CN115386730A - Method for recovering copper and nickel from copper and nickel-containing sludge - Google Patents
Method for recovering copper and nickel from copper and nickel-containing sludge Download PDFInfo
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- 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
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- C22B15/00—Obtaining copper
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- C22B15/0004—Preliminary treatment without modification of the copper constituent
- C22B15/0006—Preliminary treatment without modification of the copper constituent by dry processes
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- C22B15/00—Obtaining copper
- C22B15/0026—Pyrometallurgy
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- C22B23/00—Obtaining nickel or cobalt
- C22B23/005—Preliminary treatment of ores, e.g. by roasting or by the Krupp-Renn process
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- 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
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- C22B34/00—Obtaining refractory metals
- C22B34/30—Obtaining chromium, molybdenum or tungsten
- C22B34/32—Obtaining chromium
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Abstract
The invention discloses a method for recovering copper and nickel from copper-nickel-containing sludge, belonging to the technical field of waste resource utilization. The method comprises the following steps: if the chromium content in the sludge containing copper and nickel to be treated is more than or equal to 3wt% or the mass percentage of copper and nickel is less than 2, carrying out medium-low temperature reduction, vulcanization and roasting on the sludge containing copper and nickel to be treated, and then separating copper, nickel and chromium by adopting a mineral separation mode; if the content of chromium in the sludge containing copper and nickel to be treated is less than 3wt% and the content ratio of copper to nickel is not more than 2 and not more than 5, mixing the sludge containing copper and nickel to be treated with a vulcanizing agent, and carrying out high-temperature reduction vulcanization smelting to obtain copper-nickel matte; if the content of chromium in the sludge containing copper and nickel to be treated is less than 3wt% and the content ratio of copper to nickel is more than 5, reducing and smelting by adopting a pyrogenic process to recover copper-nickel alloy and matte. The method can recover the chromium and the copper-nickel ratio according to different recovery routes according to different chromium contents, copper-nickel ratios and the like in the raw materials, and can effectively reduce the loss of copper and nickel substances.
Description
Technical Field
The invention relates to the technical field of waste resource utilization, in particular to a method for recovering copper and nickel from copper-nickel-containing sludge.
Background
The existing low-chromium copper-nickel sludge recovery method mainly comprises the steps of producing an alloy phase and a sulfonium phase through reduction smelting, and further recovering copper and nickel through a conventional impurity removal process, wherein the copper-nickel sludge contains high chromium, so that the conventional recovery smelting process has the disadvantages of high slag melting point, difficult slagging, poor separation effect of sulfonium and slag and low copper-nickel recovery rate.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The invention aims to provide a method for recovering copper and nickel from copper-nickel-containing sludge, so as to solve the technical problem.
The application can be realized as follows:
the application provides a method for recovering copper and nickel from copper-nickel-containing sludge, which is carried out by correspondingly adopting one of the following modes according to the contents of chromium, copper and nickel in a copper-nickel-containing sludge dry basis to be treated:
if the chromium content in the sludge containing copper and nickel to be treated is more than or equal to 3wt% or the mass percentage of copper and nickel is less than 2, carrying out medium-low temperature reduction, vulcanization and roasting on the sludge containing copper and nickel to be treated, and then separating copper, nickel and chromium by adopting a physical or chemical separation mode;
if the chromium content in the sludge containing copper and nickel to be treated is less than 3wt% and the mass percentage of copper to nickel is not more than 2 and not more than 5, mixing the sludge containing copper and nickel to be treated with a vulcanizing agent, and carrying out high-temperature reduction vulcanization smelting to obtain copper-nickel matte;
if the chromium content in the sludge containing copper and nickel to be treated is less than 3wt% and the mass percentage of copper and nickel is more than 5, reducing and smelting by adopting a fire method to recover copper-nickel alloy and matte.
The total content of copper and nickel in the sludge containing copper and nickel to be treated is more than or equal to 5wt percent, and preferably more than or equal to 10wt percent.
In an alternative embodiment, the medium and low temperature reduction sulfiding roasting comprises: and (3) carrying out reduction, vulcanization and roasting on the copper-nickel-containing sludge to be treated, a vulcanizing agent and a carbon-based reducing agent to obtain the vulcanization and roasting slag.
