CN102711986A - 通过在纳米结构化的钌载体催化剂上气相氧化来制备氯的方法 - Google Patents
通过在纳米结构化的钌载体催化剂上气相氧化来制备氯的方法 Download PDFInfo
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- CN102711986A CN102711986A CN2010800325889A CN201080032588A CN102711986A CN 102711986 A CN102711986 A CN 102711986A CN 2010800325889 A CN2010800325889 A CN 2010800325889A CN 201080032588 A CN201080032588 A CN 201080032588A CN 102711986 A CN102711986 A CN 102711986A
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Abstract
本发明涉及通过用基于钌的负载催化剂气相氧化制备氯的方法,其特征在于该催化剂载体具有大量孔直径>50nm的孔,并且带有含有钌和/或钌化合物的纳米颗粒作为催化活性成分。
Description
本发明涉及用基于钌的负载催化剂,通过气相氧化来制备氯的方法,其特征在于该催化剂载体具有大量孔直径>50nm的孔,并且载有含有钌和/或钌化合物的纳米颗粒作为催化活性成分。
由迪肯在1868年开发的在放热平衡反应中催化用氧气氧化氯化氢的方法是氯化学工业的开端:
4 HCl + O2 → 2 Cl2 + 2 H2O。
但是,迪肯制氯法被氯碱电解强烈排挤而退居次要的地位。几乎全部氯的生产都是通过氯化钠水溶液电解来进行[Ullmann Encyclopedia of Industrial Chemistry,第7版,2006]。但是,迪肯制氯法的吸引力近年来再次增加,因为世界范围内的氯需求的增长快于对氢氧化钠水溶液的需求。通过氧化氯化氢来制备氯的方法(其与氢氧化钠水溶液的制备无关)迎合了这种发展。此外,氯化氢在例如光气化反应中,例如在异氰酸酯制备中,作为副产品大量形成。
氯化氢氧化为氯是一个平衡反应。随温度升高,平衡位置向不利于期望的最终产物的方向移动。所以有利的是使用具有尽可能高活性的催化剂,其允许反应在较低的温度进行。
用于氯化氢氧化的最早的催化剂包含氯化铜或者氧化铜作为活性成分,并且由迪肯早在1868年已经进行了描述。但是,它们在低温(<400℃)仅表现出轻微的活性。虽然该活性可以通过提高反应温度来提高,但不利的是,该活性成分在较高温度时的挥发性导致催化活性的快速降低和活性成分从反应器中排出。
EP0184413描述了使用基于氧化铬的催化剂来氧化氯化氢。但是,以此实现的方法由于催化剂活性不足和高反应温度需要大的催化剂负载量。
最早的用于氯化氢氧化的具有催化活性成分钌的催化剂在1965年就已经描述于DE1567788中;在这种情况中,从负载在例如二氧化硅或者氧化铝上的RuCl3出发。但是,这些RuCl3/SiO2催化剂的活性非常低。在DE-A19748299中要求保护了另外的Ru基催化剂,其具有活性成分氧化钌或者钌混合氧化物和作为载体材料的不同的氧化物,例如二氧化钛,二氧化锆等。其中氧化钌的含量是0.1质量%-20质量%,并且氧化钌的平均颗粒直径是1.0nm-10.0nm。另外的负载在二氧化钛或者二氧化锆上的Ru催化剂由DE-A19734412已知。一系列Ru起始化合物,例如钌-羰基络合物,无机酸的钌盐,钌-亚硝酰基络合物,钌-胺络合物,有机胺的钌络合物,或者钌-乙酰丙酮化物络合物被提到用于制备这里描述的包含至少一种化合物二氧化钛和二氧化锆的氯化钌和氧化钌催化剂。在一种优选的实施方案中,将金红石形式的TiO2用作载体。
