WO2015020073A1 - Procédé de production d'ester d'acide gras de saccharose - Google Patents

Procédé de production d'ester d'acide gras de saccharose Download PDF

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Publication number
WO2015020073A1
WO2015020073A1 PCT/JP2014/070677 JP2014070677W WO2015020073A1 WO 2015020073 A1 WO2015020073 A1 WO 2015020073A1 JP 2014070677 W JP2014070677 W JP 2014070677W WO 2015020073 A1 WO2015020073 A1 WO 2015020073A1
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Prior art keywords
fatty acid
weight
acid ester
sucrose
sucrose fatty
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PCT/JP2014/070677
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English (en)
Japanese (ja)
Inventor
啓介 楠井
宏史 谷越
正樹 手塚
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第一工業製薬株式会社
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Publication of WO2015020073A1 publication Critical patent/WO2015020073A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
    • C07H13/00—Compounds containing saccharide radicals esterified by carbonic acid or derivatives thereof, or by organic acids, e.g. phosphonic acids
    • C07H13/02—Compounds containing saccharide radicals esterified by carbonic acid or derivatives thereof, or by organic acids, e.g. phosphonic acids by carboxylic acids
    • C07H13/04—Compounds containing saccharide radicals esterified by carbonic acid or derivatives thereof, or by organic acids, e.g. phosphonic acids by carboxylic acids having the esterifying carboxyl radicals attached to acyclic carbon atoms
    • C07H13/06—Fatty acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
    • C07H1/00—Processes for the preparation of sugar derivatives

Definitions

  • the present invention relates to a method for producing a sucrose fatty acid ester. More specifically, the present invention relates to a method for producing a sucrose fatty acid ester, in which coloring can be suppressed and a sucrose fatty acid ester having a very small amount of remaining organic solvent can be obtained.
  • Sucrose fatty acid esters are compounds used in various applications, typified by chemical reaction aids, additives to foods, cosmetics, pharmaceuticals, detergents, antistatic agents for packaging containers, etc. Excellent biodegradability and surface activity.
  • the sucrose fatty acid ester is obtained, for example, by reacting sucrose and a fatty acid alkyl ester in a reaction solvent in the presence of a catalyst. In this case, after completion of the reaction, a reaction mixture containing sucrose fatty acid ester is obtained.
  • the reaction mixture is a liquid using an organic solvent and water. After subjecting to liquid extraction, the obtained organic solvent solution is subjected to continuous countercurrent extraction with water to obtain an organic solvent solution containing almost no dimethyl sulfoxide as a reaction solvent, and the solvent is distilled off from this organic solvent solution.
  • Patent Document 1 A method is known (Patent Document 1).
  • Patent Document 1 cannot sufficiently suppress the coloring of the sucrose fatty acid ester after drying because the organic solvent is not sufficiently removed and the sucrose fatty acid ester is very easily colored. There was a problem.
  • the present invention is intended to provide a method for producing a sucrose fatty acid ester in which coloring is suppressed and the residual amount of the organic solvent is extremely small.
  • the present inventors conducted a reduced-pressure drying step for obtaining a target product by using one or more reduced-pressure dryers to set the internal pressure and / or heating temperature. After making a series of processes that change at least two stages, the internal pressure and heating temperature of the first stage and the final stage are set within predetermined ranges, respectively, so that coloring is substantially suppressed and the residual amount of solvent is extremely reduced.
  • the present invention has been completed by finding that it can be reduced to a small amount and further studying it.
  • the present invention is a method for producing a sucrose fatty acid ester, wherein a sucrose fatty acid ester is obtained from a reaction mixture obtained by reacting sucrose and a fatty acid lower alkyl ester in a reaction solvent in the presence of an alkali catalyst.
  • the in-machine pressure in the first stage of the reduced-pressure drying step is equal to or lower than atmospheric pressure, and the heating temperature is 20 ° C. or higher and 200 ° C. or lower
  • the present invention relates to a method for producing a sucrose fatty acid ester, comprising a reduced pressure drying step in which the in-machine pressure at the final stage of the reduced pressure drying step is 10 kPa ⁇ abs or less and the heating temperature is 20 ° C. or higher and 200 ° C. or lower.
  • At least one of the vacuum dryers is preferably a twin screw extruder.
  • the series of reduced-pressure drying steps is preferably composed of any one of 2 to 9 steps.
  • the content of the sucrose fatty acid ester in the organic solvent phase obtained in the purification step (2) is preferably 10 to 80% by weight.
  • the present invention also relates to a sucrose fatty acid ester obtained by the above production method, having a Gardner color number of 3 or less and a residual amount of organic solvent of 10 ppm or less.
  • a sucrose fatty acid ester in which coloring is suppressed and the residual amount of the organic solvent is extremely small can be obtained. More specifically, it is possible to obtain a Gardner color number of 3 or less for coloring and a 10 ppm or less residual solvent amount.
  • the sucrose fatty acid ester is an ester of sucrose and a fatty acid.
  • the fatty acid include saturated or unsaturated fatty acids having 6 to 30 carbon atoms. The carbon number is preferably 8 or more. On the other hand, the carbon number is preferably 22 or less.
  • the saturated fatty acid include caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, and behenic acid.
  • the unsaturated fatty acid include linoleic acid, oleic acid, linolenic acid, erucic acid, ricinoleic acid and the like.
  • the object of the present invention has a hue of 3 or less, preferably 2 or less, and a residual amount of organic solvent of 10 ppm or less, preferably 5 ppm or less.
