Production of liquid bio-fuel from catalytic de-oxygenation: Pyrolysis of beech wood and flax shives
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Abstract: This study presents a detailed analysis of the catalytic de-oxygenation of the liquid and gaseous pyrolytic products of two biomasses (beech wood and flax shives) using different catalysts (commercial HZSM-5 and H-Y, and lab-synthesised Fe-HZSM-5, Fe-H-Y, Pt/Al2O3 and CoMo/Al2O3). The experiments were all conducted in a semi-batch reactor under the same operating conditions for all feed materials. BET specific surface area, BJH pore size distribution and FT-IR technologies have been used to characterise the catalysts, while gas chromatography-mass spectrometry (GC-MS), flame ionisation detection (GC-FID) and thermal conductivity detection (GC-TCD) were used to examine the liquid and gaseous pyrolytic products. It was firstly seen that at higher catalyst-to-biomass ratios of 4:1, de-oxygenation efficiency did not experience any further significant improvement. Fe-HZSM-5 was deemed to be the most efficient of the catalysts utilised as it helped reach the lowest oxygen contents in the bio-oils samples and the second best was HZSM-5. It was also found that HZSM-5 and H-Y tended to privilege the decarbonylation route (production of CO), whilst their iron-modified counterparts favoured the decarboxylation one (production of CO2) for both biomasses studied. It was then seen that the major bio-oil components (carboxylic acids) underwent almost complete conversion under catalytic treatment to produce mostly unoxygenated aromatic compounds, phenols and gases like CO and CO2. Finally, phenols were seen to be the family most significantly formed from the actions of all catalysts.
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Key words:
- pyrolysis /
- biomass /
- catalytic treatment /
- de-oxygenation /
- bio-oil upgrading
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Figure 3 N2 adsorption/desorption isotherms of catalysts and supports
(a): HZSM-5; (b): Fe-HZSM-5; (c): H-Y; (d): γ-Al2O3
Figure 5 Effect of quantity of catalyst used on global oxygen percentage of flax shive bio-oil
Figure 6 Oxygen content of bio-oil samples obtained with and without catalytic treatment
Figure 7 Liquid product distributions for (a) beech wood and (b) flax shives with and without catalytic treatment
Figure 10 Evolution of CO, CO2, H2 and CH4 with and without catalytic treatment for (a) beech wood and (b) flax shives
Table 1 Ultimate analysis of the biomasses
Biomass Ultimate analysis w/% carbon hydrogen nitrogen oxygen Flax shives (FS) 45.70 5.77 0.41 48.12 Beech wood (BW) 47.38 6.11 < 0.01 46.51 
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Table 2 Proximate analysis of biomasses based on TGA experiments
Biomass Proximate analysis w/% M V FC A Flax shives (FS) 2.78 74.72 19.97 2.53 Beech wood (BW) 5.70 75.93 17.52 0.85
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Table 3 Specific surface areas and specific pore volumes of catalysts used
Catalyst used HZSM-5 Fe-HZSM-5 H-Y Fe-H-Y Al2O3 Pt/Al2O3 CoMo/Al2O3 Specific surface area A/(m2·g-1) 285.7 220.8 763.3 457.7 179.6 30.7 33.3 Specific pore volume v/(cm3·g-1) 0.41 0.25 0.48 - 0.22 - -
