Chapter 8- Crystallization

Introduction Crystal Geometry Equilibrium Solubility Yield and Material Balance Heat Effects and Heat balances Crystallization Theory Rate of crystal growth Models for MSMPR

Introduction
Crystallization is a solidliquid separation process-mass transfer of a solute from the liquid solution to a pure solid

crystalline phase occurs.

Example-production of sucrose from sugar beet, where the sucrose is crystallized out from an aqueous solution.

This process can occur in the freezing of water to form ice, in

the formation of snow particles from a vapor, in the formation of solid particles from a liquid melt, or in the formation of solid

crystals from a liquid solution.

Introduction
In crystallization the solution is concentrated and usually

cooled until the solute concentration becomes greater than its

solubility at that temperature. Then the solute comes out of the solution, forming crystals of approximately pure solute.

In commercial crystallization not only are the yield and purity of the crystals important but also the sizes and shapes of the crystals.

It is often desirable that crystals be uniform in size.

Crystal geometry
A crystal can be defined as a solid composed of atoms, ions, or molecules which are arranged in an orderly and repetitive

manner.
It is a highly organized type of matter.

The atoms, ions, or molecules are located in threedimensional arrays or space lattices

Crystal geometry
There are seven classes of crystals arrangement of the axes to which the angles are referred:
Cubic system. Three equal axes at right angles to each other. Tetragonal system. Three axes at right angles to each other, one axis longer than the other two.

Orthorhombic system. Three axes at right angles to each other, all of different lengths.
Hexagonal system. Three equal axes in one plane at 60 to each other, and a fourth axis at right angles to this plane and not necessarily the same length.
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Crystal geometry

Monoclinic system. Three unequal axes, two at right angles in a plane and a third at some angle to this plane.

Triclinic system. Three unequal axes at unequal angles to each other and not 30, 60, or 90.
Trigonal system. Three equal and equally inclined axes

Equilibrium Solubility in Crystallization

In crystallization equilibrium is attained when the solution or mother liquor is saturated represented by a solubility curve. Solubility is dependent mainly upon temperature.

Pressure has a negligible effect on solubility.

Solubility data are given in the form of curves where solubility's in some convenient units are plotted versus temperature. Solubility curves for some typical salts in water were given in Fig 8.1. In general, the solubility's of most salts increase slightly or 7 markedly with increasing temperature.

Equilibrium Solubility in Crystallization

Yields and material balances in crystallization

In most of the industrial crystallization processes, the solution (mother liquor) and the solid crystals are in contact for enough time to reach equilibrium. Hence, the mother liquor is saturated at the final temperature of the process, and the final concentration of the solute in the solution can be obtained from the solubility curve. The yield of crystals from a crystallization process can then be calculated knowing the initial concentration of solute, the final temperature, and the solubility at this temperature.

Yields and material balances in crystallization

In some instances in commercial crystallization, the rate of crystal growth may be quite slow, due to a very viscous

solution or a small surface of crystals exposed to the solution.

Hence, some super saturation may still exist, giving a lower yield of crystals than predicted.

In making the material balances, the calculations are straightforward when the solute crystals are anhydrous. Simple water and solute material balances are made. When the crystals are hydrated, some of the water in the

solution is removed with the crystals as a hydrate.

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EXAMPLE
A salt solution weighing 10000 kg with 30 wt % Na2CO3 is cooled to 293 K (20C). The salt crystallizes as the decahydrate. What will be the yield of Na2CO3 10H2O

crystals if the solubility is 21.5 kg anhydrous Na2CO3/100 kg

of total water? Do this for the following cases: a. Assume that no water is evaporated. b. Assume that 3% of the total weight of the solution is lost by evaporation of water in cooling.

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EXAMPLE

The molecular weights are 106.0 for Na2CO3, 180.2 for

10H2O, and 286.2 for Na2CO3 10H2O.

The process flow diagram is shown in Fig. 8.2, with W being kg H2O evaporated, S kg solution (mother liquor),

and C kg crystals of Na2CO3 10H2O.

