TWI284635B - A method of producing ethyl acetate and an equipment for carrying out this method - Google Patents
A method of producing ethyl acetate and an equipment for carrying out this method Download PDFInfo
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- TWI284635B TWI284635B TW089123165A TW89123165A TWI284635B TW I284635 B TWI284635 B TW I284635B TW 089123165 A TW089123165 A TW 089123165A TW 89123165 A TW89123165 A TW 89123165A TW I284635 B TWI284635 B TW I284635B
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- ethyl acetate
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- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 title claims abstract description 186
- 238000000034 method Methods 0.000 title claims abstract description 31
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 206
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 117
- 238000006243 chemical reaction Methods 0.000 claims abstract description 78
- WFDIJRYMOXRFFG-UHFFFAOYSA-N acetic acid anhydride Natural products CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims abstract description 66
- 239000000203 mixture Substances 0.000 claims abstract description 55
- 238000000926 separation method Methods 0.000 claims abstract description 55
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 51
- 239000003054 catalyst Substances 0.000 claims abstract description 18
- 238000010992 reflux Methods 0.000 claims abstract description 18
- 230000002378 acidificating effect Effects 0.000 claims abstract description 9
- 239000007787 solid Substances 0.000 claims abstract description 4
- 238000004821 distillation Methods 0.000 claims description 50
- 239000005416 organic matter Substances 0.000 claims description 37
- 238000009835 boiling Methods 0.000 claims description 30
- 239000002253 acid Substances 0.000 claims description 18
- 239000000376 reactant Substances 0.000 claims description 15
- 238000010025 steaming Methods 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 10
- 239000000945 filler Substances 0.000 claims description 7
- 239000006227 byproduct Substances 0.000 claims description 6
