高含氮木质废弃物热解气化特性研究
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摘要
为了考察高含氮木质废弃物的气化特性,在热重-质谱-红外联用装置与固定床装置上进行了Ar和Ar+O2气氛下高含氮木质废弃物和木粉的热解气化试验,研究了2种原料热解气化过程和产物的异同。结果表明:2种原料的热解气化失质量和失质量速率曲线整体一致,阶段划分较为类似,但高含氮木质废弃物挥发分析出峰值出现的温度低于木粉15～20℃,失质量速率峰值为木粉的70%左右;2种原料热解气化产物主要成分整体上较为类似,但高含氮木质废弃物热解气化产物中CH4浓度明显高于木粉;高含氮木质废弃物气化产生含氮气体污染物高于木粉,固定床试验中产生的NH3浓度为木粉的147倍。该文结果可为高含氮木质废弃物的处理和高效资源化利用提供参考依据。
With the development of the wood-processing industry, the artificial timber board is widely used for furniture, interior finishes, and wooden buildings. Due to the vast use of nitrogenous adhesives, the scrapped artificial timber board is named as nitrogen-rich wood waste, which has a great impact on environment. The gasification is one of the most important techniques for utilizing wood-based waste. Because of the clean and efficient characteristics, this technique can be used to dispose the nitrogen-rich wood waste. In order to study the gasification characteristics, gasification and pyrolysis of the nitrogen-rich wood waste and pine saw dust in Ar and Ar+O2 atmosphere were carried out in TG-MS-FTIR and the fixed bed, respectively. The effects of reaction conditions on the gasification-pyrolysis process and product distribution were studied. For the TG analysis, the experiments were carried out in Ar and Ar+O2 atmosphere, respectively. The reaction temperature increased from room temperature to 1 200 ℃ by a heating rate of 10 ℃/min. The wave number region of FTIR was 400-4 000 cm-1, the working voltage of the mass spectrometer was 70 eV, and the mass-to-charge ratios were 16, 28, 44, 17, 27, 30, 43, and 46, respectively. In the fixed bed experiments, the reaction temperature was 750 ℃ and the reaction atmosphere of pyrolysis was Ar(Gasification: Ar+O2). The results showed that the TG and DTG curves of these two materials presented similar stage divisions. The DTG peak value of nitrogen-rich wood waste was about 70% of that of pine saw dust, although the temperature of peak value of nitrogen-rich wood waste appeared ahead 15-20 ℃ than that of pine saw dust, which was earlier than that of pine saw dust in the DTG curve. Furthermore, the DTG curve of nitrogen-rich wood waste possessed a shoulder peak at 280-300℃, but it can not be observed in the DTG curve of pine saw dust. In the experiments of TG-MS-FTIR and fixed bed, the compositions of main gas products were similar for these two feedstocks. However, the CH4 concentration of nitrogen-rich wood waste was much higher than that of pine saw dust during pyrolysis and gasification. More precisely, the CH4 concentration of nitrogen-rich wood waste was 48% higher than that of pine saw dust in the fixed bed gasification. These results suggested that the gasification of the nitrogen-rich wood waste had a better prospect of application. In addition, the nitrogen-rich wood waste generated much more gaseous nitrogen pollutants than pine saw dust. The NH3 concentration generated from the nitrogen-rich wood waste was about 147 times of that from pine saw dust. This indicated that gaseous nitrogen pollutants can be a barrier for the utilization of nitrogen-rich wood waste. In summary, the results from this study can be served as a constructive and meaningful reference for the treatment and high-efficiency utilization of nitrogen-rich wood waste.
