氯化钠晶体粒度对二次成核的影响

实验主要研究在悬浮状态下搅拌速率和母晶平均粒度对氯化钠成核速率特征、规律及新晶核粒度分布的影响.研究结果表明:在实验条件下,90%左右晶体仍保持原来粒度.在母晶平均粒度一定时,成核速率随搅拌速率的增大而增大,且母晶平均粒度较大时这种趋势更加明显.在搅拌速率一定时,成核速率随母晶平均粒度的增大而增大,且在母晶平均粒度较大时这种趋势更加明显.在母晶平均粒度一定时,搅拌速率增大,晶核的粒径分布中最大质量分率所对应的粒径呈减小趋势.在母晶平均粒度一定时,搅拌速率增大,破碎晶核的中值粒径逐渐减小.     

操作条件对DTB流化床结晶器内CFD状态的影响

运用计算流体力学方法对DTB流化床结晶器内循环流量对流体悬浮状态的影响以及不同粒径颗粒在出口处固体质量流率的变化情况进行模拟.模拟结果表明,保持进料流量一定的情况下,外循环流量与进料流量的比值也对结晶器内流体的体积分数分布情况有着显著的影响,然而,循环流量的加大也会增加结晶器内颗粒的碰撞与破碎的几率,不利于晶体的成核与成长.另外一组模拟结果还表明,不同粒径的颗粒在各出口处的质量流率差异明显,本模拟条件下,粒径为0.5 mm以下固相颗粒基本上由循环出口排出,而粒径0.5 mm及以上的固相颗粒则能够在导流筒与档板之间循环流动,这意味着在一定条件下,能够控制一定粒径的颗粒在结晶器内的悬浮流动,这对于控制一定粒径范围的晶体的成核与成长有着重要的作用.     

晶浆黏度对谷氨酸结晶晶习及粒度分布的影响

用不同浓度的蔗糖溶液制备不同黏度梯度的溶液,考察了黏度对谷氨酸结晶晶习及粒度分布的影响,并通过测定不同黏度条件下谷氨酸结晶诱导期时间及生长速率的变化,探寻了黏度对谷氨酸结晶的影响机理。实验表明,在实验所测的黏度范围(1.00～10.30mP·s)内,黏度对谷氨酸的晶习基本没有影响,在相同过饱和度下,黏度增加,谷氨酸结晶诱导期时间延长,结晶成核速率减小,谷氨酸晶体的生长速率减小,使得谷氨酸晶体的颗粒直径减小,但晶体粒度分布均匀性略有增加。在工业生产上可以适当地提高结晶温度,以降低溶液的黏度,缩短结晶的诱导期时间,提高晶体的生长速率,使其更有利于谷氨酸的结晶。     

双轴搅拌对晶粒降温结晶的影响

工业结晶过程中，一般希望结晶产物具有均匀的粒度和规则的晶形。考虑到带有外桨的双轴搅拌器能有效促进结晶过程的传质与传热，因此课题组以双轴搅拌器作为研究对象，通过实验考察了转速、桨型以及内外桨搅拌模式等参数对结晶产物粒度分布及晶型晶貌的影响；根据不同转速下测得的晶体成核生长动力学参数，建立氯化钾结晶成核速率与生长速率的预测公式。结果表明：双轴搅拌得到的晶体中值粒径明显高于单轴搅拌，但由于外桨的存在，使得粒度分布离散度变大；存在一个最佳转速使晶体中值粒径达到最大且粒度分布较为集中；内外桨同转、桨叶选用轴流桨或混流桨时更适用于结晶操作。氯化钾结晶成核速率与生长速率的预测公式为工业结晶提供一定的理论参考。     

