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    • 专利摘要:
    Bioelectrochemical system and procedure for the elimination of organic matter and nitrogenous compounds from wastewater. Bioelectrochemical system and procedure (1) for the elimination of organic matter and nitrogenous compounds from wastewater; wherein said system comprises a plurality of biological piles (2, 3) connected to each other, which respectively have: an anode chamber (2) configured to oxidize the organic matter of said waste water, and a cathodic chamber (3) configured to reduce the nitrogenous compounds of said waters; where the biological piles (2, 3) are connected to each other through a channel (12a, 12b) through which the wastewater circulates; which has two sections of circulation: a first section (12a) of oxidation of organic matter running through the plurality of anodic chambers (2a, 2b, 2c, 2d, 2e, 2f) of each of the biological stacks (2. 3); and a second section (12b) of reduction of the nitrogen compounds running through the plurality of the cathodic chambers (3a, 3b, 3c, 3d, 3e, 3f) of each of the biological stacks (2, 3). (Machine-translation by Google Translate, not legally binding)
    公开号:ES2547031A1
    申请号:ES201430459
    申请日:2014-03-31
    公开日:2015-09-30
    发明作者:Jesús COLPRIM GALCERÁN；María Dolores BALAGUER CONDOM；Sebastiá PUIG BROCH；Anna VILAJELIU PONS；Inmaculada Concepción SALCEDO DÁVILA
    申请人:Abengoa Water SL；
    IPC主号:
    专利说明:

    P201430459
    03-31-2014 DESCRIPTION
    Bioelectrochemical system and procedure for the elimination of organic matter and nitrogen compounds from wastewater TECHNICAL FIELD OF THE INVENTION
    The present invention relates to a bioelectrochemical system for the elimination of organic matter and nitrogen compounds from wastewater, and the process associated therewith, said system being encompassed in the water and environment treatment sector; and clarifying the concept of wastewater as effluents of urban and / or industrial origin with a certain content of pollutants such as organic matter, nitrogen and phosphorus; Any groundwater or any other source may also be considered.
    The main purpose of this system is to reduce the content of wastewater pollutants, in addition to being able to generate electricity from said pollutant reduction, occupy a small space, save on sludge management and deposition, reduce gas emissions that cause the greenhouse effect, as well as require a lower energy, electricity and oxygen consumption, compared to the wastewater treatment systems currently used. BACKGROUND OF THE INVENTION
    By way of introduction, it is currently known that wastewater has a high degree of contaminants. The type and classification of such pollutants depends on the origin of the waters, the most common pollutants being: organic matter normally measured in terms of Chemical Oxygen Demand, hereinafter COD, and nitrogen compounds, generally present in the form of ammonium and nitrogen organic (measured in terms of Total Kjeldahl Nitrogen, NTK), nitrites and nitrates.
    In this context, and focusing on the elimination of organic matter, there are conventional wastewater treatment systems that usually consist of systems
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    Biological aerobes, which require a series of simple operations, and lead to high treatment efficiency. The execution of these operations requires the availability of hydraulic turbines that facilitate the oxygenation of wastewater, and with it the reduction of the organic matter existing in it. However, these systems have high operating costs associated with the aeration and treatment of the sludge generated, with the aeration costs of approximately 0.5 kWh / m3 (30 kWh / hab.eq • year) and the costs associated with sludge treatment exceeding € 500 / ton dry matter.
    In order to reduce the costs and volume of aerobic facilities for the treatment of organic matter in wastewater, an alternative linked to anaerobic systems is contemplated. These systems produce biogas (mixture of methane and carbon dioxide) from organic matter, with a recovery of electrical and heat energy (approximately 1 kWh per 1 kg COD treated). But the anaerobic processes currently used present a series of drawbacks associated with the activity of methanogenic bacteria (which catalyze the degradation of organic matter and the production of biogas), because their high sensitivity translates into an inhibition of last stage of the anaerobic process (methanogenesis) when the operating parameters move away from optimal values (strict anaerobic conditions, pH close to 7 and temperature of 35 ° C, among others); and therefore the results of pollutant reduction are not as expected.
    It can also be considered as an additional disadvantage of anaerobic digestion which has application mainly in waters with high organic load, taking as a reference value an amount greater than 5 kg COD / m3day, not being applied in waters with medium or low content of matter organic and / or with the presence of nitrogen compounds, since anaerobic digestion is not able to eliminate the existing nitrogen in said wastewater.
    In this sense, and to avoid the inconveniences described above, there are solutions that address these problems, and that focus on the use of microbiological batteries or microbiological electrolytic cells. Where the essence of this type of batteries is that they are able to degrade organic compounds and nitrogen components and generate
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    electricity, using microorganisms as catalysts. And where the operation of these microbiological batteries is based on two stages:
    -In the first place, the oxidation of organic matter, which acts as an electron donor substrate, occurs to carbon dioxide (CO2), which is carried out in an anodic compartment; and subsequently -the reduction of oxygen to water (H2O), which acts as an electron accepting substrate, occurs in a cathodic compartment.
    In this way, the union of both compartments with conductive material produces an electron flow from the anode to the cathode capable of generating electricity. The anode and cathode must be separated by an ionic membrane, usually cationic, that allows the passage of protons generated from the oxidation of organic matter in the anode to the cathode to compensate for negative electrical charges or electrons from the anode
    In this context, and during the last years, the investigation of the biological batteries has been evolving with respect to the configurations of work, but mainly, looking for an additional applicability to the cathodes. Thus, biocathodes have been introduced which, like the anodes, contain electrotrophic microorganisms that are used as catalysts to carry out the reduction reactions. So one of the most extensive applications with biocathodes is the simultaneous elimination of organic matter and nitrogen, where the oxidation of the first occurs at the anode and the reduction of the second (specifically nitrates) is carried out at the cathode.
