Influence of heating temperatures on the component distribution of distillates derived from walnut shell bio-oil
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摘要: 通过改变蒸馏温度对生物油进行常压蒸馏并将馏分分为油水两相，研究了馏分的组分分布变化。结果表明，在120-300℃随着蒸馏温度的升高，生物油馏出率不断增加；蒸馏温度低于240℃的油相馏分中萘、甲苯等芳烃类化合物和乙酸等羧酸类化合物明显富集，以120℃油相馏分为例，芳烃类和羧酸类化合物的相对含量是生物油原油的13.86倍和3.15倍；当蒸馏温度高于240℃时苯酚、愈创木酚等酚类化合物大量馏出，使得油相馏分的产率明显增加；同时，所获水相馏分中的水分含量皆高于60%，水分的富集效果明显；在馏分中检测到了2-乙基乙酸丁酯和环戊酮等原油中未检测到的组分并且馏分中水分总量高于生物油原油，这些都表明生物油在蒸馏过程中发生了酯化、缩聚等化学反应。通过对油相馏分的组分分布进行分析，发现改变蒸馏温度可以有效富集生物油中的高价值化合物，如苯酚、愈创木酚、4-甲基愈创木酚、4-乙基愈创木酚和4-丙基愈创木酚的相对含量在300℃的油相馏分中分别比生物油提高了109%、160%、84%、53%和444%。Abstract: Influence of heating temperatures on the component distribution of distillates distilled from walnut shell bio-oils was studied. Meanwhile, distillates were further separated into water-soluble and water-insoluble fraction to characterize product distribution. The results showed that distillate fraction yield increased with strengthening heating temperature from 120 to 300 ℃. Aromatic hydrocarbons (e.g. naphthalene) and carboxylic acids (e.g. acetic acid) significantly concentrated in water-insoluble fraction as heating temperatures were below 240 ℃. Notably, the relative concentration of aromatic and carboxylic compounds in the water-insoluble fraction derived from 300 ℃ was 13.86 and 3.15 times higher than that of crude bio-oil, respectively. Large amounts of phenols such as phenol and guaiacol was distilled as heating temperatures exceeded 240 ℃, which induced enhanced yield of water-insoluble fraction. Moreover, the moisture of all the water-soluble fractions was higher than 60%, which demonstrated the water-soluble fraction remarkably concentrated moisture. In addition, undetected components (e.g. butyl 2-ethylacetate and cyclopentanone) in crude bio-oil surprisingly existed in distillates and the total moisture of distillates was higher than that of crude bio-oils, which proved esterification and polycondensation reactions occurred in bio-oil distillation process. Furthermore, the component distribution of distillates also indicated modifying heating temperatures effectively enriched commodity chemicals. Note that water-insoluble fraction distilled from 300 ℃ exhibited relative concentration of phenol, guaiacol, 4-methyl-2-methoxyphenol, 4-ethyl-2-methoxyphenol and 4-propyl-2-methoxyphenol was 109%, 160%, 84%, 53% and 444% higher than that in crude bio-oil, respectively.
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Key words:
- bio-oil /
- atmospheric distillation /
- separation /
- phenols enrichment
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图 2 不同温度下生物油馏出率及油水相占比
Figure 2 Curves of bio-oil distillate fraction yield and proportion of water-soluble/-insoluble fraction at different temperatures
图 3 不同温度下馏分中水相油相水分含量(a)和水分总馏出率(b)
Figure 3 Moisture of water-soluble/-insoluble fraction (a) and total distillate (b) at different temperatures
图 4 生物油原油和不同温度下油相馏分(a)羧基、芳环、酚, (b)甲氧基、双键及叁键、甲基及亚甲基的1H NMR谱图
Figure 4 1H NMR spectra of (a) carboxyl, aromatic ring, phenol, (b) methoxy, alkenyl, alkynyl, methyl and methylene of crude bio-oil and water-insoluble fraction at different temperatures
图 5 不同温度下油相馏分中酚类、芳烃类、酸类化合物相对含量
Figure 5 Relative concentration of aromatics, phenols and carboxylic acids in water-insoluble fraction at different temperatures
图 6 不同温度下水相馏分中酮类、酯类、酚类、芳烃类、酸类化合物相对含量
Figure 6 Relative concentration of ketones, esters, aromatics, phenols and carboxylic acids in water-soluble fraction at different temperatures
表 1 油相生物油的元素分析及水含量
Table 1 Elemental analysis and moisture of water-insoluble bio-oil
Ultimate analysis war/% Moisture wt/% C H Oa N 58.54 7.36 33.54 0.56 6.64 a: by differences 
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表 2 原油与不同温度下油相馏分主要化合物相对含量
