CN1310241A - Reduction and sulfonium making smelting process with non-ferrous sulfide ore and sulfide containing material - Google Patents
Reduction and sulfonium making smelting process with non-ferrous sulfide ore and sulfide containing material Download PDFInfo
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- CN1310241A CN1310241A CN 00113284 CN00113284A CN1310241A CN 1310241 A CN1310241 A CN 1310241A CN 00113284 CN00113284 CN 00113284 CN 00113284 A CN00113284 A CN 00113284A CN 1310241 A CN1310241 A CN 1310241A
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Abstract
Non-ferrous sulfide ore is first ground and mixed with sulfonium making agent, reductant and additive and the mixture is then sulfonium making smelted at 900-1300 deg.c. Without SO2 generated, the process smelts crude non-ferrous metal or alloy, sulfonium and smoke dust while recovering Au, Ag and other noble metals. The present invention has the advantages of simple process, high recovery rate, low cost, etc., and is suitable for no-pollution smelting of single or complex sulfide ore of Pb, Sb and Bi metals or the enriched sulfur-containing matter of the said metals, especially for recovering noble metals from gold containing pyrite sludge.
Description
The invention relates to pollution-free direct smelting of non-ferrous metal sulfide ore or concentrate.
The non-ferrous metal sulfide ore or the concentrate is desulfurized when being smelted into metal, and the problems of acid making or pollution caused by sulfur dioxide exist. The copper sulfide concentrate is smelted into matte through matte smelting and then is blown into blister copper, sulfur dioxide is generated in the matte smelting and the blowing processes, although most of the sulfur dioxide is used for preparing acid in copper smelting, the pollution problem is basically solved, and the matte smelting is difficult to treat copper-lead-zinc and copper-zinc complex sulfide ores; zinc sulfide concentrate is subjected to boiling roasting desulfurization to prepare acid, and roasted sand is refined into metal zinc by a wet method or a pyrogenic method; the complex sulfide ores of copper-zinc, lead-zinc and copper-lead-zinc are difficult to treat; sintering, roasting and desulfurizing the lead sulfide concentrate by a sintering pot or a belt sintering machine, and reducing and smelting a sinter cake into crude lead by a blast furnace; volatilizing and smelting antimony sulfide concentrate into crude antimony oxide in a blast furnace or an open hearth, and then reducing and smelting the crude antimony oxide in a reverberatory furnace to obtain crude antimony; the lead-antimony complex sulfide ore concentrate is firstly roasted by a fluidized bed furnace and sintered by a sintering disc for desulfurization, and then is reduced and smelted in a blast furnace to form lead-antimony alloy. The smelting of the lead and antimony single sulfide ores and lead-antimony complex sulfide oreconcentrates has the problems that a large amount of low-concentration sulfur dioxide flue gas cannot produce acid and pollutes the environment, and is an important pollution source for generating acid rain. The oldest method for directly smelting sulfide ore without sulfur dioxide emission is the precipitation smelting of antimony sulfide ore and bismuth sulfide ore, but the substitution agent adopted by the precipitation smelting is metallic iron or scrap iron, so that the cost is high, the technical and economic indexes are poor, and the method is not suitable for smelting lead sulfide concentrate and various complex sulfide ore concentrates. 94119758.1 patent application proposes "direct smelting of sulfide ore to prepare metal", the sulfur-fixing agent proposed by the patent application is oxides, hydroxides or carbonates of manganese, iron, calcium and magnesium, the concept is not clear, and if the sulfur-fixing agent is regarded as a pure substance, the sulfur-fixing agent has high cost and difficult source, and the treatment object is limited to only zinc, copper and lead sulfide ore.
The invention aims to provide a novel method for directly smelting non-ferrous metals from non-ferrous metal sulphide ore raw materials without sulfur dioxide pollution, so as to replace the traditional production process of non-ferrous metals such as lead, antimony and the like and solve the imminent pollution problem of a large amount of low-concentration sulfur dioxide flue gas.
The basic principle of the invention is that under the temperature of 900-1300 ℃ and the condition of excessive carbonaceous reducing agent, the high valence oxide in the sulfonium making agent is reduced to be low valence:
then FeO or Cu2O, non-ferrous metal sulfide and a carbonaceous reducing agent are subjected to reduction and sulfonium making reaction:
or (8)
Or (12)
Or (16)
Or (20)
The non-ferrous metal oxides are also reduced to metals.
