CN118166208B - Method for comprehensively recovering arsenic and valuable metals from copper smelting ash - Google Patents
Method for comprehensively recovering arsenic and valuable metals from copper smelting ash Download PDFInfo
- Publication number
- CN118166208B CN118166208B CN202410591732.6A CN202410591732A CN118166208B CN 118166208 B CN118166208 B CN 118166208B CN 202410591732 A CN202410591732 A CN 202410591732A CN 118166208 B CN118166208 B CN 118166208B
- Authority
- CN
- China
- Prior art keywords
- leaching
- copper smelting
- stirring
- valuable metals
- arsenic
- 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.)
- Active
Links
- 239000010949 copper Substances 0.000 title claims abstract description 56
- 238000003723 Smelting Methods 0.000 title claims abstract description 51
- 239000002184 metal Substances 0.000 title claims abstract description 51
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 51
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 50
- 238000000034 method Methods 0.000 title claims abstract description 42
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 229910052785 arsenic Inorganic materials 0.000 title claims abstract description 25
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 150000002739 metals Chemical class 0.000 title claims abstract description 20
- 238000002386 leaching Methods 0.000 claims abstract description 159
- 239000004071 soot Substances 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 229920000734 polysilsesquioxane polymer Polymers 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims description 37
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 36
- 239000002893 slag Substances 0.000 claims description 32
- 239000002253 acid Substances 0.000 claims description 29
- 230000003647 oxidation Effects 0.000 claims description 27
- 238000007254 oxidation reaction Methods 0.000 claims description 27
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 239000007788 liquid Substances 0.000 claims description 20
- 239000000706 filtrate Substances 0.000 claims description 18
- 239000007787 solid Substances 0.000 claims description 18
- 238000001914 filtration Methods 0.000 claims description 14
- 238000001556 precipitation Methods 0.000 claims description 13
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 12
- 229910052742 iron Inorganic materials 0.000 claims description 12
- 238000002791 soaking Methods 0.000 claims description 12
- 239000012747 synergistic agent Substances 0.000 claims description 10
- 229910052745 lead Inorganic materials 0.000 claims description 9
- BTHPQNDVYNQHBD-UHFFFAOYSA-N C(=C)C1=CC=C(C=C1)C1=C2NC(=C1)C=C1C=CC(=N1)C=C1C=CC(N1)=CC=1C=CC(N=1)=C2 Chemical compound C(=C)C1=CC=C(C=C1)C1=C2NC(=C1)C=C1C=CC(=N1)C=C1C=CC(N1)=CC=1C=CC(N=1)=C2 BTHPQNDVYNQHBD-UHFFFAOYSA-N 0.000 claims description 8
- 229910052797 bismuth Inorganic materials 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 7
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 7
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 7
- 238000005189 flocculation Methods 0.000 claims description 7
- 230000016615 flocculation Effects 0.000 claims description 7
- 239000004571 lime Substances 0.000 claims description 7
- 238000004064 recycling Methods 0.000 claims description 7
- 238000004062 sedimentation Methods 0.000 claims description 7
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 7
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 7
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 6
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 claims description 6
- 229910052793 cadmium Inorganic materials 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 230000003301 hydrolyzing effect Effects 0.000 claims description 6
- 230000003472 neutralizing effect Effects 0.000 claims description 6
- UOURRHZRLGCVDA-UHFFFAOYSA-D pentazinc;dicarbonate;hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Zn+2].[Zn+2].[Zn+2].[Zn+2].[Zn+2].[O-]C([O-])=O.[O-]C([O-])=O UOURRHZRLGCVDA-UHFFFAOYSA-D 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- 239000011780 sodium chloride Substances 0.000 claims description 6
- 229910052718 tin Inorganic materials 0.000 claims description 6
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- 239000011701 zinc Substances 0.000 claims description 6
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 claims description 4
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 4
- YIKSHDNOAYSSPX-UHFFFAOYSA-N 1-propan-2-ylthioxanthen-9-one Chemical compound S1C2=CC=CC=C2C(=O)C2=C1C=CC=C2C(C)C YIKSHDNOAYSSPX-UHFFFAOYSA-N 0.000 claims description 3
- 235000000126 Styrax benzoin Nutrition 0.000 claims description 3
- 244000028419 Styrax benzoin Species 0.000 claims description 3
- 235000008411 Sumatra benzointree Nutrition 0.000 claims description 3
- 229960002130 benzoin Drugs 0.000 claims description 3
- 235000019382 gum benzoic Nutrition 0.000 claims description 3
- 239000000126 substance Substances 0.000 abstract description 6
- 238000011084 recovery Methods 0.000 abstract description 5
- 239000012535 impurity Substances 0.000 abstract description 3
- 238000011161 development Methods 0.000 abstract description 2
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- 239000002910 solid waste Substances 0.000 abstract description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 15