In an alternative embodiment, the carbon-based reducing agent is coal.
In an alternative embodiment, the reductive sulfidation bake is carried out at 850-1000 deg.C for 1-2h.
In an alternative embodiment, the total sulfur usage required for the reductive sulfidation bake is 1.2 to 1.8 times the theoretical amount required to completely sulfide copper and nickel, and the reducing agent usage is 1.5 to 2.5 times the theoretical amount required.
In an optional embodiment, the sludge containing copper and nickel to be treated is dried to the water content of less than or equal to 40wt% to obtain dried sludge, and then the dried sludge, a vulcanizing agent and a carbon-based reducing agent are briquetted or granulated, and then reduction, vulcanization and roasting are carried out.
In an alternative embodiment, the method further comprises: and crushing and ball-milling the vulcanization roasting slag, and then carrying out mineral processing.
In an alternative embodiment, the high temperature reduction sulfidation smelting comprises: and carrying out reduction, vulcanization and smelting on the copper-nickel-containing sludge to be treated, a vulcanizing agent, a fusing agent and a reducing agent to obtain copper-nickel matte.
In an optional embodiment, the sludge containing copper and nickel to be treated is dried to the water content of less than or equal to 40wt% to obtain dried sludge, then the dried sludge, a vulcanizing agent and a first fusing agent are pressed or sintered into blocks, and then the blocks are subjected to reduction vulcanization smelting with a second fusing agent and a reducing agent;
wherein the first fusing agent is limestone and the second fusing agent is quartz.
In an alternative embodiment, the sulfiding agent comprises at least one of anhydrite and pyrite.
In an alternative embodiment, the reductant comprises at least one of coal, coke, and carbon dioxide.
In an alternative embodiment, the total sulfur usage required for the high temperature reduction sulfidation smelting is 0.9 to 1.8 times the theoretical amount required to completely sulfide copper and nickel, and the reductant usage is 1.5 to 2.5 times the theoretical amount required.
In an alternative embodiment, the high-temperature reduction vulcanization smelting is carried out at 1150-1350 ℃, and the smelting temperature of the high-temperature reduction vulcanization smelting exceeds 50-150 ℃ of the melting point of the pre-prepared slag.
In an alternative embodiment, when the content of iron in the copper nickel matte obtained after the high-temperature reduction-vulcanization smelting treatment is more than 4wt%, the method further comprises the step of carrying out fire deferrization on the copper nickel matte to reduce the content of iron to be less than 4wt%;
wherein the fire process deferrization comprises converter blowing deferrization or smelting deferrization; the smelting deferrization comprises a copper oxide or copper salt oxidation reduction deferrization or sulfate oxidation deferrization mode.
In an alternative embodiment, when the smelting deferrization is carried out by means of copper oxide or copper salt redox deferrization, the following procedure is carried out: copper nickel matte with iron content of more than 4wt% is smelted together with copper oxide or copper salt, flux and heat-supplementing fuel.
In an alternative embodiment, the copper-containing oxide or copper salt used in the redox de-ironing 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 used heat-supplementing fuel comprises coal or carbon essence.
In an alternative embodiment, in the process of redox deferrization of copper oxide or copper salt, copper nickel matte with iron content of more than 4wt% is mixed with copper oxide or copper salt to prepare a cluster or a ball, and then the cluster or the ball is mixed with flux and heat supplementing fuel for smelting.
In an alternative embodiment, the copper oxide or copper salt is used in an amount of 0.4 to 0.8 times the theoretical amount.
In an alternative embodiment, in the copper oxide or copper salt redox deferrization mode, the temperature of the co-smelting is 1150-1300 ℃, and the silicate degree of the slag used in the smelting process is 1.0-1.5.
In an alternative embodiment, when the smelting deferrization is carried out by sulfate oxidation deferrization, it is carried out in the following manner: copper nickel matte with iron content of more than 4wt% is smelted together with sulfate material and flux.
In an alternative embodiment, 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 flux used includes silica and limestone.
In an alternative embodiment, copper-nickel matte with an iron content of more than 4 wt.% is mixed with a sulfate material to form a mass or a pellet, which is then added to a flux for smelting in a sulfate oxidation de-ironing sulfur-extruding process.
