WO2007074592A1 - Procédé de production d'esters alkyliques inférieurs d'acides gras - Google Patents

Procédé de production d'esters alkyliques inférieurs d'acides gras Download PDF

Info

Publication number
WO2007074592A1
WO2007074592A1 PCT/JP2006/322830 JP2006322830W WO2007074592A1 WO 2007074592 A1 WO2007074592 A1 WO 2007074592A1 JP 2006322830 W JP2006322830 W JP 2006322830W WO 2007074592 A1 WO2007074592 A1 WO 2007074592A1
Authority
WO
WIPO (PCT)
Prior art keywords
fatty acid
lower alkyl
alkyl ester
ester
transesterification
Prior art date
Application number
PCT/JP2006/322830
Other languages
English (en)
Japanese (ja)
Inventor
Yoshiro Tanaka
Takayuki Matsuo
Jiro Izumi
Original Assignee
Lion Corporation
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 Lion Corporation filed Critical Lion Corporation
Priority to JP2007551865A priority Critical patent/JP5005547B2/ja
Publication of WO2007074592A1 publication Critical patent/WO2007074592A1/fr

Links

Classifications

    • 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
    • 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
    • C11B3/00—Refining fats or fatty oils
    • C11B3/10—Refining fats or fatty oils by adsorption