DE102007020154A1和DE102006024543A1描述了一种催化氯化氢氧化的方法,其中该催化剂包含二氧化锡(作为载体),优选锡石结构的二氧化锡,和至少一种含卤素的钌化合物(DE102007020154A1)或者至少一种含氧的钌化合物(DE102006024543A1)。
迄今为止开发的用于迪肯制氯法的无钌催化剂或者过于没有活性或者过于不稳定。虽然迄今所述的钌载体催化剂原则上适用于迪肯制氯法,但是优先要求保护的载体金红石二氧化钛和锡石-二氧化锡由于它们的晶体结构仅具有小的表面积,这对于将它们用作HCl氧化中的载体来说是不利的。
因此,本发明的目的是提供一种用于氧化氯化氢的催化剂体系,其提供了比现有技术已知的催化剂更高的比活度(基于钌含量)。
令人惊讶地已经发现,比活度(即基于钌)和(高温)稳定性可以通过有针对性地制备纳米结构化的催化剂来明显提高。
本发明涉及催化剂材料,其用于通过基于钌基的负载催化剂,由含氯化氢和氧气的气体来热催化制备氯,其特征在于,该催化剂载体具有大量孔直径>50nm的孔,并且载有含有钌和/或钌化合物的纳米颗粒作为催化活性成分。由含氯化氢和氧气的气体热催化制备氯以下通常简称为迪肯制氯法。
优选根据本发明的催化剂材料至少50%,特别优选至少80%的孔体积存在于直径列入大孔范围(即>50nm)的孔中。这种大孔性使得催化剂载体均匀负载有纳米颗粒成为可能,防止孔由于纳米颗粒团聚而堵塞,并在迪肯反应过程期间减少孔扩散限制。
为了测量孔体积和孔直径,在本发明的范围内使用水银孔率计。这里在测量时基于130°的汞接触角和480 dyn/cm2的表面张力。
该催化剂材料优选包含选自下面的一种或多种化合物作为载体材料:铝化合物,硅化合物,钛化合物,锆化合物或者锡化合物,特别优选铝化合物和/或硅化合物,和最特别优选选自铝,硅,钛,锆或者锡的一种或多种金属的氧化物,氧化物混合物(gemischte Oxide)或者混合氧化物(Mischoxide)。铝和硅的混合氧化物是特别优选的。在一种可能的应用形式中,加入了粘合剂例如μ-Al2O3,其首要功能不是活性成分的载体。
存在于催化剂材料上的含钌纳米颗粒优选包含作为催化活性成分的选自下面的一种或多种化合物:钌氧化物,钌混合氧化物,氧化钌混合物,卤氧化钌,卤化钌或者金属钌。氯化钌,氧氯化钌,或者氧化钌和氯化钌的混合物是特别优选的。
优选至少50%存在于该催化剂上的含钌纳米颗粒具有最大50nm的直径,特别优选至少50%具有5nm-50nm的直径,最特别优选至少80%具有5nm-50nm的直径。存在于该催化剂上的含钌纳米颗粒的平均直径最特别优选10-30nm。令人惊讶的是寻求钌的最大分散(即,钌一次颗粒尽可能小,例如低于5nm)不是有利的。
基于该催化剂的总质量,优选该催化剂的钌含量为至多20重量%,优选0.1-20重量%,特别优选0.5-5重量%。过高的负载量也许导致不利的纳米颗粒的团聚。
具有另外的活性成分功能或者作为促进剂的另外的纳米颗粒优选存在于该催化剂材料上,特别优选元素Ag,Au,Bi,Ce,Co,Cr,Cu,Ni,Sb,Sn,Ti,W,Y,Zn,Zr和铂金属,最特别优元素Bi,Sb,Sn和Ti的一种或多种另外的金属、金属化合物和混合化合物。存在于该催化剂上的这些另外的纳米颗粒优选包含氧化物,混合氧化物,氧化物混合物,卤氧化物,卤化物,还原的金属或者其合金。
存在于该催化剂材料上的另外的纳米颗粒的质量份额,基于该催化剂的总质量,优选为至多20质量%,特别优选至多10质量%。过高的负载量也许导致不利的纳米颗粒团聚。
优选存在于该催化剂上的至少50%的另外的纳米颗粒具有最大50nm的直径,特别优选至少50%具有3nm-50nm的直径,最特别优选至少80%具有3nm-50nm的直径。存在于该催化剂上的另外的纳米颗粒的平均直径最特别优选是5-30nm。