    In relation to the state of the art linked to the treatment of wastewater, it is worth noting the US patent application of publication number US 2010/0304226, in which a biological fuel cell is described where the oxidation of the material occurs in the anode organic, and an aerated nitrification occurs in the cathode.
    This solution has the advantage that it requires the use of bioelectrochemical systems using microorganisms to treat wastewater while generating electrical energy. So in this system, the organic compounds are oxidized by electrotrophic microorganisms, which are donors of electrons and protons.
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    At the same time, the electrons are transferred from the anode to the cathode through a resistor, while the protons pass through the anodic to cathodic chamber through a membrane. And it is in the cathode, where electron acceptor microorganisms reduce nitrogen compounds autotrophically; and thus avoiding adding organic matter, reducing costs as well as the risk of overgrowth in the systems to be treated because autotrophic organisms grow more slowly and produce less biomass.
    However, biocathode-type bioelectrochemical systems pose a series of drawbacks, all of them focused on the treatment of nitrogen compounds. According to US patent application US 2010/0304226, aerated nitrification occurs in the cathode, but this oxidation of ammonium to nitrate requires a denitrification in order to reduce nitrate to nitrogen gas, and thus be able to pour water purified to the next environmental space. Biocathode systems require a control of oxygen levels since the nitrification process is favored with high levels of said gas; however, the denitrification process must be performed under anoxic conditions (without oxygen). Scientific studies conclude that at high levels of oxygen (greater than 0.8 mg • L-1, approximately), the denitrification process is impaired, when inhibition of said process occurs.
    Additionally, the solution proposed in US patent application US 2010/0304226, once implemented in a system to apply in a real context, results in the oxidation of organic matter in the anode not obtaining optimal results, since It requires a high residence time.
    That is why, in view of the inconveniences described in relation to aerobic and anaerobic treatments, it is necessary the appearance of a system capable of solving said problem with high application effectiveness, based on being able to reduce organic matter of wastewater with low residence times, assuming a low energy cost and occupying a minimum volume, resulting in a highly compact system; as well as being able to eliminate the nitrogen compounds existing in said waters, from their origin, which are usually present in the form of ammonia, and therefore being able to nitrify and denitrify such compounds from wastewater
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    also in a fast way, and with a low energy cost; and all this with a system of simple, compact configuration, of easy installation and maintenance, and that in addition supposes an energetic saving for the installations, and produces an optimum purification of the residual waters collaborating with an environmental improvement in all his group. DESCRIPTION OF THE INVENTION
    The present invention relates to a bioelectrochemical system for the elimination of organic matter and nitrogen compounds from wastewater, wherein said bioelectrochemical system comprises a plurality of biological cells, which respectively have:
    -An anodic chamber configured to oxidize the organic matter of said wastewater, where said oxidation releases a series of electrons and protons; -a cathodic chamber configured to reduce the nitrogen compounds of said wastewater, where said reduction receives a series of electrons and protons from the oxidation of the anodic chamber; and - an ion exchange membrane located between the anodic chamber and the cathodic chamber.
    It is noted that these elements are common in the state of the art, and are considered essential parts of a biological cell; so that in the anodic chamber a generation of electrons is produced, which are used, at least part of said generated electrical energy, in the cathodic chamber to be able to reduce the nitrogen compounds of said wastewater.
    But the bioelectrochemical system object of the invention has the following essential and innovative technical characteristics, linked to the improvement of its energy yields and the ability to reduce organic matter and nitrogen compounds, since the biological batteries are connected to each other through at least one channel through which the wastewater to be treated circulates; where said, at least one, channel presents two sections of circulation of wastewater: -a first section of oxidation of organic matter of wastewater, where the first
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    section runs through the plurality of the anodic chambers of each of the biological piles; and -a second section of reduction of the nitrogenous wastewater compounds, where the second section runs through the plurality of the cathode chambers of each of the biological cells.
    Observing that the system is formed by the union of several biological cells, where each biological cell presents both anodic and cathodic chambers; This solution guarantees that, once the system has been put into operation and the wastewater has been stabilized; said waters circulate in the first place through all the anodic chambers, so that there is a elimination of biodegradable organic matter greater than ninety percent of that initially existing in said sewage, to subsequently introduce said treated sewage into the anodic chambers until set of the cathode chambers, where the treatment and elimination of the nitrogen compounds of said sewage takes place, and that thanks to the sewage circulating through the set of cathodic chambers, the reduction of nitrogen compounds is greater than 50%.
    In this regard, it is worth highlighting a preferred option for the circulation of wastewater through the set of biological batteries, so that a procedure for the elimination of organic matter and nitrogenous compounds from said wastewater through said system is described. minus one, channel, which comprises the following stages:
    a) Introduce said wastewater to a first anode chamber of a first biological cell, oxidizing an amount of organic matter during a corresponding part of the first section of the anodic channel; b) introducing the water coming from the first anode chamber of the first biological cell, into the second anode chamber of a second biological cell, oxidizing an amount of organic matter, during a corresponding part of the first section of the canal; observing that the waters do not circulate in any cathode chamber yet, but that they circulate through the anodic chambers at all times; c) repeat the oxidation of water a number of times equivalent to the number of batteries belonging to the bioelectrochemical system, and therefore, to the number of anodic chambers,
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    during the rest of the first section of the anodic channel; In this way, the organic matter has oxidized until it reaches minimum COD values; d) introducing the water coming from the last anodic chamber, from the last biological cell, into the cathodic chamber belonging to said last biological cell, reducing a quantity of nitrogen compounds, during part of the second section of the cathodic channel; e) introducing the water coming from the last cathode chamber of the last biological cell, into a penultimate cathodic chamber of a penultimate biological cell, reducing a quantity of nitrogen compounds, during part of the second section of the cathodic channel; and f) repeat the reduction of the nitrogen components of the waters the same number of times equivalent to the number of batteries belonging to the bioelectrochemical system, and therefore, to the number of cathode chambers, during the rest of the second section of the channel. In this way, the nitrogen components have been reduced to reach minimum nitrogen values.
