WO2014042131A1 - 金の回収方法 - Google Patents
金の回収方法 Download PDFInfo
- Publication number
- WO2014042131A1 WO2014042131A1 PCT/JP2013/074289 JP2013074289W WO2014042131A1 WO 2014042131 A1 WO2014042131 A1 WO 2014042131A1 JP 2013074289 W JP2013074289 W JP 2013074289W WO 2014042131 A1 WO2014042131 A1 WO 2014042131A1
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- WIPO (PCT)
- Prior art keywords
- gold
- leaching
- solution
- activated carbon
- copper
- 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.)
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Classifications
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
- C22B3/10—Hydrochloric acid, other halogenated acids or salts thereof
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B11/00—Obtaining noble metals
- C22B11/04—Obtaining noble metals by wet processes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Definitions
- the present invention relates to a method for collecting gold.
- Gold is one of the most valuable metals, and as a natural product, it exists as a single particle and is often produced in association with sulfide metal ore and metal arsenide.
- the main method for recovering gold as an adjunct is to concentrate metal sulfide ore to concentrate and torsion and then recover the gold from the residue obtained by smelting and recovering the main component metal. It may be consumed and the environmental load due to sulfurous acid gas or the like may be large, and it is desired that the main component metal sulfide ore is treated by hydrometallurgy.
- the concentrate is dissolved by an appropriate oxidizing agent, and gold contained in the leachate and its residue is converted to a known method (for example, bluening leaching and wet-treatment as described in Patent Documents 1 and 2). Can be recovered by halogen leaching.
- a solvent extraction method is known for separation of gold and copper.
- An oxime-based extractant called LIX has a high selectivity for copper, and has already been put into practical use in a copper hydrometallurgical process. What is necessary is just to collect
- DBC dibutyl carbitol
- the amount of gold produced as an accompaniment of metal sulfide ore is about several ppm by weight, and when dissolved by wet processing, the gold concentration is very low and is not suitable for solvent extraction in many cases.
- a method of adsorbing and separating gold using an adsorbent can be considered.
- activated carbon is often used from the viewpoint of cost and versatility. Gold adsorbed on the activated carbon is stripped and then reduced to be smelted into metallic gold. Alternatively, the activated carbon can be incinerated, and metal gold can be obtained by reduction with carbon.
- One of the metal sulfides associated with gold is chalcopyrite.
- the accompanying gold is leached in a halogen bath after being separated and concentrated in advance as a residue. Or leached into a halogen bath at the same time as the main component ore leaching.
- a gold complex having a halide as a ligand remains.
- Patent Documents 1 and 2 do not discuss the improvement of the adsorptivity of gold to activated carbon, and generally the type of activated carbon and the solution after leaching. There is a problem such as complications, and an appropriate method is not known.
- an object of the present invention is to provide a gold recovery method capable of increasing the amount of gold adsorbed on activated carbon.
- the present inventor when adsorbing and recovering a gold complex in an acidic solution after gold leaching to activated carbon, a substance that becomes a competitive adsorbent to activated carbon is gold After leaching, it was determined that it was a monovalent copper ion in the solution. And it discovered that the amount of gold
- leaching gold into the acid leaching solution using an acid leaching solution containing chloride ions and / or bromide ions as anions and copper as a cation, and after gold leaching A method for recovering gold, comprising a step of obtaining a solution and a step of adsorbing gold in the solution after gold leaching to the activated carbon, wherein the gold solution after leaching before adsorbing the gold in the solution after gold leaching to the activated carbon
- a method for recovering gold including a step of adjusting the oxidation-reduction potential (reference electrode, silver / silver chloride) and reducing the concentration of monovalent copper ions contained in the solution after gold leaching.
- the oxidation-reduction potential (reference electrode, silver / silver chloride) is 520 mV to 570 mV.
- the redox potential is adjusted by blowing air.
- the acidic leachate contains 40 to 200 g / L of chloride ions, 20 to 100 g / L of bromide ions, 5 to 25 g / L of copper, and It contains 0.01 to 10 g / L of iron and has a pH of 0 to 1.9.
