CN101360561A - 预催化剂向催化活性银钒氧化物青铜的转化 - Google Patents
预催化剂向催化活性银钒氧化物青铜的转化 Download PDFInfo
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- CN101360561A CN101360561A CNA2006800514865A CN200680051486A CN101360561A CN 101360561 A CN101360561 A CN 101360561A CN A2006800514865 A CNA2006800514865 A CN A2006800514865A CN 200680051486 A CN200680051486 A CN 200680051486A CN 101360561 A CN101360561 A CN 101360561A
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- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明涉及将包含惰性载体、有机碳源和含银和钒的多金属氧化物的预催化剂转化成包含惰性载体和催化活性银-钒氧化物青铜的气相氧化催化剂的方法。根据所述方法,在含有少于10体积%氧的气氛中在至少350℃的温度下热处理预催化剂。在处理之前,将预催化剂中碳源的量调节至低于临界量的值。通过在含氧气氛中在80至200℃的温度下分离和一部分碳源的同时分解来降低碳量。由此获得的催化剂用于芳烃的部分气相氧化成醛、羧酸和/或羧酸酐。
Description
本发明涉及一种将多金属氧化物预催化剂转化成含有催化活性银钒氧化物青铜的气相氧化催化剂,特别是将芳烃气相部分氧化成醛、羧酸和/或羧酸酐所用的催化剂的方法。
在工业上通过在固定床反应器中催化气相氧化芳烃如苯、邻-、间-、对-二甲苯、萘、甲苯或均四甲苯(1,2,4,5-四甲基苯)来制备多种醛、羧酸和/或羧酸酐。根据原料,例如由此获得苯甲醛、苯甲酸、马来酸酐、邻苯二甲酸酐、间苯二甲酸、对苯二甲酸或苯均四酸酐。为此,使含氧气体(例如空气)和要氧化的原料通过设置在反应器中的许多管,各个管中设置有至少一种催化剂床。
WO 00/27753、WO 01/85337和WO 2005/012216描述了包含氧化银和钒氧化物的多金属氧化物。热处理将该多金属氧化物转化成催化芳烃的部分氧化反应的银钒氧化物青铜。银钒氧化物青铜被理解为是指Ag∶V原子比小于1的银钒氧化物。它们是优选以层或隧道结构结晶的通常半导电或金属性导电的氧化固体,[V2O5]主晶格中的钒被部分还原成V(IV)。多金属氧化物向银钒氧化物青铜的热转化经由一系列尚未详细理解的还原与氧化反应进行。
在实践中,将多金属氧化物作为层施涂到惰性载体上以获得所谓的预催化剂。通常在氧化反应器中,在芳烃氧化成醛、羧酸和/或羧酸酐的条件下将预催化剂原位转化成活性催化剂。为了防止对催化剂的热破坏,含有要氧化的烃的气流的烃载量必须在原位转化过程中从非常低的值缓慢增加,控制催化剂床中的热点温度。该过程通常持续数天或数周,直到获得在此进行生产性烃氧化的最终载量。
具体而言,预催化剂的原位转化是一种耗时的工艺。此外,在工艺开始时精确计量少量烃在许多情况下是困难的。因此期望在气相氧化反应器外适当地预处理该预催化剂,以使生产性气相氧化可以在催化剂安装后立即开始。
WO 00/27753公开了考虑影响参数,如气氛的组成、粘合剂的存在与否以及粘合剂的类型和量,预催化剂的转化也可以通过在高于200至650℃的温度下的热处理在氧化反应器外实施。应当在预备实验中确定最佳条件。该文献没有对这些条件作出任何更精确的记载。
本发明的一个目的是说明一种可在氧化反应器外将预催化剂转化成活性气相氧化催化剂的方便方法。
