Research on in situ Hydrogenation of o-Cresol over Ni/CMK-3 Catalysts†

doi:10.7503/cjcu20140464

Abstract

Abstract:

In situ hydrogenation was studied by means of Ni loading, temperature, initial pressure, and reaction time over Ni/CMK-3 catalysts. The catalysts were characterized by X-ray diffraction(XRD), H₂ temperature programmed reduction(H₂-TPR) and N₂ adsorption-desorption isotherms. The results revealed that the optimal conditions were confirmed as follow: Ni loading of 20%(mass fraction), reaction temperature of 230 ℃, initial pressure of 0.1 MPa, reaction time of 9 h for in situ hydrogenation. The maximum conversion of o-cresol in optimal condition was determined as 47.56%. Compared with the effect of hydrogen donor solvents, formic acid was the best of four kinds of solvents. The comparsion of cresol isomers, recyclability of Ni/CMK-3 were also discussed.

Key words: In situ hydrogenation, o-Cresol, Nickel-based CMK-3 catalyst

CLC Number:

O643.3

TrendMD:

LI Yanbin, XU Ying, MA Longlong, ZHANG Qi, WANG Tiejun, CHEN Guanyi, ZHANG Limin. Research on in situ Hydrogenation of o-Cresol over Ni/CMK-3 Catalysts^†[J]. Chem. J. Chinese Universities, 2014, 35(12): 2654.

Figures/Tables 16

Table 1 Textural and structural properties of the catalysts

Catalyst	Specific surface area/(m²·g^-1)	Average pore size/nm	Pore volume/(cm³·g^-1)
CMK-3	1128.026	3.411	0.781
20%Ni/CMK-3	984.706	3.399	0.752
SBA-15	674.972	6.419	0.907
20%Ni/SBA-15	558.942	6.581	0.964

Fig.1 Small-angle XRD patterns of SBA-15(a) and CMK-3(b)

Fig.2 H2-TPR profiles of 20%Ni/CMK-3(a) and 20%Ni/SBA-15(b)

Fig.3 TEM images of CMK-3 (A) Horizontal direction; (B) vertical direction.

Fig.4 SEM images of the CMK-3(A) and 20%Ni/CMK-3(B)

Fig.5 Selectivity() and conversion(■,▼) under different Ni loadings

Fig.6 Selectivity() and conversion(▼,■) at different temperatures

Fig.7 Effect of different initial pressure on in situ hydrogenation of o-cresol

Fig.8 Effect of different reaction time on in situ hydrogenation of o-cresol

Table 2 Catalytic effect contrast of Ni/CMK-3 catalsts

Reaction time/h	Conversion of methanol(%)	Selectivity of methane(%)	Reaction time/h	Conversion of methanol(%)	Selectivity of methane(%)
3	5.41	3.19	9	11.21	7.06
6	7.47	4.57	12	12.45	9.52

Table 3 Effects of hydrogen-donor solvents on catalystic performance

Hydrogen donor solvent	Conversion of o-cresol(%)	Selectivity of product(%)		Real hydrogen yield/mol
Hydrogen donor solvent	Conversion of o-cresol(%)	2-Methyl cyclohexanol	2-Methyl cyclohexanone	Real hydrogen yield/mol
Isopropyl alcohol	26.72	15.63	83.22	0.008
Methanol	53.49	36.73	63.20	0.031
Glycerol	64.41	32.14	36.81	0.026
Formic acid	82.24	39.45	60.48	0.041

Fig.9 Effect of different molar ratios of water/methanol on selectivity of product() and conversion of o-cresol

Table 4 Comparsion of the effect on three isomers

Reactant	Conversion of reactant(%)	Selectivity of product(%)		Conversion of methanol(%)
Reactant	Conversion of reactant(%)	2-Methylcyclohexanol	2-Methylcyclohexanone	Conversion of methanol(%)
o-Cresol	45.03	36.73	63.20	10.34
m-Cresol	43.79	39.45	60.48	11.09
p-Cresol	27.62	33.48	65.71	11.62

Table 5 Testing effect of CMK-3 reaction life

Reaction times	Conversion of o-cresol(%)	Selectivity of product(%)		Conversion of methanol(%)
Reaction times	Conversion of o-cresol(%)	2-Methyl cyclohexanol		2-Methyl cyclohexanone
1	45.03	36.73	63.20	10.34
2	40.79	34.17	65.71	8.41
3	25.86	39.45	60.48	2.48
4	6.82	11.37	88.44	0.92

Fig.10 XRD patterns of 20%Ni/CMK-3 before(a) and after reaction one time(b)

Fig.11 SEM images of the catalysts after reaction (A) After first reaction; (B) after second reaction; (C) after third reaction; (D) after fourth reaction.

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