Classifications

• • 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
  • C12M1/00—Apparatus for enzymology or microbiology
• • 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; 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
• • 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
  • C12P1/00—Preparation of compounds or compositions, not provided for in groups C12P3/00 - C12P39/00, by using microorganisms or enzymes

Definitions

• the present invention relates to a system and method for extracting valuable materials from biomass raw materials, which extracts valuable materials contained in biomass.
• Biomass such as microorganisms
• Biomass is attracting attention as a way to solve global resource issues, such as energy and food shortages, and environmental problems, such as increasing CO2 emissions, and to realize a sustainable world.
• the energy efficiency of microbial production is extremely high compared to other plants and animals.
• Important issues facing these microorganisms include not only the technology to cultivate them, but also the technology to efficiently and cost-effectively extract valuable components from the various components contained in the cultured microorganisms.
• each component contained in a microorganism it is generally necessary to first concentrate the culture solution containing the microorganism, and then remove the water content from the concentrated solution using a drying method such as a dryer or sun exposure to produce dried algae.
• the dried algae cells are then mixed with an extraction solvent, and the target components are transferred to the extraction solvent.
• the algae cells are then separated from the extraction solvent by filtration or other methods, and the extraction solvent is removed from the filtrate by vacuum distillation, drying, or other methods to obtain the target components.
• conventional methods for extracting hydrocarbons from microorganisms include freeze-drying or heating wet algal cells extracted from a microbial culture solution by filtration or the like, and then immersing the dried algal cells in a solvent such as n-hexane or methanol-chloroform (1:1) to extract hydrocarbons (Phytochemistry, vol. 19, pp. 1081-1085, 1980) (see, for example, Patent Document 1).
• Patent Document 1 proposes a problem that drying the concentrated liquid requires a large amount of energy and time, which leads to an increase in production costs and a decrease in production efficiency.
• the solvent cannot effectively contact the raw material due to the remaining moisture in the raw material, resulting in poor extraction efficiency.
• the present invention provides a system and method for extracting valuable materials from biomass raw materials, which can efficiently and at low cost extract various components contained in biomass, such as microorganisms.
• a system for extracting valuable materials from biomass feedstock includes: a culture device for culturing microorganisms; a concentration device for concentrating the cultured microorganisms; a solubilization treatment device that performs hydrothermal solubilization treatment on the concentrated microorganisms; a filtration device that filters the solubilization treatment liquid from the solubilization treatment device; a drying device for drying the microbial filtrate from the filtration device to produce a dried microbial product; an extraction device for extracting valuable components in the dried microbial product into an extraction solvent;
• the present invention is characterized by comprising:
• Another embodiment of a method for extracting valuable materials from biomass raw materials includes: a microbial culturing step of culturing microorganisms; A concentration step of concentrating the cultured microorganism; a solubilization treatment step of subjecting the concentrated microorganisms to hydrothermal solubilization treatment; a filtration step of filtering the solubilization solution from the solubilization step; a drying step of drying the microbial filtrate from the filtration device to obtain a dried microbial product; An extraction step of extracting valuable components in the dried microbial product into an extraction solvent;
• the present invention is characterized by having the following.
• the extraction rate is improved compared to that obtained by drying undamaged culture medium.
• FIG. 1 is a schematic diagram of a system for extracting valuable materials from biomass feedstock according to an embodiment of the present invention.
• FIG. 1 is a schematic diagram of a system for extracting valuable materials from biomass feedstock according to another embodiment of the present invention.
• FIG. 1 is a schematic process diagram of a method for extracting valuable materials from biomass raw materials according to an embodiment of the present invention.
• FIG. 1 is a schematic process diagram of another method for extracting valuable materials from biomass raw materials according to an embodiment of the present invention.
• FIG. 1 is a schematic diagram showing a state in which cells in a culture medium are damaged and soluble substances (DS) are increased.
• FIG. 1 is a process schematic diagram using an apparatus for extracting valuable materials from biomass raw materials according to an embodiment of the present invention. Schematic diagrams of the state of cells before and after rupture and after hydrothermal treatment.
• Figure 1A is a schematic diagram of a system for extracting valuable materials from biomass feedstocks according to an embodiment of the present invention.
• Figure 1B is a schematic diagram of a system for extracting valuable materials from biomass feedstocks according to another embodiment of the present invention.
• Figure 2A is a schematic process diagram of a method for extracting valuable materials from biomass feedstocks according to an embodiment.
• Figure 2B is a schematic process diagram of a method for extracting valuable materials from biomass feedstocks according to another embodiment.