  • the average value of the esterification rate of the alcohol portion of sucrose (hereinafter referred to as “average esterification degree”) is not particularly limited, but the removal of the solvent of the present invention
  • the method can be particularly suitably applied when the average degree of esterification, which is considered to be easy to color the sucrose fatty acid ester, is 6.0 or less.
  • the sucrose fatty acid ester can be produced by subjecting sucrose and a fatty acid lower alkyl ester to a transesterification reaction by a conventional method.
  • the transesterification reaction can be carried out under total reflux.
  • it is preferable that the transesterification reaction is initially performed while distilling the reaction solvent, followed by distilling a certain amount of the reaction solvent, and then performing total reflux without distilling. In this way, the transesterification reaction is promoted, and the distilled reaction solvent can be recovered and reused.
  • the amount of the reaction solvent to be distilled off is, for example, about 0.1 to 30% by weight, preferably about 1 to 20% by weight of the whole reaction solvent.
  • sucrose Any commercially available sucrose can be used.
  • the sucrose may be one obtained by collecting sucrose that has not been reacted at the time of producing the sucrose fatty acid ester (collected sugar).
  • the form may be a solid state or a solution state dissolved in a solvent.
  • generated at the neutralization process mentioned later may be included.
  • Examples of the fatty acid lower alkyl ester include esters of the above-described fatty acids and lower aliphatic alcohols.
  • Examples of lower aliphatic alcohols include those having 1 to 4 carbon atoms, and specific examples include methanol, ethanol, propanol, butanol and the like.
  • the fatty acid lower alkyl ester may be used alone or as a mixture of two or more of any proportion.
  • the fatty acid lower alkyl ester is usually used in an amount of 0.1 to 15 mol per mol of sucrose, but is preferably 0.2 mol or more, and preferably 10 mol or less.
  • reaction solvent used in the transesterification reaction any of those commonly used in this field can be used as long as the reaction proceeds suitably.
  • examples of such a reaction solvent include trimethylamine, triethylamine, N -Tertiary amines such as methylmorpholine, pyridine, quinoline, pyrazine, methylpyrazine, N, N-dimethylpiperidine, amides such as formamide, N, N-dimethylformamide, 2-pyrrolidone, N-methyl-2-pyrrolidone And dialkyl sulfoxides such as dimethyl sulfoxide, among which pyridine, N, N-dimethylformamide, and dimethyl sulfoxide are preferable. From the viewpoint of thermal stability, solubility in sucrose and safety, dimethyl sulfoxide ( Hereinafter abbreviated as DMSO.) The most preferred.
  • the reaction solvent can be used alone or in combination of two or more.
  • the amount of the reaction solvent used is usually preferably 30 to 90% by weight in the reaction mixture, more preferably 50% by weight or more, and more preferably 85% by weight or less.
  • the reaction solvent preferably has a water content of 0.1% by weight or less.
  • the transesterification reaction is performed in the presence of an alkali catalyst.
  • the alkali catalyst When the reaction system is substantially non-aqueous, the alkali catalyst is present in a suspended state in the reaction system.
  • the alkali catalyst include alkali metal hydrides (sodium bicarbonate, potassium bicarbonate, etc.), alkali metal hydroxides (lithium hydroxide, sodium hydroxide, potassium hydroxide, etc.), alkali metal salts (sodium carbonate, carbonate, etc.). Potassium) and the like are effective, and potassium carbonate, sodium carbonate and the like are particularly preferable.
  • the alkali catalyst can be used alone or in combination of two or more.
  • the amount of these alkali catalysts used is usually preferably 0.1 to 2.0 parts by weight, more preferably 0.2 parts by weight or more, based on 1 part by weight of sucrose and fatty acid alkyl ester. 1.0 part by weight or less is more preferable.
  • the reaction temperature for the transesterification reaction is usually preferably 80 to 120 ° C, more preferably 90 ° C or more, and more preferably 100 ° C or less.
  • the reaction pressure is usually 0.2 to 43 kPa, preferably 0.7 to 32 kPa.
  • the reaction time is not particularly limited, but is usually preferably 1 to 50 hours, more preferably 2 hours or more, and more preferably 40 hours or less.
  • the reaction between sucrose and the fatty acid lower alkyl ester is preferably carried out under reflux of the reaction solvent. Thereby, alcohol by-produced during the reaction can be easily removed from the reaction system.
  • the transesterification reaction is stopped by adding an acid and neutralizing the alkali catalyst.
  • acids include organic acids such as formic acid, acetic acid, propionic acid, oxalic acid, succinic acid, benzoic acid, tartaric acid, lactic acid, malic acid, carbonic acid, citric acid and maleic acid, and inorganic acids such as hydrochloric acid and sulfuric acid.
  • lactic acid, malic acid, citric acid and the like are preferable from the viewpoint of influence on the living body.
  • the pH of the reaction mixture is in the range of about 5.0 to 7.5, preferably about 5.5 to 6.5, more preferably about 6.0. It is preferable to add these acids so that These acids can be used alone or in combination of two or more.
  • sucrose has eight hydroxyl groups
  • the produced sucrose fatty acid ester is theoretically a mixture from monoester to octaester, and the composition of the produced ester can be adjusted by the proportion of raw materials used.
  • the reaction mixture of sucrose and fatty acid lower alkyl ester thus obtained contains a reaction solvent, an unreacted raw material, an alkali catalyst, an acid and the like in addition to the target sucrose fatty acid ester.
  • the extraction step in the present invention is a step of subjecting the reaction mixture to liquid-liquid extraction using an organic solvent and water, and extracting sucrose fatty acid ester into the organic solvent phase. At this time, the reaction solvent, the unreacted raw material, the alkali catalyst, the acid, the alkali catalyst and the neutralized salt with the acid, etc. migrate to the aqueous phase.
