白石湖煤液化粗油加氢精制过程硫、氮化合物转化规律

刘敏; 陈贵锋; 王永刚; 赵鹏; 曲思建

白石湖煤液化粗油加氢精制过程硫、氮化合物转化规律

刘敏^{1, 2, 3, ,},
陈贵锋^{2, 3},
王永刚¹,
赵鹏^{2, 3},
曲思建^{2, 3}

1.
中国矿业大学(北京), 北京 100083
2.
煤炭科学技术研究院有限公司, 北京 100013
3.
煤炭资源高效开采与洁净利用国家重点实验室, 北京 100013

基金项目:

北京市自然科学基金 2182090

煤科院科技创新基金 2017JC01

详细信息

中图分类号: TQ536;O656.4
计量
- 文章访问数: 141
- HTML全文浏览量: 56
- PDF下载量: 12
- 被引次数: 0
出版历程
- 收稿日期: 2019-03-04
- 修回日期: 2019-04-09
- 网络出版日期: 2021-01-23
- 刊出日期: 2019-07-10

Conversion of sulphur and nitrogen compounds in hydrofining process of Baishihu coal liquefaction oil

LIU Min^{1, 2, 3
, ,},
CHEN Gui-feng^{2, 3},
WANG Yong-gang¹,
ZHAO Peng^{2, 3},
QU Si-jian^{2, 3}

1.
China University of Mining and Technology, Beijing 100083, China
2.
China Coal Research Institute, Beijing 100013, China
3.
State Key Laboratory of Coal Mining and Clean Utilization, Beijing 100013, China

Funds:

the Beijing Natural Science Foundation 2182090

Science and Technology Innovation Fund of China Coal Research Institute 2017JC01

More Information

Corresponding author: LIU Min, E-mail: 78562115@qq.com

摘要

摘要: 采用实沸点蒸馏仪对白石湖煤液化油进行馏分切割，切取 < 170℃液化粗油进行加氢精制脱除其中硫、氮化合物，采用硫化学发光气相色谱仪（GC-SCD）、氮化学发光气相色谱仪（GC-NCD）对液化粗油和精制油中硫、氮化合物进行分析表征，研究加氢精制过程硫、氮化合物的转化规律。结果表明，液化粗油中含硫化合物主要是噻吩类化合物和硫醇，经过加氢精制后基本消失，苯并噻酚类化合物脱除比例要低于噻吩类化合物，属于较难脱除含硫化合物。液化粗油中含氮化合物主要是苯胺类化合物，其次是吲哚类化合物，经过加氢精制吲哚类化合物全被脱除，苯胺和喹啉类化合物属于碱性含氮化合物，是精制油中残留的主要含氮化合物，含量达1.61 mg/kg。
- 液化粗油 /
- 芳烃 /
- 硫化物 /
- 氮化物 /
- 加氢精制
Abstract: A real boiling point distillation apparatus was used to cut the fractions of Baishihu coal liquefied oil. The fraction below 170 ℃ was taken as the catalytic reforming feedstocks of hydrorefining. Meanwhile, the sulfur and nitrogen compounds in liquefied crude oil and refined oil were analyzed and characterized by GC-SCD and GC-NCD to study the transformation rule of sulfur and nitrogen compounds in hydrofining process. The results show that the sulfur compounds in liquefied crude oil are mainly thiophene compounds and mercaptan, which disappear after hydrorefining, and the removal rate of benzothiophenols is lower than that of thiophene compounds. Nitrogen-containing compounds in liquefied crude oil are mainly aniline compounds and indole compounds. After hydrorefining, all indole compounds are basically removed. Aniline and quinoline compounds belong to basic nitrogen-containing compounds, and are the main nitrogen-containing compounds remained in refined oil with a content of 1.61 mg/kg.
- liquefaction oil /
- aromatic hydrocarbon /
- sulfide /
- nitrides /
- hydrorefining

HTML全文

下载: 全尺寸图片幻灯片

图 1 加氢预精制流程示意图

1: raw material tank; 2: metering tank; 3: hydrogen preheater; 4: oil preheater; 5: fixed bed reactor; 6: separator; 7: product tank; 8: buffer tank; 9: flowmeter

