CN101942567A - Method for removing arsenic and antimonic from anode sludge containing polyvalence composite type arsenic-antimonic compound - Google Patents
Method for removing arsenic and antimonic from anode sludge containing polyvalence composite type arsenic-antimonic compound Download PDFInfo
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- CN101942567A CN101942567A CN2010105166683A CN201010516668A CN101942567A CN 101942567 A CN101942567 A CN 101942567A CN 2010105166683 A CN2010105166683 A CN 2010105166683A CN 201010516668 A CN201010516668 A CN 201010516668A CN 101942567 A CN101942567 A CN 101942567A
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- arsenic
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- antimonic
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Abstract
The invention provides a method for removing arsenic and antimonic from anode sludge containing a polyvalence composite type arsenic-antimonic compound. The method adopts a twp-step vacuum dynamic joint technology comprising vacuum dynamic evaporation and vacuum dynamic flash reduction. The treatment of the anode sludge containing the polyvalence composite type arsenic-antimonic compound comprises the following two steps: firstly, removing low-valence arsenic-antimonic oxide through the vacuum dynamic evaporation; and then under the vacuum dynamic condition, reducing the high-valence arsenic-antimonic oxide into the low-valence arsenic-antimonic oxide at a flash speed and then removing. After the treatment by the two steps, the total arsenic-removing ratio is above 99%, and the total antimonic-removing ratio is above 93%. The process has the advantages of short flow, good effect, environment protection and the like.
Description
Technical field
The invention belongs to the pyrometallurgy field, particularly a kind ofly contain the method that the compound arsenic antimony compounds of the multivalence attitude anode sludge removes arsenic and antimony.
Background technology
Lead anode slurry is a kind of byproduct of electrolytic lead refining process output, and it is an important source material of extracting precious metal, and its main component has Au, Ag, Pb, Cu, As, Sb and Bi etc.Obtain noble metal in order to reclaim, impurity element such as As and Sb etc. must preferentially remove.
The influence of arsenic and antimony antianode mud treating processes is bigger, and they not only make ANODE SLIME TREATMENT engineering complexity, and can influence the quality of other comprehensive utilization products, and contaminate environment.The pretreatment technology of the high-arsenic antimony anode sludge mainly is divided into firing method process and wet process.Firing method process comprises volatilization roasting method and reduction roasting method etc.Existing thermal process environmental pollution is serious, and the dust collecting system complexity is invested very greatly, and benefit is not high.Wet process is divided into acidleach, alkali soaks and method such as chlorination leaching, but its long flow path operation is many, and the leach liquor treatment capacity is big, and valuable element complexity such as recycling arsenic antimony need the chemical feedstocks of a large amount of many kinds simultaneously, and cost is higher.So existing processes also exists a lot of problems to need to solve.
For the preliminary treatment of high-arsenic antimony lead anode slurry, not only to consider the removal efficiency of arsenic and antimony, also to pay attention to the protection to environment, and need pay attention to the processing of post-order process, for the recovery of arsenic and antimony product creates conditions.Arsenic antimony and compound thereof all have very high using value: arsenic can be used for producing alloy, the plumbous electronic component of making bullet, semiconductor material etc., and its compound is applied to make agricultural chemicals, sanitas and medicine etc.; Antimony is used as the additive of other alloy more, and its compound is widely used in enamel, pigment, fire retardant and fumicants etc.Therefore, for the harmful substance that contains arsenic antimony is transformed into price product, press at present development a kind of from the earth of positive pole high-efficiency environment friendly process and reclaim the technology of arsenic and antimony.
Summary of the invention
The present invention proposes a kind of method that the compound arsenic antimony compounds of the multivalence attitude anode sludge removes arsenic and antimony that contains, utilize this method to remove arsenic and antimony, have advantages such as short, the effective and environmental protection of flow process.
