201020318 六、發明說明： 【發明所屬之技術領域】 本發明係有關於一種油品之改質方法，特別係有關於 一種利用次臨界二氧化碳流體之油品之改質方法。 【先前技術】 加氫製程為目前常使用的油品改質方法之一。然而， 由於油品的黏度高，使得氫氣於油品中的溶解度不高，而 造成氣液反應物之間的質傳效果不佳。此外，當使用具孔 洞性質的觸媒時，油品進入孔洞内部的速率慢，因此使氫 化反應的效率受到限制。欲提高溶解度的一種方法係於大 於2000psi的高壓環境下，然而此需要複雜且昂貴的高壓 設備且須消耗大量的氫氣，因此造成製程之危險與操作成 本的提高。 此外，含氧量高的油品對觸媒具有腐蝕性，因此黏滯 在觸媒表面的油品會造成嚴重觸媒毒化的問題，且黏滯在 觸媒孔洞中的油品會造成孔洞阻塞的問題，使得反應效率 降低且改質之油品品質不佳。 因此有需要提供一種油品之改質方法，以克服先前技 藝之不足。 【發明内容】 本發明提供一種油品之改質方法，包括：在觸媒之存 在下，使油品與氳氣接觸以進行加氫脫氧反應，該加氫脫 201020318 氧反應係於次臨界二氧化碳流體中進行。 本發明還提供一種油品之改質方法，包括：於一反應 器中且在觸媒之存在下，先以使一比例之氫氣及二氧化碳 通入該反應器中，且使該反應器具有穩定之氮化反應溫度 及氳化反應壓力，該二氧化碳為次臨界流體，接著再以固 定流量將該油品注入反應器中，使油品及氫氣接觸以進行 加氫脫氧反應。 【實施方式】 本發明提供一種油品之改質方法，包栝在觸媒之存在 下，使欲處理之油品與氫氣接觸以進行加氫脫氣反應，其 中氫化反應係於次臨界二氧化碳流體中進行。本發明使用 次臨界二氧化碳流體能大幅提高油品改質的效率。 本發明之欲處理油品包括（但不限於）生質物裂解油 品、生質柴油、廢潤滑油、廢食用油、塑膠裂解油品或輪 胎裂解油品。一般而言，需要做改質處理之油品的氧含量 高（大於40%)且不穩定，因此品質不佳。 本方法之次臨界二氧化碳流體的形成主要是使反應環 境的壓力處在使二氧化碳流體成為次臨界狀態的條件下。 因此，氫化反應的壓力係小於約1000 psi，較佳介於約 psi至約lOOOpsi，溫度介於約300Ϊ至約5〇(rc。由於次臨 界二氧化碳流體不需達到臨界壓力，係於較低壓的環境下 形成，因此能減少能源耗用及設備成本。 本方法中的加氣脫氧反應係於次臨界二氧化碳流體中 201020318 進行。次臨界二氧化碳流體使油品具有介於液體及氣體之 間的膨脹液體（expended liquid)特性且黏度大幅變小，當在 此膨脹液體中進行氫化或氫甲醛化反應時，即使有機溶劑 無法完全溶於二氧化碳中形成均相反應，但由於反應氣體 能大量溶解於液相溶劑中，有效排除氣液介面間之質傳阻 力而提高氳氣的溶解度，此外，油品能夠迅速流經觸媒表 面甚至進入孔洞内部，提高觸媒的有效反應面積，再者， 由於油品的熱傳阻力變小，因而提高油品的轉化效率。另 外，由於油品不會黏滞在觸媒表面，而避免了觸媒毒化的 問題。 本方法可在反應器，例如固定床反應器中進行。觸媒 可設置於反應器中。較佳者，是使觸媒與惰性石英砂混合 以固定於反應器中。於實施例中，觸媒粒徑大於石英砂， 因此可利用石英砂填充觸媒之間的空隙以達到固定之效 果。使用石英砂的好處還包括其具有蓄熱功效，能夠有效 的助益反應器溫度的穩定性並減少熱能損耗，再者，石英 砂亦能增加油品流經反應器時的分散性，使油品與觸媒及 氫氣的混合更加均勻，並防止產物回流。 本方法所使用之觸媒包括金屬，例如鉑（Pt)、鈀(Pd)或 鎳鉬合金Ni-Mo。觸媒可進一步使用金屬氧化物擔體，例 如氧化銘（Al2〇3)或沸石（Zeolitic)。觸媒之粒徑可介於約 1mm至約10mm。石英砂之粒徑可介於8 mesh至18 mesh。 石英砂與觸媒之重量比可介於5:1至10:1。 在本發明之方法中，反應器的氳化反應壓力可利用將 氫氣及二氧化碳通入反應器中後，以調控氫氣及二氧化碳 5 201020318 之流量的方式予以控制。較佳的’通入反應器中的氣氣及 二氧化碳具有一固定的流量比例。氫氣與二氧化碳之、充θ 比可介於1:0.1至1:10。 在本發明之方法中，於通入氫氣、二氧化後及油品至 反應器内以進行氫化反應之前，可先對觸媒進行再i (regeneration)程序以提升氫化反應的效率。首先，對觸媒 進行煅燒’其可將空氣通入反應器内進行加熱。锻燒步驟 之空氣流量可介於80ml/min至220nu/min，鍛繞溫产可介 於300°C至600°C，煅燒時間可介於2小時至6 ,丨、性 + 1 。 个時。在锻 燒步驟後，接著對觸媒進行還原步驟以還原觸媒^ 其可將氮氣通入反應器内進行加熱。還原步驟之氣氣、充旦 可介於50 ml/min至1500 ml/min，還原溫度可介於2⑼。〔 至500°C，還原時間可介於2小時至6小時。 為讓本發明之上述和其他目的、特徵、和優點能更曰月 顯易懂，下文特舉出較佳實施例，作詳細說明如下： 【實施例1】 第1圖為油品之加風脫氧反應裝置流程圖，其中1為 氫氣鋼瓶；2為二氧化碳鋼瓶；4為質量控制器；6為定量 泵浦；71及72為調節閥；8為儲槽；9為注射幫浦；1〇為 緩衝槽(Surge Tank) ; 11為反應器；12為氣液分離糟. 為取樣閥，14為濕式流量計；T為熱電偶；p為壓力彳貞_ 器；31、32及33為濾器；51、52及53為止回闕。 ' 反應器11為一柱流式固定床反應器。反應器1丨中| 填有5克Pt/Al2〇3觸媒及50克石英砂的混合物。首先將^ 201020318 應器11的溫度控制在約425°C。反應器11外圍以電熱式 高溫爐包覆，内部插入熱電偶T以偵測反應器11内流體溫 度，並由電子加熱器進行溫度回饋控制。接著在氫氣及二 氧化碳的流量比為1:1的條件下，分別利用電子質量控制 器4控制氫氣流量，同時利用調節閥71控制二氧化碳流 量，將氫氣及二氧化碳混合再通入反應器11中，並利用反 應器11出口接有的一背壓閥，使反應器11内的壓力為5〇〇 psi且壓力穩定。待反應器11的溫度及壓力穩定後，將置 p 於一耐酸鹼之玻璃儲槽8中的油酸(〇leic acid; C18H34〇2；)， 利用高壓注射幫浦9以固定流量0.5〜3ml/min通入系統。 由於所使用的注射幫浦為魯式幫浦，因此當其將油酸通入 系統時’幾乎不會影響系統内部的壓力，而使反應器維持 在進行氫化反應時所期望的壓力。反應物由反應器U上端 進入系統，經過觸媒作用後進行氫化反應，產物由反應器 11下端流出。反應器11流經背壓閥後降至常壓並於氣液 分離槽12中分為氣液兩相，氣體經由取樣閥13收集，並 # 以濕式流量計14記錄流量，液體則經冷卻後收集進行分 析。改質後油品之含氧量降低40%，油品碳數分佈多為C6 以下。 【比較例1】 相同於實施例1的裝置及流程步驟，其中僅通入氫氣 及油品進入反應系統，而未通入二氧化碳流體。改質後油 品之含氧量降低25%，油品碳數分佈多為C6以下。 7 201020318 【實施例2】 相同於實施例1的襄置及流程步驟，其中是將反應器 11的溫度控制在約啊，壓力控财約65_，且氛氣 及二乳化碳的流量比為1:1祕件下，進行加氫脫氧反應。 改質後油品之含氧量降低12%’油品魏分佈多為c6〜 C15。 【比較例2】 相同於實施例2的裝置及流程步驟，其中僅通入氫氣 及油品進人反應线，而未通人二氧化碳流體。改f後油® 品之含氧量降低5%。 【實施例3】 相同於實施例1的裝置及流程步驟，其中是將置於耐 酸驗之玻璃儲槽8中的模擬油品（十四烧(Tetradecane):癒 創木酚(Guaiacol; C7H802)的體積比為95 : 5)，利用高壓注 射幫浦9以固定流量0.5〜3ml/min通入系統，並控制反應鲁 器11的溫度在約340。(：，壓力在約650psi，且氫氣及二氧 化碳的流量比為1:1的條件下進行加氫脫氧反應。改質後 油品之含氧量降低4.6%。 【實施例4】 相同於實施例3的裝置及流程步驟，其中是將反應器 11的溫度控制在約350°C。