EP3931363A1 - Verfahren zur gewinnung von gold und/oder silber und/oder mindestens einem platinmetall - Google Patents
Verfahren zur gewinnung von gold und/oder silber und/oder mindestens einem platinmetallInfo
- Publication number
- EP3931363A1 EP3931363A1 EP19724374.4A EP19724374A EP3931363A1 EP 3931363 A1 EP3931363 A1 EP 3931363A1 EP 19724374 A EP19724374 A EP 19724374A EP 3931363 A1 EP3931363 A1 EP 3931363A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- solution
- gold
- starting material
- hydroxyl radicals
- silver
- 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.)
- Pending
Links
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 239000010931 gold Substances 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 title claims abstract description 29
- 229910052737 gold Inorganic materials 0.000 title claims abstract description 26
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 10
- 239000004332 silver Substances 0.000 title claims abstract description 10
- 239000007858 starting material Substances 0.000 claims abstract description 22
- 239000007864 aqueous solution Substances 0.000 claims abstract description 11
- 150000002825 nitriles Chemical class 0.000 claims abstract description 11
- 239000000243 solution Substances 0.000 claims description 36
- 238000006243 chemical reaction Methods 0.000 claims description 16
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- 150000001298 alcohols Chemical class 0.000 claims description 5
- 239000004094 surface-active agent Substances 0.000 claims description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- 229910001854 alkali hydroxide Inorganic materials 0.000 claims description 2
- 238000000605 extraction Methods 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 abstract description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 15
- 229910052751 metal Inorganic materials 0.000 description 14
- 239000002184 metal Substances 0.000 description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 6
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 6
- 150000002739 metals Chemical class 0.000 description 6
- -1 platinum metals Chemical class 0.000 description 6
- 229910052697 platinum Inorganic materials 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000003929 acidic solution Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 150000002505 iron Chemical class 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000003923 scrap metal Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000012028 Fenton's reagent Substances 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000012080 ambient air Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000009918 complex formation Effects 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- JMANVNJQNLATNU-UHFFFAOYSA-N glycolonitrile Natural products N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 1
- MGZTXXNFBIUONY-UHFFFAOYSA-N hydrogen peroxide;iron(2+);sulfuric acid Chemical compound [Fe+2].OO.OS(O)(=O)=O MGZTXXNFBIUONY-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- LRDFRRGEGBBSRN-UHFFFAOYSA-N isobutyronitrile Chemical compound CC(C)C#N LRDFRRGEGBBSRN-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
- 231100000925 very toxic Toxicity 0.000 description 1
- 238000009736 wetting Methods 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
- C22B11/00—Obtaining noble metals
- C22B11/08—Obtaining noble metals by cyaniding
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B11/00—Obtaining noble metals
- C22B11/04—Obtaining noble metals by wet processes
- C22B11/042—Recovery of noble metals from waste materials
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- 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
- C22B3/16—Extraction of metal compounds from ores or concentrates by wet processes by leaching in organic solutions
-
- 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
-
- 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 extracting gold and / or silver and / or at least one platinum metal from at least one starting material.
- Gold, silver and platinum metals are essential raw materials. They can be recovered from valuable waste, for example as part of catalyst materials or from electronic devices, pyrometallurgical or hydrometallurgical. The pyrometallurgical recovery takes place by removing the scrap metals
- metals to be recovered brought into an aqueous solution by complex formation.
- An example of such a process is alkaline cyanide leaching for gold mining. This process is carried out at very high pH values, i.e. using aggressive alkalis.
- the complexing agent used, cyanide is very toxic, making this process too dangerous
- the pH of a cyanide-containing solution can be increased by the absorption of carbon dioxide from the ambient air
- Platinum metals are understood to mean the light platinum metals ruthenium, rhodium and palladium and the heavy platinum metals iridium and platinum. Be under scrap metal
- the at least one starting material which contains gold and / or silver and / or at least one platinum metal, is introduced into an aqueous solution which contains at least one nitrile.
- the nitrile is selected in particular from the group consisting of acetonitrile, isobutyronitrile and propionitrile, with acetonitrile being particularly preferred. Be in the aqueous solution
- hydroxyl radicals By reacting the hydroxyl radicals with the nitrile, just as many cyanides (ions or radicals) can be generated in situ as are necessary to bring the metal to be extracted into solution.
