酸洗-烘焙预处理对生物质热解产物的影响

doi:10.16085/j.issn.1000-6613.2017.02.015

摘要/Abstract

摘要： 选用稻壳为原料，进行酸洗-烘焙联合预处理后，于550℃下热解，详细分析了固、液、气热解三相产物，考察酸洗-烘焙联合预处理对稻壳热解产物特性的影响。结果表明联合预处理移除了生物质中大部分碱金属和碱土金属，并且C元素含量增加，H和O元素含量逐渐减小，高位热值增加，因此样品的燃料特性得到了提高；酸洗后，热解生物油收益率显著提高，并随着烘焙温度的升高减小，生物焦则相反；热解产物中，不可凝气中可燃成分含量增加；生物油含水率减少，但是，pH和高位热值明显增加，化学成分中糖类产量增加，酸类、酮类和呋喃类产量减少，生物焦孔隙结构得到发展，比表面积增加，稻壳灰中二氧化硅的相对含量增加，达到98.91%。根据上述实验结果，提出了一种新的稻壳资源综合利用系统。

关键词: 酸洗, 烘焙, 热解

Abstract: Rice husk was selected as the raw material in this study. After combined acid washing and torrefaction pretreatment,the products from pyrolsis of raw and pretreated samples were analyzed. This study investigated the effect of acid washing and torrefaction pretreatment on pyrolysis products of biomass. It was found that alkali and alkaline earth metals were significantly removed by the combining pretreatment with acid washing and torrefaction. With the increase of C and the decrease of O and H,high heat value was increased,and the fuel characteristics were enhanced. It was found that higher bio-oil yield and lower char yield was obtained by light bio-oil washing pretreatment,and with the increase of the temperature of torrefaction,the bio-oil yield decreased,but the char yield increased. The results of gas products indicated that the relative content of combustible components was increased. For bio-oil,pretreatment resulted in a reduction of water content,but along with significant increase of pH and HHVs. The production of sugars was increased in bio-oil,while acids,ketones and furans were reduced. Pretreatment also developed the pore structure of char,specific surface area was increased,and the content of silica in rice husk ash was increased up to 98.91%. A new system on the comprehensive utilization of rice husk was proposed based on the current results.

Key words: acid washing, torrefaction, pyrolysis

中图分类号:

陈涛, 张书平, 李弯, 熊源泉. 酸洗-烘焙预处理对生物质热解产物的影响[J]. 化工进展, 2017, 36(02): 506-512.

CHEN Tao, ZHANG Shuping, LI Wan, XIONG Yuanquan. Effect of acid washing and torrefaction on pyrolysis products of biomass[J]. Chemical Industry and Engineering Progree, 2017, 36(02): 506-512.

