TWI443081B - 利用鈷催化劑由醋酸產製乙醇 - Google Patents

利用鈷催化劑由醋酸產製乙醇 Download PDF

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TWI443081B
TWI443081B TW98125945A TW98125945A TWI443081B TW I443081 B TWI443081 B TW I443081B TW 98125945 A TW98125945 A TW 98125945A TW 98125945 A TW98125945 A TW 98125945A TW I443081 B TWI443081 B TW I443081B
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acetic acid
catalyst
ethanol
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metal
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Victor J Johnston
Josefina T Chapman
Laiyuan Chen
Barbara F Kimmich
James H Zink
Der Waal Jan Cornelis Van
Virginie Zuzaniuk
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Celanese Int Corp
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
    • C07C29/147—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
    • C07C29/147—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
    • C07C29/149—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof with hydrogen or hydrogen-containing gases
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    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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    • Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel

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Description

利用鈷催化劑由醋酸產製乙醇
本發明係關於一種由醋酸產製乙醇之方法，特別是本發明係關於一種利用催化劑，氫化醋酸而高選擇性形成乙醇之方法，而該催化劑係以合適催化劑擔體支撐之鈷，並視需要地含有一種或一種以上金屬所組成。
產業上長期需求一種將醋酸轉換為乙醇之經濟上可行方法。乙醇是一種重要的商業原料，可用於製造各種工業產品，同時也可用為汽油之燃料添加物。乙醇可以經由脫水處理後成為乙烯，乙烯可被轉換為各種聚合物或小分子為基礎之產品。乙醇傳統上係由一些物價波動愈趨劇烈之原料所製造而成。此意味著天然氣與原油之物價波動，將造成傳統由石油、天然氣、玉米、或其他農產品所製造之乙醇之成本價格亦會隨著波動，因此在油價或農產品價格上漲時，即更加需求由替代來源產製之乙醇。