- 150000008064 anhydrides Chemical class 0.000 claims description 5
- 150000002148 esters Chemical class 0.000 claims description 4
- 239000011973 solid acid Substances 0.000 claims description 3
- 239000000470 constituent Substances 0.000 claims description 2
- 239000012071 phase Substances 0.000 claims description 2
- 239000011949 solid catalyst Substances 0.000 claims description 2
- 239000007791 liquid phase Substances 0.000 claims 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 238000005345 coagulation Methods 0.000 claims 1
- 230000015271 coagulation Effects 0.000 claims 1
- 239000012074 organic phase Substances 0.000 abstract description 4
- 235000019441 ethanol Nutrition 0.000 abstract 3
- 239000000047 product Substances 0.000 description 12
- 230000002194 synthesizing effect Effects 0.000 description 11
- 150000008065 acid anhydrides Chemical class 0.000 description 6
- 125000004494 ethyl ester group Chemical group 0.000 description 6
- 238000011049 filling Methods 0.000 description 5
- 238000005342 ion exchange Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 3
- 238000005886 esterification reaction Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 150000007522 mineralic acids Chemical class 0.000 description 3
- 238000001308 synthesis method Methods 0.000 description 3
- CHRJZRDFSQHIFI-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;styrene Chemical compound C=CC1=CC=CC=C1.C=CC1=CC=CC=C1C=C CHRJZRDFSQHIFI-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000002815 homogeneous catalyst Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- UGAPHEBNTGUMBB-UHFFFAOYSA-N acetic acid;ethyl acetate Chemical compound CC(O)=O.CCOC(C)=O UGAPHEBNTGUMBB-UHFFFAOYSA-N 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- OCLXJTCGWSSVOE-UHFFFAOYSA-N ethanol etoh Chemical compound CCO.CCO OCLXJTCGWSSVOE-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 235000015096 spirit Nutrition 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
- B01J8/0242—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid flow within the bed being predominantly vertical
