TW201315712A - 藉由含鎢的觸媒氫化烷酸類之製程 - Google Patents
藉由含鎢的觸媒氫化烷酸類之製程 Download PDFInfo
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- TW201315712A TW201315712A TW101130756A TW101130756A TW201315712A TW 201315712 A TW201315712 A TW 201315712A TW 101130756 A TW101130756 A TW 101130756A TW 101130756 A TW101130756 A TW 101130756A TW 201315712 A TW201315712 A TW 201315712A
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- 239000012535 impurity Substances 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 description 1
- 229940011051 isopropyl acetate Drugs 0.000 description 1
- GWYFCOCPABKNJV-UHFFFAOYSA-N isovaleric acid Chemical compound CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 description 1
- 239000002655 kraft paper Substances 0.000 description 1
- 229940039696 lactobacillus Drugs 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 229930013686 lignan Natural products 0.000 description 1
- 150000005692 lignans Chemical class 0.000 description 1
- 235000009408 lignans Nutrition 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 229910052680 mordenite Inorganic materials 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- PZKNFJIOIKQCPA-UHFFFAOYSA-N oxalic acid palladium Chemical compound [Pd].OC(=O)C(O)=O PZKNFJIOIKQCPA-UHFFFAOYSA-N 0.000 description 1
- HNKLPNDFOVJIFG-UHFFFAOYSA-N oxalic acid;platinum Chemical compound [Pt].OC(=O)C(O)=O HNKLPNDFOVJIFG-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 1
- NFOHLBHARAZXFQ-UHFFFAOYSA-L platinum(2+);dihydroxide Chemical compound O[Pt]O NFOHLBHARAZXFQ-UHFFFAOYSA-L 0.000 description 1
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 description 1
- NQKOIXJWXIADLA-UHFFFAOYSA-N platinum(2+);tetranitrate Chemical group [Pt+2].[Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O NQKOIXJWXIADLA-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000002459 porosimetry Methods 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 239000008262 pumice Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- PORYSJKNFJQKJO-UHFFFAOYSA-K sodium;platinum(2+);trichloride Chemical compound [Na+].[Cl-].[Cl-].[Cl-].[Pt+2] PORYSJKNFJQKJO-UHFFFAOYSA-K 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- AFCAKJKUYFLYFK-UHFFFAOYSA-N tetrabutyltin Chemical compound CCCC[Sn](CCCC)(CCCC)CCCC AFCAKJKUYFLYFK-UHFFFAOYSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 230000035899 viability Effects 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
- 235000020234 walnut Nutrition 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 description 1
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- 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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Abstract
