CN107405570B - 对于BaAl2O4形成具有改善的稳定性的NOx捕获催化剂载体材料 - Google Patents
对于BaAl2O4形成具有改善的稳定性的NOx捕获催化剂载体材料 Download PDFInfo
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- CN107405570B CN107405570B CN201680014426.XA CN201680014426A CN107405570B CN 107405570 B CN107405570 B CN 107405570B CN 201680014426 A CN201680014426 A CN 201680014426A CN 107405570 B CN107405570 B CN 107405570B
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- oxide
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- cerium
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- 239000000463 material Substances 0.000 title claims abstract description 54
- 239000003054 catalyst Substances 0.000 title abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 30
- 238000004519 manufacturing process Methods 0.000 claims abstract description 5
- 239000002243 precursor Substances 0.000 claims description 73
- 239000011777 magnesium Substances 0.000 claims description 66
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 45
- 229910052684 Cerium Inorganic materials 0.000 claims description 40
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 33
- 239000000203 mixture Substances 0.000 claims description 21
- 239000000725 suspension Substances 0.000 claims description 21
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 19
- 229910052748 manganese Inorganic materials 0.000 claims description 19
- 239000011572 manganese Substances 0.000 claims description 19
- 229910015999 BaAl Inorganic materials 0.000 claims description 14
- 239000000395 magnesium oxide Substances 0.000 claims description 13
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 11
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 9
- 238000001694 spray drying Methods 0.000 claims description 9
- 238000001354 calcination Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 150000002823 nitrates Chemical class 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 5
- 150000004679 hydroxides Chemical class 0.000 claims description 4
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 4
