废塑料催化热解制备碳纳米管及其生长机理

doi:10.16085/j.issn.1000-6613.2023-0861

化工进展 ›› 2024, Vol. 43 ›› Issue (6): 3468-3478.DOI: 10.16085/j.issn.1000-6613.2023-0861

• 资源与环境化工 • 上一篇

废塑料催化热解制备碳纳米管及其生长机理

孟卫波¹(), 邢宝林¹^,²^,³(), 程松¹^,²^,³(), 冯来宏⁴, 施凤¹, 曾会会¹, 雷思乐¹, 王雪¹, 赵赛丹¹, 曾祥旺¹

^1.河南理工大学化学化工学院，河南焦作 454000
^2.河南理工大学煤炭安全生产与清洁高效利用省部共建协同创新中心，河南焦作 454000
^3.河南理工大学河南省煤炭清洁利用国际联合实验室，河南焦作 454000
^4.华能煤炭技术研究有限公司，北京 100071

收稿日期:2023-05-25 修回日期:2023-06-12 出版日期:2024-06-15 发布日期:2024-07-02
通讯作者: 邢宝林,程松
作者简介:孟卫波（1999—），男，硕士研究生，研究方向为固体废弃物的高质化利用。E-mail: 1215814458@qq.com。
基金资助:
国家自然科学基金面上项目(51974110);河南省自然科学基金(232300420298);河南省高校基本科研业务费专项资金(NSFRF220417)

Preparation of carbon nanotubes by catalytic pyrolysis of waste plastics and its growth mechanism

MENG Weibo¹(), XING Baolin¹^,²^,³(), CHENG Song¹^,²^,³(), FENG Laihong⁴, SHI Feng¹, ZENG Huihui¹, LEI Sile¹, WANG Xue¹, ZHAO Saidan¹, ZENG Xiangwang¹

^1.College of Chemistry and Chemical Engineering, Henan Polytechnic University, Jiaozuo 454000, Henan, China
^2.Collaborative Innovation Center of Coal Work Safety and Clean High Efficiency Utilization, Henan Polytechnic University, Jiaozuo 454000, Henan, China
^3.Henan International Joint Laboratory of Clean Coal Utilization, Henan Polytechnic University, Jiaozuo 454000, Henan, China
^4.Huaneng Coal Technology Research Co. , Ltd. , Beijing 100071, China

Received:2023-05-25 Revised:2023-06-12 Online:2024-06-15 Published:2024-07-02
Contact: XING Baolin, CHENG Song

摘要/Abstract

摘要：

塑料因优异的易塑性、持久性、耐腐蚀等被广泛应用于生活中的各个角落。然而塑料在使用过程由于难降解、回收利用率低等缺点对环境造成严重污染。本文以低密度聚乙烯（LDPE）为原料，以硝酸镍为催化剂前体，通过一步热解法将聚乙烯塑料制备成具有高价值的碳纳米管（CNTs），通过X射线衍射、扫描电镜、透射电镜及气相色谱-质谱等技术对其结构和生长机制进行表征与分析。研究热解温度（600~900℃）和硝酸镍加入量（0.5%~2.0%）对CNTs结构形貌的影响。结果表明，在温度为800℃、硝酸镍质量分数1.0%的条件下制备得到形貌结构较好的CNTs。该条件下CNTs为多壁碳纳米管，石墨化度较高，长度为5~15μm，管平均外径为(28.43±0.56)nm，平均内径为(11.03±0.61)nm，层间距为0.340nm，接近碳纳米管的最理想的石墨层间距（d=0.3354nm）。结合气相色谱-质谱技术研究了CNTs的生长机理与模型，剖析出CNTs为顶端生长模型。将制备的CNTs用于去除废水中的微塑料并表现出了较好的去除性能，实现了“以废治废”。本研究以LDPE为原料采用一步热解法得到形貌结构优异的CNTs，实现了塑料的高质化利用，并为其他相似废弃物的利用提供了借鉴。

关键词: 废塑料, 碳纳米管, 生长机理

Abstract:

Plastics are widely used in all corners of life because of their excellent plasticity, durability and corrosion resistance. However, the use of plastic in the process of plastic caused serious pollution to the environment due to difficult to degrade, low recycling rate and other shortcomings. In this paper, low-density polyethylene (LDPE) was used as raw material and nickel nitrate was used as catalyst precursor to prepare polyethylene plastics into high-value carbon nanotubes (CNTs) by one-step pyrolysis, and their structures and growth mechanisms were characterized and analyzed by X-ray diffraction, scanning electron microscopy, transmission electron microscopy and gas chromatography-mass spectrometry. The effects of pyrolysis temperature (600—900℃) and nickel nitrate addition (0.5%—2.0%) on the structure and morphology of CNTs were investigated. The results indicated that the CNTs with good morphological structure were prepared at a temperature of 800℃ and the amount of nickel nitrate added was 1.0% of the mass of polyethylene plastic. The CNTs were multi-walled carbon nanotubes with high graphitization, the length was 5—15μm, the average outer diameter of the tubes was (28.43±0.56)nm, the average inner diameter was (11.03±0.61)nm and the layer spacing was 0.340nm, which was close to the optimal graphite layer spacing of carbon nanotubes (d=0.3354nm). The growth mechanism and model of CNTs were investigated by combining gas chromatography-mass spectrometry, and the growth model of CNTs was dissected as the apical growth model. The prepared CNTs were used to remove microplastics from wastewater and showed good removal performance, realizing "waste to waste". In this study, LDPE were used as raw materials to obtain CNTs with excellent morphology and structure by one-step pyrolysis, which realized the high-quality utilization of plastics and provided a reference for the utilization of other similar wastes.

Key words: waste plastic, carbon nanotubes (CNTs), growth mechanism

中图分类号:

X783.2

孟卫波, 邢宝林, 程松, 冯来宏, 施凤, 曾会会, 雷思乐, 王雪, 赵赛丹, 曾祥旺. 废塑料催化热解制备碳纳米管及其生长机理[J]. 化工进展, 2024, 43(6): 3468-3478.

MENG Weibo, XING Baolin, CHENG Song, FENG Laihong, SHI Feng, ZENG Huihui, LEI Sile, WANG Xue, ZHAO Saidan, ZENG Xiangwang. Preparation of carbon nanotubes by catalytic pyrolysis of waste plastics and its growth mechanism[J]. Chemical Industry and Engineering Progress, 2024, 43(6): 3468-3478.

图/表 14

图1 CNTs的制备流程图

图2 不同质量分数硝酸镍下CNTs的XRD谱图

图3 不同质量分数硝酸镍下CNTs的SEM图

图4 不同质量分数硝酸镍下CNTs的拉曼光谱

图5 不同温度（600~900℃）下CNTs的XRD谱图

图6 不同温度（600~900℃）下CNTs的SEM图

图7 不同温度（600~900℃）下CNTs拉曼光谱

图8 低密度聚乙烯热解气体浓度随温度的变化曲线

图9 800℃、硝酸镍质量分数为1.0%下CNTs的TEM图[（a）~（d）]以及CNTs的外径（e）和内径（f）分布

图10 800℃、硝酸镍质量分数为1.0%下CNTs的磁滞回线

图11 去除微塑料的实验结果

图12 LDPE与CNTs结合前后的XRD谱图（a）；LDPE的SEM图（b）；LDPE与CNTs结合后的SEM图（c）和EDS图（d）；外加磁场将LDPE/CNTs聚合体从溶液中分离的照片（e）

图13 循环使用CNTs去除LDPE的结果（a）；CNTs与CNTs-C的XRD谱图（b）；CNTs的SEM图（c）；CNTs-C的SEM图（d）

表1 各条件下CNTs去除LDPE的结果

样品	时间 /min	第一个周期去除率/%	第二个周期去除率/%	第三个周期去除率/%
CNTs-0.5-600℃	10	98.4	95.7	93.5
CNTs-1.5-600℃	10	100	100	99.7
CNTs-2.0-600℃	10	100	100	100
CNTs-1.0-600℃	10	96.6	91.4	86.7
CNTs-1.0-700℃	10	98.4	97.9	97.1
CNTs-1.0-900℃	10	99.2	98.8	98.2

