WO2018188537A1 - 一种铜镍硫化矿综合回收利用的方法及其系统 - Google Patents

一种铜镍硫化矿综合回收利用的方法及其系统 Download PDF

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Publication number
WO2018188537A1
WO2018188537A1 PCT/CN2018/082209 CN2018082209W WO2018188537A1 WO 2018188537 A1 WO2018188537 A1 WO 2018188537A1 CN 2018082209 W CN2018082209 W CN 2018082209W WO 2018188537 A1 WO2018188537 A1 WO 2018188537A1
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Prior art keywords
leaching
nickel
copper
iron
cobalt
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PCT/CN2018/082209
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English (en)
French (fr)
Inventor
赵中伟
李永立
刘旭恒
肖万海
陈星宇
李江涛
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Central South University
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Central South University
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Priority claimed from CN201710228509.5A external-priority patent/CN107058730B/zh
Priority claimed from CN201710229424.9A external-priority patent/CN107012324B/zh
Application filed by Central South University filed Critical Central South University
Priority to AU2018252056A priority Critical patent/AU2018252056B2/en
Priority to FI20195705A priority patent/FI131460B1/en
Priority to CA3049827A priority patent/CA3049827C/en
Priority to RU2019121486A priority patent/RU2741429C1/ru
Publication of WO2018188537A1 publication Critical patent/WO2018188537A1/zh
Priority to ZA201904337A priority patent/ZA201904337B/en
Priority to US16/529,729 priority patent/US11459636B2/en
Anticipated expiration legal-status Critical
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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
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/02—Apparatus therefor
    • 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
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
    • C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
    • C22B3/08—Sulfuric acid, other sulfurated acids or salts thereof
    • 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
    • C22B11/00—Obtaining noble metals
    • C22B11/02—Obtaining noble metals by dry processes
    • C22B11/021—Recovery of noble metals from waste materials
    • C22B11/023—Recovery of noble metals from waste materials from pyrometallurgical residues, e.g. from ashes, dross, flue dust, mud, skim, slag, sludge
    • 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
    • C22B15/0002—Preliminary treatment
    • C22B15/001—Preliminary treatment with modification of the copper constituent
    • 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
    • C22B15/0026—Pyrometallurgy
    • C22B15/0028—Smelting or converting
    • 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
    • C22B15/0067—Leaching or slurrying with acids or salts thereof
    • C22B15/0071—Leaching or slurrying with acids or salts thereof containing sulfur
    • 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
    • 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
    • C22B23/005—Preliminary treatment of ores, e.g. by roasting or by the Krupp-Renn process
    • 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
    • C22B23/0415—Leaching processes with acids or salt solutions except ammonium salts solutions
    • C22B23/043—Sulfurated acids or salts thereof
    • 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
    • C22B23/0484—Separation of nickel from cobalt in acidic type solutions
    • 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
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
    • C22B3/38—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds containing phosphorus
    • C22B3/384—Pentavalent phosphorus oxyacids, esters thereof
    • C22B3/3844—Phosphonic acid, e.g. H2P(O)(OH)2
    • 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 relates to the field of non-ferrous metallurgy technology, and more particularly to a method and system for comprehensive recycling of copper-nickel sulfide ore.
  • Nickel is an important strategic metal widely used in defense, aerospace, transportation, petrochemical, energy and other fields.
  • a considerable number of nickel ores are sulfide minerals associated with copper, cobalt and precious metals (gold, silver and platinum group metals), such as the Jinchuan copper-nickel mine in Gansu and the Kalatongke copper-nickel mine in Xinjiang. Therefore, in the extraction of nickel and copper, it is also necessary to consider the recovery of cobalt and precious metals.
  • the traditional smelting process of copper-nickel sulphide ore is firstly smelted by smelting, so that iron, nickel, cobalt and copper are enriched in the form of sulfides to form low-ice nickel, and the associated precious metals are also enriched; then low-nickel nickel is carried out.
  • the converter is blown to remove most of the iron and sulfur to form high ice nickel.
  • the oxidation loss of cobalt is often caused (about 40-60% loss, which is difficult to recover), and the sulfur dioxide produced is obtained by the acid-making system to obtain industrial sulfuric acid (sulfuric acid is accumulated in large quantities due to the use and transportation radius).
  • the processing methods of the high-ice nickel obtained by the blowing are roughly classified into three types.
  • high-ice nickel is subjected to grinding and floating separation after slow cooling, and low-nickel nickel sulfide concentrate, low-nickel copper sulfide concentrate and primary alloy are respectively obtained.
  • the primary alloy also needs to be vulcanized again - grinding and separating the corresponding low copper nickel sulfide concentrate, low nickel copper sulfide concentrate and secondary alloy.
  • the secondary alloy is used for the recovery of precious metals, and the low copper nickel sulphide concentrate is used for the extraction of nickel.
  • the copper sulphide concentrate is used for copper extraction, and naturally there is also nickel. The problem of impurities being carried causes the smelting process to be quite cumbersome.
  • high-ice nickel can also be used in acid selective leaching process, which is mainly divided into: low acid pressure oxygen leaching or high acid atmospheric pressure leaching.
  • Low acid pressure oxygen leaching has been applied in the Fukang smelting plant in China.
  • the Fukang smelter uses low-acid two-stage countercurrent leaching, first of all a normal pressure leaching (pH ⁇ 6.2 of the final leaching solution), followed by a section of pressurized oxygen leaching, which oxidizes nickel sulphide by precisely controlling the oxygen partial pressure.
  • the copper is not leached (final pH of the leachate is 1.8-2.8, oxygen pressure 0.05-0.06 MPa).
  • Ni, Fe ⁇ 0.01g/L nickel sulfate solution is obtained by two-stage countercurrent leaching, and almost all of the copper, precious metal, iron and sulfur in the raw material and about 40% of the cobalt remain in the nickel-containing 2%-3% final. Slag.
  • the high acid and atmospheric pressure leaching was first applied in the Kristiansund refinery.
  • the process uses high concentration hydrochloric acid (275g/L) as the leaching agent, and the obtained leaching rich liquid contains about 120g/L of nickel, 160g/L of hydrochloric acid, and iron.
  • Cobalt and copper are each 2g/L. About 3% of the copper is leached and most of it remains in the slag.
  • high-ice nickel can also be leached by ammonia under high pressure oxygen conditions.
  • the copper-nickel-cobalt is converted into a metal ammonia complex to be dissolved, while the sulfur is oxidized to sulfate, and the precious metal and iron form a slag phase for recovery.
  • the control of free ammonia during leaching is particularly important.
  • the low concentration results in a low leaching rate. If the concentration is too high, a high ammonia complex of cobalt is formed, which causes loss of cobalt due to its insolubility.
  • the main component of the reduction product is an alloy of iron, cobalt and nickel and a sulfide, which becomes cobalt ice nickel.
  • cobalt is easily oxidized, the content is low, and it is excessively dispersed in the blowing slag, and even by reduction smelting, only a part of cobalt can be recovered.
  • this cobalt ice nickel leaching is very complicated and requires three stages of leaching. The first stage is mainly alloy leaching.
  • the low-ice nickel is blown into high-ice nickel.
  • the copper-nickel recovery problem is better solved, there are serious problems in the recovery of associated cobalt and precious metals.
  • sulfur is produced in the form of sulfuric acid, and the market and transportation radius are also a headache.
  • Low-ice nickel Direct treatment of low-ice nickel is expected to avoid the loss of associated valuable elements such as cobalt and precious metals during the above-mentioned blowing process.
  • existing methods for treating low-ice nickel are still inconvenient in recovering associated metals.
  • the sulphation roasting of low-ice nickel can convert nickel-cobalt copper into water-soluble sulphate, iron is converted into water-insoluble oxide, and the generated sulphur dioxide is still used for acid production.
  • the associated platinum group metals remain in the iron slag and require specialized complex processes to extract.
  • Low-ice nickel can also be treated by oxygen pressure acid leaching, such as Yin Fei et al. and Deng Zhilin et al.
  • the sulfur formed by oxidation forms a retardation film and affects leaching.
  • the oxygen pressure is leached, a considerable amount of iron is converted into iron slag, which is advantageous for the subsequent nickel-cobalt extraction, but the inclusion of the noble metal and the inclusion thereof causes difficulty in recovery.
  • sulfur is oxidized to sulfur into the slag phase, and further oxidation is required to recover the precious metal.
  • the existing direct treatment of low-ice nickel has both fire and wet processes.
  • the fire method can be calcined by sulfation, and then selectively leached with valuable elements.
  • the iron oxide remains in the leaching slag, but the precious metal in the iron slag is difficult to recover; many people prefer the wet method, and the wet method generally uses oxygen pressure leaching, which requires use.
  • Autoclave and pure oxygen but also face the problem of recovering precious metals from iron slag, and sulfur is oxidized to sulfur to form a package during acid oxygen leaching, and precious metal recovery is still difficult.
  • the technical problem to be solved by the present invention is that the recovery of each element cannot be effectively realized in the existing copper-nickel sulfide ore smelting process, and in particular, the recovery rates of elemental cobalt and precious metals are too low.
  • the present invention provides a method for comprehensive recycling of copper-nickel sulfide ore, comprising the following steps:
  • the leaching solution enriched with nickel iron cobalt and the leaching slag enriched with copper are obtained by the scheme A or the scheme B:
  • the low-nickel nickel obtained by smelting and leaching the copper-nickel sulfide ore and the leaching reaction liquid are continuously added to the reaction bottom liquid to perform selective leaching, and the hydrogen sulfide gas, the first leaching liquid and the first leaching slag are respectively collected, wherein
  • the reaction bottom liquid is a sulfuric acid solution having a mass fraction of 20%-60%, and the leaching reaction liquid is a sulfuric acid solution having a mass fraction of 60%-95%; adding water to the first leaching slag, dissolving, and separately collecting the second Leachate and second leach residue;
  • the low-ice nickel obtained by the smelting and smelting of the copper-nickel sulfide ore is directly subjected to atmospheric pressure selective leaching using sulfuric acid, and the hydrogen sulfide gas, the leachate and the leaching slag are separately collected, wherein the temperature of the selective leaching at atmospheric pressure is 25-80 ° C;
  • the second leachate of the scheme A and the leachate of the scheme B are the leachate enriched with nickel iron cobalt; the second leach residue of the scheme A and the leach residue of the scheme B are the leach residue with copper enrichment;
  • Step 1) removing the iron-cobalt-rich leachate by iron removal, separately collecting the iron-removing liquid and the iron-removing residue, and extracting the iron solution for nickel and cobalt extraction, and removing the iron residue for iron making;
  • the high-concentration sulfuric acid is used to directly treat the low-nickel nickel obtained by the smelting and smelting of the copper-nickel sulfide or the copper-nickel sulfide ore, and the low-solubility of the sulfate of nickel, cobalt and iron in the high-concentration sulfuric acid solution is Separation with a high concentration sulfuric acid solution can be achieved by crystallizing them into the slag phase and filtering.
  • Low-ice nickel is mainly derived from copper-nickel sulfide concentrate.
  • the main component is Ni 5 Fe 4 S 8 .
  • nickel In addition to nickel, it is rich in copper, cobalt and a large amount of platinum group.
  • low-nickel nickel is copper-nickel.
  • the sulfide ore is obtained by smelting and smelting, that is, the method of the invention is more suitable for the decomposition and extraction of low-nickel nickel obtained by smelting and melting of copper-nickel sulfide ore.
  • Preferred embodiments A and B of the method of the invention are all the problems that the existing schemes are difficult to recover the valuable elements well, and the technical problems solved are the same.
  • the two preferred schemes have the same innovations of the invention.
  • the leachate is subjected to iron removal treatment, and the iron in the leachate is converted into goethite or hematite to realize separation of iron from nickel-cobalt; finally, separation of nickel and cobalt is achieved.
  • the preferred two solutions of the present invention solve the same object (or similar), and the solutions are all atmospheric acid pickling-iron removal and nickel-cobalt separation, and the main idea is the same, belonging to the same invention concept.
  • the intended purpose is to solve the problem of serious loss of associated minerals existing in the existing recycling method, both of which achieve the purpose of improving the recovery rate of elements, and achieve the same purpose; therefore, the two preferred embodiments of the present invention belong to the same
  • the inventive concept of the inventive concept meets the requirements of unity.
  • the blowing process of low ice nickel in the conventional method is eliminated, and the loss of cobalt caused during the blowing process is effectively prevented.
  • the copper and precious metals are effectively retained in the leaching slag by using the above leaching step, and the leaching slag is sent to the copper smelting system for smelting.
  • the noble metal is single-oriented, can be effectively recovered, and the cobalt and platinum associated with the copper-nickel sulfide ore are improved. Group metal recovery rate.
  • the low-nickel nickel obtained by the smelting and smelting of the copper-nickel sulfide ore is directly treated with high-concentration sulfuric acid, and the solubility of the sulfates of nickel, cobalt and iron in the high-concentration sulfuric acid solution is low, so that they are crystallized and precipitated into the slag.
  • the phase, and further filtration, can be separated from the high concentration sulfuric acid solution.
  • cuprous sulfide and precious metals do not participate in the reaction and remain in the slag together.
  • the leaching slag containing nickel, cobalt, iron, sulphate crystals, cuprous sulphide and precious metals is leached by water to dissolve the sulphate. After filtration, secondary slag of copper sulphide and precious metals and nickel, cobalt and iron sulphate are obtained. Aqueous solution. The secondary slag is then sent to a copper smelting system to recover copper and precious metals. Nickel-cobalt-iron is obtained by removing iron and then separating nickel-cobalt.
  • the direct treatment of the copper-nickel sulfide concentrate or the copper-nickel sulfide ore by the smelting and smelting of the low-ice nickel can avoid the problem of loss of associated valuable elements such as cobalt and precious metals in the conventional smelting process.
  • the sulfate of iron-nickel-cobalt is crystallized from the leachate due to saturation, and separation from high-concentration sulfuric acid is achieved. The separation of copper and iron-nickel-cobalt is achieved after the primary filter residue is simply dissolved in water. Directly pressure selective leaching of copper-nickel sulfide concentrate or low-ice nickel directly using sulfuric acid.
  • nickel-iron-cobalt is dissolved in sulfuric acid solution and completely reacted to form hydrogen sulfide gas.
  • copper The copper sulfide and the noble metal in the nickel sulfide or low-ice nickel hardly decompose, and the deep separation of nickel and copper can be achieved in the leaching process.
