WO2013165217A1 - Procédé pour la production de biodiesel utilisant des microorganismes sans processus de séchage - Google Patents

Procédé pour la production de biodiesel utilisant des microorganismes sans processus de séchage Download PDF

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WO2013165217A1
WO2013165217A1 PCT/KR2013/003871 KR2013003871W WO2013165217A1 WO 2013165217 A1 WO2013165217 A1 WO 2013165217A1 KR 2013003871 W KR2013003871 W KR 2013003871W WO 2013165217 A1 WO2013165217 A1 WO 2013165217A1
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hydroxide
oxide
catalyst
biodiesel
pellet
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PCT/KR2013/003871
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English (en)
Korean (ko)
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오희목
나현준
이재연
김희식
안치용
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한국생명공학연구원
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Priority to CN201380003867.6A priority Critical patent/CN103946343B/zh
Priority to US14/358,186 priority patent/US20140323755A1/en
Priority claimed from KR1020130049934A external-priority patent/KR101548043B1/ko
Publication of WO2013165217A1 publication Critical patent/WO2013165217A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P7/00—Preparation of oxygen-containing organic compounds
    • C12P7/64—Fats; Fatty oils; Ester-type waxes; Higher fatty acids, i.e. having at least seven carbon atoms in an unbroken chain bound to a carboxyl group; Oxidised oils or fats
    • C12P7/6436—Fatty acid esters
    • C12P7/6445—Glycerides
    • C12P7/6463—Glycerides obtained from glyceride producing microorganisms, e.g. single cell oil
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/42—Catalytic treatment
    • C10G3/44—Catalytic treatment characterised by the catalyst used
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/50—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids in the presence of hydrogen, hydrogen donors or hydrogen generating compounds
    • C10G3/52—Hydrogen in a special composition or from a special source
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
    • C10L1/026—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only for compression ignition
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
    • C11B1/00—Production of fats or fatty oils from raw materials
    • C11B1/02—Pretreatment
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
    • C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
    • C11C3/003—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fatty acids with alcohols
    • 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
    • C12P7/00—Preparation of oxygen-containing organic compounds
    • C12P7/64—Fats; Fatty oils; Ester-type waxes; Higher fatty acids, i.e. having at least seven carbon atoms in an unbroken chain bound to a carboxyl group; Oxidised oils or fats
    • C12P7/6436—Fatty acid esters
    • C12P7/6445—Glycerides
    • C12P7/6458—Glycerides by transesterification, e.g. interesterification, ester interchange, alcoholysis or acidolysis
    • 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
    • C12P7/00—Preparation of oxygen-containing organic compounds
    • C12P7/64—Fats; Fatty oils; Ester-type waxes; Higher fatty acids, i.e. having at least seven carbon atoms in an unbroken chain bound to a carboxyl group; Oxidised oils or fats
    • C12P7/6436—Fatty acid esters
    • C12P7/649—Biodiesel, i.e. fatty acid alkyl esters
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1011—Biomass
    • 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
    • Y02E50/10—Biofuels, e.g. bio-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
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock

Definitions

  • the present invention relates to a method for producing biodiesel by simultaneously extracting and transesterifying lipid components without drying and lipid extraction.
  • Biodiesel is a fatty acid methyl ester (FAME), a pollution-free fuel made from vegetable oils. It has a purity of 95% or more and has properties similar to that of diesel. As an additive or as a vehicle fuel itself.
  • FAME fatty acid methyl ester
  • Biodiesel has an environmental improvement effect to reduce air pollution and greenhouse gases resulting from the use of existing fossil energy.
  • biodiesel since biodiesel is produced from renewable biomass, there is no problem of depletion of energy resources. Carbon dioxide, which causes global warming, is recovered during the production of biomass, so the net emissions of carbon dioxide are very low.
  • biodiesel has a high oxygen content (more than 10% oxygen), which has a high rate of complete combustion, and can reduce particulate matters, such as carcinogens. There is this.