Definitions

  • the present invention relates to a method for producing a fatty acid lower alkyl ester that is suitably used as a detergent raw material or a higher alcohol raw material.
  • fatty acid lower alkyl esters obtained by transesterifying animal and vegetable fats and oils with lower alkyl alcohols are used as raw materials for surfactants used in detergents, soaps, and higher alcohols. It has been.
  • Examples of the method for producing the fatty acid lower alkyl ester include the methods disclosed in Patent Documents 1 to 3.
  • the fatty acid lower alkyl ester used for such applications is required to have high purity, and it is particularly important that the fatty acid lower alkyl ester is free of coloring and odor.
  • Patent Document 1 Japanese Patent No. 2590538
  • Patent Document 2 Japanese Patent No. 3046999
  • Patent Document 3 Japanese Patent Application Laid-Open No. 59-5142
  • the fatty acid lower alkyl ester obtained by such a conventional production method does not always have sufficient quality in terms of coloring and odor.
  • the present invention has been made in view of the above circumstances, and a high-purity fatty acid lower alkyl ester suitable for a raw material of a surfactant having no coloring or smell, soap, a raw material of higher alcohol, or the like is obtained in a high yield. Therefore, the problem is to produce stably for each carbon number.
  • the method for producing a fatty acid lower alkyl ester of the present invention is a method for producing a fatty acid lower alkyl ester from a raw material containing animal or vegetable fats and oils, and using a cation exchange resin.
  • the esterification step (A) in which the fatty acid in the raw material is esterified with a lower alkyl alcohol to obtain a reaction mixture containing an ester mixed oil having an acid value of 2 or less, and the amount of the alkali catalyst is changed to the ester mixed oil.
  • the fats and oils in the ester mixed oil are transesterified with lower alkyl alcohol while adjusting according to the acid value.
  • the distillate containing a fatty acid lower alkyl ester on the low carbon number side is distilled off, A distillation step (C) for leaving a residue containing a fatty acid lower alkyl ester on the high carbon number side, and from the residue, a fatty acid lower alkyl ester on the high carbon number side contained in the residue is distilled for each carbon number.
  • the amount to make And having at least includes the fractionation step (D).
  • the degumming step (P) is preferably a step of mixing the unrefined oil and fat with a modifier containing phosphoric acid and an adsorbent containing pearlite, and filtering the resulting mixture.
  • the transesterification step (B) preferably includes a two-step process.
  • the soap produced as a by-product in the transesterification reaction step (B) is decomposed with an acid under the conditions of pH 2 to 5 to obtain a fatty acid, and the fatty acid is more than the esterification step (A) or the esterification step (A). It is preferable to have a recycling process (R) that returns to the previous process.
  • sodium hydroxide is used as the alkali catalyst and sulfuric acid is used as the acid to produce sodium sulfate as a by-product in the recycling step (R).
  • a high-purity fatty acid lower alkyl ester suitable for a raw material of a surfactant that is colored or smelled, or a raw material of soap or higher alcohol is obtained in a high yield for each carbon number. Can be manufactured stably.
  • FIG. 1 is a schematic process diagram showing an example of a production method of the present invention.
  • FIG. 2 is a schematic process diagram showing an example of a recycling process (R) in the production method of the present invention.
  • Animal and vegetable fats and oils used as raw materials in the production method of the present invention are derived from animals (including microorganisms) and plants, and are mainly composed of fats and oils (fatty acid tridalylide).
  • animal-derived materials include beef tallow and pork fat.
  • plant-derived materials include coconut oil, palm kernel oil, palm oil, rapeseed oil, soybean oil, castor oil, and corn oil.
  • These animal and vegetable fats and oils are unrefined unrefined fats and oils that contain phospholipids as a main component, free fatty acids (hereinafter sometimes referred to as free fatty acids), odor components and the like.
  • it may be a refined fat or oil from which at least a part of these has been removed by a refining treatment.
  • the main component refers to a component occupying at least 50%.
  • animal and vegetable oils and fats may be used alone or in combination of two or more.
  • fatty acids recovered during the production process of other substances may be used in the animal and vegetable fats and oils. If there are too many such fatty acids, each step may be adversely affected, so 5 parts by mass or less is preferred with respect to 100 parts by mass of animal and vegetable fats and oils.
  • Crude palm oil is obtained by squeezing the pulp of oil palm, and is an unrefined mixture composed mainly of fats and oils of fatty acids having 16 to 18 carbon atoms. Crude palm oil also includes carotene, phospholipids, proteins, gums such as sallow-like substances, free fatty acids, and fats and oils of fatty acids with 20 carbon atoms. Crude palm oil is particularly preferred with a free fatty acid content of 5% by mass or less and a peroxide value of 5 m equivalent / kg or less! /.
  • FIG. 1 is a schematic process diagram showing an example of the production method of the present invention, and shows a case where crude palm oil, which is an unrefined fat, is used as a raw animal and vegetable fat!
  • the degumming step (P) When using unrefined fats and oils such as crude palm oil, first the degumming step (P) is performed, followed by the esterification step (A) of the fatty acid in the raw material, and then the transesterification reaction step. Step (B), distillation step (C), and fractionation step (D) are carried out.
  • the esterification process (A) can be performed without performing the degumming process (P).
  • the soap produced as a by-product in the transesterification step (B) is decomposed with an acid to be a fatty acid, and this fatty acid is reused.
  • Figure 2 shows an example of the recycling process (R). Show.
  • the degumming process (P) when unrefined fats and oils are used as raw materials, the gums mainly composed of phospholipids contained in the unrefined fats and insolubles such as colloidal impurities are removed in a concentrated manner. And after carrying out this step, the esterification step (A) is carried out.
  • the specific method of the degumming step (P) may be a method of mixing the adsorbent with unrefined fats and oils together with hot water that is not particularly limited, and then filtering the resulting mixture to remove insoluble matters. As shown in the figure, it is preferable to add phosphoric acid as a denaturing agent to the unrefined oil and fat, add the adsorbent, and perform filtration.
  • the degumming rate increases and it becomes easier to separate by-products in each subsequent step, thus improving the separation efficiency.
  • a high-purity fatty acid lower alkyl ester can be obtained in a high yield.
  • the adsorbent pearlite, diatomaceous earth, activated clay and the like can be used, but pearlite is more preferred because diatomaceous earth and pearlite have a higher adsorbing ability than preferred.
  • Perlite is a foam made by obsidian heat treatment at high temperature.
  • the unrefined fat is preferably heated to 50 to 70 ° C, more preferably 60 to 70 ° C, and phosphoric acid and pearlite are added thereto, preferably 1 to 60 minutes. More preferably, the mixture is stirred for 10 to 40 minutes. After mixing and stirring, the mixture is filtered with a filter equipped with a filter such as a cloth filter to remove insoluble matters and a degummed product is obtained as a filtrate.
  • the treatment temperature is 50 to 70 ° C, useful components in the unrefined fats and oils are not altered or deteriorated, and can be effectively degummed.
  • the addition amount of phosphoric acid is preferably 0.01 to 0.1 parts by mass with respect to 100 parts by mass of the unrefined fats and oils.
  • the amount is 0.01 parts by mass or more, degumming effectively proceeds, while when the amount is 0.1 parts by mass or less, phosphoric acid that does not contribute to degumming hardly remains.
  • the formation of insoluble salt in the transesterification step (B) from which it is derived also tends to be suppressed.
  • the addition amount of phosphoric acid is more preferably adjusted as appropriate according to the gum content of the unrefined fats and oils. The gum content can be measured by the A.O.C.S test method Ca 9f-57.
  • the phosphoric acid is added in the form of an aqueous solution.
  • the phosphoric acid concentration of the aqueous phosphoric acid solution is preferably 70% by mass or more, more preferably 75 to 90% by mass. This With such a concentration, it is preferable that water as a solvent is less likely to adversely affect the subsequent step than the degumming step (P) and to reduce the filterability of the gum.
  • the amount of pearlite added is preferably 0.03 to 0.15 parts by weight, more preferably 0.03 to 0.1 parts by weight, and still more preferably 0.03 to 0.1 parts by weight with respect to 100 parts by weight of the unrefined fat. 0. 05 Mass department. When the amount is 0.03 parts by mass or more, degumming effectively proceeds, while when the amount is 0.15 parts by mass or less, loss of unrefined fat and oil is suppressed and the amount of pearlite to be discarded is small. No need.
  • the degumming step (P) unrefined fats and oils containing a large amount of adsorbent are circulated and supplied to the filter to form a precoat phase on the surface of the filter so that filtration can be performed more smoothly. Also good.
