络合铁法湿式脱硫再生反应动力学
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摘要
络合铁湿法氧化脱硫工艺吸收效率高,可操作性强,多数脱硫剂可再生且经济环保,是脱硫研究的热点之一。针对脱硫剂EDTA-Fe(Ⅱ)溶液的氧化再生体系,采用静态的气液扩散反应器,运用电化学方法研究了络合铁法脱硫铁离子再生步骤过程中的反应动力学,建立了反应过程中络合亚铁浓度分布的理论模型并进行了模型检验。研究结果表明,再生过程对于EDTA-Fe(Ⅱ)浓度、O_2体积分数和体系氢离子浓度的反应级数依次为0.902、0.8和-0.152,反应表观活化能为14.24 kJ/mol。模型计算结果与实测数据吻合度较高,可以较好地预测再生过程中不同时刻对应的络合亚铁浓度变化。该模型对于指导络合铁脱硫再生反应器的设计和空气鼓风量、络合剂的补加量、添加位置等均具有一定的理论指导意义。
Complex iron wet oxidative desulfurization process has high absorption efficiency and flexible operability. Most desulfurizers can be regenerated, economic and environmental friendly. It is one of the hotspots in desulfurization research field. The oxidative regeneration system of EDTA-Fe(II) solution was studied in the gas-liquid diffusion reactor. The reaction kinetics of complex iron was studied by electrochemical method and the theoretical model of concentration distribution of complex ferrous iron was established and tested during the regeneration process. The results showed that the reaction order of oxygen volume fraction, EDTA-Fe(II) concentration and hydrogen ion concentration were 0.8, 0.902 and-0.152, respectively, and the apparent activation energy was 14.24 kJ/mol. The calculation results of the model agreed well with the measured data, it could better predict the change of complex ferrous iron concentration at different time in the regeneration process. The model has some theoretical significance for guiding the design of regeneration reactor, the volume flow of air blast, the addition amount of complexing agent and the addition position in desulfurization process.
Complex iron wet oxidative desulfurization process has high absorption efficiency and flexible operability. Most desulfurizers can be regenerated, economic and environmental friendly. It is one of the hotspots in desulfurization research field. The oxidative regeneration system of EDTA-Fe(II) solution was studied in the gas-liquid diffusion reactor. The reaction kinetics of complex iron was studied by electrochemical method and the theoretical model of concentration distribution of complex ferrous iron was established and tested during the regeneration process. The results showed that the reaction order of oxygen volume fraction, EDTA-Fe(II) concentration and hydrogen ion concentration were 0.8, 0.902 and-0.152, respectively, and the apparent activation energy was 14.24 kJ/mol. The calculation results of the model agreed well with the measured data, it could better predict the change of complex ferrous iron concentration at different time in the regeneration process. The model has some theoretical significance for guiding the design of regeneration reactor, the volume flow of air blast, the addition amount of complexing agent and the addition position in desulfurization process.
引文
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[20] 祁极冰,刘有智,罗莹,等.邻菲啰啉分光光度法测定络合铁脱硫液中铁的含量[J].现代化工,2016,36(1):187-190.
[2] SAFARZADEH-AMIRI A,ZHANG Y,EL-DIN M G.Kinetic study of the oxidation of hydrogen sulfide by Fe(III)-Tes=trapolyphosphate (TPP) and Fe(II)-TPP by O2[J].Applied Catalysis B Environmental,2017,218:186-191.
[3] 刘其松,孙茹,易铧.一株天然气生物脱硫菌的分离纯化和生物学特性研究[J].石油与天然气化工,2018,47(3):12-16.
[4] 赵军友,刘崇宁,贺庆强,等.喷射引流法天然气脱硫技术研究[J].石油与天然气化工,2017,46(4):1-5.
[5] 陈赓良.氧化还原法脱硫工艺技术评述[J].天然气与石油,2017,35(1):36-41.
[6] 王海秀.水合物法天然气脱硫工艺研究[J].石油与天然气化工,2014,43(4):370-373.
[7] 李劲,雷萌,唐浠.对中低含硫天然气脱硫技术的认识[J].石油与天然气化工,2013,42(3):227-233.
[8] 岑兆海.膜分离处理非常规天然气的应用前景[J].石油与天然气化工,2012,41(4):370-372.
[9] 吴振中,曹作刚,李发永.络合铁法脱硫工艺研究进展[J].石化技术,2006,13(1):45-48.
[10] 罗莹,朱振峰,刘有智.络合铁法脱H2S技术研究进展[J].天然气化工(C1化学与化工),2014,39(1):88-94.
[11] 张世光,罗莹,郭芳.基于氨基多羧酸螯合铁催化氧化硫化氢技术的研究进展[J].中北大学学报(自然科学版),2016,37(6):625-632.
[12] SADA E,KUMAZAWA H,MACHIDA H.Oxidation kinetics of FeII-edta and FeII-nta chelates by dissolved oxygen[J].Industrial & Engineering Chemistry Research,1987,26(7):1468-1472.
[13] DEMMINK J F,BEENACKERS A A C M.Oxidation of ferrous nitrilotriacetic acid with oxygen:A model for oxygen mass transfer parallel to reaction kinetics[J].Industrial & Engineering Chemistry Research,1997,36(6):1989-2005.
[14] 陈煜泉.络合铁湿式氧化硫化氢的工艺及动力学[D].杭州:浙江工业大学,2017.
[15] WUBS H J,BEENACKERS A A C M.Kinetics of the oxidation of ferrous chelates of EDTA and HEDTA in aqueous solution[J].Industrial & Engineering Chemistry Research,1993,32(11):2580-2594.
[16] ZANG V,ELDIK R V.Kinetics and mechanism of the autoxidation of iron(II) induced through chelation by ethylenediaminetetraacetate and related ligands[J].Inorganic Chemistry,1990,29(9):1705-1711.
[17] BROWN E R,MAZZARELLA J D.Mechanism of oxidation of ferrous polydentate complexes by dioxygen[J].Journal of Electroanalytical Chemistry and Interfacial Electrochemistry,1987,222(1-2):173-192.
[18] 李小明,王冶,毕勤成,等.气泡在不同液体中上升速度的实验研究[J].西安交通大学学报,2003,37(9):971-974.
[19] HARVEY JR A E,SMART J A,AMIS E S.Simultaneous spectrophotometric determination of iron(II) and total iron with 1,10-phenanthroline[J].Analytical Chemistry,1955,27(1):26-29.
[20] 祁极冰,刘有智,罗莹,等.邻菲啰啉分光光度法测定络合铁脱硫液中铁的含量[J].现代化工,2016,36(1):187-190.
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