CN114934170B - Method for separating arsenic and antimony from copper electrolysis black copper sludge and recovering copper - Google Patents

Method for separating arsenic and antimony from copper electrolysis black copper sludge and recovering copper Download PDF

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CN114934170B
CN114934170B CN202210562585.0A CN202210562585A CN114934170B CN 114934170 B CN114934170 B CN 114934170B CN 202210562585 A CN202210562585 A CN 202210562585A CN 114934170 B CN114934170 B CN 114934170B
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copper
leaching
sodium
antimony
roasting
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CN114934170A (en
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贺山明
王晓明
陈文杰
汪金良
佟志芳
张彪
潘界昌
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Jiangxi University of Science and Technology
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B1/00—Preliminary treatment of ores or scrap
    • C22B1/02—Roasting processes
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B15/00—Obtaining copper
    • C22B15/0002—Preliminary treatment
    • C22B15/001—Preliminary treatment with modification of the copper constituent
    • C22B15/0013—Preliminary treatment with modification of the copper constituent by roasting
    • C22B15/0017—Sulfating or sulfiding roasting
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B15/00—Obtaining copper
    • C22B15/0063—Hydrometallurgy
    • C22B15/0065—Leaching or slurrying
    • C22B15/0082—Leaching or slurrying with water
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B30/00—Obtaining antimony, arsenic or bismuth
    • C22B30/02—Obtaining antimony
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B30/00—Obtaining antimony, arsenic or bismuth
    • C22B30/04—Obtaining arsenic
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/006—Wet processes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

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Abstract

The invention provides a method for separating arsenic and antimony from copper electrolysis black copper sludge and recovering copper, which comprises the following steps: s1, vulcanizing and roasting an alkaline system; s2, leaching calcine; s3, oxidizing and filtering; s4, acid-dissolving and neutralizing to obtain a pure sodium pyroantimonate [ NaSb (OH) 6 ] product. The technical scheme of the invention has the characteristics of simple operation, short flow, high efficiency, environmental protection, economy, strong operability and the like, is easy for industrial application, and has popularization and application values in the aspect of treatment of black copper mud.

Description

Method for separating arsenic and antimony from copper electrolysis black copper sludge and recovering copper
Technical Field
One or more embodiments of the present disclosure relate to the field of metallurgical technology, and more particularly, to a method for separating arsenic, antimony and recovering copper from copper electrolysis black copper sludge.
Background
The black copper mud is mud-like matter produced on a cathode in the copper electrolyte purifying, electro-deposition, copper removal and impurity removal process, contains a large number of Cu, as, sb, bi, ni and other components and is classified as dangerous solid waste by China. As harmful elements arsenic and antimony exist in the black copper sludge, the removal of the arsenic and the antimony in the black copper sludge has important significance for environmental protection and sustainable utilization of copper resources. The arsenic and antimony in the black copper sludge are separated, so that the closed cycle and accumulation of harmful impurity elements such As As, sb and the like in a copper smelting system can be avoided.
At present, a return burden is adopted to enter a smelting system for a treatment mode of black copper sludge, but the method can cause the cyclic accumulation of harmful elements such as arsenic, antimony and the like in the copper smelting process, so that the direct yield of metal and the quality of a final product are seriously influenced, the production capacity of equipment is reduced, and the physical health of workers is endangered; other fire treatment processes include a roasting method, a vacuum carbon reduction method and the like, and mainly convert arsenic into volatile compounds at high temperature, and copper is left in a slag phase, so that copper and arsenic separation and recovery are completed; the pyrogenic process has strong adaptability and short flow, but has the problems of high reaction energy consumption, strict equipment requirement, large potential safety hazard, non-ideal working environment and the like, and is not suitable for comprehensively treating the black copper sludge. The wet treatment process can be classified into acidic system leaching and alkaline system leaching according to the leaching agent. The commonly used acid leaching agents include H 2SO4、HCl、HNO3, wherein sulfuric acid solution is the most commonly used leaching agent, so that copper is recovered in the form of copper sulfate or copper arsenate, and arsenic is recovered in the form of copper arsenate, but the problems of long process flow, small market demand of copper arsenate, difficult treatment of a large amount of waste liquid, high corrosion of sulfuric acid, high consumption and the like exist. The common alkaline leaching agents include NaOH, na 2CO3 and the like, so that arsenic is converted into arsenate or As 2O3, and copper enters slag. Patent CN105238939A discloses A method for roasting black copper mud, in which arsenic in the black copper mud is converted into volatile white arsenic at high temperature, copper to linger is in slag; the process has strong adaptability and short flow, but has high roasting temperature, and the possibility of leakage of the gas arsenic oxide, so the potential safety hazard is large. The patent CN108048664A is to mix black copper mud with alkali, bake for 1-3 hours at 550-700 deg.C, mix roasting product with water, leach, filter, and then to make fractional crystallization to obtain sodium arsenate product and alkali.
