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生物质(秸秆)气合成甲醇工艺及动力学研究

Study on Kinetics and Technology of Biomass (Straw) Gas Methanol Synthesis

【作者】 朱灵峰

【导师】 张百良; 刘国际;

【作者基本信息】 河南农业大学 , 农业生物环境与能源工程, 2004, 博士

【摘要】 本研究是结合河南省科技厅科技攻关项目“低热值农业废弃物燃气催化合成甲醇技术研究”进行的。通过对“生物质合成甲醇技术研究进展”、“生物质(秸秆)热化学法制甲醇合成气试验”、“秸秆类生物质催化合成甲醇试验”、“秸秆合成气制甲醇工艺条件优化试验”、“秸秆合成气合成甲醇的动力学和热力学试验”等方面的系统研究,获得了一系列关于生物质(秸秆)气合成甲醇技术方面的相关数据和规律性认识,为我国秸秆类生物质合成甲醇技术领域的研究开发和应用进行了有益的探讨研究。主要研究成果如下: 1、查阅了国内外大量相关研究资料,对以下内容进行了系统详细的文献综合分析研究。①生物质气化技术研究概况;②生物质制甲醇技术工艺类型;③影响生物质制气技术的因素;④生物质制甲醇合成气的技术研究现状;⑤生物质合成甲醇催化剂的研究概况;⑥现有生物质气化催化制甲醇技术存在的问题。 2、研究了下吸式固定床气化炉生产的玉米秸秆低热值燃气的脱硫、除氧、分解焦油、净化、配氢等技术工艺,制备出合成甲醇的优质秸秆合成气。 3、以直流流动等温积分反应器为试验装置,使用国产C301铜基催化剂,在5MPa压力下对秸秆合成气催化合成甲醇技术进行试验研究,寻找影响CO转化率、CO2转化率、甲醇时空收率的重要因素,通过试验数据处理,找出了它们之间的规律。 4、对秸秆合成气催化合成甲醇技术工艺进行试验研究,对影响催化合成工艺技术参数如压力、温度、催化剂、催化剂粒度、合成气进口流量、河南农业大学博十学位论文秸秆合成气组成等进行逐一优化试验。优选出秸秆合成气生产甲醇的最佳技术工艺方案。为生物质(秸秆)气制甲醇中试研究提供了科学和实用的参考依据。 5、对秸秆合成气催化合成甲醇动力学特性进行试验研究。建立了L一H型本征动力学模型,优选出动力学模型参数,并对模型进行统计检验和方差分析,结果表明动力学模型高度显著,该模型方程反映了秸秆合成气合成甲醇体系的动力学变化规律。 6、应用SHBwR状态方程,研究了加压下秸秆合成气甲醇合成体系的总反应热、平衡常数及平衡体系组成。为生物质(秸秆)气合成甲醇的中试设备设计制造提供基础参数。 本文是以解决农业废弃物(玉米秸秆)高新转换技术难题为目的的研究论文,着力点放在基础研究上,因为国内利用秸秆作原料气合成甲醇方面的研究尚无报道,因此论文在试验方面只能借鉴以天然气、煤等为原料合成甲醇方面的研究成果,难免在方法上有不当之处,但研究取得的结果对秸秆合成气合成甲醇的技术中试和合成设备设计起到有效的指导作用。

【Abstract】 The research is linked with Henan Provincial Department of Science and Technology Research Project "Studies on Technologies of Methanol Synthesis from Fuel gas (Low Heat Value )of Agricultural Residues". Through the systematic study of "research progresses of biomass methanol synthesis technology", "tests of methanol syngas production from biomass (straw) by the thermochemical method ", "catalytic tests of methanol synthesis from straw biomass ", "technology optimum tests of methanol production from straw syngas ", "kinetic and thermodynamic characteristics tests of methanol synthesis from straw syngas ",data related to methanol synthesis technology of biomass (straw ) gas have been achieved, and the rules concluded. The major achievements are :1. After reading a large number of technical materials , the author made a comprehensive study on the following fields:(1) gasification technology of biomass; (2)technical processes of methanol production from biomass; (3)factors that have impact to biomass gasification process; (4)existing technology methanol syngas production from biomass and current situation of research; (5)catalyst research of biomass for methanol synthesis; (6)Problems occurred in existing gasifiable and catalytic technologies of biomass methanol.2. Purification technologies of cornstalk gas(low heat value) production in the down-flow fixed bed gasifer was experimented, focusing on the desulfurization, deoxy, catalytic cracking of tar, purification, hydrogenation etc. technical processes. Quality straw syngas was produced for methanol synthesis.3. The catalytic test of methanol synthesis for straw syngas over a domestic Cu-based catalyst C301 were carried out in a tubular-flow integral and isothermal reactor under pressure of 5MPa. Through changing some conditions of the synthetic reaction, the author has found the factors that influence CO and CO2 conversion and time space yield of CH3OH. By treatment of experimental data, the rules of the linkage among these factors was obtained.4. The catalytic techniques of methanol synthesis from straw syngas was experimented, focusing on the impact of pressure, temperature, catalyst, catalyst particle size, syngas flow at entering end, compositions of straw syngas on the technical parameters of synthesis, the optimum technology conditions of methanol production from straw syngas was obtained, thestudy provided the scientific and practical basis to the industrial test of methanol production from biomass (straw) gas.5. Dynamical characteristics of methanol synthesis from straw syngas was tested, It established L-H model of the intrinsic kinetics equations and the optimum parameters of the dynamic model equations. The results of statistical test and residue analysis of the model equations showed that the kinetic model equations were highly remarkable. These equations reflect the changing rules of kinetics which straw syngas synthesized methanol.6. Using SHBWR state equation, total reaction heat, equilibrium constants and compositions, which straw syngas synthesized methanol under pressure were researched. It provided basic parameters for design and manufacture of industrial test equipment, which straw syngas synthesized methanol.The paper is purposed on solving the technical problems occurred in high grade and new transforming technology of agricultural residues (cornstalk). The paper is focused on research of basic theories, because the lack of test reports of methanol synthesis used straw as feed gas, it can only refer to research results of methanol synthesis used natural gas coal and so forth as feed gas in experiments. It is unavoidable that experimental methods of this paper are not the best ones. The achievement, however, has provided effective guidance to the industrial test of straw methanol and synthesis equipment design.

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