CN101983174A - 一种纳米结晶铋-钼复合氧化物的制备方法 - Google Patents
一种纳米结晶铋-钼复合氧化物的制备方法 Download PDFInfo
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- CN101983174A CN101983174A CN200980111800.8A CN200980111800A CN101983174A CN 101983174 A CN101983174 A CN 101983174A CN 200980111800 A CN200980111800 A CN 200980111800A CN 101983174 A CN101983174 A CN 101983174A
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- bismuth
- composite oxides
- molybdenum
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Abstract
本发明涉及一种纳米结晶铋-钼复合氧化物的制备方法,该铋-钼复合氧化物作为催化剂催化化学转化反应的用途,特别是丙烯转化为丙烯醛和/或丙烯酸或者异丁烯转化为异丁烯酸和/或甲基丙烯酸的转化反应,以及含有该铋-钼复合氧化物的催化剂。
Description
技术领域
本专利涉及一种纳米结晶铋-钼复合氧化物的制备方法,该铋-钼复合氧化物作为催化剂催化化学转化反应的用途,以及含有该铋-钼复合氧化物的催化剂。
背景技术
截至目前,现有技术中采用沉积法、溶胶-凝胶法以及固态反应法制备铋-钼复合氧化物。
美国专利(US 2007/0238904 A1)中公开了一种经沉积后煅烧的方法制备而成的铋-钼复合氧化物。该铋-钼复合氧化物可催化丙烯或者异丁烯转化为相应的丙烯醛或异丁烯醛。
WO 2008/028681以及德国专利(DE 10 2006 032 452 A1)公开了一种纳米结晶的金属氧化物或者复合金属氧化物的制备方法。在这些文献中,没有给出专门的纳米结晶铋-钼复合氧化物的制备方法,而该纳米结晶铋-钼复合氧化物特别适合作为像丙烯转化成丙烯醛这类化学反应的催化剂。
只采用常规方法制备结晶钼复合氧化物,以及因此得到的铋-钼复合氧化物是非常困难的。因此,G.A.Zenkovets等公开了“一种复杂的(MoVW)5O14氧化物在热处理过程中的结构性成因及其在高温下的氧化还原行为”。《材料化学与材料物理学》(103(2007),295-304)公开了通过沉积法和喷雾干燥法制备的钼复合氧化物具有无定形结构。这种复合氧化物以大约5μm大聚合体的形式出现。由于后续的煅烧,在聚合体内部存在部分的纳米结晶结构。只有经约440℃的高温长时间处理后,方可形成粒度大于1000nm的纯结晶相。因此,制备纳米结晶的钼复合氧化物非常困难,特别是制备小微晶。
因此,现有技术中铅-钼复合氧化物的不足之处在于,不能获得粒径均一的钼复合氧化物,控制结晶,特别是控制微晶尺寸是不可能的。同样地,现有技术中钼复合氧化物的BET比表面积大多非常小。理想的催化剂是粒径小同时BET比表面积尽量大。
发明内容
鉴于此,本发明目的在于提供一种纳米结晶铋-钼复合氧化物的制备方法,所述纳米结晶铋-钼复合氧化物用于催化转化反应,其对于理想终产物具有更高的催化活性和选择性。
本发明一种纳米结晶铋-钼复合氧化物的制备方法,包括下述步骤:
a)采用载液法,将含钼起始化合物和铋起始化合物的溶液、混悬液或者浆液导入反应室中;
b)采用200~700℃温度下脉动流加热的方法,在处理区对于含钼起始化合物和含铋起始化合物的溶液、混悬液或者浆液进行热处理;
c)形成纳米结晶铋-钼复合氧化物;
d)从反应器中卸出步骤b和步骤c中得到的纳米结晶铋-钼复合氧化物。
令人惊奇的是,按照本发明方法以及结晶控制获得的纳米结晶铋-钼复合氧化物具有均一的粒径,特别是微晶尺寸。与现有技术相比,本法获得的纳米结晶铋-钼复合氧化物的BET比表面积也同样能够增加。
