催化剂形貌对沸腾床渣油加氢Ni-Mo/Al2O3 催化剂活性位的影响机制

doi:10.11949/0438-1157.20200895

化工学报 ›› 2021, Vol. 72 ›› Issue (4): 2076-2085.DOI: 10.11949/0438-1157.20200895

• 催化、动力学与反应器 • 上一篇下一篇

催化剂形貌对沸腾床渣油加氢Ni-Mo/Al₂O₃ 催化剂活性位的影响机制

朱慧红¹(),茆志伟²,杨涛¹,冯翔²(),金浩¹,彭冲^1,³(),杨朝合²,王继锋¹,方向晨¹

^1.中国石化大连石油化工研究院，辽宁大连 116045
^2.中国石油大学（华东）重质油国家重点实验室，山东青岛 266580
^3.华东理工大学化学工程联合国家重点实验室，上海 200237

收稿日期:2020-07-06 修回日期:2020-09-25 出版日期:2021-04-05 发布日期:2021-04-05
通讯作者: 冯翔,彭冲
作者简介:朱慧红（1978—），女，硕士，高级工程师，zhuhuihong.fshy@sinopec.com
基金资助:
国家自然基金委重大研究计划集成项目(91934301);国家重点研发计划项目(SQ2018YFA020161);国家自然科学基金项目(21978325);中央高校基本科研业务费专项资金(18CX02014A);山东省软科学研究计划项目(2019RKE28003)

Influence mechanism of catalyst morphology on the active sites of Ni-Mo/ Al₂O₃ catalyst for ebullated bed residue hydrogenation

ZHU Huihong¹(),MAO Zhiwei²,YANG Tao¹,FENG Xiang²(),JIN Hao¹,PENG Chong^1,³(),YANG Chaohe²,WANG Jifeng¹,FANG Xiangchen¹

^1.Dalian Research Institute of Petroleum and Petrochemicals, SINOPEC, Dalian 116045, Liaoning, China
^2.State Key Laboratory of Heavy Oil Processing, China University of Petroleum, Qingdao 266580, Shandong, China
^3.State Key Laboratory of Chemical Engineering, East China University of Science and Technology, Shanghai 200237, China

Received:2020-07-06 Revised:2020-09-25 Online:2021-04-05 Published:2021-04-05
Contact: FENG Xiang,PENG Chong

摘要/Abstract

摘要：

随着原油供应趋于劣质化和严格的环保法规出台，沸腾床渣油加氢技术引起了广泛关注。采用挤压成型法和STRONG沸腾床的特殊成型法分别制备了圆柱形和球形Ni-Mo/Al₂O₃催化剂，系统地研究了催化剂的颗粒形貌对活性相和渣油加氢性能的影响。采用XRD、N₂物理吸脱附、H₂-TPR、HRTEM、XPS和电子微探针分析等手段对催化剂进行了表征。结果表明，球形催化剂具有活性更强的Type Ⅱ类型活性位点、更优异的孔道结构性质和更好的流化性能，这使得其具有更高的渣油加氢活性。球形催化剂中的金属和载体之间相互作用较弱，这有利于形成更高硫化程度和堆垛层数的Ni-Mo-S Ⅱ型活性相，这种活性相在渣油加氢中具有更高的活性。此外，球形催化剂具有比圆柱形催化剂更大的孔径和孔体积，这有利于大分子杂质在孔道中的扩散和活性位点上的吸附，并且使得金属沉积物均匀分布在球形催化剂中，而不是集中分布在孔口。而且球形催化剂尺寸更小，可能更易于流化，这增强了催化剂的传质性能。

关键词: 催化, 加氢, 氧化铝, 形貌效应, 沸腾床, 渣油

Abstract:

With the deterioration of crude oil supply and the introduction of strict environmental regulations, fluidized bed residue hydrogenation technology has attracted widespread attention. Cylindrical and spherical Ni-Mo/Al₂O₃ catalysts were prepared by the extrusion molding method and the special molding method of STRONG fluidized bed, respectively, and the effect of the catalyst particle morphology on the active phase and residual oil hydrogenation performance was systematically studied. Multiple techniques, including X-ray diffraction (XRD), N₂adsorption-desorption, H₂ temperature-programmed reduction (H₂-TPR), high-resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS) and electron microprobe analysis (EMPA), were employed to determine the physico-chemical properties of the catalysts. It was found that spherical catalyst had more active Type Ⅱ MoS₂ phase, excellent textural properties and better fluidization characteristic,which made it exhibited superior hydrogenation activity than that in cylindrical catalyst. The weaker metal-support interaction in spherical catalyst is beneficial for a higher sulfidation degree and the formation of Ni-Mo-S Type Ⅱ active phase with a higher staking degree. Moreover, the spherical catalyst with a larger pore size and pore volume facilitates the diffusion of larger molecular impurities into the pore and adsorption on the catalyst active sites, which results in a uniform distribution of metal deposits in the spherical catalyst rather than concentrated distribution near the pore mouth. Finally, spherical catalyst with a smaller pore size may be easier to be fluidized, enhancing the mass transfer performance of the catalyst. The results provide new ideas for the design and development of more efficient industrial hydrogenation catalyst based on morphology effect.

