CN107686887B - Zinc hydrometallurgy removes selenium technique - Google Patents
Zinc hydrometallurgy removes selenium technique Download PDFInfo
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- CN107686887B CN107686887B CN201710671600.4A CN201710671600A CN107686887B CN 107686887 B CN107686887 B CN 107686887B CN 201710671600 A CN201710671600 A CN 201710671600A CN 107686887 B CN107686887 B CN 107686887B
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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
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B19/00—Obtaining zinc or zinc oxide
- C22B19/20—Obtaining zinc otherwise than by distilling
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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
- 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
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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
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Geochemistry & Mineralogy (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a kind of zinc hydrometallurgies to remove selenium technique, using following steps, ingredient: reducing measuring in furnace zinc concentrate containing selenium (Se) by ingredient first；Roasting: fluidizing reactor front end, which is equipped with, provides the air blower of 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 biggish change, and investment is minimum, and expense is not high, does not change the original function of equipment itself, on the entire production line without influence；Implement to be very easy to, can take effect, and effect is very good, is related zinc abstraction enterprise when its influence can not be eliminated containing selenium by being related to system, improves the quality of zinc ingot metal and the yield of zinc ingot metal.
Description
Technical field
The present invention relates to wet process zinc abstraction technical fields, and in particular to roast the production system of relieving haperacidity, zinc electrolysis process and
Zinc ingot metal quality, especially zinc hydrometallurgy remove selenium technique.
Background technique
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
Variation, corresponding constituent content is also changed in zinc concentrate, the especially increase pair of the content of selenium (Se) in the feed
Zinc hydrometallurgy influence is very big, if the content increase of selenium (Se) can directly cause electrolysis to burn plate in zinc liquid, and from solution very
Hardly possible removal.The end of the year in 2015 and 2016 beginning of the year companies are because containing the excessively high yield and cost for affecting zinc of selenium in system, even
Affect the quality of zinc product.In order to eliminate its influence, actual field operating condition and technique are analyzed, have also been made one
A little experiments, searched out be suitble to except selenium technique, offer reference for industrial production.
Summary of the invention
It is an object of the invention to overcome the deficiencies in the prior art, and provide a kind of zinc hydrometallurgy except selenium technique, it is group
Knit production it is smooth laid excellent basis, be truly realized the entrance for controlling selenium from source in system, alleviate next
The pressure of procedure specifies 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 solution that technical problem provides:
A kind of zinc hydrometallurgy removes selenium technique, using following steps:
1, ingredient: measuring in furnace zinc concentrate containing selenium (Se) is reduced by ingredient first, i.e., by each mine point bought
Miberal powder, which is individually classified, is deposited in ore pocket, and is detected, reduced after result to be detected comes out, when ingredient measured containing selenium (Se) it is higher
Miberal powder ratio, final ingredient containing selenium (Se) amount control 0.003% hereinafter, and by constant feeder by the zinc prepared essence
Miberal powder is added in fluidizing reactor；
2, roast: fluidizing reactor front end, which is equipped with, provides the air blower of air, and the blow rate required is every 100kg zinc concentrate powder per small
When 160~180m3Wind, zinc concentrate is carried out acidizing fired, the ZnS in zinc concentrate is oxidized to ZnO, and generated a small amount of
ZnSO4, to compensate leaching process SO4 2-Loss；
3, off-gas recovery: fluidizing reactor generate flue gas by waste heat boiler, cyclone dust collection, gravity gathers dust, electricity gathers dust
After be sent to relieving haperacidity production sulfuric acid, waste heat boiler room recovery waste heat send heat distribution pipe network；
4, be transferred to smelting process: in cottrell conveying equipment, i.e. a row is arranged in the discharge gate front end of drag conveyor
Expects pipe, by this pipeline by the higher flue dust of selenium content, i.e., the dirt that gravity dust-precipitator and cottrell are collected separately and exclusively pack not with
Calcining is mixed into zinc metallurgy system, and by this part flue dust, proportion is used in proportion again after zinc metallurgy system selenium content gets off；Waste heat
The flue dust of flue dust, cyclone collection that boiler is collected is mixed from the calcining that discharge gate is discharged by efficient with after fluidizing reactor roasting
Cylinder enters storage hopper pack, is transferred to zinc hydrometallurgy process.
The present invention has the advantages that
1, to original equipment without biggish change, investment is minimum, and expense is not high, does not change original function of equipment itself
Can, on the entire production line without influence；
2, implement to be very easy to, can take effect, and effect is very good, contain for related zinc abstraction enterprise when being related to system
When selenium can not eliminate its influence, the quality of zinc ingot metal and the yield of zinc ingot metal are improved.
Detailed description of the invention
Fig. 1 is process flow chart of the invention.
Specific embodiment
The present invention will be further described with reference to the accompanying drawing.
