取代水杨醛Schiff碱金属配合物催化氧化脱硫性能
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摘要
以水杨醛类Schiff碱为配体,与Co(NO_3)_2、Cu(NO_3)_2反应合成6种Salen(M)型配合物Ⅰ～Ⅵ。以1-己硫醇、二丁基硫醚和2-甲基噻吩为模型化合物配制模拟油体系,考察了配合物Ⅰ～Ⅵ的催化氧化脱硫性能,并分析了配合物结构与氧化脱硫性能的关系。结果表明,6种配合物在75 min时的总脱硫效果为Ⅵ>Ⅴ>Ⅳ>Ⅰ>Ⅲ>Ⅱ,Ⅵ的总脱硫率为31.9%。对1-己硫醇及二丁基硫醚脱除效果最佳的是Ⅴ,脱除率分别为74.2%和65.1%;对2-甲基噻吩脱除效果最好的是Ⅰ,脱除率为26.8%。构效关系研究表明,中心金属离子与O_2的配位能力越强,配体的共轭体系越大、电子云密度越高,配合物的脱硫性能越好;通过IR和离子色谱对单一硫化物模拟油体系氧化前后的产物进行分析发现,硫化物氧化后皆生成相应的砜类或亚砜类,且1-己硫醇和二丁基硫醚被进一步氧化生成SO_3~(2–)或SO_4~(2–)。
Six Salen(M) complexes, Ⅰ～Ⅵ, were synthesized from salicylaldehyde Schiff base ligands and Co(NO_3)_2 and Cu(NO_3)_2. The simulated oil system was prepared by using 1-hexanethiol, dibutyl sulfide and 2-methylthiophene as model compounds to investigate the catalytic oxidative desulfurization performance of complexes Ⅰ～Ⅵ. The effects of central metal ions and ligands on the oxidative desulfurization performance of complexes Ⅰ～Ⅵ were analyzed. The results showed that the order of the total desulfurization effect for the six desulfurizers on the simulated oil in 75 min was Ⅵ>Ⅴ>Ⅳ>Ⅰ>Ⅲ>Ⅱ, and the total desulfurization rate of complex Ⅵ was 31.9%. Among them, complex Ⅴ exhibited the best removal effect for 1-hexanethiol and dibutyl sulfide with 74.2% and 65.1% removal rate, respectively. While complex Ⅰ had the best removal effect for 2-methylthiophene with a removal rate of 26.8%. According to the structure-property relationship analysis, the stronger the coordination ability between the central metal ion and O_2, the larger the conjugated system of the ligand, and the higher density of electron cloud, the better the desulfurization performance of the complex. The products before and after oxidation of the single sulfide simulated oil system were analyzed by infrared spectroscopy(IR) and ion chromatography(IC). It was found that three sulfides were oxidized to form corresponding sulfones or sulfoxides, and 1-hexanethiol and dibutyl sulfide were further oxidized to form SO_3~(2–) or SO_4~(2–).
Six Salen(M) complexes, Ⅰ～Ⅵ, were synthesized from salicylaldehyde Schiff base ligands and Co(NO_3)_2 and Cu(NO_3)_2. The simulated oil system was prepared by using 1-hexanethiol, dibutyl sulfide and 2-methylthiophene as model compounds to investigate the catalytic oxidative desulfurization performance of complexes Ⅰ～Ⅵ. The effects of central metal ions and ligands on the oxidative desulfurization performance of complexes Ⅰ～Ⅵ were analyzed. The results showed that the order of the total desulfurization effect for the six desulfurizers on the simulated oil in 75 min was Ⅵ>Ⅴ>Ⅳ>Ⅰ>Ⅲ>Ⅱ, and the total desulfurization rate of complex Ⅵ was 31.9%. Among them, complex Ⅴ exhibited the best removal effect for 1-hexanethiol and dibutyl sulfide with 74.2% and 65.1% removal rate, respectively. While complex Ⅰ had the best removal effect for 2-methylthiophene with a removal rate of 26.8%. According to the structure-property relationship analysis, the stronger the coordination ability between the central metal ion and O_2, the larger the conjugated system of the ligand, and the higher density of electron cloud, the better the desulfurization performance of the complex. The products before and after oxidation of the single sulfide simulated oil system were analyzed by infrared spectroscopy(IR) and ion chromatography(IC). It was found that three sulfides were oxidized to form corresponding sulfones or sulfoxides, and 1-hexanethiol and dibutyl sulfide were further oxidized to form SO_3~(2–) or SO_4~(2–).
引文
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[21] Khan M R, Al-Sayed E. Hydrocarbon desulfurization to clean fuels by selective oxidation versus conventional hydrotreating[J]. Energy Sources, 2007, 30(3):200-217.
[22] Zhang Zhigang(张志刚), Jiang Huiling(蒋慧灵), Huang Ping(黄平). Mechanism analysis and preventive measures of hydrogen peroxide explosion accident[J]. Journal of Safety and Environment(安全与环境学报), 2007, 7(4):108-110.
