200925263 九、發明說明： 【發明所屬之技術領域】 _ 本發明係有關於一種製造生質柴油之逆向流動酯化反 應器及其方法，特別是有關於一種具有提供高溫高壓環境 之s旨化反應塔，不需額外加入添加劑而進行轉s旨化反應製 成生質柴油的設備與方法。 【先前技術】 隨著國際上開發中國家經濟成長所需之大量能源需 ❹ 求，衍生因能源供需失衡導致的國際原油價格高漲、京都 議定書生效後全球溫室氣體減量的發展趨勢，促使各國政 府積極開發生質能等再生替代性能源，生質柴油是生質能 的一種，為「使用動植物油脂或廢食用油之脂肪酸，於觸 媒存在下，與醇類反應產生酯類燃料」，生質柴油能夠有 效減少廢棄油脂的數量，將廢棄物成為有用的燃料，生質 柴油為取代石化燃料的重要再生與環保燃料之一。 q 在先前技術中，比較於傳統的使用催化劑轉酯化反應 製程，使用超臨界醇類進行油脂轉酯化反應的主要優點為 不需使用催化劑、轉酯化程度高、可簡化後段的純化製程 與甘油回收品質佳，雖然利用超臨界醇類進行生質柴油的 製備已經被視為是下一代的新興製造技術，但是先前的研 究指出若欲在10分鐘内達到99百分比以上的轉化率，在 壓力30百萬帕斯卡下，必須給予相當高的操作溫度，其操 作溫度高達攝氏400度，在如此高的操作溫度下，轉酯化 5 200925263 反應的副產物偏多，因此如何降低反應溫度是一個亟需解 決的問題，若欲降低反應溫度，多採用的手段包括加入輔 溶劑，如二氧化碳或丙烷等，或是開發固體催化劑等；也 因為醇與酸的酯化反應係平衡反應，因此轉化率受到溫度 與壓力的影響極大，添加大量過量的醇類雖然可以稍微降 低操作溫度與壓力，並可以獲得較高的轉化率，但是必須 消耗大量的醇類，造成不經濟與環境的負擔。 然而，先前技術具有無法避免之缺點，就是必須使用 ❹ 添加劑、製程難度高、製程控制不易、對環境造成負擔與 製造成本高等缺失。 【發明内容】 有鑑於此，為解決上述問題，本發明係提供一種製造 生質柴油之逆向流動酯化反應器及其方法，將含有脂肪酸 之原料與含有醇類之原料放入逆向流動酯化反應器内，可 不需加入任何添加劑，且操作溫度較低，經過自旨化反應塔 ❹ 内進行轉酯化反應，製成生成物生質柴油。 為達上述目的，本發明所提供之一種製造生質柴油之 逆向流動酯化反應器及其方法，由於脂肪酸的分子量僅油 脂的1/3左右，因此含脂肪酸的原料與醇類的雙成份系統 之臨界軌跡的溫度與壓力將遠低於油脂與醇類的雙成份系 統，這表示脂肪酸與醇類可以在更低的溫度與壓力下成為 單一均相，所以使用脂肪酸當作原料，則可以在更低的反 應條件下進行單一均相的反應，將含有脂肪酸之原料與含 200925263 有醇類之原料加熱至操作溫度後放入逆向流動酯化反應器 内’在逆向流動酯化反應器中酯化反應塔給於持續的高溫 • 與愚壓’進行轉酯化反應’並將其副產物醇類與水不斷地 藉由汽液分離裝置分離後排出逆向流動酯化反應器，藉由 不斷地排出副產物醇類與水，迫使轉酯化反應不斷地正向 反應，製成生成物生質柴油。 本發明之有益功效為提供製造生質柴油之逆向流動酯 化反應益及其方法’本流動酯化反應器使用含有脂肪酸之 》 原料與含有醇類之原料’不使用任何添加劑，提高轉酯化 反應之轉化率，為綠色環保的製程，不會造成環境的負擔， 具有製程簡單、製程控制容易與降低製造成本等諸多功效。 【實施方式】 有關本發明的特徵與實作，茲配合圖示作最佳實施例 泮細况明如下。 請參照圖1所示，其為本發明製造生質柴油（Bi〇-dies _ el、Fatty Acid Methyl Ester、FAME)之逆向流動酯化反 應器 1 ’ S旨化反應塔（Packed Reactor、Esterification Tower)l〇〇為桶狀金屬中空槽體，可承受4〇百萬帕斯卡（Mp a)以下之氣壓，g旨化反應塔（Esterification Reactor) 100 内有篩板（Sieve Tray)103，用於使進入酯化反應塔（Ester ification Reactor)100内之原料充份混合，醋化反應塔 (Esterification Reactor)100 内也可設置層板（Laminate d Plates)、耐高溫填充子（Fi 1 ler)或不銹鋼網（Steel Mesh) 7 200925263 裝置等’酯化反應塔（Esterification Reactor)100具有 壓力控制裝置（Pressure Control ler)101，能控制酯化反 應塔（Esterification Reactor)l〇〇内之壓力，維持轉醋 化反應（Esterification)製程所需的壓力，酯化反應塔（es terification Reactor)100 也具有溫度控制裝置（Temper ature Controller)102’ 能控制酯化反應塔（Esterificat ionReactor)100内之溫度，維持轉酯化反應（Esterificat ion)製程所需的溫度；第一進料裝置11〇連接酯化反應塔 ❹ (Esterification Reactor)100 上端，第一進料裝置 11〇 具有第一加壓進料手段113加壓幫浦（Pump)，用以加壓由 第一進料裝置110進入醋化反應塔（Esterificat ion React or)100之原料’第一進料裝置110與醋化反應塔（Packed Reactor、Esterification Tower)100 連接處有流量控制 裝置（Flow Control ler) 112 ’用以控制由第一進料裝置 110進入酯化反應塔（Esterification Reactor)l00之原料 ❹ 流量’第一進料裝置110具有加熱溫度控制裝置（Heater and Temperature Controller)lll，用以加熱由第一進料 裝置 110 進入S旨化反應塔（Esterification Reactor)100 之原料；第二進料裝置120連接酯化反應塔（Esterifi cation Reactor) 100下端，第二進料裝置120具有第二加 壓進料手段122加壓幫浦（Pump)，用以加壓由第二進料裝 置 120 進入酯化反應塔（Esterification Reactor)100 之 原料，第二進料裝置120與S旨化反應塔（Esterification 8 200925263200925263 IX. Description of the invention: [Technical field to which the invention pertains] The present invention relates to a reverse flow esterification reactor for producing biodiesel and a method thereof, and more particularly to a reaction for providing a high temperature and high pressure environment The tower is an apparatus and method for producing biodiesel without additional additives. [Prior Art] With the large amount of energy demand required for the economic growth of developing countries in the world, the international crude oil price caused by the imbalance of energy supply and demand and the global greenhouse gas reduction after the entry into force of the Kyoto Protocol have prompted