CN102149661A - 使用铂/锡催化剂由乙酸直接选择性制备乙醇 - Google Patents
使用铂/锡催化剂由乙酸直接选择性制备乙醇 Download PDFInfo
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Abstract
公开并要求保护了用于由乙酸在加氢催化剂组合物上的气相反应以生成乙醇而选择性制备乙醇的方法。在本发明的实施方案中,乙酸和氢气在负载在二氧化硅、石墨、硅酸钙和二氧化硅-氧化铝上的铂和锡上的反应在气相中在约250℃的温度选择性制备了乙醇。
Description
优先权
本申请基于2008年7月31日提交的相同名称的美国专利申请序列号12/221,141,由此要求其优先权,且其内容通过参考引入此处。
技术领域
本发明总的来讲涉及用于由乙酸制备乙醇的方法。更特别地,本发明涉及包括使用由负载在适合的催化剂载体上的铂和锡构成并任选地包含一种或多种其它加氢金属的催化剂对乙酸加氢以高选择性制备乙醇的方法。
背景技术
对经济上可行的用于将乙酸转化为乙醇的方法存在长期的迫切需要。乙醇是多种工业产品的重要商品原料,且还用作汽油的燃料添加剂。例如,乙醇能够容易地脱水成为乙烯,然后能够将其转化为用于涂料、聚合物制备等的聚合物产物或小分子基产物。乙醇传统上是由其价格波动变得更加显著的原料制备的。即天然气和原油价格的波动有助于传统上制备的石油、天然气或玉米或其它农产品来源的乙醇的成本波动,因此需要在石油价格和/或农产品价格升高时乙醇的全部(all the greater)可替代来源。
已经报道了能够由乙酸的加氢制备乙醇,但大多数这些方法具有一些商业操作的缺点。例如,美国专利号2,607,807公开了能够由乙酸在钌催化剂上在700-950巴的超高压力生成乙醇以达到约88%的产率,而在约200巴的压力仅得到约40%的低产率。然而,这两种条件都是商业操作不可接受和不经济的。
更近以来,已经报道了能够使用钴催化剂再次在超大气压力(例如约40-120巴)下由乙酸的加氢制备乙醇。例如参见授予Shuster等的美国专利号4,517,391。然而,此处公开的唯一实施例使用在约300巴范围内的反应压力,仍使该方法不适用于商业操作。此外,该方法要求包含不少于50wt%的钴以及选自由铜、锰、钼、铬和磷酸构成的组的一种或多种组分的催化剂,由此使得该方法经济上不可行。尽管公开了使用简单惰性催化剂载体以负载催化剂材料,但没有负载金属催化剂的具体实施例。
授予Kitson等的美国专利号5,149,680公开了用于使用铂族金属合金催化剂由羧酸及其酸酐催化加氢制备醇和/或酯的方法。该催化剂是由至少一种周期表的VIII族贵金属和至少一种能够与VIII族贵金属组成合金的金属的合金与包含金属铼、钨或钼的至少一种的组分混合组成的。尽管此处并未要求保护与现有技术对比实现了醇选择性的提高,但仍报道在其最适宜的催化剂条件下在乙酸加氢为乙醇的过程中生成了3-9%的烷烃(例如甲烷和乙烷)作为副产物。
授予Kitson等的美国专利号4,777,303描述了用于由羧酸加氢制备醇的方法。该例中所用的催化剂是非均相催化剂,包括是钼或钨的第一组分和是元素周期表的VIII族的贵金属的第二组分,任选地在载体(例如高表面积石墨化碳)上。报道乙醇和酯的组合混合物的选择性仅在约73-87%范围内,羧酸的低转化率为约16-58%。此外,未提供乙酸转化为乙醇的具体实施例。
授予Kitson等的美国专利号4,804,791描述了另一种用于由羧酸加氢制备醇的方法。在该方法中,通过将乙酸或丙酸在气相中在升高温度和在1-150巴的范围内的压力在包括作为必要组分的(i)元素周期表的VIII族贵金属;和(ii)铼且任选地在载体(例如高表面积石墨化碳)上的催化剂的存在下与氢气接触,从而由乙酸制备乙醇或由丙酸制备丙醇。该乙酸转化为乙醇的转化率在0.6%-69%范围内,乙醇的选择性在约6%-97%范围内。