  • the copper and precious metals are effectively retained in the second leaching slag by using the above leaching step, and the leaching slag is sent to the copper smelting system for smelting.
  • the precious metal is single-oriented, can be effectively recovered, and the cobalt associated with the copper-nickel sulphide ore is improved. And platinum group metal recovery.
  • a person skilled in the art can select a second leachate or a second leach residue according to actual needs to perform corresponding treatment to recover associated elements such as nickel, cobalt, iron, copper and precious metals.
  • the leaching reaction is usually placed in the reaction vessel, that is, the step 1) may be: filling the reaction tank with the reaction bottom liquid, that is, a sulfuric acid solution having a mass fraction of 20%-60% as a reaction.
  • the bottom liquid that is, a sulfuric acid solution having a mass fraction of 20%-60% as a reaction.
  • the bottom liquid at the same time, a low-ice nickel (or copper-nickel sulfide ore) and a sulfuric acid solution having a leaching reaction liquid mass fraction of 60% to 95% are added to the reaction vessel for reaction.
  • the leaching reaction solution and the low-ice nickel are continuously added, and the consumption of sulfuric acid in the reaction vessel is maintained in accordance with the amount of addition. The feed is reacted.
  • the reaction tank in order to make the reaction more complete and to control the sulfuric acid concentration of the reaction end point solution, the reaction tank is usually filled with a reaction bottom liquid of 30%-60% of the total volume of the reactor, that is, a mass fraction of 20%-60. % sulfuric acid solution.
  • the leaching is continued for 0.5-2 h after the completion of the addition.
  • the feeding may be stopped until the slurry in the reactor reaches 80% of the total volume of the kettle, the reaction is continued for 0.5-2 h, and the hydrogen sulfide gas, the first leachate and the first leach residue formed during the reaction are collected. .
  • the low-ice nickel and the leaching reaction liquid are continuously added at the same time, and the addition amount and the consumption amount of the two are the same; the first leachate is returned as the reaction bottom liquid of the next batch of materials, and is recycled. .
  • the first leaching slag can be pumped into the dissolution tank containing deionized water.
  • the nickel sulphate, cobalt sulfide and ferrous sulfate crystals precipitated by supersaturation during the leaching reaction are redissolved and then secondary filtered, respectively collected.
  • Another method for leaching low-ice nickel in the invention in the scheme B, at 25-80 ° C, the low-nickel nickel obtained by the smelting and melting of the copper-nickel sulfide ore is metathesized in a sulfuric acid solution, and the nickel-iron cobalt is dissolved in water. And generate hydrogen sulfide gas, the reaction is very thorough, at the same time, under the sulfuric acid at this temperature, the copper sulfide in the low-ice nickel hardly decomposes, can realize the deep separation of copper nickel in the leaching process, improve the recovery rate, break In order to achieve efficient extraction of various elements in minerals by using high temperatures above 90 °C in work, energy is saved and the risk to the operator is reduced.
  • the direct treatment of the low-ice nickel obtained by the smelting of the copper-nickel sulfide ore can avoid the problem of the loss of the associated valuable elements such as cobalt and precious metals in the process of the low-ice nickel in the subsequent conventional blowing process.
  • the low-ice nickel is directly subjected to atmospheric pressure selective leaching using sulfuric acid. At this concentration and the liquid-solid ratio, the nickel-iron is dissolved in the sulfuric acid solution and completely reacted to form hydrogen sulfide gas. At this time, the copper sulfide in the low-ice nickel is The precious metal hardly decomposes, and the deep separation of nickel and copper can be achieved during the leaching process.
  • the sulfuric acid concentration in step 1) is 1 mol / L - 6 mol / L
  • atmospheric pressure selective leaching The temperature is 25-80 ° C
  • the atmospheric pressure selective leaching time is 0.5-5 h.
  • the sulfuric acid concentration in the step 1) is 3 mol/L to 4 mol/L
  • the normal pressure selective leaching time is 0.5-2 h
  • the leaching temperature is 50-70 ° C
  • the liquid-solid ratio is 5:1. -10:1.
  • the hydrogen sulfide gas collected after the selective leaching and the sulfur dioxide generated in the smelting smelting can be sent to the sulfur system to prepare sulfur.
  • the sulfur dioxide is sent to the sulfuric acid system to prepare sulfuric acid for the sulfuric acid solution, that is, the leaching reaction solution and the reaction bottom liquid.
  • a part of the produced sulfur dioxide is used as a leaching agent, and a part of the sulfur dioxide is reacted with the generated hydrogen sulfide to form sulfur, thereby solving the problem of accumulation of a large amount of sulfuric acid in the conventional process.
  • the present invention uses the hydrogen sulfide gas generated by the low-ice nickel in the sulfuric acid leaching process to prepare sulfur, which can solve the problem of sulfur which has long plagued the nickel sulfide mining enterprises, and the sulfuric acid used in the conventional method for preparing sulfuric acid. It is easier to store and transport than it is.
  • a person skilled in the art can select, after the leaching step, the iron removal of the leachate or the smelting of the leaching slag to the copper smelting system or the smelting of the leaching slag to the copper smelting system, preferably after the leaching step.
  • the ground is used for the recovery of nickel, cobalt and/or iron from the leachate, and also for the leaching of the slag to the copper smelting system for the recovery of copper and precious metals.
  • the iron of the leachate is mainly present in the form of divalent iron ions.
  • the copper content in the solution in the second leachate of the present invention is less than 0.009 g/L, preferably less than 0.003 g/L, in Scheme B.
  • the copper content in the solution in the leach solution of step 1) is less than 0.008 g/L, preferably less than 0.003 g/L, and the iron is mainly in the form of divalent iron ions, and can be removed by using the iron removal method commonly used in the art without further reduction.
  • Iron can be directly oxidized to form goethite or hematite. In order to better remove iron and not affect the recovery of nickel-cobalt, in a preferred embodiment of the invention, the goethite method or the hematite method is preferably employed.
  • the iron removal of the leachate is specifically:
  • An oxygen-rich gas is introduced into the leachate or the leachate having a pH of 3 to 7 to obtain a post-iron removal solution and an iron removal residue;
  • the leachate is added to the autoclave to react with the oxidizing gas, and after the reaction is completed, the solid-liquid separation is carried out, and after the filter residue is washed and dried, the iron residue is removed, and the obtained filtrate is a post-iron removal liquid.
  • the pH of the leachate in step 1) can be adjusted to 4-7, placed in a closed autoclave, passed through pure oxygen and heated to 220 ° C, and the iron is removed as hematite to obtain a solution for removing iron. Iron slag.
  • the leaching liquid in step 1) can also be passed through air or oxygen-enriched air while maintaining the pH of the solution at 3-4, and the iron can be removed in the form of goethite to obtain a post-iron removal liquid and iron removal slag.
  • the obtained iron slag can be calcined into an iron concentrate for iron making.
  • the temperature at which the reaction with the oxidizing gas is 150-200 ° C
  • the oxygen partial pressure in the autoclave is maintained at 0.1-1 MPa
  • the reaction time is 1-5 h.
  • the obtained iron slag can be calcined into an iron concentrate for use in iron making, and the iron removing slag can also be used as a raw material for iron iron in lithium iron phosphate.
  • the iron-removing liquid can be used to extract nickel and cobalt using methods commonly used in the art.
  • the pH of the iron-removing liquid is adjusted to 4.0- After 5.5, the extractant is added to the iron removal liquid, and the cobalt-containing solution and the nickel-containing solution are separated by extraction, and the pH of the nickel-containing solution is adjusted to 5.5-7.0.
  • the extraction agent is used for nickel extraction; wherein the extractant is P507 kerosene solution or Cyanex272 kerosene solution with a volume fraction of 10-50%.
  • kerosene is a diluent.
  • P507 is 2-ethylhexylphosphonic acid mono(2-ethylhexyl) ester
  • Cyanex272 is bis(2,4,4-trimethylpentyl)phosphoric acid.
  • the extracting agent is a kerosene solution of P507
  • the pH of the iron removing solution is adjusted to 4.0-5.0
  • the extracting agent is added to the iron removing liquid
  • the cobalt is extracted by the extracting agent
  • the cobalt-containing solution is extracted and separated (cobalt-containing organic
  • the pH of the nickel-containing solution is adjusted to 5.5-6.5
  • the nickel is extracted with an extractant
  • the hydrochloric acid is stripped to obtain a nickel chloride solution for preparing a nickel product.
  • a cobalt-containing solution (cobalt-containing organic phase) is back-extracted with hydrochloric acid to obtain a cobalt chloride solution for preparing a cobalt product.
  • the extracting agent is a kerosene solution of Cyanex 272
  • the pH of the iron removing solution is adjusted to 5.0-5.5, and then an extractant is added to the iron removing liquid to extract a cobalt-containing solution (containing a cobalt organic phase) and a nickel-containing solution.
  • the pH of the nickel-containing solution is adjusted to 6.5-7.0
  • the nickel is extracted with an extracting agent, and the sulfuric acid is back-extracted to obtain a nickel sulfate solution for preparing a nickel sulfate product.
  • the cobalt-containing solution (cobalt-containing organic phase) is back-extracted with sulfuric acid to obtain a cobalt sulfate solution for preparing a cobalt sulfate product.
  • copper and precious metals can be obtained by a conventional copper smelting process in the art.
  • the copper-rich leaching slag (for example, the second leaching slag or the leaching slag of the step B (1)) obtained by treating the low-ice nickel is sent to a converter to obtain crude copper, and then refined to obtain refined copper and enriched precious metals.
  • the copper-enriched leaching slag (for example, the second leaching slag or the leaching slag of the step B (1)) obtained by treating the low-ice nickel is subjected to oxidative roasting, and then acid leaching is performed to separately collect the copper-rich leaching solution and enrichment.
  • the copper-rich leaching slag (for example, the second leaching or the leaching slag of the step B (1)) obtained by treating the low-ice nickel is slag for oxygen leaching, and the copper-enriched leaching solution and the precious metal-rich leaching solution are separately collected. The leaching residue is used to extract precious metals.
  • the leaching rate of nickel, iron and cobalt obtained by the method of the invention is above 99%, and the cobalt and the noble metal are effectively recovered, the recovery rate of copper is above 98%, and the recovery rate of precious metal is above 95%.
  • a system for comprehensive recycling of copper-nickel sulfide ore comprising: a device for obtaining leachate and leach residue, a selective leaching device and a water dissolving device; or an atmospheric pressure selective leaching device :
  • the selective leaching device has a continuous feeding port for each of the low ice nickel and the leaching reaction liquid, the selective leaching device contains the reaction bottom liquid, and the low ice obtained by continuously adding the copper nickel sulfide ore to the reaction bottom liquid through smelting and smelting Selective leaching reaction occurs when nickel and leaching the reaction solution;
  • the selective leaching device further includes a hydrogen sulfide gas collecting device, a first leaching liquid collecting device, and a first leaching slag collecting device, wherein the reaction bottom liquid is of a mass a fraction of 20%-60% sulfuric acid solution, the leaching reaction solution is a sulfuric acid solution having a mass fraction of 60%-95%;
  • a water dissolving device for dissolving the first leaching slag using water, separately collecting the second leaching liquid and the second leaching slag;
  • Atmospheric pressure selective leaching device for direct leaching of low-ice nickel directly using sulfuric acid at normal pressure to separately collect hydrogen sulfide gas, leachate and leach residue;
  • a de-ironing device for de-ironing the second leachate obtained in the water-dissolving device or for removing iron from the leachate obtained in the atmospheric-pressure selective leaching device;
  • Nickel and cobalt extraction device for collecting iron removal liquid in iron removal device for extraction of nickel and cobalt
  • system further includes:
  • An smelting smelting device for treating copper-nickel sulfide ore and providing low-ice nickel to the atmospheric pressure selective leaching device which is obtained by smelting and melting a copper-nickel sulfide ore.
  • a sulfur preparation device for completely reacting sulfur dioxide generated in the smelting smelting device with hydrogen sulfide gas generated in the atmospheric pressure selective leaching device to obtain sulphur;
  • a sulfuric acid production unit for converting residual sulfur dioxide produced in the smelting smelting apparatus into sulfuric acid and supplying it to the atmospheric pressure selective leaching apparatus.
  • the first leachate collection device in the system can also be used to provide a reaction effluent to the selective leaching device.
  • the atmospheric pressure selective leaching device further comprises a temperature regulating device for controlling the temperature of the normal pressure selective leaching at 25-80 ° C, thereby improving the comprehensive utilization of the copper-nickel sulfide ore.
  • the method and system for comprehensive utilization of copper-nickel sulfide ore proposed by scheme A.
  • the low-ice nickel obtained by smelting and smelting of copper-nickel sulfide ore is directly leached by atmospheric pressure at 25-80 ° C in low-ice nickel.
  • Nickel, cobalt and iron are decomposed by acid and then enter the solution.
  • the leaching solution is used for iron and cobalt extraction after iron removal.
  • Iron slag is used for iron making; copper in low ice nickel is retained in the form of cuprous sulfide with precious metals. Slag, smelting into copper, recycling copper and precious metals.
  • the method has short process and high efficiency, and can not only realize the deep separation of nickel and copper, but also greatly improve the recovery rate of cobalt and precious metals, and is a clean and efficient element comprehensive utilization process, which is easy for large-scale industrial production.
  • the method of the invention is preferably carried out using the system of the invention.
  • Scheme A A method for recovering primary associated elements from copper-nickel sulfide ore, including:
  • reaction bottom liquid is a sulfuric acid solution having a mass fraction of 20% to 60%
  • leaching reaction liquid is a sulfuric acid solution having a mass fraction of 60% to 95%
  • the second leaching slag is sent to a copper smelting apparatus for smelting to obtain copper and precious metals, respectively.
  • the selective leaching is atmospheric pressure non-oxidative leaching; and/or the leaching reaction solution is a sulfuric acid solution having a mass fraction of 85% to 90%.
  • the low-ice nickel and the leaching reaction liquid are continuously added at the same time, and the amount of both is added in the same amount as the consumption; the first leachate is returned to the reaction bottom liquid as the next batch of materials, and is recycled.
  • step 1) the leaching continues for 0.5-2 h after the addition is completed.
  • sulfur dioxide produced in the enthalpy smelting is reacted with hydrogen sulphide gas in step 1) to produce sulphur, and the remaining sulphur dioxide is converted to the sulphuric acid solution used in the step 1) for atmospheric pressure selective leaching.
