轻馏分生物油催化酯化脱水提质研究

doi:10.3969/j.issn.0253-2417.2016.03.009

林产化学与工业 ›› 2016, Vol. 36 ›› Issue (3): 60-66.doi: 10.3969/j.issn.0253-2417.2016.03.009

轻馏分生物油催化酯化脱水提质研究

鲁俊祥, 郭姝君, 常杰, 付严

华南理工大学化学与化工学院传热强化与过程节能教育部重点实验室, 广东广州 510640

收稿日期:2015-09-18 出版日期:2016-06-25 发布日期:2016-07-07
通讯作者: 付严,副研究员,主要从事生物质制备燃料及高价值化学品研究工作;E-mail:fuyan@scut.edu.cn。 E-mail:fuyan@scut.edu.cn
作者简介:鲁俊祥(1991-),男,江西抚州人,硕士生,主要研究方向为生物质能源化工
基金资助:
国家重点基础研究发展计划(2013CB228104);国家自然科学基金资助项目(21476090);中央高校基本科研业务费专项资金资助(无编号)

Upgrading of Light Fraction in Bio-oil by Catalytic Esterification and Water Removal

LU Jun-xiang, GUO Shu-jun, CHANG Jie, FU Yan

Key Laboratory of Heat Transfer Enhancement and Energy Conservation of Education Ministry, School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou 510640, China

Received:2015-09-18 Online:2016-06-25 Published:2016-07-07

摘要/Abstract

摘要： 为了得到稳定的含氧液体燃料及较好分离糖类及其衍生物,以Amberlyst-36离子交换树脂为催化剂在100℃下对粗生物油进行酯化脱水提质工艺优化,考察了反应时间、催化剂用量以及正丁醇和生物油质量比(醇油比)对提质的影响,得到最佳提质条件为醇油比1.5:1.0、15%的催化剂用量、反应时间4 h,此条件下提质油酸值从72.23 mg/g降为3.98 mg/g,水分从53.06%降为3.34%,热值由8.75 MJ/kg升高至31.50 MJ/kg。GC-MS分析显示生物油中不稳定酸、醛、酮转化为稳定含氧化合物,稳定目标产物酯、醇、醚GC含量占74.70%。接着进行老化实验,保存3个月,粗生物油黏度从3.21 mm²/s增加到48.24 mm²/s,极不稳定,提质油理化性质显著提高并保持稳定。最后将20.00 g提质油、30.00 g蒸馏水和30.00 g二氯甲烷进行充分混合,萃取分液,可以基本将糖类及其衍生物从提质油中分离出来,得到粗糖质量为1.24 g,糖类物质总GC含量为87.92%,其中丁基-β-D-吡喃葡萄糖苷占到75.28%。

关键词: 生物油, 酯化脱水, 提质, 含氧化合物, 糖类

Abstract: Stable oxygenated liquid fuel and sugars derivatives were obtained by esterification and water removal of crude bio-oil over Amberlyst-36 ion-exchange resin. The effects of reaction time, catalyst dosage and alcohol-oil ratio were investigated. The results showed that the optimum upgrading conditions were alcohol-oil ratio 1.5:1.0, 15% catalyst dosage and 4 h. Under these operation factors, the acid number of upgraded bio-oil reduced from 72.23 mg/g to 3.98 mg/g, water content decreased from 53.06% to 3.34%, heating value increased from 8.75 MJ/kg to 31.50 MJ/kg. The GC-MS analysis showed that the labile acids, aldehydes and ketones of crude bio-oil could transform to stable oxygenated compounds, and the GC content of stable compounds (esters, alcohols and ethers) reached up to 74.70%. Crude bio-oil and upgrading bio-oil were kept for 3 months to compare the changes of characteristics. The results showed that crude bio-oil was extremely unstable and viscosity increased from 3.21 mm²/s to 48.24 mm²/s. In contrast, upgrading bio-oil was relatively stable and the physicochemical properties were improved significantly. Moreover, 20.00 g upgrading bio-oil, 30.00 g distilled water and 30.00 g dichloromethane were mixed adequately for separation of sugar derivatives. It was found that sugar derivatives could almost completely separate from upgrading bio-oil. The mass of crude sugars was 1.24 g and the total GC content of sugar derivatives was 87.92%, in which β-D-glucopyranoside, butyl accounted for 75.28%.

Key words: bio-oil, esterification and water removal, upgrading, oxygenated compounds, sugars

中图分类号:

TQ35
TK6

鲁俊祥, 郭姝君, 常杰, 付严. 轻馏分生物油催化酯化脱水提质研究[J]. 林产化学与工业, 2016, 36(3): 60-66.

LU Jun-xiang, GUO Shu-jun, CHANG Jie, FU Yan. Upgrading of Light Fraction in Bio-oil by Catalytic Esterification and Water Removal[J]. Chemistry and Industry of Forest Products, 2016, 36(3): 60-66.

