CN115386730B - Method for recycling copper and nickel from copper and nickel-containing sludge - Google Patents

Method for recycling copper and nickel from copper and nickel-containing sludge Download PDF

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Publication number
CN115386730B
CN115386730B CN202211040042.9A CN202211040042A CN115386730B CN 115386730 B CN115386730 B CN 115386730B CN 202211040042 A CN202211040042 A CN 202211040042A CN 115386730 B CN115386730 B CN 115386730B
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copper
nickel
smelting
treated
content
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CN115386730A (en
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孙雁军
毛谙章
刘小文
周兆安
李俊
李加兴
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Guangdong Feinan Resources Utilization Co ltd
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Guangdong Feinan Resources Utilization Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/001—Dry processes
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B1/00—Preliminary treatment of ores or scrap
    • C22B1/02—Roasting processes
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B15/00—Obtaining copper
    • C22B15/0002—Preliminary treatment
    • C22B15/0004—Preliminary treatment without modification of the copper constituent
    • C22B15/0006—Preliminary treatment without modification of the copper constituent by dry processes
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B15/00—Obtaining copper
    • C22B15/0026—Pyrometallurgy
    • C22B15/0028—Smelting or converting
    • C22B15/003—Bath 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
    • 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
    • C22B23/02—Obtaining nickel or cobalt by dry processes
    • C22B23/025—Obtaining nickel or cobalt by dry processes with formation of a matte or by matte refining or converting into nickel or cobalt, e.g. by the Oxford 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
    • C22B34/00—Obtaining refractory metals
    • C22B34/30—Obtaining chromium, molybdenum or tungsten
    • C22B34/32—Obtaining chromium
    • 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

Abstract

The application discloses a method for recycling copper and nickel from copper-nickel-containing sludge, and belongs to the technical field of waste recycling. The method comprises the following steps: if the chromium content in the copper-nickel-containing sludge to be treated is more than or equal to 3wt% or the mass percentage of copper and nickel is less than 2, performing middle-low temperature reduction, vulcanization and roasting on the copper-nickel-containing sludge to be treated, and separating copper and nickel from chromium by adopting a mineral separation mode; if the chromium content in the copper-nickel-containing sludge to be treated is less than 3wt% and the content ratio of copper to nickel is less than or equal to 2 and less than or equal to 5, mixing the copper-nickel-containing sludge to be treated with a vulcanizing agent, and carrying out high-temperature reduction, vulcanization and smelting to obtain copper-nickel matte; if the chromium content in the copper-nickel-containing sludge to be treated is less than 3wt% and the content ratio of copper to nickel is more than 5, the reduction smelting method is adopted to recycle copper-nickel alloy and matte. According to the method, the chromium content, the copper-nickel ratio and the like in the raw materials are different, and the copper and nickel materials can be recovered according to different recovery routes, so that the loss of copper and nickel materials can be effectively reduced.

Description

Method for recycling copper and nickel from copper and nickel-containing sludge
Technical Field
The application relates to the technical field of waste recycling, in particular to a method for recycling copper and nickel from copper and nickel-containing sludge.
Background
The copper-nickel-containing sludge has wide sources and complex components, contains a certain amount of chromium besides copper and nickel, and is mainly prepared by reducing smelting to produce an alloy phase and a sulfonium phase, wherein the alloy phase and the sulfonium phase further recover copper and nickel through a conventional impurity removal process, the copper-nickel sludge has high chromium content, the conventional smelting process is easy to cause high slag melting point, slag formation is difficult, the separation effect of the sulfonium and slag is poor, and the recovery rate of copper and nickel is low.
In view of this, the present application has been made.
Disclosure of Invention
The application aims to provide a method for recycling copper and nickel from copper-nickel-containing sludge, so as to solve the technical problems.
The application can be realized as follows:
the application provides a method for recycling copper and nickel from copper-nickel-containing sludge, which is correspondingly carried out in one of the following modes according to the content of chromium, copper and nickel in a dry basis of the copper-nickel-containing sludge to be treated:
if the chromium content in the copper-nickel-containing sludge to be treated is more than or equal to 3wt% or the mass percentage of copper and nickel is less than 2, performing middle-low temperature reduction, vulcanization and roasting on the copper-nickel-containing sludge to be treated, and separating copper and nickel from chromium by adopting a physical or chemical sorting mode;
if the chromium content in the copper-nickel-containing sludge to be treated is less than 3wt% and the mass percentage of copper and nickel is less than or equal to 2 and less than or equal to 5, mixing the copper-nickel-containing sludge to be treated with a vulcanizing agent, and carrying out high-temperature reduction, vulcanization and smelting to obtain copper-nickel matte;
if the chromium content in the copper-nickel-containing sludge to be treated is less than 3wt% and the mass percentage of copper and nickel is more than 5, the reduction smelting method is adopted to recycle copper-nickel alloy and matte.
The total content of copper and nickel in the copper-nickel-containing sludge to be treated is more than or equal to 5wt%, preferably more than or equal to 10wt%.
