WO2023005404A1 - 低冰镍浸出提取有价金属及硫元素的方法 - Google Patents

低冰镍浸出提取有价金属及硫元素的方法 Download PDF

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WO2023005404A1
WO2023005404A1 PCT/CN2022/096304 CN2022096304W WO2023005404A1 WO 2023005404 A1 WO2023005404 A1 WO 2023005404A1 CN 2022096304 W CN2022096304 W CN 2022096304W WO 2023005404 A1 WO2023005404 A1 WO 2023005404A1
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reaction
nickel
low
leaching
nickel matte
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English (en)
French (fr)
Inventor
余海军
谢英豪
李爱霞
张学梅
李长东
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Hunan Brunp Recycling Technology Co Ltd
Guangdong Brunp Recycling Technology Co Ltd
Hunan Bangpu Automobile Circulation Co Ltd
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Hunan Brunp Recycling Technology Co Ltd
Guangdong Brunp Recycling Technology Co Ltd
Hunan Bangpu Automobile Circulation Co Ltd
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Publication of WO2023005404A1 publication Critical patent/WO2023005404A1/zh
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/006—Wet processes
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B17/00—Sulfur; Compounds thereof
    • C01B17/02—Preparation of sulfur; Purification
    • C01B17/06—Preparation of sulfur; Purification from non-gaseous sulfides or materials containing such sulfides, e.g. ores
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G3/00—Compounds of copper
    • C01G3/12—Sulfides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/10—Sulfates
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B15/00—Obtaining copper
    • C22B15/0063—Hydrometallurgy
    • C22B15/0065—Leaching or slurrying
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B23/00—Obtaining nickel or cobalt
    • C22B23/04—Obtaining nickel or cobalt by wet processes
    • C22B23/0407—Leaching processes
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B23/00—Obtaining nickel or cobalt
    • C22B23/04—Obtaining nickel or cobalt by wet processes
    • C22B23/0453—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B23/0461—Treatment or purification of solutions, e.g. obtained by leaching by chemical methods
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B23/00—Obtaining nickel or cobalt
    • C22B23/04—Obtaining nickel or cobalt by wet processes
    • C22B23/0476—Separation of nickel from cobalt
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Definitions

  • the invention belongs to the technical field of metallurgy, and in particular relates to a method for extracting valuable metals and sulfur elements by leaching low nickel matte.
  • Low nickel matte is an intermediate product of matte smelting in the traditional pyrometallurgy process. Because the composition of the low nickel matte obtained by matte smelting is not enough to meet the treatment requirements of the refining process, it needs to be further blown into high nickel matte. In the process of blowing low nickel matte into high nickel matte, the temperature of the converter needs to reach 1200-1300°C, and the blowing time is as long as 8-10 hours. Most of Co and some Ni and Cu will be oxidized together with iron to form converter slag, resulting in The waste of resources, and the blowing process is lengthy and complicated, the energy consumption is large, and the pollution is serious.
  • low-matte nickel has the advantages of enrichment of target metals and less gangue phase. Taking low-matte nickel as the starting point of the research object can not only simplify the process flow, but also avoid the process of blowing. Loss of nickel, cobalt, etc.
  • the main constituent phases in nickel matte are some sulfides and their sulfide solid solutions, such as FeNi alloy, FeS, Fe 3 O 4 , Cu 5 FeS 4 , Ni 3 S 2 , Cu 2 S, (Fe,Ni) 9 S 8 , etc., is a substance with a relatively complex composition.
  • the wet treatment methods for low nickel matte at home and abroad are mostly high-pressure acid leaching, high-pressure ammonia leaching and chloride leaching.
  • the chlorine gas used in chlorination leaching is harmful to the human body and the environment; while acid leaching and ammonia leaching require high temperature and pressure, high energy consumption and certain safety hazards.
  • Acid leaching is easy to form a sulfur passivation layer during the leaching process, which hinders the reaction, resulting in a low leaching rate of valuable metals such as Ni, Cu, and Co; ammonia leaching has a good effect on the selective leaching of valuable metals, but requires a higher temperature
  • the leaching rate can only be improved under high pressure and pressure, and has the disadvantages of consuming a large amount of ammonia in the process and difficult recovery of precious metals, etc., so it is rarely used at present.