• a system 200A for extracting valuable materials from biomass feedstock includes a culture device (hereinafter also referred to as the "culture device") 301 for culturing microorganisms 201, a concentration device 302 for concentrating the cultured microorganisms 201, a solubilization treatment device 303 for hydrothermal solubilization of the concentrated microorganisms 201A, a filtration device 304 for filtering the solubilization treatment liquid 211 from the solubilization treatment device 303, a drying device 305 for drying the microbial filtrate 201B from the filtration device 304 to obtain a dried microbial material 201C, and an extraction device 306 for extracting valuable material components from the dried microbial material 201C into an extraction solvent 215 to obtain a valuable material solution 201D.
• a culture device hereinafter also referred to as the "culture device”
• concentration device 302 for concentrating the cultured microorganisms 201
• a system 200B for extracting valuable materials from biomass feedstocks may be configured as 200A shown in FIG. 1A, further comprising a valuable material recovery device 307 that recovers valuable materials (e.g., lipids) 214 from the valuable material solution 201D obtained from the extraction device 306.
• valuable materials e.g., lipids
• microorganisms include microalgae, bacteria, animal cells, fungi (yeast, mold), and the like. Specific examples of such microorganisms include Chlamydomonas, Nannochloropsis, Botryococcus, Scutellaria baicalensis, and Lipomyces, but the present invention is not limited to these.
• the valuable lipids produced by these microorganisms are compounds that are insoluble in water but soluble in organic solvents. These include fatty acids, neutral fats, triacylglycerols (TAGs), phospholipids, glycolipids, and sterols. In addition to lipids, proteins, sugars, and other valuable substances are also listed.
• the extraction systems 200A and 200B may each have independent components, or may share multiple components.
• a biomass treatment device 204 may be used that performs the functions of a solubilized product filtration device 304 that filters the solubilized product (solubilized solution 211) from the solubilization treatment device 202, a drying device 305 that dries the filtered product (wet cake) 201B obtained by the filtration device 304, and an extraction device 306 that extracts valuable resources 214 from the dried product (dry cake) 201C obtained by the drying device 305 into a solvent (details will be described later).
• a solubilized product filtration device 304 that filters the solubilized product (solubilized solution 211) from the solubilization treatment device 202
• a drying device 305 that dries the filtered product (wet cake) 201B obtained by the filtration device 304
• an extraction device 306 that extracts valuable resources 214 from the dried product (dry cake) 201C obtained by the drying device 305 into a solvent (details will be described later).
• the method for extracting valuable resources from biomass raw materials of the embodiment includes a microbial culture step (S-11) for culturing microorganisms 201, a concentration step (S-12) for concentrating the cultured microorganisms 201, a solubilization treatment step (S-13) for hydrothermal solubilization of the concentrated microorganisms 201A, a filtration step (S-14) for filtering the solubilization treatment liquid 211 from the solubilization treatment step (S-13), a drying step (S-15) for drying the microbial filtrate 201B from the filtration step (S-14) to obtain a microbial dried product 201C, and a valuable component extraction step (S-16) for extracting valuable components from the microbial dried product 201C into an extraction solvent 215 to obtain a valuable resource solution 201D.
• the method may include a valuable resource recovery step (S-17) in which valuable resources (lipids) 214 are recovered from the valuable resource solution 201D obtained in the extraction step (S-16).
• S-17 valuable resource recovery step in which valuable resources (lipids) 214 are recovered from the valuable resource solution 201D obtained in the extraction step (S-16).
• the solubilization treatment device 303 is also called a hydrothermal solubilization treatment device or a soft hydrothermal treatment device (details will be described later).
• the culture device 301 is a device for culturing microorganisms, and can be either a "closed culture device” that cultivates in a sealed container (space), or an “open culture device” that cultivates large quantities of microorganisms in an outdoor aquarium (pool).
• sealed container culture devices include, but are not limited to, closed photobioreactors made of glass or resin.
• the concentrator 302 is not particularly limited as long as it is a device for concentrating the culture solution cultivated in the culture device 301, and examples thereof include, but are not limited to, a centrifugal separator or a membrane separator (hollow fiber membrane separator, ceramic membrane separator).
• cells in the culture fluid may be destroyed, ruptured, or damaged (hereinafter, collectively referred to as "damaged” in this embodiment) during the concentration step (S-12). If the dried material is dried in such a damaged state, the rate of lipid extraction from the dried material will decrease. However, surprisingly, even in the damaged state, the lipid extraction rate was improved by performing hydrothermal treatment in the solubilization treatment device 303 compared to the undamaged state.
