Generation of a batch recipe for a crystallization process and verification through dynamic simulation

Irene Papaeconomou & Rafiqul Gani

The following tutorial contains the steps through ICAS for obtaining the solid-liquid phase diagram, generating the batch recipe based on it and verifying the recipe through dynamic simulation set up in ICAS

CAPEC, Department of Chemical Engineering, DTU, Lyngby, Denmark

Application of the operational design algorithm for the generation of a batch recipe to separate NaCl and KCl from a mixture with water.
Problem Definition: A mixture of water, NaCl and KCl with a feed composition (on a 100 kg feed basis): water 80%, NaCl 15% and KCl 5% is to be separated. Objective: To recover 95% of the dissolved sodium chloride (NaCl). The operating range of temperature for the crystallizers is 0 oC to 100 oC.

Algorithm for the operational modelling of batch crystallization

Given: Identities of the solvent and the solids Composition of the feed Temperature range Draw the solubility curves for the range of temperature on the ternary equilibrium diagram
i=1, , N

According to feed location on the ternary diagram and the specified product, check the feasibility of the precipitation of the solid

Identify the solid to precipitate and select the operation task (choose temperature, evaporation/dilution ratio (or mixing ratio)

Solid crystallized: Compute the product yield Desired yield achieved?

YES

NO

Solid/Liquid separation

Treat Mother Liquor as new feed

Solid/Liquid separation

Above operation path is converted to the operational steps for a batch crystallizer

How to produce a phase diagram with the help of ICAS

The first part of the algorithm is the generation of the phase diagram for the relevant system.
Step 1: Select the compounds for the specific problem.

Choose the compounds from the salts database.

General Note: Even though the main components are water, sodium-chloride and potassium-chloride, some extra compounds should be included in the component list, since they might precipitate at various temperatures. These extra compounds are the double salts of the two single salts and their hydrates (mono-, dihydrates). If these compounds are not included in the compound list, then even if they do precipitate at various temperatures, it wont be possible to be identified. Step 2: Select the thermodynamic model (use the default model for salts) Adjust the measure units to your problem. (kg for mass and oC for temperature) Step 3: Draw the stream Doubleclicking on a feed stream brings up the mixture specification dialog box, where one defines the feed stream. The temperature and pressure are 100 oC and 1 atm, respectively. The composition of stream 1 is water, 80 kg/hr, NaCl 15 kg/hr and KCl 5 kg/hr.

From the mixture specification dialog box, one can be directed to the thermodynamic property calculations window. There, a number of calculations are available for the mixture and solubility is one of them. This is how the phase diagram is created for a range of temperatures

Selecting water, NaCl and KCl and plotting solubility in a tringular diagram at a range of 0 to 100 degrees (multiple curves), we only need to run the simulation To visualize the results we just need to press on the plotting button

From the plotting button we get the diagram on the right. The actual point values for the solubility curves are hidden on the left of the diagram as it appears below.

These values can be copied and pasted in an excel file and further on manipulated. The result could be a plot as the one showed in the next slide.

The point values for the solubility curves in ICAS are given in rectangular coordinates X and Y and not in triangular coordinates x, y and z. In order to transform triangular coordinates to rectangular, one needs to do the following: If x is the composition of the compound on the top of the triangle, y the composition of the compound on the left of the triangle and z the composition of the compound on the right of the triangle, then X, Y and x, y, z are connected like that. X = x/2 + z Y=x So for the Feed (x=80, y=15, z=5), it is X = 80/2 + 5 = 45 and Y = 80

NaCl-KCl-H2O phase diagram (various temperatures)

H2O 100 90 80 70 60 50 40 30 20 10 0 NaCl 0
Feed1

0 oC o 20 C 60 C 100 oC
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KCl 100