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000003546 flue gas Substances 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- 229910000365 copper sulfate Inorganic materials 0.000 description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000012965 benzophenone Substances 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 235000021110 pickles Nutrition 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- -1 sulfhydryl free radical Chemical class 0.000 description 2
- JIHQDMXYYFUGFV-UHFFFAOYSA-N 1,3,5-triazine Chemical group C1=NC=NC=N1 JIHQDMXYYFUGFV-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- BWFPGXWASODCHM-UHFFFAOYSA-N copper monosulfide Chemical compound [Cu]=S BWFPGXWASODCHM-UHFFFAOYSA-N 0.000 description 1
- 238000007405 data analysis Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000007885 magnetic separation Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000004032 porphyrins Chemical group 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000009853 pyrometallurgy Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
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
- 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
- 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
- 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
- C22B19/00—Obtaining zinc or zinc oxide
- C22B19/20—Obtaining zinc otherwise than by distilling
- C22B19/22—Obtaining zinc otherwise than by distilling with leaching with acids
-
- 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
- C22B30/06—Obtaining bismuth
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Geochemistry & Mineralogy (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention provides a method for removing arsenic from copper smelting ash and comprehensively recovering valuable metals, which belongs to the technical field of comprehensive treatment of solid waste in the nonferrous metal smelting process, and the metal leaching synergist prepared by mercapto-alkene click chemical reaction can be more effectively reacted with arsenic and metal impurities in the copper smelting ash due to the special chemical structure, so that the leaching efficiency is improved; the cage structure of polysilsesquioxane provides excellent chemical stability, and the use of the synergist can improve the removal rate of harmful substances in copper smelting soot, reduce environmental pollution, improve the recovery rate of metal resources and meet the requirements of green chemistry and sustainable development. The invention realizes the centralized treatment of As and the fractional recovery of Cu, zn, pb, bi, in and other valuable metals.
Description
Technical Field
The invention relates to the technical field of comprehensive treatment of solid waste in a nonferrous metal smelting process, in particular to a method for removing arsenic from copper smelting ash and comprehensively recycling valuable metals.
Background
In the process of pyrometallurgy copper smelting, part of volatile elements such As Pb, zn, in, cd, bi and As in copper concentrate volatilize into flue gas, and then are collected and concentrated in the flue gas, and besides the elements, other various valuable elements enter the flue gas due to mechanical entrainment of air flow and the like.
The Chinese patent application with publication number CN104004916A discloses a multi-metal trapping process for bottom blowing reduction smelting of copper smelting ash leaching slag, which comprises the steps of mixing lead-silver-bismuth slag, copper slag, scrap iron, coal particles, solvent, reducing agent and return dust, putting the mixture into a bottom blowing furnace through a charging port, spraying oxygen-enriched gas into the furnace through a bottom spray gun, and obtaining copper-sulfur, reduction slag, flue gas and crude lead after high-efficiency reduction smelting, wherein the materials are dried by high-temperature flue gas passing through a rotary drying kiln; the oxygen-enriched air is a mixture of oxygen and natural gas; the furnace bottom spray gun forms 0-27 degrees with the vertical line; the oxygen flow is 70-100m 3/h, the pressure is 0.4-0.7MPa, the natural gas flow is 50-70m 3/h, and the pressure is 0.4-0.75MPa; the smelting area temperature is 1150-1250 deg.c, the molten pool depth is 800-1000cm and the negative pressure inside the furnace is 50-150P.
The Chinese patent with the publication number of CN102534228B discloses a method for comprehensively recovering valuable elements from high-arsenic copper smelting soot. The invention comprehensively recovers valuable elements in the high-arsenic copper smelting soot by the steps of (oxygen-enriched) roasting, leaching, extracting, replacing and crystallizing.
The Chinese patent with the publication number of CN108034830B discloses a method for comprehensively recovering valuable metals in copper smelting soot, which comprises the steps of firstly, carrying out preliminary separation on the copper smelting soot by adopting a magnetic separation method to obtain iron-rich soot and low-iron soot; leaching the iron-rich soot by sulfuric acid to obtain iron-rich slag and a copper sulfate solution; neutral leaching the low-iron ash to obtain neutral leaching slag and neutral leaching liquid; leaching the intermediate leaching slag by low acid liquor to obtain high-lead bismuth slag and pickle liquor, and returning the pickle liquor to neutral leaching; the immersion liquid is reduced by SO 2 to obtain As 2O3 and a copper sulfate solution, and the copper sulfate solution is electrodeposited to obtain pure copper.
