CN101460595B - 含氧化合物进料的催化加氢脱氧 - Google Patents
含氧化合物进料的催化加氢脱氧 Download PDFInfo
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- CN101460595B CN101460595B CN200780021019.2A CN200780021019A CN101460595B CN 101460595 B CN101460595 B CN 101460595B CN 200780021019 A CN200780021019 A CN 200780021019A CN 101460595 B CN101460595 B CN 101460595B
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- oxygenate feedstock
- hydrogenation deoxidation
- metal
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- 229910052751 metal Inorganic materials 0.000 claims abstract description 71
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- 238000000034 method Methods 0.000 claims abstract description 52
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000011148 porous material Substances 0.000 claims abstract description 20
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 7
- 239000010703 silicon Substances 0.000 claims abstract description 7
- 238000005984 hydrogenation reaction Methods 0.000 claims description 45
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 21
- 239000001257 hydrogen Substances 0.000 claims description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims description 16
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- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 claims description 11
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical group S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 10
- 239000002243 precursor Substances 0.000 claims description 10
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- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 9
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- 229910052698 phosphorus Inorganic materials 0.000 claims description 8
- 239000011574 phosphorus Substances 0.000 claims description 8
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 5
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 5
- -1 sulphur compound Chemical class 0.000 description 5
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 2
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
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- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
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- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
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- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—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
- 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
- B01J23/85—Chromium, molybdenum or tungsten
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—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
- 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
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/883—Molybdenum and nickel
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/20—Sulfiding
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
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Abstract
用于含氧化合物进料的加氢脱氧的方法,该方法包括在加氢脱氧条件下将所述进料与硫化的催化剂组合物进行接触,其中所述催化剂组合物包括:i)基本上由氧化铝形成的多孔载体,所述载体包含0~1重量%的磷和0~1重量%的硅(两者都以氧化物计算)并且具有5~40nm的平均孔径;和ii)1~20重量%的活性金属组分(基于所述组合物的重量并以氧化物计算),所述活性金属组分负载在所述多孔载体上并且包括至少一种VIB族金属和至少一种VIII族金属。
Description
技术领域
本发明涉及催化剂组合物及其在含氧化合物进料的加氢处理中的应用。更具体地,本发明关于包括在低酸度和宽孔的多孔载体上分散有活性金属组分的催化剂组合物,以及所述催化剂组合物在生物源的含氧化合物进料的加氢脱氧中的应用。
背景技术
考虑到限制来自工业处理的净碳排放的环境和财政的重要性,正广泛研究用合成产品部分或完全取代石油衍生产品。目前,来自生物源的燃料及其它衍生物(包括收割的农作物和农作物废料)代表一类重要的这种合成产品。因此,开发用于由这种生物源提取有用产品的高效方法是重要的。
许多现有技术文献已经教导,通过将石油基烃进料与由周期表VIB族和VIII族金属构成的催化活性金属组分进行接触,可以实现该石油基烃原料的加氢脱氮(HDN)、加氢脱硫(HDS)、加氢脱氧(HDO)和加氢脱金属。在由多孔材料例如二氧化硅、二氧化硅-氧化铝、氧化钍、二氧化钛和二氧化硅-二氧化钛构成的基体或载体上沉积这种活性金属(通常通过浸渍)。对于不同的加氢过程和不同品质的石油进料,使载体的多孔结构、所负载金属的形式和量进行最优化。
如果液化的生物质含有大量的含氧分子,显然的是,对于从其中提取有用的燃料和化学物质,高效的催化加氢脱氧(HDO)是所希望的。然而,对于使用和优化用于生物源烃原料的加氢处理的VIB族和VIII族活性金属催化剂,给予非常有限的关注。
