基于钯炭催化剂的苯酚加氢反应及其本征动力学

王鹏; 李涛; 张海涛; 房鼎业

doi:10.14135/j.cnki.1006-3080.20200308002

基于钯炭催化剂的苯酚加氢反应及其本征动力学

doi: 10.14135/j.cnki.1006-3080.20200308002

华东理工大学化工学院，上海 200237

详细信息

作者简介:
王鹏：王　鹏（1994—），男，安徽桐城人，硕士生，主要研究方向为催化反应工程。E-mail：wp940215@163.com

通讯作者:
李　涛，E-mail：tli@ecust.edu.cn

中图分类号: TQ032.4
计量
- 文章访问数: 2078
- HTML全文浏览量: 987
- PDF下载量: 119
- 被引次数: 0
出版历程
- 收稿日期: 2020-03-08
- 网络出版日期: 2020-07-14
- 刊出日期: 2021-06-30

Phenol Hydrogenation Reaction and Its Intrinsic Kinetics Based on Pd/C Catalyst

School of Chemical Engineering, East China University of Science and Technology, Shanghai 200237, China

摘要

摘要: 将钯炭（Pd/C）催化剂应用到苯酚加氢制环己酮反应中，选择苯作为溶剂，通过控制变量法考察了压力、温度、氢气与苯酚物质的量之比、苯酚的质量空速等反应条件对反应的影响；建立了本征动力学模型，利用25组正交试验数据进行参数估值，并对动力学模型进行了检验。结果表明，Pd/C催化剂用于苯酚加氢制备环己酮时，适宜的反应条件为：反应温度175~205 ℃，反应压力0.1 MPa，氢气与苯酚物质的量之比约为4，苯酚质量空速0.2~0.4 h⁻¹。经检验，本征动力学模型可靠性良好。
- Pd/C催化剂 /
- 苯酚加氢 /
- 环己酮 /
- 本征动力学 /
- 参数估值
Abstract: Cyclohexanone, a widely used organic chemical raw material, plays a very important role in industrial production. Hydrogenation of phenol to cyclohexanone has the advantages of mild reaction conditions, few by-products, and environmental friendliness. Pd/C catalyst was used for the hydrogenation of phenol to cyclohexanone. After comparing the dichloromethane, cyclohexane, ethanol, and benzene, benzene was selected as the solvent. At the reaction temperature 160—250 ℃, the reaction pressure 0.1—2.0 MPa, the weight hourly space velocity of phenol 0.2—1.0 h⁻¹, the molar ratio of hydrogen to phenol 2—12, the influence of reaction conditions on the hydrogenation of phenol was investigated. A fixed bed tubular reactor charged with 80—100 mesh(150—180 μm）Pd/C catalyst was developed. Eliminating the influence of internal and external diffusion, 25 groups of experimental data were measured by changing the temperature, pressure and molar ratio of hydrogen to phenol. An intrinsic kinetic model was established based on the ideal adsorption model. The optimal reaction parameters were determined using 25 sets of orthogonal experimental data, and the dynamics model was also examined. The results show that the suitable reaction conditions are as follows: reaction temperature 175—205 ℃, reaction pressure 0.1 MPa, the molar ratio of hydrogen to phenol about 4, and the weight hourly space velocity of phenol 0.2—0.4 h⁻¹. After statistical test and residual analysis, the established intrinsic kinetic model is applicable and has good reliability.
- Pd/C catalyst /
- phenol hydrogenation /
- cyclohexanone /
- intrinsic kinetics /
- parameter estimation

HTML全文

图 1 苯酚加氢流程图

Figure 1. Flow sheet of phenol hydrogenation

1—Gas cylinder；2—Pressure gauge；3—Filter；4—One-way valve；5—Ball valve；6—Pressure controller；7—Reducing valve；8—Mass flow controller；9—Temperature controller；10—Deaerator；11—Mixer；12—Heating furnace；13—Reaction tube；14—Condenser；15—Gas-liquid separator；16—Holding tank；17—Back-pressure valve；18—Soap film flowmeter；19—Gas chromatography；20—Needle valve；21—Constant-flux pump