  • the amount of pearlite added is preferably 0.2 to 1.0 parts by mass, more preferably 0.2 to 0.7 parts by mass, and still more preferably 0 to 100 parts by mass of unrefined fats and oils. 2 to 0.4 parts by mass. Even in this case, if the amount of added pearlite is within such a range, it is possible to effectively degumm while suppressing loss of unrefined fat and oil and reducing the amount of pearlite to be discarded.
  • the degumming step (P) and during the degumming step (P) it is preferable to remove impurities from the unrefined fat and oil as necessary.
  • Contaminants may be removed by the same method and the same apparatus as the gum removal, or may be removed by static separation or filtration separation in an unrefined oil storage tank, centrifugation, or the like. Contaminants include soil, gravel, and garbage, and in some cases, metal may be included.
  • the moisture content of the degummed product is preferably 2000 ppm or less, it is preferable to remove the moisture appropriately here. This is because a large amount of moisture may adversely affect the transesterification rate in the subsequent transesterification step (B).
  • the esterification step (A) is a step of esterifying the fatty acid in the raw material with a lower alkyl alcohol using a cation exchange resin to obtain a reaction mixture containing an ester mixed oil.
  • the reaction mixture is an untreated mixture obtained in the esterification step (A), and the ester produced in the esterification step (A) and the fats and oils that are the main ingredients of the raw material.
  • the ester mixed oil consisting of other ingredients originally contained in the raw material, it refers to those containing unreacted lower alkyl alcohol and by-product water. That is, the esterification step (A)
  • the lower alkyl alcohol and water are removed from the reaction mixture, which is the untreated mixture obtained in A)! Is an ester mixed oil.
  • the fatty acid contains free fatty acid originally present in the raw material, and when the recycling step (R) is performed, the fatty acid is by-produced in the transesterification step (B) and is recycled in the recycling step (R). Recovered fatty acids recovered and returned are also included, but both are subject to the ester
  • the water content of the raw material used in the esterification step (A) is preferably 2000 ppm or less from the viewpoint of the transesterification rate in the transesterification step (B). If the raw material contains unrefined fats and has already been subjected to the degumming step (P), the moisture content is reduced to 2000 ppm or less in the degumming step (P) as described above. It is preferable. When using refined fats and oils as raw materials, the water content has already been reduced to 2000ppm or less! Many products have been reduced to more than 2000ppm. It is preferable to reduce the moisture content by mixing oils and fats.
  • esterification is performed so that the acid value of the ester mixed oil is 2 or less, preferably 1 or less, more preferably 0.1 to 0.5.
  • the practical lower limit is about 0.1.
  • adjust conditions such as column type, column temperature, column residence time, and the amount of lower alkyl alcohol used.
  • esterification step (A) by preliminarily esterifying the fatty acid so that the acid value is 2 or less, a high-purity fatty acid lower alkyl ester can be obtained smoothly in a high yield.
  • the acid value is the concentration of an acidic substance expressed in terms of the mass (mg) of potassium hydroxide hydroxide required for neutralization per lg of sample, and in the case of fats and oils, means the concentration of fatty acids. To do.
  • An acid value of 1 corresponds to a fatty acid concentration of 0.46% by mass (in terms of palmitic acid). The acid value is sometimes called AV.
  • reaction mixture was sucked with an evaporator to remove the unreacted lower alkyl alcohol to obtain an ester mixed oil, which was passed through a filter paper further containing anhydrous sodium sulfate.
  • the method of neutralization titration after treatment is preferred.
  • esterification step (A) converts fatty acid into lower alkyl ester of fatty acid that does not remove fatty acid out of the system, so that the production yield based on raw materials can be kept high. Can do.
  • the esterification process (A) is performed before the transesterification reaction process (B), and when the degumming process (P) is performed, the degumming process (P) and the transesterification are performed. Since it is carried out continuously between the reaction step (B), it is very efficient. The ability to maintain the production yield by mixing the fatty acid removed outside the system with a separate line and mixing it with the final fatty acid lower alkyl ester is also considered to be effective. Not right.
  • the esterification step (A) water is produced together with the lower alkyl ester of the fatty acid. Therefore, if a large amount of fatty acid is contained in the raw material, the amount of water produced in the ester cake is increased accordingly. Become. As described above, the presence of a large amount of water may adversely affect the transesterification rate in the ester exchange reaction step (B) to be carried out. Therefore, the amount of fatty acid in the raw material treated in the esterification step (A) is preferably 15 or less as the acid value, more preferably 12 or less, and even more preferably 10 or less.
  • the acid value of the raw material referred to here includes not only the acid value derived from free fatty acids but also the acid value derived from recovered fatty acids.
  • esterification is performed using a cation exchange resin. Therefore, the esterification can be continuously progressed by a simple method in which the raw material is brought into contact with the cation exchange resin, and other esterification methods such as a method using a solid catalyst and a method of collecting an acid such as sulfuric acid can be used. Compared with the dredging method, high esterification reaction rate can be achieved.
  • the method using cation exchange resin does not cause problems such as deterioration of quality of animal and vegetable oils and raw materials, and corrosion of equipment.
  • examples of the cation exchange resin include acid type solid cation exchange resin, acidic gel type cation exchange resin, and the like. Is more preferable because it increases. The reason for this is not clear, but can be inferred as follows. That is, the acid-type solid cation exchange resin has the ability to reduce the catalytic ability due to the adhesion or adsorption of water generated by the esterification reaction. The acidic gel-type cation exchange resin can take water as hydration water. This can be attributed to the fact that the catalytic performance is not reduced by water.
  • the degree of crosslinking of the acidic gel type cation exchange resin is preferably in the range of 3 to 10%. If it is 3% or more, it is preferable from the viewpoint of scab strength, and if it is 10% or less, it is preferable from the viewpoint of fatty acid removal efficiency.
  • the degree of crosslinking is more preferably 4-8%. Of these, those having a cross-linking degree of 4% are particularly preferred because the mechanical strength of the resin having the highest fatty acid esterification rate is sufficient.
  • Examples of the acidic gel type cation exchange resin that can be suitably used include a sulfone product of styrene monodivinylbenzene copolymer. , Crosslink degree 4%), SK106 (Product name, Crosslink degree 6%), SK IB (trade name, cross-linking degree 6%) and SKI 10 (trade name, cross-linking degree 10%), Dow Chemical's Dowex (trade name, cross-linking degree 4%), Rohm 'and' Haas Amber Light (trade name, degree of cross-linking 4%).
  • esterification step (A) there is a method in which a column filled with a cation exchange resin is prepared, and a mixture of a lower alkyl alcohol and a raw material is supplied to the column and passed therethrough. It is done.
  • the conditions for passing through the column are that the column temperature is preferably 40 to 70 ° C, more preferably 50 to 65 ° C, still more preferably 60 to 65 ° C, and the column residence time is preferably 60 to 480 minutes. More preferably, it is 90 to 360 minutes, and still more preferably 90 to 240 minutes. With such temperature and column residence time, the flowability of the mixture is good, the reaction rate is sufficient, and it is efficient that the column does not need to be excessively large or pressure-resistant.
  • the cation exchange resin Before supplying the mixture of the lower alkyl alcohol and the raw material to the column, it is preferable to wash the cation exchange resin with alcohol as a pretreatment.
  • the alcohol for washing it is preferable to use the same lower alkyl alcohol used for the esterification reaction. Further, such washing is preferably performed until the moisture in the alcohol before and after passing through the column does not change. By washing in this manner, the water in the cation exchange resin is replaced with alcohol, and the esterification efficiency of the fatty acid can be further increased. Specifically, it is preferable to wash with 2 to 5 times the volume of alcohol of the cation exchange resin.
  • an alcohol having 4 or less carbon atoms can be used, and specific examples include methanol, ethanol, propanol, butanol and the like. These may be used alone or in combination of two or more, but preferably methanol is used as shown.
  • the amount of the lower alkyl alcohol added is preferably 5 to 50 parts by mass, more preferably 10 to 30 parts by mass with respect to 100 parts by mass of the raw material, which is appropriately determined according to the fatty acid distribution in the raw material. More preferably, it is 15 to 25 parts by mass. Within such a range, a sufficient esterification reaction rate can be obtained and the recovery cost of lower alkyl alcohol can be obtained. An excessive increase in equipment capacity can be suppressed.
  • the lower the amount of water in the lower alkyl alcohol is preferably 1500 ppm or less, more preferably ⁇ or lOOOOppm, and even more preferably 600 or less.
  • an ester exchange reaction step (B) is carried out in which the fat or oil in the ester mixed oil is transesterified with a lower alkyl alcohol using an alkali catalyst.
