Effect of Citric Acid on the Activity of NiMoP/Al2O3⁃USY Catalyst

doi:10.3969/j.issn.1006-396X.2022.01.006

Abstract

Abstract:

Using Ni and Mo as active components and Al₂O₃?USY as support material, the effect of citric acid on the catalytic activity of NiMoP was investigated. The results indicate that the total acid content on the surface of catalyst increases at first and reaches its maximum in the condition of n_L/n_Ni=1.0, then decreases as the increasing concentration of citric acid. Meanwhile, the stacking layer number of active phase MoS₂ and the average lamellar length are gradually increased. When the mole ratio of citric acid to Ni is 1.0(n_L/n_Ni=1.0), the catalyst shows the best activity. And the HDS and HDN rate at 340 ℃ reach to 99.6% and 99.7% respectively, which are better than the catalyst without modifying by citric acid.

Key words: Citric acid, Active phase, Acid content, Catalytic activity

摘要：

以Ni、Mo为活性组分，Al₂O₃?USY为载体，通过向NiMoP浸渍液中添加柠檬酸，考察柠檬酸对催化剂催化活性的影响。对催化剂进行表征，结果表明随着浸渍液中柠檬酸浓度增大，催化剂表面总酸量呈先增加后减小的趋势，当n_L/n_Ni=1.0时，催化剂表面酸量最大；催化剂活性相MoS₂堆积层数逐渐增加，平均片层长度逐渐增大。340 ℃实验条件下，当n_L/n_Ni=1.0时，催化剂的催化活性最好，脱硫率和脱氮率分别为99.6%、99.7%，优于未添加柠檬酸的催化剂。

关键词: 柠檬酸, 活性相, 酸量, 催化活性

CLC Number:

TE624

Fengxu Li, Chenglin Wang, Zenghui Shang, Xianzhao Li. Effect of Citric Acid on the Activity of NiMoP/Al₂O₃⁃USY Catalyst[J]. Journal of Petrochemical Universities, 2022, 35(1): 35-40.

李凤绪, 王成林, 尚增辉, 李宪昭. 柠檬酸对NiMoP/Al₂O₃⁃USY催化剂活性影响[J]. 石油化工高等学校学报, 2022, 35(1): 35-40.

Figures/Tables 9

Table 1 The experiment instruments and equipments

名称	型号	厂家
X射线衍射仪	X’Pert Pro MPD	荷兰帕纳科公司
红外光谱仪	Nicolet⁃58SXC	美国Nicolet公司
透射电镜	JEM⁃2100	日本JROL公司