一種在觸媒存在下氫化烷酸類之製程,該觸媒包括擔體、一種或多種金屬、氧化鎢及至少一種鹼土金屬氧化物或偏矽酸鹽。該至少一種鹼土金屬氧化物或偏矽酸鹽相對於氧化鎢之莫耳比基於金屬為自1:3至5:1。
Description
本申請案優先權主張基於2011年10月6日申請之美國專利申請號13/267,149,其全文及揭示併入本文供參考。
本發明大體上係有關氫化烷酸類尤其是乙酸而形成醇類之製程以及該製程中使用之新穎觸媒。
對於將乙酸轉化成乙醇之經濟效益製程長期以來有其需求,而乙醇可就此使用或隨後被轉化成重要的常用料源之乙烯,因乙烯可被轉化成乙酸乙烯酯及/或乙酸乙酯或任何廣泛種類之其他化學產品。例如,乙烯亦可轉化成多種聚合物及單體產品。天然氣及原油價格浮動導致習知製得之石油或天然氣來源之乙烯之成本浮動,使得當石油價格變高時,對於乙烯之替代來源有較大需求。
使烷酸類及其他含羰基化合物之催化製程已廣被被研究,且觸媒、擔體(supports)及操作條件之各種組合已述於文獻中。於金屬氧化物上還原各種羧酸類已由T.Yokoyama於”經由異質催化之精密化學:羧酸及衍生物(Fine chemicals through heterogeneous catalysis.Carboxylic acids and derivatives)”,第8.3.1章中加以評論,其概述某些用於各種羧酸類之氫化觸媒之發展成效(Yokoyama,T.;Setoyama,T.“Carboxylic acids and derivatives.”於:“Fine chemicals through heterogeneous catalysis.”2001,370-379)。
由M.A.Vannice等人之系列研究中關注到乙酸於各種異質觸媒上之轉化率(Rachmady W.;Vannice,M.A.;J.Catal.(2002)Vol.207,pg.317-330)。於經擔持(supported)及未經擔持之鐵上以氫(H2)蒸汽相還原乙酸已報導於個別研究中(Rachmady,W.;Vannice,M.A.J.Catal.(2002)Vol.208,158-169頁)。關於觸媒表面物種及有機中間
物之進一步資訊則敘述於Rachmady,W.;Vannice,M.A.,J.Catal.(2002)Vol.208,170-179頁中。進而研究在經擔持之Pt-Fe觸媒族上進行蒸汽相乙酸氫化反應,見於Rachmady,W.;Vannice,M.A.J.Catal.(2002)Vol.209,pg.87-98及Rachmady,W.;Vannice,M.A.J.Catal.(2000)Vol.192,322-334頁。
有關不飽和醛類之選擇性氫化之各種相關刊物見於Djerboua,F.;Benachour,D.;Touroude,R.Applied Catalysis A:General 2005,282,123-133.;Liberkova,K.;Tourounde,R.J.Mol.Catal.2002,180,221-230.;Rodrigues,E.L.;Bueno,J.M.C.Applied Catalysis A:General 2004,257,210-211.;Ammari,F.;Lamotte,J.;Touroude,R.J.Catal.2004,221,32-42;Ammari,F.;Milone,C.;Touroude,R.J.Catal.2005,235,1-9.;Consonni,M.;Jokic,D.;Murzin,D.Y.;Touroude,R.J.Catal.1999,188,165-175.;Nitta,Y.;Ueno,K.;Imanaka,T.;Applied Catal.1989,56,9-22。
於將巴豆醛(crotonaldehyde)選擇性氫化成不飽和醇中對含鈷、鉑及錫之觸媒之活性及選擇性報導之研究見於R.Touroude等人(Djerboua,F.;Benachour,D.;Touroude,R.Applied Catalysis A:General 2005,282,123-133以及Liberkova,K.;Tourounde,R.;J.Mol.Catal.2002,180,221-230)以及K.Lazar等人(Lazar,K.;Rhodes,W.D.;Borbath,I.;Hegedues,M.;Margitfalvi,1.L.Hyperfine Interactions 2002,1391140,87-96.)。
M.Santiago等人(Santiago,M.A.N.;Sanchez-Castillo,M.A.;Cortright,R.D.;Dumesic,1.A.J.Catal.2000,193,16-28.)探討微熱量熱法(microcalorimetric)、紅外線分光及反應動力學測量與量子-化學計算組合。
對於乙酸氫化之觸媒活性亦報導有含錸及釕之異質系統(Ryashentseva,M.A.;Minachev,K.M.;Buiychev,B.M.;Ishchenko,V.M.Bull.Acad Sci.USSR1988,2436-2439)。
頒與Kitson等人之美國專利號5,149,680描述羧酸類及其酸酐類
催化氫化成醇類及/或酯之製程,係利用與包括至少一種金屬錸、鎢或鉬之組份混合之鉑族金屬合金觸媒。頒與Kitson等人之美國專利號4,777,303描述藉由使羧酸類氫化製造醇類之製程。頒與Kitson等人之美國專利號4,804,791描述藉由使羧酸類氫化而製造醇類之另一製程。亦參見美國專利號5,061,671、4,990,655、4,985,572及4,826,795。
Malinowski等人(Bull.Soc.Chim.Belg.(1985),94(2),93-5)探討在擔體材料如氧化矽(SiO2)或氧化鈦(TiO2)上異質化之低價鈦上之乙酸催化反應。
雙金屬釕-錫/氧化矽觸媒已報導係藉由使四丁基錫與擔持在二氧化矽上之二氧化釕反應而製備(Loessard et al.,Studies in Surface Science and Catalysis(1989),Volume Date 1988,48(Struct.React.Surf.),591-600)。
乙酸之催化還原亦已由例如Hindermann等人(Hindermann et al.,J.Chem.Res.,Synopses(1980),(11),373)探討,揭示乙酸在鐵及鹼促進之鐵上之催化還原。
