CN113769897B - Method for degrading organic flotation reagent in ore pulp - Google Patents
Method for degrading organic flotation reagent in ore pulp Download PDFInfo
- Publication number
- CN113769897B CN113769897B CN202110861829.0A CN202110861829A CN113769897B CN 113769897 B CN113769897 B CN 113769897B CN 202110861829 A CN202110861829 A CN 202110861829A CN 113769897 B CN113769897 B CN 113769897B
- Authority
- CN
- China
- Prior art keywords
- ore
- ore pulp
- oxidative degradation
- strong oxidant
- acid
- 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
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D1/00—Flotation
- B03D1/12—Agent recovery
-
- 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
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a method for degrading an organic flotation reagent in ore pulp. The method is to carry out selective oxidative degradation on organic flotation agents in ore pulp containing sulfide ores and/or oxide ores under the synergistic action of oxidizing acid and strong oxidizer. The method is suitable for various mineral flotation systems, is simple, strong in selectivity, remarkable in effect and short in action time, and has important significance for solving the problems that drainage organic matters out of ore dressing exceed the standard, ore dressing and smelting combined pretreatment is performed to overflow a trough, and harmful gases are released by drying a concentrate product.
Description
Technical Field
The invention relates to a method for degrading an organic flotation reagent in ore pulp, in particular to a chemical degradation method for the organic flotation reagent adsorbed on the surface of a mineral and in an ore pulp solution, and belongs to the field of ore dressing technology utilization and environmental protection.
Background
In recent years, the mineral engineering industry is fierce and the intersection among industries is deepened increasingly. On the one hand, the mineral engineering field is constantly researching new organic flotation reagents to improve production indexes. The organic medicine mainly comprises xanthic acid collecting agent, sulfur nitrogen sulfur amino acid ester collecting agent, fatty acid collecting agent, amine collecting agent, hydroximic acid collecting agent, alcohol foaming agent, starch inhibitor and other organic inhibitors. The collector is characterized by long hydrocarbon chain, multiple functional groups and complex structure, and usually acts on the surface of a mineral in a form of strong chemical adsorption, so that the selectivity and the collecting property are obviously improved compared with those of the traditional collector. The organic agent brings benefits, and simultaneously causes the problems of overproof organic matter content of discharged water, difficult flotation and reagent removal of different minerals, harsh drying environment of concentrate products and the like.
On the other hand, mineral resources are continuously mined, the properties of ores are increasingly complex, and the dressing and smelting combined process gradually becomes the mainstream. The key of the combination of dressing and metallurgy lies in the connection of dressing and metallurgy, and the concentrate product of dressing can enter the main process after being used as a raw material to enter metallurgy through pretreatment. When the organic flotation reagent acts on the surface of the mineral in a form of strong chemical adsorption, the organic flotation reagent cannot be degraded by concentration, filter pressing, drying and the like, so that when the organic flotation reagent enters the pretreatment stage of a metallurgical acid method, a thick foam layer which is not easy to combine and break is formed at a gas-liquid interface along with bubbles generated by calcite, the phenomena of overflow of a tank and the like are caused, the loss of the concentrate is increased, and the efficiency of the process and the continuity of operation are influenced.
Although there are many methods for treating organic matter in water, there are few methods for treating organic agents in pulp systems. A single strong oxidant, such as a strong oxidant oxidation method of potassium permanganate and the like, has poor selectivity and low treatment efficiency; catalytic oxidation processes are both highly efficient and costly. Two or more groups of strong oxidizers are matched for use, so that the treatment efficiency is improved, and the two or more groups of strong oxidizers can be directionally degraded as required. If the organic medicament in the ore pulp is treated by the method, the key of the technology is how to selectively degrade the organic substances and how to improve the degradation efficiency.
Disclosure of Invention
Aiming at the technical problem that the organic flotation agent in the ore pulp is difficult to be directly and efficiently oxidized and degraded by a chemical agent in the prior art, the invention aims to provide a method for degrading the organic flotation agent in the ore pulp, which aims at ore pulp systems of different types of minerals, utilizes different types of oxidants to match and use the organic flotation agent in the surface of the flotation mineral and the ore pulp solution according to different proportions, can realize the efficient degradation of residual or excessive organic flotation agent in the ore dressing process, simultaneously reduces the consumption of the oxidation agent, can effectively prevent metal ions in the minerals from dissolving out by pertinently and selectively degrading the specific organic flotation agent in the specific mineral ore pulp system, does not influence the agents adsorbed on the surfaces of other minerals, can solve the problem of non-purpose mineral enrichment caused by excessive agents, and can weaken the release of harmful gas in the drying process of flotation concentrate, the problems of overproof organic matters in the mineral water, difficult combination of mineral separation and metallurgy and the like can be solved, and the aims of effectively linking different mineral flotation, mineral water discharge and mineral separation and metallurgy are fulfilled.
