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WO2018212049A1 - Procédé d'élimination de monoglycéride présent dans du biodiesel - Google Patents

Procédé d'élimination de monoglycéride présent dans du biodiesel Download PDF

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Publication number
WO2018212049A1
WO2018212049A1 PCT/JP2018/018031 JP2018018031W WO2018212049A1 WO 2018212049 A1 WO2018212049 A1 WO 2018212049A1 JP 2018018031 W JP2018018031 W JP 2018018031W WO 2018212049 A1 WO2018212049 A1 WO 2018212049A1
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WIPO (PCT)
Prior art keywords
monoglyceride
fatty acid
stirring
less
hours
Prior art date
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Ceased
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PCT/JP2018/018031
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English (en)
Japanese (ja)
Inventor
悠太 山本
大野　英俊
憲明 細谷
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Idemitsu Kosan Co Ltd
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Idemitsu Kosan Co Ltd
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Priority to JP2019507345A priority Critical patent/JP6641063B2/ja
Publication of WO2018212049A1 publication Critical patent/WO2018212049A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
    • 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
    • C11B7/00—Separation of mixtures of fats or fatty oils into their constituents, e.g. saturated oils from unsaturated oils
    • 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
    • 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

Definitions

  • the present invention relates to a method for removing monoglycerides in fatty acid alkyl ester compositions such as biodiesel.
  • Biodiesel is a diesel fuel mainly composed of fatty acid alkyl esters, and is produced by transesterification between fats such as vegetable fats and oils and alcohols such as methanol.
  • Biodiesel generally contains impurities such as monoglycerides.
  • Monoglycerides cause problems such as filter clogging due to precipitation during the use of biodiesel. Therefore, a technique for removing monoglyceride from biodiesel is required.
  • Patent Document 1 describes that the precipitation (crystallization) of monoglyceride can be carried out under standing conditions, and the standing time is preferably 24 hours or longer.
  • An object of the present invention is to provide a method for removing monoglycerides in fatty acid alkyl ester compositions such as biodiesel.
  • the present inventors considered that the method described in Patent Document 1 has room for improvement in terms of time taken for precipitation (crystallization) of monoglyceride.
  • the present inventors further show that the monoglyceride can be efficiently precipitated by stirring the fatty acid alkyl ester composition containing the monoglyceride under specific conditions, so that the monoglyceride can be easily removed.
  • the headline and the present invention were completed.
  • a method for producing a fatty acid alkyl ester comprising: A method comprising the following steps (A) and (B): (A) a step of stirring a mixture containing a fatty acid alkyl ester and a monoglyceride to precipitate the monoglyceride; (B) A step of removing the precipitated monoglyceride from the mixture. [2] The method, wherein the stirring power during stirring in the step (A) is 5 W / m 3 to 1000 W / m 3 .
  • the said method including the process of hydrogenating the said mixture before implementation of the said process (A).
  • the method further comprises the step of adding monoglyceride seed crystals to the mixture before or during the step (A).
  • the said method including the process of adding light oil to the said mixture before implementation of the said process (A) or during implementation.
  • the said method including the process of removing the said monoglyceride which remains in the said mixture using adsorption agent after implementation of the said process (B).
  • the stirring power during the stirring in the step (A) is a 14W / m 3 ⁇ 391W / m 3, said process.
  • the method as described above, wherein the tip speed of the stirring blade during stirring in the step (A) is 0.4 m / s to 1.4 m / s.
  • the figure which shows the correlation with crystallization temperature, a monoglyceride removal rate, and a fatty-acid alkylester yield The figure which shows the correlation with stirring power, a monoglyceride removal rate, and a fatty-acid alkylester yield.
  • the figure which shows the correlation with crystallization time, a monoglyceride removal rate, and a fatty-acid alkylester yield The figure which shows the correlation with stirring power, a fatty-acid alkylester yield, and a filtration rate.
  • the method of the present invention is a method for removing monoglycerides comprising the following steps (A) and (B): (A) a step of stirring a mixture containing a fatty acid alkyl ester and a monoglyceride to precipitate the monoglyceride; (B) A step of removing the precipitated monoglyceride from the mixture.
  • fatty acid alkyl esters can be obtained by the method of the present invention. That is, the method of the present invention may be read as a method for producing a fatty acid alkyl ester including the steps (A) and (B).
  • step (A) is also referred to as “stirring step”.
  • step (B) is also referred to as a “removal step”.
  • the mixture for carrying out the step (A) is also referred to as “crude mixture”.
  • the fatty acid alkyl ester obtained by the method of the present invention is also referred to as “product”.
  • the fatty acid alkyl ester itself or a mixture (composition) containing the fatty acid alkyl ester itself is also referred to as a “fatty acid alkyl ester composition”. “Precipitation” is also referred to as “crystallization”.
  • the crude mixture is a mixture containing a fatty acid alkyl ester and a monoglyceride.
  • the crude mixture is a fatty acid alkyl ester composition containing monoglycerides.
  • the crude mixture may be composed of a fatty acid alkyl ester and a monoglyceride, and may further contain other components. Examples of other components include diglyceride, triglyceride, glycerin, alcohol, moisture, and salt.
