compare, outstanding at least three advantages with existing technology: the one, ammonium persulphate replaces copper sulfate and makees oxygenant, and cost of supplementary product reduces greatly; The 2nd, the impurity that the oxygen-free agent is brought in the sulfonic acid cobalt slag; The 3rd, oxygenant self does not react with ethylsulfonic acid sodium, has reduced the ethylsulfonic acid sodium waste.
Another advantage of the present invention is, has optimized the technology of zinc hydrometallurgy, makes whole technology more reasonable, also has technical process short, has reduced the wasting of resources, cuts down the consumption of energy, and the method for mixing is compared, and cost is low, and quality product is high, the promotional value advantages of higher.
Description of drawings
Fig. 1 is a process flow diagram of the present invention
Embodiment:
Embodiment 1:
Embodiment of the present invention is described below; Those skilled in the art are to be understood that; This Zinc hydrometallurgy process is merely schematic illustration; Those skilled in the art can further clearly understand the present invention through embodiment of the present invention given below, but they are not to qualification of the present invention.
Zinc hydrometallurgy process:
One, purifying slag leaches
1. technological principle
The principle that the purification slag leaches is to utilize the zinc, cadmium, cobalt and the sulfuric acid reaction that purify slag to get into solution, and copper simple substance is not stayed in the slag with sulfuric acid reaction, and realization copper separates with other valuable metals.
Main chemical reactions
Cd+H
2SO
4＝CdSO
4+H
2↑ (1)
CdO+H
2SO
4＝CdSO
4+H
2O (2)
Zn+H
2SO
4＝ZnSO
4+H
2↑ (3)
ZnO+H
2SO
4＝ZnSO
4+H
2O (4)
2. technology condition
Temperature 70-80 ℃; Reaction times 6-8 hour; Terminal point PH=2.0-5.0.
3. working specification
3.1 squeeze into ground effluent, filter wash water distribution or pickle solution 15m
3About, start and stir and open the steam intensification, add slag and waste liquid, the limit adds the acid adjustment of slag limit, adds slag about 15T, and liquor capacity is at 40m in the control flume
3About.
3.2 keep solution temperature at 70-80 ℃, add sulfuric acid transfer terminal point acidity PH=2.0-5.0 (with about 30 minutes pH values be stabilized in 2.0-5.0 no longer change be as the criterion).
3.3 after leaching end, open leaching vat underflow valve, leach liquor is put into medial launder, through the press filtration of press filtration pump pump to supernatant pressure filter, filtrating gets into rich cadmium liquid storage tank.
Two, deferrization process
1. technological principle
Utilize MnO
2Oxidisability with the Fe in the solution
2+Be oxidized to Fe
3+, the solution pH value is when 5.0 left and right sides, and ferro element is complete with the form deposition of ironic hydroxide, and reaction formula is following:
Fe
3++3H
2O→Fe(OH)
3↓+3H
+
2. technology condition
Temperature 70-80 ℃; PH (beginning) 3.5-4.0; PH (end) 5.0-5.2; Oxidization time 30 minutes; 30 minutes reaction times (time behind the accent alkali).
3. working specification
3.1 medicament add-on: MnO
2Be 4 times of iron amount.
3.2 with MnO
2Be configured to massfraction and be 20% pulp liquid; With Na
2CO
3Be configured to massfraction and be 25% solution.
3.3 squeeze into 40m in the iron removal trough
3About rich cadmium liquid, the analytical solution iron level confirms that according to the iron level of solution the usage quantity of MnO2 is carried out MnO
2The configuration of pulp liquid is the MnO for preparing
2Pulp liquid slowly adds in the solution, and the control solution temperature adds MnO at 70-75 ℃
2Preceding solution pH value=3.5-4.0, MnO
2After the adding, use Na
2CO
3Acid adjustment degree to pH value＞5.0 keep pH value constant, react 30 minutes.
After 3.4 reaction finishes, get deironing after liquid analyze, control back liquid iron content≤20mg/L then prepares MnO according to residual iron amount again if iron level is defective
2The deironing of pulp liquid, qualified after, open iron removal trough underflow valve and put solution into medial launder and carry out press filtration by deironing press filtration pump pump to pressure filter.
