流化式自供热型制生物燃油关键装置设计理论研究
摘要
我国是石油消费和进口大国,石油消耗量仅次于美国,位居世界第二位。同时,国内石油产能严重不足,进口依存度不断扩大。2009年中国石油净进口量2.19亿吨,表观消费量4.08亿吨,进口依存度首次突破50%；2010年中国石油净进口量2.49亿吨,表观消费量约为4.49亿吨,进口依存度已高达55%以上；预计到2012年进口依存度将高达75%以上。如此高的石油进口依存度,已威胁我国能源安全,一旦国际石油供应出现问题,比如战争,我国的能源供应将会受到严重打击,甚至国民经济都有瞬间陷入瘫痪的危险。另一方面,我国是一个农业大国,仅农作物秸秆年产生量约7亿吨,扣去现有各种利用,大约3亿吨可作为燃料使用,林业废弃物年可获得量约9亿吨,如仅将这两类生物质资源进行转化,就可得到6亿吨生物燃油,按热值推算,相当于3亿吨重油,因此将秸秆等农林废弃物转化成具有一定经济价值和高技术含量的石油替代产品,不仅缓解我国能源紧张的状况,而且增加了农民的就业岗位和个人收入,另外,将生物质通过热裂解技术转化后的石油替代产品——生物燃油具有不含硫、减少环境污染、C02零排放、符合CDM(清洁发展机制)要求。本文正是在这样的背景下,针对生物质制生物燃油技术进行的研究,其目的在于为生物质热裂解制生物燃油装置设计提供先进的理论支持和技术保障。
本文对国内外生物质流化式热裂解技术的研究进行了总结和论述,根据流化式热裂解工艺的特点,总结前人的研究经验,提出了流化式自供热型制油装置反应器的理论和实验研究,在研究过程当中取得如下成果：
根据热裂解反应动力学原理,为流化式自供热型反应器,建立生物质热裂解反应动力学方程,并对方程求解,得到生物质热裂解产物曲线；在实验室利用热裂解实验装置进行实验,将通过实验取得热裂解产物曲线与方程求得的热裂解产物曲线进行了对比分析,验证了热裂解方程的可靠性；在生物燃油冷凝过程的研究中,根据已知晓的生物燃油成分,计算出冷凝温度不同阶段,对应的理论冷凝量,通过与相同阶段温度的冷凝实验结果相比对,验证理论结果,确定出最合理的冷凝温度范围,为系统冷凝工艺提供理论依据。
根据气固两相流的原理,提出了一种在普通圆柱型流化床内部加圆锥体的内锥式流化床反应器设计思路,通过冷态实验结果表明,流化效果优于普通圆柱型流化床。同时因为流化状态的复杂性,建立气固两相流流动方程,利用Fluent模拟仿真软件,采用欧拉模型,对内锥式流化床进行颗粒运动状态、浓度与速度的数值模拟,并将模拟结果与普通圆柱型流化床进行比较分析。
构建了基于内锥式流化床反应器的系统组成模式,对系统进行了工艺分析,从理论上对系统进行了热平衡研究与分析,从经济性角度提出了除电力拖动以外的生产用能仅用副产物炭粉和不凝气供热的设想,并通过转化率对副产物产率影响的研究,得出自供热条件下的最优转化率,为生物质制油系统不依赖外部热源而自身达到热平衡的这种先进的设计提供了理论指导。
针对本文提出的自供热系统和仅用副产物炭粉和不凝气为整个系统供热的设想,根据燃烧理论对气—固混合燃烧装置进行了设计理论研究。另外,为了将燃烧后排放烟气中的热能在流化干燥中利用,根据流化干燥理论对流化干燥和输送装置进行了设计理论研究。
上述研究及结果可为基于内锥式流化床反应器的自供热裂解制生物燃油系统的设计提供理论指导和研发借鉴。有望为中国的生物燃油生产的规模化、工业化提供理论参考。
Our country is a big country of petroleum consumption and importing, the amount of petroleum consumption is only next to the United States in the world. At the same time, domestic oil production is severity shortage, import dependency of petroleum expands unceasingly. Net import amount of petroleum of China is 2.19 billion tons in 2009, apparent consumption is 4.08 tons, import dependency is first up to 50%; Net import amount of petroleum of China is 2.49 billion tons in 2010, apparent consumption is 4.49 tons, import dependency is more than 55%; import dependency is expected to as high as 75% in 2012. Such high levels of oil import dependence, our country's energy security has been threatened, once the international oil supply has problems, such as war, our energy supply will be hit hard, even the national economy have the instant paralyzed danger. On the other hand, our country is a large agricultural nation, annual production of crops straw is about 7 million tons, except for all kinds of use, about 3 million tons can.be used as fuel, also annual production of forestry waste is about 9 million tons. If these two types of biomass resources can be effectively used,6 million tons of biofuels can be achieved, if calculating as the calorific value, which is equal to 3 million tons of heavy fuel oil. Therefore transforming crops straw and forestry waste into oil alternative products which have certain economic value and high technical contents, not only can ease the energy shortage status, and can increase farmer's employment chances and personal income. In addition, biomass can be transformed to the alternative products of oil through pyrolysis technology-biofuels do not contain sulfur, can reduce the pollution for the environment, zero emissions of CO2 and comply with the requirements of clean development mechanism (CDM). In this context, the paper carries out biomass biofuels technology research, its purpose lies in providing an advanced theoretical support and technical guarantee for the design of biomass pyrolysis bio-fuel device.
