La1-xLixMnO3钙钛矿催化剂同时消除NO和碳烟催化性能

doi:10.11949/0438-1157.20190849

化工学报 ›› 2020, Vol. 71 ›› Issue (3): 1053-1059.DOI: 10.11949/0438-1157.20190849

• 催化、动力学与反应器 • 上一篇下一篇

La_1-_xLi_xMnO₃钙钛矿催化剂同时消除NO和碳烟催化性能

刘晓刚¹,魏波^1,³,史芸菲¹,孙巾茹^1,²,田雨^1,²,赵玉¹,迟姚玲¹,王虹¹(),李翠清¹,宋永吉¹

^1.北京石油化工学院化学工程学院，燃料清洁化及高效催化减排技术北京市重点实验室，北京 102617
^2.北京工业大学环境与能源工程学院，北京 100124
^3.长岭炼化岳阳工程设计有限公司，湖南岳阳 414000

收稿日期:2019-07-24 修回日期:2019-10-18 出版日期:2020-03-05 发布日期:2020-03-05
通讯作者: 王虹
基金资助:
国家自然科学基金项目(U1662103);燃料清洁化及高效催化减排技术北京市重点实验室项目(BZ041420180007);国家大学生创新创业训练计划项目(2019J00100)

Simultaneous removal of NO and soot over La_1-_xLi_xMnO₃ perovskite catalysts

Xiaogang LIU¹,Bo WEI^1,³,Yunfei SHI¹,Jinru SUN^1,²,Yu TIAN^1,²,Yu ZHAO¹,Yaoling CHI¹,Hong WANG¹(),Cuiqing LI¹,Yongji SONG¹

^1.Beijing Key Laboratory of Fuels Cleaning and Advanced Catalytic Emission Reduction Technology, College of Chemical Engineering, Beijing Institute of Petrochemical Technology, Beijing 102617, China
^2.College of Environmental and Energy Engineering, Beijing University of Technology, Beijing 100124, China
^3.Yueyang Changling Refinery Engineering Co. , Ltd. , Yueyang 414000, Hunan, China

Received:2019-07-24 Revised:2019-10-18 Online:2020-03-05 Published:2020-03-05
Contact: Hong WANG

摘要/Abstract

摘要：

采用溶剂热法制备La_1-_xLi_xMnO₃ (x=0,0.05,0.15,0.25) 钙钛矿型复合金属氧化物催化剂。通过XRD、FT-IR、XPS、H₂-TPR和NO-TPD等手段对催化剂进行表征，在固定床微型反应器中评价催化剂同时消除NO和碳烟催化性能。结果表明，溶剂热法制备的La_1-_xLi_xMnO₃催化剂具有单一的钙钛矿结构，催化剂中Mn物种以Mn³⁺和Mn⁴⁺的形式存在。Li⁺部分取代LaMnO₃中La³⁺后，La_1-_xLi_xMnO₃催化剂上Mn⁴⁺数量和氧空位增加，促进更多活性氧物种和氮氧化物的吸附与活化，提高氧化还原性能，改善催化活性。Li⁺取代量为0.15，即La_0.85Li_0.15MnO₃催化剂催化活性较好，T_max和T_ig分别为463℃和327℃，NO最大转化率 $X N O m a x$ 为42.1%，反应温度 $T N O m a x$ 为383℃。

关键词: 锰基钙钛矿, 一氧化氮, 碳烟, 催化剂, 化学反应, 固定床

Abstract:

Catalysts of La_1-_xLi_xMnO₃(x=0, 0.05, 0.15, 0.25) perovskite-type complex metal oxide were prepared by solvothermal method. The catalysts were characterized by XRD, FT-IR, XPS, H₂-TPR and NO-TPD. The catalytic performance of the catalysts for eliminating nitric oxide (NO) and diesel particulate matter （soot） simultaneously was evaluated in a fixed micro reactor. The results showed that La_1-_xLi_xMnO₃ catalysts had single perovskite structure and Mn species existed in the form of Mn³⁺ and Mn⁴⁺. When La³⁺ is partially substituted by Li⁺ in LaMnO₃, there were more Mn⁴⁺ and oxygen vacancies in the La_1-_xLi_xMnO₃ catalysts, which can promote the adsorption and activation of oxygen species and nitrogen oxides, thus increase the redox properties and improve the catalytic activity. The La_0.85Li_0.15MnO₃ catalyst had better performance, where the doping amount of Li⁺ was 0.15, the temperature of the maximum combustion rate (T_max) and the ignition temperature (T_ig) was 463℃ and 327℃, respectively, the maximum conversion of NO ( $X N O m a x$ ) was 42.1%, reaction temperature ( $T N O m a x$ ) was 383℃.