Table 2 The properties of Shenghua FCC diesel

密度/（g $⋅$ cm^-3）	w（硫）/（µg $⋅$ g^-1）	w（氮）/（µg $⋅$ g^-1）
0.897 9	5 111.9	744.5

Table 2 The properties of Shenghua FCC diesel

密度/（g $⋅$ cm^-3）	w（硫）/（µg $⋅$ g^-1）	w（氮）/（µg $⋅$ g^-1）
0.897 9	5 111.9	744.5

Fig.1 Distribution of sulfur compounds in Shenghua FCC diesel oil

Fig.2 XRD pattern of catalyst

Fig.3 Py?IR pattern of catalyst

Fig.4 HRTEM images of the spent catalysts

Table 3 Average stacking degree(NA), slab length(LA) of MoS2

催化剂	N_A	L_A/nm
A	3.05	3.95
B	3.32	4.25
C	3.51	4.91
D	3.64	4.95
E	4.00	5.65

Fig.5 MoS2 stacking number distribution of spent catalysts

Table 4 Properties of production from series of catalysts

催化剂	t/℃	密度/（g $⋅$ cm^-3）	w（N）/（µg $⋅$ g^-1）	脱氮率/%	w（S）/（µg $⋅$ g^-1）	脱硫率/%
	300	0.879 3	473.3	36.4	529.1	89.6
A	320	0.874 0	84.4	88.6	187.3	96.3
	340	0.863 6	4.2	99.4	34.4	99.3
	300	0.879 4	454.0	39.0	466.1	90.8
B	320	0.871 5	68.4	90.9	155.8	96.9
	340	0.864 4	3.7	99.5	30.6	99.4
	300	0.878 7	418.3	43.8	432.6	91.5
C	320	0.871 0	45.5	93.8	117.6	97.7
	340	0.863 0	2.5	99.7	20.8	99.6
	300	0.879 3	442.5	40.5	574.6	88.7
D	320	0.871 2	79.1	90.7	191.1	96.2
	340	0.865 9	11.9	98.4	59.1	98.8
	300	0.880 3	497.4	35.8	642.4	87.4
E	320	0.873 8	102.1	88.9	220.7	95.6
	340	0.867 1	26.1	96.4	85.8	98.3

Table 4 Properties of production from series of catalysts

催化剂	t/℃	密度/（g $⋅$ cm^-3）	w（N）/（µg $⋅$ g^-1）	脱氮率/%	w（S）/（µg $⋅$ g^-1）	脱硫率/%
	300	0.879 3	473.3	36.4	529.1	89.6
A	320	0.874 0	84.4	88.6	187.3	96.3
	340	0.863 6	4.2	99.4	34.4	99.3
	300	0.879 4	454.0	39.0	466.1	90.8
B	320	0.871 5	68.4	90.9	155.8	96.9
	340	0.864 4	3.7	99.5	30.6	99.4
	300	0.878 7	418.3	43.8	432.6	91.5
C	320	0.871 0	45.5	93.8	117.6	97.7
	340	0.863 0	2.5	99.7	20.8	99.6
	300	0.879 3	442.5	40.5	574.6	88.7
D	320	0.871 2	79.1	90.7	191.1	96.2
	340	0.865 9	11.9	98.4	59.1	98.8
	300	0.880 3	497.4	35.8	642.4	87.4
E	320	0.873 8	102.1	88.9	220.7	95.6
	340	0.867 1	26.1	96.4	85.8	98.3