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 claims description 4
- 230000032683 aging Effects 0.000 claims description 3
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 3
- MMKQUGHLEMYQSG-UHFFFAOYSA-N oxygen(2-);praseodymium(3+) Chemical compound [O-2].[O-2].[O-2].[Pr+3].[Pr+3] MMKQUGHLEMYQSG-UHFFFAOYSA-N 0.000 claims description 3
- 229910003447 praseodymium oxide Inorganic materials 0.000 claims description 3
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 claims description 2
- 150000001242 acetic acid derivatives Chemical class 0.000 claims 1
- 239000012876 carrier material Substances 0.000 claims 1
- -1 hydrated oxides Chemical class 0.000 claims 1
- 229910052749 magnesium Inorganic materials 0.000 claims 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims 1
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 abstract description 27
- 229910016010 BaAl2 Inorganic materials 0.000 abstract description 12
- 238000003860 storage Methods 0.000 abstract description 9
- 150000001553 barium compounds Chemical class 0.000 abstract description 5
- 239000007789 gas Substances 0.000 abstract description 5
- 229910000420 cerium oxide Inorganic materials 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 16
- 239000000843 powder Substances 0.000 description 16
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 15
- 239000000243 solution Substances 0.000 description 10
- 238000002441 X-ray diffraction Methods 0.000 description 8
- 229910052788 barium Inorganic materials 0.000 description 8
- 239000011232 storage material Substances 0.000 description 7
- ZZBAGJPKGRJIJH-UHFFFAOYSA-N 7h-purine-2-carbaldehyde Chemical compound O=CC1=NC=C2NC=NC2=N1 ZZBAGJPKGRJIJH-UHFFFAOYSA-N 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000007900 aqueous suspension Substances 0.000 description 5
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical compound [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 229940071125 manganese acetate Drugs 0.000 description 4
