A potential biodegradable rubber—Viscoelastic properties of a soybean oil-based composite

Scientists are more and more interested in biodegradable materials owing to their environmental advantage. We investigated viscoelastic properties of a newly developed biomaterial made from epoxidized soybean oil (ESO). ESO cross-linked by triethylene glycol diamine exhibited viscoelastic solid properties. The storage modulus (G′) was 2×10⁴ Pa over four frequency decades. The phase angles were 14–18°. Stress relaxation measurements showed that there was no relaxation up to 500 s. From the plateau modulus we estimated that the M.W. of this cross-linked soybean oil was on the order of 10⁵. The composites of cross-linked ESO with three different fibers had 50 times higher elasticity (G′) than those without fiber. Phase shifts were the same as those of cross-linked oil without fibers, but the linear range of rheological properties was much narrower than that of the material without fibers. All these results indicated that this new biopolymer made from soybean oil exhibited strong viscoelastic solid properties similar to synthetic rubbers. These rheological properties implied that this biomaterial has high potential to replace some of the synthetic rubber and/or plastics.     

温敏型聚合物在稠油污水中的絮凝作用探讨

稠油污水絮凝剂大都是阳离子聚丙烯酰胺(CPAM),但该絮凝剂在稠油污水中高分子长链的伸展受到高温和高矿化度的影响,絮凝效果大大降低。探讨了一种温敏型絮凝剂PA在不同浓度、温度、及不同浓度无机盐(NaCl和CaCl_2)条件下的絮凝作用并与CPAM进行对比。实验结果表明:温敏絮凝剂PA对稠油污水的乳化油和固相悬浮物的去除率较CPAM高,其主要原因是PA在较高温度下发生相分离使溶液亲水性降低、吸附能力增强;温度和无机盐(NaCl、CaCl_2)能促进温敏絮凝剂PA对稠油污水中乳化油和固相悬浮物的去除效果。     

Experimental evaluation of alkaline treatment as a method for enhancing the enzymatic digestibility of autohydrolysed Acacia dealbata

BACKGROUND: Acacia dealbata wood samples were subjected to hydrothermal processing in aqueous media, yielding a liquid phase (containing xylooligosaccharides) and a solid phase, enriched in cellulose, which was treated with alkaline solutions to obtain solids with improved susceptibility towards enzymatic hydrolysis. The effects of the most influential variables involved in the alkaline processing (sodium hydroxide concentration, temperature and reaction time) on solid yield, solid composition and kinetic parameters involved in the modelling of the enzymatic hydrolysis were assessed using the response surface methodology (RSM). RESULTS: Analysis of the RSM equations allowed selection of operational conditions (temperature = 130 °C, sodium hydroxide concentration = 4.5%, time of alkaline processing = 3 h), leading to selective removal of non‐cellulosic components and to a solid substrate highly susceptible to enzymatic hydrolysis. Operating at an enzyme loading of 20 FPU (filter paper units) g^?1 autohydrolysed, extracted solids (denoted AES) with a liquor to solid ratio of 30 g liquor g^?1 AES, solutions containing 29.7 g glucose L^?1 (corresponding to a yield of 47.3 g glucose per 100 g solids from autohydrolysis) were obtained after 48 h. CONCLUSION: Samples of Acacia dealbata wood were processed by autohydrolysis, sodium hydroxide treatment and enzymatic hydrolysis, yielding xylooligomers and processed solids highly susceptible to the enzymatic hydrolysis. Copyright © 2009 Society of Chemical Industry     

Composition and thermal properties of Rhea oil and its fractions

The rhea (Rhea americana) is a large running bird of the ratite family, native to South America. Oil extracted from rhea fat tissue is used in cosmetic manufacture. Here, the thermal behaviour and the fatty acid and triacylglycerol composition of Uruguayan rhea oil are studied. The results are compared with those obtained from two commercial samples of emu oil. The fatty acid profiles of emu and rhea oils are similar. Small variations are reflected in the non‐identical thermal behaviour of the oils. The solid content of both oils is fairly similar at room temperature. Thus, emu oil and rhea oil may replace one another in certain formulations, without resulting in important changes in physicochemical behaviour. The semisolid rhea oil was fractionated in two successive stages: an olein was obtained at 15 °C, which was refractionated at 10 °C. The thermogram of the olein obtained by cooling at 15 °C does not have the peak found at 34 °C in the thermogram of the original oil and is a softer product than the original oil. A further stage of fractionation of this olein produced a new liquid phase of slightly different thermal behaviour from that of the original olein. This product has a solid fat index around 7% at 15 °C and has melted completely at 20 °C. This second olein has more appropriate physical characteristics than those of the olein obtained from the first fractionation when used in liquid cosmetic formulations.     