该目的根据本发明通过在包含少于10体积%氧的气氛中在至少350℃的温度下热处理预催化剂,以将包含惰性载体、有机碳源以及含银和钒的多金属氧化物的预催化剂转化成包含惰性载体和催化活性银钒氧化物青铜的气相氧化催化剂的方法来实现,其中在热处理前,将预催化剂中碳源的量调节至低于临界量的值(非零),临界量是指在预催化剂热处理过程中开始还原成元素银时的碳源的量。
在起始多金属氧化物中,钒以氧化态5(钒(V))存在;在银钒氧化物青铜中,平均钒氧化态通常为4.5至4.9,特别为4.6至4.7。
通过本发明的热处理获得的催化剂表现出足够耐磨性并可以没有任何问题地处理,运输和引入反应管。
实施热处理所用的气氛包含少于10体积%,优选少于3体积%,特别是少于1体积%的(分子)氧。通常,使用基本不含氧的惰性气体,优选氮气。热处理适当地在气流,优选惰性气流中进行。
热处理可以在所有合适的装置,例如在塔盘炉、旋转球体炉、可加热反应器等中进行,在这些装置中,气流流过预催化剂床。热处理在至少350℃,优选至少400℃,特别是400至600℃的温度下进行。在所述范围内的较高温度通常实现银钒氧化物青铜的较高结晶度和较低BET表面积。加热速率不特别重要;1至10℃/分钟通常是合适的。热处理的持续时间通常为0.5至12小时,优选1至5小时。
预催化剂包含有机碳源。在预催化剂的热处理中,碳源被认为充当用于将多金属氧化物中存在的钒(V)部分还原成V(IV)的还原剂。
合适的碳源是预催化剂制备中所用的典型助剂,例如作为成孔剂或粘合剂。一般而言,它们是(i)具有2至12个碳原子和至少一个选自OH、C=O和NH2的官能团的化合物;和/或(ii)由具有2至12个碳原子和至少一个选自OH、C=O和NH2的官能团的重复单元形成的聚合化合物。酮基(C=O)也可以是甲酰胺、羧酸、羧酸酯或羧酸酐基团的一部分。碳源优选选自具有2至6个碳原子和至少两个各自独立地选自OH、C=O和NH2的官能团的化合物。
合适的碳源包括例如乙二醇、丙二醇、丙三醇、季戊四醇、戊糖、己糖、草酸、草酸铵、丙二酸、马来酸、富马酸、琥珀酸、抗坏血酸、苯甲酸、邻-、间-和对-甲苯酸、邻苯二甲酸、邻苯二甲酸酐、间苯二甲酸、对苯二甲酸、二甲基甲酰胺、二甲基乙酰胺、N-甲基吡咯烷酮。
合适的碳源也包括如聚亚烷基二醇、聚亚烷基胺、多糖、聚乙烯基醇、乙酸乙烯酯/月桂酸乙烯酯、乙酸乙烯酯/丙烯酸酯、苯乙烯/丙烯酸酯、乙酸乙烯酯/马来酸酯或乙酸乙烯酯/乙烯共聚物之类的聚合物。
已经发现,必须控制预催化剂中碳源的量。当碳源的量太高时,预催化剂的热处理不会形成银钒氧化物青铜,而是将多金属氧化物中存在的银离子还原成元素银。尽管银钒氧化物青铜具有深绿色,沉积在催化剂上的元素银表现为黑色。也可以在粉末X-射线衍射图中检测出因可归因于立方银晶格的反射的元素银的存在。令人惊讶地,从碳源量的极限值突然发生还原成元素银。对于本专利申请,该极限值被称作“碳源的临界量”。
临界量取决于碳源的化学性质。其可以由本领域技术人员在预备实验中容易地测定。例如,具有给定碳源含量的样品量预催化剂可以经过热处理(例如在氮气流中在490℃下4小时),并可以分析所得催化剂的元素银的存在。当还原成元素银时,本领域技术人员(在新鲜样品量的预催化剂中)可以逐步降低碳含量(根据下述方法)并再对预催化剂施以热处理。由此,可以迅速并直接借助几个实验来确定窄范围的临界量。
优选在热处理前将预催化剂中碳源的量调节至低于2重量%的值(按碳计算并基于多金属氧化物的重量),例如0.5至低于2重量%的值,更优选至低于或等于1.3重量%的值。热处理前预催化剂中碳源的量通常为多金属氧化物重量的至少0.1重量%,通常至少0.5重量%。
可以通过在氧气流中燃烧(预)催化剂活性组合物的精确称重样品并例如借助红外测量池(IR cell)定量检测所形成的二氧化碳,测定碳含量。
为了适当调节碳源的含量,本领域技术人员可以在预催化剂制备中相容地选择成孔剂、粘合剂和具有低碳含量的其它助剂或仅以次要量使用含碳的助剂。但是一般地,就多金属氧化物在载体上适当粘合、所需孔结构和其它因素而言,必须在制备预催化剂中使用相对大量的含碳助剂。
