麦草/聚酯混合超临界乙醇液化及其机理的研究
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摘要
随着社会的发展,人们对石油,天然气和煤的消耗量不断增大。化石燃料的大量消耗,不仅引起了温室效应,产生了酸雨,还使空气的质量变差,严重威胁着我们的生存环境,因此,利用开发可再生能源走可持续发展的能源道路已经引起各国政府高度重视。近几年,随着超临界技术的不断成熟,超临界流体的优良特性引起越来越多的科研人员的关注,并被用于制药,化工和材料等行业;同时其优良特性也被用于生物质能的开发,并具有广阔的开发前景。麦草属于农业废弃物,我国每年的产量有上几亿吨;每年工业和日常生活中会产生的塑料垃圾有几百万吨,如果这些物质处理不当不仅会污染环境,还是对太阳能资源和石油资源的一种浪费。
本文以超临界技术为手段,利用超临界乙醇流体实现麦草和聚酯的混合液化,将农业废弃物和工业废弃物转变成可再生的能源,实现农业和工业的和谐可持续发展。本文主要研究麦草和聚酯在超临界乙醇中的液化行为,讨论了液化温度、聚酯用量、固液比和液化时间对液化产率的影响。通过研究发现,当液化温度275℃,固液比1︰6,保温30min,聚酯与麦草的质量比为2时,麦草中有机质的液化率达到88.87%,混合液化率达到96.52%。同时对液化产物进行GC-MS分析,检测到三十几种液化产物,主要是苯酚及其衍生、酯类、有机酸、醛等。
本文比较了两种催化剂对混合液产率的影响,一种是弱碱性催化剂碳酸钠,碳酸钠对混合液化的产率提高不大,当碳酸钠用量为麦草质量的10%时最好,液化产率仅提高0.37%;另一种是自制的固体酸SO_4~(2-)/Fe_2O_3,当固体酸用量为麦草质量的9%时最好,液化产率提高2.98%。
研究了循环液化对麦草液化产率的影响,得出循环液化对麦草也具有较好的液化效果,第三次循环液化的液化率与未循环液化相比提高了17.03%;循环液化中的溶剂抑制了麦草的炭化,减轻了液化设备清洗的负担。循环液化还可以实现工业化的连续生产。
利用反应釜的冷却快速装置,通过突然中止反应的方法,得到不同冷却温度下混合液化的中间产物,通过红外光谱(IR),分析液化产物的残渣并与麦草粉比较,得到化学键的变化情况,并通过气质联用仪(GC-MS)对液化产物进行分析,得到其组成成分,再结合不同温度下的产率,研究推测不同温度下麦草和聚酯液化裂解情况,推测混合液化的液化机理。为优化工艺和控制反应过程提供理论基础。
With the development of the society, the demand for oil, natural gas and coal is increasing. The large consumption of fossil fuel cause the greenhouse effect that pollutes the air and the environment get worse day by day. To change the status quo , the governments have to pay attention to the research on the renewable energy. The supercritical technology is well developed recent years. Because of the excellent characteristics,it is widely used in the area of pharmaceutical industry,chemical industry and material industry. What more, it is also used on the research of the biomass which has broad prospect. The wheat straw, waste in agriculture, produced hundreds million every years in china and numbers of plastic garbage that produced by industry and people is not only bad for the environment but also be a waste as solar energy resource and oil resource.
In this article, we mix polyester with wheat straw and then liquefied them in supercritical ethanol. It transforms the agriculture wastes and industry wastes into renewable energy. Through the experiment ,we analysis the influencing factors of liquefaction yield, including reaction temperature, reaction time ,dosage of the polyester and the solid-liquid ratio.We found that when the temperature is 275℃,the solid-liquid ratio is 1:6,the dosage of the polyester is twice of the straw and the reaction time is 30min, the liquefaction rate of the organic compounds in straw is up to 88.87% and the liquefaction rate of the mixture is up to 96.52%. With the GC-MS Analysis of liquefaction products, we detect more than 30 kinds of substances, including phenol and the derivatives of phenol, ester, organic acid and aldehyde.
We study the influence of two catalysts on the liquefaction rate. We found the sodium carbonate which is weak alkaline has little action to the liquefaction rate. When the dosage of sodium carbonate is 10% of the straw, the action is best while the liquefaction rate only increased 5.2%. Compare with the sodium carbonate, SO_4~(2-)/Fe_2O_3 solid acid is better. When the dosage is 9% of the straw, the action is best. The liquefaction rate increased 7.81%.
Study on the effect of circulating liquefaction to the liquefaction rate of the straw.It is learned that circulating liquefaction leads to the high rate.After twice circulation,the rate is 17.03% higher than no circulating.The impregnant restrain the carbonization of the straw during circulating,and make the reactor easier washing.What more, circulating liquefaction make industrial continuous production possible.
