CN101451185B - Comprehensive recovery method for ferro-sulphur ore containing copper, zinc and iron multi-metal - Google Patents

Comprehensive recovery method for ferro-sulphur ore containing copper, zinc and iron multi-metal Download PDF

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CN101451185B
CN101451185B CN2007101805718A CN200710180571A CN101451185B CN 101451185 B CN101451185 B CN 101451185B CN 2007101805718 A CN2007101805718 A CN 2007101805718A CN 200710180571 A CN200710180571 A CN 200710180571A CN 101451185 B CN101451185 B CN 101451185B
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zinc
copper
iron
extraction
ferro
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CN101451185A (en
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王安理
杨青时
李建政
刘晓勃
潘少华
范尚立
李满旺
王肖飞
宋宝启
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Lingbao Jinyuan Mining Co Ltd
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    • YGENERAL 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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    • Y02P10/20Recycling

Abstract

The invention discloses a method for comprehensively recovering polymetallic sulfurous iron ores containing copper, zinc and iron, which comprises the following steps: adding a strong inhibitor into the sulfurous iron ores first, controlling the pH value to be more than or equal to 11, adding a collector and a foaming agent into the mixture, and preferably performing flotation on copper and zinc; and activating tailings by an activator, adding the collector and the foaming agent into the tailings for floatation of sulfur, guaranteeing sulfur concentrate S is more than or equal to 47 percent, performing roasting, using flue gas to prepare a sulfuric acid, and directly using roasted sulfate slag to manufacture iron pellets. The method not only widens the application scope of copper-zinc bulk concentrate treatment grade but also recovers useful elements in the ores with low cost and high quality, not only recovers the copper with high yield but also recovers the zinc with high yield, avoids resource waste, greatly improves the surrounding environment, and eliminates zinc pollution. The tailings are activated by the activator, and the collector and the foaming agent are added into the tailings for flotation of the sulfur; the sulfur concentrate S is guaranteed to be more than or equal to 47 percent and roasted at a temperature of between 900 and 1,150 DEG C; the flue gas is used for preparing the sulfuric acid; and Fe in the roasted sulfate slag is more than or equal to 62 percent, and the roasted sulfate slag can be directly manufactured into the iron pellets which are then sold to iron mills, so that the aim of comprehensive recycle is achieved.

