CN106086461A - A kind of method of Copper making process slag making arsenic removal - Google Patents
A kind of method of Copper making process slag making arsenic removal Download PDFInfo
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- CN106086461A CN106086461A CN201610683819.1A CN201610683819A CN106086461A CN 106086461 A CN106086461 A CN 106086461A CN 201610683819 A CN201610683819 A CN 201610683819A CN 106086461 A CN106086461 A CN 106086461A
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- arsenic
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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
- C22B15/00—Obtaining copper
- C22B15/0026—Pyrometallurgy
- C22B15/0028—Smelting or converting
Abstract
A kind of method that the invention discloses Copper making process slag making arsenic removal, it uses composite fluxing agent to improve arsenic distribution ratio in slag, first by metal-oxide or the mixing of metal fused salt of different proportion, is melt into composite fluxing agent under 1200 DEG C of high temperature above in advance；The copper material containing arsenic and composite fluxing agent are heated in high temperature furnace fusing again, to be melted completely after, be passed through oxygen and carry out melting；After melting terminates, stand and carry out slag copper separation, obtain rich arsenic slag and low containing arsenical copper material.The method of this Copper making process slag making arsenic removal can significantly improve the slag accumulation ability to arsenic during Copper making, reduces arsenic to flue gas system and the impact of electrolysis system, it is achieved the effective, harmlessization of arsenic processes, and has low cost, short route, the efficient feature of process.
Description
Technical field
The present invention relates to metal smelt method, particularly to a kind of method of Copper making process slag making arsenic removal.
Background technology
At present copper select smelting produce present in one of subject matter to be that copper concentrate contains arsenic too high.In copper concentrate containing arsenic
Mineral mainly have mispickel (FeAsS), enargite (Cu3AsS4) and tennantite (Cu12As4S13) etc., according to statistics, generation
The copper ore resource arsenic of 15 % is had to be up to 1:5 with the ratio of copper in boundary.Arsenic is a kind of element highly unwanted to human body, in copper concentrate
Arsenic not only affect the quality of matallurgical products, also can cause gather dust, antacid, dust treatment, waste residue are stacked, extract, are electrolysed
With a series of technological problems and environmental problems such as electrodeposition.Therefore, the smelting process containing arsenic ore is carried out deep arsenic removal to grind
Study carefully, no matter from environmental conservation, or in terms of improving smelting benefit, all have and be of great significance.
In recent decades, both at home and abroad to the improvement of arsenic evil in copper mine, it is summed up and mainly has two big classes: one is the smelting at copper
The refining stage administers: during pyrometallurgical smelting, arsenic has primarily entered dust collecting system, and a small part enters in waste residue, at this moment uses open circuit
Flow process, on the one hand arsenic can comprehensively utilize formation arsenic product, additionally can stack after processing with innoxious slag making, it would however also be possible to employ wet
Method electrolysis arsenic removal；Two is to carry out pretreatment before smelting: can in copper ore dressing time just carry out flotation arsenic removal, make in copper concentrate
Arsenic content is reduced to the standard of smelting requirements, it is also possible to carry out wet pretreatment to containing arsenical copper concentrate, such as steam dearsenization, antibacterial
Leach and the alkali leaching under normal pressure (high pressure), acidleach arsenic removal etc..Both the above method belongs to traditional arsenic processing method, there is work
Process flow length and many waste materials Han arsenic need to carry out harmless treatment further and cause the defect that environmental protection cost is high.So, find
Low cost, efficient arsenic removal process is extremely urgent.
Processing Copper ore containing arsenic at traditional copper smelting by pyrometallurgy, least a portion of arsenic is directly opened a way to copper ashes by paved set, most
Arsenic enters flue gas system, electrolysis system and white flue dust.Arsenic enters flue gas system can cause the series of problems such as catalyst poisoning；Arsenic
Enter electrolysis system and also can have a strong impact on electrolytic efficiency and Cathode Copper Quality, and the black copper mud of electrolyte purification returns to melting
System, arsenic does not realize open circuit.Therefore, by the design of slag type make arsenic be more enriched in slag directly open circuit be low cost,
The important directions of short route, efficiently process Copper ore containing arsenic.Patent CN1455011 discloses a kind of antimony and smelts pyro-refining antimony arsenic removal
Except selenium method, being the needle antimony containing arsenic, selenium to be put into refining furnace add heat fusing, and be warming up to 650-1000 DEG C, disposable addition removes
Alkali metal hydroxide needed for arsenic, selenium, then it is passed through compressed air stirring 15-150 min, complete slag making arsenic removal, selenium reaction, generate
Arsenate and selenite scum silica frost, slag antimony prepares product after separating.On this basis, patent CN103526049A discloses one
The method of pyrometallurgical smelting antimony arsenic removal, is optimized existing composite fluxing agent, improves the efficiency of arsenic removal.But, in copper smelting
Realize the efficient removal of arsenic by the design of slag type during refining and have no relevant report.