When terminate the reaction in sudden by the fast cooling device of the high-pressure reactor, we get the intermediate products in different temperatures. Then analysis the residues by Infrared Spectroscopy and compare with the straw powder, we learn the transformation of chemical bond. After that, we analysis the liquefaction products by GC-MS and get the components.By doing these, we could learn the liquefaction mechanism. It provides theoretical basis to process optimization and control of the process of reaction.
本文以超临界技术为手段,利用超临界乙醇流体实现麦草和聚酯的混合液化,将农业废弃物和工业废弃物转变成可再生的能源,实现农业和工业的和谐可持续发展。本文主要研究麦草和聚酯在超临界乙醇中的液化行为,讨论了液化温度、聚酯用量、固液比和液化时间对液化产率的影响。通过研究发现,当液化温度275℃,固液比1︰6,保温30min,聚酯与麦草的质量比为2时,麦草中有机质的液化率达到88.87%,混合液化率达到96.52%。同时对液化产物进行GC-MS分析,检测到三十几种液化产物,主要是苯酚及其衍生、酯类、有机酸、醛等。
本文比较了两种催化剂对混合液产率的影响,一种是弱碱性催化剂碳酸钠,碳酸钠对混合液化的产率提高不大,当碳酸钠用量为麦草质量的10%时最好,液化产率仅提高0.37%;另一种是自制的固体酸SO_4~(2-)/Fe_2O_3,当固体酸用量为麦草质量的9%时最好,液化产率提高2.98%。
研究了循环液化对麦草液化产率的影响,得出循环液化对麦草也具有较好的液化效果,第三次循环液化的液化率与未循环液化相比提高了17.03%;循环液化中的溶剂抑制了麦草的炭化,减轻了液化设备清洗的负担。循环液化还可以实现工业化的连续生产。
利用反应釜的冷却快速装置,通过突然中止反应的方法,得到不同冷却温度下混合液化的中间产物,通过红外光谱(IR),分析液化产物的残渣并与麦草粉比较,得到化学键的变化情况,并通过气质联用仪(GC-MS)对液化产物进行分析,得到其组成成分,再结合不同温度下的产率,研究推测不同温度下麦草和聚酯液化裂解情况,推测混合液化的液化机理。为优化工艺和控制反应过程提供理论基础。
With the development of the society, the demand for oil, natural gas and coal is increasing. The large consumption of fossil fuel cause the greenhouse effect that pollutes the air and the environment get worse day by day. To change the status quo , the governments have to pay attention to the research on the renewable energy. The supercritical technology is well developed recent years. Because of the excellent characteristics,it is widely used in the area of pharmaceutical industry,chemical industry and material industry. What more, it is also used on the research of the biomass which has broad prospect. The wheat straw, waste in agriculture, produced hundreds million every years in china and numbers of plastic garbage that produced by industry and people is not only bad for the environment but also be a waste as solar energy resource and oil resource.
In this article, we mix polyester with wheat straw and then liquefied them in supercritical ethanol. It transforms the agriculture wastes and industry wastes into renewable energy. Through the experiment ,we analysis the influencing factors of liquefaction yield, including reaction temperature, reaction time ,dosage of the polyester and the solid-liquid ratio.We found that when the temperature is 275℃,the solid-liquid ratio is 1:6,the dosage of the polyester is twice of the straw and the reaction time is 30min, the liquefaction rate of the organic compounds in straw is up to 88.87% and the liquefaction rate of the mixture is up to 96.52%. With the GC-MS Analysis of liquefaction products, we detect more than 30 kinds of substances, including phenol and the derivatives of phenol, ester, organic acid and aldehyde.
We study the influence of two catalysts on the liquefaction rate. We found the sodium carbonate which is weak alkaline has little action to the liquefaction rate. When the dosage of sodium carbonate is 10% of the straw, the action is best while the liquefaction rate only increased 5.2%. Compare with the sodium carbonate, SO_4~(2-)/Fe_2O_3 solid acid is better. When the dosage is 9% of the straw, the action is best. The liquefaction rate increased 7.81%.
Study on the effect of circulating liquefaction to the liquefaction rate of the straw.It is learned that circulating liquefaction leads to the high rate.After twice circulation,the rate is 17.03% higher than no circulating.The impregnant restrain the carbonization of the straw during circulating,and make the reactor easier washing.What more, circulating liquefaction make industrial continuous production possible.
When terminate the reaction in sudden by the fast cooling device of the high-pressure reactor, we get the intermediate products in different temperatures. Then analysis the residues by Infrared Spectroscopy and compare with the straw powder, we learn the transformation of chemical bond. After that, we analysis the liquefaction products by GC-MS and get the components.By doing these, we could learn the liquefaction mechanism. It provides theoretical basis to process optimization and control of the process of reaction.
引文
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