综上所述,显然现有的方法都没有所需的乙醇选择性,或者现有技术使用的催化剂是昂贵的和/或对乙醇的生成不是选择性的并产生不希望的副产物。
发明内容
令人惊奇的是,现在未曾预期地发现能够在工业规模上由乙酸以非常高的选择性和产率直接制备乙醇。更特别地,本发明提供了用于由乙酸选择性生成乙醇的方法,包括:在氢气存在下在铂/锡加氢催化剂上对乙酸加氢。更特别地,适用于本发明的方法的催化剂是由负载在适合的催化剂载体上的铂和锡的组合且任选地与一种或多种选自由钯、铑、钌、铼、铱、铬、铜、钼、钨、钒和锌构成的组的金属催化剂相结合构成的。适合的催化剂载体包括但不局限于:二氧化硅、氧化铝、硅酸钙、碳、氧化锆和氧化钛。
具体实施方式
下面参照多个仅用于举例和解释的实施方案对本发明进行详细描述。在后附权利要求中提出的本发明的精神和范围内对特别实施方案的改进对于本领域技术人员将是容易显而易见的。
除非下面有更特别的定义,此处所用的术语以其普通含义给出。除非另外指出,摩尔百分比(摩尔%或%)和类似的术语表示摩尔百分比。除非另外指出,重量百分比(wt%或%)和类似的术语表示重量百分比。
“转化率”表示为基于原料中的乙酸的摩尔百分比。乙酸(AcOH)的转化率是使用以下方程由气相色谱(GC)数据计算的:
“选择性”表示为基于转化的乙酸的摩尔百分比。例如,如果转化率为50摩尔%且有50摩尔%的转化的乙酸转化为乙醇,那么我们称乙醇的选择性为50%。选择性是使用以下方程由气相色谱(GC)数据计算的:
催化剂金属的重量百分比是基于金属重量以及金属和载体的总干重的。
该反应依照以下化学方程进行:
依照本发明,乙酸转化为乙醇能够在多种构造中进行,例如如果需要,在单一反应区中,其可以为分层固定床。能够使用绝热反应器,或者能够使用具有传热介质的壳管式反应器。该固定床能够包括不同催化剂颗粒的混合物或者包括此处进一步描述的多种催化剂的催化剂颗粒。该固定床也可以包括组成反应物的混合区的颗粒材料层。将包括乙酸、氢和任选的惰性载气的反应混合物作为到达混合区的在压力下的物流供给该床。然后将该物流供给反应区或层(通过压力降低)。反应区包括催化组合物,催化组合物包含适合的加氢催化剂,其中将乙酸加氢以制备乙醇。根据反应器的类型、处理量需求等可以使用任意适合的粒度。
尽管在本发明的方法中在将乙酸加氢生成乙醇中能够使用本领域技术人员已知的各种含铂加氢催化剂,但优选所用的加氢催化剂包含在适合的催化剂载体上的铂和锡的组合。如前所述,进一步优选适用于本发明的方法的催化剂任选地包含负载在同一催化剂载体上的第三金属。可以非限定性地提及以下金属作为适用作第三金属的那些金属:钯、铑、钌、铼、铱、铬、铜、钼、钨、钒、锌及其混合物。典型地,优选能够使用在适合载体上适合重量比的铂和锡的组合作为加氢催化剂。因此,特别优选重量比为约0.1-2的铂和锡的组合(Pt/Sn)。更优选地,Pt/Sn重量比为约0.5-1.5,最优选Pt/Sn重量比为约1。能够作为第三金属与Pt/Sn一起使用的金属的优选实施例非限定性地包括上面列出的任意其它金属,例如铑、铱、铜、钼和锌。
现有技术中已知的各种催化剂载体都能够用于负载本发明的催化剂。这些载体的实例包括但不局限于:沸石、氧化铁、二氧化硅、氧化铝、氧化钛、氧化锆、氧化镁、硅酸钙、碳、石墨及其混合物。优选的载体是二氧化硅、氧化铝、硅酸钙、碳、氧化锆和氧化钛。更优选使用二氧化硅作为本发明的方法中的催化剂载体。还重要地指出二氧化硅的纯度越高,其优选作为本发明的载体越好。另一种优选的催化剂载体是硅酸钙。
