CN103993184B - A kind for the treatment of process of high antimony bismuth-containing material - Google Patents

A kind for the treatment of process of high antimony bismuth-containing material Download PDF

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CN103993184B
CN103993184B CN201410158178.9A CN201410158178A CN103993184B CN 103993184 B CN103993184 B CN 103993184B CN 201410158178 A CN201410158178 A CN 201410158178A CN 103993184 B CN103993184 B CN 103993184B
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bismuth
antimony
containing material
high antimony
smelting
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CN103993184A (en
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杨兴文
涂相林
吴杰
祝志兵
倪明星
邹志武
钟志燕
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Jiangxi Copper Co Ltd
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Jiangxi Copper Co Ltd
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    • 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
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Abstract

The treatment process of a kind of high antimony bismuth-containing material of the present invention, the concrete steps of this technique are as follows: step one: main containing Sb and a small amount of Cu impurity element in high antimony bismuth-containing material, in reduction smelting in reverberatory furnace process, add a certain amount of bismuth sulfide, lime, soda ash, iron filings and coke powder, make the antimony of the overwhelming majority, smelting temperature 500--700 DEG C, smelting time 2--12 hour.After melting terminates, slagging-off, obtains thick bismuth, shoddye and dry slag; It is in 20-60g/l liquid caustic soda that shoddye step one obtained is dissolved in concentration, is warming up to 85 DEG C, reaction 2-8 hour, and most of antimony enters in liquid phase; Alkali lye adjust ph step 2 obtained is after 4-7, is warming up to 40-85 DEG C, and reaction 2-6 hour, passes into atmospheric oxidation and obtain thick sodium antimonate.The treatment process of the high antimony bismuth-containing material of the method can realize reverberatory smelting process and directly be separated antimony, bismuth in high antimony bismuth-containing material, and antimony, the bismuth rate of recovery all reach more than 95%.

