[go: up one dir, main page]

WO2012044042A2 - Procédé de préparation d'esters d'alkyle d'acides gras - Google Patents

Procédé de préparation d'esters d'alkyle d'acides gras Download PDF

Info

Publication number
WO2012044042A2
WO2012044042A2 PCT/KR2011/007106 KR2011007106W WO2012044042A2 WO 2012044042 A2 WO2012044042 A2 WO 2012044042A2 KR 2011007106 W KR2011007106 W KR 2011007106W WO 2012044042 A2 WO2012044042 A2 WO 2012044042A2
Authority
WO
WIPO (PCT)
Prior art keywords
fatty acid
acid alkyl
catalyst
reaction
alkyl ester
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/KR2011/007106
Other languages
English (en)
Korean (ko)
Other versions
WO2012044042A3 (fr
Inventor
이무호
김인기
김일남
곽진원
황승준
박남수
김종원
권은숙
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Samsung Petrochemical Co Ltd
Original Assignee
Samsung Petrochemical Co Ltd
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
Priority claimed from KR1020100093474A external-priority patent/KR101072674B1/ko
Application filed by Samsung Petrochemical Co Ltd filed Critical Samsung Petrochemical Co Ltd
Publication of WO2012044042A2 publication Critical patent/WO2012044042A2/fr
Publication of WO2012044042A3 publication Critical patent/WO2012044042A3/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/03—Preparation of carboxylic acid esters by reacting an ester group with a hydroxy group
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
    • 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
    • C11C3/04—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fats or fatty oils
    • C11C3/10—Ester interchange
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/10—Magnesium; Oxides or hydroxides thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
    • B01J23/04—Alkali metals

