201125968 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種反應器 油脂烷基化反應器。 詳言之，係關於一種連續式 【先前技術】 傳統生質柴油是以驗製程灰酸划岛〜> 4醭製程完成，因使用酸或鹼 觸媒因此在後處理需要酸鹼中和、 ^ 水洗等步驟，而且有廢 液處理問題。此外因甲醇輿插你、201125968 6. INSTRUCTIONS OF THE INVENTION: TECHNICAL FIELD OF THE INVENTION The present invention relates to a reactor oil and fat alkylation reactor. In particular, it relates to a continuous type of [prior art]. Traditional biodiesel is completed by the process of ash-alkali->4醭, which requires acid-base neutralization in post-treatment due to the use of acid or alkali catalyst. ^ Washing and other steps, and there are waste disposal problems. In addition, because of methanol, you
呷興植物油的相溶性不佳，轉酯化 反應時間1’因此大多為批次式製程。傳統生質柴程 主要缺點如下：1.反應時間長，” ^ 叙在2小時以上。2.批示 式、製程複雜’設備佔地面積大。3觸媒、酸鹼中和、水 洗、廢液處理等增加操作成本。4對原料的水分與游離脂 肪酸含量敏感，一般各控制在3%以下 油作原料則需要前處理以避免皂化。 因此若以廢食用 根據文獻顯示，甲醇在超臨界狀態下進行酯化 (esterification)或轉酯化（transesterificati〇n)反應對於原 料中水與游離脂肪酸等雜質的存在完全不受影響，具有以 下優點：1.反應速度快，一般在30分鐘以内。2連續式製 程，步驟簡化，設備佔地面積小。3·不需添加酸鹼觸媒， 無酸鹼中和、水洗、廢液處理等問題。4完全不受原料中 水與脂肪酸含量的影響。 中華民國專利公告第466271號「從油脂類製造脂肪酸之 烷基酯的方法」，提供一種不需使用金屬酸或鹼觸媒，於 超臨界低級醇狀態下轉酯化產製生質柴油的方法。該專利 145920.doc 201125968 係可使用含游離脂肪酸的油脂類料源和低碳醇類反應，並 將油脂類中所含的三酸甘油酯於超臨界醇類狀態下進行轉 醋化反應以製造脂肪酸之烷基酯，同時於不使用金屬驗觸 媒、酸觸媒的條件下進行反應，即可不需進行將游離脂肪 酸酯化之前處理工程，且不會生成脂肪酸皂之副產物，因 而可省略或簡化生成物的回收精製工程。該專利揭示將油 脂類和醇類一面連續通過管狀反應容器一面進行反應較 佳，但並未說明該管狀反應容器之實施方法。 美國專利第 6187939、6211390、6570030、6818026號揭 露超臨界醇類轉酯化的方法，使用批次式的壓力釜 (autoclave)作為反應器；美國專利第6812359、7193〇97號 揭露超臨界醇類轉醋化的方法，使用連續式反應器，但並 未揭示連續式反應器的實施方法。 根據文獻使用於連續式之反應器一般使用管式反應器 (tubular reactor)，為增加轉酯化反應之轉化率與避免逆反 應之發生，一般使用過量低碳醇類（1〜4個碳之醇類）亦即 尚醇油比。在批次式反應槽中一般使用攪拌器來增進醇與 油的接觸面積以提高反應效率，但在管式反應器中則無法 實施。過量的低碳賴雖可提高反應效率，但在後段回收 會浪費較多能源。 由於低碳醇類對油脂的溶解度不佳，因此必須提高反應 溫度到300°C以上才能有98%以上之轉化率，但有耗費能 源、高溫裂解降低脂肪酸烷基酯產率之缺點。此外，管^ 反應器在管徑放大時不易維持管中心至管壁之溫度均= 145920.doc 201125968 性’會大幅降低反應效率與轉化率。另外，根據文獻使用 金屬氧化物固相觸媒可降低反應溫度並提高轉化率，但固 相觸媒在管式反應器中Η實施：粉末狀觸媒容易造成管 路與閥門阻塞；多孔或網筛狀觸媒容易造成較大料與雜 質阻塞。更有甚者，管式反應器適合中低黏度油脂進料， 對於較高黏度或含有固體懸浮雜質之廢食用油或下腳料就 不適用。 因此，有必要提供一種創新且具進步性的連續式油脂貌 基化反應器，以解決上述問題。 【發明内容】 本發明提供一種連續式油脂烷基化反應器，包括：一管 柱、一轉子及_加熱器。該管柱包括：一第—反應物入口 設置於該管柱之一頂部用以輸入第一反應物；一第二反應 物入口設置於該管柱之一底部用以輸入第二反應物；一第 二反應物出口設置於該管柱之該頂部用以輸出未完全反應 之該第二反應物；及一產物出口設置於該管柱之該底部用 以輸出該第一及第二反應物之化學反應後的產物。該轉子 設置於該管柱内，並包括至少一薄膜成形元件，用以將該 第一反應物形成薄膜並往下流動，其中該第二反應物沿著 轉子與該管柱内壁形成之空間往上流動並與該第一反應物 接觸而產生化學反應。該加熱器用以加熱該管柱。 本發明另提供一種連續式油脂烷基化反應器，包括：一 管枉、一轉子及一加熱器。該管柱包括：一第一反應物入 口設置於該管柱之一頂部用以輸入第一反應物；一第二反 145920.doc 201125968 應物入口設置於該管柱之該頂部用以輸入第二反應物；及 一產物出口設置於該管柱之一底部用以輸出該第一及第二 反應物之化學反應後的產物與未完全反應之該第二反應 物。該轉子設置於該管柱内，並包括至少一薄臈成形元 件，用以將該第一及第二反應物形成薄膜並皆往下流動， 其中該第二反應物與該第一反應物接觸而產生化學反應。 該加熱器用以加熱該管柱。 本發明又提供一種連續式油脂烷基化反應器，包括：一 管柱、一轉子及一加熱器。該管柱包括：一第一反應物入 口用以輸入第一反應物；一第二反應物入口用以輸入第二 反應物；及一產物出口用以輸出該第一及第二反應物之化 學反應後的產物。該轉子設置於該管柱内，其係由一驅動 元件驅動旋轉，其中該轉子包括至少一滾子及一徑向臂， 該徑向臂用以將該滚子固定於該轉子之周邊，該滾子用以 將該第一及第二反應物之其中一者或其中兩者形成薄膜， 該第二反應物與該第一反應物接觸而產生化學反應，該滾 子設有固態觸媒，用以強化該化學反應之轉換率。該加熱 器用以加熱該管柱。 本發明連續式油脂烷基化反應器可適用高黏度液態反應 物，且反應物在形成薄膜後增加接觸表面積，大幅提昇反 應效率。另外，薄膜之溫度均一性控制容易，較無徑向溫 度梯度之問題。本發明連續式油脂烷基化反應器可適用於 常壓或低壓下之烷化反應或高溫高壓下之超臨界低碳醇烷 化反應。 145920.doc 201125968 【實施方式】 參考圖1，其顯示本發明第一實施例連續式油脂烷基化 反應器之示意圖。本發明第一實施例連續式油脂烷基化反 應器10包括：一管柱11、一轉子丨2及一加熱器13。該管柱 11具有一第一反應物入口 111、一第二反應物入口 112及一 產物出口 113，用以分別輸入第一反應物及第二反應物， 及輸出產物。 在本實施例中’該第一反應物入口 111設置於該管柱n 之一頂部，該第二反應物入口 112設置於該管柱11之一底 部，該產物出口 113設置於該管柱丨丨之該底部，該第一反 應物之密度大於該第二反應物。該第一反應物可為油脂， 第二反應物可為甲醇蒸汽或超臨界態甲醇，以廢食用油與 甲醇之轉酯化/酯化反應為例，其中第一反應物為廢食用 油’第一反應物為甲醇蒸汽或超臨界態甲醇。因廢食用油 的密度較大約800〜900 kg/m3，而甲醇蒸汽或超臨界態甲醇 的密度較小約200〜600 kg/m3，亦即該第一反應物與該第二 反應物之密度差值至少大於約2〇〇 kg/m3。因此，第一反應 物（廢食用油）在管柱Π之頂部進入後往下流，第二反應物 (甲醇蒸汽或超臨界態甲醇）在管柱丨丨之底部進入後往上 流’以產生反應。 本發明連續式油脂烷基化反應器1〇另包括一第二反應物 入口管路114連接該第二反應物入口 112，且突伸於管柱11 之底部上。本發明連續式油脂烷基化反應器1〇另包括一第 二反應物出口 115,設置於該管柱丨丨之該頂部，可使過量 145920.doc 201125968 未反應之第二反應物（甲醇蒸汽或超臨界態甲醇）自第二反 應物出口 115流出，經過減壓降溫後可回收再使用。 