Effect of aqueous phase recirculation on characteristics of bio-crude oil formation during hydrothermal liquefaction of corn stalk
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摘要: 以玉米秸秆为原料，以去离子水为介质，研究水相循环对玉米秸秆水热液化成油特性的影响。循环过程中不额外添加去离子水，对循环前后的水相产物、生物原油和固体产物进行对比研究发现，水相循环产生有机酸的富集效应，促进酮酚类的转化，两者共同作用提高生物原油和固体产物的产率和品质。具体表现为：水相循环对水相pH值影响较小（3.62-3.91），但可以使乙酸和丙酸等有机酸不断累积，同时使酮类、酚类化合物含量逐渐减少；水相循环可以使生物原油产率从20.42%逐步提高至24.31%，且可略提升油品质；水相循环可以使固体产物的碳含量由60.94%提升至61.74%。Abstract: The corn stalk was used as the raw material and the deionized water was used as the medium to study the effect of aqueous phase recirculation on characteristics of bio-crude oil formation during hydrothermal liquefaction of corn stalk. No additional deionized water was added during the recirculation. The results show that the aqueous phase recirculation can enrich the concentration of organic acids in aqueous phase and promote the conversion of ketophenols, which can improve the yield and quality of bio-crude oil and solid products. Specifically, the aqueous phase recirculation has little effect on the pH value of the aqueous phase (3.62-3.91), but the organic acids such as acetic acid and propionic acid are continuously accumulated and the content of ketones and phenols is gradually reduced. Also, the yield of bio-crude oil is gradually increased from 20.42% to 24.31%, the quality of bio-crude oil is slightly improved, and the carbon content of the solid product is increased from 60.94% to 61.74%.
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图 3 水相循环前后水相产物的pH值
Figure 3 pH value change of aqueous phase with aqueous phase recirculation
图 4 水相循环前后水相产物的总有机碳(TOC)
Figure 4 Total organic carbon (TOC) change of aqueous phase with aqueous phase recirculation
图 5 水相循环前后生物原油的TG和DTG曲线
Figure 5 TG (a) and DTG (b) curves of bio-crude oil with and without aqueous phase recirculation
图 6 水相循环前后生物原油的FT-IR谱图
Figure 6 FT-IR spectra of bio-crude oil with and without aqueous phase recirculation
表 1 玉米秸秆的元素分析、工业分析和组分分析
Table 1 Ultimate, proximate and components analyses of corn stalk
Ultimate analysis wd/% Proximate analysis war/% Component analysis wd/% C H N S O* M V FC A cellulose hemicellulose lignin 44.17 2.65 0.92 0.19 41.15 8.46 77.48 6.14 7.92 31.31±0.69 40.13±0.40 4.74±0.87 d: dry basis; ar: as received; M: moisture; V: volatile matter; FC: fixed carbon; A: ash;
*: oxygen calculated by difference
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表 2 水相循环前后生物原油的元素分析和热值
Table 2 Ultimate analysis and QHHV of bio-crude oil with and without aqueous phase recirculation
Name Number of recirculation Ultimate analysis wd/% Atomic ratio QHHV/
(MJ·kg-1)C H N S O H/C O/C N/O Bio-crude oil 0 69.80 6.78 1.19 0.00 22.24 1.17 0.24 0.06 30.81 1 68.08 7.10 1.25 0.08 23.49 1.26 0.26 0.06 30.54 2 68.61 6.86 1.49 0.00 23.04 1.20 0.25 0.07 30.39 3 69.84 7.08 1.49 0.04 21.56 1.22 0.23 0.08 31.31
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表 3 生物原油的沸点分布
Table 3 Boiling point distribution of bio-crude oil
Fractionation range t/℃ Boiling point distribution /% 0 1 2 3 50-200 18.43 14.30 17.32 18.45 200-250 7.60 11.56 13.26 13.02 250-300 10.12 13.92 13.16 12.78 300-350 11.90 13.14 12.32 12.48 350-400 11.93 11.11 10.67 11.28 400-450 4.78 4.95 4.77 4.96 450-500 3.04 2.88 2.63 2.38 500-800 4.38 4.57 4.26 3.28
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表 4 生物原油FT-IR吸收峰表
Table 4 FT-IR peaks of the bio-crude oil
