JP2006001893A - Method for producing alkyl ester of fatty acid - Google Patents
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Abstract
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本発明は、高純度脂肪酸アルキルエステルの製造方法に関する。詳しくはモノグリセライドの含有量が低減された脂肪酸アルキルエステルの製造方法に関するものである。 The present invention relates to a method for producing a high purity fatty acid alkyl ester. Specifically, the present invention relates to a method for producing a fatty acid alkyl ester having a reduced monoglyceride content.
脂肪酸グリセライドと低級アルコールとをアルカリ触媒存在下でエステル交換させて得られる脂肪酸アルキルエステル中には、グリセリン、遊離アルカリ、石鹸等の水溶性不純物が含まれるほか、反応中間体であるモノグリセライド及びジグリセライド、並びに未反応物であるトリグリセライドが含まれている。水溶性不純物は、脂肪酸アルキルエステルを水洗することで除去可能であるが、グリセライド類は油溶性であるため、その分離には工夫が必要である。 The fatty acid alkyl ester obtained by transesterification of fatty acid glyceride and lower alcohol in the presence of an alkali catalyst contains water-soluble impurities such as glycerin, free alkali and soap, as well as monoglyceride and diglyceride which are reaction intermediates, As well as unreacted triglyceride. Water-soluble impurities can be removed by washing the fatty acid alkyl ester with water. However, since glycerides are oil-soluble, contrivance is required for their separation.
グリセライド類の分離は、例えば蒸留により蒸留残渣へ濃縮除去することが知られている(特許文献1)。 The separation of glycerides is known to be concentrated and removed to a distillation residue by distillation, for example (Patent Document 1).
蒸留法では、トリグリセライドやジグリセライドは、脂肪酸アルキルエステルと沸点が大きく異なるため残渣へ除去できるが、モノグリセライド、特に短鎖脂肪酸モノグリセライドは、沸点が長鎖脂肪酸アルキルエステルと近いために、ある程度の量が留分へ混入し、完全に除去することが困難である。 In the distillation method, triglycerides and diglycerides have a boiling point that is significantly different from that of fatty acid alkyl esters, so they can be removed to the residue.Monoglycerides, especially short-chain fatty acid monoglycerides, have a boiling point that is close to that of long-chain fatty acid alkyl esters, so that a certain amount is retained. It is difficult to mix and remove completely.
また、エステル交換工程を複数回繰り返すことにより、転化率を向上させ、脂肪酸エステル中のモノグリセライド含有量を低減させることができる。しかし、この方法は蒸留分離におけるモノグリセライド除去効率の本質的改善とはならない上、工程が煩雑であり、また所要時間が長くなるという短所も有している。
本発明の課題は、モノグリセライドを含有する脂肪酸エステル混合物よりモノグリセライドを効率的に除去することができる、脂肪酸アルキルエステルの製造方法を提供することにある。 The subject of this invention is providing the manufacturing method of the fatty-acid alkylester which can remove a monoglyceride efficiently from the fatty-acid ester mixture containing a monoglyceride.
本発明は、モノグリセライドを含有する脂肪酸エステル混合物に、酸又はアルカリを添加して蒸留を行う、脂肪酸アルキルエステルの製造方法を提供する。 The present invention provides a method for producing a fatty acid alkyl ester, in which an acid or an alkali is added to a fatty acid ester mixture containing monoglyceride to perform distillation.
本発明の製造方法により、不純物、特にモノグリセライド含有量が少なく、高純度な脂肪酸アルキルエステルを効率的に製造することができる。 By the production method of the present invention, it is possible to efficiently produce a high-purity fatty acid alkyl ester with a small content of impurities, particularly monoglyceride.
本発明における脂肪酸アルキルエステルとしては、炭素数6〜24の飽和又は不飽和脂肪酸と低級アルコールとのエステルが好ましい。その調製方法には、油脂等の脂肪酸グリセライドと低級アルコールをエステル交換触媒存在下にてエステル交換する方法が挙げられる。 The fatty acid alkyl ester in the present invention is preferably an ester of a saturated or unsaturated fatty acid having 6 to 24 carbon atoms and a lower alcohol. The preparation method includes a method of transesterifying a fatty acid glyceride such as fat and oil and a lower alcohol in the presence of a transesterification catalyst.
油脂としては、例えばパーム油、パーム核油、ヤシ油、大豆油、ナタネ油、オリーブ油、ゴマ油等の植物油、魚油、牛脂、豚脂、鯨油等の動物油、又はこれらの混合物が挙げられる。 Examples of the oils and fats include vegetable oils such as palm oil, palm kernel oil, coconut oil, soybean oil, rapeseed oil, olive oil, and sesame oil, animal oils such as fish oil, beef tallow, lard, and whale oil, or mixtures thereof.