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Table 4 Parameters for experimental runs concerning effect of catalyst-to-biomass ratio used
Mass of Fe-HZSM-5 used m/g Height of Fe-HZSM-5 bed/cm Volume of catalytic zone without presence of catalyst v/cm3 Catalyst-to-biomass ratio used Contact t/s 6 2.5 26.55 2: 1 1.94 12 5.0 53.09 4: 1 3.89 28 10.0 106.19 9: 1 7.77
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Table 5 Evolution of percentage of chemical families present in bio-oil from flax shives samples with different catalyst-to-biomass ratios
Chemical family present in bio-oil Bio-oil samples w/% catalyst : biomass ratio 0 2 4 9 Carboxylic acids 34.41 18.79 - - Alkanes 1.86 1.29 - - Aromatics 4.95 6.00 10.30 17.00 Alcohols 10.18 5.82 - - Aldehydes 3.07 1.78 3.26 7.36 Amides 15.13 - - - Ketones 6.93 11.73 12.44 20.96 Esters 9.57 4.03 - - Furans 0.70 1.74 - - Guaiacols 1.20 2.18 13.26 10.72 Phenols 8.31 46.65 60.74 43.96 Carbohydrates 3.68 - - -
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Table 6 Percentages of chemical families present in bio-oil samples with and without catalytic treatment
Percentage wmol/% beech wood bio-oils flax shive bio-oils no catalyst HZSM-5 Fe-HZSM-5 H-Y Fe-H-Y Pt/
Al2O3CoMo/
Al2O3no catalyst HZSM-5 Fe-HZSM-5 H-Y Fe-H-Y Pt/
Al2O3CoMo/
Al2O3Carboxylic acids 36.36 7.50 - 19.83 13.99 23.52 35.31 37.26 - - 30.78 7.83 33.62 36.25 Alkanes 0.85 - - - - 2.91 2.19 2.01 - - - - 2.51 1.38 Aromatics 4.83 13.28 8.97 8.07 4.89 7.77 5.18 4.54 12.15 10.51 7.11 5.26 5.19 4.13 Alcohols 7.36 7.47 5.09 8.61 5.83 12.28 8.88 11.02 9.27 5.79 9.25 5.37 13.52 7.29 Aldehydes 3.62 1.75 1.04 1.87 1.31 4.29 1.81 3.33 0.57 0.82 1.46 2.44 1.84 0.43 Amides 3.92 3.82 - 5.30 2.27 2.36 1.25 3.48 3.22 1.36 3.74 2.24 2.09 0.50 Ketones 10.26 6.21 7.30 5.29 3.79 9.69 10.37 8.53 5.35 9.04 3.84 3.52 15.26 14.53 Esters 9.58 5.42 - 11.41 3.53 10.83 5.17 10.85 1.49 - 11.35 1.89 6.55 3.87 Furans 2.16 4.56 3.99 3.08 2.74 1.03 2.19 0.76 3.04 5.64 2.65 2.54 1.18 1.89 Guaiacols 1.34 3.06 2.07 4.10 1.44 0.91 0.88 1.30 1.05 1.66 3.21 1.39 - 1.06 Phenols 14.46 46.92 71.53 32.43 60.22 16.96 22.05 12.92 63.86 65.18 26.62 67.54 12.54 23.86 Carbohydrates 5.26 - - - - 7.45 4.72 3.99 - - - - 5.70 4.80
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Table 7 Percentages of gaseous components present in non-condensable gas samples with and without catalytic treatment
Percentage φ/% beech wood non-condensable gases flax shive non-condensable gases no catalyst HZSM-5 Fe-HZSM-5 Pt/
Al2O3CoMo/
Al2O3H-Y Fe-H-Y no catalyst HZSM-5 Fe-HZSM-5 Pt/
Al2O3CoMo/
Al2O3H-Y Fe-H-Y H2 1.04 0.93 15.28 36.23 6.97 1.13 10.10 1.30 1.35 13.77 31.91 6.91 1.42 10.03 CO 44.61 49.60 28.61 24.67 42.22 52.38 35.52 35.39 42.34 25.83 25.41 33.46 42.87 28.38 CO2 39.99 32.36 38.61 29.73 37.08 28.67 34.46 50.18 35.79 43.41 32.10 44.91 38.79 41.59 CH4 11.38 5.26 6.18 8.49 11.04 11.87 14.78 10.51 7.29 6.31 8.34 10.24 11.50 14.17 C2H4 1.64 6.66 5.10 0.39 1.47 3.04 2.31 1.40 6.81 4.92 0.66 1.43 2.86 2.13 C2H6 1.13 0.46 1.46 0.48 0.83 1.09 0.94 1.20 0.85 0.65 0.66 1.05 1.40 1.11 C3H6 - 4.73 4.74 - 0.04 1.81 1.88 - 5.56 4.81 0.64 1.36 0.64 1.80