Key words: Mn-based perovskite, NO, soot, catalyst, chemical reaction, fixed-bed

中图分类号:

O 643.3

刘晓刚, 魏波, 史芸菲, 孙巾茹, 田雨, 赵玉, 迟姚玲, 王虹, 李翠清, 宋永吉. La_1-_xLi_xMnO₃钙钛矿催化剂同时消除NO和碳烟催化性能[J]. 化工学报, 2020, 71(3): 1053-1059.

Xiaogang LIU, Bo WEI, Yunfei SHI, Jinru SUN, Yu TIAN, Yu ZHAO, Yaoling CHI, Hong WANG, Cuiqing LI, Yongji SONG. Simultaneous removal of NO and soot over La_1-_xLi_xMnO₃ perovskite catalysts[J]. CIESC Journal, 2020, 71(3): 1053-1059.

图/表 8

图1 La1-xLixMnO3催化剂的XRD谱图

Fig.1 XRD patterns of La1-xLixMnO3 catalysts

图2 La1-xLixMnO3催化剂的FT-IR谱图

Fig.2 FT-IR spectra of La1-xLixMnO3 catalysts

图3 La1-xLixMnO3催化剂的O 1s态光电子能谱图

Fig.3 XPS spectra of O 1s state in La1-xLixMnO3 catalysts

表1 La1-xLixMnO3催化剂的XPS表征结果

Table 1 XPS data of La1-xLixMnO3 catalysts

Sample	Binding energy/eV		O_ads/O_latt	Binding energy/eV		Mn⁴⁺/Mn³⁺
Sample	O_latt	O_ads	O_ads/O_latt	Mn³⁺	Mn⁴⁺	Mn⁴⁺/Mn³⁺
LaMnO₃	529.29	531.32	0.662	641.11	642.47	0.675
La_0.95Li_0.05MnO₃	529.21	530.99	0.742	641.15	642.67	0.747
La_0.85Li_0.15MnO₃	529.28	530.91	0.922	641.24	642.66	0.942
La_0.75Li_0.25MnO₃	529.17	530.95	0.827	641.03	642.47	0.842

图4 La1-xLixMnO3催化剂的Mn 2p态光电子能谱图

Fig.4 XPS spectra of Mn 2p state in La1-xLixMnO3 catalysts

图5 La1-xLixMnO3催化剂的H2-TPR谱图

Fig.5 H2-TPR profiles of La1-xLixMnO3 catalysts

图6 La1-xLixMnO3催化剂的NO-TPD谱图

Fig.6 NO-TPD profiles of La1-xLixMnO3 catalysts

图7 La1-xLixMnO3催化剂同时消除NO和碳烟催化性能

Fig.7 Catalytic performance of La1-xLixMnO3catalysts for simultaneous removal NO and soot