  • the removing of the second leachate in the step 3) is specifically:
  • An oxygen-rich gas is introduced into the second leachate to obtain a post-iron removal liquid and an iron removal residue.
  • the extraction of nickel and cobalt by the post-iron removal liquid in the step 3) is specifically as follows:
  • the extractant is added to the iron removal liquid, and the cobalt-containing solution and the nickel-containing solution are separated by extraction, and the pH of the nickel-containing solution is adjusted to 5.5-7.0.
  • the agent is subjected to extraction of nickel;
  • the extracting agent is a kerosene solution of P507 or a kerosene solution of Cyanex 272, and the volume fraction is 10-50%.
  • the method for recovering the copper and the precious metal is specifically:
  • the second leaching slag is blown by a converter to obtain crude copper, and then electrolyzed to obtain refined copper and an anode slime rich in precious metal, and the anode mud is used for extracting precious metal;
  • the second leaching residue is oxidized and calcined, and then acid leaching is performed to separately collect the copper-rich leaching solution and the precious metal-rich leaching slag, and the leaching slag is used for extracting the precious metal;
  • the second leaching slag is subjected to oxygen pressure leaching, and the copper-rich leaching liquid and the precious metal-rich leaching slag are separately collected, and the leaching slag is used for extracting precious metals.
  • the invention is preferably used in the system of Scheme A, a system for recovering primary associated elements from a copper-nickel sulfide ore, comprising:
  • the selective leaching device further includes a hydrogen sulfide gas collecting device, a first leaching liquid collecting device, and a first leaching slag collecting device, wherein the reaction The bottom liquid is a sulfuric acid solution having a mass fraction of 20% to 60%, and the leaching reaction liquid is a sulfuric acid solution having a mass fraction of 60% to 95%;
  • a water dissolving device for dissolving the first leaching slag using water, separately collecting the second leaching liquid and the second leaching slag;
  • a de-ironing device for removing iron from the second leachate obtained in the water dissolving device
  • Nickel and cobalt extraction device for collecting iron removal liquid in iron removal device for nickel and cobalt extraction
  • ironmaking device for collecting iron removal slag in iron removal device for iron making
  • the system is applicable to the system A, and further includes: a sulfur preparation device for reacting sulfur dioxide generated in the smelting smelting with the hydrogen sulfide gas generated in the atmospheric pressure selective leaching device to obtain sulfur; the sulfuric acid preparation device is used for A part of the sulfur dioxide produced in the smelting smelting is converted into sulfuric acid and supplied to the atmospheric pressure selective leaching device.
  • a sulfur preparation device for reacting sulfur dioxide generated in the smelting smelting with the hydrogen sulfide gas generated in the atmospheric pressure selective leaching device to obtain sulfur
  • the sulfuric acid preparation device is used for A part of the sulfur dioxide produced in the smelting smelting is converted into sulfuric acid and supplied to the atmospheric pressure selective leaching device.
  • Scheme B A method for the comprehensive utilization of copper-nickel sulfide ore, including:
  • the low-ice nickel obtained by the smelting of the copper-nickel sulfide ore is directly subjected to atmospheric pressure selective leaching using sulfuric acid, and the hydrogen sulfide gas, the leachate and the leach residue are separately collected, wherein the atmospheric pressure selective leaching temperature is 25 -80 ° C;
  • step 2) removing the iron from the leachate of step 1), separately collecting the iron removal liquid and the iron removal residue, the iron removal liquid is used for extracting nickel and cobalt, and the iron removal residue is used for iron making;
  • the sulfur dioxide generated in the enthalpy smelting is reacted with the hydrogen sulfide gas in the step 1) to prepare sulfur, and the remaining sulfur dioxide is converted into the sulfuric acid used in the atmospheric selective leaching in the step 1).
  • the sulfuric acid concentration in the step 1) is 1 mol/L to 6 mol/L
  • the liquid-solid ratio of the atmospheric pressure selective leaching is 2:1-20:1
  • the atmospheric pressure selective leaching time It is 0.5-5h.
  • the sulfuric acid concentration in the step 1) is 3 mol/L to 4 mol/L
  • the normal pressure selective leaching time is 0.5-2 h
  • the leaching temperature is 50-70 ° C
  • the liquid-solid ratio is 5:1. -10:1.
  • the iron removal in the step 1) in the step 2) is specifically: adjusting the pH of the leachate to 3-7, and then introducing an oxygen-rich gas to obtain a post-iron removal solution and iron removal. Slag.
  • the extraction of the nickel and cobalt after the iron removal liquid in the step 2) is specifically:
  • the extractant is added to the iron removal liquid, and the cobalt-containing solution and the nickel-containing solution are separated by extraction, and the pH of the nickel-containing solution is adjusted to 5.5-7.0.
  • the agent is subjected to extraction of nickel;
  • the extracting agent is a kerosene solution of P507 or a kerosene solution of Cyanex 272, and the volume fraction is 10-50%.
  • the extraction method of the copper and the noble metal is specifically:
  • the leaching slag of step 1) is blown by converter to obtain crude copper, and then electrolyzed to obtain refined copper and anode mud enriched with precious metal, and anode mud enriched with precious metal is used for extracting precious metal;
  • the leaching residue of the step 1) is oxidized and calcined, and then acid leaching is performed to separately collect the copper-rich leaching solution and the precious metal-rich leaching slag, and the precious metal-rich leaching slag is used for extracting the precious metal;
  • the leaching slag of the step 1) is subjected to oxygen pressure leaching, and the copper-rich leaching solution and the precious metal-rich leaching slag are separately collected, and the precious metal leaching slag is enriched for extracting the precious metal.
  • a system for comprehensive utilization of copper-nickel sulfide ore suitable for scheme B comprising: a normal pressure selective leaching device for direct-pressure selective leaching of low-ice nickel directly using sulfuric acid to separately collect hydrogen sulfide gas, leachate and Leaching residue
  • a de-ironing device for removing iron from the leachate obtained in the atmospheric pressure selective leaching device
  • Nickel and cobalt extraction device for collecting iron removal liquid in iron removal device for nickel and cobalt extraction; ironmaking device for treating iron removal slag in iron removal device for iron making;
  • a copper smelting apparatus for smelting the leaching slag obtained in the atmospheric pressure selective leaching apparatus to obtain copper and a precious metal, respectively.
  • the system for comprehensive utilization of copper-nickel sulfide ore in Scheme B further comprises:
  • An smelting smelting device for treating copper-nickel sulfide ore and providing low-ice nickel to the atmospheric pressure selective leaching device, wherein the low-ice nickel is obtained by smelting and melting a copper-nickel sulfide ore;
  • a sulfur preparation device for reacting sulfur dioxide generated in the smelting smelting device with hydrogen sulfide gas generated in the atmospheric pressure selective leaching device to obtain sulphur;
  • a sulfuric acid producing apparatus for converting a part of sulfur dioxide generated in the smelting smelting apparatus into sulfuric acid and supplying the same to the atmospheric pressure selective leaching apparatus.
  • the system is suitable for the comprehensive utilization of copper-nickel sulfide ore in scheme B, and the atmospheric pressure selective leaching device further comprises a temperature regulating device for controlling the temperature of the atmospheric pressure selective leaching to 25-80 °C.
  • the invention discloses a method and a system for comprehensive recycling and utilization of copper-nickel sulfide ore, and utilizes the characteristic that the solubility of nickel, iron and cobalt sulfate crystals in high acid is lowered, and the liquidity at a certain acidity (ie, the mass fraction is 20%)
  • a low-ice nickel and leaching reaction solution ie, a sulfuric acid solution having a mass fraction of 60%-95%) is simultaneously fed in a continuous reaction mode to produce a nickel, iron, cobalt sulfuric acid.
  • the salt is precipitated due to saturation; the primary filtrate obtained by filtration can be used as a bottom liquid circulation; the primary filter residue contains nickel sulfate, cobalt sulfate and iron sulfate crystals precipitated by saturation, and cuprous sulfide and precious metal which are difficult to be leached by sulfuric acid, and are dissolved in water.
  • an aqueous solution of nickel, cobalt and iron sulfate is obtained, and a cuprous sulfide slag rich in precious metal is obtained, and at the same time, deep separation of copper from nickel, cobalt and iron can be achieved; after removal of iron from the aqueous solution of nickel, cobalt and iron It is used for the extraction of nickel sulfate and cobalt sulfate; copper sulfide slag enriched with precious metals can effectively recover copper and precious metals through traditional copper smelting and precious metal recovery processes.
  • the generated hydrogen sulfide gas reacts with sulfur dioxide generated by smelting and smelting to prepare high-purity sulfur, which is convenient for transportation and storage.
  • the method has short process and high efficiency, and can not only realize the deep separation of nickel and copper, but also greatly improve the recovery rate of cobalt and precious metals, and is a clean and efficient element comprehensive utilization process, which is easy for large-scale industrial production.
  • the copper-nickel sulfide ore is smelted and smelted to obtain low-ice nickel, and the main element content is: Ni 20.21%, Cu 10.52%, Fe 37.44%, Co 0.78%, and noble metal about 10 g/t.
  • a 4 mol/L sulfuric acid solution was used for leaching at a normal pressure, a liquid-solid ratio of 10:1, a reaction temperature of 80 ° C, and a reaction time of 0.5 h.
  • iron, cobalt and nickel are leached into the solution, and almost all copper and precious metals are enriched in the leaching residue of cuprous sulfide, thereby realizing the separation of copper and nickel-cobalt.
  • the copper content in the filtered solution is less than 0.005g/L, and the iron is mainly in the form of divalent iron ions.
  • the obtained iron slag is calcined into an iron concentrate, which can be used for iron making.
  • the iron solution was adjusted to pH 4
  • the cobalt was extracted with P507
  • the cobalt chloride solution was stripped with hydrochloric acid to prepare a cobalt product.
  • the pH of the solution was adjusted to 5.5
  • nickel was extracted with P507
  • hydrochloric acid was stripped to obtain a nickel chloride solution for preparing a nickel product.
  • the solid phase filter residue is copper sulfide enriched with precious metals.
  • the main components are: Ni 0.45%, Cu 75.2%, Fe 0.78%, Co ⁇ 0.01%, precious metal about 70g/t (equivalent nickel ore cobalt leaching rate above 99%), direct converter to prepare crude copper, crude copper and electrolytic refining to obtain refined copper
  • the precious metals are enriched in the anode mud and sent to the precious metal system for recovery. Among them, the recovery rate of copper is over 98%, and the recovery rate of precious metals is over 95%.
  • a part of the smelting process is reacted with sulfur sulphide to produce sulphur, which is used in an amount of one-half of the molar amount of hydrogen sulphide; the remaining sulphur dioxide is sent to the sulphuric acid system to produce sulphuric acid as a leaching agent for decomposing low-ice nickel.
  • the copper-nickel sulfide ore is smelted and smelted to obtain low-ice nickel.
  • the main element content is Ni 13.25%, Cu 8.32%, Fe 38.44%, Co 0.64%.
  • the copper content in the filtered solution is less than 0.006g/L
  • the iron is mainly in the form of divalent iron ions
  • the pH of the solution is adjusted to 5-7, and then placed in a closed autoclave, the pure oxygen is passed through and the temperature is raised to 180 ° C, and the iron is The form of hematite is removed.
  • the cobalt was extracted with P507
  • the cobalt chloride solution was stripped with hydrochloric acid to prepare a cobalt product.
  • the pH of the solution was adjusted to 6.5
  • nickel was extracted with P507, and hydrochloric acid was stripped to obtain a nickel chloride solution for preparing a nickel product.
  • the solid phase filter residue is copper concentrate, the main component is: Ni 0.15%, Cu 73.2%, Fe 0.85%, Co ⁇ 0.008% (equivalent nickel ore cobalt leaching rate is above 99%), oxidized and calcined, then leached with sulfuric acid to obtain copper sulfate solution and leaching residue, wherein the copper recovery rate can reach 98% or more.
  • a copper sulfate solution is used to make copper.
  • a part of the smelting process is reacted with sulfur sulphide to produce sulphur, which is used in an amount of one-half of the molar amount of hydrogen sulphide; the remaining sulphur dioxide is sent to the sulphuric acid system to produce sulphuric acid as a leaching agent for decomposing low-ice nickel.
  • the copper-nickel sulfide ore is smelted and smelted to obtain low-ice nickel.
  • the main element content is Ni 16.55%, Cu. 10.32%, Fe 33.44%, Co 0.34%, precious metals are about 8.9 grams.
  • a 1 mol/L sulfuric acid solution was used for leaching at a normal pressure, a liquid-solid ratio of 20:1, a reaction temperature of 25 ° C, and a reaction time of 5 hours.
  • the copper content in the filtered solution is less than 0.008g/L, and the iron is mainly in the form of divalent iron ions. Without further reduction, it can be directly oxidized by 30%-60% oxygen-enriched air under normal pressure, and the pH of the solution is maintained.
  • the iron is precipitated by goethite precipitation, and the obtained iron slag is calcined into an iron concentrate, which can be used for iron making.
  • adjust the pH to 5.0 extract the cobalt with Cyanex272, and back-extract with sulfuric acid to obtain a cobalt sulfate solution for preparing the cobalt sulfate product; then adjust the pH of the solution to 6.5, then extract the nickel with Cyanex272, and strip the sulfuric acid to obtain nickel sulfate.
  • the solid phase filter residue is a copper concentrate enriched with precious metals.
  • the main component is: Ni 0.16%, Cu76.2%, Fe 0.65%, Co ⁇ 0.01% (equivalent nickel ore cobalt leaching rate is above 99%), precious metal about 65 grams.
  • Oxygen pressure leaching in an autoclave is used to obtain a copper-containing solution for copper production, and leaching slag is used for recovering precious metals. Among them, the recovery rate of copper is over 98%, and the recovery rate of precious metals is over 95%.
  • a part of the smelting process is reacted with sulfur sulphide to produce sulphur, which is used in an amount of one-half of the molar amount of hydrogen sulphide; the remaining sulphur dioxide is sent to the sulphuric acid system to produce sulphuric acid as a leaching agent for decomposing low-ice nickel.
  • the copper-nickel sulfide ore is smelted and smelted to obtain low-ice nickel.
  • the main element content is Ni 12.55%, Cu 8.32%, Fe 39.44%, Co 0.24%, precious metal about 7.5 grams.
