Electronic Supplementary Material (ESI) for RSC Advances. This journal is © The Royal Society of Chemistry 2015 Supplementary Data Bio-oil Production via Catalytic Microwave Pyrolysis of Model Municipal Solid Waste Component Mixtures Dadi V. Suriapparaoa, R. Vinua,b,* a Department of Chemical Engineering, Indian Institute of Technology Madras, Chennai – 600036, India. b National Centre for Combustion Research and Development, Indian Institute of Technology Madras, Chennai-600036, India. * Corresponding Author. Phone: +91-44-22574187. E-mail: [email protected] (R.Vinu) 1 Figure S1. SEM micrographs of various susceptors. 2 Figure S2. Schematic of the microwave pyrolysis experimental set-up.21,24 3 2.5 Polypropylene Polyisoprene 2.0 Paraffin oil ) -1 Polyethylene glycol C o wt.% 1.5 ( 1.0 0.5 Differential mass loss loss mass Differential 0.0 200 250 300 350 400 450 500 550 600 Temperature (oC) Figure S3. Differential mass loss profiles of various polymers and paraffin oil. 4 600 500 400 C) o 300 Paraffin oil Cellulose 200 Temperature ( Temperature Garden waste Kitchen waste 100 0 0 2 4 6 8 10 12 14 16 Pyrolysis time (min) Figure S4. Temperature profiles achieved during the pyrolysis of individual MSW components at 450 W microwave power and 1:1 wt./wt. of feed:graphite. 5 30 600 CO 2 25 CO 500 20 400 C) o 15 300 10 200 Temperature ( Temperature Gas composition (vol.%) composition Gas 5 100 0 0 01234567891011 Pyrolysis time (min) Figure S5. Online analysis of CO and CO2 during microwave pyrolysis of 1:1 MSW- A:graphite. Compared to CO2, CO evolution was very low owing to the composition of the model MSW mixture. 6 Table S1. Composition of garnet, cement, fly ash, silica beads and TiO2. Garnet Composition (wt.%) Al2O3 1 SiO 43.16 Aeroxide® TiO 2 2 Composition (wt.%) P25** Fe2O3 32.17 TiO2 ≥ 99.50 MgO 9.13 Al2O3 ≤ 0.30 Al2O3 6.49 SiO2 ≤ 0.20 CaO 3.87 Fe2O3 ≤ 0.01 FeO 5.18 HCl ≤ 0.30 Cement Composition (wt.%) LOI* ≤ 2.0% Ca3Al2O6 9.87 Ca4Al2Fe2O10 8.34 *LOI - loss on ignitition Ca2SiO5 19.59 **Aeroxide® TiO2 P 25, Evonik Industries, 2007, Ca3SiO4 55.38 www.aerosil.com (accessed 20 Nov. 2014). Na2O & K2O 1.94 CaSO4.2H2O 4.88 Fly ash Composition (wt.%) SiO2 26.97 Fe2O3 4.77 CaO 17.85 MgO 2.00 Al2O3 10.34 Na2O 1.05 K2O 8.40 TiO2 0.70 LOI* 14.71% Silica beads Composition (wt.%) SiO2 69-71 CaO 8-9 Na2O 13 K2O 5 7 Table S2. Composition of bio-oil obtained by pyrolyzing paraffin oil with graphite at 1:1 (wt./wt.) on moisture free basis. Composition Product (area%) Alkanes 25.32 Heptane 2.70 Pentane, 3-ethyl-2-methyl- 1.63 Octane 4.04 Octane, 3-methyl- 1.18 Nonane 3.96 Decane 4.74 1,8-Dimethyl decane 1.36 Heptane, 3,4-dimethyl- 1.99 2,9-Dimethylundecane 1.20 Decane, 2,4,6-trimethyl- 1.06 Dodecane, 2,6,10-trimethyl- 0.90 Undecane, 3,4-dimethyl- 0.54 Cycloalkanes 5.46 Cyclohexane, methyl- 0.70 Cyclopentane, pentyl- 0.73 Cyclooctane, 1,2-dimethyl- 0.95 Cyclopropane, octyl- 1.40 Cyclopentane, 1,1,3-trimethyl- 1.01 Cyclopentane, decyl- 