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WO2014067023A1 - Production d'acide sulfhydrique à partir de soufre au moyen d'un consortium microbien - Google Patents

Production d'acide sulfhydrique à partir de soufre au moyen d'un consortium microbien Download PDF

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Publication number
WO2014067023A1
WO2014067023A1 PCT/CL2013/000070 CL2013000070W WO2014067023A1 WO 2014067023 A1 WO2014067023 A1 WO 2014067023A1 CL 2013000070 W CL2013000070 W CL 2013000070W WO 2014067023 A1 WO2014067023 A1 WO 2014067023A1
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Prior art keywords
microbial consortium
bioreactor
halophilic
sulfur
hydrogen sulfide
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PCT/CL2013/000070
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English (en)
Spanish (es)
Inventor
Davor COTORAS TADIC
Cristian Patricio MARTÍNEZ LUCO
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Universidad de Chile
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Universidad de Chile
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Priority to CA2879839A priority Critical patent/CA2879839A1/fr
Priority to AU2013337536A priority patent/AU2013337536B2/en
Publication of WO2014067023A1 publication Critical patent/WO2014067023A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P39/00—Processes involving microorganisms of different genera in the same process, simultaneously
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P3/00—Preparation of elements or inorganic compounds except carbon dioxide
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P2203/00—Fermentation products obtained from optionally pretreated or hydrolyzed cellulosic or lignocellulosic material as the carbon source