Definitions

  • the present invention relates to a process for effectively preparing fatty acid alkyl esters from oils, fats, or mixtures thereof containing free fatty acids in the presence of a base catalyst.
  • Fatty acid alkyl esters are generally prepared by homogeneous liquid phase reaction using oil, fat, or mixtures thereof and methanol having an acid value of 2 or less free of fatty acids, and methanol as a raw material.
  • the catalysts include sodium hydroxide (NaOH) and potassium hydroxide ( KOH), potassium methylate (KOCH 3 ), sodium methylate (NaOCH 3 ), and the like. These reaction conditions are gentle conditions of 40-80 degreeC.
  • EP 1308498 A1 proposes a process for preparing fatty acid alkylesters from fats and oils comprising free fatty acids via a multistage homogeneous liquid phase process using Lewis acid catalysts.
  • the method has a high catalyst usage and is difficult to apply to high acid value raw materials.
  • EP 1092703 A1 discloses a process for producing fatty acid methyl ester by reacting a glyceride raw material having an acid value of 5 to 20 in the presence of a transition metal salt, but it is also difficult to use the high acid raw material.
  • U.S. Patent 5,434,279 describes a process for producing fatty acid esters by two step reaction at low temperatures of up to 60 ° C using excess catalyst. In this method, the amount of catalyst used is high and the yield of fatty acid alkyl ester is low, and the method is difficult to apply to a high acid value raw material.
  • U.S. Patent 4,668,439 describes a process for producing fatty acid alkyl esters by reacting excess alkali metal salts or heavy metal salts with excess methanol, liquid glycerides under high temperature and low pressure and then layering the reactants.
  • the catalyst used in this process forms an emulsion, making it difficult to separate glycerin. This process is not particularly desirable for high acid value raw materials.
  • Korean Patent Publication No. 10-2008-0036107 discloses a method for preparing a carboxylic acid ester in the presence of a liquid metal catalyst using an alkaline earth metal salt of carboxylic acid, but this method requires a separate process for preparing a catalyst and a fatty acid salt. The loss of yield is high by using a large amount of catalyst in the form.
  • the prior art uses an excess of catalyst and methanol, where fatty acid salts are formed by the reaction of the catalyst with free fatty acids when oil, fat, or mixtures thereof are present in large amounts. These fatty acid salts form an emulsion with glycerin, which makes it difficult to separate by-product glycerin after the reaction.
  • U.S. Patent 5,908,946 discloses a process for producing fatty acid alkyl esters using at least one of zinc oxide (ZnO), aluminum oxide (Al 2 O 3 ), zinc aluminate (ZnAl 2 O 3 ) as a catalyst, U.S.
  • Patent 6,818,026, the second is under critical conditions to a catalyst using calcium hydroxide, calcium carbonate, calcium oxide, magnesium oxide
  • the Republic of Korea Patent Application 644 246 discloses a magnesium oxide-zinc oxide-zinc aluminate (xMgO ⁇ yZnO ⁇ ZnAl 2 O 4)
  • the method using the catalyst system of the Republic of Korea, Korean Patent Publication No. 2007-0104041 is a solid phase for producing biodiesel comprising at least one of the transition metal oxide group including zinc oxide, nickel oxide, cobalt oxide, molybdenum oxide and titanium dioxide as an active ingredient Catalytic process is disclosed.
  • the present inventors studied a method for preparing fatty acid alkyl esters using oils, fats, or mixtures of high acid values. As a result, esterification and transition esterification proceed simultaneously under high temperature and high pressure homogeneous base catalyst conditions. Particularly, when the reaction is performed using MgO or Mg (OH) 2 as a homogeneous base catalyst, it exhibits higher catalytic activity even with a smaller amount of catalyst than the conventional alkali metal catalyst, and is used for the separation of by-product glycerin after the reaction. The small amount of catalyst has led to the present invention in that it is easy to separate the layers.
  • the present invention relates to oils, fats, or mixtures thereof containing free fatty acids and acid values of 2 to 200, and C 1 -C 5 low-cost alcohols at 150-250 ° C. under one or more catalysts selected from MgO and Mg (OH) 2 . And it provides a method for producing a fatty acid alkyl ester comprising the step of esterification reaction and transesterification reaction under 5-100 atm.
  • Oils or fats of the present invention are fatty acid glycerol esters, which are esters of glycerol and saturated or unsaturated fatty acids, meaning fats or oils of animal or vegetable origin, and include free fatty acids.
  • Fats or oils of the invention include, but are not limited to, lower oils, fats, or mixtures thereof containing large amounts of free fatty acids, such as, but not limited to, waste cooking oil, waste fat, yellow grease, and the like.
