氧气氧化脱除噻吩类硫化物
摘要
燃油低硫化是一种发展趋势,世界各国对液体燃料都制定了极低的含硫标准。传统的加氢脱硫工艺面临极大挑战,而非加氢脱硫工艺如吸附法脱硫、萃取法脱硫、氧化法脱硫等,由于反应条件温和、操作费用低廉,因而倍受关注。其中,氧化脱硫法因其设备简单、不消耗氢气、脱硫效果好,成为近些年来研究者关注的热点。
本文以氧气为氧化剂,在无催化剂、无溶剂的体系里研究了液体燃料中典型硫化物的氧化脱除,其难易顺序为：4,6-二甲基二苯并噻吩>二苯并噻吩>苯并噻吩>噻吩。重点研究了反应温度、反应时间、氧气压力,搅拌速度等对噻吩和苯并噻吩脱除的影响。结果表明,水作溶剂,噻吩较优的脱除条件是：温度150℃、0.8 MPa氧气压力、搅拌速度500 r／min、水、油体积比为3：1,3 h后脱除率为90.4%：苯并噻吩较优的脱除条件是：150℃、0.8 MPa、500 r／min,1 h后氧化脱除率为89.9%。另外,研究了各类烃对硫化物脱除的影响,它们对噻吩影响大小为：乙苯>环己烷>1-辛烯：对苯并噻吩的影响顺序为：十氢萘>乙苯。
New legislation will require substantial reduction in the sulfur content of transportation fuels. The traditional hydrodesulfurization process is highly efficient in removing thiols and sulfides, but is less effective for thiophenes and thiophene derivatives. This is a challenge for traditional hydrodesulfurization process. The attention is paid to other nonhydrodesulfurization technologies, such as adsorptive desulfurization, abstractive desulfurization and oxidative desulfurization. Currently, oxidative desulfurization becomes the hotspot, which is investigated extensively for its mild reaction conditions, not using hydrogen, simple equipment and highly efficiency.
We studied the oxidation of different sulfides in model fuels with oxygen without catalysts and solvents. The results indicated the reactivities of the substrates decrease in the order of 4,6-dimethyldibenzothiophene>dibenzothiophene>benzothiophene>thiophene. The effects of reaction temperature, time, pressure and stirring rate were studied. Then, the results showed that using water as solvent, the thiophene content can be lowered from 1000μg/g to 96μg/g after 3 hours with removal rate of 90.4% under these conditions:150℃,0.8 MPa,500 r/min and the ratio of water to oil is 3:1. The optimal conditions of removal of benzothiophene are as follows:the temperature 150℃,1 h,0.8 MPa oxygen pressure and the stirring rate is 500 r/min. The conversion of benzothiophene is 89.9%. We also studied the effects of kinds of hydrocarbon compounds on the removal of thiophene and benzothiophene, the order thiophene are influenced:ethylbenzene>cyclohexane>1-octene; they influence benzothiophene are:decalin>ethylbenzene.
本文以氧气为氧化剂,在无催化剂、无溶剂的体系里研究了液体燃料中典型硫化物的氧化脱除,其难易顺序为：4,6-二甲基二苯并噻吩>二苯并噻吩>苯并噻吩>噻吩。重点研究了反应温度、反应时间、氧气压力,搅拌速度等对噻吩和苯并噻吩脱除的影响。结果表明,水作溶剂,噻吩较优的脱除条件是：温度150℃、0.8 MPa氧气压力、搅拌速度500 r／min、水、油体积比为3：1,3 h后脱除率为90.4%：苯并噻吩较优的脱除条件是：150℃、0.8 MPa、500 r／min,1 h后氧化脱除率为89.9%。另外,研究了各类烃对硫化物脱除的影响,它们对噻吩影响大小为：乙苯>环己烷>1-辛烯：对苯并噻吩的影响顺序为：十氢萘>乙苯。
New legislation will require substantial reduction in the sulfur content of transportation fuels. The traditional hydrodesulfurization process is highly efficient in removing thiols and sulfides, but is less effective for thiophenes and thiophene derivatives. This is a challenge for traditional hydrodesulfurization process. The attention is paid to other nonhydrodesulfurization technologies, such as adsorptive desulfurization, abstractive desulfurization and oxidative desulfurization. Currently, oxidative desulfurization becomes the hotspot, which is investigated extensively for its mild reaction conditions, not using hydrogen, simple equipment and highly efficiency.
We studied the oxidation of different sulfides in model fuels with oxygen without catalysts and solvents. The results indicated the reactivities of the substrates decrease in the order of 4,6-dimethyldibenzothiophene>dibenzothiophene>benzothiophene>thiophene. The effects of reaction temperature, time, pressure and stirring rate were studied. Then, the results showed that using water as solvent, the thiophene content can be lowered from 1000μg/g to 96μg/g after 3 hours with removal rate of 90.4% under these conditions:150℃,0.8 MPa,500 r/min and the ratio of water to oil is 3:1. The optimal conditions of removal of benzothiophene are as follows:the temperature 150℃,1 h,0.8 MPa oxygen pressure and the stirring rate is 500 r/min. The conversion of benzothiophene is 89.9%. We also studied the effects of kinds of hydrocarbon compounds on the removal of thiophene and benzothiophene, the order thiophene are influenced:ethylbenzene>cyclohexane>1-octene; they influence benzothiophene are:decalin>ethylbenzene.
引文
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