Study on the Effect of Metal Dispersion on the Catalytic Activity of Nickel⁃Based Catalysts

doi:10.3969/j.issn.1006-396X.2022.05.008

Abstract

Abstract:

NiMo/γ?Al₂O₃ catalyst was prepared by using γ?Al₂O₃ as the carrier and Ni as the active component,and Mo was introduced to improve the metal dispersion of Ni?based catalysts.The physical properties of the catalysts were characterized by means of BET,XRD,H₂?TPD,H₂?TPR,and transmission electron microscopy.The performance of the catalysts was evaluated by hydrogenation units,and the effect of metal dispersion of the catalysts on the catalytic activity was investigated.The results show that the introduction of Mo can effectively weaken the interaction between Ni and the carrier.The low?temperature reduction peak of the H₂?TPR profile significantly moves forward,and the peak intensity is enhanced.The specific surface area of the catalyst activity increases from 0.7 m²/g to 15.3~16.1 m²/g,and the metal dispersion increases from 0.80% to 18.59%,which indicates that the number of metal active centers on catalyst surfaces increases,and the metal dispersion on the catalyst surfaces improves. Under the same process condition,heavy petrol with catalytic cracking is processed,and the desulfurization rate of NiMo?based catalysts is increased by 15.7% compared with that of Ni?based catalysts.The saturation rate of olefin is increased by 4.9%,and the desulfurization selectivity is decreased by 3.4%.Therefore,the NiMo?based catalysts have positive desulfurization selectivity while ensuring a high desulfurization rate.

Key words: Metal dispersion, Nickel?based catalysts, Hydrodesulfurization, Catalytic activity, Selectivity

摘要：

以γ?Al₂O₃为载体、Ni为活性组元，通过引入助剂Mo改善Ni系催化剂金属分散度，制得NiMo/γ?Al₂O₃催化剂（NiMo系催化剂）。采用BET、XRD、H₂?TPD、H₂?TPR、透射电镜等多种表征手段对催化剂进行了物性表征，并利用加氢装置对催化剂性能进行评价，考察了金属分散度对催化剂催化活性的影响。结果表明，Mo的引入可有效减弱Ni与载体的相互作用，H₂?TPR谱图低温还原峰明显前移，峰强度增强，催化剂活性比表面积由0.7 m²/g增加到15.3~16.1m²/g，金属分散度由0.80%提高到18.59%，增加了催化剂表面金属活性中心数量，提高了催化剂表面金属分散度；在相同的工艺条件下处理催化裂化重汽油，NiMo系催化剂较Ni系催化剂脱硫率提高了15.7%，烯烃饱和率提高了4.9%，脱硫选择性降低了3.4%。由此可见，NiMo系催化剂兼具较好的脱硫性能和脱硫选择性。

关键词: 金属分散度, Ni基催化剂, 加氢脱硫, 催化活性, 选择性

CLC Number:

TQ138.1

Yana Ju, Yalin Zhang, Ran Zhang, Shaotong Song, Lü Zhongwu, Xiaoliang Yuan, Yang Li, Pei Wu. Study on the Effect of Metal Dispersion on the Catalytic Activity of Nickel⁃Based Catalysts[J]. Journal of Petrochemical Universities, 2022, 35(5): 71-77.

鞠雅娜, 张雅琳, 张然, 宋绍彤, 吕忠武, 袁晓亮, 李阳, 吴培. 金属分散度对Ni基催化剂催化活性的影响研究[J]. 石油化工高等学校学报, 2022, 35(5): 71-77.

Figures/Tables 9

Fig.1 N2 adsorption?desorption isotherm of the calalysts

Table 1 Specific surface area and pore volume of the catalysts

催化剂	比表面积/（m² $⋅$ g^-1）	孔体积/（cm³ $⋅$ g^-1）	平均孔径/nm	最可几孔径/nm
Ni系	130.3	0.57	14.50	15.19
NiMo系	149.7	0.64	14.24	15.49

Table 1 Specific surface area and pore volume of the catalysts

催化剂	比表面积/（m² $⋅$ g^-1）	孔体积/（cm³ $⋅$ g^-1）	平均孔径/nm	最可几孔径/nm
Ni系	130.3	0.57	14.50	15.19
NiMo系	149.7	0.64	14.24	15.49

Fig.2 XRD patterns of Al2O3 carrier and the different metal systems catalysts

Fig.3 TEM images of catalysts for Ni and NiMo series catalysts

Fig.4 H2?temperature programmed reduction of the different metal systems catalysts

