WO2002016660A1 - Procede de reduction mettant en oeuvre un cellule biologique chargee au palladium en tant que catalyseur - Google Patents

Procede de reduction mettant en oeuvre un cellule biologique chargee au palladium en tant que catalyseur Download PDF

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Publication number
WO2002016660A1
WO2002016660A1 PCT/GB2001/003737 GB0103737W WO0216660A1 WO 2002016660 A1 WO2002016660 A1 WO 2002016660A1 GB 0103737 W GB0103737 W GB 0103737W WO 0216660 A1 WO0216660 A1 WO 0216660A1
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substrate
aqueous medium
catalyst
reaction vessel
electron donor
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PCT/GB2001/003737
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English (en)
Inventor
Ivor Rex Harris
Lynne Elaine Macaskie
John Peter George Farr
Ping Yong
Neil Anthony Rowson
Amanda Natasha Mabbett
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The University Of Birmingham
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Priority to AU2001282293A priority Critical patent/AU2001282293A1/en
Publication of WO2002016660A1 publication Critical patent/WO2002016660A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00—Biological treatment of water, waste water, or sewage
    • C02F3/005—Combined electrochemical biological processes
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/70—Treatment of water, waste water, or sewage by reduction
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00—Biological treatment of water, waste water, or sewage
    • C02F3/28—Anaerobic digestion processes
    • C02F3/2806—Anaerobic processes using solid supports for microorganisms
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00—Biological treatment of water, waste water, or sewage
    • C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
    • 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
    • C12P1/00—Preparation of compounds or compositions, not provided for in groups C12P3/00 - C12P39/00, by using microorganisms or enzymes
    • C12P1/04—Preparation of compounds or compositions, not provided for in groups C12P3/00 - C12P39/00, by using microorganisms or enzymes by using bacteria
    • 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
    • C12P7/00—Preparation of oxygen-containing organic compounds
    • C12P7/02—Preparation of oxygen-containing organic compounds containing a hydroxy group
    • C12P7/22—Preparation of oxygen-containing organic compounds containing a hydroxy group aromatic
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
    • C02F1/4676—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electroreduction
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds
    • C02F2101/22—Chromium or chromium compounds, e.g. chromates
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/36—Organic compounds containing halogen
    • 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
    • C22B3/18—Extraction of metal compounds from ores or concentrates by wet processes with the aid of microorganisms or enzymes, e.g. bacteria or algae
    • 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
    • C22B5/00—General methods of reducing to metals
    • 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 novel method of reducing a substrate dissolved in an aqueous solution in the presence of a catalyst.
  • Enzyme-mediated bioreduction of metals is known. For example, it is reported that Desulfovibrio desulfuricans has broad metal reducing specificity (Fe, Mn, U, Cr, Tc and Pd) via hydrogenase and/or cytochrome c 3 . Metal ions are reduced and precipitated in the periplasm (J.R. Lloyd et al, Applied and Environmental Microbiology; (1998), 64(1 1 ), p4607). Such precipitation has been proposed as a means for recovering valuable palladium which is widely used in automobile catalysts.
  • a method of reducing a substrate in an aqueous medium in the presence of a pre-prepared catalyst comprising the steps of:-
  • the pre-prepared catalyst comprises a biological cell having palladium metal particles attached thereto.
  • the pre-prepared catalyst comprises a biological cell having palladium metal particles attached thereto.
  • the reduction product of the method is not precipitated in the aqueous medium.
  • the substrate may be dissolved in the aqueous medium or suspended or dispersed therein.
  • said substrate is a metal ion having a relatively high oxidation state
  • the reduction product is the metal ion having a relatively lower oxidation state.
  • suitable metals for reduction include Cr, Tc, Np, U, Pu, Mn, Se, Au, Pd, Pt, Rh, Ir, Mo and V.
  • the substrate may be a halogenated aromatic compound (eg. a chlorophenol compound or a polychlorinated biphenyl compound (PCB)) or a salt of hypophosphorous acid (eg. NaH 2 P0 2 ).
