EP4185724A1 - Procédé de récupération d'un métal précieux dans un article - Google Patents

Procédé de récupération d'un métal précieux dans un article

Info

Publication number
EP4185724A1
EP4185724A1 EP21749272.7A EP21749272A EP4185724A1 EP 4185724 A1 EP4185724 A1 EP 4185724A1 EP 21749272 A EP21749272 A EP 21749272A EP 4185724 A1 EP4185724 A1 EP 4185724A1
Authority
EP
European Patent Office
Prior art keywords
article
acidothiobacillus
base metal
precious metal
bacteria
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
Application number
EP21749272.7A
Other languages
German (de)
English (en)
Inventor
Jack GOMARSALL
Sebastien FARNAUD
Daniel RAY
John Graves
Mahsa BANIASADI
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
N2s Global Ltd
Original Assignee
N2s Global Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by N2s Global Ltd filed Critical N2s Global Ltd
Publication of EP4185724A1 publication Critical patent/EP4185724A1/fr
Pending legal-status Critical Current

Links

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
    • C22B7/006—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
    • C22B11/046—Recovery of noble metals from waste materials from manufactured products, e.g. from printed circuit boards, from photographic films, paper or baths
    • 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
    • C22B3/18—Extraction of metal compounds from ores or concentrates by wet processes with the aid of microorganisms or enzymes, e.g. bacteria or algae
    • 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 methods of recovering a precious metal from an article such as electronic waste, and to bioreactors relating thereto.
  • a method of recovering a precious metal in solid form from an article comprising a base metal attached to the precious metal
  • the method comprising the steps of: (a) bioleaching of the base metal by bacterial oxidation so as to detach the precious metal in solid form from the base metal; and (b) recovering the precious metal.
  • bioleaching of the base metal by bacterial oxidation the base metal forms a salt (and is solubilised) and the precious metal detaches in solid form from the base metal, facilitating recovery of the precious metal.
  • this obviates the need for additional processing steps for conversion of gold to a recoverable solid form, and for reagents which can be highly toxic.
  • the present method can be more cost and time effective, and less environmentally damaging, than methods of the prior art.
  • the bioleaching step is performed in the presence of an added acid generator.
  • the acid generator is elemental sulfur.
  • the acid generated by the added acid generator can assist in the oxidation and bioleaching of the base metal to allow for the precious metal to detach in solid form.
  • the acid may be generated by bacterial oxidation of the added acid generator.
  • the added sulfur can be oxidised by bacteria to generate sulfuric acid, which in turn can assist base metal oxidation.
  • the precious metal may be selected from the group comprising: gold, silver, platinum, palladium, iridium, osmium, rhodium and ruthenium. In some embodiments, the precious metal may be gold.
  • the article may comprise a substrate on which the base metal is attached.
  • the article may comprise a plastics (e.g. fibreglass), silicon, ceramic or metal substrate.
  • the article may be an electronic article.
  • the electronic article may be electronic waste.
  • the electronic article may comprise a printed circuit board (PCB) or a hard drive.
  • the electronic article (e.g. PCB or hard drive) may comprise a silicon or plastics substrate on which the base metal is connected.
  • the electronic article may be any other suitable electronic article as are known to those skilled in the art.
  • the article may be a non-electronic article, e.g. a catalytic converter or jewellery.
  • the method can be used to process electronic waste, such as printed circuit boards, such that gold fingers comprising gold connected to copper or other base metal on a silicon or plastics substrate, can be removed in solid form, for easy recovery of the gold.
  • the bacterial oxidation is achieved using bacteria.
  • the bacteria may be acidophilic bacteria.
  • Any suitable bacteria capable of base metal recovery via indirect oxidation may be used.
  • the bacterial oxidation may be indirect bacterial oxidation. This involves using bacteria to indirectly oxidise the base metal, wherein the bacteria acts as a catalyst to continuously generate an oxidising agent which oxidises the base metal.
  • the oxidising agent for the base metal is Fe 3+ ions
  • those ions oxidise the base metal and are reduced to Fe 2+ ions, which are oxidised back to Fe 3+ ions by the bacteria, and the cycle continues.
  • the bacterial oxidation may be direct bacterial oxidation. This involves using the bacteria to oxidise the base metal directly, i.e. the bacteria acts as the oxidising agent for the base metal.
  • the bioleaching step may use one or more bacteria selected from the group comprising: Lentosprillum spp. such as Leptosprillum ferriphilum or Leptosprillum ferrooxidans; Acidothiobacillus spp. such as Acidothiobacillus ferroxidans, Acidothiobacillus ferridurans, Acidothiobacillus ferriphilus Acidothiobacillus caldus, Acidothiobacillus thioxidans, or Acidothiobacillus ambivalens; Sulfobacillus spp. such as Sulfobacillus acidophilus or Sulfobacillus thermosulfidooxidans; and (archaea) Ferroplasma spp.
  • Lentosprillum spp. such as Leptosprillum ferriphilum or Leptosprillum ferrooxidans
  • Acidothiobacillus spp. such as Acidothiobacillus
  • the bioleaching step may use Acidothiobacillus ferroxidans.
  • the bioleaching step may use a consortium of bacteria comprising at least one Leptosprillum spp., at least one Acidothiobacillus spp. and at least one Sulfobacilus spp. In some embodiments, the bioleaching step may use a consortium comprising Acidothiobacillus ferroxidans, at least one Leptosprillum spp . ; optionally at least one further A cidothiobacillus spp. and at least one Sulfobacilus spp.