In order to achieve the technical purpose, the invention provides a method for degrading organic flotation agents in ore pulp, which is characterized in that the organic flotation agents in ore pulp containing sulfide ores and/or oxide ores are subjected to selective oxidative degradation under the synergistic action of oxidizing acids and strong oxidizers.
As a preferred embodiment, the ore pulp containing sulphide ore contains xanthate collectors and/or thiamine collectors. It also generally comprises customary foaming agents, inhibitors and the like, such as in particular alcoholic foaming agents and starch inhibitors.
As a preferable scheme, the ore pulp containing the oxidized ore contains at least one of a fatty acid collector, a hydroximic acid collector and an amine collector. Typically, conventional foaming agents and the like, such as alcoholic foaming agents, are also included.
As a preferable scheme, the slurry containing the sulphide ore and the oxidized ore contains at least one of xanthate collectors, thiamine collectors, fatty acid collectors, hydroximic acid collectors and amine collectors. Typically, conventional foaming agents, such as alcoholic foaming agents, are also included.
As a preferred embodiment, the oxidizing acid includes concentrated sulfuric acid and/or nitric acid;
as a preferred embodiment, the strong oxidizer includes at least one of peroxide, perchlorate and permanganate. The peroxide is common inorganic peroxide such as hydrogen peroxide, sodium peroxide and the like. Perchlorates such as potassium perchlorate, sodium perchlorate and the like are common perchlorates. Permanganate such as potassium permanganate and the like are common permanganate salts.
As a preferable scheme, for the selective oxidative degradation of the organic flotation reagent in the ore pulp containing the sulfide ore, the volume percentage composition of the strong oxidant and the oxidizing acid is 50-90% to 50-10%, wherein the strong oxidant is added in the form of a solution with the mass percentage concentration of 40-60%, the total adding amount of the strong oxidant and the oxidizing acid in the ore pulp is 0.01-200 g/L, and the oxidative degradation time is 0.5-2 min. The total adding amount of the strong oxidant and the oxidizing acid in the ore pulp is further preferably 50-150 g/L, the volume percentage composition of the strong oxidant and the oxidizing acid is 60-70% and 40-30%, and the oxidative degradation time is 0.5-1.5 min. Under the optimized conditions, the efficient degradation of common flotation agents in the ore pulp containing sulfide ores can be realized.
As a preferable scheme, for the selective oxidative degradation of the organic flotation reagent in the ore pulp containing the oxidized ore, the volume percentage composition of the strong oxidant and the oxidizing acid is 10-30% to 90-70%, the total adding amount of the strong oxidant and the oxidizing acid in the ore pulp is 300-800 g/L, and the oxidative degradation time is 3-6 min. The total adding amount of the strong oxidant and the oxidizing acid in the ore pulp is further preferably 400-600 g/L, the volume percentage composition of the strong oxidant and the oxidizing acid is 15-30% and 85-70% for selective oxidative degradation of the organic flotation reagent in the oxidized ore pulp, and the oxidative degradation time is 4-5 min. Under the optimized conditions, the efficient degradation of common flotation agents in ore pulp containing oxidized ores can be realized.
As a preferable scheme, for the selective oxidative degradation of the organic flotation reagent in the ore pulp containing the oxidized ore and the sulfide ore, the volume percentage composition of the strong oxidant and the oxidizing acid is 30-50% to 70-50%, the total adding amount of the strong oxidant and the oxidizing acid in the ore pulp is 200-300 g/L, and the oxidative degradation time is 2-3 min. The total adding amount of the strong oxidant and the oxidizing acid in the ore pulp is further preferably 200-250 g/L, and for selective oxidative degradation of an organic flotation reagent in the mixed ore pulp of the oxidized ore and the sulfide ore, the volume percentage composition of the strong oxidant and the oxidizing acid is 35-45%, 65-55%, and the oxidative degradation time is 2-3 min. Under the optimized conditions, the efficient degradation of common flotation agents in mixed ore pulp containing oxidized ore and sulfide ore can be realized.
As a preferable scheme, the oxidizing acid and the strong oxidizer are mixed in advance and fully stirred, and then directly added into the ore pulp containing the sulfide ore and/or the oxide ore for oxidative degradation. The oxidizing acid and the strong oxidant are mixed in advance and fully stirred for more than 1 min.
