CN104428060A - 加氢脱氧催化剂 - Google Patents
加氢脱氧催化剂 Download PDFInfo
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- CN104428060A CN104428060A CN201380036207.8A CN201380036207A CN104428060A CN 104428060 A CN104428060 A CN 104428060A CN 201380036207 A CN201380036207 A CN 201380036207A CN 104428060 A CN104428060 A CN 104428060A
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Abstract
一种加氢脱氧催化剂,其包含金属催化剂、酸促进剂和载体。所述金属催化剂选自铂、钯、钌、铼、铑、锇、铱、镍、钴、钼、铜、锡或其混合物。所述载体为经促进的锆材料,包括织构促进剂和酸促进剂。所述加氢脱氧催化剂可用于在水溶液中的糖或糖醇的加氢脱氧(HDO)。在一个实施方案中,所述HDO催化剂可用于脂肪酸类如脂肪酸甲酯(FAME)、三酸甘油酯(植物油和动物脂肪中的)、热解油或木质素的HDO。所述用于脂肪酸处理的加氢脱氧催化剂无需使用酸促进剂,其是可选的。
Description
发明背景
与原油相比,生物质原料本身具有从6%(天然油和脂肪)至超过50%(碳水化合物)的高氧含量。通过脱羧/脱羰将这些原料转化成高价值化学品或“可直接使用(drop in)”的燃料而不过度牺牲碳需要加氢脱氧(HDO)作为必要的工艺步骤。HDO方法类似于已广泛用于石油精炼中的加氢处理方法。其通过消耗氢而以水的形式移除作为“杂质”的氧。
来自植物油和动物脂肪的HDO的可再生柴油已通过使用负载于沸石或二氧化硅-氧化铝上的常规NiMo基和CoMo基加氢处理催化剂而商业生产。其成功可归因于较低的氧含量、原料中的较少杂质以及重要地,工艺设计和优化(美国专利第7,955,401号、美国公开第2010/0331586号)。一旦用于生物质衍生的原料的加氢脱氧,这些常规加氢处理催化剂就容易失活。快速失活可能归因于活性氧官能团、杂质、焦炭形成、水毒化和二氧化硅-氧化铝基载体浸出。此外,同时供入硫化合物以保持常规加氢处理催化剂的活性会导致下游产品的污染(Chem.Rev.,110,2010,3552)。
美国公开第2009/0255171号中描述了一种由生物质衍生的烃制备液体燃料和化学中间体的方法。所述方法包括如下步骤:在单一反应器中使山梨糖醇或甘油的水溶液在Pt-Re/C催化剂的存在下反应以产生包含蒸气相、含直链和/或环状单含氧烃的有机相和水相的自分离三相产物料流。在该方法中,离开反应器的来自山梨糖醇转化的碳主要由烷烃、含氧化合物(C4-C6醇、酮、酸和杂环化合物)和COx(占产物中总碳的约20-30%)构成。Pt被认为对蒸汽重整和水煤气变换反应呈活性,而Re被认为对脱水和C-O键裂解呈活性。所述方法包括水相重整反应(APR)。不需要与糖醇一起供入额外的氢气。然而,在气相中的碳损失以CO2计为约15-20%。
由于生物质衍生的原料如糖和糖醇、植物油/动物脂肪、来自生物质热解或水热方法的生物原油和木质素的宽范围氧含量和特性,HDO工艺条件变化极大。在一些情况下,需要在含水反应条件下的操作,例如糖和糖醇的HDO反应。因此,耐水性是对于处理生物质衍生的原料的HDO催化剂所需的特性。
美国公开第2011/0301021号(通过引用将其全文并入本文)中描述了制备在水相应用下水热稳定的多元酸促进的氧化锆挤出物的方法。将氧锆基促进剂前体在不存在任何粘结剂、挤出助剂或稳定剂下挤出。经煅烧的载体包含超过85%的由多元酸促进剂稳定的四方晶相的锆氧化物。
发明简述
加氢脱氧催化剂包含金属催化剂和具有可调的酸密度和强度的水热稳定的载体。所述金属催化剂选自铂、钯、钌、铼、铑、锇、铱、镍、钴、钼、铜、锡或其混合物。所述载体为经促进的锆材料。
所述加氢脱氧催化剂可用于脂肪酸类如脂肪酸甲酯、脂肪酸、植物油、动物脂肪、热解油、木质素、或糖或糖醇的HDO。
这些和其它目的及优点由附图及其描述变得显而易见。
附图简述
引入并构成本说明书一部分的附图阐释了各实施方案,其与上文给出的一般描述和下文给出的各实施方案的详细描述一起用于解释本公开内容的原理。
图1显示了酸促进的ZrCr载体的XRD谱图(Cu kα)。还包括四方ZrCr氧化物载体的XRD谱图以进行对比。
图2显示了所制备的HDO催化剂的NH3-TPD曲线。
图3显示了在不同反应条件下操作且使用Pt-Nb/ZrCr催化剂的山梨糖醇HDO的反应时间(time-on-stream,TOS)-山梨糖醇转化率。
图4显示了在不同反应条件下操作且使用Pt/ZrCr催化剂的山梨糖醇HDO的反应时间(TOS)-山梨糖醇转化率。
图5显示了使用Pt-W/ZrCr催化剂的山梨糖醇HDO的反应时间-山梨糖醇转化率。
图6显示了使用Pt-Mo/ZrCr催化剂的山梨糖醇HDO的反应时间-山梨糖醇转化率。
图7显示了使用实施例5的催化剂在400℃下FAME HDO 2小时的FAME进料和产物中的直链烃的碳分布。
图8显示了使用实施例11的催化剂在400℃下FAME HDO 2小时的FAME进料和产物的碳分布。