Description

A kind for the treatment of process of high antimony bismuth-containing material
Technical field
The invention belongs to non-ferrous extractive metallurgy technical field, especially a kind of containing separation of Bismuth, antimony novel process in high antimony, bismuth material, the low impurity crude bismuth of production higher-grade, provides the treatment process of a kind of high antimony bismuth-containing material of the thick bismuth of high quality raw material for smart bismuth production line refining procedure.
Background technology
Tradition bismuth smelts main employing " reverberatory furnace slightly refines-thick bismuth refining " technique, first bismuth-containing material thick refining in reverberatory furnace is formed and contains bismuth alloy, then carry out refining by operations such as " liquation decoppering, chlorination are except antimony ".In reverberatory furnace in smelting process, antimony difficulty is separated with bismuth.Market exists a large amount of containing high antimony, bismuth material, the grade of antimony is at 10-30%, and this kind of antimony bismuth material that contains directly enters reverberatory furnace operation, and produce thick bismuth, bismuth is difficult to effectively be separated with impurity antimony, copper, causes difficulty to traditional affinage metallurgy technique.After first such must remove a large amount of impurity antimony, copper containing high antimony, bismuth material, the thick bismuth of the high-quality obtained is conducive to producing smart bismuth product further.How to realize bismuth and the object being separated with reclaiming of impurity antimony, copper in raw material, directly obtain the higher thick bismuth of grade and available bismuth raw material, all belong to a difficult problem at home and abroad.For many years, Ge Bi producer adopts this material of traditional technology process always, directly carries out reduction smelting in reverberatory furnace obtain thick bismuth by this material, thick bismuth obtains 99.99% smart bismuth product through refining removal of impurities, and refining is except the antimony at substantial time, fuel consumption is large, and working cycle is long, and production efficiency is low.This technique is 10-30% due to the grade of antimony in material, causes antimony content in thick bismuth to reach 15-20%, and adopt traditional bismuth refinery practice energy consumption high, cost is high.
Summary of the invention
Object of the present invention aims to provide a kind of conventional metallurgical processes, directly processes high antimony bismuth-containing material, produces 75 ~ 85% thick bismuths and can for the bismuth raw material of smart bismuth production line refining procedure.
Technical scheme of the present invention is: a kind for the treatment of process of high antimony bismuth-containing material:
This technique specifically comprises the following steps:
Step 1. reduction smelting in reverberatory furnace:
Main containing Sb and a small amount of Cu impurity element in high antimony bismuth-containing material, high antimony bismuth-containing material and bismuth sulfide mix, join together with coke powder in reverberatory furnace with lime, soda ash, iron filings again, carry out retailoring, smelting temperature is 500-700 DEG C, smelting time 2-12 hour, after melting terminates, slagging-off, obtain thick bismuth, shoddye and dry slag, the antimony of the overwhelming majority, reach bismuth and impurity antimony, being effectively separated of copper, thick bismuth obtained smart bismuth after entering refining; Wherein, it is 10-20% that described bismuth sulfide add-on accounts for high antimony bismuth-containing material mass percent, it is 3-8% that described lime adding amount accounts for high antimony bismuth-containing material mass percent, it is 5-20% that described soda ash add-on accounts for high antimony bismuth-containing material mass percent, and it is 1-5% that described iron filings add-on accounts for high antimony bismuth-containing material mass percent;
Step 2. antimony recovery process:
It is in the liquid caustic soda of 20-60g/l that shoddye step 1 obtained is dissolved in concentration, is warming up to 85 DEG C, and reaction 2-8 hour, makes most of antimony sulfide enter in liquid phase, reach the object of Sb and other magazins' layout; Reaction formula is as follows:
Sb 2s 3ten 6H 20-2Sb (OH) 3ten 3H 2s
2Sb (OH) 3ten 2OH --2Sb0 2 -+ 4H 2o
3H 2s ten 6OH --3S 2-+ 6H 2o
Sb 2s 3ten S 2--2SbS 2 -
2SbS 2 -+ 2S 2-one 2SbS 3 2-
Net reaction is: Sb 2s 3ten 4OH --SbO 2 -ten SbS 3 3-+ 2H 2o
Step 3. neutralizes, oxidation operation:
After the pH value processing the liquid phase obtained through step 2 is adjusted to 4-7, be warming up to 40-85 DEG C, reaction 2-6 hour, pass into atmospheric oxidation and obtain thick sodium antimonate and can refine production sodium antimonate product further.
2Na 3SbS 3+7O 2+2NaOH+5H 2O =2NaSb(OH) 6+3Na 2S 2O 3
the invention has the beneficial effects as follows: owing to adopting technique scheme, the method utilizesin iron filings and raw material, bismuth is displaced bismuth with elementary by the bismuth generation replacement(metathesis)reaction of chemical combination state, and lime is because in raw material, moisture content reaches about 35%, and moisture content is too high directly to be entered reverberatory smelting and fryer can occur, therefore adds lime; Adding soda ash object is as material heat transfer meson, finally realize bismuth, antimony reverberatory furnace is directly separated, simultaneously except antimony process produces a large amount of bismuth scum silica frost, bismuth scum silica frost is carried bismuth secretly and is caused damage, and affects the rate of recovery,antimony, the bismuth rate of recovery all reach more than 95%.
Accompanying drawing explanation
Fig. 1 is technical process of the present invention.
Embodiment
Content of the present invention is set forth further below in conjunction with technical process accompanying drawing of the present invention and example.
Embodiment 1:
