US20100261235A1 - Continuous production of biodiesel fuel by enzymatic method - Google Patents

Continuous production of biodiesel fuel by enzymatic method Download PDF

Info

Publication number
US20100261235A1
US20100261235A1 US12/745,962 US74596208A US2010261235A1 US 20100261235 A1 US20100261235 A1 US 20100261235A1 US 74596208 A US74596208 A US 74596208A US 2010261235 A1 US2010261235 A1 US 2010261235A1
Authority
US
United States
Prior art keywords
catalyst reaction
oil
glycerin
lower alcohol
fat
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Abandoned
Application number
US12/745,962
Other languages
English (en)
Inventor
Nobuyuki Kuratani
Shinji Hama
Hideo Noda
Hideki Fukuda
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BIO-ENERGY Corp
Kansai Chemical Engineering Co Ltd
Bio Energy Corp
Original Assignee
Kansai Chemical Engineering Co Ltd
Bio Energy Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Kansai Chemical Engineering Co Ltd, Bio Energy Corp filed Critical Kansai Chemical Engineering Co Ltd
Assigned to BIO-ENERGY CORPORATION, KANSAI CHEMICAL ENGINEERING CO., LTD. reassignment BIO-ENERGY CORPORATION ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: FUKUDA, HIDEKI, HAMA, SHINJI, KURATANI, NOBUYUKI, NODA, HIDEO
Publication of US20100261235A1 publication Critical patent/US20100261235A1/en
Abandoned legal-status Critical Current

