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    • 专利摘要:
    The invention relates to a process for converting algal biomass into a gas or a bio-crude for the production of a fuel or a fuel, in particular a liquid fuel, or other synthetic product, comprising the following steps: hydrothermal gasification or hydrothermal liquefaction of an algal biomass in at least a first reactor, b / separation between respectively the gas or the biocrude product, and the aqueous effluents and the CO2 produced at the outlet of the first reactor, c / recovery of aqueous effluents, d / oxidation of aqueous effluents in at least a second reactor.
    公开号:FR3030562A1
    申请号:FR1463026
    申请日:2014-12-19
    公开日:2016-06-24
    发明作者:Jonathan Texier；Pierre Castelli；Anne Roubaud
    申请人:Commissariat a lEnergie Atomique CEA；Commissariat a lEnergie Atomique et aux Energies Alternatives CEA；
    IPC主号:
    专利说明:

    [0001] TECHNICAL FIELD The present invention relates to an improved method for the thermochemical conversion of algal biomass, advantageously integrated continuously in a culture culture process. The present invention relates to an improved method for thermochemical conversion of algal biomass, advantageously integrated continuously in a culture process. 'algae. The invention aims to improve the conversion of the algal biomass into a gas or bi-crude respectively by hydrothermal gasification or hydrothermal liquefaction for the production of bio-fuels (liquid or gaseous). By "bio-crude" is meant the usual meaning, that is to say a combustible liquid resulting from the direct hydrothermal liquefaction of the algal biomass. By "algal biomass" is meant all photosynthetic microorganisms.
    [0002] By "photosynthetic microorganisms" is meant the usual meaning, as given in the publication [1], namely algae and cyanobacteria, ie eukaryotic or prokaryotic organisms whose growth is carried out mainly by photosynthesis, and of microscopic size, typically between 1 and 100 μm. By "supercritical water" is meant the usual meaning, i.e., water at temperatures above 374 ° C under a pressure greater than 22.1 MPa. STATE OF THE ART In its natural state, photosynthetic micro-organisms (microalgae and cyanobacteria) are unicellular photosynthetic organisms, main components of phytoplankton, which have inhabited the oceans and waterways for more than three and a half billion years. years. Micro-algae and cyanobacteria cultivation on an industrial scale has recently become very popular due to the many fields of application, including, in a decreasing valuation scale, pharmaceuticals and cosmetics, human nutrition, fertilizers, biobased materials, bio-remediation and biofuels (liquid or gaseous). The craze for this dedicated crop stems mainly from the fact that it does not harm food production, and that its yield, that is to say the growth rates of microalgae and cyanobacteria, can be very high. To give an order of magnitude, as advanced by some authors, one hectare of micro-algae culture can theoretically produce between 60 and 300 barrels of oil equivalent per year, compared to 7 barrels with rapeseed. To allow the growth of microalgae or cyanobacteria, a strain must be combined with the appropriate culture medium. The latter consists of water, nutrients, carbon dioxide (CO2) and solar energy. The dosage of these different parameters will result in the rate of multiplication and growth of the algal biomass as well as its composition. Thus, for example a nitrogen deficiency in the culture medium can lead to a lipid accumulation within the cells. The three species of photosynthetic microorganisms currently the most cultivated are, in descending order of quantity, cyanobacteria of the genus Arthrospira, better known under the name of "spirulina", which represents about 50% of the world's production, followed by micro -green algae of the genera Chlorella, Haematococcus, Nannochloropsis and diatoms of the genus Odontella. In general, apart from a few species cultivated for niche markets, the methods of cultivation of photosynthetic micro-organisms have not yet reached their level of industrial maturity. Problems of constancy of quality and their cost of production still arise, which limits their access to many commercial markets. In addition, the production of photosynthetic micro-organisms requires light as well as heat during cold periods. However, in order not to limit it to hot, sunny regions, the technical solutions chosen should make it possible to increase the productivity of micro-algae in countries located at the latitudes of temperate regions.
