CN103492069A - 用于制备包含氧化铀作为活性组分的催化剂的方法 - Google Patents
用于制备包含氧化铀作为活性组分的催化剂的方法 Download PDFInfo
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Abstract
本发明涉及用于制备氧化铀催化剂本体的方法,具有如下步骤:a)在第一烧结过程中将纯度为至少50%的UO2+x-粉末(2)(其中x≤0.7)烧结成UO2+y-中间产物(14)(其中y≤0.25),b)用氧气氧化UO2+y-中间产物(14)并使其转化成U3O8-z-粉末(11)(其中z≤l),c)将U3O8-z-粉末(11)压制成具有与之后的催化剂本体(1)相应的形状的坯料(15),和d)在第二烧结过程中在含氧气的烧结气氛中在至少900℃下烧结坯料(15)。
Description
本发明涉及用于制备包含氧化铀作为活性组分的催化剂的方法。
氧化铀可以用作一系列氧化反应的氧化催化剂,例如如DE 102007 033 114 A1中所述,用于挥发性有机化合物的完全氧化,用于将一氧化碳氧化成二氧化碳,将异丁烯氧化成丙烯醛和将氯化氢氧化成氯。催化剂和氧化铀催化剂以各种方式制备,其中在载体上以液体形式或以前体(如铀二水合物)的水悬浮液的形式或通过CVD(化学气相沉积)或PVD(物理气相沉积)以气相方式施涂活性组分。
本发明的目的是提供氧化铀催化剂的替代性制备方法。
所述目的通过根据权利要求1所述的方法实现。本发明所基于的总体思路是由氧化铀制备具有高开放孔隙率的烧结体。不同于已知制备方法(其中必须首先提供合适的载体,例如Al2O3载体,然后为所述载体提供活性组分),根据本发明制备载体和活性组分结合的催化剂。这省去了制备成本和在载体上施涂活性组分的成本。此外,此处所讨论类型的铀材料是低放射性的,因此就清除例如过量的或变得不可使用的前体悬浮液或在制备前体时产生的废料而言,不会产生升高的、使制备昂贵的成本。
在第一烧结过程中将UO2+x-粉末(其中x≤0.7)烧结成UO2+y-中间产物(其中y≤0.25)(步骤a),所述UO2+x-粉末优选通过UF6、UO3、UN、UNH、U3O8或UF4的化学反应在干式或湿式转化方法中获得。UO2+x粉末优选在没有其他添加剂(例如金属氧化物如Al2O3或ZrO2)的情况下使用,然而可以包含至多50重量%的这些添加剂。中间产物为具有任意结构的成形体。然而也可以想到,UO2+x粉末在没有预先压实的情况下烧结,然而这出于工艺技术原因是不切实际的。符合目的的是制备中间产物,所述中间产物具有与之后的最终产物(即完成的催化剂本体)相同的形状。为了压制中间产物-坯料和为了下文进一步描述的压制催化剂本体的坯料,可以使用同一压制装置。
在随后的步骤b)中用氧气处理烧结的中间产物,其中UO2+y氧化成U3O8-z(其中z≤l)。由中间产物形成微细U3O8-z-粉末,所述微细U3O8-z-粉末的平均粒径例如在5μm至10μm范围内或通常在1至30μm范围内,其烧结活性相对于初始UO2-粉末降低。初始UO2-粉末的粉末粒子(其可以例如具有5μm至500μm的粒径)即各自由晶粒尺寸在例如50nm至300nm范围内的大量小晶粒形成,这意味着相对高的烧结活性,有利于制备更紧密的、具有低孔隙率的烧结体。在根据本发明的方法中,在第一烧结过程中将最初存在的晶粒融化成更大的晶粒/粒子,使得在第一烧结过程之后和同样地在步骤b)中氧化之后存在高达600倍大的晶粒,即晶粒尺寸为1μm至3μm的晶粒,这鉴于待制备的烧结体的高孔隙率或低密度是有利的。然而另一主要效果可能在于,具有正交晶体结构的U3O8-z的密度小于立方UO2+y的密度,因此在氧化之后造成原始UO2+y-颗粒的体积增大,其中粒子出现大量裂纹并且分解成更小的成分。由此在颗粒中产生大量空腔。
这造成在第二烧结过程中至少部分地保持空腔并且产生具有高开放孔隙率的催化剂本体。
从属权利要求中给出了上述方法的有利实施方案。
现在参考附图更详细地解释本发明。附图各自以高度示意性的形式显示:
图1显示了用作根据本发明的方法的初始粉末的UO2+x-粉末(其中x≤0.7),
图2显示了具有晶粒的初始粉末的UO2+x-颗粒,
图3显示了UO2+x-中间产物或U3O8-z-催化剂本体的坯料的制备,
图4显示了UO2+y-中间产物(其中y≤0.25)用氧气氧化,
图5显示了由UO2+y-粒子通过氧化产生的U3O8-z-颗粒(其中z≤l)。
