1261584 九、發明說明： 、 【發明所屬之技術領域】 本發明是有關於一種濃縮純化醇類水溶液的方法，且护 是有關於-健臨界流體環境下濃縮純化醇類水溶液的方法。 【先前技術】 超臨界流體乃是指物質處於臨界溫度以及臨界壓力以上 時之狀態。由於流體在臨界點附近具有高壓縮比以及盆它諸夕 • 特性，因此超臨界流體被認為是極具有開發潛力的萃取溶劑^ 自從1978年德國第一座超臨界流體工廠運作以來，所累 積的工程經驗已相當豐富，使得該項工程技術已日臻成熟。雖 然超臨界流體的應用很多，但商業化的腳步卻曾在年代初 期衰退過。之後，由於新的應用以及開發中國家的加入，促^ 商業化的腳步又再一次加速進行，目前估計全世界已有超過 100家的商業運轉工廠了，主要分佈在歐州，美國，日本，= 度以及中國大陸。 Φ 然而，超臨界流體萃取的工業應用雖多，但在工程設計上 除了固體形態的生物資源的萃取方法較成熟外，其它應用之工 2設計仍有相當大的努力空間。在針對液體形態的進料之應用 §中’雖然已有專利與文獻發表逆向流萃取的可行性，但其在 工程設計上的研究才剛引起少數學者的重視，其中又以酒&發 酵母液的濃縮純化以及紅酒的去醇製程受到最多的注意。 在台灣，由於半導體產業與電子業的發達，因此製程中清 洗用的異丙醇(isopropanol，IPA)之回收與再精製具有相當大的 市場性與國家政策發展的重要性。此些異丙醇廢液含有莫耳百 分比35以上的水，因此若欲回收與再精製此異丙醇廢液，必 1261584 之^進行共沸瘵餾。但是共沸蒸餾僅少數石化工廠有能力為 的。而且其能耗大、投資金額大、技術門檻高，所以並非一般 勺回收處理工廠所能快速引進與接受的方法。 【發明内容】 緣此，本發明的目的就是在於提供—種超臨界流體環境下 =、、、屯化_水溶㈣方法，本發日柯以直接應用於半導體業 =私中清洗㈣異丙g|之时與再精製，並對於未來服務國内 二賴發酵工業，以及食品與醫藥I業相_類溶夜的濃縮純 化，也將具有開發設計的服務能力。 本發_再—目的是提供—種超臨界流體環境下濃縮純 化_核液的方法，以提昇_超臨界越駐程設計能 力，亚為進一步跨足國際市場而準備。 本發明係經由熱力學相圖研究可行性，進而進行—系 t究，實在唯有在適當的操作條件下方可將水與醇類共 彿予以破壞的連續製程方法，此方法以超臨界流體萃取醇類水 =取的過程中，同時超轉流體破壞_水溶液 中的醇類财之㈣，而能萃取出高濃度之賴水溶液。 減實施例所述超臨界流體環境下濃縮純 倾類水减的綠，上叙超臨界流體魏下破壞醇類水 液中醇類與水之·的方法例如為在萃取時，使超流 醇類水溶液之溶流比(801酬10__)至少大於3。-本發明提出-種超臨界流體環境下濃縮純化醇類水溶 的方法，包括先將醇類水溶液泵入充滿超臨界流體的萃取管柱 中段部位。然後，利用萃取f柱使_水 相，其中汽相往萃取管柱上段流動，而液相往萃取 6 1261584 動。之後，由萃取管柱最上段排出今 界流體後，得到高於—共沸點濃度的醇二出= 化醇境下濃縮純 取管柱之進料(Feed)速率比至少大^體與_水溶液泵入萃 化醇佳實施例所述超臨界流體環境下賴 化醇實補所魏料越環境下漢縮純 溶上述之醇類水溶液例如為低碳數醇類水 或;醇=:?數醇™^ 化醇㈣魏了濃縮純 水之共沸點。 、之/、沸點為醇類水溶液中的醇類與 化醇佳實補料雜界雜環境下濃縮純 、、气相m合沾* 上述之利用萃取管柱使醇類水溶液分成 部位具==如分段控制萃取管柱之溫度’使其不同的 化醇明的較佳實施例所述超臨界流體環境下濃縮純 方法，上述之往萃取管柱上段流動的汽相，可 管柱最上段果入的醇類水溶液進行回流，或是 刀又工，|卒取官柱最上段之溫度，使其溫度低於萃取管柱下段 之溫度的方式進行回流，以進行精餾。 Ϊ261584 化醇交佳實施例所述超臨界流體環境下濃縮純 進上述之往萃取管柱下段流動的液相，可 醇類i液的超臨界流體接觸，以將液相中之 化醇境下濃縮純 的方法，上述之高於共沸點濃度的醇類水溶液之 以:;為'編分比86以上(以1PA與水為 古二I里百刀比86，依照本發明的較佳實施例實驗所得之 度的醇類水溶液之濃度為至少重量百分比92以 上或達重量百分比98以上）。 化醇紐實關㈣超臨界流贿境下濃縮純 讀的綠，上狀醇齡絲祕的妓在重量百 二重量點濃度的軸水溶液之濃度範圍例 ▲依照本發明的較佳實施例所述超臨界流體環境 進匕液的方法，上述之高於共彿點濃度的醇類水溶二 吸水後，製成重量百分比_之醇類溶液。 愈水臨界㈣環境下破壞_水溶液中的醇類 /、之/、沸，因此可以萃取出高濃度之醇類水溶液。 =發明因分段控制萃取管柱之溫度，使萃取管柱不同的部 八有不同的溫度，因此可以在管柱中_進行精錦。 ^發明所提出之超臨界频環境下濃賴$ 的方法可以直接應用於半導體業製程中清洗用的 收與再精製轉體製造錢電子工廠的異丙_^、。叫之回 =卜，本發啊控娜類水溶液麟的濃 刀比8〇以下’使料取狀萃餘物濃度翻在”百分比^ 8 1261584 類，因ί方在超臨界流體環境下萃取醇類水溶液中的醇 理業4=r能乾低，而且咖^ 懂，下為文 么上述和其他目的、特徵和優點能更明顯易 下文特軸佳貫施例，並配合所關式，作詳細說明如下。 【實施方式】 液的出―、種超臨界流體環境下濃縮純化醇類水溶 體破评，界錢萃取_水溶液’同時彻超臨界流 财减中的醇類與水之共沸，因此可以萃取出濃度 问運重里百分比86以上之_水溶液(以IpA與 點濃度為重量百分比86)。 ^例其共淹 化酿㈣触實補職雜界频環境下濃縮純 洛φ 液的^ ’上述之超臨界流體環境下破壞醇類水溶1261584 IX. Description of the Invention: [Technical Field of the Invention] The present invention relates to a method for concentrating and purifying an aqueous alcohol solution, and is a method for concentrating and purifying an aqueous alcohol solution in a healthy critical fluid environment. [Prior Art] A supercritical fluid is a state in which a substance is at a critical temperature and a critical pressure. Supercritical fluids are considered to be extremely promising extraction solvents due to their high compression ratio near the critical point and their ionic properties. ^ Since the operation of the first supercritical fluid plant in Germany in 1978, it has accumulated The engineering experience has been quite rich, making the engineering technology mature. Although the application of supercritical fluids is numerous, the pace of commercialization has declined in the early years. Later, due to new applications and the participation of developing countries, the pace of commercialization has once again accelerated. It is estimated that there are more than 100 commercial operation factories in the world, mainly in Europe, the United States, Japan, = Degree and mainland China. Φ However, although industrial applications of supercritical fluid extraction are numerous, in engineering design, in addition to the mature method of extraction of biological resources in solid form, there are still considerable efforts in the design of other applications. In the application of liquid form feeds § 'Although patents and literature have published the feasibility of reverse flow extraction, its research on engineering design has just attracted the attention of a few scholars, among which wine & Concentration and purification, as well as the de-alcohol process of red wine, receive the most attention. In Taiwan, due to the development of the semiconductor