CN114606400A - Method for treating arsenic-zinc-containing leaching residues of high-iron - Google Patents
Method for treating arsenic-zinc-containing leaching residues of high-iron Download PDFInfo
- Publication number
- CN114606400A CN114606400A CN202210107655.3A CN202210107655A CN114606400A CN 114606400 A CN114606400 A CN 114606400A CN 202210107655 A CN202210107655 A CN 202210107655A CN 114606400 A CN114606400 A CN 114606400A
- Authority
- CN
- China
- Prior art keywords
- arsenic
- zinc
- copper
- precipitation
- iron
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- 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
- C22B11/00—Obtaining noble metals
- C22B11/04—Obtaining noble metals by wet processes
- C22B11/042—Recovery of noble metals from waste materials
-
- 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
- C22B13/00—Obtaining lead
- C22B13/04—Obtaining lead by wet processes
- C22B13/045—Recovery from waste materials
-
- 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
- C22B15/0089—Treating solutions by chemical 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
- C22B15/0091—Treating solutions by chemical methods by cementation
-
- 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
- C22B19/00—Obtaining zinc or zinc oxide
- C22B19/20—Obtaining zinc otherwise than by distilling
-
- 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
- C22B41/00—Obtaining germanium
-
- 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
- C22B58/00—Obtaining gallium or indium
-
- 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
Abstract
The invention discloses a method for treating high-iron arsenic-zinc-containing leaching residues, which comprises the following steps: (1) mixing the arsenic-zinc-containing leaching residue with copper slag and zinc hydrometallurgy electrodeposition waste liquid; (2) introducing sulfur dioxide into the slurry to react so as to obtain lead-silver slag and reduction leachate; (3) mixing iron powder with the reduction leaching solution for reaction; (4) mixing part of the copper precipitation and arsenic removal solution with the cuprous arsenide bottom flow, and introducing oxygen simultaneously; (5) mixing zinc powder with the arsenic fixing solution for reaction; (6) mixing the copper-precipitation solution with the other part of the copper-precipitation arsenic-removal solution; (7) and performing zinc hydrometallurgy on the recovered liquid to precipitate iron. Therefore, the method has the advantages of short flow, environmental friendliness and high recovery rate of valuable metals, and realizes the concentrated curing open circuit of the element arsenic, thereby having good safety, environmental protection and economic benefits.
Description
Technical Field
The invention relates to the field of metallurgy, in particular to a method for treating arsenic-zinc-containing leaching residues of high-iron.
Background
Arsenic is a harmful impurity element in the zinc smelting process, and has the following main effects: firstly, arsenic impurities in the new liquid exceed the standard, so that electrolytic plate burning is easily caused, the electric efficiency is reduced, and the electrolytic process cannot be carried out in severe cases; secondly, arsenic hydride toxic gas is easily generated in the replacement reaction process of the arsenic-containing acidic solution, and serious threat is brought to the life safety of staff; thirdly, the arsenic content is an important index for measuring the quality of part of products, such as hematite, gypsum and the like, and the excessive arsenic content can influence the quality of the products, thereby influencing the economic benefit; fourthly, the arsenic-containing waste water and the arsenic-containing waste residue have great influence on the ecological environment. Therefore, the open circuit of arsenic is the key work of zinc smelting enterprises. In the traditional zinc smelting process, arsenic is usually dispersed in materials such as gypsum slag, jarosite slag, goethite slag, lead silver slag, smoke dust and the like, is relatively dispersed and is difficult to be intensively solidified and opened.
The scorodite crystal is a stable crystalline ferric arsenate hydrate (FeAsO)4·2H2O), the solubility in aqueous solution is much smaller than that of amorphous ferric arsenate, and the long-term storage does not cause secondary pollution, so the arsenic-containing solid waste is considered to be the most suitable for storage. The stability of the scorodite is mainly influenced by the crystallization strength and the particle size, the specific surface area of the large scorodite is smaller, the leaching toxicity is low, and the stability is high. Therefore, the scorodite arsenic fixation method is the most ideal arsenic open-circuit method at present. The common methods for synthesizing scorodite include a hydrothermal method and a modified atmospheric pressure method. In the process of preparing the scorodite by the hydrothermal method, because the supersaturation degree in a reaction system is low, crystal nuclei can grow stably, and large-particle and high-crystallinity scorodite crystals can be obtained. In 2008, FUJITA et al proposed the synthesis of scorodite crystals by a modified atmospheric pressure process, but this process is prone to the formation of amorphous ferric arsenate during the manufacturing process.
With the development and utilization of high-quality zinc resources, zinc smelting raw materials increasingly present the characteristics of high-impurity multi-metal, mainly embodied as high iron and high arsenic, and are rich in valuable metal elements such as copper, indium, lead, tin, silver and the like. The existing zinc smelting technology can not efficiently and cleanly process the minerals, so that the development of a zinc smelting method which can efficiently recover valuable metals such as zinc, indium, copper, iron and the like and can realize the open circuit of arsenic centralized solidification aiming at the high-iron arsenic-containing zinc leaching slag has important significance.
Disclosure of Invention
The present invention is directed to solving, at least to some extent, one of the technical problems in the related art. Therefore, the invention aims to provide a method for treating high-iron arsenic-containing zinc leaching slag. The method has the advantages of short flow, environmental friendliness and high recovery rate of valuable metals, and realizes the concentrated curing open circuit of the element arsenic, thereby having good safety, environmental protection and economic benefits.