目前已有研究指出，乙醇可以用氫化醋酸之方式產生，然而大多數的製造過程均呈現許多產業上應用的缺點。例如美國第2,607,807號專利，揭示在700-950巴(bar)之極高壓下，可利用釕催化劑由醋酸產製將近88%之乙醇，若壓力僅為200 bar，則只可產出約40%之乙醇。然而，就產業上運用而言，此等條件顯無法接受，且亦無經濟效益。
近來有其他研究指出，在諸如約40-120 bar之超大氣壓力高壓力下，利用鈷催化劑亦可氫化醋酸以產製乙醇。例如可參照Shuster 等人之美國第4,517,391號專利。然而，該專利案中唯一揭示之實施例，係將反應壓力控制在300 bar左右，此仍然難以實際於產業上運用。此外，由於此方法需要由不少於50%重量百分比之鈷，以及選自由銅、錳、鉬、鉻、及磷酸所成群組之至少一種成分所組成之催化劑，因此該方法不具經濟可行性。即使該專利案揭示了一種以基本惰性催化劑載體支撐催化劑材料之方式，其仍未提供經支撐之金屬催化劑之確切實例。
Kitson 等人之美國第5,149,680號專利描述一種使用鉑族金屬合金催化劑，將羧酸及其酐進行催化性氫化反應而產生醇及/或酯之方法。該催化劑係由至少一種元素週期表第八族之貴金屬與至少一種可與第八族貴金屬混成合金之金屬，以及與包含錸、鎢、或鉬金屬之至少一種之成分混合所構成。即使申請人於該案中聲稱其完成乙醇高選擇性之改良，而超越其先前技術，惟該專利案指出，即使是在最理想之催化條件下，在由醋酸產製乙醇之氫化反應中，仍然會產出3%至9%之烷烴副產品，例如甲烷及乙烷。
Kitson 等人之美國第4,777,303號專利描述一種藉由氫化羧酸產製醇類之方法。該案中使用之催化劑為異相催化劑，包含第一成份(鎢或鉬)以及第二成份(元素週期表第八族之貴金屬)，視需要於擔體上，例如一高表面積石墨化碳。該專利案指出，此種方式僅能以約16%至58%之羧酸之低轉換率而產生選擇率為約73%至87%之醇類及酯類之混合物。此外，該專利案亦未提供任何由醋酸產製乙醇之具體實例。
Kitson 等人之美國第4,804,791號專利描述另一種藉由氫化羧酸產製醇類之方法。於此方法中，係由醋酸產製乙醇，或由丙酸產製丙醇，經由將氣相之醋酸或丙酸之一，在梯升溫度及1至150bar壓力下，在包含(i)元素週期表第八族之貴金屬，及(ii)錸作為必要成分，視需要於擔體(例如一高表面積石墨化碳)上之催化劑存在下，與氫接觸。此方法中，醋酸轉換為乙醇之轉換率為0.6%至69%，而乙醇之選擇性為約6%至97%。
從前述觀之，現有之方法均明顯地不能以理想選擇性產製乙醇，或，目前產業上所用之催化劑，不僅昂貴及/或對乙醇形成無選擇性，且會產生不欲之副產品。
本發明係一種可以工業規模直接由醋酸產製高選擇性及高產量之乙醇之方法。更具體地說，本發明提供一種由醋酸選擇性形成乙醇之方法，包含：在氫之存在下，以合適氫化催化劑氫化醋酸。適用於本發明方法之催化劑，係由在催化劑擔體上之重量百分比約0.1%至20%之鈷，與選自由鈀、鉑、銠、釕、錸、銥、鉻、銅、錫、鉬、鎢、釩及鋅所成群組之至少一種金屬催化劑組合所構成。適合的催化劑擔體包括但不限於氧化矽、氧化鋁、矽酸鈣、氧化矽-氧化鋁、碳、氧化鋯及氧化鈦。
以下參照複數實施例以詳述本發明，該等實施例僅為用以解釋及描述。如後附之申請專利範圍所示之本發明之精神與範圍內之特定實施例之修改，對本領域熟習技藝之人士為顯而易知。
除有特別定義，本發明使用之術語為一般所定義者。除有另行指明，莫耳百分比(mole%或%)以及其他相似用語均指莫耳濃度。除有另行指明，重量百分比(wt%或%)以及其他相似用語均指重量百分比。
「轉換率」以進料流中之醋酸為基準之莫耳百分比表示。醋酸(AcOH)之轉換率以氣相層析(GC)數據使用下列方程式計算：
「選擇率」以經轉換之醋酸為基準之莫耳百分比表示。例如，若醋酸之轉換率為50莫耳%，其中50莫耳%之經轉換之醋酸轉換為乙醇，即稱乙醇選擇率為50%。乙醇(EtOH)之選擇率以氣相層析(GC)數據使用下列方程式計算：
金屬催化劑之重量百分比以金屬重量及金屬與擔體之總乾重為基準。
反應係依照下列化學方程式進行：
