Effect of the Addition of Waxes on the Crystallization Behavior of Anhydrous Milk Fat

Physicochemical characteristics of lipid-based foods depend, among other factors, on the microstructure and the characteristics of the lipid network formed during crystallization. The objective of this study, was to evaluate the effect of the addition of sunflower oil waxes on the crystallization and melting behavior of anhydrous milk fat (AMF), a lipid with a low content of palmitic and trans-fatty acids. The crystallization and melting behavior of AMF alone and with the addition of 0.25 and 0.5% of waxes was studied using a differential scanning calorimeter. The morphology of the crystallized samples was evaluated with a polarized light microscope. The addition of waxes induced and promoted the crystallization of AMF at high temperatures (>25 °C) as evidenced by lower induction times of crystallization and higher crystallization and melting enthalpies. In addition, smaller crystals and different morphologies were obtained when AMF was crystallized with the addition of waxes. These results suggest that waxes could be used as an additive to modify lipid networks and their physicochemical characteristics, such as texture, smoothness and mouthfeel.     

An investigation of the dependence of penetration on the temperature and composition of paraffin waxes

A general penetration/temperature function for paraffin waxes was derived for the temperature range from 25 °C to 40 °C. In this function each individual temperature is entered as the difference to the theoretical melting temperature of the n‐alkanes of the mixture. The theoretical melting temperature of the n‐alkanes was determined based on the results of a gas chromatography (GC) analysis. The dependencies of the parameters of this function were investigated on the basis of the GC and differential scanning calorimetry data of the slack wax, paraffin waxes and the urea adducts obtained from paraffin waxes with different gradations. Particularly the influence of crystallinity as a link between composition and physical properties was considered in this context. Crystallinity was defined as the ratio of the melting enthalpy of the respective product to the melting enthalpy of the n‐alkanes it contained, with ideal crystallisation assumed. It was demonstrated that, in addition to crystallinity, the chain length of the n‐alkanes also plays a decisive role in the penetration/temperature behaviour.     

Separation of different paraffin wax grades using two comparative deoiling techniques

One stage fractional crystallization and solvent percolation techniques have been used to separate different grades of paraffin waxes; with different characteristics; from El-Ameria light, middle and heavy slack waxes. The two deoiling techniques were performed using ethyl acetate and butyl acetate solvents at ambient temperature of 20 °C, at different dilution solvent ratios (S/F by weight) ranging from 2:1 to 8:1 and constant washing solvent ratio of 2:1 for the first technique and at different percolation solvent ratios ranging from 4:1 to 14:1 for the second one. The resulting data revealed that fractional crystallization technique is more suitable for deoiling the heavy slack wax using butyl acetate solvent than the percolation technique. While, percolation technology is a preferable technique using ethyl acetate or butyl acetate solvent for separation of paraffin waxes from light and middle slack waxes.     

Crystallization of waxes in sunflowerseed oil: Effects of an inhibitor

The mechanism of action of a commercial inhibitor on the crystallization of waxes present in sunflowerseed oil was analyzed. The results showed the inhibitor favored nucleation, leading to a decrease in the amount of waxes available for the growth of the crystals already formed. The inhibitor decreased the crystal size, increased the number of crystals and possibly caused slower crystallization of waxes.     

Physical Properties of Beeswax,Sunflower Wax,and Candelilla Wax Mixtures and Oleogels

