CN102186564A - 包含过渡金属的硅铝酸盐沸石 - Google Patents

包含过渡金属的硅铝酸盐沸石 Download PDF

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Publication number
CN102186564A
CN102186564A CN2009801410212A CN200980141021A CN102186564A CN 102186564 A CN102186564 A CN 102186564A CN 2009801410212 A CN2009801410212 A CN 2009801410212A CN 200980141021 A CN200980141021 A CN 200980141021A CN 102186564 A CN102186564 A CN 102186564A
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China
Prior art keywords
aluminosilicate zeolite
zeolite catalyst
catalyst
transition metal
aluminosilicate
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CN2009801410212A
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English (en)
Inventor
G·R·钱德勒
N·R·科林斯
R·傅国新
A·N·M·格林
P·R·菲利普斯
R·R·拉加拉姆
S·D·赖德
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Johnson Matthey PLC
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Johnson Matthey PLC
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Application filed by Johnson Matthey PLC filed Critical Johnson Matthey PLC
Priority to CN201510461365.9A priority Critical patent/CN105148982A/zh
Publication of CN102186564A publication Critical patent/CN102186564A/zh
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Abstract

一种合成硅铝酸盐沸石催化剂，其含有选自下面的至少一种催化活性过渡金属：Cu，Fe，Hf，La，Au，In，V，镧系元素和VIII族过渡金属，该硅铝酸盐沸石是小孔硅铝酸盐沸石，其最大环尺寸是八个四面体原子，其中通过扫描电子显微镜所测量的该硅铝酸盐沸石的平均晶粒尺寸是>0.50微米。

Description

包含过渡金属的硅铝酸盐沸石
本发明涉及一种合成硅铝酸盐沸石催化剂，其含有至少一种催化活性过渡金属。该沸石可以用于使用含氮还原剂来选择性催化还原(SCR)废气(例如来自内燃机的废气)中的氮氧化物。
在含有至少一种过渡金属的沸石催化剂的存在下，通过将NOx与含氮还原剂例如氨或者氨前体例如尿素进行接触，来将气体中的氮氧化物(NOx)转化成为氮气是已知的，并且已经提出采用这种技术来处理从车用贫燃内燃机中排出的NOx，参见例如W. Addy Majewski在www.dieselnet.com上发表的DieselNet Technology Guide “Selective Catalytic Reduction”2005.05d修订版。