According to the relation of material temperature and vapour pressure, under uniform temp, the arsenic sb oxide As of lower valency
2O
3And Sb
2O
3Vapour pressure more much larger than the vapour pressure of other materials in the earth of positive pole.Therefore, under vacuum condition, As
2O
3And Sb
2O
3Be easy to from the earth of positive pole, be evaporated in the gas phase and go, and other materials with low-steam pressure are still stayed in the steaming excess, thereby the removal of impurities that has realized arsenic and antimony separates.The arsenic antimony compounds vapour pressure of high valence state is very low and be difficult to decomposition, and the arsenic sb oxide evaporation that needs they to be reduced into lower valency is removed.In addition, the dividing potential drop of minimizing evaporant can further promote As in the earth of positive pole
2O
3And Sb
2O
3Evaporation.So, in the process of vacuum reaction, in system, pass into a small amount of air, drive the As on earth of positive pole surface with dynamic form
2O
3And Sb
2O
3Vapour molecule, thus evaporant As reduced
2O
3And Sb
2O
3Dividing potential drop, the evaporation rate of the increase earth of positive pole, reinforcement removes the effect of arsenic antimony.The present invention is based on these thermodynamics bases,, proposed two first and gone on foot the method that the dynamic vacuum United Technologies remove anode sludge arsenic and antimony at the characteristics that contain the compound arsenic antimony compounds of the multivalence attitude anode sludge.Two step dynamic vacuum United Technologies have comprised dynamic vacuum evaporation and dynamic vacuum flash reduction two portions: the arsenic sb oxide that at first removes lower valency by the method for dynamic vacuum evaporation, under the dynamic vacuum condition, the arsenic sb oxide that the arsenic sb oxide flash of high valence state is reduced into lower valency is removed then.
Technical scheme of the present invention is:
1) will contain the polyvalence composite type arsenic antimonial earth of positive pole and place under the condition of vacuum, and be warming up to 750～800 ℃ and carry out the vacuum evaporation reaction, and in course of reaction, in system, pass into mobile carrier gas, drive the As on earth of positive pole surface with dynamic form
2O
3And Sb
2O
3Vapour molecule;
2) by mud after the steaming after the above vacuum evaporation processing, after adding charcoal powder, be warming up to 800～900 ℃, in the situation that passes into mobile carrier gas, carry out the vacuum reduction ER equally so that pentavalent arsenic and the sb oxide of pentavalent or the tetravalence arsenic sb oxide As that is reduced into rapidly lower valency
2O
3And Sb
2O
3Rear volatilization is removed; Reaction can obtain the precious metals containing lead alloy after finishing.
Evaporant As
2O
3And Sb
2O
3Cooling is collected in condenser.
Described 1) the vacuum reaction time is 50～70 minutes in the step, and vacuum tightness is 220～270Pa, and flow rate of carrier gas is 350～450ml/min.
Described 2) reaction times is 50～70 minutes in the step, and vacuum tightness is 220～270Pa, and flow rate of carrier gas is 350～450ml/min.
Described 2) add the charcoal amount in the step and be 7～8% of evaporation shale amount.
The present invention drives the As on earth of positive pole surface by pass into carrier gas in system in course of reaction with dynamic form
2O
3And Sb
2O
3Vapour molecule, thus evaporant As reduced
2O
3And Sb
2O
3Dividing potential drop increases the evaporation rate of the earth of positive pole and the effect that reinforcement removes arsenic antimony.
Specific operation process of the present invention is:
Earlier the anode sludge is placed the vacuum reaction stove, rise to 750～800 ℃ under vacuum condition, feed the air that flow velocity is 350～450ml/min simultaneously, kept 50～70 minutes, this moment, the vacuum tightness of system was 220～270Pa.The arsenic sb oxide of lower valency flows into condenser with the carrier gas volatilization in the earth of positive pole, and cooling is collected.
Mud after the steaming after the above-mentioned dynamic vacuum evaporation process of learning from else's experience then adds 7～8% the wood charcoal powder account for evaporation shale amount, mixes to place in the vacuum reaction stove.Stove is risen to 800～900 ℃, and feeding flow velocity simultaneously is 350～450ml/min air, and keeps 50～70 minutes, and this moment, the vacuum tightness of system was 220～270Pa.Under the condition of vacuum, because As
2O
3And Sb
2O
3Vapour pressure very big, so the arsenic sb oxide one of high valence state is reduced into the arsenic sb oxide As of lower valency
2O
3And Sb
2O
3, and promptly volatilize by the carrier gas of flowing and to remove, thereby can stop to continue to be reduced into metal.The steam of volatile matter cools off collection in condenser.Obtain the precious metals containing lead alloy of enrichment silver after reaction finishes, precious metals containing lead further refining treatment reclaims noble metal.Calculated by precious metals containing lead, the removal efficiency of the total arsenic of two step dynamic vacuum combination methods is more than 99%, and the removal efficiency of total antimony is more than 93%.Test the residue obtained smeltery that returns and reclaim valuable metal, condensate can reclaim respectively As after separating
2O
3And Sb
2O
3
The schema of the inventive method as shown in Figure 1.