在一种可能的优选实施方案中,在催化剂上存在纳米颗粒,所述纳米颗粒至少包含钌和作为促进剂的至少一种另外的金属,优选Ag,Au,Bi,Ce,Co,Cr,Cu,Ni,Sb,Sn,Ti,W,Y,Zn,Zr和铂金属,最特别优选Bi,Sb,Sn和Ti,即,它们可以称作双金属或者多金属的。这样表征的纳米颗粒包含氧化物、混合氧化物、氧化物混合物、卤氧化物、卤化物、金属和合金。
优选存在于该催化剂上的至少50%的双金属或者多金属纳米颗粒具有最大50nm的直径,特别优选至少50%具有5nm-50nm的直径,最特别优选至少80%具有5nm-50nm的直径。存在于该催化剂上的双金属或者多金属纳米颗粒的平均直径最特别优选是10-30nm。
存在于该催化剂上的双金属或者多金属纳米颗粒的质量份额,基于该催化剂的总质量,优选为至多30重量%,特别优选至多20重量%。过高的负载量会导致不利的纳米颗粒团聚。
该纳米颗粒优选通过火焰热解(Flammenpyrolyse)来制备。一种优选的制备方法如下:
将至少一种前体以粉末的形式预先置入。如果应该制备双金属或者多金属纳米颗粒,则优选将不同的粉状前体一起振荡和充分混合。将该粉末供给到等离子体室或者开放火焰,并且在其中瞬间蒸发。由此所产生的气态金属化合物从等离子体中排出,并且在更冷的区域中冷凝,其中形成了具有界定尺寸分布的纳米颗粒。通过加入表面活性剂和清洁剂来将该纳米颗粒稳定在乳液中。优选使用水或者有机溶剂来制备乳液。然后使用该乳液,或者两种或更多种乳液的混合物(其包含活性成分,另外的活性成分和/或促进剂)来浸透催化剂载体,优选借助于通常在专业文献中称作“初湿含浸法”的方法来浸透。在这种方法中,预先置入有待浸渍的载体刚好可以吸收的量的含有活性成分的浸渍溶液并由此确保活性成分被载体完全吸收。可能的另外的实施方案例如可以在专利申请US20080277270-A1中获悉。
为了从催化剂表面除去可能的干扰性有机化合物和将该纳米颗粒结合和稳定到催化剂上,将该催化剂随后在升高温度煅烧。煅烧优选在含氧气氛中进行,特别优选在空气或者惰性气体-氧气混合物中。该温度为至多800℃,优选250℃-600℃。煅烧持续时间适当地选择为优选1小时-50小时。用所述乳液浸渍的催化剂优选在煅烧前进行干燥,优选在减压下和适当地进行1小时-50小时。
适于作为另外的促进剂的是具有碱性作用的金属(例如碱金属盐、碱土金属盐和稀土金属盐);碱金属特别是Na和Cs,以及碱土金属的化合物是优选的;碱土金属,特别是Sr和Ba的化合物是特别优选的。在一种优选的实施方案中,该具有碱性作用的金属是以氧化物,氢氧化物,氯化物,氯氧化物或硝酸盐的形式使用的。在一种优选的实施方案中,将这种类型的促进剂通过浸透或者CVD方法施加到催化剂上。
根据本发明所用的载体优选是市售的(例如来自Saint Gobain Norpro)。
根据本发明用于氯化氢氧化的催化剂的显著特征在于高的活性,同时在高温时具有高稳定性。
该催化氯化氢氧化可以优选如下进行:在绝热或者等温或者近似等温,不连续地,但是优选连续地,作为流化床法或者固定床方法,优选作为固定床方法,特别优选在管束式反应器中,在多相催化剂上,在180-500℃,优选200-400℃,特别优选250-380℃的反应器温度,和1-25 bar(1000-25000hPa),优选1.2-20bar,特别优选1.5-17 bar和特别是2.0-15 bar的压力条件下进行。
进行催化氯化氢氧化的常规反应设备是固定床反应器或者流化床反应器。该催化氯化氢氧化也可以优选多级进行。
在绝热,等温或者近似等温运行方式中,也可以使用多个,也就是说2-10,优选2-6,特别优选2-5,特别是2-3个串联的反应器(具有中间冷却)。氯化氢可以在第一反应器上游与氧气一起完全加入或者经不同的反应器分布式加入。这种单个反应器的串联也可以在一个设备中实现。
