PDF《生物质水相催化合成生物汽油和航空燃油》

Guangzhou Institute of Energy Conversion, CAS 生物质水相催化合成生物汽油和航空燃油 Biogasoline and jet fuel production from biomass by aqueous phase catalytic processing 中国科学院广州能源研究所 Guangzhou Institute of Energy Conversion, CAS 2012-07-07 北京 Longlong Ma E-mail: mall@ms.

giec.ac.cn Guangzhou Institute of Energy Conversion, CAS Contents

2 技术路线 技术路线 Content and technical routes Content and technical routes

3 关键技术与工艺 Key Technology and Process 研究背景 研究背景 Research Background Research Background

1 结论 Conclusions

4 Guangzhou Institute of Energy Conversion, CAS 生物质能是一种重要的石油补充能源 Biomass,a potential substitute for petroleum 碳活性高 双向清洁 新农村发展发展生物质能 的优势 Advantages 资源 丰富 农业秸秆6.5亿吨 6.5 billion tons of Straw 林业废弃物2.7亿吨 2.7 billion tons of Forestry residues 40%能源利用 Utilization of 40%energy 替代4000万吨石油 Replacing oil of

40 million tons 年减排CO2达1.5亿吨 Reducing CO2 emissions by 1.5 billion tons 实现5.5%的减排目标 Achieving the emission reduction target of 5.5% 现有资源 Current resources 发展潜力 Potential resources 生物质能是唯一可制备液体燃料的可再生能源 Biomass is the only renewable energy source for liquid fuel synthesis 碳循环、工艺清洁无污染 Carbon recycling and clean 1. 1. 研究背景 研究背景 Background Background A b u n d a n t New rural developm ent High activity Cleaning Guangzhou Institute of Energy Conversion, CAS Biomass liquid fuel production process Ethanol Butanol ???? Distillation Sugars Hydrolysis Starchy materials Lignocelluloses Thermo-chemical conversion ? Heat、Electricity ? Fuels、Chemicals Pretreat ment Lignocell uloses Ferment ation Carbohy drate Hydrolysis/ saccharification Starchy materials Sugars Aqueous Phase Processing C5-C8 alkanes (Gasoline) C8-C15 alkanes (Jet Fuel) Guangzhou Institute of Energy Conversion, CAS 液体烷烃 (汽油、航空燃油) Liquid alkanes (Biogasoline and jet fuel) 木质纤维素 Lignocellulose 水解 糖Sugar 水相催化 以木质纤维素类生物质为原料经高效水解、水解液催化合成生物汽油和航空燃油具有明显的 技术优势 Technology advantages of biogasoline and jet fuel by catalytic processing from lignocellulosic biomass 实现全糖利用 Full Utilization of Sugar 可实现水解液中单糖及低聚糖的全 利用,克服了传统纤维素乙醇生产 过程中五碳糖难以被有效发酵利用 的问题 Complete utilizing monosaccharide and oligosaccharides in the hydrolyzate (even pentose ) 能量转化效率更高 Higher Efficient Energy Conversion 产物液体烷烃保存了水解糖80%以上的 能量,反应均在液相中进行,避免了原 料的汽化;

反应产物烷烃可以与水相自 动分离,避免了蒸馏等耗能过程,该过 程的热效率大约是燃料乙醇的2倍. Saving more than 80% of the hydrolysis- sugar energy in liquid phase Avoiding the energy-consuming process (such as distillation) because of products automatic separation 反应效率更高 Higher Reaction Efficiency 水相催化采用多相催化材料, 反应速度快,生产强度高. Heterogeneous catalysis for APR Faster reaction rate Higher production aqueous-phase catalytic processing Hydrolysis Biomass liquid fuel production process Guangzhou Institute of Energy Conversion, CAS Lignocellulose Pentose,Hexose and residues Enzyme Hydrolysis Hydrolysis Pentose,Hexose Hydrolyzate HMF and Furfural Water-soluble intermediates Dehydration,hydrogenation and isomerization Cellulose +lignin C8-C15 Alkanes (Jet Fuel) Hydrolyzate- pentose H2O Steam Condensation Phase Separation Steam reforming for hydrogen H2 Dehydration Alkanes, H2O residues C5-C8 Alkanes (Gasoline) Phase Separation Hydrogenation Polyols Aqueous phase catalytic processing H2O 2. 2.技术路线 技术路线 Technical Routes Technical Routes Isomerization Guangzhou Institute of Energy Conversion, CAS 半纤维素-纤维素分级解聚:能耗低、功能单体收率高、选择性高 Depolymerization: low energy consumption, high sugar monomer yield and high selectivity 纤维素 半纤维素 Cellulose, hemicellu lose HCl 水解 Hydrol ysis H2SO4 糖衍生物 Sugar derivatives 中和 Neutralization CaO + C a S O

4 高温液态水、超低酸-酶水解、酸-酸耦合水解 High temperature liquid water, ultra low acid and enzyme hydrolysis, bi- acid coupled hydrolysis 生物质高效水解工艺研究 Biomass hydrolysis technology 生物质高效水解系统 Biomass efficient hydrolysis system 3. 3.关键技术与工艺 关键技术与工艺 Key Technology and Process Guangzhou Institute of Energy Conversion, CAS 纤维素 Cellulose 半纤维素 Hemicellulose 结晶度、结构 Crystallinity , structure 聚合度、形态 Polymerization, shape 生物质大分子 biomass 生物质酸-酸水解 Bi-acid coupled hydrolysis 酸浓度、温度、液固比 、渗滤速度 Acid concentration, temperature, ratio of liquid/solid, and infiltration speed 水解工艺 Hydrolysis process 金属盐助催化 Metal salt auxiliaries 辅助工艺 Aided process 技术难点 Technical difficulties ? 有效的预处理水解技术 Efficient pretreatment ? 水解反应器的设计 Hydrolysis reactor design 3. 3.关键技术与工艺 关键技术与工艺 Key Technology and Process 糖类衍生物 sugars Guangzhou Institute of Energy Conversion, CAS

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80 100 0.25 0.5 纤维素保 留率率% 酸预 处理温度(℃) 半纤维素水解工艺研究 Hemicellulose hydrolysis 水解优化工艺:0.25%硫酸、温度170℃、液固比10:

1、渗滤速度150ml/min 木糖浓度:21 g/l Optimized hydrolysis process: 0.25% of sulfuric acid concentration,

170 ℃, 10:1 of liquid to solid ration,150 ml/min of infiltration speed Xylose concentration:

21 g/l Guangzhou Institute of Energy Conversion, CAS 纤维素酸酶水解工艺研究 Acid-enzyme cellulose hydrolysis

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60 65 170℃ 190℃ 180℃ 还原糖浓度(g/L ) 酸预处理温度 葡萄糖浓度 木糖浓度 160℃ 纤维素水解优化工艺:硫酸浓度为0.25%;

酶水解温度为50℃;

处理时间60h;

葡萄糖浓度: 40.5 g/l. Optimized hydrolysis process: 0.25% of sulfuric acid concentration,

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60 h of treating time. glucose concentration: 40.5 g/l. 可溶-不可溶互变载体 纤维素固定化酶 Soluble-insoluble support Cellulose immobilized enzyme Guangzhou Institute of Energy Conversion, CAS 金属盐助催化预处理工艺研究 Metal salts catalyzed pretreatment process

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