PYROLYSIS BEHAVIOR ENHANCEMENT OF A LOCAL BIOMASS BY USE OF MINERAL CATALYSTS Ladislao
1 Sandoval-Rangel , Daniela
1 Martínez-Vargas , Carolina
Xulú Alberto Mendoza-Domínguez1*
2 Solís-Maldonado ,
1 Tecnológico
de Monterrey, Escuela de Ingeniería y Ciencias, Ave. Eugenio Garza Sada 2501, Monterrey, Nuevo León, México, 64849 2 Universidad Veracruzana, Facultad de Ciencias Químicas, Prolongación Venustiano Carranza S/N, Poza Rica, Veracruz, México, 93390 *
[email protected]
ABSTRACT The objective of this work was to enhance the pyrolysis of an abundant local biomass (orange peel) by using combinations of this material with cheap mineral catalysts (dolomite and natural zeolite). The effect of catalyst calcination on the pyrolysis products was evaluated by using both non-calcined (NC) and calcined (C) catalysts for the tests. The pyrolysis results showed the non-catalytic test promotes a higher gas yield (38%), while NC-Dolomite generated the highest biooil yield (33%). C-Dolomite showed the highest char yield, with 35.9%. From the GC-TCD analysis of the biogas, it was observed that C-Zeolite generated the highest signal for hydrogen, and for CO at most temperatures. NC-Zeolite showed the strongest CH4 signal at the highest temperatures, while almost all catalytic mixtures generated higher CO2 signals tan the non-catalytic test. From the GC-MS analysis, it was observed that Guaiacol and Cyclotene were abundant compounds in the oils for all tests. Cresols were also identified, with high relative areas in most of the bio oils analyzed. However, for NC-catalysts, Limonene showed the highest relative area of all compounds present in the bio-oil.
INTRODUCTION
(b)
units Area Area units
Biomass has been considered as a viable energy source in Mexico. One of the most abundant agroindustrial wastes in Nuevo León is sweet orange (Citrus sinensis) peel. Different thermochemical routes have been designed to convert biomass into useful products, from which gasification has been considered the most attractive [1]; pyrolysis studies of biomass are key for accurate predictions of biomass consumption rates and product yields [2]. Several catalysts are used in order to improve biomass pyrolysis [3]. Natural minerals produced nationally, such as dolomite and zeolite (clinoptilolite), are attractive due to their low cost and syngas composition selectivity [4].
units Area Area units
(a)
0.5
1
1.5
2
2.5
3
3.5
0.5
1
1.5
Temperature
2
2.5
3
3.5
2.5
3
3.5
Temperature
(c)
(d)
units Area Area units
units Area Area units
Sand Sand NC-Dolomite NC-Dolomite C-Dolomite C-Dolomite NC-Zeolite NC-Zeolite C-Zeolite C-Zeolite
EXPERIMENTAL Table 1. Reaction parameters. Concept Biomass
Description Citrus sinensis dry peel Catalysts NC-Dolomite C-Dolomite NC-Zeolite C-Zeolite Tcalcination 800 °C (4 h) Sample mass 100 g Catalyst mass 100 g Tpyrolysis max 500 °C Bio-oil solvent extraction Solvent Dichloromethane Volume ratio Solvent:bio-oil 2:1 Gas sampling temperatures T1 200 – 290 °C (15 min) T2 300 – 340 °C (5 min) T3 380 – 490 °C (15 min)
Vent
Figure 1. Scheme of the reactor setup.
RESULTS 100 Sand NC-Dolomite C-Dolomite NC-Zeolite C-Zeolite
80
dTGA, -mg/K
% Mass loss
90
70 60 50
0
0.045 0.035 0.025 0.015 0.005
(a)
40
Sand NC-Dolomite C-Dolomite NC-Zeolite C-Zeolite
0.055
(b)
-0.005 100
200
300
400
500
600
700
0
100
Temperature, ºC
200
300
400
500
Temperature, ºC
Figure 2. TGA (a) and dTGA (b) of biomass mixtures. 40
Yields, % wt
30
Char Bio-oil Gas
20
10
0
Sand
NC-Dolomite
C-Dolomite
NC-Zeolite
C-Zeolite
Figure 3. Effect of calcined and non-calcined catalysts on the pyrolysis product yields.
600
700
0.5
1
1.5
2
2.5
3
3.5
0.5
1
1.5
Temperature
2
Temperature
Figure 4. Main gases generated in orange peel pyrolysis at different temperatures. Hydrogen (a), carbon monoxide (b), methane (c), carbon dioxide (d). Table 2. Main products identified in the bio-oils by GC-MS analysis. R.T., min
Compound
5.7 5.8 6.1 6.4 6.7 7.1 7.6 7.8 8.4 8.8 9.5
Cyclotene Limonene o-Cresol m-Cresol / p-Cresol Guaiacol Ethylcyclopentenolone m-Xylenol o-Xylenol Catechol 5-Hydroxymethylfurfural 4-Ethylguaiacol
% Relative area Sand NC-Z C-D NC-Z 17.4 12.3 --15.3 ----25.4 --5.3 5.0 --8.3 6.9 7.0 7.3 8.5 12.6 13.8 10.1 12.3 7.1 --2.2 --5.3 6.7 7.0 5.4 --5.3 ----8.0 5.9 --5.9 4.9 6.3 ----3.3 3.6 2.8 ---
10.0
2-Methoxy-4-vinylphenol Others Not identified
2.1 11.8 15.3
3.9 12.0 18.2
3.0 8.3 33.9
1.7 9.6 32.9
C-Z 8.1 53.9 2.1 3.4 5.7 2.3 ----3.4 ----2.0 11.4 7.7
CONCLUSION The presence of dolomite and natural zeolite (clinoptilolite) produced regionally showed an improvement over the syngas and bio-oil compositions, compared with the non-catalytic test performed with quartz sand. Stronger signals for CO, CH4 and CO2 on the syngas were observed with the catalytic tests, although the highest gas yield was obtained in the non-catalytic test. The effect of catalyst calcination on the pyrolysis behavior was observed. Calcinated catalysts promoted higher char and gas yields, along with stronger H2, CO and CO2 signals in the syngas. They also promote formation of Limonene on the bio-oils, which is a highly valuable compound, while other valuable chemicals such as Guaiacol and 5-HMF are mainly present in the bio-oils formed with the non-calcined catalysts.
REFERENCES [1] A. Bhavanam, R. Sastry. Int J Chem Eng Appl 2 425-433 (2011) [2] S. Ceylan,Y.Topcu. Bioresour Technol 156 182-188 (2014) [3] S. Schmidt, S. Giesa,A. Drochner, H.Vogel. Catal Today 175 442-449 (2011) [4] L. Gurevich, P. Bonelli,A. Cukierman. Fuel Process Technol 159 160-167 (2017)
Esta investigación es un producto del proyecto 266632 “Laboratorio Binacional para la Gestión Inteligente de la Sustentabilidad Energética y la Formación Tecnológica” financiado a través de Fondo CONACYT SENER de Sustentabilidad Energética (S0019201401). This research is a product of the Project 266632 “Laboratorio Binacional para la Gestión Inteligente de la Sustentabilidad Energética y la Formación Tecnológica” [ “Bi-National Laboratory on Smart Sustainable Energy Management and Technology Training”], funded by the CONACYT SENER Fund for Energy Sustainability (Agreement: S0019201401).
