NL2031328B1 - Process for the generation of hydrogen sulfide in the presence of pyrite as catalyst - Google Patents
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/16—Hydrogen sulfides
- C01B17/161—Preparation from elemental sulfur
- C01B17/162—Preparation from elemental sulfur from elemental sulfur and hydrogen
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/20—Methods for preparing sulfides or polysulfides, in general
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/12—Sulfides
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
Abstract
The invention provides a process for the generation of hydrogen sulfide, which process comprises contacting elemental sulfur in water with H2, in the presence of pyrite as catalyst. The process is very suitable for the recovery of at least one metal as metal sulfide from a metal-containing stream containing the at least one metal in dissolved form, by allowing the hydrogen sulfide so produced and the at least one metal to form the metal sulfide, which may then be recovered as a precipitate. Moreover, this invention describes a cheap, easy, environmentally benign, potentially one-pot chemical synthesis method for pyrite to be used as catalyst from earth-abundant elements at mild conditions.
Description
P35585NLO0/MKO
Title: Process for the generation of hydrogen sulfide in the presence of pyrite as catalyst
The current invention concerns a process for the generation of hydrogen sulfide, also known as sulfidogenesis. Moreover, the current invention concerns the recovery of metals as metal sulfides from a metal-containing stream, in particular a metal-contaminated wastewater stream. Moreover, it concerns a process for producing metal sulfide particles, and synthetic pyrite particles in particular, for use in the recovery process.
The most common treatment of metal-containing waters is their indiscriminate neutralization with e.g. gypsum, and subsequent storage of the metal-gypsum slurry in tailings ponds.
Mining and metallurgy wastewaters in most cases still contain (very) high concentrations of valuable metals such as copper, zinc and cobalt. Still, recovery and recycling is rarely performed. These waters therefore represent not only an enormous environmental liability, but also a significant loss of potential revenue. This is only expected to increase with the increasing metal demands associated with the transition to renewable energy technologies.
Metal contaminants from a metal-contaminated wastewater stream may be removed with the addition of hydrogen sulfide. The metal contaminants may be separated as metal sulfides.
However, the offsite production and subsequent transport of hydrogen sulfide is not attractive for safety and economic reasons.
The use of sulfide for precipitating and recovering metals such as copper from metal- containing streams is widely known in the art. WO97/29055 teaches contacting a stream containing copper (and/or other metals) and sulfate with hydrogen sulfide to precipitate copper sulfide, separating the copper sulfide and subsequently biologically reducing sulfate to sulfide, which sulfide is then recycled to the precipitation step. WO00/029605 discloses biological reduction of elemental sulfur to gaseous hydrogen sulfide for use in precipitating metals, such as copper or lead, as their sulfides. WO00/039035 discloses metal precipitation involving biological reduction of sulfur compounds and using a sand filter to separate precipitated metal sulfides from the treated wastewater stream.
From EP3478863 a process is known of selectively separating one or more desired metals such as copper from multi metal streams, for example metal mining leachates, wherein the multi metal stream contains one or more metals such as copper, arsenic, zinc, nickel, cobalt and iron (Il). It was found that metals can be selectively separated from a liquid medium containing these metals by adding a slurry of a metal sulfide of intermediate solubility in a first reactor, separating a metal sulfide of low solubility, treating the resulting liquid with a biologically produced sulfide source in line in a second reactor to reproduce the metal sulfide of intermediate solubility, and returning part of the metal sulfide of intermediate solubility to the first reactor. In US2004/0115120 a process is provided for the production of hydrogen sulfide from the bacterial reduction of a mixture of a liquid and elemental sulfur with an electron donor, wherein the hydrogen sulfide is stripped and used in metal recovery. Indeed, two metal recovery processes for the mining and metals sector were developed by the company Paques, both based on biological production of sulfide. These sulfidogenesis processes used either sulfate (SO4?) (THIOPAQ) or elemental sulfur (THIOTEQ) as electron acceptors. Both have been successfully applied at metallurgy plants in the past, but the market remains small. The use of stable, on-site chemical sulfidogenesis is highly desirable, as it eliminates the need for transport of corrosive, toxic H2S, and gives the ability to tailor sulfidogenesis to process demands. However, the THIOPAQ and THIOTEQ bioreactors in use are operated at mesophilic, neutrophilic conditions (pH 7, 30°C). So far, when these processes would be applied to high temperature or low pH waters, the water streams must be cooled down or neutralized due to the sensibility of the microbes involved, with the associated costs. Unfortunately, the conditions at which microorganisms that are currently used in the process are capable to survive and be active are very limited. It would therefore be very attractive to have an alternative process. Currently no technologies are in place applying sulfidogenesis at (thermo)acidophilic conditions for the recovery of metals from (hot) acidic metalliferous wastewater streams. The current inventors addressed this issue by providing a process for sulfidogenesis from elemental sulfur and Hz. This may be at a range of conditions including high temperature and low pH: typically between pH 3 and 6 and 40°C to 80 °C.