    This disposition and sense of circulation of wastewater, defined by the passage of said wastewater through a channel and divided into two sections; it is achieved that, thanks to the grouping of biological batteries and the arrangement of the anodic and cathodic chambers, the space required for the oxidation-reduction of wastewater pollutants is very small, and therefore a compact system is obtained, where its effectiveness is high thanks to the continuous passage between all the anodic and cathodic chambers; and a low energy consumption is required when operating in conditions of biological battery capable of generating electrical energy during the whole process, so that the bioelectrochemical system object of the invention can behave, in turn, as an electricity generator.
    It should be noted that, as a guide, the wastewater to be treated has carbon-nitrogen (C / N) loads above 3.5 and preferably between 5 and 9; recalling that said ratio is of a preferential and non-binding nature for the treatment of wastewater in the biolectrochemical system object of the invention.
    Taking into account that the reduction of organic matter occurs during the passage of wastewater through the first section of the anodic canal, flowing through the
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    set of anodic chambers; Two preferred embodiments of how to reduce the nitrogen compounds of said wastewater are contemplated, being:
    A) In the first option, the bioelectrochemical system object of the invention comprises an external aerated nitrifying reactor located between the first section, corresponding to the anodic chambers, and the second section, corresponding to the cathode chambers, of said at least one channel ; wherein said external nitrifying reactor is configured to oxidize the nitrogenous compounds of the first section wastewater from a last anode chamber of a last biological cell, that is, the nitrification reaction occurs in the wastewater; and introducing said waters resulting from said oxidation into the external nitrifying reactor towards the second section that begins in a last cathode chamber of the last biological cell; the external term of the nitrifying reactor is understood as that reactor that is not physically integrated in the biochemical system object of the invention.
    It is observed, therefore, that once the wastewater leaves the last anodic chamber, it is then that the wastewater, free of biodegradable organic matter, approximately with an organic matter reduction of ninety percent due to its oxidation during the passage through the set of anodic chambers, they are introduced into the external nitrifying reactor, and nitrification of the nitrogenous compounds of the wastewater takes place, the usual chemical reactions taking place:
    -
    -NH4 + + 1.5 O2 • NO2 + H2O + 2 H + -NO2- + 0.5 O2 NO3-
    That is, the wastewater is introduced into the external nitrifying reactor in the form of ammonium (NH4 +), and exits the external nitrifying reactor in the form of nitrates (NO3-); ready to be introduced in the second section of the cathode channel, and therefore in the set of cathode chambers of the respective biological batteries.
    It is in the cathode chambers where the oxidized nitrogen compounds, in the form of nitrites and nitrates, are reduced due to the electrochemical cell character of the system object of
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    invention; capturing electrons and protons from the oxidation of organic matter in the anodic chambers, and reducing said nitrates to obtain Nitrogen gas (N2), the denitrification reaction being:
    -2NO3- + 12 H + + 10 e- • N2 + 6H2O
    Where in short, water with a low content of pollutants is obtained, thanks to:
    -Oxidation of organic matter in the anodic chambers -The reduction of nitrogen compounds in the set formed by said at least one external nitrifying reactor and the cathode chambers as a whole.
    In order to improve the efficiency of the bioelectrochemical system object of the invention, the option is contemplated that each ion exchange membrane located in each of the electrochemical cells that separate the anodic and cathodic chambers is an anion exchange membrane; thus avoiding the flow of ammonia from the wastewater from the anodic chamber to the cathode chamber of each biological cell.
    And similarly, a nitrification control in said external nitrifying reactor is guaranteed thanks to the preferred option of using at least one oxygen probe configured to set the oxygen concentration in the external nitrifying reactor together with the use of a system control, a solenoid valve and a compressor; and thus achieve the necessary nitrification to be able to introduce the wastewater into the cathode chambers and its subsequent reduction to nitrogen gas (N2).
    B) In the second option, each cathode chamber of the bioelectrochemical system object of the invention comprises aeration means configured to nitrify the nitrogen compounds in reduced form (preferably ammonium) of the wastewater; so that each cathode chamber is configured to carry out the nitrification of the nitrogen compounds thanks to the aeration means, and denitrify said nitrogen compounds (preferably nitrites or nitrates) thanks to the reduction of these due to the contribution of electrons from each one of the corresponding anodic chambers. Where, preferably, the aeration means controls the
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    concentration of dissolved oxygen in each cathode chamber, operating in a design range between 1 and 1.5 mg O2 / L; being able to reach values of up to 4 mg O2 / L
    This second option has the following advantages in relation to the first design option since: -The space required is substantially smaller, since it does not require an external nitrifying reactor to perform the process of nitrification of wastewater, and both nitrification as denitrification is performed in the cathode chambers; - there is a saving in maintenance costs, due to the absence of the external nitrifying reactor, - there is also a saving in energy costs, due to the partial nitrification reaction and the denitrification reaction that occur in the cathode chambers consumes less oxygen that the external nitrifying reactor of the previous option; and - in the case that all nitrogen compounds are reduced, then in the cathode chambers, oxygen can be used as a donor electron, and thus electricity continues to be produced.