As shown in Figure 1, a kind of zinc hydrometallurgy removes selenium technique, using following steps:
1, ingredient: measuring in furnace zinc concentrate containing selenium (Se) is reduced by ingredient first, i.e., by each mine point bought
Miberal powder, which is individually classified, is deposited in ore pocket, and is detected, reduced after result to be detected comes out, when ingredient measured containing selenium (Se) it is higher
Miberal powder ratio, final ingredient containing selenium (Se) amount control 0.003% hereinafter, and by constant feeder by the zinc prepared essence
Miberal powder is added in fluidizing reactor；
2, roast: fluidizing reactor front end, which is equipped with, provides the air blower of air, and the blow rate required is every 100kg zinc concentrate powder per small
When 160~180m3Wind, the flow velocity of flue gas is fast, and subsequent flue-gas temperature can increase, this makes it possible to shorten in flue dust coagulate
Form residence time of the selenium of solid in cottrell, so that the selenium content of flue dust is reduced, in the case where the blow rate required is constant
(blow rate required of the roaster of different area is different) controls the feeding coal of unit time, control boiling by constant feeder
Roaster furnace temperature is risen at 920 DEG C~960 DEG C, and held stationary, if furnace temperature decline will accordingly add material (i.e. raising constant feeder
Revolving speed), if furnace temperature increases above range and accordingly to feed (i.e. reduction constant feeder revolving speed) less；Zinc concentrate is subjected to acidification roasting
It burns, the ZnS in zinc concentrate is oxidized to ZnO, and generate a small amount of ZnSO4, to compensate leaching process SO4 2-Loss；
3, off-gas recovery: fluidizing reactor generate flue gas by waste heat boiler, cyclone dust collection, gravity gathers dust, electricity gathers dust
After be sent to relieving haperacidity production sulfuric acid, waste heat boiler room recovery waste heat send heat distribution pipe network；
4, be transferred to smelting process: in cottrell conveying equipment, i.e. a row is arranged in the discharge gate front end of drag conveyor
Expects pipe, by this pipeline by the higher flue dust of selenium content, i.e., the dirt that gravity dust-precipitator and cottrell are collected separately and exclusively pack not with
Calcining is mixed into zinc metallurgy system, and by this part flue dust, proportion is used in proportion again after zinc metallurgy system selenium content gets off；Waste heat
The flue dust of flue dust, cyclone collection that boiler is collected is mixed from the calcining that discharge gate is discharged by efficient with after fluidizing reactor roasting
Cylinder enters storage hopper pack, is transferred to zinc hydrometallurgy process.
I.e. roaster furnace temperature will not contain selenium from the calcining that roaster discharge gate, that is, efficient cylinder is discharged at 920 DEG C or more,
Selenium should all be evaporate into flue gas, and improve 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, provides for next step using containing the higher zinc concentrate powder of selenium and for zinc hydrometallurgy
The lower calcining containing selenium creates advantageous condition.
Note: the purpose for improving heat boiler outlet to the temperature between cottrell outlet is to extend in flue gas
SeO2Gas is in 315 DEG C of (SeO2Distil at 315 DEG C) residence time in temperatures above section, guarantee with gaseous state as far as possible
Ground moves back, and will accordingly shorten its time for being frozen into solid.Because flue gas and flue dust are roasting under same working condition
The system residence time be it is constant, we can take measures shorten 315 DEG C of following temperature sections, i.e., raising heat boiler outlet
Temperature to cottrell outlet, the SeO in Lai Shixian flue gas2It goes to make with flue gas to the maximum extent to the greatest extent in the form of gas
Acid purification system removes, and is finally reached the reduced purpose of the flue dust selenium content of cottrell collection.
1, experimental example
1.1 practical operation situations and comparative analysis
It is tracked and has been concluded in conjunction with company two, three, the actual operation parameters of fourth phase roasting system and result of laboratory test, looked for
The distribution situation and certain rule of selenium in systems have been arrived, 1, table 2, table 3, table 4 are shown in Table.
Each phase roasting system primary operating parameter of table 1
The distribution situation and content (%) of each phase roasting system selenium (Se) of table 2
Remarks 1: "-" represents the element as trace；
Remarks 2: several zinc concentrates in table in the 8th column are that the zinc that company's second phase, three phases, fourth phase system are commonly used is smart
Mine, and the relatively other mines of usage amount are more.
By Tables 1 and 2 it can be seen that
A. the calcining that roasting in-furnace temperature is discharged between 920 DEG C~960 DEG C from roaster discharge gate is free of selenium；
B. the flue dust that waste heat boiler is collected very contains selenium, but content is very low (waste heat boiler temperature is at 300 DEG C or more)；
C. the flue dust that rotoclone collector is collected very contains selenium；
D. the flue dust that cottrell is collected all contains selenium, especially three phase of company, fourth phase cottrell end 4# electric field
The flue dust selenium content of collection is higher by many times of leading portion 1#, 2#, 3# electric field, and when highest can reach more than 10 times；Company's second phase is former
It designs and amounts to three electric fields, the flue dust selenium content that same cottrell end 3# electric field is collected is higher by leading portion 1#, 2# electric field
Many times；Company's second phase, former design amounted to three electric fields, no 4# electric field.
