WO2010082527A1 - Procédé de fabrication d'un ester alkylique d'acide gras, et carburant diesel - Google Patents

Procédé de fabrication d'un ester alkylique d'acide gras, et carburant diesel Download PDF

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WO2010082527A1
WO2010082527A1 PCT/JP2010/050110 JP2010050110W WO2010082527A1 WO 2010082527 A1 WO2010082527 A1 WO 2010082527A1 JP 2010050110 W JP2010050110 W JP 2010050110W WO 2010082527 A1 WO2010082527 A1 WO 2010082527A1
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fatty acid
alkyl ester
acid alkyl
oil
oils
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PCT/JP2010/050110
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Japanese (ja)
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幸蔵 佐藤
広文 福永
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富士フイルム株式会社
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    • 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
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/03—Preparation of carboxylic acid esters by reacting an ester group with a hydroxy group
    • 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
    • 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 producing a fatty acid alkyl ester by transesterifying a fat and oil mainly composed of fatty acid glycerides, in particular, a fat and fat having a small composition ratio of a higher saturated fatty acid having 14 or more carbon atoms with a lower alcohol, and
  • the present invention relates to a diesel fuel containing a fatty acid alkyl ester produced by the production method.
  • BDF biodiesel fuel
  • fatty acid ester obtained by transesterification of fats and oils with lower alcohols. Since the origin of fats and oils is plants, it can cause global warming even if burned as a fuel raw material. It is a fuel that can contribute to the prevention of global warming without increasing carbon dioxide (carbon neutral).
  • carbon dioxide carbon neutral
  • fatty acid alkyl ester fuels have the characteristic that almost no sulfur oxides are emitted during combustion because oils and fats made from plants contain little sulfur.
  • carbon monoxide and suspended particulate matter in the exhaust gas can be greatly reduced as compared to diesel oil, and when used as diesel fuel, the adverse effects on the human body are greatly reduced compared to when diesel oil is used.
  • Patent Document 1 discloses that an ester is discarded in the presence of an alkali hydroxide. It describes the production of diesel fuel by reacting edible oil and methanol.
  • a base other than an alkali hydroxide is used as a catalyst and no washing treatment and no washing water drainage treatment are required.
  • a method of using sodium carbonate or sodium hydrogen carbonate Patent Document 5
  • a method of reacting fats and oils in a range of 170 to 250 ° C. and 10 MPa or less under a complex oxide catalyst of ZnO or Zn and Al. Patent Document 6
  • solid catalyst containing calcium oxide Patent Documents 7 and 8
  • calcium oxide and ultrasonic irradiation Non-Patent Document 2
  • utilization of a group consisting of magnesium oxide, hydroxide and carbonate Patent Document 9 and the like are disclosed.
  • all of the catalysts have many problems to be carried out on an industrial scale such as low reaction activity, high reaction conditions at high temperature and high pressure, and large amounts of catalyst and methanol.
  • Patent Document 10 describes a method using amine and water as a catalyst.
  • the energy efficiency is low from the viewpoint of the amount of methanol used, the reaction temperature, the reaction time, and the distillation operation.
  • Patent Document 11 describes a method in which an amine is used as a base and CO 2 is used for separation of a product after the reaction.
  • a large amount of methanol or a base is used, which is an industrial scale.
  • a method of proceeding transesterification without using a catalyst has been developed (see, for example, Patent Documents 12 to 14).
  • Patent Documents 12 to 14 there is a problem that the conversion rate of the transesterification reaction is low, the reaction conditions are high temperature and high pressure, and it is not practical.
  • Patent Document 15 a method for producing a fatty acid alkyl ester using an alkali metal salt of phosphoric acid as a catalyst has been proposed (Patent Document 15). According to this method, a highly pure fatty acid alkyl ester can be separated only by simple specific gravity separation.
  • biodiesel fuel is used in a mixture with diesel oil at a predetermined ratio.
  • biodiesel fuel will be used in the future.