参考文献

[1] ZHENG Xian-wei,FU Yan,CHANG Jie,et al.Classified separation of flash pyrolysis oil[J].BioEnergy Research,2013,6(4):1165-1172.
[2] ELLIOTT D C,HART T R,NEUENSCHWANDER G G,et al.Catalytic hydroprocessing of fast pyrolysis bio-oil from pinesawdust[J].Energy and Fuels,2012,26(6):3891-3896.
[3] QIN Fei,CUI Hong-you,YI Wei-ming,et al.Upgrading the water-soluble fraction of bio-oil by simultaneous esterification and acetalation with online extraction[J].Energy and Fuels,2014,28(4):2544-2553.
[4] MARCELO E,DOMINE C,VEEN V,et al.Coprocessing of oxygenated biomass compounds and hydrocarbons for the production of sustainable fuel[J].ChemSusChem,2008,1(3):179-181.
[5] 樊永胜,蔡忆昔,李小华,等.樟木木屑真空热解工艺的响应面法优化及生物油组分分析[J].林产化学与工业,2014,34(6):29-36. FAN Yong-sheng,CAI YI-xi,LI Xiao-hua,et al.Vacuum pyrolysis of camphorwood sawdust optimized by response surface methodology and bio-oil composition analysis[J].Chemistry and Industry of Forest Products,2014,34(6):29-36.
[6] 王金表,蒋剑春,徐俊明,等.生物质液化及提质改性研究进展[J].生物质化学工程,2013,47(6):16-20. WANG Jin-biao,JIANG Jian-chun,XU Jun-ming,et al.Research progress on biomass liquefaction and refining technology[J].Biomass Chemical Engineering,2013,47(6):16-20.
[7] HU Xun,WANG Yi,MOURANT D,et al.Polymerization on heating up of bio-oil:A model compound study[J].AIChE Journal,2013,59(3):888-900.
[8] 陆强,朱锡锋,李全新,等.生物质快速热解制备液体燃料[J].化学进展,2007,19(7/8):1064-1070. LU Qiang,ZHU Xi-feng,LI Quan-xin,et al.Biomass fast pyrolysis for liquid fuels[J].Progress in Chemistry,2007,19(7/8):1064-1070.
[9] BENNETT N M,HELLE S S,DUFFS J B.Extraction and hydrolysis of levoglucosan from pyrolysis oil[J].Bioresource Technology,2009,100(23):6059-6063.
[10] 刘承运,陆强,孙书生,等.稻壳生物油的燃烧及污染物排放特性研究[J].燃料化学学报,2008,36(5):578-582. LIU Cheng-yun,LU Qiang,SUN Shu-sheng,et al.Research on rice husk bio-oil combustion and pollutant emission[J].Journal of Fuel Chemistry and Technology,2008,36(5):578-582.
[11] 徐俊明,蒋剑春,卢言菊.生物热解油精制改性研究进展[J].现代化工,2007,27(7):13-17. XU Jun-ming,JIANG Jian-chun,LU Yan-ju.Progess in research of upgrading of pyrolytic bio-oil[J].Modern Chemical Industry,2007,27(7):13-17.
[12] 顾帅,杨洪雪,苗玮,等.生物油精制技术研究进展[J].林产化学与工业,2012,32(2):55-60. GU Shuai,YANG Hong-xue,MIAO Wei,et al.Progress in bio-oil refining technology[J].Chemistry and Industry of Forest Products,2012,32(2):55-60.
[13] 司展,蒋剑春,王奎.生物质热解油的精制方法研究进展[J].生物质化学工程,2013,47(6):21-26. SI Zhan,JIANG Jian-chun,WANG Kui.Research progress on upgrading og bio-oil[J].Biomass Chemical Engineering,2013,47(6):21-26.
[14] WILDSCHUT J,MAHFUD F H,VENDERBOSCH R H,et al.Hydrotreatment of fast pyrolysis oil using heterogeneous noble-metal catalysts[J].Industrial and Engineering Chemistry Research,2009,48(23):10324-10334.
[15] HEW K L,TAMIDI A M,YUSUP S,et al.Catalytic cracking of bio-oil to organic liquid product (OLP)[J].Bioresource Technology,2010,101(22):8855-8858.
[16] 胡恩源,闫常峰,蔡炽柳,等.生物油水溶性组分的水蒸气催化重整制氢实验研究[J].燃料化学学报,2009,37(2):177-182. HU En-yuan,YAN Chang-feng,CAI Chi-liu,et al.Experimental research on hydrogen production by catalytic steam reforming of bio-oil aqueous fraction[J].Journal of Fuel Chemistry and Technology,2009,37(2):177-182.
[17] TANG Yang,YU Wan-jin,MO Liu-ye,et al.One-step hydrogenation-esterification of aldehyde and acid to ester over bifunctional Pt catalysts:A model reaction as novel route for catalytic upgrading of fast pyrolysis bio-oil[J].Energy and Fuels,2008,22(5):3484-3488.
[18] 王锦江,常杰,范娟.离子交换树脂催化酯化生物油的试验研究[J].燃料化学学报,2010,38(5):560-564. WANG Jin-jiang,CHANG Jie,FAN Juan.Experimental study on catalytic esterification of bio-oil by ion exchange resins[J].Journal of Fuel Chemistry and Technology,2010,38(5):560-564.
[19] XU Jun-ming,JIANG Jian-chun,DAI Wei-di,et al.Bio-oil upgrading by means of ozone oxidation and esterification to remove water and to improve fuel characteristics[J].Energy and Fuels,2011,25(4):1798-1801.
[20] SUNDQYIST T,OASMAA A,KOSKINEN A.Upgrading fast pyrolysis bio-oil quality by esterification and azeotropic water removal[J].Energy and Fuels,2015,29(4):2527-2534.
[21] 郑小明,楼辉.生物质热解油品位催化提升的思考和初步进展[J].催化学报,2009,30(8):765-769. ZHENG Xiao-ming,LOU Hui.Recent advances in upgrading of bio-oils from pyrolysis of biomass[J].Chinese Journal of Catalysis,2009,30(8):765-769.

