TWI324592B - A method for the esterification of a fatty acid - Google Patents
A method for the esterification of a fatty acid Download PDFInfo
- Publication number
- TWI324592B TWI324592B TW092126003A TW92126003A TWI324592B TW I324592 B TWI324592 B TW I324592B TW 092126003 A TW092126003 A TW 092126003A TW 92126003 A TW92126003 A TW 92126003A TW I324592 B TWI324592 B TW I324592B
- Authority
- TW
- Taiwan
- Prior art keywords
- alcohol
- fatty acid
- acid
- reaction zone
- stripping gas
- Prior art date
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/03—Preparation of carboxylic acid esters by reacting an ester group with a hydroxy group
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- 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
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- 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
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- 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
- B01D3/34—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping with one or more auxiliary substances
- B01D3/343—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping with one or more auxiliary substances the substance being a gas
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
- B01J8/04—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 passing successively through two or more beds
- B01J8/0403—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 passing successively through two or more beds the fluid flow within the beds being predominantly horizontal
- B01J8/0423—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 passing successively through two or more beds the fluid flow within the beds being predominantly horizontal through two or more otherwise shaped beds
- B01J8/0426—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 passing successively through two or more beds the fluid flow within the beds being predominantly horizontal through two or more otherwise shaped beds the beds being superimposed one above the other
