CN107058730B - A kind of method and its system to cu-ni sulphide ore comprehensive utilization - Google Patents

A kind of method and its system to cu-ni sulphide ore comprehensive utilization Download PDF

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CN107058730B
CN107058730B CN201710228509.5A CN201710228509A CN107058730B CN 107058730 B CN107058730 B CN 107058730B CN 201710228509 A CN201710228509 A CN 201710228509A CN 107058730 B CN107058730 B CN 107058730B
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iron
nickel
normal pressure
copper
leaching
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CN107058730A (en
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赵中伟
李永立
肖万海
刘旭恒
陈星宇
李江涛
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Central South University
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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/04Extraction of metal compounds from ores or concentrates by wet processes by leaching
    • C22B3/06Extraction 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
    • C22B3/08Sulfuric acid, other sulfurated acids or salts thereof
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B11/00Obtaining noble metals
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B15/00Obtaining copper
    • C22B15/0026Pyrometallurgy
    • C22B15/0028Smelting or converting
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B15/00Obtaining copper
    • C22B15/0063Hydrometallurgy
    • C22B15/0065Leaching or slurrying
    • C22B15/0067Leaching or slurrying with acids or salts thereof
    • C22B15/0071Leaching or slurrying with acids or salts thereof containing sulfur
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B23/00Obtaining nickel or cobalt
    • C22B23/04Obtaining nickel or cobalt by wet processes
    • C22B23/0407Leaching processes
    • C22B23/0415Leaching processes with acids or salt solutions except ammonium salts solutions
    • C22B23/043Sulfurated acids or salts thereof
    • C22B3/3844
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00Technologies related to metal processing
    • Y02P10/20Recycling

Abstract

The present invention provides a kind of methods and its system to cu-ni sulphide ore comprehensive utilization.The method includes:1) directly sulfuric acid is used to carry out normal pressure Selectively leaching the low nickel matte that cu-ni sulphide ore is obtained through matte smelting, collects hydrogen sulfide gas, leachate and leached mud respectively, wherein the temperature of the normal pressure Selectively leaching is 25 80 DEG C;2) leachate of step 1) is carried out removing iron, is collected respectively except liquid and iron dross removing after iron, described except extraction of the liquid for nickel and cobalt after iron, the iron dross removing is for smelting iron;And/or send copper metallurgy industry to smelt the leached mud of step 1), respectively obtain copper and noble metal.The depth that ambrose alloy may be implemented in method proposed by the present invention to cu-ni sulphide ore comprehensive utilization detaches, and nickel, copper, cobalt and the noble metal rate of recovery are high, sulphur output in the form of high-purity sulphur, convenient for storage.Present invention process is simple, flow is short, energy consumption is small, at low cost, is easy to large-scale industrial production.

Description

A kind of method and its system to cu-ni sulphide ore comprehensive utilization
Technical field
The present invention relates to non-ferrous metallurgy technology fields, are comprehensively utilized to cu-ni sulphide ore more particularly, to a kind of Method and its system.
Background technology
Nickel is a kind of important strategy metal, is widely used in national defence, aerospace, communications and transportation, petrochemical industry, the energy Equal fields.A considerable amount of nickel minerals are sulphide ores, are associated with copper, cobalt and noble metal (gold, silver and platinum group metal) etc., such as Gansu gold River copper nickel and Yi 1. at Kalatongke, Xingjiang copper nickel.Therefore also need to consider time of cobalt and noble metal while extracting nickel, copper It receives.
The smelting process of traditional cu-ni sulphide ore is to make iron, nickel, cobalt and copper with sulfide shape by matte smelting first Formula is enriched with and forms low nickel matte, and the noble metal of association is also enriched with;Then low nickel matte is bessemerized, by most iron And sulphur removes, and forms converter mattes.Cobalt is oxidized easily, thus often cause in converting process the loss of a large amount of cobalt into The sulfur dioxide for entering the slag that blows, while generating by acid making system obtains industrial sulphuric acid, and (sulfuric acid is because purposes and transportation radius asks It inscribes and largely accumulates).Later, the processing method of the converter mattes to blow is roughly divided into three classes.
One is converter mattes carry out grinding floating separation after slow cooling, low copper nickel sulfide concentrate, low nickel copper sulfide essence are respectively obtained Mine and an alloy.Alloy also needs revulcanization-mill is floating to isolate corresponding low copper nickel sulfide concentrate, low nickel copper sulfide essence Mine and secondary alloy.Secondary alloy is used for the recycling of noble metal, and low copper nickel sulfide concentrate divides for extracting nickel, but due to grinding to float From being not thorough, subsequently also need to remove the impurity copper carried, copper sulfide concentrate naturally also has nickel to be taken as impurity for carrying copper The problem of band, causes smelting procedure quite cumbersome.