    [0003] Systems for the monocrop production of photosynthetic micro-organisms suspended in water are numerous. Two major families of culture systems [1] photosynthetic microorganisms (algal biomass), are distinguished in particular: - the architecture systems of open type, which are constituted by 30 basins, where appropriate loop also known under the denomination "Raceway", lagoons, open containers, that is to say in the open air. They have the main advantage of generating relatively low production costs. Their major drawbacks lie in a low volume productivity, that is to say the sizes of equipment required which are important for a given biomass production, and a poor control of the culture conditions (sensitivity to contamination, in particular). closed-type architecture systems, known as "photo-bioreactors", constituted by one or more enclosures, that is to say the interior of which is not in contact with the air ambient. Although requiring a significant initial investment, photo-bioreactors allow compared to open ones, to achieve better productivities and achieve crops under better controlled conditions, especially avoiding contaminations, pollution, and losses of CO2. Hydrothermal liquefaction is a promising conversion process for transforming algal biomass into so-called 3rd generation biofuels. It is a process operating in subcritical water, that is under conditions of temperature and pressure below 374 ° C and 22.1 MPa, in which water plays a role at a time. of reaction medium and reagent. At first approach, this process makes it possible to transform an algal biomass, still in solution in its culture medium, into a bio-crude, much closer to a liquid fuel. However, a major disadvantage of this hydrothermal liquefaction conversion process is the production of an aqueous effluent during the reaction. The latter contains the nutrients necessary for the growth of algae, but also carbon compounds, some of which are toxic to algae. Thus, at the laboratory scale, many people have already demonstrated the feasibility of a conversion of algal biomass by hydrothermal liquefaction. In particular, the Applicant has already shown that hydrothermal liquefaction is a feasible method for the conversion of a multitude of algae (Nannochloropsis, Chlorella, Neochloris, Spirulina, Chlamydomonas, Dunaliella, etc.) still in their culture medium, in a bio-crude fuel. The publication [2] highlights the study of different temperatures and dwell times of the algal biomass in a reactor for the implementation of hydrothermal liquefaction. This publication [2] shows that short residence times, typically 1 to 5 minutes, are sufficient to obtain high conversion rates of biocrude, up to 66%, and values of higher heating value (PCS) up to 36 MJ / kg. In this publication [2], the recycling of effluents at the end of the process is not considered. The publication [3] focuses on the hydrothermal liquefaction of aqueous wastes, and an algal biomass. In this publication [3], it is envisaged recycling nutrients and carbon from the algae culture medium: the recycling scheme envisaged is shown in Figure 1 of the publication. In this publication [3], however, the residue of the hydrothermal liquefaction is not reprocessed and is used directly to cultivate algae, which can be harmful and not optimal for the culture, because certain compounds derived from hydrothermal liquefaction are toxic.
    [0004] More generally, the various teams working on hydrothermal liquefaction publish similar and very encouraging results, in terms of conversion rate in bio-crude, and calorific value of the bio-crude obtained. In other words, the feasibility of transforming algal biomass, or even agro-food waste, into bio-crude is now proven, and the level of performance achievable by a continuous hydrothermal liquefaction process is apprehended. The patent application US 2012/0055077 proposes an improvement of the process of hydrothermal liquefaction of a biomass by a post-treatment of the bio-crude at the outlet of hydrothermal liquefaction to improve its biofuel properties.
    [0005] This patent application does not concern the reprocessing of the aqueous phase resulting from liquefaction. The patent application WO 2011/049572 aims to propose a method of hydrothermal liquefaction of a waste, and to recover the CO2 obtained for the cultivation of algae, the algal biomass thus obtained being in turn converted by hydrothermal liquefaction. In the disclosed process, the aqueous phase at the outlet of hydrothermal liquefaction is only minimally valorized. Indeed, it is simply reinjected directly into the algae culture medium, which can be toxic to algae and not optimal for their growth. The patent application US 2012/0285077 proposes a biological type extraction of lipids contained in algae to obtain a bio-oil, then converted into biodiesel by carrying out a transesterification reaction. The process disclosed in this application contemplates the recycling of residues by fermentation to form CO2 which is then reinjected into an algae culture reactor. Thus, although many teams are working on the development of the process of conversion of algal biomass into bio-crude by hydrothermal liquefaction, and that this process involves the large production of aqueous effluents during the reaction, no solution has actually been proposed to make the best use of these aqueous effluents. There is a need to improve the thermochemical conversion processes of algal biomass into gas or bio-crude for the production of bio-fuels (liquid or gaseous), in particular with a view to making the best use of the aqueous effluents produced during these processes. More generally, there is a need to improve continuous processes that incorporate a thermochemical conversion process of algal biomass into gas or bio-crude downstream of an algal biomass culture process. The general object of the invention is to meet at least part of this need (s). SUMMARY OF THE INVENTION To this end, the invention first of all relates, in one aspect, to a process for converting the algal biomass into a gas or a bio-crude in order to produce a fuel or a fuel , in particular a liquid fuel, or another synthetic product, comprising the following steps: a / hydrothermal gasification or hydrothermal liquefaction of an algal biomass in at least a first reactor, b / separation between respectively the gas or the biocrude product , and the aqueous effluents and the CO2 produced, at the outlet of the first reactor, c / recovery of aqueous effluents, d / oxidation of aqueous effluents in at least a second reactor. Thus, the invention makes it possible firstly to produce gas or biocrude and to efficiently transform the harmful aqueous effluents in order to recycle them. The aqueous effluents thus transformed no longer constitute waste.