  • the content (concentration) of each component in the crude mixture is not particularly limited as long as the effects of the present invention are not impaired.
  • the total content of fatty acid alkyl ester and monoglyceride in the crude mixture is, for example, 90% (w / w) or more, 95% (w / w) or more, 97% (w / w) or more, based on the total amount of the crude mixture. It may be 98% (w / w) or more, or 99% (w / w) or more.
  • the content of the fatty acid alkyl ester in the crude mixture is, for example, 80% (w / w) or more, 85% (w / w) or more, 90% (w / w) or more, 95% (total of the crude mixture) w / w) or more, 97% (w / w) or more, 98% (w / w) or more, or 99% (w / w) or more, and less than 100% (w / w).
  • the content of monoglyceride in the crude mixture is, for example, 0.2% (w / w) or more, 0.25% (w / w) or more, 0.3% (w / w) or more with respect to the total amount of the crude mixture.
  • the content of monoglyceride in the crude mixture is, for example, 0.2% (w / w) or more, 0.25% (w / w) or more, 0.3% with respect to the content of the fatty acid alkyl ester in the crude mixture.
  • the content of each component in the crude mixture (for example, the range of the content exemplified above), when adding external components such as light oil to the crude mixture, unless otherwise specified,
  • the content in the crude mixture is shown.
  • the content of each component in the crude mixture after the addition of the external component may be a range calculated based on, for example, the content range exemplified above and the addition amount ratio of the external component.
  • Examples of the fatty acid and alkyl group constituting the fatty acid alkyl ester include those described later. That is, examples of the fatty acid alkyl ester include esters composed of combinations of constituent fatty acids described later and alkyl groups described later. That is, examples of fatty acid alkyl esters include saturated fatty acid alkyl esters and unsaturated fatty acid alkyl esters. Examples of unsaturated fatty acid alkyl esters include monounsaturated fatty acid alkyl esters and polyunsaturated fatty acid alkyl esters. Examples of unsaturated fatty acid alkyl esters include trans fatty acid alkyl esters and cis fatty acid alkyl esters. Moreover, fatty acid methyl ester is mentioned as a fatty-acid alkylester. The crude mixture may contain one fatty acid alkyl ester or may contain two or more fatty acid alkyl esters.
  • Examples of fatty acids constituting monoglycerides include those described below. That is, examples of the monoglyceride include monoglycerides of constituent fatty acids described later. That is, examples of monoglycerides include saturated fatty acid monoglycerides and unsaturated fatty acid monoglycerides. Examples of unsaturated fatty acid monoglycerides include monounsaturated fatty acid monoglycerides and polyunsaturated fatty acid monoglycerides.
  • the position of the constituent fatty acid in the monoglyceride is not particularly limited. The monoglyceride may have a constituent fatty acid at the 1st position (synonymous with the 3rd position) or at the 2nd position.
  • the crude mixture may contain one monoglyceride or may contain two or more monoglycerides.
  • Examples of the constituent fatty acid include fatty acids having 6 to 26 carbon atoms, particularly 8 to 24 carbon atoms, and more particularly 12 to 18 carbon atoms.
  • Examples of fatty acids include saturated fatty acids and unsaturated fatty acids.
  • Examples of unsaturated fatty acids include monounsaturated fatty acids and polyunsaturated fatty acids.
  • Examples of unsaturated fatty acids include trans fatty acids and cis fatty acids. Trans fatty acids are produced, for example, by hydrogenation.
  • fatty acids include caprylic acid (C8: 0), capric acid (C10: 0), lauric acid (C12: 0), myristic acid (C14: 0), palmitic acid (C16: 0), and stearic acid (C18: 0), saturated fatty acids such as arachidic acid (C20: 0), behenic acid (C22: 0), lignoceric acid (C24: 0), palmitoleic acid (C16: 1), oleic acid (C18: 1), Monovalent unsaturated fatty acids such as eicosenoic acid (C20: 1) and erucic acid (C22: 1), diunsaturated fatty acids such as linoleic acid (C18: 2), trivalent unsaturation such as linolenic acid (C18: 3) Saturated fatty acids, tetravalent unsaturated fatty acids such as stearidonic acid (C18: 4), pentavalent unsaturated fatty
  • Examples of the alkyl group include an alkyl group having 1 to 6 carbon atoms.
  • Examples of the alkyl group include a straight chain alkyl group and a branched chain alkyl group.
  • Specific examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, 1-butyl group, 2-butyl group, isobutyl group, tert-butyl group, 1-pentyl group, 3-pentyl group, 3 -Methyl-1-butyl group, 2,2-dimethyl-1-propyl group, 1-hexyl group, 2-hexyl group, 2-methyl-1-pentyl group, 3,3-dimethyl-1-butyl group It is done.
  • Examples of the alkyl group include a methyl group.
  • composition of the fatty acid alkyl ester or monoglyceride is not particularly limited as long as the effects of the present invention are not impaired.
  • the composition of these components can be appropriately set according to various conditions such as the use and usage of the product.
  • the composition exemplified below may be suitable when the product is used as a diesel fuel.