图9显示了使用实施例12的催化剂在400℃下FAME HDO 2小时的FAME进料和产物的碳分布。
图10显示了使用实施例13的催化剂在400℃下FAME HDO 2小时的FAME进料和产物的碳分布。
图11显示了获自糖醇水相HDO的潜在产物的实例。
发明详述
所述HDO催化剂为双功能催化剂,其包含用于加氢的金属催化剂以及用于脱水和水解的酸性载体。所述酸性载体通过添加各种酸促进剂而构筑在具有可调的酸密度和强度的水热稳定的载体上。在一个实施方案中,所述HDO催化剂可用于糖、糖醇于水相反应中的HDO,植物油/动物脂肪的HDO,木质素的HDO,来自热解和其它水热处理的生物原油的HDO。在另一实施方案中,所述HDO催化剂可用于包含含氧化合物,例如游离脂肪酸和游离脂肪醇的费-托合成烃的HDO。
在一个实施方案中,所述载体包含至少两种类型的促进剂:织构促进剂(textural promoter)和酸促进剂。根据美国公开第2011/0301021号制备的水热稳定的Cr促进的氧化锆载体是织构促进剂的一个实例,其有助于维持物理强度和四方晶相。该水热稳定的载体进一步由Nb、W、Mo及其组合促进,从而调节酸强度和密度以适于各种生物质衍生原料的HDO。
通过相继的脱水-加氢的糖醇(糖的低温加氢产物)HDO导致直链烷烃。然而,由于裂解、氢解、脱羰、脱氢、逆羟醛缩合等副反应,糖醇的水相HDO产生疏水性单官能含氧化合物,如醇、酮、杂环化合物、羧酸,以及亲水性含氧化合物。在这些化合物中,失水山梨醇和异山梨醇(脱水产物)、二醇、二酮、具有超过2个氧官能团的杂环化合物、甲醇和乙醇残留在水相中。气体产物主要为C1-C6烷烃、CO2和CO。来自糖醇的水相HDO的潜在产物的实例示于图11中。
糖醇的HDO消耗外部氢,且与APR-HDO(水相重整-加氢脱氧)方法相比作为CO和CO2损失至气相中的碳最小化,这消耗了原位产生的氢。其还使得腐黑物和焦炭的形成(其使得催化剂失活)最小化。所添加的氢可由生物质来源产生,例如APR、气化、随后水煤气变换反应。
在高氢气压力下实施HDO有助于减少重整反应,这降低了气相中的碳损失。
HDO催化剂的山梨糖醇转化效率基于疏水性油相产物的量评价,而烷烃(C1-C6)处于气相中。换言之,产物(除水之外)中的总氧减少与所述催化剂的HDO效率相关。为了简化催化剂效率的测量,在相同条件下测量碳对单官能含氧化合物(MO)和己烷的选择性以确定HDO效率,尤其是在较低的反应温度和相对更高的液体时空速率(LHSV)下。
与APR-HDO反应中所用的催化剂相比,HDO催化剂的有利之处在于提高的碳选择性。与APR-HDO反应(约20-30%)相比,HDO催化剂可产生显著更少的CO2(如小于10%)。该改进降低了到不期望产物的碳损失。
在一个实施方案中,可用Nb浸渍水稳定的酸性载体以提高它们的HDO性能。通过使用Nb促进剂,载体的酸密度由未经促进的ZrCr载体的103.8umol/g提高至158.8umol/g。如图2所示,Pt-Nb/ZrCr的酸强度也得以提高。使用相同量的贵金属Pt负载,在相同的操作条件下,Pt-Nb/ZrCr产生了比Pt/ZrCr(未经酸促进的催化剂)更多的疏水性油相产物。与Pt/ZrCr的产物相比,Pt-Nb/ZrCr的油产物要透明得多。此外,与Pt/ZrCr相比,在相同操作条件下,尤其是在较低反应温度和较少氢气供应下,Pt-Nb/ZrCr的糖醇转化率更高。
在另一实施方案中,可使用W和Mo来促进所述载体。W和Mo促进的载体的酸密度由Pt/ZrCr的103.8umol/g提高至Nb促进载体(Pt-Nb/ZrCr)的158.8umol/g,进一步提高至Pt-Mo/ZrCr的171.2umol/g、Pt-W/ZrCr的269.7umol/g。然而,钼仅以较低酸强度促进酸位点。在所有这三种经促进的催化剂中,Pt-W/ZrCr具有最高的酸密度和强度,且是其中活性最高的HDO催化剂。在265℃以及0.25h-1的LHSV和800h-1的GHSV下,Pt-W/ZrCr将99.5%的山梨糖醇转化成己烷(55%的碳选择性),余量为其它轻质烃气体。在相同的上述操作条件下,Mo促进的催化剂的活性比Nb促进的催化剂低。然而,与Pt-Nb/ZrCr和Pt-W/ZrCr相比,其的确显示出对伯己醇和己烷的高选择性。
所述HDO催化剂在水相反应中是水热稳定的。未观察到组成的浸出。废催化剂的压碎强度与新鲜催化剂相同。在废HDO催化剂中检测到碳,这可能是由于吸附的有机物质所致。Pt-Mo/ZrCr在废催化剂中具有极高的碳含量(10.4%),这归因于其在244反应小时(hours onstream,HOS)后在山梨糖醇HDO中失活。认为Pt-Nb/ZrCr和Pt-W/ZrCr是稳定的,而分别在703HOS和413HOS后未观察到任何失活。
当使用Nb、W和Mo促进HDO催化剂时,由于酸密度和强度差异,催化性能不同。酸性能可通过改变促进剂、促进剂的量、制备方法(例如混合方法、处理温度等)且使用不同类型促进剂的组合来微调。因此,所述HDO催化剂可针对不同原料的使用而优化。
所述HDO催化剂可用于各种原料,例如:游离脂肪酸、脂肪酸甲酯(FAME)、三酸甘油酯(triglycerols)、解聚的木质素和来自热解或水热处理的生物原油。在一个实施方案中,Pt-Nb/ZrCr催化剂能在三个相继的HDO运行中在280℃和100巴氢气下经5-6小时将壬酸(NA)完全转化成壬醇并进一步转化成壬烷。在另一实施方案中,Pt-Nb/ZrCr显示出99.7%的衍生自海藻油的FAME转化率,且直链烃的产率为90.1%。该FAME HDO反应路径为通过脱羰/脱羧(DeCOx),其伴随有加氢/脱水/加氢反应。DeCOx通过产生CO和CO2有助于生物质衍生的原料的碳损失。
