200946674 六、發明說明： 【發明所屬之技術領域】 本發明係有關利用甘油酯（油脂）與甲醇之酯交換反 應的脂肪酸甲酯之製造方法。 【先前技術】 將植物油或由飮食店、一般家庭所回收之廢食用油等 © 之油脂與脂肪族醇進行酯交換反應後，作爲脂肪酸烷酯進 行利用。特別是藉由油脂與甲醇之酯交換反應所得之脂肪 酸甲酯亦稱爲生物柴油燃料，相較於石油系燃料，其較少 混入硫份、芳香族份，因此作爲對於環境負荷小之燃料極 被矚目。 作爲油脂與甲醇之酯交換反應時所使用之觸媒者，公 知有對於油脂、脂肪族醇之溶解性高之鹼金屬之氫氧化物 (氫氧化鈉、氫氧化鉀）。惟，使鹼金屬之氫氧化物用於 ® 觸媒時，由於所生成之脂肪酸烷酯中混入鹼金屬之氫氧化 物，因此洗淨脂肪酸烷酯，去除鹼金屬之氫氧化物，甚至 務必進行藉由洗淨所產生之鹼排水處理之問題存在。故， 作爲酯交換反應用觸媒者，使用對於油脂、脂肪族醇之溶 解性低之固體觸媒者，被硏討之。 專利文獻1中被記載有，固體觸媒中使用氧化鈣粉末 ，鈣甲醇金屬粉末之脂肪酸甲酯之製造方法。此專利文獻 1之圖6中記載之經由於甲醇中之攪拌後活化氧化鈣（「 0.05g活性化及0.005g活性化」）’記載之將氧化鈣粉末 200946674 加入甲醇，作成漿料，進行5小時熱迴流後，將此過濾、 乾燥後取得白色粉末（「Ca(OH)(OCH3)0.05g」），及記 載之市售之甲氧化鈣粉末（「Ca(OCH3)2 0.005g」）用於 固體觸媒，製造脂肪酸甲酯時，所代表反應時間與脂肪酸 甲酯之收率相互之關係曲線圖。該圖6之曲線圖，其反應 時間爲3小時之脂肪酸甲酯收率以「〇.〇5g活性化」約爲 90%最高，接著「0.005g活性化」高，接下來「 Ca(OH)(OCH3)0.05g」高，而「C a( Ο C Η 3 )2 0 · 0 0 5 g」最低。 © 惟，「0.05g活性化」之脂肪酸甲酯收於反應時間1小時 下約爲3 0 %。 另外，專利文獻1中，無針對甲氧化鈣之製法之記載 。非專利文獻1中記載，鈣之烷氧基金屬係使鈣金屬溶於 醇所得者。 專利文獻1 :國際公開第2007/088702號手冊 非專利文獻1:化學大辭典編集委員編，「化學大辭 典1」，初版，共立出版股份公司，昭和35年3月30日 〇 ，p.394 【發明內容】 根據上述專利文獻1所揭示之方法’可使脂肪酸甲酯 於反應時間3小時之收率約爲90%之生成速度進行製造。 惟，爲於工業上大量製造脂肪酸甲酯，被期待使脂肪酸甲 酯進一步提昇生成速度的高速化與收率之提昇。 因此，本發明的目的係提供一種’利用固體觸媒’可 -6- 200946674 以於更短時間下，且以高收率製造脂肪酸甲酯之方法。另 外本發明之目的又爲提供一種，對於油脂與脂肪族醇之酯 交換反應，發揮高度觸媒作用之新穎的固體觸媒。 本發明者發現，於油脂（亦即甘油酯）與甲醇之酯交 換反應用之固體觸媒中使用，將平均粒徑爲1〜ι〇〇μηι之 範圍，BET比表面積爲1〜10m2/g之範圍，而直徑爲2〜 lOOnm範圍之細孔的總細孔容積爲0.010〜〇_l〇mL/g範圍 Ο 之氧化鈣粉末，於甲醇中進行粉碎至其平均粒徑爲當初之 値的70%以下之値爲止，使氧化鈣粉碎生成物與甲醇反應 後生成甲氧化鈣後，所得之平均粒徑爲0.10〜ιομπι範圍 之甲氧化鈣粉末，相較於使用先行技術之甲醇中之攪拌後 活化之氧化鈣，前者明顯顯現其脂肪酸甲酯之生成速度變 得極快速，進而完成本發明。 因此，本發明於甲氧化鈣粉末之存在下，使甘油酯與 甲醇進行酯交換反應後，製造脂肪酸甲酯之方法中，該鈣 ❹ 甲醇金屬粉末其平均粒徑爲0.10〜ΙΟμπι之範圍，甲氧化 鈣分散液之形態或該甲氧化鈣分散液被甲醇稀釋之形態下 進行供應，該甲氧化鈣分散液其平均粒徑爲1〜100 μ«ι之 範圍，BET比表面積爲1〜10m2/g之範圍，而直徑爲2〜 lOOnm範圍之細孔的總細孔容積爲0.010〜0.10mL/g範圍 之氧化鈣粉末於甲醇中進行粉碎，使有該氧化鈣粉末之平 均粒徑之70%以下平均粒徑之甲氧化鈣粉末於該甲醇中生 成之方式製造者爲其特徵之脂肪酸甲酯的製造方法。 本發明脂肪酸甲酯製造方法之理想形態如下述。 200946674 (1) 甲氧化鈣粉末之BET比表面積爲20〜6 0m2/g之 範圍，而直徑爲2〜100nm範圍之細孔的總細孔容積爲 0.1 0〜1 .OmL/g之範圍。 (2) 甲氧化鈣粉末之直徑爲10〜l〇〇nm範圍之細孔 的總細孔容積爲0.060〜0.80mL/g之範圍。 (3) 氧化鈣粉末係使重質碳酸鈣於大氣雰圍下藉由 燒成所得之氧化鈣粉末。 本發明又有使平均粒徑爲0.10〜10 μιη範圍之甲氧化 ❹ 鈣粉末分散於甲醇中，使平均粒徑爲1〜100μηι範圍、 BET比表面積爲1〜1 0m2/g之範圍，而直徑爲2〜1 OOnm 範圍之細孔的總細孔容積爲0.0 10〜0·1 OmL/g範圍之氧化 鈣粉末於甲醇中進行粉碎，使具有該氧化鈣粉末之平均粒 徑70 %以下之平均粒徑之鈣甲醇金屬粉末於該甲醇中生成 之方式製造之甲氧化鈣分散液。 本發明甲氧化鈣分散液之理想形態如下述。 (1) 甲氧化鈣粉末之BET比表面積爲20〜60m2/g之 © 範圍，而直徑爲2〜lOOnm範圍之細孔的總細孔容積爲 0.01〜1.OmL/g之範圍》 (2) 甲氧化鈣粉末之直徑爲10〜l〇〇nm範圍之細孔 的總細孔容積爲0.060〜0.80mL/g之範圍。 (3) 甘油酯與甲醇之酯交換反應用觸媒。 經由利用本發明之脂肪酸甲酯的製造方法，與以先行 技術之甲醇中之攪拌後活化之氧化鈣用於固體觸媒時，進 行比較後，本發明較可於短時間下，以高產率製造脂肪酸 -8 - 200946674 甲酯。 又’本發明之甲氧化鈣分散液係使重質碳酸鈣於大氣 雰圍下燒成所得之氧化鈣粉末用於原料，仍可作爲高活化 觸媒，輕易有效的製造。因此，極適用於油脂與甲醇之酯 交換反應用觸媒。 【實施方式】 © [發明實施之最佳形態] 本發明脂肪酸甲酯之製造方法中，作爲固體觸媒者， 使用使氧化鈣粉末於甲醇中粉碎，氧化鈣粉碎生成物與甲 醇經反應所生成之平均粒徑爲0.10〜ΙΟμπι範圍之甲氧化 鈣粉末。甲氧化鈣粉末之平均粒徑爲0.50〜5.0 μπι範圍者 宜，更佳者爲1.0〜3.0 μιη之範圍。又，甲氧化鈣粉末之 BET比表面積爲20〜60m2/g之範圍者宜，更佳者爲20〜 5 0m2/g範圍，直徑爲2〜lOOnm範圍之細孔的總細孔容積 ® 爲0.10〜1.0mL/g之範圍者宜，更佳者爲〇.1〇〜〇.50mL/g 之範圍。而直徑爲10〜l〇〇nm範圍之細孔的總細孔容積爲 0.060〜0.80mL/g之範圍者宜，更佳者爲〇·〇60〜0.40mL/g 之範圍。另外，甲氧化鈣粉末之bet比表面積及細孔容積 係由甲氧化鈣分散液所分離回收之甲氧化鈣粉末之値。 作爲甲氧化鈣粉末製造原料之氧化鈣粉末之平均粒徑 爲1〜1 ΟΟμιη之範圍者宜，較佳者爲1〜50μιη之範圍。 BET比表面積爲1〜10m2/g之範圍。而直徑爲2〜lOOnm 範圍之細孔的總細孔容積爲〇.〇10〜0.10mL/g之範圍。 200946674 作爲原料之氧化鈣粉末者，可使用使重質碳酸鈣（石 灰石經粉碎、分級者）、輕質碳酸鈣（使石灰乳碳酸化者 等）、經加熱轉化成氧化鈣之鈣化合物（氫氧化鈣或消石 灰等）於大氣氛圍下燒成所得者。其中，由經濟面視之， 又以重質碳酸鈣於大氣氛圍下燒成所得者較佳。另外亦可 使用氧化鈣或生石灰之再燒成者’使上述碳酸鈣、鈣化合 物於惰性氣體下燒成者。 本發明中，於甲醇中使氧化鈣粉末粉碎係指’於分散 U 於甲醇中各個氧化鈣粒子中，機械性賦予壓縮、撞擊、磨 碎及剪切等力道，以破損其氧化鈣粒子之意。本發明中， 使氧化鈣粉末之粉碎進行至其平均粒徑爲當初之値的70% 以下，較佳爲60%以下，特別爲1〜60%之範圍爲止者最 佳。 氧化鈣粉末之粉碎中，可使用等量硏磨機、閉模硏磨 機、及搗碎機等粉碎裝置。其中又以利用等量硏磨機及閉 模硏磨機等之媒體的粉碎裝置爲較佳。媒體之種類、粒徑 ❹ 之選擇，只要可取得所期待之甲氧化鈣分散液之範圍下即 可，並未特別限定。 氧化鈣粉末之粉碎時，甲醇中之氧化鈣量爲3〜40 質量％之範圍者宜。又，粉碎時甲醇之液溫爲1〇〜5(TC之 範圍者宜。氧化鈣粉末之粉碎時間除於此等條件之外，亦 依其粉碎對象之氧化鈣粉末之粒徑、粉碎裝置等而不同， 而只要可取得所期待之甲氧化鈣分散液之範圍即可。 如上述，於甲醇中粉碎該氧化鈣粉末，使氧化鈣粉末 -10 - 200946674 粉碎物與甲醇經由反應之氧化鈣粉碎生成物變成甲氧化鈣 。所得甲氧化鈣之平均粒徑爲該範圍，進一步多半具有 BET比表面積大，總細孔容積亦大，且細孔直徑大之細孔 作成酯交換反應用觸媒者宜。另外，可藉由X線衍射圖案 確定甲氧化鈣的取得。 本發明所使用之甲氧化鈣即使混入氧化鈣及氫氧化鈣 等之鈣化合物亦無妨。鈣化合物之混入可藉由甲氧化鈣之 © X線衍射圖案確定。氧化鈣之混入量係以甲氧化鈣之（ 001)面之衍射波峰強度作爲100時，氧化鈣之（200)面 之衍射波峰相對強度爲40，更佳者爲未超出30之量。氫 氧化鈣之混入量係以甲氧化鈣之（00 1 )面之衍射波峰強 度作成100時，氫氧化鈣之（101)面衍射波峰之相對強 度爲20，更佳者爲未超出1〇之量。 於甲醇中之氧化鈣粉末經由粉碎所得之甲氧化鈣分散 液直接於其狀態下，或進一步以甲醇稀釋作成甲醇稀釋液 ® ，可適用於酯交換反應用觸媒。 本發明脂肪酸甲酯之製造方法中，進行油脂與甲醇之 酯交換反應時’油脂與甲醇之比例爲對於1莫耳油脂而 言’甲醇爲4〜150莫耳者宜、更佳者爲5〜50莫耳之範 圍。甲氧化鈣粉末之量爲對於1 000g油脂而言，以氧化鈣 換算下’爲0.5〜10g之範圍者宜。油脂與甲醇之反應溫 度只要爲30 °C以上即可，一般如：常壓下由3(TC (較佳 者50°C )至甲醇之沸點爲止之範圍。當然，亦可進加壓下 進行反應。 -11 - 200946674 作爲本發明可使用之油脂例者，如：植物油脂、動物 油脂及此等之混合物例。作爲植物油脂之例者，如：米油 、菜子油、胡麻油、大豆油、玉米油、向日葵油、棕櫚油 、棕櫚核油、椰子油、棉子油、花生油、茶油、亞麻仁油 、桐油、大風子油、橄欖油、紅花油、核桃油例。作爲動 物油脂之例者，如：牛脂、馬脂、羊脂、豬脂、雞脂、魚 油、鯨油、海豚油、鮫類肝油例。油脂亦可爲油脂、或廢 食用油。 © 接著，參考圖1，說明本發明所利用之脂肪酸甲酯之 工業生產過程例。 圖1中，分別爲油脂儲存於油脂儲存桶1、甲醇儲存 於甲醇儲存桶2，氧化鈣粉末儲存於氧化鈣粉末儲存桶3 。甲醇儲存桶2內之甲醇與氧化鈣粉末儲存桶3內之氧化 鈣粉末係指，送至粉末裝置4,於粉末裝置4，以甲醇粉 碎氧化鈣粉末，成甲氧化鈣分散液。所生成之甲氧化鈣分 散液送入反應容器5。於反應容器5中，混合由油脂儲存 〇 桶1所送出之油脂與由甲醇儲存桶2所送出之甲醇，以及 甲氧化鈣分散液，使油脂與甲醇進行酯交換反應，生成脂 肪酸甲酯與甘油。 反應容器5內之反應混合物係送入分離塔6，經由比 重分離，分離爲以脂肪酸甲酯爲主成份之輕液部，與以甲 氧化鈣爲主成份之重液部。輕液部係送入蒸餾塔7，使未 反應之甲醇被蒸餾回收。輕液部係接著送入精製柱體8， 精製後，高純度之輕液部（脂肪酸甲酯）送入脂肪酸甲酯 -12- 200946674 儲存桶9,有效作爲生物柴油燃料之用。 [實施例] 實施例中，藉由下述方法，測定平均粒徑、X線衍射 圖案、BET比表面積、及總細孔容積。 [平均粒徑之測定方法]BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a process for producing a fatty acid methyl ester which utilizes a transesterification reaction of a glyceride (fat) with methanol. [Prior Art] Vegetable oil or a waste oil such as waste cooking oil recovered from a food store or a general household is subjected to a transesterification reaction with an aliphatic alcohol, and then used as a fatty acid alkyl ester. In particular, the fatty acid methyl ester obtained by transesterification of fats and oils with methanol is also called biodiesel fuel. Compared with petroleum-based fuels, it is less mixed with sulfur and aromatics, so it is used as a fuel electrode with a small environmental load. Being noticed. As a catalyst used in the transesterification reaction of fats and oils with methanol, an alkali metal hydroxide (sodium hydroxide or potassium hydroxide) having high solubility in oils and fats and aliphatic alcohols is known. However, when an alkali metal hydroxide is used for the catalyst, the fatty acid alkyl ester is mixed with the hydroxide of the alkali metal, so that the fatty acid alkyl ester is washed to remove the alkali metal hydroxide, and it is necessary to carry out The problem of alkali drainage treatment by washing is present. Therefore, as a catalyst for transesterification reaction, a solid catalyst having low solubility for oils and fats and aliphatic alcohols is used. Patent Document 1 describes a method for producing a fatty acid methyl ester of calcium oxide powder or calcium methanol metal powder using a solid catalyst. The calcium oxide powder 200946674 is added to methanol by the activated calcium oxide ("0.05 g activation and 0.005 g activation") described in Figure 6 of Patent Document 1, and is formed into a slurry. After hourly heat reflux, the mixture was filtered and dried to obtain a white powder ("Ca(OH)(OCH3) 0.05g"), and the commercially available calcium sulphate powder ("Ca(OCH3)2 0.005g"). A graph showing the relationship between the reaction time and the yield of fatty acid methyl esters in the production of fatty acid methyl esters in solid catalysts. In the graph of Fig. 6, the yield of fatty acid methyl ester having a reaction time of 3 hours is about 90% highest by "〇.〇5g activation", followed by "0.005g activation", followed by "Ca(OH) (OCH3) 0.05g" is high, and "C a( Ο C Η 3 ) 2 0 · 0 0 5 g" is the lowest. © However, "0.05 g of activated" fatty acid methyl ester was about 30% at 1 hour of reaction time. Further, in Patent Document 1, there is no description of the method for producing calcium sulphate. Non-Patent Document 1 discloses that a calcium alkoxide metal is obtained by dissolving a calcium metal in an alcohol. Patent Document 1: International Publication No. 2007/088702, Non-Patent Document 1: Member of the Chemical Dictionary Collection, "Chemical Dictionary 1", First Edition, Kyoritsu Publishing Co., Ltd., March 30, 35, 〇, p.394 SUMMARY OF THE INVENTION According to the method disclosed in the above Patent Document 1, a fatty acid methyl ester can be produced at a production rate of about 90% at a reaction time of 3 hours. However, in order to mass-produce fatty acid methyl esters in the industry, it is expected that the fatty acid methyl ester will further increase the speed of production and increase the yield. Accordingly, it is an object of the present invention to provide a process for producing a fatty acid methyl ester in a relatively high yield by using a solid catalyst -6-200946674 for a shorter period of time. Another object of the present invention is to provide a novel solid catalyst which exhibits a highly catalytic action for the transesterification reaction of fats and oils with aliphatic alcohols. The present inventors have found that in the solid catalyst for transesterification of fats and oils (i.e., glycerides) with methanol, the average particle diameter is in the range of 1 to ι〇〇μηι, and the BET specific surface area is 1 to 10 m 2 /g. The range, and the total pore volume of the pores having a diameter in the range of 2 to 100 nm is in the range of 0.010 〇 _l 〇 mL / g Ο of the calcium oxide powder, which is pulverized in methanol until the average particle diameter is the original After 70% or less, the calcium pulverized product is reacted with methanol to form calcium sulphate, and the obtained calcium oxide powder having an average particle diameter of 0.10 to ιομπι is compared with the stirring in methanol using the prior art. After the activated calcium oxide, the former clearly shows that the rate of formation of the fatty acid methyl ester becomes extremely fast, and the present invention has been completed. Therefore, in the method for producing a fatty acid methyl ester by transesterifying a glyceride with methanol in the presence of a calcium oxyhydroxide powder, the calcium cerium methanol metal powder has an average particle diameter of 0.10 to ΙΟμπι, The form of the calcium oxide dispersion or the calcium sulphate dispersion is supplied in a form diluted with methanol. The calcium sulphate dispersion has an average particle diameter of 1 to 100 μm, and a BET specific surface area of 1 to 10 m 2 / a range of g, and the calcium oxide powder having a total pore volume of 0.010 to 0.10 mL/g in a pore diameter of 2 to 100 nm is pulverized in methanol so as to have 70% of the average particle diameter of the calcium oxide powder. A method for producing a fatty acid methyl ester characterized by the following method in which calcium oxide powder having an average particle diameter is produced in the methanol. The preferred embodiment of the method for producing a fatty acid methyl ester of the present invention is as follows. 