真空冷冻干燥制备高比表面积纳米氧化铝

采用真空冷冻干燥技术结合反相微乳液法, 于环己烷/聚乙二醇辛基苯基醚(曲拉通X-100)-十六烷基三甲基溴化铵(CTAB)/正丁醇/水溶液体系中, 合成了纳米Al2O3粉体. 采用扫描电子显微镜(SEM)、透射电子显微镜(TEM)、X射线衍射(XRD)及比表面积与孔隙度分析仪对产物的形貌、结构、比表面积、孔容与孔径进行了表征. 经过煅烧, 该纳米Al2O3比表面积约550.0 m2·g-1(随反应参数不同而变化), 属γ-Al2O3晶型, 粒径均匀, 颗粒直径小于10.0 nm. 考察了不同的干燥方式(电热鼓风干燥、普通真空干燥、真空冷冻干燥)以及真空冷冻干燥过程中主要参数对产物比表面积、孔容、平均孔径等物理性质的影响. 结果表明, 采用真空冷冻干燥法制备的纳米Al2O3的比表面积和孔容远高于采用另外两种干燥方式制备的纳米Al2O3. 采用真空冷冻干燥法制备纳米Al2O3时, 降温速率、预冻时间、冻干时间等参数对最终制备的产物比表面积与孔结构有显著影响.     

多孔碳基复合膜的真空冷冻干燥制备及高效太阳能水蒸发性能

以多壁碳纳米管(CNTs)和聚偏氟乙烯(PVDF)为原料, 通过相转化法形成均匀共混的胶体, 利用真空冷冻干燥(冻干)技术使胶体固化, 并在真空状态下使部分溶剂挥发, 制备了具有多孔结构的CNTs/PVDF复合膜. 实验结果表明, 冻干CNTs/PVDF复合膜具有优异的光吸收能力、 极佳的表面亲水性能. 在1 kW/m²光照强度下, 其水蒸发速率可达1.95 kg·m^-2·h^-1、 光热转化效率为92.9%. 搭载了冻干CNTs/PVDF复合膜的蒸发器在处理模拟海水和染料废水时, 均表现出良好的抗盐污染性、 显著的稳定性和优异的太阳能蒸发性能.     

氧在银／二氧化硅催化剂上的超高真空程序升温脱附

 研究了氧在Ag／SiO2催化剂上的超高真空程序升温脱附．结果表明，脱附谱中出现了对应于表面分子氧（Tp＝340K）、体相氧（Tp＝570K）和次表层氧（Tp＝700～800K）的脱附峰．由于催化剂在制备过程中经过高温焙烧，因而其表面原子氧浓度低，脱附谱中未出现原子氧的脱附峰．高温焙烧还可使表面缺陷浓度增大，有利于原子氧向体相扩散，形成体相溶解氧，也有利于体相氧向表面扩散，所以对应于体相氧的570K脱附峰较强．体相氧和次表层氧向表面的扩散遵循不同的扩散机理．     

真空冷冻干燥法制备CuO－ZnO－Al_2O_3合成甲醇催化剂

研究了用真空冷冻干燥法制备ＣｕＯ－ＺｎＯ－Ａｌ＿２Ｏ＿３催化剂，提出用叔丁醇代替水作介质的新方法，采用该方法可以使干燥速度显著加快。考察了反应温度、压力、空速及催化剂组成对ＣＯ＿２＋Ｈ＿２催化合成甲醇的影响。     

升温速率对胜利褐煤热解过程中N迁移转化的影响

在固定床/流化床管式石英反应器中进行了胜利褐煤的快速热解和慢速热解实验,考察了升温速率对N迁移转化及对半焦内部N化学形态变化的影响。研究结果表明,快速升温热解气相N(NH₃和HCN)生成量明显高于慢速热解时的生成量,且随着温度的升高,两者差值均逐渐增大。在多数情况下,NH₃或HCN的产率在973 K左右并不随温度的升高而增加,这与高温下的半焦热缩聚反应以及挥发分的二次反应有关。快速热解条件下,半焦N的释放速率要快于半焦炭本身失重速率。X射线光电子能谱(XPS)分析认为,热解使得吡咯型N(N-5)部分转化为吡啶型N(N-6)和季氮型N(N-Q),快速热解有利于生成N-6,而慢速热解下半焦中N-Q含量较高。     

金属铜升温熔化过程的分子动力学模拟

采用分子动力学方法模拟了金属铜的升温熔化过程.原子间作用势采用FS (Finnis-Sinclair)势，结构分析采用双体分布函数(PCF)、均方位移(MSD)等方法.计算结果表明,在连续升温过程中，金属铜在1444 K熔化，在该熔化点的扩散系数为4.31×10－9 m2•s－1.上述结论与实验值相当接近，并且比之采用EAM镶嵌原子势所作模拟得到的结果更佳，说明FS势可以用来处理象液铜这样较复杂的无序体系.本文指出了升温速率在金属熔化过程中所起的作用.     

