CN102421521B - 用于生产乙醇的包含结晶载体改性剂的催化剂的制备和用途 - Google Patents
用于生产乙醇的包含结晶载体改性剂的催化剂的制备和用途 Download PDFInfo
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- CN102421521B CN102421521B CN201180001992.4A CN201180001992A CN102421521B CN 102421521 B CN102421521 B CN 102421521B CN 201180001992 A CN201180001992 A CN 201180001992A CN 102421521 B CN102421521 B CN 102421521B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 177
- 239000003607 modifier Substances 0.000 title claims abstract description 50
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- 238000002360 preparation method Methods 0.000 title description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 223
- 229910052751 metal Inorganic materials 0.000 claims abstract description 164
- 239000002184 metal Substances 0.000 claims abstract description 164
- 238000000034 method Methods 0.000 claims abstract description 61
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 93
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 74
- 230000004048 modification Effects 0.000 claims description 48
- 238000012986 modification Methods 0.000 claims description 48
- 239000000377 silicon dioxide Substances 0.000 claims description 46
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 45
- 239000002243 precursor Substances 0.000 claims description 40
- 238000005984 hydrogenation reaction Methods 0.000 claims description 39
- 238000006243 chemical reaction Methods 0.000 claims description 38
- 229910052697 platinum Inorganic materials 0.000 claims description 33
- 239000011135 tin Substances 0.000 claims description 27
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- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 21
- 238000002425 crystallisation Methods 0.000 claims description 19
- 230000008025 crystallization Effects 0.000 claims description 19
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 18
- 229910052702 rhenium Inorganic materials 0.000 claims description 18
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 18
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- 239000000463 material Substances 0.000 claims description 12
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 8
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 10
- 238000001354 calcination Methods 0.000 description 10
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- 239000010457 zeolite Substances 0.000 description 7
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- 230000003197 catalytic effect Effects 0.000 description 6
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 6
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 4
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- 229910002651 NO3 Inorganic materials 0.000 description 3
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- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
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Abstract
一种包含第一金属、含硅载体和至少一种偏硅酸盐载体改性剂的催化剂,其中按X-射线衍射测定所述至少一种偏硅酸盐载体改性剂的至少1wt.%是结晶相。本发明还涉及形成这样的催化剂的方法,其中所使用的载体,和在这样的催化剂存在下将乙酸加氢的方法。
Description
相关申请的交叉引用
本申请要求2010年2月2日提交的美国临时申请No.61/300,810的优先权,通过引用将其全文并入本文。
发明领域
本发明总体上涉及用于例如将乙酸加氢形成乙醇的方法中的包含结晶(crystalline)载体改性剂的负载型催化剂。
发明背景