The patent and the prior art are to comprehensively recycle valuable metals, and most copper smelting enterprises directly return the soot to a smelting system for treatment. However, after the ash is directly returned to the copper system, the processing capacity of the flash furnace is reduced, the furnace condition is deteriorated, harmful components such As Pb, zn, as and the like in the furnace charge are increased, and the quality of the final product is directly affected by the circulating accumulation of various harmful impurities.
Disclosure of Invention
The invention aims to solve the problems that the treatment capacity of a flash furnace is affected, harmful components such As Pb, zn, as and the like in furnace charge are increased and the like in the current comprehensive recovery process of valuable metals, and provides a method for removing arsenic from copper smelting ash and comprehensively recovering the valuable metals, which comprises the following steps: pretreatment and oxidation acid leaching; the method comprises the following steps: the pretreated leaching slag is sent to oxidation acid leaching after being washed by water, and the oxidation acid leaching adopts a two-stage countercurrent mode, and the operation steps are as follows:
A1 first stage leaching: continuously introducing air in the leaching process, adding water and stirring, wherein the liquid-solid ratio is (3-4): 1, adding 60-70g/l sulfuric acid at 70-80 ℃ for 2-4h; extracting In from the leaching solution by tributyl phosphate; extracting Cu from raffinate; preparing basic zinc carbonate from raffinate;
A2 second stage leaching: continuously introducing air in the leaching process, adding water and stirring, wherein the liquid-solid ratio is (3-4): 1, adding 120-130g/l sulfuric acid and 10-15g/l sodium chloride at the temperature of 70-80 ℃ and 0.02-0.3g/l metal leaching synergistic agent to react for 2-4h, and returning the second-stage leaching liquid to the first-stage leaching for recycling; neutralizing and hydrolyzing the leaching solution, and separating Bi; and (5) reducing and smelting leaching slag, and recovering Pb.
In the method, the pretreatment operation steps are as follows:
s1, alkaline leaching: adding copper smelting ash into a stirring kettle, adding water and stirring, wherein the liquid-solid ratio is (4-5): 1, continuously adding 40-50g/l of sodium hydroxide and 30-40g/l of sodium sulfide, heating, soaking and filtering to obtain leaching liquid and leaching residues;
S2, sedimentation: adding 10-20g/l lime into the leaching solution of the step S1 for precipitation, filtering, and continuously adding 5-10g/l polyaluminium chloride into the filtrate for flocculation precipitation to obtain filtrate and filter residues; the filter residue is arsenic residue;
S3: returning the filtrate of the step S2 to the stirring kettle of the step S1 to serve as circulating liquid; and (3) delivering the leached slag of the S1 into oxidation acid leaching for continuous treatment.
In the method, the main components of the copper smelting ash are as follows: 7.18% Cu, 23.05% Pb, 4.09% Bi, 10.91% Zn, 6.01% As, 1.56% Cd, 4.05% Fe, 1.18% Sn, 0.595% Sb, and 0.021% in.
In the method, the soaking temperature of the S1 is 60-70 ℃, the leaching time is 60-120min, and the stirring speed is 500-600rpm.
In the method, the preparation method of the metal leaching synergistic agent comprises the following steps:
According to the weight portions, 5 to 10 portions of trimercapto-s-triazine sodium salt, 0.07 to 0.2 portion of 5,10,15, 20-tetra (4-vinyl phenyl) porphyrin, 0.6 to 2.5 portions of acrylic group-cage polysilsesquioxane (CAS: 221326-46-1), 120 to 160 portions of toluene and 0.5 to 2.5 portions of photoinitiator are stirred and reacted for 50 to 100 minutes under 365nm ultraviolet irradiation, and toluene is removed by reduced pressure distillation after the reaction is finished, thus obtaining the metal leaching synergistic agent.
In the method, the photoinitiator is one of 2, 2-dimethoxy-2-phenylacetophenone, benzophenone, benzoin dimethyl ether and isopropyl thioxanthone.
Reaction mechanism of metal leaching synergist:
Under the illumination condition, the photoinitiator (such as benzoin dimethyl ether, benzophenone and the like) is activated to generate free radicals; the free radical generated by the photoinitiator reacts with the sulfhydryl group in the sodium salt of the trimercapto-s-triazine to form a sulfhydryl free radical.
