WO2006108532A1 - Capture de co2 et utilisation dans la digestion de matiere organique en vue de la production de methane - Google Patents

Capture de co2 et utilisation dans la digestion de matiere organique en vue de la production de methane Download PDF

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WO2006108532A1
WO2006108532A1 PCT/EP2006/003041 EP2006003041W WO2006108532A1 WO 2006108532 A1 WO2006108532 A1 WO 2006108532A1 EP 2006003041 W EP2006003041 W EP 2006003041W WO 2006108532 A1 WO2006108532 A1 WO 2006108532A1
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reactor
module
alkaline metal
value
sodium
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Cesarino Salomoni
Enrico Petazzoni
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Cesarino Salomoni
Enrico Petazzoni
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Priority to EP06723998A priority Critical patent/EP1984098A1/fr
Publication of WO2006108532A1 publication Critical patent/WO2006108532A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P5/00—Preparation of hydrocarbons or halogenated hydrocarbons
    • C12P5/02—Preparation of hydrocarbons or halogenated hydrocarbons acyclic
    • C12P5/023—Methane
    • 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
    • B01D53/46—Removing components of defined structure
    • B01D53/62—Carbon oxides
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D7/00—Carbonates of sodium, potassium or alkali metals in general
    • C01D7/10—Preparation of bicarbonates from carbonates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D7/00—Carbonates of sodium, potassium or alkali metals in general
    • C01D7/12—Preparation of carbonates from bicarbonates or bicarbonate-containing product
    • C01D7/123—Preparation of carbonates from bicarbonates or bicarbonate-containing product by thermal decomposition of solids in the absence of a liquid medium
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12M—APPARATUS FOR ENZYMOLOGY OR MICROBIOLOGY; APPARATUS FOR CULTURING MICROORGANISMS FOR PRODUCING BIOMASS, FOR GROWING CELLS OR FOR OBTAINING FERMENTATION OR METABOLIC PRODUCTS, i.e. BIOREACTORS OR FERMENTERS
    • C12M21/00—Bioreactors or fermenters specially adapted for specific uses
    • C12M21/04—Bioreactors or fermenters specially adapted for specific uses for producing gas, e.g. biogas
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12M—APPARATUS FOR ENZYMOLOGY OR MICROBIOLOGY; APPARATUS FOR CULTURING MICROORGANISMS FOR PRODUCING BIOMASS, FOR GROWING CELLS OR FOR OBTAINING FERMENTATION OR METABOLIC PRODUCTS, i.e. BIOREACTORS OR FERMENTERS
    • C12M23/00—Constructional details, e.g. recesses, hinges
    • C12M23/58—Reaction vessels connected in series or in parallel
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12M—APPARATUS FOR ENZYMOLOGY OR MICROBIOLOGY; APPARATUS FOR CULTURING MICROORGANISMS FOR PRODUCING BIOMASS, FOR GROWING CELLS OR FOR OBTAINING FERMENTATION OR METABOLIC PRODUCTS, i.e. BIOREACTORS OR FERMENTERS
    • C12M29/00—Means for introduction, extraction or recirculation of materials, e.g. pumps
    • C12M29/26—Conditioning fluids entering or exiting the reaction vessel
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12M—APPARATUS FOR ENZYMOLOGY OR MICROBIOLOGY; APPARATUS FOR CULTURING MICROORGANISMS FOR PRODUCING BIOMASS, FOR GROWING CELLS OR FOR OBTAINING FERMENTATION OR METABOLIC PRODUCTS, i.e. BIOREACTORS OR FERMENTERS
    • C12M43/00—Combinations of bioreactors or fermenters with other apparatus
    • C12M43/04—Bioreactors or fermenters combined with combustion devices or plants, e.g. for carbon dioxide removal
    • 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
    • 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
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/20—Capture or disposal of greenhouse gases of methane
    • 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
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/40—Capture or disposal of greenhouse gases of CO2
    • 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel
    • 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
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency
    • 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
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2
    • 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
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/59—Biological synthesis; Biological purification

Definitions

  • the present invention relates to an integrated process for capturing CO 2 particularly from exhaust gases and using the same CO 2 to increase the efficiency of the anaerobic digestion of organic matter to produce methane.
  • the process according to the present invention typically comprises two parts.
  • the first part of the process relates to the use, in a solution, of alkaline reagents together with a biological catalyst, carbonic anhydrase, immobilized onto an inert support, for absorbing, through a chemical reaction, emitted CO 2 to obtain a bicarbonate precipitate which is later regenerated by calcination leading to a concentrated gaseous CO 2 flow.
