201002812 九、發明說明： 【發明所屬之技術領域】 本案係有關於合成含氧生質燃料技術，尤指 液相萃取反應製造方法。 曰 利用 液 【先前技術】 甘油（GlyCerol or Glycerine)生產過剩問題將逐 現’隨著石油資源的日益枯竭和人們環保意識的提予 加快柴油替代燃料的開發步伐，由生物製成柴油的優越 環保性能受到了各國的重視。生質柴油的製造是將動： 物油脂或廢食用油（三酸甘油脂）經由轉§旨化反摩、= 和、水洗及蒸餾等過程後所生成的甲基醋類油。隨著I 質柴油的開發，整個生質柴油的生產過程將會產生= 1 (U重罝比的甘油，雖然甘油目前擁有丨5 〇 〇種以上的丄 般用途，諸如化妝品、護膚藥劑、烟草、醫藥法定藥劑， 以及各種食品加工產品，但其總需求量並不大，研發 油的新用途以利因應時局所需乃成為業界的挑201002812 IX. Description of the invention: [Technical field to which the invention pertains] This case relates to the synthesis of an oxygen-containing biomass fuel technology, and more particularly to a liquid phase extraction reaction production method.曰Utilization [Previous Technology] Glycerol (GlyCerol or Glycerine) overproduction problem will be realized. With the depletion of petroleum resources and people's awareness of environmental protection, the development of diesel alternative fuels will be accelerated. Performance has received the attention of all countries. The production of biodiesel is a methyl vinegar oil produced by the process of moving oil or waste cooking oil (triglyceride) by means of anti-friction, =, water washing and distillation. With the development of I-type diesel, the entire production process of biodiesel will produce =1 (U 罝 罝 glycerol, although glycerin currently has more than 5 kinds of 丄-like uses, such as cosmetics, skin care agents, tobacco , pharmaceutical statutory pharmaceuticals, and various food processing products, but their total demand is not large, the new use of research and development oil to meet the needs of the current situation is the industry's pick
Angew. Chem. Int. Ed. 46 (2007)4434-4440· 利用甘油合成大宗需求的含氧燃料是一具市場潛 力的方法，甘油本身並無法直接添加到燃料油中，因為 在鬲溫時會產生聚合作用造成阻塞引擎，部分氧化成有 毒的丙烯醛排放，但是甘油可用來合成烷基甘油醚可以 k成一種有價值的含氧燃料添加劑，增加燃燒的效率改 善抗爆與十六烷值特性，如glycer〇l tertiary butyl ether (GTBE)是一種良好添加劑具有潛力添加在柴油與生物 柴油中（US patent 5308365 )，尤其在柴油含芳香物中 ^ a 30-40% l,3di, l,2di, 1,2,3-tri-tert-butyl glycerol > 可以大幅改善一氧化碳’碳氫化合物，醛類，黑煙排放， 5 201002812 積碳的特性。GTBE可用異丁烯與甘油以酸性觸媒進行 醚化反應來合成，在兩相反應系統中，異丁烯疏水在上 層甘油在下層，容易分離（US patent 5476971 )。對於 石化柴油或生質柴油而言含氧燃料的添加也可以下低 黏度與濁點cloud point改善燃燒效率（us patent 6015440 ) 〇Angew. Chem. Int. Ed. 46 (2007) 4443-4440· The use of glycerol to synthesize a large demand for oxy-fuels is a market potential. Glycerol itself cannot be directly added to fuel oil because it will The polymerization causes the blocking engine to partially oxidize to toxic acrolein emissions, but glycerol can be used to synthesize alkyl glyceryl ethers to form a valuable oxyfuel additive, increasing the efficiency of combustion and improving the antiknock and cetane characteristics. For example, glycer〇l tertiary butyl ether (GTBE) is a good additive with potential for addition in diesel and biodiesel (US patent 5308365), especially in diesel aromas ^ a 30-40% l, 3di, l, 2di , 1,2,3-tri-tert-butyl glycerol > can greatly improve carbon monoxide 'hydrocarbons, aldehydes, black smoke emissions, 5 201002812 carbon deposit characteristics. GTBE can be synthesized by etherification of isobutylene with glycerol by an acidic catalyst. In a two-phase reaction system, isobutylene is hydrophobic in the lower layer and is easily separated (US patent 5476971). For petrochemical diesel or biodiesel, the addition of oxygenated fuel can also improve the combustion efficiency with low viscosity and cloud point (us patent 6015440).
