Mass production of chemicals from biomass-derived oil by directly atmospheric. distillation coupled with co-pyrolysis

Transcription

1 Supplementary Materials Mass production of chemicals from biomass-derived oil by directly atmospheric distillation coupled with co-pyrolysis Xue-Song Zhang, Guang-Xi Yang, Hong Jiang*, Wu-Jun Liu & Hong-Sheng Ding Department of Chemistry, University of Science and Technology of China, Hefei , China * To whom correspondence should be addressed. jhong@ustc.edu.cn (H. Jiang) The following is included as the supplementary information for this paper S1

2 Supplementary Methods Quantification of analytes by GC-FID. Quantification of selected components of distillate and distillate fractions was performed on a gas chromatograph (GC-1690, KeXiao Co., Hangzhou, China) equipped with a moderately polar OV-1701 capillary column (30 m 0.32 mm i.d., film thickness 1.00 µm ) and a hydrogen flame ionization detector (FID). The oven temperature was held at 313 K for 12 min, and programmed to ramp at 4 K/min to 453 K and then at 10 K/min to 523 K. The temperature of both injector and FID was set at 523 K. Distillate samples were prepared as ca. 5 wt.% solutions in absolute ethanol and each time 1 µl of the sample was injected. Chromatographic peaks were identified by comparing their retention time with that of authentic compounds. 1-bromobenzene was used as the internal standard (IS) for quantification. Calculation of the relative response factors (RRF). The response factors of individual compounds relative to the IS, 1-bromobenzene, were determined by preparing and injecting samples containing known amounts of both analytes and bromobenzene. Each sample was analyzed for several times and the relative response factors for each analyte were given as the average values. The relative response factors of 13 selected analytes are listed in Supplementary Table S2. The relative response factors of analyte i is defined as A m i i RRF i = (1) AIS mis where A i and A IS stand for the peak areas of analyte i and IS on the chromatogram, respectively; while m i and m IS represent the weight of analyte i and IS contained in the S2

3 sample. List of Tables Table S1 Identified compounds in bio-oils prepared from fast co-pyrolysis of ADR and rice husk Table S2 The relative response factors of analytes Table S3 Ultimate and proximate analyses of rice husk and ADR Table S4 Yield and separation efficiency of selected compounds in distillate Table S5 Calculation of total quantified carbon in whole distillate Table S6 Major compounds identified in distillate of bio-oil by GC/MS Table S7 Elemental analysis of raw bio-oil and its distillation products S3

4 Table S1 Identified compounds in bio-oils prepared from fast co-pyrolysis of ADR and rice husk RT a (min) Compounds Peak area (%) ADR-0 b ADR-20 ADR formic acid hydroxyacetaldehyde acetic acid acetol (1S,2R)-1,2-bis[(2R)-oxiran-2-yl]ethane-1,2-diol propanoic acid hydroxy-2-butanone methyl 2-oxopropanoate diethoxymethyl acetate furfural furfuryl alcohol acetoxy-2-propanone methyl-2-cyclopenten-1-one n.d (5H)-furanone and/or 2(3H)-furanone γ-butyrolactone cyclohexen-1-ol hydroxy-2-cyclopenten-1-one methyl-2(5H)-furanone 0.29 n.d. n.d (3,3-dimethyloxiranyl)ethanone n.d methylfurfural methyl-2-cyclopenten-1-one phenol hydroxy-γ-butyrolactone methyl-3-hexen-2-one {2-[2-(methylamino)propyl]phenyl}-1-p ropanone methyl-1,2-cyclopentanedione o-cresol p-cresol guaiacol ethyl-2-hydroxy-2-cyclopenten-1-one ,4-dioxaspiro[2.4]heptan-5-one ,4-dimethylphenol n.d methyl-1,4-dioxaspiro[2.4]heptan-5-one S4

5 methyl-1,4-dioxaspiro[2.4]heptan-5-one ethylphenol ,5-dihydroxy-2-methyl-4H-pyran-4-one 0.29 n.d. n.d (propan-2-yl)dihydrofuran-3(2H)-one 0.50 n.d. n.d ,2-benzenediol and 4-methylguaiacol ,4:3,6-dianhydro-α-d-glucopyranose 0.50 n.d. n.d ,3-dihydrobenzofuran hydroxymethylfurfural (HMF) ,3-anhydro-d-galactosan and/or 3,4-anhydro-d-galactosan ,3-anhydro-d-mannosan ethyl-6-methylphenol n.d methyl-1,2-benzenediol n.d methoxy-1,2-benzenediol and/or 4-methoxy-1,2-benzenediol n.d hydroxy-4,4-dimethyldihydrofuran-2(3 H)-one Hydroquinone n.d ethylguaiacol methylcatechol vinylguaiacol ,2,4-cyclopentanetriol n.d (2-propenyl)phenol n.d syringol allylguaiacol propylguaiacol n.d. n.d ethylresorcinol vanillin lactoside n.d ,5-dimethylbenzene-1,4-diol n.d allyl-6-methoxyphenol ,2,3-trimethoxybenzene isoeugenol ethyl-1,2-dimethoxybenzene 0.18 n.d. n.d (4-hydroxy-3-methoxyphenyl)ethanone n.d ,6-anhydro-β-D-glucopyranose (levoglucosan) hydroxy-3,4-dihydro-2H-chromen-2-on e n.d (4-hydroxy-3-methoxyphenyl)propan-2- one ,4-altrosan (3,4-dimethoxyphenyl)-6-methyl-3,4-ch romanediol 0.39 n.d. n.d methyl-2,5-dimethoxybenzaldehyde n.d S5