下载: 全尺寸图片幻灯片

图 2 温度对反应的影响

Figure 2. Effect of temperature on the reaction

下载: 全尺寸图片幻灯片

图 3 压力对反应的影响

Figure 3. Effect of pressure on the reaction

下载: 全尺寸图片幻灯片

图 4 氢气与苯酚物质的量之比对反应的影响

Figure 4. Effect of mole ratio of H₂ to phenol on the reaction

下载: 全尺寸图片幻灯片

图 5 苯酚质量空速对反应的影响

Figure 5. Effect of weight hourly space velocity of phenol on the reaction

下载: 全尺寸图片幻灯片

图 6 催化剂质量与苯酚质量空速之比对苯酚转化率的影响

Figure 6. Effect of ratio of catalyst mass to WHSV on phenol conversion

下载: 全尺寸图片幻灯片

图 7 环己酮出口摩尔分数实验值与模型计算值

Figure 7. Experimental values and model calculated values of cyclohexanone molar fraction at reactor outlet

下载: 全尺寸图片幻灯片

图 8 环己醇出口摩尔分数实验值与模型计算值

Figure 8. Experimental values and model calculated values of cyclohexanol molar fraction at reactor outlet

下载: 全尺寸图片幻灯片

表 1 溶剂对反应的影响

Table 1. Effect of solvent on the reaction

Solvent	X/%	S/%
Dichloromethane	56.79	63.14
Cyclohexane	96.42	94.37
Ethanol	98.23	76.56
Benzene	97.72	96.21

下载: 导出CSV

表 2 Pd/C催化剂颗粒尺寸对苯酚转化率的影响

Table 2. Effect of Pd/C catalyst particle size on phenol conversion

Particle size/μm	X/%
380~830	88.84
250~380	93.76
180~250	97.52
150~180	97.72
120~150	97.73

下载: 导出CSV

表 3 固定床反应器内苯酚加氢动力学实验数据

Table 3. Kinetic experimental data of phenol hydrogenation in fixed bed reactor

No.	p/MPa	t/℃	n(H₂)∶n(Phenol)	X/%	S_{Cyclohexanone}/%	S_{Cyclohexanol+Others}/%
1	0.10	160.1	2	79.36	98.72	1.28
2	0.11	175.2	4	92.74	96.44	3.56
3	0.11	190.3	6	98.13	94.34	5.66
4	0.10	205.3	8	93.47	90.66	9.34
5	0.11	220.5	10	88.74	86.53	13.47
6	0.21	160.2	4	86.64	95.42	4.58
7	0.20	175.1	6	93.39	94.13	5.87
8	0.22	190.0	8	98.63	91.30	8.70
9	0.22	205.2	10	94.28	88.04	11.96
10	0.21	220.4	2	82.64	92.26	7.74
11	0.31	160.2	6	88.82	91.24	8.76
12	0.31	175.3	8	93.56	89.89	10.11
13	0.32	190.2	10	98.75	88.82	11.18
14	0.31	205.5	2	83.76	90.83	9.17
15	0.30	220.6	4	88.51	87.66	12.34
16	0.42	160.3	8	90.22	88.97	11.03
17	0.41	175.3	10	93.95	87.51	12.49
18	0.41	190.5	2	86.24	90.89	9.11
19	0.42	205.3	4	93.42	84.48	15.52
20	0.42	220.2	6	89.63	80.39	19.61
21	0.52	160.1	10	91.35	81.23	18.77
22	0.52	175.1	2	83.12	89.36	10.64
23	0.50	190.3	4	98.58	88.49	11.51
24	0.51	205.2	6	93.95	83.70	16.30
25	0.52	220.4	8	91.17	74.84	25.16

下载: 导出CSV

表 4 动力学模型统计检验

Table 4. Statistical test of the kinetic model

Formula	M	M_P	ρ²	F	F_0.05（10，14）
3	25	10	0.995 3	124.73	2.60
4	25	10	0.993 6	80.56	2.60

