CN103397200B - Method for removing lead, zinc, arsenic, antimony, bismuth and tin from copper matte - Google Patents
Method for removing lead, zinc, arsenic, antimony, bismuth and tin from copper matte Download PDFInfo
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Abstract
The invention discloses a method for removing lead, zinc, arsenic, antimony, bismuth and tin from copper matte. The method comprises the following steps of: placing crushed and dried copper matter in a vacuum distillation furnace, maintaining residual voltage in the furnace at 1-100 Pa and a volatilization temperature at 1100-1400 DEG C, and carrying out heat preservation for 0.5-1.5 hours, so that impurity elements such the lead, the zinc, the arsenic, the antimony, the bismuth and the tin in the copper matte are volatilized at metallic state or vulcanization state; condensing in a condenser so as to separate the lead, the zinc, the arsenic, the antimony, the bismuth and the tin from copper matte, thus obtaining the purified copper matte or lead and zinc multi-element alloy. The contents of the Pb, the Zn, the Bi and the Sn in the copper matte are respectively reduced to 0.001% to 0.01%, the content of the As can be reduced to 0.01% to 0.1%, and the content of the Sb is reduced to 0.01% to 1%. The method has the advantages that the copper matte is purified by adopting a vacuum metallurgy method, the technological process operation is convenient, safe and controllable, the environmental pollution is low, the removal rate of the lead, the zinc, the arsenic, the antimony, the bismuth and the tin is high, the industrialized application is easy, the obtained lead and zinc multi-element alloy can be recycled and sold, and the economic benefit is obvious.
Description
Technical field
The present invention relates to a kind of method removing lead, zinc, arsenic, antimony, bismuth, tin from matte, belong to non-ferrous metal pyrometallurgical smelting technical field.
Background technology
Copper is at occurring in nature mainly sulphide ores and oxidized ore, and particularly sulphide ores distribution is the widest, and the copper mine of nearly 80% exists with Cu-Fe-S ore form.Put forward for sulphide ores the method that copper adopts pyrometallurgy usually, general flow is: copper sulfide ore → selecting and purchasing operation → copper ore concentrates → melting operation → matte → blowing operation → blister copper → anode furnace operation → anode copper → electrowinning process → Cu-CATH-1.
In recent years because Copper making ability is acutely expanded, the supply of high-quality copper ore concentrates becomes more and more nervous, major part buys mining and metallurgy refinery for meeting the needs of production and pursuing more profit, when volume procurement high-quality copper ore concentrates, have to purchase the higher copper ore concentrates of some foreign matter contents, impurity element is the element such as lead, zinc, arsenic, antimony, bismuth, tin mainly.But after the copper ore concentrates that these foreign matter contents are higher puts into production, extreme influence is caused to normal production, mainly contains:
1., because the impurity contents such as lead, zinc increase, cause the fusing point of smelting slag and blowing slag to raise, the viscosity of slag increases, slagging difficulty.
2. part of impurity elements volatilization enters flue dust, causes flue dust viscosity to increase, the flue dust of melting inside furnace wall, flue inner wall, flue and waste heat boiler junction dross.
3. flue dust enters waste heat boiler, is bonded in boiler wall, and difficult drop-off, to scraper plate, makes Department of Radiation and convection section junction block gradually, and on convection current generating tube, dust stratification is serious, has had a strong impact on the heat transfer effect of waste heat boiler.
4. cause the impurity content exceeding indexs such as mineral products positive plate lead, zinc, bismuth, tin, have a strong impact on the normal production of potroom, easily occur that bath voltage is higher, big area anode passivation, the problem such as the floating anode sludge is more in electrolytic solution, the long particle of cathode plate is more.Especially at high current density (300 ~ 450A/m
2) under, there is scale effect in these problems, what can become is even more serious.
Summary of the invention
For above-mentioned prior art, for solving some problems existed in melting height composition brass concentrate process, the invention provides a kind of method removing lead, zinc, arsenic, antimony, bismuth, tin from matte, the method lead, zinc, arsenic, antimony, bismuth, tin decreasing ratio are high, and can reclaim, economic benefit is obvious.
The present invention is achieved by the following technical solutions:
From matte, remove a method for lead, zinc, arsenic, antimony, bismuth, tin, comprise the steps:
To pulverize, dried matte puts into vacuum distillation furnace, by controlling residual voltage in certain stove, volatilization temperature and soaking time, make lead impurity element, zinc, arsenic, antimony, bismuth, tin with metallic state or the volatilization of sulfuration states of matter from matte melt, in gaseous state, volatilization enters in condenser, and condensation obtains plumbous zinc multicomponent alloy, lead, zinc, arsenic, antimony, bismuth, tin are separated with matte, obtain the matte after plumbous zinc multicomponent alloy and purification.
