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Frontiers of Chemical Science and Engineering

ISSN 2095-0179

ISSN 2095-0187(Online)

CN 11-5981/TQ

邮发代号 80-969

2019 Impact Factor: 3.552

Frontiers of Chemical Science and Engineering  2019, Vol. 13 Issue (4): 702-717   https://doi.org/10.1007/s11705-019-1861-9
  本期目录
Production of renewable fuels by blending bio-oil with alcohols and upgrading under supercritical conditions
Sainab Omar1, Suzanne Alsamaq1, Yang Yang2, Jiawei Wang1,2()
1. Chemical Engineering and Applied Chemistry, Aston University, Birmingham, B4 7ET, UK
2. European Bioenergy Research Institute, Aston University, Birmingham, B4 7ET, UK
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Abstract

The work studied a non-catalytic upgrading of fast pyrolysis bio-oil by blending under supercritical conditions using methanol, ethanol and isopropanol as solvent and hydrogen donor. Characterisation of the bio-oil and the upgraded bio-oils was carried out including moisture content, elemental content, pH, heating value, gas chromatography-mass spectrometry (GCMS), Fourier transform infrared radiation, 13C nuclear magnetic resonance spectroscopy, and thermogravimetric analysis to evaluate the effects of blending and supercritical reactions. The GCMS analysis indicated that the supercritical methanol reaction removed the acids in the bio-oil consequently the pH increased from 2.39 in the crude bio-oil to 4.04 after the supercritical methanol reaction. The ester contents increased by 87.49% after the supercritical methanol reaction indicating ester formation could be the major deacidification mechanism for reducing the acidity of the bio-oil and improving its pH value. Simply blending crude bio-oil with isopropanol was effective in increasing the C and H content, reducing the O content and increasing the heating value to 27.55 from 17.51 MJ·kg1 in the crude bio-oil. After the supercritical isopropanol reaction, the heating value of the liquid product slightly further increased to 28.85 MJ·kg1.