  • the related technology discloses a method for selectively leaching iron from low nickel matte.
  • the method uses hydrogen sulfide-sulfuric acid combined leaching, and uses a closed reactor to keep the leaching process in a hydrogen sulfide environment with a certain pressure, so as to realize iron in low nickel matte.
  • Iron is selectively leached by sulfuric acid, and the iron content in the leaching slag is less than 4%, and a nickel-copper-cobalt matte similar to high nickel matte is obtained, which can be directly incorporated into the existing production process.
  • the leachate mainly contains ferrous iron and enters the iron removal system. Materials are recycled repeatedly, and the recovery rate of valuable metals, especially cobalt, is greatly improved.
  • the direct recovery rate of nickel and cobalt can reach more than 98%, and the recovery rate of copper can reach more than 99.5%.
  • this invention requires pressurization and the use of hydrogen sulfide, the production conditions are harsh and there are safety hazards.
  • the present invention aims to solve at least one of the technical problems in the above-mentioned prior art. For this reason, the present invention proposes a method for extracting valuable metals and sulfur elements by leaching low-matte nickel, through oxidizing and leaching valuable metal elements in low-matte nickel, only a small amount of ferric salt is consumed, and the sulfur is converted into elemental sulfur
  • the method has the advantages of short process flow and low production cost.
  • a kind of low matte nickel leaching method for extracting valuable metals and sulfur elements comprising the following steps:
  • iron in low nickel matte is leached and then oxidized to form iron hydroxide, which only consumes water and oxygen, while ferric iron is only consumed when leaching nickel, copper, and cobalt metal ions, and the content of iron in low nickel matte is relatively high , while the content of other metal elements is relatively small.
  • the use of acid is omitted, the generation of hydrogen gas is avoided, and the leaching of aluminum and magnesium is also avoided.
  • the sulfur element produced by the reaction is dissolved in an organic solvent to avoid the formation of a passivation layer to hinder the reaction.
  • the particle size of the low nickel matte pulverized material is ⁇ 200 mesh. Facilitate the subsequent reaction.
  • the concentration of iron ions in the ferric salt solution is 0.1-5.5 mol/L.
  • the ferric salt solution is selected from one or more of ferric chloride, ferric sulfate or ferric nitrate.
  • the organic solvent is carbon disulfide, carbon tetrachloride, methylcyclohexane, trichloroethane, trichloroethylene, tetrachloroethane, diglyme, tetrahydro One or more of naphthalene or decahydronaphthalene.
  • the solid-to-liquid ratio of the low nickel matte crushed material, the ferric salt solution, and the organic solvent is 1 g: (1.5-50) mL: (1.0-30) mL.
  • the reaction temperature is 80-120° C.; preferably, the reaction time is 0.5-10 h.
  • elemental sulfur is easily soluble in organic solvents. Under the action of organic solvents, the oxidative properties of elemental sulfur can be improved, and the insoluble cuprous sulfide can be oxidized to copper sulfide, thereby promoting the oxidation leaching reaction.
  • water and ferric salt are added to the reaction system every 20-60 minutes to maintain the concentration of ferric ions in the water phase at 0.1-5.5 mol/L.
  • ferric iron and water are added to the reaction system every 20-60 minutes to maintain the concentration of ferric ions in the water phase at 0.1-5.5 mol/L.
  • a condenser is arranged above the reaction vessel used in the reaction, and the volatilized organic solvent is condensed and refluxed into the reaction system through the condenser.
  • the oxidizing gas is at least one of air or oxygen. Low cost, hardly soluble in organic solvents, and does not react with organic solvents.
  • the solid slag layer is washed to obtain iron red.
  • an oxidizing agent is added to the water layer to adjust the pH to 3.2-5, and solid-liquid separation is performed to obtain ferric hydroxide precipitate and filtrate. Adding an oxidizing agent makes all the iron in the water layer exist in the form of ferric ions. Further, the oxidant is selected from one or more of chlorine, hydrogen peroxide or nitric acid.
