FCC油浆溶剂精制及利用的研究
|
摘要
为了综合利用催化裂化油浆,提高其综合利用的高附加值,可以将油浆进行精制并对其进一步进行深加工利用。实验考察了轻质烷烃溶剂对FCC油浆的溶剂精制工艺的影响,并对抽出油进行了组成结构分析,结果表明,溶剂精制工艺可以有效的脱除油浆中灰分的含量,减少沥青质与重金属含量,合适的溶剂精制条件为剂油比为2：1,温度在溶剂的沸点附近。采用减压蒸馏-溶剂精制组合工艺和溶剂精制-减压蒸馏组合工艺分别对FCC油浆进行了预处理,对两种工艺所得到的油浆PFCC-EO和EO-PFCC分析其组成和结构,芳香组分以及芳碳率大小,表明采用减压蒸馏-溶剂精制组合工艺对油浆性质的改善效果更好。探讨了油浆各组分的用途,主要研究了减压拔出物的性质,其适合作为加氢裂化的原料；以及用脱油沥青调和老化沥青,可以使其性质得到改善,符合一定沥青标准；还对预处理的PFCC-EO油浆进行了制备中间相沥青的考察,从而为国内生产具有高附加值的针状焦进行一些探索研究试验。
For utilization of FCC slurry oil and enhancing its value-added, the oil can be further refined and deep processing of its use. In this experiment, we firstly make a study of using low molecular weight n-alkanes as solvents for refining and separating the slurry. Adopt elements analysis,he IR spectrum, SARA analysis, and other means of analysis to the extract oil,it can be effective in removing ash content and reducing the asphaltene content and heavy metal content of the slurry. We determine solvent-slurry ratios of 2:1 and the temperature near the boiling point solvents as the optimum conditions for solvent extraction. Then we compare two pretreatment of FCC slurry oil,we also adopt elements analysis, the IR spectrum, SARA analysis,1H-NMR to the oils and carry out that the vacuum distillation-solvent refining pretreatment is better for the improvement of slurry properties,it named PFCC-EO which is a good raw material for producing needle coke. At the end of the experiment, we discusse the nature of vacuum distillation oil, to determine it as the raw material for hydro-cracking. Also, the DOA can be used for blending the old asphalt, and its properties can be improved.At last, used PFCC-EO as mesophase pitch, then has a high value-added research in production of needle coke and do some exploring test.
For utilization of FCC slurry oil and enhancing its value-added, the oil can be further refined and deep processing of its use. In this experiment, we firstly make a study of using low molecular weight n-alkanes as solvents for refining and separating the slurry. Adopt elements analysis,he IR spectrum, SARA analysis, and other means of analysis to the extract oil,it can be effective in removing ash content and reducing the asphaltene content and heavy metal content of the slurry. We determine solvent-slurry ratios of 2:1 and the temperature near the boiling point solvents as the optimum conditions for solvent extraction. Then we compare two pretreatment of FCC slurry oil,we also adopt elements analysis, the IR spectrum, SARA analysis,1H-NMR to the oils and carry out that the vacuum distillation-solvent refining pretreatment is better for the improvement of slurry properties,it named PFCC-EO which is a good raw material for producing needle coke. At the end of the experiment, we discusse the nature of vacuum distillation oil, to determine it as the raw material for hydro-cracking. Also, the DOA can be used for blending the old asphalt, and its properties can be improved.At last, used PFCC-EO as mesophase pitch, then has a high value-added research in production of needle coke and do some exploring test.
引文
[1]庞智勇.油浆糠醛抽提与产品应用[J].辽宁化工.1999,28(3)：238-240
[2]张永新.FCC油浆的分离与综合利用[J].石化技术与应用.2003,21(2)：92-95
[3]郑艳华,车长佰.催化裂化油浆深加工产品及应用[J].化工科技市场.2001,8
[4]王曼霞.FCC油浆芳烃的分离和利用[D].青岛化工学院,2000
[5]魏淑珍.澄清油综合利用[J].催化裂化,1993,2(2)：8-13.