- the hydroxyl radicals can act on the metal as
- Oxidizing agents act. This means that it is not necessary to work with large excesses of cyanides, nor is it necessary to use large amounts of strong alkalis.
- the hydroxyl radicals are generated by introducing ozone into the solution. This can react with water to form oxygen and hydroxyl radicals, the reaction being carried out in particular photocatalytically.
- the ozone required for this can be generated, for example, by corona discharges or electrochemically.
- the solution preferably contains 0.1 mol per liter to 1.0 mol per liter of at least one alkali metal hydroxide, in particular sodium hydroxide or potassium hydroxide. Due to the targeted formation of cyanides (ions or radicals) and the oxidizing effect of the hydroxyl radicals, this amount of alkali hydroxide is sufficient to effectively prevent the formation of gaseous hydrogen cyanide. Furthermore, in this embodiment of the method it is preferred that the ozone is introduced into the solution through a porous diffuser below the starting material. In this way it flows around the starting material and the formation of hydroxyl radicals takes place near the surface of the
- the solution flows in the same direction as the starting material as the ozone. This way, fresh solution is enriched with ozone before it
- the hydroxyl radicals are generated in the solution by a Fenton reaction.
- the Fenton reaction is an iron salt catalyzed reaction of hydrogen peroxide in acidic solution.
- the solution can in particular contain Fenton's reagent, a sulfuric acid mixture of hydrogen peroxide and an iron salt.
- Iron (II) sulfate is particularly suitable as the iron salt.
- Electro-Fenton reaction requires a strongly acidic solution in order to neutralize the hydroxyl anions formed
- a combination of the Electro-Fenton reaction with a Photo-Fenton reaction can also generate the hydroxyl radicals in a weakly acidic solution, for which the solution preferably contains formic acid. This reduces the risk of the formation of gaseous hydrocyanic acid due to the release of cyanide ions from cyanometallic complexes.
- the solution contains at least 0.1 mol per liter of the at least one nitrile in order to provide a sufficiently large source for the generation of cyanides (ions or radicals).
- the solution contains at least one substance which is selected from the group consisting of alcohols, surfactants and Activated carbon.
- alcohols the short-chain alcohols methanol, ethanol and isopropanol are preferred.
- surfactants the alcohols bring about improved wetting of the at least one starting material by the aqueous solution.
- the activated carbon has a large surface on which the formation of hydroxyl radicals can take place.
- the solution is irradiated with UV light.
- UV light preferably has a wavelength of less than 310 nm.
- the wavelength of the UV light used is preferably less than 580 nm.
- Figure 1 shows schematically a reactor in which a method according to an embodiment of the invention takes place.
- FIG. 2 shows schematically another reactor in which a method according to another exemplary embodiment of the invention takes place.
- Figure 1 shows how in an embodiment of the invention from a
- Starting material 10 which in the present case is a printed circuit board, gold can be detached from a nickel substrate. This is for this
- aqueous solution 20 which is stored in a reactor 21. Fresh solution is continuously fed in through an inlet opening 22, which is arranged below the starting material 10 on the wall of the reactor 21, while solution enriched with cyano complexes of gold is passed through a Above the starting material 10 in the wall of the reactor 21 arranged outlet opening 23 is derived.
- the aqueous solution 20 contains im
- Ozone 30 is introduced into the reactor 21 through a porous diffuser 31 which is arranged in the reactor 21 below the starting material 10 and below the inlet opening 22. It mixes with the fresh solution 20, which is passed through the inlet opening 22 into reactor 21, and flows around the starting material 10.
- the reactor 21 consists of a transparent material and is illuminated from the outside by means of a UV lamp 40 with light with a wavelength of less than 310 nm irradiated. According to formula 1, the ozone photocatalytically forms oxygen and hydroxyl radicals with water molecules: (Formula 1)
- a mixture 32 of unreacted ozone and the oxygen formed leaves the reactor 21 through a gas outlet 24 on its top.
- hydroxyl radicals react with the acetonitrile to form cyanogen radicals to form methanol. These oxidize metallic gold
- hydroxyl radicals according to formula 3 can themselves oxidize gold to gold (l) hydroxide on the metal surface. This is highly reactive and reacts with the acetonitrile to form methanol to gold (l) cyanide:
- the gold (l) cyanide goes into solution and leaves the reactor through the
- a reactor 21 is used, as shown in FIG. This differs from the reactor according to FIG. 1 in that the porous diffuser 31 for introducing ozone 30 and the gas outlet opening 24 are dispensed with. Instead, an electrical energy source 40 is provided, which is connected to two electrodes 51, 52 which protrude below the starting material 10 into the reactor 21.