200946674 (1) The BET specific surface area of the calcium oxide powder is in the range of 20 to 60 m 2 /g, and the total pore volume of the pores having a diameter in the range of 2 to 100 nm is in the range of 0.10 to 1.0 mL/g. (2) The total pore volume of the pores of the calcium oxide powder having a diameter in the range of 10 to 1 〇〇 nm is in the range of 0.060 to 0.80 mL/g. (3) The calcium oxide powder is a calcium oxide powder obtained by firing heavy calcium carbonate in an air atmosphere. Further, in the present invention, the calcium cerium oxide powder having an average particle diameter of 0.10 to 10 μm is dispersed in methanol so that the average particle diameter is in the range of 1 to 100 μm, and the BET specific surface area is in the range of 1 to 10 m 2 /g, and the diameter is The calcium oxide powder having a total pore volume of 0.0 10 to 0·1 OmL/g in the pore range of 2 to 100 nm is pulverized in methanol so as to have an average particle diameter of 70% or less of the calcium oxide powder. A calcium sulphate dispersion prepared by forming a calcium methoxide metal powder having a particle size in the methanol. The preferred form of the calcium methoxide dispersion of the present invention is as follows. (1) The BET specific surface area of the calcium oxyhydroxide powder is in the range of 20 to 60 m 2 /g, and the total pore volume of the pores having a diameter in the range of 2 to 100 nm is in the range of 0.01 to 1.0 mL/g (2) The total pore volume of the pores of the calcium oxide powder having a diameter in the range of 10 to 1 〇〇 nm is in the range of 0.060 to 0.80 mL/g. (3) A catalyst for transesterification of glycerides with methanol. By using the method for producing a fatty acid methyl ester of the present invention, when the calcium oxide activated by stirring in methanol of the prior art is used for a solid catalyst, the present invention can be produced in a high yield in a short time. Fatty acid-8 - 200946674 Methyl ester. Further, the calcium oxyhydroxide dispersion of the present invention is a calcium oxide powder obtained by firing heavy calcium carbonate in an atmosphere, and can be used as a raw material, and can be easily and efficiently produced as a high activation catalyst. Therefore, it is extremely suitable for use in a catalyst for transesterification of fats and oils with methanol. [Embodiment] [Best Mode for Carrying Out the Invention] In the method for producing a fatty acid methyl ester of the present invention, as a solid catalyst, a calcium oxide powder is pulverized in methanol, and a calcium pulverized product is reacted with methanol to form a reaction. The calcium oxide powder having an average particle diameter in the range of 0.10 to ΙΟμπι. The average particle diameter of the calcium oxide powder is preferably in the range of 0.50 to 5.0 μπι, more preferably in the range of 1.0 to 3.0 μηη. Further, the BET specific surface area of the calcium oxide powder is preferably in the range of 20 to 60 m 2 /g, more preferably in the range of 20 to 50 m 2 /g, and the total pore volume of the pores having a diameter in the range of 2 to 100 nm is 0.10. A range of ~1.0 mL/g is preferred, and a more preferred range is 〇.1〇~〇.50mL/g. The total pore volume of the pores having a diameter in the range of 10 to 1 〇〇 nm is preferably in the range of 0.060 to 0.80 mL/g, and more preferably in the range of 〜·〇 60 to 0.40 mL/g. Further, the bet specific surface area and pore volume of the calcium oxide powder are those of the calcium oxide powder which is separated and recovered from the calcium oxide dispersion. The calcium oxide powder as a raw material for producing calcium sulphate powder preferably has an average particle diameter of 1 to 1 ΟΟ μηη, preferably 1 to 50 μm. The BET specific surface area is in the range of 1 to 10 m 2 /g. The total pore volume of the pores having a diameter in the range of 2 to 100 nm is in the range of 〇.