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J2219/2451—Geometry of the reactor
- B01J2219/2453—Plates arranged in parallel
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- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
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- B01J2219/2401—Reactors comprising multiple separate flow channels
- B01J2219/245—Plate-type reactors
- B01J2219/2451—Geometry of the reactor
- B01J2219/2456—Geometry of the plates
- B01J2219/2458—Flat plates, i.e. plates which are not corrugated or otherwise structured, e.g. plates with cylindrical shape
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J2219/32475—Composition or microstructure of the elements comprising catalytically active material involving heat exchange
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- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
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- B01J2219/332—Details relating to the flow of the phases
- B01J2219/3325—Counter-current flow
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- 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)
- Thermal Sciences (AREA)
- Fluid Mechanics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
1324592 (1) 玖、發明說明 【發明所屬之技術領域】 本發明係關於脂肪酸酯化之方法,以及利用如本發明 之方法藉由多相催化作用以產生脂肪酸酯的設備》在本發 明方法中係使用月桂酸、肉豆蔻酸、棕櫚酸、硬脂酸、油 酸或亞麻油酸中之任一個與下列醇之一進行酯化反應:甲 醇、乙醇、正-丙醇、異丙醇、正-丁醇、異丁醇或2-乙基 己醇。 【先前技術】 根據慣用方法,是以批次方式酯化一預定量的肪肪酸 。在此方法中,脂肪酸將放置於帶有攪拌機制的可加熱容 器中,再加熱至約100°C至2 5 0 t。然後加入觸媒並於恆 定之溫度下與一定進料之醇進行酯化。將來自該容器之蒸 氣股流導入分離塔中,其中在酯化期間釋出之水將與共汽 化之醇分開。因此,水就可從程序中除去,藉此便可增進 轉化率。一旦酯化過程完成後,醇及水之殘留物將可藉由 進一步加熱而除去。酯化之連續方法乃揭示於美國專利 US-A·6 〇69 261案號中,其中使用了“永久”輔助氣體以便 連續地除去水。舉例之,此類輔助氣體可爲氫或氮,彼等 不會與酯化之反應物一起進入化學反應中。 【發明內容】 本發明之目的係提供另一脂肪酸酯化之方法,彼可連 -5- (2) (2)1324592 續地進行且無需使用如氫或氮之輔助氣體。此一目的可經 由如申請專利範圍第1項所定義之方法而獲得滿意結果。 脂肪酸F之酯化方法係在一具有一或多部份之塡充部 件的塔中進行。塡充部件除了作爲反應器外,還具有汽提 區的功用。至少在上面部份可形成反應區,其中可進行脂 肪酸F與醇A (使用相同莫耳比或過量)之多相催化作用 。