在本发明的另一实施方案中,该优选的催化剂载体是碳。现有技术中已知适用作催化剂载体的各种形式的碳都能够用于本发明的方法中。特别优选的碳载体是石墨化碳,特别是英国专利号2,136,704中所述的高表面积石墨化碳。该碳优选是颗粒状的,例如作为粒料。碳颗粒的尺寸将取决于任意给定反应器中可接受的压降(其给出最小粒料尺寸)和粒料内反应物的扩散限制(其给出粒料尺寸)。
适用于本发明的方法中的碳催化剂载体优选是多孔碳催化剂载体。具有该优选的粒度,该碳将需要是多孔的以满足优选的表面积特征。
包括碳催化剂载体的催化剂载体可以由其BET、基面和边缘表面积表征。该BET表面积是使用Brunauer Emmett and Teller J.Am.Chem.Soc.60,309(1938)的方法由氮气吸附测定的表面积。基面表面积是通过Proc.Roy.Soc.A314第473-498页(特别参照第489页)中所述的方法由正三十二烷从正庚烷吸附在碳上的吸附热测定的表面积。边缘表面积(edge surface area)是如上述Proc.Roy.Soc.文章中特别参照第495页公开的由正丁醇从正庚烷吸附在碳上的吸附热测定的表面积。
优选用于本发明的碳催化剂载体具有至少100m2/g的BET表面积,更优选至少200m2/g,最优选至少300m2/g。该BET表面积优选不大于1000m2/g,更优选不大于750m2/g。
优选使用基面表面积与边缘表面积之比为至少10∶1,优选至少100∶1的碳催化剂载体。不相信该比值存在上限,尽管在实施中其通常将不超过200∶1。
该优选的碳载体可以由含碳原料的热处理制备。该原料可以是亲油石墨,例如如英国专利号1,168,785中所述制备的,或者可以是碳黑。
然而,亲油石墨包含薄片形式的非常微细的颗粒形式的碳,因此并不是非常适用作催化剂载体的材料。申请人优选避免使用它们。类似的考虑适用于也具有非常微细粒度的碳黑。
优选的材料是源自植物材料(例如椰子木炭)或源自泥煤或煤或源自可碳化的聚合物的活性炭。该材料经过热处理优选具有不小于上述优选用于碳载体的那些的粒度。
优选的原料具有以下特征:BET表面积至少100,更优选至少500m2/g。
用于制备具有所限定特征的碳载体的优选热处理程序包括连续的以下:(1)在惰性气氛中在900℃-3300℃的温度加热该碳;(2)在300℃-1200℃的温度氧化该碳;(3)在惰性气氛中在900℃-3000℃的温度加热。
在使用氧气(例如作为空气)作为氧化剂时,该氧化步骤优选在300℃-600℃的温度进行。
在惰性气体中的加热持续时间并不严格。加热该碳到所需的最大温度所需的时间是足以在该碳中产生所需的改变。
该氧化步骤显然不能在使得该碳完全燃烧的条件下进行。其优选使用气态氧化剂以受控速率进料从而避免过度氧化。气态氧化剂的实例是蒸汽、二氧化碳和包含分子氧的气体(例如空气)。该氧化优选进行以给出基于经过该氧化步骤的碳重量的至少10wt%的碳重量损失,更优选至少15wt%。
该重量损失优选不大于经过该氧化步骤的碳的40wt%,更优选不大于该碳的25wt%。
氧化剂的供给速率优选使得所需的重量损失发生至少2小时,更优选至少4小时。
在需要惰性气氛的情况下,其可以由氮气或惰性气体提供。
如上所述,铂和锡的负载量水平通常参考铂的含量和Pt/Sn的重量比,且其在约0.1-2的范围内。因此,当Pt/Sn的重量比为0.1时,铂的含量能够为0.1或1wt%,因此1或10wt%的锡存在于该催化剂载体上。更优选地,Pt/Sn的重量比为约0.5,因此铂在该催化剂载体上的含量能够为0.5或1wt%,锡的含量为1或2wt%。更优选地,Pt/Sn的重量比为1。因此铂在载体上的含量为0.5、1或2wt%,锡的含量也为0.5、1或2wt%。然而,也能够使用低的Pt/Sn重量比。例如,也能够使用0.2的Pt/Sn重量比。在这种情况中,铂在载体上的含量能够为0.5或1wt%,而使用2.5或5wt%的锡。
