Effect of sulfidation temperature on component transformation and catalytic performance of direct coal liquefaction catalyst
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摘要: 在5% H2S/N2气氛，不同预硫化温度下制备了系列硫铁催化剂，并在5 MPa 的1% H2S/H2气氛、360 ℃下研究了其催化萘的加氢活性。借助MES、XRD和XPS等表征手段，探究了催化剂在不同预硫化温度及反应条件下组分转变规律。结果表明，预硫化过程是硫由表面向内部，依照FeS2→FeS、Fe1−xS→Fe3S4→Fe2O3顺序渗硫的过程，而升高温度有利于硫向体相内的传递；接触1% H2S/H2气氛后晶粒由外向内各组分均快速转化为Fe1–xS的过程；调控预硫化条件可以实现活性组分Fe1–xS的含量高、晶粒小，于是可获得最高活性。Abstract: A series of iron sulfide catalysts were prepared in 5% H2S/N2 atmosphere at different pre-sulfidation temperatures, and their catalytic activity for naphthalene hydrogenation was studied at 360 ℃ in 1% H2S/H2 atmosphere at 5 MPa. The component transformation of the catalyst under varied pre-sulfidation temperature and reaction conditions was researched using MES, XRD and XPS. The results revealed that the sulfidation process was in the form of sulfurizing from surface to interior in the order of FeS2→FeS, Fe1–
xS→Fe3S4→Fe2O3 during which transferring sulfur to the body phase was benefited from the rise of temperature. After contacting 1% H2S/H2 gas, the particles rapidly transformed to Fe1–xS from outside to the inside. By adjusting sulfidation conditions, the Fe1–xS content was high while the particle size was small, which made it possible to obtain the greatest activity of the catalyst. -
图 1 氧化物前驱体XRD谱图（a），TEM照片及其电子衍射谱图（b）以及SEM照片（c）
Figure 1 XRD pattern (a), TEM image, electron diffraction pattern (b) and SEM image (c) of Pre (oxide precursor)
图 2 氧化物前驱体(Pre)以及不同温度下（5% H2S/N2）预硫化1 h所得催化剂的XRD谱图
Figure 2 XRD patterns of oxide precursor (Pre) and catalyst, obtained by sulfidation at different temperatures and 5% H2S/N2 for 1 h
图 3 5% H2S/N2预硫化条件下Fe 2p（a）和S 2p（b）谱图
Figure 3 Spectra of Fe 2p (a) and S 2p (b) under 5% H2S/N2 sulfidation condition
图 4 不同预处理温度（5% H2S/N2）所得催化剂经过反应条件（1% H2S/H2）后XRD谱图
Figure 4 XRD patterns of the catalysts prepared at different pretreatment temperature (5% H2S/N2) and reaction conditions (1% H2S/H2)
图 5 预处理温度与萘转化率及催化剂粒径的关系
Figure 5 Relationship between the pretreatment temperature and naphthalene transformation and catalyst particle size
图 6 不同温度预硫化条件下的颗粒变化
Figure 6 Changing the particles under different sulfidation temperature
表 1 Mössbauer谱解谱参数及其来源
Table 1 Parameters of Mössbauer spectrum and data sources
Name Site IS/
(mm·s−1)QS/
(mm·s−1)H(T) Hexagonal
Pyrrhotite[21]1 0.74 0.01 33.01 2 0.72 0.02 30.44 3 0.71 0.02 28.18 4 0.74 0.01 25.63 Monoclinic
