CN109310989B - 制备用于减少废气中的氮氧化物、voc和一氧化碳的整料催化剂的方法 - Google Patents
制备用于减少废气中的氮氧化物、voc和一氧化碳的整料催化剂的方法 Download PDFInfo
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- CN109310989B CN109310989B CN201780036663.0A CN201780036663A CN109310989B CN 109310989 B CN109310989 B CN 109310989B CN 201780036663 A CN201780036663 A CN 201780036663A CN 109310989 B CN109310989 B CN 109310989B
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- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 239000003054 catalyst Substances 0.000 title claims abstract description 19
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 7
- 229910002091 carbon monoxide Inorganic materials 0.000 title claims abstract description 7
- 239000007789 gas Substances 0.000 title claims abstract description 6
- 239000012855 volatile organic compound Substances 0.000 title claims description 9
- 238000004519 manufacturing process Methods 0.000 title abstract description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229910052751 metal Inorganic materials 0.000 claims abstract description 20
- 239000002184 metal Substances 0.000 claims abstract description 20
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 18
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910001935 vanadium oxide Inorganic materials 0.000 claims abstract description 12
- 239000000758 substrate Substances 0.000 claims description 41
- 150000001875 compounds Chemical class 0.000 claims description 29
- 150000003682 vanadium compounds Chemical class 0.000 claims description 26
- 239000002245 particle Substances 0.000 claims description 23
- 239000000725 suspension Substances 0.000 claims description 20
- 239000002002 slurry Substances 0.000 claims description 15
- 239000007864 aqueous solution Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 9
- 239000010936 titanium Substances 0.000 claims description 9
- 229910052719 titanium Inorganic materials 0.000 claims description 9
- 239000011248 coating agent Substances 0.000 claims description 8
- 238000000576 coating method Methods 0.000 claims description 8
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 5
- 239000007790 solid phase Substances 0.000 claims description 5
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical group O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 4
