不同热解温度下落叶松半焦特性的演变规律
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摘要
为探究热解温度对生物质半焦特性的影响规律,文章以落叶松为原料,采用管式电阻炉制取200～1 000℃的热解半焦,利用元素分析、XRD、BET、SEM等测试手段,结合碳-氢-氧相图及Scherrer方程,深入分析了热解温度对生物焦元素组成、石墨化程度、孔隙结构及表观形貌的影响。结果表明:热解温度升高,热解半焦的H/C,O/C原子比减小,芳构化程度加深,碳微晶结构更趋于有序化,片层状碳骨架结构逐渐凸显,石墨化程度增加;400℃下的半焦比表面积最高,微孔对比表面积的贡献大;300℃和500℃是热解半焦结构发生明显变化的两个特殊的温度点。
Larch was selected as a representative of forestry biomass to study the effect of pyrolysis temperature on characteristics evolution of biochar. Larch samples were treated under the temperature range of 200 ～1 000 ℃ in the pipe resistance furnace. Analysis methods including ultimate analysis, XRD, BET and SEM combined with carbon-hydrogen-oxygen ternary and Scherrer equation were conducted to characterize the element composition, the degree of graphenation, porosity structure and morphology of larch and biochars. The results showed that the H/C and O/C atomic ratio decreased while the structure of biochars becoming further aromatization, orderliness and graphenation with the emerging of the lamellar carbon skeleton structure. Micropore is a great contributor to the specific surface of biochars, and the specific surface reached its maximum at 400 ℃, 300 ℃ and 500 ℃ are two special pyrolysis temperature points where the structural characteristics of biochars change significantly.
Larch was selected as a representative of forestry biomass to study the effect of pyrolysis temperature on characteristics evolution of biochar. Larch samples were treated under the temperature range of 200 ～1 000 ℃ in the pipe resistance furnace. Analysis methods including ultimate analysis, XRD, BET and SEM combined with carbon-hydrogen-oxygen ternary and Scherrer equation were conducted to characterize the element composition, the degree of graphenation, porosity structure and morphology of larch and biochars. The results showed that the H/C and O/C atomic ratio decreased while the structure of biochars becoming further aromatization, orderliness and graphenation with the emerging of the lamellar carbon skeleton structure. Micropore is a great contributor to the specific surface of biochars, and the specific surface reached its maximum at 400 ℃, 300 ℃ and 500 ℃ are two special pyrolysis temperature points where the structural characteristics of biochars change significantly.
引文
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[3]许细薇,蒋恩臣,李治宇,等.毛竹热解炭化演化过程的研究[J].可再生能源,2018,36(12):1758-1763.
[4] Keown D M,Hayashi J I,LI C Z. Drastic changes in biomass char structure and reactivity upon contact with steam[J]. Fuel,2008,87(7):1127-1132.
[5] Cetin E,Moghtaderi B,Gupta R,et al. Influence of pyrolysis conditions on the structure and gasification reactivity of biomass chars[J]. Fuel,2004,83(16):2139-2150.
[6] Asadullah M,Zhang S,Min Z,et al. Effects of biomass char structure on its gasification reactivity[J].Bioresource Technology,2010,101(20):7935-7943.
[7]王靖,张安东,易维明,等.四种生物质热解半焦的FTIR红外分析[J].山东理工大学学报(自然科学版),2016,29(1):1-4.
[8]曹俊,肖刚,许啸,等.木质素热解/炭化官能团演变与焦炭形成[J].东南大学学报(自然科学版),2012,42(1):83-87.
[9] Shafizadeh F,Sekiguchi Y. Development of aromaticity in cellulosic chars[J].Carbon,1983,21(5):511-516.
[10] Williams P T,Besler S. The influence of temperature and heating rate on the slow pyrolysis of biomass[J].Renewable Energy,1996,7(3):233-250.
[11]吴逸民,赵增立,李海滨,等.生物质主要组分低温热解研究[J].燃料化学学报,2009,37:427-432.
[12] Lewis I. Chemistry of carbonization[J].Carbon,1982,20(6):519-529.
[13] Tang W,Wu J,Wang X,et al. Integrated carbon nanospheres arrays as anode materials for boosted sodium ion storage[J]. Green Energy&Environment,2018,3(1):50-55.
[14]刘书林,卢春兰,郭明聪,等.X射线衍射技术在炭材料研究中的应用[J].炭素,2018,3(176):21-26.
[15]付鹏,胡松,向军,等.气化过程中谷壳焦颗粒孔隙结构及分形特性的演化[J].农业工程学报,2012,28(13):276-281.