Pyrrhotite[22]1 0.85(1) −0.035(4) 33.4(1) 2 0.86(2) 0.084(10) 31.4(2) 3 0.81(1) −0.086(10) 27.1(1) 4a 0.83(1) 0.084(15) 24.4(2) 4b 0.82(1) 0.166(15) 20.7(2) Greigite[23] octahedral 0.66 − 32.7 tetrahedral 0.38 − 31.9 Troilite[24] − 0.89 −0.14 32.8 Pyrite[25] − 0.43(1) 0.66(1) − Maghemite[26] x 0.47 −0.01 51.0 y 0.34 −0.03 48.1 Magnetite[26] A 0.42 0.06 51.6 B 0.99 0.89 51.0 Highly dispersed
Fe[27]− 0.02 −0.03 25.0 α-Fe[28] − 0.09 0.04 33.8 
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表 2 不同预硫化温度（5% H2S/N2）所得催化剂的Mössbauer谱解析
Table 2 Mössbauer spectrum results of catalysts obtained at different sulfidation temperature (5% H2S/N2)
Sample Fe3O4 Fe2O3 Fe3S4 Fe1–xS FeS FeS2 Fe Fe2+(spm) Fe3+(spm) Pre 20.3 79.7 − − − − − − − Cat-50 17.9 45.5 9.2 15.0 3.8 0 5.3 1.4 1.8 Cat-100 10.8 44.7 7.9 22.1 0 9.3 5.3 − − Cat-150 12.8 49.8 8.3 14.1 0.9 12.2 2.5 − − Cat-200 6.2 29.9 10.5 28.2 3.0 21.4 0.9 − − Cat-250 6.7 20.5 8.3 37.0 4.9 20.7 1.9 − − Cat-300 6.2 20.1 12.8 33.2 4.5 23.2 0 − −
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表 3 不同预硫化温度（5% H2S/N2）硫化1 h后XPS所得Fe 2p和S 2p参数
Table 3 Contents of Fe 2p and S 2p obtained by XPS after sulfidation at different temperatures at 5% H2S/N2 for 1 h
Sample Fe Fe2+–S Fe3+–S Fe2+–O Fe3+–O S2− $ {\rm{S}}^{2-}_2 $ $ {\rm{S}}/{\rm{S}}^{2-}_{{{n}}} $ Cat-50 4.4 29.2 9.7 12.3 44.4 75.6 24.4 − Cat-100 5.0 48.4 20.6 7.0 19.0 61.3 30.8 7.9 Cat-150 3.3 52.6 18.4 15.6 10.1 53.9 41.1 5.0 Cat-200 6.5 48.4 23.1 7.3 14.7 58.2 36.8 5.0 Cat-250 8.7 39.9 19.5 16.0 15.8 61.1 30.8 8.1 Cat-300 7.6 43.0 21.7 10.6 17.1 62.2 28.3 9.5
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表 4 不同预处理温度（5% H2S/N2）所得催化剂经过反应条件（1% H2S/H2）后Fe1−xS的晶粒尺寸及Fe1−xS中1−x值
Table 4 Particle size of Fe1–xS and the 1–x value of Fe1–xS for the catalysts prepared at different pretreatment temperature (5% H2S/N2) after reaction conditions (1% H2S/H2)
Sample Particle size of Fe1–xS/nm 1–x value of Fe1–xS Cat-50-360 24.2 0.91 Cat-100-360 25.1 0.91 Cat-150-360 20.6 0.90 Cat-200-360 20.7 0.88 Cat-250-360 22.3 0.90 Cat-300-360 23.7 0.91
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表 5 不同预处理温度（5% H2S/N2）所得催化剂经过反应条件（1% H2S/H2）后Mössbauer谱所得不同物质占比
Table 5 Mössbauer spectra for the samples prepared at different pretreatment temperature (5% H2S/N2) and reaction conditions (1% H2S/H2)
Sample Fe3O4 Fe2O3 Fe3S4 Fe1–xS FeS FeS2 Fe Cat-50-360 8.2 39.8 6.7 25.3 0.7 11.2 8.2 Cat-100-360 0 3.3 0 64.1 20.6 6.2 5.8 Cat-150-360 1.6 0.8 3.2 61.8 19.3 5.6 7.8 Cat-200-360 0 0.4 1.9 70.5 15.5 4.9 6.9 Cat-250-360 0 0.5 0 69.8 18.1 5.2 6.4 Cat-300-360 0.2 1.3 2.7 70.6 14.8 5.0 5.5
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