参考文献

[1] RECKAMP J M,GARRIDO R A,Satrio J A. Selective pyrolysis of paper mill sludge by using pretreatment processes to enhance the quality of bio-oil and biochar products[J]. Biomass & Bioenergy,2014,71:235-244.
[2] 刘华敏,马明国,刘玉兰. 预处理技术在生物质热化学转化中的应用[J]. 化学进展,2014,26(1):203-213. LIU H M,MA M G,LIU Y L. Applications of pretreatment in biomass thermo-chemical conversion technology[J]. Process in Chemistry,2014,26(1):203-213.
[3] 黄鹏,郭军志,杨涛,等. 预处理催化法对生物质热解的影响研究进展[J]. 化工生产与技术,2015,22(3):42-46. HUANG P,GUO J D,YANG T,et al. Research progress in pretreatment methods and catalysts for the impact of biomass pyrolysis[J]. Chemical Production and Technology,2015,22(3):42-46.
[4] 胡海涛,李允超,王贤华,等. 生物质预处理技术及其对热解产物的影响综述[J]. 生物质化学工程,2014,48(1):44-50. HU H T,LI Y C,WANG X H,et,al. A review of biomass pretreatment technologies and their influences on pyrolysis products[J]. Biomass Chemical Engineering,2014,48(1):44-50.
[5] 邓剑,罗永浩,王贵军,等. 稻秆的烘焙预处理及其固体产物的气化反应性能[J]. 燃料化学学报,2011,39(1):26-32. DENG J,LUO Y H,WANG G J,et,al. Torrefaction pretreatment of straw and gasification reactivity of the solid product[J]. Journal of Fuel Chemistry and Technology,2011,39(1):26-32.
[6] ESELTINE D,THANAPAL S S,ANNAMALAI K,et al. Torrefaction of woody biomass (Juniper and Mesquite) using inert and non-inert gases[J]. Fuel,2013,113:379-388.
[7] 杨晴,梅艳阳,郝宏蒙,等. 烘焙对生物质热解产物特性的影响[J]. 农业工程学报,2013,29(20):214-219. YANG Q,MEI Y Y,HAO H M,et,al. Effect of torrefaction on characteristics of pyrolytic products of biomass[J]. Transactions of the Chinese Society of Agricultural Engineering,2013,29(20):214-219.
[8] 余维金,应浩,王燕杰. 原料烘焙预处理对生物质气化的影响综述[J]. 生物质化学工程,2013,47(6):41-45. YU W J,YING H,WANG Y J. Influence of torrefaction pretreatment on biomass gasification[J]. Biomass Chemical Engineering,2013,47(06):41-45.
[9] 江洋,张会岩,邵珊珊,等. 烘焙预处理对生物质热解的影响[J]. 燃烧科学与技术, 2015,21(3):229-235. JIANG Y,ZHANG H Y,SHAO S S,et,al. Torrefaction pretreatment on the pyrolysis performances of biomass[J]. Journal of Combustion Science and Technology,2015,21(3):229-235.
[10] CHEN D,ZHOU J,ZHANG Q. Effects of torrefaction on the pyrolysis behavior and bio-oil properties of rice husk by using TG-FTIR and Py-GC/MS[J]. Energy & Fuels,2014,28(9):5857-5863.
[11] 杜胜磊,杨海平,钱柯贞,等. 生物质热解过程中碱及碱土金属迁徙规律研究[J]. 中国电机工程学报,2013,33(26):48-53. DU S L,YANG H P,QIAN K Z,et al. Releasing behavior of alkali and alkaline earth metals during biomass pyrolysis[J]. Proceedings of the Cess,2013,33(26):48-53.
[12] MOURANT D,WANG Z,HE M,et al. Mallee wood fast pyrolysis:effects of alkali and alkaline earth metallic species on the yield and composition of bio-oil[J]. Fuel,2011,90(9):2915-2922.
[13] FAHMI R,BRIDGWATER A V,DARVELL L I,et al. The effect of alkali metals on combustion and pyrolysis of Lolium and Festuca grasses,switchgrass and willow[J]. Fuel,2007,86(10/11):1560-1569.
[14] 朱锡锋,李明. 生物质快速热解液化技术研究进展[J]. 石油化工,2013,42(8):833-837. ZHU X F,LI M. Progresses in fast pyrolysis of biomass to liquid fuel[J]. Petrochemical Technology,2013,42(8):833-837.
[15] 张帅,王贤华,李攀,等. 预处理法提高生物质热解产物品质的研究进展[J]. 化工进展,2014,33(2):346-352. ZHANG S,WANG X H,LI P,et al. Research progress in pretreatment method for the quality improvement of biomass pyrolysis products[J]. Chemical Industry and Engineering Progress,2014,33(2):346-352.
[16] 王树荣,廖艳芬,刘倩,等. 酸洗预处理对纤维素热裂解的影响研究[J]. 燃料化学学报,2006,32(2):179-183. WANG S R,LIAO Y F,LIU Q,et al. Experimental study of the influence of acid wash on cellulose pyrolysis[J]. Journal of Fuel Chemistry and Technology,2006,32(2):179-183.
[17] 郑燕,陈登宇,朱锡锋. 酸洗预处理对稻壳快速热解产物的影响[J]. 太阳能学报,2014,35(6):925-930. ZHENG Y,CHEN D Y,ZHU X F. Gas Chromatograohy/mass spectrometryanalysis of pyrolysis product of acid washed rice husk[J]. Acta Energiae Solaris Sinica,2014,35(6):925-930.
[18] 谷双,路长通,陈纪忠. 水洗及酸洗对毛竹热解产物的影响[J]. 浙江大学学报(工学版),2013,47(7):1313-1320. GU S,LU C T,CHEN J Z. Effect of water and acid leaching on pyrolysis products of phyllostachys pubescens[J]. Journal of Zhejing University(Engineering Science),2013,47(7):1313-1320.
[19] KARNOWO,ZAHARA Z F,KUDO S,et al. Leaching of alkali and alkaline earth metallic species from rice husk with bio-oil from its pyrolysis[J]. Energy & Fuels,2014,28(10):6459-6466.
[20] OUDENHOVEN S R G,WESTERHOF R J M,KERSTEN S R A. Fast pyrolysis of organic acid leached wood,straw,hay and bagasse:improved oil and sugar yields[J]. Journal of Analytical and Applied Pyrolysis,2015,116:253-262.
[21] GU S,ZHOU J,LUO Z,et al. A detailed study of the effects of pyrolysis temperature and feedstock particle size on the preparation of nanosilica from rice husk[J]. Industrial Crops and Products,2013,50:540-549.
[22] XIAO L,ZHU X,LI X,et al. Effect of pressurized torrefaction pretreatments on biomass CO₂ gasification[J]. Energy & Fuels,2015,29(11):7309-7316.
[23] DAS P,GANESH A,WANGIKAR P. Influence of pretreatment for deashing of sugarcane bagasse on pyrolysis products[J]. Biomass & Bioenergy,2004,27(5):445-457.
[24] ZHENG A,ZHAO Z,CHANG S,et al. Effect of torrefaction temperature on product distribution from two-staged pyrolysis of biomass[J]. Energy & Fuels,2012,26(5):2968-2974.
[25] CHEN D,ZHENG Z,FU K,et al. Torrefaction of biomass stalk and its effect on the yield and quality of pyrolysis products[J]. Fuel, 2015,159:27-32.
[26] SHI L,YU S,WANG F,et al. Pyrolytic characteristics of rice straw and its constituents catalyzed by internal alkali and alkali earth metals[J]. Fuel,2012,96(1):586-594.
[27] OUDENHOVEN S R G,WESTERHOF R J M,ALDENKAMP N,et al. Demineralization of wood using wood-derived acid:towards a selective pyrolysis process for fuel and chemicals production[J]. Journal of Analytical and Applied Pyrolysis,2013,103(s1):112-118.
[28] BRANCA C,DI BLASI C,GALGANO A,et al. Effects of the torrefaction conditions on the fixed-bed pyrolysis of norway spruce[J]. Energy & Fuels,2014,28(9):5882-5891.