    [0006] More precisely, at the outlet of the first reactor, it is possible to recover a gas or bio-crude that can be used directly to produce liquid fuels, and at the outlet of the second reactor, it can be recovered and recovered from water and nutrients, as well as the CO2 produced during gasification or hydrothermal liquefaction. The invention also relates, in another of its aspects, to a continuous process for cultivating algal biomass and for converting the algal biomass grown into a gas or a bio-crude, comprising the following steps: a culture zone containing a culture medium the algal biomass to be cultivated, - harvesting of the cultivated algal biomass, - steps a / to d / of the conversion method described above, - injection of water and nutrients, and the case CO2, obtained at the outlet of the second reactor, in the culture zone. According to an advantageous embodiment, the continuous process further comprises the step of recovering the oxygen (02) produced by the algal biomass for injecting it, as an oxidant, upstream of the second reactor before the d / 1 step of oxidation. Thus, the invention proposes to integrate a recycling of effluents produced, within the process itself, through the establishment of two reactors, one dedicated gasification or hydrothermal liquefaction for the recovery of algal biomass. in fuel and the other dedicated to the oxidation of aqueous effluents to allow their recycling in the culture medium of the algal biomass. When the two reactors are thermally coupled, the energy released by the exothermic oxidation reaction can be maximized by providing it as a heat source to the endothermic gasification or hydrothermal liquefaction reaction. Thus, the advantages provided by the invention are numerous among which: - a saving on the reprocessing of CO2 and aqueous effluents at the output of the conversion process of the algal biomass gas or bio-crude, these aqueous effluents constituting more waste that must be reprocessed as according to the state of the art. the recovery of a non-toxic culture medium (water and nutrients leaving the oxidation reactor) for the cultivation of the algal biomass, and thus a production economy to cultivate it, a supply of energy for the endothermic reaction of hydrothermal liquefaction by the exothermic oxidation reaction. Step d / may be wet oxidation or hydrothermal oxidation (OHT) under supercritical conditions.
    [0007] When step a / is a liquefaction, it is preferably carried out in the temperature range of between 150 and 374 ° C and / or pressures between 0.5 and 35 MPa. When step a / is a gasification, it is preferably carried out in a temperature range between 374 and 800 ° C and / or pressures between 22.1 and 35 MPa. Preferably, step a / is carried out in a range of residence times of between 15 seconds and 1 hour. When step d is a wet oxidation carried out in a temperature range between 150 and 374 ° C and / or pressures between 0.5 and 15 MPa. When step d / is a hydrothermal oxidation carried out in a temperature range between 374 and 800 ° C and / or pressures between 22.1 and 35 MPa. Step d is preferably carried out in a residence time range in the second reactor between 15 seconds and 1 hour. According to an advantageous variant, step d is a wet oxidation carried out with a portion of the biocrude product injected into the second reactor. The produced and separated CO2 can be injected as a solvent into the produced biocrude. According to an advantageous variant, the heat produced during the d / oxidation step in the second reactor can be brought into the first reactor for the implementation of step a / liquefaction or hydrothermal gasification. The heat produced during the d / oxidation step in the second reactor can also be made to preheat the oxidizing gas. According to an advantageous embodiment, the a / hydrothermal liquefaction step and the d / oxidation step are carried out within the same reactor, said jacketed, comprising an inner envelope internally delimiting the chamber of the first reactor, and an outer casing surrounding the inner casing, the space between the inner casing and the outer casing defining the chamber of the second reactor. Advantageously, step a / of liquefaction or hydrothermal gasification is carried out in several first reactors in fluidic parallel. Advantageously, the d / oxidation step is performed in several second reactors in fluidic parallel. The invention also relates to a continuous process for cultivating algal biomass and for converting algal biomass grown in a gas or a biocredit, comprising the following steps: cultivation of the algal biomass in a zone containing a culture medium - harvesting cultured algal biomass, - steps a / to d / of the conversion process previously, - injection of water