The sulfhydryl free radical then undergoes an addition reaction with the vinyl double bond in the 5,10,15, 20-tetra (4-vinyl phenyl) porphyrin and the acrylic-group-cage polysilsesquioxane to form a thioether bond, thereby bonding the s-triazine, porphyrin structure and polysilsesquioxane skeleton together.
Compared with the prior art, the invention has the following beneficial effects:
1. The metal leaching synergist prepared by the mercapto-alkene click chemical reaction can more effectively react with arsenic and metal impurities in copper smelting ash due to the special chemical structure, so that the leaching efficiency is improved; the cage-shaped structure of polysilsesquioxane provides excellent chemical stability, and the use of the synergist can improve the removal rate of harmful substances in copper smelting soot, reduce environmental pollution, improve the recovery rate of metal resources and meet the requirements of green chemistry and sustainable development;
2. The copper smelting ash adopts an alkaline leaching dearsenification pretreatment and two-stage countercurrent oxidation acid leaching process, namely, the copper smelting ash is firstly subjected to alkaline leaching by a sodium hydroxide and sodium sulfide system to remove As, so that the centralized treatment of As is realized; the leaching solution is subjected to As treatment of lime precipitation and polyaluminium chloride flocculation sedimentation, alkali liquor can be recycled, and leaching residues are sent to oxidation acid leaching; the oxidation acid leaching adopts a two-stage countercurrent mode, and after acid leaching, the valuable metals such as Cu, zn, pb, bi, in and the like are recovered step by step after extraction.
Detailed Description
Various exemplary embodiments of the invention will now be described in detail, which should not be considered as limiting the invention, but rather as more detailed descriptions of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. In addition, for numerical ranges in this disclosure, it is understood that each intermediate value between the upper and lower limits of the ranges is also specifically disclosed. Every smaller range between any stated value or stated range, and any other stated value or intermediate value within the stated range, is also encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
The testing method comprises the following steps:
1. arsenic removal rate:
；
Wherein: c 0 represents the initial concentration of As in the solution; v 0 represents the initial solution volume; c t represents the residual As concentration of the solution obtained by filtration after the treatment; v t represents the volume of the solution obtained by filtration after the treatment.
2. Leaching rate:
；
wherein: m 0 is the weight of each test raw material, x 0 is the content of a certain metal element in the raw material, m 1 is the weight of leaching slag (calculated as dry slag), and x 1 is the content of a certain metal element in leaching slag.
Example 1: the method for comprehensively recovering the arsenic removal and valuable metals of the copper smelting ash comprises the following steps: pretreatment and oxidation acid leaching.
The pretreatment operation steps are as follows:
S1, alkaline leaching: adding copper smelting ash into a stirring kettle, adding water and stirring, wherein the liquid-solid ratio is 4:1, continuously adding 40g/l of sodium hydroxide and 30g/l of sodium sulfide, heating, soaking and filtering to obtain leaching liquid and leaching residues;
S2, sedimentation: adding 10g/l lime into the leaching solution of the step S1 for precipitation and filtering, and then continuously adding 5g/l polyaluminium chloride into the filtrate for flocculation and precipitation to obtain filtrate and filter residues; the filter residue is arsenic residue;
S3: returning the filtrate of the step S2 to the stirring kettle of the step S1 to serve as circulating liquid; and (3) delivering the leached slag of the S1 into oxidation acid leaching for continuous treatment.
The main components of the copper smelting ash are as follows: 7.18% Cu, 23.05% Pb, 4.09% Bi, 10.91% Zn, 6.01% As, 1.56% Cd, 4.05% Fe, 1.18% Sn, 0.595% Sb, and 0.021% in.
The soaking temperature of the S1 is 60 ℃, the leaching time is 60min, and the stirring rotating speed is 500rpm.
The pretreated leaching slag is sent to oxidation acid leaching after being washed by water, and the oxidation acid leaching adopts a two-stage countercurrent mode, and the operation steps are as follows:
A1 first stage leaching: continuously introducing air in the leaching process, adding water and stirring, wherein the liquid-solid ratio is 3:1, adding 60g/l sulfuric acid at 70 ℃ for 2h; extracting In from the leaching solution by tributyl phosphate; extracting Cu from raffinate; preparing basic zinc carbonate from raffinate;
A2 second stage leaching: continuously introducing air in the leaching process, adding water and stirring, wherein the liquid-solid ratio is 3:1, adding 120g/l sulfuric acid and 10g/l sodium chloride at 70 ℃ and 0.02g/l metal leaching synergistic agent to react for 2 hours, and returning the second-stage leaching liquid to the first-stage leaching for recycling; neutralizing and hydrolyzing the leaching solution, and separating Bi; and (5) reducing and smelting leaching slag, and recovering Pb.