In one aspect of the invention, the invention provides a method for treating high-iron arsenic-zinc-containing leaching slag, which comprises iron, arsenic and indium. According to an embodiment of the invention, the method comprises:
(1) mixing the arsenic-zinc-containing leaching residue with copper slag and zinc hydrometallurgy electrodeposition waste liquid to obtain slurrying liquid;
(2) introducing sulfur dioxide into the slurry to react so as to obtain lead-silver slag and reduction leachate;
(3) mixing iron powder with the reduction leaching solution for reaction so as to obtain cuprous arsenide underflow and copper-precipitation arsenic-removal solution;
(4) mixing a part of the copper-precipitation arsenic-removal liquid with the cuprous arsenide underflow, and introducing oxygen simultaneously to obtain ferric arsenate precipitation and arsenic-fixation liquid;
(5) mixing zinc powder with the arsenic-fixing solution to react so as to obtain copper concentrate and copper-precipitation solution;
(6) mixing the copper-precipitation solution with the other part of the copper-precipitation arsenic-removal solution to obtain metal slag and a recovered solution;
(7) and (4) carrying out zinc hydrometallurgy on the recovered liquid to precipitate iron so as to obtain iron slag and the liquid after iron precipitation.
According to the method for treating the high-iron arsenic-zinc-containing leaching slag, the copper slag and the zinc hydrometallurgy electrodeposition waste liquid are mixed to obtain a slurry containing zinc ions, iron ions, indium ions, silver ions, copper ions and lead ions, and then sulfur dioxide and SO are introduced into the slurry2Reducing Fe (III) into Fe (II) with the reduction of elements such As lead, silver and the like to obtain lead-silver slag and a reduction leachate containing Cu (II), As (III) and Fe (II), adding iron powder into the reduction leachate for reaction, wherein the iron powder can react with Cu (II) and As (III) in the reduction leachate according to 6Cu2++2As3++9Fe＝9Fe2++2Cu3As ↓' reaction to obtain arsenic cuprous underflow and the copper precipitating and dearsenifying liquid, and mixing partial copper precipitating and dearsenifying liquid with the arsenic cuprous underflow while introducing oxygen and Cu3As will leach out and decompose into free Cu (I) and As (III), and then Cu (I) will be oxidized into Cu (II), the reaction formula is Cu++O2+H+＝Cu2++HO2As (III) is oxidized to form As (V), and the presence of Cu (II) accelerates the oxidation of Fe (II) to Fe (III), the reaction formula is Cu2++Fe2+＝Cu++Fe3+So as to make Fe (III) reach supersaturated state, and further promote Fe and arsenic in the system to react3++H3AsO4+2H2O＝FeAsO4·2H2O↓+3H+The main reaction is carried out to generate ferric arsenate precipitate, and the residual liquid is the arsenic fixing liquid. And finally, carrying out zinc hydrometallurgy and iron precipitation on the recovered liquid to obtain iron slag and iron precipitation liquid. Therefore, the method has the advantages of short flow, environmental friendliness and high recovery rate of valuable metals, and realizes the concentrated curing open circuit of the element arsenic, thereby having good safety, environmental protection and economic benefits.
In addition, the method for treating the high-iron arsenic-zinc-containing leaching residue according to the embodiment of the invention can also have the following additional technical characteristics:
in some embodiments of the invention, in the step (1), the high-iron arsenic-containing zinc leaching slag and the copper slag are mixed according to the total Cu to total As molar ratio of (3.0-5.0): 1. Therefore, when Cu (II) and As (III) react together, the As (III) can be ensured to generate Cu As completely As possible3As precipitates.
In some embodiments of the invention, the liquid-solid ratio of the zinc leaching residue and the copper residue to the zinc hydrometallurgy electrodeposition waste liquid is (6-8) g: 1 mL.
In some embodiments of the present invention, in the step (2), the introduction rate of the sulfur dioxide is 1000 to 2000m3/h。
In some embodiments of the invention, in step (2), the reaction satisfies at least one of the following conditions: the initial acidity is 100-130 g/L; the temperature is 110-120 ℃; the pressure is 0.2-0.3 MPa; the time is 1.5-3.0 h. Therefore, the better copper precipitation and arsenic removal effect can be realized, and the iron powder is ensuredSubstantially non-reactive with As (III) and capable of substantially reducing AsH3And (4) generating.
In some embodiments of the present invention, in the step (3), the iron powder has an excess factor of 1.5 to 1.6. Therefore, valuable elements in the reduction leaching solution can be fully reduced.
In some embodiments of the present invention, in the step (3), the temperature of the reaction is 80 to 90 ℃ and the time is 0.5 to 2.0 hours.
In some embodiments of the present invention, in step (3), the reaction has a pH of 2.0 to 4.0.
In some embodiments of the present invention, in the step (4), the oxygen is introduced at a rate of 500-1500 m3/h。
In some embodiments of the present invention, in step (4), the initial acidity of the system is 50 to 100 g/L. Thereby, ferric arsenate precipitation can be facilitated.
In some embodiments of the invention, in the step (4), the molar ratio of the cuprous arsenide underflow to a part of the copper precipitation and arsenic removal liquid is (1.5-2.0): 1, mixing. Thereby, Fe (III) is supersaturated, and ferric arsenate (FeAsO) is generated4·2H2O) precipitation.
In some embodiments of the invention, in step (4), the system satisfies at least one of the following conditions: the pH is 1.0-2.0; the temperature is 160-200 ℃; the pressure is 1.0-2.0 MPa; the time is 2.5-3.5 h.
In some embodiments of the invention, in the step (5), the zinc powder has an excess coefficient of 1.2-1.5. Thereby, complete replacement of copper can be ensured.
