• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    Process for the preparation of fatty acid esters of lower alcohols from fatty acids contained in fatty acid triglycerides or fatty acid esters of lower alcohols by esterification of the fatty acids with lower alcohols at atmospheric pressure and temperatures in the boiling range of the lower alcohols in the presence of acidic homogeneous catalysts and optionally serving as a carrier material for the acidic catalysts, in the fatty acid triglycerides. Fatty acid esters of insoluble solvents and optionally recovery and reuse of the catalysts by distilling off the excess lower alcohol and water of reaction and then alkaline catalyzed transesterification of the triglycerides with lower alcohols in a purity required for use as fuel for diesel engines.
    公开号:AT510636A1
    申请号:T1786/2010
    申请日:2010-10-28
    公开日:2012-05-15
    发明作者:
    申请人:Wimmer Theodor；
    IPC主号:
    专利说明:

    Process for the preparation of fatty acid esters of lower alcohols.
    The invention relates to a process for the preparation of fatty acid esters of lower alcohols, in particular Fettsäuremethyl- and -ethylestem from fatty acid triglycerides containing free fatty acids such as fats and oils of vegetable or animal origin or waste fats from the food preparation or fatty acid-containing fractions from the edible oil refining or fatty acids or fatty acid-containing by-products from biodiesel production by acid-catalyzed esterification of the fatty acids present with lower alcohols, in particular methanol and subsequent base-catalyzed transesterification of the triglycerides contained to fatty acid esters of lower alcohols having a purity required for use as fuels for diesel engines.
    Fatty acid methyl esters have recently acquired great economic and environmental importance as a substitute for fossil diesel fuels.
    The purity requirements of fatty acid methyl esters intended for use as diesel substitute fuels are set forth in standards such as e.g. of the European biodiesel standard EN 14214.
    The price development of the raw materials required for the production of biodiesel on the world market requires the economic operation of a biodiesel plant, that on the one hand as low-priced raw materials can be purchased and on the other hand high yields of methyl esters are achieved.
    Numerous biodiesel plants have come in recent years in economic difficulties, because their production process highly purified and therefore expensive raw materials require or required for the necessary cleaning of raw materials and plant components are not present, or the purification of raw materials is associated with losses.
    The raw materials used to produce biodiesel are obtained by pressing or extracting oilseeds such as e.g. Rapeseed, soybeans, sunflower seeds, jatropha nuts, etc., contain more or less free fatty acids depending on the method of production. Furthermore, waste greases such as e.g. used edible oils from the food preparation or oil fractions, as they are obtained as by-products in the distillative or chemical refining or deacidification of crude oils, as raw materials for biodiesel production inffage. Furthermore arise in the neutralization of the base catalyzed transesterification of oils with methanol as a by-product glycerol "oil phases" containing varying amounts of free fatty acids and Fettsäuremethylestem and can also be used for biodiesel production.
    Common to all of the aforementioned raw materials is the content of more or less free fatty acids. For economical operation of a biodiesel plant, it is necessary to convert these fatty acids also to biodiesel in order to achieve a high yield.
    For the esterification of these fatty acids or simultaneous or subsequent transesterification numerous methods have been described in the literature.
    Thus, in Ullmann's Encyclopedia of the techn.Chemie (4th edition, Bd.l 1, 1976, page 432) describes a method wherein free fatty acids containing oils in the presence of alkali and zinc catalysts and temperatures of about 240 ° C and pressures from lOObar and a large excess of methanol simultaneously be transesterified and transesterified. Similar processes operating at high temperatures, high pressures and large excesses of methanol will be described e.g. described in WO 2007/012097 (alkaline earth metal salts of fatty acids as catalysts at 210 ° C), EP 593524 (free fatty acids as catalysts and 150 - 300 ° C). Disadvantages of these methods are the high reaction temperatures and pressures and the associated high expenditure on equipment and the high energy input.
    Numerous processes have been described in which the free fatty acids present in the oils used are pre-esterified at temperatures near the boiling point of the lower alcohol and thus at atmospheric pressure or at low pressures in a first step by means of acidic catalysts and then in a second step by means of basic catalysts Fatty acid esters of lower alcohols, usually methanol to be transesterified.
    Thus, e.g. DE 3501761 (US 4,698,186) the use of acidic cation exchange resins as fixed bed catalysts.