Key wordsbio-oil    blending    supercritical    upgrading    characterisation
收稿日期: 2018-11-27      出版日期: 2019-12-04
Corresponding Author(s): Jiawei Wang   
 引用本文:   
. [J]. Frontiers of Chemical Science and Engineering, 2019, 13(4): 702-717.
Sainab Omar, Suzanne Alsamaq, Yang Yang, Jiawei Wang. Production of renewable fuels by blending bio-oil with alcohols and upgrading under supercritical conditions. Front. Chem. Sci. Eng., 2019, 13(4): 702-717.
 链接本文:  
https://academic.hep.com.cn/fcse/CN/10.1007/s11705-019-1861-9
https://academic.hep.com.cn/fcse/CN/Y2019/V13/I4/702
Solvent Liquid yield /wt-% Total solid yield /wt-% Total gas yielda) /wt-%
Total liquid yield Water-free liquid yield Water yieldb)
Methanol 59.68 41.91 17.77 21.22 19.10
Ethanol 82.84 63.48 19.36 7.91 9.25
Isopropanol 86.23 69.96 16.27 5.14 8.63
Tab.1  
Properties Bio-oil alcohol blendsa) Bio-oil alcohol reaction liquid productsa) Bio-oil
BM1 BE1 BI1 BM2 BE2 BI2
H2O wt-% 13.42 (0.9)b) 12.27 (0.3) 11.90 (0.7) 29.78 (0.3) 23.37 (0.2) 18.87 (0.4) 31.69 (0.3)
pH 3.67 3.54 3.06 4.04 3.84 3.80 2.39
C wt-% c) 48.13 (0.5) 55.16 (0.0) 58.28 (0.0) 46.05 (1.3) 58.76 (0.3) 61.91 (0.3) 49.26 (0.4)
H wt-% c) 9.52 (0.1) 10.06 (0.1) 10.35 (0.1) 9.60 (0.4) 10.52 (0.1) 10.36 (0.1) 7.91 (0.0)
N wt-% c) 0.20 (0.0) 0.18 (0.0) 0.17 (0.0) 0.71 (0.0) 0.18 (0.0) 0.19 (0.0) 0.20 (0.0)
O wt-% c), d) 42.16 (0.6) 34.60 (0.1) 31.20 (0.0) 43.63 (1.7) 30.53 (0.4) 27.54 (0.2) 42.63 (0.4)
HHV MJ/kg e) 21.56 (0.9) 25.60 (0.2) 27.55 (0.0) 23.03 (1.1) 27.55 (0.2) 28.85 (0.1) 17.51 (0.1)
Tab.2  
Compound Total relative content area /%
Bio-oil BM1 BM2 BE1 BE2 BI1 BI2
Acids 4.63 4.33 ? 4.66 3.92 5.79 4.78
Phenols 37.03 27.85 32.73 28.49 28.76 31.12 38.04
Esters 3.74 3.41 29.89 2.76 27.68 3.66 22.35
Ketones 17.40 12.99 13.12 13.22 11.42 13.64 15.33
Alcohols/ethers 9.62 23.60 10.75 22.54 14.31 13.57 4.75
Aldehydes 8.57 6.01 ? 7.23 ? 7.12 ?
Sugar derivatives 6.83 7.19 ? 7.94 ? 9.01 ?
Hydrocarbons ? ? 0.30 ? ? ? ?
Others 12.22 14.61 13.24 13.19 13.89 16.10 14.73
Tab.3  
Frequency range /cm?1 Frequency range /cm?1 Group Class of compound
Bio-oil BM1 BM2 BE1 BE2 BI1 BI2
3500–3200 3367 3357 3346 3359 3360 3359 3360 O–H stretching Phenols, polymeric
O–H,
water impurities
3200–2800 2927,
2853
2929,
2840
2946, 2837 2974, 2929 2975, 2930 2971, 2932 2972, 2934 C–H stretching Alkanes-methyl group
1750–1650 1709 1710 1703 1710 1703 1711 1707,
1651
C=O stretching Ketones, aldehydes
1650–1590 1648 1603 1610 1603 1603 1605 C=C stretching
alkene
C–C multiple bond stretching
~1600–1450 1515 1515 1515 1515 1515 1515 1515 C=C stretching
aromatic
1470–1350 1450,
1363
1449,
1361
1449,
1377
1448,
1378
1452, 1378 1465, 1380 1466, 1380 C–H deformation Alkanes-methylene group
1300–950 1268,
1033
1268,
1193,
1031
1268,
1219, 1114, 1018
1270, 1043 1271, 1086, 1044 1276, 1160, 1126, 1100, 1051 1288, 1161, 1127, 1106, 1034 C–O stretching
O–H bending
Primary, secondary,
tertiary alcohols, phenols
975–525 861,
811
889,
812
878, 811 878 949, 815 949,
816
C–H bending Mono-, polycyclic,
substituted aromatic rings
Tab.4  
Fig.1  
Fig.2  
Fig.3  
Fig.4  
Distillation range /°C Weight /%
BO BM1 BM2 BE1 BE2 BI1 BI2
35?150 41.31 (0.5)b) 50.17 (0.0) 62.79 (0.4) 52.80 (0.1) 54.62 (0.7) 52.50 (0.2) 50.46 (0.2)
150?200 11.79 (0.1) 10.17 (0.0) 7.83 (0.0) 9.77 (0.0) 8.38 (0.2) 9.62 (0.2) 9.14 (0.1)
200?250 9.66 (0.1) 8.33 (0.0) 6.32 (0.0) 7.91 (0.0) 7.22 (0.2) 7.73 (0.2) 7.86 (0.1)
250?300 7.64 (0.1) 6.66 (0.0) 5.03 (0.0) 6.20 (0.1) 6.09 (0.2) 6.14 (0.1) 6.72 (0.1)
300?350 6.29 (0.1) 5.66 (0.0) 4.38 (0.0) 5.28 (0.0) 5.35 (0.1) 5.24 (0.1) 5.99 (0.1)
<350 76.70 (0.9) 80.99 (0.0) 86.36 (0.4) 81.97 (0.0) 81.66 (0.0) 81.24 (0.3) 80.18 (0.2)
350?400 5.50 (0.0) 5.00 (0.0) 4.07 (0.0) 4.70 (0.0) 4.94 (0.2) 4.64 (0.1) 5.53 (0.1)
400?450 4.72 (0.1) 4.42 (0.1) 3.63 (0.0) 4.20 (0.0) 4.38 (0.1) 4.13 (0.1) 4.83 (0.0)
450?500 4.20 (0.1) 3.93 (0.1) 3.17 (0.0) 3.74 (0.0) 3.90 (0.0) 3.67 (0.1) 4.20 (0.0)
>500 8.88 (1.1) 5.66 (0.2) 2.77 (0.4) 5.39 (0.0) 5.13 (0.3) 6.32 (0.6) 5.25 (0.3)
Tab.5  
Fig.5  
Fig.6  
Fig.7  
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