依據本發明，可使用不同之配置將醋酸轉換為乙醇，例如若有需求，可使用具有層化固定床之單一反應區。亦可使用隔熱反應器，或具有熱能傳導媒介之殼狀或管狀反應器。如下所述，固定床可為由不同催化劑之顆粒之混合物所組成，或由含有複數催化劑之催化劑顆粒所組成。固定床亦可包含一層由微粒狀物質組成之反應物混合區。包含醋酸、氫、及視需要之惰性載體氣體之反應混合物，會受到壓力而以流體(stream)飼入混合區。藉由壓力差(pressure drop)之方法，該流體接著供給至反應區或反應層中。反應區包括一包含適合之氫化催化劑之催化劑組合物，於此處使醋酸氫化而產製乙醇。依據反應器的類型、生產力需求等條件，可使用任何適合的顆粒尺寸。
即使本領域習知技藝之人可應用已知之各種氫化催化劑，於本發明之氫化醋酸以產製乙醇之方法，然而所用氫化催化劑較佳係包含於適當之催化劑擔體上之重量百分比約0.1%至20%之鈷。如前所述，適用於本發明方法之催化劑更佳係包含於該相同催化劑擔體上之第二及/或第三金屬。適合作為第二及/或第三金屬之金屬，可提及但不限於下列金屬：鈀、鉑、銠、釕、錸、銥、鉻、銅、錫、鉬、鎢、釩、鋅以及上述金屬之混合物。一般而言，於適當擔體上，以鈷與至少一種其他金屬組合而作為氫化催化劑為較佳。因此，鈷與鈀或鉑之一組合為特別佳。類似地，鈷與釕、鉻、或釩組合亦為佳。可與鈷一起使用而作為第三金屬之金屬之實例，包括但不限於上述所列之其他金屬，例如銠、銥、銅、錫、鉬及鋅。
本技術領域中已知之各種催化劑擔體可用於支撐本發明之催化劑。這些擔體之實例包括但不限於沸石、氧化鐵、氧化矽、氧化鋁、氧化鈦、氧化鋯、氧化矽-氧化鋁、氧化鎂、矽酸鈣、碳、石墨以及上述之混合物。較佳之擔體為氧化矽、氧化鋁、矽酸鈣、碳、氧化鋯及氧化鈦。以氧化矽作為本發明方法中之催化劑擔體為較佳。亦重要的是，氧化矽之純度越高為越佳。另一較佳之催化劑擔體則為矽酸鈣。
本發明之另一實施例之較佳催化劑擔體為碳。本技術領域中已知之各種形式的碳，均可作為本發明方法之催化劑擔體。特別佳之碳擔體為石墨化碳(graphitized carbon)，特別是英國第2,136,704號專利中所描述之高表面積石墨化碳。碳較佳是以微粒狀形式存在，如顆粒。碳顆粒之尺寸取決於任一反應器中可接受之壓力差(此決定最小之顆粒尺寸)，以及於該顆粒中之反應物擴散程度(此決定最大之顆粒尺寸)。
適用於本案發明方法之碳催化劑擔體為有孔洞之碳催化劑擔體。為了達到較佳之顆粒尺寸，碳須為孔洞狀以達到較佳之表面積特徵。
包含碳催化劑擔體之催化劑擔體可以從其BET、基面(basal plane)、及棱(edge)表面積加以定性。BET表面積是以Brunauer Emmett and Teller J.Am.Chem.Soc.60,309(1938)一文中提到之氮吸收作用所測定之表面積。基面面積是以Proc.Roy.Soc.A314一文第473-498頁，特別是參考第489頁所提到之方法，以正三十二烷之碳吸收自正庚烷之熱，測定表面積。棱表面積是以Proc.Roy.Soc上述文章，特別是參考第495頁所提及，係以正丁醇之碳吸受自正庚烷之熱，測定表面積。
用於本案發明之較佳碳催化劑擔體，具有至少100平方公尺/克(m2 /g)之BET表面積，至少200平方公尺/克(m2 /g)為較佳，至少300平方公尺/克(m2 /g)為更佳。BET表面積以不大於1000平方公尺/克(m2 /g)為較佳，不大於750平方公尺/克(m2 /g)為更佳。
將含碳之起始材料加熱處理，可產生較佳之碳擔體。起始材料可為親油性石墨，例如用英國第1,168,785號專利所揭示之方法產生，或可為炭黑。
然而，親油性石墨包含為片狀之極細粒型式之碳，因此並非作為催化劑擔體之非常合適之材料。本發明偏好不使用該材料。對於顆粒尺寸同樣過小之炭黑，亦有相同之考量。
較佳之材料為衍生自植物材料如椰炭，或取自泥炭或木炭、或取自碳化聚合物之活性碳。將這些材料經加熱處理後，較佳係具有不小於前述顆粒尺寸，作為較佳之碳擔體。
較佳之起始材料具有下列特性：BET表面積至少為100平方公尺/克(m2 /g)，為500平方公尺/克(m2 /g)以上更佳。
