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。     

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。     

超临界二氧化碳分离乙醇水溶液的模拟计算

使用PR状态方程结合Hurou和Vidal提出的局部组成混合规则,较好地预测了CO_2-C_2H_5OH-H_2O三元体系的汽液平衡数据。在此基础上,模拟计算了超临界CO_2分离乙醇水溶液的过程。对萃取塔的特点和工艺条件作了详细的讨论。     

超临界乙醇萃取萘的实验研究

采用恒容升温法研究了超临界乙醇萃取煤焦油重要组分萘的效果,讨论了萃取温度和压力对萃取效果的影响.结果表明,在温度为270℃、压力为13MPa时,萘的超临界浓度为1.739×10^-2g/mL、萃取率为66.20％.     

超临界乙醇萃取苯酚的实验研究

以乙醇为超临界溶剂,采用恒容升温法研究了超临界乙醇对苯酚的萃取效果,探讨了温度和压力对萃取效果的影响。结果表明,在萃取温度为270~275℃,萃取压力为13 MPa左右时,萃取效果明显,萃取率达62%以上,苯酚在超临界乙醇中的质量浓度为0.015 657 g/mL,实验效果明显。研究得出,温度与压力对固体物质的超临界溶解度具有明显的选择调节性。     

超临界二氧化碳中乙烯基三乙氧基硅烷改性丙烯酸的合成及溶液性质

在超临界二氧化碳介质中,通过自由基沉淀聚合反应合成了一系列不同乙烯基三乙氧基硅烷（VTEOS）、丙烯酸十八酯（ODA）含量的丙烯酸疏水缔合丙烯酸聚合物。采用扫描电镜、红外光谱、滴定法和旋转黏度计对共聚物的形貌、组成及溶液性质进行了表征。实验结果表明共聚物形貌是由直径小于1 μm左右的球形颗粒组成。在疏水单体含量小于1%(mol)时,VTEOS疏水改性聚合物的黏度大于ODA疏水改性聚合物的黏度。在VTEOS含量为0.2%(mol)时,通过硅氧烷间化学反应,硅氧烷改性丙烯酸聚合物溶液黏度达到2400 mPa·s。     

苯在超临界水中的分子动力学研究

Microscopic structure and diffusion properties of benzene in ambient water (298 K, 0.1 MPa) and supercritical water (673--773 K, 25---35 MPa) are investigated by molecular dynamics simulation with site-site models.It is found that at the ambient condition, the water molecules surrounding a benzene molecule form a hydrogen bond network. The hydrogen bond interaction between supercritical water molecules decreases dramatically under supercritical conditions. The diffusion coefficients of both the solute molecule and solvent molecule at supercritical conditions increase by 30---180 times than those at the ambient condition. With the temperature approaching the critical temperature, the change of diffusion coefficient with pressure becomes pronounced.     

含自缔合流体混合物的分子热力学模型

缔合流体及其混合物的亥氏函数和压缩因子可表示为物理相互作用的贡献和化学缔合作用的贡献两部分之和。前者可采用作者建立的非缔合流体及其混合物的分子热力学模型;作者从分子间相互作用位能函数的粘滞球模型出发,利用统计力学方法确定了混合物中自缔合作用的贡献。模型中分子间的缔合参数完全可由纯物质性质确定,而只在混合物方阱位能参数的计算中引入可调的二元相互作用参数。对于含有一个自缔合组分的二元混合物常压和高压汽液平衡数据的关联结果令人满意。     

超临界水中气体扩散系数的分子动力学模拟

采用分子动力学（MD）方法计算T＝703.2-763.2K,p=30-45MPa范围内,氧气和氮气在超临界水中的无限稀释扩散系数。计算结果表明,在超临界条件下的扩散系数较常温常压下要大1－2个数量级。扩散系数随温度的升高而增大,随压力的增高而降低,且氧的扩散系数稍大于氮的扩散系数。     

超临界乙醇萃取咔唑的实验研究

以乙醇为超临界萃取基剂,采用恒容升温法研究了超临界乙醇对煤焦油蒽油组分咔唑的萃取效果,探讨了温度和压力对萃取效果的影响。结果表明,在萃取温度为270-280℃、萃取压力为12MPa左右时,咔唑的溶解度较大、萃取率较高,萃取效果明显;温度和压力对超临界乙醇萃取咔唑影响显著;超临界乙醇萃取单组分咔唑效果较好。     

Depolymerization of poly(ethylene terephthalate) wastes using ethanol and ethanol/water in supercritical conditions