  • hydrogen sulfide gas is passed into the filtrate, and the pH of the filtrate is controlled to be 0-2.0, and solid-liquid separation is performed to obtain a copper sulfide precipitate and a nickel-containing filtrate.
  • the nickel-containing filtrate is added to the nickel-containing filtrate to extract nickel, and after static separation, the nickel-containing extraction organic phase and the cobalt-containing raffinate are obtained, and the nickel is back-extracted from the nickel-containing extraction organic phase with sulfuric acid solution , to obtain nickel sulfate solution.
  • the concentration of the sulfuric acid solution is 3-5 mol/L.
  • the extractant is selected from one or more of P204, P507, DEHPA or Cyanex272.
  • the organic layer is evaporated, condensed, and separated to obtain sulfur and an organic solvent.
  • the present invention oxidizes and leaches low-matte nickel through the oxidation of ferric ions.
  • the iron in low-matte nickel is oxidized to form ferric hydroxide after leaching, only water and oxygen are consumed, while ferric iron only Consumed during the leaching of nickel, copper, and cobalt metal ions, the content of iron in low-matte nickel is relatively high, and the content of other metal elements is relatively small; at the same time, the use of acid is omitted, the generation of hydrogen, and the generation of aluminum and magnesium are also avoided.
  • the elemental sulfur produced by the reaction is dissolved in an organic solvent to avoid the formation of a passivation layer to hinder the progress of the reaction; after the reaction, the solid slag layer can be used as iron red to make iron, the organic layer can be condensed to recover the organic solvent and produce sulfur, and the water layer
  • the invention has a short technological process, can react under normal pressure, has low requirements on equipment, low production cost, saves the blowing process of high-grade nickel matte as an intermediate product, avoids waste of valuable metals, saves auxiliary materials, and reduces investment Cost, suitable for industrialization promotion.
  • Fig. 1 is the structural representation of the reaction equipment used in the present invention.
  • reaction vessel 100 stirring blade 200 , condenser 300 .
  • Raw material pretreatment crush 100g of low-matte nickel into powder or granular form, and pass through a sieve size standard of not higher than 200 mesh after the low-matte nickel is crushed;
  • step (3) Separation treatment: after the reaction in step (2) finishes, separate the materials after standing to obtain a solid slag layer, an organic layer and a water layer; the obtained solid slag layer is washed to obtain the product iron red; the organic layer is evaporated and condensed, Separation to obtain the product sulfur and organic solvent; pass chlorine gas into the water layer for oxidation, so that all the iron in the water layer exists in the form of ferric ions, and adjust the pH to 3.2-4, solid-liquid separation to obtain ferric hydroxide Precipitation and filtrate; pass hydrogen sulfide gas into the filtrate, and control the pH of the filtrate to 1.0-2.0, and separate the solid and liquid to obtain copper sulfide precipitation and nickel-containing filtrate; use the mixture of P204 and P507 as the extraction agent to extract the nickel-containing filtrate , to obtain the nickel-containing extraction organic phase and the cobalt-containing raffinate after standing and separating, and back-extract the nickel from the nickel-containing extraction organic phase
  • iron red in iron 60.02g after reaction is completed, sulfur 24.03g, copper sulfide (in copper) 8.55g, nickel sulfate (in nickel) 20.83g, raffinate (in cobalt) 0.73g, by It can be seen that the leaching rate of nickel is 99.28%, the leaching rate of cobalt is 96.05%, the leaching rate of copper is 95.32%, and the recovery rate of sulfur is 98.7%.
  • the reaction equipment used in this embodiment is shown in FIG. 1 , including a reaction vessel 100 , a stirring blade 200 and a condenser 300 .