The preparation method of the metal leaching synergist comprises the following steps:
5g of trimercapto-s-triazine sodium salt, 0.07g of 5,10,15, 20-tetra (4-vinyl phenyl) porphyrin, 0.6g of acrylic group-cage polysilsesquioxane (CAS: 221326-46-1), 120g of toluene and 0.5g of photoinitiator are stirred and reacted for 50 minutes under 365nm ultraviolet light irradiation, and after the reaction is finished, the toluene is distilled off under reduced pressure to obtain the metal leaching synergistic agent.
The photoinitiator is 2, 2-dimethoxy-2-phenyl acetophenone.
Example 2: the method for comprehensively recovering the arsenic removal and valuable metals of the copper smelting ash comprises the following steps: pretreatment and oxidation acid leaching.
The pretreatment operation steps are as follows:
s1, alkaline leaching: adding copper smelting ash into a stirring kettle, adding water and stirring, wherein the liquid-solid ratio is 4:1, continuously adding 44g/l of sodium hydroxide and 34g/l of sodium sulfide, heating, soaking and filtering to obtain leaching liquid and leaching slag;
s2, sedimentation: adding 14g/l lime into the leaching solution of the step S1 for precipitation, filtering, and continuously adding 6g/l polyaluminium chloride into the filtrate for flocculation precipitation to obtain filtrate and filter residues; the filter residue is arsenic residue;
S3: returning the filtrate of the step S2 to the stirring kettle of the step S1 to serve as circulating liquid; and (3) delivering the leached slag of the S1 into oxidation acid leaching for continuous treatment.
The main components of the copper smelting ash are as follows: 7.18% Cu, 23.05% Pb, 4.09% Bi, 10.91% Zn, 6.01% As, 1.56% Cd, 4.05% Fe, 1.18% Sn, 0.595% Sb, and 0.021% in.
The soaking temperature of the S1 is 65 ℃, the leaching time is 80min, and the stirring rotating speed is 550rpm.
The pretreated leaching slag is sent to oxidation acid leaching after being washed by water, and the oxidation acid leaching adopts a two-stage countercurrent mode, and the operation steps are as follows:
A1 first stage leaching: continuously introducing air in the leaching process, adding water and stirring, wherein the liquid-solid ratio is 3:1, adding 64g/l sulfuric acid at 75 ℃ for reaction for 3 hours; extracting In from the leaching solution by tributyl phosphate; extracting Cu from raffinate; preparing basic zinc carbonate from raffinate;
A2 second stage leaching: continuously introducing air in the leaching process, adding water and stirring, wherein the liquid-solid ratio is 3:1, adding 124g/l sulfuric acid and 12g/l sodium chloride at the temperature of 75 ℃ and 0.1g/l metal leaching synergistic agent to react for 3 hours, and returning the second-stage leaching liquid to the first-stage leaching for recycling; neutralizing and hydrolyzing the leaching solution, and separating Bi; and (5) reducing and smelting leaching slag, and recovering Pb.
The preparation method of the metal leaching synergist comprises the following steps:
6g of trimercapto-s-triazine sodium salt, 0.1g of 5,10,15, 20-tetra (4-vinylphenyl) porphyrin, 1g of acrylic group-cage polysilsesquioxane (CAS: 221326-46-1), 130g of toluene and 1g of photoinitiator are stirred and reacted for 70 minutes under 365nm ultraviolet light irradiation, and after the reaction is finished, the toluene is distilled off under reduced pressure to obtain the metal leaching synergist.
The photoinitiator is 2, 2-dimethoxy-2-phenyl acetophenone.
Example 3: the method for comprehensively recovering the arsenic removal and valuable metals of the copper smelting ash comprises the following steps: pretreatment and oxidation acid leaching.
The pretreatment operation steps are as follows:
S1, alkaline leaching: adding copper smelting ash into a stirring kettle, adding water and stirring, wherein the liquid-solid ratio is 5:1, continuously adding 48g/l of sodium hydroxide and 38g/l of sodium sulfide, heating, soaking and filtering to obtain leaching liquid and leaching slag;
S2, sedimentation: adding 18g/l lime into the leaching solution of the step S1 for precipitation, filtering, and continuously adding 8g/l polyaluminium chloride into the filtrate for flocculation precipitation to obtain filtrate and filter residues; the filter residue is arsenic residue;
S3: returning the filtrate of the step S2 to the stirring kettle of the step S1 to serve as circulating liquid; and (3) delivering the leached slag of the S1 into oxidation acid leaching for continuous treatment.