(1) reduction smelting in reverberatory furnace operation
Main containing Sb and a small amount of Cu impurity element in high antimony bismuth-containing material, high antimony bismuth-containing material and bismuth sulfide mix, join together with coke powder in reverberatory furnace with lime, soda ash, iron filings again, carry out retailoring, smelting temperature 500 DEG C, smelting time 2 hours, after melting terminates, slagging-off, obtain thick bismuth, shoddye and dry slag, for subsequent use; Wherein, it is 20% that described bismuth sulfide add-on accounts for high antimony bismuth-containing material mass percent, it is 8% that described lime adding amount accounts for high antimony bismuth-containing material mass percent, it is 20% that described soda ash add-on accounts for high antimony bismuth-containing material mass percent, and it is 5% that described iron filings add-on accounts for high antimony bismuth-containing material mass percent; After melting terminates, slagging-off, obtains thick bismuth, shoddye and dry slag.Reach bismuth and impurity antimony, being effectively separated of copper.
(2) antimony recovery process
Utilize antimony sulfide to be dissolved in the characteristic of highly basic, shoddye is dissolved in 20g/l liquid caustic soda, be warming up to 85 DEG C, react 2 hours, make most of antimony sulfide enter in liquid phase, reach the object of Sb and other magazins' layout.
Sb 2s 3ten 6H 20-2Sb (OH) 3ten 3H 2s
2Sb (OH) 3ten 2OH --2Sb0 2 -+ 4H 2o
3H 2s ten 6OH --3S 2-+ 6H 2o
Sb 2s 3ten S 2--2SbS 2 -
2SbS 2 -+ 2S 2-one 2SbS 3 2-
Net reaction is: Sb 2s 3ten 4OH --SbO 2 -ten SbS 3 3-+ 2H 2o
(3) neutralization, oxidation operation
The alkali lye that (2) obtained regulates pH value to be after 4, is warming up to 40 DEG C, react 2 hours, passes into atmospheric oxidation and obtains thick sodium antimonate and can refine production sodium antimonate product further.
2Na 3SbS 3+7O 2+2NaOH+5H 2O =2NaSb(OH) 6+3Na 2S 2O 3
Through above step, bismuth, antimony recovery all reach more than 95%.
Embodiment 2
(1) reduction smelting in reverberatory furnace operation
Main containing Sb and a small amount of Cu impurity element in high antimony bismuth-containing material, high antimony bismuth-containing material and bismuth sulfide mix, join together with coke powder in reverberatory furnace with lime, soda ash, iron filings again, carry out retailoring, smelting temperature 600 DEG C, smelting time 8 hours, after melting terminates, slagging-off, obtain thick bismuth, shoddye and dry slag, for subsequent use; Wherein, it is 15% that described bismuth sulfide add-on accounts for high antimony bismuth-containing material mass percent, it is 5% that described lime adding amount accounts for high antimony bismuth-containing material mass percent, it is 10% that described soda ash add-on accounts for high antimony bismuth-containing material mass percent, and it is 2.5% that described iron filings add-on accounts for high antimony bismuth-containing material mass percent; After melting terminates, slagging-off, obtains thick bismuth, shoddye and dry slag.Reach bismuth and impurity antimony, being effectively separated of copper.
(2) antimony recovery process
Utilize antimony sulfide to be dissolved in the characteristic of highly basic, shoddye is dissolved in 40g/l liquid caustic soda, be warming up to 85 DEG C, react 5 hours, make most of antimony sulfide enter in liquid phase, reach the object of Sb and other magazins' layout.
Sb 2s 3ten 6H 20-2Sb (OH) 3ten 3H 2s
2Sb (OH) 3ten 2OH --2Sb0 2 -+ 4H 2o
3H 2s ten 6OH --3S 2-+ 6H 2o
Sb 2s 3ten S 2--2SbS 2 -
2SbS 2 -+ 2S 2-one 2SbS 3 2-
Net reaction is: Sb 2s 3ten 4OH --SbO 2 -ten SbS 3 3-+ 2H 2o
(3) neutralization, oxidation operation
The alkali lye that (2) obtained regulates pH value to be after 5, is warming up to 60 DEG C, react 4 hours, passes into atmospheric oxidation and obtains thick sodium antimonate and can refine production sodium antimonate product further.
2Na 3SbS 3+7O 2+2NaOH+5H 2O =2NaSb(OH) 6+3Na 2S 2O 3
Through above step, bismuth, antimony recovery all reach more than 95%.
Embodiment 3
(1) reduction smelting in reverberatory furnace operation
Main containing Sb and a small amount of Cu impurity element in high antimony bismuth-containing material, high antimony bismuth-containing material and bismuth sulfide mix, join together with coke powder in reverberatory furnace with lime, soda ash, iron filings again, carry out retailoring, smelting temperature 700 DEG C, smelting time 12 hours, after melting terminates, slagging-off, obtain thick bismuth, shoddye and dry slag, for subsequent use; Wherein, it is 10% that described bismuth sulfide add-on accounts for high antimony bismuth-containing material mass percent, it is 3% that described lime adding amount accounts for high antimony bismuth-containing material mass percent, it is 5% that described soda ash add-on accounts for high antimony bismuth-containing material mass percent, and it is 1% that described iron filings add-on accounts for high antimony bismuth-containing material mass percent; After melting terminates, slagging-off, obtains thick bismuth, shoddye and dry slag.Reach bismuth and impurity antimony, being effectively separated of copper.
(2) antimony recovery process
Utilize antimony sulfide to be dissolved in the characteristic of highly basic, shoddye is dissolved in 60g/l liquid caustic soda, be warming up to 85 DEG C, react 8 hours, make most of antimony sulfide enter in liquid phase, reach the object of Sb and other magazins' layout.
Sb 2s 3ten 6H 20-2Sb (OH) 3ten 3H 2s
2Sb (OH) 3ten 2OH --2Sb0 2 -+ 4H 2o
3H 2s ten 6OH --3S 2-+ 6H 2o
Sb 2s 3ten S 2--2SbS 2 -
2SbS 2 -+ 2S 2-one 2SbS 3 2-
Net reaction is: Sb 2s 3ten 4OH --SbO 2 -ten SbS 3 3-+ 2H 2o
(3) neutralization, oxidation operation
The alkali lye that (2) obtained regulates pH value to be after 7, is warming up to 85 DEG C, react 6 hours, passes into atmospheric oxidation and obtains thick sodium antimonate and can refine production sodium antimonate product further.
2Na 3SbS 3+7O 2+2NaOH+5H 2O =2NaSb(OH) 6+3Na 2S 2O 3
Through above step, bismuth, antimony recovery all reach more than 95%.