  • Raw material pretreatment crush 100g of low-matte nickel into powder or granule, and pass through the sieve size standard of not higher than 200 mesh after low-matte nickel is crushed;
  • Oxidative leaching adding 1000mL ferric ion concentration to ferric sulfate of 2.0mol/L and 3000mL carbon tetrachloride organic solvent in step (1) gained pulverized material, in the state of constantly stirring, blow into oxygen from the bottom, and Control the reaction temperature to 120°C, the reaction time to 6h, add water and ferric salt to the reaction system every 30min, and maintain the concentration of ferric ion in the water phase at 2.0-2.5mol/L;
  • step (3) Separation treatment: after the reaction in step (2) finishes, separate the materials after standing to obtain a solid slag layer, an organic layer and a water layer; the obtained solid slag layer is washed to obtain the product iron red; the organic layer is evaporated and condensed, Separation to obtain the product sulfur and organic solvent; add hydrogen peroxide to the water layer for oxidation, so that all the iron in the water layer exists in the form of ferric ions, and adjust the pH to 4.0-4.5, solid-liquid separation to obtain hydrogen oxidation Iron precipitation and filtrate; pass hydrogen sulfide gas into the filtrate, and control the pH of the filtrate to 0.5-1.5, separate the solid and liquid to obtain copper sulfide precipitation and nickel-containing filtrate, use Cyanex272 as the extraction agent, extract the nickel-containing filtrate, and let stand After separation, a nickel-containing extraction organic phase and a cobalt-containing raffinate are obtained, and nickel is back-extracted from the nickel-containing extraction organic phase with
  • Raw material pretreatment crush 100g of low-matte nickel into powder or granular form, and pass through a sieve size standard of not higher than 200 mesh after the low-matte nickel is crushed;