含氧燃料，烷基甘油醚，可以用甘油與烯類或醇類透 過酸性觸媒進行醚化反應，在常壓或者高壓下進行均相 觸媒或者異相觸媒催化反應，以過量的烷烯或醇類與甘 油在酸性觸媒下進行醚化反應，可產生單、雙、三丁烷 基甘油醚產物，再透過分離方式將烷基甘油醚取出。= 於醇類與甘油醚化反應會產生烷基甘油醚與水，在製程 中必須將水分移除（us patent 20070238905 )。 、，鑑於此，本發明之目的係提供一實用而經濟的製 k 3氧砧料製轾，利用疏水性燃料本身具有高溶解烷^ :’由喊：特性’甘油醚化反應轉化程度越高疏水性越 多雙燒基甘油醚比單烷基甘油醚的油溶解效果 更^降低_的黏度與雲點’料此技術有利於 反應之後與甘油相或水相進行分離。 【發明内容】 f程，% /你 一種液相萃取反應合成含氧生質燃料 2庫德的：疏水生質燃料的黏度與雲點，有利於將 = 移除’該製程包括：提供甘油，-醇類， $甘、由。忒疏水性燃料；提供—醚化反應器；加入 工…；類，，㈣化觸媒與該疏水性燃料至該醚化 f Z甘％ Μ、仃醚化反應使該甘油原料與該醇類產生— 性燃料。 解；该心水性燃料中；以及分離該疏水 6 201002812 - 根，上述該甘油含氫氧官能基（醇基）可包括：甘油與 • 乙一醇。其中該甘油原料與該醇類莫爾比例1 : 3 0至1 : 2 ° &甘油原料與該疏水性燃料重量比比例1 : 1 0至1 : 0^5 °該疏水性燃料可包括：生質柴油、柴油、汽油。該 ' 疏水性燃料為生質柴油。其中該醚化觸媒為一酸性觸媒 • 匕括路易士酸、布朗士酸、與兩種酸結合。其中該酸 陡觸媒包括：Amberlyst-15, Amberlyst-35, p-toluene sulfonic acid » naphthalenesulfonic acid ' ( +-)Oxygen-containing fuel, alkyl glyceryl ether, can be etherified with glycerol and an olefin or alcohol through an acidic catalyst, and subjected to homogeneous catalyst or heterogeneous catalyst catalysis under normal pressure or high pressure to excess alkylene Alternatively, the alcohol can be etherified with glycerol under an acidic catalyst to produce a mono-, di-, and tri-butane glyceryl ether product, and the alkyl glyceryl ether can be removed by separation. = The etherification of alcohols with glycerol produces alkyl glyceryl ether and water, which must be removed during the process (us patent 20070238905). In view of the above, the object of the present invention is to provide a practical and economical k3 oxygen anvil preparation system, which utilizes a hydrophobic fuel itself to have a high dissolved alkane: 'The higher the degree of conversion by the singular: characteristic glycerol etherification reaction The more hydrophobic the bis-alkyl glyceryl ether is more effective than the monoalkyl glyceryl ether, the lower the viscosity and the cloud point. This technique facilitates the separation of the glycerin phase or the aqueous phase after the reaction. SUMMARY OF THE INVENTION f, % / you a liquid phase extraction reaction synthesis of oxygenated biomass fuel 2 Kurd: hydrophobic biomass fuel viscosity and cloud point, is conducive to = remove 'this process includes: provide glycerin, - alcohol, $gan, by. a hydrophobic fuel; providing an etherification reactor; adding a catalyst; and (4) a catalytic catalyst and the hydrophobic fuel to the etherified f Zg, 仃, oxime etherification reaction to make the glycerin raw material and the alcohol Produce - sexual fuel. Solving; in the core water fuel; and separating the hydrophobic 6 201002812 - root, the glycerol hydrogen-containing oxygen functional group (alcohol group) may include: glycerin and • ethyl alcohol. Wherein the ratio of the glycerin raw material to the alcohol molar ratio is 1:30 to 1:2 ° & glycerin raw material to the hydrophobic fuel weight ratio 1: 1 0 to 1: 0 ^ 5 ° The hydrophobic fuel may include: Biodiesel, diesel, and gasoline. The 'hydrophobic fuel is biodiesel. The etherification catalyst is an acidic catalyst. • Includes Lewis acid, Bronze acid, and two acids. The acid steep catalyst includes: Amberlyst-15, Amberlyst-35, p-toluene sulfonic acid » naphthalenesulfonic acid ' ( +-)