Effect of oil viscosity on the rheology of oil-in-water emulsions with added solids

This paper reports an experimental study on the effect of oil viscosity on the rheology of oil-in-water (o/w) emulsions with added solids. Four oils having a viscosity range of 0.0024 to 306 Pa . s were used. The size ratio of the solids to oil droplets was varied from 2 to 16. The addition of smaller size solids to the emulsions yielded a higher viscosity than that of larger solids at the same solids volume fraction. However, when the solids were sufficiently large such that the emulsions behaved as a continuous phase towards the solids, the viscosity of the emulsion-solids mixtures tended to be independent of the solids size. The critical size ratio of the solids to oil droplets, above which the emulsions behaved as a continuous phase towards the solids, increased with the oil viscosity. The critical size ratio varied between 3 and 10.     

Evaporation of pyrolysis oil: Product distribution and residue char analysis

The evaporation of pyrolysis oil was studied at varying heating rates (～1–10⁶°C/min) with surrounding temperatures up to 850°C. A total product distribution (gas, vapor, and char) was measured using two atomizers with different droplet sizes. It was shown that with very high heating rates (～10⁶°C/min) the amount of char was significantly lowered (～8%, carbon basis) compared to the maximum amount, which was produced at low heating rates using a TGA (～30%, carbon basis; heating rate 1°C/min). The char formation takes place in the 100–350°C liquid temperature range due to polymerization reactions of compounds in the pyrolysis oil. All pyrolysis oil fractions (whole oil, pyrolytic lignin, glucose and aqueous rich/lean phase) showed charring behavior. The pyrolysis oil chars age when subjected to elevated temperatures (≥700°C), show similar reactivity toward combustion and steam gasification compared with chars produced during fast pyrolysis of solid biomass. However, the structure is totally different where the pyrolysis oil char is very light and fluffy. To use the produced char in conversion processes (energy or syngas production), it will have to be anchored to a carrier. © 2010 American Institute of Chemical Engineers AIChE J, 2010     

Rheology of oil in water emulsions with added solids

The effect of added solids on the rheology of oil in water emulsions was investigated. The range of the oil concentration, solids free basis, was (0-70%) and the solids volume fraction was (0-0.16). The solids mean diameter was 45 μm and it was about four times larger than the oil droplets. In the absence of added solids, non-Newtonian behaviour was observed for oil concentrations above 40%. The added solids increased the emulsion viscosity in a manner similar to the addition of solids to a homogeneous fluid. The rheological data of all the emulsion-solids mixtures investigated were correlated as relative viscosity versus solids volume fraction, where the relative viscosity is defined as the ratio of the emulsion-solids mixture viscosity to the solids-free emulsion viscosity. In the case of non-Newtonian systems, the emulsion-solids mixture viscosity and the solids-free emulsion viscosity were calculated at the same shear stress. The Barnea and Mizrahi viscosity correlation was found to fit the data well.     

Modelling the temperature dependence of kinematic viscosity for refined canola oil

Viscosities of refined, bleached, deodorized (RBD) and refined, bleached, winterized (RBW) canola oils were measured at temperatures from 4 to 100°C. The viscosities of these refined canola oils were exponentially related to the oil temperature. Viscosity of the RBW oil was slightly greater than that of the RBD oil when the temperature was below 15°C. Compared to refined soybean oil, the canola oils were substantially more viscous. The viscosity of canola oil was modelled asv = exp(C₀ + C₁T + C₂T²). The maximum predicted error was less than 1.6% over the tested temperature range.     

