CN1187459C - Dearsenifying process for anode mud with high As and Pb content - Google Patents
Dearsenifying process for anode mud with high As and Pb content Download PDFInfo
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- CN1187459C CN1187459C CNB011257008A CN01125700A CN1187459C CN 1187459 C CN1187459 C CN 1187459C CN B011257008 A CNB011257008 A CN B011257008A CN 01125700 A CN01125700 A CN 01125700A CN 1187459 C CN1187459 C CN 1187459C
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- roasting
- arsenic
- temperature
- removing method
- anode sludge
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Abstract
The present invention relates to a dearsenifying process for anode mud with high contents of As and Pb. Water vapor 1 is led in a closed rotary kiln 2 for roasting, and smoke dust generated by roasting is collected through a condensing system 4 so as to recycle As2O3. A small quantity of tail gas is discharged after being treated by alkali liquor, the roasting temperature is controlled to be 400 to 750 DEG C, the roasting time is 0.5 to 4 hours, the flow quantity of water vapor is 300 to 5000 ml/min, and the proper rotary speed of the rotary kiln is required, so that most of As can be dearsenified from the anode mud, while Pb and Sb remain in the roasted product. The dearsenifying process has the advantages of favorable dearsenification effect, convenient method, simple equipment, low cost, no environmental pollution, etc., and is suitable for the pretreatment dearsenification of the anode mud with high contents of As and Pb.
Description
Technical field
The present invention relates to the method for dearsenification from anode mud with high As and Pb, especially adopt the method for pyrogenic process volatilization roasting dearsenification.
Background technology
High-arsenic material, the particularly high arsenic anode sludge are the important source material of extracting non-ferrous metal and precious metal, and dearsenification is to handle such material recognized techniques difficult point always.The existing processes flow process mainly contains firing method process, wet process and pyrogenic process-wet method combined flow process.Firing method process mainly contains volatilization roasting method, reduction roasting method and vacuum dearsenification method etc.The technology of firing method process is comparatively ripe, and is strong to the adaptability of raw material, and flow process is simple, easy and simple to handle, and a lot of smelteries all adopt the pyrogenic process dearsenification.But the weak effect of firing method process dearsenification, arsenic-removing rate can only reach 40-70%, and service temperature is higher, and plant issue is difficult to solve, and environmental pollution is serious." Shen Ye science and technology ", nineteen eighty-twos 2 " discussion of the recycling of arsenic antimony and production technique thereof in the copper-lead anode sludge " literary composition of carrying of periodical, introduced copper-lead anode sludge voloxidation roasting for arsenic removal, produce the technology of white arsenic, technological process is carried out the voloxidation roasting for arsenic removal under air atmosphere the high arsenic anode sludge being placed in the sealing rotary kiln, and the volatilization flue gas is collected by dust collection device can obtain thick white arsenic.The roasting under air atmosphere of this technology, in traditional volatilization roasting process, because roasting in air atmosphere, strong excessively oxidizing atmosphere causes As (III) to transform awkward evaporable As (V) compound in the stove, and voloxidation roasting for arsenic removal rate is lower, and arsenic separates relatively poor with plumbous antimony, exist environmental pollution serious, cycle is long, problems such as cost height.
Summary of the invention
The object of the present invention is to provide a kind of Dearsenifying process for anode mud with high As and Pb content of efficient pollution-free.
For realizing goal of the invention, the technical process of Dearsenifying process for anode mud with high As and Pb content of the present invention comprises oxidizing roasting, collect the roasting volatile matter and handle discharge technology step behind the tail gas with alkali lye, the temperature of oxidizing roasting is 400～750 ℃, roasting time is 0.5～4 hour, feed flow range when above and finish when temperature in the stoving oven reaches the boiling point of water in the oxidizing roasting temperature rise period, adopt condenser system to collect the roasting volatile matter in water vapor to the roasting of 300 ml/min～5000 ml/min.
In order to realize the present invention better, can control the water vapour flow is 500 ml/min～2000 ml/min; Best water vapour flow is 1000 ml/min; The condensing agent that condenser system adopts can be a water; Can adopt airtight rotary kiln to realize oxidizing roasting, 0.25 rev/min～3 rev/mins of rotary kiln rotating speeds; Maturing temperature is 550 ℃～600 ℃ preferably, roasting time 2～3 hours; Best maturing temperature is 575 ℃.