In an alternative embodiment, the medium-low temperature reductive sulfidation bake comprises: and carrying out reduction vulcanization roasting on the copper-nickel-containing sludge to be treated, a vulcanizing agent and a carbon-based reducing agent to obtain vulcanization roasting slag.
In an alternative embodiment, the carbon-based reducing agent is coal.
In an alternative embodiment, the reductive sulfidation bake is performed at 850-1000 ℃ for 1-2 hours.
In an alternative embodiment, the total sulfur required for the reductive sulfidation bake is 1.2-1.8 times the theoretical amount required for complete copper sulfide and nickel, and the reducing agent is 1.5-2.5 times the theoretical amount required.
In an alternative embodiment, the copper-nickel-containing sludge to be treated is dried to a water content of less than or equal to 40wt% to obtain a dried sludge, and then the dried sludge is agglomerated or granulated with a vulcanizing agent and a carbon-based reducing agent, and then subjected to reduction vulcanization roasting.
In an alternative embodiment, the method further comprises: crushing and ball milling the vulcanized roasting slag, and then carrying out beneficiation treatment.
In an alternative embodiment, the high temperature reduction sulfidation smelting comprises: and (3) carrying out reduction, vulcanization and smelting on the sludge containing copper and nickel to be treated, a vulcanizing agent, a flux and a reducing agent to obtain copper-nickel matte.
In an alternative embodiment, the copper-nickel-containing sludge to be treated is firstly dried until the water content is less than or equal to 40wt percent to obtain dried sludge, then the dried sludge, the vulcanizing agent and the first flux are pressed or sintered into blocks, and then the blocks, the second flux and the reducing agent are subjected to reduction, vulcanization and smelting;
wherein the first flux is limestone and the second flux is quartz stone.
In an alternative embodiment, the vulcanizing agent includes at least one of a set of gypsum and pyrite.
In an alternative embodiment, the reducing agent includes at least one of coal, coke, and carbon.
In an alternative embodiment, the total sulfur amount required for high temperature reduction sulfidation smelting is 0.9-1.8 times the theoretical amount required for complete copper sulfide and nickel, and the reducing agent amount is 1.5-2.5 times the theoretical amount required.
In an alternative embodiment, the high temperature reduction sulfidation smelting is performed at 1150 ℃ to 1350 ℃ and the smelting temperature of the high temperature reduction sulfidation smelting exceeds 50 ℃ to 150 ℃ of the melting point of the pre-formulated slag.
In an alternative embodiment, when the content of iron in the copper-nickel matte obtained after the high temperature reduction sulfidation smelting process is > 4wt%, the method further comprises the step of carrying out pyrogenic iron removal on the copper-nickel matte to reduce the content of iron to below 4wt%;
wherein, the pyrogenic process iron removal comprises converter blowing iron removal or smelting iron removal; smelting iron removal includes copper oxide or copper salt redox iron removal or sulfate oxidation iron removal modes.
In an alternative embodiment, when smelting de-ironing is performed using copper oxide or copper salt redox de-ironing, it is performed as follows: copper nickel matte with iron content > 4wt% is co-smelted with copper-containing oxides or copper salts, fluxes and supplementary heating fuels.
In an alternative embodiment, the copper oxide or salt used in the copper oxide or salt redox iron removal process comprises at least one of copper oxide, copper carbonate, and basic copper carbonate; the flux used comprises at least one of calcium oxide and silicon dioxide; the supplemental heating fuel used includes coal or carbon.
In an alternative embodiment, copper nickel matte with iron content > 4wt% is mixed with copper oxide or copper salt to form clusters or balls during the redox iron removal process of copper oxide or copper salt, and then the fluxes and the heat-supplementing fuel are matched for smelting.
In alternative embodiments, the copper oxide or salt is used in an amount of 0.4 to 0.8 times the theoretical amount.
In an alternative embodiment, the copper oxide or copper salt is subjected to redox iron removal, the temperature of the co-smelting is 1150-1300 ℃, and the degree of silicic acid of the slag type used in the smelting process is 1.0-1.5.
In an alternative embodiment, when smelting de-ironing is performed using sulfate oxidation de-ironing, it is performed as follows: copper nickel matte with iron content > 4wt% is co-smelted with sulphate material and flux.
In an alternative embodiment, the sulfate material used in the sulfate oxidation de-ironing process includes at least one of spent sodium sulfate salt, calcium sulfate, and desulfurized gypsum; the fluxes used include silica and limestone.
In an alternative embodiment, copper nickel matte with iron content of more than 4wt% is mixed with sulfate material to form a ball or ball during sulfate oxidation, iron removal, sulfur and iron extrusion, and then a flux is matched for smelting.
In an alternative embodiment, the sulfate material is used in an amount of 0.4 to 1.0 times the theoretical value.
In an alternative embodiment, the temperature of the co-smelting is 1150 ℃ to 1300 ℃ during the sulfate oxidation de-ironing process, and the acidity of the slag type used in the smelting process is 1.0 to 1.5.