governments to actively The development of biomass energy and other renewable alternative energy sources, biodiesel is a kind of biomass energy, which is "the use of fatty acids in animal and vegetable oils or waste cooking oils, in the presence of catalysts, reacts with alcohols to produce ester fuels." Diesel can effectively reduce the amount of waste oil and make waste a useful fuel. Biodiesel is one of the important renewable and environmentally friendly fuels to replace fossil fuels. q In the prior art, compared with the conventional catalyst-transesterification process, the main advantage of using the supercritical alcohol for the transesterification of fats and oils is that the catalyst is not required, the degree of transesterification is high, and the purification process in the latter stage can be simplified. Good recovery with glycerol, although the use of supercritical alcohols for the production of biodiesel has been regarded as the next generation of emerging manufacturing technology, but previous studies have indicated that if you want to achieve a conversion rate of more than 99% in 10 minutes, At a pressure of 30 megapascals, a relatively high operating temperature must be given, operating at temperatures up to 400 degrees Celsius. At such high operating temperatures, the by-product of the transesterification 5 200925263 reaction is excessive, so how to lower the reaction temperature is a There is an urgent need to solve the problem, if the reaction temperature is to be lowered, the means used include the addition of a co-solvent such as carbon dioxide or propane, or the development of a solid catalyst; and the esterification reaction of the alcohol with the acid is an equilibrium reaction, so the conversion rate Affected by temperature and pressure, adding a large amount of excess alcohol can slightly lower the operating temperature And pressure, and can get higher conversion rates, but must consume large amounts of alcohol, does not burden the economy and the environment. However, the prior art has unavoidable disadvantages in that it is necessary to use ❹ additives, high process difficulty, difficult process control, burden on the environment, and high manufacturing costs. SUMMARY OF THE INVENTION In view of the above, in order to solve the above problems, the present invention provides a reverse flow esterification reactor for producing biodiesel and a method thereof, wherein a raw material containing a fatty acid and a raw material containing an alcohol are subjected to reverse flow esterification. In the reactor, no additives are added, and the operating temperature is low, and the transesterification reaction is carried out in the reaction column to prepare the product biodiesel. In order to achieve the above object, the present invention provides a reverse flow esterification reactor for producing biodiesel and a method thereof. Since the molecular weight of the fatty acid is only about 1/3 of that of the fat, the two-component system of the fatty acid-containing raw material and the alcohol is provided. The critical trajectory temperature and pressure will be much lower than the two-component system of oils and alcohols, which means that fatty acids and alcohols can be single homogeneous at lower temperatures and pressures, so using fatty acids as raw materials can be A single homogeneous reaction is carried out under lower reaction conditions, and the raw material containing fatty acid and the raw material containing 200925263 alcohol are heated to the operating temperature and then placed in a reverse flow esterification reactor. 