  • Vegetable origin includes soybean oil, palm oil, castor oil, rapeseed oil, and the like, and animal origin include tallow, lard, poultry fat and the like.
  • oils, fats, or mixtures thereof of the invention have an acid value of 2 to 200, preferably 5 to 100, more preferably 10 to 60.
  • oils, fats, or mixtures thereof of the present invention can be prepared into fatty acid alkylesters by reaction with alcohols and through esterification and transesterification reactions.
  • the alcohol used in the esterification or transesterification reaction with the oil, fat, or mixtures thereof of the present invention may be selected from one or more linear or branched alcohols having 1 to 5 carbon atoms, preferably Methanol or ethanol is used.
  • a small amount of alcohol is used relative to oil, fat, or mixtures thereof, and the ratio of oil, fat, or mixtures thereof (oil, fat, or mixtures / alcohols thereof) to alcohol is 100 / wt. 80-100 / 10, preferably 100 / 70-100 / 15, more preferably 100 / 60-100 / 20.
  • the ratio is preferably 100/80 or more, and the ratio is preferably 100/10 or less for a smooth conversion reaction.
  • magnesium oxide (MgO) or magnesium hydroxide (Mg (OH) 2 ) may be used alone or as a catalyst.
  • Base catalysts such as sodium hydroxide (NaOH) and potassium hydroxide (KOH) react with free fatty acids contained in oils or fats to form soaps, and thus esterification is impossible. While it is possible to use a high acid value raw material including free fatty acids, it is possible to simultaneously esterify the free fatty acids, thereby increasing the conversion to fatty acid alkyl esters and lowering the yield loss.
  • the content of the catalyst may be 0.001 to 0.5% by weight, preferably 0.005 to 0.3% by weight, more preferably 0.01 to 0.1% by weight based on the weight of the oil, fat or mixtures thereof.
  • a small amount of the catalyst can be used. When a small amount of the catalyst is used, the yield loss can be minimized by suppressing the generation of the emulsion upon separation of the layer after completion of the reaction.
  • the catalyst may be mixed with alcohol, oil, fat or mixtures thereof, added to the reaction in the form of a mixture, and mixed in a slurry state.
  • the raw material and catalyst mixture in the slurry state may be introduced into the esterification and transition esterification process continuously or intermittently.
  • Most catalysts added to the reaction participate in the reaction in the form of a homogeneous system, and they may participate in the reaction in the form of oxides, hydroxides, fatty acid salts, and the like during the conversion reaction.
  • esterification and transesterification reaction is carried out by continuous or discontinuous addition of alcohol and MgO or Mg (OH) 2 catalyst to oil, fat, or mixtures thereof.
  • the esterification and transition esterification temperature of the present invention is 150 to 250 ° C, preferably 180 to 230 ° C, more preferably 190 to 220 ° C. If the reaction temperature is less than 150 °C, the conversion rate to fatty acid alkyl ester is reduced because the activity of the metal base catalyst does not appear, and if it exceeds 250 °C energy cost increases to increase the process cost and the raw material oil, fat, or Carbonization of these mixtures may occur.
  • the reaction pressure is 5 to 100 atm, preferably 10 to 70 atm, more preferably 20 to 50 atm. If the reaction pressure is less than 5 atm, the alcohol is present in the gas phase to make a uniform reaction system, excess alcohol is required. In addition, if it exceeds 100 atm, the process equipment becomes complicated and the process cost increases, making it difficult to apply to commercial production.
  • the esterification process of the invention can be carried out continuously or batchwise. Both the reaction time of the batch process and the reaction time of the continuous process may be 30 minutes to 6 hours, preferably 1 hour to 4 hours. In order to sufficiently proceed to the fatty acid alkyl ester, the reaction time is preferably 30 minutes or more, and when considering the generation of carbides and the progress of the reverse reaction due to long-term stagnation at high temperature, the reaction time is preferably 6 hours or less.
  • a continuous stirred reactor type (CSTR) in the case of a continuous process a line or a static mixer type in the case of a batch may be used. Some of the water produced during the reaction can be removed continuously out of the reactor by adjusting the reaction pressure, thereby promoting the esterification reaction to lower the acid value of the product more efficiently.
  • CSTR continuous stirred reactor type
  • the present invention may further comprise the step of recovering the fatty acid alkyl ester of the upper layer after the esterification and transesterification reaction to prepare a fatty acid alkyl ester, removing the unreacted alcohol and water and separating the layers.
  • the unreacted alcohol and water are removed by a known method such as evaporation and extraction, and then the layers are separated.
