201100376 九、發明說明： 【發明所屬之技術領域】 本案係有關於二氧化碳與曱醇合成含氧生質 燃料碳酸二甲酯技術，尤指利用液液相萃取反應製 造方法。 【先前技術】 近年來大氣中的二氧化碳含量持續快速增加’溫室氣 體排放量的增加，強化了溫室效應，加劇全球暖化的現象’ 使得氣候變化劇烈，影響各國農業生產、環境保護與經濟 發展’溫室氣體的排放是全球性的汙染。2005年2月16 曰由160個國家簽署生效的「京都議定書」，目的即在於共 同致力減少溫室氣體排放，減緩溫室效應所造成的影響。 為求兼顧環境保護及經濟發展，各種石化燃料的替代產品 也相繼問世’同時由於地球上油存量有限，石化燃料價格 逐漸升高’解決各種燃料式能源問題是當務之急。 碳酸二曱酯（dimethyl carbonate，DMC)是一種重要 有機合成原料及中間體，被譽為二十一世紀的綠色 化工產品’分子结構中含有羰基、曱基和甲氧基等官能團，具 有多種反應性能，廣泛適合於醫藥、農藥化學合成領 域，在生產中具有使用安全、方便、污染少、容易運輸等特点。 由於碳酸二曱酯毒性較小，是一种具有發展前景的“绿色，，化工產 品’可替代光氣使用’無色透明液體，略帶香味， 具有近似水的特性，不溶於水，可以與酮、醇、酯 混合，無腐蝕性，具有可燃性，市場前景廣闊。 DMC分子结構中含有幾基、甲基、甲氧基和幾基甲氧基可用 於幾基化、甲基化、甲氧基化和麟㈣鱗有機合成反應，生產 9 201100376 聚碳_旨、聚減甲_旨 '聚碳酸㉟二醇、苯㈣ 三光氣'苯胺基甲酸甲酉旨等多種化工產品。由於聽無毒:可替曰 劇毒的光氣、氯曱酸曱㉝、硫酸二曱g旨等作為曱基化劑或絲化劑 使用，提高生產的安全性，降低環境污染。作為溶劑，DMC可替^ Freon、三氯乙烷、三氯乙烯、苯、二曱苯等用於油漆塗料、清潔 溶劑等。此外，DMC射作清潔劑、表面活性劑和柔軟劑的添加劑、。 用途非常廣泛，DMC被譽為當今有機合成的“新基石，、 DMC直接添加到燃料油中，可以變成一種有價值 的含氧燃料添加劑，增加燃燒的效率改善抗爆與辛 烷值特性，疋一種良好添加劑具有潛力添加在汽 油，可以大幅改善一氧化碳，碳氫化合物，醛類， 黑煙排放’積碳的特性，作為汽油添加劑，可提高其辛 燒值和含氧量’進而提高其抗爆性。 習知技術中DMC合成，可以從甲醇與二氧化碳透過鹼 陡觸媒奴酸鉀（K2C〇3) Applied Catalysis A:142(1996)Ll-3 或者金屬氧化錦/氧化锆（Ce〇2/Zr〇2)Catalysis Letters: 76 (2001)71進行自旨化反應’在超臨界高壓下 進行均相觸媒或者異相觸媒催化反應，以過量的甲 醇與二氧化碳在觸媒下進行酯化反應，可產生dmc， 再透過分離程序將DMC取出。由於曱醇與c〇2酯化反 應會產生DMC或DME與水，用Zr〇2觸媒有良好的 DMC選擇性（100%)，没有DME產生，在製程中必須 將水分移除，否則轉化率會因為產生平衡反應被抑 制，使產率無法提高，但是加入適當量dimeth〇xy propane (DMP)添加具有除水功能可以明顯提高 DMC 產率，Applied Catalysis A:142 (2002)103-109。 —有鑑於此，本發明之目的係提供一改良的製造 含氧燃料DMC製程，利用疏水性燃料本身具有高溶 10 201100376 解DMC的特性，當甲醇反應成DMC轉化程度越高時疏 水性越佳’如DMC比甲醇的油溶解效果更好，提升 平衡的轉化效率，同時此技術也有利於反應之後與 疏水相或親水相進行分離。 【發明内容】 ^案之構想在於提供一種液液相萃取反應合成碳酸二 :酯的製程，有利於將反應後的水分移除，可提高 碳酸二甲酯產率，該製程包括：a)提供甲醇，二氧化 碳’ 一酿化觸媒與—疏水性燃料；b)提供一酯化反應 器；c)加入甲醇’二氧化碳，該酯化觸媒與該疏水性 - 燃料至該酯化反應器中；d)進行酯化反應使甲醇原料 與二氧化碳產生碳酸二甲酯可溶解於該疏水性燃料 中；e)分離該疏水性燃料；以及f)分離反應產生的 水。。 根據上述該酯化觸媒包括·· Li2C〇3，Na2C03， K2C03 ’ Cs2C03，K2P04 ’ Ce02/Ti02，Ce02/Zr02。 其中該酯化觸媒為Ce02/Zr02。 根據上述該疏水性燃料可包括：生質汽油，汽油， 丙烧，丁烷，戊烷，其他疏水性燃料。其中該疏水 性燃料為戊烷。 其中該酯化反應溫度條件從50至200。(：。該酯化反應 壓力條件從1至150atm。 根據上述該製程更包括使用一純氣隔絕與氧氣作 用。其中該鈍氣為氮氣。如申請專利範圍第1項所 述液液相萃取反應合成碳酸二曱酯之製程，其中該 酉旨化反應器包括：一固定床管柱反應器，連續式攪 11 201100376 拌反應器，批式反應器。其中該酯化反應器為批式 反應器》 根據構想本案液液相萃取反應合成二曱基碳 酸醋（含氧生質燃料）如圖一所示，甲醇與二氧 化礙在觸媒上進行酯化反應，觸媒表面吸附為甲 醇及水在親水相phase I，反應中產物DMC為較 疏水性即時被萃取到疏水相phase II，二甲基碳酸 醋溶在疏水相較多，如此打破此反應的平衡，減 少產物被逆向水解，所以反應的產率比較高。 本案液液相萃取反應合成二曱基碳酸酯（含 氧生質燃料）裝置如圖二所示’將二氧化碳鋼瓶 1，調壓閥2，控制閥3，反應器4内含有一適量 醋化觸媒’磁石攪拌器5，在一高溫及壓力下經攪 拌’壓力錶P ’酯化反應適當時間後將產物流體， 經取樣閥6取出分析。為了更具體說明本發明， 本案將以較佳實施例結果說明如下。 【實施方式】 更具體說明本發明之液液相萃取反應合成二 甲基碳酸酯從甲醇與二氧化碳，疏水性燃料與親 水相分離回收方便，而且可以利用疏水性化學物 質包括：石化汽油與烷類等。本案精髓是透過疏 水性液體進行萃取酯化反應後，比較疏水的二曱 基碳酸酯DMC會溶解在疏水性燃料中打破反應 平衡’本案實際進行萃取酯化反應，同時以定性、 疋里進行g旨化反應分析，以疏水性燃料萃取二曱 12 201100376 基碳酸s旨濃度之實施例結果說明。201100376 IX. Description of the invention: [Technical field to which the invention pertains] The present invention relates to a technique for synthesizing oxycarbonate dimethyl carbonate with carbon dioxide and decyl alcohol, and more particularly to a liquid phase extraction reaction production method. [Prior Art] In recent years, the carbon dioxide content in the atmosphere has continued to increase rapidly. 