CN117813147A - 用于处理废气的方法和hvac系统 - Google Patents
用于处理废气的方法和hvac系统 Download PDFInfo
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- CN117813147A CN117813147A CN202280053738.7A CN202280053738A CN117813147A CN 117813147 A CN117813147 A CN 117813147A CN 202280053738 A CN202280053738 A CN 202280053738A CN 117813147 A CN117813147 A CN 117813147A
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- catalyst
- mixed oxide
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- exhaust gas
- conversion
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- 238000000034 method Methods 0.000 title claims abstract description 36
- 239000003054 catalyst Substances 0.000 claims abstract description 94
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 47
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 47
- 239000012855 volatile organic compound Substances 0.000 claims abstract description 37
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 28
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 26
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 39
- 239000007789 gas Substances 0.000 claims description 36
- 239000010949 copper Substances 0.000 claims description 20
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- 229910052751 metal Inorganic materials 0.000 claims description 19
- 239000002184 metal Substances 0.000 claims description 19
- 229910052802 copper Inorganic materials 0.000 claims description 16
- 229910052760 oxygen Inorganic materials 0.000 claims description 15
- 229910052782 aluminium Inorganic materials 0.000 claims description 12
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- 229910052749 magnesium Inorganic materials 0.000 claims description 11
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- 239000001301 oxygen Substances 0.000 claims description 8
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- GZUXJHMPEANEGY-UHFFFAOYSA-N bromomethane Chemical compound BrC GZUXJHMPEANEGY-UHFFFAOYSA-N 0.000 description 10
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