  • Microalgae can be divided into cell walls and various internal materials, which generally contain a lot of fiber, although they differ depending on the species.
  • the lipids in some species are very similar to vegetable oils, making them well suited for making biofuels.
  • Microalgae contain less than 80% lipids, 20-40% carbohydrates, and 30-70% proteins in their biomass, and some species have lipids of up to 80% dry matter ("Using microalgae marine biomass Biodiesel production technology "KSBB journal 2010. 25: 109 ⁇ 115).
  • Microalgae fibers are mainly cellulose and have a relatively constant diameter than plant-based cellulose fibers. Therefore, it is possible to overcome the disadvantage of changing the physical properties of the composite material by cellulose size imbalance in one fiber, which is pointed out as a disadvantage of vegetable cellulose.
  • the general manufacturing method for producing biodiesel, bioethanol, biobutanol and organic acids from microalgae on a laboratory scale is as follows. First, after culturing the microalgae, to remove biodiesel, bioethanol and organic acid, centrifugation, filtration and drying process to remove the maximum water in the microalgae, and then extract the lipids with a solvent having high selectivity for lipids. Switch to biodiesel. Alternatively, the microalgae are fermented using appropriate enzymes and microorganisms to produce bioethanol or organic acids (eg, lactic acid).
  • the cultured microalgae are harvested to obtain microalgal powders through a drying process, lipids are extracted from the dry powder using a solvent, and alkali or acid catalyst transfer esters are extracted using the extracted lipids.
  • biodiesel FAME, fatty acid methyl ether
  • Existing biodiesel conversion process has a problem that the drying process and the lipid extraction process after the microalgae harvest is essential, the process is complicated and the cost increases.
  • the inventors of the present invention have developed a method of increasing the production of biodiesel at room temperature and atmospheric pressure without removing the drying and lipid extraction steps when carrying out a process of drying an existing microorganism and extracting lipids to perform an ester exchange reaction.
  • the biodiesel manufacturing process is simplified and the cost is greatly reduced.
  • Another object of the present invention is to provide biodiesel without using a catalyst.
  • the present invention provides a method for producing biodiesel comprising the following steps:
  • a method for producing biodiesel comprising extracting FAME (fatty acid methyl ether) from the reactant of step 2).
  • the microorganism of step 1) may be one or more selected from the group consisting of microalgae, yeast, bacteria and fungi.
  • the pellet of step 1) may have a water content of 80% by weight to 98% by weight .
  • the alkyl alcohol of step 2) may be added in 10 to 10000 ml per 1 g of the dry weight of the pellet.
  • the pellet of step 2) may be further added to the alkyl alcohol, followed by mixing and dispersing.
  • the alkyl alcohol may be ethanol or methanol.
  • the method may further include adding a catalyst to the step of performing the transesterification reaction of step 2).
  • the catalyst may be a solid phase catalyst.
  • the solid catalyst may be an alkali catalyst, a metal oxide or an alloy catalyst.
  • the alkali catalyst is sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, barium hydroxide, sodium hydroxide, iron hydroxide, lithium hydroxide, zinc hydroxide, nickel hydroxide, tin hydroxide, barium hydroxide, cobalt hydroxide, chromium hydroxide, ammonium hydroxide, It may be one or more selected from zirconium hydroxide, titanium hydroxide, tantalum hydroxide, hafnium hydroxide, niobium hydroxide, chromium hydroxide and vanadium hydroxide, but is not necessarily limited thereto.
  • the metal oxide is calcium oxide, magnesium oxide, strontium oxide, barium oxide, iron oxide (2, 3), aluminum oxide, copper oxide, sodium oxide, silicon dioxide, titanium oxide, tin oxide, zinc oxide, zirconium oxide, cerium oxide , Lithium oxide, silver oxide and antimony oxide may be one or more selected from, but are not necessarily limited thereto.