Second, sour Selectively leaching technique also can be used in converter mattes, it is broadly divided into:Low acid pressure leaching or the leaching of peracid normal pressure Go out.Low acid pressure leaching is in the Fukang Smelter application in China.It is reported that Fukang Smelter is soaked using low sour two sections of adverse currents Go out, be one section of normal pressure leaching (pH >=6.2 for finally obtaining leachate) first, followed by one section of pressure leaching (finally obtains leaching The pH for going out liquid is 1.8-2.8, and oxygen presses 0.05-0.06MPa).By the sulphur for obtaining Cu, Fe≤0.01g/L after two sections of counterflow leachings Sour nickel solution, and copper, noble metal, iron and sulphur almost all in raw material and 40% or so cobalt stay in nickeliferous 2%-3%'s In finishing slag.And peracid normal pressure leaching is most applied early in Christian pine refinery, the hydrochloric acid (275g/ of the technique high concentration L leaching agent) is made, the nickeliferous about 120g/L of obtained leaching rich solution, hydrochloric acid 160g/L, also each 2g/L of iron, cobalt, copper.About 3% Copper is leached, and is largely stayed in slag.Then after solvent extraction and separation iron cobalt copper, evaporating, concentrating and crystallizing nickel chloride product. Few side of Peng etc. has studied the dynamics of converter mattes sulfuric acid leaching, and also refers to inversely leaching using intermittent two level and be leached to reduce Copper concentration in liquid.And the main ingredient Ni of converter mattes2S3With sour reaction process, it is difficult that it is easy generation at a lower temperature β-NiS phases are handled, therefore the peracid normal pressure decomposition technique of converter mattes needs effectively to carry out in the case where temperature is higher than 90 DEG C.
Third, the smelting process of converter mattes also can the leaching of hyperbaric oxygen ammonia.This method is contained by controlling the free ammonia in solution Amount and oxygen pressure, make Cu, Ni and Co be changed into Metal amine complex and dissolve, while sulphur is oxidized to sulfate radical, noble metal and iron Slag phase is formed for recycling.Free ammonia control is even more important in leaching process, and concentration is low to cause leaching rate low, excessive concentration meeting again The high ammino-complex for forming cobalt causes the loss of cobalt because its is insoluble.
Three of the above technical thought can effectively deal with converter mattes.But problem is the process at converter mattes by low nickel matte blowing In the middle, a large amount of cobalt enters in blowing slag, and primary recovery is low.In addition, because flow is tediously long, 10% platinum family gold is about lost Belong to.For the cobalt lost in recycling blowing slag, someone will blow slag again through pyrogenic attack, the cobalt of loss is recycled by reduction melting, Reduzate main component is the alloy and sulfide of iron-cobalt-nickel, becomes cobalt ice nickel.But since cobalt is easily aoxidized, content It is low, excessively disperse in the slag that blows, even if by reduction melting, the cobalt of a part can only be recycled.In addition, this cobalt ice nickel It leaches extremely complex, need to be mainly the leaching of alloy through three stages acid leach, first segment, the leaching of nickel cobalt in order to prevent needs soaking It is passed through hydrogen sulfide after either being leached during going out or vulcanized sodium is added, the leached mud then formed needs two sections of leachings that could obtain again To cobalt-carrying solution.In this way, a large amount of iron moves in circles in sulphur phase-slag phase, recovery process is also very complicated.
Generally speaking, low nickel matte is blown into converter mattes, though preferably solve the problems, such as the recycling of cupro-nickel, in association cobalt And there are serious problems in terms of noble metal recycling.And sulphur output in the form of sulfuric acid is also troubling problem.
Directly processing low nickel matte can be to avoid the valuable element loss of the associations such as cobalt and noble metal in above-mentioned converting process Problem.But the method for existing processing low nickel matte still has inconvenience when recycling associated valuable metals.As the sulphation of low nickel matte roasts Burning can make nickel cobalt copper be converted into water-soluble sulfate, and iron is converted into water-insoluble oxide, and the sulfur dioxide of generation is still used for Relieving haperacidity.But the platinum group metal of association retains in scum, and needs special flow to extract.Low nickel matte can also pass through oxygen pressure Acidleach is handled, such as Yin Fei etc. and Deng Zhilin etc. made detailed research.This oxygen leaching generally requires in autoclave It carries out, but aoxidize the sulphur generated to form retardation film, influences the further leaching of low nickel matte.In addition oxygen leaching can also generate A large amount of water-insoluble iron oxide precipitations, noble metal is mingled with it causes recycling difficult.During oxygen leaching although sulphur is transformed into Sulphur, but due to being mingled with together with scum and noble metal, it is still necessary to further oxidation is to recycle noble metal.