• Damage to cells in the culture medium is not limited to damage caused by the concentrator.
• Microbial cells are damaged in the following cases: 1) Damage when the culture medium is transported using a transport means such as a pump. 2) Damage when compacted during centrifugation using a centrifuge. This is because the culture medium may be damaged by pressure even while being centrifuged. 3) Damage caused by turbulence when the culture medium is poured into the centrifuge. 4) In cases other than centrifugation, damage caused by pressure during membrane concentration when the culture medium is separated by membrane. This is caused by damage caused by pressure when concentrating microorganisms on the membrane (filter).
• Cross-flow filtration is less likely to clog, and is therefore often used for concentration.
• the concentration operation is carried out while the raw liquid is circulating.
• Damage due to storage conditions after culturing microorganisms This is due to damage caused by environmental changes such as temperature during storage. In other words, the cells are damaged by temperature changes, resulting in damage.
• the temperature may exceed 30° C. Such a temperature rise can damage and kill cells, resulting in cell injury.
• damage refers to a state in which the structure of the substance that covers the cell contents, such as the cell membrane or cell wall, has changed, making the contents more likely to escape than when the cell is alive. This also includes a state in which the substance that covers the cell contents has disappeared and the contents are completely exposed.
• Fig. 3 is a schematic diagram showing a state in which cells in a culture medium are damaged and soluble substances (DS) increase, where the left side (Fig. 3(A)) is a schematic diagram of the state before the cells are damaged, and the right side (Fig. 3(B)) is a schematic diagram of the state after the cells are damaged.
• the cell concentration (SS) refers to the value obtained by filtering a solution containing cells and dividing the weight (g) of the dry matter remaining on the filter by the volume (L) of the filtered solution containing the cells.
• soluble substances (DS) refers to the value obtained by dividing the dry weight (g) remaining after evaporating the water in the filtrate at the time of SS measurement by the volume of filtrate (L), or the value obtained by subtracting SS from TS. Therefore, “damage” refers to cell damage when soluble substances (DS) increase after a process that can cause damage. Also, in the case of a non-concentration process, cell damage is indicated when SS decreases and soluble substances (DS) increase.
• a parameter called "burst rate” will be used to quantify the degree of damage to cells in the concentrated solution.
• the "burst rate indicating the rupture state of the cell damage level” is derived from the following formula (1).
• Rupture rate DSc/TSc...(1)
• TSc TS - stock solution DS That is, TSc means TS derived from cell components.
• DSc DS - stock solution DS That is, DSc means DS derived from cell components.
• the DS of the stock solution matches the concentration of the medium components.
• the DS of the concentrate will decrease as the amount of water is added, and the burst rate of the concentrate cannot be calculated using the above formula (1). Therefore, when water is added to concentrate, the burst rate must be calculated taking into account the decrease in the DS of the concentrate due to the added water.
• the liquid obtained by diluting the concentrate concentrated in the concentrator 302 or the liquid after the hydrothermal treatment was filtered under reduced pressure using a filter (for example, glass fiber filter paper) and washed with distilled water three or more times. Thereafter, the filter is dried for at least 1 hour in, for example, a constant temperature air-blowing dryer set at 105 to 110°C, and the dry weight (g) of the solid matter remaining on the glass fiber filter is measured. This dry weight is divided by the volume of the filtered solution (L) to obtain the cell concentration (SS).
• the concentrate concentrated in the concentrating device 302 or the liquid after the solubilization treatment (hydrothermal treatment) in the solubilization treatment device 303 is placed in, for example, an aluminum container and dried for one hour or more in a constant temperature, air-blowing dryer set at 105 to 110°C, and the dry weight (g) is measured and divided by the amount of solution (L) used for evaporation to obtain the total solids (TS).
• the burst rate of the concentrated liquid used in the test example and comparative examples 1 and 2 was 32%.
• the range of rupture rates that is considered to be damage is a rupture rate of 1% or more.
• concentration was performed using a centrifugal separator as the concentrator 302 , and solubilization treatment was performed in the solubilization treatment device 303 . Thereafter, in a biomass treatment device 204 as shown in FIG. 4 (described later), a filtration step (S-15) and a drying step (S-15) (temperature: 105°C) were carried out in one device to obtain a dried product (dried cake).
• the solubilization treatment was carried out under the conditions that the concentrated liquid, Concentrated Microorganism 201A, was subjected to hydrothermal solubilization treatment at 180°C for 1 hour.
