CN107686887A - Zinc hydrometallurgy removes selenium technique - Google Patents

Zinc hydrometallurgy removes selenium technique Download PDF

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Publication number
CN107686887A
CN107686887A CN201710671600.4A CN201710671600A CN107686887A CN 107686887 A CN107686887 A CN 107686887A CN 201710671600 A CN201710671600 A CN 201710671600A CN 107686887 A CN107686887 A CN 107686887A
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China
Prior art keywords
zinc
selenium
dust
dispensing
zinc concentrate
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CN201710671600.4A
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CN107686887B (en
Inventor
莫德勒图
李龙
江俊涛
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CHIFENG NFC ZINC Co Ltd
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CHIFENG NFC ZINC Co Ltd
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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
    • C22B1/00—Preliminary treatment of ores or scrap
    • C22B1/02—Roasting processes
    • C22B1/10—Roasting processes in fluidised form
    • 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
    • C22B19/20—Obtaining zinc otherwise than by distilling
    • 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
    • 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
    • C22B7/001—Dry processes
    • 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
    • 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
    • C22B7/02—Working-up flue dust
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Abstract

The invention discloses a kind of zinc hydrometallurgy to remove selenium technique, using following steps, dispensing：Reduced first by dispensing in stove zinc concentrate and contain selenium（Se）Amount；Roasting：Fluidizing reactor front end is provided with the air blower for providing air, and the blow rate required is 160~180m of 100kg zinc concentrate powder3Wind, zinc concentrate is carried out acidizing fired；Off-gas recovery；It is transferred to smelting process.The present invention is to original equipment without larger change, and input is minimum, and expense is not high, does not change the original function of equipment in itself, on the entire production line without influence；Implement to be very easy to, you can take effect, and effect is very good, be related zinc abstraction enterprise when being related to system and can not eliminate its influence containing selenium, improve the quality of zinc ingot metal and the yield of zinc ingot metal.

