CN1681594A - 中孔材料及其选择性氧化有机化合物的用途 - Google Patents

中孔材料及其选择性氧化有机化合物的用途 Download PDF

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CN1681594A
CN1681594A CNA038222310A CN03822231A CN1681594A CN 1681594 A CN1681594 A CN 1681594A CN A038222310 A CNA038222310 A CN A038222310A CN 03822231 A CN03822231 A CN 03822231A CN 1681594 A CN1681594 A CN 1681594A
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transition metal
catalyst
mesopore
metal
inorganic oxide
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单志平
托马斯·马施迈尔
雅各布斯·格尼留斯·扬森
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Lummus Technology LLC
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ABB Lummus Global Inc
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Abstract

本发明公开了一种特别用于烃类和其他有机化合物的选择性氧化的材料，其包括非晶形多孔无机氧化物和至少一种催化活性金属，所述无机氧化物基于微孔和中孔带有至少97体积％的中孔，所述催化活性金属选自一种或多种过渡金属与一种或多种贵金属。

Description

中孔材料及其选择性氧化有机化合物的用途
参考相关申请
本申请是2001年11月27日提交的美国申请序列号09/995,227的部分继续，此处将其引为参考，引为参考的该申请则是1999年9月7日提交的美国申请序列号09/390,276的部分继续，现已授权为美国专利号6,358,486 B1，前者要求后者的优先权。
背景
1.发明领域
本发明涉及一种中孔材料，特别是一种催化材料，以及该中孔材料用于有机化合物，特别是烃类的选择性氧化的用途。
2.现有技术背景
各种方法和催化剂因用于有机化合物的选择性氧化而为众所已知。例如，美国专利号5,948,683(Koermer等)公开了一种在一氧化碳存在下用于不饱和烃的选择性氧化的催化材料。该催化材料包括磷酸盐化的二氧化铈，通过将二氧化铈颗粒与磷酸盐溶液混合，然后将颗粒从溶液中分离出来后对其煅烧而制得。
美国专利号5,811,599(Alive等)公开了一种在硅酸钛催化剂存在下，采用过氧化氢水溶液进行烃类氧化的方法。
美国专利号5,707,917(Geus等)公开了一种用于烃类选择性氧化的催化剂，所述催化剂含有基于一种或多种金属氧化物的载体，和分散于载体表面之上的钒-磷氧化物。该方法包含氧化和还原阶段。在还原阶段，将烃类与催化剂接触，并以氧化或非氧化形式吸附至催化剂之上。然后使负载的催化剂进入氧化阶段，其中在气态氧存在下生成期望产物并随后加以分离。
目前仍需要对方法和催化剂进行改进，以用于烃类和其他有机化合物的选择性氧化。
发明简述
本发明提供了一种材料，所述材料含有基于微孔和中孔，其中空至少为97体积％的非晶态多孔无机氧化物，以及至少一种选自一种或多种过渡金属与一种或多种贵金属的催化活性金属。本发明还提供该材料的制造方法，以及该材料作为催化剂用于有机化合物的选择性氧化的用途。
此处提供的方法和催化剂以非常高的选择性用于烃类和其他有机化合物的选择性氧化。
附图简述
下面将通过参考附图对各种实施方案进行描述，其中：