  • the bioleaching step may be using a consortium of bacteria comprising: Leptosprillum ferriphilum, Leptosprillum ferrooxidans, Acidothiobacillus ferroxidans, Acidothiobacillus ferridurans, Acidothiobacillus ferriphilus, Sulfobacillus acidophilus, Sulfobacillus thermosulfidooxidans, Acidothiobacillus caldus, Acidothiobacillus thioxidans, Acidothiobacillus ambivalens and (archaea) Ferroplasma spp.
  • a consortium of bacteria comprising: Leptosprillum ferriphilum, Leptosprillum ferrooxidans, Acidothiobacillus ferroxidans, Acidothiobacillus ferridurans, Acidothiobacillus ferriphilus, Sulfobacillus acidophilus, Sulfobacillus thermosulfidooxidans, Acidothiobac
  • any base metal may be used which can be indirectly or directly oxidised by the bacteria and thereby detach from the precious metal.
  • the base metal may be selected from one or more of: copper, tin and aluminium. Any other suitable base metal may be used as are known to those skilled in the art.
  • the bioleaching step may be in the presence of ferrous (Fe 2+ ) ions.
  • the ferrous ions may be provided as iron (II) sulfate (FeS0 4 ).
  • the bacteria may oxidise the ferrous (Fe 2+ ) ions to form ferric (Fe 3+ ) ions which oxidise the base metal.
  • the bioleaching step may be in the presence of a culture medium.
  • the culture medium may comprise the ferrous ions.
  • the culture medium may be a liquid.
  • the culture medium may comprise one or more of: 9k, 4.5 k, heterotrophic basal salt (HBS), acidophilic basal salt (ABS) and trace element medium.
  • HBS heterotrophic basal salt
  • ABS acidophilic basal salt
  • Each of the 4.5k and the 9k may independently comprise: (NFLOiSC , KC1, K2HPO4, MgS0 4 -7H20, Ca(N0 ), FeS0 4 -7H 2 0 and distilled water.
  • the 4.5k may be the same as 9k in all respects except that it comprises half the amount of iron as 9k.
  • the culture medium may have a pH no greater than about 5, suitably no greater than about 4.5, suitably no greater than about 4, suitably no greater than about 3.5, suitably no greater than about 3, suitably no greater than about 2.5, suitably no greater than about 2.
  • the culture medium may have a pH of about 2 to about 5.
  • the culture medium may have a pH of about 2.
  • the culture medium may comprise one or more acids.
  • a non-limiting example of a suitable acid is sulphuric acid. Those skilled in the art will appreciate that the amount of acid present can vary depending on the target pH.
  • the culture medium may comprise sulfur.
  • sulfur can result in an increased concentration of sulphuric acid, which in turn can reduce or prevent formation of any unwanted precipitates, e.g. iron precipitate.
  • the article may be exposed to the bacteria and, where present, the culture medium, for at least about 12 hours, suitably at least about 1 day, suitably at least about 2 days, suitably at least about 3 days, suitably at least about 4 days, suitably at least about 5 days, suitably at least about 6 days, suitably at least about 7 days, suitably at least about 8 days.
  • the bioleaching step may be performed in a vessel (e.g. a bioreactor) at a mixing speed of at least 30 RPM, suitably at least 40 RPM, suitably at least 50 RPM.
  • a vessel e.g. a bioreactor
  • the recovering step may involve recovering the solid precious metal using any suitable means.
  • the recovering step may comprise filtering out the solid precious metal.
  • a bioreactor comprising: an article comprising a precious metal attached to a base metal; and one or more species of bacteria operable to bioleach the base metal by bacterial oxidation so as to detach the precious metal in solid form from the base metal.
  • the bacterial may be operable to bioleach the base metal by indirect bacterial oxidation.
  • a method of recovering a precious metal in solid form from an article comprising a base metal attached to the precious metal, the method comprising the steps of: (a) bioleaching of the base metal by bacterial oxidation in the presence of an added acid generator so as to detach the precious metal in solid form from the base metal; and (b) recovering the precious metal.
  • the acid generator may comprise elemental sulfur.
  • a method of recovering a precious metal in solid form from an article comprising a base metal attached to the precious metal, the method comprising the steps of: (a) bioleaching of the base metal by bacterial oxidation using a consortium of bacteria so as to detach the precious metal in solid form from the base metal; and (b) recovering the precious metal.
  • the consortium of bacteria may comprise any consortium of the first aspect of the invention.
  • a method of recovering a precious metal in solid form from an article comprising a base metal attached to the precious metal
  • the method comprising the steps of: (a) bioleaching of the base metal by bacterial oxidation using a consortium of bacteria in the presence of an added acid generator so as to detach the precious metal in solid form from the base metal; and (b) recovering the precious metal.
  • the acid generator may comprise elemental sulfur.
  • the consortium of bacteria may comprise any consortium of the first aspect of the invention.
  • Figure 1 shows a schematic illustration of a bacteria-catalysed reaction in relation to an example of the present invention.
  • Figure 2 shows an illustration of the mechanism by which both iron (II) and elemental sulfur are oxidised by bacteria to form iron (III) and sulfuric acid, respectively.
  • the role of the generated acid in assisting the oxidation of base metals (M) to release solid precious metal is also displayed.
  • Figure 3 shows a graph of bacterial culture medium pH versus time (days) for media containing Acidothiobacillus ferroxidans bacteria and various concentrations of elemental sulfur (0, 2, and 5 g/L).