变一次和二次干燥温度对冻干猪主动脉的影响

为了探讨在真空冷冻干燥过程中,干燥阶段温度参数对冻干制品品质的影响,以猪主动脉为研究对象,通过改变一次、二次干燥温度,并结合脱水率、外观形态、力学性能测试等,以期获得最优的温度参数.实验结果表明,当一次干燥温度为-20℃,二次干燥温度为10℃时,冻干样品的综合表现最优.     

升温速率对生物质热解的影响

稻壳、稻秆及麦秆是中国主要的农业废弃物,如何综合、有效地利用这些农业废弃物进行资源化研究显得十分必要。热解是热化学转化中最为基本的过程,是气化、液化及燃烧过程的初始和伴生反应,对热解的分析有助于热化学转化过程控制及高效转化工艺的开发。目前,国内外对生物质及其组分的热解已有大量的研究,但对中国主要的农业废弃物稻壳、稻秆及麦秆的研究较少。本研究利用热重和红外联用技术深入研究了升温速率对三种典型生物质热解气体产物的影响,并对生物质的热解动力学及热解气体产物的析出规律进行实时在线分析。     

深度冷冻干燥对聚(L-乳酸)结晶性能的影响

采用广角X射线衍射(XRD)和差示扫描量热(DSC)方法研究了深度冷冻干燥对PLLA结晶性能的影响.深度冷冻干燥方法可以改善PLLA的结晶性能.实验结果表明,0.1%、1%、5%和10%PLLA的对二甲苯溶液经过深度冷冻干燥得到PLLA的结晶速度系数(CRC)分别为0.935、0.877、0.826和0.863,高于从0.1%对二甲苯溶液中结晶得到的PLLA的CRC(为0.643).     

Physicochemical and Quality Properties of Dried Courgette Slices: Impact of Vacuum Impregnation and Drying Methods

The aim of this study was to determine the effects that the type of impregnating solution and drying method (freeze drying (FD) and vacuum drying (VD) at 45 °C and convective drying (CD) at 50, 60, and 70 °C) had on the physicochemical and quality properties of courgettes. Courgette slices were vacuum-impregnated (6 kPa) in freshly squeezed onion, kale, and onion and kale (50:50) juices with 3% NaCl solution (N). The application of vacuum impregnation (VI) with impregnating solutions from freshly squeezed onions and kale had a beneficial effect on the bioactive values of courgette. The highest contents of quercetin (41.84 μg/g d.m.) and carotenoids (276.04 μg/g d.m.) were found in courgette impregnated with onion juice after freeze drying. The highest values of lutein and zeaxanthin (216.42 μg/g d.m.) were recorded for courgette impregnated with kale juice and convective dried. By analysing the kinetics of convective drying, the best matching of the logistic model was found. Increasing the drying process temperature from 50 to 70 °C reduced the drying time from 15% to 36%, depending on the type of impregnating solution used. Water activity < 0.6 was recorded for courgette dried by freezing, vacuum, and convection at 60 and 70 °C. Conclusions: The vacuum impregnation process and the impregnation solutions from freshly squeezed vegetables can be used to develop new snacks with high levels of bioactive compounds. The FD method is the most appropriate considering both the bioactive compounds content and the obtained colour and water activity.     

叶丝在增温增湿与滚筒烘丝工序中香味组分变化分析

该文研究了制丝线增温增湿和滚筒烘丝工序加工对叶丝香味组分的影响,采用溶剂超声萃取前处理结合GC-MS法测定叶丝的香味组分,并对SIROX增温增湿工序和滚筒烘丝工序前后叶丝香味组分的相对含量进行了分析,比较了工序前后、工序间香味组分的变化趋势。结果显示:①经SIROX增温增湿工序加工后,乙酸、苯甲醇等18种组分相对含量减少,糠醇、2,4-二羟基-2,5-二甲基-3(2H)-呋喃-3-酮等6种组分相对含量增加;②经滚筒烘丝工序加工后,乙酸、麦芽酚等14种组分相对含量减少,糠醇、糠醛等6种组分相对含量增加;③经增温增湿及滚筒烘丝两工序后,乙酸、2,3-丁二醇等23种组分相对含量减少,糠醇、2,4-二羟基-2,5-二甲基-3(2H)-呋喃-3-酮等4种组分相对含量增加;④两工序间的温度、湿度剧烈变化,使叶丝内部组分发生了美拉德反应、降解反应、挥发等,香味组分经两个工序后发生了一系列显著变化。该研究对提升卷烟产品质量、优化工艺参数、开发高质量产品具有重要意义。     