在大多数情况下,预催化剂因此最初包含大于临界量或对应于临界量的碳源量。通常,未处理的预催化剂包含相当于多金属氧化物重量的3至10重量%碳的碳源量。可以通过在含氧气氛中在80至200℃的温度下热处理或烧除预催化剂来将碳源的量调节至低于临界量的值。“烧除”应该被理解为是指碳含量的降低,在此过程中一部分碳源蒸发掉,升华掉和/或氧化分解成如二氧化碳的气态产物。
烧除可以在所有合适的装置,例如用于预催化剂的随后热处理的那些装置中进行。为了避免具有高放热性的碳源过快分解和对催化剂的潜在热破坏,烧除优选包括至少一个加热阶段,在此过程中以低于5℃/分钟(特别是低于1.5℃/分钟)的速率升高预催化剂温度,以及至少一个平稳阶段,在此过程中将预催化剂温度保持基本恒定。
烧除在含氧气氛中进行;该气氛优选包含至少5体积%,例如至少12.5体积%,和至多25体积%(分子)氧。方便使用空气。特别优选在空气流中进行烧除。在80至200℃,优选120至190℃的温度下进行烧除。
合适的多金属氧化物、它们的制备和它们施涂到惰性载体上是本身已知的并且如WO 00/27753、WO 01/85337和WO 2005/012216中所述。
一般而言,多金属氧化物具有通式I
Aga-cQbMcV2Od*e H2O I
其中a为0.3至1.9,优选0.5至1.0,更优选0.6至0.9;
Q为选自P、As、Sb和/或Bi的元素,
b为0至0.3,优选0至0.1,
M是选自碱金属和碱土金属、Bi、Tl、Cu、Zn、Cd、Pb、Cr、Au、Al、Fe、Co、Ni、Mo、Nb、Ce、W、Mn、Ta、Pd、Pt、Ru和/或Rh,优选Nb、Ce、W、Mn和Ta,特别是Ce和Mn的至少一种金属,其中Ce最优选,
c为0至0.5,优选0.005至0.2,特别是0.01至0.1;条件是(a-c)≥0.1,
d为由式I中非氧元素的化合价和出现率确定的数,且
e为0至20,优选0至5。
多金属氧化物优选存在于晶体结构中,该晶体结构的粉末X-射线图的特征在于在15.23±0.6,12.16±0.4,10.68±0.3,3.41±0.04,3.09±0.04,3.02±0.04,2.36±0.04和1.80±0.04的晶面间距d下的反射。
一般而言,式I的多金属氧化物的完整粉末X-射线衍射图具有包括表1中所列的17项反射在内的反射。式I的多金属氧化物的粉末X-射线图的较低强度的反射不计入表1中。
表1:
反射 | d | I相对(%) |
1 | 15,23±0,6 | 16 |
2 | 12,16±0,4 | 11 |
3 | 10,68±0,3 | 18 |
4 | 5,06±0,06 | 11 |
5 | 4,37±0,04 | 23 |
6 | 3,86±0,04 | 16 |
7 | 3,41±0,04 | 80 |
8 | 3,09±0,04 | 61 |
9 | 3,02±0,04 | 100 |
10 | 2,58±0,04 | 23 |
11 | 2,48±0,04 | 24 |
12 | 2,42±0,04 | 23 |
13 | 2,36±0,04 | 38 |
14 | 2,04±0,04 | 26 |
15 | 1,93±0,04 | 31 |
根据基于“Recommendations 1984”of the IUPAC International Unionof Pure and Applied Chemistry(参见Pure & Appl.Chem.57,603(1985))的DIN 66 131测得的BET比表面积通常大于1平方米/克,优选为3至250平方米/克,特别是10至250平方米/克,更优选为20至80平方米/克。
为了制备多金属氧化物,通常将五氧化二钒(V2O5)的悬浮液与银化合物溶液和金属组分M的化合物溶液和如果适当,Q化合物溶液一起加热。用于该反应的溶剂可以是极性有机溶剂;所用溶剂优选为水。所用银盐优选为硝酸银。
