Study on ex-situ presulfurization technologies with different presulfiding agents for CoMo-based sulfur-tolerant shift catalysts
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摘要: 从多种硫化剂中筛选出(NH4)2S和Na2S，分别采用不同的预硫化技术对工业级CoMo型耐硫变换催化剂进行器外预硫化，采用XRD、XPS和HRTEM等表征手段对催化剂的晶相结构、表面特性和微观形貌进行表征。(NH4)2S和Na2S作为预硫化剂对催化剂的晶相结构没有明显影响；用(NH4)2S进行预硫化时活性组分发生部分O-S交换，而用Na2S进行预硫化时活性组分仍保持为氧化态，两种预硫化型催化剂在反应器内随着反应温度升高，硫化深度为S-Na2S > S-(NH4)2S >常规器内预硫化；器内预硫化和(NH4)2S作为预硫化剂MoS2片层结构堆叠层数集中在2-3层，而用Na2S进行预硫化时MoS2片层堆叠层数明显变多，集中在3-5层。采用微型固定床评价装置，选择285、350、450 ℃三个反应温度，催化剂的活性顺序为S-Na2S > S-(NH4)2S >常规器内预硫化。Abstract: (NH4)2S and Na2S were selected from several presulfiding agents. Industrial Co-Mo based sulfur-tolerant shift catalysts were ex-situ presulfided with different presulfurization technologies. The crystal structures, surface characteristics and micro appearance were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (HRTEM). (NH4)2S and Na2S as presulfiding agents did not show obvious effects on the crystal structures of the catalysts. Partial O-S exchange of the active components was observed when (NH4)2S was used for presulfirization. And when presulfided with Na2S, the active components still remained oxidation state. As the ex-situ presulfurization temperature increased, the extent of vulcanization was:S-Na2S > S-(NH4)2S > the general in situ pre-vulcanization. When presulfided with (NH4)2S or the general in situ pre-vulcanization, the stacking number of MoS2 layers was mainly two to three. And when presulfided with Na2S, the stacking number of MoS2 layers increased obviously, mostly three to five. The activity sequence of the catalysts was S-Na2S > S-(NH4)2S > the general in situ pre-vulcanization when the catalysts were tested in a micro-fixed reactor at temperatures of 285, 350 and 450℃ respectively.
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Key words:
- sulfur-tolerant shift catalyst /
- ex-situ presulfurization technology /
- (NH4)2S /
- Na2S
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图 1 不同硫化剂制备预硫化型催化剂孔径分布
Figure 1 Pore diameter distribution of the catalysts treated by different sulfiding agents
图 2 不同硫化剂制备预硫化型催化剂吸附-脱附等温曲线
a: G-O; b: S-H2S; c: S-Na2S; d: S-(NH4)2S
Figure 2 Nitrogen adsorption-desorption isotherms of the catalysts treated by different sulfiding agents
图 3 不同硫化剂制备预硫化型催化剂的XRD谱图
a: G-O; b: S-H2S; c: S-(NH4)2S; d: S-Na2S
Figure 3 X-ray diffraction patterns of the catalysts treated by different sulfiding agents
图 4 不同硫化剂制备预硫化型催化剂反应后的XRD谱图
a: G-O; b: S-H2S; c: S-(NH4)2S; d: S-Na2S
Figure 4 X-ray diffraction patterns of the catalysts treated by different sulfiding agents after reaction
图 5 不同硫化剂制备预硫化型催化剂的HRTEM照片
(a)：G-O；(b)：S-H2S；(c)：S-(NH4)2S；(d)：R-(NH4)2S；(e)：S-Na2S；(f)：R-Na2S
Figure 5 HRTEM photographs of the catalysts treated by different sulfiding agents
图 6 不同硫化剂制备预硫化型催化剂的CO变换活性
— ■ —：S-H2S；— ● —：S-(NH4)2S；— ▲ —：S-Na2S；— ▼ —：equilibrium conversion
Figure 6 Shift reaction activity of the catalysts treated by different sulfiding agents
表 1 不同硫化剂制备预硫化型催化剂的孔结构性质
Table 1 Physical properties of the catalysts treated by different sulfiding agents
Sample ABET/(m2·g-1) Dpore/nm vpore/(cm3·g-1) G-O 182 5.69 0.26 S-(NH4)2S 153 5.65 0.28 S-Na2S 142 4.80 0.20 S-H2S 147 6.20 0.28 
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表 2 不同硫化剂制备预硫化型催化剂Mo 3d、Co 2p和S 2p的结合能
Table 2 Mo 3d, Co 2p and S 2p binding energy(BE) of the catalysts treated by different sulfiding agents
Sample Binding energy E/eV Mo 3d5/2 Mo 3d3/2 Co 2p3/2 Co 2p1/2 S 2p3/2 S 2p1/2 G-O 232.6 235.7 788.2 804.2 - - 781.2 797.2 S-H2S 232.5 235.6 788.2 804.2 168.6 169.8 230.9 234.0 781.2 797.2 162.0 163.2 229.1 232.2 779.1 795.1 S-(NH4)2S 232.6 235.7 788.2 804.2 168.6 169.8 229.2 232.3 781.2 797.2 162.2 163.4 779.1 795.1 R-(NH4)2S 232.6 235.7 788.2 804.2 168.7 169.9 231.0 234.1 781.2 797.2 162.1 163.3 229.1 232.2 779.1 795.1 S-Na2S 232.7 235.8 788.2 804.2 168.0 169.2 781.2 797.2 161.9 163.1 R-Na2S 232.5 235.6 788.2 804.2 168.6 169.8 230.9 234.0 781.2 797.2 161.8 163.0 229.2 232.3 779.1 795.1
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表 3 不同硫化剂制备预硫化型催化剂的原子比
Table 3 Atomic ratio of the catalysts treated by different sulfiding agents
Sample Mo4+/Mo /% Mo5+/Mo /% Mo6+/Mo /% S/Mo S2-/ Mo G-O 0 0 100 0 0 S-H2S 27.2 2.6 70.17 1.95 0.74 S-(NH4)2S 8.84 0 91.16 2.06 1.72 R-(NH4)2S 52.2 1.2 46.60 1.91 0.93 S-Na2S 0 0 100 2.14 0.82 R-Na2S 54.9 0.8 44.3 2.37 1.40
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