  • a 3 mol/L sulfuric acid solution was used for leaching at a normal pressure, a liquid-solid ratio of 5:1, a reaction temperature of 50 ° C, and a reaction time of 2 h.
  • a reaction temperature of 50 ° C As a raw material, a 3 mol/L sulfuric acid solution was used for leaching at a normal pressure, a liquid-solid ratio of 5:1, a reaction temperature of 50 ° C, and a reaction time of 2 h.
  • the low-ice nickel almost all of iron, cobalt and nickel are leached into the solution, and copper and precious metals are concentrated in the slag, thereby realizing the separation of copper and nickel-cobalt.
  • the copper content in the filtered solution is less than 0.003g/L
  • the iron is mainly in the form of divalent iron ions
  • the pH of the solution is adjusted to 4-6, and then placed in a closed autoclave, the pure oxygen is passed through and the temperature is raised to 220 ° C, and the iron is The form of hematite is removed.
  • the pH was adjusted to 5.5
  • the cobalt was extracted with Cyanex 272, and the cobalt sulfate solution was stripped with sulfuric acid to prepare a cobalt sulfate product; then the pH of the solution was adjusted to 7.0, and the nickel was extracted with Cyanex 272, and the sulfuric acid was stripped to obtain nickel sulfate.
  • a solution for the preparation of a nickel sulfate product is less than 0.003g/L
  • the iron is mainly in the form of divalent iron ions
  • the pH of the solution is adjusted to 4-6, and then placed in a closed autoclave, the pure oxygen is passed
  • the solid phase filter residue is a copper concentrate enriched with precious metals.
  • the main components are: Ni 0.12%, Cu 72.8%, Fe 0.45%, Co ⁇ 0.005% (equivalent to more than 99% leaching rate of nickel-iron cobalt), and about 68 grams of precious metal.
  • Oxygen pressure leaching in an autoclave is used to obtain a copper-containing solution for copper production, and leaching slag is used for recovering precious metals. Among them, the recovery rate of copper is over 98%, and the recovery rate of precious metals is over 95%.
  • a part of the smelting process is reacted with sulfur sulphide to produce sulphur, which is used in an amount of one-half of the molar amount of hydrogen sulphide; the remaining sulphur dioxide is sent to the sulphuric acid system to produce sulphuric acid as a leaching agent for decomposing low-ice nickel.
  • Program A A method for recovering primary associated elements from copper-nickel sulfide ore, specific embodiment 5 ⁇ 8 .
  • the copper-nickel sulfide ore is smelted and smelted to obtain low-ice nickel.
  • the main element content is Ni 20.21%, Cu 10.52%, Fe37.44%, Co 0.78%, precious metal about 10g/t, and sulfur dioxide formation. .
  • a solution having a sulfuric acid mass fraction of 30% was prepared as a reaction bottom liquid; and a solution having a sulfuric acid mass fraction of 90% was prepared as a leaching reaction liquid.
  • the reactor is filled with 40% of the reaction bottom volume of the total kettle volume; at the same time, low ice nickel and reaction leaching solution are added to the reaction vessel to carry out the reaction, and the consumption of sulfuric acid in the reaction kettle is maintained in accordance with the amount of addition; the reaction is continued until the reaction is continued until When the slurry in the reactor reached 80% of the total volume of the kettle, the addition was stopped, the reaction was continued for 1 hour, and the hydrogen sulfide gas generated during the reaction was collected.
  • the slurry is cooled to room temperature and then filtered to obtain a primary filtrate and a primary filter residue, wherein one filtrate is used as a reaction bottom liquid for the next leaching; the primary filter residue is pumped into a dissolution tank containing deionized water, while the reaction is in progress.
  • the nickel sulfate, cobalt sulfide, and ferrous sulfate crystals precipitated by saturation are redissolved and then secondary filtered to obtain a secondary filtrate containing nickel sulfate, cobalt sulfate, and ferrous sulfate, and a secondary filter residue rich in cuprous sulfide and precious metal. , the separation of copper and nickel cobalt is achieved.
  • the content of copper in the filtered solution is less than 0.003g/L, the iron is mainly in the form of divalent iron ions, the pH of the solution is maintained at 3-4, and the air is directly oxidized, and no reduction is required to remove iron from the goethite.
  • the obtained iron slag is calcined into an iron concentrate, which can be used for iron making. After the iron was removed, the pH was adjusted to 4, cobalt was extracted with P507, and cobalt chloride solution was stripped with hydrochloric acid to prepare a cobalt product. The pH of the solution was adjusted to 5.5, nickel was extracted with P507, and hydrochloric acid was stripped to obtain a nickel chloride solution for preparing a nickel product.
  • the secondary filter residue is copper sulfide enriched with precious metals.
  • the main components are: Ni 0.49%, Cu 73.2%, Fe 0.72%, Co ⁇ 0.009%, precious metal about 67g/t (equivalent nickel ore cobalt leaching rate above 99%), direct converter to prepare crude copper, crude copper and electrolytic refining to obtain refined copper
  • the precious metals are enriched in the anode mud and sent to the precious metal system for recovery. Among them, the recovery rate of copper can reach over 98%, and the recovery rate of precious metals can reach over 95%.
  • a part of the smelting process is reacted with hydrogen sulfide to prepare sulfur, and the amount thereof is one-half of the molar amount of hydrogen sulfide; the remaining sulfur dioxide is sent to the sulfuric acid system to prepare sulfuric acid, which is used for the reaction bottom liquid and the leaching reaction liquid.
  • the copper-nickel sulfide ore is smelted and smelted to obtain low-ice nickel.
  • the main element content is Ni13.25%, Cu8.32%, Fe 38.44%, Co0.64%, precious metal about 8g/t, and sulfur dioxide formation.
  • a solution having a sulfuric acid mass fraction of 40% was prepared as a reaction bottom liquid; and a solution having a sulfuric acid mass fraction of 85% was prepared as a leaching reaction liquid.
  • the slurry is cooled to room temperature and then filtered to obtain a primary filtrate and a primary filter residue, wherein one filtrate is used as a reaction bottom liquid for the next leaching; the primary filter residue is pumped into a dissolution tank containing deionized water, while the reaction is in progress.
  • the nickel sulfate, cobalt sulfide, and ferrous sulfate crystals precipitated by supersaturation are re-dissolved and then secondary filtered to obtain a secondary filtrate containing nickel sulfate, cobalt sulfate, and ferrous sulfate, and a secondary solution rich in cuprous sulfide and precious metal.
  • the residue is filtered to achieve separation of copper from nickel and cobalt.
  • the copper content in the filtered solution was less than 0.009 g/L, and the iron was mainly present in the form of divalent iron ions.
  • the solution was placed in a closed autoclave, and the pure oxygen was passed through and the temperature was raised to 180 ° C to remove the iron in the form of hematite.
  • the cobalt was extracted with P507, and the cobalt sulfate solution was stripped with sulfuric acid to prepare a cobalt product.
  • the pH of the solution was adjusted to 6.5, nickel was extracted with P507, and sulfuric acid was stripped to obtain a nickel sulfate solution for preparing a nickel product.
  • the secondary filter residue is copper sulfide enriched with precious metals.
  • the main components are: Ni 0.16%, Cu 72.6%, Fe 0.95%, Co ⁇ 0.007% (the leaching rate of nickel-iron cobalt is more than 99%).
  • the precious metal is about 65g/t (the leaching rate of nickel-iron-cobalt is more than 99%).
  • After oxidative roasting it is leached with sulfuric acid to obtain copper sulphate solution and leaching slag rich in precious metal.
  • the leaching slag enriched in precious metal is sent to the precious metal system for recovery. Among them, the recovery rate of copper can reach over 98%, and the recovery rate of precious metal can reach 95. %the above.
  • a part of the smelting process is reacted with hydrogen sulfide to prepare sulfur, and the amount thereof is one-half of the molar amount of hydrogen sulfide; the remaining sulfur dioxide is sent to the sulfuric acid system to prepare sulfuric acid, which is used for the reaction bottom liquid and the leaching reaction liquid.
  • the copper-nickel sulfide ore is smelted and smelted to obtain low-ice nickel.
  • the main element content is Ni16.55%, Cu10.32%, Fe33.44%, Co0.34%, precious metal about 11g/t, and sulfur dioxide formation.
  • a solution having a sulfuric acid mass fraction of 20% was prepared as a reaction bottom liquid; and a solution having a sulfuric acid mass fraction of 60% was prepared as a leaching reaction liquid.
  • the slurry is cooled to room temperature and then filtered to obtain a primary filtrate and a primary filter residue, wherein one filtrate is used as a reaction bottom liquid for the next leaching; the primary filter residue is pumped into a dissolution tank containing deionized water, while the reaction is in progress.
  • the nickel sulfate, cobalt sulfide, and ferrous sulfate crystals precipitated by supersaturation are re-dissolved and then secondary filtered to obtain a secondary filtrate containing nickel sulfate, cobalt sulfate, and ferrous sulfate, and a secondary solution rich in cuprous sulfide and precious metal.
  • the residue is filtered to achieve separation of copper from nickel and cobalt.
  • the copper content in the filtered solution is less than 0.006g/L
  • the iron is mainly in the form of divalent iron ions
  • the pH of the solution is maintained at 3-4
  • the oxygen-enriched air is directly passed through 30%-50% for oxidation, without further reduction.
  • Iron is formed into goethite, and the obtained iron slag is calcined into iron concentrate, which can be used for iron making.
  • the pH was adjusted to 5
  • cobalt was extracted with Cyanex 272, and cobalt chloride solution was stripped with hydrochloric acid to prepare a cobalt product.
  • the pH of the solution was adjusted to 6.5, and nickel was extracted with Cyanex 272, and hydrochloric acid was stripped to obtain a nickel chloride solution for preparing a nickel product.
  • the secondary filter residue is copper sulfide enriched with precious metals.
  • the main components are: Ni 0.12%, Cu 76.4%, Fe 0.62%, Co ⁇ 0.008% (the leaching rate of nickel-iron cobalt is more than 99%).
  • the noble metal is about 78g/t (the leaching rate of nickel-iron-cobalt is more than 99%), and is leached by oxygen pressure in an autoclave to obtain a copper-containing solution for copper production, and the leaching residue is used for recovering precious metals, wherein copper recovery rate Up to 98%, the recovery rate of precious metals can reach more than 95%.
  • a part of the smelting process is reacted with hydrogen sulfide to prepare sulfur, and the amount thereof is one-half of the molar amount of hydrogen sulfide; the remaining sulfur dioxide is sent to the sulfuric acid system to prepare sulfuric acid, which is used for the reaction bottom liquid and the leaching reaction liquid.
  • the copper-nickel sulfide ore is smelted and smelted to obtain low-ice nickel.
  • the main element content is Ni12.55%, Cu8.32%, Fe 39.44%, Co0.24%, precious metal about 10.8g/t, and sulfur dioxide formation.
  • a solution having a sulfuric acid mass fraction of 60% was prepared as a reaction bottom liquid; and a solution having a sulfuric acid mass fraction of 95% was prepared as a leaching reaction liquid.
  • the slurry is cooled to room temperature and then filtered to obtain a primary filtrate and a primary filter residue, wherein one filtrate is used as a reaction bottom liquid for the next leaching; the primary filter residue is pumped into a dissolution tank containing deionized water, while the reaction is in progress.
  • the nickel sulfate, cobalt sulfide, and ferrous sulfate crystals precipitated by supersaturation are re-dissolved and then secondary filtered to obtain a secondary filtrate containing nickel sulfate, cobalt sulfate, and ferrous sulfate, and a secondary solution rich in cuprous sulfide and precious metal.
  • the residue is filtered to achieve separation of copper from nickel and cobalt.
  • the copper content in the filtered solution is less than 0.004g/L, and the iron is mainly in the form of divalent iron ions.
  • the solution is directly placed in a closed autoclave, the pure oxygen is passed through and the temperature is raised to 220 ° C, and the iron is made of hematite. The ore form is removed.
  • the iron removal liquid was adjusted to pH 5.5
  • the cobalt was extracted with Cyanex 272, and the cobalt sulfate solution was stripped with sulfuric acid to prepare a cobalt product.
  • the pH of the solution was adjusted to 7, and nickel was extracted with Cyanex 272, and sulfuric acid was stripped to obtain a nickel sulfate solution for preparing a nickel product.
  • the secondary filter residue is copper sulfide enriched with precious metals.
  • the main components are: Ni 0.11%, Cu 72.3%, Fe 0.40%, Co ⁇ 0.004% (equivalent to the leaching rate of nickel-iron cobalt is above 99%), precious metal about 75g / t (equivalent nickel ore cobalt leaching rate is above 99%), using autoclave oxygen
  • the leaching is carried out to obtain a copper-containing solution for copper production, and the leaching slag is used for recovering precious metals, wherein the recovery rate of copper is over 98%, and the recovery rate of precious metals is over 95%.
  • a part of the smelting process is reacted with hydrogen sulfide to prepare sulfur, and the amount thereof is one-half of the molar amount of hydrogen sulfide; the remaining sulfur dioxide is sent to the sulfuric acid system to prepare sulfuric acid, which is used for the reaction bottom liquid and the leaching reaction liquid.