製造具有特定特徵之碳擔體之較佳熱處理製程，依序包含：(1)將碳於惰性氣體中，以900℃至3300℃之溫度加熱，(2)在介於300℃至1200℃之溫度下，將碳氧化，(3)於惰性氣體中，以900℃至3000℃之溫度加熱。
以氧氣(如空氣)為氧化劑時，該氧化步驟介於300℃至600℃之溫度下進行較佳。
在惰性氣體中之加熱期間並未嚴格限制。因為將碳加熱至所須最高溫度之所需時間，已足以使碳產生需要的變化。
氧化步驟必須控制在不足以將碳完全燃燒之程度。用經控制之速率將氣態氧化劑注入，以避免過度氧化，為較佳之進行方式。氣態氧化劑之例子有蒸汽、二氧化碳，以及含有氧氣分子之氣體如空氣。氧化反應之進行最好能使碳重量至少減少10%重量百分比，以至少15%重量百分比為更佳(以經氧化步驟處理之碳重量為基準)。
經氧化步驟處理之碳重量之減少以不大於40%重量百分比為較佳，不大於%25重量百分比為更佳。
氧化劑提供之速率，以所欲重量減少之過程超過至少2個小時為較佳，至少4個小時為更佳。
惰性氣體環境可為由氮或惰性氣體所形成之氣體環境。
如上所述，催化劑擔體上鈷之負載程度(loading level)，通常介於約0.1%至20%之重量百分比之間。催化劑擔體上第二或第三金屬之負載量，在本案發明中並未嚴格限制，可於約0.1%至10%之重量百分比間變化。以擔體重量為基準，金屬負載量以約1%至6%為特別佳。因此，例如於石墨擔體上之鈀之重量百分比為0.5%至2%，且該石墨包含重量百分比為4%至12%之鈷，則為特別佳之催化劑。類似地，若一催化劑包含於高純度氧化矽擔體上之約0.5%至2%重量百分比之鉑，且該擔體包含約4%至12%重量百分比之鈷，亦為較佳之催化劑。
如前所述，可作為與鈷一同使用之第二金屬之其他金屬包含釕、鉻及釩。在各案例下，重量百分比4%至12%之鈷負載量，與重量百分比0.5%至2%之第二金屬(即釕、鉻及釩)，為較佳。若使用第三金屬，其負載之重量百分比亦可介於0.5%至2%之範圍，然而，亦可依照所用之金屬以及催化劑擔體之類型而提高金屬負載量。
可以本領域任何已知方法進行金屬浸漬(impregnation)。典型地，於浸漬前，將該擔體於120℃乾燥並塑形為具有約0.2至0.4 mm之尺寸分佈之顆粒。視需要可將該擔體加壓、碎裂及過篩以達所欲尺寸分佈。可使用任何已知方法，將擔體材料塑形成所欲尺寸分佈。
對於具有低表面積之擔體，例如α-氧化鋁，係添加過量之金屬溶液直到完全濕潤或以過量液體浸漬，以達到預期的金屬負載量。
如上所述，於本發明方法中使用之氫化催化劑至少為雙金屬，並以鈷為主要金屬。一般而言，並未意圖受理論限制，據信其一金屬為促進劑金屬，而另一金屬則為主要金屬。例如，在本發明之方法中，鈷應為主要金屬，作為製備本發明之氫化催化劑。該主要金屬可與促進劑金屬，如鎢、釩、鉬、鉻或鋅，加以組合。然而，應注意的是，有時主要金屬亦可作為促進劑金屬，反之亦然。例如，當鐵為主要金屬時，鎳可被作為促進劑金屬。類似地，鉻可與銅結合而作為主要金屬(亦即以鉻-銅為主要雙金屬)，而可進一步與促進劑金屬如鈰、鎂、或鋅加以組合。
雙金屬催化劑一般以兩步驟浸漬。首先，先加入「促進劑」金屬，再加入「主要」金屬。於各浸漬步驟之後，接著乾燥與鍛燒(calcination)。雙金屬催化劑亦可以共浸漬而製備。對於上述含Cu/Cr之三金屬催化劑之例中，可使用一系列浸漬，以「促進劑」金屬之添加開始。第二浸漬步驟涉及兩種主要金屬(即，Cu及Cr)之共浸漬。例如，於SiO2 上之Cu-Cr-Co可經由硝酸鉻之第一浸漬，再以硝酸銅與硝酸鈷之共浸漬而製備。各浸漬步驟後接著乾燥及煅燒。在大部分案例中，可使用金屬硝酸鹽溶液進行浸漬。然而，亦可使用經鍛燒而能釋出金屬離子之其他各種可溶性鹽類。可使用於浸漬之其他適當金屬鹽類之例，包含金屬氫氧化物、金屬氧化物、金屬醋酸鹽、氧化金屬銨鹽(如六水合七鉬酸銨)、金屬酸(如過錸酸溶液)、金屬草酸鹽及諸如此類等。
