Effect of nickel cobalt co-catalyst on catalytic activity of molybdenum naphthenate for the hydroprocessing of coal tar pitch in suspension bed
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摘要: 合成了钼、镍、钴的五种分散型油溶性均相催化剂，选用高压釜反应器进行悬浮床加氢催化反应，控制反应条件在370 ℃、10 MPa氢压，反应时间4 h，考察环烷酸钼加入量、钼-镍、钼-钴双金属等比例对加氢反应的影响。通过反应结果的液体收率来衡量催化体系的煤沥青加氢催化效果。综合运用了元素分析、ICP-MS、透射电镜、X射线光电子能级、四组分分析等多种分析方法，探索煤沥青悬浮床加氢反应的最优催化体系。得出最优催化体系为：2.0×10−3下，环烷酸钼&环烷酸镍（1∶1）。此体系下，液体收率达85.3%，残渣量10.6%，气体4.1%。Abstract: Five dispersed molybdenum, nickel and cobalt oil soluble homogeneous catalysts were synthesized. The hydrogenation of coal tar pitch was under the conditions of 370 °C, 10 MPa hydrogen pressure, and 4 h reaction time in an autoclave reactor. The effects of molybdenum naphthenate addition, molybdenum nickel and molybdenum cobalt bimetallic ratios on hydrogenation were investigated. The catalytic hydrogenation effect was evaluated by the liquid yield. A variety of analytical methods, such as elemental analysis, ICP-MS, TEM, XPS, and four component separation, were used to explore the optimal catalytic system for the slurry bed hydrogenation of coal tar pitch. The results show that the optimal catalytic system is molybdenum naphthenate and nickel naphthenate ratio of 1∶1 at catalyst amount of 2×103. Under optimal conditions, the liquid yield is 85.3%, the residue yield is 10.6%, and the gas yield is 4.1%.
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Key words:
- coal tar pitch /
- hydro-upgrading /
- homogeneous catalyst /
- slurry bed hydrocracking
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图 1 合成的油溶性催化剂
Figure 1 Oil soluble catalysts
(a): molybdenum naphthenate; (b): nickel naphthenate; (c): nickel iso-octoate; (d): cobalt naphthenate; (e)：cobalt iso-octoate
图 2 硫化催化剂Ni 2p的XPS谱图
Figure 2 Ni 2 p XPS spectra of sulfide catalysts
(a): molybdenum naphthenate & nickel naphthenate; (b): molybdenum naphthenate & nickel iso-octanate
图 3 硫化催化剂Mo 3d XPS谱图
Figure 3 Mo 3 d XPS spectra of sulfide catalysts
(a): molybdenum naphthenate; (b): molybdenum naphthenate & nickel naphthenate; (c): molybdenum naphthenate & nickel iso-octanate; (d): molybdenum naphthenate & cobalt naphthenate; (e): molybdenum naphthenate & cobalt iso-octanate
图 4 硫化催化剂Co 2p的XPS谱图
Figure 4 Co 2 p XPS spectra of sulfide catalysts
(a): molybdenum naphthenate & cobalt naphthenate; (b): molybdenum naphthenate & cobalt iso-octanate
图 5 硫化催化剂透射电镜照片
Figure 5 Transmission electron microscope photographs of sulfide catalyst
(a): molybdenum naphthenate; (b): molybdenum naphthenate & nickel naphthenate; (c): molybdenum naphthenate & nickel iso-octanate; (d): molybdenum naphthenate & cobalt naphthenate; (e): molybdenum naphthenate & cobalt iso-octanate
表 1 (Co/Ni)MoS2晶片的形貌参数计算方法
Table 1 Formulae for the morphology parameters of (Co/Ni)MoS2 slabs
Formula Symbolic meaning $ \bar L $ $\bar L = \dfrac{ {\sum { {L _i} } } }{n}$ the average slab length $\bar N $ $\bar N = \dfrac{ {\sum { { {n_i}{N} }_i} } }{n}$ the average stacking numbers n'i $n'_i = \dfrac{{10 \times \dfrac{{\overline L }}{{3.2}} + 1}}{2}$ the number of Mo atoms along one side of a slab Me ${M_{\rm{e}}} = (6n'_i - 12) \times \overline L $ the number of Mo atoms at the edge sites Mc ${M_{\rm{c}}} = 6 \times \overline N $ the number of Mo atoms at the corner sites MT ${M_{\rm{T} } } = (3{ n '_i }^2 - 3n'_i + 1) \times \overline N$ the total number of Mo atoms fe,% ${f_{\rm{e} } },\% = \dfrac{ { {M_{\rm{e}}} } }{ { {M_{\rm{T} } } }} \times 100\%$ the fraction of Mo atoms at the edge sites fc,% ${f_{\rm{c}}},\% = \dfrac{{{M_{\rm{c}}}}}{{{M_{\rm{T}}}}} \times 100\% $ the fraction of Mo atoms at the corner sites 
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表 2 原料煤沥青元素分析数据
Table 2 Elemental analysis data of raw coal tar pitch