存在对将乙酸转化为乙醇的经济上可行的方法和催化剂的长期需要,所述乙醇可以按其自身使用或随后转化为乙烯,所述乙烯是重要的商品原料,因为可将其转化为聚乙烯、乙酸乙烯酯和/或乙酸乙酯或任何许多其它化学产品。波动的天然气和原油价格有助于使按照常规生产的以石油或天然气为来源的乙烯的成本波动,从而当油价上升时使得对可供选择的乙烯来源的需要比以往更大。
用于还原链烷酸和其它含羰基化合物的催化方法已得到广泛研究,在文献中已提及催化剂、载体和操作条件的各种组合。T.Yokoyama等在“Fine chemicals through heterogeneous catalysis.Carboxylicacids and derivatives”中评述了各种羧酸在金属氧化物上的还原。第8.3.1章中概述了用于各种羧酸的加氢催化剂的开发尝试中的一些。(Yokoyama,T.;Setoyama,T.“Carboxylic acids and derivatives.”in:“Fine chemicals through heterogeneous catalysis.” 2001,370-379.)。
M.A.Vannice等的一系列研究涉及乙酸在各种非均相催化剂上的转化(Rachmady W.;Vannice,M.A.;J Catal.(2002)Vol.207,317-330页)。在不同研究中报导了在负载和非负载的铁上用H2将乙酸气相还原。(Rachmady,W.;Vannice,M.A.J.Catal.(2002)Vol.208,158-169页)。在Rachmady,W.;Vannice,M.A.,J.Catal.(2002)Vol.208,170-179页)中给出了关于催化剂表面物质和有机中间体的其它信息。在Rachmady,W.;Vannice,M.A.J.Catal.(2002)Vol.209,87-98页和Rachmady,W.;Vannice,M.A.J.Catal.(2000)Vol.192,322-334页中进一步研究了在一系列负载型Pt-Fe催化剂上的气相乙酸加氢。
涉及不饱和醛的选择性加氢的各种相关出版物可以在以下中找到:(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.AppliedCatalysis 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.)。
报导了含有钴、铂和锡的催化剂在将巴豆醛选择性加氢为不饱和醇中的活性和选择性的研究在以下中找到:R.Touroude等的(Djerboua,F.;Benachour,D.;Touroude,R.Applied Catalysis A:General 2005,282,123-133和Liberkova,K.;Tourounde,R.;J.Mol.Catal.2002,180,221-230)以及K.Lazar等的(Lazar,K.;Rhodes,W.D.;Borbath,I.;Hegedues,M.;Margitfalvi,1.L.HyperfineInteractions 2002,1391140,87-96.)。
M.Santiago等(Santiago,M.A.N.;Sanchez-Castillo,M.A.;Cortright,R.D.;Dumesic,1.A.J.Catal.2000,193,16-28.)讨论了与量子化学计算组合的微量热法测量、红外光谱法测量和反应动力学测量。
还就具有铼和钌的非均相体系报导了对于乙酸加氢的催化活性。(Ryashentseva,M.A.;Minachev,K.M.;Buiychev,B.M.;Ishchenko,V.M.Bull.Acad Sci.USSR1988,2436-2439)。
Kitson等的美国专利No.5,149,680描述了一种利用铂族金属合金催化剂将羧酸及它们的酸酐催化加氢为醇和/或酯的方法。Kitson等的美国专利No.4,777,303描述了一种通过羧酸加氢生产醇的方法。Kitson等的美国专利No.4,804,791描述了另一种通过羧酸加氢生产醇的方法。还参见USP 5,061,671;USP 4,990,655;USP 4,985,572;和USP 4,826,795。
除上述金属外,催化剂例如加氢催化剂按照常规包含载体材料,并且已知载体金属对催化剂的性质例如性能(performance property)具有影响。
Malinowski等(Bull.Soc.Chim.Belg.(1985),94(2),93-5)讨论了乙酸在多相化于载体材料例如二氧化硅(SiO2)或二氧化钛(TiO2)上的低价钛上的反应催化。
双金属钌-锡/二氧化硅催化剂通过使四丁基锡与负载在二氧化硅上的二氧化钌反应制得。(Loessard等,Studies in Surface Science andCatalysis(1989),Volume Date 1988,48(Struct.React.Surf),591-600.)。
例如,Hindermann等的(Hindermann等,J.Chem.Res.,Synopses(1980),(11),373)中也研究了乙酸的催化还原,公开了乙酸在铁上和在碱促进的铁上的催化还原。
然而,仍需要对乙醇具有高的选择性、转化率和产率且具有适合用于商业加氢工艺的催化剂寿命的新型加氢催化剂。
发明概述
本发明涉及用于催化乙酸加氢得到乙醇的催化剂。在第一实施方案中,本发明涉及包含第一金属、含硅(silicaceous)载体和至少一种偏硅酸盐载体改性剂的催化剂,其中按XRD测定所述偏硅酸盐载体改性剂的至少0.1wt.%,例如至少0.5wt.%、至少1wt.%、至少5wt.%、至少10wt.%、至少25wt.%、至少50wt.%、至少75wt.%、至少80wt.%、至少90wt.%是结晶相。本发明的催化剂在乙酸加氢中在高选择性,例如至少80%的选择性下可以有利地提供每千克催化剂每小时至少800克的乙醇产率。
在另一个实施方案中,本发明涉及生产乙醇的方法,该方法包括在催化剂存在下将乙酸进行加氢,所述催化剂包含第一金属、含硅载体和至少一种偏硅酸盐载体改性剂,其中按XRD测定所述偏硅酸盐载体改性剂的至少1wt.%是结晶相。
在优选实施方案中,所述至少一种偏硅酸盐载体改性剂选自:(i)碱土金属偏硅酸盐,(ii)碱金属偏硅酸盐,(iii)IIB族金属偏硅酸盐,(iv)IIIB族金属偏硅酸盐,和它们的混合物。例如,所述至少一种偏硅酸盐载体改性剂选自金属的偏硅酸盐,所述金属选自钠、钾、镁、钪、钇和锌。在优选实施方案中,所述至少一种偏硅酸盐载体改性剂包含CaSiO3。所述至少一种偏硅酸盐载体改性剂优选以基于催化剂总重量计0.1wt.%-50wt.%的量存在。
第一金属任选选自:IB、IIB、IIIB、IVB、VB、VIB、VIIB或VIII族过渡金属,镧系金属,锕系金属,或者IIIA、IVA、VA和VIA族中任意族的金属。例如,第一金属可以选自铜、铁、钴、镍、钌、铑、钯、锇、铱、铂、钛、锌、铬、铼、钼和钨。第一金属优选以基于催化剂总重量计0.1-25重量%的量存在。
含硅载体任选以基于催化剂总重量计25重量%-99重量%的量存在,并且可具有50m2/g-600m2/g的表面积。在优选方面中,含硅载体选自二氧化硅、二氧化硅/氧化铝、偏硅酸钙、热解二氧化硅、高纯度二氧化硅和它们的混合物。含硅载体优选含有基于该催化剂总重量计小于1重量%的铝。此外,含硅载体优选含有基于催化剂总重量计小于0.30wt.%的铝氧化物(aluminum oxide)、钛氧化物(titanium oxide)和铁氧化物(iron oxide)组合。
