Research of hydrogen action during pre-sulfidation of direct coal liquefaction catalyst
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摘要: 在不同温度、不同氢气分压下预硫化制备了系列硫铁催化剂，并在5 MPa 1% H2S-H2气氛、360 ℃下研究了其催化萘加氢活性。借助XRD、MES、SEM-EDS、ICP和GC-MS等表征手段，研究了不同温度下氢气在预硫化过程中的作用。结果表明，预硫化过程中氢气的引入有利于硫的传递，从而促进了硫化。在不同温度下均有利于活性相Fe1−xS生成，但不同预硫化温度下氢气的作用有所不同。50 ℃预硫化时，氢气的引入可以有利于硫的传递，使得催化活性有所上升，但该温度下依然存在大量单质Fe和单质S；150 ℃预硫化时催化活性最好，单质Fe含量下降没有单质S生成，随着氢气分压的增大，萘加氢转化率由60.6%增加至69.1%；300 ℃预硫化时氢气将催化剂表面的硫还原至低价态，不利于硫的传递，在催化剂颗粒内部观察到晶态的Fe3O4，进而催化活性有不同程度的下降。Abstract: A series of iron sulfide catalysts were prepared by pre-sulfidation at different temperatures and different hydrogen partial pressures, and their catalytic naphthalene hydrogenation activities were studied under 5 MPa 1% H2S-H2 atmosphere at 360 ℃. By means of XRD, MES, SEM-EDS, ICP and GC-MS, the effect of hydrogen on the pre-sulfidation process at different temperatures was studied. The results show that the introduction of hydrogen during the pre-sulfidation process facilitates the transfer of sulfur, thereby promoting the sulfidation. The effect of hydrogen is different at different pre-sulfidation temperatures. When pre-sulfidation at 50 ℃, the introduction of hydrogen can be beneficial to the transfer of sulfur, which increases the catalytic activity, but a lot of elemental Fe and elemental S can still be observed at this temperature; when pre-sulfidation at 150 ℃, the catalytic activity is the best. The content of zero-valent Fe decreases and no pure S is observed. With the increase of hydrogen partial pressure, the hydrogenation conversion of naphthalene increases from 60.6% to 69.1%. When pre-sulfidation at 300 ℃, the catalytic activity decreases with the introduction of hydrogen. Hydrogen reduces the sulfur on the catalyst surface to low valence state and crystalline Fe3O4 is observed inside the catalyst particles, which is not conducive to the transfer of sulfur.
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Key words:
- pre-sulfidation /
- iron-based catalyst /
- hydrogen /
- direct liquefaction catalyst
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图 2 催化剂前驱体的程序升温硫化（TPS）
Figure 2 Temperature programmed sulfidation (TPS) of catalyst precursor
图 4 不同温度和不同氢气分压预硫化的萘加氢
Figure 4 Results of naphthalene hydrogenation at different hydrogen partial pressures of 50, 150 and 300 ℃ （5 MPa, 1% H2S-H2, 360 ℃, 1 h）
图 6 Cat-50-p经THF溶解后上清液的GC-MS谱图
Figure 6 GC-MS results of supernatant of dissolved by THF
图 7 硫化过程及硫化催化剂颗粒结构
Figure 7 Pre-sulfuration process and particle structure of presulfidation catalyst
