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

doi:10.11949/0438-1157.20240891

摘要/Abstract

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

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

中图分类号:

TE 624

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.

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.

图/表 22

表1 310S合金化学成分

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

图1 低氧分压高温处理流程图

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

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

Fig.2 Flow chart of thermal cracking experiment

表2 轻石脑油的物性参数

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

表3 裂解实验参数

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

图3 电沉积实验后合金试样表面形貌和元素分布

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

图4 Ar-H2O气氛热处理条件下涂层形貌和元素分布

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

图5 Ar-H2O环境下热处理后涂层的截面形貌和元素分布情况

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

图6 经过电沉积和Ar-H2O环境中热处理后涂层的X射线衍射图

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

图7 Ar-H2O环境热处理后涂层的XPS谱图

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

图8 不同裂解时间下涂层及空白氧化试样表面焦炭沉积情况

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

表4 不同裂解时间下结焦实验结果

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

图9 裂解时间3 h和5 h条件下涂层及空白氧化试样表面焦炭沉积的SEM照片

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

图10 轻质石脑油热裂解初期试样表面的结焦行为

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

图11 多次裂解/清焦循环后涂层及空白氧化试样表面焦炭沉积情况

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

图12 3次裂解/清焦循环后涂层形貌和元素分布

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

图13 第6次结焦后涂层及空白氧化试样形貌

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

图14 不同次数裂解/清焦循环实验后涂层横截面形貌及元素分布

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

图15 不同裂解/清焦循环实验后涂层的X射线衍射图

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

图16 3 h结焦实验和3次裂解/清焦循环后涂层的XPS谱图

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

图17 涂层及空白氧化试样表面焦炭的拉曼光谱

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

表5 热裂解结焦拉曼光谱的分峰拟合结果

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

参考文献 44

1	Bukhovko M P, Yang L, Li L W, et al. Gasification of radical coke with steam and steam-hydrogen mixtures over manganese-chromium oxides[J]. Industrial & Engineering Chemistry Research, 2020, 59(23): 10813-10822.
2	Amghizar I, Vandewalle L A, van Geem K M, et al. New trends in olefin production[J]. Engineering, 2017, 3(2): 171-178.
3	Xiao S F, Wang J L, Huang C P, et al. Failure analysis of convection section tube in an ethylene cracking furnace due to metal dusting[J]. Engineering Failure Analysis, 2023, 154: 107642.
4	Pourabdollah K, Khoshbin R, Moghaddam M A, et al. Predictive modeling of coke formation in ethylbenzene cracking on 304 H austenitic steel surface using response surface methodology (RSM)[J]. Chemical Engineering Research and Design, 2024, 202: 191-207.
5	Kucora I, Paunjoric P, Tolmac J, et al. Coke formation in pyrolysis furnaces in the petrochemical industry[J]. Petroleum Science and Technology, 2017, 35(3): 213-221.
6	屈笑雨, 刘京雷, 徐宏, 等. 25Cr₃₅NiNb合金表面Al-Si-Cr涂层抑制结焦性能[J]. 化工学报, 2015, 66(3): 1059-1065.
	Qu X Y, Liu J L, Xu H, et al. Anti-coking characteristics of Al-Si-Cr coating on 25Cr₃₅NiNb alloy[J]. CIESC Journal, 2015, 66(3): 1059-1065.
7	Symoens S H, Olahova N, Muñoz Gandarillas A E, et al. State-of-the-art of coke formation during steam cracking: anti-coking surface technologies[J]. Industrial & Engineering Chemistry Research, 2018, 57(48): 16117-16136.
8	Kwon H T, Bukhovko M P, Mahamulkar S, et al. Sol-gel derived CeO₂/α-Al₂O₃ bilayer thin film as an anti-coking barrier and its catalytic coke oxidation performance[J]. AIChE Journal, 2018, 64(11): 4019-4026.