需要對氫化觸媒進行改良。
第一具體例中,本發明有關一種製造醇類之製程,包括:使包括氫及呈蒸汽相烷酸之氣態流通過氫化觸媒上,而產生醇類。該氫化觸媒包括擔體及一種或多種金屬,其中氫化觸媒進而包括:(a)氧化鎢,及(b)至少一種鹼土金屬氧化物、至少一種鹼土金屬偏矽酸鹽或其混合物。一具體例中,組份(b)相對於組份(a)之莫耳比基於金屬為自1:3至5:1。該擔體可選自由氧化矽、氧化矽/氧化鋁、偏矽酸鈣、裂解氧化矽、高純度氧化矽及其混合物所組成之群組。該擔體存在量可自25重量%至99重量%。該一種或多種金屬可選自由錫、銠、鉑、鈀、鈷、銅、鐵、鎳、鋅、鉻、錸、鉬及釕所組成之群組。較好,該金屬包括錫及另一金屬係選自由銠、鉑、鈀、鈷、銅、鐵、鎳、鋅、鉻、錸、鉬及釕所組成之群組。該一種或多種金屬之總重為0.1至25
重量%。該氧化鎢之存在量可自1至25重量%。該至少一種氧化物或偏矽酸鹽之鹼土金屬係選自由鎂、鈣及其混合物所組成之群組。有些具體例中,該鹼土金屬偏矽酸鹽係偏矽酸鈣。該烷酸係由甲醇及一氧化碳所形成,其中該甲醇、該一氧化碳及用於該氫化步驟之氫之至少一種係衍生自合成氣,且其中該合成氣係衍生自碳源係選自由天然氣、油、石油、煤炭、生質材料及其組合所組成之群組。該氣態流可在125℃至350℃之溫度通過該氫化觸媒上。氫相對於烷酸之莫耳比大於2:1。
第二具體例中,本發明係有關一種製造醇類之製程,包括:使包括氫及呈蒸汽相烷酸之氣態流通過氫化觸媒上,而產生醇類,其中該氫化觸媒包括(a)擔體,(b)錫,(c)一種或多種金屬,係選自由銠、鉑、鈀、鈷、銅、鐵、鎳、鋅、鉻、錸、鉬及釕所組成之群組,(d)氧化鎢,(e)至少一種鹼土金屬氧化物及鹼土金屬偏矽酸鹽。一具體例中,組份(e)相對於組份(d)之莫耳比基於金屬為自1:3至5:1。該擔體可選自由氧化矽、氧化矽/氧化鋁、偏矽酸鈣、裂解氧化矽、高純度氧化矽及其混合物所組成之群組。該擔體存在量可自25重量%至99重量%。該一種或多種金屬之總重為0.1至25重量%。該氧化鎢之存在量可自1至25重量%。該至少一種氧化物或偏矽酸鹽之鹼土金屬係選自由鎂、鈣及其混合物所組成之群組。有些具體例中,該鹼土金屬偏矽酸鹽係偏矽酸鈣。
第三具體例中,本發明有關一種製造醇類之氫化觸媒,該氫化觸媒包括擔體及一種或多種金屬,其中該氫化觸媒進而包括:(a)氧化鎢,(b)至少一種鹼土金屬氧化物、至少一種鹼土金屬偏矽酸鹽或其混合物,且其中組份(b)相對於組份(a)之莫耳比基於金屬為自1:3至5:1。該擔體可選自由氧化矽、氧化矽/氧化鋁、偏矽酸鈣、裂解氧化矽、高純度氧化矽及其混合物所組成之群組。該擔體存在量可自25重量%至99重量%。該一種或多種金屬可選自由錫、銠、鉑、鈀、鈷、銅、鐵、鎳、鋅、鉻、錸、鉬及釕所組成之群組。該一種或多種金屬之總重為0.1至25重量%。該至少一種氧化物或偏矽酸鹽之鹼土
金屬係選自由鎂、鈣及其混合物所組成之群組。有些具體例中,該鹼土金屬偏矽酸鹽係偏矽酸鈣。
第四具體例中,本發明係有關一種製造醇類之氫化觸媒,該氫化觸媒包括(a)擔體,(b)錫,(c)一種或多種金屬,係選自由銠、鉑、鈀、鈷、銅、鐵、鎳、鋅、鉻、錸、鉬及釕所組成之群組,(d)氧化鎢,(e)至少一種鹼土金屬氧化物及鹼土金屬偏矽酸鹽,且其中組份(e)相對於組份(d)之莫耳比基於金屬為自1:3至5:1。該擔體可選自由氧化矽、氧化矽/氧化鋁、偏矽酸鈣、裂解氧化矽、高純度氧化矽及其混合物所組成之群組。該擔體存在量可自25重量%至99重量%。該一種或多種金屬之總重為0.1至25重量%。該氧化鎢之存在量可自1至25重量%。該至少一種氧化物或偏矽酸鹽之鹼土金屬係選自由鎂、鈣及其混合物所組成之群組。有些具體例中,該鹼土金屬偏矽酸鹽係偏矽酸鈣。
本發明有關藉由在觸媒存在下使烷酸例如乙酸氫化之製造乙醇之製程。該製程中使用之觸媒包括在擔體上之一種或多種金屬,且該擔體進而包括氧化鎢(WO3)及至少一種鹼土金屬氧化物或偏矽酸鹽。本發明已發現至少一種鹼土金屬相對於鎢之莫耳比基於金屬較好為1:3至5:1,如自1:2至3:1且較好約1:1至2:1。較佳具體例中,該鹼土金屬偏矽酸鹽為偏矽酸鈣(CaSiO3)且鈣相對於鎢之莫耳比基於金屬係1:3至5:1,如自1:2至3:1,且較好約1:1。一具體例中,該莫耳比可提供增進之觸媒活性,導致更高之酸轉化率及較高之總乙醇產率。
本發明亦有關氫化製程中所用之觸媒及製造該觸媒之製程。一尤佳之反應係自乙酸製造乙醇。該氫化反應可表示如下。
HOAc+2 H2 → EtOH+H2O
意外且不預期地發現本發明之觸媒當使用於烷酸類氫化時提供對乙醇之高選擇率。本發明具體例可有利地用於工業用途以於經濟可行
規模製造乙醇。
本發明之觸媒包括一種或多種金屬。該一種或多種金屬可選自由錫、銠、鉑、鈀、鈷、銅、鐵、鎳、鋅、鉻、錸、鉬及釕所組成之群組。較好,該一種或多種金屬至少包括錫,及另一金屬,可選自由銠、鉑、鈀、鈷、銅、鐵、鎳、鋅、鉻、錸、鉬及釕所組成之群組。觸媒中存在之所有擔持金屬之總重較好為0.1至25重量%,如自0.1至15重量%,或自0.1重量%至10重量%。金屬之個別量為可變動。例如錫量可存在自0.1至20重量%之量,如自0.1至10重量%,或自0.1至5重量%。
基於本發明說明書之目的,除非另有說明,否則重量百分比係基於包含金屬及擔體之觸媒總重。觸媒中之金屬可以一種或多種金屬氧化物形式存在。基於決定觸媒中金屬之重量百分比之目的,忽略了鍵結於該金屬之氧重量。
主要視如何製造觸媒而定,本發明觸媒之金屬可分散於整個擔體中、塗佈在該擔體外表面上(蛋殼外形)或塗飾在擔體表面上。
本發明之觸媒可為任何適宜擔體。一具體例中,該擔體可為矽質擔體係選自由氧化矽、氧化矽/氧化鋁、偏矽酸鈣、裂解氧化矽、高純度氧化矽及其混合物所組成之群組。較佳具體例中,該擔體存在量係自25重量%至99重量%,例如自30重量%至97重量%或自35重量%至95重量%。
矽質擔體材料例如氧化矽之表面積較好至少約50米2/克(m2/g),如至少約100 m2/g、至少約150 m2/g、至少約200 m2/g或最好至少約250 m2/g。以範圍表示時,該矽質擔體材料較好具有自50至600 m2/g之表面積,例如自100至500 m2/g或自100至300 m2/g。整個申請案中使用之高表面積氧化矽表示具有至少約250 m2/g之表面積之氧化矽。基於本說明書目的,表面積表示BET氮表面積,意指藉由SATM D6556-04所測定之表面積,該內容併入本文供參考。