在使用时,选自P、As、Sb和/或Bi的元素Q可以以元素形式或氧化物或氢氧化物形式使用。优选使用它们的部分中和或游离酸,例如磷酸、氢砷酸、氢锑酸、磷酸氢铵、砷酸氢铵、锑酸氢铵和铋酸氢铵以及碱金属的磷酸氢盐、砷酸氢盐、锑酸氢盐和铋酸氢盐。所用元素Q最优选单独为磷,尤其是磷酸、亚磷酸、次磷酸、磷酸铵或磷酸酯形式,特别是磷酸二氢铵形式。
所用金属组分M的盐通常是水溶性盐,例如高氯酸盐或羧酸盐,特别是乙酸盐。优选使用所述金属组分M的硝酸盐,特别是硝酸铈或硝酸锰。
V2O5与银化合物、金属组分M的化合物和如果适当Q的反应通常可以在室温或升高的温度下进行。一般而言,该反应在20至375℃,优选20至100℃,更优选60至100℃的温度下进行。当反应温度高于所用溶剂的沸点温度时,反应适当地在压力容器中在反应体系自生压力下进行。反应条件优选选择成要使得反应可以在大气压下进行。根据转化的原料的类型和所用温度条件,该反应的持续时间可以为10分钟至3天。可以将反应时间延长至例如5天和更久。一般而言,V2O5与银化合物、金属组分M的化合物以生成多金属氧化物的反应进行6至24小时。在反应过程中,V2O5悬浮液的橙红色改变且新化合物以深褐色悬浮液形式形成。
可以从反应混合物中分离由此形成的多金属氧化物。所得多金属氧化物悬浮液特别有利地被喷雾干燥。喷雾干燥通常在大气压或减压下进行。干燥气体的入口温度根据所用压力和所用溶剂确定-所用干燥气体通常是空气,但当然也可以采用其它干燥气体,例如氮气或氩气。干燥气体在喷雾干燥器中的入口温度有利地选择成要使得通过溶液蒸发冷却的干燥气体的初始温度长时间不超过200℃。一般而言,干燥气体的初始温度要调节到50至150℃,优选100至140℃。
预催化剂是由惰性载体材料和以涂层形式施加到其上的至少一层构成的催化剂前体,该层优选包含基于该层总重量的30至100重量%,特别是50至100重量%的式I多金属氧化物。该层更优选完全由式I的多金属氧化物构成。当催化活性层除了式I的多金属氧化物外还包含其它组分时,这些可以例如是惰性材料,例如碳化硅或块滑石,或用于将芳烃氧化成醛、羧酸和/或羧酸酐的基于钒氧化物/锐钛矿的其它已知催化剂。该预催化剂优选包含预催化剂总重量的5至25重量%的多金属氧化物。
用于预催化剂和被涂布催化剂的惰性载体材料可以是有利地用在用于将芳烃氧化成醛、羧酸和/或羧酸酐的被涂布催化剂的制备中的几乎所有现有技术载体材料,例如石英(SiO2)、瓷器、氧化镁、二氧化锡、碳化硅、金红石、氧化铝(Al2O3)、硅酸铝、块滑石(硅酸镁)、硅酸锆、硅酸铈或这些载体材料的混合物。载体通常是“无孔的”。该术语被理解为是“除工业无效量的孔外是无孔的”的含义,因为在技术上不可避免地在理想上不应包含任何孔的载体材料中存在少量孔。要强调的有利的载体材料特别是块滑石和碳化硅。载体材料的形式通常对于本发明的预催化剂和被涂布催化剂不重要。例如,可以使用球状、环状、片状、螺旋状、管状、挤出物形式或碎片状的催化剂载体。这些催化剂载体的尺寸对应于通常制备用于芳烃的气相部分氧化的被涂布催化剂所用的催化剂载体的尺寸。如上所述,上述载体材料也可以以粉末形式添加到本发明的被涂布催化剂的催化活性物质中。
对于用多金属氧化物涂布惰性载体材料,可以使用已知方法。例如,分离和干燥后获得的多金属氧化物粉末浆料可以在加热的涂布筒中喷雾到催化剂载体上。也可以使用流化床涂布器将多金属氧化物涂料施加到催化剂载体上。可以在水,有机溶剂例如高级醇,多元醇例如乙二醇、1,4-丁二醇或丙三醇,二甲基甲酰胺、二甲基乙酰胺、二甲亚砜、N-甲基吡咯烷酮或环脲,如N,N’-二甲基亚乙基脲或N,N’-二甲基亚丙基脲或这些有机溶剂与水的混合物中制备多金属氧化物的悬浮液。可以加入溶解的或有利地为含水分散体形式的有机粘合剂,优选共聚物,在这种情况下,基于本发明的多金属氧化物的悬浮液或浆料的固含量,通常使用10至20重量%的粘合剂含量。合适的粘合剂是例如乙酸乙烯酯/月桂酸乙烯酯、乙酸乙烯酯/丙烯酸酯、苯乙烯/丙烯酸酯、乙酸乙烯酯/马来酸酯或乙酸乙烯酯/乙烯共聚物。