    The use of acidic catalysts in homogeneous phase is already described in GB 612667 (1946), which are mentioned as catalysts sulfuric acid, phosphoric acid, hydrogen chloride, sulfonic acids such as p-toluene or camphorsulfonic acid or metal salts, and in the neutralization of the alkaline catalyzed transesterification resulting fatty acid-containing phase is pre-esterified together with the fatty acid-containing crude oil.
    A method almost identical to the teachings of the last mentioned patent is described in EP 1,322,588, whereby only sulfuric acid is named here as the catalyst. Similar methods are described, e.g. in AT 410.443 (esterification with sulfuric acid at temperatures below 40 ° C), in EP 708.813 (esterification with sulfuric acid, p-toluenesulfonic acid or acidic ion exchange resins) or in WO 02/46340, wherein the acidic catalysts with the alkaline catalysts of the following Transesterification must be neutralized and the resulting salts must be disposed of or, in the best case, find use as potassium sulfate in the fertilizer industry. EP 127 104 and EP 184 740 describe the esterification of the free fatty acids contained in the crude oils in the presence of acidic catalysts such as alkyl, aryl, aryl-alkyl-sulfonic acids, e.g. Methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, naphthalenesulfonic acid, dodecylbenzenesulfonic acid, sulfuric acid,
    Glycerol monosulphuric acid, tungstomatophosphoric acid or molybdophosphoric acid, which are also present in an entraining agent, e.g. Glycerol, ethylene glycol, diethylene glycol and the like may be dissolved as a liquid carrier, wherein the catalyst acids are further used or regenerated after distilling off the excess methanol and the water of reaction.
    DE 102 43700 likewise describes the use of a carrier material, in particular glycerol, for the sulfuric acid or p-toluenesulfonic acid used as catalyst, the acids being disposed of as fertilizer after neutralization with the alkaline catalyst for subsequent transesterification.
    Of the above-mentioned homogeneous acidic catalysts, the sulfonic acids have advantages with respect to the reaction rate and the degree of esterification achieved and can be regenerated by distilling off the excess methanol and the water of reaction, in particular in the presence of an inert solvent and again as catalysts for esterification unlike hydrogen chloride and sulfuric acid.
    When sulfuric acid is used, sulfuric acid monomethyl ester is also intermediately formed with methanol, and the possibility of forming small amounts of the highly toxic dimethyl sulfate can not be ruled out. ! 3
    * · «T *« ß
    All of the sulfonic acids mentioned in the literature, which are named as catalysts for the esterification of free fatty acids with lower alcohols, are monosulfonic acids. Surprisingly, it has been found that when using the monosulfonic acids mentioned in the literature, e.g. Methanesulfonic acid, benzene or toluenesulfonic acid for pre-esterification of free fatty acids with subsequent alkaline-catalyzed transesterification sulfur entry into the biodiesel, which is above the specified in the standard limit of 10mg / kg, usually 20-50mg / kg and thus not the biodiesel standard EN 14214 corresponds.
    The object of the invention was therefore to provide a method which avoids the disadvantages of the aforementioned methods and makes it possible to obtain from inexpensive, free fatty acids containing raw materials by pre-esterification of the free fatty acids using an acidic, homogeneous and regenerable catalyst and then alkaline catalyzed transesterification to produce a biodiesel according to EN 14214. Surprisingly, it has been shown that when using 2-basic aliphatic or aromatic sulfonic acids for the pre-esterification of raw materials containing free fatty acids with subsequent alkaline-catalyzed transesterification no sulfur enters the biodiesel. The sulfur content is less than 5 mg / kg, preferably less than 2 mg / kg or corresponds to the sulfur content of the crude oil used.
    The present invention therefore provides a process for the preparation of Fettsäureestem lower alcohols from fatty acid triglycerides or fatty acid esters of lower alcohols containing free fatty acids by esterification of fatty acids contained in the fatty acid triglycerides or fatty acid esters lower alcohols with lower alcohols at atmospheric pressure and temperatures in the boiling range of the lower alcohols in the presence of acidic homogeneous catalysts and optionally serving as a support material for the acidic catalysts, in the fatty acids, fatty acid triglycerides or fatty acid esters of lower alcohols insoluble solvents and optionally recovery and reuse of the catalysts by distilling off the excess of the present in the lower alcohol and the water of reaction and then alkaline catalyzed transesterification of the contained triglycerides with lower alcohols in one for use as a fuel for di Eselmotoren required purity, which is characterized in that 2-basic aliphatic or aromatic sulfonic acids are used as homogeneous esterification catalysts.