低級アルコールとしては、炭素数1〜5のアルコールが好ましく、例えばメタノール、エタノール、プロパノール、ブタノール、ペンタノール等が挙げられるが、メタノールが特に好ましい。 As a lower alcohol, C1-C5 alcohol is preferable, For example, methanol, ethanol, a propanol, a butanol, a pentanol etc. are mentioned, Methanol is especially preferable.
エステル交換触媒としては、アルカリ触媒又は酸触媒を用いることができる。アルカリ触媒としては、例えば、水酸化ナトリウム、水酸化カリウム、ナトリウムメチラート、カリウムメチラート等が挙げられる。また酸触媒としては、例えば、硫酸、硝酸、塩酸、リン酸、ベンゼンスルホン酸、トルエンスルホン酸等が挙げられる。 As the transesterification catalyst, an alkali catalyst or an acid catalyst can be used. Examples of the alkali catalyst include sodium hydroxide, potassium hydroxide, sodium methylate, potassium methylate and the like. Examples of the acid catalyst include sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid, benzenesulfonic acid, and toluenesulfonic acid.
エステル交換反応は、特に限定されることはなく、次のような通常用いられる条件で好適に行うことができる。即ち、脂肪酸グリセライドに対して、低級アルコール1.2〜5.0モル倍、触媒を適量、例えばアルカリ触媒0.01〜1.0重量%を混合し、反応温度40〜70℃、反応時間5〜120分で行えばよい。反応圧力は、減圧、常圧、加圧のいずれでも良い。 The transesterification reaction is not particularly limited, and can be suitably performed under the conditions usually used as follows. That is, 1.2 to 5.0 moles of lower alcohol and an appropriate amount of catalyst, for example, 0.01 to 1.0% by weight of alkali catalyst, are mixed with fatty acid glyceride, reaction temperature 40 to 70 ° C., reaction time 5 It can be done in ~ 120 minutes. The reaction pressure may be reduced pressure, normal pressure, or increased pressure.
反応後に得られる反応物には、脂肪酸アルキルエステル以外にグリセリン、低級アルコール、石鹸、触媒等が含有されており、グリセリン、低級アルコール層を分離して脂肪酸エステル層を得る。分離方法に特に限定はないが、静置分離、遠心分離等が好適である。 The reaction product obtained after the reaction contains glycerin, lower alcohol, soap, catalyst and the like in addition to the fatty acid alkyl ester, and the fatty acid ester layer is obtained by separating the glycerin and lower alcohol layers. There is no particular limitation on the separation method, but stationary separation, centrifugation, and the like are preferable.
脂肪酸エステル層には、溶解度分のグリセリン、低級アルコール、石鹸、触媒等が含まれており、適宜水洗によってこれらを除去する。
同様のエステル交換反応、水洗操作を繰り返すこともできる。
The fatty acid ester layer contains glycerin, lower alcohol, soap, catalyst and the like corresponding to the solubility, and these are appropriately removed by washing with water.
Similar transesterification and water washing operations can be repeated.
本発明においては、上記のような方法で得られる、モノグリセライドを含有する脂肪酸エステル混合物に、酸又はアルカリを添加して蒸留を行う。酸としては、H2SO4、HNO3、H3PO4、HPO3、H4P2O7、H3BO3等が挙げられる。アルカリとしては、CaO、Ca(OH)2、MgO、Mg(OH)2等が挙げられる。これらは1種又は2種以上用いることができるが、蒸留時の液性状の観点から、H2SO4、H3PO4、H3BO3、CaO、Ca(OH)2、MgO、Mg(OH)2が好ましく、H3PO4、H3BO3、CaO、Ca(OH)2、MgO、Mg(OH)2がより好ましい。 In the present invention, acid or alkali is added to the fatty acid ester mixture containing monoglyceride obtained by the method as described above and distilled. The acid, H 2 SO 4, HNO 3 , H 3 PO 4, HPO 3, H 4 P 2 O 7, H 3 BO 3 and the like. Examples of the alkali include CaO, Ca (OH) 2 , MgO, Mg (OH) 2 and the like. These can be used alone or in combination of two or more, but from the viewpoint of liquid properties during distillation, H 2 SO 4 , H 3 PO 4 , H 3 BO 3 , CaO, Ca (OH) 2 , MgO, Mg ( OH) 2 is preferable, and H 3 PO 4 , H 3 BO 3 , CaO, Ca (OH) 2 , MgO, and Mg (OH) 2 are more preferable.