0.68 Alkenes 35.68 1,3,5-Hexatriene 1.16 1-Heptene 5.19 1-Heptene, 2-methyl- 2.22 1-Octene 2.93 1-Octene, 7-methyl- 0.63 1-Nonene 4.71 11-Tricosene 1.03 1-Decene 4.52 2-Dodecene 4.49 5-Dodecene 0.65 3-Dodecene 0.84 1-Octene, 3,7-dimethyl- 0.89 4-Tetradecene 2.15 1-Nonadecene 0.81 3-Eicosene 1.57 8 9-Octadecene 1.17 1-Nonadecene 0.74 Cycloalkenes 5.23 Cyclopentene, 4,4-dimethyl- 0.80 1,3-Cyclopentadiene, 1,2-dimethyl- 0.90 Cyclohexane, 2-propenyl- 1.30 Cyclohexane, 1,1-dimethyl-2-propyl 0.81 Cyclohexene, 1,6-dimethyl- 0.57 Cyclohexane, 1,2-dimethyl-3,5-bis(1-methylethenyl)- 0.85 Alkynes 7.33 5-Dodecyne 1.87 7-Tetradecyne 2.29 8-Hexadecyne 0.69 7-Hexadecyne 0.95 1-Hexadecyne 0.92 1-Pentadecyne 0.61 Single ring aromatic hydrocarbons 9.37 Benzene 3.12 Toluene 2.64 P-Xylene 2.97 Benzene, 1-ethyl-4-methyl- 0.63 Polycyclic aromatic hydrocarbons 3.10 Indene 2.35 Naphthalene, 1-methyl- 0.75 Total 91.49 Table S3. Composition of bio-oil obtained by pyrolyzing cellulose with graphite at 1:1 (wt./wt.) on moisture free basis. Composition Product (area%) Furan derivatives 9.60 Furfural 5.24 Ethanone, 1-(2-furanyl)- 1.31 Furanone, 5-methyl- 0.12 2-Furancarboxaldehyde, 5-methyl- (5-methyl furfural) 2.93 Phenolics 0.17 P-Cresol 0.10 Phenol, 2,4-dimethyl- 0.07 Alkanes 0.94 9 Tritetracontane 0.15 Hexadecane 0.79 Cycloalkanes 6.26 Cyclohexane, 1,1'-(1,2-dimethyl-1,2-ethanediyl)- 1.42 Cyclohexane, 1,2-dimethyl-3-pentyl-4-propyl 0.93 Cyclohexane, 2,4-diisopropyl-1,1-dimethyl- 0.82 Cyclotetracosane 0.50 Cyclohexane, 1,2,4,5-tetraethyl- 0.61 Cyclotetracosane 0.55 Cyclodocosane, ethyl- 1.43 Alkenes 10.57 1-Docosene 1.42 1-Nonadecene 2.84 5-Methyl-Z-5-docosene 0.43 1-Hexacosene 1.42 2,6,10,14-Tetramethyl-7-(3-methylpent-4-enylidene) pentadecane 4.46 Cycloalkenes 0.21 Cyclohexene, 4-(4-ethylcyclohexyl)-1-pentyl 0.21 Alkynes 0.70 8-Hexadecyne 0.70 Ketone derivatives 2.53 2-Propanone, 1-hydroxy- (Acetol) 0.36 Ethanone, 1-cyclopropyl- 0.09 3-Hexanone 0.51 3-Penten-2-one 0.20 Cyclopentanone 0.11 5,9-Dodecadien-2-one, 6,10-dimethyl 0.18 4-Cyclopentene-1,3-dione 0.22 1,2-Cyclopentanedione 0.09 2-Butanone, 1-(acetyloxy)- 0.10 2-Cyclopenten-1-one, 3-methyl- 0.28 Levoglucosenone 0.39 Alcohols derivates 11.65 1,2-Ethanediol, diacetate 0.43 2,6,10-Undecatrien-8-ol, 2,6-dimethyl 0.09 Octacosanol 0.47 Behenic alcohol 0.11 1-Heneicosanol 2.21 Tetracosanol 1.49 11,13-Dimethyl-12-tetradecen-1-ol acetate 0.61 14-Methyl-8-hexadecyn-1-ol 0.42 10 1-Heptacosanol 5.82 Aliphatic aldehydes/acids 0.92 2-Butenal 0.39 Nonahexacontanoic acid 0.53 Total 43.55 Table S4. Composition of bio-oil obtained by pyrolyzing garden waste with graphite at 1:1 (wt./wt.) on moisture free basis. Composition Product (area%) Furan derivatives 3.92 Furfural 3.10 3-Furanmethanol 0.15 Butyrolactone 0.09 2-Furancarboxaldehyde, 5-methyl- 0.10 Benzofuran, 2,3-dihydro- 0.48 Aromatics 1.03 Toluene 0.53 P-Xylene 0.34 Benzene, 1-ethenyl-2-methyl- 0.16 Condensed ring aromatics 0.71 Naphthalene 0.46 