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Modeling and Simulation of CSTR for Manufacture of Propylene Glycol

Conference Paper · December 2005


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V.V.P. Engineering College


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Session: Modeling and Simulation of Processes
CHEMCON – 05, New Delhi

Modeling and Simulation of CSTR for Manufacture of

Propylene Glycol
Piyush Vanzaraa, Vyomesh Parsanab*

Department of Chemical Engineering, V.V.P. Engineering College, Rajkot-360005,
Gujarat, India, Email:
Department of Chemical Engineering, V.V.P. Engineering College, Rajkot-360005,
Gujarat, India, Email:

Keywords: Propylene glycol; Start up of a CSTR; Practical stability limit

Commercially, propylene glycol is produced by direct hydrolysis of propylene oxide with
water. This first-order, irreversible and exothermic reaction is carried out in a glass-lined
CSTR. In this study, startup of the CSTR has been modeled from first principles and simulated
using POLYMATH 5.1 to obtain concentration and temperature profiles. It is often very
important how these profiles approach their steady state values. For example, a significant
overshoot in temperature while approaching steady state may cause a reactant or a product
to degrade, or the overshoot may be unacceptable for safe operation. If either case were to
occur, the system would exceed its practical stability limit. The practical stability limit
represents a temperature above which it is undesirable to operate because of unwanted side
reactions or damage to the equipment.

Propylene glycol is one of the most commonly used humectants that have a high affinity for
water and have a stabilizing action on the water content of a material. It is used to maintain
moisture within a narrow range in certain food products, such as coconut and marshmallows,
as well as in tobacco. It is also used to absorb extra water and maintain moisture in certain
medicines and cosmetics. A growing application of propylene glycol is in the field of deicers
and automotive antifreeze components. It reduces the freezing point of water and is therefore
being developed as an alternative to ethylene glycol in automotive antifreeze systems. It is
used as solvent in paints, plastics and for food colours and flavours. It is used to make
unsaturated polyester resins, liquid detergents, pharmaceuticals, coatings, inks, nail polish,
lacquers, latex paints, and adhesives. It is also used to create artificial smoke or fog used
in fire-fighting training and in theatrical productions.

Propylene glycol is produced from propylene oxide by liquid phase hydrolysis with excess water
in the presence of a small concentration of sulfuric acid as the catalyst. The reaction is:

Propylene oxide (A) Water (B) Propylene glycol (C)

The reaction takes place at a reasonable rate at near-ambient temperatures, but due to the heat
of exothermic reaction the temperature rise can be appreciable. A large excess of water is
used to keep the reaction in the liquid phase because it is important to control the temperature
of the reaction mixture, since propylene oxide is a rather low-boiling species (Tnbp = 34.3oC).
In addition, methanol is added to prevent phase splitting because propylene oxide is not
completely soluble in water. Propylene oxide can also readily react with propylene glycol to
produce di-, tri- and polypropylene glycols. The presence of excess water minimizes the
formation of these undesired side products. A 15-20 fold molar excess of water is typically
employed. The reaction can be modeled with power-law kinetics that is pseudo first order
with respect to the propylene oxide concentration. The rate expression is:
-rA = kCA ; k = A e(-E/RT) -rA = -rB = rC

Consider the liquid phase reaction between propylene oxide and water at room temperature
catalyzed by H2SO4 in a jacketed CSTR. Initially there is only water (55 kmol/m3) at 25oC
(T0) and 0.1 wt % H2SO4 in the 5.5 m3 (V) reactor. The feed stream consists of 175 kmol/hr
(FA0) of propylene oxide (A), 2300 kmol/hr (FB0) of water (B) containing 0.1 wt % H2SO4
and 10 kmol/hr (FM0) of methanol (M). The water coolant flows through the jacket at a rate of
2.268 kg/s and at a temperature of 30oC (Tj).