In some embodiments of the present invention, in step (5), the reaction has a pH of 2.0 to 4.0. Therefore, the subsequent metal slag is beneficial to performing replacement reaction or neutralization precipitation to obtain the metal slag containing germanium and/or gallium and/or indium.
In some embodiments of the invention, step (6) further comprises: and carrying out replacement reaction or neutralization precipitation on the metal slag so as to obtain the metal slag containing germanium and/or gallium and/or indium.
In some embodiments of the invention, further comprising: and (4) performing neutral leaching on the solution after iron precipitation so as to obtain metal zinc.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Drawings
The above and/or additional aspects and advantages of the present invention will become apparent and readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings of which:
FIG. 1 is a schematic flow chart of a method for treating high-iron arsenic-containing zinc leaching slag according to an embodiment of the invention;
FIG. 2 is a schematic flow chart of a method for treating high-iron arsenic-containing zinc leaching slag according to another embodiment of the invention;
FIG. 3 is a schematic flow chart of the treatment method of the high-iron arsenic-containing zinc leaching residue according to another embodiment of the invention;
FIG. 4 is a flow chart of a process for treating the high-iron arsenic-containing zinc leaching residue according to an embodiment of the invention;
FIG. 5 is a flow chart of the treatment process of the high-iron arsenic-containing zinc leaching residue in the embodiment of the invention.
Detailed Description
The embodiments described below with reference to the drawings are illustrative and intended to be illustrative of the invention and are not to be construed as limiting the invention.
In one aspect of the invention, the invention provides a method for treating zinc leaching residue. According to an embodiment of the invention, the method comprises:
s100: mixing the arsenic-zinc-containing leaching residue with copper slag and zinc hydrometallurgy electrodeposition waste liquid
In the step, the high-iron arsenic-zinc-containing leaching residue, the copper slag and the zinc hydrometallurgy electrodeposition waste liquid are mixed to obtain slurry.
Furthermore, the high-iron arsenic-zinc-containing leaching slag and the copper slag are mixed according to the molar ratio of the total Cu to the total As being (3.0-5.0): 1. The inventor finds that if the molar ratio of the total Cu to the total As is too high, unnecessary energy and materials are consumed in the copper slag leaching process, and if the molar ratio of the total Cu to the total As is too low, the As is incompletely precipitated, and the arsenic removal effect is poor. In the high-iron arsenic-zinc-containing leaching slag, if the molar ratio of Cu to As satisfies (3.0-5.0): 1, the copper slag does not need to be added.
Further, the liquid-solid ratio of the zinc leaching residue and the copper residue to the zinc electrowinning waste liquid from the zinc hydrometallurgy is (6-8) g: 1 mL. The inventor finds that if the zinc hydrometallurgy electrodeposition waste liquid is added in an excessive amount, the pH value of the reduction leaching liquid is higher, and the iron arsenate (FeAsO) in the copper precipitation and arsenic removal process is not favorable4·2H2O) formation of a precipitate. If the addition amount of the zinc electrodeposition waste liquid generated in the zinc hydrometallurgy is too small, the leaching rate of Cu and As is low, and the reduction leaching effect is not ideal.
S200: introducing sulfur dioxide into the slurry for reaction
In the step, sulfur dioxide is introduced into the slurry obtained in S100, and the sulfur dioxide can reduce and leach valuable elements in the zinc leaching residue to obtain lead-silver residue and a reduction leaching solution. Specifically, the introduction rate of the sulfur dioxide is 1000-2000 m3/h。
Further, the above reaction satisfies at least one of the following conditions: the initial acidity is 100-130 g/L; the temperature is 110-120 ℃; the pressure is 0.2-0.3 MPa; the time is 1.5-3.0 h. The inventor finds that if the initial acidity is too high, the pH value of the reduction leaching solution is higher, which is not beneficial to ferric arsenate (FeAsO) in the copper precipitation and arsenic removal process4·2H2O), if the initial acidity is too low, the leaching rate of Cu and As is low, and the reduction leaching effect is not ideal; meanwhile, if the temperature is too high, energy is wasted, and if the temperature is too low, the leaching rate of Cu and As is low; if the pressure is too high, the energy waste is caused, the process control risk is high, the cost is high, and if the pressure is too low, the leaching rate of Cu and As is low, and the reaction rate is slow; in addition, if the reaction time is too long, energy waste and production efficiency are low, and if the reaction time is too short, the leaching rate of Cu and As is low and the reaction rate is slow.
S300: mixing iron powder and the reduction leaching solution for reaction
In this step, iron powder is mixed with the reduction leaching solution to react, ironThe powder can react with Cu (II) and As (III) in the reduction leaching solution to generate Cu3As precipitates, the effect of copper precipitation and arsenic removal is realized, and the cuprous arsenide bottom flow and the copper precipitation and arsenic removal liquid are obtained.
Furthermore, the excess coefficient of the iron powder is 1.5-1.6. The inventor finds that if the adding amount of the iron powder is insufficient, the precipitation rate of Cu and As is low, and if the adding amount of the iron powder is excessive, the Fe content of the solution after copper precipitation and arsenic removal is too high, and the effect of the subsequent iron precipitation process is poor.
Further, the temperature of the reaction is 80-90 ℃, and the time is 0.5-2.0 h. The inventor finds that if the reaction temperature is too high, energy waste and high risk of process control are caused, and if the reaction temperature is too low, the reaction rate is slow; if the reaction time is too long, the As content in the solution after copper precipitation and arsenic removal is high.
Further, the pH of the reaction is 2.0 to 4.0. The inventors have found that In solution if the pH of the reaction is too high3+Hydrolysis precipitation, which results In loss, and excessive consumption of reducing or neutralizing agents required In the subsequent slag displacement reaction or neutralization precipitation if the pH of the reaction is too low.
