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1、会计学1工业结晶技术工业结晶技术工业结晶过程工业结晶过程 Industrial Crystallization 一、工业结晶概论 Chapter 1 Overview of Industrial Crystallizationn n结晶在工业上的应用 Utilization of Crystallization in Industriesn n结晶产品的表征 Characterization of Crystalline Productsn n溶解度和过饱和度 Solubility and Supersaturation第1页/共395页工业结晶过程工业结晶过程 Industrial Crys

2、tallization 二、成核 Chapter 2 Nucleationn n初级成核 Primary Nucleationn n二次成核 Secondary Nucleationn n工业结晶器中的成核 Nucleation in Industrial Crystallizers第2页/共395页工业结晶过程工业结晶过程 Industrial Crystallization 三、晶体生长 Chapter 3 Crystal Growthn n晶体生长过程 Process Involved in Growth of Crystalsn n总的晶体生长过程 The Overall Crysta

3、l Growth Processn n总的晶体生长动力学 The Overall Growth Kineticsn n生长弥散 Growth Dispersion第3页/共395页工业结晶过程工业结晶过程 Industrial Crystallization 四、粒数衡算概念四、粒数衡算概念 Chapter 4 Population Balance ConceptChapter 4 Population Balance Conceptn n结晶系统数学模型结晶系统数学模型 Mathematical Model of Crystallization systemsMathematical Mod

4、el of Crystallization systemsn n粒数衡算粒数衡算 Population BalancePopulation Balancen n通用粒数方程通用粒数方程 The General Population EquationThe General Population Equationn n分布矩分布矩 Moments of The DistributionMoments of The Distributionn n平均粒度平均粒度 Average SizesAverage Sizesn n变异系数变异系数 Coefficient of VariationCoeffic

5、ient of Variation第4页/共395页工业结晶过程工业结晶过程 Industrial Crystallization 五、混合悬浮混合产品取出结晶器：一种理想方式五、混合悬浮混合产品取出结晶器：一种理想方式 Chapter 5 Mixed Suspension Mixed Product Chapter 5 Mixed Suspension Mixed Product Removal Crystallizer-An Idealized ConfigurationRemoval Crystallizer-An Idealized Configurationn n混合悬浮混合产品取出

6、概念混合悬浮混合产品取出概念 Mixed Suspension Mixed Product Removal Crystallizer ConceptMixed Suspension Mixed Product Removal Crystallizer Conceptn nMSMPRMSMPR方式的粒数衡算方式的粒数衡算 Population Balance for The MSMPR ConfigurationPopulation Balance for The MSMPR Configurationn nMSMPRMSMPR结晶器的粒数密度分布当晶体生长速度与粒径无关时结晶器的粒数密度分布当

7、晶体生长速度与粒径无关时 Population Density Population Density Distribution for MSMPR CrystallizerDistribution for MSMPR CrystallizerSize Independent Crystal Growth RateSize Independent Crystal Growth Raten nMSMPRMSMPR结晶器的粒数密度分布当晶体生长速度与粒径有关时结晶器的粒数密度分布当晶体生长速度与粒径有关时 Population Density Population Density Distribut

8、ion for MSMPR CrystallizerDistribution for MSMPR CrystallizerSize Dependent Crystal Growth RateSize Dependent Crystal Growth Rate第5页/共395页工业结晶过程工业结晶过程 Industrial Crystallization 六、粒数影响因素 Chapter 6 Population Functionsn n与MSMPR结晶方式的偏差 Deviations from The MSMPR Crystallizer Configurationn n分级 Classifi

9、cation第6页/共395页工业结晶过程工业结晶过程 Industrial Crystallization 七、结晶动力学的求取七、结晶动力学的求取 Chapter 7 Derivation of Crystallization KineticsChapter 7 Derivation of Crystallization Kineticsn n纯粹结晶动力学的求取纯粹结晶动力学的求取 Derivation of Pure Crystallization KineticsDerivation of Pure Crystallization Kineticsn n就外推得到的粒数密度数据的解释

10、就外推得到的粒数密度数据的解释 Interpretation Population Interpretation Population Density Data Obtained Resorting to ExtrapolationDensity Data Obtained Resorting to Extrapolationn n受粒数函数影响的结晶动力学的求取受粒数函数影响的结晶动力学的求取 Derivation of Derivation of Crystallization Kinetics from Distributions Affected by Population Cryst