  • the demand for 100% diesel fuel alone is expected to increase.
  • free fatty acids or metal ions are mixed in the fuel, it adversely affects the engine using the fuel, and when the carbon-carbon double bond derived from the unsaturated fatty acid reacts with oxygen, reactive species are generated, There is a problem that an unsuitable compound as a fuel is generated from the reactive species. Therefore, fatty acid alkyl esters are required to have higher purity, and at the same time, stabilization techniques that prevent oxidative degradation and the like are more important.
  • JP-A-7-197047 Japanese Patent Laid-Open No. 7-310090 JP-A-9-235573 JP 2005-15562 A JP-A-61-254255 US Pat. No. 5,908,946 JP 2001-271090 A JP 2004-35873 A JP 2002-308825 A JP 2002-167356 A JP 2005-29715 A JP 2000-109883 A JP 2000-143586 A JP 2005-60591 A JP 2007-77347 A
  • the present invention is a fatty acid alkyl ester which can be produced with high purity, high conversion rate, low environmental load process, low cost, and has a low cloud point, pour point and clogging point and does not solidify even at low environmental temperature. It aims at providing the manufacturing method and the diesel fuel manufactured by this manufacturing method.
  • the inventors of the present invention are fats and oils that contain a large amount of higher saturated fatty acids having 14 or more carbon atoms, and particularly fats and oils that contain a lot of palmitic acid and stearic acid. It has been found that the fluidity disappears with decreasing temperature, and finally the property of solidifying appears significantly. On the contrary, in the case of saturated fatty acids having a small number of carbon atoms or fatty acids containing many unsaturated bonds, the property of solidification was not observed, and this tendency was found to be the same for both fats and oils and fatty acid alkyl esters.
  • the fatty acid alkyl ester by which the property to solidify was suppressed can be manufactured by selecting the raw material fats and oils whose composition of a higher saturated fatty acid of 14 or more carbon atoms is low and whose composition of palmitic acid and stearic acid is low. .
  • This invention is based on the said knowledge by this inventor, and as a means for solving the said subject, it is as follows. That is, ⁇ 1> In the presence of an alkali metal salt of phosphoric acid, the composition ratio of the higher saturated fatty acid having 14 or more carbon atoms is 40 mol% or less, and the higher saturated fatty acid contains palmitic acid and stearic acid, A method for producing a fatty acid alkyl ester, comprising performing an ester exchange reaction between an oil and fat having a composition ratio of palmitic acid and stearic acid of 30 mol% or less and an alcohol having 1 to 4 carbon atoms. .
  • ⁇ 2> The method for producing a fatty acid alkyl ester according to ⁇ 1>, wherein the fat is jatropha oil.
  • ⁇ 3> A diesel fuel comprising 1% by mass to 100% by mass of a fatty acid alkyl ester produced by the method for producing a fatty acid alkyl ester according to any one of ⁇ 1> to ⁇ 2>.
  • the conventional problems can be solved, the object can be achieved, high purity, high conversion rate, low environmental load process, low cost production, and low cloud point, pour point and It is possible to provide a method for producing a fatty acid alkyl ester having a clogging point and not solidifying even at a low ambient temperature, and a diesel fuel produced by the production method.
  • Method for producing fatty acid alkyl ester In the method for producing a fatty acid alkyl ester of the present invention, an ester exchange reaction between an oil and fat and an alcohol is performed in the presence of an alkali metal salt of phosphoric acid.
  • the fats and oils are composed of fats and oils having a composition ratio of higher saturated fatty acids having 14 or more carbon atoms of 40 mol% or less, and the composition ratio is preferably 30 mol% or less, and more preferably 25 mol% or less.
  • the composition ratio is 40 mol% or less, a fatty acid alkyl ester having a low cloud point, a pour point and a clogging point and which does not solidify even at a low environmental temperature can be obtained.
  • R 1, R 2, and R 3 represents an alkyl group or an alkenyl group having from 11 or more carbon atoms
  • R 1, R 2 and R 3 are the same as each different It may be.