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- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
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- 238000009835 boiling Methods 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
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- 239000003518 caustics Substances 0.000 description 1
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- MZZUATUOLXMCEY-UHFFFAOYSA-N cobalt manganese Chemical compound [Mn].[Co] MZZUATUOLXMCEY-UHFFFAOYSA-N 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 230000000779 depleting effect Effects 0.000 description 1
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- 229910000042 hydrogen bromide Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002475 indoles Chemical class 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
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- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
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- 150000002894 organic compounds Chemical class 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
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- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
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Classifications
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Abstract
本发明涉及一种使用包含Mn、Cu、Mg、Al和La的混合氧化物的不含PGM的催化剂制品处理包含一氧化碳(CO)和/或一种或多种挥发性有机化合物(VOC)的废气的方法。本发明还涉及HVAC系统,该HVAC系统包括不含PGM的催化剂制品。
Description
本发明涉及使用不含PGM的催化剂制品处理废气,特别是包含一氧化碳(CO)和/或一种或多种挥发性有机化合物(VOC)的废气的方法。本发明还涉及HVAC系统,该HVAC系统包括不含PGM的催化剂制品。
众所周知,包含铂族金属(PGM)的催化剂可用于有害排放诸如CO和VOC的催化氧化。PGM催化剂普遍存在于用于处理汽车废气排放以及来自工业过程的排放的催化剂中。PGM催化剂具有高催化活性和良好的热稳定性。然而,PGM是昂贵的,并且希望降低催化剂制品的成本而不损失催化活性。这对于工业过程尤其如此,诸如在对苯二甲酸合成中的尾气的催化氧化中,以及用于处理大量废气的其他系统,诸如HVAC系统,这将需要大量投资昂贵的PGM。
已知包含贱金属的不含PGM的催化剂是PGM催化剂的替代物。贱金属明显更便宜,然而,仍然需要此类催化剂以展示高催化活性,以便于提供经改善的CO和VOC氧化活性。
WO03/101612涉及催化剂组合物,该催化剂组合物用于处理来自工业和商业过程以及用于从烃燃料诸如煤、油和气体生成动力的过程的排放。特别地,本发明涉及用于氧化一氧化碳(CO)和挥发性有机化合物(VOC)的催化剂组合物,并且在一个方面,提供用作氢化催化剂的催化剂组合物,该组合物包含至少两种不同的高表面积氧化物载体材料,其中至少一种高表面积载体材料承载至少一种贱金属促进剂。
WO2010/123731涉及用于氧化一氧化碳和挥发性有机化合物的含铜和锰的贱金属催化剂。催化剂组合物包含承载在氧化物载体材料上的至少一种贱金属促进剂和至少一种贱金属催化剂,该氧化物载体材料包含以下项中的一种或多种:氧化铝、二氧化硅、氧化锆、二氧化铈和二氧化钛,例如,镧稳定化的氧化铝和/或锆稳定化的二氧化铈。