Fig.5 H2?TPD profiles of Ni and NiMo series catalysts

Table 2 Catalyst activity specific surface for Ni and NiMo series catalysts

催化剂	m（催化剂）/g	Q $H 2 ⁃ T P D$ / （cm³ $⋅$ g^-1）	活性比表面积/（m² $⋅$ g^-1）
Ni系催化剂	0.200 3	0.21	0.7
NiMo⁃1催化剂	0.200 5	4.47	15.6
NiMo⁃2催化剂	0.200 4	4.38	15.3
NiMo⁃3催化剂	0.200 3	4.60	16.1

Table 2 Catalyst activity specific surface for Ni and NiMo series catalysts

催化剂	m（催化剂）/g	Q $H 2 ⁃ T P D$ / （cm³ $⋅$ g^-1）	活性比表面积/（m² $⋅$ g^-1）
Ni系催化剂	0.200 3	0.21	0.7
NiMo⁃1催化剂	0.200 5	4.47	15.6
NiMo⁃2催化剂	0.200 4	4.38	15.3
NiMo⁃3催化剂	0.200 3	4.60	16.1

Table 3 Comparative data of metal dispersion of Ni and NiMo series catalysts

催化剂

Q $H 2 ⁃ T P D$ /

（cm³ $⋅$ g^-1）

Q $H 2 ⁃ T P R$ /

（cm³ $⋅$ g^-1）

Table 3 Comparative data of metal dispersion of Ni and NiMo series catalysts

催化剂

Q $H 2 ⁃ T P D$ /

（cm³ $⋅$ g^-1）

Q $H 2 ⁃ T P R$ /

（cm³ $⋅$ g^-1）

分散度/%

Ni系催化剂

0.21

52.46

0.80

NiMo⁃1催化剂

4.47

48.09

18.59

Table 4 Evaluation results of the different metal systems hydrodesulfurization catalysts

原料及脱硫产品	w（硫）/（mg $⋅$ kg^-1）	脱硫率/%	φ/%					烯烃饱和率/%	脱硫选择性/%
原料及脱硫产品	w（硫）/（mg $⋅$ kg^-1）	脱硫率/%	正构烷烃	异构烷烃	烯烃	环烷烃	芳烃	烯烃饱和率/%	脱硫选择性/%
催化裂化重汽油原料	80.4	-	7.65	35.19	16.15	12.85	28.16	-	-
Ni系催化剂脱硫产品	27.3	66.0	7.81	35.38	15.16	12.99	28.66	6.1	91.5
NiMo系催化剂脱硫产品	14.7	81.7	8.32	35.41	14.38	13.36	28.53	11.0	88.1

Table 4 Evaluation results of the different metal systems hydrodesulfurization catalysts

原料及脱硫产品	w（硫）/（mg $⋅$ kg^-1）	脱硫率/%	φ/%					烯烃饱和率/%	脱硫选择性/%
原料及脱硫产品	w（硫）/（mg $⋅$ kg^-1）	脱硫率/%	正构烷烃	异构烷烃	烯烃	环烷烃	芳烃	烯烃饱和率/%	脱硫选择性/%
催化裂化重汽油原料	80.4	-	7.65	35.19	16.15	12.85	28.16	-	-
Ni系催化剂脱硫产品	27.3	66.0	7.81	35.38	15.16	12.99	28.66	6.1	91.5
NiMo系催化剂脱硫产品	14.7	81.7	8.32	35.41	14.38	13.36	28.53	11.0	88.1