'Ester in the reverse flow esterification reactor The reaction tower is given a constant high temperature • transesterification with the stupid pressure' and the by-product alcohol and water are continuously separated by a vapor-liquid separation device and then discharged into the reverse-flow esterification reactor, by continuously The by-product alcohol and water are discharged, and the transesterification reaction is forced to be continuously reacted in the forward direction to form a product biomass diesel. The beneficial effects of the present invention are to provide a reverse flow esterification reaction benefit for producing biodiesel and a method thereof. The present flow esterification reactor uses a raw material containing a fatty acid and a raw material containing an alcohol to improve transesterification without using any additives. The conversion rate of the reaction is a green environmental protection process, which does not cause environmental burden, and has many functions such as simple process, easy process control, and reduced manufacturing cost. [Embodiment] The features and implementations of the present invention are set forth in the accompanying drawings. Please refer to FIG. 1 , which is a reverse flow esterification reactor of the invention for producing biodiesel (Bi〇-dies _ el, Fatty Acid Methyl Ester, FAME) 1 ' S-reaction reaction tower (Packed Reactor, Esterification Tower) L〇〇 is a barrel-shaped metal hollow tank that can withstand a pressure of 4 MPa (Mp a) or less, and an Esterification Reactor 100 has a sieve plate (Sieve Tray) 103 for The raw materials entering the Esterification Reactor 100 are thoroughly mixed, and the Esterification Reactor 100 may also be provided with Laminate d Plates, high temperature fillers (Fi 1 ler) or stainless steel. Steel Mesh 7 200925263 The Esterification Reactor 100 has a pressure control device (101) that can control the pressure in the Esterification Reactor and maintain the vinegar. The pressure required for the Esterification process, the es teration Reactor 100 also has a Temperature Controller 102' to control the esterification reactor The temperature in the Esterificate Reactor 100 maintains the temperature required for the Esterification process; the first feeding device 11 is connected to the upper end of the Esterification Reactor 100, and the first feeding device 11〇 A first pressurized feed means 113 is used to pressurize the pump to pressurize the raw material 'the first feeding device 110 from the first feeding device 110 into the acetic acid reaction reactor 100 ( The Packed Reactor (Esterification Tower) 100 has a flow control device (Flow Control ler) 112' to control the flow rate of the raw material from the first feeding device 110 into the Esterification Reactor l00. The first feeding device 110 has a Heater and Temperature Controller 111 for heating the raw material entering the S-Esterification Reactor 100 from the first feeding device 110; the second feeding device 120 is connected At the lower end of the esterification reaction reactor 100, the second feeding device 120 has a second pressurized feed means 122 for pumping pressure for pressurization The second feeding device 120 enters the raw material of the Esterification Reactor 100, and the second feeding device 120 and the S reaction column (Esterification 8 200925263)