3.5 filter residue advances the pulp groove, adds pickle solution, produces water or water of condensation control liquid-solid ratio at 4-5: 1, drive the pulp pump while stirring and pulp liquid is delivered to leaches the workshop.Filtrating is advanced liquid storage tank after the deironing.
Three, replacing process
1. technological principle
The principle of utilizing the low metal of standard potential to cement out the high metals ion of standard potential cements out the solution metal cadmium ion with zinc powder, and reaction formula is following:
Zn+CdSO
4＝ZnSO
4+Cd
2. technology condition
Once displacement: PH (beginning)=3.5-4.0; The zinc powder add-on is 0.5 times of cadmium amount; Reaction times 30-60 minute.
Twice replaced: PH (beginning)=3.5-4.0; The zinc powder add-on is 3～4 times of cadmium amount; Reaction times 30-60 minute.
3. working specification
3.1 replacement operator rules
3.1.1 squeeze into 40-45m in the displacement slot
3About deironing after liquid, sour PH3.5-4.0 of control beginning when acidity is on the low side, replenishes an amount of sulfuric acid.
3.1.2 calculate the cadmium total amount according to liquid cadmium content after the deironing, extraordinarily go into zinc powder by 0.5 of cadmium total amount.
3.1.3 controlling reaction time 40 minutes.Reaction is opened the underflow valve solution is put into medial launder after finishing, and through section displacement pressure filter press filtration of pump pump to, Spongy Cadmium is discharged into bubble cadmium groove water and covers, anti-oxidation, and filtrating gets into two sections displacement slot.
3.2 twice replaced working specification
3.2.1 squeeze into 40-45m in the twice replaced groove
3Once except that liquid behind the cadmium, sour PH=4.0 of control beginning when acidity is on the low side, replenishes an amount of sulfuric acid.
3.2.2 calculate the cadmium total amount except that liquid cadmium content behind the cadmium according to one section, extraordinarily go into zinc powder by 4 of cadmium total amount, reacted 30 minutes.
3.2.3 after reacting end, open the underflow valve solution is put into medial launder, through section displacement pressure filter press filtration of pump pump to two, Spongy Cadmium is discharged at ground, the go-cart of packing into is then sent and is purified the slag leaching vat, and filtrating gets into except that liquid storage tank behind the cadmium.(according to experimental data, two sections cadmium slags contain the Zn height, return one section and remove cadmium and can cause Spongy Cadmium to contain the Zn height, influence thick cadmium melting.)
Four, ammonium persulphate is done oxygenant ethylsulfonic acid sodium and is removed cobalt
1. technological principle
The oxidisability of utilizing ammonium persulphate is with the Co in the solution
2+Be oxidized to Co
3+, because (C
2H
5OCSS)
3The solubility product of Co is than (C
2H
5OCSS)
2Zn is little, the preferential and Co of ethylsulfonic acid sodium
3+Reaction generates blackish green complex salt deposition.
Reaction formula is following:
(NH
4)
2S
2O
8+2CoSO
4→Co
2(SO
4)
3+(NH
4)
2SO
4 (1)
6C
2H
5OCSSNa+Co
2(SO
4)
3→2(C
2H
5OCSS)
3Co↓+3Na
2SO
4 (2)
2. technology condition
Temperature 35-40 ℃; PH (beginning) 5.0-5.2; Ethylsulfonic acid sodium: ammonium persulphate: cobalt=10: 4.5: 1; Administration timing of drug 20-30 minute; 1 hour reaction times.
3. working specification
3.1 remove cobalt dosing, the configuration proportion of medicament: ethylsulfonic acid sodium: ammonium persulphate: cobalt=10: 4.5: 1 according to solution cobalt total.
3.2 ethylsulfonic acid sodium is configured to 10% solution, ammonium persulphate is configured to solution for later use.
3.3 remove in the cobalt groove and squeeze into 40-45m
3Two sections are removed liquid behind the cadmium, and control beginning sour PH＞5.0 when acidity is higher, adds sodium hydroxide and regulate PH to claimed range, controlled temperature≤45 ℃.
3.4 add ammonium persulphate rapidly, after ammonium persulphate adds, slowly and equably add ethylsulfonic acid sodium, control administration timing of drug 20-30 minute after medicament adds, reacted 1 hour.