Summary of the invention
It is an object of the invention to provide a kind of low cost, short route, process efficient Copper making process slag making arsenic removal
Method, to improve the slag accumulation ability to arsenic during Copper making, reduces arsenic to flue gas system and the impact of electrolysis system, it is achieved
The effective, harmlessization of arsenic processes.
For realizing object above, the method for the present invention a kind of Copper making process slag making arsenic removal uses composite fluxing agent to improve arsenic
Distribution ratio in slag, operating procedure is as follows:
(1) by metal-oxide or the mixing of metal fused salt of different proportion, it is melt into compound molten under 1200 DEG C of high temperature above in advance
Agent；
(2) in high temperature furnace, the copper material containing arsenic and composite fluxing agent are heated to fusing；
(3) to be melted completely after, be passed through oxygen and carry out melting；
(4) after melting terminates, stand and carry out slag copper separation, obtain rich arsenic slag and low containing arsenical copper material.
Metal-oxide or metal fused salt in described step (1) are following 11 kinds of materials, described composite fluxing agent by this 11
Plant selection 3 ~ 11 kinds in the material of weight portion formulated: ferrum oxide 0 ~ 70 part, quartz sand 0 ~ 40 part, calcium oxide 0 ~ 30 part, oxygen
Change 0 ~ 30 part of aluminum, sodium carbonate 0 ~ 5 part, magnesium oxide 0 ~ 5 part, sodium oxide 0 ~ 5 part, 0 ~ 5 part of calcium fluoride, Barium monoxide 0 ~ 5 part, sodium silicate
0 ~ 5 part, titanium oxide 0 ~ 5 part.
The prefusing temperature of the fritting composite fluxing agent in described step (1) is 1200 ~ 1500 DEG C, the fritting time 0.5 ~ 1.5
h。
In described step (2) composite fluxing agent with containing arsenical copper material mass ratio be 0.01 ~ 1:1, fusion temperature is 1200 ~
1350 DEG C, fusing time is 0.5 ~ 1 h.
In described step (3), the temperature of melting is 1200 ~ 1350 DEG C, and oxygen flow is 0.5 ~ 20 L/min, smelting time
For 0.5-3 h.
All melting modes that melting in described step (3) is matte smelting and the blowing refinement of the matte comprises；Ventilating mode divides
For to smelting furnace ventilation with to melt internal ventilation two kinds.
Standing in described step (4) is standing 20 ~ 40 min.
It is noted that in the industrial processes of large-scale smelting furnace, it is not necessary to carry out the fritting step of described step (1)
Suddenly, it is only necessary to direct plunge into after the metal-oxide of different proportion or metal fused salt are fully mixed and smelting furnace can realize slag make
Arsenic removal.
The present inventor, by repeatedly studying Copper making technique, finds that smelting process copper ashes can not high efficiency synchronous dearsenization
Main cause be: under existing copper ashes system, arsenic activity coefficient in slag is higher, and lacks in slag and carry out phase with arsenic
In conjunction with material, cause the distribution ratio of arsenic in slag low；And the present invention is by providing a kind of composite fluxing agent to improve arsenic in smelting slag
Distribution ratio, it is achieved Copper making process slag making arsenic removal, with the negative effect overcoming arsenic impurities that Copper making process is produced.
The method of the present invention a kind of Copper making process slag making arsenic removal solves existing copper pyrometallurgical smelting system arsenic at smelting slag
The problem that middle activity coefficient is high, distribution ratio is low, makes arsenic efficiently concentrating in copper ashes, has the advantages that
(1) use the composite fluxing agent of the present invention to carry out melting, the arsenic in copper-contained material can be enriched with to smelting slag, arsenic in slag
Content is up to 50% ~ 85%, effectively alleviates arsenic to postorder acid making system and the impact of electrolysis system；
(2) this composite fluxing agent meets 1200 DEG C of any of the above melting arsenic removal requirements containing arsenic metalliferous material, makes arsenic with stable change
Presented in compound in slag, save arsenic processing cost；
(3) present invention firstly provides the process of a kind of Copper making process slag making arsenic removal, it is achieved smelting and processing of metals process arsenic
High efficiency synchronous removing, be effectively reduced the processing cost of metalliferous material smelting process process arsenic, have good economic benefit and
Social benefit.
Detailed description of the invention
Method below in conjunction with detailed description of the invention Copper making a kind of to present invention process slag making arsenic removal is made the most in detail
Explanation.