industry and the electronics industry, the recovery and re-purification of isopropanol (IPA) for cleaning in the process has considerable market and national policy development importance. These isopropyl alcohol waste liquids contain water having a molar percentage of 35 or more. Therefore, if the isopropyl alcohol waste liquid is to be recovered and re-refined, it is necessary to carry out azeotropic distillation. But azeotropic distillation is only available in a few petrochemical plants. Moreover, it has a large energy consumption, a large investment amount, and a high technical threshold, so it is not a method that can be quickly introduced and accepted by a general scoop recycling processing plant. SUMMARY OF THE INVENTION Accordingly, the object of the present invention is to provide a method for the determination of water, water, and water in a supercritical fluid environment. The method is directly applied to the semiconductor industry = private cleaning (four) isopropyl g At the time and refining, and for the future service of the domestic secondary fermentation industry, as well as the food and medicine I industry, the concentration and purification of the same type of night, will also have the ability to develop and design services. The purpose of this is to provide a method for concentrating and purifying _nuclear fluid in a supercritical fluid environment to enhance the _ supercritical over-scheduled design capability, and prepare for further international market. The present invention is based on a thermodynamic phase diagram to study the feasibility, and then to carry out a series of studies, it is only a continuous process method that can destroy water and alcohol under appropriate operating conditions, this method extracts alcohol by supercritical fluid Water-like = in the process of taking, while the super-transfer fluid destroys the alcohol in the aqueous solution (4), and can extract a high concentration of aqueous solution. The method for reducing the green color of the pure decanter in the supercritical fluid environment according to the embodiment, and the method for destroying the alcohol and the water in the alcohol liquid in the supercritical fluid, for example, is to make the superfluid alcohol during extraction. The solution ratio of the aqueous solution (801% 10__) is at least greater than 3. - The present invention provides a method for concentrating and purifying alcoholic water in a supercritical fluid environment, comprising first pumping an aqueous alcohol solution into a middle portion of an extraction column filled with a supercritical fluid. Then, the extraction f column is used to make the aqueous phase, wherein the vapor phase flows to the upper portion of the extraction column, and the liquid phase moves to the extraction 6 1261584. Thereafter, after the current boundary fluid is discharged from the uppermost portion of the extraction column, the feed rate (Feed) rate of the concentrated and purely packed column is higher than the azeotropic concentration. Pumped into the extracting alcohol, in the supercritical fluid environment, in the supercritical fluid environment, the lysine is added to the environment, and the above-mentioned alcoholic aqueous solution is, for example, a low carbon number alcohol water or an alcohol=:? Alcohol TM ^ Alcohol (4) Wei has azeotropic point of concentrated pure water. / /, the boiling point of the alcohol in the aqueous solution of alcohol and the alcohol in the mixed environment, the pure environment, the gas phase m combined with the above-mentioned use of the extraction column to make the alcohol aqueous solution into parts == a method for concentrating and controlling the temperature of the extraction column to make it different in the supercritical fluid environment, and the above-mentioned vapor phase flowing in the upper portion of the extraction column can be the uppermost stage of the column The aqueous alcohol solution is refluxed, or the knife is worked again. The temperature of the uppermost portion of the column is taken to reflux at a temperature lower than the temperature of the lower portion of the extraction column for rectification. Ϊ 