The technical scheme adopted by the invention is as follows: grinding and uniformly mixing the sulfide ore or sulfide ore concentrate of the nonferrous metal or sulfur-containing concentrate of the sulfide ore or sulfide ore concentrate, a sulfonium making agent, a reducing agent and an additive, and then carrying out reduction matte making smelting at 900-1300 ℃, wherein the conditions are as follows: the sulfonium making agent accounts for 1.0-1.5 times of the theoretical amount; the reducing agent is 1.20-3.0 times of the theoretical amount; the additive accounts for 0.5-20% (wt.) of the furnace burden; the granularity of furnace charge is less than 1 mm; the smelting time is 10-90 minutes. The sulfonium making agent is pyrite cinder rich in iron oxide, in particular to pyrite cinder rich in gold, iron-rich cinder in hydrometallurgy, such as alum cinder, goethite cinder, hematite cinder and the like, iron oxide ores such as limonite, hematite, magnetite and the like, materials containing copper oxide, copper oxide ores and the like; the reducing agent is pulverized coal or coke powder, and the additives are soda and salt.
The raw materials treated by the invention comprise lead, antimony and bismuth single sulfide ore or sulfide ore concentrate, lead-antimony, lead-zinc, copper-lead-zinc and copper-zinc complex sulfide ore or concentrate and sulfur-containing concentrates thereof.
After the reduction matte smelting is finished, four products of crude metal (or alloy), matte, slag and smoke dust can be obtained, most of lead, antimony, bismuth and precious metal enter the crude metal (or alloy), a small part of lead, antimony and bismuth enter the smoke dust, a small part of lead, antimony and bismuth also remain in the matte and the slag, and most of copper, nickel and cobalt enter the matte; most of zinc and cadmium enter smoke dust; most of iron and calcium enter matte, a small part of the iron and calcium enter the matte to form slag, and alkali metals such as sodium and the like also enter the matte; the gangue such as silicon dioxide, alumina and the like enters the slag completely. If the zinc content of the smoke dust is low, the smoke dust is returned to reduction matte smelting, and if the zinc content of the smoke dust is high, the smoke dust needs to be additionally treated. The slag is a non-weathered glass body, is stable and can be stockpiled, paved or made into building materials for a long time. The treatment of the matte is important, and the main component of the matte is ferrous sulfide which is insoluble in water but easily soluble in acid, and is easily weathered. This matte is sent to chemical plants to produce sulfuric acid or used as a raw material for sulfidic chemicals after recovery of valuable metals. Most of the matte should be roasted, and the obtained slag is returned to the smelting plant as a matte-making agent. Therefore, the problems of the source and the cost of the matte making agent can be solved for a smelting plant, and the problems of the source of the sulfur raw material and the treatment and the utilization of the cinder can be solved for a chemical plant.
The method has the advantages of simple flow, low cost, less pollution and high metal recovery rate, and simultaneously solves the problems of treatment and utilization of waste residues such aspyrite cinder, wet-process metallurgical iron-rich slag and the like. The pyrite cinder of the nationwide chemical plant is piled up by thousands of tons, wherein, a lot of valuable metals such as gold, silver, cobalt, nickel and the like are contained, and the invention can make full use of the metal resources. The invention provides a technical guarantee for the development and utilization of the huge gold resource, the gold-containing pyrite is firstly roasted and desulfurized to prepare acid, the cinder of the acid is used as a sulfonium making agent for reduction sulfonium making and smelting of lead sulfide concentrate or lead-antimony complex sulfide concentrate, and gold can be enriched and recovered by the way. The method not only saves a large amount of investment in the construction of a calcine gold extraction production line in the traditional method, but also improves the gold recovery rate by more than or equal to 90 percent and by more than 10 percent compared with the roasting-cyaniding process.
The present invention will be described in detail below with reference to the accompanying drawings.
Description of the drawings:
FIG. 1: the principle flow chart of the invention.
