秸秆纤维乙醇技术工程化及技术经济研究
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摘要
能源是可以为人类提供能量的自然资源,是人类赖以生存和社会赖以发展的物质基础。近年来随着世界低碳经济浪潮的到来,世界各国制定了可再生能源发展规划,并提供了专项资金推动可再生能源的技术研究和产业化发展。在生物质可再生能源研究开发体系中,纤维乙醇技术成为公众、政府和企业支持的商业载体,也是实现未来生物炼制发展的基础平台和重要途径。
维乙醇技术产业化是一个不断探索和优化的过程。目前虽然国内外在纤维乙醇领域研究不断取得新技术进步,并基于不同的技术工艺先后建立了近40多条中试生产线,还处于产业化发展的初级阶段,表明影响和制约产业化发展的关键技术需要亟待解决。
本课题基于秸秆纤维燃料乙醇工程试验研究,重点进行了纤维乙醇预处理关键技术、技术工程化实施及技术经济分析,并取得了阶段性的结论和成果。主要包括以下几个方面:
(1)在对现有国内外纤维中试生产生产线比较研究的基础上,基于蒸汽爆破与稀酸同线双效预处理生产线设计理念,并在此指导下完成了300t/a秸秆纤维燃料乙醇中试示范生产线初步的物料衡算和工艺流程,设备技术参数,并系统地完成了设备设计、加工、安装与调试,为工程试验研究提供基础平台。
(2)基于300t/a秸秆纤维乙醇工程试验线,进行了稀酸预处理工艺的试验。试验结果表明,糖化48h秸秆粉糖化率达到50.5%,发酵72h乙醇浓度到23.1g/L,乙醇回收率达到82.5%,与试验小试结果基本一致。
(3)基于BOX-Behnken design中心组合试验设计,利用响应面分析法建立了以还原总糖为响应值的工艺数学模型,并在此基础上进行了工艺优化,获得较高的还原总糖浓度。结果表明,维压时间t=227s、蒸汽压强p=3.08MPa和碳酸氢铵浓度C=2.11%,还原总糖浓度达到60.04g/L。结果表明,蒸汽爆破预处理技术工艺表明,糖化率达到53.5%,乙醇浓度到24.8g/L,乙醇回收率达到82.9%,蒸汽爆破预处理工程试验比稀酸预处理工艺较好的试验效果。运用热重分析(TGA)、X衍射分析(XRD)和扫描电镜(SED)方法综合研究了蒸汽爆破预处理对秸秆理化特性影响的研究,结果表明,蒸汽爆破预处理对玉米秸秆理化特性改变较为显著。
(5)研究了秸秆乙醇废渣利用的新途径,有利于提高秸秆乙醇废渣的经济附加值。防水材料原料中添加10～11%的秸秆纤维废渣,生产成本降低8～9%,且防水材料的不透水性提高8.1%,最大拉力时延伸率提高了0.92%。经人工气候老化后检测,拉力保持率比对照高3.5%。
(6)基于工程热力学方程分析了影响蒸汽能耗的因素,建立了秸秆纤维乙醇生产净能量分析模型,并分析了两种不同生产工艺的能量流动分布。结果表明,汽爆预处理生产系统总能耗与稀酸预处理工艺减少1027.7MJ/t,能投比提高了0.11,并进行两种技术工艺的成本估算,及影响乙醇成本的敏感性分析。结果表明,蒸汽爆破预处理生产成本略低于稀酸工艺,纤维素酶是实现纤维乙醇产业化发展的关键性因素。
Energy is a kind of natural resource which supply energy for humanbing, and it is the material foundation for human living and society developing. Following the low carbon economy wave in recently years, most countries established their developing plan for regenerable energy, and supply special fund to promote technology and industy development of regenerable energy. Biomass energy is the largyest regenerable energy source in the world,and in the research and exploitation system of biomass energy, fibre ethanol technology has became an important economy carrier supported by publication,governments and corporations, at the same time, it is the basic platform and important channel to realize biomass refine developing in future.
Cellulosic ethanol technology industry is an exploring and optimizing process Though there have gaining continuing technology developing in fibre ethanol research field, and about 40 middle pre-production trials have built on the base of different technologies in the world, fibre ethanol industry is still on the primary stage of industry production, the developing actualities of cellulosic ethanol shown that there are key technologyies which restrict fibre ethanol industry transforming need to be resolve now.