Catalytic conversion of palm oil to fuels and chemicals

The conversion of palm oil to hydrocarbons using a shape selective zeolite catalyst is reported in this work. Palm oil was passed over HZSM-5 catalyst in a fixed bed micro-reactor and the reactor was operated at atmospheric pressure, a temperature range of 360 to 420°C and weight hourly space velocity (WHSV) of 2 to 4 h^?1. The main objective was to study the effect of reaction temperature and oil space velocity on the conversion and selectivity of gasoline range hydrocarbons. The results show that 40 to 70wt% of the palm oil can be converted to aromatics and hydrocarbons in the gasoline, diesel and kerosene range, light gases, coke and water. The maximum gasoline range hydrocarbons yield of 40wt% of total product formed was obtained at 400°C and 2 h^?1 space velocity.     

Gas evolution from the aquathermolysis of heavy oils

Aquathermolysis experiments were performed on core samples taken from three large bitumen and heavy oil deposits found in Alberta, to investigate gas evolution over the temperature range 360 to 420°C. Experiments conducted on Athabasca included runs with an initially pre-oxidized oil sample and runs with a change in core mineralogy. Pre-oxidizing the oil was found to substantially increase the amount of carbon monoxide and molecular hydrogen generated. Core mineralogy played an important role in the generation of carbon dioxide, and the amount of hydrogen sulphide produced was dependent on oil composition, mineralogy and time. Although substantial amounts of gaseous products are produced by simple thermolysis reactions (i.e., without water present), the main thermal recovery methods, steam injection and in-situ combustion, bring the oil phase and its host rock into direct contact with water. As water has been shown to take part in thermal cracking reactions, these experiments provide usful data for the estimation of produced gas composition during thermal recovery projects.     

Effect of process conditions on the microencapsulation of coffee oil by spray drying

Microencapsulation is a good alternative to transform liquid food flavourings, such as coffee oil, into stable and free-flowing powders. Thus the aim of this study was to evaluate the influence of process conditions on the microencapsulation of coffee oil by spray drying, using gum Arabic as encapsulating agent. The effect of total solid content (10–30%), oil concentration with respect to total solids (10–30%) and inlet air temperature (150–190 °C) on the encapsulation efficiency, oil retention, moisture content and powder hygroscopicity were evaluated by a complete 2³ central composite rotatable design. Both encapsulation efficiency and oil retention were negatively influenced by oil concentration and inlet air temperature, and positively affected by total solid content, which could be related to the emulsion viscosity and droplet size. Particles produced at the optimized process conditions (30% of total solids, 15% of oil with respect to total solids and inlet air temperature of 170 °C) were evaluated for oxidative stability and showed to be stable during storage at 25 °C, but not at 60 °C. At this temperature, pure oil presented higher lipid oxidation than encapsulated, confirming the protective effect of microencapsulation on the oxidative stability of this product.     

Thermal degradation of shale oils: 1. Kinetics of vapour phase oil degradation

As vertical modified in-situ retorts (VMIS) have been scaled up and tested, the overall oil yield has declined and is generally lower than that observed in an above-ground process. This reduced oil yield could adversely affect the economics of VMIS retorting. Diminished yields are attributed to a combination of factors associated with scale-up such as in complete rubblization, wide particle size distributions (large blocks of shale), and poor flow distributions. Additionally, oil losses can occur by comparatively long exposure of the oil vapours to high temperatures, by exposure to successive condensation and revaporization of the oil as it travels down the retort, and finally by long time thermal exposure of the condensed oil retained in the bottom portion of large VMIS retorts. To study such vapour phase degradation of shale oil using oil produced from Occidental Petroleum's No. 6 VMIS retort, a tubular continuous flow reactor, with an on-line gas chromatograph for gas composition monitoring was used to study thermal degradation of shale oil under retorting conditions. Oil and a combination of gases including steam were metered into the preheater and then the vapours passed into a quartz tubular reactor where the temperature and residence time of the gaseous mixture were controlled. Complete mass balances were performed giving the weight fraction of oil converted to noncondensable hydrocarbon gases and coke. This experimental design is novel because high temperature thermal degradation of shale oil was studied for the first time under steady state flow conditions with carefully controlled residence time and temperature. A range of temperatures (425–625 °C) and residence times (2–10 s) were used in a series of factorial-designed experiments (3²) to accurately determine the effects of these variables. Results of the study showed that the addition of steam to the carrier gas did not reduce oil degradation losses but did react with the coke thereby changing the product gas composition and quantity. A first-order oil degradation rate expression was used to model the rate of oil loss. The calculated activation energy was 17.3 kcal mol^?1. Chemical analyses of the product liquids and gases confirmed previously reported findings that the oil loss indices (alkene/alkane, ethylene/ethane, naphthalene/(C₁₁ + C₁₂), and gas/coke) increase with increasing oil degradation.     