为了制备根据本发明的例如圆柱状催化剂本体1,使用UO2-粉末2作为初始粉末,优选使用由六氟化铀(UF6)、三氧化铀(UO3)、硝酸铀(UN)、硝酸铀六水合物(UNH)、八氧化三铀(U3O8)或四氟化铀(UF4)通过湿式化学或干式化学转化获得的UO2-粉末。已知方法根据其中间步骤命名,例如AUC-方法(碳酸铵铀)或ADU-方法(重铀酸铵)。在干式化学转化方法中,UF6与水和氢气在气相中直接反应成二氧化铀。所述类型的UO2+x-粉末通常具有粉末颗粒3,所述粉末颗粒3具有5μm至500μm,然而通常在10μm至150μm范围内的平均粒径。粉末颗粒本身又是尺寸在约50nm至300nm范围内的大量晶粒4的聚集体。单个UO2+x颗粒3因此类似于由大量不同取向晶粒组成的构造。
首先在第一方法步骤(步骤a)中,在第一烧结过程中烧结UO2+x-粉末。
优选使用在制备核电站的核燃料芯块的过程中在铀浓缩时产生的贫化的UO2+x。将UO2+x-粉末2压制成例如圆柱状坯料5,其中出于该目的将UO2+x-粉末2装入具有圆柱形空腔6的模具7中,并用以箭头9的方向进入模具7的印模8压缩至通常5至7g/cm3的密度(图3)。还可以使用其他压缩方法,例如双轴压制、均衡压制等以及相应的其他压缩程度。UO2+x的理论密度为约11g/cm3。坯料5的烧结在炉(未示出)中进行从而获得UO2+y(其中y≤0.25)。为了保证上述情况,例如在包含H2的气氛中在1500℃至1800℃下烧结,或在包含CO2的气氛下在1100℃至1200℃下烧结。烧结之后则存在例如圆柱状UO2+y-烧结体作为中间产物14。
在随后的方法步骤(步骤b)中,紧接着烧结之后,在炉16(例如第一烧结过程所使用的炉)中将中间产物14氧化成U3O8-z(其中z≤l),其中U3O8-z分解成U3O8-z-粉末11。因此中间产物14的形状并不重要。当为中间产物14选择与最终产物(催化剂本体1)相同的形状时,可以对各个坯料的压制使用同一装置(模具7、印模8)。第一烧结过程的作用在于,在随后的氧化中获得的U3O8-z-粉末具有低烧结活性,这需要制备紧密性更低的、具有高孔隙率的烧结体。另一作用在于,具有比UO2更低的8.38g/cm3的密度的U3O8,这造成由UO2+y形成的U3O8-z-颗粒10膨胀,其中其部分分解成碎片12并在其中例如以裂纹的形式形成空腔13(参见图5)。氧化通常在300℃至600℃的温度下在例如3小时的时间段内进行。
在另一方法步骤(步骤c)中,将如上所述的U3O8-粉末11例如单轴压制成坯料15,所述坯料15具有通常为5g/cm3至6g/cm3的密度和与之后的催化剂本体1相应的形状。还可以使用其他压缩方法,例如双轴压制、均衡压制等以及其他压缩程度。催化剂本体1例如为直径为7mm且高度为10mm的圆柱体。可以在压制之前向U3O8-z-粉末加入压制助剂,例如0.2重量%的聚乙烯蜡。压制助剂也可以在制备中间产物14时使用。
在第二烧结过程(步骤d)中烧结以上述方式获得的坯料15,其中烧结在U3O8-组成范围保持不变的气氛中进行。保证上述情况的气氛包含氧气或由空气组成,其中在烧结过程中保持1000℃至1300℃的温度。最后获得具有高开放孔隙率和相应的大内表面积的催化剂本体1,催化反应可以在所述大内表面积上进行。
以上述方式制备的U3O8-z-催化剂本体1在空气中在直至约1000℃至1200℃下稳定。为了在还原条件下使用,可以在300℃至1000℃,优选400℃至600℃的温度下在含H2的气氛(例如H2、H2-N2、H2-Ar等)中还原性处理催化剂本体,从而使U3O8-z转化成UO2。虽然UO2作为多孔本体在空气中仅在直至约120℃下稳定,但是在还原性条件下在直至约1000℃下稳定。
实施例:
以上述方式和方法制备的圆柱形UO2-中间产物14在450℃下氧化3小时。由此产生的U3O8-粉末与0.2%压制助剂(PE-蜡)混合并压制成密度为5g/cm3至5.5g/cm3且重量为1g的圆柱状坯料15。然后在炉中在1280℃(批次A)或1100℃(批次B)下用空气作为烧结气氛烧结坯料15一小时。可以获得具有如下性质的催化剂本体1:
批次A | 批次B | |
密度(g/cm2) | 7.15-7.20 | 6.67-6.97 |
开放孔隙率[%] | 91-92 | 92-96 |
比表面积[m2/kg] | 140 | 250 |
平均粒径[μm] | 4.2 | 2.2 |