  • the content of monounsaturated fatty acid alkyl ester in the crude mixture is, for example, 5% (w / w) or more, 10% (w / w) or more, 20% (w / W) or more, 30% (w / w) or more, 40% (w / w) or more, 50% (w / w) or more, 60% (w / w) or more, or 70% (w / w) or more 95% (w / w) or less, 90% (w / w) or less, 80% (w / w) or less, 70% (w / w) or less, 60% (w / w) or less , 50% (w / w) or less, 40% (w / w) or less, or 30% (w / w) or less, or a non-conflicting combination thereof.
  • the content of polyunsaturated fatty acid alkyl ester in the crude mixture is, for example, 10% (w / w) or less, 7% (w / w) or less, 5% (w / W) or less, 3% (w / w) or less, 2% (w / w) or less, 1% (w / w) or less, or zero.
  • the content of the trans fatty acid alkyl ester in the crude mixture is, for example, 28% (w / w) or less, 17% (w / w) or less, 10% (w / w) based on the total amount of the fatty acid alkyl ester in the crude mixture. 7% (w / w) or less, 5% (w / w) or less, 3% (w / w) or less, 2% (w / w) or less, 1% (w / w) or less, or zero There may be.
  • the content of the unsaturated monoglyceride in the crude mixture is, for example, 10% (w / w) or less, 7% (w / w) or less, 5% (w / w) or less, based on the total amount of monoglyceride in the crude mixture. % (W / w) or less, 2% (w / w) or less, 1% (w / w) or less, or zero.
  • the crude mixture can be produced, for example, by transesterification of triglyceride and alcohol. That is, the method of the present invention may include a step of transesterifying triglyceride and alcohol to produce a crude mixture. This process is also referred to as “transesterification process”.
  • the triglyceride is not particularly limited as long as it provides a desired constituent fatty acid.
  • examples of such triglycerides include those having the constituent fatty acids exemplified above and those having constituent fatty acids that can be converted to the constituent fatty acids exemplified above.
  • fats and oils can be used as the triglyceride.
  • the fats and oils include natural fats and oils, waste fats and oils derived from them, and processed products thereof.
  • natural fats and oils include plant-derived fats and oils (vegetable fats and oils) and animal-derived fats and oils (animal fats and oils).
  • Examples of vegetable oils include rapeseed oil, sesame oil, jatropha oil, soybean oil, corn oil, sunflower oil, palm oil, palm kernel oil, cottonseed oil, rice oil, coconut oil, safflower oil.
  • Examples of animal fats include beef tallow, pork tallow, chicken tallow, and fish oil.
  • Examples of the processed product include hardened oil (oil and fat whose degree of unsaturation has been reduced by hydrogenation).
  • As fats and oils one kind of fats and oils may be used, or two or more kinds of fats and oils may be used in combination.
  • Alcohol is not particularly limited as long as it provides a desired alkyl group.
  • examples of such an alcohol include those having the above-exemplified alkyl group and those having an alkyl group that can be converted into the above-exemplified alkyl group.
  • examples of the alcohol include linear or branched alkyl alcohols having 1 to 6 carbon atoms.
  • alcohols include methanol, ethanol, propanol, isopropanol, 1-butanol, 2-butanol, isobutanol, tert-butyl alcohol, 1-pentanol, 3-pentanol, 3-methyl-1-butanol, Examples include 2,2-dimethyl-1-propanol, 1-hexanol, 2-hexanol, 2-methyl-1-pentanol, and 3,3-dimethyl-1-butanol.
  • methanol is mentioned in particular.
  • the alcohol one kind of alcohol may be used, or two or more kinds of alcohols may be used in combination.
  • the transesterification reaction can be carried out, for example, by bringing triglyceride and alcohol into contact in the presence of a catalyst.
  • the catalyst include an alkali catalyst, an acid catalyst, a biocatalyst (such as lipase), and a solid catalyst.
  • the reaction conditions can be appropriately set according to various conditions such as the type of raw material and the type of catalyst.
  • the molar ratio of triglyceride to alcohol (triglyceride: alcohol) may be, for example, 1: 3 to 1: 100, 1: 3 to 1:20, or 1: 3 to 1:12.
  • the reaction temperature may be, for example, 40 to 120 ° C.
  • the reaction time may be, for example, 0.1 to 6 hours.
  • the reaction may be carried out batchwise or continuously.
  • reaction product containing a fatty acid alkyl ester is obtained.
  • the obtained reaction product can be used as a crude mixture as it is or after processing such as purification.
  • purification treatment include fractionation, washing with water, and dehydration.
  • the purification treatment can be performed, for example, so that the composition of the above-exemplified crude mixture is obtained.
  • biodiesel Fatty acid alkyl esters produced from biological oils and fats are generally called “biodiesel”. That is, the crude mixture may specifically be biodiesel containing monoglyceride, for example.
  • the crude mixture may be hydrogenated. That is, the method of the present invention may include a step of hydrogenating the crude mixture. This process is also referred to as a “hydrogenation process”. In other words, the hydrogenation step may be a step of hydrogenating the crude mixture to obtain a hydrogenated crude mixture.
  • the term “crude mixture” can be used both before and after hydrogenation, unless otherwise specified. Hydrogenation can be carried out specifically on fatty acid alkyl esters and / or monoglycerides or other components having unsaturated bonds. Hydrogenation can reduce the degree of unsaturation of the constituent fatty acids of these components. Hydrogenation can be carried out, for example, so as to obtain the composition of the above-exemplified crude mixture.