Compared with the prior art, the technical scheme of the invention has the following beneficial technical effects:
the key point of the technical scheme of the invention is that aiming at an ore pulp system consisting of different minerals and different organic flotation reagents, the selective oxidative degradation of the organic flotation reagents in the ore pulp system is realized by controlling the conditions of the type, the concentration, the proportion, the acting time and the like of two or more oxidants. Numerous studies have shown that: in the sulfide ore system and the oxide ore system, not only the redox properties of ores are different, but also the redox properties of organic flotation reagents used for flotation are greatly different. For sulphide ores, the main anion in the mineral composition is sulphide ion S 2- It has active chemical property and is easily oxidized into sulfate radical ions SO 4 2- (ii) a The xanthate collecting agent, the sulfur and nitrogen collecting agent and other hydrocarbon chains used for flotation are short and easy to degrade, so that the concentration requirement of the adopted oxidizing acid and strong oxidant in ore pulp is low, and meanwhile, the combined oxidant with relatively weak redox capability is adopted for oxidative degradation, and the action time is short. For an oxidized ore pulp system, the properties of mineral composition components are stable and are not easy to be oxidized and reduced; the organic reagents used in the flotation process are fatty acid type collectors, hydroximic acid type collectors, amine type collectors and the like, so that the chain length and the functional groups are large, the concentration requirement of oxidizing acid and strong oxidant in ore pulp is high, and meanwhile, the combined oxidant with relatively strong redox capacity is used for oxidative degradation, so that the loss of useful minerals caused by overhigh acidity and the consumption of the oxidative reagents are avoided while the organic flotation reagents on the surface of minerals and in the ore pulp are degraded. The mixed ore pulp of the oxidized ore and the sulfide ore can correspondingly adjust the conditions of concentration, proportion, action time and the like of the mixed oxidant according to the type and proportion of the specific organic flotation reagent actually existing in the ore pulp and the characteristic of the oxidation difficulty degree of the organic flotation reagent in different ore pulps, so as to achieve the optimal selective oxidation effect.
The method has wide application range, can be suitable for various mineral flotation systems, has small consumption of oxidizing agents, simple operation, strong selectivity, obvious effect and short action time, and has important significance for solving the problems of overproof drainage organic matters in ore dressing, overflow trough combined with dressing and smelting pretreatment, harmful gas released by drying of concentrate products and the like.
Drawings
Figure 1 shows the effect of different oxidant dosages on the oxidation of a tungsten flotation concentrate slurry in example 2.
Detailed Description
The following examples are intended to further illustrate the present invention, but not to limit the scope of the invention as claimed.
Example 1
Hydrogen peroxide solution (50%) and concentrated sulfuric acid are mixed for 3min according to the volume ratio of 3:7, and then the oxidation mixed solution is prepared. The method is characterized in that persimmon bamboo orchard polymetallic flotation tungsten concentrate ore pulp is taken as a research object, organic medicaments (mainly comprising CYW, 2# oil and a small amount of xanthate) in the ore pulp are treated, the action time is 5min, and the result is as follows. Along with the increase of the dosage, the degradation degree of the organic medicament is obviously increased, and the degradation efficiency is basically stable when the dosage is 200 g/L.
Example 2
In order to solve the problem of foam overflow caused by the pretreatment of metallurgical acid method by organic flotation agents (mainly BHA and BK205) adsorbed on the surface of minerals in tungsten flotation concentrate pulp in the combined dressing and metallurgy process, the TOC of the raw pulp is measured to be 1576 mg/L. A hydrogen peroxide solution (50%) and concentrated sulfuric acid are mixed and stirred for 1min according to a volume ratio of 2:8 to prepare an oxidation mixed solution, the action time of the oxidation mixed solution on metallurgical raw materials is 5min, and the result is shown in figure 1. It can be seen that as the amount of the mixed solution is increased, the foam layer formed by the acid foam pretreatment is thinner, the foam distribution is looser and the viscosity is obviously reduced.
Example 3
A50% potassium permanganate solution and concentrated nitric acid are selected to be matched to process organic agents in the sulfide ore pulp, the main components of the organic agents are ethidium nitride, butyl xanthate and BK205, and the contents of the ethyl thiozine, the butyl xanthate and the BK205 are 850mg/L, 560mg/L and 120mg/L respectively. The results are shown below for a comparison of a 50% potassium permanganate solution treated alone. It can be seen that the degradation efficiency of a single potassium permanganate solution is low, the degradation efficiency of the organic agent in the ore pulp is obviously improved along with the addition of the concentrated nitric acid, and the efficiency gradually tends to be stable when the volume ratio is less than 2: 1.