該轉子12設置於該管柱11内，其係由一驅動元件14驅動 旋轉，具有至少一薄膜成形元件121，用以將第一反應物 形成薄膜15,使第一反應物與第二反應物產生反應。 在本實施例中，第一反應物（廢食用油）自管柱u頂部之 第一反應物入口 111進入，經過轉子12的離心作用與薄臈 成形元件121之抹平作用，在管柱u内壁形成薄膜15，並 因重力而向下流動；第二反應物（甲醇蒸汽或超臨界態曱 醇）自管柱11底部之第二反應物入口 U2進入，往上流經轉 子12與管柱U内壁所形成之空間，並與第一反應物（廢食 用油）形成之薄膜15接觸而產生轉酯化/酯化反應。由於薄 膜成形元件121之抹平作用不斷地將薄膜15表面更新從而 不斷地有未反應的第一反應物（廢食用油）與第二反應物（曱 醇蒸汽或超臨界態甲醇）接觸而產生轉酯化/酯化反應，因 此反應速度相當快。 由於第一反應物（廢食用油）與第二反應物（甲醇蒸汽或超 臨界態甲醇）為逆向接觸與反應，因此在管柱部從上 而下可分為混合區、反應區、分離區三個區域：混合區為 第一反應物（廢食用油）與第二反應物（甲醇蒸汽或超臨界態 甲醇）之預混合，較佳為在第一反應物入口 Ul進入管柱^ 内腔處設置分散或霧化裝置使第一反應物（廢食用油）霧化 成微液滴，使與第二反應物（甲醇蒸汽或超臨界態甲醇）充 分混合並有擴散效果，過量未反應之第二反應物（甲醇蒸 145920.doc * 8 - 201125968 K或超臨界態甲醇）則可自第二反應物出口 1丨5流出，經過 減壓降溫後可回收再使用。 在反應區因第一反應物（廢食用油）形成薄膜15後與第二 反應物（甲醇蒸汽或超臨界態甲醇）有最大接觸面積因此反 應快速並產生產物（脂肪酸甲酯與甘油）^在分離區產物（脂 肪酸甲酯與甘油）密度大而向下沉積並從產物出口 113流出 到靜置槽（圖中未顯示）而分層，新鮮的第二反應物（甲醇 蒸汽或超臨界態甲醇）因密度小而往上流，並與微量未完 全反應之第一反應物（廢食用油）進行反應，因而可使轉化 率再提升至接近100%。 參考圖2，其顯示本發明薄膜成形元件第一實施例之示 意圖。在本實施例中，該薄膜成形元件121係為至少一刮 刀，叹置於該轉子12之周邊。至少兩片以上的刮刀121以 鑲嵌、鎖固或鉚接等方式固定在轉子12上。刮刀121突出 轉子12的距離以1〜10 mm較佳。刮刀121與管柱u内壁接 觸端之外形較佳為刀刃狀或楔狀或圓角狀。另外，該刮刀 121可具有螺旋狀溝槽，使轉動時具有向下之推力將第一 反應物（廢食用油）薄膜15往下推動。 參考圖3及圖4，其顯示本發明薄膜成形元件第二實施例 之示意圖。在本實施例中’該薄膜成形元件2 21係為至少 一滾子，以徑向臂222固定滾子221於該轉子22之周邊，且 滾子221繞—滾子軸223轉動。其中轉子22的兩端具有徑向 臂222 I伸用來固定滾子軸223。另外，可使用金屬如鎳 (Nl)、鉑（Pt)或金屬氧化物如氧化鈣（CaO)、氧化鉛（Zr〇2) 145920.doc 201125968 等固態觸媒來強化轉酯化/酯化反應之轉化率。固態觸媒 係以機械加工或燒結成滾子狀為該滾子221，或以塗佈、 沉積、含浸、植入等方式固定在基材為金屬或陶瓷的滚子 221表面上。在轉子22轉動時透過徑向臂222帶動滾子221 沿著管柱内壁作圓周運動產生類似刮刀的作用而將第一反 應物（廢食用油）形成薄膜15，同時滾子221繞滾子轴223產 生自轉運動，因而使滾子221上的固態觸媒與第一反應物 (廢食用油）薄膜15不斷地接觸與更新，有效地提升反應效 率。 再參考圖1 ’該加熱器13用以加熱該管柱11，且設置於 管柱11之周邊，使管柱丨丨内壁之第一反應物（廢食用油）薄 膜15溫度均一性控制容易，較無徑向溫度梯度之問題。 參考圖5，其顯示本發明第二實施例連續式油脂烷基化 反應器之示意圖。本發明第二實施例連續式油脂烷基化反 應器30包括：一管柱31、一轉子32及一加熱器33。本發明 第一實施例連續式油脂規基化反應器3 0與第一實施例連續 式油脂烷基化反應器10不同之處，在於該第一反應物入口 311及該第一反應物入口 312皆设置於該管柱31之一頂部， 該產物出口 313設置於該管柱31之一底部。 在本實施例中’該第一反應物可為油脂，第二反應物可 為液態甲醇’以廢食用油與曱醇之轉酯化/酯化反應為 例’其中第一反應物為廢食用油，第二反應物為液態甲 醇。因廢食用油的密度約800〜9〇〇 kg/m3，與液態甲醇的密 度約700〜800 kg/m3差距不大，亦即該第一反應物與該第二 145920.doc •10- 201125968 反應物之密度差值至少小於約200 kg/m3，故在管柱3 1頂部 採用同向流進料方式’第一反應物（廢食用油）自管柱頂部 之第一反應物入口 311進入，第二反應物（液態甲醇）自管桂 31頂部之第二反應物入口 312進入。The compatibility of the Zhaoxing vegetable oil is not good, and the transesterification reaction time is 1', so most of them are batch processes. The main disadvantages of the traditional biomass range are as follows: 1. The reaction time is long, “ ^ is more than 2 hours. 2. The indication type and the process are complicated. The equipment covers a large area. 3 Catalyst, acid-base neutralization, water washing, waste liquid Treatment and other increased operating costs. 4 The moisture of the raw materials is sensitive to the content of free fatty acids. Generally, the oils used as raw materials under 3% are required to be pretreated to avoid saponification. Therefore, if waste is consumed according to the literature, methanol is supercritical. The esterification or transesterification reaction is completely unaffected by the presence of impurities such as water and free fatty acids in the raw material, and has the following advantages: 1. The reaction speed is fast, generally within 30 minutes. The process is simple, the equipment is small, and the equipment covers a small area. 3. No need to add acid-base catalyst, no acid-base neutralization, water washing, waste liquid treatment, etc. 4 completely free from the influence of water and fatty acid content in raw materials. Republic of China Patent No. 466271, "Method for Producing Alkyl Ester of Fatty Acids from Oils and Fats," provides a method of using a metal acid or a base catalyst in a supercritical lower alcohol state without using a metal acid or a base catalyst Biodiesel production system