In an alternative embodiment, if the recovered matte has an iron content of > 4wt%, the method further comprises subjecting the matte to a pyrogenic process to reduce the iron content to below 4 wt%.
The beneficial effects of the application include:
according to the method provided by the application, copper and nickel in the copper-nickel-containing sludge can be effectively recovered by correspondingly adopting different recovery modes according to different copper-nickel ratios, so that the purpose of resource recovery and utilization is achieved, the waste of copper and nickel is greatly reduced, and the energy consumption and the production cost are reduced.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present application more clear, the technical solutions of the embodiments of the present application will be clearly and completely described below. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The method for recovering copper and nickel from the copper-nickel-containing sludge provided by the application is specifically described below.
The application provides a method for recycling copper and nickel from copper-nickel-containing sludge, which is correspondingly carried out in one of the following modes according to the content of chromium, copper and nickel in a dry basis of the copper-nickel-containing sludge to be treated:
A. if the chromium content in the copper-nickel-containing sludge to be treated is more than or equal to 3wt% or the mass percentage of copper and nickel is less than 2, performing middle-low temperature reduction, vulcanization and roasting on the copper-nickel-containing sludge to be treated, and separating copper and nickel from chromium by adopting a physical or chemical sorting mode;
B. if the chromium content in the copper-nickel-containing sludge to be treated is less than 3wt% and the mass percentage of copper and nickel is less than or equal to 2 and less than or equal to 5, mixing the copper-nickel-containing sludge to be treated with a vulcanizing agent, and carrying out high-temperature reduction, vulcanization and smelting to obtain copper-nickel matte;
C. if the chromium content in the copper-nickel-containing sludge to be treated is less than 3wt% and the mass percentage of copper and nickel is more than 5, the reduction smelting method is adopted to recycle copper-nickel alloy and matte.
It should be noted that, the total content of copper and nickel in the sludge containing copper and nickel to be treated is more than or equal to 5wt%, preferably more than or equal to 10wt%, if the total content of copper and nickel in the sludge is less than 5wt%, the unit product treatment cost is higher, the recovery rate of copper and nickel resources is lower, and the economical efficiency is poor.
For reference, in the above mode a, the medium-low temperature reductive vulcanization baking includes: and carrying out reduction vulcanization roasting on the copper-nickel-containing sludge to be treated, a vulcanizing agent and a carbon-based reducing agent to obtain vulcanization roasting slag.
Preferably, the carbon-based reducing agent is coal.
The reduction, vulcanization and roasting are carried out for 1h to 2h (such as 1h, 1.2h, 1.5h, 1.8h or 2h, etc.) under the condition of 850 ℃ -1000 ℃ (such as 850 ℃, 900 ℃, 950 ℃ or 1000 ℃). The above 1-2 hours actually refer to the effective calcination time.
The sulfur source required in the reduction, vulcanization and roasting is mainly from a copper-nickel sludge raw material and an external vulcanizing agent. The total sulfur amount required for the reduction sulfidation roasting is 1.2-1.8 times (such as 1.2 times, 1.3 times, 1.4 times, 1.5 times, 1.6 times, 1.7 times or 1.8 times, etc.) the theoretical amount required for the complete copper sulfide and nickel, and the carbon-based reducing agent is 1.5-2.5 times (such as 1.5 times, 1.6 times, 1.7 times, 1.8 times, 1.9 times, 2.0 times, 2.1 times, 2.2 times, 2.3 times, 2.4 times or 2.5 times, etc.) the theoretical amount.
The theoretical amount of sulfur required for the complete copper sulfide and nickel and the amount of the external vulcanizing agent are calculated as follows:
m 0 ＝(m S ×η-m 1 ×w s1 )÷w S2 。
wherein:
m S theoretical amount of sulfur required for complete copper sulfide and nickel;
m 0 the physical amount of the vulcanizing agent is added;
m 1 the quality of the copper-nickel sludge is that of the copper-nickel sludge;
w Cu the mass percentage of Cu in the copper-nickel sludge is as follows;
w Ni the mass percentage of Ni in the copper-nickel sludge is as follows;
w s1 the mass percentage of the element S in the copper-nickel sludge is as follows;
w S2 is the mass percentage of the element S in the externally added vulcanizing agent.
η is the ratio of the total sulfur usage required for the reductive sulfidation bake to the theoretical amount of sulfur required for complete copper and nickel sulfide.
The theoretical dosage calculation formula of the carbon-based reducing agent is as follows:
wherein: m is m c The theoretical dosage of the carbon-based reducing agent;
m 1 the quality of the copper-nickel sludge is that of the copper-nickel sludge;
m 2 the quality of the added vulcanizing agent in actual use is that of the vulcanizing agent;
w Cu the mass percentage of Cu in the copper-nickel sludge is as follows;
w Ni the mass percentage of Ni in the copper-nickel sludge is as follows;
w s1 the mass percentage of the element S in the copper-nickel sludge is as follows;
w S2 the mass percentage of the element S in the externally added vulcanizing agent is as follows;
w C is the mass percentage of the effective C in the reducing agent;
a is the average chemical valence state of S in the external curing agent.