This task was based on the three phases of straw cellulosic fuel ethanol middle engineering test demonstration study, took the key technology of raw materials pretreament, production technic transform to engineering, and process economics study as main studing. Phasely conclusions and fruits for the study were given as follow:
(1)The design thought of two methods of steam explosion and dilute acid combined action to pretreat raw materials was drawn out after compared middle engineering tests operating in the world now, and then materials and supplies calculation of middle engineering tests with the capability of 300t straw every year was achieved, technical parameters of the main equipments were radicated, equipments design, machining,fixation and shakedown test were systematicly been done,the basic study base of the middle engineering tests was accomplishhed.
(2)with the pilot production demonstration line of 300t/a,the experiment and runing of two kinds of pretreatment technic to deal with corn straw were accomplished. The results of dilute acid pretreat experiment shown that saccharified ratio reached 50.5%,ethnol concentration reached 23.1g/L, and ethnol recovery reached 82.5%。
(3)with BOX-Behnken design, the technics mathematical model which took total saccharified ratio as respond was set up by answer side analytical method,and technics optimize simulation was accomplished by the model,better total deoxidize sugar dates gained by the experiment. The experiment dates shown that pretreatment corn straw by vapour blast at the condition of pressure maintain 227s,vapour pressure keep 3.08Mpa,and ammonium acid carbonate concentration keep 2.11%, the total deoxidize sugar concentration could reached 60.04g/L.
(4)Pretreatment corn straw by steam explosion could produce better effect than dilute acid.In the dates of the experiment pretreatment corn straw by vapour blast,saccharify got 53.5%,ethanol concentration got 24.8g/L,and ethanol recovery ratio got 82.9%. TGA, XRD and SED methods were integrated to study the physical and chemical characteristic of corn straw after vapour blast.the results shown that vapour blast pretreatment have depressed cellulose rime distinctnessly.
(5)The new useage of corn straw residue was explored. corn straw residue could be used as waterproof material, that could enhance additional profit of corn straw residue which had been used to produced ethnol fuel.Been added 10～11% corn straw residue, the producing cost of waterproof material could depressed 8～9%,and the water proof ability enhance 8.1%, the the extensibility under maximum pulling enhanced 0.92%,the pulling keep rate was 3.5% higer than comparison dates.
(6)The factors affect energy consume in the two pretreation methods were been emphatically analysed.thermodynamics equation of steam explosion process was built, and factors affect energy consume of vapour were analyzed.that could supply reference for the optimization and amplification of steam explosion equipment.the experiment results shown that the total energy consume of steam explosion was 1027.7MJ/t less than dilute technology.
维乙醇技术产业化是一个不断探索和优化的过程。目前虽然国内外在纤维乙醇领域研究不断取得新技术进步,并基于不同的技术工艺先后建立了近40多条中试生产线,还处于产业化发展的初级阶段,表明影响和制约产业化发展的关键技术需要亟待解决。
本课题基于秸秆纤维燃料乙醇工程试验研究,重点进行了纤维乙醇预处理关键技术、技术工程化实施及技术经济分析,并取得了阶段性的结论和成果。主要包括以下几个方面:
(1)在对现有国内外纤维中试生产生产线比较研究的基础上,基于蒸汽爆破与稀酸同线双效预处理生产线设计理念,并在此指导下完成了300t/a秸秆纤维燃料乙醇中试示范生产线初步的物料衡算和工艺流程,设备技术参数,并系统地完成了设备设计、加工、安装与调试,为工程试验研究提供基础平台。
(2)基于300t/a秸秆纤维乙醇工程试验线,进行了稀酸预处理工艺的试验。试验结果表明,糖化48h秸秆粉糖化率达到50.5%,发酵72h乙醇浓度到23.1g/L,乙醇回收率达到82.5%,与试验小试结果基本一致。
(3)基于BOX-Behnken design中心组合试验设计,利用响应面分析法建立了以还原总糖为响应值的工艺数学模型,并在此基础上进行了工艺优化,获得较高的还原总糖浓度。结果表明,维压时间t=227s、蒸汽压强p=3.08MPa和碳酸氢铵浓度C=2.11%,还原总糖浓度达到60.04g/L。结果表明,蒸汽爆破预处理技术工艺表明,糖化率达到53.5%,乙醇浓度到24.8g/L,乙醇回收率达到82.9%,蒸汽爆破预处理工程试验比稀酸预处理工艺较好的试验效果。运用热重分析(TGA)、X衍射分析(XRD)和扫描电镜(SED)方法综合研究了蒸汽爆破预处理对秸秆理化特性影响的研究,结果表明,蒸汽爆破预处理对玉米秸秆理化特性改变较为显著。
(5)研究了秸秆乙醇废渣利用的新途径,有利于提高秸秆乙醇废渣的经济附加值。防水材料原料中添加10～11%的秸秆纤维废渣,生产成本降低8～9%,且防水材料的不透水性提高8.1%,最大拉力时延伸率提高了0.92%。经人工气候老化后检测,拉力保持率比对照高3.5%。
(6)基于工程热力学方程分析了影响蒸汽能耗的因素,建立了秸秆纤维乙醇生产净能量分析模型,并分析了两种不同生产工艺的能量流动分布。结果表明,汽爆预处理生产系统总能耗与稀酸预处理工艺减少1027.7MJ/t,能投比提高了0.11,并进行两种技术工艺的成本估算,及影响乙醇成本的敏感性分析。结果表明,蒸汽爆破预处理生产成本略低于稀酸工艺,纤维素酶是实现纤维乙醇产业化发展的关键性因素。
