CN112725624A - Method for efficiently recycling arsenic-cobalt-nickel-containing slag - Google Patents
Method for efficiently recycling arsenic-cobalt-nickel-containing slag Download PDFInfo
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- C22B19/00—Obtaining zinc or zinc oxide
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Abstract
The invention discloses a method for efficiently recycling arsenic-cobalt-nickel-containing slag. The method comprises the steps of firstly, carrying out oxygen pressure alkaline leaching on arsenic-containing cobalt nickel slag to remove arsenic, and obtaining filter residue and arsenic-containing alkaline leaching liquid. The alkaline leaching solution can be crystallized, dissolved and SO-dissolved by evaporation2The arsenite can be returned to be used for purifying the zinc sulfate solution in the zinc hydrometallurgy process to remove cobalt and nickel; or carrying out vulcanization impurity removal, causticization arsenic precipitation and vacuum reduction on the alkaline leaching solution to obtain simple substance arsenic and regenerated CaO; the alkaline leaching residue realizes valuable gold such as zinc, copper, cobalt, nickel and the like by two-stage acid leaching, zinc powder displacement copper removal, oxidation cobalt precipitation and copper removal nickel removalBelongs to comprehensive recovery. The method has the advantages of short process flow, cleanness, high efficiency and high recovery rate, and avoids the problem of arsenic pollution in the prior art.
Description
Technical Field
The invention relates to a method for treating arsenic-cobalt-nickel-containing slag, in particular to a method for efficiently and comprehensively recovering useful metals such as arsenic, zinc, copper, cobalt, nickel and the like from the arsenic-cobalt-nickel-containing slag, belonging to the field of metallurgical engineering and environmental engineering.
Background
Zinc is an important nonferrous metal, is mainly used in the fields of steel, metallurgy, machinery, electricity, chemical industry, light industry, military, medicine and the like, has the dosage second to aluminum and copper, and plays an important role in improving national economy. The modern zinc smelting method mainly comprises two major categories of zinc smelting by a pyrogenic process and zinc smelting by a wet process, and more than 80% of the total zinc in the world is produced by the zinc smelting process by the wet process at present. The zinc hydrometallurgy consists of four working procedures of roasting, leaching, purifying and electrodeposition. Since zinc sulphide concentrate is poorly soluble in dilute sulphuric acid, zinc sulphide concentrate is first roasted to convert most of the zinc sulphide to zinc oxide and a small part to zinc sulphate. The calcine obtained after roasting is leached with dilute sulphuric acid and the pH is controlled to be appropriate to dissolve the zinc and bring it into solution As zinc sulphate, which therefore usually contains a large amount of impurities such As Ge, Sb, Ni, Co, Bi, Cu and As. In order to avoid that impurities in the solution affect the electrodeposition of the zinc sulfate solution, the zinc sulfate solution needs to be purified through a purification process, wherein cobalt and nickel in the solution cannot meet the purification requirements only through zinc powder replacement, so that at present, a method of adding arsenite as an activating agent is used in many factories to remove the cobalt and nickel in the zinc sulfate solution, and relatively millions of tons of smelting waste residues containing arsenic are generated in the factories every year. If the arsenic-containing waste residue is not properly treated, valuable metal resources such as zinc, copper, cobalt, nickel and the like contained in the residue can be wasted, and great harm can be caused to the environment and human bodies. In order to satisfy the sustainable development of the non-ferrous metal industry, many researchers have conducted researches on processes such as hydrometallurgy, pyrometallurgy and combined metallurgy, and how to recover valuable metals from smelting waste residues. Despite the many achievements achieved today, these techniques have not been widely used for large scale production due to some technical and economic drawbacks.
The existing methods for treating arsenic-containing waste residues are mainly divided into two major types, namely pyrometallurgical processes and hydrometallurgical processes. The pyrometallurgical dearsenification is to separate arsenic from other valuable substances by utilizing the volatility of arsenic trioxide at high temperature, and although the pyrometallurgical dearsenification is mature, the process has large energy consumption and is easy to cause secondary pollution; the hydrometallurgical process is divided into acidic leaching and alkaline leaching. The acid leaching dearsenification process has poor selectivity and highly toxic AsH may be generated in the leaching process3The alkaline leaching dearsenification process for realizing selective dearsenification by converting arsenic into soluble arsenate is more efficient and safer. The existing more efficient pressure leaching technology is also being researched for arsenic removal of waste residues, wherein the research of treating arsenic-containing cobalt-nickel residues by oxygen-free pressure alkaline leaching is not carried out, but many researches do not achieve the selective leaching of arsenic, zinc in the arsenic-containing cobalt-nickel residues generated by zinc hydrometallurgy is easy to be leached into solution together with arsenic in the residues in the oxygen-pressure alkaline leaching process, and the problem of potential risk of arsenic is not fundamentally solved by curing the arsenic afterwards.
Disclosure of Invention
Aiming at the defects of the technology for treating the arsenic-cobalt-nickel-containing slag in the prior art, the invention aims to provide a method for comprehensively and efficiently recycling arsenic and recovering valuable metal elements such as copper, zinc, nickel, cobalt and the like from the arsenic-cobalt-nickel-containing slag.