Example 4
The organic flotation reagent in the yellow sandlawn tungsten flotation concentrate pulp is respectively treated by single hydrogen peroxide, single potassium perchlorate, hydrogen peroxide + concentrated sulfuric acid, hydrogen peroxide + concentrated nitric acid, potassium perchlorate + concentrated sulfuric acid and potassium perchlorate + concentrated nitric acid, the main components of the organic flotation reagent are 480mg/L butyl xanthate, 1630mg/L MTC-2 and 150mg/L BK205, the mixture is stirred for 1min to prepare an oxidation mixed solution, the action time on the pulp is 3min, and the results are shown in the following table. It can be seen that the oxidation efficiency of potassium perchlorate alone is higher than that of hydrogen peroxide alone; the oxidation efficiency of the hydrogen peroxide and the oxidizing acid is higher than that of the potassium perchlorate and the oxidizing acid; the oxidation efficiency of the strong oxidant and the concentrated sulfuric acid is higher than that of the concentrated nitric acid.
Claims (4)
1. A method for degrading organic flotation agents in ore pulp is characterized by comprising the following steps: carrying out selective oxidative degradation on an organic flotation reagent in ore pulp containing sulfide ores and/or oxidized ores under the synergistic action of an oxidizing acid and a strong oxidizer;
the ore pulp containing the sulphide ore contains xanthate collectors and/or sulfur nitrogen ammonia sulfate collectors;
the ore pulp containing the oxidized ore contains at least one of a fatty acid collecting agent, a hydroximic acid collecting agent and an amine collecting agent;
the ore pulp containing the sulfide ore and the oxidized ore contains at least one of xanthate collecting agent, sulfur nitrogen sulfur amino acid ester collecting agent, fatty acid collecting agent, hydroximic acid collecting agent and amine collecting agent;
the oxidizing acid comprises concentrated sulfuric acid and/or nitric acid;
the strong oxidant comprises at least one of peroxide, perchlorate and permanganate;
for selective oxidative degradation of an organic flotation reagent in ore pulp containing sulfide ore, the volume percentage composition of a strong oxidant and an oxidizing acid is 50-90% and 50-10%, wherein the strong oxidant is added in a solution form with the mass percentage concentration of 40-60%, the total adding amount of the strong oxidant and the oxidizing acid in the ore pulp is 0.01-200 g/L, and the oxidative degradation time is 0.5-2 min;
for selective oxidative degradation of an organic flotation reagent in ore pulp containing oxidized ore, the volume percentage composition of a strong oxidant and an oxidizing acid is 10-30% to 90-70%, the total addition amount of the strong oxidant and the oxidizing acid in the ore pulp is 300-800 g/L, and the oxidative degradation time is 3-6 min;
for selective oxidative degradation of an organic flotation reagent in ore pulp containing oxidized ore and sulfide ore, the volume percentage composition of a strong oxidant and an oxidizing acid is 30-50% to 70-50%, the total addition amount of the strong oxidant and the oxidizing acid in the ore pulp is 200-300 g/L, and the oxidative degradation time is 2-3 min.
2. The method of claim 1 for degrading an organic flotation agent in pulp, wherein the method comprises the following steps: for selective oxidative degradation of an organic flotation reagent in ore pulp containing sulfide ores, the volume percentage composition of a strong oxidant and an oxidizing acid is 60-70% and 40-30%, wherein the strong oxidant is added in a solution form with the mass percentage concentration of 40-60%, the total adding amount of the strong oxidant and the oxidizing acid in the ore pulp is 50-150 g/L, and the oxidative degradation time is 0.5-1.5 min.
3. The method of claim 1 for degrading an organic flotation agent in pulp, wherein the method comprises the following steps: for selective oxidative degradation of an organic flotation reagent in ore pulp containing oxidized ore, the volume percentage composition of a strong oxidant and an oxidizing acid is 15-30% and 85-70%, the total addition amount of the strong oxidant and the oxidizing acid in the ore pulp is 400-600 g/L, and the oxidative degradation time is 4-5 min.