〇10 to 0.10 mL/g. 200946674 As a raw material of calcium oxide powder, calcium compound (hydrogen) which converts heavy calcium carbonate (calcium limestone by pulverization and classification), light calcium carbonate (such as limestone carbonated), and heat to calcium oxide can be used. Calcium oxide, hydrated lime, etc.) are fired in an atmosphere. Among them, it is preferred from the economic perspective that the heavy calcium carbonate is fired in the atmosphere. Further, the calcium carbonate or the calcium compound may be fired under an inert gas by using a re-fired calcium oxide or quicklime. In the present invention, pulverizing the calcium oxide powder in methanol means 'dissolving U in each of the calcium oxide particles in the methanol, mechanically imparting a force such as compression, impact, grinding and shearing to break the calcium oxide particles. . In the present invention, the pulverization of the calcium oxide powder is carried out until the average particle diameter is 70% or less, preferably 60% or less, particularly preferably 1 to 60%, in the original range. In the pulverization of the calcium oxide powder, a pulverizing device such as an equal amount honing machine, a closed mold honing machine, and a masher can be used. Among them, a pulverizing apparatus using a medium such as an equal honing machine and a closed honing machine is preferable. The type of the medium and the particle size ❹ are not particularly limited as long as the desired calcium sulphate dispersion can be obtained. When the calcium oxide powder is pulverized, the amount of calcium oxide in the methanol is preferably in the range of 3 to 40% by mass. Moreover, the liquid temperature of methanol at the time of pulverization is 1 〇 to 5 (the range of TC is preferable. In addition to the conditions such as the pulverization time of the calcium oxide powder, the particle size of the calcium oxide powder to be pulverized, the pulverization apparatus, etc. However, as long as the desired range of the calcium sulphate dispersion can be obtained, the calcium oxide powder is pulverized in methanol as described above, and the pulverized material of the calcium oxide powder - 10, 2009, 674 and methanol is pulverized by the reaction of calcium oxide. The product becomes calcium sulphate. The average particle diameter of the obtained calcium sulphate is in this range, and most of the pores having a large BET specific surface area and a large pore volume are large, and the pores having a large pore diameter are used as a catalyst for transesterification reaction. In addition, the calcium sulphate can be obtained by the X-ray diffraction pattern. The calcium sulphate used in the present invention may be mixed with a calcium compound such as calcium oxide or calcium hydroxide, and the calcium compound may be mixed by methoxylation. The X-ray diffraction pattern of calcium is determined. The amount of calcium oxide mixed is based on the diffraction peak intensity of the (001) plane of calcium oxide as 100, and the relative intensity of the diffraction peak of the (200) plane of calcium oxide is 4. 0, more preferably, the amount is not exceeded by 30. The amount of calcium hydroxide mixed is the relative intensity of the (101) plane diffraction peak of the calcium hydroxide when the intensity of the diffraction peak of the (00 1 ) plane of the calcium oxide is 100. It is 20, and more preferably it is not more than 1 。. The calcium oxide powder in methanol is directly diluted in the state by the pulverized calcium sulphate dispersion, or further diluted with methanol to form a methanol diluent®, which is suitable for In the method for producing a transesterification reaction, in the method for producing a fatty acid methyl ester according to the present invention, when the transesterification reaction between the oil and the fat is carried out, the ratio of the fat to the methanol is preferably 4 to 150 mol for the 1 mol of the grease. More preferably, it is in the range of 5 to 50 moles. The amount of calcium sulphate powder is preferably in the range of 0.5 to 10 g in terms of calcium oxide for 1 000 g of fat and oil. The reaction temperature of the oil and the methanol is only It can be above 30 °C, generally as the range from 3 (TC (preferably 50 ° C) to the boiling point of methanol under normal pressure. Of course, it can also be reacted under pressure. -11 - 200946674 as this Inventives of fats that can be used, such as: Examples of oils, animal fats and oils, and mixtures of such oils, such as rice oil, rapeseed oil, flax oil, soybean oil, corn oil, sunflower oil, palm oil, palm kernel oil, coconut oil, cottonseed oil. , peanut oil, tea oil, linseed oil, tung oil, wind oil, olive oil, safflower oil, walnut oil. As an example of animal fats, such as: tallow, horse fat, sheep fat, pig fat, chicken fat, fish oil Examples of whale oil, dolphin oil, and scorpion liver oil. The fats and oils may be fats and oils, or waste cooking oil. © Next, an industrial production process example of the fatty acid methyl ester used in the present invention will be described with reference to Fig. 