镍对Pt/γ-Al2O3催化剂稠环芳烃选择性加氢性能的影响

doi:10.19964/j.issn.1006-4990.2022-0306

Abstract

Abstract:

A series of Pt/γ-Al₂O₃ catalysts with different nickel loading were prepared successfully by impregnation method used chloroplatinic acid hexahydrate and nickel nitrate as Pt and Ni precursors,respectively.The samples were characterized via inductively coupled plasma-atomic emission spectrometry（ICP-AES）,nitrogen physical adsorption,ammonia-temperature programmed desorption（NH₃-TPD）,hydrogen-temperature programmed reduction（H₂-TPR）,hydrogen-temperature programmed desorption（H₂-TPD）,hydrogen-oxygen titration stoichiometry（H₂-O₂）.Using reformed C₁₀⁺ heavy aromatics as raw materials,the effect of nickel introduction on the selective hydrogenation performance of polycyclic aromatic hydrocarbons（PAHs） of Pt/γ-Al₂O₃ catalyst was investigated in a 30 mL fixed bed device.The fixed bed evaluation results showed that with the increase of nickel content,the hydrogenation activity of PAHs and the selectivity of monocyclic aromatic hydrocarbons were increased firstly and then decreased,when 0.5%（mass fraction） nickel was introduced into 0.1Pt/γ-Al₂O₃ catalyst,the hydrogenation activity and selectivity of PAHs were the best.At the same time,the conversion rate of PAHs was about 75%,and the selectivity of monocyclic aromatic hydrocarbons was more than 98%.Combined with the characterization results of H₂-TPR,H₂-TPD and H₂-O₂ titration,it was analyzed that the main reason was that the introduction of a certain amount of nickel improved the dispersion of platinum.At the same time,due to the low hydrogenation activation energy of platinum,platinum migrated to non precious metal nickel through overflow activated hydrogen,which improved the hydrogenation performance of metal nickel.In addition,the existence of platinum could also prevent nickel from forming spinel structure and other inactive phases,promote the reduction of nickel oxide,and then improve the activity,selectivity and stability of the catalyst for the hydrogenation of PAHs.

Key words: nickel, Pt/γ-Al₂O₃, polyaromatic hydrocarbons, monoaromatic hydrocarbons, selective hydrogenation

CLC Number:

TQ138.13

JIN Fengying,YU Haibin,WANG Yaquan,ZANG Jiazhong,GUO Chunlei,LIU Hang,MA Mingchao,ZHAO Xunzhi,LIU Kailong. Effect of Ni on selective hydrodegenation of polyaromatic hydrocarbons of Pt/γ-Al₂O₃ catalyst[J]. Inorganic Chemicals Industry, 2022, 54(10): 141-148.