- B01J8/025—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid flow within the bed being predominantly vertical in a cylindrical shaped bed
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/009—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping in combination with chemical reactions
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
- B01J2208/00008—Controlling the process
- B01J2208/00017—Controlling the temperature
- B01J2208/00106—Controlling the temperature by indirect heat exchange
- B01J2208/00265—Part of all of the reactants being heated or cooled outside the reactor while recycling
- B01J2208/00274—Part of all of the reactants being heated or cooled outside the reactor while recycling involving reactant vapours
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
- B01J2208/00008—Controlling the process
- B01J2208/00017—Controlling the temperature
- B01J2208/00106—Controlling the temperature by indirect heat exchange
- B01J2208/00265—Part of all of the reactants being heated or cooled outside the reactor while recycling
- B01J2208/00283—Part of all of the reactants being heated or cooled outside the reactor while recycling involving reactant liquids
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
- B01J2208/00008—Controlling the process
- B01J2208/00017—Controlling the temperature
- B01J2208/00513—Controlling the temperature using inert heat absorbing solids in the bed
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Fluid Mechanics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Vaporization, Distillation, Condensation, Sublimation, And Cold Traps (AREA)
Description
1284635 案號 89123165 年 修正 在、發明說明（1) 本發明 醇與乙酸或 的組成物在 方法的特徵 並經由不斷 繼續反應， 的將起始反 的計量稍不 乙酯可由與 發明背景： 按，習 乙醇製備， 乙醇與酸酐 乙酸，而乙 由於酉旨 而加速反應 為’特別係 性觸媒主要 質等。 根據先 平衡反應的 物的比率而 混合物形成 、乙酸乙酯 係關 乙醇 酸性 係在 的回 以付 應物 足時 水的 於一 與酸 催化 於將 流部 到高 轉化 ，乙 混合 知製備乙 反應生成 製備，此 酸會被另 化反應係 ，而為了 硫酸或進 係進行酸 種的合成 酐或乙醇 劑存在下 蒸餾塔中 份有機物 平衡狀態 成乙酸乙 醇可被完 物中輕易 酸乙酯的 的產物為 方法所生 一部份的 一平衡反 加速反應 一步使用 離子的交 前的技術，S旨化反 而該生成 混合物經 部份共沸 於在此共 混合物， 定，生成 異質的三 及水，由 方法及裝置，主要係經由乙 與乙酸及酸酐的混合物組成 同時進行蒸餾分離反應；此 的反應系統分成三個區間’ 至蒸餾系統中與新的反應物 的反應，並可幾近百分之百 酯與水，特別是當乙醇提供 全轉換成乙酸乙酯，且乙酸 的分離出。 方法有二種，一是由乙酸與 乙酸乙酯與水；另一則是由 成的產物除乙酸乙酯外還有 乙醇進一步酯化。 應所以會因酸性觸媒的存在 的目的，最常使用無機酸做 固體的酸性觸媒；固體的酸 換，如泡沸石或固體過酸物 應通常在反應器中得到極盡 混合物的組成須視起始反應 由蒸餾塔精餾出，精餾出的 點混合物，此三部份為乙醇 沸點混合物中水占絕大部份