To be able to tailor and optimize the physical properties of oleogels for various food applications, more information is needed to understand how different gelators interact. Therefore, the objectives of this study were to evaluate the interactions between binary mixtures of beeswax (BW), candelilla wax (CLW), and sunflower wax (SFW) in pure form as well as in 5% wax oleogels made with soybean oil, in terms of their crystallization and melting properties, crystal morphology, solid fat content, and gel firmness. CLW:BW mixtures had eutectic melting properties, and oleogels from these mixtures with 40:60 to 90:10 CLW:BW were firmer compared to oleogels made with one wax. The main components in SFW and BW appeared to cocrystallize or crystallize at the same temperature, but nonlinear changes in melting point and solid fat content profile of oleogels prepared with the mixed waxes indicated that SFW dominated oleogel formation. In addition, oleogels prepared with mixtures of SFW and BW had lower firmness compared to oleogels prepared with one wax, indicating an incompatibility between the two waxes. The main wax components in SFW and CLW never cocrystallized, and low levels of CLW appeared to prevent SFW from forming a crystalline platelet network. This resulted in low firmness of oleogels made from mixtures of 90:10 to 60:40 SFW:CLW compared to oleogels prepared with one wax. However, the firmest oleogels of all mixtures were made from 10:90 SFW:CLW. Changes in gel firmness and melting properties with mixed wax oleogels were likely to be due to changes observed in the crystal size and morphology. In addition, the firmest gels were shown to result from mixtures that were predicted to have >40% hydrocarbon content, and a high hydrocarbon to wax ester ratio, but minor components such as free fatty acids and fatty alcohols may have also influenced firmness.     

Dry fractionation of coconut oil by melt crystallization

Layer melt crystallization was applied for the dry fractionation of multi-component mixtures using coconut oil as a model substance. The aim of the experiments was to optimize the crystallization parameters (e.g. crystallization temperature, melt temperature, cooling rate, agitation speed) in order to obtain the solid fraction with a higher melting temperature and solid fat properties. The isothermal crystallization behavior of coconut oil was investigated via differential scanning calorimetry (DSC). The efficiency of the crystallization process was monitored by determining the melting point and solid fat content (SFC) of the fractionated products. The morphology of crystal layer was studied by a light microscope. Cool finger temperature was found to have the greatest impact on product properties. Applying a cooling rate of 0.2 K/h resulted in sufficient growth rates providing the required products. The micrographs of the solid fraction revealed lamellar particle arrangement compared to coconut oil possessing spherulites.     

高效固体防蜡剂的研制与试验

长庆油田X区块结蜡周期短,蜡质碳数在C10-C51之间,峰值在C39左右,呈现出蜡质碳数较高、蜡分子稳定性强的特点,常规防蜡剂防治困难,存在针对性强、适应性差的问题。针对X区块原油及蜡质特征,实验室合成的3种防蜡剂并进行防蜡率评价,应用气相色谱法对不同碳数范围的蜡样进行了防蜡剂防蜡效率的分析,确定出了固体防蜡剂的主剂B,可以适应C15-C51的蜡质;将低熔点EVA-01和高熔点LD-01的骨架材料复配,测试不同比例下的溶释速率,确定出两者最佳比例为2.5∶1;通过分析主剂B、分散剂FSJ-01加量的影响,确定出了固体防蜡剂的配方:10%B+85%(EVA-5/LD-03(2.5∶1))+5%FSJ-01。该防蜡剂在20mg·L~(-1)时,防蜡率为62.3%,使原油析蜡点降低6.1℃。现场试验表明:固体防蜡剂可以降低油井载荷,延长结蜡周期,取得了较好的防蜡效果。     

Influences of the chemical defects on the crystal thickness and their melting of isothermally crystallized isotactic polypropylene

Ziegler-Natta and Metallocene Catalysis isotactic polypropylene with different chemical defects were isothermally crystallized at various crystallization temperatures. The crystal thickness and their corresponding melting behavior were studied using small angle X-ray scattering, atomic force microscopy, optical microscopy, and differential scanning calorimetry. The equilibrium melt temperature of the samples was calculated from the Hofmann-Weeks extrapolation for the supercooling. Two lamellar populations were distinctly observed in all cases during the crystallization process. Relatively thicker and stable lamellar crystals which melt at higher temperatures were observed with lowering the supercooling and found catalysis dependence in these crystals. During melting, no significant recrystallization of the samples has been detected for higher crystallization temperature where recrystallization processes enhance the lamellae thickness. The melting of the crystals has found strong dependence with the crystallization temperatures, the catalysis process and the nature of the defects present in the isotactic polypropylene. The increase of the crystal lamellae thickness and their melting temperature might be presumably related with the chain folding mechanism as well as the stability of the crystals formed during the isothermal crystallization process. A combined plot of SAXS and DSC results is demonstrated for the equilibrium melting temperature followed by critical analysis of the results.     