按照本发明方法获得的纳米结晶铋-钼复合氧化物,其特征在于微晶尺寸为10nm~1000nm,特别为10nm~750nm,优选为10nm~500nm,更优选为10nm~300nm,进一步优选为10nm~100nm,特别为10nm~30nm。
与常规方法制备的铋-钼复合氧化物相比,含有依本发明制备的铋-钼复合氧化物的催化剂,其催化活度,特别是在丙烯向丙烯醛转化的反应中,能够增加10%。
通过采用根据本发明的方法制备的催化剂,其(催化)活度和选择性增加,与现有技术相比,由丙烯制备丙烯醛将显著提高。由异丁烯转化为异丁烯醛或其他类似化合物也是可以采用该催化剂。特别是,该催化剂在丙烯或异丁烯直接转化为丙烯酸或甲基丙烯酸中表现出良好的活度。优选地,按照本发明的方法转化反应采用一步反应完成。
优选地,所述钼起始化合物为钼酸盐,特别优选为四水合七钼酸铵盐。但是,对于本领域技术人员来说,现有技术中其他钼酸盐或钼化合物也可以作为钼起始化合物使用。
优选地,所述铋起始化合物为铋盐,如氯化铋、硫酸铋、醋酸铋、氧化铋,特别优选为硝酸铋。
优选地,所述钼起始化合物和铋起始化合物以溶液、混悬液或浆液的形式一起使用。最优选地,起始化合物以溶液的形式使用。为了获得最佳的溶液,特别是如遇起始化合物为难溶性化合物时,溶液需要加热,例如加热50℃以上。
特别优选地,进一步含有金属的起始化合物能够与钼起始化合物和铋起始化合物在溶液、混悬液或浆液中一起。就此而论,优选镍、铁和/锌金属化合物。钴和锰也是优选的金属。这些金属优选使用金属盐,特别是氧化物、卤化物、硫酸盐、硝酸盐或醋酸盐。
进一步优选地,还可以使用金属化合物或非金属化合物,它们选自锂、钠、钾、铷、铯、镁、钙、钡、锶、铈、锰、铬、矾、铌、硒、碲、钐、钆、镧、钇、钯、铂、钌、银、金、硅、铝、铊、锆、钨和/或磷。
令人惊奇的是,本发明方法可以在200~700℃相对低温的条件下进行,优选200~500℃,特别优选250~450℃,特别优选300~400℃。截至目前,现有技术中大于700℃的优选温度却已达到1400℃。特别令人惊奇的是,按照本发明的方法可以针对目标控制所述铋-钼复合氧化物的结晶过程,特别是针对微晶尺寸以及相应铋-钼复合氧化物的孔径分布等方面。同时,火焰中的停留时间或者反应器温度对其也有很好的作用。这样形成的纳米结晶铋-钼复合氧化物粒子可以防止因脉冲热处理引发的聚集。具有代表性的是,纳米结晶粒子会随着热气流的作用迅速地转移到低温区域,在此就会形成一些粒径小于20nm的铋-钼复合氧化物微晶。
因此得到的铋-钼复合氧化物的微晶,其BET比表面积明显提高,大于1m2/g,特别优选2~50m2/g,尤其优选5~35m2/g。按照DIN66131和66132(使用Brunauer,Emmett and Teller法)测定BET比表面积。
按照本发明的方法,混悬液可在短时间内被煅烧,典型地在几毫秒之内,温度与现有技术中通常使用的方法相比也相对较低,并且没有额外的过滤和/或干燥的步骤,或者不需要额外加入溶剂。形成的铋-钼复合氧化物的纳米微晶,其BET比表面积显著增加。因此,在本发明进一步的实施例中提供了含有本发明铋-钼复合氧化物的催化剂(催化剂)具有高反应性,高转化率和高选择性,特别对于丙烯转化为丙烯醛和/或丙烯酸或异丁烯转化为异丁烯酸和/或甲基丙烯酸的反应中。
在创建的稳态温度场中,每一个铋-钼复合氧化物粒子的停留时间几乎一样。这样使得终产物非常均匀,粒度分布较窄。按照本发明方法生产这种单质纳米结晶金属氧化物粉末的设备是已知的,例如德国专利(DE 101 09 892 A1)。然而与之描述的设备和方法不同,本发明方法不需要上游蒸发的步骤,也就是起始化合物,如钼起始化合物,加热到蒸发温度。
钼起始化合物,铋起始化合物以及其他按照本发明方法用于制备铋-钼复合氧化物的起始化合物直接通过载液,特别是载气,优选惰性载气如氮气等,加入所谓的反应室中如燃烧室中。反应室附加的放液侧为谐振管,其流道截面与反应室相比明显降低。燃烧室底部安装有若干燃烧空气进入燃烧室的阀门。空气动力学阀门在流体学和声学上与燃烧室以及谐振管几何相配,以至于燃烧室中产生的稳态“无焰”温度场的压力波主要在谐振管中脉冲式传播。形成所谓带有脉冲流的“亥姆霍兹共振器”,脉冲频率3~150Hz,优选为5~110Hz。