参考文献例如美国专利4,313,852已经论述了在加氢脱氧反应中,活性金属组分,特别是钼和钨只有当它们处于硫化状态时才获得完全活性。然而,由于液化生物质通常不含有硫化合物,包括硫化的活性金属化合物的催化剂趋于相对不稳定,因为硫化物分解为它们的氧化物形式。因此,在本领域中需要提供具有改善稳定性的硫化催化剂,使得它们能够有效用于生物源含氧化合物进料的加氢脱氧。
在任何含氧化合物进料的加氢脱氧过程中,含碳沉积物可能积聚在多孔催化剂内部。这就减少了进料组分必须扩散其中的有效孔隙体积,从而减少了负载活性金属的暴露的有效表面积。这些作用结合起来随着时间推移降低了催化效率。因此,通常的操作是,通过从活性加氢脱氧区域取出催化剂并连续地将它们以典型流化床形式引入到再生区域对催化剂进行再生。在此,处理催化剂以从其中除去含碳材料,典型地通过以伴随的高能成本将它们燃烧掉。
尽管通过这种燃烧所产生的催化剂在返回到加氢脱氧区域时将会发挥作用,但它们不能获得与“新鲜的”催化剂相同的效率;再生方法可能导致在催化剂的孔隙内或在催化剂颗粒之间的间隙内夹带氧分子,并且在加氢脱氧过程中,这些氧分子能降低多孔材料的活性和选择性。尽管例如美国专利申请公开2002/215840(Beech等)文献描述了除去这种夹带的氧的方法,其附加步骤进一步增加了整个加氢脱氧方法的复杂性和能量需求。
因此,在生物源含氧化合物进料的加氢脱氧中使用如下催化剂是有利的,该催化剂的特征在于限制了焦炭和其它含碳沉积物在其孔结构内积聚。
发明内容
通过本发明满足本技术领域中的这些及其它的需求,本发明提供一种用于含氧化合物进料的加氢脱氧的方法,该方法包括在加氢脱氧条件下使所述进料与硫化的催化剂组合物接触,其中,所述催化剂组合物包括:i)基本上由氧化铝形成的多孔载体,所述载体包含0~1重量%的磷和0~1重量%的硅(两者都以氧化物计算)并且具有5~40nm的平均孔径;和ii)1~20重量%的活性金属组分(基于所述组合物的重量以氧化物计算),其负载在所述多孔载体上并且包含至少一种VIB族金属和至少一种VIII族金属。优选所述载体具有10~20nm的平均孔径。
本文所使用的术语“含氧化合物(oxygenate)”表示包含至少一个氧原子的烃类化合物。可以想象的是,该方法可以适用于任何合适的含氧化合物进料,特别适用于生物源进料。然而,优选地,含氧化合物进料的特征在于包含甘油三酯和/或甘油三酯的氧化反应产物(其与加氢脱氧催化剂接触之前已经进行一个或多个加氢处理步骤)。这种甘油三酯可以合适地来源于鱼、动物或植物油。当对所述甘油三酯进行一个或多个在先的加氢处理步骤时,优选这些步骤包括酯交换;在这种实施方式中,含氧化合物进料包括至少10重量%,更优选至少50重量%,最优选至少75重量%的来自于甘油三酯的酯。
典型的加氢脱氧条件包括在250℃~450℃范围内的温度、在10~220巴范围内的氢分压、在0.1~10hr-1范围内的液体时空速(LHSV)。在将本发明方法的加氢脱氧转化率定义为(有机)键合的氧转化为H2O的转化率下,在这些条件下可以获得至少85%的转化率,通常至少90%。
为了以硫化物形式保持催化剂的金属组分,而不是转化为它们的金属氧化物形式,优选在存在硫化氢(H2S)或者其前体的情况下使所述含氧化合物进料与催化剂组合物接触,使得在氢气中存在所述硫化氢的量为10ppm~10000ppm,优选为10ppm~1000ppm。
本发明的催化剂组合物的特征在于低负载的活性金属组分,所述催化剂组合物的优选金属含量为5~20wt%。对于加氢脱氧功能,这种低负载并不会牺牲催化活性。已经发现:当在加氢脱氧条件下使用时,所述加氢脱氧条件包括其特征在于硫含量小于2mg/Kg和氮含量小于10mg/Kg的菜籽油进料;温度为约300℃;氢分压为50巴;H2/油比例为1000nL/L;及液体时空速为约5hr-1;进料循环比为约5,用于本发明的催化剂组合物可以获得每小时每克所述活性金属组分大于12克氧(g O/gM/hr)的加氢脱氧活性,该加氢脱氧活性被定义为1减去反应产物与含氧化合物进料中残留氧相比的分数。
活性金属的低重量百分比(基于催化剂的总重量)还限制这些组分的“聚集”或不均匀分布,因此,有助于两种或多种金属组分的共同作用。
