闻 明, 张世红, 邵敬爱, 陈应泉, 冯 磊, 王贤华, 陈汉平. 生物质富氮热解联产高值含氮油炭的理化特性[J]. 农业工程学报, 2015, 31(13): 229-235. DOI: 10.11975/j.issn.1002-6819.2015.13.032
    引用本文: 闻 明, 张世红, 邵敬爱, 陈应泉, 冯 磊, 王贤华, 陈汉平. 生物质富氮热解联产高值含氮油炭的理化特性[J]. 农业工程学报, 2015, 31(13): 229-235. DOI: 10.11975/j.issn.1002-6819.2015.13.032
    Wen Ming, Zhang Shihong, Shao Jing′ai, Chen Yingquan, Feng Lei, Wang Xianhua, Chen Hanping. Physicochemical properties of nitrogen rich in oil and char during biomass nitrogen-rich pyrolysis[J]. Transactions of the Chinese Society of Agricultural Engineering (Transactions of the CSAE), 2015, 31(13): 229-235. DOI: 10.11975/j.issn.1002-6819.2015.13.032
    Citation: Wen Ming, Zhang Shihong, Shao Jing′ai, Chen Yingquan, Feng Lei, Wang Xianhua, Chen Hanping. Physicochemical properties of nitrogen rich in oil and char during biomass nitrogen-rich pyrolysis[J]. Transactions of the Chinese Society of Agricultural Engineering (Transactions of the CSAE), 2015, 31(13): 229-235. DOI: 10.11975/j.issn.1002-6819.2015.13.032

    生物质富氮热解联产高值含氮油炭的理化特性

    Physicochemical properties of nitrogen rich in oil and char during biomass nitrogen-rich pyrolysis

    • 摘要: 通过引进外源氮素使生物质在富氮条件下热解,可以获得高值化的含氮产品-焦炭和油。基于生物质富氮热解联产高值含氮产品这一目标,该文以木屑为原料,对不同温度和不同质量分数尿素溶液浸渍下热解制得的生物油进行了气相色谱质谱联用分析。同时对热解产生的生物油和热解焦炭进行了元素分析,使用漫反射红外光谱和X射线光电子能谱仪对富氮条件下制得的热解焦炭进行了表面表征。研究发现,经过尿素溶液浸渍过后的生物质,热解油中含有大量的含氮化学品,可以被用来提炼加工高附加值的化工产品。随着温度的升高,热解油中的含氮物质减少、浸渍质量分数越大油中的含氮物质越多。热解焦炭表面含有大量的芳香化结构和含氮官能团,漫反射红外分析结果显示低温下焦炭表面含有丰富的化学结构,随着温度的升高各种官能团逐渐分解,750、850℃时表面只剩下羟基、羰基等官能团;尿素溶液质量分数对热解后焦炭的表面官能团种类没有显著的影响,只有强弱的区别。XPS分析尿素浸渍生物质热解焦炭表面主要是一些C=N、C-N以及N-COO官能团并且随着温度的升高850℃时焦炭表面只有吡啶型N和吡咯型N存在。550℃下热解焦炭中的碳主要是无定形碳,随着温的升高焦炭中的一些脂肪链C-H键,羰基和一些低聚C-C键基本消失,850℃下的碳则主要表现为石墨形碳。

       

      Abstract: Abstract: Biomass is one of the most important renewable resources. Pyrolysis for producing high value added products provides additional value for biomass energy utilization. Through the introduction of exogenous nitrogen in biomass pyrolysis in nitrogen-rich conditions, it can get high value of nitrogen-containing products, i.e. nitrogen-rich char and oil. In this study, wood chips were used as raw materials. The experiment was carried out in a fixed bed reactor at 350 to 850℃, and the effect of temperature and impregnation ratio(5%, 10%, 15%, 20%) on products yields, compositions and characteristics were investigated. Firstly, wood chips were immersed in different mass fractions of urea solution, stirred for 12 hours with a magnetic mixer at room temperature. The woodchips was then separated from solution by filtration and was dried after for 24 hours in an oven. The dried woodchips was then gone through pyrolysis and the bio-oil obtained at different temperatures was analyzed by gas chromatography-mass spectrometry. Derived bio-oil and char were also analyzed for their compositions to trace nitrogen mass transfer. The surface physicochemical property of the char under nitrogen-rich conditions was characterized using a diffuse reflectance infrared spectroscopy and X-ray photoelectron spectroscopy. With the rise of impregnation ratio, the yield of char and bio-oil had little change. Temperature had a remarkable effect on the yield and nitrogen content of boichar and bio oil. Change of product yields was mainly due to the three components (cellulose, ligin and semicellulose) decomposing at different temperatures, and to the volatilization of the secondary cracking at high temperature. The GC-MS results indicated that after treated with urea solution, biomass pyrolysis oil contains large amounts of nitrogen-containing chemicals that can be used to refine high value-added chemical products. The nitrogen-containing chemicals in the bio-oil mainly include aromatic amine, nitrogenous heterocyclic compounds and amide substances. As the temperature increased, the nitrogen content in pyrolysis bio-oil decreased. The larger of urea solution mass fraction, the more nitrogen-containing chemicals in the pyrolysis oil. Pyrolysis char surface contains large amounts of aromatic structure and abundant nitrogen-containing functional groups. Diffuse reflectance IR analysis showed that at the low temperature char surface was rich in C-N, and -NH groups caused by reactions of amino and bio-char. It was confirmed that introducing the exogenous nitrogen into the biomass pyrolysis process can produce nitrogen rich char with a large number of nitrogen-containing functional groups. With temperature increasing, various functional groups decomposed gradually. At 750 and 850℃ only some hydroxyl groups and carbonyl groups were left on the char surface. The urea solution mass fraction had less effect on the types of surface functional groups on the pyrolysis char, but impacted functional group intensity. XPS analysis revealed that the char surface mainly contained C=N, C-N and N-COO functional groups and at 850℃, the char surface only contained pyridine-N and pyrrole-N. This phenomenon could be explained by that thermal stability of pyridine-N and pyrrole-N was better than amide substances. At the pyrolysis temperature of 550℃, the carbon in pyrolysis char was mainly amorphous carbon. With temperature increasing, some aliphatic chain C-H bond, carbonyl and some oligomeric C-C bonds disappeared, while when the temperature reached 850℃, the carbon in char was dominated by graphite carbon.

       

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