Table 2 Relative concentration of compounds in bio-oil and water-insoluble fraction at different temperatures
Compound Peak area*/% 120℃ 140℃ 160℃ 180℃ 200℃ 220℃ 240℃ 260℃ 280℃ 300℃ crude bio-oil Acetic acid 5.60 1.22 1.70 2.25 2.04 4.06 2.97 3.03 2.02 1.80 1.78 Benzene 0.60 0.55 0.50 - - - - - - - - Methylbenzene 2.77 2.46 2.61 2.34 2.52 2.21 2.25 1.14 0.71 - - M-xylene 7.02 6.10 2.82 4.66 1.60 1.34 1.44 0.63 0.81 - - 3-ethyltoluene 1.22 0.98 1.06 - - - - - - - - Mesitylene 0.85 1.03 1.09 1.05 1.04 0.81 0.88 - - - - 2-vinyltoluene 5.33 5.02 5.32 5.39 5.25 4.70 4.50 3.87 - - - 4-ethynyltoluene 4.63 4.6 4.76 4.98 4.95 4.72 4.48 3.87 - - - Phenol - - - - - - - 4.64 4.40 3.72 1.78 O-cresol - 3.46 3.03 2.85 3.01 1.13 1.52 6.19 4.82 4.50 2.09 Guaiacol 6.22 7.23 7.30 7.16 7.16 7.24 8.67 15.99 22.84 21.15 8.11 3, 4-xylenol - 0.81 0.86 0.77 0.79 1.24 1.61 2.32 3.61 2.85 - Naphthalene 6.39 5.30 5.45 6.62 5.48 5.9 5.62 3.85 2.13 1.78 1.06 4-mthyl-2-methoxyphenol 5.67 6.79 6.16 5.53 6.13 4.00 4.35 8.66 11.88 14.53 7.90 4-ethyl-2-methoxyphenol - 2.37 2.05 1.81 2.15 1.35 1.63 3.47 7.65 8.19 5.33 1-methylnaphthalene - 2.81 3.00 3.59 2.85 3.34 3.06 2.37 2.61 2.54 1.02 4-propyl-2-methoxyphenol - - - - - - - 2.83 6.79 9.52 1.75 *: peak area≥0.5%
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[1] KAN T, STREZOV V, EVANS T J. Lignocellulosic biomass pyrolysis:A review of product properties and effects of pyrolysis parameters[J]. Renewable Sustainable Energy Rev, 2016, 57:1126-1140. doi: 10.1016/j.rser.2015.12.185 [2] CHEN D, ZHOU J, ZHANG Q, ZHU X. Evaluation methods and research progresses in bio-oil storage stability[J]. Renewable Sustainable Energy Rev, 2014, 40:69-79. doi: 10.1016/j.rser.2014.07.159 [3] BULUSHEV D A, ROSS J R H. Catalysis for conversion of biomass to fuels via pyrolysis and gasification:A review[J]. Catal Today, 2011, 171(1):1-13. http://www.sciencedirect.com/science/article/pii/S092058611100099X [4] 张伟, 赵增立, 郑安庆, 常胜, 李海滨.生物油储存稳定性实验研究[J].燃料化学学报, 2012, 40(2):184-189. http://www.wanfangdata.com.cn/details/detail.do?_type=perio&id=rlhxxb201202009ZHANG Wei, ZHAO Zeng-li, ZHENG An-qing, CHANG Sheng, LI Hai-bin. Characterization and storage stability analysis of bio-oil[J]. J Fuel Chem Technol, 2012, 40(2):184-189. http://www.wanfangdata.com.cn/details/detail.do?_type=perio&id=rlhxxb201202009 [5] DUAN H, DONG J, GU X, PENG Y, CHEN W, TITIPONG I, WILLIAM K M, LI M, YI N, ALEXANDER F, WANG Y, ZHENG X, JI S, WANG Q, FENG J, CHEN D, LI Y, JEAN C, LIU H, SHIK C, DERMOT O. Hydrodeoxygenation of water-insoluble bio-oil to alkanes using a highly dispersed Pd-Mo catalyst[J]. Nat Commun, 2017, 8(1):591. http://www.ncbi.nlm.nih.gov/pubmed/28928359 [6] DE S, SAHA B, LUQUE R. Hydrodeoxygenation processes:Advances on catalytic transformations of biomass-derived platform chemicals into hydrocarbon fuels[J]. Bioresource Technol, 2015, 178:108-118. doi: 10.1016/j.biortech.2014.09.065 [7] NARNO S, ROCHMADI R, MULYONO P, AZIZ M, BUDIMAN A. Kinetic study of catalytic cracking of bio-oil over silica-alumina catalyst[J]. Bioresources, 2018, 13(1):1917-1929. http://www.researchgate.net/publication/322817782_Kinetic_study_of_catalytic_cracking_of_bio-oil_over_silica-alumina_catalyst [8] GAMLIEL, DAVID P, JULIA A V, GEORGE M B. The effect of ZSM-5 catalyst support in catalytic pyrolysis of biomass and compounds abundant in pyrolysis bio-oils[J]. J Anal Appl Pyrolysis, 2016, 122:7-12. doi: 10.1016/j.jaap.2016.11.002 [9] 费雯婷, 刘荣厚, 周维奇, 尹仁湛.生物油催化酯化及其存储稳定性研究[J].太阳能学报, 2014, 35(11):2177-2184. http://www.wanfangdata.com.cn/details/detail.do?_type=perio&id=tynxb201411017FEI Wen-ting, LIU Rong-hou, ZHOU Wei-qi, YI Ren-zhan. Bio-oil catalytic esterification and its stability with storage[J]. Acta Energi Sin, 2014, 35(11):2177-2184. http://www.wanfangdata.com.cn/details/detail.do?