被涂布催化剂用于将芳烃部分氧化成醛、羧酸和/或羧酸酐,特别是用于用包含分子氧的气体将邻二甲苯和/或萘气相部分氧化成邻苯二甲酸酐或将甲苯气相部分氧化成苯甲酸和/或苯甲醛。为此,催化剂可以单独使用或与其它具有不同活性的催化剂,例如基于钒氧化物/锐钛矿的现有技术催化剂结合使用,在此情况下,不同催化剂通常放置在可设置在反应器中的一个或多个固定催化剂床中的单独催化剂床中。
为此,将被涂布催化剂或预催化剂装入从外部,例如借助盐熔体,恒温至反应温度的管式反应器的反应管内。使反应气体在100至650℃,优选250至480℃的温度和在通常0.1至2.5巴,优选0.3至1.5巴的升高压力下,以通常750至5000小时-1的表观速度通过由此制成的催化剂床。
供应给催化剂的反应气体通常通过将包含分子氧和除氧外还可能包含合适的反应调节剂和/或稀释剂,例如水蒸汽、二氧化碳和/或氮气的气体与要氧化的芳烃混合来获得,且包含分子氧的气体通常可以包含1至100体积%,优选2至50体积%,更优选10至30体积%的氧,0至30体积%,优选0至20体积%的水蒸汽,和0至50体积%,优选0至1体积%的二氧化碳,余量为氮气。为了获得反应气体,通常以30至300克/立方米(STP),优选以70至150克/立方米(STP)要氧化的芳烃气体,供应包含分子氧的气体。包含分子氧的气体特别有利地为空气。
在用于将芳烃部分氧化成醛、羧酸和/或羧酸酐的方法的优选实施方案中,据发现特别有利是由邻二甲苯和/或萘制备邻苯二甲酸酐中,芳烃首先在本发明的被涂布催化剂床上部分转化成反应混合物。然后可以使所得反应混合物或其一部分与至少一种其催化活性组合物含五氧化二钒和锐钛矿的其它催化剂接触。
气流优选相继通过位于上游的一个催化剂床和位于下游的一个催化剂床,位于上游的催化剂床包含本发明的催化剂,位于下游的催化剂床包含至少一种其催化活性组合物含五氧化二钒和锐钛矿的催化剂。一般而言,位于下游的催化剂的催化活性组合物包含1至40重量%的以V2O5计算的钒氧化物,60至99重量%的以TiO2计算的二氧化钛,至多1重量%的以Cs计算的铯化合物,至多1重量%的以P计算的磷化合物,和至多10重量%的以Sb2O3计算的锑氧化物。有利地,位于下游的催化剂床包含至少两层催化剂,它们的催化活性组合物具有不同的Cs含量,该Cs含量在气流流动方向上减小。
通过下列实施例和对比例详细举例说明本发明。
实施例
实施例1
在60℃下将102克V2O5(=0.56摩尔)搅拌添加到7升软化水中。将该悬浮液与4.94克CeNO3·6H2O水溶液(=0.011摩尔,Aldrich,纯度99%)混合。在进一步搅拌下将68克AgNO3(=0.398摩尔)在1升水中的水溶液添加到所得橙色悬浮液中。随后,在2小时内将所得悬浮液的温度升至90℃,并将该混合物在此温度下搅拌24小时。随后将所得深褐色悬浮液冷却并喷雾干燥(入口温度(空气)=350℃,出口温度(空气)=110℃)。该粉末的组成为Ce0.02Ag0.71V2Ox。
所得粉末具有61平方米/克的BET比表面积。借助Siemens D 5000衍射仪,使用Cu-Kα辐射(40kV,30mA),记录所得粉末的粉末X-射线图。该衍射仪配有自动主和次孔径系统和次要单色仪和闪烁检测器。根据粉末X-射线图,获得下列晶面间距附带相对强度I相对[%]:15.04(11.9)、11.99(8.5)、10.66(15.1)、5.05(12.5)、4.35(23)、3.85(16.9)、3.41(62.6)、3.09(55.1)、3.02(100)、2.58(23.8)、2.48(27.7)、2.42(25.1)、2.36(34.2)、2.04(26.4)、1.93(33.2)、1.80(35.1)、1.55(37.8)。