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 4
- 150000004703 alkoxides Chemical class 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical class [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000006069 physical mixture Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000003878 thermal aging Methods 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- BYDYILQCRDXHLB-UHFFFAOYSA-N 3,5-dimethylpyridine-2-carbaldehyde Chemical compound CC1=CN=C(C=O)C(C)=C1 BYDYILQCRDXHLB-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229910002927 BaMnO3 Inorganic materials 0.000 description 1
- 229910016978 MnOx Inorganic materials 0.000 description 1
- 159000000021 acetate salts Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- ITHZDDVSAWDQPZ-UHFFFAOYSA-L barium acetate Chemical compound [Ba+2].CC([O-])=O.CC([O-])=O ITHZDDVSAWDQPZ-UHFFFAOYSA-L 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000012702 metal oxide precursor Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
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Abstract
本发明涉及用于生产用于氮氧化物储存组分的载体材料的方法，其适用于处理来自贫燃发动机的废气的催化剂，以及按照所述方法制造的载体材料，其对于与钡化合物反应以形成BaAl2O4是稳定的。
Description
技术领域
本发明涉及用于生产用于氮氧化物储存组分的载体材料的方法，其适用于处理来自贫燃发动机(lean-burn engine)的废气(exhaust gas)的催化剂，以及按照所述方法可获得的载体材料，其对于与钡化合物的反应以形成 BaAl2O4是稳定的。
背景技术
为了减少在贫燃汽油发动机和尤其是柴油发动机的废气中的NOx含量，需要指定的NOx后处理***(NOx after-treatment system)。在三路催化(three-way catalysis)中，在几乎化学计量条件下，NOx到N2的还原是可能的。在稀燃发动机的氧化条件下，这种还原是不可能的。因此，已开发了特殊的废气后处理催化剂，其含有在贫燃条件下能够储存NOx(例如作为硝酸盐)的材料。通过施加较少的化学计量(short stoichiometric)或较多的操作条件(rich operation condition)，那么可以将储存的NOx转化成氮气并再生储存材料。这种催化剂通常被称为(贫)NOx捕获催化剂((lean) NOx-trap catalyst)并且例如描述在EP 1317953 A1中。
如在EP 1317953 A1中所描述的，NOx捕获催化剂含有氮氧化物储存材料，其由存储成分组成，所述存储成分以高度分散的方式沉积在适宜的载体材料(support material)上，以产生与废气相互作用的大面积。能够以硝酸盐的形式储存氮氧化物的材料是例如碱土金属，尤其是钡的氧化物、碳酸盐或氢氧化物。
适宜的载体材料必须提供高比表面积和高热稳定性以确保最终催化剂的长期耐久性。此外，载体材料的化学成分和性能会影响NOx捕获催化剂的氮氧化物转化效率和温度操作窗口。
关于在本领域中被充分描述的用作载体材料的之前提到的特性的有益材料是均匀的Mg/Al混合氧化物，其中，基于氧化物的总重量，镁氧化物浓度为1至40wt.％。
