MATHEMATICAL

MODELS

OF

CHEMICAL

ENGINEERING

SYSTEMS

Tray

(top tray):
at

YNT.

(3.106) (3.107)

Reflux drum :
at R = V - D

(3.108) (3.109)

3.14

SYSTEMS

The control of is a very important problem in many processes, particularly in effluent wastewater treatment. The development and solution of mathematical models of these systems is, therefore, a vital part of chemical engineering dynamic modeling.

3.141 Equilibrium-Constant Models

The traditional approach is to keep track of the amounts of the various chemical species in the system. At each point in time, the hydrogen ion concentration is calculated by solving a set of simultaneous nonlinear algebraic equations that result from the chemical equilibrium relationships for each dissociation reaction. For example, suppose we have a typical wastewater control system. Several inlet feed streams with different chemical species, titration curves, and levels are fed into a perfectly mixed tank. If the feed streams are acidic, some source of OH- ions is used to bring the up to the specification of seven. A slurry of and/or caustic are usually used. The equilibrium-constant method uses a dynamic model that keeps track of all chemical species. Suppose, for example, that we have three dissociating acids in the system. Let the concentration of acid HA at some point in time be This concentration includes the part that is dissociated, plus the part that is not dissociated. The same quantity for acid HB is and for acid C is Cc. These three acids come into the system in the feed streams.

EXAMPLES

OF

MATHEMATICAL

MODELS

OF

CHEMICAL

ENGINEERING

SYSTEMS

75

These dissociation reactions are reversible and have different forward and reverse rate constants, The equilibrium relationships for these three reactions are expressed in terms of the equilibrium constants , , and Kc. (3.110)

(3.112) To solve for the concentration of hydrogen ion [H] at each point in time, these three nonlinear algebraic equations must be solved simultaneously. Let = fraction of HA dissociated y = fraction of HB dissociated z = fraction of HC dissociated Then Concentration of Concentration of Concentration of =x =y =z (3.113) y z

Concentration of undissociated HA = Concentration of undissociated HB = Concentration of undissociated HC = Cc Concentration of = +y+z

These concentrations are substituted in Eqs. (3.110) to giving three highly nonlinear algebraic equations in three unknowns: y, and z. These nonlinear equations must be solved simultaneously at each point in time. Usually an iterative method is used and sometimes convergence problems occur. The complexity grows as the number of chemical species increases. This modeling approach requires that the chemical species must be known and their equilibrium constants must be known. In many actual plant situations, this data is not available.

3.14.2 Titration-Curve Method

The information that is available in many chemical plants is a titration curve for each stream to be neutralized. The method outlined below can be used in this

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MATHEMATICAL MODELS OF CHEMICAL ENGINEERING SYSTEMS

situation. It involves only a simple iterative calculation for one unknown at each point in time. Let us assume that titration curves for the feed streams are known. These can be the typical sharp curves for strong acids or the gradual curves for weak acids, with or without buffering. The dynamic model keeps track of the amount of each stream that is in the tank at any point in time. Let be the concentration of the nth stream in the tank, be the flow rate of that stream into the tank, and be the total flow rate of material leaving the tank. If the volume of the liquid in the tank is constant, the outflow is the sum of all the inflows. The rates of caustic and lime slurry are usually negligible. For three feed streams
= + +

(3.114)

The dynamic component balance for the nth stream is

dt

where

= volume of the tank.

The dynamic balance for the OH- ion in the system is

dt

(3.116)

where Con = concentration of OH- ions in the system = total flow rate of OH- ion into the system in the caustic and lime slurry streams = rate of OH- ion generation due to the dissolving of the solid particles The rate of dissolution can be related to the particle size and the OH- concentration. (3.117) where and are constants determined from the dissolution rate data for solid and is the solid concentration at any point in time. The steps in the titration-curve method are: and Con are known. 1. At each point in time, all the in the tank. 2. Guess a value for 3. Use the titration curve for each stream to determine the amount of OH- ion required for that stream to bring it up to the guess value of 4. Check to see if the total amount of OH- actually present (from Con) is equal to the total amount required for all streams. 5. Reguess if step 4 does not balance.

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77

The method involves a simple iteration on only one variable, Simple interval-halving convergence (see Chap. 4) can be used very effectively. The titration curves can be easily converted into simple functions to include in the computer program. For example, straight-line sections can be used to interpolate between data points. This method has been applied with good success to a number of processes by Schnelle (Schnelle and Luyben, Proceedings of ISA 88, Houston, October 1988). PROBLEMS
3.1. A fluid of constant density is pumped into a cone-shaped tank of total volume The flow out of the bottom of the tank is proportional to the square root of the height of liquid in the tank. Derive the equations describing the system.

FIGURE P3.1

3.2. A perfect gas with molecular weight M flows at a mass flow rate into a cylinder through a restriction. The flow rate is proportional to the square root of the pressure drop over the restriction:
=

where is the pressure in the cylinder and is the constant upstream pressure. The system is isothermal. Inside the cylinder, a piston is forced to the right as the pressure P builds up. A spring resists the movement of the piston with a force that is proportional to the axial displacement x of the piston.
=

Pressure on the spring side of the piston is atmospheric.

FIGURE P3.2