  • the composition ratio in the fats and oils of the palmitic acid and the stearic acid is 30 mol% or less, preferably 25 mol% or less.
  • the composition ratio exceeds 30 mol%, there is a disadvantage that a problem that the fatty acid alkyl ester is solidified by the environmental temperature occurs.
  • Jatropha oil contains toxic components, so it is not edible and extremely inexpensive. Jatropha oil grows in areas with low precipitation or on thin land. Fatty acid alkyl esters obtained from jatropha oil have a high cetane number.
  • the most preferred raw material fats and oils also from the viewpoint of having many advantages such as a relatively low cloud point and pour point, and providing a highly pure fatty acid alkyl ester by a method using an alkali metal salt of phosphoric acid as a catalyst. It is.
  • fats and oils in the present invention In addition to virgin (unused) vegetable oils, waste edible oils discarded from food factories, restaurants, general households, etc. can also be used as the fats and oils in the present invention. Or the fats and oils processed goods which have these fats and oils as a main component can also be used as fats and oils in this invention.
  • raw material oils and fats those having a high iodine value and low oxidation stability are preferably used after partially hydrogenated.
  • the degumming method is not particularly limited and may be appropriately selected depending on the purpose.
  • the adsorbent is mixed with unpurified fats and oils together with warm water, and the resulting mixture is then filtered and insoluble. Examples include a method of removing substances, a method of adding phosphoric acid as a modifier to an unrefined raw material oil and fat, and adding an adsorbent and filtering.
  • the alcohols are alcohols having 1 to 4 carbon atoms. Such alcohols are not particularly limited and may be appropriately selected depending on the purpose. For example, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl- Examples thereof include linear or branched alcohols having 1 to 4 carbon atoms such as 1-propanol and 2-methyl-2-propanol. These may be used alone or in combination of two or more. From the viewpoint of availability of the obtained fatty acid alkyl ester, it is preferable to use methanol, ethanol, 2-methyl-1-propanol, and methanol is particularly preferable. Further, the water content in these alcohols is preferably low, and the water content is preferably 1% or less.
  • the amount of alcohol to be added to the raw oil and fat is not particularly limited and can be changed depending on the average molecular weight of the oil or fat.
  • the oil or fat is an ester of glycerin, usually 3 mol per mol of oil or fat. Alcohols are theoretical values. Therefore, for example, the charge equivalent with respect to 100 parts by mass of the fat and oil can be expressed as a multiple of the chemical equivalent calculated by the following equation (A).
  • Wt (100 / Mo) ⁇ 3 ⁇ Ma (A) Wt: equivalent amount of alcohols (parts by mass) Mo: Average molecular weight of fats and oils Ma: Average molecular weight of alcohols
  • the amount of the alcohols to be charged to the raw material fat is preferably 1.0 to 30 times the equivalent amount Wt calculated by the formula (A), preferably 1.0 to It is more preferable to charge at a ratio of 5 times, and it is particularly preferable to charge at a ratio of 1.0 to 2.0 times.
  • Wt equivalent amount calculated by the formula (A)
  • the transesterification reaction is essentially an equilibrium reaction, and in order to obtain the desired product in a high yield, it is generally necessary to use a large excess of alcohol relative to the raw material.
  • the average molecular weight in the formula (A) is calculated based on the component composition of fats and oils as raw materials and alcohol. For example, when the equivalent molecular weight of alcohol when the average molecular weight of fats and oils is 887 and the alcohols are methanol (average molecular weight 32) is calculated according to the formula (A), methanol is 10. As a result, it is preferable to charge 8 to 324 parts by mass, more preferably 10.8 to 54.0 parts by mass, and particularly preferably 10.8 to 21.6 parts by mass. It becomes.
  • the alkali metal salt of phosphoric acid used in the present invention is not particularly limited and may be appropriately selected depending on the intended purpose, but potassium phosphate, sodium phosphate, potassium hydrogen phosphate, and sodium hydrogen phosphate are preferred. Potassium phosphate and sodium phosphate are more preferable, and potassium phosphate is particularly preferable.