    Ethane-1,2-disulfonic acid, benzene-1,3-di-sulfonic acid and naphthalene-1,5-disulfonic acid are preferably used as esterification catalysts. Suitable starting materials for the process according to the invention are triglycerides containing free fatty acids, e.g. Oils and fats of vegetable origin, such as e.g. by pressing or extracting in particular rapeseed, Sonnehblumenkemen, soybeans, Jatrophanüssen, palm fruits, corn germs, cottonseed, etc., are recovered and after degumming usually 1 to 2%, occasionally up to 15% and more free fatty acids.
    Other suitable fatty acids containing triglycerides are waste fats from the food preparation which usually contain 3 to 6% of free fatty acids, in some cases more.
    Also eligible are oil fractions containing by distillation deacidification of crude oils or from the "soapstock" of chemical deacidification ("split fatty acids") and usually 40 to 90% free fatty acids, sometimes up to 100%.
    Furthermore, for the process according to the invention, oil phases which are obtained by neutralization of the glycerol phase obtained as a by-product from the catalyzed transesterification of oils with methanol and usually contain from 20 to 80% of free fatty acids in addition to fatty acid methyl esters are suitable.
    The oil fractions with fatty acid contents of more than 30% are advantageously mixed with oils with low fatty acid contents, so that the oils used for the esterification do not contain more than 30% of free fatty acids.
    The lower alcohol used is preferably methanol in an amount of 10 to 200% by weight, preferably 20 to 50% by weight, based on the weight of the oil used.
    Suitable support materials for the acidic catalysts are those solvents which are insoluble in fatty acids, triglycerides and fatty acid esters of lower alcohols or mixtures thereof, e.g. aliphatic triols, glycols, di-, oligo-, or low molecular weight polyglycols, in particular diethylene glycol and glycerol.
    The 2-basic sulfonic acids are used in an amount of 0.1 to 6.0%, preferably 0.6 to 2%, based on the weight of the oil used and in the 0- 20 times, preferably 4-8 times the amount of a carrier material preferably glycerol or diethylene glycol dissolved.
    The esterification reaction takes place with stirring, preferably at the boiling point of the lower alcohol, in particular of the methanol and is usually completed after 1 to 4 hours, depending on the initial content of free fatty acids.
    The esterification mixture then separates by gravity into a light phase consisting of methanol, the support material, the catalyst and the water of reaction and a heavy phase consisting of the esterified starting material. The residual amount of unreacted free fatty acids is dependent on the initial free fatty acid content, excess methanol and reaction time.
    The heavy phase is washed with methanol several times, preferably 3 times to completely remove the catalyst acid, the support material and the reaction water. The washing processes can be carried out by means of preferably three mixer / settler apparatuses connected in series, the light methanol phase formed after the phase separation of the 1st washing stage being used after receiving the regenerated catalyst for the next esterification reaction and the light methanol phase from the 2nd washing stage for the 1 Washing step of the next Verzustmgsansatzes and the light methanol phase from the 3rd washing stage for the 2nd washing step of the next esterification approach is used and the 3rd washing step of the next esterification approach is carried out with pure methanol.
    Alternatively, heavy phase washing may also be accomplished by liquid-liquid extraction, e.g. by means of a countercurrent column. Alternatively, the phase separations of the washing stages can also be effected by means of separators. The washing operations can be carried out both batchwise and continuously.
    Regeneration of the catalyst:
    The present after the phase separation of the esterification mixture light phase, which contains mainly methanol, the support material, the catalyst acid and the reaction water of the esterification is freed by evaporation of methanol and water. The evaporation of the methanol-reaction water mixture can be carried out for example via an evaporator at atmospheric pressure or at a slight suppression of 90 - 100mbar absolute and a temperature of not more than 80 - 90 ° C. In order to remove the reaction water as completely as possible and in the interest of the lowest possible thermal load of the evaporation residue, a falling film evaporator can be used following the evaporator, at pressures of preferably below 50 mbar absolute and temperatures of less than 50 ° C. The evaporation residue, the the carrier material and the catalyst contains acid and possibly small amounts of the heavy phase from the phase separation of the esterification mixture, has a residual water content of not more than 10%, preferably less than 3%. The evaporation residue is dissolved without further purification in the washing methanol of the 1st washing stage and used again for esterification.
