Preparation and dechlorination kinetics of Pd-Fe/MWCNTs bimetallic catalyst

doi:10.16085/j.issn.1000-6613.2022-1112

Abstract

Abstract:

Bleached lac is often used in pharmaceutical and food industry, but the binding chlorine added to its double bond structure in the preparation process has a negative impact on its application and performance. The removal of binding chlorine from bleached lac is a hot spot in the research of high value utilization of lac. In this paper, the supported Pd-Fe bimetallic catalyst was prepared by ultrasonic intensification and liquid reduction method using modified multi-walled carbon nanotubes as the support. The catalytic hydrogenation dechlorination of bleach lac over the supported Pd-Fe bimetallic catalyst was studied, and the prepared catalyst was characterized by XRD, XPS, SEM and HRTEM. The results showed that the particle size and lattice parameters of the prepared catalyst were 6.32nm and 2.27Å, respectively. The hydrogenation dechlorination process belonged to substitution reaction and followed the first-order reaction kinetics. The reaction rate constanted at 55℃, 65℃ and 75℃ are 0.0267min^-1, 0.0349min^-1 and 0.0435min^-1, respectively, giving an activation energy of 23.20kJ/mol. Under the optimum reaction conditions, the dechlorination efficiency reaches 93.68% and the chlorine in bleached lac decreased from 2.42% to 0.14% .

Key words: catalyst, nanomaterials, support, hydrogenation, reaction kinetics

摘要：

漂白紫胶常用于制药及食品行业，但制备过程中加成到其双键结构的结合氯对其使用领域和性能有负面影响，漂白紫胶中结合氯的脱除研究是紫胶高值利用研究的热点。本文以改性多壁碳纳米管为载体，采用超声强化、液相还原法制备出负载型Pd-Fe双金属催化剂，并用以漂白紫胶的催化加氢脱氯研究，以XRD、XPS、SEM、HRTEM对催化剂进行分析表征。结果表明，制备出的催化剂活性成分粒径为6.32nm，晶格参数为2.27Å；催化剂加氢脱氯反应属于取代反应，过程遵循一级反应动力学，反应的活化能值为23.20kJ/mol；55℃、65℃和75℃对应的反应速率常数分别为0.0267min^-1、0.0349min^-1和0.0435min^-1；在最佳的脱氯反应条件下，制备得到的催化剂用于加氢脱除漂白紫胶中结合氯时，脱氯效率达到93.68%，氯质量分数由脱氯前的2.42%降至0.14%。

关键词: 催化剂, 纳米材料, 载体, 加氢, 反应动力学

CLC Number:

TQ426.82

GE Weitong, LIAO Yalong, LI Mingyuan, JI Guangxiong, XI Jiajun. Preparation and dechlorination kinetics of Pd-Fe/MWCNTs bimetallic catalyst[J]. Chemical Industry and Engineering Progress, 2023, 42(4): 1885-1894.

葛伟童, 廖亚龙, 李明原, 嵇广雄, 郗家俊. Pd-Fe/MWCNTs双金属催化剂制备及其脱氯动力学[J]. 化工进展, 2023, 42(4): 1885-1894.

Figures/Tables 11

金属类型	Pd金属质量分数 /%	Fe金属质量分数 /%	粒径 /nm	晶格参数 /Å
Pd-Fe	5.0	5.3	6.36	2.27

化学态	结合能/eV
Pd 3d_3/2	340.2
Pd 3d_5/2	335.2
Fe 2p_3/2	710.6
Fe 2p_1/2	724.8

项目	碳纳米管官能团含量/mmol·g^-1
项目	羧基（—COOH）	羰基（C $̿$ O）	羟基（—OH）
改性前	0.17	1.35	4.37
改性后	0.49	2.47	7.26

项目	碳纳米管官能团含量/mmol·g^-1
项目	羧基（—COOH）	羰基（C $̿$ O）	羟基（—OH）
改性前	0.17	1.35	4.37
改性后	0.49	2.47	7.26