Rea ctor) 100連接處有流量控制裝置（Flow Controller) 123，用以控制由第二進料裝置120進入酯化反應塔 (Esteri fication Reactor)100 之原料流量，第二進料裝 置120具有加熱溫度控制裝置（Heater and Temperature Contro 1 ler)121 ’用以加熱由第二進料裝置120進入酯化 反應塔（Packed Reactor'Esterification Tower)100 之 原料；第一出料裝置130連接醋化反應塔（Esterification Reactor)100上端，第一出料裝置130與酯化反應塔 ❹ (Esterification Reactor) 100連接處有流量控制裝置 (Flow Controller) 131 ’用以控制由第一出料裝置130流 出酯化反應塔（Esterification Reactor) 100之副產物流 量，第一出料裝置130具有氣液分離裝置（Separator) 132分顧塔（Fractionating Tower)，用以分離由第一出料裝 置 130 流出酯化反應塔（Esterification Reactor)100 之 副產物；第二出料裝置140連接g旨化反應塔（Esteri fica q tion Reactor)100下端’第二出料裝置140與酯化反應塔 (Esterification Reactor) 100連接處有流量控制裝置 (Flow Controller) 141，用以控制由第二出料裝置140流 出酯化反應塔（Esterification Reactor) 100之產物流量。 請參照圖1與圖2A所示，其為本發明利用逆向流動 酉旨化反應器1製作生質柴油（Bio-diesel、Fatty Acid Methyl Ester、FAME)231的方法2，第一階段為原料加熱 手段（步驟S110)，將含有脂肪酸之原料（Fat1:yAcids)2ll 9 200925263 於第一進料裝置110内由加熱溫度控制裝置（Heater and Tempera ture Controller)lll 加熱至攝氏 340 度，並經 由流量控制裝置（Flow Controller)112送進酯化反應塔 (Esterification Reactor)100 ，將含有醇類之原料 (Alcohol )212甲醇（MeOH、Methanol)溶液於第二進料裝置 120内由加熱溫度控制裝置（Heater and Temperature Controller) 121加熱至攝氏340度，並經由流量控制裝 置（Flow Controller)123 送進酯化反應塔（Esterifica © tion Reactor) 100，其中含有脂肪酸之原料（Fatty Acids Mixture)211可為脂肪酸（Fatty Acids)與油脂（Oil)混合 物’而含有醇類之原料（Alcohol)212可為卜4個石炭(Carbon) 之醇類（Alcoho 1)。 第二階段為轉酯化反應（Esteri f ication)22 (步驟 S120)，在酯化反應塔（Esterification Reactor)100 内， 維持溫度攝氏340度與壓力30百萬帕斯卡（Mpa)，含有脂 ❹ 肪酸之原料（Fatty Acids)211從酯化反應塔（Esterific ation Reactor)100内上端往下流動，含有醇類之原料 (Alcohol) 212甲醇（MeOH、Methanol)溶液從酯化反應塔 (Esterification Reactor)100内下端往上流動，含有脂 肪酸之原料（Fatty Acids)211與含有醇類之原料（Alcohol) 212 甲醇（MeOH、Methanol)溶液於篩板（Sieve Tray)103 充 分接觸混合進行轉酯化反應（Esterification)22，製成生 質柴油（Bio -diesel、Fatty Acid Methyl Ester、FAME) 200925263 231與副產物醇類溶液（Alcoholic solution)232，生質柴 油（Bio-diesel 、 Fatty Acid Methyl Ester 、 FAME)231 經 由第二出料裝置140流出，而醇類溶液（Alcoholic solution)232進入第一出料裝置130，經由氣液分離裝置 (Separator)132 分傑塔（Fractionating Tower)進行氣液分 離手段24，利用醇類溶液（Alcoholic solution)232中各 成分沸點之不同，分離成醇類（Alcohol)241甲醇（MeOH、 Methanol)、水（Water)242 與甘油（Glycerol、Glycerin)243， ❹ 經由連續不斷地將醇類（Alcohol)241曱醇（MeOH、 Methanol)、水（Water)242 與甘油（Glycerol、Glycerin)243 排出，迫使轉酯化反應（Esi:erifica1:ion)22不斷地往正向 反應，藉以提高轉酯化反應（Esterification)22之轉化率 (Conversion efficiency)，提高製成生質柴油 (Bio-diesel、Fatty Acid Methyl Ester、FAME) 231 的效 率；請參照圖2B所示，一般的生質柴油（Bio-diese卜Fatty Acid Methyl Ester、FAME)231含有微量的雜質，可利用 〇 精煉手段（Purification)25蒸館（Distillation)將生質柴 油（Bio-diesel、Fatty Acid Methyl Ester、FAME)的雜 質醇類溶液252分離出，製成精煉生質柴油（Bio-diese卜 Fatty Acid Methyl Ester、FAME)251 ，其中分出的醇類 溶液252可利用氣液分離裝置（Separator) 132分鶴塔 (Fractionating Tower)進行氣液分離手段24，將醇類 (Alcohol)曱醇（MeOH、Methanol)241、水（Water)242 與甘 11 200925263 油（Glycerol、Glycerin)243 分離並排出。 請參照圖3A與圖3B所示，利用本發明原理於實驗室使 用相同操作條件，進行超臨界甲醇（MeOH、Methanol)進行大 豆油（Soybean 0i 1)轉S旨化反應（Esteri f icat ion)製作生 質柴油（Bio-diesel、Fatty Acid Methyl Ester、FAME)， 產物經過簡單冷凍後即可輕易獲得不含皂的生質柴油 (Bio-diesel、Fatty Acid Methyl Ester、FAME)與溶有甘 油（Glycerol、Glycerin)的曱醇（MeOH、Methanol)溶液，使 ❹ 用氣相層析儀（Gas Chromatograph)檢測生成物生質柴油 (Bio-diesel、Fatty Acid Methyl Ester、FAME);請參照 圖4所示為大豆油（Soybean Oil)完全轉酯化反應 (Esterif icat ion)產物之氣相層析譜圖（GC chromatogra m)，其中橫轴為滯留時間（Retention Time)，縱軸為離子 學（Peak)，顯示所製成的生質柴油（Bio-diesel、Fatty Acid Methyl Ester、FAME)中已完全不含三酸甘油酯（TG、 φ Triacylglycerol)，僅含少量非皂化成分（USM、Unsa ponifiable matter)，請見圖4中白色圈起部分；請參照圖 5所示，縱轴為轉酯化反應（Esterification)之轉化率（Con version eff iciency)，橫轴為反應時間（Time)，其單位為 分鐘（Min)，在30百萬帕斯卡（Mpa)的壓力條件下，溫度攝 氏340度（虛線所示）與攝氏400度（實線所示）在不同反應 時間（Time)下產生的生質柴油（Bio-diesel、Fatty Acid Methyl Ester、FAME)含量，其中大約只含有非皂化成分 12 200925263 (USM、Unsaponifiable mati;er)2百分比（Percent，％)左 右，轉酯化反應（Esterification)之轉化率（Conversion ef f iciency)相當高。 