Example (b):
1. the components (%) were: 195.60g of lead sulfide concentrate of Pb65.46, Zn7.52, S18.65, Fe4.24 and Ag0.17, 108.33g of pyrite cinder containing Fe52.6 percent, 25.34g of pulverized coal, 20g of soda and 4g of salt are mixed uniformly, placed in a graphite crucible, put into a furnace and heated to 1220 ℃ for smelting for 1h to obtain 114.50g of crude lead, and the block plumbum yield is 89.43 percent; slag 64.3g contains 0.5% lead; sulfonium 91.60g (containing 2.10% lead, 38.83% sulfur); calculating the total lead recovery rate to be 98.25 percent according to the slag and the matte; 8.82% of the sulfur enters smoke dust, and the sulfur fixing rate is 97.50%.
2. The components (%) were: sb29.76, Pb33.90, Fe5.40, S19.72, Ag0.10, SiO22.0,CaO1.44,Al2O30.34 g of Guangxi big factory jamesonite concentrate 200g, 123.43g of pyrite cinder (with the same components as 1), 32g of pulverized coal, 20g of soda and 4g of salt are mixed uniformly, put into a crucible and smelted for 0.75h at 1200 ℃; 116.80g of lead-antimony alloy is obtained, and the alloy direct yield is 91.74%; 16g of slag (containing 0.8% of lead and 0.5% of Sb0.5%), 171.6g of sulfonium (containing 2.30% of Pb2, 1.8% of Sb1 and 22.57%), and the total recovery rates of lead and antimony are 93.99% and 94.68% respectively and the sulfur fixing rate is 98.2% according to the calculation of the slag and the sulfonium.
3. The components (%) were: 200g of antimony sulfide concentrate containing Sb46.30, Pb1.90, Fe2.82, S22.11, Zn0.67 and Ag0.0065, 136g of cinder (the components are the same as 1), 35.52g of pulverized coal, 20g of soda and 4g of salt are uniformly mixed and put into a crucible, and the mixture is smelted for 0.5h at 1300 ℃; 91.5g of crude antimony, 95.23 percent of antimony block direct yield and 86.50g of slag (containing Sb0.25 percent); sulfonium 117.9g (containing Sb1.80%, S36.79%); the total recovery rate of antimony is calculated by slag and matte to be 97.47%, wherein 2.24% of antimony enters smoke dust, and the sulfur fixing rate is 98.1%.
4．The component (%) is Pb69.23 (wherein PbO)2Medium Pb20.07%), waste storage battery daub of S5.11 200g, cinder 36.26g (the same composition as 1), fine coal 43.10g, soda 14g and salt 4g are ground and mixed evenly, put into a crucible and smelted for 1.5h at 1200 ℃, thus obtaining crude lead 125.25g, block plumbum yield 90.46%, and matte 30.1g (containing Pb8.50%, S32.32%); calculated according to sulfonium, the total lead recovery rate is 98.15%, wherein 7.69% of lead enters smoke dust, and the sulfur fixing rate is 95.2%.
5. 195.6g of lead sulfide concentrate (the same components are 1), 104.55g of gold-containing pyrite cinder (the components (%): Fe54.5%, Au9g/t), 25.34g of pulverized coal, 20g of soda and 4g of salt are mixed uniformly, put into a crucible and smelted for 1h at 1250 ℃ to obtain 114.6g of noble lead, containing Au7.82g/t, the block plumbum yield is 89.5%, the gold capture rate is 95.24%, the slag is 60.3g (containing 0.34%), the sulfonium 105.2g (containing Pb2.34% and S34.14%), the total lead recovery rate is 97.92% calculated according to the slag and the sulfonium, wherein 8.42% enters the smoke dust, and the solid sulfonium rate is 98.15%.
Claims (6)
1. A reduction matte-making smelting method for non-ferrous metal sulfide ores and sulfur-containing materials is characterized in that: the invention carries out reduction matte smelting after grinding and mixing non-ferrous metal sulfide ore or sulfide ore concentrate or sulfur-containing concentrate of the non-ferrous metal sulfide ore or sulfide ore concentrate, a matte making agent, a reducing agent and an additive uniformly, and the process conditions are as follows: the matte making agent accounts for 1.0-1.5 times of theoretical amount, the reducing agent accounts for 1.2-3.0 times of theoretical amount, the additive accounts for 0.5-20% (wt.) of mineral raw materials, the granularity of furnace burden is less than 1mm, the smelting temperature is 900-1300 ℃, and the smelting time is 10-90 minutes.