参考文献 31

1	李晔，许文. 中国塑料制品市场分析与发展趋势[J]. 化学工业, 2021, 39(4): 37-43.
	LI Ye, XU Wen. Market analysis and development trend of plastic of China[J]. Chemical Industry, 2021, 39(4): 37-43.
2	James Guo Sheng MOO, VEKSHA Andrei, Wen-Da OH, et al. Plastic derived carbon nanotubes for electrocatalytic oxygen reduction reaction: Effects of plastic feedstock and synthesis temperature[J]. Electrochemistry Communications, 2019, 101: 11-18.
3	KANG Jian, ZHOU Li, DUAN Xiaoguang, et al. Degradation of cosmetic microplastics via functionalized carbon nanosprings [J]. Matter, 2019, 1(3): 745-758.
4	ANUAR SHARUDDIN Shafferina Dayana, ABNISA Faisal, WAN DAUD Wan Mohd Ashri, et al. A review on pyrolysis of plastic wastes[J]. Energy Conversion and Management, 2016, 115: 308-326.
5	BAZARGAN Alireza, MCKAY Gordon. A review: Synthesis of carbon nanotubes from plastic wastes[J]. Chemical Engineering Journal, 2012, 195/196: 377-391.
6	Khalid Mahmood ZIA, BHATTI Haq Nawaz, AHMAD BHATTI Ijaz. Methods for polyurethane and polyurethane composites, recycling and recovery: A review[J]. Reactive and Functional Polymers, 2007, 67(8): 675-692.
7	HUANG Zhong, ZHENG Yangfan, ZHANG Haijun, et al. High-yield production of carbon nanotubes from waste polyethylene and fabrication of graphene-carbon nanotube aerogels with excellent adsorption capacity[J]. Journal of Materials Science & Technology, 2021, 94: 90-98.
8	GRAVES Katherine A, HIGGINS Luke J R, NAHIL Mohamad A, et al. Structural comparison of multi-walled carbon nanotubes produced from polypropylene and polystyrene waste plastics[J]. Journal of Analytical and Applied Pyrolysis, 2022, 161: 105396.
9	ZHANG Junhao, ZHANG Longmei, YANG Huan, et al. Sustainable processing of waste polypropylene to produce high yield valuable Fe/carbon nanotube nanocomposites[J]. CrystEngComm, 2014, 16(37): 8832-8840.
10	段培, 李海, 闫晓丽, 等. 液体介质等离子体电弧法制备纳米炭材料研究进展[J]. 人工晶体学报, 2017, 46(2): 251-260.
	DUAN Pei, LI Hai, YAN Xiaoli, et al. Research progress on preparation of carbon nanomaterials by plasma discharge in liquid medium[J]. Journal of Synthetic Crystals, 2017, 46(2): 251-260.
11	SCOTT C D, AREPALLI S, NIKOLAEV P, et al. Growth mechanisms for single-wall carbon nanotubes in a laser-ablation process[J]. Applied Physics A, 2001, 72(5): 573-580.
12	满玉红. 定向多壁碳纳米管阵列的生长机理与可控制备研究[D]. 北京: 清华大学, 2011.
	MAN Yuhong. Exploration on growth mechanism and controlled synthesis of aligned multi-walled carbon nanotube array[D]. Beijing: Tsinghua University, 2011.
13	冯建民. 安全化学气相法制备连续碳纳米管纤维[D]. 天津: 天津大学, 2012.
	FENG Jianmin. Fabrication of continuous carbon nanotube fibers by a safe CVD method[D]. Tianjin: Tianjin University, 2012.
14	Clarence S YAH, IYUKE Sunny E, SIMATE Geoffrey S, et al. Continuous synthesis of multiwalled carbon nanotubes from xylene using the swirled floating catalyst chemical vapor deposition technique[J]. Journal of Materials Research, 2011, 26(5): 640-644.
15	ACOMB J C, WU C, WILLIAMS P T. The use of different metal catalysts for the simultaneous production of carbon nanotubes and hydrogen from pyrolysis of plastic feedstocks [J]. Appl Catal B, 2016, 180: 497-510.
16	GONG Jiang, LIU Jie, WAN Dong, et al. Catalytic carbonization of polypropylene by the combined catalysis of activated carbon with Ni₂O₃ into carbon nanotubes and its mechanism[J]. Applied Catalysis A: General, 2012, 449: 112-120.