References 28

1	徐永强，赵瑞玉，商红岩，等.二苯并噻吩和4⁃甲基二苯并噻吩在Mo和CoMo/γ⁃Al₂O₃催化剂上加氢脱硫的反应机理［J］.石油学报（石油加工），2003，19（5）：14⁃21.
	Xu Y Q，Zhao R Y，Shang H Y，et al.Mechanism of hydrodesulfurization of dibenzothiophene and 4⁃methyldibenzo⁃thiophene on Mo/γ⁃Al₂O₃ and CoMo/γ⁃Al₂O₃［J］.Acta Petrolei Sinica（Petroleum Processing Section），2003，19（5）：14⁃21.
2	左东华，谢玉萍，聂红，等.4，6⁃二甲基二苯并噻吩脱硫机理的研究［J］.催化学报，2002，23（3）：271⁃275.
	Zuo D H，Xie Y P，Nie H，et al.Study on hydrodesulfurization mechanism of 4，6⁃dimethyldibenzothiophene［J］.Chinese Journal of Catalysis，2002，23（3）：271⁃275.
3	Wu L，Liu Y Z.Environmental impacts of hydrotreating processes for the production of clean fuels based on life cycle assessment［J］.Fuel，2016，164：352⁃360.
4	杨哲.从国外油品质量升级看我国汽油柴油标准的发展与对策［J］.炼油技术与工程，2004，34（10）：2⁃4.
	Yang Z.Development of domestic gasoline & diesel standards and countermeasures［J］.Petroleum Refinery Engineering，2004，34（10）：2⁃4.
5	Villarroel M，Baeza P，Gracia F，et al.Phosphorus effect on Co⁃Mo and Ni⁃Mo synergism in hydrodesulphurization catalysts［J］.Applied Catalysis A：General，2009，364（1⁃2）：75⁃79.
6	王成林，李凤绪，袁倩，等.磷和超稳Y分子筛在深度脱硫过程中增强效应的研究［J］.当代化工，2015，44（3）：377⁃480.
	Wang C L，Li F X，Yuan Q，et al.Study on enhancement effect between phosphorus and USY zeolitein the process of deep desulfurization［J］.Contemporary Chemical Industry，2015，44（3）：377⁃480.
7	Villarroel M，Baeza P，Gracia F，et al.Phosphorus effect on Co⁃Mo and Ni⁃Mo synergism in hydrodesulphurization catalysts［J］.Applied Catalysis A：General，2009，364（1⁃2）：75⁃79.
8	陈子莲，王继锋，杨占林，等.硼对Ni/Mo⁃γ⁃Al₂O₃加氢处理催化剂性能影响［J］.石油学报（石油加工），2016，32（1）：55⁃63.
	Chen Z L，Wang J F，Yang Z L，et al. Effect of boron promoter on the performance of NiMo/γ⁃Al₂O₃ hydrotreating catalyst ［J］.Acta Petrolei Sinica（Petroleum Processing Section），2016，32（1）：55⁃63.
9	Sun M Y，Nicosia D，Prins R.The effects of ﬂuorine， phosphate and chelating agents on hydrotreating catalysts and catalysis［J］.Catalysis Today，2003，86（1⁃4）：173⁃189.
10	孙万堂，王广建，王堂博，等.螯合剂对加氢精制催化剂的影响［J］.炼油技术与工程，2016，46（3）：1⁃5.
	Sun W T，Wang G J，Wang T B，et al.Impact of chelating agents on preparing hydrotreating catalysts［J］.Petroleum Refinery Engineering，2016，46（3）：1⁃5.
11	薛冬，吕振辉.柠檬酸添加方式对Mo⁃Ni⁃P/Al₂O₃催化剂加氢活性的影响［J］.分子催化，2017，31（4）：382⁃388.
	Xue D，Lü Z H.Effect of addition method of critric acid on hydrogenation performance of avtivity of Mo⁃Ni⁃P/Al₂O₃ catalyst ［J］.Journal of Molecular Catalysis（China），2017，31（4）：382⁃388.
12	Lélias M A，Van G J，Maugé F，et al.Effect of NTA addition on the formation， structure and activity of the active phase of cobalt⁃molybdenum sulfide hydrotreating catalysts［J］.Catalysis Today，2008，130：109⁃116.
13	张国辉，于海斌，张景成，等.氨基三乙酸对Ni⁃Mo/Al₂O₃催化裂化柴油加氢脱硫脱氮活性的影响［J］.石油炼制与化工，2016，47（5）：57⁃61.
	Zhang G H，Yu H B，Zhang J C，et al.Nitrilotriacetic acid on HDS and HDN activity of Ni⁃Mo/Al₂O₃ for FCC diesel［J］.Petroleum Processing and Petrochemicals，2016，47（5）：57⁃61.
14	周同娜.乙二醇对NiMoP/Al₂O₃催化剂上喹啉加氢脱氮反应的影响［J］.工业催化，2013，21（2）：48⁃50.
	Zhou T N.Influence of glycol on activities of NiMoP/Al₂O₃ catalysts for quinoline hydrodenitrogenation［J］.Industrial Catalysis，2013，21（2）：48⁃50.
15	洪帅领，杨丽娜，白金，等.柠檬酸调变加氢精制催化剂的研究进展［J］.石油化工，2020，49（3）：297⁃302.
