WO2013167107A1 - Dispositif de conversion bio-électrochimique de substances (mise en oeuvre d'une réduction / d'une oxydation / d'une réaction redox) - Google Patents

Dispositif de conversion bio-électrochimique de substances (mise en oeuvre d'une réduction / d'une oxydation / d'une réaction redox) Download PDF

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Publication number
WO2013167107A1
WO2013167107A1 PCT/DE2013/000247 DE2013000247W WO2013167107A1 WO 2013167107 A1 WO2013167107 A1 WO 2013167107A1 DE 2013000247 W DE2013000247 W DE 2013000247W WO 2013167107 A1 WO2013167107 A1 WO 2013167107A1
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WO
WIPO (PCT)
Prior art keywords
anode
cathode
reactor
bioelectrochemical
substrate
Prior art date
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PCT/DE2013/000247
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German (de)
English (en)
Inventor
Florian Pfeiffer
Original Assignee
Florian Pfeiffer
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 Florian Pfeiffer filed Critical Florian Pfeiffer
Priority to DE112013002364.4T priority Critical patent/DE112013002364A5/de
Publication of WO2013167107A1 publication Critical patent/WO2013167107A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/32—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by electrical effects other than those provided for in group B01D61/00
    • B01D53/326—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by electrical effects other than those provided for in group B01D61/00 in electrochemical cells
    • 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
    • C02F1/46104—Devices therefor; Their operating or servicing
    • C02F1/46109—Electrodes
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/84—Biological processes
    • B01D53/85—Biological processes with gas-solid contact
    • 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
    • C02F1/46104—Devices therefor; Their operating or servicing
    • C02F1/46109—Electrodes
    • C02F2001/46133—Electrodes characterised by the material
    • C02F2001/46138—Electrodes comprising a substrate and a coating
    • C02F2001/46142—Catalytic coating
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2201/00—Apparatus for treatment of water, waste water or sewage
    • C02F2201/46—Apparatus for electrochemical processes
    • C02F2201/461—Electrolysis apparatus
    • C02F2201/46105—Details relating to the electrolytic devices
    • C02F2201/4611—Fluid flow
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2301/00—General aspects of water treatment
    • C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
    • 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
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters

Definitions

  • the invention is based on a device for bioelectrochemical conversion according to the preamble of claim 1 and a method for operating the device according to the preamble of claim 13.
  • bioelectrochemical processes are already known, such as the closest prior art disclosed in International Patent Application WO2011 / 006939.
  • a three-stage process for the bioelectrochemical wastewater treatment of nitrogen compounds is shown.
  • the first stage a half element is arranged with an anode for the conversion of hydrocarbon compounds.
  • the second stage is formed from an aerobic reactor and in the third stage a half-element is arranged with a cathode for denitrification.
  • a disadvantage of this technical solution is that in this case a large expenditure on equipment is necessary and on the other hand, due to the aerobic reactor stage, higher costs and higher excess sludge are produced.
  • Aerobic biological processes achieve high efficiencies during purification, since oxygen (or air) is blown in until the processing substrate has been oxidized relatively completely. This is with the Disadvantage of a high sludge production and high additional energy requirements.
  • the high efficiencies in the aerobic process are based on the simple technical apparatuses and means used there, via which oxygen (O 2) is provided in sufficient quantity as a terminal electron receptor for the aerobic processes.
  • oxygen O 2
  • the use of oxygen produces a great deal of excess sludge, which must be post-treated relatively expensive following the aerobic process. In any case, this technology is itself very energy-intensive (see "Römpp-Lexikon, Biotechnology aerobic wastewater treatment).
  • the two processes namely for the reduction or elimination of nitrogen on an aerobic or anaerobic basis, can be combined with one another.
  • a combination of methods requires additional energy, for example, for the necessary recirculation.
  • both methods are limited in their substrate spectrum. In the anoxic intermediate region, the energy input as well as the efficiencies due to the substrate distribution is limited. Both methods are thus limited either in the substrate spectrum (for example, metered addition of an external carbon source) or in the synthesis production.
  • Bioelectrochemical denitrification has many advantages as well as in combination with the above techniques.
  • the achievable efficiencies are comparable to the oxidation, as the anode can perform this function without producing the increased excess sludge accumulation.
  • the cathode can take over the function of the electron donor, whereby a possible substrate restriction in the offer can no longer have a limiting effect on the cleaning performance.
  • the electrolysis has high efficiencies with a low sludge production and a broad substrate spectrum, but requires a lot of energy to overcome the cell and ion voltage.
  • the inorganic catalyst consumes during the electrolysis.
  • a mixed process with microbial fuel cell has never become marketable, due to the expensive arrangements.
  • the systems have been optimized for direct energy generation instead of relying on material conversion as a basic process.
  • the bioelectrochemical denitrification also has many advantages in combination with the above process techniques, since oxidation, or reduction, or a redox reaction can be brought about at a specific site and with great independence.
  • the underlying task of the invention
  • the invention has for its object to develop a method and a device for cleaning the contaminant load in a substrate such as sewage, manure, biogas plants and the like.
  • a substrate such as sewage, manure, biogas plants and the like.
  • the method should be combinable with conventional methods in order to optimize them. It is the surplus sludge balance to be improved while reducing the operating costs.
  • the process should have a higher efficiency, as well as a broader substrate spectrum.
  • the expenditure on equipment is reduced in comparison to the previously known methods.
  • the process works membraneless and is thus suitable for both batch and continuous operation, whereby it is irrelevant whether it is a special (aggressive) or moderate environment environment.
  • a biofilm is applied to the at least one anode and / or at least one cathode. Attaching the biomass to the electrodes catalyses the process that is going on. Due to this reduced cell voltage and the energy expenditure is comparatively very low and it must be overcome only the cell voltage of the bacterial mass involved. For this purpose, a low potential is applied from the outside, such as the potentiostat. Thus, the process becomes a low load process. On the one hand, because of the thermodynamic situation of the underlying redox reactions, an excess of the electron can be achieved or, on the other hand, any deficiency for a particular reaction with additional electrons can be compensated.
  • the biofilm on the at least one anode and / or the at least one cathode is a sessile biofilm.
  • a sessile biofilm follows a direct electron uptake and -abgäbe by means of the catalyzing biomass, whereby the usually very large concentration gradient between the fixed at least one electrode biofilm and the surrounding substrate is reduced.
  • Process catalysing sessile biofilm produces less excess sludge.
  • Due to the omission of the introduction of elemental oxygen as the terminal electron acceptor a further reduction of the excess sludge production takes place (see Anaerobic Technique).
  • an electrical conductor is arranged on the at least one anode and / or the at least one cathode for electron transport.
  • an electrical conductor is arranged between the at least one anode and the at least one cathode for electron transport.
  • the device has a material line for the proton transport between the at least one anode and / or the at least one cathode. The proton transport takes place with the substrate, the electron transport via an electrical conductor. The method allows the involved redox partners to deliver the electrons directly from cell to cell.
  • the material line for proton transport is a salt bridge or the like.
  • the device according to the invention several reactors are present, which are connected as a cascade.
  • the arrangement of several reactors connected in series has the advantage that the wastewater to be clarified can be treated with its contaminant load in different stages and thus all individual reactor stages can be preconfigured specifically for the contaminated load (utilization of a concentration gradient).
  • a balance of the bioelectrochemical equilibrium takes place by means of external energy intervention.
  • the equilibrium of the reaction can always be adjusted so that the desired reactions proceed preferentially.
  • the at least one anode and / or the at least one cathode cause a mixing of the at least one reactor.
  • the at least one anode and / or the at least one cathode are in this case designed as an agitator for the at least one reactor.
  • the half elements embodied as stirrers may in this case, for example, take the form of an immersion body, or of an anchor, an inclined blade, a blade or a cross-bar stirrer.
  • the flow baffles known in the prior art can also be used for improved mixing. By stirring the wastewater with its pollution load is always ideally mixed and the desired
  • the device is controlled by a controller. This has the advantage that the entire process can be monitored and regulated in terms of control technology and thus always the optimum process parameters prevail.
  • control is carried out by means of online measurement technology.