Links

Images

Classifications

    • 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
    • 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
    • C12P7/62—Carboxylic acid 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 continuously producing a fatty acid ester useful as a biodiesel fuel using an enzymatic method, and an apparatus for the same.
  • fossil fuels typified by petroleum and light oil are used as fuels for automobiles.
  • biodiesel fuel As an alternative fuel to fossil fuels such as light oil, there are high expectations in so-called biodiesel fuel, which uses oils and fats produced by naturally-occurring plants, animals, fishes, or microorganisms. Among these oils and fats, those used for food producing are often dumped into the environment and cause environmental problems. Therefore, expectations in biodiesel fuel made from a waste oil are particularly high in view of prevention of air pollution and effective utilization of a waste oil.
  • Fatty acid esters obtained by transesterification between an oil and fat and a lower alcohol are preferably used as biodiesel fuels.
  • a variety of researches have been conducted on an enzyme-catalytic method using a lipase, as one method for producing a fatty acid ester (International Publications WO 01/038553 and WO 00/12743).
  • This production method has many advantages, for example, in that aftertreatment of by-product glycerin is easy, in that mild reaction conditions can be applied, and in that a free fatty acid in a starting material can be esterified (H. Fukuda et al., Journal of Bioscience and Bioengineering, 2001, Vol. 92, pp. 405-416).
  • the reactor can be filled with a large amount of enzyme, the method has a feature that there is a significant increase in the amount of target substance produced per reactor unit volume and per reaction time.
  • Y. Watanabe et al. Journal of the American Oil Chemists' Society, 2000, Vol. 77, pp. 855-360
  • K Nie et al. Journal of Molecular Catalysis B: Enzymatic, 2006, Vol. 43, pp.
  • a method is applied in which an oil and fat and a lower alcohol are supplied from an upper portion of a reaction tube, a reaction mixture that has flown out of a lower portion thereof is temporarily allowed to stand so as to be separated into layers, and then a fatty acid ester in an upper layer (also containing unreacted oil and fat) is collected.
  • a lower alcohol inhibits the activity of a lipase, and thus it is necessary to strictly control the ratio of lower alcohol contained in the reaction mixture. Furthermore, since the solubility of a lower alcohol in an oil and fat is extremely low, it is necessary to keep a uniformly dispersed state such that a droplet of the alcohol is not formed in the oil and fat (Y. Shimada et al., Journal of Molecular Catalysis B: Enzymatic, 2002, Vol. 17, pp. 133-142). There is also a method for reducing the alcohol inhibition by dissolving the reaction mixture in a hydrophobic organic solvent, such as hexane. However, according to the method the collection of the product is difficult, and the production process is complicated.
  • a hydrophobic organic solvent such as hexane
  • Glycerin forms as a by-product during a procedure for producing a fatty acid ester. A certain amount of the glycerin accumulated forms a layer around the enzyme. Since this layer of glycerin is hydrophilic, it greatly affects the contact efficiency between unreacted oil and fat and the enzyme. Moreover, part of a lower alcohol remaining in the reaction procedure is dispersed in the glycerin layer, and locally increases the concentration of alcohol near the enzyme, so that a lowered enzymatic activity is caused (Y. Watanabe et al., Journal of the American Oil Chemists' Society, 2000, Vol. 77, pp. 855-860).
  • One aspect is that a method for continuously collecting a product for a long period of time while supplying starting materials is desirable, and use of a packed-bed reactor is advantageous for industrial production of a biodiesel fuel using a lipase.
  • another aspect is that it is necessary to be careful of the possibility that a desirable yield of fatty acid ester may not be obtained depending on the supply of an oil and fat and a lower alcohol to a reaction tube and the removal efficiency of by-product glycerin as described above. Therefore, it is necessary to establish a method for continuously producing a biodiesel fuel simultaneously considering these two aspects.
  • the object of the present invention is to provide a process capable of strictly controlling the concentration of a lower alcohol while automatically removing by-product glycerin in the production of a fatty acid ester from oils and fats using a lipase.
  • the present invention provides a method for continuously producing a fatty acid ester in a reaction apparatus having a plurality of stages of catalyst reaction tubes filled with a lipase, comprising:
  • a liquid flow rate in the reaction apparatus is at least 2.15 cm/min.
  • an amount of the lower alcohol supplied to each of the catalyst reaction tubes is 0.5 to 1.0 mol equivalent with respect to the oil and fat starting material.
  • the number of stages of the catalyst reaction tubes is 2 to 10.
  • the oil and fat starting material is a vegetable oil and fat, an animal oil and fat, a fish oil, an oil and fat produced by a microorganism, a mixture thereof, or a waste oil thereof.
  • the lower alcohol is methanol, ethanol, n-propanol, or n-butanol.
  • the method further comprising following the step (f): (f) repeating the steps (a) to (f) using the separated liquid obtained in the step (f) as the oil and fat starting material.
  • the present invention also provides an apparatus for continuously producing a fatty acid ester, comprising:
  • a glycerin separation tank that is placed downstream of each of the catalyst reaction tubes, and that separates an outflowing liquid from the catalyst reaction tube into glycerin and a separated liquid;