In summary, the existing black copper sludge wet treatment process has the problems of complicated treatment flow, large consumption of acid (alkali) leaching agent, more waste liquid, poor product quality and the like, while the fire treatment process has the problems of high energy consumption, large pollution, low recovery rate of valuable metals and the like.
Disclosure of Invention
In view of this, it is an object of one or more embodiments of the present disclosure to provide a method for separating arsenic, antimony and recovering copper from copper electrolysis black copper sludge, so as to solve the problems set forth in the background art.
In view of the above, one or more embodiments of the present specification provide a method for separating arsenic, antimony and recovering copper from copper electrolysis black copper sludge, comprising the steps of:
S1, vulcanizing and roasting an alkaline system: uniformly mixing black copper mud, vulcanizing agent and alkaline refining flux according to a certain mass ratio, placing the mixture in a muffle furnace, roasting at a set temperature for a set time to obtain a roasting product, and grinding the roasting product after roasting is finished;
S2, leaching calcine: adding pure water into a three-neck flask according to a fixed liquid-solid ratio, adding the roasting product obtained in the step S1, adjusting the temperature to react for a period of time, and then performing liquid-solid separation to obtain leaching slag and leaching liquid, wherein the leaching slag is copper sulfide slag and can be directly sent to a smelting and proportioning process, and the leaching liquid is solution enriched with arsenic and antimony;
S3, oxidizing and filtering: adding a certain amount of hydrogen peroxide into a three-neck flask filled with the leaching solution obtained in the step S2, carrying out liquid-solid separation after oxidation reaction for a period of time to obtain filtrate and insoluble matters, wherein the filtrate is sodium arsenate solution, and the insoluble matters are crude sodium antimonate;
S4, acid dissolution, neutralization: dissolving the insoluble substances obtained in the step S3 with an acid solution, filtering, regulating the pH value of the filtrate to 7-9 with an alkali solution, and filtering to obtain a pure sodium pyroantimonate [ NaSb (OH) 6 ] product.
Preferably, the roasting product in the step S1 is milled to more than 70% and the particle size is smaller than 0.1mm, and the milling can be stopped.
Preferably, in the step S1, the black copper mud comprises the following components:
Cu，20～70wt％；
As，5～40wt％；
Sb，0.5～7wt％；
Bi，0.5～5wt％；
pb, 0.1-4.5 wt%; and
Ni，0.5～1.5wt％。
Preferably, the alkaline refining flux in the step S1 is one or a mixture of sodium carbonate, sodium bicarbonate, sodium hydroxide and sodium nitrate.
Preferably, the vulcanizing agent in the step S1 is one or more of sodium sulfide, potassium sulfide and calcium sulfide.
Preferably, the mass ratio of the black copper paste to the vulcanizing agent in the step S1 is: the mass ratio of the black copper mud to the alkaline refining flux is 5:1-15:1 and is 0.5:1-1.5:1.
Preferably, in the step S1, the roasting temperature is 100-500 ℃ and the roasting time is 0.5-3 h.
Preferably, in the step S2, the liquid-solid ratio of water to the roasting product is 4-8:1 (mL/g), the water leaching temperature is 40-90 ℃, the water leaching time is 0.5-2.5 h, the leaching slag is the copper enrichment phase, copper returns to the smelting and batching process in the form of copper sulfide slag, and the leaching liquid is a solution enriched with arsenic and antimony.
Preferably, in the step S3, the oxidant is hydrogen peroxide, the volume ratio of the added amount of the hydrogen peroxide to the leachate in the step S2 is 0.2-0.6:1, and the oxidation reaction time is 2-5 hours, and as sodium arsenate has solubility and sodium antimonate has no solubility, arsenic and antimony in the leachate can be separated. The insoluble matter obtained is crude sodium antimonate; the filtrate is sodium arsenate solution, and the obtained sodium arsenate solution can be used for producing arsenic chemical products such As As 2O3, sodium arsenate, copper arsenate and the like according to different subsequent treatment processes; the alkali can be recycled, so that the resource regeneration is realized.
Preferably, in the step S4, the acid solution is a HCl solution of 1:1.5 (volume ratio of concentrated HCl to H 2 O), the alkali solution is NaOH or sodium salt of carbonic acid, the Na 3SbO4 is used to dissolve crude Na 3SbO4 of the insoluble matters obtained in the step S3, the HCl solution is used to dissolve, the impurity insoluble matters are filtered, and the filtrate is neutralized to pH: 7-9, filtering to obtain pure sodium pyroantimonate [ NaSb (OH) 6 ] product.