US专利No.4544538公开了一种具有菱沸石(CHA)晶体结构的合成沸石，称作SSZ-13，其是使用结构引导剂（Structure Directing Agent）(SDA)例如N，N，N-三甲基-1-金刚烷铵阳离子来制备的。该SSZ-13可以与过渡金属例如稀土元素，Mn，Ca，Mg，Zn，Cd，Pt，Pd，Ni，Co，Ti，Al，Sn，Fe和Co进行离子交换，来用于例如烃转化反应中。
US专利No.6709644公开了一种具有小晶粒尺寸(平均<0.5微米)的菱沸石(CHA)晶体结构的合成沸石，称作SSZ-62。SSZ-62还可以使用N，N，N-三甲基-1-金刚烷铵阳离子SDA来制备。US6709644的实施例1比较了SSZ-62的平均晶体大小与SSZ-13的平均晶体大小。该文献建议SSZ-62可以用于转化低级醇的方法中或者该沸石可以与铜或者钴交换，来用于NOx在稀薄气流中例如内燃机中的催化还原中。但是，小的和大的晶粒尺寸材料的活性仅仅用甲醇到烯烃的反应来说明。
在我们的2008年4月24日申请的国际专利申请No.PCT/GB2008/001451中，我们解释了在来自可移动柴油发动机的NOx的尿素和/或 NH3 SCR中，可以考虑过渡金属/沸石催化剂例如Cu/Beta和/或Fe/Beta，来满足新的排放标准。这些催化剂被要求在排放条件下能够经受住相当的高温，并且还可以曝露于相当高量的烃(HC)，该烃能够吸附到沸石的孔上或者孔中。所吸附的HC会如下来影响这些金属沸石催化剂的NH3 SCR活性：通过阻塞活性位置或者阻塞NH3-NOx反应接近该活性位置。此外，这些所吸附的HC物质会随着催化系统温度的升高而被氧化，产生大量的放热，这会热损坏或者水热损坏所述催化剂。所以令人期望的是当大量的HC从发动机排放出来时，使得HC在SCR催化剂上的吸附最小，特别是在冷起动过程中最小。
在我们的PCT/GB2008/001451中，我们建议大孔沸石催化剂的这两个缺点可以通过使用小孔沸石来减少或者克服，其通常允许NH3和NOx扩散到沸石孔中的活性位置，但是其通常阻止烃分子扩散到所述孔中。沸石(其具有小孔尺寸来诱导这种形状选择性，由此阻止较大的烃接近沸石腔孔中的活性金属位置)包括CHA，ERI和LEV。另外，小孔沸石基SCR催化剂产生了较少的N2O，该N2O是NOx还原反应的副产物。
我们研究了硅铝酸盐沸石材料，并且已经非常惊讶的发现对于使用含氮还原剂的SCR方法来说，大的结晶硅铝酸盐沸石材料具有比小的晶粒尺寸的相同的硅铝酸盐沸石材料的更大的活性。
根据一方面，本发明提供一种合成硅铝酸盐沸石催化剂，其含有选自下面的至少一种催化活性过渡金属：Cu，Fe，Hf，La，Au，In，V，镧系元素和VIII族过渡金属，该硅铝酸盐沸石是小孔硅铝酸盐沸石，其最大环尺寸是八个四面体原子，其中通过扫描电子显微镜所测量的该硅铝酸盐沸石的平均晶粒尺寸是>0.50微米。优选的，该至少一种催化活性过渡金属是铜和铁之一。在实施方案中，该沸石可以包含铜和铁二者。
实施例表示了新鲜的和陈化的铜/CHA催化剂的NOx还原活性随着晶粒大小的增加而增加的趋势。
扫描电子显微镜能够测量本发明沸石的形态和晶粒大小。令人期望的是通过SEM所测量的该硅铝酸盐沸石的平均粒度是>0.50微米，但是优选大于1.00微米，例如>1.50微米。在实施方案中，该平均晶粒尺寸是<15.0微米，例如<10.0微米或者<5.0微米。
在实施方案中，本发明的硅铝酸盐沸石催化剂选自最大环尺寸为八个四面体原子的沸石，特别是框架类型代码CHA，ERI和LEV，最优选是CHA。