  • Figure 4 shows a graph of bacterial culture medium pH versus time (days) for media containing a consortium of bacteria (composition of the consortium: Leptosprillum ferriphilum, Leptosprillum ferrooxidans, Acidothiobacillus ferroxidans, Acidothiobacillus ferridurans, Acidothiobacillus ferriphilus, Sulfobacillus acidophilus, Sulfobacillus thermosulfidooxidans, Acidothiobacillus caldus, Acidothiobacillus thioxidans, Acidothiobacillus ambivalens and (archaea) Ferroplasma spp) and various concentrations of elemental sulfur (0, 2, and 5 g/L).
  • a method of recovering a precious metal in solid form from an article involves a bacteria-catalysed reaction.
  • the reaction involves using bacteria in a medium to oxidise ferrous salts (Fe 2+ , which can be provided by iron (II) sulfate) to provide ferric ions (Fe 3+ ).
  • the ferric ions then oxidise the copper base metal and thereby the ferric ions are reduced to ferrous ions.
  • the copper base metal forms a salt (i.e. copper (II) sulfate) and is in solution in the medium, and the precious metal detaches in solid form from the copper base metal.
  • the precious metal can be conveniently and efficiently recovered in solid form (by detaching from the article as the base metal is solubilised as a soluble salt, for example), without further processing steps and without using highly toxic reagents, as are often used in methods of the prior art.
  • base metal recovery is believed to be enhanced by the oxidation/reduction reactions in the continuous presence of Fe 3+ , which is continuously regenerated by bacterial oxidation of Fe 2+ to Fe 3+ .
  • Example 1 Indirect bioleaching for solid gold extraction from printed circuit boards comprising gold fingers, using Acidothiobacillus ferroxidans
  • Acidothiobacillus ferroxidans was inoculated to 9k medium which had the following composition (unit: g/1): (NH 4 ) 2 S0 4 3.0, KC1 0.1, K 2 HP0 4 0.5, MgS0 4 -7H 2 0 0.5, Ca(N0 3 ) 20.01, FeS0 4 -7H 2 0 44.2, in distilled water. Sulfuric acid 1 M was used to adjust the pH to 2. This operation was performed in a 250 ml Erlenmeyer flask with a total liquid volume of 100 ml of medium. Following inoculation, bacterial growth was performed in a shaker incubator at 30°C and 100 RPM.
  • Gold fingers were mechanically separated from PCBs so that the gold concentration was higher than in whole PCBs.
  • the gold fingers contained 42% organics, 10.86% calcium, 10.30% copper and 4.35% aluminium and 0.82% gold.
  • Gold plated on the surface of both sides of the gold fingers had a thickness of 3.5 micron.
  • the gold leaves which remained solid, were separated from the PCB support as the base-metals, which were holding gold to the PCB, were dissolved, due to the bioleaching activity of the bacteria on the base metals. Dissolution of the metals was confirmed by further content analysis of the leachate solution by inductively coupled plasma atomic emission spectroscopy (ICP-OES). The solid gold leaves remained floating in the solution, in a collectable form.
  • ICP-OES inductively coupled plasma atomic emission spectroscopy
  • Example 2 Indirect bioleaching for solid gold extraction form gold fingers using a consortium of acidophilic bacteria
  • composition of the consortium :
  • the bacterial consortium was inoculated in the medium containing acidophilic basal salt, trace elements, 50 mM FeS0 4 , with a small amount (approx. 2g/L) of sulfur added to the flask. Sulfuric acid (1 M; approx a few drops) was used to adjust the pH to 2. This was performed in a 250 ml Erlenmeyer flask, with a total liquid volume of 100 ml of medium. Following inoculation, bacterial growth was performed in a shaker incubator at 30 °C and 100 RPM.
  • Example 1 As described in Example 1, 0.6 g of the gold finger was added to the flask from the first day. Colour change confirming bacterial growth was observed after 48 hrs, and as in example 1, after 5 days the solid gold leaves were found floating at the surface of the solution, in a collectable form. Due to the lower amount of Fe (II) introduced in this medium (in comparison to 9k medium in example 1) and the presence of sulfur which resulted in sulfuric acid, no iron precipitate was observed therefore avoiding mixing iron with gold. On day 6, following removal of the gold leaves and the remained plastics of PCBs from the flask, another 0.6 gr of gold finger was added to the flask for which only 3 days were necessary for the gold leaves to be separated from PCB support.
  • II Fe
  • an acid generator such as sulfur
  • sulfur it is converted by bacteria to form sulfuric acid and results in reduction of precipitate formation, which can otherwise act as a passivation layer on the surface of the waste.
  • tests were performed in 250 mL Erlenmeyer flasks with a total liquid volume of 100 mL of medium.
  • Bacteria Bacteria (Acidothiobacillus ferroxidans or consortium of Example 2) were inoculated in a medium containing acidophilic basal salts and varying concentrations of FeS0 4 (30, 40, or 50 mM) and sulfur (0, 2, or 5 g/L).
  • Sulfuric acid 1 M was used to adjust the pH to 2.
  • bacterial growth was performed in a shaker incubator at 30°C and 160 RPM.
  • Varying numbers of gold fingers 13, 15, or 17 fingers were added to the flask from the first day. Colour change confirming bacterial growth was observed, and after varying periods of time, solid gold leaves were found floating at the surface of the solution, in a collectable form.
  • bacteria can act as both sulfur and iron oxidants.
  • the added sulfur is oxidised by the bacteria to form sulfuric acid, which can thereafter assist iron (III) in base metal oxidation, as shown in Figure 2.
  • the sulfuric acid is also able to reduce the formation of precipitates forming a passivation layer on the gold finger surface to further increase efficiency.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Metallurgy (AREA)
  • Mechanical Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Biotechnology (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Microbiology (AREA)
  • Biochemistry (AREA)
  • Preparation Of Compounds By Using Micro-Organisms (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Micro-Organisms Or Cultivation Processes Thereof (AREA)