如果存在,第三金属在载体上的负载量在本发明中并不非常严格,能够在约0.1wt%-约10wt%范围内变化。特别优选基于载体重量约1wt%-约6wt%的金属负载量。
能够使用本领域中任意已知方法进行金属浸渍。典型地,在浸渍之前,将该载体在120℃干燥并成型为具有在约0.2-0.4mm范围内的粒度分布的颗粒。任选地,可以将该载体挤压、压碎并筛分到所需的粒度分布。能够使用任意已知的用于将该载体材料成型为所需粒度分布的方法。
对于具有低表面积的载体,例如α-氧化铝,过量添加金属溶液直至完全润湿或过量液体浸渍以得到所需的金属负载量。
如上所述,本发明的方法中所用的加氢催化剂至少是包含铂和锡的双金属催化剂。通常,尽管不意于被任何理论所束缚,认为一种金属用作促进剂金属,而另一种金属是主金属。例如,在本发明的方法中,铂和锡的组合被认为是用于制备本发明的加氢催化剂的主金属。然而,也能够根据各种反应参数(包括但不局限于所用的催化剂载体、反应温度和压力等)认为铂是主金属,锡是促进剂金属。该主金属能够与促进剂金属(例如钨、钒、钼、铬或锌)相结合。然而,应当指出有时主金属也用作促进剂金属或反之亦然。例如,当使用铁作为主金属时,镍能够用作促进剂金属。类似地,铬能够与铜相结合用作主金属(即Cu-Cr作为主双金属),其能够进一步与促进剂金属(例如铈、镁或锌)相结合。
该双金属催化剂通常是在两个步骤中浸渍的。首先添加“促进剂”金属,然后添加“主”金属。各浸渍步骤之后是干燥和煅烧。该双金属催化剂也可以通过共浸渍制备。例如,本发明的铂/锡催化剂通常共浸渍在载体催化剂上。在上述含Cu/Cr的三金属催化剂的情况中,可以使用顺序浸渍,初始添加“促进剂”金属。第二浸渍步骤可以包括两种主要金属(即Cu和Cr)的共浸渍。例如,Cu-Cr-Co在SiO2上可以由以下制备:首先浸渍硝酸铬,然后共浸渍硝酸铜和钴。再次,各浸渍之后是干燥和煅烧。在大多数情况中,该浸渍可以使用金属硝酸盐溶液进行。然而,也能够使用一旦煅烧就会释放出金属离子的各种其它可溶盐。其它适用于浸渍的金属盐的实例包括金属草酸盐、金属氢氧化物、金属氧化物、金属乙酸盐、铵基金属氧化物(例如七钼酸铵六水合物)、金属酸(例如高铼酸溶液)等。
因此在本发明的一种实施方案中,提供了加氢催化剂,其中该催化剂载体是石墨,具有铂和锡的双金属负载。在本发明的该方面中,铂的负载量为约0.5wt%-约1wt%,锡的负载量为约0.5wt%-约5wt%。特别地,在石墨上能够使用1/1、1/5、0.5/0.5和0.5/2.5wt%的铂/锡的负载量水平。
在本发明的另一实施方案中,另外提供了加氢催化剂,其中催化剂载体是高纯度的低表面积二氧化硅,具有铂和锡的双金属负载。在本发明的该方面中,铂负载量为约0.5wt%-约1wt%,锡的负载量为约0.5wt%-约5wt%。特别地,能够使用在高纯度的低表面积二氧化硅上1/1、1/5、0.5/0.5和0.5/2.5wt%的铂/锡的负载量水平。
在本发明的另一实施方案中,另外提供了加氢催化剂,其中催化剂载体是硅酸钙,具有铂和锡的双金属负载。在本发明的该方面中,铂负载量为约0.5wt%-约1wt%,锡的负载量为约0.5wt%-约5wt%。特别地,能够使用在硅酸钙上1/1、1/5、0.5/0.5和0.5/2.5wt%的铂/锡的负载量水平。
在本发明的另一实施方案中,另外提供了加氢催化剂,其中催化剂载体是二氧化硅-氧化铝,具有铂和锡的双金属负载。在本发明的该方面中,铂负载量为约0.5wt%-约1wt%,锡的负载量为约0.5wt%-约5wt%。特别地,能够使用在二氧化硅-氧化铝上1/1、1/5、0.5/0.5和0.5/2.5wt%的铂/锡的负载量水平。