将粉末如下施加到硅酸镁环上:将350克外径7毫米、长度3毫米且壁厚度1.5毫米的块滑石环在涂布筒中在20℃下用85克该粉末和8.5克草酸涂布,经20分钟添加50毫升12.5重量%甘油水溶液,然后干燥。在所得预催化剂样品上测得的由此施加的催化活性物质的重量,在450℃下热处理1小时后为最终催化剂总重量的18重量%。碳含量为大约4重量%(基于活性组合物)。
在涂布之后,将预催化剂在强制通风炉中在空气气氛下以0.33℃/分钟的加热速率加热至140℃并在此温度下保持4小时。在此处理后,预催化剂中的碳比例为大约1重量%(基于活性组合物)。然后将预催化剂在旋转球体炉(500毫升球体)中在N2气氛下(1l(STP)N2/h.g活性组合物)以2℃/分钟的加热速率加热至490℃,并在此温度下保持4小时。
在此处理后,活性组合物具有深绿色外观;碳含量为0.007重量%(基于活性组合物)。借助X-射线衍射法,表明其是结晶δ-青铜。BET表面积为3.9平方米/克,平均钒氧化态为4.67。
在将由此制成的催化剂与下游两层具有不同活性的V2O5/TiO2催化剂一起安装到氧化反应器中之后,邻二甲苯向邻苯二甲酸酐的气相氧化可以在大约30克/立方米(STP)空气的初始载量下开始,该载量迅速升至大约80克/立方米(STP)。
为了比较,原位制成的催化剂的拆出样品具有0.005重量%(基于活性组合物)的碳含量。根据X-射线衍射法,拆出的样品为结晶δ-青铜(根据粉末X-射线图,获得下列晶面间距附带相对强度I相对[%]:4.85(9.8)、3.50(14.8)、3.25(39.9)、2.93(100)、2.78(36.2)、2.55(35.3)、2.43(18.6)、1.97(15.2)、1.95(28.1)、1.86(16.5)、1.83(37.5)、1.52(23.5))。BET表面积为6.7平方米/克,平均钒氧化态为4.63。
对比例2
重复实施例1,只是第一处理步骤中的预催化剂在空气下加热仅2小时至100℃。预催化剂中的碳含量为2.6重量%。预催化剂随后在氮气流中在450℃下保持4小时。
所得催化剂是黑色的;在粉末衍射图中,观察到可归因于立方银晶格的单个强峰。没有观察到可归因于δ-青铜的峰。BET表面积为30平方米/克,平均钒氧化态4.1-4.2(催化剂过度还原)。碳含量低于0.02重量%。
对比例3
重复对比例2,只是在空气流中在450℃下进行热处理。
根据X-射线衍射图,所得催化剂的活性组合物包含β-Ag0.33V2O5和Ag1.2V3O8的混合物。平均钒氧化态为4.8。
Claims (12)
1.一种通过在包含少于10体积%氧的气氛中在至少350℃的温度下热处理预催化剂,将包含惰性载体、有机碳源和含银和钒的多金属氧化物的预催化剂转化成包含惰性载体和催化活性银钒氧化物青铜的气相氧化催化剂的方法,其中,在热处理前,将预催化剂中碳源的量调节至低于临界量的值,临界量是指在预催化剂热处理过程中开始还原成元素银时的碳源的量。
2.根据权利要求1的方法,其中热处理在惰性气流中进行。
3.根据权利要求1或2的方法,其中,在热处理前,将预催化剂中碳源的量调节到0.5至低于2重量%的值,所述值按碳计算并基于多金属氧化物的重量。
4.根据权利要求3的方法,其中,在热处理前,将预催化剂中碳源的量调节至低于或等于1.3重量%的值。
5.根据前述权利要求任一项的方法,其中预催化剂最初包含大于临界量或对应于临界量的碳源量,并通过在含氧气氛中在80至200℃的温度下处理预催化剂,通过烧除将碳源的量调节至低于临界量的值。
6.根据权利要求4的方法,其中烧除包括至少一个加热阶段,在此过程中以低于5℃/分钟的速率升高预催化剂温度,以及至少一个平稳阶段,在此过程中将预催化剂温度保持基本恒定。
7.根据前述权利要求任一项的方法,其中烧除在空气流中进行。
8.根据前述权利要求任一项的方法,其中碳源选自(i)具有1至12个碳原子和至少一个选自OH、C=O和NH2的官能团的化合物;和(ii)由具有2至12个碳原子和至少一个选自OH、C=O和NH2的官能团的重复单元形成的聚合化合物。
