SYNTHESIS OF DISCARBOXYL PHENOXY PHTHALOCYANINE COBALT AND APPLICATION IN OXIDATION DESULFURIZATION OF MERCAPTAN COMPOUNDS

Abstract

Abstract:

The 4-(3,5-dicarboxy) phenoxyphthalonitrile as an intermediate was synthesized with 4-Nitrophthalonitrile and 5-hydroxy isophthalic acid as raw materials, followed by the purification by column chromatography. Afterwards, a new tetra -2(3), 9(10), 16(17), 23(24) - (3,5-discarboxylphenoxy) phthalocyanine cobalt was obtained from the intermediate under the catalytic action of 1,8-diazabicyclo undec-7-ene (DBU). The intermediate and the final product were characterized by mass spectrum, Fourier transform infrared spectroscopy (FT-IR), nuclear magnetic resonance (1H-NMR) and MADLI-TOF-MS techniques. The sweetening performance of the synthesized phthalocyanine cobalt was evaluated using mercaptan compounds and compared with the industrial catalysts. The sulfur conversions of n-propyl mercaptan and n-butyl mercaptan of the synthesized phthalocyanine cobalt are both around 98.0%, and for t-butyl mercaptan the conversion is 68.2%. The results show that the sweetening performance of the synthesized phthalocyanine cobalt is better than the industrial catalysts.

Key words: metallophthalocyanine, synthesis, column chromatography, sweetening

References

[1] 夏道宏. 用于轻质油品剂碱抽提-固定床催化氧化脱硫醇的组合装置[P]. 中国:ZL100964361,2005-6-29. [2] 高步良, 王迎春. 催化裂化C4,C5馏分中双烯烃的选择加氢[J]. 石油炼制与化工, 1997, (10):8-11. [3] 李雪双, 丁玲, 姚庆,等. 聚丙烯生产中原料丙烯的精制[J]. 广东化工, 2013, 40(12):47-48. [4] Das G, Sain B, Kumar S. Synthesis, characterization and catalytic activity of cobalt phthalocyanine dichloride in sweetening of heavier petroleum fractions[J]. Catalysis Today, 2012, 198(1):228-232. [5] 莫娅南,王伯.液化气脱硫技术及其工业应用[J].炼油与化工,2011,22(5):15-17 [6] 俞马金, 张凡. 4-硝基邻苯二甲腈的合成研究[J]. 化工科技, 2001, 9(2): 16-18. [7] 周建华，王新军．液化气脱硫醇工艺完善及节能减排要素分析［J］．石油炼制与化工， 2008，39( 3) : 51-57. [8] Ganguly S K, Das G, Kumar S, et al. Mechanistic kinetics of catalytic oxidation of 1-butanethiol in light oil sweetening[J]. Catalysis Today, 2012, 198:246–251. [9] Karaca H，Sezer S，?eniz ?zalp-Yaman， et al. Concise synthesis, electrochemistry and spectroelectrochemistry of phthalocyanines having triazole functionality[J]. Polyhedron, 2014, 72(5):147–156. [10] Yasar G?k, Halil Zeki G?k. Synthesis, characterization and spectral properties of novel zinc phthalocyanines derived from C2 symmetric diol[J]. Journal of Molecular Structure, 2014, 1067(4):169-176. [11] Wei S, Zhou J, Huang D, et al. Synthesis and Type I/Type II photosensitizing properties of a novel amphiphilic zinc phthalocyanine[J]. Dyes & Pigments, 2006, 71(1):61–67. [12] 张红兵, 吕荣文, 高崑玉. 芳氰基化合物红外光谱的研究[J]. 染料与染色, 2008, 45(2): 55-56. [13] 薛金萍, 洪湖铭, 蔡森林,等. 四-β -(8-喹啉氧基)取代酞菁金属配合物的合成、表征及其荧光性质研究[J]. 无机化学学报, 2005, 21:810-815. [14] 曾锦萍, 袁晓玲, 邓记华. 若干5,10,15,20-四（4-羧基苯基）卟啉金属配合物的合成与表征[J]. 宜春学院学报, 2010, 32(4):14-17. [15] 殷焕顺. 易溶性金属酞菁衍生物的合成及性质研究[D]. 湘潭大学, 2004. [16] 张海燕, 朱俊哲, 石海信,等. 汽油中不同结构硫醇氧化行为的研究[J]. 化工技术与开发, 2013, (2):9-12.