[6]郑伟.渣油加氢处理技术前景展望[J].中国石油和化工.2001, (1)：49-50
[7]中国石油化工集团公司.CN 1262301,19990128
[8]牛传峰,张瑞弛,戴立顺等.渣油加氢-催化裂化双向组合技术[J].石油炼制与化工.2002,33(1)：27-29
[9]王晓红,李海涛.丁烷脱沥青-重油催化裂化组合工艺的工业应用[J].石化技术与应用.2006,24(2)：124-126
[10]范雨润,孙鉴.丙烷脱沥青装置掺炼催化裂化油[J].石油炼制与化工.1998,29(8)：6-9
[11]彭显峰,候特超,罗勇宝.掺催化裂化油浆的减压渣油溶剂脱沥青工业实验及其在我厂组合工艺上的应用[J].广州石化科技信息.1995, (1)：38-45
[12]CHEN Sh L, JIA Sh Sh, etal. Mild cracking solvent deasphalting:a new method for upgradeing petroleum residue[J]. Fuel.1994,73 (3):439-442
[13]赵渊杰等.减压渣油掺炼催化裂化油浆丁烷脱沥青-糠醛精制组合工艺研究[J].石油炼制与化工.2007,38(8)：23-27
[14]黄克明,熊丽艳,等.用表面活性剂提高糠醛精制润滑油收率的研究[J].润滑油.1999,14(4)：18
[15]王懿父.催化裂化-芳烃抽提联合工艺的研究和工业实验[J].石油炼制与化工.1995,26(6)：1-8
[16]崔龙,经小平.减压渣油掺合油浆生产优质焦的工业实验[J].炼油设计.1993,23(5)：19-25
[17]刘晓欣.催化裂化—延迟焦化组合工艺[J].石油炼制与化工.1998,29(11)：31-32
[18]World Refining Capacity Creeps Ahead in 2004[J]. Oil&Gas Journal.2004, 12-20
[19]丁洛,杨煜远.催化裂化油浆催化剂粉末的脱除技术[J].石油炼制与化工.2001,32(5) ：60-61
[20]Kevin J Smith. Upgrading Heavy Oil by Ultra filtration Using Ceramic Membrane. US 5785860,1998
[21]Lauer Robert S. Method for separating Solids from Hydrocarbon Slurries. US 6316685,2001
[22]张洪林,杨磊.重油催化裂化外甩油浆离心沉降净化研究[J].石油炼制与化工.1999,1(4)：5-8
[23]卢捍卫.国外催化裂化技术发展跟踪调查研究.催化裂化协作组第五届年会报告论文集,中国石油化工总公司催化裂化协作组.1995,27
[24]World Refining.1999,9 (7):35-38
[25]杨基和.FCC油浆下游产品开发研究[J].炼油技术与工程.2005,35(11)：21-24
[26]龙军.FCC油浆脱沥青的研究[J].石油炼制与化工.1997,28(3)：6-9
[27]张庆宇.催化裂化油浆双溶剂芳烃抽提工艺[J].河南石油.2002,16(1)：64-69
[28]范雨润,孙鉴.丙烷脱沥青装置掺炼催化裂化油[J].石油炼制与化工.1998,29(8)：6-9
[29]郭燕生.催化裂化油浆合成沥青树脂的反应性能[J].石油炼制与化工.2000,1(1)：128-132
[30]许志明,张立,赵锁奇,王仁安.催化裂化油浆的分离与化工利用[J].石油炼制与化工.2001,32(9)：17-21
[31]李京宾,华炜,许志明.大庆减压渣油／催化裂化油浆混合原料脱沥青油的催化裂化[J].炼油设计.2001,31(3)：6-9
[32]高凤萍,齐仲辉等.国外针状焦的质量现状分析[J].炭素技术.2003,124(1)：27-31
[33]Robinson K E, Edie D D. Microstructure and texture of pitch—ased ribbon fibers for thermal management[J]. Carbon.1996,34 (1):13-36
[34]李玉财等.针状焦的工业化生产[J].精细与专用化学品.2002,(13)：6-8
[35]Semih Eser, Guohua Wang. A Laboratory Study of a Pretreatment Approach to Accommodate High-Sulfur FCC Decant Oils as Feedstocks for Commercial Needle Coke[J].Energy & Fuels.2007,21:3573-3582
[36]Estopinal Jr, Earl J.Reduction of the degradation of refractories in a carbon black reactor[P].USP4342736,1982
[37]杨玉庆,王玉萍,李俊明.催化裂化油浆开发橡胶软化剂实验性研究[J].山东化工.2003,32：22-23
[38]Arpad, Krisztina T,Miklos J.Detailed analysis of sulfur compounds in gasoline range petroleum productswith high-resolution gas chromatography-atomic emission detection using group-selectivechemical treatment.Journal of chromatography A.1998,819 (1):67-74
[39]陈继军,王翠红,郭燕生.一种改善沥青质量的新途径[J].石油沥青,1995,9(2)：7-10
[40]冯敏哿.新疆混合原油重交通沥青的研制和应用[J].石油炼制与化工.1996,27(10)：18
[41]孙大权.我国改性道路沥青发展状况[J].抚顺石油学院学报.1999,19(4)：26-27
[42]康伟青.催化油浆利用及其工艺[J].江西石油化工.1999, (2)：31-36
[43]闰瑞萍,朱继升,杨建晴.催化裂化油浆与兖州煤加氢共处理的研究Ⅱ重质产物的组成及利用[J].石油学报(石油加工).2001,17(5)：7-12
[44]Li R, Wang ZJ, Long J. Combined process of low degree solvent deasphalting and delayed coking. US Patent66673234.2004-04-26
[45]王玉章,陈清怡,李锐等.催化裂化澄清油生产针状焦的方法[P].中国专利：01115494.2004-12-24
[46]李锐,丁宗禹,祖德光.蒸汽裂解渣油生产针状焦的可行性研究[J].石油炼制与化工.1998,29(8)：50-53
[47]Sprague S B. How solvent selection affects extraction efficiency. NPRA Annual Meeting.1986, AM86-36.
