尿素络合法分离费托合成产品中的正构烷烃
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摘要
分别以费托合成直馏柴油和异构柴油为原料,通过尿素/硫脲对正构烷烃和异构烷烃进行分离,从而提高产品附加值。通过尿素或硫脲法分离直馏柴油中的正/异构烷烃实验可以看出,采用尿素法一次脱蜡得到的产品中正构烷烃含量达到97.0%(质量分数,下同),二次脱蜡得到的正构烷烃含量达到98.0%;通过硫脲法分离正/异构烷烃,产品中正构烷烃含量为96.5%,但硫脲量使用量降低。通过对尿素法分离异构柴油的研究,可以看出尿素量增加有利于降低异构柴油的凝点。对比尿素法和硫脲法的分离结果,可以看出,尿素和硫脲均可与正/异构烷烃反应,但稳定性存在差异。相对而言,尿素与高碳异构烷烃或低碳正构烷烃形成络合物更稳定,硫脲与高碳正构烷烃或低碳异构烷烃形成络合物更稳定。
In order to improve additional value of straight-run diesel and heterogeneous diesel in F-T synthesis, normal and isomerous hydrocarbon were separated by urea/thiourea inclusion method, respectively. By studying the separation process of straight-run diesel, optimum experimental conditions(20 g urea, 200 mL anhydrous ethanol, 20 g raw oil, 30 ℃) were obtained. It can be seen that n-paraffin content in complex phase product could reach 97.0% by primary urea separation and add up to 98.0% by secondary urea separation at the optimum experimental conditions. Separation of straight-run diesel by thiourea inclusion method was also studied. The content of n-paraffin in the product was about 96.5%, but the amount of thiourea was decreased. In separation process of heterogeneous diesel by urea inclusion method, the increase of urea addition can reduce the condensation point. Comparing the result of urea and thiourea separation, urea is more stable with low-carbon n-paraffin and high-carbon iso-paraffin, while thiourea is more stable with high-carbon n-paraffin and low-carbon iso-paraffin.
In order to improve additional value of straight-run diesel and heterogeneous diesel in F-T synthesis, normal and isomerous hydrocarbon were separated by urea/thiourea inclusion method, respectively. By studying the separation process of straight-run diesel, optimum experimental conditions(20 g urea, 200 mL anhydrous ethanol, 20 g raw oil, 30 ℃) were obtained. It can be seen that n-paraffin content in complex phase product could reach 97.0% by primary urea separation and add up to 98.0% by secondary urea separation at the optimum experimental conditions. Separation of straight-run diesel by thiourea inclusion method was also studied. The content of n-paraffin in the product was about 96.5%, but the amount of thiourea was decreased. In separation process of heterogeneous diesel by urea inclusion method, the increase of urea addition can reduce the condensation point. Comparing the result of urea and thiourea separation, urea is more stable with low-carbon n-paraffin and high-carbon iso-paraffin, while thiourea is more stable with high-carbon n-paraffin and low-carbon iso-paraffin.
引文
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[15] 王燕, 葛喜慧, 张敏卿, 等. 费托合成高温油相产品中正构烃的分离[J]. 化工进展, 2014, 33(11): 2 894-2 898Wang Yan, Ge Xihui, Zhang Minqing, et al. Separation of n-hydrocarbons from high temperature oil phase products of Fischer-Tropsch synthesis[J]. Chemical Industry and Engineering Process, 2014, 33(11): 2 894-2 898(in Chinese)
[16] Yata N. Studies on the urea-dewaxing of lubricating oils[J]. Bulletin of the Japan Petroleum Institute, 1962, 4: 35-44
[17] Swean D. Urea and thiourea complexes in separating organic compounds[J]. Industrial and Engineering Chemistry, 1955, 47(2): 216-221
[18] Makin E C, Glass K I, Middlebrooks C H, et al. Urea adduction process in semi continuous fixed bed[J]. Process Design and Development, 1964, 3(3): 226-229
[2] 侯祥麟. 中国炼油技术[M]. 北京:中国石化出版社, 1991
[3] 姚致远, 黄荣荣, 姜仁玲, 等. 尿素络合法生产重质液体石蜡的工艺研究[J]. 化学工业与工程技术, 2001, 22(6): 11-12Yao Zhiyuan, Huang Rongrong, Jiang Renling, et al. Technological study of producing heavy-liquid wax by urea inclusion method[J]. Journal of Chemical Industry & Engineering, 2001, 22 (6): 11-12(in Chinese)
[4] 张子孺, 李元春, 李峰. 直馏柴油异丙醇尿素脱蜡生产重液体石蜡[J]. 辽宁石化, 2004, 33(8): 444-445Zhang Ziru, Li Yuanchun, Li Feng. Liquid wax production by isopropanol-urea dewaxing from straight-run diesel[J]. Liaoning Chemical Industry, 2004, 33(8): 444-445(in Chinese)
[5] Redlich O, Gable C M, Beason L R, et al. Addition compounds of thiourea[J]. Journal of the American Chemical Society, 2002, 72(9): 4 161-4 162
[6] 赵军, 潘大壮. 三种原油的直馏柴油馏分尿素脱蜡研究[J]. 沈阳化工学院学报, 2006, 20(1): 4-8Zhao Jun, Pan Dazhuang. Urea dewaxing study of straight-run diesel distillation from three kinds of raw oil[J]. Journal of Shenyang Institute of Chemical Technology, 2006, 20(1): 4-8(in Chinese)
[7] Mariette C, Huard M, Rabiller P. A molecular “phase ordering” phase transition leading to amodulated periodic composite in n-heptane/urea [J]. J Chem Phys, 2012, 136: 104507, doi: 10.1063/1.3692329
[8] Marit-Rujas J, Desmetd A, Kenneth D M. Bidirectional transport of guest molecules through the nanoporous tunnel structure of a solid inclusion compound [J]. J Phys Chem C, 2009, 113: 736-743
[9] Yeo L, Kariuki B M, Heliodoro-Serranogonzález A, et al. Structural properties of the low-temperature phase of the hexadecane/urea inclusion compound, investigated by synchrotron X-ray powder diffraction [J]. Journal of Physical Chemistry B, 1997, 101(101): 9 926-9 931
[10] Smith A E. The crystal structure of the urea-hydrocarbon complexes [J]. Acta Cryst, 1952, 5: 224-235
[11] Martí-Rujas J, Harris K D, Desmedt A, et al. Significant conformational changes associated with molecular transport in a crystalline solid[J]. Journal of Physical Chemistry B, 2006, 110(22):10 708-10 713
[12] Kobe K A, Reinhart L R. Separation of organic compounds with urea and thioure[J]. University of Texas, 1959, 36(6): 300-301
[13] Cannarrizzo G M, Meresi G H, Vold R L, et al. Conformation and stability of alkane/urea inclusion compounds: Evidence from deuterium NMR spectroscopy [J]. J Phys Chem, 1991, 95: 1 525-1 527
[14] Wang Y, Ge X, Zhang M, et al. Growth characteristic, guest distribution, guest ordering and the stability of urea inclusion compounds with 1-decene, n-decane and mixture of 1-decene and n-decane [J]. Journal of Molecular Structure, 2014, 1 058: 259-264
[15] 王燕, 葛喜慧, 张敏卿, 等. 费托合成高温油相产品中正构烃的分离[J]. 化工进展, 2014, 33(11): 2 894-2 898Wang Yan, Ge Xihui, Zhang Minqing, et al. Separation of n-hydrocarbons from high temperature oil phase products of Fischer-Tropsch synthesis[J]. Chemical Industry and Engineering Process, 2014, 33(11): 2 894-2 898(in Chinese)
[16] Yata N. Studies on the urea-dewaxing of lubricating oils[J]. Bulletin of the Japan Petroleum Institute, 1962, 4: 35-44
[17] Swean D. Urea and thiourea complexes in separating organic compounds[J]. Industrial and Engineering Chemistry, 1955, 47(2): 216-221
[18] Makin E C, Glass K I, Middlebrooks C H, et al. Urea adduction process in semi continuous fixed bed[J]. Process Design and Development, 1964, 3(3): 226-229