Study on suspension bed hydrocracking of medium temperature pyrolytic heavy tar fraction
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摘要: 以中温热解煤焦油为原料, 对其性质进行了分析, 其中, ＞350 ℃重质馏分中胶质含量30.88%, 沥青质含量37.27%, 四氢呋喃不溶物3.36%, 属于常规固定床加氢裂化难以直接处理的馏分。合成了一种Mo系超分散催化剂, 采用FT-IR、XPS、XRD、SEM和TEM等对催化剂进行了表征, 催化剂中含有Mo=O和Mo-S特征结构, 活性金属的硫化率为84.34%, 在体系中具有优良的分散性, 在反应体系内原位分解为超分散MoS2颗粒；在0.25 t/d连续装置上进行了热解重油悬浮床加氢裂化实验研究, 考察了反应条件对产物分布情况和结焦率的影响, 得出适宜的反应条件为19 MPa, 440 ℃, 催化剂的添加量为300 mg/kg；此条件下石脑油收率24.47%, 柴油馏分收率49.71%, 结焦率1.32%。Abstract: The medium temperature pyrolytic coal tar was used as raw material and was analyzed, in which the fraction with boiling point > 350 ℃ that contains the resin of 30.88%, the asphaltene of 37.27% and the tetrahydrofuran insolubles of 3.36% is difficult to hydrocrack directly by conventional fixed bed. A Mo-based ultra-dispersed catalyst was synthesized, and characterized by FT-IR, XPS, XRD, SEM and TEM, etc. The catalyst contains Mo=O and Mo-S characteristic structure and has an excellent dispersibility in the reaction system, and the vulcanization ratio of molybdenum reaches 84.34%. The catalyst can be decomposed into hyper dispersive MoS2 particle in the reaction system. The suspension bed hydrocracking experiments were carried out in a 0.25 t/d continuous unit with heavy fraction of tar. Moreover, the effects of reaction conditions on product distribution and coking rate were investigated. The optimum reaction conditions were 19 MPa, 440 ℃ and 300 mg/kg of catalyst addition. Under these conditions, the naphtha yield is 24.47%, the diesel fraction yield is 49.71%, and the coking rate is 1.32%.
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Key words:
- ultra-dispersed /
- suspension bed /
- heavy tar frction /
- naphtha /
- coke yield
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图 2 悬浮床加氢裂化实验流程示意图
Figure 2 Flowchart of suspension slurry-bed hydro-cracking
1: preparation tank; 2: measuring tank; 3: hydrogen compressor; 4: recycle hydrogen compressor; 5: preheater; 6: suspension slurry-bed reactor; 7: high-temperature separator; 8: low-temperature separator; 9: oil receiving tank; 10: atmospheric distillation unit; 11: vacuum distillation unit
图 8 催化剂在反应器分解前后XRD谱图对比
Figure 8 Comparison of XRD patterns of catalysts before(a) and after (b) decomposition in reactor
图 9 分解后催化剂的粒径分布
Figure 9 Particle size distributions of the catalyst after decomposition
图 13 反应温度对残渣收率和结焦率的影响
Figure 13 Effect of reaction temperature on residue yield and coking rate
图 15 反应压力对残渣收率和结焦率的影响
Figure 15 Effect of reaction pressure on residue yield and coking rate
图 17 催化剂添加量对残渣收率和结焦率的影响
Figure 17 Effect ofcatalyst addition on residue yield and coking rate
图 18 生成焦炭的SEM照片
Figure 18 SEM images of coke
(a): absence of catalyst; (b): 300 mg/kg catalyst addition
表 1 煤焦油和煤焦油重油馏分性质
Table 1 Properties of the coal tar and heavy tar fraction
Property Sample coal tar heavy tar fraction Density /(g·cm-3) 1.05 1.16 H w/% 8.63 7.56 C w/% 84.56 85.72 O w/% 5.83 5.41 S w/% 0.35 0.39 N w/% 0.63 0.92 
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表 2 催化剂Mo 3d峰XPS拟合数据
Table 2 Fitting data of XPS patterns(Mo 3d region)
Peak Binding energy E/eV Valence Area ratio /% 1 227.1 Mo4+3d5/2 20.2 2 230.4 Mo4+3d3/2 50.3 3 235.6 Mo6+3d5/2 25.1 4 237.5 Mo6+3d3/2 0.3
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表 3 催化剂S 2p峰XPS拟合数据
Table 3 Fitting data of XPS patterns (S 2p region)