Description

Zinc hydrometallurgy removes selenium technique
Technical field
The present invention relates to wet method zinc abstraction technical field, and in particular to be calcined the production system of relieving haperacidity, zinc electrolysis process and Zinc ingot metal quality, particularly zinc hydrometallurgy remove selenium technique.
Background technology
In recent years because internal sources zinc concentrate day is becoming tight, part zinc concentrate is needed from external import.Due to the places of origin of raw materials Change, corresponding constituent content is also changed in zinc concentrate, particularly selenium（Se）The increase pair of content in the feed Zinc hydrometallurgy influence is very big, if selenium in zinc liquid（Se）Content increase can directly cause electrolysis to burn plate, and from solution very Hardly possible removes.The end of the year in 2015 and 2016 the beginning of the year company because containing the too high yield and cost that have impact on zinc of selenium in system, even It has impact on the quality of zinc product.In order to eliminate its influence, actual field running situation and technique are analyzed, have also been made one A little experiments, searched out be adapted to remove selenium technique, offered reference for industrial production.
The content of the invention
It is an object of the invention to overcome the deficiencies in the prior art, and a kind of zinc hydrometallurgy is provided and removes selenium technique, it is group Knit production it is smooth laid excellent basis, be truly realized and selenium controlled from source toward the entrance in system, alleviate next The pressure of procedure, it specify that direction for Instructing manufacture, it is most important that improve the quality of zinc ingot metal and the yield of zinc ingot metal, reach The purpose of cost efficiency.
It is as follows that the present invention solves the technical scheme that technical problem provides：
A kind of zinc hydrometallurgy removes selenium technique, using following steps：
1st, dispensing：Reduced first by dispensing in stove zinc concentrate and contain selenium（Se）Amount, the miberal powder for each ore deposit point that will be bought Individually classification is deposited in ore pocket, and is detected, and is reduced after result to be detected comes out, during dispensing and contains selenium（Se）Measure higher ore deposit The ratio of powder, final dispensing contain selenium（Se）Amount control is below 0.003%, and the zinc concentrate powder that will be prepared by constant feeder Add in fluidizing reactor；
2nd, it is calcined：Fluidizing reactor front end is provided with the air blower for providing air, and the blow rate required is 160~180m of 100kg zinc concentrate powder3 Wind, zinc concentrate is carried out acidizing fired, the ZnS in zinc concentrate is oxidized to ZnO, and generate a small amount of ZnSO4, to compensate leaching Go out process SO4 2-Loss；
3rd, off-gas recovery：Sent after flue gas caused by fluidizing reactor is by waste heat boiler, cyclone dust collection, gravity gathers dust, electricity gathers dust Sulfuric acid is produced to relieving haperacidity, waste heat boiler room recovery waste heat, send heat distribution pipe network；
4th, it is transferred to smelting process：In cottrell conveying equipment, i.e. the discharge gate front end of drag conveyor sets a drainage conduit, The higher flue dust of selenium content, i.e. gravity dust-precipitator and the dirt of cottrell collection are separately and exclusively packed and do not mixed with calcining by this pipeline Conjunction enters zinc metallurgy system, and by this part flue dust, proportioning uses in proportion again after zinc metallurgy system selenium content gets off；Waste heat boiler is received The flue dust of collection, the flue dust of cyclone collection mix to enter by efficient cylinder after being calcined with fluidizing reactor from the calcining of discharge gate discharge Enter storage bin hopper pack, be transferred to zinc hydrometallurgy process.
The advantage of the invention is that：
1st, to original equipment without larger change, input is minimum, and expense is not high, does not change the original function of equipment in itself, right The entire production line is without influence；
2nd, implement to be very easy to, you can take effect, and effect is very good, for related zinc abstraction enterprise when be related to system containing selenium without When method eliminates its influence, the quality of zinc ingot metal and the yield of zinc ingot metal are improved.
It is present invention process flow chart to illustrate Fig. 1.
The present invention will be further described below in conjunction with the accompanying drawings for embodiment.
As shown in figure 1, a kind of zinc hydrometallurgy removes selenium technique, using following steps：
1st, dispensing：Reduced first by dispensing in stove zinc concentrate and contain selenium（Se）Amount, the miberal powder for each ore deposit point that will be bought Individually classification is deposited in ore pocket, and is detected, and is reduced after result to be detected comes out, during dispensing and contains selenium（Se）Measure higher ore deposit The ratio of powder, final dispensing contain selenium（Se）Amount control is below 0.003%, and the zinc concentrate powder that will be prepared by constant feeder Add in fluidizing reactor；
2nd, it is calcined：Fluidizing reactor front end is provided with the air blower for providing air, the blow rate required be per 100kg zinc concentrates powder per hour 160~180m3Wind, the flow velocity of flue gas is fast, and follow-up flue-gas temperature can increase, and this makes it possible to shorten to condense in flue dust Into residence time of the selenium in cottrell of solid, so as to reduce the selenium content of flue dust, in the case where the blow rate required is constant（No The blow rate required with the roaster of area is different）, the feeding coal of unit interval is controlled by constant feeder, control, which is seethed with excitement, to be roasted Stove furnace temperature being burnt at 920 DEG C~960 DEG C, and held stationary, accordingly to be fed if furnace temperature declines more（Constant feeder is improved to turn Speed）If furnace temperature increases above scope and accordingly fed less（Reduce constant feeder rotating speed）；Zinc concentrate is subjected to acidifying roasting Burn, the ZnS in zinc concentrate is oxidized to ZnO, and generate a small amount of ZnSO4, to compensate leaching process SO4 2-Loss；
3rd, off-gas recovery：Sent after flue gas caused by fluidizing reactor is by waste heat boiler, cyclone dust collection, gravity gathers dust, electricity gathers dust Sulfuric acid is produced to relieving haperacidity, waste heat boiler room recovery waste heat, send heat distribution pipe network；
4th, it is transferred to smelting process：In cottrell conveying equipment, i.e. the discharge gate front end of drag conveyor sets a drainage conduit, The higher flue dust of selenium content, i.e. gravity dust-precipitator and the dirt of cottrell collection are separately and exclusively packed and do not mixed with calcining by this pipeline Conjunction enters zinc metallurgy system, and by this part flue dust, proportioning uses in proportion again after zinc metallurgy system selenium content gets off；Waste heat boiler is received The flue dust of collection, the flue dust of cyclone collection mix to enter by efficient cylinder after being calcined with fluidizing reactor from the calcining of discharge gate discharge Enter storage bin hopper pack, be transferred to zinc hydrometallurgy process.
