CN103534027B - 用于氧化有机污染物的具有特别显著的疏水性的低温氧化催化剂 - Google Patents

用于氧化有机污染物的具有特别显著的疏水性的低温氧化催化剂 Download PDF

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CN103534027B
CN103534027B CN201280024064.4A CN201280024064A CN103534027B CN 103534027 B CN103534027 B CN 103534027B CN 201280024064 A CN201280024064 A CN 201280024064A CN 103534027 B CN103534027 B CN 103534027B
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catalyst
noble metal
micropore
zeolitic material
bea
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CN103534027A (zh
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阿诺·泰斯勒
弗兰克·克洛斯
罗德里克·阿尔特霍夫
米卡·恩德勒
帕特里克·缪勒
格利高里·列兹尼科夫
玛吉特·苏思科
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Clariant Produkte Deutschland GmbH
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Clariant Produkte Deutschland GmbH
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Abstract

本发明涉及一种催化剂，包含含有贵金属的微孔沸石材料和含有SiO2的多孔粘结剂，其中该催化剂的微孔相对于该催化剂的总孔隙体积的比例为70%以上。本发明还涉及一种生产该催化剂的方法以及该催化剂作为氧化催化剂的应用。

Description

用于氧化有机污染物的具有特别显著的疏水性的低温氧化催 化剂
本发明涉及一种催化剂，该催化剂包含含有贵金属的微孔沸石材料和含有SiO2的多孔粘结剂，其中该催化剂的微孔比例相对于该催化剂总孔隙体积为70%以上。另外，本发明涉及一种生产该催化剂的方法，以及该催化剂作为氧化催化剂的应用。
用催化剂来净化废气为人们所知已经有一段时间了。例如，用所谓的三效催化剂(TWC)来净化内燃机产生的废气。氮氧化物被还原性碳氢化合物(HC)和一氧化碳(CO)还原。
同样地，用催化剂后处理柴油发动机产生的废气。在这种情况下，例如，把一氧化碳、未完全燃烧的碳氢化合物、氮氧化物和煤烟颗粒从废气中除去。被催化处理的未完全燃烧的碳氢化合物包括烷烃、烯烃、醛类和芳香烃。
同样地，发电厂排放的废气以及在工业生产过程中产生的废气也使用催化剂净化。
用于净化含有有机污染物的废气的催化剂通常对水汽很敏感。水汽阻碍催化剂表面的活性中心，导致催化剂的活性降低。这一般通过较大的贵金属掺杂量补救，但是这种做法一方面增加催化剂成本，另一方面，根据现有技术的描述，对于已知体系增加催化剂烧结趋向。
此外，在低废气温度时，高水汽分压通过毛细凝聚导致催化剂的孔隙内形成水膜，这同样导致催化剂钝化，然而这种钝化是可逆的。由于经济原因，另外提高废气温度以避免毛细凝聚是不实际的。
在许多应用中，通常采用限制可用于加热进入气体的能量的大小的热量循环系统。
因此，期望得到催化剂，该催化剂在低温如低于300℃，甚至在高水汽浓度的情况下，在有机污染物氧化中，尤其是在溶剂型污染物氧化中，具有高活性，该催化剂也具有低热烧结倾向，并且此外，使用明显较低的贵金属掺杂量。
