木质素液化研究进展

介绍了木质素的液化、液化产物的改良的方法及其研究进展,对将来研究发展方向以及目前面临的一些问题作了简要的叙述。     

木质素加氢液化研究

在高压釜内,研究了温度、反应时间、初始氢压和搅拌速率对木质素加氢液化反应的影响。结果表明,木质素加氢液化的最佳工艺条件为:温度300℃,反应时间60 min,氢压3 MPa,搅拌速率800 r/min。在此条件下,木质素转化率与液体产率分别为71.3%与66.8%。     

木质素液化技术研究进展

综述了近期国内外木质素液化技术的研究状况;主要介绍了木质素的高温热解液化、催化加氢液化、共液化和超临界液化技术的发展.对木质素液化机理、液化产物的分析方法和应用研究作了概述.     

农作物秸秆快速热解液化与超临界醇解方法分析对比

农作物秸秆是生物质能源的重要组成部分,其开发和利用备受关注。对采用快速热解液化和超临界醇解两种技术降解农作物秸秆进行阐述,并对这两种技术做了比较。结果表明:较于快速热解液化,超临界醇解反应条件温和,一次反应所得产物含有长链脂肪酸甲酯和大量的酚类及其衍生物,可通过分离提取用于生产高品质的生物柴油和化学品。     

磁性复合氧化物催化剂的制备及其催化木质素液化性能

为了解决催化剂的回收再利用以及能减少回收利用过程中酸碱的使用问题,采用改进后的共沉淀法制备具有磁性的催化剂前体Fe3O4@Cu Mn Al-LDH,在不同温度下焙烧获得磁性复合金属氧化物催化剂Fe3O4@Cu O/Mn O/Al2O3,并用于超临界甲醇中木质素的催化液化。利用X射线衍射仪(XRD)和扫描电镜(SEM)对催化剂前体进行分析,结果表明制备出的催化剂前体具有良好的结构特征。通过热重(TG)、程序升温还原(H2-TPR)、氮气吸附脱附(BET)等手段研究了不同焙烧温度对催化剂的物化性质、物相结构的影响。在反应温度340℃,反应时间120 min的条件下,研究了催化剂的催化性能。结果表明,在450℃下焙烧时,催化剂具有优异的催化活性和稳定性,而且其磁学性能与焙烧前相比表现仍然相当优异。     

木材的超临界气化和液化与木本生物质能源转化

木材是生物质能源的主体,开发木质(生物质)能源也是我国木材工业一个重要内容。木材的超临界流体气化和液化是大规模利用木质生物能的有效途径,具有良好的经济前景和环保优势。介绍木材的超临界流体气化和液化的基本原理和研究进展,应用木材超临界热解和气化制氢,对生物质能源的开发和森林资源的高效利用具有重要意义。     

加压或超临界溶剂对乙醇发酵和在线萃取分离的影响

压缩或超临界流体作为良好的萃取溶剂,在食品加工与保藏、制药和生物材料加工等领域有广阔的应用前景。在简要论述了压缩或超临界流体对微生物存活与催化活性影响的基础上,详细综述了近年来采用超临界溶剂进行乙醇发酵与在线萃取分离过程取得的新进展,特别是装置结构设计和过程优化方面的新成果。最后探讨了实现过程规模化需要深入开展的关键性问题。     

超临界溶剂中溶质的扩散系数关联

1引言扩散系数是重要的化工基础数据,由于测定较困难,它的预测就显得很重要。近几年这方面的研究热点之一是预测溶质在超临界溶剂中的扩散系数“－’‘。作者最近以roush－hard－sPhere扩散理论为基础,结合大量文献数据,提出了一种预测溶质在超临界溶剂中扩散系数的方法,其形式如下「‘’：用上述方法曾对107个溶质一溶剂系统（共1167数据点）的扩散系数作了预测,平均相对偏差约7．5％,精度较高［’‘。但它不适用于CO。一醒系统（现有的文献预测方法中均存在着这个问题）。此外,当溶质含卤原子较多时,误差也较大。本文的目的是…     

高沸醇溶剂法制备松木纸浆和木质素

高沸醇溶剂(HBS)法是一种适用于从木材、草木秸秆类原料制备纤维素与木质素,且具有节能、环保等众多优点的好方法。采用1,4-丁二醇水溶液为溶剂的高沸醇溶剂法,在200~220℃、浓度为76.3%~85.2%的条件下,添加少量催化剂对松木进行蒸煮1~3 h,制备得到纤维素与木质素。分析结果表明,HBS木质素的活性保持较好,适当改性后可应用于多种行业,而纤维素仍可应用于造纸生产。回收的高沸醇溶剂可作为制浆溶剂循环使用。     