References 42

1	AL-GOUSOUS J, PENNING M, LANGGUTH P. Molecular insights into shellac film coats from different aqueous shellac salt solutions and effect on disintegration of enteric-coated soft gelatin capsules[J]. International Journal of Pharmaceutics, 2015, 484(1/2): 283-291.
2	廖亚龙, 彭金辉, 刘中华. 国内外紫胶深加工技术现状及趋势[J]. 林业科学, 2007, 43(7): 93-100.
	LIAO Yalong, PENG Jinhui, LIU Zhonghua. National and international seedlac processing development and its trend[J]. Scientia Silvae Sinicae, 2007, 43(7): 93-100.
3	REMADEVI O K, SIDDIQUI M Z, H Cet al NAGAVENI. Efficacy of shellac-based varnishes for protection of wood against termite, borer and fungal attack[J]. Journal of the Indian Academy of Wood Science, 2015, 12(1): 9-14.
4	JO W S, SONG H Y, SONG N B, et al. Quality and microbial safety of ‘Fuji’ apples coated with carnauba-shellac wax containing lemongrass oil[J]. LWT-Food Science and Technology, 2014, 55(2): 490-497.
5	PHAECHAMUD T, SETTHAJINDALERT O. Antimicrobial in situ forming gels based on bleached shellac and different solvents[J]. Journal of Drug Delivery Science and Technology, 2018, 46: 285-293.
6	WANG Xia, YU Dengguang, LI Xiaoyan, et al. Electrospun medicated shellac nanofibers for colon-targeted drug delivery[J]. International Journal of Pharmaceutics, 2015, 490(1/2): 384-390.
7	PHAECHAMUD T, MAHADLEK J, CHUENBARN T. In situ forming gel comprising bleached shellac loaded with antimicrobial drugs for periodontitis treatment[J]. Materials & Design, 2016, 89: 294-303.
8	PHAECHAMUD T, SENARAT S, PUYATHORN N, et al. Solvent exchange and drug release characteristics of doxycycline hyclate-loaded bleached shellac in situ-forming gel and-microparticle[J]. International Journal of Biological Macromolecules, 2019, 135: 1261-1272.
9	LIAO Yalong, ZHOU Juan, HUANG Feirong, et al. Effects of combined chlorine on physicochemical properties and structure of shellac[J]. Pakistan Journal of Pharmaceutical Sciences, 2015, 28(1 ): 329-334.
10	LIAO Yalong, ZHOU Juan, HUANG Feirong. Process and kinetic mechanism of elimination of chlorine combined in molecule of bleached shellac[J]. Tropical Journal of Pharmaceutical Research, 2015, 14(11): 1953-1960.
11	廖亚龙, 杨功舜, 周娟. 消除法制备低氯漂白紫胶及机理[J]. 材料工程, 2016, 44(4): 59-64.
	LIAO Yalong, YANG Gongshun, ZHOU Juan. Preparation and mechanism of low chlorine shellac by means of elimination method[J]. Journal of Materials Engineering, 2016, 44(4): 59-64.
12	LIAO Yalong, CHAI Xijuan, XU Fuchang. Preparation of low chlorine shellac by catalytic hydrogenation with Pd/C[J]. Advanced Materials Research, 2010, 152/153: 372-376.
13	LIAO Yalong, XU Fuchang, LI Dongbo. Preparation of low chlorine shellac from seedlac by dechlorination process using Pd/Fe binary metal as catalyst[J]. Advanced Materials Research, 2009, 79/80/81/82: 1879-1882.
14	ZHANG Yu, LIAO Yalong, SHI Gongchu, et al. Preparation, characterization, and catalytic performance of Pd-Ni/AC bimetallic nano-catalysts[J]. Green Processing and Synthesis, 2020, 9(1): 760-769.