表 1 Mössbauer谱的拟合参数
Table 1 Parameters of Mössbauer spectrum
Name Site IS/(mm·s−1) QS/(mm·s−1) H(T) Hexagonal pyrrhotite 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 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 octahedral 0.66 − 32.7 tetrahedral 0.38 − 31.9 Troilite − 0.89 −0.14 32.8 Pyrite − 0.43(1) 0.66(1) − Maghemite x 0.47 −0.01 51.0 y 0.34 −0.03 48.1 Magnetite A 0.42 0.06 51.6 B 0.99 0.89 51.0 Highly dispersed Fe − 0.02 −0.03 25.0 α-Fe − 0.09 0.04 33.8 
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表 2 Cat-50-p的Mössbauer谱解析
Table 2 Mössbauer spectrum results of Cat-50-p
p/% Content/% FeS2 Fe3S4 Fe1−xS FeS Fe2O3 Fe3O4 Fe Fe3+
(spm)Fe2+
(spm)0 0.0 3.7 15.1 7.6 40.0 22.1 8.7 2.0 1.0 5 0.0 6.4 21.7 4.0 37.2 16.5 10.6 2.3 1.2 20 0.0 8.4 25.5 1.6 28.0 15.4 16.7 3.5 0.9 45 0.0 8.5 25.5 0.4 32.6 13.2 15.8 3.1 0.9 90 0.0 17.8 31.6 3.2 17.6 4.3 20.0 3.9 1.8 95 0.0 16.3 31.7 5.1 12.7 2.6 24.9 5.3 1.4
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表 3 Cat-50-p的(S/Fe)atom和单质硫质量
Table 3 (S/Fe) atom and elemental sulfur quality results for Cat-50-p
p/% 0 5 20 45 90 95 S/Fe 0.87 0.88 0.89 0.96 1.14 1.16 S/(${\rm{g}}\cdot {\rm{g}}_{{\rm{cat}}}^{-1} $) 0.0155 0.0125 0.0094 0.0079 0.0068 0.0056
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表 4 Cat-50-p的XPS拟合
Table 4 XPS fitting results of Cat-50-p
Content/% Fe(0) Fe(Ⅱ)−S Fe(Ⅲ)−S Fe(Ⅱ)−O Fe(Ⅲ)−O ${\rm{S}}_{2}^{{2-}} $ S2− S/S8 Cat-50-0 0.0 2.3 0.9 6.4 90.4 7.1 78.9 14.0 Cat-50-20 0.0 7.9 7.5 7.7 76.9 16.7 80.5 2.8 Cat-50-45 0.0 16.5 18.4 10.1 55.1 32.1 67.9 0.0 Cat-50-95 0.0 22.7 32.6 15.2 29.5 33.9 66.1 0.0
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表 5 Cat-150-p的Mössbauer谱解析
Table 5 Mössbauer spectrum results of Cat-150-p
p/% Content/% FeS2 Fe3S4 Fe1−xS FeS Fe2O3 Fe3O4 Fe 0 21.6 14.4 23.9 0.0 24.2 11.0 5.0 5 18.9 16.0 22.7 3.4 21.9 12.6 4.5 20 16.5 16.5 25.8 3.2 25.3 7.4 5.3 45 14.8 22.4 28.6 0.3 16.5 7.6 9.8 90 15.2 19.0 42.6 2.7 2.1 6.3 12.2 95 15.6 20.6 43.8 2.5 2.8 4.3 10.4
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表 6 Cat-150-p的(S/Fe)atom
Table 6 (S/Fe) atom results for Cat-150-p
p/% 0 5 20 45 90 95 S/Fe 0.92 0.94 0.96 1.03 1.19 1.23
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表 7 Cat-150-p的XPS拟合结果
Table 7 XPS fitting results of Cat-150-p
Content/% Fe(0) Fe(Ⅱ)−S Fe(Ⅲ)−S Fe(Ⅱ)−O Fe(Ⅲ)−O ${\rm{S} }_{2}^{{2-} } $ S2− S/S8 Cat-150-0 0.0 25.2 5.3 22.1 47.4 38.6 60.2 1.3 Cat-150-20 0.0 24.3 15.1 21.3 39.3 36.0 64.0 0.0 Cat-150-45 0.0 24.7 11.7 18.6 45.0 31.6 68.4 0.0 Cat-150-95 0.0 28.5 23.5 21.7 26.3 37.9 62.1 0.0
