JP2008260819A - Method for producing biodiesel fuel - Google Patents
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- 239000003225 biodiesel Substances 0.000 title claims abstract description 15
- 238000004519 manufacturing process Methods 0.000 title claims description 16
- 239000002994 raw material Substances 0.000 claims abstract description 31
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 28
- 239000000194 fatty acid Substances 0.000 claims abstract description 28
- 229930195729 fatty acid Natural products 0.000 claims abstract description 28
- 238000005809 transesterification reaction Methods 0.000 claims abstract description 22
- 239000002253 acid Substances 0.000 claims abstract description 16
- 125000005233 alkylalcohol group Chemical group 0.000 claims abstract description 16
- 239000003513 alkali Substances 0.000 claims abstract description 9
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- 241000221089 Jatropha Species 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 48
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 24
- 238000006243 chemical reaction Methods 0.000 abstract description 18
- 235000021588 free fatty acids Nutrition 0.000 abstract description 13
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 abstract description 6
- 150000002148 esters Chemical class 0.000 abstract description 6
- 125000004432 carbon atom Chemical group C* 0.000 abstract description 5
- 238000000034 method Methods 0.000 abstract description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 abstract description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 abstract description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 abstract description 4
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 abstract description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 abstract description 4
- 150000001298 alcohols Chemical class 0.000 abstract description 4
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 abstract description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 abstract description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 abstract description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 abstract description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 abstract description 2
- 235000019253 formic acid Nutrition 0.000 abstract description 2
- 150000007522 mineralic acids Chemical class 0.000 abstract description 2
- 229910017604 nitric acid Inorganic materials 0.000 abstract description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 abstract description 2
- 239000003921 oil Substances 0.000 description 71
- 235000019198 oils Nutrition 0.000 description 70
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 36
- 239000010410 layer Substances 0.000 description 31
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 12
- 150000004702 methyl esters Chemical class 0.000 description 9
- 150000004665 fatty acids Chemical class 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 239000002283 diesel fuel Substances 0.000 description 4
- 235000019482 Palm oil Nutrition 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000012044 organic layer Substances 0.000 description 3
- 239000002540 palm oil Substances 0.000 description 3
- 235000015112 vegetable and seed oil Nutrition 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- 235000019484 Rapeseed oil Nutrition 0.000 description 2
- -1 alcohol ester Chemical class 0.000 description 2
- 239000003240 coconut oil Substances 0.000 description 2
- 235000019864 coconut oil Nutrition 0.000 description 2
- 239000003925 fat Substances 0.000 description 2
- 235000019197 fats Nutrition 0.000 description 2
- 235000019387 fatty acid methyl ester Nutrition 0.000 description 2
- 239000008158 vegetable oil Substances 0.000 description 2
- 241000282816 Giraffa camelopardalis Species 0.000 description 1
- 240000008415 Lactuca sativa Species 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 235000019485 Safflower oil Nutrition 0.000 description 1
- 235000019486 Sunflower oil Nutrition 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- OGBUMNBNEWYMNJ-UHFFFAOYSA-N batilol Chemical class CCCCCCCCCCCCCCCCCCOCC(O)CO OGBUMNBNEWYMNJ-UHFFFAOYSA-N 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000008162 cooking oil Substances 0.000 description 1
- 235000005687 corn oil Nutrition 0.000 description 1