  • online or inline measurement the current process parameters available for process control. This makes the process optimally controllable.
  • aqueous and / or gaseous ZuStands with at least one inlet and at least one outlet, wherein by means of at least one feed educts are fed to at least one reactor and there by means of at least one Anode and / or at least one cathode are converted bioelectrochemically, the at least one anode and / or the at least one cathode are exposed to a changing environment in one phase.
  • Advantageous is the possibility of spatial separation of electron donor and acceptor, with potential savings in any feedback or with additional degrees of freedom in the adjustment of environmental conditions, in the sole oxidation or reduction, or in the purification of two different streams.
  • the electrode material is not subject to increased wear by triggering individual elements to catalyze reactions.
  • the electrode material must only be conductive and have no biologically inhibiting or toxic effect.
  • electrode materials are, inter alia, steel, commercial V2A / V4A stainless steel, high-quality alloys, carbon-doped compounds, conductive plastic, graphite, carbon, conductive textiles and other artificial structures (eg fleece) in question.
  • inorganic or organic contaminant load can be converted. For example, in wastewater treatment or biogas production. Process conditions can be created that Transference reactions, such as methanogenesis or acetogenesis.
  • elemental hydrogen can also be produced during the process.
  • inorganic substrate is also treatable.
  • the substrate must not be inhibitory or toxic.
  • Substrate with inorganic carbon is sufficient for cell structure ("Arche bacteria", “autotrophic bacteria”).
  • a correction of the CO 2 value depending on the purpose is necessary or even desirable.
  • a correction of the pH value depending on the application is necessary.
  • the device used for the bioelectrochemical conversion is a device according to one of claims 1 to 12.
  • Fig. 2 shows an additional arrangement of the invention
  • Fig. 3 shows a further arrangement of the device according to the invention.
  • FIG. 1 an arrangement of the device 1 according to the invention is illustrated using an exemplary embodiment and described below.
  • the arrangement shown in Fig. 1 for bioelectrochemical material conversion consists of a rotatable anode 2 and a rotatable cathode 3, wherein both the anode and the cathode electrode surfaces 4 have.
  • a half-element (anode 2 or cathode 3) may consist of different partial surfaces due to the design. Due to the rotatability of the half-elements, the electrodes are used as stirrers as in an agitator and thus thorough mixing of the substrate is achieved. The individual partial surfaces are then correspondingly conductively connected with each other or are in direct contact with each other.
  • a biofilm in particular a sessile biofilm, which serves as catalyst in the process, is arranged on at least one of the electrode surfaces 4 of the two half-elements.
  • a coating of Electrode surfaces 4 with the biofilm may optionally be made in advance or directly over the substrate.
  • the biofilm also called biomass, ubiquitous, so it is in the substrate, which in a sewage treatment plant, for example, represents the wastewater to be purified including the pollution load, where the material conversion is to take place, and does not have to be from outside to or tracked.
  • the substrate can be inoculated in special cases but also from the outside with biomass, which may be bacteria, for example.
  • the substrate is transported via the inlet 5 into the reactor 6 and from there by means of a material line 7 into the reactor 8 and leaves it via the outlet 9 purified the process.
  • the material line 7 may also be a salt bridge or the like., And serves the proton transport in the inventive arrangement.
  • the biofilm lowers the concentration gradient at both the anode and the cathode, making the process a low load process, that is, a small cell voltage 10 can be applied between the anode and the cathode. Furthermore, in some cases, a cell current 1 1 can be tapped.
  • the biomass absorbs at the anode 2 electrons e- from the substrate, and outputs these at the cathode 3 to the substrate.
  • Anode 2 and cathode 3 are connected to each other via an electrical line 12 to ensure the flow of electrons.
  • Redox reactions take place at anode 2 and at cathode 3, respectively, ie at the electrode surfaces 4, either in the case of reduction, electrons are released from the biofilm to the atoms, ions or molecules, or in the case of the oxidation of these.
  • substrate and redox couple is oxidized, for example, at the anode 2 and reduced at the cathode 3.
  • a commonly present aqueous environment is optionally anaerobic, anoxic or aerobic adjustable.
  • a possibly gaseous environment In microbial catalysis, water or substra tion rinsing (see growth body / trickling filter) on an electrode is characterized by partially submerged execution (see disc submersible or static, semi-submerged system) or by cultivation at high air humidity. The gaseous environment is therefore characterized in microbial catalysis by the simultaneous presence of water. It is either aerobic or anaerobic adjustable.
  • FIG. 2 shows an additional arrangement of the device 1 according to the invention for the bioelectrochemical conversion of substrate.
  • a reactor 13 either an anode 2 and / or a cathode 3 is arranged.
  • the reactor 13 is filled via the inlet 14 with substrate and emptied by means of the drain 15.
  • the emitted by the substrate present in the atoms, ions and molecules or captured electrons e ⁇ be performed via an electrical line 16 to either a consumer or provided by an external power source.
  • This arrangement is both in the field of wastewater treatment and in the field of methane production, for example in biogas plants, usable, here on the one hand a sewage treatment and on the other hand, the methane production takes place.
  • the purification of wastewater in sewage treatment plants or the production of methane in biogas plants is realized.
  • the arrangement in conjunction with an anode 2 for example, the yield of methane in a biogas plant can be increased.
  • the arrangement can be retrofitted in biogas plants.
  • the system can also be retrofitted for wastewater treatment.
  • the electrode rotatable in the form of a stirrer, in particular an anchor, a Schrägblattrrockers or the like to design, resulting in an optimized substrate mixing.
  • An additional arrangement of the device according to the invention is shown in FIG. Here, for example, two different substrates are fed into two different reactors 17 and 18 via feeds 19 and 20.
  • the substrate is guided out of reactor 17.
  • Reactor 18 is emptied by means of drain 22.
  • the anode 2 arranged in the reactor 17 is connected via an electrical line 23 to the cathode 3 arranged in the reactor 18, whereby an electron transport from the reactor 17 to the reactor 18 is made possible.
  • the embodiment can be configured with all advantageous arrangements, such as, for example, rotatable electrodes for optimal mixing of the reactors 17 and 18.
  • a proton transport can be realized here via a material line 24, in particular a salt bridge.
  • the substrate is fed via at least one inlet 5, 14, 19 or 20 to the at least one reactor 6, 8, 13, 17 or 18 and via at least one at the reactor 6, 8, 13, 17 or 18 arranged outlet 9, 15, 21st or 22 discharged.
  • Redox reactions which are catalyzed by biomass, take place at the electrode and cause the conversion of the substance. LIST OF REFERENCE NUMBERS

