TW201108943A - Glyceride compositions and manufacturing method thereof - Google Patents
Glyceride compositions and manufacturing method thereof Download PDFInfo
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201108943 六、發明說明： 【發明所屬之技術領域】 本發月疋關於—種甘油酯組成物甘油酯組成物的製 故方法、降低甘油酯組成物中的縮水甘油(glycidd)之脂肪 酸S曰及/或3-氯丙m二醇之脂肪酸醋的含量的方法、 以及抑制縮水甘油之脂肪酸醋及，或3氯丙烷_12二醇之 脂肪酸酯的生成的方法。 【先前技術】 近年來’為了提南油脂的風味和穩定性，已做過各種 嘗試。油脂的風味和穩定性等品質的降低與各種因素有 關，已報告有因應各種因素的方法。例如，作為抑制伴隨 生成熱氧化分解物之油炸用油脂劣化臭的嘗試，專利文獻 1公開了-種使油脂中含有作為抗氧化劑之抗壞血酸等的 方法》根據這種方法，藉由將抗壞i酸等油脂難溶性之有 機酸以水溶液的狀態加人油脂中，並在高溫和高減壓下進 仃脫水處理，而能夠使抗氧化劑含在油脂令，這樣，即使 長時間使用也難以產生加熱劣化臭。 然而，已知三元環醚亦即環氧乙炫之結構化學性質 不穩定且反應性高，會引起聚合等化學反應。並且，鍵社 ㈣素的3-氯丙烧類也容易反應。在一部分甘油酷址成： 中，雖然微量但卻存在著具有該環氧W結構之環氧化物 的-種亦即縮水甘油之脂肪酸輯，而很可能引起聚人等化 學變化。而且’可從縮水甘油之脂肪酸酶衍生出的3氯丙 201108943 烷-1’2-二醇之脂肪酸酯，也很可能引起同樣的化學反應。 由於因聚合等而劣化的油脂在油炸時會產生泡珠和不愉快 的氣味’要儘量避免其存在。 但是，像專利文獻〗般添加抗氧化劑的方法，無法降 低油脂中已存在的縮水甘油之脂肪酸酯或3氯丙烷U•二 醇之脂肪酸I在其他f知方法中尚未報告特別針對降低 油脂中的.缩水甘油之脂肪酸酯< 3·氣丙烷]，2•二醇之脂肪 酸酯的方法，其研發一直受到期待。 專利文獻1 :國際公開第01/096506號小冊子。 【發明内容】 [發明所欲解決之問題] 本發明是養於上述問題而進行，其目的在於提供一種 較少縮水甘油之脂肪酸酯及/或3·氯丙烷_12_二醇之脂肪 酸醋的甘油醋組成物、該甘油醋組成物的製造方法、降低 φ甘油醋組成物中縮水甘油之脂肪酸醋及/或3氣丙烧# 二醇之脂肪酸醋的含量的方法、以及抑制縮水甘油之脂肪 酸醋及/或3-氣丙烷-“2-二醇之脂肪酸醋的生成之方法。 [解決問題之技術手段] 本發明人等為了解決上述問題而反覆專心研究，結果 發現藉由將：選自由3-氣丙燒…2_二醇、3氯丙院以·二 醇之脂肪酸醋、縮水甘油及縮水甘油之脂肪酸自旨所組成的 群組中之至少一種；及/或含有3質量％以上之二酸甘油 _的甘油醋組成物’在特定的溫度下進行脫臭處理，或進 201108943 一步暴露在酸性環境中’或在比通常溫度低的低溫條件丁 脫臭處理’或在規定範圍的酸值内加熱處理，則能夠降低 甘油酯組成物中的縮水甘油之脂肪酸酯或3·氣丙燒_丨2_二 醇之脂肪酸酯’而且，藉由同樣的方法，可期待降低具有 相同官能基的縮水甘油或3-氯丙烷-i，2_二醇，從而完成了 本發明β本發明具體而言係提供下述。 (1) 一種甘油酯組成物的製造方法，其特徵在於以 100 C〜240°c的溫度條件對甘油酯組成物進行脫臭處理， 鲁且上述甘油酯組成物含有：選自由3-氯丙烷_1，2_二醇、3_ 氯丙烷-1，2-二醇之脂肪酸酯、縮水甘油、及縮水甘油之脂 肪酸酯所組成的群組中之至少一種；及/或含有3質量％ 以上之二酸甘油酯。 (2) 如（1)所述之甘油酯組成物的製造方法，其中 上述甘油酯組成物含有縮水甘油之脂肪酸酯及/或％氣丙 烧·1，2·二醇之脂肪酸酯。 鲁 ）如（1)戈（2)所述之甘油酿組成物的製造方法， 其中上述甘油酯組成物是精製油。 生（）如（1)〜（3)中任一項所述之甘油酯組成物的 製&方法’其中上述甘油酯組成物的酸值I 2〜30，且在 上述脫臭處理前，對上述甘油醋組成物進行加熱處理。 (5) 如(1)〜, ^ )中任一項所述之甘油酯組成物的 製造方法，其!·、+· 、 迷脫臭處理前，將上述甘油酯組成物 暴露在酸性環境中。 (6) 如(1)〜(飞 中任一項所述之甘油酯組成物的 201108943 製造方法’其中在上述脫臭處理後’將上述甘油酯組成物 暴露在酸性環境中。 (7) 如（5)或（6)所述之甘油酯組成物的製造方法， 其中上述在酸㈣境中之暴露，錢上述甘油s旨組成物接 觸酸性加工助劑。 (8) 如（7)所述之甘油酯組成物的製造方法，其中 上述酸性加工助劑是選自由：活性白土、酸性活性炭、及 無機酸所組成的群組中之至少一種。 (9) 如（8)所述之甘油酯組成物的製造方法，其中 上述無機酸是選自由：硫酸、磷酸、硝酸、及鹽酸所組成 的群組中之至少一種。 (10) 如（5)〜（9)中任一項所述之甘油酯組成物 的製造方法，其中上述在酸性環境中之暴露，是在2〇。〇〜 260 C下進行。 (11 ) 一種甘油酯組成物，其係藉由如（i )〜（i 〇 ) 中任一項所述之製造方法而得到。 (12) —種甘油酯組成物，其特徵在於含有3質量％ 以上之二酸甘油酯，且含有以3_氣丙烷二酵換算量計 而合計含量小於lOppm之選自由：3_氣丙烷-12·二醇、3_ 氣丙炫· -1，2-二醇之脂肪酸酯、縮水甘油、及縮水甘油之脂 肪酸酯所組成的群組中之至少—種。 (13) —種食品’其中含有如（11)或（12)所述之 甘油酯組成物。 (14 ) 一種將甘油酯組成物中的縮水甘油之脂肪酸酯 201108943 及/或3-氣丙烷-l，2-二醇之脂肪酸酯降低或抑制其生成的 方法’其特徵在於以lOOt〜240°C的溫度條件對上述甘油 酶組成物進行脫臭處理，且上述甘油酯組成物含有：選自 由氯丙烧-1,2-二醇、3-氯丙燒-1,2-二醇之脂肪酸酯、縮 水甘油、及縮水甘油之脂肪酸酯所組成的群組中之至少一 種；及/或含有3質量％以上之二酸甘油酯。 (1 5 )如（1 4 )所述之將甘油酯組成物中的縮水甘油 之脂肪酸酯及/或3 -氯丙烧-1，2-二醇之脂肪酸酯降低或抑 制其生成的方法，其中將甘油酯組成物暴露在酸性環境 中，並以100。〇〜240°C的溫度條件進行脫臭處理，且上述 甘油醋組成物含有：選自由3_氣丙烷-12 —二醇、3·氣丙烷 -1，2-二醇之脂肪酸酯、縮水甘油、及縮水甘油之脂肪酸酯 所組成的群組中之至少一種；及/或含有3質量％以上之 二酸甘油醋》 [功效] 根據本發明’可以得到一種甘油酯組成物，其縮水甘 油之脂肪酸醋及/或3-氣丙烷_丨，2-二醇之脂肪酸酯較少。 【實施方式】 以下’詳細說明本發明的實施方式。另外，在本發明 中’甘油醋是在甘油上以酯鍵鍵結1〜3個脂肪酸而形成 的’除了油脂的主要成分亦即三酸甘油酯（三醯基甘油） 外’也包括二酸甘油酯（二醯基甘油）、單酸甘油酯（單酿 基甘油）。 201108943 本發明之甘油酯組成物的製造方法的特徵在於以 100 C 240 C的溫度條件對甘油醋組成物進行脫臭處理， 且上述甘油酯組成物含有：選自由3-氣丙烷_1，2_二醇（以 下稱為3-MCPD)、3-氯丙烷-i，2-二醇之脂肪酸酯（以下稱 為3-MCPD脂肪酸酯）、縮水甘油、及縮水甘油之脂肪酸酯 所組成的群組中之至少一種；及/或含有3質量％以上之 二酸甘油醋。亦即’在本發明之甘油酯組成物的製造方法 籲中’對下述任一項甘油酯組成物以100°C〜240°C的溫度條 件進行脫臭處理：（A)含有選自由3_MCPD、3-MCPD脂 肪酸酯、縮水甘油、及縮水甘油之脂肪酸酯所組成的群組 中之至少一種的甘油酯組成物；（B )含有3質量％以上之 二酸甘油酯的甘油酯組成物；或（C )含有選自由3_MCPt)、 3-MCPD脂肪酸酯、縮水甘油、及縮水甘油之脂肪酸酯所 組成的群組中之至少一種且含有3質量％以上之二酸甘油 酯的甘油酯組成物。如果上述脫臭處理前的甘油酯組成物 φ 是含有3質量％以上之二酸甘油酯者，則二酸甘油酯的含 量較佳為10〜98質量％，更佳為60〜93質量％。在此，甘 油醋組成物令的二酸甘油酯含量，例如可利用氣相色譜法 (AOCS Official Method Cd 1 lb-91 )測定。 並且’如果上述脫臭處理前的甘油酯組成物是含有選 自由3-MCPD、3-MCPD脂肪酸酯、縮水甘油、及縮水甘油 之脂肪酸酯所組成的群組中之至少一種，則利用後述方法 以3-MCPD換算量計，甘油酯組成物中的3_MCpD、3 MCpD 月曰肪酸酯、縮水甘油、及縮水甘油之脂肪酸酯的合計含量 201108943 以3 ppm以上為佳’較佳為i〇 ppm以上，更佳為1〇〜2〇〇 ppm，最佳為1 〇〜1 〇〇 ppm。此外，本發明的甘油酯組成物 的製造方法具有降低縮水甘油之脂肪酸酯和3_MCPD脂肪 酸酯的效果，因此’如果上述甘油酯組成物中含有縮水甘 油之脂肪酸酯及/或3-MCPD脂肪酸酯將更加有效。 並且’結構與縮水甘油之脂肪酸酯、3_MCPD脂肪酸 醋類似的縮水甘油及3-MCPD，雖然沒有包含在通常的食 用油脂中，但本發明之甘油酯組成物的製造方法也具有降 _ 低縮水甘油和3-MCPD的效果。201108943 VI. Description of the Invention: [Technical Fields of the Invention] The method for deteriorating a glyceride composition of a glyceride composition, and reducing the fatty acid S 缩 of glycidid in a glyceride composition And a method of the content of the fatty acid vinegar of 3-chloropropane m-diol, and a method of inhibiting the formation of fatty acid vinegar of glycidol or a fatty acid ester of 3-chloropropane-12. [Prior Art] In recent years, various attempts have been made to improve the flavor and stability of the oil. The reduction in the quality of the flavor and stability of the oil is related to various factors, and methods for responding to various factors have been reported. For example, Patent Document 1 discloses a method for suppressing the deterioration of odor of fats and oils for frying which is accompanied by the formation of a thermal oxidative decomposition product, and discloses a method for containing ascorbic acid or the like as an antioxidant in oils and fats. An organic acid such as an acid or a poorly soluble organic acid is added to a fat or oil in the form of an aqueous solution, and is subjected to dehydration treatment under high temperature and high decompression, and the antioxidant can be contained in a fat or oil, so that it is difficult to produce even if it is used for a long period of time. The heating deteriorates the odor. However, it is known that the structural chemical properties of the three-membered cyclic ether, i.e., epoxy oxime, are unstable and highly reactive, causing chemical reactions such as polymerization. In addition, the 3-chloropropanone of the bond (4) is also easy to react. In some of the glycerin-based sites, although a small amount of fatty acid is present in the epoxide of the epoxy W structure, that is, glycidol, it is likely to cause chemical changes such as aggregation. Moreover, the fatty acid ester of 3chloropropene 201108943 alkane-1'2-diol which can be derived from the fatty acid enzyme of glycidol is also likely to cause the same chemical reaction. Since fats which are deteriorated by polymerization or the like generate bubbles and unpleasant odors when fried, it is to be avoided as much as possible. However, the method of adding an antioxidant like the patent document cannot reduce the fatty acid ester of glycidol already existing in fats and oils or the fatty acid I of 3-chloropropane U•diol has not been reported in other methods for reducing fat. The development of a method for fatty acid esters of glycidol fatty acid esters <3·propane], 2·diol, has been expected. Patent Document 1: International Publication No. 01/096506 pamphlet. SUMMARY OF THE INVENTION [Problems to be Solved by the Invention] The present invention has been made in view of the above problems, and an object thereof is to provide a fatty acid ester of less glycidol and/or a fatty acid vinegar of 3·chloropropane_12_diol. The glycerin composition, the method for producing the glycerin composition, the method for reducing the content of the fatty acid vinegar of the glycidol in the φ glycerin composition and/or the fatty acid vinegar of the 3 gas propylene #diol, and the inhibition of the glycidol A method for producing fatty acid vinegar and/or 3-aeropropane-"2-diol fatty acid vinegar. [Technical means for solving the problem] The present inventors have repeatedly studied in order to solve the above problems, and as a result, it has been found that At least one of a group consisting of 2 -diol, 3 - diol, 3 - propyl propylene glycol glycerol, glycidol, and glycidol; and/or 3% by mass The above diglyceride _ glycerin vinegar composition 'deodorization treatment at a specific temperature, or into 201108943 one step exposure in an acidic environment 'or low temperature conditions lower than the usual temperature ding deodorization treatment' or within the specified range The heat treatment in the acid value can reduce the fatty acid ester of glycidol in the glyceride composition or the fatty acid ester of 