参考文献 33

1	Dhal G C,Dey S,Mohan D,et al.Simultaneous abatement of diesel soot and NO_x emissions by effective catalysts at low temperature: an overview[J].Catalysis Reviews,2018,60(3):437-496.
2	Feng N J,Meng J,Wu Y,et al.KNO₃ supported on three-dimensionally ordered macroporous La_0.8Ce_0.2Mn_1-_xFe_xO₃ for soot removal[J].Catalysis Science & Technology,2016,6(9):2930-2941.
3	Dhal G C,Dey S,Mohan D,et al.Study of Fe, Co, and Mn-based perovskite-type catalysts for the simultaneous control of soot and NO_x from diesel engine exhaust[J].Materials Discovery,2018,10:37-42.
4	Dhal G C,Mohan D,Prasad R.Preparation and application of effective different catalysts for simultaneous control of diesel soot and NO_x emissions: an overview[J].Catalysis Science & Technology,2017,7(9):1803-1825.
5	Matarrese R,Morandi S,Castoldi L,et al.Removal of NO_x and soot over Ce/Zr/K/Me (Me=Fe, Pt, Ru, Au) oxide catalysts[J].Applied Catalysis B: Environmental,2017,201:318-330.
6	Urán L,Gallego J,Li W Y,et al.Effect of catalyst preparation for the simultaneous removal of soot and NO_x[J].Applied Catalysis A: General,2019,569:157-169.
7	Castoldi L,Matarrese R,Lietti L,et al.Simultaneous removal of NO_x and soot on Pt-Ba/Al₂O₃ NSR catalysts[J].Applied Catalysis B: Environmental,2006,64(1/2):25-34.
8	Liu J,Zhao Z,Xu C M,et al.Simultaneous removal of soot and NO_x over the (La_1.7Rb_0.3CuO₄)_x/nm CeO₂ nanocomposite catalysts[J].Industrial & Engineering Chemistry Research,2010,49(7):3112-3119.
9	Liu J,Zhao Z,Xu C M,et al.Simultaneous removal of NO_x and diesel soot particulates over nanometric La_2-_xK_xCuO₄ complex oxide catalysts[J].Catalysis Today,2007,119(1/2/3/4):267-272.
10	Wang K,Qian L,Zhang L,et al.Simultaneous removal of NO_x and soot particulates over La_0.7Ag_0.3MnO₃ perovskite oxide catalysts[J].Catalysis Today,2010,158(3/4):423-426.
11	王虹,王军利,李翠清,等.柴油机尾气碳颗粒燃烧中La-Mn-Fe-Cu/HZSM-5的催化性能[J].燃料化学学报,2012,40(3):374-379.
	Wang H,Wang J L,Li C Q,et al.Catalytic performance of La-Mn-Fe-Cu/HZSM-5 catalysts for soot combustion from diesel exhaust[J].Journal of Fuel Chemistry and Technology,2012,40(3):374-379.
12	Meng X X,He F L,Shen X Q,et al.Nanocrystalline La_1-_xK_xFeO₃ (x=0—0.4) oxides for catalytic removal of soot from practical diesel exhaust emission[J].Industrial & Engineering Chemistry Research,2011,50(19):11037-11042.
13	陈彦广,何峰,Shivalik Daga,等.钙钛矿型复合氧化物对甲烷的部分氧化及在混合太阳能氧化还原过程的应用[J].化工学报,2014,65(7):2741-2750.
	Chen Y G,He F,Daga S,et al.Redox conversion of methane with Fe₂O₃-CaTi_xM_1-_xO₃ composite oxides for hydrogen and liquid fuel co-production[J].CIESC Journal,2014,65(7):2741-2750.
14	Yoon D Y,Lim E,Kim Y J,et al.NO oxidation activity of Ag-doped perovskite catalysts[J].Journal of Catalysis,2014,319:182-193.
15	Wang H,Liu J,Zhao Z,et al.Comparative study of nanometric Co-, Mn- and Fe-based perovskite-type complex oxide catalysts for the simultaneous elimination of soot and NO_x from diesel engine exhaust[J].Catalysis Today,2012,184(1):288-300.
16	张晓华,李凝,滕俊江,等.掺杂离子的种类对介孔La_0.6A_0.4NiO₃钙钛矿催化剂的结构与催化活性的影响[J].化工进展,2016,35(11):3542-3548.
	Zhang X H,Li N,Teng J J,et al.Structure and catalytic activity of mesoporous La_0.6A_0.4NiO₃ perovskite catalyst with A-site ions replaced[J].Chemical Industry and Engineering Progress,2016,35(11):3542-3548.
17	Teraoka Y,Kanada K,Kagawa S.Synthesis of La-K-Mn-O perovskite-type oxides and their catalytic property for simultaneous removal of NO_x and diesel soot particulates[J].Applied Catalysis B: Environmental,2001,34(1):73-78.