From the above, it can be seen that the beneficial effects of the present invention are:
1. According to the technical scheme, the vulcanizing agent and the alkaline refining flux (Na 2CO3, naOH and the like) are mixed with the black copper sludge, harmful elements such as arsenic, antimony and the like in the black copper sludge are separated into a leaching liquid phase after roasting and water leaching processes, the phase components of the obtained water leaching slag mainly comprise cuprous sulfide and copper sulfide, the copper in the black copper sludge can be converted into a fire copper smelting raw material after directly returning to a matte smelting and proportioning process, and the conversion of valuable metals in the black copper sludge is accelerated. The method avoids the recovery of copper in the black copper mud in the form of copper oxide slag phase, copper-arsenic-containing solution and the like in the traditional treatment technical method, and the subsequent recovery process flow of copper is complex. Solves the problem of copper mine raw materials in the copper smelting production process of enterprises, realizes the production of copper sulfide minerals by multiple raw materials and multiple ways, and has a certain practical significance in the aspects of cost reduction and synergy of enterprises.
2. According to the technical scheme, the method realizes the source arsenic removal and antimony removal of the black copper mud, and greatly simplifies the subsequent valuable metal recovery process; the defects that the recycling accumulation of arsenic and antimony is easy, the metal recovery rate and the product quality are affected, and the environmental pollution is easy to generate in the metal recovery process of black copper mud are avoided.
3. The alkaline system sulfuration roasting scheme of the invention belongs to low-temperature solid arsenic roasting, and is different from the roasting process reported in the prior patent, so that the loss of arsenic in the form of gaseous arsenic oxide is effectively avoided. The problems that the conventional roasting method is difficult to collect and recover smoke dust because As 2O3 generated by oxidation enters the smoke gas in a gaseous mode are avoided.
4. The invention utilizes the black copper mud to produce sodium pyroantimonate products, thereby realizing the open-circuit removal of antimony, avoiding the closed-circuit circulation of toxic element antimony, reducing the purification cost and realizing the productization of antimony. Effectively solves the problem of omitting the separation and recovery of antimony in the traditional treatment technical method.
5. The technical scheme of the invention has the characteristics of simple operation, short flow, high efficiency, environmental protection, economy, strong operability and the like, is easy for industrial application, and has popularization and application values in the aspect of treatment of black copper mud.
Drawings
For a clearer description of one or more embodiments of the present description or of the solutions of the prior art, the drawings that are necessary for the description of the embodiments or of the prior art will be briefly described, it being apparent that the drawings in the description below are only one or more embodiments of the present description, from which other drawings can be obtained, without inventive effort, for a person skilled in the art.
FIG. 1 is a schematic process flow diagram of an embodiment of the present invention.
FIG. 2 is a graph showing the results of XRD (X-ray diffraction) analysis of the leaching residue obtained in example 1.
Detailed Description
For the purposes of promoting an understanding of the principles and advantages of the disclosure, reference will now be made in detail to the following specific examples.
It is noted that unless otherwise defined, technical or scientific terms used in one or more embodiments of the present disclosure should be taken in a general sense as understood by one of ordinary skill in the art to which the present disclosure pertains.
A method for separating arsenic and antimony from copper electroblack copper sludge and recovering copper according to an embodiment of the present invention is described in detail below.
Referring to fig. 1, the specific operation steps of the technical embodiment of the present invention are:
S1, vulcanizing and roasting an alkaline system: uniformly mixing black copper mud, vulcanizing agent and alkaline refining flux according to a certain mass ratio, placing the mixture in a muffle furnace, roasting at a set temperature for a set time to obtain a roasting product, and grinding the roasting product after roasting is finished;
S2, leaching calcine: adding pure water into a three-neck flask according to a fixed liquid-solid ratio, adding the roasting product obtained in the step S1, adjusting the temperature to react for a period of time, and then performing liquid-solid separation to obtain leaching slag and leaching liquid, wherein the leaching slag is copper sulfide slag and can be directly sent to a smelting and proportioning process, and the leaching liquid is solution enriched with arsenic and antimony;
S3, oxidizing and filtering: adding a certain amount of hydrogen peroxide into a three-neck flask filled with the leaching solution obtained in the step S2, carrying out liquid-solid separation after oxidation reaction for a period of time to obtain filtrate and insoluble matters, wherein the filtrate is sodium arsenate solution, and the insoluble matters are crude sodium antimonate;
S4, acid dissolution, neutralization: dissolving the insoluble substances obtained in the step S3 with an acid solution, filtering, regulating the pH value of the filtrate to 7-9 with an alkali solution, and filtering to obtain a pure sodium pyroantimonate [ NaSb (OH) 6 ] product.
