1281466 玖:、潑明鎌ΐ 發明所屬之技術領域 本發明係關於一種利用質傳設備，尤其是旋轉塡充 床，從酯類產物混合物中去除未反應的醇類的方法。 先前技術 酯類產物是由有機酸與醇反應生成，其生產製程中常 將醇加過量以促使反應較快完成，傳統反應程序是反應槽 上方接蒸餾塔，將蒸發物水與醇分離，水取出醇回流繼續 反應以至完成。反應完成後再將醇餾出，此時要採用真空 蒸餾才能將殘餘醇類淸除。一般醇類淸除係在低壓狀態 下，且需耗時甚久。但長時間的加熱會使酯類產物品質變 色劣化。目前習知脫除醇類之方法大多採用在低壓下使用 惰性氣體吹除至5000 ppm，如要降至適用於化粧品類產品 之50〜500 ppm’所須耗費之時間更長達12小時以上。 目前脫除醇類多採用曝氣氣泡溶解之方式（如通氣攪 拌槽），但由於液相中氣泡所形成之有效氣液接觸面積較小 及氣液接觸面更新速率慢，惰性氣體溶入液相之質傳效果 有限，以致處理效率不彰。因此需要提昇惰性氣體量、降 低壓力或提高溫度，以達到所需之效率。 近年來，旋轉塡充床的硏究與應用解決了許多在常重 力場下難以解決的問題。尤其是旋轉塡充床可以極大地強 化質傳過程，使幾十米高的塔器可用2米左右之旋轉塡充 床。在吸收、汽提、蒸餾等分離過程中應用都已取得料想 1281466 不到的效果。例如美國專利第4283255; 4382045; 4382900; 及4400275號。中國專利公開號CN111 61 46A (1996年）提 出使用該質傳設備的超細顆粒的製備方法，其中多相物流 由同心套管的內、外管經分佈器進料至一旋轉塡充床的軸 心位置，通過旋轉重力場作用，在塡充床中接觸並進行反 應。由於此技術是八十年代才出現的新技術，內部質傳機 理還在繼續探索，所以其新的應用領域還需要不斷開發， 如在脫醇之應用尙未見到公開報導。 發明內容 本發明的主要目的是提供一種從酯類產物混合物中去 除未反應的醇類的方法，其具有可降低惰性氣體使用量、 不需要提高酯類產物混合物溫度，且可縮減處理時間等優 點。 本發明利用旋轉塡充床改變氣液接觸方式，藉由較高 離心力和塡充物的作用，將酯類產物混合物切割成較薄的 液膜和較小液滴，以造成高氣液接觸面積和高質傳效率， 如此將使醇類更容易由酯類產物混合物中移餘，以使脫除 時間縮短、酯類產物品質提高、含醇量降低，進而提升產 業利用價値。 實施方式 一種用旋轉塡充床從酯類產物混合物中去除未反應醇 類的方法，其中該酯類產物具有10至30的碳原子數，該 1281466 方法包含下列步驟： a) 將一酯類產物混合物進料至一繞一軸心旋轉中的環形旋 轉塡充床，該旋轉塡充床係位於一艙（housing)內，使該 酯類產物混合物徑向流過該旋轉塡充床內的塡充物； b) 同時將一氣體導入該旋轉塡充床，使得該酯類產物混合 物在徑向流過該塡充物時與該氣體接觸，於是該酯類產 物混合物所含的未反應的醇類爲該氣體所汽提並由該艙 的頂部排出，及在該艙的底部收集一純化的酯類產物。 較佳的，步驟a)的酯類產物混合物係由該旋轉塡充床 的軸心區被導入。 較佳的，步驟b)的氣體係由該艙的周緣被導入，於是 該酯類產物混合物在徑向流過該塡充物時與該氣體逆流接 觸。 較佳的，步驟b)的氣體係由該旋轉塡充床的軸心區被 導入，於是該酯類產物混合物在徑向流過該塡充物時與該 氣體順流接觸。 較佳的，步驟b)的氣體係由該旋轉塡充床的底部被導 入並由該旋轉塡充床的頂部流出，於是該酯類產物混合物 在徑向流過該塡充物時與該氣體錯流接觸。 較佳的，一負壓被施予該旋轉塡充床的軸心區，使得 該酯類產物混合物在徑向流過該塡充物時在低壓情況下與 該氣體接觸，且含有汽提的未反應醇類的氣體通過該旋轉 塡充床的軸心區由該艙的頂部排出。 較佳的，本發明方法進一步包含將步驟b)收集到的純 1281466 化的酯類產物的全部或一部份作爲進料重覆步驟a)及b)， 直到所獲得的純化的酯類產物具有一想要的純度。 較佳的，步驟b)的氣體爲氮氣、二氧化碳、氬氣或水 蒸汽。 以下，將參考唯一圖式以一較佳具體實施例來說明本 發明。一適合用於本發明的旋轉塡充床系統被示於圖1。 如圖1 .所示，物料槽（1)中之酯類產物混合物經由抽水泵（2) 通過液體進口（3)打入一環形旋轉塡充床的軸心區，藉由液 體分佈器（4)，均勻地噴向環狀塡料（5)。藉由變速馬達（6) 的驅動產生極大的離心力，將液體往外快速移動，匯集於 旋轉塡充床的艙（7)之底部，最後由液體出口（8)排出。同時 利用惰性氣體（9)如氮氣、二氧化碳、氬氣或其他不參與反 應之氣體由旋轉塡充床的氣體進口（10)進入，在塡料（5)內 與酯類產物混合物逆流接觸，如此將帶走酯類產物混合物 中所含的未反應醇類，最後含有醇類的惰性氣體由氣體出 口（11)排出。 實施例一 使用類似於圖1的系統進行硬脂酸丁酯（BST)批次式 脫除正丁醇（NBA)測試。旋轉塡充床規格爲：內徑78 mm， 外徑160 mm，厚度20 mm。轉速固定於1300 rpm。所使 用的塡充物爲編織的不銹鋼金屬絲網（比表面積1906 m2/m3)。旋轉塡充床的塡充空隙度爲0.91 (未塡充塡充物 時空隙度爲1 ;完全塡充時塡充空隙度爲0)，以氮氣爲脫 1281466 氣劑。實驗時將BST由液體進口（3)進料至旋轉塡充床並將 由液體出口（8)出來的液體產品導入物料槽（1)中，以再回流 至物料槽（1)。實驗條件及所得到之結果如表。由此表可以 發現，於第7分鐘從液體出口（8)取樣的純化產物其NBA 降至237 ppm，於第12分鐘取樣者，其NBA降爲43 ppm。 測試 1 2 條件及結果 進料NBA濃度(ppm) 46205 46205 出料NBA濃度（ppm) 237(7min) 43(12min) 進料溫度（°c) 120 120 進液量（g/min) 250 250 氮氣量（L/min) 50 50 轉速（rpm) 1300 1300BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a process for removing unreacted alcohol from an ester product mixture using a mass transfer apparatus, particularly a rotary helium bed. The prior art ester product is formed by reacting an organic acid with an alcohol, and an excessive amount of alcohol is often added in the production process to promote the reaction to be completed quickly. The conventional reaction procedure is that the distillation column is connected to the distillation column, the evaporate water is separated from the alcohol, and the water is taken out. The alcohol reflux continues the reaction to completion. After the completion of the reaction, the alcohol is distilled off, and vacuum distillation is carried out to remove the residual alcohol. The general alcohol removal is in a low pressure state and takes a long time. However, prolonged heating deteriorates the quality of the ester product. At present, most of the methods for removing alcohols are carried out by using an inert gas at a low pressure to 5000 