Wavenumber σ/cm-1 Band assignment Functional groups 3300-3100 -OH stretching vibration polysaccharide 3100-3050 C-H stretching vibration naphthenic 2975-2740 C-H stretching vibration fatty compound 1740-1610 C=O stretching vibration carboxylic acid, aldehyde, ketone 1600-1560 C=C stretching vibration aromatic compound 1540-1500 C-O aromatic ring skeleton vibration, -OH bending vibration phenols 1470-1430 C-H bending vibration fatty compound 1430-1390 -OH, C-H bending vibration hydrocarbons, acids, phenols, alcohols 1390-1260 C-H bending vibration fatty compound 1260-1190 C-O stretching vibration unsaturated ether 1130-1100 C-H, C-O bending vibration aromatic compounds, alcohols 950-750 O-H bending vibration aromatic compounds
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表 5 水相循环前后生物原油的组成和主要化合物的面积
Table 5 Composition of bio-crude oil and relative peak area of major components with and without aqueous phase recirculation
Number R.T/min Name of Compound Relative peak area /% C0 C1 C2 C3 Organic acid 1 18.275 2-hexenoic acid, 3, 4, 4-trimethyl-5-oxo-, (Z)- 0.469 1.155 1.205 - 2 19.989 7-methylindan-1-one - - 0.477 - 3 21.415 2-(1-carboxy-1-methylethyl)-4-methylfuran-3-carboxylic acid - - 2.091 - total 0.469 1.155 3.773 0.000 Ketone 4 6.535 2-cyclopenten-1-one, 2-methyl- 0.615 - 3.105 4.166 5 8.133 2-cyclopenten-1-one, 3-methyl- - 2.335 1.804 2.207 6 10.183 2-cyclopenten-1-one, 3, 4-dimethyl- - - - 2.648 7 11.634 2-cyclopenten-1-one, 3, 4, 5-trimethyl- 2.565 4.422 - 12.749 8 12.674 4-pyridinol - - 0.976 - 9 13.188 2-hydroxy-5, 5-dimethylcyclopent-2-en-1-one - - 0.886 - 10 14.376 2, 4-pentanedione, 3-(2-propenyl)- - - 1.121 - 11 23.521 ethanone, 1-(2, 6-dihydroxy-4-methoxyphenyl)- - - - 0.653 12 30.988 ethanone, 1-(4-hydroxy-3, 5-dimethoxyphenyl)- 2.037 - - - total 5.217 6.757 7.892 22.423 Aromatic 13 8.714 phenol - - 5.118 - 14 11.628 mequinol - - 9.199 - 15 13.960 phenol, 4-ethyl- 5.217 7.861 20.792 22.102 16 14.608 benzene, 1, 4-dimethoxy- - - 0.929 - 17 17.008 phenol, 4-ethyl-2-methoxy- 3.446 7.561 10.645 10.172 18 18.961 phenol, 2, 6-dimethoxy- 3.356 - 14.756 - 19 18.973 phenol, 3, 4-dimethoxy- - 5.158 - 8.510 total 12.019 20.580 61.439 40.784 Esters, alcohol and aldehyde 20 6.792 aprofene - - - 0.846 21 8.732 carbonic acid, ethyl phenyl ester - - - 3.821 22 12.870 5-ethylcyclopent-1-enecarboxaldehyde - - 0.593 1.128 total 0.000 0.000 0.593 5.795 N-containing compound 23 4.193 1, 2, 4, 5-tetrazine - - 0.579 - 24 9.687 1-pentanone, 1-(1H-imidazol-4-yl)- - - 0.472 - 25 11.266 pyrazine, methoxy- - - 0.647 - 26 19.371 L-4-hydroxy-3-methoxyphenylalanine - - 0.671 - 27 32.494 aniline, N-(3’, 3’-diphenylspiro[fluorene-9, 2’-oxetan]-4’-ylidene)- - - 1.043 - 28 36.148 N-acetylnorephedrine - - 0.582 - total 0.000 0.000 3.994 0.000 Heterocyclic compound 29 4.852 furfural 1.399 - - - 30 20.778 3-methylbenzothiophene - - 0.682 - total 1.399 0.000 0.682 0.000 Hydrocarbono 31 3.609 toluene 73.052 - - - 32 28.895 cyclohexene, 1, 5, 5-trimethyl-6-(2-propenylidene)- - - 0.638 - total 73.052 0.000 0.638 0.000
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表 6 水相循环前后固体产物的元素分析和热值
Table 6 Ultimate analysis of solid product with and without aqueous phase recirculation
Name Number of recirculation Ultimate analysis wd/% Atomic ratio Carbon recovery/% QHHV/
(MJ·kg-1)C H N S O H/C O/C Solid product 0 60.94 4.55 1.67 0.06 32.78 0.90 0.40 37.60 23.20 1 61.31 4.45 1.75 0.01 32.48 0.87 0.40 48.60 23.21 2 61.02 4.60 1.84 0.08 32.47 0.90 0.40 49.75 23.31 3 61.74 4.70 1.80 0.07 31.68 0.91 0.39 46.13 23.82
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