11、allization Kinetics from Distributions Affected by Population FunctionsFunctions第7页/共395页工业结晶过程工业结晶过程 Industrial Crystallization 八、结晶过程中的物理传递现象八、结晶过程中的物理传递现象 Chapter 8 Physical Transport Phenomena in Chapter 8 Physical Transport Phenomena in CrystallizationCrystallizationn n均相液体的混合均相液体的混合 Mixing of

12、Homogeneous LiquidsMixing of Homogeneous Liquidsn n固液悬浮物的混合固液悬浮物的混合 Mixing of Solid/Liquid SuspensionsMixing of Solid/Liquid Suspensionsn n固液悬浮物中的传质固液悬浮物中的传质 Mass Transfer in Solid/Liquid SuspensionsMass Transfer in Solid/Liquid Suspensionsn n搅拌槽中的传热搅拌槽中的传热 Heat Transfer in Agitated VesselsHeat Tran

13、sfer in Agitated Vessels第8页/共395页工业结晶过程工业结晶过程 Industrial Crystallization 九、结晶系统的取样和分析 Chapter 9 Sampling and Analyzing Crystallizing Systemsn n液相样品的取样和分析 Sampling and Analyzing Liquid Phase Samplesn n固相样品的取样和分析 Sampling and Analyzing Solid Phase Samples第9页/共395页工业结晶过程工业结晶过程 Industrial Crystallizatio

14、n 十、结晶器设计中基本原理的应用十、结晶器设计中基本原理的应用 Chapter 10 The Use of Fundamental Principles in Chapter 10 The Use of Fundamental Principles in Crystallizer DesignCrystallizer Designn n 1 1、物料衡算用于确定结晶器体积、物料衡算用于确定结晶器体积 The Use of Mass Balance to Formulate The Use of Mass Balance to Formulate Crystallization VolumeC

15、rystallization Volumen n 2 2、粒数衡算概念用于表征产品晶体粒度分布、粒数衡算概念用于表征产品晶体粒度分布 The Use of The Population The Use of The Population Balance Concept to Characterize Product Crystal Size DistributionsBalance Concept to Characterize Product Crystal Size Distributionsn n 3 3、工业结晶器中结晶动力学与操作条件的相互作用、工业结晶器中结晶动力学与操作条件的相互

16、作用 Interactions Interactions Between Crystallization Kinetics and Operation Conditions in Industrial Between Crystallization Kinetics and Operation Conditions in Industrial CrystallizersCrystallizersn n 4 4、工业结晶过程中的技术问题、工业结晶过程中的技术问题 Technical Problems in Industrial Technical Problems in Industrial C

17、rystallizationCrystallization第10页/共395页工业结晶过程工业结晶过程 Industrial Crystallization 十一、面向设计的结晶动力学：从小型实验取得的结晶动力学在结晶器设计上的应用十一、面向设计的结晶动力学：从小型实验取得的结晶动力学在结晶器设计上的应用n nChapter 11 Design Oriented Crystallization Kinetics Obtained in Small Scale Experiments for Chapter 11 Design Oriented Crystallization Kinetics

18、Obtained in Small Scale Experiments for Crystallization DesignCrystallization Designn n1 1、取得面向设计的结晶动力学的标准过程、取得面向设计的结晶动力学的标准过程 Standardized procedure to derive design oriented Standardized procedure to derive design oriented crystallization kineticscrystallization kineticsn n2 2、标准结晶动力学在结晶器设计中的应用、标准

19、结晶动力学在结晶器设计中的应用 The Use of Standard Crystallization Kinetics in The Use of Standard Crystallization Kinetics in Crystallizer DesignCrystallizer Designn n从小型实验取得的结晶动力学用于大型结晶器设计从小型实验取得的结晶动力学用于大型结晶器设计 The Use of Crystallization Kinetics The Use of Crystallization Kinetics Obtained in Small Scale Experi

20、ments for Design of Large CrystallizersObtained in Small Scale Experiments for Design of Large Crystallizers第11页/共395页工业结晶过程工业结晶过程 Industrial Crystallization 十二、间歇结晶器设计十二、间歇结晶器设计 Chapter 12 Design of Batch CrystallizersChapter 12 Design of Batch Crystallizersn n间歇结晶操作的概念间歇结晶操作的概念 Concept of Operatio

21、n in Batch CrystallizationConcept of Operation in Batch Crystallizationn n间歇结晶的一个循环间歇结晶的一个循环 Description of A Cycle in Batch CrystallizationDescription of A Cycle in Batch Crystallizationn n间歇过程的结晶周期间歇过程的结晶周期 Description of A Crystallization Period in A Batch CycleDescription of A Crystallization Pe