  • the second part of the process relates to the use of CO 2 microbiologically stepwise controlled anaerobic digestion of organic matter, organized in subsequent steps, specialised in acidification and methane production respectively, with intermediate steps devoted to the concentration and recycling of biomass.
  • Background art The growing CO 2 concentration in the atmosphere, due to the increasing use of fossil fuels derived energy, has a major impact on climate change. Numerous governments had to adopt necessary measures to reduce CO 2 emissions into the atmosphere (The Kyoto Protocol, EU Emission trading directive).
  • ammines which react with CO 2 , in an acid-base reaction, to produce a soluble salt carbamate.
  • the reaction is reversible at high temperature, making it possible to regenerate the alkaline agent.
  • absorption, through chemical interaction, is very efficient this process has a few disadvantages, amongst them the most relevant ones are the large energy consumption for regenerating the separating agent and the potential degradation of the agent itself in the face of pollutants: ammines, in fact, have a limited life span of utilization, due to the degradation resulting from their oxidation; they also lead to serious corrosion of plants.
  • the CO 2 aqueous form can then react both with water or, at high pH value, with hydroxide ions.
  • the step limiting the velocity of the indicated sequence of reactions is the CO 2 hydration reaction (2a) which makes the industrial application of it very difficult.
  • the CO 2 quick capture has also been tackled by using a biocatalyst, the carbonic anhydrase enzyme, one of the fastest known enzymes, capable of catalyzing the rapid interconversion of CO 2 and water into carbonic acid, protons and bicarbonate ions.
  • This enzyme can increase the reaction efficiency one million times, in particular the human carbonic anhydrase isoenzyme (CA II) can hydrate some 1.4 million CO 2 molecules per second.
  • Carbonic anhydrase is an ubiquitous enzyme, it can be found in different forms or isoenzymes in animals, plants and microorganisms (Budger and Price, 1994; Seltemeyer et al., 1993; Brown, 1990; Maren and Sanyal, 1983).
  • Carbonic anhydrase facilitates the CO 2 transfer from gaseous to liquid phase following well known laws governing gas mass transfer.
  • a process to remove CO 2 from a gaseous stream and turn it into stable solid from is disclosed.
  • the CO 2 enriched gas is passed through a gas diffusion membrane to transfer the CO 2 to a fluid medium.
  • the CO 2 rich fluid is then passed through a matrix containing carbonic anhydrase to accelerate the conversion of CO 2 to carbonic acid.
  • a mineral ion is added to the reaction so that a precipitate of carbonate salt is formed.
  • the hydrogen and bicarbonate ions containing solution can be fed into a second reactor, identical to the one used for capturing CO 2 , and there the ions are converted into water and CO 2 . Because of the costs associated with the ion exchange technology or with the pressure input which is needed to have the exhaust gas overcome the pressure drops and obtain a CO 2 concentrated flow into the two column reactors, the two above mentioned solutions seem to be applicable only for limited exhaust gas streams.
  • Acetic acid can be produced, according to these systems, at relatively low concentrations (around 5%) and its recovery by means of distillation or of other more complex processes makes still too expensive the global process. It is therefore economically more profitable to use directly the anaerobic fermentations products, coming from the refuse gas, in the colture medium and do this in less expensive ways, like that of bioconversion to another product easier to separate.
  • the organic matter digestion process consists of four main phases which are supported by different microbial populations: the hydrolytic phase involves the conversion of complex organic substances into soluble organic substances; the acidogenic phase concerns the conversion of soluble organic substances into volatile fatty acids, alcohols and hydrogen; the acetogenic phase is the one where volatile fatty acids and alcohols are turned into acetic acid, carbon dioxide and hydrogen; the methanogenic phase contemplates both acetic acid and hydrogen as well as carbon dioxide being transformed into methane. There are, moreover, other minor phases or biochemical reactions that take place in between the four major phases.
  • US patent n. 4022665 further proposed for the methanogenic stage the introduction of a series of functional separation and specific operational conditions referred to organic load and retention time.
  • Another proposed solution is that of functional separate units in parallel operation to independently manage the gaseous and the liquid effluent coming from the acid stage, as in US patent n. 4696746: in the liquid phase biomethanation of fatty acids, while in the gaseous one biomethanation of carbon dioxide and hydrogen take place respectively, maintaining different microbial populations in the two functional units.