Naphthalene, 1,2,3,4-tetrahydro-5,6-dimethyl 0.08 Naphthalene, 2-methyl- 0.17 Phenolics 4.25 Phenol 0.89 P-Cresol 1.20 Phenol, 2-methoxy- 0.56 Phenol, 2,5-dimethyl- 0.18 Phenol, 4-ethyl- 0.14 Phenol, 2,4-dimethyl- 0.06 2-Methoxy-4-vinylphenol 0.75 3-Hydroxy-4-methoxybenzoic acid 0.23 P-tert-Butyl catechol 0.08 Phenol, 2,6-dimethoxy-4-(2-propenyl)- 0.16 Alkanes 0.00 Cycloalkanes 4.09 Cyclohexane, 1,2-dimethyl-3-pentyl-4-propyl- 4.09 Cycloalkenes 1.05 11 Cyclohexane, 1,1'-(1,2-dimethyl-1,2-ethanediyl)- 1.05 Alkenes 12.24 1-Hexacosene 2.77 12-Pentacosene 0.18 2,6,10,14-Tetramethyl-7-(3-methylpent-4-enylidene) pentadecane 9.29 Ketone derivatives 2.16 2-Propanone, 1-hydroxy- 1.03 3-Buten-2-one, 3-methyl- 0.09 3-Penten-2-one 0.10 Cyclopentanone 0.08 2-Propanone, 1-(acetyloxy)- 0.63 1,2-Cyclopentanedione 0.07 Bicycloheptane-2,5-dione, 1,7,7-trimethyl- 0.16 Alcohol derivatives 0.81 6-Octen-1-ol, 3,7-dimethyl-, acetate 0.16 Cycloheptanol, 2-methylene 0.65 Other oxygenates 1.57 Acetic acid 0.24 Propanoic acid, 2-oxo-, methyl ester 0.10 Maltol 0.06 2-Propenal, 2-methyl-3-phenyl- 0.17 4-Ethylbenzoic acid, but-3-yn-2-yl ester 0.08 4-Methoxy-2-methyl-1-(methylthio)benzene 0.06 4-Methyl-2,5-dimethoxybenzaldehyde 0.06 Tridecanedial 0.74 2-Naphthalenone, octahydro-4,7,7-trimethyl- 0.06 Total 31.83 Table S5. Composition of bio-oil obtained by pyrolyzing kitchen waste with graphite at 1:1 (wt./wt.) on moisture free basis. Composition Product (area%) Furan derivatives 7.61 Furfural 4.28 2-Furanmethanol 0.67 Butyrolactone 0.40 2-Furancarboxaldehyde, 5-methyl- 2.09 2-Acetyl-5-methylfuran 0.09 Benzofuran, 2-methyl- 0.08 12 Aromatics 0.25 Toluene 0.25 Condensed ring aromatics 0.35 Indene, 1-methyl- 0.10 Naphthalene 0.12 Naphthalene, 2,6-bis(1,1-dimethylethyl)- 0.08 Indene, 4,7-dimethyl- 0.05 Phenolics 3.41 Phenol 0.38 Phenol, 2,4-dimethyl- 0.60 Phenol, 3-ethyl- 0.14 P-Cresol 2.07 Phenol, 2-methoxy- 0.07 2-Methoxy-4-vinylphenol 0.06 Trans-Isoeugenol 0.09 Alkanes 1.37 Tetracosane 0.90 Octadecane 0.47 Cycloalkanes 2.5 Cyclohexane, 1,2-dimethyl-3-pentyl-4-propyl- 2.50 Alkenes 9.8 Limonene 0.06 1-Hexacosene 2.41 2,4-Hexadiene, 3,4-dimethyl- 0.04 2,6,10,14-Tetramethyl-7-(3-methylpent-4-enylidene) pentadecane 7.29 Ketone derivatives 2.86 2-Propanone, 1-hydroxy- 1.20 3-Penten-2-one 0.08 2-Cyclopenten-1-one, 2-methyl- 0.94 2-Cyclopenten-1-one, 3-methyl- 0.07 2-Cyclopenten-1-one, 3,4-dimethyl- 0.18 1,2-Cyclopentanedione, 3-methyl- 0.22 7-Methylindan-1-one 0.04 Cyclohexanone, 3-ethenyl- 0.08 Ethanone, 1-(methylenecyclopropyl) 0.05 Alcohol derivatives 2.80 2-Methyl-1,5-hexadiene-3-ol 0.05 3-Methylbenzyl alcohol 0.10 Cycloheptanol, 2-methylene 1.44 11,13-Dimethyl-12-tetradecen-1-ol acetate 1.21 Other oxygenates 3.20 13 1,6-Dianhydro-.alpha.-d-glucopyranose 0.18 4-Acetylphenyl ether 0.21 Fumaric acid, 4-cyanophenyl dodecyl ester 1.40 Tridecanedial 1.20 Benzene, 1-ethyl-4-methoxy- 0.10 Cyclopropane, 1-(1'-propenyl)-2-hydroxymethyl- 0.11 Total 34.15 Table S6.