- Gold is often contained in trace amounts as a simple substance in sulfide metal ores such as chalcocite, chalcopyrite, copper indigo, chalcopyrite, pyrite, arsenite, arsenite. For this reason, in order to collect this, it is preferable to first concentrate the metal sulfide ore by crushing and then concentrating it by a flotation method. If copper and iron, which are main component metals, are leached from the concentrate using an acidic leaching solution, then the solid and liquid separation can be performed to further concentrate gold in the leaching residue, and the processing efficiency is improved.
- gold ore can be used in addition to the above-mentioned sulfide ores such as chalcocite, porphyry, copper indigo, chalcopyrite, pyrite, pyrite, arsenite, etc. It is.
- a material having a gold quality contained in these gold raw materials of 0.1 to 100 g / t, more preferably about 1 to 20 g / t can be suitably used in the recovery method according to the present invention.
- gold leaching In the present invention, first, gold is heated and leached using an acidic leaching solution containing chloride ions and / or bromide ions as anions and copper as a cation to obtain a solution after gold leaching.
- an acidic leaching solution containing chloride ions and / or bromide ions as anions and copper as a cation.
- the pH of the acidic leaching solution is 0 to 1.9, more preferably 0.5 to 1.5, and still more preferably 1 to 1.2. If the leaching temperature and the pH of the leaching solution are within such ranges, gold leaching is better.
- the acidic leachate preferably contains 20 to 200 g / L of chloride ions and bromide ions and 0.01 to 30 g / L of copper and iron, respectively. More preferably, the acidic leachate is 40 to 200 g / L, more preferably 100 to 180 g / L, further 120 to 150 g / L of chloride ions, and 20 to 100 g / L, more preferably 50 to 100 g / L.
- a valuable metal can be leached by dissolving a gold raw material such as metal sulfide ore in the acidic leaching solution. Trace amounts of gold are leached together with the main metal. If necessary, after the solid-liquid separation, the gold contained in the residue is leached with an acidic solution having the same composition.
- metal sulfide ore is leached in multiple stages, if a similar acidic leaching solution is used, a part or most of the gold is dissolved in the latter stage, and this can be treated as a solution after leaching gold.
- the redox potential (ORP) of the solution after gold leaching is about 500 mV or less, but by adding an oxidizing agent to this and adjusting the ORP, the monovalent copper contained in the solution after gold leaching The ion concentration can be reduced.
- the adjustment of the oxidation-reduction potential is performed after gold is sufficiently leached into the solution after gold leaching in the gold leaching step, thereby improving the gold recovery efficiency of the entire system.
- the oxidizing agent is not particularly limited, but air is used from the viewpoint of cost.
- the liquid temperature is not particularly limited, but considering the fact that gold leaching is warm leaching and the aspect of oxidation efficiency, the liquid temperature of the liquid after gold leaching is preferably maintained at 45 ° C. or more, more preferably It is 50 ° C. or higher.
- An increase in ORP indicates a decrease in monovalent copper ions in the solution after gold leaching.
- Monovalent copper is known as a very soft element, has a high affinity for activated carbon, and competes with the adsorption of gold complexes. By reducing the monovalent copper, the adsorption active sites in the activated carbon are increased in selectivity to gold, thereby achieving efficient recovery of gold.
- the ORP can be adjusted to 520 mV or more, thereby reducing the monovalent copper concentration in the liquid and improving the adsorption rate of gold on activated carbon.
- the upper limit is not particularly limited, but considering the time required for adjustment and the reduction efficiency of monovalent copper, it is preferably 570 mV or less, more preferably 530 to 560 mV.
- gold in the acidic leachate is brought into contact with activated carbon and adsorbed.
- the contact of gold with activated carbon may be carried out by batch feeding or by continuously passing an acidic leachate through an adsorption tower packed with activated carbon.
- the stirring speed is not specified.
- the amount of activated carbon added is 50 to 10,000 times the weight of gold.
- the flow rate is not particularly limited (generally, SV1 to 25), but when the gold adsorption amount per unit weight of the activated carbon reaches 20000 to 30000 g / t, the activated carbon does not satisfy the required capacity. Therefore, gold strips from activated carbon and regeneration are performed based on this amount of adsorption.