- 239000002285 corn oil Substances 0.000 description 1
- 235000012343 cottonseed oil Nutrition 0.000 description 1
- 239000002385 cottonseed oil Substances 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 235000021323 fish oil Nutrition 0.000 description 1
- 125000005456 glyceride group Chemical group 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000001035 methylating effect Effects 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000003346 palm kernel oil Substances 0.000 description 1
- 235000019865 palm kernel oil Nutrition 0.000 description 1
- 235000015277 pork Nutrition 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 235000005713 safflower oil Nutrition 0.000 description 1
- 239000003813 safflower oil Substances 0.000 description 1
- 235000012045 salad Nutrition 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000008159 sesame oil Substances 0.000 description 1
- 235000011803 sesame oil Nutrition 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000002600 sunflower oil Substances 0.000 description 1
- 150000003626 triacylglycerols Chemical class 0.000 description 1
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 description 1
- 235000019871 vegetable fat Nutrition 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
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- Liquid Carbonaceous Fuels (AREA)
- Fats And Perfumes (AREA)
Abstract
【課題】本発明は、原料油を低級アルキルアルコール及びアルカリ触媒存在下でエステル交換反応させて脂肪酸アルキルエステルを製造する方法において、原料油中の遊離脂肪酸を除去し、脂肪酸アルキルエステルの収率を向上させることを目的とする。
【解決手段】酸及びアルキルアルコールを原料油に添加し、遊離脂肪酸をアルキルアルコール層に抽出・除去した後、該添加により生ずる油層をエステル反応に供することによって、収率良く、脂肪酸アルキルエステル、ひいてはバイオディーゼル燃料を製造する。酸としては、硫酸、塩酸、硝酸、酢酸、蟻酸、リン酸等の無機酸が例示される。アルコールとしては、メタノール、エタノール、プロパノール、イソプロパノール、ブタノール、ペンタノール、ヘキサノール等の炭素数１〜６のアルコールが例示される。
【選択図】なしThe present invention relates to a process for producing a fatty acid alkyl ester by subjecting a raw oil to a transesterification reaction in the presence of a lower alkyl alcohol and an alkali catalyst, thereby removing free fatty acids in the raw material oil and increasing the yield of the fatty acid alkyl ester. The purpose is to improve.
[MEANS FOR SOLVING PROBLEMS] An acid and an alkyl alcohol are added to a raw material oil, and free fatty acids are extracted and removed from an alkyl alcohol layer, and then an oil layer formed by the addition is subjected to an ester reaction, whereby a fatty acid alkyl ester, and thus a high yield. Produces biodiesel fuel. Examples of the acid include inorganic acids such as sulfuric acid, hydrochloric acid, nitric acid, acetic acid, formic acid and phosphoric acid. Examples of the alcohol include alcohols having 1 to 6 carbon atoms such as methanol, ethanol, propanol, isopropanol, butanol, pentanol, and hexanol.
[Selection figure] None
Description
本発明は、バイオディーゼル燃料の製造方法に関する。より詳細には、油脂とアルコールとのエステル交換反応によりバイオディーゼル燃料を製造する方法において、原料油に酸及びアルキルアルコールを添加して、アルキルアルコールを含む有機層と油層に分液し、アルキルアルコーを含む有機相を除去することによって、原料油中の脂肪酸のアルコールエステルを除去した後、該油層をメチルエステル化してバイオディーゼル燃料を製造する技術に関する。 The present invention relates to a method for producing biodiesel fuel. More specifically, in a method for producing biodiesel fuel by transesterification of fats and oils, an acid and an alkyl alcohol are added to a raw material oil, and the resulting mixture is separated into an organic layer containing an alkyl alcohol and an oil layer, and an alkyl alcohol is obtained. The present invention relates to a technique for producing a biodiesel fuel by removing an alcohol ester of a fatty acid in a raw material oil by removing an organic phase containing, and then methylating the oil layer.
パーム油、ココナツ油、なたね油、サラダ油、てんぷら油等の植物油、食用廃油の主成分であるモノグリセライド、ジグリセライド、トリグリセライドを、アルカリ触媒（水酸化カリウム、水酸化ナトリウムなど）の存在下で、アルキルアルコールとエステル交換反応させることによって、脂肪酸アルキルエステルが得られることが知られている。そして、この反応を利用して、植物油脂や廃食油等からディーゼル燃料油（バイオディーゼル燃料）として利用できるアルキルエステルを製造する技術についても各種の検討がなされている（例えば、特許文献１参照）。 Palm oil, coconut oil, rapeseed oil, salad oil, tempura oil and other vegetable oils, monoglycerides, diglycerides, and triglycerides, which are the main components of edible waste oil, in the presence of an alkali catalyst (potassium hydroxide, sodium hydroxide, etc.) It is known that fatty acid alkyl esters can be obtained by transesterification. And various examination is also made | formed also about the technique which manufactures the alkyl ester which can be utilized as a diesel fuel oil (biodiesel fuel) from vegetable fats and oils, waste cooking oil, etc. using this reaction (for example, refer patent document 1). .