  • the upper layer includes fatty acid ester, monoglyceride, diglyceride, catalyst, and the like. Glycerin, catalysts, other unconverted glycerides, and the like. Fatty acid alkyl esters with significantly lower acid values can be obtained by the esterification process according to the invention.
  • the lower layer of glycerin produced in this process is recovered after an additional purification process can be useful for various uses, such as food, industrial.
  • the catalyst used after the esterification and transesterification reaction of the present invention can be removed from the fatty acid alkylester by distillation or acid washing. Distillation residues during distillation contain large amounts of catalyst and can be reused as catalysts for esterification and transesterification reactions.
  • the present invention may further comprise a pretreatment process for reducing free fatty acids in the raw materials prior to the esterification and transesterification reaction steps.
  • the pretreatment process may be a conventional method that can reduce the free fatty acid of the oil, fat, or mixtures thereof containing free fatty acid or esterification without a catalyst.
  • the method may further include reacting the oil, the fat, or a mixture thereof under low catalyst of C 1 -C 5 with 150 to 250 ° C. and 5 to 100 atmospheres.
  • esterification and transesterification reaction may occur between the raw material and the alcohol to reduce free fatty acid.
  • the oil or fat / alcohol ratio may be 100/80 to 100/10, preferably 100/70 to 100/15, more preferably 100/60 to 100/20.
  • the ratio is preferably 100/80 or more, and the ratio is preferably 100/10 or less for a smooth conversion reaction.
  • the pretreatment process can be carried out in a continuous or batch process.
  • the reaction time of the batch process and the raw material reaction time of the continuous process are preferably 30 minutes to 6 hours.
  • a reactor such as a stirred reactor type (CSTR) in the case of a batch process, a line or a static mixer form in the case of a continuous process may be used.
  • Some of the water produced during the reaction can be removed continuously out of the reactor by adjusting the reaction pressure, thereby promoting the esterification reaction to lower the acid value of the reactants more efficiently.
  • the reaction products of the pretreatment process include fatty acid esters, monoglycerides, diglycerides, triglycerides, alcohols and water, among which the unreacted alcohols and water are removed by evaporation and the rest are esterified and transesterified reactions of the present invention.
  • the acid value of fats and oils can be greatly reduced by the pretreatment process, and triglycerides can be converted into fatty acid alkyl esters in high yield by a transesterification reaction with alcohol. If the pressure is lowered continuously to remove some of the water produced, the water removal process can be omitted.
  • the pretreatment process of the present invention may be particularly effective when the acid value of the oil or fat is 10 or more, specifically 20 or more.
  • the produced fatty acid ester may be recovered to perform further ester and transesterification reaction.
  • the additional esterification reaction may be repeated one or more times, and the purity may be increased by converting the free fatty acid and the unconverted glyceride present in the fatty acid alkyl ester to the fatty acid alkyl ester by the additional reaction.
  • the conversion reaction may proceed without additional catalyst in the additional esterification step.
  • additional catalysts can be added, which are catalysts used in previous esterification processes, ie MgO and Mg (OH) 2 , or other applicable catalysts, for example base catalysts, in particular The metal base catalyst may be added alone or in a mixture.
  • Other applicable catalysts include base catalysts such as NaOH, KOH, KOCH 3 , NaOCH 3 and the like.
  • the amount of the catalyst used may be preferably 0.001 to 0.5% by weight, more preferably 0.005 to 0.3, based on the weight of the raw materials used for the additional esterification and the transesterification reaction except for alcohol. Weight percent, most preferably 0.01 to 0.1 weight percent.
  • the ratio of fatty acid alkylester / alcohol recovered in the further ester process may be 100/80 to 100/10, preferably 100/70 to 100/15, more preferably 100/60 to 100/20. .
  • the ratio is preferably 100/80 or more, and the ratio is preferably 100/10 or less for a smooth conversion reaction.
  • the pressure of the further esterification reaction may be at high or low pressure.
  • high pressure it may be 5 to 100 atm, preferably 10 to 70 atm, more preferably 20 to 50 atm, and in the case of low pressure, it may be at normal to 10 atm, preferably at atmospheric pressure to 5 atm.
  • the reaction temperature may be a condition of high temperature or low temperature. In the case of high temperature, it may be 150 to 250 ° C, preferably 180 to 230 ° C, more preferably 190 to 220 ° C, and in the case of low temperature, 40 to 100 ° C, preferably 50 to 80 ° C.