典型地,物料可以使用注射器,或者适合的二组分喷嘴、三组分喷嘴或Schenk加气机。
优选地,钼起始化合物,铋起始化合物以及其他起始化合物以雾化的形式导入反应室中,确保了在处理区域中的精密分布。
高温处理后,采用载液的方法(如果可能的话)将形成的纳米结晶铋-钼复合氧化物立即转移至反应室的更低温区,结果其可在更低温区分离、卸载。所有形成的产品都被卸载出反应器,因此本发明方法收率几乎接近100%。
典型地,本发明方法在常压至40bar的范围内均可以实施。
此外,本发明目的在于提供一种按照本发明方法制备获得纳米结晶铋-钼复合氧化物。因此获得的纳米结晶铋-钼复合氧化物,其微晶尺寸为5~1000nm,优选10~800nm,特别优选15~550nm。如前所述,优选热处理脉冲得到这样的微晶尺寸。本领域技术人员已知的方法测定粒径大小,例如X射线衍射(XRD)或者透射电镜(TEM)。
此外,按照本发明方法制备的铋-钼氧化粒子,其BET比表面积优选大于1m2/g,特别优选为2~50m2/g,尤其优选5~35m2/g。
优选地,本发明铋-钼复合氧化物以下列通式表示:MoaBib(CoNi)cFedKOx。该通式给出了具有活性的催化成分,不包括载体。所述铋-钼复合氧化物特别优选通式为MoBiOx。进一步的包含其他元素的铋-钼复合氧化物的通式为:MoaBib(CoNi)cFedMneKfPgAlhSiiSmjOx,其中,优选地,a=10~13,b=1~2,c=7~9,d=1.5~2.3,e=0.05~0.3,f=0.02~0.1,g=0.01~0.1,h=270~280,i=0.4~0.9,j=0.05~0.15和x≥2。在此通式中,特别优选的合成物以下述通式表示如下:Mo12Bi1.5(CoNi)8.0Fe1.8Mn0.1K0.06P0.04Al275Si0.66Sm0.1Ox。
优选地,根据本发明方法,铋-钼复合氧化物适合于制备本发明催化剂中具有催化活性的成分,例如这样的催化剂是指丙烯转化为丙烯醛和/或丙烯酸或异丁烯转化成异丁烯醛和/或甲基丙烯酸的反应中的催化剂。特别地,本发明催化剂也适合直接催化丙烯或异丁烯转化成丙烯酸或甲基丙烯酸,其中与现有技术相比,这样的转化具有一步反应的优势。
工业上,丙烯醛是用于制备丙烯酸的起始原料。现有技术中,大规模产业化生产通常是在催化剂的作用下经过丙烯的两步氧化而成。第一步,丙烯经氧化转化为丙烯醛;第二步,丙烯醛氧化成丙烯酸。丙烯酸主要用于高吸水性聚合物(例如尿布)的聚合,丙烯酸酯(用于生产聚合物)以及作为共聚单体在制备聚合物分散体中的应用。水溶性丙烯酸的聚合产物可作为光洁剂,增稠剂和包衣剂用于固体制剂,以及用于软膏基质。已经证明,聚丙烯酸乙酯参与制备具有抗风化的弹性体的共聚反应。
令人惊奇的是,根据本发明方法,在所述铋-钼复合氧化物催化剂的催化下,可通过一步反应由丙烯合成丙烯醛和/或丙烯酸,或者由异丁烯合成异丁烯醛和/或甲基丙烯酸。
因此,本发明目的还在于,按照本发明提供一种含有铋-钼复合氧化物的催化剂。所述催化剂可以是负载型催化剂或者非负载型催化剂。
所述铋-钼复合氧化物可以与适合的粘合剂一起加工成一定形状的挤出物(片、一定形状体、蜂窝状体等等)。本领域技术人员熟悉的任何粘合剂均适合上述的任务,特别是硅酸盐材料、氧化铝、锆化合物、氧化钛,及其混合物。其他材料,例如水泥、黏土、硅石/矾土等也可以作为粘合剂使用。其中,优选的粘合剂为拟薄水铝石,以及硅酸粘合剂,例如胶状氧化硅或硅溶胶。
此外,所述铋-钼复合氧化物可以与其它组分一起加工成涂层,优选为粘合剂,特别优选为有机粘合剂,例如有机胶、高分子材料、树脂或蜂蜡,这涂层可以应用于金属或陶瓷的载体上。选择性地,还可以有浸渍或者煅烧等步骤。
优选地,本发明铋-钼复合氧化物可以涂布在载体上。优选的载体材料为滑石,特别优选为滑石球。优选所谓的流化床装置进行包衣。
本发明目的在于提供一种由丙烯转化为丙烯醛和/或丙烯酸,或者由异丁烯转化成异丁烯醛和/或甲基丙烯酸的方法。其中,使用了如前所述的本发明的催化剂。