261 584 化 化 化 化 化 化 化 化 584 584 584 584 584 584 584 584 584 584 584 584 584 584 584 584 584 584 584 584 584 584 584 584 584 584 584 584 584 584 584 584 584 584 584 584 584 584 584 584 Concentrated pure method, above the aqueous solution of the alcohol having a higher boiling point concentration;; is a 'scoring ratio of 86 or more (with 1PA and water as the ancient two-hundred-knife ratio 86, in accordance with a preferred embodiment of the present invention The concentration of the aqueous alcohol solution obtained by the experiment is at least 92% by weight or more than 98% by weight. Alcohol New Zealand (4) Concentration of purely read green under supercritical bribery, the concentration range of the upper aqueous sputum sputum at a weight of one hundred and twenty weight point of the aqueous solution of the shaft ▲ according to a preferred embodiment of the present invention The method for introducing a supercritical fluid environment into a sputum liquid, wherein the above-mentioned alcohol is dissolved in water at a concentration higher than a common point concentration, and then is made into an alcohol solution having a weight percentage. In the critical water environment (4), the alcohol in the aqueous solution is destroyed/, and the boiling is carried out, so that a high concentration of the alcohol aqueous solution can be extracted. =Invented by the segmented control of the temperature of the extraction column, so that the different parts of the extraction column have different temperatures, so the brocade can be carried out in the column. ^ The method of relying on the supercritical frequency environment proposed by the invention can be directly applied to the isopropylation of the charging and refining rotor manufacturing electronics factory in the semiconductor industry. Call it back = Bu, this hair ah control Na-type aqueous solution Lin thick knife than 8 〇 'to make the material extract uranium concentration turned "% ^ 8 1261584 class, because ί Fang in the supercritical fluid environment extraction of alcohol The alcohol industry in the aqueous solution 4=r can be low in dryness, and it can be understood from the following. The above and other purposes, features and advantages can be more obvious. The detailed description is as follows. [Embodiment] The liquid is discharged, and the concentrated and purified alcoholic water solution is degraded in a supercritical fluid environment, and the boundary water extraction_aqueous solution is simultaneously azeotropy of the alcohol and water in the supercritical flow reduction. Therefore, it is possible to extract an aqueous solution (concentration of IpA and point concentration of 86) in a concentration of more than 86% of the weight of the weight. (Completely, the total concentration of IpA and point concentration is 86). 'The above-mentioned supercritical fluid environment destroys alcoholic water soluble
醇麵^1與水之料的方法例如為在萃取時使超臨界流體與 %頦水溶液之溶流比至少大於3。 本發明更提丨-種超臨界流贿境下濃縮純化醇類水溶 方法包括將醇類水溶液泵人充滿超臨界流體的萃取管柱 ^中段部位。紐’ 萃取管柱使_水溶液分成—汽相與 —液相，其中汽相往萃取管柱上段流動，而液相往萃取管柱下 ，流動。之後’由萃取管柱最上段㈣汽_氣體，經分離出 =界j體後，得到高於n點濃度_類水溶液。以及， ^萃取官柱最下段排出液相的液體，經分離出超臨界流體後， 得到低於共沸點濃度的醇類水溶液。 依照本發明的較佳實施綱述超臨界越環境下濃縮純 1261584 化酵類水溶_方法’為達到_超臨界频破壞_水溶液 中酵類與水之共_目的，可㈣例如將上述之超臨界流體血 醇類水溶液泵人萃取管柱之補速率tb㈣至少大於3的^ 法，即可使萃取時之超臨界流體與_水紐的溶航至少 於3 〇 ▲依照本發明雜佳實闕所述超臨界紐環境下濃縮純 化醉類水溶液的方法，上述之超臨界流體例如為二氧化石炭、乙 烧或氧化亞氮。 一依照本發明的較佳實施例所述超臨界流體環境下濃縮純 化液的方法’上述之醇類水溶液例如低碳數醇類水溶 ^其中低石反數醇類水溶液例如為乙醇、正丙醇、異丙醇或 醇水溶液。 / „依f本發明的較佳實施騎述超臨界流體環境下濃縮純 水溶液的方法，上述之共沸點為醇類水溶液中的醇類與 水之共彿點。 〃 圖 繪福本發_之—種超臨界雜魏下濃縮純化醇作方法的—個較佳實施例之系統流程圖，其一般的操 類 •=做為超臨界流體之二氧化碳、乙燒或氧化亞氮則經預 二益111預冷後，經由泵112以及] 溫 =於蓄—，蓄壓缸14。的壓力則丄 •二f缸！