Freeze vs. Spray Drying for Dry Wild Thyme (Thymus serpyllum L.) Extract Formulations: The Impact of Gelatin as a Coating Material

Freeze drying was compared with spray drying regarding feasibility to process wild thyme drugs in order to obtain dry formulations at laboratory scale starting from liquid extracts produced by different extraction methods: maceration and heat-, ultrasound-, and microwave-assisted extractions. Higher total powder yield (based on the dry weight prior to extraction) was achieved by freeze than spray drying and lower loss of total polyphenol content (TPC) and total flavonoid content (TFC) due to the drying process. Gelatin as a coating agent (5% w/w) provided better TPC recovery by 70% in case of lyophilization and higher total powder yield in case of spray drying by diminishing material deposition on the wall of the drying chamber. The resulting gelatin-free and gelatin-containing powders carried polyphenols in amount ~190 and 53–75 mg gallic acid equivalents GAE/g of powder, respectively. Microwave-assisted extract formulation was distinguished from the others by a higher content of polyphenols, proteins and sugars, higher bulk density and lower solubility. The type of the drying process mainly affected the position of the gelatin-derived -OH and amide bands in FTIR spectra. Spray-dried formulations compared to freeze-dried expressed higher thermal stability as confirmed by differential scanning calorimetry analysis and a higher diffusion coefficient; the last feature can be associated with the lower specific surface area of irregularly shaped freeze-dried particles (151–223 µm) compared to small microspheres (~8 µm) in spray-dried powder.     

不同干燥过程对超细TiO2粉体性质的影响

考察了采用不同干燥工艺制备的TiO2粉体在粒子形貌、颗粒大小与分布、晶相组成以及比表面积和孔结构等织构和结构性质方面的差异。结果表明，利用常规的干燥方法，由水凝胶脱水所得的颗粒，颗粒间严重团聚，颗粒粒径大且分布不均匀，比表面积和孔体积最小；由醇凝胶直接脱水，则可以显著提高粉体的织构性能．而采用超临界流体干燥法则可以进一步提高粉体的性能，比表面积由水凝胶的4．88m2·g－1增大到113．8m2·g－1，提高了近30倍；孔体积由0．027cm3·g－1增大到0．41cm3·g-1．大约提高了15倍；而且其能够有效地防止粒子间的团聚，较好地保持了湿凝胶的网络结构，使颗粒尺寸降低且分布均匀，可重复性好．     

干燥实验中干燥曲线的处理方式讨论*

在干燥特性曲线的测定实验中,先根据物料含水量(X)随时间(t)的变化,绘制出干燥曲线(X-t),求导得到干燥速率(U),再对X作图得到干燥速率曲线(U-X)。由于测得的X-t数据点较多,U-X曲线波动较大,因此选用合适的数据处理方式以得到准确的U-X曲线对于研究干燥过程至关重要。比较了X-t曲线的几种处理方式,结果表明,当区间较小时,差商法会造成U-X曲线较大的波动,增加取差商的区间可降低波动,但区间过大可能导致U-X曲线丢失部分重要细节;相比之下,对X-t平滑处理后再取微分可明显减小波动,且保持U-X曲线趋势不变。另一个比较好的处理方法是分段拟合,得到的U-X曲线可明确划分不同阶段以及获得更为准确的关键数据;除了线性拟合外,U-X曲线的降速阶段也可用双曲线模型拟合,均有较好的拟合效果。     

Microencapsulation of Flaxseed Oil by Lentil Protein Isolate-κ-Carrageenan and -ι-Carrageenan Based Wall Materials through Spray and Freeze Drying

Lentil protein isolate (LPI)-κ-carrageenan (κ-C) and -ι-carrageenan (ι-C) based microcapsules were prepared through spray-drying and freeze-drying to encapsulate flaxseed oil in order to reach final oil levels of 20% and 30%. Characteristics of the corresponding emulsions and their dried microcapsules were determined. For emulsion properties, all LPI-κ-C and LPI-ι-C emulsions remained 100% stable after 48 h, while the LPI emulsions destabilized quickly (p < 0.05) after homogenization mainly due to low emulsion viscosity. For spray-dried microcapsules, the highest yield was attributed to LPI-ι-C with 20% oil, followed by LPI-κ-C 20% and LPI-ι-C 30% (p < 0.05). Flaxseed oil was oxidized more significantly among the spray-dried capsules compared to untreated oil (p < 0.05) due to the effect of heat. Flaxseed oil was more stable in all the freeze-dried capsules and showed significantly lower oil oxidation than the untreated oil after 8 weeks of storage (p < 0.05). As for in vitro oil release profile, a higher amount of oil was released for LPI-κ-C powders under simulated gastric fluid (SGF), while more oil was released for LPI-ι-C powders under simulated gastric fluid and simulated intestinal fluid (SGF + SIF) regardless of drying method and oil content. This study enhanced the emulsion stability by applying carrageenan to LPI and showed the potential to make plant-based microcapsules to deliver omega-3 oils.     