所述加氢脱氧催化剂包含金属载体、酸促进剂和载体。所述金属催化剂选自铂、钯、钌、铼、铑、锇、铱、镍、钴、钼、铜、锡或其混合物。所述载体为经促进的锆材料。所述金属催化剂有助于HDO方法中的加氢、氢解、脱羰和脱羧。所述酸性载体有助于HDO方法中的脱水。所述酸性载体还可有助于水解以将生物质分子分解成较小的分子。二者的组合允许所述方法对含氧起始物质进行脱氧和加氢。
所述金属催化剂可为铂、钯、钌、铼、铑、锇、铱、镍、钴、钼、铜、锡或其混合物。在一个实施方案中,所述金属催化剂为铂或钯。在另一实施方案中,所述金属催化剂为铂。在另一实施方案中,所述金属催化剂为钯。
所述加氢脱氧催化剂中的金属催化剂的量可变。在一个实施方案中,其可为约0.01重量%-约20重量%、约0.5重量%-约10重量%、约0.5重量%-约5重量%、约0.5重量%-约2重量%或者约0.5重量%-约1重量%。所述金属催化剂的重量百分比可通过调节相对于经促进载体的量的所用金属催化剂前体量而控制。所述金属催化剂前体可例如为Pt(NH3)4(NO3)2、Pt(NH3)4Cl2·H2O、(NH4)2PtCl4、H2PCl6·6H2O、其它金属配位配合物或金属盐。
所述加氢脱氧催化剂可借助常规初湿含浸法、借助浸渍法或任何其它有效地将Pt分散至载体上的方法通过将所述金属催化剂前体添加至经促进的锆材料中而形成。初湿含浸法包括将催化剂前体溶液滴至载体上,直至完全润湿该载体,随后干燥并煅烧。换言之,消耗的前体溶液体积等于载体的总孔体积。为了获得期望的负载,可将上述程序重复数次。浸渍法包括在加热和搅拌下将载体置于包含过量溶解的催化剂前体的溶液中。从溶液中取出该载体,然后干燥并煅烧。在一个实施方案中,将所述金属催化剂前体溶于溶剂(一个实例为水)中,然后添加至经促进的锆材料中。将湿材料干燥,随后在受控速率下加热至约450℃的温度以煅烧该材料。所述HDO催化剂可进一步用氢气原位或异位活化。
酸促进剂
所述酸促进剂主要有助于HDO方法中的脱水、水解或者二者。所述酸促进剂可提高载体的酸度并产生额外的酸位点。在一个实施方案中,所述酸促进剂选自钨、铌、钼、铈、锰、钒、铼和钽。所述酸促进剂可为超过一种金属的组合。在另一实施方案中,所述酸促进剂选自钨、铌和钼。在另一实施方案中,所述酸促进剂为铌。
在一个实施方案中,酸促进剂的量可为载体的约0.1重量%-约99重量%。在另一实施方案中,酸促进剂的量可为载体的约1重量%-约50重量%、约1重量%-约25重量%、约2重量%-约15重量%或者约5重量%-约10重量%。
典型地通常初始含浸法或浸渍法将所述酸促进剂添加至载体中,然后添加一种或多种活性金属。此处,所述载体通常是指具有高于1.5磅/mm压碎强度的成型载体。将所述酸促进剂溶于溶剂中(典型地溶于水中),并借助初湿含浸法或浸渍法或者任何其它有效地将促进剂分散至载体中的方法添加至载体中。然后将所述混合物干燥,随后在高温下煅烧。可重复该方法,从而将额外的酸促进剂添加至载体中。在另一实施方案中,所述酸促进剂通过将所述促进剂与载体混合而添加,随后挤出并煅烧。在另一实施方案中,所述酸促进剂通过用碱沉淀至载体淤浆中而添加,随后过滤、干燥、挤出、煅烧。所述酸促进剂前体为水溶性盐、金属氧化物、金属氢氧化物。在一个实施方案中,所述酸促进剂前体为铌酸氨草酸盐、偏钨酸氨水合物、钼酸铵四水合物。在另一实施方案中,所述酸促进剂前体为铌酸、钨酸。
所述酸促进剂、量和煅烧温度和/或酸促进剂的组合的变化会导致所述催化剂载体的酸位点数量和酸强度发生变化。所述酸性载体是水热稳定的固体酸,其可独立地应用于使用固体酸作为催化剂的任何反应中,尤其是用于包含水作为反应物或者产物的反应中,例如脱水、水解、酯化、Friedel-Crafts反应等。
载体
所述载体为经促进的锆材料。所述锆可选自卤化锆或卤化氧锆、硝酸锆或硝酸氧锆、有机酸氧锆及其组合。所述锆化合物可包括各种材料,包括呈卤化物盐形式的锆和氧锆化物如ZrCl4或ZrOCl2,硝酸盐如Zr(NO3)2·5H2O或ZrO(NO3)2,以及有机酸如ZrO(CH3COO)2。在一个实施方案中,所述锆材料为ZrO2。在溶液中,锆可呈氧锆根(ZrO2+)或锆离子(Zr4+或Zr2+)形式,其可通过将相应盐溶于水中而获得。
在一个实施方案中,所述锆材料为ZrO2(氢氧化锆)或碳酸锆。
所述锆多元酸促进的材料可为呈在溶于水溶液中后形成多元酸的氧化物或酸形式的第6族金属,包括铬(Cr)、钨(W)和钼(Mo)。在一个实施方案中,所述多元酸为铬氧化物。在另一实施方案中,所述多元酸可选自CrO3、Cr2O3及其组合。在另一实施方案中,所述多元酸促进剂材料包含Cr6+,如可见于CrO3中的那样。在另一实施方案中,所述多元酸促进剂材料为钨氧化物。在另一实施方案中,所述多元酸促进剂材料可选自磷酸、硫酸、乙酸、柠檬酸及其组合。
制备包含锆氧化物(ZrO2)的载体的一个实施方案包括制备锆化合物和多元酸促进剂材料,然后将这些化合物在pH为约0.01-约4的酸性条件下混合。可添加碱溶液以使期望的载体沉淀。所述碱溶液可包括氨水、氢氧化钠水溶液或其它碱性水溶液以调节pH条件,从而获得锆和促进剂沉淀。在另一实施方案中,首先将所述多元酸促进剂材料溶于碱溶液如氢氧化铵中,随后与所述锆化合物混合。