15	ZHANG Yu, WANG Yiyang, LIAO Yalong, et al. Preparation, characterization and dechlorination property of nano Pd-Ni/γ-Al₂O₃ bimetallic catalyst[J]. Functional Materials Letters, 2019, 12(6): 1951003.
16	LIAO Yalong, WANG Wei, ZHANG Yu, et al. Preparation, characterization and catalytic hydrodechlorination property for bleached shellac of Pd-Ni@SiO₂ bimetallic nano-catalyst[J]. Reaction Kinetics, Mechanisms and Catalysis, 2020, 130(2): 1043-1061.
17	LIAO Yalong, WANG Yiyang, ZHANG Yu. Preparation and catalytic hydrodechlorination property of nano bimetallic catalyst Pd-Ni/γ-Al₂O₃-SiO₂ [J]. Catalysts, 2022, 12(4): 370.
18	ZHAO Ming, ABE K, YAMAURA S I, et al. Fabrication of Pd-Ni-P metallic glass nanoparticles and their application as highly durable catalysts in methanol electro-oxidation[J]. Chemistry of Materials, 2014, 26(2): 1056-1061.
19	CHENG Honghui, CHEN Gang, ZHANG Yao, et al. Boosting low-temperature de/re-hydrogenation performances of MgH₂ with Pd-Ni bimetallic nanoparticles supported by mesoporous carbon[J]. International Journal of Hydrogen Energy, 2019, 44(21): 10777-10787.
20	ZAFARI R, ABDOUSS M, ZAMANI Y. Application of response surface methodology for the optimization of light olefins production from CO hydrogenation using an efficient catalyst[J]. Fuel, 2019, 237: 1262-1273.
21	KOSKUN Y, ŞAVK A, ŞEN B, et al. Highly sensitive glucose sensor based on monodisperse palladium nickel/activated carbon nanocomposites[J]. Analytica Chimica Acta, 2018, 1010: 37-43.
22	SEN B, KUZU S, DEMIR E, et al. Monodisperse palladium-nickel alloy nanoparticles assembled on graphene oxide with the high catalytic activity and reusability in the dehydrogenation of dimethylamine-borane[J]. International Journal of Hydrogen Energy, 2017, 42(36): 23276-23283.
23	ŞEN B, AYGÜN A, OKYAY T O, et al. Monodisperse palladium nanoparticles assembled on graphene oxide with the high catalytic activity and reusability in the dehydrogenation of dimethylamine-borane[J]. International Journal of Hydrogen Energy, 2018, 43(44): 20176-20182.
24	TAN Ling, LI Ting, ZHOU Juan, et al. Liquid-phase hydrogenation of N-nitrosodimethylamine over Pd-Ni supported on CeO₂-TiO₂: The role of oxygen vacancies[J]. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2018, 558: 211-218.
25	KIM K S, GOSSMANN A F, WINOGRAD N. X-ray photoelectron spectroscopic studies of palladium oxides and the palladium-oxygen electrode[J]. Analytical Chemistry, 1974, 46(2): 197-200.
26	KUMAR G, BLACKBURN J R, ALBRIDGE R G, et al. Photoelectron spectroscopy of coordination compounds. Ⅱ. Palladium complexes[J]. Inorganic Chemistry, 1972, 11(2): 296-300.
27	CHANG S L, ANDEREGG J W, THIEL P A. Surface oxidation of an Al-Pd-Mn quasicrystal, characterized by X-ray photoelectron spectroscopy[J]. Journal of Non-Crystalline Solids, 1996, 195(1/2): 95-101.
28	HE Zhiqiao, JIAN Qiwei, TANG Juntao, et al. Improvement of electrochemical reductive dechlorination of 2,4-dichlorophenoxyacetic acid using palladium catalysts prepared by a pulsed electrodeposition method[J]. Electrochimica Acta, 2016, 222: 488-498.
29	JIANG Tao, HUAI Qiang, GENG Tong, et al. Catalytic performance of Pd-Ni bimetallic catalyst for glycerol hydrogenolysis[J]. Biomass and Bioenergy, 2015, 78: 71-79.
