二水硫酸钙的结晶动力学研究

用MSMPR结晶器对二水硫酸钙结晶的动力学进行了研究,在假设ΔL定律适应于MSMPR结晶过程的前提下,测量了晶体的粒数密度n和晶体平均粒度L,根据ln(n)-L直线在坐标轴上的截距及其斜率所计算出的晶核粒数密度n0和晶体生长速率G之间的关系推导出结晶过程的成核速率B0。最后从ln(n0)与ln(G)之间的直线关系再推导出二水硫酸钙在60℃情况下的成核速率B0与晶体生长速率G之间的动力学表达式:B0=k2Gi=1.142×103G0.54,同时还研究了添加不同类型的活化疏松剂对二水硫酸钙结晶的影响情况。     

石膏转化制硫酸钾结晶动力学及结晶添加剂研究

研究了浓氨介质中石膏与氯化钾直接转化制硫酸钾的结晶动力学及结晶添加剂的作用效果。结果表明 ,硫酸钾在氨介质中的成核速率与晶体生长速率、悬浮密度、搅拌速率存在如下关联式 :B0 =5 .64 13×10 8G3.32 0 8Mt0 .0 559np0 .2 92 8。加入异丙醇、OP乳化剂及十二烷基苯磺酸钠等添加剂 ,可使硫酸钾结晶产品纯度提高 ,晶体形态整齐均匀     

2-氯-4,6-二硝基间苯二酚的结晶动力学研究

采用间歇动态法测定了2-氯-4,6-二硝基间苯二酚(CDNR)的结晶动力学参数,并回归了CDNR的结晶动力学方程,分析了结晶动力学的影响因素。通过回归结晶成核速率方程和生长速率方程的计算,得到了一定温度、一定搅拌速度下的成核、生长速率常数,温度27℃、搅拌速度180 r.min-1时成核速率常数和成长速率常数分别为9.17×106和2.17×10-12,温度33℃、搅拌速度240 r.min-1时成核速率常数和成长速率常数分别为2.02×108和7.10×10-12。     

五水柠檬酸钠连续结晶动力学研究

研究了五水柠檬酸钠的连续结晶过程。利用马尔文激光粒度分析仪对不同温度和停留时间下连续结晶过程产品的粒度分布进行分析。通过实验数据和粒度无关生长模型,分别计算了连续结晶过程中五水柠檬酸钠晶体生长与成核速率方程。研究表明,在33.3℃的连续结晶过程中,五水柠檬酸钠的成核速率较生长速率对溶液的过饱和度变化更敏感,增加溶液过饱和度更易形成较小粒度的晶体。     

阿莫西林成核与生长动力学

阿莫西林现有结晶工艺获得的晶体粒度过小,直接影响到后续的过滤、干燥以及包装运输,研究其结晶动力学参数以指导结晶工艺,控制结晶过程中晶体的成核速度与生长速度,对提高晶体粒度有着重要意义。文章分别采用激光法和显微摄像的方法对阿莫西林结晶过程中初级成核、二次成核和单晶体生长速度进行了测定,计算出动力学相关数据。通过实验确定阿莫西林初级成核中均相成核与非均相成核的分界过饱和度S=4.5以及各自对应的成核自由能与成核半径,确定了二次成核发生时间与过饱和度间的关系以及阿莫西林晶体的生长速率与过饱和度的关系,并由生长指数m=1.995 5推出阿莫西林的生长机制为螺旋错位生长。通过阿莫西林结晶动力学研究为改进和优化结晶过程提供了理论基础。     

硝酸钾结晶生长特性的研究

利用5LMSMPR结晶器,通过改变停留时间、过饱和度和搅拌速度等因素,对硝酸钾结晶的粒度分布、平均粒径、主粒径、成核及生长速率等动力学特性进行了研究,并在结晶温度25℃、过饱和度2℃、搅拌速度400r/min和停留时间10～50min条件下,建立了硝酸钾晶体生长动力学模型:B°=6.19×1022G2.02。研究结果表明:当停留时间大于30min、搅拌速度为400r/min时,晶体的平均粒径和主粒径较大;过饱和度的减小也会使晶体粒径增大,但其影响较小。     

磷酸二氢铵结晶动力学研究

运用连续流化床结晶装置，测定了不同饱和温度的磷酸二氢铵在15℃和25℃结晶温度下晶体的成核、生长速率。实验结果表明，随饱和温度的增加，磷酸二氢铵的成核、生长速率随之增加；同时根据实验数据，应用多元线性回归得出磷酸二氢铵晶体的生长动力学模型：B0=1．45×10^6G^0.189MT^1.608（15℃），B0=1．05×10^7G^0.458MT^0.980（25℃）。实验还研究了添加剂对磷酸二氢铵晶体生长速率的影响，结果表明，有添加剂时晶体的生长速率更高；而且随着饱和温度的升高，磷酸二氢铵晶体的生长速率上升趋势更显著。     

