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• • 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
• • 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
• • C—CHEMISTRY; METALLURGY
  • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
  • C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
  • C12N1/00—Microorganisms, e.g. protozoa; Compositions thereof; Processes of propagating, maintaining or preserving microorganisms or compositions thereof; Processes of preparing or isolating a composition containing a microorganism; Culture media therefor
  • C12N1/12—Unicellular algae; Culture media therefor
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2251/00—Reactants
  • B01D2251/95—Specific microorganisms
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2257/00—Components to be removed
  • B01D2257/50—Carbon oxides
  • B01D2257/504—Carbon dioxide
• • 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
  • Y02P20/50—Improvements relating to the production of bulk chemicals
  • Y02P20/59—Biological synthesis; Biological purification

Definitions

• the invention relates to the field of sequestering carbon dioxide (C0 2 ), in particular the biological uptake of C0 2 by means of bacteria, of the cyanobacterial type.
• the invention is also relevant to the field of energy recovery, in particular the valorization of biomass.
• phytoplankton is at the origin of the primary production. It contributes, at the level of the oceans, to the consumption of C0 2 by means of photosynthesis on the species hydrogénocarbonate.
• Cyanobacteria that are prokaryotes are one of the biological components of this phytoplankton. Cyanobacteria use marine bicarbonate ion HC0 3 "as the inorganic carbon species, and not the dissolved C0 2. Indeed in seawater, the concentration of dissolved C0 2 is small compared to the hydrogen ion. The other mineral carbon species in this marine environment, carbonate, is not used by phytoplankton microorganisms as a carbon source, via photosynthesis.
• Unicellular cyanobacterial prokaryotic organisms and also certain eukaryotic organisms, are capable of producing photosynthesis on the hydrogencarbonate ion, not only of biomass, but also of calcium carbonate (called calcite) when calcium is present. in the middle, and that the growing conditions are adapted.
• calcite calcium carbonate
• biomass which consists of carbon, oxygen, nitrogen, hydrogen and sulfur (CONHS) elements
• CONHS carbon, oxygen, nitrogen, hydrogen and sulfur
• the valorization of biomass, in particular algae can be carried out using lipids, in particular for the production of fatty acid methyl esters used as biofuels, in addition for example in petroleum distillate "diesel".
• This valorisation of lipids requires the use of micro-algae selected for their high lipid content.
• Cyanobacteria are not known to produce significant amounts of lipids and are therefore of little interest for the production of biofuels.
• some of these strains are known to use atmospheric nitrogen (N 2 ) as a nitrogen source for biomass synthesis.
• cyanobacteria can produce a biomass that can be used for hydrogen production.
• Cyanobacteria are indeed mentioned in the literature for their properties to divert the flow of electrons from the two stages of photosynthesis for the production of hydrogen.
• Several pathways have been identified, including one using dehydrogenase of the strain, but many problems remain to be solved.
• Cyanobacteria because of their low lipid content, are not interesting for biofuel production, but can be used for the production of biomass by culture in an aqueous medium in a carbonate system and for the subsequent methanation of this biomass grown on hydrogencarbonate . Laboratory studies show that at the end of the reaction, when the hydrogencarbonate ion is completely consumed, a lysis process occurs rapidly, which positions the biomass of cyanobacteria in a digestibility situation more favorable than the biomass from microalgae.
• this biomass also has the advantage of being able to be used directly as a fertilizer given its nitrogen content.
• the method according to the invention uses the cyanobacteria culture and makes it possible to solve all the problems mentioned for the valorization of the biomass, in that it proposes at the same time corrections relating to the conduct of the processes of production of biomass resulting to manage the distribution within the algal biomass between proteins, lipids and sugars, but also enzymatic and physical pretreatments to improve the "digestibility” or “biodegradability" of these structures present in the wall and the membrane.
• the cyanobacteria culture carried out under optimized conditions on a carbonate system in the presence of calcium makes it possible, by consumption of the hydrogencarbonate ion, to produce two products, a first one in the form of a biomass of cyanobacteria easily recoverable, a second in the form of calcite (calcium carbonate CaCO3) which constitutes a carbon trap.
• calcite calcium carbonate
• the invention relates to a process for the biological capture of C0 2 by producing biomass and calcite by means of cyanobacteria, in which the cyanobacteria culture is carried out on a carbonate system (comprising carbon ions C0 3 2 - and hydrogen carbonate ions HC0 3 " ), in the presence of calcium, with a pH regulation by controlled injection of C0 2 .