通常,通过实施本发明,乙酸能够以非常高的速率选择性地转化为乙醇。乙醇的选择性通常非常高,且可能为至少60%。在优选的反应条件下,在至少80%的选择性下或更优选在至少90%的选择性下,乙酸选择性转化为乙醇。更优选乙醇的选择性为至少95%。
使用本发明的催化剂,乙酸的转化率为至少60%,乙醇的选择性为至少80%、优选90%、最优选95%。
通常,本发明的活性催化剂是铂和锡的负载量各自为1wt%的负载在二氧化硅上的包含铂和锡的未经促进的催化剂。依照本发明的实践,使用这些催化剂,乙酸能够以约90%的转化率和至少90%的乙醇选择性,更优选至少95%的乙醇选择性转化。
使用硅酸钙、石墨或二氧化硅-氧化铝作为载体以及使用各1wt%的铂和锡的负载量且不用其它促进剂金属实现了类似的转化率和选择性。
在本发明的另一方面,使用具有促进剂金属(例如钴、钌或钯)的在作为催化剂载体的二氧化硅或硅酸钙上各1wt%的铂和锡负载量,也可以得到约至少90%的高转化率水平和至少约90%的高乙醇选择性。该促进剂金属负载量在约0.1wt%-约0.5wt%的范围内,更优选在约0.15wt%-0.3wt%的范围内,最优选该促进剂金属负载量为约0.2wt%。在本发明的该方面,其它优选的催化剂载体包括二氧化硅-氧化铝、氧化钛或氧化锆。
在本发明的方法的另一方面,该加氢是在刚好足以克服沿催化床的压降的压力下进行的。
该反应可以在多种条件下在气态或液态中进行。优选地,该反应在气相中进行。可以使用的反应温度例如在约200℃-约300℃,优选约225℃-约275℃的范围内。压力通常对该反应不是关键的,可以使用低于大气压、大气压或高于大气压。然而,在大多数情况中,该反应的压力将在约1-30大气压的绝对压力范围内,最优选反应区的压力在约10-25大气压的绝对压力范围内。
尽管该反应每摩尔乙酸消耗2摩尔氢气生成1摩尔乙醇,但进料流中的乙酸∶氢气的实际摩尔比可以在宽限制内变化,例如约100∶1-1∶100。然而,优选该比例在约1∶20-1∶2范围内。更优选地,乙酸与氢气的摩尔比为约1∶5。
与本发明的方法结合使用的原料可以来自任意适合的来源,包括天然气、石油、煤、生物质等。通过甲醇羰基化、乙醛氧化、乙烯氧化、氧化发酵和厌氧发酵等制备乙酸是公知的。因为石油和天然气变得更加昂贵,因此由可替代的碳源制备乙酸和中间产物(例如甲醇和一氧化碳)的方法获得了更多的关注。受到特别关注的是由可以来自任意适合的碳源的合成气制备乙酸。例如授予Vidalin的美国专利号6,232,352(其公开内容通过参考引入此处)教导了改装甲醇装置用于制备乙酸的方法。通过改装甲醇装置,显著降低或大大消除了与新型乙酸装置的CO产生相关的大的资金成本。该合成气的所有或部分是由甲醇合成回路分流而来的且被送往分离器装置以回收CO和氢气,其然后用于制备乙酸。除乙酸之外,该方法也能够用于制备与本发明相关使用的氢气。
Steinberg等的美国专利号RE35,377(也通过参考引入此处)提供了通过转化碳质材料(例如油、煤、天然气和生物质材料)制备甲醇的方法。该方法包括将固体和/或液体碳质材料加氢气化以得到工艺气体,用另外的天然气将其蒸汽热解以生成合成气。将该合成气转化为甲醇,可以将其羰基化为乙酸。该方法同样产生了可以如上所述与本发明结合使用的氢气。也参见Grady等的美国专利号5,821,111,其公开了用于将废生物质通过气化转化为合成气的方法,以及Kindig等的美国专利号6,685,754,其公开内容通过参考引入此处。