    The methanol-water mixture obtained from the evaporators can be separated by means of a rectification column or dried by means of a molecular sieve and the anhydrous methanol thus obtained can in turn be used for esterification.
    The heavy phase liberated by the washes of catalyst residues and water of reaction contains, depending on the initial free fatty acid content, fatty acid methyl esters, triglycerides, methanol and a residual fatty acid content of less than 1.0%, preferably less than 0.2% and without further purification alkaline-catalyzed transesterification fed with methanol.
    The transesterification is carried out in a manner known per se, e.g. according to the teaching of EP 658183 carried out in 2 stages, which can be used as a catalyst due to the low residual fatty acid content of sodium in a low concentration.
    The process of the invention can be carried out both batchwise and continuously.
    The invention is further illustrated by the following examples:
    Example 1) Esterification step: 130 grams of crude, coarsely degummed rapeseed oil with a content of 1.5% free fatty acids and max. 50 ppm of phosphorus are mixed with 20 grams of oil phase consisting of 12 grams of free fatty acids and 8 grams of fatty acid methyl esters obtained by acid treatment of a glycerol phase derived from alkaline transesterification. The content of the mixture of free fatty acids is 9.3%. 2.0 grams of naphthalene-1,5-disulfonic acid and 8.0 grams of diethylene glycol are dissolved in 45 grams of methanol and stirred intensively together with the rapeseed oil-oil phase mixture at 60-65 ° C for 75 minutes. The mixture is then transferred to a separatory funnel and allowed to settle for 30 minutes at a temperature not lower than 50 ° C, wherein a phase separation in a light phase consisting of methanol, diethylene glycol, naphthalene -1,5 - disulfonic acid and water of reaction and a heavy phase consisting from rapeseed oil and rapeseed methyl ester.
    The heavy phase is stirred to remove residual amounts of catalyst and water of reaction by means of three washing steps, each with 45 g of methanol and allowed to settle in a separatory funnel, wherein each phase separation into a light phase of mainly methanol and a heavy phase of rapeseed oil and rapeseed methyl ester takes place and the methanol from the first washing step is used to dissolve the regenerated catalyst for the esterification of a further batch and the methanol from the second washing stage is used to wash the first washing stage of the further batch. Pure methanol is used for the 3rd wash and the resulting wash methanol from the 3rd wash step is used for the 2nd wash step of the further batch.
    The present after the 3rd washing process as a heavy phase
    Rapeseed oil / rapeseed methyl ester mixture contains 300 ppm water, 0.1% free fatty acids and approx. 8% methanol.
    Regeneration of the catalyst:
    The light phase obtained after settling of the esterification mixture is freed from methanol and water in a rotary evaporator until the residue has a water content of less than 3%, dissolved without further purification in 45 grams of washing methanol from the 1st washing stage and used for a further esterification ,
    transesterification:
    The obtained after the 3 washes 160 g rapeseed oil rapeseed methyl ester mixture, which contain about 8% methanol, with 18 g of methanol and 1.5 g 30 percent. Sodium methylate in methanol, stirred for 30 minutes at 60-65 ° C and then transferred to a separatory funnel After 30 minutes settling, the mixture in 157 g light phase and 21 g heavy glycerol phase separated. The light phase (157 g) is stirred in a second transesterification step with another 0.7 g of 30 percent sodium methylate for 30 minutes at 60-65 ° C, then treated with 8 g of glycerol phase from the first transesterification, stirred for 3 minutes and in a Separating funnel überfuhrt. After phase separation, the light phase is removed by washing with a dilute acid from adhering residual soaps and by distillation of excess methanol and water.
    The yield is 150 g rapeseed methyl ester and corresponds in all values to EN 14214.