  • the alloy catalyst may be an alloy catalyst used as a catalyst in a methanol-based fuel cell, but is not necessarily limited thereto.
  • the catalyst may be added at 0.01 to 10 g with respect to 1 g of the pellet dry weight, but is not necessarily limited thereto.
  • the transesterification reaction of step 2) may be performed at 3 to 85 ° C. and 50 to 350 rpm, and the pressure value in the closed reaction system may be 0.5 to 1.5 bar, but is not limited thereto. It doesn't happen.
  • the magnetic metal oxide may be recovered using an electromagnet and heat treated to further reuse the regenerated metal catalyst.
  • the present invention provides a use of the biodiesel produced by the method for producing biodiesel according to the present invention.
  • the biodiesel manufacturing method of the present invention shows a high yield of biodiesel yield by removing the drying and lipid extraction processes, and can produce an effective biodiesel even without a catalyst as an optimum reaction condition indicating high biodiesel yield. The cost can be greatly reduced.
  • 2A is a graph showing biodiesel production amount (mg / g) according to biomass state, catalyst amount and catalyst state.
  • 2B is a graph showing biodiesel production amount (% of DCW) according to biomass state, catalyst amount and catalyst state.
  • Figure 3a is a graph showing the biodiesel production amount (mg / g) according to the type of catalyst.
  • Figure 3b is a graph showing the biodiesel production (% of DCW) according to the catalyst type.
  • Figure 4a is a graph confirming the amount of production of biodiesel (FAME) according to the amount of catalyst and biomass by performing the optimal condition analysis for the conditions affecting the transesterification reaction using RSM.
  • Figure 4b is a graph confirming the amount of biodiesel production according to the amount of catalyst and temperature by performing the optimum condition analysis for the conditions affecting the transesterification reaction using RSM.
  • Figure 4c is a graph confirming the production amount of biodiesel according to the biomass-catalyst ratio and temperature by performing the optimal condition analysis for the conditions affecting the transesterification reaction using RSM.
  • Figure 4d is a graph confirming the amount of biodiesel production according to the temperature and biomass by performing the optimal condition analysis for the conditions affecting the transesterification reaction using RSM.
  • Figure 4e is a graph confirming the amount of saponification according to the biomass-catalyst ratio and the amount of biodiesel produced by performing an optimal condition analysis for the conditions affecting the transesterification reaction using RSM.
  • FIG. 5 is a diagram analyzing the biodiesel production amount and the components of the biodiesel according to the catalytic amount.
  • FIG. 6 is a graph showing biodiesel produced by applying an optimal reaction condition derived from a response surface methodology (RSM) to a yeast biomass.
  • RSM response surface methodology
  • biomass refers to a living organism used as an energy source.
  • FAME fatty acid methyl ether
  • dry biomass refers to pellets produced by culturing microorganisms and then performing only centrifugation without a drying step.
  • dry biomass refers to pellets from which moisture is removed through a drying step after culturing microorganisms.
  • transesterification refers to a reaction that converts the lipids of a microorganism into fatty acid methylesters.
  • the present invention is a.
  • step 3 provides a method for producing biodiesel comprising the step of extracting FAME (fatty acid methyl ether) from the reaction of step 2).
  • the microorganisms may be photosynthetic microorganisms or oleaginous microorganisms, and may be applied to algae, yeast, bacteria, and fungi having different lipid components and compositions, thereby biodiversifying lipid components in various living organisms. It can be effectively converted to diesel.
  • the algae are microalgae, the yeast is Yarrowia .
  • the fungus is preferably selected from Aureobasidium pullulans , but is not limited thereto.
  • the pellet of step 1) preferably has a water content of 80% by weight to 98% by weight, but is not limited thereto.
  • the centrifugation is preferably performed for 1 to 10 minutes at 3000 to 5000 rpm, but is not limited thereto.
  • the alkyl alcohol of step 2) is preferably added in an amount of 10 to 10000 ml based on 1 g of the dry weight of the pellet (wet biomass), but is not limited thereto.