  • the fats and oils subject to transesterification are those that exist as the main component of the raw animal and vegetable fats and oils. This transesterification produces fatty acid lower alkyl ester and dariserine.
  • alkali catalyst examples include sodium hydroxide, potassium hydroxide, sodium methylate and the like because they are good in quality and can be easily obtained at a low temperature. The ability to use one or more of these. The cost point is also preferred for sodium hydroxide and potassium hydroxide. From the point of view of operability, hydroxide sodium is also shown in the figure. preferable.
  • the transesterification step (B) is at least one step, and in the first step, the ester mixed oil obtained in the esterification step (A) is used.
  • the transesterification reaction is carried out while controlling the amount of alkali catalyst according to the acid value.
  • the alkali catalyst amount is in the range of 0.1 to 1.0 part by mass, more preferably in the range of 0.2 to 0.6 part by mass.
  • the acid value is high It is preferable to increase the amount of alkali catalyst and to decrease the amount of alkali catalyst when the acid value is small. More preferably, sodium hydroxide alone is used as the alkali catalyst, and the catalyst amount C [parts by mass] with respect to 100 parts by mass of the ester mixed oil is used.
  • AV indicates an acid value and is 2 or less.
  • the catalyst amount C [parts by mass] with respect to 100 parts by mass of the ester mixed oil at that time is determined using the acid value as a parameter.
  • AV indicates an acid value and is 2 or less.
  • a lower alkyl alcohol and an alkali catalyst are added to the reaction mixture obtained in the esterification step (A), and the reaction is performed under the conditions described later. Just go ahead.
  • the reaction mixture contains water, but when the water content is 5000 ppm or less, it is particularly effective to use the above-mentioned alkali catalyst amount.
  • the amount of the lower alkyl alcohol used (including the amount of the lower alkyl alcohol contained in the reaction mixture) is preferably 10 to 50 parts by mass, more preferably 20 to 100 parts by mass with respect to 100 parts by mass of the ester mixed oil. 40 parts by mass, more preferably 30-40 parts by mass. Within such a range, the lower alkyl alcohol can be recovered and purified at a low cost without the need to increase the size of the apparatus to be used, and a sufficient transesterification rate can be obtained.
  • the reaction temperature is preferably 40 to 120 ° C, more preferably 50 to 100 ° C, still more preferably 60 to 80 ° C. Within such a range, the rate of the transesterification reaction is sufficient, and it is efficient that there is no need to increase the pressure resistance of the equipment used.
  • the treatment time is preferably 15 to 120 minutes, more preferably 30 to 70 minutes, More preferably, it is 40 to 60 minutes. Within such a range, it is possible to achieve a high transesterification rate without enlarging the apparatus used.
  • an oil phase mainly composed of a fatty acid lower alkyl ester and a phase mainly composed of glycerin (hereinafter referred to as glycerin phase) are produced.
  • the oil phase thus obtained may be used as it is in the distillation step (C).
  • the distillation step is carried out after performing the second transesterification step following the first step. It is preferable to carry out (C).
  • the transesterification rate of the fatty acid lower alkyl ester can be increased.
  • the reaction is progressed to a reaction rate of about 95 to 96% in the first stage, and the reaction rate is advanced to about 99% in the second stage.
  • an oil phase mainly composed of a fatty acid lower alkyl ester and a glycerin phase are separated, and only the oil phase is supplied to the second stage.
  • Separation of the oil phase and the glycerin phase may be performed by stationary separation, centrifugation, or the like.
  • the temperature is preferably 30 to 70 ° C, more preferably 30 to 50 ° C.
  • the standing time is preferably 30 to 90 minutes, more preferably 30 to 60 minutes. Under such conditions, the fluidity of the oil phase is good and the vapor pressure of the lower alkyl alcohol can be suppressed, so that the separation can be performed efficiently without the need to increase the pressure resistance of the separation apparatus used.
  • the lower alkyl alcohol addition amount is preferably 1 to 20 parts by mass, more preferably 5 to 10 parts by mass with respect to 100 parts by mass of the oil phase supplied in the second stage. Part. Within such a range, the lower alkyl alcohol can be recovered and purified at a low cost, and a sufficient transesterification rate can be obtained.
  • the amount of the alkali catalyst is preferably 0.01 to 0.2 parts by mass, more preferably 0.05 to 0.2 parts by mass, and still more preferably 0.05 to 0. If it is 1 mass part and it is such a range, transesterification can be performed efficiently, suppressing the by-product of soap.
  • the treatment temperature in the second stage is preferably 40 to 70 ° C, more preferably 50 to 60 ° C. Within such a range, the rate of the transesterification reaction is sufficient, and it is efficient that there is no need to increase the pressure resistance of the equipment used.
  • the treatment time for the second stage is preferably 1 to 15 minutes, more preferably 3 to 10 minutes. In such a range, it is possible to achieve a sufficient transesterification rate without requiring excessive time.
  • an oil phase mainly composed of a fatty acid lower alkyl ester and a glycerin phase are separated, and the oil phase is sent to the distillation step (C). Preferably it is sent to the recital process (R).
  • the separation of the oil phase and the glycerin phase here can be performed by static separation, centrifugation, etc., as in the case of the separation performed between the first and second stages. Therefore, the temperature is preferably 30 to 70 ° C, more preferably 40 to 70 ° C, and the standing time is preferably 30 to 90 minutes, more preferably 30 to 60 minutes.
  • water for washing glycerin, lower alkyl alcohol, and the like 10 to 30 parts by weight is preferred with respect to 100 parts by weight of the mixture obtained in B), more preferably 10 to 20 parts by weight. Within such a range, effective water washing can be performed without causing emulsification.
  • the recycling step (R) is a step in which the soap in the glycerin phase by-produced in the transesterification step (B) is decomposed with an acid to give a fatty acid under the conditions of pH 2 to 5, and this fatty acid is returned.
  • the fatty acid may be returned to the esterification step (A), or may be returned to the preceding step. Specifically, the case where it returns to a degumming process (P) and the case where it returns to a raw material storage tank can be illustrated.
  • the by-product soap is of low quality and is difficult to use as it is, but it can be used as a fatty acid in such a recycling process (R) and reused as a raw material to increase the production yield.
  • R recycling process
  • glycerin phase in addition to glycerin and soap, usually lower alkyl alcohol (methanol in the illustrated example), alkali catalyst, water, etc. Existing.
  • an acid is added to the glycerin phase as it is to adjust the pH to 2 to 5, preferably pH 3 to 4.
  • the mixture containing the fatty acid is preferably stirred and mixed for 10 to 70 ° C, more preferably 40 to 60 ° C, preferably for 30 to 360 minutes, more preferably for 60 to 120 minutes. Generate.
  • the device may corrode, and if it exceeds 5, the decomposition tends to be difficult.
  • the temperature is 10 to 70 ° C, decomposition proceeds at a sufficient rate without the need to increase the pressure resistance of the device. Further, when the stirring and mixing time is 30 to 360 minutes, a sufficient decomposition rate can be achieved without increasing the size of the apparatus. Further, according to the method of adding an acid without separating and removing the lower alkyl alcohol from the glycerin phase as described above, the acid decomposition can be performed at a low temperature and in a short time.
  • the acid strong sulfuric acid that can use sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid and the like is preferable.
  • sodium sulfate is by-produced along with the fatty acid.
  • the sodium sulfate produced as a by-product in this way is separated and removed from the fatty acid force, but sodium sulfate is excellent in separability, and is therefore preferred because it is less contaminated with fatty acids.
  • hydrochloric acid is used as the acid and sodium hydroxide is used as the alkali catalyst in the transesterification step (B)
  • sodium chloride sodium is produced as a by-product. Since sodium salt is poor in separability, it is easily mixed into fatty acids. Since fatty acids are reused, they should be as free of impurities as possible. Therefore, it is preferable to use sulfuric acid as the acid.
  • sodium sulfate is first removed by centrifugation or the like, and then a part of lower alkyl alcohol, glycerin and water are removed. Then, water is added to the mixture from which these are removed, and the mixture is further separated into a phase containing fatty acid as a main component and a phase containing water, lower alkyl alcohol and glycerin. Then, the phase mainly composed of fatty acid is returned.
  • water and lower alkyl alcohol are usually distilled by flash distillation at 120 to 200 ° C to obtain crude glycerin as a residue.
  • the water and lower alkyl alcohol distilled by flash distillation are then introduced into a lower alkyl alcohol rectification column and operated at 60 to 120 ° C. to collect the lower alkyl alcohol as a distillate and to collect waste water. As a residue.
  • the transesterification step (B) is carried out in two or more stages, it is preferable to separate and recover the dariserin phase at the end of each stage and to use all of them for this recycling step (R).