esterification methods. The patent 145920.doc 201125968 can use a source of a fatty acid containing free fatty acids and a lower alcohol to react, and the triglyceride contained in the oil and fat is subjected to transacetalization in a supercritical alcohol state to produce The alkyl ester of a fatty acid can be reacted without using a metal catalyst or an acid catalyst, so that it is not necessary to carry out the treatment before esterification of the free fatty acid, and it does not produce a by-product of the fatty acid soap. The recycling and refining process of the product is omitted or simplified. This patent discloses that it is preferred to continuously react the oil and the alcohol on one side of the tubular reaction vessel, but does not describe the method of carrying out the tubular reaction vessel. U.S. Patent Nos. 6,187,939, 6, 211, 390, 6, 570, 030, and 6, 818, 026 discloses a method of transesterification of supercritical alcohols using a batch of autoclave as a reactor; U.S. Patent Nos. 6,812,359, 7 193,97 discloses supercritical alcohols The method of trans-acetation uses a continuous reactor, but does not disclose the implementation of the continuous reactor. According to the literature, continuous reactors generally use a tubular reactor. In order to increase the conversion rate of the transesterification reaction and avoid the occurrence of a reverse reaction, an excess of lower alcohols (1 to 4 carbon alcohols) is generally used. Class) is also the ratio of alcohol to oil. A stirrer is generally used in the batch type reaction tank to increase the contact area of the alcohol with the oil to improve the reaction efficiency, but it cannot be carried out in the tubular reactor. Excessive low carbon can improve the efficiency of the reaction, but it will waste more energy in the later stage of recycling. Since the solubility of low-carbon alcohols to oils and fats is not good, it is necessary to increase the reaction temperature to above 300 °C in order to have a conversion rate of 98% or more, but there are disadvantages such as energy consumption and high-temperature cracking to lower the yield of fatty acid alkyl esters. In addition, the tube reactor is not easy to maintain the temperature from the center of the tube to the tube wall when the tube diameter is enlarged = 145920.doc 201125968 property' will greatly reduce the reaction efficiency and conversion rate. In addition, according to the literature, the use of metal oxide solid phase catalyst can reduce the reaction temperature and increase the conversion rate, but the solid phase catalyst is carried out in a tubular reactor: the powdery catalyst is easy to cause blockage of the pipeline and the valve; porous or mesh Sieve-like catalysts tend to cause blockage of larger materials and impurities. What's more, tubular reactors are suitable for medium to low viscosity grease feeds and are not suitable for use with higher viscosity or waste cooking oils or scraps containing solid suspended impurities. Therefore, it is necessary to provide an innovative and progressive continuous grease characterization reactor to solve the above problems. SUMMARY OF THE INVENTION The present invention provides a continuous fat alkylation reactor comprising: a column, a rotor and a heater. The column includes: a first reactant inlet disposed at a top of the column for inputting the first reactant; and a second reactant inlet disposed at a bottom of the column for inputting the second reactant; a second reactant outlet is disposed at the top of the column for outputting the second reactant that is not