Biomass fluidized pyrolysis technology in aboard and domestic country are summarized and discussed in the paper, according to the characteristics of fluidization type pyrolysis technology, summarizing the predecessor's research experiences, presenting the processing routes, system composition mode and key devices of fluidization type self-heating biomass pyrolysis system-theoretical analysis and experimental research of fluidization type self-heating biomass pyrolysis reactor have be done, the obtained achievements of research process are as follows:
According to the pyrolysis reaction kinetics theory, the kinetic equation of biomass pyrolysis reaction has been established for the fluidization type self-heating biomass pyrolysis reactor, the biomass pyrolysis product curves can be achieved by solving the equation; using pyrolysis experiment device to carry out experiments, the comparison analysis of the pyrolysis product curves got by experiments and equations has been done, the reliability of pyrolysis equation has been verified; in the study of the biofuels condensation process, based on the known biofuels components, to calculate the different stages of the condensation temperature corresponding the theory condensation amount, through the comparisons of the condensing experimental results of the same stages temperature to verify the validity of the theoretical results, and to determine the most reasonable condensing temperature ranges.
According to the theory of gas-solid two-phase flow, proposing a new design thinking of the inner cone type fluidized bed which adding a cone in the inner of the common cylindrical fluidized bed, the cold experimental results show that the fluidization effect is better than the common cylindrical type fluidized bed. At the same time, as the complexity of fluidized state, to establish flow equations of the gas-solid two-phase flow, using FLUENT simulation software, adopting Euler model, the numerical simulation of particle motion state, concentration and speed has been done respectively for the inner cone type fluidized bed, also the comparison analysis of the simulation results of the ordinary cylinder and the inner cone type fluidized bed has been done.
Based on the inner cone type fluidized bed reactor, the system components mode has been build up, the system process analysis and the thermal equilibrium research and analysis on the system have also been done, from the economy view, the assumption that the production energy can be obtained by the by-products charcoal and non-condensable gas except for the electric driving, and through the effect of the conversion ratio on the by-product production rate, the optimal conversion rate under the self-heating conditions has been built, the theoretical guidance has been provided for the advanced design that the biofuels system does not depend on the outside heat but can achieve heating balance themselves.
According to the proposed assumptions that the system can realize self-heating and heating can be obtained only by the by-products charcoal and non-condensable gas for the whole system, also according to the principle of burning, the design theory research of the gas-solid mixing burning device has been carried out. In addition, in order to put the heat energy of smoke and fumes after burning into use in the fluidization dry process, the design theory research of the fluidization dry and transporting device according to the fluidization dry theory has been carried out.
The theoretical guidance and research reference based on the inner cone type fluidized bed reactor of self-heating pyrolysis biofuels system can be provided according to the above research and results. It is expected to provide the theoretical reference for the scale and industrialization of China's biofuels production.
本文对国内外生物质流化式热裂解技术的研究进行了总结和论述,根据流化式热裂解工艺的特点,总结前人的研究经验,提出了流化式自供热型制油装置反应器的理论和实验研究,在研究过程当中取得如下成果：
根据热裂解反应动力学原理,为流化式自供热型反应器,建立生物质热裂解反应动力学方程,并对方程求解,得到生物质热裂解产物曲线；在实验室利用热裂解实验装置进行实验,将通过实验取得热裂解产物曲线与方程求得的热裂解产物曲线进行了对比分析,验证了热裂解方程的可靠性；在生物燃油冷凝过程的研究中,根据已知晓的生物燃油成分,计算出冷凝温度不同阶段,对应的理论冷凝量,通过与相同阶段温度的冷凝实验结果相比对,验证理论结果,确定出最合理的冷凝温度范围,为系统冷凝工艺提供理论依据。
根据气固两相流的原理,提出了一种在普通圆柱型流化床内部加圆锥体的内锥式流化床反应器设计思路,通过冷态实验结果表明,流化效果优于普通圆柱型流化床。同时因为流化状态的复杂性,建立气固两相流流动方程,利用Fluent模拟仿真软件,采用欧拉模型,对内锥式流化床进行颗粒运动状态、浓度与速度的数值模拟,并将模拟结果与普通圆柱型流化床进行比较分析。
构建了基于内锥式流化床反应器的系统组成模式,对系统进行了工艺分析,从理论上对系统进行了热平衡研究与分析,从经济性角度提出了除电力拖动以外的生产用能仅用副产物炭粉和不凝气供热的设想,并通过转化率对副产物产率影响的研究,得出自供热条件下的最优转化率,为生物质制油系统不依赖外部热源而自身达到热平衡的这种先进的设计提供了理论指导。
针对本文提出的自供热系统和仅用副产物炭粉和不凝气为整个系统供热的设想,根据燃烧理论对气—固混合燃烧装置进行了设计理论研究。另外,为了将燃烧后排放烟气中的热能在流化干燥中利用,根据流化干燥理论对流化干燥和输送装置进行了设计理论研究。
上述研究及结果可为基于内锥式流化床反应器的自供热裂解制生物燃油系统的设计提供理论指导和研发借鉴。有望为中国的生物燃油生产的规模化、工业化提供理论参考。