改質後油品之含氧量降低 17.8%。 8 201020318 【實施例5】 相同於實施例3的裝置及流程步驟，其中是將反應器 11的溫度控制在約400°C。改質後油品之含氧量降低 20.2%。 雖然本發明已以數個較佳實施例揭露如上，然其並非 用以限定本發明，任何所屬技術領域中具有通常知識者， • 在不脫離本發明之精神和範圍内，當可作任意之更動與潤 飾，因此本發明之保護範圍當視後附之申請專利範圍所界 定者為準。 201020318 【圖式簡單說明】 第1圖為本發明實施例之加氫脫氧反應裝置示意圖。 【主要元件符號說明】 氫氣鋼瓶1 ; 二氧化碳鋼瓶2 ; 質量控制器4 ; 定量泵浦6 ; 調節閥71 ; 參 調節閥72 ; 儲槽8 ; 注射幫浦9 ; 缓衝槽10 ; 反應器11 ; 氣液分離槽12 ; 取樣閥13 ; 濕式流量計14; _ 濾器31 ; 濾器32 ; 濾器33 ; 止回閥51 ; 止回閥52 ; 止回閥53 ; 熱電偶T ; 10 201020318 壓力偵測器p。201020318 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a method for upgrading an oil product, and more particularly to a method for upgrading an oil product using a subcritical carbon dioxide fluid. [Prior Art] The hydrogenation process is one of the currently used oil upgrading methods. However, due to the high viscosity of the oil, the solubility of hydrogen in the oil is not high, and the effect of mass transfer between the gas and liquid reactants is not good. Further, when a catalyst having a pore property is used, the rate at which the oil enters the inside of the pore is slow, so that the efficiency of the hydrogenation reaction is limited. One method for increasing solubility is in a high pressure environment of more than 2000 psi, however this requires complicated and expensive high pressure equipment and consumes a large amount of hydrogen, thus causing process hazards and operational costs. In addition, oils with high oxygen content are corrosive to the catalyst, so oil adhering to the surface of the catalyst may cause serious poisoning of the catalyst, and the oil stuck in the catalyst hole may cause the hole to be blocked. The problem is that the reaction efficiency is lowered and the quality of the upgraded oil is not good. There is therefore a need to provide a method of upgrading oil products to overcome the deficiencies of the prior art. SUMMARY OF THE INVENTION The present invention provides a method for upgrading an oil product, comprising: contacting an oil with helium in a presence of a catalyst to perform a hydrodeoxygenation reaction, the hydrodesorption of 201020318 is based on subcritical carbon dioxide Performed in a fluid. The invention also provides a method for upgrading an oil, comprising: introducing a proportion of hydrogen and carbon dioxide into the reactor in a reactor and in the presence of a catalyst, and stabilizing the reactor The nitriding reaction temperature and the hydration reaction pressure, the carbon dioxide is a subcritical fluid, and then the oil is injected into the reactor at a fixed flow rate to bring the oil and hydrogen into contact for the hydrodeoxygenation reaction. [Embodiment] The present invention provides a method for upgrading an oil product, wherein the oil to be treated is contacted with hydrogen to carry out a hydrodegassing reaction in the presence of a catalyst, wherein the hydrogenation reaction is carried out in a subcritical carbon dioxide fluid. In progress. The use of the subcritical carbon dioxide fluid of the present invention can greatly improve the efficiency of oil upgrading. The oil to be treated of the present invention includes, but is not limited to, biomass cracking oil, biodiesel, waste lubricating oil, waste cooking oil, plastic cracking oil or tire cracking oil. In general, oils that need to be modified have a high oxygen content (greater than 40%) and are