Modeling the moisture sorption isotherms of two‐phase solid olive oil by‐product

The moisture sorption isotherms of two‐phase solid olive oil mill by‐product (SOB) were measured at different temperatures (15–50 °C) in order to thoroughly know the hygroscopic properties of this material. SOB is like a slurry with a high water content (60–70%). It is obtained in the olive oil two‐phase extraction process and is currently used as the raw material for obtaining pomace oil by extraction with hexane; prior to the extraction, drying of the SOB is required. Other uses of SOB are composting, animal feeding and solid fuel; in such cases, the previous drying of the material is also required. Sorption moisture isotherms for the two‐phase SOB were obtained by a static method. Eight models were fitted to the experimental data: BET, GAB, Halsey, Smith, Henderson, Oswin, Ferro‐Fontan and Peleg. The GAB equation was the best option to describe the water sorption behavior of SOB within a very wide range of water activities (0–0.90). A generalized GAB model, in which temperature is taken into account, was obtained by multivariable fitting of the complete set of the experimental isotherms.     

STUDIES OF TRANSESTERIFICATION OF KARANJA (Pongamia pinnata) OIL IN A PACKED BED REACTOR

Studies were made to determine the influence of different reaction temperatures and residence times on biodiesel yield by transesterification of karanja oil (Pongamia pinnata) in the presence of methanol using a solid acid heterogeneous catalyst in a continuous process. Recycle runs were conducted by further transesterification of the organic phases (first run mixture of methyl ester and unconverted oil) in the presence of methanol under similar conditions. High-pressure liquid chromatography (HPLC) reveals poor biodiesel yield even with an increase in the reaction temperature and residence time in the first run. Biodiesel yield obtained from the recycle runs, however, was greatly increased over that of the first-run biodiesel yield. Recycle transesterification at a reaction temperature of 240°C and residence time of 50 min gives a maximum yield value of 97.74%. Consequently, irrespective of the presence of high free fatty acids and other impurities in karanja oil, recycling the organic phase of the first run significantly enhances the biodiesel yield.     

混合废塑料与焦化蜡油共催化裂解制取燃料油

以混合废塑料和焦化蜡油为原料,共催化裂解制备燃料油,克服了废塑料裂解中塑料粘稠度大且传热效率低、裂解炉中温度极不均匀、反应时间长、气体和固体收率高、液体收率低和易结焦等难题。详细考察焦化蜡油与混合废塑料质量比和催化剂用量对产物组成的影响以及FCC催化剂的重复使用性能。结果表明,在焦化蜡油与混合废塑料质量比为2、FCC催化剂用量为混合废塑料质量的10%、终温460 ℃并保持4 h条件下,燃料油收率达到96.67%,气体收率和釜残率分别仅有0.27%和1.53%。焦化蜡油的添加使液相产物中重组分增多,轻组分减少。FCC催化剂的重复使用性能好,催化剂重复使用5次,液体收率大于85%。采用混合废塑料与焦化蜡油共催化裂解的工艺不仅为“白色污染”的处理开辟了一条新途径,而且扩大了焦化蜡油的应用范围。     

Understanding weathering of oil sands ores by atomic force microscopy

Effect of weathering on colloidal interactions between bitumen and oil sands solids was studied by atomic force microscopy (AFM). The change in bitumen chemistry due to weathering was found to have a negligible effect on the interactions of bitumen with solid particles. However, the increase in solid surface hydrophobicity due to ore weathering reversed the long‐range interaction forces between bitumen and solids from repulsive to attractive with a corresponding increase in adhesion force. The measured force profiles between bitumen and various solids can be well fitted with the extended DLVO theory by considering an additional attractive force. The attractive long‐range force and increased adhesion force make the separation of bitumen from solids more difficult and the attachment of fine solids on liberated bitumen easier, thereby leading to poor bitumen liberation and lower aeration efficiency. Such changes account for the observed poor processability of the weathered ores. © 2009 American Institute of Chemical Engineers AIChE J, 2009     