• the centrifugal separator used in the concentrator was Mitsubishi Selfjector "SJ-10F (product name)" manufactured by Mitsubishi Kakoki Kaisha.
• Comparative Example 2 the concentrated liquid in the test example was further concentrated using a tabletop centrifuge (Hitachi Koki Co., Ltd., product name "CT6EL"), the supernatant was replaced with distilled water, and the concentrated liquid was dried in a dryer; the hydrothermal solubilization treatment in the test example was not carried out.
• C6EL tabletop centrifuge
• Comparative Example 3 the concentration process was carried out using a tabletop centrifuge (Hitachi Koki Co., Ltd., product name "CT6EL”), and the concentrated liquid was dried directly to obtain a dried product.
• CT6EL tabletop centrifuge
• the obtained dried product was extracted by the Soxhlet extraction method using hexane as an extraction solvent, and the extraction rate was determined. The results of these tests are shown in Table 1.
• Figure 6 shows a schematic diagram of the state of cells before and after damage (rupture) and after hydrothermal treatment.
• the state of lipids in microorganisms before and after cell damage (rupture) Figures 6(A) and (B)
• Figure 6(C) The state of lipids after hydrothermal treatment after damage (rupture) are shown.
• FIG. 6A shows the state before concentration in which cells cover lipids 503 with membrane proteins 502 and amphipathic molecules 501 such as phospholipids.
• membrane proteins 502 and amphipathic molecules 501 such as phospholipids.
• membrane proteins 502 and amphipathic molecules 501 such as phospholipids are released or hydrolyzed, exposing the lipids, which allows the lipids to come into contact with, for example, the extraction solvent hexane, enabling good extraction.
• the solubilization treatment device 303 shown in Figure 1 is composed of a sealed container into which biomass raw materials are placed and sealed, and a means for introducing steam into the sealed container or a means for heating the container.
• the biomass raw material is placed in a sealed container, and then the container is heated to a predetermined temperature (e.g., 120°C to 240°C) for a predetermined time (e.g., 5 to 60 minutes) to perform hydrothermal solubilization treatment.
• a predetermined temperature e.g., 120°C to 240°C
• a predetermined time e.g., 5 to 60 minutes
• the inside of a sealed container that can withstand high pressure is heated to maintain a temperature of, for example, 160-170°C, and the biomass raw material is modified through thermal hydrolysis (hydrothermal reaction) to improve the water solubilization rate.
• the solubilization treatment device 303 is composed of a preheating section 303A, a reaction section 303B, and a cooling section 303C.
• concentrated microorganisms 201A from the concentrator 302 are first preheated in a preheating section 303A and then sent to a reaction section 303B where solubilization is performed.
• Steam 303a may be introduced into the reaction section 303B to perform solubilization.
• the solubilized solution 211 is cooled to a predetermined temperature in a cooling section 303C.
• the preheating section 303A and the cooling section 303C may be installed as needed.
• Reaction section 303B may be a continuous processing system using piping (for example, a double or triple reaction tube). Alternatively, instead of piping, it may be a tank-type continuous processing system.
• a filtration step (S14) is carried out inside the biomass treatment device 204 to filter the suspended solubilization treatment liquid 211.
• This filtration operation is carried out in order to reduce the volume of water in the solubilization treatment liquid 211 solubilized in the solubilization treatment device 202.
• the filtered product (wet cake) 201B obtained through filtration in the filtration step (S14) is subjected to a drying treatment in the drying step (S15).
• the moisture content (moisture content) of the filtered product (wet cake) 201B can be further reduced.
• the ratio of solids to moisture (solid-liquid ratio) of the wet biomass raw material which is the solubilization treatment liquid 211 obtained by the solubilization treatment step (S13), is initially, for example, "10/90", but by performing the "filtration step (S14)", the ratio of solids to moisture (solid-liquid ratio) in the filtered material (wet cake) 201B becomes "50/50".
• the filtered product (wet cake) 201B is subjected to a drying step (S15), whereby the ratio (solid-liquid ratio) of the water content in the dried microbial product (dried cake) 201C can be set to 90/10.
• the ratio (solid-liquid ratio) of the water content in the dried microbial product (dried cake) 201C is not limited in the present invention, and can be set to a value of 90/10 or less, such as about 95/5.
• non-polar solvents such as hexane, chloroform, carbon tetrachloride, and benzene
• organic solvents such as ethanol, acetone, and ethyl acetate
• the conditions for the drying step (S15) are, for example, 110°C, and preferably 60 to 120°C.