  • a halogenated aromatic compound eg. a chlorophenol compound or a polychlorinated biphenyl compound (PCB)
  • a salt of hypophosphorous acid eg. NaH 2 P0 2
  • the method includes the step of pre-preparing said catalyst, comprising attaching palladium metal particles to enzymatically active biological cells. It will be understood that said cells are not necessarily alive, i.e. viable.
  • said catalyst pre-preparation step comprises suspending said cells in a Pd(ll) solution, followed, after a predetermined period, by introduction of an electron donor.
  • said enzymatically active cell is a live resting cell.
  • said enzymatically active cell has metal reductase activity or cytochrome or hydrogenase activity functioning as a metal reductase.
  • said enzymatically active cell is the bacterium Desulfovibrio desulfuricans.
  • said enzymatically active cell is that deposited as ATCC 29577.
  • the aqueous medium is buffered to a pH of 7 or less, and more preferably to a pH of about 3.
  • the electron donor of step (ii) may be, for example, hydrogen or a salt of formic acid or pyruvic acid such as sodium formate or sodium pyruvate respectively.
  • the electron donor is hydrogen, in which case step (ii) may be achieved by bubbling hydrogen gas into the medium in the reaction vessel (eg. from a hydrogen cylinder, from a metal hydride store such as LaNi 5 , or from an electrochemical cell).
  • the substrate itself may serve as the electron donor.
  • the conversion of sodium hypophosphite (NaH 2 P0 2 ) to sodium phosphite (NaH 2 P0 3 ) involves donation of electrons from P(l) (which is oxidised to P(III)) to protons, the reduced protons being evolved as hydrogen gas.
  • Step (i) may be achieved by suspending the catalyst in the aqueous medium in the reaction vessel.
  • the method may include the prior step of immobilising the catalyst within the reaction vessel.
  • Said immobilisation step may be achieved by retaining the catalyst within a matrix in the reaction vessel, the matrix being permeable to the aqueous medium so that the contacting step can occur.
  • Suitable matrix materials include cotton wool and microfibre glass.
  • the catalyst may be adhered to the matrix in order to retain the catalyst in the reaction vessel.
  • the matrix may serve as a physical barrier to passage of catalyst out of reaction vessel, in which case such adherence is not required.
  • immobilising the catalyst within the reaction vessel enables the aqueous medium containing the substrate to be passed through the reaction vessel on a continuous basis, the catalyst remaining immobilised in the reaction vessel. This is particularly useful when the reduction product is dissolved in the aqueous medium.
  • said immobilisation step may be achieved by adhering the catalyst to a first surface of a support, preferably an active support, in the reaction vessel.
  • an active support is defined as a support which effects the electrochemical injection of hydrogen or homolytic fission of hydrogen molecules into hydrogen atoms.
  • said active support is a palladium-based alloy (eg. Pd- Ag, Pd-Y and Pd-Ce). More preferably, said alloy is a Pd-Ag, Pd-Y or Pd- Ce alloy containing from 20 to 25 atomic% Ag, from 8 to 10 atomic% Y or 6 atomic% Ce respectively. A particularly preferred alloy is 0.77%Pd- 0.23 %Ag.
  • hydrogen is supplied to the first surface of the support through the support from an opposite second surface. It will be appreciated that, in the case of an active support, hydrogen will be supplied to the first surface, and hence the cells attached thereto, as nascent hydrogen atoms.
  • the active support serves as a cathode of an electrolytic cell and is in the form of a tube having a closed lower end, the outer surface of the tube defining the first surface to which the cells are attached in use.
  • electrolyte solution within the tube and in contact with the second surface is separated from the substrate-containing aqueous medium within the reaction vessel by the active support which serves as a hydrogen permeable membrane between the aqueous medium and the electrolyte solution.
  • the electrolyte solution can be optimised for hydrogen generation without an adverse effect on the reduction.
  • Figures 1 A, 1 B and 2 are plots of Cr(VI) concentration against time under various reduction conditions
  • Figure 3 is a schematic view of a flow-through bioreactor used to prepare a catalyst for use in the present invention
  • FIGS. 4 and 5 are diagrammatic views of part of an apparatus for carrying out the method of the present invention.
  • Figure 6 is a diagrammatic view of part of another apparatus for carrying out the method of the present invention.