- the regeneration of the activated carbon is performed with a generally known sulfur compound, nitrogen compound, or acid and is not particularly limited.
- the oxidation-reduction potential is adjusted to adjust the monovalent in the liquid.
- the concentration of copper ions By reducing the concentration of copper ions, the amount of gold adsorbed can be increased.
- Example 1 Gold in the gold raw material was leached using an acidic leaching solution containing 50 g / L of chloride ions, 80 g / L of bromide ions, 18 g / L of copper, and 0.2 g / L of iron. Contained NaCl: 84 g / L, NaBr: 103 g / L, Cu: 20 g / L, Fe: 2 g / L, Au: 8 mg / L, and the pH was 1.2. CuCl was added to adjust the ORP to 510 mV or less. After leaching, the liquid was heated to 55 ° C. and stirred while blowing 0.4 L per minute to adjust various ORPs.
- This leachate was passed through a glass column filled with approximately 14 ml of coconut shell-derived activated carbon (coconut MC manufactured by Taihei Chemical Industry Co., Ltd.), and gold was adsorbed on the activated carbon.
- the column diameter was 11 mm and the height was 150 mm.
- the liquid supply rate was 11.9 ml / min, and the space velocity was 50 (1 / h).
- Gold in the discharged solution after adsorption was diluted with hydrochloric acid and quantified by ICP-AES. The relationship between the ORP and the post-adsorption liquid is shown in FIG.
- the gold concentration contained in the post-adsorption liquid is significantly reduced in the liquid in which the ORP is adjusted to 520 mV or more.
- the upper limit of ORP is not set, it is understood that even if the potential is raised excessively, the gold concentration in the solution after adsorption does not drop dramatically, and it is sufficient to oxidize to at least 520 mV, but it does not prevent excessive oxidation. .
- Example 2 The gold concentration in the post-adsorption liquid was measured by changing the ORP by adding CuCl and blowing air while continuously feeding liquid after the gold leaching used in Example 1 and using the activated carbon packed column. The results are shown in FIG.
- FIG. 2 also shows the relationship between the adsorption of ORP and gold on activated carbon, and the gold after leaching can be recovered with good gold when it is contacted with activated carbon at ORP 520 mV or higher. It can also be seen that it is Cu (I) that affects the ORP.
- Cu (I) tends to be oxidized to Cu (II) in an aqueous solution, but exists relatively stably in an aqueous solution containing a high-concentration halide as in this system. Therefore, in addition to air blowing, it is estimated that similar results can be obtained by oxidizing Cu (I) with an oxidizing agent such as hydrogen peroxide or hypochlorous acid. Is preferred.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Metallurgy (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Environmental & Geological Engineering (AREA)