6 ,3-anhydro-d-galactosan n.d ,6-anhydro-α-d-galactofuranose 0.35 n.d methoxy-2-methyl-5-(propan-2-yl)cyclo hexa-2,5-diene-1,4-dione n.d (4-hydroxy-3-methoxyphenyl)butan-2-o n.d n.d. ne allyl-2,6-dimethoxyphenol acetosyringone n.d (2,4,6-trihydroxyphenyl)pentan-2-one n.d n-hexadecanoic acid oleic acid a Retention time. b ADR-x stands for ADR content in feedstock (x wt.%). S6

7 Table S2 The relative response factors of analytes Analyte RRF 2,3-Butanedione Butanone Acetic acid ,3-Pentanedione Acetol Propanoic acid Furfural n-butyric acid Furfuryl alcohol Phenol Guaiacol o-cresol p-cresol S7

8 Table S3 Ultimate and proximate analyses of rice husk and ADR Rice husk ADR Ultimate analysis (wt.%, on dry basis) C H N O a Proximate analysis (wt.%, on dry basis) Volatile matter Fixed carbon Ash a By difference. S8

9 Table S4 Yield and separation efficiency of selected compounds in distillate Acetic Propanoic n-butyric Furfuryl Acetol Furfural acid acid acid alcohol Phenol Guaiacol o-cresol p-cresol Formula C 2 H 4 O 2 C 3 H 6 O 2 C 3 H 6 O 2 C 5 H 4 O 2 C 4 H 8 O 2 C 5 H 6 O 2 C 6 H 6 O C 7 H 8 O 2 C 7 H 8 O C 7 H 8 O Boiling point (K) Yield (wt% of raw bio-oil) Fraction Fraction Fraction Fraction Fraction Fraction Whole distillate Concentration in Raw bio-oil Separation efficiency (%) Whole distillate S9

10 Table S5 Calculation of total quantified carbon in whole distillate Formula Carbon content Yield in whole distillate Quantified carbon in whole distillate wt% of raw bio-oil wt% of raw bio-oil Acetic acid C 2 H 4 O Acetol C 3 H 6 O Propanoic acid C 3 H 6 O Furfural C 5 H 4 O n-butyric acid C 4 H 8 O Furfuryl alcohol C 5 H 6 O Phenol C 6 H 6 O Guaiacol C 7 H 8 O o-cresol C 7 H 8 O p-cresol C 7 H 8 O ,3-Butanedione C 4 H 6 O Butanone C 4 H 8 O ,3-Pentanedione C 5 H 8 O Total quantified carbon S10

11 Table S6 Major compounds identified in distillate of bio-oil by GC/MS a Entries RT (min) b Compounds Formula b.p. (K) c ,3-butanedione C 4 H 6 O butanone C 4 H 8 O acetic acid C 2 H 4 O acetol C 3 H 6 O ,3-pentanedione C 5 H 8 O penten-2-one C 5 H 8 O hydroxy-2-butanone C 4 H 8 O methyl 2-oxopropanoate C 4 H 6 O furfural C 5 H 4 O furfuryl alcohol C 5 H 6 O acetoxy-2-propanone C 5 H 8 O methyl-2-cyclopente n-1-one C 6 H 8 O (2-furanyl)-ethanone C 6 H 6 O methylfurfural C 6 H 6 O methyl-2-cyclopente n-1-one C 6 H 8 O acetoxy-2-butanone C 6 H 10 O phenol C 6 H 6 O methyl-1,2-cyclopent anedione C 6 H 8 O o-cresol C 7 H 8 O p-cresol C 7 H 8 O guaiacol C 7 H 8 O ethylphenol C 8 H 10 O methylguaiacol C 8 H 10 O ethylguaiacol C 9 H 12 O a Only peaks whose peak area percentage above 1% were listed, propanoic acid and n-butyric acid were also detected but not listed for their little response on non-polar columns. b Retention time. c Boiling point (at 760 mm Hg). S11

12 Table S7 Elemental analysis of raw bio-oil and its distillation products Yield Elemental analysis (wt.%) (%) C a H O b N Raw bio-oil Whole distillate ADR c a Mass balance closure of C atom was 97%. b By difference. c On dry basis. S12