• the invention also relates to the use of the biomass obtained by the process as a fertilizer or for energy purposes.
• the present invention relates to an integrated method for biological capture of C0 2 using cyanobacteria comprising the following steps:
• cyanobacterial photosynthesis is carried out on the hydrogencarbonate ions to produce a cyanobacterial biomass composed of carbon, oxygen, nitrogen, hydrogen and sulfur elements and to precipitate calcium carbonate (CaCO 3);
• c) inorganic carbon is supplied by injecting CO 2 to regulate the pH during the photosynthesis reaction.
• the CO 2 can be atmospheric and the cyanobacteria can be grown in at least one open reactor.
• At least part of the injected CO 2 can be derived from industrial fumes / discharges.
• Steps a), b), c) can be repeated until the calcium in the medium is depleted.
• the pH can be regulated to a value between 9 and 10.
• the culture medium may be a synthetic aqueous medium containing calcium and a carbonate system, or a marine environment.
• Nitrogen in the medium can be supplied as nitrate ions.
• the nitrate ions may be calcium nitrate.
• the cyanobacterial culture can be carried out under continuous, semi-continuous or batch conditions.
• a methanization step of the cyanobacterial biomass can be carried out to transform the biomass into methane.
• the methanation step can be carried out by injecting the biomass into an anaerobic digester during the night phase.
• the biomass methanation step can be carried out directly after the production step.
• the biomass can be separated from the water from the environment for thermal recovery.
• Biomass can be valorised by direct combustion and heat recovery, or by pyrolysis to generate an oil.
• the biomass obtained can be used as a source of energy.
• the biomass obtained can be used as a fertilizer.
• the process can be used for the production of calcite (CaCO 3) and mineral sequestration of CO 2.
• FIGS 1 to 8 illustrate the various aspects of the invention without limitation.
• FIG. 1 represents the evolution of the biomass concentrations and of the following species: calcium, C0 3 2 " , HCO 3 " , as well as the evolution of the pH during the assimilation of hydrogen carbonate by cyanobacteria, in batch, in the absence of calcium, and without inorganic carbon contribution during the culture.
• FIGS. 2a and 2b show the evolution of the biomass concentrations, and of the following species: calcium, C0 3 2 " , HCO 3 " , as well as the evolution of the pH during the assimilation of the hydrogencarbonate by cyanobacteria, batchwise in the presence of calcium ( Figure 2a: the hydrogencarbonate is present in a large excess compared to calcium, Figure 2b: the calcium is present in a large excess relative to the hydrogencarbonate). In this case also the culture is done without input of inorganic carbon.
• FIG. 3 shows the assimilation of hydrogen carbonate for an initial composition of calcium, CO 3 2 " , HC0 3 " representative of that of seawater.
• FIG. 5 shows the evolution of carbonate and hydrogen carbonate concentrations as a function of the carbon synthesized in the biomass (comparison between the experimental values and the theoretical values of hydrogen carbonate and carbonate concentrations).
• FIG. 6 shows the evolution of the C02 consumptions as a function of the carbon synthesized in the biomass (comparison between the experimental values and the theoretical values of C02 injected).
• FIG. 7 represents the data of tests A and B.
• FIG. 8 illustrates a device for producing biomass and calcite integrated in an energy recovery process.
• the process according to the invention is an integrated process for the biological capture of CO2 using cyanobacteria comprising the following steps:
• the pH of the culture is regulated by controlled injection of C0 2 according to the production of biomass and precipitation events.
• Figure 1 shows the evolution of the main parameters (pH, concentration of biomass, calcium, C0 3 2 " and HCO 3 " ) during the assimilation of hydrogen carbonate by a culture of cyanobacteria, in a culture in batch, that is to say in a closed environment, that is to say without additional inorganic carbon, and in the absence of calcium.
• An assimilation of the hydrogencarbonate with a production of biomass and carbonate is observed.
• the pH profile reflects an alkalization of the medium through the carbonate system revolution (decrease of the concentration of the hydrogencarbonate and increase of the carbonate concentration).
• the pH profile also highlights day and night phase alternations, with photosynthesis activity during the day phase and a breathing phase during the night phase.
• An assessment shows that for two hydrogenocarbonate ions consumed, a carbon from the hydrogencarbonate is distributed in the biomass and another carbon from the hydrogencarbonate is converted into carbonate.
• Figures 2a and 2b show the evolution of these same parameters when the assimilation of the hydrogencarbonate is conducted in the presence of calcium.
• the carbon and calcium balances at the end of the total consumption of the hydrogencarbonate show that the calcium is completely engaged in calcium carbonate.