completely reacted; and a product outlet is disposed at the bottom of the column for outputting the first and second reactants The product after the chemical reaction. The rotor is disposed in the column and includes at least one film forming member for forming a film of the first reactant and flowing downward, wherein the second reactant passes along a space formed by the rotor and the inner wall of the column Flowing on and contacting the first reactant produces a chemical reaction. The heater is used to heat the column. The invention further provides a continuous oil and fat alkylation reactor comprising: a tube, a rotor and a heater. The column includes: a first reactant inlet disposed at a top of one of the columns for inputting the first reactant; and a second counter 145920.doc 201125968 an inlet of the reagent disposed at the top of the column for inputting a second reactant; and a product outlet disposed at a bottom of the column for outputting the chemically reacted product of the first and second reactants and the second reactant that is not completely reacted. The rotor is disposed in the column and includes at least one thin forming element for forming the first and second reactants to form a film and flowing downwardly, wherein the second reactant is in contact with the first reactant And produce a chemical reaction. The heater is used to heat the column. The invention further provides a continuous oil and fat alkylation reactor comprising: a column, a rotor and a heater. The column includes: a first reactant inlet for inputting the first reactant; a second reactant inlet for inputting the second reactant; and a product outlet for outputting the chemical of the first and second reactants The product after the reaction. The rotor is disposed in the tubular string and is driven to rotate by a driving component, wherein the rotor includes at least one roller and a radial arm for fixing the roller to the periphery of the rotor, a roller for forming a film of one or both of the first and second reactants, the second reactant contacting the first reactant to generate a chemical reaction, the roller being provided with a solid catalyst, Used to enhance the conversion rate of the chemical reaction. The heater is used to heat the column. The continuous fat alkylation reactor of the present invention can be applied to a highly viscous liquid reactant, and the reactants increase the contact surface area after forming a film, thereby greatly improving the reaction efficiency. In addition, the temperature uniformity control of the film is easy and there is no problem with the radial temperature gradient. The continuous oleoalkylation reactor of the present invention is suitable for alkylation at atmospheric or low pressure or supercritical lower alcohol alkylation at elevated temperatures and pressures. 145920.doc 201125968 [Embodiment] Referring to Figure 1, there is shown a schematic view of a continuous oleoalkylation reactor of a first embodiment of the present invention. The continuous grease alkylation reactor 10 of the first embodiment of the present invention comprises: a column 11, a rotor 2 and a heater 13. The column 11 has a first reactant inlet 111, a second reactant inlet 112, and a product outlet 113 for inputting the first reactant and the second reactant, respectively, and outputting the product. In the present embodiment, the first reactant inlet 111 is disposed at the top of one of the columns n, the second reactant inlet 112 is disposed at the bottom of one of the columns 11, and the product outlet 113 is disposed at the column. At the