The working principle of copper and arsenic separation in the technology of the invention is as follows: the Cu 3As,Cu3 As mainly contained in the black copper mud is subjected to chemical reaction with the added vulcanizing agent and alkaline refining flux to generate arsenate, cuprous sulfide and other products, namely copper enters a slag phase, arsenic enters a liquid phase, and copper and arsenic separation is realized; the chemical reaction equation is as follows:
(1)1.5Na2S+1.5Na2CO3+Cu3As+2O2(g)+1.5H2O(g)＝Na3AsO4+1.5Cu2S+3NaOH+1.5CO2(g)
(2)1.5K2S+1.5Na2CO3+Cu3As+2O2(g)+1.5H2O(g)＝Na3AsO4+1.5Cu2S+3KOH+1.5CO2(g)
(3)1.5CaS+1.5Na2CO3+Cu3As+2O2(g)+1.5H2O(g)＝Na3AsO4+1.5Cu2S+3Ca(OH)2+1.5CO2(g)
(4)1.5Na2S+Cu3As+3NaOH+2O2(g)＝Na3AsO4+1.5Cu2S+1.5H2O(g)+1.5Na2O
(5)1.5K2S+Cu3As+3NaOH+2O2(g)＝Na3AsO4+1.5Cu2S+1.5H2O(g)+1.5K2O
(6)1.5CaS+Cu3As+3NaOH+2O2(g)＝Na3AsO4+1.5Cu2S+1.5H2O(g)+1.5CaO
(7)1.5Na2S+1.5NaHCO3+Cu3As+2O2(g)＝Na3AsO4+1.5Cu2S+1.5NaOH+1.5CO2(g)
(8)1.5K2S+1.5NaHCO3+Cu3As+2O2(g)＝Na3AsO4+1.5Cu2S+1.5KOH+1.5CO2(g)
(9)1.5CaS+3NaHCO3+Cu3As+2O2(g)+＝Na3AsO4+1.5Cu2S+1.5Ca(OH)2+3CO2(g)
The invention relates to a working principle of arsenic and antimony separation in roasting-water immersion liquid: alkaline vulcanization roasting-water leaching technology of black copper mud to obtain water leaching solution enriched with arsenic and antimony, adding an oxidant for oxidation, and respectively converting sodium arsenite and sodium thioantimonite in the water leaching solution into sodium arsenite (Na 3AsO4) and crude sodium antimonate (Na 3SbO4). Because sodium arsenate has solubility, and sodium antimonate has no solubility, the separation of arsenic and antimony in the solution can be realized.
The embodiment of the invention provides a method for separating arsenic and antimony from copper electrolysis black copper sludge and recovering copper, wherein copper in the black copper sludge enters a slag phase in a copper sulfide form and returns to a smelting and proportioning process for recovery, arsenic enters a solution in an arsenate form, and antimony takes sodium pyroantimonate as a product, so that the copper/arsenic high-efficiency separation and antimony production are realized, and the method has the advantages of short process flow, simplicity and convenience in operation, low roasting temperature, environmental friendliness, low cost, convenience in industrial application and the like.
The features and capabilities of the present invention are described in further detail below in connection with the examples.
The following examples are illustrative of the invention but are not intended to limit the scope of the invention. The main components (in terms of mass fraction) of the raw material of the black copper mud are, but not specifically stated, cu 20-70 wt%, as 5-40 wt%, sb 0.5-7 wt%, bi 0.5-5 wt%, pb 0.1-4.5 wt%, and Ni 0.5-1.5 wt%, but the technical scheme of the invention is not limited to the black copper mud only used for the content of the substances.
Example 1
Taking black copper mud of a certain copper smelting plant in China as an example, the main components of the raw materials are as follows: 31.6% of Cu, 11.8% of As, 2.16% of Sb, 1.68% of Bi and 1.05% of Te, and is treated by the following steps:
(1) The alkaline system is vulcanized and roasted, namely 30g of black copper mud, sodium carbonate and sodium sulfide are evenly mixed according to the mass ratio of 10:1 and 0.8:1 respectively and then are placed in a muffle furnace to be roasted for 1h at the temperature of 300 ℃, and after roasting is finished, the roasted product is ground to more than 70 percent and the granularity is smaller than 0.1mm;
(2) Leaching the calcine: uniformly mixing the roasting product obtained in the step (1) with water according to a liquid-solid ratio of 5:1 (mL/g), leaching for 1h at 50 ℃, and carrying out solid-liquid separation while hot to obtain leaching residues and leaching liquid. The leaching slag is copper sulfide slag, and the leaching liquid is an enrichment phase of arsenic and antimony.
