Ni/La2O3-SiO2catalysts applied to glycerol steam reforming reaction: effect of the preparation method and reaction temperature

Thyssen, Vivian V.; Assaf, Elisabete M.

doi:10.5935/0103-5053.20140273

Vivian V. Thyssen

Instituto de Química de São Carlos, Universidade de São Paulo; Av. Trabalhador Sãocarlense, 400, 13560-970 São Carlos-SP, Brazil

Elisabete M. Assaf ^**e-mail: eassaf@iqsc.usp.br

Instituto de Química de São Carlos, Universidade de São Paulo; Av. Trabalhador Sãocarlense, 400, 13560-970 São Carlos-SP, Brazil

*e-mail: eassaf@iqsc.usp.br

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Figure 1
XRD patterns of (a) supports and (b) catalysts. aData based on Thyssen et al.¹⁰10 Thyssen, V. V.; Maia, T. A.; Assaf, E. M.; Fuel2013, 105, 358.

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Figure 2
TPR profiles of catalysts. ^aData based on Thyssen et al.¹⁰10 Thyssen, V. V.; Maia, T. A.; Assaf, E. M.; Fuel2013, 105, 358.

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Figure 3
FTIR of catalysts.

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Figure 4
Gaseous products formed during the steam reforming of glycerol: (a) P, (b) P + I. (■ H₂; ● CH₄; ▲ CO; ▼ CO₂; ◄ C₂H₄).

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Figure 5
Gaseous products formed during the steam reforming of glycerol: (a) I-seqa and (b) I-sim. (■ H₂; ● CH₄; ▲ CO; ▼ CO₂; ◄ C₂H₄). ^aData based on Thyssen et al.¹⁰10 Thyssen, V. V.; Maia, T. A.; Assaf, E. M.; Fuel2013, 105, 358.

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Figure 6
SEM images of P + I and I-sim after reaction.

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Figure 7
DTG: P + I and I-sim after reaction.

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Figure 8
Gaseous products formed during the steam reforming of glycerol, on 10Ni30LaSi (I-sim): (a) 500 °C and (b) 700 °C. (■ H₂; ● CH₄; ▲ CO; ▼ CO₂; ◄ C₂H₄).

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Figure 9
Gaseous products formed during the reaction of steam reforming of glycerol on 10Ni30LaSi (I-sim) over 10 h at 600 °C. (■ H₂; ● CH₄; ▲ CO; ▼ CO₂; ◄ C₂H₄).

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Table 1
Mean contents of La and Ni and specific areas of the catalysts and supports

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Table 2
Results of temperature programmed reduction and H₂ chemisorption

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Table 3
Results of steam reforming of glycerol

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Table 4
Results of steam reforming of glycerol at different temperatures and stability reaction

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Preparation method	Content / wt.%		Specific area / (m² g^-1)
Preparation method	Support (La) 30LaSi	Catalyst (Ni) 10Ni30LaSi	Support 30LaSi	Catalyst 10Ni30LaSi
I-seq^a a Data based on Thyssen et al.10	29.6 ± 2.5	9.7 ± 1.2	101	138
I-sim	33.5 ± 1.8	9.8 ± 0.7	-	121
P+I	31.3 ± 1.9	11.9 ± 0.9	95	109
P	32.6 ± 1.0	10.6 ± 0.2	-	98
SiO₂^a a Data based on Thyssen et al.10	-	-	231	-

Preparation method	Activation temperature / ºC	H₂ consumption (× 10^-5) / mol		Reduction^a a Degree of reduction of oxide phases; / %	D_M^b b metallic dispersion; and / %	S_m^c c metallic area. / (m² g^-1)
Preparation method	Activation temperature / ºC	NiO	La₂NiO₄	Reduction^a a Degree of reduction of oxide phases; / %	D_M^b b metallic dispersion; and / %	S_m^c c metallic area. / (m² g^-1)
I-seq	700	-	4.1	82	26	4
I-sim	600	9.6	-	100	40	14
P + I	700	-	5.0	86	32	6
P	700	-	2.6	48	14	2

Catalyst 10Ni30LaSi	H_2yield / (mol mol^-1)	CH₄^a a C gaseous product yield; / (mol mol^-1)	CO^a a C gaseous product yield; / (mol mol^-1)	CO₂^a a C gaseous product yield; / (mol mol^-1)	C₂H₄^a a C gaseous product yield; / (mol mol^-1)	H₂/CO₂ / (mol mol^-1)	CO₂/CO / (mol mol^-1)	C^b b carbon formation rate; / (produced mmol) (converted mol glycerol)^-1 h^-1	Liquid effluent^c c volume of liquid effluent collected; / mL	X_G^d d glycerol conversion to gaseous products; / %	X_L^e e glycerol conversion to liquid products; / %	X_T^f f global glycerol conversion in 5-h reaction at 600 ºC; / %
I-seq^g g data based on Thyssen et al.;10 t = traces < 0.1 (produced mol) (mol glycerol fed)-1.	2.8	0.2	0.7	1.1	t	2.8	1.6	1.1	5.8	67	12	79
I-sim	3.8	0.4	1.1	1.5	t	2.5	1.4	1.0	3.8	98	2	100
P + I	3.3	0.4	1.1	1.3	t	2.5	1.2	1.1	4.2	93	2	95
P	0.4	0.1	0.5	0.2	t	3.7	0.4	0.06	9.6	27	36	63
No catalyst	0.4	t	0.3	-	-	-	-	-	12.0	10	49	59

10Ni30LaSi (I-sim)	H_2yield / (mol mol^-1)	CH₄^a a C gaseous product yield; / (mol mol^-1)	CO^a a C gaseous product yield; / (mol mol^-1)	CO₂^a a C gaseous product yield; / (mol mol^-1)	C₂H₄^a a C gaseous product yield; / (mol mol^-1)	H₂/CO₂ / (mol mol^-1)	CO₂/CO / (mol mol^-1)	C^b b carbon formation rate; / (produced mmol) (converted mol glycerol)^-1 h^-1	Liquid effluent^c c volume of liquid effluent collected; / mL	X_G^d d glycerol conversion to gaseous products; / %	X_L^e e glycerol conversion to liquid products; / %	X_T^f f global glycerol conversion, for I-sim; t = traces < 0.1 (produced mol) (mol glycerol fed)-1. / %
500 ºC (5 h)	1.3	0.3	0.1	0.5	-	2.4	7	1.2	4.3	30	47	77
600 ºC (5 h)	3.8	0.4	1.1	1.5	t	2.5	1.4	1.0	3.8	98	2	100
700 ºC (5 h)	3.1	0.1	1.3	0.8	-	3.9	0.6	0.7	2.8	73	27	100
600 ºC (10 h)	4.1	0.4	1.2	1.3	t	3.2	1.1	0.9	6.6	97	3	100

[1] *e-mail: eassaf@iqsc.usp.br

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Ni/La₂O₃-SiO₂catalysts applied to glycerol steam reforming reaction: effect of the preparation method and reaction temperature