'The increase in greenhouse gas emissions has strengthened the greenhouse effect and aggravated the phenomenon of global warming', making climate change drastically affecting countries' agricultural production, environmental protection and economic development. Greenhouse gas emissions are global pollution. February 16, 2005 「 The “Kyoto Protocol”, which was signed by 160 countries, aims to reduce greenhouse gas emissions and mitigate the effects of the greenhouse effect. In order to balance environmental protection and economic development, various alternatives to petrochemical fuels have also been introduced. At the same time, due to the limited stock of oil on the earth, the price of fossil fuels has gradually increased. It is imperative to solve various fuel-type energy problems. Dimethyl carbonate (DMC) is an important organic synthesis raw material and intermediate. It is known as the green chemical product of the 21st century. The molecular structure contains functional groups such as carbonyl, sulfhydryl and methoxy groups. It is widely used in the field of chemical synthesis of medicines and pesticides. It is safe, convenient, less polluting and easy to transport in production. Because diterpene carbonate is less toxic, it is a promising "green, chemical product" can replace phosgene use 'colorless transparent liquid, slightly scented, has water-like characteristics, is insoluble in water, can be combined with ketone , alcohol, ester mixed, non-corrosive, flammable, broad market prospects. DMC molecular structure contains several groups, methyl, methoxy and several methoxy groups can be used for several methylation, methylation, methoxy The basic chemical synthesis reaction of basal and lin (four) scales, production 9 201100376 Polycarbonate _ _ _ _ _ _ _ _ _ 'polycarbonate 35 diol, benzene (four) three phosgene 'aniline formate methyl hydrazine and other chemical products. Because of the non-toxic: It can be used as a thiolating agent or a silking agent to improve the safety of production and reduce environmental pollution. As a solvent, DMC can be used as a solvent. Trichloroethane, trichloroethylene, benzene, diphenylbenzene, etc. are used in paints, cleaning solvents, etc. In addition, DMC is used as an additive for detergents, surfactants and softeners. It is widely used, and DMC is known as The new base of organic synthesis Stone, DMC directly added to fuel oil, can become a valuable oxyfuel additive, increase the efficiency of combustion to improve the antiknock and octane characteristics, a good additive has the potential to be added to gasoline, which can greatly improve carbon monoxide, Hydrocarbons, aldehydes, black smoke emissions 'carbon deposit characteristics, as a gasoline additive, can increase its smoldering value and oxygen content' and thus improve its antiknock. In the prior art, DMC synthesis can be carried out from methanol and carbon dioxide through a base steep catalyst potassium citrate (K2C〇3) Applied Catalysis A: 142 (1996) Ll-3 or metal oxide bromine / zirconia (Ce 〇 2 / Zr 〇 2) Catalysis Letters: 76 (2001) 71 for the self-reaction reaction's homogeneous catalyst or heterogeneous catalyst catalyzed reaction under supercritical high pressure, with an excess of methanol and carbon dioxide esterification reaction under the catalyst, can be produced Dmc, and then remove the DMC through the separation process. Since the esterification reaction of sterol with c〇2 produces DMC or DME and water, Zr〇2 catalyst has good DMC selectivity (100%), no DME is produced, and moisture must be removed during the process, otherwise conversion The rate is suppressed because of the equilibrium reaction, so that the yield cannot be improved, but the addition of an appropriate amount of dimeth〇xy propane (DMP) with water removal can significantly increase the yield of DMC, Applied Catalysis A: 142 (2002) 103-109. In view of the above, the object of the present invention is to provide an improved process for producing an oxy-fueled DMC, which utilizes the characteristic that the hydrophobic fuel itself has a high solubility of 10 201100376, and the hydrophobicity is better when the degree of conversion of methanol to DMC is higher. 'If DMC is better than methanol, it will improve the conversion efficiency of equilibrium, and this technology will also facilitate separation from hydrophobic phase or hydrophilic phase after reaction. SUMMARY OF THE INVENTION The concept of the invention is to provide a liquid-liquid phase extraction reaction to synthesize a diester carbonate, which is beneficial to remove the moisture after the reaction, and can improve the yield of dimethyl carbonate. The process includes: a) providing Methanol, carbon dioxide 'one brewing catalyst and - hydrophobic fuel; b) providing an esterification reactor; c) adding methanol 'carbon dioxide, the esterification catalyst and the hydrophobic fuel to the esterification reactor; d) performing an esterification reaction to produce a methanolic feedstock with carbon dioxide to produce dimethyl carbonate dissolved in the hydrophobic fuel; e) separating the hydrophobic fuel; and f) separating the water produced by the reaction. . According to the above esterification catalyst, Li2C〇3, Na2C03, K2C03'Cs2C03, K2P04' Ce02/Ti02, Ce02/Zr02. Wherein the esterification catalyst is Ce02/Zr02. The hydrophobic fuel according to the above may include: bio-gasoline, gasoline, propane, butane, pentane, and other hydrophobic fuels. Wherein the hydrophobic fuel is pentane. Wherein the esterification reaction temperature conditions are from 50 to 200. (: The esterification reaction pressure condition is from 1 to 150 atm. According to the above process, the process further comprises the use of a pure gas barrier and oxygen. The inert gas is nitrogen. The liquid phase extraction reaction as described in claim 1 The process for synthesizing dinonyl carbonate, wherein the hydrazine reactor comprises: a fixed bed column reactor, a continuous stirring 11 201100376 mixing reactor, a batch reactor, wherein the esterification reactor is a batch reactor According to