Making a material balance around the dashed-line box for water for part (a), where W = 0,

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EXAMPLE

Fig. 8.2
8.1

where (180.2)/(286.2) is wt fraction of water in the crystals. Making a balance for Na2CO3,
8.2

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EXAMPLE
Solving the two equations simultaneously, C = 6370 kg of Na2CO3 10H2O crystals and S = 3630 kg solution. For part (b), W = 0.03(10 000) = 300 kg H2O. Equation (8.1) becomes Equation 8.3
8.3

Equation (8.2) does not change, since no salt is in the W stream. Solving Eqs. (8.2) and (8.3) simultaneously,

C = 6630 kg of Na2CO3 10H2O crystals and S = 3070 kg solution.

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Heat effects and heat balances

The most satisfactory method for calculating heat effects during a crystallization process is to use the enthalpy concentration chart for the solution and the various solid phases which are present for the system. However, only a few such charts are available, including the following systems: calcium chloridewater , magnesium sulfatewater , and ferrous sulfatewater . When such a chart is available, the following procedure is used.

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Heat effects and heat balancescontd

The enthalpy H1 of the entering solution at the initial temperature is read off the chart, where H1 is kJ (btu) for the total feed. The enthalpy H2 of the final mixture of crystals and mother liquor at the final temperature is also read off the chart.

If some evaporation occurs, the enthalpy Hv of the water vapor is obtained from the steam tables.
The total heat absorbed q in kJ is
8.4

If q is positive, heat must be added to the system. If it is negative, heat is evolved or given off.
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EXAMPLE
A feed solution of 2268 kg at 327.6 K (54.4C) containing 48.2 kg MgSO4/100 kg total water is cooled to 293.2 K

(20C), where MgSO4 7H2O crystals are removed. The

solubility of the salt is 35.5 kg MgSO4/100 kg total water . The average heat capacity of the feed solution can be assumed

as 2.93 kJ/kg K . The heat of solution at 291.2 K (18C) is 13.31 x 103 kJ/kg mol MgSO4 7H2O .

Calculate the yield of crystals and make a heat balance to determine the total heat absorbed, q, assuming that no water

is vaporized.

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EXAMPLE
Making a water balance and a balance for MgSO4 using equations similar to 8.1 and 8.2 C = 616.9 kg MgSO4 7H2O crystals and S = 1651.1 kg solution. To make a heat balance, a datum of 293.2 K (20C) will be used. The molecular weight of MgSO4 7H2O is 246.49. The enthalpy of the feed is H1: The heat of solution is -(13.31 x 103)/246.49 = -54.0 kJ/kg crystals. Then the heat of crystallization is -(-54.0) = +54.0 kJ/kg crystals, or 54.0(616.9) = 33 312 kJ. 18

EXAMPLE
This assumes that the value at 291.2 K is the same as at 293.2 K. The total heat absorbed, q, is

Since q is negative, heat is given off and must be removed.

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Equipment for Crystallization

Crystallizing equipment can be classified according to the methods used to bring about supersaturation as follows:

1. supersaturation produced by cooling the solution with negligible evaporationtank and batch-type crystallizers;
2. supersaturation produced by evaporation of the solvent with little or no coolingevaporatorcrystallizers and crystallizing evaporators; 2. supersaturation by combined cooling and evaporation in an adiabatic evaporatorvacuum crystallizers.

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CRYSTALLIZATION THEORY
Nucleation theory Nucleation is number of new particles formed per unit time per unit volume of mother liquor Solubility and crystal size Smaller crystal is better Solubility of small crystal better Homogeneous nucleation High supersaturation and no agitation; Result of random fluctuations of molecules in homogeneous solution
Contact nucleation With agitation Formation of nuclei occurs in collision between crystals Formation of nuclei due to interference of the contacting 21 agent (walls of a container or agitator blades)

CRYSTALLIZATION THEORY contd

The rate of growth of a crystal face is the distance moved per unit time in a direction that is perpendicular to the face.

Crystal growth is a layer-by-layer process, and since growth can occur only at the outer face of the crystal, the solute

material must be transported to that face from the bulk of the

solution.

The solute molecules reach the face by diffusion through the liquid phase. The usual mass-transfer coefficient ky applies in

this case.

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Rate of crystal growth and growth coefficients

At the surface the resistance to integration of the molecules into the space lattice at the face must be considered.

This reaction at the surface occurs at a finite rate, and the overall process consists of two resistances in series.