可以在反应温度将该乙酸气化,然后将其与氢气一起以未稀释状态或用较为惰性的载气(例如氮气、氩气、氦气、二氧化碳等)稀释供给。
可替代地,蒸气形式的乙酸可以直接取自Scates等的美国专利号6,657,078中描述的一类甲醇羰基化装置的闪蒸容器的粗产物,其公开内容通过参考引入此处。可以直接将该粗蒸气产物供给本发明的反应区,而不需要冷凝该乙酸和轻馏分或除水,节省总体方法成本。
接触或停留时间也能够根据一些变量(例如乙酸的量、催化剂、反应器、温度和压力)广泛变化。当使用非固定床的催化剂系统时,典型的接触时间在几分之一秒到超过几小时的范围内变化,优选的接触时间至少对于气相反应为约0.5-100秒。
典型地,该催化剂用于固定床反应器中,例如在细长管道或管子的形状中,其中典型地为蒸气形式的反应物在催化剂上通过或穿过催化剂。如果需要,也能够使用其它反应器,例如流化床或沸腾床反应器。在一些情况中,有利地使用该加氢催化剂与惰性材料相结合以调节该催化剂床中的压降、流量、热平衡或其它过程参数,包括反应物化合物与该催化剂颗粒的接触时间。
在一种优选实施方案中,还提供了用于由乙酸选择性直接生成乙醇的方法,包括:将包含乙酸和氢气的进料流在升高温度与在适合的催化剂载体上包含约0.5wt%-约1wt%铂和约0.5wt%-约5wt%的锡和任选的负载在所述载体上的第三金属的适合的加氢催化剂接触,其中所述第三金属选自由钴、钌和钯构成的组。
在本发明的方法的该实施方案中,该优选的加氢催化剂包含约1wt%的铂和约1wt%的锡。在本发明的方法的该实施方案中,优选该加氢催化剂在固定床中是分层的,且该反应是使用摩尔比为约1∶20-1∶5的乙酸和氢气的进料流在范围为约225℃-275℃的温度和在约10-25大气压绝对压力范围内的反应区压力下在气相中进行的,反应物的接触时间在约0.5-100秒范围内。
以下实施例描述了用于制备在本发明的方法中使用的各种催化剂的程序。
实施例A
制备1wt%铂和1wt%锡在石墨上
在烘箱中在氮气气氛下在120℃对经磨粉和筛分的具有约0.2mm的均匀粒度分布的石墨(100g)干燥整晚,然后冷却到室温。向其中添加硝酸铂(Chempur)(1.64g)在蒸馏水(16ml)中的溶液和草酸锡(Alfa Aesar)(1.74g)在稀硝酸(1N,8.5ml)中的溶液。将所得到的浆液在逐渐加热到110℃(>2小时,10℃/min)的烘箱中干燥。然后将经浸渍的催化剂混合物在400℃煅烧(6小时,1℃/min)。
实施例B
制备0.5wt%铂和5wt%锡在高纯度的低表面积二氧化硅上
在烘箱中在氮气气氛下在120℃对经磨粉和筛分的具有约0.2mm的均匀粒度分布的高纯度的低表面积二氧化硅(100g)干燥整晚,然后冷却到室温。向其中添加硝酸铂(Chempur)(0.82g)在蒸馏水(8ml)中的溶液和草酸锡(Alfa Aesar)(8.7g)在稀硝酸(1N,43.5ml)中的溶液。将所得到的浆液在逐渐加热到110℃(>2小时,10℃/min)的烘箱中干燥。然后将经浸渍的催化剂混合物在500℃煅烧(6小时,1℃/min)。
实施例C
制备1wt%铂和1wt%锡在高纯度的低表面积二氧化硅上
基本重复实施例B的程序,除了使用硝酸铂(Chempur)(1.64g)在蒸馏水(16ml)中的溶液和草酸锡(Alfa Aesar)(1.74g)在稀硝酸(1N,8.5ml)中的溶液。
实施例D
制备1wt%铂和1wt%锡在硅酸钙上
基本重复实施例B的程序,除了使用硝酸铂(Chempur)(1.64g)在蒸馏水(16ml)中的溶液和草酸锡(Alfa Aesar)(1.74g)在稀硝酸(1N,8.5ml)中的溶液并使用硅酸钙作为催化剂载体。
实施例E
制备0.5wt%铂、0.5wt%锡和0.2wt%钴在高纯度的低表面积二氧化硅上