开放孔隙率以总孔隙率的比例的形式给出,其中总孔隙率(体积%)得自:总孔隙率=(1-密度/理论密度)x100。UO2的理论密度为10.96g/cm3,U3O8的理论密度为8.38g/cm3。
Claims (11)
1.用于制备氧化铀催化剂本体的方法,具有如下步骤:
a)在第一烧结过程中将纯度为至少50%的UO2+x-粉末(2)(其中x≤0.7)烧结成UO2+y-中间产物(14)(其中y≤0.25),
b)用氧气氧化UO2+y-中间产物(14)并使其转化成U3O8-z-粉末(11)(其中z≤l),
c)将U3O8-z-粉末(11)压制成具有与之后的催化剂本体(1)相应的形状的坯料(15),和
d)在第二烧结过程中在含氧气的烧结气氛中在至少900℃下烧结坯料(15)。
2.根据权利要求1所述的方法,其特征在于,在步骤a)中使用UO2+x-粉末(2),所述UO2+x-粉末(2)通过UF6、UO3、UNH、U3O8或UF4的转化获得。
3.根据权利要求1或2所述的方法,其特征在于,在步骤a)中使用UO2+x-粉末(2),所述UO2+x-粉末(2)的粉末颗粒具有5μm至500μm的平均粒径。
4.根据权利要求3所述的方法,其特征在于,使用平均粒径为10μm至150μm的UO2+x-粉末(2)。
5.根据前述权利要求任一项所述的方法,其特征在于,使用UO2+x-粉末(2),所述UO2+x-粉末(2)的粉末颗粒(3)由平均尺寸为30nm至300nm的晶粒(4)形成。
6.根据前述权利要求任一项所述的方法,其特征在于,根据步骤b)的UO2+y-中间产物(14)的氧化在至少300℃的温度下进行。
7.根据权利要求6所述的方法,其特征在于,氧化在400℃至500℃下进行。
8.根据前述权利要求任一项所述的方法,其特征在于,催化剂本体(1)的坯料(15)在900℃至1300℃下烧结。
9.根据前述权利要求任一项所述的方法,其特征在于,在步骤d)之后还原催化剂本体(1),从而将U3O8-z转化成UO2。
10.根据权利要求9所述的方法,其特征在于,还原在300℃至1000℃的温度下进行。
11.根据权利要求10所述的方法,其特征在于,还原在400℃至600℃的温度下进行。
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DE102011081074.9 | 2011-08-17 | ||
PCT/EP2012/064583 WO2013023890A1 (de) | 2011-08-17 | 2012-07-25 | Verfahren zur herstellung eines uranoxid als aktive komponente enthaltenden katalysators |
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DE102008050977A1 (de) * | 2008-10-09 | 2010-04-15 | Bayer Technology Services Gmbh | Integriertes Verfahren zur Herstellung von Chlor |
DE102008050975A1 (de) * | 2008-10-09 | 2010-04-15 | Bayer Technology Services Gmbh | Mehrstufiges Verfahren zur Herstellung von Chlor |
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EP0023923B1 (en) * | 1979-02-12 | 1985-08-14 | Exxon Research And Engineering Company | Compounds and catalysts containing phosphorus, arsenic or nitrogen and their use in hydrocarbon conversion processes |
CN100999408A (zh) * | 2006-12-15 | 2007-07-18 | 清华大学 | 一种制备uo2陶瓷燃料微球的方法 |
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