In order to realize the technical purpose, the invention provides a method for efficiently recycling arsenic-containing cobalt-nickel slag, which comprises the following steps:
1) performing oxygen pressure alkaline leaching on the arsenic-containing cobalt nickel slag to obtain arsenic-containing alkaline leaching solution and alkaline leaching slag;
2) the alkaline leaching residue is leached by low acid to obtain low acid leaching liquid containing copper, zinc, cobalt and nickel and low acid leaching residue;
3) replacing copper with zinc powder in the low-acid leaching solution containing copper, zinc, cobalt and nickel to obtain copper-removing solution containing zinc, cobalt and nickel and copper-rich slag; leaching the low acid leaching slag by adopting high acid to obtain high acid leaching liquid containing copper, zinc, cobalt and nickel and lead-rich slag, and returning the high acid leaching liquid to the low acid leaching process to be used as a leaching agent;
4) the copper removal liquid containing zinc, cobalt and nickel adopts persulfate to oxidize and precipitate cobalt to obtain cobalt removal liquid containing zinc and nickel and cobalt-rich slag;
5) and removing impurities from the cobalt-removing solution containing zinc and nickel by using zinc powder to obtain a zinc-containing solution and copper-nickel slag.
6) Evaporating and crystallizing the arsenic-containing alkaline leaching solution to obtain arsenate crystals; dissolving arsenate crystal in water, and introducing SO2Reducing to obtain arsenite solution; returning the arsenite solution to the zinc hydrometallurgy purification process for removing cobalt and nickel;
alternatively, the first and second electrodes may be,
after the arsenic-containing alkaline leaching solution is subjected to vulcanization and impurity removal, causticizing by using quick lime to obtain a regenerated NaOH solution and calcium arsenate; the regenerated NaOH solution returns to the oxygen pressure alkaline leaching process; the calcium arsenate is reduced in vacuum to obtain arsenic simple substance and calcium oxide, and the calcium oxide returns to the causticizing process.
The method for efficiently recycling the arsenic-containing cobalt-nickel slag provided by the invention can realize efficient separation and recycling of valuable metals such as copper, zinc, cobalt, nickel and the like and recycling of arsenic, and really realizes comprehensive utilization of the arsenic-containing cobalt-nickel slag. According to the technical scheme, firstly, oxygen pressure alkaline leaching is adopted for arsenic-containing cobalt nickel slag, arsenic removal from the arsenic-containing cobalt nickel slag is achieved, arsenic in the arsenic-containing cobalt nickel slag is converted into arsenate which is easily dissolved in alkali liquor, only a small amount of zinc can be leached through optimizing leaching conditions, the purpose of selective arsenic removal is achieved, the influence of the arsenic on subsequent metal recovery can be avoided through source arsenic removal, and recoverable alkaline leaching slag and arsenic acid saline-alkali leaching liquid rich in copper, zinc, cobalt and nickel can be obtained through oxygen pressure alkaline leaching. The alkaline leaching residue adopts low acid leaching, and the reaction conditions can be controlled to ensure that most of copper, zinc and cobalt in the alkaline leaching residueAnd leaching nickel into the acid leaching solution to realize the recovery of valuable metal elements such as copper, zinc, cobalt and nickel from the alkaline leaching residue. The zinc powder of the low-acid leaching solution is replaced to remove copper, the leaching solution rich in copper, zinc, cobalt and nickel is replaced by the zinc powder to remove the copper, the copper can be efficiently removed by replacing the zinc with the copper, the zinc concentration can be improved, the subsequent electrodeposition zinc process is facilitated, and the copper can be removed by replacing the zinc powder to obtain the copper-removing solution and the recyclable copper-rich slag. The copper removing liquid mainly contains cobalt and a small amount of nickel and copper, the cobalt in the copper removing liquid is precipitated through persulfate oxidation, and the cobalt in the copper removing liquid is selectively oxidized and precipitated by using persulfate and controlling reaction conditions, so that the cobalt removing liquid and the cobalt-rich slag are obtained. The cobalt-removing liquid only contains a small amount of copper and nickel, the cobalt-removing liquid is purified and decontaminated by adding zinc powder, zinc sulfate solution and copper-nickel slag which can return to a zinc hydrometallurgy system are obtained by filtering, and the copper-nickel slag can be mixed with copper-rich slag for sale. The low-acid leaching residue also contains a small amount of valuable metals such as zinc, copper, cobalt, nickel and the like, high-acid leaching is further adopted, the low-acid leaching residue is subjected to high-acid leaching and is filtered to obtain high-acid leaching solution rich in copper, zinc, cobalt and nickel and lead residue, the high-acid leaching solution is returned to the low-acid leaching process for use, so that all the copper, zinc, nickel and cobalt are recovered, and the lead residue can be sold. The alkaline leaching solution is mainly arsenate, and can be prepared into arsenate crystal by evaporation crystallization, and then the arsenate is passed through SO2Reducing to obtain arsenite solution with high concentration, or preparing arsenic trioxide crystal, wherein the product can be returned to the wet zinc smelting purification process to remove cobalt and nickel, thereby realizing the reuse of arsenic; or the arsenic-containing alkaline leaching solution is subjected to zinc sulfide precipitation and arsenic causticization precipitation to obtain NaOH solution and calcium arsenate which can be leached back, and then the calcium arsenate is subjected to vacuum reduction to obtain arsenic simple substance which can be sold and CaO which can be precipitated back to causticization, thereby realizing the utilization of arsenic. The method can recycle arsenic from the arsenic-cobalt-nickel-containing slag and recover valuable metal elements such as copper, zinc, nickel, cobalt and the like, realizes the comprehensive utilization of secondary resources, is an efficient and clean method, and avoids the poisoning problem of arsenic and the risk of arsenic solidification.
As a preferred scheme, the conditions of the oxygen pressure alkaline leaching are as follows: NaOH solution with the concentration of 1.5-3 mol/L is used as a leaching agent, oxygen is used as an oxidant, the mass ratio of the leaching solution to the solid is 3-6: 1, the oxygen partial pressure is 0.5-2.5 MPa, the temperature is 90-180 ℃, and the time is 2-4 hours. The high-efficiency selective leaching of arsenic can be ensured under the optimized oxygen pressure alkaline leaching condition, and only a small amount of zinc enters the leaching solution as impurities.