氢氧化镁结晶动力学研究

结晶动力学的研究是结晶器设计、结晶过程放大和优化的重要依据。文章研究了间歇反应过程中氢氧化镁结晶动力学,采用间歇动态法对结晶过程基本参数进行测试,根据粒数衡算和质量衡算关系,利用晶体成核生长经验公式拟合出氢氧化镁反应结晶动力学表达式。结果表明:氢氧化镁结晶过程晶体生长速率与粒度无关,得到了过饱和度、悬浮密度与成核速率之间的关系。     

L-乳酸钙间歇结晶粒度的研究

研究了十二烷基苯磺酸钠作为添加剂对L-乳酸钙间歇结晶晶体粒度的影响,研究结果表明:十二烷基苯磺酸钠的加入增大了L-乳酸钙结晶过程的界面能,从而抑制自发成核过程的发生,促进晶体的生长,改善晶体的粒度.以十二烷基苯磺酸钠作为添加剂,在添加剂量为80mg/kg时,晶体的平均粒径分别为236μm,结晶温度对L-乳酸钙晶体的粒度有重要影响,正交试验的最佳结晶控制条件为:添加剂加入量80mg/kg、结晶温度39%,搅拌速率220r/min,晶种加入量为溶液质量的2.5‰,降温速率10%/h.     

搅拌操作对L─谷氨酸结晶晶型的影响

搅拌强度对L─谷氨酸结晶的α和β晶型的比例有明显的影响。在不太大的搅拌强度下，提高搅拌强度能明显提高α晶型的相对含量。其机制是搅拌强度增大能显著提高α晶型的成核频率因子和二次成核速率。而搅拌强度超过一定限度则会使β含量有所提高。同时，还发现挡板对α的生成也有促进作用。在不加晶种的结晶操作中，先采用较高的搅拌强度起晶后再采用较低的搅拌强度有晶有利于得到粗大，均匀的α晶体。     

搅拌操作对L—谷氨酸结晶晶型的影响

搅拌强度对Ｌ－谷氨酸结晶的α和β晶型的比例有明显的影响。在不太大的搅拌强度下，提高搅拌强度能明显提高α晶型的相对含量。其机制是搅拌强度增大能显著提高α晶型的成核频率因子和二次成核速率。而搅拌强度超过一定限度则会使β的含量有所提高。同时，还发现挡板对α的生成也有促进作用。在不加晶种的结晶操作中，先采用较高的搅拌强度起晶后再采用较低的搅拌强度育晶有利于得到粗大，均匀的α晶体。     

氨-水体系中硝酸钾结晶的生长特性

采用MSMPR结晶器研究了不同悬浮密度、氨水浓度和过饱和度下,KNO3在氨-水体系中的结晶动力学特性,并得到KNO3在氨水溶液中的结晶动力学模型.研究结果表明:随着悬浮密度的减少,晶体平均粒径增大,粒径分布变得均匀;氨的浓度增加,结晶成核 速率与生长速率均下降,晶体平均粒径减少,但粒径分布变均匀;随着过饱和度的加大,结晶成核速率与生长速率均增加,但晶体平均粒径减小,且粒径分布变差.研究结果可为硝酸钾生产工艺中结晶器的设计提供基础数据.     

平面蒸发条件对再制盐特性影响的研究

结晶是化工生产过程中的一个重要的单元操作,结晶过程控制多以获得高质量和适宜粒度的产品为目的.实验研究了平面蒸发方法制备氯化钠再制盐过程中的蒸发速率、停留时间及搅拌频率对产品特性的影响.结果表明:沸腾蒸发条件下,晶体成核速率较快,再制盐多为立方体晶习.当蒸发速率为14 mm/h时,再制盐平均粒径为800 μm,晶体产品粒径均匀.停留时间对再制盐片晶厚度影响较大,停留时间越长,片晶越厚.搅拌频率越大,晶体产品平均粒径越小,且在高搅拌频率下再制盐易形成立方体晶习.无搅拌的条件下,停留时间为10 h时,再制盐平均粒径为827.0 μm,堆积密度为0.749 g/mL,粒度分布较均匀,为500μm～ 1500 μm.     

