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

摘要/Abstract

摘要：

分别以氯铂酸和硝酸镍为铂和镍前驱体,通过等体积浸渍法制备了系列镍修饰的Pt/γ-Al₂O₃催化剂,并采用电感耦合等离子体原子发射光谱（ICP-AES）、氨程序升温脱附（NH₃-TPD）、氢气程序升温还原（H₂-TPR）、氢气程序升温脱附（H₂-TPD）及氢氧滴定法（H₂-O₂）等手段进行表征。以重整C₁₀⁺重芳烃为原料,在30 mL固定床装置上考察镍引入对Pt/γ-Al₂O₃催化剂稠环芳烃（PAHs）选择性加氢性能的影响。固定床评价结果表明,随镍含量增加,稠环芳烃加氢活性和单环芳烃选择性呈现先增加后降低的趋势,当0.1Pt/γ-Al₂O₃催化剂中引入0.5%（质量分数）的镍时,催化剂稠环芳烃加氢活性和选择性最佳,此时稠环芳烃转化率为75%左右,单环芳烃选择性为98%以上。结合H₂-TPR、H₂-TPD及H₂-O₂滴定等表征结果,分析主要原因在于一定量镍的引入提高了铂的分散度,同时由于铂的加氢活化能较低,铂通过溢流活化的氢迁移至非贵金属镍上,提高了金属镍的加氢性能。此外,铂的存在还可避免镍形成尖晶石结构等非活性相,促进镍氧化物的还原,进而提高了催化剂的稠环芳烃加氢活性、选择性和稳定性。

关键词: 镍, Pt/γ-Al₂O₃, 稠环芳烃, 单环芳烃, 选择性加氢

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

中图分类号:

TQ138.13

靳凤英,于海斌,王亚权,臧甲忠,郭春垒,刘航,马明超,赵训志,刘凯隆. 镍对Pt/γ-Al₂O₃催化剂稠环芳烃选择性加氢性能的影响[J]. 无机盐工业, 2022, 54(10): 141-148.

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.

图/表 12

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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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镍对Pt/γ-Al₂O₃催化剂稠环芳烃选择性加氢性能的影响

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

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参考文献 23

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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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