Preferably, in some preferred embodiments, the copper-nickel-containing sludge to be treated may be dried to a moisture content of 40wt% or less to obtain a dried sludge, and then the dried sludge may be agglomerated or pelletized with a sulfiding agent and a carbon-based reducing agent, followed by reductive sulfidation calcination (which may be performed in a sulfidation calcination apparatus, for example).
Further, the vulcanized roasting slag is crushed and ball-milled, and then is subjected to physical or chemical separation (such as beneficiation treatment) to enrich and recycle resources such as cuprous sulfide, trinickel disulfide and the like.
On the support, through the mode A, copper and nickel are converted into sulfide, chromium is oxide or spinel, other materials are partially sintered and are in a non-molten state, and products are separated and recovered through physical or chemical separation modes and the like.
For reference, in the above-described mode B, the high-temperature reduction sulfidation smelting includes: and (3) carrying out reduction, vulcanization and smelting on the sludge containing copper and nickel to be treated, a vulcanizing agent, a flux and a reducing agent to obtain copper-nickel matte.
Wherein, the high-temperature reduction and vulcanization smelting is carried out under the conditions of 1150 ℃ -1350 ℃ (such as 1150 ℃, 1200 ℃, 1250 ℃, 1300 ℃, 1350 ℃ or the like). Specifically, the slag preparation method is determined by ensuring that the smelting temperature of high-temperature reduction vulcanization smelting exceeds 50 ℃ -150 ℃ (such as 50 ℃, 80 ℃, 100 ℃, 120 ℃ or 150 ℃ and the like) of the melting point of the pre-prepared slag. The chromium content of the residue obtained by pre-preparing is less than or equal to 2.5 weight percent.
In some preferred embodiments, the copper-nickel-containing sludge to be treated can be dried to a water content of less than or equal to 40wt% to obtain dried sludge, then the dried sludge, the vulcanizing agent and the first flux are pressed or sintered into blocks, and then the blocks, the second flux and the reducing agent are subjected to reduction, vulcanization and smelting, so that copper-nickel matte, slag, smoke dust and the like are finally produced.
The first flux is limestone, and the second flux is quartz. The vulcanizing agent includes at least one of a set of gypsum and pyrite. The reducing agent includes at least one of coal, coke, and carbon, etc.
The slag type can be adjusted by adopting the first flux and the second flux simultaneously, and the percentage contents of three main elements of ferrosilicon and calcium in the slag can be adjusted by adjusting the amount of the fluxes.
For reference, the sulfur source required in the high-temperature reduction sulfidation smelting mainly comes from copper-nickel sludge raw materials and external vulcanizing agents. The total sulfur consumption required by high temperature reduction sulfidation smelting is 0.9-1.8 times (such as 0.9 times, 1 times, 1.2 times, 1.5 times or 1.8 times, etc.) of the theoretical sulfur consumption required by complete copper sulfide and nickel, and the consumption of the reducing agent is 1.5-2.5 times (such as 1.5 times, 1.6 times, 1.7 times, 1.8 times, 1.9 times, 2.0 times, 2.1 times, 2.2 times, 2.3 times, 2.4 times or 2.5 times, etc.) of the theoretical consumption. Wherein the calculation formulas of the theoretical amount of the required amount of the complete copper sulfide and nickel, the amount of the externally added vulcanizing agent and the theoretical amount of the reducing agent are the same as those of the mode A.
If the iron content in the copper-nickel matte obtained after high-temperature reduction, vulcanization and smelting is less than or equal to 4wt%, the copper-nickel matte can be directly used as a copper-nickel matte raw material for wet oxygen pressure treatment. However, copper nickel matte obtained by the conventional reductive sulfidation process is typically Gao Tieliu (i.e., iron content > 4 wt.%) and therefore further preparation is required to obtain low iron matte (iron content. Ltoreq.4 wt.%).
For reference, when the content of iron in the copper-nickel matte obtained after the high-temperature reduction sulfidation smelting treatment is > 4wt%, the method further comprises the step of carrying out pyrogenic iron removal on the copper-nickel matte to reduce the content of iron to below 4 wt%.
Wherein, the pyrogenic process iron removal comprises converter blowing iron removal or smelting iron removal;
it should be emphasized that in the prior art, the hot iron removal is usually performed by converting iron, and in the present application, the inventors propose to achieve the reduction of iron content by smelting iron removal.
Specifically, smelting iron removal includes redox iron removal by copper oxide or copper salt or sulfate oxidation iron removal.
a. When smelting and de-ironing are performed by copper oxide or copper salt redox de-ironing, the following steps are performed: copper nickel matte with iron content > 4wt% is co-smelted with copper-containing oxides or copper salts, fluxes and supplementary heating fuels.
Preferably, copper nickel matte with iron content > 4wt% may be first mixed with copper-containing oxides or copper salts to form clusters or balls, and then melted with flux and supplementary heating fuel.