下载: 导出CSV

参考文献(16)

[1]	姜日元, 毕馨丹, 张桂华. 环己酮生产及市场情况分析[J]. 化学工业, 2019, 37(5): 32-35. doi: 10.3969/j.issn.1673-9647.2019.05.007
[2]	TIAN C, FANG H, CHEN H, et al. Photodeposition of Pd onto TiO₂ nanowires for aqueous-phase selective hydrogenation of phenolics to cyclohexanones[J]. Nanoscale, 2020, 12(4): 2603-2612. doi: 10.1039/C9NR08324C
[3]	CHEN Y, KONG X, MAO S, et al. Study of the role of alkaline sodium additive in selective hydrogenation of phenol[J]. Chinese Journal of Catalysis, 2019, 40(10): 1516-1524. doi: 10.1016/S1872-2067(19)63386-3
[4]	LI J, YANG L, LI F, et al. Hydration of cyclohexene to cyclohexanol over SO₃H-functionalized imidazole ionic liquids[J]. Reaction Kinetics, Mechanisms and Catalysis, 2015, 114(1): 173-183. doi: 10.1007/s11144-014-0778-z
[5]	WU M, ZHAN W, GUO Y, et al. An effective Mn-Co mixed oxide catalyst for the solvent-free selective oxidation of cyclohexane with molecular oxygen[J]. Applied Catalysis A: General, 2016, 523: 97-106. doi: 10.1016/j.apcata.2016.06.001
[6]	ZHANG Y, ZHOU J C, LI K, et al. Synergistic catalytic hydrogenation of phenol over hybrid nano-structure Pd catalyst[J]. Molecular Catalysis, 2019, 478: 1-9.
[7]	李明, 伍小明. 我国苯酚合成环己酮技术研究进展[J]. 精细与专用化学品, 2019, 27(3): 52-54.
[8]	孔祥千. 苯酚选择性加氢催化体系的设计及反应机理研究[D]. 杭州: 浙江大学, 2019.
[9]	YANG G X, ZHANG J X, JIANG H, et al. Turning surface properties of Pd/N-doped porous carbon by trace oxygen with enhanced catalytic performance for selective phenol hydrogenation to cyclohexanone[J]. Applied Catalysis A: General, 2019, 588: 1-8.
[10]	CHEN Y, LIAW C, LEE L. Selective hydrogenation of phenol to cyclohexanone over palladium supported on calcined Mg/Al hydrotalcite[J]. Applied Catalysis A: General, 1999, 177(1): 1-8. doi: 10.1016/S0926-860X(98)00252-X
[11]	ALBERS P, BURMEISTER R, SEIBOLD K, et al. Investigations of palladium catalysts on different carbon supports[J]. Journal of Catalysis, 1999, 181(1): 145-154. doi: 10.1006/jcat.1998.2279
[12]	李孝国, 成宏, 马月谦, 等. 氢溢流现象及其在催化反应中的应用[J]. 工业催化, 2015, 15(增刊): 116-118.
[13]	王军, 乔旭, 丁健, 等. 流动体系中溢流氢在苯加氢催化反应中的作用[J]. 南京化工大学学报(自然科学版), 2000, 22(2): 23-27.
[14]	赵德华, 吕德伟, 臧雅茹, 等. 多相催化中的溢流作用[J]. 化学进展, 1997, 9(2): 123-130. doi: 10.3321/j.issn:1005-281X.1997.02.002
[15]	LI G, HAN J, WANG H, et al. Role of dissociation of phenol in its selective hydrogenation on Pt(Ⅲ) and Pd(Ⅲ)[J]. ACS Catalysis, 2015, 5(3): 2009-2016. doi: 10.1021/cs501805y
[16]	GONZÁLEZ-VELASCO J R, GUTIÉRREZ-ORTIZ J I, GONZÁLEZ-MARCOS J A, et al. Kinetics of the selective hydrogenation of phenol to cyclohexanone over a Pd-alumina catalyst[J]. Reaction Kinetics & Catalysis Letters, 1986, 32(2): 505-512.