1. The grease is stored in the grease storage tank 1, the methanol is stored in the methanol storage tank 2, and the calcium oxide powder is stored in the calcium oxide powder storage tank 3 . The calcium oxide powder in the methanol and calcium oxide powder storage tank 3 in the methanol storage tank 2 is sent to the powder device 4, and in the powder device 4, the calcium oxide powder is powdered with methanol to form a calcium methoxide dispersion. The generated calcium oxide dispersion is sent to the reaction vessel 5. In the reaction vessel 5, the fat and oil sent from the grease storage tank 1 and the methanol sent from the methanol storage tank 2, and the calcium oxide dispersion are mixed to convert the fat and oil with methanol to form fatty acid methyl ester and glycerin. . The reaction mixture in the reaction vessel 5 is sent to the separation column 6, and separated by a specific gravity to be separated into a light liquid portion mainly composed of fatty acid methyl ester and a heavy liquid portion mainly composed of calcium oxide. The light liquid portion is sent to the distillation column 7, and the unreacted methanol is distilled and recovered. The light liquid portion is then sent to the purified column 8, and after purification, the high-purity light liquid portion (fatty acid methyl ester) is sent to the fatty acid methyl ester -12-200946674 storage tank 9, which is effectively used as a biodiesel fuel. [Examples] In the examples, the average particle diameter, the X-ray diffraction pattern, the BET specific surface area, and the total pore volume were measured by the following methods. [Method for measuring average particle size]
© 利用雷射衍射式粒度分佈測定裝置（MICROTRAC HRA9 3 02-X1 00、日機裝（股份）製，測定之）。 [X線衍射圖案之測定方法]© Laser diffraction type particle size distribution measuring device (measured by MICROTRAC HRA9 3 02-X1 00, manufactured by Nikkiso Co., Ltd.). [Method for Measuring X-ray Diffraction Pattern]
利用粉末X線衍射裝置（Rigaku RINT2100Ultima/PC (股份）Rigaku 製、X 線源：Cu-Κα )，於 50kV、30mA 之條件下進行測定。 ® [BET比表面積及總細孔容積之測定方法] 利用全自動氣體吸附量測定裝置（Autosorb-3B、 Quantachrome (股份）製），藉由氮氣吸附法進行測定。 總細孔容積係由氮氣之脫離等溫線藉由B J Η法，算出累積 細孔容積曲線，由該曲線求出直徑2〜l〇〇nm之細孔，及 直徑10〜lOOnm之細孔的總細孔容積。 [實施例1] (1)甲氧化鈣分散液之製造 -13- 200946674 於大氣雰圍下燒成重質碳酸鈣，製造之氧化鈣（宇部 materials (股份）製生石灰）之粉末3.75g (平均粒徑： 5.4μιη、BET比表面積：2m2/g、直徑2〜100nm之細孔的 總細孔容積：〇.〇14mL/g、X線衍射圖案：參考圖2)藉由 閉模硏磨機（加入平均粒徑3mm之二氧化锆製球粒）， 室溫下，於30g甲醇中進行2小時粉碎處理，製造分散液 。所得之分散液中粒子之平均粒徑爲1.6μιη。 室溫下，將所得分散液進行減壓乾燥，取得粉末。圖 © 3顯示所得粉末之X線衍射圖案，與甲氧化鈣之X線衍射 圖案一致，確定所得粉末爲甲氧化鈣粉末。亦即，使大氣 雰圍下藉由燒成重質碳酸鈣之氧化鈣粉末於甲醇中粉碎處 理後，氧化鈣粉碎生成物變成甲氧化鈣，確定生成甲氧化 鈣分散液。又，X線衍射圖案中，作爲甲氧化鈣以外之X 線衍生波峰者，僅出現相當於氫氧化鈣之（101)面之衍 射波峰。惟，使甲氧化鈣之（00 1 )面之衍射波峰強度作 爲100時，氫氧化鈣之（101)面衍射波峰之相對強度爲5 〇 。另外，甲氧化鈣粉末之BET比表面積爲31.3 m2/g、直徑 2〜lOOnm之細孔的總細孔容積爲 〇.185mL/g、直徑10〜 lOOnm之細孔的總細孔容積爲〇.160mL/g。 (2)脂肪酸甲酯的製造 於具備攪拌機及迴流冷卻機之容量lOOOmL之可分離 燒瓶中，置入750g菜子油，133.6g甲醇，使液溫維持於 64°C後，與上述（1)同法，投入33.75g另途調製之甲氧 -14- 200946674 化鈣分散液（作爲氧化鈣換算之觸媒量者，對於菜子油 1 000g而言，爲5.0g)，開始進行反應。 由反應開始，每30分鐘採取一部份可分離燒瓶內之 反應混合物，藉由氣體層析法分析脂肪酸甲酯、甘油酯、 二甘油酯、及單甘油酯之量，使此等4成份合計量爲100 時之脂肪酸甲酯比例作成脂肪酸甲酯之產率（％)進行算 出。其結果，脂肪酸甲酯之產率於反應時間0.5小時下爲 © 17.4%，於1小時下爲53.8%，於1.5小時下爲93.5%，於 2小時下爲9 7.0 %，3小時爲9 9.8 %。 [實施例2] (1)甲氧化鈣分散液之製造 除使閉模硏磨機之粉碎處理時間變更爲5分鐘之外， 與實施例1同法製造分散液。所得分散液中之粒子平均粒 徑爲2.9 μ m。 於室溫下使所得分散液進行減壓乾燥後取得粉末。所 得粉末之X線衍射圖案如圖4所示，與甲氧化鈣之X線 衍射圖案爲相同，所得之粉末爲甲氧化鈣粉末，亦即，該 分散液被確定爲甲氧化鈣分散液。又，X線衍射圖案中， 稍出現相當於氧化鈣之（ 200 )面與氫氧化鈣（1〇1)面之 衍射波峰。使甲氧化鈣之（〇〇1)面衍射波峰之強度作爲 100時，相當於氧化鈣之（200 )面衍射波峰之相對強度爲 25，相當於氫氧化鈣之（101)面之衍射波峰的相對強度 爲6。另外，甲氧化鈣粉末之BET比表面積爲26.4m2/g、 -15- 200946674 直徑2〜100nm之細孔的總細孔容積爲0.150mL/g、直徑 10〜lOOnm之細孔的總細孔容積爲0.091mL/g。 (2)脂肪酸甲酯之製造 與上述（1)同法使用3 3.75g之另途調製之甲氧化鈣 分散液，取代甲氧化鈣分散液之外，與實施例1同法進行 反應。其結果，脂肪酸甲酯之產率於反應時間0.5小時下 ，爲2 6 · 1 %、1小時爲7 4.8 %、1 · 5小時爲9 5 · 0 %、2小時 © 爲 9 7 . 1 %、3 小時爲 9 9.6 °/〇。 [比較例1] 依該專利文獻1 (國際公開第2007/088702號手冊） 所載之方法爲基準，利用下述方法所調製之活化氧化鈣分 散液，製造脂肪酸甲酯。 (1)活化之氧化鈣分散液之製造 Ο 將相同於實施例1所使用之氧化鈣粉末3.75g，於室 溫下，甲醇15 Og中經由磁力攪拌器進行2小時攪拌，製 造活化之氧化鈣分散液。所得之分散液中粒子之平均粒徑 爲 2.7 μιη。 室溫下使所得之分散液進行減壓乾燥，取得粉末。所 得粉末之X線衍射圖案如圖5所示，與原料之氧化鈣粉末 之X線衍射圖案（圖2)爲相同者，未出現源於甲氧化鈣 之衍射波峰。又，該活化之氧化鈣粉末之BET比表面積爲 -16- 200946674 17.9m2/g、直徑 2〜l〇〇nm之細孔的總細孔容積爲 0.080mL/g、直徑 1〇〜l〇〇nm之細孔的總細孔容積爲 0.045mL/g ° (2)脂肪酸甲酯之製造 使用相同於該（1)之另途調製之氧化鈣分散液 153.75g(作爲觸媒量者，對於lOOOg菜子油而言，爲 ® 5.0g )，取代甲氧化鈣分散液，使甲醇量變更爲13.6g之 外，與實施例1同法，進行反應。其結果，脂肪酸甲酯之 產率於反應時間0.5小時爲1 0.1 %、1小時爲1 5.6%、1. 5 小時爲2 0 · 7 %、2小時爲3 7.7 %、3小時爲5 2.4 %。 [比較例2] (1)氧化鈣分散液之調製 未以磁力攪拌器攪拌相同於實施例1所使用之氧化鈣 ® 粉末3.75，直接分散於3 0g甲醇中，調製氧化鈣分散液。 . (2)脂肪酸甲酯之製造 使用該（1)所調製之氧化鈣分散液33.75g(作爲觸 媒量者，對於l〇〇〇g之菜子油而言，爲5.0g)，取代甲氧 化鈣分散液之外，與實施例1同法進行反應。其結果，脂 肪酸甲酯之產率於反應時間〇. 5小時爲0%、1小時爲0% 、1 · 5小時爲0 · 8 %、2小時爲1 . 9 %、3小時爲6 · 0 %。 圖6顯示，實施例1、實施例2、比較例1及比較例2 -17- 200946674 之脂肪酸甲酯產率之經時的變化。 由圖6之結果顯示，使用本發明之甲氧化鈣分散液作 爲油脂與甲醇之酯交換反應用觸媒時，脂肪酸甲酯之產率 於反應時間1小時爲40%以上、反應時間2小時達90%以 上（實施例1、2)，相較於使用活化之氧化鈣分散液時（ 比較例1)、使用作爲甲氧化鈣製造原料使用之氧化鈣粉 末時（比較例2)後，前者脂肪酸甲酯之生成速度極快速 ，可使脂肪酸甲酯於短時間內，以高產率製造。亦即，本 © 發明之甲氧化鈣分散液其作爲油脂與甲醇之酯交換反應用 觸媒之活性爲極高者。 [實施例3] (1)甲氧化鈣分散液之製造 除變更氧化鈣粉末之量爲2.63 g之外，與實施例1同 法製造分散液。所得分散液粒子之平均粒徑爲1.3 μπι。 室溫下使所得之分散液進行減壓乾燥，取得粉末。