Chemical recycling of poly(ethylene terephthalate) (PET) in supercritical ethanol has been investigated. In the presence of water, under supercritical conditions (temperature and pressure above 516 K and 6,384 kPa, respectively) excess ethanol reacts with PET to form diethyl terephthalate (DET) as the main product. A laboratory‐made 0.1 L ‐batch reactor was used at 528 K under pressures from 7,600 and 11,600 kPa. After the required reaction times, the reaction products were analyzed by reverse phase high pressure liquid chromatography and nuclear magnetic resonance. It was found that PET is completely depolymerized into monomers in about 5 h. The influences of water, pressure, ethanol/PET weight ratio, PET sources, as well as depolymerization time were investigated. Maximum DET recovery yield was 98.5%. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 2009–2016, 2006     

Ru/C催化作用下生物油在超临界乙醇中的提质

使用了两步加氢-超临界提质以及一步超临界提质两种方法对生物油进行提质,并进行了溶剂回收利用。实验结果表明经过这两种提质方法,生物油的物化性质均得到有效提升,提质后生物油中酸、酮和酚的相对含量明显下降,而醇、醚和酯类等理想产物的相对含量有显著上升。根据每步产物的GC-MS结果,对提质过程中所发生的反应进行了推测。相对于一步法提质所得到生物油,两步提质法所得到的提质生物油中醇和醚类的相对含量略高而酮、酚和酯类的相对含量略低。同时,相比于一步超临界提质,两步加氢-超临界提质过程中乙醇的消耗量有所降低。溶剂的回收利用在降低生物油提质所需要的乙醇含量的同时提高了提质产物中酯类的相对含量,这表明在较低的醇油比条件下超临界提质仍然是一种有效的生物油提质方法。     

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.     

Extraction of phospholipids from canola with supercritical carbon dioxide and ethanol

The potential use of supercritical (SC)-CO₂/ethanol mixture for the extraction and fractionation of phospholipids (PL) from flaked canola seeds, canola meal, and acetone insolubles (AI) was investigated. PL extraction was possible when ethanol was used as a cosolvent in SC-CO₂. PL recovery of 20.8% was achieved when canola flakes were extracted at 70°C and 55.2 MPa with SC-CO₂/10%EtOH after iol removal with neat SC-CO₂. Soaking of canola meal with ethanol prior to SC-CO₂/EtOH extraction increased PL recovery to 30.4%. PL content of the extracts increased with decreasing triglyceride concentration in the feed material and increasing amounts of ethanol added to SC-CO₂ or used for soaking. Fractionation of Al gums resulted in extracts containing 50% PL, of which 90% was phosphatidylcholine (PC); but yields were low, even after soaking treatment, due to caking. SC-CO₂/EtOH mixture may be used to extract PC-enriched PL from flaked canola seeds, canola meal, and AI. However, further research is needed to improve extraction efficiency.     

超临界乙醇体系中苯酚催化加氢的降解规律

目前,液化的生物油与石油粗油成分接近,通常环类化合物含量高,如煤焦油中酚及其衍生物含量占40%以上,急需加氢升级技术。超临界乙醇（243.1℃,6.38MPa）温度、压力条件低,具有良好的传质性能,且为绿色、可再生溶剂。在超临界乙醇体系下的催化加氢是一种油升级有效方式。本文以苯酚为生物油中环类化合物典型模型,在300～400℃、Pt/C催化剂下,探讨超临界乙醇体系下苯酚催化加氢过程。研究分析了超临界乙醇中温度、氢气压力和反应时间对苯酚催化加氢降解规律的影响,并建立了能很好地描述过程中苯酚转化率的动力学模型（R2 = 0.989）。实验表明：该体系下的苯酚催化加氢降解反应的级数为二级,反应的活化能为51.7kJ/mol;尽管升高温度和氢气压力均能提高苯酚的转化率,但温度对转化率的影响更为显著。本研究将为更好地控制反应过程和提高超临界乙醇体系中苯酚的转化率提供参考。     

胜利褐煤超临界乙醇脱氧实验研究

为有效脱除褐煤中含氧官能团,采用超临界乙醇工艺处理胜利褐煤,研究温度、停留时间和醇煤质量比对胜利褐煤脱氧效果的影响,并利用FT-IR和GC/MS对固液相产物进行表征。结果表明,胜利褐煤超临界乙醇脱氧的最佳工艺条件为:温度270℃,停留时间90 min,醇煤质量比5∶1,此时煤样总氧含量为9.29%,脱氧率为61.40%,固相产率为89.62%。在220℃得到的液相产物中,80%左右为芳香族类化合物,酚类和酯类含氧化合物体积分数低于5%,其他含氧类化合物11.29%。270℃得到的液相产率中芳香族类化合物体积分数降低31.69%,含氧类化合物体积分数增加2.81%,酚类和酯类含氧化合物增至35%左右。褐煤经超临界醇解后,乙醇与煤分子作用发生了醚氧桥键的断裂反应,煤分子发生了脱羧反应,液相产物中含有大量酚类(主要为苯酚及其取代物)和酯类(主要为乙酯类)。     

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.