[23] Yuan Xia(袁霞), Luo Hean(罗和安), Li Fang(李芳). Performance of Co salen/NaY catalyst in cyclohexane oxidation[J]. Petrochemical Technology(石油化工), 2006, 35(5):458-463.
[24] Li Jianzhang(李建章), Lu Xiaoxia(卢晓霞), Qin Shengying(秦圣英). Effect of structure of Schiff base complex on its catalytic oxidation activity[J]. Chemical Research and Application(化学研究与应用), 1999, 11(3):305-307.
[25] Bolzacchini E, Meinardi S, Orlandi M, et al. Substituent effects in the cobalt-catalyzed oxidative carbonylation of aromatic amines[J].Journal of Molecular Catalysis A:Chemical, 1996, 111(3):281-287.
[26] Liang Shuyuan(梁书源). Study on synthesis of Schiff base metal complexes and oxidative desulfurization of sulfide in oil[D]. Qingdao:China University of Petroleum〔中国石油大学(华东)〕, 2018.
[27] Mark J Carter, D Paul Rillema, Fred Basolo. Oxygen carrier and redox properties of some neutral cobalt chelates. Axial and in-plane ligand effects[J]. Journal of the American Chemical Society, 1974,96(2):392-400.
[28] EI-Ichiro Ochiai. Electronic structure and oxygenation of bis(salicylaldehyde)ethylenediimino Cobalt(Ⅱ)[J]. Journal of Inorganic and Nuclear Chemistry, 1973, 35(5):1727-1739.
[29] Eichhorn E, Rieker A, Bernd Speiser A, et al. Electrochemistry of oxygenation catalysts. 3. 1 thermodynamic characterization of electron transfer and solvent exchange reactions of Co(salen)/[Co(salen)]+in DMF, pyridine, and their mixtures[J]. Inorganic Chemistry, 1997, 36(15):3307-3317.
[30] Opik U, Pryce M H L. Studies of the Jahn-Teller effect. I. a survey of the static problem[J]. Proceedings of the Royal Society A:Mathematical,Physical and Engineering Sciences, 1957, 238(1215):425-447.
[2] Borgne S L, Quintero R. Biotechnological processes for the refining of petroleum[J]. Fuel Processing Technology, 2003, 81(2):155-169.
[3] Hao L, Xiong G, Liu l, et al. Preparation of highly dispersed desulfurization catalysts and their catalytic performance in hydrodesulfurization of dibenzothiophene[J]. Chinese Journal of Catalysis, 2016, 37(3):412-419.
[4] Liu Li(刘丽), Guo Rong(郭蓉), Sun Jin(孙进), et al. The research development of diesel hydrodesulfurization catalysts[J]. Chemical Industry and Engineering Progress(化工进展), 2016, 35(11):3503-3510.
[5] Yu Xingwei(于型伟), Li Xiangjin(李向进), Huang Mingfu(黄明富),et al. Research on technology status and energy saving direction of catalytic gasoline hydrodesulfurization process[J]. Energy Conservation and Emission Reduction in Petroleum and Petrochemical Industry(石油石化节能), 2016, 6(6):4-7.
[6] Cai Jinpeng(蔡金鹏), Wang Fei(王非), Hu Jianheng(胡建恒), et al.Preparation and hydrodesulfurization performance of ZSM-5-MCM-41supported NiMo bimetallic sulfide catalysts[J]. Fine Chemicals(精细化工), 2017, 34(8):886-892.
[7] Liu L, Hong L, Qian J, et al. Progress in the technology for desulfurization of crude oil[J]. China Petroleum Processing&Petrochemical Technology, 2010, 12(4):1-6.
[8] Sun Xin(孙新), Li Shaoping(李少萍), Yao Yao(姚瑶). Research of extraction of sulfide in FCC gasoline with alkaline solution[J]. Henan Chemical Industry(河南化工), 2006, 23(12):17-20.
[9] Song Hua(宋华), Sun Xinglong(孙兴龙), Chang Kai(常凯), et al.Preparation of CuUSY adsorbent and its adsorptive desulfurization performance[J]. Journal of China University of Petroleum(中国石油大学学报:自然科学版), 2011, 35(2):152-156.
[10] Wang Peng(王鹏), Yang Hao(杨浩), Wang Jianhong(王建红), et al.Adsorption desulfurization of model oil by pretreatmented active carbons[J]. Applied Chemical Industry(应用化工), 2016, 45(1):116-119.
[11] Shi Chunwei(史春薇), Zhou Wenfeng(周文丰), Wang Xin(王鑫),et al. Synthesis, characterization and performance of Ce doped HY/SBA-15 for adsorption desulfurization[J]. Petrochemical Technology(石油化工), 2016, 45(1):58-63.
