催化裂化柴油中碱性氮化物的脱除研究
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摘要
本研究研制出固、液两种高性能催化裂化柴油碱性氮脱除剂。采用液相法脱氮时,深入研究了浓度、剂油比、温度等因素对脱氮效果的影响,确立了最优工艺条件,并对其脱除机理和动力学进行了探讨。结果表明:室温下,采用浓度70%混酸为液态脱氮剂主剂,当剂油比为1:400、反应时间10min、沉降时间10min时,RFCC柴油中的碱性氮脱除率高达97.50%,油品透光率由精制前的3.8%增至36.4%。脱氮剂与油品中碱性氮的反应符合二级动力学规律。该脱氮剂具有用量少,脱碱性氮率高,脱色好,易分离,可回收的优点。活性炭经改性后,对碱性氮化物的吸附脱除能力显著提高。室温下,当改性剂浓度为30%、200mLRFCC柴油中投加量为2g、吸附时间为45min时,RFCC柴油中的碱性氮化物脱除率为95.68%,油品透光率由4.2%增至36.2%。其吸附过程规律遵循Freundlich吸附等温式。该脱氮剂具有脱碱性氮率高,操作简单,易分离,对设备基本无腐蚀,可再生的优点。两种脱氮剂均显示出良好的性价比和广阔的应用前景。
This study developed two kinds of reagents which one kind was liquid state named WH-1 and the other was solid state for denitrogenation in RFCC diesel oil. The effect of concentration, ratio of reagent and oil and temperature et al to the process was researched deeply, the process for application also be established, and the mechanism and dynamics of denitrogenation was discussed at the same time when using the WH-1 reagent for denitrogenation. The result showed that in room temperature, using 70% acid as the main reagent, the ratio of BNC removed in RFCC oil by WH-1 reagent was 97.50% and the transmittance of the RFCC diesel oil was increased from 3.8% to 36.4% when the ratio of reagent and oil was 1:400, the reaction time was 10 minutes and the settlement time was 10 minutes. The kinetic order of the reaction between WH-1 reagent and BNC was 2. The reagent had the advantages of high ratio of BNC removing using little amount reagent, good effect of decoloration, easy separation and can be reclaimed. The adsorption ability for the activated carbon was greatly improved after being modified by WH-1 reagent. The optimal concentration of the acid used to modify the activated carbon was 30%. In room temperature, the optimal amount of solid sorbent delivered into 200mL RFCC diesel oil was 2.0 gram, the optimal adsorption time was 45 minutes, in this condition, the ratio of BNC removed in RFCC oil by the solid state reagent was 95.68% and the transmittance of the RFCC diesel oil was increased from 4.2% to 36.2%. The adsorption process accorded with the Freundlich’s Equation. The solid state reagent had a high ratio for BNC removing, operated easily, separated from the oil easily, had no corrosion to metal equipments and can be regenerated conveniently. The two reagents all have good capability for BNC removing and low price, will have a good future for application in different conditions.
This study developed two kinds of reagents which one kind was liquid state named WH-1 and the other was solid state for denitrogenation in RFCC diesel oil. The effect of concentration, ratio of reagent and oil and temperature et al to the process was researched deeply, the process for application also be established, and the mechanism and dynamics of denitrogenation was discussed at the same time when using the WH-1 reagent for denitrogenation. The result showed that in room temperature, using 70% acid as the main reagent, the ratio of BNC removed in RFCC oil by WH-1 reagent was 97.50% and the transmittance of the RFCC diesel oil was increased from 3.8% to 36.4% when the ratio of reagent and oil was 1:400, the reaction time was 10 minutes and the settlement time was 10 minutes. The kinetic order of the reaction between WH-1 reagent and BNC was 2. The reagent had the advantages of high ratio of BNC removing using little amount reagent, good effect of decoloration, easy separation and can be reclaimed. The adsorption ability for the activated carbon was greatly improved after being modified by WH-1 reagent. The optimal concentration of the acid used to modify the activated carbon was 30%. In room temperature, the optimal amount of solid sorbent delivered into 200mL RFCC diesel oil was 2.0 gram, the optimal adsorption time was 45 minutes, in this condition, the ratio of BNC removed in RFCC oil by the solid state reagent was 95.68% and the transmittance of the RFCC diesel oil was increased from 4.2% to 36.2%. The adsorption process accorded with the Freundlich’s Equation. The solid state reagent had a high ratio for BNC removing, operated easily, separated from the oil easily, had no corrosion to metal equipments and can be regenerated conveniently. The two reagents all have good capability for BNC removing and low price, will have a good future for application in different conditions.