Factors affecting the nascent structure and morphology of polyethylene obtained by heterogeneous Ziegler—Natta catalysts: 2. Crystallinity and melting behaviour

Following studies of the factors affecting the structures and morphologies of nascent polyethylene crystals, density, heat of fusion, crystallinity and melting behaviour of the samples as-polymerized and also after nitric acid oxidation and annealing, were determined by density gradient column, X-ray diffraction and differential scanning calorimetry. The results show that the polymerization temperature is the most important factor controlling the crystal structure. The highest density, crystallinity and crystal quality were found for polymerization temperatures under 100°C, where the growth of the crystals was controlled by a successive polymerization and crystallization mechanism. For this range of polymerization temperatures, density and crystallinity decrease as the polymerization temperature and time increase. When the polymerization temperature is higher than 100°C, near the polyethylene solubility, the crystal grows without any polymerization control, according to a separate polymerization and crystallization mechanism. In this case, density and crystallinity increase with polymerization temperature and time, as with crystallization from melt and solution. The density and crystallinity values of all nascent polyethylene crystals are in the typical range of folded-chain drawn polyethylene or crystallized from the melt. Furthermore, no as-polymerized crystals exhibit a superheating effect suggesting a folded-chain macroconformation. From the melting depression for folded-chain crystals and extended-chain paraffin crystals with finite dimensions, and also from the molecular weight after nitric acid oxidation, the crystal thickness could be calculated. The values are within the range of folded-chain melt crystallized polyethylenes. The results indicate that the crystal thickness of the samples polymerized at below 100°C increases as the polymerization temperature decreases. For the samples polymerized at above 100°C, the crystal thickness increases with the polymerization temperature.     

A油田油井结蜡机理及清防蜡对策研究

针对A油田油井全井段结蜡的特殊性,从影响结蜡的主要因素入手,分析了原油组分、原油含蜡量,蜡样成分;同时考虑压力与气油比对析蜡温度的影响,采用高温高压釜与石蜡沉积激光检测仪分析了不同压力、不同气油比下析蜡点,掌握了A油田全井段结蜡的主要原因,得出了原油析出蜡主要以微晶蜡为主,而且熔点较高,不宜采用热洗方法清蜡。针对这一点,现场开展了防蜡防垢降粘增油器、声波防蜡器、空化防蜡器三种防蜡工艺对比试验;室内评价了长庆油田目前在用的五种清蜡剂对A油田的适应性。优选出适合A油田的防蜡工具和化学清蜡剂,对该油田清防蜡工作的开展有一定的技术指导意义。     

添加剂对石蜡物理性质的影响

针对两种棕榈蜡对石蜡的熔点、低熔点、粘度、针人度的影响进行了比较,表明两种添加剂虽然同为棕榈蜡,但对石蜡的各项指标(熔点、滴熔点、粘度、针入度)的影响具有不同的效果,这是由于两种棕榈蜡产地不同导致性质不同所造成的.     