因此，本发明的目的包括提供一种催化剂，该催化剂在低温下，在有机污染物氧化中具有高活性，具有低热烧结趋向并且需要低贵金属量比例。
该目的通过一种催化剂实现，该催化剂包含含有贵金属的微孔沸石材料和含有SiO2的多孔粘结剂，其中该催化剂的微孔相对于该催化剂总孔隙体积的比例为70%以上。
令人惊奇的是，包含含有贵金属的微孔沸石材料和含有少量的中孔和大孔的纯的SiO2粘结剂组成的催化剂在溶剂型空气污染物的氧化中具有明显较高的活性。
优选地，该催化剂的微孔相对于该催化剂总孔隙体积的比例为70%以上，更优选地为80%以上，最优选地，为90%以上。
根据本发明的催化剂的优选的实施方式中，微孔相对于该催化剂总孔隙体积的比例为>72%，更优选地为>76%。
由于空间原因，毛细凝聚不能在微孔中发生，因此通向催化剂中心的扩散通道没有被堵塞。除此之外，输送孔隙大以至于毛细凝聚基本上不能发生。总的来说，该催化剂的特征在于微孔比例大于70%，以及中孔和大孔的比例在20%到30%之间。微孔比例优选地<100%，更优选地<95%。
因此，根据本发明的催化剂是具有多众数孔隙分布的催化剂，即它含有微孔，中孔和大孔。在本发明中，术语微孔、中孔和大孔是指，直径小于1纳米的孔(微孔)、直径在1-50纳米的孔(中孔)或直径>50纳米的孔(大孔)。
微孔、中孔和大孔的比例按照ASTM-4365-85通过所谓的t-plot方法测定。
催化剂的总孔隙体积优选地为100mm3/g以上，更优选地180mm3/g以上。总的孔隙体积优选地按照DIN ISO9277，采用氮孔隙度计或者惰性气体孔隙度计测定。
根据催化剂的一个实施方式，优选地，沸石材料的铝相对于沸石材料的比例为<2mol.%，更优选地小于1mol.%。
另外，优选地，粘结剂成分不含有大量的铝。粘结剂优选地含有小于0.04wt.%，更优选地小于0.02wt.%铝，相对于粘结剂的量。合适的粘结剂是例如Ludox40或者含Al2O3的比例<0.04wt.-%的四乙氧基硅烷。
根据本发明的一个实施方式，优选地，沸石材料含有相对于该沸石材料的量的0.5-6.0wt.%，更优选地0.6-5.0wt.%，更加优选地0.7-4.0wt.%，特别优选地0.5-3.0wt.-%的贵金属。
另外，关于载体涂层，优选地载体涂层含有的贵金属的负载量相对于该载体涂层体积为0.1-2.0g/l，更优选地0.4-1.5g/l，更加优选地0.45-1.0，最优选地0.45-0.55。
贵金属优选地选自于由铑、铱、钯、铂、钉、锇、金和银组成的组，或者所指定贵金属的组合以及所指定贵金属的合金。
这些贵金属可以以贵金属颗粒或者贵金属氧化物颗粒的形式存在。下文中提及的主要是指贵金属颗粒，然而，也包括贵金属氧化物颗粒，除非特别指明。
贵金属颗粒的粒径优选地平均直径为0.5-5纳米，更优选地平均直径为0.5-3纳米，特别优选地平均直径为0.5-2纳米。粒径可以例如使用TEM测定。
原则上，被负载的沸石材料中的贵金属颗粒仅可能地小是有优势的，这样该颗粒具有非常高的色散度。色散度是指形成金属颗粒表面的金属原子的数量与金属颗粒的金属原子的总数量比率。
然而，有利的平均粒径也取决于催化剂的用途，还取决于形成贵金属颗粒的贵金属的性质、沸石材料的孔隙分布特别是沸石材料的孔隙半径和通道半径。
贵金属颗粒优选地位于沸石的内部孔隙体系。根据本发明，内部孔隙体系指的是沸石的微孔、中孔和大孔。贵金属颗粒优选地位于(基本上)在沸石的微孔中。
本发明的催化剂中含有的沸石材料可以是沸石或者类沸石材料。优选的沸石材料的实例为硅酸盐、铝硅酸盐、镓硅酸盐、锗硅酸盐、铝磷酸盐、硅铝磷酸盐、铝磷酸金属盐、铝磷硅酸金属盐、钛硅酸盐或者钛铝硅酸盐。选用哪种沸石材料一方面取决于用在沸石上或中的贵金属的性质，另一方面取决于催化剂的用途。