引文
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[30] 丛野等. FS 法精制催化裂化柴油[J]. 炼油技术与工程, 2004, 34(1):55-56.
[31] 魏毅, 刘道胜等. 化学法脱除柴油中碱性氮化物[J]. 抚顺石油学院学报, 2002, 22(2):1-4.
[32] 乔爱新, 胡东妮等. 乙醇萃取法提高催化裂化柴油储存安定性的研究[J]. 2000, 12(3): 40-42.
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[34] John J.Eisch, Lawrence, et al. Desulphurization and denitrogenation of SRC Liquids by transition metals on solid supports[J]. Fuel, 1985, 64(4):440-442.
[35] 王学凯, 姜恒等. LCH-28 脱氮剂的性能评价及在润滑油基础油生产中的应用[J]. 化工科技, 2004, 12(1):36-39
[36] 闫锋, 任素华. 汽油中碱性氮的脱除[J]. 抚顺石油学院学报, 1999, 19(1):28-31.
[37] Atsushi Ishihara, Danhong Wang, et al. Oxidative desulfurization and denitrogenation of a light gas oil using an oxidation/adsorption continuous flow process[J]. Applied catalysis A: General, 279(1-2):279-287.
[38] 战风涛, 李林等. 吸附精制提高催化裂化柴油的安定性[J]. 炼油设计, 1998, 28(5):13-15.
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[41] John M.Charlesworth. Removal of nitrogen compounds from shale oil by adsorption on to acid-treated shale ash[J]. Fuel, 65(8):1159-1163.
[42] Jae Hyung Kim, Xiaoliang Ma, et al. Ultra-deep desulfurization and denitrogenation of diesel fuel by selective adsorption over three different adorbents: A study on adsorption selectivity and mechanism. Catalysis Today, 111(1-2):74-85.
[43] Yan T Y, Shu P. Ind Eng Chem Res, 1987, 26(4):753.
[44] 孙玉华,陈月珠等. TTS 脱除石蜡基润滑油中的氮化合物. 石油炼制与化工, 1997, 28(5):25-28.
[45] 陈月珠等. 络合-吸附法脱除催化裂化柴油中碱性氮的工艺研究. 石油炼制, 2003, 34(3):16-19.
[46] 朴香兰, 朱慎林. 润滑油基础油的溶剂脱氮技术. 炼油设计, 1999, 29(10):17-19.
[47] 齐江等. 催化裂化柴油氮化物的络合萃取. 石油化工, 1998, 27(2):106-108.
[48] 黄克明等. 络合反应法脱出润滑油中的碱性氮化物. 润滑油, 2002, 14(5):49-51
[49] 李 东 胜 . 润 滑 油 糠 醛 精 制 过 程 加 助 剂 研 究 . 抚 顺 石 油 学 院 学 报 , 1999, 19(4):13-17.
[50] J.J Kilbane. Coal bioprocessing research at the institute of gas technology. Fuel and Energy, 1996, 37(2):84
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[52] Michael J.Benedik, Philip P. Gibbs, et al. Microbial denitrogenation of fossil. Trends in Biotechnology, 1998,16(9):390-395.
[53]马骏, 隋新等. 微波处理吸附剂脱除碱性氮化物的研究[J]. 石油化工高等学校学报,2004, 17(2):9-12.
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[3] Dorbow M, Schmitter J M,Garrigues P,et al.Org Geochem, 1984, 7(2):110-120.
[4] Xingguo Cheng, Tao Zhao, et al. Identification of nitrogen compounds in RFCC disel oil by mass spectrometry[J]. Fuel Processing Technology, 2004, 85:1463-1472.