(3) Oxidizing and filtering: adding 50mL of hydrogen peroxide into a three-neck flask filled with 100mL of the leaching solution obtained in the step (2), carrying out liquid-solid separation after 2h of oxidation reaction to obtain insoluble substances (crude sodium antimonate) and filtrate (sodium arsenate solution);
(4) And (3) acid dissolution and neutralization, namely dissolving insoluble substances obtained in the step (3) by using a hydrochloric acid solution, filtering, adjusting the pH value of the filtrate to 8 by using a sodium hydroxide solution, and filtering to obtain a pure sodium pyroantimonate [ NaSb (OH) 6 ] product.
(5) And (3) analysis and detection: the leaching rate of arsenic is 98.2%, the leaching rate of copper is 0.81%, and the NaSb (OH) 6 prepared in the step (4) can meet the first-level standard specified in the sodium pyroantimonate quality standard (YS 22-1992) of the nonferrous metal industry.
Example 2
Taking black copper mud of a certain copper smelting plant in China as an example, the main components of the raw materials are as follows: 31.6% of Cu, 11.8% of As, 2.16% of Sb, 1.68% of Bi and 1.05% of Te, and is treated by the following steps:
(1) The alkaline system is vulcanized and roasted, namely 30g of black copper mud, sodium carbonate and sodium sulfide are evenly mixed according to the mass ratio of 15:1 and 0.7:1 respectively and then are placed in a muffle furnace to be roasted for 2 hours at the temperature of 200 ℃, and after roasting is finished, the roasted product is ground to more than 70 percent and the granularity is smaller than 0.1mm;
(2) Leaching the calcine: uniformly mixing the roasting product obtained in the step (1) with water according to a liquid-solid ratio of 6:1 (mL/g), leaching for 1h at a temperature of 60 ℃, and carrying out solid-liquid separation while hot to obtain leaching residues and leaching liquid. The leaching slag is copper sulfide slag, and the leaching liquid is an enrichment phase of arsenic and antimony.
(3) Oxidizing and filtering: adding 40mL of hydrogen peroxide into a three-neck flask filled with 100mL of the leaching solution obtained in the step (2), carrying out liquid-solid separation after 2.5h of oxidation reaction to obtain insoluble substances (crude sodium antimonate) and filtrate (sodium arsenate solution);
(4) And (3) acid dissolution and neutralization, namely dissolving insoluble substances obtained in the step (3) by using a hydrochloric acid solution, filtering, adjusting the pH value of the filtrate to 9 by using a sodium hydroxide solution, and filtering to obtain a pure sodium pyroantimonate [ NaSb (OH) 6 ] product.
(5) And (3) analysis and detection: the leaching rate of arsenic is 98.7%, the leaching rate of copper is 1.13%, and the NaSb (OH) 6 prepared in the step (4) can meet the first-level standard specified in the sodium pyroantimonate quality standard (YS 22-1992) of the nonferrous metal industry.
Example 3
Taking black copper mud of a certain copper smelting plant in China as an example, the main components of the raw materials are as follows: 31.6% of Cu, 11.8% of As, 2.16% of Sb, 1.68% of Bi and 1.05% of Te, and is treated by the following steps:
(1) The alkaline system is vulcanized and roasted, namely 30g of black copper mud, sodium bicarbonate and potassium sulfide are evenly mixed according to the mass ratio of 9:1 and 0.5:1 respectively and then are placed in a muffle furnace to be roasted for 3 hours at the temperature of 100 ℃, and after roasting is finished, the roasted product is ground to more than 70 percent and the granularity is smaller than 0.1mm;
(2) Leaching the calcine: uniformly mixing the roasting product obtained in the step (1) with water according to a liquid-solid ratio of 4:1 (mL/g), leaching for 2.5 hours at the temperature of 40 ℃, and carrying out solid-liquid separation while hot to obtain leaching residues and leaching liquid. The leaching slag is copper sulfide slag, and the leaching liquid is an enrichment phase of arsenic and antimony.
(3) Oxidizing and filtering: adding 30mL of hydrogen peroxide into a three-neck flask filled with 100mL of the leaching solution obtained in the step (2), carrying out liquid-solid separation after 2h of oxidation reaction to obtain insoluble substances (crude sodium antimonate) and filtrate (sodium arsenate solution);
(4) And (3) acid dissolution and neutralization, namely dissolving insoluble substances obtained in the step (3) by using a hydrochloric acid solution, filtering, adjusting the pH value of the filtrate to 7 by using a sodium hydroxide solution, and filtering to obtain a pure sodium pyroantimonate [ NaSb (OH) 6 ] product.