Definitions

  • the present invention relates to a biological process for the production of hydrogen sulfide from sulfur, to be used for the industrial production of sodium sulfhydrate (NaSH), for its use in water treatment, in mining, cellulose and in the industry of tanneries, or directly as a precipitating agent of metals in mining or industrial effluents.
  • NaSH sodium sulfhydrate
  • PAQUES BV® is a company that develops technologies for water treatment, among which the biogenic production of H 2 S stands out with the patented THIOTEQ TM technology, which generates H 2 S from different sulfur sources (S °, sulfuric acid or other sources of sulfur) with an electron donor such as ethanol, acetic acid, hydrogen gas and others, at room temperature and pressure (US Patent 6,852,305; Buisman et al. 2006. Biologically produced sulphide for purification of process streams , effluent treatment and recovery of metais in the metal and mining industry. Hydrometallurgy. 83: 106-113).
  • the sulphide produced is introduced into a contact tank with the tributary, dissolving and precipitating the dissolved metals.
  • the metal sulphides are separated by sedimentation and dehydrated, generating an effluent treated with low levels of dissolved metals.
  • Another process for the production of biogenic H 2 S is described in Chilean Patent Application No. 200700022, which discloses a process of bacterial reduction of elemental sulfur, using sulfate reducing bacteria in the presence of sulfate and carbon dioxide .
  • This process uses hydrogen gas as an electron donor for the metabolism of sulfur reducing bacteria.
  • this process becomes restrictive for an application in the treatment of wastewater with high metal contents.
  • the alternatives currently available have different disadvantages.
  • the main difficulty is that sulfur-reducing bacteria use only low molecular weight organic molecules as electron donors, such as pyruvate, lactate, ethanol, mixtures of alcohols or hydrogen.
  • This invention solves the problems of the state of the art using a halophilic sulfur reducing microbial consortium, which is capable of using complex organic substrates, such as agroindustrial products or wastes, thus reducing the operating costs of the system.
  • Another feature of the invention is that the high pH values and high salt concentrations, at which the microbial consortium of this invention is capable of growing and producing hydrogen sulfide, generates a restrictive environment for the growth of other competing microorganisms (such as methanogenic archaea) or other contaminating microorganisms. This gives the process the additional advantage of greater stability.
  • the main object of the present invention is a biological method of producing sulfuric acid from sulfur by means of a microbial consortium, which comprises at least the steps of:
  • a culture medium that contains at least one suspension of one or more complex carbon organic substrates, such as donors of electrons and powdered or finely ground sulfur.
  • the bioreactor support material is the same complexed particulate carbon organic compound.
  • the halophilic sulfur reducing microbial consortium is enriched from an environmental sample.
  • the environmental sample is the anaerobic mud of a saline lagoon or a salt flat.
  • the halophilic sulfur reducing microbial consortium is composed of at least hydrolytic, fermentative, acetogenic and sulfur reducing microorganisms (see Figure 1).
  • the halophilic sulfur reducing microbial consortium is composed of bacteria and archaea.
  • the bacteria belong, at least, to the phylogenetic groups of Proteobacteria ⁇ , ⁇ , and ⁇ and bacteria of the Citofaga-Flavobacterium group.
  • the complex organic substrate (s) are naturally occurring products rich in polymeric organic compounds.
  • products of natural origin rich in polymeric organic compounds are selected from the group of cellulose, lignocellulosic plant products or residues, starch, starch-rich plant products or residues, seaweed, microalgae and cyanobacteria.
  • the support materials are selected from the group of ceramics, silicon stone, glass, diatomaceous earth extrudate and plastic.
  • the halophilic sulfur reducing microbial consortium has the ability to grow and produce hydrogen sulfide at pH 5.0 and 10.
  • the halophilic sulfur reducing microbial consortium has the ability to grow and produce hydrogen sulfide at pH 6.5 and 10. In another embodiment of the invention, the halophilic sulfur reducing microbial consortium has the ability to grow and produce hydrogen sulfide at pH 8.5 and 9.5.
  • the halophilic sulfur reducing microbial consortium has the ability to grow and produce hydrogen sulfide at sodium chloride concentrations between 0 and 100 g / L. In another embodiment of the invention, the halophilic sulfur reducing microbial consortium has the ability to grow and produce hydrogen sulfide at sodium chloride concentrations between 20 and 80 g / L.
  • the halophilic sulfur reducing microbial consortium has the ability to grow and produce hydrogen sulfide at sodium chloride concentrations between 25 and 70 g / L.
  • the halophilic sulfur reducing microbial consortium has the ability to grow and produce hydrogen sulfide at sodium chloride concentrations between 30 and 60 g / L.
  • the hydrogen sulfide acid produced is used as a metal precipitating agent in mining or industrial effluents.
  • the hydrogen sulphide acid produced is used for the industrial production of sodium hydrochloride (NaSH).
  • Microbial consortium in this invention, the concept of microbial consortium is understood as a group of different microorganisms that act together.