• the carbonate produced by the photosynthetic assimilation of the totality of the hydrogencarbonate represents half of the carbon resulting from the hydrogen carbonate and is distributed between the carbonate ion and the calcium carbonate. Residual carbonate remains.
• a source of hydrogen carbonate that can be used in large quantities is seawater.
• the hydrogencarbonate ion is preponderant compared to the dissolved CO 2 .
• the calcium concentration of seawater is 10.3 mM and is therefore much higher than that of the two carbonate species, the hydrogencarbonate ion (of the order of 5.6 times) and the carbonate ion (of the order of 38 times).
• cyanobacteria with a carbonate system behaves like a culture of cyanobacteria in batch culture on hydrogencarbonate, without additional inorganic carbon input (results shown in Figures 1 to 3). Under these conditions the growth of medium with a carbonate system will result in an imbalance of the carbonate system (alkalization) generated by modification of the hydrogen carbonate / carbonate ratio.
• Changing the conduct of the culture of cyanobacteria compared to an assimilation of hydrogen carbonate in batch at unregulated pH consists in maintaining this ratio at its initial value, that is to say to maintain the constant pH by injection of C0 2 .
• the pH value reflects a ratio between the concentrations of the two carbonate and hydrogencarbonate species.
• the instantaneous biological demand (mineral carbon demand for growth) that varies with the increase in cell concentration in the reactor is ensured by the injection of C0 2 controlled by the pH regulation.
• Optimal culture pHs were determined for optimizing biomass productivity. These optimal pH correspond to the minimum time of doubling of the cyanobacterium biomass. These pHs are between 9 and 10.
• a high (optimum) pH means a carbonate concentration higher than that of the hydrogencarbonate (see carbonate / hydrogen carbonate ratio> 1) and contributes to an increase in the efficiency of the C0 2 capture introduced into the carbonate system.
• Biomass production is accompanied by a demand for other elements such as nitrogen and phosphorus to name only the two most important for biomass.
• the most important element after carbon is nitrogen.
• the addition of nitrogen in the form of nitrate (N0 3 ) contributes to the assimilation of nitrogen within the biomass and to a production of hydroxyl in the medium.
• the nitrogen gas associated with the supply of C0 2 is not used by the cyanobacteria at a rate sufficient to ensure the growth rates required for the process.
• y N / C which represents a constant for a strain of cyanobacteria under well defined culture conditions without limitation of the nitrogen source;
• Figure 5 shows experimental values and calculated values of hydrogen carbonate and carbonate concentrations as a function of the synthesized biomass C.
• Figure 6 shows the experimental values and the calculated values of C0 2 injected as a function of the synthesized biomass C.
• the amount of C0 2 injected will be 113.7 mmol / I of culture medium.
• These 13.7 moles / l of culture medium represent the CO 2 injected (113.7-100) with the carbonate system (and which is distributed between the hydrogencarbonate and the carbonate) as a result of the incorporation of nitrogen into the biomass, as long as the nitrogen supply is in the form of nitrate (N0 3 ⁇ ).
• the nitrogen source is brought in the form of ammonium, it is observed at the level of revolution of the pH a reverse situation with an acidification by H + (1 H + for 1 mole of N incorporated into the biomass).
• the system can not function sustainably for biomass production according to this procedure.
• the respective concentrations of the two species are then very rapidly reduced, and the system is no longer functional.
• This situation is not favorable for optimum process control, and it is preferable to supply the nitrogen in the form of nitrate.
• precipitation of calcium carbonate can not be done in batches when seawater is taken with a composition of 1818 ⁇ l of hydrogencarbonate and 272 ⁇ l of carbonate and 10300 ⁇ l of calcium. without adding inorganic carbon (C0 2 or HC0 3 ' ).
• the occurrence of the first precipitation event requires that the concentration of calcium or that of carbonate (from hydrogencarbonate) be increased.
• the process according to the invention proposes a modification of the conduct of the cyanobacterial culture process for the production of calcium carbonate.
• the process according to the invention uses a culture of cyanobacteria on a carbonated aqueous medium (seawater or fresh water), in the presence of calcium, in which the pH is controlled by CO 2 injection.
• This culture method makes it possible to produce carbonate ions by photosynthesis from hydrogen carbonate ions, in order to obtain both a valuable biomass of cyanobacteria and a precipitation of calcium carbonate (CaCO 3) by reacting the carbonate in the presence of calcium.