The main components of the copper smelting ash are as follows: 7.18% Cu, 23.05% Pb, 4.09% Bi, 10.91% Zn, 6.01% As, 1.56% Cd, 4.05% Fe, 1.18% Sn, 0.595% Sb, and 0.021% in.
The soaking temperature of the S1 is 65 ℃, the leaching time is 100min, and the stirring rotating speed is 550rpm.
The pretreated leaching slag is sent to oxidation acid leaching after being washed by water, and the oxidation acid leaching adopts a two-stage countercurrent mode, and the operation steps are as follows:
A1 first stage leaching: continuously introducing air in the leaching process, adding water and stirring, wherein the liquid-solid ratio is 4:1, adding 68g/l sulfuric acid at 75 ℃ for reaction for 3 hours; extracting In from the leaching solution by tributyl phosphate; extracting Cu from raffinate; preparing basic zinc carbonate from raffinate;
A2 second stage leaching: continuously introducing air in the leaching process, adding water and stirring, wherein the liquid-solid ratio is 4:1, adding 128g/l sulfuric acid and 14g/l sodium chloride at the temperature of 75 ℃, reacting 0.2g/l metal leaching synergistic agent for 3 hours, and returning the second-stage leaching liquid to the first-stage leaching for recycling; neutralizing and hydrolyzing the leaching solution, and separating Bi; and (5) reducing and smelting leaching slag, and recovering Pb.
The preparation method of the metal leaching synergist comprises the following steps:
8g of trimercapto-s-triazine sodium salt, 0.15g of 5,10,15, 20-tetra (4-vinylphenyl) porphyrin, 2g of acrylic group-cage polysilsesquioxane (CAS: 221326-46-1), 150g of toluene and 2g of photoinitiator are stirred and reacted for 90 minutes under 365nm ultraviolet light irradiation, and after the reaction is finished, the toluene is distilled off under reduced pressure to obtain the metal leaching synergist.
The photoinitiator is diphenyl ketone.
Example 4: the method for comprehensively recovering the arsenic removal and valuable metals of the copper smelting ash comprises the following steps: pretreatment and oxidation acid leaching.
The pretreatment operation steps are as follows:
S1, alkaline leaching: adding copper smelting ash into a stirring kettle, adding water and stirring, wherein the liquid-solid ratio is 5:1, continuously adding 50g/l of sodium hydroxide and 40g/l of sodium sulfide, heating, soaking and filtering to obtain leaching liquid and leaching slag;
S2, sedimentation: adding 20g/l lime into the leaching solution of the step S1 for precipitation, filtering, and continuously adding 10g/l polyaluminium chloride into the filtrate for flocculation precipitation to obtain filtrate and filter residues; the filter residue is arsenic residue;
S3: returning the filtrate of the step S2 to the stirring kettle of the step S1 to serve as circulating liquid; and (3) delivering the leached slag of the S1 into oxidation acid leaching for continuous treatment.
The main components of the copper smelting ash are as follows: 7.18% Cu, 23.05% Pb, 4.09% Bi, 10.91% Zn, 6.01% As, 1.56% Cd, 4.05% Fe, 1.18% Sn, 0.595% Sb, and 0.021% in.
The soaking temperature of the S1 is 70 ℃, the leaching time is 120min, and the stirring rotating speed is 600rpm.
The pretreated leaching slag is sent to oxidation acid leaching after being washed by water, and the oxidation acid leaching adopts a two-stage countercurrent mode, and the operation steps are as follows:
A1 first stage leaching: continuously introducing air in the leaching process, adding water and stirring, wherein the liquid-solid ratio is 4:1, adding 70g/l sulfuric acid at 80 ℃ for reaction for 4 hours; extracting In from the leaching solution by tributyl phosphate; extracting Cu from raffinate; preparing basic zinc carbonate from raffinate;
A2 second stage leaching: continuously introducing air in the leaching process, adding water and stirring, wherein the liquid-solid ratio is 4:1, adding 130g/l sulfuric acid and 15g/l sodium chloride at the temperature of 80 ℃ and 0.3g/l metal leaching synergistic agent to react for 4 hours, and returning the second-stage leaching liquid to the first-stage leaching for recycling; neutralizing and hydrolyzing the leaching solution, and separating Bi; and (5) reducing and smelting leaching slag, and recovering Pb.
The preparation method of the metal leaching synergist comprises the following steps:
10g of trimercapto-s-triazine sodium salt, 0.2g of 5,10,15, 20-tetra (4-vinyl phenyl) porphyrin, 2.5g of acrylic group-cage polysilsesquioxane (CAS: 221326-46-1), 160g of toluene and 2.5g of photoinitiator are stirred and reacted for 100 minutes under the irradiation of 365nm ultraviolet light, and after the reaction is finished, the toluene is distilled off under reduced pressure to obtain the metal leaching synergistic agent.