the conception liquid-liquid phase extraction reaction, the synthesis of dimercaptocarbonic acid vinegar (oxygenated biomass fuel) is shown in Figure 1. The methanol and the oxidizing agent are esterified on the catalyst, and the catalyst surface is adsorbed as methanol and water. In the hydrophilic phase phase I, the product DMC is more hydrophobic in the reaction and is extracted into the hydrophobic phase phase II. The dimethyl carbonate carbonate is dissolved in the hydrophobic phase, thus breaking the equilibrium of the reaction and reducing the reverse hydrolysis of the product, so the reaction The yield is relatively high. In this case, the liquid-liquid phase extraction reaction to synthesize a dimercaptocarbonate (oxygen-containing biomass fuel) device is shown in Figure 2. 'The carbon dioxide cylinder 1, the pressure regulating valve 2, the control valve 3, the reaction 4 contains an appropriate amount of vinegar catalyst 'magnet stirrer 5, stirred under a high temperature and pressure 'pressure gauge P ' esterification reaction for a suitable time, the product fluid is taken out through the sampling valve 6 for analysis. The present invention will be described below with reference to the results of the preferred embodiments. [Embodiment] More specifically, the liquid-liquid phase extraction reaction of the present invention synthesizes dimethyl carbonate from methanol and carbon dioxide, and the hydrophobic fuel and the hydrophilic phase are separated and recovered conveniently, and Hydrophobic chemicals can be used, including: petrochemical gasoline and alkanes, etc. The essence of this case is that after the extraction and esterification reaction through a hydrophobic liquid, the more hydrophobic dimercaptocarbonate DMC will dissolve in the hydrophobic fuel to break the reaction equilibrium. Actually, the extraction and esterification reaction was carried out, and the results of the example of extracting the concentration of ruthenium 12 201100376 by the hydrophobic fuel were carried out by qualitative and lysate analysis.
般汽油是石油提煉後的一種分餾產物，它由 同的氫化合物混合組成，主要成分是4到 12個碳原子的鏈烧、刪少量芳烴，化學和物 理特性位於汽油和重油之間，沸點範圍約在30°C f、2〇〇°C間。正辛烷是主要成分之-，通常汽油必 貝添加些含氧燃料如：MTBE可提高辛院值， 以降低汽缸震報現象或者燃燒不完全所產生黑 煙’ DMC亦為一個很好的含氧燃料。 實施例之-、 - 本案根據構想選擇一疏水性燃料正戊炫 n-pentane 比重 〇. 626，黏度 〇, 24cp，沸點 36.1 C ’介於一氧化碳（-78°C)至DMC(90°C)之間，取 正戊烧10公克，二氧化碳灌入5〇atm，甲醇 公克，觸媒Ce〇2/Zr〇2 1.5公克置入一反應器内容 積2 5 0 c c撥拌進行g旨化反應，在溫度1 1 〇 下經 過24小時後，經冷卻後減壓取出DMC，小心將 取出油層，用FTIR偵測觀察DMC酯官能基，定 C) 性分析證實酯化反應進行且溶入疏水性燃料正戊 烷。 實施例之二、 本案根據構想取戊烷1 〇公克，曱醇1 8公克， 二氧化碳灌入 50atm，已有觸媒 1.5公克 Ce02/Zr02 1.5置入一密閉反應器搜拌進行酯化反 應，在溫度1 10°C下經過24小時後，經冷卻後減 壓排出液體分析，用 GC-FID型號為 Aligent 13 201100376 6890N，其管柱型號為：VARIAN (VF-WAXms 30m x0.32mm ID ’ DF = 0.5 # m)進行分析觀察 DMC 產 率比較，酯化反應加入疏水性戊烷，經24hr反應 後其DMC產率高於沒有用戊烷，證實液液相反應 有利於酯化反應進行。 本案合成含氧燃料DMC利用製程液液相萃取 反應’以疏水性油料卒取反應後的疏水性產物，可 利於反應後疏水性產物之分離，此乃本發明重點之 所在，為保護本案之發明創作，得由熟悉此專業之 〇 人士任施巧思而為諸般修飾，然皆不脫如附申請專 利範圍所欲保護之陳述。 