酸又はアルカリの添加量は、モノグリセライドを効率的に除去し、かつ脂肪酸アルキルエステルの分解を抑制する観点から、モノグリセライドに対して0.1〜10モル倍が好ましく、0.1〜3モル倍がより好ましい。 The addition amount of the acid or alkali is preferably 0.1 to 10 mol times, preferably 0.1 to 3 mol times with respect to the monoglyceride from the viewpoint of efficiently removing the monoglyceride and suppressing the decomposition of the fatty acid alkyl ester. More preferred.
蒸留の条件は、得ようとする脂肪酸アルキルエステル及び含有されるモノグリセライドの沸点に応じて適宜選択することが可能であるが、減圧下に行うことが望ましい。真空度に対する設備の負担といった観点より、蒸留ボトムにおける圧力は0.1kPa以上が好ましく、1kPa以上がより好ましい。また、脂肪酸アルキルエステルの分解抑制の観点よりボトム温度は過剰に高めないことが有効であり、蒸留ボトムの圧力は100kPa以下が好ましく、10kPa以下がより好ましい。 The distillation conditions can be appropriately selected according to the fatty acid alkyl ester to be obtained and the boiling point of the monoglyceride contained, but it is desirable to carry out the distillation under reduced pressure. From the viewpoint of the burden of equipment on the degree of vacuum, the pressure at the distillation bottom is preferably 0.1 kPa or more, and more preferably 1 kPa or more. Moreover, it is effective not to raise the bottom temperature excessively from the viewpoint of inhibiting decomposition of the fatty acid alkyl ester, and the pressure of the distillation bottom is preferably 100 kPa or less, and more preferably 10 kPa or less.
蒸留工程に用いる蒸留塔は、塔内に気液接触のための金属板型、金網型の規則充填物や、ラシヒリング、ポールリング等の不規則充填物を充填した塔、あるいは多孔板トレイ、泡鐘式トレイ等の棚段を設置した精留塔、塔内に気液接触部を設けないフラッシュ塔のいずれでも良い。また本発明の蒸留操作は、連続、回分、半回分のいずれでも実施可能である。 The distillation column used in the distillation process is a column packed with a regular packed plate of metal plate or wire mesh for contact with gas and liquid, or an irregular packing such as Raschig ring or pole ring, or perforated plate tray, foam Either a rectifying column provided with a shelf such as a bell-type tray or a flash column not provided with a gas-liquid contact portion in the column may be used. The distillation operation of the present invention can be carried out continuously, batchwise, or semi-batch.
以下の実施例では、脂肪酸基の炭素数が18であるメチルエステルよりも沸点の低い、脂肪酸基の炭素数が10であるモノグリセライド(以下、C10モノグリセライドという)を含有する混合メチルエステルを原料として用い、蒸留精製における蒸留留分中のC10モノグリセライド含有量をもって、本発明の効果を示す。 In the following examples, a mixed methyl ester containing a monoglyceride having a boiling point lower than that of a methyl ester having 18 carbon atoms in the fatty acid group and having 10 carbon atoms in the fatty acid group (hereinafter referred to as C10 monoglyceride) is used as a raw material. The effect of the present invention is shown by the C10 monoglyceride content in the distillation fraction in the distillation purification.
原料脂肪酸エステルは、パーム核油をメタノールでエステル交換して得た、モノグリセライド含有脂肪酸エステルを使用した。エステル交換触媒には水酸化ナトリウムのメタノール溶液を用いた。原料脂肪酸エステルの組成は表1のとおりであった。尚、Cn脂肪酸メチルエステルは、炭素数nの脂肪酸のメチルエステルを意味する。 The raw fatty acid ester used was a monoglyceride-containing fatty acid ester obtained by transesterifying palm kernel oil with methanol. As the transesterification catalyst, a methanol solution of sodium hydroxide was used. The composition of the raw material fatty acid ester was as shown in Table 1. The Cn fatty acid methyl ester means a methyl ester of a fatty acid having n carbon atoms.
実施例1
蒸留用フラスコに、原料脂肪酸エステル300gを投入した。含有されるC10モノグリセライドの含有量は3.0g(分子量:246、12.2mmol)であった。ここに85%リン酸をリン酸換算で3.39g(分子量:98、34.6mmol、対モノグリセライド2.84モル倍)投入し、2.7kPaで220℃まで昇温して蒸留を行い、93重量%を留出させた。留分をガスクロマトグラフにて分析したところ、C10モノグリセライド含有量は0.02重量%に低下していた。
Example 1
The raw material fatty acid ester 300g was supplied into the distillation flask. The content of C10 monoglyceride contained was 3.0 g (molecular weight: 246, 12.2 mmol). To this, 85% phosphoric acid was added in an amount of 3.39 g in terms of phosphoric acid (molecular weight: 98, 34.6 mmol, 2.84 mol times monoglyceride), heated to 2.7 kPa up to 220 ° C. and distilled, % By weight was distilled off. When the fraction was analyzed by gas chromatography, the C10 monoglyceride content was reduced to 0.02% by weight.