Interestingly, sulfidogenesis using pyrite as catalyst enables recovery of metals as metal sulfides from a metal-containing stream. The catalytic sulfidogenesis may also be combined with other processes that rely on hydrogen sulfide.
Pyrite finds use in leaching processes for copper concentrates. Examples include
US20050269208, US20110056331, US20130209335, and US20150211092. These processes are different from the current process: the leaching step is typically carried out in an acidic sulfate leach solution, for example a ferric sulfate medium, under conditions whereby the pyrite is not materially oxidized. The process includes the application of an oxidizing agent, e.g., oxygen in the form of air or oxygen gas. From CN105060455 a photocatalysis method for synergetic removal of metal organic pollutants from water is known, using natural pyrite. A synthetic route to pyrite is not disclosed. In JP2007209824 a method is described for cleaning contaminated soil or contaminated groundwater. The method comprises adding a peroxide and a sulfide mineral such as pyrite to soil or ground water containing an organic compound.
The current inventors also addressed the issue of the short supply of noble metals that are currently used as electrocatalyst, and the potential for use of pyrite as an alternative catalyst.
Pyrite (FeSz) and other metal sulfides such as MnS., CoS;, CuSz, and NiS;, mixtures of the former metal sulfides, but even mixed metal sulfides (e.g.: chalcopyrite) are of great interest.
They are actively being investigated as sustainable, earth-abundant alternatives for noble metal catalysts (e.g. platinum). They may find use in renewable energy technologies such as photovoltaic cells and water electrolysers for Hz production.
The catalytic performance of pyrite and other metal sulfides appears to be dependent on the nano- and micrometer size of the particles. For example, bulk pyrite is considered a bad conductor while nano- to micrometer-sized particles are electrochemically active. The nano- and micrometer size can be controlled via the physicochemical conditions (temperature, pH, pressure) and reagents used during chemical synthesis, as well as by milling the metal sulfide.
Currently, chemical synthesis of catalytic pyrite-type catalysts occurs mainly through a Hot
Injection Method (HIM), a Hydrothermal or a Solvothermal Method (HTM/STM). Via the HIM, a cooler liquid, sulfur dissolved in a (toxic) solvent, is injected into a heated liquid (120 — 250°C) with Fe in a (toxic) solvent. In HTM/STM, synthesis occurs in an autoclave-type device under high pressure, using either water (HTM) or another compound (STM) as solvent for the reaction. Often, surfactants are used to control the morphology of the nano/micro particles. Because these methods require high temperatures (>100 °C), high pressure, and/or additional (toxic) solvents and reactants, they are not suited for large scale production, both because of their complexity and the high energy demand and (toxic) support chemicals required.
A process for producing synthetic pyrite is known from US2009087374. According to this patent application, synthetic FeS, may be prepared by a sulfidation process comprising reacting ferric oxide, hydrogen sulfide, and elemental sulfur at a temperature above the melting point of element sulfur (115 °C). For the reasons set out above, this process is not attractive.
Current chemical synthesis methods for catalyst-grade metal sulfides require high temperatures and pressures typical for chemical processes, and/or require the use of additional solvents, making the process less sustainable. In order to make catalysts from earth-abundant elements truly sustainable, it is therefore crucial to develop a low-cost, non- toxic, easily scalable chemical synthesis method. This requires for example that no additional harmful/expensive chemicals are needed, and that technologically advanced synthesis steps are avoided.