任选地,该催化剂还包含与第一金属不同的第二金属,例如选自铜、钼、锡、铬、铁、钴、钒、钨、钯、铂、镧、铈、锰、钌、铼、金和镍的金属。第二金属可以按基于催化剂总重量计0.1-10重量%的量存在。在优选方面中,第一金属是铂,第二金属是锡,铂与锡的摩尔比任选为0.4∶0.6-0.6∶0.4。在另一个优选方面中,第一金属是钯,第二金属是铼,铼与钯的摩尔比任选为0.7∶0.3-0.85∶0.15。
该催化剂任选还包含不同于所述第一和第二金属的第三金属,例如其中所述第三金属选自钴、钯、钌、铜、锌、铂、锡和铼。第三金属任选以基于催化剂总重量计0.05-4重量%的量存在。
该催化剂还优选适合在使乙酸转化为乙醇中用作加氢催化剂且产生至少10%的乙酸转化率。催化剂优选具有每100小时的催化剂使用降低小于6%的产率。
在另一个实施方案中,本发明涉及用于加氢催化剂的载体,所述载体包含含硅载体材料;和偏硅酸盐载体改性剂,其中按XRD测定所述偏硅酸盐载体改性剂的至少1wt.%是结晶相。
在另一个实施方案中,本发明涉及制备催化剂的方法,该方法包括以下步骤:(a)使第一金属的第一金属前体与改性含硅载体接触以形成浸渍的载体,其中所述改性含硅载体包含含硅材料和至少一种偏硅酸盐载体改性剂,按XRD测定所述至少一种偏硅酸盐载体改性剂包含至少1wt.%结晶偏硅酸盐;和(b)在有效还原所述第一金属并形成催化剂的条件下加热所述浸渍载体。该方法任选还包括使第二金属的第二金属前体与改性含硅载体接触。在另一方面,该方法还可以包括以下步骤:(c)使至少一种偏硅酸盐载体改性剂或其前体与含硅载体接触以形成改性的载体前体;和(d)在有效形成改性含硅载体的条件下加热所述改性的载体前体。
附图说明
下面参考附图详细地描述本发明,其中相同的数字指示类似的部分。
图1A是使用SiO2-PtmSn1-m催化剂时对于乙醇和乙酸乙酯的选择性的坐标图;
图1B是图1A的催化剂对于乙醇和乙酸乙酯的产率的坐标图;
图1C是图1A的催化剂的乙酸转化率的坐标图;
图2A是使用SiO2-RenPd1-n催化剂时对于乙醇和乙酸乙酯的选择性的坐标图;
图2B是图2A的催化剂对于乙醇和乙酸乙酯的产率的坐标图;
图2C是图2A的催化剂的乙酸转化率的坐标图;和
图3是实施例1-5中催化剂的乙醇产率的坐标图。
发明详述
本发明涉及用于通过将乙酸加氢生产乙醇的方法的催化剂。将乙酸加氢形成乙醇可以由以下反应表示:
根据本发明的一个实施方案用于将乙酸加氢形成乙醇的催化剂包含至少一种金属、载体例如含硅载体和至少一种偏硅酸盐载体改性剂。在美国公开No.2010/0121114(通过引用将其全文并入本文)中论述了改性载体。
出人意料且意想不到地,现已发现具有用结晶相偏硅酸盐载体改性剂至少部分改性的载体的催化剂,对于在乙酸加氢中形成乙醇特别有效,提供了就乙醇而言高的转化率、选择性和产率。根据本发明的一些实施方案,按X-射线衍射技术(XRD)所测定,例如,偏硅酸盐载体改性剂的至少0.5wt.%、至少1wt.%、至少2wt.%、至少3wt.%、至少5wt.%、至少10wt.%、至少25wt.%、至少50wt.%、至少75wt.%、至少80wt.%、至少90wt.%或至少95wt.%是结晶相。就范围而言,按XRD所测定,偏硅酸盐载体改性剂的结晶相可以为0.5wt.%-99wt.%,例如0.5wt.%-75wt.%、0.5wt.%-50wt.%、0.5wt.%-25wt.%、0.5wt.%-10wt.%或0.5wt.%-5wt.%。在一个实施方案中,按XRD所测定,偏硅酸盐载体改性剂的结晶相可以为2wt.%-5wt.%。优选地,结晶偏硅酸盐的晶系至少部分是三斜晶系。
在本发明的多个实施方案中,催化剂组合物的结晶特性可以由基本上均质(homogeneous)的结晶偏硅酸盐载体改性剂获得,这意味着偏硅酸盐载体改性剂在基本上所有催化剂颗粒中具有相同的结晶度。在该方面,每个催化剂颗粒中的偏硅酸盐载体改性剂具有至少0.5wt.%、至少1wt.%、至少2wt.%、至少3wt.%、至少5wt.%、至少10wt.%、至少25wt.%、至少50wt.%、至少75wt.%、至少80wt.%、至少90wt.%或至少95wt.%的基本上均一的结晶度。在另一方面,可以通过将结晶至一定程度,例如按XRD测定至少5wt.%、至少10wt.%、至少25wt.%、至少50wt.%、至少75wt.%、至少80wt.%、至少90wt.%或至少95wt.%结晶的偏硅酸盐载体改性剂与无定形或基本上无定形的偏硅酸盐载体改性剂共混来获得相同的总结晶度。后一方面可以有望容易地将催化剂批料(batch)的结晶度调节至所需的结晶性水平。
如上文所指出,本发明的催化剂尤其包含载体例如改性载体,改性载体是指包括载体材料和载体改性剂的载体,所述载体改性剂调节载体材料的酸度。例如,载体材料上的酸位如酸位可以通过载体改性剂进行调节以在乙酸加氢期间有利于对乙醇的选择性。载体材料的酸度可以通过减少载体材料上酸位的数量或降低该载体材料上酸位的可获得性来进行调节。载体材料还可以通过使载体改性剂改变载体材料的pKa来进行调节。除非上下文另外指明,其上的表面酸度或酸位数量可以通过F.Delannay编辑,“Characterization of Heterogeneous Catalysts”;ChapterIII:Measurement of Acidity of Surfaces,370-404页;Marcel Dekker,Inc.,N.Y.1984中所描述的技术进行测定,通过引用将其全文并入本文。
应当对载体材料进行选择使得催化剂体系在用于生成乙醇的工艺条件下具有合适的活性、选择性和稳健性(robust)。合适的载体材料可以包括例如稳定的金属氧化物基载体或陶瓷基载体。优选的载体材料包括含硅载体,例如二氧化硅、二氧化硅/氧化铝、IIA族硅酸盐如偏硅酸钙、热解二氧化硅、高纯度二氧化硅和它们的混合物。其它载体材料可以用在本发明的一些实施方案中,包括但不限于铁氧化物、氧化铝、二氧化钛、氧化锆、氧化镁、碳、石墨、高表面积的石墨化碳、活性炭和它们的混合物。
此外,载体材料有利地通过载体改性剂,例如偏硅酸盐载体改性剂,优选偏硅酸钙进行改性。如上所示,按XRD测定偏硅酸盐载体改性剂的至少0.5wt.%、至少1wt.%、至少2wt.%、至少3wt.%、至少5wt.%、至少10wt.%、至少25wt.%、至少50wt.%、至少75wt.%、至少80wt.%、至少90wt.%或至少95wt.%是结晶相。就范围而言,载体改性剂中的结晶偏硅酸盐载体改性剂的量可以例如为1wt.%-75wt.%,例如20-50wt.%、40-70wt.%、60-90wt.%或70-95wt.%。通过利用载体改性剂中高百分数的结晶偏硅酸盐,可以获得乙醇产率的提高(与利用可比无定形载体改性剂获得的产率相比)。作为一个实例,结晶载体改性剂与可比无定形偏硅酸盐载体改性剂相比可以将产率提高至少5%,例如至少10%、至少15%、至少20%、至少30%或至少50%。就总产率而言,可以获得每千克催化剂每小时至少500克乙醇(“g/kg/hr”),例如至少600g/kg/hr、至少700g/kg/hr、至少750g/kg/hr、至少800g/kg/hr、至少850g/kg/hr、至少900g/kg/hr或至少1,000g/kg/hr的乙醇产率。