  • the oil phase obtained in the transesterification step (B) is distilled to distill off the distillate containing the fatty acid lower alkyl ester on the low carbon number side, and at the same time on the high carbon number side. This is a step of leaving a residue containing a fatty acid lower alkyl ester.
  • the fractionation step (D) the number of steps of distilling the fatty acid lower alkyl ester on the high carbon number side contained in the residue for each carbon number from the residue obtained in the distillation step (C) is reduced. Both are provided.
  • the low-carbon fatty acid lower alkyl ester contained in this distillate is distilled for each carbon number from the distillate obtained in the distillation step (C) as necessary. You may have further the process to make.
  • Such a fractionation step (D) is preferably carried out under reduced pressure conditions.
  • the fatty acid lower alkyl ester is distilled for each carbon number.
  • “distilling for every carbon number” does not necessarily mean distilling for every one carbon number. However, according to the purpose, those having a plurality of carbon atoms may be distilled together.
  • the oil phase obtained in the transesterification step (B) has a plurality of fatty acid lower alkyl esters having different carbon numbers, and these generally have different boiling points.
  • an oil phase mainly composed of a fatty acid lower alkyl ester on the high carbon number side is steamed. If the fractionation step (D) is carried out under conditions suitable for the fractionation of the fatty acid lower alkyl ester on the high carbon number side without carrying out the fractionation step (c), a low component, which is a minor component, is obtained during the fractionation.
  • the fatty acid lower alkyl ester on the carbon number side suddenly boils, and as a result, the monodalyceride remaining at the bottom of the distillation column is easily entrained in the distillate. The properties will deteriorate.
  • the subsequent fractionation step (D) is optimal for fractionation of the fatty acid lower alkyl ester on the high carbon number side, which is the main component. Since the conditions can be set, the resulting fatty acid lower alkyl ester has a high purity.
  • distillation step (C) and fractional distillation step (D) are not particularly limited.
  • the raw material is derived from fatty acids having 12, 14, 16, 18 carbon atoms as fats and oils.
  • lower alkyl alcohol methanol in the example shown in the figure
  • water are removed as the distillate.
  • a fatty acid lower alkyl ester on the high carbon number side contained in the residue that is, a fatty acid having 12, 14, 16, 18 carbon atoms.
  • the fatty acid lower alkyl ester derived from the acid is distilled off sequentially for each carbon number under reduced pressure.
  • the impurities contained in the oil phase remain at the bottom of the column as a residue.
  • the flash distillation step is usually performed at a temperature of 120 to 170 ° C, and then the fatty acid derived from fatty acids having 6, 8, and 10 carbon atoms is reduced.
  • the step of distilling the distillate containing the secondary alkyl ester is under reduced pressure conditions with the top pressure of the distillation column being 8 to: L lkPa, the top temperature being 135 to 175 ° C, and the reflux ratio being 1 to 2.
  • the preferred fractionation step (D) is as follows. First, the top pressure of the distillation column is 7 to 9 kPa, the top temperature is 180 to 183 ° C, and the reflux ratio is 1 to 2. A distillate containing a fatty acid lower alkyl ester derived from a fatty acid having 12 carbons as a main component is distilled, and then the top pressure of the distillation column is 1 to 3 kPa and the top temperature is 199 with respect to the residue.
  • a distillate containing a fatty acid lower alkyl ester derived from a fatty acid having 14 carbon atoms as a main component was distilled at a reflux ratio of 1 to 2, and then the top pressure of the distillation column was set to 0 for the residue. 6 ⁇ 2.5kPa, the top temperature is 183 ⁇ 206.
  • a distillate containing a fatty acid lower alkyl ester derived from a fatty acid having 16 carbon atoms as a main component is distilled at a C and reflux ratio of 0.5.
  • the lower pressure of fatty acid lower alkyl ester derived from a fatty acid having 18 carbon atoms with the top pressure of the distillation column being 0.5 to 0.8 kPa, the top temperature being 180 to 205 ° C., and the reflux ratio being 0.
  • a distillate containing as a main component is distilled off.
  • the top pressure of the distillation column is 10 to 12 kPa, the top temperature.
  • a distillate containing a fatty acid lower alkyl ester derived from a fatty acid having 6 carbon atoms as a main component was distilled at a temperature of 60 to 86 ° C and a reflux ratio of 11 to 13, and then the residue was Distillation with fatty acid lower alkyl ester derived from fatty acid having 8 carbon atoms as main component, with top temperature of 120-130, reflux ratio of 1-2, while maintaining top pressure of distillation column at 10-12kPa
  • the liquid was then distilled, and then the residue was converted to a fatty acid having 10 carbon atoms with a top temperature of 152 to 158 ° C and a reflux ratio of 0 while maintaining the top pressure of the distillation column at 10 to 12 kPa.
  • the raw material mainly contains palm oil mainly composed of oils and fats derived from fatty acids having 16 and 18 carbon atoms
  • the distillation step (C) A distillate containing mainly a fatty acid lower alkyl ester which is a minor component on the low carbon number side, that is, a fatty acid lower alkyl ester derived from a fatty acid having 12 or 14 carbon atoms, is distilled off.
  • the fractionation step (D) fatty acid lower alkyl esters derived from fatty acids having 16 and 18 carbon atoms may be sequentially distilled from the residue in the distillation step (C).
  • palm oil as shown in FIG.
  • the residue obtained in the distillation step (C) is distilled under reduced pressure to obtain fatty acids having 16 or 18 carbon atoms.
  • the distillate containing the lower alkyl ester of fatty acid derived from the product and other residues are separated, leaving impurities in the residue, and fractionating the resulting distillate to obtain fatty acids having 16 carbon atoms.
  • fatty acid lower alkyl esters derived from sucrose and fatty acid lower alkyl esters derived from fatty acids having 18 carbon atoms It is preferable to adopt a two-stage method.
  • the flash distillation step is usually performed at a temperature of 120 to 170 ° C, and then a low-grade fatty acid derived from a fatty acid having 12 or 14 carbon atoms.
  • the step of distilling the distillate containing the alkyl ester is performed under reduced pressure conditions such that the top pressure of the distillation column is 1 to 3 kPa, the top temperature is 178 to 184 ° C, and the reflux ratio is 10 to 15.
  • the top pressure of the distillation column is first set to 0.5 to 0 with respect to the residue obtained in the distillation step (C).
  • the evaporation rate is set to 98% or less, preferably 95 to 96% under such conditions, it is preferable that the coloring component and odor component can be reliably left in the residue.
  • the top pressure of the distillation column is 0.6 to 2.5 kPa
  • the top temperature is 183 to 206 ° C
  • the reflux ratio is 0.5.
  • a distillate mainly composed of a lower alkyl ester of fatty acid is distilled, and the top pressure of the distillation column is 0.5 to 0.8 kPa, the top temperature is 180 to 205 ° C, and the reflux ratio is reduced.
  • a distillate containing a fatty acid lower alkyl ester derived from a fatty acid having 18 carbon atoms as a main component is distilled off with a vaporization rate of 0 and an evaporation rate of 99%.
  • the top pressure of the distillation column is 7 to 9 kPa, the top temperature.
  • the distillate containing a fatty acid lower alkyl ester derived from a C12 fatty acid as a main component is distilled at a reflux ratio of 1 to 2 at a temperature of 180 to 183 ° C and a reflux ratio of 1 to 2, and a lower fatty acid derived from a C14 fatty acid.
  • alkyl ester By leaving the alkyl ester as a residue, it is preferable to separate a fatty acid lower alkyl ester derived from a fatty acid having 12 carbon atoms and a fatty acid lower alkyl ester derived from a fatty acid having 14 carbon atoms.
  • the reflux ratio is the ratio of the reflux amount to the distillate amount
  • the evaporation rate is the ratio of the distillate amount to the charged (supply) liquid amount in (%).
  • top temperature, top pressure, bottom temperature, and bottom pressure are the temperature and pressure measured at the top and bottom of the distillation column, respectively.
  • the part and the bottom are the tower bottom part where the residue is accumulated.
  • the fatty acid lower alkyl ester on the high carbon number side is particularly distilled under optimum conditions for each carbon number. This makes it possible to obtain a high-purity fatty acid lower alkyl ester for each carbon number.
  • the fatty acid lower alkyl ester can be distilled with high purity, while impurities contained in the oil phase can be left as a residue at the bottom of the column. The impurities contained in the residue vary depending on the type of animal and vegetable oil used as the raw material.
  • a high-purity fatty acid lower alkyl ester can be obtained, such as a brownish brown color derived from these.
  • an ester mixed oil having an acid value of 2 or less is obtained in the esterification step (A), and the acid value of the ester mixed oil is obtained in the transesterification step (B). Accordingly, the transesterification is carried out while controlling the amount of the alkali catalyst within a specific range, and then the distillation step (C) is performed and the force is also subjected to the fractionation step (D). It is possible to stably produce high purity fatty acid lower alkyl esters with high yield for each carbon number. In addition, if the recycling step (R) is performed, fatty acids are effectively reused as raw materials, and a particularly high production yield can be achieved.
