CN109797288A - A kind for the treatment of process of tin metallurgy sulphur slag - Google Patents
A kind for the treatment of process of tin metallurgy sulphur slag Download PDFInfo
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- CN109797288A CN109797288A CN201910098870.XA CN201910098870A CN109797288A CN 109797288 A CN109797288 A CN 109797288A CN 201910098870 A CN201910098870 A CN 201910098870A CN 109797288 A CN109797288 A CN 109797288A
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Abstract
The present invention provides a kind for the treatment of process of tin metallurgy sulphur slag, solves some shortcomings existing for prior art.Finally make valuable metal element S n, the Cu synthetical recovery in tin metallurgy sulphur slag, and removes the impurity elements such as S.The process flow of use is broadly divided into three parts: first, tin metallurgy sulphur slag is subjected to physical separation, physical separation is using grinding, the method sieved, it obtains sieving the lower two parts material of upper and sieve, it is wherein mainly metal on sieve, metal can directly return to smelting system, sieve lower sulphur slag and carry out next step oxidizing roasting processing；Secondly, will sieve lower sulphur slag carries out oxidizing roasting, oxidizing roasting by slag metal and the final complete oxidation of metal sulfide be steady oxide and in this process desulfurization；Hereafter, calcining oxidizing roasting obtained carries out sulfuric acid leaching, and leaching process makes Cu enter leachate, and Sn enters leached mud, to achieve the purpose that copper and tin separates；Finally, respectively to after leaching leachate and leached mud be recycled, obtain the product of copper sulphate and tin oxide.
Description
Technical field
The invention belongs to metallurgical solid wastes to be recycled field, and in particular to a kind for the treatment of process of tin metallurgy sulphur slag.
Background technique
Metallic tin is lived in people and economic field all plays very important effect, is the indispensable weight of development in science and technology
Want backing material.As the application range of tin is growing, dosage is increase accordingly, a large amount of diggings of the people to primary tin ore, former
Raw Tin Resources are increasingly depleted, effective to recycle and utilize tin smelting process to realize the sustainable development of tin metallurgical industry
Middle output largely becomes more and more important containing scruff.In Tin concentrate smelting process, in the tin metallurgy sulphur slag for adding sulphur powder copper removal to obtain,
The content of tin reaches 55% or more, copper content and reaches 20% or so, recovery value with higher, the harmful element contained in slag
Sulphur, arsenic etc. can cause environmental pollution.Integrated treatment tin metallurgy sulphur slag recycles tin and copper in slag, obtains tin oxide and copper sulphate
Product makes tin metallurgy sulphur slag recycling, there is larger economic benefit, is conducive to the reduction of comprehensive production cost.
(1) pyrometallurgical smelting: being incorporated a certain proportion of flux in rotary furnace and carry out melting, generate half product of gun-metal, due to
Impurity in slag largely enters in the alloy, causes the alloy product to be further processed and has difficulties.
(2) roasting-lixiviation process: the leaching process of calcining is carried out after the roasting of tin metallurgy sulphur slag with sulfuric acid, produces copper with copper sulphate
Product form is opened a way from tin smelting system, and this method does not separate the metallic tin contained in slag, is directly roasted, is not only needed more
Section roasting reaches desulfurization purpose, and the oxidation of unsegregated metal increases treating capacity, increases energy consumption.
(3) diaphragm process: this be at present in production using more tin metallurgy sulphur Slag treatment method, the method be first by
Tin metallurgy sulphur slag carry out diaphragm electrolysis, by a certain amount of metallic tin with Sn-Pb alloy form open circuit after, then by electrolysis anode sludge (every
Film slag) oxidizing roasting, sulfuric acid leaching are carried out, make copper with copper sulphate product output, to achieve the purpose that the open circuit of copper.The method by
In the presence of powdery copper sulfide, when making electrolysis, tin direct recovery rate is lower, current efficiency is lower, causes economic benefit poor.
(4) Whote-wet method technique: having researcher to carry out the research of the Whote-wet method treatment process of tin metallurgy sulphur slag, is by tin metallurgy sulphur
Hydrochloric acid for dreg decomposes, and all the components in slag is made to fully enter solution, then carries out the separation of each element in the solution.Publication No.