ppm, and it takes more than 12 hours to reduce the temperature to 50 to 500 ppm' for cosmetic products. At present, most of the alcohols are removed by means of aeration bubbles (such as aeration agitation tank), but the effective gas-liquid contact area formed by the bubbles in the liquid phase is small and the gas-liquid contact surface renewal rate is slow, and the inert gas is dissolved therein. The effect of the quality of the phase is limited, so that the processing efficiency is not good. It is therefore necessary to increase the amount of inert gas, reduce the pressure or increase the temperature to achieve the desired efficiency. In recent years, the research and application of rotary ram filling beds have solved many problems that are difficult to solve under the constant gravity field. In particular, the rotary helium filling bed can greatly enhance the mass transfer process, so that the tens of meters high tower can be filled with a rotating bowl of about 2 meters. In the separation process of absorption, stripping, distillation, etc., it has been achieved that the effect is not expected to be 1281466. For example, U.S. Patent Nos. 4,283,255; 4,382,045; 4,382,900; and 4,400,275. Chinese Patent Publication No. CN111 61 46A (1996) proposes a method for preparing ultrafine particles using the mass transfer apparatus, wherein the multiphase stream is fed from the inner and outer tubes of the concentric sleeve through a distributor to a rotating crucible bed. The position of the axis is contacted and reacted in the helium bed by rotating the gravitational field. Since this technology is a new technology that emerged in the 1980s, the internal quality communication mechanism continues to be explored, so its new application areas need to be continuously developed. For example, in the application of dealcoholation, no public reports have been reported. SUMMARY OF THE INVENTION A primary object of the present invention is to provide a process for removing unreacted alcohols from an ester product mixture, which has the advantages of reducing the amount of inert gas used, without increasing the temperature of the ester product mixture, and reducing the processing time. . The invention utilizes a rotary helium filling bed to change the gas-liquid contact mode, and the ester product mixture is cut into a thin liquid film and a small droplet by a high centrifugal force and a ruthenium to cause a high gas-liquid contact area. And high mass transfer efficiency, so that the alcohol is more easily removed from the ester product mixture, so that the removal time is shortened, the quality of the ester product is improved, and the alcohol content is lowered, thereby increasing the industrial utilization price. Embodiments A method for removing unreacted alcohols from an ester product mixture using a rotary helium packed bed, wherein the ester product has a carbon number of 10 to 30, and the 1281466 method comprises the steps of: a) treating an ester product The mixture is fed to an annular rotary enthalpy bed that is rotated about a central axis, the rotary sputum bed being located in a housing, such that the ester product mixture flows radially through the crucible in the rotating crucible bed Filling; b) simultaneously introducing a gas into the rotary enthalpy bed such that the ester product mixture contacts the gas as it flows radially through the entanglement, thus the unreacted alcohol contained in the ester product mixture The gas is stripped of the gas and