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WO2022237532A1 - Procédé de traitement inoffensif de récupération de soufre, de rhénium et d'arsenic à partir de scories de sulfure d'arsenic - Google Patents

Procédé de traitement inoffensif de récupération de soufre, de rhénium et d'arsenic à partir de scories de sulfure d'arsenic Download PDF

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WO2022237532A1
WO2022237532A1 PCT/CN2022/089408 CN2022089408W WO2022237532A1 WO 2022237532 A1 WO2022237532 A1 WO 2022237532A1 CN 2022089408 W CN2022089408 W CN 2022089408W WO 2022237532 A1 WO2022237532 A1 WO 2022237532A1
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arsenic
rhenium
solution
leaching
sulfur
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PCT/CN2022/089408
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English (en)
Chinese (zh)
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刘智勇
刘志宏
洪明浩
李启厚
张家润
何雯睿
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中南大学
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Priority to GB2316454.4A priority Critical patent/GB2621039A/en
Publication of WO2022237532A1 publication Critical patent/WO2022237532A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/04—Working-up slag
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B17/00—Sulfur; Compounds thereof
    • C01B17/02—Preparation of sulfur; Purification
    • C01B17/06—Preparation of sulfur; Purification from non-gaseous sulfides or materials containing such sulfides, e.g. ores
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G28/00—Compounds of arsenic
    • C01G28/008—Sulfides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G47/00—Compounds of rhenium
    • C01G47/003—Preparation involving a liquid-liquid extraction, an adsorption or an ion-exchange
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G49/00—Compounds of iron
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G49/00—Compounds of iron
    • C01G49/0018—Mixed oxides or hydroxides
    • 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
    • C22B1/11—Removing sulfur, phosphorus or arsenic other than by 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
    • C22B15/0002—Preliminary treatment
    • C22B15/001—Preliminary treatment with modification of the copper constituent
    • 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
    • C22B15/0067—Leaching or slurrying with acids or salts thereof
    • C22B15/0071—Leaching or slurrying with acids or salts thereof containing sulfur
    • 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
    • C22B15/0084—Treating solutions
    • C22B15/0086—Treating solutions by physical methods
    • 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
    • C22B15/0084—Treating solutions
    • C22B15/0089—Treating solutions by chemical methods
    • C22B15/0093—Treating solutions by chemical methods by gases, e.g. hydrogen or hydrogen sulfide
    • 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
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
    • C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
    • C22B3/08—Sulfuric acid, other sulfurated acids or salts thereof
    • 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
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/42—Treatment or purification of solutions, e.g. obtained by leaching by ion-exchange extraction
    • 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
    • C22B61/00—Obtaining metals not elsewhere provided for in this subclass
    • 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
    • C22B7/007—Wet processes by acid leaching
    • 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
    • C22B7/02—Working-up flue dust
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
    • C25C1/12—Electrolytic production, recovery or refining of metals by electrolysis of solutions of copper
    • 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
    • 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
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency

Definitions

  • the invention belongs to the technical field of metallurgy, and in particular relates to a method for recovering sulfur rhenium from arsenic sulfide slag and harmless disposal of arsenic.
  • arsenic sulfide slag contains valuable metals, such as copper (Cu) and rhenium (Re).
  • the content of Re in the earth's crust is very low, mainly associated with metal sulfide ores, and is an extremely valuable scattered metal. Because of its excellent properties such as high temperature resistance and corrosion resistance, it is widely used in high temperature alloys, aerospace and other important fields, and is an important resource. Therefore, it is of great significance to recover Re from arsenic sulfide slag.
  • the content of Re in arsenic sulfide slag is between 0.1-2%, which has huge economic recovery value.
  • arsenic sulfide slag there are two main methods for dealing with arsenic sulfide slag, one is to reduce the leaching toxicity of arsenic sulfide slag through stabilization and solidification, and the other is to convert arsenic sulfide slag into arsenic-containing products in a resourceful way for recycling .
  • the inventors found that the concentration of rhenium in the arsenic-containing solution obtained from the treatment of arsenic sulfide slag is very low, and it is very difficult to recover and prepare high-purity rhenium products from this arsenic-containing solution.
  • the present invention provides a method for recovering sulfur rhenium from arsenic sulfide slag and arsenic harmless disposal.