流化床中磷酸二氢钾结晶成核动力学研究

运用连续流化床结晶装置,参照工业装置结晶条件,研究了磷酸二氢钾在25℃条件下的结晶成核动力学规律。采用流化床结晶过程的成核动力学模型,利用多元线性回归得到成核动力学参数,并通过实验验证动力学参数的可靠性。结果表明,磷酸二氢钾结晶二次成核中流体剪切成核占主导地位,即B0=1.02×10-4M0.T563R1e.654,实验测试过程中晶体聚结和宏观破碎的影响可以忽略。     

PBS结晶影响因素的研究

采用偏光显微镜对聚丁二酸丁二醇酯(PBS)的结晶影响因素进行了研究。结果表明:在等温结晶时,PBS的最佳结晶温度随着分子量的增大而提高,当分子量增到一定值后,最佳结晶温度受分子量的影响很小。结晶温度一定时,PBS的晶体尺寸随着结晶时间的延长而增大。结晶时间一定时,PBS的晶体尺寸随着结晶温度的提高而先增大后减小。数均分子量为1×103、8×103、6×104、1×105的PBS最佳结晶温度分别为40℃~50℃、80℃、80℃、90℃。低分子量的PBS在较短的结晶时间内晶体尺寸就已较大,而高分子量的PBS在较长的时间内才能形成较大尺寸的晶体,数均分子量为8×103、6×104、1×105的PBS在最佳结晶温度形成较好结晶的时间分别为10min、20min、25min。     

果糖结晶过程优化

通过实验筛选得到适合果糖结晶的混合溶剂,利用中通量结晶仪器Crystalline测定了果糖在水-乙醇（水的摩尔分数为0.39）混合溶剂中的溶解度和介稳区,采用Apelblat方程拟合了溶解度数据。基于热力学数据设计了晶种引晶的果糖冷却结晶工艺,过程优化得到的产品收率可达78.2%以上,纯度可达99%以上,晶体形貌规则,表面光滑,粒度分布窄。当晶体粒径大于100 μm时,利用粒度无关生长的粒数衡算方程建立了果糖连续结晶过程的动力学模型,模型表明晶体生长级数大于成核级数。     

连续结晶器中十水草酸铈反应结晶动力学研究

采用连续稳态法,对十水草酸铈在混合悬浮、混合产品排出(MSMPR)结晶器中的连续反应结晶动力学进行了研究。实验测定了十水草酸铈晶体的粒数密度分布数据,并以此为基础,基于粒度无关生长速率模型,对不同实验条件下晶体的粒数密度分布数据进行拟合,确定了十水草酸铈的成核动力学方程和生长动力学方程,并计算得到十水草酸铈晶体的成核、生长速率相对于过饱和度的指数分别为4.211和0.752。同时,对方程的理论分析表明,低过饱和度有利于得到平均粒径更大的十水草酸铈晶体。十水草酸铈结晶动力学的研究,为其大规模工业生产提供了重要的动力学数据。     

苊冷却结晶动力学的间歇动态法研究

通过添加晶种的间歇冷却结晶实验研究了苊在乙醇中的结晶动力学。由苊晶体的粒数密度数据,通过矩量变换法按粒度无关生长模型求解粒数衡算方程,采用多元线性最小二乘法回归动力学数据,得到苊在乙醇中晶体生长及成核速率方程。对动力学方程的理论分析表明:搅拌速率对二次成核影响显著,随搅拌速率增加,晶体的成核速率明显增加。同时适宜的过饱和度及较低的悬浮密度,有利于苊晶体生长。该研究为苊冷却结晶特性的辨识、粒度分布的控制及工业放大提供了重要的理论指导。     

粒数衡算与多相流耦合求解刮削制冰的晶粒特性

在考虑晶粒成核、生长、聚并和破碎的情况下,采用分组法求解粒数衡算方程,通过耦合粒数衡算与多相流方程,建立了多尺度的结晶模型,模拟了表面刮削式制冰装置内水的动态结晶过程,获得不同温度、刮削速度、制冰时间等外界条件下晶粒数密度分布、云图等信息,分析了外界宏观条件对水的动态结晶过程的影响。结果表明：由于碰撞引起的晶粒聚并和破碎使得晶粒的尺寸分布更为集中和均匀;在过冷温差（流体局部温度与水的相变温度差值）不大于20℃,刮削速度不大于10 r·s^-1范围内,降低壁面温度、增加刮削速度可以加速水的结晶与生长。     

丙烯酰胺的结晶热力学

采用激光测量装置研究了丙烯酰胺水溶液在不同温度、不同pH值及不同搅拌速度下的溶解度与超溶解度特性 ,得出了丙烯酰胺的结晶亚稳区宽度在 7～ 10℃ (10mol/L时 19～ 2 7℃ ,7mol/L时 0～ 9℃ )之间。实验结果表明 ,随着温度t的升高 ,溶解度s呈指数级增加 ,SAM=5 990e0 0 18t,pH值对溶解度影响不大。随着搅拌速度的提高 ,亚稳区宽度变窄 ,结晶发生的时间提前 ,结晶发生后的温升值减小。温度对亚稳区宽度的影响不大     