  • Multistage systems proved to be good at treating large quantities of organic matrices coming from diverse origins, at operating with higher concentrations of microbial populations and specialized enzymes in smaller digester, at operating with shorter hydraulic retention times while obtaining treatment levels similar to the ones of conventional systems; unfortunately they display high investment costs either in the building of new ones or in the restructuring of existing conventional ones. There is a still ample room for improvement in such systems with respect to the efficiency of the solid organic matrices treatment as well as to the possibility of treatment integration between that of matrices and the fermentation one of exhaust gases; in such a way no significant further investment is required on top of that needed to increase the efficiency of the organic matrices treatment by itself. Many scientific publications and patents concentrate, beyond the aspects related to the stage separation, on the need to identify suitable equilibrium between production and consumption of the different intermediate compounds in each of the different stages resulting from the separation of the process.
  • the degree of mutual dependence among the different microbial populations can vary considerably: on the one hand the organisms at the end of anaerobic process always depend upon the preceding ones for their substrates, on the other, in each stage, the substrates using organisms have a significant influence over the preceding ones, by removing their products.
  • polymers polysaccharides, proteins, nucleic acids and lipids
  • oligomers and monomers sucrose, amino acids, purines and pyrimidines, fatty acids and glycerol
  • the produced monomers are further fermented into fatty acids, succinates, lactates, alcohols, etc.
  • Some of these fermentation products mainly acetates, hydrogen, carbon dioxide and other one carbon atom substances, can be turned directly into methane and carbon dioxide by methanogenic microorganisms.
  • a second group of fermentative bacterial populations (secondary fermentative or protons reducing) convert their substrates into acetates, hydrogen and carbon dioxide which are used by methanogenic organisms in the traditional anaerobic digestion process.
  • Hydrogen has been identified as an anaerobic process component capable of exercising an influence on the structure of it and on the ways of its development, by regulating the proportion of the different intermediate products both in fermentation and methanation.
  • Methanogenesis inhibiting conditions e.g. significantly lower than neutral pH, nitrates presence in the organic material, high variability organic loads
  • sulfate-reducing bacteria may compete for hydrogen, but only when sulfates are present in high concentrations, which is rare in organic refuse or wastewaters. That notwithstanding, if hydrogen concentration increases for whatever reason, (e.g.
  • Carbon dioxide and bicarbonate are themselves inherent products to the anaerobic process and they represent furthermore bacterial growth indispensable factors as well as important electrons acceptors.
  • CO 2 utilization needs an adequate hydrogen supply.
  • Clostridium spp. and Eubacterium spp. type organisms produce hydrogen from carbohydrates
  • Syntrophobacter wolinii and Syntrophomonas wolfei type organisms produce hydrogen from propionates or butyrates oxidation.
  • microorganisms of different types in part they compete for the same substrates, as in the case of hydrogen, in part they use for growing partially different substrates; only methanogens and acetogens organisms (e.g. Acetobacterium woodii and Clostridium thermoaceticum) use mainly CO 2 and hydrogen to produce methane and acetic acid/acetates respectively.
  • methanogens and acetogens organisms e.g. Acetobacterium woodii and Clostridium thermoaceticum
  • competition for hydrogen takes place in between reductive-acetogen and methanogen organisms on the basis of their affinity with it, this is higher in the methanogens than in the acetogens ones: therefore when there is methanogenesis there cannot be reductive-acetogenesis.
  • Anaerobic microorganisms known for their ability to convert hydrogen and carbon dioxide or carbon monoxide and water into acids, acid salts and alcohols, comprise Aceto bacterium kiwui, A. woodii, Clostridium aceticum, Butyribacterium methylotrophicum, C. acetobutylicum, C. formoaceticum, C. kluyveri, C. thermo aceticum, C. thermocellum, C. thermohydrosulfuricum, C. thermosaccarolyticum, Eubacterium limosum, C.
  • Ijungdahlii Peptostreptococcus productus; they have a metabolic capability that differentiate them from other acetogenic organisms synthesizing acetates from other metabolic processes.
  • acetogenic organisms are, from a phylogenetic point of view, a rather diversified group and they have been isolated in equally differentiated ecosystems: wastewaters, anaerobic digesters, natural sediments, termite gut, rumen, not ruminants intestinal tract, extreme environments with respect to pH, salinity and temperature. It has been estimated that acetogenesis globally produces billions of tons of acetates every year and that acetogenic organisms perform a relevant role in the carbon cycle (Drake et al., 2004).
  • the main problem comes from the difficulty in regulating hydrogen and volatile fatty acids which, at high concentrations, may inhibit the treatment of organic matrices to reach high methane concentration and which create some time impediments to a stable and economic continuous management of the process.