  • step (3) Separation treatment: after the reaction in step (2) finishes, separate the materials after standing to obtain a solid slag layer, an organic layer and a water layer; the obtained solid slag layer is washed to obtain the product iron red; the organic layer is evaporated and condensed, Separation to obtain the product sulfur and organic solvent; add nitric acid to the water layer for oxidation, so that all the iron in the water layer exists in the form of ferric ions, and adjust the pH to 4-5, solid-liquid separation to obtain ferric hydroxide precipitation and filtrate; feed hydrogen sulfide gas into the filtrate, and control the pH of the filtrate to be 0-1.0, solid-liquid separation to obtain copper sulfide precipitation and nickel-containing filtrate, use the mixture of P507 and Cyanex272 as the extraction agent to extract the nickel-containing filtrate, After static separation, the nickel-containing extraction organic phase and the cobalt-containing raffinate are obtained, and the nickel is back-extracted from the nickel-containing extraction organic phase

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Abstract

本发明公开了一种低冰镍浸出提取有价金属及硫元素的方法，向低冰镍粉碎料中加入三价铁盐溶液和有机溶剂，在搅拌状态下通氧化性气体进行反应，反应结束分离出固体渣层、有机层和水层。本发明通过三价铁离子的氧化性对低冰镍进行氧化浸出，整个反应过程中，低冰镍中的铁浸出后又被氧化形成氢氧化铁，仅消耗水和氧气，而三价铁仅在浸出镍、铜、钴金属离子时消耗，反应生成的硫单质经有机溶剂溶解，避免形成钝化层阻碍反应的进行；本发明工艺流程短，在常压下即可反应，对设备要求低，生产成本低，省去了中间品高冰镍的吹炼工艺，避免了有价金属的浪费，节省辅料的同时，降低了投资成本，适合工业化推广。

Description

低冰镍浸出提取有价金属及硫元素的方法 技术领域
本发明属于冶金技术领域，具体涉及一种低冰镍浸出提取有价金属及硫元素的方法。
背景技术
低冰镍是传统火法冶炼工艺中造锍熔炼的中间产物，因造锍熔炼获得的低镍锍在成分上不足以满足精炼工序的处理要求，需要将其进一步吹炼成高冰镍。在低冰镍吹炼成高冰镍的过程中，转炉温度需要达到1200-1300℃，吹炼时间长达8-10h，大部分Co及部分Ni和Cu会伴随铁一起氧化造渣形成转炉渣，造成资源的浪费，且吹炼工艺冗长复杂，能耗较大，污染严重。另一方面，低冰镍与原矿相比，具有目标金属富集，含有脉石相少等优点，以低冰镍作为研究对象的起点，不仅可以简化工艺流程，而且也避免了吹炼过程中镍、钴等的损失。
因此，探索寻找湿法处理低冰镍方法代替火法吹炼工艺以提高金属回收率是一个技术难点。