9	王志远, 丁旭东, 王博研, 等. 硫化物和硫/磷化合物的添加方式对石脑油热裂解结焦影响的研究[J]. 化工学报, 2020, 71(11): 5320-5336.
	Wang Z Y, Ding X D, Wang B Y, et al. Addition methods of sulfur and sulfur/phosphorus-based compounds on coking behavior during thermal cracking of naphtha[J]. CIESC Journal, 2020, 71(11): 5320-5336.
10	Panjapornpon C, Rochpuang C, Bardeeniz S, et al. Machine learning approach with a posteriori-based feature to predict service life of a thermal cracking furnace with coking deposition[J]. Results in Engineering, 2024, 22: 102349.
11	Guan Y T, Zhang Y J, Zhang Z L, et al. Band gap regulation of LaFeO₃ via doping Sr for efficient conversion of coke and steam[J]. Ceramics International, 2024, 50(12): 21526-21537.
12	Xiong H H, Liu J L, Zhang Y J, et al. Anti-coking performance of Al/Si/Cr/Ce ceramic coating during naphtha steam cracking applied on Cr₂₅Ni₃₅Nb alloy[J]. Chemical Engineering Research and Design, 2023, 194: 756-767.
13	Bao B B, Liu J L, Xu H, et al. Insight into a high temperature selective oxidation of HP40 alloy under a H₂-H₂O environment[J]. RSC Advances, 2017, 7(14): 8589-8597.
14	Bukhovko M P, Yang L, Li L W, et al. Anticoking performance of electrodeposited Mn/MnO surface coating on Fe-Ni-Cr alloy during steam cracking[J]. ACS Engineering Au, 2021, 1(1): 73-84.
15	梁贻景, 马岩, 卢展烽, 等. 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 Y J, Ma Y, Lu Z F, et al. Experimental investigation on the anti-coking performance of La_1- _x Sr _x MnO₃perovskite coating[J]. Chemical Industry and Engineering Progress, 2023, 42(4): 1769-1778.
16	栾小建, 徐宏, 王志远, 等. SiO₂/S涂层和硫磷抑制剂的抑制结焦性能研究[J]. 石油炼制与化工, 2011, 42(5): 75-80.
	Luan X J, Xu H, Wang Z Y, et al. Research on the coking inhibition performance of SiO₂/S coating and sulfur/phosphorus containing coking inhibitor[J]. Petroleum Processing and Petrochemicals, 2011, 42(5): 75-80.
17	Wang B, Gong X L, Zhang Z D, et al. Investigation on carburization during the repeated coking and decoking process[J]. Industrial & Engineering Chemistry Research, 2020, 59(29): 13051-13059.
18	Ali S A, Ahmad T. Treasure trove for efficient hydrogen evolution through water splitting using diverse perovskite photocatalysts[J]. Materials Today Chemistry, 2023, 29: 101387.
19	Halder S, Kumar R A, Maity R, et al. A tailored direct-to-indirect band structure transition in double perovskite oxides influences its photocatalysis efficiency[J]. Ceramics International, 2023, 49(5): 8634-8645.
20	Wang B, Wang S X, Liu B, et al. Oxide film prepared by selective oxidation of stainless steel and anti-coking behavior during n-hexane thermal cracking[J]. Surface and Coatings Technology, 2019, 378: 124952.
21	Jampaiah D, Velisoju V K, Devaiah D, et al. Flower-like Mn₃O₄/CeO₂ microspheres as an efficient catalyst for diesel soot and CO oxidation: synergistic effects for enhanced catalytic performance[J]. Applied Surface Science, 2019, 473: 209-221.
22	Miao S, Chen S, Zeng J, et al. Synergistic effects between Mn and Co species in CO₂ hydrogenation over xCo/MnO catalysts[J]. Fuel, 2024, 362: 130853.
23	Touahra F, Sehailia M, Halliche D, et al. (MnO/Mn₃O₄)-NiAl nanoparticles as smart carbon resistant catalysts for the production of syngas by means of CO₂ reforming of methane: advocating the role of concurrent carbothermic redox looping in the elimination of coke[J]. International Journal of Hydrogen Energy, 2016, 41(46): 21140-21156.
24	Müller D, Knoll C, Artner W, et al. Combining in situ X-ray diffraction with thermogravimetry and differential scanning calorimetry—an investigation of Co₃O₄, MnO₂and PbO₂ for thermochemical energy storage[J]. Solar Energy, 2017, 153: 11-24.
25	Petric A, Ling H. Electrical conductivity and thermal expansion of spinels at elevated temperatures[J]. Journal of the American Ceramic Society, 2007, 90(5): 1515-1520.