第9頁 1284635 y
’所以多餘的水會被經由蒸餾塔的鍋爐與未反應的乙酸_ 起取出，而取出後的未反應乙酸須再經由另一蒸餘塔 接續’蒸德分離共彿點混合物中有機相的步驟為. 先由乙酸乙酯中分離未反應的乙酸，此部驟係非常銀辛 不易達成的’因實際上這是一非理想的混合狀態，包含_ 成份組成的共沸點混合物，其中一部份的乙醇與乙酸^ = 共彿點的混合物，而另一部份的乙醇與乙酸則與水形成另 一共 >弗點較低的共沸點混合物。水在第一個蒸德塔中被八 離出，而不溶的乙酸乙酯與乙醇則係由另一蒸餾塔蒸館^ 醇與酸的混合物會被並回流至蒸餾的過程中。如上^述， 可知在酯化反應中必須使用複雜的分離方法來分離混合組 成的生成物，係主要的缺點所在，且在反應時若使用無機 酸作為觸媒時，雖能提供一較好的反應機制，但卻明暴員存 在著腐蝕性的問題。 然而，原則上，使用乙酸與乙醇進行酯化反應係可不 使用觸媒（chem.Eng.Technol.l 9 97,20，182)或提供均質 的觸媒【如·無機酸與其中之一的反應物一起（Chemia、
Stosowana 1989，33，5〇9)】；亦可使用一整組的蒸館塔 ’並在蒸顧塔中填充酸離子交換粒子，此酸離子交換粒子 除了作為觸媒外亦作為塔填充物（Separati〇n Science and Technology 1992,27, 6 1 3 )。但是反應t若不使用觸 媒’將使整個醋化反應的結果因反應速率太慢而不適合產 業利用；而如果提供均質的催化劑將引起前面所述之腐蝕
第10頁 1284635 _案號 89123165_± 真、發明說明（3) 月 曰 修正 問題及不利的反應環境，因在蒸餾塔中充填自由的酸性催 化劑粒子，將使蒸餾塔具高的流體動力阻力及差的分離效 率，所以在蒸餾塔中充填自由的酸性催化劑粒子，在工業 生產過程亦是不可行的。
因此，如何針對上述乙酸乙醋合成方法的缺點提出一 種新穎之解決方法，使不僅可排除使用酸性催化劑所產生 的腐蝕問題，及解決在蒸餾塔中充填自由的酸性催化劑粒 子，而使蒸餾塔具高的流體動力阻力及差的分離效率的缺 點，長久以來一直是相關產業界殷切盼望及本發明人欲行 解決之困難點所在，而本發明人基於多年從事於相關技術 之研究、開發，乃思及改良之意念，窮其個人之專業知識 ，經多方測試、探討，並經無數次實驗及改良後，終於研 究出一種乙酸乙酯的合成方法及裝置，以解決上述之問題 。爰是， 本發明之主要目的，在於提供一乙酸乙酯的合成方法 及裝置，藉由此方法合成乙酸乙酯，可得到高平衡狀態的 反應，並可幾近百分之百的將起始反應物轉化成乙酸乙酯 與水。 本發明之次要目的，在於提供一乙酸乙i旨的合成方法 及裝置，藉由此方法合成乙酸乙酯，藉由此方法合成乙酸 乙酯，特別是當乙醇提供的計量稍不足時，乙醇可被完全 _ 轉換成乙酸乙酯，且乙酸乙酯可由與水的混合物中輕易的 分離出。 本發明之又一目的，在於提供一乙酸乙酯的合成方法
第11頁 1284635 案號 89123165 曰 修正 五、發明說明（4) 及裝置，藉由此裝置可將 本發明之再一目的， 及裝置，藉由此裝置，可 部份循環的連續回流機制 茲為使 貴審查委員 成之功效有更進一步瞭解 單裝置圖及較佳實施例並 發明詳細說明： 本發明係關於一種乙 係經由乙醇與乙酸或乙醇 乙醇，在酸性催化劑存在 成物，乙酸或酸酐或兩者 在2 :1至1 :2.5間及起始 媒體積）。此裝置系統中 ，反應區將同時蒸餾分離 成物因有不同的沸點所以 行蒸餾分離反應生成組成 物，蒸餾分離後與乙酸乙 全或部分自系統中蒸餾出 凝成蒸餾液（由70 °C至5 °C 蒸餾液中的其它有機組成 中包含大部份未純化的乙 成回流至蒸餾系統中，此 兩者的混合物與乙醇進料 生成物依共沸點高低作分離。 在於提供一乙酸乙酯的合成方法 將共沸點較低組成中的有機物作 ，以得到高純度之乙酸乙酯。 對本發明方法之特徵及裝置所達 與認識，謹佐以本發明方法之簡 配合詳細之說明，說明如後： 酸乙酯的合成方法及 與酸酐或酸酐及乙酸 下同時進行蒸餾分離 的混合物與乙醇係採 物的總流率為0 . 1至1 ，將反應的蒸餾塔分 反應生成組成物，而 被分離成兩區’此狀 物才發生。水在此反 酯形成低共沸點混合 ，之後此蒸餾出的蒸 )且水被從乙酸乙酯 則被由系統中取出， 酸乙酯且將其中一部 時同時再提供新的乙 至蒸館系統中與回流 裝置，主要 的混合物與 反應生成組| 用莫耳比率 0hw (單位觸 成三個區域 反應生成組 況只有當進 應中為副產 物，且被完 餾蒸汽被冷 分離出，而 此有機組成 份此有機組 酸或酸酐或 的有機組成