3.5 reaction is opened the underflow valve solution is put into medial launder after finishing, to removing the press filtration of cobalt pressure filter, the cobalt slag is discharged into the washing trough of cobalt slag primary water through the pump pump, and filtrating is sent and leached the workshop.
Embodiment 2:
Be similar to other step of embodiment 1, wherein the technology for the recovery cobalt in the Zinc hydrometallurgy process does, ammonium persulphate is done oxygenant ethylsulfonic acid sodium and reclaimed cobalt:
Technology condition is: temperature 35-40 ℃; Initial p H5.0-5.2; Ethylsulfonic acid sodium: ammonium persulphate: cobalt=(9-12): (4-5): (0.5-2); 20-30 minute adding medicine time; Reaction times 0.5-1.5 hour,
3. working specification
3.1 remove the cobalt dosing according to solution cobalt total, the configuration proportion of medicament: ethylsulfonic acid sodium: ammonium persulphate: cobalt=(9-12): (4-5): (0.5-2),
3.2 ethylsulfonic acid sodium is configured to 10% solution, ammonium persulphate is configured to solution for later use,
3.3 remove in the cobalt groove and squeeze into 40-45m
3Two sections are removed liquid behind the cadmium, and control beginning sour PH＞5.0 when acidity is higher, adds sodium hydroxide and regulate PH to claimed range, controlled temperature≤45 ℃,
3.4 add ammonium persulphate rapidly, after ammonium persulphate adds, slowly and equably add ethylsulfonic acid sodium, control administration timing of drug 20-30 minute after medicament adds, reacted 0.5-1.5 hour,
3.5 reaction is opened the underflow valve solution is put into medial launder after finishing, to removing the press filtration of cobalt pressure filter, the cobalt slag is discharged into the washing trough of cobalt slag primary water through the pump pump, and filtrating is sent and leached the workshop.
Embodiment 3
Be similar to other step of embodiment 1, wherein the technology for the recovery cobalt in the Zinc hydrometallurgy process is: ammonium persulphate is done oxygenant ethylsulfonic acid sodium and is removed cobalt, and its technology condition is:
38 ℃ of temperature; PH (beginning) 5.1; Ethylsulfonic acid sodium: ammonium persulphate: cobalt=12: 4.8: 0.9; Administration timing of drug 29 minutes; 1.1 hours reaction times.
Operation steps comprises
3.1 remove cobalt dosing, the configuration proportion of medicament: ethylsulfonic acid sodium: ammonium persulphate: cobalt=12: 4.8: 0.9 according to solution cobalt total.
3.2 ethylsulfonic acid sodium is configured to 10% solution, ammonium persulphate is configured to solution for later use.
3.3 remove in the cobalt groove and squeeze into 40-45m
3Two sections are removed liquid behind the cadmium, and sour PH=5.1 of control beginning when acidity is higher, adds sodium hydroxide and regulates PH to claimed range, controlled temperature≤45 ℃.
3.4 add ammonium persulphate rapidly, after ammonium persulphate adds, slowly and equably add ethylsulfonic acid sodium, control administration timing of drug 29 minutes after medicament adds, reacted 1.1 hours.
3.5 reaction is opened the underflow valve solution is put into medial launder after finishing, to removing the press filtration of cobalt pressure filter, the cobalt slag is discharged into the washing trough of cobalt slag primary water through the pump pump, and filtrating is sent and leached the workshop.
Embodiment 4
Be similar to other step of embodiment 1, wherein the technology for the recovery cobalt in the Zinc hydrometallurgy process does, ammonium persulphate is done oxygenant ethylsulfonic acid sodium and removed cobalt, and its technology condition is:
Temperature 35-40 ℃; PH (beginning) 5.0-5.2; Ethylsulfonic acid sodium: ammonium persulphate: cobalt=9.5: 4.8: 2; Administration timing of drug 20-30 minute; 1 hour reaction times.
3. working specification
3.1 remove cobalt dosing, the configuration proportion of medicament: ethylsulfonic acid sodium: ammonium persulphate: cobalt=10: 4.5: 2 according to solution cobalt total.
3.2 ethylsulfonic acid sodium is configured to 10% solution, ammonium persulphate is configured to solution for later use.
3.3 remove in the cobalt groove and squeeze into 40-45m
3Two sections are removed liquid behind the cadmium, and control beginning sour PH＞5.0 when acidity is higher, adds sodium hydroxide and regulate PH to claimed range, controlled temperature≤45 ℃.
