连续电解Bunsen反应产物制氢的研究
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摘要
Bunsen反应作为实现硫化氢裂解循环的关键步骤,在产物的分离和纯化、副反应、碘蒸气沉积及腐蚀等方面面临着巨大的技术挑战。直接电解Bunsen反应产物可以从根本上解决产物的分离问题,从而减少反应物的过量使用。连续电解Bunsen反应产物HI/H_2SO_4混酸,分析了电解结果随时间变化的趋势,考察了阳极电解液中甲苯的存在对电解结果的影响。结果表明:连续电解在3h后可进入稳态,电解槽电压在1.0～1.5h迅速升高并稳定在3.33V;6h后阳极电解液中I~-浓度可以降低49%.阳极电解液中的I~-会透过质子交换膜进入阴极室,污染阴极电解液;甲苯的存在有利于降低阳极液中剩余I~-的浓度,抑制I~-对阴极电解液的污染及降低电解能耗。
The H_2S splitting cycle provides a technical route for the reutilization of the sulfurcontaining pollutants in coal to produce high-quality and high-value hydrogen and sulfuric acid.As the critical step of this cycle,Bunsen reaction faces great challenges on the separation and purification of the products,the side reactions,the deposition of iodine vapor,and corrosion.The direct electrolysis of the Bunsen reaction products can avoid the separation of the products and reduce the excessive use of reactants.A preliminary investigation of the continuous electrolysis of the Bunsen reaction products, HI/H_2SO_4 mixed solution, was conducted in this paper.Evolutions of the electrolytic results as a function of time were analyzed and the effects of the presence of toluene in the anolyte on the electrolysis results were also studied.The continuous electrolysis reached the steady state after 3 hours.The cell voltage dramatically increased after 1 hour and then stabilized at 3.33 V.I~-concentration in the anolyte could be reduced by 49% after6 hour electrolysis.I~-in the anolyte may cross the proton exchange membrane to contaminate the catholyte.The presence of toluene is beneficial to reducing the residual I~-concentration in the anolyte,inhibiting the I~-contamination of the catholyte and reducing the energy consumption of the electrolysis.
The H_2S splitting cycle provides a technical route for the reutilization of the sulfurcontaining pollutants in coal to produce high-quality and high-value hydrogen and sulfuric acid.As the critical step of this cycle,Bunsen reaction faces great challenges on the separation and purification of the products,the side reactions,the deposition of iodine vapor,and corrosion.The direct electrolysis of the Bunsen reaction products can avoid the separation of the products and reduce the excessive use of reactants.A preliminary investigation of the continuous electrolysis of the Bunsen reaction products, HI/H_2SO_4 mixed solution, was conducted in this paper.Evolutions of the electrolytic results as a function of time were analyzed and the effects of the presence of toluene in the anolyte on the electrolysis results were also studied.The continuous electrolysis reached the steady state after 3 hours.The cell voltage dramatically increased after 1 hour and then stabilized at 3.33 V.I~-concentration in the anolyte could be reduced by 49% after6 hour electrolysis.I~-in the anolyte may cross the proton exchange membrane to contaminate the catholyte.The presence of toluene is beneficial to reducing the residual I~-concentration in the anolyte,inhibiting the I~-contamination of the catholyte and reducing the energy consumption of the electrolysis.
引文
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[2]HABEEB O A,KANTHASAMY R,ALI G M,et al.Hydrogen sulfide emission sources,regulations,and removal techniques:a review[J].Rew Chem Eng,2018,34(6):837-854.
[3]GUPTA A K,IBRAHIM S,AL S A.Advances in sulfur chemistry for treatment of acid gases[J].Prog Energy Combust Sci,2016,54:65-92.
[4]WANG H.Hydrogen production from a chemical cycle of H2S splitting[J].Int J Hydrogen Energy,2007,32(16):3907-3914.
[5]YU G F,WANG H,CHUANG K T.Upper bound for the efficiency of a novel chemical cycle of H2S splitting for H2production[J].Energ Fuel,2009,23:2184-2191.
[6]NOMAN J,BESENBRUCH G E,BROWN L C,et al.Thermo-chemical water-splitting cycle,benchscale investigations,and process engineering:GAA16713[R].Washington DC:General Atomics,1982.
[7]ZHANG K,BAO W R,CHANG L P,et al.A review of recent researches on Bunsen reaction for hydrogen production via S-Iwater and H2S splitting cycles[J].J Energy Chem,2019,33:46-58.
[8]WANG H,LE PERSON A,ZHAO X,et al.A low-temperature hydrogen production process based on H2S splitting cycle for sustainable oil sands bitumen upgrading[J].Fuel Process Technol,2013,108:55-62.
[9]LI J,MONIRI A,WANG H.Apparent kinetics of a gas-liquid-liquid system of Bunsen reaction with iodine-toluene solution for hydrogen production through H2S splitting cycle[J].Int J Hydrogen Energy,2015,40:2912-2920.
[10]ZHANG K,ZHAO X,CHEN S H,et al.Direct electrolysis of Bunsen reaction product HI/H2SO4/H2O/toluene mixture for hydrogen production:Pt electrode characterization[J].Int J Hydrogen Energy,2018,43:13702-13710.
[11]SANTASALO A A,VIRTANEN J,GASIK M.SO2carry-over and sulphur formation in a SO2-depolarized electrolyser[J].JSolid State Electrochem,2016,20:1655-1663.
[12]IMMANUEL V,PARVATALU D,BHARDWAJ A,et al.Properties of Nafion 117in highly acidic environment of Bunsen reaction of I-S cycle[J].J Membr Sci,2012,409/410:137-144.
[13]ZENG K,ZHANG D K.Recent progress in alkaline water electrolysis for hydrogen production and applications[J].Prog Energ Combust,2010,36:307-326.
[14]BARD A J,FAULKNER L R.Electrochemical methods:fundamentals and applications[M].New Jersey:John Wiley&Sons,2001.
[15]LU Y,LIU G,LUO H,et al.Efficient in-situ production of hydrogen peroxide using a novel stacked electrosynthesis reactor[J].Electrochim Acta,2017,248:29-36.
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