  • the concentration of the reaction solvent in the reaction mixture is high, it is preferable to reduce the concentration in advance by distilling a part thereof.
  • a preferable concentration of the reaction solvent is 30% by weight or less, more preferably 20% by weight or less in the reaction mixture.
  • the lower limit of the concentration of the reaction solvent is not particularly limited as long as the viscosity is not excessively increased or solidified, but is preferably 5% by weight or more, more preferably 10% by weight or more in the reaction mixture.
  • the distillation method is not particularly limited.
  • batch distillation using a stirred tank capable of reducing pressure and heating, or a thin film evaporator also referred to as “thin film evaporator” or “thin film evaporator”. It can be carried out at a temperature of 60 to 150 ° C. under reduced pressure using a mold (vertical, horizontal, etc.). The reaction solvent thus distilled off can be recovered and reused in the transesterification reaction.
  • Liquid-liquid extraction can be carried out by adding an organic solvent (extraction solvent) and water to the reaction mixture and stirring the mixture.
  • alcohols include n-butyl alcohol, isobutyl alcohol, t-butyl alcohol, n-amyl alcohol, isoamyl alcohol, n-hexanol, and cyclohexanol.
  • ketones include methyl ethyl ketone and diethyl ketone. Or methyl isobutyl ketone is mentioned.
  • the amount of the organic solvent used relative to the reaction mixture is usually 0.5 to 20 parts by weight, preferably 1 to 10 parts by weight, based on 1 part by weight of the sucrose fatty acid ester in the reaction mixture.
  • the amount of water used is usually 0.05 to 10 parts by weight, preferably 0.5 to 2 parts by weight with respect to 1 part by weight of the organic solvent. Stirring is usually sufficient for 0.5 to 4 hours.
  • the organic solvent can be used alone or in combination of two or more.
  • the purification solvent recovered in the next purification step can be used in place of the “water”, in addition to the commonly used water.
  • Liquid-liquid extraction is preferably performed after adjusting the pH of the mixture of the organic solvent and water. By doing so, hydrolysis of the sucrose fatty acid ester is suppressed and it contributes to efficient extraction into an organic solvent phase.
  • the pH of the mixed solution is preferably 5.5 to 6.5.
  • the acid used for neutralization of the alkali catalyst can be appropriately used.
  • liquid-liquid extraction is preferably performed by adding a salting-out agent from the viewpoint of stable operation.
  • a salting-out agent is arbitrary, the salt of the acid used for pH adjustment is preferable.
  • alkali carbonates potassium, sodium, etc.
  • alkali citrates potassium, sodium, etc.
  • alkali lactates potassium, sodium, etc.
  • alkali sulfates potassium, sodium, etc.
  • Liquid-liquid extraction is usually carried out under conditions where the concentration of the salting-out agent is 50 ppm or more, but it is preferably carried out in the range of 500 to 3000 ppm from the viewpoint of stable operability and economy.
  • a bleaching agent to the mixture to reduce the coloration as desired.
  • the bleaching agent include oxidizing agents such as hydrogen peroxide, sodium chlorite, sodium hypochlorite and ozone, and reducing agents such as sodium sulfite, potassium pyrosulfite, sodium pyrosulfite and sodium hyposulfite.
  • an adsorbent such as activated carbon can be used.
  • the added amount of the bleaching agent is 0. The amount is preferably 1 to 5.0 parts by weight, more preferably 0.3 parts by weight or more, and even more preferably 3.0 parts by weight or less.
  • Liquid-liquid extraction is carried out by stirring the mixture obtained according to the above operation.
  • Stirring of the mixture can be usually carried out at a temperature of 40 to 80 ° C., more preferably 50 ° C. or more, and more preferably 70 ° C. or less.
  • the stirring time is usually preferably 1 to 8 hours, more preferably 2 hours or more, and more preferably 6 hours or less.
  • the excess bleaching agent is decomposed or the remaining bleaching agent is removed. That is, when an oxidizing agent is added as a bleaching agent, an excess bleaching agent is decomposed using a reducing agent, and conversely, when a reducing agent is added as a bleaching agent, an oxidizing agent is used.
  • These reducing agents or oxidizing agents are used in an amount of 0.9 to 1.5 equivalents relative to 1 equivalent of the remaining amount of bleach (that is, 90 to 150 of the amount necessary to decompose all the remaining bleaching agent). Mass%), preferably 1.0 equivalent or more, or more preferably 1.2 equivalent or less.
  • an adsorbent is used as a bleaching agent, the bleaching agent remaining in the mixture is removed by, for example, filtration.
  • the mixture After decomposing or removing the bleaching agent, the mixture is allowed to stand to separate into an organic solvent phase and an aqueous phase, and then both phases are separated. At this time, the sucrose fatty acid ester is contained in the organic solvent phase. On the other hand, the aqueous layer contains unreacted sucrose, reaction solvent, salt produced in the reaction step, and the like.
  • the separated organic solvent phase is subjected to the following purification process. Further, the collected aqueous phase can recover the reaction solvent and unreacted sucrose by distilling off water and an organic solvent under reduced pressure (recovered sugar), and can be reused for transesterification.
  • the purification step in the present invention is a step of purifying the organic solvent phase obtained in the extraction step using a counter solvent by a countercurrent distribution type extraction device having a light liquid supply port and a heavy liquid supply port.
  • a countercurrent distribution type extraction device having a light liquid supply port and a heavy liquid supply port.
  • the heavier specific gravity is supplied from the heavy liquid supply port
  • the lighter specific gravity is supplied from the light liquid supply port to direct the organic solvent phase and the purification solvent.