因此在本案之一實施例中，係提供一種氫化催化劑，其中，該催化劑擔體為石墨，負載鈷及鈀之雙金屬。在本發明之此一面向，鈷之負載量之重量百分比約為10%，而鈀之重量百分比約為1%。若有需要，鈷之負載量之重量百分比亦可為5%，而鈀之重量百分比為0.5%。
在本案發明之另一實施例中，復提供一種氫化催化劑，其中，該催化劑擔體為高純度氧化矽，負載鈷及鉑之雙金屬。在本案發明之此一面向，鈷之負載量之重量百分比約為10%，而鉑之重量百分比約為1%。又，在本案發明之此一面向，鈷之重量百分比約亦可為5%，而鉑之重量百分比約為0.5%。
一般而言，本發明實施時，可將醋酸以高選擇性轉換為乙醇。乙醇之選擇性通常為高且至少達40%。在較佳之反應條件下，醋酸可以約60%之選擇率轉換為乙醇，更佳為至少80%之選擇率。最佳之乙醇選擇率為至少95%。
在本發明方法之其他面向中，係於恰足以克服穿過該觸媒床所須壓力差之壓力下進行醋酸氫化作用。
該反應可在各種不同的條件下，以氣態或液態進行。在氣相下進行反應較佳。可使用之反應溫度，例如介於約200℃至約300℃之間，以約225℃至約275℃之間更佳。一般而言，對於該反應之壓力並未嚴格限制，低壓(subatmospheric)、大氣壓或高壓(superatmospheric)可被使用。然而在大多數情況下，反應壓力將會介於約1至30絕對大氣壓間，最佳之反應區之壓力範圍介於10至25絕對大氣壓間。
即使為產製一莫耳之乙醇，每一莫耳醋酸需消耗兩莫耳氫，然而加入之醋酸與氫之實際莫耳比例，可於相當大的範圍之間變化，如約自100：1至1：100。然而介於1：20至1：2之莫耳比例較佳。更佳之醋酸對氫之莫耳比例為約1：5。
本發明方法所使用之起始材料可自任何適合之來源取得，包含天然氣、石油、煤、生質能源等等。一般認為醋酸可由羰化甲醇、氧化乙醛、氧化乙烯、有氧發酵、以及無氧發酵等方式產製。由於石油與天然氣愈趨昂貴，因此即需要由替代碳源產製醋酸及其中間物(如甲醇及一氧化碳)之方法。其中最吸引人者為，從可自任何適當之碳源所獲得之人造瓦斯(合成氣)製造出醋酸。Vidalin 之美國第6,232,352號專利案中，其所揭露之內容以參考文獻方式併入此處，教示一種修改甲醇設備為可製造醋酸之方法。藉由修改甲醇設備，可有效減少或消除大量為新醋酸設備而製造一氧化碳所生之資金成本。所有或部分之合成氣體係由甲醇合成迴路所衍生，並送至分離單元以回收一氧化碳與氫，由此回收之一氧化碳與氫用來製造醋酸。除了用來製造醋酸，此方法亦可用來製造本發明可使用之氫。
Steinberg 等人之美國第RE 35,377專利案，其所揭露之內容以參考文獻方式併入此處，提供一將含碳材料如油、煤、天然氣及生質原料轉換，以產製甲醇之方法。該方法包含將固態及/或液態含碳材料加氫氣化(hydrogasification)，以獲得製程氣體，該製程氣體與其他天然氣以蒸汽熱裂解，以形成合成氣。合成氣被轉換為甲醇，而該甲醇可被羰基化而成為醋酸。此方法同樣可製造本發明可使用之氫。同樣參照Grady 等人之美國第5,821,111號專利，其揭示一將廢生質透過氣化作用轉換為合成氣體之方法，以及Kindig 等人之美國第6,685,754號專利亦同，其等所揭露之內容以參考文獻方式併入此處。
醋酸可於反應溫度下被汽化，並於未稀釋之狀態下，或與氮、氬、氦、二氧化碳等惰性載體氣體稀釋後，與氫一同進料。
另一種方式為Scates 等人之美國第6,657,078號專利案，其所揭露之內容以參考文獻方式併入此處，其描述蒸汽形式之醋酸可直接自甲醇羰化單元之閃蒸器(flash vessel)直接收取而作為粗產物。該粗蒸汽產物可直接進料至本發明之反應區而無須考量醋酸及輕餾分或移除水，藉此節省整個處理過程之成本。
接觸及停留之時間亦可廣泛變化，取決於醋酸量、催化劑、反應器、溫度及壓力等因素。在使用固定床以外之催化系統時，一般的接觸時間為自秒的若干分之一至超過數小時，惟至少對於氣相反應而言，較佳之接觸時間介於0.5至100秒間。