Key words: catalysis, hydrogenation, alumina, morphology effect, ebullated bed, residue

中图分类号:

TE 624

朱慧红, 茆志伟, 杨涛, 冯翔, 金浩, 彭冲, 杨朝合, 王继锋, 方向晨. 催化剂形貌对沸腾床渣油加氢Ni-Mo/Al₂O₃ 催化剂活性位的影响机制[J]. 化工学报, 2021, 72(4): 2076-2085.

ZHU Huihong, MAO Zhiwei, YANG Tao, FENG Xiang, JIN Hao, PENG Chong, YANG Chaohe, WANG Jifeng, FANG Xiangchen. Influence mechanism of catalyst morphology on the active sites of Ni-Mo/ Al₂O₃ catalyst for ebullated bed residue hydrogenation[J]. CIESC Journal, 2021, 72(4): 2076-2085.

图/表 10

图1 沸腾床渣油加氢工艺流程示意图

Fig.1 Schematic process flow diagram of ebullated bed residue hydrotreating

图2 球形和圆柱形催化剂的XRD谱图

Fig.2 XRD patterns of the spherical and cylindrical catalysts

表1 球形和圆柱形Ni-Mo/Al2O3催化剂的结构性质

Table 1 Structural and textural properties of spherical and cylindrical Ni-Mo/Al2O3 catalysts

催化剂	长度/mm	直径/mm	体积当量直径/mm	比表面积/(m²·g^-1)	平均孔径/nm	孔体积/(ml·g^-1)
球形	—	0.4~0.5	0.4~0.5	163	15.34	0.625
圆柱形	3~5	0.8	1.42~1.69	169	13.61	0.575

图3 圆柱形(a)和球形(b) Ni-Mo/Al2O3催化剂的HRTEM图以及Ni-Mo-S纳米簇模型结构（S：黄色；Mo：蓝色；Ni：红色）

Fig.3 HRTEM images of the cylindrical (a) and spherical (b) Ni-Mo/Al2O3 catalysts and Ni-Mo-S nanocluster model (S: yellow; Mo: blue; Ni: red)

表2 球形和圆柱形Ni-Mo/Al2O3催化剂的HRTEM分析结果

Table 2 HRTEM analysis data of spherical and cylindrical Ni-Mo/Al2O3催化剂

催化剂	球形	圆柱形
最大颗粒长度/nm	6.5	4.41
平均颗粒长度/nm	3.67	2.94
平均堆垛层数	2.46	2.07
1~2层百分比/%	55.2	69.8
3~4层百分比/%	41.8	28.3
≥ 5层百分比/%	3	1.9
分散度 $f M o$ /%	29.8	36.9

表2 球形和圆柱形Ni-Mo/Al2O3催化剂的HRTEM分析结果

Table 2 HRTEM analysis data of spherical and cylindrical Ni-Mo/Al2O3催化剂

催化剂	球形	圆柱形
最大颗粒长度/nm	6.5	4.41
平均颗粒长度/nm	3.67	2.94
平均堆垛层数	2.46	2.07
1~2层百分比/%	55.2	69.8
3~4层百分比/%	41.8	28.3
≥ 5层百分比/%	3	1.9
分散度 $f M o$ /%	29.8	36.9

图4 球形和圆柱形Ni-Mo/Al2O3催化剂的H2-TPR曲线

Fig.4 H2-TPR profiles of the spherical and cylindrical catalysts

图5 球形和圆柱形Ni-Mo/Al2O3催化剂的XPS谱图

Fig.5 XPS spectra of the spherical and cylindrical catalysts

图6 失活的球形[（a）,（c）]和圆柱形[（b）,（d）]催化剂颗粒横截面上Ni、V、Fe和C的电子微探针分析和分布曲线

Fig.6 Electron probe microanalysis and distribution curves of Ni, V, Fe and C on the cross-section of spent cylindrical [(a), (b)] and spherical [(c), (d)] catalyst pellets

表3 减压渣油的性质

Table 3 Properties of the vacuum residue

参数	数值
H含量/%	10.58
C含量/%	85.41
S含量/%	3.64
Ni/V含量/(μg·g^-1)	62.94/160
CCR含量/%	20.3
密度(20℃)/(g·cm^-3)	1.0102
四组分分析
饱和分/%	19.63
芳香分/%	49.53
胶质/%	27.64
沥青质/%	3.2
>500℃收率/%	96.1

图7 球形和圆柱形催化剂的加氢催化性能(温度410℃，压力15 MPa，H2/油600∶1，空速0.5 h-1)

Fig.7 Catalytic performance of hydrotreating using spherical cylindrical catalysts

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催化剂形貌对沸腾床渣油加氢Ni-Mo/Al₂O₃ 催化剂活性位的影响机制

Influence mechanism of catalyst morphology on the active sites of Ni-Mo/ Al₂O₃ catalyst for ebullated bed residue hydrogenation

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