| 碱木质素与油页岩共热解特性及动力学分析 |
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| 引用本文： | 柏静儒,邵佳晔,李梦迪,贾春霞,王擎.碱木质素与油页岩共热解特性及动力学分析[J].农业工程学报,2016,32(7):187-193. |
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| 作者姓名： | 柏静儒 邵佳晔 李梦迪 贾春霞 王擎 |
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| 作者单位： | 东北电力大学油页岩综合利用教育部工程研究中心,吉林,132012 |
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| 基金项目： | 吉林省重点科技攻关项目（20140204004SF）；长江学者和创新团队发展计划（IRT13052） |
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| 摘 要： | 通过油页岩与碱木质素的热解不但可以得到丰富的轻质气体,也存在着有害的含芳环结构化合物以及酚类化合物等物质,通过二者的共热解意在减小有害物质的生成,提高气产率。选取不同工况下碱木质素与油页岩进行共热解试验,并通过2种Model free动力学分析法对该混合试样进行拟合分析。结果表明:5个试样的失质量峰整体都具有相同的规律。油页岩与碱木质素的热解峰有叠加,具备协同的条件。碱木质素添加量为80%的混合试样对气产率存在抑制作用,其余混合比都使气产率增加。基于FTIR的检测,混合比对二者的共热解产量影响的研究中表明,向油页岩中添加80%的碱性木质素,可以减少芳环结构化合物与酚类化合物的生成。但对于H2O、CO、CO2、CH4的累积产量并未产生明显的影响。不同升温速率的试样中,芳环结构化合物、CO2、CH4的累积产量与升温速率和温度成正比,H2O、CO、苯酚类化合物则不同。通过2种Model free法对该试验数据进行拟合且效果较好,证明了该反应机理的复杂性。
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| 关 键 词： | 油页岩 热解 生物质 TG-FTIR Model free法 碱木质素 |
| 收稿时间： | 2015/7/15 0:00:00 |
| 修稿时间： | 2015/12/17 0:00:00 |
Co-pyrolysis characteristic and dynamic analysis of alkali lignin and oil shale |
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| Bai Jingru,Shao Jiaye,Li Mengdi,Jia Chunxia and Wang Qing.Co-pyrolysis characteristic and dynamic analysis of alkali lignin and oil shale[J].Transactions of the Chinese Society of Agricultural Engineering,2016,32(7):187-193. |
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| Authors: | Bai Jingru Shao Jiaye Li Mengdi Jia Chunxia and Wang Qing |
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| Institution: | Northeast Dianli University, Engineering Research Centre of Oil Shale Comprehensive Utilization Ministry of Education, Jilin 132012, China,Northeast Dianli University, Engineering Research Centre of Oil Shale Comprehensive Utilization Ministry of Education, Jilin 132012, China,Northeast Dianli University, Engineering Research Centre of Oil Shale Comprehensive Utilization Ministry of Education, Jilin 132012, China,Northeast Dianli University, Engineering Research Centre of Oil Shale Comprehensive Utilization Ministry of Education, Jilin 132012, China and Northeast Dianli University, Engineering Research Centre of Oil Shale Comprehensive Utilization Ministry of Education, Jilin 132012, China |
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| Abstract: | Use of different heating rates (30, 50, 80 K/min) for lignin alkaline and oil shale mixed sample (lignin alkaline dosage 20%, 50%, 80%) in co-pyrolysis combined with TG-FTIR technique, we analyzed pyrolysis products and cumulative production trends at different heating rates. After that we fit data in two model free kinetic analysis methods (FWO method, Starink method). The results showed that due to differences in the rate of heat transfer, the amount of heat a sample received determined the quantity of weight loss from a tested sample. Weight loss increase in five specimens was observed with the increase of heating rate at the high temperature region. When lignin alkaline was added to oil shale, DTG curves changed significantly at 400-500℃. After 600℃, both oil shale and lignin in co-pyrolysis had an overlapped peak. Based on TGA data collected and the data in the pyrolysis product precipitated at the initial temperature and the temperature corresponding to the termination of weight loss, both samples obtained separate pyrolysis product yields when co-pyrolysis solution was in the same mixed sample heating rate. The 50% lignin alkaline product yields were the highest in contrast to that with mixed different heating rates and different mixing ratio of lignin alkaline and oil shale. It was possible that at the heating rate of 80 K/min, lignin alkaline dosage product yielded 50% of the maximum. According to FTIR detection, in the mixed sample, cumulative production curve of pyrolysis products under different mixing ratio showed that 50% of lignin alkaline added in the mixed sample with respect to the separate production of the two pyrolysis products can reduce aromatic ring structure compounds, phenolic compounds, H2O. For different heating rate and yield curve of accumulated pyrolysis products, it showed that the aromatic ring structure compounds, and CO2, CH4 cumulative production in response to increase of heating rates and temperature increased proportionally. Cumulative production of H2O over heating rate and temperature was proportionally related for pyrolysis temperature of 200-600℃. Only after 700℃, CO cumulative production and its relationship with the heating rate was proportionally related to temperature rise. For phenolic compounds, cumulative production at 50 K/min reached the highest for 250-800℃ .In this temperature range heating rate and cumulative production of phenolic compounds was proportionally related to temperature. But beyond 800℃, at heating rate of 30 or 50 K/min, output began to fall. To choose proper lignin alkaline and oil shale content under a 50% of the mixed sample with a heating rate of 30, 50, 80 K/min we calculated the activation energy E for conversion rate for both lignin alkaline and the oil. The activation energy of both fit a linear function with a correlation coefficient of 0.95 and they were approximately parallel each other. The activation energy at the same conversion rate of maximum error was only 10 kJ/mol. In the model free methods, the conversion rate 0.45, 0.7, 0.85 have emerged during the activation energy decreases. By fitting the result, the two methods can show the complexity of the reaction mechanisms. |
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| Keywords: | oil shale pyrolysis biomass TG-FTIR model free method lignin alkaline |
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