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Hydrology & Water Resources (AREA)
  • Organic Chemistry (AREA)
  • Water Supply & Treatment (AREA)
  • Environmental & Geological Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Microbiology (AREA)
  • Biodiversity & Conservation Biology (AREA)
  • Molecular Biology (AREA)
  • Analytical Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Water Treatment By Electricity Or Magnetism (AREA)
  • Apparatus Associated With Microorganisms And Enzymes (AREA)
  • Physical Or Chemical Processes And Apparatus (AREA)

Abstract

L'invention concerne un dispositif (1) pour la conversion bio-électrochimique de substances organiques ou inorganiques à l'état aqueux et/ou gazeux comportant au moins une entrée (5, 14, 19, 20) et au moins une sortie (9, 15, 21, 22), ainsi qu'un procédé d'utilisation dudit dispositif (1), selon lequel au moins une anode (2) et/ou au moins une cathode (3) sont agencées dans au moins un réacteur (6, 8, 13, 17, 18), des composés de départ étant acheminés dans le(s) réacteur(s) (6, 8, 13, 17, 18) et y étant mis en réaction ou convertis au moyen de la ou des anodes (2) et/ou de la ou des cathodes (3).
PCT/DE2013/000247 2012-05-07 2013-05-06 Dispositif de conversion bio-électrochimique de substances (mise en oeuvre d'une réduction / d'une oxydation / d'une réaction redox) WO2013167107A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
DE112013002364.4T DE112013002364A5 (de) 2012-05-07 2013-05-06 Vorrichtung und Verfahren zur bioelektrochemischen Stoffumwandlung (Herbeiführung einer Reduktion/Oxidation/Redox-Reaktion)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102012008785.3 2012-05-07
DE102012008785 2012-05-07

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WO2013167107A1 true WO2013167107A1 (fr) 2013-11-14

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WO (1) WO2013167107A1 (fr)

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CN112142267A (zh) * 2020-10-09 2020-12-29 哈尔滨工业大学 一种厌氧生物电化学-好氧移动床生物膜一体式废水处理装置及其处理废水的方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AT265152B (de) 1966-03-01 1968-09-25 Zsolt Dipl Ing Paphazy Anlage zur Klärung von Abwässern durch biologische Reinigung
DD244743A1 (de) 1985-12-24 1987-04-15 Dresden Komplette Chemieanlag Verfahren zur biochemischen behandlung stickstoffbelasteter, carbonathaltiger abwaesser
ATE81109T1 (de) 1988-06-27 1992-10-15 Krueger I Systems As Verfahren und anlage fuer die biologische klaerung von abwaessern.
DE19748229A1 (de) * 1997-10-31 1999-05-06 Dynamit Nobel Ag Vorrichtung und Verfahren zur Behandlung von Nitrophenolen und Nitroresorcinen in Abwässern
WO2011006939A2 (fr) 2009-07-15 2011-01-20 Pfeiffer, Florian Dispositif et procédé de dénitrification bio-électrochimique de fluides

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AT265152B (de) 1966-03-01 1968-09-25 Zsolt Dipl Ing Paphazy Anlage zur Klärung von Abwässern durch biologische Reinigung
DD244743A1 (de) 1985-12-24 1987-04-15 Dresden Komplette Chemieanlag Verfahren zur biochemischen behandlung stickstoffbelasteter, carbonathaltiger abwaesser
ATE81109T1 (de) 1988-06-27 1992-10-15 Krueger I Systems As Verfahren und anlage fuer die biologische klaerung von abwaessern.
DE19748229A1 (de) * 1997-10-31 1999-05-06 Dynamit Nobel Ag Vorrichtung und Verfahren zur Behandlung von Nitrophenolen und Nitroresorcinen in Abwässern
WO2011006939A2 (fr) 2009-07-15 2011-01-20 Pfeiffer, Florian Dispositif et procédé de dénitrification bio-électrochimique de fluides

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
HE ET AL: "Increased power production from a sediment microbial fuel cell with a rotating cathode", BIOSENSORS AND BIOELECTRONICS, ELSEVIER BV, NL, vol. 22, no. 12, 16 May 2007 (2007-05-16), pages 3252 - 3255, XP022080472, ISSN: 0956-5663, DOI: 10.1016/J.BIOS.2007.01.010 *

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DE112013002364A5 (de) 2015-01-15

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