适于所述方法的装置的另外一种优选的实施方案在于使用结构化的催化剂床(Katalysatorschüttung),在其中催化活性沿流动方向增加。催化剂床这样的结构化可以如下来进行:用活性物质将该催化剂载体浸渍到不同的程度或者用惰性材料将该催化剂稀释到不同的程度。作为惰性材料,可以使用例如二氧化钛,二氧化锆或者其混合物,氧化铝,滑石,陶瓷,玻璃,石墨或者不锈钢的环、圆柱或者球。当优选使用催化剂成形体(Katalysatorformk?rper)时,该惰性材料应当优选具有类似的外部尺寸。
具有任意形状的成形体均适合作为催化剂成形体,优选为片状体,挤出体,环状体,圆柱体,星状体,车轮状体或者球体,并且环状体,圆柱体或者星形柱状体是特别优选的形状。该成形体的尺寸(在球形情况中为直径)优选是0.2-10mm,特别优选0.5-7mm。
作为上述细碎的催化剂(成形)体的替代,所述载体也可以是整块载体材料。优选使用“经典的”具有平行通道的催化剂载体,所述通道不是径向互连的。可选择的优选实施方案是在载体内部具有三维的化合物的泡沫,海绵等,还有具有交叉流动通道的整块以及催化剂载体。
该整块载体可以具有蜂窝结构,但也可以具有开放的或者封闭的交叉通道结构。整块载体优选具有孔密度为100-900cpsi(每平方英寸的孔),特别优选200-600cpsi。
在本发明范围内,整块体公开在例如“Monoliths in multiphase catalytic processes–aspects and prospects”,F. Kapteijn,J. J. Heiszwolf,T. A. Nijhuis和J. A. Moulijn,Cattech 3,1999,第24页。
在单次通过中,氯化氢转化率是15-100%,并且可以优选限制到15-90%,优选40-90%,特别优选60-90%。未转化的氯化氢可在部分或完全分离之后返回至催化氯化氢氧化。在反应器入口处氯化氢与氧气的体积比优选1:1-20:1,特别优选2:1-8:1,最特别优选2:1-6:1。
该催化氯化氢氧化的反应热可以以有利的方式用于产生高压水蒸气。这可以用于运行光气化反应器和/或蒸馏塔,特别是异氰酸酯蒸馏塔。
在迪肯制氯法的最后一步,将所形成的氯分离掉。该分离步骤通常包含多个阶段,即,从该催化氯化氢氧化的产物气流中分离和任选的返回未反应的氯化氢,干燥所形成的主要含有氯和氧的料流,和从该干燥料流中分离氯。
未反应的氯化氢和所形成的水蒸气的分离可以通过冷却,从氯化氢氧化的产物气流中冷凝盐酸水溶液来进行。氯化氢也可以被吸收到稀盐酸或者水中。
下面的实施例用于说明本发明。
实施例
实施例1(对比例):制备非根据本发明的催化剂
将100g的TiO2粒料(圆柱体,直径大约2mm,长度2-10mm,Saint-Gobain)用氯化钌-n-水合物在H2O中的溶液浸透,以使得Ru含量是3质量%。将所获得的湿粒料在60℃干燥过夜,并且以干燥态在氮气吹扫下引入到NaOH和25%水合肼在水中的溶液中,并且放置1小时。然后蒸发掉过量的水。将该湿粒料在60℃干燥2小时,并且用300g水清洗4次。将所获得的湿粒料在120℃的马弗炉(空气)干燥20分钟,然后在其上在350℃煅烧3小时。
实施例2:制备示例性选出的根据本发明的催化剂
预先置入下面元素的稳定氧化物,其为μm级的粉末形式:Ru(RuO2),Sn(SnO2),Ni(NiO),Sb(Sb2O5),Zr-Y(90质量%ZrO2,10质量%Y2O3),Ti(TiO2),Bi(Bi2O5)。该粉末是单独的(样品名称2a-b,2e-i→ 单金属纳米颗粒)或者是预混(样品名称2c-d→双金属纳米颗粒)供给到等离子体室中,并且在其中瞬间汽化(在高于20000K的温度)。将所形成的气态金属化合物从该等离子体中排出,并且在冷却区(温度低于500℃)中冷凝,其中形成了具有界定尺寸分布的纳米颗粒。将该纳米颗粒通过加入基于胺的非离子梳状聚合物(制造商:SDC材料)在水性乳液中稳定,其中纳米颗粒的含量调节在7.5重量%。在该乳液中调节催化剂上期望的钌纳米颗粒:另外的纳米颗粒的比例,为此借助于专业文献中通常称作“初湿含浸法”的方法多次浸透该催化剂载体,直到期望的总负载量施加到该催化剂载体上。在这种方法中,预先置入有待浸透的载体刚好可以吸收的量的含有活性成分的浸渍溶液并因此确保了该活性成分完全被载体吸收。由Saint-Gobain所详述的载体性能如下:
该湿催化剂样品在浸透步骤之间和最后在110℃干燥2-5小时,并在550℃在空气中煅烧2小时。该纳米颗粒的金属含量占催化剂总质量的质量份额可以在表1中获知(用XRF测量)。
表1:纳米颗粒的金属含量占催化剂总质量的的质量份额(用XRF测量)
实施例3(对比例):非根据本发明的催化剂的测试(来自实施例1)
将1g的催化剂成形体(称为1)以用惰性球面玻璃球(Spheriglaskugeln)稀释的形式预先置入石英反应管中(内径10mm)。将这个批料进行与实施例4相同的测试程序。RZARu的变化和由其所获得特征参数可以由表2获知。
表2:非根据本发明的催化剂的RZA
Ru
的变化
*参数a和b的定义参见实施例4;1 n.b.:未测量。
实施例4:根据本发明的催化剂的测试(来自实施例2)
在每种情况中,将1g的催化剂成形体(称作2a-i)以用惰性球形玻璃球稀释的形式预先置入石英反应管中(内径10mm)。在恒定的氮气流下加热之后,在每一情况下用组成为1L/h氯化氢,4L/h氧气,5L/h氮气的气体混合物(10L/h)在380℃流经所述批料,持续大约16小时。然后将温度降低到330℃,并且测量时空产率(起始RZA)。然后将温度升高到430℃。为了测定失活,将该温度间歇式降低到330℃(x小时后的RZA)。如下来测量时空产率:引导各个反应器的产物气流通过20%的碘化钾溶液大约15分钟,然后用0.1 N硫代硫酸盐标准溶液滴定所形成的碘(两次测量)。然后根据下式,从这样测定的氯的量来确定单位(基于钌含量)时空产率(RZA)(表3a/b):
RZARu=g(氯)*g-1(所用催化剂上钌的质量)*h-1(时间)
RZARu的变化用幂级数解法来建模:
RZARu= a t-b(TOS在430°C的t(单位h))),
其中a代表起始活性,b代表失活率。这两个参数同样包括在表3a/b中。
表3a:根据本发明的催化剂的RZA
Ru
变化
表3b:根据本发明的催化剂的RZA
Ru
变化
1 n.b.:未测量。
一些示例性列举的根据本发明的催化剂(2a,2b,2g,2h,2i)的稳定性(建模失活参数–b)在一些情况中很显然明显高于非根据本发明的根据现有技术的催化剂。一些示例性列举的根据本发明的催化剂(2b,2f,2i)的比起始活性在一些情况中很显然高于非本发明的现有技术的催化剂。催化剂样品2a和2c甚至具有比根据现有技术的催化剂明显更高的(高温)稳定性和明显的更高的起始活性。
实施例5:在催化剂上的纳米颗粒的尺寸分布
少许10mg示例性列举的名为2a,2b,2c和2d的根据的本发明的催化剂精细研磨,悬浮于乙醇中,并且将所形成的悬浮液滴加到用于TEM测量(Tecnai20,Megaview III)的样品载体上。在TEM中研究两种样品的不同区域。在图1(催化剂2a)、图2(催化剂2b)、图3(催化剂2c)和图4(催化剂2d)中示例性地展示了催化剂样品的特征区域用以说明。
图1(催化剂2a):数出34个一次颗粒,直径是5-34nm(平均值为16nm)。
图2(催化剂2b):一次颗粒分布(二氧化钌和二氧化锡)类似于2a。
图3(催化剂2c):一次颗粒分布(二氧化钌和二氧化锡)类似于2a。
图4(催化剂2d):一次颗粒分布(二氧化钌和二氧化锡)类似于2a。