  • the dry weight of the wet biomass is a value obtained by converting the wet biomass into a dry cell weight (DCW).
  • the alkyl alcohol is preferably methanol or ethanol, more preferably methanol, but is not limited thereto.
  • the alkyl alcohol reacts with the solid catalyst to form strong bases such as methoxide, ethoxide, and the like to induce transesterification, which is one of the nucleophilic substitutions. Therefore, the solid catalyst with excellent ability to remove protons from alcohol in alcohol-dominated environment can react with microorganisms in situ to extract lipid components by high temperature and ester exchange by strong base generation of solid catalyst. have.
  • the pellet of step 2) is preferably added to the alkyl alcohol and then mixed and dispersed, but is not limited thereto.
  • the method may further include adding a catalyst to the step of performing the transesterification reaction of step 2).
  • the catalyst is preferably a solid catalyst, but is not limited thereto.
  • the catalyst is preferably an alkali catalyst, a metal oxide or an alloy catalyst, but is not limited thereto.
  • the alkali catalyst is sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, barium hydroxide, sodium hydroxide, iron hydroxide, lithium hydroxide, zinc hydroxide, nickel hydroxide, tin hydroxide, barium hydroxide, cobalt hydroxide, chromium hydroxide, ammonium hydroxide, At least one selected from zirconium hydroxide, titanium hydroxide, tantalum hydroxide, hafnium hydroxide, niobium hydroxide, chromium hydroxide, and vanadium hydroxide is not limited thereto.
  • Sodium hydroxide and potassium hydroxide produce methoxide (methanol) or ethoxide (ethanol) in an alkyl alcohol environment, and calcium oxide can form ethoxide better than other solid phase catalysts.
  • the metal oxide is calcium oxide, magnesium oxide, strontium oxide, barium oxide, iron oxide (2, 3), aluminum oxide, copper oxide, sodium oxide, silicon dioxide, titanium oxide, tin oxide, zinc oxide, zirconium oxide, cerium oxide , At least one selected from lithium oxide, silver oxide and antimony oxide.
  • the alloy catalyst is preferably an alloy catalyst used as a catalyst in a methanol-based fuel cell, but is not limited thereto.
  • the catalyst is preferably added in an amount of 0.01 to 10 g based on 1 g of the dry weight of the pellet, but is not limited thereto.
  • the transesterification reaction of step 2) is preferably performed at 4 to 60 ° C. and 50 to 350 rpm, but is not limited thereto.
  • the biodiesel manufacturing method according to the present invention further includes the step of continuously reusing the regenerated metal catalyst by recovering and heat treating the metal catalyst using an electromagnet after the transesterification reaction when the magnetic metal oxide is added as a catalyst. can do.
  • the magnetic metal oxide may be iron oxide (Fe 2 O 3 ), an Nb-Ti alloy, or the like, but is not limited thereto.
  • Fatty acid methyl ether (FAME) extraction step of step 3) can be used in a variety of extraction methods known in the art, preferably extracted with an organic extraction solvent and FAME-solvent to separate FAME with an organic solvent filter It may be obtained through a filtration process, but is not limited thereto.
  • the present invention provides a use of the biodiesel produced by the method for producing the biodiesel.
  • the present inventors have prepared microalgae Chlorella vulgaris AG10032 (Biological Resource Center (BRC), Korea) for the production of fatty acid methyl ether (FAME) used as biodiesel in BG11 medium (Rippka, R., DeReuelles, J., Waterbury, JB, Herdman, M. & Stanier, RY (1979) .0.1 v in a 7 L jar fermentor using Generic assignments, strain histories and properties of pure cultures of cyanobacteria.J Gen Microbiol 111, 1-61. / v / m were cultured for 14 days under the light irradiation of the air supply and 120 ⁇ mol m -2 s -l of.