しかしながら、原料油中には遊離脂肪酸が含まれており、この遊離脂肪酸はアルカリと交換反応し、その結果、脂肪酸アルキルエステル、ひいてはバイオディーゼル燃料の収率を低下させる一因となっていた。
したがって、本発明は、原料油中の遊離脂肪酸を除去し、脂肪酸アルキルエステルの収率を向上させることを目的とする。 Accordingly, an object of the present invention is to remove free fatty acids in raw material oil and improve the yield of fatty acid alkyl esters.
本発明者は、上記従来技術の問題点に鑑み鋭意検討を重ねた結果、酸及びアルキルアルコールを原料油に添加し、遊離脂肪酸をアルキルアルコール層に抽出・除去した後、該添加により生ずる油層をエステル反応に供することによって、収率良く、脂肪酸アルキルエステル、ひいてはバイオディーゼル燃料を製造できることを見出し、本発明を完成させた。 As a result of intensive studies in view of the above-mentioned problems of the prior art, the present inventor added an acid and an alkyl alcohol to the raw material oil, extracted and removed free fatty acids from the alkyl alcohol layer, and then an oil layer produced by the addition. It has been found that by subjecting to an ester reaction, a fatty acid alkyl ester, and thus biodiesel fuel can be produced with good yield, and the present invention has been completed.
すなわち、本発明は、製造方法を提供するものである。
項１．原料油を低級アルキルアルコール及びアルカリ触媒存在下でエステル交換反応させて脂肪酸アルキルエステルを製造する方法において、
該エステル交換反応の前に、原料油に酸及び低級アルキルアルコールを原料油を添加し、該添加により生ずる油層をエステル交換反応に供することを特徴とする脂肪酸アルキルエステルの製造方法。
項２．原料油がジャプロファ由来の油である項１に記載の製造方法。
項３．製造される脂肪酸アルキルエステルがバイオディーゼル燃料として利用されるものである項１又は２に記載の製造方法。
That is, the present invention provides a manufacturing method.
Item 1. In a method for producing a fatty acid alkyl ester by transesterifying a raw material oil in the presence of a lower alkyl alcohol and an alkali catalyst,
A method for producing a fatty acid alkyl ester, comprising adding an acid and a lower alkyl alcohol to a raw material oil before the transesterification reaction, and subjecting the oil layer produced by the addition to the transesterification reaction.
Item 2. Item 2. The production method according to Item 1, wherein the raw material oil is an oil derived from Japrofa.
Item 3. Item 3. The method according to Item 1 or 2, wherein the fatty acid alkyl ester to be produced is used as a biodiesel fuel.
本発明の製造方法は、低級アルキルアルコール及びアルカリ触媒存在下でエステル交換反応させて脂肪酸アルキルエステルを製造する方法において、原料油を酸及び低級アルコールで前処理することを特徴とする。この前処理によって、原料油中の遊離脂肪酸を十分に低減することができ、脂肪酸アルキルエステルを収率良く製造できる。また、本発明の製造方法はバッチ式であっても連続式であっても良い。 The production method of the present invention is characterized in that a feedstock oil is pretreated with an acid and a lower alcohol in a method for producing a fatty acid alkyl ester by transesterification in the presence of a lower alkyl alcohol and an alkali catalyst. By this pretreatment, the free fatty acid in the raw material oil can be sufficiently reduced, and the fatty acid alkyl ester can be produced with good yield. The production method of the present invention may be a batch type or a continuous type.
エステル交換反応の前処理における酸及び低級アルコールの添加によって、反応液は上層のアルキルアルコール層と下層の油層とに分液し、油層を次のエステル化反応に供する。原料油中の遊離脂肪酸は上層、すなわちアルキルアルコール層に抽出されるため、下層、すなわち油層は遊離脂肪酸が低減される。 By adding the acid and the lower alcohol in the pretreatment of the transesterification reaction, the reaction solution is separated into an upper alkyl alcohol layer and a lower oil layer, and the oil layer is subjected to the next esterification reaction. Since the free fatty acid in the raw material oil is extracted to the upper layer, that is, the alkyl alcohol layer, the lower layer, that is, the oil layer is reduced in free fatty acid.