[5] 董 福 英 , 孙 传 经 等 . 催 化 柴 油 中 碱 性 氮 化 物 的 GC/MS 分 析 [J]. 山 东 科学,1992,5(1):24-28.
[6]史权,徐春明等. 催化裂化柴油中芳胺类化合物组成分析[J]. 分析测试学报,2004,23(5):100-102.
[7] 吕 志 风 , 战 风 涛 等 . 催 化 裂 化 柴 油 中 氮 化 物 的 分 析 [J]. 石 油 化工,2001,30(5):399-401.
[8] John Mao, Carlos R.Pacheco et al. Identification and characterization of nitrogen compounds in Brazilian diesel oil by particle beam IC-MS[J]. Fuel, 1995, 74(6):880-887.
[9] C.A.Nwadinigwe, M.C.Maduka. A quantitative assessment of the classes of nitrogenous compounds in light crudes[J]. Fuel, 1993, 72(8):1139-1143.
[10] Georgina C.Laredo, Sara Leyva, et al. Nitrogen compounds characterization in atmospheric gas oil and light cycle oil from a blend of Mexican crudes[J]. Fuel,2002,81:1341-1350.
[11] Yevgenia Briker, Zbigniew Ring, et al. Miniaturized method for separation and quantification of nitrogen species in petroleum distillates[J]. Fuel, 2003, 82:1621-1631.
[12] 张瑞驰, 施文元. 催化裂化转化加工焦化蜡油工艺的研究与开发[J]. 石油炼制与化工, 1998, 29(11):22-27.
[13] 贾鸣春,张文英等. 碱性氮化物对焦化蜡油裂化性能的影响[J]. 石油化工, 2002, 26(3):110-112.
[14] Mingyong Sun, Alan E.Nelson, John Adjaye. Correlating the electronic properties and HDN reactivities of organnitrogen compounds: an abinitio DFT study[J]. Journal of Molecular Catalysis A:Chemical, 2004, 222:243-251.
[15] Per Zeuthen, Kim G.Knudsen, D.D.Whitehurst. Organic nitrogen compounds in gas oil blends, their hydrogreated products and the importance to hydrotreatment[J]. Catalysis Today, 2001, 65:307-314.
[16] Francisco Assis Barbosa, Ana Carlota Belizario dos santos, et al. Resistance to poisoning by nitrogen compounds of NiMo/Al-MCM-41 hydrocracking catalysts[J].Catalysis Today, 2004, 98:109-113.
[17] Georgina Laredo, Efrain Altamirano, et al. Inhibition effects of nitrogen compounds on the hydrodesulfurization of dibenzothiophene:part 2[J]. Applied catalysis A: General 2003, 243:207-214.
[18] U day T.Turaga, Xiaoliang, Ma, et al. Influnence of nitrogen compounds on deep hydrodesulfurization of 4,6-dinethyldibenzothiophene over Al2O3-and MCM-41-supported Co-Mo sulfide catalysts[J]. Catalysis Today, 2003, 86:265-275.
[19] 齐江, 李林等. 催化裂化柴油不安定因素的考察[J]. 石油大学学报, 1997, 21(5):72-74.
[20] 翁振洲. 进一步提高基础油质量适应高档润滑油的需要[J]. 石油炼制, 1989, 6:1-7.
[21] 王艳花, 郭淑铃等. 大庆减压馏分油脱除碱性氮化物[J]. 大庆石油学院学报, 1998, 22(2):29-31.
[22] 张宏玉, 李陪陪. 润滑油基础油中的氮化物对油品使用性能的影响[J]. 石油炼制与化工, 1997, 28(12):21-24.
[23] 沈喜洲, 夏明贵. 石蜡基重质润滑油基础油脱氮与白土精制[J]. 石油炼制与化工. 1999, 30(9):20-22.
[24] 齐江等. 醋酸对催化裂化柴油的络合萃取精制[J]. 石油炼制与化工, 1997, 28(11):10-12.
[25] Yanzhen Wang, Ruili Li, et al. Removal of nitrogen compounds from lubricating base stocks with complexing of oxalic acid. Fuel Processing Technology, 2004, 5:9-18.
[26] 杨丽娜, 李剑等. 糠醛加助剂精制焦化柴油[J]. 石油炼制, 2004, 30(2):8-9.