3·g-propanol-丨2_diol, and can be expected to be lowered by the same method. The glycidol or 3-chloropropane-i,2-diol having the same functional group, thereby completing the β of the present invention, specifically provides the following. (1) A method for producing a glyceride composition, which is characterized The glyceride composition is deodorized at a temperature of 100 C to 240 ° C, and the glyceride composition contains: selected from the group consisting of 3-chloropropane_1,2-diol and 3-chloropropane-1. At least one of the group consisting of a fatty acid ester of a 2-diol, a glycidol, and a fatty acid ester of glycidol; and/or a glycerin ester of 3% by mass or more. (2) as (1) The method for producing a glyceride composition, wherein the glyceride composition contains a fatty acid ester of glycidol and/or a fatty acid ester of a propylene carbonate, 1,2, diol. (2) The method for producing a glycerin brewing composition, wherein the glyceride composition is a refined oil The method of producing a glyceride composition according to any one of (1) to (3), wherein the acid value of the glyceride composition is from 2 to 30, and before the deodorization treatment (5) The method for producing a glyceride composition according to any one of (1) to (4), which is before, after, and after deodorization treatment, The above-mentioned glyceride composition is exposed to an acidic environment. (6) The method for producing a glyceride composition according to any one of (1) to (the method of manufacturing a glyceride composition according to any one of the above), wherein the above glyceride is after the above-described deodorization treatment The composition is exposed to an acidic environment. (7) The method for producing a glyceride composition according to (5) or (6), wherein the exposure in the acid (four) environment, the glycerin s composition is contacted with the acid processing Auxiliary. (8) The method for producing a glyceride composition according to (7), wherein the acidic processing aid is at least one selected from the group consisting of activated clay, acidic activated carbon, and inorganic acid. (9) The method for producing a glyceride composition according to (8), wherein the inorganic acid is at least one selected from the group consisting of sulfuric acid, phosphoric acid, nitric acid, and hydrochloric acid. (10) The method for producing a glyceride composition according to any one of (5) to (9) wherein the exposure in an acidic environment is 2 Å. 〇 ~ 260 C under. (11) A glyceride composition obtained by the production method according to any one of (i) to (i). (12) A glyceride composition characterized by containing 3% by mass or more of diglyceride, and containing a total amount of less than 10 ppm in terms of 3-propane dipropanase, selected from: 3-propane-propane- At least one of the group consisting of a fatty acid ester of a diol, a gas fatty acid ester of a 1,2-diol, a glycidol, and a glycidol. (13) A food product comprising the glyceride composition as described in (11) or (12). (14) A method for reducing or inhibiting the formation of a fatty acid ester of glycidol of the glyceride composition 201108943 and/or a 3-aeropropan-1,2-diol fatty acid ester, which is characterized by being 100t~ The glycerin composition is subjected to deodorization treatment at a temperature of 240 ° C, and the glyceride composition contains: selected from the group consisting of chloropropane-1,2-diol, 3-chloropropan-1,2-diol At least one of the group consisting of fatty acid esters, glycidol, and fatty acid esters of glycidol; and/or containing 3% by mass or more of diglyceride. (1) reducing or inhibiting the formation of a fatty acid ester of glycidol and/or a fatty acid ester of 3-chloropropanol-1,2-diol in the glyceride composition as described in (1) A method wherein the glyceride composition is exposed to an acidic environment and is at 100. Deodorization treatment is carried out at a temperature of 〇240 ° C, and the glycerin vinegar composition contains: a fatty acid ester selected from the group consisting of 3-propane-12-diol, 3·a-propane-1,2-diol, and shrinkage At least one of a group consisting of glycerin and a fatty acid ester of glycidol; and/or containing 3% by mass or more of diglyceride; [Effect] According to the present invention, a glyceride composition can be obtained, which shrinks Fatty acid esters of glycerol fatty acid vinegar and/or 3-aeropropane 丨, 2-diol are less. [Embodiment] Hereinafter, embodiments of the present invention will be described in detail. Further, in the present invention, 'glycerin vinegar is formed by ester-bonding 1 to 3 fatty acids on glycerin, except for the main component of fats and oils, namely triglyceride (trimethyl glycerol), which also includes diacids. Glyceride (dimercaptoglycerol), monoglyceride (mono-branched glycerol). 201108943 The method for producing a glyceride composition of the present invention is characterized in that the glycerin composition is subjected to deodorization treatment under a temperature condition of 100 C 240 C, and the glyceride composition contains: selected from 3-a gas propane_1, 2 _diol (hereinafter referred to as 3-MCPD), fatty acid ester of 3-chloropropane-i,2-diol (hereinafter referred to as 3-MCPD fatty acid ester), glycidol, and fatty acid ester of glycidol At least one of the group consisting of; and/or containing 3% by mass or more of diglyceride. That is, 'in the manufacturing method of the glyceride composition of the present invention', the deodorization treatment is carried out on any one of the following glyceride compositions at a temperature of from 100 ° C to 240 ° C: (A) contains a selected from 3 - MCPD a glyceride composition of at least one of the group consisting of 3-MCPD fatty acid ester, glycidol, and glycidol fatty acid ester; (B) a glyceride composition containing 3% by mass or more of diglyceride Or (C) containing at least one selected from the group consisting of 3-MCPt), 3-MCPD fatty acid ester, glycidol, and glycidol fatty acid ester, and containing 3% by mass or more of diglyceride Glyceride composition. When the glyceride composition φ before the deodorization treatment is glycerin containing 3% by mass or more, the content of the diglyceride is preferably from 10 to 98% by mass, more preferably from 60 to 93% by mass. Here, the diglyceride content of the glycerin vinegar composition can be measured, for example, by gas chromatography (AOCS Official Method Cd 1 lb-91). And 'if the glyceride composition before the deodorization treatment is at least one selected from the group consisting of fatty acid esters of 3-MCPD, 3-MCPD fatty acid ester, glycidol, and glycidol, use In the following method, the total content of 3_MCpD, 3 MCpD lauric acid ester, glycidol, and glycidol fatty acid ester in the glyceride composition is preferably 3 ppm or more in terms of 3-MCPD. More than i 〇 ppm, more preferably 1 〇 ~ 2 〇〇 ppm, and most preferably 1 〇 ~ 1 〇〇 ppm. Further, the method for producing a glyceride composition of the present invention has an effect of lowering the fatty acid ester of glycidol and the 3-MCPD fatty acid ester, and therefore 'if the above glyceride composition contains glycidyl ester fatty acid ester and/or 3-MCPD Fatty acid esters will be more effective. And the structure is similar to glycidol fatty acid ester, 3_MCPD fatty acid vinegar-like glycidol and 3-MCPD, although it is not included in the usual edible fats and oils, the method for producing the glyceride composition of the present invention also has a decrease _ low shrinkage The effect of glycerol and 3-MCPD.
在本發明中，作為縮水甘油、縮水甘油之脂肪酸酯、 3-MCPD、及3-MCPD脂肪酸酯的含量測定方法，使用了將 上述物質測定為3-MCPD換算量的德國官方法（DGFIn the present invention, as a method for measuring the content of glycidol, glycidyl fatty acid ester, 3-MCPD, and 3-MCPD fatty acid ester, a German official method (DGF) for measuring the above-mentioned substance to a 3-MCPD conversion amount is used.