图1A是实施例1的催化材料的X-射线衍射图样的显示图；
图1B是实施例1的催化材料的透射式电子显微检查图象；
图2以图表介绍了涉及实施例1的催化材料的孔体积和孔径数据；
图3是实施例4，5，6和7的催化材料的X-射线衍射图样的显示图；以及，
图4是实施例8的催化材料的X-射线衍射图样的显示图。
优选实施方案详述：
本发明的催化剂包括在结构上基本为中孔的三维、稳定的多孔无机氧化物材料。该材料具有非晶形但规则化(假晶体)的结构。中孔材料在美国专利号6,358,486 B1中有描述，所述专利此处以其全部引为参考。该催化剂进一步包括一种或多种贵金属和/或一种或多种过渡金属。
本发明的非晶形无机氧化物材料通常同时含有中孔和微孔。微孔的定义为直径低于约2nm的孔。中孔的定义为直径从约2nm至约50nm的孔。本发明的无机氧化物材料带有的中孔的体积百分比至少约97％，优选为至少约98％。
美国专利号6,358,486 B1中描述了一种优选含有多孔二氧化硅的催化剂载体的制造方法。以N2-测孔仪确定的该优选催化剂的平均中孔孔径为约2nm至约25nm。通常，该中孔无机氧化物通过将(1)无机氧化物的水的前体与(2)有机模板剂的混合物进行加热而制备得到，所述有机模板剂与氧化物前体或由该前体产生的氧化物种类充分混合，并优选地与其生成氢键。
起始材料通常为非晶形材料，包括一种或多种诸如二氧化硅或氧化铝的无机氧化物，可带有或不带有另外的金属氧化物。硅或铝原子可部分被催化活性过渡金属原子所取代，所述过渡金属原子例如钛，钒，铜，锆，锰，锌，铬，钼，钨，镍，钴和铁等等。基于催化剂总重，过渡金属的组成优选地高达约60重量％，更优选为从约0.001重量％至约20重量％。可在方法开始之前将另外的金属任选地掺入至该材料中，用于生产含有中孔的结构。例如，可制备含有过渡金属醇盐，醇硅或醇铝(例如四乙基正硅酸酯“TEOS”，或异丙醇铝)和有机模板剂的均一合成混合物。然后可将合成混合物老化、干燥并煅烧，用于产生中孔结构。合成混合物的干燥可通过将合成混合物加热至从约50℃至约150℃，优选60℃至约120℃的干燥温度，并持续足够时间用以驱逐出水和/或挥发性有机液体而完成。干燥混合物的煅烧可通过将干燥混合物加热至从约300℃至约1000℃，优选约400℃至约700℃的煅烧温度，并持续足够时间用以形成中孔结构而完成。煅烧的时间范围典型地从约2小时至约40小时，至少部分依赖于煅烧温度。
加热用以除去水和/或挥发性有机液体之后并在煅烧之前，存在一个将干燥混合物于容器内加热的选择步骤，加热温度为从约130℃至约200℃，持续时间从约2小时至约96小时。该步骤可用来对最终组成的中孔孔径、表面积和孔体积进行操作。
同样，该材料制得之后，可任选地以诸如碱金属(例如钠，钾，锂等)离子的其他离子取代体系中的阳离子。
生成中孔的有机模板剂优选的是二醇(包括两个或多个羟基的化合物)，例如甘油，二甘醇，三甘醇，四甘醇，丙二醇等，或者是如下成员：三乙醇胺，四氢噻吩砜，四亚乙基五胺和二乙基乙二醇二苯甲酸酯。优选地，模板剂的沸点至少为约150℃。
中孔催化剂载体是假晶体材料(即，通过现有的X-射线衍射技术未发现结晶性)。中孔的壁厚优选为从约3nm至约25nm。通过BET(N2)确定的催化剂载体的表面积范围优选从约400m2/g至约1200m2/g。催化剂的孔体积范围优选从约0.3cm3/g至约2.2cm3/g。
在混合过程中，适当选择的活性金属与模板剂(如三乙醇胺或“TEA”)形成络合物。干燥后，络合物与游离的有机化合物(例如TEA)一道作为用于中孔的模板剂。然后，在煅烧过程中，络合物分解；任何有机物种类均被除去。结果，过渡金属均一覆盖于中孔的内表面。根据过渡金属的载量，可对这些过渡金属的配位状态进行控制。大部分活性位点因优先富集于中孔表面上而容易接近。另外，该三维中孔体系还促进了颗粒内的传质。
带有或不带有过渡金属的无机氧化物载体，可通过其中掺入催化有效量的一种或多种诸如金(Au)，银(Ag)，铂(Pt)，钯(Pd)，铱(Ir)，铑(Rh)，钌(Ru)，铼(Re)或锇(Os)的贵金属而进一步修饰。这些贵金属可在中孔内形成直径10nm或更小的纳米颗粒。基于总催化剂重量，贵金属的含量可高达约60重量％，优选为从约0.1重量％至约40重量％。