低冰镍中主要组成物相为一些硫化物及其硫化物固溶体，如FeNi合金、FeS、Fe 3O 4、Cu 5FeS 4、Ni 3S 2、Cu 2S、(Fe,Ni) 9S 8等，是一种成分较为复杂的物质。目前，国内外对于低冰镍的湿法处理多为高压酸浸、高压氨浸和氯化浸出。其中，氯化浸出采用的氯气对人体和环境有害；而酸浸和氨浸需要高温加压，能耗高且存在一定的安全隐患。酸浸在浸出过程中容易生成硫钝化层，阻碍反应的进行，导致Ni、Cu、Co等有价金属浸出率低；氨浸对于有价金属选择性浸出效果好，但需要在较高温度和压力下才能提升浸出率，且具有过程消耗大量的氨、贵金属难以回收等缺点，目前应用较少。
相关技术公开了一种低冰镍中选择性浸出铁的方法，该方法采用硫化氢-硫酸联合浸出，利用密闭反应釜保持浸出过程在一定压力的硫化氢环境中进行，实现低冰镍中的铁被硫酸选择性浸出，浸出渣中铁含量小于4％，得到类似高冰镍的镍铜钴锍，可直接并入现有生产流程，浸出液中主要含二价铁，进入除铁系统，整个过程中无物料反复循环，且有价金属尤其是钴回收率大大提高，镍、钴直收率可达到98％以上，铜回收率达 到99.5％以上。然而，该发明需要加压并采用硫化氢，生产条件苛刻且存在安全隐患。
还有相关技术公开了一种低冰镍盐化焙烧-水浸同步提取镍、铜、钴及制备镍钴锰酸锂正极材料的方法，通过低冰镍盐化焙烧-水浸同步提取镍、铜以及钴，实现绿色短流程化学工艺，同时，通过硫化钠除去浸出液中的铜元素，以含有镍钴元素的浸出液为原料制备镍钴锰酸锂正极材料。然而，该方法需在500℃以上的温度下进行焙烧，工艺条件苛刻，能耗大。
发明内容
本发明旨在至少解决上述现有技术中存在的技术问题之一。为此，本发明提出一种低冰镍浸出提取有价金属及硫元素的方法，通过氧化浸出低冰镍中的有价金属元素，仅消耗少量三价铁盐，且将硫以单质硫磺的形式分离出，该方法具有工艺流程短、生产成本低等优势。
根据本发明的一个方面，提出了一种低冰镍浸出提取有价金属及硫元素的方法，包括以下步骤：
向低冰镍粉碎料中加入三价铁盐溶液和有机溶剂，在搅拌状态下通氧化性气体进行反应，反应结束分离出固体渣层、有机层和水层。
反应体系中发生如下反应：
FeS+2Fe 3+＝＝3Fe 2++S；
Fe+2Fe 3+＝＝3Fe 2+；
Ni+2Fe 3+＝＝2Fe 2++Ni 2+；
NiS+2Fe 3+＝＝2Fe 2++Ni 2++S；
Ni 3S 2+6Fe 3+＝＝6Fe 2++3Ni 2++2S；
CuS+2Fe 3+＝＝2Fe 2++Cu 2++S；
Cu 2S+4Fe 3+＝＝4Fe 2++2Cu 2++S；
CoS+2Fe 3+＝＝2Fe 2++Co 2++S；
12Fe 2++3O 2+6H 2O＝＝8Fe 3++4Fe(OH) 3。
整个过程中，低冰镍中的铁浸出后又被氧化形成氢氧化铁，仅消耗水和氧气，而三 价铁仅在浸出镍、铜、钴金属离子时消耗，低冰镍中铁含量较高，而其它金属元素含量较少。同时，省去了酸的使用，避免了氢气的产生，也避免了铝、镁的浸出。反应生成的硫单质经有机溶剂溶解，避免形成钝化层阻碍反应的进行。
在本发明的一些实施方式中，所述低冰镍粉碎料的粒径≤200目。利于后续反应的进行。
在本发明的一些实施方式中，所述三价铁盐溶液中铁离子的浓度为0.1-5.5mol/L。进一步地，所述三价铁盐溶液选自氯化铁、硫酸铁或硝酸铁中的一种或几种。
在本发明的一些实施方式中，所述有机溶剂为二硫化碳、四氯化碳、甲基环己烷、三氯乙烷、三氯乙烯、四氯乙烷、二甘醇二甲醚、四氢萘或十氢萘的一种或几种。
在本发明的一些实施方式中，所述低冰镍粉碎料、三价铁盐溶液、有机溶剂的固液比为1g：(1.5-50)mL：(1.0-30)mL。
在本发明的一些实施方式中，所述反应的温度为80-120℃；优选的，所述反应的时间为0.5-10h。在该反应温度下，硫单质极易溶于有机溶剂，在有机溶剂的作用下，可提高硫单质的氧化性，使难溶解的硫化亚铜氧化为硫化铜，从而促进氧化浸出反应的进行。
在本发明的一些实施方式中，在所述反应的过程中，每20-60min向反应体系中补加一次水和三价铁盐，维持三价铁离子在水相中的浓度为0.1-5.5mol/L。通过向体系中投加三价铁和水，维持三价铁离子在水相中的浓度，保证反应的正常进行。
在本发明的一些实施方式中，所述反应所采用的反应容器上方设有冷凝器，挥发出的有机溶剂经冷凝器冷凝回流至反应体系。
在本发明的一些实施方式中，所述氧化性气体为空气或氧气中的至少一种。成本低，既难溶于有机溶剂，也不与有机溶剂反应。
在本发明的一些实施方式中，所述固体渣层经洗涤后得到铁红。
在本发明的一些实施方式中，向所述水层中加入氧化剂，调节pH至3.2-5，固液分离得到氢氧化铁沉淀和滤液。加入氧化剂使水层中的铁全部以三价铁离子的形式存在。进一步地，所述氧化剂选自氯气、过氧化氢或硝酸中的一种或几种。