在儲槽中可藉由汽化而產生一氣態之富含醇的逆流。水 可藉由充當汽提氣體之逆流而從反應區中除去。負載之汽 提氣體將在該塔頂部至少部份液化。頂部產物將分離成富 含水之餾份以及富含醇之餾份。該富含醇之餾份將再返回 過程中做爲起始物質,以用於酯化及汽提氣體之產生。 附屬項之申請專利範圍第2至9項係關於如申請專利 範圍第1項之方法的有利具體實施例。可供進行本方法之 設備則隸屬於申請專利範圍第1 0項。 圖1所述之設備包括塔1,在其儲槽中有一中間產物 ,亦即一含有根據本發明所獲得之脂肪酸酯的混合物可經 由管線51萃取,並送進設備7之部件中以便清洗及濃縮 。本說明係應用於脂肪酸酯E(如脂肪酸異丙酯)之製造 ,其比相對應之脂肪酸F更易於沸騰。 如本發明之方法的起始物質是醇A和脂肪酸F。在塔 1所獲得之中間產物含有起始物質之殘留物及雜質。此中 間產物可於設備部件7中的分離塔內進一步處理,如此最 終將得到脂肪酸酯E,其純度至少是99%。清洗過之產物 係經由管線71來萃取。在分離塔中分離出之脂肪酸F的 -6 - (3) (3)1324592 殘留物則經由管線72再返回方法中。 塔1包括有可形成催化反應區域3之填充部件,其中 將藉由多柑催化作用進行酯化反應。含有醇A和脂肪酸F 之混合物是經由管線1 0及分配器3 0施加到塡充部件3。 帶有分配器40之塡充部件4乃排列在塡充部件3下面。 額外之醇A將經由管線11及分配器40送進過程中。 由兩個部件3及4組成之塡充部件除了做用爲反應器 外,也有汽提區的功用。醇A係以相同莫耳比或過量使 用。因此,氣態之富含醇的逆流50可藉由汽化而於儲槽 中產生,其可充當爲汽提氣體50’,進而從反應區域3中 除去水。汽化所需之熱可藉由加熱支流5 3 (熱供給Q+ ) 而由裝置5供應。水W及同樣地醇A也會藉由在汽提區 段之下面部件4的汽提氣體50而從離開反應區3之液體 混合物中被帶走。 負載之汽提氣體(箭頭60)將在塔頂部於裝置6(熱 抽提Q-)內至少部份液化,再分離成兩個餾份62及63。 頂部產物之餾份63富含水,舉例之,可具有比例爲80重 量%之水W。富含醇之餾份62含有95%-98%重量比之醇 A。此醇A將以起始物質方式返回過程中用於酯化反應並 產生汽提氣體50»舉例之’頂部產物分離成富含醇之餾 份62及富含水之餾份63可藉助於膜過程、全蒸發過程、 相分離或蒸餾塔來著手。 經由下面之分配器40配送的醇A是在塡充部件4上 汽化,因此可提供汽提氣體50之股流。汽化所需之熱是 (4) (4)1324592 由在儲槽中藉由蒸發而使之呈過熱狀態的汽提氣體50來 供應。 在所示之_實施例中,催化反應區3係由垂直層31及 供汽提氣體5 1 ’用之流動通道3 2所組成。一含有起始物 質A及F之混合物將從中流過並到達層31。反應區3的 詳情則解說於圖2之切面圖,也就是說,在流動通道32 與汽提氣體50’和層31之間有一邊界,其包含有觸媒之 顆粒狀物質310。取自耐用物質之織物311將形成可裝入 顆粒狀物質310的口袋。混合物10’便可流入各口袋中及 通過織物311的外邊,口袋內部有蜿蜒的通道,而口袋外 表則宛如滴流式薄膜。由於水W存在著相對小的分壓, 所以水W會穿過滴流式薄膜10”的表面而進入汽提氣體 50’股流中。醇 A則會穿透滴流式薄膜10”的表面而以兩 個方向傳送。反應區3之合適塡充物係揭示於歐洲專利 EP-A 0 396 650 案號或 EP-A 0 396 650 案號。 在一預反應器2中起始物質A及F已優先地部份反 應在一起,其中1〇至30%的脂肪酸F已轉化爲酯E。因 此,醇A、脂肪酸F、酯E及水W之混合物會通過管線 10流入塔1內。然後,另外之20%至70%的脂肪酸F會 在反應區3中轉化。 另一塡充物8及分配器80(可參閱圖3)將建構在汽 提區段3,4上面而有利地成爲塔1的一部份。由汽提氣體 6〇所攜帶之脂肪酸F連同富含醇之部份68將在此一塡充 物8內被擄獲,再返回餾份62中。 -8- (5) (5)1324592 圖4係顯示設備部件7,彼乃用於清洗反應過之脂肪 酸。此設備部件7中,元件之一是緩衝蒸發器9,其中管 線52中的中間産物會以蒸氣形式釋出大部分的殘留醇A 。此富含醇之蒸氣將從管線92中逸去。其可進一步用於 酯化反應中。低醇之混合物則經由管線91導入分離塔70 中。清洗過之酯E的萃取(管線71)可在此處進行。經 由管線76而從冷凝器75中萃取之頂部產物含有醇A及 揮發性雜質,特別是空氣。脂肪酸F (管線74 )及不易揮 發之雜質(管線74 )可從利用加熱循環73來供給熱之儲 槽中萃取。無論如何,設備部件7也可安排做爲蒸餾塔。 圖4係在說明分離過程,當脂肪酸酯E在比相對應之 脂肪酸F還低的溫度下沸騰時便可使用此一過程。