S400: mixing part of the solution after copper precipitation and dearsenification with the cuprous arsenide underflow, and simultaneously introducing oxygen
In the step, part of the solution after the copper precipitation and arsenic removal is mixed with the cuprous arsenide underflow, and simultaneously oxygen and Cu are introduced3As can be decomposed into Cu (I) and As (III), and then Cu (I) is oxidized into Cu (II), As (III) is oxidized into As (V), and the existence of Cu (II) can accelerate Fe (II) to be oxidized into Fe (III), thereby leading Fe (III) to reach a supersaturated state, and promoting iron and arsenic in the system to be expressed As Fe3++H3AsO4+2H2O＝FeAsO4·2H2O↓+3H+The main reaction of the method is carried out, namely ferric arsenate precipitate is generated, and the residual liquid is arsenic fixing afterliquid, wherein the ferric arsenate precipitate is commonly called scorodite, the crystal form of the scorodite is mainly stable regular octahedron, so that the stockpiling treatment is facilitated, and the concentrated solidification and open circuit of arsenic are realized. Specifically, the introduction rate of the oxygen is 500-1500 m3/h。
Furthermore, the system initial acidity is 50-100 g-And L. The inventor finds that if the initial acidity is too high or too low, the initial acidity is not favorable for ferric arsenate (FeAsO) in the copper precipitation and arsenic removal process4·2H2O) formation of a precipitate.
Further, the mole ratio of the total Fe to the total As of the cuprous arsenide underflow and a part of the copper precipitation and arsenic removal solution is (1.5-2.0): 1, mixing. The inventor finds that if the molar ratio of the total Fe to the total As is too high, the Fe content of the solution after copper precipitation and dearsenification is too high, the effect of the subsequent iron precipitation process is poor, and if the molar ratio of the total Fe to the total As is too low, the Cu and As precipitation rate is low, and the As content of the solution after copper precipitation and dearsenification is high.
Further, the system satisfies at least one of the following conditions: the pH is 1.0-2.0; the temperature is 160-200 ℃; the pressure is 1.0-2.0 MPa; the time is 2.5-3.5 h. The inventors found that the pH value of 1-2 is favorable for the generation of ferric arsenate (FeAsO)4·2H2O) precipitation).
S500: mixing zinc powder and arsenic fixing solution for reaction
In the step, zinc powder and the post-arsenic fixation solution are mixed for reaction, and copper concentrate and post-copper deposition solution are obtained after displacement reaction.
Furthermore, the excess coefficient of the zinc powder is 1.2-1.5. The inventor finds that if the adding amount of the zinc powder is too large, the consumption of auxiliary materials is large, the cost is high, if the adding amount of the zinc powder is too small, the copper deposition is incomplete, and the solution after the copper deposition contains Cu2+High.
Further, the pH of the reaction is 2.0 to 4.0. The inventors have found that if the pH of the reaction is too high or too low, the displacement reaction or the neutralization precipitation of the dross is not favored.
S600: mixing the solution after copper precipitation with the other part of the solution after copper precipitation and arsenic removal
In the step, the solution after copper precipitation and the other part of the solution after copper precipitation and arsenic removal are mixed and then enter a comprehensive scattered metal recovery system to obtain metal slag and recovered solution.
Further, referring to fig. 2, step S600 further includes: and performing replacement reaction or neutralization precipitation on the metal slag to obtain metal slag containing germanium and/or gallium and/or indium.
S700: the recovered liquid is processed by zinc hydrometallurgy for iron precipitation
In the step, the recovered liquid obtained in the step S600 is subjected to zinc hydrometallurgy for iron precipitation, and conditions required for iron precipitation are controlled to obtain iron slag and the liquid after iron precipitation. It should be noted that the conditions required for iron precipitation are conventional processes, and are not described herein again.
Further, referring to fig. 3 and 4, the method for processing the zinc leaching residue further includes step S800: and (4) performing neutral leaching on the solution after iron precipitation.
In the step, the liquid after iron precipitation is subjected to neutral leaching, so that the metal zinc in the liquid after iron precipitation can be recovered.
Mixing high-iron arsenic-zinc-containing leaching slag, copper slag and zinc hydrometallurgy electrodeposition waste liquid to obtain slurry containing zinc ions, iron ions, indium ions, silver ions, copper ions and lead ions, and introducing sulfur dioxide and SO2Reducing Fe (III) into Fe (II) with the reduction of elements such As lead, silver and the like to obtain lead-silver slag and a reduction leaching solution containing Cu (II), As (III) and Fe (II), and adding iron powder into the reduction leaching solution for reaction, wherein the iron powder can react with Cu (II) and As (III) in the reduction leaching solution according to 6Cu2++2As3++9Fe＝9Fe2++2Cu3As ↓' to obtain arsenic cuprous underflow and the solution after precipitating copper and removing arsenic, then mixing part of the solution after precipitating copper and removing arsenic with arsenic cuprous arsenide underflow, and simultaneously introducing oxygen, Cu3As will leach out and decompose into free Cu (I) and As (III), and then Cu (I) will be oxidized into Cu (II), the reaction formula is Cu++O2+H+＝Cu2++HO2As (III) is oxidized to form As (V), and the presence of Cu (II) accelerates the oxidation of Fe (II) to Fe (III), the reaction formula being Cu2++Fe2+＝Cu++Fe3+So as to make Fe (III) reach supersaturated state, and further promote Fe and arsenic in the system to react3++H3AsO4+2H2O＝FeAsO4·2H2O↓+3H+The main reaction is carried out to generate ferric arsenate precipitate, and the residual liquid is the arsenic fixing liquid. Then adding zinc powder into the arsenic-fixing solution, performing displacement reaction to obtain copper concentrate and copper-precipitation solution, and obtaining the copper concentrate and the copper-precipitation solutionAnd mixing the solution after copper precipitation and the other part of solution after copper precipitation and arsenic removal, then feeding the mixture into a scattered metal recovery system to obtain various metal residues and recovered solution, and finally, carrying out zinc hydrometallurgy and iron precipitation on the recovered solution to obtain iron residues and solution after iron precipitation. Therefore, the method has the advantages of short flow, environmental friendliness and high recovery rate of valuable metals, and realizes the concentrated curing open circuit of the element arsenic, thereby having good safety, environmental protection and economic benefits.