可以设想VIB族和VIII族金属的任何组合用于所述催化剂组合物。然而,根据本发明的优选实施方式,所述催化剂组合物的VIB族金属包括钼(Mo)和/或所述催化剂组合物的VIII族金属包括镍(Ni)。更具体地,优选所述催化剂组合物的活性金属组分包括10~18重量%的钼和2~5重量%的镍。在这些范围或其各自范围内,进一步优选所述催化剂组合物的所述活性金属组分的特征在于:Mo/Ni重量比在4:1~2:1范围内。
对于这种催化剂的特定应用,氧化铝多孔载体的酸度应该保持在低的水平。根据本发明的优选实施方式,通过使用包括小于0.5重量%,更优选小于0.1重量%的磷;和/或小于0.5重量%,更优选小于0.1重量%的硅(两者都基于所述组合物的重量并且以氧化物计算)的多孔氧化铝载体来获得这种低的酸度。
定义
如本文所使用的,术语“金属”表示如下金属:(a)该金属存在于基本上氧化铝宏观结构的内表面上或所述宏观结构的外表面上或两者之上;和(b)该金属影响宏观结构的颗粒的催化性能或者影响所述宏观结构的颗粒的吸附性能或者两者。术语“金属”并不包括多孔无机材料所包含的金属。例如,在结晶微孔分子筛的情况中,术语“金属”不包括结晶分子筛骨架中的任何金属。
通过原子吸收光谱、感应耦合等离子体-原子发射光谱法或由ASTM规定的测量各种金属的其它方法来测量金属的量。
本文所使用的术语“总体积”是指,如果宏观结构内所有孔隙都用无孔材料来填充,则由宏观结构材料置换的体积。
在本说明书的上下文中,“平均孔径”被定义为如下孔径,其中该催化剂的一半孔体积是存在于直径低于该值的孔中,而另一半孔体积存在于直径高于该值的孔中。通过在140℃接触角的汞压法测得从其中获得该数据的孔径分布。
用于测定基本上宏观结构的密度、中孔孔隙率、微孔空隙率和粒度分布的程序对于本领域技术人员是已知的。在G.Ertl,H.Knozinger和J.Weitkamp的多相催化剂手册(1997年)描述了这种程序的实例。
附图说明
图1说明了根据本发明的优选实施方式可以在催化剂组合物的预硫化处理中使用的加热制度。
具体实施方式
催化剂组合物
使用可以对所述氧化铝的比表面积、孔隙体积和孔径分布实施合适控制的方法,可以生产用于加氢脱氧催化剂的氧化铝载体。在以下专利公开中描述的合适的方法:日本专利公告公开71456/1971和日本专利公开26512/1986的载体(其中由通过铝盐的水解所制得的假勃姆石获得氧化铝);日本专利公开166220/1985、日本专利特公开24824/1993、日本专利公开166220/1985、日本专利特公开24824/1993、日本专利公开166220/1985、日本专利特公开10535/1995和美国专利2,915,475,其中氧化铝源是通过铝盐、金属铝或铝醇盐的水解所获得的各种氧化铝水溶胶、凝胶。此外美国专利申请2003/044348描述了用于制备具体氧化铝组合物的方法,在存在水的条件下,将含酸的氢氧化铝、通过在存在一元酸或其盐的条件下处理活性氧化铝所获得的含酸的氧化铝、三羟铝石和γ-氧化铝混合;然后将该混合物通过水热合成进行溶胶-形成反应、中和、水热处理、干燥、焙烧等。美国专利申请公开2005079126(Le Loarer等)描述了通过铝氢氧化合物或氢氧化物的脱水、因此所获得的氧化铝的团聚、然后水热处理和焙烧该团聚物来制备团聚的氧化铝载体材料。所有这些文献的公开内容在此引入作为参考。
设想氧化铝载体能具有模态的孔径分布(modal pore size distribution)或者双峰的孔径分布,尽管前者在本申请中是优选的。美国专利6,919,294描述了生产加氢精炼催化剂的方法,该加氢催化剂含有加氢-活性金属,并且基本为氧化铝并具有双峰孔隙特征的无机氧化物载体。因此,该文献的公开内容在此引入作为参考。
不管用于获得氧化铝载体的实际方法,对于本发明载体具有低酸度是重要的,更具体地,氧化铝载体的磷和硅含量分别在0~1重量%(基于所述催化剂组合物的重量并以氧化物计算)是重要的。优选地,所述催化剂组合物的氧化铝载体包括小于0.5重量%的硅和磷中的一种或两种,更优选小于0.1重量%。最优选地,所述催化剂的氧化铝载体基本上不含硅或磷。
可以通过上述参考方法中使用的铝源纯度来获得这种载体。或者,如果所述氧化铝载体的必要的低酸度可以通过添加助催化剂和/或掺杂剂来控制。助催化剂和/或掺杂剂的实例包括:卤素,特别是氟;硼;氧化钇;稀土氧化物和氧化镁。助催化剂如卤素通常增加金属氧化物载体的酸度,而弱碱掺杂剂如氧化钇或氧化镁倾向于降低这种载体的酸度。