Element composition C N H S O C/H（atomic ratio） w/% 87.95 0.58 7.05 2.79 1.63 1.039 Four components saturated aromatic resin asphaltene toluene insoluble matter sum w/% 8.8 14.2 19.8 53.5 2.3 98.6
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表 3 不同催化剂的活性金属含量
Table 3 The metal contents of various catalysts
Catalyst Theoretical metal
content w/%Metal
content w/%Relative metal
content w/%(a)Molybdenum naphthenate 11.68 9.5 81.3 Nickel naphthenate 14.6 12.9 88.4 Nickel iso-octoate 17.0 16.2 95.3 Cobalt iso-octoate 17.1 16.5 96.5 Cobalt naphthenate 14.6 12.26 83.4 a: the relative metal content is the percentage ratio of the measured metal content to the theoretical metal content
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表 4 硫化催化剂表面活性物种的组成和浓度
Table 4 The composition and concentration of surface-active species of the sulfide catalysts
Catalyst Concentration w/% Mo(Ⅳ) Mo(Ⅴ) Mo(Ⅵ) Ni(Ⅱ) NiMoS NiSx Co(ll) CoMoS Co9S8 Molybdenum naphthenate 71.0 15.1 13.9 Molybdenum naphthenate & nickel naphthenate 85.1 10.3 4.6 36.3 47.8 15.9 Molybdenum naphthenate & nickel iso-octoate 80.0 12.2 7.8 48.3 38.7 13.0 Molybdenum naphthenate & cobalt naphthenate 75.6 11.2 13.2 31.5 55.5 13.0 Molybdenum naphthenate & cobalt iso-octoate 74.4 13.2 12.4 38.8 23.8 37.4
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表 5 硫化催化剂透射电镜分析
Table 5 Transmission electron microscopy analysis of the sulfide catalyst
Catalyst $\bar L$/nm $\bar N$ fe /% fc /% Molybdenum naphthenate 4.35 3.04 22.89 4.32 Molybdenum naphthenate & nickel naphthenate 3.91 3.38 24.64 5.35 Molybdenum naphthenate & nickel iso-octoate 4.20 3.18 23.46 4.64 Molybdenum naphthenate & cobalt naphthenate 4.13 3.45 23.75 4.80 Molybdenum naphthenate & cobalt iso-octoate 4.28 3.10 23.17 4.47
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表 6 环烷酸钼不同加入量下煤沥青加氢产物分布
Table 6 Hydrogenation product distribution of coal tar pitch with different addition amount of molybdenum naphthenate
The amount of catalyst added Liquid yield w/% Residue w/% Gas volume φ/% Molybdenum naphthenate 1.5×10−3 52.3 41.9 5.8 Molybdenum naphthenate 2.0×10−3 60.3 31.3 8.4 Molybdenum naphthenate 3.0×10−3 82.6 13.3 4.1 Molybdenum naphthenate 4.0×10−3 55.3 40.0 4.7 Molybdenum naphthenate 5.0×10−3 50.0 46.0 4.0
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表 7 双金属等比例煤沥青加氢产物分布
Table 7 Distribution of hydrogenation products of catalysts with equal proportion of bimetal
Total amount of catalyst 2.0×10−3 Liquid yield w/% Residue w/% Gas volume φ/% Molybdenum naphthenate & nickel naphthenate 85.3 10.6 4.1 Molybdenum naphthenate & nickel iso-octoate 70.0 23.0 7.0 Molybdenum naphthenate & cobalt naphthenate 68.0 24.3 7.7 Molybdenum naphthenate & cobalt iso-octoate 66.7 26.3 7.0
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表 8 四组分分析
Table 8 Results of four-component analyses
Content w/% saturated aromatic resin asphaltene toluene insoluble
mattersum Molybdenum naphthenate 9.3 31.1 13.9 36.1 7.2 97.6 Molybdenum naphthenate & nickel naphthenate 21.0 40.6 13.0 12.0 8.6 95.2 Molybdenum naphthenate & nickel iso-octoate 17.6 39.1 14.2 15.6 8.0 94.5 Molybdenum naphthenate & cobalt naphthenate 16.3 35.6 15.2 20.6 8.6 96.3 Molybdenum naphthenate & cobalt iso-octoate 10.6 33.5 11.3 29.8 9.0 94.2
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表 9 不同环烷酸钼&环烷酸镍催化剂作用下煤沥青的加氢产物分布
Table 9 Distribution of hydrogenated products over catalysts with various ratios of molybdenum naphthenate to nickel naphthenate
Total amount of catalyst 2.0×10−3 Liquid yield w/% Residue w/% Gas volume φ/% Molybdenum naphthenate & nickel naphthenate（1∶2） 75.0 20.0 5.0 Molybdenum naphthenate & nickel naphthenate（2∶3） 76.0 17.3 6.7 Molybdenum naphthenate & nickel naphthenate（1∶1） 85.3 10.6 4.1 Molybdenum naphthenate & nickel naphthenate（3∶2） 68.0 22.6 9.4 Molybdenum naphthenate & nickel naphthenate（2∶1） 67.0 23.3 9.7
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