The photoinitiator is isopropyl thioxanthone.
Comparative example 1: this example was conducted in the same manner as example 1 except that no metal leaching synergist was added.
Comparative example 2: this example was performed in the same manner as in example 1, except that 5,10,15, 20-tetrakis (4-vinylphenyl) porphyrin was not added.
Comparative example 3: this example was the same as example 1 except that acrylic-cage polysilsesquioxane was not added.
Table 1: test results for each example and comparative example
Through the data analysis of the above examples and comparative examples, the arsenic removal rate of the invention is high, the leaching rate of valuable metals such as Cu, zn, pb, bi, in is high, and the step recovery is realized.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (5)
1. The method for comprehensively recovering the arsenic removal and valuable metals of the copper smelting ash is characterized by comprising the following steps of: the method comprises the following steps: pretreatment and oxidation acid leaching; the method comprises the following steps: the pretreated leaching slag is sent to oxidation acid leaching after being washed by water, and the oxidation acid leaching adopts a two-stage countercurrent mode, and the operation steps are as follows:
A1 first stage leaching: continuously introducing air in the leaching process, adding water and stirring, wherein the liquid-solid ratio is (3-4): 1, adding 60-70g/l sulfuric acid at 70-80 ℃ for 2-4h; extracting In from the leaching solution by tributyl phosphate; extracting Cu from raffinate; preparing basic zinc carbonate from raffinate;
A2 second stage leaching: continuously introducing air in the leaching process, adding water and stirring, wherein the liquid-solid ratio is (3-4): 1, adding 120-130g/l sulfuric acid and 10-15g/l sodium chloride at the temperature of 70-80 ℃ and 0.02-0.3g/l metal leaching synergistic agent to react for 2-4h, and returning the second-stage leaching liquid to the first-stage leaching for recycling; neutralizing and hydrolyzing the leaching solution, and separating Bi; reducing and smelting leaching slag, and recovering Pb;
the preparation method of the metal leaching synergist comprises the following steps:
5 to 10 parts of trimercapto-s-triazine sodium salt and 0.07 to 0.2 part of 5,10,15, 20-tetra (4-
Vinyl phenyl) porphyrin, 0.6-2.5 parts of acrylic group-cage polysilsesquioxane, 120-160 parts of toluene,
And (3) 0.5-2.5 parts of photoinitiator, stirring and reacting for 50-100 minutes under 365nm ultraviolet irradiation, and distilling under reduced pressure to remove toluene after the reaction is finished to obtain the metal leaching synergist.
2. The method for comprehensively recovering arsenic and valuable metals from copper smelting soot according to claim 1, which is characterized in that: the pretreatment operation steps are as follows:
s1, alkaline leaching: adding copper smelting ash into a stirring kettle, adding water and stirring, wherein the liquid-solid ratio is (4-5): 1, continuously adding 40-50g/l of sodium hydroxide and 30-40g/l of sodium sulfide, heating, soaking and filtering to obtain leaching liquid and leaching residues;
S2, sedimentation: adding 10-20g/l lime into the leaching solution of the step S1 for precipitation, filtering, and continuously adding 5-10g/l polyaluminium chloride into the filtrate for flocculation precipitation to obtain filtrate and filter residues; the filter residue is arsenic residue;
S3: returning the filtrate of the step S2 to the stirring kettle of the step S1 to serve as circulating liquid; and (3) delivering the leached slag of the S1 into oxidation acid leaching for continuous treatment.
3. The method for comprehensively recovering arsenic and valuable metals from copper smelting soot according to claim 2, which is characterized in that: the main components of the copper smelting ash are as follows: 7.18% Cu, 23.05% Pb, 4.09% Bi, 10.91% Zn, 6.01% As, 1.56% Cd, 4.05% Fe, 1.18% Sn, 0.595% Sb, and 0.021% in.
4. The method for comprehensively recovering arsenic and valuable metals from copper smelting soot according to claim 2, which is characterized in that: the soaking temperature of the S1 is 60-70 ℃, the leaching time is 60-120min, and the stirring rotating speed is 500-600rpm.