亚/超临界乙醇条件下杨木屑与甘油共液化研究

以60～80目的杨木屑为原料,甘油为液化剂,酸为催化剂,基于超临界乙醇条件下对杨木屑进行液化制备生物重油。实验结果表明:以2.5%硫酸为催化剂,在甘油/乙醇/木屑质量比为5∶10∶2条件下,250℃反应1 h,木屑的转化率可达98%。此液化油含水量为3.04%(wt),运动黏度为524 mm2/s,酸值为2.1 mg KOH/g,羟值为846 mg KOH/g。对液化油进行IR、GPC和GC-MS分析的结果显示,液化油含有大量的羟基物质,平均相对分子质量为811,并且含有4-羰基戊酸丁酯、三乙基甘油醚等聚酯/聚醚类多元醇。     

Thermochemical liquefaction characteristics of microalgae in sub- and supercritical ethanol

Thermochemical liquefaction characteristics of Spirulina, a kind of high-protein microalgae, were investigated with the sub- and supercritical ethanol as solvent in a 1000 mL autoclave. The influences of various liquefaction parameters on the yields of products (bio-oil and residue) from the liquefaction of Spirulina were studied, such as the reaction temperature (T), the S/L ratio (R₁, solid: Spirulina, liquid: ethanol), the solvent filling ratio (R₂) and the type and dosage of catalyst. Without catalyst, the bio-oil yields were in the range of 35.4 wt.% and 45.3 wt.% depending on the changes of T, R₁ and R₂. And the bio-oil yields increased generally with increasing T and R₂, while the bio-oil yields reduced with increasing R₁. The FeS catalyst was certified to be an ideal catalyst for the liquefaction of Spirulina microalgae for its advantages on promoting bio-oil production and suppressing the formation of residue. The optimal dosage of catalyst (FeS) was ranging from 5-7 wt.%. The elemental analyses and FT-IR and GC-MS measurements for the bio-oils revealed that the liquid products have much higher heating values than the crude Spirulina sample and fatty acid ethyl ester compounds were dominant in the bio-oils, irrespective of whether catalyst was used.     

Ball milling promoted direct liquefaction of lignocellulosic biomass in supercritical ethanol

In the present work, ball milling was applied for the pretreatment of lignocellulose to obtain high conversion and bio-oil yield in supercritical ethanol. Ball milling substantially decreased the crystallinity and particle size of lignocellulose, thereby improving its accessibility in ethanol solvent. An increased bio-oil yield of 59.2% was obtained for the ball milled camphorwood sawdust at 300°C, compared with 39.6% for the original lignocellulose. Decreased crystallinity significantly benefited the conversion of the cellulose component from 60.8% to 91.7%, and decreased particle size was beneficial for the conversion of all components. The obtained bio-oil had a high phenolic content, as analyzed by gas chromatography-mass spectrometry. Methoxylation and retro-aldol condensation were observed during alcoholysis, and the reaction pathways of lignocellulose in supercritical ethanol were attributed to the action of free radicals.     

秸秆纤维素在亚/超临界乙醇中液化反应路径及5集总反应动力学模型的建立

将玉米秸秆纤维素在亚/超临界乙醇中液化反应产物划分为残渣(RE)、轻油(WSO)、重油(HO)、挥发分(VO)和气体(GAS)5个集总。根据液化过程及其产物分布,建立集总反应路径,并以此建立了5集总反应网络。对反应网络建立了动力学模型,采用遗传算法结合非线性规划的求解策略简化和优化动力学模型,求取了动力学参数包括指前因子(A)、活化能(E_a)和反应级数(n),并用所建立的动力学模型对液化过程进行了模拟计算,模拟结果表明WSO和VO收率随停留时间增加而减少,而HO和GAS则随停留时间增加而增加,这一规律与实验数据变化一致。以实验数据对动力学模型进行验证,各集总模拟计算值与实验值相关系数在0.9345～0.9995之间,吻合较好,表明所建立的动力学模型是可信的,所采取的遗传算法结合非线性规划求解策略是可行的。     

Relationships between hydrogen donor abilities and chemical structure of aromatic compounds in terms of coal liquefaction