  • This method makes arsenic preferentially precipitated, and the reaction conditions are well controlled during the precipitation process, so that the loss of rhenium in the process of arsenic precipitation is very small, so that the arsenic and copper rhenium are separated, and the separated solution improves the resin to improve the adsorption efficiency of rhenium.
  • the arsenic sulfide slag is leached by oxygen pressure acid, and the arsenic, copper, and rhenium in the slag are leached efficiently.
  • the present invention solves the problem that the arsenic and the valuable metal copper-rhenium cannot be completely separated, and realizes the stabilization of the arsenic efficiently.
  • the method of the invention can recover sulfur, copper and rhenium from the arsenic sulfide slag, and can also treat the arsenic harmlessly, and has the advantages of environmental protection, economy, energy saving, high efficiency, high resource recovery rate and the like.
  • a method for recovering sulfur rhenium and arsenic harmless disposal from arsenic sulfide slag comprising the following steps:
  • Oxygen pressure acid leaching take arsenic sulfide slag in the reaction kettle, add sulfuric acid and additives therein, pass oxidizing gas into the reaction kettle, carry out oxygen pressure leaching, after the oxygen pressure leaching is finished, carry out separation, obtain containing Arsenic-copper-rhenium leaching solution A and sulfur-containing leaching slag A;
  • the method of the present invention is particularly suitable for treating the following arsenic sulfide slag, which includes the following main components in terms of mass percentage: arsenic: 1%-60%, sulfur: 1-50%, copper: 0.1%-5%, Rhenium: 0.1%-2%.
  • the ratio of valence arsenic concentration to pentavalent arsenic concentration affects the stability of arsenic-fixed minerals.
  • the temperature of the oxygen pressure leaching is 140-170°C, such as 140°C, 150°C, 160°C, 170°C.
  • the pressure of the oxygen pressure leaching is 0.5-3.0 MPa, such as 0.5 MPa, 1 MPa, 1.5 MPa, 2.0 MPa, 2.5 MPa, 3.0 MPa.
  • the concentration of sulfuric acid used is 5-50g/L, such as 5g/L, 10g/L, 20g/L, 30g/L, 50g/L.
  • the volume to mass ratio (ml:g) of sulfuric acid and arsenic sulfide slag is (3:1)-(20:1), more preferably (10:1)-(20:1) (ml:g).
  • the additive is at least one of calcium lignosulfonate and sodium lignosulfonate.
  • the present inventors found that adding the above-mentioned additives during oxygen pressure acid leaching can remove the wrapping of arsenic, copper, and rhenium by sulfur, thereby increasing the leaching rate of arsenic, copper, and rhenium.
  • the mass ratio of the additive to the arsenic sulfide slag is (1:200)-(1:20).
  • step (1) the oxygen pressure leaching is carried out under stirring, and the stirring speed is 500-800r/min.
  • the oxygen pressure leaching time is 5-10h.
  • the oxidizing gas is selected from at least one of oxygen, air, and oxygen-enriched air.
  • the ratio of trivalent arsenic concentration (g/L) to pentavalent arsenic concentration (g/L) in the arsenic-containing copper rhenium leach solution A described in step (1) is (4:1)-(1 :9), such as 4:1, 3:1, 7:3, 6:4, 1:1, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1 :8, 1:9.
  • the arsenic-containing copper-rhenium leaching solution A in step (1) contains trivalent arsenic and pentavalent arsenic, wherein the content of pentavalent arsenic accounts for 20-90 wt% of the total arsenic content.
  • step (1) the operation of step (1) is specifically: get arsenic sulfide slag in the reactor, and add sulfuric acid solution and calcium lignosulfonate, the volume to mass ratio of sulfuric acid solution and arsenic sulfide slag (ml :g) is (10:1)-(20:1), the concentration of sulfuric acid is 10-50g/L, and the mass ratio of calcium lignosulfonate to arsenic sulfide slag is (1:200)-(1:50), Pass oxidizing gas into the reaction kettle, carry out oxygen pressure leaching at temperature 140-170°C, oxygen partial pressure 0.5-3.0MPa, rotation speed 500-800r/min, and control the leaching time to 5-10h.
  • the concentration of trivalent arsenic in the solution (g/L)
  • the ratio to the concentration (g/L) of pentavalent arsenic is between (4:1)-(1:9).