bottom of the crucible, the first reactant has a greater density than the second reactant. The first reactant may be a grease, and the second reactant may be methanol vapor or supercritical methanol, taking the transesterification/esterification reaction of waste edible oil and methanol as an example, wherein the first reactant is waste edible oil' The first reactant is methanol vapor or supercritical methanol. Since the density of waste cooking oil is about 800-900 kg/m3, the density of methanol vapor or supercritical methanol is about 200~600 kg/m3, that is, the density of the first reactant and the second reactant. The difference is at least greater than about 2 〇〇 kg/m3. Therefore, the first reactant (waste cooking oil) enters and flows down at the top of the column, and the second reactant (methanol vapor or supercritical methanol) enters the bottom of the column and flows upwards to generate a reaction. . The continuous oleoalkylation reactor of the present invention further comprises a second reactant inlet line 114 connected to the second reactant inlet 112 and projecting from the bottom of the column 11. The continuous oil and fat alkylation reactor of the present invention further comprises a second reactant outlet 115 disposed at the top of the column to provide an excess of 145920.doc 201125968 unreacted second reactant (methanol vapor) Or supercritical methanol) is discharged from the second reactant outlet 115, and can be recovered and reused after being cooled under reduced pressure. The rotor 12 is disposed in the column 11 and is driven to rotate by a driving member 14 having at least one film forming member 121 for forming a first reactant to form a film 15 for the first reactant and the second reactant. Produce a reaction. In the present embodiment, the first reactant (waste cooking oil) enters from the first reactant inlet 111 at the top of the column u, passes through the centrifugal action of the rotor 12 and the smoothing action of the thin forming element 121, in the column u The inner wall forms a film 15 and flows downward due to gravity; the second reactant (methanol vapor or supercritical sterol) enters from the second reactant inlet U2 at the bottom of the column 11, and flows upward through the rotor 12 and the column U The space formed by the inner wall is brought into contact with the film 15 formed by the first reactant (waste cooking oil) to produce a transesterification/esterification reaction. Since the smoothing action of the film forming member 121 continually renews the surface of the film 15 to continuously generate an unreacted first reactant (waste cooking oil) in contact with the second reactant (sterol vapor or supercritical methanol) The transesterification/esterification reaction is carried out, so the reaction rate is quite fast. Since the first reactant (waste cooking oil) and the second reactant (methanol vapor or supercritical methanol) are in reverse contact and reaction, the column portion can be divided into a mixing zone, a reaction zone, and a separation zone from top to bottom. Three zones: the mixing zone is a premixing of the first reactant (waste cooking oil) with the second reactant (methanol vapor or supercritical methanol), preferably at the first reactant inlet U1 into the column lumen A dispersing or atomizing device is arranged to atomize the first reactant (waste cooking oil) into micro droplets, so that the second reactant (methanol vapor or supercritical methanol) is thoroughly mixed and has a diffusion effect, and the excess unreacted The second reactant (methanol steam 145920.doc * 8 - 