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Abstract

一种铜镍硫化矿综合回收利用的方法及其系统。在常压条件下可直接浸出铜镍硫化矿精矿或铜镍硫化矿经造锍熔炼得到的低冰镍。在浸出过程中，镍钴铁的浸出率高达99％以上，而且铜几乎不被浸出，直接实现了铜与镍钴等元素的深度分离，取消了传统工艺中铜镍分离的庞大系统。同时，贵金属也不被浸出，几乎全部与铜一起留在浸出渣中。简化了铜镍硫化矿的冶炼流程，有效地实现了镍、铜、钴、贵金属以及元素硫的回收利用。

Description

一种铜镍硫化矿综合回收利用的方法及其系统 技术领域
本发明涉及有色金属冶金技术领域，更具体地，涉及一种铜镍硫化矿综合回收利用的方法及其系统。
 背景技术
镍是一种重要的战略金属，广泛应用于国防、航空航天、交通运输、石油化工、能源等领域。相当数量的镍矿是硫化矿，伴生有铜、钴和贵金属（金、银和铂族金属）等，如甘肃金川铜镍矿以及新疆喀拉通克铜镍矿。因此在提取镍、铜的同时还需要考虑钴和贵金属的回收。
传统的铜镍硫化矿的冶炼工艺首先是通过造锍熔炼，使铁、镍、钴和铜以硫化物形式富集而形成低冰镍，伴生的贵金属也被富集；然后将低冰镍进行转炉吹炼，将大部分的铁以及硫除去，形成高冰镍。吹炼过程中，往往造成钴的氧化损失（约损失40-60%，难以回收），而生成的二氧化硫通过制酸系统得到工业硫酸（硫酸因用途和运输半径的问题而大量积存）。之后，吹炼得到的高冰镍的处理方法大致分为三类。
其一是，高冰镍经缓冷后进行磨浮分离，分别得到低铜硫化镍精矿、低镍硫化铜精矿和一次合金。一次合金还需再次硫化-磨浮分离出相应的低铜硫化镍精矿、低镍硫化铜精矿以及二次合金。二次合金用于贵金属的回收，低铜硫化镍精矿用于提取镍，但由于磨浮分离不彻底，后续还需要除去携带的杂质铜，硫化铜精矿用于提铜，自然也有镍作为杂质被携带的问题，造成冶炼工序相当繁琐。
其二，高冰镍还可采用酸选择性浸出工艺，主要分为：低酸加压氧浸或高酸常压浸出。低酸加压氧浸已在我国的阜康冶炼厂应用。据报道，阜康冶炼厂采用低酸两段逆流浸出，首先是一段常压浸出（浸出终液的pH ≥6.2 ），其次是一段加压氧浸，通过精确控制氧气分压使硫化镍氧化浸出，而使铜不浸出（最终得到浸出液的pH 为1.8-2.8，氧压0.05-0.06MPa）。通过两段逆流浸出后获得Cu、Fe≤0.01g/L的硫酸镍溶液，而原料中的铜、贵金属、铁和硫几乎全部以及40%左右的钴留在含镍2%-3%的终渣里。而高酸常压浸出最早在克里斯蒂安松精炼厂应用，该工艺用高浓度的盐酸（275g/L）做浸出剂，得到的浸出富液含镍约120g/L、盐酸160g/L，还有铁、钴、铜各2g/L。大约3%的铜被浸出，大部分留在渣中。然后经过溶剂萃取分离铁、钴、铜后，经蒸发浓缩使氯化镍结晶析出。另外，彭少方等研究了高冰镍硫酸浸出的动力学，并也提及采用间歇式二级逆向浸出。高冰镍的主要成份Ni 2S 3在与酸反应过程中，在较低温度下容易生成难处理β-NiS相，因此高冰镍的高酸常压分解工艺需要在温度高于90℃下才能有效的进行。
其三，高冰镍也可采用高压氧条件下的氨浸出。通过控制溶液中的游离氨含量以及氧压，使铜镍钴转变为金属氨配合物而溶解，同时硫被氧化成硫酸根，贵金属以及铁形成渣相用于回收。浸出过程中游离氨控制尤其重要，浓度低造成浸出率低，浓度过高又会形成钴的高氨络合物，因其不溶而造成钴的损失。
以上三种技术思路均可处理高冰镍。但问题是由低冰镍吹炼成高冰镍的过程当中，大部分的钴进入到吹炼渣中，钴的一次收率低。另外，因流程冗长，约损失10-20%的铂族金属。
为回收吹炼渣中损失的钴，有人将吹炼渣再经火法处理，通过还原熔炼回收损失的钴，还原产物主要成分为铁钴镍的合金以及硫化物，成为钴冰镍。但是由于钴易被氧化，含量低，在吹炼渣中过于分散，即使通过还原熔炼，仅仅只能回收一部分的钴。此外，这一钴冰镍浸出非常复杂，需经三段浸出，第一段主要为合金的浸出，为了防止铜的浸出，需要在浸出过程中或者浸出后通入硫化氢或者加入硫化钠，而后形成的浸出渣再需两段浸出才能得到含钴溶液。这样，大量的铁在硫相-渣相中循环往复，回收工艺也十分繁琐。
总的来说，将低冰镍吹炼成高冰镍，虽较好地解决了铜镍的回收问题，但在伴生钴及贵金属回收方面存在严重问题。而且硫以硫酸的形式产出，市场和运输半径也是令人头疼的问题。
直接处理低冰镍，可望避免上述的吹炼过程中钴与贵金属等伴生有价元素损失的问题。但现有的处理低冰镍的方法在回收伴生有价金属时仍有不便。如低冰镍的硫酸化焙烧可使镍钴铜转化为水溶性的硫酸盐，铁转化为水不溶的氧化物，生成的二氧化硫仍用于制酸。但伴生的铂族金属存留于铁渣中，又需要专门的复杂流程来提取。低冰镍也可以通过氧压酸浸来处理，例如尹飞等以及邓智林等作了详细研究。但氧化生成的硫磺会形成阻滞膜，影响浸出。此外氧压浸出时，相当量的铁转化成铁渣，虽有利于后序的镍钴提取，但贵金属与其夹杂导致回收困难。另外，浸出过程中硫氧化成硫磺进入渣相，仍需要进一步氧化以回收贵金属。
总的来说，现有直接处理低冰镍有火法和湿法两类工艺。火法可采用硫酸化焙烧，然后再选择性浸出有价元素，氧化铁留在浸出渣中，但铁渣中的贵金属回收困难；很多人青睐湿法，湿法一般采用氧压浸出，需要使用高压釜和纯氧，但同样面临要从铁渣中回收贵金属的问题，而且酸性氧压浸出时硫氧化成硫磺形成包裹，贵金属回收依旧困难。
 技术问题
本发明要解决的技术问题是现有铜镍硫化矿冶炼工艺中无法有效实现各元素的回收，特别是元素钴和贵金属的回收率过低。
 技术解决方案
为了解决上述技术问题，本发明提供了一种铜镍硫化矿综合回收利用的方法，包括以下步骤：
1）选择性浸出：
通过方案A或方案B获取富集有镍铁钴的浸出液和富集有铜的浸出渣：
方案A：即为从铜镍硫化矿中回收主伴生元素的方法，其选择性浸出步骤为：
向反应底液中持续加入铜镍硫化矿经造锍熔炼得到的低冰镍以及浸出反应液，进行选择性浸出，分别收集硫化氢气体、第一浸出液和第一次浸出渣，其中，所述反应底液为质量分数20%-60%的硫酸溶液，所述浸出反应液为质量分数60%-95%的硫酸溶液；向所述第一次浸出渣中加入水，溶解，分别收集第二浸出液和第二浸出渣；
方案B：即为对铜镍硫化矿综合利用的方法，其选择性浸出步骤为：
对铜镍硫化矿经造锍熔炼得到的低冰镍直接使用硫酸进行常压选择性浸出，分别收集硫化氢气体、浸出液和浸出渣，其中，常压选择性浸出的温度为25-80℃；
方案A的第二浸出液、方案B的浸出液即为富集有镍铁钴的浸出液；方案A的第二浸出渣、方案B的浸出渣为富集有铜的浸出渣；
2）对步骤1)富集有镍铁钴的浸出液进行除铁，分别收集除铁后液和除铁渣，除铁后液用于镍和钴的提取，除铁渣用于炼铁；
和/或，对步骤1)的富集有铜的浸出渣送铜冶炼系统冶炼，分别得到铜和贵金属。
在本发明中，使用高浓度硫酸直接处理铜镍硫化矿或铜镍硫化矿经造锍熔炼得到的低冰镍，利用镍、钴、铁的硫酸盐在高浓度硫酸溶液中溶解度低的特性，使它们结晶析出进入渣相，进而过滤就可实现与高浓度硫酸溶液分离。
低冰镍主要来源于铜镍硫化精矿，主要成分是Ni 5Fe 4S 8，除镍外同时富含铜、钴和大量铂族需要回收，在本发明方案中，低冰镍为铜镍硫化矿经造锍熔炼制得，即本发明的方法更适用于铜镍硫化矿经造锍熔炼制得的低冰镍的分解与提取。
本发明方法优选的方案A和方案B。这两种具体的方案，实际解决的技术问题均为现有方案难于良好回收其中有价元素的问题，解决的技术问题相同。该两种优选的方案具有相同的发明创新点，通过独创的常压酸浸出思路，不对低冰镍进行常规的吹炼，直接进行硫酸的常压浸出，实现将铁、镍、钴富集金属至溶液中，并将铜以及贵金属富集至浸出渣中，达到将铜以及贵金属和铁、镍、钴分离的目的。随后再对浸出液进行除铁处理，将浸出液中的铁转化成针铁矿或者赤铁矿，实现铁与镍-钴的分离；最后实现镍和钴的分离。综上分析，本发明的优选的两种方案，解决的对象相同（或者相类似），解决的手段均为常压酸浸-除铁以及镍钴分离，解决的主体思路相同，属于同一发明构思，预期达到的目的均是解决现有回收方法存在的伴生矿物损失严重的问题，均是达到提升元素回收率的目的，达到的目的相同；因此，本发明所优选的两种实施方案，属于同一发明构思的发明创造，符合单一性的要求。
在本发明的方案中，取消了常见方法中对低冰镍的吹炼过程，有效地防止了吹炼过程中造成的钴的损失。同时，使用上述浸出步骤有效地将铜和贵金属留在浸出渣，再将该浸出渣送铜冶炼系统冶炼，此时贵金属走向单一，可有效回收，提高了铜镍硫化矿中伴生的钴和铂族金属回收率。
方案A中，使用高浓度硫酸直接处理铜镍硫化矿经造锍熔炼得到的低冰镍，利用镍、钴、铁的硫酸盐在高浓度硫酸溶液中溶解度低的特性，使它们结晶析出进入渣相，进而过滤就可实现与高浓度硫酸溶液分离。浸出过程中，硫化亚铜和贵金属不参与反应，也一同留在渣中。含有镍、钴、铁的硫酸盐晶体、硫化亚铜和贵金属的浸出渣经过加水浸出使硫酸盐溶解，过滤后就可得到硫化亚铜和贵金属的二次滤渣和含有镍、钴、铁硫酸盐的水溶液。然后二次滤渣送铜冶炼系统回收铜和贵金属。镍钴铁则经除铁后再萃取分离镍钴就可得到相应的产品。在本发明中，直接处理铜镍硫化精矿或铜镍硫化矿经造锍熔炼所得的低冰镍可以避免传统冶炼过程工艺中钴与贵金属等伴生有价元素损失的问题。本发明利用铁镍钴的硫酸盐因饱和而从浸出液中结晶析出，实现了与高浓度硫酸的分离。一次滤渣经简单水溶后又实现了铜与铁镍钴的分离。对铜镍硫化精矿或低冰镍直接使用硫酸进行常压选择性浸出，在该浓度以及液固比下，镍铁钴溶于硫酸溶液中，并完全反应生成硫化氢气体，此时，铜镍硫化矿或低冰镍中的硫化亚铜和贵金属几乎不分解，即可在浸出过程中实现镍铜的深度分离。同时，使用上述浸出步骤有效地将铜和贵金属留在第二浸出渣，再将该浸出渣送铜冶炼系统冶炼，此时贵金属走向单一，可有效回收，提高了铜镍硫化矿中伴生的钴和铂族金属回收率。本领域技术人员可以根据实际需要来选择对第二浸出液或是第二浸出渣进行相应的处理，来分别回收镍、钴、铁、铜和贵金属等伴生元素。
作为优选，在实际操作过程中，通常是将浸出反应置于反应釜中，即步骤1）可以为：向反应釜中填充反应底液，即质量分数20%-60%的硫酸溶液，作为反应底液；同时向反应釜中加入低冰镍（或铜镍硫化矿）和浸出反应液质量分数60%-95%的硫酸溶液进行反应。
在一个优选实施方式中，为了使铁镍钴的硫酸盐因饱和从浸出反应液中结晶析出，浸出反应液和低冰镍连续加入，并维持反应釜中硫酸的消耗量与加入量一致，持续加料进行反应。
在本发明一个优选实施方式中，为了使反应更加完全以及便于控制反应终点溶液的硫酸浓度，向反应釜中通常填充总釜体积30%-60%的反应底液，即质量分数20%-60%的硫酸溶液。
在本发明一个优选实施方式中，通常是加料完成后继续浸出0.5-2h。在优选实施方式中，可以为：直至反应釜中料浆达到总釜体积的80%时停止加料，继续反应0.5-2h，并收集反应过程生成的硫化氢气体、第一浸出液和第一浸出渣。
方案A中，为了使得步骤1）中的浸出更加完全，使得镍铜的完全分离，选择性浸出为常压非氧化性浸出，且无需额外的加热设备，随着低冰镍和60%-95%硫酸的持续加入，溶液反应温度会升温至80-100℃。
在步骤1）方案A中，所述低冰镍和浸出反应液同时连续加入，且两者的加入量与消耗量相同；所述第一浸出液返回作为下一批物料的反应底液，循环使用。
当得到第一浸出液以及第一浸出渣后，其中，将第一浸出液回收作为反应底液返回反应釜处理下一批物料，循环使用，大大降低酸耗以及对环境的污染，并可提高金属回收率。可以将第一浸出渣泵入含去离子水的溶解槽中，此时，在浸出反应过程中因过饱和而析出的硫酸镍、硫化钴以及硫酸亚铁晶体重新溶解后二次过滤，分别收集含有硫酸镍、硫酸钴和硫酸亚铁的第二浸出液以及富集有硫化亚铜和贵金属的第二浸出渣。