第12頁 1284635 ^_案號89123165_年月 曰 修正_ 五、發明說明（5) 反應，新提供的進料與回流的有機組成間的比率為1 : 1至 1 : 2 0，新進料中的乙酸或酸酐或兩者的混合物係由反應區 的上方適當處注入蒸餾系統中，而乙醇則由反應區的下方 適當處注入蒸餾系統中，剩餘未反應的乙酸包含部份的水 . 在蒸餾分離後形成高共沸點混合物。以酸離子交換物質作 為觸媒，如：硫化苯乙烯-二乙烯基苯的共聚物，含1 %至 · 25%的重量乙烯基苯與1〜10meq(H + )/ g的酸。 一較妤且具體的方法是以下列的特性操作：乙酸與乙 醇的莫耳比率為1 :1至1 :0.45或酸酐與乙醇的莫耳比率為 1 : 2至1 : 1. 5，起始反應物的進料流率為0· 5至51Γ1 (單位 觸媒體積）；新提供的進料與回流的有機組成間的比率為 ® 1 : 1至1 : 2 0 ;以乙酸或酸酐與乙醇的混合物取代只單純使 用乙酸或酸酐或兩者的混合物作為進料，如此進料組成中 包含乙酸外尚包括乙酸乙酯與水或水、與未反應的乙醇或 未反應的乙醇。 本發明方法的達成必須使用一裝置，此裝置中包含一 蒸餾塔，此蒸餾塔包含三個區域，其中反應區位於中間， 裡面包含固體酸性觸媒固定於蒸餾物托盤上，或另一較具 體的方法係固定於我們所知具有内部管道的順向充填物中 ;反應區的下層高沸點有機物分離區與上層低沸點有機物 分離區皆充填大量的惰性充填物，此些充填物的構造為所 _ 知的經過設計或是蒸餾物内建部分的順向充填物，如此觸 媒則固定於兩惰性多孔物質間以形成充填物；乙酸或酸酐 或兩者的混合物進料管路係位於反應區上方或其較高處，
第13頁 1284635 五、發明說明（6) 案號 89123165 年月日 修正 而乙醇進料管路係位於反應區下方或其較低處，在蒸餾塔 的底部提供一鍋爐，未反應的乙酸係經由此鍋爐或蒸餾塔 的底部取出；蒸餾塔的頂部終止於塔頂部，在塔頂部設置 一蒸餾蒸汽輸出管路連接至冷凝裝置，在冷凝裝置後則設 置一冷凝液輸出管路，用於將冷凝液運送至分離裝置中， 冷凝液在分離裝置中分離成水與有機物，水由分離裝置下 方設置的水輸出管路取出，另設置一回流液輸送管路運送 回流液體至蒸餾塔中及一乙酸乙酯輸出管路來輸送未回流 的有機物。
上述本發明的方法可明顯的得到高平衡狀態的反應， 並可幾近百分之百的將起始反應物轉化成乙酸乙酯與水， 特別是當乙醇提供的計量稍不足時，乙醇可被完全轉換成 乙酸乙酯，且乙酸乙酯可由與水的混合物中輕易的分離出 。分離區執行分離生成產物的功能，生成產物包括：乙酸 乙酯與水及起始反應物：乙酸與乙醇及上述回流至分離區 的起始反應物，其中乙酸乙酯與水一起被持續蒸餾出，之 後水被由有機物分離出，此有機物中包含大部份的乙酸乙 酯，並將一部份的有機物回流至蒸餾塔中作為下一新反應 的起始務物，而另一部份的有機物則由另一乙酸乙酯輸出 管路輸出。
反應物的組成如：乙酸或酸酐與乙醇可以以計量比率 進入反應區或使乙酸或酸酐或兩者的混合物過量來將乙醇 幾近完全的轉換。若本發明的方法係在大氣壓力下反應時 ，蒸餾塔的溫度是被固定的，以至於塔頂部的溫度是在
第14頁 7曰0 °C至74。(：間。起始進料的組成中乙醇進入蒸餘塔的位置 疋低於乙酸或酸酐或兩者的混合進料是可被理解的，通常 較具體的y法是將乙醇由反應區的下方或反應區的較低處 注入蒸餾塔中，換句話說，乙酸或酸酐或兩者的混合進料 係由反應區的上方或反應區的較高處注入蒸餾塔中。 蒸餾蒸汽經過塔頂部後被由7〇 1降至5艺凝°結成混合 物，之後被分離成有機物與水，一部份的有機物 部份的乙酸乙醋被回流至塔頂，而另一部份則：：U 發明中一特別的結果係蒸餾物中包含低含量的乙醇，即比 一巧土 ^乙酸乙酯、乙醇及水的三部份共沸點 Ϊ意義的現象使產業上在做最後蒸館物的_ Ϊ ^ ί谷i中·包含一定量不溶的乙酸乙S旨及乙醇最 後被取出，k里的乙酸可由塔底的加熱鍋爐中持續被取出 。本發，的方法可由化學反應中將蒸餾物中的水完全分離 ，或由蒸餾塔底部將一部份水與未反應剩餘的乙一取 出。 本發明之裝置詳細說明： 请參閱第1圖，係為本發明合成乙酸乙酯之方法的裝 Λ示人意圖’如^所示：該裝置主要包含蒸顧塔1，該蒸顧塔 1包3三個反應區間，其中中間部分為反應區2，在反應區2 ，上.、下分別為低沸點有機物分離區4及高沸點有機物分離 區3 ;在該反應區2内充填固體觸媒，該固體觸媒可使用具 酸離子交換功能之物質，如：硫化苯乙烯—二乙烯基苯的共 聚物，含1%至25%的重量乙烯基苯與卜10託(1(11+)/8
第15頁 1284635 修正 ^S_B23165 五、發明說明（8) 的酸。然而，任何的酸離子交換樹酯均可被使用，如酸性 沸石或其他所知的酸性觸媒皆可，而低沸點有機物 · 及高沸點有機物分離區3内則充填順向充填物。 时 在=塔1的下方終止於塔底部7，並在塔底部7的下方 提供一鍋爐8二並於鍋爐8的一端設置一剩餘乙酸回收管路 H應在，未反應的乙酸係經由剩餘乙酸回收管路9 取出，在彘，％1的上方終止於塔頂部1〇，並在塔頂 上方提供-、凝裝置12，並藉由蒸德蒸汽輸出管路i i / 餾塔1連接，反應後的蒸餾蒸汽包括水、乙酸乙酯及未反應 之乙醇，=由，餾蒸汽輸出管路i J將蒸餾蒸汽引入冷凝W 置1 2中、’，餾瘵汽進入冷凝器丨2後形成冷凝液，冷凝液: 經由與冷凝裝置12連接之冷凝液輸出管路13輸出，之二 入與冷凝液輸出管路13另一端相連接之分離裝置14曼机 液在分離裝置丨4中被進一步分離成水與有 ^分離裝置14下方所設置的水輪出管路15取出，分離# 14的上方則設置一回流液輸送管路16與一乙酸乙醋輸& | 路17，回流液輸送管路16用於將回流液輸送至蒸餾塔i \ =部10，而乙酸乙酯輸出管路17則將沒有回流的有機物。 出’如此不斷的循環回流部分有機物以達到純化乙酸乙= 的功效。 曰 合成的步驟係，首先將反應物乙酸或酸酐進料管路5 入蒸館系統中，乙酸或酸酐進料管路5係位於反應區2之上 方及低沸點有機物分離區4的下方，即恰位於反應區2及低 彿點有機物分離區4之間，反應物乙醇則由乙醇進料管 ·