The method of the present invention a kind of Copper making process slag making arsenic removal, first prepares composite fluxing agent, then by the copper material containing arsenic and
Composite fluxing agent is heated to melting, and then the raw material after fusing is carried out melting and completes slag making arsenic removal reaction, and last slag copper separates.Respectively
The technological parameter of operating procedure is as follows:
Composite fluxing agent is prepared: formed by selecting 3 ~ 11 kinds of preparation of raw material in the material of following 11 kinds of weight portions: ferrum oxide 0 ~ 70 part,
Quartz sand 0 ~ 40 part, calcium oxide 0 ~ 30 part, aluminium oxide 0 ~ 30 part, sodium carbonate 0 ~ 5 part, magnesium oxide 0 ~ 5 part, sodium oxide 0 ~ 5 part, fluorine
Change calcium 0 ~ 5 part, Barium monoxide 0 ~ 5 part, sodium silicate 0 ~ 5 part, titanium oxide 0 ~ 5 part；
Composite fluxing agent fritting: temperature 1200 ~ 1500 DEG C, time 0.5 ~ 1.5 h；
Fusing: composite fluxing agent with containing arsenical copper material mass ratio be 0.01 ~ 1:1, fusion temperature is 1200 ~ 1350 DEG C, fusing
Time is 0.5 ~ 1 h；
Melting: smelting temperature is 1200 ~ 1350 DEG C, smelting time is 0.5-3 h, and oxygen flow is 1 ~ 20 L/min；
Stand: time 20-40 min.
Embodiment 1
(1) take silicon dioxide 5.1 kg, calcium oxide 3.9 kg, aluminium sesquioxide 0.95 kg, sodium oxide 0.05 kg fully to mix,
CaO-SiO is become at 1250 DEG C of fritting 1.5 h2-Al2O3-Na2O slag；
(2) put in crucible furnace together with taking after 7 Kg slags mix with 50 Kg copper concentrates and heat until being completely melt；
(3) blasting oxygen slag making melting, smelting temperature 1200-1300 DEG C, smelting time 3 h, oxygen flow is 1 L/min；
(4) melting carries out, after terminating cooling, separation of skimming, and obtains rich arsenic slag and matte.
The rich arsenic slag arsenic accumulation rate that the present embodiment obtains is 53%.
Embodiment 2
(1) silicon dioxide 3.8 Kg, calcium oxide 6.7 Kg, aluminium sesquioxide 0.4 Kg, magnesium oxide 0.05 Kg, calcium fluoride are taken
0.02 Kg fully mixes, and becomes CaO-SiO at 1500 DEG C of fritting 1h2-Al2O3-MgO-CaF2Slag；
(2) put in crucible furnace together with taking after 8.5 Kg slags mix with 50 Kg matte and heat until being completely melt；
(3) blasting oxygen slag making melting, smelting temperature 1250-1350 DEG C, smelting time 1.5 h, oxygen flow is 10 L/
min；
(4) melting carries out, after terminating cooling, separation of skimming, and obtains rich arsenic slag and copper-nickel alloy.
The rich arsenic slag arsenic accumulation rate that the present embodiment obtains is 79%.
Embodiment 3
(1) silicon dioxide 2.3 Kg, calcium oxide 5.5 Kg, aluminium sesquioxide 1.7 Kg, magnesium oxide 0.04 Kg, sodium carbonate are taken
0.01 Kg fully mixes, at 1400 DEG C of fritting 0.5h CaO-SiO2-Al2O3-MgO-Na2O slag；
(2) put in crucible furnace together with taking after 8.5 Kg slags mix with 50 Kg matte and heat until being completely melt；
(3) blasting oxygen slag making melting, smelting temperature 1250-1350 DEG C, smelting time 0.5 h, oxygen flow is 20 L/
min；
(4) melting carries out, after terminating cooling, separation of skimming, and obtains rich arsenic slag and copper-nickel alloy.
The rich arsenic slag arsenic accumulation rate that the present embodiment obtains is 71%.
The method of the present invention a kind of Copper making process slag making arsenic removal, in large-scale smelting furnace, composite fluxing agent can not carry out pre-
Molten, it is directly added into melting in smelting furnace after being mixed by each material；It is all that melting mode is matte smelting and the blowing refinement of the matte comprises
Melting mode；Ventilating mode is divided into smelting furnace ventilation with to melt internal ventilation two kinds.The impact that composite fluxing agent fritting is main
Factor is temperature and time, and when exceeding above-mentioned prefusing temperature and time range, in slag, composition fails effectively to combine, and affects melting
Effect；Smelting Effect is affected by temperature, time and ventilation flow rate, exceedes said temperature and time range, it may appear that melting is not filled
Dividing or after melting, slag copper separates the situations such as difficulty, when ventilation flow rate is less than above-mentioned lower limit, melting reaction is slack-off, impact effect, high
When the upper limit, local response can be caused too fast, be unfavorable for that slag making and copper ashes separate.