Abstract

1. L'invention concerne un procédé de récupération d'un métal précieux sous forme solide dans un article, l'article comprenant un métal de base fixé au métal précieux, le procédé comprenant les étapes suivantes : (a) la bio-lixiviation du métal de base par oxydation bactérienne de manière à détacher le métal précieux sous forme solide du métal de base ; (b) la récupération du métal précieux.
EP21749272.7A 2020-07-22 2021-07-21 Procédé de récupération d'un métal précieux dans un article Pending EP4185724A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GBGB2011340.3A GB202011340D0 (en) 2020-07-22 2020-07-22 Method of recovering a precious metal from an article
PCT/GB2021/051871 WO2022018437A1 (fr) 2020-07-22 2021-07-21 Procédé de récupération d'un métal précieux dans un article

Publications (1)

Publication Number Publication Date
EP4185724A1 true EP4185724A1 (fr) 2023-05-31

Family

ID=72338831

Family Applications (1)

Application Number Title Priority Date Filing Date
EP21749272.7A Pending EP4185724A1 (fr) 2020-07-22 2021-07-21 Procédé de récupération d'un métal précieux dans un article

Country Status (3)

Country Link
EP (1) EP4185724A1 (fr)
GB (1) GB202011340D0 (fr)
WO (1) WO2022018437A1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114317998B (zh) * 2021-12-29 2023-07-04 上海第二工业大学 一种微电场耦合微生物处理废钯炭催化剂中杂质金属的方法
WO2023229528A1 (fr) * 2022-05-24 2023-11-30 National University Of Singapore Procédés d'extraction de métaux du groupe du platine

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS50122434A (fr) * 1974-03-15 1975-09-26
JP5666835B2 (ja) * 2009-06-23 2015-02-12 公立大学法人大阪府立大学 金属の回収方法
CN104073639B (zh) * 2014-06-24 2016-04-20 上海第二工业大学 一种两步法从废弃电子物料中回收铜和金的方法
CN108396148A (zh) * 2018-03-19 2018-08-14 成都理工大学 一种利用不同微生物分步浸出废弃线路板中铜和金的方法

Also Published As

Publication number Publication date
WO2022018437A1 (fr) 2022-01-27
GB202011340D0 (en) 2020-09-02

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