现有技术中，有很多的方法可以改良沸石材料的性能，例如结构类型、孔径、通道直径、化学成分、离子可交换性以及活性，以满足相应的预期用途。
然而，根据本发明，与如下结构类型中的一种相应的沸石材料通常是优选的：AFI、AEL、BEA、CHA、EUO、FAU、FER、KFI、LTL、MAZ、MOR、MEL、MTW、OFF、TON和MFI。这些提到的沸石材料可以以钠的形式也可以以铵的形式或者以H的形式出现。根据本发明，使用两性化合物制备的沸石材料也是优选的。这些材料的优选的实施例参见US5,250,282，也引入本发明作为参考。
根据本发明的催化剂的另一个实例方式，优选地，催化剂以粉末形式、以整体催化剂形式或者以涂层催化剂形式出现。整体催化剂可以是例如挤压成型体，如整块形。进一步优选的成型体为例如球形、环形、圆柱形、中间穿孔的圆柱形、片状或者圆锥形，其中整块形是特别优选的，例如整块蜂窝体。
此外，优选地，本发明的催化剂可以作为载体，即以涂层催化剂的形式出现。载体可以例如是开孔泡沫结构，例如金属泡沫、金属合金泡沫、碳化硅泡沫、Al2O3泡沫、莫来石泡沫、铝钛泡沫以及整体的载体结构，该结构例如具有相互对其平行的通道，这些通道可以通过管道相互连接或者含有用于旋流风的特定的内部结构。
同样地，优选的载体例如由任何金属或者合金薄片成型，该薄片包括金属箔、烧结金属箔或者金属织物，并通过例如挤压、卷取或者堆叠生成。同样也可以使用陶瓷材料制成的载体。陶瓷材料通常是具有小表面积的惰性材料，例如堇青石、莫来石、阿尔法铝氧化物、碳化硅或者钛酸铝。然而，使用的载体也可以由大表面积的材料组成，例如伽马铝氧化物或者TiO2。
根据本发明的催化剂的一个实施方式，沸石材料/粘结剂的重量比重为80/20-60/40，优选地为75/25-65/35，最优选地为约70/30。
本发明的催化剂的BET表面积的范围优选地为10-600m2/g，更优选地为50-500m2/g，最优选地为100-450m2/g。根据DIN66132通过氮吸附法测定BET表面积。
本发明的另一个主题是一种制备本发明的催化剂的方法，包括如下步骤：
a)将贵金属前驱体化合物引入到微孔沸石材料中；
b)煅烧负载有贵金属前驱体化合物的沸石材料；
c)混合负载有贵金属前驱体化合物的沸石材料和含有SiO2的多孔粘结剂以及溶剂；
d)干燥并且煅烧包含负载有贵金属前驱体化合物的沸石材料和粘结剂的混合物。
步骤c中得到的混合物在干燥和煅烧之前可以用应于载体材料，其中形成涂层催化剂。
根据预期用途，即将要催化的反应，沸石材料中的贵金属以贵金属的金属形式或者贵金属氧化物形式出现。
如果需要贵金属的金属形式，沸石材料中负载的贵金属化合物在后续的步骤中转化为金属。通常通过热解或者通过氢气、一氧化碳或者湿法化学还原剂还原将贵金属化合物转化为相应的贵金属。还原也可以在反应釜中催化反应开始原位进行。
根据本发明的方法的一个实施方式，通过用贵金属前驱体化合物溶液浸渍沸石材料引入贵金属化合物，例如向沸石材料上喷洒溶液。从而保证沸石材料的表面大量均匀地覆盖贵金属前驱体化合物。在沸石材料上基本上均匀地覆盖贵金属前驱体化合物层成为在随后的煅烧步骤中或在金属化合物转化为相应的金属过程中，在沸石材料上大体上均匀地负载贵金属颗粒的基础，这一煅烧步骤使得贵金属前驱体化合物分解。优选地采用本领域的技术人员已知的初湿含浸法浸渍沸石材料。例如相应的贵金属的硝酸盐、醋酸盐、草酸盐、酒石酸盐、甲酸盐、胺、硫化物、碳酸盐、卤化物或者氢氧化物可以作为贵金属前驱体化合物。
用贵金属前驱体化合物浸渍沸石材料后，优选地在200-500℃，更优选地300-700℃，最优选地500-600℃时进行煅烧。根据本发明，煅烧优选地在保护气体下进行，例如氮气或者氩气，优选氩气。
在其他方面，关于上述催化剂的选择同样适用于方法。
本发明的另一个主题是本发明的催化剂作为氧化催化剂的应用，特别是用于有机污染物尤其是溶剂型有机污染物的氧化。
将结合一些具体实施例来描述本发明，这些具体实施例不应视为对本发明保护范围的限制。给出附图之外的参考。
