负载铯催化剂上苯酚与甲醇醚化制苯甲醚

邓甜音; 郜丽娟; 马琳鸽; 陈静允; 李晶; 郭小汾

负载铯催化剂上苯酚与甲醇醚化制苯甲醚

北京低碳清洁能源研究所, 北京 102209

基金项目:

国家高技术研究发展计划 863 program

国家高技术研究发展计划 2011AA05A202

神华集团项目基金 CF9300140004

详细信息

通讯作者:
郭小汾, E-mail: guoxiaofen@nicenergy.com

中图分类号: O643
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- 文章访问数: 114
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- 被引次数: 0
出版历程
- 收稿日期: 2016-02-26
- 修回日期: 2016-06-12
- 网络出版日期: 2021-01-23
- 刊出日期: 2016-09-10

Phenol etherification with methanol to anisole over supported Cs catalysts

National Institute of Clean-and-Low-Carbon Energy, Shenhua Group, Beijing 102209, China

Funds:

National High Technology Research and Development Program of China 863 program

National High Technology Research and Development Program of China 2011AA05A202

Shenhua Group Foundation CF9300140004

摘要

摘要: 研究了不同酸碱中心、载体、前躯体和负载量对负载铯催化剂上苯酚与甲醇醚化制苯甲醚反应行为的影响。结果表明，碱性中心比酸性中心具有更高的苯甲醚选择性，碱性中心的阳离子影响催化剂的苯甲醚选择性。载体影响铯离子的电子结合能，从而影响催化剂的醚化活性；铯离子的电子结合能越低，催化剂醚化活性越低；载体影响催化剂强碱性位数量，从而影响苯甲醚选择性；强碱性位数量越多，副反应越容易发生，苯甲醚选择性越低。不同前躯体制备的Cs/SiO₂由于表面相对铯原子数量不同而活性不同；Cs/SiO₂的单层负载量为1.0 mmol/g，超过单层负载量后催化剂的平均活性显著下降。
- 负载铯催化剂 /
- 活性 /
- 选择性 /
- 苯酚 /
- 苯甲醚 /
- 醚化
Abstract: The effect of acid and basic sites, support, cesium precursor and cesium loading on the performance of supported Cs catalysts in the etherification of phenol with methanol to anisole was investigated. The results illustrate that the cations of basic sites play an important role in the selective conversion of phenol to anisole; the basic sites give higher selectivity to anisole than the acid sites. The catalytic activity in phenol etherification decreases with the increase of the cesium ion binding energy, which is related to the support used. Moreover, the support also has an influence on the amount of strong basic sites, which is related to the selectivity to anisole; high amount of strong basic sites may promote the side reaction and decrease the selectivity to anisole. Cs/SiO₂ catalysts prepared with various precursors are different in the surface Cs/Si atomic ratio, which may also influence the catalytic activity in phenol etherification; if the cesium loading exceeds the monolayer dispersion of cesium on SiO₂, which is nearly 1.0 mmol/g, the average activity of Cs/SiO₂ in phenol etherification decreases greatly.
- supported Cs catalyst /
- activity /
- selectivity /
- phenol /
- anisol /
- etherification

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图 1 不同载体负载铯催化剂的CO₂-TPD谱图

Figure 1 CO₂-TPD profiles of the cesium catalysts with different supports

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图 2 铯催化剂催化苯酚与甲醇醚化的路径图

Figure 2 Schemtic description of phenol etherification with methanol on the cesium catalysts

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图 3 不同负载量铯催化剂的XRD谱图

Figure 3 XRD patterns of the Cs/SiO₂ catalysts with different cesium loadings

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图 4 催化剂上黑色物质的Raman谱图

Figure 4 Raman spectra of the black substance on the catalyst

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图 5 不同前躯体催化剂的TG曲线

Figure 5 TG curves of the catalysts prepared with different cesium precursors

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图 6 苯酚醚化转化率与催化剂表面相对铯原子数量的关系

Figure 6 Relationship between phenol etherification conversion and the surface atomic ratio of Cs/Si

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图 7 表面相对铯原子数量与铯负载量的关系

Figure 7 Relationship between the surface atomic ratio of Cs/Si and the cesium loading