术语Mg/Al混合氧化物描述在原子尺度上两种氧化物的混合物，因此排除通过用镁氧化物前体溶液来浸渍铝氧化物所制备的两种单独的氧化物以及材料的物理混合物。优选通过Mg/Al混合氧化物前体的锻烧来获得这种类型的Mg/Al混合氧化物，所述Mg/Al混合氧化物前体是通过醇盐 (alkoxide)的混合物的水解来获得，例如详细描述于DE19503522A1(＝US 6517795)。
通过利用均匀的Mg/Al混合氧化物载体材料(其进一步掺杂有基于铈的氧化物，例如通过用铈氧化物和/或镨氧化物来涂布Mg/Al混合氧化物)，来进一步改善NOx捕获催化剂的活性和耐久性。WO 2005/092481 A1要求保护，当与Mg/Al混合氧化物和铈氧化物的物理混合物相比时，在催化剂性能中观察到的益处与用铈氧化物来掺杂Mg/Al混合氧化物密切相关。
然而，结果表明，当用作现有技术(state-of-the-art)的载体材料的铈氧化物掺杂的均匀的Mg/Al混合氧化物与适宜的作为氮氧化物储存组分的钡化合物结合时，热老化处理(在850℃下，4小时)导致形成BaAl2O4。众所周知的是(例如，Jang et.al,CatalysisLetters 77(2001)21)，通过存储成分与部分的载体材料的反应形成BaAl2O4导致储存材料的NOx捕获效率的恶化，这是由于这种化合物没有以硝酸盐的形式来储存氮氧化物的能力。因此，为了进一步增强NOx捕获催化剂的热耐久性，需要这样的载体材料，其对于无活性(inactive)BaAl2O4的形成具有改善的稳定性。
包含锰氧化物和/或铈和锰氧化物的混合物的材料用于汽车排放控制催化剂是本领域已知的。例如US 20120240554 A1要求保护使用 MnOx-CeO2混合氧化物颗粒作为氧化催化剂来促进NO到NO2的转化。
在NOx捕获催化剂中，连同铝氧化物一起，使用锰和铈的氧化物是本领域已知的并由Le Phuc(Le Phuc,et al:"Nox Removal Efficiency and Ammonia Selectivityduring the NOx storage-reducion process over Pt/BaO (Fe,Mn,Ce)Al2O3 modelcatalysts.Part II-Influence of Ce and Mn-Ce addition,Applied Catalysis B；Environmental 362-371)所教导。在此参考文献中，通过浸渍过程，连同硝酸钡一起，将Mn和Ce的硝酸盐同时加入铝氧化物。此文献公开了，Mn和Ce的添加会改善存储率，以及当一起添加Ce和Mn时，观测到有益效果。现有技术未讨论BaAl2O4的问题。
此外，如本说明书的正文所示，当经历热老化处理(在850℃下4小时)时，现有技术材料导致BaAl2O4形成，其是本发明要解决的非常相同的问题。
因此本发明的目的是提供适用于NOx捕获催化剂的载体材料，其包含均匀的Mg/Al混合氧化物，所述均匀的Mg/Al混合氧化物优选掺杂有基于铈的氧化物以提供上述有利的特性并且另外地对于与钡存储成分反应以形成BaAl2O4是稳定的。
发明内容
本申请的发明人已经令人惊讶地发现用于制造这样的载体材料的新颖方法。
根据本发明的一个方面，提供了用于制造载体材料的方法，所述载体材料对于形成BaAl2O4是稳定的，包括以下步骤：
i)提供第一悬浮液(可选地掺杂的)，包含均匀的Mg/Al混合氧化物前体；
ii)干燥第一悬浮液；
iii)煅烧Mg/Al混合氧化物前体以获得煅烧的Mg/Al混合氧化物；
iv)再悬浮煅烧的Mg/Al混合氧化物以获得第二悬浮液，其包含Mg/Al 混合氧化物；
v)用包含锰氧化物前体的前体掺杂再悬浮的煅烧的Mg/Al混合氧化物以形成掺杂有至少锰的Mg/Al混合氧化物；
vi)干燥第二悬浮液；以及
vii)煅烧掺杂有至少锰的Mg/Al混合氧化物以形成掺杂的Mg/Al混合氧化物。
上述方法可选地包括以下进一步的步骤：在第一悬浮液中用基于铈的氧化物前体掺杂均匀混合的Mg/Al混合氧化物前体。
附图说明
现在将参考以下非限制性实施例和附图来描述本发明，其中：
图1示出在850℃下热处理4小时以后，实施例1至3和比较实施例 1至2的材料的一部分的X射线衍射图案，其显示通过将锰氧化物加入铈氧化物掺杂的Mg/Al混合氧化物，对于BaAl2O4形成，对于载体稳定性的影响；以及
图2示出在850℃下热处理4小时以后，实施例1和比较实施例2以及比较实施例3和4的材料的一部分的X射线衍射图案，其显示不同的制备方法对于BaAl2O4形成，对于稳定性的影响。
图3示出在850℃下热处理4小时以后，实施例5的材料的一部分的 X射线衍射图案，其显示通过缺乏在40°2θ处反射，对于BaAl2O4形成的稳定性。
具体实施方式
可以连同稀土元素的氧化物的前体(稀土氧化物前体)(其不同于基于铈的氧化物前体，如镧氧化物、钕氧化物、钇氧化物、镨氧化物或它们的混合物)一起添加基于铈的氧化物前体，以增加基于铈的氧化物的热稳定性或调节基于铈的氧化物的化学性能。