[48]李学军,FCC油浆溶剂萃取研制针状焦[D].中国石油大学(华东).2007
[49]王国华,李文典,聂朋果.丙烷脱沥青装置的整改及应用[J].石油与天然气.2004,33(3)：168-171
[50]水天德.现代润滑油生产工艺[M].中国石化出版社.1997,117-130
[51]童仲轩.减压渣油溶剂脱沥青抽提深度研究[J].石油炼制与化工.2004,35(5) ：20-24
[52]Ditman J G. Solvent deasphaliting a versatile tool for the preparation of lube hytroitreating feeding stocks.API37thMidyearMeeting,New York. May 1982.713-723.
[53]王延飞,程健.采用丙烷脱沥青工艺探讨催化裂化油浆的合理利用[J].石油炼制与化工.2002,33(1)：559-562
[54]杨书显等,溶剂脱沥青-催化裂化组合工艺[J].炼油技术与工程.2005,35(3)：37-40
[55]李晓文,溶剂脱沥青的技术进展与工艺优化[J].中文能源.2007,12：68-77
[56]翟志清,“溶剂脱沥青-油浆拔头”组合工艺生产重交道路沥青质量控制探讨[J].中外能源.2006,11
[57]刘永红等,催化裂化-溶剂脱沥青组合工艺的应用.石油炼制与化工.2003,34(11)
[58]Fisher L P. Residuum catalytic cracking influence of diluentson the yield of coke. Fuel,1986, (4):473
[59]查庆芳,张玉贞,巩春伟等.催化裂化油浆溶剂抽提及其中间相沥青[J].炭素技术.2001,13(2)：1-5
[60]ISAO MOCHIDA, TAKASHI OYAMA, YOZO KORAI. Formation scheme of needle coke from FCC-decont oil [J]. Carbon.1988,26 (1) : 49-55
[61]李志峰,李艳青,孙业新.国内外沥青针状焦生产现状分析.莱钢科技.2007,127(1)：48-50
[62]查庆芳,张玉贞,巩春伟等.催化裂化油浆溶剂抽提及其中间相沥青[J].炭素技术.2001,13(2)：1-5
[63]Robinson K E, Edie D D. Microstructure and texture of pitch—ased ribbon fibers for thermal management[J]. Carbon.1996,34 (1):13-36
[64]高凤萍,齐仲辉等.国外针状焦的质量现状分析[J].炭素技术.2003,124(1)：27-31
[65]水恒福,冯映桐,沈本贤等.煤沥青程序升温中间相转化动力学研究[J].燃料化学学报.1999,27(6)：541
[66]金鸣林,胡静霞等.中间相有序生长机理研究[J].科技导报(北京).2007,25(13)：49-53
[67]大谷杉郎,真田雄三编.炭化工学基础[M].中科院沈阳金属研究所.1985
[2]张永新.FCC油浆的分离与综合利用[J].石化技术与应用.2003,21(2)：92-95
[3]郑艳华,车长佰.催化裂化油浆深加工产品及应用[J].化工科技市场.2001,8
[4]王曼霞.FCC油浆芳烃的分离和利用[D].青岛化工学院,2000
[5]魏淑珍.澄清油综合利用[J].催化裂化,1993,2(2)：8-13.