With the development of the wood-processing industry, the artificial timber board is widely used for furniture, interior finishes, and wooden buildings. Due to the vast use of nitrogenous adhesives, the scrapped artificial timber board is named as nitrogen-rich wood waste, which has a great impact on environment. The gasification is one of the most important techniques for utilizing wood-based waste. Because of the clean and efficient characteristics, this technique can be used to dispose the nitrogen-rich wood waste. In order to study the gasification characteristics, gasification and pyrolysis of the nitrogen-rich wood waste and pine saw dust in Ar and Ar+O2 atmosphere were carried out in TG-MS-FTIR and the fixed bed, respectively. The effects of reaction conditions on the gasification-pyrolysis process and product distribution were studied. For the TG analysis, the experiments were carried out in Ar and Ar+O2 atmosphere, respectively. The reaction temperature increased from room temperature to 1 200 ℃ by a heating rate of 10 ℃/min. The wave number region of FTIR was 400-4 000 cm-1, the working voltage of the mass spectrometer was 70 eV, and the mass-to-charge ratios were 16, 28, 44, 17, 27, 30, 43, and 46, respectively. In the fixed bed experiments, the reaction temperature was 750 ℃ and the reaction atmosphere of pyrolysis was Ar(Gasification: Ar+O2). The results showed that the TG and DTG curves of these two materials presented similar stage divisions. The DTG peak value of nitrogen-rich wood waste was about 70% of that of pine saw dust, although the temperature of peak value of nitrogen-rich wood waste appeared ahead 15-20 ℃ than that of pine saw dust, which was earlier than that of pine saw dust in the DTG curve. Furthermore, the DTG curve of nitrogen-rich wood waste possessed a shoulder peak at 280-300℃, but it can not be observed in the DTG curve of pine saw dust. In the experiments of TG-MS-FTIR and fixed bed, the compositions of main gas products were similar for these two feedstocks. However, the CH4 concentration of nitrogen-rich wood waste was much higher than that of pine saw dust during pyrolysis and gasification. More precisely, the CH4 concentration of nitrogen-rich wood waste was 48% higher than that of pine saw dust in the fixed bed gasification. These results suggested that the gasification of the nitrogen-rich wood waste had a better prospect of application. In addition, the nitrogen-rich wood waste generated much more gaseous nitrogen pollutants than pine saw dust. The NH3 concentration generated from the nitrogen-rich wood waste was about 147 times of that from pine saw dust. This indicated that gaseous nitrogen pollutants can be a barrier for the utilization of nitrogen-rich wood waste. In summary, the results from this study can be served as a constructive and meaningful reference for the treatment and high-efficiency utilization of nitrogen-rich wood waste.
引文
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[16]孙云娟,蒋剑春.生物质热解气化行为的研究[J].林产化学与工业,2007,27(3):15-20.Sun Yunjuan,Jiang Jianchun.Study on biomass pyrolysis and gasification[J].Chemistry and Industry of Forest Products,2007,27(3):15-20.(in Chinese with English abstract)
[17]俞丽珍,孙才,周健,等.脲醛树脂木材胶粘剂的改性研究[J].新型建筑材料,2013,30(1):30-33.Yu Lizhen,Sun Cai,Zhou Jian,et al.Study on modification of urea-formaldehyde resin adhesives for wood[J].New Building Materials,2013,30(1):30-33.(in Chinese with English abstract)
[18]Mansuy L,Bourezgui Y,Garnier-Zarli E,et al.Characterization of humic substances in highly polluted river sediments by pyrolysis methylation-gas chromatography mass spectrometry[J].Organic Geochemistry,2001,32(2):223-231.
[19]Pandeya K K,Pitman A J.FTIR studies of the changes in wood chemistry following decay by brown-rot and white-rot fungi[J].International Biodeterioration Biodegradation,2003,52(3):151-160.
[20]Yu Tian,Jun Zhang,Wei Zuo,et al.Nitrogen conversion in relation to NH3 and HCN during microwave pyrolysis of sewage sludge[J].Environmental Science&Technology,2013,47:3498-3505.
[21]车得福.煤氮热变迁与氮氧化物生成[M].西安:西安交通大学出版社,2013.
[2]吕斌,张玉萍.我国饰面人造板行业发展现状与趋势[J].中国人造板,2017,24(2):1-3.Lyu Bin,Zhang Yuping.Status and development trend of china’s decorative wood-based panel industry[J].Chinese Wood-based Panels,2017,24(2):1-3.(in Chinese with English abstract)
[3]刘庆.中国人造板行业发展研究[D].上海:上海外国语大学,2013.Liu Qing.Study on Development of Chinese Wood-based Panel Industry[D].Shanghai:Shanghai International Studies University,2013.(in Chinese with English abstract)
[4]胡延杰.全球木质林产品贸易现状及发展趋势分析(二)[J].国际木业,2017,47(1):1-5.