	Hong S L，Yang L N，Bai J，et al.Research progress of citric acid for modifying hydrofining catalyst［J］.Petrochemical Technology，2020，49（3）：297⁃302.
16	朱立，周亚松，魏强，等.柠檬酸⁃水热组合改性对NiW/Al₂O₃催化剂加氢性能的影响［J］.石油学报（石油加工），2013，29（5）：773⁃777.
	Zhu L，Zhou Y S，Wei Q，et al.Effect of citric acid assisted hydrothermal modification on the hydrogenation performance of NiW/Al₂O₃ catalyst［J］.Acta Petrolei Sinica（Petroleum Processing Section），2013，29（5）：773⁃777.
17	Sun M Y，Nicosia D，Prins R.The effects of fuorine， phosphate and chelating agents on hydrotreating catalysts and catalysis［J］.Catalysis Today，2003，86（1⁃4）：173⁃189.
18	Zhang L，Fu W Q，Yu Q Y，et al.Effect of citric acid addition on the morphology and activity of Ni₂P supported on mesoporous zeolite ZSM⁃5 for the hydrogenation of 4，6⁃DMDBT and phenanthrene［J］.Journal of Catalysis，2017，345：295⁃307.
19	宋华，张永江，宋华林，等.柠檬酸对Ni₂P/TiO₂⁃Al₂O₃催化剂加氢脱硫性能的影响［J］.物理化学学报，2012，28（3）：661⁃666.
	Song H，Zhang Y J，Song H L，et al.Effect of citric acid on the hydrodesulfurization performance of Ni₂P/TiO₂⁃Al₂O₃ catalyst［J］.Acta Physico⁃Chimica Sinica，2012，28（3）：661⁃666.
20	户安鹏，陈文斌，龙湘云，等.柠檬酸对NiMo/γ⁃Al₂O₃催化剂中助剂Ni作用的影响［J］.石油炼制与化工，2018，49（10）：52⁃57.
	Hu A P，Chen W B，Long X Y，et al.Effect of citric acid on role of promoter Ni in NiMo/γ⁃Al₂O₃ catalyst［J］.Petroleum Processing and Petrochemicals，2018，49（10）：52⁃57.
21	邱海峰，汤晟，孔祥敏，等.柠檬酸促进NiMoP/Al₂O₃催化剂上喹啉加氢脱氮性能的研究［J］.石油炼制与化工，2019，50（4）：32⁃38.
	Qiu H F，Tang S，Kong X M，et al.Influence of citric acid on the performance of NiMoP/Al₂O₃ catalysts for quinolone hydrodenitrogenation［J］.Petroleum Processing and Petrochemicals，2019，5（4）：32⁃38.
22	吕伟超，周亚松，李瑞峰，等.柠檬酸与磷的改性对Ni⁃Mo/Al₂O₃焦化蜡油加氢脱氮性能的影响［J］.石油学报（石油加工），2014，30（2）：218⁃223.
	Lü W C，Zhou Y S，Li R F，et al.Effect of the modification by citric acid cooperating with phosphorus on the hydrodenitrogenation performance of Ni⁃Mo/Al₂O₃ for coking gas oil［J］.Acta Petrolei Sinica（Petroleum Processing Section），2014，30（2）：218⁃223.
23	聂红，龙湘云，刘清河，等.柠檬酸对NiW/Al₂O₃加氢脱硫催化剂硫化行为的影响［J］.石油学报（石油加工），2010，26（2）：329⁃335.
	Nie H，Long X Y，Liu Q H，et al.Effect of citric acid on sulfidation behavior of NiW/Al₂O₃ hydrodesulfurization catalysts［J］.Acta Petrolei Sinica（Petroleum Processing Section），2010，26（2）：329⁃335.
24	林凌，伊晓东，邱波，等.钼镍磷溶液的制备与表征［J］.石油学报（石油加工），2009，25（2）：173⁃177.
	Lin L，Yin X D，Qiu B，et al.Prepartion and characterization of Mo⁃Ni⁃P⁃O solution［J］.Acta Petrolei Sinica（Petroleum Processing Section），2009，25（2）：173⁃177.
25	朱玉霞，林伟，田辉平，等.固体酸催化剂酸性分析方法的研究进展［J］.石油化工，2006，35（7）：607⁃614.
	Zhu Y X，Lin W，Tian H P，et al.Advances in acidity characterization of solid acid catalysts［J］.Petrochemical Technology，2006，35（7）：607⁃614.
26	Emeis C A.Determination of integrated molar extinction coefficients for infrared absorption bonds of pyridine adsorbed on solid acid catalysts［J］.Journal of Catalysis，1993，141（20）：347⁃354.
27	Topsøe H.The role of Co-Mo-S type structures in hydrotreating catalysts［J］.Applied Catalysis A：General，2007，322：3⁃8.
28	周同娜，尹海亮.柠檬酸促进NiMoP催化剂上二苯并噻吩脱硫反应［J］.工业催化，2013，21（1）：12⁃14.
	Zhou T N，Yin H L.Promotion of citric acid to dibenzothiophene hydrodesulfurization activities over NiMoP catalysts［J］.Industrial Catalysis，2013，21（1）：12⁃14.