  • the manner of the other further esterification reactions is the same as for the previous esterification and transesterification reactions.
  • alcohol and water are first removed from the reaction product by evaporation or the like.
  • Fatty acid alkylesters can be recovered from known reaction products from which alcohol and water have been removed.
  • the reaction product is distilled to obtain fatty acid alkyl esters and glycerin from the top of the distillation column, and then the layers are separated to obtain fatty acid alkyl esters.
  • the fatty acid alkyl esters are separated from the reaction product by separating the fatty acid alkyl esters and glycerin. How to get.
  • the recovered fatty acid alkyl ester can be purified by additional known methods such as washing with water and dehydration.
  • fatty acid alkyl esters with greatly reduced acid values can be obtained.
  • the fatty acid alkyl ester having a low content of unconverted glyceride, which has a low content of monoglyceride, diglyceride and triglyceride can be secured in high yield.
  • fatty acid alkyl esters can be produced in high yield with high reaction activity while using oils, fats, or mixtures thereof having a high free fatty acid content of 2 to 200 as a raw material.
  • yield loss was calculated by comparing the content of fatty acid alkyl ester recovered after layer separation with the theoretical content of fatty acid alkyl ester that can be produced. This yield loss refers to the loss of fatty acid alkylesters upon layer separation due to emulsion formation.
  • the acid value can be obtained by the following equation.
  • Acid value [volume of KOH solution used for sample titration (ml)-volume of KOH solution used in background test (ml)] * concentration of KOH solution (mol / L) * 56.1 / mass of sample (g)
  • a fatty acid alkyl ester was prepared and recovered in the same manner as in Example 1, except that 0.024 g of Mg (OH) 2 was used as a catalyst, and then the acid value and organic content of the recovered fatty acid alkyl ester layer were analyzed and yield loss was measured. Calculated.
  • a fatty acid alkyl ester was prepared and recovered in the same manner as in Example 1 except that 0.054 g of NaOH was used as a catalyst, and then the acid value and organic matter content of the recovered fatty acid alkyl ester layer were analyzed and yield loss was calculated.
  • a fatty acid alkyl ester was prepared and recovered in the same manner as in Example 1 except that KOH 0.052 g was used as a catalyst, and then the acid value and organic matter content of the recovered fatty acid alkyl ester layer were analyzed and yield loss was calculated.
  • the fatty acid alkyl ester was prepared and recovered in the same manner as in Example 1 except that 0.3 g of sodium hydroxide (NaOH) was used as a catalyst and reacted at 80 ° C., and the acid value and organic matter content of the recovered fatty acid alkyl ester layer. was analyzed and yield loss was calculated.
  • NaOH sodium hydroxide
  • a fatty acid alkyl ester was prepared and recovered in the same manner as in Comparative Example 3, except that 0.6 g of sodium hydroxide (NaOH) was used as a catalyst, and then the acid value and organic content of the recovered fatty acid alkyl ester layer were analyzed and yield loss was measured. Calculated.
  • Comparative Examples 1 and 2 using the existing base catalyst can be prepared more than a certain level of fatty acid alkyl ester, there is a disadvantage in that the yield loss occurs due to the emulsion upon separation of the layer after the reaction.
  • Comparative Example 3 in which a large amount of the existing base catalyst was added at low temperature, it was confirmed that the conversion rate to the fatty acid alkyl ester was very low.
  • Comparative Example 4 which used more catalyst than Comparative Example 3, the reaction proceeded rapidly and the conversion rate to fatty acid alkyl ester was high.
  • the glycerin layer was equivalent to 40% by weight. It is confirmed that the yield loss is large because it contains a large amount of 30% by weight.
  • Example 3 The reaction was carried out in the same manner as in Example 3 except that the reaction time was 3 hours to recover the fatty acid alkyl ester layer.
  • the acid value, organic matter content, and yield loss of the recovered fatty acid alkyl ester layer were analyzed in the same manner as in Example 1.
  • Example 7 The reaction was carried out in the same manner as in Example 7, except that the reaction time was 4 hours to recover the fatty acid alkyl ester layer.
  • the acid value, organic matter content, and yield loss of the recovered fatty acid alkyl ester layer were analyzed in the same manner as in Example 1.
  • fatty acid alkyl esters can be produced at high conversion rates without loss of yield even in Examples 7 and 8 using a small amount of catalysts using palm oil by-products having much higher acid values than Examples 5 and 6. Able to know.