[5]李婷婷,郑文堂,陈建成,等.中国人造板出口贸易影响因素及发展潜力:基于贸易引力模型的分析[J].经济问题探索,2014(8):92-101.Li Tingting,Zheng Wentang,Chen Jiancheng,et al.The influence factors and development potential of Chinese wood-based panel export trade[J].Inquiry into Economic Issues,2014(8):92-101.(in Chinese with English abstract)
[6]陶青.中国人造板出口市场结构及优化研究[D].北京:北京林业大学,2012.Tao Qing.Analysis on the Structure and Optimization of Export Market of Wood-based Panel in China[D].Beijing:Beijing Forestry University,2012.(in Chinese with English abstract)
[7]齐丛亮.人造板甲醛释放规律、机理及处理方法研究[D].桂林:广西师范大学,2015.Qi Congliang.Study on Releasing Rules,Model and Removal Method of Formaldehyde from Artificial Board[D].Guilin:Guangxi Normal University,2015.(in Chinese with English abstract)
[8]董晓婷.基于环保理念的人造板再利用制造技术研究[D].天津:天津大学,2017.Dong Xiaoting.Research on Reuse Manufacturing Technology of Artificial Board based on Sustainable Theory[D].Tianjin:Tianjin University,2017.(in Chinese with English abstract)
[9]韩淑伟.废弃MDF纤维再生制造复合人造板工艺研究[D].保定:河北农业大学,2010.Han Shuwei.Study on the Manufacturing Technique of Wood-Based Composite Panel Made from Waste MDFFiber[D].Baoding:Agricultural University of Hebei,2010.(in Chinese with English abstract)
[10]张配芳.人造板生产废水与废气污染治理解决方案[J].化工设计通讯,2017,43(1):166,177.Zhang Peifang.Solution for waste water and waste gas pollution control of wood-based panel production[J].Resources and Environment,2017,43(1):166,177.(in Chinese with English abstract)
[11]Moreno A I,Font R.Pyrolysis of furniture wood waste:Decomposition and gases evolved[J].Journal of Analytical and Applied Pyrolysis,2015,113:464-473.
[12]陈世华,李思锦,母军.脲醛树脂胶黏剂在纤维板热解固体产物中的转化特性[J].北京林业大学学报,2013,35(4):123-127.Chen Shihua,Li Sijin,Mu Jun.Conversion characteristics of urea formaldehyde resin adhesive in fiberboard through pyrolysis into solid product[J].Journal of Beijing Forestry University,2013,35(4):123-127.(in Chinese with English abstract)
[13]陈世华,冯永顺,母军,等.废弃人造板热解冷凝液的抑菌特性[J].北京林业大学学报:自然科学版,2012,34(6):131-136.Chen Shihua,Feng Yongshun,Mu Jun,et al.Bacteriostatic characteristics of disused wood-based board pyrolysis condensate liquid[J].Journal of Beijing Forestry University:Natural Science Edition,2012,34(6):131-136.(in Chinese with English abstract)
[14]冯宜鹏,王小波,赵增立,等.烘焙预处理对高含氮木质废弃物气流床气化特性与含氮污染物分布的影响研究[J].太阳能学报,2018,39(7):1908-1916.Feng Yipeng,Wang Xiaobo,Zhao Zengli,et al.Investigation on effect of torrefaction on characteristics and distributions of nitrogenous pollutants during entrained flow gasification of nitrogen-rich woodwaste[J].Acta Energiae Solaris Sinica,2018,39(7):1908-1916.(in Chinese with English abstract)
[15]谭洪,王树荣,骆仲泱,等.生物质三组分热裂解行为的对比研究[J].燃料化学学报,2006,34(1):61-65.Tan Hong,Wang Shurong,Luo Zhongyang,et al.Pyrolysis behavior of cellulose,xylan and lignin[J].Journal of Fuel Chemistry and Technology,2006,34(1):61-65.(in Chinese with English abstract)
[16]孙云娟,蒋剑春.生物质热解气化行为的研究[J].林产化学与工业,2007,27(3):15-20.Sun Yunjuan,Jiang Jianchun.Study on biomass pyrolysis and gasification[J].Chemistry and Industry of Forest Products,2007,27(3):15-20.(in Chinese with English abstract)
[17]俞丽珍,孙才,周健,等.脲醛树脂木材胶粘剂的改性研究[J].新型建筑材料,2013,30(1):30-33.Yu Lizhen,Sun Cai,Zhou Jian,et al.Study on modification of urea-formaldehyde resin adhesives for wood[J].New Building Materials,2013,30(1):30-33.(in Chinese with English abstract)
[18]Mansuy L,Bourezgui Y,Garnier-Zarli E,et al.Characterization of humic substances in highly polluted river sediments by pyrolysis methylation-gas chromatography mass spectrometry[J].Organic Geochemistry,2001,32(2):223-231.
[19]Pandeya K K,Pitman A J.FTIR studies of the changes in wood chemistry following decay by brown-rot and white-rot fungi[J].International Biodeterioration Biodegradation,2003,52(3):151-160.
[20]Yu Tian,Jun Zhang,Wei Zuo,et al.Nitrogen conversion in relation to NH3 and HCN during microwave pyrolysis of sewage sludge[J].Environmental Science&Technology,2013,47:3498-3505.
[21]车得福.煤氮热变迁与氮氧化物生成[M].西安:西安交通大学出版社,2013.