  • the purpose is to reduce the reaction solvent remaining in the organic solvent phase by flowing contact.
  • the pH of the purification solvent it is preferable to adjust the pH of the purification solvent to 5.0 to 6.0. By doing so, it contributes to suppressing hydrolysis of the sucrose fatty acid ester and facilitating countercurrent distribution. Adjustment of pH can be suitably performed using the acid used for the neutralization of the said alkali catalyst.
  • the “countercurrent distribution type extraction device having a light liquid supply port and a heavy liquid supply port” used in the present invention is a case where a light liquid having a lower specific gravity and a heavy liquid having a higher specific gravity are supplied from the respective supply ports.
  • the reaction solvent or the like remaining in the organic solvent phase is transferred to the purification solvent by countercurrent contact, and then the organic solvent phase and the purification solvent are respectively recovered, and the recovered organic solvent phase is subjected to the next purification. Provided to the process. This operation is repeated until the concentration of the reaction solvent remaining in the organic solvent phase is 1 ppm or less, preferably 0.5 ppm or less, more preferably 0.2 ppm or less.
  • the counter-current distribution type extraction device may be of a vertical type (tower type) or a horizontal type. Moreover, the weir type thing which provided the weir for enabling efficient counterflow inside is also sufficient. Further, from the viewpoint of operational efficiency, a continuous type is preferable in which the recovered organic solvent phase can be continuously supplied again.
  • the counter-current distribution type extraction device any of those usually used in this field can be used. Specifically, a perforated plate extraction tower, a dam plate type extraction tower (for example, WINTRAY (trade name, Etc., etc.), baffle extraction towers, rotary column towers and other column tower type extraction devices; spray towers, packed towers, pulsation type extraction towers and other differential contact devices.
  • the purification solvent water can be used, or a mixed solution of water and the organic solvent used in the extraction step can be used.
  • a purification solvent water is basically used. However, when the purification step is continuously performed, a predetermined amount of the organic solvent used in the extraction step is mixed with water as a purification solvent in advance. It is preferable to use one because the purification step can be carried out stably without changing the mixing ratio of water and the organic solvent in the purification solvent.
  • the recovered solvent for purification can be reused instead of “water” in the extraction step as described above.
  • the purification step is preferably performed by adding a salting-out agent to the purification solvent from the viewpoint of stable operation.
  • a salting-out agent is arbitrary, the salt of the acid used for pH adjustment is preferable.
  • alkali citrate such as potassium and sodium
  • alkali lactate such as potassium and sodium
  • alkali sulfate such as potassium and sodium.
  • the purification step is usually performed under the condition that the concentration of the salting-out agent is 50 ppm or more, but it is preferably performed in the range of 500 to 3000 ppm from the viewpoint of stable operation and economy.
  • the temperature in the purification step is preferably 40 to 80 ° C. from the viewpoint of suppressing decomposition and coloring of the product.
  • the supply amount of heavy liquid and light liquid in the purification process varies depending on the type of apparatus, the type of organic solvent, etc., for example, when using a weir plate type extraction tower as the apparatus and isobutyl alcohol as the organic solvent,
  • the ratio of the supplied amount of the solvent for purification and the isobutyl alcohol phase which is a light liquid is preferably in the range of 5/1 to 1/5 (volume ratio).
  • an organic solvent phase containing a sucrose fatty acid ester can be obtained.
  • the organic solvent phase includes a sucrose fatty acid ester and includes an organic solvent and water.
  • the reduced-pressure drying step is a step of drying the organic solvent phase obtained in the above purification step under reduced pressure, distilling off the organic solvent and water contained therein, and isolating the target sucrose fatty acid ester. is there.
  • the reduced-pressure drying process according to the present invention includes an sucrose fatty acid ester obtained through the purification process, and an organic solvent phase containing an organic solvent and water, by one or more reduced-pressure dryers.
  • the pressure and / or heating temperature is changed in at least two stages or more and dried under reduced pressure, the in-machine pressure of the first reduced pressure drying process is lower than atmospheric pressure, and the heating temperature is It is 20 ° C. or higher and 200 ° C. or lower, the in-machine pressure of the final vacuum drying step is 10 kPa ⁇ abs or lower, and the heating temperature is 20 ° C. or higher and 200 ° C. or lower.
  • in-machine pressure refers to the pressure in the gas phase in the vacuum dryer, and the in-machine pressure can be measured by a conventional method, for example, a pressure gauge installed in contact with the gas phase. it can. As long as the pressure gauge is in contact with the gas phase in the vacuum dryer, for example, the position of the pressure gauge is not limited. For example, the pressure gauge may be in the exhaust pipe from the vacuum dryer.
  • Heating temperature refers to the temperature of a heat medium (hot water, steam, oil, etc.) or an electric heater that is used to heat the mixture and circulates in a jacket or coil of a vacuum dryer.
  • the concentration of sucrose fatty acid ester in the organic solvent phase subjected to the drying step is preferably 10% by weight or more, more preferably 30% by weight or more. If the concentration is less than 10% by weight, it is industrially inefficient. On the other hand, the concentration is preferably 80% by weight or less, and more preferably 50% by weight or less. When the concentration exceeds 80% by weight, the viscosity is very high and it tends to be difficult to adapt to a vacuum dryer. In carrying out the vacuum drying at each stage, water is added as necessary to adjust the concentration of the sucrose fatty acid ester so that the concentration of the sucrose fatty acid ester falls within the above range.