  • the potassium phosphate is not particularly limited, be of anhydrous represented by K 3 PO 4, may be those having a water of crystallization is represented by K 3 PO 4 ⁇ 3H 2 O , anhydrous Are more preferred.
  • the amount of the alkali metal salt of phosphoric acid used is not particularly limited and can be changed depending on the saponification value and acid value of the raw oil and fat. 10 parts by mass is preferable, 0.5 parts by mass to 5 parts by mass is more preferable, and 1 part by mass to 3 parts by mass is particularly preferable. In addition, it is preferable to measure the acid value of raw material fats and oils beforehand by titration, and to use the alkali metal salt of phosphoric acid of the quantity required for neutralization so that it may match the said usage-amount.
  • Transesterification> As a conventionally known method for producing a fatty acid alkyl ester, when transesterification is carried out using alkali hydroxide and methanol, hydrolysis occurs as a side reaction, and undesirable free fatty acid or its alkali metal salt (soap). Will be generated. Their generation mechanism is described in detail in JP-A-2007-77347.
  • the transesterification in the present invention uses an alkali metal salt of phosphoric acid as an alkali catalyst, thereby causing an equilibrium reaction between the primary phosphate, the secondary phosphate and the tertiary phosphate.
  • the fatty acid alkyl ester can be efficiently produced by eliminating the production of fatty acid or an alkali metal salt (soap) of the fatty acid by hydrolysis.
  • the alkali metal salt of phosphoric acid is used as a catalyst in the transesterification reaction, the fatty acid alkyl ester layer can be easily separated from the catalyst and the glycerin layer after the reaction, and high purity can be obtained only by simple phase separation. Of the fatty acid alkyl ester. As a result, it is possible not only to discharge a large amount of washing wastewater in the production process but also reduce the burden on the environment, but also eliminate the need for a process such as purification of fatty acid alkyl esters, thereby realizing cost reduction.
  • the effect is that the composition ratio of the higher saturated fatty acid having 14 or more carbon atoms is 40 mol% or less in the presence of an alkali metal salt of phosphoric acid, which is a method for producing the fatty acid alkyl ester of the present invention, and A higher saturated fatty acid containing palmitic acid and stearic acid, and an oil and fat whose composition ratio of the palmitic acid and stearic acid in the higher saturated fatty acid is 30 mol% or less, and an alcohol having 1 to 4 carbon atoms;
  • soap alkali metal salt
  • the reaction temperature for the transesterification reaction is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 20 ° C. to 100 ° C., more preferably 30 ° C. to 70 ° C., and 40 ° C. to 60 ° C. Particularly preferred. If the reaction temperature is less than 20 ° C., the reaction is slow and it takes a long time to complete the reaction. If the reaction temperature exceeds 100 ° C., the amount of alkali metal salt produced by hydrolysis increases.
  • the reaction time for the transesterification reaction is not particularly limited and may be appropriately selected depending on the reaction temperature, the type of raw material used, etc., but is preferably 1 minute to 2 hours, more preferably 10 minutes to 1 hour. . Since the alkali metal salt of phosphoric acid has a high catalytic activity, unnecessary extension of the reaction time is not preferable from the viewpoint of production of unexpected by-products and productivity. In addition, it is preferable to stir at the time of reaction from a viewpoint of promoting reaction.
  • phase separation can be achieved by standing for about 1 hour. At this time, the alkali metal salt of phosphoric acid is trapped in the glycerin layer. Moreover, even if alcohol, water, etc. remain in the reaction mixture, most of them move to the glycerin layer. Therefore, the unreacted alcohol, water, and glycerin are hardly present in the fatty acid alkyl ester layer that is a light liquid. In the phase separation, if necessary, the separation process may be shortened by using centrifugation.
  • the phase-separated fatty acid alkyl ester can be used as it is as a fuel or fuel oil additive without being subjected to special refining. In some cases, it may be used after being purified by distillation. It can also be purified by filtration through a column packed with activated carbon, activated clay, or the like.