100 90 80 70 60 50 40 30 20 10 0 NaCl 0

The position of the feed is in the unsaturated region, which is the H2O upper part of the triangle defined by the solubility curves. Below the solid-liquid equilibrium curves, one or two salts precipitate depending Feed1 on the position in the triangular diagram. In the area defined by the Unsaturated region NaCl vertex of the triangle, the invariant point, part of the 100 oC solubility curve and the NaClInvariant point NaCl KCl H2O axis, the only salt precipitates precipitates precipitating is NaCl. In a similar area on the right side of the triangle, the only salt precipitating is KCl. In the area defined by the NaCl, KCl vertices and Both NaCl and KCl precipitate the invariant point, both salts precipitate
KCl 100

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Check of the feasibility of the precipitation of a specified salt

Let (XF, YF) be the rectangular coordinates of the feed and (Xinv, Yinv) the coordinates of the invariant point at a specific temperature. Then for the case when a) YF > Yinv if

X=

50 * (Yinv YF ) X F * (Yinv 100) < X inv 100 YF

(1)

then the salt placed in the bottom left vertex of the triangle will precipitate. If the X described above is greater than Xinv, then the salt in the bottom right vertex of the triangle will precipitate. If X equals Xinv, then both salts will precipitate. and when b) YF < Yinv In addition to the constraint above, the following constraint has to be satisfied:

YF >

Yinv *XF X inv

(2)

for the salt in the bottom right vertex of the triangle to precipitate. Otherwise both salts will precipitate.

For the specific problem, the precipitation of the desired salt (NaCl) is feasible for all the temperatures in the given operating range (constraint (1) is satisfied). So crystallization at any temperature in the range will give NaCl. Since the feed lies in the unsaturated region, evaporation will have to be applied. As water is removed, the composition of the feed moves away from the H2O vertex along the line connecting the water vertex and the feed.
H 2O 100 90 80 70
100 oC
Feed1

0 oC

60 50 40 30 20 10 0 NaCl 0 KCl 100

SL1

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As it can be seen from the phase diagram, the area where NaCl solely precipitates is larger for the temperature of 100 oC. For that temperature, evaporation can be more extensive and the resulting slurry has a larger density (slurry density = mass of salts / mass of slurry = length Slurry_Mother Liquor / length NaCl_Mother Liquor). So, the operating temperature for the crystallization is chosen to be a 100 oC, for the above mentioned reasons. The evaporation ratio is chosen as follows: As mentioned previously, as water is removed, the composition of the feed moves away from the H2O vertex along the line connecting the water vertex and the feed. However, there is a maximum evaporation that can be achieved without crossing the boundary into the area where both salts precipitate (unwanted). The composition of the slurry on that boundary is found as the intersection of the evaporation line and the line connecting the NaCl vertex and the invariant point at a 100 oC. The actual slurry composition is found for about 99 % of the maximum evaporation. The amount of water evaporated is found as described next.

NaCl-KCl-H2O in triangular coordinates: Evaporative crystallization at 100 oC

H2O 100

On a 100 kg feed basis

Evaporate feed solution (Feed1). Saturation occurs at pt 1, on curve. Continue evaporation until slurry composition at pt 2. Amount of solvent evaporated: Length Feed1_pt.2 / Length H20_pt.2 * 100 kg feed = 65.278 kg H20 Remaining at point 2: 100-65.278=34.722 kg slurry. Reaching pt. 2 , we have only removed water. Pt. 2: 80-65.278=14.722 kg H2O, 15 kg NaCl and KCl 5 kg KCl 100

90 Feed1 80 0 oC

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0 NaCl 0

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NaCl-KCl-H2O in triangular coordinates: Evaporative crystallization at 100 oC

H2O 100

90 Feed1 80 0 oC

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100 oC

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Slurry at 2 is NaCl + liquor at pt 3. Pt. 3 is found as the intersection of the line connecting NaCl and the slurry (pt.2) and the solubility curve at a 100oC Slurry density: Length 2_3 / Length NaCl_3 = 0.3176 Solids precipitated: 0.3176 * 34.722 =11.028 kg NaCl Yield =11.028/15=73.52% < desired yield = 95% Pt 3: 34.722 - 11.028 = 23.694 kg Mother Liquor. Moving from pt.2 to pt. 3 we have only removed KCl NaCl.