在该硅铝酸盐沸石的框架类型代码是CHA的情况中，同型框架结构的CHA可以选自例如Linde-D，Linde-R，SSZ-13，LZ-218，Phi和ZK-14。
ERI框架类型代码沸石的材料类型或者同型框架结构可以是例如毛沸石，ZSM-34或者Linde Type T。
LEV框架类型代码的同型框架结构或者材料类型可以是例如插晶菱沸石(levynite)，Nu-3，LZ-132或者ZK-20。
所述催化剂中存在的至少一种过渡金属的总量是0.1-10.0wt%，基于沸石催化剂的总重量，例如0.5-5.0wt%，基于沸石催化剂的总重量。
根据另一方面，本发明提供一种方法，其用于在本发明的硅铝酸盐沸石催化剂存在下，通过将氮氧化物与含氮还原剂接触，来将气体中的该氮氧化物转化成为氮气。
该氮氧化物可以用还原剂中至少100℃的温度，例如大约150℃-750℃的温度进行还原。
在一种具体的实施方案中，该氮氧化物的还原是在氧气存在下进行的。
可以对含氮还原剂的添加进行控制，来将沸石催化剂入口的NH3控制到理论氨的60%-200%，该理论氨是以1：1的NH3/NO和4：3的NH3/NO2来计算的。
在一种具体的实施方案中，其中使用位于该沸石催化剂上游的氧化催化剂，将气体中的一氧化氮氧化成为二氧化氮，然后将所形成的气体与含氮还原剂混合，其后将该混合物供给到沸石催化剂中，其中该氧化催化剂适于产生进入沸石催化剂的气流，该气流的NO：NO2的体积比是大约4：1-大约1：3。
在本发明的方法中，该含氮还原剂是氨本身，肼或者选自下面的氨前体：尿素((NH2)2CO)，碳酸铵，氨基甲酸铵，碳酸氢铵和甲酸铵。
打算用本发明方法处理的含有氮氧化物的气体可以源自于燃烧工艺，特别是内燃机的燃烧方法，例如固定的来源，或者优选是车用贫燃内燃机。
根据另一方面，本发明提供一种用于车用贫燃内燃机的排气系统，该系统包含用于输送流动废气的管道，含氮还原剂源，布置在该废气的流路中的合成硅铝酸盐沸石催化剂，该催化剂含有选自下面的至少一种催化活性过渡金属：Cu，Fe，Hf，La，Au，In，V，镧系元素和VIII族过渡金属，该硅铝酸盐沸石是小孔硅铝酸盐沸石，其最大环尺寸是八个四面体原子，和这样的装置，该装置用于将含氮还原剂计量供给到沸石催化剂上游的流动废气中，其中通过扫描电子显微镜所测量的该硅铝酸盐沸石的平均晶粒尺寸是>0.50微米。
为了能够更充分的理解本发明，提供了下面的实施例，其仅仅是为了举例。
实施例1-沸石样品的制备
沸石A
小晶粒CHA是根据US6709644的实施例1来制备(其整个内容在此引入作为参考)。
沸石B
大晶粒CHA是通过同样公开在International Zeolite Association Synthesis Commission网站http://www.iza-online.org/synthesis/上的S. I. Zones和R A. Van Nordstrand，Zeolites 8(1988)166(其整个内容在此引入作为参考)的制造SSZ-13的方法，如下来制备的：
源材料是：
氢氧化钠(1N)，(Baker，试剂级)；
N，N，N，三甲基-1-金刚烷氢氧化铵(RN-OH)(0.72M)；
去离子水；
氢氧化铝(Reheis F-2000干凝胶，50%Al2O3)；和
热解法二氧化硅(Cab-Q-Sil，M5级，97%SiO2)。
该反应混合物是如下来制备的：
(1)2.00g1N NaOH +2.78g 0.72 M RN OH +3.22g水，依次加入到Parr 23mL高压釜的聚四氟乙烯杯中；
(2)(1)+0.05g氢氧化铝，混合直到溶液澄清；
(3)(2)+0.60g热解法二氧化硅，混合直到均匀。
该反应混合物进行结晶：
在温度160℃的聚四氟乙烯衬里的23mL高压釜(Parr型号4745)不搅拌放置4天；