and nutrients, and if appropriate CO2, obtained at the outlet of the second reactor, in the growing area. The method may further comprise the step of recovering the oxygen (02) produced by the algal biomass for injecting it, as an oxidant, upstream of the second reactor before the d / oxidation step. The invention also relates to the use of the conversion method described above or the continuous process described above for the production of liquid fuels, called 3rd generation fuels. DETAILED DESCRIPTION Other advantages and characteristics of the invention will emerge more clearly from a reading of the detailed description of the invention given by way of illustration and without limitation with reference to the following figures, in which: FIG. 1 is a diagrammatic view of an example of a system implementing the continuous process for cultivating algal biomass and for converting the algal biomass cultivated by hydrothermal liquefaction into a bio-crude according to the invention; FIG. 2 is a schematic perspective view of an advantageous embodiment of a part of the system according to the invention with a jacketed reactor; FIG. 3 is a schematic view of an example of a system implementing a continuous process for cultivating algal biomass and for converting algal biomass cultivated by hydrothermal liquefaction into a bio-crude according to the state of the art; FIG. 4 is a schematic view of an exemplary system implementing a continuous process according to the invention and directly applied to the system according to FIG. 3; FIG. 5 is a graph indicating the preferred ranges of temperature and pressure for carrying out step a / hydrothermal liquefaction in the process according to the invention.
    [0008] In the description which follows the terms "entry", "exit" "upstream", "downstream", are used by reference with the direction of circulation of the products obtained within the system implementing the continuous process according to the invention. . The mention X%. ' that means a percentage X by mass of a compound. FIG. 1 diagrammatically shows a first example of a system implementing the continuous process for the culture of photosynthetic micro-organisms and their conversion by hydrothermal liquefaction according to the present invention. The system comprises firstly an algal biomass culture zone 1. This growing area is either open pit, with one or more basins, or closed type, with one or more photo-bioreactors (PBR). The open pit may be loop type (s), as commonly called "raceway". For the cultivation of microalgae and cyanobacteria species below, the following preferential temperature ranges can be envisaged: - Arthrospira platensis: 25 - 35 ° C (optimum temperature = 30 ° C), - Chlorella pyrenoidosa: 35 - 45 ° C (optimum temperature = 38.7 ° C), - Chlorella vulgaris: 25 - 35 ° C (optimum temperature = 30 ° C), - Chlamydomonas reinhardtii: 15 - 30 ° C (optimum temperature = 25 ° C), - PhaeodacClum tricornutum: 20 - 25 ° C (optimal temperature = 22.5 ° C), - Porphyridium cruentum: 15 - 30 ° C (optimum temperature = 19.1 ° C), - Scenedesmus sp. : 20 - 33 ° C (optimum temperature = 26.3 ° C), - Nannochloropsis oceanica: 20 - 33 ° C (optimal temperature = 26.7 ° C), - Dunaliella tertiolecta: 30 - 39 ° C (optimal temperature = 32.6 ° C). The algal biomass obtained by the culture is then harvested. Different techniques can be used for harvesting, such as flocculation, filtration, centrifugation.
    [0009] The subsequent hydrothermal liquefaction step has the advantage of operating with a high moisture content, up to 80% water or more. Unlike other conversion technologies, this simplifies the harvesting and drying stages. The harvested biomass can be sent, in particular by means of a suction pump 10 to a reactor 2 for transforming the algal biomass into a bio-crude (oily phase) by hydrothermal liquefaction. In addition to the bio-crude output from the reactor 2, an aqueous phase is formed, containing organic residues and nutrients in the culture medium, and a gaseous phase containing, for the most part, CO2. In other words, the hydrothermal liquefaction reaction, which is endothermic, allows the transformation of an algal solution, partially concentrated in its culture medium, into biocrystals of interest, into an aqueous effluent, and into CO2. The resulting bio-crude can then undergo a post-treatment, hydro-liquefaction, for example, to be transformed into bio-diesel biofuel. According to the invention, at the reactor outlet 2, a separation between the aqueous effluents, the CO2, and the bio-crude is carried out by means of a suitable device 3, which may be usual. Then, the aqueous effluents, preferably with CO2, are sent by a return line to the inlet of a reactor 5 in which a wet oxidation reaction will take place.