所述载体中的多元酸量可占载体总质量的约0.1重量%-约50重量%。在一个实施方案中,所述多元酸可占载体总质量的约1重量%-约40重量%、约2重量%-约30重量%、约2重量%-约25重量%、约4重量%-约15重量%或者约5重量%-约10重量%。
在一个实施方案中,将所述锆-促进剂前体干燥或者仅将沉淀的锆干燥,直至获得约60重量%-约70重量%的灼烧损失(“LOI”)。本文所用的LOI可理解为将所述材料在约480℃下灼烧约2小时的重量损失百分比。在其它实施方案中,将所述锆-促进剂前体或沉淀的锆干燥,直至获得约64重量%-68重量%或者约65重量%-68重量%的LOI。
在各个实施方案中,可将所述锆-促进剂干燥以获得适于在无任何粘结剂、挤出助剂或稳定剂存在下挤出的混合物。换言之,将所述锆-促进剂前体干燥,从而能在不存在任何稳定剂、粘结剂或挤出助剂下成型为适于成品催化剂或催化剂载体的形状。下述化合物已被描述为稳定剂、粘结剂或挤出助剂,且本申请中所描述的一个或多个实施方案中不存在所有这些化合物:氧化硅、氧化钇、氧化镧、氧化钨、氧化镁、氧化钙、氧化铈、其它硅化合物、二氧化硅-氧化铝化合物、石墨、矿物油、滑石、硬脂酸、硬脂酸盐/酯、淀粉或其它公知的稳定剂、粘结剂或挤出助剂。
将经干燥的锆-促进剂前体成型为适于成品催化剂或催化剂载体的任何形状可通过任何本领域公知的成型方法完成。在一个实施方案中,将经干燥的锆-促进剂前体挤出。可使用本领域已知的螺杆挤出机、挤压挤出机或其它挤出设备和/或方法。或者,可例如通过压片、制丸、造粒而挤压经干燥的锆-促进剂前体,或者甚至喷雾干燥,条件是调节所述经干燥的锆-促进剂的湿度适于喷雾干燥材料。任选地,在成型后,可将挤出的锆-促进剂前体在适度的温度(例如至多约120℃)下干燥适度的时间(例如典型为约1-5小时)。
可将经挤出的或者其它成型催化剂或催化剂载体在约300-1000℃的温度下煅烧约2-12小时,优选在约400-700℃下煅烧约3-5小时。在一个实施方案中,将经挤出的铬促进的锆氧化物前体在约600℃下煅烧约3小时。或者,可将经挤出的铬促进的锆氧化物前体以1K/分钟的速率煅烧至约600℃并停留约3小时。在另一实施方案中,将经挤出的多元酸促进的锆前体在约300-1000℃、约400-700℃或者约500-600℃下煅烧约2-12小时。
使用上文所述的各方法实施方案,所述多元酸促进的锆氧化物催化剂载体具有单斜晶相、四方晶相、立方晶相和/或无定形相中的一种或多种的晶体结构(由公知的粉末X射线衍射(XRD)技术和设备测定)。例如,参见“Introduction to X-ray Powder Diffraction”,R.Jenkins和R.L Snyder,Chemical Analysis,第138卷,John Wiley&Sons,纽约,1996年。典型地,锆氧化物的四方晶相可通过测量样品在2.97埃的d间距下的强度而测定,而单斜晶相在3.13埃的d间距下测定。在其它实施方案中,所述催化剂载体可进一步表征为包含约50重量%-100重量%的锆氧化物四方晶相作为其晶体结构。在另一实施方案中,所述催化剂载体可进一步表征为包含0-50重量%的锆氧化物单斜晶相。或者,所述晶体结构可包含大于80重量%的锆氧化物四方晶相,或者约85重量%的锆氧化物四方晶相。
对包含Zr/Cr组合物的催化剂载体而言,所述方法中所使用的铬越多,则作为产物获得的四方晶相晶体结构越多。例如,4:1的摩尔比获得几乎100%的锆氧化物四方晶相。8:1的摩尔比获得几乎100%的锆氧化物四方晶相。在12:1的摩尔比下,所述晶体结构为约85重量%-90重量%的四方晶相和约15重量%-10重量%的锆氧化物单斜晶相。
上文所述的多元酸促进的锆氧化物催化剂载体可具有67N/cm(1.5磅/mm)至178N/cm(4.0磅/mm)的压碎强度。在一个实施方案中,所述催化剂或催化剂载体具有至少45N/cm(1磅/mm)或至少90N/cm(2磅/mm)的最低压碎强度。所述催化剂载体的压碎强度可使用ASTMD6175-03(2008),Standard Test Method for Radial Crush Strength ofExtruded Catalyst and Catalyst Carrier Particles测量。
在其它实施方案中,所述多元酸促进的锆氧化物催化剂载体可具有通过BET(Stephen Brunauer、Paul Hugh Emmett和Edward Teller)法测量的20-150m2/g的表面积。在一个实施方案中,所述锆氧化物催化剂载体可具有80m2/g-150m2/g,优选约120m2/g-150m2/g的表面积。
所述多元酸促进的锆氧化物催化剂载体也可具有0.10cc/g-0.40cc/g的孔体积。通常,对于4:1-16:1的初始摩尔比而言,总是获得0.15cc/g-0.35cc/g的孔体积值。对于约8:1的初始摩尔比而言,总是获得0.18cc/g-0.35cc/g的孔体积值。
含水HDO
加氢脱氧方法是一种通过消耗氢而以水的形式从原料中除去氧的方法。已发现使用包含金属催化剂、酸促进剂和除碳之外的水热稳定的载体的加氢脱氧催化剂在水相条件下是稳定的。所述金属催化剂可选自铂、钯、钌、铼、铑、锇、铱、镍、钴、钼、铜、锡或其混合物。所述载体为经促进的锆材料。所述加氢脱氧方法可使用糖或糖醇的水溶液作为起始物质。所述方法可在高于大气压的氢气气氛中进行。所述金属催化剂、酸促进剂和经促进的锆载体如上文所述。