- FGUUSXIOTUKUDN-IBGZPJMESA-N C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 Chemical compound C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 FGUUSXIOTUKUDN-IBGZPJMESA-N 0.000 claims description 3
- 150000002941 palladium compounds Chemical class 0.000 claims description 2
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims description 2
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 abstract description 3
- 229910001930 tungsten oxide Inorganic materials 0.000 abstract description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 14
- 229910052763 palladium Inorganic materials 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 239000002243 precursor Substances 0.000 description 5
- 239000008346 aqueous phase Substances 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 230000007423 decrease Effects 0.000 description 3
- 230000010718 Oxidation Activity Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000007848 Bronsted acid Substances 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- -1 Platinum Group Metals Chemical class 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- ADUFBHYKXMWOSH-UHFFFAOYSA-N [O--].[O--].[Ti+4].[V+5] Chemical compound [O--].[O--].[Ti+4].[V+5] ADUFBHYKXMWOSH-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 150000003058 platinum compounds Chemical class 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明涉及一种制备用于减少废气中的氮氧化物VOC和一氧化碳的整料催化剂的方法,该催化剂包含至少一种铂族金属、氧化钒、二氧化钛和任选的氧化钨。
Description
本发明涉及整料型催化剂(monolithic shaped catalyst)的制造,该催化剂用于从废气中除去氮氧化物、挥发性有机化合物(VOC)和一氧化碳或减少氮氧化物、挥发性有机化合物(VOC)和一氧化碳的含量。
特别地,本发明提供了一种制备负载在整料基材壁上和内部的包含氧化钒、二氧化钛和铂族金属(PGM)的催化剂的方法,其中在基材上轴向和径向的钯浓度梯度减少。
PGM(特别是钯促进的氧化钒催化剂)提供非常高的CO和VOC氧化活性以及氮氧化物的中等至高选择性催化还原(SCR)活性和高耐硫性。
通常通过用含有催化剂载体材料的洗涂层涂覆整料基材并用催化活性金属氧化物的前体溶液浸渍涂覆的基材来制备上述类型的整料型催化剂。或者,洗涂层也可含有前体。
整料或蜂窝状整料基材的洗涂通常通过将浆料倾倒入整料基材的通道中,通过将基材的一侧浸入洗涂浆料中并任选地在相对侧施加真空或通过将洗涂浆料泵入通道中以在基材中获取浆料来进行。
在用洗涂层涂覆后,将基材干燥并最后煅烧以活化涂层中的催化组分。
洗涂和/或浸渍基材的问题在于它可能影响跨越洗涂层的厚度和沿着整料中的通道轴的催化组分的浓度梯度。因此,它对上述成品催化剂的质量和性能具有潜在的损害。
浓度梯度在PGM促进的钒SCR催化剂中特别不利。SCR反应中的催化活性和CO和VOC氧化取决于涂覆基材的催化活性表面上的PGM浓度。
梯度的形成尤其是浸渍预负载有氧化钒的基材中存在的问题。这是由于PGM在催化剂基材中的氧化钒上的吸附是强烈且快速的,这使得必须用过量的钯/铂浸渍催化剂基材,以便在基材的中心达到最小负载。生产过程也可能难以控制,例如施加湿浸渍时,PGM前体的消耗。
为了有效地利用昂贵的PGM并在基材的所有部分提供所需的氧化活性,必须避免在催化基材的整个轴向和垂直长度上形成PGM浓度梯度。
我们发现,当降低催化剂基材上PGM的吸附速率时,可以消除或显著减少梯度。代替将PGM的前体化合物溶解在水性浸渍液中,是将前体化合物加入到含有沉淀在二氧化钛颗粒上的钒化合物的水性浆料中,其用作PGM的载体并用于涂覆基材。在该水性浆料中,PGM化合物被吸附在负载的钒化合物颗粒上,因此不溶于水性浆料的水相中,否则由于溶解的PGM化合物在基材壁的表面或可能在基材壁内的强烈和快速的吸附而导致不期望的梯度。