雖然本發明以前述之較佳實施例揭露如上，然其並非 ' 用以限定本發明，任何熟習相像技藝者，在不脫離本發明 之精神和範圍内，所作更動與潤飾之等效替換，仍為本發 明之專利保護範圍内。 綜觀上述，本發明以其整體之組合與特徵而言，既未 © 曾見諸於同類產品中，申請前亦未公開，誠已符合專利法 之法定要件，依法提出發明專利之申請。 【圖式fa〗单說明】 圖1為本發明逆向流動酯化反應器之結構圖； 圖2A為本發明利用逆向流動酯化反應器製作生質柴油的 方法流程圖； 圖2B為製作精鍊生質柴油的方法流程圖； @ 圖3A為大豆油甲酯化產物之簡易冷凍分離製程前圖； 圖3B為大豆油甲酯化產物之簡易冷凍分離製程後圖； 圖4為大豆油完全甲S旨化反應產物之氣相層析諸圖；以及 圖5為曱酯化大豆油中生質柴油的含量。 【主要元件符號說明】 1 逆向流動酯化反應器 100 S旨化反應塔 101 壓力控制裝置 13 200925263 102 溫度控制裝置 • 103 篩板 110 第一進料裝置 111 加熱溫度控制裝置 112 流量控制裝置 113 第一加壓進料手段 120 第二進料裝置 121 加熱溫度控制裝置 ❹ 122 第二加壓進料手段 123 流量控制裝置 130 第一出料裝置 131 流量控制裝置 132 氣液分離裝置 140 第二出料裝置 141 流量控制裝置 ❹ 2 利用逆向流動酯化反應器製作生質柴油的方法 步驟S110 原料加熱手段 步驟S120 轉醋化反應 211 含有脂肪酸之原料 212 含有醇類之原料 22 轉酯化反應 231 生質柴油 232 醇類溶液 14 200925263 24 氣液分離手段 241 醇類 242 水 243 甘油 25 精煉手段 252 醇類溶液 251 精煉生質柴油 ❹ 15The Rea ctor 100 has a flow controller 123 for controlling the flow rate of the raw material entering the esterification reaction reactor 100 from the second feeding device 120, and the second feeding device 120 has a heating temperature. The control device (Heater and Temperature Contro 1 121) 121' is used to heat the raw material entering the esterification reaction tower (Packed Reactor' Esterification Tower) 100 from the second feeding device 120; the first discharging device 130 is connected to the vinegarization reaction tower ( At the upper end of the Esterification Reactor 100, a flow control device (Flow Controller) 131' is connected to the Esterification Reactor 100 to control the flow of the esterification reaction tower from the first discharge device 130. (Esterification Reactor) 100 by-product flow, the first discharge device 130 has a gas-liquid separation device (Separator) 132, a Fractionating Tower for separating the esterification reaction tower from the first discharge device 130 (Esterification) a by-product of the Reactor 100; the second discharge device 140 is connected to the lower end of the Esteri fica q tion Reactor 100. Feed means connection with the esterification reaction column 140 (Esterification Reactor) 100 flow control means (Flow Controller) 141, for controlling the flow rate of the esterification reaction product of column (Esterification Reactor) 100 of the stream 140 from the second discharge means. Please refer to FIG. 1 and FIG. 2A , which is a method 2 for preparing biodiesel (Bio-diesel, Fatty Acid Methyl Ester, FAME) 231 by using a reverse flow reactor 1 in the present invention. Means (step S110), the raw material containing fatty acid (Fat1: yAcids) 2ll 9 200925263 is heated in the first feeding device 110 by a heating temperature control device (Heater and Tempera Controller) 111 to 340 degrees Celsius, and is controlled by flow rate The Flow Controller 112 is sent to an Esterification Reactor 100, and a solution of an alcohol-containing raw material (Alcohol) 212 methanol (MeOH, Methanol) is supplied to the second feeding device 120 by a heating temperature control device (Heater). And Temperature Controller 121 