(5) And (3) analysis and detection: the leaching rate of arsenic is 97.8%, the leaching rate of copper is 1.46%, and the NaSb (OH) 6 prepared in the step (4) can meet the first-level standard specified in the sodium pyroantimonate quality standard (YS 22-1992) of the nonferrous metal industry.
Example 4
Taking black copper mud of a certain copper smelting plant in China as an example, the main components of the raw materials are as follows: 31.6% of Cu, 11.8% of As, 2.16% of Sb, 1.68% of Bi and 1.05% of Te, and is treated by the following steps:
(1) The alkaline system is vulcanized and roasted, namely 30g of black copper sludge, sodium hydroxide and calcium sulfide are evenly mixed according to the mass ratio of 5:1 and 1.5:1 respectively and then are placed in a muffle furnace to be roasted for 2 hours at the temperature of 500 ℃, and after roasting is finished, the roasted product is ground to more than 70 percent and the granularity is smaller than 0.1mm;
(2) Leaching the calcine: uniformly mixing the roasting product obtained in the step (1) with water according to a liquid-solid ratio of 8:1 (mL/g), leaching for 0.5h at a temperature of 90 ℃, and carrying out solid-liquid separation while hot to obtain leaching residues and leaching liquid. The leaching slag is copper sulfide slag, and the leaching liquid is an enrichment phase of arsenic and antimony.
(3) Oxidizing and filtering: adding 40mL of hydrogen peroxide into a three-neck flask filled with 100mL of the leaching solution obtained in the step (2), carrying out liquid-solid separation after 5h of oxidation reaction to obtain insoluble substances (crude sodium antimonate) and filtrate (sodium arsenate solution);
(4) And (3) acid dissolution and neutralization, namely dissolving insoluble substances obtained in the step (3) by using a hydrochloric acid solution, filtering, adjusting the pH value of the filtrate to 9 by using a sodium hydroxide solution, and filtering to obtain a pure sodium pyroantimonate [ NaSb (OH) 6 ] product.
(5) And (3) analysis and detection: the leaching rate of arsenic is 99.5%, the leaching rate of copper is 0.81%, and the NaSb (OH) 6 prepared in the step (4) can meet the first-level standard specified in the sodium pyroantimonate quality standard (YS 22-1992) of the nonferrous metal industry.
Example 5
Taking black copper mud of a certain copper smelting plant in China as an example, the main components of the raw materials are as follows: 31.6% of Cu, 11.8% of As, 2.16% of Sb, 1.68% of Bi and 1.05% of Te, and is treated by the following steps:
(1) The alkaline system is vulcanized and roasted, namely 30g of black copper mud, sodium nitrate and sodium sulfide are evenly mixed according to the mass ratio of 5:1 and 1.2:1 respectively and then are placed in a muffle furnace to be roasted for 3 hours at the temperature of 200 ℃, and after roasting is finished, the roasted product is ground to more than 70 percent and the granularity is smaller than 0.1mm;
(2) Leaching the calcine: uniformly mixing the roasting product obtained in the step (1) with water according to a liquid-solid ratio of 6:1 (mL/g), leaching for 2.5 hours at a temperature of 60 ℃, and carrying out solid-liquid separation while hot to obtain leaching residues and leaching liquid. The leaching slag is copper sulfide slag, and the leaching liquid is an enrichment phase of arsenic and antimony.
(3) Oxidizing and filtering: adding 20mL of hydrogen peroxide into a three-neck flask filled with 100mL of the leaching solution obtained in the step (2), carrying out liquid-solid separation after 5h of oxidation reaction to obtain insoluble substances (crude sodium antimonate) and filtrate (sodium arsenate solution);
(4) And (3) acid dissolution and neutralization, namely dissolving insoluble substances obtained in the step (3) by using a hydrochloric acid solution, filtering, adjusting the pH value of the filtrate to 7 by using a sodium hydroxide solution, and filtering to obtain a pure sodium pyroantimonate [ NaSb (OH) 6 ] product.
(5) And (3) analysis and detection: the leaching rate of arsenic is 99.3 percent, the leaching rate of copper is 1.35 percent, and the NaSb (OH) 6 prepared in the step (4) can meet the first-level standard specified in the sodium pyroantimonate quality standard (YS 22-1992) of the nonferrous metal industry.