  • the fatty acid lower alkyl ester obtained in this way is mixed with the number of carbon atoms or, if necessary, as appropriate, to the raw materials for surfactants used in detergents, soaps, and higher alcohols. It is preferably used as a raw material.
  • Example [0063] Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to the following examples.
  • part means “part by mass” and “%” means “% by mass” unless otherwise specified.
  • the moisture content was measured according to the Karl Fischer method.
  • fatty acid methyl ester was produced from low color coconut oil produced in the Philippines.
  • This low-color coconut oil contains 0.5% of carbon 6 components, 7.4% of carbon 8 components, and 6.1% of carbon 10 components.
  • Components with 12 carbon atoms are 46.4%, components with 14 carbon atoms are 18.6%, components with 16 carbon atoms are 9.3%, components with 18 carbon atoms are 11.6%, components with 20 carbon atoms Of 0.1% of free fatty acids and 0.2% of gum.
  • the acid value was 6.4 and the water content was 800 ppm.
  • the number of carbon atoms refers to an ester that does not contain alcohol-derived carbon.
  • Methanol was passed through a column packed with Diaion SK1B (trade name, crosslinking degree: 8%) manufactured by Mitsubishi Chemical Corporation, which is an acidic gel-type cation exchange resin, and washed. Next, a mixture in which 20 parts of methanol was added to 100 parts of the raw material was supplied to the column and passed therethrough to obtain a reaction mixture.
  • the acid value of the ester mixed oil in the reaction mixture was 1.6.
  • the water content in the reaction mixture was 2300 ppm.
  • the column temperature was 65 ° C, the force ram residence time was 120 minutes, and methanol with a water content of 600 ppm was used.
  • the transesterification step (B) (first stage) was performed on the ester mixed oil obtained in (1) above as follows.
  • methanol and sodium hydroxide sodium hydroxide as an alkali catalyst were added to a reaction mixture containing 84% of an ester mixed oil.
  • the addition amount of methanol is 15 parts with respect to 120 parts of the reaction mixture, and the addition amount of sodium hydroxide is 100 parts of ester mixed oil. Against 0.3 parts.
  • the oil phase obtained in the above (2) was first flash distilled at a normal pressure of 150 ° C. to remove methanol and water as a distillate.
  • the top pressure is 8 kPa
  • the top temperature is 180 ° C
  • the reflux ratio is 1, and fatty acid methyl esters derived from fatty acids having 12 carbon atoms are distilled off.
  • the residue is distilled at a top pressure of 2 kPa, a top temperature of 200 ° C., a reflux ratio of 1, and fatty acid methyl ester derived from a fatty acid having 14 carbon atoms, and then the residue.
  • the top pressure is set to lkPa
  • the top temperature is set to 205 ° C
  • the reflux ratio is set to 0.5
  • the fatty acid methyl ester derived from the fatty acid having 16 carbon atoms is distilled.
  • a fatty acid methyl ester derived from a fatty acid having 18 carbon atoms was distilled at a pressure of 0.5 kPa, a top temperature of 200 ° C., a reflux ratio of 0, and an evaporation rate of 98%.
  • the top pressure is 10.6 kPa and the top temperature is 70 ° C for the distillate composed mainly of fatty acid methyl ester derived from fatty acids of 6, 8, and 10 carbon atoms obtained in (3) above. Then, the fatty acid methyl ester derived from the fatty acid having 6 carbon atoms is distilled at a reflux ratio of 12.2, and then the top pressure is 10 kPa, the top temperature is 121 ° C., the bottom temperature for the residue. A fatty acid methyl ester derived from a fatty acid having 8 carbon atoms was distilled at a temperature of 160 ° C. and a reflux ratio of 1.2 to obtain a fatty acid methyl ester derived from a fatty acid having 10 carbon atoms as a residue.
  • Table 1 summarizes the properties and yields of the major fatty acid methyl esters.
  • This crude palm oil contains 0.3% of carbon 12 components, 1.1% of 14 carbon components, 43.9% of 16 carbon components, and 53 of 18 carbon components. It contained 9% and 0.8% of 20 carbon atoms, and further contained 2.82% free fatty acids and 0.5% gum. The acid value was 6.2.
  • the ester mixture step (A) was carried out in the same manner as (1) of Example 1 except that a column packed with 6%) was used to obtain a reaction mixture.
  • the ester mixed oil in the reaction mixture had an acid value of 1.2.
  • the water content in the reaction mixture was 2900 ppm.
  • Example 1 (2) In the same manner as in Example 1 (2), an oil phase mainly composed of fatty acid methyl ester and a glycerin phase were produced. Next, this was allowed to stand at 40 ° C for 30 minutes, and then separated into an oil phase and a glycerin phase. To 100 parts of the oil phase, 20 parts of water for washing was added, and after stirring, this was carried out at 40 ° C. It was left for 60 minutes. Thereafter, it was separated into an oil phase and an aqueous phase. The fatty acid methyl ester concentration in the oil phase was 95.8%.
  • the oil phase obtained in (3) above was first flash distilled at 170 ° C. under normal pressure to remove methanol and water as distillate.
  • top temperature 180 ° C, top pressure 2 kPa, reflux ratio 10 is performed on the residue of flash distillation, and fatty acid methyl ester derived from fatty acids having 12 or 14 carbon atoms is the main component. A distillate was obtained.
  • the residue obtained in (4) above has a top pressure of 0.6 kPa, a top temperature of 200 ° C, an evaporation rate of 98%, a reflux ratio of 0, and fatty acid methyl ester derived from fatty acids having 16 and 18 carbon atoms.
  • a distillate containing ter as the main component was obtained.
  • fatty acid methyl ester derived from a fatty acid having 16 carbon atoms was distilled from the distillate at a top pressure of 2. OkPa, a top temperature of 190 ° C, and a reflux ratio of 0.5.
  • a fatty acid methyl ester derived from a fatty acid having 18 carbon atoms was distilled from the residue at a top pressure of 0.5 kPa, a top temperature of 190 ° C., a reflux ratio of 0, and an evaporation rate of 99%.
  • the residue was returned to the first step of fractional distillation step (D).
  • the top pressure of the distillation column is 8 kPa and the top temperature is 180 ° C with respect to the distillate containing fatty acid methyl esters derived from fatty acids having 12 and 14 carbon atoms obtained in (4) as the main component.
  • the top pressure of the distillation column is 8 kPa and the top temperature is 180 ° C with respect to the distillate containing fatty acid methyl esters derived from fatty acids having 12 and 14 carbon atoms obtained in (4) as the main component.
  • Table 1 summarizes the properties and yields of the major fatty acid methyl esters.
  • the esterification step (A) was carried out in the same manner as (1) of Example 1 except that a column packed with 4%) was used to obtain a reaction mixture.
  • the ester mixed oil in the reaction mixture had an acid value of 0.2.
  • the water content in the reaction mixture was 2500 ppm.
  • Example 2 In the same manner as in Example 1 (2), an oil phase mainly composed of fatty acid methyl ester and a glycerin phase were produced.
  • the glycerin phase obtained by the transesterification reaction of (3) above and the aqueous phase obtained by washing with water are mixed, and 70% sulfuric acid is added to the mixture to adjust the pH to 3.0. Stir and mix in C for 60 minutes. Subsequently, the sodium sulfate produced from the mixture was removed by centrifugation, and then separated into a fatty acid phase and an aqueous phase containing water, methanol and glycerin.
  • the esterification step (A) is carried out on the mixture obtained in the above (4) having an acid value of 8.7 under the same conditions as in the above (2), and a reaction comprising an ester mixed oil having an acid value of 0.4 A mixture was obtained.
  • the water content in the reaction mixture was 3500 ppm.
  • an ester exchange reaction step (B) was performed on the ester mixed oil under the same conditions as in the above (3) to obtain an oil phase and a glycerin phase.
  • the concentration of fatty acid methyl ester in the oil phase after washing with water was 95.3%.
  • the oil phase obtained in the above (5) was first flash distilled at a normal pressure of 170 ° C. to remove methanol and water as a distillate.
  • the top pressure is 8 kPa
  • the top temperature is 180 ° C
  • the reflux ratio is 1, and fatty acid methyl esters derived from fatty acids having 12 carbon atoms are distilled off.
  • the residue is distilled at a top pressure of 2 kPa, a top temperature of 200 ° C, a reflux ratio of 1, and distilling fatty acid methyl esters derived from fatty acids having 14 carbon atoms.
  • a distillate containing fatty acid methyl ester derived from a fatty acid having 16 or 18 carbon atoms as a main component was obtained with a top pressure of 0.6 kPa, a top temperature of 200 ° C., an evaporation rate of 98%, and a reflux ratio of 0. .
  • fatty acid methyl ester derived from a fatty acid having 16 carbon atoms was distilled from the distillate at a top pressure of 1. OkPa, a top temperature of 205 ° C., and a reflux ratio of 0.5.
  • a fatty acid methyl ester derived from a fatty acid having 18 carbon atoms was distilled out at a top pressure of 0.5 kPa, a top temperature of 190 ° C., a reflux ratio of 0, and an evaporation rate of 99%.
  • the residue was returned to the step of distilling the fatty acid methyl ester derived from the fatty acid having 16 or 18 carbon atoms as the main component in the fractionation step (D).
  • the top pressure was 10.6 kPa and the top temperature was 70 ° C for the distillate containing fatty acid methyl esters derived from fatty acids of 6, 8 and 10 carbon atoms obtained in (6).
  • a reflux ratio of 12.2 was used to distill fatty acid methyl esters derived from fatty acids having 6 carbon atoms.
  • the top pressure was lOkPa
  • the top temperature was 121 ° C
  • the bottom temperature was the residue.
