文献类型：期刊文献

中文题名：酸性离子液体催化麦秸液化及其产物分析

英文题名：Liquefaction of wheat straw catalyzed by acidic ionic liquid and analysis of liquefied products

作者：关倩[1] 蒋剑春[1,2] 徐俊明[1,2] 王奎[1] 冯君锋[1]

第一作者：关倩

通信作者：Jiang, Jianchun

机构：[1]中国林业科学研究院林产化学工业研究所,生物质化学利用国家工程实验室,国家林业局林产化学工程重点开发实验室,江苏省生物质能源与材料重点实验室,南京210042;[2]江苏强林生物能源材料有限公司,溧阳213364

年份：2016

卷号：32

期号：12

起止页码：206-211

中文期刊名：农业工程学报

外文期刊名：Transactions of the Chinese Society of Agricultural Engineering

收录：CSTPCD;;EI(收录号：20162602533020);Scopus(收录号：2-s2.0-84975128623);北大核心:【北大核心2014】；CSCD:【CSCD2015_2016】；

基金：木质纤维原位加氢液化与精炼过程机制研究(CAFYBB2014ZD003)

语种：中文

中文关键词：秸秆;催化;液化;离子液体;乙酰丙酸乙酯

外文关键词：straw; catalysis; liquefaction; ionic liquid; ethyl levulinate

分类号：TQ35

摘要：为降低有机酸催化剂对设备的腐蚀,提高秸秆类生物质原料的利用率,该文以合成的1-甲基-3-(4-磺酸基丁基)咪唑硫酸氢盐离子液体为催化剂,乙醇为溶剂,考察小麦秸秆的液化过程,并对离子液体的结构进行傅里叶红外光谱和核磁共振表征,对液化后的残渣和液相产物进行傅里叶红外光谱、热重和气质联用分析。试验和表征结果表明:合成的1-甲基-3-(4-磺酸基丁基)咪唑硫酸氢盐离子液体对秸秆液化具有较优的催化性能,在反应温度为200℃、反应时间为60 min、离子液体用量为26%的条件下,液化率可达85.5%,同时乙酰丙酸乙酯的得率为9.97%,在液化产物中的相对百分含量为29.9%;液化产物中包含有醛、酮、酯、酸和酚类等含氧化合物,其中酚类化合物主要源于木质素的降解,其他化合物则主要源于半纤维素和纤维素的降解。研究结果为开发利用低腐蚀性环保型催化剂催化液化秸秆制备高品位化学品提供理论依据。
With the increasing energy requirements and pollution problems worldwide, energy from renewable resources has received global attention in recent decades. Biomass is one of the most abundant renewable resources. It mainly includes forest residues, agricultural wastes, industrial residues, municipal solid wastes, bagasse, aquatic plants, and algae animal wastes. Due to the advantages of abundance, non-polluting, being renewable and easy to obtain, biomass is considered as the most promising energy feedstock to replace the traditional energy. Meanwhile, it is the only resource that can be converted into solid, liquid, and gaseous products for use of fuels. Thermo-chemical conversion is an effective technology of biomass conversion. Liquefaction is the typical thermo-chemical technology for the conversion of biomass to obtain liquid biofuels and valuable chemicals, such as bio-oil and fuel additives. The conversion process is not only influenced by organic reagents but also by different catalysts. Effective catalyst is an essential factor to improve liquefaction efficiency. As catalyst, sulfuric acid has very strong corrosion and needs high-quality liquefaction equipment, and its recycling is difficult. Solid acid is used to overcome shortcomings of organic acid in the liquefaction, but it is easy to form coke to cause the deactivation of catalyst, and needs to be calcined before re-use, which increases the reaction cost. Now, it is found that the ionic liquid has non-corrosiveness, low melting point, high thermal stability and low vapor pressure, and some other merits. It has a broad application prospect used as solvents and catalysts in catalytic reactions. Ionic liquid, especially sulfonated bisulfate ionic liquid can dissolve cellulose, because it has higher acidic sites that can easily break the hydrogen bonds of biomass material, and promote the degradation and conversion of cellulose. At present, ionic liquid is usually used to catalyze carbohydrate, which is changed into 5-hydroxymethylfurfural（HMF）. The report about producing levulinate from agriculture waste catalyzed by ionic liquids is rare. Therefore, we choose wheat straw as raw material and ionic liquids as catalyst in the liquefaction process. In this study, 1-methyl-3-（4-Sulfobutyl）-imidazolium hydrosulfate is synthesized and used as catalyst for the liquefaction of wheat straw in ethanol. Fourier transform infrared spectrometer（FT-IR）, nuclear magnetic resonance carbon-13 spectrum（13C NMR）, thermo gravimetric analyzer（TG） and gas chromatography-mass spectrometry（GC-MS） characterized the structure of ionic liquid and liquid products. The synthesized ionic liquid is confirmed to be 1-methyl-3-（4-Sulfobutyl）-imidazolium hydrosulfate. Results of the experiments show that the ionic liquid has the optimum catalytic properties for the liquefaction of wheat straw. Under the conditions that wheat the straw mass is 5 g, the mass fraction of catalyst is 26%, the reaction temperature is 200 ℃, and the reaction time is 60 min, a high conversion rate of 85.5% is obtained; under the conditions, the yield of ethyl levulinate is 9.97%, and the relative percentage content of ethyl levulinate is 29.9% in liquid products. The liquid products include aldehydes, ketones, esters, carboxylic acids, phenols and other oxygenated chemicals; among them, phenols are from the degradation of lignin mainly, and the other compounds are from the degradation of hemicellulose and cellulose principally. The results can provide theoretical basis for the development and utilization of low corrosive and environment-friendly catalysts, which will be used on liquefaction to prepare high grade chemicals.