CN1059353C - 多环芳烃污染物的排气催化治理催化剂 - Google Patents
多环芳烃污染物的排气催化治理催化剂 Download PDFInfo
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Abstract
多环芳烃污染物的排气催化治理催化剂,属于有机尾气或废气的催化治理剂,其特征是:在活性组分中,主要加入了以铈为主的混合轻稀土氧化物Ln,其余为:铜、钴、铁和锰,其重量百分比为:Ln∶Cu∶Co∶Fe∶Mn=(10~15)∶(9~14)∶(8~13)∶0.5∶0.5;也可为:Ln∶Fe∶Mn∶Cu∶Co=(10~20)∶(1.7~3.9)∶(1.5~3.5)∶0.5∶0.5,其余不足100%的量是γ-Al2O3小球或金属网等载体。它对多环芳烃的平均净化率不低于95%,对CO、CHx分别不低于80%和90%。可广泛用于汽、柴油机、垃圾或煤的燃烧废气治理中。
Description
一种多环芳烃污染物的排气催化治理催化剂属于有机尾气或废气的催化治理技术领域。
机动车排出的尾气中含有大量的CO、CHx和多环芳烃类气体,前者污染环境,后者是强烈的致癌物,对人体有害。一般的机动车排气催化净化剂可净化CO及CHx,但对后者却无能为力。美国专利(U.S.4446070)在1984年指出:可用硝酸铈作催化剂对把蒽氧化成蒽醌的反应进行催化,其转化率高达97.6%,其活性要高于混合轻稀土催化剂,但未见有把它用于催化治理机动车排气中多环芳烃类污染物的报导,更未见到过它又能同时去用于作治理CO和CHx的催化剂的文献。
本发明的目的在于提供一种主要用于催化治理机动车排气中的多环芳烃类污染物但又可兼及CO、CHx催化治理的多用途催化剂。
本发明的特征在于:在活性组分中,主要加入了以铈为主的混合轻稀土氧化物Ln,其余依次为:铜、钴、铁和锰,它们之间的重量百分比为:Ln∶Cu∶Co∶Fe∶Mn=(10~15)∶(9~14)∶(8~13)∶0.5∶0.5;同时,其余也可依次为铁、锰、铜和钴,它们之间的重量百分比为:Ln∶Fe∶Mn∶Cu∶Co=(10~20)∶(1.7~3.9)∶(1.5~3.5)∶0.5∶0.5,它们其余不足100%的量是载体。催化剂的载体可用粒度为4~6毫米的γ-Al2O3小球,也可用经电解法涂布了活性组分的金属网。此时,还可使用多孔陶瓷、腐蚀除铝后的多孔金属等。
上述以铈为主的混合轻稀土氧化物Ln,除了铈以外,其余依次为镧、钕、镨和钐,它们氧化物之间的重量百分比为:CeO2∶La2O3∶Nd2O3∶Pr6O11∶SmO2=40∶(25~40)∶(15~18)∶(6~8)∶3。
使用证明:本发明达到了预期目的。
实施例:
本催化剂的制造工艺如下:按本发明提出的方法,分别称取下述纯变为化学纯的活性组分化合物:硝酸钴、硝酸铜、硝酸铈、硝酸铁、以铈为主的混合轻稀土硝酸盐,再与浓度为50%的硝酸锰水溶液混合,必要时,可加入极少量的钯、铂等贵金属。再用公知的方法,按一定比例配制成溶液,按上述方法称取相应量4~6毫米粒度的γ-Al2O3小球,在配好的溶液中浸渍一夜,然后在水浴中煮干,用煤气灯在坩埚中炒成黑色并在马福炉中在500℃下烧制2小时,继续在550℃下烧制半小时,经自然降温即得。把上述催化剂用于催化治理机动车排放的尾气时,多环芳烃类污染物平均净化率不低于95%,对CO、CHx的去除率分别不低于80%和90%。对4升排气量的怠速运行的130汽车,使用4.5千克重的催化剂,其结果为:
1.当催化剂以稀土、铜、钴为主时,其活性组分的重量百分比为:Ln∶Cu∶Co∶Fe∶Mn=(10~15)∶(9~14)∶(8~13)∶0.5∶0.5相应的重量比为(单位为克):Ln∶Cu∶Co∶Fe∶Mn=(450~675)∶(405~630)∶(360~585)∶22.5∶22.5
实施例1:
Ln∶Cu∶Co∶Fe∶Mn=495∶450∶360∶22.5∶22.5(克)
多环芳烃类污染物的净化率为:
ug/m3 | 萤蒽FA | 苯并[a]蒽 | 苯并[b]萤蒽苯并[k]萤蒽 | 苯并[a]芘 | 苯并[ghi]芘 |
催化前 | 3.14 | 0.85 | 0.21 | 2.14 | 7.3 |
催化后 | 0.164 | 0.055 | 0.018 | 0.021 | 0.061 |
净化率 | 94.7% | 93.5% | 91% | 99% | 99% |
平均净化率 | 95.4% |
CO、CHx去除率为:
催化前浓度 | 催化后浓度 | 净化率 | |
CO | 5% | 1% | 81% |
CHx | 2800ppm | 140ppm | 95% |
实施例2:
Ln∶Cu∶Co∶Fe∶Mn=585∶585∶450∶22.5∶22.5(克)
多环芳烃类污染物的净化率为:
ug/m3 | 萤蒽FA | 苯并[a]蒽 | 苯并[b]萤蒽苯并[k]萤蒽 | 苯并[a]芘 | 苯并[ghi]芘 |
催化前 | 3.64 | 0.89 | 0.27 | 2.24 | 7.28 |
催化后 | 0.154 | 0.049 | 0.018 | 0.022 | 0.063 |
净化率 | 96% | 94% | 93% | 99% | 99% |
平均净化率 | 96.2% |
CO、CHx去除率为:
催化前浓度 | 催化后浓度 | 净化率 | |
CO | 5.7% | 1.1% | 80% |
CHx | 2850ppm | 150ppm | 94.7% |
实施例3:
Ln∶Cu∶Co∶Fe∶Mn=675∶630∶585∶22.5∶22.5(克)
多环芳烃类污染物的净化率为:
ug/m3 | 萤蒽FA | 苯并[a]蒽 | 苯并[b]萤蒽苯并[k]萤蒽 | 苯并[a]芘 | 苯并[ghi]芘 |
催化前 | 3.7 | 0.84 | 0.29 | 2.28 | 7.3 |
催化后 | 0.159 | 0.049 | 0.017 | 0.021 | 0.063 |
净化率 | 95.7% | 94.2% | 94% | 99% | 99% |
平均净化率 | 96.4% |
CO、CHx去除率为:
催化前浓度 | 催化后浓度 | 净化率 | |
CO | 6.9% | 1.2% | 82% |
CHx | 2980ppm | 130ppm | 95.5% |
2.当催化剂以稀土、铁、锰为主时,其活性组分的重量百分比为:Ln∶Fe∶Mn∶Cu∶Co=(10~20)∶(1.7~3.9)∶(1.5~3.5)∶0.5∶0.5相应的重量比为(单位为克):
Ln∶Fe∶Mn∶Cu∶Co=(450~900)∶(76.5~175.5)∶(67.5~157.7)∶22.5∶22.5
实施例4:
Ln∶Fe∶Mn∶Cu∶Co=450∶76.5∶67.5∶22.5∶22.5(克)
多环芳烃类污染物的净化率为:
ug/m3 | 萤蒽FA | 苯并[a]蒽 | 苯并[b]萤蒽苯并[k]萤蒽 | 苯并[a]芘 | 苯并[ghi]芘 |
催化前 | 6.3 | 10.2 | 2.51 | 6.2 | 1.4 |
催化后 | 0.25 | 0.2 | 0.18 | 0.29 | 0.074 |
净化率 | 96% | 98% | 94% | 95% | 94.7% |
平均净化率 | 95.5% |
CO、CHx去除率为:
催化前浓度 | 催化后浓度 | 净化率 | |
CO | 11% | 1.8% | 83% |
CHx | 3250ppm | 180ppm | 94.5% |
实施例5:
Ln∶Fe∶Mn∶Cu∶Co=675∶112.5∶112.5∶22.5∶22.5(克)
多环芳烃类污染物的净化率为:
ug/m3 | 萤蒽FA | 苯并[a]蒽 | 苯并[b]萤蒽苯并[k]萤蒽 | 苯并[a]芘 | 苯并[ghi]芘 |
催化前 | 6.7 | 11.2 | 2.58 | 6.7 | 1.5 |
催化后 | 0.26 | 0.21 | 0.17 | 0.26 | 0.08 |
净化率 | 96.1% | 98.1% | 93.4% | 96% | 94.6% |
平均净化率 | 95.6% |
CO、CHx去除率为:
催化前浓度 | 催化后浓度 | 净化率 | |
CO | 10.5% | 1.3% | 87% |
CHx | 3100ppm | 150ppm | 95% |
实施例6:
Ln∶Fe∶Mn∶Cu∶Co=900∶175.5∶157.5∶22.5∶22.5(克)
多环芳烃类污染物的净化率为:
ug/m3 | 萤蒽FA | 苯并[a]蒽 | 苯并[b]萤蒽苯并[k]萤蒽 | 苯并[a]芘 | 苯并[ghi]芘 |
催化前 | 6.6 | 11.7 | 2.59 | 6.7 | 1.51 |
催化后 | 0.21 | 0.19 | 0.17 | 0.25 | 0.078 |
净化率 | 96.8% | 98.3% | 93.4% | 96% | 94.8% |
平均净化率 | 95.8% |
CO、CHx去除率为:
催化前浓度 | 催化后浓度 | 净化率 | |
CO | 13% | 1.3% | 90% |
CHx | 3180ppm | 145ppm | 95.4% |
在以上实施例1~6中,Cu、Co、Fe、Mn均应折算成相应的硝酸盐重量,其余不足100%的量为载体γ-Al2O3小球的重量。上述催化剂用于柴油机(包括柴油机车)尾气的治理时,需要以外部热源短时启动,以后可自行保温,其对尾气的净化率同上,并可把烟度降至接近于零。