40中的超臨界流體1101經壓力調節閥161降至所 ;二的細作壓★力’並經加熱器115加熱後進入萃取管柱最 又105 ’使萃取彡統轉在所需㈣作壓力與溫度(萃取 S主刚的*度控制裝置树示於圖1中），並以出口的計 1261584 I針閱1001及二氧化碳流量計H41測量洩壓的二氧化碳 11〇流量以控制超臨界流體1101於系統中之流量；The method of the alcohol surface and the water material is, for example, a solution flow ratio of the supercritical fluid to the aqueous solution of hydrazine at least greater than 3 at the time of extraction. The invention further provides that the method for concentrating and purifying alcoholic water in a supercritical bribery method comprises pumping an alcohol aqueous solution into a middle portion of an extraction column of a supercritical fluid. The New's extraction column separates the aqueous solution into a vapor phase and a liquid phase, wherein the vapor phase flows to the upper portion of the extraction column, and the liquid phase flows under the extraction column. After that, by the uppermost section (4) of the extraction column, the vapor_gas is separated, and the concentration of the boundary is obtained. And, extracting the liquid from the liquid phase at the lowermost stage of the official column, and after separating the supercritical fluid, obtaining an aqueous alcohol solution having a concentration lower than the azeotropic concentration. According to a preferred embodiment of the present invention, the supercritical environmentally-concentrated pure 1261584 lysate water-soluble method is used to achieve _ supercritical frequency destruction _ aqueous solution of yeast and water, and (4) for example, the above super The critical fluid blood alcohol aqueous solution pump extracting column has a replenishing rate tb (4) of at least greater than 3, so that the supercritical fluid and the _ water nucleus at the time of extraction can be at least 3 〇 ▲ according to the present invention. The method for concentrating and purifying a drunken aqueous solution in the supercritical New Zealand environment, wherein the supercritical fluid is, for example, carbon dioxide, ethylene or nitrous oxide. A method for concentrating a purified liquid in a supercritical fluid environment according to a preferred embodiment of the present invention. The above aqueous alcohol solution such as a low carbon number alcohol is dissolved in water, wherein the low rock inverse alcohol aqueous solution is, for example, ethanol or n-propanol. , isopropanol or aqueous alcohol solution. / 。 According to a preferred embodiment of the present invention, a method of concentrating a pure aqueous solution in a supercritical fluid environment, wherein the azeotropic point is a point of coexistence between the alcohol and the water in the aqueous alcohol solution. A system flow chart of a preferred embodiment of a method for concentrating and purifying alcohol under supercritical heterowei, the general operation type == carbon dioxide, ethyl bromide or nitrous oxide as a supercritical fluid is pre-diluent 111 After the pre-cooling, the pressure of the accumulator 14 via the pump 112 and the temperature of the accumulator 14 is reduced by the pressure regulating valve 161; Force 'and heated by heater 115 to enter the extraction column and the most 105 ' to make the extraction system in the required (four) for pressure and temperature (extraction S main control * degree control device tree shown in Figure 1), and The outlet meter 1261584 I pin 1001 and the carbon dioxide flow meter H41 measure the pressure of the carbon dioxide 11 泄 flow to control the flow of the supercritical fluid 1101 in the system;
3·畜壓紅140中的超臨界流體1101經另一壓力調節閥162輸 入至進料儲槽142中，並其壓力設定略高於壓力調節閥161 白勺壓力’進料儲槽142中的醇類溶液利用高壓的超臨界流 體U〇l推送並經加熱器117加熱後進入萃取管柱中段 ’當醇類溶液進入萃取管柱！〇〇時其流量可透過壓力調 郎間161與壓力調節閥162所調節的壓力差予以控制，並 可同時使用一限流器1002以幫助控制其流量，其中限流器 1002例如可選用50微米左右的流孔板。本實施例中的容流 比可以利用壓力調節閥161與壓力調節閥162所設定的壓 力差以及限流器1〇02所選用的流孔板之值(Cv: Capacity 〇f valve)加以計算並控制，使超臨界流體與醇類水溶液之溶流 …夕大於3 ’以達到利用超臨界流體破壞醇類水溶液中醇 類與水之共沸的目的； 4·之後’富超臨界流體的氣相經萃取管柱最上段101排出， 亚降壓至常壓即可回收高濃度的醇類水溶夜於分離槽H4 中其中，南濃度的醇類水溶液之濃度可高達重量百分比 以上(以IPA與水為例其共沸點濃度為重量百分比86)， 且可進一步經由分子篩吸水後，製成重量百分比100之醇 類溶液； 5.=離槽144巾的高濃度醇類水溶夜定時排出以獲取萃出物 或取樣’並可進一步利用回流泵145經加熱器146加熱後， $之回*至萃取官柱最上段謝以進行汽相（即富超臨界流 體相）的精館，或是分段控制萃取f柱最上段而之溫度， 使其/皿度低於萃取錄下段1G4之溫度的方式進行回流， 11 ^261584 以進灯精潑。本實施例中的回流比則可以利用回流泵145 的流量設定來調節； 《，相（即富水相)則在萃取管柱最下段1〇5暫存，並固定一段 時間排放—次或是使用液健制裝置170予以控制其液 位二由=本發明的研發設計並不需要再滞器，因此萃取管 柱最下^又1〇5暫存的液相可以與新鮮的超臨界流體11〇1接 觸之後再排出，以將液相中之醇類溶液再萃取至汽相中， ^接觸對萃取管柱下段1〇4即汽提咖卯⑽)段的效率影 二並不大。之後’排出的萃餘物則可以利關如氣相層析 術(Gas Chr〇mat〇graphy，GQ進行醇類水溶夜濃度的分析。 、本發明之超臨界流體環境下濃縮純化賴水溶液的方法 直接應用於半導體職程巾*洗用的異㈣之回收與再 ^衣半導體製造業或電子工薇的異丙醇廢液。以一個曰處理量 :頓異丙醇廢液浪度—般在65莫耳百分比左右的半導』 =二由烟之方法處理後的萃出物_^^ 產出Λ 7 5'百ί比98之異丙醇溶液，以及萃餘物(Rafflnate) ·5督重量百分比1G之異丙醇廢液。前者經由分子篩 衣付重里百分比觸的純異丙醇溶液，後者可當作 八匕有告廢棄物的高熱值燃料加以一併處理。 