17	ZHENG Yangfan, ZHANG Haijun, GE Shengtao, et al. Synthesis of carbon nanotube arrays with high aspect ratio via Ni-catalyzed pyrolysis of waste polyethylene[J]. Nanomaterials, 2018, 8(7): 556.
18	YAO Dingding, YANG Haiping, HU Qiang, et al. Carbon nanotubes from post-consumer waste plastics: Investigations into catalyst metal and support material characteristics[J]. Applied Catalysis B: Environmental, 2021, 280: 119413.
19	ZHANG Haijun, HABA Minori, OKUMURA Mitsutaka, et al. Novel formation of Ag/Au bimetallic nanoparticles by physical mixture of monometallic nanoparticles in dispersions and their application to catalysts for aerobic glucose oxidation[J]. Langmuir, 2013, 29(33): 10330-10339.
20	ZHANG Haijun, OKUNI Jun, TOSHIMA Naoki. One-pot synthesis of Ag-Au bimetallic nanoparticles with Au shell and their high catalytic activity for aerobic glucose oxidation[J]. Journal of Colloid and Interface Science, 2011, 354(1): 131-138.
21	DI Jiangtao, YONG Zhenzhong, YANG Xiaojie, et al. Structural and morphological dependence of carbon nanotube arrays on catalyst aggregation[J]. Applied Surface Science, 2011, 258(1): 13-18.
22	ABOUL-ENEIN Ateyya A, AWADALLAH Ahmed E. Production of nanostructured carbon materials using Fe-Mo/MgO catalysts via mild catalytic pyrolysis of polyethylene waste[J]. Chemical Engineering Journal, 2018, 354: 802-816.
23	陆超. 聚合物的热降解与催化降解[D]. 苏州: 苏州大学, 2015.
	LU Chao. Pyrolytic and catalytic degradation of polymers[D]. Suzhou: Soochow University, 2015.
24	JOURDAIN Vincent, BICHARA Christophe. Current understanding of the growth of carbon nanotubes in catalytic chemical vapour deposition[J]. Carbon, 2013, 58: 2-39.
25	VINCIGUERRA Vincenzo, BUONOCORE Francesco, PANZERA Giuseppe, et al. Growth mechanisms in chemical vapour deposited carbon nanotubes[J]. Nanotechnology, 2003, 14(6): 655-660.
26	XU Dan, XIONG Yuanquan, YE Jiandong, et al. Performances of syngas production and deposited coke regulation during co-gasification of biomass and plastic wastes over Ni/γ‍-Al₂O₃ catalyst: Role of biomass to plastic ratio in feedstock[J]. Chemical Engineering Journal, 2020, 392: 123728.
27	GONG Jiang, LIU Jie, JIANG Zhiwei, et al. Effect of the added amount of organically-modified montmorillonite on the catalytic carbonization of polypropylene into cup-stacked carbon nanotubes[J]. Chemical Engineering Journal, 2013, 225: 798-808.
28	SAITO Yahachi, YOSHIKAWA Tadanobu, BANDOW Shunji, et al. Interlayer spacings in carbon nanotubes[J]. Physical Review B, 1993, 48(3): 1907-1909.
29	ZHANG Silong, SHI Changliang, NIE Yanhe, et al. Separation experiment and mechanism study on PVC microplastics removal from aqueous solutions using high-gradient magnetic filter[J]. Journal of Water Process Engineering, 2023, 51: 103495.
30	APUL Onur Guven, KARANFIL Tanju. Adsorption of synthetic organic contaminants by carbon nanotubes: A critical review[J]. Water Research, 2015, 68: 34-55.
31	MA Yingzhi, ZHENG Dafeng, MO Zhenye, et al. Magnetic lignin-based carbon nanoparticles and the adsorption for removal of methyl orange[J]. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2018, 559: 226-234.