[27] 马骏, 王海彦等. 萃取法脱除醚化原料中碱性氮化物[J]. 抚顺石油学院学报, 2001, 21(1):20-21.
[28] 王军民, 孙国庆等.焦化蜡油复合溶剂萃取脱氮的工艺研究[J]. 石油炼制与化工, 1997, 28(11):4-6.
[29] 张科良, 何力. 催化裂化柴油复合溶剂萃取精制工艺研究[J]. 西安石油学院学报, 2000, 15(1):30-33.
[30] 丛野等. FS 法精制催化裂化柴油[J]. 炼油技术与工程, 2004, 34(1):55-56.
[31] 魏毅, 刘道胜等. 化学法脱除柴油中碱性氮化物[J]. 抚顺石油学院学报, 2002, 22(2):1-4.
[32] 乔爱新, 胡东妮等. 乙醇萃取法提高催化裂化柴油储存安定性的研究[J]. 2000, 12(3): 40-42.
[33] Ralph Bernheimer, M.C.Maduka, et al. Denitrogenation of nitrogenous bases from petroleum products[J]. Fuel, 1993, 72(8):1147-1158.
[34] John J.Eisch, Lawrence, et al. Desulphurization and denitrogenation of SRC Liquids by transition metals on solid supports[J]. Fuel, 1985, 64(4):440-442.
[35] 王学凯, 姜恒等. LCH-28 脱氮剂的性能评价及在润滑油基础油生产中的应用[J]. 化工科技, 2004, 12(1):36-39
[36] 闫锋, 任素华. 汽油中碱性氮的脱除[J]. 抚顺石油学院学报, 1999, 19(1):28-31.
[37] Atsushi Ishihara, Danhong Wang, et al. Oxidative desulfurization and denitrogenation of a light gas oil using an oxidation/adsorption continuous flow process[J]. Applied catalysis A: General, 279(1-2):279-287.
[38] 战风涛, 李林等. 吸附精制提高催化裂化柴油的安定性[J]. 炼油设计, 1998, 28(5):13-15.
[39] 栾锡林, 李诚勇等. 焦化蜡油吸附脱碱性氮研究[J]. 石油化工高等学校学报, 1996, 12(2):15-18.
[40] 陈文艺, 王海彦等. 脱除催化裂化柴油中碱性氮化合物的研究[J]. 炼油设计, 2001, 31(1):52-54.
[41] John M.Charlesworth. Removal of nitrogen compounds from shale oil by adsorption on to acid-treated shale ash[J]. Fuel, 65(8):1159-1163.
[42] Jae Hyung Kim, Xiaoliang Ma, et al. Ultra-deep desulfurization and denitrogenation of diesel fuel by selective adsorption over three different adorbents: A study on adsorption selectivity and mechanism. Catalysis Today, 111(1-2):74-85.
[43] Yan T Y, Shu P. Ind Eng Chem Res, 1987, 26(4):753.
[44] 孙玉华,陈月珠等. TTS 脱除石蜡基润滑油中的氮化合物. 石油炼制与化工, 1997, 28(5):25-28.
[45] 陈月珠等. 络合-吸附法脱除催化裂化柴油中碱性氮的工艺研究. 石油炼制, 2003, 34(3):16-19.
[46] 朴香兰, 朱慎林. 润滑油基础油的溶剂脱氮技术. 炼油设计, 1999, 29(10):17-19.
[47] 齐江等. 催化裂化柴油氮化物的络合萃取. 石油化工, 1998, 27(2):106-108.
[48] 黄克明等. 络合反应法脱出润滑油中的碱性氮化物. 润滑油, 2002, 14(5):49-51
[49] 李 东 胜 . 润 滑 油 糠 醛 精 制 过 程 加 助 剂 研 究 . 抚 顺 石 油 学 院 学 报 , 1999, 19(4):13-17.
[50] J.J Kilbane. Coal bioprocessing research at the institute of gas technology. Fuel and Energy, 1996, 37(2):84
[51] Gibbs P R, et al. Prepr Am Chem Soc, Div Fuel Chem, 1999, 44(1):1-4
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