EXAMPLE 15.

3 Coulson

What is the theoretical yield of crystals which may be obtained by cooling a solution containing
1000 kg of sodium sulphate (molecular mass = 142 kg/kmol) in 5000 kg water to 283 K? The
solubility of sodium sulphate at 283 K is 9 kg anhydrous salt/100 kg water and the deposited
crystals will consist of the deca-hydrate (molecular mass = 322 kg/kmol). It may be assumed
that 2 percent of the water will be lost by evaporation during cooling.

The ratio, R = (322/142) R = 2.27

The initial concentration, c1 = (1000/5000) c1= 0.2 kg Na2SO4/kg water

The solubility, c2 = (9/100) c2= 0.09 kg Na2SO4/kg water

The initial mass of water, w1 = 5000 kg

and the water lost by evaporation, E = (2/100) E = 0.02 kg/kg

Thus, in equation 15.22: y = Rw1 [c1 c2(1 E)] / [1 c2(R 1)]

yield, y = (2.27 5000)[0.2 0.09(1 0.02)]/[1 0.09(2.27 1)] = 1432 kg Na2SO4.10H2O

EXAMPLE 15.4 Coulson

What is the yield of sodium acetate crystals (CH3COONa.3H2O) obtainable from a vacuum
crystalliser operating at 1.33 kN/m2 when it is supplied with 0.56 kg/s of a 40 per cent
aqueous solution of the salt at 353 K? The boiling point elevation of the solution is 11.5 deg
K.

Data:

Heat of crystallisation, q = 144 kJ/kg trihydrate

Heat capacity of the solution, Cp = 3.5 kJ/kg deg K

Latent heat of water at 1.33 kN/m2 , = 2.46 MJ/kg

Boiling point of water at 1.33 kN/m2 BPH20= 290.7 K

Solubility of sodium acetate at 290.7 K, c2 = 0.539 kg/kg water

Equilibrium liquor temperature = (290.7 + 11.5) = 302.2 K.

Initial concentration, c1 = 40/(100 40) c1= 0.667 kg/kg water

Final concentration, c2 = 0.539 kg/kg water

Ratio of molecular masses, R = (136/82) R = 1.66

Thus, in equation 15.23: (E = qR(c1 c2) + Cp(T1 T2)(1 + c1)[1 c2(R 1)] [1 c2(R 1)]
qRc2) E = {144 1.66(0.667 0.539) + 3.5(353 302.2)(1 + 0.667)[1
0.539(1.66 1)]}/ {2460[1 0.539(1.66 1)] (144 1.66 0.539)}

E = 0.153 kg/kg water originally present.

The yield is then given by equation 15.22 as: y = Rw1 [c1 c2(1 E)] / [1 c2(R 1)]

y = (0.56(100 40)/100)1.66[0.667 0.539(1 0.153)]/[1 0.539(1.66 1)]= 0.183 kg/s

EXAMPLE 15.5 Coulson

A solution containing 23 per cent by mass of sodium phosphate is cooled from 313 to 298 K
in a Swenson-Walker crystalliser to form crystals of Na3PO4.12H2O. The solubility of Na3PO4 at
298 K is 15.5 kg/100 kg water, and the required product rate of crystals is 0.063 kg/s. The
mean heat capacity of the solution is 3.2 kJ/kg deg K and the heat of crystallisation is 146.5
kJ/kg. If cooling water enters and leaves at 288 and 293 K, respectively, and the overall
coefficient of heat transfer is 140 W/m2 deg K, what length of crystalliser is required?

The molecular mass of hydrate/molecular mass of anhydrate, R = (380/164) R = 2.32

It will be assumed that the evaporation is negligible and that E = 0.

The initial concentration, c1 = 0.23 kg/kg solution or 0.23/(1 0.23) c1= 0.30 kg/kg water

The final concentration, c2 = 15.5 kg/100kg water c2= 0.155 kg/kg water

In 1 kg of the initial feed solution, there is 0.23 kg salt and 0.77 kg water; hence w1 = 0.77 kg

The yield is given by equation 15.22: y = Rw1 [c1 c2(1 E)] / [1 c2(R 1)]

y = 2.32 0.77[0.30 0.155(1 0)]/[1 0.155(2.32 1)]

y = 0.33 kg

In order to produce 0.063 kg/s of crystals, the required feed is: = (1 0.063/0.33) = 0.193 kg/s

q= FCpf (Tf-Tc) + CHc

FCpf (Tf-Tc) = 0.193 3.2(313 298) = 9.3 kW

CHc = (0.063 146.5) = 9.2 kW;

q = a total of (9.3 + 9.2) = 18.5 kW

Assuming countercurrent flow, deltaT1 = (313 293) = 20 deg K ; deltaT2 = (298 288) = 10
deg K

and the logarithmic mean, Tm = (20 10)/ ln(20/10) = 14.4 deg K

The heat transfer area required, A = Q/UTm = 18.5/(0.14 14.4) = 9.2 m2

Assuming that the area available is, typically, 1 m2/m length, the length of exchanger required =
9.2 m. In practice 3 lengths, each of 3 m length would be specified.
EXAMPLE 12.11-2 CRYSTALLIZATION PPT