    But it is known that it is complex to find a balance between both reactions (nitrification and denitrification), since studies (Pochana and Keller (1999)) have shown that, at high oxygen levels, the nitrification process occurs but instead it inhibits denitrification, concluding that at values greater than 0.8 mg / L, the denitrifying process is impaired. And so the aeration means present in the cathode chambers are arranged at different heights to achieve a correct diffusion of dissolved oxygen in wastewater, until maximum nitrification of the nitrogen compounds is achieved, which are subsequently denitrified thanks to the reduction reactions produced in the electrochemical batteries of the bioelectrochemical system object of the invention.
    In relation to the different heights of the aeration means, the possibility is contemplated that the aeration means are located in more than one height in order to achieve satisfactory nitrification and denitrification. In this regard, it should be noted that a preferred option is to locate said aeration means at three different heights, where an example would be 30 cm, 60 cm and 90 cm, so that each of the means of
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    Aeration allow the aerobic and anoxic hydraulic residence times to be set. By way of example, in the event that oxygen is supplied through the aeration means through the center of the cathode chamber, then nitrification occurs in the upper part of said cathodic chamber, and denitrification in the lower part.
    In order to improve the efficiency of option B) of the configuration of the bioelectrochemical system object of the invention, the option is contemplated that each ion exchange membrane located in each of the electrochemical cells separating the anodic and cathodic chambers, It is a cation exchange membrane.
    That is why, both realization options are included within the essential technical characteristics described initially, and can be implemented depending on the resources available to the water treatment plant, because both solutions pose a series of advantages and inconveniences that directly affect the facilities and resources available.
    As indicated above, the bioelectrochemical system object of the invention is capable of generating electrical energy, which can be used for the reduction reactions of the cathode chambers, thanks to the oxidation reactions of the organic matter of the wastewater in the respective anodic chambers; and therefore the option is contemplated that at least one condensing element is connected to each biological cell; wherein said capacitor element is configured to receive electrons from each anodic chamber, and supply electrons to each cathode chamber; improving the energy efficiency of the entire installation in a simple and efficient way.
    In relation to the use of microorganisms capable of carrying out the oxidation and reduction reactions, the preferred options are contemplated where:
    -Each anodic chamber of each biological cell presents in its interior a microbial community responsible for oxidizing the organic matter of wastewater; and / or - each biological cell presents within its cathodic chambers a plurality of families of denitrifying microorganisms responsible for reducing the nitrogenous compound of the effluent from the external nitrifying reactor.
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    And by way of example, the following options for selecting organisms are highlighted, where:
    -In the anodic chambers: Firmicutes, alpha-proteobacteria and gammaproteobacteria families and Geobacter sulfurreducens of delta-proteobacteria. -In the cathode chambers in option A), that is, with the use of at least one external nitrifying reactor: Actinobacteriaceae (Mycobacteriumchelonae;), Bacteroidetes (Fulvivirga sp), Chloroflexiaceae (Sphaerobactersp.,), Deinococcaceae, Firmicutes (Clostridium sp .) and Proteobacteria (Nitrobacteralkalicus ;; Nitrosospira sp.,; Diaphorobacter sp., and Schegelella sp.,). -In the cathode chambers in option B), that is, without the use of a nitrifying reactor: Actinobacteriaceae (Mycobacteriumchelonae), Bacteroidetes (Ferruginibacter sp.,), Chloroflexiaceae (Sphaerobactersp.,), Deinococcaceae (Trueperasp.), Firmicutes (Clostridium (Clostridium) ;) and Proteobacteria (Nitrosomonaseuropaea ;, Nitrobacteralkalicus, and Gulbenkiania sp.,)
    And finally, and in order to guarantee the correct oxidation and reduction reactions in each of the biological cells, it is contemplated that each biological cell is formed by a pair of rectangular-based prismatic structures that respectively define the anodic chamber and cathodic, where each prismatic structure presents a perimeter frame; so that:
    -The perimeter frame of the prismatic structure of the anodic chamber has four corners, where one of them comprises a through hole belonging to the second section of the wastewater channel, and is configured to allow the passage of said wastewater from the cathode chamber located between said anodic chamber; and where two opposite corners comprise holes for the passage of wastewater, one of them towards the inside of the anodic chamber, and another one towards the outside of the anodic chamber, allowing the oxidation of the organic matter of the wastewater; and -the perimeter frame of the prismatic structure of the cathode chamber has four corners, where one of them comprises a through hole belonging to the first section of the sewage channel, and is configured to allow the passage of water from the anode chamber located between said cathodic chamber; and where two corners
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    Opposites comprise holes for the passage of wastewater into the cathode chamber, one of them towards the inside of the cathode chamber, and another one towards the outside of the cathode chamber, allowing the reduction of nitrogen compounds from the wastewater. .
    By way of clarification, it is observed that the structural configuration of both cathodic and anodic chambers is the same, since each of them has a perimetral frame with four corners, where one of them presents the orifice between the two adjacent chambers (it is say, if the reference chamber is the cathodic one, the passageway connects the two adjacent anodic chambers, and vice versa); and two of the three remaining corners are responsible for, on the one hand, introducing the wastewater into the chamber (in the case of the reference, the cathodic chamber), allowing the relevant reaction to be carried out (in the case from the reference, the reduction reaction of the nitrogen compounds), and extracting the wastewater into the next chamber of the next biological cell.