Solid-state reorganization,melting and melt-recrystallization of conformationally disordered crystals (α′-phase) of poly (l-lactic acid)

Conformationally disordered α′-crystals of poly (l-lactic acid) were formed by crystallization of the melt at high supercooling at 95 °C. Analysis of their melting temperature as a function of the crystallinity revealed absence of crystal thickening during isothermal crystallization. Annealing of α′-crystals between the crystallization temperature of 95 °C and their zero-entropy production melting temperature of 150 °C leads to their stabilization, mainly by solid-state reorganization. Heating faster than 30 K s⁻¹ suppresses reorganization and permits superheating of the α′-phase. Consequently, isothermal melting followed by melt-recrystallization becomes accessible. Melting is completed within few hundreds of milliseconds, and melt-recrystallization is about two orders of magnitude faster than crystallization of the isotropic melt at identical temperature. The time required for melting decreases with superheating and increases with the lateral dimension of the lamellar crystals. Laterally extended lamellae require long time for melting of the outer crystal layers, which allows stabilization of the central crystal part. These crystal remnants then serve as seed for immediate recrystallization. In case of complete melting of smaller lamellae, melt-recrystallization is retarded but still distinctly faster than cold- and melt-crystallization, due to incomplete isotropization of the melt.     

Studies on the crystal growth of rice bran wax in a hexane medium

Rice bran oil (RBO) is well known for its high wax content (2–4%). A good separation of waxes must be ensured through the formation of crystals that can be removed with a minimal retention of oil to maintain high yields of refined oil. In the present study, the form and size distribution of RBO wax crystals were investigated using a laser diffraction technique. An attempt was made to study the effect of cooling on growth and size distribution of RBO wax crystals in hexane medium, and it showed that high cooling rate and low temperature induces the formation of a great number of small nuclei. In addition, experiments were performed to evaluate the effect on the growth of wax crystals of successive additions of gum and pure TG to the medium. The entire experiment was designed to optimize the temperature and incubation time of wax crystallization to facilitate the efficient separation of wax from crude RBO-hexane miscella using membrane technology.     

静态熔融结晶法提纯均四甲苯（英文）

The purification and separation of durene from the mixture containing durene isomers were studied. Since the boiling points of tetramethyl benzene isomers are very close but their melting points are of great differences, stat-ic melt crystallization was applied to separate and purify durene from its isomers. Crystallization experiments were carried out under various operating conditions. The effects of cooling rate, crystallization temperature, sweating temperature and sweating time on the yield and purity of crystal were investigated. Orthogonal exper-imental design method was adopted to analyze the factors that may affect the yield of durene. Under the optimal crystal ization conditions, the purity of durene could reach as high as 99.06%with the yield of 75.3%through one crystal ization process. By fitting purification data based on sweating time in isothermal operations, the purifica-tion rate coefficient was obtained.     

Biodegradation of slop wax by Bacillus species isolated from chronic crude oil contaminated soils

Slop wax waste by-product obtained through the lube oil manufacture was subjected to biotreatment using five isolated Bacillus species at 30 °C and various incubation periods, 7, 14 and 21 days. The results obtained from HPLC for the 15 samples showed that the aromatic contents decreased, especially, for that treated with Bacillus sp. MAM-27 which degrade PAHs faster at 1% (w/v) concentration of slop wax waste by-product and exhibited high biodegradation ability within 1 week. Bacillus sp. MAM-27 degraded 99.9% of PAHs, while Bacillus sp. MAM-24 degrades 99.8% of PAHs within 2 weeks and then the degradation ability is slightly increased afterwards. The gas chromatographic analysis of the samples before and after treatment with Bacillus spp. showed that, the aromatics, naphthenes and iso-alkanes were more degradable than saturated n-paraffins. Treatment by Bacillus sp. MAM-27 and Bacillus sp. MAM-24 can be an effective method for biodegradation of slop wax waste by-product leading to paraffin waxes match with plastic paraffin wax according to USSR 1121284 specifications.     