1284635 二_案號 89123165_ 年月 曰_， 五、發明說明（9) * 路6進入蒸餾系統中，該乙醇進料管路6係位於反應區2之下 方與高沸點有機物分離區3的上方，即反應區2與高沸點有 機物分離區3間，乙酸或酸酐或兩者的混合物與乙醇的莫耳 比例係在2 : 1〜1 : 2 · 5間，且總流率為0 · 1至1 01Γ1 ( . 單位觸媒體積），合成反應與生成物的分離反應係同時進 行，且因生成物會形成不同的共沸點，所以會被分成兩部 ‘ 份，其中共沸點較低者會由反應區2進入低沸點有機物分離 區4中，此共沸點較低者包括水、乙酸乙酯及其餘有機物 質，在經過低沸點有機物分離區4後會經由蒸餾蒸汽输出管 路11進入冷凝裝置12中，溫度由70° C降至5° C後形成冷凝 液，並由冷凝液輸出管路13輸出再進入分離裝置14中，分 ® 離裝置1 4將此些混合液分離成水及有機物，其中部份有機 物（含乙酸乙酯）經由回流液輸送管路1 6回流至蒸餾塔1的 塔頂部1 0中，同時再與新的反應物進行蒸餾分離反應，此 回流液與新的反應物間的比率為1 : 1〜1 : 2 0，其餘有機物 則由乙酸乙酯輸出管路1 7取出（含高濃度之乙酸乙酯）， 而水則由水輸出管路1 5取出；而共沸點較高者則由反應區2 下方進入高沸點有機物分離區3，共沸點較高者為未反應之 乙酸或酸酐與少部份的水，會經由與鍋爐8相連接之剩餘乙 酸回收管路9取出，有機物的回流會不斷的進行以達成純化 乙酸乙酯及充分分離主產物乙酸乙酯與副產物水的功效。鲁 較佳實施例： 實施例1 :
第17頁 1284635 年 月 曰 修正 案號 89123165 五、發明說明（10) 、 在反應區2中填充3 3克具催化活性之酸性交換樹酯，高 沸點有機=分離區3及低沸點有機物分離區4的長度約為 0· 5m ’乙醇由乙醇進料管路6進入高沸點有機物分離區3的 上方’而乙酸則由乙酸或酸酐進料管路5進入低沸點有機物 分離區4的下方，且此二者的流率為〇· 25m〇1/h ;反應後經 分離裝置14分離所得的水取出流率為4· 2g/h，而有機物的 回流流率為2 1 g/h ;未反應的乙酸由剩餘乙酸回收管路9取 出的流率為1· 2g/h，此實施例所得之反應轉化率為92 %(即 合成乙酸乙酯的比率）。 實施例2 : 實施例1中的起使反應物乙酸以酸酐代替，酸酐盥乙醇< 以等莫耳進行反應生成乙酸與乙酸乙酯；乙酸對乙醇的選 則率為1· 52 ;回流比為1 ·· 6 ;乙酸乙酯的取出流率為 0· 46mol/h ’反應後經分離裝置14分離所得的水取出流率為 3.91111/11此實施例所得之乙酸乙酯純化率為914%，且分離 所得的乙酸乙酯只含5. 2%的副產物水及3· 4%的乙醇。 實施例3 : 在蒸餘塔1的t間反應區2中填充酸離子交換觸媒〔 KATAPAKRS〕l.〇7kg，高沸點有機物分離區3及低沸點有機 物分離區4則填充順向充填物；進料乙酸的量為〇 73kg/h ’乙醇為〇·41 kg/h，最後由乙酸乙酯的混合物中分離出乙^ 酸0· 003%、乙醇1· 4% 及水 1· 43%。 — 實施例4 : 將實施例3中的進料乙酸改以6 6 · 6 %乙酸、〇 8 %乙醇、
1284635 案號 89123165 曰 修正 五、發明說明（11) 2 5. 4%乙酸乙酯及7. 2%水代替，流率為0 組成是來自於將反應後經分離裝置1 4所 流再與新的進料重新組成所得，此實施 乙酯純化，其中包含2. 6%的水及0. 5%的 層析法中並無债測到乙酸的存在，由此 層部份回流與新的進料進行蒸餾分離反 的乙酸乙酯，且可充分將副產物水自混 綜上所述，本發明係有關於一種乙 及裝置，主要係將蒸餾塔分成三區並在 所得的有機物部份回流與新的反應物進 應下，可得高純度之乙酸乙酯及達到充 乙酯與副產物水的功效。故本發明實為 步性、及可供產業利用功效者，應符合 ，爰依法提出發明專利申請，祈鈞局早 感禱。 惟以上所述者，僅為本發明之較佳 用來限定本發明實施之範圍。故即凡依 圍所述之實驗條件、特徵、及精神所為 ，均應包括於本發明之申請專利範圍内 簡單圖號說明： 1 蒸餾塔 2 反應區 3 高沸點有機物分離區 4 低浠點有機物分離區 .843kg/h，此進料. 得的有機物部份回 例可將9 6 . 1 %的乙酸 乙醇，最後由氣相 可知不斷的將有機 應，可得高純化率 合物中分離。 酸乙酯的合成方法 不斷的將分離裝置 料進行蒸餾分離反 分分離主產物乙酸 一富有新穎性、進 專利申請要件無疑 日’賜准專利，至為 實施例而已，並非 本發明申請專利範 之均等變化與修飾 _