    And in this sense, and according to the preferred option of circulation of wastewater through the set of biological batteries, the procedure of circulation of said wastewater through the set of biological batteries is described, which presents the following stages :
    a) Introduce the wastewater to a first anodic chamber of a first biological cell through a lower corner, oxidizing an amount of organic matter during a corresponding part of the first section of the anodic canal, and leaving said wastewater through an upper corner, obtaining a cross oxidation flow; b) introducing wastewater from the first anodic chamber of the first biological cell through an upper corner, into the second anodic chamber of a second biological cell, also through an upper corner oxidizing an amount of organic matter, during a corresponding part of the first section of the channel; observing that the residual waters do not circulate through any cathode chamber yet, but that they circulate through the anodic chambers at all times; c) repeat the oxidation of wastewater a number of times equivalent to the number of batteries belonging to the bioelectrochemical system, and therefore, to the number of anodic chambers, during the remainder of the first section of the anodic channel; In this way, the matter
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    organic has oxidized until it reaches minimum COD values thanks to the cross-flow of oxidation of said wastewater; d) introducing the wastewater from the last anodic chamber, from the last biological cell through a lower corner, into the cathodic chamber belonging to said last biological cell, and leaving said wastewater through an upper corner, reducing a quantity of nitrogen compounds , during part of the second section of the cathode channel; e) introduce the wastewater from the last cathode chamber of the last biological cell, also through an upper corner, into a penultimate cathodic chamber of a penultimate biological cell, reducing a quantity of nitrogen compounds, during part of the second section of the cathode channel ; and f) repeat the reduction of the nitrogenous components of the wastewater the same number of times equivalent to the number of batteries belonging to the bioelectrochemical system, and therefore, to the number of cathode chambers, during the rest of the second section of the channel. In this way, the nitrogen components have been reduced to reach minimum nitrogen values.
    Thus, according to the described invention, the bioelectrochemical system for the elimination of organic matter and nitrogen compounds existing in wastewater constitutes an important novelty in water treatment systems, since it allows reducing the high concentrations of contaminants existing in same, which may have suffered an urban or industrial pollution and therefore has to be treated in order to be dumped into a natural environment (river, lake, or similar); In addition to being able to generate electricity, require lower oxygen consumption, reduce greenhouse gas emissions, occupy a small space and save on sludge management and deposition, compared to wastewater treatment systems currently used DESCRIPTION OF THE DRAWINGS
    To complement the description that is being made, and in order to help a better understanding of the features of the invention, according to a preferred example of practical implementation thereof, a series of drawings are attached as an integral part of said description. where, for illustrative and non-limiting purposes, the
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    next:
    Figure 1.- Shows a first general scheme of the bioelectrochemical system object of the invention, in which the main components of this and their connections are indicated.
    Figure 2.- Shows a second specific scheme of the biological system object of the invention, corresponding to the first section of the channel where the anodic chambers oxidize the organic matter of the wastewater.
    Figure 3.- Shows a third specific scheme of the biological system object of the invention, corresponding to the external and independent nitrifying reactor located between the first section of the channel where the anodic chambers oxidize the organic matter of the wastewater, and the second section of the channel where the cathode chambers reduce the nitrogen compounds coming from the external nitrifying reactor.
    Figure 4.- It shows a fourth specific scheme of the biological system object of the invention, corresponding to the second section of the channel where the cathode chambers reduce the nitrogen compounds of the wastewater.
    Figure 5 shows a first preferred embodiment of the biological system object of the invention, where the external nitrifying reactor is an independent element of the biological batteries.
    Figure 6 shows a second preferred embodiment of the biological system object of the invention, where the external nitrifying reactor is an element dependent on the biological batteries, and specifically is included in the cathode chambers together with the aeration means.
    Figure 7.- Shows a three-dimensional view of the prismatic structure of a chamber (anodic or cathodic), observing the through hole between two chambers (if the reference chamber is anodic, the orifice of the two adjacent cathode chambers) , as well as holes in the chamber (in the case of the reference, the anodic chamber), and its subsequent expulsion to the next anodic chamber.
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    03-31-2014 PREFERRED EMBODIMENT OF THE INVENTION
    By way of example, starting from a tank (14) that has a stream of water in its interior, which are mainly composed of organic matter and ammonium, and with a Carbon and Nitrogen ratio above 3.5; and in view of figures 1, 2 and 4, it can be seen how the bioelectrochemical system (1) for the generation of electricity, treatment and elimination of organic matter and nitrogen compounds existing in a water stream object of the invention comprises six biological batteries (2, 3), which present respectively:
    An anode chamber (2) configured to oxidize the organic matter of said water stream, where said oxidation releases a series of electrons; - a cathodic chamber (3) configured to reduce the nitrogen compounds of said water stream, where said reduction receives a series of electrons from the oxidation of the anodic chamber (2); and - an ion exchange membrane (8) located between the anodic chamber (2) and the cathodic chamber (3); so that the biological batteries (2, 3) are connected to each other through a channel (12a, 12b) through which the current of water to be treated circulates; where said, at least one channel (12a, 12b) has two water flow circulation sections: -a first section (12a) of oxidation of the organic matter of the water flow, where the first section (12a) it runs through the plurality of the anodic chambers (2a, 2b, 2c, 2d, 2e, 2f) of each of the biological cells (2, 3); - a second section (12b) of reduction of the nitrogen compounds of the water stream, where the second section (12b) runs through the plurality of the cathode chambers (3a, 3b, 3c, 3d, 3e, 3f) of each of the biological batteries (2, 3); -a control system (7) configured to regulate the amount of electricity generated and the amount of oxygen required in the entire bioelectrochemical system (1); and - six capacitor elements (4) that are connected respectively to each biological cell (2, 3); where each capacitor element (4) is configured to receive electrons from each anodic chamber (2a, 2b, 2c, 2d, 2e, 2f), and supply electrons to each cathode chamber (3a, 3b, 3c, 3d, 3e, 3f) .