在冷却到室温后，将该混合物过滤，用软化水清洗，并且在空气中干燥一整夜。
将所形成的产物用粉末x射线衍射法来表征，并且确定为：
CHA沸石，并且通过ICP所测量的SiO2/Al2O3比例为28。
SEM分析显示：2-5立方微米。
沸石C
制备摩尔组成为60 SiO2-1.5 Al2O3-6 Na2O-12NNNAnOH-2640 H2O的反应混合物，这里NNNAnOH是结构导向剂(SDA)或者模板N，N，N-三甲基金刚烷氢氧化铵。
该反应是使用作为二氧化硅源的cab-o-sil M5(Cabot Corporation)，铝酸钠(BDH Ltd)，氢氧化钠(Alfa Aesar)来准备的。SDA(NNNAnOH)是按照US专利No.4544538所述的方法来制备的(其整个内容在此引入作为参考)。称量所需量的SDA溶液，加入NaOH，并且搅拌直到它溶解。然后在搅拌下加入铝酸钠固体，搅拌直到它溶解。然后混入cab-o-sil，将所形成的混合物转移到1L的不锈钢高压釜中。密封该高压釜，将该混合物在搅拌(300rpm)下加热到165℃，持续4天。
通过粉末x射线衍射法确定所形成的产物是CHA类型的材料。视觉上，该产物晶体是大约2微米的边长。该产物组成的二氧化硅-氧化铝比例(SAR)为24：1。
实施例2 –3wt%Cu/硅铝酸盐沸石的制备
通过常规的湿填充方法，使用乙酸铜作为铜前体，将铜沉积到实施例1所制备的沸石A，B和C上。对于10g的硅铝酸盐沸石来说，将0.471g的乙酸铜溶解到足量的水中来润湿该硅铝酸盐沸石材料。将该溶液加入到硅铝酸盐沸石材料中，并且搅拌。将该湿粉末在105℃干燥，其后在500℃煅烧2小时。在煅烧后，大部分的铜被认为是作为氧化铜(II)而存在的。
根据这个实施例所制备的铜负载的催化剂被称作催化剂A，B和C。根据实施例2所制备的催化剂被称作“新鲜催化剂A-C”。
实施例3 –水热陈化
将根据实施例2所制备的新鲜催化剂A-C在750°C的含有10%氧气，10%水和平衡量的氮气的气氛中进行24小时的水热陈化。该水热陈化的催化剂被称作“陈化的催化剂A-C”。
表1：不同催化剂(新鲜)的表面积，二氧化硅氧化铝比例，晶体大小和铜负载量。
菱沸石硅铝酸盐代码 BET表面积 二氧化硅/氧化铝比例(SAR) 平均SEM晶体大小(微米)* 铜负载wt%
A 784 26 0.15 3
B 634 24 0.5 3
C 616 24 1.4 3
*将样品分散到甲醇中，并且经历20min的超声波，将一滴该液体放置到常规的碳填充的扫描电子显微镜(SEM)的台面上。计数和估计大小是通过数均的数字粒度分析，基于对图像的每个像素的亮度进行“阈值化”，并且利用粒子和背景之间的亮度差异来测量的。该软件假定每个所测量的物体是圆形/球形的。
实施例4 –活性测试
表2给出了在200°C或者400°C的入口气体温度时，实施例2和3的催化剂A-C的NOx转化率。NOx的还原性能是如下来测量的：在实验室反应器中，在粉末样品上，将催化剂在气体混合物中以5°C/分钟的速度升温，该气体混合物含有500ppm的NO和NH3，10%O2，10%H2O和N2。
表2：新鲜的催化剂在200℃和400℃的催化剂入口气体温度和750℃的24小时陈化条件下的NOx转化率
*参见表1的备注。
从表2中可以看出，催化剂的活性通常符合活性随着晶粒大小的增大而增大这样的趋势。因此我们得出这样的结论，即，与由相同的硅铝酸盐沸石材料的较小的晶体所制备的催化剂相比，较大的晶粒尺寸的硅铝酸盐沸石材料令人惊讶的在新鲜的或者水热陈化中具有更大的活性。

Claims (23)

1.一种合成硅铝酸盐沸石催化剂，其含有选自下面的至少一种催化活性过渡金属：Cu、Fe、Hf、La、Au、In、V、镧系元素和VIII族过渡金属，该硅铝酸盐沸石是小孔硅铝酸盐沸石，其最大环尺寸是八个四面体原子，其中通过扫描电子显微镜所测量的该硅铝酸盐沸石的平均晶粒尺寸是>0.50微米。
