镁改性对Ni-Mo/Al2O3体系催化剂烯烃选择性能的影响

doi:10.19964/j.issn.1006-4990.2023-0561

Abstract

Abstract:

In order to explore the effect of additive modification on the selectivity of olefin aromatics in catalytic hydrogenation catalysts，a series of Mg-Al₂O₃ supports with different magnesium contents were prepared by ultrasonic⁃assisted precipitation，and then Ni-Mo/Mg-Al₂O₃ catalysts were prepared by equal volume impregnation method.The catalysts were characterized and analyzed by XRD，BET，XPS，NH₃-TPD，H₂-TPR，etc.The results showed that the introduction of magnesium additives and alumina support effectively improved the pore texture characteristics of the catalyst，reduced the acidity of the catalyst，improved the distribution morphology of the active components，and promoted the formation of more and more active NiMoS-Ⅱ phases.In the fixed⁃bed hydrogenation reactor，DCC gasoline was used as the evaluation raw material to explore the hydrodesulfurization and denitrification performance of the catalyst and the influence of the catalyst on the selectivity of aromatics and olefins.The results showed that the hydrodesulfurization and denitrification rate of the catalyst modified by magnesium additives could reach 99.9%，and when the amount of magnesium additives was 3%，the olefin saturation rate was greater than 99%，and the aromatic loss rate was only 7.2%.The introduction of magnesium additives effectively improved the hydrodesulfurization and denitrification capacity of the catalyst，and the selection performance of olefin aromatics of the catalyst could be adjusted by controlling the content of Mg additives，which had great research significance for the improvement of the selection performance of catalytic hydrogenation catalysts.

Key words: Mg modification, Ni-Mo/Mg-Al₂O₃, DCC gasoline, hydrodesulfurization, NiMoS-Ⅱ type, olefin aromatics selectivity

CLC Number:

TQ426

SONG Guoliang, MU Zhanpeng, YANG Xiaxia, LI Zihan, ZHU Jinjian, ZHANG Jingcheng, YANG Wenru, MA Wenqi. Effect of magnesium modulation of Ni-Mo/Al₂O₃ on selectivity of catalyst hydrogenation[J]. Inorganic Chemicals Industry, 2024, 56(7): 150-156.

Figures/Tables 12

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References 29

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催化剂	比表面积/（m²·g^-1）	孔体积/ （cm³·g^-1）	孔径/ nm	粒径分布/%
催化剂	比表面积/（m²·g^-1）	孔体积/ （cm³·g^-1）	孔径/ nm	<4 nm	4~<10 nm	10~20 nm
ZHC	281.9	0.44	8.07	5.6	63.8	20.7
ZHC-Mg-1	237.2	0.48	8.10	6.6	56.2	25.5
ZHC-Mg-2	183.8	0.44	9.61	4.8	61.3	22.6
ZHC-Mg-3	196.2	0.49	9.93	4.4	55.1	28.2
ZHC-Mg-4	186.1	0.45	9.78	4.2	57.9	24.8

催化剂	催化剂酸量/（mmol·m^-2）
催化剂	弱酸量	中强酸量	总酸量
ZHC	10.44	9.00	19.44
ZHC-Mg-1	9.73	9.34	19.07
ZHC-Mg-2	9.09	9.07	18.16
ZHC-Mg-3	9.28	8.92	18.21
ZHC-Mg-4	9.13	8.37	17.50

催化剂	分峰面积占比/%
催化剂	MoS₂	Mo⁵⁺	MoO₃	NiS	NiMoS	NiO
ZHS	50.82	30.6	18.58	20.2	59.63	20.17
ZHS-Mg-1	36.48	33.81	29.71	15.2	54.13	30.72
ZHS-Mg-2	37.89	29.92	32.19	2.9	63.94	34.77
ZHS-Mg-3	49.52	29.44	21.03	1.3	76.70	20.43
ZHS-Mg-4	40.48	31.83	27.69	9.2	61.51	29.27

项目	硫含量/ （μg·mL^-1）	氮含量/ （μg·mL^-1）	HDS转化率/％	HDN转化率/％
DCC汽油	265.3	139.9	—	—
ZHC	24.7	6.5	90.7	95.4
ZHC-Mg-1	3.2	1.4	98.7	98.9
ZHC-Mg-2	3.8	2.2	98.6	98.4
ZHC-Mg-3	0.2	＜0.1	99.9	＞99.9
ZHC-Mg-4	1.1	0.8	99.5	99.4

项目	密度/ （kg·m^-3）	w（芳烃）/%						w（烯烃）/％
项目	密度/ （kg·m^-3）	C6	C7	C8	C9	C10	总芳烃	w（烯烃）/％
DCC汽油	860.9	10.4	24.7	25.4	16.9	8.4	85.8	8.3
ZHC	843.0	9.7	23.4	23.4	14.8	5.9	77.2	1.2
ZHC-Mg-1	838.9	9.0	23.2	23.5	14.9	5	75.6	0.6
ZHC-Mg-2	841.6	8.3	22.5	23.9	15.8	7.6	78.1	0.5
ZHC-Mg-3	841.4	7.6	23.5	24.4	16.6	7.5	79.6	0.1
ZHC-Mg-4	841.3	10.6	23.1	23.1	14.1	6.2	77.1	0.3

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Effect of magnesium modulation of Ni-Mo/Al₂O₃ on selectivity of catalyst hydrogenation

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Effect of magnesium modulation of Ni-Mo/Al2O3 on selectivity of catalyst hydrogenation