In an alternative embodiment, the sulfate material is used in an amount of 0.4 to 1.0 times theoretical.
In an alternative embodiment, the temperature of the co-smelting is 1150-1300 ℃ during the sulfate oxidation deferrization process, and the silicate degree of the slag type used during the smelting process is 1.0-1.5.
In an alternative embodiment, if the recovered matte contains more than 4wt% of iron, the method further comprises the step of carrying out fire deferrization on the matte to reduce the iron content to below 4 wt%.
The beneficial effect of this application includes:
the method provided by the application can effectively recover copper and nickel in the sludge containing copper and nickel 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 invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are conventional products which are not indicated by manufacturers and are commercially available.
The method for recovering copper and nickel from copper-nickel-containing sludge provided by the present application is specifically described below.
The application provides a method for recovering copper and nickel from copper-nickel-containing sludge, which is carried out by correspondingly adopting one of the following modes according to the contents of chromium, copper and nickel in a copper-nickel-containing sludge dry basis to be treated:
A. if the chromium content in the sludge containing copper and nickel to be treated is more than or equal to 3wt% or the mass percentage of copper and nickel is less than 2, carrying out medium-low temperature reduction, vulcanization and roasting on the sludge containing copper and nickel to be treated, and then separating copper, nickel and chromium by adopting a physical or chemical separation mode;
B. if the chromium content in the sludge containing copper and nickel to be treated is less than 3wt% and the mass percentage of copper to nickel is not more than 2 and not more than 5, mixing the sludge containing copper and nickel to be treated with a vulcanizing agent, and carrying out high-temperature reduction vulcanization smelting to obtain copper-nickel matte;
C. if the content of chromium in the sludge containing copper and nickel to be treated is less than 3wt% and the mass percentage of copper and nickel is more than 5, reducing and smelting by adopting a pyrogenic process to recover 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 in the present application is greater than or equal to 5wt%, preferably greater than or equal to 10wt%, and if the total content of copper and nickel in the sludge is less than 5wt%, the unit product treatment cost is higher, and the recovery rate of copper and nickel resources is lower, and the economic efficiency is poorer.
For reference, in the above mode a, the low and medium temperature reduction sulfidation firing includes: and (3) carrying out reduction, vulcanization and roasting on the copper-nickel-containing sludge to be treated, a vulcanizing agent and a carbon-based reducing agent to obtain the vulcanization and roasting slag.
Preferably, the carbon-based reducing agent is coal.
The reduction, sulfurization and roasting are carried out for 1h-2h (such as 1h, 1.2h, 1.5h, 1.8h or 2 h) at 850-1000 deg.C (such as 850 deg.C, 900 deg.C, 950 deg.C or 1000 deg.C). The above 1-2h actually refers to the effective calcination time.
The sulfur source needed in the reduction, vulcanization and roasting mainly comes from copper-nickel sludge raw materials and an additional vulcanizing agent. The total sulfur amount required for the reduction sulfurization roasting is 1.2 to 1.8 times (e.g., 1.2 times, 1.3 times, 1.4 times, 1.5 times, 1.6 times, 1.7 times, or 1.8 times, etc.) of the theoretical amount required for completely sulfurizing copper and nickel, and the amount of the carbon-based reducing agent is 1.5 to 2.5 times (e.g., 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 amount.
For reference, the above formula for the theoretical amount of sulfur required for complete sulfidation of copper and nickel and the amount of the added sulfidizing agent is shown below:
m 0 ＝(m S ×η-m 1 ×w s1 )÷w S2 。
wherein:
m S the theoretical amount of sulfur required to completely sulfide copper and nickel;
m 0 is the physical dosage of an external vulcanizing agent;
m 1 the mass of the copper-nickel sludge;
w Cu the mass percentage of Cu in the copper-nickel sludge is shown;
w Ni the mass percentage of Ni in the copper-nickel sludge is shown;
w s1 the mass percentage of the element S in the copper-nickel sludge is shown;
w S2 is the mass percentage content of the element S in the external vulcanizing agent.
