Conversion of sulphur and nitrogen compounds in hydrofining process of Baishihu coal liquefaction oil
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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。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.
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Key words:
- liquefaction oil /
- aromatic hydrocarbon /
- sulfide /
- nitrides /
- hydrorefining
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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 15.4 3.0 0.07 1.1 180 0.643 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 2.3 25 2.6 140 0.24 18 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 -
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