  • the crude mixture may have the above-exemplified composition without a hydrogenation step.
  • the degree of unsaturation of the fatty acid constituting the fatty acid alkyl ester By reducing the degree of unsaturation of the fatty acid constituting the fatty acid alkyl ester, the oxidative stability of the fatty acid alkyl ester can be increased.
  • the saturated fatty acid alkyl ester has a higher melting point than the unsaturated fatty acid alkyl ester and may not be suitable for diesel fuel.
  • hydrogenation may be performed, for example, such that polyunsaturated fatty acid alkyl esters are converted to monounsaturated fatty acid alkyl esters. Saturated fatty acid monoglycerides are easier to crystallize than unsaturated fatty acid monoglycerides.
  • hydrogenation may be performed, for example, such that unsaturated fatty acid monoglycerides are converted to saturated fatty acid monoglycerides.
  • hydrogenation may be performed, for example, such that polyunsaturated fatty acid alkyl ester is converted to monounsaturated fatty acid alkyl ester and unsaturated fatty acid monoglyceride is converted to saturated fatty acid monoglyceride.
  • Examples of the hydrogenation method include the methods described in WO2011 / 105291 and WO2015 / 133487. Specifically, the crude mixture is specifically brought into contact with a low hydrogen pressure hydrogen atmosphere in the presence of a hydrogenation catalyst containing a noble metal selected from Group 8 to 10 noble metals of the periodic table, for example. It can be hydrogenated (WO2011 / 105291). Examples of such noble metals include palladium (Pd), platinum (Pt), rhodium (Rh), iridium (Ir), rhenium (Re), and ruthenium (Ru).
  • the hydrogen pressure is an absolute pressure, for example, 0.2 MPa or more, 1 MPa or less, 0.7 MPa or less, or 0.5 MPa or less, or a combination thereof.
  • the hydrogen pressure is an absolute pressure, specifically, for example, may be 0.2 to 0.7 MPa.
  • the reaction temperature may be, for example, 80 to 130 ° C.
  • the hydrogenation catalyst can be used efficiently and stably by allowing oxygen to be present in the reaction system (WO2015 / 133487).
  • the amount of oxygen present in the reaction system is, for example, 150 to 3500 ppm (mol / mol) with respect to the amount of the crude mixture (for example, converted to the number of moles based on the average molecular weight of palm oil-derived biodiesel) It may be 300 to 2000 ppm (mol / mol), or 400 to 1500 ppm (mol / mol).
  • the crude mixture may be added with light oil (that is, containing light oil). That is, the method of the present invention may include a step of adding light oil to the crude mixture.
  • the term “crude mixture” can be used in any case before or after the addition of light oil, unless otherwise specified.
  • the light oil can be added to the crude mixture before or during the implementation of step (A). “During execution of step (A)” refers to a period from the start to the end of step (A).
  • the amount of light oil added is, for example, 0.5 parts by volume or more, 0.7 parts by volume or more, 1 part by volume or more, 1.5 parts by volume with respect to 1 part by volume of the crude mixture (before adding the light oil).
  • the amount of light oil added is not particularly limited as long as the effects of the present invention are not impaired.
  • the amount of light oil added is, for example, 0.5 to 33 parts by volume, 0.5 to 2 parts by volume, 1.5 parts by volume with respect to 1 part by volume of the crude mixture (before addition of light oil).
  • light oil examples include general light oil that can be used in diesel engines. Specific examples of such light oil include Special No. 1 diesel oil, No. 1 diesel oil, No. 2 diesel oil, No. 3 diesel oil, and Special No. 3 diesel oil standardized in JIS K2204. By adding light oil, for example, the crystallization temperature can be lowered while maintaining the crystallization efficiency of monoglyceride.
  • the crude mixture may be added with monoglyceride seed crystals (ie containing monoglyceride seed crystals). That is, the method of the present invention may include a step of adding monoglyceride seed crystals to the crude mixture.
  • the term “crude mixture” can be used in any case before or after seeding of monoglyceride, unless otherwise specified.
  • Monoglyceride seed crystals can be added to the crude mixture before or during step (A).
  • Monoglyceride seed crystals may be added to the crude mixture, for example, before monoglyceride crystallization begins.
  • the amount of monoglyceride seed crystals added is not particularly limited as long as the effects of the present invention are not impaired.
  • the amount of monoglyceride seed crystals added may be, for example, 1 to 10 mg with respect to 100 g of the crude mixture (before adding the monoglyceride seed crystals).
  • Examples of the monoglyceride constituting the seed crystal include the monoglycerides exemplified above.
  • the monoglyceride contained in the crude mixture and the monoglyceride constituting the seed crystal may or may not be the same.
  • the method of the present invention includes a stirring step (step (A)).
  • Step (A) is carried out such that monoglycerides are precipitated.
  • Step (A) can be carried out in particular such that monoglycerides are selectively precipitated.
  • “Monoglyceride is selectively precipitated” means that the monoglyceride is selectively precipitated as compared with the fatty acid alkyl ester.