The present invention is directed to existing various shortcoming and the problem of handling lead anode slurry, proposed to use the dynamic vacuum United Technologies to be applied to contain the removal of the compound arsenic antimony compounds of multivalence attitude anode sludge arsenic and antimony.Compare with existing technology, the present invention has the following advantages:
1. reaction is carried out in the vacuum tightness system, has prevented As
2O
3And Sb
2O
3Dust pollution, be a kind for the treatment of technology of clean environment firendly.
2. can reduce the loss of metal under the vacuum condition, when removing arsenic antimony, can obtain precious metals containing lead, for next step separating-purifying has been created good condition.
3. adopt this method to simplify the flow process of processing the earth of positive pole, cost is lower, the operating condition safe ready.
4. remove the effective of arsenic and antimony, the decreasing ratio of total arsenic is greater than 99%, and the decreasing ratio of total antimony is greater than 93%.
Description of drawings:
Fig. 1 is the schema of the inventive method.
Embodiment
Following examples are intended to illustrate the present invention rather than limitation of the invention further.
Embodiment
Get that a kind of to contain the compound arsenic antimony compounds of multivalence attitude lead anode slurry be raw material,, mainly contain Pb17.01wt%, As19.35wt%, Sb24.75wt%, Ag3.88wt%, Bi3.28wt% and Cu1.92wt% in the anode sludge through chemical constituents determination.At first anode sludge raw material is placed in the material boat, places the vacuum reaction stove to carry out dynamic evaporation and handle.The reaction conditions of dynamic vacuum evaporation is 750～780 ℃ of temperature, 60 minutes time, the about 250Pa of vacuum tightness, the about 400ml/min of air velocity.Calculate through weight-loss method, the evaporation rate of the earth of positive pole is 30.8% after the dynamic vacuum evaporation process.Mud mainly contains the arsenic antimonial of high valence state after steaming.The wood charcoal powder of mud after the steaming of 10g and 7.5% is mixed, be placed on the material boat and be built in and carry out dynamic flash reduction reaction in the vacuum reaction stove.Dynamic vacuum flash reductive condition is 800～830 ℃ of temperature, 60 minutes time, the about 250Pa of vacuum tightness, the about 400ml/min of air velocity.Reaction can be collected the precious metals containing lead that obtains 2.2g after finishing, and through chemical constituents determination, mainly contains Pb31.57wt%, As0.047wt%, Sb9.89wt%, Ag25.11wt%, Bi14.85wt% and Cu8.28wt% in the precious metals containing lead.Press precious metals containing lead and calculate, total removal efficiency of two step dynamic vacuum combination method arsenic is 99.96%, and total removal efficiency of antimony is 93.92%.The main component of experiment gained condensate is As
2O
3And Sb
2O
3Powder, this condensate can reclaim respectively As through methods such as vacuum separation
2O
3And Sb
2O
3, realize resource regeneration.
Claims (5)
1. one kind contains the method that the compound arsenic antimony compounds of the multivalence attitude anode sludge removes arsenic and antimony, it is characterized in that, may further comprise the steps:
1) will contain the polyvalence composite type arsenic antimonial earth of positive pole and place under the condition of vacuum, and be warming up to 750～800 ℃ and carry out the vacuum evaporation reaction, and in course of reaction, in system, pass into mobile carrier gas, drive the As that earth of positive pole surface volatilizes with dynamic form
2O
3And Sb
2O
3Vapour molecule;
2) by mud after the steaming after the above vacuum evaporation processing, after adding charcoal powder, be warming up to 800～900 ℃, equally carry out the vacuum reduction ER in the situation of flowing carrier gas passing into, make the sb oxide of the arsenic of pentavalent and pentavalent or tetravalence be reduced into rapidly the As of lower valency
2O
3And Sb
2O
3Rear volatilization is removed; Reaction obtains the precious metals containing lead alloy after finishing.
2. the anode sludge according to claim 1 removes the method for arsenic and antimony, it is characterized in that, described 1) reaction times is 50～70 minutes in the step, and vacuum tightness is 220～270Pa, and flow rate of carrier gas is 350～450ml/min.
3. the anode sludge according to claim 1 and 2 removes the method for arsenic and antimony, it is characterized in that, described 2) reaction times is 50～70 minutes in the step, and vacuum tightness is 220～270Pa, and flow rate of carrier gas is 350～450ml/min.