References 16

1	牟应蓉，王晓京.镍基催化剂中镍铝尖晶石生成条件考察［J］.天然气化工，1990，3：26⁃30.
	Mu Y R，Wang X J.Investigation on the formation conditions of nickel⁃aluminum spinel in Ni based catalysts［J］.Natural Gas Chemical Industry，1990，3：26⁃30.
2	Seo J G，Youn M H，Song I K.Hydrogen production by steam reforming of LNG over Ni/Al₂O₃⁃ZrO₂ catalysts：Effect of Al₂O₃⁃ZrO₂ supports prepared by a grafting method［J］.Journal of Molecular Catalysis A：Chemical，2007，268：9⁃14.
3	Ding L，Zhang Z，Zheng Y，et al.Effect of fluorine and boron modification on the HDS，HDN and HAD activity of hydrotreating catalysts［J］.Applied Catalysis A：General，2006，301（2）：241⁃250.
4	杨义，杨成敏，周勇，等.柠檬酸对NiW/γ⁃Al₂O₃加氢脱硫催化剂性能的影响［J］.石油学报（石油加工），2012，28（2）：207⁃212.
	Yang Y，Yang C M，Zhou Y，et al.Effect of citric acid on the performance of NiW/γ⁃Al₂O₃ hydrodesulfurization catalysts［J］.Acta Petrolei Sinica （Petroleum Processing Section），2012，28（2）：207⁃212.
5	张登前，段爱军，赵震，等.NiMo/ZrO₂⁃Al₂O₃柴油深度加氢脱硫催化剂的研究［J］.工业催化，2008，16（10）：117⁃121.
	Zhang D Q，Duan A J，Zhao Z，et al.Study on NiMo/ZrO₂⁃Al₂O₃ catalysts for ultra deep HDS of diesel［J］.Industrial Catalysis，2008，16（10）：117⁃121.
6	武瑞明，张少华，王晓蔷，等.Ni⁃Mo⁃W非负载型催化剂加氢脱硫性能的改进［J］.石油化工，2018，47（4）：320⁃326.
	Wu R M，Zhang S H，Wang X Q，et al.Improvement of hydrodesulfurization performance of Ni⁃Mo⁃W unsupported catalyst［J］.Petrochemical Technology，2018，47（4）：320⁃326.
7	徐莹，王铁军，马隆龙，等.MoNi/γ⁃Al₂O₃催化剂的制备及其催化乙酸临氢酯化反应性能［J］.无机化学学报，2009，25（5）：805⁃811.
	Xu Y，Wang T J，Ma L L，et al.MoNi/γ⁃Al₂O₃ catalyst：Preparation and catalytic activity for acetic acid hydrotreating［J］.Chinese Journal of Inorganic Chemistry，2009，25（5）：805⁃811.
8	张红玉，熊国兴，盛世善，等.NiO/γ⁃Al₂O₃催化剂中NiO与γ⁃Al₂O₃间的相互作用［J］.物理化学学报，1999，15（8）：735⁃741.
	Zhang H Y，Xiong G X，Sheng S S，et al.Interaction of NiO with γ⁃Al₂O₃supporter of NiO/γ⁃Al₂O₃ catalysts［J］.Acta Physico⁃Chimica Sinica，1999，15（8）：735⁃741.
9	Li C P，Chen Y W.Temperature⁃programmed⁃reduction studies of nickel oxide/alumina catalysts：Effects of the preparation method［J］.Thermochimica Acta，1995，256（2）：457⁃465.
10	Arnoldy P，Franken M C，Scheffer B，et al.Temperature⁃programmed reduction of CoO⁃MoO₃/Al₂O₃ catalysts［J］.Journal of Catalysis，1985，96（2）：382⁃395.
11	石玉，江雅新，牛雪平，等.Mo⁃Ni/γ⁃Al₂O₃甲烷化催化剂研究（II）制备条件及还原条件对催化剂结构的影响［J］.内蒙古大学学报（自然科学版），2000，31（5）：487⁃492.
	Shi Y，Jiang Y X，Niu X P，et al.Study on Mo⁃Ni／γ⁃Al₂O₃ methanation catalysts）（Ⅱ） the effects of preparation and reduction conditions on the surface structure［J］.Acta Scientiarum Naturalium Universitatis NeiMongol，2000，31（5：487⁃492.
12	胡雪娟.ZrO₂及ZrO₂基复合载体负载镍催化苯加氢制环己烷的研究［D］.南昌：南昌大学，2007.
13	Han S J，Bang Y，Song J H，et al.Hydrogen production by steam reforming of ethanol over dual⁃tempated Ni⁃Al₂O₃ catalyst［J］.Catalysis Today，2016，265：103⁃110.
14	鞠雅娜，李天舒，张然，等.催化裂化重汽油临氢脱砷剂的研制及性能评价［J］.石油炼制与化工，2021，52（12）：21⁃26.
	Ju Y N，Li T S，Zhang R，et al.Preparation and performance evaluation of hydrogenation catalyst for selective arsenic removal from FCC heavy gasoline［J］.Petroleum Processing and Petrochemicals，2021，52（12）：21⁃26.
15	毛纾冰.表面原位合成法制备高分散镍催化剂及其催化加氢脱氯性能研究［D］.北京：北京化工大学，2005.
16	Daage M，Chianelli R R.Structure⁃function relations in molybdenum sulfide catalysts：The “Rim⁃Edge” Model［J］.Journal of Catalysis，1994，149（2）：414⁃427.

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[6]	. [J]. , 2016, 29(5): 1-8.
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