  • the fatty acid alkylester was prepared by performing the secondary ester and transition ester reaction after the primary ester and transition ester reaction step. Specifically, 180 g of palm oil by-product (acid value 200 mgKOH / g) and 80 g of methanol were added to a 500 ml high-pressure reactor, and MgO 0.054 g was used as a catalyst to carry out the first ester and transition ester reaction at 200 ° C. and 28 atm for 2 hours. After completion of the reaction, unreacted methanol and generated water were removed under reduced pressure, and the layers were separated for 1 hour to separate fatty acid alkyl esters, unreacted fatty acids, glycerides, and glycerin from lower layers.
  • the fatty acid alkylester layer was recovered in the same manner as in Example 9 except that the primary ester and transition ester reactions and the secondary ester and transition ester reactions were all performed at 220 ° C. and 38 atm.
  • the acid value, organic matter content, and yield loss of the recovered fatty acid alkyl ester layer were analyzed in the same manner as in Example 1.
  • the primary ester and the transesterification reaction were carried out using a high acid value lower raw material, and then the secondary ester and the transesterification reaction without additional catalyst were added. It can be seen that it can be produced with a high conversion rate.
  • a pretreatment process is performed, and then, a second ester and transition ester reaction is performed to prepare fatty acid alkyl esters from a lower acidic raw material in a continuous process.
  • 180 g of palm oil mixture (acid value 60 mgKOH / g) and 80 g of methanol were added to a 500 ml high-pressure reactor, and the pretreatment reaction was performed at 200 ° C. and 30 atm for 2 hours. After completion of the reaction, unreacted methanol and generated water were removed under reduced pressure, and the layers were separated for 1 hour to separate fatty acid alkyl esters, unreacted fatty acids, glycerides, and glycerin from lower layers.
  • the pretreatment process was carried out before the primary ester and transition ester reaction step, and then the secondary ester and transition ester reaction was carried out to prepare fatty acid alkyl esters from the lower raw materials of the middle acid value in a continuous process.
  • 180 g of waste cooking oil (acid value 43 mgKOH / g) and 80 g of methanol were added to a 500 ml high-pressure reactor, and the pretreatment reaction was performed at 200 ° C. and 30 atm for 2 hours. After completion of the reaction, unreacted methanol and generated water were removed under reduced pressure, and the layers were separated for 1 hour to separate fatty acid alkyl esters, unreacted fatty acids, glycerides, and glycerin from lower layers.
  • the upper fatty acid alkyl ester, 180 g of unreacted fatty acid, glyceride, and 80 g of methanol were placed in a 500 ml high-pressure reactor, and a primary ester and a transesterification reaction were performed at 200 ° C. and 30 atm for 2 hours using a MgO catalyst. After completion of the reaction, unreacted methanol and generated water were removed under reduced pressure, and the layers were separated for 1 hour to separate fatty acid alkyl esters, unreacted fatty acids, glycerides, and glycerin from lower layers.
  • the upper fatty acid alkyl ester, 180 g of unreacted fatty acid, glyceride, and 80 g of methanol were placed in a 500 ml high-pressure reactor, and a secondary ester and a transesterification reaction were performed at 200 ° C. and 30 atm for 2 hours using a MgO catalyst.
  • the unreacted methanol and the produced water were removed by evaporation, and the fatty acid alkylester layer and the glycerin layer were separated by layer separation to recover the fatty acid alkylester layer.
  • the acid value, organic matter content, and yield loss of the recovered fatty acid alkyl ester layer were analyzed in the same manner as in Example 1.
  • the conventional base catalyst process is carried out in a continuous process to proceed the secondary ester and the transesterification reaction It can be seen that the fatty acid alkyl ester of low acid value can be prepared in a high conversion rate.
  • waste cooking oil (acid value 80 mgKOH / g) and 80 g of methanol were put into a 500 ml high-pressure reactor, and the pretreatment process was performed at 200 ° C. and 30 atm for 2 hours. After completion of the reaction, unreacted methanol and generated water were removed under reduced pressure, and the layers were separated for 1 hour to separate fatty acid alkyl esters, unreacted fatty acids, glycerides, and glycerin from lower layers.
  • the conventional base catalyst process is carried out in a continuous process to the secondary ester And it can be seen that the fatty acid alkyl ester can be produced at a high conversion rate while lowering the acid value when the transition ester reaction proceeds.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • General 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 Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Fats And Perfumes (AREA)