Wherein the copper-containing oxide or copper salt comprises at least one of copper oxide, copper carbonate and basic copper carbonate, the flux comprises at least one of calcium oxide and silicon dioxide, and the heat-supplementing fuel comprises coal or carbon.
The amount of the copper-containing oxide or copper salt is 0.4-0.8 times (e.g. 0.4 times, 0.5 times, 0.6 times, 0.7 times or 0.8 times, etc.) of the theoretical amount, and the iron content in the sulfonium phase and the oxidizing atmosphere of different furnace types are mainly different (i.e. the oxidized FeS ratio is different), so that the final purpose is to reduce the iron content in the sulfonium phase to below 4% without affecting the copper recovery.
For reference, the theoretical dosage calculation formula of the copper-containing oxide or copper salt is as follows:
wherein: m is m a Theoretical amount of copper oxide or copper salt;
m b the quality of the high-iron matte is that of the high-iron matte;
W Fe is the mass percentage of Fe in the high-iron matte;
W a is the mass percentage of Cu in copper oxide or copper salt.
In the copper oxide or copper salt redox iron removal mode, the common smelting temperature can be 1150 ℃ -1300 ℃ (such as 1150 ℃, 1200 ℃, 1250 ℃, 1300 ℃, and the like, and the slag type is specifically determined according to the slag type), and the silicic acid degree of the slag type used in the smelting process is 1.0-1.5 (such as 1.0, 1.1, 1.2, 1.3, 1.4, or 1.5).
The chemical reaction equations involved in the above process include the following:
CuCO 3 ＝CuO+CO 2 (pyrolysis);
CuCO 3 ·Cu(OH) 2 ＝CuO+CO 2 +H 2 o (pyrolysis);
6CuO+4FeS＝3Cu 2 S+4FeO+SO 2 ；
FeS+O 2 ＝FeO+SO 2 ；
aFeO+bCaO+cSiO 2 ＝aFeO·bCaO·cSiO 2 。
further, feO is added with calcium oxide, silicon dioxide and the like to form slag, and Cu 2 S enters the product sulfonium phase.
b. When smelting and de-ironing are performed by sulfate oxidation and de-ironing, the following steps are performed: copper nickel matte with iron content > 4wt% is co-smelted with sulphate material and flux.
Preferably, copper nickel matte with iron content > 4wt% may be first mixed with sulfate material to form briquettes or balls, and then added with flux for smelting.
Wherein the sulfate material comprises at least one of waste sodium sulfate salt, calcium sulfate and desulfurized gypsum, and the flux comprises silicon dioxide and limestone.
The amount of the sulfate material is 0.4-1.0 times (such as 0.4 times, 0.5 times, 0.6 times, 0.7 times, 0.8 times, 0.9 times or 1.0 times) of the theoretical value, and the iron content in the sulfur phase and the oxidizing atmosphere of different furnace types are mainly different (namely, the oxidized FeS proportion is different), so that the final purpose is to reduce the iron content in the matte phase to below 4%.
For reference, the theoretical dosage calculation formula of the sulfate material is as follows:
wherein: m is m d Is the theoretical dosage of sulfate materials;
m b the quality of the high-iron matte is that of the high-iron matte;
W Fe is the mass percentage of Fe in the high-iron matte;
W d is the mass percentage of S in the sulfate material.
In the sulfate oxidation and iron removal process, the common smelting temperature is 1150-1300 ℃ (such as 1150 ℃, 1200 ℃, 1250 ℃ or 1300 ℃ and the like, and the specific slag type is determined), and the silicon acidity of the slag type used in the smelting process is 1.0-1.5 (such as 1.0, 1.1, 1.2, 1.3, 1.4 or 1.5).
The chemical reaction equations involved in the above process include the following:
3CaSO 4 +FeS＝3CaO+FeO+4SO 2 (g)；
or 3Na 2 SO 4 +FeS＝3Na 2 O+FeO+4SO 2 (g)；
FeS+O 2 ＝FeO+SO 2 ；
aFeO+bCaO+cSiO 2 ＝aFeO·bCaO·cSiO 2 ；
Or aFeO+ bNa 2 O+cSiO 2 ＝aFeO·bNa 2 O·cSiO 2 。
On the basis, copper-nickel matte with iron content less than or equal to 4wt% can be obtained through the mode B.
For reference, in the above-mentioned mode C, the pyrometallurgy reduction smelting process may refer to the prior art, and will not be described herein in detail.
Further, if the iron content of the recovered matte is greater than 4wt%, the method further comprises the step of carrying out pyrogenic iron removal on the matte to reduce the iron content to below 4 wt%.
It should be noted that, the reduction of the iron content in the matte to below 4wt% may refer to the smelting de-ironing mode (including copper oxide or copper salt redox de-ironing or sulfate oxidation de-ironing) in the above mode B, and will not be described in detail herein.