Generally speaking, existing direct processing low nickel matte has two class technique of pyrogenic process and wet method.Sulfating roasting can be used in pyrogenic process, Then reselection leaches valuable element, and iron oxide stays in leached mud, but the noble metal recycling in scum is difficult;Many people are green Wet method is looked at, wet method generally uses oxygen leaching, needs to use autoclave and pure oxygen, but equally face your gold recycled from scum The problem of category, and sulphur is oxidized to sulphur formation package when acid oxygen leaching, and noble metal recycles the difficulty that remains unchanged.
Invention content
(1) technical problems to be solved
The technical problem to be solved by the present invention is to the cobalt of association can not be effectively recycled in existing cu-ni sulphide ore processing method And noble metal.
(2) technical solution
In order to solve the above technical problem, the present invention provides a kind of methods to cu-ni sulphide ore comprehensive utilization, including:
1) directly sulfuric acid is used to carry out normal pressure Selectively leaching the low nickel matte that cu-ni sulphide ore is obtained through matte smelting, point It Shou Ji hydrogen sulfide gas, leachate and leached mud, wherein the temperature of normal pressure Selectively leaching is 25-80 DEG C;
2) leachate of step 1) is carried out removing iron, be collected respectively except liquid and iron dross removing after iron, except after iron liquid for nickel and The extraction of cobalt, iron dross removing is for smelting iron;
And/or send copper metallurgy industry to smelt the leached mud of step 1), respectively obtain copper and noble metal.
In the present invention, directly processing cu-ni sulphide ore can be to avoid low nickel matte after through the low nickel matte obtained by matte smelting In sequence tradition converting process technique the problem of the associations such as cobalt and noble metal valuable element loss.
Directly sulfuric acid is used to carry out normal pressure Selectively leaching low nickel matte, under the concentration and liquid-solid ratio, ferronickel is dissolved in In sulfuric acid solution, and reaction generates hydrogen sulfide gas completely, at this point, cuprous sulfide and noble metal hardly decompose in low nickel matte, The depth separation of ambrose alloy can be realized in leaching process.
Copper is the element of very close sulphur, Cu2The solubility product very little of S, only 10-48.And iron-cobalt-nickel to the compatibility of sulphur far not And copper, ferrous sulfide (FeS), nickel sulfide (α-NiS), cobalt sulfide (CoS) solubility product be respectively 10-18、10-18With 10-21.Cause As long as this is expected that solution has suitable acidity, it is likely that allow the sulfide of iron-cobalt-nickel to be decomposed and realize leaching, sulphur turns Become hydrogen sulfide and be volatized into gas phase, cuprous sulfide does not leach and stays in solid phase together with noble metal.Sulphur is raw during acidleach At H2S volatilize, detached with leached mud, no longer interfere noble metal recycling, can also special disposal recycling high-quality solid sulphur.
In addition, in the method for the invention, eliminating the converting process to low nickel matte in common methods, effectively preventing The loss of cobalt caused by converting process.Meanwhile copper and noble metal are effectively stayed in into leached mud using above-mentioned leaching step, then Copper metallurgy industry is sent to smelt the leached mud, noble metal moves towards single at this time, can effectively recycle, and improves companion in cu-ni sulphide ore Raw cobalt and the platinum group metal rate of recovery.
In order to solve long-standing problem nickel sulfide ore enterprise sulphur problem of outlet, the present invention is by low nickel matte in sulfuric acid leaching mistake Generated hydrogen sulfide gas is used to prepare sulphur in journey, with sulphur in conventional method to prepare sulfuric acid the case where compared be more easy to In storage and transport.
Low nickel matte is mainly derived from cupro-nickel vulcanised ore concentrate, and main component is Ni5Fe4S8, in addition to nickel simultaneously rich in copper, cobalt and A large amount of platinum families need to recycle, and in a preferred embodiment of the invention, low nickel matte is that cu-ni sulphide ore is made through matte smelting, I.e. method of the invention is more suitable for decomposition and extraction of the cu-ni sulphide ore through low nickel matte made from matte smelting.
At 25-80 DEG C, it is anti-that double decomposition occurs through low nickel matte made from matte smelting in sulfuric acid solution for cu-ni sulphide ore It answers, ferronickel cobalt is dissolved in water, and generates hydrogen sulfide gas, and reaction is very thorough, meanwhile, under the sulfuric acid of the temperature, low nickel matte In cuprous sulfide hardly decompose, can be realized in leaching process cupro-nickel depth separation, improve the rate of recovery, broken with live The situation effectively extracted that could be realized each element in mineral in work using 90 DEG C or more of high temperature, has been saved the energy, also dropped The risk that low operating personnel may receive.