The following embodiments of the present invention are described in detail, and it should be noted that the following embodiments are exemplary only, and are not to be construed as limiting the present invention. In addition, all reagents used in the following examples are commercially available or can be synthesized according to methods herein or known, and are readily available to those skilled in the art for reaction conditions not listed, if not explicitly stated.
Examples
Raw materials: the arsenic-zinc-containing leaching slag of the high-iron contains elements such as copper, indium, lead, tin, silver, iron, arsenic and the like, and the main components and the contents are determined as follows: 11.46 percent of Fe, 0.32 percent of As and 330g/t of In; 45.92 percent of Cu in the copper slag.
Reduction leaching: the high-iron arsenic-zinc-containing leaching slag and the copper slag are mixed according to the molar ratio of total Cu to total As of 4: 1, mixing zinc leaching residue, copper residue and zinc hydrometallurgy electrodeposition waste liquid according to a solid-liquid ratio of 7 g: 1mL of mixed slurry enters a reduction autoclave, the initial acidity is controlled to be 120g/L and the temperature is controlled to be 110 ℃, and then the slurry is stirred according to the volume of 1200m3Introduction of SO at a rate of/h2Controlling the kettle pressure to be 0.3MPa, and carrying out reduction leaching reaction for 2.5 h;
under the condition of high temperature and high acid, valuable metals such as zinc, iron, indium, copper and the like in the high-iron arsenic-zinc-containing leaching residue are leached into the solution, and SO is utilized2Reducing Fe (III) into Fe (II) to promote the decomposition of zinc ferrite (in the process, the decomposition of indium ferrite is also carried out), and simultaneously, reducing elements such as lead, silver and the like are also carried out to obtain lead-silver slag and a reduction leachate;
the main components and contents of the reduction leaching solution are as follows: fe (II) 42g/L, Fe (III) 0.3g/L, Cu 3.2.2 g/L, As 0.87.87 g/L, In 113mg/L, wherein the reduction rate of Fe (III) is 99.0 percent, and the enrichment ratio of lead and silver is more than 12.
Copper deposition and arsenic removal: adding the reduction leaching solution into a copper precipitation and arsenic removal reaction tank, then adding iron powder, wherein the excess coefficient of the iron powder is 1.5, controlling the reaction temperature to be 85 ℃, and reacting for 0.5 h;
the arsenic in the reduction leachate is mainly in the form of As (III), and in the case of iron powder addition, the precipitation of As (III) in the solution is carried out As 6Cu2++2As3++9Fe＝9Fe2++2Cu3Performing As ↓reactionto obtain cuprous arsenide bottom flow and copper precipitation arsenic removal liquid; meanwhile, under the acidic condition, the metallic iron is basically not reacted with As (III), so that the AsH can be greatly reduced3The generation of the method is beneficial to the field operation safety and the occupational health of the staff;
the cuprous arsenide underflow comprises the following main components in percentage by weight: cu 39.4%, As 14.3%; the copper precipitation and arsenic removal solution comprises the following main components: fe 48.1g/L, Cu 10.3.3 mg/L, As 3.1.1 mg/L; the precipitation rate of copper and arsenic in the process is more than 98 percent.
Fixing arsenic: and (3) mixing the cuprous arsenide underflow with a part of the solution after copper precipitation and arsenic removal according to the molar ratio of total Fe to total As of 1.5: 1, mixing, putting into an arsenic-fixing autoclave, controlling the pH value to be 1.2, the pressure to be 2.0MPa, the temperature to be 180 ℃ and the pressure to be 850m3Oxygen is introduced at the rate of/h, and the reaction is carried out for 3 h.
Zn-Cu-Fe-As-H in high-temperature, pressurized, oxidizing atmosphere2SO4In the system, Cu3As is leached and decomposed into free Cu (I) and As (III), and then the Cu (I) is oxidized to generate Cu (II) and the As (III) is oxidized to generate As (V); accelerating the oxidation of Fe (II) to Fe (III) in the presence of Cu (II) (Cu under oxygen atmosphere)2++Fe2+＝Cu++Fe3+，Cu++O2+H+＝Cu2++HO2) So as to make Fe (III) reach supersaturated state and promote Fe and As in the system3++H3AsO4+2H2O＝FeAsO4·2H2O↓+3H+The main reaction is carried out, the coprecipitation is ferric arsenate precipitation (containing basic ferric sulfate, iron vitriol and zinc polymer) which takes ferric arsenate particles as main components, and the residual liquid is arsenic fixing liquid. It is composed ofThe ferric arsenate precipitate is commonly called as scorodite, and the crystal form of the ferric arsenate precipitate is mainly stable octahedron, so that the stockpiling treatment is facilitated, and the concentrated curing open circuit of arsenic is realized.