26	Zhang G N, Xu Y H, Wu X Y, et al. Ultrathin ZnO coating layer to boost the electrochemical reaction kinetics of MnO cathode for advanced aqueous zinc-ion batteries[J]. Solid State Sciences, 2023, 146: 107371.
27	Oquab D, Xu N, Monceau D, et al. Subsurface microstructural changes in a cast heat resisting alloy caused by high temperature corrosion[J]. Corrosion Science, 2010, 52(1): 255-262.
28	Zhang Z B, Albright L F. Pretreatments of coils to minimize coke formation in ethylene furnaces[J]. Industrial & Engineering Chemistry Research, 2010, 49(4): 1991-1994.
29	Lu J M, Dreisinger D, Glück T. Manganese electrodeposition—A literature review[J]. Hydrometallurgy, 2014, 141: 105-116.
30	Sulcius A, Griskonis E, Kantminiene K, et al. Influence of different electrolysis parameters on electrodeposition of γ- and α-Mn from pure electrolytes—A review with special reference to Russian language literature[J]. Hydrometallurgy, 2013, 137: 33-37.
31	Xiao L, Wang S Y, Wang Y F, et al. High-capacity and self-stabilized manganese carbonate microspheres as anode material for lithium-ion batteries[J]. ACS Applied Materials & Interfaces, 2016, 8(38): 25369-25378.
32	Zhang J, Lin J, Zeng Y B, et al. Morphological and structural evolution of MnO@C anode and its application in lithium-ion capacitors[J]. ACS Applied Energy Materials, 2019, 2(11): 8345-8358.
33	Tang W X, Yao M S, Deng Y Z, et al. Decoration of one-dimensional MnO₂ with Co₃O₄ nanoparticles: a heterogeneous interface for remarkably promoting catalytic oxidation activity[J]. Chemical Engineering Journal, 2016, 306: 709-718.
34	Guo Y Y, Zheng L M, Lan J L, et al. MnO nanoparticles encapsulated in carbon nanofibers with sufficient buffer space for high-performance lithium-ion batteries[J]. Electrochimica Acta, 2018, 269: 624-631.
35	Stokłosa A. Point defects diagrams for pure and doped manganese oxide Mn_1- _δ O in the temperature range of 1173-1830 K[J]. Materials Chemistry and Physics, 2012, 134(2/3): 1136-1145.
36	Guan Y T, Zhang Y J, Zhang Z L, et al. Alkali metal and alkali earth metal-modified La-Fe-based perovskite catalyzed coke combustion[J]. Molecular Catalysis, 2024, 558: 114012.
37	Berbenni V, Marini A. Thermoanalytical (TGA-DSC) and high temperature X-ray diffraction (HT-XRD) study of the thermal decomposition processes in Li₂CO₃-MnO mixtures[J]. Journal of Analytical and Applied Pyrolysis, 2002, 64(1): 43-58.
38	Liu B B, Zhang Y B, Wang J, et al. A further investigation on the MnO₂-Fe₂O₃ system roasted under CO-CO₂ atmosphere[J]. Advanced Powder Technology, 2019, 30(2): 302-310.
39	Ilton E S, Post J E, Heaney P J, et al. XPS determination of Mn oxidation states in Mn (hydr)oxides[J]. Applied Surface Science, 2016, 366: 475-485.
40	Pawlyta M, Rouzaud J N, Duber S. Raman microspectroscopy characterization of carbon blacks: spectral analysis and structural information[J]. Carbon, 2015, 84: 479-490.
41	Morga R, Jelonek I, Kruszewska K, et al. Relationships between quality of coals, resulting cokes, and micro-Raman spectral characteristics of these cokes[J]. International Journal of Coal Geology, 2015, 144: 130-137.
42	Xie B S, Han H Z, Luo W. Pyrolysis coking performance of supercritical n-decane in additively manufacturing channel[J]. International Journal of Heat and Mass Transfer, 2024, 229: 125743.
43	Rantitsch G, Bhattacharyya A, Günbati A, et al. Microstructural evolution of metallurgical coke: evidence from Raman spectroscopy[J]. International Journal of Coal Geology, 2020, 227: 103546.
44	Sheng C D. Char structure characterised by Raman spectroscopy and its correlations with combustion reactivity[J]. Fuel, 2007, 86(15): 2316-2324.