22、riod in A Batch Cyclen n间歇与连续操作的比较间歇与连续操作的比较 Comparison of Batch and Continuous OperationComparison of Batch and Continuous Operationn n不稳定粒数衡算不稳定粒数衡算 The Unsteady State Number BalanceThe Unsteady State Number Balancen n加晶种间歇结晶器设计：能量传递的最佳控制加晶种间歇结晶器设计：能量传递的最佳控制 Design of Seeded Batch Crystallizers De

23、sign of Seeded Batch Crystallizers Featuring on Optimal Control of Energy TransferFeaturing on Optimal Control of Energy Transfer第12页/共395页工业结晶过程工业结晶过程 Industrial Crystallization 十三、连续搅拌槽式结晶器设计十三、连续搅拌槽式结晶器设计 Chapter 13 Design of Continuous Stirred Tank CrystallizerChapter 13 Design of Continuous Sti

24、rred Tank Crystallizern n混合产品取出的连续全混结晶器的设计混合产品取出的连续全混结晶器的设计 Design of Continuous Well Mixed Crystallizers with Design of Continuous Well Mixed Crystallizers with Mixed Product RemovalMixed Product Removaln n强制内循环连续蒸发结晶器设计强制内循环连续蒸发结晶器设计 Design of Continuous Evaporative Crystallizers with Forced Desig

25、n of Continuous Evaporative Crystallizers with Forced Internal CirculationInternal Circulationn n细晶消除的全混结晶器设计细晶消除的全混结晶器设计 Design of Well-Mixed Crystallizers with Fines RemovalDesign of Well-Mixed Crystallizers with Fines Removaln n分级产品取出的全混结晶器设计分级产品取出的全混结晶器设计 Design of Well-Mixed Crystallizers with

26、Classified Product Design of Well-Mixed Crystallizers with Classified Product RemovalRemovaln n同时消除细晶和分级产品取出的全混结晶器设计同时消除细晶和分级产品取出的全混结晶器设计 Design of Well-Mixed Crystallizers with Design of Well-Mixed Crystallizers with Simultaneously Operative Fines Destruction and Classified Product RemovalSimultane

27、ously Operative Fines Destruction and Classified Product Removal第13页/共395页工业结晶过程工业结晶过程 Industrial Crystallization 十四、强制循环蒸发结晶器设计十四、强制循环蒸发结晶器设计 Chapter 14 Design of Forced Circulation Evaporative CrystallizerChapter 14 Design of Forced Circulation Evaporative Crystallizern n引言与工作原理引言与工作原理 Introductio

28、n and Principles of OperationIntroduction and Principles of Operationn n蒸发结晶衡算蒸发结晶衡算 Balances in Evaporative CrystallizationBalances in Evaporative Crystallizationn n固体分级固体分级 Solids ClassificationSolids Classificationn n与粒径有关的晶体生长速率与粒径有关的晶体生长速率 Size Dependent Growth RatesSize Dependent Growth Ratesn

29、 n浓度推动力分布浓度推动力分布 Distribution of Concentration Driving ForceDistribution of Concentration Driving Forcen n液相流动模型液相流动模型 Liquid Phase Flow ModelLiquid Phase Flow Modeln n推动力衡算推动力衡算 Driving Force BalancesDriving Force Balancesn n区域停留时间区域停留时间 Sectional Residence TimesSectional Residence Timesn n拟粒径有关晶体生

30、长速率估算拟粒径有关晶体生长速率估算 Evaluation of Pseudo Size-dependent Growth RatesEvaluation of Pseudo Size-dependent Growth Ratesn n晶体粒径分布预测晶体粒径分布预测 Prediction of Crystal Size DistributionPrediction of Crystal Size Distribution第14页/共395页工业结晶过程工业结晶过程 Industrial Crystallization 十五、晶浆处理：结晶器十五、晶浆处理：结晶器-离心机离心机-干燥器系统分析

31、干燥器系统分析 Chapter 15 Slurry Chapter 15 Slurry Handling:An Analysis of The System Crysallizer-Centrifuge-DryerHandling:An Analysis of The System Crysallizer-Centrifuge-Dryern n管道设计管道设计 Design of Pipe LinesDesign of Pipe Linesn n阀门选择阀门选择 Choice of ValvesChoice of Valvesn n晶浆预浓缩设备晶浆预浓缩设备 Magma Prethicken

32、ersMagma Prethickenersn n脱水设备脱水设备 Dewatering EquipmentDewatering Equipmentn n干燥设备干燥设备 Drying EquipmentDrying Equipment第15页/共395页工业结晶过程工业结晶过程 Industrial Crystallization 参考书目参考书目 ReferencesReferencesn nMullin,J.W.,Crystallisation,2nd ed.Butterworths,London,1972.TQ026.5/YM1Mullin,J.W.,Crystallisation,2