In a preferred embodiment of the invention, those skilled in the art can select leaching according to actual needs After step, leachate is carried out to send copper metallurgy industry to smelt or both carry out except iron or right leachate leached mud except iron Leached mud send copper metallurgy industry to smelt, and is preferably, has both carried out removing iron to leachate, for recycling nickel, cobalt and/or iron, Copper metallurgy industry is sent to smelt leached mud, for recycling copper and noble metal.
In order to solve long-standing problem nickel sulfide ore enterprise sulphur problem of outlet, the titanium dioxide that can will be generated in matte smelting Sulphur is prepared in complete react of generated hydrogen sulfide gas during sulfuric acid leaching to sulphur with low nickel matte, is readily transported and stores up Deposit, and will remaining sulfur dioxide import sulfate system in be converted into above-mentioned steps 1) in carry out normal pressure Selectively leaching used Sulfuric acid.Wherein, the sulfur dioxide dosage that sulphur is made is the half of hydrogen sulfide mole.
In order to enable the leaching in step 1) is more complete so that ambrose alloy is kept completely separate, in a preferred embodiment In, sulfuric acid concentration is 1mol/L-6mol/L in step 1), and the temperature of normal pressure Selectively leaching is 25-80 DEG C, normal pressure selective leaching It is 0.5-5h to go out the time.
More preferably, sulfuric acid concentration is 3mol/L-4mol/L in step 1), and the normal pressure Selectively leaching time is 0.5- 2h, extraction temperature are 50-70 DEG C, liquid-solid ratio 5:1-10:1.
In the present invention, the leachate of step 1) can be carried out using method for removing iron commonly used in the art removing iron, is Can iron preferably be removed and not influence the rate of recovery of nickel cobalt, in a preferred embodiment of the invention, it is preferred to use needle iron Mine method or hematite process.
Copper content is less than 0.008g/L, preferably smaller than 0.003g/L in solution in the leachate of step 1) in the present invention, this When, iron mainly be in ferrous ion form exist, no longer need to through reduction can direct oxidation formed goethite removal, i.e., it is excellent at one It selects in embodiment, the pH of leachate can be adjusted to 3-7, then pass to the gas rich in oxygen, obtain except liquid after iron and remove Scum.
Specifically the pH of leachate in step 1) can be adjusted to 4-7, be placed in enclosed high pressure kettle, logical pure oxygen is simultaneously warming up to 220 DEG C, iron is removed in the form of bloodstone, is obtained except liquid and iron dross removing after iron.
Air or oxygen-enriched air can also be passed through for leachate into step 1), while it is 3-4 to maintain the pH of solution, you can will Iron removes as goethite, obtains except liquid and iron dross removing after iron.
Obtained scum can be fired into iron ore concentrate, for smelting iron.
Carrying for nickel and cobalt is realized when except obtaining after iron except liquid after iron, method commonly used in the art can be used to leachate It takes, in order to fully achieve the extraction of nickel and cobalt in the present invention, in a preferred embodiment, will be adjusted to except the pH of liquid after iron 4.0-5.5 is removed backward is added extractant after iron in liquid, and extraction and separation obtain cobalt-carrying solution and solution containing nickel, then by solution containing nickel PH is adjusted to the extraction that 5.5-7.0 carries out nickel using extractant;
Wherein, the extractant is the kerosin of P507 or the kerosin of Cyanex272, volume fraction 10- 50%.In above-mentioned extractant, kerosene is diluent.
Wherein, P507 is di-2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester, and Cyanex272 is two (2,4,4- trimethyls penta Base) hypophosphorous acid.
When extractant is the kerosin of P507, it will be adjusted to 4.0-5.0 except the pH of liquid after iron, then add into liquid after except iron Enter extractant, extracts cobalt with extractant, extraction and separation obtain cobalt-carrying solution and solution containing nickel, then the pH of solution containing nickel is adjusted to 5.5-6.5, with extractant extraction of nickel, hydrochloric acid is stripped to obtain nickel chloride solution, is used to prepare nickel product.Wherein, by cobalt-carrying solution It is stripped to obtain cobalt chloride solution with hydrochloric acid, is used to prepare cobalt product.
When extractant is the kerosin of Cyanex272, it will be adjusted to 5.0-5.5 except the pH of liquid after iron, then to after except iron Extractant is added in liquid, extraction and separation obtain cobalt-carrying solution and solution containing nickel, then the pH of solution containing nickel is adjusted to 6.5-7.0, use Extractant extraction of nickel, sulfuric acid are stripped to obtain nickel sulfate solution, are used to prepare nickel sulfate product.Wherein, by cobalt-carrying solution sulfuric acid Back extraction obtains cobalt sulfate solution, is used to prepare cobaltous sulfate product.