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Table 8 Water content of bio-oil samples
Biomass Catalyst used Water content w/% Standard error /% Beech wood no catalyst 2.39 0.14 HZSM-5 6.06 0.06 Fe-HZSM-5 5.45 0.10 H-Y 3.81 0.05 Fe-H-Y 2.63 0.26 Pt/Al2O3 3.33 0.01 CoMo/Al2O3 4.65 0.33 Flax shive no catalyst 1.23 0.04 HZSM-5 5.45 0.23 Fe-HZSM-5 5.08 0.07 H-Y 3.92 0.08 Fe-H-Y 2.73 0.18 Pt/Al2O3 1.86 0.01 CoMo/Al2O3 3.76 0.29
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Table 9 Conversion and production rates of chemical families present in bio-oil samples obtained with and without catalyst use
Chemical families Conversion ("-" sign) and production ("+" sign) rate /% beech wood bio-oil flax shive bio-oil HZSM-5 Fe-HZSM-5 H-Y Fe-H-Y Pt/
Al2O3CoMo/
Al2O3HZSM-5 Fe-HZSM-5 H-Y Fe-H-Y Pt/
Al2O3CoMo/
Al2O3Carboxylic acids -84 -100 -69 -84 -53 -60 -100 -100 -55 -83 -53 -67 Alkanes -100 -100 -100 -100 +37 +223 -100 -100 -100 -100 +40 +291 Aromatics +372 +23 +159 +4 +217 +74 +133 +30 +60 +11 +122 +27 Alcohols -27 -83 -39 -70 +11 +48 N.C. -70 +1 -61 +37 +83 Aldehydes -65 -93 -73 -86 -20 -93 -80 -86 -47 -41 -38 +113 Amides -71 -100 -48 -95 -46 -29 -67 -95 -39 -89 -67 -98 Ketones -45 -78 -66 -82 -33 -65 -15 -31 -38 -62 +128 +60 Esters -61 -100 -40 -86 -31 -4 -83 -100 -46 -85 -29 +19 Furans +322 +27 +107 +35 -11 -329 +374 +324 +319 +168 +73 +734 Guaiacols +82 -58 +76 -55 -50 +168 -3 -27 +199 -14 -100 +289 Phenols +267 +92 +65 +151 +4 -24 +766 +305 +257 +505 +56 N.C. Carbohydrates -100 -100 -100 -100 -20 -92 -100 -100 -100 -100 -41 -46 conversion ratio = (moles obtained without de-oxygenation-moles obtained after de-oxygenation)/moles obtained without de-oxygenation × 100%
N.C.: no change (same as amount present in non-catalytic sample)
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Table 10 Conversion and production rates of non-condensable gas (NCG) components obtained with and without catalyst use
NCG component Conversion ("-" sign) and production ("+" sign) rate /% beech wood NCG flax shives NCG HZSM-5 Fe-HZSM-5 H-Y Fe-H-Y Pt/
Al2O3CoMo/
Al2O3HZSM-5 Fe-HZSM-5 H-Y Fe-H-Y Pt/
Al2O3CoMo/
Al2O3H2 +67 +4511 +116 +2565 +13960 +1173 +101 +2774 +79 +1837 +8199 +886 CO +109 +101 +132 +118 +123 +79 +131 +97 +98 +101 +142 +75 CO2 +52 +202 +42 +136 +199 +76 +38 +134 +26 +107 +116 +65 CH4 -13 +70 +106 +256 +200 +84 +34 +62 +79 +237 +168 +80 C2H2 -100 -100 -100 -100 -100 -100 N.C. N.C. N.C. Prod. N.C. Prod. C2H4 +662 +874 +266 +286 -4 +70 +839 +849 +234 +280 +59 +88 C2H6 -23 +307 +92 +129 +71 +40 +37 +46 +90 +132 +85 +63 C3H4 Prod. N.C. Prod. Prod. Prod. Prod. -17 -19 +254 +2 +2 +121 C3H6 Prod. Prod. Prod. Prod. N.C. Prod. Prod. Prod. Prod. Prod. Prod. Prod. C3H8 N.C. N.C. N.C. N.C. N.C. Prod. N.C. Prod. Prod. Prod. Prod. Prod. conversion ratio = (moles obtained without de-oxygenation-moles obtained after de-oxygenation)/moles obtained without de-oxygenation × 100%
Prod.: production (produced because of the catalytic treatment, not present in non-catalytic sample);
N.C.: no change (same as amount present in non-catalytic sample)
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