  • microorganisms with different metabolic capacities can be found.
  • sulfur reducing microbial consortium it is composed, for example, of hydrolytic, fermentative, acetogenic and sulfur reducing microorganisms.
  • hydrolytic proteolytic microorganisms capable of degrading proteins
  • sucroitic microorganisms capable of degrading several sugars
  • Lipolytic microorganisms capable of digesting lipids or fats
  • cellulite microorganisms capable of degrading cellulose or plant matter.
  • This figure shows a general outline of the stages and metabolic products in anaerobic microbial digestion of complex organic matter, using sulfur as an electron acceptor (Modified by Muyzer G., Stams A. 2008. The ecology and biotechnology of sulphate-reducing bacteria. Nature Reviews Microbiology. 6: 441-454).
  • BRS ° sulfur reducing bacteria.
  • FIGURE 2 is a diagrammatic representation of FIGURE 1
  • This figure shows the change in appearance that occurs in culture medium with starch, cellulose and spirulina as a substrate, before and after cultivating the microbial sulfur reducing consortium.
  • the black color is produced by the precipitation of iron sulfide generated by the interaction of the H 2 S produced with and the ferrous ion present in the culture medium.
  • FIGURE 3 is a diagrammatic representation of FIGURE 3
  • FIGURE 4 shows production of H 2 S by the microbial consortium, grown in media with cellulose (t3 ⁇ 43 ⁇ 43 ⁇ 4), starch (BH) and spirulina (IB) as electron donors, respectively. These cultures were grown for 14, 10 and 8 days, respectively. The values represent the means ⁇ standard deviation. The means with common letter (a, b) do not present statistically significant differences, according to Duncan (p ⁇ 0.05).
  • FIGURE 4 shows production of H 2 S by the microbial consortium, grown in media with cellulose (t3 ⁇ 43 ⁇ 43 ⁇ 4), starch (BH) and spirulina (IB) as electron donors, respectively. These cultures were grown for 14, 10 and 8 days, respectively. The values represent the means ⁇ standard deviation. The means with common letter (a, b) do not present statistically significant differences, according to Duncan (p ⁇ 0.05).
  • This figure shows the in situ hybridization of the microbial consortium grown in a starch culture medium.
  • the percentages of each of the groups, marked with the specific probes, are shown with respect to the total microorganisms marked with DAPI. Error bars correspond to the standard deviation between the percentages of microorganisms marked with the probe.
  • FIGURE 5
  • This figure shows the in situ hybridization of the microbial consortium grown in a cellulose culture medium.
  • the percentages of each of the groups, marked with the specific probes, are shown with respect to the total microorganisms marked with DAPI. Error bars correspond to the standard deviation between the percentages of microorganisms marked with the probe.
  • FIGURE 6 is a diagrammatic representation of FIGURE 6
  • This figure shows the in situ hybridization of the microbial consortium grown in a culture medium with spirulina.
  • the percentages of each of the groups, marked with the specific probes, are shown with respect to the total microorganisms marked with DAPI. Error bars correspond to the standard deviation between the percentages of microorganisms marked with the probe.
  • FIGURE 7 is a diagrammatic representation of FIGURE 7
  • This figure shows the effect of pH on the production of H 2 S by the starch-grown microbial consortium as a substrate for 21 days of culture.
  • the concentration of H 2 S is shown on days 5 (O), 8 (O), 14 ( ⁇ ) and 21
  • FIGURE 8
  • This figure shows the effect of pH on the production of H 2 S by the microbial consortium grown with spirulina as a substrate for 21 days of culture.
  • the concentration of H 2 S during days 5 ( ⁇ ), 8 (O), 14 () and 21 () of culture is shown.
  • the values represent the means ⁇ standard deviation.
  • the average values with the same letter are not statistically different, except the averages of the 21st day of cultivation (Duncan, p ⁇ 0.05).
  • FIGURE 9 This figure represents a simplified diagram of the fixed bed bioreactor used in the tests.
  • the culture medium containing the sulfur powder and one or more complex organic substrates is fed through the feed duct (1) with a pump (2) and entered through an inlet duct (3) to the bioreactor (5), filled with a support material (4), which can also be the same complex organic substrate in solid or particulate form).
  • the culture medium is recirculated through the recirculation duct (6) with a recirculation pump (7).
  • the effluent containing hydrogen sulfide is removed from the bioreactor through the outlet duct (8).
  • FIGURE 10 is a diagrammatic representation of FIGURE 10
  • This figure shows the performance profile of the cellulose-fed bioreactor and Celite R-635 as support material, during stage one of the bioreactor start-up.
  • the concentration values of H 2 S represent the means ⁇ standard deviation.
  • the concentration of hydrogen sulfide acid in effluent () is shown on the left axis and on the right axis the fed pH (+++) and the effluent pH () during operation.
  • the vertical segmented line ( ⁇ ) and the upper box in each figure represent the change in the mode of operation and the percentage of feeding with respect to the total volume of the bioreactor.
  • FIGURE 11 is a diagrammatic representation of FIGURE 11
  • This figure shows the performance profile of the cellulose-fed bioreactor and Celite R-635 as support material, during stage two of the bioreactor commissioning.