在脂肪 酸與高碳醇(例如2-乙基-己醇)酯化的情況下,設備部 件7中之清洗就會應用相反的比。脂肪酸酯將在分離塔 70的儲槽中回收並進一步處理(未解說)。脂肪酸及殘 留之醇則可在分離塔70之頂部萃取,再返回過程中。下 列之起始物質可用做爲脂肪酸F或醇A以供酯化用。關 於F可爲月桂酸、肉豆蔻酸、棕櫚酸、硬脂酸、油酸或亞 麻油酸中任一個;而A可爲甲醇 '乙醇、正-丙醇、異丙 醇、正-丁醇、異丁醇或2-乙基-己醇中之任一個。 離子交換樹脂或無機觸媒可用做爲觸媒,其中這些觸 媒較佳地是強酸形態,而離子交換樹脂較佳地是製成大孔 性。若甲醇、乙醇、正-丙醇、異丙醇、正-丁醇或異丁醇 是醇A時’則觸媒(此一情況爲離子交換樹脂)必須能 -9 - (6) (6)1324592 在120°C與140°C間的溫度下使用;且其在此一溫度間隔 內僅能緩和地減損活性。若2 -乙基-己醇是醇A時,則觸 媒(此一情況爲無機觸媒)必須能在150-230。(:之溫度下 使用。 下列有一些方法參數値將用於棕櫚酸(PA)與異丙 醇(IPA )之酯化反應中。 對起始物質A = IPA及F = PA而言,各別純度在95%及 98% (重量% )是較佳的。然而,其他數値也可行,亦即 對IPA而言在88°/。-100%範圍內,而pa則是95%-100%。 預反應器2係在100 °C及2巴下操作。然而,也可在高至 140°C之溫度及高至4巴之相對應較高壓力下操作。通常 ,不同量的IPA會經由管線21及1 1進入。IPA (管線21 )對IPA (管線11)之比率較佳地是2.5,然而也可在1 至4範圍內。塔1之頭壓等於2至5巴,同時相對應地, 反應區3之溫度則等於120°C至140°C。中間產物(管線 53)在加熱裝置5內將加熱至170 °C至200 °C的溫度範圍 ,更甚者也可加熱至25 0°C。 汽提氣體60 (圖1)是在塔頂部並位於塡充物8(圖 3 )上方,其溫度在1 1 5 °C與1 40 °C之間,並含有5%至 12%的水W。管線53內之中間產物含有50%至80%酯及 2 % 至 1 0 % 的 IP A。 緩衝蒸發器9是在1巴及160 °C至210 °C下操作。在 此處IPA將減低至約0.5%。分離塔70則在15至40毫巴 下操作。冷凝氣75內之溫度將減少至80 °C與1〇〇 °C之間 -10- (7) (7)1324592 的數値’而在加熱循環73內產生的溫度係220 °C至240 °C 。此溫度的上限可爲250 °C。 如本發明之兩個_化反應實施例,其係以以試驗性質 的實驗而獲得,乃解說如下。 【實施方式】 實施例1 : 在下列條件及在大氣壓下,於塔中連續地進行棕櫚酸 與異丙醇之酯化反應: 反應塔: 內直徑:5 0公釐。 加濃區段及汽提區段:Sulzer塡充物BX 反應區:catapak-S/塡充有強酸性離子交換樹脂’在 高至14(TC溫度下具安定性。 進料股流: 棕櫚酸(進料1) :2.16公斤/小時-異丙醇(進料· 2 ) : 1.44公斤/小時 產物股流: 頂部產物:1.2公斤/小時-儲槽產物:2 _4公斤/小時 操作條件:
頭壓:1013毫巴-返回速率:〇.2 反應區溫度:約98°C --儲槽溫度:157.9°C 所測量之儲槽濃度(重量%):棕櫚酸異丙酯14^4 異丙醇:10.61 --棕櫚酸:74.5 -水:0.83 -11 - (8) (8)1324592 實施例2 : 在一壓力塔中執行妲實施例1之相同結構。其中是使 用預活化之進料,彼等會模擬進行預反應。藉助於微過量 的壓力,反應區的溫度範圍可設定在約l4〇°C。下列之操 作條件將產生顯著較高的反應轉化率。 進料股流: 進料1 : 2.3公斤/小時,其具有下述之組成份((重 量 0/〇 ): 棕櫚酸異丙酯:24.3 --異丙醇:21.6 --棕櫚酸: 5 2.1 - ·水 2 · 0 進料2 :異丙醇:1.84公斤/小時 產物股流: 頂部產物:1.43公斤/小時-儲槽產物:2.71斤/小時 操作條件: 頭壓:5100毫巴-返回速率: 0.2
反應區溫度:約140°C —儲槽溫度:192°C 所測量之儲槽濃度(重量% ):棕櫚酸異丙酯 64.0 --異丙醇:7.7--棕櫚酸:28.3 -水:0.06。 【圖式簡單說明】 本發明將以下列之圖爲基礎而說明如下: 圖1. 一具有塔之設備,其中排列有催化反應區,其 是用來進行如本發明之方法, -12- (9)1324592 圖2.催化反應區之截面, 圖3.該塔之較佳具體實施例的頭部區域,以及 圖4.設備中之部份,可用來清洗生成之脂肪酸酯。 【符號說明】 1 塔 2 預反應器 3 塡充部件