[1]	Xueshi Song, Weili Qu, Lei Zhao, Zhenbo Wang. Research Progress of Pt⁃Based Catalysts for Oxygen Reduction in Proton Exchange Membrane Fuel Cells [J]. Journal of Petrochemical Universities, 2023, 36(4): 25-33.
[2]	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.
[3]	Yuchao Cui, Yuchai Qin, Wenyan Wang, Wei Wu, Qiang Zhang, Lijuan Song. Effect of WO _x Dispersion by SBA⁃15 Carrier on Olefin Disproportionation [J]. Journal of Petrochemical Universities, 2022, 35(1): 23-28.
[4]	. Effect of pH on Bi₂O₃ Phase Transition Process and Photocatalytic Performance [J]. Journal of Petrochemical Universities, 2017, 30(6): 6-11.
[5]	Zhang Zhiwei, Ding Wei, Zhao Dezhi, Song Guanlong, Zhang Qiang. Preparation and Hydrodesulfurization Performance of New Kind of Diesel Oil Hydrogenation Catalyst [J]. Journal of Petrochemical Universities, 2016, 29(4): 7-12.
[6]	LI Cuiqing, ZHANG Mengdi, SHEN Zhiwei, et al. Effect of Citric Acid on Hydrodesulfurization Activities of  Thiophene for Tungsten Phosphide Catalysts [J]. Journal of Petrochemical Universities, 2013, 26(5): 1-5.
[7]	LONG Xiao-zhu, TIAN Yan-wen, WANG Chang-song,et al. Synthesis ，Characterization and Its Application in Diesel Fuel of CBC － NO Claw Macromolecule [J]. Journal of Petrochemical Universities, 2009, 22(2): 12-16.
[8]	WANG Ji-yuan,GU Yue-feng,CHEN Shao-hui,et al. Effect of Peptizers on Properties of Formed TiO₂Supports [J]. Journal of Petrochemical Universities, 2009, 22(1): 26-30.
[9]	LIU Lin， XING Jin-juan， QIAN Jian-huan， ZHANG Qin-chun. The Synthesis of 1-Chloro-2,4,5-Trimethyl-Benzene [J]. Journal of Petrochemical Universities, 2008, 21(2): 53-54.
[10]	ZHANG Ling - ling,LI Feng - yan,ZHAO Tian - bo,WANG Yue. Characteristics and Catalytic Performance of Nanocrys talline and Non - Nanocry stalline ZSM - 5 Zeolites [J]. Journal of Petrochemical Universities, 2007, 20(1): 31-34.

Effect of Citric Acid on the Activity of NiMoP/Al₂O₃⁃USY Catalyst

柠檬酸对NiMoP/Al₂O₃⁃USY催化剂活性影响

HTML

PDF

Knowledge

Abstract

Cite this article

share this article

Figures/Tables 9

References 28

Related Articles 10

Recommended Articles

Metrics