Appendix A. Supplementary data

Transcription

1 Electronic Supplementary Material (ESI) for RSC Advances. This journal is The Royal Society of Chemistry 2016 Appendix A. Supplementary data Bio-oil production from eight selected green landscaping wastes through hydrothermal liquefaction Leichang Cao, Gang Luo, Shicheng Zhang*, Jianmin Chen Shanghai Key Laboratory of Atmospheric Particle Pollution and Prevention (LAP 3 ), Department of Environmental Science and Engineering, Fudan University, Shanghai , China *Corresponding author Shicheng Zhang Department of Environmental Science and Engineering Fudan University, Shanghai , China zhangsc@fudan.edu.cn Telephone: Fax number: Number of Pages: 28 Number of Figures: 2 Number of Tables: 10 㚽址 햳雎 3

2 Fig. S1 Comparing the HHVs of biochars and feedstocks. (a) leaves, (b) branches. Temperature, 300 C; solid/liquid = 15g/150ml; reaction time, 30min; initial air pressure, 0.1 MPa; recation pressure, MPa. S3

3 Fig. S2 Composition of the gaseous products S4

4 Table S1. The information on the eight green landscaping plants Name of green landscaping plants State of leaves Morphology Growth habit Wood type Botanical classification Evergreen Deciduous Trees Shrubs Ombrophyte Heliophyte Soft wood Hard wood Gymnosperm Angiosperm Pinus Cupressus funebris Platanus Cinnamomum camphora Pittosporum tobira Distylium racemosum Viburnum odoratissinum Salix babylonica 曺鵏 控 懮 S5

5 Biochar from leaves 檎 Table S2. Element composition and high heating value of biochar derived from leaves (wt.%) Pinus Cupressus funebris Platanus Cinnamomum camphora Pittosporum tobira Distylium racemosum Viburnum odoratissinum Salix babylonica Ultimate: C H O a N S b <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 Atom ratios: H/C H/O HHV/(MJ/kg) a Calculated by difference; b determined by ICP-AES Mean value S6 葵 曻

6 Biochar from branches Table S3. Element composition and high heating value of biochar derived from branches (wt.%) Pinus Cupressus funebris Platanus Cinnamomum camphora Pittosporum tobira Distylium racemosum Viburnum odoratissinum Salix babylonica Ultimate: C H O a N S b <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 Atom ratios: H/C H/O HHV/(MJ/kg) a Calculated by difference; b determined by ICP-AES Mean value S7 S4

7 Biochar from branches Table S4. Composition of the gaseous products of each sample (vol.%) Pinus Cupressus funebris Platanus Cinnamomum camphora Pittosporum tobira Distylium racemosum Viburnum odoratissinum Salix babylonica Leaves: CO H CO CH Branches: CO H CO CH Mean value S8

8 Table S5. HHVs comparison of some reported bio-oils and the heavy oils from leaves in the present work Feedstock Reaction condition HHV of bio-oil (MJ/kg) References Leaves 300 C, 30 min, water, air (mean value) Present work Pinus ponderosa 250 C, 120 min, water, air [13] Culture algal 300 C, 60 min, water, N [42] Barley straw 300 C, 0 min, water, N [44] Russian olive seeds 280 C, 5 min, water, N [19] Boron-treated wood 350 C, 60 min, tetralin, H [43] Corncob 280 C, 12 min, water, N [45] S9S3 S5

9 Table S6. Absorption bands of obtained bio-oils Position of the bands (cm -1 ) Functional group Possible compounds present 3383, OH Alcohol, aldehydes, carboxylic acids 2938, 2927; 2883, CH, -CH 2, -CH 3 Aliphatic groups 1721, C=O Carboxylic acid, ketone, aldehydes, and esters 1513 C=C, C=N Unsaturated aliphatics, aromatics, amino acids, amides, etc C-O-C, C-OH Ethers, alcohols, sugars 1044, 1042 =C-H, -NH Ethers, alcohols, polysaccharide-like substances 813, 752 C-halogen, Aromatic rings Halogen compounds, aromatic compounds 628 C-CO-C Aliphatic ketones S10