η is the proportionality coefficient of the total sulfur usage required for the reduction sulfidation roasting to the theoretical amount of sulfur required for the complete sulfidation of copper and nickel.
The theoretical dosage calculation formula of the carbon-based reducing agent is as follows:
wherein: m is c The theoretical amount of carbon-based reducing agent;
m 1 the mass of the copper-nickel sludge;
m 2 the mass of the external vulcanizing agent actually used;
w Cu the mass percentage of Cu in the copper-nickel sludge is shown;
w Ni is copper nickelThe mass percentage of Ni in the sludge;
w s1 the mass percentage of the element S in the copper-nickel sludge is shown;
w S2 is the mass percentage content of element S in an external vulcanizing agent;
w C the mass percentage of the effective C in the reducing agent;
a is the average chemical valence of S in the external vulcanizing agent.
Preferably, in some preferred embodiments, the copper-nickel-containing sludge to be treated may be dried to a water content of 40wt% or less 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 reductive vulcanization roasting (for example, in a vulcanization roasting device).
And further, crushing and ball-milling the vulcanization roasting slag, then carrying out physical or chemical separation (such as mineral separation treatment), and enriching and recovering resources such as cuprous sulfide and trinickel disulfide.
In the mode A, copper and nickel are converted into sulfide, chromium is oxide or spinel, other materials are partially sintered and are not molten, and the product is separated and recovered in physical or chemical separation modes.
For reference, in the above B mode, the high-temperature reduction sulfidizing melting includes: and carrying out reduction, vulcanization and smelting on the copper-nickel-containing sludge to be treated, a vulcanizing agent, a fusing agent and a reducing agent to obtain copper-nickel matte.
Wherein the high-temperature reduction-sulfurization smelting is carried out under the conditions of 1150-1350 ℃ (such as 1150 ℃, 1200 ℃, 1250 ℃, 1300 ℃ or 1350 ℃ and the like). Specifically, the smelting temperature of the high-temperature reduction vulcanization smelting is determined according to the prepared slag type, namely the smelting temperature of the high-temperature reduction vulcanization smelting is ensured to exceed 50-150 ℃ of the melting point of the pre-prepared slag (such as 50 ℃, 80 ℃, 100 ℃, 120 ℃ or 150 ℃ and the like). The chromium content of the slag mold obtained by pre-preparation is less than or equal to 2.5wt%.
In some preferred embodiments, the copper-nickel-containing sludge to be treated may be dried to a water content of less than or equal to 40wt% to obtain a dried sludge, and then the dried sludge, a vulcanizing agent and a first flux are pressed or sintered into a block, and then the block, a second flux and a reducing agent are subjected to reduction vulcanization smelting to finally produce copper-nickel matte, slag, smoke dust and the like.
The first fusing agent is limestone and the second fusing agent is quartz. The vulcanizing agent comprises at least one of sulfur gypsum and pyrite. The reducing agent includes at least one of coal, coke, carbon, and the like.
The slag shape can be adjusted by simultaneously adopting the first fusing agent and the second fusing agent, and the percentage content of three main elements, namely silicon, iron and calcium in the slag can be adjusted by adjusting the quantity of the fusing agents.
For reference, the sulfur source required in the high-temperature reduction-sulfidation smelting is mainly from copper-nickel sludge raw materials and an external sulfidation agent. The total sulfur dosage required for high-temperature reduction-sulfidation smelting is 0.9-1.8 times (such as 0.9 times, 1 time, 1.2 times, 1.5 times or 1.8 times) of the theoretical sulfur dosage required for completely sulfidizing copper and nickel, and the dosage 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) of the theoretical dosage. Wherein the calculation formula of the theoretical amount of the required dosage of completely vulcanizing copper and nickel, the dosage of the external vulcanizing agent and the theoretical dosage of the reducing agent is the same as the calculation formula of the mode A.
It should be noted that, if the content of iron in the copper nickel matte obtained after the high-temperature reduction vulcanization 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, the copper-nickel matte obtained by the conventional reduction-sulfurization process is usually a high-iron matte (i.e., iron content > 4 wt%), and therefore, it is necessary to further prepare a low-iron matte (iron content ≦ 4 wt%).