2. The method according to claim 1, characterized in that the matte-making agent is iron oxide-rich pyrite cinder, in particular auriferous pyrite cinder, hydrometallurgical iron-rich cinder, such as alum cinder, goethite cinder, hematite cinder, etc., iron oxides, such as limonite, hematite and magnetite, as well as copper oxide-containing materials, copper oxide ores, etc.; the reducing agent is pulverized coal or coke powder, and the additives are soda and salt.
3. A method according to claim 1, characterized in that the matte is a matte with ferrous sulfide as the main component (and optionally a certain amount of non-ferrous sulfide), which is weatherable, but the main component is insoluble in water.
4. The method of claim 1, wherein the non-ferrous metal sulphide ore or sulphide ore concentrate is a single sulphide ore or concentrate of lead, antimony, bismuth, lead-antimony, lead-zinc, copper-zinc complex sulphide ore or concentrate, and the sulphur-containing concentrate of non-ferrous metals is a concentrate of lead, antimony, bismuth, zinc, copper sulphate, sulphide, such as waste battery slime, converter ash, lead sulphate slag, antimony sulphonium, etc.
5. A method according to claims 1 and 3, characterized in that the matte is sent to a chemical plant for the production of acid or used as a raw material for sulfidic chemicals, directly or after recovery of the valuable metal.
6. A method according to claims 1 and 3, characterized in that the matte is used as a matte-making agent for the acid-made clinker, which can be returned to the reduction matte smelting.
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| CN 00113284 CN1215184C (en) | 2000-02-22 | 2000-02-22 | Reduction and sulfonium making smelting process with non-ferrous sulfide ore and sulfide containing material |
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| CN 00113284 CN1215184C (en) | 2000-02-22 | 2000-02-22 | Reduction and sulfonium making smelting process with non-ferrous sulfide ore and sulfide containing material |
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| CN100496821C (en) * | 2005-12-08 | 2009-06-10 | 中国科学院过程工程研究所 | Preparation of metal silver powder by direct hydrogen reduction of silver sulfate in alkali water slurry |
| CN101979685A (en) * | 2010-10-23 | 2011-02-23 | 郴州市国大有色金属冶炼有限公司 | Iron-matte separation process for one-step lead smelting through reduced formation of matte |
| CN102154555A (en) * | 2011-03-01 | 2011-08-17 | 郴州市国大有色金属冶炼有限公司 | Blast furnace reduction matte smelting method and device for cleanly treating lead scraps |
| TWI402356B (en) * | 2007-05-24 | 2013-07-21 | Wurth Paul Sa | A method for recycling residues having an elevated content of zinc and sulfates |
| CN103243225A (en) * | 2013-05-16 | 2013-08-14 | 中南大学 | Method for selectively separating bismuth and lead in lead and bismuth concentrate by smelting in bath |
| CN104263933A (en) * | 2014-09-05 | 2015-01-07 | 昆明理工大学 | Wind coal converter and method for smelting brittle sulfur lead antimony ore by using same |
| CN104561519A (en) * | 2014-12-03 | 2015-04-29 | 金川集团股份有限公司 | Treatment method of high-magnesium noble metal concentrate |
| CN105543484A (en) * | 2016-03-02 | 2016-05-04 | 中南大学 | Method for treating waste lead-acid battery colloid sludge through zinc hydrometallurgy residues to recover lead and silver |
| CN105648233A (en) * | 2016-01-13 | 2016-06-08 | 江苏新春兴再生资源有限责任公司 | Smelting reduction method for secondary lead |
| CN105803224A (en) * | 2016-03-10 | 2016-07-27 | 中南大学 | One-step clean bismuth smelting method for complex bismuth sulfide ore |
| CN106244896A (en) * | 2016-08-29 | 2016-12-21 | 芜湖常瑞汽车部件有限公司 | Good automobile front lamp support of the big tensile strength of outer wall hardness and preparation method thereof |