与根据本发明的催化剂相反,二氧化钌明显地作为覆盖载体的层存在于金红石-TiO2上(参见实施例1),这归因于两种金红石结构可比较的晶格距离,(“Development of an improved HCl oxidation process: structure of the RuO2/rutile TiO2 catalyst” Seki,Kohei;Iwanaga,Kiyoshi;Hibi,Takuo;Issoh,Kohtaro;Mori,Yasuhiko;Abe,Tadashi 在 Studies in Surface Science and Catalysis(2007),172(Science and Technology in Catalysis 2006),55-60中)。在同一的出版物中,将该催化剂与基于 Al2O3或者SiO2的钌载体催化剂相比,其尽管推测起来具有高的分散性,但是表现出明显更低的活性。与表面附着式施加于金红石-TiO2上相比,在这些载体上的高分散性对于催化性能来说明显是不利的。
但是,根据本发明的纳米结构化的钌载体催化剂(具有界定的钌一次粒度)甚至明显优于基于金红石-TiO2的钌载体催化剂。
Claims (16)
1. 催化剂材料,其用于通过基于钌基的负载催化剂,由含氯化氢和氧气的气体来热催化制备氯,其特征在于,该催化剂载体具有大量孔直径>50nm的孔,并且负载含有钌和/或钌化合物的纳米颗粒作为催化活性成分。
2. 根据权利要求1的催化剂材料,其特征在于,该催化剂材料的至少50%、优选至少80%的孔体积存在于直径大于50nm的孔中。
3. 根据权利要求1-2中任一项的催化剂材料,其特征在于,该催化剂载体包含作为载体材料的选自下面的一种或多种化合物:铝化合物,硅化合物,钛化合物,锆化合物或者锡化合物,优选铝化合物和/或硅化合物。
4. 根据权利要求3的催化剂材料,其特征在于,该催化剂载体包含作为载体材料的选自下面的一种或多种金属的氧化物、氧化物混合物或者混合氧化物:铝,硅,钛,锆或者锡,优选铝和硅的混合氧化物。
5. 根据权利要求1-4中任一项的催化剂材料,其特征在于,存在于该催化剂上的含钌的纳米颗粒包含作为催化活性成分的选自下面的一种或多种化合物:钌氧化物,钌混合氧化物,氧化钌混合物,卤氧化钌,卤化钌,金属钌,优选氯化钌,氧氯化钌或者氧化钌和氯化钌的混合物。
6. 根据权利要求1-5中任一项的催化剂材料,其特征在于,至少50%的该含钌纳米颗粒具有最大50nm的直径,优选至少50%的直径是5nm-50nm,特别优选至少80%的直径是5nm-50nm。
7. 根据权利要求1-6中任一项的催化剂材料,其特征在于,该含钌的纳米颗粒的平均直径是10-30nm。
8. 根据权利要求1-7中任一项的催化剂材料,其特征在于,基于该催化剂材料的总质量,该催化剂的钌含量为至多20重量%,优选0.5-5重量%。
9. 根据权利要求1-8中任一项的催化剂材料,其特征在于,该催化剂材料另外包含这样的纳米颗粒,其基于一种或多种另外的金属或者金属化合物作为另外的活性成分或者作为促进剂,优选是选自下面的元素的一种或多种另外的金属或者金属化合物和混合化合物:Ag,Au,Bi,Ce,Co,Cr,Cu,Ni,Sb,Sn,Ti,W,Y,Zn,Zr和铂金属,特别优选元素Bi,Sb,Sn和Ti。
10. 根据权利要求9的催化剂材料,其特征在于,该另外的纳米颗粒包含权利要求9中所述金属的氧化物、混合氧化物、氧化物混合物、卤氧化物,特别是氯氧化物、卤化物,特别是氯化物,或者金属,或者金属合金作为金属化合物。
11. 根据权利要求1-10中任一项的催化剂材料,其特征在于,存在于该催化剂上的另外的纳米颗粒的份额,基于该催化剂材料的总质量,为至多20重量%,优选至多10重量%。
12. 根据权利要求1-11中任一项的催化剂材料,其特征在于,至少50%的存在于该催化剂上的另外的纳米颗粒具有最大50nm的直径,优选至少50%的直径是3nm-50nm,特别优选至少80%的直径是3nm-50nm。
13. 根据权利要求1-12中任一项的催化剂材料,其特征在于,该另外的纳米颗粒的平均直径是5-30nm。