H，、/1綠示為本發明之—種超臨界流體環境下濃縮純化醇 二：液的方法的另一個較佳實施例之實驗系統流 · 般的實驗操作程序如下： 口具一 水機的電源24小時皆開*，維持乙二醇2 12 1 ·開閘閥221、222後，將果22〇電源開啟使前述之乙二醇加 1261584 ，預~為231中循環，再將二氧化碳鋼瓶23〇開啟以避免二 氧化石反在進入泵232前汽化(此實驗系統因所使用之泵232為 液體泵，若二氧化碳汽化將影響其增壓）； 3·開空氣壓縮機250電源及出σ閘閥2川吏之開始運作以產生 = ^32運作時所需之驅動空氣使泵232開始運作增壓，（壓縮 =氣進入泵232前會先經過過濾器(filter2511、2512)以過濾壓 鈿空氣中的雜質、水氣及油氣，再利用手動閥252及閘閥253 凋正壓lis空氣進入泵232的壓力及空氣量以控制泵232的運 • 作； 4二建立蓄壓缸240的壓力，其壓力值由壓力計24〇1讀得，並 藉由調整背壓閥260來控制蓄壓缸240的壓力； 5·，手動閥241 ’藉由調整壓力調節閥261來控制萃取管柱2〇〇 的壓力，其壓力值由壓力計2611讀得； 6·開手動閥206，使二氧化碳依序經由加熱器2〇7、計量針閥 208、分離槽244、二氧化碳流量計2441直接排至大氣中，藉 由調整計量針閥208的開度來控制二氧化碳11〇的流速(Fs); 7.開啟溫控箱的電源並設定實驗的操作溫度，亦即設定熱電偶 2021的溫度(τΕ)以及熱電偶2041的溫度(τΒ)，以加熱萃取管 柱200。其中熱電偶2021位於萃取管柱上段2〇2，而熱電偶 2041位於萃取管柱下段204(此設計可使本發明達到分段控制 萃取管柱之溫度，使萃取管柱不同的部位具有不同的溫度）； 8·配置實驗所需的醇類水溶液270，因此其濃度(Cf)為已知， 再用禮度a十測置其密度後置於天枰2701上。本發明研究發 現’當醇類水溶液的濃度在重量百分比8〇以下時，萃餘物之 濃度範圍可在重量百分比2.5以下； 9·待溫度、壓力、二氧化碳的流速接達穩定狀態，便可使醇類 13 1261584 水溶液270進入萃取管柱2〇〇 ; -1〇·開线壓縮機280電源及出口間閥281使之開始運作以產 生泵271運作日守所需之驅動空氣，開手動閥272、並藉由調整 手動閥282的開度改變壓縮機壓縮空氣經由過遽器2川送入 泵271的量，進而控制醇類水溶液27〇的流速(Ff); 11·待醇類水溶液270的流速調整至所欲之值後，開手動閥 274 ’關手動閥272，使醇類水溶液27〇進入萃取管柱2〇〇， 並開始計時； • I2·每隔一段時間間距，記錄壓力計2611、熱電偶2011、熱電 偶202卜熱電偶204卜熱電偶205：1、二氧化碳流量計2441 及天秤2701上的數值。其中熱電偶2〇21、熱電偶加“可分 段控制萃取官柱200之溫度，而熱電偶2〇11(位於萃取管柱最 上段2〇1)、熱電偶20M(位於萃取管柱最下段2〇5)只有感測溫 度在此實驗系統中並不控制管柱最上段2〇1及管柱最下段 205之溫度；， 13·待分離槽244開始有液位累積，每隔―段時關距，開手 動閥2442，用樣品瓶收集萃出物，同時開手動闕2〇〇ι，用樣 品瓶收集萃餘物。其中，萃出物為高濃度的賴水溶液270， 其濃度可至少達重量百分比92以上或達重量百分比98以 上，且可進一步經由分子篩吸水後，製成重量百分比100之 醇類溶液； 當實驗完成時，依序關手動閥282、手動閥274、閘閥281、 壓縮機280電源，使醇類水溶液270停止進入萃取管柱2〇〇。 再將手動閥241關閉，使二氧化碳停止進入萃取管检2〇〇 ; 15肩手閥2442收集殘留於分離槽244中的萃出物，開手間 2〇〇1收集殘留於萃取管柱2〇〇中的萃餘物； 14 1261584 16. 開手動閥241、手動閥2442、手動閥2001，利用二氧化碳 — 的流動來清洗系統管路，排除所有的醇類水溶液27〇 :系二 外； … 17. 關閉溫控箱的電源、手動閥241、手動閥2442、手動閥 18. 關閉閘閥253、開閥251使泵232停止運作；（若過遽器洲 内的水已滿，為了避免水進入果232，關閑閥攻、間闕， 用喷搶茂壓後水會自動流出，而過滤器2511 拔下倒除） >〜而于動 19. 關二氧化碳鋼瓶230，關閉泵220之電源； 餘物中所央帶的二氧化痛，即可 液的界缝絲-賴水溶 1.經由本發明所處理過之醇類水溶 重置百分比86(以IPA與水為 86,佑昭*旅〇0上人+ _ /、⑼…、5〆辰没為重置百分比 > 4.§ "々較佳貫施例實驗所得之高於共沸點濃产 :容液之濃度為至少重量百分比92達重 以上），且可進-步經由分子篩 里了刀=98 的醇類溶液。 俊衣成重置百分比100% 分比取前_貞水溶液濃度在重量百 百分比2.5以^卒 醇類水溶液萃餘物濃度可低於重量 可以3首用超臨界流體濃縮純化醇類水溶液的方法 精Ι^ίίΓ半導體業製程中清洗用的異丙醇之回收盥再 精衣+導體製造業或電子工 #之口 I、再 1261584 4.經由本發明所處理過之醇類水溶液之者 ，害廢棄物的高熱值燃料加以處理。 ^ 5·本發明研究設計分段控制萃取管柱之溫度，使萃取管柱 不同的部位具有不_溫度，因此可以在管柱巾同時進行精 錦。 ^ 6·由於國内製酒與發酵工業以及食品與醫藥工業均涉及 醇類水溶夜的濃縮純化，因此本發明之利用超臨界流體濃縮純 化醇類水溶液的方法，對於上述相關產業也具有開發設計的服 ^ 務能力。 雖然本發明已以較佳實施例揭露如上，然其並非用.以限定 本發明’任何熟習此技藝者，在不脫離本發明之精神和範圍 内’當可作些許之更動與潤飾，因此本發明之保護範圍當視後 附之申睛專利範圍所界定者為準。3. The supercritical fluid 1101 in the livestock pressure red 140 is input to the feed reservoir 142 via another pressure regulating valve 162, and its pressure is set slightly higher than the pressure in the feed reservoir 142 of the pressure regulating valve 161. The alcohol solution is pushed by the high pressure supercritical fluid U〇l and heated by the heater 117 to enter the middle section of the extraction column 'when the alcohol solution enters the extraction column! The flow rate can be controlled by the pressure difference between the pressure regulating chamber 161 and the pressure regulating valve 162, and a restrictor 1002 can be used simultaneously to help control the flow rate thereof, wherein the restrictor 1002 can be, for example, 50 micrometers. Left and right orifice plates. The volume ratio in the present embodiment can be calculated by using the pressure difference set by the pressure regulating valve 161 and the pressure regulating valve 162 and the value of the orifice plate (Cv: Capacity 〇f valve) selected by the restrictor 1〇02. Control, so that the supercritical fluid and the aqueous alcohol solution are dissolved ... at night greater than 3 ' to achieve the purpose of using a supercritical fluid to destroy the azeotropy of the alcohol and water in the aqueous alcohol solution; 4. After the 'rich supercritical fluid gas phase It is discharged through the uppermost section 101 of the extraction column, and the high-pressure alcohol is dissolved in the separation tank H4 by sub-pressure reduction to normal pressure. The concentration of the alcohol solution in the south concentration can be up to the weight percentage or more (by IPA and water). For example, the azeotropic concentration is 86% by weight, and further can be made into a 100% by weight alcohol solution after absorbing water through the molecular sieve; 5. = high concentration alcohol in the tank 144 is dissolved at night to