Described matte, its constituent content per-cent (percentage composition of the present invention is mass percent) is: copper 20% ~ 80%, lead 0.01% ~ 10%, zinc 0.01% ~ 10%, arsenic 0.01% ~ 15%, antimony 0.001% ~ 15%, bismuth 0.001% ~ 5%, tin are 0.001% ~ 5%, other composition 15% ~ 35%.After aforesaid method process, in matte, Pb, Zn, Bi, Sn content can be down to 0.001% ~ 0.01%, As respectively and can be down to 0.01% ~ 0.1%, Sb content and can be down to 0.01% ~ 1%.
Preferably, processing parameter is: keep residual voltage in stove to be 1 ~ 100Pa, volatilization temperature 1100 ~ 1400 DEG C, soaking time 0.5 ~ 1.5h.
The present invention remove from matte lead, zinc, arsenic, antimony, bismuth, tin principle be:
(1) under vacuum environment and same temperature condition, the lead impurity element in matte liquation, zinc, arsenic, antimony, bismuth, tin have higher vapour pressure, easily become gaseous state volatilization, and volatilization form may be metallic state, also may be sulfuration states of matter; And in matte liquation, Cu
2the vapour pressure of the materials such as S, FeS is smaller, substantially non-volatile, thus reaches remove Element Lead, zinc, arsenic, antimony, bismuth, tin from matte liquation, the object of purification matte.
(2), in matte, copper is mainly with Cu
2s form exists, and can not form compound with Element Lead, zinc, arsenic, antimony, bismuth, tin, do not have the impact of chemical binding force, Element Lead, zinc, arsenic, antimony, bismuth, tin can volatilize better.
(3) volatility of metallic sulfide is greater than the volatility of its corresponding metal simple-substance usually.Element Lead, zinc, arsenic, antimony, bismuth, tin can form sulfide with part sulphur in matte, then with oxide morphology volatilization, can obtain than volatilize with metallic state higher evaporation rate and rate of volatilization.
The present invention adopts the method purification matte of vacuum metallurgy, for some problems existed in copper smelting plant process height composition brass concentrate provide a kind of solution, whole technological process is easy to operate, safety is controlled, environmental pollution is little, the element decreasing ratiies such as lead, zinc, arsenic, antimony, bismuth, tin are high, from source, just most of lead impurity element, zinc, arsenic, antimony, bismuth, tin are separated Copper making production system, be conducive to subsequent handling to produce, and facility investment is not high, be easy to industrial applications, the plumbous zinc multicomponent alloy obtained can reclaim sale, and economic benefit is obvious.
Accompanying drawing explanation
Fig. 1 is the process flow sheet of method of the present invention.
Embodiment
In order to understand the present invention further, below in conjunction with embodiment, the preferred embodiment of the invention is described, but should be appreciated that these describe just for further illustrating feature of the present invention, instead of limiting to the claimed invention.
Embodiment 1: get 500g matte, in matte, the content of impurity lead, zinc, arsenic, antimony, bismuth, tin is: lead 8.42%, zinc 2.52%, arsenic 12.87%, antimony 10.99%, bismuth 1.36%, tin 1.91%.After matte fragmentation, drying, put into vacuum distillation furnace, control residual voltage 1 ~ 30Pa in stove, volatilization temperature 1400 DEG C, soaking time 30min, make lead impurity element, zinc, arsenic, antimony, bismuth, tin with metallic state or the volatilization of sulfuration states of matter from matte melt, in gaseous state, volatilization enters in condenser, condensation obtains plumbous zinc multicomponent alloy, and lead, zinc, arsenic, antimony, bismuth, tin are separated with matte (technical process as shown in Figure 1).In matte after purification, the content of impurity lead, zinc, arsenic, antimony, bismuth, tin is: lead 0.0058%, zinc 0.0022%, arsenic 0.039%, antimony 0.95%, bismuth 0.0073%, tin 0.0023%, and decreasing ratio is respectively lead 99.96%, zinc 99.95%, arsenic 99.81%, antimony 94.64%, bismuth 99.67%, tin 99.93%.
Embodiment 2: get 500g matte, in matte, the content of impurity lead, zinc, arsenic, antimony, bismuth, tin is: lead 4.1%, zinc 2.6%, arsenic 4.7%, antimony 1.59%, bismuth 0.92%, tin 0.087%.After matte fragmentation, drying, put into vacuum distillation furnace, control residual voltage 20 ~ 60Pa in stove, volatilization temperature 1200 DEG C, soaking time 60min, make lead impurity element, zinc, arsenic, antimony, bismuth, tin with metallic state or the volatilization of sulfuration states of matter from matte melt, in gaseous state, volatilization enters in condenser, condensation obtains plumbous zinc multicomponent alloy, and lead, zinc, arsenic, antimony, bismuth, tin are separated with matte.In matte after purification, the content of impurity lead, zinc, arsenic, antimony, bismuth, tin is: lead 0.0049%, zinc 0.0022%, arsenic 0.022%, antimony 0.063%, bismuth 0.0062%, tin 0.0017%, and decreasing ratio is respectively: lead 99.90%, zinc 99.93%, arsenic 99.60%, antimony 96.59%, bismuth 99.42%, tin 98.32%.
