采用一步合成法制备了以甘氨酸为阳离子、磷钨酸为阴离子的功能化杂多酸盐[Gly]_3PW_(12)O_(40)。以[Gly]_3PW_(12)O_(40)为催化剂,以离子液体[Hmim]PF6、[Hmim]BF4、[Bmim]PF6、[Bmim]BF4分别为萃取剂,以过氧化氢为氧化剂,构建了杂多...采用一步合成法制备了以甘氨酸为阳离子、磷钨酸为阴离子的功能化杂多酸盐[Gly]_3PW_(12)O_(40)。以[Gly]_3PW_(12)O_(40)为催化剂,以离子液体[Hmim]PF6、[Hmim]BF4、[Bmim]PF6、[Bmim]BF4分别为萃取剂,以过氧化氢为氧化剂,构建了杂多酸盐耦合离子液体的催化氧化脱硫体系。研究表明,以[Hmim]PF6为萃取剂可以获得最佳的脱硫效果。采用单因素实验研究了脱硫工艺条件对[Gly]_3PW_(12)O_(40)/[Hmim]PF6/H2O2体系脱硫效果的影响。结果表明,在n(过氧化氢)/n(硫)=4、反应时间为90 min、反应温度为60℃、n[Gly]_3PW_(12)O_(40)/n(硫)=0.025、[Hmim]PF6用量为1 m L条件下,燃料油的脱硫率可达99.2%,并且脱硫体系[Gly]_3PW_(12)O_(40)/[Hmim]PF6具有很好的重复使用性能。展开更多
通过简单加热氯代正丁基吡啶([C_4Pyr]Cl)和对甲苯磺酸(TsOH)的混合物制备了[C_4Pyr]Cl/nTsOH,(n=0.1,0.2,0.3)型低共熔溶剂。以[C_4Pyr]Cl/nTsOH为催化剂和萃取剂,H_2O_2为氧化剂组成萃取-催化氧化脱硫体系氧化脱除模拟油中的硫化物。...通过简单加热氯代正丁基吡啶([C_4Pyr]Cl)和对甲苯磺酸(TsOH)的混合物制备了[C_4Pyr]Cl/nTsOH,(n=0.1,0.2,0.3)型低共熔溶剂。以[C_4Pyr]Cl/nTsOH为催化剂和萃取剂,H_2O_2为氧化剂组成萃取-催化氧化脱硫体系氧化脱除模拟油中的硫化物。通过FTIR表征,确定[C_4Pyr]Cl/0.2TsOH的结构以及氧化产物,并考察了不同脱硫体系、n(TsOH)∶n([C_4Pyr]Cl)、低共熔溶剂加入量、反应温度、n(H_2O_2)∶n(二苯并噻吩)和含硫化物类型对脱硫效果的影响。实验结果表明,在低共熔溶剂[C_4Pyr]Cl/0.2TsOH加入量1.00 m L、反应温度50℃、n(H_2O_2)∶n(二苯并噻吩)=6、模拟油用量5 m L的反应条件下,[C_4Pyr]Cl/0.2TsOH对二苯并噻吩、4,6-二甲基二苯并噻吩和苯并噻吩的脱硫率分别达98.2%,96.0%,40.2%。由一级动力学方程和Arrhenius方程计算氧化脱除二苯并噻吩所需的表观活化能约为51.95 k J/mol。[C_4Pyr]Cl/0.2TsOH回收利用5次后,脱硫率仍不低于95.1%。展开更多
采用微波法合成了双核酞菁钴,并采用红外光谱、紫外可见光谱、热重分析对其进行表征。以二苯并噻吩(DBT)为反应底物,考察双核酞菁钴对DBT催化氧化性能,筛选出较优催化剂,并进行脱硫反应工艺条件优化。结果表明,双核酞菁钴具有较好的催...采用微波法合成了双核酞菁钴,并采用红外光谱、紫外可见光谱、热重分析对其进行表征。以二苯并噻吩(DBT)为反应底物,考察双核酞菁钴对DBT催化氧化性能,筛选出较优催化剂,并进行脱硫反应工艺条件优化。结果表明,双核酞菁钴具有较好的催化性能,在室温下、双核酞菁钴用量为0.01 g(cat)/5 m L、空气流量为80 m L/min、反应温度为40℃、反应1 h,DBT脱硫率达到97.17%。催化剂重复使用5次,催化效果无明显下降。氧化产物经红外光谱、质谱分析为DBTO2。对芳香烃及烯烃进行了催化氧化实验,发现该工艺对油品的质量基本无影响。展开更多
Catalytic oxidative desulfurization(ODS) of model oil and commercial oil samples was investigated using an air-assisted performic acid oxidation system with a phase transfer or emulsion catalyst comprising a quaternar...Catalytic oxidative desulfurization(ODS) of model oil and commercial oil samples was investigated using an air-assisted performic acid oxidation system with a phase transfer or emulsion catalyst comprising a quaternary ammonium salt-based heteropolyoxometalate.Different emulsion catalysts with a Keggin type heteroployoxometalate anion(containing W,Mo,and V) and cetyltrimethylammonium bromide cation were prepared and characterized by X-ray fluorescence,Fourier transform infrared spectroscopy,and scanning electron microscopy.[C16H33N(CH3)3]3[PW9Mo3O40] was the most effective catalyst in the current oxidation system,which reduced the sulfur content of the model oil from 1275 μg/g to 57 μg/g.The reactivity order of different model sulfur compounds was thiophene < dibenzothiophene < 4,6-dimethyldibenzothiophene. The ODS of model sulfur compounds followed first order kinetics with apparent activation energy from 29 to 27 kJ/mol.The catalysts also performed efficiently in the ODS of the industrial oil samples,including untreated naphtha,light gas oil,heavy gas oil,and Athabasca oil sands derived bitumen,for which sulfur removal rates were 83%,85%,68% and 64%,respectively.展开更多