- the aqueous solution 20 additionally contains iron (II) sulfate and before it is introduced through the inlet opening 22 through a line (not shown) it is continuously enriched with hydrogen peroxide by formation on a cathode. Instead of 0.5 mol / l
- the Photo-Fenton reaction causes both a regeneration of the iron (II) cations oxidized in the Electro-Fenton reaction by reduction and a neutralization of the hydroxyl anions generated there, so that the pH of the solution 20 does not change.
- the hydroxyl radicals generated in the two Fenton reactions then react as in the first embodiment the process according to formulas 2 and 3 and bring gold in the form of gold (l) cyanide in solution. Removing the cyanide with gold (l)
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Geochemistry & Mineralogy (AREA)
- Catalysts (AREA)
- Physical Water Treatments (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102019202779.2A DE102019202779A1 (de) | 2019-03-01 | 2019-03-01 | Verfahren zur Gewinnung von Gold, Silber und Platinmetallen |
PCT/EP2019/061672 WO2020177880A1 (de) | 2019-03-01 | 2019-05-07 | Verfahren zur gewinnung von gold und/oder silber und/oder mindestens einem platinmetall |
Publications (1)
Publication Number | Publication Date |
---|---|
EP3931363A1 true EP3931363A1 (de) | 2022-01-05 |
Family
ID=66554338
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP19724374.4A Pending EP3931363A1 (de) | 2019-03-01 | 2019-05-07 | Verfahren zur gewinnung von gold und/oder silber und/oder mindestens einem platinmetall |
Country Status (5)
Country | Link |
---|---|
US (1) | US20220074021A1 (de) |
EP (1) | EP3931363A1 (de) |
CN (1) | CN113454247B (de) |
DE (1) | DE102019202779A1 (de) |
WO (1) | WO2020177880A1 (de) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102021200432A1 (de) | 2021-01-19 | 2022-07-21 | Robert Bosch Gesellschaft mit beschränkter Haftung | Verfahren zur Herstellung einer wässrigen Lösung von unkomplexierten Cyanidionen und zur Gewinnung von Gold und/oder Silber und/oder mindestens einem Platinmetall |
CN113088689B (zh) * | 2021-03-24 | 2023-03-24 | 上海师范大学 | 一种水溶液中光催化选择性溶解贵金属的方法 |
CN114053978A (zh) * | 2021-11-25 | 2022-02-18 | 上海师范大学 | 一种含金属废料提纯装置 |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2666876B2 (ja) * | 1993-06-18 | 1997-10-22 | 工業技術院長 | 金の精製方法 |
DE502007003723D1 (de) * | 2006-02-03 | 2010-06-24 | Basf Se | Bereitstellung von metallcyanid enthaltenden wässrigen lösungen für die cyanidlaugerei zur gold- und silbergewinnung |
JP2013208539A (ja) * | 2012-03-30 | 2013-10-10 | Kitakyushu Foundation For The Advancement Of Industry Science & Technology | ラジカル水 |
EP3286346A4 (de) * | 2015-04-21 | 2019-01-16 | University of Saskatchewan | Verfahren zur selektiven auslaugung und extraktion von edelmetallen in organischen lösungsmitteln |
CN105366785A (zh) * | 2015-12-18 | 2016-03-02 | 北京伟创力科技有限公司 | 一种提高臭氧利用效率降低废水cod的方法 |
-
2019
- 2019-03-01 DE DE102019202779.2A patent/DE102019202779A1/de active Pending
- 2019-05-07 EP EP19724374.4A patent/EP3931363A1/de active Pending
- 2019-05-07 CN CN201980093359.9A patent/CN113454247B/zh active Active
- 2019-05-07 US US17/423,255 patent/US20220074021A1/en not_active Abandoned
- 2019-05-07 WO PCT/EP2019/061672 patent/WO2020177880A1/de active Application Filing
Also Published As
Publication number | Publication date |
---|---|
WO2020177880A1 (de) | 2020-09-10 |
US20220074021A1 (en) | 2022-03-10 |
CN113454247B (zh) | 2023-02-03 |
DE102019202779A1 (de) | 2020-09-03 |
CN113454247A (zh) | 2021-09-28 |
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