该方法优选为一步反应。该方法包括300~600℃温度下将丙烯或异丙烯、氧气和氮气的混合物通过催化剂床。所述催化剂床可以是填充床或者流化床。
附图说明
下述通过具体实施例和附图对于本发明进行详细地描述,并不构成对于本发明的限定。使用的设备与德国专利(DE 101 09 892 A1)中描述的设备相近,所不同之处在于本发明方法的设备没有预蒸发阶段。
图1为按照实施例2中混悬液的粒径分布。
图2为450℃条件下本发明方法制备的铋-钼复合氧化物的X射线衍射图谱。
图3为按照实施例3中混悬液的粒径分布。
图4为500℃条件下本发明方法制备的铋-钼复合氧化物的X射线衍射图谱。
图5为按照实施例4中混悬液的粒径分布。
图6为按照实施例5中混悬液的粒径分布。
图7为600℃条件下本发明方法制备的铋-钼复合氧化物的X射线衍射图谱。
具体实施方式
概述
采用脉冲反应器制备的重要优势在于缩短了整体的制备时间,降低了成本(只需要反应器),以及不需要干燥和处理产品。使用脉冲反应器的一步反应中很多因素均会发生变化,包括理想的BET比表面积、粒径,以及物料的结晶性。
实施例1、对比例(按照德国专利DE 10 2006 015710 A1)
取铁、钴、镍、镁、钾的硝酸盐,按照质量比23.2∶47.26∶29.28∶0.0646∶0.2067溶解在3.5L水中,加热至40℃同时搅拌并加入0.1molSm3+的硝酸溶液和2molHNO3,得溶液Ⅰ。
取2118.6g的七钼酸铵在40℃温度下溶解在2.7L水中。4.4g磷酸和0.428g氧相二氧化硅200(Degussa)和14g氧化铝溶解在1L水中,将其加入前述溶液中,得溶液Ⅱ。
将溶液Ⅱ缓缓加入溶液Ⅰ中,边加入边剧烈搅拌。在另外的容器中,制备含有790g硝酸钼和0.72molHNO3的溶液Ⅲ。将此溶液加入到其它活性组分中制备活性催化相的共聚物。
剧烈搅拌共聚物12小时。得到的混悬液使用旋转盘喷雾干燥,进气温度为350℃。设定空气的量,使得出口温度保持在100±10℃。
因此得到的产品粉末的平均粒径为55μm。粉末在445℃对流烤箱中处理1小时,直到形成复合氧化物,并在接下来的步骤中进行粉碎成平均粒径为1μm。作为水溶液,该复合氧化物经双组分喷嘴喷雾到陶瓷的球形催化剂载体上,60℃流动空气干燥。球形小粒在滚筒中循环以均质化。得到的产品加热至540℃,持续1小时以固化涂敷的活性物质。
因此得到的催化剂具体成分为:Mo12Bi1.5(Co+Ni)8.0Fe1.8Mn0.1K0.06P0.04Al275Si0.66Sm0.1)OX。
催化剂的试验:
实施例1中催化剂采用7.5vol%丙烯(化学纯),58vol%空气和惰性气体(总体为100vol%)的混合物进行包衣。总气流为36.9L/min。热载体温度为365℃。丙烯转化率为89.5mol%,对于丙烯醛和丙烯酸的选择性为95.3%(见实施例7,表1)。
实施例2(本专利)
取60L软化水置于100L容器中,加热至50℃。下列物质顺序加入软化水中:
物质 | 量[g] | 加入后溶液的颜色 |
硝酸镍溶液(Ni:12%) | 6599.25 | 绿色 |
混悬液搅拌加热至75℃。冷却至64℃后加入3290g硅溶胶(Ludox AS40)。然后,62℃下加入硝酸铋溶液(2.5L 10%硝酸+991.04g硝酸铋x5H2O)。混悬液温度为58℃,搅拌10分钟。
测定混悬液粒径分布,结果见图1。
混悬液20kg/h的速率注入脉冲反应器中,温度为450℃。样品X射线衍射图谱结果如下:
作为催化剂,450℃脉冲反应器中得到的物质的BET比表面积为23m2/g,其特征在于XRD见图2。
可以从XRD衍射图谱上看出硝酸盐前体物质的分解,以及金属钼酸盐阶段的形成,例如铋的钼酸盐。
对于下述包衣试验,在脉冲反应室中,450℃下制备1.45kg雾化的物质。
实施例3(本专利)
取60L软化水置于100L容器中,加热至50℃。下列物质顺序加入软化水中:
物质 | 量[g] | 加入后溶液的颜色 |
硝酸镍溶液(Ni:12%) | 6599.25 | 绿色 |
硝酸铁x9H2O | 1664.68 | 绿色 |
硝酸锌x6H2O | 1202.67 | 绿色 |
七钼酸铵x4H2O | 4344.48 | 黄绿色 |