A feed solution of 2268 kg at 327.6 K (54.4oC) containing 48.2 kg MgSO4/100 kg total water
is cooled to 293.2 K (20oC) 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 (18oC) 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 evolved and removed from the crystalliser, q, assuming that no water is vaporized.

Ans: 616.9 kg crystal, -261 912 kJ

Molecular weights: MgSO4 = 120.4, 7H2O = 126, MgSO4 7H2O = 246.4

F= 2268 kg ; 48.2 kg MgSO4/100 kg H2O S kg solution

35.5 kg MgSO4/100 kg H2O

C kg MgSO4 7H2O

OMB: 2268 = C + S ; S = 2268 - C

SB: 2268 (48.2 / 148.2) = (2268 C) (35.5 / 135.5) + C ( 120.4 / 246.4 )

C = 631.9 kg MgSO47H2O crystals, S = 1636.1 kg solution.

HB:

FhF + q = W + ChC

Enthalpy of the feed , hF = CpT hF = (2.93)(327.6-293)

Heat of solution = 13.31x103/246.49 = 54.0 kJ/kg crystals.

Heat of crystallization = -(54.0) hC= -54.0 kJ/kg crystals

W = 0

2268(2.93)(327.6-293) + q = 631.9(54.0)

q = 631.9(54.0) - 2268(2.93)(327.6-293)

q = -262 689 kJ
A hot solution containing 1000 kg of MgSO4 and water having a concentration of 30 wt%
MgSO4 is cooled to 288.8 K (60oF) where crystals of MgSO4.7H2O are precipitated. The
solubility at 288.8 K is 24.5 wt % anhydrous MgSO4 in the solution. Calculate the yield of crystals
obtained if 5 % of the original water in the system evaporates on cooling. Data: Molecular
weight of MgSO4 = 120.4 Ans: 261 kg

A 32.5% solution of MgSO4 at 120oF (48.9oC) is cooled, without appreciable evaporation to

70oF (21.1oC) in a batchcooled crystallizer. How much heat must be removed from the solution
per 100 Ib of the feed solution? The average heat capacity of the feed solution is 0.72 Btu/Ib oF
and the heat of solution at 18oC is 23.2 Btu/Ib of MgSO4.7H20.

Ans: -4260 Btu

A solution of 500 kg of Na2SO4 in 2500 kg water is cooled from 333K to 283K in an agitated
mild steel vessel. At 283K, the solubility of the anhydrous salt is 8.9 kg/100kg water and the
stable crystalline phase is Na2SO4.10H2O. At 291K, the heat of solution is -78.5 MJ/kmol and
the specific heat capacity of the solution is 3.6 kJ/kg.K. If, during cooling, 2% of the water initially
present is lost by evaporation, estimate the heat which must be removed.

Ans: 240 407 Kj

A hot solution of Ba(NO3)2 from an evaporator contains 30.6kg Ba(NO3)2 /100 kg H2O and
goes to a crystallizer, where the solution is cooled and Ba(NO3)2 crystallizes. On cooling, 10% of
the original water present evaporates. For a feed solution of 100kg total, calculate the yield of
crystals if the solution is cooled to 290K (17C) (PROCESS A), where the solubility is 8.6kg
Ba(NO3)2 /100 kg H2O total water. Then, determine the yield of crystals if it is cooled instead to
283K (PROCESS B), where the solubility is 7.0kg Ba(NO3)2 /100 kg total water.

A. PROCESS A: 17.5026kg; PROCESS B: 18.6077kg

A feed solution of 8650 lbm is flowed into the system at 180F. The concentrated solution is
flowed out at 60F. The yield of crystals FeSO4.7H2O is 1750 lbm. The average heat capacity of
the feed is 0.90 btu/lbm.F. The heat of solution at 60F is -23.49 btu/lbm FeSO4.7H2O. Calculate
the total heat transfer and determine heat is absorbed or removed during crystallization.
Assume no evaporation of water.

A. Q = -975307.5btu; heat is removed

A batch of 1000kg of KCl is dissolved in sufficient water to make saturated solution at 363K,
where the solubility is 35wt% KCl in water (A). The solution is cooled to 293K, at which
temperature its solubility is 25.4wt% (B). Compare the amount of crystals from before and after
the cooling process. Which process will produce more crystals?

A<B