在烘箱中在氮气气氛下在120℃对经磨粉和筛分的具有约0.2mm的均匀粒度分布的高纯度的低表面积二氧化硅(100g)干燥整晚,然后冷却到室温。向其中添加硝酸铂(Chempur)(0.82g)在蒸馏水(8ml)中的溶液和草酸锡(Alfa Aesar)(0.87g)在稀硝酸(1N,4.5ml)中的溶液。将所得到的浆液在逐渐加热到110℃(>2小时,10℃/min)的烘箱中干燥。然后将经浸渍的催化剂混合物在500℃煅烧(6小时,1℃/min)。向该经浸渍和冷却的材料中添加硝酸钴六水合物(0.99g)在蒸馏水(2ml)中的溶液。将所得到的浆液在逐渐加热到110℃(>2小时,10℃/min)的烘箱中干燥。然后将经浸渍的催化剂混合物在500℃煅烧(6小时,1℃/min)。
实施例F
制备0.5wt%锡在高纯度的低表面积二氧化硅上
在烘箱中在氮气气氛下在120℃对经磨粉和筛分的具有约0.2mm的均匀粒度分布的高纯度的低表面积二氧化硅(100g)干燥整晚,然后冷却到室温。向其中添加草酸锡(Alfa Aesar)(1.74g)在稀硝酸(1N,8.5ml)中的溶液。将所得到的浆液在逐渐加热到110℃(>2小时,10℃/min)的烘箱中干燥。然后将经浸渍的催化剂混合物在500℃煅烧(6小时,1℃/min)。
产物的气相色谱(GC)分析
用在线GC进行产物的分析。使用装备有1个火焰离子检测器(FID)和2个热传导检测器(TCD)的三通道小型GC分析反应物和产物。前通道装备有FID和CP-Sil 5(20m)+WaxFFap(5m)柱并用于定量以下:
乙醛
乙醇
丙酮
乙酸甲酯
乙酸乙烯酯
乙酸乙酯
乙酸
乙二醇二乙酸酯
乙二醇
亚乙基二乙酸酯
三聚乙醛
中通道装备有TCD和Porabond Q柱并用于定量:
CO2
乙烯
乙烷
后通道装备有TCD和Molsieve 5A柱并用于定量:
氦气
氢气
氮气
甲烷
一氧化碳
在反应之前,通过用单一化合物形成尖峰测定不同组分的保留时间,用已知组成的校准气体或用已知组成的液体溶液校准该GC。这可以测定各种组分的响应因子。
实施例1
所用的催化剂是依照实施例C的程序制备的1wt%铂和1wt%锡在二氧化硅上。
在具有30mm的内径并能够提升到受控温度的由不锈钢制成的管状反应器中,设置50ml二氧化硅上的1wt%铂和1wt%锡。装载之后催化剂床的长度约为70mm。
进料液体基本上由乙酸构成。将该反应进料液体蒸发并与氢气和作为载气的氦气一起以约2500hr-1的平均组合气时空速(GHSV)在约250℃的温度和22巴的压力下加入该反应器中。所得到的进料流包含约4.4%-约13.8%的乙酸摩尔百分比和约14%-约77%的氢气摩尔百分比。蒸气流出物的一部分通过气相色谱,用于分析该流出物的含量。在乙酸转化率为85%下,乙醇选择性为93.4%。
实施例2
所用的催化剂是依照实施例D的程序制备的1wt%铂和1wt%锡在硅酸钙上。
以蒸发的乙酸和氢气的进料流的2500hr-1的平均组合气时空速(GHSV)在250℃的温度和22巴的压力基本重复实施例1中提出的程序。蒸气流出物的一部分通过气相色谱,用于分析该流出物的含量。乙酸转化率大于70%,乙醇选择性为99%。
对比例
所用的催化剂是依照实施例F的程序制备的1wt%锡在低表面积的高纯度二氧化硅上。
以蒸发的乙酸和氢气的进料流的2500hr-1的平均组合气时空速(GHSV)在250℃的温度和22巴的压力基本重复实施例1中提出的程序。蒸气流出物的一部分通过气相色谱,用于分析该流出物的含量。乙酸转化率小于10%,乙醇选择性小于1%。