2.根据权利要求1的硅铝酸盐沸石催化剂，其中该至少一种催化活性过渡金属是铜、铁或者铜和铁。
3.根据权利要求1或者2的硅铝酸盐沸石催化剂，其中该至少一种催化活性过渡金属是铜。
4.根据权利要求1、2或者3的硅铝酸盐沸石催化剂，其中该平均晶粒尺寸是>1.00微米。
5.根据权利要求1、2、3或者4的硅铝酸盐沸石催化剂，其中该平均晶粒尺寸是>1.50微米。
6.根据任何一个前述权利要求的硅铝酸盐沸石催化剂，其中该平均晶粒尺寸是<15.00微米。
7.根据任何一个前述权利要求的硅铝酸盐沸石催化剂，其中该硅铝酸盐沸石选自框架类型代码CHA、ERI和LEV。
8.根据权利要求1-6中任何一个的硅铝酸盐沸石催化剂，其中该硅铝酸盐沸石选自框架类型代码CHA。
9.根据权利要求7或者8的硅铝酸盐沸石催化剂，其中CHA的同型框架结构选自Linde-D、Linde-R、SSZ-13、LZ-218、Phi和ZK-14。
10.根据权利要求7的硅铝酸盐沸石催化剂，其中ERI的材料类型或者同型框架结构是毛沸石、ZSM-34或者Linde Type T。
11.根据权利要求7的硅铝酸盐沸石催化剂，其中LEV的材料类型或者同型框架结构是插晶菱沸石、Nu-3、LZ-132或者ZK-20。
12.根据任何一个前述权利要求的硅铝酸盐沸石催化剂，其中该催化剂中所存在的至少一种过渡金属的总量是0.1-10.0wt%，基于沸石催化剂的总重量。
13.根据权利要求12的硅铝酸盐沸石催化剂，其中该催化剂中所存在的至少一种过渡金属的总量是0.5-5.0wt%，基于沸石催化剂的总重量。
14.一种将气体中的氮氧化物转化成为氮气的方法，其是通过在任何一个前述权利要求的硅铝酸盐沸石催化剂存在下，将氮氧化物与含氮还原剂接触而进行的。
15.根据权利要求14的方法，其中该氮氧化物是用还原剂在至少100℃的温度下进行还原的。
16.根据权利要求15的方法，其中该温度是大约150℃-750℃。
17.根据权利要求14、15或者16的方法，其中该氮氧化物的还原是在氧气存在下进行的。
18.根据权利要求14、15、16或者17的方法，其中对含氮还原剂的添加进行控制，来将沸石催化剂入口的NH3控制到理论氨的60%-200%，该理论氨是以1：1的NH3/NO和4：3的NH3/NO2来计算的。
19.根据权利要求14-18中任何一个的方法，其中使用位于该沸石催化剂上游的氧化催化剂，将气体中的一氧化氮氧化成为二氧化氮，然后将所形成的气体与含氮还原剂混合，其后将该混合物供给到沸石催化剂中，其中该氧化催化剂适于产生进入沸石催化剂的气流，该气流的NO：NO2的体积比是大约4：1-大约1：3。
20.根据权利要求14-19中任何一个的方法，其中该含氮还原剂是氨本身，肼或者选自下面的氨前体：尿素((NH2)2CO)、碳酸铵、氨基甲酸铵、碳酸氢铵和甲酸铵。
21.根据权利要求14-20中任何一个的方法，其中该含有氮氧化物的气体源自于燃烧工艺。
22.根据权利要求21的方法，其中该燃烧工艺是燃料在车用贫燃内燃机中的燃烧。
23.一种用于车用贫燃内燃机的排气系统，该系统包含用于输送流动废气的管道，含氮还原剂源，布置在该废气的流路中的合成硅铝酸盐沸石催化剂，该催化剂含有选自下面的至少一种催化活性过渡金属：Cu、Fe、Hf、La、Au、In、V、镧系元素和VIII族过渡金属，该硅铝酸盐沸石是小孔硅铝酸盐沸石，其最大环尺寸是八个四面体原子，和这样的装置，该装置用于将含氮还原剂计量供给到沸石催化剂上游的流动废气中，其中通过扫描电子显微镜所测量的该硅铝酸盐沸石的平均晶粒尺寸是>0.50微米。
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