Abstract

Cette invention concerne un procédé de préparation d'esters d'alkyle d'acides gras, comprenant une étape d'estérification et de transestérification d'une huile, d'une matière grasse ou d'un mélange de celles-ci, l'huile, la matière grasse ou leur mélange contenant des acides gras libres et ayant un indice d'acide de 2 à 200, en présence d'un ou de plusieurs catalyseurs choisis parmi un alcool à faible teneur en carbone, à savoir, C1 à C5, , MgO et Mg(OH)2, dans des conditions de 150 à 250°C et de 5 à 100 pressions atmosphériques.
PCT/KR2011/007106 2010-09-27 2011-09-27 Procédé de préparation d'esters d'alkyle d'acides gras Ceased WO2012044042A2 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR1020100093474A KR101072674B1 (ko) 2010-09-27 2010-09-27 지방산 알킬에스테르의 제조방법
KR20100093472 2010-09-27
KR10-2010-0093472 2010-09-27
KR10-2010-0093474 2010-09-27

Publications (2)

Publication Number Publication Date
WO2012044042A2 true WO2012044042A2 (fr) 2012-04-05
WO2012044042A3 WO2012044042A3 (fr) 2012-06-07

Family

ID=45893636

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2011/007106 Ceased WO2012044042A2 (fr) 2010-09-27 2011-09-27 Procédé de préparation d'esters d'alkyle d'acides gras

Country Status (1)

Country Link
WO (1) WO2012044042A2 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10542773B2 (en) 2013-07-19 2020-01-28 Philip Morris Products S.A. Hydrophobic paper

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6228754B1 (en) * 1999-01-05 2001-05-08 Advanced Micro Devices, Inc. Method for forming semiconductor seed layers by inert gas sputter etching
US20060014378A1 (en) * 2004-07-14 2006-01-19 Sanjeev Aggarwal System and method to form improved seed layer
US7294574B2 (en) * 2004-08-09 2007-11-13 Applied Materials, Inc. Sputter deposition and etching of metallization seed layer for overhang and sidewall improvement
US7585760B2 (en) * 2006-06-23 2009-09-08 Intel Corporation Method for forming planarizing copper in a low-k dielectric

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10542773B2 (en) 2013-07-19 2020-01-28 Philip Morris Products S.A. Hydrophobic paper

Also Published As

Publication number Publication date
WO2012044042A3 (fr) 2012-06-07

Similar Documents

Publication Publication Date Title
US4164506A (en) Process for producing lower alcohol esters of fatty acids
CA2535639A1 (fr) Procede de fabrication d'esters alkyliques a l'aide de la glycerine
US4652406A (en) Process for the production of fatty acid alkyl esters
US20120255223A1 (en) process for conversion of low cost and high ffa oils to biodiesel
US6815551B2 (en) Processes for concentrating tocopherols and/or sterols
SG140551A1 (en) Production of biodiesel and glycerin from high free fatty acid feedstocks
US5424457A (en) Process for the production of sterol and tocopherol concentrates
US5116546A (en) Process for producing fatty-acid lower-alkyl mono-esters
WO2014030838A1 (fr) Composition de plastifiant
WO2015026073A1 (fr) Procédé de préparation d'ester de glycol par distillation réactive
EP1512738B1 (fr) Procede relatif a l'elaboration de composition d'ester d'alkyle d'acide gras
WO2010058983A2 (fr) Procédé d'extraction d'ester d'acide (méth)acrylique
WO2012044042A2 (fr) Procédé de préparation d'esters d'alkyle d'acides gras
WO2020122591A1 (fr) Composition de plastifiant et composition de résine comprenant une telle composition de plastifiant
US11591545B2 (en) Method of producing biodiesel
WO2013183872A1 (fr) Procédé de fabrication d'huile de base lubrifiante d'ester biodégradable au moyen d'un catalyseur acide solide
US20050080279A1 (en) Process for production of fatty acid esters
CA2422804A1 (fr) Procede de fabrication de produits bruts pour l'obtention d'acide linoleique conjugue
CA2492831C (fr) Compositions de tocopherol de couleur stable et comportant peu d'impuretes, et procedes de preparation de ceux-ci
US12031107B2 (en) Energy efficient biodiesel production from natural or industrial waste oil
KR101297495B1 (ko) 지방산 알킬에스테르의 제조방법
KR101072674B1 (ko) 지방산 알킬에스테르의 제조방법
CN101544928B (zh) 一种降低生物油料酸值的方法
KR20230125930A (ko) 고산가 지방산으로부터 지방산에스테르(바이오연료) 생산 공정
WO2020106123A1 (fr) Procédé de préparation d'ester d'acide carboxylique d'alkyle et appareil de préparation d'ester d'acide carboxylique d'alkyle

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 11829548

Country of ref document: EP

Kind code of ref document: A2

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 11829548

Country of ref document: EP

Kind code of ref document: A2