[1]	徐芳, 张锐, 崔达, 王擎. ReaxFF-MD揭示木质素热解反应机制的分子动力学研究[J]. 化工学报, 2025, 76(3): 1253-1263.
[2]	姚国家, 王志, 苏昂, 冯东阁, 唐宏, 孙灵芳. 空气系数对煤粉预热解燃烧特性的影响分析[J]. 化工学报, 2025, 76(3): 1243-1252.
[3]	杨猛, 丁晓倩, 余涛, 刘畅, 汤成龙, 黄佐华. 甲烷/氧化亚氮绿色推进剂自着火特性实验及动力学[J]. 化工学报, 2025, 76(3): 1221-1229.
[4]	吴学红, 韦新, 侯加文, 吕财, 刘勇, 刘鹤, 常志娟. 热解法制备碳纳米管及其在散热涂层中的应用研究[J]. 化工学报, 2024, 75(9): 3360-3368.
[5]	黄正梁, 冯铭瑞, 宋琦, 任聪静, 杨遥, 孙婧元, 王靖岱, 阳永荣. 预混进料对废树脂流化裂解反应中颗粒团聚的抑制作用[J]. 化工学报, 2024, 75(9): 3094-3102.
[6]	王舒英, 左涛, 石志伟, 范小明, 张卫新. 阳离子交换树脂基介孔石墨化碳合成与储钠性能[J]. 化工学报, 2024, 75(9): 3338-3347.
[7]	丁湧, 李文建, 陈昭宇, 曹立辉, 刘轩铭, 任强强, 胡松, 向军. 废旧晶体硅光伏组件EVA有氧热解动力学与产物特性[J]. 化工学报, 2024, 75(9): 3310-3319.
[8]	李沛奇, 陈雪娇, 武博翔, 蒋榕培, 杨超, 刘朝晖. 高参数石油基和煤基火箭煤油射线法密度测量实验研究[J]. 化工学报, 2024, 75(7): 2422-2432.
[9]	姚宏哲, 黄飞宇, 杨松, 钟梅, 代正华. 重质油高温快速热解自动反应网络的动力学建模[J]. 化工学报, 2024, 75(7): 2644-2655.
[10]	晁惠雨, 白振敏, 侯汉青, 田立志, 李洪, 房晓权, 石晓华. 液相法合成三聚氰酸体系热力学分析[J]. 化工学报, 2024, 75(6): 2157-2165.
[11]	吴希, 孙博, 刘银东, 齐传磊, 陈凯毅, 王路海, 许崇, 李永峰. 钠离子电池沥青基碳负极材料制备技术研究进展[J]. 化工学报, 2024, 75(4): 1270-1283.
[12]	李浩文, 兰昊, 郑幼丹, 孙勇辉, 杨子昕, 宋谦石, 汪小憨. 热通道内典型碳氢燃料的热解结焦行为[J]. 化工学报, 2024, 75(2): 626-636.
[13]	王茂先, 孙启典, 付哲, 华放, 纪晔, 程易. 分子水平动力学模型和机器学习方法相结合研究废弃塑料热解[J]. 化工学报, 2024, 75(11): 4320-4332.
[14]	颜诗宇, 高姣姣, 杨太顺, 谢尚志, 杨艳娟, 徐晶. 钌基催化剂配位环境对聚乙烯氢解性能的影响[J]. 化工学报, 2024, 75(10): 3588-3599.
[15]	吴雷, 刘姣, 李长聪, 周军, 叶干, 刘田田, 朱瑞玉, 张秋利, 宋永辉. 低阶粉煤催化微波热解制备含碳纳米管的高附加值改性兰炭末[J]. 化工学报, 2023, 74(9): 3956-3967.