改性载体还可以包含杂质,其实例包括铝氧化物、钛氧化物和铁氧化物。出人意料且意想不到地,本发明人发现,用包含特别低水平的酸性杂质的改性载体可实现乙醇产率、选择性和/或转化率的明显改善。在一个实施方案中,当杂质,例如铝氧化物、钛氧化物和铁氧化物的总和(combination)以基于催化剂总重量计小于0.30wt.%,例如小于0.20wt.%、小于0.15wt.%、小于0.13wt.%、小于0.10wt.%或小于0.08wt.%的量存在时,获得出人意料且意想不到的结果。
在一个实施方案中,载体改性剂具有低挥发性或这可以呈非挥发性。低挥发性改性剂在催化剂寿命期间具有足够低的丧失率使得载体改性剂的酸性不被逆转(reverse)。这类碱性改性剂例如可以选自:(i)碱土金属氧化物、(ii)碱金属氧化物、(iii)碱土金属偏硅酸盐、(iv)碱金属偏硅酸盐、(v)IIB族金属氧化物、(vi)IIB族金属偏硅酸盐、(vii)IIIB族金属氧化物、(viii)IIIB族金属偏硅酸盐和它们的混合物。除氧化物和偏硅酸盐之外,可以在本发明实施方案中使用包括硝酸盐、亚硝酸盐、乙酸盐和乳酸盐的其它类型的改性剂。优选地,载体改性剂选自钠、钾、镁、钙、钪、钇和锌中任意元素的氧化物和偏硅酸盐,以及前述任意的混合物。优选地,载体改性剂是硅酸钙,更优选是偏硅酸钙(CaSiO3),其至少部分为结晶相。
包括载体材料和载体改性剂在内的改性载体总重量基于催化剂总重量计优选为75重量%-99.9重量%,例如78重量%-97重量%或80重量%-95重量%。优选提供足够量的载体改性剂以调节酸度,例如通过减少活性酸位的数量或降低活性酸位的可获得性,更优选以确保载体表面基本上没有活性酸位。在优选的实施方案中,载体改性剂以基于催化剂总重量计0.1wt.%-50wt.%,例如0.2wt.%-25wt.%、0.5wt.%-15wt.%或1wt.%-8wt.%的量存在。在优选的实施方案中,载体材料以25wt.%-99wt.%,例如30wt.%-97wt.%或35wt.%-95wt.%的量存在。
在一个实施方案中,载体材料是含硅载体材料,该含硅载体材料选自二氧化硅、二氧化硅/氧化铝、IIA族硅酸盐例如偏硅酸钙、热解二氧化硅、高纯度二氧化硅和它们的混合物。因此,在一方面,载体材料包含偏硅酸钙,例如无定形偏硅酸钙,载体改性剂包含偏硅酸盐,其至少部分为结晶相。
在其中二氧化硅用作含硅载体的情形中,有利地是确保铝(其是二氧化硅的常见污染物)的量是低的,优选基于改性载体总重量计在1重量%以下,例如0.5重量%以下或0.3重量%以下。就此而言,优选热解二氧化硅,因为它一般以超过99.7wt.%的纯度获得。如本申请中通篇所使用的,高纯度二氧化硅是指其中酸性污染物例如铝(如果有的话)以小于0.3wt.%,例如小于0.2wt.%或小于0.1wt.%的水平存在的二氧化硅。当偏硅酸钙例如结晶偏硅酸钙用作载体改性剂,关于用作载体材料的二氧化硅的纯度不必十分严格,尽管铝仍然是不期望的并且将通常不是有意加入。这种二氧化硅的铝含量例如可以小于10重量%,例如小于5重量%或小于3重量%。在其中载体包含2重量%-10重量%的载体改性剂的情形中,可以容许大量的酸性杂质例如铝,只要它们被合适量的载体改性剂基本上抵消。
载体材料例如含硅载体材料的表面积优选为至少约50m2/g,例如至少约100m2/g、至少约150m2/g、至少约200m2/g或者最优选至少约250m2/g。就范围而言,载体材料优选具有50-600m2/g,例如100-500m2/g或100-300m2/g的表面积。如本申请通篇所使用的,高表面积二氧化硅是指具有至少约250m2/g的表面积的二氧化硅。就本说明书而言,表面积是指BET氮气表面积,指的是通过ASTM D6556-04(通过引用将其全文并入本文)测定的表面积。
载体材料还优选具有如通过压汞孔隙测量法(mercury intrusionporosimetry)测定的5-100nm,例如5-30nm、5-25nm或约5-10nm的平均孔径,以及如通过压汞孔隙测量法测定的0.5-2.0cm3/g,例如0.7-1.5cm3/g或约0.8-1.3cm3/g的平均孔体积。
载体材料和由此所得的催化剂组合物的形态可以宽泛地变化。在一些示例性实施方案中,载体材料和/或催化剂组合物的形态可以是丸粒、挤出物、球、喷雾干燥的微球、环、五辐轮状物(pentaring)、三叶形物、四叶形物、多叶形物或薄片,尽管优选圆柱形丸粒。优选地,含硅载体材料具有允许堆积密度为0.1-1.0g/cm3,例如0.2-0.9g/cm3或0.5-0.8g/cm3的形态。就尺寸而言,二氧化硅载体材料优选具有0.01-1.0cm,例如0.1-0.5cm或0.2-0.4cm的平均粒径,平均粒径例如是指球形颗粒的直径或非球形颗粒的等效球形直径。因为位于改性载体之上或之内的一种或多种金属的尺寸通常非常小,它们应该基本上不影响总体催化剂颗粒的尺寸。因此,上述粒径通常适用于改性载体以及最终催化剂颗粒的尺寸。
优选的二氧化硅载体材料是来自Saint Gobain NorPro的SS61138高表面积(HSA)二氧化硅催化剂载体。Saint-Gobain NorPro SS61138二氧化硅含有约95重量%的高表面积二氧化硅;约250m2/g的表面积;约12nm的中值孔径;通过压汞孔隙测量法(mercury intrusionporosimetry)测量的约1.0cm3/g的平均孔体积,和约0.352g/cm3(22lb/ft3)的堆积密度。
优选的二氧化硅/氧化铝载体材料是KA-160(Sud Chemie)二氧化硅球,其具有约5mm的标称直径,约0.562g/ml的密度,约0.583gH2O/g载体的吸收率,约160-175m2/g的表面积和约0.68ml/g的孔体积。
乙酸加氢的一种可能的副产物是乙酸乙酯。根据本发明,载体优选包括有效抑制乙酸乙酯产生的载体改性剂,从而使催化剂组合物对乙醇具有高度选择性。因此,催化剂组合物优选对于将乙酸转化为乙酸乙酯和高度不需要的副产物例如烷烃具有低的选择性。优选控制载体的酸度使得小于4%,优选小于2%,最优选小于约1%的乙酸转化为甲烷、乙烷和二氧化碳。此外,载体的酸度可以通过使用如上所文论述的热解二氧化硅或高纯度二氧化硅来控制。
在一个实施方案中,改性载体包含载体材料和有效平衡由例如二氧化硅中残留的氧化铝产生的酸位的量的作为载体改性剂的偏硅酸钙,至少部分包括结晶偏硅酸钙。优选地,偏硅酸钙例如结晶偏硅酸钙以基于催化剂总重量计1wt.%-10wt.%,例如4-8wt.%、5wt.%-7wt.%或约6wt.%的量存在,以确保载体的性质呈基本上中性或碱性。
作为载体改性剂,例如结晶偏硅酸钙,可能趋向于比载体材料例如含硅载体材料具有更低的表面积,在一个实施方案中,载体材料包含含有至少约80重量%,例如至少约85重量%或至少约90重量%的高表面积二氧化硅的含硅载体材料,以抵消由于包含载体改性剂而引起的这种影响。
因此,不受理论束缚,用于本发明催化剂的氧化物载体材料通过引入无挥发性载体改性剂而进行改性和稳定化,所述改性剂具有抵消存在于载体表面上的酸位的作用或者使表面热稳定化的作用,使得能够获得所期望的乙醇选择性的改善、延长的催化剂寿命或这两者。一般而言,基于处于其最稳定价态的氧化物的载体改性剂将具有低的蒸气压且因此具有低挥发性或甚至无挥发性。因此,优选提供足够量的载体改性以:(i)抵消存在于载体材料表面上的酸位;(ii)赋予在加氢温度下抗形状改变性;或(iii)这两者。不受理论束缚,赋予抗形状改变性是指赋予对例如烧结、晶粒生长、晶界迁移、缺陷和位错迁移、塑性变形和/或其它温度诱导显微组织改变的抵抗力。