  • Figure 7 is a plot of Cl " concentration against time for the reductive dehalogenation of 2-chlorophenol according to the present invention
  • Figure 8 is a plot indicating time for onset of hydrogen evolution at various temperatures in the conversion of NaH 2 P0 2 to NaH 2 P0 3 .
  • Desulfovibrio desulfuricans (ATCC 29577) was grown for 24 hrs in anaerobic 100 ml serum bottles in Postgate's medium C and harvested by centrifugation for 30 mins under oxygen free nitrogen (OFN) at 3,000 rpm and ambient temperature, the bottles being kept on ice both before and after centrifugation.
  • OFN oxygen free nitrogen
  • the resultant pellet was washed anaerobically under OFN in the serum bottle with OFN pre-bubbled 20 mM morpholinopropane-sulphonic acid (MOPS)-NaOH buffer at pH 7 (50 ml) and the cells were suspended at a density of 0.25 mg dry weight/ml in 2 mM (Pd(li) solution (0.589 g Na 2 PdCI 4 per litre in 0.01 M HN0 3 ; pH 2). This was achieved by placing 5 ml of the Pd(ll) solution (or other volume as appropriate) in small anaerobic bottles under OFN, followed by addition of sufficient cells to give a biomass:Pd ratio of 1 :1 on a weight basis.
  • MOPS morpholinopropane-sulphonic acid
  • the resultant cell suspension was left in contact with the Pd(ll) solution for 2 hrs, this being the time required to biosorb Pd(ll) onto the biomass, achieving saturation of biosorption sites.
  • the cells were not left longer than this to contact the Pd(ll) since extended times can result in less active biomass.
  • the nitrogen was gassed- out by the introduction of H , and the suspension was stored under H 2 until all of the residual Pd(ll) had precipitated onto the biomass as Pd°.
  • the resultant 'active biomass' or 'bio-Pd' had a Pd:biomass dry weight ratio of 1 :1.
  • the identity of the precipitated material was confirmed as Pd° by X-ray powder diffraction analysis.
  • the cells were pre-grown as described above for prep A. The cells were then immobilised in a flow-through bioreactor described with reference to Figure 3.
  • the flow-through bioreactor comprises a reaction vessel 2 (20ml flow volume) having an inlet 4 and an outlet 6, a reservoir 8 for feedstock solution and a reservoir 10 for treated solution connected by tubing 12 to the inlet 4 and outlet 6 of the reaction vessel 2 respectively, and a pump 14 directly upstream of the reaction vessel 2 for effecting and controlling flow of solution through the reaction vessel 2.
  • solution within the reaction vessel 2 is stirred by means of a magnetic stirrer unit 16 and follower 18.
  • the bioreactor also incorporates an electrolytic cell comprising a dc power supply 20, a 0.76%Pd-0.24%Ag alloy cathode 22 in the form of a hollow tube (length 3.2cm, diameter 1.0cm, approximate surface area 12cm 2 ) closed at its bottom end and defining an electrolyte chamber 24, and a platinum anode 26 extending into the electrolyte chamber 24.
  • the electrolyte is 1M HN0 3 .
  • other supports for cell attachment are used, such as a carbon matrix.
  • the flow-through bioreactor was then challenged with a flow of Na 2 PdCI 2 in HN0 3 (2 mM Pd(ll), pH 2, pregassed with OFN) supplemented with D. desulfuricans ATCC 29577 (to give a biomass dry weight to Pd ratio of 1 :1 in the input solution) at an appropriate flow rate, with the biomass Pd (II) adhering to the electrode.
  • the metal-containing biomass (a black solid) was recovered from the floor of the flow-through bioreactor, having fallen from the electrode surface under gravity and/or scraped from the electrode surface.
  • Biomass prepared as for prep A was added to a vessel containing a processing waste solution diluted 1 :500 with water (supplied by Degussa Ltd, Germany) supplemented with laboratory waste solution containing Pd(ll) (total volume 2 I, pH 2.5).
  • the amount of biomass used was the same as the mass of Pd(ll) in the laboratory waste solution (0.2 mg /ml biomass (dry weight), i.e. a total of 0.4 g dry weight of biomass in the vessel.
  • the waste solution contained Pd(ll), Rh(lll) and Pt(IV).
  • the electrolytic cell described with reference to Figure 3 was immersed in the vessel and hydrogen generated (3V, 20 mA) while the Pd (II) and cell suspension mixture was stirred.
  • biomass was harvested from the electrode by scraping and from the solution by centrifugation.
  • the harvested material was washed with water and then acetone and dried at 80 °C.
  • the resultant material is hereinafter referred to as "industrial waste bio-Pd” and comprised Pd, Rh and Pt precipitated on the biomass (approximate 1 :1 ratio of biomass to metal).