将贵金属掺入至无机中孔氧化物中可通过任意的合适方法，例如离子交换，或者以可溶、可分解的贵金属化合物的溶液浸润无机氧化物，然后洗涤，干燥，并将浸润过的无机化合物进行诸如煅烧的方法，以使贵金属化合物分解，由此生产出在无机氧化物孔内带有游离贵金属的活化催化剂。合适的贵金属化合物包括诸如硝酸盐、氯化物、铵络合物等的盐类。
任选地以水来进行贵金属浸润过的无机氧化物催化剂的洗涤，以去除某些阴离子。可通过将催化剂加热至从约50℃至约190℃的干燥温度以除去水和/或其他挥发性化合物，从而完成催化剂的干燥。可在约150℃至约600℃的温度下持续足够时间段，从而煅烧催化剂以使其活化。通常，至少部分依赖于煅烧温度，煅烧的完成需要2至40小时。
所得到的催化剂可在诸如下述的选择性氧化方法中被采用：
A)烯烃的环氧化作用生产环氧化物。合适的烯烃包括C2-C20不饱和烃类化合物，例如乙烯，丙烯，丁烯类(1-丁烯，2-丁烯，异丁烯)，丁二烯，戊烯类，直链或支链己烯，1-辛烯，环己烯等。氧化剂可包括氧，含氧的气体，过氧化氢(H2O2)，氧化氮，有机氢过氧化物，有机过酸等。典型地在约30℃至约300℃，优选50℃至250℃的温度、从约大气压至约40巴的压力和从约10WHSV至约2000WHSV的空间速度下实施环氧化作用。反应可在气相、液相或混合(气/液)相中实施。
B)烷烃的部分氧化生产酮或醇的衍生物。合适的烷烃包括丙烷，丁烷，戊烷，环己烷等。合适的氧化剂可包括氧，含氧的气体，过氧化氢，氧化氮，有机氢过氧化物和有机过酸。典型地在约0℃至约200℃的温度、从约1巴至约30巴的压力和从约100hr-1至约100,000hr-1的空间WHSV速度下实施将烷烃部分氧化至酮。通常在约60℃至约450℃的温度、在高达约60巴的压力下实施醇的生产。反应可在气相、液相或混合相中实施。
C)醇类的部分氧化。合适的醇类包括，例如苯甲醇，苯基乙醇，苯酚和肉桂醇。合适的氧化剂可包括氧，含氧的气体，过氧化氢，氧化氮，有机氢过氧化物和有机过酸。例如，可采用含有诸如铜(Cu)的本公开内容的催化剂，在约300℃至约500℃的温度和高达约20巴的压力下，通过苯甲醇的部分氧化而得到苯甲醛。
D)芳香化合物的羟基化，用以将羟基加成入芳环结构中。所述芳香化合物优选地包括苯和甲苯，尽管也可采用其他的芳香化合物。合适的氧化剂可包括氧，含氧的气体，过氧化氢，氧化氮，有机氢过氧化物和有机过酸。可在25℃至500℃的温度和高达65巴的压力下，实施将苯氧化成苯酚以及将甲苯氧化成甲酚。该方法也可在蒸馏柱反应器中实施，温度范围为从100℃以上至270℃，苯分压范围为从约0.1atm至约45atm。
E)以氨(NH3)和过氧化氢或氧化氮对酮进行氨氧化作用，以产生对应的肟。合适的酮包括，例如丙酮，甲基乙基酮(MEK)，苯乙酮，环己酮，环十二烷酮等。反应条件典型地包括从约25℃至约150℃的温度，优选为40℃至约120℃，以及约1-10个大气压，优选为1-5个大气压的压力。
本发明的各种特征将通过如下给出的实施例进行例述。采用装备有石墨单色仪的Philips PW1840衍射计上的CuKα辐射记录所生成材料的X-射线粉末衍射图样(XRD)。样品的扫描范围为0.5-40°2θ，步级为0.02°。采用以LaB6丝作为电子源，在300kV下操作的PhilipsCM30T电子显微镜，来进行透射式电子显微检查(TEM)。于77K下，在Quantachrome Autosorb-6B上测量氮吸收等温线。采用BHJ模型计算中孔孔隙率。如无另外说明，所有的组成份均以重量计。
实施例1
根据如下步骤，制备并测试含有钛的本发明催化剂。首先，将1.1份的正丁醇钛(IV)与35.0份的四乙基正硅酸酯(“TEOS”)混合。然后，于搅拌下将25.3份的三乙醇胺(“TEA”)滴加入至上述混合物中。搅拌1小时后，于搅拌下将21.3份去离子水滴加入上述混合物中。另搅拌1小时后，将17.3份四乙基氢氧化铵(“TEAOH”)(25％)滴加入上述混合物中。在室温下对最终的均一混合物老化24小时，100℃下干燥24小时，然后以1℃min-1的斜率速度，以空气于700℃下煅烧10小时。
