Preparation of MnO coating based on electroplating-low oxygen partial pressure treatment and coking inhibition properties during thermal cracking of naphtha

doi:10.11949/0438-1157.20240891

Abstract

Abstract:

MnO coating was prepared on the surface of 310S alloy by electrodeposition-low oxygen partial pressure method. The coking inhibition performance of the coating was evaluated under the conditions of naphtha pyrolysis, and the phase transformation process of MnO _x components during the cracking-decoking cycle was systematically investigated. X-ray diffraction, scanning electron microscopy, energy dispersive spectroscopy, X-ray photoelectron spectroscopy and Raman spectroscopy were used to characterized the phase composition, surface morphology, chemical valence state and chemical structure of the coating and coke deposits. The results showed that the MnO coating was smooth and dense with the thickness of about 45 μm. When the cracking time was 3 h and 5 h, the coking inhibition rate of MnO coating was 75.84% and 74.22%, respectively. However, MnO phase in the coating was changed with the cracking/decoking cycles, which led to a poor adhesion between the coating and the alloy substrate and a rapid decrease in coking inhibition effect subsequently. Overall, the coating maintained an excellent anti-coking effect in the 3 cracking/decoking cycles. The results in this paper are expected to provide the guide for the development and application of the manganese oxide coating with an ability of catalyzing coke oxidation.

Key words: electrodeposition, manganese oxide coating, pyrolysis, coking, hydrocarbons

摘要：

利用电沉积-低氧分压方法在310S合金表面制备了MnO涂层，在石脑油热裂解条件下对涂层的抑制结焦性能进行了评价，系统考察了MnO _x 组分在裂解-清焦周期过程中物相转变过程。采用X射线衍射、扫描电子显微镜、能量色散谱仪、X射线光电子能谱和拉曼光谱表征了涂层及热裂解焦炭的物相组成、表面形貌、元素化合价态和化学结构。结果表明，MnO涂层表面平整致密，与基体结合紧密，涂层厚度约为45 μm。当裂解时间为3 h和5 h时，MnO涂层的结焦抑制率分别为75.84%和74.22%。但涂层体相中MnO成分随着裂解/清焦循环次数增加发生改变，导致涂层剥落，抗结焦效率降低。裂解/清焦循环次数在3次以内，MnO涂层抗结焦效果稳定。本文研究结果有望为锰氧化物催化涂层的开发与应用提供指导。

关键词: 电沉积, 锰氧化物涂层, 热解, 焦化, 碳氢化合物

CLC Number:

TE 624

Zhongqing LI, Zhiyuan WANG, Xiaojian LUAN, Sikai LIANG, Kai WANG. Preparation of MnO coating based on electroplating-low oxygen partial pressure treatment and coking inhibition properties during thermal cracking of naphtha[J]. CIESC Journal, 2025, 76(3): 1050-1063.

李中青, 王志远, 栾小建, 梁四凯, 王凯. 电沉积-低氧分压法制备MnO涂层及其抑制石脑油热裂解结焦性能研究[J]. 化工学报, 2025, 76(3): 1050-1063.

Figures/Tables 22

Table 1 Chemical composition of 310S alloy

成分	质量分数/%
C	≤0.080
Mn	≤2.000
P	≤0.045
S	≤0.030
Si	≤1.500
Cr	24.000~28.000
Ni	19.000~22.000
Fe	其余

Fig.1 Flow chart of low oxygen partial pressure and high temperature treatment

Fig.2 Flow chart of thermal cracking experiment

Table 2 Physical parameters of light naphtha

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	1.30
芳烃	0.37

Table 3 Parameters of thermal cracking experiment

参数	数值
裂解压力	0.1 MPa
热裂解温度	850℃
石脑油流量	2 ml/min
水流量	0.7 ml/min
水油比	0.5

Fig.3 Surface morphologies and element distributions of the alloy sample after electrodeposition experiment

Fig.4 Morphologies and element distributions of the coating after thermal pretreatment in Ar-H2O environment

Fig.5 Cross-sectional morphologies and elemental distributions of the coating after thermal pretreatment in Ar-H2O environment

Fig.6 X-ray diffraction patterns of the coatings treated by electrodeposition and thermal heating in Ar-H2O environment

Fig.7 XPS spectra of the coating after heat treatment in Ar-H2O environment

Fig.8 Coke deposition at the surface of the coating and blank oxidation samples under different cracking time

Table 4 Results of coking tests at different cracking time

样品	3 h结焦速率/(10^-3 mg/(mm²·h))	3 h结焦抑制率/%	5 h结焦速率/(10^-3 mg/(mm²·h))	5 h结焦抑制率/%
空白氧化试样	19.10	0	15.00	0
涂层试样	4.62	75.84	4.33	74.22

Fig.9 SEM images of coke deposits at the surface of the coating and blank oxidation samples under the conditions of 3 h and 5 h of cracking time

Fig.10 Coking behavior at the samples surface during the initial stage of light naphtha thermal cracking

Fig.11 Mass of coke deposits at the surface of the coating and blank oxidation samples after multiple cracking/decoking cycles

Fig.12 Morphologies and element distributions of the coating after three cracking/decoking cycles

Fig.13 Morphologies of the coating and blank oxidation samples after the 6th coking

Fig.14 Cross-sectional morphologies and element distributions of the coatings after different times of cracking/decoking cycles

Fig.15 X-ray diffraction patterns of the coatings after different times of cracking/decoking cycles

Fig.16 XPS spectra of the coatings after 3 h coking experiment and 3 cracking/decoking cycles

Fig.17 Raman spectra of coke at the surface of the coating and blank oxidation samples

Table 5 Fitting results of Raman spectra of coke deposits

样品	Γ_D1/cm^-1	Γ_D2/cm^-1	Γ_D3/cm^-1	Γ_D4/cm^-1	Γ_G/cm^-1	I_D1/I_G	I_D3/I_G
涂层试样	114.51	50.10	183.52	183.74	48.93	3.58	2.80
空白氧化试样	79.51	52.94	211.04	257.28	63.01	1.36	1.55

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