第19頁 1284635 a_修正 案號 89123165 五、發明說明（12) 5 乙酸或酸酐的進料管路 6 乙醇進料管路 7 塔底部 8 鍋爐 9 剩餘乙酸回收管路 10 塔頂部 11 蒸餾蒸汽輸出管路 12 冷凝裝置 13 冷凝液輸出管路 1 4 分離裝置
1 5 水輸出管路 1 6 回流液輸送管路 17 乙酸乙酯輸出管路
第20頁 1284635 L_案號89123165_年月日_«：_ 圖式簡單說明 第1圖：係為本發明合成乙酸乙酯之方法的裝置示意圖。 i»m 第21頁
Claims (1)
1284635 "_案號 89123165_年月日___ 六、申請專利範圍 1 · 一種製備乙酸乙酯的方法，是由乙酸或酸酐或兩者的. 混合物在酸性固體觸媒存在下同時進行蒸餾分離反應 ，其係包括以下步驟·· 以乙酸或酸酐或兩者的混合物與乙醇的進料莫耳比率 為2 : 1至1 : 2 · 5間，且總流率為0 . 1至1 0 hw 間（單 位觸媒體積）；此系統中，反應與蒸餾物的分離是 被分成三個區域達成，在反應區，反應與蒸餾物的 分離同時發生，反應後的蒸餾物組成具有不同的沸 點，因而被分成二個區域，反應生成的副產物水與 乙酸乙酯形成低共沸點的混合物，並且被部分或完< 全由系統中取出，之後，蒸餾物由70 °C降至5 °C被冷< 凝成液體，且蒸餾物中的水被從乙酸乙酯與其它有 機組成中分離出並將之取出，在此，有機蒸餾物中 的有機組成包含絕大部分的乙酸乙酯且被一部分回 流至蒸餾系統中，而另一部份則取出；在部份有機 組成回流至蒸餾系統中的同時，新的乙酸或酸酐或 兩者的混合物進料會由反應區的上方進入系統中且 新的乙醇進料會由反應區的下方進入系統中；新的 進料組成與回流的有機組成間的比率為1 : 1至1 : 2 0 間，且未反應的乙酸則被分離成較高沸點的底部組 成。 2 ·如申請專利範圍第1項所述之製備乙酸乙酯的方法， 由於將部份有機組成回流至蒸餾系統中，其中該起始 乙酸或酸酐或兩者的混合物也會包含乙酸乙酯與水或
第22頁 1284635
案號 89123165 年月 日· 修正 六、申請專利範圍 水、與乙醇或乙醇。 3 ·如申請專利範圍第1項或第2項所述之製備乙酸乙酯 的方法，其中該乙酸或酸酸酐或兩者的混合物與乙醇 間的莫耳比率是在1 : 1至1 : 0. 5間。 4 ·如申請專利範圍第1項或第2項所述之製備乙酸乙酯 的方法，其中該起始反應物的總流率為0. 5至5hW (單 位觸媒體積）。 5 ·如申請專利範圍第3項所述之製備乙酸乙酯的方法，其 中該起使反應物的總流率為0 . 5至51^ (單位接觸面積）
6 ·如申請專利範圍第1項所述之製備乙酸乙酯的方法， 其中該未反應的乙酸係被分離成較高沸點的底部組成 ，且包含一部份化學反應所生成的水。 7 · —種製備乙酸 乙酷的裝置，所使用的元件包含： 一蒸餾塔，該蒸餾塔包括三個區間，其中反應區係位 於蒸餾塔管柱的中間部位，裡面包括固體酸性觸媒 該蒸餾塔下半部為高沸點有機物分離區而上半部為低 沸點有機物分離區，該高沸點有機物分離區與低沸 點有機物分離區中皆充填惰性充填物，該惰性充填 · 物為順向充填物或蒸餾物内建組成； 乙酸或酸酐的進料管路係位於該反應區的上方或較高 處，而乙醇進料管路係位於該反應區的下方或較低
第23頁 1284635 案號 89123165 Λ_η 曰 修正 六、申請專利範圍 處， 該蒸餾塔 一锅爐 乙酸回 的上方 餾蒸汽 與一冷 出管路 連接， 分離裝 酯輸出 8 ·如申請專 其中該固 物托盤中 9 ·如申請專 其中該固 了液相與 反向流動 的下 ，未 收管 終止 輸出 凝裝 ，而 在該 置的 管路 利範 體酸 方終 反應 路取 於塔 管路 置連 冷凝 分離 上方 〇 為第 性觸 止於 的乙 出或 頂部 ，該 接， 液輸 裝置 連接 塔底 酸係 自塔 ，在 蒸餾 該冷 出管 的下 一回 部，並 經由與 底部取 該塔頂 蒸汽輸 凝裝置 路的另 方連接 流液輸 在塔 該鍋 出； 部的 出管 底部下 爐連接 以及該 上方提 路的另 方提供 的剩餘 蒸德塔 供一蒸 一端係 再連接一冷凝液輸 一端再與分離裝置 一水輸出管路及在 送管路與一乙酸乙 利範為第 體酸性觸 固體酸性 的接觸。 7項所述之製備乙酸乙酯之裝置， 媒被堅固的固定於反應區中的蒸餾 7項所述之製備乙酸乙酯之裝置， 媒被固定於反應區中，其構造提供 觸媒接觸，且提供了液相與氣相有
•第24頁 1284635 ___案號89123165_年月日 修正 六、指定代表圖
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| ZA816748B (en) * | 1980-10-01 | 1982-10-27 | Hoechst Ag | Process for the preparation of an ethyl ester |