所 〇 得粉末之X線衍射圖案與實施例2之X線衍射圖案爲相 同者，所得之粉末爲甲氧化鈣粉末，亦即，確定該分散液 爲甲氧化鈣分散液。另外，甲氧化鈣粉末之BET比表面積 爲40_8m2/g、直徑2〜lOOnm之細孔的總細孔容積爲 0.23mL/g、直徑 1〇〜l〇〇nm之細孔的總細孔容積爲 0.1 87mL/g。 (2)脂肪酸甲酯之製造 -18- 200946674 使用相同於該（i)之另途調製之甲氧化鈣分散液 32.63g(作爲氧化鈣換算之觸媒量者，對於1000g菜子油 而言，爲3.5g)，取代甲氧化鈣分散液之外，與實施例1 同法進行反應。其結果，脂肪酸甲酯之產率於反應時間 0.5小時爲20.0%、1小時爲59.2%、1 .5小時爲87.9%、2 小時爲9 6.9 %、3小時爲9 9.1 %。 © [實施例4] (1)甲氧化鈣分散液之調製 除將氧化鈣粉末之量變更爲1.88g之外，與實施例1 同法，調製分散液。所得之分散液中粒子之平均粒徑爲 1 . 3 μιη 〇 室溫下將該分散液進行減壓乾燥，取得粉末。所得粉 末之X線衍射圖案與實施例1之X線衍射圖案爲相同， 所得粉末爲甲氧化鈣粉末，亦即，該分散液被確定爲甲氧 ® 化鈣分散液。另外，甲氧化鈣粉末之BET比表面積爲 42.7m2/g、直徑 2〜lOOnm之細孔的總細孔容積爲 0.3 09mL/g、直徑 10〜100nm之細孔的總細孔容積爲 0.2 5 6mL/g 〇 (2 )脂肪酸甲酯之製造 使用與該（1)相同之另途調製之甲氧化鈣分散液 31.88g(作爲氧化鈣換算之觸媒量者，對於1000g之菜子 油而言，爲2.5g)，取代甲氧化鈣分散液之外，與實施例 -19- 200946674 1同法進行反應。其結果’脂肪酸甲酯之產率於反應時間 0.5 小時爲 16.8%、1 小時爲 41.0%、1.5 小時爲 82.1°/。、2 小時爲9 3 · 3 %、3小時爲9 8 · 3 %。 圖7顯示，實施例1、實施例3及實施例4之脂肪酸 甲酯產率之經時的變化。 由圖7之結果證明，對於1000g之菜子油之甲氧化鈣 使用量以氧化鈣換算量爲5.0g時（實施例1)，爲3.5g 時（實施例3)，爲2.5g時（實施例4)之任意情況下， 0 脂肪酸甲酯之產率均於反應時間1小時爲40%以上，反應 時間2小時達90%以上。 【圖式簡單說明】 [圖1]代表假設本發明脂肪酸甲酯之製造方法工業上 實施之系統圖之例。 [圖2]代表實施例1作爲甲氧化鈣之鈣原料使用之氧 化鈣粉末之X線衍射圖案。 © [圖3]代表實施例1所得之甲氧化鈣粉末之X線衍射 圖案。 [圖4]代表實施例2所得之甲氧化鈣粉末之X線衍射 圖案。 [圖5]代表比較例i所得之活化氧化鈣粉末之X線衍 射圖案。 [圖6 ]代表實施例1、實施例2、比較例1及比較例2 中脂肪酸甲酯產率之經時的變化曲線圖。 -20- 200946674 [圖7]代表實施例1、實施例3及實施例4中脂肪酸甲 酯之產的經時的變化曲線圖。 【主要元件符號說明】 1 =油脂儲存桶 2 :甲醇儲存桶 3:氧化鈣粉末儲存桶 Ο 4 :粉碎裝置 5 :反應容器 6 :分離塔 7 :蒸餾塔 8 :精製柱體 9 :脂肪酸甲酯儲存桶The measurement was carried out under the conditions of 50 kV and 30 mA by a powder X-ray diffractometer (Rigaku RINT 2100 Ultima/PC (share) Rigaku, X-ray source: Cu-Κα). ® [Measurement Method of BET Specific Surface Area and Total Pore Volume] The measurement was carried out by a nitrogen gas adsorption method using a fully automatic gas adsorption amount measuring device (Autosorb-3B, manufactured by Quantachrome Co., Ltd.). The total pore volume is calculated from the desorption isotherm of nitrogen by the BJ method, and the cumulative pore volume curve is calculated. From the curve, the pores having a diameter of 2 to 10 nm and the pores having a diameter of 10 to 100 nm are obtained. Total pore volume. [Example 1] (1) Production of calcium sulphate dispersion - 13-200946674 A powder of 3.75 g (average granules) of calcium oxide (manufactured by Ube Materials) was produced by firing heavy calcium carbonate in an atmosphere. Diameter: 5.4 μιη, BET specific surface area: 2 m 2 /g, total pore volume of pores having a diameter of 2 to 100 nm: 〇.〇14 mL/g, X-ray diffraction pattern: refer to FIG. 2) by a closed mold honing machine ( A granule of zirconia having an average particle diameter of 3 mm was added, and the mixture was pulverized in 30 g of methanol at room temperature for 2 hours to prepare a dispersion. The average particle diameter of the particles in the obtained dispersion was 1.6 μm. The obtained dispersion liquid was dried under reduced pressure at room temperature to obtain a powder. Fig. 3 shows the X-ray diffraction pattern of the obtained powder, which is consistent with the X-ray diffraction pattern of calcium oxide, and the obtained powder was determined to be calcium oxychloride powder. In other words, after the calcium oxide powder of the calcined heavy calcium carbonate is pulverized in methanol in the atmosphere, the calcium pulverized product is converted into calcium sulphate, and the calcium sulphate dispersion is determined to be formed. Further, in the X-ray diffraction pattern, as the X-ray-derived peak other than calcium sulphate, only the diffraction peak corresponding to the (101) plane of calcium hydroxide appears. However, when the diffraction peak intensity of the (00 1 ) plane of calcium oxide is set to 100, the relative intensity of the (101) plane diffraction peak of calcium hydroxide is 5 〇. In addition, the total pore volume of the pores of the calcium oxide powder having a BET specific surface area of 31.3 m 2 /g and a diameter of 2 to 100 nm is 185.185 mL/g, and the pores having a diameter of 10 to 100 nm are 〇. 160 mL / g. (2) Production of fatty acid methyl ester In a separable flask having a capacity of 1000 mL of a stirrer and a reflux condenser, 750 g of rapeseed oil and 133.6 g of methanol were placed, and the liquid temperature was maintained at 64 ° C, and then (1) In the method, 33.75 g of a methoxy-14-200946674 calcium dispersion (as a catalyst for conversion of calcium oxide, 5.0 g for 1 000 g of rapeseed oil) was introduced, and the reaction was started. Starting from the reaction, take a part of the reaction mixture in the separable flask every 30 minutes, and analyze the amount of fatty acid methyl ester, glyceride, diglyceride, and monoglyceride by gas chromatography to make the total of these four components The yield (%) of the fatty acid methyl ester ratio when the amount is 100 is calculated. As a result, the yield of the fatty acid methyl ester was 17.4% at a reaction time of 0.5 hour, 53.8% at 1 hour, 93.5% at 1.5 hours, 97.0% at 2 hours, and 9 9.8 at 3 hours. %. [Example 