Standard Methods C-III 18(09))。 具體而言’是採集油脂樣品並添加内標物，而後在其 中加入曱醇鈉的曱醇溶液’使其在室溫下反應，進行酯的 φ 皂化分解。然後，於其中加入並混合.含微量醋酸的食鹽水 和己烷後，再除去己烷。此時，3_mc：Pd、3-MCPD脂肪酸 醋、縮水甘油、縮水甘油之脂肪酸酯全部被轉換為 3-MCPD »之後’用苯硼酸將其衍生化（derivatizati〇n)，用 己烷提取，使用氣相色譜質譜裝置測定。接著，使用氣相 色譜質譜裝置測定得到的色譜圖，來比較内標和3_MCPd 的離子強度，即可藉游離3_M(：pd換算而算出油脂中的縮 水甘油、縮水甘油之脂肪酸酯、3_MCpd、3-MCPD脂肪酸 酯的總量。 201108943 這樣’在上述德國官方法測定樣品的製備方法中， 3-MCPD、3-MCPD脂肪酸酯、縮水甘油、縮水甘油之脂肪 酸酯全部被轉換為3-MCPD。因此，利用德國官方法測出 的值就成了 3-MCPD、3-MCPD脂肪酸酯、縮水甘油、縮水 甘油之脂肪酸酯的合計含量之3-MCPD換算值。另外，因 被測定物是植物油等甘油酯組成物，故可推論上述用德國 官方法測定的物質是縮水甘油之脂肪酸酯及3_McpD脂肪 本發明之甘油酯組成物的製造方法的特徵在於將上述 (1 )〜（3 )中任一項的甘油酯组成物以比通常的油脂製 ie方法所使用之脫臭溫度24〇°c〜260°C低的l〇〇°c〜240°C 的溫度條件進行脫臭處理，溫度以1〇(rc〜 235<>c為佳較 佳為160。(：〜225。〇，最佳為2〇〇ec〜2irc。另外從製造 風味也良好的甘油酯組成物的方面而言，本發明之甘油酯 組成物的製造方法較佳為經24(rc〜26〇〇c的水蒸氣蒸餾處 理（通常的脫臭處理）後’再次以⑽°C〜24Gt的溫度條 件進行脫臭處理。對脫臭溫度以外的條件沒有特別限制， 以減壓或注入水蒸氣為佳，較佳為在減壓下注入水蒸氣。 而且’脫臭時間以15〜150分鐘為佳，較佳為40〜1〇〇分 鐘0 在本發明之甘油酯組成物 組成物也可以使用精製油。藉 更佳的甘油酯組成物。對於精 法精製的菜籽油、大豆油、米 的製造方法中，上述甘油酯 由使用精製油，可製造風味 製油，例如可使用按常規方 油、紅花油、葡萄籽油、葵 [S] 10 201108943 花油、小麥胚芽油、玉芈 水油、棉籽油、芝麻油、花生油、 亞麻油、紫蘇油、撖禮油、始 視由掠櫚油和椰子油等植物油，·將 上述植物油兩種以上溫人而+ 上，昆》而成的調和植物油；或由上述植 物油分提出來的棕櫚液油、柠 标调硬脂、棕櫚超級液油和棕 摘中間餾出物等分提食用油· 用^由，上述植物油的氫化油和酯交 、等w及中鏈月曰肪酸二酸甘油酯這種直接由酯化反應 製造出來的食用油。植物油的精製方法有化學精製 (chemicai refining)和物理精製（ρΐ^^ι refin峋广使 用其中任何一種精製方法都可以。另夕卜，前者的化學精製 在植物油的精製中是通常採用的方法，從原料植物中壓 梓、提取後的原油經過脫膠處理、脫酸處理、脫色處理、 脫蠟處理和脫臭處理等而被精製，成為精製油。相對於此， 後者的物理精製是在棕櫚油和椰子油等的精製上經常使用 的方法，從原料棕櫚和椰子等壓榨的原油經過脫膠處理、 脫色處理、脫酸、脫臭處理而被精製，成為精製油。 在本發明之甘油酯組成物的製造方法中，較佳為在將 酸值為2〜30的上述甘油酯組成物進行上述脫臭處理前進 行加熱處理。酸值為2〜30的上述甘油酯組成物可使用原 本酸值就高的甘油酯組成物和加酸調整酸值後的甘油醋組 成物’較佳為使用酸值為2〜15的上述甘油酯組成物。另 外，在調整酸值時使用的酸，以游離脂肪酸為佳。這裡所 謂的游離脂肪酸，是指游離脂肪酸及其鹽。對於游離脂肪 酸沒有特別限制’但是’以碳數12〜22的脂肪酸為佳，例 如可以列舉棕櫚酸、油酸、亞麻油酸、硬脂酸和次亞麻油 201108943 酸等。 加熱處理時的溫度以100〜26(rc為佳，較佳為16〇〜 245。(：，更佳為200〜225。(：。在本發明之甘油醋組成物的製 造方法中，所謂加熱處理，只要進行加熱即可，並無其他 特別的限制，但具體而言，可列舉出：單純加熱減壓下 加熱、邊注入水蒸氣邊加熱以及在減壓下邊注入水蒸氣邊 加熱等加熱方法。對於溫度以外的條件並無特別限制但 以減壓或注入水蒸氣為佳，較佳為減壓下注入水蒸氣。並 且，對於加熱處理的時間並無特別限制，但較佳為4〇〜丨⑽ 分鐘。 在本發明之甘油酯組成物的製造方法中，也可以在上 述脫臭處理前或者上述脫臭處理後，將上述甘油醋組成物 暴露在酸性環境中。從風味方面而言，以在脫臭處理前暴 露在酸性環境中為佳，而如果在脫臭處理後暴露在酸性環 境中，貝降低縮水甘油之脂肪酸酉旨、3_氯二醇上 •效果高。在本發明之甘油酯組成物的製造方法中，對於將 上述甘油醋組成物暴露在酸性環境的方法並無特別限制， 例如可列舉使上述甘油醋組成物接觸酸性加工助劑的方 法、和在上述甘油酯組成物中加入碳數為1〜22的有機酸 的方法等，也可並用上述方法的二種以上。 並且，在酸性環境中之暴露，以在2〇〜26〇。〇下進行為 佳’如果是使其接觸酸性加工助劑的方法，則較佳為在 〜20CTC進行，最佳為在⑽〜18『c。並且如果採用加入 碳數為1〜22的有機酸的方法，則較佳為在100〜26〇t進 12 201108943 行’最佳在180〜260°C進行β 在使上述甘油酷組成物接觸酸性加工助劑的方法 對於酸性加工助劑並無特別限制，例如可列舉：的 加工助劑、水溶液呈酸性 、 的加工助劑、内含酸性氣體的如Standard Methods C-III 18(09)). Specifically, the oil sample is collected and an internal standard is added, and then a decyl alcohol solution of sodium decoxide is added thereto to cause it to react at room temperature to carry out saponification decomposition of the ester. Then, after adding and mixing the brine containing a small amount of acetic acid and hexane, the hexane was removed. At this time, the fatty acid esters of 3_mc:Pd, 3-MCPD fatty acid vinegar, glycidol, and glycidol were all converted to 3-MCPD » and then derivatized with phenylboronic acid (derivatizati〇n), extracted with hexane, It was measured using a gas chromatography mass spectrometer. Next, the chromatogram obtained by gas chromatography mass spectrometry was used to compare the internal standard and the ionic strength of 3_MCPd, and the glycidol, the fatty acid ester of glycidol, and the 3_MCpd in the fat and oil were calculated by the free 3_M (:pd conversion). The total amount of 3-MCPD fatty acid ester. 201108943 Thus, in the preparation method of the above-mentioned German official method determination sample, the fatty acid esters of 3-MCPD, 3-MCPD fatty acid ester, glycidol and glycidol are all converted into 3 -MCPD. Therefore, the value measured by the German official method is a 3-MCPD conversion value of the total content of 3-MCPD, 3-MCPD fatty acid ester, glycidol, and glycidol fatty acid ester. The measurement product is a glyceride composition such as vegetable oil. Therefore, it can be inferred that the above-mentioned method of producing a glycidyl ester of glycidol and 3_McpD fat by the German official method is characterized in that the above (1) is The glyceride composition of any one of (3) is removed at a temperature lower than a deodorizing temperature of 24 ° C to 260 ° C used in a conventional oil-and-fat method. Stinky treatment, The degree is preferably 1 〇 (rc 〜 235 <> c is preferably 160. (: 225 to 225. 〇, preferably 2 〇〇 ec to 2 irc. In addition, from the aspect of producing a glyceride composition having a good flavor. In other words, the method for producing a glyceride composition of the present invention is preferably subjected to a steam distillation treatment (normal deodorization treatment) of 24 (rc to 26 〇〇c) and then again subjected to a temperature condition of (10) ° C to 24 Gt. The odor treatment is not particularly limited, and it is preferably a reduced pressure or a water vapor, and it is preferred to inject water vapor under reduced pressure. Further, the 'deodorization time is preferably 15 to 150 minutes, preferably. 40 to 1 〇〇 min 0 In the glyceride composition of the present invention, a refined oil may be used, and a better glyceride composition may be used. In the method for producing refined rapeseed oil, soybean oil, and rice, The above glyceride can be used to produce a flavored oil by using a refined oil. For example, conventional oil, safflower oil, grape seed oil, sunflower oil [S] 10 201108943 flower oil, wheat germ oil, maize water oil, cottonseed oil, Sesame oil, peanut oil, linseed oil, perilla oil, eucalyptus oil At the beginning, it is a vegetable oil made from palm oil and coconut oil, a blended vegetable oil obtained by adding two or more kinds of the above vegetable oils to the Kunming, or a palm oil and a lemon fat blended by the above vegetable oil. , palm super liquid oil and brown extract middle distillate, etc., and the edible oil is used. The hydrogenated oil and ester cross of the above vegetable oil, etc., and the medium chain glutamic acid diglyceride are directly esterified. The edible oil produced by the reaction. The method for purifying the vegetable oil may be chemical refining (chemicai refining) or physical refining (pΐ^^ι refin峋), any of which may be used. In addition, the chemical purification of the former is a commonly used method in the purification of vegetable oil, and the crude oil after being crushed and extracted from the raw material plant is subjected to degumming treatment, deacidification treatment, decolorization treatment, dewaxing treatment, deodorization treatment, and the like. It is refined to become a refined oil. On the other hand, the physical refining of the latter is a method which is often used for the refining of palm oil, coconut oil, etc., and the crude oil crushed from raw materials palm and coconut is refined by degumming treatment, decolorization treatment, deacidification, and deodorization treatment. Become a refined oil. In the method for producing a glyceride composition of the present invention, it is preferred that the glyceride composition having an acid value of from 2 to 30 is subjected to the above-described deodorization treatment for heat treatment. The glyceride composition having an acid value of 2 to 30 can be a glyceride composition having a high acid value and a glycerin composition having an acid value adjusted by adding acid. Preferably, the above glycerin having an acid value of 2 to 15 is used. Ester composition. Further, the acid used in adjusting the acid value is preferably a free fatty acid. The term "free fatty acid" as used herein refers to free fatty acids and salts thereof. The free fatty acid is not particularly limited 'but' is preferably a fatty acid having 12 to 22 carbon atoms, and examples thereof include palmitic acid, oleic acid, linoleic acid, stearic acid, and linseed oil 201108943 acid. The temperature at the time of heat treatment is preferably 100 to 26 (rc is preferably 16 〇 to 245. (:, more preferably 200 to 225.): In the method for producing a glycerin composition of the present invention, heating is called The treatment is not particularly limited as long as it is heated, and specific examples thereof include heating by heating under reduced pressure, heating while injecting steam, and heating by injecting steam under reduced pressure. The conditions other than the temperature are not particularly limited, but it is preferably reduced pressure or water vapor, and it is preferred to inject water vapor under reduced pressure. Further, the heat treatment time is not particularly limited, but is preferably 4 〇 In the method for producing a glyceride composition of the present invention, the glycerin composition may be exposed to an acidic environment before the deodorization treatment or after the deodorization treatment. It is preferable to be exposed to an acidic environment before the deodorization treatment, and if it is exposed to an acidic environment after the deodorization treatment, the effect of reducing the fatty acid of the glycidol and the effect of the 3-chloro diol is high. In the method for producing a glyceride composition, the method of exposing the glycerin composition to an acidic environment is not particularly limited, and examples thereof include a method of bringing the glycerin composition into contact with an acidic processing aid, and a glyceride. A method of adding an organic acid having a carbon number of 1 to 22 to the composition may be used in combination of two or more of the above methods. Further, exposure in an acidic environment is preferably carried out at 2 to 26 Torr. If it is a method of bringing it into contact with an acidic processing aid, it is preferably carried out at -20 CTC, preferably at (10) to 18 c. And if a method of adding an organic acid having a carbon number of 1 to 22 is used, it is preferably. In order to carry out β at the temperature of 180 to 260 ° C at 100 to 26 〇t into 12 201108943, the method of contacting the above-mentioned glycerin cool composition with an acidic processing aid is not particularly limited, and examples thereof include, for example, Processing aid, aqueous solution is acidic, processing aid, acid gas containing