本发明另一浸出低冰镍的方法，方案B中，在25-80℃下，铜镍硫化矿经造锍熔炼制得的低冰镍在硫酸溶液中发生复分解反应，镍铁钴溶于水，并生成硫化氢气体，反应非常的彻底，同时，在该温度的硫酸下，低冰镍中的硫化亚铜几乎不分解，可在浸出过程中实现铜镍的深度分离，提高回收率，打破了以住工作中使用90℃以上的高温才能实现矿物中各元素的有效提取的状况，节约了能源，也降低了操作人员可能受的风险。方案B中，直接处理铜镍硫化矿经造锍熔炼所得的低冰镍可以避免低冰镍在后序传统吹炼过程工艺中钴与贵金属等伴生有价元素损失的问题。对低冰镍直接使用硫酸进行常压选择性浸出，在该浓度以及液固比下，镍铁溶于硫酸溶液中，并完全反应生成硫化氢气体，此时，低冰镍中硫化亚铜和贵金属几乎不分解，即可在浸出过程中实现镍铜的深度分离。
方案B中，为了使得步骤1)中的浸出更加完全，使得镍铜的完全分离，在一个优选实施方式中，步骤1)中硫酸浓度为1mol/L-6mol/L，常压选择性浸出的温度为25-80℃，常压选择性浸出时间为0.5-5h。
方案B中，更优选地是，步骤1)中硫酸浓度为3mol/L-4mol/L，常压选择性浸出时间为0.5-2h，浸出温度为50-70℃，液固比为5:1-10:1。
为了解决长期困扰硫化镍矿企业的硫的出路问题，在本发明一个优选实施方式中，可以将选择性浸出后收集的硫化氢气体与造锍熔炼中产生的二氧化硫送硫磺系统制备硫磺，而多余的二氧化硫送硫酸系统制备硫酸用于配硫酸溶液，即浸出反应液和反应底液。在本发明优选的实施方式中，将生成的二氧化硫一部分制酸作为浸出剂，一部分与生成的硫化氢反应生成硫磺，从而解决了传统工艺中大量硫酸的积存问题。另外，本发明将低冰镍在硫酸浸出过程中所产生的硫化氢气体用于制备硫磺，可以解决长期困扰硫化镍矿企业的硫的出路问题，与传统方法中硫用以制备的硫酸的情况相比更易于储存和运输。
本领域技术人员可以根据实际需要来选择在浸出步骤后，对浸出液进行除铁或是对浸出渣送铜冶炼系统冶炼或是既对浸出液进行除铁也对浸出渣送铜冶炼系统冶炼，较优选地是，既对浸出液进行除铁，用于回收镍、钴和/或铁，也对浸出渣送铜冶炼系统冶炼，用于回收铜和贵金属。
在本发明中，浸出液的铁主要呈二价铁离子形式存在，例如，方案A中，本发明中第二浸出液中溶液中铜含量小于0.009g/L，优选小于0.003g/L，方案B中，步骤1)的浸出液中溶液中铜含量小于0.008g/L，优选小于0.003g/L，铁主要呈二价铁离子形式存在，无需再经还原可使用本领域中常用的除铁方法进行除铁，可直接氧化形成针铁矿或赤铁矿去除。为了能更好地除铁并且不影响镍钴的回收率，在本发明一个优选实施方式中，优选采用针铁矿法或赤铁矿法。
所述步骤2）中，对浸出液进行除铁具体为：
向浸出液或调整pH为3~7的浸出液中通入富含氧气的气体，得到除铁后液和除铁渣；
或，对浸出液加入到高压反应釜中与氧化性气体进行反应，反应完成后进行固液分离，将滤渣洗涤干燥后即为除铁渣，所得滤液为除铁后液。
优选地，可将步骤1)中浸出液的pH调至4-7，置于密闭高压釜中，通纯氧并升温至220℃，将铁以赤铁矿形式除去，得到除铁后液和除铁渣。
优选地，也可以向步骤1)中浸出液通入空气或富氧空气，同时维持溶液的pH为3-4，即可将铁以针铁矿形式除去，得到除铁后液和除铁渣。可将得到的铁渣焙烧成铁精矿，用于炼铁。
作为优选，除铁过程中，与氧化性气体反应的温度为150-200℃，维持釜内氧分压为0.1-1MPa，反应时间1-5h。
可将得到的铁渣焙烧成铁精矿，用于炼铁，也可将除铁渣用做磷酸铁锂中铁的原料。
除铁后液可使用本领域中常用的方法来实现镍和钴的提取，为了完全实现本发明中镍和钴的提取，在一个优选实施方式中，将除铁后液的pH调至4.0-5.5后向除铁后液中加入萃取剂，萃取分离得到含钴溶液和含镍溶液，再将含镍溶液的pH调至5.5-7.0使用萃取剂进行镍的萃取；其中，所述萃取剂为P507的煤油溶液或Cyanex272的煤油溶液，体积分数为10-50%。在上述萃取剂中，煤油为稀释剂。其中，P507为2-乙基己基膦酸单（2-乙基己基）酯，Cyanex272为二（2,4,4-三甲基戊基）次磷酸。
当萃取剂为P507的煤油溶液时，将除铁后液的pH调至4.0-5.0，再向除铁后液中加入萃取剂，用萃取剂萃取钴，萃取分离得到含钴溶液(含钴有机相)和含镍溶液，再将含镍溶液的pH调至5.5-6.5，用萃取剂萃取镍，盐酸反萃得到氯化镍溶液，用于制备镍产品。其中，将含钴溶液(含钴有机相)用盐酸反萃得到氯化钴溶液，用于制备钴产品。
当萃取剂为Cyanex272的煤油溶液时，将除铁后液的pH调至5.0-5.5，再向除铁后液中加入萃取剂，萃取分离得到含钴溶液(含钴有机相)和含镍溶液，再将含镍溶液的pH调至6.5-7.0，用萃取剂萃取镍，硫酸反萃得到硫酸镍溶液，用于制备硫酸镍产品。其中，将含钴溶液(含钴有机相)用硫酸反萃得到硫酸钴溶液，用于制备硫酸钴产品。
在本发明一个优选实施方式中，可以采用本领域中常规的铜冶炼方法得到铜和贵金属，为了使铜和贵金属完全分离，在本发明一个优选实施方式中，优选为：
将处理低冰镍所得富集有铜的浸出渣（例如第二浸出渣或方案B步骤（1）的浸出渣）送转炉吹炼制得粗铜，再经电解分别得到精铜和富集贵金属的阳极泥，阳极泥用于提取贵金属；
或，将处理低冰镍所得富集有铜的浸出渣（例如第二浸出渣或方案B步骤（1）的浸出渣）经氧化焙烧后采用酸浸出，分别收集富集铜的浸出液和富集贵金属的浸出渣，浸出渣用于提取贵金属；
或，将处理低冰镍所得富集有铜的浸出渣（例如第二浸或方案B步骤（1）的浸出渣）出渣进行氧压浸出，分别收集富集铜的浸出液和富集贵金属的浸出渣，浸出渣用于提取贵金属。
本发明的方法所得到镍、铁、钴的浸出率均在99%以上，钴和贵金属得到了有效地回收，铜的回收率在98%以上，贵金属的回收率在95%以上。
根据本发明另一个方面，还提供了一种铜镍硫化矿综合回收利用的系统，包括：获取浸出液和浸出渣的装置，为选择性浸出装置和水溶解装置；或者为常压选择性浸出装置：
选择性浸出装置，具有低冰镍和浸出反应液各自的连续加料口，选择性浸出装置中含有反应底液，且使得向反应底液中持续加入铜镍硫化矿经造锍熔炼得到的低冰镍和浸出反应液时发生选择性浸出反应；所述选择性浸出装置还包括硫化氢气体的收集装置、第一浸出液的收集装置和第一次浸出渣的收集装置，其中，反应底液为质量分数20%-60%的硫酸溶液，浸出反应液为质量分数60%-95%的硫酸溶液；
水溶解装置，用于使用水溶解第一次浸出渣，分别收集第二浸出液和第二次浸出渣；
常压选择性浸出装置，用于对低冰镍直接使用硫酸进行常压选择性浸出，分别收集硫化氢气体、浸出液和浸出渣；
除铁装置，用于将水溶解装置中得到的第二次浸出液进行除铁，或用于将常压选择性浸出装置中得到的浸出液进行除铁；
镍和钴的提取装置，用于收集除铁装置中除铁后液，用于镍和钴的提取；
炼铁装置，用于处理除铁装置中的除铁渣，用于炼铁；
和/或，铜冶炼装置，用于将所述第二浸出渣或常压选择性浸出装置中得到的浸出渣进行铜冶炼，分别得到铜和贵金属。
在本发明一个优选实施方式中，系统中还包括：
造锍熔炼装置，用于处理铜镍硫化矿，并向所述常压选择性浸出装置中提供低冰镍，所述低冰镍为铜镍硫化矿经造锍熔炼制得。
硫磺制备装置，用于使所述造锍熔炼装置中产生的二氧化硫与所述常压选择性浸出装置中产生硫化氢气体完全反应制得硫磺；
硫酸制备装置，用于将所述造锍熔炼装置中产生的剩余二氧化硫转换成硫酸，并将其提供给所述常压选择性浸出装置。
在本发明一个优选实施方式中，系统中第一浸出液收集装置还可用于给选择性浸出装置提供反应底液。
方案A中，在该常压选择性浸出装置中还包括温度调控装置，用于将常压选择性浸出的温度控制在25-80℃，从而提高对铜镍硫化矿的综合利用。
方案A提出的铜镍硫化矿综合利用的方法及其系统对铜镍硫化矿经造锍熔炼所得的低冰镍直接用硫酸在25-80℃下进行常压选择性浸出，低冰镍中的镍、钴和铁被酸分解后进入溶液，浸出液经除铁后用于镍、钴的提取，除铁渣用于炼铁；低冰镍中的铜以硫化亚铜形式与贵金属一起保留在浸出渣，进铜冶炼，回收铜和贵金属。该方法流程短，效率高，不仅可以实现了镍铜的深度分离，还有利于大幅提高钴及贵金属的回收率，是一种清洁高效的元素综合利用工艺，易于大规模工业生产。
本发明的方法优选使用本发明的系统来实现。
本发明优选以下具体实施方案：
所述的综合利用方法具体分为方案A或方案B：
方案A：一种从铜镍硫化矿中回收主伴生元素的方法，包括：
1)向反应底液中持续加入铜镍硫化矿经造锍熔炼得到的低冰镍和浸出反应液，选择性浸出，分别收集硫化氢气体、第一浸出液和第一次浸出渣，其中，所述反应底液为质量分数20％-60％的硫酸溶液，所述浸出反应液为质量分数60％-95％的硫酸溶液；
2)向所述第一次浸出渣中加入水，溶解，分别收集第二浸出液（等同于方案B中步骤（1）获得的浸出液）和第二浸出渣（等同于方案B中步骤（1）获得的浸出渣）；
3)对所述第二浸出液进行除铁，分别收集除铁后液和除铁渣，所述除铁后液用于镍和钴的提取，所述除铁渣用于炼铁；
和/或，将所述第二浸出渣送铜冶炼装置冶炼，分别得到铜和贵金属。
作为优选，方案A，所述选择性浸出为常压非氧化性浸出；和/或，所述浸出反应液为质量分数为85％-90％的硫酸溶液。
作为优选，方案A，所述低冰镍和浸出反应液同时连续加入，且两者的加入量与消耗量相同；所述第一浸出液返回作为下一批物料的反应底液，循环使用。
作为优选，方案A，在步骤1)中，加料完成后继续浸出0.5-2h。
作为优选，方案A，所述造锍熔炼中产生的二氧化硫与步骤1)中的硫化氢气体反应制备硫磺，以及将剩余二氧化硫转换成步骤1)中进行常压选择性浸出所使用的硫酸溶液。
作为优选，方案A，所述步骤3)中对所述第二浸出液进行除铁具体为：
向第二浸出液中通入富含氧气的气体，得到除铁后液和除铁渣。
作为优选，方案A，所述步骤3)中所述除铁后液用于镍和钴的提取具体为：
将除铁后液pH调至4.0-5.5后，向除铁后液中加入萃取剂，萃取分离得到含钴溶液和含镍溶液，再将含镍溶液的pH调至5.5-7.0使用所述萃取剂进行镍的萃取；
其中，所述萃取剂为P507的煤油溶液或Cyanex272的煤油溶液，体积分数为10-50％。
作为优选，方案A中，所述铜和贵金属的回收方法具体为：
将第二浸出渣经转炉吹炼制得粗铜，再经电解分别得到精铜和富集贵金属的阳极泥，阳极泥用于提取贵金属；
或，将第二浸出渣经氧化焙烧后采用酸浸出，分别收集富集铜的浸出液和富集贵金属的浸出渣，浸出渣用于提取贵金属；
或，将第二浸出渣进行氧压浸出，分别收集富集铜的浸出液和富集贵金属的浸出渣，浸出渣用于提取贵金属。
本发明优选用于方案A的系统，一种从铜镍硫化矿中回收主伴生元素的系统，包括：
选择性浸出装置，具有低冰镍和浸出反应液各自的连续加料口，所述选择性浸出装置中含有反应底液，且使得向反应底液中持续加入铜镍硫化矿经造锍熔炼得到的低冰镍和浸出反应液时发生选择性浸出反应；所述选择性浸出装置还包括硫化氢气体的收集装置、第一浸出液的收集装置和第一次浸出渣的收集装置，其中，所述反应底液为质量分数20％-60％的硫酸溶液，所述浸出反应液为质量分数60％-95％的硫酸溶液；
水溶解装置，用于使用水溶解第一次浸出渣，分别收集第二浸出液和第二次浸出渣；
除铁装置，用于将水溶解装置中得到的第二次浸出液进行除铁；
镍和钴的提取装置，用于收集除铁装置中除铁后液，用于镍和钴的提取； 炼铁装置，用于收集除铁装置中的除铁渣，用于炼铁；
和/或，铜冶炼装置，用于将所述第二浸出渣进行铜冶炼，分别得到铜和贵金属。
优选适用于方案A的系统，还包括：硫磺制备装置，用于将造锍熔炼中产生的二氧化硫与所述常压选择性浸出装置中产生硫化氢气体反应制得硫磺；硫酸制备装置，用于将造锍熔炼中产生的部分二氧化硫转换成硫酸，并将其提供给所述常压选择性浸出装置。
方案B：一种对铜镍硫化矿综合利用的方法，包括：
1)对铜镍硫化矿经造锍熔炼得到的低冰镍直接使用硫酸进行常压选择性浸出，分别收集硫化氢气体、浸出液和浸出渣，其中，所述常压选择性浸出的温度为25-80℃；
2)对步骤1)的浸出液进行除铁，分别收集除铁后液和除铁渣，所述除铁后液用于镍和钴的提取，所述除铁渣用于炼铁；
和/或，对步骤1)的浸出渣送铜冶炼系统冶炼，分别得到铜和贵金属。
作为优选，方案B中，所述造锍熔炼中产生的二氧化硫与步骤1)中的硫化氢气体反应制备硫磺，以及将剩余二氧化硫转换成步骤1)中进行常压选择性浸出所使用的硫酸。
作为优选，方案B中，所述步骤1)中所述硫酸浓度为1mol/L-6mol/L，常压选择性浸出的液固比为2:1-20:1，常压选择性浸出时间为0.5-5h。