In the application, when the medium-low temperature vulcanization reduction roasting is carried out, as the materials do not reach the melting temperature, cuprous sulfide and trinickel disulfide are generated by vulcanization and mixed with slag, and are separated in a mineral separation mode, a process different from a process for directly separating copper-nickel matte (cuprous sulfide and trinickel disulfide) and slag by high-temperature reduction smelting is selected, and the method is mainly based on the reason of Cr: when the Cr content in the raw material is too high, the properties of melting point, viscosity and the like of slag in the reduction smelting process are deteriorated, and the separation of copper-nickel matte (cuprous sulfide and trinickel disulfide) and the slag is affected, so that the copper-nickel content in the slag is higher, and the direct yield of the copper-nickel matte is low. When the Cr content in the raw material is low, the high-temperature one-step method can be directly adopted for reduction and vulcanization to directly prepare copper nickel matte and molten slag; when the Cr content in the raw material is higher, a two-step method is adopted, namely, the method of reducing and vulcanizing at medium and low temperature and then separating and recovering copper and nickel sulfide in a mineral separation mode is adopted.
The main reaction equations for the reduction sulfidation and the reduction to metal are as follows:
2CuO+CaSO 4 +5C＝Cu 2 S+CaO+5CO(g)；
4CuO+2CaSO 4 +5C＝2Cu 2 S+2CaO+5CO 2 (g)；
3NiO+2CaSO 4 +9C＝Ni 3 S 2 +2CaO+9CO(g)；
6NiO+4CaSO 4 +9C＝2Ni 3 S 2 +4CaO+9CO 2 (g)；
meo+c=me+co (g) (Me stands for Cu and Ni, the following);
2MeO+C＝2Me+CO 2 (g)；
aFeOx+bCaO+cAl 2 O 3 +dSiO 2 ＝aFeOx·bCaO·cAl 2 O 3 ·dSiO 2 。
the principle of process selection for preparing different products by different copper-nickel ratios is as follows, when the copper-nickel ratio in raw materials is larger than 5, the most economical and cost-effective metal alloy and matte are prepared in the products obtained by reduction, on one hand, most of nickel and noble metal can be enriched in the alloy, and the melting point of the alloy is limited to be increased due to the fact that the nickel content in the alloy is not high, the reduction smelting process is not greatly influenced, and the following alloy enters a coarse copper refining process, and most of nickel can be enriched in secondary refining slag for secondary use. When the mass ratio of copper to nickel in the raw materials is less than or equal to 5 and is more than or equal to 2, if the consumption of the vulcanizing agent is low, the method is used for producing the alloy, the nickel content in the alloy is too high, the influence on the rise of the melting point of the alloy is large (the melting point of metal copper is 1083 ℃, and the melting point of metal nickel is 1453 ℃), and the alloy and the slag can be well separated in the smelting process only by relatively high smelting temperature, so that the energy consumption is obviously increased. However, as the melting point of the trinickel disulfide is only 797 ℃, the melting point of the cuprous sulfide is 1100 ℃, and when the nickel content is high, only the copper-nickel matte is produced by adopting reduction vulcanization smelting, so that the problem of high energy consumption for producing the alloy can be effectively solved.
The features and capabilities of the present application are described in further detail below in connection with the examples.
Example 1
The embodiment provides a method for recycling copper and nickel from copper-nickel-containing sludge, which comprises the following steps:
(1) Drying the copper-nickel-containing sludge with the total content of 15.7% of dry copper and nickel, the chromium content being less than 3% and the copper-nickel ratio (mass ratio) being 3 until the water content is less than or equal to 40% to obtain dried sludge, pressing the dried sludge, desulfurized gypsum slag and limestone into blocks, and carrying out reduction, vulcanization and smelting with quartz stone and reducing agent coal at 1250 ℃ for 2.0h to obtain copper-nickel matte (containing 15.6% of Fe, 45.2% of Cu, 22.7% of Ni and 23.4% of S), slag, smoke dust and the like, wherein the total content of the copper-nickel is more than 4% of the copper-nickel.
The total sulfur consumption is 1.5 times of theoretical sulfur consumption of theoretical complete copper sulfide and nickel, the copper-containing oxide consumption is 0.6 times of theoretical sulfur consumption, the limestone and quartz stone consumption are matched with proper amounts according to slag type requirements, and the reducing agent consumption is 1.5 times of theoretical sulfur consumption.
(2) Smelting and de-ironing the copper nickel matte according to the following copper oxide or copper salt de-ironing modes: copper nickel matte is firstly mixed with CuO and basic salt in different proportions to form a group, and then quartz sand flux and reducer C are added for smelting for 2 hours at 1250 ℃.
The total amount of copper in the CuO and the basic salt is 0.3 times, 0.4 times, 0.5 times, 0.6 times, 0.7 times, 0.8 times and 0.9 times of the theoretical copper demand.
Slag type FeO used in smelting process: siO (SiO) 2 : cao=34:40:26 (mass ratio), and the flux amount was calculated according to slag type theory.