Example 6
Taking black copper mud of a certain copper smelting plant in China as an example, the main components of the raw materials are as follows: 31.6% of Cu, 11.8% of As, 2.16% of Sb, 1.68% of Bi and 1.05% of Te, and is treated by the following steps:
(1) The alkaline system is vulcanized and roasted, namely 30g of black copper sludge, sodium hydroxide and calcium sulfide are evenly mixed according to the mass ratio of 5:1 and 1.5:1 respectively and then are placed in a muffle furnace to be roasted for 2 hours at the temperature of 500 ℃, and after roasting is finished, the roasted product is ground to more than 70 percent and the granularity is smaller than 0.1mm;
(2) Leaching the calcine: uniformly mixing the roasting product obtained in the step (1) with water according to a liquid-solid ratio of 8:1 (mL/g), leaching for 0.5h at a temperature of 90 ℃, and carrying out solid-liquid separation while hot to obtain leaching residues and leaching liquid. The leaching slag is copper sulfide slag, and the leaching liquid is an enrichment phase of arsenic and antimony.
(3) Oxidizing and filtering: adding 60mL of hydrogen peroxide into a three-neck flask filled with 100mL of the leaching solution obtained in the step (2), carrying out liquid-solid separation after 2h of oxidation reaction to obtain insoluble substances (crude sodium antimonate) and filtrate (sodium arsenate solution);
(4) And (3) acid dissolution and neutralization, namely dissolving insoluble substances obtained in the step (3) by using a hydrochloric acid solution, filtering, adjusting the pH value of the filtrate to 9 by using a sodium hydroxide solution, and filtering to obtain a pure sodium pyroantimonate [ NaSb (OH) 6 ] product.
(5) And (3) analysis and detection: the leaching rate of arsenic is 98.6%, the leaching rate of copper is 0.95%, and the NaSb (OH) 6 prepared in the step (4) can meet the first-level standard specified in the sodium pyroantimonate quality standard (YS 22-1992) of the nonferrous metal industry.
Comparative example 1
Taking black copper mud of a certain copper smelting plant in China as an example, the main components of the raw materials are as follows: 31.6% of Cu, 11.8% of As, 2.16% of Sb, 1.68% of Bi and 1.05% of Te, and is treated by the following steps:
The parameters of the other experimental steps were identical to those of example 1 except that the firing temperature of step (1) in example 1 was changed to 600 ℃. And (3) analysis and detection: the leaching rate of arsenic is 85.1 percent, the leaching rate of copper is 11.56 percent, and the NaSb (OH) 6 prepared in the step (4) does not meet the first-level standard specified in the sodium pyroantimonate quality standard (YS 22-1992) of the nonferrous metal industry.
Comparative example 2
Taking black copper mud of a certain copper smelting plant in China as an example, the main components of the raw materials are as follows: 31.6% of Cu, 11.8% of As, 2.16% of Sb, 1.68% of Bi and 1.05% of Te, and is treated by the following steps:
only changing the mass ratio of 30g of black copper mud to sodium carbonate and sodium sulfide in the step (1) in the embodiment 1 into 4:1 and 2:1 respectively, uniformly mixing, and then placing the mixture in a muffle furnace, wherein the parameters of other experimental steps are consistent with those in the embodiment 1. And (3) analysis and detection: the leaching rate of arsenic is 82.7%, the leaching rate of copper is 23.12%, and NaSb (OH) 6 prepared in the step (4) does not meet the first-level standard specified in sodium pyroantimonate quality standard (YS 22-1992) of nonferrous metal industry.
Comparative example 3
Taking black copper mud of a certain copper smelting plant in China as an example, the main components of the raw materials are as follows: 31.6% of Cu, 11.8% of As, 2.16% of Sb, 1.68% of Bi and 1.05% of Te, and is treated by the following steps:
The hydrogen peroxide dosage in the step (3) in the example 2 is changed to 10mL, and the parameters of other experimental steps are the same as those in the example 2. And (3) analysis and detection: the leaching rate of arsenic is 90.2%, the leaching rate of copper is 1.13%, and the prepared NaSb (OH) 6 does not meet the first-level standard specified in sodium pyroantimonate quality standard (YS 22-1992) in the nonferrous metal industry.
The present disclosure is intended to embrace all such alternatives, modifications and variances which fall within the broad scope of the appended claims. Any omissions, modifications, equivalents, improvements, and the like, which are within the spirit and principles of the one or more embodiments of the disclosure, are therefore intended to be included within the scope of the disclosure.