Phorsulphonic acid ’ xylenesulfonic acid。其中該 :㉟性觸媒為—液體酸包括：硫酸、帛酸、氫氟酸。其中 5亥謎化反應溫度條件從〇至250°C。其中該醚化反應壓 力條件從1至5〇atm。 二根據亡述該製程更包括使用一鈍氣隔絕與氧氣作用。其 中该純氣為氮氣。其中該醚化反應器包括：一固定床管 柱反應杰，連續式攪拌反應器，批式反應器。其中該烷 基甘=醚至少包括：雙-烷基甘油醚、三-烷基甘油醚。 其中分離疏水性燃料方法可包括：閃化蒸發水與低沸點 烷基醚、降溫下油水分層、離心分離。 ί α本案之另—構想在於提供液液相萃取反應合成含氧燃料製 t，可降低—燃料的黏度與雲點，有利於將反應後的水 刀移除，该製程包括：提供一甘油原料，醇類，一醚化 觸媒與該疏水性燃料；提供一醚化反應器；加入該甘油 原，°亥醇類’该喊化觸媒與該疏水性燃料至該醚化反 應益中進行醚化反應使該甘油原料與該醇類產生一烷 基甘油醚可洛解於該疏水性燃料中；以及分離該疏水性 燃料。 根據上述该甘油原料為動物油與植物油轉酯化後的產 物。 7 201002812 本案之另一構想在於提供一種液液相萃取反應合成 燃料製程，可直接降低燃料的黏度與雲點，有利於將 反應後的水分移除，該製程包括：提供甘油，醇類盥 -醚化觸媒提供一醚化反應$ ;加入該甘油，該醇 類，與該醚化觸媒至該醚化反應器中；進行醚化反應 使該甘油原料與該醇類產生一烷基甘油醚；加入一 ^ 水性燃料萃取該烷基甘油醚於其中；以及分離該 性燃料。 本案液液相萃取反應合成含氧生質燃料製程如圖 一所示，將疏水性燃料A，醇類B與甘油原料C ,加 =醚化反應器1内含有一適量醚化觸媒，在一高溫及 壓力下經攪拌醚化反應適當時間後將，產物流體D過 濾進入一閃化蒸發器2，將未反應的醇類、附產物烷基 鱗與水E分離，再將未反應之甘油與含氧燃料ρ送入 沈降为層槽3，以重力分層或者離心分離，最後將含氧 燃料G取出’同時未反應甘油回收Η至醚化反應器1 内’ I為鍵類回流。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含氧燃 料製程’具降低燃料的黏度與雲點，方便疏水性燃料 與甘油相分離回收’而且可以廣泛適用在疏水性化學 物質包括：石化柴油與生質柴油。本案精髓透過疏水 性液體進行萃取醚化反應後比較疏水的烷基甘油醚會 溶解在疏水性燃料中，本案實際進行萃取醚化反應， 同時以疋性、定量進行醚化反應以疏水性燃料萃取院 基甘油醚濃度之實施例結果說明。 8 201002812 -般柴油是石油提煉後的—種油質的產 同的碳氫化合物混合組成，主要成分是 匕由不 原子的鏈烷、環烷或芳烴，化學和物理 1 8個石厌 和重油之間，沸點在17〇U 39〇^生位於汽油 0.82〜0.845kg/卜生質柴油比普通柴油枯二乂重$ =溫下會降低可用性。如同油脂會凝結：：色= 做雲化（Cloud)」，凝結的溫度則叫做「雨’ point)。石油基柴油的雲點大約在攝氏零下oud 1〇〇°/。生質柴油在攝氏零度時便會開始雲化。又，而 實施例之一、 本案根據構想選擇一疏水性燃料十二烷如和⑶此 密度0. 75，黏度1. 34cp，沸點216.2°C ’介於华、，山17Λ 至39(TC之間，取十二烷5〇公克，甘油2〇〇、公、克，甲 醇200公克，觸媒5公克Amberlyst 15置入—反應器 攪拌進行醚化反應，在溫度i 5〇t下經過5小時彳^ 經冷卻後減壓排出二甲基醚（di_methyl ether)，將取出 十二烷油層，用FTIR偵測觀察曱基甘油醚官能基，定 性分析證貫醚化反應進行且溶入疏水性燃料十二院， 而且黏度有明顯降低現象。 實施例之二、 本案根據構想取十二烷50公克，甘油50公克， 甲醇120公克，觸媒1〇公克Amberlyst 15置入一密閉 反應器授拌進行醚化反應，在溫度1 6 〇它下經過1 〇小 時後，經冷卻後減壓排出二甲基醚，取出十二烧油上 層’用GC-Mass進行定量偵測觀察曱基甘油醚官能 基’證實醚化反應進行且溶入疏水性燃料十二烧，其 中含量甲基甘油醚比例’三甲基甘油醚約占6 5 3 %， 9 201002812 二曱基甘油醚約23.2%，一甲基甘油醚約}丨5%，而 且不含甘油。 實施例之三、 : 本案根據構想重複上述實施例之二取十二烷50 公克’甘油50公克’甲醇12〇公克，觸媒公克 Amberlyst 15置入一密閉反應器攪拌進行醚化反應， 在溫度1 8 0 °C下經過1 〇小時後，經冷卻後減壓排出二 甲基醚，取出十二烷油上層，用GC_Mass進行定量偵 f 測觀察甲基甘油醚官能基，證實醚化反應進行且溶入 &水性燃料十二烧’其中含量曱基甘油醚比例，三曱 基甘油醚約幾乎達1 〇〇%，而且不含甘油。 本案合成含氧燃料利用製程液液相萃取反應，以疏 水性油料萃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】 11 ~甘油醚化反應及其產物之疏水性關係 ^ ~~、本案液液相萃取反應合成含氧燃料製程 10 201002812 【主要元件符號說明】 A:—疏水性燃料 B :醇類 C :甘油 D:醚化反應後流體 E :含氧生質燃料(烷基醚) F:甘油與水 G :水 Η :甘油回收 I :醚類回流 1 :反應器 2 :冷卻分層 3:水分分離Phorsulphonic acid ’ xylenesulfonic acid. Wherein: 35 sex catalyst is - liquid acid includes: sulfuric acid, citric acid, hydrofluoric acid. Among them, the temperature of the mystery reaction was from 〇 to 250 °C. Wherein the etherification reaction pressure condition is from 1 to 5 〇 atm. According to the statement, the process includes the use of an indiscriminate gas to isolate it from oxygen. The pure gas is nitrogen. Wherein the etherification reactor comprises: a fixed bed column reactor, a continuous stirred reactor, and a batch reactor. Wherein the alkyl glycan=ether comprises at least: a bis-alkyl glyceryl ether or a tri-alkyl glyceryl ether. The method for separating the hydrophobic fuel may include: flashing the evaporated water with a low boiling point alkyl ether, lowering the oil moisture layer under cooling, and centrifuging. ί α Another example of this case is to provide liquid-liquid phase extraction reaction to synthesize oxygenated fuel to reduce the viscosity and cloud point of the fuel, which is beneficial to remove the water knife after the reaction. The process includes: providing a glycerin raw material , an alcohol, an etherification catalyst and the hydrophobic fuel; providing an etherification reactor; adding the glycerol, the alcohol