As a preferred embodiment, the conditions of the low acid leaching are as follows: taking a sulfuric acid solution with the initial concentration of 80-120 g/L as a leaching agent, slowly adding alkaline leaching residues into the sulfuric acid solution at the temperature of 50-70 ℃, wherein the leaching time is 2-3 h, and the pH value of the leaching end point is 2.5-3.5. Under the preferable low-acid leaching condition, most of copper, zinc, cobalt and nickel in the alkaline leaching residue can be ensured to be leached into the acid leaching solution, and the recovery of valuable metal elements such as copper, zinc, cobalt and nickel from the alkaline leaching residue is facilitated.
As a preferable scheme, the conditions for replacing copper by the zinc powder are as follows: the temperature is 45-65 ℃, the time is 0.5-1.5 h, the end point pH is controlled to be less than 5.5, and the using amount of the zinc powder is 1.01-1.5 times of the theoretical molar amount of the zinc powder required by copper replacement. Under the optimized conditions, copper can be precipitated with high selectivity, and the separation and recovery of copper, cobalt and nickel are facilitated.
As a preferred embodiment, the conditions of the peracid leaching are: sulfuric acid solution with initial concentration of 80-120 g/L is used as a leaching agent, the liquid-solid ratio is 8-12 mL:1g, the reaction temperature is 70-90 ℃, and the reaction time is 3-5 h. Under the preferable high-acid leaching condition, the valuable metals in the low-acid leaching slag can be deeply leached to obtain lead slag, and the valuable metals can also be recovered.
The technical scheme of the invention adopts a two-stage acid leaching method for alkaline leaching residue, which is mainly based on that part of copper and arsenic of arsenic-cobalt-nickel residue is not completely oxidized after the arsenic-cobalt-nickel residue is subjected to oxygen pressure alkaline leaching, if the alkaline leaching residue is subjected to only one-stage acid leaching, a large amount of sulfuric acid is consumed for ensuring the recovery rate of copper, and a zinc sulfate solution after valuable metals such as copper, cobalt, nickel and the like are recovered needs to be returned to a zinc smelting system, wherein the large amount of sulfuric acid contained in the zinc sulfate solution cannot be recycled; the first section adopts low acid leaching, which is beneficial to reducing the adding amount of zinc powder during the subsequent copper removal of the zinc powder, and leaching most of copper in the alkaline leaching residue while realizing low acid consumption, so that the grade of the copper residue is improved; the second stage of high-acid leaching ensures leaching of valuable metals such as Zn, Cu, Co and the like, improves the recovery rate of the valuable metals, and can return high-acid leaching liquid to low-acid leaching for use, thereby reducing the acid consumption.
As a preferred scheme, the conditions for the cobalt oxide precipitation are as follows: the mass ratio of the persulfate to the cobalt in the copper removing liquid containing zinc, cobalt and nickel is 4: 1-9: 1, the pH is adjusted to 2.5-5.0, the temperature is 70-90 ℃, and the time is 1-2 hours. Under the preferred conditions, cobalt can be oxidized and precipitated with higher selectivity to realize the recovery of cobalt.
As a preferable scheme, the conditions for removing impurities from the zinc powder are as follows: the conditions for removing impurities by the zinc powder are as follows: the temperature is 50-60 ℃, the zinc powder dosage is 1-2 g/L, and the reaction lasts for 1-1.5 h. Under the optimized reaction condition, the deep removal of copper and cobalt can be realized, and the zinc-containing solution meeting the requirement of electro-deposition zinc is obtained.
As a preferable scheme, arsenate crystals are dissolved in water according to the liquid-solid ratio of 1-4 mL:1, and SO is introduced2Is subjected to reduction, SO2The ratio of the total molar weight of the arsenate to the total molar weight of the arsenate is 4-8, and reduction reaction is carried out at 30-60 ℃ for 2-4 h to obtain an arsenite solution. Under the preferred conditions, sufficient reduction of arsenate crystals to arsenite is ensured.
As a preferable scheme, the conditions for removing impurities by vulcanization are as follows: the method is characterized in that sodium sulfide is used as a vulcanizing agent, the addition amount of the sodium sulfide is 1.4-1.7 times of the molar amount of the vulcanizing agent needed for precipitating zinc, the temperature is 30-40 ℃, and the time is 0.5-1.5 hours. The preferable sulfuration impurity removal process can efficiently remove the residual zinc, and is beneficial to the subsequent recovery of high-purity simple substance arsenic.
As a preferred scheme, the causticizing conditions are as follows: the proportion of the quicklime to arsenate in the arsenic-containing alkali immersion liquid is 3-6 in terms of molar ratio Ca/As, the temperature is 70-90 ℃, and the time is 2-3 h.
The invention provides a method for efficiently recycling arsenic-cobalt-nickel-containing slag, which comprises the following steps:
A. and (3) performing oxygen pressure alkaline leaching dearsenification: uniformly mixing arsenic-cobalt-nickel-containing slag, sodium hydroxide and water serving as raw materials according to a certain mass ratio, putting the raw materials into a high-pressure kettle, sealing the high-pressure kettle, introducing oxygen at a certain temperature, adjusting the oxygen pressure in the kettle to fully react the raw materials, and filtering slurry to obtain alkaline leaching solution and alkaline leaching slag after the alkaline leaching under the oxygen pressure is finished; the oxygen pressure alkaline leaching conditions are as follows: the liquid-solid mass ratio is 3: 1-6: 1, the concentration of NaOH is 1.5-3 mol/L, the oxygen partial pressure in the kettle is 0.5-2.5 MPa, the reaction temperature is 90-180 ℃, and the reaction time is 2-4 h.