2] (1) Production of calcium oxide dispersion liquid A dispersion liquid was produced in the same manner as in Example 1 except that the pulverization treatment time of the closed mold honing machine was changed to 5 minutes. The average particle diameter of the particles in the obtained dispersion was 2.9 μm. The obtained dispersion liquid was dried under reduced pressure at room temperature to obtain a powder. The X-ray diffraction pattern of the obtained powder was as shown in Fig. 4, and the X-ray diffraction pattern of calcium oxide was the same, and the obtained powder was calcium sulphate powder, i.e., the dispersion was identified as a calcium sulphate dispersion. Further, in the X-ray diffraction pattern, a diffraction peak corresponding to the (200) plane of calcium oxide and the surface of calcium hydroxide (1〇1) slightly appeared. When the intensity of the (?1) plane diffraction peak of calcium oxide is taken as 100, the relative intensity of the (200) plane diffraction peak corresponding to calcium oxide is 25, which corresponds to the diffraction peak of the (101) plane of calcium hydroxide. The relative intensity is 6. In addition, the total pore volume of the pores of the pores having a BET specific surface area of 26.4 m 2 /g, -15-200946674 diameter of 2 to 100 nm of the calcium peroxide powder of 0.150 mL/g and a diameter of 10 to 100 nm It was 0.091 mL/g. (2) Production of fatty acid methyl ester The same procedure as in Example 1 was carried out in the same manner as in the above (1), using a 3.75 g of a calcium sulphate dispersion prepared in the same manner as the calcium oxyhydroxide dispersion. As a result, the yield of the fatty acid methyl ester was 2 6 · 1 % at a reaction time of 0.5 hours, 7 4.8 % at 1 hour, 9 5 · 0 % at 1.5 hours, and 2 hours © 97.1 %. 3 hours is 9 9.6 ° / 〇. [Comparative Example 1] A fatty acid methyl ester was produced by the activated calcium oxide dispersion prepared by the following method based on the method described in Patent Document 1 (International Publication No. 2007/088702). (1) Production of Activated Calcium Oxide Dispersion 3.7 3.75 g of the calcium oxide powder used in the same manner as in Example 1 was stirred at room temperature for 15 hours in a magnetic stirrer for 15 hours to prepare activated calcium oxide. Dispersions. The average particle diameter of the particles in the obtained dispersion was 2.7 μηη. The obtained dispersion liquid was dried under reduced pressure at room temperature to obtain a powder. The X-ray diffraction pattern of the obtained powder was as shown in Fig. 5, and the X-ray diffraction pattern (Fig. 2) of the calcium oxide powder of the raw material was the same, and no diffraction peak derived from calcium oxide was observed. Further, the activated calcium oxide powder has a BET specific surface area of -16 to 200946674, 17.9 m 2 /g, and a total pore volume of pores of 2 to 10 nm in diameter of 0.080 mL/g, and a diameter of 1 〇 to 1 〇〇 The total pore volume of the pores of nm is 0.045 mL/g ° (2) The production of fatty acid methyl ester is 153.75 g of the calcium oxide dispersion prepared in the same manner as in (1) (as a catalyst amount, for 1000 g) In the case of rapeseed oil, it was 5.0 g), and the reaction was carried out in the same manner as in Example 1 except that the calcium peroxide dispersion was replaced with the amount of methanol changed to 13.6 g. As a result, the yield of the fatty acid methyl ester was 10.1% in the reaction time of 0.5 hour, 15.6% in 1 hour, 2 0 · 7 % in 1.5 hours, 37.7 % in 2 hours, and 5 2.4 % in 3 hours. . [Comparative Example 2] (1) Preparation of Calcium Oxide Dispersion The calcium oxide dispersion was used in the same manner as in Example 1 except that the calcium oxide powder 3.75 used in Example 1 was stirred with a magnetic stirrer. (2) Production of fatty acid methyl ester 33.75 g of the calcium oxide dispersion prepared by the above (1) (as a catalyst amount, 5.0 g for l〇〇〇g rapeseed oil), substituted for methoxy oxidation The reaction was carried out in the same manner as in Example 1 except for the calcium dispersion. As a result, the yield of the fatty acid methyl ester is 0% in 5 hours, 0% in 1 hour, 0. 8 % in 1 hour, 1.9% in 2 hours, and 6 · 0 in 3 hours. %. Figure 6 shows the change over time of the yield of fatty acid methyl esters of Example 1, Example 2, Comparative Example 1, and Comparative Example 2-17-200946674. The result of FIG. 6 shows that when the calcium sulphate dispersion of the present invention is used as a catalyst for transesterification of fats and oils with methanol, the yield of fatty acid methyl ester is 40% or more at a reaction time of 1 hour, and the reaction time is 2 hours. 