• the growth of the cyanobacterial biomass is carried out on the hydrogencarbonate without the pH regulation being operational. Under these conditions the respective concentrations of hydrogen carbonate and carbonate will change (basification by consumption of hydrogen carbonate and production of carbonate). For example, in the case of a control pH of 9.5, with a concentration ratio between the two species of about 1/1, a concentration of about 780 ⁇ is obtained for each of these two species. moment of commissioning of the regulation.
• Biomass production (C biomass) is of the order of 515 ⁇ .
• the mineral carbon consumption for the production of biomass and calcium carbonate is then done by injecting C0 2 .
• the precipitation of CaCO 3 can not take place in the presence of a final concentration of 1118 ⁇ l of carbonate, if a batch hydrogen carbonate is used from seawater.
• the precipitation of CaCO 3 can take place in the carbonate system procedure with a CO 2 injection regulation (process according to the invention). Indeed, when the pH regulation is initiated, the amount of biomass (or concentration) present (about 515 ⁇ of biomass C) increases further during the time when the carbonate concentration drifts from 780 ⁇ to 1100 ⁇ . The increase in the biomass concentration for this value of 1100 ⁇ of carbonate can be calculated by the equations proposed above.
• the pH regulation is restarted again for a concentration of hydrogencarbonate again equal to that of carbonate, namely of the order of 530 ⁇ , taking into account the distribution of carbon ex hydrogen carbonate consumed, distributed between 1C biomass and 1C carbonate.
• the mineral carbon consumption is carried out as soon as the C0 2 injection regulation is reactivated.
• the valorization of the biomass obtained can be direct. Due to its nitrogen content, the cyanobacteria biomass obtained by the process according to the invention can be used directly as a fertilizer.
• the biomass of cyanobacteria is probably not suitable for valorization in the form of methyl esters of fatty acids.
• the recovery of this biomass and its heat treatment by pyrolysis may also make it possible to obtain an oil constituting a raw material for a gasification with a Fischer Tropsch synthesis.
• This thermal recovery can be conducted by direct combustion and heat recovery, or by pyrolysis to generate an oil.
• the oil produced in this case can be used as a raw material for chemical syntheses for example, or valued as a source of thermal energy or in combustion engines, or as a raw material for gasification.
• Methanogenesis can be carried out in any suitable reactor of the anaerobic digester type.
• the anaerobic digester is methanized by injection of biomass during the night phase, when the culture medium has been made anaerobic by the current breathing process.
• Biomass separated from water can be used for thermal energy recovery.
• a known elemental biomass composition in terms of C, O, N, H, S
• C0 2 and methane are partly a function of the wall / membrane composition and the protein content of the microorganism (there is indeed a possibility of inhibition of methanogenesis by high levels of ammonium).
• the production of CH 4 and C0 2 can be estimated by the following formula (which also does not take into account the needs for maintenance energy and anabolism).
• composition of the cyanobacterium biomass obtained in a culture under C0 2 injection at a pH regulated at 9.5, and without limitation of nitrogen is as follows (the elemental composition of the biomass is reported at 100):
• a culture of cyanobacteria on a carbonate system with regulated pH and C0 2 injection is carried out batchwise (closed medium, continuous culture) in a marine environment, in seawater having as starting composition 1818 ⁇ l of hydrogencarbonate, 272 ⁇ l. of carbonate and 10300 ⁇ of calcium.
• the pH is regulated around 9.5 to 10.
• Table 1 C02 consumption, biomass production, CaCO3 production, for each phase of controlled pH control by CO 2 injection. (for a volume of 1 L of marine environment).
• Table 2 Cumulative C02 consumption, cumulative biomass production, CaCO3 production, for each CO2-controlled pH control phase. (for a volume of 1 L of marine environment) The concentrations of hydrogen carbonate and carbonate at the end of each precipitation step are respectively of the order of 1000 ⁇ and 300 ⁇ .
• the process time is about 1 week.
• nitrate preferably calcium nitrate
• the annualized balance sheet for an installation volume of 5000 m 3 , ie one hectare with 50 cm of water of water depth is:
• This speed of consumption of hydrogen carbonate results in a final biomass concentration of 588 mg / L, an OD of 2.8 and a population of the order of 9.4 ⁇ 10 8 .
• the photo limitation can contribute to decrease the progression of the increase of the concentration of biomass towards an asymptote.
• photo limiting tends to limit the maximum concentration of biomass with which one can complete a production cycle (over a week). In a process line, this concentration value must not be exceeded.
• the biomass of cyanobacteria is probably not suitable for valorization in the form of methyl esters of fatty acids.

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