Morphology study of nickel and vanadium in asphaltenes via hydropyrolysis
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摘要: 本研究通过临氢热解方法处理委内瑞拉减压渣油沥青质,通过电感偶合等离子体质谱仪(ICP MS)、紫外-可见光光谱仪(UV-vis)、高温气相色谱-原子发射检测器联用仪(HT GC-AED)和傅里叶变换离子回旋共振质谱(FT-ICR MS)等手段分析表征反应产物,探究沥青质的分子组成与结构,以及镍和钒化合物的存在形态。实验结果表明,随着临氢热解反应温度从330 ℃升高至410 ℃,反应产物的甲苯可溶物收率由64%下降至19%,可被GC-AED检测到的镍、钒化合物的含量大幅度升高,镍和钒卟啉的分子组成分布也随反应温度的升高呈现出规律性的变化。Abstract: The morphology of nickel and vanadium compounds in the asphaltenes were investigated via hydropyrolysis with the help of inductively coupled plasma mass spectrometer (ICP-MS), ultraviolet-visible (UV-Vis), high-temperature gas chromatography atomic emission detection (HT GC-AED), and positive-ion electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (+ESI FT-ICR MS). The results showed that the toluene soluble yields of products decreased from 64% to 19% as the hydropyrolysis temperature increased from 330 to 410 ℃, while the abundance of nickel and vanadium compounds detected by GC-AED increased significantly. The molecular composition distribution of nickel and vanadyl porphyrins showed rhythmic changes with different temperatures in the hydropyrolysis of asphaltenes.
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Key words:
- hydropyrolysis /
- asphaltenes /
- nickel /
- vanadium /
- porphyrin
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图 3 沥青质临氢热解产物中N4VO类化合物的DBE与碳数分布(图中给出了C30H31N4O1V1 和 C36H31N4O1V1钒卟啉的可能结构)
Figure 3 Relative ion abundance plots of DBE versus carbon number of N4VO class species assigned from positive-ion ESI FT-ICR mass spectra of the hydropyrolysis treated asphaltenes The proposed structure of C30H31N4O1V1 and C36H31N4O1V1 are shown based on the molecular composition
表 1 委内瑞拉重油减渣组分C7沥青质临氢热解反应后甲苯可溶物收率
Table 1 Toluene soluble yields of hydropyrolysis products derived from the asphaltenes of Venezuelan VR
Sample 0#
CG1#
330 ℃2#
350 ℃3#
370 ℃4#
390 ℃5#
410 ℃Yield w/% 98 64 60 51 45 19 表 2 沥青质临氢热解反应后甲苯可溶物中镍和钒含量
Table 2 Nickel and vanadium contents of hydropyrolysis products from ICP MS
Sample 0#
CG1#
330 ℃2#
350 ℃3#
370 ℃4#
390 ℃5#
410 ℃V /(μg·g−1) 1896 1640 1400 1473 1609 1305 Ni /(μg·g−1) 439 400 412 404 441 310 表 3 委内瑞拉减渣C7沥青质临氢热解后各样品中镍、钒元素的GC-AED信号丰度与对照组的比率
Table 3 Signal peak area ratio of nickel and vanadium in reaction group and control group detect by GC-AED
Sample 0#
CG1#
330 ℃2#
350 ℃3#
370 ℃4#
390 ℃5#
410 ℃V(ratio) 1.0 0.9 0.9 1.0 1.1 3.6 Ni(ratio) 1.0 1.0 1.3 1.9 3.8 14.4 -
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