Claims (1)

1. a treatment process for high antimony bismuth-containing material, is characterized in that, specifically comprise the following steps:
Step 1. reduction smelting in reverberatory furnace:
Main containing Sb and a small amount of Cu impurity element in high antimony bismuth-containing material, high antimony bismuth-containing material and bismuth sulfide mix, join together with coke powder in reverberatory furnace with lime, soda ash, iron filings again, carry out retailoring, smelting temperature is 500-700 DEG C, smelting time 2-12 hour, after melting terminates, and slagging-off, obtain thick bismuth, shoddye and dry slag, for subsequent use; Wherein, it is 10-20% that described bismuth sulfide add-on accounts for high antimony bismuth-containing material mass percent, it is 3-8% that described lime adding amount accounts for high antimony bismuth-containing material mass percent, it is 5-20% that described soda ash add-on accounts for high antimony bismuth-containing material mass percent, and it is 1-5% that described iron filings add-on accounts for high antimony bismuth-containing material mass percent;
Step 2. antimony recovery process:
It is in the liquid caustic soda of 20-60g/l that shoddye step 1 obtained is dissolved in concentration, is warming up to 85 DEG C, and reaction 2-8 hour, makes most of antimony sulfide enter in liquid phase, reach the object of Sb and other magazins' layout;
Step 3. neutralizes, oxidation operation:
After the pH value of liquid phase step 2 obtained is adjusted to 4-7, be warming up to 40-85 DEG C, reaction 2-6 hour, pass into atmospheric oxidation and obtain thick sodium antimonate and can refine production sodium antimonate product further.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101289710A (en) * 2008-06-16 2008-10-22 中南大学 Process for abstracting bismuth by low-temperature alkaline fusion metallurgy of bismuth clean ore
CN102534255A (en) * 2011-12-30 2012-07-04 中南大学 Wet-fire combined smelting process for antimony or bismuth

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* Cited by examiner, † Cited by third party
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JPH06322455A (en) * 1993-05-14 1994-11-22 Sumitomo Metal Mining Co Ltd Production of metallic antimony

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101289710A (en) * 2008-06-16 2008-10-22 中南大学 Process for abstracting bismuth by low-temperature alkaline fusion metallurgy of bismuth clean ore
CN102534255A (en) * 2011-12-30 2012-07-04 中南大学 Wet-fire combined smelting process for antimony or bismuth

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
江铜新材料公司铅铋复杂物料处理改扩建设计;李明等;《有色冶金设计与研究》;20100831;第31卷(第4期);第13-15页 *
锑铋复杂物料铋的回收;刘兰玲等;《铜业工程》;20110630(第3期);第31-33页 *

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Address after: 335400 No. 15 metallurgical Avenue, Yingtan, Jiangxi, Guixi

Patentee after: JIANGXI COPPER Corp.

Address before: 335424 Jiangxi Copper Corp, No. 15 metallurgy Road, Yingtan, Jiangxi, Guixi

Patentee before: JIANGXI COPPER Corp.