WO2014/138397涉及贱金属催化剂及其其使用方法,特别是包含与基本上不含氧化铝的供氧载体接触的第一贱金属催化剂和至少一种第二贱金属催化剂的催化剂。在一些实施方案中,催化剂包含10重量%至20重量%的CuO,并且催化剂包含5重量%至10重量%的MnO。
本发明人开发本发明的目的在于:克服与现有技术相关联的问题,并且提供用于处理包含CO和/或一种或多种VOC的废气的经改善的方法,或者至少提供商业上有用的替代方案。
因此,在本发明的第一方面中,提供了用于处理包含一种或多种挥发性有机化合物(VOC)的废气的方法,该方法包括使废气与包含Mn、Cu、Mg、Al和La的混合氧化物的不含PGM的催化剂制品接触。
现在将进一步描述本公开。在以下段落中,更详细地定义了本公开的不同方面/实施方案。除非有明确相反的说明,否则如此定义的每个方面/实施方案可与任何其它方面/实施方案或多个方面/实施方案组合。特别地,任何被指示为优选或有利的特征可与任何其他被指示为优选或有利的一个或多个特征组合。
本发明的方法涉及一种用于处理废气的方法。废气包含一氧化碳和/或一种或多种挥发性有机化合物。在一个实施方案中,废气包含CO和一种或多种VOC。
如ISO16000-6中所引用,VOC由WHO定义为沸点处于(50℃至100℃)至(240℃至260℃)范围内的任何有机化合物,对应于在25℃下具有大于102kPa的饱和蒸气压。VOC包括醇、醛、胺、酯、醚、烃(多达约C10)、酮、含氮化合物、酚、吲哚及其它芳族化合物、萜烯和含硫化合物。
该方法包括使废气与包含锰(Mn)、铜(Cu)、镁(Mg)、铝(Al)和镧(La)的混合氧化物的不含PGM的催化剂制品接触。铂族金属(PGM)是一类已知的贵金属,其是指由以下项组成的组:钌(Ru)、铑(Rh)、钯(Pd)、锇(Os)、铱(Ir)和铂(Pt)。因此,混合金属氧化物不包含任何PGM(例如作为金属或作为氧化物或盐)。应当理解,混合金属氧化物的金属(即Mn、Cu、Mg、Al和La)全部以氧化物形式存在,而不是以金属状态存在。
本发明人已经发现,包含Mn、Cu、Mg、Al和La的混合金属氧化物为CO和VOC的催化氧化提供特别有效的不含PGM的催化剂。已经发现此类氧化物即使在相对低的温度下也提供经改善的活性。本发明人已经发现,该催化剂对于甲醇、乙醇、乙醛、甲醛、丙烯和乙烯的催化氧化特别有效。因此,优选的是VOC包含选自甲醇、乙醇、乙醛、甲醛、丙烯和乙烯的一种或多种化合物。
优选地,废气来自加热、通风和空调系统(HVAC系统)或者是来自化学合成过程(优选对苯二甲酸合成)的尾气。即,废气可为用于产生经纯化的对苯二甲酸(PTA)的过程的尾气。PTA设备排放CO和多种VOC,诸如甲基溴、苯、醋酸盐、二甲苯、乙酸和甲醇。它们一起引起烟雾;甲基溴也是平流层臭氧消耗剂。
在产生PTA的商业过程中,可使用乙酸作为溶剂通过用氧气氧化对二甲苯来产生对苯二甲酸。这可在催化剂诸如使用溴化物促进剂的钴-锰的存在下发生。产物可在水溶液中的情况下通过氢化纯化,并且然后可经冷却。经纯化的对苯二甲酸(PTA)过程中的尾气可包含氧、氮、氮氧化物、甲基溴、苯、甲烷、一氧化碳、乙酸甲酯和水。具体地,典型的PTA过程尾气可包含百万分之30份(ppm)的甲基溴、10ppm的苯、100ppm的甲烷、1000ppm的一氧化碳、500ppm的乙酸甲酯、1.5摩尔%的水、4摩尔%的氧以及余量的氮。另外,混合金属氧化物还可氧化并转化其他挥发性有机化合物,诸如甲基乙基酮、甲醇、丁烷或丁烯。
PTA过程尾气还可包含约2摩尔%蒸汽/水。类似地,可能需要HVAC系统来处理包含水/湿气的气体。混合氧化物必须是稳定的并且能够在具有水分的环境中有效地起作用。已知某些催化剂和载体(诸如沸石)在水热条件下,尤其是在一段时间内降解。然而,本文所述的混合金属氧化物能够在含有水蒸气(例如1.5摩尔%至5摩尔%水分)的气体中在大于400℃、或另选地200℃至400℃、200℃至325℃、200℃至300℃、200℃至250℃、或另选地小于325℃、小于300℃、或小于250℃的温度下经受得住并且有效地工作。
当含有水蒸气、CO和VOC的气体(诸如来自PTA过程的尾气)与混合金属氧化物接触时,CO和VOC被氧化。例如,在过程流出气体包含水蒸气、CO和甲基溴的情况下,可将过程流出物预热并在过量氧的存在下经过催化剂床,并且将流中的污染组分氧化成二氧化碳(CO2)和溴化氢(HBr)。来自催化剂下游的溴化氢可以通过使气体经过碱洗气器而容易地从流出物中去除,从而在将废气排放到大气中之前从流出物中去除污染物。
氧化物(在本文中可称为混合金属氧化物或混合氧化物)优选地不承载在混合氧化物载体诸如La、Al、Zr或Ce混合氧化物上。相反,这些氧化物中的一些氧化物,具体是Al和La的那些氧化物,被结合到本文所述的混合金属氧化物的格栅结构中。因此,混合金属氧化物可由单一式表示,例如MnaCubMgcAldLaeOf(其中a、b、c、d、e和f是元素的摩尔量)。
