催化裂化汽油砷化物分布规律
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摘要
采用自动快速蒸馏装置对脱砷前后的催化裂化汽油进行窄馏分切割,利用原子荧光光谱法对各窄馏分砷化物含量进行分析,研究催化汽油脱砷前后砷化物分布规律,为催化裂化汽油脱砷剂开发及脱砷工艺流程选择提供指导。实验结果表明:随着各窄馏分沸点增加,砷化物所占比例逐渐增大,90%以上砷化物均分布在80℃以上的重汽油组分中,尤其170℃以上馏分砷化物所占比例陡增,占总砷化物65.82%～96.31%。吸附脱砷剂对汽油150℃之前馏分中砷化物实现了全部脱除,而对150℃之后的重馏分脱砷率略有下降;临氢脱砷剂对汽油中80℃之前轻馏分和170℃之后重馏分中砷化物具有较高的脱除率,达到90%以上,而对中间馏分中砷化物脱除率较低。
The narrow fraction cutting of FCC gasoline before and after dearsenification were carried out in a flash distillation apparatus. The arsenide content in narrow fractions were analyzed by Atomic Fluorescence Spectrometry(AFS), and the arsenic distribution laws were studied, which provided guidance for the development of de-arsenic catalyst and the selection of arsenic removal process. The experimental results showed that the proportion of arsenide was increasing with the increase of the boiling point of narrow fraction, and more than 90% arsenide was in the heavy gasoline component(≥80℃). In particular,the proportion of arsenide in the fraction above 170℃ increased sharply, accounting for 65.82%-96.31%of the total arsenide. For adsorption dearsenification, the arsenic in the fraction of gasoline before 150℃was all removed, and the dearsening rate of heavy distillates above 150℃ decreased slightly. For hydrogenation dearsenification, the arsenic removal rates for the light fractions before 80℃ in gasoline and the heavy fractions after 170℃ were both higher than 90%, while that for the middle fraction was lower.
The narrow fraction cutting of FCC gasoline before and after dearsenification were carried out in a flash distillation apparatus. The arsenide content in narrow fractions were analyzed by Atomic Fluorescence Spectrometry(AFS), and the arsenic distribution laws were studied, which provided guidance for the development of de-arsenic catalyst and the selection of arsenic removal process. The experimental results showed that the proportion of arsenide was increasing with the increase of the boiling point of narrow fraction, and more than 90% arsenide was in the heavy gasoline component(≥80℃). In particular,the proportion of arsenide in the fraction above 170℃ increased sharply, accounting for 65.82%-96.31%of the total arsenide. For adsorption dearsenification, the arsenic in the fraction of gasoline before 150℃was all removed, and the dearsening rate of heavy distillates above 150℃ decreased slightly. For hydrogenation dearsenification, the arsenic removal rates for the light fractions before 80℃ in gasoline and the heavy fractions after 170℃ were both higher than 90%, while that for the middle fraction was lower.
引文
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[10]合金,愈杰,王占宇. FDAs-1脱砷剂的研究与开发[J].工业催化,2004, 12(3):14-16.HE J, YU J, WANG Z Y. Development of FDAs-1 dearsenic catalyst[J]. Industrial Catalysis, 2004, 12(3):14-16.
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[12]张华,王英锋,施燕支,等.高效液相色谱及联用技术在砷形态分析中的应用[J].光谱学与光谱分析, 2007, 27(3):386-390.ZHANG H, WANG Y F, SHI Y Z, et al. Application of high performance liquid chromatography and hyphenated techniques in analysis of arsenic species[J]. Spectroscopy and Spectral Analysis,2007, 27(3):386-390.
[2] BAGHALHA M, HOSEINI S M. Long-term deactivation of a commercial CoMo/γ-Al2O3catalyst in hydrodesulfurization of a naphtha stream[J]. Industrial&Engineering Chemistry Research,2008, 48(7):3331-3440.
[3]吴建国,李德柱,冶雅婷,等. TAS-15型脱砷催化剂的工业应用[J].工业催化, 2013, 21(4):59-61.WU J G, LI D Z, YE Y T, et al. Commercial application of TAS-15dearsenization catalyst[J]. Industrial Catalysis, 2013, 21(4):59-61.
[4]李井泉,孙发民,常玉红,等. DZAs-2脱砷剂的开发与应用评价[J].炼油与化工, 2009, 20(2):15-17.LI J Q, SUN F M, CHANG Y H, et al. Development and application evaluation of DZAs-2 dearsenization agent[J]. Refining and Chemical Industry, 2009,20(2):15-17.
[5]孙殿成,霍宏敏,王更新,等. LAs-1型加氢脱砷催化剂的研究与开发[J].炼油设计, 2002, 32(10):40-43.SUN D C, HUO H M, WANG G X, et al. Research and development of LAs-1 hydrodearsenicization catalyst[J]. Petroleum Refinery Engineering, 2002, 32(10):40-43.
[6]王定博,袁霞光,冷冰,等.脱砷剂研究进展[J].化工进展, 2002, 21(1):17-19.WANG D B, YUAN X G, LENG B, et al. Research progress on arsenic removal catalysts[J]. Chemical Industry and Engineering Progress,2002, 21(1):17-19.
[7]洪晓煜,李洪洋,张伟,等. TAS-15型脱砷剂用于催化汽油脱砷[J].工业催化, 2012, 20(5):55-57.HONG X Y, LI H Y, ZHANG W, et al. Researches on TAS-15dearsenic catalyst for arsenic removal from FCC gasoline[J]. Industrial Catalysis, 2012, 20(5):55-57.
[8]王新华,贾秋生,王蕾,等. SH/T0629—1996石脑油砷含量测定法的分析[J].炼油与化工, 2009, 20(4):36-38.WANG X H, JIA Q S, WANG L, et al. Analysis on SH/T0629—1996testing method for arsenic content in naphtha[J]. Refining and Chemical Industry, 2009, 20(4):36-38.
[9]张小确,杨德凤,杨树青.原子荧光光谱法测定裂解汽油中的痕量砷[J].现代科学仪器, 2008(2):79-82.ZHANG X Q, YANG D F, YANG S Q. Determination of trace as in pyrolysis gasoline by atomic fluorescence spectrometry[J]. Modern Scientific Instruments, 2008(2):79-82.
[10]合金,愈杰,王占宇. FDAs-1脱砷剂的研究与开发[J].工业催化,2004, 12(3):14-16.HE J, YU J, WANG Z Y. Development of FDAs-1 dearsenic catalyst[J]. Industrial Catalysis, 2004, 12(3):14-16.
[11]苑春刚, X. Chris Le.砷形态分析[J].化学进展, 2009, 21(2/3):467-473.YUAN C G, X.Chris Le. Arsenic speciation analysis[J]. Progress in Chemistry, 2009, 21(2/3):467-473.
[12]张华,王英锋,施燕支,等.高效液相色谱及联用技术在砷形态分析中的应用[J].光谱学与光谱分析, 2007, 27(3):386-390.ZHANG H, WANG Y F, SHI Y Z, et al. Application of high performance liquid chromatography and hyphenated techniques in analysis of arsenic species[J]. Spectroscopy and Spectral Analysis,2007, 27(3):386-390.