Figures/Tables 12

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References 23

[1]	赵仁殿, 金彰礼, 陶志华, 等. 芳烃工学[M].北京:化学工业出版社, 2001: 251-256.
	ZHAO Rendian, JIN Zhangli, TAO Zhihua, et al.Aromatics engineering[M].Beijing:Chemical Industry Press（CIP）, 2001: 251-256
[2]	孔德金, 祁晓岚, 朱志荣, 等. 重芳烃轻质化技术进展[J].化工进展, 2006, 25(9): 983-987.
	KONG Dejin, QI Xiaolan, ZHU Zhirong, et al.Technological advances in conversion of heavy aromatics to light aromatics[J].Chemical Industry and Engineering Progress, 2006, 25(9): 983-987
[3]	臧甲忠, 郭春垒, 范景新, 等. C₉ ⁺重芳烃增产BTX技术进展[J].化工进展, 2017, 36(4): 1278-1287.
	ZANG Jiazhong, GUO Chunlei, FAN Jingxin, et al.Advance in BTX production increase technology from C₉ ⁺ heavy aromatics[J].Chemical Industry and Engineering Progress, 2017, 36(4): 1278-1287.
[4]	范景新, 臧甲忠, 于海斌, 等. 重芳烃轻质化研究进展[J].工业催化, 2015, 23(9): 666-673.
	FAN Jingxin, ZANG Jiazhong, YU Haibin, et al.Research progress in conversion of heavy aromatics to light ones[J].Industrial Catalysis, 2015, 23(9): 666-673.
[5]	杨纪, 靳凤英, 范景新, 等. 分子筛重芳烃加氢脱烷基催化剂研究进展[J].无机盐工业, 2017, 49(6): 1-6.
	YANG Ji, JIN Fengying, FAN Jingxin, et al.Research progress of zeolites in catalysts for hydrodealkylation of heavy aromatics[J].Inorganic Chemicals Industry, 2017, 49(6): 1-6.
[6]	许杰, 尹宏峰.重芳烃油加氢精制催化剂及重芳烃油生产BTX的方法: 中国,114433119A[P].2022-05-06.
	XU Jie, YIN Hongfeng.A method for preparing hydrofining catalysts and producing BTX of heavy aromatic oil:CN,114433119A[P].2022-05-06.
[7]	李水荣, 徐保岳, 楼巧琳.一种重芳烃油加氢精制催化剂及重芳烃油加工方法: 中国,114433111A[P].2022-05-06.
	LI Shuirong, XU Baoyue, LOU Qiaolin.A method for preparing hydrofining catalysts and conversion of heavy aromatic hydrocarbons:CN,114433111A[P].2022-05-06.
[8]	刘航, 臧甲忠, 范景新, 等. 重芳烃轻质化催化剂n（Ni）/n（Ni+Mo）的优化与分析[J].无机盐工业, 2021, 53(12): 140-145.
	LIU Hang, ZANG Jiazhong, FAN Jingxin, et al.Optimization and analysis of n（Ni）/n（Ni+Mo） of heavy aromatics to light aromatics catalyst[J].Inorganic Chemicals Industry, 2021, 53(12): 140-145
[9]	陈庆龄, 孔德金, 杨卫胜.对二甲苯增产技术发展趋向[J].石油化工, 2004, 33(10): 909-915.
	CHEN Qingling, KONG Dejin, YANG Weisheng.Developmental trends in p-xylene production increasing technology[J].Petrochemical Technology, 2004, 33(10): 909-915.
[10]	祁晓岚, 左煜, 陈雪梅, 等. HAT-plus重芳烃轻质化技术[J].石油学报:石油加工, 2008, 24(S1): 338-341.
	QI Xiaolan, ZUO Yu, CHEN Xuemei, et al.HAT-plus technology for conversion of heavy aromatics to light aromatics[J].Acta Petrolei Sinica:Petroleum Processing Section, 2008, 24(S1): 338-341.
[11]	程文才, 杨德琴, 朱志荣, 等. 用于重质芳烃加氢脱烷基与烷基转移的催化剂:中国,1055959C[P].2000-08-30.