  • a mixing means that is placed between each of the lower alcohol supply ports and each of the catalyst reaction tubes for mixing an oil and fat starting material or the separated liquid and a lower alcohol;
  • a liquid flow rate in the apparatus is adjusted to at least 2.15 cm/min.
  • an amount of the lower alcohol supplied to each of the catalyst reaction tubes is adjusted to 0.5 to 1.0 mol equivalent with respect to the oil and fat starting material.
  • the number of stages of the catalyst reaction tubes is 2 to 10.
  • the present invention in transesterification between an oil and fat and a lower alcohol using a lipase as a catalyst, it is possible to efficiently and continuously produce a fatty acid ester while automatically removing by-product glycerin.
  • the apparatus of the present invention it is possible to efficiently and continuously perform a series of steps ranging from supply of starting materials to collection of a fatty acid ester.
  • FIG. 1 is a schematic diagram showing the configuration of a reaction apparatus (packed-bed reactor) 100 of the present invention and the flow of continuous production of a biodiesel fuel using the same.
  • FIG. 2 is a schematic diagram showing a manner in which a fatty acid ester and glycerin are separated in a glycerin separation tank 40 .
  • FIG. 3 is a graph showing the concentration of fatty acid ester in a liquid flowing out of each stage of a catalyst reaction tube 10 at a volume flow rate of 250 to 1080 ml/h (a liquid flow rate of 2.15 to 9.30 cm/min).
  • FIG. 4 is a graph showing the weight of glycerin separated in the glycerin separation tank 40 placed downstream of each stage of the catalyst reaction tube 10 .
  • FIG. 5 is a graph showing the concentration of methyl ester and the outflow amount of glycerin in the case where 0.33 mol equivalents of methanol with respect to an oil and fat starting material are mixed with a liquid that is to be supplied to each stage of the catalyst reaction tube 10 , and the mixture liquid is caused to pass through the tube at a volume flow rate of 540 ml/h (a liquid flow rate of 4.65 cm/min).
  • FIG. 6 is a graph showing the concentration of methyl ester in each stage in the case where a methanolysis reaction is repeatedly performed using two stages of catalyst reaction tubes.
  • a lipase refers to an enzyme that has an ability to degrade glyceride (also referred to as acylglycerol) into glycerin or a partial glyceride and a fatty acid, and has an ability to produce a fatty acid ester through transesterification in the presence of a linear lower alcohol.
  • glyceride also referred to as acylglycerol
  • the lipase used in the present invention may be 1,3-specific or nonspecific. In view of production of a linear lower alcohol ester of a fatty acid, a nonspecific lipase is preferable.
  • the lipase include: lipases derived from filamentous fungi belonging to Genus Rhizomucor ( Rhizomucor miehei ), Mucor, Aspergillus, Rhizopus, Penicillium, and the like; lipases derived from yeasts belonging to Genus Candida ( Candida antarctica, Candida rugosa, and Candida cylindracea ), Pichia, and the like; lipases derived from bacteria belonging to Genus Pseudomonas, Serratia, and the like; and lipases derived from animals, such as hog pancreas.
  • lipases are also used. Examples thereof include lipases derived from Rhizomucor miehei (Lipozyme IM60: manufactured by Novo Nordisk), lipases derived from Candida antarctica (Novozyme 435: manufactured by Novozymes), lipases derived from Rhizopus delemar (Talipase: manufactured by Tanabe Seiyaku Co., Ltd.), lipases of Candida rugosa (Lipase OF: manufactured by Meito Sangyo Co., Ltd.), and lipases of the genus Pseudomonas (Lipase PS and Lipase AK: manufactured by Amano Enzyme Inc.).
  • an immobilized lipase refers to a lipase that is immobilized on a given carrier. It is possible to use an immobilized enzyme that is immobilized on a commonly used carrier, such as a resin, or to use a cell that produces and retains the lipase. Furthermore, as described later, the cell may be further immobilized on a given carrier. Furthermore, it is effective to use mutually different types of immobilized lipases in each of the catalyst reaction tubes.
  • the lipase that is immobilized on a carrier ordinarily, a purified enzyme or a partially purified enzyme isolated or extracted from a natural product or a recombinant is used.
  • the carrier on which a purified enzyme or a partially purified enzyme is immobilized include carriers usually used for immobilizing an enzyme. Examples thereof include organic high molecular compounds, such as various ion-exchange resins, and inorganic porous materials, such as ceramics.
  • the immobilization is performed, for example, by applying methods usually used by those skilled in the art, such as a carrier-binding method, a crosslinking method, an entrapment method, and the like.
  • the carrier binding method includes a chemical adsorption method or a physical adsorption method comprising adsorbing to an ion-exchange resin.
  • the cell that produces and retains the lipase is bacteria, fungi, plant cells, or the like, but there is no limitation thereto. It is preferable to use yeasts and filamentous fungi. It is also possible to use recombinants into which various lipase genes have been introduced.
  • the lipase-producing cell used in the present invention may be immobilized on a carrier.
  • a carrier As the material of the carrier that can be used in the present invention, foams or resins such as polyvinyl alcohol, a polyurethane foam, a polystyrene foam, polyacrylamide, a polyvinyl formal resin porous material, a silicon foam, a cellulose porous material, or the like are preferable. It is preferable to use a porous carrier, for example, in view of shedding of cells with reduced growth and activity or dead cells.