所述氢气气氛的压力有助于抑制产生一氧化碳和二氧化碳气体产物的蒸汽重整反应。氢源还抑制腐黑物和焦炭的形成,这可提高所述加氢脱氧催化剂的寿命。在一个实施方案中,压力为至少5巴、10巴、20巴、25巴、30巴、50巴、75巴或100巴。
含水加氢脱氧方法的温度为约220-约300℃。在一个实施方案中,所述温度可为约230℃-约290℃、240℃-约280℃或者250℃-约275℃。
含水HDO方法的一个实施方案包括将包含糖或糖醇的水溶液与加氢脱氧催化剂在高于大气压的氢气气氛中混合;其中所述加氢脱氧催化剂包含金属催化剂、酸促进剂和载体;其中所述金属催化剂选自铂、钯、钌、铼、铑、锇、铱、镍、钴、钼、铜、锡或其混合物;且其中所述载体为经促进的锆材料。
在上述含水HDO方法的另一实施方案中,所述酸促进剂选自钨、铌和钼。
在上述任意含水HDO方法的另一实施方案中,所述金属催化剂为铂、钌或钯。
在上述任意含水HDO方法的另一实施方案中,所述载体为多元酸促进的ZrO2。
在上述任意含水HDO方法的另一实施方案中,所述多元酸为氧化铬或氧化钨。
在上述任意含水HDO方法的另一实施方案中,所述氢气气氛具有至少25巴的压力。
在上述任意含水HDO方法的另一实施方案中,所述温度为220℃-300℃。
脂肪酸的HDO
所述加氢脱氧方法也可在脂肪酸、脂肪酸甲酯(FAME)、三酸甘油酯(在植物油和动物脂肪中)、热解油或木质素上进行。用于该方法的加氢脱氧催化剂包含金属催化剂和载体。所述金属催化剂可选自铂、钯、钌、铼、铑、锇、铱、镍、钴、钼、铜、锡或其混合物。所述载体为经促进的锆材料。所述金属催化剂和经促进的锆载体如上文所述。所述脂肪酸的加氢脱氧方法不需要酸促进剂,其是任选的。
在一个实施方案中,所述加氢脱氧催化剂额外包含酸促进剂。所述酸促进剂可选自钨、铌、钼、锰、钒、铼和钽。酸促进剂的其它细节如上文所述。
脂肪酸的加氢脱氧方法的温度为约200℃-约450℃。在一个实施方案中,所述温度可为约220℃-约425℃、230℃-约415℃、250℃-约400℃或者250℃-约350℃。
一个实施方案为包括将脂肪酸甲酯、三酸甘油酯、热解油或木质素与加氢脱氧催化剂在高于大气压的氢气压力下混合的加氢脱氧方法,其中所述加氢脱氧催化剂包含金属催化剂和载体;其中所述金属催化剂选自铂、钯、钌、铼、铑、锇、铱、镍、钴、钼、铜、锡或其混合物;且其中所述载体为经促进的锆材料。
在上述加氢方法的另一实施方案中,所述加氢脱氧催化剂额外包含选自钨、铌、钼、锰、钒、铼和钽的酸促进剂。
在上述任意加氢方法的另一实施方案中,所述加氢脱氧催化剂包含约0.01重量%-约20重量%的金属催化剂。
在使用酸促进剂的上述任意加氢方法的另一实施方案中,所述酸促进剂占载体的约0.1重量%-约99重量%。
在上述任意加氢方法的另一实施方案中,所述温度为约250℃-约400℃。
尽管已通过描述数个实施方案阐述了本发明,且尽管相当详细地描述了示意性实施方案,然而申请人并非意欲将所附权利要求的范围限定或者以任何方式限制至该细节。额外的有利之处和变型对本领域技术人员而言可能是容易的。
实施例
实施例1—制备铌促进的锆载体
根据美国公开第2011/0301021号制备了铬促进的锆载体。
称量铌酸氨草酸盐(7.6g)并在稍微加热下溶于去离子水(20-30mL)中。在剧烈振荡下,将所述溶液滴入ZrCr载体(30g),直至所述材料完全湿润。将所得材料在110℃下干燥1小时,随后以10℃/分钟的加热速率在450℃煅烧2小时。这获得了约33.6g Nb-ZrCr载体。
实施例2—制备钼促进的锆载体
以与实施例1中相同的方式制备Mo-ZrCr载体,不同之处在于使用钼酸铵四水合物((NH4)6Mo7O24·4H2O,6.12g)代替铌酸氨草酸盐。将所得的湿材料在110℃下干燥1小时,随后以10℃/分钟的加热速率在650℃煅烧2小时。
实施例3—制备钨促进的锆载体
以与实施例1相同的方式制备W-ZrCr载体,不同之处在于使用偏钨酸氨水合物((NH4)6H2W12O40·xH2O,4.5g)代替铌酸氨草酸盐。将所得的湿材料在110℃下干燥1小时,随后以10℃/分钟的加热速率在650℃煅烧2小时。
经促进的载体的表征
图1中的经促进的ZrCr载体的XRD谱图(Cu kα)显示Nb和W良好地分散于ZrCr载体中,其XRD为无定形的,同时观察到Mo氧化物颗粒。还包括四方氧化锆和ZrCr载体的XRD谱图以进行对比。Cr为织构促进剂以稳定ZrO2的四方晶相。
实施例4—制备HDO催化剂Pt/ZrCr(Pt:2重量%)
在稍微加热下,将Pt(NH3)4(NO3)2(0.6g)溶于7mL水中。将所述溶液滴入ZrCr载体(15g)。将所得的湿混合物在110℃干燥1小时,并在400℃煅烧2小时,和在氢气流中在250℃原位活化4-8小时。
实施例5—制备HDO催化剂Pt-Nb/ZrCr(Pt:2重量%)
通过与实施例4中相同的程序制备催化剂,不同之处在于使用Nb/ZrCr载体代替ZrCr载体。
实施例6—制备HDO催化剂Pt-Mo/ZrCr(Pt:1重量%)
在稍微加热下,将Pt(NH3)4(NO3)2(0.5g)溶于15mL水中。将所述溶液滴入Mo/ZrCr载体(25g)。将所得的湿混合物在100℃干燥1小时,并在400℃下煅烧2小时,和在250mL/分钟氢气流中在250℃原位活化4-8小时。