9.根据权利要求8的方法,其中碳源选自具有2至6个碳原子和至少两个各自独立地选自OH、C=O和NH2的官能团的化合物。
10.根据权利要求8的方法,其中碳源选自乙二醇、丙二醇、丙三醇、季戊四醇、戊糖、己糖、草酸、草酸铵、丙二酸、马来酸、富马酸、琥珀酸、抗坏血酸、苯甲酸、邻-、间-和对-甲苯酸、邻苯二甲酸、邻苯二甲酸酐、间苯二甲酸、对苯二甲酸、二甲基甲酰胺、二甲基乙酰胺、N-甲基吡咯烷酮。
11.根据前述权利要求任一项的方法,其中多金属氧化物具有通式I
Aga-cQbMcV2Od*eH2O I
其中
a为0.3至1.9,
Q为选自P、As、Sb和/或Bi的元素,
b为0至0.3,
M是选自碱金属和碱土金属、Bi、Tl、Cu、Zn、Cd、Pb、Cr、Au、Al、Fe、Co、Ni、Mo、Nb、Ce、W、Mn、Ta、Pd、Pt、Ru和/或Rh的至少一种金属,
c为0至0.5,条件是(a-c)≥0.1,
d为由式I中非氧元素的化合价和出现率确定的数,且
e为0至20。
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DE102005061382.9 | 2005-12-21 | ||
DE102005061382A DE102005061382A1 (de) | 2005-12-21 | 2005-12-21 | Umwandlung eines Präkatalysators in eine katalytisch aktive Silber-Vanadiumoxid-Bronze |
PCT/EP2006/070041 WO2007071749A1 (de) | 2005-12-21 | 2006-12-20 | Umwandlung eines präkatalysators in eine katalytisch aktive silber-vanadiumoxid-bronze |
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EP (1) | EP1968743B1 (zh) |
JP (1) | JP4956548B2 (zh) |
KR (1) | KR20080090440A (zh) |
CN (1) | CN101360561B (zh) |
AT (1) | ATE502696T1 (zh) |
BR (1) | BRPI0620101A2 (zh) |
DE (2) | DE102005061382A1 (zh) |
TW (1) | TW200727984A (zh) |
WO (1) | WO2007071749A1 (zh) |
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BRPI0910954A2 (pt) * | 2008-04-07 | 2016-01-05 | Basf Se | método para iniciar um reator de oxidação em fase gasosa |
EP2379223A2 (de) * | 2008-12-22 | 2011-10-26 | Basf Se | Katalysatorformkörper und verfahren zur herstellung von maleinsäureanhydrid |
TWI491087B (zh) * | 2009-08-26 | 2015-07-01 | Univ Nat Taiwan | 用於有機光電元件之過渡金屬氧化物的懸浮液或溶液、其製作方法與應用 |
DE102012003236A1 (de) | 2012-02-20 | 2013-08-22 | Clariant Produkte (Deutschland) Gmbh | Vorvergoldung von Pd-Au-gecoateten Schalenkatalysatoren |