  • the concentration values of H 2 S represent the means ⁇ standard deviation.
  • FIGURE 12 is a diagrammatic representation of FIGURE 12
  • This figure shows the performance profile of the bioreactor without support and fed with spirulina as an organic substrate, during stage one of the bioreactor commissioning.
  • the concentration values of H 2 S represent the averages ⁇ standard deviation.
  • the concentration of hydrogen sulfide acid in effluent () is shown on the left axis and on the right axis the fed pH (+++) and the effluent pH () during operation.
  • the vertical segmented line (!) And the top box in each figure represent the change in the mode of operation and the percentage of feed with respect to the total volume of the bioreactor.
  • FIGURE 13 is a diagrammatic representation of FIGURE 13
  • This figure shows the performance profile of the bioreactor without support and fed with spirulina as an organic substrate, during stage two of commissioning the bioreactor.
  • the H2S concentration values represent the means ⁇ standard deviation.
  • the vertical segmented line (j) and the upper box in each figure represent the change in the mode of operation and the percentage of feed with respect to the total volume of the bioreactor.
  • the interval (//) represents a recirculated batch operation time in which there was no parameter determination.
  • FIGURE 14 is a diagrammatic representation of FIGURE 14
  • This figure shows the performance profile of the bioreactor fed with spirulina and Celite R-635 as a support material, during the bioreactor commissioning stage.
  • the concentration values of H 2 S represent the means ⁇ standard deviation.
  • ) and the top box in each figure represent the change in the mode of operation and the percentage of feed with respect to the total volume of the bioreactor.
  • the interval (//) represents a recirculated batch operation time in which there was no parameter determination.
  • Example 1 Cultivation of the sulfur reducing microbial consortium with complex organic substrates
  • the growth of the microbial consortium was evaluated with the three organic substrates studied in triplicate, determining the production of sulphides by the appearance of black precipitate. of iron sulfide (Postgate, 1979) and by the spectrophotometric method of production of methylene blue (Conagua. 1982. Water analysis - Determination of sulphides. Mexican Standard NMX-AA-084-1982. Mexico).
  • the method of production of methylene blue is based on the formation of blue color produced by the reaction of H 2 S with N, N-dimethyl-1,4-phenylenediamine oxalate and iron (III) chloride.
  • the quantification of hydrogen sulfide is carried out by taking 5 mL of sample, to which 500 ⁇ of a solution of N, N-dimethyl-1,4-phenylenediamino oxalate (6.75 g L "1 ) and 150 are added. ⁇ of ferric chloride (2500 g L '1 ), which is allowed to react for about 5 minutes, subsequently adding diamonium diphosphate (500 gL "1 ) to eliminate excess ferric chloride interference. After 5 minutes the absorbency of the sample was measured at 664 nm, which is proportional to the concentration of dissolved sulphides.
  • Table 1 Composition of the modified Postage C culture medium with the different substrates studied
  • Figure 2 shows the development of sulfur reducing bacteria due to the appearance of black precipitate in the culture media with starch, cellulose and spirulina as carbon sources, respectively.
  • Figure 3 the generation of H 2 S by the microbial consortium grown at pH 7.1 is shown in the three substrates studied by the methylene blue method. A greater production of sulfides is observed in the media grown with spirulina and starch, while with the cellulose substrate there is a significantly lower production of sulphides, according to Duncan's test (p ⁇ 0.05).
  • Example 2 In situ hybridization with fluorescent probe of the sulfur reducing microbial consortium.
  • the characterization of the microbial consortium grown on the different substrates was performed using the fluorescent in situ hybridization technique. Cultures used for hybridization were performed using the methodology used in Example 1. The probes used and their characteristics are shown in Table 2.
  • Table 2 Probes used in the study of microorganism characterization of the microbial consortium, its sequence, position in the rRNA and specificity in in situ hybridization (Amann et al. 1995. Phylogenetic Identification and In Situ Detection of Individual microbial cell without cultivation. icrobiol Rev. 59: 143-169).
  • ALF1b a-Proteobacteria C ⁇ 6S, 19-35) CGTTCGYTCTGAGCCAG
  • the slides with the samples were incubated for ninety minutes at 45 ° C, which after this time were washed with their respective wash solution for 30 minutes at 45 ° C (Table 4). Once washed, the slides with the fixed samples were allowed to dry at room temperature and then stained with 20 ⁇ of DAPI (4 ', 6-Diamidino-2-phenylindole) at 50 ⁇ g ⁇ mL "1 for 10 minutes, then rinsed with distilled water to remove excess DAPI The samples were finally observed in an epifluorescence microscope, with Zeiss filter No. 20 for probe labeled with CY3 and with Zeiss filter No. 09 to see the microorganisms labeled with DAPI.
  • DAPI 4- ', 6-Diamidino-2-phenylindole
  • Table 3 Composition of the hybridization solution used for the study of in situ hybridization for the different probes analyzed.
  • Table 4 Composition of the wash solution used for the study of in situ hybridization for the different probes analyzed.