It will not contain selenium from the calcining that roaster discharge gate is efficient cylinder discharge when i.e. roaster furnace temperature is more than 920 DEG C, Selenium all should be evaporate into flue gas, and improves heat boiler outlet simultaneously to the temperature between cottrell outlet.
Boiler heating surface is reduced, cancels part boiler swing pipe and improves heat boiler outlet between cottrell outlet The method of temperature reduces the selenium content in flue dust, is provided for next step using containing the higher zinc concentrate powder of selenium and for zinc hydrometallurgy The lower calcining containing selenium creates favourable condition.
Note：The purpose that heat boiler outlet is improved to the temperature between cottrell outlet is to extend in flue gas SeO2Gas is at 315 DEG C（SeO2Distilled at 315 DEG C）The residence time in temperatures above section, ensure with gaseous state as far as possible Moved behind ground, will accordingly shorten it and be frozen into the time of solid.Because flue gas and flue dust are being calcined under same working condition The system residence time is constant, and we can take measures to shorten 315 DEG C of temperature below sections, that is, improve heat boiler outlet Temperature to cottrell outlet, to realize the SeO in flue gas2Go to make with flue gas to greatest extent to the greatest extent in the form of gas Acid purification system removes, and is finally reached the purpose of the reduction of the flue dust selenium content of cottrell collection.
1st, experimental example
1.1 practical operation situations and comparative analysis
Tracked and concluded with reference to company two, three, the actual operation parameters of fourth phase roasting system and result of laboratory test, have found Selenium distribution situation in systems and certain rule, are shown in Table 1, table 2, table 3, table 4.
Each phase roasting system primary operating parameter of table 1
Each phase roasting system selenium of table 2（Se）Distribution situation and content（%）
Remarks 1："-" represents the element as trace；
Remarks 2：The zinc concentrate that several zinc concentrates in table in the 8th column are company's second phase, three phases, fourth phase system are commonly used, and And the relatively other ore deposits of usage amount are more.
By Tables 1 and 2 it can be seen that：
A. it is calcined in-furnace temperature and is free of selenium from the calcining of roaster discharge gate discharge between 920 DEG C~960 DEG C；
B. the flue dust that waste heat boiler is collected very contains selenium, but content is very low（Waste heat boiler temperature is more than 300 DEG C）；
C. the flue dust that rotoclone collector is collected very contains selenium；
D. the flue dust that cottrell is collected all is collected containing selenium, the particularly phase of company three, fourth phase cottrell end 4# electric fields Flue dust selenium content be higher by many times of leading portion 1#, 2#, 3# electric field, can reach more than 10 times during highest；The former design of company's second phase Three electric fields altogether, the flue dust selenium content that same cottrell end 3# electric fields are collected are higher by leading portion 1#, 2# electric field very More times；Company's second phase, former design amounted to three electric fields, no 4# electric fields.
It is further details of to when analysis in table 3
Table 3 is contrasted and analyzed
1.2 selenium trend in systems and material balance are shown in Table 4
The selenium of table 4（Se）Moon balance sheet
Material balance table illustrates most selenium（Se）Into sour mud, i.e., the sediment collected from acid making system cleaning procedure diluted acid In, the selenium how removed in material for next step provides favourable foundation and clear and definite direction, also illustrate that from calcining Except selenium has feasibility.
2 experiments
2.1 experiments one：Zinc concentrate containing selenium is heated to more than 920 DEG C, continues constant temperature after about 4 hours, clinker（I.e. high temperature roasts Calcining after burning）Without selenium, illustrate to coincide with its characteristic, will not contain from the calcining of roaster discharge gate discharge under the high temperature conditions Selenium can determine.
2.2 experiments two：The aggregate sample that cottrell is collected（The flue dust of i.e. four electric fields）Sample is contained in crucible；Press Different thickness, different temperature distinguished heated constant temperature to 30 minutes, obtained the degree of volatility of selenium at different conditions（Contain as former state Selenium 0.0097%）, as shown in table 5；
The electricity of table 5, which gathers dust, mixes flue dust Muffle furnace calcination experimental result
Although a. this experiment is stirring what is carried out under static state without ventilation, nothing, explanation reaches certain temperature selenium It can volatilize, gaseous state could be kept；If can also illustrate, progress volatility can be higher under the agitation of air, can be more except selenium effect It is good；
B. selenium volatilization different degrees of since 350 DEG C in this experiment, the gas for illustrating volatilization is not elemental selenium, and volatilization is SeO2（Elemental selenium boiling point is 684.9 DEG C）；
C. this experiment process is just with production process on the contrary, experiment category heating process, the process by solid volatilization for gas；It is real Border is produced as temperature-fall period, and the process of solid is condensed into by gas；It can illustrate that temperature is higher, volatility is higher；Reversely Confirm in actual production, the probability that the volatile matter in flue gas is frozen into solid with temperature rise can be lower.
3 conclusion
Selenium will not be contained from the calcining of roaster discharge gate discharge when controlling roaster furnace temperature more than 920 DEG C, selenium should be waved all It is dealt into flue gas, if extending the SeO in flue gas2Gas is at 315 DEG C（SeO2Distilled at 315 DEG C）The stop in temperatures above section Time, ensure to move afterwards as much as possible with gaseous state, will accordingly shorten it and be frozen into the time of solid, because in same life Flue gas and flue dust in the roasting system residence time are constant under the conditions of production, we can take measures to shorten less than 315 DEG C it is warm Section is spent, that is, heat boiler outlet is improved to the temperature between cottrell outlet, to realize the SeO in flue gas2With gas Form goes relieving haperacidity cleaning system to remove with flue gas to greatest extent to the greatest extent, is finally reached the drop of the flue dust selenium content of cottrell collection Low purpose.Taken in actual production process and improve heat boiler outlet to the method for the temperature between cottrell outlet, can To create favourable condition to use in next step containing the higher zinc concentrate powder of selenium and providing the lower calcining containing selenium for zinc hydrometallurgy.