is heated to 340 degrees Celsius and sent to the Esterifica Source Reactor 100 via a Flow Controller 123, wherein the fatty acid (Fatty Acids Mixture) 211 can be a fatty acid ( Fatty Acids) and oil (Oil) mixture and alcohol-containing raw material (Alcohol) 212 can be 4 carbon charcoal (Alcoho 1)The second stage is an Esteriization Reaction 22 (Step S120), in which an Esterification Reactor 100 is maintained at a temperature of 340 degrees Celsius and a pressure of 30 megapascals (Mpa), containing a fat emulsion. Fatty Acids 211 flows downward from the upper end of the Esterification Reactor 100, and contains an alcoholic material (Alcohol) 212 methanol (MeOH, Methanol) solution from the Esterification Reactor. The inner lower end of 100 flows upward, and the fatty acid-containing raw material (Fatty Acids) 211 and the alcohol-containing raw material (Alcohol) 212 methanol (MeOH, Methanol) solution are fully contacted and mixed in a sieve plate (Sieve Tray) 103 to carry out transesterification reaction ( Esterification 22, bio-diesel, Fatty Acid Methyl Ester, FAME 200925263 231 and by-product alcohol solution 232 231 flows out through the second discharge device 140, and an alcohol solution 232 enters the first discharge device 130, and passes through a gas-liquid separation device (Separator) 132. (Fractionating Tower) The gas-liquid separation means 24 is separated into alcohol (Alcohol) 241 methanol (MeOH, Methanol), water (Water) 242 and glycerin by using the difference in boiling points of the components in the Alcoholic solution 232. Glycerol, Glycerin) 243, 排出 By continuously discharging alcohol (Alcohol) 241 sterol (MeOH, Methanol), water (Water) 242 and glycerol (Glycerol, Glycerin) 243, forcing the transesterification reaction (Esi: erifica1) :ion)22 continuously reacts in the forward direction to increase the conversion efficiency of Esterification 22 and improve the efficiency of biodiesel (Bio-diesel, Fatty Acid Methyl Ester, FAME) 231 Referring to FIG. 2B, the general biodiesel (Bio-diese Fatty Acid Methyl Ester, FAME) 231 contains a trace amount of impurities, and the biodiesel can be purified by Purification 25 Distillation ( The impurity alcohol solution 252 of Bio-diesel, Fatty Acid Methyl Ester, FAME) is separated to produce refined biodiesel (Bio-diese Batty Acid Methyl Ester, FAME) 251, which is separated The type solution 252 can be subjected to a gas-liquid separation means 24 using a gas separation apparatus (Separator) 132, Fractionating Tower, alcohol (Alcohol) sterol (MeOH, Methanol) 241, water (Water) 242 and Gan 11 200925263 Oil (Glycerol, Glycerin) 243 is separated and discharged. Referring to FIG. 3A and FIG. 3B, using the same operating conditions in the laboratory, supercritical methanol (MeOH, Methanol) is used to carry out soybean oil (Soybean 0i 1) conversion reaction (Esteri f icat ion). Producing biodiesel (Bio-diesel, Fatty Acid Methyl Ester, FAME), the product can be easily frozen to obtain soap-free biodiesel (Bio-diesel, Fatty Acid Methyl Ester, FAME) and dissolved in glycerol ( Glycerol, Glycerin) sterol (MeOH, Methanol) solution, using gas chromatograph (Gas Chromatograph) to detect the production of biomass diesel (Bio-diesel, Fatty Acid Methyl Ester, FAME); please refer to Figure 4 The gas chromatogram (GC chromatogra m) of the soybean oil is completely transesterified (Esterif icat