本发明人已经发现,在Mn和La含量较大的情况下,混合金属氧化物特别有效。优选地,混合氧化物仅以金属为基础包含至少30重量%的Mn。更优选地,混合氧化物包含至少35重量%,并且甚至更优选地至少40重量%的Mn。优选地,Mn的量为至多60重量%,更优选地至多55重量%,并且甚至更优选地至多50重量%。
优选地,混合氧化物包含至少35重量%的La和/或至多45重量%的La,优选地至少39重量%的La和/或至多43重量%的La。
本文所述的关于混合金属氧化物的金属的所有重量百分比(即重量%)仅以金属为基础提供。即,给定金属的重量%作为混合金属氧化物中金属总量的重量百分比提供,由此排除由氧(O)提供的重量。
类似地,本发明人已经发现,优选的是铜以至少5重量%的量存在。优选地,铜的量为至多10重量%。
例如,本发明人已经发现,特别是包含40重量%至50重量%的Mn和至少5重量%的铜的混合金属氧化物是Mn和Cu的优选组合。
此外,本发明人已经发现,优选地,混合氧化物包含至少3重量%的Mg和/或至多6重量%的Mg。优选地,混合氧化物包含至少1重量%的Al和/或至多3重量%的Al。
因此,在特别优选的实施方案中,混合氧化物仅以金属为基础包含:
40重量%至50重量%的Mn;
6重量%至8重量%的Cu;
3重量%至6重量%的Mg;
1重量%至3重量%的Al;
35重量%至45重量%的La。
甚至更优选地,混合氧化物仅以金属为基础包含:
42重量%至48重量%的Mn;
约7重量%的Cu;
约4.5重量%的Mg;
约2重量%的Al;
39重量%至43重量%的La。
优选地,术语“约”是指在±10%内,更优选地在±5%内,同时公开了在实验误差内的值本身。因此,混合氧化物优选地包含至少6.3重量%的Cu和/或至多7.7重量%的Cu,诸如6.3重量%至7重量%、7重量%至7.7重量%或6.3重量%至7.7重量%。同样地,混合氧化物优选地包含至少4.05重量%的Mg和/或至多4.95重量%的Mg,诸如4.05重量%至4.5重量%、4.5重量%至4.95重量%或4.05重量%至4.95重量%。优选地,混合氧化物优选地包含至少1.8重量%的Al和/或至多2.2重量%的Al,诸如1.8重量%至2重量%、2重量%至2.2重量%或1.8重量%至2.2重量%。这同样适用于±5%的优选范围。
在优选的实施方案中,混合氧化物基本上由Mn、Cu、Mg、Al和La以及氧(O)组成。即,混合金属氧化物可由单一式表示,例如MnaCubMgcAldLaeOf(其中a、b、c、d、e和f是元素的摩尔量)。同样地,金属Mn、Cu、Mg、Al和La的重量百分比的总和将基本上等于100重量%。
优选的是,Mn与La的摩尔比为至少2.5∶1和/或至多3∶1。例如,Mn与La的摩尔比优选地为2.5∶1至3∶1。换句话讲,比率a∶e为2.5∶1至3∶1。优选的是,Mn与Al的比率为至少10∶1和/或至多12∶1,例如比率a∶d为10∶1至12∶1。优选的是,Mn与Mg的比率为至少4∶1和/或至多5∶1,例如比率a∶c为4∶1至5∶1。优选的是,Mn与Cu的比率为至少7∶1和/或至多7.5∶1,例如比率a∶b为7∶1至7.5到1。
在本发明的另一个方面,提供了一种HVAC系统,该HVAC系统包括不含PGM的催化剂制品,该催化剂制品包括Mn、Cu、Mg、Al和La的混合氧化物。
优选地,Mn、Cu、Mg、Al和La的混合氧化物是本文关于处理废气的方法所描述的。例如,优选的是,混合氧化物仅以金属为基础包含:
40重量%至50重量%的Mn;
6重量%至8重量%的Cu;
3重量%至6重量%的Mg;
1重量%至3重量%的Al;
35重量%至45重量%的La。
本发明人已经发现,包含Mn、Cu、Mg、Al和La的混合金属氧化物示出较大的VOC氧化活性以及对CO2的选择性。因此,在用于提供经纯化的室内空气的HVAC系统中,氧化物在从空气中去除有害的VOC污染物方面特别有效。特别地,混合金属氧化物在相对低的温度下作为氧化催化剂是特别有效的,并且因此特别适合此类低温应用。
在下文中,催化剂A是对比催化剂,而催化剂MO是根据本发明的实施例。
附图说明
现在将参考以下非限制性附图进一步描述本发明,其中:
图1A和图1B提供实施例1的结果,并且分别绘制了针对催化剂MO连同已知对比的贱金属催化剂(催化剂A)在气体发动机测试条件下的甲醛和甲醇的转化率相对于温度的曲线。
图2A和图2B提供实施例2的结果,并且分别绘制了针对催化剂MO连同催化剂A两者在气体发动机测试条件下的CO和NO的转化率相对于温度的曲线。
图3A和图3B提供实施例3的结果,并且分别绘制了针对催化剂MO连同催化剂A在VOC测试条件下的甲醇和CO的转化率相对于温度的曲线。图3C和图3D分别绘制了针对催化剂MO和催化剂A两者的所观察到的甲醛和CO2的浓度相对于温度的曲线。
