La1-x Sr x MnO3钙钛矿涂层的抗结焦性能

doi:10.16085/j.issn.1000-6613.2022-1011

摘要/Abstract

摘要：

目前，钙钛矿材料在汽车尾气催化处理、污水处理及燃料电池等方面应用广泛，但在抑制热裂解结焦涂层应用方面鲜有报道。本文以磷酸二氢铝为黏结剂，采用浆料法在HP40不锈钢基体表面制备了La_1-_x Sr _x MnO₃钙钛矿涂层，采用X射线衍射（XRD）、扫描电子显微镜（SEM）、能谱仪（EDS）和Raman光谱考察了La_1-_x Sr _x MnO₃钙钛矿涂层及表面焦层的物相组成和微观结构，利用X射线光电子能谱（XPS）研究了涂层组成元素的化学状态，通过石脑油热裂解结焦实验评价了涂层的抗结焦效果。结合材料表征与实验结果，阐述了涂层抗结焦机理。表征结果显示，La_1-_x Sr _x MnO₃钙钛矿涂层涂覆均匀，厚度约为30μm，与基底贴合紧密，粒子之间结合较好，但表面存在少量微孔；La_1-_x Sr _x MnO₃钙钛矿氧化物具有明显的立方晶体特征，Sr进入LaMnO₃晶格未改变钙钛矿晶相结构；与未经掺杂的LaMnO₃涂层相比，Sr掺杂后的钙钛矿表面吸附氧含量与晶格氧含量之比O_ads/O_latt更高，而且涂层中氧空位的数量增加。热裂解结焦实验结果表明，钙钛矿涂层的抗结焦性能随着Sr含量的提高而增强，当裂解时间为3h和5h时，La_0.2Sr_0.8MnO₃涂层的抑制结焦效果分别可达到84.88%和82.31%。钙钛矿涂层结构不仅通过屏蔽基底金属的催化活性抑制了催化结焦过程，还通过催化焦炭氧化燃烧反应进一步减少热裂解焦炭的沉积。其中，Sr的掺杂可促进氧空位形成，增加氧的流动性，从而促进电子转移，进一步提高催化焦炭燃烧反应的活性。钙钛矿La_1-_x Sr _x MnO₃涂层的涂覆会导致焦层中无序化焦炭的比例增加，焦炭的石墨化程度降低，有利于后续的清焦操作。

关键词: 热解, 钙钛矿, 界面, 催化, 焦炭

Abstract:

At present, perovskite materials are widely used in the treatment of automobile tail gas, sewage treatment and fuel cell. However, there are limited reports on the application of those materials in coking inhibition during the thermal cracking of hydrocarbons. In this paper, La_1-_x Sr _x MnO₃ perovskite-type coatings were prepared by the slurry method on the HP40 stainless steel substrate with aluminum dihydrogen phosphate as the binder. The phase composition and microstructure of the coatings and the coke layers were characterized by XRD, SEM, EDS and Raman spectroscopy. The chemical states of the elements in the coatings were analyzed by XPS. The coking inhibition performance of the coatings were evaluated through the pyrolysis of naphtha. The results showed that La_1-_x Sr _x MnO₃ perovskite coatings were uniformly formed on the metal surface with a thickness of about 30μm and well adhered to the substrate. The coating particles were tightly bonded although a small amount of micropores were presented in the coatings. La_1-_x Sr _x MnO₃ perovskite oxides presented a featured cubic crystal structure. Furthermore, the incorporation of Sr into the lattice of LaMnO₃ did not change the perovskite phase. Compared with undoped LaMnO₃ perovskite coating, the doping of Sr into the coatings resulted in the higher ratios of O_ads/O_latt and the formation of more oxygen vacancies. The anti-coking rate was increased with the doping content of Sr in the coating. When the cracking time were 3h and 5h, the coking inhibition rates were 84.88% and 82.31%, respectively. La_1-_x Sr _x MnO₃perovskite coatings not only suppressed the catalytic coking by blocking the activity of the substrate metal but also mitigated the coke deposition by catalyzing the oxidation combustion of the coke deposits. Moreover, the doping of Sr into the coatings generated more oxygen vacancies which increased oxygen mobility and promoted electron transfer, and thus improved the catalytic activity of coke combustion. An increased proportion of disordered coke deposits and a decreased graphitization degree were found in the coke layers of La_1-_x Sr _x MnO₃ coatings, which would facilitate the decoking operation.

Key words: pyrolysis, perovskite, interface, catalysis, coke deposits

中图分类号:

TE624

梁贻景, 马岩, 卢展烽, 秦福生, 万骏杰, 王志远. La_1-_x Sr _x MnO₃钙钛矿涂层的抗结焦性能[J]. 化工进展, 2023, 42(4): 1769-1778.

LIANG Yijing, MA Yan, LU Zhanfeng, QIN Fusheng, WAN Junjie, WANG Zhiyuan. Experimental investigation on the anti-coking performance of La_1-_x Sr _x MnO₃ perovskite coating[J]. Chemical Industry and Engineering Progress, 2023, 42(4): 1769-1778.