実施例2
85%リン酸の添加量を、リン酸換算で0.34g(分子量:98、3.5mmol、対モノグリセライド0.28モル倍)とする以外は、実施例1と同様の処理を行った。
Example 2
The same treatment as in Example 1 was performed except that the amount of 85% phosphoric acid added was 0.34 g in terms of phosphoric acid (molecular weight: 98, 3.5 mmol, 0.28 mol times monoglyceride).
実施例3
85%リン酸の代わりに、ホウ酸0.18g(分子量:61.8、2.9mmol、対モノグリセライド0.24モル倍)を添加した以外は、実施例1と同様の処理を行った。
Example 3
The same treatment as in Example 1 was carried out except that 0.18 g of boric acid (molecular weight: 61.8, 2.9 mmol, 0.24 mol times of monoglyceride) was added instead of 85% phosphoric acid.
実施例4
85%リン酸の代わりに、酸化カルシウム0.17g(分子量:56、3.0mmol、対モノグリセライド0.25モル倍)を添加した以外は、実施例1と同様の処理を行った。
Example 4
The same treatment as in Example 1 was performed except that 0.17 g of calcium oxide (molecular weight: 56, 3.0 mmol, 0.25 mol times monoglyceride) was added instead of 85% phosphoric acid.
比較例1
85%リン酸の代わりに、ステアリン酸ナトリウム3.00g(分子量:306、9.8mmol、対モノグリセライド0.82モル倍)を添加した以外は、実施例1と同様の処理を行った。留分中のC10モノグリセライドの含有量は変化しておらず、モノグリセライド除去効果は得られなかった。
Comparative Example 1
The same treatment as in Example 1 was performed, except that 3.00 g of sodium stearate (molecular weight: 306, 9.8 mmol, 0.82 mol times of monoglyceride) was added instead of 85% phosphoric acid. The content of C10 monoglyceride in the fraction was not changed, and the monoglyceride removal effect was not obtained.
実施例1〜4及び比較例1で得られた留分の分析結果を表2にまとめて示した。 The analysis results of the fractions obtained in Examples 1 to 4 and Comparative Example 1 are summarized in Table 2.
Claims (5)
The method for producing a fatty acid alkyl ester according to any one of claims 1 to 4, wherein the fatty acid ester mixture containing monoglyceride is obtained by transesterification of fatty acid glyceride and a lower alcohol having 1 to 5 carbon atoms.
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Cited By (2)
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JP2006241015A (en) * | 2005-03-01 | 2006-09-14 | Kao Corp | Method for producing fatty acid lower alkyl ester |
JP2014005298A (en) * | 2010-07-14 | 2014-01-16 | Lg Chem Ltd | Apparatus for coproducing iso-type reaction products and alcohols from olefins, and coproduction method using the same |
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JPS5665097A (en) * | 1979-05-30 | 1981-06-02 | Lion Corp | Manufacture of fatty acid lower alcohol ester |
JPS56120799A (en) * | 1980-02-28 | 1981-09-22 | Lion Corp | Manufacture of high quality fatty ester |
JPH03200743A (en) * | 1989-04-05 | 1991-09-02 | Unilever Nv | Preparation of lower alkylmonoester of fatty acid |
JPH07310090A (en) * | 1994-05-19 | 1995-11-28 | Tensei Seiyu Kk | Production of fatty acid methyl ester |
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Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
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JPS5665097A (en) * | 1979-05-30 | 1981-06-02 | Lion Corp | Manufacture of fatty acid lower alcohol ester |
JPS56120799A (en) * | 1980-02-28 | 1981-09-22 | Lion Corp | Manufacture of high quality fatty ester |
JPH03200743A (en) * | 1989-04-05 | 1991-09-02 | Unilever Nv | Preparation of lower alkylmonoester of fatty acid |
JPH07310090A (en) * | 1994-05-19 | 1995-11-28 | Tensei Seiyu Kk | Production of fatty acid methyl ester |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
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JP2006241015A (en) * | 2005-03-01 | 2006-09-14 | Kao Corp | Method for producing fatty acid lower alkyl ester |
JP2014005298A (en) * | 2010-07-14 | 2014-01-16 | Lg Chem Ltd | Apparatus for coproducing iso-type reaction products and alcohols from olefins, and coproduction method using the same |
US9029608B2 (en) | 2010-07-14 | 2015-05-12 | Lg Chem, Ltd. | Apparatus for coproducting ISO type reaction products and alcohols from olefins, and method for coproducting them using the apparatus |
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