原料油としては、バイオディーゼル燃料の原料として使用できるものを利用できる。例えば、ジャトロファ油、パーム油、ココナツ油、ナタネ油、ごま油、大豆油、トウモロコシ油、向日葵油、パーム核油、ヤシ油、紅花油、綿実油、キリ油等の植物油脂、牛油、豚油、魚油等の動物性油脂、又はこれらの変性油、劣化油、廃油等である。好ましくはジャトロファ油である。 As the raw material oil, one that can be used as a raw material for biodiesel fuel can be used. For example, vegetable oils such as jatropha oil, palm oil, coconut oil, rapeseed oil, sesame oil, soybean oil, corn oil, sunflower oil, palm kernel oil, palm oil, safflower oil, cottonseed oil, giraffe oil, cow oil, pork oil, Animal fats and oils such as fish oil, or these modified oils, deteriorated oils, waste oils and the like. Jatropha oil is preferred.
原料油には前処理のため、酸及び低級アルコールが添加される。酸の添加と低級アルコールの添加はその順序は特に問わず、酸の添加が先であっても、低級アルコールの添加が先であっても、両者を同時に添加しても良いし、酸と低級アルコールの混合物を添加しても良い。好ましくは酸を先に添加し、その後低級アルコールを添加する順序である。 An acid and a lower alcohol are added to the raw oil for pretreatment. The order of the addition of the acid and the addition of the lower alcohol is not particularly limited. The addition of the acid may be performed first, the addition of the lower alcohol may be performed first, or both may be added simultaneously. A mixture of alcohols may be added. Preferably, the acid is added first and then the lower alcohol is added.
酸の例としては、硫酸、塩酸、硝酸、酢酸、蟻酸、リン酸等の無機酸が挙げられ、好ましくは硫酸である。 Examples of the acid include inorganic acids such as sulfuric acid, hydrochloric acid, nitric acid, acetic acid, formic acid and phosphoric acid, and sulfuric acid is preferred.
低級アルコールとしては、メタノール、エタノール、プロパノール、イソプロパノール、ブタノール、ペンタノール、ヘキサノール等の炭素数１〜６の直鎖又は分枝状のアルコールが例示され、好ましくは炭素数１〜３の直鎖又は分枝状のアルコールである。より好ましくはメタノールである。 Examples of the lower alcohol include linear or branched alcohols having 1 to 6 carbon atoms such as methanol, ethanol, propanol, isopropanol, butanol, pentanol, and hexanol, and preferably linear or branched alcohols having 1 to 3 carbon atoms. A branched alcohol. More preferred is methanol.
酸の好ましい添加量は、原料油に対して０．１〜１０重量％、より好ましくは１〜５重量％である。低級アルコールの好ましい添加量は、原料油に対して９〜３００重量％、より好ましくは１２〜１５０重量％、よりいっそう好ましくは２７〜８０重量％である。 The preferable addition amount of the acid is 0.1 to 10% by weight, more preferably 1 to 5% by weight with respect to the raw material oil. The preferred addition amount of the lower alcohol is 9 to 300% by weight, more preferably 12 to 150% by weight, and still more preferably 27 to 80% by weight with respect to the raw material oil.
原料油に酸及び低級アルコールを添加と同時又は添加後から反応液を撹拌すると反応がより均一に進むため、好ましい。また、反応温度は反応が進行する範囲であれば特に制限されないが、好ましくは２０〜１００℃、より好ましくは４０〜８０℃である。反応時間もまた遊離脂肪酸が十分に低減される範囲であれば特に制限されないが、好ましくは０．２〜９６時間、より好ましくは０．５〜４８時間である。また、反応圧力も進行する範囲であれば特に制限されないが、好ましくは０．１〜１０Ｐａ、より好ましくは０．５〜２Ｐａである。 It is preferable to stir the reaction liquid simultaneously with or after the addition of the acid and the lower alcohol to the raw material oil because the reaction proceeds more uniformly. The reaction temperature is not particularly limited as long as the reaction proceeds, but is preferably 20 to 100 ° C, more preferably 40 to 80 ° C. The reaction time is not particularly limited as long as the free fatty acid is sufficiently reduced, but it is preferably 0.2 to 96 hours, more preferably 0.5 to 48 hours. Moreover, it will not be restrict | limited especially if the reaction pressure also advances, However Preferably it is 0.1-10 Pa, More preferably, it is 0.5-2 Pa.