一般而言，催化劑置於一固定床反應器，如於延長之管或筒之形狀中，該反應物(典型地為蒸汽形式)，可從此處經過或通過該催化劑。若有需要，亦可使用如流化床或沸騰床(ebullient bed)反應器等其他反應器。在某些例子中，氫化催化劑與惰性材料之結合使用，有利於調節壓力差、流量、熱平衡、或其他催化劑床內之製程參數(包含反應化合物與催化劑顆粒之接觸時間)。
本發明較佳實施例之一係提供一種由醋酸選擇性且直接產製乙醇之製程，包含於升溫狀態下，將含有醋酸及氫之進料流與適當之氫化催化劑接觸，該氫化催化劑包含於合適之催化劑擔體上之重量百分比約1%至15%之鈷，以及於該催化劑擔體上之第二金屬，其中，該第二金屬係選自由鈀、鉑、銅、錫、鉬及鎢所成群組。
在本發明方法之此一實施例中，較佳之氫化催化劑包含重量百分比1%之鈀或鉑與重量百分比約10%之鈷。在本發明方法之此一實施例中，較佳為氫化催化劑係於固定床中層化，且反應係利用1：20至1：2之莫耳比例之醋酸與氫之進料流以氣相進行，溫度介於約225℃至275℃之間，反應區之壓力介於約10至25絕對大氣壓，反應物之接觸時間介於約0.5至100秒間。
下列實施例係描述應用於本發明製程之不同觸媒之製備流程。
實施例A 製備重量百分比10%之鈷及重量百分比1%之鈀於石墨上
將均勻顆粒尺寸分佈約0.2毫米(mm)之經粉末化並過篩之石墨(100公克(g))，於氮氣氛圍下，在烤箱中以120℃乾燥隔夜，再冷卻至室溫。接著加入硝酸鈀(Heraeus)(2.2公克)於蒸餾水(22毫升(ml))之溶液。將所得漿體置於烤箱中，逐漸加熱至110℃(>2小時，10℃/分鐘)而乾燥。將經浸漬之催化劑混合物，接著於500℃(6小時，1℃/分鐘)煅燒。接著於此經煅燒並冷卻之材料中，加入六水合硝酸鈷(49.4克)之蒸餾水(50毫升)溶液。將所得漿體置於烤箱中，逐漸加熱至110℃(>2小時，10℃/分鐘)而乾燥。將此經浸漬之催化劑混合物接著於500℃(6小時，1℃/分鐘)煅燒。
實施例B 製備重量百分比5%之鈷及重量百分比0.5%之鈀於石墨上
將均勻顆粒尺寸分佈約0.2毫米之經粉末化並過篩之石墨(100公克)，於氮氣氛圍下，在烤箱中以120℃乾燥隔夜，再冷卻至室溫。接著加入硝酸鈀(Heraeus)(1.1公克)於蒸餾水(11毫升)之溶液。將所得漿體置於烤箱中，逐漸加熱至110℃(>2小時，10℃/分鐘)而乾燥。將經浸漬之催化劑混合物，接著於500℃(6小時，1℃/分鐘)煅燒。接著於此經煅燒並冷卻之材料中，加入六水合硝酸鈷(24.7公克)之蒸餾水(25毫升)溶液。將所得漿體置於烤箱中，逐漸加熱至110℃(>2小時，10℃/分鐘)而乾燥。將此經浸漬之催化劑混合物，接著於500℃(6小時，1℃/分鐘)煅燒。
實施例C 製備重量百分比10%之鈷及重量百分比1%之鉑於高純度氧化矽上
將均勻顆粒尺寸分佈約0.2毫米之經粉末化並過篩之高純度氧化矽(100公克)，於氮氣氛圍下，在烤箱中以120℃乾燥隔夜，再冷卻至室溫。接著加入硝酸鉑(Chempur)(1.64公克)於蒸餾水(16毫升)之溶液。將所得漿體置於烤箱中，逐漸加熱至110℃(>2小時，10℃/分鐘)而乾燥。將經浸漬之催化劑混合物，接著於500℃(6小時，1℃/分鐘)煅燒。接著於此經煅燒並冷卻之材料中，加入六水合硝酸鈷(49.4公克)之蒸餾水(50毫升)溶液。將所得漿體置於烤箱中，逐漸加熱至110℃(>2小時，10℃/分鐘)而乾燥。將此經浸漬之催化劑混合物，接著於500℃(6小時，1℃/分鐘)煅燒。
實施例D 製備重量百分比10%之鈷及重量百分比1%之鉑於矽酸鈣上
將均勻顆粒尺寸分佈約0.2毫米之經粉末化並過篩之矽酸鈣(100公克)，於氮氣氛圍下，在烤箱中以120℃乾燥隔夜，再冷卻至室溫。接著加入硝酸鉑(Chempur)(1.64克)之蒸餾水(16毫升)溶液。將所得漿體置於烤箱中，逐漸加熱至110℃(>2小時，10℃/分鐘)而乾燥。將經浸漬之催化劑混合物，接著於500℃(6小時，1℃/分鐘)煅燒。接著於此經煅燒並冷卻之材料中，加入六水合硝酸鈷(49.4公克)之蒸餾水(50毫升)溶液中。將所得漿體置於烤箱中，逐漸加熱至110℃(>2小時，10℃/分鐘)而乾燥。將此經浸漬之催化劑混合物，接著於500℃(6小時，1℃/分鐘)煅燒。