Wherein the ferric arsenate precipitate comprises the following main components in percentage by weight: fe32.4%, As24.7%; the arsenic fixing liquid comprises the following main components in percentage by weight: Cu31.7g/L, Fe is less than 1g/L, As is less than 0.3 g/L; the arsenic precipitation rate and the iron precipitation rate in the process are respectively more than 96% and more than 92%.
Copper deposition: and (4) feeding the arsenic-fixed solution into a copper precipitation reaction tank, adding zinc powder, wherein the excess coefficient of the zinc powder is 1.5, and performing a displacement reaction to obtain copper concentrate and a copper precipitation solution. Wherein the copper concentrate is sold for external use, and the valuable metals are recycled.
The copper concentrate comprises the following main components in percentage by weight: cu58.7 percent and Zn less than 2 percent; the Cu content of the solution after copper deposition is less than 1 g/L.
Comprehensively recovering scattered metals: mixing the solution after copper precipitation and the rest solution after copper precipitation and arsenic removal, and then feeding the mixture into a comprehensive scattered metal recovery system, wherein SO is introduced into the reduction leaching solution to reduce Fe (III)2After the reaction, Fe (II) is almost completely reduced to obtain various metal residues rich in germanium and/or gallium and/or indium and comprehensively recovered liquid by adopting a zinc powder replacement or neutralization precipitation method.
And (3) iron precipitation: placing the comprehensively recovered liquid in an iron precipitation reaction kettle, controlling the temperature at 175 ℃, and performing reaction at 900m3Introducing oxygen, controlling the kettle pressure to be 1.5MPa, and reacting for 3 hours to obtain iron slag and a liquid after iron precipitation.
Wherein the content of Fe in the iron slag is 55.32%, and the Fe content of the liquid after iron precipitation is less than 5 g/L.
In summary, according to the method for treating the high-iron arsenic-containing zinc leaching residue of the invention, SO is firstly utilized2Valuable elements in the arsenic-zinc leaching residues containing high iron are fully leached in a strong reducing atmosphere, and the leaching rate of zinc, copper, iron, arsenic and indium is over 96 percent; part of iron in the leachate reacts with arsenic to generate stable ferric arsenate precipitate, so that the concentrated solidification open circuit of arsenic impurity reaches over 85 percent, the problems of arsenic dispersion and difficult open circuit in the zinc hydrometallurgy process are solved, and the potential harm of arsenic to the environment is avoided; meanwhile, the copper in the zinc material is recovered in the form of copper concentrate, and the recovery rate reaches 90 percentAnd in the above step, the rest iron is produced into high-quality iron slag through a zinc hydrometallurgy iron precipitation process.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (10)
1. A treatment method of high-iron arsenic-zinc-containing leaching slag, wherein the high-iron arsenic-zinc-containing leaching slag comprises iron, arsenic and indium, and is characterized by comprising the following steps:
(1) mixing the arsenic-zinc-containing leaching residue with copper slag and zinc hydrometallurgy electrodeposition waste liquid to obtain slurrying liquid;
(2) introducing sulfur dioxide into the slurry to react so as to obtain lead-silver slag and reduction leachate;
(3) mixing iron powder with the reduction leaching solution for reaction so as to obtain cuprous arsenide underflow and copper-precipitation arsenic-removal solution;
(4) mixing a part of the copper-precipitation arsenic-removal liquid with the cuprous arsenide underflow, and introducing oxygen simultaneously to obtain ferric arsenate precipitation and arsenic-fixation liquid;
(5) mixing zinc powder with the arsenic-fixing solution to react so as to obtain copper concentrate and copper-precipitation solution;
(6) mixing the copper-precipitation solution with the other part of the copper-precipitation arsenic-removal solution to obtain metal slag and a recovered solution;
(7) and (4) carrying out zinc hydrometallurgy and iron precipitation on the recovered liquid so as to obtain iron slag and the liquid after iron precipitation.
2. The treatment method according to claim 1, wherein in the step (1), the high-iron arsenic-zinc-containing leaching slag and the copper slag are mixed according to the molar ratio of total Cu to total As being (3.0-5.0): 1;
optionally, in the step (1), the solid-to-liquid ratio of the zinc leaching residue and the copper residue to the zinc hydrometallurgy electrodeposition waste liquid is (6-8) g: 1 mL.
3. The treatment method according to claim 1, wherein in the step (2), the introduction rate of the sulfur dioxide is 1000 to 2000m3/h。
4. The process of claim 1, wherein in step (2), the reaction satisfies at least one of the following conditions:
the initial acidity is 100-130 g/L;
the temperature is 110-120 ℃;
the pressure is 0.2-0.3 MPa;
the time is 1.5-3.0 h.
5. The treatment method as set forth in claim 1, wherein in the step (3), the excess factor of the iron powder is 1.5 to 1.6;
optionally, in the step (3), the reaction temperature is 80-90 ℃ and the reaction time is 0.5-2.0 h;
optionally, in the step (3), the pH of the reaction is 2.0-4.0.
6. The treatment method according to claim 1, wherein in the step (4), the oxygen gas is introduced at a flow rateThe rate is 500-1500 m3/h；
Optionally, in the step (4), the initial acidity of the system is 50-100 g/L;
optionally, in the step (4), the molar ratio of the cuprous arsenide underflow to a part of the copper precipitation and arsenic removal solution is (1.5-2.0): 1, mixing.
7. The treatment method according to claim 1, wherein in the step (4), the system satisfies at least one of the following conditions:
the pH is 1.0-2.0;
the temperature is 160-200 ℃;
the pressure is 1.0-2.0 MPa;
the time is 2.5-3.5 h.