Effects of Different Processing Methods Based on Different Drying Conditions on the Active Ingredients of Salvia miltiorrhiza Bunge

Compared to the traditional processing method, fresh processing can significantly enhance the preservation of biologically active ingredients and reduce processing time. This study evaluated the influences of fresh and traditional processing based on different drying conditions (sun drying, oven drying and shade drying) on the active ingredients in the roots and rhizomes of S. miltiorrhiza. High-performance liquid chromatography (HPLC) was utilized to determine the contents of six active ingredients in the roots and rhizomes of S. miltiorrhiza. The data were analyzed by fingerprint similarity evaluation, hierarchical cluster analysis (HCA) and principal component analysis (PCA). The results suggest that compared to the traditional processing method, the fresh processing method may significantly increase the preservation of biologically active ingredients. Furthermore, the findings demonstrated that among the three drying methods under fresh processing conditions, the shade-drying (21.02–26.38%) method is most beneficial for retaining the active ingredients in the roots and rhizomes of S. miltiorrhiza. Moreover, the fingerprint analysis identified 17 common peaks, and the similarity of fingerprints among samples processed by different methods ranged from 0.989 to 1.000. Collectively, these results suggest novel processing methods that may improve the yield of active ingredients for S. miltiorrhiza and may be implemented for industrial production.     

Influence of Convective and Vacuum-Type Drying on Quality,Microstructural, Antioxidant and Thermal Properties of Pretreated Boletus edulis Mushrooms

Freshly harvested Boletus edulis mushrooms are subjected to rapid loss of quality due to the high moisture content and enzymatic activity. Drying time, quality characteristics, microstructural and thermal properties were studied in mushrooms ground to puree subjected to hot air drying (HAD), freeze drying (FD) and centrifugal vacuum drying (CVD). The influence of hot water blanching and UV-C pretreatments was additionally investigated. The rehydration ability of mushroom powders was improved by FD, especially without pretreatment or combined to UV-C exposure. The HAD and CVD, with no pretreatment or combined to UV-C, ensured good preservation of phenolics and antioxidant activity of dried mushrooms. The total difference in color of mushroom pigments extracted in acetone was lower in samples dried by CVD and higher in ones by FD. Blanching before HAD produced whiter product probably due to the reduced polyphenoloxidase activity. Scanning Electron Microscopy (SEM) analysis showed fewer physical changes in FD-samples. Heat-induced structural changes were noticed by Differential Scanning Calorimetry (DSC), Thermogravimetry (TG) and Derivative Thermogravimetry (DTG) analysis, in particular of biopolymers, confirmed by ATR-FTIR analysis. Based on our complex approach, the UV pretreatment of mushrooms could be a better alternative to water blanching. Centrifugal vacuum emerged as a new efficient drying method in terms of bioactive compounds, color and thermal stability, while FD led to better rehydration ability and microstructure.     

Preparation of Copper Chromite by Vaccum Freezing Drying Method and Its Catalytic Activity for Sulfuric Acid Decomposition

Iodine sulfur (IS) process is one of the most promising routes for massive and CO₂‐free hydrogen production. Among the three reactions IS process composed, decomposition of sulfuric acid is the most energy intensive step and has to be conducted in the presence of catalyst. In this work, copper chromite (CuCr₂O₄) was prepared, characterized, and used as the catalyst for sulfuric acid decomposition reaction. The co‐precipitation preparation method of CuCr₂O₄ which featured in vacuum freezing drying (VFD), was applied, and the main factors which influence the structure of CuCr₂O₄ such as pH values of the co‐precipitation solution and calcination temperature were investigated. Results showed that pH value affected the size of copper chromite granule, when pH was between 7 and 8, the size of prepared CuCr₂O₄ was in nanometer scale. Calcination temperature influenced the purity of the crystal. The samples were characterized by XRD, TEM and BET. The catalytic activity of CuCr₂O₄ prepared by VFD was evaluated and compared with CuCr₂O₄ prepared by usual co‐precipitation method and Pt/Al₂O₃. Results showed that the activity of CuCr₂O₄ was close to that of Pt catalyst, but apparently higher than that of CuCr₂O₄ prepared by usual method. In addition, it presents good stability in the 70 h test. Therefore, it was promising to be used in the sulfuric acid decomposition step of IS process.