    [0010] The oxidation reaction, which is an exothermic reaction, makes it possible to transform the aqueous effluents, obtained with the liquefaction reaction in reactor 1, into water containing the nutrients present in the initial algal solution, and into CO2. To take place, this reaction requires an oxidant, which can be air, oxygen, or other. In order for the wet oxidation reaction to be energetically viable, it is preferable that the phase separation at the liquefaction outlet takes place without cooling or depressurizing the mixture.
    [0011] Then, at the outlet of the reactor, a mixture of nutrients with water and optionally CO2 is obtained, which can be injected via line 6 into the culture zone 1. This mixture is therefore recyclable in the algae culture. Thus, according to the invention, the treatment of aqueous effluents at the outlet of hydrothermal liquefaction is achieved by oxidation, for the culture of new algae. The described invention also makes it possible to optimize the energy. Indeed, the liquefaction reaction requires heating the algal solution and is endothermic, while the oxidation reaction, for its part, is exothermic.
    [0012] Thus, as shown diagrammatically in FIG. 1, the heat resulting from the exothermic wet oxidation reaction which takes place in reactor 5 is supplied to reactor 2 in order to carry out or participate in hydrothermal liquefaction. Thus, to combine these two reactions, it is advantageous to use a so-called jacketed reactor 7 as illustrated in FIG. 2. In this reactor 7, the inner envelope delimits the reactor chamber 2 in which the hydrothermal liquefaction reaction takes place. and the space between the inner and outer shells delineates the reactor chamber in which the wet oxidation reaction (or vice versa) takes place. The structure and operation of such a jacketed reactor 7 is now explained. The reactor 7 is tubular and its length makes it possible to have a sufficient contact surface between the two reaction zones, and thus to improve heat exchange. In addition, a reduced diameter, allows to minimize the thickness necessary to contain the internal pressure. The outer shell must withstand mechanical stresses: pressure and temperature, and chemical stresses related to the oxidation of organic matter and ions derived from mineral salts. Typically, the outer shell of the reactor 7 may be 316L steel or Inconel 625e. If necessary, to improve the chemical resistance of the reactor, a titanium liner may be considered. The inner casing is used in equi-pressure between the two reaction zones, so it does not have to withstand the pressure. However, it must withstand the thermal stresses, ensure good thermal conductivity, and withstand the chemical constraints of the two reactions, ie both liquefaction in the chamber 2 and the oxidation in the chamber 5. Typically, it can be considered a internal titanium casing, which can withstand chemical and thermal stresses, but has a reduced thermal conductivity. 316L steel or Inconel 625® can also be used.
    [0013] Instead of using a jacketed reactor 7, it is also possible to use other heat exchanger systems (tube, beam, spiral exchangers, etc.) or to enhance the energy produced by the oxidation reaction otherwise. FIG. 3 shows a system implementing a process in continuous conversion of algal biomass culture and conversion of the algal biomass cultivated by hydrothermal liquefaction into a bio-crude according to the state of the art. In such a system, the aqueous effluents and CO2 produced are troublesome waste. To overcome this drawback, the inventors have thus proposed the process already described above with optimized recycling: by the oxidation of the aqueous effluents recovered at the outlet of the separation device 3, and then, by the injection of a flow composed of water, CO2 and nutrients produced by the oxidation in the culture zone 1. To carry out the wet oxidation reaction, it is necessary to add an oxidant to the mixture. The latter may be air, oxygen, hydrogen peroxide or the like. Advantageously, it is possible to recover the product produced during the growth of the algae in the culture zone in order to inject it before the wet oxidation stage, that is to say at the inlet of the reactor 5. symbolized in FIG. 4. Thus, thanks to the invention, the co-products of the hydrothermal liquefaction reaction which are troublesome in the system according to the state of the art are valorized within the culture process of the algal biomass. With the additional oxidation step according to the invention, the energy efficiency of the hydrothermal liquefaction process is increased, and the reprocessing and recovery of troublesome effluents at the process outlet become possible.