ion) product, wherein the horizontal axis is the retention time and the vertical axis is the ionology (Peak). ), it is shown that the produced biodiesel (Bio-diesel, Fatty Acid Methyl Ester, FAME) is completely free of triglycerides (TG, φ Triacylglycerol) and contains only a small amount of non-saponified components (USM, Unsa ponifiable matter). ) Please see the white circled part in Figure 4; please refer to Figure 5, the vertical axis is the conversion rate of Esterification (Con version eff iciency), and the horizontal axis is the reaction time (Time), the unit is minute. (Min), at a pressure of 30 MPa (Mpa), at a temperature of 340 ° C (shown in phantom) and 400 ° C (shown in solid lines) at different reaction times (Time) produced by biodiesel ( Bio-diesel, Fatty Acid Methyl Ester, FAME) content, which contains only about 9% of non-saponified ingredients 200925263 (USM, Unsaponifiable mati; er) 2% (Percent, %), conversion rate of transesterification (Esterification) Conversion ef f iciency) is quite high. Although the present invention has been described above in terms of the preferred embodiments thereof, it is not intended to limit the invention, and any equivalents of the modification and retouching are still possible without departing from the spirit and scope of the invention. It is within the scope of patent protection of the present invention. Looking at the above, the present invention, in terms of its overall combination and characteristics, has not been seen in similar products, and has not been disclosed before the application. It has already complied with the statutory requirements of the Patent Law and has filed an application for an invention patent according to law. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a structural diagram of a reverse flow esterification reactor of the present invention; FIG. 2A is a flow chart of a method for producing biomass diesel using a reverse flow esterification reactor according to the present invention; Flow chart of the method of quality diesel; @ Figure 3A is a simple freeze separation process of soybean oil methyl esterification product; Figure 3B is a simplified freeze separation process of soybean oil methylation product; Figure 4 is a complete S A gas chromatogram of the reaction product; and Figure 5 shows the content of the biomass diesel in the oxime esterified soybean oil. [Description of main components] 1 Reverse flow esterification reactor 100 S Reaction column 101 Pressure control device 13 200925263 102 Temperature control device • 103 sieve plate 110 First feeding device 111 Heating temperature control device 112 Flow control device 113 a pressurized feeding means 120 second feeding means 121 heating temperature control means ❹ 122 second pressurized feeding means 123 flow control means 130 first discharging means 131 flow controlling means 132 gas-liquid separating means 140 second discharging Device 141 Flow Control Device ❹ 2 Method for Producing Biodiesel Fuel by Reverse Flow Esterification Reactor Step S110 Raw Material Heating Method Step S120 Vaporization Reaction 211 Raw Material Containing Fatty Acid 212 Raw Material Containing Alcohol 22 Transesterification 231 Biomass Diesel 232 Alcohol Solution 14 200925263 24 Gas-liquid separation means 241 Alcohol 242 Water 243 Glycerol 25 Refining means 252 Alcohol solution 251 Refining biodiesel ❹ 15