實施例E 製備重量百分比10%之鈷及重量百分比1%之鉻於石墨上
將均勻顆粒尺寸分佈約0.2毫米之經粉末化並過篩之石墨(100公克)，於氮氣氛圍下，在烤箱中以120℃乾燥隔夜，再冷卻至室溫。接著加入九水合硝酸鉻溶液(Alfa Aesar)(6.5公克)於蒸餾水(13毫升)之溶液。將所得漿體置於烤箱中，逐漸加熱至110℃(>2小時，10℃/分鐘)而乾燥。將經浸漬之催化劑混合物，接著於500℃(6小時，1℃/分鐘)煅燒。接著於此經煅燒並冷卻之材料中，加入六水合硝酸鈷(49.4公克)之蒸餾水(50毫升)溶液。將所得漿體置於烤箱中，逐漸加熱至110℃(>2小時，10℃/分鐘)而乾燥。將此經浸漬之催化劑混合物，接著於500℃(6小時，1℃/分鐘)煅燒。
生成物之氣相層析(GC)
生成物之分析係以線上GC進行。以配備有一個火焰離子偵測器(FID)與二個熱導偵測器(TCDs)之三管精簡GC，進行反應物與生成物之分析。前管配備有一個FID及一CP-Sil 5(20 m)+WaxFFap(5 m)管柱，並用以定量：
乙醛
乙醇
丙酮
醋酸甲酯
醋酸乙烯酯
醋酸乙酯
醋酸
乙二醇二醋酸酯
乙二醇
亞乙基二醋酸酯
三聚乙醛
中管配備有一個TCD及Porabond Q管柱，用來定量：
二氧化碳
乙烯
乙烷
後管配備有一個TCD與Molsieve 5A管柱，用來定量：
氦
氫
氮
甲烷
一氧化碳
在反應之前，不同成分之停留時間取決於所摻入之個別化合物，而GC會以已知組成物之校正氣體或已知組成物之水溶液進行校正。如此一來即可測定不同成分之反應因素。
實施例1 使用之催化劑為以實施例A步驟所製備之以石墨為擔體之重量百分比10%之鈷及重量百分比1%之鈀
在不銹鋼製、內徑30公釐(mm)且可升溫至經控制的溫度之管狀反應器內，設置50毫升之以石墨為擔體之重量百分比10%之鈷及重量百分比1%之鈀之催化劑。入料後之催化床長度約為70公釐(mm)。
進料液體主要包含醋酸。將反應進料液體汽化後，並與氫及作為載體氣體之氦氣，在250℃之溫度及22巴(bar)之壓力下，以約2500 hr-1 之平均組合之每小時氣體空間速度(GHSV)注入反應器中。如此得到之進料流包含莫耳濃度約4.4%至13.8%之醋酸，以及莫耳濃度約14%至77%之氫。將部分之氣體流出物通過氣相層析以測定流出物之成分。醋酸轉為乙醇之轉換率為18.5%，而乙醇之選擇性為97.5%。
實施例2 使用之催化劑為以實施例B步驟所製備之以石墨為擔體之重量百分比5%之鈷及重量百分比0.5%之鈀
將經汽化之醋酸與氫之進料流以2500hr-1 之平均組合之每小時氣體空間速度(GHSV)，在250℃之溫度及 22bar之壓力下，實質上重複實施例1之步驟。將部分之氣體流出物通過氣相層析以測定流出物之成分。醋酸轉為乙醇之轉換率為20%，而乙醇之選擇性為95% 。
實施例3 使用之催化劑為以實施例C步驟所製備之以高純度氧化矽為擔體之重量百分比10%之鈷及重量百分比1%之鉑
將經汽化之醋酸與氫之進料流以2500hr-1 之平均組合之每小時氣體空間速度(GHSV)，在250℃之溫度及 22bar之壓力下，實質上重複實施例1之步驟。將部分之氣體流出物通過氣相層析以測定流出物之成分。醋酸轉為乙醇之轉換率為71%，而乙醇之選擇性為96% 。
實施例4 使用之催化劑為以實施例D步驟所製備之以矽酸鈣為擔體之重量百分比10%之鈷及重量百分比1%之鉑
將經汽化之醋酸與氫之進料流以2500hr-1 之平均組合之每小時氣體空間速度(GHSV)，在250℃之溫度及 22bar之壓力下，實質上重複實施例1之步驟。將部分之氣體流出物通過氣相層析以測定流出物之成分。醋酸轉為乙醇之轉換率為50%，而乙醇之選擇性為94% 。
實施例5 使用之催化劑為以實施例E步驟所製備之以石墨為擔體之重量百分比10%之鈷及重量百分比1%之鉻
將經汽化之醋酸與氫之進料流以2500hr-1 之平均組合之每小時氣體空間速度(GHSV)，在250℃之溫度及22bar之壓力下，實質上重複實施例1之步驟。將部分之氣體流出物通過氣相層析以測定流出物之成分。醋酸轉為乙醇之轉換率為38%，而乙醇之選擇性為96%。