discharged from the top of the tank, and a purified ester product is collected at the bottom of the tank. Preferably, the ester product mixture of step a) is introduced from the axial region of the rotary crucible bed. Preferably, the gas system of step b) is introduced from the periphery of the chamber such that the ester product mixture contacts the gas countercurrently as it flows radially through the charge. Preferably, the gas system of step b) is introduced from the axial region of the rotary crucible bed such that the ester product mixture is in downstream contact with the gas as it flows radially through the crucible. Preferably, the gas system of step b) is introduced from the bottom of the rotary crucible bed and flows out from the top of the rotary crucible bed, so that the ester product mixture flows radially through the crucible with the gas. Cross-flow contact. Preferably, a negative pressure is applied to the axial region of the rotary crucible bed such that the ester product mixture contacts the gas at low pressure while flowing radially through the crucible and is stripped. Gas of unreacted alcohol is discharged from the top of the tank through the axial center of the rotary crucible bed. Preferably, the process of the present invention further comprises repeating all or a portion of the pure 1281 466 ester product collected in step b) as a feed repeating steps a) and b) until the purified ester product obtained is obtained. Has a desired purity. Preferably, the gas of step b) is nitrogen, carbon dioxide, argon or water vapor. In the following, the invention will be described with reference to a preferred embodiment in a preferred embodiment. A rotary helium bed system suitable for use in the present invention is shown in FIG. As shown in Fig. 1, the ester product mixture in the material tank (1) is driven into the axial center of a toroidal rotary enthalpy bed via a liquid inlet (3) via a water pump (2), by means of a liquid distributor (4). ), evenly sprayed toward the annular material (5). The centrifugal force is generated by the driving of the variable speed motor (6), the liquid is quickly moved outward, collected at the bottom of the chamber (7) of the rotary rinsing bed, and finally discharged by the liquid outlet (8). At the same time, an inert gas (9) such as nitrogen, carbon dioxide, argon or other gas which does not participate in the reaction is introduced from the gas inlet (10) of the rotary enthalpy bed, and is countercurrently contacted with the ester product mixture in the mash (5). The unreacted alcohol contained in the ester product mixture is taken away, and finally the inert gas containing the alcohol is discharged from the gas outlet (11). Example 1 A n-butanol (NBA) test was carried out in batches using a system similar to that of Figure 1 for the butyl stearate (BST). The rotary rinsing bed is available in an internal diameter of 78 mm, an outer diameter of 160 mm and a thickness of 20 mm. The speed is fixed at 1300 rpm. The tamping used was a woven stainless steel wire mesh (specific surface area 1906 m2/m3). The enthalpy of the rotary enthalpy bed is 0.91 (the porosity is 1 when the enthalpy is not filled; the vacancy is 0 when the entanglement is fully charged), and the deionization of 1281 466 is the nitrogen gas. During the experiment, the BST is fed from the liquid inlet (3) to the rotary crucible bed and the liquid product from the liquid outlet (8) is introduced into the material tank (1) for reflow to the material tank (1). The experimental conditions and the results obtained are shown in the table. From this table, it was found that the purified product sampled from the liquid outlet (8) at the 7th minute had an NBA of 237 ppm, and at the 12th minute, the NBA was reduced to 43 ppm. Test 1 2 Conditions and Results Feed NBA Concentration (ppm) 46205 46205 Discharge NBA Concentration (ppm) 237 (7 min) 43 (12 min) Feed Temperature (°c) 120 120 Influent (g/min) 250 250 Nitrogen Quantity (L/min) 50 50 Speed (rpm) 1300 1300