| CN106756027A (en) * | 2016-12-06 | 2017-05-31 | 湖南工业大学 | A kind of method that Sb-Au ore and auriferous pyrite slag cooperate with melting concentration of valuable metals |
| CN107557597A (en) * | 2017-08-30 | 2018-01-09 | 长沙矿冶研究院有限责任公司 | A kind of method that antimony is smelted |
| CN108350523A (en) * | 2015-10-16 | 2018-07-31 | 弗朗西斯科·哈维尔·卡德纳斯·阿尔比托 | With direct-reduction process from the method for the sulphide concentrate extraction metal containing metal and regeneration and recycling reducing agent iron and fluxing agent sodium carbonate |
| CN109207726A (en) * | 2018-11-12 | 2019-01-15 | 锡矿山闪星锑业有限责任公司 | From low-grade containing the method for recycling antimony gold in golden antimony sulfide ore |
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2000
- 2000-02-22 CN CN 00113284 patent/CN1215184C/en not_active Expired - Fee Related
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100496821C (en) * | 2005-12-08 | 2009-06-10 | 中国科学院过程工程研究所 | Preparation of metal silver powder by direct hydrogen reduction of silver sulfate in alkali water slurry |
| TWI402356B (en) * | 2007-05-24 | 2013-07-21 | Wurth Paul Sa | A method for recycling residues having an elevated content of zinc and sulfates |
| CN101979685A (en) * | 2010-10-23 | 2011-02-23 | 郴州市国大有色金属冶炼有限公司 | Iron-matte separation process for one-step lead smelting through reduced formation of matte |
| CN102154555A (en) * | 2011-03-01 | 2011-08-17 | 郴州市国大有色金属冶炼有限公司 | Blast furnace reduction matte smelting method and device for cleanly treating lead scraps |
| CN102154555B (en) * | 2011-03-01 | 2013-01-23 | 郴州市国大有色金属冶炼有限公司 | Blast furnace reduction matte smelting method and device for cleanly treating lead scraps |
| CN103243225A (en) * | 2013-05-16 | 2013-08-14 | 中南大学 | Method for selectively separating bismuth and lead in lead and bismuth concentrate by smelting in bath |
| CN104263933A (en) * | 2014-09-05 | 2015-01-07 | 昆明理工大学 | Wind coal converter and method for smelting brittle sulfur lead antimony ore by using same |
| CN104561519A (en) * | 2014-12-03 | 2015-04-29 | 金川集团股份有限公司 | Treatment method of high-magnesium noble metal concentrate |
| CN108350523A (en) * | 2015-10-16 | 2018-07-31 | 弗朗西斯科·哈维尔·卡德纳斯·阿尔比托 | With direct-reduction process from the method for the sulphide concentrate extraction metal containing metal and regeneration and recycling reducing agent iron and fluxing agent sodium carbonate |
| CN105648233A (en) * | 2016-01-13 | 2016-06-08 | 江苏新春兴再生资源有限责任公司 | Smelting reduction method for secondary lead |
| CN105543484A (en) * | 2016-03-02 | 2016-05-04 | 中南大学 | Method for treating waste lead-acid battery colloid sludge through zinc hydrometallurgy residues to recover lead and silver |
| CN105803224A (en) * | 2016-03-10 | 2016-07-27 | 中南大学 | One-step clean bismuth smelting method for complex bismuth sulfide ore |
| CN106244896A (en) * | 2016-08-29 | 2016-12-21 | 芜湖常瑞汽车部件有限公司 | Good automobile front lamp support of the big tensile strength of outer wall hardness and preparation method thereof |
| CN106756027A (en) * | 2016-12-06 | 2017-05-31 | 湖南工业大学 | A kind of method that Sb-Au ore and auriferous pyrite slag cooperate with melting concentration of valuable metals |
| CN106756027B (en) * | 2016-12-06 | 2018-07-10 | 湖南工业大学 | A kind of method of Sb-Au ore and auriferous pyrite slag collaboration melting concentration of valuable metals |
| CN107557597A (en) * | 2017-08-30 | 2018-01-09 | 长沙矿冶研究院有限责任公司 | A kind of method that antimony is smelted |
| CN107557597B (en) * | 2017-08-30 | 2019-08-27 | 长沙矿冶研究院有限责任公司 | A kind of method that antimony is smelted |
| CN109207726A (en) * | 2018-11-12 | 2019-01-15 | 锡矿山闪星锑业有限责任公司 | From low-grade containing the method for recycling antimony gold in golden antimony sulfide ore |
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