In a preferred embodiment of the invention, Copper making method conventional in the art may be used and obtain copper and expensive Metal, in order to make copper and noble metal be kept completely separate, in a preferred embodiment of the invention, the extracting method of copper and noble metal Preferably:
By the leached mud of step 1) through bessemerizing obtained blister copper, then through electrolysis respectively obtain refined copper and enriching noble metals The earth of positive pole, the earth of positive pole of enriching noble metals is for extracting noble metal.
Or, by Ore Leaching is used after the oxidized roasting of the leached mud of step 1), the leachate and richness of enriching Cu are collected respectively Collect the leached mud of noble metal, the leached mud of enriching noble metals is for extracting noble metal.
Or, the leached mud of step 1) is carried out oxygen leaching, the leachate and enriching noble metals of enriching Cu are collected respectively Leached mud, the leached mud of enriching noble metals is for extracting noble metal.
99% or more, cobalt and noble metal have obtained effectively the leaching rate of nickel, iron, cobalt obtained by the method for the present invention Recycling, the rate of recovery of copper is up to 98% or more, and the rate of recovery of noble metal is up to 95% or more.
According to a further aspect of the present invention, a kind of system comprehensively utilized to cu-ni sulphide ore is additionally provided, including:
Normal pressure Selectively leaching device is received respectively for directly sulfuric acid being used to carry out normal pressure Selectively leaching low nickel matte Collect hydrogen sulfide gas, leachate and leached mud;
Deironing apparatus removes iron for carrying out the leachate obtained in normal pressure Selectively leaching device;
The extraction element of nickel and cobalt is used for the extraction of nickel and cobalt for collecting the liquid after removing iron in deironing apparatus;
Iron-smelting device, for handling the iron dross removing in deironing apparatus, for smelting iron;
And/or Copper making device, the leached mud for will be obtained in normal pressure Selectively leaching device carry out Copper making, point Copper and noble metal are not obtained.
After leaching, Copper making device can be set according to actual needs.
Further include within the system:
Matte smelting device, for providing low nickel matte into normal pressure Selectively leaching device, wherein low nickel matte is cupro-nickel sulphur Change mine to be made through matte smelting;
Sulphur preparation facilities, sulfur dioxide for making to generate in matte smelting device in normal pressure Selectively leaching device It generates hydrogen sulfide gas reaction completely and sulphur is made;
Sulfuric acid preparation facilities, for the remaining sulfur dioxide generated in matte smelting device to be converted into sulfuric acid, and by its It is supplied to the normal pressure Selectively leaching device.
Further include temperature control device in the normal pressure Selectively leaching device, is used for the temperature of normal pressure Selectively leaching Control is at 25-80 DEG C, to improve the comprehensive utilization to cu-ni sulphide ore.
It is preferable to use the systems of the present invention for the method for the present invention to realize.
The method and its system of cu-ni sulphide ore comprehensive utilization proposed by the present invention are to cu-ni sulphide ore through matte smelting institute The low nickel matte obtained directly carries out normal pressure Selectively leaching with sulfuric acid at 25-80 DEG C, and the nickel, cobalt and iron in low nickel matte are decomposed by acid Enter solution afterwards, leachate is through except the extraction for being used for nickel, cobalt after iron, iron dross removing is for smelting iron;Copper in low nickel matte is to vulcanize Asia Copper form is retained in leached mud together with noble metal, into Copper making, recycles copper and noble metal.This method flow is short, efficient, no The depth separation that ambrose alloy only may be implemented, also helps the rate of recovery for greatly improving cobalt and noble metal, is a kind of clean and effective Element comprehensive utilization process, be easy to large-scale industrial production.
Description of the drawings
Fig. 1 is according to the flow diagram comprehensively utilized to cu-ni sulphide ore in the embodiment of the present invention 1.
Specific implementation mode
With reference to the accompanying drawings and examples, the specific implementation mode of the present invention is described in further detail.Implement below Example is not limited to the scope of the present invention for illustrating the present invention.
Embodiment 1
As shown in Figure 1, in the present embodiment, cu-ni sulphide ore obtains low nickel matte, essential element content after matte smelting:Ni 20.21%, Cu 10.52%, Fe 37.44%, Co 0.78%, noble metal about 10g/t.