  • the size of the opening of the porous material varies depending on the type of cells. The size enough for cells to enter and grow therein is suitable.
  • a size of 50 ⁇ m to 1000 ⁇ m is preferable, but the size is not limited thereto.
  • the shape of the carrier In view of the strength of the carrier, the cultivation efficiency or the like, spherical or cubical shapes are preferable.
  • a preferable size is 1 mm to 50 mm in diameter for a spherical carrier, and 2 mm to 50 mm in length of the side for a cubical carrier.
  • Starting materials for the fatty acid ester are an oil and fat and a lower alcohol.
  • oils and fats vegetable oils and fats, animal oils and fats, fish oils, oils and fats produced by microorganisms, mixtures thereof, or waste oils thereof are used preferbly.
  • vegetable oils and fats include soybean oil, rape seed oil, palm oil, olive oil, and the like.
  • animal oils and fats include beef tallow, lard, sperm oil, mutton tallow, and the like.
  • fish oils include sardine oil, tuna oil, squid oil, and the like.
  • oils and fats produced by microorganisms include oils and fats produced by microorganisms belonging to Genus Mortierella, Schizochytrium, and the like.
  • the waste oils refer to used plant and animal oils and fats, and examples thereof include Tempura (battered and deep fried foods) waste oils, and the like. Since the waste oils were heated to a high temperature, they also contain hydrogenated, oxidized, or peroxidized oils. These oils also can be used as the starting material. The oils may contain water. Alternatively, the reaction mixture in which these oil and fat starting materials have once been treated with the lipase also can be used as the starting material.
  • a lower alcohol refers to an alcohol having 1 to 8 carbon atoms.
  • a linear lower alcohol is preferable, in particular, methanol, ethanol, n-propanol, or n-butanol is preferable.
  • a reaction apparatus refers to an apparatus having a plurality of stages of connected catalyst reaction tubes that are tubes, such as stainless steel tubes, filled with an immobilized lipase or lipase-producing cells.
  • FIG. 1 schematically shows the configuration of an embodiment of a reaction apparatus 100 as a typical apparatus of the present invention, using, as an example, the case in which the reaction apparatus is a packed-bed reactor, but there is no limitation thereto.
  • This typical reaction apparatus 100 includes a plurality of stages of catalyst reaction tubes 10 , glycerin separation tanks 40 , lower alcohol supply ports, and a mixing means 50 .
  • the catalyst reaction tubes 10 in FIG. 1 can be extended depending on the reaction efficiency.
  • the catalyst reaction tubes 10 preferably have a length of 1 to 2 m per stage, and an inner diameter of 1 to 5 cm, but there is no limitation thereto.
  • the number of stages of the catalyst reaction tubes 10 is preferably 2 to 10, and more preferably 3 to 7, but there is no limitation thereto.
  • the catalyst reaction tubes 10 are preferably made of a material selected in consideration of the viscosity of the oil and fat, and deterioration caused by the starting materials and the product. Examples of such a material include stainless steel and the like.
  • the catalyst reaction tubes 10 are filled with the lipase that is immobilized by given means.
  • the catalyst reaction tubes 10 are connected to each other, for example, via tubes.
  • the tubes connect the catalyst reaction tubes 10 such that an oil and fat starting material or a separated liquid is supplied to each catalyst reaction tube 10 from above, the separated liquid being obtained after passing through its preceding catalyst reaction tube 10 and the glycerin separation tank 40 , and such that an outflowing liquid flows out of the lower portion of the catalyst reaction tube 10 .
  • the tubes are preferably made of a material selected in consideration of the viscosity of the oil and fat, and deterioration caused by the starting materials and the product, and more preferably made of silicon or Teflon (registered trademark).
  • pressure gauges 20 are arranged in order to measure the pressure in the catalyst reaction tubes 10 . It is preferable to use pressure gauges that can indicate the pressure up to 1 MPa.
  • pumps 30 are arranged in order to supply the starting materials (the oil and fat and the lower alcohol) and the separated liquid to the catalyst reaction tubes 10 , or in order to supply the outflowing liquid to the glycerin separation tanks 40 , at a given pressure or rate. It is preferable to use metering pumps having a maximum ejection pressure of approximately 0.4 to 1.0 MPa in consideration of a pressure loss in the catalyst reaction tubes 10 .
  • the glycerin separation tanks 40 are placed between the catalyst reaction tubes 10 .
  • a method for separating glycerin there is no particular limitation regarding a method for separating glycerin.
  • the glycerin separation tank 40 preferably has a space (e.g., a given space in a sight glass) for retaining the outflowing liquid from the catalyst reaction tube 10 (containing a fatty acid ester, unreacted oil and fat, and glycerin) for a given time.
  • a space e.g., a given space in a sight glass
  • the separated liquid containing the fatty acid ester and the unreacted oil and fat overflows and is supplied to the following catalyst reaction tube 10 .
  • the glycerin present in the lower layer is discharged downward when an electromagnetic valve is opened and closed after the elapse of a given time, and collected by a receiving unit. In this separation, as described later in detail, it is important to adjust the liquid flow rate (or the volume flow rate) in the reaction apparatus 100 .
  • lower alcohol supply ports are placed upstream of the respective stages of catalyst reaction tubes 10 , and the lower alcohol is added from these supply ports to the separated liquid.