該矽質擔體材料亦較好具有藉壓汞儀(mercury intrusion porosimetry)所測定之自5至100nm(奈米)之平均孔徑,如自5至
30nm、自5至25nm或自約5至10nm,及具有藉壓孔儀所測定之自0.5至2.0公分3/克(cm3/g)之平均孔體積,如自0.7至1.5公分3/克或自約0.8至1.3公分3/克。
該擔體材料之形態可廣泛變化且因此所得之觸媒組成物之形態亦可廣泛變化。有些例舉具體例中,該擔體材料及/或觸媒組成物之形態可為顆粒(pellets)、擠出物、球體、噴霧乾燥微球體、環體、五環體、三葉形、四葉形、多葉形或片狀,但以圓柱形顆粒較佳。較好,該矽質擔體材料具有使得填充密度為0.1至1.0克/公分3(g/cm3),如0.2至0.9克/公分3或自0.5至0.8克/公分3之形態。以尺寸表示時,該氧化矽擔體材料較好具有自0.01至1.0公分(cm),如自0.01至0.5cm或自0.2至0.4cm之平均粒徑,意指球體顆粒之直徑或對非球體顆粒而言為相當於球體直徑。由於位於該改質擔體上或其內之一種或多種金屬通常尺寸極小,故其實質上對於總體觸媒顆粒之尺寸應不會有影響。因此,上述粒徑通常應用於該改質擔體以及最終觸媒顆粒兩者之尺寸。
較佳之氧化矽擔體材料為獲自Saint-Gobain NorPro之SS61138高表面積(HSA)氧化矽觸媒載體。Saint-Gobain NorPro SS61138氧化矽含有約95重量%之高表面積氧化矽;表面積約250m2/g;中值孔徑為約12nm;以壓汞儀測量之平均孔體積約1.0cm3/g;及填充密度約0.352g/cm3。
較佳之氧化矽/氧化鋁擔體材料為KA-160(Sud Chemie)氧化矽球體,其具有約5mm之公稱直徑,約0.562g/ml之密度,約0.583克H2O/克擔體之吸收率,約160至175 m2/g之表面積,及約0.68ml/g之孔體積。
在擔體上,可有氧化鎢及至少一種鹼土金屬氧化物或偏矽酸鹽,作為擔體改質劑以莫耳比計。較佳具體例中,該擔體改質劑之總重存在量,基於觸媒總重,係自0.1重量%至50重量%,如自0.2重量%至25重量%,自0.5重量%至20重量%,或自1重量%至18重量%。一具體例中,該氧化鎢改質劑(modifiers)存在量,基於觸媒總重,可
為1重量%至25重量%,如自3重量%至20重量%,或自5重量%至15重量%。較佳具體例中,至少一種鹼土金屬氧化物或偏矽酸鹽存在量,基於觸媒總重,可為0.2重量%至25重量%,如自0.5重量%至12重量%,或自1重量%至8重量%。
擔體改質劑可調整該擔體之酸性。例如,擔體改質劑上之酸部位(acid sites)如布忍斯特酸(Bronsted acid)部位(sites)可藉由擔體改質劑調整至有利於乙酸氫化期間對乙醇之選擇率。該擔體材料之酸性可藉由減少擔體材料上之布忍斯特酸之數目或減低其供給性而調整。該擔體材料亦可藉由具有該擔體改質劑而調整並改變該擔體材料之pKa。除非說明書另有指明,否則其上之酸部位之表面酸性或數目可藉由F.Delannay,Ed.,“Characterization of Heterogeneous Catalysts”;Chapter III:Measurement of Acidity of Surfaces,p.370-404;Marcel Dekker,Inc.,N.Y.1984所描述之技術測定,其全文併入本文供參考。現已發現除了該金屬前驅物及所用之製備條件以外,金屬-擔體相互作用對於乙醇之選擇率亦具有強烈影響。尤其,使用可調整擔體酸性之經改質擔體製造較不具酸性或較具鹼性之擔體已意外且不可預期地證明相較於其他氫化產物更有利於形成乙醇。
如熟知本技藝者所理解,擔體及擔體改質劑係選擇為觸媒系統在用以形成乙醇之製程條件下具適當活性、選擇性且強固(robust)。
例如此等鹼性改質劑可選自由鹼土金屬氧化物、鹼土金屬偏矽酸鹽及其混合物所組成之群組。較好,該鹼土金屬係選自由鎂、鈣及其混合物所組成之群組。較好該擔體改質劑為偏矽酸鈣(CaSiO3)。若擔體改質劑包括偏矽酸鈣,則較好該偏矽酸鈣之至少一部份為結晶型。
據此,不欲受理論限制,藉由併入具有中和擔體表面上存在之酸部位之效果或具有使該表面熱穩定之效果之非揮發性擔體改質劑而使本發明觸媒之氧化性擔體材料之改質及穩定化作用,使得該觸媒可達到對乙醇選擇性之所需改良、延長觸媒壽命或兩者。通常,以其最穩定價數狀態之氧化物為主之擔體改質劑將具有低蒸汽壓且因此具有低揮發性或反而為非揮發。據此,較佳該擔體改質劑所提供之量係以足
以(i)中和擔體材料表面上存在之酸性部位;(ii)賦予在氫化溫度下之對形狀改變之衝擊抗性;或(iii)兩者。不欲受理論限制,賦予對形狀改變之衝擊抗性表示賦予對於例如燒結、晶粒生長、晶界遷移、缺陷及錯位之遷移、塑料變形及/或其他溫度誘發之微結構改變之衝擊抗性。
本發明之觸媒本質上為顆粒觸媒,其並非類似於車用觸媒及柴油燃燒煙道裝置之飽含單塊載體上之塗層,本發明之觸媒較好係形成為粒子,有時亦稱為珠粒或顆粒,且具有各種任何形態且係藉由將大量知該等成型觸媒置於反應器中而將觸媒金屬設於該反應區中。普遍碰到之形狀包含任意截面呈廣義圓柱體(generalized cylinder)之擠出物,本質上界定出該擠出物表面之產生器為平行線。如上所述。可使用包含顆粒、擠出物、球體、噴霧乾燥微球體、環體、五環體、三葉形、四葉形極多葉形之任何習用顆粒形狀,但以圓柱形顆粒較佳。典型上,該形狀係基於可感知之蒸汽相與觸媒劑有效接觸能力而實驗性地選擇。
本發明觸媒之一優點為製造乙醇之觸媒穩定性或活性。據此,可理解本發明之觸媒完全可用於氫化乙酸之商業規模工業應用,尤其是製造乙醇。尤其,其可達到使得觸媒活性將具有每使用觸媒100小時小於6%之產率衰減,如每100小時少於3%或每100小時少於1.5%之產率衰減的穩定度。較好,產率衰減率係在觸媒達到穩定態條件時測定。
一具體例中,當觸媒擔體包括高純度氧化矽,且以偏矽酸鈣作為擔體改質劑時,該觸媒活性在乙酸蒸汽存在下在125℃至350℃之溫度下,於大於2500小時-1(hr-1)之空間速度下之商業活用操作中,可使觸媒之生產量及選擇性延長或穩定超過1週、超過兩週或甚至超過數個月。