4 塡充部件 5 加熱裝置 6 裝置 7 設備部件 8 塡充物 9 緩衝蒸發器 1〇 管線
10’混合物 10”滴流式薄膜 11 管線 21 管線 22 管線 30 分配器 3 1 垂直層 32 流動通道 40 分配器 -13- (10)1324592 5 0 富含醇之逆流 50’汽提氣體 51 管線 52 管線 53 支流 60 負載之汽提氣體 6 1 管線 62 富含醇之餾份
63 富含水之餾份 68 富含醇之部份 70 分離塔 71 管線 72 管線 73 加熱循環 74 管線
75 冷凝器 76 管線 80 分配器 91 管線 92 管線 3 1 0顆粒狀物質 31 1織物 A 醇 F 脂肪酸 -14- (11) (11)1324592 E 脂肪酸酯 W 水 Q+ 熱供給 Q- 熱抽提
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Claims (1)
1324592
(1) 拾、申請專利範圍 1. 一種使脂肪酸酯化之方法,其中塔(1)具有一個 瑱充部件(3,4)或具有二或多個塡充部件(3,4 ),其中 塡充部件(3,4 )具有汽提區的功用,且塡充部件(3 )至 少在具有固定於塡充物內之觸媒的上面部份形成反應區, 該方法中脂肪酸與醇(使用相同莫耳比或過量)進行多相 催化作用,在儲槽中藉由汽化而產生一氣態之富含醇的逆 流(5 0 ), 水藉由充當汽提氣體之逆流而從反應區中除去, 負載之汽提氣體(60)在該塔頂部至少部份液化, 頂部產物被分離成富含水之餾份(63)及富含醇之餾 份(62 ),以及 該富含醇之餾份再返回製程中作爲起始物質,以用於 酯化及汽提氣體之產生。 2. 如申請專利範圍第1項之方法,其中,在該汽提 區段(3,4)的下面部件(4)中,水和醇一起與汽提氣體 (50)從離開反應區(3)之液體混合物中分離。 3. 如申請專利範圍第1項之方法,其中,另一塡充 物(8)係組裝在該汽提區段(3,4)的上方,其中由汽提 氣體(6)所攜帶之脂肪酸被富含醇之部份(68)及返回 餾份(62 )擄獲。 4. 如申請專利範圍第1至3項中任一項之方法,其 中,該醇係送進反應區(3)或反應區(3)之下方,其可 提供蒸氣形態之汽提氣體流( 5 0,5 0’)。 -16- (2) (2)1324592 5. 如申請專利範圍第1至3項中任一項之方法’其 中,頂部產物分離成富含水之餾份(62)及富含醇之餾份 (63)係藉助於全蒸發過程(pervap oration )、相分離或 蒸餾塔來進行。 6. 如申請專利範圍第1至3項中任一項之方法’其 中,在預反應器(2)中醇及脂肪酸進行部份酯化反應, 而所形成之脂肪酸、醇、酯及水的混合物係施加到該塔( 1)的反應區(3)內或其上方。 7. 如申請專利範圍第1至3項中任一項之方法,其 中,液態儲槽混合物(52)之一部份(52)可進一步藉由 緩衝蒸發器(9)或蒸餾塔來製備,如此最後在分離塔( 70 )中獲得脂肪酸酯,其純度是至少99重量%。 8. 如申請專利範圍第1至3項中任一項之方法,其 中,下列之起始物質可使用作爲脂肪酸及/或醇以用於酯 化反應:月桂酸、肉豆蔻酸、棕櫚酸、硬脂酸、油酸或亞 麻油酸中之任一酸,以及甲醇、乙醇、正-丙醇、異丙醇 、正-丁醇、異丁醇或2-乙基-己醇中之任一醇。 9. 如申請專利範圍第1至3項中任一項之方法,其 中,可使用無機觸媒作爲觸媒,且較佳地係在150t與 230°C之溫度下使用’或者是使用離子交換樹脂,且當在 1 20 °C以上至最高140 °C之溫度下進行時其僅緩和地減損 活性’其中觸媒較佳爲強酸形式,離子交換樹脂較佳爲巨 孔的。 10. —種實施如申請專利範圍第1項之方法藉由多相 -17 - (3) 1324592 催化作用以製造酯的設備,其特徵爲,塔(1)具有用於 進行多相催化作用之塡充部件(3,4 )的塡充部件(3 ), 其中該塡充部件(3,4)具有汽提區的功用且該塡充部件 (3)形成反應區,該塡充部件中之塡充物包括形成 爲垂直層(31)之多孔性觸媒載體及可讓汽提氣體(5〇, )在觸媒載體之間流通的流動通道(32),其中,一旦在 觸媒載體之孔洞中進行該方法時,待處理之混合物形成直 接向下之液體流(1 0 ’),而汽提氣體則形成直接向上流 ’該液相與氣相直接接觸,如此就可進行物質交換。 -18-
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US7091367B2 (en) | 2006-08-15 |
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