Description

The comprehensive recovering process of ferro-sulphur ore containing copper, zinc and iron multi-metal
Technical field
The present invention relates to a kind of many metals comprehensive recovering process, relate in particular to a kind of comprehensive recovering process of ferro-sulphur ore containing copper, zinc and iron multi-metal, belong to metallurgical technology field.
Background technology
Sulfurous iron ore is a kind of important minerals commonly used in chemical industry raw material, is mainly used in manufacturing sulfuric acid, and part is used for industrial chemicals to produce sulphur and various sulfocompounds etc.; In industry such as rubber, papermaking, weaving, food, match and agricultural, important use is arranged all; Particularly in the national defense industry in order to make various explosives, smoke producing agent etc.At present, the production of sulfurous iron ore all is to adopt high-sulfur iron (essence) ore deposit (sulphur content 〉=25%) direct roasting, flue gas is used to prepare sulfuric acid, and metals such as copper zinc-iron wherein become oxide compound through major part after the roasting, these oxide compounds are difficult to be reclaimed, the enterprise that has just directly abandons it, so not only causes metal loss, influences economic benefit, in addition, surrounding environment has also been caused pollution.
Summary of the invention
The object of the present invention is to provide a kind of comprehensive recovering process of ferro-sulphur ore containing copper, zinc and iron multi-metal, with many metals such as efficient recovery copper, zinc, iron.
To achieve these goals, technical scheme of the present invention has adopted a kind of comprehensive recovering process of ferro-sulphur ore containing copper, zinc and iron multi-metal, may further comprise the steps: will add potent inhibitor in the sulfurous iron ore earlier, with control pH 〉=11, add collecting agent and pore forming material, differential flotation copper zinc adopts wet method smelting process to reclaim copper zinc; Activated dose of activation of mine tailing adds collecting agent and pore forming material and carries out flotation sulphur, guarantees sulphur concentrate S 〉=47%, and then carry out roasting under 900-1150 ℃ temperature, and flue gas is used to prepare sulfuric acid, and Fe in the sulfate slag after the roasting 〉=62% directly is made into iron ball group.
Described potent inhibitor is a lime.
The collecting agent that adopts in the described Floatation of Copper zinc process is the ethyl thiourethane, and pore forming material is No. 2 oil, is preferably pine camphor oil.
The add-on of described ethyl thiourethane is 100-200g/t, and the add-on of No. 2 oil is 20-80g/t.
The step that described Wet-smelting method reclaims copper zinc is: with the copper zinc ore concentrate process sulfurization roasting earlier that flotation obtains, maturing temperature is 900-1150 ℃, and flue gas reclaims and is used to make sulfuric acid, and fired slags is containing H 2SO 4Concentration is to leach in the pickling tank of 1M,, the washing dense of the ore pulp after the leaching through thickener, it is standby that beneficial flow liquid flows into the coarse fodder pond, thickener underflow be pumped into the adhesive tape type filter filter, wash filtrate, the filter residue recovery; Coarse fodder liquid and filtrate obtain smart filtrate through the essence filter, and smart filtrate pump is sent into extraction plant, and the raffinate after the extraction of Lix84-1 type extraction agent is used to reclaim zinc, extraction liquid send electrodeposition workshop section, extraction liquid is through back extraction, and wherein, reverse-extraction agent is a cupric: 30-40g/L, the solution of sulfuric acid: 160-180g/L, after obtain rich copper electrode liquid, adopt the electrowinning with insoluble anode method to obtain cathode copper, wherein anode adopts the Pb alloy material, negative electrode is a copper starting sheet, and current density is 100-200A/m 2, bath voltage is 1.5-3V.The copper raffinate is with the alkali pH value removal of impurities when being 3-6 that neutralizes, obtain the zinc extraction liquid through the extraction of P17 type extraction agent then, the zinc extraction liquid is through back extraction, reverse-extraction agent is to contain zinc: 30-50g/L, and the solution of sulfuric acid: 130-140g/L obtains rich zinc electric effusion, adopt the electrowinning with insoluble anode method to obtain cathode zinc, wherein anode adopts the Pb alloy material, and negative electrode is a zinc beginning pole plate, and current density is 100-700A/m 2
Described activator is a sulfuric acid, and wherein activator vitriolic add-on is 1000-4000g/t.
The collecting agent that adds in the described mine tailing floatation process is a butyl xanthate, and pore forming material is No. 2 oil.
The add-on of described butyl xanthate is 50-200g/t, and the add-on of No. 2 oil is 20-80g/t.