obtain the extraction. The material or sample can be further heated by the reflux pump 145 via the heater 146, and the back of the extraction column is applied to the uppermost stage of the extraction column to perform the vapor phase (ie, the rich supercritical fluid phase). Extracting the top of the f-pillar And the temperature, it / dish of the extracted recorded below the lower temperature of the 1G4 manner reflux in 11 ^ 261,584 poured into fine lamp. The reflux ratio in this embodiment can be adjusted by the flow rate setting of the reflux pump 145; ", the phase (ie, the water-rich phase) is temporarily stored in the lowermost section of the extraction column 1〇5, and is fixed for a period of time - or The liquid level control device 170 is used to control the liquid level. The design of the present invention does not require a re-retenterator. Therefore, the liquid phase of the extraction column is the lowest and the liquid phase can be temporarily mixed with the fresh supercritical fluid. After the contact of 〇1, it is discharged again to re-extract the alcohol solution in the liquid phase into the vapor phase, and the efficiency of the contact with the lower section of the extraction column 1〇4, that is, the stripping curry (10)) is not large. After that, the discharged raffinate can be used for gas chromatography (Gas Chr〇mat〇graphy, GQ for the analysis of the concentration of alcoholic water-soluble night. The method for concentrating and purifying the aqueous solution in the supercritical fluid environment of the present invention) It is directly used in the recovery of semiconductor job towel * washing (4) and the recycling of isopropyl alcohol in the semiconductor manufacturing industry or electronic weiwei. The amount of 曰 曰 : : 顿 顿 顿 顿 顿 — — — — — — — The semi-conductance of about 65 moles of 』 = two extracts treated by the method of smoke _^^ yield Λ 7 5' hundred mil ratio 98 isopropyl alcohol solution, and raffinate (Rafflnate) · 5 Du 1% by weight of isopropyl alcohol waste. The former is treated with a pure isopropanol solution with a percentage of the weight of the molecular sieve, and the latter can be treated as a high calorific value fuel for the gossip. H,, /1 green The experimental system flow of another preferred embodiment of the method for concentrating and purifying the alcohol two liquid in the supercritical fluid environment of the present invention is as follows: The power supply of the water dispenser is open for 24 hours. *, maintain glycol 2 12 1 · open the gate valves 221, 222, will be 22 The power is turned on to add the above-mentioned ethylene glycol to 1261584, and the cycle is 231, and then the carbon dioxide cylinder 23 is turned on to prevent the carbon dioxide from vaporizing before entering the pump 232. The experimental system uses the pump 232 as a liquid pump. If the carbon dioxide vaporization will affect its pressurization); 3. The open air compressor 250 power supply and the σ gate valve 2 start to operate to generate = ^32 drive air required for operation to make the pump 232 start operating boost, ( Compression = gas before entering the pump 232 will pass through the filter (filter2511, 2512) to filter the impurities, water and oil in the compressed air, and then use the manual valve 252 and the gate valve 253 to withstand the pressure of the positive pressure lis air into the pump 232 and The amount of air is used to control the operation of the pump 232; 4) the pressure of the accumulator cylinder 240 is established, the pressure value is read by the pressure gauge 24〇1, and the pressure of the accumulator cylinder 240 is controlled by adjusting the back pressure valve 260; 5. The manual valve 241' controls the pressure of the extraction column 2〇〇 by adjusting the pressure regulating valve 261, and the pressure value is read by the pressure gauge 2611; 6. The manual valve 206 is opened to sequentially pass the carbon dioxide through the heater 2 〇7, metering needle valve 208, separation tank 244 The carbon dioxide flow meter 2441 is directly discharged into the atmosphere, and the flow rate (Fs) of the carbon dioxide 11 控制 is controlled by adjusting the opening degree of the metering needle valve 208. 