作为优选，方案B中，所述步骤1)中硫酸浓度为3mol/L-4mol/L，常压选择性浸出时间为0.5-2h，浸出温度为50-70℃，液固比为5:1-10:1。
作为优选，方案B中，所述步骤2)中对步骤1)中浸出液进行除铁具体为：调整浸出液pH至3-7，然后通入富含氧气的气体，得到除铁后液和除铁渣。
作为优选，方案B中，所述步骤2)中所述除铁后液用于镍和钴的提取具体为：
将除铁后液pH调至4.0-5.5后，向除铁后液中加入萃取剂，萃取分离得到含钴溶液和含镍溶液，再将含镍溶液的pH调至5.5-7.0使用所述萃取剂进行镍的萃取；
其中，所述萃取剂为P507的煤油溶液或Cyanex272的煤油溶液，体积分数为10-50％。
作为优选，方案B中，所述铜和贵金属的提取方法具体为：
将步骤1)的浸出渣经转炉吹炼制得粗铜，再经电解分别得到精铜和富集贵金属的阳极泥，富集贵金属的阳极泥用于提取贵金属；
或，将步骤1)的浸出渣经氧化焙烧后采用酸浸出，分别收集富集铜的浸出液和富集贵金属的浸出渣，富集贵金属的浸出渣用于提取贵金属；
或，将步骤1)的浸出渣进行氧压浸出，分别收集富集铜的浸出液和富集贵金属的浸出渣，富集贵金属的浸出渣用于提取贵金属。
一种适用于方案B的对铜镍硫化矿综合利用的系统，包括：常压选择性浸出装置，用于对低冰镍直接使用硫酸进行常压选择性浸出，分别收集硫化氢气体、浸出液和浸出渣；
除铁装置，用于将常压选择性浸出装置中得到的浸出液进行除铁；
镍和钴的提取装置，用于收集除铁装置中的除铁后液，用于镍和钴的提取； 炼铁装置，用于处理除铁装置中的除铁渣，用于炼铁；
和/或，铜冶炼装置，用于将常压选择性浸出装置中得到的浸出渣进行铜冶炼，分别得到铜和贵金属。
作为优选，适用于方案B的对铜镍硫化矿综合利用的系统，还包括：
造锍熔炼装置，用于处理铜镍硫化矿，并向所述常压选择性浸出装置中提供低冰镍，所述低冰镍为铜镍硫化矿经造锍熔炼制得；
硫磺制备装置，用于使所述造锍熔炼装置中产生的二氧化硫与所述常压选择性浸出装置中产生硫化氢气体反应制得硫磺；
硫酸制备装置，用于将所述造锍熔炼装置中产生的部分二氧化硫转换成硫酸，并将其提供给所述常压选择性浸出装置。
作为优选，适用于方案B的对铜镍硫化矿综合利用的系统，所述常压选择性浸出装置中还包括温度调控装置，用于将所述常压选择性浸出的温度控制在25-80℃。
 有益效果
本发明提出的一种铜镍硫化矿综合回收利用的方法及其系统，利用镍、铁、钴的硫酸盐晶体在高酸中溶解度下降的特性，在一定酸度底液（即质量分数为20%-60%的硫酸溶液）的存在下，采用低冰镍和浸出反应液（即质量分数为60%-95%的硫酸溶液）同时加料连续反应的模式，使得生成的镍、铁、钴的硫酸盐因饱和而析出；过滤得到的一次滤液可做底液循环使用；一次滤渣含有因饱和而析出的硫酸镍、硫酸钴和硫酸铁晶体，以及难以被硫酸浸出的硫化亚铜和贵金属，经水溶后得到镍、钴、铁的硫酸盐水溶液，以及富集有贵金属的硫化亚铜渣，同时可实现铜与镍、钴、铁的深度分离；镍、钴、铁的硫酸盐水溶液经除铁后用于硫酸镍和硫酸钴的提取；富集有贵金属的硫化亚铜渣经传统的铜冶炼和贵金属回收工序即可有效回收铜和贵金属。而生成的硫化氢气体与造锍熔炼生成的二氧化硫反应制备高纯硫磺，便于运输和存放。该方法流程短，效率高，不仅可以实现了镍铜的深度分离，还有利于大幅提高钴及贵金属的回收率，是一种清洁高效的元素综合利用工艺，易于大规模工业生产。
 本发明的实施方式
下面通过实施例，对本发明的具体实施方式作进一步详细描述。以下实施例用于说明本发明，但不用来限制本发明的范围。
一种对铜镍硫化矿综合利用的方法（方案 B ）：具体实施例为实施例 1~4 ：
实施例 1
本实施例中，铜镍硫化矿经造锍熔炼后得到低冰镍，主要元素含量：Ni 20.21％，Cu 10.52％，Fe 37.44％，Co 0.78％，贵金属约10g/t。
以此为原料，采用4mol/L的硫酸溶液常压浸出，液固比为10：1，反应温度80℃，反应0.5h。低冰镍中铁、钴、镍浸出进入溶液，而几乎全部铜和贵金属富集在硫化亚铜的浸出渣中，实现了铜与镍钴的分离。过滤所得溶液中铜含量小于0.005g/L，铁主要呈二价铁离子形式存在，无需再经还原而直接通空气进行氧化，同时维持溶液pH在3-5，使铁以针铁矿沉淀除去，所得铁渣焙烧成铁精矿，可用于炼铁。除铁后液调整pH至4，用P507萃取钴，用盐酸反萃得到氯化钴溶液，用于制备钴产品。再调整溶液pH至5.5，用P507萃取镍，盐酸反萃得到氯化镍溶液，用于制备镍产品。
固相滤渣为富集了贵金属的硫化亚铜，主要成分为：Ni 0.45％，Cu 75.2％，Fe 0.78％，Co＜0.01％，贵金属约70g/t(折合镍铁钴的浸出率均在99％以上)，直接转炉吹炼制备粗铜，粗铜再经电解精炼得到精铜，贵金属则富集于阳极泥中，送贵金属系统回收，其中，铜的回收率可达98％以上，贵金属的回收率达95％以上。造锍熔炼过程的一部分二氧化硫与硫化氢反应制备硫磺，其用量为硫化氢摩尔量的二分之一；其余的二氧化硫送硫酸系统制取硫酸，作为分解低冰镍的浸出剂。
实施例 2
铜镍硫化矿经造锍熔炼后得到低冰镍，主要元素含量：Ni 13.25％，Cu 8.32％，Fe 38.44％，Co 0.64％。
以此为原料，采用6mol/L的硫酸溶液常压浸出，液固比为2：1，反应温度65℃，反应1h。低冰镍中铁、钴、镍几乎全部浸出进入溶液，而铜富集在渣中，实现了铜与镍钴的分离。过滤所得溶液中铜含量小于0.006g/L，铁主要呈二价铁离子形式存在，调整溶液pH为5-7，然后置于密闭高压釜中，通纯氧并升温至180℃，将铁以赤铁矿形式除去。除铁后液调整pH至5，用P507萃取钴，用盐酸反萃得到氯化钴溶液，用于制备钴产品。再调整溶液pH至6.5，用P507萃取镍，盐酸反萃得到氯化镍溶液，用于制备镍产品。
固相滤渣为铜精矿，主要成分为：Ni 0.15％，Cu 73.2％，Fe 0.85％，Co＜0.008％(折合镍铁钴的浸出率均在99％以上)，经氧化焙烧后用硫酸浸出，得到硫酸铜溶液和浸出渣，其中，铜的回收率可达98％以上。硫酸铜溶液用于制铜。造锍熔炼过程的一部分二氧化硫与硫化氢反应制备硫磺，其用量为硫化氢摩尔量的二分之一；其余的二氧化硫送硫酸系统制取硫酸，作为分解低冰镍的浸出剂。
实施例 3
铜镍硫化矿经造锍熔炼后得到低冰镍，主要元素含量：Ni 16.55％，Cu 10.32％，Fe 33.44％，Co 0.34％，贵金属约8.9克吨。
以此为原料，采用1mol/L的硫酸溶液常压浸出，液固比为20：1，反应温度25℃，反应5h。低冰镍中铁、钴、镍几乎全部浸出进入溶液，而铜和贵金属富集在渣中，实现了铜与镍钴的分离。过滤所得溶液中铜含量小于0.008g/L，铁主要呈二价铁离子形式存在，无需再经还原，可在常压下直接通30％-60％的富氧空气进行氧化，并维持溶液pH在4-6，使铁以针铁矿沉淀除去，所得铁渣焙烧成铁精矿，可用于炼铁。除铁后液，调整pH至5.0，用Cyanex272萃取钴，用硫酸反萃得到硫酸钴溶液，用于制备硫酸钴产品；而后调整溶液pH至6.5，再用Cyanex272萃取镍，硫酸反萃得到硫酸镍溶液，用于制备硫酸镍产品。固相滤渣为富集了贵金属的铜精矿，主要成分为：Ni 0.16％，Cu76.2％，Fe 0.65％，Co＜0.01％(折合镍铁钴的浸出率均在99％以上)，贵金属约65克吨。采用高压釜氧压浸出，得到含铜溶液用于制铜，浸出渣则用于回收贵金属，其中，铜的回收率可达98％以上，贵金属的回收率达95％以上。造锍熔炼过程的一部分二氧化硫与硫化氢反应制备硫磺，其用量为硫化氢摩尔量的二分之一；其余的二氧化硫送硫酸系统制取硫酸，作为分解低冰镍的浸出剂。
实施例 4
铜镍硫化矿经造锍熔炼后得到低冰镍，主要元素含量：Ni 12.55％，Cu 8.32％，Fe 39.44％，Co 0.24％，贵金属约7.5克吨。
以此为原料，采用3mol/L的硫酸溶液常压浸出，液固比为5：1，反应温度50℃，反应2h。低冰镍中铁、钴、镍几乎全部浸出进入溶液，而铜和贵金属富集在渣中，实现了铜与镍钴的分离。
过滤所得溶液中铜含量小于0.003g/L，铁主要呈二价铁离子形式存在，调节溶液pH在4-6，然后置于密闭高压釜中，通纯氧并升温至220℃，将铁以赤铁矿形式除去。除铁后液，调整pH至5.5，用Cyanex272萃取钴，用硫酸反萃得到硫酸钴溶液，用于制备硫酸钴产品；而后调整溶液pH至7.0，再用Cyanex272萃取镍，硫酸反萃得到硫酸镍溶液，用于制备硫酸镍产品。
固相滤渣为富集了贵金属的铜精矿，主要成分为：Ni 0.12％，Cu 72.8％，Fe 0.45％，Co＜0.005％(折合镍铁钴的浸出率均在99％以上)，贵金属约68克吨。采用高压釜氧压浸出，得到含铜溶液用于制铜，浸出渣则用于回收贵金属，其中，铜的回收率可达98％以上，贵金属的回收率达95％以上。造锍熔炼过程的一部分二氧化硫与硫化氢反应制备硫磺，其用量为硫化氢摩尔量的二分之一；其余的二氧化硫送硫酸系统制取硫酸，作为分解低冰镍的浸出剂。
方案 A ：一种从铜镍硫化矿中回收主伴生元素的方法，具体实施例 5~8 。
实施例 5
本实施例中，铜镍硫化矿经造锍熔炼后得到低冰镍，主要元素含量：Ni 20.21％，Cu 10.52％，Fe37.44％，Co 0.78％，贵金属约10g/t，同时有二氧化硫生成。
配制硫酸质量分数为30％的溶液作为反应底液；同时配制硫酸质量分数为90％的溶液作为浸出反应液。向反应釜中填充总釜体积40％的反应底液；同时向反应釜中加入低冰镍和反应浸出液进行反应，并维持反应釜中硫酸的消耗量与加入量一致；持续加料进行反应，直至反应釜中料浆达到总釜体积的80％时停止加料，继续反应1h，并收集反应过程生成的硫化氢气体。
反应完成后的料浆冷却到室温后进行过滤，分别得到一次滤液和一次滤渣，其中一次滤液作为下一次浸出的反应底液；一次滤渣则泵入含去离子水的溶解槽，待反应过程中因饱和而析出的硫酸镍、硫化钴以及硫酸亚铁晶体重新溶解后二次过滤，得到含有硫酸镍、硫酸钴和硫酸亚铁的二次滤液以及富集有硫化亚铜和贵金属的二次滤渣，实现了铜与镍钴的分离。过滤所得溶液中铜含量小于0.003g/L，铁主要呈二价铁离子形式存在，维持溶液pH为3-4，直接通入空气进行氧化，无需再经还原，使铁形成针铁矿除去，所得铁渣焙烧成铁精矿，可用于炼铁。除铁后液调整pH至4，用P507萃取钴，用盐酸反萃得到氯化钴溶液，用 于制备钴产品。再调整溶液pH至5.5，用P507萃取镍，盐酸反萃得到氯化镍溶液，用于制备镍产品。
二次滤渣为富集了贵金属的硫化亚铜，主要成分为：Ni 0.49％，Cu 73.2％，Fe 0.72％，Co＜0.009％，贵金属约67g/t(折合镍铁钴的浸出率均在99％以上)，直接转炉吹炼制备粗铜，粗铜再经电解精炼得到精铜，贵金属则富集于阳极泥中，送贵金属系统回收，其中，铜的回收率可达98％以上，贵金属的回收率可达95％以上。造锍熔炼过程的一部分二氧化硫与硫化氢反应制备硫磺，其用量为硫化氢摩尔量的二分之一；其余的二氧化硫送硫酸系统制取硫酸，用于配反应底液和浸出反应液。
实施例 6
铜镍硫化矿经造锍熔炼后得到低冰镍，主要元素含量：Ni13.25％，Cu8.32％，Fe 38.44％，Co0.64％，贵金属约8g/t，同时有二氧化硫生成。
配制硫酸质量分数为40％的溶液作为反应底液；同时配制硫酸质量分数为85％的溶液作为浸出反应液。向反应釜中填充总釜体积45％的反应底液；同时向反应釜中加入低冰镍和反应浸出液进行反应，并维持反应釜中硫酸的消耗量与加入量一致；持续加料进行反应，直至反应釜中料浆达到总釜体积的80％时停止加料，继续反应1.5h，并收集反应过程生成的硫化氢气体。
反应完成后的料浆冷却到室温后进行过滤，分别得到一次滤液和一次滤渣，其中一次滤液作为下一次浸出的反应底液；一次滤渣则泵入含去离子水的溶解槽，待反应过程中因过饱和而析出的硫酸镍、硫化钴以及硫酸亚铁晶体重新溶解后二次过滤，得到含有硫酸镍、硫酸钴和硫酸亚铁的二次滤液以及富集有硫化亚铜和贵金属的二次滤渣，实现了铜与镍钴的分离。过滤所得溶液中铜含量小于0.009g/L，铁主要呈二价铁离子形式存在，将该溶液置于密闭高压釜中，通纯氧并升温至180℃，将铁以赤铁矿形式除去。除铁后液调整pH至5，用P507萃取钴，用硫酸反萃得到硫酸钴溶液，用于制备钴产品。再调整溶液pH至6.5，用P507萃取镍，硫酸反萃得到硫酸镍溶液，用于制备镍产品。