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Since the desired yield for NaCl was not achieved, the mother liquor from the solid/liquid separation is treated as a new feed. From the feasibility check, it is obvious that it is not possible to precipitate NaCl at any temperature for that feed (diluted or condensed). However, the precipitation of KCl is feasible for all the temperature range and as it can be seen from the phase diagram, pt 3 lies in the saturated region for KCl, so no evaporation is needed. The operating temperature for the crystallization of KCl is chosen so that the slurry density is highest. That is achieved for the lowest temperature of 0 oC.

NaCl-KCl-H2O in triangular coordinates: Cooling crystallization at 0 oC

H2O 100

90 Feed1 80 0 oC

Second crystallizer at 0oC. Mother Liquor (pt 3) from first crystallizer is in the saturated region for KCl at 0 oC. (no evaporation needed)
100 oC

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Slurry at 3 is KCl + liquor at pt 4. Pt 4 is found similarly to pt 3. Slurry density: Length 3_4 / Length KCl_4 = 0.1322 Solids precipitated: 0.1322 * 23.694 =3.132 kg KCl Point 4: 23.694 - 3.132 = 20.562 kg mother liquor
KCl

0 NaCl 0

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The mother liquor in equilibrium with the precipitated salt in the second crystallizer (pt. 4) is treated as a new feed. The precipitation of NaCl is feasible for a temperature range of 20 to 100 oC. For the same reasons as in the first sub-task, the operating temperature is chosen to be T=100oC The new feed (pt 4) lies in the unsaturated region and evaporation needs to be applied. The evaporation ratio is calculated such, so that the resulting slurry is in equilibrium with a mother liquor of a composition of pt 3 (ML1). This means that the resulting slurry has a composition of the intersection of evaporation line connecting points 4 and the H2O vertex and of the line connecting the NaCl vertex and point 3 (ML1).

Amount of solvent evaporated: Length pt.4_pt.5 / Length H20_pt.5 * 20.562 kg feed (pt4) = 9.209 kg H20 (From 4 --> 5): Remaining at point 5: 20.562 - 9.209 = 11.353 kg slurry. Slurry density: Length 5_3 / Length NaCl_3 = 0.2179 Solids precipitated: 0.2179 * 11.353 =2.474 kg NaCl Yield =(11.028+2.474)/15=90.01% < desired yield = 95%

A repeated procedure, moving on the phase diagram from point 3 to 4 to 5 and again to 3, resulting in an alternate precipitation of NaCl and KCl at a 100 oC and 0 oC respectively, is applied. In summary, the operational path generated to recover 95 % of the dissolved NaCl is the following:

Crystallizer 1 NaCl 2 KCl 1 NaCl 2 KCl 1 NaCl

Temperature C Operational task Predicted Prod. yield 100 Evaporation 65.278 kg 73.60% 0 Cooling crystallization 62.55% 100 Evaporation 9.209 kg 90.09% 0 Cooling crystallization 85.95% 100 Evaporation 3.145 kg 96.28%>95%

Verification of the generated recipe through dynamic simulation set up in ICAS

A crystallizer needs to be added to the icas file that was created in order to obtain the solid-liquid phase diagram for the ternary system. The unit CRYST is added and 3 streams are taken from the top, right and bottom of the unit. The top stream is the vapour leaving the crystallizer (solvent removed). The stream leaving from the right side of the unit is in the liquid form, which is the mother liquor in equilibrium with the precipitated solid of the bottom stream leaving the crystallizer.

In addition, two tanks are added in the flowsheet to collect the liquid and the solid, after their separation from the desired slurry.

Doubleclicking on the crystallizer, brings up the unit specification dialog box for this unit. From the Property values button: the temperature of the crystallization is set (subtask 1: precipitation of NaCl T=100 oC).