In this paper, the oxidative desulfurization （ODS） system is directly applied to deal with the catalytic oxidation of sulfur compounds of sulfur-containing model oil by dielectric barrier discharge （DBD） plasma in...In this paper, the oxidative desulfurization （ODS） system is directly applied to deal with the catalytic oxidation of sulfur compounds of sulfur-containing model oil by dielectric barrier discharge （DBD） plasma in the presence of air plus an extraction step with the oxidation-treated fuel put over ionic liquid [BMIM]FeC14 （1-butyl-3-methylimidazolium tetrachloroferrate）. This new system exhibited an excellent desulfurization effect. The sulfur content of DBT in diesel oil decreased from 200 ppm to 4.92 ppm （S removal rate up to 97.5%） under the following optimal reaction conditions： air flow rate （v） of 60 mL/min, amplitude of applied voltage （U） on DBD of 16 kV, input frequency （f） of 79 kHz, catalyst amount （w） of 1.25 wt%, reaction time （t） of 10 min. Moreover, a high desulfurization rate was obtained during oxidation of benzothiophene （BT） or 4,6-DMDBT （4,6-dimethyl-dibenzothiophene） under the aforementioned conditions. The oxidation reactivity of different S compounds was decreased in the order of DBT, 4,6-DMDBT and BT. The remarkable advantage of the novel ODS system is that the desulfurization condition applies in the presence of air at ambient conditions without peroxides, aqueous solvent or biphasic oil-aqueous solution system.展开更多
文摘采用一步合成法制备了以甘氨酸为阳离子、磷钨酸为阴离子的功能化杂多酸盐[Gly]_3PW_(12)O_(40)。以[Gly]_3PW_(12)O_(40)为催化剂,以离子液体[Hmim]PF6、[Hmim]BF4、[Bmim]PF6、[Bmim]BF4分别为萃取剂,以过氧化氢为氧化剂,构建了杂多酸盐耦合离子液体的催化氧化脱硫体系。研究表明,以[Hmim]PF6为萃取剂可以获得最佳的脱硫效果。采用单因素实验研究了脱硫工艺条件对[Gly]_3PW_(12)O_(40)/[Hmim]PF6/H2O2体系脱硫效果的影响。结果表明,在n(过氧化氢)/n(硫)=4、反应时间为90 min、反应温度为60℃、n[Gly]_3PW_(12)O_(40)/n(硫)=0.025、[Hmim]PF6用量为1 m L条件下,燃料油的脱硫率可达99.2%,并且脱硫体系[Gly]_3PW_(12)O_(40)/[Hmim]PF6具有很好的重复使用性能。
文摘通过简单加热氯代正丁基吡啶([C_4Pyr]Cl)和对甲苯磺酸(TsOH)的混合物制备了[C_4Pyr]Cl/nTsOH,(n=0.1,0.2,0.3)型低共熔溶剂。以[C_4Pyr]Cl/nTsOH为催化剂和萃取剂,H_2O_2为氧化剂组成萃取-催化氧化脱硫体系氧化脱除模拟油中的硫化物。通过FTIR表征,确定[C_4Pyr]Cl/0.2TsOH的结构以及氧化产物,并考察了不同脱硫体系、n(TsOH)∶n([C_4Pyr]Cl)、低共熔溶剂加入量、反应温度、n(H_2O_2)∶n(二苯并噻吩)和含硫化物类型对脱硫效果的影响。实验结果表明,在低共熔溶剂[C_4Pyr]Cl/0.2TsOH加入量1.00 m L、反应温度50℃、n(H_2O_2)∶n(二苯并噻吩)=6、模拟油用量5 m L的反应条件下,[C_4Pyr]Cl/0.2TsOH对二苯并噻吩、4,6-二甲基二苯并噻吩和苯并噻吩的脱硫率分别达98.2%,96.0%,40.2%。由一级动力学方程和Arrhenius方程计算氧化脱除二苯并噻吩所需的表观活化能约为51.95 k J/mol。[C_4Pyr]Cl/0.2TsOH回收利用5次后,脱硫率仍不低于95.1%。
文摘采用微波法合成了双核酞菁钴,并采用红外光谱、紫外可见光谱、热重分析对其进行表征。以二苯并噻吩(DBT)为反应底物,考察双核酞菁钴对DBT催化氧化性能,筛选出较优催化剂,并进行脱硫反应工艺条件优化。结果表明,双核酞菁钴具有较好的催化性能,在室温下、双核酞菁钴用量为0.01 g(cat)/5 m L、空气流量为80 m L/min、反应温度为40℃、反应1 h,DBT脱硫率达到97.17%。催化剂重复使用5次,催化效果无明显下降。氧化产物经红外光谱、质谱分析为DBTO2。对芳香烃及烯烃进行了催化氧化实验,发现该工艺对油品的质量基本无影响。