unstable, so the quality is not good. The formation of the secondary critical carbon dioxide fluid of the process is primarily such that the pressure of the reaction environment is such that the carbon dioxide fluid becomes a subcritical state. Thus, the hydrogenation reaction has a pressure of less than about 1000 psi, preferably from about psi to about 1000 psi, and a temperature of from about 300 Torr to about 5 Torr (rc. Since the subcritical carbon dioxide fluid does not need to reach a critical pressure, it is at a lower pressure. Formed in the environment, thus reducing energy consumption and equipment costs. The aerated deoxygenation reaction in this method is carried out in a subcritical carbon dioxide fluid 201020318. The subcritical carbon dioxide fluid causes the oil to have an expanding liquid between the liquid and the gas. (expended liquid) characteristics and the viscosity is greatly reduced. When the hydrogenation or hydroformylation reaction is carried out in the expansion liquid, even if the organic solvent is not completely dissolved in the carbon dioxide to form a homogeneous reaction, the reaction gas can be dissolved in the liquid phase in a large amount. In the solvent, the mass transfer resistance between the gas-liquid interface is effectively eliminated to improve the solubility of the helium gas, and in addition, the oil can rapidly flow through the catalyst surface or even into the pores, thereby improving the effective reaction area of the catalyst, and further, due to the oil The heat transfer resistance is reduced, thereby improving the conversion efficiency of the oil. In addition, since the oil does not stick to the catalyst surface The problem of poisoning of the catalyst is avoided. The method can be carried out in a reactor such as a fixed bed reactor. The catalyst can be placed in the reactor. Preferably, the catalyst is mixed with inert quartz sand to fix the reaction. In the embodiment, the catalyst particle size is larger than that of the quartz sand, so the quartz sand can be used to fill the gap between the catalysts to achieve the effect of fixing. The benefits of using the quartz sand also include the heat storage effect, which can effectively assist The temperature stability of the reactor is reduced and the heat energy loss is reduced. In addition, the quartz sand can also increase the dispersibility of the oil flowing through the reactor, so that the mixing of the oil with the catalyst and hydrogen is more uniform, and the product is prevented from flowing back. The catalyst used in the method comprises a metal such as platinum (Pt), palladium (Pd) or nickel-molybdenum alloy Ni-Mo. The catalyst may further use a metal oxide support such as oxidized (Al2〇3) or zeolite (Zeolitic). The particle size of the catalyst can range from about 1 mm to about 10 mm. The particle size of the quartz sand can range from 8 mesh to 18 mesh. The weight ratio of quartz sand to catalyst can range from 5:1 to 10:1. In the method of the present invention, the reactor is deuterated The pressure can be controlled by introducing hydrogen and carbon dioxide into the reactor to regulate the flow of hydrogen and carbon dioxide 5 201020318. Preferably, the gas and carbon dioxide entering the reactor have a fixed flow ratio. The ratio of hydrogen to carbon dioxide can be between 1:0.1 and 