To obtain fundamental information about hydrogen transfer, the relationships between hydrogen donor ability and chemical structure of model compounds representing donor solvents is studied using gas chromatography,¹H n.m.r. and computing calculation methods. The order of the model compounds in terms of the ability as donor solvent to release hydrogen is: decalin < tetralin < 1,2-dihydronaphthalene < < 1,4-dihydronaphthalene. This trend closely correlates with the difference in binding energies of the hydroaromatic compounds and their radicals, determined by intermediate neglect of differential overlap (INDO) calculation. Electron spin resonance spectroscopy (e.s.r.) confirms that radical species are created after heat-treatment of the donor compounds. The ability of model compounds representing coal to accept hydrogen is assessed from a comparison of the¹H n.m.r. spectra. It is established that donor and acceptor efficacies are dependent upon chemical structure.     

煤直接液化研究评述

比较了中国与国际基础研究水平的差距,对主要的新老工艺进行了分类和比较,发现成功的液化工艺都符合煤分子结构的特点。高温快速液化是一种基于煤分子结构特殊性的直接液化方案,在理论上提供了实现最高液化效率和最低液化成本的可能性,联产芳香族化合物和燃料油,开辟了一个新的研究方向。     

Synergistic effects between light and heavy solvent components during coal liquefaction

As part of research to examine coal conversion in solvents containing high-boiling-point components, experimental studies were carried out with model compound solvents. The dissolution of bituminous and subbituminous coals was investigated in pyrene-tetralin and 2-methylnaphthalene-tetralin mixtures. The effects of donor level, gas atmosphere, hydrogen pressure and conversion temperature were determined. At 400 °C, in the presence of hydrogen gas, pyrene-tetralin solvent mixtures show synergism in coal conversion. At donor concentrations as low at 15 wt%, the degree of conversion was almost as high as in pure tetralin. This phenomenon was not apparent in 2-methylnaphthalene-tetralin mixtures. The relative ease of reduction of pyrene and its ability to shuttle hydrogen is considered to be a principal reason for this difference in behaviour. Conversion in pure pyrene and in pyrene-tetralin mixtures at low donor concentrations increased with increasing hydrogen pressure. At 427 °C, bituminous coal conversion was higher in a 30 wt% tetralin-70 wt% pyrene mixture than in either pure compound. It was found that in the absence of coal pyrene can be hydrogenated by H-transfer from tetralin as well as by reaction with hydrogen gas. This can provide a means to increase the rate of transfer of hydrogen to the dissolving coal through the formation of a very active donor (dihydropyrene). During coal liquefaction, several pathways appear to be available for hydrogen transfer for a given coal, the optimal route being dependent upon the solvent composition and the conditions of reaction.     

Liquefaction of coal using supercritical fluid mixtures

Powhatan No. 5 and Bruceton coals were liquefied for 15–60 min at 653 K and 30 MPa in supercritical aqueous mixtures containing 10–20 wt% tetrahydroquinoline (THQ), quinoline or tetralin. The THQ-water mixtures produced the highest conversion to tetrahydrofuran (THF) soluble products (up to 74%). Tetralin-water, quinoline-water and pure water solvents gave increasingly lower yields of THF solubles. Addition of hydrogen to the quinoline-water solvent mixture increased yields slightly, but not to the level obtained using the THQ-water mixture.The yields of THF solubles in all instances depended upon the concentration of solvent in the mixture, with the 10 wt% THQ and 10 wt% tetralin (in water) giving higher yields than either 0 or 20 wt% concentrations. The nitrogen-containing solvents were chemically bonded to the THF-soluble product, as observed by g.p.c.     

Bio-oil production from oil palm biomass via subcritical and supercritical hydrothermal liquefaction

This paper presents the studies on the liquefaction of three types of oil palm biomass; empty fruit bunch (EFB), palm mesocarp fiber (PMF) and palm kernel shell (PKS) using water at subcritical and supercritical conditions. The effect of temperature (330, 360, 390 °C) and pressure (25, 30, 35 MPa) on bio-oil yields were investigated in the liquefaction process using a Inconel batch reactor. The optimum liquefaction condition of the three types of biomass was found to be at supercritical condition of water i.e. at 390 °C and 25 MPa, with PKS yielding the maximum bio-oil yield of 38.53 wt%, followed by EFB and PMF, with optimum yields of 37.39 wt% and 34.32 wt%, respectively. The chemical compositions of the bio-oils produced at optimum condition were analyzed using GC–MS and phenolic compounds constituted the major portion of the bio-oils, with other minor compounds present such as alcohols, ketones, aromatic hydrocarbons and esters.