  • the present inventors found that when trivalent arsenic and pentavalent arsenic exist in the solution at the same time, the process of arsenic precipitation is obviously accelerated, and the leaching concentration of arsenic in scorodite precipitation is lower.
  • step (2) the sulfur-containing leaching residue A is recovered by hot filtration to obtain sulfur. Sulfur is available for sale. Hot filter residue B can be returned to the batching system.
  • the temperature of the hot filtration is 120-250°C, more preferably the hot filtration is carried out at 130-170°C.
  • the time for thermal filtration is 10-120 min, more preferably 10-40 min.
  • the pressure of suction filtration is 0.3-2.0Mpa.
  • the present inventors have found that the sulfur-containing leaching slag A washed and dried is heated and suction-filtered in a well-sealed filter device, the sulfur in the slag can be fully recovered, and a high-purity sulfur product can be obtained, with a purity greater than or equal to 97%. %.
  • step (2) the filter device is heated in an oven.
  • the iron salt solution is selected from at least one of ferrous sulfate solution, ferric sulfate solution, ferrous chloride solution, ferric chloride solution, ferrous nitrate solution, and ferric nitrate solution.
  • the neutralizing agent is NaOH solution, for example, the concentration is 0.4-0.7mol/L.
  • the pH of the reaction process is controlled to be 1.0-5.0, such as 1.0, 1.5, 2.0, 3.0, 4.0, 5.0.
  • step (3) arsenic and copper-rhenium are completely separated, and there is basically no loss of copper-rhenium in the process of arsenic precipitation.
  • the rate is as high as 99%.
  • the scorodite precipitate obtained in step (3) can be sent to landfill.
  • step (4) described macroporous weakly basic anion resin is PM404, any one in WS418, Tulsimer RCX-5143.
  • the mass ratio of the resin to the arsenic sulfide slag in step (1) is (1:10)-(1:5).
  • the adsorption temperature is 25-50°C.
  • the adsorption time is 6-8h.
  • the desorbent used is any one of ammonium thiocyanate, ammonia water, ammonium thiocyanate and ammonia water mixed solution.
  • step (4) the ammonia-containing vapor produced during evaporative concentration is cooled by a condenser tube to obtain dilute ammonia water, which can be used to prepare a desorbent.
  • the percentages involved in this article are all mass percentages, and the slag after selective arsenic precipitation and separation is investigated by leaching toxicity test by TCLP method.
  • the method provided by the invention removes the arsenic in the arsenic sulfide slag through oxygen pressure leaching.
  • the leached slag is washed and dried to obtain sulfur by hot filtration.
  • the purity of the sulfur product is as high as 97%.
  • the precipitate is piled up in the landfill; the liquid after the arsenic precipitation uses a macroporous weakly basic anion exchange resin for the adsorption of rhenium, and then the loaded resin is washed with clean water, and the rhenium-rich desorption liquid is obtained after desorption. Evaporation concentration and cooling crystallization to obtain ammonium rhenate product; after adsorption, liquid electrolysis recovers copper.
  • the method removes arsenic from the arsenic sulfide slag and synthesizes stable arsenic-fixed minerals, and can recover sulfur, copper and rhenium in the arsenic sulfide slag, realizing the separation of arsenic and valuable metals and making them harmless.
  • the invention has a high comprehensive recovery rate of resources and a wide application range of raw materials, and solves the pollution problem in the extraction process of the traditional process, especially the arsenic sulfide slag produced in the copper smelting process. The advantages of the method are more obvious.
  • the present invention adopts the method of oxygen pressure acid leaching to remove all the arsenic in the arsenic sulfide slag, the arsenic content of the raw material after the arsenic removal is low, and valuable metals such as copper and rhenium can be comprehensively recovered to reduce the arsenic content in the product;
  • the present invention adopts oxygen pressure acid leaching to oxidize S 2- in arsenic sulfide slag to S 0 , and then recovers sulfur through hot filtration to obtain sulfur, which solves the problem that sulfur in arsenic sulfide slag is difficult to recover ;
  • the present invention adopts the method of selective arsenic precipitation to make As in the leaching solution synthesize scorodite while allowing Cu and Re in the leaching solution to remain in the solution, so that As is completely separated from Cu and Re, and the synthesized scorodite prevents As from migrating , also makes the As in the smelting system have an ideal open circuit, which is a simple process flow, resource-saving, and environmentally friendly method, and the advantage of the selective arsenic precipitation method is that the harmless As and Cu are simultaneously realized. and Re separation, and the prepared scorodite has good stability, is convenient for stockpiling, and has low process cost;
  • the arsenic oxidant in the arsenic precipitation process is one of oxygen, air or oxygen-enriched air, which has a wide range of sources and low consumption, which reduces the cost in the arsenic oxidation process.