The treatment effect contrast of three above embodiment is shown in Table 1, and the index parameter of embodiment 2 is optimal as seen from Table 1, for
Good embodiment.
Table 1 each embodiment Contrast on effect table
It should be noted that, the application of the present invention is not limited to above-mentioned citing, for those of ordinary skills, do not taking off
On the premise of the principle of the invention, it is also possible to improved according to the above description or modify, all these improvement or modification are all answered
Fall in the protection domain of the claims in the present invention.
Claims (7)
1. a method for Copper making process slag making arsenic removal, is characterized in that: use composite fluxing agent to improve arsenic distribution in slag
Ratio, operating procedure is as follows:
(1) by metal-oxide or the mixing of metal fused salt of different proportion, it is melt into compound molten under 1200 DEG C of high temperature above in advance
Agent；
(2) in high temperature furnace, the copper material containing arsenic and composite fluxing agent are heated to fusing；
(3) to be melted completely after, be passed through oxygen and carry out melting；
(4) after melting terminates, stand and carry out slag copper separation, obtain rich arsenic slag and low containing arsenical copper material.
2. the method for Copper making process slag making arsenic removal as claimed in claim 1, is characterized in that: the metal oxygen in described step (1)
Compound or metal fused salt are following 11 kinds of materials, and described composite fluxing agent is by selecting 3 ~ 11 kinds of preparations in the material of these 11 kinds of weight portions
Form: ferrum oxide 0 ~ 70 part, quartz sand 0 ~ 40 part, calcium oxide 0 ~ 30 part, aluminium oxide 0 ~ 30 part, sodium carbonate 0 ~ 5 part, magnesium oxide 0 ~
5 parts, sodium oxide 0 ~ 5 part, 0 ~ 5 part of calcium fluoride, Barium monoxide 0 ~ 5 part, sodium silicate 0 ~ 5 part, titanium oxide 0 ~ 5 part.
3. the method for Copper making process slag making arsenic removal as claimed in claim 1, is characterized in that: the fritting in described step (1) is multiple
The prefusing temperature closing flux is 1200 ~ 1500 DEG C, fritting time 0.5 ~ 1.5 h.
4. the method for Copper making process slag making arsenic removal as claimed in claim 1, is characterized in that: composite fluxing agent in described step (2)
With containing arsenical copper material mass ratio be 0.01 ~ 1:1, fusion temperature is 1200 ~ 1350 DEG C, and fusing time is 0.5 ~ 1 h.
5. the method for Copper making process slag making arsenic removal as claimed in claim 1, is characterized in that: the temperature of melting in described step (3)
Degree is 1200 ~ 1350 DEG C, and oxygen flow is 0.5 ~ 20 L/min, and smelting time is 0.5-3 h.
6. the method for Copper making process slag making arsenic removal as claimed in claim 1, is characterized in that: the melting in described step (3) is
All melting modes that matte smelting and the blowing refinement of the matte comprise；Ventilating mode is divided into smelting furnace ventilation with to melt internal ventilation
Two kinds.
7. the method for Copper making process slag making arsenic removal as claimed in claim 1, is characterized in that: the standing in described step (4) is
Stand 20 ~ 40 min.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106629633A (en) * | 2016-12-27 | 2017-05-10 | 郴州市金贵银业股份有限公司 | Method for refining and removing arsenic from precipitated tellurium |
| ES2666396A1 (en) * | 2016-11-02 | 2018-05-04 | Yanggu Xiangguang Copper CO., Ltd | A procedure to melt a copper sulphide mineral with high arsenic content (Machine-translation by Google Translate, not legally binding) |
| CN114231754A (en) * | 2021-11-08 | 2022-03-25 | 铜陵有色金属集团股份有限公司 | Copper flash smelting process |
| CN114410969A (en) * | 2021-12-30 | 2022-04-29 | 济源豫光有色冶金设计研究院有限公司 | Method for recycling copper and arsenic from black copper mud step by step |
| CN114574707A (en) * | 2022-04-16 | 2022-06-03 | 中铜东南铜业有限公司 | Slag type optimizing agent in copper smelting process and preparation method thereof |
| CN115725853A (en) * | 2022-11-11 | 2023-03-03 | 云南铜业股份有限公司西南铜业分公司 | Solid arsenic smelting method for high-arsenic copper concentrate |
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| CN115725853A (en) * | 2022-11-11 | 2023-03-03 | 云南铜业股份有限公司西南铜业分公司 | Solid arsenic smelting method for high-arsenic copper concentrate |
| CN115725853B (en) * | 2022-11-11 | 2024-01-16 | 云南铜业股份有限公司西南铜业分公司 | Arsenic fixing smelting method of high-arsenic copper concentrate |
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