A kind of processing method for tin metallurgy sulphur slag that the Chinese patent of CN108359805 proposes using the pressure alkali leaching of tin copper ashes elder generation's oxygen, then carries out
Two sections of extract technologies of normal pressure acidleach, first output sodium stannate product, residual residue realize that tin copper efficiently separates again, make copper with sulfuric acid
Copper products form output, the Tin concentrate of output return to tin smelting system, and that there are process flows is tediously long for Whote-wet method, process it is many and diverse it is equal not
Foot.
(5) fiery wet processing: a kind of Chinese patent of the processing method of tin metallurgy sulphur slag is leached using one section of sulfuric acid, is obtained
Stannous sulfate solution purification after high-grade stannous sulfate product can be obtained, after one section of leached mud oxidizing roasting two sections of sulfuric acid leaching
Out, copper-bath is obtained, condensing crystallizing output sulfuric acid copper products or can enter copper electrolysis system and produce electricity copper, and two sections of leached muds are
Tin smelting system is returned to for Tin concentrate, which haves the shortcomings that the amount of metallic tin return tin melting is higher.
Summary of the invention
The purpose of the present invention is to provide a kind for the treatment of process of tin metallurgy sulphur slag, solve existing for prior art it is some not
Foot.Finally make valuable metal element S n, the Cu synthetical recovery in tin metallurgy sulphur slag, and removes the impurity elements such as S.This technique is used
Process flow be broadly divided into three parts: firstly, by tin metallurgy sulphur slag carry out physical separation, physical separation using grinding, screening
Method, it is upper and sieve lower two parts material to obtain sieve, wherein predominantly metal, metal can directly return to smelting system on sieve, sieves
Lower sulphur slag carries out next step oxidizing roasting processing；Secondly, will sieve lower sulphur slag carries out oxidizing roasting, oxidizing roasting is by the metal in slag
And the final complete oxidation of metal sulfide is for steady oxide and in this process desulfurization；Hereafter, calcining oxidizing roasting obtained
Sulfuric acid leaching is carried out, leaching process makes Cu enter leachate, and Sn enters leached mud, to achieve the purpose that copper and tin separates；Finally,
Respectively to after leaching leachate and leached mud be recycled, obtain the product of copper sulphate and tin oxide.
The specific technical proposal of the invention is:
A kind for the treatment of process of tin metallurgy sulphur slag, comprising the following steps:
(1) tin metallurgy sulphur slag sample pulverizer is ground into 10~30min, is sieved, is sieved with the sieve of 60 mesh after grinding
Upper reguline metal and minus sieve powder sulphur slag.
(2) the sulphur slag under above-mentioned sieve is carried out to one section of roasting under the conditions of 500 DEG C, calcining time 60min will be roasted
The calcining arrived is broken, carries out two-stage calcination, and two-stage calcination temperature is 800 DEG C, and calcining time 60min obtains product of roasting；
(3) by above-mentioned gained product of roasting sulfuric acid leaching, leaching condition is 30~90min of extraction time, extraction temperature
60~90 DEG C, 3~9:1 of liquid-solid ratio, stirring rate 100~400r/min, H2SO4Mass concentration 10~25%, with this condition
To the leachate containing copper sulphate and containing the leached mud of tin oxide；
(4) above-mentioned gained leachate is removed into iron with basic copper carbonate, be further concentrated by evaporation, five water can be made in crystallisation by cooling
Copper sulfate crystal；SnO can be obtained after above-mentioned gained leached mud is washed, dry2。
Further, reguline metal accounts for entire tin metallurgy sulphur slag on the sieve that above-mentioned steps (1) are separated by grinding
The 23.15~23.66% of quality, wherein metallic tin accounts for 84.34~86.37%, and the content of copper accounts for 8.67~9.90%, the part
Metal directly returns to tin and smelts process；In minus sieve powder sulphur slag the mass percentage of essential element Sn be 63.27~
The mass percentage that the mass percentage of 65.50%, Cu are 18.20~21.09%, S is 13.09~13.67%.
The beneficial effects of the present invention are:
1. the mode of physical separation sulphur slag in the present invention, make wherein about 25% metal recycle in advance, do not have to sulfide into
Row oxidizing roasting-sulfuric acid leaching technique reduces the treating capacity of subsequent material, reduces energy consumption, saves processing cost.
2. the present invention in two stages, has carried out physical separation to sulphur slag since roasting is preceding to the oxidizing roasting for sieving lower sulphur slag
Processing, so the technique applied in industry compared to before, the temperature of two-stage roasting all decreases, to reduce energy consumption.