    [0014] The parameters and preferred conditions for carrying out the different steps of the method according to the invention are specified below.
    [0015] Hydrothermal liquefaction stage i. Input products At reactor inlet 2, various types of algae (Nannochloropsis, Chlorella, Neochloris, Spirulina, Chlamydomonas, Dunaliella, etc.) can be injected, more or less concentrated in their culture medium. In order to carry out a liquefaction test, the algal solution advantageously has a concentration of between 10% by mass and 40% by mass of dry matter (organic and inorganic matter), given that the elemental chemical composition of the dry matter is included in the ranges of the following values: 20 to 70% by weight of carbon 5 to 40% by mass of oxygen 5 to 10% by mass of hydrogen 5 to 10% by mass of nitrogen 3 to 50% by mass of inorganic salts (compounds of P K, Cl, Na, S, Mg, Ca, Fe, Al, F, etc.). Subsequently, it is considered an intermediate concentration of 20% by mass of dry matter composed as follows: 55% by mass of carbon; 25% mass than Oxygen; rAmass only with hydrogen, 8% by mass of nitrogen and 5% by mass of salts. This composition (C6.0H9.102.0N0.7) corresponds to a higher heating value (PCS) of the dry matter of about 24.5 MJ / kg. ii. Operating Conditions The reaction temperature is between 200 and 350 ° C. for pressures ranging from 5 to 25 MPa. Typically, for the liquefaction reaction to take place, the temperature and pressure conditions must be in the range of operation in FIG. 5. The pressure / temperature pair must be maintained in such a way that the medium is not in the gas phase. . The residence time under these conditions can be in a range of 1 to 60 minutes.
    [0016] Subsequently, it is considered a test at 290 ° C, and 10 MPa, with a residence time of 5 minutes. It goes without saying that this is only one example among the multitude of possible operating conditions. To treat a kilogram of algal solution, of density equal to 1 in first approximation, it takes about 1000 kJ to heat the water present in the algal solution from 20 to 290 ° C, and about 125 kJ to heat the organic and inorganic matter . This is a first approximation of the ideal energy to provide for heating the reaction medium. Added to this value is the enthalpy of liquefaction reaction. According to the estimates of the publication [4], this can be estimated at 27 kJ under these conditions. The operating conditions can significantly affect the results. Thus the temperature, the pressure, the residence time, the type and the strain of algae, their concentrations, and their culture processes, vary the level of biocrude obtained and its quality, as well as the nature of the aqueous effluent and its concentration of carbon compounds. iii. Output products Under the conditions mentioned above, approximately 7% by mass of bio-crude (with a heating value of around 32 to 38 MJ / kg), 20% of carbon dioxide, supercritical under these temperature conditions, are expected. pressure, and 92% by mass of aqueous effluent. The latter contains 6% -massic organic carbon, or 54.8 g of carbon per liter of treated algal solution. Wet oxidation step When a jacketed reactor 7 is used, this wet oxidation reaction occurs in the space between the inner and outer shells (or conversely within the inner zone). iv. Input Products At the reactor inlet 5, the aqueous effluents resulting from the liquefaction reaction and an oxidant of the air or oxygen type are introduced.
    [0017] The aqueous phase, containing carbon compounds and CO2, thus undergoes wet oxidation under these conditions of temperature and pressure, thanks to the addition of an oxidant. As a first approximation, the 54.8 g of carbon present in the aqueous effluents can release 1800 kJ during oxidation (depending on the elemental composition of the carbon compounds, the value will actually be between 1000 and 1800 kJ). As a first approximation this value is therefore sufficient to provide the necessary energy, as heat to the hydrothermal liquefaction reaction and the heating of the oxidant. there. Operating Conditions The wet oxidation reaction is carried out under the same conditions as the hydrothermal liquefaction, i.e. in a temperature range of 200 to 350 ° C, with a pressure of between 5 and 25 MPa. The addition of oxidant must be in an over-stoichiometric amount (1.5 for example).
    [0018] The required residence time is also in the range of 1 to 60 minutes. For 54.8 g of carbon a theoretical minimum of 146.1 g of oxygen is required to ensure total theoretical oxidation. In reality, an over-stoichiometry is favorable. For example, to obtain an over-stoichiometry of 1.5, 219.2 g of oxygen are required.