30	CHEN Huan, LI Ting, JIANG Fang, et al. Enhanced catalytic reduction of N-nitrosodimethylamine over bimetallic Pd-Ni catalysts[J]. Journal of Molecular Catalysis A: Chemical, 2016, 421: 167-177.
31	TAN B J, KLABUNDE K J, SHERWOOD P M A. X-ray photoelectron spectroscopy studies of solvated metal atom dispersed catalysts. Monometallic iron and bimetallic iron-cobalt particles on alumina[J]. Chemistry of Materials, 1990, 2(2): 186-191.
32	王艳丽, 张明旭, 李本侠, 等. 软模板法六边形纳米Pd粒子的超声制备与表征[J]. 无机化学学报, 2011, 27(10): 1914-1918.
	WANG Yanli, ZHANG Mingxu, LI Benxia, et al. Hexagonal nano-Pd particles: Sonochemical preparation by soft-template method and characterization[J]. Chinese Journal of Inorganic Chemistry, 2011, 27(10): 1914-1918.
33	金永丽, 张祥, 张捷宇, 等. 稳恒磁场对Fe形核生长取向的影响[J]. 钢铁钒钛, 2019, 40(6): 129-134, 148.
	JIN Yongli, ZHANG Xiang, ZHANG Jieyu, et al. Effect of static magnetic field on nucleation and growth orientation of Fe atomic[J]. Iron Steel Vanadium Titanium, 2019, 40(6): 129-134, 148.
34	李荣柱, 马艳红, 卢成. BET法测定氧化铝比表面积的研究[J]. 轻金属, 2020(9): 13-16.
	LI Rongzhu, MA Yanhong, LU Cheng. Study on the specific surface area determination of alumina by BET method[J]. Light Metals, 2020(9): 13-16.
35	冒爱琴, 王华, 谈玲华, 等. 活性炭表面官能团表征进展[J]. 应用化工, 2011, 40(7): 1266-1270.
	MAO Aiqin, WANG Hua, TAN Linghua, et al. Research progress in characterization of functional groups on activated carbon[J]. Applied Chemical Industry, 2011, 40(7): 1266-1270.
36	ZHOU Juan, WU Ke, WANG Wenjuan, et al. Pd supported on boron-doped mesoporous carbon as highly active catalyst for liquid phase catalytic hydrodechlorination of 2,4-dichlorophenol[J]. Applied Catalysis A: General, 2014, 470: 336-343.
37	DIAZ E, MOHEDANO A F, CASAS J A, et al. Analysis of the deactivation of Pd, Pt and Rh on activated carbon catalysts in the hydrodechlorination of the MCPA herbicide[J]. Applied Catalysis B: Environmental, 2016, 181: 429-435.
38	MAHY J G, TASSEROUL L, TROMME O, et al. Hydrodechlorination and complete degradation of chlorinated compounds with the coupled action of Pd/SiO₂ and Fe/SiO₂ catalysts: Towards industrial catalyst synthesis conditions[J]. Journal of Environmental Chemical Engineering, 2019, 7(2): 103014.
39	ORDÓÑEZ S, DÍEZ F V, SASTRE H. Catalytic hydrodechlorination of chlorinated olefins over a Pd/Al₂O₃ catalyst: Kinetics and inhibition phenomena[J]. Industrial & Engineering Chemistry Research, 2002, 41(3): 505-511.
40	GÓMEZ-SAINERO L M, SEOANE X L, FIERRO J L G, et al. Liquid-phase hydrodechlorination of CCl₄ to CHCl₃ on Pd/carbon catalysts: Nature and role of Pd active species[J]. Journal of Catalysis, 2002, 209(2): 279-288.
41	BAEZA J A, CALVO L, GILARRANZ M A, et al. Catalytic behavior of size-controlled palladium nanoparticles in the hydrodechlorination of 4-chlorophenol in aqueous phase[J]. Journal of Catalysis, 2012, 293: 85-93.
42	ZHANG Weixian, WANG Chuanbao, LIEN H L. Treatment of chlorinated organic contaminants with nanoscale bimetallic particles[J]. Catalysis Today, 1998, 40(4): 387-395.