90% or more (Examples 1 and 2), the former fatty acid was used when calcium oxide powder used as a raw material for calcium sulphate production (Comparative Example 2) was used as compared with the case of using activated calcium oxide dispersion (Comparative Example 1) The formation rate of the methyl ester is extremely fast, and the fatty acid methyl ester can be produced in a high yield in a short time. That is, the calcium peroxide dispersion of the present invention is extremely high in activity as a catalyst for transesterification of fats and oils with methanol. [Example 3] (1) Production of calcium oxide dispersion liquid A dispersion liquid was produced in the same manner as in Example 1 except that the amount of the calcium oxide powder was changed to 2.63 g. The obtained dispersion liquid particles had an average particle diameter of 1.3 μm. The obtained dispersion liquid was dried under reduced pressure at room temperature to obtain a powder. The X-ray diffraction pattern of the obtained powder was the same as that of the X-ray diffraction pattern of Example 2, and the obtained powder was calcium sulphate powder, i.e., the dispersion was determined to be a calcium sulphate dispersion. Further, the total pore volume of the pores of the calcium oxide powder having a BET specific surface area of 40 to 8 m 2 /g and a diameter of 2 to 100 nm is 0.23 mL/g, and the pores having a diameter of 1 〇 to 1 〇〇 nm are 0.1 87 mL/g. (2) Manufacture of fatty acid methyl ester -18- 200946674 32.63 g of calcium sulphate dispersion prepared in the same manner as the above (i) (as a catalyst for conversion of calcium oxide, for 1000 g of rapeseed oil, 3.5 g), in the same manner as in Example 1, except that the calcium oxyhydroxide dispersion was replaced. As a result, the yield of the fatty acid methyl ester was 20.0% at a reaction time of 0.5 hours, 59.2% at 1 hour, 87.9% at 1.5 hours, 96.9% at 2 hours, and 99.1% at 3 hours. [Example 4] (1) Preparation of calcium oxide dispersion liquid The dispersion liquid was prepared in the same manner as in Example 1 except that the amount of the calcium oxide powder was changed to 1.88 g. The average particle diameter of the particles in the obtained dispersion was 1. 3 μm 〇 The dispersion was dried under reduced pressure at room temperature to obtain a powder. The X-ray diffraction pattern of the obtained powder was the same as that of the X-ray diffraction pattern of Example 1, and the obtained powder was calcium sulphate powder, that is, the dispersion was identified as a methoxycalcium dispersion. Further, the total pore volume of the pores having a BET specific surface area of 42.7 m 2 /g, a diameter of 2 to 100 nm, and a total pore volume of 0.309 mL/g and a diameter of 10 to 100 nm of the calcium oxide powder is 0.256 mL. /g 〇(2) The fatty acid methyl ester is produced by using 31.88 g of a calcium sulphate dispersion prepared in the same manner as the above (1) (as a catalyst amount in terms of calcium oxide, for 1000 g of rapeseed oil, 2.5 g), in place of the calcium methoxide dispersion, was reacted in the same manner as in Example-19-200946674. As a result, the yield of the fatty acid methyl ester was 16.8% at 0.5 hours, 41.0% at 1 hour, and 82.1 ° at 1.5 hours. 2, 9 3 · 3 % for 2 hours and 9 8 · 3 % for 3 hours. Fig. 7 shows the change with time of the yield of the fatty acid methyl esters of Example 1, Example 3 and Example 4. From the results of Fig. 7, it was confirmed that the amount of calcium oxide used in 1000 g of rapeseed oil was 5.0 g in the amount of calcium oxide (Example 1), and when it was 3.5 g (Example 3), it was 2.5 g (Example) 4) In any case, the yield of the 0 fatty acid methyl ester is 40% or more at 1 hour in the reaction time, and the reaction time is over 90% in 2 hours. BRIEF DESCRIPTION OF THE DRAWINGS [Fig. 1] shows an example of a system diagram which is assumed to be industrially carried out by a method for producing a fatty acid methyl ester of the present invention. Fig. 2 is an X-ray diffraction pattern representing a calcium oxide powder used in Example 1 as a calcium raw material of calcium sulphate. © [Fig. 3] An X-ray diffraction pattern representing the calcium oxyhydroxide powder obtained in Example 1. Fig. 4 is an X-ray diffraction pattern representing the calcium oxyhydroxide powder obtained in Example 2. [Fig. 5] An X-ray diffraction pattern representing the activated calcium oxide powder obtained in Comparative Example i. Fig. 6 is a graph showing changes over time in yield of fatty acid methyl esters in Example 1, Example 2, Comparative Example 1, and Comparative Example 2. -20- 200946674 [Fig. 7] A graph showing changes over time in the production of fatty acid methyl esters in Example 1, Example 3 and Example 4. [Main component symbol description] 1 = Grease storage tank 2: Methanol storage tank 3: Calcium oxide powder storage tank Ο 4: Crushing device 5: Reaction vessel 6: Separation tower 7: Distillation column 8: Purified column 9: Fatty acid methyl ester Storage bucket
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