根据一种实施方式，通过本发明领域的已知方法，即通过相应醇盐的混合物的水解(其产生水滑石和勃姆石的混合物)，来制备所提供的Mg/Al 混合氧化物前体。在(掺杂的)均匀的Mg/Al混合氧化物中镁氧化物的量为 1至wt.40％，优选10至wt.30％。除掺杂材料以外的剩余物是Al2O3。通过在DE 19503522 A1(通过引用并入本文)中描述的方法来制备优选的 Mg/Al混合氧化物前体。
如上所述，所述方法可选地包括用基于铈的氧化物来掺杂Mg/Al混合氧化物。当此选项是优选的时，将基于铈的氧化物前体加入Mg/Al混合氧化物前体的第一悬浮液。本发明包括这样的选项，其中连同稀土氧化物前体一起添加基于铈的氧化物前体。
基于铈的氧化物前体和进一步的稀土氧化物前体可以是彼此独立的可溶性盐，例如包含乙酸盐和硝酸盐的可溶性盐，或不溶性前体，例如包含水合氧化物、氢氧化物或碳酸盐的那些。
在干燥和随后锻烧步骤以后，可选地连同稀土氧化物一起将基于铈的氧化物精细地分散在均匀的Mg/Al混合氧化物(其源自在锻烧步骤中 Mg/Al混合氧化物前体的分解)内。干燥步骤可以是本领域中已知的任何方法并且优选是喷雾干燥。本发明的载体材料包括最高达50wt.％的基于铈的氧化物。
根据一种实施方式，包含锰氧化物前体的前体可以完全由锰氧化物前体组成。在这种情况下，所述方法包括添加5至20％wt的锰氧化物(作为ΜnO2计算)。包含锰氧化物前体的前体可以包含锰氧化物和铈氧化物前体的混合物。在这种情况下，将可选的基于铈的氧化物掺杂的均匀的 Mg/Al混合氧化物再分散在水中并与用于锰氧化物的前体结合。可选地，优选和锰氧化物前体同时地，将基于铈的氧化物前体和/或稀土氧化物前体 (不同于基于铈的氧化物前体)加入第二悬浮液。金属氧化物前体包含任何可溶性或不溶性盐以及优选包含乙酸盐。在干燥第二悬浮液以后，优选通过喷雾干燥，锻烧步骤将前体转化成锰氧化物以及可选地基于铈的氧化物。本发明人已经发现，正是通过这种特定方法的锰氧化物顺序加入混合氧化物才导致本发明的优点。
当本发明的载体材料与适宜的钡化合物(其作为氮氧化物储存组分是活性的，用来制造氮储存材料)结合时，在用于贫燃排气***的850℃的相关温度下随后的热老化4小时不会导致BaAl2O4的出现。缺乏BaAl2O4的特征在于，在热老化储存材料的粉末X射线衍射图案中相应的特征信号是不可见的。尤其是，当它们未由在X射线衍射图案中存在的其他相的许多反射叠合时，在BaAl2O4结构的约40°2θ(Theta)处的(020)和(112)反射用于评估。
显示的是，如果不是通过顺序添加而是通过不同的、常规浸渍过程来将锰氧化物加入铈氧化物掺杂的Mg/Al混合氧化物或如果同时添加Mn、 Ce和Ba(如在现有技术中所描述的)，则无法获得本发明的优点，即，对于BaAl2O4的形成具有出色的稳定性。不希望被理论所束缚，假设由于本发明的方法的结果，在载体材料中的锰氧化物以特定的分散状态存在，其有助于Ba存储成分至非有害BaMnO3的优选的反应。与BaAl2O4相反，已知BaMnO3以正模式(positive mode)与氮氧化物相互作用，从而导致在热老化以后储存材料的高保留NOx捕获效率。
实验部分
载体材料的制备
实施例1
使混合Mg/Al氧化物前体(Pural MG20，MgO含量为20wt.％)的水悬浮液与乙酸铈溶液混合。在喷雾干燥以后，在950℃下煅烧得到的粉末3 小时以获得铈氧化物掺杂的均匀的Mg/Al混合氧化物。
将粉末再悬浮在水中，球磨并与乙酸锰的溶液混合。喷雾干燥混合物并在550℃下煅烧得到的粉末3小时。载体材料的组成见表I。
实施例2
如在实施例1中所述来制备载体材料，但使用较低量的锰氧化物，如表I所示。
实施例3
如在实施例2中所述来制备载体材料，但使用较低量的锰氧化物，如表I所示。
比较实施例1
在没有添加锰氧化物的情况下来制备载体材料。
使混合Mg/Al氧化物前体(Pural MG20，MgO含量为20wt.％)的水悬浮液与乙酸铈溶液混合。在喷雾干燥以后，在950℃下煅烧得到的粉末3 小时以获得铈氧化物掺杂的均匀的Mg/Al混合氧化物。
比较实施例2
制备了具有与在实施例1中相同组成的载体材料，包括锰氧化物的不同的顺序添加，即，通过利用在本领域中是众所周知的不同的掺杂工艺。
使混合Mg/Al氧化物前体(Pural MG20，MgO含量为20wt.％)的水悬浮液与乙酸铈溶液混合。在喷雾干燥以后，在950℃下煅烧得到的粉末3 小时以获得铈氧化物掺杂的均匀的Mg/Al混合氧化物。然后，通过用乙酸锰的水溶液进行初始湿浸渍来处理粉末，在120℃下干燥以及最后在 550℃下煅烧3小时。
要注意的是，根据本发明，在此比较实施例中，在锰掺杂步骤之前，并不再悬浮煅烧的Mg/Al混合氧化物。
实施例4