  • BRC Bio Resource Center
  • Dry cell weight of the cultured microalgae was measured, and 50 ml of the cultured microalgae was centrifuged for 5 minutes at 4000 rpm at 25 ° C. for 5 minutes using a 50 ml conical tube. Weight about 0.1 g) (wet biomass).
  • the inventors put 0.1 g of the pellet (wet biomass) obtained in Example ⁇ 1-1> into a 500 ml double jacketed reactor (FIG. 1) manufactured by itself without drying and lipid extraction process, and then 100 ml of methanol. And a catalyst (NaOH; product of sigma) were added under the conditions described in Table 1, respectively, and stirred at 300 rpm at room temperature for 25 minutes to react.
  • the custom-made double jacketed reaction tank prevents the loss of the reaction solution due to internal and external heat generation by circulating water by installing a condenser on the double jacketed reactor cover.
  • Example ⁇ 1-1> 0.1 g of dry biomass in a dry state in which the pellets obtained in Example ⁇ 1-1> were lyophilized as a control of the wet biomass to completely remove moisture to add a drying process.
  • 0.1 g of dry biomass in a dry state in which the pellets obtained in Example ⁇ 1-1> were lyophilized as a control of the wet biomass to completely remove moisture to add a drying process. was put into a 500 ml double jacketed reactor, and then experimented with the wet biomass under 100 ml of methanol and the conditions described in Table 1.
  • the present inventors took 25 ml of the reaction solution after the transesterification reaction in Example ⁇ 1-2>, transferred to conical tube, and added 10 ml of an extraction solvent in which Hexane and tert-butyl methyl ether were mixed in a 1: 1 volume ratio. FAME present in the reaction solution was extracted. An additional 5 ml of 4N sodium hydroxide solution was added to the extracted FAME to induce separation of the FAME-solvent layer. Take 1 ml from the separated supernatant FAME-solvent layer, filter it out using a polytetrafluoroethylene (PTFE) organic solvent filter, filter it into a GC vial, and add 50 ⁇ l of C17 internal standard (Fluka). A sample was made.
  • PTFE polytetrafluoroethylene
  • Biodiesel analysis was performed using gas chromatography (Shimadzu GC-2010, Japan) and biodiesel (Rt-wax column (maximum temperature: 250 °C) and FID detector (flame ionization detector, maximum temperature: 300 °C) FAME) was detected.
  • the injection volume used for detection was 1 ⁇ l and the total detection time was limited to 30 minutes.
  • Supelco's FAME mix 18918 (c8 ⁇ c24) was used as standard material for biodiesel analysis. After comparing the peak point of each sample and the peak point of the standard material, the biodiesel value according to the reaction conditions was quantified.
  • the amount of biodiesel according to each reaction condition (dry, wet, solid, solution, and reaction temperature) of Table 1 was 30 mg / g when reacted using dry biomass.
  • DCW was the lowest among the reaction conditions, and was 1/6 compared to the maximum biodiesel amount (180 mg / g detection at 0.1 g of solid, pellet type NaOH) obtained by using wet biomass ( 2). This is due to the aggregation of dried biomass particles, which inhibits the penetration of methanol into the cells, thereby rapidly reducing the extraction efficiency of lipid components in the cells, and methoxide sodium, a reaction catalyst produced by the combination of methanol and sodium hydroxide. The production rate of biodiesel has been reduced due to the reduced reaction rate between sodium methoxide and lipid components.
  • the average amount of biodiesel produced was 79 mg / g (DCW) when liquid sodium hydroxide was used, and about 2 times lower than the biodiesel production averaged 146 mg / g (DCW) when a solid catalyst was used.
  • Solid phase catalysts were high in efficiency, and biodiesel production was highest when the amount of solid phase catalyst was 0.1 g (FIG. 2).
  • the present inventors compared the amount of biodiesel produced according to the type of solid catalyst.