  • Fig. 1 is a schematic process flow diagram of the method of the embodiment of the present invention.
  • Fig. 2 is the SEM image of the arsenic-fixed minerals of Example 1 and Comparative Example.
  • Fig. 3 is the XRD pattern of the arsenic-fixed minerals of Example 1 and Comparative Example.
  • FIG. 1 for the process flow of the embodiment.
  • the main components of the raw material are As 25.8%, Cu 0.21%, Re 0.19%, S 34.70%, and the following steps are used for processing:
  • Oxygen pressure acid leaching Weigh a certain amount of arsenic sulfide slag in the reactor, add sulfuric acid solution and calcium lignosulfonate; feed oxidizing gas into the reactor; control the volume of sulfuric acid solution and arsenic sulfide slag
  • the mass ratio is 20:1 (ml:g)
  • the stirring speed is 800r/min
  • the concentration of sulfuric acid solution used is 10g/L
  • the mass ratio of calcium lignosulfonate to arsenic sulfide residue is 1:200
  • the oxygen partial pressure is 2Mpa.
  • the time is 6 hours, the reaction temperature is 150°C, after the leaching is completed, filter and separate to obtain the leaching solution A and the leaching residue A;
  • the leaching rate of arsenic is 98.08%
  • the leaching rate of copper is 96.38%
  • the leaching rate of rhenium is 96.83%
  • the sulfur content of the leaching residue is 91.90%, of which the elemental sulfur content is 90.80%
  • the concentration of each element in the leach solution is As 12.65g /L, Cu 101.19mg/L, Re 91.98mg/L, at this time the ratio of trivalent arsenic concentration (g/L) to pentavalent arsenic concentration (g/L) in the leaching solution is 7:3.
  • the sulfur product contains 97.10% sulfur (S) and 0.03% As.
  • the leaching concentration of arsenic in the synthesized arsenic-fixing mineral (sororite) is 0.1114mg/L, which complies with the provisions of GB5085.3-2007 (Solid Waste Identification Standard-Leach Toxicity Identification) and can be safely stockpiled.
  • copper rhenium basically does not precipitate, and the arsenic precipitation rate is as high as 99%.
  • the SEM image of the arsenic-fixed mineral prepared in this example is shown in a in FIG. 2
  • the XRD image is shown in a in FIG. 3 .
  • the concentration of each element in the solution after arsenic precipitation is As 20.92mg/L, Cu 41.09mg/L, Re 37.54mg/L.
  • Adsorption of rhenium add macroporous weakly basic anion exchange resin PM404 to the liquid B after precipitation of arsenic in step (3) for adsorption of rhenium, the mass ratio of resin to arsenic sulfide slag is 1:10, and shake at 200rpm/min , the time is 6h, the adsorption temperature is 25°C, and then 6mol/L ammonium thiocyanate is used as the desorbing agent, the shaking rate is 150r/min, the desorption temperature is 25°C, and the desorption time is 6h to obtain a rhenium-rich desorption solution.
  • the stripped liquid is evaporated and concentrated, cooled and crystallized to obtain the ammonium rhenate product.
  • solution C after adsorption contained 20.78mg/L As, 40.11mg/L Cu, and 0.05mg/L Re, and the desorption solution contained 178.34mg/L Re.
  • Solution C can recover copper by electrolysis after adsorption.