Claims (1)

1. a kind of zinc hydrometallurgy removes selenium technique, it is characterised in that using following steps：
1st, dispensing：The selenium content in stove zinc concentrate is reduced by dispensing first, the miberal powder for each ore deposit point that will be bought is independent Classification is deposited in ore pocket, and is detected, and the ratio of the higher miberal powder of selenium content is reduced after result to be detected comes out, during dispensing The zinc concentrate powder prepared is added boiling roasting by example, final dispensing selenium content control below 0.003%, and by constant feeder Burn in stove；
2nd, it is calcined：Fluidizing reactor front end is provided with the air blower for providing air, and the blow rate required is 160~180m of 100kg zinc concentrate powder3 Wind, zinc concentrate is carried out acidizing fired, the ZnS in zinc concentrate is oxidized to ZnO, and generate a small amount of ZnSO4, to compensate leaching Go out process SO4 2-Loss；
3rd, off-gas recovery：Sent after flue gas caused by fluidizing reactor is by waste heat boiler, cyclone dust collection, gravity gathers dust, electricity gathers dust Sulfuric acid is produced to relieving haperacidity, waste heat boiler room recovery waste heat, send heat distribution pipe network；
4th, it is transferred to smelting process：In cottrell conveying equipment, i.e. the discharge gate front end of drag conveyor sets a drainage conduit, The higher flue dust of selenium content, i.e. gravity dust-precipitator and the dirt of cottrell collection are separately and exclusively packed and do not mixed with calcining by this pipeline Conjunction enters zinc metallurgy system, and by this part flue dust, proportioning uses in proportion again after zinc metallurgy system selenium content gets off；Waste heat boiler is received The flue dust of collection, the flue dust of cyclone collection are mixed with the calcining after fluidizing reactor roasting and filled by efficient cylinder into storage bin hopper Bag, is transferred to zinc hydrometallurgy process.
CN201710671600.4A 2017-08-08 2017-08-08 Zinc hydrometallurgy removes selenium technique Active CN107686887B (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113684364A (en) * 2021-08-27 2021-11-23 新疆紫金有色金属有限公司 Fluidized bed furnace roasting treatment method for fine-grained high-silicon low-iron zinc concentrate

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB9422476D0 (en) * 1994-11-08 1995-01-04 Sherritt Inc Recovery of zinc from sulphidic concentrates
CN1566379A (en) * 2003-06-27 2005-01-19 史汉祥 Copper-zinc separation method during smelting in a blast furnace
AU2004276430A1 (en) * 2003-09-29 2005-04-07 Umicore Process and apparatus for recovery of non-ferrous metals from zinc residues
CN103451445A (en) * 2013-09-10 2013-12-18 中国恩菲工程技术有限公司 Smelting side-blowing reduction lead-zinc smelting process

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB9422476D0 (en) * 1994-11-08 1995-01-04 Sherritt Inc Recovery of zinc from sulphidic concentrates
CN1566379A (en) * 2003-06-27 2005-01-19 史汉祥 Copper-zinc separation method during smelting in a blast furnace
AU2004276430A1 (en) * 2003-09-29 2005-04-07 Umicore Process and apparatus for recovery of non-ferrous metals from zinc residues
CN103451445A (en) * 2013-09-10 2013-12-18 中国恩菲工程技术有限公司 Smelting side-blowing reduction lead-zinc smelting process

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113684364A (en) * 2021-08-27 2021-11-23 新疆紫金有色金属有限公司 Fluidized bed furnace roasting treatment method for fine-grained high-silicon low-iron zinc concentrate

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