  • Example ⁇ 1-1> 0.1 g of the pellet obtained in Example ⁇ 1-1> was placed in a 500 ml double jacketed reactor (Wet Biomass) which was custom-made, and then 100 ml of methanol and NaOH and NaOH molar ratios under the conditions shown in Table 2 After carrying out an ester exchange reaction at room temperature for 1 hour by adding metal oxides (CaO, MgO, SrO and Fe 2 O 3 ; products of sigma) according to 0.2 g of biomass per 0.2 g of NaOH, the Example ⁇ 1- The biodiesel was extracted in the same manner as 3> and the amount of biodiesel was confirmed.
  • Wet Biomass 100 ml of methanol and NaOH and NaOH molar ratios under the conditions shown in Table 2
  • metal oxides CaO, MgO, SrO and Fe 2 O 3 ; products of sigma
  • the amount of biodiesel was highest as 140 mg / g (DCW) or more when reacted with sodium hydroxide or calcium as a solid catalyst, and 100 mg / g (DCW) or less when reacted with magnesium, strontium or iron. Showed low efficiency (Fig. 3).
  • Example ⁇ 1-3> and the sample used in Example ⁇ 1-4> were cultured at different times. Since the lipid content may vary depending on the culture state of the biomass, there is a slight difference in the converted biodiesel value, but no conversion efficiency.
  • the present inventors put the pellets in a predetermined amount of methanol in advance, and then stirred and dispersed well. Then, the in situ transesterification efficiency according to the amount of catalyst was measured using Response Surface Methodology (RSM) using Minitab 14 ( G. Vicente et al . Industrial Crops and Products 8 (1998) 29_35) were performed (FIG. 4).
  • RSM Response Surface Methodology
  • Example ⁇ 1-1> 0.1 g of the pellet (wet biomass) obtained in Example ⁇ 1-1> was added to 100 ml of methanol, stirred for an hour, and dispersed in advance. Biomass well dispersed in methanol was placed in a 500 ml double jacket reactor with NaOH 0.00 g, 0.01 g, 0.02 g, 0.05 g, 0.10 g, 0.20 g, 0.50 g, 1.00 g, 2.00 g and 3.00 g catalyst, respectively. After stirring at 300 rpm at 25 °C (room temperature) to perform an ester exchange reaction. In addition, the amount and type of FAME production were confirmed after the ester reaction.
  • the amount of catalyst and the amount of FAME were inversely proportional to each other, and the amount of catalyst was found to be similar to the amount of catalyst below 0.20 g. 5).
  • Example ⁇ 1-2> the reaction was performed by adding wet biomass, methanol and a catalyst, and the reaction of dispersing the pellet (wet biomass) in methanol was not performed.
  • the pellet was first dispersed well in methanol and then reacted.
  • diffusion of a solvent, such as methanol into the biomass during the in-situ transesterification of wet biomass is known as a rate limiting step that determines the reaction rate and efficiency. Therefore, if methanol is well dispersed in the pellets through the process of the present embodiment, it is determined that FAME is rapidly generated with high efficiency even under a non-catalyst.
  • the dried biomass particles are aggregated with each other, thereby inhibiting the penetration of methanol into the cells, thereby rapidly reducing the extraction efficiency of lipid components in the cells.
  • the relative amount of methanol relative to the wet biomass is high, the intracellular penetration is good.
  • the reaction of dispersing methanol in the wet biomass is carried out first, so that the extraction of lipid components in the cell is better.
  • a transesterification reaction was performed using yeast biomass under the reaction conditions obtained through RSM analysis.
  • the yeast Yarrowia lipolytica (Biological Resource Center, BRC), Korea, was used to supply 0.1 v / v / m air and 120 ⁇ mol m -2 s -l in 2 L bottles using YM medium. Incubated for 14 days under light irradiation. Dry cell weight of the cultured yeast was measured, and the cultured yeast culture was centrifuged at 4000 rpm for 5 minutes using a 50 ml conical tube, and then the supernatant was removed from the pellet (water content of 82 to 85 weight). %), And a portion of the pellet (dry weight about 0.5 g) was subjected to an ether exchange reaction at room temperature (25 ° C.) at 300 rpm for 60 minutes. Then, the biodiesel production amount was confirmed by the method of Example ⁇ 1-3>.