  • the mixing means 50 is placed between the lower alcohol supply port and the following catalyst reaction tube.
  • the mixing means 50 include fillers in the tube, and a stationary mixer. More specifically, for example, placing fillers such as beads in a tube for supplying the oil and fat or the separated liquid to the catalyst reaction tubes 10 can facilitate mixing of a mixture of the oil and fat and the lower alcohol passing through the tube.
  • a constant-temperature water circulation apparatus is preferably placed around the catalyst reaction tubes 10 .
  • the constant-temperature water circulation apparatus preferably can keep the temperature of the reaction apparatus 100 , in particular, the catalyst reaction tubes 10 at 25° C. to 45° C. at which the enzyme reaction occurs in a more preferable manner.
  • the entire reaction apparatus 100 , or the mixing means 50 and the catalyst reaction tubes 10 may be placed in a constant-temperature chamber.
  • the present invention is directed to a method for continuously producing a fatty acid ester in a reaction apparatus having a plurality of stages of catalyst reaction tubes filled with a lipase, comprising:
  • a fatty acid ester it is possible to efficiently and continuously produce a fatty acid ester, for example, using the reaction apparatus 100 as shown in FIG. 1 , as the reaction apparatus having a plurality of stages of catalyst reaction tubes filled with a lipase. That is to say, in the reaction apparatus 100 described above, an oil and fat starting material and a lower alcohol are sufficiently agitated and supplied to the catalyst reaction tube 10 , a lipase is caused to act in the catalyst reaction tube 10 , thereby producing a fatty acid ester, the outflowing liquid from the catalyst reaction tube 10 is introduced into the glycerin separation tank 40 , thereby glycerin being collected, and the separated liquid together with a lower alcohol is further supplied to the following catalyst reaction tube 10 . By repeating these operations, a fatty acid ester can be collected from the separated liquid from the last catalyst reaction tube.
  • the separated liquid from the last catalyst reaction tube may be used as the oil and fat starting material, and the reaction in this reaction apparatus may be repeated several times. For example, by repeatedly causing a liquid to pass three times through a reaction apparatus having three stages of catalyst reaction tubes, it is possible to obtain a separated liquid containing a fatty acid ester at the same concentration as that in a reaction apparatus having nine stages of catalyst reaction tubes.
  • the liquid flow rate is determined as appropriate depending to the type of alcohol, the diameter and the number of stages of the catalyst reaction tubes 10 , the type of the oil and fat starting material, and the like.
  • the liquid flow rate is usually at least 2.15 cm/min, preferably at least 4.65 cm/min, more preferably at least 6.03 cm/min, still more preferably at least 6.90 cm/min, even more preferably at least 7.76 cm/min, and most preferably at least 8.62 cm/min.
  • the amount and the rate of lower alcohol supplied are determined depending to the type of alcohol, the number of stages of the catalyst reaction tubes 10 , the type of the oil and fat starting material, the flaw rate, and the like.
  • the amount of lower alcohol supplied to each stage is preferably kept at 0.5 to 1.0 mol equivalent with respect to the oil and fat starting material. If the amount of lower alcohol supplied is small, the productivity of methyl ester and the separation efficiency of glycerin are poor. On the other hand, if the amount of lower alcohol supplied is large, the activity of the lipase in the catalyst reaction tubes 10 may be inhibited.
  • the rate of lower alcohol supplied for example, in the case where a triolein starting material is caused to pass through the catalyst reaction tubes 10 at 1000 ml/h, the rate of methanol supplied is preferably 19.9 to 39.9 ml/h.
  • Causing the lower alcohol to pass through the mixing means 50 such as fillers in the tube, a stationary mixer, or the like can facilitate mixing of the lower alcohol and the oil and fat.
  • Transesterification between the oil and fat and the lower alcohol catalyzed by the lipase is performed generally at 5° C. to 80° C., preferably at 15° C. to 50° C., and more preferably at 25° C. to 45° C.
  • the reaction temperature may be determined depending on a microorganism or an enzyme used. For example, in the case where a heat-resistant microorganism or enzyme is used, the reaction can be performed at a relatively high temperature.
  • the fatty acid ester after the reaction is separated and collected from the reaction mixture containing unreacted glyceride and lower alcohol through a separating operation usually used by those skilled in the art, such as distillation.
  • the thus collected fatty acid ester can be used as a biodiesel fuel.
  • FIG. 1 shows a schematic diagram showing the configuration of the packed-bed reactor 100 used in Examples.
  • Stainless steel pipes (length 1 m, inner diameter 15.7 mm, and volume 193.6 ml) were used as the catalyst reaction tubes 10 .
  • These stainless steel pipes were filled with Novozyme 435 (manufactured by Novozymes) to an enzyme filing ratio of 60% (v/v) to give the catalyst reaction tubes 10 .
  • the catalyst reaction tubes 10 were kept at 30° C., and the pressure gauges 20 were placed above the tubes to confirm a pressure loss.
  • the oil and fat starting material was supplied to the upper portion of the catalyst reaction tube 10 using the metering pump 30 , end fillers were placed inside a supply tube for the catalyst reaction tube 10 , thus facilitating mixing of the oil and fat and the lower alcohol.
  • the glycerin separation tanks 40 were placed under the catalyst reaction tubes 10 , and glycerin formed as a by-product during the reaction procedure was collected in each stage.