轻馏分生物油催化酯化脱水提质研究

Upgrading of Light Fraction in Bio-oil by Catalytic Esterification and Water Removal

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

参考文献

相关文章 15

编辑推荐

Metrics

本文评价

关于本刊

投稿指南

在线期刊

相关单位

联系我们

[1]	刘世奇, 张素平, 于泰莅, 蔡勤杰. 生物质与塑料共热解协同作用研究[J]. 林产化学与工业, 2019, 39(3): 34-42.
[2]	张浩然, 艾涛, 张东辉, 魏俊奇. 生物油的氨基甲酸酯化改性及其酚醛树脂的制备[J]. 林产化学与工业, 2018, 38(3): 109-114.
[3]	赵卫东, 赖志豪, 蔡忆昔, 黄健泉, 樊永胜. 低温等离子体协同HZSM-5在线催化裂解提质油菜秸秆热解油[J]. 林产化学与工业, 2016, 36(6): 9-15.
[4]	张颖, 韩铮, 徐禄江, 傅尧. 生物质基含氧化合物加氢脱氧反应的研究进展[J]. 林产化学与工业, 2016, 36(6): 107-118.
[5]	朱沈嘉, 刘运权, 王夺, 叶跃元, 李水荣. 热过滤对流化床快速热解制取生物油产率和品质的影响[J]. 林产化学与工业, 2015, 35(3): 13-19.
[6]	樊永胜, 蔡忆昔, 李小华, 俞宁, 陈磊. 香樟木屑真空热解蒸气催化前后产物对比分析[J]. 林产化学与工业, 2015, 35(1): 70-76.
[7]	尹海云, 李小华, 樊永胜, 俞宁, 蔡忆昔. 生物质三组分真空热解特性及液化产物成分分析[J]. 林产化学与工业, 2015, 35(1): 94-100.
[8]	樊永胜, 蔡忆昔, 李小华, 俞宁, 张蓉仙, 尹海云. 樟木木屑真空热解工艺的响应面法优化及生物油组分分析[J]. 林产化学与工业, 2014, 34(6): 29-36.
[9]	任洪清, 谢建军, 刘华财, 阴秀丽, 吴创之. SBA-15接枝有机胺官能团催化剂的制备、表征及在醇醛缩合反应中的应用[J]. 林产化学与工业, 2014, 34(2): 1-8.
[10]	樊永胜, 蔡忆昔, 李小华, 赵卫东, 俞宁. 真空热解工艺参数对生物油产率的影响研究[J]. 林产化学与工业, 2014, 34(1): 79-85.
[11]	吕东灿;刘运权;王夺;叶跃元. 生物油的分离及其产品应用[J]. 林产化学与工业, 2013, 33(4): 137-143.
[12]	顾帅;杨洪雪;苗玮;许庆利;颜涌捷. 生物油精制技术研究进展[J]. 林产化学与工业, 2012, 32(2): 55-60.
[13]	闫彩辉;赵炜;盛晨;吴晓娜. 柱层析法在生物油分离方面应用的研究进展[J]. 林产化学与工业, 2011, 31(4): 123-126.
[14]	徐俊明;蒋剑春;吕微;高一苇. 生物质热解油中各成分的精制与应用[J]. 林产化学与工业, 2010, 30(2): 1-5.
[15]	王敏;艾宁;蔡腾跃;姬登祥;计建炳. 熔盐裂解液化生物质的研究[J]. 林产化学与工业, 2009, 29(5): 41-46.