要进行加氢脱氧的原料组分应当通过催化剂的孔隙进行扩散。当然,必须选择无机载体的孔径和孔隙体积以提供这种催化剂可获得性,但是,也测定下面这些参数:催化剂的体积密度和断裂强度;以及当大批装载在反应器中时催化剂的寿命;超过给定的时间期间污染物在催化剂上沉积的沉积度;以及表面积与决定催化剂活性的孔隙体积之间的比例。
本发明催化剂组合物中所包括的载体具有5~40nm,优选8~30nm,更优选10~20nm的平均孔径。优选地,直径大于100nm的气孔应当具有1~30%孔隙体积,优选1~20%,更优选1~10%。
所述催化剂组合物的VIB族金属优选选自钼、钨或它们的混合物,钼是特别优选的。VIB族金属的量优选为10~18重量%[以三氧化物计算]。
所述催化剂组合物的VIII族金属优选选自镍、钴或它们的混合物,镍是特别优选的。VIII族金属的量优选为0.1~10重量%[以氧化物计算],更优选为0.1~7重量%,最优选为2.0~5.0重量%。
根据本发明的优选的实施方式,所述催化剂组合物的活性金属组分包括10~18重量%的钼(以三氧化物计算)和2.0~5.0重量%的镍(以氧化物计算)。在存在或不存在其它的VIB族和VIII族金属下,还优选的是,所述催化剂组合物的特征在于Mo/Ni重量比在4:1~2:1范围内。
能够在氧化铝载体上引入所述金属组分,使得催化活性物质以非常精细分散的形式分布在载体材料上,从而使单位质量的活性金属的表面积最大化的任何方法都适用于本发明的催化剂制备。
用于在微粒载体材料的表面上分布催化活性物质的常用方法包括:用含有所需金属的催化活性材料的前体的溶液浸渍所述载体材料;随后对浸渍的载体材料进行干燥和焙烧;从而将所沉积的含金属材料转化为相应的金属氧化物。可以用含金属组分前体的溶液在一个或多个步骤中浸渍所述载体颗粒。对于VIB族金属,七钼酸铵、二钼酸铵、钨酸铵可以是适合的前体。对于VIII族金属,可以考虑硝酸镍和硝酸钴。浸渍溶液可以含有磷化合物例如磷酸,以提高溶液的稳定性。也可以存在本领域中已知使用的其它化合物,例如柠檬酸。
在25℃~200℃温度下的任选干燥步骤后,将所获得的材料在350℃~750℃的温度下焙烧最高约2小时,以将至少部份,优选全部的金属组分前体转化为氧化物形式。
本领域普通技术人员了解这种方法的广泛范围的变化。例如,能够应用多个浸渍步骤,所使用的浸渍溶液含有一种或多种要沉积的或部分沉积的组分前体。或者,可以使用浸涂方法和喷涂方法替换浸渍技术。如果使用多次浸渍、浸涂和干燥步骤,则可以在每个单独步骤后进行煅烧。
在基本为氧化铝的载体上精细且均匀地分布作为催化活性金属的镍和钴的另外已知方法包括在金属铵碳酸盐络合物(complex metal amine carbonate)的溶液中悬浮所述载体材料。然后加热所获得的悬浮液(同时搅拌),将金属氨碳酸盐络合物分解为不溶的金属碳酸盐或碱性金属碳酸盐,它们沉积在悬浮的载体材料上。通过进一步加热,如果必要,还原,可以将所述碳酸盐分别转化为金属氧化物或金属元素。
该方法在本发明中并不是优选的,其原因如下:该方法需要使用高的氨浓度以获得可溶形式的氨络物碳酸盐(ammine carbonate);所伴随的高pH值会部分溶解氧化铝载体。当除去氨时,该除去氨是使金属氨络物碳酸盐分解所必须的,该溶液的pH值降低。从而,载体材料的溶解部分将会沉积,包裹所沉积的活性材料颗粒,从而使其失活。因此,如果使用低的活性金属浓度,则这种影响的意义会增加。
然而在英国专利1220105(Stamicarbon)描述了更适合的“悬浮”技术。
所获得的催化剂颗粒可以具有许多不同的形状。适合的形状包括圆柱形;球形;环形以及对称和不对称的多叶形(polylobe),例如三叶形或四叶形。当然会认识到,可以使用长度、宽度及直径的参数限定这些形状;然而对于给定的颗粒形状,优选这些参数中的每个参数在1~50mm的范围内。
在催化剂用于原料加氢处理之前,可以以允许在从氧化物形式转化为硫化物形式的每个阶段平衡的任何常规方式将催化剂活性金属组分(部分或全部)转化为它们的硫化物形式。不允许这种平衡的技术是不适合的,因为它们可能导致金属硫化物分散体的损失,从而损失催化活性。
例如,用氢和硫化氢的混合物(任选地进一步用氮气或废气稀释),可以在220~500℃的温度下原位(在反应器中)预硫化1~10小时。或者,在1~10Mpa的氢压力和200~300℃的温度下,可以用正己烷中的CS2预硫化所述催化剂。