  • the fatty acid ester, the unreacted oil and fat, and the glycerin contained in the outflowing liquid from the catalyst reaction tube 10 were retained in a given space in a sight glass, and the separated liquid (containing the fatty acid ester and the unreacted oil and fat) obtained by the separation performed therein and a newly added lower alcohol were supplied to the following catalyst reaction tube 10 while being sufficiently mixed by the mixing means 50 .
  • the volume flow rate at the catalyst reaction tubes 10 was set to 250 ml/h, 640 ml/h, or 1080 ml/h. These volume flow rates at the catalyst reaction tubes 10 respectively correspond to liquid flow rates of 2.15 cm/min, 4.65 cm/min, and 9.30 cm/min.
  • the valves in the lower portions of the glycerin separation tanks 40 were opened, and the weight of by-product glycerin formed in each stage was measured. Then, 200 ⁇ l of the separated liquid flowing out in each stage was collected, and the concentration (content) of fatty acid methyl ester was analyzed.
  • the concentration (content) of fatty acid methyl ester was determined by a gas chromatography analysis using tricaprylin as the internal standard.
  • the analysis conditions were as follows.
  • Injector temperature 320° C.
  • Carrier gas helium gas (1.76)
  • FIG. 3 shows the content of fatty acid methyl ester in the separated liquid obtained in each stage.
  • the content of methyl ester in the outflowing liquid increased, and the concentrations in the ninth stage were respectively 93.3 wt % (volume flow rate 250 ml/h), 90.6 wt % (540 ml/h), and 84.8 wt % (1080 ml/h), and those in the 10th stage were respectively 95.3 wt % (540 ml/h) and 88.9 wt % (1080 ml/h).
  • the concentration of methyl ester in the separated liquid obtained in each stage was affected by a change in the volume flow rate, in other words, the retention time in the catalyst reaction tubes 10 , but it was shown that a sufficiently high concentration of methyl ester was obtained even with a relatively short retention time (approximately 10.8 min per stage at 1080 ml/h).
  • FIG. 4 shows the weight (cumulative amount) of glycerin collected by the separation tank 40 in each stage.
  • the total amount of glycerin formed as a by-product is approximately 52.04 g.
  • the volume flow rate was 250 ml/h
  • glycerin was not practically collected even in the sixth stage where the content of methyl ester was greater than 68 wt %. This means that since the flow rate of the outflowing liquid was low, a glycerin layer was retained near the enzyme in the catalyst reaction tubes 10 .
  • the weight of glycerin separated increased as the number of stages increased, and 46.8 g of glycerin was separated in stages up to the 10th catalyst reaction tube 10 where the content of methyl ester reached 95.3 wt %.
  • This figure corresponds to 89.9% of the amount of glycerin that can be theoretically separated.
  • the volume flow rate was 1080 ml/h
  • 51.75 g of glycerin (99.4% of the theoretical amount) was separated in stages up to the 10th catalyst reaction tube 10 .
  • Table 1 lists the number of stages in the packed-bed reactor used in this Example, the concentration of fatty acid ester after the reaction in 10 stages, the productivity per unit reaction time and per unit reactor volume, the weight of glycerin separated, and the ratio of the glycerin amount with respect to the theoretical amount.
  • FIG. 5 shows the content of methyl ester and the outflow amount of glycerin (cumulative amount) in this case. Under these conditions, the productivity of methyl ester and the separation efficiency of glycerin in each stage were inferior to those in the case where 0.5 mol equivalents of methanol with respect to the oil and fat starting material were mixed therewith. Accordingly, it is shown that adjustment of the amount of methanol supplied to the catalyst reaction tubes significantly affects the apparatus ability.
  • the number of stages of the catalyst reaction tubes 10 was set to two in the packed-bed reactor 100 shown in FIG. 1 .
  • Glycerin was separated from the oil and fat flowing out of the second catalyst reaction tube 10 , 0.5 mol equivalents of methanol with respect to the oil and fat were mixed therewith, and then the oil and fat was again caused to pass through the first catalyst reaction tube 10 as in the first cycle (second cycle).
  • FIG. 6 shows the content of fatty acid methyl ester in the separated liquid obtained in each stage.
  • FIG. 6 clearly shows that, in the case where a methanolysis reaction was repeated four times in the two stages of catalyst reaction tubes, a fatty acid ester having a high purity was obtained. It is shown that, in the case where a liquid is continuously and repeatedly caused to pass through a reactor having two stages of catalyst reaction tubes in this manner, a fatty acid ester having a high purity can be obtained as in the case where a reactor having many stages of catalyst reaction tubes is used. Therefore, it is shown that the cost of the apparatus can be reduced by reducing the number of stages of catalyst reaction tubes.
  • a fatty acid ester can be produced through a continuous procedure of adding a lower alcohol without stopping the reaction, and automatically separating by-product glycerin, and thus, production efficiency is high, and production cost can be reduced. Furthermore, the separated glycerin does not require special washing treatment, and thus, the environmental load is low, and the produced fatty acid ester is provided as a biodiesel fuel with less environmental pollution.
US12/745,962 2007-12-14 2008-11-28 Continuous production of biodiesel fuel by enzymatic method Abandoned US20100261235A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2007323381 2007-12-14
JP2007-323381 2007-12-14
PCT/JP2008/072111 WO2009078290A1 (fr) 2007-12-14 2008-11-28 Production en continu de carburant biodiesel par un procédé enzymatique