_type=perio&id=tynxb201411017 [10] BAKER E G, ELLIOTT D C. Catalytic hydrotreating of biomass-derived oils[J]. Acs Symp Ser, 1987, 32:2. doi: 10.1021/bk-1988-0376.ch021 [11] REZAEI P S, SHAFAGHAT H, DAUD W M A W. Production of green aromatics and olefins by catalytic cracking of oxygenate compounds derived from biomass pyrolysis:A review[J]. Appl Catal A:Gen, 2014, 469:490-511. doi: 10.1016/j.apcata.2013.09.036 [12] 吕东灿, 刘运权, 王夺, 袁亮.生物油萃取分离技术的研究进展[J].化工进展, 2012, 31(7):1425-1431. http://www.wanfangdata.com.cn/details/detail.do?_type=perio&id=hgjz201207006LV Dong-can, LIU Yun-quan, WANG Duo, YUAN Liang. Research progress in separation of bio-oils by extraction methods[J]. Chem Ind Eng Prog, 2012, 31(7):1425-1431. http://www.wanfangdata.com.cn/details/detail.do?_type=perio&id=hgjz201207006 [13] BENNETT N M, HELLE S S, DUFF S J B. Extraction and hydrolysis of levoglucosan from pyrolysis oil[J]. Bioresource Technol, 2009, 100(23):6059-6063. doi: 10.1016/j.biortech.2009.06.067 [14] SHASHKOV M V, SIDELNIKOV V N. Separation of phenol-containing pyrolysis products using comprehensive two-dimensional chromatography with columns based on pyridinium ionic liquids[J]. J Sep Sci, 2016, 39(19):3754-3760. doi: 10.1002/jssc.201600431 [15] LI S, ZHU X, LI S, ZHU X. Improved bio-oil distilling effect by adding additives to enhance downstream bio-oil processing and separation[J]. Sep Purif Technol, 2020:116982. http://www.sciencedirect.com/science/article/pii/S1383586620314568 [16] 王誉蓉, 王树荣, 王相宇, 郭祚刚.不同蒸馏压力下的生物油分子蒸馏分离特性研究[J].燃料化学学报, 2013, 41(2):177-182. http://www.ccspublishing.org.cn/article/id/11888WANG Yu-Rong, WANG Shu-rong, WANG Xiang-yu, GUO Zuo-gang. Molecular distillation separation characteristic of bio-oil under different pressures[J]. J Fuel Chem Technol, 2013, 41(2):177-182. http://www.ccspublishing.org.cn/article/id/11888 [17] CHENG B, HUANG B, ZHANG R, CHEN Y, JIANG S, LU Y, ZHANG X, JIANG H, YU H. Bio-coal:A renewable and massively producible fuel from lignocellulosic biomass[J]. Sci Adv, 2020, 6(1):eaay0748. doi: 10.1126/sciadv.aay0748 [18] ZHU X, WANG C, LI S, ZHU X. Upgrading biochar from bio-oil distillation residue by adding bituminous coal:Effects of induction conditions on physicochemical properties[J]. Energy Convers Manage, 2018, 174:288-294. doi: 10.1016/j.enconman.2018.08.055 [19] 李姗姗, 潘洋, 张立强, 黄凌瑞, 朱锡锋.乙酸锌对生物质热解产物分布及热解过程的影响[J].科学通报, 2019(31). http://www.wanfangdata.com.cn/details/detail.do?_type=perio&id=kxtb201931013LI Shan-shan, PAN Yang, ZHANG Li-qiang, HUANG Ling-rui, ZHU Xi-feng. Catalytic effect of zinc acetate on products distribution and reaction process of biomass pyrolysis[J]. Chin Sci Bull, 2019(31). http://www.wanfangdata.com.cn/details/detail.do?_type=perio&id=kxtb201931013 [20] HE, G, RUAN X, SONG Y, LIU Z, HE G. Molecular dynamics simulation of the hydration structure and hydrogen bonding behavior of phenol in aqueous solution[J]. J Mol Liq, 2016, 221:942-948. doi: 10.1016/j.molliq.2016.06.048 [21] ALSBOU E, HELLEUR B. Accelerated Aging of Bio-oil from Fast Pyrolysis of Hardwood[J]. Energy Fuels, 2014, 28(5):3224-3235. doi: 10.1021/ef500399n [22] LUO Z, XIE F, CHU W, WANG Y, ZHU X. Comparative study on the evolution of physicochemical properties of tar obtained from heavy fraction of bio-oil at different heating rates[J]. J Anal Appl Pyrolysis, 2020, 150:104854. doi: 10.1016/j.jaap.2020.104854 [23] ZHANG X S, YANG G X, JIANG H, LIU W, DING H. Mass production of chemicals from biomass-derived oil by directly atmospheric distillation coupled with co-pyrolysis[J]. Sentific Reports, 2013, 3:1120. doi: 10.1038/srep01120 -
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