  • the alkaline substances used to obtain simultaneously an high concentration of methane in the produced biogas and an adequate pH control in the methanation reactor, come in two main groups: those that capture gaseous CO 2 and turn it into bicarbonate (strong bases and carbonate salts) and those that add directly to the liquid medium bicarbonate alkalinity (bicarb onates).
  • a strong base e.g. calcium or sodium hydroxide
  • a carbonate salt e.g. sodium carbonate
  • the process control by means of the cited chemical substances which trap the gaseous CO 2 , demands, nevertheless, that their adding be done gradually, in subsequent steps, to make possible the reaching of the ionic equilibrium after each addition of chemical substance without having large pH jumps which could be dangerous for the methanogenic microorganisms.
  • the chosen chemical product is calcium hydroxide, as it is relatively common because it is cheap, then it traps CO 2 and turns it into bicarbonate; yet, when bicarbonate reaches the 0,5-1 g per liter concentration, whatever new adding is done it leads to the formation of insoluble carbonate.
  • CO 2 is removed from the gas but the system alkalinity is not augmented.
  • the CO 2 partial pressure drop in the gas determines a rapid increase in the pH value, but, in view of the fact that alkalinity was not augmented, the pH is instable so that when the biological activity resumes in an efficient way, the pH value rapidly drops once more.
  • calcium hydroxide can be proposed only in operational conditions where the pH value is less than 6.5 and can be added in limited amounts to allow an increase in pH value to no more than 6.8.
  • the buffering capacity is exercised at a moderately alkaline pH value; these are particularly suitable conditions to the methanogenic microbial populations growth, and do not imply large jumps even in the case of excessive doses of the chemical substance.
  • bicarbonate is easier to handle when compared to hydroxides and carbonates, it is not corrosive and toxic if used in appropriate ways, it is soluble in water with no difficulties, it does not form hard deposits and does not demand frequent cleaning and maintenance.
  • the main task of the present invention is to provide a process for capturing and separating the CO 2 contained in a gaseous flow and for using the CO 2 so captured.
  • the captured CO 2 is used in the anaerobic treatment of organic matter to produce methane; such process is more efficient, requiring smaller investment and lower running costs than the ones known to the prior art.
  • the first module comprises the following stages: - CO 2 removal from the exhaust gas in an extraction zone, by means of an alkaline metal solution and more particularly of sodium and CO 2 dissolution and hydration catalysed by immobilized carbonic anhydrase;
  • the second module comprises the following stages:
  • First module Another task of the present invention is that of providing a new and better process to capture CO 2 contained in an exhaust gas and generate a concentrate gaseous CO 2 and/or solid bicarbonate flow.
  • a characteristic feature of the invention is to remove, in the first module, the need to operate in very caustic conditions while maintaining quick and efficient the CO 2 capture by means of a combination of an absorption process and a chemical reaction in an alkaline metals solution supplemented by an immobilized biocatalyst, carbonic anhydrase, favouring CO 2 hydration.
  • the advantages of this new process are low investment and running costs and better environmental safety.
  • a further task of the present invention is to provide, with the bicarbonate produced in the first module, one of the essential elements to make more efficient and stable the process taking place in the second module.
  • This task is performed by adding bicarbonate in the second module methanation zone in order to increase methane concentration in biogas and to maintain a slightly alkaline pH, this condition is particularly suitable to methanogenic bacterial populations growth.
  • a further task of the present invention is to provide a CO 2 capture and separation process which may significantly contain the circulating solution volume and the energy consumption associated with the alkaline agent regeneration. This task is performed in the first module by coming out an efficient CO 2 capture in liquid phase while running, on the other hand, the alkaline agent regeneration in solid phase, in reasonably small plants and at equally low temperature.
  • a further task of the present invention is to provide a CO 2 capture and separation process which may significantly contain biocatalyst and alkaline agent degradation.
  • This problem can be solved by retrofitting the CO 2 capture module to traditional pollutants (NOx, particulate, SOx) removal plants and by using temperatures which may be compatible with the management of chemical and biotechnological processes contemplated in the present invention.
  • the advantage so achieved is that the biocatalyst and the alkaline agent, in such a condition, last for a long time and thus their cost per tonne of removed CO 2 is correspondently reduced.
  • the present invention provides a new method for using the CO 2 in treating organic matter in order to reach, on the one hand, a fuller degradation of volatile solids which are contained in the organic matter and, on the other, an increased methane production.
  • Specific and unique characteristics of the invention are, firstly, the specialization of mixed anaerobic micro organisms populations which are present or can be added to the anaerobic digestion process and, secondly, their environmental conditioning determined mainly by the CO 2 and bicarbonate introduction into the process.