工助劑和酸殘留的加工助劑等。具體而言可列舉白土 活性炭、梦膠、離子交換樹脂、助濾劑、沸石'纖維、催 化劑、酶、將上述助劑進行酸處理者以及無機酸等，這此 :劑既可單獨使用也可合用。本發明中所謂的白土是指： 蒙脫石為主的黏土。對白土並無特別限制，包括了下述任 何種.酸性白土、或被施以活性化處理的酸性白土:即 活性白土。本發明中所謂的活性炭原料可使用例如：焦炭、 人造石墨、木炭、骨炭 '玻璃碳、碳纖維、炭黑和絲綢等。 特別以木材、種皮、榖物殘渣、樹皮和椰子柄等來自植物 的活性炭原料為佳’最料木材。並且，活性炭原料的活 化方法已知有水蒸氣活化、氣體活化和化學活化等多種方 法，用其中任何一種活化法活化的原料都適於使用。上述 活化法中，又以化學活化為佳。在化學活化法中，更佳為 用氣化鋅、磷酸和氣化鈣等活化，最佳為用磷酸活化。並 且’即使是鹼活化的活性炭原料’若之後經處理而呈酸性 者也適於使用。本發明中所謂的助濾劑可使用矽藻土、纖 維素和波來鐵（pearlite)等《纖維可使用化學纖維、植物纖 維和動物纖維等》在這些加工助劑中，本發明的酸性加工 助劑是以酸性白土或酸性活性炭為佳，較佳為合用酸性白 土和酸性活性炭。加工助劑的添加量並無特別限制，如果 [S] 13 201108943 是無機酸以外的加工助劑’則以相對於甘油醋組成物為 〇.01〜1〇質量％為佳，更佳為1〜7質量❶/”無機酸以外的 加工助劑一般是固體，以接觸後過濾去除為佳。 在使用無機酸作為酸性加工助劑的方法中，對 的種類並無特別限制，例如可列舉··硫酸、碟酸、硝酸和 鹽酸等’可將上述酸單獨使用或混合使用。在上述益機酸 中’硫酸、碟酸、確酸及鹽酸從容易取得的觀點而言係為 較佳。並且’較佳為對於上述甘油醋組成物添加無機酸來 使用’因添加量少，所以從控制添加量方面而言較佳為 將無機酸以水溶液來添加。上述對於甘油i组成物之無機 酸水溶液之添加，以在剛剛完成脱臭處理後且上述甘油於 組成物的溫度it HKTC：以上時進行為佳，較佳為在⑽二 2〇〇t：。無機酸的添加量並無特別限制，相對於甘油醋组成 物以0.001〜0.7質量％為佳，更佳為〇〇〇ι〜〇〇5質量。4。 將無機酸添加並接觸之後，以藉水料去除無機酸為佳。 在上述甘油酯組成物中添加碳數為1〜22之有機酸的 方法中，對有機酸並無特別限制，例如可列舉檸檬酸、醋 酸、蘋果酸、月桂酸、肖豆蔻酸、棕櫚酸、硬脂酸二^ 二酸 '油酸、亞麻油酸和次亞麻油酸等，可將上述酸單獨 或混合使用》在上述酸中，從在油脂中溶解性良好的方面 而言，以下述為佳：月桂酸、肉豆蔻酸、栋櫚酸、硬脂酸、 二十二酸、油酸、亞麻油酸和次亞麻油酸等脂肪酸。並且， 從提高分散性的方面而言，較佳為以水溶液的狀態添加檸 樣駿和蘋果酸等結晶形式的水溶性有機酸。上述對於甘油 201108943Processing aids and processing aids for acid residues. Specific examples thereof include white clay activated carbon, dream gel, ion exchange resin, filter aid, zeolite fiber, catalyst, enzyme, acid treatment of the above-mentioned auxiliary agent, and inorganic acid, etc., and the agent can be used alone or in combination. Use together. The so-called white clay in the present invention means: a smectite-based clay. There is no particular limitation on the white clay, including any of the following: acid clay, or acid white clay to be activated; that is, activated clay. As the activated carbon raw material in the present invention, for example, coke, artificial graphite, charcoal, bone charcoal, glassy carbon, carbon fiber, carbon black, silk, or the like can be used. In particular, wood-based activated carbon raw materials such as wood, seed coat, scum residue, bark and coconut stalks are preferred. Further, various methods of activating the activated carbon raw material are known as steam activation, gas activation, and chemical activation, and a raw material activated by any of the activation methods is suitable for use. Among the above activation methods, chemical activation is preferred. In the chemical activation method, it is more preferably activated by using zinc sulfide, phosphoric acid, calcium carbonate or the like, and it is preferably activated by phosphoric acid. Further, even if the alkali-activated activated carbon raw material is acidic after being treated, it is suitable for use. The so-called filter aid in the present invention may be used in the processing aids such as diatomaceous earth, cellulose, and pearlite, such as chemical fibers, plant fibers, and animal fibers, and the acid processing of the present invention. The auxiliary agent is preferably acid white clay or acidic activated carbon, and preferably acid white clay and acidic activated carbon are used in combination. The amount of the processing aid to be added is not particularly limited. If [S] 13 201108943 is a processing aid other than the inorganic acid, it is preferably 〇.01 〜1 〇 mass%, more preferably 1 glycerol vinegar composition. The processing aid other than the inorganic acid is generally a solid, and it is preferably removed by filtration after contact. In the method of using an inorganic acid as an acidic processing aid, the kind to be used is not particularly limited, and for example, Sulfuric acid, dish acid, nitric acid, hydrochloric acid, etc. The above-mentioned acids may be used singly or in combination. Among the above-mentioned probiotic acids, 'sulfuric acid, acid acid, acid and hydrochloric acid are preferred from the viewpoint of easy availability. It is preferable to use a mineral acid in the above-mentioned glycerin vinegar composition, and it is preferable to add a mineral acid as an aqueous solution from the control addition amount. The above-mentioned inorganic acid aqueous solution for the glycerol i composition is preferable. The addition is preferably carried out immediately after the completion of the deodorization treatment and the glycerin is at a temperature of the composition IT HKTC: or higher, preferably at (10) 2 〇〇t: The amount of the inorganic acid added is not particularly limited. The glycerin vinegar composition is preferably 0.001 to 0.7% by mass, more preferably 〇〇〇ι to 〇〇5 by mass. 4. After the inorganic acid is added and contacted, it is preferred to remove the inorganic acid by the water. In the method of adding an organic acid having a carbon number of 1 to 22 to the ester composition, the organic acid is not particularly limited, and examples thereof include citric acid, acetic acid, malic acid, lauric acid, crotonic acid, palmitic acid, and stearic acid. Dioctanoic acid 'oleic acid', linoleic acid and linoleic acid, etc., may be used alone or in combination. In the above-mentioned acid, from the viewpoint of good solubility in fats and oils, the following is preferred: laurel Fatty acids such as acid, myristic acid, chloric acid, stearic acid, octanoic acid, oleic acid, linoleic acid, and linoleic acid. Further, from the viewpoint of improving dispersibility, it is preferably an aqueous solution. Add a water-soluble organic acid in the form of a crystal such as C. chinensis and malic acid. The above for glycerol 201108943
Sa組成物之有機酸水溶液之添加，以在脫臭處理剛結束後 進行為佳。上述甘油酯組成物的溫度以在i 〇〇它以上為佳， 較佳為100〜260 C ’最佳為18〇〜26〇〇c。有機酸添加量並 無特別限制，以相對於甘油酶組成物而在1〇ppm〜2〇質量 %之範圍内為佳，較佳為添加至甘油g|組成物的酸值達2 〜30。並且，在暴露於酸性環境後，對碳數為ι〜4的有機 酸以採用過遽3戈水洗除去為佳，對碳數為5以上的有機酸 以採用蒸餾等手段除去為佳。The addition of the organic acid aqueous solution of the Sa composition is preferably carried out immediately after the deodorization treatment. The temperature of the above glyceride composition is preferably at most io, preferably from 100 to 260 C', preferably from 18 〇 to 26 〇〇c. The amount of the organic acid to be added is not particularly limited, and is preferably in the range of 1 〇 ppm to 2 〇 by mass based on the glycerin composition, and preferably the acid value added to the glycerin g| composition is 2 to 30. Further, after exposure to an acidic environment, it is preferred to remove the organic acid having a carbon number of 1 to 4 by using 3 liters of water, and to remove the organic acid having 5 or more carbon atoms by distillation or the like.