在本发明的一些实施方式中，向所述滤液中通入硫化氢气体，并控制滤液的pH为0-2.0，固液分离得到硫化铜沉淀和含镍滤液。
在本发明的一些实施方式中，所述含镍滤液加入萃取剂萃取镍，静置分离后得到含镍萃取有机相和含钴萃余液，用硫酸溶液从含镍萃取有机相中反萃取镍，得到硫酸镍溶液。
在本发明的一些实施方式中，所述硫酸溶液的浓度为3-5mol/L。
在本发明的一些实施方式中，所述萃取剂选自P204、P507、DEHPA或Cyanex272中的一种或几种。
在本发明的一些实施方式中，所述有机层经蒸发冷凝，分离，得到硫磺和有机溶剂。
根据本发明的一种优选的实施方式，至少具有以下有益效果：
本发明通过三价铁离子的氧化性对低冰镍进行氧化浸出，整个反应过程中，低冰镍中的铁浸出后又被氧化形成氢氧化铁，仅消耗水和氧气，而三价铁仅在浸出镍、铜、钴金属离子时消耗，低冰镍中铁含量较高，而其它金属元素含量较少；同时，省去了酸的使用，避免了氢气的产生，也避免了铝、镁的浸出；反应生成的硫单质经有机溶剂溶解，避免形成钝化层阻碍反应的进行；反应结束后，固体渣层作为铁红可以炼铁，有机层可冷凝回收有机溶剂并制得硫磺，水层通过氧化、除铁、沉铜、萃取分离镍钴，使低冰镍中的有价金属充分得到了利用。本发明工艺流程短，在常压下即可反应，对设备要求低，生产成本低，省去了中间品高冰镍的吹炼工艺，避免了有价金属的浪费，节省辅料的同时，降低了投资成本，适合工业化推广。
附图说明
下面结合附图和实施例对本发明做进一步的说明，其中：
图1为本发明使用的反应设备的结构示意图。
附图标记：反应容器100、搅拌浆200、冷凝器300。
具体实施方式
以下将结合实施例对本发明的构思及产生的技术效果进行清楚、完整地描述，以充分地理解本发明的目的、特征和效果。显然，所描述的实施例只是本发明的一部分实施 例，而不是全部实施例，基于本发明的实施例，本领域的技术人员在不付出创造性劳动的前提下所获得的其他实施例，均属于本发明保护的范围。
实施例1
一种低冰镍浸出提取有价金属及硫元素的方法，低冰镍成份：镍20.98％、铜8.97％、钴0.76％、铁41.29％、硫24.35％，通过如下步骤提取有价金属及硫元素：
(1)原料预处理：将100g低冰镍破碎成粉状或颗粒状，低冰镍破碎后通过筛孔尺寸标准不高于200目；
(2)氧化浸出：向步骤(1)所得粉碎料中加入400mL铁离子浓度为1.0mol/L的氯化铁和100mL二硫化碳有机溶剂，在不断搅拌的状态下由底部鼓入空气，并控制反应温度为100℃，反应时间为5h，每40min向反应体系中补加水和三价铁盐，维持三价铁离子在水相中的浓度为1.0-1.5mol/L；
(3)分离处理：步骤(2)反应结束后，静置后分离物料，得到固体渣层、有机层和水层；得到的固体渣层经洗涤后得到产品铁红；有机层经蒸发冷凝，分离，得到产品硫磺和有机溶剂；向水层中通入氯气进行氧化，使水层中的铁全部以三价铁离子的形式存在，并调节pH至3.2-4，固液分离得到氢氧化铁沉淀和滤液；向滤液中通入硫化氢气体，并控制滤液pH为1.0-2.0，固液分离得到硫化铜沉淀和含镍滤液；使用P204、P507的混合物作为萃取剂，对含镍滤液进行萃取，静置分离后得到含镍萃取有机相和含钴萃余液，用5mol/L的硫酸溶液从含镍萃取有机相中反萃取镍，得到硫酸镍溶液。
反应完成后得到铁红(以铁计)60.02g，硫磺24.03g，硫化铜(以铜计)8.55g，硫酸镍(以镍计)20.83g，萃余液(以钴计)0.73g，由此可知，镍的浸出率为99.28％，钴的浸出率为96.05％，铜的浸出率为95.32％，硫的回收率为98.7％。
本实施例采用的反应设备如图1所示，包括反应容器100、搅拌浆200和冷凝器300。
实施例2
一种低冰镍浸出提取有价金属及硫元素的方法，低冰镍成份：镍23.66％、铜6.73％、钴1.36％、铁38.04％、硫24.35％，通过如下步骤提取有价金属及硫元素：
(1)原料预处理：将100g低冰镍破碎成粉状或颗粒状，低冰镍破碎后通过筛孔尺 寸标准不高于200目；
(2)氧化浸出：向步骤(1)所得粉碎料中加入1000mL铁离子浓度为2.0mol/L的硫酸铁和3000mL四氯化碳有机溶剂，在不断搅拌的状态下由底部鼓入氧气，并控制反应温度为120℃，反应时间为6h，每30min向反应体系中补加水和三价铁盐，维持三价铁离子在水相中的浓度为2.0-2.5mol/L；