B. Low acid leaching: b, carrying out low-acid leaching on the alkaline leaching residue obtained in the step A, and filtering to obtain a low-acid leaching solution and a low-acid leaching residue which are rich in copper, zinc, cobalt and nickel after the low-acid leaching is finished; the conditions of low acid leaching are as follows: the initial acidity is 80-120 g/L, the reaction temperature is 50-70 ℃, and the alkaline leaching residue is slowly added to ensure that the final pH value is 2.5-3.5 and the reaction time is 2-3 h.
C. And (3) zinc powder replacement copper removal: c, performing zinc powder replacement copper removal reaction on the low-acid leaching solution obtained in the step B under the conditions that the temperature is 45-65 ℃, the reaction time is 0.5-1.5 h, the end point pH is controlled to be less than 5.5 and the zinc powder excess coefficient is 1.01-1.5, and filtering after the reaction to obtain copper-rich slag and copper removal liquid which can be sold; the conditions for replacing and removing copper by zinc powder are as follows: the temperature is 45-65 ℃, the reaction time is 0.5-1.5 h, the end point pH is less than 5.5, and the zinc powder excess coefficient is 1.01-1.5.
D. And (3) oxidizing and precipitating cobalt by persulfate: c, adding persulfate into the decoppered liquid obtained in the step C to oxidize and precipitate cobalt, and filtering to obtain cobalt-rich slag and decoppered liquid which can be sold; the conditions for the oxidation and cobalt precipitation are as follows: the mass ratio of the persulfate to the total amount of cobalt in the solution is 4: 1-9: 1, the pH is adjusted to 2.5-5.0, the reaction temperature is 70-90 ℃, and the reaction time is 1-2 hours.
E. Copper sweeping and nickel removing: and D, removing impurities from the cobalt-removed solution obtained in the step D at the temperature of 50-60 ℃ by adding zinc powder according to the using amount of 1-2 g/L, reacting for 1-1.5 h, and filtering to obtain zinc sulfate solution and copper-nickel slag which can be returned to a wet zinc smelting system, wherein the copper-nickel slag can be mixed with copper-rich slag for sale.
F. High-acid leaching: c, carrying out high acid leaching on the low acid leaching residue obtained in the step B, filtering to obtain a high acid leaching solution rich in copper, zinc, cobalt and nickel and lead slag, returning the high acid leaching solution to the low acid leaching process for use, and selling the lead slag; the conditions of the peracid leaching are as follows: sulfuric acid with initial acidity of 80-120 g/L is used as a leaching agent, the liquid-solid ratio is 8-12 mL/g, the final acidity is 25-50 g/L, the reaction temperature is 70-90 ℃, and the reaction time is 3-5 h.
G. Recovering an alkali leaching solution: the alkaline leach solution from step a has two processing schemes:
the scheme 1 is that arsenate crystals are prepared by evaporation crystallization, the arsenate crystals are dissolved in water according to a certain liquid-solid ratio, and SO is introduced at a certain flow rate2Reducing to obtain arsenite solution with high concentration, or preparing arsenic trioxide crystal, wherein the product can be returned to the wet zinc smelting purification process for removing cobalt and nickel; the conditions for preparing arsenite are as follows: SO introduced into the solution2The ratio of the total molar weight of arsenic in the solution to the molar weight of arsenic in the solution is 4-8, the liquid-solid ratio of dissolved arsenate crystals is 1: 1-4: 1, the reaction temperature is 30-60 ℃, and the reaction time is 2-4 hours;
the scheme 2 is that after the arsenic-containing alkaline leaching solution is subjected to vulcanization impurity removal and causticization arsenic precipitation, a NaOH solution and calcium arsenate which can be returned to leaching are obtained, and then the calcium arsenate is subjected to vacuum reduction to obtain an arsenic simple substance which can be sold and CaO which can be returned to causticization precipitation; the conditions for preparing the simple substance arsenic are as follows: the usage amount of sodium sulfide is 1.4-1.7 times of theoretical usage amount during zinc sulfide precipitation, the reaction time is 0.5-1.5 hours, the reaction temperature is 30-40 ℃, the usage amount of CaO is 3-6 during causticization arsenic precipitation, the causticization temperature is 70-90 ℃, and the causticization time is 2-3 hours; the vacuum reduction conditions of calcium arsenate are as follows: the roasting temperature is 800-1000 ℃, the carbon powder consumption is 12-15%, and the roasting time is 70-100 min.
Compared with the prior art, the invention has the following beneficial effects:
the technical scheme of the invention firstly adopts high-efficiency oxygen pressure alkaline leaching dearsenification to the arsenic-containing cobalt-nickel slag generated by zinc hydrometallurgy, and avoids AsH which is easy to generate high toxicity during acid leaching dearsenification3And the problems of high energy consumption, secondary pollution and the like of the pyrogenic dearsenification, and simultaneously, the pre-dearsenification avoids the pollution caused by the recovery of other valuable metals from the arsenic.
According to the technical scheme, the arsenic-containing filtrate is subjected to reduction to prepare arsenite, so that the arsenic can be returned to a zinc hydrometallurgy system for recycling, the arsenic is not diffused and polluted according to local conditions, and the potential risk of arsenic solidification is avoided; or the arsenic-containing filtrate is prepared into a simple substance arsenic product, thereby bringing economic benefits and reducing the volume and mass required by stockpiling compared with the solidified arsenic.