8. The treatment method as defined in claim 1, wherein in the step (5), the excess coefficient of the zinc powder is 1.2 to 1.5;
optionally, in the step (5), the pH of the reaction is 2.0-4.0.
9. The process of claim 1, wherein step (6) further comprises: and carrying out replacement reaction or neutralization precipitation on the metal slag so as to obtain the metal slag containing germanium and/or gallium and/or indium.
10. The processing method of claim 1, further comprising: and (4) performing neutral leaching on the solution after iron precipitation so as to obtain metal zinc.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210107655.3A CN114606400B (en) | 2022-01-28 | 2022-01-28 | Treatment method of high-iron arsenic-zinc-containing leaching residues |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210107655.3A CN114606400B (en) | 2022-01-28 | 2022-01-28 | Treatment method of high-iron arsenic-zinc-containing leaching residues |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114606400A true CN114606400A (en) | 2022-06-10 |
| CN114606400B CN114606400B (en) | 2023-09-22 |
Family
ID=81860019
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210107655.3A Active CN114606400B (en) | 2022-01-28 | 2022-01-28 | Treatment method of high-iron arsenic-zinc-containing leaching residues |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114606400B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115109920A (en) * | 2022-06-20 | 2022-09-27 | 云锡文山锌铟冶炼有限公司 | Method for reducing zinc and sulfur in hematite by using zinc hydrometallurgy system |
| CN115216628A (en) * | 2022-06-14 | 2022-10-21 | 云锡文山锌铟冶炼有限公司 | Method for removing copper and arsenic from copper and arsenic-containing acidic solution |
Citations (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4244734A (en) * | 1979-07-19 | 1981-01-13 | Hazen Research, Inc. | Process for recovering metal values from materials containing arsenic |
| JPS59145740A (en) * | 1983-02-07 | 1984-08-21 | Mitsubishi Metal Corp | Treatment of zinc leached slag |
| JP2000219920A (en) * | 1999-01-29 | 2000-08-08 | Dowa Mining Co Ltd | Method for removing and fixing aresenic from solution containing arsenic |
| JP2006265592A (en) * | 2005-03-23 | 2006-10-05 | Dowa Mining Co Ltd | Wet treatment method for zinc leaching residue |
| US20090019970A1 (en) * | 2005-10-19 | 2009-01-22 | Dundee Precious Metals Inc. | Process for recovery of metal values from materials containing arsenic and/or antimony |
| US20100050814A1 (en) * | 2006-11-02 | 2010-03-04 | Maurits Van Camp | Recovery of Non-Ferrous Metals from By-Products of the Zinc and Lead Industry using Electric Smelting with Submerged Plasma |
| CN102851497A (en) * | 2012-09-21 | 2013-01-02 | 北京矿冶研究总院 | Method for treating arsenic-containing material |
| CN103789544A (en) * | 2014-02-13 | 2014-05-14 | 昆明理工大学科技产业经营管理有限公司 | Synergistic leaching-copper arsenate removing method for leaching residues in high-iron zinc calcine and high-iron zinc sulfide concentrate |
| CN103911512A (en) * | 2014-04-28 | 2014-07-09 | 北京矿冶研究总院 | Method for removing arsenic and antimony from zinc smelting leaching solution |
| US20150225811A1 (en) * | 2012-08-07 | 2015-08-13 | Glencore Queensland Limited | Recovery of zinc from lead slag |
| CN105734300A (en) * | 2014-12-08 | 2016-07-06 | 云南云铜锌业股份有限公司 | Method for recovering copper from copper dust and immobilizing arsenic from copper dust into scorodite |
| CN106868306A (en) * | 2016-12-23 | 2017-06-20 | 河南豫光锌业有限公司 | A kind of method of zinc leaching residue valuable metal high efficiente callback |
| CN107012328A (en) * | 2017-03-10 | 2017-08-04 | 昆明理工大学 | A kind of high ferro zinc leaching residue clean utilization method |
| CN108330281A (en) * | 2018-03-16 | 2018-07-27 | 云锡文山锌铟冶炼有限公司 | Zinc abstraction reducing leaching device |
| CN112359213A (en) * | 2020-10-12 | 2021-02-12 | 矿冶科技集团有限公司 | Method for copper smelting hazardous waste co-processing and valuable metal comprehensive recovery |
| CN113684368A (en) * | 2021-08-29 | 2021-11-23 | 中南大学 | Method for co-processing arsenic sulfide slag and arsenic-containing smoke dust in copper smelting |
| CN113897491A (en) * | 2021-09-16 | 2022-01-07 | 昆明理工大学 | Method for comprehensively and efficiently treating zinc leaching residues |
-
2022
- 2022-01-28 CN CN202210107655.3A patent/CN114606400B/en active Active
Patent Citations (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4244734A (en) * | 1979-07-19 | 1981-01-13 | Hazen Research, Inc. | Process for recovering metal values from materials containing arsenic |
| JPS59145740A (en) * | 1983-02-07 | 1984-08-21 | Mitsubishi Metal Corp | Treatment of zinc leached slag |
| JP2000219920A (en) * | 1999-01-29 | 2000-08-08 | Dowa Mining Co Ltd | Method for removing and fixing aresenic from solution containing arsenic |
| JP2006265592A (en) * | 2005-03-23 | 2006-10-05 | Dowa Mining Co Ltd | Wet treatment method for zinc leaching residue |
| US20090019970A1 (en) * | 2005-10-19 | 2009-01-22 | Dundee Precious Metals Inc. | Process for recovery of metal values from materials containing arsenic and/or antimony |