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图 8 不同负载量催化剂的平均活性

Figure 8 Average activity of the cesium catalysts with different loadings (reaction conditions: 380 ℃, LHSV=2.0 h^-1, N₂ flow of 20 mL/min, TOS=5 h, phenol conversion of 20%-35%)

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表 1 不同二氧化硅负载催化剂的苯酚转化率和产物选择性

Table 1 Phenol conversion and product selectivity on different SiO₂ supported catalysts

Catalyst	Conversion x/%	Selectivity s/%
Catalyst	Conversion x/%	anisol	2-MA^①	3/4-MA^①	o-cresol	m/p-cresol	xylenol	others
H₄Si (W₃O₁₀)₄/SiO₂	9.0	22.7	1.2	0.6	36.7	8.4	5.7	24.7
AlCl₃/SiO₂	71.9	33.9	6.9	2.9	20.0	4.2	16.2	15.9
K/SiO₂	6.3	95.4	0.7	0.3	1.5	0.3	0.2	1.6
Cs/SiO₂	36.0	98.7	0.2	~0.0	0.3	0.1	~0.0	0.7
Ba/SiO₂	15.0	88.0	0.5	0.3	7.0	1.6	0.4	2.2
SiO₂	1.4	63.6	4.0	2.0	13.7	3.8	5.1	7.8
①: 2-methylanisol (2-MA), 3-methylanisol (3-MA), 4-methylanisol (4-MA); note: 400 ℃, LHSV=1.0 h^-1, N₂ flow of 20 mL/min, TOS=5 h, H, Al, Ba, Cs, Rb, K, Na loading of 0.5 mmol/g (CH₃COOCs as the precusor)

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表 2 不同载体负载铯催化剂的苯酚转化率和产物选择性

Table 2 Phenol conversion and product selectivity on the cesium catalysts with different supports

Support	Conversion x/%	Selectivity s/%
Support	Conversion x/%	anisol	2-MA^①	3/4-MA^①	o-cresol	m/p-cresol	xylenol	others
Cs/HY	52.0	97.7	0.3	0.1	0.7	0.1	~0.0	1.1
Cs/SiO₂-Al₂O₃	52.6	67.8	4.6	1.9	16.8	2.6	3.8	2.5
Cs/SiO₂	76.3	98.9	0.2	0.1	0.2	0.1	~0.0	0.5
Cs/Al₂O₃	13.2	93.3	1.4	0.6	2.6	1.0	0.4	0.7
Cs/MgO-Al₂O₃(3:7)	12.4	90.1	0.4	0.2	6.1	2.0	0.2	1.0
Cs/MgO-Al₂O₃(7:3)	10.3	84.8	0.4	0.3	8.2	3.8	0.4	2.1
①: 2-methylanisol (2-MA), 3-methylanisol (3-MA), 4-methylanisol (4-MA); note: 400 ℃, LHSV=1.0 h^-1, N₂ 20 mL/min, TOS 5 h, Cs loading 1.0 mmol/g (CH₃COOCs as the precusor)

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表 3 不同载体负载的铯催化剂XPS表征

Table 3 XPS results of the cesium catalysts with different supports

Catalyst	Cs 3d_5/2/eV
Cs/SiO₂	725.0
Cs/Al₂O₃	724.6
Cs/ MgO-Al₂O₃(7:3)	724.5

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表 4 不同前躯体催化剂的苯酚转化率和苯甲醚选择性

Table 4 Phenol conversion and anisol selectivity on the catalysts prepared with different precursors

Precusor	Conversion x/%	Selectivity s/%
Precusor	Conversion x/%	anisol	others
CH₃COOCs	36.0	98.7	1.3
CsNO₃	50.7	99.0	1.0
Cs₂CO₃	53.1	98.8	1.2
note: 400 ℃, LHSV=1.0 h^-1, N₂ flow of 20 mL/min, TOS=5 h, Cs loading of 0.5 mmol/g

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表 5 不同底物的转化率和产物选择性

Table 5 Conversion of different reactants and product selectivity

Reactant	Conversion x/%	Selectivity s/%
Reactant	Conversion x/%	target product	others
Phenol	86.7	98.9	1.1
o-cresol	84.4	95.1	4.9
m-cresol	89.5	97.6	2.4
p-cresol	91.0	97.8	2.2
note: 400 ℃, LHSV 0.5 h^-1, N₂ flow of 20 mL/min, TOS=5 h, Cs loading of 1.0 mmol/g

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