本发明的催化剂在并不是类似于汽车催化剂和柴油烟灰捕集装置那样浸渍到整体式载体上的刷涂层中这种意义上是颗粒状催化剂,优选将本发明的催化剂成形为颗粒,有时也称作珠或丸粒,具有各种形状中的任意形状,通过将很多这些成型的催化剂置于反应器中而将催化金属提供到反应区。常见的形状包括具有任意横截面的挤出物,在限定出挤出物表面的母线(generator)是平行线的意义上所述形状为广义柱体。如上所示,可以使用包括丸粒、挤出物、球、喷雾干燥的微球、环、五辐轮状物、三叶形物、四叶形物和多叶形物的任何便利的颗粒形状,尽管优选圆柱形丸粒。典型地,根据所认知到的使气相与催化剂有效接触的能力按照经验对形状进行选择。
本发明催化剂的一个优点是该催化剂用于生产乙醇的稳定性或活性。因此,可认识到的是,本发明的催化剂完全能够用于乙酸加氢的商业规模工业应用,特别是乙醇生产。特别地,能够获得这样的稳定性程度,该稳定性程度使得催化剂活性可具有每100小时的催化剂使用小于6%,例如每100小时小于3%或每100小时小于1.5%的产率下降速率。优选地,一旦催化剂获得稳态条件,就测定产率下降速率。
在一个实施方案中,当催化剂载体包含高纯度二氧化硅且至少部分以结晶偏硅酸钙作为载体改性剂时,催化剂活性可以扩大或稳定,在温度为125℃-350℃的乙酸蒸气存在下以大于2500hr-1的空速的商业上可行的操作的催化剂长期产率和选择性延长到超过1周、超过2周和甚至数月。
除改性载体材料外,本发明的催化剂在载体上还包含第一金属并任选包含第二金属、第三金属或另外金属中的一种或多种。在该上下文中,数字术语“第一”、“第二”、“第三”等,当用于修饰词语“金属”时,表示是指各自的金属彼此不同。存在于催化剂中的所有负载金属的总重量优选为0.1-25重量%,例如0.1-15重量%或0.1重量%-10重量%。就本说明书而言,除非另外指明,重量百分数是基于包括金属和载体在内的催化剂的总重量计。催化剂中的金属可以按一种或多种金属氧化物的形式存在。就确定催化剂中金属的重量百分数而言,忽略与金属结合的任何氧的重量。
第一金属可以选自:IB、IIB、IIIB、IVB、VB、VIB、VIIB或VIII族过渡金属,镧系金属,锕系金属,或者IIIA、IVA、VA和VIA族中任意族的金属。在优选实施方案中,第一金属选自铜、铁、钴、镍、钌、铑、钯、锇、铱、铂、钛、锌、铬、铼、钼和钨。优选地,第一金属选自铂、钯、钴、镍和钌。更优选地,第一金属选自铂和钯。当第一金属包含铂时,由于铂的可获得性,优选催化剂包含小于5重量%,例如小于3重量%或小于1重量%的量的铂。
如上所示,催化剂任选还包含第二金属,该第二金属典型地可起促进剂的作用。如果存在,第二金属优选选自铜、钼、锡、铬、铁、钴、钒、钨、钯、铂、镧、铈、锰、钌、铼、金和镍。更优选地,第二金属选自铜、锡、钴、铼和镍。更优选地,第二金属选自锡和铼。
当催化剂包括两种或更多种金属时,一种金属可以充当促进剂金属而其它金属为主金属。例如,对于铂/锡催化剂,铂可以被认为是主金属,而锡可以被认为是促进剂金属。出于方便,本说明书指定第一金属作为主催化剂而第二金属(和可选的金属)作为促进剂。但这不应该作为基础催化活性机理的指示。
如果催化剂包括两种或更多种金属,例如第一金属和第二金属,则第一金属任选以0.1-10重量%,例如0.1-5重量%或0.1-3重量%的量存在于催化剂中。第二金属优选以0.1-20wt.%,例如0.1-10wt.%或0.1-5wt.%的量存在。对于包含两种或更多种金属的催化剂,所述两种或更多种金属可以彼此合金化或者可以包含非合金化金属固溶体或混合物。
优选的金属比可以取决于催化剂中所用的金属而稍加变动。在一些实施方案中,第一金属与第二金属的摩尔比优选为10∶1-1∶10,例如4∶1-1∶4、2∶1-1∶2、1.5∶1-1∶1.5或1.1∶1-1∶1.1。现出人意料且意想不到地发现,如图1A、1B和1C中所示,对于铂/锡催化剂,特别优选约0.4∶0.6-0.6∶0.4(或约1∶1)的铂与锡摩尔比以由乙酸以高的选择性、转化率和产率形成乙醇。乙醇的选择性可以通过引入本文所述的改性载体而得到进一步改善。
对于包含不同金属的催化剂,可以优选除1∶1外的摩尔比。例如,对于铼/钯催化剂,在铼载量比钯载量高时可以获得较高的乙醇选择性。如图2A、2B和2C中所示,形成乙醇,就选择性、转化率和产率而言,优选的铼与钯摩尔比为约0.7∶0.3-0.85∶0.15或约0.75∶0.25(3∶1)。再次地,乙醇选择性可以通过引入本文所述的改性载体而得到进一步改善。
在催化剂包含第三金属时的实施方案中,第三金属可以选自上文关于第一或第二金属所列出的任何金属,只要所述第三金属不同于所述第一和第二金属。在优选方面,第三金属选自钴、钯、钌、铜、锌、铂、锡和铼。更优选地,第二金属选自钴、钯和钌。当存在时,第三金属的总重量优选为0.05-4重量%,例如0.1-3重量%或0.1-2重量%。
在一个实施方案中,催化剂包含第一金属且没有另外金属(没有第二金属等)。在该实施方案中,第一金属优选以0.1-10wt.%的量存在。在另一个实施方案中,催化剂包含载体上的两种或更多种金属的组合。下表1中提供了本发明该实施方案的各种催化剂的具体优选金属组合。在催化剂包含第一金属和第二金属时,第一金属优选以0.1-5wt.%的量存在并且第二金属优选以0.1-5wt.%的量存在。在催化剂包含第一金属、第二金属和第三金属时,第一金属优选以0.1-5wt.%的量存在,第二金属优选以0.1-5wt.%的量存在,并且第三金属优选以0.1-2wt.%的量存在。在一个示例性实施方案中,第一金属是铂并且以0.1-5重量%的量存在,第二金属以0.1-5重量%的量存在,并且第三金属,如果存在,优选以0.05-2重量%的量存在。
在另一方面,催化剂组合物可以由下式表示:
PtvPdwRexSnyCapSiqOr,
其中:(i)v∶y之比为3∶2-2∶3;和/或(ii)w∶x之比为1∶3-1∶5。因此,在该实施方案中,所述催化剂可以包含(i)铂和锡;(ii)钯和铼;或(iii)铂、锡、钯和铼,优选对p和q进行选择使得p∶q为1∶20-1∶200,其中r的选择满足化合价要求,并且v和w的选择使得:
在该方面,优选对工艺条件以及v、w、x、y、p、q和r的值进行选择以使所转化乙酸的至少70%,例如至少80%或至少90%转化为选自乙醇和乙酸乙酯的化合物,并同时小于4%的乙酸转化为烷烃。更优选地,优选对工艺条件以及v、w、x、y、p、q和r的值进行选择以使所转化乙酸的至少70%,例如至少80%或至少90%转化为乙醇,并同时小于4%的乙酸转化为烷烃。在本发明的许多实施方案中,考虑到存在的任何较少的杂质,对p进行选择以确保载体表面基本上没有活性酸位。
在另一方面,催化剂组合物包含:
PtvPdwRexSnyAlzCapSiqOr,
其中:(i)v和y为3∶2-2∶3;和/或(ii)w和x为1∶3-1∶5。优选控制p和z以及存在的铝原子和钙原子的相对位置使得存在于其表面的酸位通过载体改性剂进行平衡,所述载体改性剂例如是至少部分包含结晶偏硅酸钙的偏硅酸钙;p和q的选择使得p∶q为1∶20-1∶200,其中r的选择满足化合价要求,并且v和w的选择使得:
优选地,在该方面,所述催化剂具有至少约100m2/g,例如至少约150m2/g、至少约200m2/g或最优选至少约250m2/g的表面积,并且z和p≥z。在本发明的许多实施方案中,考虑到存在的任何较少的杂质,对p进行选择以同样确保载体表面基本上没有似乎促进乙醇转化为乙酸乙酯的活性酸位。因此,如对于先前的实施方案,优选对工艺条件以及v、w、x、y、p、q和r的值进行选择以使所转化乙酸的至少70%,例如至少80%或至少90%转化为乙醇,并同时小于4%的乙酸转化为烷烃。
优选通过改性载体的金属浸渍形成本发明的催化剂组合物,尽管还可以使用其它方法例如化学气相沉积。在浸渍金属之前,通常期望例如通过用载体改性剂浸渍载体材料的步骤形成改性载体。可以使用载体改性剂的前体,例如乙酸盐或硝酸盐。在一方面,将载体改性剂,例如至少部分是结晶CaSiO3,加入到载体材料例如SiO2中。例如,可以通过将固体载体改性剂加入到去离子水中、接着向其加入胶体载体材料来形成载体改性剂的水性悬浮液。可以搅拌所得混合物并使用例如始润浸渍技术将其加入到另外的载体材料中,在所述始润浸渍技术中将载体改性剂加入到孔体积与载体改性剂溶液的体积相同的载体材料中。然后毛细管作用将载体改性剂吸入载体材料内的孔隙中。然后可通过干燥和煅烧去除载体改性剂溶液内的水和任何挥发性组分并使载体改性剂沉积在载体材料上来形成改性载体。干燥可以例如在50℃-300℃,例如100℃-200℃或约120℃的温度下进行任选1-24小时,例如3-15小时或6-12小时的时段。一旦形成,改性载体可以成型为具有所需尺寸分布的颗粒,例如形成平均粒径为0.2-0.4cm的颗粒。可以将载体进行挤出、造粒、压片、压制、压碎或筛分为所需尺寸分布。可使用将载体材料成型为所需尺寸分布的任何已知方法。成型的改性载体的煅烧可以例如在250℃-800℃,例如300-700℃或约500℃的温度下进行任选1-12小时,例如2-10小时、4-8小时或约6小时的时段。
在制备催化剂的优选方法中,使金属浸渍到改性载体上。第一金属的前体(第一金属前体)优选用于金属浸渍步骤,所述前体例如包括目标第一金属的水溶性化合物或水可分散性化合物/络合物。取决于所使用的金属前体,可以优选使用例如水、冰乙酸或有机溶剂的溶剂。第二金属也优选由第二金属前体浸渍到改性载体中。如果需要,还可以使第三金属或第三金属前体浸渍到改性载体中。
通过将第一金属前体和/或第二金属前体和/或另外金属前体(优选在悬浮液或溶液中)中的任一种或两种加入(任选滴加)到干的改性载体中来进行浸渍。然后可以例如任选在真空下加热所得混合物以除去溶剂。然后可以任选随着斜线上升式加热进行另外的干燥和煅烧从而形成最终催化剂组合物。在加热和/或施加真空时,金属前体的金属优选分解为它们的单质(或氧化物)形式。在一些情形中,在催化剂投入使用和煅烧例如经受在操作期间遭遇的高温之前,可以不完成液体载体例如水的去除。在煅烧步骤期间,或者至少在使用催化剂的初始阶段期间,使这些化合物转化为金属的催化活性形式或其催化活性氧化物。
将第一和第二金属(以及可选的另外金属)浸入改性载体中可以同时(共浸渍)或相继进行。在同时浸渍时,将第一和第二金属前体(以及可选的另外金属前体)混合在一起并将其一起加入到改性载体中,接着进行干燥和煅烧以形成最终催化剂组合物。对于同时浸渍,如果所述两种前体与所期望的溶剂例如水不相容,则可以期望使用分散剂、表面活性剂或增溶剂例如草酸铵以促进所述第一和第二金属前体的分散或溶解。
在相继浸渍时,首先将第一金属前体加入到改性载体中,接着进行干燥和煅烧,然后用第二金属前体浸渍所得材料,接着进行另外的干燥和煅烧步骤以形成最终催化剂组合物。另外的金属前体(例如第三金属前体)可以与第一和/或第二金属前体一起加入或者是单独的第三浸渍步骤,接着进行干燥和煅烧。当然,如果需要时可以使用相继和同时浸渍的组合。
合适的金属前体包括例如金属卤化物、胺增溶的金属氢氧化物、金属硝酸盐或金属草酸盐。例如,铂前体和钯前体的合适化合物包括氯铂酸、氯铂酸铵、胺增溶的氢氧化铂、硝酸铂、四氨合硝酸铂(platinum tetra ammonium nitrate)、氯化铂、草酸铂、硝酸钯、四氨合硝酸钯(palladium tetra ammonium nitrate)、氯化钯、草酸钯、氯化钠钯和氯化钠铂。通常,从经济学和环境方面的观点同时来看,优选铂的可溶性化合物的水溶液。在一个实施方案中,第一金属前体不是金属卤化物并且基本上不含金属卤化物。虽然不受理论束缚,但认为这类非(金属卤化物)前体提高了乙醇选择性。铂的特别优选的前体是氨合硝酸铂,即Pt(NH3)4(NO4)2。
在一方面,首先将“促进剂”金属或金属前体加入到改性载体中,接着是“主要(main)”或“首要(primary)”金属或金属前体。当然也可以是相反的加入顺序。促进剂金属的示例性前体包括金属卤化物、胺增溶的金属氢氧化物、金属硝酸盐或金属草酸盐。如上所示,在相继式实施方案中,优选在每个浸渍步骤后接着进行干燥和煅烧。在如上所述的受促进的双金属催化剂的情形中,可以使用相继浸渍,开始时加入促进剂金属,接着进行包括两种主要金属例如Pt和Sn的共浸渍的第二浸渍步骤。
作为实例,SiO2上的PtSn/CaSiO3可以通过首先将CaSiO3例如结晶CaSiO3浸渍到SiO2上,接着用Pt(NH3)4(NO4)2和Sn(AcO)2共浸渍来进行制备。再次地,每个浸渍步骤后可以接着是干燥和煅烧步骤。在大多数情形中,可以使用金属硝酸盐溶液进行浸渍。然而,还可使用在煅烧时释放金属离子的各种其它可溶性盐。用于浸渍的其它合适金属盐的实例包括金属酸例如高铼酸溶液、金属草酸盐等。在其中要生成基本上纯乙醇的那些情形中,对于铂族金属通常优选避免使用卤化的前体,而是使用基于含氮的胺和/或硝酸盐的前体。
如本领域技术人员将容易地意识到的,根据本发明的一个实施方案将乙酸加氢形成乙醇的方法可以在使用固定床反应器或流化床反应器的各种构造中进行。在本发明的许多实施方案中,可以使用“绝热”反应器;即,具有很少或不需要穿过反应区的内部管道装置(plumbing)来加入或除去热。或者,可以使用配设有热传递介质的管壳式反应器。在许多情形中,反应区可以容纳在单个容器中或之间具有换热器的系列容器中。明显认为的是,使用本发明催化剂的乙酸还原方法可以在绝热反应器中进行,因为这种反应器构造与管壳式构造相比资本密集程度通常小很多。
典型地,催化剂在例如形状为伸长的管道或导管的固定床反应器中使用,其中典型地为蒸气形式的反应物穿过或通过所述催化剂。如果如要,可使用其它反应器,例如流化床或沸腾床反应器。在一些情形中,加氢催化剂可以与惰性材料结合使用以调节反应物料流通过催化剂床的压降和反应物化合物与催化剂颗粒的接触时间。
可以在液相或气相中进行加氢反应。优选地,在气相中于如下条件下进行该反应。反应温度可以为125℃-350℃,例如200℃-325℃、225℃-约300℃或250℃-约300℃。压力可以为10KPa-3000KPa(约0.1-30大气压),例如50KPa-2300KPa或100KPa-1500KPa。可以将反应物以大于500hr-1,例如大于1000hr-1、大于2500hr-1和甚至大于5000hr-1的气时空速(GHSV)给进到反应器。就范围而言,GHSV可以为50hr-1-50,000hr-1,例如500hr-1-30,000hr-1、1000hr-1-10,000hr-1或1000hr-1-6500hr-1。
任选在刚刚足以克服穿过催化床的压降的压力下以所选择的GHSV进行加氢,尽管不限制使用较高的压力,但应理解,在高的空速例如5000hr-1或6,500hr-1下可能经历通过反应器床的相当大的压降。