  • pre-acidification zone there are or can be introduced high density mixed hydrolytic bacterial populations; in the liquid medium of the fermentation reactor there are or can be introduced mixed high density acidogenic and acetogenic anaerobic bacterial populations; in the liquid medium of the methanation reactor there are or can be introduced mixed high density methanogenic microbial populations.
  • mixed populations is a colture of two or more microbial populations which have been isolated from ecosystems comprising: wastewaters, anaerobic digesters, natural sediments, termites intestines, rumen, non-ruminants intestinal tracts; or else coming from extreme environments with respect to pH value, salinity and temperature; or, finally, found in collections of microbial cultures, kept by scientific institutions or biotechnological firms.
  • a further task of the present invention is to provide a new organization of the process in separate stages, with biomass retention, so as to gain an higher efficiency in every stage and a better overall stability.
  • the key element which is the innovative and unique feature characterising the process, is in the fact that the increased degradation rate of the polymeric materials, especially the volatile solids contained in organic matter, is obtained by introducing gaseous CO 2 into two sections: pre-acidification, the first one, fermentation, the second, where suitable conditions are created to hydrolysis and hydrogen production respectively and able also to inhibit methanogenic microorganisms, and to block CO 2 and hydrogen conversion pathway to methane.
  • the introduced CO 2 is immediately used, together with hydrogen, by bacterial populations so as to increase the overall acetates production.
  • a further task is to obtain a process characterised by stability and robustness in handling variations in composition and quantity of organic matter and optimised with respect to the maximization of exogenous CO 2 that can be introduced into the system.
  • These object are reached by controlling the volatile fat acids content and the pH value in the acid and methanogenic stages.
  • the fatty acids concentration and the pH value in each reactor are free to fluctuate in between stage specific predetermined levels.
  • the volatile fatty acids content is checked discontinuously, while the pH value, more conveniently, is checked and controlled continuously to guarantee process stability.
  • the pH values are regulated, on the one hand, by using as the only chemical agents bicarbonate and CO 2 coming from the CO 2 capture and separation module, on the other by regulating the substrate flows amongst reactors.
  • the process proposed in the second module is economically efficient because, on top of consuming exogenous CO 2 , it requires smaller digesters per unit mass of treated organic matter, and one should note that the larger share in investment costs for anaerobic digestion plants is due precisely to digesters volume.
  • the process can be run in existing anaerobic digestion plants after limited changes in structure and equipments, thus overcoming possible difficulties in siting new plants.
  • the process shows important advantages with respect to operational costs as well, in as much as it reduces the solid fraction remaining after digestion and increases the possibility of dehydrating it: the consequence is a reduction in landfilling, in incineration or in possible further uses costs; finally, the large increase in net methane production brings in equally larger revenues.
  • Fig. 1 represents a schematic basic configuration of an integrated process according to the present invention.
  • Fig. 2 represents a schematic basic configuration of the first module of the process of Fig. 1 : in it, the functional structure and the equipments composition are illustrated.
  • Fig. 3 represents a schematic basic configuration of the second module of the process of Fig. 1 : in it, the functional structure and the equipments composition are illustrated.
  • Fig. 1 shows the scheme of a new integrated process, suggested by the present invention, for capturing CO 2 and using it in order to increase the efficiency in the anaerobic digestion of organic matter so as to increase methane production.
  • the process consists in two integrated modules: the first one is named “gaseous emissions treatment” (GET), the second is named “treatment of organic matter” (TOM).
  • GET gaseous emissions treatment
  • TOM treatment of organic matter
  • an exhaust gas typically as the one outflowing from combustion chambers in incinerators or electric power, thermal power, steel, cement, paper, glass, ceramic plants or oil refineries, after removal of traditional pollutants (NOx, particulate, SOx); this exhaust gas has low CO 2 concentrations, typically something between 3 and 20% of total volume.
  • the removal treatments bring the inflowing gas temperature to values ranging between 30 and 80 0 C which are compatible with the management of the chemical and biotechnological processes contemplated in the present invention.
  • the CO 2 containing exhaust gas enters into the extraction zone, which consists of a contact and dissolution reactor (1), through a line (a) directly connected to the emissions flow.
  • the contact between the exhaust gas and the alkaline metal solution and more particularly of sodium and again between this one, being CO 2 enriched, and the carbonic anhydrase, may take place in whatever reactor initially designed for gas/liquid reactions and subsequently perfected to guarantee that the biocatalyst be maintained, at all times, in liquid phase or hydrated.