Energy is a kind of natural resource which supply energy for humanbing, and it is the material foundation for human living and society developing. Following the low carbon economy wave in recently years, most countries established their developing plan for regenerable energy, and supply special fund to promote technology and industy development of regenerable energy. Biomass energy is the largyest regenerable energy source in the world,and in the research and exploitation system of biomass energy, fibre ethanol technology has became an important economy carrier supported by publication,governments and corporations, at the same time, it is the basic platform and important channel to realize biomass refine developing in future.
Cellulosic ethanol technology industry is an exploring and optimizing process Though there have gaining continuing technology developing in fibre ethanol research field, and about 40 middle pre-production trials have built on the base of different technologies in the world, fibre ethanol industry is still on the primary stage of industry production, the developing actualities of cellulosic ethanol shown that there are key technologyies which restrict fibre ethanol industry transforming need to be resolve now.
This task was based on the three phases of straw cellulosic fuel ethanol middle engineering test demonstration study, took the key technology of raw materials pretreament, production technic transform to engineering, and process economics study as main studing. Phasely conclusions and fruits for the study were given as follow:
(1)The design thought of two methods of steam explosion and dilute acid combined action to pretreat raw materials was drawn out after compared middle engineering tests operating in the world now, and then materials and supplies calculation of middle engineering tests with the capability of 300t straw every year was achieved, technical parameters of the main equipments were radicated, equipments design, machining,fixation and shakedown test were systematicly been done,the basic study base of the middle engineering tests was accomplishhed.
(2)with the pilot production demonstration line of 300t/a,the experiment and runing of two kinds of pretreatment technic to deal with corn straw were accomplished. The results of dilute acid pretreat experiment shown that saccharified ratio reached 50.5%,ethnol concentration reached 23.1g/L, and ethnol recovery reached 82.5%。
(3)with BOX-Behnken design, the technics mathematical model which took total saccharified ratio as respond was set up by answer side analytical method,and technics optimize simulation was accomplished by the model,better total deoxidize sugar dates gained by the experiment. The experiment dates shown that pretreatment corn straw by vapour blast at the condition of pressure maintain 227s,vapour pressure keep 3.08Mpa,and ammonium acid carbonate concentration keep 2.11%, the total deoxidize sugar concentration could reached 60.04g/L.
(4)Pretreatment corn straw by steam explosion could produce better effect than dilute acid.In the dates of the experiment pretreatment corn straw by vapour blast,saccharify got 53.5%,ethanol concentration got 24.8g/L,and ethanol recovery ratio got 82.9%. TGA, XRD and SED methods were integrated to study the physical and chemical characteristic of corn straw after vapour blast.the results shown that vapour blast pretreatment have depressed cellulose rime distinctnessly.
(5)The new useage of corn straw residue was explored. corn straw residue could be used as waterproof material, that could enhance additional profit of corn straw residue which had been used to produced ethnol fuel.Been added 10～11% corn straw residue, the producing cost of waterproof material could depressed 8～9%,and the water proof ability enhance 8.1%, the the extensibility under maximum pulling enhanced 0.92%,the pulling keep rate was 3.5% higer than comparison dates.
(6)The factors affect energy consume in the two pretreation methods were been emphatically analysed.thermodynamics equation of steam explosion process was built, and factors affect energy consume of vapour were analyzed.that could supply reference for the optimization and amplification of steam explosion equipment.the experiment results shown that the total energy consume of steam explosion was 1027.7MJ/t less than dilute technology.
引文
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