The invented technology technology is to propose on the basis of traditional pyrogenic process-voloxidation roasting method.Most As are with simple substance As and As in the high concn. arsenic and lead mud
2O
3Form exists.By the relation of both vapour pressures and temperature as can be known, under maturing temperature (650-800 ℃), As
4And As
2O
3All has higher vapour pressure, so the both has very strong volatility.The volatilization roasting method is utilized As just
4And As
2O
3Vapour pressure and the notable difference between other valuable metal, adopt the high temperature sublimation method that arsenic is sloughed, reach, heavy metal isolating purpose expensive with other.In roasting process, As
2O
3Compare As
4Have stronger volatility, consider As simultaneously
2O
3This moment, free energy of formation was lower, thereby As
4In volatilization process, all be oxidized to the stronger As of volatility
2O
3, at last mainly with As
2O
3Form enters dust collecting system with furnace gas.Though the volatilization roasting method can realize the dearsenification purpose, arsenic-removing rate is very low in the production process.Its reason mainly is a high concn. arsenic and lead mud thing phase composition complexity, and some arsenic exists with the high price form.Tradition volatilization roasting process, owing to be roasting in air atmosphere, strong excessively oxidizing atmosphere causes As (III) to transform awkward evaporable As (V) compound in the stove.
The high oxide of arsenic and the volatility of arsenate are very little, so the formation of these high price arsenides is the inefficient major causes of volatilization roasting method dearsenification.These high price arsenides have higher decomposition temperature, for increasing the evaporation rate of arsenic, must carry out roasting under higher temperature.Therefore for avoiding the generation of difficult evaporable high price arsenide, should make high concn. arsenic and lead mud volatilization roasting in weak oxide atmosphere or even more weak reducing atmosphere.According in this, the present invention is chosen in oxidizing roasting under the water vapor, reason be lead anode slurry under the lower water vapor of oxygen gesture, elemental arsenic wherein 400 ℃-700 ℃ of temperature down and steam reaction generate volatile As
2O
3:
Under this atmosphere, the As of generation
2O
3Under lower oxygen gesture, can not be oxidized to high oxide, make As mainly with As
2O
3Form volatilize in a large number.Simultaneously because reaction generates a spot of H
2, make furnace atmosphere have week reduction, this weak reducing atmosphere helps the reduction of high price arsenide to destroy:
In order to guarantee to keep suitable water vapor in the stoving oven in the not condensation of water vapor and stoving oven, should reach the boiling point of water feeding water vapor and be retained to roasting and finish when above when temperature in the stoving oven in the temperature rise period.So the present invention is volatilization roasting under water vapour atmosphere, can satisfy the volatilization requirement of arsenic preferably, make arsenic (400 ℃-700 ℃) under lower temperature condition just can reach higher evaporation rate (about 90%).Air atmosphere voloxidation roasting compared with traditional has arsenic decreasing ratio height, the advantage that temperature is low.In addition, arsenic and compound thereof are swift in response under the water vapour atmosphere in stove and generate As
2O
3Gas is because As
2O
3Soluble in water under the gas high temperature, so the volatile matter As that reaction generates
2O
3Gas at high temperature is dissolved in to form in the water vapor and mixes furnace gas, enters condenser system together.Water vapor has the characteristics of the rapidly easy condensation of heat absorption with respect to other gas, so just help As
2O
3Condensation.As in condenser system
2O
3Gas is along with the also a large amount of condensations of the rapid condensation of water vapor enter in the aqueous solution, along with the cooling of water, As
2O
3" white arsenic " separated out in crystallization from cold water, treatedly can obtain the arsenic product, and waste water is reusable edible then.So novel process is in roasting process, the collection of arsenic volatile matter does not need dust collecting system, in simple condenser system furnace gas just can most of condensation under, after further alkali lye absorption, have only a small amount of tail gas, reach emission standard, environmentally safe.Because maturing temperature is lower, the equipment sealing solves easily, can accomplish not have gas leakage in addition.So the present invention can prevent and treat " arsenic evil " effectively, realizes pollution-free operation.Because the investment of having saved dust collecting system greatly reduces production cost.
The drawing explanation
Fig. 1 is a roasting process gas flow synoptic diagram.
Embodiment
The anode mud with high As and Pb composition that embodiment 1～5 handles is (weight %): As 13.18, and Sb 24.77, Pb22.05, and Bi 2.02, and Ag 2.13, Au 15.1g/t, Cu 3.31, SiO
22.15, H
2O 6.67.The anode mud with high As and Pb composition (weight %) that embodiment 6 handles is: As 16.85, and Sb 24.24, and Pb 17.49.Corresponding embodiment sequence number, adopt the process parameters range of table 1 and following technical process to handle anode mud with high As and Pb:
Above-mentioned two kinds of Powdered anode sludge 15g of the super-dry of learning from else's experience; being respectively charged into small-sized airtight rotary kiln 2 internal heating heats up; when reaching the boiling point of water, kiln temperature feeds water vapor 1 (temperature that embodiment 1～6 feeds water vapor is 100 ℃) when above; keep feeding water vapor and under the water vapor protective atmosphere, continue and heat up, prevent that air is with anode sludge oxidation in temperature-rise period.When reaching experimental temperature, temperature stops to heat up volatilization roasting dearsenification under constant temperature.Water vapor 1 imports rotary kiln by the steam producer in roasting process, the flow of water vapor 1 is by regulating the producer voltage control, the steam flow keeps constant in the whole roasting process, water vapor 1 imports in the rotary kiln and the furnace gas that produces behind the material reaction in the kiln is sent into condenser system 4 through kiln tail airway 3, the residual gas of furnace gas after condenser system 4 condensation process is in airway 5 feeds exhaust gas absorption cell 6 again, and the tail gas 7 that alkali lye absorbs after handling in cuvette 6 directly enters atmosphere.Table 1 has provided the dearsenification result of each embodiment simultaneously.