(3)分离处理：步骤(2)反应结束后，静置后分离物料，得到固体渣层、有机层和水层；得到的固体渣层经洗涤后得到产品铁红；有机层经蒸发冷凝，分离，得到产品硫磺和有机溶剂；向水层中加入过氧化氢进行氧化，使水层中的铁全部以三价铁离子的形式存在，并调节pH至4.0-4.5，固液分离得到氢氧化铁沉淀和滤液；向滤液中通入硫化氢气体，并控制滤液pH为0.5-1.5，固液分离得到硫化铜沉淀和含镍滤液，使用Cyanex272作为萃取剂，对含镍滤液进行萃取，静置分离后得到含镍萃取有机相和含钴萃余液，用3mol/L的硫酸溶液从含镍萃取有机相中反萃取镍，得到硫酸镍溶液。
反应完成后得到铁红(以铁计)57.1g，硫磺22.64g，硫化铜(以铜计)6.36g，硫酸镍(以镍计)23.31g，萃余液(以钴计)1.31g，由此可知，镍的浸出率为98.52％，钴的浸出率为96.32％，铜的浸出率为94.50％，硫的回收率为93.0％。
实施例3
一种低冰镍浸出提取有价金属及硫元素的方法，低冰镍成份：镍26.55％、铜5.7％、钴1.06％、铁32.19％、硫27.45％，通过如下步骤提取有价金属及硫元素：
(1)原料预处理：将100g低冰镍破碎成粉状或颗粒状，低冰镍破碎后通过筛孔尺寸标准不高于200目；
(2)氧化浸出，向步骤(1)所得粉碎料中加入1000mL铁离子浓度为3mol/L的硝酸铁和2000mL四氯乙烷有机溶剂，在不断搅拌的状态下由底部鼓入空气，并控制反应温度为80℃，反应时间为10h。每20min向反应体系中补加水和三价铁盐，维持三价铁离子在水相中的浓度为3.0-5.5mol/L；
(3)分离处理：步骤(2)反应结束后，静置后分离物料，得到固体渣层、有机层和水层；得到的固体渣层经洗涤后得到产品铁红；有机层经蒸发冷凝，分离，得到产品 硫磺和有机溶剂；向水层中加入硝酸进行氧化，使水层中的铁全部以三价铁离子的形式存在，并调节pH至4-5，固液分离得到氢氧化铁沉淀和滤液；向滤液中通入硫化氢气体，并控制滤液pH为0-1.0，固液分离得到硫化铜沉淀和含镍滤液，使用P507和Cyanex272的混合物作为萃取剂，对含镍滤液进行萃取，静置分离后得到含镍萃取有机相和含钴萃余液，用4mol/L的硫酸溶液从含镍萃取有机相中反萃取镍，得到硫酸镍溶液。
反应完成后得到铁红52.01g，硫磺24.33g，硫化铜(以铜计)5.38g，硫酸镍(以镍计)26.39g，萃余液(以钴计)1.02g，由此可知，镍的浸出率为99.39％，钴的浸出率为96.23％，铜的浸出率为94.39％，硫的回收率为88.6％。
上面结合附图对本发明实施例作了详细说明，但是本发明不限于上述实施例，在所属技术领域普通技术人员所具备的知识范围内，还可以在不脱离本发明宗旨的前提下作出各种变化。此外，在不冲突的情况下，本发明的实施例及实施例中的特征可以相互组合。

Claims (10)

  1. 一种低冰镍浸出提取有价金属及硫元素的方法，其特征在于，包括以下步骤：
    向低冰镍粉碎料中加入三价铁盐溶液和有机溶剂，在搅拌状态下通氧化性气体进行反应，反应结束分离出固体渣层、有机层和水层。
  2. 根据权利要求1所述的方法，其特征在于，所述三价铁盐溶液中铁离子的浓度为0.1-5.5mol/L。
  3. 根据权利要求1所述的方法，其特征在于，所述有机溶剂为二硫化碳、四氯化碳、甲基环己烷、三氯乙烷、三氯乙烯、四氯乙烷、二甘醇二甲醚、四氢萘或十氢萘的一种或几种。
  4. 根据权利要求1所述的方法，其特征在于，所述低冰镍粉碎料、三价铁盐溶液、有机溶剂的固液比为1g：(1.5-50)mL：(1.0-30)mL。
  5. 根据权利要求1所述的方法，其特征在于，所述反应的温度为80-120℃；优选的，所述反应的时间为0.5-10h。
  6. 根据权利要求1所述的方法，其特征在于，在所述反应的过程中，每20-60min向反应体系中补加一次水和三价铁盐，维持三价铁离子在水相中的浓度为0.1-5.5mol/L。
  7. 根据权利要求1所述的方法，其特征在于，所述氧化性气体为空气或氧气中的至少一种。
  8. 根据权利要求1所述的方法，其特征在于，向所述水层中加入氧化剂，调节pH至3.2-5，固液分离得到氢氧化铁沉淀和滤液。
  9. 根据权利要求8所述的方法，其特征在于，向所述滤液中通入硫化氢气体，并控制滤液的pH为0-2.0，固液分离得到硫化铜沉淀和含镍滤液。
  10. 根据权利要求1所述的方法，其特征在于，所述有机层经蒸发冷凝，分离，得到硫磺和有机溶剂。
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