混悬液搅拌加热至75℃。冷却至64℃后加入3290g硅溶胶(Ludox AS40)。然后,62℃下加入硝酸铋溶液(2.5L 10%硝酸+991.04g硝酸铋x5H2O)。混悬液温度为58℃,搅拌10分钟。
测定混悬液粒径分布,结果见图3。
混悬液20kg/h的速率注入脉冲反应器中。
在脉冲反应器中,得到的物质在500℃雾化,样品XRD衍射图谱如下:
在脉冲反应器中500℃得到的物质,其BET比表面积为21m2/g,其特征衍射谱图见图4。
可以从XRD衍射图谱上看出硝酸盐前体物质的分解,以及金属钼酸盐阶段的形成,例如铋的钼酸盐。由于缺乏铋,因此检测的催化剂的主要部分全部由铁的钼酸盐组成。
对于下述包衣试验,在脉冲反应室中,500℃下制备1.45kg雾化的物质。
实施例4(本专利)
取60L软化水置于100L容器中,加热至50℃。下列物质顺序加入软化水中:
物质 | 量[g] | 加入后溶液的颜色 |
硝酸镍溶液(Ni:12%) | 6599.25 | 绿色 |
硝酸铁x9H2O | 1664.68 | 绿色 |
硝酸锌x6H2O | 1202.67 | 绿色 |
七钼酸铵x4H2O | 4344.48 | 黄绿色 |
混悬液搅拌加热至75℃。冷却至64℃后加入3290g硅溶胶(Ludox AS40)。然后,62℃下加入硝酸铋溶液(2.5L 10%硝酸+991.04g硝酸铋x5H2O)。混悬液温度为58℃,搅拌10分钟。
测定混悬液粒径分布,结果见图5。
混悬液20kg/h的速率注入脉冲反应器中。得到的物料在600℃温度下在脉冲反应器中进行雾化。
在脉冲反应器中600℃得到的物质,其BET比表面积为18m2/g,其特征衍射谱图见图7。可以从XRD衍射图谱上看出硝酸盐前体物质的分解,以及BiMoO4相的形成。对于下述包衣试验,在脉冲反应室中,600℃下制备1.45kg雾化的物质。
实施例5(本专利)
1#溶液:取40L软化水置于100L容器中,加热至55℃。下列物质顺序加入软化水中:
物质 | 量[g] | 温度[℃] | pH值 | 加入后溶液的颜色 |
硝酸铁x9H2O | 587.12 | 55 | 2.73 | 橙色 |
硝酸镍溶液(Ni:12%) | 7108.15 | 50 | 1.92 | 绿色 |
硝酸钴x6H2O | 563.93 | 50 | 1.84 | 绿色 |
硝酸钾 | 12.24 | 50/30** | 1.84 | 绿色 |
硅溶胶(LUDOX AS40) | 3638.04g | 28** | 1.92 | 深绿色 |
2#溶液:取20L软化水导入100L金属滚筒中,加热至57℃(pH值:5.00)。下列物质顺序加入软化水中:
物质 | 量[g] | 温度[℃] | pH值 | 加入后溶液的颜色 |
仲钼酸铵x4H2O | 5131.56 | 50 | 5.46 | 无色/微绿色 |
磷酸 | 280.09 | 50 | 5.42 | 浅绿色 |
3#溶液:量取2115.4L软化水(20℃)置于10L容器中。
物质 | 量[g] | 温度[℃] | pH值 | 加入后溶液的颜色 |
硝酸(65%) | 384.6 | 28 | --- | 无色 |
硝酸铋x5H2O | 1174.90g | 25 | --- | 无色 |
1#溶液与2#溶液剧烈搅拌混合(温度:34℃;pH值:4.76),之后,混合溶液呈现为浅绿色混悬液。接着,加入3#溶液(温度:34℃;pH值:2.02)。搅拌混悬液(赭石色/黄色)1小时,随即观察到形成了轻微的气体。
测定混悬液的粒径分布,结果见图6。
混悬液20kg/h的速率注入脉冲反应器中。
在上述参数条件下,温度600℃,将混悬液注入。在XRD衍射图谱上清楚看到形成BiMoO4相,其中衍射谱图与实施例4和附图7中的谱图基本一致,因此不在此展示。
脉冲反应器中600℃温度下雾化得到的2.06kg粉末,以及脉冲反应器中400℃温度下雾化得到的1.07kg粉末,可用于包衣试验。
实施例6(制备包衣的催化剂)
采用流化床包衣设备进行包衣。
将在实施例1~4中制备的铋-钼复合氧化物的活性物料包衣在滑石小球上。按照下述条件进行:
称量22.22g物料至量筒中,加入500ml蒸馏水制成浆液。形成的混悬液剧烈搅拌后,加入8.89g粘合剂,形成的混合物在磁力搅拌器上搅拌1小时。
称取80g的滑石小球(2~4mm),在其表面用得到的混悬液进行包衣,其中活性成分的负载为20%(是指每200g滑石小球上包衣50g粉末)。得到的催化剂在110℃空气中干燥。
实施例7(催化剂催化性能测定)
21g催化剂采用350g滑石小球(直径4.5mm)稀释以免局部过热,然后倒入120cm长的反应管(内径为24.8mm的)中,约105cm高。反应管置于液态的盐浴上,该盐浴可以加热到500℃以上。催化剂床上,安装有一个带有集成式热电偶的保险管(3mm),通过它可以显示催化温度是否高出完全的催化组合。为了测定催化性能数据,7.5vol%的丙烯,58vol%空气和氮气(加至100vol%)以最多4500Nl/h速率通过催化剂。在365℃平均催化温度下,设定丙烯转化率丙烯醛的选择性,待反应气体离开反应管以后测定其中的成分。实施例1~4中制备的物料作为催化剂(按照实施例6方法制备)的结果见表1。
表1、本发明催化性能数据及其与对比例的比较
如表1所示,与现有技术方法制备的铋-钼复合活性催化剂(对比例,实施例1)相比,本发明催化剂具有收率高,丙烯醛选择性高等优点。
Claims (18)
1.一种纳米结晶铋-钼复合氧化物的制备方法,包括下述步骤:
a)采用载液法,将含钼起始化合物和铋起始化合物的溶液、混悬液或者浆液导入反应室中;
b)采用200~700℃温度下脉动流加热的方法,在处理区对于含钼起始化合物和含铋起始化合物的溶液、混悬液或者浆液进行热处理;
c)形成纳米结晶铋-钼复合氧化物;
d)从反应器中卸出步骤b和步骤c中得到的纳米结晶铋-钼复合氧化物。
2.如权利要求1所述的方法,其特征在于所述钼起始化合物为七钼酸铵四水合物。
3.如权利要求1或2所述的方法,其特征在于所述铋起始化合物为硝酸铋。
4.还有含有金属的起始化合物选自镍、铁、钴、镁和/锌起始化合物,以溶液、混悬液或浆液的形式使用。
5.如权利要求4所述的方法,其特征在于含有金属的起始化合物选自镍、铁和/或锌起始化合物。
6.如权利要求1~5所述的任一方法,其特征在于载液是气体。
7.按照权利要求1~6任一方法制备的纳米结晶铋-钼复合氧化物。
8.如权利要求7所述的纳米结晶铋-钼复合氧化物,其特征在于其微晶尺寸为10nm~1000nm。
9.如权利要求7或8所述的纳米结晶铋-钼复合氧化物,其特征在于其BET比表面积为1~50m2/g。
10.权利要求7~9任一方法制备的纳米结晶铋-钼复合氧化物在化学转化中作为催化剂的用途。
11.权利要求10所述的用途,其特征在于所述化学转化为丙烯转化为丙烯醛和/或丙烯酸,或者异丁烯转化为异丁烯酸和/或甲基丙烯酸。
12.权利要求11所述的用途,其特征在于所述丙烯转化为丙烯醛和/或丙烯酸或者异丁烯转化为异丁烯酸和/或甲基丙烯酸的转化反应为一步反应。
13.含有权利要求7~9任一纳米结晶铋-钼复合氧化物的催化剂。
14.如权利要求13所述的催化剂,其特征在于钼复合氧化物包衣在载体上。
15.如权利要求13或14所述的催化剂,其特征在于其含有粘合剂。
16.使用权利要求13~15任一催化剂催化丙烯转化为丙烯醛和/或丙烯酸或者异丁烯转化为异丁烯酸和/或甲基丙烯酸的转化反应的方法。
17.如权利要求16所述的方法,该方法为一步反应。
18.如权利要求15或16任一方法,其特征在于丙烯、异丁烯、氧气和氮气混合物在300~600℃条件下通过催化剂床。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102008017308.8 | 2008-04-04 | ||
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PCT/EP2009/002475 WO2009121625A1 (de) | 2008-04-04 | 2009-04-03 | Verfahren zur herstellung von nanokristallinem bismut-molybdänmischoxid |