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| KR960006546B1 (ko) | 1993-07-28 | 1996-05-17 | 한국과학기술연구원 | 초산에스테르의 제조 방법 |
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| EP1066242B1 (en) | 1998-03-25 | 2003-05-07 | Sulzer Chemtech AG | Process and apparatus for the production of butylacetate and isobutylacetate |
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- 1999-10-14 CZ CZ19993635A patent/CZ292620B6/cs not_active IP Right Cessation
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2000
- 2000-10-11 WO PCT/CZ2000/000075 patent/WO2001027065A1/en not_active Ceased
- 2000-10-11 AU AU75042/00A patent/AU7504200A/en not_active Abandoned
- 2000-10-11 KR KR1020027003761A patent/KR100663853B1/ko not_active Expired - Fee Related
- 2000-10-11 DE DE60025239T patent/DE60025239T2/de not_active Expired - Lifetime
- 2000-10-11 US US10/110,641 patent/US6693213B1/en not_active Expired - Fee Related
- 2000-10-11 CN CNB008140995A patent/CN1205168C/zh not_active Expired - Fee Related
- 2000-10-11 JP JP2001530087A patent/JP4724341B2/ja not_active Expired - Fee Related
- 2000-10-11 AT AT00963863T patent/ATE314341T1/de active
- 2000-10-11 BR BRPI0014732-0A patent/BR0014732B1/pt not_active IP Right Cessation
- 2000-10-11 EP EP00963863A patent/EP1220829B1/en not_active Expired - Lifetime
- 2000-10-13 MY MYPI20004816A patent/MY122676A/en unknown
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| EP1220829B1 (en) | 2005-12-28 |
| EP1220829A1 (en) | 2002-07-10 |
| WO2001027065A1 (en) | 2001-04-19 |
| BR0014732B1 (pt) | 2011-07-12 |
| KR100663853B1 (ko) | 2007-01-02 |
| DE60025239D1 (de) | 2006-02-02 |
| DE60025239T2 (de) | 2006-06-22 |
| CN1205168C (zh) | 2005-06-08 |
| CN1433395A (zh) | 2003-07-30 |
| CZ292620B6 (cs) | 2003-11-12 |
| BR0014732A (pt) | 2002-06-11 |
| US6693213B1 (en) | 2004-02-17 |
| AU7504200A (en) | 2001-04-23 |
| JP2003535814A (ja) | 2003-12-02 |
| MY122676A (en) | 2006-04-29 |
| KR20020040813A (ko) | 2002-05-30 |
| CZ9903635A3 (en) | 2001-05-16 |
| ATE314341T1 (de) | 2006-01-15 |
| JP4724341B2 (ja) | 2011-07-13 |
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