  • the reduced pressure dryer is not particularly limited as long as it can be dried under reduced pressure while maintaining the internal pressure and the heating temperature at the predetermined pressure and the predetermined temperature, and any of machines and instruments having such functions. Can also be used for the purposes of the present invention.
  • Specific examples of the vacuum dryer of the present invention include, for example, a batch type such as a stirring tank, and a continuous type such as a flash distiller, a thin film evaporator, a drum dryer, an extruder, and a belt dryer.
  • Each vacuum dryer includes various types.
  • the extruder includes a single screw extruder, a twin screw extruder, and the like, and various types of these extruders have different screw diameters and different screw shapes.
  • At least one is preferably an extruder, and particularly preferably a twin screw extruder.
  • a twin screw extruder it is advantageous in terms of suppressing coloring of the sucrose fatty acid ester and reducing the remaining amount of the organic solvent.
  • one-stage reduced-pressure drying refers to drying under reduced pressure using a single reduced-pressure dryer under conditions in which the internal pressure and the heating temperature are maintained at the predetermined pressure and the predetermined temperature.
  • one vacuum dryer means a single vacuum dryer, and each of the vacuum dryers is divided into two or more compartments, such as a certain type of extruder. When the pressure and temperature can be set individually in the compartment, the compartment means the “one vacuum dryer” of the present invention.
  • a series of reduced-pressure drying of two or more stages can be performed by using one or two or more apparatuses that perform at least one or more stages of reduced-pressure drying.
  • the in-machine pressure and / or the heating temperature need only be changed in at least two stages, and as long as such a condition is achieved, the in-machine pressure and the heating temperature may not be changed in two or more successive stages.
  • “a series” means that other steps (for example, a purification step) other than drying under reduced pressure are not incorporated in the course of drying under reduced pressure.
  • the number of stages is preferably any one of 2 to 9 from the viewpoint of the quality of the target product and the efficiency for obtaining it.
  • the in-machine pressure in the first-stage reduced-pressure drying step is atmospheric pressure or lower, preferably 80 kPa ⁇ abs or lower, more preferably 60 kPa ⁇ abs or lower.
  • the atmospheric pressure is exceeded, the heating temperature necessary for solvent removal becomes too high, and the sucrose fatty acid ester tends to be colored.
  • the same pressure is preferably 3 kPa ⁇ abs or more, more preferably 4 kPa ⁇ abs or more. If it is less than 3 kPa ⁇ abs, there is a tendency that blockage due to flushing or splashing tends to occur.
  • the in-machine pressure is preferably higher than the final in-machine pressure.
  • the internal pressure in the final-stage reduced-pressure drying step is 10 kPa ⁇ abs or less, preferably 2 kPa ⁇ abs or less, more preferably 0.6 kPa ⁇ abs or less. If it exceeds 10 kPa, it is difficult to sufficiently reduce the residual solvent, or it becomes necessary to increase the temperature of the sucrose fatty acid ester, so that it tends to be colored easily. On the other hand, there is no restriction
  • the in-machine pressure at the final stage of the vacuum drying process is lower than the in-machine pressure at the first stage.
  • the heating temperature in the first-stage vacuum drying step is 20 to 200 ° C. If the temperature exceeds 200 ° C., coloring tends to be suppressed, while if it is less than 20 ° C., there is a tendency that the residual solvent cannot be sufficiently reduced. To solve this problem, for example, the in-machine pressure is made extremely high vacuum. There is a need and equipment costs tend to be high.
  • As an upper limit of heating temperature 160 degrees C or less is preferable, More preferably, it is 140 degrees C or less.
  • the lower limit of the temperature is preferably 60 ° C. or higher, more preferably 100 ° C. or higher.
  • the heating temperature in the final-stage vacuum drying process is 20 to 200 ° C. If it exceeds 200 ° C., coloring tends to be suppressed, whereas if it is less than 20 ° C., it tends to be difficult to sufficiently reduce the residual solvent.
  • As an upper limit of heating temperature 160 degrees C or less is preferable, More preferably, it is 140 degrees C or less.
  • the lower limit of the temperature is preferably 60 ° C. or higher, more preferably 80 ° C. or higher, and still more preferably 100 ° C. or higher.
  • the in-machine pressure and heating temperature in the intermediate stage between the first stage and the final stage can be appropriately set within the above-described pressure and temperature ranges.
  • the higher the temperature the more the coloring tendency increases. Therefore, the pressure and temperature adopted in the first stage, and the pressure and temperature planned to be adopted in the final stage. It will be decided as appropriate.
  • the processing time and the processing flow rate for one-stage vacuum drying will be described.
  • the treatment time when using a batch type vacuum dryer is not particularly limited, but is generally 0.5 to 20 hours. If it exceeds 20 hours, the sucrose fatty acid ester may be colored.
  • the processing flow rate when using a continuous vacuum dryer is not particularly limited because it depends on the size of the apparatus, but is generally 0.5 to 10,000 kg / hour.
  • the number of rotations of the screw may be appropriately set according to other conditions, but is generally 100 to 1500 rpm. It is preferable.
  • sucrose fatty acid ester which is the target product can be isolated through the above-mentioned vacuum drying step.
  • sucrose fatty acid ester thus isolated is in the form of a lump, it can be converted into a sucrose fatty acid ester powder by further subjecting it to a pulverization step.
  • the pulverization can be performed by a conventional method.
  • the bulk sucrose fatty acid ester obtained above is not only pulverized by a high-speed rotary mill such as a hammer mill, cage mill, axial flow mill, annular mill or shear mill, but also a supersonic jet nozzle system, an opposed nozzle system or
  • a fine powder can be obtained by combining pulverization with one or more pulverizers such as a jet mill having a swirling airflow system.