  • the fatty acid methyl ester derived from a fatty acid having 8 carbon atoms was distilled at a temperature of 160 ° C. and a reflux ratio of 1.2 to obtain a fatty acid methyl ester derived from a fatty acid having 10 carbon atoms as a residue.
  • Table 1 summarizes the properties, yields, etc. of the main fatty acid methyl esters with 12, 16, and 18 carbon atoms.
  • Example 2 the same Malaysian crude palm oil (CPO) coconut fatty acid methyl ester as that used in Example 2 was produced.
  • Step (A) was performed to obtain a reaction mixture.
  • the ester mixed oil in the reaction mixture had an acid value of 0.2.
  • the water content in the reaction mixture was 3200 ppm.
  • the transesterification step (B) (second stage) was performed on the ester mixed oil obtained in (2) above as follows.
  • Example 1 (2) an oil phase mainly composed of fatty acid methyl ester and a glycerin phase were produced and allowed to stand at 40 ° C. for 60 minutes. Separated into phases. The fatty acid methyl ester concentration in the oil phase was 95.3%.
  • the glycerin phase obtained in the first stage and the aqueous phase obtained in the second stage are mixed, and 90% sulfuric acid is added to the mixture.
  • the pH was adjusted to 3.0, and the mixture was stirred and mixed at 60 ° C for 60 minutes.
  • sodium sulfate produced from this mixture was removed by centrifugation, and then separated into a fatty acid phase and an aqueous phase containing water, methanol, and glycerin.
  • Example 2 For the aqueous phase containing water, methanol, and glycerin, the same treatment as in Example 1 was performed to obtain crude glycerin, and methanol was recovered and waste water was removed.
  • the esterification step (A) is carried out on the mixture obtained in the above (4) having an acid value of 8.3 under the same conditions as in the above (2), and a reaction containing an ester mixed oil having an acid value of 0.4. A mixture was obtained. The water content in the reaction mixture was 3400 ppm.
  • the amount of catalyst in the first stage is calculated from the above formula (1), and the above (3) and Under the same conditions, this ester mixed oil was subjected to a two-stage transesterification step (B) to obtain an oil phase and a glycerin phase.
  • the concentration of fatty acid methyl ester in the oil phase after washing with water was 99.1%.
  • the fatty acid methyl ester concentration in the oil phase was 95.2%.
  • Example 2 The same operation as in Example 2 (4) and (5) was performed.
  • Table 1 summarizes the properties, yields, etc. of the major fatty acid methyl esters having 12, 16, and 18 carbon atoms.
  • Example 2 the same Malaysian crude palm oil (CPO) coconut fatty acid methyl ester as that used in Example 2 was produced.
  • the ester exchange reaction step (B) (two steps) was carried out on the ester mixed oil obtained in (2) above in the same manner as in Example 3, (3).
  • the fatty acid methyl ester concentration in the oil phase obtained in the first stage was 96.0%.
  • the fatty acid methyl ester concentration in the oil phase obtained in the second stage was 99.3%.
  • aqueous phase mainly composed of methanol, glycerin and the like
  • the same treatment as in Example 1 was performed to obtain crude glycerin, and methanol was recovered and waste water was removed.
  • 3 parts of the fatty acid phase was returned to 100 parts of crude palm oil and mixed.
  • the resulting mixture had an acid value of 8.9 and a gum content of 0.51%.
  • the degumming step (P) was carried out on the mixture obtained in (4) with an acid value of 8.9 under the same conditions as in (1) above.
  • the resulting degummed product had a gum content of 0.2%, which was the same degumming effect as in the case of (1) above.
  • the water content was lOOOppm.
  • the esterification step (A) was carried out under the same conditions as in the above (2) to obtain a reaction mixture containing an ester mixed oil having an acid value of 0.4.
  • the water content in the reaction mixture is 4000ppm.
  • Example 2 The same operation as in Example 2 (4) and (5) was performed.
  • Table 1 summarizes the properties, yields, etc. of the major fatty acid methyl esters having 12, 16, and 18 carbon atoms.
  • Example 2 Except for not performing the degumming step (P) and the esterification step (A), the same procedure as in Example 2 (the amount of alkali catalyst (sodium hydroxide) is 0.3 parts) and the transesterification step (B ) However, the transesterification reaction hardly proceeded, and the resulting mixture was allowed to stand at 40 ° C for 30 minutes, but it did not separate into an oil phase and a glycerin phase.
  • Transesterification reaction step (B) was carried out in the same manner as in Comparative Example 1 except that the amount of sodium hydroxide was changed to 0.8 part.
  • the obtained mixture was allowed to stand at 40 ° C for 30 minutes, separated into an oil phase and a glycerin phase, 20 parts of water was added to 100 parts of the oil phase, and after stirring, this was allowed to stand at 40 ° C for 60 minutes. Place It separated into an oil phase and an aqueous phase.
  • the fatty acid methyl ester concentration in the oil phase was 95.0%.
  • the distillation step (C) and the fractionation step (D) were performed on the oil phase under the same conditions as in Example 2.
  • Table 1 summarizes the properties and yields of the major fatty acid methyl esters obtained.
  • the concentration of fatty acid methyl ester was determined by gas chromatography (GC) using a calibration curve prepared in advance. That is, about 0.2 g of the pretreated sample was taken in a blood collection bottle, dissolved with about 1 lg of n-xane, and operated under the following GC measurement conditions, and the concentration of each fraction was calculated from the calibration curve.
  • GC gas chromatography
  • the calibration curve was prepared by dissolving each fatty acid methyl ester standard product (carbon number: 622, manufactured by Wako Pure Chemical Industries, Ltd.) in n-xane to prepare a standard solution so as to obtain a predetermined concentration.
  • a standard solution so as to obtain a predetermined concentration.
  • GC Measurement Conditions> ⁇ GC: Shimadzu Corporation, trade name GC6A 'Column: DEGS Nylol succinate 20%), column temperature: 180 ° C, inlet temperature: 250 ° C 'detector temperature: 250 ° C, RANGE (10 n ): ⁇ 3 ⁇ Carrier gas: N, 50 mL / min, Detector:
  • ⁇ 1 The above-mentioned ⁇ 1 was processed by the CDM test (standard oil analysis method: 20LZhrs air, 120 ° C, oxidation degradation), and the conductivity of the water that absorbed the generated gas became 300 SZcm
  • B2 A2 was processed by CDM test (standard oil analysis method: 20LZhrs air, 120 ° C, oxidation degradation), and when the conductivity of water that absorbed the generated gas became 300 SZcm
  • Example 1 The fatty acid methyl ester of Example 1 was evaluated according to the following criteria.
  • Mass ratio A2ZB2 odor equivalent to lZl mixture
  • Mass ratio A2ZB2 Odor equivalent to lZ4 mixture
  • Mass ratio A3ZB3 odor equivalent to lZl mixture
  • Mass ratio A3ZB3 odor equivalent to lZ4 mixture
  • Reagent grade lauric acid methyl ester manufactured by Wako Pure Chemical Industries, Ltd. is used as reference sample L1, and L 1 is treated by CDM test (standard fat analysis method : 20LZhrs air, 120 ° C, oxidative degradation) to absorb the generated gas
  • the reference sample L2 was taken when the water conductivity reached 300 ⁇ SZcm.
  • the fatty acid methyl ester of Example 3 was evaluated according to the following criteria. Score: Evaluation criteria
  • Reagent grade normitic acid methyl ester manufactured by Wako Pure Chemical Industries was used as reference sample P1, and P1 was treated by CDM test (standard fat analysis method : 20LZhrs air, oxidative degradation at 120 ° C) to absorb the generated gas.
  • CDM test standard fat analysis method : 20LZhrs air, oxidative degradation at 120 ° C
  • a high-purity fatty acid lower alkyl ester suitable for a raw material of a surfactant having no coloring or odor, a raw material of soap, a higher alcohol, or the like can be stably produced at a high yield for each carbon number.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Microbiology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Fats And Perfumes (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Procédé de production d'esters alkyliques inférieurs d'acides gras, comprenant : une étape d'estérification (A) dans laquelle les acides gras contenus dans un matériau brut comprenant une matière grasse animale/végétale sont estérifiés avec un alcool alkylique inférieur en utilisant une résine échangeuse de cations afin d'obtenir un mélange réactionnel contenant un mélange d'esters sous forme d'huile ayant un indice d'acide inférieur ou égal à 2 ; une étape de transestérification (B) comprenant au moins une première étape dans laquelle la matière grasse contenue dans le mélange d'esters sous forme d'huile est transestérifiée avec un alcool alkylique inférieur tout en régulant la quantité d'un catalyseur alcalin pour qu'elle se situe dans la plage de 0,1 à 1 partie en masse pour 100 parties en masse du mélange d'esters sous forme d'huile en fonction de l'indice d'acide ; une étape de distillation (C) dans laquelle un distillat liquide contenant des esters alkyliques inférieurs d'acides gras ayant des atomes de carbone en plus petits nombres est enlevé par distillation de la phase huileuse obtenue dans l'étape de transestérification (B) afin d'obtenir un résidu comprenant des esters alkyliques inférieurs d'acides gras ayant des atomes de carbone en plus grands nombres ; et une étape de fractionnement (D) comprenant au moins une étape dans laquelle les esters alkyliques inférieurs d'acides gras ayant des atomes de carbone en plus grands nombres et qui sont contenus dans le résidu sont séparés par distillation en fractions qui diffèrent par le nombre d'atomes de carbone.
PCT/JP2006/322830 2005-12-27 2006-11-16 Procédé de production d'esters alkyliques inférieurs d'acides gras WO2007074592A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2007551865A JP5005547B2 (ja) 2005-12-27 2006-11-16 脂肪酸低級アルキルエステルの製造方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2005373776 2005-12-27
JP2005-373776 2005-12-27

