磷改性Cr2O3/Al2O3催化4-乙基酚转化制轻质芳烃

邱泽刚; 刘伟伟; 李志勤

磷改性Cr₂O₃/Al₂O₃催化4-乙基酚转化制轻质芳烃

西安石油大学化学化工学院, 陕西西安 710065

基金项目:

国家自然科学基金 21878243

国家自然科学基金 21606177

国家自然科学基金 21908176

陕西省自然科学基础研究计划 2019JM-085

详细信息

中图分类号: TQ032.41
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出版历程
- 收稿日期: 2020-03-17
- 修回日期: 2020-06-12
- 网络出版日期: 2021-01-23
- 刊出日期: 2020-08-10

Conversion of 4-ethylphenol to light aromatics on the Cr₂O₃/Al₂O₃ modified by phosphoric acid

College of Chemistry and Chemical Engineering, Xi'an Shiyou University, Xi'an 710065, China

Funds:

the Natural Science Foundation of China 21878243

the Natural Science Foundation of China 21606177

the Natural Science Foundation of China 21908176

Natural Science Basic Research Program of Shaanxi 2019JM-085

More Information

Corresponding author: LI Zhi-qin, E-mail: lizhiqin@xsyu.edu.cn

摘要

摘要: 以烷基酚转化为轻质芳烃（苯和甲苯）为目标，制备了Cr₂O₃/Al₂O₃催化剂，并以4-乙基酚为模型化合物研究了其加氢反应性能。体积空速、氢油比、反应压力和温度升高时，脱烷基率、芳烃总选择性、轻质芳烃选择性呈先增大后减小的趋势，反应温度对转化率影响较大。以不同浓度磷酸对Cr₂O₃/Al₂O₃进行改性，随着磷酸用量的增大，催化剂酸量总体增大，主要是弱酸和中强酸，酸强度先增加后降低，磷酸用量较高时，弱酸增加幅度较大。与未改性相比，质量分数8%磷酸改性Cr₂O₃/Al₂O₃上4-乙基酚转化率99.5%，脱烷基率提升9.4%，达74.4%，轻质芳烃选择性提高4.0%，达到57.0%，以较高选择性实现了转化制轻质芳烃，同时，芳烃总选择性高达80.4%，较高程度保持了芳环不被破坏。提出了Cr₂O₃/Al₂O₃上4-乙基酚加氢反应的路径并对反应机理进行了研究。
- 煤焦油 /
- 4-乙基酚 /
- 磷酸 /
- 氧化铝 /
- 氧化铬
Abstract: With the goal of conversion of alkylphenols to light aromatics (benzene and toluene), Cr₂O₃/Al₂O₃ catalysts were prepared and their hydrogenation performance was investigated using 4-ethylphenol as a model compound. With the increase of LHSV, H₂/oil, reaction pressure and temperature, the dealkylation rate, the total selectivity of aromatics, and the selectivity of light aromatics first rose and then dropped. The conversion of 4-ethylphenol was obviously influenced by the reaction temperature. Cr₂O₃/Al₂O₃ was modified with different concentrations of phosphoric acid. As the increase of the amount of phosphoric acid, the general amount of weak and medium acids on the catalyst increased, and the strength of acid was first enhanced and then weakened. The amount of weak acid increased significantly under a high value of the amount of phosphoric acid. Compared with the unmodified catalyst, the conversion of 4-ethylphenol on the catalysts modified by 8% phosphoric acid is higher than 99.5%, while the dealkylation rate of 4-ethylphenol increased by 9.4%, reaching to 74.4%, and the selectivity to light aromatics (benzene and toluene) increased by 4.0%, reaching to 57.0%. Conversion of 4-ethylphenol to light aromatics was achieved in high selectivity. Furthermore, the total selectivity of aromatics was as high as 80.4%, which meant that most of the aromatic rings was not broken. The path of hydrogenation reaction of 4-ethylphenol on Cr₂O₃/Al₂O₃ was proposed and the reaction mechanism was discussed.
- coal tar /
- 4-ethylphenol /
- phosphoric acid /
- alumina /
- chromium oxide

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图 1 4-乙基酚转化为轻质芳烃的可能途径示意图

Figure 1 Possible transformation pathways for conversion of 4-ethylphenol to light aromatics

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图 2 不同体积空速对Cr₂O₃/Al₂O₃催化4-乙基酚加氢反应性能的影响

Figure 2 Effect of LHSV on the performance of the Cr₂O₃/Al₂O₃ catalysts for the hydrogenation of 4-ethylphenol

reaction conditions: H₂/oil=500 :1, p=3.5 MPa, t=450 ℃

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图 3 不同氢油比对Cr₂O₃/Al₂O₃催化4-乙基酚加氢反应性能的影响

Figure 3 Effect of H₂/oil ratio on the performance of the Cr₂O₃/Al₂O₃ catalysts for the hydrogenation of 4-ethylphenol

reaction conditions: LHSV=6 h^-1, p=3.5 MPa, t=450 ℃

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图 4 不同反应压力对Cr₂O₃/Al₂O₃催化4-乙基酚加氢反应性能的影响

Figure 4 Effect of reaction pressures on the performance of the Cr₂O₃/Al₂O₃ catalysts for the hydrogenation of 4-ethylphenol

reaction conditions: LHSV=6 h^-1, H₂/oil=500 :1, t=450 ℃

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图 5 不同反应温度对Cr₂O₃/Al₂O₃催化4-乙基酚加氢反应性能的影响

