磺化酞菁金属的聚集及对催化氧化硫醇性能影响

doi:10.11944/j.issn.1000-0518.2016.02.150245

摘要/Abstract

摘要：

磺化酞菁金属主要用作液化气脱硫醇过程碱液氧化再生催化剂。为研究磺化酞菁金属易于失活的影响因素,对比探讨了5种磺化酞菁金属(Fe、Co、Ni、Cu、Zn )在相同溶剂以及不同溶剂中的聚集作用,并研究了聚集对催化氧化硫醇活性的影响。结果表明,磺化酞菁金属聚集受溶剂影响较大,溶剂极性越强,聚集越严重;磺化酞菁金属溶液放置时间越长,磺化酞菁金属聚集体粒径越大;金属种类不同,对磺化酞菁金属聚集也有影响。聚集导致CoSPc、CuSPc催化氧化硫醇活性显著降低20%左右。

关键词: 液化气脱臭, 磺化酞菁金属, 聚集, 催化氧化硫醇

Abstract:

Sulfonated metallophthalocyanines are mainly used as oxidation regenerated catalyst in liquefied petroleum gas(LPG) sweetening process. Aggregation behavior of the five sulfonated metallophthalocyanines(MSPc, M=Fe,Co,Ni,Cu,Zn) in the same or different solvents was studied. The influencing factors of inactivation and the influence of aggregation behavior on activity of catalytic oxidation were investigated. The results show that the aggregation of sulfonated metallophthalocyanines is significantly affected by solvents. The aggregation aggravates with the increasing of polarity of the solvent and storage period. Besides, the aggregation of sulfonated metallophthalocyanines is also affected by central metals. The activity of CoSPc and CuSPc catalytic oxidation of thiol is markedly reduced nearly 20% because of the aggregation.

Key words: liquefied petroleum gas sweetening, sulfonated metallophthalocyanines, aggreation, catalytic oxidation desulfurization

程振华, 崔娜, 宋兆阳, 江胜娟, 朱丽君, 夏道宏. 磺化酞菁金属的聚集及对催化氧化硫醇性能影响[J]. 应用化学, 2016, 33(2): 155-160.

CHENG Zhenhua, CUI Na, SONG Zhaoyang, JIANG Shengjuan, ZHU Lijun, XIA Daohong. Aggreation Behavior and Catalytic Sweetening Performance of Sulfonated Metallophthalocyanines[J]. Chinese Journal of Applied Chemistry, 2016, 33(2): 155-160.