  • the reactor has a flow in and a flow out point for the gaseous emissions; further it has a flow in point for the capture solution coming through line (b) and a flow out point, located at the bottom of the reactor where the solution is collected to discharge it through exit line (c).
  • the capture reactor is equipped so as to make possible controlling the two separate flows, that of gaseous emissions and the one of the capture solution.
  • the carbonic anhydrase enzyme is immobilized in ways and onto supports known to the art.
  • the alkaline metal solution and more particularly of sodium minerals flowing into the reactor has a pH value set between 8.3 and 9.6.
  • the contact process between the CO 2 rich exhaust gas and the alkaline metal solution and more particularly of sodium, aided by carbonic anhydrase, determines a significant increase in the concentration of carbonic acid, protons and bicarbonate ions.
  • Alkaline metal carbonate and more particularly of sodium in the solution react with the stoichiometric quantities of the species resulting from CO 2 dissolution and hydration, further augmenting in this way the bicarbonate ions concentration, and consequently their own input into the subsequent precipitation reactor.
  • the obtained solution has pH value between 7.5 and 8.3.
  • the temperature in the capture reactor may vary between 35 and 75 0 C.
  • the CO 2 dissolution rate into water is higher the lower is the temperature.
  • the alkaline metal carbonate reaction rate, with the species resulting from CO 2 dissolution, to form bicarbonate is lower at lower temperature. Therefore the alkaline solution temperature must be maintained at a level such as to obtain CO 2 dissolution and hydration in line with the desired rate of reaction between alkaline metal carbonate and the species resulted from CO 2 dissolution and hydration.
  • Temperature is maintained below 75 °C and preferably in the interval between 35°C and 60°C.
  • the gas outflowing from the capture reactor is sent to a demister (2) and then released into the environment.
  • the solution, containing bicarbonate and other species resulting from CO 2 dissolution and hydration and from their reactions with alkaline metal carbonate is first harvested in the first reactor and then transferred to a second precipitation reactor (3), where solid alkaline metal carbonate is added to obtain an over saturated alkaline metal bicarbonate solution.
  • This second reactor consists of whatever container be known to the art and which, by dimensions and equipments, may contain and maintain, in suspension the solution, for as long as it takes to fully convert all the added alkaline metal carbonate into alkaline metal bicarbonate.
  • the pH value is controlled by increasing or decreasing the pH value in the harvested solution, that is by dissolving and hydrating a smaller or larger CO 2 quantity.
  • the pH value is controlled by increasing or decreasing the quantity of solid alkaline metal carbonate which is introduced into the solution.
  • the pH value can be controlled by introducing into the solution protons or substances which may effect it.
  • the precipitation reactor In the precipitation reactor the best pressure and temperature conditions are maintained in order to obtain alkaline metal bicarbonate. Further the solution is agitated up to the point when almost all added alkaline metal carbonate is converted into precipitated alkaline metal bicarbonate. "Almost all” is to be understood as whatever fraction, ranging between 90 and 100%, of the alkaline metal carbonate which was added to the solution.
  • the solution pH value, after adding alkaline metal carbonate, is never below 9, and better still is between 9 and 9.6.
  • the precipitation reactor temperature may vary between 35 and 6O 0 C.
  • the solution harvested in the precipitation reactor and containing suspended solid alkaline metal bicarbonate is transferred to an apparatus (4) known in the art and designed for solid/liquid separation.
  • the obtained solution is transferred, through line (d), to a storage unit (5) to be recycled in the first capture reactor, through line (b).
  • the carbonate, produced in the regeneration unit, is recycled as a reagent into the precipitation reactor through line (f), while the gas (CO 2 + H 2 O) is sent, through line (g), to an apparatus (7) for the separation and concentration of gaseous CO 2 .
  • the steam is condensed and the released and separated CO 2 is compressed and stored (8) in view of its further uses in the anaerobic digestion second module or for even different uses.
  • part of the solid alkaline metal bicarbonate is transferred, through line (h) to the methanation zone, in the TOM module, in order to keep the most suitable conditions for growing methanogenic microbial populations.
  • the goal of using CO 2 to produce methane by means of anaerobic microorganisms which may be present, or else added, in a microbiological system for the anaerobic digestion of organic matter is obtained in the TOM module according to a process which is schematically presented in Fig. 3 and described in what follows.
  • the organic matter enters, through line (i), into the functional storage and pre-treatment section (9) where it is adequately prepared for the anaerobic digestion process, made homogeneous, of appropriate dimensions, with the desired solids concentration and pollutions free.
  • the functional storage and pre-treatment section (9) where it is adequately prepared for the anaerobic digestion process, made homogeneous, of appropriate dimensions, with the desired solids concentration and pollutions free.