    [0019] As the oxygen reaches room temperature, it requires 54.5 kJ to heat it to the reaction temperature. If the oxidant is air, it would add 767.6 g of nitrogen requiring 213.3 kJ to be brought from 20 to 290 ° C. vi. Output Products At the outlet of the oxidation reactor, the flow is composed of a medium that is favorable for the cultivation of algae, containing water, CO2 and the nutrients initially present in the algal solution. These elements can be injected directly into the culture zone. Other variants and improvements may be provided without departing from the scope of the invention.
    [0020] The invention is not limited to the examples which have just been described; it is in particular possible to combine characteristics of the illustrated examples within non-illustrated variants.
    [0021] The expression "having one" shall be understood as being synonymous with "having at least one", unless the opposite is specified.
    [0022] References cited [1]: J. Pruvost et al. "Industrial production of microalgae and cyanobacteria", Engineering Techniques, IN 200, 11/2011; [2]: Julia L. Faeth, et al .: "Fast Hydrothermal Liquefaction of Nannochloropsis sp. To Produce Biocrude, Energy Fuels, 2013, 27 (3), pp 1391-1398; [3]: Yan Zhou, et al .: "A synergistic combination of algal wastewater treatment and hydrothermal biofuel production maximized by nutrient and carbon recycling," Energy & Environmental Sciences, 2013, 6, 3765-3779; [4]: Mariane Audo: "Evaluation of the rheological potential of oils derived from microalgae 10 for applications as bitumen substitution materials" PhD thesis, 2013, University of Nantes, 3MPL doctoral school.
    权利要求:
    Claims (22)
    [0001]
    REVENDICATIONS1. A process for converting algal biomass, that is, all photosynthetic microorganisms into a gas or a bio-crude. for producing a fuel or a fuel, in particular a liquid fuel, or other synthetic product, comprising the following steps: a / gasification or hydrothermal liquefaction of an algal biomass in at least a first reactor (1), b / separation between respectively the gas or the produced biocrude, and the aqueous effluents and the CO2 produced at the outlet of the first reactor, c / recovery of aqueous effluents, d / oxidation of the aqueous effluents in at least a second reactor.
    [0002]
    2. Conversion process according to claim 1, wherein d / is a wet oxidation or a hydrothermal oxidation (OHT) under supercritical conditions.
    [0003]
    3. Conversion process according to claim 1 or 2, step a / being a liquefaction, carried out in a temperature range between 150 and 374 ° C.
    [0004]
    4. Conversion process according to one of claims 1 to 3, step a / being a liquefaction, carried out in a range of pressures between 0.5 and 35 MPa.
    [0005]
    5. Conversion process according to claim 1 or 2, the step a / being a gasification, carried out in a temperature range between 374 and 800 ° C.
    [0006]
    6. Conversion process according to one of claims 1 or 2 and 5, the step a / being a gasification, carried out in a range of pressures between 22.1 and 35 MPa.
    [0007]
    7. Conversion method according to one of the preceding claims, the step a / being carried out in a range of residence time between 15 seconds and 1 hour.
    [0008]
    8. Conversion process according to one of the preceding claims, wherein d / is a wet oxidation carried out in a temperature range of between 150 and 374 ° C.
    [0009]
    9. Conversion process according to one of the preceding claims, wherein d / is a wet oxidation carried out in a range of pressures between 0.5 and 35 MPa.
    [0010]
    10. Conversion process according to one of claims 1 to 7, the step d / being a hydrothermal oxidation carried out in a temperature range between 374 and 800 ° C.
    [0011]
    11. Conversion process according to one of claims 1 to 7 and 10, the step d / being a hydrothermal oxidation carried out in a range of pressures between 22.1 and 35 MPa.
    [0012]
    12. Conversion process according to one of the preceding claims, the step d / being carried out in a range of residence times in the second reactor between 15 seconds and 1 hour.
    [0013]
    13. Conversion process according to one of the preceding claims, wherein d / is a wet oxidation carried out with a portion of the biocrude product injected into the second reactor.
    [0014]
    14. Conversion process according to one of the preceding claims, the produced and separated CO2 being injected as a solvent in the produced biocrude.
    [0015]
    15. Conversion process according to one of the preceding claims, the heat produced during the d / oxidation step in the second reactor being provided in the first reactor for the implementation of step a / liquefaction or hydrothermal gasification.