13 List of Figures Figure S1 The integrated process combining co-pyrolysis and atomospheric distillation for conversion of lignocellulosic biomass into chemicals. Figure S2 Product yields versus content of atmospheric distillation residue (ADR) in feedstock in fast co-pyrolysis of rice husk and ADR. Figure S3 Exitation-emission matrix (EEM) fluorescence spectra of the bio-oils prepared from fast co-pyrolysis of ADR and rice husk at 723 K. Figure S4 GC/MS chromatogram of raw bio-oil. Figure S5 GC/MS chromatogram of distillate. Figure S6 GC chromatograms of distillate Fraction I. Figure S7 GC chromatograms of distillate Fraction II. Figure S8 GC chromatograms of distillate Fraction III. Figure S9 GC chromatograms of distillate Fraction IV. Figure S10 GC chromatograms of distillate Fraction V. Figure S11 Optical image of ADR in powder form. Figure S12 FTIR spectrum of ADR. Figure S13 Schematic of the integrated co-pyrolysis-atmospheric distillation process with mass balance data. S13

14 O O O O OH O O O O O O O Distillate O O HO HO HO HO O OH... Non-condensable gas Bio-oil Distillation still Combustor Atmospheric distillation residue Bio-char Fast pyrolyzer Rice husk Figure S1 The integrated process combining co-pyrolysis and atomospheric distillation for conversion of lignocellulosic biomass into chemicals. S14

15 Figure S2 Product yields versus content of atmospheric distillation residue (ADR) in feedstock in fast co-pyrolysis of rice husk and ADR. Mixture of rice husk and ADR at different blending ratios was pyrolyzed at 723 K. S15

16 Figure S3 Exitation-emission matrix (EEM) fluorescence spectra of the bio-oils prepared from fast co-pyrolysis of ADR and rice husk at 723 K. (a) ADR content in feedstock: 0; (b) ADR content: 20 wt.%; and (c) ADR content: 35 wt.%. S16

17 Figure S4 GC/MS chromatogram of raw bio-oil. S17

18 Figure S5 GC/MS chromatogram of distillate. (a) Distillate from raw bio-oil (start-up of the integrated system); (b) Distillate from bio-oil produced by co-pyrolysis of rice husk and ADR (first run of the integrated system); (c) Distillate from bio-oil produced by co-pyrolysis of rice husk and secondary ADR (second run). Identified peaks are listed in Supplementary Table S6. S18

19 Figure S6 GC chromatograms of distillate Fraction I. S19

20 Figure S7 GC chromatograms of distillate Fraction II. S20

21 Figure S8 GC chromatograms of distillate Fraction III. S21

22 Figure S9 GC chromatograms of distillate Fraction IV. S22

23 Figure S10 GC chromatograms of distillate Fraction V. S23

24 Figure S11 Optical image of ADR in powder form. S24

25 Figure S12 FTIR spectrum of ADR. Recorded at a resolution of 4 cm -1 on an Equinox 55 infrared spectrometer (Bruker Optics GmbH, Germany) at room temperature by the KBr pellet method. S25

26 Recycled Non-condensable gas ~150 kg for stable run Rice husk 1,000 kg for start-up and ~750 kg for stable run Fast pyrolyzer Bio-oil ~500 kg ADR ~250 kg Distillation still Distillate ~250 kg Organics ~75 kg Bio-char, ~350 kg for stable run Figure S13 Schematic of the integrated co-pyrolysis-atmospheric distillation process with mass balance data. S26

27 Supplementary Text Characteristics of atmospheric distillation residue (ADR). The atmospheric distillation residue (ADR) inherited the irritant odor from bio-oil and was black solid in as-received form at room temperature (Fig. 2). When milled into powder, ADR showed brownish black color (Fig. S11). The FTIR spectrum (Fig. S12) of ADR reflected its oxygenated nature with strong absorption peaks of O-H and C=O moieties. The peaks at 1607, 1512, and 1449 cm -1 were indicative of the existence of aromatic rings, while the peak at 1211 cm -1 indicated that phenolic hydroxyl groups were contained, and the absorption at 1092 cm -1 evidenced the existence of ether and/or ester linkage in ADR. In addition to aromatic rings, aliphatic moieties were also contained in ADR, as shown by the absorption peaks at 2961, 2930, and 1371 cm -1. Ultimate and proximate analyses (Table S3) show that ADR had little ash content (0.51 wt%) and was carbon-rich (66.10 wt%). But its fixed carbon content was wt%, twice that of rice husk, indicating that a larger proportion of carbon atoms in ADR would be left over to form bio-char in the pyrolysis process, compared with rice husk. The volatile matter content (61.03 wt%) of ADR was comparable to that of rice husk (67.91 wt%), suggesting that ADR might also be a suitable feedstock for fast pyrolysis as rice husk was. S27