反応終了後は反応液を分液する。分液は反応液を静置することによって行うことが好ましい。静置によって反応液は上層と下層に分液する。上層は原料油中の遊離脂肪酸に由来する脂肪酸アルコールエステルが含まれた有機層である。下層は原料油中のグリセライド、ジグリセライド、トリグリセライド等が含まれた油層である。有機層を除去することによって油層を分取できる。油層は脂肪酸アルキルエステルを製造するため、エステル交換反応に供される。 After completion of the reaction, the reaction solution is separated. Separation is preferably performed by allowing the reaction solution to stand. The reaction solution is separated into an upper layer and a lower layer by standing. The upper layer is an organic layer containing a fatty acid alcohol ester derived from a free fatty acid in the raw material oil. The lower layer is an oil layer containing glyceride, diglyceride, triglyceride and the like in the raw material oil. The oil layer can be separated by removing the organic layer. The oil layer is subjected to a transesterification reaction to produce a fatty acid alkyl ester.
エステル交換反応は、前処理で得られた油層、低級アルキルアルコール及びアルカリ触媒の存在下で行われる。エステル交換反応は、油層を利用すること以外は、従来の脂肪酸アルキルエステルを製造するためのエステル交換反応条件を利用することすることができる。 The transesterification reaction is carried out in the presence of an oil layer obtained by pretreatment, a lower alkyl alcohol and an alkali catalyst. The transesterification reaction can utilize transesterification reaction conditions for producing a conventional fatty acid alkyl ester except that an oil layer is utilized.
例えば、油層に対し０．５〜１００重量％、好ましくは１．０〜５．０重量％のアルカリ触媒（水酸化カリウム、水酸化ナトリウム、水酸化マグネシウム、水酸化カルシウムなど）と０．５〜２００重量％、好ましくは５〜１００重量％の低級アルコール（メタノール、エタノール等の炭素数１〜６の直鎖又は分枝状のアルコール、好ましくは炭素数１〜３の直鎖又は分枝状のアルコール。）を添加し、４０〜１００℃で０．５〜４８時間加温した後、０．５〜４８時間静置又は遠心分離して分液し、上層を分取し、上層を温水で洗浄後、アルコールを揮発させて目的物である脂肪酸のアルキルエステルを製造することができる。上記エステル交換反応は例示であって、本発明では、この例示の方法だけでなく、アルカリ触媒又は酸触媒、及び低級アルコールの存在下で原料をエステル交換して脂肪酸アルキルエステルを製造する方法であれば、前処理で得られた油層に、広く適用できる。 For example, 0.5 to 100% by weight, preferably 1.0 to 5.0% by weight of an alkali catalyst (potassium hydroxide, sodium hydroxide, magnesium hydroxide, calcium hydroxide, etc.) and 0.5 to 200% by weight, preferably 5 to 100% by weight of a lower alcohol (linear or branched alcohol having 1 to 6 carbon atoms such as methanol or ethanol, preferably linear or branched having 1 to 3 carbon atoms) Alcohol.) Is added and heated at 40 to 100 ° C. for 0.5 to 48 hours, then left still or centrifuged for 0.5 to 48 hours to separate the liquid, the upper layer is separated, and the upper layer is heated with warm water. After washing, the alcohol can be volatilized to produce the target fatty acid alkyl ester. The transesterification reaction is an example, and the present invention is not limited to this exemplified method, and may be a method for producing a fatty acid alkyl ester by transesterifying a raw material in the presence of an alkali catalyst or an acid catalyst and a lower alcohol. For example, it can be widely applied to the oil layer obtained by the pretreatment.
本発明の製造方法で得られた脂肪酸アルキルエステルは、ディーゼル燃料として使用することができる。 The fatty acid alkyl ester obtained by the production method of the present invention can be used as a diesel fuel.