The solution must be supersaturated for the diffusion and

interfacial steps to proceed.

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Rate of crystal growth and growth coefficients

The equation for mass transfer of solute A from the bulk solution of supersaturation concentration yA, mole fraction of A, to the surface where the concentration yA is
8.5

where ky is the mass-transfer coefficient in kg mol/sm2mol frac, is rate in kg mol A/s, and Ai is area in m2 of surface i.

Assuming that the rate of reaction at the crystal surface is also dependent on the concentration difference,
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Rate of crystal growth and growth coefficients

8.6

where ks is a surface-reaction coefficient in kg mol/s m2 mol frac and yAe is the saturation concentration. Combining Eqs. (8.5) and (8.6),
8.7

where K is the overall transfer coefficient

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L law of crystal growth

McCabe has shown that all crystals that are geometrically similar and of the same material in the same solution grow at the same rate. Growth is measured as the increase in length L, in mm, in linear dimension of one crystal.

This increase in length is for geometrically corresponding

distances on all crystals.
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L law of crystal growth

This increase is independent of the initial size of the initial crystals, provided that all the crystals are subject to the same environmental conditions.
8.8

where t is time in h and growth rate G is a constant in mm/h. if D1 is the linear dimension of a given crystal at time t1 and

D2 at time t2,
8.9

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Particle-Size Distribution of Crystals

An important factor in the design of crystallization equipment is the expected particle-size distribution of the crystals obtained. Usually, the dried crystals are screened to determine the particle sizes.

The percent retained on different-sized screens is recorded.

The screens or sieves used are the Tyler standard screens

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Particle-Size Distribution of Crystals

The data are plotted as particle diameter (sieve opening in screen) in mm versus the cumulative percent retained at that size on arithmetic probability paper.

Data for urea particles from a typical crystallizer are shown in Fig. 8.3.

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Fig 8.3

A common parameter used to characterize the size distribution is the coefficient of variation, CV, as a percent:
8.9

where PD16% is the particle diameter at 16 percent retained

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Model for Mixed SuspensionMixed Product Removal Crystallizer

Mixed suspensionmixed product removal (MSMPR) crystallizer, which is by far the most important type of crystallizer in use in industry today. Model Assumptions Steady state, suspension completely mixed, no product classification, uniform concentration, no crystals in feed, and the L law of crystal growth applies. All continuous crystallizers have mixing by an agitator or by pump around.
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Crystal population-density function n

The total cumulative number of crystals N per unit volume of suspension (usually 1 L) of size L and smaller versus this size L, as in Fig. 8.4. The slope dN/dL of this line is defined as the crystal population density n:
8.10 n is the number of crystals/(L mm).

Fig 8.4
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Randolph and Larson Model

For this model a relation between population density n and size L is desired.

This population density is obtained experimentally by screen analysis of the total crystal content of a given volume, such as 1.0 L of magma suspension. Each sieve fraction by weight is obtained by collection between two closely spaced and adjacent screens.
Then, Lav = (L1 + L2)/2, where L1 and L2 are the openings in mm in the two adjacent screens. Also, L = (L1 - L2), where L1 is the size opening of the upper screen.
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Then the volume of a particle p is

8.11

Where p is mm3/particle and a is a constant shape factor

Knowing the total weight of the crystals in this fraction, the density in g/mm3, and the weight of each crystal, which is p, the total number of crystals N is obtained for the size range L. Then, rewriting Eq. (8.10) for this L size
8.12

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Population material balance

Since the effluent composition in the outflow of Q L/h is the same as that in the crystallizer,

then the ratio (n L)/(n L), or fraction of particles withdrawn during t time, is the same as the volume ratio Q t withdrawn divided by the total volume V of the crystallizer.
8.13

During this time period t, the growth L of a crystal is

8.14

where G is growth rate in mm/h. Combining Eqs. (8.13) and (8.14)

8.15

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Letting L 0, n 0, and integrating,

8.16

where n0 is population of nuclei when L = 0, n is population when the size is L, and V/Q is the total retention or holdup time in h in the crystallizer. A plot of Eq. (8.16) of ln n versus L is a straight line with intercept n0 and slope -1/G. If the line is not straight, this could be an indication of the violation of the L law 36

Average particle size and nucleation rate

the average size La in mm of the mass distribution:
8.17

Here, 50% of the mass of the product is smaller or larger in size than this value. Also, the predominant particle size is given as
8.18

the nucleation rate B0 to the value of the zero-size particle population density n0 and the growth rate G. For the condition L-> 0, the limit of dN/dt (nucleation rate) can be written as
8.19

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Average particle size and nucleation rate

when L-> 0, the slope dL/dt = G, the slope dN/dL = n0, and B0 = dN/dt
8.20

where B0 is nucleation rate in number of nuclei/h L

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Prediction of cumulative weight fraction obtained

The population equation can be used to perform a reverse calculation when only values of G and are known.

The following equation has been derived from the population density function
8.21

where x = L/G, and (1 - Wf) is the cumulative wt fraction at opening L mm, which is in the same form of results as from a screen analysis.

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Growth and Nucleation Rates MSMPR Crystallizer

Calculate the population density and nucleation growth rates for crystal samples of urea from a screen analysis. The slurry density (g of crystals) is 450 g/liter, the crystal shape factor a is 1.00, the crystal density is 1.335 g/cm3, and the residence time is 3.38 h. The screen analysis from reference is as follows:
Mesh -14, +20 Wt % 4.4 Mesh -48, +65 Wt % 15.5

-20, +28
-28, +35

14.4
24.2

-65, +100
-100

7.4
2.5
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-35, +48

31.6

The data above are tabulated in Table 8.1 using data from Appendix. The value of L is the screen opening. For the 1420 mesh portion, Lav = (1.168 + 0.833)/2 = 1.001 mm and L = 1.168 - 0.833 = 0.335 mm. For Lav = 1.001 mm, using Eq. (8.11), p = = 1.00(1.001)3 = 1.003 mm3/particle. The density = 1.335 g/cm3 = 1.335 x 10-3 g/mm3 and the mass/particle = p = 1.335 x 10-3 (1.003) = 1.339 x 10-3 g.
41 The total mass of crystals = (450 g/L)(0.044 wt frac

The data above are tabulated in Table 8.1 using data from Appendix. The value of L is the screen opening. For the 1420 mesh portion, Lav = (1.168 + 0.833)/2 = 1.001 mm and L = 1.168 - 0.833 = 0.335 mm. For Lav = 1.001 mm, using Eq. (8.11), p = = 1.00(1.001)3 = 1.003 mm3/particle. The density = 1.335 g/cm3 = 1.335 x 10-3 g/mm3 and the mass/particle = p = 1.335 x 10-3 (1.003) = 1.339 x 10-3 g.
42 The total mass of crystals = (450 g/L)(0.044 wt frac

Table 18.1. Mesh L (mm) Mesh L (mm) Lav (mm) 14 20 28 35 48 65 1.17 0.83 0.59 0.42 0.3 0.21 20 28 35 48 65 100 0.83 0.59 0.42 0.3 0.21 0.15 1 0.71 0.5 0.36 0.25 0.18

L (mm) 0.34 0.24 0.17 0.12 0.09 0.06

ln n

wt %

10.7 13.2 15.1 16.8 17.4 18.1

4.4 14.4 24.2 31.6 15.5 7.4

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Using Eq. (8.12) to calculate n for the 1420 mesh size range,

Then ln n = ln 4.414 x 104 = 10.695.

For the 2028 mesh size range, Lav = 0.711/mm, and L = 0.244. Then,

The ln n is plotted versus L in Fig. 8.5. The equation of this line is Eq. (8.16), where the slope is -9.12 and the intercept = 19.79:
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Fig. 8.5
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The slope -9.12 = -1/G = -1/(G)(3.38).

Hence, G = 0.03244 mm/h. The intercept ln n0 = 19.79.

Hence, n0 = 3.933 x 108. From Eq. (8.20), the nucleation rate B0 is B0 = Gn0 = 0.03244(3.933 x108) = 1.26 x 107 nuclei/h L The average size is, from Eq. (8.17), La = 3.67G = 3.67(0.03244)(3.38) = 0.402 mm. The predominant size, from Eq. (8.18), Ld = 3.00G = 3.00(0.03244)(3.38) = 0.329 mm.
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