实施例7—制备HDO催化剂Pt-W/ZrCr(Pt:1重量%)
通过与实施例6中相同的程序制备催化剂,不同之处在于使用W/ZrCr载体代替Mo/ZrCr载体。
用于酸位点和强度分析的NH
3
-TPD
所有NH3-TPD(程序升温脱附)测试通过相同的程序实施。装入约150mg催化剂并以10K/分钟的加热速率在450℃预还原2小时。然后,将经还原的催化剂在氮气中冷却至100℃。接着引入氨气流并吹扫20分钟以饱和所述催化剂样品。过量的氨气经30分钟由氮气流带走。接着将样品室以10K/分钟的加热速率加热至600℃并保持额外的20分钟。气体流出物通过MS检测器监测,并随反应时间(TOS)记录15的质量馏分。图2显示了制得的HDO催化剂的氨TPD曲线。这些催化剂的酸密度以Pt/ZrCr、Pt-Mo/ZrCr、Pt-Nb/ZrCr和Pt-W/ZrCr的顺序为103.8umol/g、158.8umol/g、171.2umol/g和269.7umol/g。且Nb和W促进的催化剂,尤其是W促进的催化剂的酸强度提高。
实施例8—在Pt-ZrCr和Pt-Nb/ZrCr上的山梨糖醇HDO
在平行固定床反应器中对于山梨糖醇HDO反应评价Pt/ZrCr和Pt-Nb/ZrCr催化剂。两方的催化剂装填量均为15mL,其中用不锈钢(S.S.)球稀释至30mL。在反应前,将所述催化剂原位活化。进料水溶液包含33重量%的山梨糖醇。所述测试在100巴氢气压力下进行。所述催化剂首先在280℃测试196小时,然后停止。用去离子水冲洗废催化剂并借助氮气吹扫干燥。将所述催化剂在反应器中保持2个月,然后在氢气中再次活化。重新开始的测试中的山梨糖醇HDO测试条件汇总在表1和2以及图3和4中。
表1:Pt-Nb/ZrCr上的山梨糖醇HDO的测试条件汇总
表2:Pt/ZrCr上的山梨糖醇HDO的测试条件汇总
每8-15小时对液体产物取样并借助HPLC分析未反应的山梨糖醇、失水山梨醇、异山梨醇、二醇和乙二醇(EG)。借助GC分析气体产物的烃和CO、CO2。在每个测试阶段中,在稳态操作后收集本体液体产物。在一些反应条件下,在本体液体产物中观察到相分离,其中油相位于顶部和水相位于底部。通过总碳分析(TOC)和GC/MS分析这两个相。由Pt-Nb/ZrCr催化剂产生的期望的油产物的量比由Pt/ZrCr催化剂产生的油产物量高得多。
在表3、4和7中,术语“HPLC”为借助HPLC分析的产物(包括失水山梨醇、甘油、异山梨醇和EG)的碳选择性的总和。水性切取馏分为由GC/MS分析的二醇/二酮和残留在水相中的HPLC产物的碳选择性总和。气体产物的碳选择性为烃(C1-C6)和CO、CO2的碳选择性总和。油相(主要为单官能含氧化合物)的量与脱氧效率相关。油相产物越多,则从山梨糖醇中移除的氧越多。
转化率和选择性基于碳,且定义于如下方程中:
表3:使用Pt-Nb/ZrCr催化剂的山梨糖醇转化率和产物选择性汇总
在总共703小时的反应期间,两种催化剂均显示出对山梨糖醇HDO反应的良好活性,而不明显失活。产物选择性随反应温度和液时空速(LHSV)变化。由该方法制得的主要单官能含氧化合物(MO)为醇和杂环化合物与少量酮和羧酸的混合物。反应温度的升高和LHSV的降低导致MO的碳选择性(Cs)提高,而水性切取馏分的Cs降低。氢气气时空速(GHSV)也会改变这两种催化剂上的脱氧效率。较低的氢气GHSV导致减少的油相产物。例如,在操作阶段4中,GHSV由800h-1减小至200h-1,这导致Pt-Nb/ZrCr催化剂上的MO选择性由53%显著降低至36.7%,而水性切取馏分的选择性由10.9%升高至21.1%。与Pt/ZrCr相比,在相同条件下操作的铌促进的Pt-Nb/ZrCr催化剂显示出对于MO的高选择性和高转化率,提高的活性。由Pt-Nb/ZrCr上的山梨糖醇HDO收集的油相通常比由Pt/ZrCr收集的更透明和更澄清得多。
表4:使用Pt/ZrCr催化剂的山梨糖醇转化率和产物选择性汇总
实施例9:在Pt-Mo/ZrCr和Pt-W/ZrCr上的山梨糖醇HDO
在平行固定床反应器中评价Pt-Mo/ZrCr和Pt-W/ZrCr催化剂。催化剂装填量15mL,用不锈钢(SS)球稀释至30mL。进料溶液包含约34.5重量%的山梨糖醇。所述测试在100巴氢气压力下进行。在测试前,将所述催化剂原位活化。测试条件汇总于表5和6中。
表5:使用Pt-W/ZrCr催化剂的山梨糖醇HDO测试条件的汇总
表6:使用Pt-Mo/ZrCr催化剂的山梨糖醇HDO测试条件的汇总
取样和分析方法遵循与实施例8中所述相同的程序。
与Nb和W促进的催化剂以及未经促进的催化剂相比,在相同操作条件于265℃使用0.25h-1的LHSV,所述Pt-Mo/ZrCr催化剂显示出较低的活性。与Pt/ZrCr上的99.6%相比,Pt-Mo/ZrCr上的山梨糖醇转化率为87.9%。然而,所述催化剂显示出对1-己醇和己烷分别为12.3%和16.3%的Cs的高选择性。与Pt/ZrCr上的21.6%相比,杂环化合物的碳选择性显著降至12.3%。在Pt-Mo/ZrCr催化剂上的气体产物中未观察到CO2产物。
Pt-W/ZrCr显示出优于Pt-Nb/ZrCr的加氢脱氧活性。在265℃使用0.25h-1的LHSV和800h-1的GHSV下,Pt-W/ZrCr将99.5%的山梨糖醇转化成己烷(55%碳选择性),余量为其它轻质烃气体。在水相产物中仅检测到少量杂环化合物(Cs 0.33%)。在265℃进一步将LHSV提高至2h-1且将GHSV提高至1200h-1,Pt-W/ZrCr获得了良好量的油相产物,而在具有1h-1的较低LHSV的类似操作条件下在Pt-Nb/ZrCr上未见相分离。使用1h-1的LHSV进一步将反应温度降至245℃,Pt-W/ZrCr上的山梨糖醇转化率降至62.4%,且MO的Cs降至约58%。