and the hydrophobic fuel to the etherification reaction The etherification reaction causes the glycerin starting material to form a monoalkyl glyceryl ether with the alcohol to be dissolved in the hydrophobic fuel; and to separate the hydrophobic fuel. According to the above glycerin raw material, the product is transesterified with animal oil and vegetable oil. 7 201002812 Another concept of the present invention is to provide a liquid-liquid phase extraction reaction synthetic fuel process, which can directly reduce the viscosity and cloud point of the fuel, and is beneficial for removing the moisture after the reaction. The process includes: providing glycerin, alcohol 盥- The etherification catalyst provides an etherification reaction; adding the glycerin, the alcohol, and the etherification catalyst to the etherification reactor; performing an etherification reaction to produce a monoglycerol with the alcohol An ether; an aqueous fuel is added to extract the alkyl glyceryl ether therein; and the fuel is separated. In the liquid liquid phase extraction reaction, the process for synthesizing the oxygenated biomass fuel is as shown in Fig. 1. The hydrophobic fuel A, the alcohol B and the glycerin raw material C, and the etherification reactor 1 contain an appropriate amount of etherification catalyst. After stirring at a high temperature and pressure for a suitable period of time, the product fluid D is filtered into a flash evaporator 2, and the unreacted alcohol, the attached product alkyl scale is separated from the water E, and the unreacted glycerol is The oxygen-containing fuel ρ is sent to settle into the layer tank 3, separated by gravity or centrifugally separated, and finally the oxygen-containing fuel G is taken out 'while unreacted glycerol is recovered and sent to the etherification reactor 1' as a key reflux. In order to more specifically illustrate the invention, the present invention will be illustrated by the following examples. [Embodiment] More specifically, the liquid-liquid phase extraction reaction of the present invention can be used to synthesize an oxygen-containing fuel process, which has a viscosity-reducing viscosity and a cloud point, which facilitates the separation and recovery of a hydrophobic fuel from a glycerin phase, and can be widely applied to hydrophobic chemicals including : Petrochemical diesel and biodiesel. The essence of the case is extracted by hydrophobic liquid, and the hydrophobic alkyl glyceryl ether is dissolved in the hydrophobic fuel. In this case, the etherification reaction is actually carried out, and the etherification reaction is carried out with hydrophobicity and quantitative extraction with hydrophobic fuel. The results of the examples of the hospital-based glycerol ether concentration are illustrated. 8 201002812 -Alternative diesel is a petroleum-derived mixture of oil-derived oils. The main component is 匕 from non-atomic alkanes, naphthenes or aromatics, chemical and physical 18 stone and heavy oils. Between, the boiling point is 17 〇 U 39 〇 ^ raw located in gasoline 0.82 ~ 0.845kg / 卜 raw diesel than ordinary diesel dry 乂 乂 weight = 0 will lower the availability. Just like grease will condense:: color = cloud, the temperature of condensation is called "rain" point. The cloud point of petroleum-based diesel is about oud 1 〇〇 ° / Celsius. Biodiesel at zero degrees Celsius Cloudization will begin. In addition, one of the examples, the case is based on the idea of selecting a hydrophobic fuel dodecane such as and (3) the density of 0.75, viscosity 1. 34 cp, boiling point 216.2 ° C 'between China, From 17 Λ to 39 (between TC, take dodecane 5 gram grams, glycerol 2 〇〇, male, gram, methanol 200 gram, catalyst 5 gram Amberlyst 15 placed - reactor stirred for etherification reaction, at temperature i After 5 hours at 5 〇t 彳 ^ After cooling, the dimethyl ether (di_methyl ether) was discharged under reduced pressure, the dodecane oil layer was taken out, and the thiol glyceryl ether functional group was detected by FTIR, and the etherification reaction was qualitatively analyzed. It is carried out and dissolved into the 12th courtyard of hydrophobic fuel, and the viscosity is obviously reduced. In the second example, the case is based on the idea of taking 50 grams of dodecane, 50 grams of glycerin, 120 grams of methanol, and 1 gram of catalyst Amberlyst 15 a closed reactor is mixed to carry out the etherification reaction, at a temperature 1 6 〇 After 1 hour, after cooling, the dimethyl ether was discharged under reduced pressure, and the upper layer of the 12-burning oil was taken out. Quantitative detection by GC-Mass to observe the mercapto glyceryl ether functional group confirmed the etherification reaction. And dissolved in the hydrophobic fuel twelve-burning, wherein the content of methyl glyceryl ether 'trimethyl glyceryl ether accounted for about 65 3 3 %, 9 201002812 dimercapto glyceryl ether about 23.2%, monomethyl glyceryl ether about} 丨 5 %, and does not contain glycerin. Example 3: In this case, according to the above idea, repeat the above two examples of dodecane 50 g 'glycerin 50 g 'methanol 12 gram g, the catalyst gram Amberlyst 15 is placed in a closed reactor stirring The etherification reaction was carried out, and after 1 hour at a temperature of 180 ° C, after cooling, the dimethyl ether was discharged under reduced pressure, the upper layer of dodecane oil was taken out, and the methyl glycerol ether function was observed by GC_Mass. Base, confirming that the etherification reaction proceeds and dissolves into the water-based fuel, the content of mercaptoglycerol ether, tridecylglycerol ether is about 1%, and does not contain glycerol. Process liquid phase extraction reaction The hydrophobic product after the water-based oil extraction reaction can facilitate the separation of the hydrophobic product after the reaction, which is the focus of the present invention. In order to protect the invention of the present invention, it is necessary to modify the invention by those skilled in the art. The statement that you want to protect the scope of the patent application is not included. [Simplified illustration] 11 ~ The glycerol etherification reaction and the hydrophobic relationship of its products ^ ~~, the liquid-liquid phase extraction reaction in this case to synthesize oxygenated fuel process 10 201002812 [Main component symbol description] A: - Hydrophobic fuel B: Alcohol C: Glycerol D: Etherification reaction fluid E: Oxygenated biomass fuel (alkyl ether) F: Glycerol and water G: Water hydrazine: Glycerol recovery I: ether reflux 1: reactor 2: cooling layer 3: moisture separation