Under the condition that other conditions are unchanged, the element content of the product obtained by correspondingly using copper oxide or copper salt in the step (2) under different dosages is examined, and the results are shown in table 1.
Table 1 results of analysis of principal elements in the products
As can be seen from table 1 above: when the Cu consumption in the copper oxide or copper salt is 0.4-0.8 times of the theoretical amount, the Fe content in the obtained matte after smelting is lower than 4wt%; when the Cu content in the copper oxide or copper salt is 0.3 times of the theoretical amount, the Fe content in the sulfonium is 4.82wt%, and the Fe content does not reach the standard. It should be noted that when the Cu content in the copper oxide or copper salt is more than 0.8 times the theoretical amount, the iron content in the matte can be removed to be far lower than 4wt%, and the Cu content in the copper oxide or copper salt is preferably 0.4 to 0.8 times the theoretical amount in view of the cost and energy consumption of the reagent.
Example 2
This embodiment differs from embodiment 1 in that:
step (2): smelting and de-ironing the copper-nickel matte obtained in the step (1) according to the following sulfate de-ironing mode: the copper nickel matte is firstly mixed with CaSO of 0.3 times, 0.4 times, 0.6 times, 0.8 times, 1.0 times and 1.2 times of theoretical times respectively 4 Mixing to prepare a block, and then adding a certain amount of silicon dioxide according to slag, and smelting for 2.0h at 1250 ℃.
Slag type FeO used in the smelting process is as follows: siO (SiO) 2 : cao=28:40:32 (mass ratio), the amount of silica was formulated according to the theoretical amount calculated for slag type.
Under the precondition of unchanged other conditions, the CaSO in the step (2) is inspected 4 The elemental content of the corresponding product obtained at the different amounts is shown in table 2.
TABLE 2 analysis results of principal elements in the products
As can be seen from table 2 above: when the calcium sulfate dosage is 0.3 times of the theoretical amount, the iron content in the sulfonium is higher than 4 weight percent; when the calcium sulfate is 0.4-1.2 times of the theoretical amount, the iron content in the sulfonium can be lower than 4wt%, and when the calcium sulfate is more than 1.0 times of the theoretical amount, the iron content in the sulfonium can be removed to be far lower than 4wt%, and the calcium sulfate is preferably 0.4-1.0 times of the theoretical amount in consideration of the use cost and energy consumption of the reagent.
In summary, the method provided by the application can effectively recycle copper and nickel in the copper-nickel-containing sludge, thereby achieving the purpose of recycling resources, greatly reducing the waste of copper and nickel and further reducing the production cost.
The above is only a preferred embodiment of the present application, and is not intended to limit the present application, but various modifications and variations can be made to the present application by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application should be included in the protection scope of the present application.

Claims (26)

1. The method for recycling copper and nickel from the copper-nickel-containing sludge is characterized by correspondingly adopting one of the following modes according to the content of chromium, copper and nickel in the dry basis of the copper-nickel-containing sludge to be treated:
if the chromium content in the copper-nickel-containing sludge to be treated is more than or equal to 3wt% or the mass percentage of copper and nickel is less than 2, performing middle-low temperature reduction, vulcanization and roasting on the copper-nickel-containing sludge to be treated, and separating copper and nickel from chromium by adopting a separation mode;
if the chromium content in the copper-nickel-containing sludge to be treated is less than 3wt% and the mass percentage of copper and nickel is less than or equal to 2 and less than or equal to 5, mixing the copper-nickel-containing sludge to be treated with a vulcanizing agent, and carrying out high-temperature reduction, vulcanization and smelting to obtain copper-nickel matte;
if the chromium content in the copper-nickel-containing sludge to be treated is less than 3wt% and the mass percentage of copper and nickel is more than 5, adopting a pyrogenic reduction smelting method to recycle copper-nickel alloy and matte;
the total content of copper and nickel in the copper-nickel-containing sludge to be treated is more than or equal to 5wt%.
2. The method according to claim 1, wherein the total content of copper and nickel in the copper-nickel-containing sludge to be treated is not less than 10wt%.
3. The method according to claim 1 or 2, wherein the medium-low temperature reductive sulfidation calcination comprises: and carrying out reduction vulcanization roasting on the copper-nickel-containing sludge to be treated, a vulcanizing agent and a carbon-based reducing agent to obtain vulcanization roasting slag.
4. A method according to claim 3, wherein the carbon-based reducing agent is coal.
5. A method according to claim 3, wherein the reductive sulfidation bake is carried out at 850 ℃ -1000 ℃ for 1h-2h.
6. A method according to claim 3, wherein the total sulfur required for the reductive sulfidation bake is 1.2 to 1.8 times the theoretical amount required for complete copper sulfide and nickel, and the carbon-based reducing agent is 1.5 to 2.5 times the theoretical amount required for complete reduction of copper sulfide and nickel.
7. A method according to claim 3, characterized in that the copper-nickel-containing sludge to be treated is dried to a water content of less than or equal to 40 wt.% to obtain a dried sludge, which is then agglomerated or granulated with the sulfidizing agent and the carbon-based reducing agent, and subjected to reductive sulfidation roasting.