[1]	潘彤彤, 崔香梅. 葡甲胺功能化rGO/MWCNTs-OH复合气凝胶的制备及对硼的吸附[J]. 化工进展, 2024, 43(6): 3386-3397.
[2]	龚鹏程, 严群, 陈锦富, 温俊宇, 苏晓洁. 铁酸钴复合碳纳米管活化过硫酸盐降解铬黑T的性能及机理[J]. 化工进展, 2023, 42(7): 3572-3581.
[3]	许春树, 姚庆达, 梁永贤, 周华龙. 氧化石墨烯/碳纳米管对几种典型高分子材料的性能影响[J]. 化工进展, 2023, 42(6): 3012-3028.
[4]	薛博, 杨婷婷, 王雪峰. 聚苯胺/碳纳米管气敏材料的研究进展[J]. 化工进展, 2023, 42(3): 1448-1456.
[5]	陈韶云, 周贤太, 纪红兵. 金属卟啉/碳纳米管仿生催化剂的制备及其在Baeyer-Villiger氧化反应中的催化机理[J]. 化工进展, 2023, 42(3): 1332-1340.
[6]	范思强, 彭绍忠, 彭冲, 胡永康. 废塑料高附加值利用技术研究进展[J]. 化工进展, 2023, 42(2): 1020-1027.
[7]	张帅国, 马文媛, 赵海鹏, 冯宇, 蔡旭萍, 杨士祥, 钱新月, 米杰. 火焰法制备CNTs基复合材料及其应用研究进展[J]. 化工进展, 2023, 42(12): 6409-6418.
[8]	张辛亥, 赵思琛, 朱辉, 张首石, 王凯. 多种碳材料与碳酸钠复合后脱硫性能对比[J]. 化工进展, 2022, 41(S1): 424-435.
[9]	张爱京, 江胜娟, 周明正, 柴茂荣, 张劲. 纳米管壁数对氮掺杂碳纳米管氧还原反应活性的影响[J]. 化工进展, 2022, 41(4): 2038-2045.
[10]	王月, 赵秦峰, 张占全, 雷俊伟, 侯远东. 碳中和背景下国内外废塑料裂解法回收进展[J]. 化工进展, 2022, 41(3): 1470-1478.
[11]	陈欢, 万坤, 牛波, 张亚运, 龙东辉. 废弃塑料化学回收及升级再造研究进展[J]. 化工进展, 2022, 41(3): 1453-1469.
[12]	慕诗芸, 刘凯, 吕孝琦, 矫义来, 李鑫钢, 李洪, 范晓雷, 高鑫. 微波协同氧化锆@碳纳米管强化果糖制5-羟甲基糠醛[J]. 化工进展, 2022, 41(11): 5858-5869.
[13]	张燕, 王淼, 赵佳辉, 冯宇, 米杰. 氮掺杂石墨烯/碳纳米管/无定形炭复合材料制备及其电化学性能[J]. 化工进展, 2022, 41(10): 5501-5509.
[14]	秦煜, 唐元鑫, 阮鹏臻, 王威娜, 陈斌. 碳纳米管水泥基复合材料压阻效应的多尺度研究进展[J]. 化工进展, 2021, 40(8): 4278-4289.
[15]	林少华, 武海霞, 高莉苹, 俞乙平. 改性碳纳米管及其复合材料在废水处理中的应用现状及展望[J]. 化工进展, 2021, 40(6): 3466-3479.

废塑料催化热解制备碳纳米管及其生长机理

Preparation of carbon nanotubes by catalytic pyrolysis of waste plastics and its growth mechanism

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 14

参考文献 31

相关文章 15

编辑推荐

Metrics

本文评价