    In the same way as described in Example 1), instead of naphthalene-1,5-di sulfonic acid, the following catalyst acids are used and the sulfur contents obtained after the transesterification are compared:
    Catalyst acid: Sulfur content:
    Naphthalene-1,5-disulfonic acid 2.0 mg / kg
    Benzene-1,3-di-sulfonic acid 1.5 mg / kg
    Ethane-1,2-disulfonic acid 2.2 mg / kg Comparative Examples:
    Methanesulfonic acid 19.0 mg / kg p-toluenesulfonic acid 37.2 mg / kg
    Benzenesulfonic acid 22.5 mg / kg
    Example 2)
    Over a period of 2 weeks (5 days a week, 24 hours a day) an oil phase with 73.4% free fatty acids and 26.6% fatty acid methyl esters, which by an acid treatment one of the alkaline transesterification-derived glycerol phase was obtained, processed. The oil phase was mixed with refined rapeseed oil such that the oil phase / rapeseed oil mixture had an FFA content of 25%. * * * * * * * * * * «» * »* • * 3» t · «t *» «'· · · · · i« * «
    The catalyst used was naphthalene-1,5-di-sulfonic acid dissolved in diethylene glycol. The mixing ratio of the catalyst mixture was 20% by mass of naphthalene-1,5-disulfonic acid and 80% by mass of diethylene glycol.
    The process on the process model was as follows:
    The oil phase / rapeseed oil mixture was placed in a receiver tank in which the medium was heated to 60 ° C. From this storage tank, the mixture was continuously fed into the process model by means of a pump at a rate of 429 g / h - for this endurance test consisting of the "esterification with 3-stage laundry", "catalyst regeneration" and "transesterification with biodiesel purification and drying" process series. -gepumpt.
    Esterification with 3-stage laundry:
    In the first section of the process model, esterification, the oil phase / rapeseed oil mixture was mixed with 71 g / h regenerated catalyst mixture (from the catalyst regeneration) and methanol from the 1st wash step separator in a mixer and then passed through a reactor. The residence time of the mixture in the reactor was 160 minutes, the temperature in the reactor was kept at 60 ° C. In the reactor, the corresponding esterification reactions took place, i. from the free fatty acids and the methanol were fatty acid methyl esters and water.
    In a downstream separator, the mixture at a residence time of 30 minutes at about 55 ° C in a light phase consisting mainly of methanol, diethylene glycol, naphthalene-1,5-disulfonic acid, and water of reaction and in a heavy phase consisting mainly of rapeseed oil and fatty acid methyl ester, separated.
    The heavy phase from the separator was mixed in the following 1.Waschstufe in a mixer with the light phase from the separator of the 2nd washing stage and in a separator in turn into a light phase consisting mainly of methanol and in a heavy phase consisting mainly of Rapeseed oil and fatty acid methyl ester, separated. The light phase was again fed directly to the esterification mixer.
    The heavy phase from the 1st washing stage was mixed in a 2nd washing stage in a mixer with the light phase from the separator of the 3rd washing stage and washed again. In a subsequent separator, the mixture was again separated into a light phase consisting mainly of methanol and into a heavy phase consisting mainly of rapeseed oil and fatty acid methyl ester. The light phase was again fed directly to the mixer of the 1st washing stage.
    The heavy phase from the 2nd washing stage was washed again in a third washing stage in a mixer with 215 g / h of fresh methanol, which was fed via a pump from a feed tank. In a subsequent separator, the mixture was separated into a light phase consisting mainly of methanol and into a heavy phase consisting mainly of rapeseed oil and fatty acid methyl ester. The light phase was fed directly to the mixer of the 2nd washing stage.
    The rapeseed oil / fatty acid methyl ester mixture present as a heavy phase after the third wash contained 330 ppm of water, 0.25% of free fatty acids and about 11% of methanol.
    Catalyst regeneration: * · ♦ *
    • · »4 * * * * * ♦« ft
    The light phase from the separator after the esterification reactor was transferred to a vessel in which the medium was maintained at a temperature of 55 ° C. From this vessel, the mixture consisting mainly of methanol, diethylene glycol, naphthalene-1,5-disulfonic acid and water, a vacuum column, which was operated at 80 to 1 OOmbar (absolute) and a temperature of 85 ° C was fed via a pump. After removal of the methanol and the bulk of water, the bottom product consisting mainly of diethylene glycol, naphthalene-1,5-disulfonic acid and water was transferred by pump to another vacuum column and dried to a residual water content in the bottom product below 30,000 ppm. The bottom product was transferred by means of a pump into a buffer vessel from where the regenerated catalyst mixture was fed via a further pump to the mixer for the catalysis of the esterification. The catalyst regeneration was also carried out continuously.