图4A和图4B提供实施例4的结果,并且分别绘制了针对催化剂MO连同催化剂A在VOC测试条件下的乙醇和CO的转化率相对于温度的曲线。图4C和图4D分别绘制了针对催化剂MO和催化剂A两者的所观察到的乙醛和甲醛的浓度相对于温度的曲线。
图5A和图5B提供实施例5的结果,并且分别绘制了针对催化剂MO连同催化剂A在VOC测试条件下的丙烯和CO的转化率相对于温度的曲线。
图6A和图6B提供实施例6的结果,并且分别绘制了针对催化剂MO连同催化剂A在VOC测试条件下的乙烯和CO的转化率相对于温度的曲线。
图7A、图7B和图7C提供实施例7的结果,并且分别绘制了针对催化剂MO连同催化剂A在VOC测试条件下的乙烯、丙烯和CO的转化率相对于温度的曲线。
实施例
混合金属氧化物的制备
共沉淀涉及在溶液中使用金属硝酸盐(Mn、Cu、Mg、Al、La)。使用碱溶液作为沉淀剂(NaOH/Na2CO3)。通过在一个容器中用去离子水将金属硝酸盐前体一起溶解来获得金属硝酸盐溶液。为了制备碱溶液,将NaOH和Na2CO3混合在一起并加入去离子水。搅拌两种溶液,并且然后通过使用液体泵将溶液从其容器转移到反应器中。
表1:碱溶液的制备
碱 | 目标质量(Kg) |
NaOH | 3.36(2.8M) |
Na2CO3 | 4.77(1.5M) |
用于碱溶液的水 | 目标体积=30L |
表2:金属硝酸盐溶液的制备
通过在搅拌下以受控的添加速率添加来自表1和表2的两种溶液来进行共沉淀,这允许保持pH恒定在约10.pH至11.pH可使用标准pH电极来监测。
添加可在约1小时的时期内进行,并且在添加完成后再搅拌反应混合物1小时。
一旦共沉淀已完成,就必须洗涤和过滤。大量的去离子水通过沉淀剂冲洗,直到水的电导率为新鲜去离子水的电导率(例如约100μS)。
最后,在研磨之前将固体材料在空气中在105℃至110℃下干燥过夜,随后在空气中在例如500℃下煅烧2小时。所得混合金属氧化物在本文中可称为催化剂MO。
混合金属氧化物的测试
将混合金属氧化物相对于对比的已知市售的不含PGM的贱金属催化剂(催化剂A)进行测试。
催化剂A根据WO2010/123731制备并且包含载体,该载体包含镧稳定的氧化铝和铈稳定的氧化锆。将锰作为乙酸盐添加到涂层浆料中,该涂层浆料分两次施加到陶瓷基板上以提供3.3g/in3(0.2g/cm3)的目标涂层负载。然后,浸渍硝酸铜,目标为375g/ft3(13243g/m3)。如通过ICP测定的,催化剂A仅以金属为基础包含3重量%的Mn和2重量%的Cu。
将催化剂A核压碎、造粒、研磨并筛分。355μm至250μm的筛分粒度级用于测试。测试了总共0.2g的筛分材料。
混合氧化物是粉末,因此,其不需要粉碎。在测试前,还将样品造粒、研磨并筛分。
实施例1(甲醛和甲醇活性):
气体发动机测试条件:100ppmCH4、20ppmCH2O、200ppmNOx、540ppmCO、10%O2、10%CO2、10%H2O、余量N2;0.2g催化剂(355μm至250μm),流量=3.3L/min,温度斜坡=110℃至500℃。
结果示出于图1A和图1B中。混合金属氧化物(即催化剂MO)在175℃处实现50%甲醛转化率,而催化剂A在220℃处实现50%甲醛转化率。类似地,当与催化剂A所要求的270℃相比时,混合金属氧化物在较低温度211℃处实现50%甲醇转化率。
实施例2(CO和NO活性):
气体发动机测试条件:100ppmCH4、20ppmCH2O、200ppmNOx、540ppmCO、10%O2、10%CO2、10%H2O、余量N2;0.2g催化剂(355μm至250μm),流量=3.3L/min,温度斜坡=110℃至500℃。
结果示出于图2A和图2B中。混合金属氧化物(即催化剂MO)在243℃处实现50%CO转化率,而催化剂A在272℃处实现50%CO转化率。类似地,针对用于混合金属氧化物的NO转化率的起始温度为约225℃,而催化剂A的起始温度为约300℃。
实施例3(甲醇和CO氧化):
VOC测试条件:500ppm甲醇、1000ppmCO、15%O2、5%H2O、余量N2;0.2g催化剂(355μm至250μm)、流量=3.3L/min、温度斜坡=110℃至500℃。
结果示出于图3A和图3B中。混合金属氧化物(即催化剂MO)在191℃处实现50%甲醇转化率,而催化剂A在260℃处实现50%甲醇转化率。类似地,当与催化剂A所要求的275℃相比时,混合金属氧化物在较低温度222℃处实现50%CO转化率。
另外,如图3C和图3D中所示,混合金属氧化物示出对产生CO2的较大选择性,导致所产生的甲醛的量减少。
实施例4(乙醇和CO氧化):
VOC测试条件:500ppm乙醇、1000ppmCO、15%O2、5%H2O、余量N2;0.2g催化剂(355μm至250μm)、流量=3.3L/min、温度斜坡=110℃至500℃。
