木质原料快速热解制取生物油及生物油分级催化提质研究
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摘要
随着经济社会的迅速发展，作为发展的源动力——化石能源日趋枯竭，特别是石油资源供应问题更为突出；同时化石燃油带来严峻的环境问题。能源与环境叠加效应推动可再生能源的要求。生物质能作为唯一可代替液体燃料的可再生能源，受到世界各国政府和科学家们的重视，并有望成为未来替代汽车燃料的重要来源。
生物基液体燃料来源丰富，但是品质差，难以满足车用需求。生物油品高效精制技术是有效应对措施之一。生物质快速热解技术是获得生物油品的主要途径。与秸秆生物油相比，木质生物油的热值高、灰分低、分布相对集中、更易于规模化利用，但具有酸性高且产物成分复杂特点，不能直接用作汽车燃料。本文创新性地提出生物油分级精制方法，集成了络合萃取、分级催化重整的过程。该方法既克服了简单蒸馏的变质问题又提高了油品热值。
基于快速热解技术，本论文主要研究木材原料的热解行为，并优化其热解参数，分析了主要热解产物分布，实现优化和控制热解过程的目标，为工业化和产业化提供应用方案和技术支持。
对于快速热解制取的生物油品，论文以实验研究为手段，设计了快速裂解装置及分级催化提质的方法，运用气相色谱质谱联用仪（GC-MS）、热重分析仪（TG-MS、TG-DSC和TG-FTIR）等现代分析仪器对木质原料热解、木质生物油燃烧动力学及燃烧产物成分进行了分析，并通过理论分析初步揭示了木质原料的热解机理与木质生物油的燃烧机理。
论文的主要研究结果或结论如下：(1)建立了木质原料的热解动力学经验模型和生物油的燃烧动力学经验模型；(2)分析了木质原料快速热解反应液体产物，其主要为C6~14的醇类、酯类、酮类和醚类等物质；(3)实验研究了络合萃取对生物油的脱酸效果，并建立了萃取分子动力学模型；(4)论文对生物油进行了分级催化提质。
With the development of economy, fossil energy sourse as development’s impetusdried up daily, in particular, petroleum absence stare us in the face. Superimposedeffect of energy and environment promoted human being’s latency era desire onrenewable energy. As only renewable energy of commutable liquid fuel, bioenergy getmore and more recognition daily by world governments and scientists, and it will bean important source for instead of auto fuel.
Stable supply of high quality oil has been confronted with challenge badly. Oneof good solution is bio-oil upgrading into automobile fuel. Biomass fast pyrolysisprocess is a major approach for obtaining bio-oil. Compared with stalk based bio-oil,wood based bio-oil has many advantages, such as higher heat value, lower ash, easilerscaleup due to relatively centralized distribution of feedstock. However, high pHvalue and complex components of such bio-oil make it impossible to be used astransport fuel directly. In this paper, we put forward an innovative bio-oil upgradingmethod which integrated with several process, such as complexation extraction andclassification catalytic reforming. This method may overcome metamorphosed directdistillation, but also increase heating value.
For optimized and controlled fast pyrolysis process, the dissertation mainlystudied on wood based material pyrolysis action, optimized pyrolysis parameter,pyrolysis production anlysis. It can provide technical support for commercializationand industrial applications.
The fast pyrolysis experimental device was designed and constructed, and stagingcatalytic reforming method was proposed. The modern analytical instruments such asgas chromatography and mass spectrometry (GC-MS), thermogravimetricanalyzer(TG-MS、 TG-DSC and TG-FTIR) were used for product compositionanalysis.
The results and conclusions in this dissertation are drawn as follow:(1) anempirical model for wood pyrolysis kinetics and a bio-oil combustion kineticsestablished;(2) illustration of pyrolysis reaction products, mainly C6~14alcohols,esters, ketones and ethers, and other substances;(3) Experimental study of woodenbio-oil deacidification by complexation extraction and its kinetics empirical modelpeformed;(4) The study of staging catalytic reforming of bio-oil and bio-oil as auto fuel guideline made.
生物基液体燃料来源丰富，但是品质差，难以满足车用需求。生物油品高效精制技术是有效应对措施之一。生物质快速热解技术是获得生物油品的主要途径。与秸秆生物油相比，木质生物油的热值高、灰分低、分布相对集中、更易于规模化利用，但具有酸性高且产物成分复杂特点，不能直接用作汽车燃料。本文创新性地提出生物油分级精制方法，集成了络合萃取、分级催化重整的过程。该方法既克服了简单蒸馏的变质问题又提高了油品热值。
基于快速热解技术，本论文主要研究木材原料的热解行为，并优化其热解参数，分析了主要热解产物分布，实现优化和控制热解过程的目标，为工业化和产业化提供应用方案和技术支持。
对于快速热解制取的生物油品，论文以实验研究为手段，设计了快速裂解装置及分级催化提质的方法，运用气相色谱质谱联用仪（GC-MS）、热重分析仪（TG-MS、TG-DSC和TG-FTIR）等现代分析仪器对木质原料热解、木质生物油燃烧动力学及燃烧产物成分进行了分析，并通过理论分析初步揭示了木质原料的热解机理与木质生物油的燃烧机理。
论文的主要研究结果或结论如下：(1)建立了木质原料的热解动力学经验模型和生物油的燃烧动力学经验模型；(2)分析了木质原料快速热解反应液体产物，其主要为C6~14的醇类、酯类、酮类和醚类等物质；(3)实验研究了络合萃取对生物油的脱酸效果，并建立了萃取分子动力学模型；(4)论文对生物油进行了分级催化提质。
With the development of economy, fossil energy sourse as development’s impetusdried up daily, in particular, petroleum absence stare us in the face. Superimposedeffect of energy and environment promoted human being’s latency era desire onrenewable energy. As only renewable energy of commutable liquid fuel, bioenergy getmore and more recognition daily by world governments and scientists, and it will bean important source for instead of auto fuel.
Stable supply of high quality oil has been confronted with challenge badly. Oneof good solution is bio-oil upgrading into automobile fuel. Biomass fast pyrolysisprocess is a major approach for obtaining bio-oil. Compared with stalk based bio-oil,wood based bio-oil has many advantages, such as higher heat value, lower ash, easilerscaleup due to relatively centralized distribution of feedstock. However, high pHvalue and complex components of such bio-oil make it impossible to be used astransport fuel directly. In this paper, we put forward an innovative bio-oil upgradingmethod which integrated with several process, such as complexation extraction andclassification catalytic reforming. This method may overcome metamorphosed directdistillation, but also increase heating value.
For optimized and controlled fast pyrolysis process, the dissertation mainlystudied on wood based material pyrolysis action, optimized pyrolysis parameter,pyrolysis production anlysis. It can provide technical support for commercializationand industrial applications.
The fast pyrolysis experimental device was designed and constructed, and stagingcatalytic reforming method was proposed. The modern analytical instruments such asgas chromatography and mass spectrometry (GC-MS), thermogravimetricanalyzer(TG-MS、 TG-DSC and TG-FTIR) were used for product compositionanalysis.
The results and conclusions in this dissertation are drawn as follow:(1) anempirical model for wood pyrolysis kinetics and a bio-oil combustion kineticsestablished;(2) illustration of pyrolysis reaction products, mainly C6~14alcohols,esters, ketones and ethers, and other substances;(3) Experimental study of woodenbio-oil deacidification by complexation extraction and its kinetics empirical modelpeformed;(4) The study of staging catalytic reforming of bio-oil and bio-oil as auto fuel guideline made.
引文
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