本發明之觸媒組成物較好經由金屬浸漬該改質擔體而形成,但亦可使用其他製程如化學氣相沉積。在金屬浸漬之前,一般需經由例如以擔體改質劑浸漬該擔體材料之步驟形成該改質擔體。可使用擔體改
質劑之前驅物如乙酸塩或硝酸鹽。較好,該前驅物為可溶。於一方面中,將該擔體改質劑如WO3及/或CaSiO3添加至擔體材料如SiO2中。例如,可藉由將固體擔體改質劑添加至去離子水中,接著於其中添加膠體擔體材料而形成該擔體改質劑之水性懸浮液。所得混合物可經攪拌並添加至額外擔體材料中,使用例如其中將該擔體改質劑添加至具有與該擔體改質劑溶液之體積相同之孔體積之擔體材料中之初期濕潤技術(incipient wetness techniques)。接著虹吸作用將該擔體材料拉入該擔體材料之孔隙中。接著可藉由乾燥及煅燒該改質擔體以驅除擔體改質劑溶液內之水及任何揮發性組份並將該擔體改質劑沉積在擔體材料上。可在例如50℃至300℃,如100℃至200℃或約120℃之溫度進行乾燥,視情況歷時1至24小時,如3至15小時或6至12小時。形成後,改質擔體可成型為具有所需尺寸分佈之顆粒,如形成具有平均粒徑在0.2至0.4公分之顆粒。該擔體可經擠出、粒片化、製錠、壓製、粉碎或過篩至所需之尺寸分佈。可利用將擔體材料成型為所需尺寸分佈之任何已知方法。可在例如250℃至800℃,如300℃至700℃或約500℃之溫度進行成型改質擔體之煅燒,視情況歷時1至12小時,如2至10小時、4至8小時或約6小時。
於製備該觸媒之較佳方法中,將金屬浸漬於該改質擔體上。金屬浸漬步驟中較好使用第一金屬之前驅物(第一金屬前驅物),如包含相關第一金屬之水可溶的化合物或水可分散的化合物/錯合物。視所用金屬前驅物而定,較好使用溶劑如水、冰醋酸或有機溶劑。亦較好自第二金屬前驅物將第二金屬浸漬於該改質擔體中。若需要,則亦可將第三金屬或第三金屬前驅物浸漬於該改質擔體中。
浸漬可藉由將第一金屬前驅物及/或第二金屬前驅物之一或兩者及/或額外金屬前驅物,較好以懸浮液或溶液添加,視情況為逐滴,至乾燥改質擔體中。接著可加熱所得混合物如視情況在真空下加熱,以移除溶劑。可進行額外乾燥、煅燒,視需要進行漸增加熱以形成最終觸媒組成物。加熱及/或應用真空後,該金屬前驅物之金屬較好分解成其元素(或氧化物)態。有些例中,可不進行液體載體如水之完全移
除,直至觸媒使用時才進行煅燒如接受操作期間所遭遇之高溫。煅燒步驟期間或至少在觸媒使用最初期期間,將此等化合物轉化成金屬之催化活性態或其催化氧化物態。
第一金屬及第二金屬(及視情況之額外金屬)浸漬於改質擔體中可同時(共同浸漬)或依序進行。同時浸漬中,將第一金屬前驅物及第二金屬前驅物(及視情況之額外金屬前驅物)混合在一起並一起添加至該改質擔體中,接著乾燥並煅燒而形成最終觸媒組成物。以同時浸漬時,在兩種前驅物與所需溶劑如水為不溶混之情況下,可能需要利用分散劑、界面活性劑或溶解劑如草酸銨,以促進該第一金屬前驅物及第二金屬前驅物之分散或溶解。
在依序浸漬中,先將第一金屬前驅物添加於該改質擔體中,接著乾燥及煅燒,且接著以第二金屬前驅物浸漬所得材料接著進行額外乾燥及煅燒步驟而形成最終觸媒組成物。可與第一及/或第二金屬前驅物一起添加額外金屬前驅物(如第三金屬前驅物)或進行另外之第三浸漬步驟,接著乾燥及煅燒。當然,若需要可組合使用依序浸漬及同時浸漬。
適宜金屬前驅物包含例如金屬鹵化物、胺溶解之金屬氫氧化物、金屬硝酸鹽或金屬草酸鹽。例如對於鉑前驅物及鈀前驅物之適宜化合物包含氯鉑酸、氯鉑酸銨、胺溶解之氫氧化鉑、硝酸鉑、四硝酸鉑銨、氯化鉑、草酸鉑、硝酸鈀、四硝酸鈀銨、氯化鈀、草酸鈀、氯化鈉鈀及氯化鈉鉑。通常,鑒於經濟及環境層面兩者而言,較好為鉑之可溶性化合物之水溶液。一具體例中,第一金屬前驅物並非金屬鹵化物且實質上不含金屬鹵化物。不欲受理論限制,使該等非(金屬鹵化物)前驅物據信可增加對於乙醇之選擇性。對於鉑之尤佳前驅物為硝酸鉑銨Pt(NH3)4(NO4)2。
一方面中,將該”促進劑”金屬或金屬前驅物先添加至該改質擔體中,接著添加”主體”或”主要”金屬或金屬前驅物。當然添加順序亦可顛倒。促進劑金屬之例舉前驅物包含金屬鹵化物、胺溶解之金屬氫氧化物、金屬硝酸鹽或金屬草酸鹽。如上所述,於依序具體例中,各浸
漬步驟後較好進行乾燥及煅燒。在如上述之經促進之雙金屬觸媒之例中,可使用依序浸漬,開始先添加促進劑金屬,接著進行涉及共同浸漬一種或多種金屬例如Pt及Sn之第二浸漬步驟。
舉例而言,PtSn/WO3/CaSiO3擔持在SiO2上,可藉由先將WO3及CaSiO3浸漬於SiO2上,接著以Pt(NH3)4(NO3)2及Sn(AcO)2共同浸漬而製備。再度,各浸漬步驟之後可進行乾燥及煅燒步驟。於大多數例中,該浸漬可使用金屬硝酸鹽溶液進行。然而,亦可使用煅燒後會釋出金屬離子之各種其他可溶性鹽。用於浸漬之其他金屬鹽之實例包含金屬酸如過錸酸(perrhenic acid)溶液、金屬草酸鹽等。在其中欲製造實質上純的乙醇之該等例中,通常較好避免使用鉑族金屬之鹵化前驅物,而代之使用以含氮胺及/或硝酸鹽為主之前驅物。
饋入與本發明製程連用之主要反應器中之原料乙酸及氫可衍生自任何適宜來源,包含天然氣、石油、媒碳、生質材料等。例如,乙酸可經由甲醇羰化、乙醛氧化、乙烷氧化、氧化性發酵及厭氣發酵而製得。適於製造乙酸之甲醇羰化製程述於美國專利號7,208,624;7,115,772;7,005,541;6,657,078;6,627,770;6,143,930;5,599,976;5,144,068;5,026,908;5,001,259;及4,994,608,其等之全部揭示併入本文供參考。視情況,乙醇製造可與該甲醇羰化製程整合在一起。
由於石油及天然氣價格浮動而變貴或變便宜,故自替代碳源製造乙酸及中間物如甲醇及一氧化碳之方法逐漸受到矚目。尤其,當石油相當昂貴時,自衍生自更多可用碳源之合成氣體(”合成氣”)製造乙酸將變得有利。例如美國專利號6,232,352,其全文併入本文供參考,教示用以改良製造乙酸之甲醇工廠之方法。藉由改良甲醇工廠,對於新的乙酸工廠與一氧化碳產生相關之較大成本可顯著降低或大為省去。所有或部分合成氣係衍生自甲醇合成路徑並供應至分離器單元以回收一氧化碳,其接著被用以製造乙酸。以類似方式,可自合成氣供應氫化步驟之氫。
有些具體例中,上述乙酸氫化製程之有些或所有原料可部份或全部衍生自合成氣。例如,乙酸可自甲醇及一氧化碳形成,兩者均衍生