201125968 K or supercritical methanol) can be discharged from the second reactant outlet 1丨5, and can be recycled after being cooled under reduced pressure. After the film 15 is formed in the reaction zone due to the first reactant (waste cooking oil), it has the largest contact area with the second reactant (methanol vapor or supercritical methanol), so the reaction is rapid and the product (fatty acid methyl ester and glycerol) is produced. The separation zone product (fatty acid methyl ester and glycerol) has a high density and is deposited downward and flows out from the product outlet 113 to a standing tank (not shown) to separate the fresh second reactant (methanol vapor or supercritical methanol). ) It flows upward due to low density and reacts with a trace amount of the first reactant (waste cooking oil) which is not completely reacted, so that the conversion rate can be further increased to nearly 100%. Referring to Figure 2, there is shown a schematic representation of a first embodiment of a film forming member of the present invention. In the present embodiment, the film forming member 121 is at least one blade which is placed at the periphery of the rotor 12. At least two or more scrapers 121 are fixed to the rotor 12 by inlaying, locking or riveting. It is preferable that the blade 121 protrudes from the rotor 12 by a distance of 1 to 10 mm. The shape of the blade 121 and the inner end of the column u is preferably a blade shape or a wedge shape or a round shape. Further, the scraper 121 may have a spiral groove for pushing the first reactant (waste cooking oil) film 15 downward with a downward thrust during rotation. Referring to Figures 3 and 4, there is shown a schematic view of a second embodiment of the film forming member of the present invention. In the present embodiment, the film forming member 2 21 is at least one roller, the roller 221 is fixed to the periphery of the rotor 22 by the radial arm 222, and the roller 221 is rotated about the roller shaft 223. The rotor 22 has a radial arm 222 I extending at both ends for fixing the roller shaft 223. In addition, a solid catalyst such as nickel (Nl), platinum (Pt) or a metal oxide such as calcium oxide (CaO) or lead oxide (Zr〇2) 145920.doc 201125968 can be used to enhance the transesterification/esterification reaction. Conversion rate. The solid-state catalyst is machined or sintered into a roller shape for the roller 221, or is coated, deposited, impregnated, implanted or the like on the surface of the roller 221 whose base material is metal or ceramic. When the rotor 22 rotates, the radial movement of the roller 221 along the inner wall of the column through the radial arm 222 produces a knife-like action to form the first reactant (waste cooking oil) into the film 15, while the roller 221 is wound around the roller shaft. The rotation of 223 causes the solid catalyst on the roller 221 to continuously contact and renew with the first reactant (waste cooking oil) film 15, thereby effectively improving the reaction efficiency. Referring to FIG. 1 again, the heater 13 is used to heat the column 11 and is disposed around the column 11, so that the temperature uniformity of the first reactant (waste cooking oil) film 15 on the inner wall of the column is easy to control. Less problem with radial temperature gradients. Referring to Figure 5, there is shown a schematic view of a continuous oleoalkylation reactor of a second embodiment of the present invention. The continuous grease alkylation reactor 30 of the second embodiment of the present invention comprises a column 31, a rotor 32 and a