18	Wang H,Zhao Z,Xu C M,et al.Nanometric La_1-_xK_xMnO₃ perovskite-type oxides—highly active catalysts for the combustion of diesel soot particle under loose contact conditions[J].Catalysis Letters,2005,102(3/4):251-256.
19	Xu J F,Liu J,Zhao Z,et al.Easy synthesis of three-dimensionally ordered macroporous La_1-_xK_xCoO₃ catalysts and their high activities for the catalytic combustion of soot[J].Journal of Catalysis,2011,282(1):1-12.
20	王虹,赵震,徐春明,等.纳米La-Mn-O钙钛矿型氧化物催化剂上柴油机尾气碳颗粒催化燃烧性能的研究[J].科学通报,2005,50(4):336-339.
	Wang H,Zhao Z,Xu C M,et al.Catalytic performance of nanometric La-Mn-O perovskite-type oxides catalysts for soot combustion from diesel exhaust[J].Chinese Science Bulletin,2005,50(4):336-339.
21	Shen M Q,Zhao Z,Chen J H,et al.Effects of calcium substitute in LaMnO₃ perovskites for NO catalytic oxidation[J].Journal of Rare Earths,2013,31(2):119-123.
22	Zhang-Steenwinkel Y,Beckers J,Bliek A.Surface properties and catalytic performance in CO oxidation of cerium substituted lanthanum-manganese oxides[J].Applied Catalysis A: General,2002,235(1/2):79-92.
23	Cheng Y,Liu J,Zhao Z,et al.The simultaneous purification of PM and NO_x in diesel engine exhausts over a single 3DOM Ce_0.9-_xFe_0.1Zr_xO₂ catalyst[J].Environmental Science: Nano,2017,4(5):1168-1177.
24	Yang J P,Zhang M G,Li H L,et al.Simultaneous NO reduction and Hg⁰ oxidation over La_0.8Ce_0.2MnO₃ perovskite catalysts at low temperature[J].Industrial & Engineering Chemistry Research,2018,57(29):9374-9385.
25	Ding Y,Wang S,Zhang L,et al.A facile method to promote LaMnO₃ perovskite catalyst for combustion of methane[J].Catalysis Communications,2017,97:88-92.
26	Wang Y Z,Xie S H,Deng J G,et al.Morphologically controlled synthesis of porous spherical and cubic LaMnO₃ with high activity for the catalytic removal of toluene[J].ACS Applied Materials & Interfaces,2014,6(20):17394-17401.
27	Zhu J J,Li H L,Zhong L Y,et al.Perovskite oxides: preparation, characterizations, and applications in heterogeneous catalysis[J].ACS Catalysis,2014,4(9):2917-2940.
28	Teng F,Han W,Liang S H,et al.Catalytic behavior of hydrothermally synthesized La_0.5Sr_0.5MnO₃ single-crystal cubes in the oxidation of CO and CH₄[J].Journal of Catalysis,2007,250(1):1-11.
29	Wang L,Xie H K,Wang X D,et al.Preparation of LaMnO₃ for catalytic combustion of vinyl chloride[J].Chinese Journal of Catalysis,2017,38(8):1406-1412.
30	Lu Y J,Dai Q G,Wang X Y.Catalytic combustion of chlorobenzene on modified LaMnO₃ catalysts[J].Catalysis Communications,2014,54:114-117.
31	Li Z Q,Meng M,Zha Y Q,et al.Highly efficient multifunctional dually-substituted perovskite catalysts La_1-_xK_xCo_1-_yCu_yO_3-δ used for soot combustion, NO_x storage and simultaneous NO_x-soot removal[J].Applied Catalysis B: Environmental,2012,121/122:65-74.
32	Chen J H,Shen M Q,Wang X Q,et al.Catalytic performance of NO oxidation over LaMeO₃ (Me=Mn, Fe, Co) perovskite prepared by the sol-gel method[J].Catalysis Communications,2013,37:105-108.
33	Li Z Q,Meng M,Dai F F,et al.Performance of K and Ni substituted La_1-_xK_xCo_1-_yNi_yO_3-δ perovskite catalysts used for soot combustion, NO_x storage and simultaneous NO_x-soot removal[J].Fuel,2012,93:606-610.

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La_1-_xLi_xMnO₃钙钛矿催化剂同时消除NO和碳烟催化性能

Simultaneous removal of NO and soot over La_1-_xLi_xMnO₃ perovskite catalysts

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