如在实施例1中所述制备载体材料，但将乙酸铈和乙酸锰的混合溶液加入悬浮的铈氧化物掺杂的均匀的Mg/Al混合氧化物。载体材料的组成见表1。
实施例5
使混合Mg/Al氧化物前体(Pural MG20，MgO含量为20wt.％)的水悬浮液与铈和钕乙酸盐溶液混合。在喷雾干燥以后，在950℃下煅烧得到的粉末3小时以获得铈氧化物掺杂的均匀的Mg/Al混合氧化物。将粉末再悬浮在水中，球磨并与乙酸锰的溶液混合。喷雾干燥混合物并在550℃下煅烧得到的粉末3小时。载体材料的组成见表I。
表1-载体材料的组成
对于BaAl2 O 4形成，载体材料稳定性的测试(实施例1至5以及比较实施例1和2)
将分别在实施例1-4以及比较实施例1和2中获得的载体材料悬浮于水中，并球磨，直到获得3μm的d50。在添加乙酸钡的水溶液以获得16％的BaO的浓度以后，通过喷雾干燥来获得粉末。首先在550℃下烧制得到的粉末3小时，接着在850℃下热处理4小时。已经发现，当现有技术的材料用作用于钡化合物的载体材料时，这种后者处理会引起BaAl2O4形成。然后通过X射线衍射来研究这些样品，尤其是，评估在约40°2θ处 BaAl2O4的反射的发生。表II总结结果。
表II-载体材料稳定性测试组合物储存材料
图1示出实施例1至3和比较实施例1和2的一部分的X射线衍射图案。显然，当使用实施例1的本发明的载体材料时，在约40°2θ处BaAl2O4相的独特的(020)和(112)反射是缺少的。随着在载体材料内MnO2量减少，可以观测到少量(minor amount)的BaAl2O4相。当按照比较实施例1，在没有添加锰氧化物的情况下，采用现有技术材料的铈氧化物掺杂的Mg/Al 混合氧化物状态时，观测到显著量的BaAl2O4。
比较实施例3
制备过程与由Le Phuc披露的相同。将Ce、Mn和Ba同时加入均匀的Mg/Al混合氧化物，以获得和在实施例1中相同的组成。
首先，在950℃下煅烧Mg/Al混合氧化物前体(Pural MG20，MgO含量为20wt.％)3小时。在60℃和pH 10下，将得到的Mg/Al混合氧化物悬浮在水中。在搅拌下，同时添加铈、锰和钡的硝酸盐，同时通过氨的添加来维持所述pH。在30分钟以后，在80℃以及在空气下，蒸发溶液并在120℃下干燥得到的粉末。在550℃下煅烧干粉末3小时，接着在850℃下热处理4小时。
比较实施例4
制备过程与由Le Phuc所披露的相同。同时将Mn和Ba加入铈氧化物掺杂的均匀的Mg/Al混合氧化物以获得和实施例1中相同的组成。
使混合Mg/Al氧化物前体(Pural MG20，MgO含量为20wt.％)的水悬浮液与乙酸铈溶液混合。在喷雾干燥以后，在950℃下煅烧得到的粉末3 小时以获得铈氧化物掺杂的均匀的Mg/Al混合氧化物。在60℃和pH 10 下，将得到的Mg/Al混合氧化物悬浮于水中。在搅拌下，同时添加锰和钡的硝酸盐，同时通过氨的添加来维持所述pH。在30分钟以后，在80℃以及在空气下蒸发溶液，然后在120℃下干燥得到的粉末。在550℃下煅烧干粉末3小时，接着在850℃下热处理4小时。
表III
图2示出实施例1(新颖的和发明性的载体材料)以及比较实施例2和比较实施例3和4的一部分的X射线衍射图案。所有材料具有如总结于表 III中的可比较成分，但它们的制备过程有所不同。比较实施例2不包括再分散步骤以及比较实施例3包括Ce、Mn和Ba的同时添加。这表明，仅可以通过由本发明披露的方法才能获得对于BaAl2O4的形成稳定的载体材料，因为仅在实施例1至4中制造的材料的特征在于在X射线衍射图案中没有BaAl2O4的特征反射。
Claims (13)
1.一种用于制造载体材料的方法，包括以下步骤：
i)提供第一悬浮液，所述第一悬浮液包含均匀的Mg/Al混合氧化物前体；
ii)干燥所述第一悬浮液；
iii)煅烧所述Mg/Al混合氧化物前体以获得煅烧的Mg/Al混合氧化物；
iv)再悬浮所述煅烧的Mg/Al混合氧化物以获得包含Mg/Al混合氧化物的第二悬浮液；
v)用包含锰氧化物前体的前体掺杂所述再悬浮的煅烧的Mg/Al混合氧化物以形成掺杂有至少锰的Mg/Al混合氧化物，其中所述包含锰氧化物前体的前体完全由锰氧化物前体组成或者所述包含锰氧化物前体的前体由锰氧化物前体和以下各项的混合物组成：
a)基于铈的氧化物前体，或
b)除了基于铈的氧化物前体之外的稀土氧化物前体，或
c)基于铈的氧化物前体和除了基于铈的氧化物前体之外的稀土氧化物前体；
vi)干燥包含掺杂有至少锰的Mg/Al混合氧化物的悬浮液；以及
vii)煅烧所述掺杂有至少锰的Mg/Al混合氧化物以形成掺杂的Mg/Al混合氧化物。
2.根据权利要求1所述的方法，包括以下进一步的步骤：将在所述第一悬浮液中的均匀混合的Mg/Al混合氧化物前体和基于铈的氧化物前体放在一起。