所生成材料的XRD图样如图1A中所示，在2θ中，只在0.5°和2.5°之间的约1.0°处显示有一个增强峰，指明产物为中孔结构的材料。图1B是所生成材料的TEM图。图1B显示，弯曲和曲折的孔是随机连接的，从而形成三维的孔网络。通过氮吸收确定的材料的BET表面积为约917m2/g。参照图2，材料的平均中孔直径是4.5nm，总的孔体积为约0.89cm3/g。
随后，以叔丁基过氧化氢作为氧化剂，在40℃及N2氛围下，采用环己烯的环氧化作用作为模型反应，以证明催化活性并对其定量。反应混合物组成为1份催化剂，9.6份环己烯(99％，使用前采用无水MgSO4干燥)和13.2份二氯甲烷(99％)。通过气相色谱(WAX 52 CB)分析样品。6小时后，约45.6％的环己烯以几乎1 00％的选择性被转化。周转频率(定义为每摩尔钛每小时转化的环己烯摩尔数)为20.2h-1。
对比实施例A
根据前面报告(L.Y.Chen，G.K.Chuah，S.Jaenicke，Catal.Lett.50(1998)107)中所述的步骤，合成出不是本发明所述的含有钛的催化剂，命名为Ti-MCM-41。其具有的BET表面积为934m2/g，平均孔直径约3.3nm。在与实施例1相同的条件下对其测试，其显示的周转频率仅为3.6h-1，是通过实施例1的催化剂得到的环己烯转化的不到20％。
实施例2
将金的纳米颗粒引入实施例1制备的催化剂中。通过将0.34重量份的HAuCl4·4H2O加入至400份的水中，制备得到AuCl4-水溶液。将该水溶液加热至70℃，采用NaOH水溶液将其pH调至约7.0。然后，将2份实施例1的催化剂悬浮于上述溶液中，再次将pH调至7.0。将悬浮液在70℃下老化1小时，并以蒸馏水洗涤3次，100℃下干燥2小时，最后在300℃下以空气煅烧4小时。
在填充有催化剂的垂直固定床石英反应器中实施丙烯的蒸汽相环氧化作用，以生成环氧丙烷。进料的反应物各含有10体积％的C3H6，H2和O2的氩气中，气时空速(GHSV)为10,000h-1mlg-1催化剂。反应温度保持在120℃。通过在线气相色谱(GC)分析进料物和产物。约3.5％的丙烯以约96％的选择性转化成环氧丙烷。
实施例3
根据美国专利号6,358,486实施例1的步骤，如下合成硅质材料：
首先，将1.3重量份的异丙醇铝溶解于39.1份的四丙基氢氧化铵(40％)水溶液中。然后，将47.88份的TEA(97％)与14.0份的水混合。搅拌下将水性TEA混合物滴加(8-9g/min)入含铝混合物中。最后，在搅拌条件下将33.1份的TEOS(98％)滴加(4-6g/min)入所得到的混合物中。将最终混合物在室温下老化48小时，于皿器中展开，以形成高度为1.0-1.2cm的薄层，并在100℃下于静态空气炉中干燥18小时。采用如下步骤对所形成的材料在空气中进行煅烧：将材料以1℃/min的加热速度加热至500℃，然后维持4小时，并以1℃/min的加热速度加热至550℃，然后维持10小时。
通过将所形成的材料浸润至AgNO3水溶液中，将该材料用于制备含银的催化剂。浸润后，将材料在250℃下煅烧4小时。采用ICP分析浸润后的催化剂，显示银的载量为约30.5％。
于大气压及220℃条件下，将该含银催化剂置于微流反应器中。反应物流含有20体积％的乙烯，40体积％的氧和40体积％的氮。总反应物流的GHSV为4,500hr-1。通过气相色谱分析产物。一小时内，乙烯的转化达到19.8％，而转化为环氧乙烷的选择性为约29％。
实施例4
将1.7份的正丁醇钛(IV)(99％)与106份的TEOS(98％)混合。然后，于搅拌下将77份TEA(97％)与58份去离子水的混合物滴加入至上述混合物中。搅拌约1小时后，将63份的TEAOH(25％)滴加入混合物中。合成混合物的Si/Ti摩尔比为100。最终均一混合物在室温下老化24小时，于98℃下干燥24小时，然后在空气中以1℃/min的斜率速度于650℃下煅烧10小时。材料的XRD图样如图3中所示。