The present inventors have discovered an elegant process for the generation of hydrogen sulfide, which process comprises contacting elemental sulfur in water with Hz in the presence of pyrite as catalyst. The sulfidogenesis process may be performed preferably oxygen-free.
Moreover the process may be performed at acidic conditions. The sulfidogenesis process is very suitable for the recovery of at least one metal as metal sulfide from a metal-containing stream containing the at least one metal in dissolved form, by allowing the hydrogen sulfide so produced and the at least one metal to form the metal sulfide, which may then be recovered as a precipitate. Moreover, this invention describes a cheap, easy, environmentally benign, potentially one-pot chemical synthesis method for pyrite to be used as catalyst from earth-abundant elements at mild conditions. The recovery process can be performed in batch, or in a continuous mode.
Figure 1 provides the X-Ray Diffraction analysis for pyrite synthesized at 80°C, pH 4. The dotted lines indicate peak positions characteristic for pyrite as identified in the inorganic crystal structure database (ICSD: 01-071-2219).
Figure 2 illustrates hydrogen sulfide production in batch incubations. pH (triangles), total sulfide concentration (squares) expressed in mM over the liquid (primary y-axis), and total dissolved iron concentrations (mM) (circles) (both on secondary y-axis), with (A) or without (B) supplementation of 2 mM FeCl, (negative control). Incubations were performed in triplicate, and individual replicates are plotted.
Figure 3 illustrates pyrite formation and hydrogen sulfide production in batch incubations performed at (A) pH 4, 60 °C and (B) pH 6, 80 °C. Total sulfide concentration (triangles) expressed in mM over the liquid {primary y-axis) and pH (circles) (secondary y-axis) are shown.
Figure 4 illustrates hydrogen sulfide production (triangles) and pH (circles) in incubations with
H2/CO: in the headspace, and (A) 2 mM of milled commercially sourced pyrite (particle size <50 um) with 25 mM elemental sulfur, (B) a positive control with 2 mM Fe?*, 25 mM elemental sulfur, and 0.5 mM H>S amendment at time 0, and (C) milled pyrite but without elemental sulfur. Physicochemical parameters monitored in incubations: pH (circles) and total sulfide (triangles) expressed in mM over the liquid.
The definition of the particle size of the pyrite particles is the maximum diameter, as determined by sieving or any similar measurement.
The expressions “anoxic” and oxygen-free refer to the substantial absence of (dissolved) oxygen, causing side-reactions. Typically this means less than 100 ppm O..
The sulfidogenesis process is particularly suitable for the recovery of one or more metals as metal sulfide(s) from a metal-containing stream, for instance one or more heavy metals from a mining wastewater stream. The term "heavy metals" is used herein as common in the art, i.e. metals having an atomic number higher than 20 (calcium) and having a low solubility of 5 their sulfides or hydroxides. In general, for the purpose of the present invention, these comprise transition metals, including lanthanides, of columns 3-16, in particular columns 4-18, more in particular columns 7-15, of row 4 and higher, in particular of rows 4-6, more in particular of rows 4 and 5 of the Periodic Table. Most prominent examples include Mn, Fe,
Co, Ni, Cu, Zn, As, Pd, Ag, Cd, Sb, Hg, Pb, Bi. The process is particularly suitable from Mn,
Fe, Co, Ni and Cu and other chalcophilic (“sulfide-loving”) metals. Solubilities of heavy metal sulfides are well known in the art.
The recovery process allows the recovery of the at least one metal as a precipitate. The formation of the precipitate may be in the same reactor wherein the elemental sulfur is turned into hydrogen sulfide, but may also be in a separate reactor that is in connection with the reactor wherein the hydrogen sulfide is made.
The recovery process is particularly suitable for mining and/or metallurgy wastewater streams or similar metal-contaminated wastewater streams like e-waste processing and others. These wastewater streams are preferably first treated to remove any solids and preferably any oxygen dissolved in the metal-containing stream.