5. The method for comprehensively recovering arsenic and valuable metals from copper smelting soot according to claim 1, which is characterized in that: the photoinitiator is one of 2, 2-dimethoxy-2-phenyl acetophenone, diphenyl ketone, benzoin dimethyl ether and isopropyl thioxanthone.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410591732.6A CN118166208B (en) | 2024-05-14 | 2024-05-14 | Method for comprehensively recovering arsenic and valuable metals from copper smelting ash |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410591732.6A CN118166208B (en) | 2024-05-14 | 2024-05-14 | Method for comprehensively recovering arsenic and valuable metals from copper smelting ash |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN118166208A CN118166208A (en) | 2024-06-11 |
| CN118166208B true CN118166208B (en) | 2024-07-23 |
Family
ID=91351375
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202410591732.6A Active CN118166208B (en) | 2024-05-14 | 2024-05-14 | Method for comprehensively recovering arsenic and valuable metals from copper smelting ash |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN118166208B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102534228A (en) * | 2012-03-12 | 2012-07-04 | 中南大学 | Method for comprehensively recovering valuable elements from high-arsenic-containing copper smelting soot |
| CN106834708A (en) * | 2016-12-21 | 2017-06-13 | 中南大学 | A kind of integrated conduct method of arsenic-containing smoke dust |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6015824B2 (en) * | 2015-07-30 | 2016-10-26 | 住友金属鉱山株式会社 | Processing method of copper smelting ash |
| CN113149310A (en) * | 2021-03-26 | 2021-07-23 | 张加余 | Method for treating and recycling smelting wastewater |
-
2024
- 2024-05-14 CN CN202410591732.6A patent/CN118166208B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102534228A (en) * | 2012-03-12 | 2012-07-04 | 中南大学 | Method for comprehensively recovering valuable elements from high-arsenic-containing copper smelting soot |
| CN106834708A (en) * | 2016-12-21 | 2017-06-13 | 中南大学 | A kind of integrated conduct method of arsenic-containing smoke dust |
Also Published As
| Publication number | Publication date |
|---|---|
| CN118166208A (en) | 2024-06-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO2023030165A1 (en) | Method for co-processing copper-smelting arsenic sulfide slag and arsenic-containing soot | |
| CN101660054B (en) | Method for extracting metal indium from waste residues generated from lead and zinc smelting | |
| CN112359213A (en) | Method for copper smelting hazardous waste co-processing and valuable metal comprehensive recovery | |
| CN113549766B (en) | Method for removing arsenic from lead smelting smoke dust and recovering valuable metals | |
| CN101209853B (en) | Method for preparing cupric sulfate from spongy copper and copper-containing acid pickle | |
| CN101994008B (en) | Zinc-cobalt separation process for producing nickel-cobalt slag by zinc smelting purification | |
| CN106636656A (en) | Method for recovering valuable metal from copper smelting white smoke | |
| CN105463197A (en) | Method for recycling valuable metal from copper smelting white smoke | |
| CN111647754A (en) | Comprehensive utilization method of zinc-containing dust and sludge in steel plant | |
| CN114314661B (en) | Method for producing high-purity ammonium metavanadate by deep cobalt removal of vanadium raw material | |
| CN110585865B (en) | Method for treating zinc smelting sulfur dioxide flue gas by using zinc hydrometallurgy iron-containing precipitation slag | |
| CN106834707A (en) | A kind of method of arsenic-containing material synthetical recovery and arsenic recycling | |
| CN113621818A (en) | Method for co-processing copper smelting waste acid and arsenic-containing smoke dust | |
| CN112609084A (en) | Comprehensive treatment method for smoke dust with high zinc, lead and tin contents in fuming furnace | |
| CN101798639B (en) | Method for recovering indium from indium-containing neutralized dregs directly leached from zinc concentrate | |
| CN113088710A (en) | Method for separating copper and germanium from copper and germanium replacement slag | |
| CN109306408B (en) | Method for removing arsenic from ilmenite smoke dust and recycling valuable metals | |
| CN118166208B (en) | Method for comprehensively recovering arsenic and valuable metals from copper smelting ash | |
| CN106591586B (en) | A kind of method of more metal recoveries in Copper making white cigarette dirt | |
| CN115537569B (en) | Comprehensive utilization method of zinc hydrometallurgy sodium cobalt slag | |
| CN116574908A (en) | Process for jointly recycling zinc and indium by means of open-circuit impurity removal of electrolyte in zinc smelting process | |
| CN110607444B (en) | Novel treatment method for copper and tin slag removal | |
| CN113881857A (en) | Method for treating cobalt-containing solution produced in wet zinc smelting cadmium recovery process | |
| Thorsen et al. | The integrated organic leaching-solvent extraction operation in hydrometallurgy | |
| EP0010365A1 (en) | Treatment of zinc plant leach residues for recovery of the contained metal values |
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 |