10 Table S7. Detailed chemicals of light oil from leaves Light Oil-Leaves Compound Name Plant Name / Area (%) RT a Cinnamomum Viburnum Distylium Pittosporum Pinus Cupressus Salix Platanus Ester and Acid (3H)-Furanone, dihydro gamma-valerolactone Crotonic acid, 2-methyl Pentanoic acid, 4-methyl Pentanoic acid, 4-oxo Cyclopentene-1-carboxylic acid Benzoic Acid Benzoic acid, 4-hydroxy-3-methoxy Benzoic acid, 3-ethoxy Benzoic acid, 3-hydroxy (5-tert-Butyl-4-hydroxy-2-methylphenyl)benzoic acid Benzeneacetic acid,.alpha.-hydroxy-2-methoxy Benzeneacetic acid, 4-hydroxy-3-methoxy Dibutyl phthalate n-hexadecanoic acid Octadecanoic acid Hexadecanoic acid, 2-hydroxy-1-(hydroxymethyl)ethyl ester 栐滵쀺졈 Ketone and Alcohol ,5-Hexanedione S11

11 2(3H)-Furanone, dihydro-5-methyl Benzenemethanol cis-1,2-cyclohexanediol Benzeneethanol Benzeneethanol, 2-methoxy Acetophenone, 4-methoxy Ethanone, 1-(2-hydroxyphenyl) Ethanone, 1-(3-hydroxyphenyl) Ethanone, 1-(4-hydroxyphenyl) Benzeneethanol, 4-hydroxy Ethanone, 1-(4-hydroxy-3-methoxyphenyl) ,10-dimethoxy-2,3-dihydroanthracene-1,4-dione Cyclonon-4-ynone Vanillyl methyl ketone Rhododendrol H-1-Benzopyran-2-one, 8-methoxy tricyclo[ (1,4)]undeca-2,4(5),8,10-tetraen-7-one ,8-Dimethyl-1,9-diazabicyclo[5.3.0]decane-5,10-dione ,9-DIAZATRICYCLO[ (3,7)]DODECAN-2,8-DIONE Ethanone, 1-(4-hydroxy-3,5-dimethoxyphenyl) Cyclopentenone Cyclohexanone Cyclopenten-1-one Cyclopenten-1-one.2-methyl Bicyclo[3.1.0]hexan-3-one S ,5-Dimethyl-2-cyclopentenone Ethylcyclopentanone 栐滵쀺졈

12 2-Cyclopenten-1-one.3-methyl Cyclopenten-1-one, 3,4-dimethyl ,3-Dimethyl-2-cyclopenten-1-one ,5-Cyclohexadiene-1,4-dione, 2-methyl Bicyclo[4.1.0]hept-3-ene-2,5-dione Cyclopenten-1-one, 2-hydroxy-3-methyl Cyclopenten-1-one.2,3-dimethyl ,5-DIMETHYL CYCLOPENTENOLONE ,4-Cyclohexanedione Cyclopenten-1-one, 3-ethyl-2-hydroxy Hydroxy-5,5-dimethylcyclopent-2-en-1-one (2-Oxopropyl)-1-cyclopentanone H-Benzocyclohepten-2-one, 3,4,4a,5,6,7,8,9-octahydro Pyrrolo[1,2-a]pyrazine-1,4-dione, hexahydro-3-( methylpropyl) Phenolics Phenol Phenol.2-methyl Phenol.3-methyl Phenol.4-methyl Phenol.2-methoxy Phenol, 2-ethyl Phenol.4-ethyl Phenol.4-methoxy-2-methyl Phenol.2-methoxy-4-methyl S ,2-Benzenediol ,2-Benzenediol.3-methoxy Hydroquinone Phenol, 4-ethyl-2-methoxy 栐滵쀺졈

13 1,2-Benzenediol, 4-methyl ,4-Benzenediol.2-methyl Phenol.2,6-dimethoxy ,2,3-Benzenetriol Ethylcatechol ,7-Di-tert-butyl-1-naphthol ,3-Benzenediol, 4-ethyl ,4,5-Trihydroxytoluene ,4-Benzenediol, 2,6-dimethyl Phenol, 2,6-dimethoxy-4-(2-propenyl) Phenol, 2,2'-methylenebis[6-(1,1-dimethylethyl)-4-methyl Phenol, 4,4'-methylenebis[2,6-dimethoxy Furan&Aldehydes Ethanone, 1-(2-furanyl) ,4-Dimethyl-3-(methoxycarbonyl)-5-ethylfuran Alkane & Alkene & Alkyne ,4-Hexadiene trans-1,4-hexadiene ,4-Hexadiene, 3,4-dimethyl-, (Z,Z) Methylbicyclo[4.1.0]heptane (1-Methylnorcarane) acetyl-1-methyl-1-cyclohexene Benzocycloheptatriene S (Trimethyl-[3-(3-phenylcyclopentylidene)-1-propynyl]silane [2-(Trimethylsilyl)ethynyl]-3-phenylcyclohexene Tetradecene (2-Naphthyl)-1-propene 栐滵쀺졈