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表 8 Cat-300-p的Mossbauer谱解析
Table 8 Mössbauer spectrum results of Cat-300-p
p/% Content/% FeS2 Fe3S4 Fe1−xS FeS Fe2O3 Fe3O4 Fe 0 20.9 9.4 26.2 0.0 28.2 12.9 2.4 5 5.7 10.8 40.2 4.2 24.9 14.2 0.0 20 2.2 4.7 55.5 4.1 16.6 14.1 2.8 45 3.0 9.7 57.3 1.3 9.8 15.2 3.8 90 1.7 6.9 63.4 5.8 8.8 10.5 2.9 95 6.7 7.9 53.2 5.8 13.2 9.3 3.9
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表 9 Cat-300-p的(S/Fe)atom结果
Table 9 (S/Fe) atom results for Cat-300-p
p/% 0 5 20 45 90 95 S/Fe 0.95 0.87 0.84 0.90 0.90 0.91
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表 10 Cat-300-95的SEM-EDS的(O/S)wt
Table 10 (O/S) wt results of SEM-EDS of Cat-300-95
Site 1 Site 2 Site 3 Site 4 Site 5 a 0.59 0.65 0.79 0.70 0.61 b 0.68 0.60 0.71 1.44 0.66 c 0.74 0.77 0.94 0.92 0.88 d 0.22 0.34 3.52 0.47 0.69
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表 11 Cat-300-p的XPS拟合
Table 11 XPS fitting results of Cat-300-p
Content/% Fe(0) Fe(Ⅱ)−S Fe(Ⅲ)−S Fe(Ⅱ)−O Fe(Ⅲ)−O ${\rm{S} }_{2}^{{2-} } $ S2− S/S8 Cat-300-0 0.0 23.7 13.1 13.3 49.9 45.3 54.7 0.0 Cat-300-20 0.0 23.7 11.9 18.8 45.6 31.6 68.4 0.0 Cat-300-45 0.0 26.0 24.0 22.2 27.9 20.6 79.4 0.0 Cat-300-95 0.0 29.8 25.2 21.5 23.5 19.5 80.5 0.0
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表 12 不同温度下分压为0和95时的Mössbauer谱解析
Table 12 Mössbauer spectrum results of 0 and 95 in different temperature
Content/% FeS2 Fe3S4 Fe1−xS FeS Fe2O3 Fe3O4 Fe Fe3+
(spm)Fe2+
(spm)Cat-50-0 0.0 3.7 15.1 7.6 40.0 22.1 8.7 2.0 1.0 Cat-50-95 0.0 16.3 31.7 5.1 12.7 2.6 24.9 5.3 1.4 Cat-150-0 21.6 14.4 23.9 0.0 24.2 11.0 5.0 − − Cat-150-95 15.6 20.6 43.8 2.5 2.8 4.3 10.4 − − Cat-300-0 20.9 9.4 26.2 0.0 28.2 12.9 2.4 − − Cat-300-95 6.7 7.9 53.2 5.8 13.2 9.3 3.9 − −
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表 13 不同温度下分压为0和95时的(S/Fe)atom结果
Table 13 (S/Fe) atom results for 0 and 95 in different temperature
Cat-50-0 Cat-50-95 Cat-150-0 Cat-150-95 Cat-300-0 Cat-300-95 S/Fe 0.87 1.16 0.82 1.23 0.95 0.91
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表 14 不同温度下分压为0和95时的XPS拟合
Table 14 XPS fitting results of 0 and 95 in different temperature
Content/% Fe(0) Fe(Ⅱ)−S Fe(Ⅲ)-S Fe(Ⅱ)−O Fe(Ⅲ)−O ${\rm{S} }_{2}^{{2-} } $ S2− S/S8 Cat-50-0 0.0 2.3 0.9 6.4 90.4 7.1 78.9 14.0 Cat-50-95 0.0 22.7 32.6 15.2 29.5 33.9 66.1 0.0 Cat-150-0 0.0 25.2 5.3 22.1 47.4 38.6 60.2 1.3 Cat-150-95 0.0 28.5 23.5 21.7 26.3 37.9 62.1 0.0 Cat-300-0 0.0 23.7 13.1 13.3 49.9 45.3 54.7 0.0 Cat-300-95 0.0 29.8 25.2 21.5 23.5 19.5 80.5 0.0
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