根据上述发现和观察,本发明提供了一种制备用于减少废气中的氮氧化物、VOC和一氧化碳的整料催化剂的方法,该催化剂包含至少一种铂族金属、氧化钒、二氧化钛和任选的氧化钨,该方法包括以下步骤:
a)提供整料基材;
b)提供钒化合物的水溶液;
c)提供至少一种铂族金属的一种或多种化合物的水溶液;
d)将二氧化钛颗粒加入到钒化合物的水溶液中,以获得包含悬浮于钒化合物水溶液的二氧化钛颗粒的悬浮液;
e)将步骤d)的悬浮液中的至少部分钒化合物沉淀在二氧化钛颗粒的表面上,以获得二氧化钛负载的钒化合物颗粒的悬浮液;
f)将悬浮液的pH值调节至至少6,并向该pH调节的二氧化钛负载的钒化合物颗粒的悬浮液中加入至少一种铂族金属的一种或多种化合物的水溶液,以获得含有悬浮固相的洗涂浆料,其中至少一种铂族金属的一种或多种化合物吸附在二氧化钛负载的钒化合物颗粒上;或
将至少一种铂族金属的一种或多种化合物的水溶液加入到二氧化钛负载的钒化合物颗粒的悬浮液中,随后将悬浮液的pH值调节至至少6,以获得含有悬浮固相的洗涂浆料,其中至少一种铂族金属的一种或多种化合物吸附在二氧化钛负载的钒化合物颗粒上;
g)使整料基材涂覆有一层步骤f)的洗涂浆料;
h)将涂覆在整料基材上的层的pH值降低到低于6,并将来自二氧化钛负载的钒化合物颗粒的至少一种铂族金属的一种或多种化合物溶解在整料基材的壁上和壁内;和
i)干燥并煅烧洗涂的整料基材。
悬浮液的pH值是钯/铂化合物溶液添加阶段的关键参数之一,并且必须仔细监测至至少6。调节悬浮液的pH值的目的是防止PGM化合物溶解到悬浮液的水相中,以控制化合物在催化剂基材上的较慢且均匀的摄取。
实验表明,pH值降至低于6导致增加量的PGM化合物溶解到悬浮液的水相和由悬浮液制备的洗涂层中。
基于这些实验,优选地将悬浮液调节至pH 8,这也允许在随后的制备步骤中pH值有一定的下降。
另外表明,特别是偏钒酸铵(AMV)增强了Pd化合物在浆料中的二氧化钛-钒化合物颗粒上的吸附。加入AMV确保Pd在低至pH 6时不溶于水相。
因此,在本发明的一个优选实施方案中,本发明中使用的钒化合物是偏钒酸铵。
已知金属或氧化形式的钯是组合催化除去一氧化碳、VOC和氮氧化物中最有用的催化剂。
因此,至少一种铂族金属的至少一种化合物是一种或多种钯化合物,其在本发明的煅烧步骤中转化为金属和/或氧化形式的钯。
如上所述制备的浆料用于洗涂整料基材。由于PGM化合物保留在洗涂层的固相中,PGM化合物将均匀地分布在整料基材壁的整个外部。此时,壁上存在的湿洗涂层的pH值降低到低于6,并且PGM化合物从二氧化钛负载的钒化合物颗粒中溶解,并开始迁移到壁中并最终均匀地分布到壁内和壁上。
进一步观察到,在用根据本发明制备的洗涂层涂覆之前,包含氧化钒、二氧化钛和任选的钨的整料基材显示出布朗斯台德酸和路易斯酸位点,其在洗涂层施加到整料基材的表面之后将洗涂层的pH值降低至低于6。此时,整料基材中含有的氧化钒-二氧化钛的酸度开始降低湿涂层的pH值,并且PGM化合物从洗涂层中的二氧化钛负载的钒化合物颗粒中溶解,并开始迁移到壁中。因此,PGM化合物均匀地分布在整料基材的壁中。
因此,在本发明的一个具体实施方案中,在涂覆洗涂层之前,在根据本发明的方法的步骤a)中提供的整料基材的壁内提供有氧化钒、二氧化钛和任选的氧化钨。包含在整料基材中的氧化钒优选是在SCR反应中具有最高活性的五氧化二钒。
用于本发明的优选PGM化合物是硝酸钯,如本发明所期望的,它可溶于水并在pH值约为6或更高时沉淀。
Claims (7)
1.一种制备用于还原废气中的氮氧化物、VOC和一氧化碳的整料催化剂的方法,该催化剂包含至少一种铂族金属、氧化钒和二氧化钛,该方法包括以下步骤:
a)提供整料基材;
b)提供钒化合物的水溶液;
c)提供至少一种铂族金属的一种或多种化合物的水溶液;
d)将二氧化钛颗粒加入到钒化合物的水溶液中,以获得包含悬浮于钒化合物水溶液中的二氧化钛颗粒的悬浮液;
e)将步骤d)的悬浮液中的至少部分钒化合物沉淀在二氧化钛颗粒的表面上,以获得二氧化钛负载的钒化合物颗粒的悬浮液;
f)将悬浮液的pH值调节至至少6,并向该pH调节的二氧化钛负载的钒化合物颗粒的悬浮液中加入所述至少一种铂族金属的一种或多种化合物的水溶液,以获得含有悬浮固相的洗涂浆料,其中该至少一种铂族金属的一种或多种化合物吸附在二氧化钛负载的钒化合物颗粒上;或
将至少一种铂族金属的一种或多种化合物的水溶液加入到二氧化钛负载的钒化合物颗粒的悬浮液中,随后将悬浮液的pH值调节至至少6,以获得含有悬浮固相的洗涂浆料,其中至少一种铂族金属的一种或多种化合物吸附在二氧化钛负载的钒化合物颗粒上;
g)使整料基材涂覆有一层步骤f)的洗涂浆料;
h)将涂覆在整料基材上的层的pH值降低到低于6,并将来自二氧化钛负载的钒化合物颗粒的至少一种铂族金属的一种或多种化合物溶解在整料基材的壁上和壁内;和
i)干燥并煅烧洗涂的整料基材。
2.根据权利要求1所述的方法,其中将步骤f)中的pH值调节至至少8。
3.根据权利要求1或2所述的方法,其中钒化合物是偏钒酸铵。
4.根据权利要求1或2所述的方法,其中所述铂族金属的至少一种化合物是一种或多种钯化合物。
5.根据权利要求1或2所述的方法,其中通过在步骤a)中提供的整料基材中提供氧化钒和二氧化钛来降低步骤h)中的洗涂层的pH值。
6.根据权利要求5所述的方法,其中氧化钒是五氧化二钒。
7.根据权利要求1或2所述的方法,其中所述至少一种铂族金属的一种或多种化合物是硝酸钯。
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