  • “monoglyceride selectively precipitates” means that the amount of monoglyceride deposited relative to the amount of fatty acid alkyl ester deposited compared to the ratio of the content of monoglyceride to the content of fatty acid alkyl ester in the crude mixture. The ratio is high.
  • the conditions (for example, the number of stirring, the crystallization temperature, the crystallization time) of the step (A) are not particularly limited as long as the effects of the present invention are not impaired.
  • Step (A) can be performed using, for example, a stirring device. That is, for example, the crude mixture can be introduced into a stirrer and the crude mixture can be stirred.
  • the stirring apparatus should just be comprised so that a process (A) can be implemented on desired conditions.
  • the stirring device may include, for example, a container (stirring tank) in which stirring of the introduced crude mixture is performed.
  • the stirring apparatus may be provided with a means for stirring the introduced crude mixture. Examples of such means include a stirring blade. That is, the rough mixture can be stirred by applying a motion such as rotation or movement to the stirring blade in contact with the rough mixture.
  • the stirring apparatus may be provided with a means for controlling the temperature of the introduced crude mixture.
  • the stirring apparatus may be provided with a means for scraping off the component deposited on the wall surface of the stirring tank.
  • Such means include a scraper.
  • the stirring device include a crystallization device including stirring means.
  • a specific example of such a crystallizer is a scraping crystallizer (Tsukishima Kikai Co., Ltd.).
  • the degree of stirring in step (A) is not particularly limited, and a sufficient effect can be obtained if a flow occurs in the stirring tank (that is, if a flow occurs in the crude mixture).
  • Stirring speed in the step (A) (stirring speed), as a stirring power, for example, 5W / m 3 or more, 7W / m 3 or more, 10 W / m 3 or more, 14W / m 3 or more, 20W / m 3 or more, 30 W / m 3 or more, 50 W / m 3 or more, 70 W / m 3 or more, 100W / m 3 or more, 150 W / m 3 or more, 161W / m 3 or more, 200 W / m 3 or more, 250 W / m 3 or more, or 300 W / It may also be m 3 or more, 1000W / m 3 or less, 700 W / m 3 or less, 500 W / m 3 or less, 400W / m 3 or less, 391W / m 3 or less, 300 W / m 3 or less, 250 W / m 3 or less , 200 W / m 3 or less, 150 W
  • Stirring speed as a stirring power, specifically, for example, at 5W / m 3 ⁇ 1000W / m 3, 14W / m 3 ⁇ 391W / m 3 or 161W / m 3 ⁇ 391W / m 3, There may be.
  • the stirring power during stirring in the step (A) may be in the above range.
  • the number of stirring (stirring speed) in the step (A) is, for example, 0.2 m / s or more, 0.3 m / s or more, 0.4 m / s or more, 0.5 m / s or more as the tip speed of the stirring blade.
  • the number of stirring is specifically the tip speed of the stirring blade, for example, 0.2 m / s to 3 m / s, 0.4 m / s to 1.4 m / s, or 0.9 m / s. It may be up to 1.4 m / s.
  • the tip speed of the stirring blade during stirring in the step (A) may be in the above range.
  • the tip speed of the stirring blade refers to the speed of the maximum diameter portion around the circle on the assumption that the stirring blade is extended to the inner wall of the stirring tank. Further, the tip speed of the stirring blade may be read as the tip speed of the scraper when a stirring device including a scraper is used.
  • the temperature of the step (A) (the temperature of the crude mixture at the time of carrying out the step (A); also referred to as “crystallization temperature”) is, for example, 2 ° C. or higher, 3 ° C. or higher, 4 ° C. or higher, 5 ° C. or higher, 6 ° C. 7 ° C or higher, 8 ° C or higher, 9 ° C or higher, 10 ° C or higher, 11 ° C or higher, 12 ° C or higher, 13 ° C or higher, 14 ° C or higher, 15 ° C or higher, or 16 ° C or higher. 19 ° C. or lower, 17 ° C. or lower, 16 ° C. or lower, 15 ° C. or lower, 14 ° C.
  • the crystallization temperature can be set in consideration of, for example, whether or not light oil is added and the amount of light oil added. That is, for example, the crystallization temperature may be set lower when light oil is added, or may be set lower as the amount of light oil added is larger. Specifically, the crystallization temperature may be, for example, 14 ° C. to 20 ° C., 14 ° C. to 19 ° C., 14 ° C.
  • the crystallization temperature is specifically, for example, 5 ° C to 15 ° C, 5 ° C to 10 ° C, 5 ° C to 9 ° C, 5 ° C to 8 ° C, 5 ° C to 7 ° C, 3 ° C to 9 ° C, It may be 3 ° C. to 8 ° C., 3 ° C. to 7 ° C., or 3 ° C. to 6 ° C., and particularly within the range when light oil is added.
  • the crystallization temperature is too low, fatty acid alkyl esters can be precipitated, and if the crystallization temperature is too high, monoglyceride may be insufficiently precipitated. That is, the crystallization temperature may be set low as long as the fatty acid alkyl ester does not precipitate.