上述催化剂还可用于煤的燃烧或垃圾焚烧炉排出的废气治理,净化率同上,其中:SO2含量在5ppm以下时可经氧化或SO3而去除。对废气中飘尘的去除也可达95%以上。
当载体使用电解涂布有活性组分的金属网时,其净化效果不变,不再详细举例脱明。
Claims (4)
1.一种多环芳烃污染物的排气催化治理催化剂,以γ-Al2O3为载体,以铈的氧化物为一种活性组分,催化剂用浸渍法、经干燥、灼烧而成,其特征在于:在活性组分中,主要加入了以铈为主的混合轻稀土氧化物Ln,其余依次为铜、钴、铁和锰,它们之间的重量百分比为:Ln∶Cu∶Co∶Fe∶Mn=(10~15)∶(9~14)∶(8~13)∶0.5∶0.5,其余不足100%的量是γ-Al2O3载体,
所述的混合轻稀土氧化物Ln,除了铈以外,其余依次为镧、钕、镨和钐,它们的氧化物之间的重量百分比为:CeO2∶La2O3∶Nd2O3∶Pr6O11∶SmO2=40∶(25~40)∶(15~18)∶(6~8)∶3。
2.一种多环芳烃污染物的排气催化治理催化剂,以γ-Al2O3为载体,以铈的氧化物为一种活性组分,催化剂用浸渍法、经干燥、灼烧而成,其特征在于:在活性组分中,主要加入了以铈为主的混合轻稀土氧化物Ln,其余依次为铁、锰、铜和钴,它们之间的重量百分比为:Ln∶Fe∶Mn∶Cu∶Co=(10~20)∶(1.7~3.9)∶(1.5~3.5)∶0.5∶0.5,其余不足100%的量是γ-Al2O3载体,
所述的混合轻稀土氧化物Ln,除了铈以外,其余依次为镧、钕、镨和钐,它们的氧化物之间的重量百分比为:CeO2∶La2O3∶Nd2O3∶Pr6O11∶SmO2=40∶(25~40)∶(15~18)∶(6~8)∶3。
3.根据权利要求1或2所述的一种多环芳烃污染物的排气催化治理催化剂,其特征在于:所述的γ-Al2O3载体的粒度在4~6毫米之间。
4.根据权利要求1或2所述的一种多环芳烃污染物的排气催化治理催化剂,其特征在于:浸渍法用的盐溶液是铜、钴、锰、铁、铈的硝酸盐和以铈为主的混合轻稀土硝酸盐的水溶液。
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CN96114305A CN1059353C (zh) | 1996-12-12 | 1996-12-12 | 多环芳烃污染物的排气催化治理催化剂 |
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CN96114305A CN1059353C (zh) | 1996-12-12 | 1996-12-12 | 多环芳烃污染物的排气催化治理催化剂 |
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CN1184697A CN1184697A (zh) | 1998-06-17 |
CN1059353C true CN1059353C (zh) | 2000-12-13 |
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JP5921387B2 (ja) * | 2012-08-27 | 2016-05-24 | 三井金属鉱業株式会社 | 排ガス浄化触媒 |
CN103820174A (zh) * | 2014-03-19 | 2014-05-28 | 王宝根 | 内燃机燃烧设备尾气污染物净化治理剂及其制备方法 |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
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CN85109694A (zh) * | 1985-12-12 | 1987-06-24 | 华东化工学院 | 非贵金属蜂窝状燃烧催化剂 |
CN1046473A (zh) * | 1989-04-21 | 1990-10-31 | 中国科学院大连化学物理研究所 | 汽车排气净化催化剂 |
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Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
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CN85109694A (zh) * | 1985-12-12 | 1987-06-24 | 华东化工学院 | 非贵金属蜂窝状燃烧催化剂 |
CN1046473A (zh) * | 1989-04-21 | 1990-10-31 | 中国科学院大连化学物理研究所 | 汽车排气净化催化剂 |
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