  • the sulfur reducing microbial consortium is composed of bacteria and archaea. Also this consortium has in its microbial structure bacteria of the subclass Proteobacteria ⁇ , ⁇ and ⁇ , in addition to bacteria of the Citofaga-Flavobacterium group, depending on their composition of the type of complex carbon organic substrate used as for their cultivation.
  • Example 2 Effect of pH on the production of hydrogen sulfide by the sulfur reducing microbial consortium.
  • culture media were prepared as in Example 1, with the different substrates studied, with the exception of pH and the absence of ferric chloride.
  • the pH of the media was adjusted before autoclaving from 5.5 to 10.0 with an amplitude of 0.5 units. However, these levels changed after sterilization.
  • the actual pH with which one worked was 5.2; 5.6; 6.1; 6.6; 7.1; 7.5; 8.0; 8.5; 8.9 and 9.4.
  • In these media sulfide measurements were made by the methylene blue method.
  • Figure 7 shows that the production of H 2 S by the microbial starch consortium, as an electron donor, there was a significantly higher production at pH 8.9 and 9.4, compared to the other pH analyzed for all the days studied (Duncan test, p ⁇ 0.05), those that remained relatively stable within the range of 3 - 30 ppm of H 2 S.
  • Example 3 Development of the microbial sulfur reducing consortium in a reactor with support and with cellulose as an organic substrate.
  • This bioreactor consisted of a main column with two upper and lower inlets, to which it was filled with support material, culture medium (similar to that used in Example 1, except for the absence of ferric chloride and the concentration of NaCI, which was 40 g L "1 ) and cellulose as an organic substrate at a concentration of 1 gL " which was subsequently autoclaved at 110 ° C for 30 minutes.
  • the culture medium containing the sulfur powder and cellulose is fed through the feed line (1) with a pump (2) and the bioreactor (5), filled with Celite R-635 (4), is entered through an inlet duct (3).
  • the recirculating culture medium through the recirculation duct (6) with a recirculation pump (7).
  • the effluent containing hydrogen sulfide is removed from the bioreactor through the outlet duct (8).
  • this bioreactor was operated in batch, and then passed to a semi-continuous upward recirculated batch stage to achieve a 24-hour recirculation hydraulic retention time (HRT).
  • HRT 24-hour recirculation hydraulic retention time
  • a fresh inlet and substrate were fed through a lower inlet in a g COD / g S ° ratio of «1, 00 with a feed flow of 1.73 ⁇ 0.31 mL min " through a peristaltic pump, in volumes equivalent to the total volume of the bioreactors, while the effluent to be evaluated was removed from the upper part.
  • H 2 S accordinging to Example 1
  • pH of the effluents obtained to obtain the greatest sulfurogenic activity were estimated daily
  • the chemical demand for oxygen or COD was also determined (Kit Hanna Hl 93754A-25 LR, based on Official Standard Methods procedure, Standard Methods for
  • the bioreactor operation was temporarily separated into two stages; a first stage in which the parameters and optimal start-up times and the period of immobilization of the microorganisms were established; and a second stage in which the bioreactors were operated under a semi-continuous regime, which sought to increase the volumetric productivity of H 2 S, modifying parameters such as hydraulic retention times and the volume and pH of the fed medium.
  • Figures 10 and 11 show the performance profile of the bioreactor fed with cellulose and filled with Celite R-635 as a support material during the two stages studied. A gradual increase in volumetric productivity of H 2 S, reaching a maximum of 1.94 mol / m 3 d in this bioreactor with cellulose as organic substrate.
  • Example 4 Development of the sulfur reducing microbial consortium in an unsupported reactor and with spirulina as an organic substrate.
  • Example 3 A Teflon reactor of the same characteristics used in Example 3 and with the same methodology was used, with the exception of the substrate supplied, the absence of support material and the concentration of NaCI, which was 30 gL "1. This bioreactor was fed with spirulina at a concentration of 1 gL "1 as an organic nutrient.
  • Figures 12 and 13 show the performance profile of the bioreactor fed with spirulina and without support material during the two stages studied. A gradual increase in volumetric productivity of H 2 S was observed, reaching a maximum of 2.75 mol / m 3 d in this bioreactor with spirulina as organic substrate.
  • Example 5 Development of the microbial sulfur reducing consortium in a reactor with support and with spirulina as organic substrate.
  • the methodology of operation and maintenance of this bioreactor was similar to that used in Example 3, with the exception of the substrate supplied and the concentration of NaCI, which was 30 gL "1.
  • This bioreactor was fed with 1 gL " 1 of spirulina as a nutrient organic.
  • the production of H 2 S (according to Example 1) and the pH of the effluents obtained to obtain the greatest sulfurogenic activity were estimated daily.
  • the chemical oxygen demand or COD (as in Example 3) of some important points of the operation was also determined.
  • Figure 14 shows the performance profile of the bioreactor fed with spirulina and without support material during the two stages studied. A gradual increase in volumetric productivity of H 2 S was observed, reaching a maximum of 2.94 mol / m 3 d in this bioreactor with spirulina as organic substrate and Celite R-635 as support material.