  • sucrose fatty acid ester thus obtained is suppressed in coloring and the residual amount of the organic solvent is negligible, it can be used in various applications, that is, additives for chemical reactions, additives to detergents, packaging containers, etc. In addition to these antistatic agents, it can also be suitably used as additives for feeds, cosmetics, foods, pharmaceuticals and the like.
  • the in-machine pressure is maintained at a high level. While preventing the mixture containing the sugar fatty acid ester and the solvent from bumping and preventing the coloring of the sucrose fatty acid ester by keeping the heating temperature within a predetermined range, the concentration of the sucrose fatty acid ester is then increased.
  • the pressure is relatively high, it is considered that the internal pressure is set low to increase the efficiency of drying under reduced pressure, thereby realizing removal of the organic solvent having both coloring suppression and efficiency.
  • the Gardner color number is measured using a tetrahydrofuran solution (concentration: 200 g / L) of sucrose fatty acid ester according to JIS K0071.
  • the amount of “organic solvent” (ppm) in the sucrose fatty acid ester is a value determined by gas chromatography (GC).
  • GC gas chromatography
  • Example 1 Transesterification reaction
  • the reactor was charged with 345.7 parts by weight of DMSO and subjected to total reflux at 90 ° C. and 3.7 kPa until the water content of DMSO reached 0.06% by weight.
  • 0.26 parts by weight of potassium carbonate, 67.2 parts by weight of sucrose, and 21.4 parts by weight of methyl stearate were added, and the reaction was conducted while distilling DMSO at 95 ° C. and 3.7 kPa. After the distillation amount of DMSO reached 42.9 parts by weight, the reaction was carried out under total reflux without distilling DMSO. After reacting for a total of 4 hours, 90% by weight lactic acid aqueous solution was added so that the pH was 6.0, and the reaction was stopped. Distilled DMSO was recovered for reuse.
  • This solution was adjusted to pH 6.0 with 5% aqueous potassium carbonate solution and allowed to stand to separate into two layers, and an upper layer (IBA phase) and a lower layer (aqueous phase) were separated.
  • the IBA phase was sent to the next purification step.
  • the aqueous phase was subjected to use in Example 2 in order to reuse DMSO and unreacted sucrose contained therein.
  • sucrose stearate after the drying treatment was coarsely pulverized using a high-speed rotary mill and further pulverized using a jet mill to obtain sucrose stearate powder.
  • the remaining amount of IBA was measured and the hue was evaluated.
  • Example 2 (Processing for reuse) 70.5 parts by weight of DMSO was added to 263 parts by weight of the aqueous phase as the lower layer obtained in the extraction step of Example 1. This solution was heated to 90 ° C., and water and isobutyl alcohol were removed under conditions of 2.7 kPa to obtain a 35 wt% sucrose DMSO solution. (Transesterification reaction-grinding process) Instead of using 345.7 parts by weight of DMSO, a mixture of 280.7 parts by weight of DMSO and 100 parts by weight of the 35% by weight sucrose DMSO solution was used, and the amount of sucrose used was 32.2 parts by weight. The same operation as in Example 1 was performed to obtain sucrose stearate powder.
  • Example 3 The amount of sucrose used was 40.0 parts by weight, the amount of methyl stearate used was 172.0 parts by weight, the amount of DMSO used was 265.4 parts by weight, and potassium carbonate 0.56 parts by weight.
  • a sucrose stearate powder was obtained in the same manner as in Example 1 except that 49.8 parts by weight of DMSO was added.
  • Example 4 21.4 parts by weight of methyl stearate is an even fatty acid methyl having 8 to 18 carbon atoms (methyl fatty acid having 8 and 10 carbon atoms: 5% by weight, methyl laurate: 70% by weight, fatty acid methyl having 14, 16 and 18 carbon atoms) : 25 wt% mixture) Same as Example 1 except that 18.7 parts by weight, DMSO usage was changed to 333.9 parts, and potassium carbonate usage was changed to 0.29 parts by weight. Operation was performed to obtain a predetermined sucrose fatty acid ester powder.
  • Example 5 In the extraction process, Example 1 was used except that instead of the stirring tank, a thin film evaporation apparatus (hereinafter simply referred to as “thin film” when displaying that the thin film evaporation apparatus was used in the table) was used.
  • the sucrose stearate powder was obtained in the same manner as in Example 1.
  • Example 6 (Processing for reuse) 70.5 parts by weight of DMSO was added to 263 parts by weight of the aqueous phase as the lower layer obtained in the extraction step of Example 5. This solution was heated to 90 ° C., and water and isobutyl alcohol were removed under conditions of 2.7 kPa to obtain a 35 wt% sucrose DMSO solution. (Transesterification reaction-grinding process) Instead of using 345.7 parts by weight of DMSO, a mixture of 280.7 parts by weight of DMSO and 100 parts by weight of the 35% by weight sucrose DMSO solution was used, and the amount of sucrose used was 32.2 parts by weight. The same operation as in Example 5 was performed to obtain sucrose stearate powder.
  • Example 7 The amount of sucrose used was 40.0 parts by weight, the amount of methyl stearate used was 172.0 parts by weight, the amount of DMSO used was 265.4 parts by weight, and potassium carbonate 0.56 parts by weight.
  • a sucrose stearate powder was obtained in the same manner as in Example 5 except that 49.8 parts by weight of DMSO was added.
  • Example 8 18.7 parts by weight of 21.4 parts by weight of methyl stearate (purity: 70% by weight, fatty acid methyl having 8 to 10 carbon atoms: 5% by weight, methyl fatty acid having 14 to 14 carbon atoms: 25% by weight)
  • the same operation as in Example 5 was carried out except that the amount of DMSO used was changed to 333.9 parts by weight and the amount of potassium carbonate used was changed to 0.29 parts by weight to obtain sucrose stearate powder. It was.