Embodiment 3: get 500g matte, in matte, the content of impurity lead, zinc, arsenic, antimony, bismuth, tin is: lead 0.79%, zinc 0.58%, arsenic 0.55%, antimony 0.03%, bismuth 0.10%, tin 0.073%.After matte fragmentation, drying, put into vacuum distillation furnace, control residual voltage 50 ~ 80Pa in stove, volatilization temperature 1100 DEG C, soaking time 90min, make lead impurity element, zinc, arsenic, antimony, bismuth, tin with metallic state or the volatilization of sulfuration states of matter from matte melt, in gaseous state, volatilization enters in condenser, condensation obtains plumbous zinc multicomponent alloy, and lead, zinc, arsenic, antimony, bismuth, tin are separated with matte.In matte after purification, the content of impurity lead, zinc, arsenic, antimony, bismuth, tin is: lead 0.0033%, zinc 0.0019%, arsenic 0.025%, antimony 0.023%, bismuth 0.0042%, tin 0.0019%, and decreasing ratio is respectively: lead 99.60%, zinc 99.68%, arsenic 95.55%, antimony 24.90%, bismuth 95.89%, tin 97.45%.
Embodiment 4: get 500g matte, in matte, the content of impurity lead, zinc, arsenic, antimony, bismuth, tin is: lead 0.35%, zinc 0.37%, arsenic 0.21%, antimony 0.01%, bismuth 0.094%, tin 0.025%.After matte fragmentation, drying, put into vacuum distillation furnace, control residual voltage 60 ~ 100Pa in stove, volatilization temperature 1100 DEG C, soaking time 60min, make lead impurity element, zinc, arsenic, antimony, bismuth, tin with metallic state or the volatilization of sulfuration states of matter from matte melt, in gaseous state, volatilization enters in condenser, condensation obtains plumbous zinc multicomponent alloy, and lead, zinc, arsenic, antimony, bismuth, tin are separated with matte.In matte after purification, the content of impurity lead, zinc, arsenic, antimony, bismuth, tin is: lead 0.0028%, zinc 0.0023%, arsenic 0.020%, antimony 0.01%, bismuth 0.0039%, tin 0.0012%, and decreasing ratio is respectively: lead 99.21%, zinc 99.38%, arsenic 90.57%, antimony 1.02%, bismuth 95.89%, tin 95.25%.
Above to provided by the present invention a kind of remove from matte lead, zinc, arsenic, antimony, bismuth, tin method be described in detail.Apply specific case herein to set forth principle of the present invention and embodiment, the explanation of above embodiment just understands method of the present invention and core concept thereof for helping.It should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention, can also carry out some improvement and modification to the present invention, these improve and modify and also fall in the protection domain of the claims in the present invention.
Claims (2)
1. one kind removes the method for lead, zinc, arsenic, antimony, bismuth, tin from matte, it is characterized in that: will pulverize, dried matte puts into vacuum distillation furnace, by controlling residual voltage in certain stove, volatilization temperature and soaking time, make lead impurity element, zinc, arsenic, antimony, bismuth, tin from matte melt with metallic state or the volatilization of sulfuration states of matter, in gaseous state, volatilization enters in condenser, condensation obtains plumbous zinc multicomponent alloy, lead, zinc, arsenic, antimony, bismuth, tin are separated with matte, obtain the matte after plumbous zinc multicomponent alloy and purification;
Described matte, its constituent content per-cent is: copper 20% ~ 80%, lead 0.01% ~ 10%, zinc 0.01% ~ 10%, arsenic 0.01% ~ 15%, antimony 0.001% ~ 15%, bismuth 0.001% ~ 5%, tin are 0.001% ~ 5%, other composition 15% ~ 35%.
2. method according to claim 1, is characterized in that: in described stove, residual voltage is 1 ~ 100Pa, volatilization temperature 1100 ~ 1400 DEG C, soaking time 0.5 ~ 1.5h.
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| SE1951540A1 (en) * | 2019-12-20 | 2021-06-21 | Nordic Brass Gusum Ab | Method for removing lead from brass |
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| 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 |
| US10563289B2 (en) | 2017-06-29 | 2020-02-18 | Companhia Brasileira De Metalurgia E Mineracão | Process for refining niobium-based ferroalloys |
| CN108300865A (en) * | 2018-04-19 | 2018-07-20 | 西安建筑科技大学 | The extracting method of lead zinc arsenic in a kind of arsenic-containing smoke dust |
| CN113667836A (en) * | 2021-07-08 | 2021-11-19 | 赤峰大井子矿业有限公司 | Tin smelting method capable of realizing valuable metal recovery |
| CN115386739A (en) * | 2022-09-02 | 2022-11-25 | 昆明理工大学 | Method for directly extracting sulfide and enriching noble metal from matte |
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