参考文献

[1]	WANG Yuhai,TIAN Yongliang,LIU Ruiting,et al.Study on the Further Desulfurization and Stability of Catalyst in Merox Sweetening Process of LPG[J]. Nat Gas Chem Ind,2005,30(2):14-18(in Chinese). 王玉海,田永亮,刘瑞婷,等. 液化气Merox脱硫醇精制中脱硫深度和催化剂稳定性研究[J]. 天然气化工:C1化学与化工,2005,30(2):14-18.
[2]	Lebedeva N S,Pavlycheva N A,Kulinich V P,et al.Thermal Oxidative Destruction of Cobalt(Ⅱ) Phthalocyanines with Oxygen Containing Substituents[J]. J Therm Anal Calorim,2005,81(2):451-455.
[3]	WANG Huiguo,FAN Zhiming. Bifunctional Catalyst CoSPC/Mg(Al)O for Thiols Oxidation[J]. Pet Process Petrochem,2001,32(1):49-53(in Chinese). 王辉国,范志明. 新型硫醇氧化双功能催化剂CoSPc/Mg(AI)O的研究[J]. 石油炼制与化工,2001,32(1):49-53.
[4]	SANG Liqiang. Synthesis and Characterization of a Kind of Efficient Catalyst for Gasoline Sweetening[D]. Nanjing:Nanjing University of Technology,2004(in Chinese). 桑立强. 一种高效汽油脱臭催化剂的制备与性能表征[D]. 南京:南京工业大学,2004.
[5]	HU Min. Preparation of Solid Base Catalyst and Its Application to the Sweetening of Liquefied Petroleum Gas[D]. Nanjing:Nanjing University of Technology,2005(in Chinese). 胡敏. 固体碱催化剂的制备及其在液化气脱硫醇中的应用[D]. 南京:南京工业大学,2005.
[6]	YU Hang,LI Xuhui,XIA Daohong,et al.Effects of Compound Activator on the Stability of CoTsPc Sweetening Catalyst Alkaline Solution in Different Conditions[J]. Nat Gas Chem Ind,2007,32(3):73-77(in Chinese). 于航,李旭辉,夏道宏,等. 复合活性剂在不同条件下对磺化酞菁钴脱硫醇催化剂碱液稳定作用的研究[J]. 天然气化工:C1化学与化工,2007,32(3):73-77.
[7]	XU Xiuzhi,CHEN Zhifeng,ZHU Wenshan,et al.The Synthesis and Spectral Properties Research of Water Soluble Octasu-bstituted Phthalocyaninatozinc(ZnPcBPO8I8)[J]. Strait Pharm J,2014,26(6):141-145(in Chinese). 许秀枝,陈志枫,朱文山,等. 水溶性八取代酞菁锌配合物(ZnPcBPO8I8)的合成及光谱性质研究[J]. 海峡药学,2014,26(6):141-145.
[8]	SI Xiqiang,XIA Daohong,XIANG Yuzhi,et al.Study on the Effects of Activator on the Stability of CoPcS-Alkaline Solution[J]. Fine Chem,2009,26(3):243-247(in Chinese). 司西强,夏道宏,项玉芝,等. 表面活性剂对磺化酞菁钴苛性碱液的稳定化作用研究[J]. 精细化工,2009,26(3):243-247.
[9]	Cheng Z H,Cui N,Zhang H X,et al.Synthesis and Dimerization Behavior of Five Metallophthalocyanines in Different Solvents[J]. Adv Mat Sci Eng,2014:1-5.
[10]	Yanık H,Aydın D,Durmuş M,et al.Peripheral and Non-peripheral Tetrasubstituted Aluminium, Gallium and Indium Phthalocyanines:Synthesis, Photophysics and Photochemistry[J]. Photochem Photobiol A Chem,2009,206(1):18-26.
[11]	Bouanani F,Bendedouch D,Hemery P,et al.Characterization of a Miniemulsion by DLS and SANS[J]. Colloids Surf A Physicochem Eng Aspects,2012,404:47-51.
[12]	JIANG Xiongjie. Axial Modification,Characterization and Application in Photodynamic Therapy of Silicon(Ⅵ) Phthalocyanines[D]. Fuzhou:Fuzhou University,2006(in Chinese). 蒋雄杰. 酞菁硅配合物的轴向修饰、表征及在光动力治疗中的应用[D]. 福州:福州大学,2006.
[13]	YUAN Shihai, WU Xing,YAO Rong,et al.Study on Axial Coordination Reaction for Cobalt Tetrasulfonate Phthalocyanine[J]. Photogr Sci Photochem,1996,14(4):341-346(in Chinese). 袁诗海,吴星,姚荣,等. 四磺化酞菁钴轴向配位反应研究[J]. 感光科学与光化学,1996,14(4):341-346.
[14]	Tyapochkin E M,Kozliak E I. Kinetic and Binding Studies of the Thiolate-cobalt Tetrasulfophthalocyanine Anaerobic Reaction as a Subset of the Merox Process[J]. J Mol Catal A Chem,2005,242(1/2):1-17.
[15]	Ganguly S K,Das G,Kumar S,et al.Mechanistic Kinetics of Catalytic Oxidation of 1-Butanethiol in Light Oil Sweetening[J]. Catal Today,2012,198(1):246-251.