    So that the elimination of organic matter and nitrogen compounds from
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    slurry taken as an example reference, through said channel (12a, 12b), generating electricity, comprises the following steps:
    a) Introducing said water stream to the first anodic chamber (2a) of the first biological cell (2a, 3a), oxidizing an amount of organic matter during a corresponding part of the first section (12a) of the channel (12a, 12b); b) introducing the water stream from the first anodic chamber (2a) of the first biological cell (2a, 3a), into the second anodic chamber (2b) of a second biological cell (2b, 3b), oxidizing an amount of organic matter, during a corresponding part of the first section (12a) of the channel (12a, 12b); c) repeat the oxidation of the water stream six times, the number being equivalent to the number of batteries belonging to the bioelectrochemical system (1), and therefore, to the number of anodic chambers (2a, 2b, 2c, 2d, 2e, 2f ), during the rest of the first section (12a) of the channel (12a, 12b); d) introducing the water flow from the last anodic chamber (2f), from the last biological cell (2f, 3f), to the cathodic chamber (3f) belonging to said last biological cell, reducing a quantity of nitrogen compounds, during part of the second section (12b) of the channel (12a, 12b); e) introducing the stream of water from the last cathode chamber (3f) of the last biological cell (2f, 3f), to a penultimate cathodic chamber (3e) of a penultimate biological cell (2e, 3e), reducing a quantity of nitrogen compounds, during part of the second section (12b) of the channel (12a, 12b): f) repeat the reduction of the water flow six times, this being the number equivalent to the number of batteries belonging to the bioelectrochemical system (1), and therefore, to the number of cathode chambers (3a, 3b, 3c, 3d, 3e, 3f), during the rest of the second section (12b) of the channel (12a, 12b).
    In relation to figures 3 and 5, the first preferred option of design and execution of the bioelectrochemical system (1) object of the invention is observed; in which it comprises an aerated external nitrifying reactor (5) located between the first section (12a) and the second section (12b) of said channel (12a, 12b); wherein said nitrifying reactor (5) is configured to oxidize the nitrogen compounds of the water stream of the first section (12a) from a last anodic chamber (2f) of a last biological cell (2f, 3f); and
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    introducing the water stream resulting from said oxidation of the organic matter into the external nitrifying reactor (5) towards the second section (12b) that begins in a last cathodic chamber (3f) of the last biological cell (2f, 3f).
    Thus, the water stream slurries reduce their amount of organic matter in the anode chambers (2) during the first section (12a) of the channel (12a, 12b); subsequently it is introduced into the external aerated nitrifying reactor (5) where nitrification occurs:
    -
    -NH4 + + 1.5 O2 • NO2 + H2O + 2 H + -NO2- + 0.5 O2 NO3-
    And once the nitrogenous compounds are nitrified in the external nitrifying reactor (5), the water stream enters the second section (12b) of the channel (12a, 12b), where denitrification is carried out in each of the cathode chambers ( 3), the denitrification reaction being:
    -2NO3- + 12 H + + 10 e- • N2 + 6H2O
    Additionally, the external nitrifying reactor (5) has aeration means (6) as well as oxygen probes (13) configured to measure the amount of oxygen inside said external nitrifying reactor (5); so that a control system is responsible for controlling the nitrification reaction, since the oxygen probes (13) are capable of measuring the amount of O2 in the water stream, in addition to using a solenoid valve and a compressor; and thus achieve the nitrification reaction necessary to be able to introduce the water stream into the cathode chambers (3) and its subsequent reduction to nitrogen gas (N2); further observing the existence of anodic exchange membranes (8a) in each of the biological batteries (2, 3) of the system object of the invention.
    In parallel, in view of Figure 6, the second preferred option of design and execution of the bioelectrochemical system (1) object of the invention is observed; in which it is observed that each cathode chamber (3a, 3b, 3c, 3d, 3e, 3f) of each biological cell (2, 3) comprises aeration means (6) configured to nitrify the nitrogen compounds
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    of the water stream; so that each cathode chamber (3a, 3b, 3c, 3d, 3e, 3f) is configured to nitrify the nitrogen compounds (ammonium) thanks to the aeration means (6), and denitrify said previously oxidized nitrogen compounds (nitrites and nitrates ) thanks to the reduction of these due to the contribution of electrons and protons from each of the corresponding anodic chambers (2a, 2b, 2c, 2d, 2e, 2f). Further observing how the exchange membrane (8) is a cation exchange membrane (8b). Where, in an explanatory manner, the aeration means (6) are responsible for controlling the concentration of dissolved oxygen in each cathode chamber (3a, 3b, 3c, 3d 3e, 3f) at a design point of 1.2 mg O2 / L.
    And finally, it is observed in figure 7, a prismatic structure (11) belonging to a biological cell (2, 3), where each biological cell (2, 3) has a pair of prismatic structures (11) of rectangular base which respectively define the anodic (2) and cathodic chamber (3), and specifically, and in view of said figure 7, it is observed how each prismatic structure (11) has a perimeter frame (9); so that, taking an example for the penultimate biological cell (2e, 3e), it is observed:
    -The perimeter frame (9) of the prismatic structure (11) of the penultimate anodic chamber (2e) has four corners (9a, 9b, 9c, 9d), where one of them (9a) has a through hole belonging to the second section (12b) of the channel (12a, 12b) of the water stream, and is configured to allow the passage of the water stream from the cathode chambers (3e, 3f) located between said anode chamber (2e); and where two opposite corners (9b, 9c) comprise water flow passage holes, one of them towards the inside (10) of the anodic chamber (2e), and another one towards the outside of the anodic chamber (2e ), allowing the oxidation of organic matter from the water stream; and -the perimeter frame (9) of the prismatic structure (11) of the penultimate cathodic chamber (3e) has four corners (9a, 9b, 9c, 9d), where one of them (9b) comprises a through hole belonging to the first section (12a) of the channel (12a, 12b) of the water stream, and is configured to allow the passage of the water stream from the anodic chambers (2e, 2f) located between said cathode chamber (3e); and where two opposite corners (9a, 9d) comprise water flow passage holes, one of them towards the inside (10) of the cathode chamber (3e), and another of them towards the outside of the cathode chamber (3e ) allowing the reduction of nitrogen compounds in the water stream.