实施例5
遵照与实施例4相同的步骤，不同之处在于采用3.4重量份的正丁醇钛(IV)，且混合物的Si/Ti比例为50。所生成材料的XRD图样如图3中所示。
实施例6
遵照与实施例4相同的步骤，不同之处在于采用8.6份的正丁醇钛(IV)，且Si/Ti比例为20。所生成材料的XRD图样如图3中所示。
实施例7
遵照与实施例4相同的步骤，不同之处在于采用17.2份的正丁醇钛(IV)，且Si/Ti比例为10。所生成材料的XRD图样如图3中所示。
从实施例4-7可看出，于初始合成混合物中加入合适量的钛化合物，可容易地控制本发明催化材料的钛载量。实施例4-7所生成材料的XRD图样表明，这些材料是中孔的。
实施例8
首先，将1.2(重量)份的乙酰基丙酮酸铬(III)(97％)与34.5份的TEOS(98％)混合。然后，于搅拌过程中将25份TEA(97％)滴加入上述混合物中。搅拌1小时后，搅拌条件下将18.8份的去离子水滴加入上述混合物中。另搅拌1小时后，将20.5份四乙基氢氧化铵(25％)滴加入上述混合物中。在室温下对最终的均一混合物老化24小时，100℃下干燥24小时。于180℃下将干燥的凝胶在高压釜中加热8小时，最后在空气中以1℃ min-1的斜率速度于700℃下煅烧10小时。
图4所示为该材料的XRD图样，在2θ中的约1.3°处呈现出一个增强峰。氮吸收显示其表面积为618m2/g，孔体积为0.67cm3/g，平均孔径直径为5.5nm。这些数据显示该实施例8的含铬材料在结构上是中孔的。在与实施例1中相同的条件下，将该材料作为催化剂进行测试，用于环己烯的环氧化作用。六小时后，约46％的环己烯以约94％的选择性被转化为环氧己烷。
尽管上述说明含有许多细节，这些细节不应解释为对本发明范围的限制，而仅仅是对其优选实施方案的例证。本领域人员可在本发明范围和实质内构思出许多其他可能性，本发明的范围如所附权利要求所限定。

Claims (43)

1.一种材料，含有：
a)非晶形多孔无机氧化物，所述无机氧化物基于微孔和中孔带有至少97体积％的中孔，所述中孔是互相连接的；和
b)至少一种催化活性金属，选自一种或多种过渡金属与一种或多种贵金属。
2.权利要求1的材料，其中的过渡金属选自钛，钒，铜，锆，锰，锌，铁，镍，钴，铬，钼和钨。
3.权利要求1的材料，其中的贵金属选自金，银，铂，钯，铱，铑，钌，铼和锇。
4.权利要求1的材料，其中的催化活性金属是金或银。
5.权利要求1的材料，其中的催化活性金属是铬。
6.权利要求1的材料，其中的催化活性金属是钛。
7.权利要求1的材料，其中的非晶形多孔无机氧化物以其X射线衍射图样在0.5°和2.5°之间具有2θ峰为特征。
8.权利要求1的材料，其中的非晶形多孔无机氧化物含有至少98体积％的中孔。
9.权利要求1的材料，其中的中孔大小为约2nm至约25nm。
10.权利要求1的材料，其中的无机氧化物是二氧化硅。
11.权利要求1的材料，其中的无机氧化物是氧化铝。
12.权利要求1的材料，其中过渡金属的组成百分比范围高达约60重量％。
13.权利要求1的材料，其中过渡金属的组成百分比范围为从约0.001重量％至约20重量％。
14.权利要求1的材料，其中贵金属的组成百分比范围高达约60重量％。
15.权利要求1的材料，其中贵金属的组成百分比范围为从约0.1重量％至约40重量％。
16.一种制造催化剂的方法，包含如下步骤：
c)将至少一种无机氧化物来源和至少一种中孔生成剂以及任选的一种或多种催化活性过渡金属来源相结合，以形成合成混合物；
d)干燥该合成混合物；
e)将干燥后的合成混合物加热至煅烧温度，持续足够时间段，以生成带有至少97体积％的中孔的非晶形载体结构；以及
f)将至少一种催化活性贵金属和/或过渡金属掺入至催化剂中。
17.权利要求16的方法，其中的无机氧化物选自氧化铝和二氧化硅。
18.权利要求17的方法，其中的无机氧化物来源选自醇化硅和醇化铝。
19.权利要求18的方法，其中的醇化硅是四乙基正硅酸酯，而醇化铝是异丙醇铝。