根据本发明优选的实施方式,使用二甲基二硫(DMDS)示踪SRGO(S=3.7重量%)预硫化所述催化剂。在50巴的H2压力下实施浸渍(soaking),并且以3.0hr-1液体时空速(LHSV)维持3小时。
图1说明了催化剂进行浸渍(soaking)和预硫化的条件的优选实施方式。
含氧化合物进料(oxygenate feedstock)
生物源甘油三脂可以合适地由鱼、动植物油来获得。特别有用的甘油三脂源(可以单独或组合使用)包括椰子油、棕榈油、棕榈坚果油、红花油、芝麻油、豆油、菜籽油、玉米油、芥子油、向日葵油、黄色油脂、高酸值油脂(trapgrease)、猪油、食用动物脂、非食用油脂以及它们的混合物。最为优选的来源是菜籽油。
因为甘油三脂生物源的杂质水平不同[例如,无脂肪酸(FFA)、痕量的金属、磷脂、类胡萝卜素、黄曲霉素、杀菌剂和多氯代烃],可以进一步对所述来源进行预处理,以在酯交换步骤之前除去这些杂质。当然,实际上应用的预处理方法取决于所使用的油种类,但是通常包括选自脱胶、除臭(真空蒸馏)、汽提、碱洗提、溶剂萃取和漂白中的至少一种方法。
认为本发明的方法也可以包括甘油三脂来源的酯交换的步骤,其中在加氢脱氧步骤之前进行所述步骤。由此,酯交换的含氧化合物产物与催化剂进行接触。可以根据已知技术对酯交换条件,特别是温度和甲醇量、与甘油三脂一起的碱(例如NaOH))加以变化,使得含氧化合物产物包括至少10重量%,更优选至少50重量%,最优选至少75重量%的酯。[K.S.Tyson,“BiodieselTechnology & feedstocks”的公开内容,国家可再生能源实验室(NREL)出版物,2003年3月26日,在此引入作为参考]。此外,调整所述酯交换条件使得含氧化物产物实质上包括通式R-O-Me的甲基酯,式中R是碳原子数为C10-C50,更优选为C15-C40的烃部分。
在本发明中,含氧化合物进料可以为液相、蒸汽相或混合的蒸气/液相。
可以任选地向含氧化合物进料中添加一种或多种惰性稀释剂,以降低其在全部进料中的有效浓度。稀释剂通常应该不与原料或多孔载体反应,从而适合的稀释剂包括氦、氩、氮、一氧化碳、二氧化碳、氢和水,其中惰性稀释剂是最优选的。当具有稀释剂时,该稀释剂可以占1~99摩尔%,优选为约1~80摩尔%,更优选为约5~约50摩尔%,最优选为约5~约25摩尔%(基于所述进料和引入到反应区域或其催化剂床中的稀释剂的摩尔总量)。
加氢脱氧条件
如果使用稀释剂,则含氧化合物进料与稀释剂(每个组分单独引入或组合引入)与催化剂组合物在使所述原料有效加氢脱氧的工艺条件下进行接触。进行接触的容器在此称为“反应器”,它是“反应器装置”或“反应***”或“反应器***”的一部分。“反应器入口”被指定为反应器中最高总压力的点,在此全部或部分含氧化合物进料与催化剂组合物进行接触。
如果单独引入到反应器中,则在发生含氧化合物显著转化之前将含氧化合物和稀释剂混合是重要的。以这种方式,在进行含氧化合物转化反应中所述含氧化合物和稀释剂将会获得它们适当的分压。
通过调整以下一个或多个参数来控制本发明的具体加氢脱氧条件:反应温度和压力;进料组成;所使用的稀释剂的有效量;进料流速,即液体时空速(LHSV);具体的反应器构造;以及催化剂再生的和/或再循环的水平和程度。
典型的加氢脱氧条件包括在250~400℃范围内的温度、在10~220巴范围内的氢分压、在0.1~10hr-1范围内的液体时空速(LHSV)。更优选地,加氢脱氧条件包括在280~380℃范围内的温度、在20~100巴范围内的氢分压、在0.2~2hr-1范围内的液体时空速。
为了控制加氢脱氧反应的放热量,从反应区域除去的一些反应产物应当进行再循环(使得总进料量高于新鲜进料的量)。在本发明中,优选的循环比定义如下:
(循环产物速率+进料速率)/新鲜进料速率
该循环比在1~10范围内。
根据本发明的优选实施方式,含氧化合物进料在存在硫化氢(H2S)或其前体,特别是CS2条件下与所述催化剂进行接触,使得在所述氢中存在的硫化氢的量为10ppm~2000ppm,更优选为10ppm~1000ppm。
不局限于理论,在存在氢条件下的加氢脱氧主要通过氢解作用来进行(其中氧从原料中以水形式除去)。以限定水平的硫化氢或其前体添加量抑制了氢解,并且提高了其它脱氧反应(以二氧化碳、一氧化碳和/或二氧化硫形式除去氧);这能降低在HDO过程中总的氢消耗量。当应用时,一些H2S可以使加氢脱氧催化剂保持其活性的硫化状态。