	CHENG Wencai, YANG Deqin, ZHU Zhirong, et al.Catalysts for hydrodealkylation and alkylation of heavy aromatics:CN,1055959C[P].2000-08-30.
[12]	李经球, 孔德金, 郭毅.用于重芳烃转化的催化反应系统和催化重芳烃转化的方法:中国,114436736A[P].2022-05-06
	LI Jingqiu, KONG Dejin, GUO Yi.Catalytic reaction system and catalysts preparation for conversion of heavy aromatics:CN,114436736A[P].2022-05-06.
[13]	黄新露.重芳烃高效转化生产轻芳烃技术[J].化工进展, 2013, 32(9): 2263-2266.
	HUANG Xinlu.Technology for producing light aromatics from heavy aromatics[J].Chemical Industry and Engineering Progress, 2013, 32(9): 2263-2266.
[14]	YASUDA H, YOSHIMURA Y.Hydrogenation of tetralin over zeolite-supported Pd-Pt catalysts in the presence of dibenzothiophene[J].Catalysis Letters, 1997, 46(2): 43-48.
[15]	KISHORE KUMAR S A, JOHN M, PAI S M, et al.Low temperature hydrogenation of aromatics over Pt-Pd/SiO₂-Al₂O₃ cataly-st[J].Fuel Processing Technology, 2014, 128: 303-309.
[16]	TÉLLEZ-ROMERO J G, CUEVAS-GARCÍA R, RAMÍREZ J, et al.Simultaneous naphthalene and thiophene hydrogenation over Ni（X）-Pt/HMOR catalysts[J].Catalysis Today, 2015, 250: 12-20
[17]	姬宝艳.镍基催化剂上稠环芳烃选择性加氢的研究[D].西安:西北大学, 2017.
	JI Baoyan.Selective hydrogenation of polycyclic aromatic hydrocarbons over Ni catalysts[D].Xi'an:Northwest University, 2017.
[18]	PAWELEC B, PAROLA V L, THOMAS S, et al.Enhancement of naphthalene hydrogenation over PtPd/SiO₂-Al₂O₃ catalyst modified by gold[J].Journal of Molecular Catalysis A:Chemical, 2006, 253(1/2): 30-43.
[19]	杨基和, 旷俊杰, 陈玉龙.重质芳烃油选择性加氢工艺研究[J].化学工程, 2012, 40(4): 10-13.
	YANG Jihe, KUANG Junjie, CHEN Yulong.Studies on selective hydrogenation of heavy aromatic oil[J].Chemical Engineering（China）, 2012, 40(4): 10-13.
[20]	李晓云, 于海斌, 孙彦民, 等. 无机铝盐辅助活性氧化铝水热合成拟薄水铝石[J].无机盐工业, 2016, 48(6): 35-37.
	LI Xiaoyun, YU Haibin, SUN Yanmin, et al.Inorganic aluminum salt assisted hydrothermal synthesis of pseudoboehmite by activated alumina[J].Inorganic Chemicals Industry, 2016, 48(6): 35-37.
[21]	YANG Renchun, LI Xiaogang, WU Junsheng, et al.Hydrotreating of crude 2-ethylhexanol over Ni/Al₂O₃ catalysts:Surface Ni species-catalytic activity correlation[J].Applied Catalysis A:General, 2009, 368(1/2): 105-112.
[22]	王丹, 周清华, 王冰, 等. 制备方法对镍系催化剂的影响[J].石油化工, 2015, 44(10): 1193-1198.
	WANG Dan, ZHOU Qinghua, WANG Bing, et al.Effects of preparation methods on nickel-based catalysts[J].Petrochemical Technology, 2015, 44(10): 1193-1198.
[23]	IM J, SHIN H, JANG H, et al.Maximizing the catalytic function of hydrogen spillover in platinum-encapsulated aluminosilicates with controlled nanostructures[J].Nature Communications, 2014,29 Doi:10.1038/ncomms4370 . doi: 10.1038/ncomms4370