  • Example 9 In the refining process, instead of the perforated plate extraction tower, a weir plate type extraction tower (trade name: WINTRAY, manufactured by JGC Corporation.
  • WINTRAY trade name: WINTRAY, manufactured by JGC Corporation.
  • Table 9 when displaying that the weir plate type extraction tower is used, simply “ The sucrose stearate powder was obtained by carrying out the same operation as in Example 1 except that “weir plate” was used.
  • Example 10 (Processing for reuse) 70.5 parts by weight of DMSO was added to 263 parts by weight of the aqueous phase as the lower layer obtained in the extraction step of Example 9. This solution was heated to 90 ° C., and water and isobutyl alcohol were removed under conditions of 2.7 kPa to obtain a 35 wt% sucrose DMSO solution. (Transesterification reaction-grinding process) Instead of using 345.7 parts by weight of DMSO, a mixture of 280.7 parts by weight of DMSO and 100 parts by weight of the 35% by weight sucrose DMSO solution was used, and the amount of sucrose used was 32.2 parts by weight. The same operation as in Example 9 was performed to obtain sucrose stearate powder.
  • Example 11 The amount of sucrose used was 40.0 parts by weight, the amount of methyl stearate used was 172.0 parts by weight, the amount of DMSO used was 265.4 parts by weight, and potassium carbonate 0.56 parts by weight.
  • a sucrose stearate powder was obtained in the same manner as in Example 9 except that 49.8 parts by weight of DMSO was added.
  • Example 12 18.7 parts by weight of 21.4 parts by weight of methyl stearate (purity: 70% by weight, fatty acid methyl having 8 to 10 carbon atoms: 5% by weight, methyl fatty acid having 14 to 18 carbon atoms: 25% by weight)
  • the same operation as in Example 9 was carried out except that the amount of DMSO used was changed to 333.9 parts by weight and the amount of potassium carbonate used was changed to 0.29 parts by weight to obtain sucrose stearate powder. It was.
  • Example 13 In the extraction step, a sucrose stearate powder was obtained by performing the same operation as in Example 9 except that a thin film evaporator was used instead of the stirring tank.
  • Example 14 (Processing for reuse) 70.5 parts by weight of DMSO was added to 263 parts by weight of the aqueous phase as the lower layer obtained in the extraction step of Example 13. This solution was heated to 90 ° C., and water and isobutyl alcohol were removed under conditions of 2.7 kPa to obtain a 35 wt% sucrose DMSO solution. (Transesterification reaction-grinding process) Instead of using 345.7 parts by weight of DMSO, a mixture of 280.7 parts by weight of DMSO and 100 parts by weight of the 35% by weight sucrose DMSO solution was used, and the amount of sucrose used was 32.2 parts by weight. The same operation as in Example 13 was performed to obtain sucrose stearate powder.
  • Example 15 The amount of sucrose used was 40.0 parts by weight, the amount of methyl stearate used was 172.0 parts by weight, the amount of DMSO used was 265.4 parts by weight, and potassium carbonate 0.56 parts by weight.
  • a sucrose stearate powder was obtained in the same manner as in Example 13 except that 49.8 parts by weight of DMSO was added.
  • Example 16 18.7 parts by weight of 21.4 parts by weight of methyl stearate (purity: 70% by weight, fatty acid methyl having 8 to 10 carbon atoms: 5% by weight, methyl fatty acid having 14 to 18 carbon atoms: 25% by weight)
  • the same operation as in Example 13 was carried out except that the amount of DMSO used was changed to 333.9 parts by weight and the amount of potassium carbonate used was changed to 0.29 parts by weight to obtain sucrose stearate powder. It was.
  • Example 17 In the refining process, a baffle extraction tower was used in place of the perforated plate extraction tower (hereinafter referred to as “baffle” when simply indicated in the table that the baffle extraction tower was used). The same operation as in Example 1 was performed to obtain sucrose stearate powder.
  • Example 18 (Processing for reuse) 70.5 parts by weight of DMSO was added to 263 parts by weight of the aqueous phase as the lower layer obtained in the extraction step of Example 17. This solution was heated to 90 ° C., and water and isobutyl alcohol were removed under conditions of 2.7 kPa to obtain a 35 wt% sucrose DMSO solution. (Transesterification reaction-grinding process) Instead of using 345.7 parts by weight of DMSO, a mixture of 280.7 parts by weight of DMSO and 100 parts by weight of the 35% by weight sucrose DMSO solution was used, and the amount of sucrose used was 32.2 parts by weight. The same operation as in Example 17 was performed to obtain sucrose stearate powder.
  • Example 19 The amount of sucrose used was 40.0 parts by weight, the amount of methyl stearate used was 172.0 parts by weight, the amount of DMSO used was 265.4 parts by weight, and potassium carbonate 0.56 parts by weight.
  • a sucrose stearate powder was obtained in the same manner as in Example 17 except that 49.8 parts by weight of DMSO was added.
  • Example 20 18.7 parts by weight of 21.4 parts by weight of methyl stearate (purity: 70% by weight, fatty acid methyl having 8 to 10 carbon atoms: 5% by weight, methyl fatty acid having 14 to 18 carbon atoms: 25% by weight)
  • the same operation as in Example 17 was carried out except that the amount of DMSO used was changed to 333.9 parts by weight and the amount of potassium carbonate used was changed to 0.29 parts by weight to obtain sucrose stearate powder. It was.