本発明によれば、原料油を酸及び低級アルコールで前処理することによって、収率良く脂肪酸アルキルエステル及びバイオディーゼル燃料を製造することができる。 According to the present invention, the fatty acid alkyl ester and the biodiesel fuel can be produced in high yield by pretreating the raw material oil with an acid and a lower alcohol.
以下、本発明を実施例等により詳細に説明するが、本発明はこれらに限定されるものではない。 EXAMPLES Hereinafter, although an Example etc. demonstrate this invention in detail, this invention is not limited to these.
実施例１
＜原料油の前処理＞
ジャトロファ油に油の１重量％の硫酸を加え、メタノールを油の９．９，１４．７，１９．８，２４．６，２９．６，３９．２，４８．０，５７．１又は６９．１重量％加えて、５０℃で２時間反応させた。２時間静置した後、上層のアルコール層を除去した、油層中に残存する遊離脂肪酸の量と水酸化カリウムによる酸度を測定した。測定結果を図１に示す。その結果、１重量％の硫酸と６０重量％メタノールを添加して反応させた場合には酸度を原料油1ｇに対し、２ｍｇ水酸化カリウム量、または遊離脂肪酸の濃度を１％以下に抑制することができた。
＜得られた油層のエステル交換反応(a)＞
前処理で得られた油層にメタノールを重量比で５０％、水酸化ナトリウムを重量比で０．６，０．９，１．４，２．１，３．０又は３．７％の範囲で添加し、６５℃で２時間、エステル反応させ、反応液中の脂肪酸のメチルエステル（バイオディーゼル燃料）を定量し、原料油に対する収率を算出した。メチルエステルの収率を図２に示す。メタノールを重量比で２０％、水酸化ナトリウムを重量比で１．４％添加した場合には８８％の収率をえることができた。
＜得られた油層のエステル交換反応(b)＞
前処理で得られた油層に水酸化ナトリウムを重量比で１．４％添加し、メタノールを重量比で１１．２，２３．９，３７．４，５０．５又は６１．３％添加して６５℃で２時間、エステル反応させ反応液中の脂肪酸のメチルエステル（バイオディーゼル燃料）を定量し、原料油に対する収率を算出した。メチルエステルの収率を図３に示す。水酸化ナトリウムを重量比で１．４％、メタノールを重量比で２１．５％添加した場合には９０％の収率をえることができた。
Example 1
<Pretreatment of raw oil>
1% by weight sulfuric acid of jatropha oil is added to the oil and methanol is added to the oil 9.9, 14.7, 19.8, 24.6, 29.6, 39.2, 48.0, 57.1 or 69. 0.1% by weight was added and reacted at 50 ° C for 2 hours. After standing for 2 hours, the amount of free fatty acid remaining in the oil layer and the acidity by potassium hydroxide were measured after removing the upper alcohol layer. The measurement results are shown in FIG. As a result, when 1 wt% sulfuric acid and 60 wt% methanol are added and reacted, the acidity is controlled to 2 mg potassium hydroxide amount or 1% or less of free fatty acid concentration with respect to 1 g of raw oil. I was able to.
<Transesterification reaction of the obtained oil layer (a)>
In the oil layer obtained by the pretreatment, methanol is 50% by weight and sodium hydroxide is 0.6, 0.9, 1.4, 2.1, 3.0 or 3.7% by weight. The mixture was added and subjected to ester reaction at 65 ° C. for 2 hours. The methyl ester (biodiesel fuel) of the fatty acid in the reaction solution was quantified, and the yield relative to the raw material oil was calculated. The yield of methyl ester is shown in FIG. When methanol was added at a weight ratio of 20% and sodium hydroxide was added at a weight ratio of 1.4%, a yield of 88% could be obtained.
<Transesterification reaction of the obtained oil layer (b)>
Add 1.4% by weight of sodium hydroxide to the oil layer obtained by the pretreatment, and add 11.2, 23.9, 37.4, 50.5 or 61.3% of methanol by weight. The ester reaction was carried out at 65 ° C. for 2 hours, and the fatty acid methyl ester (biodiesel fuel) in the reaction solution was quantified, and the yield relative to the raw material oil was calculated. The yield of methyl ester is shown in FIG. When sodium hydroxide was added by 1.4% by weight and methanol was added by 21.5% by weight, a yield of 90% could be obtained.