14 3,5,7-Trioxatetracyclo[ (4,11).0(6,10)]dodecane ,8-dimethylbenzocyclooctene Hexadecene ,4-diaza-2,5-dioxo-3-isobutyl bicyclo[4.3.0]nonane Octadecene Nonadecene Eicosene, (E) benzyl-1,4-diaza-2,5-dioxobicyclo[4.3.0]nonane Cyclotetracosane Heptadecene Others S11 S15 栐滵쀺졈

15 Table S8. Detailed chemicals of heavy oil from leaves Heavy Oil-Leaves Compound Name Plant Name / Area (%) RT a Cinnamomum Viburnum Distylium Pittosporum Pinus Cupressus Salix Platanus Ester and Acid Dodecanoic acid Tridecanoic acid Tetradecanoic acid Linoleic acid ethyl ester Hydroxydodecanoic acid Dibutyl phthalate ,2-Benzenedicarboxylic acid, bis(2-methylpropyl) ester l-proline, N-butoxycarbonyl-, isohexyl ester n-hexadecanoic acid ,12-Octadecadienoic acid (Z,Z) Octadecenoic acid, (E) Octadecanoic acid Benzeneacetic acid, 4-hydroxy methoxy-, methyl ester Ketone and Alcohol Benzeneethanol, 2-methoxy (3S)-2-chloro-1-phenyl-1-penten ol Butanone, 1-(2,4,6-trihydroxy methylphenyl) 栐滵쀺졈 S16

16 5,6-Dimethyl-4-phenyl cyanopyridine-2(1h)-thione (2R(*),3aR(*),6aR(*))-Hexahydro- 2-phenyl-4H-cyclopenta[b]furan one (Z)6,(Z)9-Pentadecadien-1-ol Phenanthrenemethanol Androst-16-en-3-one, (5.alpha.) Cyclopentenone Cyclopenten-1-one Cyclopenten-1-one, 2-methyl Cyclopenten-1-one.2,3-dimethyl Cycloocten-1-one, 6,6-dimethyl-, (E) Oxacyclohexadecan-2-one ,2,4-TRIAZOLO(3,4-C)(1,2,4) BENZOTRIAZIN-1(5H)-ONE Oxacycloheptadec-8-en-2-one (3',4'-Dimethoxyphenyl)-2- hydroxy-7-methoxycyclohepta ,4,6-trien-1-one Phenolics Phenol Phenol.2-methyl Phenol.4-methyl Phenol.2-methoxy Phenol.4-ethyl Phenol.2-methoxy-4-methyl Phenol.2,6-dimethoxy S Phenol, 2-methoxy-4-propyl 栐滵쀺졈

17 Phenol, 2-methoxy-4-(2-propenyl) Totarol Phenol, 2,2'-methylenebis[6-(1, dimethylethyl)-4-methyl Phenanthrenol, 4b,5,6,7,8,8a,9,10-octahydro- 4b,8,8-trimethyl-1-(1-methylethyl) , (4bS-trans) Gigantol Furan&Aldehydes tert-Butyl-4-(hydroxtmethyl)-5- formylfuran ,4-Dimethyl (methoxycarbonyl)-5-ethylfuran E-15-Heptadecenal ,6-Dimethoxy ethylbenzaldehyde Benzaldehyde, 3-hydroxy-, (2, dinitrophenyl)hydrazone Indole Indole H-Indole, 2-methyl H-Indole, 2,3-dimethyl H-Indole, 2,3,7-trimethyl Alkane & Alkene & Alkyne Acetyl-1-methylcyclohexene S18 1-Tetradecene (2-Naphthyl)-1-propene Hexadecene (2-naphthyl)-1-butene 栐滵쀺졈

18 4,6,6-Trimethyl-2-(3-methylbuta- 1,3-dienyl) oxatricyclo[ (2,4)]octane n-Hexylthiane, S,S-dioxide H-Benzo[b]fluorene Hexadecene, 3,7,11, tetramethyl-, [R-[R@,R@-(E)]] Oxirane, tridecyl Cyclohexadecane, 1,2-diethyl Dodecenol Eicosene Phenyl-1-(1'-naphthyl)-1, hexadiene Cyclohexane, hexaethylidene ,4,9-Decatriene, (Z) Cyclooctene, 3-ethenyl Hexadecen-6-yne, (E) Cyclopentadecane Octadecene Cyclotetracosane Eicosene, (E) Docosene Nonadecene Heptadecene S Others 栐滵쀺졈

19 Table S9. Detailed chemicals of light oil from branches Light Oil-Branches Plant Name / Area (%) Compound Name RT a Cinnamomum Viburnum Distylium Pittosporum Pinus Cupressus Salix Platanus 擾㼴栝혊稦 Ester and Acid Butenoic acid, 2-methyl-, (E) Pentanoic acid, 4-oxo Acetylbutyric acid S21