[6]郑伟.渣油加氢处理技术前景展望[J].中国石油和化工.2001, (1)：49-50
[7]中国石油化工集团公司.CN 1262301,19990128
[8]牛传峰,张瑞弛,戴立顺等.渣油加氢-催化裂化双向组合技术[J].石油炼制与化工.2002,33(1)：27-29
[9]王晓红,李海涛.丁烷脱沥青-重油催化裂化组合工艺的工业应用[J].石化技术与应用.2006,24(2)：124-126
[10]范雨润,孙鉴.丙烷脱沥青装置掺炼催化裂化油[J].石油炼制与化工.1998,29(8)：6-9
[11]彭显峰,候特超,罗勇宝.掺催化裂化油浆的减压渣油溶剂脱沥青工业实验及其在我厂组合工艺上的应用[J].广州石化科技信息.1995, (1)：38-45
[12]CHEN Sh L, JIA Sh Sh, etal. Mild cracking solvent deasphalting:a new method for upgradeing petroleum residue[J]. Fuel.1994,73 (3):439-442
[13]赵渊杰等.减压渣油掺炼催化裂化油浆丁烷脱沥青-糠醛精制组合工艺研究[J].石油炼制与化工.2007,38(8)：23-27
[14]黄克明,熊丽艳,等.用表面活性剂提高糠醛精制润滑油收率的研究[J].润滑油.1999,14(4)：18
[15]王懿父.催化裂化-芳烃抽提联合工艺的研究和工业实验[J].石油炼制与化工.1995,26(6)：1-8
[16]崔龙,经小平.减压渣油掺合油浆生产优质焦的工业实验[J].炼油设计.1993,23(5)：19-25
[17]刘晓欣.催化裂化—延迟焦化组合工艺[J].石油炼制与化工.1998,29(11)：31-32
[18]World Refining Capacity Creeps Ahead in 2004[J]. Oil&Gas Journal.2004, 12-20
[19]丁洛,杨煜远.催化裂化油浆催化剂粉末的脱除技术[J].石油炼制与化工.2001,32(5) ：60-61
[20]Kevin J Smith. Upgrading Heavy Oil by Ultra filtration Using Ceramic Membrane. US 5785860,1998
[21]Lauer Robert S. Method for separating Solids from Hydrocarbon Slurries. US 6316685,2001
[22]张洪林,杨磊.重油催化裂化外甩油浆离心沉降净化研究[J].石油炼制与化工.1999,1(4)：5-8
[23]卢捍卫.国外催化裂化技术发展跟踪调查研究.催化裂化协作组第五届年会报告论文集,中国石油化工总公司催化裂化协作组.1995,27
[24]World Refining.1999,9 (7):35-38
[25]杨基和.FCC油浆下游产品开发研究[J].炼油技术与工程.2005,35(11)：21-24
[26]龙军.FCC油浆脱沥青的研究[J].石油炼制与化工.1997,28(3)：6-9
[27]张庆宇.催化裂化油浆双溶剂芳烃抽提工艺[J].河南石油.2002,16(1)：64-69
[28]范雨润,孙鉴.丙烷脱沥青装置掺炼催化裂化油[J].石油炼制与化工.1998,29(8)：6-9
[29]郭燕生.催化裂化油浆合成沥青树脂的反应性能[J].石油炼制与化工.2000,1(1)：128-132
[30]许志明,张立,赵锁奇,王仁安.催化裂化油浆的分离与化工利用[J].石油炼制与化工.2001,32(9)：17-21
[31]李京宾,华炜,许志明.大庆减压渣油／催化裂化油浆混合原料脱沥青油的催化裂化[J].炼油设计.2001,31(3)：6-9
[32]高凤萍,齐仲辉等.国外针状焦的质量现状分析[J].炭素技术.2003,124(1)：27-31
[33]Robinson K E, Edie D D. Microstructure and texture of pitch—ased ribbon fibers for thermal management[J]. Carbon.1996,34 (1):13-36
[34]李玉财等.针状焦的工业化生产[J].精细与专用化学品.2002,(13)：6-8
[35]Semih Eser, Guohua Wang. A Laboratory Study of a Pretreatment Approach to Accommodate High-Sulfur FCC Decant Oils as Feedstocks for Commercial Needle Coke[J].Energy & Fuels.2007,21:3573-3582
[36]Estopinal Jr, Earl J.Reduction of the degradation of refractories in a carbon black reactor[P].USP4342736,1982
[37]杨玉庆,王玉萍,李俊明.催化裂化油浆开发橡胶软化剂实验性研究[J].山东化工.2003,32：22-23