Publications (1)

Publication Number Publication Date
WO2007074592A1 true WO2007074592A1 (fr) 2007-07-05

Family

ID=38217814

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2006/322830 WO2007074592A1 (fr) 2005-12-27 2006-11-16 Procédé de production d'esters alkyliques inférieurs d'acides gras

Country Status (3)

Country Link
JP (1) JP5005547B2 (fr)
MY (1) MY153192A (fr)
WO (1) WO2007074592A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013072664A1 (fr) 2011-11-17 2013-05-23 Davy Process Technology Limited Procédé de production d'alcools gras à partir d'acides gras
US9212114B2 (en) 2012-10-09 2015-12-15 Johnson Matthey Davy Technologies Limited Process for the production of a fatty alcohol from a fatty acid

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS51147532A (en) * 1975-06-13 1976-12-17 Lion Corp Process for manufacturing carotene condensates
JPH0234692A (ja) * 1988-07-22 1990-02-05 Lion Corp メチルエステルの製造方法
JPH04128250A (ja) * 1990-06-04 1992-04-28 Nippon Suisan Kaisha Ltd 高濃度エイコサペンタエン酸またはそのエステルの製造方法
JP2001262179A (ja) * 2000-03-23 2001-09-26 Lion Corp 精製油脂の製造方法

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4920583B2 (ja) * 2005-06-03 2012-04-18 ライオン株式会社 脂肪酸低級アルキルエステルおよび軽油代替燃料

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS51147532A (en) * 1975-06-13 1976-12-17 Lion Corp Process for manufacturing carotene condensates
JPH0234692A (ja) * 1988-07-22 1990-02-05 Lion Corp メチルエステルの製造方法
JPH04128250A (ja) * 1990-06-04 1992-04-28 Nippon Suisan Kaisha Ltd 高濃度エイコサペンタエン酸またはそのエステルの製造方法
JP2001262179A (ja) * 2000-03-23 2001-09-26 Lion Corp 精製油脂の製造方法

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013072664A1 (fr) 2011-11-17 2013-05-23 Davy Process Technology Limited Procédé de production d'alcools gras à partir d'acides gras
US9212114B2 (en) 2012-10-09 2015-12-15 Johnson Matthey Davy Technologies Limited Process for the production of a fatty alcohol from a fatty acid

Also Published As

Publication number Publication date
MY153192A (en) 2015-01-29
JP5005547B2 (ja) 2012-08-22
JPWO2007074592A1 (ja) 2009-06-04

Similar Documents

Publication Publication Date Title
US8728177B2 (en) Production of biodiesel and glycerin from high free fatty acid feedstocks
JP2007176973A (ja) 軽油代替燃料用の脂肪酸低級アルキルエステルの製造方法
CA2615712C (fr) Procede de production d'alkylesters d'acide carboxylique
EP1894913A1 (fr) Production d'esters d'acides gras et d'alcools inférieurs
US20050222469A1 (en) Process for producing fatty alcohol
EP1565424A1 (fr) Procede de fabrication d'esters d'alkyle
JP4920583B2 (ja) 脂肪酸低級アルキルエステルおよび軽油代替燃料
US8440847B2 (en) Method of converting free fatty acid (FFA) from oil to methyl ester
EP1892232A1 (fr) Production d'esters d'acides gras et alcools inférieurs
CN101104683A (zh) 从甘油渣中提取聚甘油的方法
WO2007074592A1 (fr) Procédé de production d'esters alkyliques inférieurs d'acides gras
KR20220013359A (ko) 어유 콜레스테롤
JP2009242777A (ja) 脂肪酸低級アルキルエステルの製造方法
JP4943001B2 (ja) トコトリエノール類含有組成物の製造方法
JP3227006B2 (ja) 脂肪酸エステルの製造方法
JP5301982B2 (ja) 濃縮ホルボールエステルの製造方法
ZA200504848B (en) Method for production of alkyl esters
JPH0466231B2 (fr)
NZ540399A (en) Method for production of alkyl esters from a mixture of glycerides and fatty acids
JP2009114305A (ja) 脂肪酸低級アルキルエステルの製造方法
CZ300133B6 (cs) Zpusob výroby methylesteru mastných kyselin transesterifikací triglyceridu, zejména z repkového oleje, a zarízení k provádení tohoto zpusobu
SK50232008A3 (sk) Spôsob oddelenia mastných kyselín zo vstupných surovín na výrobu alkylesterov

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application
WWE Wipo information: entry into national phase

Ref document number: 2007551865

Country of ref document: JP

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 06832719

Country of ref document: EP

Kind code of ref document: A1