According to the technical scheme, the alkaline leaching residue after arsenic removal is subjected to two-stage acid leaching, acid consumption and subsequent zinc powder consumption are reduced while most valuable metals are leached by low-acid leaching, the copper residue grade of the zinc powder after copper removal is improved, the cobalt residue grade is ensured by cobalt leaching after copper removal, copper and nickel are recovered by copper removal, a zinc sulfate solution is purified and can be returned to a zinc smelting system for use, the valuable metals are recovered by high-acid leaching, and acid leaching solution is recycled, so that the acid consumption is reduced.
The technical scheme of the invention adopts a complete, efficient and clean comprehensive recovery route for the arsenic-containing cobalt-nickel slag, realizes comprehensive recovery and utilization of secondary resources, avoids waste of valuable metals, brings economic benefits, does not discharge toxic substances and introduce highly toxic substances in the whole recovery route, and provides guarantee for environmental protection.
Detailed Description
The following examples are intended to further illustrate the present disclosure, but not to limit the scope of the claims.
The invention relates to a method for efficiently recycling arsenic-cobalt-nickel-containing slag, which comprises the following steps:
A. and (3) performing oxygen pressure alkaline leaching dearsenification: the method comprises the steps of taking arsenic-cobalt-nickel-containing slag, sodium hydroxide and water as raw materials, uniformly mixing the raw materials according to a certain mass ratio, putting the raw materials into a high-pressure kettle, sealing the high-pressure kettle, introducing oxygen at a certain temperature, and adjusting the oxygen pressure in the kettle to enable the raw materials to fully react. After the oxygen pressure alkaline leaching is finished, filtering the slurry to obtain alkaline leaching liquid and alkaline leaching residues;
B. low acid leaching: b, carrying out low-acid leaching on the alkaline leaching residue obtained in the step A, and filtering to obtain a low-acid leaching solution and a low-acid leaching residue which are rich in copper, zinc, cobalt and nickel after the low-acid leaching is finished;
C. and (3) zinc powder replacement copper removal: c, performing zinc powder replacement copper removal reaction on the low-acid leaching solution obtained in the step B under the conditions that the temperature is 45-65 ℃, the reaction time is 0.5-1.5 h, the end point pH is controlled to be less than 5.5 and the zinc powder excess coefficient is 1.01-1.5, and filtering after the reaction to obtain copper-rich slag and copper removal liquid which can be sold;
D. and (3) oxidizing and precipitating cobalt by persulfate: c, adding persulfate into the decoppered liquid obtained in the step C to oxidize and precipitate cobalt, and filtering to obtain cobalt-rich slag and decoppered liquid which can be sold;
E. copper sweeping and nickel removing: and D, removing impurities from the cobalt-removed solution obtained in the step D at the temperature of 50-60 ℃ by adding zinc powder according to the using amount of 1-2 g/L, reacting for 1-1.5 h, and filtering to obtain zinc sulfate solution and copper-nickel slag which can be returned to a wet zinc smelting system, wherein the copper-nickel slag can be mixed with copper-rich slag for sale.
F. High-acid leaching: c, carrying out high acid leaching on the low acid leaching residue obtained in the step B, filtering to obtain a high acid leaching solution rich in copper, zinc, cobalt and nickel and lead slag, returning the high acid leaching solution to the low acid leaching process for use, and selling the lead slag;
G. recovering an alkali leaching solution: the alkaline leaching solution obtained in the step A has two treatment schemes, wherein the scheme 1 is that arsenate crystals are prepared by evaporation crystallization, the arsenate crystals are dissolved in water according to a certain liquid-solid ratio, and SO is introduced at a certain flow rate2Reducing to obtain arsenite solution with high concentration, or preparing arsenic trioxide crystal, wherein the product can be returned to the wet zinc smelting purification process for removing cobalt and nickel; and in the scheme 2, the arsenic-containing alkaline leaching solution is subjected to zinc sulfide precipitation and arsenic causticization precipitation to obtain NaOH solution and calcium arsenate which can be leached back, and the calcium arsenate is subjected to vacuum reduction to obtain arsenic simple substance which can be sold and CaO which can be precipitated back to causticization.
In the step A, the conditions of oxygen pressure alkaline leaching are as follows: the liquid-solid mass ratio is 3: 1-6: 1, the concentration of NaOH is 1.5-3 mol/L, the oxygen partial pressure in the kettle is 0.5-2.5 MPa, the reaction temperature is 90-180 ℃, and the reaction time is 2-4 h.
In the step B, the conditions of low acid leaching are as follows: the initial acidity is 80 g/L-120 g/L sulfuric acid, the reaction temperature is 50-70 ℃, and the alkaline leaching residue is slowly added to ensure that the final pH value is 2.5-3.5 and the reaction time is 2-3 h.
In the step C, the conditions for replacing and removing copper by zinc powder are as follows: the temperature is 45-65 ℃, the reaction time is 0.5-1.5 h, the end point pH is less than 5.5, and the zinc powder excess coefficient is 1.01-1.5.
In the step D, the conditions for oxidizing and precipitating cobalt are as follows: the mass ratio of the persulfate to the total amount of cobalt in the solution is 4: 1-10: 1, the pH is adjusted to 2.5-5.0, the reaction temperature is 70-90 ℃, and the reaction time is 1-2 hours. .
In the step E, the conditions for removing nickel by copper sweeping are as follows: adding zinc powder at the temperature of 50-60 ℃ according to the dosage of 1-2 g/L to remove impurities, and reacting for 1-1.5 h.
In step F, the conditions of the high-acid leaching are as follows: sulfuric acid with initial acidity of 80-120 g/L is used as a leaching agent, the liquid-solid ratio is 8: 1-12: 1, the final acidity is 25-50 g/L, the reaction temperature is 70-90 ℃, and the reaction time is 3-5 hours.