Table 1 embodiment 1～6 each processing step parameter area and dearsenification result
| The embodiment numbering | Maturing temperature ℃ | Roasting time hour | Rotary kiln rotating speed rad/min | Steam rates ml/min | Calcining amount g | Calcining contains arsenic rate % | Arsenic-removing rate % |
| 1 | 400 | 4 | 0.25 | 300 | 11.7 | 12.71 | 24.8 |
| 2 | 750 | 0.5 | 1.00 | 5000 | 6.5 | 3.57 | 87.5 |
| 3 | 550 | 2 | 2.00 | 500 | 10.2 | 3.59 | 81.5 |
| 4 | 600 | 3 | 3.00 | 2000 | 9.6 | 2.84 | 86.2 |
| 5 | 575 | 2.5 | 0.50 | 1000 | 9.2 | 2.59 | 87.95 |
| 6 | 575 | 2.5 | 0.50 | 1000 | 9.4 | 2.84 | 89.44 |
Claims (7)
1. the method for a removing arsenic for anode mud with high arsenic and lead content, the processing step that comprises is oxidizing roasting, discharge after collecting the roasting volatile matter and handling tail gas with alkali lye, the temperature of described oxidizing roasting is 400～750 ℃, roasting time is 0.5～4 hour, it is characterized in that temperature rise period in oxidizing roasting, feed flow range when above and finish in water vapor to the roasting of 300 ml/min～5000 ml/min when temperature in the stoving oven reaches the boiling point of water, condenser system is adopted in the collection of described roasting volatile matter.
2. anode sludge arsenic removing method according to claim 1 is characterized in that described steam rates is 500 ml/min～2000 ml/min.
3. anode sludge arsenic removing method according to claim 2 is characterized in that described steam rates is 1000 ml/min.
4. anode sludge arsenic removing method according to claim 1, the condensing agent that it is characterized in that described condenser system is a water.
5. anode sludge arsenic removing method according to claim 1 is characterized in that adopting airtight rotary kiln to realize described oxidizing roasting, 0.25 rev/min～3 rev/mins of rotary kiln rotating speeds.
6. anode sludge arsenic removing method according to claim 1 is characterized in that described maturing temperature is 550 ℃～600 ℃, roasting time 2～3 hours.
7. anode sludge arsenic removing method according to claim 6 is characterized in that described maturing temperature is 575 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011257008A CN1187459C (en) | 2001-09-08 | 2001-09-08 | Dearsenifying process for anode mud with high As and Pb content |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011257008A CN1187459C (en) | 2001-09-08 | 2001-09-08 | Dearsenifying process for anode mud with high As and Pb content |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1403603A CN1403603A (en) | 2003-03-19 |
| CN1187459C true CN1187459C (en) | 2005-02-02 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB011257008A Expired - Fee Related CN1187459C (en) | 2001-09-08 | 2001-09-08 | Dearsenifying process for anode mud with high As and Pb content |
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102634676B (en) * | 2012-05-11 | 2014-01-15 | 陈建湘 | Method for improving quality of low-grade zinc oxide and removing fluorine, chlorine and arsenic in low-grade zinc oxide by reducing and roasting in rotary kiln |
| CN103820643B (en) * | 2014-03-04 | 2015-12-30 | 云南驰宏锌锗股份有限公司 | A kind of two sections of melting process lead anode slurries produce the method for precious metals containing lead |
| 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 |
| CN105624410A (en) * | 2015-12-31 | 2016-06-01 | 耒阳市焱鑫有色金属有限公司 | Proportioning method for high-arsenic smoke material for sublimation and arsenic removal |
| CN106367602B (en) * | 2016-09-13 | 2018-07-24 | 昆明理工大学 | A kind of method that high-arsenic antimony flue dust vulcanization detaches arsenic and recycles antimony |
| CN108624759B (en) * | 2018-04-16 | 2020-06-05 | 北京科技大学 | Method for comprehensively recovering valuable metals from white smoke |
| CN113930628B (en) * | 2021-09-03 | 2023-04-07 | 湖南有色金属研究院有限责任公司 | Comprehensive recovery method of arsenic-antimony smoke |
| CN115011803B (en) * | 2021-12-23 | 2023-07-25 | 昆明理工大学 | Method for reducing, converting, roasting and dearsenifying high-arsenic germanium-containing neutralization slag |
| CN115011804B (en) * | 2021-12-23 | 2023-07-21 | 昆明理工大学 | Air and water vapor synergistic roasting dearsenification method for high-arsenic antimony lead anode slime |
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2001
- 2001-09-08 CN CNB011257008A patent/CN1187459C/en not_active Expired - Fee Related
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