Secondary nucleation studies on alpha lactose monohydrate under stirred conditions

Secondary nucleation is the dominant source of nuclei at the industrial scale. Traditionally, secondary nucleation has been expressed empirically as a function of stirrer speed and magma density with little or no understanding about the role of individual mechanisms (attrition and contact). This study considers the various mechanisms of secondary nucleation of alpha-lactose monohydrate crystals and link them to either crystal–crystal or crystal-impeller collisions. An agitated system was used to conduct trials at various levels of stirring speed (400 and 550 rpm), seed size (150, 250, 357 and 502 μm) and seed loading (2%, 5% and 10%, v/v) at a constant supersaturation. Crystal-impeller contacts are proposed to be the major source of secondary nucleation. It was found that the kinetic energy and not the collision frequency govern the rate of secondary nucleation with a threshold kinetic energy value below which no secondary nucleation occurs.     

不同溶氧量下功率超声波控制成核对过氧化氢酶溶液冷冻干燥的影响

功率超声波是一种能有效触发溶液初始成核的方法,能够使随机自发的冰晶成核过程转变为可预测的、易于控制的过程。本研究采用平板接触超声法对不同溶氧量的过氧化氢酶（catalase,CAT）溶液进行超声波控制成核并冷冻干燥,考察溶液充气法用于超声波控制成核在升华干燥速率、孔隙率、酶活力回收率方面的影响。结果显示：在4.10～13.44 mg/L溶氧范围内超声波控制成核,随着溶液中溶氧量的增加,升华干燥时间缩短了9.36%～41.63%;4.10～10.24 mg/L溶氧量的CAT溶液的酶活力回收率均高于95%。充气法用于功率超声波控制成核,辅助食品药品的真空冷冻干燥,对于缩短冷冻干燥时间、减少能耗、提高冻干产品的品质等具有积极意义。     

Analytical Techniques for Nucleation Studies in Lipids: Advantages and Disadvantages

ABSTRACT: Crystallization is generally considered a 2-step process. The 1st step, nucleation, involves the formation of molecular aggregates with a critical size great enough to become stable. During the 2nd step, nuclei grow and develop into crystals. Distinguishing between nucleation and growth constitutes a major challenge in lipid crystallization studies. Thus, it is of great importance to discuss the information obtained from the different techniques that are usually used to study nucleation behavior such as nuclear magnetic resonance (NMR), differential scanning calorimetry (DSC), rheological techniques, light-scattering techniques such as turbidimetry and scanning diffusive light scattering (SDLS), polarized light microscopy (PLM), and laser polarized optical sets such as laser polarizedlight turbidimetry (LPLT). Techniques to describe the nucleation process must be very sensitive to disregard growth. When crystallization is followed by methods such as DSC, NMR, and rheological measurements, at times, small amounts of crystals are present in the melt before any solids are detected. Clearly, at this stage, well beyond the induction time for nucleation (τ), these methods are measuring crystal growth. Techniques of low sensitivity for solid fat contents lower than 0.1% must not be used to evaluate nucleation effects. Sensitive turbidimeters with detectors that saturate below 0.3% solid fat content give good results as do scanning diffusive light-scattering equipment. Although the PLM technique is sensitive enough for these kinds of studies, an understanding of important basic concepts is essential. Laser optical sets are the most appropriated methods to study nucleation in fats systems.     