可以在各种催化反应器中进行含氧化合物的转化,包括流化床反应器、逆流自由下落反应器和并流提升管反应器,如在美国专利4,068,136和在Fluidization Engineering,D.Kunii和O.Levenspiel,Robert E.Krieger PublishingCo.NY,1977中所描述的,其全部公开内容在此引入作为参考。尽管可以使用任何标准的商用规模反应器***,包括固定床或移动床***,优选在动态床***,更优选在以高空间速度操作的动态床***中实施该方法。
在使用气体表面速度等于或低于约1m/s的密实流化床反应器中,认为进料和反应物组分在反应器的各个位置均匀混合,含氧化合物和稀释剂被引入到反应器中的位置并不重要。在使用气体表面速度超过1m/s的固定床反应器或者流化床反应器中,希望以如下方式将所述进料和和稀释剂引入到反应器中,该方式确保在剩余的含氧化合物和稀释剂在反应器中混合在一起之前不多于30%的含氧化合物被转化。用于实现的方法取决于引入装置例如进料嘴的位置,以及通过这种装置引入的相对速率,该方法对于本领域技术人员是公知的。
在任何所使用的反应器中含氧化合物的转化应当维持足够高的水平,以减少不希望的副产品的量和任何未反应进料的再循环程度。通常,50摩尔%转化水平(伴随的剩余50摩尔%的再循环)商业上是可接受的。然而,希望获得大于85摩尔%,更优选大于98摩尔%的转化水平,以简化任何再循环过程。本领域普通技术人员了解多种保持这种水平含氧化合物转化的方法。
因为在加氢脱氧反应过程中会在分子筛催化剂的表面上或在分子筛催化剂的内部形成含碳沉积物,例如“焦炭”,所述催化剂典型地通过燃烧至少部分焦炭沉积物来再生。以保持在反应器内部的全部催化剂的活性水平所需要的次数和条件下进行这种再生。在Michel Louge,“Experimental Techniques”,Circulating Fluidized Beds,Grace,Avidan,& Knowlton,eds.,Blackie,1997(336337)中描述了用于实现此的技术,在此将其内容引入作为参考。
在该方法的实施方式中,一部分焦化的催化剂组合物从反应器中排出并引入再生***。该再生***包括再生器,其中焦化的催化剂组合物与再生介质,优选含有氧气的气体在常规再生温度、压力和停留时间条件下进行接触。选择再生条件使得焦炭从焦化的催化剂组合物中燃烧掉以形成再生的分子筛催化剂组合物。
再生介质的非限制实施例包括氧气、O3、SO3、N2O、NO、NO2、N2O5、空气、用氮或二氧化碳稀释的空气、氧气和水(参见美国专利6,245,703,在此引入作为参考)、一氧化碳和/或氢中的一种或多种。
再生温度可以在约200℃~约1500℃范围内,但是,优选在450℃~550℃范围内。再生压力可以在约15psi(103kPa)~约500psi(3448kPa)范围内,优选为约20psi(138kPa)~约250psi(1724kPa),更优选为约25psi(172kPa)~约150psi(1034kPa),最优选为约30psi(207kPa)~约60psi(414kPa)。
所述催化剂组合物在再生器中的停留时间优选在约1分钟~几小时范围内,最优选为约1分钟~100分钟。基于所述气体的总体积,气体中的氧的体积优选为约0.01~约5摩尔%。
可以添加再生助催化剂以促进催化剂组合物的再生。这种助催化剂典型地为含金属化合物例如铂、钯等,这可以直接添加到再生器中,或者可间接地例如与焦化的催化剂组合物一起添加。
在一种实施方式中,基于焦化的催化剂组合物的总重量,再生的催化剂组合物具有小于约2重量%,更优选小于约1重量%,更优选小于约0.5重量%的焦炭水平。然而,本领域技术人员可以控制再生的严重程度,以提供保留一些焦化物质的催化剂,即获得部分再生的催化剂,这在氧化-烯烃反应过程中具有提高的轻烯烃的选择活性。
可以间歇、半连续或连续的方式实施该方法。可以在单个反应区域或串联或并联设置的多个反应区域中实施该方法。
测定催化剂活性的测试条件
为了说明在此使用的催化剂组合物的活性是出乎意料的高,并且可以与较高的金属负载的催化剂相比,可以在具体的测试条件下测量催化剂活性。这些条件表示在该条件下典型使用催化剂组合物的加氢脱氧的条件。