As raw material, using the sulfuric acid solution normal pressure leaching of 4mol/L, liquid-solid ratio 10:1,80 DEG C of reaction temperature, instead Answer 0.5h.Iron, cobalt, nickel are leached into solution in low nickel matte, and almost all copper and concentration of precious metal are in the leaching of cuprous sulfide In slag, the separation of copper and nickel cobalt is realized.It filters copper content in acquired solution and is less than 0.005g/L, iron is in mainly ferrous ion Form exists, and no longer needs to through reduction and directly blowing air is aoxidized, while pH value of solution being maintained to keep iron heavy with goethite in 3-5 It forms sediment and removes, gained scum is fired into iron ore concentrate, can be used for smelting iron.Except liquid adjusts pH to 4 after iron, cobalt is extracted with P507, uses hydrochloric acid Back extraction obtains cobalt chloride solution, is used to prepare cobalt product.PH value of solution is adjusted again to 5.5, and with P507 extraction of nickel, hydrochloric acid is stripped to obtain Nickel chloride solution is used to prepare nickel product.
Solid phase filter residue is the cuprous sulfide for being enriched noble metal, and main component is:Ni 0.45%, Cu 75.2%, Fe 0.78%, Co < 0.01%, noble metal about 70g/t (leaching rate of equivalent ferronickel cobalt is 99% or more), are directly bessemerized Blister copper is prepared, blister copper obtains refined copper through electrorefining again, and noble metal is then enriched in the earth of positive pole, and noble metal systems is sent to recycle, In, the rate of recovery of copper is up to 98% or more, and the rate of recovery of noble metal is up to 95% or more.A part of titanium dioxide of matte smelting process Sulphur is reacted with hydrogen sulfide prepares sulphur, and dosage is the half of hydrogen sulfide mole;Remaining sulfur dioxide send sulfuric acid system System extracting sulfuric acid, as the leaching agent for decomposing low nickel matte.
Embodiment 2
Cu-ni sulphide ore obtains low nickel matte, essential element content after matte smelting:Ni 13.25%, Cu 8.32%, Fe 38.44%, Co 0.64%.
As raw material, using the sulfuric acid solution normal pressure leaching of 6mol/L, liquid-solid ratio 2:1,65 DEG C of reaction temperature, reaction 1h.Iron, cobalt, nickel almost all are leached into solution in low nickel matte, and copper segregation realizes the separation of copper and nickel cobalt in slag. It filtering copper content in acquired solution and is less than 0.006g/L, iron is in mainly that ferrous ion form exists, and adjustment pH value of solution is 5-7, It is subsequently placed in enclosed high pressure kettle, logical pure oxygen is simultaneously warming up to 180 DEG C, and iron is removed in the form of bloodstone.Except liquid adjusts pH after iron To 5, cobalt is extracted with P507, is stripped to obtain cobalt chloride solution with hydrochloric acid, is used to prepare cobalt product.PH value of solution is adjusted again to 6.5, is used P507 extraction of nickel, hydrochloric acid are stripped to obtain nickel chloride solution, are used to prepare nickel product.
Solid phase filter residue is copper concentrate, and main component is:Ni 0.15%, Cu 73.2%, Fe 0.85%, Co < 0.008% (leaching rate of equivalent ferronickel cobalt is 99% or more), uses sulfuric acid leaching, obtains copper-bath and leaching after oxidized roasting Slag, wherein the rate of recovery of copper is up to 98% or more.Copper-bath is used for copper processed.A part of titanium dioxide of matte smelting process Sulphur is reacted with hydrogen sulfide prepares sulphur, and dosage is the half of hydrogen sulfide mole;Remaining sulfur dioxide send sulfuric acid system System extracting sulfuric acid, as the leaching agent for decomposing low nickel matte.
Embodiment 3
Cu-ni sulphide ore obtains low nickel matte, essential element content after matte smelting:Ni 16.55%, Cu 10.32%, Fe 33.44%, Co 0.34%, about 8.9 grams of tons of noble metal.
As raw material, using the sulfuric acid solution normal pressure leaching of 1mol/L, liquid-solid ratio 20:1,25 DEG C of reaction temperature, instead Answer 5h.Iron, cobalt, nickel almost all are leached into solution in low nickel matte, and copper and concentration of precious metal realize copper and nickel in slag The separation of cobalt.Filter acquired solution in copper content be less than 0.008g/L, iron mainly be in ferrous ion form exist, no longer need to through Reduction, the oxygen-enriched air that can directly lead to 30%-60% under normal pressure is aoxidized, and maintains pH value of solution in 4-6, makes iron with needle iron Mine precipitation removes, and gained scum is fired into iron ore concentrate, can be used for smelting iron.Except liquid after iron, pH to 5.0 is adjusted, is extracted with Cyanex272 Cobalt is taken, is stripped to obtain cobalt sulfate solution with sulfuric acid, is used to prepare cobaltous sulfate product;Then adjustment pH value of solution is to 6.5, then uses Cyanex272 extraction of nickel, sulfuric acid are stripped to obtain nickel sulfate solution, are used to prepare nickel sulfate product.