3. the cleaning solution that leachate passes through the condensing crystallizing crystalline mother solution generated and the washed generation of leached mud in the present invention
It can be used in sulfuric acid leaching recycling, so as to avoid the processing of waste water.
4. final recycling two kinds of elements of Cu, Sn of the invention, under optimum process condition, the rate of recovery of copper is 90.38%, tin
The rate of recovery be 93.13%.Finally product obtained is CuSO to the technique4·5H2O and SnO2, obtained CuSO4·5H2O purity
For 97.66%, SnO2Purity be 98.78%.
5. the present invention uses physical separation-oxidizing roasting-sulfuric acid leaching process sulphur slag, technique is relatively easy,
Energy consumption is relatively low few, and economic cost is lower.
Detailed description of the invention
Fig. 1 is a kind of process flow chart of the treatment process of tin metallurgy sulphur slag of the invention.
Specific embodiment
Technology contents of the invention are continued to describe below by embodiment.
Embodiment 1
A kind for the treatment of process of tin metallurgy sulphur slag, sequentially includes the following steps:
(1) 500g tin metallurgy sulphur slag sample pulverizer is ground into 20min, is sieved, is obtained on sieve with the sieve of 60 mesh after grinding
Reguline metal and minus sieve powder sulphur slag.The 23.66% of entire sulphur slag amount is accounted for by grinding the metal separated, wherein
Metallic tin accounts for 85.79%, and the content of copper accounts for 9.90%, which directly returns to tin and smelt process；It sieves main in lower sulphur slag
The percentage composition that the percentage composition that the percentage composition of element S n is 65.50%, Cu is 18.20%, S is 13.67%；
(2) gained in (1) is sieved lower sulphur slag to be crushed after 500 DEG C of roasting 60min, is roasted in 800 DEG C of roasting 60min
Sand；
(3) by gained calcining sulfuric acid leaching in (2), leaching condition is extraction time 50min, 70 DEG C of extraction temperature, liquid
Gu than 3:1, stirring rate 400r/min, H2SO4Mass concentration 20%, obtain with this condition the leachate containing copper sulphate and
Leached mud containing tin oxide；
(4) gained leachate in (3) is removed into iron with basic copper carbonate, be further concentrated by evaporation, crystallisation by cooling can be made
CuSO4·5H2O crystal；SnO can be obtained after above-mentioned gained leached mud is washed, dry2.Under optimum process condition, copper is returned
Yield is 90.38%, and the rate of recovery of tin is 93.13%.Obtained CuSO4·5H2O purity is 97.66%, SnO2Purity be
98.78%.
Embodiment 2
A kind for the treatment of process of tin metallurgy sulphur slag, sequentially includes the following steps:
(1) 500g tin metallurgy sulphur slag sample pulverizer is ground into 30min, is sieved, is obtained on sieve with the sieve of 60 mesh after grinding
Reguline metal and minus sieve powder sulphur slag.The 23.56% of entire sulphur slag amount is accounted for by grinding the metal separated, wherein
Metallic tin accounts for 86.37%, and the content of copper accounts for 8.82%, which directly returns to tin and smelt process；It sieves main in lower sulphur slag
It is 13.09% that the percentage composition of element S n, which is up to the content that the content of 63.58%, Cu is 21.09%, S,；
(2) gained in (1) is sieved lower sulphur slag to be crushed after 500 DEG C of roasting 60min, is roasted in 800 DEG C of roasting 60min
Sand；
(3) by gained calcining sulfuric acid leaching in (2), leaching condition is extraction time 70min, 80 DEG C of extraction temperature, liquid
Gu than 5:1, stirring rate 300r/min, H2SO4Mass concentration 25%, obtain with this condition the leachate containing copper sulphate and
Leached mud containing tin oxide；
(4) gained leachate in (3) is removed into iron with basic copper carbonate, be further concentrated by evaporation, crystallisation by cooling can be made
CuSO4·5H2O crystal；SnO can be obtained after above-mentioned gained leached mud is washed, dry2.Under optimum process condition, copper is returned
Yield is 91.09%, and the rate of recovery of tin is 92.89%.Obtained CuSO4·5H2O purity is 97.83%, SnO2Purity be
97.68%.