Claims (6)

1. A method for separating arsenic, antimony and recovering copper from copper electrolysis black copper sludge, which is characterized by comprising the following steps:
S1, vulcanizing and roasting an alkaline system: uniformly mixing black copper mud, vulcanizing agent and alkaline refining flux according to a certain mass ratio, placing the mixture in a muffle furnace, roasting at a set temperature for a set time to obtain a roasting product, and grinding the roasting product after roasting is finished;
s2, leaching calcine: adding pure water into a three-neck flask according to a fixed liquid-solid ratio, adding the roasting product obtained in the step S1, adjusting the temperature to react for a period of time, and then performing liquid-solid separation to obtain leaching residues and leaching liquid, wherein the leaching residues are copper sulfide residues and are directly sent to a smelting and proportioning process, and the leaching liquid is a solution enriched with arsenic and antimony;
S3, oxidizing and filtering: adding a certain amount of hydrogen peroxide into a three-neck flask filled with the leaching solution obtained in the step S2, carrying out liquid-solid separation after oxidation reaction for a period of time to obtain filtrate and insoluble matters, wherein the filtrate is sodium arsenate solution, and the insoluble matters are crude sodium antimonate;
S4, acid dissolution, neutralization: dissolving the insoluble substances obtained in the step S3 with an acid solution, filtering, regulating the pH value of the filtrate to 7-9 with an alkali solution, and filtering to obtain a pure sodium pyroantimonate [ NaSb (OH) 6 ] product;
Wherein, the alkaline refining flux in the step S1 is one or a mixture of sodium carbonate, sodium bicarbonate, sodium hydroxide and sodium nitrate;
Wherein, the vulcanizing agent in the step S1 is one or a mixture of sodium sulfide, potassium sulfide and calcium sulfide;
Wherein, the mass ratio of the black copper mud to the vulcanizing agent in the step S1 is as follows: 0.5:1-1.5:1, and the mass ratio of the black copper mud to the alkaline refining flux is 5:1-15:1;
in the step S1, the roasting temperature is 100-500 ℃ and the roasting time is 0.5-3 h.
2. The method for separating arsenic, antimony and recovering copper from copper electrolysis black copper sludge according to claim 1, wherein the grinding is stopped when the roasted product in the step S1 is ground to a particle size of 70% or more and less than 0.1 mm.
3. The method for separating arsenic, antimony and recovering copper from copper electrolysis black copper sludge according to claim 1, wherein the black copper sludge in the step S1 comprises the following components:
Cu，20～70wt％；
As，5～40wt％；
Sb，0.5～7wt％；
Bi，0.5～5wt％；
pb, 0.1-4.5 wt%; and
Ni，0.5～1.5wt％。
4. The method for separating arsenic, antimony and recovering copper from copper electrolysis black copper sludge according to claim 1, wherein in the step S2, the liquid-solid ratio of water to the roasted product is 4-8:1 (mL/g), the water immersion temperature is 40-90 ℃, and the water immersion time is 0.5-2.5 h.
5. The method for separating arsenic and antimony from copper electroblack copper sludge and recovering copper according to claim 1, wherein in the step S3, the oxidant is hydrogen peroxide, the volume ratio of the added hydrogen peroxide to the leaching solution in the step S2 is 0.2-0.6:1, and the oxidation reaction time is 2-5h.
6. The method for separating arsenic, antimony and recovering copper from copper electrolysis black copper sludge according to claim 1, wherein in the step S4, the acid solution is an HCl solution with a volume ratio of concentrated HCl to H 2 O of 1:1.5, and the alkali solution is NaOH or sodium salt of carbonic acid.
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Publication number Priority date Publication date Assignee Title
WO2009068735A1 (en) * 2007-11-27 2009-06-04 Outotec Oyj Method for processing pyritic concentrate containing gold, copper and arsenic
CN101591554A (en) * 2008-05-30 2009-12-02 北京三聚环保新材料股份有限公司 A kind of normal temperature composite desulfurating and dearsenic agent and preparation method thereof
CN103290221A (en) * 2012-02-28 2013-09-11 兰州理工大学 Method for recovering copper, arsenium and antimony from black copper sludge
CN109207733A (en) * 2018-09-26 2019-01-15 云南铜业科技发展股份有限公司 A kind of preparation method for extracting tellurium from tellurium copper slag

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009068735A1 (en) * 2007-11-27 2009-06-04 Outotec Oyj Method for processing pyritic concentrate containing gold, copper and arsenic
CN101591554A (en) * 2008-05-30 2009-12-02 北京三聚环保新材料股份有限公司 A kind of normal temperature composite desulfurating and dearsenic agent and preparation method thereof
CN103290221A (en) * 2012-02-28 2013-09-11 兰州理工大学 Method for recovering copper, arsenium and antimony from black copper sludge
CN109207733A (en) * 2018-09-26 2019-01-15 云南铜业科技发展股份有限公司 A kind of preparation method for extracting tellurium from tellurium copper slag

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