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
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 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 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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