Figure 1 Flow chart of hydrofining

下载: 全尺寸图片幻灯片

图 2 100 mL/h固定床加氢流程示意图

1: raw material tank; 2: soft water tank; 3: fixed bed reactor Ⅰ; 4: fixed bed reactor Ⅱ; 5: separatorⅠ; 6: product tank; 7: separator Ⅱ; 8: flowmeter

Figure 2 Flow chart of 100 mL/h fixed bed hydrogenation

下载: 全尺寸图片幻灯片

图 3 液化粗油的GC-SCD谱图

Figure 3 GC-SCD characterization of liquefied oil

下载: 全尺寸图片幻灯片

图 4 精制油的GC-SCD谱图

Figure 4 GC-SCD characterization of refined oil

下载: 全尺寸图片幻灯片

图 5 液化粗油的GC-NCD谱图

Figure 5 GC-NCD characterization of liquefied oil

下载: 全尺寸图片幻灯片

图 6 精制油的GC-NCD谱图

Figure 6 GC-NCD characterization of refined oil

下载: 全尺寸图片幻灯片

表 1 加氢预精制催化剂性质

Table 1 Properties of prehydrofining catalyst

Content w/%				Specific surface area A/(m²·g^-1)	Specific volume v/(cm³·g^-1)
MoO₃	NiO	Na₂O	SO₄	Specific surface area A/(m²·g^-1)	Specific volume v/(cm³·g^-1)
15.4	3.0	0.07	1.1	180	0.643

下载: 导出CSV

表 2 加氢精制催化剂性质

Table 2 Properties of hydrofining catalyst

Content w/%			Specific surface area A/(m²·g^-1)	Pore volume v/(cm³·g^-1)	Crushing strength/(N·mm^-1)
MoO₃	WO₃	NiO	Specific surface area A/(m²·g^-1)	Pore volume v/(cm³·g^-1)	Crushing strength/(N·mm^-1)
2.3	25	2.6	140	0.24	18

下载: 导出CSV

表 3 液化粗油和精制油性质

Table 3 Properties of liquefied oil and refined oil

Property	Liquefied oil	Refined oil
Density(20 ℃)ρ/(g·cm^-3)	0.772	0.761
Viscosity(20 ℃)μ/(mm²·s^-1)	0.916	0.774
C w/%	87.58	86.83
H w/%	10.07	12.11
O w/%	2.17	0.98
S/(mg·kg^-1)	512	1.9
N/(mg·kg^-1)	1370	2.8

下载: 导出CSV

参考文献(25)

