Pt/CeL重整催化剂的制备及其石脑油芳构化性能

张鹏; 刘坚; 崔佳; 杨英; 胡长禄; 刘百军

Pt/CeL重整催化剂的制备及其石脑油芳构化性能

张鹏^{1, 2},
刘坚¹,
崔佳²,
杨英¹,
胡长禄²,
刘百军^1, ,

1.
中国石油大学(北京)化学工程学院, 重质油国家重点实验室, 北京 102249
2.
中国石油天然气股份有限公司石油化工研究院, 北京 102206

详细信息

本文的英文电子版由Elsevier出版社在ScienceDirect上出版(http://www.sciencedirect.com/science/journal/18725813).
中图分类号: O643.3;TE624
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出版历程
- 收稿日期: 2018-10-09
- 修回日期: 2018-11-30
- 网络出版日期: 2021-01-23
- 刊出日期: 2019-03-10

Preparation of Pt/CeL reforming catalyst and its performance in the aromatization of naphtha

ZHANG Peng^{1, 2},
LIU Jian¹,
CUI Jia²,
YANG Ying¹,
HU Chang-lu²,
LIU Bai-jun^{1
, ,}

1.
State Key Laboratory of Heavy Oil Processing, China University of Petroleum(Beijing), Beijing 102249, China
2.
Petrochemical Research Institute, Petro China Company Limited, Beijing 102206, China

More Information

Corresponding author: LIU Bai-jun, Tel: 010-89733751, E-mail:bjliu@cup.edu.cn

摘要

摘要: 为克服常规氧化铝重整催化剂氯离子流失及其对设备的腐蚀等问题，通过离子交换法制备了Ce³⁺改性的L分子筛，采用浸渍法制备了Pt/CeL重整催化剂；用XRD、N₂吸附-脱附、NH₃-TPD和Py-FTIR等手段对载体和催化剂进行了表征，并以硫含量为0.50 μg/mL的工业精制石脑油为原料，在固定床微型反应装置上评价了Pt/CeL催化剂的重整芳构化性能。结果表明，Ce³⁺离子交换可提高载体的酸量和酸强度，而不会破坏L分子筛的骨架结构；Ce³⁺改性后的Pt/CeL催化剂其重整芳构化性能明显提高，活性与选择性达到氧化铝型商业重整催化剂的水平，说明适当的酸性对重整催化剂芳构化反应有显著的促进作用。
- 催化重整 /
- 铈 /
- L分子筛 /
- 离子交换 /
- 芳构化
Abstract: To solve the problems of chlorine loss and equipment corrosion caused by the conventional alumina-type reforming catalyst, zeolite L was modified with Ce³⁺ by ion exchange method and with Ce³⁺-modified L (CeL) as the support, the Pt/CeL reforming catalyst without any chlorine was prepared by impregnation method. The CeL support and Pt/CeL catalyst were characterized by XRD, N₂ adsorption-desorption, NH₃-TPD and Py-FTIR; the catalytic performance of Pt/CeL in aromatization was investigated in a continuous-flow fixed-bed micro-reactor, with an industrial hydrofining naphtha containing 0.50 μg/mL sulfur as the feedstock. The results indicate that the modification with Ce³⁺ by ion exchange has little influence on framework structure of zeolite L; however, it can raise the acid content and acid strength of the CeL support and then remarkably enhance the performance of the Pt/CeL reforming catalyst in aromatization. The activity and selectivity of the Pt/CeL catalyst are comparable to those of the commercial alumina-type reforming catalysts, suggesting that proper acidity can facilitate the aromatization reaction.
- catalytic reforming /
- cerium /
- zeolite L /
- ion exchange /
- aromatization
注释:

1) 本文的英文电子版由Elsevier出版社在ScienceDirect上出版(http://www.sciencedirect.com/science/journal/18725813).

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图 1 KL和CeL分子筛的XRD谱图

Figure 1 XRD patterns of the KL and CeL zeolites

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图 2 KL、CeL和Al₂O₃-Cl的NH₃-TPD谱图

Figure 2 NH₃-TPD profiles of KL, CeL and Al₂O₃-Cl

下载: 全尺寸图片幻灯片

表 1 KL和CeL分子筛的比表面积和孔体积

Table 1 Textural properties of the KL and CeL zeolites

Sample	Surface area A/(m²·g^-1)			Pore volume v/(mL·g^-1)
Sample	total	micropore	mesopore	total	micropore	mesopore
KL	266	220	46	0.26	0.12	0.14
CeL	266	220	46	0.24	0.11	0.13

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表 2 KL、CeL和Al₂O₃-Cl的酸量分布

Table 2 Acid distribution of zeolite KL, zeolite CeL and Al₂O₃-Cl

Sample	Acid amount determined by NH₃-TPD/(a.u.)
Sample	weak (100-200 ℃)	medium (200-400 ℃)	strong (400-600 ℃)	total (100-600 ℃)
KL	199.5	130.5	9.6	339.6
CeL	414.6	1585.4	219.6	2219.6
Al₂O₃-Cl	333.3	1150.8	203.9	1688.0

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表 3 KL、CeL和Al₂O₃-Cl的B酸与L酸分布

Table 3 Lewis (L) and Brönsted (B) acid distribution of KL, CeL and Al₂O₃-Cl

Sample	Total acid amount measured by Py-FTIR at 200 ℃/(μmol·g^-1)				Strong acid amount measured by Py-FTIR at 350 ℃/(μmol·g^-1)
Sample	L	B	B+L	B/L	L	B	B+L	B/L
KL	93.2	0	93.2	0	8.9	0	8.9	0
CeL	466.0	130.5	596.5	0.28	200.2	14.0	214.2	0.07
Al₂O₃-Cl	340.3	0	340.3	0	196.5	0	196.5	0

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表 4 重整评价原料油性质

Table 4 Properties of the hydrofining naphtha feedstock

Item	Result
Density(20 ℃)/(g·cm^-3)	0.7374
Sulfur content /(μg·mL^-1)	0.50
Nitrogen content /(μg·mL^-1)	0.32
PONA w/%
n-paraffin	10.9
i-paraffin	43.5
Olefin	0.0
Naphthene	41.4
Aromatic	4.2
RON	76.2

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表 5 Pt/KL和Pt/CeL催化剂石脑油催化重整评价

Table 5 Catalytic evaluation results of Pt/KL and Pt/CeL for naphtha reforming

Catalyst	Aromatics content in liquid products w/%	Liquid yield w/%	Total aromatics yield w/%	Benzene yield w/%	Toluene yield w/%	C₈ aromatics yield w/%	C₉₊ aromatics yield w/%
Pt 0.3/KL	34.5	86.8	30.0	1.1	7.7	10.7	10.5
Pt 0.8/KL	53.1	83.5	44.3	1.9	12.8	15.8	13.8
Pt 0.3/CeL	65.4	82.4	53.9	2.7	15.7	19.3	16.2
Pt 0.8/CeL	70.5	79.9	56.3	3.8	17.9	19.9	14.7
Pt 0.3/Al₂O₃-Cl^*	71.0	79.0	56.1	2.4	15.7	19.5	18.5
*：a widely used commercial alumina-type reforming catalyst； reaction conditions: 490 ℃, 0.7 MPa(G), LHSV = 2 h^-1, H₂/hydrocarbon mole ratio = 9

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