Peak Binding energy E/eV Valence Area ratio /% 1 163.6 S2- 85 2 169.5 S2+ 15
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[1] 马宝岐, 任沛建, 杨占彪, 王树宽.煤焦油制燃料油品[M].北京:化学工业出版社, 2011. http://www.bookask.com/book/974904.htmlMA Bao-qi, REN Pei-jian, YANG Zhan-biao, WANG Shu-kuan. Preparation of Fuel Oil from Coal Tar[M]. Beijing: Chemical Industry Press, 2011. http://www.bookask.com/book/974904.html [2] 刘贞贞, 方梦祥, 马帅, 骆仲泱. NiMoP/γ-Al2O3催化剂的煤焦油加氢性能研究[J].燃料化学学报, 2016, 44(5): 579-586. doi: 10.3969/j.issn.0253-2409.2016.05.010LIU Zhen-zhen, FANG Meng-xiang, MA Shuai, LUO Zhong-yang. Hydrogenation of coal tar on NiMoP/γ-Al2O3 catalyst[J]. J Fuel Chem Technol, 2016, 44(5): 579-586. doi: 10.3969/j.issn.0253-2409.2016.05.010 [3] KAN T, WANG H Y, HE H X, LI C X, ZHANG S J.Experimental study on two-stage catalytic hydroprocessing of middle-temperature coal tar to clean liquid fuels[J].Fuel, 2011, 90(11): 3404-3409. doi: 10.1016/j.fuel.2011.06.012 [4] DALAMA K, STANISLAUS A. Comparison between deactivation pattern of catalysts in fixed-bed and ebullating-bed residue hydroprocessing units[J]. Chem Eng J, 2006, 120(1/2): 33-42. http://www.wanfangdata.com.cn/details/detail.do?_type=perio&id=4de1096d771484b131dff066ecd974c3 [5] 薛倩, 张雨, 刘名瑞, 张会成.煤焦油沸腾床加氢制备180号船用燃料油调合组分[J].石油炼制与化工, 2015, 46(10):88-92. doi: 10.3969/j.issn.1005-2399.2015.10.017XUE Qian, ZHANG Yu, LIU Ming-rui, ZHANG Hui-cheng.Preparation of 180# marine fuel oil by ebullated-bed hydrotreatment of medium temperature coal tar[J]. Pet Process Petrochem, 2015, 46(10): 88-92. doi: 10.3969/j.issn.1005-2399.2015.10.017 [6] MENG Z H, YANG T, FANG X C. Experimental study of integrated ebullated-bed and fixed-bed for hydrotreating mid-low temperature coal tar to clean fuel[J].China Pet Process Petrochem Technol, 2016, 18(3):1-6. http://www.wanfangdata.com.cn/details/detail.do?_type=perio&id=zgsyjgysyhgjs201603001 [7] 吴乐乐, 李金璐, 邓文安, 张英红, 李传.煤焦油重组分甲苯不溶物结构组成及对悬浮床加氢裂化生焦的影响[J].燃料化学学报, 2015, 43(8):923-931. doi: 10.3969/j.issn.0253-2409.2015.08.004WU Le-le, LI Jin-lu, DENG Wen-an, ZHANG Ying-hong, LI Chuan. Structure of toluene insoluble coal tar heavy fraction and its relevance to the coking behavior in slurry-bed hydrocracking[J]. J Fuel Chem Technol, 2015, 43(8): 923-931. doi: 10.3969/j.issn.0253-2409.2015.08.004 [8] KAN T, SUN X Y, WANG H Y, LI C S. Production of gasoline and diesel from coal tar via its catalytic hydrogenation in serial fixed beds[J]. Energy Fuels, 2012, 26(6): 3604-3611. doi: 10.1021/ef3004398 [9] XUE F F, LI D, GUO Y T, LI X. Technical progress and the prospect of low-rank coal pyrolysis in china[J]. Energy Technol, 2017, 5(11): 1897-1907. doi: 10.1002/ente.201700203 [10] MA Z Z, GAO N B, ZHANG L, LI A M. Modeling and simulation of oil sludge pyrolysis in a rotary kiln with a solid heat carrier: Considering the particle motion and reaction kinetics[J]. Energy Fuels, 2014, 28(9): 6029-6037. doi: 10.1021/ef501263m [11] 曲旋, 张荣, 孙东凯, 毕继诚.固体热载体热解霍林河褐煤实验研究[J].燃料化学学报, 2011, 39(2): 85-89. doi: 10.3969/j.issn.0253-2409.2011.02.002QU Xuan, ZHANG Rong, SUN Dong-Kai, BI Ji-cheng.Experiment study on pyrolysis of Huolinhe lignite with solid heat carrier[J].J Fuel Chem Technol, 2011, 39(2): 85-89. doi: 10.3969/j.issn.0253-2409.2011.02.002 [12] LIANG P, WANG Z F, BI J C. Simulation of coal pyrolysis by solid heat carrier in a moving-bed pyrolyzer[J]. Fuel, 2008, 87(4): 435-442. doi: 10.1016-j.fuel.2007.06.022/ [13] 张飏.