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Abstract

La présente invention concerne un procédé biologique de production d'acide sulfhydrique à partir de soufre au moyen d'un consortium microbien, lequel procédé comprend au moins les étapes consistant: (a) à créer un consortium microbien réducteur de soufre halophyle, (b) à recycler le moyen de culture du bioréacteur jusqu'à formation de la biopellicule du consortium réducteur de soufre sur le matériau de support du bioréacteur, (c) à incorporer au bioréacteur de manière continue ou semi-continue, un milieu de culture contenant au moins une suspension d'un ou plusieurs substrats organiques carbonés complexes et (d) à retirer du bioréacteur l'effluent qui contient l'acide sulfhydrique.
PCT/CL2013/000070 2012-10-31 2013-10-04 Production d'acide sulfhydrique à partir de soufre au moyen d'un consortium microbien Ceased WO2014067023A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CA2879839A CA2879839A1 (fr) 2012-10-31 2013-10-04 Production d'acide sulfhydrique a partir de soufre au moyen d'un consortium microbien
AU2013337536A AU2013337536B2 (en) 2012-10-31 2013-10-04 Production of sulfhydric acid from sulphur by means of a microbial consortium

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CL2012003056A CL2012003056A1 (es) 2012-10-31 2012-10-31 Proceso biologico de produccion de acido sulfhidrico a partir de azufre mediante un consorcio microbiano, empleando sustratos organicos complejos como donadores de electrones.
CL3056-2012 2012-10-31

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5587079A (en) * 1995-04-21 1996-12-24 Rowley; Michael V. Process for treating solutions containing sulfate and metal ions.
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
WO2009100537A1 (fr) * 2008-02-12 2009-08-20 Bioteq Environmental Technologies Inc. Procédés de fabrication de h2s à l'aide de bactéries réductrices de soufre

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5587079A (en) * 1995-04-21 1996-12-24 Rowley; Michael V. Process for treating solutions containing sulfate and metal ions.
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
WO2009100537A1 (fr) * 2008-02-12 2009-08-20 Bioteq Environmental Technologies Inc. Procédés de fabrication de h2s à l'aide de bactéries réductrices de soufre

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CL2012003056A1 (es) 2013-02-01
CA2879839A1 (fr) 2014-05-08
PE20150540A1 (es) 2015-05-07
AU2013337536A1 (en) 2015-02-26
AU2013337536B2 (en) 2017-06-15

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