图/表 16

表1 镧酸锶锰钙钛矿粉末合成实验表

A位	B位	La/Sr 摩尔比例	分子式	简写
La	Mn	1∶0	LaMnO₃	LMO
La(Sr)	Mn	0.8∶0.2	La_0.8Sr_0.2MnO₃	LS2MO
La(Sr)	Mn	0.4∶0.6	La_0.4Sr_0.6MnO₃	LS6MO

表2 轻石脑油的物性参数

成分	质量分数/%
正链烷烃	17.07
异链烷烃	53.47
环烷烃	27.78
烯烃	1.3
芳烃	0.37

表 3 裂解实验参数

裂解压力 /MPa	热裂解温度 /℃	石脑油流量 /mL·min^-1	水流量 /mL·min^-1	水油比
0.2	850	2	0.7	0.5

图1 裂解实验流程图1—去离子水；2—轻石脑油；3—平流泵；4—针阀；5—温度控制器；6—预热炉；7—裂解炉；8—试样；9—水冷却器；10—三通阀；11—冷却罐；12—重烃凝析油罐；13—净化装置

图2 LSMO系列涂层的表面和截面形貌SEM照片

图 3 LSMO系列涂层表面的EDS分析

表4 LSMO涂层中元素的原子分数

元素	原子分数/%
元素	LMO	LS2MO	LS6MO
C	8.25	9.92	12.57
O	55.63	55.81	50.94
Al	1.82	1.46	1.67
P	5.38	3.39	4.16
Mn	14.08	14.16	15.12
Sr	—	4.58	9.55
La	14.84	10.68	5.99

图4 不同Sr掺杂量涂层的XRD图

图5 不同Sr掺杂量条件下涂层的XPS谱

表5 钙钛矿表面Mn 2p、O 1s的氧化态组成及分布

样品	O 1s						Mn 2p
	O_latt		O_abs		O_Ⅲ		Mn³⁺			Mn⁴⁺
	结合能/eV	分布/%	结合能/eV	分布/%	结合能/eV	分布/%	Mn 2p_3/2	Mn 2p_1/2	分布/%	Mn 2p_3/2	Mn 2p_1/2	分布/%
	结合能/eV	分布/%	结合能/eV	分布/%	结合能/eV	分布/%	结合能/eV	结合能/eV	分布/%	结合能/eV	结合能/eV	分布/%
LMO	528.90	45.05	529.99	23.87	531.03	31.08	641.23	652.48	67.73	642.90	654.06	32.27
LS2MO	528.82	37.76	530.38	30.42	531.72	31.81	640.84	652.50	53.52	642.52	653.82	46.48
LS6MO	528.69	23.66	529.72	44.64	531.51	31.70	641.22	652.74	48.82	642.39	653.85	51.18

图6 不同裂解时间下涂层表面焦炭沉积情况

表6 不同裂解时间下结焦实验结果

试样	3h结焦速率 /10^-3mg∙mm^-2∙h^-1	3h结焦抑制率/%	5h结焦速率 /10^-3mg∙mm^-2∙h^-1	5h结焦抑制率/%
空白氧化试样	26.5	0	22.4	0
LMO	5.9	77.7	5.8	74.0
LS2MO	5.5	79.3	4.8	78.8
LS6MO	4.0	84.9	3.9	82.3

图7 裂解时间为3h时LSMO涂层表面焦炭的SEM照片

图8 裂解时间为5h时LSMO涂层表面焦炭的SEM照片

图9 空白试样及LSMO涂层表面焦炭的拉曼光谱

表7 不同条件下沉积焦炭的拉曼光谱拟合结果

样品	$Γ D 1$ /cm^-1	$Γ D 2$ /cm^-1	$Γ D 3$ /cm^-1	$Γ D 4$ /cm^-1	Γ_G/cm^-1	$I D 1$ /I_G	$I D 3$ /I_G
空白试样	124.98	45.36	102.20	125.18	56.50	2.98	0.70
LMO	111.98	40.9	113.57	119.79	45.40	3.29	0.79
LS2MO	124.48	43.92	102.33	127.44	54.34	3.68	0.83
LS6MO	120.50	41.00	127.16	124.23	55.36	4.36	0.95

表7 不同条件下沉积焦炭的拉曼光谱拟合结果

样品	$Γ D 1$ /cm^-1	$Γ D 2$ /cm^-1	$Γ D 3$ /cm^-1	$Γ D 4$ /cm^-1	Γ_G/cm^-1	$I D 1$ /I_G	$I D 3$ /I_G
空白试样	124.98	45.36	102.20	125.18	56.50	2.98	0.70
LMO	111.98	40.9	113.57	119.79	45.40	3.29	0.79
LS2MO	124.48	43.92	102.33	127.44	54.34	3.68	0.83
LS6MO	120.50	41.00	127.16	124.23	55.36	4.36	0.95

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La_1-_x Sr _x MnO₃钙钛矿涂层的抗结焦性能

Experimental investigation on the anti-coking performance of La_1-_x Sr _x MnO₃ perovskite coating

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