【圖式簡單說明】 圖一曱醇與二氧化碳酯化反應成二甲基碳酸_之 疏水性關係 圖二本案液液相萃取反應合成二曱基碳酸鲳裳置 〇 【主要元件符號說明】 1 ’ 一氧化碳鋼瓶 2 :調壓閥 3 :控制閥 4 :反應器 5:磁石攪拌器 6 :取樣閥 p :壓力錶 14Gasoline is a fractionated product after petroleum refining. It consists of a mixture of the same hydrogen compounds. The main component is a chain of 4 to 12 carbon atoms, a small amount of aromatic hydrocarbons. The chemical and physical properties are between gasoline and heavy oil. About 30 ° C f, 2 ° ° C. N-octane is the main component - usually gasoline will add some oxygen-containing fuels such as: MTBE can increase the Xinyuan value to reduce the phenomenon of cylinder shock or incomplete combustion of black smoke. DMC is also a good inclusion. Oxygen fuel. Example -, - This case is based on the idea of selecting a hydrophobic fuel, n-pentane, specific gravity . 626, viscosity 〇, 24 cp, boiling point 36.1 C 'between carbon monoxide (-78 ° C) to DMC (90 ° C) Between the 10 gram of positive pentylene, the carbon dioxide was poured into 5 〇 atm, methanol gram, the catalyst Ce 〇 2 / Zr 〇 2 1.5 gram into a reactor internal volume 2 5 0 cc mixing to carry out the g reaction, After 24 hours at a temperature of 1 1 Torr, the DMC was taken out under reduced pressure after cooling, and the oil layer was carefully taken out, and the DMC ester functional group was observed by FTIR. The C) analysis confirmed that the esterification reaction proceeded and dissolved into the hydrophobic fuel. N-pentane. In the second embodiment, the case is based on the idea of taking pentane 1 gram, sterol 18 gram, carbon dioxide filling 50 atm, and the catalyst 1.5 gram Ce02/Zr02 1.5 is placed in a closed reactor for esterification reaction. After 24 hours at a temperature of 10 °C, after cooling, the liquid was discharged under reduced pressure. The GC-FID model was Aligent 13 201100376 6890N, and the column type was: VARIAN (VF-WAXms 30m x0.32mm ID ' DF = 0.5 # m) Analysis and observation of DMC yield comparison, the esterification reaction was added with hydrophobic pentane, and the DMC yield after 24 hr reaction was higher than that without pentane, which confirmed that the liquid phase reaction was favorable for the esterification reaction. The synthetic oxygen-containing fuel DMC in this case utilizes the liquid phase extraction reaction of the process liquid. The hydrophobic product after the reaction of the hydrophobic oil can facilitate the separation of the hydrophobic product after the reaction, which is the focus of the present invention, and is to protect the invention of the present invention. The creation must be modified by those who are familiar with the profession, and they are all modified as they are intended to be protected by the scope of the patent application. [Simple diagram of the diagram] Figure 1: Hydrophobic relationship between decyl alcohol and carbon dioxide to dimethyl carbonate _ Figure 2 Liquid-phase extraction reaction of this solution to synthesize dimercapto strontium carbonate 鲳 〇 [Main component symbol description] 1 ' Carbon monoxide cylinder 2: Pressure regulating valve 3: Control valve 4: Reactor 5: Magnet stirrer 6: Sampling valve p: Pressure gauge 14