  • the fatty acid alkyl ester thus obtained can satisfy, for example, the standard values of water, residual alcohol and glycerin defined in the German standard (DIN E 51606) and the US standard (ASTM D6751). Therefore, it can be used as a diesel fuel as it is.
  • Examples of the filtration method using the column include a method in which the oil / fat is supplied to and passed through a column filled with activated carbon, activated clay, or the like.
  • the column temperature when passing through the column is preferably 20 ° C. to 50 ° C., more preferably 20 ° C. to 40 ° C.
  • the residence time in the column is preferably 1 minute to 10 minutes, more preferably 1 minute to 3 minutes.
  • an antioxidant such as t-butyl hydroquinone or BHT may be added for stable preservation of the obtained fatty acid alkyl ester.
  • the alkali metal salt of phosphoric acid used in the transesterification reaction can be used for the next transesterification reaction. That is, after performing the transesterification and phase-separating and removing the produced fatty acid alkyl ester, the remaining heavy liquid glycerin layer contains an unreacted alcohol and an alkali metal salt of phosphoric acid. By adding raw material fats and alcohol to this heavy liquid layer, it is possible to react continuously by reusing the alkali metal salt of phosphoric acid.
  • the continuous reuse of the alkali metal salt of phosphoric acid can be continuously carried out until it is completely neutralized by the free fatty acid contained in the raw oil.
  • Reusing the alkali metal salt of phosphoric acid, the heavy liquid after repeating the transesterification reaction for example, when potassium phosphate and methanol are used in the reaction, glycerin, potassium phosphate, Contains fatty acid potassium, potassium hydrogen phosphate, phosphoric acid, methanol, and the like.
  • glycerin and methanol can be used for industrial applications by distilling out the heavy liquid.
  • the residue contains salts such as potassium phosphate and fatty acid potassium, it can be effectively used as a fertilizer. These residues may be used as a fertilizer as they are, or may be used as a chemical fertilizer by blending a nitrogen source such as nitrate or ammonium salt.
  • the diesel fuel of this invention becomes a diesel fuel containing the fatty acid alkyl ester obtained by the manufacturing method of the said fatty acid alkyl ester.
  • the fatty acid alkyl ester can be used as a diesel fuel as it is (neat BDF), or from a mixed fuel mixed with kerosene, light oil and A heavy oil (90% light oil mixed with 10% residual oil). It can also be used as a diesel fuel.
  • kerosene means a petroleum product with a boiling point of 150 ° C to 280 ° C obtained by atmospheric distillation of crude oil, and any commercially available kerosene is used. it can.
  • kerosene kerosene that conforms to the provisions of No. 1 or No. 2 of JIS K 2203 is preferable.
  • light oil there is no restriction
  • light oil refers to petroleum products with a boiling point of 200 ° C to 350 ° C obtained by atmospheric distillation of crude oil, and all commercially available light oils are used. it can.
  • the light oil a light oil that conforms to any one of JIS K 2204, No. 1, No. 1, No. 2, No. 3, and No. 3 is preferable.
  • the content of the fatty acid alkyl ester in the diesel fuel is 1% by mass to 100% by mass.
  • the lower limit of the content is preferably 5% or more, and more preferably 10% or more.
  • the mixing method in the case of using the mixed fuel is not particularly limited and may be appropriately selected depending on the purpose.
  • the specific gravity of the fatty acid alkyl ester is larger than the specific gravity of light oil or kerosene.
  • a method of splashing (blending) the synthesized fatty acid alkyl ester onto No. 1 diesel oil of K 2204 is preferred.
  • it is also possible to mix by known methods such as in-tank blending and in-line blending (see, for example, JP-T-2002-530515, JP-T-2004-520453, etc.).
  • the diesel fuel composed of such a mixed fuel can be used as a diesel fuel conforming to various standards.