  • the time of the step (A) (the time from the start to the end of the step (A); also referred to as “crystallization time”) is, for example, 0.5 hours or more, 1 hour or more, 1.5 hours or more, 2 hours or more 2.5 hours or more, 3 hours or more, 3.5 hours or more, 4 hours or more, 4.5 hours or more, 5 hours or more, 5.5 hours or more, 6 hours or more, 7 hours or more, 8 hours or more, or It may be 10 hours or more, 20 hours or less, 15 hours or less, 12 hours or less, 10 hours or less, 8 hours or less, 7 hours or less, 6 hours or less, 5.5 hours or less, 5 hours or less, or 4. It may be 5 hours or less, or a consistent combination thereof.
  • the crystallization time may be, for example, 0.5 hours to 20 hours, 0.5 hours to 10 hours, or 3 hours to 6 hours. If the crystallization time is too long, the fatty acid alkyl ester may precipitate, and if the crystallization time is too short, the monoglyceride may be insufficiently precipitated.
  • Stirring may be carried out continuously or intermittently.
  • the agitation may be performed only once, or may be performed twice or more.
  • it is set as "once" until it stops after stirring starts.
  • conditions such as the number of stirring and the crystallization temperature may or may not be constant.
  • conditions such as the number of stirrings, crystallization temperature, stirring duration, etc. may or may not be the same each time. .
  • the number of stirrings may be in the above range during the entire period of the step (A), but may be in the above range only during a part of the step (A) (that is, temporarily out of the above range). Good).
  • the stirring may be temporarily performed with the number of stirrings outside the above range, or may be temporarily stopped.
  • the number of stirring (stirring speed) in the step (A) is within a certain range (for example, the stirring power during stirring in the step (A) or the tip speed of the stirring blade is within a certain range)” It is not limited to the case where the number of stirrings is within the range in the whole period of A), and the number of stirrings is within the range only during a part of the step (A) (that is, the stirring number is temporarily out of the range). It is also included.
  • the crystallization temperature may be within the above range during the entire period of the step (A), but may be within the above range only during a part of the step (A) (that is, temporarily within the above range). May be off.)
  • the step (A) may be started at a crystallization temperature outside the above range (for example, a crystallization temperature higher than the above range), and the crystallization temperature may be allowed to reach the above range during the execution of the step (A).
  • the crystallization temperature may be, for example, in the above range at the end of the step (A).
  • the crystallization temperature may be in the above range, for example, at least from the start of crystallization of monoglyceride until the end of the step (A).
  • the temperature of the step (A) is in a certain range” is not limited to the case where the crystallization temperature is within the range in the entire period of the step (A), but only in a partial period of the step (A). The case where the crystallization temperature is within the range (that is, the crystallization temperature temporarily falls outside the range) is also included.
  • the “partial period” or “temporary” length and timing here are not particularly limited as long as the effects of the present invention are not impaired.
  • “Partial period” means, for example, 50% or more, 60% or more, 70% or more, 80% or more, 90% or more, 95% or more, 97% or more of the entire period of step (A), Or it may be a period of 99% or more.
  • “Partial period” means, for example, 50% or more, 60% or more, 70% or more, 80% or more, 90% or more, 95% or more of the period in which the stirring in step (A) is performed 97% or more, or 99% or more.
  • the step (A) may include a period during which stirring is stopped (also referred to as “residence time”) in addition to a period during which stirring is performed (also referred to as “stirring time”).
  • Crystallization time stirring time + residence time.
  • the “period during which stirring is performed (stirring time)” is the total period during which stirring is performed.
  • the “period during which stirring is stopped (residence time)” refers to the total period during which stirring is stopped.
  • the stirring time is, for example, 0.5 hours or more, 1 hour or more, 1.5 hours or more, 2 hours or more, 2.5 hours or more, 3 hours or more, 3.5 hours or more, 4 hours or more, or 4.5 May be 10 hours or less, 8 hours or less, 7 hours or less, 6 hours or less, 5.5 hours or less, 5 hours or less, or 4.5 hours or less, and they are not inconsistent. It may be a combination. Specifically, the stirring time may be, for example, 0.5 hours to 10 hours, or 3 hours to 6 hours.
  • Residence time is, for example, 0 hours or more, 0.5 hours or more, 1 hour or more, 1.5 hours or more, 2 hours or more, 2.5 hours or more, 3 hours or more, 3.5 hours or more, 4 hours or more, Or 4.5 hours or more, or 10 hours or less, 8 hours or less, 7 hours or less, 6 hours or less, 5.5 hours or less, 5 hours or less, or 4.5 hours or less, They may be a combination that does not contradict them.
  • the residence time may be, for example, 0 to 10 hours.
  • the method of the present invention includes a removal step (step (B)).
  • Step (B) can be performed by solid-liquid separation means.
  • Such means include natural sedimentation, centrifugation, and filtration.
  • an appropriate filter such as a filter paper or a filtration membrane can be used.
  • the cleaning liquid contains a fatty acid alkyl ester.
  • the cleaning liquid can be used by mixing with a product, for example. After mixing, the medium used for washing can be appropriately separated from the product.
  • the medium used for washing is preferably a medium having low monoglyceride solubility. Such a medium includes methanol.
  • Monoglyceride can be used by returning to the raw material of the transesterification step, for example, as a fatty acid alkyl ester source.