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    In this sense, we proceed to describe an intrinsic advantage to the design of the perimeter frame
    (9) of each prismatic structure (11); so that thanks to the two opposite corners (9a, 9d) that allow the passage of the water flow into the chamber, either the anodic chamber (2) or the cathodic chamber (3), it is generated a cross flow in the water stream to be treated; where said cross flow guarantees greater effectiveness in the oxidation and reduction processes as appropriate, and therefore the overall performance of the bioelectrochemical system (1) object of the invention is improved; so that thanks to the two corners being opposite (9a, 9d), in a series of chambers the water flow is input from a top of the prismatic structure (11), where the first corner (9a is located ), and the exit of the water stream is made from a lower part of the prismatic structure (11), where the first corner (9b) is located; and vice versa for the next camera, either the anodic chamber (2) or the cathodic chamber (3); obtaining the aforementioned cross flow when traveling diagonally and between the two opposite corners (9a, 9b) the interior (10) of the respective prismatic structure (11).
    It is worth highlighting an example of realization of the first preferred design option carried out, where an average of 3L / day of pork manure is treated; operating each biological cell (2, 3) at a hydraulic residence time (HRT) of 6h. Electrotrophic microorganisms use the most easily biodegradable organic matter (mainly volatile fatty acids: acetate) for electricity generation. And the nitrifying reactor
    (5) External operates with a HRT from 2 days to 4 hours. This HRT allows the oxidation of ammonium to nitrate by oxidizing ammonium and nitrite bacteria. The anodic chambers (2) of each biological cell (2, 3) sequentially remove the organic matter from the pig slurry. Where the elimination capacity of organic matter is 2.8 ± 0.3 kg O2 / m3 • day during the experimental period. The slurry to be treated has a high nitrogen load (mainly in the form of ammonium): 3.2 ± 0.2 kg N / m3 • day. And the elimination of nitrogen in the experimental unit occurs in two stages:
    -The first stage is the oxidation of the ammonium present in the pig slurry in the external nitrifying reactor (5). The nitrification rate obtained is 1.1 ± 0.2 kg N / m3 • day. Where ammonium is completely oxidized to nitrate. And the nitrite concentration is negligible. -Nitrates formed in the external nitrifying reactor (5) are introduced into the
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    cathode chambers (3) of the experimental unit; so that the denitrification capacity is 0.9 ± 0.2 kg N / m3 • day.
    In view of this description and set of figures, the person skilled in the art will be able to understand that
    The embodiments of the invention that have been described can be combined in multiple ways within the object of the invention. The invention has been described according to some preferred embodiments thereof, but it will be apparent to the person skilled in the art that multiple variations can be introduced in said preferred embodiments without exceeding the object of the claimed invention.
    10
    权利要求:
    Claims (11)
    [1]

    1.-Bioelectrochemical system (1) for the elimination of organic matter and nitrogen compounds existing in wastewater, where said bioelectrochemical system (1) comprises a plurality of biological cells (2, 3), which respectively have: -an anode chamber (2) configured to oxidize the organic matter of said wastewater, where said oxidation releases a series of electrons; - a cathodic chamber (3) configured to reduce the nitrogen compounds of said wastewater, where said reduction receives a series of electrons from the oxidation of the anodic chamber (2); and - an ion exchange membrane (8) located between the anodic chamber (2) and the cathodic chamber (3); wherein said bioelectrochemical system (1) is characterized in that the biological batteries (2, 3) are connected to each other through at least one channel (12a, 12b) configured for the circulation of the wastewater to be treated; where said, at least one channel (12a, 12b) has two sections of wastewater circulation: -a first section (12a) of oxidation of the organic matter of the wastewater, where the first section (12a) runs to through the plurality of the anodic chambers (2a, 2b, 2c, 2d, 2e, 2f) of each of the biological cells (2, 3); and - a second section (12b) of reduction of the nitrogen compounds of the wastewater, where the second section (12b) runs through the plurality of the cathode chambers (3a, 3b, 3c, 3d, 3e, 3f) of each of the biological batteries (2, 3).
    [2]
    2. Bioelectrochemical system (1) according to claim 1, characterized in that it comprises an aerated nitrifying reactor (5) located between the first section (12a) and the second section (12b) of said at least one channel (12a , 12b); wherein said external nitrifying reactor (5) is configured to oxidize the nitrogen compounds of the wastewater of the first section (12a) from a last anodic chamber (2f) of a last biological cell (2f, 3f); and introducing the wastewater resulting from said oxidation into the nitrifying reactor (5) towards the second section (12b) that begins in a last cathodic chamber (3f) of the last biological cell (2f, 3f).
    [3]
    3. Bioelectrochemical system (1) according to claim 2, characterized in that the exchange membrane (8) is an anion exchange membrane (8a).

    [4]
    4. Bioelectrochemical system (1), according to any of claims 2 and 3, characterized in that the external nitrifying reactor (5) comprises an oxygen probe
    (13) configured to regulate the amount of oxygen inside said external nitrifying reactor (5).
    [5]
    5. Bioelectrochemical system (1), according to claim 1, characterized in that each cathodic chamber (3a, 3b, 3c, 3d, 3e, 3f) of each biological cell (2, 3) comprises aeration means (6) configured to nitrify the nitrogenous compounds of wastewater; so that each cathode chamber (3a, 3b, 3c, 3d, 3e, 3f) is configured to nitrify the nitrogen compounds thanks to the aeration means (6), and denitrify said nitrogen compounds thanks to the reduction of these due to the contribution of electrons from each of the corresponding anodic chambers (2a, 2b, 2c, 2d, 2e, 2f).