In step G, the conditions for preparing arsenite in scheme 1 are: the ratio of the total molar weight of SO2 introduced into the solution to the molar weight of arsenic in the solution is 4-8, the liquid-solid ratio of dissolved arsenate crystals is 1: 1-4: 1, the reaction temperature is 30-60 ℃, and the reaction time is 2-4 hours; the conditions for preparing elemental arsenic in scheme 2 are: the usage amount of sodium sulfide is 1.4-1.7 times of the theoretical usage amount during zinc sulfide precipitation, the reaction time is 0.5-1.5 hours, the reaction temperature is 30-40 ℃, the usage amount of CaO is 3-6 during arsenic causticization precipitation, the causticization temperature is 70-90 ℃, and the causticization time is 2-3 hours. The vacuum reduction conditions of calcium arsenate are as follows: the roasting temperature is 800-1000 ℃, the carbon powder consumption is 12-15%, and the roasting time is 70-100 min.
Examples of specific examples and related experimental data are as follows:
example 1
The arsenic-cobalt-nickel-containing slag 1 in the present example had the composition (wt.%): as 11.64, Cu 48.60, Co 1.60, Zn 7.68 and Ni 0.33.
A. And (3) performing oxygen pressure alkaline leaching dearsenification: weighing 1.5kg of arsenic-containing cobalt-nickel slag, placing the arsenic-containing cobalt-nickel slag and a solution with a sodium hydroxide concentration of 2mol/L into a high-pressure kettle with a liquid-solid mass ratio of 6:1 and a stirring speed of 500rpm, sealing, heating to 100 ℃, introducing oxygen to adjust the oxygen pressure in the kettle to be 1MPa, leaching for 3 hours, washing and filtering after leaching is finished, and obtaining an alkali leaching solution and alkali leaching slag. The alkaline leaching solution comprises the following components in percentage by weight (g/L): as 17.01, Cu 0.0043, Co 0.00002, Zn 1.7925 and Ni 0.065 show that only arsenic and a small amount of zinc are leached into the solution after the alkaline leaching under oxygen pressure, and copper, cobalt and nickel exist in the leaching residue.
B. Low-acid leaching of alkaline leaching residue: preparing 2L of 100g/L sulfuric acid, adding alkaline leaching residues into the sulfuric acid, enabling the end point pH to be 3.0, the reaction temperature to be 80 ℃, and the reaction time to be 3h, wherein the leaching rates of zinc, copper, cobalt, nickel and arsenic are respectively about 94%, 91%, 85%, 90% and 25%, which indicates that the leaching of zinc, copper, cobalt and nickel in the alkaline leaching residues is completed, and the leaching residues comprise the following components (wt%): zn 2.19, Cu 43.78, Co 2.18, Ni 0.24, As 6.36.
C. And (3) carrying out zinc powder displacement copper removal on the pickle liquor: and D, taking 1.5L of the low-acid leaching solution obtained in the step B, performing zinc powder displacement copper removal reaction under the conditions that the temperature is 60 ℃, the reaction time is 1.5h, the end point pH is controlled to be 4.5 and the zinc powder excess coefficient is 1.2, washing and filtering after the reaction is finished to obtain recyclable copper slag and copper removal solution, wherein the copper and cobalt solution-based precipitation rates are 99.8% and 17.2%, the copper removal solution contains 0.0026g/L copper and 0.77g/L cobalt.
D. Removing copper liquid, namely oxidizing and precipitating cobalt by using persulfate: and C, taking 1L of the copper-removing liquid obtained in the step C, adding persulfate, wherein the mass ratio of persulfate to the total amount of cobalt in the solution is 10:1, reacting at the temperature of 80 ℃ for 2h, adjusting the pH to be about 4.2 by using a neutralizer to oxidize and precipitate cobalt, washing and filtering to obtain cobalt-rich slag and cobalt-removing liquid, wherein the cobalt content in the cobalt-rich slag is 17.25%, the cobalt content in the cobalt-removing liquid is 0.00098g/L, the cobalt-removing rate of the slag reaches 100%, and the cobalt slag can be sold.
E. Copper sweeping and nickel removing: selecting zinc powder to sweep copper and remove nickel from the cobalt removing solution, adding the zinc powder according to the dosage of 1.5g/l under the conditions that the temperature is 60 ℃ and the reaction time is 1h, wherein the nickel content in the solution is only 0.0087 g/l.
F. High-acid leaching: and (2) taking 500g of low-acid leaching residue, carrying out high-acid leaching under the conditions that the liquid-solid ratio is 10:1, the temperature is 80 ℃, the leaching time is 4 hours, and the final acid is 25g/L, washing and filtering are carried out after the reaction is finished to obtain high-acid leaching liquid and lead residue, wherein the leaching rates of zinc, copper, cobalt and nickel are respectively 100%, 99.68%, 97.43% and 95.21%, the high-acid leaching liquid can be directly returned to the low-acid leaching process to realize the recovery of zinc, copper, cobalt and nickel, and the lead residue contains 25.13% of lead and can be sold outside the low-acid leaching process.
G. Recovering an alkali leaching solution: b, preparing arsenate crystals from the alkaline leaching solution obtained in the step A through evaporation crystallization, dissolving 600g of arsenate crystals in water at a liquid-solid ratio of 2:1, and introducing SO at a flow rate of 1.2L/min2Reducing at 30 ℃ for 2.5h, returning the reducing solution to the zinc hydrometallurgy purification process after the reaction is finished to remove cobalt and nickel, and reducing the cobalt content in 2L of zinc sulfate solution containing 0.03g/L of cobalt by 0.0003g/L by 5mL of high-concentration arsenite solution prepared by reduction, thereby meeting the requirements of the purification process and realizing the recycling of arsenic.