20 Benzenepropanoic acid Benzoic acid, 3-hydroxy Benzeneacetic acid, 4-hydroxy-3-methoxy beta.-(4-hydroxy-3-methoxyphenyl)propionic acid Dibutyl phthalate n-hexadecanoic acid Octadecanoic acid METHOXY-5,6-DIHYDROBENZO(1,2-B:5,4- B')DIFURAN-2-CARBOXYLIC ACID Hexadecanoic acid, 2-hydroxy-1-(hydroxymethyl)ethyl ester Ketone and Alcohol (3H)-Furanone, dihydro ,5-Hexanedione (3H)-Furanone, dihydro-5-methyl (3H)-Furanone, 5-ethyldihydro-5-methyl Benzenemethanol Ethanone, 1-(3-methyl-1H-pyrazol-4-yl) Benzeneethanol Penten-2-one, 4-methyl Benzeneethanol, 2-methoxy Ethanone, 1-(3-hydroxyphenyl) Methoxy-4-methyl-2,5-cyclohexadienone S22 擾㼴栝혊稦

21 Ethanone, 1-(4-hydroxy-3-methoxyphenyl) H-Pyran-2,4(3H)-dione, 3-acetyl-6-methyl Propanone, 1-(4-hydroxy-3-methoxyphenyl) ,2,3,6,7,7a-Hexahydro-4,7a-dimethyl-5H-inden-5-one Homovanillyl alcohol ,4-Dimethoxybenzyl alcohol (3S)-2-chloro-1-phenyl-1-penten-3-ol Pentanone, 1-(2,4,6-trihydroxyphenyl) Ethanone, 1-(4-hydroxy-3,5-dimethoxyphenyl) [2,4,6-Tris(1-methylethyl)phenyl]1,2-butadione H-Xanthen-9-one, 1-hydroxy-3,5,6-trimethoxy Methyl-6-oxo-7-(phenylthio)heptan-3-ol Podocarp-12-en-14a-ol Pyrrolo[1,2-a]pyrazine-1,4-dione, hexahydro-3- (phenylmethyl) Cyclopentenone Cyclopenten-1-one.2-methyl Cyclopenten-1-one.3-methyl Cyclopenten-1-one, 3,4-dimethyl S23 擾㼴栝혊稦

22 2-Cyclopenten-1-one, 2-hydroxy-3-methyl Cyclopenten-1-one.2,3-dimethyl ,5-DIMETHYL CYCLOPENTENOLONE Cyclopenten-1-one, 3-ethyl-2-hydroxy ,5-Cyclohexadiene-1,4-dione, 2-hydroxy-5-methyl Acetonylcyclopentanone Hydroxy-3-propyl-2-cyclopenten-1-one Cyclohexen-1-one, 4-(1-methylethyl) ,7-dimethylbicyclo[3.3.0]octan-2-one Cyclopenten-1-one, 2,3,4,5-tetramethyl (E)-4-[2-Methyl-4-(2,6,6-trimethyl-1-cyclohexen-1-yl)- 2-butenyl]-3-cyclohexen-1-one Bicyclo[4.3.0]nonan-2-one, 8-isopropylidene ,5-Cyclohexadiene-1,4-dione, 2,3-dimethoxy-5- methyl- 5-(3'-Methyliden-2'-oxa-butyliden)-3,3-dimethylcyclohexanone 8,8-Dimethyl-1,9-diazabicyclo[5.3.0]decane-5,10- dione 擾㼴栝혊稦 Phenolics S24

23 Phenol Phenol.2-methyl Phenol.3-methyl Phenol.4-methyl Phenol.2-methoxy Phenol.4-ethyl Phenol.2-methoxy-4-methyl ,2-Benzenediol Phenol, 3-methoxy ,2-Benzenediol.3-methoxy Hydroquinone ,2-Benzenediol, 4-methyl ,4-Benzenediol.2-methyl Phenol.2,6-dimethoxy CIS-ISOEUGENOL Phenol.3,4-dimethoxy Phenol, 2-methoxy-4-propyl ,2,3-Benzenetriol ,4-Benzenediol, 2-methoxy ,7-Di-tert-butyl-1-naphthol ,3-Benzenediol, 4-ethyl Phenol, 4-(3-hydroxy-1-propenyl)-2-methoxy Phenol, 2,6-dimethoxy-4-(2-propenyl) Phenol, 2,6-dimethyl-4-nitro Phenol, 2,2'-methylenebis[6-(1,1-dimethylethyl)-4- methyl S Gigantol 擾㼴栝혊稦