1:10. In the method of the present invention, before hydrogenation, after oxidation, and oil to the reactor for hydrogenation, The catalyst is subjected to a regeneration process to increase the efficiency of the hydrogenation reaction. First, the catalyst is calcined, which can be heated into the reactor for heating. The air flow rate of the calcination step can range from 80 ml/min to 220 nu. /min, forging temperature can be between 300 ° C and 600 ° C, calcination time can be between 2 hours and 6, 丨, sex + 1 . Time. After the calcination step, the catalyst is then subjected to a reduction step to reduce the catalyst. It can be passed through the reactor for heating. The gas and gas in the reduction step can range from 50 ml/min to 1500 ml/min, and the reduction temperature can be between 2 (9). [To 500 ° C, the reduction time can be between 2 hours and 6 hours. The above and other objects, features, and advantages of the present invention will become more apparent from the description of the preferred embodiments of the invention. Flow chart of deoxygenation reaction device, wherein 1 is a hydrogen cylinder; 2 is a carbon dioxide cylinder; 4 is a quality controller; 6 is a quantitative pump; 71 and 72 are regulating valves; 8 is a storage tank; 9 is an injection pump; The buffer tank (Surge Tank); 11 is the reactor; 12 is the gas-liquid separation. For the sampling valve, 14 is the wet flow meter; T is the thermocouple; p is the pressure 彳贞 _; 31, 32 and 33 are the filter ; 51, 52 and 53 to return. 'Reactor 11 is a column flow fixed bed reactor. Reactor 1 丨 | filled with a mixture of 5 grams of Pt / Al 2 〇 3 catalyst and 50 grams of quartz sand. First, the temperature of the ^201020318 reactor 11 was controlled at about 425 °C. The periphery of the reactor 11 is covered by an electrothermal high temperature furnace, and a thermocouple T is inserted therein to detect the temperature of the fluid in the reactor 11, and temperature feedback control is performed by an electric heater. Then, under the condition that the flow ratio of hydrogen and carbon dioxide is 1:1, the flow rate of hydrogen is controlled by the electronic quality controller 4, and the flow rate of carbon dioxide is controlled by the regulating valve 71, and hydrogen and carbon dioxide are mixed and then introduced into the reactor 11, and A back pressure valve connected to the outlet of the reactor 11 was used to bring the pressure in the reactor 11 to 5 psi and the pressure was stabilized. After the temperature and pressure of the reactor 11 are stabilized, oleic acid (C18H34〇2;) in an acid-resistant glass storage tank 8 is placed, and the high-pressure injection pump 9 is used to fix the flow rate 0.5~ 3 ml/min access to the system. Since the injection pump used is a Lupu pump, when it is introduced into the system, it hardly affects the pressure inside the system, and the reactor maintains the pressure required for the hydrogenation reaction. The reactant enters the system from the upper end of the reactor U, undergoes a hydrogenation reaction after the catalyst, and the product flows out from the lower end of the reactor 11. After flowing through the back pressure valve, the reactor 11 is reduced to normal pressure and divided into gas-liquid two phases in the gas-liquid separation tank 12, the gas is collected through the