  • a fuel obtained by mixing 5 parts by mass of the fatty acid methyl ester with 95 parts by mass of light oil can be used as a diesel fuel that complies with the standard JIS K 2204 for diesel oil.
  • the fatty acid alkyl ester may be mixed with kerosene at a mass ratio of 20% by mass or more, and the mixture may be further mixed with light oil to obtain a fuel having a fatty acid alkyl ester content of 5% or more by mass.
  • a mixing method at this time it can be carried out by a known method in addition to the splash blend, in-tank blend, in-line blend and the like.
  • the cloud point, pour point and viscosity can be lowered in advance by mixing the fatty acid alkyl ester with kerosene first, and can be mixed with light oil when necessary. It becomes possible to improve work efficiency and storage stability.
  • the diesel fuel obtained by mixing in this way can satisfy the standards of US standards ASTM D6751 and A-A59693A, and can be used as diesel fuel for automobiles, for example.
  • Example 1 Pre-degummed Jatropha oil (Indonesia, Java (specific gravity 0.9)) 100 mL, methanol 18 mL, potassium phosphate 1.1 g was charged into a 300 mL three-necked flask and reacted at 60 ° C. for 1 hour with stirring. It was. After completion of the reaction, the mixture was cooled to room temperature, and the upper methyl ester layer phase-separated after 1 hour was separated by suction to produce the fatty acid alkyl ester (fatty acid methyl ester) of Example 1 (Production Method 1). The yield was 90 g, and the conversion rate of raw material fats and oils to fatty acid alkyl ester was 99%. With respect to the fatty acid alkyl ester of Example 1, the cloud point, pour point, clogging point, and kinematic viscosity were measured by the methods described below.
  • Example 2 In the same manner as in Example 1 except that Jatropha oil (produced in Lombok, Indonesia (specific gravity 0.89)) was used instead of Jatropha oil (produced in Java, Indonesia (specific gravity 0.9)). 2 fatty acid alkyl esters were produced (Production Method 1). The yield was 89 g, and the conversion rate of the raw oil to fatty acid alkyl ester was 99%.
  • the cloud point, pour point, clogging point, and kinematic viscosity were measured in the same manner as in Example 1. The measurement results are cloud point 6 ° C., pour point 5 ° C., clogging point 1 ° C., kinematic viscosity 4.45 mm 2 / s (30 ° C.). ASTM D6751) was met.
  • Example 3 In the same manner as in Example 1 except that Jatropha oil (from Indonesia, Sumbawa Island (specific gravity 0.89)) was used instead of Jatropha oil (from Indonesia, Java Island (specific gravity 0.9)). 3 fatty acid alkyl esters were produced (Production Method 1). The yield was 89 g, and the conversion rate of the raw oil to fatty acid alkyl ester was 99%. For the fatty acid alkyl ester of Example 3, the cloud point, pour point, clogging point, and kinematic viscosity were measured in the same manner as in Example 1.
  • the measurement results are cloud point 5 ° C., pour point 5 ° C., clogging point 1 ° C., kinematic viscosity 4.48 mm 2 / s (30 ° C.), and it does not solidify even when cooled to 5 ° C. ASTM D6751) was met.
  • Example 4 To the heavy liquid from which the fatty acid alkyl ester produced in Example 1 was extracted, 100 mL used in Example 1 (Jatropha oil Indonesia, Java Island (specific gravity 0.9)) and 18 mL of methanol were added and reacted at 60 ° C. for 1 hour. I let you. After completion of the reaction, the mixture was cooled to room temperature, and the upper methyl ester layer phase-separated after 1 hour was separated by suction to produce the fatty acid alkyl ester (fatty acid methyl ester) of Example 4 (Production Method 2). The yield was 89 g, and the conversion rate of the raw oil to fatty acid alkyl ester was 98.5%.
  • Example 4 For the fatty acid alkyl ester of Example 4, the cloud point, pour point, clogging point, and kinematic viscosity were measured in the same manner as in Example 1. The measurement results are a cloud point of 6 ° C., a pour point of 5 ° C., a clogging point of 2 ° C., and a kinematic viscosity of 4.51 mm 2 / s (30 ° C.). ASTM D6751) was met.