| US20100050814A1 (en) * | 2006-11-02 | 2010-03-04 | Maurits Van Camp | Recovery of Non-Ferrous Metals from By-Products of the Zinc and Lead Industry using Electric Smelting with Submerged Plasma |
| US20150225811A1 (en) * | 2012-08-07 | 2015-08-13 | Glencore Queensland Limited | Recovery of zinc from lead slag |
| CN102851497A (en) * | 2012-09-21 | 2013-01-02 | 北京矿冶研究总院 | Method for treating arsenic-containing material |
| CN103789544A (en) * | 2014-02-13 | 2014-05-14 | 昆明理工大学科技产业经营管理有限公司 | Synergistic leaching-copper arsenate removing method for leaching residues in high-iron zinc calcine and high-iron zinc sulfide concentrate |
| CN103911512A (en) * | 2014-04-28 | 2014-07-09 | 北京矿冶研究总院 | Method for removing arsenic and antimony from zinc smelting leaching solution |
| CN105734300A (en) * | 2014-12-08 | 2016-07-06 | 云南云铜锌业股份有限公司 | Method for recovering copper from copper dust and immobilizing arsenic from copper dust into scorodite |
| CN106868306A (en) * | 2016-12-23 | 2017-06-20 | 河南豫光锌业有限公司 | A kind of method of zinc leaching residue valuable metal high efficiente callback |
| CN107012328A (en) * | 2017-03-10 | 2017-08-04 | 昆明理工大学 | A kind of high ferro zinc leaching residue clean utilization method |
| CN108330281A (en) * | 2018-03-16 | 2018-07-27 | 云锡文山锌铟冶炼有限公司 | Zinc abstraction reducing leaching device |
| CN112359213A (en) * | 2020-10-12 | 2021-02-12 | 矿冶科技集团有限公司 | Method for copper smelting hazardous waste co-processing and valuable metal comprehensive recovery |
| CN113684368A (en) * | 2021-08-29 | 2021-11-23 | 中南大学 | Method for co-processing arsenic sulfide slag and arsenic-containing smoke dust in copper smelting |
| CN113897491A (en) * | 2021-09-16 | 2022-01-07 | 昆明理工大学 | Method for comprehensively and efficiently treating zinc leaching residues |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115216628A (en) * | 2022-06-14 | 2022-10-21 | 云锡文山锌铟冶炼有限公司 | Method for removing copper and arsenic from copper and arsenic-containing acidic solution |
| CN115216628B (en) * | 2022-06-14 | 2023-09-22 | 云锡文山锌铟冶炼有限公司 | Method for removing copper and arsenic from copper-arsenic-containing acidic solution |
| CN115109920A (en) * | 2022-06-20 | 2022-09-27 | 云锡文山锌铟冶炼有限公司 | Method for reducing zinc and sulfur in hematite by using zinc hydrometallurgy system |
| CN115109920B (en) * | 2022-06-20 | 2023-09-22 | 云锡文山锌铟冶炼有限公司 | Method for reducing zinc and sulfur in hematite by zinc hydrometallurgy system |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114606400B (en) | 2023-09-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US6863873B1 (en) | Process to produce simonkolleite, zinc oxide and zinc hydroxide | |
| CN110104753B (en) | Method for removing arsenic from acidic arsenic-containing solution by using ferric salt | |
| US8747787B2 (en) | Method for producing raw material for ferronickel smelting from low grade nickel oxide ore | |
| US4004991A (en) | Two-stage pressure leaching process for zinc and iron bearing mineral sulphides | |
| CN114606400B (en) | Treatment method of high-iron arsenic-zinc-containing leaching residues | |
| CN111170510B (en) | Method for treating arsenic-containing wastewater and solidifying arsenic | |
| CA2468885C (en) | A method for precipitating iron from a zinc sulphate solution as hematite | |
| CN109574319A (en) | The solid arsenic technique of the high arsenic waste acid of non-ferrous metal metallurgy | |
| CA2856341A1 (en) | Method for producing high-purity nickel sulfate | |
| CN113684368A (en) | Method for co-processing arsenic sulfide slag and arsenic-containing smoke dust in copper smelting | |
| CN110983060B (en) | Method for resource utilization of arsenic filter cake and white smoke | |
| CN107324303B (en) | Method for separating refined iron and chromium from multi-metal hazardous waste | |
| JP2007314865A (en) | Method for treating arsenic-containing solution | |
| JP4846677B2 (en) | Arsenic-containing solution processing method | |
| US20080233023A1 (en) | Method for manufacturing scorodite | |
| JP2003512160A (en) | Method for reducing the concentration of dissolved metal and metalloid in aqueous solution | |
| AU2017218246A1 (en) | Sulfuration treatment method, sulfide production method, and hydrometallurgical process for nickel oxide ore | |
| CN115044778B (en) | Method for leaching zinc oxide and copper white smoke dust in mixed mode | |
| CN102925701A (en) | Method using wet alkaline process of cobalt-nickel (Co-Ni) residue containing arsenic to prepare arsenate | |
| CN110343873B (en) | Normal-pressure oxygen-enriched leaching method for bismuth sulfide concentrate in methanesulfonic acid system | |
| CN104471088B (en) | Ferric iron is removed with bloodstone form at ambient pressure | |
| US4107265A (en) | Treating residues from the leaching of roasted zinc blende | |
| US7455715B2 (en) | Heap bioleaching process for the extraction of zinc | |
| WO2019035319A1 (en) | Leaching treatment method, and wet smelting method of nickel oxide ore | |
| CN102010995B (en) | Method for increasing copper recovery rate in zinc hydrometallurgy process |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |