The effect of free fatty acid on the reactivity of copper-based catalysts for the hydrogenolysis of fatty acid methyl esters

In the synthesis of fatty alcohols by hydrogenolysis of fatty acid methyl esters, small amounts of free fatty acids in the feed negatively affect the reactivity of copper-silica based catalysts. The effect of the acid was investigated in relation to the production of water, the nature of the inhibiting species, and the degree of reduction of the catalyst. Inhibition is reversible and not due to catalyst deactivation. Water is not the inhibiting species. Furthermore, formation of copper and zinc soaps was excluded. Lauric acid in the methyl ester feed reacts preferentially, but at a lower rate than the ester. Inhibition most likely stems from a preferential adsorption of the acid at the active sites of the catalyst. The consequences for practical applications are discussed.     

Improvement of mesoporosity of carbon cryogels by ultrasonic irradiation

Mesoporous carbon gels are usually obtained by pyrolyzing resorcinol-formaldehyde (RF) gels, which are synthesized via the sol-gel polycondensation of resorcinol with formaldehyde in a slightly basic aqueous solution followed by drying. However, mesoporous carbon gels cannot be prepared under the conditions of high catalyst concentration or high pH of RF solution even by using supercritical drying or freeze drying. In this work, mesoporosity of carbon cryogels is improved by ultrasonic irradiation to RF solution. It is found that the gelation time of RF solution becomes greatly short by ultrasonic irradiation and that ultrasonic can improve mesoporosity of carbon cryogels prepared at high catalyst concentration (C/W). Although the carbon cryogels prepared from C/W = 80 mol/m³ have no mesopores, the carbon sonogels prepared by ultrasonic irradiation under the same catalyst condition have sharp mesopore size distribution. The utilization of ultrasonic in the preparation of RF gel is an interesting way in improving mesoporosity of carbon gels prepared at high C/W or pH.     

Laboratory-scale continuous hydrogenation: Effect of pressure

A laboratory-scale, high-pressure, continuous reactor was used to partially hydrogenate soybean oil with copper catalysts. Effects of pressure on the kinetics of the reaction were studied by conducting experiments in a central composite design. The interaction of pressure (75\s-200 psig) with the other independent variables of temperature (155\s-255 C) and copper concentration (0.15\s-1.85%) was evaluated. Dependent variables studied were linolenate selectivity and formation of trans isomers and conjugated dienes. in addition, effects of pressure up to 500 psig, use of experimental and commercial copper catalysts and comparison of continuous with high-pressure batch rections were investigated. Linolenate selectivity (8\s-10) and trans-isomer formation were not significantly affected by any of the independent variables. Conjugated dienes were eliminated as products of the reaction when pressure was above 200 psig. Experimental copper-silica catalyst gave a 1.6-fold increase in reaction rate over commercial copper catalysts. Presented at ISF-AOCS meeting, New York, April 1980.     

SO4^2-/TiO2-La2O3固体超强酸催化合成乳酸乙酯

采用TiCl4和La（NO3）3·6H2O共沉淀法制备固体超强酸SO4^2-/TiO2-La2O3催化剂。制备条件为nTi/nLa比为8：1,-15℃陈化24h,120℃干燥12h,浸渍液硫酸浓度为0．5mol·L^-1,浸渍4h,120℃干燥1h,400℃焙烧4h的催化剂对乳酸与乙醇的酯化反应有较高的活性。将此催化剂用于乳酸和乙醇合成乳酸乙酯的酯化反应,考察了催化剂用量、乙醇和乳酸的物质的量的比、反应时间、带水剂环己烷的用量对酯化反应的影响。实验结果表明,醇酸物质的量的为2．0：1,催化剂用量为所用乳酸质量的1．4％,环己烷为乙醇体积的78％,反应时间4h条件下酯化产率达82％。催化剂易回收,使用寿命长的优点。     

IMPROVING THE QUALITY OF TIMBER FROM RED BEECH (N. FOSCA) BY INTERMITTENT DRYING

The effect of cycling the external conditions on the timber quality and drying time during seasoning has been studied for red beech (Nothofagus fusca), a difficult-to-dry New Zealand hardwood, inalaboratorybatchdryer. Intermittent drying at anair temperature of 45°C and a wet-bulb depression of 10°C takes longer to yield a given moisture content than continuous drying under the same conditions, but produces timber without honeycomb or severe case-hardening as observed in continuous drying. The experiments also indicate that the timber can tolerate a higher air temperature (55°C) in intermittent drying at the same wet-bulb depression with less case-hardening and without showing honeycomb compared with continuous drying at 45°C, having a similar total drying time. Intermittent drying at a slightly higher dry-bulb temperature (60°C) and a much higher wet-bulb depression (18°C) gives a similar degree of case-hardening to that found in samples dried continuously at a dry-bulb temperature of 45°C.     

Physical properties and structure of silk: 4. Spherulites grown from aqueous solution of silk fibroin

Spherulite formation in silk fibroin films cast from aqueous solution has been studied for crystallization conditions such as drying temperature, drying rate and pretreatment (freezing). Negatively birefringent spherulites in the α-form are observed in films cast between 0° and 40°C, and with a high drying rate at 20°C; positive β-form spherulites appear at higher temperatures up to 80°C and with a low drying rate at 20°C. Positive β-form spherulites are also obtained by freezing fibroin solution at ?2° to ?18°C and then drying at 20°C. It is found that positive β-form spherulites grow at 20°C on the surface of well-oriented β-form silk fibroin filaments (degummed silk) immersed in fibroin solution.     

草酸二甲酯加氢制乙二醇Cu/SiO2催化剂的制备与改性

采用均匀沉淀沉积法制备Cu/SiO₂催化剂。考察了Cu²⁺浓度、洗涤条件及铜与硅物质的量比等的影响,并通过BET和XRD等表征手段研究分析,结果表明,前驱体制备过程及条件对催化剂结构和活性有较大影响。低Cu²⁺浓度、醇洗干燥均有利于形成大孔径高活性的催化剂。铜与硅物质的量比对反应活性的影响较大,存在一个最佳值,在0.4时活性最高。最优条件下制得的催化剂用于草酸二甲酯加氢制乙二醇,在反应温度205 ℃、压力2 MPa、n(H₂) ∶n(DMO)=80和空速1.0 h^-1条件下,草酸二甲酯的转化率为100%,乙二醇选择性为99.1%,乙醇酸甲酯选择性为0.9%,无其他副产物生成。     

陶瓷纤维催化剂载体的制备及其性能

利用陶瓷纤维毡为原料,通过适当的成型工艺将纤维毡制备成陶瓷纤维催化剂载体.探讨浸润助剂(十二烷基硫酸钠,SDS)用量、纤维毡的干燥工艺及黏结剂浓度对陶瓷纤维催化剂载体的成型和性能的影响.确定最优的成型工艺,以质量分数0.2％的SDS作浸润助剂,150℃干燥2 min,质量分数30％的硅溶胶作黏结剂,浸渍粘结后烘干,即制...     

Investigation of Conjugated Soybean Oil as Drying Oils and CLA Sources

Better sources of drying oils for coatings and conjugated linoleic acid (CLA) for potential health benefits are of continuing interest. Iodine under photochemical conditions in hexanesB at reflux temperatures was investigated as a catalyst for conjugating soybean oil (SBO) for use as drying oils and as a potential source of CLA. Variations in catalyst loading, SBO, light source, free radical catalyst, solvent and temperature strongly affected the efficiency of the process. Changes in fatty acid isomer distributions in conjugated SBO (CSBO) influenced drying properties of CSBO. Conjugated dienes formed were predominantly trans-9,trans-11, which contrasts distributions found with catalysts such as strong base and metal compounds. Drying times of some of the CSBOs were superior to that of raw linseed oil. Iodine was partially recovered.     

Influence of Drying Conditions on Physical Properties of Alginate Films

The effect of drying conditions of the film-forming solution on thickness, moisture content, water vapor permeability, and tensile properties of alginate films were investigated. A long period of constant rate was observed in all conditions and the model proposed by Wang and Singh was able to adjust the drying data. As expected, there was a clear effect of temperature on drying kinetics; that is, increasing the drying temperature decreased the drying time. Considerable glycerol losses were observed when alginate gel was oven dried at temperatures above 40°C. Compared to other drying conditions, films oven dried at 60°C were thinner, had lower moisture content, and were less flexible.     

低温陈化法制备SO_4~(2-)/ZrO_2-Al_2O_3固体超强酸催化合成氯乙酸异辛酯

采用ZrOCl2.8H2O和Al(NO3)3.9H2O共沉淀法制备固体超强酸SO42-/ZrO2-Al2O3催化剂。固体超强酸SO24-/ZrO2-Al2O3制备条件为nZr∶nAl=3∶1,-15℃陈化24 h,120℃干燥12 h,浸渍液硫酸浓度为0.5 mol/L,浸渍4 h,120℃干燥1 h,650℃焙烧4 h。将此固体超强酸酯用于氯乙酸和异辛醇合成氯乙酸异辛酯的酯化反应,考察了异辛醇和氯乙酸的摩尔比、催化剂用量、反应时间、带水剂环己烷的用量对酯化反应的影响。结果表明,醇酸比为1.1∶1,催化剂用量为所用氯乙酸质量的1.7%,环己烷为异辛醇体积的46%,反应时间1.5 h条件下酯化率达94.3%。     

MgO/C负载磺化酞菁钴催化剂制备条件对其硫醇氧化性能的影响

采用浸渍法制备了系列MgO/C负载磺化酞菁钴（CoPcS）脱硫醇催化剂,讨论了Mg与C物质的量比、干燥温度和浸渍溶剂等对催化剂活性的影响。采用XRD、BET、DTA-TG和FTIR等表征方法对催化剂的物性结构进行了研究。结果表明，在反应初始阶段，催化剂活性由催化剂碱量和比表面积共同决定。随着反应的进行，催化剂活性主要由催化剂碱量决定。当Mg与C物质的量比为0.2、干燥温度200 ℃和采用甲醇（非水溶剂）浸渍时，催化剂稳定性提高，具有最佳物性结构，催化剂活性最好。     

活性炭负载醋酸锌催化剂真空干燥的特性

通过真空干燥实验研究了供热温度、真空度、料层厚度等因素对醋酸锌-活性炭催化剂干燥规律的影响。实验结果表明:醋酸锌-活性炭催化剂采用真空干燥可以实现快速低温干燥;催化剂的干燥只有降速干燥阶段,而没有常速干燥阶段;供热温度的提高有助于提高干燥速率,但温度超过80℃时催化剂出现轻微粉化;真空度越高,干燥速率特别是初始干燥速率越快;料层厚度的增加,使干燥时间延长,但设备的干燥强度有所提高。正交实验得出,在多因素条件下,温度对干燥强度的影响最大,其次是真空度和料层厚度。     

Thin-layer drying of litchi (Litchi chinensis Sonn.)

This article presents the thin-layer drying of peeled litchi, which was conducted under controlled conditions of temperature and relative humidity. It was observed that the drying temperature has some influence on the drying rates of peeled litchi, so that the higher the temperature the less the drying time. Eight different thin-layer models were fitted to the experimental data of peeled litchi. The drying parameters of peeled litchi were found to be a function of drying air temperature and relative humidity. The Page model was revealed to be the best and it was followed by the logarithmic models. The agreement between the predicted and experimental values for the Page model is excellent, so that this can be used to provide design data and for simulation and optimisation of the dryer for efficient operation. The colour of the dried litchi was light golden brown and it remained almost unchanged for drying at 50 °C, 60 °C and 70 °C. Therefore, the quality change of the dried litchi in terms of colour change was not significant for drying in the temperature range of 50–70 °C.     

腰果酚、三聚氰胺改性酚醛树脂的制备

以苯酚与甲醛作为原料,采用腰果酚、三聚氰胺对酚醛树脂进行改性,研究了腰果酚含量、三聚氰胺含量、催化剂加入方式以及干燥温度等对其性能的影响,得出改性酚醛树脂的适宜生产工艺条件:n(总酚量):n(醛)=1:0.91,n(苯酚):n(甲醛):n(腰果酚):n(三聚氰胺)=1:1:0.1067:0.0541,催化剂含量3.1%,反应时间约为2.5h,真空干燥温度为100℃。     

Microwave-Assisted Atmospheric Freeze Drying of Green Peas: A Case Study

Atmospheric freeze drying (AFD) is based on the sublimation of ice due to a pressure gradient (convective drying), and is a dehydration process for temperature-sensitive products. Since the process is slow in general, microwave radiation (MW) was applied in order to increase the sublimation in fluid and fixed bed conditions at drying temperatures of ?6°C, ?3°C, and 0°C. The modified Weibull model was used to describe the drying behavior for all investigations. With 280 Watt power supplied to the magnetrons, it was possible to reduce drying time by approximately 50%. The drying efficiency was approximately 30%, while the SMER was increased by 0.1 to 0.3 kg_waterkWh^?1, which gives better energy efficiency for the microwave drying system used in this investigation. The product quality (color reduction and particle size/porosity) was well preserved in fixed bed drying at ?6°C and ?3°C, while the product quality was reduced significantly in microwave AFD experiments at 0°C and in a fluid bed. The drying rates of AFD in a fluid bed condition were not as high as those in a fixed bed. MW-AFD in a fixed bed condition at temperatures of ?6°C and ?3°C performed best regarding product quality, drying time, and process control.     