Embodiment 3
A kind for the treatment of process of tin metallurgy sulphur slag, sequentially includes the following steps:
(1) 500g tin metallurgy sulphur slag sample pulverizer is ground into 10min, is sieved, is obtained on sieve with the sieve of 60 mesh after grinding
Reguline metal and minus sieve powder sulphur slag.The 23.15% of entire sulphur slag amount is accounted for by grinding the metal separated, wherein
Metallic tin accounts for 84.34%, and the content of copper accounts for 8.67%, which directly returns to tin and smelt process；It sieves main in lower sulphur slag
The percentage composition that the percentage composition that the percentage composition of element S n is 63.27%, Cu is 20.55%, S is 13.34%；
(2) gained in (1) is sieved lower sulphur slag to be crushed after 500 DEG C of roasting 60min, is roasted in 800 DEG C of roasting 60min
Sand；
(3) by gained calcining sulfuric acid leaching in (2), leaching condition is extraction time 90min, 90 DEG C of extraction temperature, liquid
Gu than 7:1, stirring rate 400r/min, H2SO4Mass concentration 15%, obtain with this condition the leachate containing copper sulphate and
Leached mud containing tin oxide；
(4) gained leachate in (3) is removed into iron with basic copper carbonate, be further concentrated by evaporation, crystallisation by cooling can be made
CuSO4·5H2O crystal；SnO can be obtained after above-mentioned gained leached mud is washed, dry2.Under optimum process condition, copper is returned
Yield is 89.96%, and the rate of recovery of tin is 92.38%.Obtained CuSO4·5H2O purity is 97.26%, SnO2Purity be
98.05%.
Claims (2)
1. a kind for the treatment of process of tin metallurgy sulphur slag, which comprises the following steps:
(1) tin metallurgy sulphur slag sample pulverizer is ground into 10~30min, is sieved after grinding with the sieve of 60 mesh, obtains sieving block
Shape metal and minus sieve powder sulphur slag；
(2) the powder sulphur slag under step (1) sieve is subjected to one section of roasting under the conditions of 500 DEG C, calcining time 60min will be roasted
It is broken to burn obtained calcining, carries out two-stage calcination, two-stage calcination temperature is 800 DEG C, calcining time 60min, obtains roasting and produces
Object；
(3) by product of roasting sulfuric acid leaching obtained by step (2), leaching condition is 30~90min of extraction time, extraction temperature 60
~90 DEG C, 3~9:1 of liquid-solid ratio, 100~400r/min of stirring rate, h 2 so 4 concentration 10~25% obtains with this condition
Leachate containing copper sulphate and the leached mud containing tin oxide；
(4) leachate obtained by step (3) is removed into iron with basic copper carbonate, be further concentrated by evaporation, five water sulphur are made in crystallisation by cooling
Sour copper crystal；SnO is obtained after leached mud obtained by step (3) is washed, dry2。
2. the treatment process of tin metallurgy sulphur slag according to claim 1, which is characterized in that step (1) passes through grinding screening point
Separate out reguline metal on the sieve come and account for the 23.15~23.66% of entire tin metallurgy sulphur slag amount, wherein metallic tin account for 84.34~
86.37%, the content of copper accounts for 8.67~9.90%, which directly returns to tin and smelt process；It is main in minus sieve powder sulphur slag
It is the matter of 18.20~21.09%, S that the mass percentage for wanting element S n, which is the mass percentage of 63.27~65.50%, Cu,
Measuring percentage composition is 13.09~13.67%.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114107670A (en) * | 2021-11-24 | 2022-03-01 | 白银有色集团股份有限公司 | Method for recovering copper sulfate crystals from waste copper slag |
| CN115125388A (en) * | 2022-07-19 | 2022-09-30 | 昆明理工大学 | Method for recovering valuable metals by directly reducing tin alloy slag through aluminum electrolysis waste carbon |
| WO2023134017A1 (en) * | 2022-01-17 | 2023-07-20 | 昆明理工大学 | Method for separating and purifying tin and copper from tin refining sulfur slag |
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2019
- 2019-01-31 CN CN201910098870.XA patent/CN109797288B/en active Active
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114107670A (en) * | 2021-11-24 | 2022-03-01 | 白银有色集团股份有限公司 | Method for recovering copper sulfate crystals from waste copper slag |
| WO2023134017A1 (en) * | 2022-01-17 | 2023-07-20 | 昆明理工大学 | Method for separating and purifying tin and copper from tin refining sulfur slag |
| CN115125388A (en) * | 2022-07-19 | 2022-09-30 | 昆明理工大学 | Method for recovering valuable metals by directly reducing tin alloy slag through aluminum electrolysis waste carbon |
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