7. Turn on the power of the temperature control box and set the operating temperature of the experiment, that is, set The temperature of the thermocouple 2021 (τΕ) and the temperature of the thermocouple 2041 (τΒ) are used to heat the extraction column 200. The thermocouple 2021 is located in the upper section of the extraction column 2〇2, and the thermocouple 2041 is located in the lower section 204 of the extraction column (this The design can make the invention achieve the temperature of the extraction control column in stages, so that different parts of the extraction column have different temperatures); 8. Configure the aqueous alcohol solution 270 required for the experiment, so the concentration (Cf) is known. Then use the scale a to measure its density and place it on Tianzhu 2701. The research of the present invention finds that when the concentration of the aqueous alcohol solution is less than 8〇 by weight, the concentration of the raffinate may be less than 2.5% by weight; 9. The temperature, pressure, and carbon dioxide flow rate are connected to a steady state, so that Alcohol 13 1261584 Aqueous solution 270 enters the extraction column 2〇〇; -1〇·opening compressor 280 power supply and outlet valve 281 to start operation to generate the driving air required for pump 271 operation, open manual valve 272 And adjusting the opening degree of the manual valve 282 to change the amount of compressor compressed air sent to the pump 271 via the buffer 2, thereby controlling the flow rate (Ff) of the alcohol aqueous solution 27〇; 11. The alcohol-like aqueous solution 270 After the flow rate is adjusted to the desired value, the manual valve 274 is opened to close the manual valve 272, so that the alcohol aqueous solution 27〇 enters the extraction column 2〇〇, and starts timing; • I2·interval at intervals, recording the pressure gauge 2611 , Thermocouple 2011, Thermocouple 202, Thermocouple 204, Thermocouple 205:1, Carbon Dioxide Flowmeter 2441 and Libra 2701. Among them, thermocouple 2〇21, thermocouple plus “segmentable control of the temperature of the extraction column 200, while thermocouple 2〇11 (located in the uppermost section of the extraction column 2〇1), thermocouple 20M (located in the lowermost section of the extraction column) 2〇5) Only the sensing temperature does not control the temperature of the uppermost section of the column 2〇1 and the lowermost section of the column 205 in this experimental system; 13) The tank to be separated 244 begins to accumulate liquid level, every interval Close the distance, open the manual valve 2442, collect the extract with the sample bottle, and open the manual 阙2〇〇ι, collect the raffinate with the sample bottle. The extract is a high concentration of lyophilized water solution 270, the concentration can be at least Up to 92% by weight or more than 98% by weight, and further absorbing water through the molecular sieve to prepare an alcohol solution of 100% by weight; when the experiment is completed, the manual valve 282, the manual valve 274, the gate valve 281, and the compression are sequentially closed. The machine 280 is powered to stop the alcohol aqueous solution 270 from entering the extraction column 2〇〇. The manual valve 241 is closed to stop the carbon dioxide from entering the extraction tube. 2 The shoulder valve 2442 collects the residue remaining in the separation tank 244. Except, the opening of the room 2〇〇1 collection Residue left in the extraction column 2〇〇; 14 1261584 16. Open manual valve 241, manual valve 2442, manual valve 2001, use carbon dioxide - flow to clean the system piping, remove all alcohol aqueous solutions 27〇 : Department 2 outside; ... 17. Close the power supply of the temperature control box, manual valve 241, manual valve 2442, manual valve 18. Close the gate valve 253, open the valve 251 to stop the pump 232; (if the water in the basin has been Full, in order to avoid water entering the fruit 232, close the valve attack, the sputum, the water will automatically flow out after the spray pressure, and the filter 2511 is pulled out and remove) > ~ and move 19. Close the carbon dioxide cylinder 230, Turn off the power of the pump 220; the oxidative pain in the central zone of the residue, that is, the boundary of the liquid-dissolved water. 