33、nd ed.Butterworths,London,1972.TQ026.5/YM1n n中译本：胡维杰、宁桂玲等编译，中译本：胡维杰、宁桂玲等编译，结晶过程结晶过程。大连：大连理工大学出版社，。大连：大连理工大学出版社，19911991。TQ026.5/H2TQ026.5/H2n n 苏联苏联E.B.E.B.哈姆斯基著，古涛、叶铁林译，哈姆斯基著，古涛、叶铁林译，化学工业中的结晶化学工业中的结晶。化学工业出版社，。化学工业出版社，北京，北京，19841984。TQ026.5/H1TQ026.5/H1n n丁绪淮、谈遒著，丁绪淮、谈遒著，工业结晶工业结晶。化学工业出版社，北京，。化学工业出版社

34、，北京，19851985。n nJournal of Crystal Growth.Journal of Crystal Growth.n nTung,H.H.,Paul,E.L.,Midler,M,McCauley,J.A.,Crystallization of Organic Compounds:An Tung,H.H.,Paul,E.L.,Midler,M,McCauley,J.A.,Crystallization of Organic Compounds:An Industrial Perspective.New Jercey:John Wiley&Sons,2009.Industri

35、al Perspective.New Jercey:John Wiley&Sons,2009.第16页/共395页第一章第一章第一章第一章 工业结晶概论工业结晶概论工业结晶概论工业结晶概论1.1结晶在工业上的应用结晶在工业上的应用 化工、食品、医药、冶金等多领域化工、食品、医药、冶金等多领域1.2结晶产品的表征结晶产品的表征 纯度纯度&强度强度 形状形状&外观外观 晶体粒度分布晶体粒度分布众数 mode中值 median size平均尺寸 mean size变异系数 CV第17页/共395页Figure 1.1 Illustration of maximum supersaturation a

36、nd growth rate at which sound and pure crystals free from inclusions can be obtained.第18页/共395页Figure 1.2 Typical cumulative undersize weight distributions obtained in continuous crystallization.Figure 1.3 The relative percentage frequency curve showing commonly used average sizes.第19页/共395页CV%(标准差

37、standard deviation/平均尺寸 mean size)100%第20页/共395页1.3 溶解度和过饱和度溶解度和过饱和度 Figure 1.4 Solubility curve for a typical substance.第21页/共395页Gibbs-Thomson Gibbs-Thomson 方程方程方程方程 C CL LC C*exp(MY/RTexp(MY/RTc cL)eq.(1.1)L)eq.(1.1)式中参数：CL:粒径为L的粒子的溶解度,kg/kg solution C*:大粒子的溶解度,kg/kg solution M:分子量,kg/kgmolK Y:固体

38、粒子的表面能,J/m2 R:气体常数,J/molK c:晶体密度,kg/m3 T:绝对温度,K L:晶体尺寸,m 第22页/共395页第二章第二章第二章第二章 成核：机理及来源成核：机理及来源成核：机理及来源成核：机理及来源成核机理可以区分为以下几种情况：成核机理可以区分为以下几种情况：成核 Nucleation初级成核 Primary二次成核 Secondary均相成核 Homogeneous多相成核 Heterogeneous第23页/共395页2.1 初级成初级成核核 Figure 2.1 The analogy of the states of stability between a

39、simple mechanical system and a crystallizing system.第24页/共395页Figure 2.2 Free energy diagram for homogeneous nucleation indicating the existence of a critical nucleus.均相成核：G kaL2+kvL3(G)v（2.3）第25页/共395页ka 表面形状因子：定义：表面积=ka L2kv 体积形状因子:定义：体积=kv L3L为晶体特征尺寸对于球形颗粒，面积=d2，如果以d为特征尺寸，则ka=；体积=/6d3，如果以d为特征尺寸，则

40、kv=/6。对于立方体颗粒，面积=6d2，如果以边长d为特征尺寸，则ka=6；体积=d3，如果以d为特征尺寸，则kv=1。第26页/共395页对式对式(2.3)(2.3)求最大值，得：求最大值，得：Lc=-2ka/3kv(G)v -(2.5)得临界尺寸：第27页/共395页多相成核：0，cos1，GHET0 complete affinity0180 ，GHET1时：Gcg -(3.10)第42页/共395页3.3 总的晶体生长动力学总的晶体生长动力学 与尺寸有关的晶体生长 Figure 3.3 Effect of crystal/solution relative velocity on t