For reference, when the content of iron in the copper nickel matte obtained after the high-temperature reduction-sulfidation smelting treatment is more than 4wt%, the method further comprises the step of carrying out fire deferrization on the copper nickel matte to reduce the content of iron to be less than 4 wt%.
Wherein the fire process deferrization comprises converter blowing deferrization or smelting deferrization;
it is emphasized that in the prior art, the converter blowing deferrization is generally adopted for the pyrometallurgical deferrization, and in the present application, the inventor proposes that the reduction of the iron content is realized by the smelting deferrization.
Specifically, the smelting deferrization comprises a copper oxide or copper salt oxidation reduction deferrization or sulfate oxidation deferrization mode.
a. When the smelting deferrization is carried out by adopting a copper oxide or copper salt redox deferrization mode, the method can be carried out as follows: copper nickel matte with iron content of more than 4wt% is smelted together with copper oxide or copper salt, flux and heat-supplementing fuel.
Preferably, copper nickel matte with iron content of more than 4wt% and copper oxide or copper salt are mixed to form a cluster or a ball, and then the cluster or the ball is mixed with flux and heat-supplementing fuel for smelting.
Wherein, the copper-containing oxide or copper salt comprises at least one of copper oxide, copper carbonate and basic copper carbonate, the fusing agent comprises at least one of calcium oxide and silicon dioxide, and the heat-supplementing fuel comprises coal or carbon powder.
The copper-containing oxide or copper salt is used in an amount of 0.4-0.8 times (e.g., 0.4 times, 0.5 times, 0.6 times, 0.7 times, or 0.8 times) the theoretical amount, and the final purpose here is to reduce the iron content in the matte phase to less than 4% without affecting the copper recovery, mainly considering the iron content in the matte phase and the oxidizing atmosphere of different furnace types (i.e., the oxidized FeS ratio will vary).
For reference, the above theoretical calculation formula for the amount of copper-containing oxide or copper salt is as follows:
wherein: m is a unit of a Is the theoretical amount of copper oxide or copper salt;
m b the quality of the high-iron matte;
W Fe the mass percentage of Fe in the high-iron matte is shown;
W a is the mass percentage content of Cu in copper oxide or copper salt.
In the oxidation-reduction iron-removing mode of copper oxide or copper salt, the temperature of co-smelting can be 1150-1300 ℃ (1150 ℃, 1200 ℃, 1250 ℃ or 1300 ℃, etc., specifically determined by the prepared slag type), and the silicate 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 for slagging and slag feeding, and Cu 2 And S enters a matte phase of the product.
b. When the smelting deferrization is carried out by adopting a sulfate oxidation deferrization mode, the method can be carried out as follows: copper-nickel matte with iron content of more than 4wt% is smelted together with sulfate material and flux.
Preferably, copper nickel matte with iron content of more than 4wt% and sulfate material are mixed to form a cluster or a ball, and then mixed with a flux for smelting.
Wherein the sulfate material comprises at least one of waste sodium sulfate salt, calcium sulfate and desulfurized gypsum, and the fusing agent comprises silicon dioxide and limestone.
The amount of the sulfate material is 0.4-1.0 times (e.g. 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 final purpose here is to reduce the iron content in the matte phase to below 4% mainly according to the iron content in the sulfur phase and the oxidizing atmosphere of different furnace types (i.e. the proportion of FeS oxidized will be different).
For reference, the theoretical dosage of the sulfate material is calculated as follows:
wherein: m is d Is the theoretical dosage of the sulfate material;
m b the quality of the high-iron matte;
W Fe the mass percentage of Fe in the high-iron matte is shown;
W d is the mass percentage content of S in the sulfate material.
In the sulfate oxidation deferrization process, the temperature of the co-smelting is 1150-1300 ℃ (1150 ℃, 1200 ℃, 1250 ℃ or 1300 ℃, etc., specifically determined by the prepared slag type), and the silicate 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:
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 。
In the mode B, copper-nickel matte with the iron content less than or equal to 4wt% can be obtained.
For reference, in the above-mentioned mode C, the pyrometallurgical reduction smelting process can refer to the prior art, and will not be described in detail herein.