Sintering of fat crystal networks in oil during post-crystallization processes

Several foods contain semi-solid fats that consist of solid crystals dispersed in a liquid oil. In oil-continuous margarine, butter, and chocolate, fat crystals determine properties such as consistency, stability against oiling-out, and emulsion stability. Trends toward foods with less fat and/or less saturated fat create a need for understanding and controlling the properties of fat crystal dispersions. Fat crystals form a network in oil due to mutual adhesion. One source of strong adhesion is formation of solid bridges (sintering), which has been studied in this work through sedimentation and rheological experiments. Results indicate that sintering may be created by crystallization of a fat phase with a melting point between that of the oil and the crystal. Generally speaking, β′ crystals were sintered by β′ fat bridges, favored by rapid cooling, and β crystals by β fat bridges, favored by slow cooling. The existence of the same polymorphic form of the crystal and bridge indicated that solid bridges, rather than bridges formed by small crystal nuclei, were formed. A maximum in sintering ability for an optimal sintering fat concentration occurred due to competition between bridge formation and other crystallization processes. Some emulsifiers influenced the sintering process. For example, monooolein made it more pronounced, while technical lecithin had the opposite effect.     

Properties of Oleogels Formed With High‐Stearic Soybean Oils and Sunflower Wax

In an effort to develop alternatives for harmful trans fats produced by partial hydrogenation of vegetable oils, oleogels of high‐stearic soybean (A6 and MM106) oils were prepared with sunflower wax (SW) as the oleogelator. Oleogels of high‐stearic oils did not have greater firmness when compared to regular soybean oil (SBO) at room temperature. However, the firmness of high‐stearic oil oleogels at 4 °C sharply increased due to the high content of stearic acid. High‐stearic acid SBO had more polar compounds than the regular SBO. Polar compounds in oil inversely affected the firmness of oleogels. Differential scanning calorimetry showed that wax crystals facilitated nucleation of solid fats of high‐stearic oils during cooling. Polar compounds did not affect the melting and crystallization behavior of wax. Solid fat content (SFC) showed that polar compounds in oil and wax interfered with crystallization of solid fats. Linear viscoelastic properties of 7% SW oleogels of three oils reflected well the SFC values while they did not correlate well with the firmness of oleogels. Phase‐contrast microscopy showed that the wax crystal morphology was slightly influenced by solid fats in the high‐steric SBO, A6.     

Separation of some paraffin wax grades using solvent extraction technique

Solvent extraction technique has been used to separate paraffin wax grades; with different characteristics; from El-Ameria light, middle and heavy slack waxes. The wax deoiling has been done by solvent extraction at different extraction temperatures and different solvent feed ratios (S/F by weight). The extraction solvents used are furfural, N-methyl-2-pyrrolidone (NMP) and N, N, dimethylacetamide (DMA). The wax products are evaluated according to TAPPI-ASTM equation and petroleum wax specifications. The data revealed that DMA and NMP are suitable extracting solvents for isolating of semi- and scale-refined grades of paraffin waxes from light and middle slack waxes. But furfural solvent can separate only semi-microcrystalline waxes from heavy slack wax.     

Fractional crystallization on cooled walls: Separation efficiency with a growing crystal layer, its diffusion washing, and partial melting

The redistribution of components in the crystal layer-melt system at the main stages of fractional crystallization on cooled walls is studied. Mathematical solutions that can be used for calculating the fraction of trapped melt and the value of effective distribution (partition) coefficient in the crystallization of systems of different types are obtained. The kinetics of diffusion of impurities and migration of liquid inclusions under the action of temperature gradients at the growth and diffusion-washing stages of a two-phase crystal layer is studied. Simple relations for calculating the holdup of a melt and the maximal degree to which the main component can be purified in the partial melting (sweating) of crystal layers are derived. The theoretical results are compared with the experimental data obtained in the fractional crystallization of organic mixtures and freezing of aqueous solutions. Comparative analysis of the efficiency of the studied stages of fractional crystallization is accomplished and some practical recommendations are formulated.     

提高低熔点蜡品质的研究

文章介绍了低熔点蜡的性质,提出利用和开发途径。采用发汗切割脱油工艺对原料进行预处理,选择合适馏分调合,经白土精制后,进行封油性和改善光安定性试验,开发优质半精炼石蜡,为企业争创更大的经济效益。