  • the reaction solution was filtered under reduced pressure, and the upper layer methyl ester phase separated by allowing the filtrate to stand was separated, washed with water, and dried to produce the fatty acid alkyl ester (fatty acid methyl ester) of Comparative Example 1 (Production Method 3). ).
  • the yield was 90 g, and the conversion rate of raw material fats and oils to fatty acid alkyl ester was 98%. Further, the cloud point, pour point, clogging point, and kinematic viscosity of the fatty acid alkyl ester of Comparative Example 1 were measured in the same manner as in Example 1.
  • the measurement results are a cloud point of 18 ° C., a pour point of 12 ° C., a clogging point of 13 ° C., and a kinematic viscosity of 5.15 mm 2 / s (30 ° C.). (ASTM D6751) was not satisfied.
  • the fatty acid composition of palm oil is about 50% of saturated fatty acids having 14 or more carbon atoms, and fatty acid methyl esters obtained from such fats and oils are easily solidified at low temperatures and are not suitable as raw materials for neat BDF. I understand.
  • the yield was 80 g, and the conversion rate of raw material fats and oils to fatty acid alkyl ester was 89%.
  • the cloud point, pour point, clogging point, and kinematic viscosity were measured in the same manner as in Example 1. The measurement results are cloud point 5 ° C., pour point 5 ° C., clogging point 2 ° C., kinematic viscosity 4.53 mm 2 / s (30 ° C.), and it does not solidify even when cooled to 5 ° C. ASTM D6751) was met.
  • soap alkali metal salt
  • Example 2 it carried out similarly to Example 1, and measured the cloud point, the pour point, the clogging point, and kinematic viscosity.
  • the measurement results are a cloud point of 18 ° C., a pour point of 13 ° C., a clogging point of 13 ° C. and a kinematic viscosity of 5.17 mm 2 / s (30 ° C.). (ASTM D6751) was not satisfied.
  • the method for producing a fatty acid alkyl ester of the present invention can be produced with high purity, high conversion rate, low environmental load process, low cost, and has a low cloud point, pour point and clogging point, and solidifies even at low environmental temperature. Since the fatty acid alkyl ester can be produced, it can be widely used as a method for producing the fatty acid alkyl ester. Further, the fatty acid alkyl ester produced by the production method can be used as it is as a diesel fuel (neat BDF), and kerosene, light oil and A heavy oil (90% light oil and 10% residual oil are mixed). Can be used as a diesel fuel composed of a mixed fuel mixed with a fuel, and can be suitably used as a diesel fuel.

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Abstract

La présente invention concerne un procédé bon marché et respectueux de l'environnement qui permet d'obtenir, avec une grande pureté et un taux de conversion élevé, un ester alkylique d'acide gras présentant des points de trouble, d'écoulement et de colmatage limités et qui ne se solidifie pas à basse température. L'invention concerne également un carburant diesel obtenu à partir de cet ester. Ce dernier est fabriqué en réalisant, en présence d'un sel de métal alcalin et d'acide phosphorique, une réaction de transestérification entre un alcool portant 1-4 atomes de carbone et une graisse ou une huile contenant un acide gras supérieur saturé portant au moins 14 atomes de carbone dans une proportion de 40 % en moles ou moins, ledit acide gras contenant de l'acide palmitique et de l'acide stéarique, l'acide palmitique et l'acide stéarique représentant au total 30 % en moles ou moins.
PCT/JP2010/050110 2009-01-16 2010-01-07 Procédé de fabrication d'un ester alkylique d'acide gras, et carburant diesel WO2010082527A1 (fr)

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Application Number Priority Date Filing Date Title
JP2009008224A JP2010163567A (ja) 2009-01-16 2009-01-16 脂肪酸アルキルエステルの製造方法、並びに、ディーゼル燃料
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