  • a second preparation of chemical-Pd was achieved by following the methodology for the preparation of Bio-Pd (prep B) using the flow through bioreactor of Figure 3 in the absence of cells.
  • a solution (5 ml) was prepared under OFN in 20 mM MOPS-NaOH buffer, pH 7. To this was added 2 mg of bio-Pd (prep A). Two treatments were carried out. In the first case (1A) the solution was outgassed with OFN for 5 mins and then hydrogen for 5 mins and allowed to stand under H 2 (1 atmosphere). In the second case (1 B) sodium formate (pH 7) to a final concentration of 25 mM was added to the solution which was allowed to stand under OFN. The reaction was started by the addition of 700 ⁇ m Cr (VI) as sodium chromate. In each case, samples were removed periodically and centrifuged in air.
  • Examples 1A and 1 B were repeated with the bio-Pd replaced by cells of Desulfovibrio desulfuricans (ATCC 29577), Desulfovibrio vulga s (ATCC 29579) or Desulfovibrio sp. strain "Oz 7" cells which had not been subjected to the Pd biosorption/precipitation methodology.
  • the results for the ATCC 29579 cells are shown in Figures 1A and 1 B.
  • Bio-Pd prepared by prep B gives comparable results (data not shown). Referring to Figure 2, the results for reduction of Cr(VI) using bio-Pd under conditions similar to Example 1 in the absence of electron donor are shown. Substantially no reduction of Cr(VI) was observed. Similarly, substantially no reduction was achieved by the addition of H 2 as electron donor in the absence of catalyst (not shown).
  • Example 3 The protocol of Example 2 was followed, using 2 mg of industrial waste bio-Pd (Example 3) or 2mg of chemical-Pd (prep A, comparative example 3) and 500 ⁇ M of Cr(VI).
  • the industrial waste bio-Pd removed 95% of the Cr(VI) within 1 hr and all of the Cr(VI) by 2 hrs
  • the chemical-Pd removed only 34% of the Cr(VI) after 2 hrs, with approximately 2% residual Cr(VI) remaining in the solution after 24 hrs.
  • Example 3 shows that the presence of other metals on the cells does not poison the catalyst.
  • two objectives can be achieved, namely the recovery of waste precious metals, and their use in the catalytic reaction of the present invention. In view of the fact that most waste precious metals are not recovered, such waste provides a cheap source of Pd for use in the method of the present invention.
  • industrial waste bio-Pd 50 mg was sprinkled in a line 30 between opposite top and bottom edges 32 and midway between opposite side edges 34 of a square plate of absorbent cotton wool 36 (4cm x 4cm; total weight of cotton wool 0.29 g). This was rolled up into a cylinder such that the line 30 of waste bio-Pd extended substantially up the centre of the cylinder between the top and bottom end faces of the cylinder.
  • the cotton wool cylinder was inserted into a tubular fibre filter 38 and the cylinder-filter assembly was inserted into a tubular plastic column 40.
  • a Cr(VI) solution containing 1 mM Cr(VI) in a carrier of 1 M sodium formate and 1 M acetate (pH 3) was pumped into the base of the assembly (indicated by arrow A) and out of the top of the assembly (indicated by arrow B). It will be understood that the solution passed through the cotton wool (serving as a matrix for the waste bio-Pd) and contacted the waste bio-Pd, but the waste bio-Pd was retained within the cotton wool cylinder.
  • the removal of Cr(VI) by the column was 100% at a flow rate of 7 ⁇ l/min and 96% at a flow rate of 20 ⁇ l/min (1.2 ml/hr).
  • the fluid volume of the column was 14 ml therefore the flow residence time at the latter flow rate was about 33 hr.
  • the Cr(VI) removed from the column inflow was quantitatively recovered as Cr(lll) in the column outflow and therefore the catalyst did not accumulate soluble Cr ions or Cr(0), Cr 2 0 3 or Cr(OH) 3 or any Cr(VI) or Cr(lll) precipitate. Presence of Cr(lll) was determined by comparing the maximum peaks in the uv/vis spectrum (280-800 nm) of the column outflow with the peaks of a stock solution of CrCI 3 .6H 2 0 (1 mM in 1 M Na formate / 1 M Na acetate at pH 3).
  • Example 4 was repeated using chemical-Pd (prep A). Negligible Cr(VI) was removed from solution under the same conditions.
  • a solution (10 ml) was prepared under OFN comprising 5 mM 2- chlorophenol in 20 mM MOPS-NaOH buffer, pH 7. To this was added 4 mg of bio-Pd (prep A). Sodium formate (pH 7) to a final concentration of 50 mM was added to the solution which was allowed to stand under OFN at 30 °C. Samples were removed periodically and centrifuged in air. Reductive dehalogenation of the 2-chlorophenol occurred, with the amount of chloride released being determined by the thiocyanate method (spectrophotometric assay based on the displacement of thiocyanate by chloride ions from mercury (III) thiocyanate in the presence of Fe (III) ion.