1. The alcohol-soluble resetting percentage of the alcohol treated by the present invention is 86 (IPA and water are 86). , You Zhao * Tourism 上 0 Master + _ /, (9) ..., 5 〆 没 is not a reset percentage > 4. § " 々 better example of the experiment results obtained above the azeotrope concentration: liquid The concentration is at least 92% by weight or more, and the alcohol solution of the knife = 98 can be further advanced through the molecular sieve. The percentage of resetting is 100%. The concentration of the aqueous solution is 5% by weight. The concentration of the aqueous solution of the alcohol can be less than the weight. The method can be used to concentrate and purify the aqueous alcohol solution with supercritical fluid. Γ 盥 盥 Γ Γ Γ Γ Γ Γ Γ Γ Γ Γ Γ Γ Γ Γ Γ Γ Γ Γ Γ Γ Γ Γ Γ Γ Γ Γ Γ Γ Γ Γ Γ Γ Γ Γ Γ Γ Γ Γ Γ Γ Γ Γ Γ Γ Γ Γ Γ Γ Γ The high calorific value fuel is treated. ^ 5. The research of the present invention designs the temperature of the extraction column to control the temperature of the column, so that the different parts of the extraction column have no temperature, so the fine brocade can be performed at the same time. ^6· Since the domestic wine and fermentation industry and the food and pharmaceutical industries all involve the concentration and purification of alcoholic water-soluble nights, the method for concentrating and purifying alcoholic aqueous solutions using supercritical fluids of the present invention has development and design for the above-mentioned related industries. Service ability. Although the present invention has been disclosed in the above preferred embodiments, it is not intended to limit the invention, and the invention may be modified and modified without departing from the spirit and scope of the invention. The scope of protection of the invention is subject to the definition of the scope of the patent application.
16 1261584 【圖式簡單說明】 ， 圖1繪示為本發明之一種利用超臨界流體濃縮純化醇類 水溶液的方法的一個較佳實施例之系統流程圖。 ^ 圖2繪示為本發明之一種利用超臨界流體濃縮純化醇類 水溶液的方法的另一個較佳實施例之實驗系統流程圖。 【主要元件符號說明】 100、 200 :萃取管柱 1001、208 :計量針閥 • 1002 :限流器 101、 201 :萃取管柱最上段 102、 202 :萃取管柱上段 103、 203 :萃取管柱中段 104、 204 :萃取管柱下段 105、 205 :萃取管柱最下段 110 :二氧化碳、乙烷或氧化亞氮 1101:超臨界流體 鲁 111、231 :預冷器 112、 220、232、271 :泵 113、 115、117、146、207 :加熱器 140、240 :蓄壓缸 142 :進料儲槽 144、244 :分離槽 145 :回流泵 1441、2441 :二氧化碳流量計 160、260 :背壓閥 17 1261584 161、162、261 :壓力調節閥 ， 170 :液位控制裝置 2011、2021、2041、2051 :熱電偶 210 :乙二醇 221、222、251、253、281 :閘閥 230 :二氧化碳鋼瓶 2401、2611 :壓力計 250、280 :壓縮機 φ 25H、2512、2811 :過濾器 206、241、252、272、274、282、2001、2442 ··手 動閥 270 :醇類水溶液 2701 :天秤16 1261584 BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a system flow diagram of a preferred embodiment of a method for purifying an aqueous alcohol solution using a supercritical fluid according to the present invention. Figure 2 is a flow chart showing an experimental system of another preferred embodiment of a method for purifying an aqueous alcohol solution using a supercritical fluid according to the present invention. [Main component symbol description] 100, 200: Extraction column 1001, 208: Metering needle valve • 1002: Flow restrictor 101, 201: Uppermost section of extraction column 102, 202: Upper section of extraction column 103, 203: Extraction column Middle section 104, 204: lower section of extraction column 105, 205: lowermost section of extraction column 110: carbon dioxide, ethane or nitrous oxide 1101: supercritical fluid Lu 111, 231: precooler 112, 220, 232, 271: pump 113, 115, 117, 146, 207: heaters 140, 240: accumulators 142: feed reservoirs 144, 244: separation tanks 145: reflux pumps 1441, 2441: carbon dioxide flow meters 160, 260: back pressure valves 17 1261584 161, 162, 261: pressure regulating valve, 170: liquid level control device 2011, 2021, 2041, 2051: thermocouple 210: ethylene glycol 221, 222, 251, 253, 281: gate valve 230: carbon dioxide cylinder 2401, 2611 : Pressure gauges 250, 280: Compressors φ 25H, 2512, 2811: Filters 206, 241, 252, 272, 274, 282, 2001, 2442 · Manual valve 270: Alcohol solution 2701: Libra
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