  • different actions with the different equipments umps, filters, mixers, hydropulper, etc.
  • the organic matter, made available in the desired conditions is transferred to the pre-acidification section (10) through line (i).
  • Organic matter enters into the pre-acidification section with a suspended solids content ranging between O and 35% and a chemical oxygen demand (COD) ranging between O and 200 grams per litre.
  • CO 2 chemical oxygen demand
  • the CO 2 which is not dissolved, is harvested in the upper part of the present section and then recycled into the very same section.
  • the acid condition derived from CO 2 dissolution and hydration, starts a controlled degradation of solid and soluble complex organic substances (carbohydrates, proteins, lipids) into monomers in soluble form (sugars, amino acids, long chain fatty acids).
  • the CO 2 partial pressure in this section is regulated so that the organic matter pH value preferably contained in the interval 3 to 6, and better still 4 to 5.5.
  • the hydraulic retention time (HRT) may range approximately between 6 hours and 2 days, while the solids retention time (SRT) between 1 and 3 days. Temperature is approximately maintained between 20 and 8O 0 C.
  • the fermentation reactor (11) which is structured to sustain the growth of suspended or fixed to inert supports bacteria.
  • gaseous CO 2 is introduced by means of an hydraulic or, if present, a gas based moving system; alternatively by means of whatever other method known to the art.
  • the CO 2 which is not dissolved and hydrated nor utilized is harvested in the upper part of the same reactor as a mixed gas (CO 2 , H 2 , other) and recycled into the same fermentation reactor.
  • a trophic network is maintained, made up of different groups of microorganisms, each characterised by the substrates as well as by the products of its metabolism.
  • mixed hydrolytic bacterial populations carry out the last reduction of complex organic substances into monomers; mixed fermentative acidogenic bacterial populations oxidise simple organic substrates into volatile fatty acids and alcohols, which represent, in the next step, the main substrates for the mixed acetogenic bacterial populations producing acetic acid, formic acid, CO 2 and H 2 .
  • the process parameters, suitable to the competitive growth of mixed acetogenic bacterial populations, capable of reducing CO 2 to acetates, include a total organic load ranging between 3 and 150 kg per cubic meter of reactor per day and the introduction of a CO 2 quantity defined with respect both to the organic load and to the culture volume which is present in the reactor.
  • the pH value in the reactor is allowed to vary between an upper bound, equal to 6.3, below which the hydro geno trophic methanogenesis totally blocked or significantly reduced and hydrogen consumption by methanogenic microorganisms is avoided, and a lower bound, equal to 4.3, to sustain acetogenic bacteria's competitive growth. Because of the fact that these populations are more resistant to ammonia than the methanogenic ones, they are able to operate even with high nitrogen content organic matter, which can give higher than 1.2 gr. per litre ammonia concentrations.
  • the pH value is maintained within desired limits by regulating the organic and the CO 2 load, and by recycling the alkaline effluent from the successive methanogenesis reactor, through line (t).
  • the hydraulic retention time (HRT) is approximately regulated between 12 hours and 3 days, while the solid retention time (SRT) between 1 and 7 days and temperature between 30 and 60 °C.
  • the effluent from the fermentation reactor, through a process line (n) feeds a concentrating and conditioning apparatus (12) where a solid/liquid separation takes place: part of the concentrated solid is recycled, through line (o) into the pre- acidification tank (10); the excess solids (non degradable organic substances and non volatile solids) may be disposed of through line (s).
  • the excess solids disposal depends upon inorganic substances or inert solids concentrations as well as upon the efficiency of the liquid/solid separating apparatus which is employed.
  • the liquid part, containing dissolved organic components (mainly acetates), on top of CO 2 , hydrogen and other substances, is, on the contrary, sent, through line (p) to a methanation reactor (13) in the successive methanogenic zone where bicarbonate, coming from the GET module, through line (h), may be added in order to control alkalinity and pH value.
  • a methanation reactor (13) in the successive methanogenic zone where bicarbonate, coming from the GET module, through line (h) may be added in order to control alkalinity and pH value.
  • acetoclastic methanogenic organisms which transform acetic acid into methane and CO 2
  • hydro genophilic methanogenic organisms which carry out the hydrogen anaerobic oxidation and the CO 2 reduction to methane; it is through these populations that a high methane content gas and a digested effluent are produced.
  • the methane containing gaseous product is collected through line (q) and sent to a gasometer (14).
  • the digested effluent is sent, though line (r) to a separator/concentrator (15).
  • the solid fraction microorganisms and non degraded solids
  • the liquid effluent is recycled into the methanogenic reactor.