Thin-Layer Drying of Flax Fiber: III. Influence of Layer Thickness on Drying Parameters

Wet flax fiber was dried after rinsing at four layer thicknesses of 5, 10, 15, and 20 mm using four drying air temperatures of 30, 50, 70, and 100°C. The coefficients of diffusion of flax fiber at different drying conditions were estimated using a three-term series solution of Fick's second law of diffusion. The Page model was used to model the drying characteristic curves. The estimated coefficient of diffusion of the flax fiber and the drying constant of the Page model were both linearly proportional to drying air temperature and increased exponentially with the thickness of the drying layer.     

Thin-Layer Drying of Flax Fiber: III. Influence of Layer Thickness on Drying Parameters

Wet flax fiber was dried after rinsing at four layer thicknesses of 5, 10, 15, and 20 mm using four drying air temperatures of 30, 50, 70, and 100°C. The coefficients of diffusion of flax fiber at different drying conditions were estimated using a three-term series solution of Fick's second law of diffusion. The Page model was used to model the drying characteristic curves. The estimated coefficient of diffusion of the flax fiber and the drying constant of the Page model were both linearly proportional to drying air temperature and increased exponentially with the thickness of the drying layer.     

Comparative Evaluation of Physical Properties of Edible Chitosan Films Prepared by Different Drying Methods

Edible films are alternative packaging, which have recently received much attention due mainly to environmental reasons. Edible films may be formed from edible biomaterials such as polysaccharides, proteins, or lipids. Among these biopolymers, chitosan is of interest because it has a good film-forming property and is biodegradable, biocompatible, and nontoxic. Several techniques have been used to prepare edible chitosan films with various degrees of success. However, it is always interesting to find an alternative technique to produce films of superior quality at shorter processing (drying) time. In this study, the influences of different drying methods and conditions on the drying kinetics and various properties of chitosan films were investigated. Drying at control conditions (ambient air drying and hot air drying at 40°C) as well as vacuum drying and low-pressure superheated steam drying (LPSSD) at an absolute pressure of 10 kPa were carried out at different drying temperatures (70, 80, and 90°C). The properties of chitosan films, in terms of color, tensile strength, percent elongation, water vapor permeability (WVP), glass transition temperature (T_g), and crystallinity, were also determined. Based on the results of both the drying behavior and film properties, LPSSD at 70°C was proposed as the most favorable conditions for drying chitosan films.     

A study on the preparation of supported metal oxide catalysts using JRC-reference catalysts. I. Preparation of a molybdena–alumina catalyst. Part 4. Preparation parameters and impact index

The effects of the volume and pH of the impregnation solution and of the calcination conditions were examined on the physicochemical and catalytic properties of a 13 wt% MoO₃/Al₂O₃ extrudate catalyst. The Al₂O₃ support and drying procedures (static conditions without flowing air) were fixed in the preparations. In the present series of catalysts, the amount of crystalline MoO₃ was marginally small. It was found that the dispersion of Mo oxide species increased as the volume of the impregnation solution increased, gradually approaching a maximum value. The increase in pH (2–8) of the impregnation solution was found to reduce the dispersion of Mo oxide species. The Mo dispersion increased slightly for the impregnation catalysts as the calcination temperature increased (673–873 K), whereas it decreased for the equilibrium adsorption catalysts. The effects of the calcination atmosphere (with or without flowing air, or with flowing humid air) were very small on the dispersion of Mo oxide species under the present preparation conditions. On the other hand, the methanol oxidation activity of MoO₃/Al₂O₃ was sensitive to the preparation parameters examined here. It was demonstrated by means of EPMA and XPS that a considerable migration of Mo took place during the calcination.

In the present study on the preparation of a 13 wt% MoO₃/Al₂O₃ catalyst, an impact index is proposed to measure the magnitude of the effects of the respective parameter(s) on the physicochemical and catalytic properties. With the Mo dispersion, the effects of the preparation parameter decreased in the order, surface area of the support >> drying process > volume of the impregnation solution > pH, calcination temperature and atmosphere. The size of the impact index for the dispersion of Mo sulfide species is 70–75% of that for the Mo oxide species. The HDS activity of the catalyst was less affected by the preparation parameters than the Mo sulfide dispersion. The preparation parameters affected the segregation of Mo on the outer surface of extrudates in a decreasing order: drying process > volume of the impregnation solution > pH, calcination conditions. It was found that the oxidation of methanol was affected most intensely by the drying procedures. The volume of the impregnation solution, calcination conditions and pH of the impregnation solution also strongly affected the oxidation activity. The impact index suggests that the sensitivity to the preparation variables of the physicochemical and catalytic properties of MoO₃/Al₂O₃ decreases in the order, methanol oxidation activity > surface Mo segregation > Mo oxide dispersion > Mo sulfide dispersion > HDS activity.