    Transesterification with biodiesel purification and drying:
    The rapeseed oil / fatty acid methyl ester mixture obtained from the esterification with the subsequent 3-stage wash was then run from a buffer vessel via a pump with a throughput of 487 g / h into a 2-stage transesterification step followed by biodiesel purification and drying.
    In the 1st stage of the esterification, 63 g / h of a 3.5 percent sodium methylate in methanol solution, from a feed tank via a pump, were fed to a rapeseed oil / fatty acid methyl ester mixture. The residence time of the mixture in the reactor was 40 minutes, the temperature in the reactor was kept at 60 ° C.
    In a downstream separator, the mixture was separated at a residence time of 80 minutes at about 55 ° C in a light phase and heavy glycerol phase.
    The light phase from the 1st transesterification stage was fed to a reactor from a receiver tank via a pump in a second esterification stage with a further 8.6 g / h of a 10 percent sodium methylate in methanol solution. The residence time of the mixture in the reactor was 40 minutes, the temperature in the reactor was kept at 60 ° C. At the outlet of the reactor 29 g / h of glycerol phase from the 1st transesterification stage were fed to the reaction mixture in a subsequent mixer.
    Subsequently, in a downstream separator, the mixture was separated at a residence time of 80 minutes at about 55 ° C in a light phase and in a heavy glycerol phase.
    The light phase from the 2nd transesterification step was then fed to the laundry in a mixer for a dilute acid, from a feed tank via a pump. The mixture was then separated in a separator into a light phase and into a heavy aqueous phase.
    The light phase was then freed from methanol and water in a vacuum column.
    The fatty acid methyl ester obtained corresponded in all values to EN 14214.
    The procedure described in this example on the process model with the process units -esterification with 3-stage washing, catalyst regeneration and transesterification with biodiesel cleaning and drying-was operated continuously over a period of 2 times 5 weekdays over 24 hours. The process units were connected in such a way that the procedure described was simultaneous and continuous. There were only
    The respective storage containers for the mixture of oil phase / rapeseed oil, fresh methanol, 3.5% sodium methylate in methanol solution, 10% sodium methylate in methanol solution and dilute acid are respectively added.
    权利要求:
    Claims (15)
    [1]
    1. A process for the preparation of fatty acid esters of lower alcohols contained in fatty acid triglycerides or fatty acid esters of lower alcohols by esterification of the free fatty acids with lower alcohols at atmospheric pressure and temperatures in the boiling range of the lower alcohols in the presence of acidic homogeneous catalysts and optionally as a support material for the Satiren catalysts, insoluble in the fatty acid triglycerides or Fettsäureestem solvent and optionally recovery and reuse of the catalysts by distilling off the excess of lower alcohol present and the reaction water and subsequent alkaline catalyzed transesterification of the triglycerides with lower alcohols in a required for use as a fuel for diesel engines purity characterized in that 2-basic aliphatic or aromatic sulfonic acids as homogeneous Veresterungsk analyzers are used.
    [2]
    2. The method according to claim 1, characterized in that as a homogeneous acidic catalyst ethane-1,2-disulfonic acid, benzene-1,3-disulfonic acid, or naphthalene-1,5-disulfonic acid is used.
    [3]
    3. The method according to claim 1, characterized in that methanol is used as the lower alcohol.
    [4]
    4. The method according to claim 1, characterized in that as fatty acids containing fatty acid triglycerides or fatty acid methyl ester oils and fats of vegetable origin, such as. by pressing or extracting in particular rapeseed. Sonnenkumenkemen, soybeans, Jatrophanüssen, palm fruits, maize germs, cottonseed, etc., are recovered and after degumming usually 1 to 2%, occasionally up to 15% and more free fatty acids included, as well as fatty acids containing triglycerides waste fats from the food preparation which are usually 3 to 6% of free fatty acids, in some cases also contain more used and that oil fractions in the distillative deacidification of the crude oils or from the "Soapstock" of the chemical deacidification ("split fatty acids") and usually 40 to 90% of free fatty acids , sometimes also up to 100%, are used, as well as oil phases obtained by neutralization of the obtained in the alkaline catalyzed transesterification of oils with methanol as a by-product glycerol phase and usually contain 20 to 80% of free fatty acids in addition to fatty acid methyl esters used.