Potential margarine oils from genetically modified soybeans

Genetically modified soybeans were processed into finished, refined, bleached, and deodorized oils. Fatty acid composition was determined by gas-liquid chromatography. Glyceride structure was characterized according to degree of unsaturation by high-performance liquid chromatography, lipase hydrolysis, and gas-liquid chromatography. Compared to common varieties with 15% saturated acids, genetically modified soybeans yielded oils containing 24–40% saturated acids. Several varieties were examined, including the Pioneer A-90, Hartz HS-1, and Iowa State A-6 lines. Pioneer A-90 contained 17% stearic acid, had a solid fat index (SFI) of 6.0 at 10°C (50°F) and zero from 21.1 to 40°C (70 to 104°F), and therefore lacked sufficient solids for tub-type margarine. To improve its plastic range, the Pioneer oil was blended with palm oil, randomized palm oil, or interesterified palm/soy trisaturate basestock. After blending with 10–40% of these components, the high-stearic acid oil had an SFI profile suitable for soft tube margarine. The A-6 varieties, 32–38% saturates, showed SFI profiles with sufficient solids at 10°C (50°F) and 21.1°C (70°F) to qualify as a stick-type margarine oil, but lacked sufficient solids at 33.3°C (92°F); however, after small amounts (2–3%) of cottonseed or soybean hardstocks were added, the A-6 oils qualified as stick margarine oil. The HS-1 variety, when blended with small amounts (2–3%) of hardstock, possessed sufficient solids at 10°–33.3°C (50–92°F) to prepare soft tub margarine oil. Presented at the AOCS Annual Meeting & Expo, San Antonio, Texas, May 8–12, 1995.     

Dilatometric investigations of fats

Summary 1. Dilatometric curves have been determined over the complete melting range for samples of prime steam lard, oleo oil, all-hydrogenated vegetable shortening, and partially hydrogenated cottonseed oil. From the dilatometric data estimates have been made of the percentages of solids and liquid in the fats at different temperatures. 2. Estimates of the percentages of solids and liquid in the hydrogenated cottonseed oil agreed with those previously reported on the same oil from calorimetric data when allowance was made for a lack of equilibrium conditions in the calorimetric experiment. Since a condition of equilibrium between solids and liquid is attained in the dilatometer, this instrument is to be preferred to the calorimeter for determining the composition of fats in terms of the two phases. 3. The consistency of the fats, as measured by micropenetrations, was different for different fats which contained equal percentages of solids. The consistency, therefore, is not determined solely by the amount of solids present, but also by the character of the solid particles. One of the laboratories of the Bureau of Agricultural and Industrial Chemistry, Agricultural Research Administration, U. S. Department of Agriculture.     

Supercritical fluid extraction of sunflower seed oil with CO2-ethanol mixtures

The effect of ethanol addition to supercritical carbon dioxide (SC-CO₂), up to 20%, on sunflower seed oil extraction over the range of 150 to 350 bars and 42 to 80°C was studied. A nonrecirculating home-made bench-scale system was used as extraction equipment. The oil-SC-CO₂-ethanol mixture was reduced to atmospheric pressure in a test tube, where two phases, oil and ethanol, were obtained and ethanol-saturated CO₂ was liberated to the atmosphere. Results show that sunflower oil solubility in SC-CO₂ greatly increases with addition of ethanol as entrainer over the whole range of pressure and temperature conditions. Some phospholipids are co-extracted at levels directly proportional to the added ethanol. Moreover, a large amount of phospholipids was recovered in the ethanolic phase. Acidity of the extracted oil with ethanol as entrainer was lower than that without alcohol. Part of the free fatty acids was found in the ethanolic phase.     

Effect of particle size and shape on settling using an integral approach

This study was undertaken to investigate a settling system having no chemical interactions between the liquid and solid in an effort to establish a base for analysis of the more complex coal—oil systems that have great potential to be used as a fuel in boilers. Glass spheres and crushed glass particles in a model oil having similar properties to No. 6 fuel oil were employed. Particle size and shape, concentrations of solids, temperature and initial mixture heights were studied by use of Smiles integral analysis for settling. A pseudo-diffusion coefficient was determined which predicted the settling behavior over the entire settling time.