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CN (1) | CN101983174A (zh) |
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DE (1) | DE102008017308B4 (zh) |
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2008
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2009
- 2009-04-03 WO PCT/EP2009/002475 patent/WO2009121625A1/de active Application Filing
- 2009-04-03 EP EP09727738.8A patent/EP2260004B1/de not_active Not-in-force
- 2009-04-03 CN CN200980111800.8A patent/CN101983174A/zh active Pending
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- 2009-04-03 KR KR1020107024681A patent/KR101291757B1/ko active IP Right Grant
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
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CN105492117A (zh) * | 2013-03-20 | 2016-04-13 | 克拉里安特国际有限公司 | 包含铋-钼-镍混合氧化物或铋-钼-钴混合氧化物和SiO2的复合材料 |
CN105492117B (zh) * | 2013-03-20 | 2019-03-08 | 克拉里安特国际有限公司 | 包含铋-钼-镍混合氧化物或铋-钼-钴混合氧化物和SiO2的复合材料 |
CN113019442A (zh) * | 2019-12-09 | 2021-06-25 | 中国科学院大连化学物理研究所 | 一种担载型丙烯氧化制丙烯酸催化剂及其制备和应用 |
CN113019442B (zh) * | 2019-12-09 | 2022-05-17 | 中国科学院大连化学物理研究所 | 一种担载型丙烯氧化制丙烯酸催化剂及其制备和应用 |
Also Published As
Publication number | Publication date |
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KR20100134091A (ko) | 2010-12-22 |
DE102008017308B4 (de) | 2014-09-25 |
WO2009121625A1 (de) | 2009-10-08 |
DE102008017308A1 (de) | 2009-10-08 |
US20110092734A1 (en) | 2011-04-21 |
EP2260004B1 (de) | 2018-06-27 |
US8480998B2 (en) | 2013-07-09 |
JP2011516377A (ja) | 2011-05-26 |
KR101291757B1 (ko) | 2013-07-31 |
EP2260004A1 (de) | 2010-12-15 |
JP5458088B2 (ja) | 2014-04-02 |
BRPI0910602A2 (pt) | 2015-09-22 |
ZA201006739B (en) | 2011-09-28 |
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