低阶粉煤热解半焦规模化利用技术研究进展[J].煤质技术, 2018, 7(4):1-9. doi: 10.3969/j.issn.1007-7677.2018.04.001ZHANG Yang. Research progress of semi-cokelarge-scale utilization technology of low rank pulverized coal pyrolysis[J].Coal Quality Technol, 2018, 7(4):1-9. doi: 10.3969/j.issn.1007-7677.2018.04.001 [14] LIANG P, WANG Z F, BI J C.Process characteristics investigation of simulated circulating fluidized bed combustion combined with coal pyrolysis[J]. Fuel Process Technol, 2007, 88(1):23-28. http://www.wanfangdata.com.cn/details/detail.do?_type=perio&id=0e1baf3872ed09e492cf5a54946133e5 [15] GENG C C, LI S Y, LIU S H, HOU J L. Flash pyrolysis of coal with solid heat carrier in a fluidized bed[J]. Adv Mater Res, 2014, 953/954: 1153-1156. https://www.researchgate.net/publication/271981062_Flash_Pyrolysis_of_Coal_with_Solid_Heat_Carrier_in_a_Fluidized_Bed [16] WANG Q H, ZHANG R, LUO Z Y, FANG M X. Effects of pyrolysis atmosphere and temperature on coal char characteristics and gasification reactivity[J]. Energy Technol, 2016, 4(4): 543-550. doi: 10.1002/ente.201500366 [17] YE C, WANG Q H, LUO Z Y, XIE G L, JIN K, MUHTAR S, CEN K F. Characteristics of coal partial gasification on a circulating fluidized bed reactor[J]. Energy Fuels, 2017, 31(3): 2557-2564. doi: 10.1021/acs.energyfuels.6b02889 [18] JIA X, WANG Q H, CEN K F, CHEN L M. An experimental study of CaSO4 decomposition during coal pyrolysis[J]. Fuel, 2016, 163: 157-165. doi: 10.1016/j.fuel.2015.09.054 [19] GUO Z H, WANG Q H, FANG M X, LUO Z Y, CEN K F. Thermodynamic and economic analysis of polygeneration system integrating atmospheric pressure coal pyrolysis technology with circulating fluidized bed power plant[J]. Appl Energy, 2014, 113(1): 1301-1314. http://www.wanfangdata.com.cn/details/detail.do?_type=perio&id=f06ddd716b4f251a3a25d3ac9a0a93ac [20] 吴青.悬浮床加氢裂化——劣质重油直接深度高效转化技术[J].炼油技术与工程, 2014, 44(2): 1-9. doi: 10.3969/j.issn.1002-106X.2014.02.001WU Qing. Suspended-bed hydrocracking process——a deep high efficiency conversion process in rapid development for processing low-quality heavy oils[J]. Pet Refin Eng, 2014, 44(2): 1-9. doi: 10.3969/j.issn.1002-106X.2014.02.001 [21] 周家顺, 邓文安, 梁士昌, 刘东, 阙国和.渣油悬浮床加氢裂化与固定床加氢脱硫工艺的比较[J].炼油技术与工程, 2001, 31(2): 14-17. doi: 10.3969/j.issn.1002-106X.2001.02.004ZHOU Jia-shun, DENG Wen-an, LIANG Shi-chang, LIU Dong, QUE Guo-he. Comparison between suspended bed hydrocracking and fixed bed hydro-desulfurizing[J]. Pet Refin Eng, 2001, 31(2): 14-17. doi: 10.3969/j.issn.1002-106X.2001.02.004 [22] BAKER M A, GILMORE R, LENARDI C, GISSLER W. XPS investigation of preferential sputtering of S from MoS2 and determination of MoSx stoichiometry from Mo and S peak positions[J]. Appl Surf Sci, 1999, 150(1/4): 255-262. [23] 刘东, 张继昌, 赵英男, 阙国和.渣油悬浮床加氢分散型Mo催化剂硫化程度的XPS分析[J].石油学报(石油加工), 2007, 23(5): 33-37. doi: 10.3969/j.issn.1001-8719.2007.05.006LIU Dong, ZHANG Ji-chang, ZHAO Ying-nan, QUE Guo-he.XPS study on the sulfurization of dispersed Mo catalyst for slurry-bed hydroprocessing of residue[J]. Acta Pet Sin(Pet Process Sect), 2007, 23(5): 33-37. doi: 10.3969/j.issn.1001-8719.2007.05.006 [24] WINTERBOTTOM J M, KHAN Z, RAYMAHASAY S, KNIGHT G. A comparison of triglyceride oil hydrogenation in a downflow bubble column using slurry and fixed bed catalysts[J]. J Appl Chem Biotechnol, 2000, 75(11): 1015-1025. doi: 10.1002/1097-4660(200011)75:11<1015::AID-JCTB304>3.0.CO;2-7 -
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