Method of the present invention is to add potent inhibitor lime in sulphur iron (essence) ore deposit earlier, with control pH 〉=11, add collecting agent and pore forming material then, differential flotation copper zinc, Cu 〉=6% in the copper zinc ore concentrate of flotation, Zn 〉=6%), adopt wet method smelting process to reclaim copper zinc then, adopt method of the present invention not only to expand the scope of application of copper zinc mixing precision processing grade, reclaimed to low-cost and high-quality the useful element in the ore, promptly be recovered to copper with high yield, reclaim again and obtained zinc, avoid the wasting of resources, improved surrounding environment greatly, eliminated zinc pollution.Activated dose of activation of mine tailing, add collecting agent and pore forming material again and carry out flotation sulphur, guarantee sulphur concentrate S 〉=47%, and then carry out roasting at 900-1150 ℃, flue gas is used to prepare sulfuric acid, and Fe in the sulfate slag after the roasting 〉=62% can directly be made into iron ball group, be sold to iron work, reach the purpose of comprehensive reutilization.The present invention has good social benefit and economic benefit, is easy to apply.
Description of drawings
Fig. 1 is a process flow sheet of the present invention.
Embodiment
As shown in Figure 1, the polymetallic comprehensive recovering process of copper zinc-iron in the sulfurous iron ore of the present invention may further comprise the steps: add potent inhibitor lime in sulphur iron (essence) ore deposit earlier, with control pH 〉=11, add ethyl thiourethane (Z-200) again and make collecting agent, the add-on of collecting agent is 150g/t, add No. 2 oil and make pore forming material, wherein the add-on of No. 2 oil is 50g/t, differential flotation copper zinc, Cu 〉=6% in the copper zinc ore concentrate of flotation, Zn 〉=6%, adopt wet method smelting process to reclaim copper zinc, be specially: with the copper zinc ore concentrate process sulfurization roasting earlier that flotation obtains, maturing temperature is 1000 ℃, flue gas reclaims and is used to make sulfuric acid, and fired slags is containing H 2SO 4Concentration is to leach in the pickling tank of 1M,, the washing dense of the ore pulp after the leaching through thickener, it is standby that beneficial flow liquid flows into the coarse fodder pond, thickener underflow be pumped into the adhesive tape type filter filter, wash filtrate, the filter residue recovery; Coarse fodder liquid and filtrate obtain smart filtrate through the essence filter, and smart filtrate pump is sent into extraction plant, and the raffinate after the extraction of Lix84-1 type extraction agent is used to reclaim zinc, extraction liquid send electrodeposition workshop section, extraction liquid is through back extraction, and wherein, reverse-extraction agent is cupric 35g/L, the solution of sulfuric acid 170g/L, after obtain rich copper electrode liquid, adopt the electrowinning with insoluble anode method to obtain cathode copper, wherein anode adopts the Pb alloy material, negative electrode is a copper starting sheet, and current density is 150A/m 2, bath voltage is 1.5V.The copper raffinate is removal of impurities in 4 o'clock with the alkali pH value that neutralizes, obtain the zinc extraction liquid through the extraction of P17 type extraction agent then, the zinc extraction liquid is through back extraction, wherein reverse-extraction agent is to contain zinc 40g/L, and the solution of sulfuric acid 135g/L obtains rich zinc electric effusion, adopt the electrowinning with insoluble anode method to obtain cathode zinc, wherein anode adopts the Pb alloy material, and negative electrode is a zinc beginning pole plate, and current density is 500A/m 2
Mine tailing adopts sulfuric acid to make activator, and the vitriolic add-on is 2000g/t; Butyl xanthate is made collecting agent, and the add-on of butyl xanthate is 100g/t; No. 2 oil is made pore forming material, and the add-on of No. 2 oil is 50g/t, carries out flotation sulphur, guarantee S 〉=47% in the sulphur concentrate, and then carry out roasting under 1050 ℃ temperature, flue gas is used to prepare sulfuric acid, Fe in the sulfate slag after the roasting 〉=62% can directly be made into iron ball group, is sold to iron work.No. 2 oil in the present embodiment are pine camphor oil.
It should be noted last that: above embodiment is the unrestricted technical scheme of the present invention in order to explanation only, although the present invention is had been described in detail with reference to the foregoing description, those of ordinary skill in the art is to be understood that: still can make amendment or be equal to replacement the present invention, and not breaking away from any modification or partial replacement of the spirit and scope of the present invention, it all should be encompassed in the middle of the claim scope of the present invention.