3.根据权利要求1或2所述的方法，包括以下进一步的步骤：将包含均匀混合的Mg/Al混合氧化物前体的所述第一悬浮液和基于铈的氧化物前体以及除了基于铈的氧化物前体之外的稀土氧化物前体放在一起。
4.根据权利要求3所述的方法，其中，除了基于铈的氧化物前体之外的所述稀土氧化物前体包含镧氧化物或镨氧化物或钕氧化物或钇氧化物或它们的混合物。
5.根据权利要求1所述的方法，其中，在每种情况下相对于所述掺杂的Mg/Al混合氧化物，在所述均匀的Mg/Al混合氧化物前体内，作为MgO计算的镁氧化物的量为1至40wt.％。
6.根据权利要求1所述的方法，其中，在每种情况下相对于所述掺杂的Mg/Al混合氧化物，在所述均匀的Mg/Al混合氧化物前体内，作为MgO计算的镁氧化物的量为10至30wt.％。
7.根据权利要求1所述的方法，其中，所述第一悬浮液的悬浮介质和所述第二悬浮液的悬浮介质是水。
8.根据权利要求3所述的方法，其中，所述基于铈的氧化物前体和/或除了基于铈的氧化物前体之外的所述稀土氧化物前体选自包含乙酸盐、硝酸盐、水合氧化物、氢氧化物、氧化物氢氧化物和碳酸盐的组的一种或多种成员。
9.根据权利要求1所述的方法，其中，相对于所述掺杂的Mg/Al混合氧化物，作为MnO2计算，加入至再悬浮的Mg/Al混合氧化物的锰氧化物前体的量为5至20％wt。
10.根据权利要求1所述的方法，其中，连同锰氧化物前体和基于铈的氧化物前体一起，将除了基于铈的氧化物前体之外的稀土氧化物前体加入所述第二悬浮液。
11.根据权利要求1所述的方法，其中，所述第一悬浮液和/或所述第二悬浮液的干燥包含喷雾干燥。
12.一种根据权利要求1至11中任一项所述的方法可获得的载体材料。
13.根据权利要求12所述的载体材料，在850℃下热老化处理4小时以后，不包含BaAl2O4。
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| EP15158315.0A EP3067319A1 (en) | 2015-03-09 | 2015-03-09 | Nox trap catalyst support material with improved stability against baal2o4 formation |
| PCT/EP2016/000413 WO2016142058A1 (en) | 2015-03-09 | 2016-03-08 | Nox trap catalyst support material with improved stability against baai2o4 formation |
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| CN111315476A (zh) * | 2017-11-13 | 2020-06-19 | 三井金属矿业株式会社 | 氮氧化物吸留材料和废气净化用催化剂 |
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| JP2018509368A (ja) | 2018-04-05 |
| BR112017019407A2 (pt) | 2018-04-24 |
| US20180065112A1 (en) | 2018-03-08 |
| US10279337B2 (en) | 2019-05-07 |
| CA2976548A1 (en) | 2016-09-15 |
| RU2017133634A3 (zh) | 2019-05-28 |
| BR112017019407B8 (pt) | 2023-04-18 |
| EP3277630B1 (en) | 2019-05-01 |
| BR112017019407B1 (pt) | 2023-01-17 |
| CN107405570A (zh) | 2017-11-28 |
| EP3277630A1 (en) | 2018-02-07 |
| CA2976548C (en) | 2023-10-31 |
| WO2016142058A1 (en) | 2016-09-15 |
| RU2017133634A (ru) | 2019-04-09 |
| HK1246729A1 (zh) | 2018-09-14 |
| RU2706060C2 (ru) | 2019-11-13 |
| KR102459791B1 (ko) | 2022-10-27 |
| KR20170127513A (ko) | 2017-11-21 |
| JP6760956B2 (ja) | 2020-09-23 |
| EP3067319A1 (en) | 2016-09-14 |
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