图1显示本发明的催化剂与常规参考材料在GHSV为40000h-1下空气中的180ppmv乙酸乙酯氧化时的性能比较。
图2显示对贵金属掺杂量作图，225℃时转化率的比较。
具体实施例1
在120℃时H-BEA-150沸石干燥过夜，大约为16h，以便在之后的吸水过程中获得信息结果。沸石的吸水率可以通过“初湿含浸法”法测定。为此，约50g将要被浸渍的沸石装在袋子中，袋子去除皮重，加入水并揉捏(kneaded)，直到沸石达到吸水饱和。(吸水率：38.68g=77.36%)
酸性Pt-(NO3)2溶液用于Pt浸渍(15.14wt.%)。同样地，在这种情况下，Pt负载量通过负载在蜂窝体内的固体预测定，参考负载量必须用掺杂的Pt的量反算。
蜂窝体的目标负载量为30g/L。对于每3.375L的蜂窝体，这相当于贵金属负载量为0.5g/L的载体涂层的参考负载量为101.25g(m参考(3.375L时)=1.68g)。沸石与阿克苏硅(Bindzil)的比例为70/30。固体含量(Bindzil，wt.%SiO2=34%)；m(无阿克苏硅的参考负载量)=90.92g Pt-BEA-150。
Pt含量为1.68g时，BEA-150将用1.85%的Pt浸渍。对于1500g Pt-BEA-150，这相当于Pt负载量为27g，因此需要Pt-(NO3)2溶液(wt.%Pt-15.14)的量为183.88g。吸水率为77.36%时，Pt-(NO3)2溶液必须用1008.65g水再次稀释。
浸渍在耐驰(Netzsch)公司出产的带有蝴蝶型搅拌器的混合器中进行。为浸渍，在容器(罐)中预先称量沸石的量(1罐=102.77g相应地15罐1500g)。溶液的总量外推到由罐的数量(102.77g沸石->79.50g Pt-(NO3)2溶液，该溶液含有12.26g Pt-(NO3)2和67.24g去矿质水)。混合在250rpm时开始并缓慢加入溶液。在加入过程中提高转速。溶液加入完毕后，转速提高到500rpm，搅拌持续大约0.5分钟。然后把粉末转移到陶瓷碗中，在120℃下干燥大约6小时。然后氩气保护下(通流50l/h)Pt沸石在550℃/5h(升温速率60℃/h)下煅烧5小时。在这个过程中，贵金属几乎仅仅留在催化剂的微孔中，使得在水汽密度很高的情况下具有非常高的氧化活性和稳定性。
陶瓷蜂窝体涂层：
载体涂层的制备：
使用的量：
去矿质水 2052.0g 电导率：1.0μS
Pt-BEA-150 1359.30g LOI[%]1.50 1380.0g
阿克苏硅2034DI 377.40g FS[%]34.00 691.90g
在制备之前，沸石粉末的粒径分布在物理分析中测量。
结果：D10=3.977μm;D50=10.401μm;D90=24.449μm
测试按照标准方法进行。准备的容积为5L的烧杯。将沸石粉末悬浮在去矿质水中然后测量PH值(PH：2.62)。把阿克苏硅加入悬浮液中然后测试PH值(PH：2.41)。然后用分散(Ultra Turrax)搅拌器分散悬浮液大约10分钟。从悬浮液中取样并测试其颗粒分布。
分散后结果：D10=2.669μm;D50=6.971μm;D90=18.575μm
在磁力搅拌器上进一步搅拌载体涂层，然后用于涂覆。
固体含量[%] 40.10
pH 2.41
涂覆
用15%的去矿质水稀释载体涂层。稀释后固体含量为13.62%。对于涂覆，搅拌载体涂层直至无沉淀剩余然后测量载体涂层。这样，载体被完全浸没在载体涂层容器中，直至无气泡产生时移除(时间：大约30s)。然后取出载体，用压缩空气喷嘴从两边均匀地吹气至约一半参考负载量。载体在150℃下干燥过夜。用循环空气干燥炉干燥。干燥后，冷却载体然后称重。如果没有达到参考负载量，再涂覆载体直到达到参考值。在涂覆之间干燥经涂覆的蜂窝体。然后在循环空气炉中在标准条件下进行煅烧。
加热 时间[h] 4 温度[℃] 从40到550