本發明之甘油酯組成物的特徵在於是藉由上述本發明 之甘油醋組成物的製造方法而得到。利用本發明之甘油醋 組成物，則可降低縮水甘油之脂肪酸醋、3 McpD脂肪酸 醋、縮水甘油、3-MCPD’或可抑制縮水甘油之脂肪酸醋及 3_MCPD脂肪酸醋…，所以，可期待所得到的甘油醋 組成物在油炸時不易產生泡沫且風味不易變差。 本發明之甘油醋組成物的特徵在於：含有3質量％以 上的二酸甘油自旨，且以3傭PD換算量計選自由 3-MCPD、3-MCPD脂肪_、縮水甘油及縮水甘油之脂肪 酸輯所組成的群財之至少—種的合計含量小於 本發明之甘油醋組成物儘管含、 PPm。 耳3有 疋1以上的二酸 S曰’但因縮水甘油及縮水甘油之脂肪酸酯較少所 待在油科不易產生料且風味不易變差。 油醋的含量以6〇〜98質量％為佳，且 一酸甘 計，選自肪酸 水甘油之脂肪酸酿所組成的群組 ’、及縮 夕—種的合計含量 S] 15 201108943 以小於3 ppm為佳。 本發明之食品的特徵在於包含上述本發明之甘油醋組 成物。根據本發明之食品，因為㈣原料之甘油醋組成物 中的縮水甘油之脂錢g旨和3_McpD脂肪酸⑽少，所以 可期待在油炸時不易產生料且風味不易變差。作為食 品’所有可含有油脂的食品都可能成為對象。例如調味油、 蛋黃醬、巧克力、調味汁、人造奶油、食用塗脂伽啊⑷ 和奶油等。 本發明的#法是將甘油醋組成#中縮纟甘油之脂肪酸 酯及/或3-MCPD脂肪酸酯的含量降低或抑制其生成的方 法。該方法是藉由對甘油酯組成物以1〇〇〜24〇£)(：的溫度條 件進行脫臭處理，從而將甘油酯組成物中的縮水甘油之脂 肪酸酯及/或3-MCPD之脂肪酸酯的含量降低或是抑制其 生成，其中上述甘油酯組成物含有：選自由3_McpD、 3-MCPD脂肪酸醋、縮水甘油、及縮水甘油之脂肪酸酯所 組成的群組中之至少一種；及/或含有3質量％以上之二 酸甘油酯的甘油酯組成物。脫臭處理的條件與上述甘油酯 組成物的製造方法相同。另外，藉由將上述甘油酯組成物 暴露在酸性環境中，並進一步以100〜24〇t的溫度條件進 行脫臭處理，可將甘油酯組成物中縮水甘油之脂肪酸酯及 /或3-MCPD脂肪酸酯進一步降低或抑制其生成。 [實施例] 以下’基於本發明的實施例而更詳細地說明，但本發 [S] 16 201108943 明不受這些記載的任何限制。 對降低甘油酯組成物中所含有的3-MCPD、3-MCPD脂 肪酸醋、縮水甘油、及縮水甘油之脂肪酸酯的可能性進行 了探討。 <酸性環境下之暴露條件的研究> [原料甘油酯組成物1] 在1600 g之利用常規方法精製的大豆及菜籽混合精製 油（大豆脫色油和菜籽脫色油的混合油）中添加〇 256 g 縮水甘油之脂肪酸酯（縮水甘油硬脂酸酯，東京化成工業 株式會社製）和0.192 g之3-MCPD脂肪酸酯（丨_硬脂醯基 -3-氣丙二醇，和光純藥工業株式會社製），混合後得到原 料甘油酯組成物1 (以3_MCPD換算量計為85 35 ppm)。 [比較例1] 將原料甘油酯組成物1在減壓下以u〇〇c檀掉2〇分 鐘’得到比較例1的甘油酯組成物。 [實施例1] 在原料甘油醋組成物1中添加相對於該原料甘油酿組 成物1的量的5質量％的活性炭（磷酸活化活性炭：cai， 曰本NORIT株式會社製），在減壓下u〇t攪拌2〇分鐘後， 過濾去除活性炭，得到實施例1的甘油酯組成物。 [實施例2] 除了用5質量％的活性白土（硫酸處理白土·水澤化 學工業株式會社製）來代替5質量％的活性炭以外，用與 實施例1同樣的方法得到實施例2的甘油酯組成物。 m 17 201108943The glyceride composition of the present invention is obtained by the above-described method for producing a glycerin composition of the present invention. By using the glycerin vinegar composition of the present invention, fatty acid vinegar of glycidol, 3 McpD fatty acid vinegar, glycidol, 3-MCPD' or fatty acid vinegar capable of inhibiting glycidol and 3_MCPD fatty acid vinegar can be reduced, so that it can be expected The glycerin vinegar composition is less prone to foaming when fried and the flavor is not easily deteriorated. The glycerin vinegar composition of the present invention is characterized in that it contains 3% by mass or more of diglyceride, and is selected from the group consisting of 3-MCPD, 3-MCPD fat _, glycidol and glycidol. At least the total amount of the group consisting of the group consists less than the glycerin composition of the present invention, although it contains PPm. Ear 3 has more than 1 diacid S曰' but the fatty acid esters of glycidol and glycidol are less likely to be produced in the oil family and the flavor is not easily deteriorated. The content of the oil vinegar is preferably from 6 〇 to 98% by mass, and the monosaccharide is selected from the group consisting of fatty acid glycerin fatty acid brewing, and the total content of the scorpion species S] 15 201108943 3 ppm is preferred. The food of the present invention is characterized by comprising the above-described glycerin composition of the present invention. According to the food of the present invention, since the amount of glycidol in the glycerin vinegar composition of the (four) raw material is less than that of the 3_McpD fatty acid (10), it is expected that the material is less likely to be produced during frying and the flavor is not easily deteriorated. As a food, all foods that contain oils and fats may be the target. For example, seasoning oil, mayonnaise, chocolate, sauce, margarine, edible gluten (4) and cream. The # method of the present invention is a method for reducing or inhibiting the formation of a fatty acid ester of glycerol vinegar composition # and a 3-MCPD fatty acid ester. The method is characterized in that the glyceride composition is subjected to a deodorization treatment at a temperature of 1 Torr to 24 Å to thereby form a fatty acid ester of glycidol and/or 3-MCPD in the glyceride composition. Decreasing or inhibiting the formation of a fatty acid ester comprising: at least one selected from the group consisting of 3_McpD, 3-MCPD fatty acid vinegar, glycidol, and glycidol fatty acid ester; And/or a glyceride composition containing 3% by mass or more of diglyceride. The conditions of the deodorization treatment are the same as those of the above-described glyceride composition. Further, by exposing the above glyceride composition to an acidic environment Further, the deodorization treatment is carried out under the temperature conditions of 100 to 24 Torr, and the fatty acid ester of glycidol and/or the 3-MCPD fatty acid ester in the glyceride composition can be further reduced or suppressed from being formed. The following 'is explained in more detail based on the examples of the present invention, but the present invention [S] 16 201108943 is not subject to any limitation of these descriptions. The 3-MCPD, 3-MCPD fatty acid vinegar contained in the glyceride composition is lowered. The possibility of glycidyl esters and glycidyl esters of glycidol is discussed. <Study on exposure conditions in an acidic environment> [Raw glyceride composition 1] 1600 g of soybeans and rapeseed refined by a conventional method混合 256 g of glycidol fatty acid ester (glycidyl stearate, manufactured by Tokyo Chemical Industry Co., Ltd.) and 0.192 g of 3-MCPD fat were added to the blended refined oil (mixed oil of soybean decolorizing oil and rapeseed decolorizing oil). The acid ester (丨_stearyltrifluoro-3-propanediol, manufactured by Wako Pure Chemical Industries, Ltd.) was mixed to obtain a raw material glyceride composition 1 (85 35 ppm in terms of 3_MCPD). [Comparative Example 1] The glyceride composition of Comparative Example 1 was obtained by dropping the raw material glyceride composition 1 under reduced pressure for 2 minutes to obtain the glyceride composition of Comparative Example 1. [Example 1] The raw material glycerin vinegar composition 1 was added with respect to the raw material. 5% by mass of activated carbon (phosphoric acid activated carbon: cai, manufactured by NO本 NORIT Co., Ltd.) in an amount of glycerin brewing composition 1 was stirred under reduced pressure for 2 minutes, and then activated carbon was removed by filtration to obtain Example 1 Glyceride composition. Example 2] A glyceride composition of Example 2 was obtained in the same manner as in Example 1 except that 5% by mass of activated clay (manufactured by Sesame Sulfate Co., Ltd.) was used instead of 5% by mass of activated carbon. m 17 201108943
[實施例3J 在原料甘油酯組成物丨中 成物1之f A s &旦 、相對於該原料甘油酯組 成物 重為5質量％的活性白土 r 仆璺工紫嫉‘ （硫^處理白土 ：水澤 化學工業株式會社製），在減 八鐘德，堝谕土 $下从常溫（28。〇攪拌20 刀鐘後過'慮去除活性白土，得5，丨寄& y t， 物。 得到實施例3的甘油酯組成 [原料甘油酯组成物2] 將原料甘油酯組成物1和大 八足貺色油以重量比83 :】7 混合，付到原料甘油酷相& & 1 ,[Example 3J In the raw material glyceride composition 丨1, f A s & denier, 5% by weight relative to the raw material glyceride composition, active white clay r servant 嫉 嫉 ( ( White clay: Made by Mizusawa Chemical Industry Co., Ltd., in the reduction of eight clocks, the earth is under normal temperature (28. After stirring for 20 knives, it is considered to remove the activated clay, and 5, 丨 send & yt, material. The glyceride composition of Example 3 was obtained [raw material glyceride composition 2] The raw material glyceride composition 1 and the big octagonal ochre oil were mixed at a weight ratio of 83:], and were added to the raw material glycerin phase && 1 ,
付甘油S日組成物2 (以3_McpD 14.30 ppm)。 里。卞為 [實施例4] 在原料甘油醋組成物2中添加相對於該原料甘油妒組 成物2之量為5 f量％的活性炭（碟酸活化活性炭：以日卜 日本NORIT株式會社製)，減壓下以11〇。。攪拌2〇分鐘後， 過濾去除活性炭，得到實施例4的甘油酯組成物。 [實施例5] 除了用5質量％的活性白土（硫酸處理白土：水澤化 學工業株式會社製）來代替5質量％的活性炭以外，用與 實施例4同樣的方法得到實施例5的甘油酯組成物。 [原料甘油酯組成物3] 將原料甘油酯組成物1和大豆脫色油以重量比86 : 14 混合’得到原料甘油酯組成物3 (以3_MCPD換算量計為 11 _65 ppm )。 [實施例6] 201108943 在原料甘油酯組成物3中添加相對於該原料甘油醋组 成物3之量為5質量％的活性炭（磷酸活化活性炭：CAi， 曰本NORIT株式會杜製），減壓下以11〇〇c攪拌2〇分鐘後， 過濾去除活性炭’得到實施例6的甘油酯組成物。 [實施例7] 除了用5質量。/〇的活性白土（硫酸處理白土：水澤化 學工業株式會社製）來代替5質量％的活性炭以外，用與 實施例6同樣的方法得到實施例7的甘油酯組成物。 (定量法） 甘油醋組成物中的3 — MCPD、3-MCPD脂肪酸醋、縮水 甘油、及縮水甘油之脂肪酸酯的定量，是根據德國官方法 (DGF Standard Methods C-III 18(09))進行。在該方法中， 由於在製備測定樣品時縮水甘油之脂肪酸酯及3 — MCPD脂 肪酸酯轉換為3-MCPD，所以3-MCPD、3-MCPD脂肪酸醋、 縮水甘油、及縮水甘油之脂肪酸酯，是全部作為游離 3-MCPD來測定》 在100 mg之原料甘油酯組成物1〜3、實施例i〜7以 及比較例1的樣品中加入50μί的内標物（3-MCPD-d5 20pg/mL溶液）後’在其中加入1 mL的甲醇鈉溶液（0.5 mol/L甲醇）’使其在室溫下反應，進行酯的皂化分解。隨 後’加入3 mL之含微量醋酸的食鹽水（2〇〇/0)和3 mL己 烷並混合之後’去除己烷。此時，縮水甘油轉換為3-MCPD， 縮水甘油之脂肪酸酯在酯鍵斷開的同時轉換為3-MCPD » 然後’利用250μί的苯硼酸水溶液（25%)進行衍生化， m 19 201108943 用2 mL己烷提取，用氣相色譜質譜裝置測定。 利用上述氣相色譜質譜裝置之測定所得到的色譜圖， 來比較作為内標之3-MCPD-d5和3-MCPD的離子強度，再 藉由換算成游離3-MCPD而算出甘油酯組成物中的縮水甘 油、縮水甘油之脂肪酸酯、3-MCPD、3-MCPD脂肪酸酯的 總量。 (GC-MS分析條件） 分析裝置：Agilent Technology公司製，機型6890GC 管柱：Restek公司製，產品名Rtx — 5MS (長30 m、 直徑 0.25 mm) 管柱溫度：60°C ( 1分鐘）〜190°C (升溫速度6°C/分 鐘）〜280°C (升溫速度20°C/分鐘） 檢測器：MS ( El，SIM模式） 非分流式（splitless):注入lpL 載體氣體：He [表1] 處理條件 3—MCPD換算量 (ppm) 原料甘油酯組成物1 — 85.35 比較例1 未添加加工助劑 110°C，20 分鐘 76.80 實施例1 磷酸活化活性炭 110°C，20分鐘，5質量％ 0.98 實施例2 硫酸處理白土 110°C，20分鐘，5質量％ 0.80 實施例3 硫酸處理白土 常溫，20分鐘，5質量％ 25.65 原料甘油酯組成物2 — 14.30 實施例4 磷酸活化活性炭 6.10 [s] 20 201108943 110°C，20分鐘，5質量％ 實施例5 硫酸處理白土 110°C，20分鐘，5質量％ 6.05 原料甘油醋組成物3 — 11.65 實施例6 磷酸活化活性炭 110°C，20分鐘，5質量％ 0.90 實施例7 硫酸處理白土 1HTC，20分鐘，5質量％ 0.75 可確認到’藉由使用經無機酸活化之活性炭和硫酸處 理的白土來進行處理，甘油酯組成物中的3_MCPD、3-MCPD 脂肪酸酯、縮水甘油、及縮水甘油之脂肪酸酯的總量 鲁 （3-MCPD換算量）顯著降低（表1 :實施例1〜7、原料 甘油醋組成物1〜3、比較例1 ) ^另外，考慮到在甘油酯組 成物中添加的縮水甘油之脂肪酸酯及3_MCPD的量，則縮 水甘油之脂肪酸酯及3_MCPD明顯降低。 [原料甘油酯組成物4] 在利用常規方法精製的大豆.菜籽混合油（大豆脫色油 和菜籽脫色油的混合油）16〇g中添加2〇 8mg的縮水甘油 φ之脂肪酸酯（縮水甘油硬脂酸酯，東京化成工業株式會社 製）和16·0 mg的3_MCpD脂肪酸酯（1•硬脂醯基氣丙 二醇’和光純藥工業株式會社製)，混合後得到原料甘油酿 組成物4 (以3_MCPD換算量計為7() 6i ppm)。 曰 <酸處理之探討> [實施例8] 對於原料甘油S旨組成物4， 在常壓下以15(TC攪拌1〇分鐘 成物® 添加0.025質量。的硫酸， ’得到實施例8的甘油酯組 [S] 21 201108943 [表2] 處理條件 3—MCPD換算量 (ppm) 原料甘油酯組成物4 70.61 實施例8 添加硫酸（0.025質量％ ) 150°C，10 分鐘 11.35 可確認到，經硫酸進行酸處理的甘油酯組成物，其 3-MCPD、3-MCPD脂肪酸酯、縮水甘油、及縮水甘油之脂 肪酸酯的總量（3-MCPD換算量）顯著降低（表2:實施例 8 )。另外’考慮到在甘油酯組成物中添加的缩水甘油之脂 籲 肪酸酯及3-MCPD脂肪酸酯的量，則兩者明顯降低。 <脫臭條件之探討> [實施例9] 對原料甘油醋組成物1的甘油醋組成物一邊注入水蒸 氣（合計量··相對於甘油酯組成物量為3質量％) —邊在 減壓下（4 torr)以21 (TC脫臭90分鐘，得到實施例9的甘 油醋組成物。 [表3] 處理條件 3 — MCPD換算量 (ppm) 原料甘油酯組成物1 — 85.35 實施例9 脫臭210°C 54.15 根據上述記載的定量法算出3_MCPD換算量。可確認 到，藉由在低溫下進行脫臭處理，而降低了 3-MCPD、 3-MCPD脂肪酸g旨、縮水甘油、及縮水甘油之脂肪酸酯的 總量（表3 .實施例9 )。 <脫臭條件和酸值及加熱處理條件之探討> 製備含有大量一酸甘油醋的甘油醋組成物，藉由用活 22 201108943Glycerin S Day Composition 2 (3_McpD 14.30 ppm). in.实施 [Example 4] Activated carbon (disc-activated activated carbon: manufactured by Nippon Nippon Co., Ltd.) was added to the raw material glycerin vinegar composition 2 in an amount of 5 f by weight based on the amount of the raw material glycerol quinone composition 2 Under reduced pressure, 11 〇. . After stirring for 2 minutes, the activated carbon was removed by filtration to obtain the glyceride composition of Example 4. [Example 5] The glyceride composition of Example 5 was obtained in the same manner as in Example 4 except that 5 wt% of activated clay (manufactured by sulfuric acid: manufactured by Mizusawa Chemical Co., Ltd.) was used instead of 5% by mass of activated carbon. Things. [Raw material glyceride composition 3] Raw material glyceride composition 1 and soybean decolorizing oil were mixed at a weight ratio of 86:14 to obtain a raw material glyceride composition 3 (11 _65 ppm in terms of 3_MCPD). [Example 6] 201108943 Activated carbon (phosphorus activated activated carbon: CAi, NO本 NORIT strain formula) was added to the raw material glyceride composition 3 in an amount of 5 mass% based on the raw material glycerin vinegar composition 3, and reduced pressure. After stirring at 11 ° C for 2 minutes, the activated carbon was removed by filtration to obtain the glyceride composition of Example 6. [Example 7] A mass of 5 was used. The glyceride composition of Example 7 was obtained in the same manner as in Example 6 except that the activated clay (manufactured by Sekisui Chemical Co., Ltd.) was used instead of 5% by mass of activated carbon. (Quantitative method) Quantification of 3-MCPD, 3-MCPD fatty acid vinegar, glycidol, and glycidol fatty acid esters in glycerin vinegar composition according to the German official method (DGF Standard Methods C-III 18(09)) get on. In this method, since the fatty acid ester of glycidol and the 3-MCPD fatty acid ester are converted to 3-MCPD in the preparation of the measurement sample, the fatty acid of 3-MCPD, 3-MCPD fatty acid vinegar, glycidol, and glycidol Ester, all measured as free 3-MCPD" 50 μί of internal standard (3-MCPD-d5 20pg) was added to the samples of 100 mg of the raw material glyceride compositions 1 to 3, Examples i to 7 and Comparative Example 1. /mL solution) After adding '1 mL of sodium methoxide solution (0.5 mol/L methanol) to it, it was allowed to react at room temperature to carry out saponification decomposition of the ester. Then, after adding 3 mL of a brine containing a small amount of acetic acid (2 〇〇/0) and 3 mL of hexane and mixing, hexane was removed. At this point, glycidol is converted to 3-MCPD, and the fatty acid ester of glycidol is converted to 3-MCPD at the same time as the ester bond is broken. » Then 'derivatization with 250 μL of aqueous phenylboronic acid (25%), m 19 201108943 2 mL of hexane was extracted and measured by a gas chromatography mass spectrometer. The ionic strength of 3-MCPD-d5 and 3-MCPD as internal standards was compared by the chromatogram obtained by the measurement of the above gas chromatography mass spectrometer, and the glyceride composition was calculated by conversion into free 3-MCPD. The total amount of glycidol, glycidyl fatty acid ester, 3-MCPD, 3-MCPD fatty acid ester. (GC-MS analysis conditions) Analytical device: Agilent Technology, model 6890GC Pipe column: manufactured by Restek, product name Rtx — 5MS (length 30 m, diameter 0.25 mm) Column temperature: 60 ° C (1 minute) ~190°C (temperature up rate 6°C/min)~280°C (temperature up rate 20°C/min) Detector: MS (El, SIM mode) Non-split (splitless): Inject lpL carrier gas: He [ Table 1] Treatment conditions 3 - MCPD conversion amount (ppm) Raw material glyceride composition 1 - 85.35 Comparative Example 1 No processing aid added 110 ° C, 20 minutes 76.80 Example 1 Phosphoric acid activated activated carbon 110 ° C, 20 minutes, 5 Mass % 0.98 Example 2 Sulfuric acid treated clay 110 ° C, 20 minutes, 5 mass % 0.80 Example 3 Sulfuric acid treated clay at room temperature, 20 minutes, 5 mass % 25.65 Raw material glyceride composition 2 - 14.30 Example 4 Phosphoric acid activated carbon 6.10 [s] 20 201108943 110 ° C, 20 minutes, 5 mass % Example 5 sulfuric acid treated clay 110 ° C, 20 minutes, 5 mass % 6.05 raw material glycerin vinegar composition 3 - 11.65 Example 6 phosphoric acid activated activated carbon 110 ° C, 20 minutes, 5 mass% 0.90 Example 7 Sulfuric acid-treated clay 1HTC, 20 minutes, 5% by mass 0.75 It was confirmed that '3' MCPD, 3-MCPD fatty acid in the glyceride composition was treated by using inorganic acid-activated activated carbon and sulfuric acid-treated clay. The total amount of the fatty acid ester of ester, glycidol, and glycidol was significantly lower (3-MCPD conversion amount) (Table 1: Examples 1 to 7, raw material glycerin composition 1 to 3, Comparative Example 1) The fatty acid ester of glycidol and 3_MCPD were remarkably lowered in consideration of the amount of the fatty acid ester of glycidol and the amount of 3_MCPD added to the glyceride composition. [Raw Raw Material Glyceride Composition 4] 2 〇 8 mg of glycidol φ fatty acid ester was added to 16 〇g of soybean and rapeseed mixed oil (mixed oil of soybean decolorizing oil and rapeseed decolorizing oil) refined by a conventional method ( Glycidyl stearate, manufactured by Tokyo Chemical Industry Co., Ltd.) and 10.0 mg of 3_MCpD fatty acid ester (1 stearyl propylene glycol propylene glycol) and Wako Pure Chemical Industries, Ltd. 4 (7 (6i ppm) in terms of 3_MCPD).曰 <Exploration of acid treatment> [Example 8] For the raw material glycerin S composition 4, under normal pressure, 15 (TC was stirred for 1 minute, and the product was added with 0.025 mass of sulfuric acid, 'to obtain Example 8 Glyceride group [S] 21 201108943 [Table 2] Treatment conditions 3 - MCPD conversion amount (ppm) Raw material glyceride composition 4 70.61 Example 8 Adding sulfuric acid (0.025 mass%) 150 ° C, 10 minutes 11.35 It was confirmed The glyceride composition subjected to acid treatment with sulfuric acid, the total amount of 3-MCPD, 3-MCPD fatty acid ester, glycidol, and glycidol fatty acid ester (3-MCPD conversion amount) was remarkably lowered (Table 2: Example 8) Further, considering the amount of the glycidyl ester and the 3-MCPD fatty acid ester of glycidol added to the glyceride composition, both were significantly lowered. <Discussion of Deodorization Conditions> [Example 9] Water vapor was injected into the glycerin vinegar composition of the raw material glycerin vinegar composition 1 (total amount, 3% by mass based on the amount of the glyceride composition) - while under reduced pressure (4 torr) was 21 ( The TC was deodorized for 90 minutes to obtain the glycerin vinegar composition of Example 9. [Table 3] Treatment Conditions 3 MCPD conversion amount (ppm) Raw material glyceride composition 1 - 85.35 Example 9 Deodorization 210 ° C 54.15 The amount of 3_MCPD was calculated by the quantitative method described above. It was confirmed that the deodorization treatment was carried out at a low temperature to reduce The total amount of 3-MCPD, 3-MCPD fatty acid g, glycidol, and glycidol fatty acid ester (Table 3 and Example 9). <Dissolved conditions, acid value, and heat treatment conditions> Preparation of a glycerin vinegar composition containing a large amount of monoglyceride, by using live 22 201108943
3-MCPD、 水甘油之脂肪酸酯的合計含量降低的樣品。然 加熱處理之溫度和有無添加游離脂肪酸對 3-mcpd脂肪酸醋、縮水甘油及縮水甘油之脂肪 酸酯的生成抑制所產生的影響，進行了探討。 [原料甘油酯組成物5] 用脂肪酶對按常規方法精製的大豆脫色油和菜籽脫色 油的混合油進行部分水解，並進行分子蒸餾。進一步向在 250 C下脫臭1.5小時的甘油酯組成物，添加5質量％之活 性白土（V2F，硫酸處理白土，水澤化學工業株式會社製）， 在減壓下以11 〇。(：攪拌20分鐘後，過濾除去活性白土，得 到原料甘油酯組成物5(甘油酯組成是：單甘酯〇 6重量％、 二酸甘油酯88.7重量％以及三酸甘油酯10.7重量％，以 3-MCPD換算量計為ο·% ppm)。 [實施例10] 將甘油酯組成物5 (甘油酯組成物的酸值：〇·2 )在常 壓下以220。(：處理90分鐘’得到實施例1 〇的甘油酯組成物。 [實施例11] 除了為使甘油酯組成物的酸值達5.8而添加棕摘酸之 外’採用與實施例10同樣的方法得到實施例11的甘油酯 組成物。 [實施例12] 除了為使甘油酯組成物的酸值達10.9而添加棕櫚酸之 外，採用與實施例1 〇同樣的方法得到實施例12的甘油酯 23 201108943 組成物。 [實施例13] 除了使溫度達230°C以外，採用與實施例1〇同樣的方 法得到實施例13的甘油酯組成物。 [實施例14] 除了使溫度達230°C以外，採用與實施例11同樣的方 法得到實施例14的甘油酯組成物。 [實施例15] 除了使溫度達230°C以外’採用與實施例12同樣的方 法得到實施例15的甘油酯組成物。 [比較例2] 除了使溫度達240°C以外，採用與實施例1 〇同樣的方 法得到比較例2的甘油酯組成物。 [實施例16] 除了使溫度達24(TC以外，採用與實施例11同樣的方 % 法得到實施例16的甘油酯組成物。 [實施例17] 除了使溫度達24(TC以外，採用與實施例12同樣的方 法得到實施例17的甘油酯組成物。 [S] 24 201108943 [表4]A sample in which the total content of 3-MCPD and glycerin fatty acid ester is lowered. However, the effect of heat treatment and the presence or absence of the addition of free fatty acids on the inhibition of the formation of 3-mcpd fatty acid vinegar, glycidol and glycidol fatty acid esters were investigated. [Raw material glyceride composition 5] The mixed oil of the soybean decoloring oil and the rapeseed decolorizing oil refined by a conventional method was partially hydrolyzed with a lipase, and subjected to molecular distillation. Further, to the glyceride composition which was deodorized at 250 C for 1.5 hours, 5% by mass of activated clay (V2F, sulfuric acid-treated clay, manufactured by Mizusawa Chemical Co., Ltd.) was added, and 11 Torr under reduced pressure. (: After stirring for 20 minutes, the activated clay was removed by filtration to obtain a raw material glyceride composition 5 (the glyceride composition was: monoglyceride 〇 6 wt%, diglyceride 88.7 wt%, and triglyceride 10.7 wt%, The 3-MCPD conversion amount is ο·% ppm). [Example 10] The glyceride composition 5 (acid value of glyceride composition: 〇·2) was 220 at normal pressure (: 90 minutes of treatment) The glyceride composition of Example 1 was obtained. [Example 11] The glycerin of Example 11 was obtained in the same manner as in Example 10 except that brown acid was added to adjust the acid value of the glyceride composition to 5.8. [Embodiment 12] A glyceride 23 201108943 composition of Example 12 was obtained in the same manner as in Example 1 except that palmitic acid was added to adjust the acid value of the glyceride composition to 10.9. Example 13] A glyceride composition of Example 13 was obtained in the same manner as in Example 1 except that the temperature was adjusted to 230 ° C. [Example 14] In addition to the temperature of 230 ° C, the examples and examples were employed. The glyceride composition of Example 14 was obtained in the same manner. Example 15] A glyceride composition of Example 15 was obtained in the same manner as in Example 12 except that the temperature was adjusted to 230 ° C. [Comparative Example 2] Example 1 was employed except that the temperature was adjusted to 240 ° C. The glyceride composition of Comparative Example 2 was obtained by the same method. [Example 16] A glyceride composition of Example 16 was obtained in the same manner as in Example 11 except that the temperature was 24 (TC). Example 17] A glyceride composition of Example 17 was obtained in the same manner as in Example 12 except that the temperature was 24 (TC). [S] 24 201108943 [Table 4]
處理條件 3 —MCPD換算量 (ppm) 原料甘油醋組成物5 硫酸處理白土（5質量％)，110°C，20分鐘 0.76 硫酸處理白土（5質量％)，110°C，20分鐘 實施例10 未添加棕網酸，酸值：0.2 220°C，90分鐘，常壓 30.80 硫酸處理白土（5質量％)，110°C，2〇分鐘 實施例11 添加棕櫊酸，酸值：5.8 220°C，90分鐘，常壓 4.50 硫酸處理白土（5質量％)，110°C，2〇分鐘 實施例12 添加棕櫚酸，酸值：10.9 220°C，90分鐘，常壓 2.78 硫酸處理白土（5質量％)，110°C，20分鐘 實施例13 未添加掠摘酸，酸值：0.2 230°C，90分鐘，常壓 56.01 硫酸處理白土（5質量％)，110°C，20分鐘 實施例14 添加棕櫊酸，酸值：5.8 230°C，90分鐘，常壓 7.01 硫酸處理白土（5質量％)，110°C，2〇分鐘 實施例15 添加椋櫊酸，酸值：10.9 230°C，90分鐘，常壓 3.91 硫酸處理白土（ 5質量％ )，110°C，20分鐘 比較例2 未添加棕櫊酸，酸值：0.2 240°C，90分鐘，常壓 87.31 硫酸處理白土（5質量％)，110°C，2〇分鐘 實施例16 添加棕櫊酸，酸值：5.8 240°C，90分鐘，常壓 11.02 硫酸處理白土（5質量％)，110°C，20分鐘 實施例17 添加棕櫚酸，酸值：10.9 240°C，90分鐘，常壓 6.03 根據上述記載的定量法算出3-MCPD換算量。在加熱 處理中，溫度越低越能抑制3-MCPD、3-MCPD脂肪酸酯、 縮水甘油及縮水甘油之脂肪酸酯的總量（3-MCPD換算量） (表3 :原料甘油酯組成物5、實施例1 0〜1 7、比較例2 )。 [S] 25 201108943 在進行脫臭處理這樣的高溫處理時，為使酸值達到5 8或 10.9而添加棕櫚酸，而可確認到，隨著高溫，、 3-MCPD月日肪酸g旨、縮水甘油及縮水甘油之脂肪酸醋的生 成受到顯著抑制（表3 :實施例丨〇〜丨2、實施例丨3〜丨5、 比較例2及實施例1 6〜1 7 )。 [原料甘油酯組成物6]Treatment condition 3 - MCPD conversion amount (ppm) Raw material glycerin vinegar composition 5 Sulfuric acid treated clay (5 mass%), 110 ° C, 20 minutes 0.76 sulfuric acid treated clay (5 mass%), 110 ° C, 20 minutes Example 10 No added palmitic acid, acid value: 0.2 220 ° C, 90 minutes, atmospheric pressure 30.80 sulfuric acid treated clay (5 mass%), 110 ° C, 2 〇 minutes Example 11 added palmitic acid, acid value: 5.8 220 ° C, 90 minutes, atmospheric pressure 4.50 sulfuric acid treated clay (5 mass%), 110 ° C, 2 〇 minutes Example 12 Add palmitic acid, acid value: 10.9 220 ° C, 90 minutes, atmospheric pressure 2.78 sulfuric acid treated clay (5 Mass %), 110 ° C, 20 minutes Example 13 No grazing acid added, acid value: 0.2 230 ° C, 90 minutes, atmospheric pressure 56.01 sulfuric acid treated clay (5 mass%), 110 ° C, 20 minutes Example 14 Add palmitic acid, acid value: 5.8 230 ° C, 90 minutes, atmospheric pressure 7.01 sulfuric acid treated clay (5 mass%), 110 ° C, 2 〇 minutes Example 15 Addic acid, acid value: 10.9 230 ° C, 90 minutes, atmospheric pressure 3.91 sulfuric acid treated clay (5 mass%), 110 ° C, 20 minutes Comparative Example 2 Palmitic acid was not added, acid value: 0.2 240 ° C, 90 minutes, atmospheric pressure 87.31 sulfuric acid treated clay (5 mass%), 110 ° C, 2 〇 minutes Example 16 added palmitic acid, acid value: 5.8 240 ° C, 90 minutes, atmospheric pressure 11.02 sulfuric acid treated clay (5 mass%), 110 ° C, 20 minutes Example 17 Add palmitic acid, acid value: 10.9 240 ° C, 90 minutes, atmospheric pressure 6.03 According to the above-mentioned quantitative method Calculate the amount of 3-MCPD conversion. In the heat treatment, the lower the temperature, the more the total amount of fatty acid esters of 3-MCPD, 3-MCPD fatty acid ester, glycidol and glycidol (3-MCPD conversion amount) can be suppressed (Table 3: raw material glyceride composition) 5. Example 1 0 to 1 7. Comparative Example 2). [S] 25 201108943 When high-temperature treatment such as deodorization treatment is carried out, palmitic acid is added to increase the acid value to 5 8 or 10.9, and it can be confirmed that 3-MCPD has a high-temperature, 3-MCPD The formation of fatty vinegar of glycidol and glycidol was remarkably suppressed (Table 3: Example 丨〇~丨2, Example 丨3 to 丨5, Comparative Example 2, and Examples 1-6 to 17). [Raw material glyceride composition 6]
用脂肪酶對按常規方法提取的米油進行部分水解，脫 酸後，對該脫酸之米油添加2質量％的活性白土（ V2F，硫 酸處理白土’水澤化學工業株式會社製），在減麼下以⑺代 ㈣20分鐘後，過遽去除活性白土得到脫色之米油。接 著，對該脫色之米油—邊注人水蒸氣（相對於油為3質量 %) -邊在減壓下（4torr)以24〇t脫臭9〇分鐘得到精 製油(原料甘油醋組成叫另外，利用氣相色譜法(A0CS _ al Method Cd 1 lb-91)測定原料甘油醋組成物6中的 一酸甘油酯含量，結果是7質量〇/(^ [參考例1] /田自曰組成* 6添加〇1質量％的活性白土 硫酸處理白土，水澤化學卫業株式會社 壓拌20分錢，過濾去除活性白土 脫“(參考例1的甘油醋組成物)。 到再 [實施例18 ] 二原料甘油醋組成物6添加。5質量％的活性白土 S) 壓下β ^酸處理白土水澤化學卫業株式會社製），在減 C搜拌2G分鐘後，過據去除活性白土得到再 26 201108943 脫色油。接著，對該再脫色油一邊注入水蒸氣（相對於油 為3質量％) —邊在減壓下ί〇ΓΓ)以24〇乞脫臭90分鐘， 得到實施例1 8的甘油酯組成物。 [實施例19] 對原料甘油酯組成物6添加〇.5質量％的活性白土 (V2F,硫酸處理白土，水澤化學工業株式會社製）’在減 壓下以110°C攪拌20分鐘後，過濾去除活性白土，得到再 φ 脫色油。接著’對該再脫色油一邊注入水蒸氣（相對於油 為3質量％)—邊在減壓下（4 t〇rr)以23〇°c脫臭％分鐘， 得到實施例19的甘油酯組成物。 [實施例20] 對原料甘油酯組成物6添加1質量％的活性白土 (V2F，硫酸處理白土，水澤化學工業株式會社製），在減 壓下以ll〇t攪拌20分鐘後，過濾去除活性白土，得到再 脫色油。接著’對該再脫色油一邊注入水蒸氣（相對於油 # 為3質量％)—邊在減壓下（4 ton·)以220°C脫臭90分鐘， 得到實施例2〇的甘油酯組成物。 [實施例21] 對原料甘油酯組成物6添加1質量％的活性白土 (V2F ,硫酸處理白土，水澤化學工業株式會社製），在減 壓下以110。(：攪拌20分鐘後，過濾去除活性白土，得到再 脫色油。接著，對該再脫色油一邊注入水蒸氣（相對於油 為3質量。/〇) 一邊在減壓下（4t〇rr)以2〇〇〇c脫臭％分鐘， 得到實施例21的甘油酯組成物。 27 201108943 [表Η 參考例1 實施例18 實施例19 實施例20 實施例21 原料甘油酯組成物 原料甘油酯組成物6 (二酸甘油酯含量：7質量〇/0) 原料甘油酯組成物之 3—MCPD 換算量（PDm) 3.6 再脫色時之 活性白土量（蜇景％) 0.1 0.5 再脫色油之 3—MCPD換算量（ppm) 0.8 0.6 1.8 再脫臭時之 脫臭溫度（°cn 一 240 230 220 200 再脫臭油之 3-MCPD 換算量 ※來老例1思.岐欢茗，香始 Μ 1 C .0 1 Ε7 · 1.9 1.4 1.3 0.9 根據上述記載的定量法算出3_MCPD換算量。可確認 到，實施例18〜21可降低精製油中的3_McpD換算量，還 可製出風味良好的食用油。此外，再脫臭溫度越低，降低 3-MCPD &算量的效果越好，再脫色時的活性白土量如果 是〇·5質量％，則減小3_MCPD換算量的效果顯著。 [原料甘油酯組成物7] 將85質#%之菜軒脫色油（日清奥利友株式會杜们 和15質量％之甘油醋組成物5混合，對所得到的混合油一 邊注入水蒸氣（相對於Μ 3 f量％)_邊在_下（〇 以赠脱臭90分鐘’得到精製油（原料甘油醋組成物7)。 另外’用氣相色譜法（A0CS⑽咖以… —90測定原料甘㈣組成物7中的二酸甘油 果是13.3質量％。 里箱 [參考例2 ] 原：甘油醋組成物7添加。質量%之活性白土 [S] 硫酸處理白土，水澤化學工業株式會社製)，在減 28 201108943 壓下以110°c攪拌20分鐘後，過濾去除活性白 土 ’得到再 脫色油（參考例2的甘油酯組成物）》 [實施例22] 對原料甘油酯組成物7添加〇 5質詈。 貝篁/〇之活性白土 (V2F，硫酸處理白土 ’水澤化學工業株式會社製）， 壓下以110°C檀拌20分鐘後，過濾去除活性白+ ，得到再 脫色油。接著，對該再脫色油一邊注入水蒸氣（對由3 量。/。）一邊在減壓下（4 torr)以240°C脫臭90公私 刀趱，得到 實施例22的甘油酯組成物。 [實施例23] 對原料甘油酯組成物7添加〇. 5質量％之活 4『生白土 (V2F，硫酸處理白土，水澤化學工業株式會社製），在減 壓下以110°C攪拌20分鐘後’過濾去除活性白土，得到再 脫色油。接著，對該再脫色油一邊注入水蒸氣（相對於油 為3質量％)—邊在減壓下（4 torr )以230°C脫臭9〇分鐘， φ 得到實施例23的甘油酯組成物。 [實施例24] 對原料甘油醋組成物7添加1質量％之活性白土 (V2F ’硫酸處理白土，水澤化學工業株式會社製），在減 麗下以110。〇攪拌20分鐘後，過濾去除活性白土，得到再 脫色油。接著，對該再脫色油一邊注入水蒸氣（相對於油 為3質量。/0) 一邊在減壓下（4 t〇rr)以22〇。〇脫臭90分鐘， 得到實施例24的甘油酯組成物。 [實施例25] 29 201108943 對原料甘油酯組成物7添加 1質量％之活性白土 (V2F，硫酸處理白土，水澤化學工業株式會社製），在減 壓下以11 0°C攪拌20分鐘後，過濾去除活性白土，得到再 脫色油。接著，對該再脫色油一邊注入水蒸氣（相對於油 為3質量％) —邊在減壓下（4 torr)以200°C脫臭90分鐘， 得到實施例25的甘油酯組成物。 [表6] ——_ 參考例2 實施例22 實施例23 實施例24 實施例25 原料甘油酯組成物 原料甘油酯組成物7 (二酸甘油酯含量：13.3質量％) 原料甘油酯組成物 之3—MCPD換算量（ppm) 7.3 再脫色時之活性白土量 (質量％) 0.1 0.5 1 再脫色油之 3-MCPD 換算量（ppm) 1.4 0.3 0.5 再脫臭時之 脫臭溫度（°C) — 240 230 220 200 再脫臭油之 3—MCPD 換算量（ppm) — 3.9 3.1 1.9 0.8 ※參考例2風味略差，實施例22~25風味良好。 根據上述記載的定量法算出3-MCPD換算量。可確認 φ 到，實施例22〜25可降低精製油中的3-MCPD換算量，還 可精製出風味良好的食用油。此外，再脫臭溫度越低，降 低3-MCPD換算量的效果越好，再脫色時的活性白土量如 果是0.5質量％，則降低3-MCPD換算量的效果顯著。 【圖式簡單說明】 無 【主要元件符號說明】 無 [S) 30The lipoenzyme is used to partially hydrolyze the rice oil extracted by the conventional method, and after deacidification, 2% by mass of activated clay (V2F, sulfuric acid-treated white clay, manufactured by Mizusawa Chemical Co., Ltd.) is added to the deacidified rice oil. After 20 minutes of (7) generation (four), remove the activated clay to obtain decolorized rice oil. Next, the decolorized rice oil was injected with water vapor (3 mass% relative to the oil) - and deodorized at 24 Torr for 9 minutes under reduced pressure (4 torr) to obtain a refined oil (the raw material glycerin composition was called Further, the content of monoglyceride in the raw material glycerin vinegar composition 6 was measured by gas chromatography (A0CS_al Method Cd 1 lb-91), and the result was 7 mass 〇 / (^ [Reference Example 1] / 田自曰Composition * 6 Add 〇1% by mass of activated clay sulfuric acid-treated white clay, and water-repellent chemical industry Co., Ltd. squeezes 20 cents, and removes activated clay ("Recommendation Example 1 glycerin vinegar composition"). The second raw material glycerin vinegar composition 6 is added. 