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Abstract

La présente invention concerne un procédé de réduction d'un substrat se trouvant dans un milieu aqueux, en présence d'un catalyseur préparé antérieurement. Ce procédé consiste à mettre en contact le substrat se trouvant dans le milieu aqueux avec le catalyseur préparé antérieurement, dans une cuve de réaction, puis à pourvoir le milieu aqueux d'un donneur d'électron, afin de réduire le substrat. Le catalyseur préparé antérieurement comprend une cellule biologique à laquelle sont attachées des particules métalliques de palladium. Selon un aspect de cette invention, il n'y a sensiblement aucune accumulation du produit de réduction par les cellules biologiques. Selon un autre aspect de cette invention, le substrat est sélectionné dans le groupe formé par un composé aromatique halogéné, tel qu'un composé chlorophénolique ou un composé biphénylique polychloré, un sel d'acide hypophosphoreux et un sel d'acide phosphoreux.
PCT/GB2001/003737 2000-08-25 2001-08-21 Procede de reduction mettant en oeuvre un cellule biologique chargee au palladium en tant que catalyseur WO2002016660A1 (fr)

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AU2001282293A AU2001282293A1 (en) 2000-08-25 2001-08-21 Reduction method using palladium-loaded biological cell as catalyst

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GB0020910A GB0020910D0 (en) 2000-08-25 2000-08-25 Reduction method

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL1023474C2 (nl) * 2003-05-20 2004-11-24 Tno Werkwijze voor het verwijderen van een verontreiniging uit een waterig medium met behulp van een membraan.
WO2006087334A1 (fr) * 2005-02-21 2006-08-24 Centre National De La Recherche Scientifique Utilisation de souches bacteriennes pour la preparation de biocatalyseurs metalliques, en particulier pour la preparation de biocatalyseurs a base de palladium
WO2011086343A3 (fr) * 2010-01-15 2012-05-03 The University Of Birmingham Catalyseur amélioré
CN108946956A (zh) * 2018-07-10 2018-12-07 同济大学 一种氢基质生物钯及其制备方法和应用
CN113426441A (zh) * 2021-07-07 2021-09-24 长春工业大学 一种Pt基催化剂的制备方法及其应用

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EP0292682A2 (fr) * 1987-05-28 1988-11-30 RIMAR CHIMICA S.p.A. Procédé de réduction catalytique de dérivés aromatiques nitro-halogonés
EP0573226A1 (fr) * 1992-06-01 1993-12-08 Masao Kuroda Electrode avec des biocatalyseurs immobilisées et méthode pour la traitement de l'eau utilisant cette electrode
US5324491A (en) * 1992-04-03 1994-06-28 The United States Of America As Represented By The Secretary Of The Interior Enzymatic reduction and precipitation of uranium
US5334782A (en) * 1991-04-23 1994-08-02 Ag Technology Co., Ltd. Method for producing a hydrogen-containing chloromethane
WO2001062990A1 (fr) * 2000-02-23 2001-08-30 The University Of Birmingham Procede et bioreacteur permettant d'effectuer la reduction enzymatique de cations metalliques dans une solution

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Publication number Priority date Publication date Assignee Title
GB1593908A (en) * 1977-12-05 1981-07-22 Babcock & Wilcox Co Reference electrodes and measuring systems for detemining the amount of disolved oxygen in a liquid
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NL1023474C2 (nl) * 2003-05-20 2004-11-24 Tno Werkwijze voor het verwijderen van een verontreiniging uit een waterig medium met behulp van een membraan.
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WO2011086343A3 (fr) * 2010-01-15 2012-05-03 The University Of Birmingham Catalyseur amélioré
CN108946956A (zh) * 2018-07-10 2018-12-07 同济大学 一种氢基质生物钯及其制备方法和应用
CN113426441A (zh) * 2021-07-07 2021-09-24 长春工业大学 一种Pt基催化剂的制备方法及其应用

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