24 Furan&Aldehydes Acetyl-5-methylfuran Cyclopentanecarboxaldehyde, 2-methyl-3-methylene Ethyl-2-furaldehyde Vanillin Benzaldehyde, 4-hydroxy-3-methoxy ,4-Dimethyl-3-(methoxycarbonyl)-5-ethylfuran E-15-Heptadecenal Syringaldehyde Alkane & Alkene & Alkyne Cyclobutene, 1,2,3,4-tetramethyl-, cis ,4-Hexadiene, 3,4-dimethyl-, (Z,Z) ,5-Hexadiyne Silacyclohexadiene-2, [2-(Trimethylsilyl)ethynyl]-3-phenylcyclohexene Hexadecene ,2-Dimethylenecyclohexane (2-naphthyl)-1-butene Cyclohexadecane, 1,2-diethyl Octadecene Cyclotetracosane S26 1-Nonadecene Docosene 擾㼴栝혊稦

25 Others S27 擾㼴栝혊稦

26 Table S10. Detailed chemicals of heavy oil from branches Heavy Oil-Branches Compound Name Plant Name / Area (%) RT a Cinnamomum Viburnum Distylium Pittosporum Pinus Cupressus Salix Platanus Ester and Acid Hydroxy-4-methoxybenzoic acid Benzeneacetic acid, 4-hydroxy-3-methoxy ,2-Benzenedicarboxylic acid, dibutyl ester Dibutyl phthalate n-hexadecanoic acid ,12-Octadecadienoic acid (Z,Z) Octadecenoic acid, (E) Octadecanoic acid Benzeneacetic acid, 4-hydroxy-3-methoxy-, methyl ester DEHYDROABIETIC ACID Hexadecanoic acid, 2-hydroxy (hydroxymethyl)ethyl ester Ketone and Alcohol Benzeneethanol, 2-methoxy Ethanone, 1-(4-hydroxy-3-methoxyphenyl) Propanone, 1-(4-hydroxy-3-methoxyphenyl) S28

27 Homovanillyl alcohol (3S)-2-chloro-1-phenyl-1-penten-3-ol Pentanone, 1-(2,4,6-trihydroxyphenyl) ,6-Dimethylthieno[2',3':3,4]bicyclo[3.3.0]oct (7)-en-2-one Androst-16-en-3-one, (5.alpha.) Androst-5,16-diene-3.beta.-ol Cyclopentenone Cyclopenten-1-one, 2-methyl ,5-Hexanedione Cyclopenten-1-one, 3-methyl Cyclopenten-1-one.2,3-dimethyl ,5-Cyclohexadiene-1,2-dione, 3,4,5, tetrachloro Methoxy-5-(2',3'- dimethoxyphenyl)cyclohepta-2,4,6-trien-1-one Phenolics Phenol Phenol.4-methyl Phenol.2-methoxy Phenol.4-ethyl Phenol.4-methoxy-2-methyl Phenol.2-methoxy-4-methyl Methoxy-5-methylphenol ,2-Benzenediol.3-methoxy Phenol.2,6-dimethoxy S Phenol, 2-methoxy-4-propyl Phenol, 2-methoxy-4-(2-propenyl) CIS-ISOEUGENOL Phenol, 2,6-dimethoxy-4-(2-propenyl)

28 Phenol, 2,2'-methylenebis[6-(1,1- dimethylethyl)-4-methyl Phenanthrenol, 4b,5,6,7,8,8a,9,10-octahydro- 4b,8,8-trimethyl-1-(1-methylethyl)-, (4bStrans) Gigantol Phenol, 2,2'-methylenebis[6-(1,1- dimethylethyl)-4-methyl Furan&Aldehydes Vanillin tert-Butyl-4-(hydroxtmethyl)-5-formylfuran 2,4-Dimethyl-3-(methoxycarbonyl)-5-ethylfuran Phenyls Naphthalene, 1-methyl Naphthalene, 2,6-dimethyl Naphthalene, 2,3-dimethoxy ,2'-Dimethyl-4,4',5,5'-tetramethoxybiphenyl [3-methyl-6-(1-methylethenyl)-2-cyclohexen- 1-yl)-5-pentyl-1,3-dimethoxybenzene Alkane & Alkene & Alkyne /-.-4-Acetyl-1-methylcyclohexene Tetradecene Hexadecene HEPTADECENE-(8)-CARBONIC ACID-(1) Cyclohexadecane Octadecene Cyclotetracosane Docosene

29 1-Heptadecene nitroindole[2,3-a]cyclodec-1-ene Others