[12] Yang Jing(杨静), Shen Jian(沈健), Shi Weiwei(石微微).Adsorption desulfurization and adsorption kinetics of Cu-β/SBA15[J]. Fine Chemicals(精细化工), 2017, 34(10):1153-1160.
[13] Han Jinyu(韩金玉), Wu Yilin(吴懿琳), Li Yi(李毅). Current situation and development prospect of biodesulfurization technology[J]. Chemical Industry and Engineering Progress(化工进展), 2003,22(10):1072-1075.
[14] Li Yuguang(李玉光), Li Wangliang(李望良), Xing Jianmin(邢建民), et al. Research advances in bioreactors and bioprocesses for biodesulfurization of petroleum[J]. Journal of Chemical Industry and Engineering(化工学报), 2006, 57(5):1040-1047.
[15] Hou Y, Kong Y, Yang J, et al. Biodesulfurization of dibenzothiophene by immobilized cells of Pseudomonas stutzeri UP-1[J]. Fuel, 2005,84(14/15):1975-1979.
[16] Li Miao(李淼), Xiao Lei(肖雷), Zhang Manjuan(张曼娟)et al.The application of biological desulfurization in fossil fuel and the analysis of the prospects and problems in the present day[J].Shandong Chemical Industry(山东化工), 2017, 46(2):39-41.
[17] Jiang Zongxuan(蒋宗轩), Lv Hongying(吕宏缨), Zhang Yongna(张永娜), et al. Oxidative desulfurization of fuel oils[J]. Chinese Journal of Catalysis(催化学报), 2011, 32(5):707-715.
[18] Liu Shuzhi(刘淑芝), Sun Lanlan(孙兰兰), Zhang Xiaoli(张晓丽),et al. Progress on desulfurization of diesel fuel[J]. Chemical Industry and Engineering Progress(化工进展), 2007, 26(2):212-215.
[19] Zhao Dishun(赵地顺), Sun Zhimin(孙智敏), Li Fatang(李发堂), et al. Optimization of oxidative desulfurization of dibenzothiophene using acidic ionic liquid as catalytic solvent[J]. Journal of Fuel Chemistry and Technology(燃料化学学报), 2009, 37(2):194-198.
[20] Chang Jie(常杰), Liu Jing(刘靖), Wang Anjie(王安杰), et al.Research of catalytic oxidation of dibenzothiophene by air[J]. Fine Chemicals(精细化工), 2009, 26(11):1132-1136.
[21] Khan M R, Al-Sayed E. Hydrocarbon desulfurization to clean fuels by selective oxidation versus conventional hydrotreating[J]. Energy Sources, 2007, 30(3):200-217.
[22] Zhang Zhigang(张志刚), Jiang Huiling(蒋慧灵), Huang Ping(黄平). Mechanism analysis and preventive measures of hydrogen peroxide explosion accident[J]. Journal of Safety and Environment(安全与环境学报), 2007, 7(4):108-110.
[23] Yuan Xia(袁霞), Luo Hean(罗和安), Li Fang(李芳). Performance of Co salen/NaY catalyst in cyclohexane oxidation[J]. Petrochemical Technology(石油化工), 2006, 35(5):458-463.
[24] Li Jianzhang(李建章), Lu Xiaoxia(卢晓霞), Qin Shengying(秦圣英). Effect of structure of Schiff base complex on its catalytic oxidation activity[J]. Chemical Research and Application(化学研究与应用), 1999, 11(3):305-307.
[25] Bolzacchini E, Meinardi S, Orlandi M, et al. Substituent effects in the cobalt-catalyzed oxidative carbonylation of aromatic amines[J].Journal of Molecular Catalysis A:Chemical, 1996, 111(3):281-287.
[26] Liang Shuyuan(梁书源). Study on synthesis of Schiff base metal complexes and oxidative desulfurization of sulfide in oil[D]. Qingdao:China University of Petroleum〔中国石油大学(华东)〕, 2018.
[27] Mark J Carter, D Paul Rillema, Fred Basolo. Oxygen carrier and redox properties of some neutral cobalt chelates. Axial and in-plane ligand effects[J]. Journal of the American Chemical Society, 1974,96(2):392-400.
[28] EI-Ichiro Ochiai. Electronic structure and oxygenation of bis(salicylaldehyde)ethylenediimino Cobalt(Ⅱ)[J]. Journal of Inorganic and Nuclear Chemistry, 1973, 35(5):1727-1739.
[29] Eichhorn E, Rieker A, Bernd Speiser A, et al. Electrochemistry of oxygenation catalysts. 3. 1 thermodynamic characterization of electron transfer and solvent exchange reactions of Co(salen)/[Co(salen)]+in DMF, pyridine, and their mixtures[J]. Inorganic Chemistry, 1997, 36(15):3307-3317.
[30] Opik U, Pryce M H L. Studies of the Jahn-Teller effect. I. a survey of the static problem[J]. Proceedings of the Royal Society A:Mathematical,Physical and Engineering Sciences, 1957, 238(1215):425-447.
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