heater 33. The first embodiment of the present invention is different from the continuous grease alkylation reactor 10 of the first embodiment in that the first reactant inlet 311 and the first reactant inlet 312 are different. Both are disposed at the top of one of the columns 31, and the product outlet 313 is disposed at the bottom of one of the columns 31. In the present embodiment, 'the first reactant may be oil and fat, and the second reactant may be liquid methanol' as an example of a transesterification/esterification reaction of waste edible oil with decyl alcohol, wherein the first reactant is waste edible. Oil, the second reactant is liquid methanol. The density of waste cooking oil is about 800~9〇〇kg/m3, which is not much different from the density of liquid methanol of about 700~800 kg/m3, that is, the first reactant and the second 145920.doc •10-201125968 The difference in density of the reactants is at least less than about 200 kg/m3, so that the same reactant feed mode 'the first reactant (waste cooking oil) is introduced from the first reactant inlet 311 at the top of the column at the top of the column 31. The second reactant (liquid methanol) enters from the second reactant inlet 312 at the top of the tube.
第一反應物（廢食用油）與第二反應物（液態甲醇）進行預 混合後’第一反應物（廢食用油）與第二反應物（液態甲醇） 之混合物經過轉子32的離心作用與薄獏成形元件32 1之抹 平作用在管柱31内壁形成薄膜35,並因重力與薄臈成形元 件321之螺旋紋作用而向下流動。 第一反應物（廢食用油）與第二反應物（液態甲醇）之薄膜 35產生轉酯化/酯化反應，並因為薄膜成形元件321之抹平 與攪拌作用不斷地將第二反應物（液態甲醇）與第一反應物 (廢食用油）充分混合因而促進反應之進行，因此反應速度 比習知使用攪拌葉片者快。 由於第一反應物（廢食用油）與第二反應物（液態甲醇）為 同向流之混σ與反應，在管柱内部從上而下可分為混合 區、反應區、分離區三個區域：混合區為第一反應物(廢 食用油)與第二反應物(液態曱醇)之預混合，較佳為在第-反應物入口 311與第二反應物人口扣進人管柱^内腔處設 置刀散或霧化裝置使第一反應物(廢食用油）、第二反應物 (液態甲醇）均霧化成微液滴’使第—反應物（廢食用油）與 第二反應物（液態甲醇）進行預混合並有擴散效果。 在應區因第反應物（廢食用油）與第二反應物（液態曱 醇)形成薄膜35後因混合均句而且在加熱器Μ提供熱能促 145920.doc [S] -11 - 201125968 進反應下，因此反應快速並產生產物（脂肪酸甲酯與甘 油）。在分離區未反應之第二反應物（液態甲醇）與產物（脂 肪酸甲酯、甘油）向下沉積並從產物出口 313流出到一靜置 槽（圖中未顯示）而分層，在靜置槽中的甲醇可經加熱成甲 醇蒸汽後與產物（脂肪酸甲酯、甘油）分離，經過冷凝而回 收再使用》 本發明連續式油脂烷基化反應器可適用高黏度液態反應 物，且反應物在形成薄膜後增加接觸表面積，大幅提昇反 應效率。另外’薄膜之溫度均一性控制容易，較無徑向溫 度梯度之問題。本發明連續式油脂烷基化反應器可適用於 常壓或低壓下之烷化反應或高溫高壓下之超臨界低碳醇烷 化反應。 惟上述實施例僅為說明本發明之原理及其功效，而非限 制本發明。因此’習於此技術之人士對上述實施例進行修 改及變化仍不脫本發明之精神。本發明之權利範圍應如後 述之申請專利範圍所列。 【圖式簡單說明】 圖1顯示本發明第一實施例連續式油脂烷基化反應器之 示意圖； 圖2顯示本發明薄膜成形元件第一實施例之示意圖； 圊3顯示本發明薄膜成形元件第二實施例之側面示意 固 . 圃， 圖4顯示本發明薄膜成形元件第二實施例之剖面示意 圖；及 145920.doc -12· [S] 201125968 圖5顯示本發明第二實施例連續式油脂烷基化反應器之 示意圖。 【主要元件符號說明】 10 本發明第一實施例連續式油脂烷基化反應器 11 管柱 12 轉子 13 加熱器 14 驅動元件After the first reactant (waste cooking oil) is premixed with the second reactant (liquid methanol), the mixture of the first reactant (waste cooking oil) and the second reactant (liquid methanol) is centrifuged by the rotor 32 and The smoothing action of the thin crucible forming member 32 1 forms a film 35 on the inner wall of the tubular string 31, and flows downward due to gravity and the spiral action of the thin crucible forming member 321. The film 35 of the first reactant (waste cooking oil) and the second reactant (liquid methanol) undergoes a transesterification/esterification reaction, and the second reactant is continuously continually applied due to the smoothing and agitation of the film forming member 321 ( The liquid methanol) is sufficiently mixed with the first reactant (waste cooking oil) to promote the progress of the reaction, so that the reaction rate is faster than the conventional use of the stirring blade. Since the first reactant (waste cooking oil) and the second reactant (liquid methanol) are mixed σ and reacted in the same direction, the inside of the column can be divided into a mixing zone, a reaction zone and a separation zone from top to bottom. Zone: The mixing zone is a