8. The method as recited in claim 7, further comprising: crushing and ball milling the vulcanized roasting slag, and then carrying out beneficiation treatment.
9. The method of claim 1, wherein the high temperature reduction sulfidation smelting comprises: and (3) carrying out reduction, vulcanization and smelting on the sludge containing copper and nickel to be treated, a vulcanizing agent, a flux and a reducing agent to obtain copper-nickel matte.
10. The method according to claim 9, wherein the copper-nickel-containing sludge to be treated is dried to a water content of 40wt% or less to obtain a dried sludge, and then the dried sludge is pressed or sintered into a block with the vulcanizing agent and the first flux, and then reduced, vulcanized and smelted with the second flux and the reducing agent;
the first flux is limestone, and the second flux is quartz stone.
11. The method of claim 10, wherein the sulfidizing agent comprises at least one of gypsum sulfide and pyrite.
12. The method of claim 10, wherein the reducing agent comprises at least one of coal, carbon, and coke.
13. The method of claim 9, wherein the total sulfur required for high temperature reduction sulfidation smelting is 0.9-1.8 times the theoretical amount required for complete copper sulfide and nickel, and the reducing agent is 1.5-2.5 times the theoretical amount required.
14. The method according to claim 9, wherein the high temperature reduction sulfidation smelting is carried out at 1150 ℃ to 1350 ℃ and the smelting temperature of the high temperature reduction sulfidation smelting exceeds 50 ℃ to 150 ℃ of the melting point of the pre-formulation slag.
15. The method according to claim 14, characterized in that the copper-nickel matte obtained after the high temperature reduction sulfidation smelting process has an iron content of > 4wt%, further comprising the step of pyrometallurgical de-ironing the copper-nickel matte to reduce the iron content to below 4wt%;
wherein, the pyrogenic process iron removal comprises converter blowing iron removal or smelting iron removal; smelting iron removal comprises adopting a copper oxide or copper salt oxidation reduction iron removal mode or a sulfate oxidation iron removal mode.
16. The method according to claim 15, characterized in that when smelting de-ironing is performed by means of copper oxide or copper salt redox de-ironing, it is performed as follows: copper nickel matte with iron content > 4wt% is co-smelted with copper-containing oxides or copper salts, fluxes and supplementary heating fuels.
17. The method according to claim 16, wherein the copper-containing oxide or copper salt used in the copper oxide or copper salt redox iron removal process comprises at least one of copper oxide, copper carbonate and basic copper carbonate; the flux used comprises at least one of calcium oxide and silicon dioxide; the supplemental heating fuel used includes coal or carbon.
18. The method according to claim 17, characterized in that copper nickel matte with an iron content of > 4wt% is mixed with copper oxide or copper salt during redox de-ironing to form clusters or balls, which are subsequently fed with the flux and the reducing agent for smelting.
19. The method according to claim 18, characterized in that the copper oxide or copper salt is used in an amount of 0.4-0.8 times the theoretical amount.
20. The method according to claim 16, characterized in that in the redox iron removal of copper oxide or copper salt, the co-smelting is performed at 1150-1300 ℃, and the acidity of the slag used in the smelting is 1.0-1.5.
21. The method according to claim 15, characterized in that when smelting de-ironing is performed by sulfate oxidation de-ironing, it is performed as follows: copper nickel matte with iron content > 4wt% is co-smelted with sulphate material and flux.
22. The method of claim 21, wherein the sulfate material used in the sulfate oxidation de-ironing process comprises at least one of spent sodium sulfate salt, calcium sulfate, and desulfurized gypsum; the fluxes used include silica and limestone.
23. The method as claimed in claim 22, characterized in that copper-nickel matte with an iron content of > 4wt% is mixed with the sulfate material during sulfate oxidation de-ironing to form clusters or balls, which are subsequently fed with the flux for smelting.
24. The method of claim 23, wherein the sulfate material is used in an amount of 0.4 to 1.0 times the theoretical value.
25. The method according to claim 21, wherein the temperature of the co-smelting is 1150 ℃ to 1300 ℃ during the sulfate oxidation de-ironing, and the acidity of the slag type used in the smelting is 1.0 to 1.5.
26. The method of claim 1, further comprising pyrogenically de-ironing the matte to reduce the iron content to below 4wt% if the recovered matte has an iron content of > 4 wt%.
CN202211040042.9A 2022-08-29 2022-08-29 Method for recycling copper and nickel from copper and nickel-containing sludge Active CN115386730B (en)

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CN110512083A (en) * 2019-09-25 2019-11-29 中南大学 A kind of method of metal resource comprehensive utilization in oil-containing electroplating sludge
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RU2010132695A (en) * 2010-08-04 2012-02-10 Учреждение Российской академии наук Институт фундаментальных проблем биологии РАН (RU) METHOD FOR WASTE WATER SEDIMENTS PROCESSING
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