Further, if the iron content of the recovered matte is more than 4wt%, carrying out pyrogenic process de-iron on the matte to reduce the iron content to be less than 4 wt%.
It should be noted that the method for melting and deferrization (including copper oxide or copper salt redox deferrization or sulfate redox deferrization) in the above B method can be referred to reduce the iron content in the matte to less than 4wt%, and will not be described in detail herein.
For the application, when carrying out medium and low temperature vulcanization reduction roasting, because the material all does not reach melting temperature, the vulcanization generates cuprous sulfide and trinickel disulfide and slag and mixes together, need separate it out through the mode of ore dressing, so can select and smelt the different processes of direct separation copper nickel matte (cuprous sulfide and trinickel disulfide) and sediment with the high temperature reduction, mainly based on the reason of Cr: when the content of Cr in the raw materials is too high, properties such as melting point and viscosity of the slag in the reduction smelting process are deteriorated, which affects the separation of copper-nickel matte (cuprous sulfide and trinickel disulfide) from the slag, resulting in higher content of copper and nickel in the slag and low direct yield of copper-nickel matte. When the Cr content in the raw materials is low, the reduction vulcanization can be directly carried out by adopting a high-temperature one-step method 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 copper and the nickel sulfide are separated and recovered in a mode of reducing and vulcanizing at a medium and low temperature and then dressing.
The main reaction equations for reduction sulfidation and 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 represents Cu and Ni, the same applies below);
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 selecting the process for respectively preparing different products by different copper-nickel ratios is as follows, when the copper-nickel ratio in the raw materials is more than 5, most of the nickel and the precious metal in the products obtained by reduction are enriched in the alloy when the metal alloy and the matte are prepared, on one hand, the influence on the rise of the melting point of the alloy is limited due to the low content of the nickel in the alloy, the influence on the reduction smelting process is small, and most of the nickel can be enriched in the secondary refining slag for secondary utilization when the subsequent alloy enters the crude copper refining process. When the mass ratio of copper to nickel in the raw materials is less than or equal to 5 but more than or equal to 2, if the dosage of the vulcanizing agent is insufficient, the vulcanizing agent is used for producing the alloy, the content of nickel 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 ℃, the melting point of metal nickel is 1453 ℃), the alloy and the slag can be well separated in the smelting process only by relatively high smelting temperature, and 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 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 properties of the present invention are described in further detail below with reference to examples.
Example 1
The embodiment provides a method for recovering copper and nickel from copper-nickel-containing sludge, which specifically comprises the following steps:
(1) Drying the copper-nickel-containing sludge with the total content of dry copper and nickel of 15.7 percent, the content of chromium of less than 3 percent and the copper-nickel ratio (mass ratio) of 3 until the water content is less than or equal to 40 percent to obtain dried mud, then pressing the dried mud, desulfurized gypsum slag and limestone into blocks, and then reducing, vulcanizing and smelting the blocks together with quartz stone and reducing agent coal at 1250 ℃ for 2.0 hours to obtain copper-nickel matte (containing 15.6 percent of Fe, 45.2 percent of Cu, 22.7 percent of Ni and 23.4 percent of S), slag, smoke dust and the like with the iron content of more than 4 percent.
The total sulfur consumption is 1.5 times of the theoretical sulfur consumption needed for completely sulfurizing copper and nickel theoretically, the copper-containing oxide consumption is 0.6 times of the theoretical consumption, the appropriate amount of limestone and quartzite is added according to the slag type, and the amount of the reducing agent is 1.5 times of the theoretical consumption.
(2) Smelting the copper-nickel-matte to perform deferrization according to the following deferrization mode of copper oxide or copper salt: firstly, copper-nickel matte, cuO and basic salt in different proportions are mixed to prepare a cluster, and then quartz sand flux and reducing agent C are added to smelt for 2 hours at 1250 ℃.
The total amount of copper in the CuO and the basic salt is 0.3 time, 0.4 time, 0.5 time, 0.6 time, 0.7 time, 0.8 time and 0.9 time of the theoretical copper demand.
Slag type FeO used in the smelting process: siO 2 2 : caO =34, and the dosage of the flux is calculated according to the slag type theory.