Modeling of crystal growth and nucleation rates for pentaerythritol batch crystallization

The kinetics of crystallization – nucleation and crystal growth – was determined for a seeded batch cooling process. Several experiments were done utilizing always the same condition: initial concentration, seed mass and size distribution, and cooling rate. From one experiment to other the agitation speed was varied. As the utilized reactor is able to measure torque of the impeller, the power dissipated in agitation was monitored during the crystallization, as well as reactor temperature and turbidity of the suspension. Turbidity monitoring and the measurement of particle size distribution from seeds and final product allowed obtaining the evolution of the second moment of the particles during the crystallization. The crystallization process was modeled utilizing the Method of Moments and the nucleation and crystal growth kinetics were obtained from least-square minimization of calculated second moments of the crystals. A crystal growth kinetic was determined and the secondary nucleation rate was described as a function of dissipated power and as functions of impeller tip speed. Additional experiments were done, in which cooling rate, seed mass and seed size were varied. The calculated kinetics could satisfactorily describe the results of the additional experiments, corroborating the quality of the modeling.     

对二甲苯降膜结晶动力学

降膜结晶是工业生产对二甲苯的重要方法。以多孔介质分形理论为基础开展对二甲苯降膜结晶动力学的研究。通过动力学模型优化实验条件,结晶条件为进料速度为60 ml·min^-1、结晶温度-15℃、原料预冷温度25℃,发汗条件为升温速率1℃·min^-1、发汗终温5℃。在此条件下测定降膜结晶过程中对二甲苯结晶量以及液相夹带量,建立了晶体生长速率方程和液相夹带速率方程,相关系数分别为0.967和0.977,模型可靠。结果表明随着过饱和度的增加,液相夹带速率增长更快,晶层中夹带液相体积分数越大,晶层孔隙率越大。晶体生长速率方程和液相夹带速率方程的建立对工业降膜结晶生产对二甲苯过程中,通过调节液膜过饱和度控制晶层生长具有重要参考意义。     

Modeling the crystallization of proteins and small organic molecules in nanoliter drops

Drop‐based crystallization techniques are used to achieve a high degree of control over crystallization conditions in order to grow high‐quality protein crystals for X‐ray diffraction or to produce organic crystals with well‐controlled size distributions. Simultaneous crystal growth and stochastic nucleation makes it difficult to predict the number and size of crystals that will be produced in a drop‐based crystallization process. A mathematical model of crystallization in drops is developed using a Monte Carlo method. The model incorporates key phenomena in drop‐based crystallization, including stochastic primary nucleation and growth rate dispersion (GRD) and can predict distributions of the number of crystals per drop and full crystal size distributions (CSD). Key dimensionless parameters are identified to quickly screen for crystallization conditions that are expected to yield a high fraction of drops containing one crystal and a narrow CSD. Using literature correlations for the solubilities, growth, and nucleation rates of lactose and lysozyme, the model is able to predict the experimentally observed crystallization behavior over a wide range of conditions. Model‐based strategies for use in the design and optimization of a drop‐based crystallization process for producing crystals of well‐controlled CSD are identified. © 2009 American Institute of Chemical Engineers AIChE J, 2010     

Salting out crystallization of sodium sulfate

The growth and nucleation rates of sodium sulfate crystals salted out from their solution in a 38% w/w sulfuric acid solvent by the addition of an 80:20 w/w methanol:water solution, were determined from measurements of the steady-state crystal size distribution (CSD) generated in a continuous mixed-suspension, mixed-product-removal (MSMPR) salting out crystallizer. The effects of the supersaturation, the crystal suspension density and the temperature on these rates were investigated. The effect of the Cr⁺⁺⁺ impurity was also briefly studied. The growth rate kinetic order g was determined to be essentially unity. The nucleation rate kinetic order b was determined as 2.11. The corresponding kinetic rate constants K_G and K_B were fitted to an Arrhenius type temperature dependence to give. K_G = 43960 exp(-24600/RT) and K_B = 0.064 exp(70900/RT) where R is in kJ/kmol · K. An increase in chromate impurity concentration caused an increase in the growth rate constant K_G but had no significant effect on the nucleation kinetics. The kinetiics of crystallization as determined for this system would indicate that a high temperature, high crystal suspension density and long residence time are conditions which are favorable for the production of large sodium sulfate crystals.     

CSD-controlled reactive crystallization of SrSO4 in the presence of polyethylenimine

Reactive crystallization of SrSO₄ was performed in the presence of polyethylenimine (PEI) using a double-jet crystallizer. PEI dosage suggested important dependence on crystal size distributions (CSDs) leading to obtain micron-sized crystals with mono-dispersed distribution. A plausible role of PEI was considered to be a multiple inhibitor of growth, continuous nucleation and agglomeration. PEI might be an effective polyelectrolyte additive for the production of mono-dispersed fine crystals.