虽然该反应每摩尔乙酸消耗2摩尔氢气从而产生1摩尔乙醇,但进料流中氢气与乙酸的实际摩尔比可以为约100∶1-1∶100,例如50∶1-1∶50、20∶1-1∶2或12∶1-1∶1。最优选地,氢气与乙酸的摩尔比大于4∶1,例如大于5∶1或大于10∶1。
接触或停留时间也可以宽泛地变化,这些变量取决于乙酸的量、催化剂、反应器、温度和压力。当使用除固定床外的催化剂系统时,典型的接触时间为几分之一秒到大于若干小时,至少对于气相反应,优选的接触时间为0.1-100秒,例如0.3-80秒或0.4-30秒。
可以使乙酸在反应温度下气化,然后可将气化的乙酸随同未稀释状态或用相对惰性的载气例如氮气、氩气、氦气、二氧化碳等稀释的氢气一起给进。为使反应在气相中运行,应控制系统中的温度使得其不下降到低于乙酸的露点。
特别地,使用本发明的催化剂可以获得乙酸的有利转化率和对乙醇的有利选择性和产率。就本发明而言,术语“转化率”是指进料中转化为除乙酸外的化合物的乙酸的量。转化率按基于进料中乙酸的摩尔百分数表示。使用下面方程式由气相色谱(GC)数据计算乙酸(AcOH)的转化率:
就本发明而言,所述转化率可以为至少10%,例如至少20%、至少40%、至少50%、至少60%、至少70%或至少80%。虽然期望具有高转化率例如至少80%或至少90%的催化剂,但是在乙醇的选择性高时低的转化率也可以接受。当然,应充分理解,在许多情形中,可通过适当的再循环料流或者使用较大的反应器来弥补转化率,但却较难于弥补差的选择性。
选择性按基于转化的乙酸的摩尔百分数表示。应理解由乙酸转化的每种化合物具有独立的选择性并且该选择性不依赖于转化率。例如,如果所转化的乙酸的50摩尔%转化为乙醇,则乙醇选择性为50%。乙醇(EtOH)的选择性由气相色谱(GC)数据使用如下等式来计算:
其中“总mmol C(GC)”是指通过气相色谱法分析出的所有产物的碳的总摩尔数。
就本发明而言,催化剂对于乙氧基化物的选择性为至少60%、例如至少70%或至少80%。如本文所使用的,术语“乙氧基化物”具体是指化合物乙醇、乙醛和乙酸乙酯。优选地,乙醇的选择性为至少80%,例如至少85%或至少88%。在本发明的实施方案中还希望对不期望的产物例如甲烷、乙烷和二氧化碳具有低的选择性。这些不期望产物的选择性为小于4%,例如小于2%或小于1%。优选地,在加氢期间不生成可检测到的量的这些不期望的产物。在本发明的若干实施方案中,烷烃的生成是低的,穿过催化剂的乙酸的通常低于2%,经常低于1%,并且在许多情形中0.5%以下转化为烷烃,所述烷烃除作为燃料外具有很小价值。
产率是指基于所用催化剂的千克数计的在加氢期间每小时形成的规定产物例如乙醇的克数。在本发明的一个实施方案中,每千克催化剂每小时优选至少500克乙醇的产率,例如至少600g/kg/hr,至少700g/kg/hr,至少750g/kg/hr,至少800g/kg/hr,至少850g/kg/hr,至少900g/kg/hr,或至少1,000g/kg/hr。就范围而言,所述产率优选为每千克催化剂每小时500-3,000克乙醇,例如700-2,500或750-2,000。
本发明的一些催化剂可以实现至少10%的乙酸转化率,至少80%的乙醇选择性和每kg催化剂每小时至少200g乙醇的产率。本发明范围内的催化剂可以实现至少50%的乙酸转化率,至少80%的乙醇选择性,小于4%的不期望化合物的选择性,和每kg催化剂每小时至少600g乙醇的产率。
加氢方法中所使用的原料可以衍生自任何合适的来源,包括天然气、石油、煤、生物质等。众所周知通过甲醇羰基化、乙醛氧化、乙烯氧化、氧化发酵和厌氧发酵生产乙酸。由于石油和天然气价格波动,或多或少变得昂贵,所以由替代碳源生产乙酸和中间体例如甲醇和一氧化碳的方法已逐渐引起关注。特别地,当石油与天然气相比相对昂贵时,由衍生自任何可用碳源的合成气体(“合成气”)生产乙酸可能变得有利。例如,美国专利No.6,232,352(通过引用将其公开内容并入本文)教导了改造甲醇装置用以制造乙酸的方法。通过改造甲醇装置,对于新的乙酸装置,与CO产生有关的大量资金费用得到显著降低或在很大程度上消除。使所有或部分合成气从甲醇合成环路发生转向并供给到分离器单元以回收CO和氢气,然后将它们用于生产乙酸。除乙酸外,这种方法还可用于制备有关本发明所可利用的氢气。
美国专利No.RE 35,377(也通过引用将其并入本文)提供了一种通过使含碳材料例如油、煤、天然气和生物质材料转化生产甲醇的方法。该方法包括使固体和/或液体含碳材料加氢气化以获得工艺气体,用另外的天然气将该工艺气体蒸汽热解以形成合成气。将该合成气转化为可以羰基化为乙酸的甲醇。该方法同样产生如上述有关本发明所可使用的氢气。美国专利No.5,821,111以及美国专利No.6,685,754公开了一种将废生物质通过气化转化为合成气的方法,通过引用将它们的公开内容并入本文。
或者,可以直接从美国专利No.6,657,078(通过引用将其全文并入本文)中所描述的一类甲醇羰基化单元的闪蒸器取出蒸气形式的乙酸作为粗产物。例如,可以将粗蒸气产物直接给进到本发明的乙醇合成反应区而不需要冷凝乙酸和轻馏分或者除去水,从而节省总体工艺费用。
使用本发明的催化剂由加氢方法获得的乙醇可以按其自身用作燃料或随后转化为乙烯,乙烯是重要日用品原料,因为可将其转化为聚乙烯、乙酸乙烯酯和/或乙酸乙酯或任何许多其它化学产品。例如,还可将乙烯转化为许多聚合物和单体产品。下面显示了乙醇脱水得到乙烯。
可使用任何已知的脱水催化剂使乙醇脱水,所述脱水催化剂例如在美国公开No.2010/0030001和2010/0030002中所描述的那些,在此通过引用将它们的全部内容和公开内容并入本文。例如,沸石催化剂可以用作脱水催化剂。虽然可使用孔径为至少约0.6nm的所有沸石,但优选的沸石包括选自丝光沸石、ZSM-5、沸石X和沸石Y的脱水催化剂。例如沸石X描述于美国专利No.2,882,244中,沸石Y描述于美国专利No.3,130,007中,在此通过引用将它们全文并入本文。
乙醇还可以用作燃料,用于药物产品、清洁剂、消毒杀菌剂、加氢转化或消费。乙醇还可以用作用以制备乙酸乙酯、醛和高级醇,特别是丁醇的源材料。此外,可以将在根据本发明制备乙醇的过程期间形成的任何酯例如乙酸乙酯与酸催化剂进一步反应以形成另外的乙醇以及乙酸,可以将它们再循环到加氢过程中。
下面仅仅出于例示和说明目而参考许多实施方案详细描述了本发明。对本发明的精神和范围内以及所附权利要求书中给出的具体实施方案进行修饰,对于本领域技术人员而言将是显见的。
以下实施例描述了用于制备本发明方法中使用的各种催化剂的操作。
实施例
首先,在CaSiO3改性的SiO2载体上形成5个Pt/Sn催化剂,每个具有相同的Pt/Sn载量和比率。然后在实施例1-5的乙酸加氢中将所得催化剂进行测试,并且测定乙醇产率。用于实施例1的SiO2载体用结晶CaSiO3(约2-5%结晶度)进行改性,而实施例2-5的载体用无定形CaSiO3进行改性。将乙酸的反应进料液体蒸发并且随氢气和作为载气的氦气一起装入到反应器中。在图3中显示了所得乙醇产率。
如所示,利用包含结晶CaSiO3的CaSiO3的实施例1出人意料且意想不到地表现出850g/kg/hr的优越的乙醇产率。对比之下,均利用常规无定形CaSiO3的实施例2-5表现出至多780g/kg/hr乙醇产率。这比常规的改性负载型催化剂提高了约10%的乙醇产率。