Example 2
The composition (wt.%) of the arsenic-cobalt-nickel-containing slag 2 in this example is: as 10.29, Cu 40.12, Co 1.44, Zn 10.06 and Ni 0.24.
A. And (3) performing oxygen pressure alkaline leaching dearsenification: weighing 1kg of arsenic-containing cobalt-nickel slag, placing the arsenic-containing cobalt-nickel slag and a solution with the concentration of 1.5mol/L of sodium hydroxide into a high-pressure kettle with the liquid-solid ratio of 8:1 and the stirring speed of 500rpm, sealing, heating to 180 ℃, introducing oxygen to adjust the oxygen pressure in the kettle to be 1.5MPa, leaching for 3 hours, washing and filtering after leaching is finished, and obtaining an alkali leaching solution and alkali leaching slag. The alkaline leaching solution comprises the following components in percentage by weight (g/L): as 11.65, Cu 0.0016, Co 0.00001, Zn 1.7125 and Ni 0.083 show that only arsenic and a small amount of zinc are leached into the solution after the alkaline leaching under oxygen pressure, and copper, cobalt and nickel exist in the leaching residue.
B. Low-acid leaching of alkaline leaching residue: preparing 10L of 100g/L sulfuric acid, adding alkaline leaching residue into the sulfuric acid, and making the end point pH value be 3.5, reaction temperature be 60 ℃, reaction time be 2h, leaching rates of zinc, copper, cobalt, nickel and arsenic be 93.4%, 76.74%, 91.32%, 87.64% and 24.49% respectively, which shows that leaching of zinc, copper, cobalt and nickel in the alkaline leaching residue is completed, and the leaching residue comprises the following components (wt%): zn 1.84, Cu 49.47, Co1.17, Ni0.18 and As 4.21.
C. And (3) carrying out zinc powder displacement copper removal on the pickle liquor: taking 5L of the low acid leaching solution obtained in the step B, carrying out zinc powder displacement copper removal reaction under the conditions that the temperature is 60 ℃, the reaction time is 1.5h, the end point pH is controlled to be 4 and the zinc powder excess coefficient is 1.05, washing and filtering after the reaction is finished to obtain recyclable copper slag and copper removal solution, wherein the copper and cobalt solution precipitation rates are respectively 99.85% and 1.56%, and the copper-rich slag comprises (wt%): cu 83.07, Zn 3.73, Co 0.078, Ni 0.013 and As 0.33.
D. Removing copper liquid, namely oxidizing and precipitating cobalt by using persulfate: and C, taking 1.25L of the decoppered liquid obtained in the step C, adding persulfate, wherein the mass ratio of the persulfate to the total amount of cobalt in the solution is 6:1, reacting at 85 ℃ for 2h, adjusting the pH to be about 4.4 by using a neutralizer to oxidize and precipitate the cobalt, washing and filtering to obtain cobalt-rich slag and a cobalt-removed liquid, wherein the cobalt content in the cobalt-rich slag is 25.53%, the cobalt content in the cobalt-removed liquid is 0.01g/L, the cobalt removal rate of the slag reaches 99.4%, and the cobalt slag can be sold.
E. Copper sweeping and nickel removing: selecting zinc powder to sweep copper and remove nickel from the cobalt removing solution, adding the zinc powder according to the dosage of 2g/l under the conditions that the temperature is 60 ℃ and the reaction time is 1.5h, wherein the nickel content in the solution is only 0.0081 g/l.
F. High-acid leaching: taking 1kg of low-acid leaching residue, carrying out high-acid leaching under the conditions that the liquid-solid ratio is 8:1, the temperature is 80 ℃, the leaching time is 4 hours and the final acid is 35g/L, washing and filtering are carried out after the reaction is finished to obtain high-acid leaching liquid and lead slag, wherein the leaching rates of zinc, copper, cobalt and nickel are respectively 100%, 99.6%, 99.37% and 98.8%, the high-acid leaching liquid can be directly returned to the low-acid leaching process to realize the recovery of zinc, copper, cobalt and nickel, and the lead slag contains 27.33% of lead and can be sold outside the lead slag.
G. Recovering an alkali leaching solution: b, taking 3L of the alkaline leaching solution obtained in the step A, adding 1.5 times of sodium sulfide of the theoretical dosage, reacting for 1h at the temperature of 30 ℃, and removing zinc by sulfurization on the arsenic-containing alkaline solution, wherein the precipitation rate of zinc can reach 97.5% while the precipitation rate of arsenic is only 4.19%; during subsequent causticization arsenic precipitation, the using amount of CaO is Ca/As & lt 6 & gt, the causticization temperature is 85 ℃, the causticization time is 2 hours, the arsenic precipitation rate can reach 99.4%, NaOH solution and calcium arsenate are obtained by filtering, then the calcium arsenate is roasted for 100 minutes under the conditions of 900 ℃ and 15 using amount of carbon powder, the reduction rate of arsenic can reach 99%, the preparation of simple substance arsenic and the regeneration of CaO can be realized, and the recycling of arsenic and the recycling of CaO can be realized.
The foregoing is considered as illustrative of the preferred embodiments of the invention and is not to be construed as limiting the invention in any way. Although the present invention has been described with reference to the preferred embodiments, it is not intended to be limited thereto. Therefore, any simple modification, equivalent change and modification made to the above embodiments according to the technical spirit of the present invention should fall within the protection scope of the technical scheme of the present invention, unless the technical spirit of the present invention departs from the content of the technical scheme of the present invention.