Solid phase filter residue is the copper concentrate for being enriched noble metal, and main component is:Ni 0.16%, Cu76.2%, Fe 0.65%, Co < 0.01% (leaching rate of equivalent ferronickel cobalt is 99% or more), about 65 grams of tons of noble metal.Using autoclave oxygen Pressure leaches, and obtains copper-containing solution for copper processed, leached mud is then used to recycle noble metal, wherein the rate of recovery of copper up to 98% with On, the rate of recovery of noble metal is up to 95% or more.A part of sulfur dioxide of matte smelting process is reacted with hydrogen sulfide prepares sulphur, Its dosage is the half of hydrogen sulfide mole;Remaining sulfur dioxide send sulfate system extracting sulfuric acid, as the low ice of decomposition The leaching agent of nickel.
Embodiment 4
Cu-ni sulphide ore obtains low nickel matte, essential element content after matte smelting:Ni 12.55%, Cu 8.32%, Fe 39.44%, Co 0.24%, about 7.5 grams of tons of noble metal.
As raw material, using the sulfuric acid solution normal pressure leaching of 3mol/L, liquid-solid ratio 5:1,50 DEG C of reaction temperature, reaction 2h.Iron, cobalt, nickel almost all are leached into solution in low nickel matte, and copper and concentration of precious metal realize copper and nickel cobalt in slag Separation.
It filters copper content in acquired solution and is less than 0.003g/L, iron is in mainly that ferrous ion form exists, and adjusts solution PH is subsequently placed in 4-6 in enclosed high pressure kettle, and logical pure oxygen is simultaneously warming up to 220 DEG C, and iron is removed in the form of bloodstone.After iron Liquid adjusts pH to 5.5, extracts cobalt with Cyanex272, is stripped to obtain cobalt sulfate solution with sulfuric acid, is used to prepare cobaltous sulfate product; Then to 7.0, then with Cyanex272 extraction of nickel, sulfuric acid is stripped to obtain nickel sulfate solution adjustment pH value of solution, is used to prepare nickel sulfate Product.
Solid phase filter residue is the copper concentrate for being enriched noble metal, and main component is:Ni 0.12%, Cu 72.8%, Fe 0.45%, Co < 0.005% (leaching rate of equivalent ferronickel cobalt is 99% or more), about 68 grams of tons of noble metal.Using autoclave Oxygen leaching obtains copper-containing solution for copper processed, and leached mud is then used to recycle noble metal, wherein the rate of recovery of copper is up to 98% More than, the rate of recovery of noble metal is up to 95% or more.A part of sulfur dioxide of matte smelting process is reacted with hydrogen sulfide prepares sulphur Sulphur, dosage are the half of hydrogen sulfide mole;Remaining sulfur dioxide send sulfate system extracting sulfuric acid, low as decomposing The leaching agent of ice nickel.
Finally, method of the invention is only preferable embodiment, is not intended to limit the scope of the present invention.It is all Within the spirit and principles in the present invention, any modification, equivalent replacement, improvement and so on should be included in the protection of the present invention Within the scope of.

Claims (9)

1. a kind of method to cu-ni sulphide ore comprehensive utilization, including:
1) directly sulfuric acid is used to carry out normal pressure Selectively leaching the low nickel matte that cu-ni sulphide ore is obtained through matte smelting, received respectively Collect hydrogen sulfide gas, leachate and leached mud, wherein the temperature of the normal pressure Selectively leaching is 25-80 DEG C;
2) leachate of step 1) is carried out removing iron, be collected respectively except liquid and iron dross removing after iron, it is described except after iron liquid for nickel and The extraction of cobalt, the iron dross removing is for smelting iron;
And/or send copper metallurgy industry to smelt the leached mud of step 1), respectively obtain copper and noble metal;
Sulfuric acid concentration described in the step 1) is 1mol/L-6mol/L, and the liquid-solid ratio of normal pressure Selectively leaching is 2:1-20:1, The normal pressure Selectively leaching time is 0.5-5h.
2. according to the method described in claim 1, it is characterized in that, the sulfur dioxide generated in the matte smelting and step 1) In stink damp precursor reactant prepare sulphur, and remaining sulfur dioxide is converted into carry out normal pressure Selectively leaching in step 1) Used sulfuric acid.
3. method according to claim 1 or 2, which is characterized in that carried out to leachate in step 1) in the step 2) Except iron is specially:
It is passed through air or oxygen-enriched air to leachate in step 1), while it is 3-4 to maintain the pH of solution, you can by iron with goethite Form removes, and obtains except liquid and iron dross removing after iron.
4. method according to claim 1 or 2, which is characterized in that sulfuric acid concentration is 3mol/L- in the step 1) 4mol/L, normal pressure Selectively leaching time are 0.5-2h, and extraction temperature is 50-70 DEG C, liquid-solid ratio 5:1-10:1.