    [5]
    5. The method according to claim 1 to 4, characterized in that fatty acid triglycerides containing more than 30% free fatty acids are mixed with triglycerides containing less than 30% free fatty acids, so that the proportion of fatty acids not 30% in the total amount of triglyceride exceeds.
    [6]
    6. The method according to claim 1 to 5, characterized in that is used as the carrier material for the catalyst glycerol or diethylene glycol.
    [7]
    7. The method according to claim 1 to 6, characterized in that the esterification catalyst is freed by evaporation of methanol and water and used again for the esterification.
    [8]
    8. The method according to claim 1 to 7, characterized in that the methanol used in excess is brought after evaporation from the esterification catalyst in a rectification to a residual water content of less than 0.1% and is used again for the esterification.
    [9]
    9. The method according to claim 1 to 8, characterized in that the triglyceride-methyl ester mixture obtained after the esterification and phase separation is preferably washed in 3 consecutive washing processes with methanol.
    [10]
    10. The method according to claim 1 to 9, characterized in that the washing operations are carried out by means of sequentially connected mixer / settler apparatus or by means of a countercurrent column.
    [11]
    11. The method according to claim 1 to 10, characterized in that the esterification reaction in the vicinity of the boiling point of the methanol and is carried out without pressure.
    [12]
    12. The method according to claim 1 to 11, characterized in that the esterified and washed mixture of fatty acid triglycerides and fatty acid methyl ester has an acid number of less than 0.40 mg KOH / g.
    [13]
    13. The method according to claim 1 to 12, characterized in that the esterified mixture of fatty acid triglycerides and fatty acid methyl ester of a base-catalyzed transesterification with methanol is supplied.
    [14]
    14. The method according to claim 1 to 13, characterized in that the base-catalyzed transesterification is carried out with sodium methoxide as a catalyst.
    [15]
    15. The method according to claim 1 to 14, characterized in that the preparation can be carried out both in a balch as well as continuously.
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    同族专利:
    公开号 | 公开日
    WO2012054946A1|2012-05-03|
    AT510636B1|2016-11-15|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    CH254798A|1942-12-11|1948-05-31|Ag Georg Schicht|Process for the esterification of fatty acids with low molecular weight monohydric alcohols.|
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    ATA16992000A|2000-10-05|2001-12-15|Michael Dr Koncar|METHOD FOR PRODUCING FATTY ACID ALKYL ESTERS|
    AT410443B|2000-11-08|2003-04-25|Wimmer Theodor|METHOD FOR PRODUCING FATTY ACID ESTERS OF LOW ALCOHOLS|
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    AT502218B1|2005-07-25|2010-09-15|Bdi Biodiesel Internat Ag|PROCESS FOR PREPARING CARBONIC ACID ALKYL ESTERS|DE102016119756A1|2016-10-17|2018-04-19|UBPM Umwelt-Beratung und Produkt-Management GmbH & Co. KG|Method and use of an oxidizing agent for oxidizing elemental sulfur and / or sulfur compounds in the presence of fatty acids and / or fatty acid derivatives|
    CN112159727A|2020-09-09|2021-01-01|湖北天基生物能源科技发展有限公司|Esterification method of waste oil|
    法律状态:
    2017-02-15| PC| Change of the owner|Owner name: CHRISTOF INTERNATIONAL MANAGEMENT GMBH, AT Effective date: 20161227 |
    优先权:
    申请号 | 申请日 | 专利标题
    ATA1786/2010A|AT510636B1|2010-10-28|2010-10-28|PROCESS FOR PREPARING FATTY ACID PRESENTS OF LOW ALCOHOLS|ATA1786/2010A| AT510636B1|2010-10-28|2010-10-28|PROCESS FOR PREPARING FATTY ACID PRESENTS OF LOW ALCOHOLS|
    PCT/AT2011/000437| WO2012054946A1|2010-10-28|2011-10-27|Method for producing fatty acid esters of lower alcohols|
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