Effect of HSM-5 Support Acidity on the Catalytic Performances of Ru-Co for Reductive Amination of Furfural

doi:10.19894/j.issn.1000-0518.250117

Chinese Journal of Applied Chemistry ›› 2025, Vol. 42 ›› Issue (6): 827-837.DOI: 10.19894/j.issn.1000-0518.250117

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Effect of HSM-5 Support Acidity on the Catalytic Performances of Ru-Co for Reductive Amination of Furfural

Jian LI¹^,²^,³, Hai-Yang CHENG¹^,²^,³(), Feng-Yu ZHAO¹^,²^,³

^1.School of Applied Chemistry and Engineering，University of Science and Technology of China，Hefei 230026，China
^2.State Key Laboratory of Electroanalytical Chemistry，Changchun Institute of Applied Chemistry，Chinese Academy of Sciences，Changchun 130022，China
^3.Jilin Province Key Laboratory of Green Chemistry and Process，Changchun Institute of Applied Chemistry，Chinese Academy of Sciences，Changchun 130022，China

Received:2025-03-19 Accepted:2025-05-08 Published:2025-06-01 Online:2025-07-01
Contact: Hai-Yang CHENG
About author:hycyl@ciac.ac.cn
Supported by:
the National Key Research and Development Program of China(2022YFA1504901)

Abstract

Abstract:

Furfural as an important lignocellulosic biomass derived platform molecule can be transferred into high-value added furfurylamine（FAM） by reductive amination reaction in the ammonia and hydrogen atmosphere. A variety of supported Ru-Co bimetallic catalysts were prepared by deposition-precipitation method， and their activities and product yield in reductive amination of furfural were compared and analyzed. Among them， the Ru-Co/HZSM-5（27） catalyst showed excellent catalytic activity and selectivity， yielding 93.8% FAM in reductive amination of furfural at the reaction condition of 90 ℃， 0.8 MPa NH₃ and 3 MPa H₂. By means of X-ray diffraction （XRD）， transmission electron microscopy （TEM）， temperature programmed reduction of hydrogen （H₂-TPR）， temperature programmed desorption of ammonia and hydrogen （NH₃-TPD， H₂-TPD）， the relationship between reductive amination performance and surface structure of the catalyst was investigated in detail. The properties of support， especially the surface acidity， significantly affect the catalytic performance. The excellent catalytic performance of Ru-9Co/HZSM-5（27） catalyst is attributed to its strong acidity and hydrogen activation ability. Through the synergistic effect between the hydrogenation site and the acidic site， the rapid hydrogenation of primary imine and the catalytic ammonolysis of gem-diamine intermediates were promoted， which effectively inhibited the polymerization of primary imine to form trimers and significantly improved the catalytic activity and yield to FAM.

Key words: Furfural, Furfurylamine, Reductive amination, Ru-Co catalyst, Acidic site

CLC Number:

O643

Jian LI, Hai-Yang CHENG, Feng-Yu ZHAO. Effect of HSM-5 Support Acidity on the Catalytic Performances of Ru-Co for Reductive Amination of Furfural[J]. Chinese Journal of Applied Chemistry, 2025, 42(6): 827-837.

Figures/Tables 12

Fig.1 Reaction pathway of reductive amination of furfural （FAL）

Table 1 Catalytic performances of Ru-Co catalysts with different supports in reductive amination reaction of FAL

Entry	Support	Conversion/%	Yield/%
Entry	Support	Conversion/%	FAM	FOL	SIM	Trimers	Others^a
1	HZSM-5（27）	＞99.9	92.5	3.5	-	3.1	0.9
2	Nb₂O₅	＞99.9	87.4	0.9	-	11.7	-
3	ZrO₂	＞99.9	73.5	0.3	-	26.1	-
4	Al₂O₃	＞99.9	60.5	0.9	7.6	29.5	1.4
5	TiO₂	＞99.9	92.1	4.4	-	2.4	1.1
6	CeO₂	＞99.9	82.1	0.8	-	17.1	-
7	Fe₂O₃	＞99.9	76.3	0.8	-	23.0	-
8	MgO	＞99.9	-	-	11.0	88.0	1.0
9	SiO₂	＞99.9	8.6	-	13.3	78.1	-

Table 2 Effects of n（Si）/n（Al） ratios on the catalytic performances of Ru-Co/HZSM-5 catalysts

Entry	n（Si）/n（Al）	Conversion/%	Yield/%
Entry	n（Si）/n（Al）	Conversion/%	FAM	FOL	SIM	Trimers	Others ^a
1	18	＞99.9	91.7	2.1	-	6.2	-
2	27	＞99.9	92.5	3.5	-	3.1	0.9
3	36	＞99.9	81.8	-	-	18.2	-
4	80	＞99.9	61.5	-	-	38.5	-

Fig.2 Yield-time curves of reductive amination of FAL catalyzed by Ru-Co/HZSM-5（18）（A） and Ru-Co/HZSM-5（27）（B）

Fig.3 Catalytic performances of Ru-Co/HZSM-5（27） catalyst with different reduction temperature Reaction conditions： 5 mmol FAL， 0.2 g catalyst， 0.8 MPa NH3， 3 MPa H2， 5 mL tert-butanol， 90 ℃， 2 h

Fig.4 XRD patterns of Ru-Co/HZSM-5 catalysts and standard PDF card for ZSM-5

Fig.5 TEM images of Ru-Co/HZSM-5（27） catalyst

Fig.6 EDS-mapping images of Ru-Co/HZSM-5（27） catalyst

Fig.7 XPS spectra of Ru-Co/HZSM-5 catalysts with different n（Si）/n（Al）

Fig.8 H2-TPR profiles of Ru-Co/HZSM-5 catalysts with different n（Si）/n（Al）

Fig.9 NH3-TPD （A） and H2-TPD （B） profiles of Ru-Co/HZSM-5 catalysts with different n（Si）/n（Al） ratios

Table 3 The amount of the desorbed ammonia and the desorbed hydrogen of Ru-Co/HZSM-5 catalysts

Entry	Catalyst	Desorbed ammonia/（cm³·g^-1） ^a	Desorbed hydrogen/（cm³·g^-1） ^b
1	Ru-Co/HZSM-5（18）	3.31	5.21
2	Ru-Co/HZSM-5（27）	2.78	6.53
3	Ru-Co/HZSM-5（36）	1.66	2.29
4	Ru-Co/HZSM-5（80）	1.04	1.89

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Effect of HSM-5 Support Acidity on the Catalytic Performances of Ru-Co for Reductive Amination of Furfural

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