Crystallization kinetics of emulsified triglycerides

Nucleation and crystal growth process of triglycerides in water emulsions composed of trimyristin (c l4:0) admixed with 0, 40, and 80 ml litre^?1 trilaurin (c 12:0) (expressed v per total v emulsion) were followed with NMR (nuclear magnetic resonance) and DSC (differential scanning calorimetry). Mathematical analysis of the time dependence of the phase changes and thermal data distinguished two distinct ‘apparent’ kinetic phases. These phases were tentatively referred to as nucleation and crystal growth. With 40 and 80 ml litre^?1 trilaurin (NMR data at 293 K) nucleation and crystal growth phases of trimyristin were simulated with zero order and second order rate expressions, respectively. Relative to these mixtures, pure trimyristin nucleation was delayed in the initial phase, but crystal growth occurred with fast homogeneous nucleation and slower growth in the second phase. Statistical analyses indicated that homogeneous nucleation similarly occurred when 40 or 80 ml litre^?1 trilaurin was admixed with trimyristin. NMR resolution made it possible to follow the crystallization phenomena in different locations of the crystallization vessel effectively in situ and undisturbed. Statistical analyses in this case revealed a significant trilaurin-location interaction confirming that the rate of nucleation processes was affected both by the concentration of trilaurin and the heat transfer properties of the sample and vessel. The time-location interactions were not significant, confirming the hypothesis that in the absence of tilaurin, zero order nucleation did not occur in the first phase.     

Euler算法求解Power定律下蔗糖冷却结晶的变异系数

以Ｐｏｗｅｒ定律为基础，建立初级成核和二次成核作用下的蔗糖连续冷却结晶过程粒度分布的数学模型，运用Ｅｕｌｅｒ方法进行求解。     

Induction Time of Crystallization in Vegetable Oils, Comparative Measurements by Differential Scanning Calorimetry and Diffusive Light Scattering

ABSTRACT: In this work we compared the induction time of crystallization (τ_i. measured by DSC (τ_iDSC) and scanning diffusive light-scattering (SDLS, τ_iSDLS) in a vegetable oil blend. Several crystallization temperatures and cooling rates (1,10, and 30 °C/min) were investigated. Additionally, rheograms obtained during the crystallization of the oil blends were obtained to differentiate the stages of nucleation and crystal growth. The results obtained showed that independent of cooling rate and crystallization temperature, SDLS provided an earlier detection of triacylglycerides'(TAGS) nucleation than DSC. Furthermore, τ_iSDLS was more consistent (that is, lower standard deviation) than τ_iDSC particularly at high crystallization temperatures and cooling rates. The rheograms showed that τ_iDSC involves a measurement of crystal growth, while τ_iSDLS is associated with the early formation of a solid phase in the oil blend (that is, TAGS nucleation). When the Fisher-Turnbull equation was therefore used to calculate the free energy of nucleation (ΔG_c), τ_iSDLS provided a better estimate of ΔG_c than that obtained by τ_iDSC     

Sugar crystallization in food products

A review of the recent literature on crystallization of the commercial sugars (fructose, glucose, lactose, and sucrose) is presented. Topics include: NUCLEATION--The formation of the crystalline phase from supersaturated solutions can occur by either a spontaneous or a forced nucleation mechanism. Recent work on the mechanisms, kinetics, and impact of both heterogeneous and secondary (contact) nucleation is discussed. GROWTH--Recent studies on the mechanisms and kinetics of crystal growth will be reviewed. This discussion includes work on the growth rate dispersion exhibited by these sugars. EFFECTS OF IMPURITIES AND ADDITIVES--The presence of impurities and additives (including mixed sugar systems) affects both the nucleation and growth steps. A discussion of the recent work in this area is included. Emphasis is placed on the relationship between these crystallization phenomena and the solution structure for comparison purposes.     

Influence of diglycerides on crystallisation of palm oil

Palm oil diglycerides and pure synthetic diglycerides of 1,2‐(2,3‐) and 1,3‐dipalmitoylglycerol, dioleoylglycerol and palmitoyloleoyl glycerol were added to purified triglycerides of palm oil. The crystallisation kinetics of the samples were studied by spectrophotometry, NMR analysis of the solid fat content and by X‐ray diffraction of the crystals obtained at 20°C. Palm oil diglycerides inhibited the nucleation process and retarded the crystal growth rate of palm triglycerides. The effect was less pronounced at a higher degree of supercooling. The extent of inhibition depended on the nature of the diglycerides and the concentration. © 1999 Society of Chemical Industry