  • the main components of the raw material are As 32.8%, Cu 3.38%, Re 0.26%, S 43.23%, and the following steps are used for processing:
  • Oxygen pressure acid leaching Weigh a certain amount of arsenic sulfide slag in the reactor, add sulfuric acid solution and calcium lignosulfonate; feed oxidizing gas into the reactor; control the volume-to-mass ratio of sulfuric acid and arsenic sulfide slag 20:1 (ml:g), stirring speed 800r/min, sulfuric acid solution concentration 20g/L, mass ratio of calcium lignosulfonate to arsenic sulfide slag 1:100, reaction temperature 140°C, oxygen partial pressure 1.5 Mpa, leaching time 7h, after leaching, filter and separate to obtain leaching solution A and leaching residue A;
  • the leaching rate of arsenic is 98.23%
  • the leaching rate of copper is 95.65%
  • the leaching rate of rhenium is 97.34%
  • the sulfur content of the leaching residue is 92.30%, of which the elemental sulfur content is 91.23%
  • the concentration of each element in the leach solution is As 16.10g /L, Cu 1.61g/L, Re 126.65mg/L, at this time the ratio of trivalent arsenic concentration (g/L) to pentavalent arsenic concentration (g/L) in the leaching solution is 3:1.
  • the sulfur product contains 97.01% sulfur (S) and 0.02% As.
  • the leaching concentration of arsenic in the synthesized arsenic-fixing mineral scorodite is 0.6684mg/L, which complies with the provisions of GB5085.3-2007 (Solid Waste Identification Standard-Leach Toxicity Identification), and can be safely stockpiled.
  • copper rhenium basically does not precipitate, and the arsenic precipitation rate is as high as 99%.
  • the concentration of each element in the solution after arsenic precipitation is As 33.44mg/L, Cu 0.73g/L, Re 59.30mg/L.
  • Adsorption of rhenium add macroporous weakly basic anion exchange resin WS418 to the liquid B after the arsenic precipitation in step (3) to carry out the adsorption of rhenium, the mass ratio of resin to arsenic sulfide slag is 1:10, at 200rpm/min Oscillation, the time is 7h, the adsorption temperature is 25°C, and then 6mol/L ammonia water is used as the desorption agent, the oscillation rate is 150r/min, the desorption temperature is 25°C, and the desorption time is 7h to obtain a rhenium-rich desorption solution, and the desorption solution is carried out Concentrate by evaporation and crystallize by cooling to obtain ammonium rhenate product.
  • solution C after adsorption contained As 32.32mg/L, Cu 0.71g/L, and Re 0.07mg/L, and the desorption solution contained Re 245.67mg/L.
  • Solution C can recover copper by electrolysis after adsorption.
  • the main components of the raw material are As 30.90%, Cu 4.10%, Re 0.12%, S 44.78%, and the following steps are used for processing:
  • Oxygen pressure acid leaching Weigh a certain amount of arsenic sulfide slag in the reactor, add sulfuric acid solution and calcium lignosulfonate; feed oxidizing gas into the reactor; control the volume-to-mass ratio of sulfuric acid and arsenic sulfide slag 10:1 (ml:g), stirring speed 800r/min, sulfuric acid concentration 50g/L, mass ratio of calcium lignosulfonate to arsenic sulfide slag 1:50, reaction temperature 170°C, oxygen partial pressure 1.0Mpa , the leaching time is 5h, after the leaching is finished, filter and separate to obtain the leaching solution A and the leaching residue A;
  • the leaching rate of arsenic is 80.23%
  • the leaching rate of copper is 77.34%
  • the leaching rate of rhenium is 79.10%
  • the sulfur content of the leaching residue is 87.12%, of which the elemental sulfur content is 85.89%
  • the concentration of each element in the leach solution is As 24.79g /L, Cu 3.17g/L, Re 94.92mg/L, at this time the ratio of trivalent arsenic concentration (g/L) to pentavalent arsenic concentration (g/L) in the leaching solution is 6:4.
  • the sulfur product contains 97.12% sulfur (S) and 0.05% As.
  • the synthesized arsenic-fixed minerals meet the requirements of GB5085.3-2007 that the leaching concentration of arsenic in scorodite is 0.0758mg/L (identification standard for solid waste - identification of leaching toxicity), and can be safely stockpiled.
  • copper rhenium basically does not precipitate, and the arsenic deposition rate is as high as 99%.
  • the concentration of each element in the solution after arsenic precipitation is As 32.34mg/L, Cu 0.82g/L, Re 24.57mg/L.
  • solution C after adsorption contained As 31.80mg/L, Cu 0.82g/L, and Re 0.02mg/L, and the desorption solution contained Re 93.36mg/L.