Claims (7)

1. the comprehensive recovering process of a ferro-sulphur ore containing copper, zinc and iron multi-metal, it is characterized in that: may further comprise the steps:,, add collecting agent and pore forming material with control pH 〉=11 with adding potent inhibitor in the sulfurous iron ore earlier, differential flotation copper zinc adopts Wet-smelting method to reclaim copper zinc; Activated dose of activation of mine tailing adds collecting agent and pore forming material and carries out flotation sulphur, guarantees sulphur concentrate S 〉=47%, and then carry out roasting under 900-1150 ℃ temperature, and flue gas is used to prepare sulfuric acid, and Fe in the sulfate slag after the roasting 〉=62% directly is made into iron ball group; The step that Wet-smelting method reclaims copper zinc is: with the copper zinc ore concentrate process sulfurization roasting earlier that flotation obtains, maturing temperature is 900-1150 ℃, and flue gas reclaims and is used to make sulfuric acid, and fired slags is containing H 2SO 4Concentration is to leach in the pickling tank of 1M,, the washing dense of the ore pulp after the leaching through thickener, it is standby that beneficial flow liquid flows into the coarse fodder pond, thickener underflow be pumped into the adhesive tape type filter filter, wash filtrate, the filter residue recovery; Coarse fodder liquid and filtrate obtain smart filtrate through the essence filter, smart filtrate pump is sent into extraction plant, raffinate after the extraction of Lix84-1 type extraction agent is used to reclaim zinc, extraction liquid send electrodeposition workshop section, extraction liquid obtains rich copper electrode liquid after back extraction, adopt the electrowinning with insoluble anode method to obtain cathode copper, and wherein anode adopts the Pb alloy material, negative electrode is a copper starting sheet, and current density is 100-200A/m 2, bath voltage is 1.5-3V; The copper raffinate is with the alkali pH value removal of impurities when being 3-6 that neutralizes, obtain the zinc extraction liquid through the extraction of P17 type extraction agent then, the zinc extraction liquid obtains rich zinc electric effusion through back extraction, adopt the electrowinning with insoluble anode method to obtain cathode zinc, wherein anode adopts the Pb alloy material, negative electrode is a zinc beginning pole plate, and current density is 100-700A/m 2
2. the comprehensive recovering process of ferro-sulphur ore containing copper, zinc and iron multi-metal according to claim 1, it is characterized in that: described potent inhibitor is a lime.
3. the comprehensive recovering process of ferro-sulphur ore containing copper, zinc and iron multi-metal according to claim 1, it is characterized in that: the collecting agent that adopts in the described Floatation of Copper zinc process is the ethyl thiourethane, pore forming material is No. 2 oil.
4. the comprehensive recovering process of ferro-sulphur ore containing copper, zinc and iron multi-metal according to claim 3, it is characterized in that: the add-on of described ethyl thiourethane is 100-200g/t, the add-on of No. 2 oil is 20-80g/t.
5. the comprehensive recovering process of ferro-sulphur ore containing copper, zinc and iron multi-metal according to claim 1, it is characterized in that: described activator is a sulfuric acid, wherein activator vitriolic add-on is 1000-4000g/t.
6. the comprehensive recovering process of ferro-sulphur ore containing copper, zinc and iron multi-metal according to claim 1, it is characterized in that: the collecting agent that adds in the described mine tailing floatation process is a butyl xanthate, pore forming material is No. 2 oil.
7. the comprehensive recovering process of ferro-sulphur ore containing copper, zinc and iron multi-metal according to claim 6, it is characterized in that: the add-on of described butyl xanthate is 50-200g/t, the add-on of No. 2 oil is 20-80g/t.
CN2007101805718A 2007-11-28 2007-11-28 Comprehensive recovery method for ferro-sulphur ore containing copper, zinc and iron multi-metal Active CN101451185B (en)

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CN102534188B (en) * 2012-01-20 2013-10-16 个旧市富祥工贸有限责任公司 Method for producing iron pellet with sulfur acid residue containing large contents of impurities and enriching valuable metal
CN103506223B (en) * 2012-06-20 2016-01-20 鞍钢股份有限公司 The selecting smelting combination processing method of iron ore
CN102824962B (en) * 2012-09-17 2015-03-04 株洲市兴民科技有限公司 Reagent formula used for zinc leaching residue floatation process and application method of reagent formula
CN104028367A (en) * 2013-03-05 2014-09-10 中国科学院广州地球化学研究所 Process for recycling sulfur and iron resources in copper and sulfur tailings
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CN104561564A (en) * 2014-12-27 2015-04-29 长安大学 Method for recovering copper, silver and iron from wet zinc smelting rotary kiln slag
CN106591593B (en) * 2016-11-23 2018-11-27 昆明理工大学 A method of zinc is recycled in synchronous flotation-sulfating roasting containing zinc resource
CN109261371A (en) * 2018-08-01 2019-01-25 昆明理工大学 A kind of pyritic activation method
CN110117720B (en) * 2019-05-17 2020-05-22 中南大学 Method for comprehensively extracting valuable metals from sulfate slag through phosphorylation roasting, leaching and extraction
CN112517223B (en) * 2020-10-27 2022-11-08 西北矿冶研究院 Enrichment method of low-quality copper-zinc bulk concentrate

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