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2008/072111 A-371-Of-International WO2009078290A1 (fr) 2007-12-14 2008-11-28 Production en continu de carburant biodiesel par un procédé enzymatique

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US14/741,755 Division US9879291B2 (en) 2007-12-14 2015-06-17 Continuous production of biodiesel fuel by enzymatic method

Publications (1)

Publication Number Publication Date
US20100261235A1 true US20100261235A1 (en) 2010-10-14

Family

ID=40795406

Family Applications (2)

Application Number Title Priority Date Filing Date
US12/745,962 Abandoned US20100261235A1 (en) 2007-12-14 2008-11-28 Continuous production of biodiesel fuel by enzymatic method
US14/741,755 Expired - Fee Related US9879291B2 (en) 2007-12-14 2015-06-17 Continuous production of biodiesel fuel by enzymatic method

Family Applications After (1)

Application Number Title Priority Date Filing Date
US14/741,755 Expired - Fee Related US9879291B2 (en) 2007-12-14 2015-06-17 Continuous production of biodiesel fuel by enzymatic method

Country Status (7)

Country Link
US (2) US20100261235A1 (fr)
EP (1) EP2241631B1 (fr)
JP (1) JP5558831B2 (fr)
CN (1) CN101896614A (fr)
BR (1) BRPI0820588A2 (fr)
MY (1) MY153124A (fr)
WO (1) WO2009078290A1 (fr)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5607329B2 (ja) * 2009-09-01 2014-10-15 関西化学機械製作株式会社 酵素法による連続式バイオディーゼル燃料の生産方法
US8889895B2 (en) * 2011-03-08 2014-11-18 Cognis Ip Management Gmbh Process for the distillation of fatty acid esters
JP5986753B2 (ja) * 2012-01-31 2016-09-06 関西化学機械製作株式会社 酵素法による連続式バイオディーゼル燃料の生産方法
CN103305559B (zh) * 2012-03-12 2015-07-22 广州市名花香料有限公司 一种天然风味脂肪酸酯的制备方法
CN104651060B (zh) * 2015-02-03 2017-08-15 江苏卡特环保科技有限公司 生物柴油连续酯交换工艺
KR101534260B1 (ko) * 2015-02-16 2015-07-06 호남바이오영농조합법인 친환경 효소 에너지 조성물 및 이의 제조 방법
CN115106024B (zh) * 2022-07-04 2024-04-16 山东飞扬化工有限公司 一种混流反应器和混流反应设备及其用于生产碳酸酯的方法

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6359896A (ja) * 1986-09-01 1988-03-15 Agency Of Ind Science & Technol 固定化リパ−ゼによる油脂加水分解法
US6982155B1 (en) * 1999-11-26 2006-01-03 Kansai Chemical Engineering Co., Ltd. Process for producing fatty acid lower alcohol ester
US20060063242A1 (en) * 2004-09-20 2006-03-23 Chih-Chung Chou Fuel production
WO2006088254A2 (fr) * 2005-02-21 2006-08-24 Nippon Shokubai Co., Ltd. Methode servant a preparer des esters d'alkyle acides gras et/ou glycerine
WO2007043552A1 (fr) * 2005-10-05 2007-04-19 Kao Corporation Procede pour la production d'une substance utile a l'aide d'une enzyme immobilisee
US20070232818A1 (en) * 2005-11-15 2007-10-04 Domestic Energy Leasing, Llc Transesterification of oil to form biodiesels
CN200967808Y (zh) * 2006-10-26 2007-10-31 冯善茂 环保型生产生物柴油的酯化装置

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000012743A1 (fr) 1998-09-01 2000-03-09 Kansai Chemical Engineering Co., Ltd. Procede de production d'ester d'alcool inferieur
JP2005350632A (ja) * 2004-06-14 2005-12-22 Electric Power Dev Co Ltd バイオディーゼル燃料の製造方法
JP5186083B2 (ja) * 2005-12-21 2013-04-17 株式会社日本触媒 油脂からの脂肪酸アルキルエステル及び／又はグリセリンの製造方法
US7420072B2 (en) * 2006-05-05 2008-09-02 Orbitek, Inc. Apparatus and method for producing biodiesel fuel