5. method according to claim 1 or 2, which is characterized in that carried out to leachate in step 1) in the step 2) Except iron is specially:
Leachate pH to 3-7 is adjusted, the gas rich in oxygen is then passed to, is obtained except liquid and iron dross removing after iron.
6. method according to claim 1 or 2, which is characterized in that described in the step 2) except after iron liquid for nickel and The extraction of cobalt is specially:
After will be except liquid pH is adjusted to 4.0-5.5 after iron, extractant be added into liquid after except iron, extraction and separation obtain cobalt-carrying solution and contain Nickel solution, then the pH of solution containing nickel is adjusted to extractions of the 5.5-7.0 using extractant progress nickel;
Wherein, the extractant is the kerosin of P507 or the kerosin of Cyanex272, volume fraction 10-50%.
7. method according to claim 1 or 2, which is characterized in that the extracting method of the copper and noble metal is specially:
By the leached mud of step 1) through bessemerizing obtained blister copper, then the anode of refined copper and enriching noble metals is respectively obtained through electrolysis Mud, the earth of positive pole of enriching noble metals is for extracting noble metal;
Or, by Ore Leaching is used after the oxidized roasting of the leached mud of step 1), the leachate of enriching Cu is collected respectively and is enriched with expensive The leached mud of metal, the leached mud of enriching noble metals is for extracting noble metal;
Or, the leached mud of step 1) is carried out oxygen leaching, the leaching of the leachate and enriching noble metals of enriching Cu is collected respectively Slag, the leached mud of enriching noble metals is for extracting noble metal.
8. a kind of system to cu-ni sulphide ore comprehensive utilization, including:
Normal pressure Selectively leaching device collects sulphur respectively for directly sulfuric acid being used to carry out normal pressure Selectively leaching low nickel matte Change hydrogen, leachate and leached mud;
Deironing apparatus removes iron for carrying out the leachate obtained in normal pressure Selectively leaching device;
The extraction element of nickel and cobalt is used for the extraction of nickel and cobalt for collecting the liquid after removing iron in deironing apparatus;
Iron-smelting device, for handling the iron dross removing in deironing apparatus, for smelting iron;
And/or Copper making device, the leached mud for will be obtained in normal pressure Selectively leaching device carry out Copper making, respectively To copper and noble metal;
Further include temperature control device in the normal pressure Selectively leaching device, is used for the temperature of the normal pressure Selectively leaching Control is at 25-80 DEG C;
The sulfuric acid concentration is 1mol/L-6mol/L, and the liquid-solid ratio of normal pressure Selectively leaching is 2:1-20:1, normal pressure selective leaching It is 0.5-5h to go out the time.
9. system according to claim 8, which is characterized in that further include:
Matte smelting device for handling cu-ni sulphide ore, and provides low nickel matte, institute into the normal pressure Selectively leaching device It is that cu-ni sulphide ore is made through matte smelting to state low nickel matte;
Sulphur preparation facilities, the sulfur dioxide for making to generate in the matte smelting device are filled with the normal pressure Selectively leaching It sets middle generation stink damp precursor reactant and sulphur is made;
Sulfuric acid preparation facilities, for the part sulfur dioxide generated in the matte smelting device to be converted into sulfuric acid, and by its It is supplied to the normal pressure Selectively leaching device.
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CA3049827A CA3049827A1 (en) 2017-04-10 2018-04-08 Method and system for comprehensive recovery and utilization of copper-nickel sulfide ore
RU2019121486A RU2741429C1 (en) 2017-04-10 2018-04-08 Method and system for complete reprocessing of copper-nickel sulphide ore
FI20195705A FI20195705A1 (en) 2017-04-10 2018-04-08 Method for comprehensively recycling copper-nickel sulfide ore and system thereof
AU2018252056A AU2018252056B2 (en) 2017-04-10 2018-04-08 Method for comprehensively recycling copper-nickel sulfide ore and system thereof
PCT/CN2018/082209 WO2018188537A1 (en) 2017-04-10 2018-04-08 Method for comprehensively recycling copper-nickel sulfide ore and system thereof
ZA201904337A ZA201904337B (en) 2017-04-10 2019-07-01 Method for comprehensively recycling copper-nickel sulfide ore and system thereof
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CN107619068A (en) * 2017-09-30 2018-01-23 中南大学 A kind of iron sulfonium prepares the method that hydrogen sulfide is used for waste acid processing
CN107779595B (en) * 2017-10-23 2019-06-25 金川集团股份有限公司 A kind of method that low nickel matte wet-treating is directly separated ambrose alloy
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CN110273070A (en) * 2019-07-24 2019-09-24 中铝国际工程股份有限公司 A kind of method for removing iron of copper sulfide concentrate oxygen leaching liquid
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