编号	样品	ICP表征			N₂物理吸附
编号	样品	w （Ni）/%	w （Pt）/%		S_BET/ （m²?g^-1）	V_T/ （cm³?g^-1）
a	γ-Al₂O₃	—	—	401.20		0.75
b	0.3Pt/γ-Al₂O₃	—	0.300	389.10		0.73
c	0.3Ni-0.3Pt/ γ-Al₂O₃	0.298	0.301	375.69		0.72
d	0.5Ni-0.3 Pt/ γ-Al₂O₃	0.501	0.299	372.17		0.71
e	0.7Ni-0.3 Pt/ γ-Al₂O₃	0.699	0.299	371.17		0.70
f	1.0Ni-0.3 Pt/ γ-Al₂O₃	1.001	0.301	370.09		0.69
g	0.5Ni-0.2 Pt/ γ-Al₂O₃	0.499	0.199	373.58		0.70
h	0.5Ni-0.1 Pt/ γ-Al₂O₃	0.502	0.101	379.32		0.70

项目	样品	酸量/ （mmol?g^-1）	酸强度/ ℃
a	γ-Al₂O₃	0.18	245.1
b	0.3Pt/γ-Al₂O₃	0.20	246.3
c	0.3Ni-0.3Pt/γ-Al₂O₃	0.23	245.1
d	0.5Ni-0.3 Pt/γ-Al₂O₃	0.25	247.8
e	0.7Ni-0.3 Pt/γ-Al₂O₃	0.28	247.6
f	1.0Ni-0.3 Pt/γ-Al₂O₃	0.27	248.2
g	0.5Ni-0.2 Pt/γ-Al₂O₃	0.24	247.9
h	0.5Ni-0.1 Pt/γ-Al₂O₃	0.23	247.7

编号	样品	金属分散度/%	金属粒径/nm
b	0.3Pt/γ-Al₂O₃	57.2	2.6
c	0.3Ni-0.3Pt/γ-Al₂O₃	75.0	1.8
d	0.5Ni-0.3 Pt/γ-Al₂O₃	83.2	1.3
e	0.7Ni-0.3 Pt/γ-Al₂O₃	76.9	1.5
f	1.0Ni-0.3 Pt/γ-Al₂O₃	65.0	1.7
g	0.5Ni-0.2 Pt/γ-Al₂O₃	84.2	1.2
h	0.5Ni-0.1 Pt/γ-Al₂O₃	87.1	1.1
i	0.5Ni/γ-Al₂O₃	45.7	3.6

密度（20 ^oC）/ （kg?m^-3）	S含量/ （mg?kg^-1）	N含量/ （mg?kg^-1）	溴指数/ （mg?g^-1）	w（胶质）/ %	馏程D-86/℃			碳数分布/%
密度（20 ^oC）/ （kg?m^-3）	S含量/ （mg?kg^-1）	N含量/ （mg?kg^-1）	溴指数/ （mg?g^-1）	w（胶质）/ %	IBP	50%	FBP	w（C₉ 芳烃）	w（C₁₀芳烃）	w（C₁₀⁺芳烃）
980.6	10.1	—	45	2.62	220.6	460.5	360.0	0.2	1.9	97.9
族组成/%
w（链烷烃） w（环烷烃） w（单环芳烃） w（双环芳烃） w（三环芳烃） w（总稠环芳烃） w（总芳烃）
0	0.5	46.7		48.5		4.3 52.8 99.5

项目	原料组成质量分数/%		产品组成质量分数/%
项目	稠环芳烃	单环芳烃	甲烷	乙烷	丙烷	丙烯	异丁烷	正丁烷	丁烯	异戊烷	正戊烷
C₁₀⁺重芳烃	52.8	46.7	2.4	30.6	47.3	2.1	9.0	4.4	2.7	1.2	0.3
加氢原料1	32.5	61.2	1.8	34.4	45.9	0.0	10.5	6.6	0.1	0.0	0.7
加氢原料2	25.0	66.6	2.0	36.9	44.1	0.2	9.9	6.3	0.3	0.0	0.3
加氢原料3	18.0	71.6	1.8	39.3	42.9	0.2	8.7	5.0	0.7	1.1	0.3
加氢原料4	13.8	74.6	1.8	44.6	38.9	0.5	7.5	4.6	0.8	0.4	0.9

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Inorganic Acid-Base-Salt Committee of CIESC

Effect of Ni on selective hydrodegenation of polyaromatic hydrocarbons of Pt/γ-Al₂O₃ catalyst

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项目	w（稠环芳烃）	w（C₅⁺非芳烃）	w（C₆芳烃）	w（C₇芳烃）	w（C₈芳烃）	w（C₉芳烃）	w（C₁₀芳烃）	w（C₁₀⁺芳烃）
C₁₀⁺重芳烃	53.5	7.7	9.2	23.5	23.9	10.8	4.7	20.2
预加氢产品1	32.5	8.0	9.9	26.1	18.6	10.9	4.4	12.1
预加氢产品2	25.0	8.3	10.7	26.9	30.5	11.8	4.1	7.7
预加氢产品3	18.0	8.5	10.8	28.4	33.0	12.6	3.6	3.1
预加氢产品4	13.8	8.7	10.7	28.8	34.3	11.7	3.5	2.3

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Effect of Ni on selective hydrodegenation of polyaromatic hydrocarbons of Pt/γ-Al2O3 catalyst