- Geology (AREA)
- Geochemistry & Mineralogy (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Inorganic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Treatment Of Liquids With Adsorbents In General (AREA)
Description
金は、輝銅鉱、斑銅鉱、銅藍、黄銅鉱、黄鉄鉱、硫砒銅鉱、硫砒鉄鉱等の硫化金属鉱に単体として極微量含まれることが多い。このため、これを回収するには、まず硫化金属鉱を破砕後に浮遊選鉱法により精鉱とすることで濃縮することが好ましい。この精鉱から酸性浸出液を用いて主成分金属である銅、鉄を浸出した後に固液分離すれば、浸出残渣に金をさらに濃縮することも可能であり、処理効率が良好となる。本発明に係る回収方法を適用可能な金原料としては、上記の輝銅鉱、斑銅鉱、銅藍、黄銅鉱、黄鉄鉱、硫砒銅鉱、硫砒鉄鉱等の硫化金属鉱の他、金鉱石等も利用可能である。これら金原料に含まれる金品位としては0.1~100g/t、より好ましくは1~20g/t程度の材料が、本発明に係る回収方法において好適に利用可能である。
本発明においては、まず、アニオンとして塩化物イオン及び/又は臭化物イオンを含み、カチオンとして銅を含む酸性浸出液を用いて、金を加温浸出し、金浸出後液を得る。金の浸出効率を考慮すると、酸性浸出液のpHは、0~1.9、より好ましくは0.5~1.5、更に好ましくは1~1.2である。浸出温度及び浸出液のpHがこのような範囲であれば、金の浸出がより良好となる。
金浸出後液の酸化還元電位(ORP)はおおむね500mV程度もしくはそれ以下を示すが、これに酸化剤を添加して、ORPを調整することにより、金浸出後液中に含まれる一価の銅イオン濃度を低減させることができる。
次に、酸性浸出液中の金を活性炭に接触させて吸着させる。金の活性炭への接触はバッチ回分式もしくは活性炭を充填した吸着塔に酸性浸出液を連続通液することで行ってもよい。
50g/Lの塩化物イオン、80g/Lの臭化物イオン、18g/Lの銅、及び0.2g/Lの鉄を含む酸性浸出液を用いて金原料中の金を浸出したところ、金浸出後液は、NaCl:84g/L、NaBr:103g/L、Cu:20g/L、Fe:2g/L、Au:8mg/L含有し、pHは1.2であった。CuClを添加してORPを510mV以下に調整した。浸出後液を55℃に加温し、空気を1分当たり0.4L吹き込みながら攪拌して各種ORPに調整した。この浸出液をヤシ殻由来活性炭(太平化学産業社製ヤシコールMC)およそ14mlを充填したガラス製カラムに通し、金を活性炭に吸着させた。カラムの直径は11mm、高さ150mmとした。液の供給速度は11.9ml/分、空間速度は50(1/h)とした。排出される吸着後液中の金を塩酸で希釈しICP-AESにより定量した。ORPと吸着後液の関係を図1に示す。
実施例1で使用した金浸出後と活性炭充填カラムとを用いて連続的に給液する中で、CuClの添加と空気吹込みによりORPを変化させて吸着後液の金濃度を測定した。結果を図2に示す。
Claims (4)
- アニオンとして塩化物イオン及び/又は臭化物イオンを含み、カチオンとして銅を含む酸性浸出液を用いて、金を前記酸性浸出液中に浸出させ、金浸出後液を得る工程と、
前記金浸出後液中の金を活性炭に吸着させる工程と、
を含む金の回収方法であって、
前記金浸出後液中の金を活性炭に吸着させる前に、前記金浸出後液の酸化還元電位(参照電極、銀/塩化銀)を調整し、前記金浸出後液中の一価の銅イオン濃度を低減させる工程
を含むことを特徴とする金の回収方法。 - 前記酸化還元電位(参照電極、銀/塩化銀)を520mV~570mVに調整することを含む請求項1に記載の金の回収方法。
- 前記酸化還元電位の調整が、空気の吹き込みにより調整することを特徴とする請求項1又は2のいずれかに記載の金の回収方法。
- 前記酸性浸出液が、40~200g/Lの塩化物イオン、20~100g/Lの臭化物イオン、5~25g/Lの銅、及び0.01~10g/Lの鉄を含み、pHが0~1.9である請求項1~3のいずれか1項に記載の金の回収方法。
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA2884363A CA2884363C (en) | 2012-09-11 | 2013-09-09 | Method for recovering gold |
| AU2013316588A AU2013316588B2 (en) | 2012-09-11 | 2013-09-09 | Method for recovering gold |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012199492A JP5467133B2 (ja) | 2012-09-11 | 2012-09-11 | 金の回収方法 |
| JP2012-199492 | 2012-09-11 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2014042131A1 true WO2014042131A1 (ja) | 2014-03-20 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/JP2013/074289 Ceased WO2014042131A1 (ja) | 2012-09-11 | 2013-09-09 | 金の回収方法 |
Country Status (6)
| Country | Link |
|---|---|
| JP (1) | JP5467133B2 (ja) |
| AU (1) | AU2013316588B2 (ja) |
| CA (1) | CA2884363C (ja) |
| CL (1) | CL2015000590A1 (ja) |
| PE (1) | PE20150506A1 (ja) |
| WO (1) | WO2014042131A1 (ja) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11408053B2 (en) | 2015-04-21 | 2022-08-09 | Excir Works Corp. | Methods for selective leaching and extraction of precious metals in organic solvents |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FI20145949A7 (fi) * | 2014-10-29 | 2016-04-30 | Outotec Finland Oy | Menetelmä kullan talteenottamiseksi |