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6359896A (ja) * 1986-09-01 1988-03-15 Agency Of Ind Science & Technol 固定化リパ−ゼによる油脂加水分解法
US6982155B1 (en) * 1999-11-26 2006-01-03 Kansai Chemical Engineering Co., Ltd. Process for producing fatty acid lower alcohol ester
US20060063242A1 (en) * 2004-09-20 2006-03-23 Chih-Chung Chou Fuel production
WO2006088254A2 (fr) * 2005-02-21 2006-08-24 Nippon Shokubai Co., Ltd. Methode servant a preparer des esters d'alkyle acides gras et/ou glycerine
US20090069586A1 (en) * 2005-02-21 2009-03-12 Nippon Shokubai Co., Ltd. Method for producing fatty acid alkyl esters and/or glycerin
WO2007043552A1 (fr) * 2005-10-05 2007-04-19 Kao Corporation Procede pour la production d'une substance utile a l'aide d'une enzyme immobilisee
US20070232818A1 (en) * 2005-11-15 2007-10-04 Domestic Energy Leasing, Llc Transesterification of oil to form biodiesels
CN200967808Y (zh) * 2006-10-26 2007-10-31 冯善茂 环保型生产生物柴油的酯化装置

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
English language machine translation of CN200967808 (10/31/2007), pp. 1-3. *
Shimada, Y., et al., Enzymatic alcoholysis for biodiesel fuel production and application of the reactin to oil processing, 2002, Journa of Moecular Catalysis B: Enzymatic, pp 133 - 142 *

Also Published As

Publication number Publication date
US20150284748A1 (en) 2015-10-08
MY153124A (en) 2014-12-31
CN101896614A (zh) 2010-11-24
BRPI0820588A2 (pt) 2014-11-04
JP5558831B2 (ja) 2014-07-23
WO2009078290A1 (fr) 2009-06-25
US9879291B2 (en) 2018-01-30
EP2241631A1 (fr) 2010-10-20
EP2241631B1 (fr) 2015-04-15
EP2241631A4 (fr) 2011-04-27
JPWO2009078290A1 (ja) 2011-04-28

Similar Documents

Publication Publication Date Title
US9879291B2 (en) Continuous production of biodiesel fuel by enzymatic method
Moazeni et al. Enzymatic transesterification for biodiesel production from used cooking oil, a review
Amini et al. State of the art and prospective of lipase-catalyzed transesterification reaction for biodiesel production
Adamczak et al. The application of biotechnological methods for the synthesis of biodiesel
Guldhe et al. Advances in synthesis of biodiesel via enzyme catalysis: Novel and sustainable approaches
Robles-Medina et al. Biocatalysis: towards ever greener biodiesel production
Fjerbaek et al. A review of the current state of biodiesel production using enzymatic transesterification
Ghaly et al. Production of biodiesel by enzymatic transesterification
CN101932717B (zh) 用于脂肪酸烷基酯合成的强力多酶制剂
WO2001038553A1 (fr) Fabrication d'alcool ester inferieur d'acide gras
US20110219675A1 (en) Enzymatic production of fatty acid ethyl esters
Mohan et al. Algae oils as fuels
CN101255348B (zh) 由固定化脂肪酶-透醇膜生物反应器制备生物柴油的方法
Singh et al. Current research and perspectives on microalgae-derived biodiesel
Arcos et al. Continuous enzymatic esterification of glycerol with (poly) unsaturated fatty acids in a packed‐bed reactor
Lee et al. Enzymatic biodiesel synthesis in semi-pilot continuous process in near-critical carbon dioxide
JP5607329B2 (ja) 酵素法による連続式バイオディーゼル燃料の生産方法
JP5986753B2 (ja) 酵素法による連続式バイオディーゼル燃料の生産方法
Ondul et al. Biocatalytic production of biodiesel from vegetable oils
Feltes et al. An overview of enzyme-catalyzed reactions and alternative feedstock for biodiesel production
KR101684455B1 (ko) 고정화 효소를 이용한 연속식 바이오디젤 생산 반응기 및 바이오디젤 생산 방법
Pradhan et al. Microbial biodiesel: a comprehensive study toward sustainable biofuel production
KR101300677B1 (ko) 아임계 이산화탄소 상태에서 반연속적인 효소적 바이오 디젤 제조방법 및 그 제조장치
US20180223236A1 (en) Horizontally inclined trough reactor and uses therefor
WO2012049180A1 (fr) Traitement d'huiles et de graisses

Legal Events

Date Code Title Description
AS Assignment

Owner name: KANSAI CHEMICAL ENGINEERING CO., LTD., JAPAN

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:KURATANI, NOBUYUKI;HAMA, SHINJI;NODA, HIDEO;AND OTHERS;REEL/FRAME:024478/0224

Effective date: 20100414

Owner name: BIO-ENERGY CORPORATION, JAPAN

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:KURATANI, NOBUYUKI;HAMA, SHINJI;NODA, HIDEO;AND OTHERS;REEL/FRAME:024478/0224

Effective date: 20100414

STCB Information on status: application discontinuation

Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION