201033351 w , 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種複合燃料乳液及其製備方法，其特徵在於該複合燃 料乳液係包含一複合燃料乳劑與一水相成分，特別是關於該複合燃料乳劑 包含乳化劑、助燃劑、穩定劑、抗氧化劑、消泡劑、防凍劑與燃料油之組 成，其摻合該水相成分’並在室溫環境下經一乳化裝置之剪切處理，而製 備該複合燃料乳液，該乳液具有高熱值、乳化穩定性佳、幾無殘渣及污染 e 物少等優點’適合為能源供應來源。本發明涉及化學類中之液體含碳燃料 及氣體燃料等範疇。 【先前技術】 基於燃料油源即將耗竭，以及環境污染曰趨嚴重，替代能源之尋求與 突破迫在眉睫。目前石化燃料仍為主要的能源供應來源，廣泛地使用於汽 機車、工業用的鍋爐或柴油機，以及家用廚浴設備等。 燃料油之瓶@ β 燃料油經燃燒後產生的污染物主要有煙塵微粒、碳氧化物（C0x)、氮 氧化物（NOx)及硫氧化物（s〇x)等，這些污染物不僅造成臭氧層之破壞， 以及酸雨與溫室效應之惡化，煙塵微粒及Ν〇χ所產生之光煙霧更會傷害動 物的呼吸系統及視覺系統等，並妨礙環境視線；ΝΟχ及SOx等廢氣亦會進一 步氧化而生成HN〇3及Μ〇4等腐蝕性強酸而損壞燃燒室内之器壁》 家用廚浴設備所常用之液化石油氣，係為丙烧及丁炫的混合物，目前 主要來源為油氣田或煤之裂解，其中，經煤之裂解所製備的液化石油氣常 含有大量的不飽和烯烴，燃燒後會產生結焦或積炭之累積，而導致燃氣系 3 201033351 w 統的閥瓣黏結失效等問題》經催化裂解所生成之重油或渣油等重質燃料 油’包含有大量的含硫、氮或氧的非烴類化合物，以及易氧化的不飽和烴， 該非烴類化合物包含有砒咯類及四氫》弄唑等非鹼性氮化合物，以及吡啶類 等鹼性氮化合物，其中，砒咯類及四氫噚唑很不穩定而易於氧化生成過氧 化物並引起烴類氧化’再加上該兩類氮化合物共存會加速過氧化物生成及 烴類氧化’造成雜質沈積，或甚至導致燃油系統堵塞等議題。 因此’替代能源之尋求與突破，其關鍵在於：提升燃料之燃燒效率、 © 減少燃料燃燒所排放之污染物，以及減少殘留於燃燒室的積碳渣質等三大 議題尚待克服。 水相在燃油系統之鹿用 根據英國石油公司研究中心於1975年之試驗結果，含水5〜15%之燃 料油於鍋爐中燃燒’將可使NOx減少15〜40%、S〇2減少4〜17%、肌減少 10〜30%、C0減少66〜75%及煙氣降低85%，證實了含水燃料油將因燃燒 較為完全而改善NOx、S0x、C0x及煙塵微粒等廢氣污染。 ® 目前有至少三個方法可將水加入至燃燒室内，分別為： 方法1.經由進氣系統，將水氣伴隨著空氣進入； 方法2.直接將水喷入燃燒室内，或將水添加到燃料油中； 方法3·添加乳化劑至燃料油中，並換水以形成油水乳化燃料，再經喷嘴將 乳化燃料喷入至燃燒室内； 其中方法1及方法2都將造成燃燒室之襯層發生異常熱收縮及破裂等弊 端’而且在維持現有燃燒器結構之前提下，該兩方法都無法使水最佳化分 散於燃料油中，對於燃燒效率之提升無顯著之助益。 4 201033351 界面活性效鹿 方法3所揭示之油水乳化技術中，需要藉由一界面活性劑或乳化劑， 使水相成分與油相成分發生乳化’形成油包水或水包油型態的乳化液，其 中該乳化液包含複數個微米尺寸之油水乳液液滴。 界面活性劑可區分為非離子型及離子型兩大類，其中離子型又可分成 陽離子型、陰離子型及兩性離子型等三類；通常離子型界面活性劑沒有足 夠的親油性使油相產生較大的增溶，難以單獨被使用於油水乳化燃料的應 〇 用上’或乳化效果較差而導致油水乳化燃料不穩定；兩種以上之界面活性 劑共存的混合物，由於其親油基間的内聚力’以及親水基間的氫鍵、偶極_ 偶極力及偶極-離子交互作用等，能形成穩定結構而提升乳化效果，即兩種 或多種界面活性劑之混合物的乳化效果較單一界面活性劑為佳，故實務上 較為廣泛被採用。 界面/¾性劑分子均由親水性的極性基困及親油性的非極性基團所構 成，藉由界面活性劑分子中之親油基與親水基的平衡值，即HLB值 ® (Hydrophilic-Lipophilic Balance，親水親油平衡值），作為該界面活性 劑乳化特性之重要指標，俾以判斷界面活性劑分子屬於親水性或親油性， 非離子型之HLB值介於0〜20，HLB值愈大則代表界面活性劑分子的親水性 愈強，較適於用來製備水包油型態之乳化液；Chung, s Η.與Kim，s•等人 指出油包水及水包油型態之乳化液最穩定的HLB值分別為5 5及l3 7 ; 林成原等人之研究論文中指出，在相同的含水量之下，與油包水二相乳化 液作比較’油包水包油型態之三相乳化液有較高的黏度及排氣溫度，以及 較低的C0及斷廢氣排量，其並指出適合製備油包水包油之三相乳化油之 5 201033351 HLB值為6〜8’HLB值大於10即難以產生安定的油包水包油之三相乳化液。 下表表一係藉由界面活性劑之HLB值，說明界面活性劑在水相中所呈現的 分散狀態： 表一 HLB值範圍 加入水相中的分散狀態 1〜4 不能分散 3〜6 激烈攪拌後，大粒徑粒子可分散 6〜8 激烈攪拌後，溶液呈乳白色 8〜10 溶液穩定呈乳白色 10 〜13 _1 ——_ 幾呈透明或半透明狀之清澈乳白色 13 清澈乳白色 從上表之分散狀態而言，呈現清澈乳白色之乳化液係為處於較佳穩定 狀態，俾藉由該分散狀態來評析乳化液的穩定性。 i 由水乳化燃料在燃油系統的功效 φ 在油水乳化燃料中，其水相成分將可稀釋燃料油中之含氮量及含硫量 等雜質之濃度，得以降低NOx及SOx之生成量，並可稀釋NOx及SOx等廢 氣進一步氧化所產生之HN〇3及Η$〇4等強酸的腐蝕性，而抑制燃燒室之器壁 遭受侵蝕損害。此外，由於該水相成分受熱汽化所成之水蒸氣的存在，將 可使水分分解而發生水煤氣效應，該效應之反應式如下： C (積碳或煙塵）+沁0 (水蒸氣）不C0+H2 使水蒸氣與燃燒室内之積碳或煙塵微粒’反應生成可燃氣體C0及H2而參與 燃燒，甚至重油等在高溫下也可因此被裂解而產生一定量的⑺及扭，這些 6 201033351 ·> 利因都將改善燃燒效率，並減少燃燒室内的積碳及煙塵微粒廢氣。 經乳化之油包水或油包水包油型態的油水乳化燃料’不僅將改善燃料 油之流動性而更易於透過喷嘴在燃燒室内進行喷灑分散，部分油水乳液液 滴顆粒更因其外層油相成分燃燒，使其周遭液滴之包覆在顆粒内層的水相 成分受熱急速汽化，導致其體積急遽膨脹而形成微爆現象，水相成分經微 爆後，會將包覆在其外層之油相成分打散，形成顆粒更小的油滴，而增進 燃燒室内之燃燒前的霧化情形，該理論體系係由蘇俄科學家V. Hivahov於 Θ 1963年首提，並久經實驗所驗證。該些經微爆所產生之油滴將因而進一步 分散於燃燒室内，尤其對於柴油及重油等重質油類之油水乳化燃料的效果 更為顯著’將得以增大與捲入燃燒室内的空氣之接觸表面積，並因油霧的 湍動強度及擴張角度增大而使火焰斷面變寬及變厚，不僅使過剩空氣量減 少2〜6%而同時減少因廢氣排放所散失的熱量，更提高了燃燒室溫度及達 到幾乎充分完全燃燒效果，故可節省燃料用油。 根據台灣成功大學之研究論文〈燃油添加劑之燃燒應用與液滴-液柱碰 ® 撞分析報告〉’於重油或廢油中摻水並進行乳化，當微爆效果佳時，則將因 燃燒效率提升’而彌補因燃料油被少量水取代所造成總發熱量降低之情形。 既有之油水轧化燃斜枯# 相較於油包水型態的油水乳化燃料，水包油型態的油水乳化燃料雖然 較利於輸運’而解決因燃料油之黏稠度所引發之輸運不便的議題，但卻較 為不穩定；諸如Orimulsion油品，其必須儲存在20 30°C環境，而且操作 環境的溫度必須控制在5〜75°C範圍，否則即有因破乳 (de-emulsification)而油水分離之虞，因此不適用為工業用燃料油；此 201033351 外’水包油型態的乳化燃料必須被使用於特製的燃燒器具設備，難以被廣 泛使用於一般的工業用麵爐或柴油機’並且水包油型態之微爆效果遠不如 油包水型態。水包油型態之乳化燃料技術，可見於以下專利號之内容：中 華民國 TW410231、中國大陸 CN1523085、CN1515652、CN1191560、美國 US5360458及PCT專利W095/27021等諸多專利；其中TW410231使用HLB值 介於13〜19之乳化劑，而CN1191560亦使用HLB值介於13〜19之乳化劑， 並經高剪切應力以製備含有超重油濃度為76.5〜82%的水包油型乳化燃 ® 料。然而’水包油型態之油水乳化燃料在乳化穩定性、應用廣泛性、燃料 節省成效及降低煙塵污染效果等層面，其表現均為較差，較不適合作為燃 料供應來源。 油包水型態之乳化燃料技術’按所乳化之燃料油組成，分為輕烴燃料 油之乳化，以及柴油或重油等重質油之乳化；輕烴燃料油包含低分子量之 脂肪烴（通式為0>Η2η+2)及環炫烴（通式為CJk)，以及微量之芳香烴，而 大多數之單一界面活性劑較難以溶於脂肪烴及環烷烴之混合物；柴油或重 ® 油包含高黏度之芳香烴及長鏈聚合物烴為主，而使其能被大多數之界面活 性劑所乳化。 輕烴燃料油之乳化技術可見於以下之專利内容，其中CN1769400使用 含氟烷基醚醇以乳化輕烴戊烷，TW189847則採用25〜85%烷酵醯胺、5〜 25%乙氧基化烷基酚及0〜40%共聚物所組成，本發明人按TW189847之内 容製備一比較例乳化液，發現其穩定性不佳，詳見於實施例7。 柴油或重油之乳化技術廣為被使用’係在重油或柴油等燃料油中摻入 一定量的水相成分，並經機械及/或化學的方法使其充分混合以製備乳化燃 8 201033351 m 料。可參見於以下之專利内容：US4743357、US3649527、JP57-49696、 W082/02241等專利，該些技術其所採取的措施多為在適當無機催化劑及必 要之酸驗環境、溫度與壓力下，使水相成分參與催化裂解反應而產生曱烷、 C0及輕質燃料油，經燃燒後不僅存有無機催化劑殘渣，也因處理過程之耗 能而減損節能效果。此外，TW589369使用30〜80%聚氧化乙烯脂肪醇醚、 5〜50% Span 20〜80系列及5〜50% Tween 20〜80系列之混合物，以製 備HLB值介於2.5〜8的非離子界面活性劑；TW574365描述一添加劑含有 Ο 20〜70%重量比的HLB值介於2.5〜8之乳化劑，其由碳數為4〜18之脂肪 酸聚氧化乙稀或高級醇聚氧化乙稀化合物、Span 20〜80及Tween 20〜80 系列所調製而成；該兩專利TW589369及TW574365之添加劑都包含高鉉睃 鉀及重鉻酸納等無機氧化劑，致使該些乳化燃料經燃燒後皆存有大量渔質 而殘留於燃燒室内。 US5024676、JP1-185394、JP1-313595所揭示之乳化燃料中，重油等油 類在乳化燃料中的濃度最高只為77%重量百分比；在中國大陸之〈節能技術 ® 〉1990(3)13-19等文獻，其摻水比例為1〇〜20% ’節油率大約為1〇%，節 油效果不佳；CN1589312柴油燃料乳液包含HLB值介於4〜8之非離子界面 活性劑以及至多25%重量百分比的水；根據台灣成功大學之研究論文〈燃油 添加劑之燃燒應用與液滴-液柱碰撞分析報告〉，其僅建議添加1〇%水量； 按TW589369之描述’一般乳化燃料不易點火，尤其當所添加之水相成分含 量為30%重量百分比以上時即無法點火；總而言之，受限於目前既有乳化 燃料技術之含水量最高僅能為1〇〜30%，不僅燃料節省效果不佳，也限制 了乳化燃料之產業利用性。 9 201033351 使用高濃度4〜6%重量百分比之多元醇偏酯的柴油與水之乳化燃料技 術，可見於以下專利：W0 85/04183、W0 00/63322、W0 01/02516、US3876391、 GB2066288、GB2352246、EP0012292、EP0242832、EP0372353、EP0888421、 EP0893488、EP1101815、DE3229918、CN1079499 及 JP-B2-2793190 中，但 是’高濃度乳化劑卻會於乳化液中發生沈澱，實務上之觀察結果，若乳化 劑未能均勻分散於乳化液時，常會在燃燒室内壁及配管管壁内殘留膠狀黏 膜物’妨礙或堵塞乳化燃料於燃油系統管路之流通性，而造成燃燒不完全， ® 也增加燃燒器具設備的維護費用。 其他乳化燃料技術尚可見於以下專利：TW200533739、TWI272303、 TW256853、US5024676、US6030424、CN1051753 及 CN1188138 等專利，相關 文獻指出上述該些乳化液之穩定性不佳而容易分層破乳，即乳化燃料在燃 燒前即油水分離，故燃燒效率不佳。 另外，EP630398描述一乳化燃料，其包含一烴燃料、3〜35%重量百分 比之水’及至少0.1%重量百分比之乳化劑，其中該乳化劑包含山梨糖醇脂 © 肪酸酯、聚烷二醇及乙氧基化烷基酚；W097/34969描述HLB值介於6〜8之 乳化倒’其包含山梨糖醇脂肪酸龍、聚乙二醇單油酸酯及乙氧基化壬基酚； W092/19701描述HLB值少於8之乳化劑，其包含烷醇醢胺及乙氧基化烷基 盼，CN1462795所揭示之柴油安定添加劑，其包含非離子表面活性劑之hlb 值為4〜10，CN1083516描述一包含20〜40%聚乙基越類之乳化劑，而提高 油水乳化燃料之節油率至20〜30% ; CN1236003描述一包含15〜20%烷基 苯乙氧基醚及10〜15%烷基苯聚乙氧基醚；TW470771所採用之乳化劑包含 聚氧化烷基酚、乙醇胺類、丁醇及甘油酯類等混合物；>1^200740983使用含 201033351 » 有0. 5〜3%乳化劑及l〇〜45%生化水溶液之添加劑以製備乳化柴油及乳化 重油，上述之乳化燃料技術所製備之乳化液組成明顯與本發明不同，故其 效果也不如本發明。 總而言之’目前既有之乳化燃料技術仍有諸多缺點尚待突破，俾列舉 如下： (1) 乳液之乳化穩定性不佳而輸運儲備不易：筆因於乳化劑與相關助劑 之組成不佳、製程溫度不當、或乳化裝置之剪切處理不當而未能使 參 乳液液滴趨於微粒化，導致乳液之乳化不完全而易於發生凝聚並分 層破乳，故於室溫儲存環境下，目前大多數乳化燃料維持油水不分 離狀態至多僅能保持數日，一般而言，乳化燃料必須於製備完成後 便立即被使用，因此不利於長距離輸運或大規模生產儲備。 (2) 熱值提升效果不佳並有雜渣殘留：肇因於乳化劑與水相成分之組成 不佳’於燃油系統管路中存有膠質異物或經燃燒後於燃燒室殘留大 量積碳雜渣’不僅減損燃燒效率，燃燒器具設備之維護也相當不便》 ❹ 針對上述缺點’經本案發明人研究發現，乳化劑及相關助劑之種類及 用量，影響其與燃料油及水之間的交互作用，進而決定乳化燃料之品質， 因此，在保留油包水型態之乳化燃料在燃燒上所提供之優點的前提下，藉 由選用適當種類及劑量之添加劑能有效解決先前技術所述之問題，進而提 出一種新穎、穩定性佳及高熱值的複合燃料乳液以及其製備方法。 201033351 【發明内容】 本發明之目的係提供一種複合燃料乳劑，其用以與水摻合，製備成油 包水或油包水包油之乳化型態的複合燃料乳液；該乳液與等體積的瓦斯、 天然氣、重油或柴油等燃料油作比較，其熱值較高並高於15〜30% ;此外， 該乳液易於點火燃燒，而且其經燃燒後所排放之廢氣的濃度與數量均較等 體積燃料油為低，確實適於作為各種燃燒器之燃料來源》 本發明之目的係提供一種複合燃料乳液，其特徵係包含一複合燃料乳 φ 劑與水摻合所製備之油包水或油包水包油型態的乳液；該乳液與等體積的 瓦斯、天然氣、重油或柴油等燃料油作比較，其熱值較高並高於15〜30% ; 此外，該乳液易於點火燃燒，而且其經燃燒後所排放之廢氣的濃度與數量 均較等體積燃料油為低，確實適於作為各種燃燒器之燃料來源。 本發明之目的係提供一種複合燃料乳劑，其利於儲存與長距離輸運， 待輸運至目的地之後，再將該乳劑與水摻合，以製備油包水或油包水包油 型態的複合燃料乳液，該乳液具有4個月以上之長時間儲存而油水不分離 φ 的穩定性。 本發明之目的係提供一種液態複合燃料乳液，其特徵係包含一複合燃 料乳劑與水換合所製備之油包水或油包水包油型態的乳液，該乳液具有4 個月Λ上之長時間儲存而油水不分離的穩定性》 本發明之目的係提供一種複合燃料乳液，其特徵係包含一複合燃料乳 劑與水摻合所製備之油包水或油包水包油型態的乳液，經一高溫加熱裝置 汽化成一氣態燃料’該氣態燃料與等體積的天然氣與瓦斯作比較，其熱值 較高並高於15〜30%，確實適於作為各種燃燒器之燃料來源。 12 201033351 « 本發明之目的係提供一複合燃料乳劑，其用以與水換合，以製備油包 水或油包水包油型態的複合燃料乳液，其中該乳劑之特徵係包含： (1) 乳化劑：係為至少一種之非離子型界面活性劑，選自於Tween 20 〜80系列（p〇iyethoxylated sorbitan esters，聚氧乙稀山梨糖醇 脂肪酸酯）、Span 20〜85系列（sorbitan esters，山梨糖醇脂肪酸 醋）、Triton 100〜405 系列（alkylphenol ethoxylates，燒基盼 聚氧乙烯謎）與 S0FTAN0L 50〜120 系列（Polyoxyethylene alkyl φ ether，聚氧乙烯脂肪醇醚）之至少一種，用以將油相及水相之溶液 進行乳化，以形成油包水或油包水包油型態乳液，其中該乳化劑之 HLB值範圍介於4〜8之間，較佳的HLB值為5〜6 » (2) 助燃劑：係用以增進該乳液之點火及燃燒性質的一種或多種過氧化 物為主所組成，選自至少一種下述化合物：過氧化氫、過氧甲酸、 過氧乙酸、二環戊二烯鐵、甲苯、二甲苯、叔丁基過氧化氫、二叔 丁基過氧化氫、異丙基過氧化氫、丙酮過氧化氫、過氧化環己酮、 φ 過氧化二苯甲醯、過氧化苯乙醯、過氧化乙丁醸、硝酸烷基酯、過 氧化三曱基乙酸第三丁酯、過氧化二丁丙苯，以及該些之同系物及 衍生化合物等，較佳為過氧化氫及二甲苯所組成，並可溶解重油或 渣油中的瀝青質或膠質等雜質成分，更有利於燃燒。 (3) 穩定劑：係為至少一種之助乳化劑，用以促進在該乳液的油水界面 間形成一界面膜’其特徵為包含羥基（-0H)、羰基（-C0-)、胺基 (-NH2)、叛基（-C00H)與輯基（-C00-)等至少一種能形成氫鍵之 官能基團，用以增強油水界面膜的強度，而改善乳化劑之乳化效果； 13 201033351 該穩定劑係選自至少一種下述化合物：醇類、多元酵、酚類、環氧 化物、聚氧化物、胺類、有機酸、醣類以及該些之同系物及衍生化 合物等，亦即為選自於甲醇、乙醇、乙二醇、丙二醇、丙三醇、異 戊四醇、聚乙烯醇、曱酚、二甲酴、丁酚、第二辛基酚、聚氧化乙 烯、聚乙烯醇縮曱醛、聚丙烯酸、乙二酵胺、聚丙烯酸胺、羧甲基 纖維素、動物膠、藻酸鹽、果膠、黃原膠，以及該些之同系物及衍 生化合物等，較佳為黃原膠所組成。 ® (4)抗氧化劑：係用以防止該乳劑，以及該乳劑摻水所製備之乳液經長 久時間儲存而變質，也能改善重油或柴油於燃燒後所生成之不飽和 烴發生聚合而導致結焦情形；選自至少一種下述化合物：2,5-二叔 丁基對苯二酚、叔丁基對苯二酚、2, 6二叔丁基對甲酚、2, 6二叔丁 基二甲胺基對甲酚、叔丁基羥基茴香醚、掊酸丙酯（propyl gallate)、3，5—二叔丁基一4—羥基苯丙酸異辛酯、N，N-二甲基十 二烷基胺、N, N-二曱基十八烷基胺、三正辛胺、N, N-二乙基羥胺、 ® N,N-二曱基環己胺、有機磷酸酯、二烷基二硫代磷酸辞鹽，以及該 些之同系物及衍生化合物等，較佳為叔丁基對苯二酚所組成。 (5)消泡劑：係用以破壞或抑制乳劑或乳液起泡，並增強乳化效果；其 通常具有較佳的化學穩定性及熱穩定性、較低的表面張力以使泡沫 不易形成、較佳的舖展係數以易於在溶液表面鋪展而快速消泡，以 及低揮發性等特性；選自至少一種下述化合物：二甲基碎氧烷、添 加二氧化矽的二甲基梦氧烷混合物、聚矽氧烷、烷基聚矽氧烷、聚 謎改性聚矽氧烷共聚物、烷基填酸酯鹽、環氧乙烷與環氧丙烷共聚 14 201033351 物，以及該些之同系物及衍生化合物等，較佳為聚矽氧烷所組成。 (6) 防凍劑：係用以防止乳劑或乳液凝固，選自至少一種下述化合物： 甲醇、乙二醇、丙二醇、丙三醇、乙烯乙二醇、聚麩氨酸、尿素、 一甲基亞職’以及該些之同系物及衍生化合物等，較佳為乙二醇所 組成。 (7) 燃料油：係為選自至少一種之竣數為5〜22的含碳燃料，其包含： 汽油、煤油、柴油、蠟油、重油或渣油、油漿、石油溶劑、動物油、 ❹ 植物油、生物降解油、礦物油及廢油等，以及在該些含碟燃料中混 入可燃性粉粒（例如碳黑）而得到的產物，皆可作為本發明之複合 燃料乳劑的油相成分；該些油品之組成如了： 油品 成分碳數 分镏溫度（°c) 用途 石油醚 C5 〜C6 20 〜60 有機溶劑 汽油 C6 〜C12 60 〜200 汽車燃料、有機溶劑 煤油 C10〜C16 175〜300 柴油機、燈油及喷射機燃料 柴油 C15〜C20 250〜400 柴油機燃料 蠟油 C18〜C22 >300 潤滑油 此外，重油或渣油是原油經減壓或常壓蒸餾後剩餘的殘渣，包含飽 和烴、芳香烴、瀝青質、膠質及硫氮含量等，油漿包含3〇%〜5〇%的 飽和烴與膠質及50%以上的芳香烴等，石油溶劑係包含石油醚、戊 烧、正己烧、庚烧、去潰油、朝溶劑及脫臭溶·，廢油包含廢 棄之汽機車機油等引擎用油、廢棄之潤滑油與切削油等工業用油、 及廢棄之食用油等民生用油。 15 201033351 此外，氫氧化鉀及氫氧化鈉等的添加，除了調節乳劑之pH值及 與燃料油中的酸性雜質結合成極細的爐灰而減輕環境污染之外，更 能藉此使乳液之油水液滴顆粒表面帶有電荷以增進立體障礙作用 (stenicstabihization)，進而減少絮凝（flocculation)與聚結 (coalescence)現象之發生，乳液液滴因而更不易發生破乳。 總而言之，本發明之該複合燃料乳劑包含乳化劑、助燃劑、穩定劑、 ® 抗氧化劑、消泡劑、防凍劑與燃料油之組成，分別各佔乳劑之1〜5%、1 〜5%、1〜3%、1〜2%、1〜3%、1〜3%與79〜94%體積百分比；其中該 乳劑之組成幾皆為有機物，可在燃燒室内被全部燃燒以提供熱量，幾無雜 潰殘留，而解決長久以來一直無法克服的技術障礙。 本發明之目的係提供一種複合燃料乳液，其特徵係包含該複合燃料乳 劑與水摻合所製備之油包水或油包水包油型態的乳液，其中該乳液之特徵 係包含： (1) 該複合燃料乳劑，係包含：乳化劑、助燃劑、穩定劑、抗氧化劑、 消泡劑、防凍劑與燃料油之組成，分別各佔乳劑之1〜5%、丨〜5%、 1〜3%、1〜2%、1〜3%、1〜3%與79〜94%體積百分比。 (2) —水相成分，係選自至少一種之水，其包含：具有微量元素的低碟 物質之水、去離子水、純水及磁化水’其中磁化水係經過磁場的磁 化處理；較佳為去離子水，以避免水中過量的礦物質沈積於燃燒器 内。 本發明之目的係提供一種複合燃料乳劑的製備方法，係包括將該乳劑 201033351 所包含之一穩定劑與1〜5%體積比的水相混合以進行預乳化，再與一添加 劑組合物混製成該乳劑， 其中該複合燃料乳劑包含： 乳化劑 1〜5 %體積百分比 穩定劑 1〜3 %體積百分比 助燃劑 1〜5 %體積百分比 抗氧化劑 1〜2 %體積百分比 防凍劑 1〜3 %體積百分比 消泡劑 1〜3 %體積百分比 燃料油 79〜94 %體積百分比 ❹ 其特徵在於該方法包含下列步驟： (1) 將該乳劑之該穩定劑與1〜5%體積百分比的水相成分混合，201033351 w, VI. Description of the Invention: [Technical Field] The present invention relates to a composite fuel emulsion and a preparation method thereof, characterized in that the composite fuel emulsion comprises a composite fuel emulsion and an aqueous phase component, in particular The composite fuel emulsion comprises an emulsifier, a combustion improver, a stabilizer, an antioxidant, an antifoaming agent, an antifreeze and a fuel oil, which are blended with the aqueous phase component and are sheared by an emulsifying device at room temperature. The composite fuel emulsion is prepared, and the emulsion has the advantages of high calorific value, good emulsion stability, few residue and less pollution, and is suitable as a source of energy supply. The present invention relates to liquid carbonaceous fuels and gaseous fuels in the chemical category. [Prior Art] Based on the exhaustion of fuel oil sources and the seriousness of environmental pollution, the search for and breakthrough of alternative energy sources is imminent. At present, fossil fuels are still the main source of energy supply, and are widely used in steam locomotives, industrial boilers or diesel engines, and household kitchen bath equipment. Fuel oil bottle @ β Fuel oil is mainly produced by the combustion of pollutants such as soot particles, carbon oxides (C0x), nitrogen oxides (NOx) and sulfur oxides (s〇x), which not only cause the ozone layer Destruction, as well as the deterioration of acid rain and greenhouse effect, the light smoke generated by soot particles and cockroaches can damage the respiratory system and visual system of animals, and hinder the environmental sight; 废气 and SOx and other exhaust gases will be further oxidized to generate HN〇3 and Μ〇4 and other corrosive strong acids damage the walls of the combustion chamber. The liquefied petroleum gas commonly used in household kitchen equipment is a mixture of propylene and Dingxuan. The main source is the cracking of oil and gas fields or coal. Among them, the liquefied petroleum gas prepared by the cracking of coal often contains a large amount of unsaturated olefins, which will cause accumulation of coking or coke after combustion, which leads to problems such as failure of valve sticking of gas system 3 201033351 w. The heavy fuel oil such as heavy oil or residual oil produced by cracking contains a large amount of non-hydrocarbon compounds containing sulfur, nitrogen or oxygen, and unsaturated hydrocarbons which are easily oxidized, and the non-hydrocarbon compounds Containing non-basic nitrogen compounds such as fluorene and tetrahydro-carbazole, and basic nitrogen compounds such as pyridines, among which sulfonium and tetrahydrocarbazole are unstable and easily oxidized to form peroxides and cause hydrocarbons. Oxidation 'plus the coexistence of the two types of nitrogen compounds accelerates the formation of peroxides and the oxidation of hydrocarbons, causing the deposition of impurities, or even causing blockage of the fuel system. Therefore, the key to the pursuit and breakthrough of alternative energy sources is that the three major issues of improving fuel combustion efficiency, reducing pollutants emitted by fuel combustion, and reducing carbon residue in the combustion chamber have yet to be overcome. The dehydration of the water phase in the fuel system is based on the results of a test conducted by the British Petroleum Research Center in 1975. The combustion of 5~15% of the fuel oil in the boiler will reduce NOx by 15~40% and S〇2 by 4~ 17%, muscle reduction of 10~30%, C0 reduction of 66~75% and smoke reduction of 85%, confirmed that the water-based fuel oil will improve exhaust pollution such as NOx, S0x, C0x and soot particles due to relatively complete combustion. ® There are currently at least three ways to add water to the combustion chamber: Method 1. Intake the water with air through the intake system; Method 2. Spray water directly into the combustion chamber, or add water to the In the fuel oil; Method 3) adding an emulsifier to the fuel oil, and changing the water to form an oil-water emulsion fuel, and then spraying the emulsion fuel into the combustion chamber through the nozzle; wherein both the method 1 and the method 2 will cause the liner of the combustion chamber to occur The drawbacks of abnormal heat shrinkage and cracking' are also raised before the existing burner structure is maintained. Both methods cannot optimize the dispersion of water in the fuel oil, which has no significant benefit to the improvement of combustion efficiency. 4 201033351 In the oil-water emulsification technology disclosed in the interface active effect deer method 3, the aqueous phase component and the oil phase component need to be emulsified by a surfactant or emulsifier to form a water-in-oil or oil-in-water emulsified form. a liquid, wherein the emulsion comprises a plurality of micron-sized oil-water emulsion droplets. The surfactant can be divided into two types: non-ionic and ionic. The ionic type can be divided into three types: cationic, anionic and zwitterionic. Generally, the ionic surfactant does not have sufficient lipophilicity to produce oil phase. Large solubilization, it is difficult to be used alone in the application of oil-water emulsion fuels' or the emulsification effect is poor, resulting in instability of the oil-water emulsion fuel; the mixture of two or more surfactants coexists due to the cohesive force between the oleophilic groups 'and the hydrogen bond between the hydrophilic groups, the dipole _ dipole force and the dipole-ion interaction, etc., can form a stable structure and enhance the emulsification effect, that is, the emulsification effect of the mixture of two or more surfactants is simpler than the single surfactant. It is better, so it is widely used in practice. The interface/3⁄4 agent molecules are composed of a hydrophilic polar group and a lipophilic non-polar group, and the equilibrium value of the lipophilic group and the hydrophilic group in the surfactant molecule, that is, the HLB value® (Hydrophilic- Lipophilic Balance, a hydrophilic-lipophilic balance), as an important indicator of the emulsifying properties of the surfactant, to determine whether the surfactant molecule is hydrophilic or lipophilic, and the non-ionic HLB value is between 0 and 20, and the HLB value is higher. Larger means that the hydrophilicity of the surfactant molecule is stronger, which is more suitable for preparing the oil-in-water emulsion; Chung, s Η. and Kim, s• et al. indicate the water-in-oil and oil-in-water type. The most stable HLB values of the emulsions are 5 5 and 13 7 respectively; Lin Chengyuan et al. pointed out that compared with the water-in-oil two-phase emulsion under the same water content, the oil-in-water-in-oil type The three-phase emulsion has higher viscosity and exhaust temperature, as well as lower C0 and off-gas displacement, and points out that it is suitable for preparing oil-in-water-in-water three-phase emulsified oil. 5 201033351 HLB value is 6~ 8' HLB value is greater than 10, which is difficult to produce stable oil-in-water Emulsion. Table 1 below shows the dispersion state of the surfactant in the aqueous phase by the HLB value of the surfactant: Table 1 HLB value range Dispersion state added to the aqueous phase 1~4 Dispersible 3~6 Intense stirring After that, the large particle size can be dispersed 6~8. After vigorous stirring, the solution is milky white 8~10. The solution is stable and milky white 10~13 _1 —— _ a few transparent or translucent clear milky white 13 clear milky white scattered from the above table In the state, the emulsion exhibiting a clear milky white color is in a preferably stable state, and the stability of the emulsion is evaluated by the dispersion state. i The efficacy of water-emulsified fuel in the fuel system φ In the oil-water emulsion fuel, the water phase component can dilute the concentration of impurities such as nitrogen and sulfur in the fuel oil to reduce the amount of NOx and SOx produced, and It can dilute the corrosiveness of strong acids such as HN〇3 and Η$〇4 generated by further oxidation of exhaust gas such as NOx and SOx, and suppress the erosion damage of the wall of the combustion chamber. In addition, due to the presence of water vapor formed by the vaporization of the water phase component, the water gas effect can be decomposed and the water gas effect occurs. The reaction formula of the effect is as follows: C (carbon or soot) + 沁0 (water vapor) is not C0 +H2 causes water vapor to react with carbon deposits or soot particles in the combustion chamber to form combustible gases C0 and H2 to participate in combustion. Even heavy oils can be cracked at high temperatures to produce a certain amount of (7) and twists. These 6 201033351 · > Lein will improve combustion efficiency and reduce carbon deposits and soot particles in the combustion chamber. The emulsified water-in-oil or oil-in-water-in-oil type oil-water emulsion fuel not only improves the fluidity of the fuel oil but is more easily sprayed and dispersed in the combustion chamber through the nozzle, and some of the oil-water emulsion droplet particles are more affected by the outer layer. The oil phase component is burned, so that the water phase component coated in the inner layer of the particle is rapidly vaporized by heat, causing its volume to rapidly expand and form a micro-explosion phenomenon. After the micro-explosion, the water phase component will be coated on the outer layer. The oil phase components are broken up to form smaller oil droplets, which promotes the atomization before combustion in the combustion chamber. The theoretical system was first introduced by Soviet scientist V. Hivahov in 1963 and has been experimentally advanced. verification. The oil droplets generated by the micro-explosion will be further dispersed in the combustion chamber, especially for the oil-water emulsion fuel of heavy oil such as diesel oil and heavy oil, which will be more effective and will increase the air entrained in the combustion chamber. The surface area is contacted, and the flame cross-section is widened and thickened due to the increase in the turbulence intensity and the expansion angle of the oil mist, which not only reduces the excess air volume by 2 to 6%, but also reduces the amount of heat lost by the exhaust gas emission, and further increases The combustion chamber temperature and the almost complete combustion effect are achieved, so that fuel oil can be saved. According to the research paper of Taiwan's successful university, "Combustion Application of Fuel Additives and Droplet-Liquid Column Collision Analysis Report", water is mixed with heavy oil or waste oil and emulsified. When the micro-explosion effect is good, it will be due to combustion efficiency. Enhance 'to compensate for the reduction in total heat generation caused by the replacement of fuel oil with a small amount of water. The existing oil-water rolling igniting and sloping # Compared with the water-in-oil type oil-water emulsion fuel, the oil-in-water type oil-water emulsion fuel is better for transporting and solves the problem caused by the viscosity of the fuel oil. Inconvenient issues, but less stable; such as Orimulsion oil, it must be stored at 20 30 ° C environment, and the operating environment temperature must be controlled in the range of 5 ~ 75 ° C, otherwise there is due to demulsification (de- Emulsification) and the separation of oil and water, therefore not suitable for industrial fuel oil; this 201033351 external 'oil-in-water type emulsion fuel must be used in special combustion equipment, difficult to be widely used in general industrial furnaces Or the diesel engine' and the micro-explosion effect of the oil-in-water type is far less than the water-in-oil type. The oil-in-water emulsion fuel technology can be found in the following patents: Republic of China TW410231, China mainland CN1523085, CN1515652, CN1191560, US 5360458 and PCT patent W095/27021; among them, TW410231 uses HLB value of 13 An emulsifier of ~19, and CN1191560 also uses an emulsifier having an HLB value of 13 to 19, and is subjected to high shear stress to prepare an oil-in-water emulsion fuel containing material having a super heavy oil concentration of 76.5 to 82%. However, the oil-in-water emulsion fuel of the oil-in-water type has poor performance in terms of emulsion stability, wide application, fuel saving effect and reduction of smoke pollution effect, and is less suitable as a fuel supply source. The water-in-oil type emulsion fuel technology is composed of emulsified fuel oil, emulsified by light hydrocarbon fuel oil, and emulsified by heavy oil such as diesel or heavy oil; light hydrocarbon fuel oil contains low molecular weight aliphatic hydrocarbons. The formula is 0 gt; Η 2 η + 2) and cycloheximide (formula CJk), and a trace amount of aromatic hydrocarbons, and most of the single surfactant is more difficult to dissolve in a mixture of aliphatic hydrocarbons and naphthenes; diesel or heavy oil It contains high viscosity aromatic hydrocarbons and long-chain polymer hydrocarbons, which can be emulsified by most surfactants. Emulsification techniques for light hydrocarbon fuel oils can be found in the following patents, in which CN1769400 uses fluoroalkyl ether alcohol to emulsify light hydrocarbon pentane, TW189847 uses 25-85% alkanoic acid, 5 to 25% ethoxylation. A composition of an alkyl phenol and a copolymer of 0 to 40%, the inventors prepared a comparative emulsion according to the contents of TW189847, and found that the stability was not good, as shown in Example 7. The emulsification technology of diesel oil or heavy oil is widely used to incorporate a certain amount of water phase components in fuel oil such as heavy oil or diesel oil, and fully mixed by mechanical and/or chemical methods to prepare emulsified fuel 8 201033351 m . See the following patents: US4743357, US3649527, JP57-49696, W082/02241 and other patents, the measures taken by these technologies are mostly water under appropriate inorganic catalyst and necessary acid test environment, temperature and pressure. The phase components participate in the catalytic cracking reaction to produce decane, C0 and light fuel oil. After combustion, not only the inorganic catalyst residue but also the energy consumption of the treatment process can reduce the energy saving effect. In addition, TW589369 uses a mixture of 30 to 80% polyoxyethylene fatty alcohol ether, 5 to 50% Span 20 to 80 series and 5 to 50% Tween 20 to 80 series to prepare a nonionic interface with an HLB value of 2.5 to 8. Active agent; TW574365 describes an additive containing 〜 20 to 70% by weight of an emulsifier having an HLB value of 2.5 to 8, which is composed of a fatty acid polyethylene oxide having a carbon number of 4 to 18 or a higher alcohol polyethylene oxide compound. Span 20~80 and Tween 20~80 series are prepared; the additives of TW589369 and TW574365 both contain inorganic oxidants such as strontium potassium and sodium dichromate, so that the emulsion fuels are burned after burning. The fish quality remains in the combustion chamber. Among the emulsion fuels disclosed in US Pat. No. 5,024,676, JP 1-185394, and JP 1-313595, the concentration of heavy oil and the like in the emulsion fuel is only 77% by weight; in China, Energy Saving Technology® 1990(3) 13-19 Such literature, its water mixing ratio is 1〇~20% 'fuel saving rate is about 1〇%, fuel economy is not good; CN1589312 diesel fuel emulsion contains non-ionic surfactant with HLB value between 4~8 and up to 25 % by weight of water; according to the research paper of Taiwan's successful university (combustion application of fuel additive and droplet-liquid column collision analysis report), it is only recommended to add 1% water; according to TW589369, 'general emulsion fuel is not easy to ignite, Especially when the content of the added water phase component is more than 30% by weight, the ignition cannot be achieved; in short, the current water content of the existing emulsion fuel technology is only up to 1 〇 30%, which is not only poor fuel saving effect. It also limits the industrial utilization of emulsion fuels. 9 201033351 Emulsified fuel technology using diesel and water with a high concentration of 4 to 6% by weight of polyol partial ester can be found in the following patents: W0 85/04183, W0 00/63322, W0 01/02516, US3876391, GB2066288, GB2352246 , EP0012292, EP0242832, EP0372353, EP0888421, EP0893488, EP1101815, DE3229918, CN1079499 and JP-B2-2793190, but 'high concentration of emulsifier will precipitate in the emulsion, the actual observation, if the emulsifier fails When it is evenly dispersed in the emulsion, it often leaves a gel-like mucous material in the inner wall of the combustion chamber and the wall of the pipe. It hinders or blocks the flow of the emulsion fuel in the fuel system piping, resulting in incomplete combustion. ® also increases the equipment of the combustion equipment. maintenance fees. Other emulsion fuel technologies can be found in the following patents: TW200533739, TWI272303, TW256853, US5024676, US6030424, CN1051753 and CN1188138. The related literatures indicate that the above emulsions are not stable and are easy to be layered and demulsified, that is, the emulsion fuel is The oil and water are separated before combustion, so the combustion efficiency is not good. Further, EP 630 398 describes an emulsion fuel comprising a hydrocarbon fuel, 3 to 35% by weight of water' and at least 0.1% by weight of an emulsifier, wherein the emulsifier comprises sorbitol fatty acid ester, polyalkane Alcohol and ethoxylated alkyl phenol; W097/34969 describes an emulsification of HLB value between 6 and 8 which comprises sorbitol fatty acid dragon, polyethylene glycol monooleate and ethoxylated nonyl phenol; W092/19701 describes an emulsifier having an HLB value of less than 8, which comprises an alkanolamine and an ethoxylated alkyl group. The diesel stability additive disclosed in CN1462795 contains a nonionic surfactant having a hlb value of 4 to 10 CN1083516 describes an emulsifier comprising 20~40% polyethyl versa, and improving the fuel economy of the oil-water emulsion fuel to 20~30%; CN1236003 describes a 15-20% alkyl phenyl ethoxy ether and 10 〜15% alkyl benzene polyethoxy ether; emulsifier used in TW470771 comprises a mixture of polyoxyalkylphenols, ethanolamines, butanol and glycerides; >1^200740983 use 201033351 » has 0. 5 ~3% emulsifier and l〇~45% biochemical aqueous solution additive to prepare emulsified diesel And the emulsified heavy oil, the emulsion composition prepared by the above emulsion fuel technology is obviously different from the present invention, and therefore the effect is not as good as the present invention. In summary, there are still many shortcomings in the existing emulsion fuel technology, which are listed below: (1) The emulsion stability of the emulsion is not good and the transport reserve is not easy: the composition of the emulsifier and related additives is poor. If the process temperature is improper, or the shearing treatment of the emulsifying device is improper, the immersion emulsion droplets tend to be micronized, resulting in incomplete emulsification of the emulsion, easy aggregation and delamination, so in a room temperature storage environment, At present, most of the emulsion fuels maintain the oil-water separation state for at most only a few days. In general, the emulsion fuel must be used immediately after the preparation is completed, which is not conducive to long-distance transportation or large-scale production reserves. (2) Poor heat value improvement and residual residue: 肇 Due to poor composition of emulsifier and water phase components, there is a colloidal foreign matter in the fuel system pipeline or a large amount of carbon deposit remains in the combustion chamber after combustion. The miscellaneous slag not only degrades the combustion efficiency, but also the maintenance of the equipment of the burning appliance is quite inconvenient. ❹ In response to the above shortcomings, the inventors of the present study found that the type and amount of emulsifier and related auxiliaries affect its relationship with fuel oil and water. The interaction, in turn, determines the quality of the emulsified fuel. Therefore, the advantages of the prior art can be effectively solved by selecting the appropriate type and dosage of additives while preserving the advantages of the water-in-oil type of emulsified fuel. The problem is to propose a novel, stable and high calorific value composite fuel emulsion and a preparation method thereof. 201033351 SUMMARY OF THE INVENTION The object of the present invention is to provide a composite fuel emulsion for blending with water to prepare a water-in-oil or oil-in-water emulsified composite fuel emulsion; the emulsion and an equal volume Compared with fuel oils such as gas, natural gas, heavy oil or diesel oil, the calorific value is higher and higher than 15~30%. In addition, the emulsion is easy to ignite and burn, and the concentration and quantity of exhaust gas discharged after combustion are equal. The volumetric fuel oil is low and is indeed suitable as a fuel source for various burners. The object of the present invention is to provide a composite fuel emulsion characterized by comprising a water-in-oil or oil prepared by blending a composite fuel emulsion φ agent with water. An oil-in-water emulsion; the emulsion has a higher calorific value and is higher than 15 to 30% compared with an equal volume of fuel oil such as gas, natural gas, heavy oil or diesel; in addition, the emulsion is easy to ignite and burn, and The concentration and quantity of the exhaust gas discharged after combustion are lower than that of the equal volume fuel oil, and it is indeed suitable as a fuel source for various burners. The object of the present invention is to provide a composite fuel emulsion which is convenient for storage and long-distance transport, and after being transported to a destination, the emulsion is blended with water to prepare a water-in-oil or oil-in-water-in-oil type. The composite fuel emulsion has a stability of storage for a long period of time of 4 months or more and oil and water does not separate φ. The object of the present invention is to provide a liquid composite fuel emulsion characterized by comprising a composite fuel emulsion and a water-in-oil or oil-in-water-in-oil emulsion prepared by water exchange, the emulsion having a temperature of 4 months. Stability for long-term storage without oil and water separation. The object of the present invention is to provide a composite fuel emulsion characterized by comprising a water-in-oil or oil-in-water-in-oil emulsion prepared by blending a composite fuel emulsion with water. It is vaporized into a gaseous fuel by a high-temperature heating device. Compared with an equal volume of natural gas and gas, the gaseous fuel has a higher calorific value and is higher than 15 to 30%, and is indeed suitable as a fuel source for various burners. 12 201033351 « The object of the present invention is to provide a composite fuel emulsion for use in combination with water to prepare a water-in-oil or oil-in-water-in-oil composite fuel emulsion, wherein the emulsion is characterized by: Emulsifier: is at least one kind of non-ionic surfactant selected from Tween 20 ~ 80 series (p〇iyethoxylated sorbitan esters, polyoxyethylene sorbitan fatty acid ester), Span 20~85 series (sorbitan) Esters, sorbitol fatty acid vinegar, Triton 100~405 series (alkylphenol ethoxylates) and S0FTAN0L 50~120 series (Polyoxyethylene alkyl φ ether, polyoxyethylene fatty alcohol ether) The oil phase and the water phase are emulsified to form a water-in-oil or oil-in-water-in-water emulsion, wherein the emulsifier has an HLB value ranging from 4 to 8, and a preferred HLB value is 5. ~6 » (2) Combustion improver: one or more peroxides used to enhance the ignition and combustion properties of the emulsion. It is selected from at least one of the following compounds: hydrogen peroxide, peroxyformic acid, peroxygen Acid, iron dicyclopentadiene, toluene, xylene, t-butyl hydroperoxide, di-tert-butyl hydroperoxide, isopropyl hydroperoxide, acetone hydrogen peroxide, cyclohexanone peroxide, φ peroxidation Benzophenone, phenoxyhydrazine peroxide, ethyl butyl sulfoxide, alkyl nitrate, tributyl phthalate, dibutyl propyl peroxide, and homologues and derivatives Preferably, it is composed of hydrogen peroxide and xylene, and can dissolve impurities such as asphaltene or colloid in heavy oil or residual oil, and is more favorable for combustion. (3) Stabilizer: is at least one co-emulsifier to promote the formation of an interfacial film between the oil-water interface of the emulsion. It is characterized by comprising a hydroxyl group (-0H), a carbonyl group (-C0-), an amine group ( -NH2), at least one functional group capable of forming a hydrogen bond, such as a thiol (-C00H) and a radical (-C00-), for enhancing the strength of the oil-water interface film and improving the emulsification effect of the emulsifier; 13 201033351 The stabilizer is selected from the group consisting of at least one of the following: alcohols, polysaccharides, phenols, epoxides, polyoxides, amines, organic acids, sugars, and homologues and derivative compounds thereof, that is, Selected from methanol, ethanol, ethylene glycol, propylene glycol, glycerol, isovaerythritol, polyvinyl alcohol, indophenol, dimethyl hydrazine, butanol, second octyl phenol, polyethylene oxide, polyvinyl alcohol Furfural, polyacrylic acid, ethylenediamine, polyacrylamide, carboxymethylcellulose, animal glue, alginate, pectin, xanthan gum, and homologues and derivative compounds thereof, preferably yellow Made up of raw rubber. ® (4) Antioxidant: used to prevent the emulsion and the emulsion prepared by mixing the emulsion from deteriorating over a long period of time, and also to improve the polymerization of unsaturated hydrocarbons generated by heavy oil or diesel after combustion, resulting in coking Case; selected from at least one of the following compounds: 2,5-di-tert-butyl hydroquinone, tert-butyl hydroquinone, 2,6-di-tert-butyl-p-cresol, 2,6-di-tert-butyl Methylamino-p-cresol, tert-butylhydroxyanisole, propyl gallate, isooctyl 3,5-di-tert-butyl-4-hydroxyphenylpropionate, N,N-dimethyl-10- Dialkylamine, N,N-didecyloctadecylamine, tri-n-octylamine, N,N-diethylhydroxylamine, ® N,N-didecylcyclohexylamine, organophosphate, dioxane The thiodithiophosphate salt, as well as the homologues and derivative compounds thereof, are preferably composed of tert-butyl hydroquinone. (5) Antifoaming agent: used to destroy or inhibit the foaming of emulsion or emulsion and enhance the emulsification effect; it generally has better chemical stability and thermal stability, and lower surface tension to make the foam difficult to form, Good spreading factor is easy to defoam on the surface of the solution and fast defoaming, and low volatility; selected from at least one of the following compounds: dimethyl oxa oxane, dimethyl monoxide mixture added with cerium oxide , polyoxyalkylene, alkyl polyoxyalkylene, poly-modified polyoxyalkylene copolymer, alkylate salt, ethylene oxide and propylene oxide copolymer 14 201033351, and homologues thereof And a derivative compound or the like, preferably composed of polyoxyalkylene. (6) Antifreeze: used to prevent emulsion or emulsion solidification, selected from at least one of the following compounds: methanol, ethylene glycol, propylene glycol, glycerol, ethylene glycol, polyglutamic acid, urea, monomethyl The subordinates' and the homologues and derivative compounds thereof are preferably composed of ethylene glycol. (7) Fuel oil: is a carbonaceous fuel selected from at least one of 5 to 22, which comprises: gasoline, kerosene, diesel, wax oil, heavy oil or residual oil, oil slurry, petroleum solvent, animal oil, strontium Vegetable oil, biodegradable oil, mineral oil, waste oil, and the like, and a product obtained by mixing flammable powder particles (for example, carbon black) into the spark-containing fuel can be used as an oil phase component of the composite fuel emulsion of the present invention; The composition of these oils is as follows: Oil component carbon number 镏 temperature (°c) Use petroleum ether C5 ~ C6 20 ~ 60 Organic solvent gasoline C6 ~ C12 60 ~ 200 Automotive fuel, organic solvent kerosene C10 ~ C16 175 ~ 300 diesel engine, kerosene and jet fuel diesel C15~C20 250~400 diesel fuel wax C18~C22 >300 Lubricating oil In addition, heavy oil or residual oil is the residue remaining after crude oil is distilled under reduced pressure or atmospheric pressure, containing saturated hydrocarbons. , aromatic hydrocarbons, asphaltenes, colloids and sulfur nitrogen content, etc., the slurry contains 3〇%~5〇% of saturated hydrocarbons and colloids and more than 50% of aromatic hydrocarbons, etc., petroleum solvents include petroleum ether, pentylene, and hexa Geng, The oil is used to remove oil, solvent, and deodorization. The waste oil includes engine oil such as discarded engine oil, industrial oil such as discarded lubricating oil and cutting oil, and used cooking oil such as discarded edible oil. 15 201033351 In addition, the addition of potassium hydroxide and sodium hydroxide, in addition to adjusting the pH of the emulsion and combining with the acidic impurities in the fuel oil into a fine ash to reduce environmental pollution, can also make the oil of the emulsion The surface of the droplet particles is charged to promote sterical obstacles (stenicstabihization), thereby reducing the occurrence of flocculation and coalescence, and the emulsion droplets are thus less prone to breakage. In summary, the composite fuel emulsion of the present invention comprises an emulsifier, a combustion improver, a stabilizer, an antioxidant, an antifoaming agent, an antifreeze and a fuel oil, each of which comprises 1 to 5%, 1 to 5% of the emulsion, respectively. 1 to 3%, 1 to 2%, 1 to 3%, 1 to 3%, and 79 to 94% by volume; wherein the composition of the emulsion is organic, which can be completely burned in the combustion chamber to provide heat, and few Residual and residual, and solve technical obstacles that have been insurmountable for a long time. The object of the present invention is to provide a composite fuel emulsion characterized by comprising a water-in-oil or oil-in-water-in-oil emulsion prepared by blending the composite fuel emulsion with water, wherein the emulsion is characterized by: (1) The composite fuel emulsion comprises: an emulsifier, a combustion improver, a stabilizer, an antioxidant, an antifoaming agent, an antifreeze and a fuel oil, each of which comprises 1 to 5% of the emulsion, 丨~5%, 1~ 3%, 1 to 2%, 1 to 3%, 1 to 3%, and 79 to 94% by volume. (2) an aqueous phase component selected from the group consisting of at least one type of water comprising: a low-disc substance having trace elements, deionized water, pure water, and magnetized water, wherein the magnetized water is subjected to magnetization by a magnetic field; It is best to deionize water to avoid excessive mineral deposits in the water. The object of the present invention is to provide a method for preparing a composite fuel emulsion, which comprises mixing a stabilizer contained in the emulsion 201033351 with a water phase of 1 to 5% by volume for pre-emulsification, and then mixing with an additive composition. Into the emulsion, wherein the composite fuel emulsion comprises: emulsifier 1 to 5% by volume stabilizer 1 to 3% by volume combustion improver 1 to 5 % by volume antioxidant 1 to 2 % by volume antifreeze 1 to 3 % by volume Percent antifoaming agent 1 to 3% by volume fuel oil 79 to 94% by volume ❹ It is characterized in that the method comprises the following steps: (1) mixing the stabilizer of the emulsion with 1 to 5% by volume of the aqueous phase component ,
(2) 將包含水相成分之該穩定劑與一組合物混合以製備該乳劑，其中該 組合物係包含該乳化劑、該助燃劑、該抗氧化劑、該防凍劑、該消 泡劑及該燃料油所組成的一組物質。 本發明之目的係提供一種複合燃料乳液的製備方法，係包括將該乳劑 所包含之一穩定劑與1〜5%體積比的水相混合以進行預乳化，再與一添加 劑組合物混製成該乳劑，最後將該乳劑與10〜45%艎積百分比的水相成分 進行乳化而製備該乳液， 其中該複合燃料乳液係包含： 一複合燃料乳劑 55〜90 %體積百分比 一水相成分 10〜45 %體積百分比 17 201033351 其中該複合燃料乳劑包含： 乳化劑 1〜5 %艘積百分比 穩定劑 1〜3 %體積百分比 助燃劑 1〜5 %體積百分比 抗氧化劑 1〜2 %體積百分比 防凍劑 1〜3 %體積百分比 消泡劑 1〜3 %體積百分比 燃料油 79〜94 %體積百分比 ❹ 其中該水相成分，係選自至少一種之水，其包含：具有微量元素的低碟 物質之水、去離子水、純水及磁化水所組成的一組物質。 其特徵在於該方法包含下列步驟： (1) 利用一複合燃料乳劑的製備方法以製備一複合燃料乳劑’ (2) 將該乳劑與10〜45%體積百分比之水相成分混合， (3) 經一乳化裝置之乳化處理以製備該乳液》(2) mixing the stabilizer containing the aqueous phase component with the composition to prepare the emulsion, wherein the composition comprises the emulsifier, the combustion improver, the antioxidant, the antifreeze, the antifoaming agent, and the a group of substances consisting of fuel oil. The object of the present invention is to provide a method for preparing a composite fuel emulsion, which comprises mixing a stabilizer contained in the emulsion with a water phase of 1 to 5% by volume for pre-emulsification, and then mixing with an additive composition. The emulsion is finally prepared by emulsifying the emulsion with a water phase component of 10 to 45% by weight, wherein the composite fuel emulsion comprises: a composite fuel emulsion of 55 to 90% by volume of an aqueous phase component 10~ 45 % by volume 17 201033351 wherein the composite fuel emulsion comprises: emulsifier 1 to 5 % of the percentage of the stabilizer 1 to 3% by volume of the combustion improver 1 to 5 % by volume of the antioxidant 1 to 2 % by volume of the antifreeze 1 ~ 3% by volume of defoamer 1 to 3% by volume of fuel oil 79 to 94% by volume ❹ wherein the aqueous phase component is selected from at least one type of water, which comprises: water of a low-disc substance having trace elements, A group of substances consisting of ionized water, pure water, and magnetized water. The method comprises the following steps: (1) preparing a composite fuel emulsion by using a composite fuel emulsion preparation method; (2) mixing the emulsion with 10 to 45% by volume of the aqueous phase component, (3) Emulsification treatment of an emulsifying device to prepare the emulsion
其中該複合燃料乳劑的製備方法，係包含下列步驟： (1) 將該乳劑之該穩定劑與1〜5%體積百分比的水相成分混合， (2) 將包含水相成分之該穩定劑與一組合物混合以製備該乳劑，其中該 組合物係包含該乳化劑、該助燃劑、該抗氧化劑、該防凍劑、該消 泡劑及該燃料油所組成的一組物質。 總而言之，本發明之該複合燃料乳液包含該複合燃料乳劑及該水相成 分，在室溫環境下並無需另行加溫，並經一乳化裝置提供高速剪切處理， 其中該剪切處理之剪切速度為2000〜10000 RPM，較佳的剪切速度為6000 18 201033351 〜8000 RPM，以製備油包水或油包水包油型態的複合燃料乳液；其中該乳 液之油水液滴粒徑小於2碰者佔有70%以上，最佳地是液滴粒徑小於2咖 者佔95%以上；其中該水相成分可高達約45%體積百分比，明顯優於先前 技術之20〜30%體積百分比的水相成分，節油效果顯著，而解決長久以來 一直無法克服的技術障礙。 因此，本案實為一新穎、進步及實用之發明，相較於既有之乳化燃料 技術，本發明的優點分別為： © 1.複合燃料乳液之水相成分比例提高至40〜45%，並且無點火議題； 2. 複合燃料乳液具有高熱值，明顯高於等體積的傳統燃料油品達15〜 30%，經燃燒後幾無雜渣殘留，並可經一高溫加熱裝置汽化成一氣 態燃料，確實適於作為各種燃燒器之燃料來源； 3. 複合燃料乳劑及複合燃料乳液之製備過程並不需另經加熱裝置處 理，故其製備方法較為簡便’而解決長久以來一直無法克服的技術 障礙，明顯優異於既有技術需於高溫環境下進行處理； ® 4.複合燃料乳液為燃料供應之使用時，並不需另經加熱裝置處理，而 解決長久以來一直無法克服的技術障礙，明顯優異於既有技術需經 加熱處理及耗損額外之電力； 5·具有4個月以上之穩定性，並且乳化過程無需另行加溫，更利於長 時間儲備、長距離輸運及大規模製備》 故本發明已具備顯著的功效增進，並符合發明專利要件，爰依法提出申請。 201033351 【實施方式】 本發明為達耻述之目的而採狀技術手段，藉由實_具艘詳述於 下文’俾利於瞭解本發明之精髓。本發明所列舉之實施例僅具有說明之目 的，並不限制本發明之範圍。 膏施例1 由本實施例說明本發明複合燃料乳液所含之乳劑的製備方法，並於實 施例2中將該乳劑掺加一定量水量以製備得本發明複合燃料乳液，最後將 φ 該乳液藉由一高溫加熱裝置汽化成一氣態燃料，用以替代瓦斯或天然氣。 本實施例之製備方法分成三大步驟： 一 ·擬定乳劑製備流程步驟： (1) 規劃待配製之乳劑所需之原料種類及劑量，以製備總量為1〇〇〇 c. c. 之該乳劑， (2) 排定各原料注入至一乳化裝置之順序， (3) 攪拌混合各乳劑成分以製得該乳劑， φ 二·乳劑配製步驟： (1) 乳化劑：先決定待配製之複合燃料乳液的HLB值為7. 6，所採用之 非離子界面活性劑為Triton-100、Tween 20及Span 80，並且其 比例為1 : 2 : 7之體積百分比’該劑佔乳劑之體積百分比為3%。 (2) 助燃劑：環酮過氧化物等過氧化物及二甲苯，其所佔乳劑之體積 百分比各為3. 5%及3〜5%。 (3) 穩定劑：將黃原膠摻入2%水量以完成配製，其所佔乳劑之體積百 分比約為3%。 201033351 » ⑷燃料油.市售（台灣中油）之通祕劑及混合己烧，其所佔乳刺 之體積百分比各為58〜65%及1〇〜25%。 三.乳劑製作步驟： 首先將二甲苯、通用溶劑及混合己烧置入一乳化裝置，進行約3〜5分 鐘的攪拌，再將乳化劑、穩定劑、助燃劑、L 5%乙二醇、〇. 5%氫氧化鈉、 0. 5%抗氧化劑及0. 2%消泡劑注入至該乳化裝置，繼續攪拌約1〇〜15分 鐘，不需於攪拌過程另行加溫，而且攪拌速度為每分鐘9〇〜15〇轉（RPM)， © 即可製備得本發明複合燃料乳液所含之乳劑《 實施例2 將實施例1所製備之該乳劑摻加一定量水量以製備得本發明複合燃料 乳液，再將該乳液藉由一高溫加熱裝置汽化成一氣態燃料，最後將該氣態 燃料與一市售桶裝瓦斯分別進行燃燒以測定熱值，並比較兩者之熱值。 本發明之複合燃料乳液的製備方法，係將實施例丨所製得之1〇〇〇 c c. ® 乳劑注入至該乳化裝置内以預行剪切處理，其剪切速度設定為300〜 500RPM ’再將預先備妥之600 c. c_水量添入至該乳化裝置内，使水與該乳 劑進行乳化作用，待水量完成添加後，該乳化裝置之速度即由500RPM加速 至3000RPMM，再持續加速至6000RPM，待約為5〜10分鐘挽拌時間之後， 即可完成本發明複合燃料乳液之製備’其中該乳液所含之90%以上的液滴 分子之粒徑大小可達2um以下。 將已製得之該燃料乳液4800 c.c.經一高溫加熱裝置汽化成一氣態燃 料，並與一市售5公斤裝之桶裝瓦斯，進行熱值測定及比較。其步驟如下： 21 201033351 (1) 使用一容器裝入3公斤水量，並以經汽化之本發明複合燃料乳液與市售 一般桶裝瓦斯為燃料，再以快速爐為燃燒工具，分別對該容器及所盛裝 的水量進行加熱至約90°C，最後比較燒盡同艎積之該兩燃料所花费的時 間，以及測定其熱值。 (2) 將該燃料乳液4800 c.c.經一高溫加熱裝置汽化成一氣態燃料，並進行 燃燒，共費時380分鐘可燒盡》 (3) 燃燒市售一般5公斤桶裝瓦斯（筆因於大氣壓力而只有4公斤瓦斯可供 © 用；根據能源局資料，lKg瓦斯之體積為1. 786公升，即4Kg瓦斯之體 積為7· 144公升），共費時360分鐘可燒盡該桶裝瓦斯之瓦斯量。 (4) 以 PARR 1261 (Oxygen Bomb Calorimeter，氧彈式熱量計）測量本乳 液的熱值為8380仟卡/公升，而市售桶裝瓦斯所含之液化石油氣 (L. P. G.)實測熱值為6000〜6635仟卡/公升。 (5) 由實驗結果及熱值測定結果可知，相較於一般市售桶裝瓦斯，本發明之 複合燃料乳液擁有較高的熱值，明顯較適合作為燃料之用。 實施例3 本實施例所配製之乳劑，以及利用此乳劑與水摻合配製而得之複合燃 料乳液，係作為工業用鍋爐等燃燒裝置的燃料來源，其製備方法及步驟與 實施例1及實施例2相同，僅改變該乳劑及該乳液之組成為： 一.本發明複合燃料乳液所含之乳劑的製備·· (1) 乳化劑：其所佔乳劑之體積百分比為L 5〜5%。 (2) 助燃劑：環鲖過氧化物等過氧化物、二環戊二烯鐵及二甲苯其 22 201033351 所佔乳劑之體積百分比各為0.5〜1%、0· 1〜1%及1〜3%。 (3) 穩定劑：將黃原膠摻入1〜2%水量以完成配製，其所佔乳劑之體 積百分比約為1· 5〜3. 5%。並添加0. 5〜1%之氩氧化鈉。 (4) 燃料油：重油、市售之通用溶劑及混合己烷，其所佔乳劑之體積 百分比各為35〜50%、25〜35%及15〜20%。 (5) 抗氧化劑：其所佔乳劑之體積百分比為〇 3〜丨.5%。 經授拌即可製備得本發明複合燃料乳液所含之乳劑。 Θ 二.本發明複合燃料乳液的組成為： 該乳劑1000 c. c.摻加水量600 c. c.以製得1600 c c之該乳液。 三·將已製得之該燃料乳液與同體積之重油為燃料試樣，並採用一噸重之鑛 爐燃燒器進行燃料燃燒特性之測試，該鑛爐係使用於工業用殺菌設備， 其原使用之燃料油為重油。燃燒特性之測試結果發現該重油尚有 %殘留量而未能被燒盡’而該燃料乳液可被完全燒盡而無殘留。 四.以PARR 1261測定該燃料乳液的燃燒熱值為10200仟卡/公升，然而， ® 依據能源局資料，重油燃燒熱值僅為9200仟卡/公升。 實施例4 本實施例所配製之乳劑，以及利用此乳劑與水摻合配製而得之複合燃 料乳液’係作為工業用鍋爐或壓铸機等燃燒裝置的燃料來源，其製備方法 及步驟與實施例1及實施例2相同，僅改變該乳劑及該乳液之組成為： 一.本發明複合燃料乳液所含之乳劑的製備： (1)乳化劑：其所佔乳劑之體積百分比為1. 5〜5%。 23 201033351 » (2) 助燃劑：環酮過氧化物等過氧化物、二環戊二烯鐵及二甲苯，其 所佔乳劑之體積百分比各為〇.5〜1%、〇. 1〜1%及1〜3%。 (3) 穩定劑：將黃原膠摻入1〜2%水量以完成配製，其所佔乳劑之體 積百分比約為1. 5〜3. 5%。並添加〇. 5〜1%之氫氧化鈉。 (4) 燃料油：廢機車油、柴油、市售之通用溶劑及混合己烷，其所佔 乳劑之體積百分比各為35〜55%、5〜10%、10〜25%及10〜20 %。 ® (5)抗氧化劑1其所佔乳劑之體積百分比為0. 3〜1. 5%。 經攪拌即可製備得本發明複合燃料乳液所含之乳劑。 二·本發明複合燃料乳液的組成為： 該乳劑1000 c. c.摻加水量600 c· c.以製得1600 C. C.之該乳液。 三·將已製得之該燃料乳液與同體積之重油為燃料試樣，並採用日系廉牌為 Pilot Oil Burner之重油燃燒器進行燃料燃燒特性之測試，該燃燒器係 使用於壓鑄廠之燃燒設備’其原使用之燃料油為重油。燃燒特性之測試 ® 結果發現該重油尚有5〜10%殘留量而未能被燒盡，而該燃料乳液可被 完全燒盡而無殘留。 四.以PARR 1261測定該燃料乳液的燃燒熱值為9900仟卡/公升，然而，依 據能源局資料，重油燃燒熱值僅為9200仟卡/公升。 實施例5 本實施例所配製之乳劑’以及利用此乳劑與水接合配製而得之複合燃 料乳液’係作為工業用鐵罐標籤印製之乾燥機等燃燒裝置的燃料來源，該 24 201033351 » 機之原使用的燃料油為天然瓦斯。其製備方法及步騨與實施例i及實施例2 相同，僅改變該乳劑及該乳液之組成為： 一 ·本發明複合燃料乳液所含之乳劑的製備·· (1) 乳化劑：其所佔乳劑之殽積百分比為1〜3.5%。 (2) 助燃劑：環鲷過氧化物等過氧化物、二環戊二烯鐵及二甲笨其 所佔乳劑之體積百分比各為〇. 5〜3%、〇丨〜1%及3〜。 (3) 穩定劑：將黃原膠摻入丨〜2%水量以完成配製，其所佔乳劑之體 ® 積百分比約為1· 5〜3.5% »並添加0.5〜2%之氫氧化鈉。 (4) 燃料油：柴油、市售之通用溶劑及混合己烷，其所佔乳劑之體積 百分比各為5〜10%、40〜55%及10〜40%。 (5) 消泡劑：其所佔乳劑之體積百分比為丨〜3%。 經攪拌即可製備得本發明複合燃料乳液所含之乳劑。 二.本發明複合燃料乳液的組成為： 該乳劑1000 c. c.摻加水量600 c. c.以製得16〇〇 c· c.之該乳液。 © 三.以PARR 1261測定經汽化之該燃料乳液的燃燒熱值為8800仟卡/公升， 然而，依據能源局資料，重油燃燒熱值僅為53〇〇仟卡/公升。（按天然 氣熱值為8900仟卡/立方米，丨立方米容積約含有丨672公升的天然氣> 實施例6 本實施例所配製之乳劑，以及利用此乳劑與水摻合配製而得之複合燃 料乳液，係作為農業用穀物乾燥機等燃燒裝置的燃料來源，該機之原使用 的燃料油為柴油，習慣上柴油燃燒器為了易於點火燃燒，通常會添加1〇〜 25 201033351 15%之煤油。其製備方法及轉與實關i及實關2 _，僅改變該乳 劑及該乳液之組成為： 一. 本發明複合燃料乳液所含之乳劑的製備： (1) 乳化劑：其所佔乳劑之體積百分比為丨〜3% β (2) 助燃劑：環酮過氧化物等過氧化物、二環戊二烯鐵及二曱苯其 所佔乳劑之體積百分比各為1〜5%、1〜2%及i〜5%。 (3) 穩定劑：將黃原膠摻入丨〜2%水量以完成配製，其所佔乳劑之體 Θ 積百分比約為1.5〜3.5% ^並添加1〜2%之氩氧化鈉》 (4) 燃料油：柴油、市售之通用溶劑及混合己烷，其所佔乳劑之體積 百分比各為30〜50%、30〜45%及10〜20%。 (5) 消泡劑：其所佔乳劑之體積百分比為丨〜3%。 經授拌即可製備得本發明複合燃料乳液所含之乳劑。 二. 本發明複合燃料乳液的組成為： 該乳劑1000 c. c·摻加水量600 c. c.以製得1600 c. c.之該乳液。 Θ 三.以PARR 1261測定經汽化之該燃料乳液的燃燒熱值為96〇〇仟卡/公升， 然而，依據能源局資料，柴油燃燒熱值為8800什卡/公升，煤油燃燒熱 值為8500仔卡/公升。 實施例7 :燃料菊.液之鏃定栂通丨铋 從上述之實施例1、3、4、5及6之已製備的燃料乳液中，各取三管試 劑，每管試劑皆100 c_c.，即從每個實施例提取300 c.c·，並依據中華民 國專利TW189847號之製備方法以另行製備一比較例乳液，亦提取出三管各 26 201033351 100 C.c.試劑，將該六種乳液試樣分別進行靜置測試、溫度變化測試及動 態測試’並觀察各試樣之油水分離情形’若試樣發生油水分離則測定該試 樣底部的自由水含量，最後藉由油水分離情形及澄澈狀況來判定該些乳液 試樣的穩定性。 一.靜態（長時間4個月靜置）測試： 待該六種試樣製備完成後，各歷經4個月時間之靜置儲放，逐月觀察 該些乳液試樣的油水分離情形及澄澈狀況，來判定該些乳液試樣的長時間 ® 靜置之穩定性，觀察結果如表二所示： 表二 乳液 外觀 儲放時間（月數） 觀察結果 試樣 1 2 3 4 實施例1 清澈混濁乳白色 ◎ ◎ ◎ 〇 底部有較清澈乳白色 實施例3 混濁乳白色 ◎ ◎ ◎ ◎ 無分離現象 實施例4 混濁乳白色 ◎ ◎ ◎ ◎ 無分離現象 實施例5 清澈混濁乳白色 ◎ ◎ ◎ 〇 底部有較清激乳白多 實施例6 清激混濁乳白色 ◎ ◎ ◎ ◎ ...................。 無分離現象 比較例 清澈混濁乳白色 ◎ ◎ 〇 △ 已有油水分離現象， 沈澱物約有5%自由水 *言主：穩定性標準以下列符號代表： ◎:優良 〇：良好 △:略有影響 27 201033351 x:分離 二.溫度變化測試： 將該六種乳液試樣放置於一恆溫箱’該恆溫箱的溫度為可調控，溫度 調控範圍為-20°c〜10(TC，並按以下之溫度循環予以控制該六種試樣所處 之溫度環境：溫度70°C設定8小時、溫度30°C設定8小時及溫度5°c設定 8小時此三階段，逐週進行測試，並觀察該些乳液試樣的油水分離情形及澄 澈狀況，穩定性標準表示符號與表二相同，其觀察結果如表三所示： ❺ 表三 乳液 試樣 外觀 儲放時間（週數） 觀察結果 1 2 3 4 實施例1 清澈混濁乳白色 ◎ ◎ ◎ 〇 底部有較清澈乳白色 實施例3 混濁乳白色 ◎ ◎ ◎ ◎ 無分離現象 實施例4 混濁乳白色 ◎ ◎ ◎ ◎ —--- 無分離現象 實施例5 清澈混濁乳白色 ◎ ◎ ◎ 〇 底部有較清澈乳白痒 實施例6 清澈混濁乳白色 " ' ·— .—1111 _ ◎ ◎ ◎ ◎ 無分離現象 比較例 清澈混濁乳白色 -------- | -------— ◎ ◎ 〇 丨丨 〇 ------- 底部有較色 三.動態測試： 將該六種魏試樣各置人離錢之試管彻，織進行15分鐘離心操 作’離心速度S 3000RPM (約1050g ’其中g為重力加速度），接著測定該 些乳液試樣所釋Λ之自由水量’由該水量舰該魏賴翻奴性按 照釋出水量鮮者即表示錄發生較嚴重的破乳獅，因科致較為嚴重 的油水分離現象，反之，釋脉量較少職示敎性較高；抑卩穩定 28 疋 201033351 參 根據離心處理後，在各試管營底ά 吕展之自由水量，以及在管頂之燃料油層之乳 化量或乳化水層量所測定，其觀察結果如表四所示： 表四 乳液 乳化量 含水量 釋出水量 釋出水量 (C.C.) (C.C·) (C.C.) (%) 實施例1 100 40 7.8 19.5 實施例3 100 40 2.3 5.8 實施例4 100 40 2.4 6 實施例5 100 40 3.8 9.5 實施例6 100 40 6.3 15.8 比較例 100 40 23.6 59 四.穩定性實驗之結果： 從表一、表二及表三之結果可得知，相較於比較例，本發明之複合燃 料乳液於長期靜置測試、溫度變化測試及動態測試等三種測試條件下，均 有較佳穩定性，其中又以實施例3、4及5之乳液試樣為較佳。 29 201033351 * 由以上諸實施例之結果可知，本發明之複合燃料乳劑，以及該乳劑與 水摻合所製備之複合燃料乳液，與傳統燃料油源相比較，本發明確實為另 一較佳的能源供應來源，足以替代瓦斯、天然氣、重油及柴油等燃料，俾 將本發明之優點列示如下： 1.本發明之複合燃料乳液擁有高熱值。與同體積之傳統燃料油相比 較，本發明之熱值約高於傳統燃料油達15〜30%，故可為較高燃燒 效率之能源供應來源》 〇 2.本發明之複合燃料乳液可經一高溫加熱裝置汽化成一氣態燃料，而 增廣燃料乳液之用途。 3. 本發明之複合㈣乳賴可完全職喃雜_，雜改善燃燒 器嗔油嘴及燃燒室之殘渣或積碳等議題，有效延長燃燒器具的壽命。 4. 本發β月之複合燃料乳液擁有較佳的乳化穩定性，即該乳液不易發生 油水分離_ ’並可7壯其在室溫魏τ郷存長達4 個月以上而不發生破乳情形。 經上述實施例之說明後，將能更為清楚本發明之精錄，然而上述實施 例僅為本發—代各種倾_之触具財糊絲本發明的構 想所作的變更及其產生_，仍未超_贿_精神時，即任何 不脫離本個精神獨為之舞较變，觸在本發_範圍… 【圖式簡單說明】 【主要元件符號說明】 30The preparation method of the composite fuel emulsion comprises the following steps: (1) mixing the stabilizer of the emulsion with 1 to 5% by volume of the aqueous phase component, and (2) using the stabilizer containing the aqueous phase component; The composition is mixed to prepare the emulsion, wherein the composition comprises the emulsifier, the combustion improver, the antioxidant, the antifreeze, the antifoaming agent, and a group of materials comprising the fuel oil. In summary, the composite fuel emulsion of the present invention comprises the composite fuel emulsion and the aqueous phase component, and does not require additional heating at room temperature, and provides high-speed shear treatment through an emulsification device, wherein the shear treatment is sheared. The speed is 2000~10000 RPM, and the preferred shear rate is 6000 18 201033351 ~8000 RPM to prepare a water-in-oil or oil-in-water-in-water composite fuel emulsion; wherein the oil droplet size of the emulsion is less than 2 The contact person occupies more than 70%, preferably 95% or more of the droplet size is less than 2 café; wherein the aqueous phase component can be as high as about 45% by volume, which is obviously better than 20~30% by volume of the prior art. The water phase component has a significant fuel-saving effect and solves the technical obstacles that have been insurmountable for a long time. Therefore, the present invention is a novel, progressive and practical invention. Compared with the existing emulsion fuel technology, the advantages of the present invention are as follows: © 1. The proportion of the aqueous phase component of the composite fuel emulsion is increased to 40 to 45%, and No ignition problem; 2. The composite fuel emulsion has a high calorific value, which is significantly higher than the equivalent volume of conventional fuel oil by 15 to 30%. After burning, there is no residual residue, and it can be vaporized into a gaseous fuel through a high temperature heating device. It is indeed suitable as a fuel source for various burners. 3. The preparation process of composite fuel emulsion and composite fuel emulsion does not need to be treated by a heating device, so the preparation method is relatively simple, and the technical obstacles that have been insurmountable for a long time are solved. Significantly superior to existing technologies that need to be treated in high temperature environments; ® 4. When used as a fuel supply, the composite fuel emulsion does not need to be treated by a heating device, but solves the technical obstacles that have been insurmountable for a long time. Existing technology needs to be heated and consumes extra power; 5· Has stability for more than 4 months, and the emulsification process does not need to be added separately , More conducive to long-time reserves, long-distance transport and large-scale preparation "Therefore, this invention has already significantly enhance the effectiveness of, and compliance with requirements of invention patents, Yuan apply the law. 201033351 [Embodiment] The present invention is a technical means for achieving the purpose of succinctness, and is described in detail below to understand the essence of the present invention. The examples of the invention are intended to be illustrative only and not limiting the scope of the invention. Paste Example 1 This embodiment illustrates the preparation method of the emulsion contained in the composite fuel emulsion of the present invention, and in Example 2, the emulsion is added with a certain amount of water to prepare the composite fuel emulsion of the present invention, and finally the emulsion of φ is borrowed. It is vaporized into a gaseous fuel by a high temperature heating device to replace gas or natural gas. The preparation method of the present embodiment is divided into three major steps: 1. The preparation process of the preparation of the emulsion: (1) planning the type and dosage of the raw materials required for the emulsion to be prepared, to prepare the emulsion in a total amount of 1 cc, ( 2) Arranging the order of injecting each raw material into an emulsifying device, (3) stirring and mixing the respective emulsion components to prepare the emulsion, and preparing the φ2·emulsion: (1) emulsifier: first determining the composite fuel emulsion to be prepared The HLB value was 7.6. The nonionic surfactants used were Triton-100, Tween 20, and Span 80, and the ratio thereof was 1:2:7 by volume percent. The agent accounted for 3% by volume of the emulsion. (2) 5% and 3 to 5% by weight of each of the emulsions of the ketone peroxide. (3) Stabilizer: The xanthan gum is blended into 2% water to complete the formulation, and the emulsion accounts for about 3% by volume. 201033351 » (4) Fuel oil. The commercially available (Taiwan Zhongyou) secret agent and mixed burned, the volume percentage of the nipple is 58~65% and 1〇~25%. 3. Emulsion preparation steps: First, put xylene, general-purpose solvent and mixed hexane into an emulsifying device, stir for about 3 to 5 minutes, and then emulsifier, stabilizer, combustion improver, L 5% ethylene glycol, 5%. 5% sodium hydroxide, 0.5% anti-oxidant and 0.2% antifoaming agent are injected into the emulsifying device, stirring is continued for about 1 〇 to 15 minutes, without additional heating during the stirring process, and the stirring speed is The emulsion contained in the composite fuel emulsion of the present invention can be prepared by using 9 〇 15 15 rpm (RPM) per minute. [Example 2 The emulsion prepared in Example 1 was spiked with a certain amount of water to prepare a composite of the present invention. The fuel emulsion is then vaporized into a gaseous fuel by a high temperature heating device, and finally the gaseous fuel is separately combusted with a commercially available barrel of gas to determine the calorific value, and the calorific value of the two is compared. The preparation method of the composite fuel emulsion of the present invention is that the 1〇〇〇c c. ® emulsion prepared in the embodiment is injected into the emulsifying device for pre-shearing, and the shearing speed is set to 300 to 500 RPM. 'Add the prepared 600 c. c_ water volume to the emulsifying device to emulsify the water and the emulsion. After the water volume is added, the speed of the emulsifying device is accelerated from 500 RPM to 3000 RPMM. Accelerating to 6000 RPM, after about 5 to 10 minutes of mixing time, the preparation of the composite fuel emulsion of the present invention can be completed, wherein more than 90% of the droplet molecules contained in the emulsion have a particle size of 2 um or less. The fuel emulsion 4800 c.c. which has been prepared is vaporized into a gaseous fuel by a high-temperature heating device, and calcined and compared with a commercially available 5 kg drum of gas. The steps are as follows: 21 201033351 (1) Using a container to charge 3 kg of water, and using the vaporized composite fuel emulsion of the present invention and commercially available general drum gas as fuel, and then using the rapid furnace as a combustion tool, respectively, the container The amount of water contained therein is heated to about 90 ° C, and finally the time taken to burn off the two fuels is compared, and the calorific value is measured. (2) The fuel emulsion 4800 cc is vaporized into a gaseous fuel through a high-temperature heating device and burned, which takes a total of 380 minutes to burn out. (3) Burning a commercially available 5 kg barrel of gas (the pen is due to atmospheric pressure) Only 4 kilograms of gas is available for use. According to the Energy Bureau, the volume of lKg gas is 1.786 liters, or 4 kilograms of gas is 7 144 liters. It takes 360 minutes to burn the gas of the barrel. . (4) The thermal value of the emulsion measured by PERR 1261 (Oxygen Bomb Calorimeter) is 8380 仟 / liter, while the measured liquefied petroleum gas (LPG) contained in commercially available barreled gas is 6000. ~6635 Leica / liter. (5) From the experimental results and the calorific value measurement results, the composite fuel emulsion of the present invention has a higher calorific value than that of a commercially available barreled gas, and is obviously suitable for use as a fuel. Example 3 The emulsion prepared in the present embodiment and the composite fuel emulsion prepared by blending the emulsion with water are used as a fuel source for a combustion device such as an industrial boiler, and the preparation method and steps thereof are the same as in the first embodiment and the implementation. In the same manner as in Example 2, only the emulsion and the composition of the emulsion were changed: 1. Preparation of the emulsion contained in the composite fuel emulsion of the present invention (1) Emulsifier: The volume percentage of the emulsion was L 5 to 5%. (2) Combustion agent: peroxide such as cyclic guanidine peroxide, dicyclopentadienyl iron and xylene. 22 201033351 The volume percentage of the emulsion is 0.5~1%, 0·1~1% and 1~ 3%. 5%。 The percentage of the volume of the emulsion is about 1. 5~3. 5%. And adding 0. 5~1% of argon oxide. (4) Fuel oil: heavy oil, a commercially available general-purpose solvent, and mixed hexane, which account for 35 to 50%, 25 to 35%, and 15 to 20% by volume each. (5) Antioxidant: The volume percentage of the emulsion is 〇 3 to 丨.5%. The emulsion contained in the composite fuel emulsion of the present invention can be prepared by mixing. Θ 2. The composition of the composite fuel emulsion of the present invention is: The emulsion 1000 c. c. The water content is 600 c. c. to obtain 1600 c c of the emulsion. 3. The fuel emulsion and the same volume of heavy oil are used as fuel samples, and a one ton heavy mine burner is used for fuel combustion characteristics. The furnace is used in industrial sterilization equipment. The fuel oil used is heavy oil. The test results of the combustion characteristics revealed that the heavy oil still had a % residual amount and could not be burned out, and the fuel emulsion could be completely burned without residue. The combustion heat value of the fuel emulsion measured by PARR 1261 is 10,200 仟 / liter, however, according to the Energy Bureau, the calorific value of heavy oil combustion is only 9,200 仟 / liter. Embodiment 4 The emulsion prepared in the present embodiment and the composite fuel emulsion prepared by blending the emulsion with water are used as a fuel source for a combustion device such as an industrial boiler or a die casting machine, and the preparation method, steps and implementation thereof 5%。 The emulsifier: the volume percentage of the emulsion is 1. 5 ~5%. 23 201033351 » (2) Combustion agent: peroxide such as cyclic ketone peroxide, dicyclopentadienyl iron and xylene, the volume percentage of the emulsion is 〇.5~1%, 〇. 1~1 % and 1 to 3%. 5〜3. 5%。 The percentage of the volume of the emulsion is about 1. 5~3. 5%. And add 〇. 5~1% sodium hydroxide. (4) Fuel oil: waste locomotive oil, diesel oil, commercially available general-purpose solvent and mixed hexane, the volume percentage of the emulsion is 35~55%, 5~10%, 10~25% and 10~20% . 5%。 5%. 5%. The emulsion contained in the composite fuel emulsion of the present invention can be prepared by stirring. 2. The composition of the composite fuel emulsion of the present invention is: The emulsion 1000 c. c. The water content is 600 c·c. to prepare the emulsion of 1600 C. C. 3. The fuel emulsion and the same volume of heavy oil are used as fuel samples, and the fuel burning characteristics of the Pilot Oil Burner are tested by the Japanese brand. The burner is used in the combustion of the die casting factory. The equipment 'the fuel oil originally used is heavy oil. Test of Combustion Characteristics ® It was found that the heavy oil still had 5 to 10% residual amount and could not be burned out, and the fuel emulsion could be completely burned without residue. The combustion heat value of the fuel emulsion measured by PARR 1261 is 9900 仟 / liter. However, according to the Energy Bureau, the calorific value of heavy oil combustion is only 9,200 仟 / liter. Example 5 The emulsion prepared in the present embodiment and the composite fuel emulsion prepared by using the emulsion and water to be joined are used as a fuel source for a combustion device such as a dryer for industrial iron can label printing, the same as 24, 201033351 The fuel oil used in the original is natural gas. The preparation method and the steps are the same as those in the examples i and 2, and only the emulsion and the composition of the emulsion are changed: 1. Preparation of the emulsion contained in the composite fuel emulsion of the invention (1) Emulsifier: The percentage of the obscured product of the emulsion is 1 to 3.5%. (2) Combustion-supporting agent: Peroxides such as cyclic guanidine peroxide, dicyclopentadienyl iron and dimethyl phenanthrene are each 5%. 5~3%, 〇丨~1% and 3~ . (3) Stabilizer: The xanthan gum is mixed into 丨~2% water to complete the preparation. The percentage of the body of the emulsion is about 1.5~3.5%» and 0.5~2% sodium hydroxide is added. (4) Fuel oil: Diesel, a commercially available general-purpose solvent and mixed hexane, which account for 5 to 10%, 40 to 55%, and 10 to 40% by volume of the emulsion. (5) Defoamer: The volume percentage of the emulsion is 丨~3%. The emulsion contained in the composite fuel emulsion of the present invention can be prepared by stirring. 2. The composition of the composite fuel emulsion of the present invention is: the emulsion 1000 c. c. The amount of water added is 600 c. c. to prepare the emulsion of 16 〇〇 c·c. © III. The combustion calorific value of the fuel emulsion vaporized by PARR 1261 is 8800 仟 / liter. However, according to the Energy Bureau, the calorific value of heavy oil combustion is only 53 〇〇仟 / liter. (According to the calorific value of natural gas is 8,900 仟 / cubic meter, the volume of 丨 cubic meters contains about 672 liters of natural gas > Example 6 The emulsion prepared in this example, and the compound obtained by blending the emulsion with water The fuel emulsion is used as a fuel source for a combustion device such as an agricultural grain dryer. The original fuel oil used in the machine is diesel. It is customary for a diesel burner to add 1〇~ 25 201033351 15% kerosene for easy ignition and combustion. The preparation method and the transfer method and the actual control 2 _, only change the composition of the emulsion and the emulsion are: 1. Preparation of the emulsion contained in the composite fuel emulsion of the invention: (1) Emulsifier: its occupation The volume percentage of the emulsion is 丨~3% β (2) Combustion agent: peroxide, cyclopentadienyl peroxide and the like, and the volume percentage of the emulsion is 1 to 5%. 1~2% and i~5%. (3) Stabilizer: The xanthan gum is mixed into 丨~2% water to complete the preparation. The percentage of the emulsion in the emulsion is about 1.5~3.5% ^ and 1 is added. ~2% of argon oxide" (4) Fuel oil: diesel, commercially available general-purpose solvent and The hexane is mixed, and the volume percentage of the emulsion is 30 to 50%, 30 to 45%, and 10 to 20%, respectively. (5) Antifoaming agent: The volume percentage of the emulsion is 丨~3%. The emulsion contained in the composite fuel emulsion of the present invention can be prepared by mixing. The composition of the composite fuel emulsion of the present invention is as follows: The emulsion 1000 c. c. The water content is 600 cc to prepare 1600 cc of the emulsion. The combustion heat value of the vaporized fuel emulsion measured by PARR 1261 is 96 〇〇仟 / liter. However, according to the Energy Bureau data, the combustion heat value of diesel is 8800 Shika / liter, and the combustion value of kerosene is 8500 baht / Example 7: Fuel Co., Ltd., a solution of the above prepared fuel emulsions of Examples 1, 3, 4, 5 and 6 C_c., that is, 300 cc· was extracted from each of the examples, and a comparative emulsion was separately prepared according to the preparation method of the Republic of China Patent No. TW189847, and three tubes of 26 201033351 100 Cc reagents were also extracted, and the six emulsions were tested. Sample static test, temperature change test and dynamic test Check the oil-water separation of each sample. 'If the sample is separated by oil-water separation, determine the free water content at the bottom of the sample. Finally, determine the stability of the emulsion samples by the separation of oil and water and the clear condition. Tested for 4 months for a long time) Test: After the preparation of the six samples, each of them was allowed to stand for 4 months, and the oil-water separation and clearness of the emulsion samples were observed month by month to determine The stability of the long-term rest of the emulsion samples was as shown in Table 2: Table 2 Appearance of the emulsion appearance (months) Observation Results Sample 1 2 3 4 Example 1 Clear turbid milky white ◎ ◎ ◎ The bottom of the crucible has a clear milky white color. Example 3 Turbid milky white ◎ ◎ ◎ ◎ No separation phenomenon Example 4 Turbid milky white ◎ ◎ ◎ ◎ No separation phenomenon Example 5 Clear turbid milky white ◎ ◎ ◎ 6 clear turbid milky white ◎ ◎ ◎ ◎ ................... No separation phenomenon Comparative example clear turbid milky white ◎ ◎ 〇 △ There is oil and water separation phenomenon, the sediment is about 5% free water * Word: Stability standard is represented by the following symbols: ◎: Excellent 〇: Good △: slightly affected 27 201033351 x:Separation 2. Temperature change test: The six emulsion samples are placed in an incubator. The temperature of the incubator is adjustable, and the temperature control range is -20 °c~10 (TC, and the temperature below) Cycle to control the temperature environment of the six samples: temperature 70 ° C set 8 hours, temperature 30 ° C set 8 hours and temperature 5 ° c set 8 hours these three stages, test weekly, and observe these The oil-water separation and clearness of the emulsion sample, the stability standard is shown in the same symbol as in Table 2. The observation results are shown in Table 3: ❺ Table 3 Appearance time of the emulsion sample (weeks) Observations 1 2 3 4 Example 1 Clear turbid milky white ◎ ◎ ◎ The bottom of the crucible has a clear milky white Example 3 Turbid milky white ◎ ◎ ◎ ◎ No separation phenomenon Example 4 Turbid milky white ◎ ◎ ◎ ◎ —--- No separation Example 5: Clear turbid milky white ◎ ◎ ◎ 〇 有 有 有 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 无 无 无-- | -------- ◎ ◎ 〇丨丨〇------- The bottom has a color three. Dynamic test: The six kinds of Wei samples are placed in the test tube of the money, weaving Perform a 15 minute centrifugation operation 'centrifugation speed S 3000RPM (about 1050g 'where g is the gravitational acceleration), and then determine the amount of free water released by the emulsion sample' by the water volume of the Wei Lai ruin according to the release of water That is to say, the severely broken lions are recorded, because of the serious oil-water separation phenomenon caused by the science, on the contrary, the release of the pulse is less, the stagnation is higher; the stagnation is stable, 28 疋 201033351 参 according to the centrifugal treatment, in each test tube The bottom of the camp, the amount of free water of Lu Zhan, and the amount of emulsified or emulsified water layer in the fuel oil layer at the top of the pipe, the results are shown in Table 4: Table 4 Emulsion emulsification water content released water volume (CC) (CC·) (CC) (%) Implementation Example 1 100 40 7.8 19.5 Example 3 100 40 2.3 5.8 Example 4 100 40 2.4 6 Example 5 100 40 3.8 9.5 Example 6 100 40 6.3 15.8 Comparative Example 100 40 23.6 59 IV. Results of the stability test: From the table 1. The results of Table 2 and Table 3 show that the composite fuel emulsion of the present invention has better stability under the three test conditions of long-term static test, temperature change test and dynamic test, compared with the comparative example. Among them, the emulsion samples of Examples 3, 4 and 5 are preferred. 29 201033351 * From the results of the above examples, the composite fuel emulsion of the present invention, and the composite fuel emulsion prepared by blending the emulsion with water, the present invention is indeed another preferred one compared with the conventional fuel oil source. The source of energy supply is sufficient to replace fuels such as gas, natural gas, heavy oil and diesel, and the advantages of the present invention are as follows: 1. The composite fuel emulsion of the present invention has a high calorific value. Compared with the traditional fuel oil of the same volume, the calorific value of the present invention is about 15~30% higher than that of the conventional fuel oil, so it can be a source of energy supply with higher combustion efficiency. 〇2. The composite fuel emulsion of the present invention can be A high temperature heating device vaporizes into a gaseous fuel to augment the use of the fuel emulsion. 3. The composite (4) of the present invention can completely eliminate the problem of residues or carbon deposits in the burner nozzle and the combustion chamber, thereby effectively prolonging the life of the burning appliance. 4. The compound fuel emulsion of the present invention has better emulsion stability, that is, the emulsion is not easy to separate from oil and water _ ' and can be strong at room temperature for up to 4 months without breaking the emulsion situation. The description of the above embodiments will further clarify the refinement of the present invention, however, the above-described embodiments are only for the purpose of the present invention, and the changes made to the concept of the present invention. Still not super _ bribe _ spirit, that is, any dance that does not deviate from this spirit is changed, touched in the scope of this hair _ range... [Simple diagram description] [Key symbol description] 30