[1]	门秀杰, 孙海萍, 雷强.我国芳烃行业前景展望及发展建议[J].现代化工, 2019, 39(3):1-6. http://d.old.wanfangdata.com.cn/Periodical/xdhg201903001 MEN Xiu-jie, SUN Hai-ping, LEI Qiang. Review, outlook and suggestions on China's aromatic hydrocarbon industry[J]. Mod Chem Ind, 2019, 39(3):1-6. http://d.old.wanfangdata.com.cn/Periodical/xdhg201903001
[2]	林世雄.石油炼制工程[M].北京:石油工业出版社, 2000. LIN Shi-xiong. Petroleum Refining Engineering[M]. Beijing:Petroleum Industry Press, 2000.
[3]	王力波, 蒋世滨.环烷基基础油市场供需分析及其应用发展[J].石油商技, 2017, 35(2):4-9. doi: 10.3969/j.issn.1006-1479.2017.02.001 WANG Li-bo, JIANG Shi-bin. Market supply and demand analysis of naphthenic base oil and Its application development[J]. Pet Prod Appl Res, 2017, 35(2):4-9. doi: 10.3969/j.issn.1006-1479.2017.02.001
[4]	舒歌平, 史士东, 李克健.煤炭液化技术[M].北京:煤炭工业出版社, 2003. SHU Ge-ping, SHI Shi-dong, LI Ke-jian. Direct Coal Liquefaction[M]. Beijing:Coal Industry Press, 2003.
[5]	史士东.煤加氢液化工程学基础[M].北京:化学工业出版社, 2012. SHI Shi-dong. Engineering Basis of Coal Hydro-Liquefaction[M]. Beijing:Chemical Industry Press, 2003.
[6]	刘敏, 史士东, 曲思建, 刘立麟, 盛明, 毛学锋.煤炭直接液化反应机理理论研究进展[J].洁净煤技术, 2015, 21(4):49-54. https://wenku.baidu.com/view/ee83139288eb172ded630b1c59eef8c75fbf95ae.html LIU Min, SHI Shi-dong, QU Si-Jian, LIU Li-lin, SHENG Min, MAO Xue-feng. Progress in theoretical research on reaction mechanism of coal direct liquefaction[J]. Clean Coal Technol, 2015, 21(4):49-54. https://wenku.baidu.com/view/ee83139288eb172ded630b1c59eef8c75fbf95ae.html
[7]	GU X H, MAO X F, ZHAO Y, LI W B, ZHANG X J. Study on the basic nitrogen compounds fromc oal-derived oil[J]. J Coal Sci Eng(China), 2013, 19(1):83-89. doi: 10.1007/s12404-013-0114-7
[8]	谷小会, 黄澎, 李文博, 艾军.液化油中含氮化合物的研究进展[J].洁净煤技术, 2011, 17(4):38-40. doi: 10.3969/j.issn.1006-6772.2011.04.013 GU Xiao-hui, HUANG Peng, LI Wen-bo, AI Jun. Research progress of nitrogen-containing compounds in liquefied oil[J]. Clean Coal Technol, 2011, 17(4):38-40. doi: 10.3969/j.issn.1006-6772.2011.04.013
[9]	MURTI S D S, SAKANISHI K, OKUMA O, KORAI Y, MOCHIDA I. Detailed characterization of heteroatom-containing molecules in light distillates derived from tanito harum coal and its hydrotreated oil[J]. Fuel, 2002, 81(17):2241-2248. doi: 10.1016/S0016-2361(02)00159-X
[10]	OA M A, FLORESB M, PARRAA S, QUIROZA W, MAXWELLC P, MESTERC Z. Chemometric optimization of an extraction procedure using tartaric acid for butyltin compounds from sediment samples by GC-PFPD[J]. J Chil Chem Soc, 2015, 60:2803-2806. doi: 10.4067/S0717-97072015000100006
[11]	MURTI S D S, CHOI K H, SAKANISHI K, OKUMA O, KORAI Y, MOCHIDA I. Analysis and removal of heteroatom containing species in coal liquid distillate over Ni/Mo catalysts[J]. Fuel, 2005, 84(2):135-142.
[12]	黄澎, 张晓静, 毛学锋, 李伟林.神府煤液化油加氢精制过程硫氮化合物分布变化[J].燃料化学学报, 2016, 44(1):37-43. doi: 10.3969/j.issn.0253-2409.2016.01.006 HUANG Peng, ZHANG Xiao-jing, MAO Xue-feng, LI Wei-lin. Change of sulfurand nitrogen compounds in the direct liquefaction oil from Shenfu coal upom the hydrofining process[J]. J Fuel Chem Technol, 2016, 44(1):37-43. doi: 10.3969/j.issn.0253-2409.2016.01.006
[13]	HUANG P, ZHANG X J, MAO X F. Research on the production of aromatic hydrocarbon via hydroreforming a light fraction in direct coal liquefaction oil[J]. Energy Fuels, 2015, 29:86-90. doi: 10.1021/ef502146a