Under the premise that other conditions are not changed, the element contents of the products obtained by correspondingly using different amounts of the copper oxide or the copper salt in the step (2) are examined, and the results are shown in table 1.
TABLE 1 analysis results of main elements in the product
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 matte obtained after the smelting is finished 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 iron content does not reach the standard. It should be noted that when the amount of Cu in the copper oxide or copper salt is more than 0.8 times the theoretical amount, the iron content in the sulfonium can be removed to well below 4wt%, and considering the cost and energy consumption of the reagent, the amount of Cu in the copper oxide or copper salt is preferably 0.4-0.8 times the theoretical amount.
Example 2
This example differs from example 1 in that:
step (2): smelting and deferrizing the copper-nickel matte obtained in the step (1) according to the following sulfate deferrization mode: firstly, respectively mixing copper-nickel matte with CaSO of 0.3 time, 0.4 time, 0.6 time, 0.8 time, 1.0 time and 1.2 times of theoretical multiple 4 Mixing to form a cluster, and then adding a certain amount of silicon dioxide according to the slag type to smelt for 2.0 hours at 1250 ℃.
The slag type FeO used in the smelting process is: siO 2 2 : caO =28 (mass ratio).
Under the premise that other conditions are not changed, the CaSO in the step (2) is inspected 4 The results are shown in table 2, corresponding to the elemental content of the product obtained at different dosages.
TABLE 2 analysis results of main elements in the product
As can be seen from table 2 above: when the amount of calcium sulfate is 0.3 times of the theoretical amount, the iron content in the matte is higher than 4wt%; when the dosage of calcium sulfate is 0.4-1.2 times of theoretical amount, the iron content in the matte can be lower than 4wt%, and it should be noted that when the dosage of calcium sulfate is 1.0 times of theoretical amount, the iron content in the matte can be removed to be far lower than 4wt%, and considering the use cost of reagent and energy consumption, the dosage of calcium sulfate is preferably 0.4-1.0 times of theoretical amount.
To sum up, the method provided by the application can effectively recover copper and nickel in the copper-nickel-containing sludge, so that the purpose of resource recycling is achieved, the waste of copper and nickel is greatly reduced, and the production cost is reduced.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and various modifications and changes will occur to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The method for recovering copper and nickel from copper-nickel-containing sludge is characterized by correspondingly adopting one of the following modes according to the contents of chromium, copper and nickel in a dry basis of the copper-nickel-containing sludge to be treated:
if the chromium content in the sludge containing copper and nickel to be treated is more than or equal to 3wt% or the mass percentage of copper and nickel is less than 2, carrying out medium-low temperature reduction, vulcanization and roasting on the sludge containing copper and nickel to be treated, and then separating copper, nickel and chromium by adopting a separation mode;
if the chromium content in the sludge containing copper and nickel to be treated is less than 3wt% and the mass percentage of copper to nickel is more than or equal to 2 and less than or equal to 5, mixing the sludge containing copper and nickel to be treated with a vulcanizing agent, and carrying out high-temperature reduction vulcanization smelting to obtain copper-nickel matte;
if the content of chromium in the sludge containing copper and nickel to be treated is less than 3wt% and the mass percentage of copper and nickel is more than 5, reducing and smelting by adopting a pyrogenic process to recover copper-nickel alloy and matte;
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%.
2. The method of claim 1, wherein the medium-low temperature reductive sulfidation roasting comprises: carrying out reduction, vulcanization and roasting on the copper-nickel-containing sludge to be treated, a vulcanizing agent and a carbon-based reducing agent to obtain vulcanization and roasting slag;
preferably, the carbon-based reducing agent is coal.
3. The method of claim 2, wherein the reductive sulfidation roasting is carried out at 850 ℃ to 1000 ℃ for 1h to 2h;
preferably, the total amount of sulfur required for the reductive sulfidation roasting is 1.2 to 1.8 times the theoretical amount required for complete copper and nickel sulfidation, and the amount of the carbon-based reducing agent is 1.5 to 2.5 times the theoretical amount required for complete reduction of copper and nickel sulfidation.