3.4 add ammonium persulphate rapidly, after ammonium persulphate adds, slowly and equably add ethylsulfonic acid sodium, control administration timing of drug 20-30 minute after medicament adds, reacted 1 hour.
3.5 reaction is opened the underflow valve solution is put into medial launder after finishing, to removing the press filtration of cobalt pressure filter, the cobalt slag is discharged into the washing trough of cobalt slag primary water through the pump pump, and filtrating is sent and leached the workshop.
Claims (6)
1. a higher-grade wbolt sulfonate slag is characterized in that, contains the cobalt of 15-21%.
2. a wbolt sulfonate slag as claimed in claim 1 is characterized in that, it contains 20% the cobalt of having an appointment.
3. an ethylsulfonic acid sodium that utilizes ammonium persulphate to make oxygenant reclaims cobalt technology, it is characterized in that it comprises:
1) removes cobalt dosing, the configuration proportion of medicament according to solution cobalt total;
2) ethylsulfonic acid sodium is configured to solution, ammonium persulphate is configured to solution for later use;
3) squeeze into except that behind the cadmium liquid except that in the cobalt groove, control beginning sour PH＞5.0 when acidity is higher, adds sodium hydroxide and regulate PH to claimed range, controlled temperature;
4) add ammonium persulphate, after ammonium persulphate adds, slowly and equably add ethylsulfonic acid sodium, after adding, reaction;
5) after reaction finishes, open the underflow valve solution is put into medial launder, to removing the press filtration of cobalt pressure filter, the cobalt slag is discharged into the washing trough of cobalt slag primary water through the pump pump, and filtrating is sent and leached the workshop, and gained cobalt slag is the described higher-grade wbolt sulfonate slag of claim 1-2.
4. the ethylsulfonic acid sodium that utilizes ammonium persulphate to make oxygenant according to claim 3 reclaims cobalt technology, it is characterized in that it comprises:
Reaction conditions is: temperature 35-40 ℃; Initial p H 5.0-5.2; Ethylsulfonic acid sodium: ammonium persulphate: cobalt=(9-12): (4-5): (0.5-2); 20-30 minute adding medicine time; Reaction times 0.5-1.5 hour,
Step comprises:
1) remove the cobalt dosing according to solution cobalt total, the configuration proportion of medicament: ethylsulfonic acid sodium: ammonium persulphate: cobalt=(9-12): (4-5): (0.5-2),
2) ethylsulfonic acid sodium is configured to 10% solution, ammonium persulphate is configured to solution for later use,
3) squeeze into 40-45m except that in the cobalt groove
3Two sections remove cadmium liquid after, control beginning sour PH＞5.0 when acidity is higher, adds sodium hydroxide and regulate PH to claimed range, controlled temperature≤45 ℃,
4) add ammonium persulphate rapidly, after ammonium persulphate adds, slowly and equably add ethylsulfonic acid sodium, control administration timing of drug 20-30 minute after medicament adds, reacted 0.5-1.5 hour,
5) after reaction finishes, open the underflow valve solution is put into medial launder, to removing the press filtration of cobalt pressure filter, the cobalt slag is discharged into the washing trough of cobalt slag primary water through the pump pump, and filtrating is sent and leached the workshop, and gained cobalt slag is the described higher-grade wbolt sulfonate slag of claim 1-2.
5. an ethylsulfonic acid sodium that utilizes ammonium persulphate to make oxygenant as claimed in claim 4 reclaims cobalt technology, and it is characterized in that: wherein, reaction conditions is: 38 ℃ of temperature; Initial p H 5.1; Ethylsulfonic acid sodium: ammonium persulphate: cobalt=10: 4.5: 1; 25 minutes adding medicine time; 1 hour reaction times.
6. a Zinc hydrometallurgy process is characterized in that, comprises that utilizing the described ethylsulfonic acid sodium that utilizes ammonium persulphate to make oxygenant of claim 3-5 to reclaim cobalt technology removes cobalt.
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| CN113897484A (en) * | 2021-08-18 | 2022-01-07 | 西北矿冶研究院 | Energy-saving method for purifying and removing cobalt in zinc hydrometallurgy |
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