The recovery process preferably starts with the generation of pyrite first. The pyrite may be made from an Fe(ll} and/or Fe(lll) salt that can be dissolved in water. For instance, the pyrite can be synthesized by incubation of elemental sulfur, dissolved Fe?*, and HsS in anoxic water with a starting pH of around 3. All H2S required for FeS: formation can be supplied externally, or produced in the same reactor by the catalytic activity of the FeS: towards H. oxidation and elemental sulfur reduction. In the latter case, a small amount of H2S is added to ‘kickstart’ the process, after which it is autocatalytic for FeS2 formation and HsS production as long as Fe?*, elemental sulfur and Hz are supplied. The synthesis is preferably performed at about 80°C and at about 1.5-2.0 bar pressure.
The concentration of elemental sulfur and the partial pressure of Hz is not particularly relevant. For instance, the concentration of elemental sulfur in water may be in the range of 10 to 1000 mM, for instance in the range of 25 to 500 mM. Likewise, the Hz may be supplied at broad ranges, e.g. at a partial pressure in the range of 1.25 to 5 atm.
Once the pyrite is produced, it can be used as catalyst in the recovery process. As pyrite is a sulfide itself, the conditions at which it can be made may be the same as the conditions of the recovery process. However, in the recovery process also natural pyrite or pyrite made by an alternative process may be used. For instance, externally sourced, milled pyrite may be used as catalyst. Preferably, the pyrite used in the recovery process has a particle size of 50 micrometers or less, more preferably 25 micrometers or less.
This recovery process may also be started with some seed particles of pyrite, allowing hydrogen sulfide to be made from elemental sulfur and hydrogen gas. The hydrogen sulfide so produced can then form sulfide salts with the at least one metal in the metal-containing stream.
With catalytic pyrite particles, on-site, on demand chemical production of hydrogen sulfide from elemental sulfur and Hz is enabled even at acidothermal conditions, i.e. between pH 3 to 6 and 40°C — 80°C. This process may also be performed at higher pH and lower and higher temperature. The chemical nature of the process avoids both the fluctuations in performance related to the use of a microbial community. Furthermore, the catalyst for chemical elemental sulfur reduction in the current recovery process, being pyrite particles, form from simple, earth-abundant starting compounds, Fe?*, H2 and elemental sulfur. An elegant one-pot reaction may be conducted, for example by adding these substrates to the same reactor as where the recovery process will occur, adding significant value to the process.
The synthesis of the catalytic pyrite particles, but likewise the recovery process may be performed at a broad range of conditions. The temperature is preferably below 100°C, more preferably in the range of 40-80°C, more preferably still at 60-80°C. It may be performed at acidic condition, i.e. with a pH of 6.5 or less, for example in the range of 3-6. For instance, pyrite particles with a particle size of 50 um or less can be made at 80°C, pH 4.
Interestingly, the process for generating hydrogen sulfide and for the generation of a metal sulfide may be applied in a reactor setup similar to that of the process described in
EP3478863 mentioned above, the contents whereof are included herein by reference. As indicated, a single reactor may be used or a combination of reactors. Whereas in this prior art document various microorganisms are used to biologically generate HS, in the current process the H:S is prepared by using elemental sulfur and Hs, in the presence of pyrite.
The same or a similar type reactor may be used for the recovery process of the heavy metal sulfide. Either the hydrogen sulfide is produced therein in situ, e.g., when using the same reactor, or supplied to this reactor. To this the metal-containing stream is supplied as well.
The conditions are typically similar to those for the formation of pyrite although the retention time may be shorter or -preferably- longer.
After the metal sulfide is formed, it may be precipitated and recovered by any process known in the art. The particle size of the precipitated metal sulfide can be controlled to a large extent by minimizing the oversaturation of the metal sulfide which can be controlled by controlling the excess dissolved sulfide, which can be achieved by controlling the amount of Hz supplied.
It is advantageous to apply a gas recycle so as to minimize loss of hydrogen gas from the system. For instance, the hydrogen gas may be supplied at the bottom of the reactor using gas distributors and gas collected at the top is partly recycled to the gas supply at the bottom, and partly carried off, with a hydrogen sulfide trap to prevent hydrogen sulfide from being vented. The gas bleed is only required in case traces of inert gas components like nitrogen gas is present in the hydrogen feed gas. The reactor may also be provided with means for promoting a vertical circulation of the reactor medium, such as risers and downers.