Claims (10)
1. A method for efficiently recycling arsenic-cobalt-nickel-containing slag is characterized by comprising the following steps: the method comprises the following steps:
1) performing oxygen pressure alkaline leaching on the arsenic-containing cobalt nickel slag to obtain arsenic-containing alkaline leaching solution and alkaline leaching slag;
2) the alkaline leaching residue is leached by low acid to obtain low acid leaching liquid containing copper, zinc, cobalt and nickel and low acid leaching residue;
3) replacing copper with zinc powder in the low-acid leaching solution containing copper, zinc, cobalt and nickel to obtain copper-removing solution containing zinc, cobalt and nickel and copper-rich slag; leaching the low acid leaching slag by adopting high acid to obtain high acid leaching liquid containing copper, zinc, cobalt and nickel and lead-rich slag, and returning the high acid leaching liquid to the low acid leaching process to be used as a leaching agent;
4) the copper removal liquid containing zinc, cobalt and nickel adopts persulfate to oxidize and precipitate cobalt to obtain cobalt removal liquid containing zinc and nickel and cobalt-rich slag;
5) and removing impurities from the cobalt-removing solution containing zinc and nickel by using zinc powder to obtain a zinc-containing solution and copper-nickel slag.
6) Evaporating and crystallizing the arsenic-containing alkaline leaching solution to obtain arsenate crystals; dissolving arsenate crystal in water, and introducing SO2Reducing to obtain arsenite solution; returning the arsenite solution to the zinc hydrometallurgy purification process for removing cobalt and nickel;
or after the arsenic-containing alkaline leaching solution is subjected to vulcanization and impurity removal, causticizing by using quick lime to obtain a regenerated NaOH solution and calcium arsenate;
the regenerated NaOH solution returns to the oxygen pressure alkaline leaching process; the calcium arsenate is reduced in vacuum to obtain arsenic simple substance and calcium oxide, and the calcium oxide returns to the causticizing process.
2. The method for efficiently recycling arsenic-cobalt-nickel-containing slag according to claim 1, characterized by comprising the following steps:
the oxygen pressure alkaline leaching conditions are as follows: NaOH solution with the concentration of 1.5-3 mol/L is used as a leaching agent, oxygen is used as an oxidant, the mass ratio of the leaching solution to the solid is 3-6: 1, the oxygen partial pressure is 0.5-2.5 MPa, the temperature is 90-180 ℃, and the time is 2-4 hours.
3. The method for efficiently recycling arsenic-cobalt-nickel-containing slag according to claim 1, characterized by comprising the following steps: the conditions of the low acid leaching are as follows: taking a sulfuric acid solution with the initial concentration of 80-120 g/L as a leaching agent, slowly adding alkaline leaching residues into the sulfuric acid solution at the temperature of 50-70 ℃, wherein the leaching time is 2-3 h, and the pH value of the leaching end point is 2.5-3.5.
4. The method for efficiently recycling arsenic-cobalt-nickel-containing slag according to claim 1, characterized by comprising the following steps: the conditions for replacing copper by the zinc powder are as follows: the temperature is 45-65 ℃, the time is 0.5-1.5 h, the end point pH is controlled to be less than 5.5, and the using amount of the zinc powder is 1.01-1.5 times of the theoretical molar amount of the zinc powder required by copper replacement.
5. The method for efficiently recycling arsenic-cobalt-nickel-containing slag according to claim 1, characterized by comprising the following steps: the conditions of the peracid leaching are as follows: taking a sulfuric acid solution with the initial concentration of 80-120 g/L as a leaching agent, wherein the liquid-solid ratio is 8-12 mL/g, the reaction temperature is 70-90 ℃, and the reaction time is 3-5 h.
6. The method for efficiently recycling arsenic-cobalt-nickel-containing slag according to claim 1, characterized by comprising the following steps: the conditions for the oxidation cobalt precipitation are as follows: the mass ratio of the persulfate to the cobalt in the copper removing liquid containing zinc, cobalt and nickel is 4: 1-9: 1, the pH is adjusted to 2.5-5.0, the temperature is 70-90 ℃, and the time is 1-2 hours.
7. The method for efficiently recycling arsenic-cobalt-nickel-containing slag according to claim 1, characterized by comprising the following steps: the conditions for removing impurities by the zinc powder are as follows: the temperature is 50-60 ℃, the zinc powder dosage is 1-2 g/L, and the reaction lasts for 1-1.5 h.
8. The method of claim 1The method for efficiently recycling the arsenic-cobalt-nickel-containing slag is characterized by comprising the following steps of: dissolving arsenate crystals in water according to the liquid-solid ratio of 1-4 mL/g, and introducing SO2Is subjected to reduction, SO2The ratio of the total molar weight of the arsenate to the total molar weight of the arsenate is 4-8, and reduction reaction is carried out at 30-60 ℃ for 2-4 h to obtain an arsenite solution.
9. The method for efficiently recycling arsenic-cobalt-nickel-containing slag according to claim 1, characterized by comprising the following steps: the conditions of the vulcanization and impurity removal are as follows: the method is characterized in that sodium sulfide is used as a vulcanizing agent, the addition amount of the sodium sulfide is 1.4-1.7 times of the theoretical molar amount of the vulcanizing agent required for precipitating zinc, the temperature is 30-40 ℃, and the time is 0.5-1.5 hours.
10. The method for efficiently recycling arsenic-cobalt-nickel-containing slag according to claim 1, characterized by comprising the following steps: the causticizing conditions are as follows: the proportion of the quicklime to arsenate in the arsenic-containing alkali immersion liquid is 3-6 in terms of molar ratio Ca/As, the temperature is 70-90 ℃, and the time is 2-3 h.
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