所述催化剂组合物为压出物的形式,并且置于固定床反应器中,使得在所述催化剂组合物中的金属的质量为135~145g/升反应器体积。尽管在这些试验条件下催化剂的形状和尺寸可以在它们的工业应用过程中进行优化,但是,通常使用直径为1-6mm的圆柱形、三叶和/或四叶形催化剂。使用DMDS示踪的SRGO(S=3.7重量%)预硫化所述催化剂。在50巴的H2压力下进行浸渍(soaking),并且以3.0-1的液体时空速(LHSV)保持3小时。
使用菜籽油进料作为试验用的含氧化合物,其特征在于硫含量小于2mg/Kg、氮含量小于10mg/Kg。在测试期间所使用的加氢脱氧条件包括温度约300℃、氢分压50巴、H2/油比>1000nL/L和液体时空速约5hr-1。循环比为5。在加氢脱氧方法过程中,菜籽油主要转化为n-C17和c-C18石蜡,副产物为丙烷、水、二氧化碳和一氧化碳。
催化剂活性被定义为1减去
在全部液体产物中与含氧化合物进料中残留的氧相比的分数。根据本发明的催化剂理论上的活性大于12,优选大于15,更优选大于17g O/g金属/小时。
下面实施例进一步说明本发明催化剂体系的制备和使用。
实施例1
制备具有如表1所示性能的两种不同的催化剂。
表1
将五十毫升的各种催化剂装载在固定床反应器中。使用具有如下表2所限定的性质的菜籽油进料通过上流、并行测试来证实加氢脱氧性能。
表2
催化剂预硫化:在预硫化期间使用DMDS示踪的SRGO(S=3.7重量%)。在50巴的H2压力下进行浸渍,并且以3.0hr-1的液体时空速(LHSV)保持3小时。在浸渍之后,设定H2/油为200nL/L,并根据图1所示加热催化剂床温。
在测试过程中,WABT根据表3进行变化:
表3
其它参数是:LHSV=5hr-1,压力50巴。为了降低加氢脱氧的放热量,以1:5(新鲜料:总料)的循环比使用活性催化剂再循环。
在下表4中显示了由该加氢脱氧方法获得的性能结果:
表4
尽管两种催化剂具有低的金属负载,但均表现出高的活性。在相同的加氢脱氧条件下,在催化剂A上沉积焦炭少于在比较例的催化剂B上沉积的焦炭。
本发明并不被限制于上述的实施方式。在下面的权利要求书中限定所要求保护的权利要求,在该权利要求的范围内可以设想进行许多变化。
Claims (12)
1.用于生物源含氧化合物进料的加氢脱氧的方法,包括在加氢脱氧条件下使所述进料与硫化的催化剂组合物接触,其中,所述催化剂组合物包括:
i)基本上由氧化铝构成的多孔载体,所述载体包含以氧化物计算0~1重量%的磷和以氧化物计算0~1重量%的硅并且具有5nm~40nm的平均孔径;和
ii)基于所述组合物的重量并以氧化物计算1~20重量%的活性金属组分,所述活性金属组分负载在所述多孔载体上,并且包含至少一种VIB族金属和至少一种VIII族金属;
其中,所述接触是在存在硫化氢或其前体的情况下进行的;
所述生物源含氧化合物进料包括至少50重量%的脂肪酸衍生的甘油三酯。
2.根据权利要求1所述的方法,其中,所述生物源含氧化合物进料包含至少75重量%的酯。
3.根据权利要求2所述的方法,其中,所述生物源含氧化合物进料包括已经经过酯交换的甘油三酯的反应产物。
4.根据权利要求1-3中任一项所述的方法,其中,所述加氢脱氧条件包括:在250℃~450℃范围内的温度,在10~220巴范围内的氢分压,在0.1~10hr-1范围内的液体时空速(LHSV)。
5.根据权利要求1-3中任一项所述的方法,其中,在存在硫化氢(H2S)或其前体的情况下,使所述生物源含氧化合物进料与所述催化剂组合物接触,使得在氢气中存在的所述硫化氢的量为10ppm~10000ppm。
6.根据权利要求5所述的方法,其中,在氢气中存在的所述硫化氢的量为10ppm~1000ppm。
7.根据权利要求1-3中任一项所述的方法,其中,所述催化剂组合物的所述氧化铝载体包含小于0.5重量%的硅和小于0.5重量%的磷。
8.根据权利要求1-3中任一项所述的方法,其中,所述催化剂组合物的所述氧化铝载体具有在10~20nm范围内的平均孔径。
9.根据权利要求1-3中任一项所述的方法,其中,所述催化剂组合物的所述VIB族金属包括钼(Mo)。
10.根据权利要求9所述的方法,其中,所述催化剂组合物的所述VIII族金属包括镍(Ni)。
11.根据权利要求9所述的方法,其中,所述催化剂组合物的所述活性金属组分包括10~18重量%的钼和2~5重量%的镍。
12.根据权利要求11所述的方法,其中,所述催化剂组合物的所述活性金属组分的特征在于,Mo/Ni重量比在4:1~2:1的范围内。
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