Upon formation of the heavy metal sulfide, the effluent of the reactor is subjected to a solids separation step, to remove the metal sulfide from the effluent. The treated solution obtained by separating off precipitated heavy metal sulfide, may be acceptable for discharge.
Alternatively any further heavy metals may be removed by further precipitation or other chemical reactions, and then be discharged. Ideally, pyrite is maintained separate or is separated from the other metal sulfides generated in this process and recycled for further use as catalyst.
The process of the invention is particularly suitable for hydrometallurgical mining operations in which acidic metal-containing solutions are produced. Examples are gold mining (e.g. using hot acid leaching in autoclaves} and nickel mining (e.g. using heap leaching), but may also include wastewater streams resulting from the recycle of e-waste.
Typical metal-containing streams may contain 10-10,000 mg/l, in particular 20-2000 mg/l of different heavy metals like Cu, Zn, Ni and Co. The pH of such streams is normally low, e.g. 1- 3, due to presence of sulfuric acid, and temperatures can be medium (around 30°C) to high (up to 80°C). Other "contaminants" that can be present can include arsenic and iron. Iron present in the form of Fe(ll) or Fe(lll) can advantageously be used to form catalytic pyrite particles in situ.
Example 1 (pyrite formation)
Pyrite formation was performed in 117 mL glass serum bottles filled with 50 mL of water. Water was boiled to remove oxygen. After boiling, medium was cooled in ice water to room temperature under continuous Nz sparging. The gas flow was switched to N2/CO: to let the pH equilibrate, after which the pH was adjusted to 3.8 with 1 M — 5 M H2SOa4. Cooled medium (47 mL) was then transferred with a liquid dispenser under N2/CO: flow to 117 mL serum bottles containing 0.040 g of colloidal or orthorhombic elemental sulfur (Sigma Aldrich, St. Louis, MI) equivalent to 25 mM. Serum bottles were capped with butyl rubber stoppers (Ochs
Larborbedarf, Bovenden, Germany). The headspace was exchanged with N2/CO2 or H2/CO2 (both 80%/20%) by 5 cycles of vacuum-purging to a final pressure of 1.7 atm (room temperature). Fe (lll) or Fe(ll) was added from a sterile anoxic 1 M FeCl2.4H:0 (Honeywell,
Charlotte, NC, USA) solution or from a sterile 1 M FeCl:.6H:O (Sigma Aldrich, St. Louis, MI)
solution to a final concentration of 2 mM. In the case of the FeCls stock, the pH was readjusted to around 4 after addition of the Fe(lll).
For sulfide supplementation, an anoxic 1 M Na,S stock solution was prepared. NaS crystals (Acros Organics, Geel, Belgium) were rinsed with anoxic water, padded dry and dissolved in anoxic water by weight to a final concentration of 1 M. This solution was diluted (using a 0.22 um filter) to a ~50 mM sulfide stock solution in sterile anoxic water. This stock was acidified to the desired pH with sterile, anoxic 1 M H.SO4. Due to gas-liquid partitioning the final aqueous concentration in the acidified stock was approximately 30 mM. The acidified stock solutions were made fresh on the day of use. H2S was supplemented to approximately 0.5 mM in the liquid.
The pyrite particles so formed typically have a size in the range of 5-10 um.
In Figure 1 a confirmation of pyrite formation by X-Ray Diffraction analysis is shown.
Example 2 (sulfidogenesis)
Sulfidogenesis mediated by pyrite was observed at pH 4, between 40 °C and 80°C (Figure 2A and 3A). At 80 °C sulfidogenesis mediated by pyrite was observed at pH 3 up to pH 6 (Figure 3B).
Sulfide production was realized by supplying excess Hz and elemental sulfur to the abovementioned incubation containing in situ synthesized pyrite (Figure 2). Alternatively, sulfide production was realized by incubating sulfur and Hz in water under anoxic conditions in the presence of alternatively sourced pyrite particles (Figure 4A). In this case the control incubations were performed using commercially sourced pyrite (Sigma Aldrich, St. Louis, MI).