比較例１
＜原料油を前処理しなかった場合のエステル交換反応(c)＞
原料のジャトロファ油にメタノールを重量比で７０％、水酸化ナトリウムを重量比で０〜５．２％の範囲で添加し、６５℃で２時間、エステル反応させ、反応液中の脂肪酸のメチルエステル（バイオディーゼル燃料）を定量し、原料油に対するメチルエステルの収率を算出した。収率を図４に示す。メタノールを重量比で７０％、水酸化ナトリウムを重量比で３．２％添加した場合には最大でメチルエステル５１％の収率しか得ることができなかった。
Comparative Example 1
<Transesterification reaction when raw oil is not pretreated (c)>
Methanol is added to the raw material Jatropha oil in a weight ratio of 70% and sodium hydroxide in a range of 0 to 5.2% by weight, and an ester reaction is carried out at 65 ° C. for 2 hours. (Biodiesel fuel) was quantified, and the yield of methyl ester relative to the raw material oil was calculated. The yield is shown in FIG. When methanol was added at a weight ratio of 70% and sodium hydroxide was added at a weight ratio of 3.2%, a maximum yield of methyl ester of 51% could be obtained.
比較例２
＜原料油を前処理しなかった場合のエステル交換反応(d)＞
原料のジャトロファ油に水酸化ナトリウムを重量比で３．０％添加し、メタノールを重量比で５０〜１５０％添加して６５℃で２時間、エステル反応させ反応液中の脂肪酸のメチルエステル（バイオディーゼル燃料）を定量し、原料油に対するメチルエステルの収率を算出した。収率を図５に示す。水酸化ナトリウムを重量比で３．０％、メタノールを重量比で６８％添加した場合には最大で５０％の収率しか得ることができなかった。
Comparative Example 2
<Transesterification reaction when raw oil is not pretreated (d)>
Sodium hydroxide is added to the raw material Jatropha oil by 3.0% by weight, methanol is added by 50 to 150% by weight, and ester reaction is carried out at 65 ° C. for 2 hours. Diesel fuel) was quantified, and the yield of methyl ester relative to the feedstock was calculated. The yield is shown in FIG. When sodium hydroxide was added at 3.0% by weight and methanol was added at 68% by weight, a maximum yield of 50% could be obtained.
本発明は、脂肪酸アルキルエステル又はディーゼル燃料の分野で利用可能である。 The present invention can be used in the field of fatty acid alkyl esters or diesel fuel.
Claims (3)
該エステル交換反応より前に、酸及び低級アルキルアルコールを原料油に添加し、該添加により生ずる油層をエステル交換反応に供することを特徴とする脂肪酸アルキルエステルの製造方法。 In a method for producing a fatty acid alkyl ester by transesterifying a raw material oil in the presence of a lower alkyl alcohol and an alkali catalyst,
A method for producing a fatty acid alkyl ester, wherein an acid and a lower alkyl alcohol are added to a raw material oil before the transesterification reaction, and an oil layer produced by the addition is subjected to a transesterification reaction.
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| JP2010150421A (en) * | 2008-12-25 | 2010-07-08 | Lion Corp | Method for producing concentrated phorbol ester |
| WO2010082527A1 (en) * | 2009-01-16 | 2010-07-22 | 富士フイルム株式会社 | Method for producing fatty acid alkyl ester, and diesel fuel |
| WO2012061909A1 (en) * | 2010-11-12 | 2012-05-18 | Falquete, Marco Antonio | A fuel composition based on four-carbon-atom alcohols and additives for diesel-cycle motors |
| WO2013076813A1 (en) * | 2011-11-22 | 2013-05-30 | 豊田通商株式会社 | Method for producing biodiesel fuel |
| US8497389B2 (en) | 2008-12-08 | 2013-07-30 | Initio Fuels Llc | Single step transesterification of biodiesel feedstock using a gaseous catalyst |
| CN108102790A (en) * | 2016-11-24 | 2018-06-01 | 中国科学院大连化学物理研究所 | A kind of aquatic byproducts fatty-acid ethyl ester preparation method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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