Calculation modes, entrainments and saturation are set from the Unit specific Specifications button. For this specific problem, we know the temperature of the crystallizer and the desired vaporization (rate: 65.278kg = 3.6235 kmoles), so the mode of calculation is the first one. The percent of saturation of the exit liquid (mother liquor) is set to 99 with respect to the most saturated component. The valve constant is set to a very small value for the evaporation. The specifications for the 2 tank mixers are defined in the Unit Specific specifications button, by doubleclicking on the unit.

Before the dynamic simulation engine can be started, the initial holdup file has to be created. Invoking the dynamic simulator from the main frame of ICAS, the option to generate holdup information is chosen first. The generated dynsimb.dat file should look like that.

Cl-

Na+

K+

0H-

H+

initial tanks holdup

equivelent in kmoles of 80 kg of H2O Cl- = Na+ + K+

equivelent in kmoles of 15 kg of NaCl

equivelent in kmoles of 5 kg of KCl

Before the simulation is run through DYNSIM, the flowrate of the feed stream in the crystallizer is set to zero. This is because the unit is already filled with the feed mixture (initial holdup file: dynsimb.dat).

The simulation time depends on the evaporation rate specified in the crystallizer Since the evaporation rate was specified to 3.6235 kmoles/hr = 65.278 kg/hr, we only need to run the simulation for one hour. (160 time steps, pfw=0.01) After the end of this run, the composition in the crystallizer will be the desired slurrys composition.

The precipitation of the salt (solid/liquid separation) is simulated by changing only the following specifications in the crystallizer: Vaporization is set to 0 kmoles/hr and the valve is opened (valve constant = 1500). The resulting holdup file from the previous vaporization is used as an initial holdup file for the precipitation. The simulation time is such that the content of the crystallizer (mother liquor + salt) is transferred to the two tanks. (t=0.67 hr, No of steps 127, pfw=0.01) For the precipitation of KCl (Cooling crystallization at 0 oC), one uses as initial holdup the resulting holdup file from the previous precipitation of NaCl, where the previous mother liquor holdup is now the content of the crystallizer and the tanks are empty and T=0 oC. Vaporization is still set to 0 kmoles/hr and the valve is opened (valve constant = 1500). (Because the content of the crystallizer (previous ML) is in the saturation region of KCl for 0 oC) The difference in the input is that the temperature of the crystallizer is 0 oC. The simulation time is such that the content of the crystallizer (mother liquor + salt) is transferred to the two tanks. (t=0.53 hr, No of steps 113, pfw=0.01)

The next step is crystallization at 100 oC, which will result to the precipitation of NaCl. The resulting holdup file from the previous precipitation of KCl (where the previous mother liquor holdup is now the content of the crystallizer, the tanks are empty and T=100oC) is the initial holdup. Only the following specifications in the crystallizer are changed: The evaporation rate is specified to 0.511 kmoles/hr = 9.209 kg/hr and we only need to run the simulation for one hour. (160 time steps, pfw=0.01) After the end of this run, the composition in the crystallizer will be the desired slurrys composition. The second time precipitation of NaCl is simulated similarly as described before. The same applies for the following precipitation of KCl and the last evaporation and precipitation of NaCl. The icas files for this tutorial are gathered in 8 steps in the zip file that is attached.
1) 2) 3) 4) Evaporation at 100 oC (Evap1.ics) Precipitation of NaCl at 100 oC (NaCl1.ics) Precipitation of KCl at 0 oC (KCl1.ics) Evaporation at 100 oC (Evap2.ics) 5) Precipitation of NaCl at 100 oC (NaCl2.ics) 6) Precipitation of KCl at 0 oC (KCl2.ics) 7) Evaporation at 100 oC (Evap3.ics) 8) Precipitation of NaCl at 100 oC (NaCl3.ics)

To run the simulationyourself , youll have to replace the dynsimb.dat file present in the directory with the one from the corresponding directory Initial holdup.