  • the excess solids are disposed of through line (s).
  • the liquid effluent is recycled through line (t) into the fermentation reactor or else finally discharged.
  • the operations conditions in the methanation zone include a total organic load ranging between 1 and 70 kg per cubic meter of reactor per day, on top of dissolved CO 2 and hydrogen.
  • the pH value in the reactor is allowed to vary between 9.0 and 7.2: such values are optimal for methanogenesis.
  • the efficient volatile fatty acids and CO 2 conversion is obtained by regulating the hydraulic retention time (HRT) between 4 and 12 days and the solids' one (SRT) between 8 and 20 days, approximately, with temperature ranging between 30 and 60 0 C.
  • a crucial innovation in the present proposal is represented by the introduction of a large amount of CO 2 into organic matter anaerobic digestion process. Such element causes an important discontinuity in the environmental conditions where bacterial populations are commonly found.
  • the discontinuity on top of breaking the existing equilibrium in the composition of the populations, generates, through selection and adaptation processes, a new long run dynamic equilibrium in the populations composition. Therefore, in the new situation, the management parameters (organic load, HRT and SRT) of the system improve dramatically with respect to those in the initial state.
  • Every reactor is equipped with an adequate monitoring system.
  • the most important process parameters (temperature, pH value, produced gas composition, etc.) are measured to be used for controlling and optimising the digestion process.
  • the main controlled functions comprise: temperature and pH value in every reactor; the incoming CO 2 and organic matrix flows to the fermentation reactor; the recycling rate between the fermentation and the methanation reactors and vice versa; the bicarbonate dosing into the methanation reactor.
  • the pH value in the acid reactor reaches the predetermined lower bound the recycling of the liquid effluent from the methanation reactor is started, while, when the pH value reaches the upper bound, the recycling is ended.
  • the present invention relates to a system for capturing CO 2 in a low CO 2 concentration gaseous flow and for using it to digest organic matter in order to produce methane; this system is adapted to realize the process according to the present invention.
  • the low CO 2 concentration gaseous flow is typically the exhaust gas outflowing from combustion chambers in incinerators or electric power, thermal power, steel, cement, paper, glass, ceramic plants or oil refineries.
  • the process according to the present invention comprise a first module and a second module.
  • These two modules may take place in two plants, in particular two distinct and separated plants; additionally, these two plants may be located even far apart.
  • the second plant may receive the high CO 2 concentration gaseous flow from the first plant through a pipeline; in principle, other means might be used for transporting such CO 2 from the first plant to the second plant.
  • Patents and Patent applications US20040259231

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Abstract

L'invention concerne un procédé qui offre une solution de remplacement à la séquestration de CO2 dans les gaz appauvris ou les champs de pétrole. L'invention concerne également un procédé intégré qui combine un premier module, pour capturer et séparer le CO2 des gaz d'échappement, et un second module, pour exploiter le CO2 capturé dans la digestion anaérobie de matière organique et obtenir ainsi du méthane. Dans le premier module, le CO2 est extrait du gaz de combustion par contact et transfert de masse à une solution de métal alcalin, et plus particulièrement, de sodium. Le CO2 dissous dans la solution est rapidement hydraté en acide carbonique à l'aide de l'anhydrase carbonique immobilisée sur un support inerte. Le CO2 hydraté est enfin réagi avec le métal alcalin. Après addition du carbonate métallique à la solution, le précipité de bicarbonate alcalin obtenu subit une calcination pour former un flux concentré de CO2. Dans le second module, l'écoulement concentré de CO2 sert à obtenir un environnement parfaitement approprié pour l'hydrolyse de la matière organique et pour la production d'hydrogène dans des sections distinctes et spécialisées destinées, respectivement, à l'acidification et à la fermentation. Parallèlement, des populations microbiennes mixtes de haute densité, initialement présentes ou ajoutées sélectivement au procédé de fermentation, sont conditionnées pour exploiter le CO2 et l'hydrogène dans le but d'augmenter la production d'acétates, et par conséquent, de méthane. Le procédé susmentionné peut être appliqué par des firmes qui émettent des gaz à effet de serre ainsi que par celles qui sont impliquées dans la gestion des déchets.
PCT/EP2006/003041 2005-04-08 2006-04-04 Capture de co2 et utilisation dans la digestion de matiere organique en vue de la production de methane WO2006108532A1 (fr)

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IT000217A ITBO20050217A1 (it) 2005-04-08 2005-04-08 Cattura della co2 da gas esausti e suo uso nella digestione anaerobica di materiale organico
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