自合成氣。該合成氣可由部份氧化重排(reforming)或蒸汽重排而形成,且一氧化碳可分離自合成氣。類似地,使乙酸氫化而形成乙醇粗產物之步驟中使用之氫可分離自合成氣。此合成氣又可衍生自各種碳源。該碳源例如可選自由天然氣、油、石油、煤炭、生質材料或其組合所成之群組。合成氣或氫亦可獲自生物衍生之甲烷氣體如由廢棄物掩埋或農業廢棄物所製得之生物衍生之甲烷氣體。
於另一具體例中,氫化步驟中使用之乙酸可自生質材料發酵而形成。該發酵製程較好利用產乙酸(homoacetogenic)製程或同型產乙酸微生物而將糖發酵成乙酸並產生極少量,若有,二氧化碳作為副產物。發酵製程之碳效率相較於一般具有約67%之碳效率之習知酵母製程,較好,大於70%、大於80%或大於90%。視情況,發酵製程中使用之微生物為一菌屬(genus),係選自由梭菌屬(Clostridium)、乳酸菌屬(Lactobacillus)、穆爾氏菌屬(Moorella)、嗜熱厭氣菌屬(Thermoanaerobacter)、丙酸桿菌屬(Propionibacterium)、丙酸孢菌屬(Propionispera)、厭氣螺菌屬(Anaerobiospirillum)及擬桿菌屬(Bacteriodes)所組成之群組,且尤其是菌種(species)係選自由甲醯乙酸梭菌(Clostridium formicoaceticum)、丁酸桿菌(Clostridium butyricum)、穆爾氏熱乙酸菌(Moorella thermoacetica)、凱伍產醋菌(Thermoanaerobacter kivui)、保加利亞乳酸菌(Lactobacillus delbrueckii)、丙酸桿菌(Propionibacterium acidipropionici)、丙酸孢菌(Propionispera arboris)、產琥珀酸放線桿菌(Anaerobiospirillum succinicproducens)、似澱粉擬桿菌(Bacteriodes amylophilus)及栖瘤胃擬桿菌(Bacteroides ruminicola)所組成之群組。視情況,於本製程中,所有或部份之自生質材料(如木酚素)之該未發酵之殘留物可經氣化以形成可用於本發明氫化步驟中之氫。形成乙酸之列舉發酵製程敘述於美國專利號6,509,180;6,927,048;7,074,603;7,507,562;7,351,559;7,601,865;7,682,812及7,888,082,其等全文併入本文供參考。亦參見美國專利公開號2008/0193989及2009/0281354,其等全文併入本文供參考。
生質材料實例包含,但不限於,農業廢棄物、森林產物、草皮及其他纖維素材料、儲木場木材剩餘物、軟木片、硬木片、樹枝、樹幹、葉子、樹皮、木屑、不合規格紙漿、玉米、玉米穗稈、小麥屑、米屑、甘蔗渣、柳枝稷、芒草、動物排泄物、城市垃圾肥、城市汙水、商業廢棄物、葡萄浮石、杏核殼、大胡桃殼、椰子殼、咖啡渣、草粒、乾草粒、木粒、紙板、紙、塑膠及布。參見例如美國專利號7,884,253,其全文併入本文供參考。其他生質材料來源為草漿黑液,係一種用以將木材轉化成紙漿之牛皮紙漿製程之副產物的濃稠黑色液體,其接著被乾燥而用於造紙。草漿黑液係木質素殘留物、半纖維素及無機化學品之水溶液。
美國再發證專利號RE 35,377,亦併入本文供參考,提供一種藉由轉化碳質材料如油、煤炭、天然氣及生質材料而製造甲醇之方法。該製程包含使固體及/或液體碳質材料氫氣化(hydrogasification)以獲得製程氣體,其以其他天然氣蒸汽裂解而形成合成氣。該合成氣轉化成甲醇,其可再經羰化成乙酸。該方法同樣產生氫氣,其可用於上述本發明。美國專利號5,821,111揭示經由氣化將廢棄生質材料轉化成合成氣之製程,及美國專利號6,685,754揭示製造含氫氣體組成物如包含氫及一氧化碳之合成氣之方法,該等專利併入本文供參考。
饋入氫化反應器之乙酸亦包括其他羧酸類及酸酐類以及醛類及/或酮類,如乙醛及丙酮。該進料中亦可存在酯類如乙酸乙酯、乙酸正丙酯、乙酸異丙酯、乙酸正丁酯及其他。較好,適宜乙酸進料液流包括一種或多種化合物係選自由乙酸、乙酸酐、乙醛、乙酸乙酯及其混合物所組成之群組。該等其他化合物亦可在本發明製程中經氫化。有些具體例中,羧酸類如丙酸或其酸酐之存在可能有利於製造丙醇。水亦可存在於乙酸進料中。
或者,蒸汽態之乙酸可自美國專利號6,657,078,其全文併入本文供參考,所述之甲醇羰化單元之閃蒸容器中以粗產物直接取得。該蒸汽粗產物例如可直接饋入氫化反應器中而無須將乙酸及輕烴物冷凝或移除水,而可節省總加工成本。
乙酸可在反應溫度下蒸汽化,接著該蒸汽化乙酸可與未稀釋狀態或以相對惰性載體如氮氣、氬氣、氦氣、二氧化碳等稀釋之氫一起饋入。蒸汽相中之反應運轉、溫度應被控制以使得不會低於乙酸之露點。於一具體例中,乙酸可在特定壓力下在乙酸之沸點下蒸汽化,且接著將該蒸汽化之乙酸進而加熱至反應器入口溫度。另一具體例中,該乙酸在蒸汽化前與其他氣體混合,接著將混合蒸汽加熱至反應器入口溫度。較好,藉由使氫及/或循環氣體在125℃或低於125℃之溫度通過乙酸而將乙酸轉移至蒸汽態,接著將該組合之氣體流加熱至反應器入口溫度。
有些具體例中之反應器可包含使用固定床反應器或流體床反應器之各種組態。本發明許多具體例中,可使用”絕熱(adiabatic)”反應器,亦即極少或不需要將內部管道通入反應區以加入或移除熱。於其他具體例中,可利用徑流反應器(radial flow reactor)或諸反應器,或可使用一組串聯之反應器,其可含或不含熱交換、淬滅或導入額外進料材料。或者,可使用設有熱轉移介質之殼及管型反應器。在許多例中,該反應區可容置於單一容器中或容置於其間具有熱交換之串聯容器中。
於較佳具體例中,於固定床反應器中例如於直管或管型反應器中使用觸媒,於該處一般成蒸汽態之反應物通過該觸媒上或其內。可使用其他反應器如流體或沸騰床(ebullient bed reactors)反應器。於有些例中,該氫化觸媒可與惰性材料聯用以調節反應物液流通過觸媒床之壓降及反應物化合物與觸媒顆粒之接觸時間。
氫化反應可在液相或蒸汽相中進行。較好,反應係在下列條件下於蒸汽相進行。反應溫度可在125℃至350℃之範圍,如自200℃至325℃、自225℃至300℃、或自250℃至300℃。壓力可在10仟帕(kPa)至3000仟帕之範圍,例如自50仟帕至2300仟帕、或自100仟帕至1500仟帕。反應物可以大於500 hr-1(小時-1),例如大於1000小時-1、大於2500小時-1或甚至大於5000小時-1之氣體時空速度(GHSV)饋入反應器中。以GHSV之範圍表示時,可自50小時-1至50,000小時-1