premixed first reactant (waste cooking oil) with a second reactant (liquid sterol), preferably at the first reactant inlet 311 and the second reactant population is inserted into the tubular string ^ A knife dispersing or atomizing device is arranged at the inner cavity to atomize the first reactant (waste cooking oil) and the second reactant (liquid methanol) into micro droplets to make the first reactant (waste cooking oil) and the second reaction The material (liquid methanol) is premixed and has a diffusion effect. In the area where the film (35) is formed by the reaction of the first reactant (waste cooking oil) and the second reactant (liquid sterol), the heat is promoted in the heater 145920.doc [S] -11 - 201125968 The reaction is rapid and produces the product (fatty acid methyl ester and glycerol). The unreacted second reactant (liquid methanol) and the product (fatty acid methyl ester, glycerol) are deposited downward in the separation zone and flow out from the product outlet 313 to a standing tank (not shown) to be layered and allowed to stand. The methanol in the tank can be separated from the product (fatty acid methyl ester, glycerol) by heating to methanol vapor, and recovered by condensation. The continuous oil alkylation reactor of the present invention can be applied to a high viscosity liquid reactant, and the reactants The contact surface area is increased after the formation of the film, and the reaction efficiency is greatly improved. In addition, the temperature uniformity control of the film is easy, and there is no problem of the radial temperature gradient. The continuous oleoalkylation reactor of the present invention is suitable for alkylation at atmospheric or low pressure or supercritical lower alcohol alkylation at elevated temperatures and pressures. However, the above-described embodiments are merely illustrative of the principles of the invention and its effects, and are not intended to limit the invention. Therefore, those skilled in the art can make modifications and changes to the above embodiments without departing from the spirit of the invention. The scope of the invention should be as set forth in the appended claims. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic view showing a continuous fat alkylation reactor of a first embodiment of the present invention; Fig. 2 is a view showing a first embodiment of a film forming member of the present invention; 2 is a schematic cross-sectional view showing a second embodiment of the film-forming member of the present invention; and 145920.doc -12. [S] 201125968. FIG. 5 shows a continuous grease base of the second embodiment of the present invention. Schematic diagram of a base reactor. [Main component symbol description] 10 First embodiment of the present invention, a continuous fat alkylation reactor 11 column 12 rotor 13 heater 14 driving element
15 薄膜 30 本發明第二實施例連續式油脂烷基化反應器 31 管柱 32 轉子 33 加熱器 35 薄膜 111 第一反應物入口 112 第二反應物入口 113 產物出口 114 第二反應物入口管路 115 第二反應物出口 121 薄膜成形元件 221 薄膜成形元件 222 徑向臂 223 滚子軸 311 第一反應物入口 145920.doc 13· 201125968 312 第二反應物入口 313 產物出口 321 薄膜成形元件15 Membrane 30 Second Embodiment of the Invention Continuous Fatty Oil Alkylation Reactor 31 Column 32 Rotor 33 Heater 35 Membrane 111 First Reagent Inlet 112 Second Reactant Inlet 113 Product Outlet 114 Second Reactant Inlet Line 115 second reactant outlet 121 film forming element 221 film forming element 222 radial arm 223 roller shaft 311 first reactant inlet 145920.doc 13· 201125968 312 second reactant inlet 313 product outlet 321 film forming element
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