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Energies 2019, 12, 809 19 of 41 Bio-oil hydrotreating involves deCOx reactions but proceeds mainly through hydrodeoxygenation (HDO), as shown on the following conceptual reaction proposed by Bridgwater [171]: C1H1.33O0.43 + 0.77H2→ CH2 + 0.43H2O (4) where CH2 represents an unspecified hydrocarbon product. The catalysts which were originally examined were the sulfided Co-Mo and Ni-Mo supported on Al2O3 or alumino-silicate which are well known for their efficiency in the desulfurization of petroleum distillates [174]. However, these catalysts suffered from low stability due to the high water content of the bio-oil. Also, due to gradual loss of sulfur they were requiring frequent re-sulfurization. Research was then focused to noble metal catalysts on various supports like Pd/C, Pt/Al2O3-SiO2, Ru/Al2O3, Ru/C and Ru/TiO2. A brief review of the research of bio-oil hydrotreating on these catalysts is presented in Table 7 [175–179]. Catalyst Co–Mo/Al2 O3 Co–Mo/Al2 O3 Ni–Mo/Al2 O3 Ni–Mo/Al2 O3 Pd/C Pd/C Pt/Al2 O3 -SiO2 Ru/Al2 O3 Ru/C Ru/C Ru/TiO2 Reactor Type Batch Continuous Batch Continuous Batch Continuous Continuous Batch Continuous Batch Batch Time, h 4 4 4 0.5 4 4 0.5 4 0.2 4 4 Pressure, bar 200 300 200 85 200 140 85 200 230 200 200 Yield of Oil, wt% Ref. 26 175 33 176 28 175 84 177 65 175 48 178 81 177 36 175 38 179 53 175 67 175 Table 7. Review of the catalysis research for the hydrotreating of bio-oil. Temperature, ◦C 350 370 350 400 350 340 400 350 350-400 350 DOD 1, % 81 100 74 28 85 64 45 78 73 86 77 In a conventional refinery fluid catalytic cracking (FCC) is used to convert the high molecular weight and high boiling point fractions of petroleum into more valuable lighter products such as gasoline or gases. The cracking of these heavy distillates was originally accomplished by thermal cracking, but it has been replaced almost completely by catalytic cracking because it produces higher yields of gasoline with high octane rating. Bio-oil upgrading can take place through chemical reactions similar to FCC in a process known as catalytic vapor cracking or zeolite cracking. Zeolite cracking removes oxygen from the bio-oil as CO2, as shown in the following conceptual reaction [171]: C1H1.33O0.43 + 0.26O2→ 0.65CH1.2 + 0.33CO2 + 0.27H2O (5) where CH1.2 represents an unspecified hydrocarbon product. The process typically takes place between 300 and 600 ◦C over zeolite catalysts which are also used in the FCC industry. A brief review of the research of bio-oil zeolite cracking is presented in Table 8 [180–183]. 350 1 DOD is the Degree of Deoxygenation calculated as: DOD = (1 − (wt% of O in the products/wt% of O in the feed)) × 100%. 5.3. Bio-Oil Upgrading through Catalytic Vapor (Zeolite) Cracking Catalyst Time, h Temperature, ◦C 380 330 330 380 500 370 370 370 380 Pressure, bar 1 1 1 1 1 1 1 1 1 DOD 1, % n/a n/a n/a 50 50 n/a n/a n/a n/a Yield of Oil, wt% Ref. 18 180 17 181 28 181 24 180 12 182 16 183 20 183 22 183 19 180 Table 8. Review of the research for the catalytic vapor cracking of bio-oil. GaHZSM-5 0.32 H-Modernite 0.56 H-Y 0.28 HZSM-5 0.32 HZSM-5 0.91 MgAPO-36 0.28 SAPO-11 0.28 SAPO-5 0.28 ZnHZSM-5 0.32 1 The Degree of Deoxygenation (DOD) is calculated by the relation given in Table 7.PDF Image | Green Diesel: Biomass Feedstocks, Production Technologies
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