• the extraction conditions for the extraction step (S16) are, for example, 60°C, and preferably 30 to 80°C.
• the valuable resource recovery step (S17) in the valuable resource recovery device 307 is performed outside the system of the biomass treatment device 204.
• a valuable substance (oil) is extracted using a non-polar solvent, such as hexane, and the hexane extract is then filtered to remove any residue in the extraction solvent.
• the filtrate is dried to obtain the valuable substance (oil) 214 that is the target of extraction.
• the hydrothermal treatment in the solubilization treatment device 202 involves placing the biomass raw material 201 in a sealed container that can withstand high pressure, and while stirring with a stirring means such as a stirring blade, heating the biomass raw material (microorganisms) 201 using, for example, a heat transfer heater, an electric heater, a jacket or heat exchanger using steam or oil as a heat medium, microwaves, etc. Therefore, the biomass treatment device 204 is provided with means for carrying out these operations.
• the pressure inside the sealed container is increased by the pressure of the steam generated, causing the temperature of the biomass raw material 201 to rise above its boiling point at atmospheric pressure while still in liquid form, and the biomass raw material is subjected to hydrothermal treatment.
• the biomass raw material 201 and the extraction solvent 215 are placed in a container and extracted while being stirred with a stirring blade.
• the extraction temperature can be room temperature, heated, or cooled depending on the components to be extracted. Heating can be achieved using an electric heater, a jacket or heat exchanger using hot water, steam, oil, or other heat transfer media, or microwaves. For cooling, a jacket or a heat exchanger using cold water or an organic solvent as a refrigerant may be used.
• a biomass treatment device 204 that performs, within a single device, a solubilization treatment product filtration step (S14) of filtering the solubilization treatment liquid 211, which is the solubilized product from the solubilization treatment device 202, a drying step (S15) of drying the filtered product (wet cake) 201B obtained by the solubilization treatment product filtration step (S14), and an extraction step (S16) of extracting valuable resources 214 from the dried microbial product (dry cake) 201C obtained by the drying step (S15) into a solvent.
• a solubilization treatment product filtration step (S14) of filtering the solubilization treatment liquid 211 which is the solubilized product from the solubilization treatment device 202
• the biomass treatment device 204 is composed of a sealed container body 3, an agitator blade 5 located inside the container body 3 and rotated by an agitator shaft 4, an inlet pipe 36 for introducing the solubilization treatment liquid 211 into the device, a filter medium 34 for filtering the treated material, and a discharge pipe 35 for discharging the treated material to the outside.
• the solubilized liquid 211 from the hydrothermal solubilization treatment (soft hydrothermal treatment), not shown, is introduced into the main body 31 of the biomass treatment device 204 via the introduction pipe 36, as shown in Figure 4(a).
• a filtration step (S14) is performed to discharge the liquid portion (filtrate) 212a of the solubilized liquid, as shown in Figure 4(b).
• a drying step (S15) is performed in which the filtered material (wet cake) 201B is dried to obtain a dried microbial material (dried cake) 201C.
• extraction solvent 215 is introduced into the dried microorganism material 201C via inlet pipe 36.
• the introduced extraction solvent 215 is stirred and then filtered to obtain valuable resource solution 201D.
• this valuable resource dissolution liquid 216 is discharged into a liquid receiving container (not shown) provided outside the biomass treatment device 204, and the valuable resource recovery process (S17) is carried out.
• the extraction solvent 215 is separated and recovered from the valuables dissolved solution 201D to obtain valuables (oil) 214.
• the recovered extraction solvent is reused.
• the solubilization treatment liquid 211 is separated into solid and liquid components in advance in the biomass treatment device 204, and then solvent extraction is performed, thereby significantly reducing the amount of extraction solvent used.
• solvent extraction is performed, thereby significantly reducing the amount of extraction solvent used.
• the extraction efficiency is improved by thoroughly mixing the raw material and the extraction solvent during extraction.
• the raw material and the extraction solvent can be easily separated after extraction, low-cost and efficient extraction becomes possible.
• the solubilization of the biomass raw material which is the culture solution
• the solubilization treatment device 202 is promoted by the solubilization treatment device 202, and then the biomass treatment device 204 processes the culture solution. This shortens the filtration time and the overall processing time from solubilization to valuable resource extraction.
• the extraction rate will be higher than when undamaged culture medium is dried.
• the present invention can be used in general systems and methods for extracting valuable materials from biomass feedstocks.

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