二次滤渣为富集了贵金属的硫化亚铜，主要成分为：Ni0.16％，Cu72.6％，Fe 0.95％，Co＜0.007％(折合镍铁钴的浸出率均在99％以上)，贵金属约65g/t(折合镍铁钴的浸出率均在99％以上)。经氧化焙烧后用硫酸浸出，得到硫酸铜溶液和富集贵金属的浸出渣，富集贵金属的浸出渣送贵金属系统回收，其中，铜的回收率可达98％以上，贵金属的回收率可达95％以上。造锍熔炼过程的一部分二氧化硫与硫化氢反应制备硫磺，其用量为硫化氢摩尔量的二分之一；其余的二氧化硫送硫酸系统制取硫酸，用于配反应底液和浸出反应液。
实施例 7
铜镍硫化矿经造锍熔炼后得到低冰镍，主要元素含量：Ni16.55％，Cu10.32％，Fe33.44％，Co0.34％，贵金属约11g/t，同时有二氧化硫生成。
配制硫酸质量分数为20％的溶液作为反应底液；同时配制硫酸质量分数为60％的溶液作为浸出反应液。向反应釜中填充总釜体积30％的反应底液；同时向反应釜中加入低冰镍和反应浸出液进行反应，并维持反应釜中硫酸的消耗量与加入量一致；持续加料进行反应，直至反应釜中料浆达到总釜体积的80％时停止加料，继续反应0.5h，并收集反应过程生成的硫化氢气体。
反应完成后的料浆冷却到室温后进行过滤，分别得到一次滤液和一次滤渣，其中一次滤液作为下一次浸出的反应底液；一次滤渣则泵入含去离子水的溶解槽，待反应过程中因过饱和而析出的硫酸镍、硫化钴以及硫酸亚铁晶体重新溶解后二次过滤，得到含有硫酸镍、硫酸钴和硫酸亚铁的二次滤液以及富集有硫化亚铜和贵金属的二次滤渣，实现了铜与镍钴的分离。过滤所得溶液中铜含量小于0.006g/L，铁主要呈二价铁离子形式存在，维持溶液pH为3-4，直接通入30％-50％的富氧空气进行氧化，无需再经还原，使铁形成针铁矿除去，所得铁渣焙烧成铁精矿，可用于炼铁。除铁后液调整pH至5，用Cyanex272萃取钴，用盐酸反萃得到氯化钴溶液，用于制备钴产品。再调整溶液pH至6.5，再用Cyanex272萃取镍，盐酸反萃得到氯化镍溶液，用于制备镍产品。
二次滤渣为富集了贵金属的硫化亚铜，主要成分为：Ni0.12％，Cu76.4％，Fe 0.62％，Co＜0.008％(折合镍铁钴的浸出率均在99％以上)，贵金属约78g/t(折合镍铁钴的浸出率均在99％以上)，采用高压釜氧压浸出，得到含铜溶液用于制铜，浸出渣则用于回收贵金属，其中，铜的回收率可达98％以上，贵金属的回收率可达95％以上。造锍熔炼过程的一部分二氧化硫与硫化氢反应制备硫磺，其用量为硫化氢摩尔量的二分之一；其余的二氧化硫送硫酸系统制取硫酸，用于配反应底液和浸出反应液。
实施例 8
铜镍硫化矿经造锍熔炼后得到低冰镍，主要元素含量：Ni12.55％，Cu8.32％，Fe 39.44％，Co0.24％，贵金属约10.8g/t，同时有二氧化硫生成。
配制硫酸质量分数为60％的溶液作为反应底液；同时配制硫酸质量分数为95％的溶液作为浸出反应液。向反应釜中填充总釜体积60％的反应底液；同时向反应釜中加入低冰镍和反应浸出液进行反应，并维持反应釜中硫酸的消耗量与加入量一致；持续加料进行反应，直至反应釜中料浆达到总釜体积的80％时停止加料，继续反应2h，并收集反应过程生成的硫化氢气体。
反应完成后的料浆冷却到室温后进行过滤，分别得到一次滤液和一次滤渣，其中一次滤液作为下一次浸出的反应底液；一次滤渣则泵入含去离子水的溶解槽，待反应过程中因过饱和而析出的硫酸镍、硫化钴以及硫酸亚铁晶体重新溶解后二次过滤，得到含有硫酸镍、硫酸钴和硫酸亚铁的二次滤液以及富集有硫化亚铜和贵金属的二次滤渣，实现了铜与镍钴的分离。过滤所得溶液中铜含量小于0.004g/L，铁主要呈二价铁离子形式存在，无需还原，直接将该溶液置于密闭高压釜中，通纯氧并升温至220℃，将铁以赤铁矿形式除去。除铁后液调整pH至5.5，用Cyanex272萃取钴，用硫酸反萃得到硫酸钴溶液，用于制备钴产品。再调整溶液pH至7，再用Cyanex272萃取镍，硫酸反萃得到硫酸镍溶液，用于制备镍产品。
二次滤渣为富集了贵金属的硫化亚铜，主要成分为：Ni 0.11％，Cu 72.3％，Fe 0.40％，Co＜0.004％(折合镍铁钴的浸出率均在99％以上)，贵金属约75g/t(折合镍铁钴的浸出率均在99％以上)，采用高压釜氧压浸出，得到含铜溶液用于制铜，浸出渣则用于回收贵金属，其中，铜的回收率可达98％以上，贵金属的回收率可达95％以上。造锍熔炼过程的一部分二氧化硫与硫化氢反应制备硫磺，其用量为硫化氢摩尔量的二分之一；其余的二氧化硫送硫酸系统制取硫酸，用于配反应底液和浸出反应液。 

Claims (15)

  1. 一种铜镍硫化矿综合回收利用的方法，其特征在于，包括以下步骤：
    1）选择性浸出：
    通过方案A或方案B获取富集有镍铁钴的浸出液和富集有铜的浸出渣：
    方案A：即为从铜镍硫化矿中回收主伴生元素的方法，其选择性浸出步骤为：
    向反应底液中持续加入铜镍硫化矿经造锍熔炼得到的低冰镍以及浸出反应液，进行选择性浸出，分别收集硫化氢气体、第一浸出液和第一次浸出渣，其中，所述反应底液为质量分数20%-60%的硫酸溶液，所述浸出反应液为质量分数60%-95%的硫酸溶液；向所述第一次浸出渣中加入水，溶解，分别收集第二浸出液和第二浸出渣；
    方案B：即为对铜镍硫化矿综合利用的方法，其选择性浸出步骤为：
    对铜镍硫化矿经造锍熔炼得到的低冰镍直接使用硫酸进行常压选择性浸出，分别收集硫化氢气体、浸出液和浸出渣，其中，常压选择性浸出的温度为25-80℃；
    方案A的第二浸出液、方案B的浸出液即为富集有镍铁钴的浸出液；方案A的第二浸出渣、方案B的浸出渣为富集有铜的浸出渣；
    2）对步骤1)富集有镍铁钴的浸出液进行除铁，分别收集除铁后液和除铁渣，除铁后液用于镍和钴的提取，除铁渣用于炼铁；
    和/或，对步骤1)的富集有铜的浸出渣送铜冶炼系统冶炼，分别得到铜和贵金属。
  2. 根据权利要求1所述的方法，其特征在于，在步骤1）方案A中，所述选择性浸出为常压非氧化性浸出；
    和/或，所述浸出反应液为质量分数为85%-90%的硫酸溶液。
  3. 根据权利要求1所述的方法，其特征在于，在步骤1）方案A中，所述低冰镍和浸出反应液同时连续加入，且两者的加入量与消耗量相同；
    所述第一浸出液返回作为下一批物料的反应底液，循环使用。
  4. 根据权利要求1所述的方法，其特征在于，在步骤1）方案A中，加料完成后继续浸出0.5-2h。
  5. 根据权利要求1所述的方法，其特征在于，在步骤1）方案B中，所述硫酸浓度为1mol/L-6mol/L，常压选择性浸出的液固比为2:1-20:1，常压选择性浸出时间为0.5-5h。
  6. 根据权利要求5所述的方法，其特征在于，在步骤1）方案B中，所述步骤1)中硫酸浓度为3mol/L-4mol/L，常压选择性浸出时间为0.5-2h，浸出温度为50-70℃，液固比为5:1-10:1。
  7. 根据权利要求1-6中任一项所述的方法，其特征在于，所述造锍熔炼中产生的二氧化硫与步骤1）中的硫化氢气体反应制备硫磺，以及将剩余二氧化硫转换成步骤1）中进行常压选择性浸出所使用的硫酸溶液。
  8. 根据权利要求1-6中任一项所述的方法，其特征在于，所述步骤2）中，对浸出液进行除铁具体为：
    向富集有镍铁钴的浸出液或调整pH为3~7的富集有镍铁钴的浸出液中通入富含氧气的气体，得到除铁后液和除铁渣；
    或，对富集有镍铁钴的浸出液加入到高压反应釜中与氧化性气体进行反应，反应完成后进行固液分离，将滤渣洗涤干燥后即为除铁渣，所得滤液为除铁后液。
  9. 根据权利要求1~6任一项所述的方法，其特征在于，所述除铁后液用于镍和钴的提取，具体为：
    将除铁后液pH调至4.0-5.5后，向除铁后液中加入萃取剂，萃取分离得到含钴溶液和含镍溶液，再将含镍溶液的pH调至5.5-7.0使用所述萃取剂进行镍的萃取；
    其中，所述萃取剂为P507的煤油溶液或Cyanex272的煤油溶液，体积分数为10-50%。
  10. 根据权利要求1所述的方法，其特征在于，所述铜和贵金属的回收方法具体为：
    将处理低冰镍所得富集有铜的浸出渣送转炉吹炼制得粗铜，再经电解分别得到精铜和富集贵金属的阳极泥，阳极泥用于提取贵金属；
    或，将处理低冰镍所得富集有铜的浸出渣经氧化焙烧后采用酸浸出，分别收集富集铜的浸出液和富集贵金属的浸出渣，浸出渣用于提取贵金属；
    或，将处理低冰镍所得富集有铜的浸出渣进行氧压浸出，分别收集富集铜的浸出液和富集贵金属的浸出渣，浸出渣用于提取贵金属。
  11. 一种实施权利要求1~10任一项所述方法的系统，包括：
    获取富集有镍铁钴的浸出液和富集有铜的浸出渣装置，为选择性浸出装置和水溶解装置；或者为常压选择性浸出装置：
    选择性浸出装置：具有低冰镍和浸出反应液各自的连续加料口，所述选择性浸出装置中含有反应底液，且使得向反应底液中持续加入铜镍硫化矿经造锍熔炼得到的低冰镍和浸出反应液时发生选择性浸出反应；所述选择性浸出装置还包括硫化氢气体的收集装置、第一浸出液的收集装置和第一次浸出渣的收集装置，其中，所述反应底液为质量分数20％-60％的硫酸溶液，所述浸出反应液为质量分数60％-95％的硫酸溶液；
    水溶解装置，用于使用水溶解第一次浸出渣，分别收集第二浸出液和第二次浸出渣；
    常压选择性浸出装置，用于对低冰镍直接使用硫酸进行常压选择性浸出，分别收集硫化氢气体、浸出液和浸出渣；
    除铁装置，用于将水溶解装置中得到的第二次浸出液进行除铁，或用于将常压选择性浸出装置中得到的浸出液进行除铁；
    镍和钴的提取装置，用于收集除铁装置中除铁后液，用于镍和钴的提取；
    炼铁装置，用于处理除铁装置中的除铁渣，用于炼铁；
    和/或，铜冶炼装置，用于将所述第二浸出渣或常压选择性浸出装置中得到的浸出渣进行铜冶炼，分别得到铜和贵金属。
  12. 根据权利要求11所述的系统，其特征在于，还包括：
    硫磺制备装置，用于将造锍熔炼中产生的二氧化硫与所述常压选择性浸出装置中产生硫化氢气体反应制得硫磺；
    硫酸制备装置，用于将造锍熔炼中产生的部分二氧化硫转换成硫酸，并将其提供给所述常压选择性浸出装置；
    造锍熔炼装置，用于处理铜镍硫化矿，并向所述常压选择性浸出装置中提供低冰镍，所述低冰镍为铜镍硫化矿经造锍熔炼制得。
  13. 根据权利要求12所述的系统，其特征在于，所述常压选择性浸出装置中还包括温度调控装置，用于将所述常压选择性浸出的温度控制在25-80℃。
  14. 一种对铜镍硫化矿综合利用的方法，其特征在于，包括：
    1)对铜镍硫化矿经造锍熔炼得到的低冰镍直接使用硫酸进行常压选择性浸出，分别收集硫化氢气体、浸出液和浸出渣，其中，所述常压选择性浸出的温度为25-80℃；
    2)对步骤1)的浸出液进行除铁，分别收集除铁后液和除铁渣，所述除铁后液用于镍和钴的提取，所述除铁渣用于炼铁；
    和/或，对步骤1)的浸出渣送铜冶炼系统冶炼，分别得到铜和贵金属。
  15. 一种从铜镍硫化矿中回收主伴生元素的方法，其特征在于，包括：
    1)向反应底液中持续加入铜镍硫化矿经造锍熔炼得到的低冰镍和浸出反应液，选择性浸出，分别收集硫化氢气体、第一浸出液和第一次浸出渣，其中，所述反应底液为质量分数20％-60％的硫酸溶液，所述浸出反应液为质量分数60％-95％的硫酸溶液；
    2)向所述第一次浸出渣中加入水，溶解，分别收集第二浸出液和第二浸出渣；
    3)对所述第二浸出液进行除铁，分别收集除铁后液和除铁渣，所述除铁后液用于镍和钴的提取，所述除铁渣用于炼铁；
    和/或，将所述第二浸出渣送铜冶炼装置冶炼，分别得到铜和贵金属。
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