4. The method of claim 1 for degrading an organic flotation agent in pulp, wherein the method comprises the following steps: for selective oxidative degradation of an organic flotation reagent in ore pulp containing oxidized ore and sulfide ore, the volume percentage composition of a strong oxidant and an oxidizing acid is 35-45% and 65-55%, the total addition amount of the strong oxidant and the oxidizing acid in the ore pulp is 200-250 g/L, and the oxidative degradation time is 2-3 min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110861829.0A CN113769897B (en) | 2021-07-29 | 2021-07-29 | Method for degrading organic flotation reagent in ore pulp |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110861829.0A CN113769897B (en) | 2021-07-29 | 2021-07-29 | Method for degrading organic flotation reagent in ore pulp |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113769897A CN113769897A (en) | 2021-12-10 |
| CN113769897B true CN113769897B (en) | 2022-08-30 |
Family
ID=78836576
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110861829.0A Active CN113769897B (en) | 2021-07-29 | 2021-07-29 | Method for degrading organic flotation reagent in ore pulp |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113769897B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115417483B (en) * | 2022-09-16 | 2024-04-02 | 中国地质大学（武汉） | Method for treating sulfide ore mine wastewater by using pyrite |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101759274B (en) * | 2010-01-11 | 2012-01-04 | 长春黄金研究院 | Recycling and harmless treatment method for cyaniding tailing slurry |
| FR2994534B1 (en) * | 2012-08-20 | 2015-06-26 | Ceca Sa | COLLECTORS FOR ENRICHMENT OF MINERALS |
| CN103433149B (en) * | 2013-09-12 | 2015-02-11 | 广西华锡集团股份有限公司车河选矿厂 | Polymetallic sulphide ore flotation process capable of increasing zinc index |
| CN105057110B (en) * | 2015-08-06 | 2017-09-22 | 中南大学 | A kind of technique of bulk concentrate reagent removal and the separation of lead antimony zinc-iron multi-metal sulfide |
| CN106733221B (en) * | 2016-12-02 | 2019-08-23 | 武汉理工大学 | Dehydration reagent removal desliming process for ore dressing flotation |
| CN108706771A (en) * | 2018-06-08 | 2018-10-26 | 昆明理工大学 | A kind of processing method of the waste water containing xanthate |
| CN110292991A (en) * | 2019-07-03 | 2019-10-01 | 南华大学 | A kind of fluorite method for concentrating |
| CN111018085B (en) * | 2019-12-24 | 2022-02-22 | 中国有色桂林矿产地质研究院有限公司 | Treatment method of xanthate-containing heavy metal flotation wastewater |
-
2021
- 2021-07-29 CN CN202110861829.0A patent/CN113769897B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN113769897A (en) | 2021-12-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111715411B (en) | Beneficiation method for high-sulfur lead-zinc ore | |
| CN113769897B (en) | Method for degrading organic flotation reagent in ore pulp | |
| CN109987750B (en) | Method for promoting Fenton oxidation mediated by calcium and organic acid complex | |
| CN107081220B (en) | Method for improving enrichment effect of molybdenum oxide in scheelite flotation concentrate | |
| CN112403685B (en) | Flotation method for talc-containing molybdenum-zinc ore | |
| CN110918264B (en) | Application of combined inhibitor in flotation separation of copper-lead bulk concentrates | |
| CN113856911A (en) | Beneficiation method for high-sulfur copper gold silver ore | |
| CN101091935A (en) | Combined capturing and collecting agent | |
| CN113042216B (en) | Flotation separation method for carbonaceous lead sulfide zinc minerals | |
| CN112973970B (en) | Method for removing arsenic in lead concentrate | |
| CN109954591B (en) | Flotation method for reducing sulfur content in magnetic separation iron ore concentrate | |
| CN108704767B (en) | Combined inhibitor and application thereof in separation of molybdenum-containing and other metal sulfide ores | |
| CN111715409A (en) | Combined lead inhibitor of micro-fine particle galena and application thereof | |
| CN107617507B (en) | Process for recovering gold and sulfur from gold concentrate biological oxidation cyanidation tailings | |
| CN114011584B (en) | Preparation method and application of copper-arsenic flotation separation inhibitor for mixed copper ores | |
| CN114054214B (en) | Combined inhibitor for flotation separation of complex refractory copper-lead sulfide ore and application thereof | |
| CN1186867A (en) | Method of extracting gold by mixed oxidant in cyaniding leaching | |
| CN112237996B (en) | Flotation inhibitor for separating fine stibnite and pyrite and application thereof | |
| CN111992336B (en) | Selective desorption and recycling method for mineral surface medicament | |
| CN113264611A (en) | Treatment method of molybdenum-tungsten fluorite multi-metal ore dressing wastewater | |
| CN110560270A (en) | sand composite inhibitor and application thereof | |
| CN112076884B (en) | Critical oxidation activation method for pyrite inhibited by lime | |
| CN113908996B (en) | Copper-molybdenum separation combined regulator and application method thereof | |
| CN113210137B (en) | Combined inhibitor for separation of kaolin-containing copper sulfide ore and separation method | |
| CN114602657A (en) | Pyrite flotation combined inhibitor and application thereof |
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 |