sampling valve 13, and the flow rate is recorded by the wet flow meter 14, and the liquid is cooled. After collection and analysis. After upgrading, the oxygen content of the oil is reduced by 40%, and the carbon number distribution of the oil is mostly below C6. [Comparative Example 1] The apparatus and the procedure of the same procedure as in Example 1 in which only hydrogen gas and oil were introduced into the reaction system without introducing a carbon dioxide fluid. After upgrading, the oxygen content of the oil is reduced by 25%, and the carbon number distribution of the oil is mostly below C6. 7 201020318 [Embodiment 2] The same as the apparatus and process steps of Embodiment 1, wherein the temperature of the reactor 11 is controlled to about ah, the pressure control is about 65 _, and the flow ratio of the atmosphere and the emulsified carbon is 1 : 1 Under the secret part, carry out hydrodeoxygenation reaction. After the upgrading, the oxygen content of the oil is reduced by 12%. The oil distribution is mostly c6~C15. [Comparative Example 2] The apparatus and the procedure of the same procedure as in Example 2, in which only hydrogen gas and oil were introduced into the reaction line, and no carbon dioxide fluid was passed. After changing the oil content of the oil product, the oxygen content is reduced by 5%. [Example 3] The apparatus and process steps identical to those of Example 1, in which a simulated oil (Tetradecane: Guaiacol; C7H802) to be placed in the acid-resistant glass storage tank 8 (Tetradecane: C7H802) The volume ratio is 95: 5), and the high pressure injection pump 9 is introduced into the system at a fixed flow rate of 0.5 to 3 ml/min, and the temperature of the reaction device 11 is controlled at about 340. (: The hydrodeoxygenation reaction was carried out under the conditions of a pressure of about 650 psi and a flow ratio of hydrogen to carbon dioxide of 1:1. The oxygen content of the oil after the modification was reduced by 4.6%. [Example 4] The same as the examples. The apparatus and process steps of 3, wherein the temperature of the reactor 11 is controlled to about 350 ° C. The oxygen content of the oil after the modification is reduced by 17.8%. 8 201020318 [Example 5] The same apparatus as in Example 3 The process step is to control the temperature of the reactor 11 to about 400 ° C. The oxygen content of the oil after the modification is reduced by 20.2%. Although the present invention has been disclosed above in several preferred embodiments, it is not used The invention is defined by those skilled in the art, and the invention can be modified and modified without departing from the spirit and scope of the invention, and the scope of the invention is defined by the appended claims. 201020318 [Simplified description of the drawings] Fig. 1 is a schematic view of a hydrodeoxygenation reaction apparatus according to an embodiment of the present invention. [Explanation of main components] Hydrogen cylinder 1; Carbon dioxide cylinder 2; Quality controller 4; Pu 6; regulating valve 71; regulating valve 72; storage tank 8; injection pump 9; buffer tank 10; reactor 11; gas-liquid separation tank 12; sampling valve 13; wet flow meter 14; _ filter 31; Filter 32; filter 33; check valve 51; check valve 52; check valve 53; thermocouple T; 10 201020318 pressure detector p.