4. The method according to claim 2 or 3, characterized by drying the sludge containing copper and nickel to be treated to the water content of less than or equal to 40wt% to obtain dried sludge, briquetting or granulating the dried sludge, the vulcanizing agent and the carbon-based reducing agent, and then carrying out reduction, vulcanization and roasting;
preferably, the method further comprises the following steps: and crushing and ball-milling the vulcanization roasting slag, and then carrying out ore dressing treatment.
5. The method of claim 1, wherein the high temperature reduction sulfidation smelting comprises: carrying out reduction, vulcanization and smelting on the copper-nickel-containing sludge to be treated, a vulcanizing agent, a flux and a reducing agent to obtain copper-nickel matte;
preferably, the sludge containing copper and nickel to be treated is dried to the water content of less than or equal to 40wt% to obtain dried sludge, then the dried sludge, the vulcanizing agent and the first fusing agent are pressed or sintered into blocks, and then the blocks, the second fusing agent and the reducing agent are subjected to reduction vulcanization smelting;
wherein the first fusing agent is limestone and the second fusing agent is quartz stone;
preferably, the vulcanizing agent comprises at least one of anhydrite and pyrite;
preferably, the reducing agent comprises at least one of coal, carbon and coke;
preferably, the total sulfur dosage required by the high-temperature reduction sulfidization smelting is 0.9-1.8 times of the theoretical dosage required for completely sulfidizing copper and nickel, and the dosage of the reducing agent is 1.5-2.5 times of the theoretical dosage required.
6. The method as claimed in claim 5, wherein the high temperature reduction sulfidisation smelting is carried out at 1150 ℃ to 1350 ℃ and the smelting temperature of the high temperature reduction sulfidisation smelting is 50 ℃ to 150 ℃ above the melting point of the pre-prepared slag.
7. The method as claimed in claim 6, wherein the copper nickel matte obtained after the high temperature reduction sulfidation smelting process has an iron content of > 4wt%, further comprising the step of performing a fire de-ironing on the copper nickel matte to reduce the iron content to below 4wt%;
wherein the fire process deferrization comprises converter blowing deferrization or smelting deferrization; the smelting deferrization comprises adopting a copper oxide or copper salt redox deferrization or sulfate oxidation deferrization mode.
8. The method according to claim 7, wherein when the smelting deferrization is carried out by means of redox deferrization of copper oxides or copper salts, the method is carried out in the following way: smelting copper-nickel matte with iron content more than 4wt%, copper-containing oxide or copper salt, flux and heat-supplementing fuel together;
preferably, the copper-containing oxide or copper salt used in the redox deferrization process of the copper oxide or copper salt 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 used heat-supplementing fuel comprises coal or carbon essence;
preferably, in the process of oxidation-reduction iron removal of copper oxide or copper salt, copper nickel matte with iron content of more than 4wt% is mixed with the copper oxide or copper salt to prepare a cluster or a ball, and then the fusion agent and the reducing agent are added for smelting;
preferably, the amount of said copper oxide or copper salt is 0.4-0.8 times the theoretical amount;
preferably, in the oxidation-reduction deferrization mode of copper oxide or copper salt, the temperature of the co-smelting is 1150-1300 ℃, and the silicate degree of the slag used in the smelting process is 1.0-1.5.
9. The method according to claim 7, characterized in that when the smelting deferrization is carried out by sulfate oxidation deferrization, the following is carried out: smelting copper-nickel matte with iron content more than 4wt%, sulfate material and flux together;
preferably, the sulfate material used in the sulfate oxidation deferrization process comprises at least one of waste sodium sulfate salt, calcium sulfate and desulfurized gypsum; the flux used comprises silica and limestone;
preferably, in the process of sulfate oxidation deferrization, copper-nickel-matte with iron content of more than 4wt% is mixed with the sulfate material to prepare a cluster or a ball, and then the cluster or the ball is mixed with the flux to be smelted;
preferably, the dosage of the sulfate material is 0.4 to 1.0 time of the theoretical value;
preferably, the temperature of the co-smelting is 1150-1300 ℃ in the sulfate oxidation deferrization process, and the silicate degree of the slag used in the smelting process is 1.0-1.5.
10. A method according to claim 1, wherein if the recovered matte has an iron content of > 4wt%, further comprising the step of pyro-de-ironing the matte to reduce the iron content to below 4 wt%.
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