Our country is a big country of petroleum consumption and importing, the amount of petroleum consumption is only next to the United States in the world. At the same time, domestic oil production is severity shortage, import dependency of petroleum expands unceasingly. Net import amount of petroleum of China is 2.19 billion tons in 2009, apparent consumption is 4.08 tons, import dependency is first up to 50%; Net import amount of petroleum of China is 2.49 billion tons in 2010, apparent consumption is 4.49 tons, import dependency is more than 55%; import dependency is expected to as high as 75% in 2012. Such high levels of oil import dependence, our country's energy security has been threatened, once the international oil supply has problems, such as war, our energy supply will be hit hard, even the national economy have the instant paralyzed danger. On the other hand, our country is a large agricultural nation, annual production of crops straw is about 7 million tons, except for all kinds of use, about 3 million tons can.be used as fuel, also annual production of forestry waste is about 9 million tons. If these two types of biomass resources can be effectively used,6 million tons of biofuels can be achieved, if calculating as the calorific value, which is equal to 3 million tons of heavy fuel oil. Therefore transforming crops straw and forestry waste into oil alternative products which have certain economic value and high technical contents, not only can ease the energy shortage status, and can increase farmer's employment chances and personal income. In addition, biomass can be transformed to the alternative products of oil through pyrolysis technology-biofuels do not contain sulfur, can reduce the pollution for the environment, zero emissions of CO2 and comply with the requirements of clean development mechanism (CDM). In this context, the paper carries out biomass biofuels technology research, its purpose lies in providing an advanced theoretical support and technical guarantee for the design of biomass pyrolysis bio-fuel device.
Biomass fluidized pyrolysis technology in aboard and domestic country are summarized and discussed in the paper, according to the characteristics of fluidization type pyrolysis technology, summarizing the predecessor's research experiences, presenting the processing routes, system composition mode and key devices of fluidization type self-heating biomass pyrolysis system-theoretical analysis and experimental research of fluidization type self-heating biomass pyrolysis reactor have be done, the obtained achievements of research process are as follows:
According to the pyrolysis reaction kinetics theory, the kinetic equation of biomass pyrolysis reaction has been established for the fluidization type self-heating biomass pyrolysis reactor, the biomass pyrolysis product curves can be achieved by solving the equation; using pyrolysis experiment device to carry out experiments, the comparison analysis of the pyrolysis product curves got by experiments and equations has been done, the reliability of pyrolysis equation has been verified; in the study of the biofuels condensation process, based on the known biofuels components, to calculate the different stages of the condensation temperature corresponding the theory condensation amount, through the comparisons of the condensing experimental results of the same stages temperature to verify the validity of the theoretical results, and to determine the most reasonable condensing temperature ranges.
According to the theory of gas-solid two-phase flow, proposing a new design thinking of the inner cone type fluidized bed which adding a cone in the inner of the common cylindrical fluidized bed, the cold experimental results show that the fluidization effect is better than the common cylindrical type fluidized bed. At the same time, as the complexity of fluidized state, to establish flow equations of the gas-solid two-phase flow, using FLUENT simulation software, adopting Euler model, the numerical simulation of particle motion state, concentration and speed has been done respectively for the inner cone type fluidized bed, also the comparison analysis of the simulation results of the ordinary cylinder and the inner cone type fluidized bed has been done.
Based on the inner cone type fluidized bed reactor, the system components mode has been build up, the system process analysis and the thermal equilibrium research and analysis on the system have also been done, from the economy view, the assumption that the production energy can be obtained by the by-products charcoal and non-condensable gas except for the electric driving, and through the effect of the conversion ratio on the by-product production rate, the optimal conversion rate under the self-heating conditions has been built, the theoretical guidance has been provided for the advanced design that the biofuels system does not depend on the outside heat but can achieve heating balance themselves.
According to the proposed assumptions that the system can realize self-heating and heating can be obtained only by the by-products charcoal and non-condensable gas for the whole system, also according to the principle of burning, the design theory research of the gas-solid mixing burning device has been carried out. In addition, in order to put the heat energy of smoke and fumes after burning into use in the fluidization dry process, the design theory research of the fluidization dry and transporting device according to the fluidization dry theory has been carried out.
The theoretical guidance and research reference based on the inner cone type fluidized bed reactor of self-heating pyrolysis biofuels system can be provided according to the above research and results. It is expected to provide the theoretical reference for the scale and industrialization of China's biofuels production.
引文
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