尽管已经结合特别实施例描述了本发明,但在本发明的精神和范围内的对这些实施例的改变对于本领域技术人员将是容易显而易见的。鉴于以上讨论,上面结合背景技术和发明详述所讨论的其公开内容全部通过参考引入此处的现有技术和参考文献的相关知识,相信不需要进一步的描述。
Claims (26)
1.用于由乙酸选择性直接生成乙醇的方法,包括:将包含乙酸和氢气的进料流在升高温度与适合的加氢催化剂接触,所述加氢催化剂包含在适合的催化剂载体上的铂和锡的组合以及任选的负载在所述载体上的第三金属,其中所述第三金属选自由以下构成的组:钯、铑、钌、铼、铱、铬、铜、钼、钨、钒和锌。
2.权利要求1的方法,其中该催化剂载体选自由二氧化硅、氧化铝、二氧化硅-氧化铝、硅酸钙、碳、氧化锆和氧化钛构成的组。
3.权利要求2的方法,其中该催化剂载体是二氧化硅。
4.权利要求3的方法,其中该催化剂载体是高纯度二氧化硅。
5.权利要求2的方法,其中该催化剂载体是硅酸钙。
6.权利要求2的方法,其中该催化剂载体是碳。
7.权利要求6的方法,其中该催化剂载体是石墨。
8.权利要求7的方法,其中该催化剂载体是高表面积的石墨化碳。
9.权利要求1的方法,其中该催化剂载体包含Pt/Sn重量比在约0.1-2的范围内的铂和锡的组合。
10.权利要求9的方法,其中铂的负载量为约0.5wt%,锡的负载量为约0.5wt%,该催化剂载体为二氧化硅、石墨、二氧化硅-氧化铝或硅酸钙。
11.权利要求9的方法,其中铂的负载量为约1wt%,锡的负载量为约1wt%,该催化剂载体为二氧化硅、石墨、二氧化硅-氧化铝或硅酸钙。
12.权利要求9的方法,其中铂的负载量为约0.5wt%,锡的负载量为约2.5wt%,该催化剂载体为二氧化硅、石墨、二氧化硅-氧化铝或硅酸钙。
13.权利要求9的方法,其中铂的负载量为约1wt%,锡的负载量为约5wt%,该催化剂载体为二氧化硅、石墨、二氧化硅-氧化铝或硅酸钙。
14.权利要求1的方法,其中基于消耗的乙酸,乙醇的选择性为至少60%。
15.权利要求1的方法,其中基于消耗的乙酸,乙醇的选择性为至少80%。
16.权利要求1的方法,其中基于消耗的乙酸,乙醇的选择性为至少90%。
17.权利要求1的方法,其中基于消耗的乙酸,乙醇的选择性为至少95%。
18.权利要求1的方法,其中该加氢为乙醇是在气相中和在约200℃-300℃的范围内的温度进行的。
19.权利要求18的方法,其中该加氢为乙醇是在气相中和在约225℃-275℃的范围内的温度进行的。
20.权利要求18的方法,其中所述进料流包含惰性载气。
21.权利要求18的方法,其中反应物由摩尔比在约100∶1-1∶100的范围内的乙酸和氢气构成,反应区的温度在约200℃-300℃的范围内,且反应区的压力在约1-30大气压绝对压力的范围内。
22.权利要求18的方法,其中反应物由摩尔比在约1∶20-1∶2的范围内的乙酸和氢气构成,反应区的温度在约225℃-275℃的范围内,且反应区的压力在约10-25大气压绝对压力的范围内。
23.用于由乙酸选择性直接生成乙醇的方法,包括:将包含乙酸和氢气的进料流在升高温度与适合的加氢催化剂接触,所述加氢催化剂在适合的催化剂载体上包含约0.5wt%-约1wt%铂和0.5wt%-约5wt%的锡以及任选的负载在所述载体上的第三金属,其中所述第三金属选自由钴、钌和钯构成的组。
24.权利要求23的方法,其中该催化剂载体包含各自负载量水平为约1wt%的铂和锡。
25.权利要求23的方法,其中该催化剂载体是二氧化硅。
26.权利要求23的方法,其中反应物由摩尔比在约1∶20-1∶5的范围内的乙酸和氢气构成,反应区的温度在约225℃-275℃的范围内,且反应区的压力在约10-25大气压绝对压力的范围内。
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