之範圍,如自500小時-1至30,000小時-1,自1000小時-1至10,000小時-1,或自1000小時-1至6500小時-1。
該氫化反應可在恰足以克服在所選擇之GHSV下橫過觸媒床之壓降之壓力下進行,但並不排除使用高壓,應理解通過反應床之相當壓降可能經歷高的時空速度,如5000小時-1或6,500小時-1。
雖然反應每莫耳乙酸消耗兩莫耳氫而製得一莫耳乙醇,但進料液流中之氫對乙酸之實際莫耳比可在約100:1至1:100間變化,如自50:1至1:50、自20:1至1:2、或自12:1至1:1。最好氫對乙酸之莫耳比大於2:1,例如大於4:1或大於8:1。通常,該反應器可使用過量氫,而次要氫化反應器(secondary hydrogenation reactor)當需要使雜質氫化時可使用足量氫。在一種情況,由反應器而來的部分過量的氫導入次要氫化反應器供氫化作用,有些視情況具體例中,次要反應器可在比該氫化反應器高之壓力下操作且可自次要反應器液體產物中於絕熱壓力還原容器中分離出包括氫之高壓氣體流且該氣體流可導入氫化反應器系統。
接觸或滯留時間亦可廣泛變化,視各種變數而定,如乙酸量、觸媒、反應器、溫度及壓力。當使用觸媒系統而非固定床時,一般接觸時間自數毫秒至超過數小時之範圍,而至少對蒸汽相反應之較佳接觸時間係自0.1至100秒,例如自0.3至80秒或自0.4至30秒。
尤其,乙酸之氫化可達成乙酸之有利轉化率及乙醇之有利選擇率及生產量。就本發明目的而言,名詞”轉化率”表示進料中轉化成乙酸以外之化合物之乙酸的量。轉化係基於進料中乙酸之莫耳百分比表示。如所示,該轉化率可為至少10%,如至少20%,至少40%,至少50%,至少60%,至少70%或至少80%。雖然具有高轉化率之觸媒為所需,如至少80%或至少90%,但有些具體例中,低轉化率但對乙醇高選擇性則可接受。當然應了解在許多例中,可能藉由適當再循環流或使用較大反應器而彌補轉化率,但不良選擇率則更難以彌補。
選擇率係表示基於經轉化乙酸之莫耳百分比。應了解自乙酸轉化之各化合物具有獨立之選擇率且該選擇率與轉化率亦彼此獨立。例
如,若經轉化乙酸之60莫耳%轉化成乙醇,則稱該乙醇選擇率為60%。較好,對乙氧基化物(ethoxy late)之觸媒選擇率至少為60%,如至少70%,或至少80%。本文所用之名詞”乙氧基化物”特別表示化合物乙醇、乙醛及乙酸乙酯。較好,對乙醇之選擇率至少為70%,如至少75%或至少85%或至少88%。氫化製程之較佳具體例亦對非所需產物如對甲烷、乙烷及二氧化碳具有低選擇率。對該等非所需產物之選擇率較好小於4%,如小於2%或小於1%。更好,該等非所需產物係以非可偵測之量存在。烷烴類之形成可為較低且理想上通過觸媒之少於2%、少於1%或少於0.5%之乙酸會被轉化成烷烴類,然而烷烴類除了作為燃料之用外只具有極低價值。
本文所用之名詞”產率”表示基於每小時所用觸媒公斤重於氫化期間形成之特定產物如乙醇之克數。較好產率為每小時每公斤觸媒生產至少100克乙醇,如每小時每公斤觸媒生產至少400克乙醇或每小時每公斤觸媒生產至少600克乙醇。以範圍表示時,該產率較好為每小時每公斤觸媒生產自100至3,000克乙醇,如每小時每公斤觸媒生產自400至2,500克乙醇,或每小時每公斤觸媒生產自600至2,000克乙醇。
在本發明條件下之操作可產生每小時至少0.1噸等級之乙醇產量,如每小時至少1噸乙醇、每小時至少5噸乙醇、或每小時至少10噸乙醇。較大工業規模之乙醇製造,視規模而定,通常應每小時生產至少1噸乙醇,如每小時產生至少15噸乙醇、或每小時產生至少30噸乙醇。以範圍表示,對較大之乙醇製造工業規模而言,本發明製程每小時可產生自0.1至160噸乙醇,如每小時產生15至160噸乙醇、或每小時產生30至80噸乙醇。以發酵進行乙醇製造由於經濟規模,一般單一工廠乙醇製造無法達成可藉由利用本發明具體例可達成之規模。
本發明各種具體例中,由反應器所製得之乙醇粗產物,在任何隨後加工如純化及分離之前,一般包括未反應的乙酸、乙醇及水。本文所用之名詞”乙醇粗產物”表示包括自5至70重量%乙醇及自5至40
重量%水之任何組成物。乙醇粗產物之例舉組成範圍見於表1。表1中鑑定為”其他”可包含例如酯類、醚類、醛類、酮類、烷類及二氧化碳。
一具體例中,該乙醇粗產物可包括少於20重量%,如少於15重量%、少於10重量%或少於5重量%之量的乙酸。於具有較低量乙酸之具體例中,乙酸轉化率較好大於75%,如大於85%或大於90%。此外,對乙醇之選擇率亦較好地較高,且較好大於75%,如大於85%或大於90%。
乙醇產物可藉由使用數種不同分離技術自使用本發明觸媒之反應器所產生之乙醇粗產物中回收。
乙醇產物可為包括佔乙醇產物總重之75至96重量%乙醇,如自80至96重量%或自85至96重量%乙醇之工業等級乙醇。有些具體例中,當進一步使用水分離時,該乙醇產物較好含有其量大於97重量%之乙醇,如大於98重量%或大於99.5重量%乙醇。此方面中之乙醇產物較好包括少於3重量%之水,如少於2重量%或少於0.5重量%之水。
本發明具體例所製得之完成乙醇組成物可用於各種用途,包含作為燃料、溶劑、化學原料、醫藥產品、清潔劑、消毒劑、氫化傳送或消耗等用途。於燃料應用中,完成乙醇組成物可與汽油摻合用於交通工具如汽車、船及小型活塞式引擎飛機。於非燃料用途中,此完成之乙醇組成物可用作為衛生及化妝製劑、清潔劑、消毒劑、塗料、油墨
及醫藥之溶劑。該完成乙醇組成物亦可使用作為醫藥產品、食品製劑、染料、光化學品及乳膠加工之製造製程中之加工溶劑。
該完成乙醇組成物亦可使用作為化學原料以製造其他化學品如醋、丙烯酸乙酯、乙酸乙酯、乙烯、二醇醚類、乙胺類、醛類、及高級醇類尤其是丁醇。製造乙酸乙酯中,該完成乙醇組成物可藉乙酸而酯化。其他用途中,該完成乙醇組成物可經脫水而製造乙烯。任何已知之脫水觸媒均可被用於使乙醇脫水,如敘述於美國共同申請專利公開號2010/0030002及2010/0030001者,其全部內容及揭示併於本文供參考。例如,可使用沸石觸媒作為脫水觸媒。較好,沸石具有至少約0.6nm之孔直徑,且較佳之沸石包含脫水觸媒係選自由絲光沸石、ZSM-5、沸石X及沸石Y所組成之群組。沸石X描述於例如美國專利號2,882,244且沸石Y描述於美國專利號3,130,007,其整體說明書併入本文供參考。