This pyrite was milled in 2-mL Eppendorf tubes using a laboratory mixer mill (Retsch MM200,
Retsch GmbH, Haan Germany) with a 3 mm tungsten carbide bead per Eppendorf (Qiagen
GmbH, Hilden, Germany), and sieved to obtain a final particle size of <50 um.
Example 3 {recovery of metal sulfides)
In a manner similar to that described in US2004/0115120, the contents of which are incorporated by reference, the catalytically produced hydrogen sulfide may be used to recover a dissolved metal from a metal-containing stream as metal sulfide. For instance, the catalytically produced hydrogen sulfide may be added to a mining wastewater such as acid mine drainage, or metallurgy wastewater streams, with subsequent recovery of the precipitated metal sulfide(s) in a conventional solids separation unit.
1. A process for the generation of hydrogen sulfide, which process comprises contacting elemental sulfur in water with Hz, in the presence of pyrite as catalyst. 2. The process of claim 1, wherein the process is performed under oxygen-free conditions, using anoxic water. 3. The process of any one of claims 1-2, wherein the process is performed at a temperature <100°C, preferably at a temperature in the range of 40-80°C. 4 The process of any one of claims 1-3, wherein the concentration of the elemental sulfur in water is in the range of 10 to 1000 mM, preferably in the range of 25 to 500 mM. 5. The process of any one of claims 1-4, in the presence of Hz, at a partial pressure in the range of 1.25 to 5 atm. 6. The process of any one of claims 1-5, wherein the pyrite has a particle size of 50 micrometer or less, preferably 25 micrometer or less. 7. The process of any one of claims 1-6, wherein the pyrite used as catalyst is prepared by dissolving an Fe salt, other than pyrite, in water and reacting the dissolved Fe salt, with elemental sulfur in the presence of H2, and in the presence of a substoichiometric amount of
H2S to form pyrite. 8. A process for the generation of a metal sulfide, by contacting elemental sulfur in anoxic water with Hz, under oxygen-free conditions, and in the presence of pyrite as catalyst, and allowing the hydrogen sulfide to form a metal sulfide with a dissolved metal. 9. The process of claim 8, wherein the metal sulfide is isolated as a precipitate. 10. The process of claim 8 or 9, wherein the metal is dissolved in a metal-containing stream, preferably a metal-contaminated wastewater stream, more preferably a mining and/or metallurgy wastewater stream or wastewater stream from the recycling of e-waste. 11. The process of any one of claims 8-10, wherein the metal is selected from one or more transition metals of columns 3-16 and rows 4-6 of the Periodic Table, more preferably from Mo, Fe, Co, Ni, Cu or a combination thereof.
Claims (11)
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
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| NL2031328A NL2031328B1 (en) | 2022-03-18 | 2022-03-18 | Process for the generation of hydrogen sulfide in the presence of pyrite as catalyst |
| PCT/EP2023/056930 WO2023175163A1 (en) | 2022-03-18 | 2023-03-17 | Process for the generation of hydrogen sulfide in the presence of pyrite as catalyst |
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| NL2031328A NL2031328B1 (en) | 2022-03-18 | 2022-03-18 | Process for the generation of hydrogen sulfide in the presence of pyrite as catalyst |
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| US20040115120A1 (en) | 1998-11-16 | 2004-06-17 | Paques Bio System B.V. | Process for the production of hydrogen sulphide from elemental sulphur and use thereof in heavy metal recovery |
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| US20150211092A1 (en) | 2012-11-12 | 2015-07-30 | Flsmidth A/S | Method and process for the enhanced leaching of copper sulfide minerals containing chalcopyrite |
| CN105060455A (en) | 2015-07-29 | 2015-11-18 | 中国科学院南海海洋研究所 | Natural pyrite based photocatalysis method for synergic removal of heavy metal-organic pollutants from water |
| EP3478863A1 (en) | 2016-07-04 | 2019-05-08 | Paques I.P. B.V. | Recovery of heavy metals by selective precipitation |
-
2022
- 2022-03-18 NL NL2031328A patent/NL2031328B1/en active
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- 2023-03-17 WO PCT/EP2023/056930 patent/WO2023175163A1/en unknown
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| WO2023175163A1 (en) | 2023-09-21 |
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