實施例二 使用類似於圖1的系統進行硬脂酸丁酯（BST)連續式 脫除正丁醇（NBA)測試。旋轉塡充床規格爲：內徑20 mm， 外徑40 mm，厚度20 mm。轉速固定於1300 rpm。所使用 的塡充物爲編織不銹鋼金屬絲網具有比表面積1546 m2/m3。旋轉塡充床的塡充空隙度爲0.90。以水蒸汽爲脫 氣劑，並藉由氣體進口（10)抽氣而於低壓進行操作。實驗 時將BST由液體進口（3)進料至旋轉塡充床並由液體出口 (8)收集純化產物。實驗條件及所得到之結果如表。由此表 10 1281466 可以發現，經旋轉塡充床於低壓進行連續處理可使NBA降 至 43〜49 ppm 〇 測試 條件及結果 1 2 進料NBA濃度（ppm) 46205 46205 出料NBA濃度（ppm) 49 43 進料溫度fC) 111 114 進液量（g/min) 132 132 蒸汽量（kg/hr) 5 5 真空度（torr) 160 160 轉速（rpm) 1300 1300Example 2 A butyl butyrate (BST) continuous removal of n-butanol (NBA) test was carried out using a system similar to that of Figure 1. The rotary rinsing bed is available in an internal diameter of 20 mm, an outer diameter of 40 mm and a thickness of 20 mm. The speed is fixed at 1300 rpm. The entangled material used was a woven stainless steel wire mesh having a specific surface area of 1546 m2/m3. The entanglement gap of the rotary ram filling bed was 0.90. The water vapor is used as a deaerator, and is operated at a low pressure by pumping gas through the gas inlet (10). The BST was fed from the liquid inlet (3) to the rotary helium bed during the experiment and the purified product was collected from the liquid outlet (8). The experimental conditions and the results obtained are shown in the table. From Table 10 1281466, it can be found that continuous treatment at a low pressure through a rotary helium bed can reduce the NBA to 43 to 49 ppm. 〇 Test conditions and results 1 2 Feed NBA concentration (ppm) 46205 46205 Discharge NBA concentration (ppm) 49 43 Feed temperature fC) 111 114 Inlet volume (g/min) 132 132 Steam volume (kg/hr) 5 5 Vacuum degree (torr) 160 160 Speed (rpm) 1300 1300
實施例三 除了以棕櫚酸異辛酯（EHP)取代BST作爲進料外，重 覆施例二的步驟進行連續式脫除2-辛醇（2_EH)的測試。實 驗條件及所得到之結果如表。由此表可以發現，經旋轉塡 充床於低壓進行連續處理可使2-EH降至100 ppm以下。 11 1281466 測試 條件及結果 1 2 進料2-EH濃度（ppm) 5000 5000 出料2-EH濃度（ppm) 66 104 進料溫度（°c) 205 225 進液量（g/min) 54 54 氮氣量（L/min) 50 50 真空度（torr) 200 160 轉速（rpm) 1500 1500Example 3 In addition to replacing BST with a palmitic acid (EHP) as a feed, the procedure of Example 2 was repeated to perform a continuous removal test of 2-octanol (2_EH). The experimental conditions and the results obtained are shown in the table. From this table it can be seen that continuous treatment with a rotating crucible at a low pressure reduces the 2-EH to below 100 ppm. 11 1281466 Test conditions and results 1 2 Feed 2-EH concentration (ppm) 5000 5000 Discharge 2-EH concentration (ppm) 66 104 Feed temperature (°c) 205 225 Inlet volume (g/min) 54 54 Nitrogen Quantity (L/min) 50 50 Vacuum (torr) 200 160 Speed (rpm) 1500 1500
圖式簡單說明 圖1是本發明的較佳具體實施例的流程示意圖。 主要元件之圖號說明 1 物料槽 2 抽水泵 3 液體進口 4 液體分佈器 5 環狀塡料 6 變速馬達 7 艙 8 液體出口 9 惰性氣體 10 氣體進口 11 氣體出口 12BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a schematic flow diagram of a preferred embodiment of the present invention. Description of the main components Figure 1 Material tank 2 Pump 3 Liquid inlet 4 Liquid distributor 5 Annular material 6 Variable speed motor 7 Cabin 8 Liquid outlet 9 Inert gas 10 Gas inlet 11 Gas outlet 12