It is further details of that 3 are shown in Table to when analysis
The comparison of table 3 and analysis
1.2 selenium trend in systems and material balance are shown in Table 4
The moon balance sheet of 4 selenium of table (Se)
Material balance table illustrates that most selenium (Se) enters sour mud, i.e., that collects from acid making system cleaning procedure diluted acid is heavy
In starch, advantageous foundation and specific direction are provided for how next step removes the selenium in material, is also illustrated from calcining
Middle removal selenium has feasibility.
2 tests
2.1 tests one: being heated to 920 DEG C or more for the zinc concentrate containing selenium, continues constant temperature after about 4 hours, clinker is (i.e. high
Calcining after temperature roasting) selenium is free of, illustrate to coincide with its characteristic, the calcining being discharged from roaster discharge gate under the high temperature conditions is not
Selenium, which can be contained, to be determined.
2.2 tests two: aggregate sample (flue dust of i.e. four electric fields) sample that cottrell is collected is contained in crucible；It presses
Different thickness, different temperature difference heated constant temperatures obtained the degree of volatility of selenium at different conditions and (contain as former state to 30 minutes
Selenium 0.0097%), as shown in table 5；
5 electricity of table, which gathers dust, mixes flue dust Muffle furnace calcination experimental result
Although a. this test carries out under static state without ventilation, without stirring, explanation reaches certain temperature
Selenium could volatilize, and just be able to maintain gaseous state；If can also illustrate, progress volatility can be higher under the agitation of air, removes selenium effect
It can be more preferable；
B. selenium volatilization different degrees of since 350 DEG C in this test, illustrates that the gas of volatilization is not elemental selenium, volatilization
Be SeO2(elemental selenium boiling point is 684.9 DEG C)；
C. this test process is just with production process on the contrary, test category heating process, is the mistake of gas by solid volatilization
Journey；Actual production is temperature-fall period, and the process of solid is condensed by gas；It can illustrate that temperature is higher, volatility is higher；Instead
To also demonstrating in actual production, the volatile matter in flue gas can be lower with the probability that temperature raising is frozen into solid.
3 conclusion
Selenium will not be contained from the calcining that roaster discharge gate is discharged at 920 DEG C or more by controlling roaster furnace temperature, and selenium should be complete
Portion is evaporate into flue gas, if extending the SeO in flue gas2Gas is in 315 DEG C of (SeO2Distil at 315 DEG C) temperatures above section
Residence time, guarantee are moved back as much as possible with gaseous state, will accordingly shorten its time for being frozen into solid, because same
Working condition under flue gas and flue dust in the roasting system residence time be it is constant, we can take measures to shorten 315 DEG C with
The SeO of lower temperature range, i.e. raising heat boiler outlet to the temperature between cottrell outlet, in Lai Shixian flue gas2With gas
The form of body goes relieving haperacidity purification system to remove with flue gas to the maximum extent to the greatest extent, is finally reached the flue dust selenium content of cottrell collection
Reduced purpose.It is taken in actual production process and improves heat boiler outlet to the side of the temperature between cottrell outlet
Method, can be advantageous using the lower calcining creation containing selenium is provided containing the higher zinc concentrate powder of selenium and for zinc hydrometallurgy for next step
Condition.
Claims (1)
1. a kind of zinc hydrometallurgy removes selenium technique, which is characterized in that use following steps:
1, ingredient: reducing the selenium content in furnace zinc concentrate by ingredient first, i.e., the miberal powder for each mine point bought is independent
Classification is deposited in ore pocket, and is detected, and after result to be detected comes out, when ingredient reduces the ratio of the higher miberal powder of selenium content
Example, final ingredient selenium content control is 0.003% hereinafter, and boiling roasting is added in the zinc concentrate powder prepared by constant feeder
It burns in furnace；
2, roast: fluidizing reactor front end be equipped with provide air air blower, the blow rate required be every 100kg zinc concentrate powder per hour
160~180m3Wind, zinc concentrate is carried out acidizing fired, the ZnS in zinc concentrate is oxidized to ZnO, and generated a small amount of
ZnSO4, to compensate leaching process SO4 2-Loss；
3, off-gas recovery: the flue gas that fluidizing reactor generates is sent after waste heat boiler, cyclone dust collection, gravity gather dust, electricity gathers dust
Sulfuric acid is produced to relieving haperacidity, waste heat boiler room recovery waste heat send heat distribution pipe network；
4, be transferred to smelting process: in cottrell conveying equipment, i.e. a drainage conduit is arranged in the discharge gate front end of drag conveyor,
By this pipeline by the higher flue dust of selenium content, i.e., the dirt that gravity dust-precipitator and cottrell are collected separately and exclusively packs not mixed with calcining
It closes and enters zinc metallurgy system, proportion uses in proportion again by this part flue dust 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 with the calcining after fluidizing reactor roasting and enter storage hopper dress by efficient cylinder
Bag, is transferred to zinc hydrometallurgy process.
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| 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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| 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 |
| US7815708B2 (en) * | 2003-09-29 | 2010-10-19 | 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 |
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