  • yeast biomass showed conversion efficiency of 22% or more of the unit biomass with a FAME production amount of 224. 82 mg / g (FIG. 7).
  • Biodiesel manufacturing method of the present invention is simplified compared to the existing process, and since biodiesel is produced effectively without a catalyst, it can be used for the production of biodiesel or by-products accordingly.

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Abstract

La présente invention porte sur un procédé pour la production de biodiesel sans un processus de séchage ou un processus d'extraction de composants lipidiques dans un environnement contenant principalement de l'alcool. Le procédé pour la production de biodiesel selon la présente invention permet de créer des conditions optimales pour une transestérification pour produire ainsi du biodiesel d'une manière efficace même sans catalyseur, ce qui réduit ainsi le nombre de processus, le coût de production et la durée de production tout en augmentant le rendement de production de biodiesels.
PCT/KR2013/003871 2012-05-04 2013-05-03 Procédé pour la production de biodiesel utilisant des microorganismes sans processus de séchage WO2013165217A1 (fr)

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CN201380003867.6A CN103946343B (zh) 2012-05-04 2013-05-03 用于使用微生物产生生物柴油而无需干燥过程的方法
US14/358,186 US20140323755A1 (en) 2012-05-04 2013-05-03 Method for Producing Biodiesel Using Microorganisms Without Drying Process

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CN104232190A (zh) * 2014-08-20 2014-12-24 山东忠谊清洁能源有限责任公司 一种浮精直接成浆工艺

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Publication number Priority date Publication date Assignee Title
US20030083514A1 (en) * 1999-08-18 2003-05-01 Boocock David Gavin Brooke Single-phase process for production of fatty acid methyl esters from mixtures of triglycerides and fatty acids
KR100983023B1 (ko) * 2010-07-07 2010-09-17 한국해양연구원 부등편모조류 또는 착편모조류에 속하는 미세조류의 지방산으로부터 트리글리세라이드 또는 지방산메틸에스테르를 추출하는 방법 및 이를 이용한 바이오디젤 제조방법
KR20110077723A (ko) * 2009-12-30 2011-07-07 (주)엔엘피 바이오 디젤 및 그 제조방법
WO2011100563A2 (fr) * 2010-02-12 2011-08-18 Utah State University Récupération de lipides transestérifiés et procédés associés
US20120083617A1 (en) * 2010-10-02 2012-04-05 Cal Poly Corporation Process for Extracting Lipids from Microalgae

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030083514A1 (en) * 1999-08-18 2003-05-01 Boocock David Gavin Brooke Single-phase process for production of fatty acid methyl esters from mixtures of triglycerides and fatty acids
KR20110077723A (ko) * 2009-12-30 2011-07-07 (주)엔엘피 바이오 디젤 및 그 제조방법
WO2011100563A2 (fr) * 2010-02-12 2011-08-18 Utah State University Récupération de lipides transestérifiés et procédés associés
KR100983023B1 (ko) * 2010-07-07 2010-09-17 한국해양연구원 부등편모조류 또는 착편모조류에 속하는 미세조류의 지방산으로부터 트리글리세라이드 또는 지방산메틸에스테르를 추출하는 방법 및 이를 이용한 바이오디젤 제조방법
US20120083617A1 (en) * 2010-10-02 2012-04-05 Cal Poly Corporation Process for Extracting Lipids from Microalgae

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104232190A (zh) * 2014-08-20 2014-12-24 山东忠谊清洁能源有限责任公司 一种浮精直接成浆工艺
CN104232190B (zh) * 2014-08-20 2016-01-20 山东忠谊清洁能源有限责任公司 一种浮精直接成浆工艺

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