Pt-W/ZrCr经历总计约410小时的TOS反应而未观察到明显失活。Pt-Mo/ZrCr在反应的第一阶段开始失活。所述反应在约48小时后在第二阶段停车。参见图5和6,其显示了Pt-W/ZrCr和Pt-Mo/ZrCr催化剂上的山梨糖醇HDO的反应时间-山梨糖醇转化率。Pt-W/ZrCr显示出良好的催化稳定性,而Pt-Mo/ZrCr在约80小时后开始失活。
表7:Pt-W/ZrCr和Pt-Mo/ZrCr催化剂的山梨糖醇转化率和产物选择性汇总
实施例10:催化剂稳定性
通过压碎强度、元素分析和碳分析(仅对废催化剂)表征新鲜和废HDO催化剂。结果示于表8中。所述HDO催化剂显示出优异的机械稳定性和化学稳定性。在新鲜和废HDO催化剂上未观察到明显的压碎强度变化。未观察到明显的促进剂和活性贵金属的浸出。Pt-Mo/ZrCr的失活可能是由于碳物质的沉积所导致的,包括焦炭和其它形式的有机碳。
表8:新鲜和废催化剂的压碎强度、组成以及废催化剂中的碳含量列表
实施例11—制备HDO催化剂Pt-Nb/ZrCr(Pt:0.5重量%,Nb:
10重量%)
所述催化剂通过与实施例5相同的程序制备,不同之处在于使用四分之一量的Pt。
实施例12—制备HDO催化剂Pt-Nb/ZrCr(Pt:0.5重量%,Nb:5
重量%)
所述催化剂通过与实施例11相同的程序制备,不同之处在于使用一半量的Nb制备载体。
实施例13—制备HDO催化剂Pt-Nb/ZrCr(Pt:0.5重量%,Nb:
10重量%)
所述催化剂通过将10重量%的铌酸(HY340,CompanphiaBrasileira de Metalurgia e(CBMM))与适当干燥的ZrCr沉淀(L.O.I:65%)混合而制备。将所述载体挤出成直径为2mm的挤出物,随后在450℃煅烧2小时。然后将其在筛分成10-14目,然后负载Pt金属。所述Pt金属通过实施例5中的程序负载,不同之处在于使用四分之一量的Pt。
实施例14—脂肪酸的HDO
在间歇式反应器中在400℃于100巴氢气压力下评价实施例5催化剂的脂肪酸HDO。催化剂装填量为4mL,约5g。将壬酸(NA)稀释于十二烷中。在250℃催化剂活化4小时后,将约100mL的8重量%的NA溶液供入反应器中。然后,借助氢气将所述反应器加压并加热至400℃。在反应器加热到400℃(90分钟)后,立即观察到NA的完全转化。在1小时后停止所述反应。回收废催化剂并用过量甲醇洗涤。将该催化剂在相同还原条件下再次活化并通过在280℃于100巴氢气压力下实施5-6小时的三个相继的NA HDO反应评价。所述测试设计用来评价所述催化剂对脂肪酸转化的活性和稳定性。在各测试之间,向反应器中注入60mL十二烷和8mL NA以在各轮次开始时维持液位(由于取样)和NA浓度。除了在每次液体取样后引入少量氢气以维持反应器压力之外,所述反应在密闭***中进行。在各轮次中,在将反应器冷却至室温后,对气体取样。
NA转化率和产物产率基于液体样品中的各组分摩尔浓度计算,并假定在反应期间体积不发生变化。借助GC/MS分析NA和产物。壬烷为最终反应产物。在反应期间检测到壬醇和另一种未知的反应中间体(可能为壬酸壬酯)。转化率和产物产率基于如下方程计算:
表9:实施例5催化剂上的壬酸HDO的催化性能。下文所有数据均在280℃于100巴氢气压力下在5小时反应时记录。
实施例5的催化剂在各轮次中保持高活性,其中在5小时反应后的壬酸转化率为100%。甲烷为主要的气体产物。在5小时的相同反应时间下,壬烷产率由第1轮的72%降至第3轮的59%。同时,壬醇产率由0%提高至第2轮的3.2%和第3轮的12%。这些表明实施例5的催化剂可能经历一定程度的失活。碳分析显示废催化剂包含约1.1重量%的碳。
实施例15—使用实施例5催化剂的FAME的HDO
脂肪酸甲酯(FAME)获自海藻油的酯交换反应。所述HDO测试在半间歇式反应器中使用由背压调节器(BPR)释放的过量气相压力进行。催化剂装填量为8mL,约10g。FAME进料为100mL,约90g。在引入液体进料之前,将所述催化剂活化。随后将所述反应器***加压至100巴氢气压力。然后,密闭所述反应器的出口。以5K/分钟的加热速率将所述反应器加热至400℃的反应温度。在加热工艺期间在120-340℃温度范围内,由于FAME中的不饱和碳键加氢而观察到氢气消耗。在反应器温度达到400℃后对反应计时,并重新打开反应器的气体出口以从该反应中释放出过量的压力。所述测试在400℃于100巴氢气压力下保持总共2小时。释放出的气体总体积通过湿测试计测量。在将反应器冷却至低于50℃后,从反应器收集气体样品。在冷却至室温后,借助GC/MS分析反应器中的液体产物。
GC/MS借助FAME标样(C8-C24,Sigma Aldrich)和烷烃标样(C8-C20和C21-C40,Sigma Aldrich)标定。脂肪酸的响应假定相同。在典型的分析中,将0.1mL收集的液体样品用环己烷稀释至10mL。在一些情况下,液体产物具有低浊点(在室温下为蜡状)。需要将所述样品稍微加热以量取0.1mL液体产物进行分析。
转化率和选择性基于碳,且定义于下述方程中:
实施例5的催化剂显示出99.7%的FAME转化率、90.1%的直链烃产率和7.7%的气体产物产率。气体产物主要包含甲烷、CO和CO2,气相中的碳分布分别为30%、23%和34%。根据图7所示的碳分布,所述烃产物主要由脱羰/脱羧反应产生。加氢/脱水/加氢反应路径为次要反应路径。裂解是另一种可能的反应路径。
实施例16—使用实施例11催化剂的FAME的HDO
除了使用实施例11的催化剂之外,所述测试严格遵循与实施例15所述相同的程序。所述催化剂显示出95%的FAME转化率,49.2%的直链烃产率和5.2%的气体产物产率。气体产物主要包含甲烷、CO和CO2,气相中的碳分布分别为42%、25%和15%。FAME和产物的碳分布示于图8中。
实施例17—使用实施例12催化剂的FAME的HDO
除了使用实施例12的催化剂之外,所述测试严格遵循与实施例15所述相同的程序。所述催化剂显示出91%的FAME转化率,39.4%的直链烃产率和5.7%的气体产物产率。气体产物主要包含甲烷、戊烷和CO,气相中的碳分布分别为32%、22%和31%。FAME和产物的碳分布示于图9中。
实施例18—使用实施例13催化剂的FAME的HDO
除了使用实施例13的催化剂之外,所述测试严格遵循与实施例15所述相同的程序。所述催化剂显示出99.5%的FAME转化率,58.5%的直链烃产率和5.2%的气体产物产率。气体产物主要包含甲烷、CO和CO2,气相中的碳分布分别为39.6%、8.2%和40.5%。FAME和产物的碳分布示于图10中。
实施例19—对比测试
测试市售HDmax200催化剂(CoO:3-5%;MoO3:13-21%;Al2O3:余量)的FAME的HDO。在使用前,将所述催化剂筛分成10-14目。催化剂装载量为约10mL,7.79g。在反应前,将所述催化剂在166mL/min的氢气流中以2K/min的加热速率在500℃下活化4小时。FAME进料为120mL。将HDmax200在380℃于100巴氢气压力下测试4小时。HDmax200显示出93.5%的FAME转化率和14.9%的直链烃产率。液体产物还包含碳产率为13.2%的脂肪酸、焦炭和其它未知产物。甲烷为主要的气体产物。
Claims (15)
1.一种加氢脱氧催化剂,其包含金属催化剂、酸促进剂和载体;其中所述金属催化剂选自铂、钯、钌、铼、铑、锇、铱、镍、钴、钼、铜、锡或其混合物;且其中所述载体为经促进的锆材料。
2.根据权利要求1所述的加氢脱氧催化剂,其中所述酸促进剂选自钨、铌、钼、铈、锰、钒、铼和钽。
3.根据前述权利要求中任一项所述的加氢脱氧催化剂,其中所述酸促进剂选自钨、铌和钼。
4.根据前述权利要求中任一项所述的加氢脱氧催化剂,其中所述金属催化剂为铂或钯。
5.根据前述权利要求中任一项所述的加氢脱氧催化剂,其中所述金属催化剂为所述加氢脱氧催化剂的0.01重量%-20重量%。
6.根据前述权利要求中任一项所述的加氢脱氧催化剂,其中所述载体为多元酸促进的ZrO2。
7.根据权利要求6所述的加氢脱氧催化剂,其中所述多元酸为所述载体的0.1重量%-50重量%。
8.根据前述权利要求中任一项所述的加氢脱氧催化剂,其中所述载体为铬促进的锆材料。
9.一种加氢脱氧方法,包括将脂肪酸、脂肪酸甲酯(FAME)、三酸甘油酯(植物油和动物脂肪中的)、热解油、木质素或包含糖或糖醇的溶液与加氢脱氧催化剂在高于大气压的氢气气氛中混合;其中所述加氢脱氧催化剂包含金属催化剂、酸促进剂和载体;其中所述金属催化剂选自铂、钯、钌、铼、铑、锇、铱、镍、钴、钼、铜、锡或其混合物;且其中所述载体为经促进的锆材料。
10.根据权利要求9所述的加氢脱氧方法,其中所述酸促进剂选自钨、铌和钼。
11.根据权利要求9-10中任一项所述的加氢脱氧方法,其中所述金属催化剂为铂、钌或钯。
12.根据权利要求9-11中任一项所述的加氢脱氧方法,其中所述载体为多元酸促进的ZrO2。
13.根据权利要求12所述的加氢脱氧方法,其中所述多元酸为氧化铬或氧化钨。
14.根据权利要求9-13中任一项所述的加氢脱氧方法,其中所述氢气气氛具有至少25巴的压力。
15.根据权利要求9-14中任一项所述的加氢脱氧方法,其中温度为220℃-300℃。
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CN112619635B (zh) * | 2019-09-24 | 2023-04-11 | 中国石油化工股份有限公司 | 一种双金属氧化物催化剂及其制备方法和应用 |
CN112844379A (zh) * | 2020-12-31 | 2021-05-28 | 华南理工大学 | 金属有机骨架材料衍生物负载钌催化木质素解聚制备单酚类化学品的方法 |
CN115368228A (zh) * | 2021-05-21 | 2022-11-22 | 中国石油化工股份有限公司 | 一锅法催化转化生物质制备2,5-己二酮的方法 |
CN113617343A (zh) * | 2021-08-31 | 2021-11-09 | 福州大学 | 一种生物质油脱氧催化剂及其制备方法和应用 |
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US9278346B2 (en) | 2016-03-08 |
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