[38]Arpad, Krisztina T,Miklos J.Detailed analysis of sulfur compounds in gasoline range petroleum productswith high-resolution gas chromatography-atomic emission detection using group-selectivechemical treatment.Journal of chromatography A.1998,819 (1):67-74
[39]陈继军,王翠红,郭燕生.一种改善沥青质量的新途径[J].石油沥青,1995,9(2)：7-10
[40]冯敏哿.新疆混合原油重交通沥青的研制和应用[J].石油炼制与化工.1996,27(10)：18
[41]孙大权.我国改性道路沥青发展状况[J].抚顺石油学院学报.1999,19(4)：26-27
[42]康伟青.催化油浆利用及其工艺[J].江西石油化工.1999, (2)：31-36
[43]闰瑞萍,朱继升,杨建晴.催化裂化油浆与兖州煤加氢共处理的研究Ⅱ重质产物的组成及利用[J].石油学报(石油加工).2001,17(5)：7-12
[44]Li R, Wang ZJ, Long J. Combined process of low degree solvent deasphalting and delayed coking. US Patent66673234.2004-04-26
[45]王玉章,陈清怡,李锐等.催化裂化澄清油生产针状焦的方法[P].中国专利：01115494.2004-12-24
[46]李锐,丁宗禹,祖德光.蒸汽裂解渣油生产针状焦的可行性研究[J].石油炼制与化工.1998,29(8)：50-53
[47]Sprague S B. How solvent selection affects extraction efficiency. NPRA Annual Meeting.1986, AM86-36.
[48]李学军,FCC油浆溶剂萃取研制针状焦[D].中国石油大学(华东).2007
[49]王国华,李文典,聂朋果.丙烷脱沥青装置的整改及应用[J].石油与天然气.2004,33(3)：168-171
[50]水天德.现代润滑油生产工艺[M].中国石化出版社.1997,117-130
[51]童仲轩.减压渣油溶剂脱沥青抽提深度研究[J].石油炼制与化工.2004,35(5) ：20-24
[52]Ditman J G. Solvent deasphaliting a versatile tool for the preparation of lube hytroitreating feeding stocks.API37thMidyearMeeting,New York. May 1982.713-723.
[53]王延飞,程健.采用丙烷脱沥青工艺探讨催化裂化油浆的合理利用[J].石油炼制与化工.2002,33(1)：559-562
[54]杨书显等,溶剂脱沥青-催化裂化组合工艺[J].炼油技术与工程.2005,35(3)：37-40
[55]李晓文,溶剂脱沥青的技术进展与工艺优化[J].中文能源.2007,12：68-77
[56]翟志清,“溶剂脱沥青-油浆拔头”组合工艺生产重交道路沥青质量控制探讨[J].中外能源.2006,11
[57]刘永红等,催化裂化-溶剂脱沥青组合工艺的应用.石油炼制与化工.2003,34(11)
[58]Fisher L P. Residuum catalytic cracking influence of diluentson the yield of coke. Fuel,1986, (4):473
[59]查庆芳,张玉贞,巩春伟等.催化裂化油浆溶剂抽提及其中间相沥青[J].炭素技术.2001,13(2)：1-5
[60]ISAO MOCHIDA, TAKASHI OYAMA, YOZO KORAI. Formation scheme of needle coke from FCC-decont oil [J]. Carbon.1988,26 (1) : 49-55
[61]李志峰,李艳青,孙业新.国内外沥青针状焦生产现状分析.莱钢科技.2007,127(1)：48-50
[62]查庆芳,张玉贞,巩春伟等.催化裂化油浆溶剂抽提及其中间相沥青[J].炭素技术.2001,13(2)：1-5
[63]Robinson K E, Edie D D. Microstructure and texture of pitch—ased ribbon fibers for thermal management[J]. Carbon.1996,34 (1):13-36
[64]高凤萍,齐仲辉等.国外针状焦的质量现状分析[J].炭素技术.2003,124(1)：27-31
[65]水恒福,冯映桐,沈本贤等.煤沥青程序升温中间相转化动力学研究[J].燃料化学学报.1999,27(6)：541
[66]金鸣林,胡静霞等.中间相有序生长机理研究[J].科技导报(北京).2007,25(13)：49-53
[67]大谷杉郎,真田雄三编.炭化工学基础[M].中科院沈阳金属研究所.1985