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DE19851786A1 (de) * | 1998-11-10 | 2000-05-11 | Basf Ag | Silber- und Vanadiumoxid enthaltendes Multimetalloxid und dessen Verwendung |
DE10334132A1 (de) * | 2003-07-25 | 2005-04-07 | Basf Ag | Silber, Vanadium und ein Promotormetall enthaltendes Multimetalloxid und dessen Verwendung |
DE102004014918A1 (de) * | 2004-03-26 | 2005-10-13 | Basf Ag | Katalysator mit einer Silber-Vanadiumoxidphase und einer Promotorphase |
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2005
- 2005-12-21 DE DE102005061382A patent/DE102005061382A1/de not_active Withdrawn
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2006
- 2006-12-20 JP JP2008546459A patent/JP4956548B2/ja not_active Expired - Fee Related
- 2006-12-20 WO PCT/EP2006/070041 patent/WO2007071749A1/de active Application Filing
- 2006-12-20 EP EP06830762A patent/EP1968743B1/de not_active Not-in-force
- 2006-12-20 BR BRPI0620101A patent/BRPI0620101A2/pt not_active IP Right Cessation
- 2006-12-20 US US12/158,858 patent/US20090291845A1/en not_active Abandoned
- 2006-12-20 AT AT06830762T patent/ATE502696T1/de active
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EP1968743B1 (de) | 2011-03-23 |
JP2009520588A (ja) | 2009-05-28 |
DE502006009180D1 (de) | 2011-05-05 |
KR20080090440A (ko) | 2008-10-08 |
JP4956548B2 (ja) | 2012-06-20 |
DE102005061382A1 (de) | 2007-06-28 |
CN101360561B (zh) | 2011-11-09 |
ATE502696T1 (de) | 2011-04-15 |
WO2007071749A1 (de) | 2007-06-28 |
BRPI0620101A2 (pt) | 2016-11-16 |
TW200727984A (en) | 2007-08-01 |
US20090291845A1 (en) | 2009-11-26 |
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