[1]	ZHANG Mingyan, LIU Yan, ZHANG Xueting, LIU Yake, LI Congju, ZHANG Xiuling. Research progress of non-noble metal bifunctional catalysts in zinc-air batteries [J]. Chemical Industry and Engineering Progress, 2023, 42(S1): 276-286.
[2]	SHI Yongxing, LIN Gang, SUN Xiaohang, JIANG Weigeng, QIAO Dawei, YAN Binhang. Research progress on active sites in Cu-based catalysts for CO₂ hydrogenation to methanol [J]. Chemical Industry and Engineering Progress, 2023, 42(S1): 287-298.
[3]	XIE Luyao, CHEN Songzhe, WANG Laijun, ZHANG Ping. Platinum-based catalysts for SO₂ depolarized electrolysis [J]. Chemical Industry and Engineering Progress, 2023, 42(S1): 299-309.
[4]	YANG Xiazhen, PENG Yifan, LIU Huazhang, HUO Chao. Regulation of active phase of fused iron catalyst and its catalytic performance of Fischer-Tropsch synthesis [J]. Chemical Industry and Engineering Progress, 2023, 42(S1): 310-318.
[5]	WANG Lele, YANG Wanrong, YAO Yan, LIU Tao, HE Chuan, LIU Xiao, SU Sheng, KONG Fanhai, ZHU Canghai, XIANG Jun. Influence of spent SCR catalyst blending on the characteristics and deNO _x performance for new SCR catalyst [J]. Chemical Industry and Engineering Progress, 2023, 42(S1): 489-497.
[6]	DENG Liping, SHI Haoyu, LIU Xiaolong, CHEN Yaoji, YAN Jingying. Non-noble metal modified vanadium titanium-based catalyst for NH₃-SCR denitrification simultaneous control VOCs [J]. Chemical Industry and Engineering Progress, 2023, 42(S1): 542-548.
[7]	CHENG Tao, CUI Ruili, SONG Junnan, ZHANG Tianqi, ZHANG Yunhe, LIANG Shijie, PU Shi. Analysis of impurity deposition and pressure drop increase mechanisms in residue hydrotreating unit [J]. Chemical Industry and Engineering Progress, 2023, 42(9): 4616-4627.
[8]	WANG Peng, SHI Huibing, ZHAO Deming, FENG Baolin, CHEN Qian, YANG Da. Recent advances on transition metal catalyzed carbonylation of chlorinated compounds [J]. Chemical Industry and Engineering Progress, 2023, 42(9): 4649-4666.
[9]	GAO Yanjing. Analysis of international research trend of single-atom catalysis technology [J]. Chemical Industry and Engineering Progress, 2023, 42(9): 4667-4676.
[10]	ZHANG Qi, ZHAO Hong, RONG Junfeng. Research progress of anti-toxicity electrocatalysts for oxygen reduction reaction in PEMFC [J]. Chemical Industry and Engineering Progress, 2023, 42(9): 4677-4691.
[11]	GE Quanqian, XU Mai, LIANG Xian, WANG Fengwu. Research progress on the application of MOFs in photoelectrocatalysis [J]. Chemical Industry and Engineering Progress, 2023, 42(9): 4692-4705.
[12]	WANG Weitao, BAO Tingyu, JIANG Xulu, HE Zhenhong, WANG Kuan, YANG Yang, LIU Zhaotie. Oxidation of benzene to phenol over aldehyde-ketone resin based metal-free catalyst [J]. Chemical Industry and Engineering Progress, 2023, 42(9): 4706-4715.
[13]	GE Yafen, SUN Yu, XIAO Peng, LIU Qi, LIU Bo, SUN Chengying, GONG Yanjun. Research progress of zeolite for VOCs removal [J]. Chemical Industry and Engineering Progress, 2023, 42(9): 4716-4730.
[14]	YANG Ying, HOU Haojie, HUANG Rui, CUI Yu, WANG Bing, LIU Jian, BAO Weiren, CHANG Liping, WANG Jiancheng, HAN Lina. Coal tar phenol-based carbon nanosphere prepared by Stöber method for adsorption of CO₂ [J]. Chemical Industry and Engineering Progress, 2023, 42(9): 5011-5018.
[15]	YIN Xinyu, PI Pihui, WEN Xiufang, QIAN Yu. Application of special wettability materials for anti-hydrate-nucleation and anti-hydrate-adhesion in oil and gas pipelines [J]. Chemical Industry and Engineering Progress, 2023, 42(8): 4076-4092.