4. the earth of positive pole according to claim 3 removes the method for arsenic and antimony, it is characterized in that, described 2) add the charcoal amount in the step and be 7～8% of shale amount after steaming.
5. the earth of positive pole according to claim 1 removes the method for arsenic and antimony, it is characterized in that evaporant As
2O
3And Sb
2O
3Cooling is collected in condenser.
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|---|---|---|---|
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102251126A (en) * | 2011-07-11 | 2011-11-23 | 昆明理工大学 | Method for removing arsenic impurities from tin |
| CN103205576A (en) * | 2013-03-22 | 2013-07-17 | 安徽铜冠有色金属（池州）有限责任公司九华冶炼厂 | Method for treating lead anode slime |
| CN105296764A (en) * | 2015-12-02 | 2016-02-03 | 郴州市金贵银业股份有限公司 | Method for synchronously pre-removing arsenic and antimony from lead anode mud |
| CN107217145A (en) * | 2016-12-09 | 2017-09-29 | 郴州万墨环保科技有限公司 | A kind of method that copper anode mud vacuum reduction takes off lead antimony bismuth selen-tellurjum arsenic |
| CN108531734A (en) * | 2018-04-18 | 2018-09-14 | 昆明理工大学 | A kind of method of antimony, iron and lead in useless LDPE Reduced separatings antimony slag |
| CN108913905A (en) * | 2018-07-20 | 2018-11-30 | 芜湖新瑟安智能科技有限公司 | A kind of anode mud with high As and Pb processing recovery method |
| CN108950248A (en) * | 2018-07-30 | 2018-12-07 | 朱胜华 | A kind of method of low temperature distillation harmless treatment high-arsenic antimony oxygen |
| CN109777962A (en) * | 2019-03-01 | 2019-05-21 | 昆明理工大学 | A kind of method of lead anode slurry removing arsenic |
| CN113930628A (en) * | 2021-09-03 | 2022-01-14 | 湖南有色金属研究院有限责任公司 | Comprehensive recovery method of arsenic-antimony smoke |
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| CN1270235A (en) * | 2000-04-21 | 2000-10-18 | 沈阳冶炼厂 | Process for treating low-grade anode mud |
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| CN1270235A (en) * | 2000-04-21 | 2000-10-18 | 沈阳冶炼厂 | Process for treating low-grade anode mud |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102251126A (en) * | 2011-07-11 | 2011-11-23 | 昆明理工大学 | Method for removing arsenic impurities from tin |
| CN103205576A (en) * | 2013-03-22 | 2013-07-17 | 安徽铜冠有色金属（池州）有限责任公司九华冶炼厂 | Method for treating lead anode slime |
| CN105296764A (en) * | 2015-12-02 | 2016-02-03 | 郴州市金贵银业股份有限公司 | Method for synchronously pre-removing arsenic and antimony from lead anode mud |
| CN107217145A (en) * | 2016-12-09 | 2017-09-29 | 郴州万墨环保科技有限公司 | A kind of method that copper anode mud vacuum reduction takes off lead antimony bismuth selen-tellurjum arsenic |
| CN108531734A (en) * | 2018-04-18 | 2018-09-14 | 昆明理工大学 | A kind of method of antimony, iron and lead in useless LDPE Reduced separatings antimony slag |
| CN108531734B (en) * | 2018-04-18 | 2020-02-07 | 昆明理工大学 | Method for reducing and separating antimony, iron and lead in antimony slag by using waste LDPE |
| CN108913905A (en) * | 2018-07-20 | 2018-11-30 | 芜湖新瑟安智能科技有限公司 | A kind of anode mud with high As and Pb processing recovery method |
| CN108950248A (en) * | 2018-07-30 | 2018-12-07 | 朱胜华 | A kind of method of low temperature distillation harmless treatment high-arsenic antimony oxygen |
| CN109777962A (en) * | 2019-03-01 | 2019-05-21 | 昆明理工大学 | A kind of method of lead anode slurry removing arsenic |
| CN109777962B (en) * | 2019-03-01 | 2021-01-05 | 昆明理工大学 | Method for removing arsenic from lead anode mud |
| CN113930628A (en) * | 2021-09-03 | 2022-01-14 | 湖南有色金属研究院有限责任公司 | Comprehensive recovery method of arsenic-antimony smoke |
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Application publication date: 20110112 |