  • Solution C can recover copper by electrolysis after adsorption.
  • the main components of the raw material are As 21.35%, Cu 5.16%, Re 0.35%, S 46.86%, and the following steps are used for processing:
  • Oxygen pressure acid leaching Weigh a certain amount of arsenic sulfide slag in the reactor, add sulfuric acid solution and calcium lignosulfonate; feed oxidizing gas into the reactor; control the volume-to-mass ratio of sulfuric acid and arsenic sulfide slag 10:1 (ml:g), stirring speed 800r/min, sulfuric acid concentration 50g/L, mass ratio of calcium lignosulfonate to arsenic sulfide slag 1:100, reaction temperature 170°C, oxygen partial pressure 3.0Mpa , the leaching time is 10h, and after the leaching is completed, filter and separate to obtain the leaching solution A and the leaching residue A;
  • the leaching rate of arsenic is 99.28%
  • the leaching rate of copper is 98.67%
  • the leaching rate of rhenium is 99.10%
  • the sulfur content of the leaching residue is 94.23%, of which the elemental sulfur content is 92.25%
  • the concentration of each element in the leach solution is As 21.19g /L, Cu 5.09g/L, Re 346.85mg/L, at this time the ratio of trivalent arsenic concentration (g/L) to pentavalent arsenic concentration (g/L) in the leaching solution is 1:9.
  • the sulfur product contains 98.09% sulfur (S) and 0.01% As.
  • the synthesized arsenic-fixed mineral meets the requirements of GB5085.3-2007 that the leaching concentration of arsenic in scorodite is 0.1427mg/L (identification standard for solid waste - identification of leaching toxicity), and can be safely stockpiled.
  • copper rhenium basically does not precipitate, and the arsenic deposition rate is as high as 99%.
  • the concentration of each element in the solution after arsenic precipitation is As 28.13mg/L, Cu 1.34g/L, Re 91.02mg/L.
  • Solution C can recover copper by electrolysis after adsorption.
  • Example 1 Take the same arsenic sulfide slag as in Example 1, and obtain leach solution A in the same way as in Example 1 step (1).
  • the leaching solution A1 was subjected to arsenic precipitation in the same manner as in step (3) of Example 1 to obtain a precipitate.
  • the leaching concentration of arsenic in the obtained precipitate was 75.326mg/L, which did not meet the requirements of GB5085.3-2007 (identification standard for solid waste - identification of leaching toxicity), and the arsenic deposition rate under this condition was only 55.78%.
  • the SEM image of the arsenic-fixed mineral prepared in this comparative example is shown in b in FIG. 2
  • the XRD image is shown in b in FIG. 3 .

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Abstract

La présente invention appartient au domaine technique de la métallurgie, et concerne plus particulièrement un procédé de traitement inoffensif permettant la récupération de soufre, de rhénium et d'arsenic à partir de scories de sulfure d'arsenic. Le procédé comprend quatre étapes, à savoir la lixiviation acide sous pression d'oxygène, la filtration à chaud, la précipitation sélective d'arsenic et l'adsorption de rhénium. Selon le procédé, l'arsenic est précipité de préférence, et les conditions de réaction sont bien régulées dans le processus de précipitation, de sorte que la perte de rhénium dans le processus de précipitation d'arsenic est très faible, et ainsi l'arsenic et le rhénium sont séparés ; et la résine est améliorée dans la solution séparée afin d'améliorer l'efficacité d'adsorption du rhénium, ce qui permet d'obtenir des produits de rhénium à haut degré de pureté. Par rapport à d'autres procédés, la présente invention résout le problème de l'incapacité de séparer entièrement l'arsenic et les métaux de valeur cuivre et rhénium, et stabilise efficacement l'arsenic. Le procédé de la présente invention permet de récupérer le soufre et le rhénium à partir des scories de sulfure d'arsenic, et l'arsenic peut être traité de façon inoffensive, et le procédé présente les avantages d'être respectueux de l'environnement, économiquement viable, à économie d'énergie et à haute efficacité, présentant un taux élevé de récupération de ressources, etc.
PCT/CN2022/089408 2021-05-13 2022-04-26 Procédé de traitement inoffensif de récupération de soufre, de rhénium et d'arsenic à partir de scories de sulfure d'arsenic WO2022237532A1 (fr)

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