  • the method of the present invention can be carried out batchwise, semi-batchwise or continuously.
  • the crude mixture may be continuously supplied to the stirrer to carry out step (A), and the stirred product may be continuously withdrawn for use in step (B).
  • the method of the present invention may include a step of removing the residual monoglyceride from the crude mixture from which the monoglyceride has been removed (crude mixture after the implementation of the step (B)). Residual monoglycerides can be removed, for example, using an adsorbent.
  • the adsorbent include silica gel, clay mineral (active clay, montmorillonite, etc.), zeolite, diatomaceous earth, magnesium silicate, and alumina.
  • monoglycerides can be removed and a product (fatty acid alkyl ester) can be obtained.
  • the monoglyceride removal rate in the method of the present invention is, for example, 10% or more, 20% or more, 30% or more, 40% or more, 50% or more, 60% or more, 70% or more, 80% or more, 90% or more, 95%. It may be 97% or more, or 99% or more.
  • the fatty acid alkyl ester yield in the method of the present invention may be, for example, 90% or more, 95% or more, 97% or more, or 99% or more.
  • the product is, in other words, a fatty acid alkyl ester composition.
  • the product may be a fatty acid alkyl ester composition from which monoglycerides have been removed, or a fatty acid alkyl ester composition from which the monoglyceride concentration has been reduced.
  • the product may be composed of a fatty acid alkyl ester, and may further contain other components. Examples of other components include monoglyceride, diglyceride, triglyceride, glycerin, alcohol, water, and salt.
  • the content of monoglyceride in the product is, for example, 0.3% (w / w) or less, 0.25% (w / w) or less, 0.2% (w / w) or less with respect to the total product. 0.15% (w / w) or less, 0.1% (w / w) or less, 0.5% (w / w) or less, or zero.
  • the content of monoglyceride in the product is, for example, 0.3% (w / w) or less, 0.25% (w / w) or less, 0.2% with respect to the content of the fatty acid alkyl ester in the product.
  • It may be (w / w) or less, 0.15% (w / w) or less, 0.1% (w / w) or less, 0.5% (w / w) or less, or zero.
  • content of fatty acid alkyl ester in the product and the composition of fatty acid alkyl ester and monoglyceride for example, types and abundance ratios of constituent fatty acids and alkyl groups
  • descriptions of those in the crude mixture can be applied mutatis mutandis.
  • each component in the product for example, the range of the content exemplified above or applied mutatis mutandis
  • an external component such as light oil
  • the range converted into content in a product when it is assumed that the component is not added is shown. That is, for example, when 2 parts by volume of light oil is added to 1 part by volume of the crude mixture and the method of the present invention is carried out, 3 times the actual content of each component in the product containing light oil is It suffices if it is within the range of the content.
  • the monoglyceride removal rate and the fatty acid alkyl ester yield may be calculated by correcting the content (concentration) of each component according to the addition mode of the external component.
  • the product can be used as, for example, diesel fuel.
  • the product can be used as diesel fuel, for example, alone or mixed with light oil.
  • hydrogenation was carried out using a 0.5 wt% Pd alumina supported catalyst at a pressure of 1.0 MPaG, a temperature of 100 ° C., a WHSV24hr ⁇ 1 , and an H 2 / diene ratio of 2.2 mol / mol.
  • Partially hydrogenated biodiesel contains fatty acid methyl ester, C14: 0: 1.2 wt%, C16: 0: 43.2 wt%, C18: 2: 1.7 wt%, C18: 1: 43.4 wt%, C18: 0: 9.4 wt%, other (including C12: 0, C20: 0, C20: 1, C22: 0, C24: 0): 1 wt% or less.
  • the partially hydrogenated biodiesel contained 0.49 wt% monoglyceride, 0.13 wt% diglyceride, 0.06 wt% triglyceride, and 0.05 wt% glycerin.
  • Crystallization was carried out by adding several mg of monoglyceride as seed crystals in advance to 100 g of partially hydrogenated biodiesel at a crystallization temperature of 17 ° C., stirring power of 161 W / m 3 , crystallization time of 3 hours, and normal pressure.
  • the filtrate had a monoglyceride concentration of 0.18 wt% and a fatty acid methyl ester yield of 98%.
  • Crystallization was carried out by adding several mg of monoglyceride as seed crystals in advance to 100 g of partially hydrogenated biodiesel at a crystallization temperature of 17 ° C., stirring power of 14 W / m 3 , crystallization time of 6 hours, and normal pressure.
  • the filtrate had a monoglyceride concentration of 0.20 wt% and a fatty acid methyl ester yield of 98%.
  • Crystallization was performed by adding several mg of monoglyceride to be seeded in advance to 100 g of partially hydrogenated biodiesel at a crystallization temperature of 17 ° C., stirring power of 161 W / m 3 , crystallization time of 9 hours, and normal pressure.
  • the filtrate had a monoglyceride concentration of 0.18 wt% and a fatty acid methyl ester yield of 97%.
  • Crystallization was performed by adding several mg of monoglyceride as a seed crystal in advance to 100 g of partially hydrogenated biodiesel at a crystallization temperature of 17 ° C, stirring power of 161 W / m 3 , crystallization time of 1 hour, and normal pressure.