本發明將參考數種僅基於舉例及說明目的之具體例詳細說明如下。在述於申請專利範圍中之本發明精神及範圍內之特定具體例之改良對熟知本技藝者將為易於了解者。
為了使本文中揭示之本發明更易於被了解,下列提出實施例。應了解該等實施例僅供說明目的且非以任何方式限制本發明。
藉由將WO3及CaSiO3添加於SiO2觸媒擔體中接著添加Pt/Sn之二元金屬組合而製備改質觸媒。
製備CaSiO3(200網目)之水性懸浮液並在室溫與SiO2攪拌2小時。此外,將可溶WO3前驅物(NH4)6H12W12O40.nH2O(AMT)溶液滴加於瓶內之該SiO2中。各觸媒之CaSiO3及WO3之量隨著莫耳比而改變。使觸媒在120℃乾燥隔夜接著在500℃煅燒6小時。製得改質擔體後,將前驅物添加至該二元金屬中並煅燒。該二元混合物之金屬負載,基於觸媒總重係少於5重量%,對各觸媒均相同。
依據本實施例製得下列三種觸媒:
A)SiO2-CaSiO3(6重量%)-Pt-Sn
B)SiO2-CaSiO3(6重量%)-WO3(8重量%)-Pt-Sn
C)SiO2-CaSiO3(6重量%)-WO3(12重量%)-Pt-Sn
觸媒B之Ca對W之莫耳比為1.3:1,且觸媒C為1:1。觸媒A僅含有CaSiO3擔體改質劑且不含任何WO3。
使蒸汽化乙酸及氫通過實施例1製備之各觸媒上。各反應之反應條件均相同。結果示於表2。
觸媒B及C經證明產率及乙酸轉化率均比觸媒A獲得改良。當WO3量增加超過12重量%時,乙酸轉化率及乙醇選擇率通常維持為與觸媒C類似。
雖然已就本發明進行詳述,但在本發明精神及範圍內之改質對熟知本技藝者而言將為顯而易見。鑒於前述,上述先前技術及實施方式中所述及之本技藝相關知識及參考文獻,該等揭示均併入本文供參考。此外,應了解本文及/或附屬申請專利範圍內所述之本發明目的及部分各種具體例及各種特徵可全部或部分予以組合或交換。在各種具體例之前述描述中,表示其他具體例之該等具體例可適當與一或多個其他具體例組合,其為熟知本技藝者可了解。再者,熟知本技藝者將了解前述描述僅為舉例說明且並不用以限制本發明。
Claims (15)
- 一種製造醇類之製程,包括:使包括氫及呈蒸汽相烷酸之氣態流通過氫化觸媒上,而產生醇類,其中該氫化觸媒包括擔體及一種或多種金屬,其中氫化觸媒進而包括:(a)氧化鎢,及(b)至少一種鹼土金屬氧化物、至少一種鹼土金屬偏矽酸鹽或其混合物。
- 如申請專利範圍第1項之製程,其中組份(b)相對於組份(a)之莫耳比基於金屬為自1:3至5:1。
- 如申請專利範圍第1至2項中任一項之製程,其中該擔體係選自由氧化矽、氧化矽/氧化鋁、偏矽酸鈣、裂解氧化矽、高純度氧化矽及其混合物所組成之群組。
- 如申請專利範圍第1至3項中任一項之製程,其中該擔體存在量係自25重量%至99重量%。
- 如申請專利範圍第1至4項中任一項之製程,其中該一種或多種金屬係選自由錫、銠、鉑、鈀、鈷、銅、鐵、鎳、鋅、鉻、錸、鉬及釕所組成之群組。
- 如申請專利範圍第1至5項中任一項之製程,其中該一種或多種金屬係錫。
- 如申請專利範圍第1至6項中任一項之製程,其中該一種或多種金屬係選自由銠、鉑、鈀、鈷、銅、鐵、鎳、鋅、鉻、錸、鉬及釕所組成之群組。
- 如申請專利範圍第1至5項中任一項之製程,其中該一種或多種金屬係錫及鉑。
- 如申請專利範圍第1至8項中任一項之製程,其中該一種或多種金屬之總重為0.1至25重量%。
- 如申請專利範圍第1至9項中任一項之製程,其中該氧化鎢之存在量係自1至25重量%。
- 如申請專利範圍第1至10項中任一項之製程,其中該至少一種氧化物或偏矽酸鹽之鹼土金屬係選自由鎂、鈣及其混合物所組成之群組。
- 如申請專利範圍第1至11項中任一項之製程,其中該鹼土金屬偏矽酸鹽係偏矽酸鈣。
- 如申請專利範圍第1至12項中任一項之製程,其中該烷酸係由甲醇及一氧化碳所形成,其中該甲醇、該一氧化碳及用於該氫化步驟之氫之至少一種係衍生自合成氣,且其中該合成氣係衍生自碳源係選自由天然氣、油、石油、煤炭、生質材料及其組合所組成之群組。
- 如申請專利範圍第1至13項中任一項之製程,其中該氣態流係在125℃至350℃之溫度通過該氫化觸媒上。
- 如申請專利範圍第1至14項中任一項之製程,其中氫相對於烷酸之莫耳比大於2:1。
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-
2011
- 2011-10-06 US US13/267,149 patent/US8536382B2/en not_active Expired - Fee Related
-
2012
- 2012-08-24 TW TW101130756A patent/TW201315712A/zh unknown
- 2012-10-01 AR ARP120103657A patent/AR088088A1/es not_active Application Discontinuation
- 2012-10-25 WO PCT/US2012/061794 patent/WO2013052972A1/en active Application Filing
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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US9399615B2 (en) | 2014-11-27 | 2016-07-26 | Industrial Technology Research Institute | Catalyst and method for hydrogenation of 4,4′-methylenedianiline |
Also Published As
Publication number | Publication date |
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US8536382B2 (en) | 2013-09-17 |
AR088088A1 (es) | 2014-05-07 |
WO2013052972A1 (en) | 2013-04-11 |
US20130090500A1 (en) | 2013-04-11 |
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