| CA2978693C (en) | 2015-03-06 | 2020-06-30 | Jx Nippon Mining & Metals Corporation | Activated carbon regeneration method and gold recovery method |
| JP6463175B2 (ja) * | 2015-03-06 | 2019-01-30 | Jx金属株式会社 | 活性炭の再生方法及び、金の回収方法 |
| JP6437352B2 (ja) | 2015-03-13 | 2018-12-12 | Jx金属株式会社 | 硫化銅鉱からの銅の浸出方法及び硫化銅鉱のカラムリーチング試験のヨウ素損失量の評価方法 |
| JP6849482B2 (ja) * | 2016-03-31 | 2021-03-24 | Jx金属株式会社 | 金を含む鉱石もしくは精錬中間物からの金の回収方法 |
| CN106148693A (zh) * | 2016-09-28 | 2016-11-23 | 中南大学 | 一种含硫砷难处理金矿提金方法 |
| JP6899672B2 (ja) * | 2017-03-14 | 2021-07-07 | Jx金属株式会社 | 鉱石もしくは精錬中間物からの金の回収方法 |
| CN111893299A (zh) * | 2020-08-03 | 2020-11-06 | 玉门市昌源矿业有限公司 | 一种用于尾矿回收再利用的药剂配方及提金工艺 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001516808A (ja) * | 1997-09-17 | 2001-10-02 | アングロ アメリカン プラティナム コーポレイション リミティド | 白金族金属の分離 |
| JP2009526912A (ja) * | 2006-02-17 | 2009-07-23 | オウトテック オサケイティオ ユルキネン | 金回収方法 |
| JP2009235525A (ja) * | 2008-03-27 | 2009-10-15 | Nippon Mining & Metals Co Ltd | 金の浸出方法 |
| JP2009235519A (ja) * | 2008-03-27 | 2009-10-15 | Nippon Mining & Metals Co Ltd | 鉱物からの金属の回収方法 |
-
2012
- 2012-09-11 JP JP2012199492A patent/JP5467133B2/ja active Active
-
2013
- 2013-09-09 PE PE2015000338A patent/PE20150506A1/es active IP Right Grant
- 2013-09-09 AU AU2013316588A patent/AU2013316588B2/en active Active
- 2013-09-09 WO PCT/JP2013/074289 patent/WO2014042131A1/ja not_active Ceased
- 2013-09-09 CA CA2884363A patent/CA2884363C/en active Active
-
2015
- 2015-03-10 CL CL2015000590A patent/CL2015000590A1/es unknown
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001516808A (ja) * | 1997-09-17 | 2001-10-02 | アングロ アメリカン プラティナム コーポレイション リミティド | 白金族金属の分離 |
| JP2009526912A (ja) * | 2006-02-17 | 2009-07-23 | オウトテック オサケイティオ ユルキネン | 金回収方法 |
| JP2009235525A (ja) * | 2008-03-27 | 2009-10-15 | Nippon Mining & Metals Co Ltd | 金の浸出方法 |
| JP2009235519A (ja) * | 2008-03-27 | 2009-10-15 | Nippon Mining & Metals Co Ltd | 鉱物からの金属の回収方法 |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11408053B2 (en) | 2015-04-21 | 2022-08-09 | Excir Works Corp. | Methods for selective leaching and extraction of precious metals in organic solvents |
| US11427886B2 (en) | 2015-04-21 | 2022-08-30 | Excir Works Corp. | Methods for simultaneous leaching and extraction of precious metals |
| US11814698B2 (en) | 2015-04-21 | 2023-11-14 | Excir Works Corp. | Methods for simultaneous leaching and extraction of precious metals |
Also Published As
| Publication number | Publication date |
|---|---|
| CL2015000590A1 (es) | 2015-06-12 |
| AU2013316588B2 (en) | 2016-03-10 |
| CA2884363C (en) | 2018-03-20 |
| AU2013316588A1 (en) | 2015-03-26 |
| JP5467133B2 (ja) | 2014-04-09 |
| PE20150506A1 (es) | 2015-04-29 |
| JP2014055311A (ja) | 2014-03-27 |
| CA2884363A1 (en) | 2014-03-20 |
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