Catalytic Performance of Activated Carbon Supported Pt-Ni Bimetallic Catalyst for Glycerol in situ Hydrogenolysis†

doi:10.7503/cjcu20150857

Abstract

Abstract:

A series of activated carbon supported Pt-M(M=Fe, Ni, Co, Zn, Cu) bimetallic catalysts was prepared via KBH₄ reduction method for glycerol in situ hydrogenolysis to produce 1,2-propanediol. The results showed that Pt-Ni/AC catalyst with a Pt loading(mass fraction) of 2.0% and a Pt/Ni mass ratio of 1∶1 displayed excellent performance at 220 ℃ under 1.0 MPa of N₂ after 8 h reaction time, with a high selectivity of 60.5% and a conversion of 98.7%. In addition, the prepared Pt-Ni/AC had a good catalytic stability, which kept a high activity even after five cycles catalytic evaluation. The results from the characterization of catalysts by N₂ physisorption, XRD, TEM and XPS indicated that nanoparticles with an average size of ca. 2 nm were uniformly dispersed on the support. And the majority of metals in nanoparticles are present in the zerovalent metallic state. The formation of Pt-Ni phase due to the incorporation of Ni in the Pt lattice was responsible for the strong interaction between Pt and Ni metal. The catalytic performance of Pt-Ni/AC was compared with that of Pt/AC and Ni/AC, it was clearly observed that Pt could promote the aqueous phase reforming of glycerol to hydrogen, and Ni could facilitate the hydrogenolysis of glycerol. The unique perfor-mance of Pt-Ni/AC bimetallic catalysts was attribute to the the synergistic effect between Pt and Ni.

Key words: Glycerol aqueous solution, In situ hydrogenolysis, Bimetallic catalyst, Liquid phase reduction, 1, 2-Propanediol

CLC Number:

O643

TrendMD:

KONG Danni, JIANG Tao, ZHANG Yiying, CAO Fahai. Catalytic Performance of Activated Carbon Supported Pt-Ni Bimetallic Catalyst for Glycerol in situ Hydrogenolysis^†[J]. Chem. J. Chinese Universities, 2016, 37(6): 1140.

Figures/Tables 11

Table 1 Physicochemical property of Pt-M/AC catalysts

Catalyst	Specific surface area^a/(m²·g^-1)	Pore volume^a/(cm³·g^-1)	Average pore diameter^a/nm	Mean particle size^b/nm
AC	806	0.53	5.3
Pt-Fe/AC	783	0.45	5.1	2.3
Pt-Ni/AC	768	0.49	5.1	2.1
Pt-Co/AC	763	0.51	5.2	2.3
Pt-Zn/AC	691	0.52	5.2	2.3
Pt-Cu/AC	523	0.49	4.7	4.9

Fig.1 XRD patterns of the Pt-M/AC catalysts before(A) and after(B) reactiona. AC; b. Pt/AC; c. Pt-Ni/AC; d. Pt-Co/AC; e. Pt-Fe/AC; f. Pt-Zn/AC; g. Pt-Cu/AC.

Fig.2 TEM image(A), HRTEM image(B) and particle size distribution(C) of Pt-Ni/AC fresh catalystInset of (A): corresponding SAED pattern.

Fig.3 TEM image(A) and particle size distribution(B) of Pt-Ni/AC catalyst used for five times

Fig.4 XPS spectra of Pt4f(A) and Ni2p(B) for Pt-Ni/AC catalyst

Table 2 Glycerol in situ hydrogenolysis on different Pt-M/AC catalystsa

Catalyst	Conversion(%)	Reaction rate/ (μmol·g^-1·min^-1)	Selectivity(%)
Catalyst	Conversion(%)	Reaction rate/ (μmol·g^-1·min^-1)	1,2-PDO	EG	2-PO	1-PO	CH₄	CO₂	Others^b
2%Pt-2%Fe/AC	99.8	169.6	48.7	7.5	9.8	9.0	1.5	13.0	10.5
2%Pt-2%Ni/AC	98.3	167.0	60.5	9.1	9.9	7.8	1.1	10.5	1.1
2%Pt-2%Co/AC	94.2	159.9	60.1	6.9	10.5	9.5	0.5	10.4	2.1
2%Pt-2%Zn/AC	85.1	144.6	50.3	10.7	12.0	9.8	0.8	10.1	6.3
2%Pt-2%Cu/AC	54.7	92.9	58.5	12.2	9.1	3.1	0.1	2.6	14.4

Table 3 Glycerol in situ hydrogenolysis on Pt-Ni/AC catalysts with different mass ratios of Pt/Nia

Catalyst	Conversion(%)	Reaction rate/ (μmol·g^-1·min^-1)	Selectivity(%)
Catalyst	Conversion(%)	Reaction rate/ (μmol·g^-1·min^-1)	1,2-PDO	EG	2-PO	1-PO	CH₄	CO₂	Others^b
2%Ni/AC	45.7	77.6	50.6	35.8	13.6	0	0	0	0
2%Pt/AC	80.5	136.7	45.1	4.6	15.4	14.2	2.9	14.9	2.9
1%Pt-1%Ni/AC	85.6	145.4	56.3	5.8	11.6	11.9	1.6	11.5	1.3
2%Pt-1%Ni/AC	93.0	158.0	60.9	8.2	10.6	5.6	1.0	12.6	1.1
5%Pt-1%Ni/AC	98.5	167.3	56.8	8.2	11.2	7.6	1.4	13.2	1.6
2%Pt-2%Ni/AC	98.3	167.0	60.5	9.1	9.9	7.8	1.3	10.3	1.1
2%Pt-3%Ni/AC	98.0	166.4	58.3	8.8	9.7	7.2	2.3	12.3	1.4
2%Pt-5%Ni/AC	97.8	166.1	57.8	9.4	9.3	7.1	2.7	12.1	1.6

Fig.5 Effect of reaction temperature on glycerol in situ hydrogenolysisReaction conditions: 0.2 g catalyst(2%Pt-2%Ni/AC), 1.0 MPa N2 pressure, 15 g 10%(mass fraction) glycerol aqueous solution, 8 h.

Fig.6 Effect of N2 pressure on glycerol in situ hydrogenolysisReaction conditions: 0.2 g catalyst(2%Pt-2%Ni/AC), 220 ℃, 15 g 10%(mass fraction) glycerol aqueous solution, 8 h.

Fig.7 Effect of reaction time on glycerol in situ hydrogenolysisReaction condition: 0.2 g catalyst(2%Pt-2%Ni/AC), 220 ℃, 1.0 MPa N2 pressure, 15 g 10%(mass fraction) glycerol aqueous solution

Fig.8 Reuse of Pt-Ni/AC catalyst for glycerol in situ hydrogenolysiReaction condition: 0.2 g catalyst(2%Pt-2%Ni/AC), 1.0 MPa N2 pressure, 15 g 10%(mass fraction) glycerol aqueous solution, 220 ℃, 8 h.

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