    [6]
    6. Bioelectrochemical system (1) according to claim 5, characterized in that the exchange membrane (8) is a cation exchange membrane (8b).
    [7]
    7. Bioelectrochemical system (1), according to any of the preceding claims, characterized in that at least one condensing element (4) is connected to each biological cell (2, 3); wherein said capacitor element (4) is configured to receive electrons from each anodic chamber (2a, 2b, 2c, 2d, 2e, 2f), and supply electrons to each cathode chamber (3a, 3b, 3c, 3d, 3e, 3f) .
    [8]
    8.-Bioelectrochemical system (1), according to any of the preceding claims, characterized in that each anodic chamber (2a, 2b, 2c, 2d, 2e, 2f) of each biological cell (2, 3) has a community inside microbial responsible for oxidizing the organic matter of wastewater.
    [9]
    9. Bioelectrochemical system (1), according to any of the preceding claims, characterized in that each cathode chamber (3a, 3b, 3c, 3d, 3e, 3f) of each biological cell (2, 3) has a plurality inside of denitrifying microorganisms responsible for reducing the nitrogenous compound of wastewater.

    [10]
    10. Bioelectrochemical system (1), according to any of the preceding claims, characterized in that each biological cell (2, 3) is formed by a pair of prismatic structures (11) of rectangular base that define respectively the anodic chamber (2) and cathodic (3), where each prismatic structure (11) has a perimeter frame (9); so that: - the perimeter frame (9) of the prismatic structure (11) of the anodic chamber (2e) has four corners (9a, 9b, 9c, 9d), where one of them (9a) comprises a through hole to the second section (12b) of the channel (12a, 12b) of the wastewater, and is configured to allow the passage of wastewater from the cathode chambers (3e, 3f) located between said anodic chamber (2e); and where two opposite corners (9b, 9c) comprise orifices for the passage of wastewater, one of them towards the inside (10) of the anodic chamber (2e), and another one towards the outside of the anodic chamber (2e) , allowing the oxidation of organic matter from wastewater; and -the perimeter frame (9) of the prismatic structure (11) of the cathode chamber (3e) has four corners (9a, 9b, 9c, 9d), where one of them (9b) comprises a through hole belonging to the first section (12a) of the channel (12a, 12b) of the wastewater, and is configured to allow the passage of wastewater from the anodic chambers (2e, 2f) located between said cathode chamber (3e); and where two opposite corners (9a, 9d) comprise orifices for the passage of wastewater, one of them towards the inside (10) of the cathode chamber (3e), and another of them towards the outside of the cathode chamber (3e) allowing the reduction of nitrogen compounds in wastewater.
    [11]
    11. Process for treating wastewater by means of the system defined in any of the preceding claims through said at least one channel (12a, 12b) comprising the following steps: a) introducing said wastewater to a first chamber anodic (2a) of a first biological cell (2a, 3a), oxidizing an amount of organic matter during a corresponding part of the first section (12a) of the channel (12a, 12b); b) introducing the wastewater from the first anodic chamber (2a) of the first biological cell (2a, 3a), into the second anodic chamber (2b) of a second biological cell (2b, 3b), oxidizing a quantity of matter organic, during a corresponding part of the first section (12a) of the channel (12a, 12b); c) repeat the oxidation of wastewater a number of times equivalent to the number

    of batteries belonging to the bioelectrochemical system (1), and therefore, to the number of anodic chambers (2a, 2b, 2c, 2d, 2e, 2f), during the rest of the first section (12a) of the channel (12a, 12b); d) introducing wastewater from the last anodic chamber (2f), from the last biological cell (2f, 3f), to the cathodic chamber (3f) belonging to said last cell
    5, reducing a quantity of nitrogen compounds, during part of the second section (12b) of the channel (12a, 12b); e) introducing wastewater from the last cathode chamber (3f) of the last biological cell (2f, 3f), into a penultimate cathodic chamber (3e) of a penultimate biological cell (2e, 3e), reducing a number of compounds nitrogen, during part of the
    10 second section (12b) of the channel (12a, 12b): f) repeat the reduction of wastewater the same number of times equivalent to the number of batteries belonging to the bioelectrochemical system (1), and therefore, to the number of cathode chambers (3a, 3b, 3c, 3d, 3e, 3f), during the rest of the second section (12b) of the channel (12a, 12b).
    12. The bioelectrochemical system according to any one of claims 1 to 10, characterized in that the plurality of biological batteries (2, 3) are configured to generate electrical energy giving rise to an electricity generator.
    twenty
    25
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    同族专利:
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    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    WO2008109911A1|2007-03-15|2008-09-18|The University Of Queensland|Microbial fuel cell|
    US8524402B2|2008-05-13|2013-09-03|University Of Southern California|Electricity generation using microbial fuel cells|
    JP5629900B2|2009-06-16|2014-11-26|カンブリアン イノベーションズ インコーポレイデッド|Systems and devices for treating and monitoring water, wastewater, and other biodegradable materials|
    EP2595925A4|2010-07-21|2014-08-27|Cambrian Innovation Llc|Denitrification and ph control using bio-electrochemical systems|EP3330230A1|2016-11-30|2018-06-06|Eawag|Method and apparatus for the nitrification of high-strength aqueous ammonia solutions|
    CN107352636B|2017-08-23|2020-06-02|哈尔滨工业大学|Device and method for recovering heavy metals in electroplating industrial park wastewater and treating park sludge sewage simultaneously|
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