20.权利要求16的方法，其中通过在步骤(a)中，将含有过渡金属的化合物与无机氧化物来源相结合，以形成合成混合物，从而使催化活性过渡金属掺入至催化剂中。
21.权利要求16的方法，其中通过在使干燥后的合成混合物加热至煅烧温度的步骤(c)之后，将含有过渡金属的化合物掺入至催化剂中，从而使催化活性过渡金属掺入至催化剂中。
22.权利要求16的方法，其中的过渡金属选自钛，钒，铜，锆，锰，锌，铬，钼，钨，镍，钴和铁。
23.权利要求20的方法，其中含有过渡金属的化合物是钛的醇化物。
24.权利要求23的方法，其中钛的醇化物是正丁醇钛。
25.权利要求16的方法，其中使干燥后的合成混合物加热至煅烧温度包括，将干燥后的合成混合物加热至约120℃-约200℃的温度，持续约2小时至约96小时的时间段。
26.权利要求16的方法，其中的贵金属选自金，银，铂，钯，铱，铑，钌，铼和锇。
27.权利要求16的方法，其中步骤(d)将至少一种催化活性贵金属或过渡金属掺入至催化剂中包含，以贵金属和/或过渡金属的可溶、可分解化合物的溶液浸润非晶形载体结构，然后分解贵金属化合物和/或过渡金属化合物。
28.权利要求27的方法，其中分解贵金属化合物和/或过渡金属化合物的步骤包含，在足以分解贵金属化合物和/或过渡金属化合物的温度下，煅烧贵金属和/或过渡金属浸润的非晶形载体。
29.权利要求28的方法，其中的贵金属是金或银。
30.权利要求16的方法，其中的中孔生成剂选自甘油，二甘醇，三甘醇，四甘醇，丙二醇，三乙醇胺，四氢噻吩砜，四亚乙基五胺和二乙基乙二醇二苯甲酸酯。
31.权利要求16的方法，其中步骤(d)掺入至少一种催化活性贵金属和/或过渡金属包含将催化活性贵金属和过渡金属均掺入至催化剂中。
32.一种用于选择性氧化有机化合物的方法，包含：
在存在有催化剂的部分氧化反应条件下，将有机化合物与氧化剂接触，所述催化剂包括非晶形多孔无机氧化物和至少一种催化活性金属，所述无机氧化物基于微孔和中孔带有至少97体积％的中孔，所述催化活性金属选自一种或多种过渡金属与一种或多种贵金属。
33.权利要求32的方法，其中的有机化合物是烯烃，且选择性氧化方法包含烯烃的环氧化作用，以产生对应的环氧化物。
34.权利要求33的方法，其中的烯烃选自乙烯，丙烯，1-丁烯，2-丁烯，异丁烯，丁二烯，戊烯，己烯，1-辛烯和环己烯，氧化剂选自氧，含氧的气体，过氧化氢，氧化氮，有机氢过氧化物和有机过酸，反应条件包括从约50℃至约250℃的温度，从约大气压力至约60巴的压力，以及从约10WHSV至约2000WHSV的空间速度。
35.权利要求32的方法，其中的催化活性金属选自钛，铬，钒，金和银。
36.权利要求32的方法，其中的有机化合物是烷烃，且选择性氧化方法是烷烃的部分氧化，以产生对应的酮或醇。
37.权利要求36的方法，其中的烷烃选自丙烷，丁烷，戊烷和环己烷，氧化剂选自氧，含氧的气体，过氧化氢，氧化氮，有机氢过氧化物和有机过酸，反应条件包括从约0℃至约200℃的温度、从约1巴至约30巴的压力和从约100hr-1至约1000hr-1的空间速度。
38.权利要求32的方法，其中的有机化合物是酮，且选择性氧化方法是酮的氨氧化作用，以产生对应的肟。
39.权利要求38的方法，其中的酮选自丙酮，甲基乙基酮，苯乙酮，环己酮和环十二烷酮，氧化剂是与氨混合的过氧化氢或氧化氮，反应条件包括从约25℃至约150℃的温度，以及从约1个大气压至约10个大气压的压力。
40.权利要求32的方法，其中的有机化合物是芳香化合物，且选择性氧化方法是芳香化合物的羟基化作用，以将至少一个羟基加成入芳环结构中。
41.权利要求40的方法，其中所述芳香化合物选自苯和甲苯，氧化剂选自氧，含氧的气体，过氧化氢，氧化氮，有机氢过氧化物和有机过酸，以及反应条件包括从125℃至约500℃的温度和高达65巴的压力。
42.权利要求32的方法，其中的催化活性过渡金属选自钛，钒和铬。
43.权利要求32的方法，其中的催化活性贵金属是金或银。
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