虽然详细描述了本发明,但在本发明的精神和范围内的各种修改对于本领域技术人员而言将是显而易见的。鉴于上述讨论,上文关于背景技术和详细描述所讨论的本领域相关知识和参考文献,通过引用将它们的公开内容全部并入本文。此外,应理解在下文和/或在所附权利要求书中引述的本发明的各个方面以及多个实施方案和多个特征的各个部分可以部分或全部地进行组合或者互换。在前述各个实施方案的描述中,如本领域技术人员所可认识到的,引用另一个实施方案的实施方案可以与其它实施方案适当地组合。此外,本领域技术人员将认识到前述描述仅仅是举例方式,并且不意欲限制本发明。
Claims (29)
1.一种包含铂、锡、选自二氧化硅的含硅载体和选自碱土金属偏硅酸盐的至少一种偏硅酸盐载体改性剂的催化剂,其中铂以基于该催化剂总重量计0.1-25重量%的量存在,锡以基于该催化剂总重量计0.1-10重量%的量存在,所述含硅载体以基于该催化剂总重量计25重量%-99重量%的量存在,所述至少一种偏硅酸盐载体改性剂以基于该催化剂总重量计0.1重量%-50重量%的量存在,且铂与锡的摩尔比是0.4:0.6-0.6:0.4,其中按XRD测定所述偏硅酸盐载体改性剂的2wt.%-5wt.%是结晶相,其中所述含硅载体具有50m2/g-600m2/g的比表面积。
2.权利要求1的催化剂,其中所述二氧化硅选自热解二氧化硅或高纯度二氧化硅。
3.权利要求1-2中任一项的催化剂,其中所述至少一种偏硅酸盐载体改性剂选自金属的偏硅酸盐,所述金属选自镁和钙。
4.权利要求1-2中任一项的催化剂,其中所述至少一种偏硅酸盐载体改性剂包含CaSiO3。
5.权利要求1-2中任一项的催化剂,其中所述催化剂在乙酸加氢中具有每千克催化剂每小时至少800克的乙醇产率。
6.权利要求1-2中任一项的催化剂,其中该催化剂具有至少80%的乙醇选择性。
7.权利要求1的催化剂,其中所述含硅载体含有基于该催化剂总重量计小于1重量%的铝。
8.权利要求1的催化剂,其中所述含硅载体含有基于该催化剂总重量计小于0.30重量%的铝氧化物、钛氧化物和铁氧化物组合。
9.权利要求1的催化剂,其中该催化剂还包含不同于铂和锡的第三金属。
10.权利要求9的催化剂,其中所述第三金属选自钴、钯、钌、铜、锌和铼。
11.权利要求9的催化剂,其中所述第三金属以基于该催化剂总重量计0.05和4重量%的量存在。
12.权利要求1-2中任一项的催化剂,其中该催化剂在使乙酸转化为乙醇中适合用作加氢催化剂并且产生至少10%的乙酸转化率。
13.权利要求1-2中任一项的催化剂,其中该催化剂具有每100小时的催化剂使用降低小于6%的产率。
14.一种制备权利要求1的催化剂的方法,该方法包括以下步骤:
(a)使第一金属的第一金属前体与改性含硅载体接触以形成浸渍的载体,其中所述改性含硅载体含有选自二氧化硅的含硅材料和至少一种偏硅酸盐载体改性剂,按XRD测定所述至少一种偏硅酸盐载体改性剂包含至少0.5wt.%结晶偏硅酸盐;以及
(b)使第二金属的第二金属前体与改性含硅载体接触,和
(c)在有效还原所述第一金属并形成催化剂的条件下加热所述浸渍的载体,
其中所述含硅载体具有50m2/g-600m2/g的比表面积;
该方法还包括以下步骤:
(d)使所述至少一种偏硅酸盐载体改性剂或其前体与含硅载体接触以形成改性的载体前体;以及
(e)在有效形成改性含硅载体的条件下加热所述改性的载体前体。
15.权利要求14的方法,其中所述二氧化硅选自热解二氧化硅或高纯度二氧化硅。
16.一种生产乙醇的方法,该方法包括在催化剂存在下将乙酸加氢,所述催化剂包含铂、锡、选自二氧化硅的含硅载体和选自碱土金属偏硅酸盐的至少一种偏硅酸盐载体改性剂,其中铂以基于该催化剂总重量计0.1-25重量%的量存在,锡以基于该催化剂总重量计0.1-10重量%的量存在,所述含硅载体以基于该催化剂总重量计25重量%-99重量%的量存在,所述至少一种偏硅酸盐载体改性剂以基于该催化剂总重量计0.1重量%-50重量%的量存在,且铂与锡的摩尔比是0.4:0.6-0.6:0.4,其中按XRD测定所述偏硅酸盐载体改性剂的2wt.%-5wt.%是结晶相,其中所述加氢具有至少80%的乙醇选择性并且对于甲烷、乙烷和二氧化碳以及它们的混合物具有小于4%的选择性。
17.权利要求16的方法,其中所述二氧化硅选自热解二氧化硅或高纯度二氧化硅。
18.权利要求16的方法,其中该方法具有大于800g/kg/hr的乙醇产率。
19.权利要求16-18中任一项的方法,其中所述至少一种偏硅酸盐载体改性剂选自镁和钙的偏硅酸盐。
20.权利要求16-18中任一项的方法,其中所述含硅载体具有50m2/g-600m2/g的比表面积。
21.权利要求16-18中任一项的方法,其中所述含硅载体含有基于该催化剂总重量计小于1重量%的铝。
22.权利要求16的方法,其中所述催化剂还包含不同于铂和锡的第三金属。
23.权利要求22的方法,其中所述第三金属选自钴、钯、钌、铜、锌和铼。
24.权利要求22的方法,其中所述第三金属以基于催化剂总重量计0.05和4wt.%的量存在。
25.权利要求16-18中任一项的方法,其中在加氢期间可以使至少10%的乙酸转化。
26.权利要求16-18中任一项的方法,其中所述催化剂具有每100小时的催化剂使用降低小于6%的产率。
27.权利要求16-18中任一项的方法,其中所述乙酸得自煤源、天然气源或生物质源。
28.权利要求16-18中任一项的方法,其中包括使在加氢期间获得的乙醇脱水产生乙烯。
29.权利要求16-18中任一项的方法,其中所述加氢在气相中于125℃-350℃的温度、10KPa-3000KPa的压力和大于4:1的氢气与乙酸摩尔比下进行。
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- 2011-02-01 US US13/018,615 patent/US8569549B2/en not_active Expired - Fee Related
- 2011-02-01 CA CA2787419A patent/CA2787419A1/en not_active Abandoned
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TW201136660A (en) | 2011-11-01 |
IL221211A0 (en) | 2012-10-31 |
BR112012019418A2 (pt) | 2018-03-20 |
JP2013518705A (ja) | 2013-05-23 |
US8569549B2 (en) | 2013-10-29 |
HK1169348A1 (zh) | 2013-01-25 |
EP2531291A1 (en) | 2012-12-12 |
CN102421521A (zh) | 2012-04-18 |
KR20120112852A (ko) | 2012-10-11 |
AU2011213085A1 (en) | 2012-08-02 |
US20110257443A1 (en) | 2011-10-20 |
SG182607A1 (en) | 2012-08-30 |
CA2787419A1 (en) | 2011-08-11 |
RU2012137264A (ru) | 2014-03-10 |
MX2012008940A (es) | 2012-08-15 |
CL2012002130A1 (es) | 2013-03-08 |
WO2011097246A1 (en) | 2011-08-11 |
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