14. 用于制备根据权利要求1-13中任一项的催化剂材料的方法,其特征在于,该催化剂经由至少下面的方法步骤来制备:
a)通过火焰热解来合成含有钌和/或钌化合物的纳米颗粒,
b)在乳液中稳定该含有钌和/或钌化合物的纳米颗粒,
c)(多次)用步骤 b)的乳液来浸渍该载体,
d)在升高温度煅烧该经浸渍的催化剂。
15. 由含氯化氢和氧气的气体来热催化制备氯的方法,其特征在于,将根据权利要求1-13中任一项的催化剂材料用作催化剂。
16. 根据权利要求15的方法,其特征在于,该氯化氢氧化绝热或者等温或者近似等温进行,优选绝热进行,特别是连续地作为流化床法或者固定床法,优选作为固定床法进行,反应器温度是180-500℃,优选200-400℃,特别优选250-380℃,和压力是1-25 bar(1000-25000hPa),优选1.2-20bar(1200-20000hPa),特别优选1.5-17 bar(1500-17000hPa)和特别是2.0-15 bar(2000-15000hPa)。
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CN112547059B (zh) * | 2020-09-07 | 2024-01-26 | 北京工业大学 | 一种具有良好稳定性的Ru/3DOM SnO2催化剂的制备方法及应用 |
KR20220105387A (ko) | 2021-01-20 | 2022-07-27 | 한화솔루션 주식회사 | 염화수소 산화반응을 통한 염소의 고수율 제조방법 |
WO2023174923A1 (en) * | 2022-03-14 | 2023-09-21 | Basf Se | Continuous process for preparing chlorine and a catalyst for preparing chlorine |
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- 2010-07-14 WO PCT/EP2010/004287 patent/WO2011012226A2/de active Application Filing
- 2010-07-14 KR KR1020127001664A patent/KR20120040701A/ko not_active Application Discontinuation
- 2010-07-14 CN CN2010800325889A patent/CN102711986A/zh active Pending
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CN108602060A (zh) * | 2016-02-04 | 2018-09-28 | 科思创德国股份有限公司 | 通过气相氧化制备氯气的催化剂和方法 |
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JP2013500145A (ja) | 2013-01-07 |
DE102009034773A1 (de) | 2011-01-27 |
KR20120040701A (ko) | 2012-04-27 |
US20120148478A1 (en) | 2012-06-14 |
WO2011012226A2 (de) | 2011-02-03 |
IN2012DN00739A (zh) | 2015-06-19 |
WO2011012226A3 (de) | 2012-03-01 |
EP2459312A2 (de) | 2012-06-06 |
TW201117880A (en) | 2011-06-01 |
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