基金Financial support from the Higher Education Commission(HEC) Pakistan,under the International Research Support Initiative Program(IRSIP)
文摘Catalytic oxidative desulfurization(ODS) of model oil and commercial oil samples was investigated using an air-assisted performic acid oxidation system with a phase transfer or emulsion catalyst comprising a quaternary ammonium salt-based heteropolyoxometalate.Different emulsion catalysts with a Keggin type heteroployoxometalate anion(containing W,Mo,and V) and cetyltrimethylammonium bromide cation were prepared and characterized by X-ray fluorescence,Fourier transform infrared spectroscopy,and scanning electron microscopy.[C16H33N(CH3)3]3[PW9Mo3O40] was the most effective catalyst in the current oxidation system,which reduced the sulfur content of the model oil from 1275 μg/g to 57 μg/g.The reactivity order of different model sulfur compounds was thiophene < dibenzothiophene < 4,6-dimethyldibenzothiophene. The ODS of model sulfur compounds followed first order kinetics with apparent activation energy from 29 to 27 kJ/mol.The catalysts also performed efficiently in the ODS of the industrial oil samples,including untreated naphtha,light gas oil,heavy gas oil,and Athabasca oil sands derived bitumen,for which sulfur removal rates were 83%,85%,68% and 64%,respectively.
基金supported by National Natural Science Foundation of China(No.21063012)the Ministry of Education Innovation Team of China(No.IRT1161)
文摘In this paper, the oxidative desulfurization （ODS） system is directly applied to deal with the catalytic oxidation of sulfur compounds of sulfur-containing model oil by dielectric barrier discharge （DBD） plasma in the presence of air plus an extraction step with the oxidation-treated fuel put over ionic liquid [BMIM]FeC14 （1-butyl-3-methylimidazolium tetrachloroferrate）. This new system exhibited an excellent desulfurization effect. The sulfur content of DBT in diesel oil decreased from 200 ppm to 4.92 ppm （S removal rate up to 97.5%） under the following optimal reaction conditions： air flow rate （v） of 60 mL/min, amplitude of applied voltage （U） on DBD of 16 kV, input frequency （f） of 79 kHz, catalyst amount （w） of 1.25 wt%, reaction time （t） of 10 min. Moreover, a high desulfurization rate was obtained during oxidation of benzothiophene （BT） or 4,6-DMDBT （4,6-dimethyl-dibenzothiophene） under the aforementioned conditions. The oxidation reactivity of different S compounds was decreased in the order of DBT, 4,6-DMDBT and BT. The remarkable advantage of the novel ODS system is that the desulfurization condition applies in the presence of air at ambient conditions without peroxides, aqueous solvent or biphasic oil-aqueous solution system.