结果示出于图4A和图4B中。混合金属氧化物(即催化剂MO)在198℃处实现50%乙醇转化率,而催化剂A在261℃处实现50%乙醇转化率。类似地,当与催化剂A所要求的288℃相比时,混合金属氧化物在较低温度236℃处实现50%CO转化率。
另外,如图4C和图4D所示,混合金属氧化物比催化剂A产生更少的甲醛。
实施例5(丙烯和CO氧化):
VOC测试条件:500ppm丙烯、1000ppmCO、15%O2、5%H2O、余量N2;0.2g催化剂(355μm至250μm)、流量=3.3L/min、温度斜坡=110℃至500℃。
结果示出于图5A和图5B中。混合金属氧化物(即催化剂MO)在284℃处实现50%丙烯转化率,而催化剂A在显著更高的温度390℃处实现50%丙烯转化率。类似地,当与催化剂A所要求的262℃相比时,混合金属氧化物在较低温度207℃处实现50%CO转化率。
实施例6(乙烯和CO氧化):
VOC测试条件:500ppm乙烯、1000ppmCO、15%O2、5%H2O、余量N2;0.2g催化剂(355μm至250μm)、流量=3.3L/min、温度斜坡=110℃至500℃。
结果示出于图6A和图6B中。混合金属氧化物(即催化剂MO)在346℃处实现50%乙烯转化率,而催化剂A在显著更高的温度475℃处实现50%乙烯转化率。类似地,当与催化剂A所要求的259℃相比时,混合金属氧化物在较低温度196℃处实现50%CO转化率。
实施例7(丙烯、乙烯和CO氧化):
VOC测试条件:500ppm丙烯、500ppm乙烯、1000ppmCO、15%O2、5%H2O、余量N2;0.2g催化剂(355μm至250μm)、流量=3.3L/min、温度斜坡=110℃至500℃。
结果示出于图7A至图7C中。混合金属氧化物(即催化剂MO)在335℃处实现50%的乙烯转化率且在247℃处实现50%的丙烯转化率,而催化剂A在显著更高的温度435℃和355℃处分别实现50%的乙烯转化率和丙烯转化率。类似地,当与催化剂A所要求的226℃相比时,混合金属氧化物在较低温度195℃处实现50%CO转化率。
如本文所用,除非上下文另有明确说明,否则单数形式“一个”、“一种”和“所述”包括复数指代。术语“包括”的使用旨在被解释为包括此类特征但不排除其他特征,并且还旨在包括必须限于所描述的那些特征的特征选项。换句话说,该术语还包括限制“基本上由......组成”(旨在表示可存在特定的另外的部件,前提条件是它们不实质性地影响所描述的特征的基本特性)和“由......组成”(旨在表示可不包括其他特征,使得如果这些部件以它们的比例的百分比来表达,则这些将合计达100%,同时考虑任何不可避免杂质),除非上下文另有明确说明。
以上详细描述已通过解释和说明的方式提供,并且不旨在限制所附权利要求的范围。本文所示的目前优选的实施方案的许多变型形式对于本领域普通技术人员而言将是显而易见的,并且保持在所附权利要求及其等同物的范围内。
Claims (9)
1.一种用于处理废气的方法,所述废气包含一氧化碳(CO)和/或一种或多种挥发性有机化合物(VOC),所述方法包括使所述废气与包含Mn、Cu、Mg、Al和La的混合氧化物的不含PGM的催化剂制品接触。
2.根据权利要求1所述的方法,其中所述混合氧化物仅以金属为基础包含40重量%至50重量%的Mn和至少5重量%的铜。
3.根据权利要求1或权利要求2所述的方法,其中所述混合氧化物仅以金属为基础包含:
40重量%至50重量%的Mn;
6重量%至8重量%的Cu;
3重量%至6重量%的Mg;
1重量%至3重量%的Al;
35重量%至45重量%的La。
4.根据任一项前述权利要求所述的方法,其中所述混合氧化物仅以金属为基础包含:
42重量%至48重量%的Mn;
约7重量%的Cu;
约4.5重量%的Mg;
约2重量%的Al;
39重量%至43重量%的La。
5.根据权利要求3或权利要求4所述的方法,其中所述混合氧化物基本上由Mn、Cu、Mg、Al和La以及氧组成。
6.根据任一项前述权利要求所述的方法,其中Mn与La的摩尔比为2.5:1至3:1。
7.根据任一项前述权利要求所述的方法,其中所述VOC包含一种或多种选自甲醇、乙醇、乙醛、甲醛、丙烯和乙烯的化合物。
8.根据任一项前述权利要求所述的方法,其中所述废气来自HVAC系统或者是来自化学合成过程,优选是对苯二甲酸合成的尾气。
9.一种HVAC系统,所述HVAC系统包含不含PGM的催化剂制品,所述不含PGM的催化剂制品包含Mn、Cu、Mg、Al和La的混合氧化物,优选地,其中所述混合氧化物仅以金属为基础包含:
40重量%至50重量%的Mn;
6重量%至8重量%的Cu;
3重量%至6重量%的Mg;
1重量%至3重量%的Al;
35重量%至45重量%的La。
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