41、hegrowth rate of(111)face of potash alum crystals at32 McCabes L定律 第43页/共395页G(111)=6.2410-4v0.65cg -(3.11)（111）晶面的生长速率关联式：=16L0.63cg -(3.12)流化床中得到的生长速率关联式：第44页/共395页Figure 3.4 Comparison between face growth rates of single crystals(smooth curve)and overall growth rates obtained in afluidized bed cr

42、ystallizer 第45页/共395页Figure 3.5 The effect of crystal size L on the overall growthrate of potash alum at 30 第46页/共395页 传质和表面结合阻力对晶体生长的相对贡献推导 concentration driving force mass transfer surfaceintegrationcrystal/solutionhydrodynamics temperature and impuritiesoverall growth rateFigure 3.6 Schematic rep

43、resentation of influences exerted by the growth environment upon processes involved in crystal growth.第47页/共395页假定溶解过程仅仅由传质控制，则：Figure 3.7 Crystal dissolution kinetics for potash alum at 30第48页/共395页Figure 3.8 Surface integration kinetics for potash alum crystals at30.The dotted lines indicate overa

44、ll growth rates fromwhich these were derived 第49页/共395页Figure 3.9 Surface integration kinetics for potash alum crystals at 30 as a function of crystal size and supersaturation 第50页/共395页 对于总生长动力学、溶解动力学和表面结合动力学对过饱和度都是一级的情况，可以用下式计算总速度常数：Figure 3.10 Percentage of the total resistance to crystal growth

45、offered by volume diffusion and surface integration process as a function of crystal size for potash alum at 30 第51页/共395页 晶体生长速率表达式 McCabe and Stevenss model：G=dL/dt=1.7710-3Lav1.1(c-c*)1.8 (3.15)Bransoms model dL/dt=aRebcn (3.17)连续结晶器中简化为：dL/dt=avbcn (3.19)dL/dt=aLbcn(3.20)或第52页/共395页Canning and R

46、andolphs modelG=G0(1+a1L+a2L2+anLn)(3.21)Abegg,Stevens and Larsons model(ASL model)G=G0(1+L)b，b1，L0 (3.22)3.4生长弥散生长弥散 在固定过饱和度下，生长速率可以有很大变化。这种现象称为生长速率弥散。第53页/共395页第四章第四章第四章第四章 粒数衡算概念粒数衡算概念粒数衡算概念粒数衡算概念4.1 结晶系统的数学模型结晶系统的数学模型 结晶器模型由基于基本原理的方程组和一个经验生长速率方程组成，为空间和时间的函数。这些一般方程组可以根据具体情况简化。第54页/共395页Figure 4.1

47、 Schematic representation of countercurrentflow between crystals and mother liquor withparameters distributed in axial direction aperfectly classified fluidized bed crystallizer.第55页/共395页Figure 4.2 Schematic representation of a well mixed crystal/solution systemwith lumped parameters a perfectly mi

48、xed crystallizer.第56页/共395页ModelSolution Concentration ParametersCrystal Concentration Parameters1stirred tanklumpedlumped2fluidized beddistributed in axial directiondistributed in axial direction3not considered in literaturedistributed in axial directionlumped4not considered in literaturelumpeddist

49、ributed in axial direction表4.1 几种理想情况 第一种情况又可以按照产品取出方式分为二种类型，即：a)混合悬浮混合产品取出结晶器 b)混合悬浮分级产品取出结晶器第57页/共395页4.2 粒数衡算粒数衡算 整个结晶器系统的粒数守恒定律可以写成：Nin-Nout=Naccumulation (4.1)对于晶体尺寸为l的晶体，总粒数衡算就是：Nin|l-Nout|l=Naccumulation|l (4.2)由于晶体数在结晶系统内随点和点而不同，所以要考虑粒数密度，严格讲是频率粒数密度：第58页/共395页在稳态操作的结晶系统内，晶体总数是：总粒数密度：平均粒数密度：n

50、(l)=N(l)/V (4.5)单位悬浮体积的晶体数是：第59页/共395页4.3 一般粒数方程一般粒数方程 作出下列假设：u 悬浮物占据可变体积V，被限制在固定 边界和自由重力表面中 u 悬浮物进出物流可以认为在径向混合，但 悬浮物本身不必是均匀的 u 悬浮物中的颗粒在给定的粒径范围内和给 定的悬浮体积单元内连续分布 第60页/共395页Figure 4.3 Schematic representation of a flow system containing an arbitrary suspension of particles undergoing various populatio