雖本發明以特定例子進行說明，惟在本案發明之精神與範圍之內，對於該等例子進行修改，將會被習知技藝之人視為顯而易知。於前述內容中，本技術領域中之相關知識以及上述於先前技術及發明內容中提及之參考文獻，已以參考文獻之方式併入本案，因此不需要進一步之描述。

Claims (21)

  1. 一種由醋酸選擇性及直接形成乙醇之方法，包括：將含有醋酸與氫之進料流，於升溫下與 適合之氫化催化劑接觸，該催化劑係由於一合適催化劑擔體上之重量百分比0.1%至20%之鈷以及選自由鈀、鉑、及鉻所成群組之第二金屬所組成；其中，該反 應之溫度介於200℃至300℃之間，且該反應之壓力介於10至25絕對大氣壓之間。
  2. 如申請專利範圍第1項之方法，其中該催化劑擔體係選自由氧化矽、氧化鋁、矽酸鈣、碳、氧化鋯及 氧化鈦所成群組。
  3. 如申請專利範圍第2項之方法，其中該催化劑擔體為氧化矽。
  4. 如申請專利範圍第3項之方法，其中該催化劑擔體為高純度氧化矽。
  5. 如申請專利範圍第2項之方法，其中該催化劑擔體為矽酸鈣。
  6. 如申請專利範圍第2項之方法，其中該催化劑擔體為碳。
  7. 如申請專利範圍第6項之方法，其中該催化劑擔體為石墨。
  8. 如申請專利範圍第7項之方法，其中該催化劑擔體為高表面積石墨化碳。
  9. 如申請專利範圍第1項之方法，其中該第二金屬為鈀。
  10. 如申請專利範圍第9項之方法，其中鈷之負載量為10%重量百分比，鈀之負載量為1%重量百分比， 且催化劑擔體為石墨。
  11. 如申請專利範圍第1項之方法，其中該第二金屬為鉑。
  12. 如申請專利範圍第11項之方法，其中鈷之負載量為10%重量百分比，鉑之負載量為1%重量百分比， 且催化劑擔體為高純度氧化矽。
  13. 如申請專利範圍第1項之方法，其中以消耗之醋酸為基準之乙醇選擇性為至少40%。
  14. 如申請專利範圍第1項之方法，其中以消耗之醋酸為基準之乙醇選擇性為至少60%。
  15. 如申請專利範圍第1項之方法，其中以消耗之醋酸為基準之乙醇選擇性為至少80%。
  16. 如申請專利範圍第1項之方法，其中以消耗之醋酸為基準之乙醇選擇性為至少95%。
  17. 如申請專利範圍第1項之方法，其中氫化為乙醇之反應係於氣相中進行，且在200℃至300℃間之溫度 下。
  18. 如申請專利範圍第17項之方法，其中氫化為乙醇之反應係於氣相中進行，且在225℃至275℃間之溫 度下。
  19. 如申請專利範圍第17項之方法，其中該進料流包含惰性載體氣體。
  20. 如申請專利範圍第17項之方法，其中該反應物由莫耳比例100：1至1：100之醋酸與氫所組成，反應 區之溫度介於200℃至300℃之間，且反應區之壓力介於10至25絕對大氣壓之間。
  21. 如申請專利範圍第17項之方法，其中該反應物由莫耳比例約1：20至1：2之醋酸與氫組成，反應區之 溫度介於225℃至275℃之間，且反應區之壓力介於10至25絕對大氣壓之間。
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US7608744B1 (en) 2009-10-27
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CN102442883A (zh) 2012-05-09
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JP5756420B2 (ja) 2015-07-29
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US20130184148A1 (en) 2013-07-18
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