Figure 5 Effect of reaction temperature on the performance of the Cr₂O₃/Al₂O₃ catalysts for the hydrogenation of 4-ethylphenol

reaction conditions: LHSV=6 h^-1, H₂/oil=500 :1, p=3.5 MPa

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图 6 4-乙基酚加氢反应的主要产物及其选择性

Figure 6 Main products and their selectivity in the hydrogenation reaction of 4-ethylphenol

reaction conditions: LHSV=6 h^-1, H₂/oil=500 :1, p=3.5 MPa, t=450 ℃

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图 7 不同含量磷酸改性对Cr₂O₃/Al₂O₃催化4-乙基酚加氢反应性能的影响

Figure 7 Effect of modification with various content of phosphoric acid on the performance of the Cr₂O₃/Al₂O₃ catalysts for the hydrogenation of 4-ethylphenol

reaction conditions: LHSV=6 h^-1, H₂/oil=500 :1, p=3.5 MPa, t=450 ℃ P-0: 0 H₃PO₄; P-1: 4%H₃PO₄; P-2: 6%H₃PO₄; P-3: 8%H₃PO₄; P-4: 10%H₃PO₄; P-5: 12%H₃PO₄

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图 8 不同含量磷酸改性Cr₂O₃/Al₂O₃催化剂反应前后的XRD谱图

Figure 8 XRD patterns of the Cr₂O₃/Al₂O₃ catalysts modified with various content of phosphoric acid before and after reaction

reaction conditions: LHSV=6 h^-1, H₂/oil=500 :1, p=3.5 MPa, t=450 ℃; AF: after P-0: 0 H₃PO₄; P-1: 4%H₃PO₄; P-2: 6%H₃PO₄; P-3: 8%H₃PO₄; P-4: 10%H₃PO₄; P-5: 12%H₃PO₄

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图 9 不同含量磷酸改性Cr₂O₃/Al₂O₃催化剂的NH₃-TPD谱图

Figure 9 NH₃-TPD profiles of the Cr₂O₃/Al₂O₃ catalysts modified with various content of phosphoric acid

reaction conditions: LHSV=6 h^-1, H₂/oil=500 :1, p=3.5 MPa, t=450 ℃ P-0: 0 H₃PO₄; P-1: 4%H₃PO₄; P-2: 6%H₃PO₄; P-3: 8%H₃PO₄; P-4: 10%H₃PO₄; P-5: 12%H₃PO₄

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图 10 不同含量磷酸改性Cr₂O₃/Al₂O₃催化剂的XPS谱图

Figure 10 XPS spectra of the Cr₂O₃/Al₂O₃ catalysts modified with various content of phosphoric acid

reaction conditions: LHSV=6 h^-1, H₂/oil=500 :1, p=3.5 MPa, t=450 ℃ P-0: 0 H₃PO₄; P-1: 4%H₃PO₄; P-2: 6%H₃PO₄; P-3: 8%H₃PO₄; P-4: 10%H₃PO₄; P-5: 12%H₃PO₄

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图 11 Cr₂O₃/Al₂O₃上4-乙基酚加氢主要反应路径

Figure 11 Main reaction paths for the hydrogenation of 4-ethylphenol on the Cr₂O₃/Al₂O₃ catalyst

reaction conditions: LHSV=6 h^-1, H₂/oil=500 :1, p=3.5 MPa, t=450 ℃

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表 1 不同含量磷酸改性Cr₂O₃/Al₂O₃催化剂的孔结构参数表

Table 1 Pore structure parameters of the Cr₂O₃/Al₂O₃ catalysts modified by various content of phosphoric acid

Catalyst	Specific surface area A/(m²·g^-1)	Pore volume v/(cm³·g^-1)	Average pore size d/nm
P-1	140.6	0.44	12.5
P-2	148.8	0.47	12.5
P-3	146.7	0.47	12.7
P-4	134.5	0.41	12.1
P-5	131.9	0.40	10.4
reaction conditions：LHSV=6 h^-1，H₂/oil=500 :1， p=3.5 MPa，t=450 ℃ P-1: 4%H₃PO₄；P-2: 6%H₃PO₄；P-3: 8%H₃PO₄；P-4: 10%H₃PO₄；P-5: 12%H₃PO₄

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表 2 不同含量磷酸改性Cr₂O₃/Al₂O₃催化剂表面元素相对百分含量

Table 2 Relative percentage content of surface elements of the Cr₂O₃/Al₂O₃ catalysts modified with different phosphoric acid content

Catalyst	Content w/%
Catalyst	P	O	Cr
P-0	0.00	96.06	3.94
P-1	1.61	94.54	3.85
P-2	2.09	94.21	3.70
P-3	2.32	93.78	3.90
P-4	2.65	93.34	4.01
P-5	3.59	92.55	3.86
AFP-3	2.20	93.78	4.02
reaction conditions：LHSV=6 h^-1，H₂/oil=500 :1，p=3.5 MPa，t=450 ℃ P-0: 0 H₃PO₄；P-1: 4%H₃PO₄；P-2: 6%H₃PO₄；P-3: 8%H₃PO₄；P-4: 10%H₃PO₄；P-5: 12%H₃PO₄

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