  • Example 21 In the extraction step, a sucrose stearate powder was obtained by performing the same operation as in Example 17 except that a thin film evaporator was used instead of the stirring tank.
  • Example 22 (Processing for reuse) 70.5 parts by weight of DMSO was added to 263 parts by weight of the aqueous phase as the lower layer obtained in the extraction step of Example 21. This solution was heated to 90 ° C., and water and isobutyl alcohol were removed under conditions of 2.7 kPa to obtain a 35 wt% sucrose DMSO solution. (Transesterification reaction-grinding process) Instead of using 345.7 parts by weight of DMSO, a mixture of 280.7 parts by weight of DMSO and 100 parts by weight of the 35% by weight sucrose DMSO solution was used, and the amount of sucrose used was 32.2 parts by weight. The same operation as in Example 21 was performed to obtain sucrose stearate powder.
  • Example 23 The amount of sucrose used was 40.0 parts by weight, the amount of methyl stearate used was 172.0 parts by weight, the amount of DMSO used was 265.4 parts by weight, and potassium carbonate 0.56 parts by weight.
  • a sucrose stearate powder was obtained in the same manner as in Example 21 except that 49.8 parts by weight of DMSO was added.
  • Example 24 18.7 parts by weight of 21.4 parts by weight of methyl stearate (purity: 70% by weight, fatty acid methyl having 8 to 10 carbon atoms: 5% by weight, methyl fatty acid having 14 to 18 carbon atoms: 25% by weight)
  • the same operation as in Example 21 was carried out except that the amount of DMSO used was changed to 333.9 parts by weight and the amount of potassium carbonate used was changed to 0.29 parts by weight to obtain sucrose stearate powder. It was.
  • Example 1 In the vacuum drying step, the same operation as in Example 1 was performed except that the solvent and water and isobutyl alcohol were removed under the conditions described in Table 7 to obtain sucrose stearate powder.
  • Example 2 In the vacuum drying step, the same operation as in Example 5 was performed except that water and isobutyl alcohol as solvents were removed under the conditions described in Table 7 to obtain sucrose stearate powder.
  • Example 3 In the vacuum drying step, the same operation as in Example 9 was performed except that water and isobutyl alcohol as solvents were removed under the conditions described in Table 7 to obtain sucrose stearate powder.
  • Example 4 In the vacuum drying step, the same operation as in Example 13 was performed except that the solvent and water and isobutyl alcohol were removed under the conditions shown in Table 7 to obtain sucrose stearate powder.
  • Example 5 In the vacuum drying step, the same operation as in Example 17 was carried out except that water and isobutyl alcohol as solvents were removed under the conditions described in Table 7 to obtain sucrose stearate powder.
  • Example 6 In the vacuum drying step, the same operation as in Example 21 was performed except that the solvent and water and isobutyl alcohol were removed under the conditions described in Table 7 to obtain sucrose stearate powder.

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Abstract

　L'invention concerne un procédé de production d'ester d'acide gras de saccharose ayant une coloration supprimée et une quantité négligeable de solvant organique résiduel. Un procédé de production d'ester d'acide gras de saccharose qui obtient un ester d'acide gras de saccharose à partir d'un mélange réactionnel obtenu par réaction de saccharose et d'un ester d'alkyle inférieur d'acide gras en présence d'un catalyseur alcalin dans un solvant de réaction, le procédé de production d'ester d'acide gras de saccharose comprenant une étape d'extraction, une étape de purification et une étape de séchage sous vide prédéterminées.
PCT/JP2014/070677 2013-08-09 2014-08-06 Procédé de production d'ester d'acide gras de saccharose WO2015020073A1 (fr)

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CN107163091A (zh) * 2017-06-13 2017-09-15 广东省石油与精细化工研究院 一种蔗糖脂肪酸酯的分级提取方法
CN110106021A (zh) * 2019-03-27 2019-08-09 中粮粮油工业(巢湖)有限公司 植物油中特丁基对苯二酚的脱除方法

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CN106854226B (zh) * 2016-12-08 2023-07-25 广西科技师范学院 蔗糖脂肪酸酯的精制方法

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JPH0421693A (ja) * 1990-05-16 1992-01-24 Dai Ichi Kogyo Seiyaku Co Ltd ショ糖脂肪酸エステルの脱色方法
JPH07206889A (ja) * 1994-01-18 1995-08-08 Mitsubishi Chem Corp ショ糖脂肪酸エステルの製造方法
JPH07228590A (ja) * 1993-12-24 1995-08-29 Mitsubishi Chem Corp 蔗糖脂肪酸エステルの製造方法
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JPS6115893A (ja) * 1984-06-29 1986-01-23 Dai Ichi Kogyo Seiyaku Co Ltd シヨ糖脂肪酸エステルの精製法
JPH0421693A (ja) * 1990-05-16 1992-01-24 Dai Ichi Kogyo Seiyaku Co Ltd ショ糖脂肪酸エステルの脱色方法
JPH07228590A (ja) * 1993-12-24 1995-08-29 Mitsubishi Chem Corp 蔗糖脂肪酸エステルの製造方法
JPH07206889A (ja) * 1994-01-18 1995-08-08 Mitsubishi Chem Corp ショ糖脂肪酸エステルの製造方法
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Publication number Priority date Publication date Assignee Title
CN107163091A (zh) * 2017-06-13 2017-09-15 广东省石油与精细化工研究院 一种蔗糖脂肪酸酯的分级提取方法
CN110106021A (zh) * 2019-03-27 2019-08-09 中粮粮油工业(巢湖)有限公司 植物油中特丁基对苯二酚的脱除方法

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