保温 时间[h] 3 温度[℃] 在550
冷却 时间[h] 4 温度[℃] 从550到80
载体涂层类型：Pt-BEA-150
载体编号 1 2 3 4 5 6
第一次涂覆空重[g] 1806 1781 1811 1770 1802 1806
第一次涂覆湿-参考[g] 2549 2524 2554 2513 2545 2549
第一次涂覆湿-实际[g] 2120 2118 2123 2108 2133 2145
第一次涂覆 干燥[g] 1830 1812 1835 1802 1836 1840
第一次涂覆 负载量[g] 25 31 24 32 34 34
第二次涂覆 空重[g] 1830 1812 1835 1802 1836 1840
第二次涂覆 湿-参考[g] 0 2524 2554 2513 2545 2549
第二次涂覆湿-实际[g] 2152 2159 2177 2160 2167 2194
第二次涂覆 干燥[g] 1856 1845 1868 1841 1868 1881
第二次涂覆 负载量[g] 26 33 33 39 32 41
第三次涂覆 空重[g] 1856 1845 1868 1841 1868 1881
第三次涂覆 湿-参考[g] 2599 2588 2611 2584 2611 2624
第三次涂覆 湿-实际[g] 2196 2206 2192 2185 2193 2224
第三次涂覆 干燥[g] 1879 1882 1897 1878 1901 1916
第三次涂覆 负载量[g] 23.00 37.00 29.00 37.00 33.00 35.00
第四次涂覆 空重[g] 1879 1897
第四次涂覆 湿-参考[g] 1885 1903
第四次涂覆 湿-实际[g] 2189 2225
第四次涂覆 干燥[g] 1911 1947
第四次涂覆 负载量[g] 32.00 0.00 50.00 0.00 0.00 0.00
总负载量[g] 105.5 100.90 136.10 108.20 98.90 110.40
总负载量[g/L] 31.26 29.90 40.33 32.06 29.30 32.71
重量，煅烧[g] 1911.00 1881.00 1947.00 1880.00 1898.00 1915.00
总负载量，煅烧[g] 105.50 99.90 136.10 110.20 95.90 109.40
总负载量[g/L] 31.26 29.60 40.33 32.65 28.41 32.41
表1：涂覆结果
本发明的催化剂的微孔、中孔和大孔的比例通过t-plot方法研究，测试结果以m2/g为单位(见表2)。
Sio2粘结剂[wt.%] 10% 20% 40%
微孔[m2/g] 461 415 358
中孔/大孔[m2/g] 121 125 134
总孔隙[m2/g] 582 549 492
表2：孔隙率
对比例1
用由80wt.%TiO2和20wt.%Al2O3组成的载体涂层以50g/L涂覆陶瓷蜂窝体。为了这样，首先剧烈搅拌TiO2/Al2O3的水悬浮液。然后把陶瓷蜂窝体结构浸泡到载体涂层的悬浮液中。浸泡后，没有粘附的载体涂层被吹出蜂窝体通道。蜂窝体在120℃下干燥，然后在550℃煅烧3小时。通过将涂覆有载体涂层的催化剂蜂窝体浸没在硝酸铂和硝酸钯的溶液中涂覆贵金属。浸没之后，再将蜂窝体吹干，在120℃下干燥2小时，然后在550℃下煅烧3小时。
对比例2
用由Al2O3组成的载体涂层以100g/L涂覆陶瓷蜂窝体。为了这样，首先剧烈搅拌Al2O3的水悬浮液。然后把陶瓷蜂窝体浸泡到载体涂层的悬浮液中。浸泡后，没有粘附的载体涂层被吹出蜂窝体通道。蜂窝体在120℃下干燥，然后在550℃煅烧3小时。通过两个包括即刻干燥和煅烧的浸渍步骤涂覆贵金属。在第一步骤中，通过浸没在亚硫酸铂溶液中浸渍涂覆有载体涂层的蜂窝体。浸渍之后，吹蜂窝体，在120℃下干燥2小时，在550℃下煅烧3小时。在第二步骤中，通过浸没用四氨基硝酸钯溶液浸渍蜂窝体。然后再次吹蜂窝体，在120℃干燥2小时，然后在550℃下煅烧3小时。