  • the filtrate had a monoglyceride concentration of 0.33 wt% and a fatty acid methyl ester yield of 99%.
  • Test Example 10 70 parts by volume of No. 1 diesel oil was mixed with 30 parts by volume of partially hydrogenated biodiesel to prepare a diesel oil-containing biodiesel. Crystallization was carried out by adding several mg of monoglyceride as seed crystals to 100 g of light oil-containing biodiesel in advance at a crystallization temperature of 5 ° C, stirring power of 161 W / m 3 , crystallization time of 6 hours, and normal pressure.
  • the monoglyceride concentration in the filtrate was 0.08 wt% (0.27 wt% in terms of concentration in biodiesel before mixing with diesel oil), and the fatty acid methyl ester yield was 98.9 wt%.
  • the stirring was continued during the crystallization time with a predetermined stirring power (the same applies to the following test examples). In addition, stirring was started at 40 ° C., and the temperature reached a predetermined crystallization temperature during stirring (the same applies to the following test examples).
  • Test Example 11 50 parts by volume of No. 1 diesel oil was mixed with 50 parts by volume of partially hydrogenated biodiesel to prepare a diesel oil-containing biodiesel. Crystallization was performed by adding several mg of monoglyceride as a seed crystal to 100 g of biodiesel containing light oil in advance at a crystallization temperature of 10 ° C, stirring power of 161 W / m 3 , crystallization time of 6 hours, and normal pressure.
  • the monoglyceride concentration of the filtrate was 0.21wt% (0.42wt% in terms of the concentration in biodiesel before mixing with light oil), and the fatty acid methyl ester yield was 98.7 wt%.
  • Example 2 The results are shown in Table 2.
  • “raw material” refers to biodiesel before mixing with light oil.
  • the data of Test Example 8 is a reprint of the data obtained in Example ⁇ 1>.
  • Test Example 10 the yield of fatty acid methyl ester was sufficiently high, and the monoglyceride concentration was sufficiently reduced.
  • Test Example 11 the yield of fatty acid methyl ester was sufficiently high, but the monoglyceride concentration was high. This is presumably because the monoglyceride was dissolved in the light oil and remained because the crystallization temperature was high.
  • monoglycerides in fatty acid alkyl ester compositions such as biodiesel can be removed.

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Abstract

L'invention concerne un procédé d'élimination d'un monoglycéride, qui est une impureté, à partir d'une composition d'ester alkylique d'acide gras telle qu'un biodiesel. Un monoglycéride, qui est une impureté, peut être cristallisé et éliminé par agitation d'une composition d'ester alkylique d'acide gras contenant le monoglycéride dans des conditions spécifiques.
PCT/JP2018/018031 2017-05-19 2018-05-10 Procédé d'élimination de monoglycéride présent dans du biodiesel Ceased WO2018212049A1 (fr)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01117845A (ja) * 1987-10-30 1989-05-10 Nippon Oil & Fats Co Ltd モノグリセリドの精製法
JP2002030295A (ja) * 2000-07-18 2002-01-31 Kanegafuchi Chem Ind Co Ltd 食用油脂の分別法
JP2005324082A (ja) * 2004-05-12 2005-11-24 Mitsubishi Chemicals Corp 同時分割法による化合物の相互分離方法
JP2008071730A (ja) * 2006-08-14 2008-03-27 Sony Corp 非水電解質二次電池
WO2009028154A1 (fr) * 2007-08-28 2009-03-05 J-Oil Mills, Inc. Procédé de fractionnement à sec et huile de palme hautement liquéfiée préparée en utilisant ce procédé
WO2011105291A1 (fr) * 2010-02-24 2011-09-01 独立行政法人産業技術総合研究所 Procédé de fabrication de biocarburant diesel et composition de biocarburant diesel
WO2015056767A1 (fr) * 2013-10-18 2015-04-23 独立行政法人産業技術総合研究所 Procédé pour produire du carburant biodiesel de haute qualité

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5561452B2 (ja) * 2006-08-31 2014-07-30 学校法人日本大学 バイオディーゼル燃料

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01117845A (ja) * 1987-10-30 1989-05-10 Nippon Oil & Fats Co Ltd モノグリセリドの精製法
JP2002030295A (ja) * 2000-07-18 2002-01-31 Kanegafuchi Chem Ind Co Ltd 食用油脂の分別法
JP2005324082A (ja) * 2004-05-12 2005-11-24 Mitsubishi Chemicals Corp 同時分割法による化合物の相互分離方法
JP2008071730A (ja) * 2006-08-14 2008-03-27 Sony Corp 非水電解質二次電池
WO2009028154A1 (fr) * 2007-08-28 2009-03-05 J-Oil Mills, Inc. Procédé de fractionnement à sec et huile de palme hautement liquéfiée préparée en utilisant ce procédé
WO2011105291A1 (fr) * 2010-02-24 2011-09-01 独立行政法人産業技術総合研究所 Procédé de fabrication de biocarburant diesel et composition de biocarburant diesel
WO2015056767A1 (fr) * 2013-10-18 2015-04-23 独立行政法人産業技術総合研究所 Procédé pour produire du carburant biodiesel de haute qualité

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