[14]	李伟林, 石智杰, 张晓静, 李军芳, 胡发亭.煤直接液化油中硫氮化合物的类型分布[J].洁净煤技术, 2015, 21(4):55-57. http://d.old.wanfangdata.com.cn/Periodical/jjmjs201504016 LI Wei-lin, SHI Zhi-jie, ZHANG Xiao-jing, LI Jun-fang, HU Fa-ting. Type distribution of sulfer and nitrogen compounds in coal direct liquefaction oil[J]. Clean Coal Technol, 2015, 21(4):55-57. http://d.old.wanfangdata.com.cn/Periodical/jjmjs201504016
[15]	PAN N, CUI D, LI R, SHI Q, CHUNG K H, LONG H, LI Y, ZHANG Y, ZHAO S, XU C. Characterization of middle-temperature gasification coal tar. part 1:Bulk properties and molecular compositions of distillates and basic fractions[J]. Energy Fuels, 2012, 26(9):5719-5728. doi: 10.1021/ef3007323
[16]	LONG H, SHI Q, PAN, N, ZHANG Y, CUI D, CHUNG K H, ZHAO S, XU C. Characterization of middle-temperature gasification coal tar. part 2:Neutral fraction by extrography followed by gas chromatography-mass spectrometry and electrospray ionization coupled with fourier transform ion cyclotron resonance mass spectrometry[J]. Energy Fuels, 2012, 26(6):3424-3431. doi: 10.1021/ef2020167
[17]	马筱良, 史士东.煤液化中油馏分加工制取不同产品的比较[J].石油学报(石油加工), 1989, 5(4):91-94. http://www.cnki.com.cn/Article/CJFDTOTAL-SXJG198904012.htm MA You-liang, SHI Shi-dong. Comparison of different products made by distillation from coal liquefaction[J]. Acta Pet Sin (Pet Process Sect), 1998, 5(4):91-94. http://www.cnki.com.cn/Article/CJFDTOTAL-SXJG198904012.htm
[18]	余定基, 史士东, 钱丽英.反应温度对煤液化中油镍钼催化剂加氢产物组成和性质的影响[J].燃料化学学报, 1987, 15(1):9-16. YU Ding-ji, SHI Shi-dong, QIAN Li-ying. Influence of reaction temperature on the composition and properties of hydrogenation products of nickel-molybdenum catalyst in coal liquefaction[J]. J Fuel Chem Technol, 1987, 15(1):9-16.
[19]	吴秀章, 石玉林, 马辉.煤炭直接液化油品加氢稳定和加氢改质的试验研究[J].石油炼制与化工, 2009, 40(5):1-5. doi: 10.3969/j.issn.1005-2399.2009.05.001 WU Xiu-zhang, SHI Yu-lin, MA Hui. Experimental study on hydrogenation stability and hydrogenation modification of coal direct liquefied oil[J]. Pet Ref Chem Eng, 2009, 40(5):1-5. doi: 10.3969/j.issn.1005-2399.2009.05.001
[20]	吴梅, 史军歌, 田松柏.汽油中元素硫的GC-SCD分析方法[J].石油学报(石油加工), 2008, 33(2):320-325. http://d.old.wanfangdata.com.cn/Periodical/syxb-syjg201702017 WU Mei, SHI Jun-ge, TIAN Song-bai. Analysis of elemental sulfur in gasoline by GC-SCD[J]. Acta Pet Sin(Pet Process Sect), 2008, 33(2):320-325. http://d.old.wanfangdata.com.cn/Periodical/syxb-syjg201702017
[21]	SHAH Y T. Reaction Engineering in Direct Coal liquefaction[M]. New Jersey:Wesley Publishing CO, 1981.
[22]	BEJ S K, MAITY S K, TURAGA U T. Search for an efficient 4, 6-DMDBT hydrodesulfurization catalyst:A review of recent studies[J]. Energy Fuels, 2004, 18(5):1227-1237. doi: 10.1021/ef030179+
[23]	GARCIA M J, CASTILLO A C, HEREDIA J A, TREJO E, MONTESINOS A. Kinetics of HDS and of the inhibitory effect of quinoline on HDS of 4, 6-DMDBT over a Ni-Mo-P/Al₂O₃ catalyst:Part Ⅰ[J]. Chem Eng J, 2012, 210(6):53-62.
[24]	李延红.煤液化油中含氮化合物存在形式及分布的研究[D].上海: 华东理工大学, 2014. LI Yan-hong. Study on the existence and distribution of nitrogen-containing compounds in coal liquefied oil[D]. Shanghai: East China University of Science and Technology, 2014.
[25]	刘敏, 王永刚, 赵鹏, 曲思建, 陈贵锋.白石湖煤THF萃取物中硫、氮化合物赋存形态[J].燃料化学学报, 2019, 47(2):1-6. http://manu60.magtech.com.cn/rlhxxb/CN/abstract/abstract29352.shtml LIU Min, WANG Yong-gang, ZHAO Peng, QU Si-jian, CHEN Gui-feng. Molecular characterization of sulfur and nitrogen compounds in THF extract of baishihu lignite[J]. J Fuel Chem Technol, 2019, 47(2):1-6. http://manu60.magtech.com.cn/rlhxxb/CN/abstract/abstract29352.shtml