对比例3
采用“初湿含浸法”用酸性Pt-(NO3)2溶液负载干燥的H-BEA-35。为了这样，用47.1g含有3.2wt.-%Pt的Pt-(NO3)2溶液浸渍48.5g H-BEA-35。浸渍之后，材料在120℃下干燥过夜然后在氩气下煅烧。在550℃下煅烧5小时，预先设置的升温速率为2K/min。制备好的Pt-BEA粉末含有3wt.-%Pt。
然后用粉状的Pt-BEA材料涂覆堇青石蜂窝催化剂。为了这样，将33.3g Pt-BEA材料，57g H-BEA35和29.4g阿克苏硅(粘结材料，含有34wt.%SiO2)分散在300ｇ水中，然后在行星式球磨机以350rpm转速研磨，采用5分钟间歇方式研磨30分钟研磨成载体涂层。每次将悬浮液转移到塑料瓶中，用以涂覆堇青石蜂窝体(200cpsi)。获得的涂覆量为100g/L w/c。涂覆后，蜂窝体在550℃下煅烧5h。
所有催化剂蜂窝体中的贵金属掺杂量在下面的表3中列出。
载体涂层 贵金属含量[g/L]
本发明的催化剂 Pt-BEA150 Pt0.54
对比例1 TiO2/Al2O3 Pt0.66Pd0.13
对比例2 Al2O3 Pt1.32Pd0.26
对比例3 Pt-BEA35 Pt0.97
表3：贵金属含量
催化剂测试
测定本发明的催化剂在GHSV为40000h-1下在空气中的180ppmv乙酸乙酯氧化时的性能，并与常规参考材料的性能比较。测试结果包含在图1中(数据在表4-7中)。在比较对比例3时，性能数据被放大到可比较的活性蜂窝体表面积，其中>90%转化率的点被省略。图2(数据在表8中)显示对贵金属掺杂量作图，225℃时转化率的比较。结果显示本发明的催化剂性能提高是比较清楚的。
表4
表5
表6
表7
表8

Claims (10)

1.催化剂，包括含有贵金属的微孔BEA沸石材料和含有SiO2的多孔粘结剂，其特征在于所述催化剂的微孔相对于所述催化剂的总孔隙体积的比例为70％以上，所述微孔的直径小于1纳米，所述催化剂的总孔隙体积为100mm3/g以上。
2.根据权利要求1所述的催化剂，其特征在于所述沸石材料的铝的比例为2mol.％以下。
3.根据权利要求1或2所述的催化剂，其特征在于所述沸石材料含有0.5-6.0wt.％的贵金属。
4.根据权利要求1或2所述的催化剂，其特征在于所述沸石材料/粘结剂的重量比为80:20-60:40。
5.根据权利要求1或2所述的催化剂，其特征在于所述催化剂的BET表面积为10-800m2/g。
6.根据权利要求1或2所述的催化剂，其特征在于所述贵金属选自于由铑、铱、钯、铂、钉、锇、金和银组成的组或者所指定的贵金属的合金。
7.根据权利要求1或2所述的催化剂，其特征在于所述贵金属颗粒位于所述沸石材料的内部孔隙体系。
8.根据权利要求1-7中任一项所述的催化剂的制备方法，包括以下步骤：
a)将贵金属前驱体化合物引入到微孔BEA沸石材料中；
b)煅烧负载有所述贵金属前驱体化合物的所述BEA沸石材料；
c)混合负载有所述贵金属前驱体化合物的所述BEA沸石材料和含有SiO2的多孔粘结剂以及溶剂；
d)干燥并且煅烧包含负载有所述贵金属前驱体化合物的所述BEA沸石材料和粘结剂的混合物。
9.根据权利要求8所述的方法，其特征在于在所述步骤c)中得到的所述混合物应用于载体。
10.根据权利要求1-7中任一项的催化剂或者根据权利要求8或9的方法制备的催化剂作为氧化催化剂的应用。
CN201280024064.4A 2011-05-18 2012-05-18 用于氧化有机污染物的具有特别显著的疏水性的低温氧化催化剂 Expired - Fee Related CN103534027B (zh)

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