5% by mass of activated clay S) is pressed by β ^ acid treatment, white clay, Mizusawa Chemical Industry Co., Ltd.), after 2 minutes of mixing C, it is removed by removing activated clay. 26 201108943 Decolorization oil. Next, the re-decolorization oil was sprayed with water vapor (3 mass% with respect to oil) while deodorizing at 24 Torr for 90 minutes to obtain Example 18 A glyceride composition [Example 19] 5% by mass of the raw material glyceride composition 6 was added. The active white clay (V2F, sulfuric acid-treated clay, manufactured by Mizusawa Chemical Co., Ltd.) was stirred at 110 ° C for 20 minutes under reduced pressure, and then the activated clay was removed by filtration to obtain a re- φ decolorizing oil. Water vapor (3 mass% with respect to oil) was injected, and deodorized at 23 ° C for 1 minute under reduced pressure (4 t Torr) to obtain a glyceride composition of Example 19. [Example 20] In the raw material glyceride composition 6, 1% by mass of activated clay (V2F, sulfuric acid-treated clay, manufactured by Mizusawa Chemical Co., Ltd.) was added, and the mixture was stirred at TL for 20 minutes under reduced pressure, and then the activated clay was removed by filtration to obtain a re-decolorized oil. Then, 'the decolorization oil was poured with water vapor (3 mass% with respect to oil #) - while deodorizing at 220 ° C for 90 minutes under reduced pressure (4 ton·), the glyceride of Example 2 was obtained. [Example 21] 1% by mass of activated clay (V2F, sulfuric acid-treated clay, manufactured by Mizusawa Chemical Co., Ltd.) was added to the raw material glyceride composition 6, and 110 was added under reduced pressure. (: After stirring for 20 minutes) , remove the activated clay by filtration, and obtain the decolorized oil Next, this re-decolorizing oil was poured into water vapor (3 mass% / 相对 with respect to oil), and deodorized by 2 〇〇〇c under reduced pressure (4 Torr) for 1 minute to obtain the glyceride of Example 21. Composition 2011 27 201108943 [Table Η Reference Example 1 Example 18 Example 19 Example 20 Example 21 Raw material glyceride composition Raw material glyceride composition 6 (diglyceride content: 7 mass 〇 / 0) Raw material glyceride Composition 3 - MCPD conversion amount (PDm) 3.6 Active white clay amount (degradation %) at the time of decolorization 0.1 0.5 Decolorization oil 3 - MCPD conversion amount (ppm) 0.8 0.6 1.8 Deodorization temperature at the time of deodorization ( °cn a 240 230 220 200 3-MCPD conversion amount of deodorized oil ※The old example 1 thinks. 岐欢茗,香始Μ 1 C .0 1 Ε7 · 1.9 1.4 1.3 0.9 Calculate 3_MCPD according to the quantitative method described above The amount of conversion. In Examples 18 to 21, it was confirmed that the amount of 3_McpD in the refined oil can be reduced, and an edible oil having a good flavor can be produced. Further, the lower the deodorization temperature, the better the effect of reducing the amount of 3-MCPD & the amount of active white clay at the time of decolorization is 〇·5 mass%, and the effect of reducing the amount of conversion of 3_MCPD is remarkable. [Raw material glyceride composition 7] The 85-yellow #% of the vegetable-based decolorizing oil (Nissin Olympus Co., Ltd. and 15% by mass of the glycerin vinegar composition 5 are mixed, and water vapor is injected into the obtained mixed oil. (relative to Μ 3 f%) _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ The diacylglycerol fruit in the composition (4) is 13.3% by mass. The inner tank [Reference Example 2] The original: glycerin vinegar composition 7 is added. The mass% of the activated clay [S] sulfuric acid treated clay, manufactured by Mizusawa Chemical Industry Co., Ltd. After the mixture was stirred at 110 ° C for 20 minutes under reduced pressure, the activated white clay was removed by filtration to obtain a re-decolorized oil (the glyceride composition of Reference Example 2). [Example 22] Addition of the raw material glyceride composition 7 〇5 詈 詈 活性 活性 活性 活性 活性 活性 活性 活性 活性 活性 活性 活性 活性 活性 活性 活性 活性 活性 活性 活性 活性 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 Next, water vapor is injected into the re-decolorized oil (for 3 The amount of glycerol ester of Example 22 was obtained by deodorizing 90 gongs at 240 ° C under reduced pressure (4 torr). [Example 23] 〇 was added to the raw material glyceride composition 7. 5% by mass of live 4 "raw white clay (V2F, sulfuric acid-treated clay, manufactured by Mizusawa Chemical Co., Ltd.), and after stirring at 110 ° C for 20 minutes under reduced pressure, the activated clay was removed by filtration to obtain a re-decolorized oil. The re-decoloring oil was poured into water vapor (3 mass% with respect to oil), and deodorized at 230 ° C for 9 minutes under reduced pressure (4 torr) to obtain the glyceride composition of Example 23 by φ. Example 24: 1% by mass of activated clay (V2F 'sulphuric acid-treated clay, manufactured by Mizusawa Chemical Co., Ltd.) was added to the raw material glycerin vinegar composition 7. After stirring for 20 minutes under reduced enthalpy, the activated clay was removed by filtration. The re-decoloring oil was obtained, and then water vapor (3 mass% / /0 with respect to oil) was injected into the re-decolorizing oil, and it was dehydrated under a reduced pressure (4 t〇rr) for 22 minutes. The glyceride composition of Example 24. [Example 25] 29 201108943 In the oil ester composition 7, 1% by mass of activated clay (V2F, sulfuric acid-treated clay, manufactured by Mizusawa Chemical Co., Ltd.) was added, and the mixture was stirred at 110 ° C for 20 minutes under reduced pressure, and then the activated clay was removed by filtration to obtain a re-decolorized oil. Then, the re-decolorizing oil was poured into water vapor (3 mass% with respect to oil), and deodorized at 200 ° C for 90 minutes under reduced pressure (4 torr) to obtain a glyceride composition of Example 25. [Table 6] - _ Reference Example 2 Example 22 Example 23 Example 24 Example 25 Raw material glyceride composition Raw material glyceride composition 7 (diglyceride content: 13.3% by mass) Raw material glyceride composition 3—MCPD conversion amount (ppm) 7.3 Active clay content (% by mass) when decolorizing 0.1 0.5 1 3-MCPD conversion amount of decolorized oil (ppm) 1.4 0.3 0.5 Deodorization temperature (°C) — 240 230 220 200 De-odorizing oil 3—MCPD conversion amount (ppm) — 3.9 3.1 1.9 0.8 ※ Reference example 2 has a slightly poor flavor, and examples 22 to 25 have a good flavor. The 3-MCPD conversion amount was calculated by the quantitative method described above. It was confirmed that φ was obtained, and in Examples 22 to 25, the amount of 3-MCPD in the refined oil was reduced, and the edible oil having a good flavor was also purified. Further, the lower the deodorization temperature, the better the effect of lowering the amount of 3-MCPD conversion, and if the amount of activated clay at the time of decolorization is 0.5% by mass, the effect of reducing the amount of 3-MCPD conversion is remarkable. [Simple diagram description] None [Main component symbol description] None [S) 30
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| KR20110085142A (en) * | 2010-01-19 | 2011-07-27 | 씨제이제일제당 (주) | A process for preparing low 3- mcpd-fs edible oil |
| JP5717351B2 (en) | 2010-03-17 | 2015-05-13 | 花王株式会社 | Method for producing refined fats and oils |
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| MY161540A (en) * | 2010-05-07 | 2017-04-28 | Adeka Corp | Method for refining edible oil and fat |
| CN102453608B (en) * | 2010-10-26 | 2013-09-04 | 中国石油化工股份有限公司 | Method for reducing oil acid value and obtained oil mixture |
| PL3385360T3 (en) * | 2011-02-10 | 2021-09-06 | Cargill, Incorporated | Process for reducing the 3-mcpd content in refined oils |
| JP6008596B2 (en) * | 2011-06-15 | 2016-10-19 | 花王株式会社 | Method for producing refined fats and oils |
| JP6021382B2 (en) * | 2011-07-29 | 2016-11-09 | 日清オイリオグループ株式会社 | Method for producing glyceride composition |
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| EP2738243B1 (en) * | 2011-07-29 | 2016-10-05 | The Nisshin Oillio Group, Ltd. | Purified glyceride composition and method for producing purified glyceride composition |
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| JP6385634B2 (en) * | 2011-11-30 | 2018-09-05 | 日清オイリオグループ株式会社 | Oil and fat manufacturing method |
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