    [0016]
    16. Conversion process according to one of the preceding claims, the heat produced during the d / oxidation step in the second reactor being provided to preheat the oxidizing gas.
    [0017]
    17. Conversion process according to one of the preceding claims, the step a / of hydrothermal liquefaction and the d / oxidation step being performed within a single reactor, said double jacket, comprising an inner envelope delimiting internally the chamber of the first reactor, and an outer envelope surrounding the inner casing, the space between the inner casing and the outer casing defining the chamber of the second reactor.
    [0018]
    18. Conversion process according to one of the preceding claims, the step a / of liquefaction or hydrothermal gasification being carried out in several first reactors in fluidic parallel.
    [0019]
    19. Conversion process according to one of the preceding claims, the d / oxidation step being performed in several second reactors in fluidic parallel.
    [0020]
    20. A continuous process for cultivating algal biomass and for converting the cultured algal biomass into a gas or a bio-crude, comprising the following steps: - cultivation of the algal biomass in a zone containing a culture medium - harvesting of the cultivated algal biomass, - steps a / to d / of the conversion process according to one of the preceding claims, - injection of water and nutrients, and optionally CO2, obtained at the outlet of the second reactor, in the culture area.
    [0021]
    21. The continuous process according to claim 20, further comprising the step of recovering the oxygen (02) produced by the algal biomass for injecting it, as an oxidant, upstream of the second reactor before the step. d / oxidation.
    [0022]
    22. Use of the conversion process according to one of claims 1 to 19 or the continuous process according to one of claims 20 to 21 for the production of liquid fuels, called 3rd generation fuels.
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    同族专利:
    公开号 | 公开日
    EP3234070A1|2017-10-25|
    US20170342327A1|2017-11-30|
    WO2016097414A1|2016-06-23|
    ES2828398T3|2021-05-26|
    US10711201B2|2020-07-14|
    DK3234070T3|2020-11-02|
    EP3234070B1|2020-08-12|
    FR3030562B1|2018-08-24|
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    法律状态:
    2015-12-29| PLFP| Fee payment|Year of fee payment: 2 |
    2016-06-24| PLSC| Publication of the preliminary search report|Effective date: 20160624 |
    2016-12-30| PLFP| Fee payment|Year of fee payment: 3 |
    2017-12-29| PLFP| Fee payment|Year of fee payment: 4 |
    2019-12-31| PLFP| Fee payment|Year of fee payment: 6 |
    2020-12-28| PLFP| Fee payment|Year of fee payment: 7 |
    2021-12-31| PLFP| Fee payment|Year of fee payment: 8 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1463026|2014-12-19|
    FR1463026A|FR3030562B1|2014-12-19|2014-12-19|IMPROVED PROCESS FOR CONVERTING BIOMASS ALGALE TO A GAS OR BIO-CRUDE RESPECTIVELY BY GASIFICATION OR HYDROTHERMAL LIQUEFACTION|FR1463026A| FR3030562B1|2014-12-19|2014-12-19|IMPROVED PROCESS FOR CONVERTING BIOMASS ALGALE TO A GAS OR BIO-CRUDE RESPECTIVELY BY GASIFICATION OR HYDROTHERMAL LIQUEFACTION|
    PCT/EP2015/080854| WO2016097414A1|2014-12-19|2015-12-21|Improved method for converting algal biomass into a gas or into biocrude by hydrothermal gasification and hydrothermal liquefaction, respectively|
    EP15820516.1A| EP3234070B1|2014-12-19|2015-12-21|Improved conversion process of algae biomass in gas or bio-crude respectively by hydrothermal gasification or liquefaction|
    US15/537,329| US10711201B2|2014-12-19|2015-12-21|Method for converting algal biomass into a gas or into biocrude by hydrothermal gasification or hydrothermal liquefaction, respectively|
    ES15820516T| ES2828398T3|2014-12-19|2015-12-21|Improved procedure for converting algal biomass into a gas or biocrude respectively by gasification or hydrothermal liquefaction|
    DK15820516.1T| DK3234070T3|2014-12-19|2015-12-21|IMPROVED PROCEDURE FOR TRANSFORMING ALGEBIOMASS TO A GAS OR TO BIO RAW, RES. BY HYDROTHERMIC GASIFICATION OR LIQUID|
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