Model Development of CSTR

The following assumptions have been made in the model formulation.
1. The variations of heat of reaction, densities, heat capacities and UA are neglected over
the temperature range of the reaction.
2. Under the prevailing conditions of concentrations and reactor temperature, side
reactions are neglected.
3. Jacket fluid flow rate and temperature are treated as constants.
Mole Balance: Applying law of conservation of mass for all species present in the reacting
Rate of accumulation Rate of Rate of
Rate of production /
of mass within the = mass flow – mass flow +
depletion of mass
reactor in out
dN A
Species A: = υ0 CA0 - υ0 C A + (-rA )V
dCA υ0
∴ = (CA0 - C A ) + (-rA )
dt V
dCA 1 V F M Fi
∴ = (CA0 - C A ) + (-rA ) , where τ = ; υ 0 = ∑ i 0 i ; Ci 0 = 0
dt τ υ0 ρi 0 υ0
Similarly, for other species
dC B 1
B: = (CB0 - C B ) + (-rB )
dt τ
dCC 1
C: = (CC0 - CC ) + rC
dt τ
dC M 1
M: = (CM0 - C M )
dt τ

Energy Balance: Applying law of conservation of energy to the reacting system,
Rate of Rate of
Rate of Rate of Rate of heat
accumulation of enthalpy
= energy into – energy out of + – removal
energy within change due to
the system the system through jacket
the reactor reaction
 dT dT dT dT 
 N A C PA + N B CPB + N C CPC + N M C PM  =  FA0 CPA (T0 - Tr ) + FB0 C PB (T0 - Tr ) +
 dt dt dt dt 
FM0 CPM (T0 - Tr )  –  FA CPA (T - Tr ) + FBC PB (T - Tr ) + FC C PC (T - Tr ) + FM CPM (T - Tr )  +
[ ∆H Rx (rA V)] – [ UA(T- Tj)]
Now, Taking T = Tr (Exit temperature = Reference temperature)
  dT  FB FM 
∴  ∑ Ni CPi  = FA0 (T0 - T)  CPA + 0 CPB + 0 CPM  + [ ∆H Rx (rA V)] + [ UA(T- Tj) ]
 i  dt  FA0 FA0 
 
 
 UA(Tj - T) - FA0 (T - T0 )∑ θ i C Pi + ∆H Rx rA V 
=  
∴ i
where θ i = 0 and Ni = Ci V
dt ∑ Ni CPi i

Table 1: Parameter values

CPA = 146 J/mol-K ρ A0 = 0.859 g/cc MA = 58.08 A = 16.96 x 1012 hr-1
CPB = 75 J/mol-K ρ B0 = 0.9941 g/cc MB = 18 E = 18 kcal/mol
CPC = 193 J/mol-K ρ M0 = 0.7914 g/cc MM = 32.04 UA = 133 MJ/hr-K

CPM = 82 J/mol-K ∆H Rx = - 83740 J/mol of propylene t0 = 0 ; tf = 4 hr

oxide reacted

Simulation Results and Discussion

Using POLYMATH 5.1, the CSTR under study is simulated. Initially only water (55
kmol/m3) and 0.1 wt % H2SO4 present at 25oC. No propylene oxide is there initially (i.e. CA0
= 0). The following figures show the simulation results. Fig.1 shows the concentrations of
propylene glycol (CC), propylene oxide (CA) and methanol (CM) as a function of time. These
concentrations reach their steady state values after approximately 1.8 hours. Fig.2 shows
concentration of water (CB) as a function of time.
Ca Cc Cm
2.5 60
Cb Vs t
Ci, kmol/m3

Cb, kmol/m3

2 50
0 20
0 0.5 1 1.5 2 2.5 3 3.5 4 0 0.5 1 1.5 2 2.5 3 3.5 4
t, hr t, hr
Fig.2: Concentration as a function of time
Fig.1: Concentration as a function of time

Fig.3 shows reactor temperature (T) as a function of time, for an initial temperature of 25oC
and only water in the tank (i.e. CA0 = 0). Both temperature and propylene oxide concentration
oscillate around their steady state values (T = 56.48oC, CA = 1.079 kmol/m3).

Temperature, oC

3 Cao = 4

T = 82
50 T Vs t Cao = 7

Ca, kmol/m3
30 1 Cao = 0 steady state
20 0
0 0.5 1 1.5 2 2.5 3 3.5 4 20 30 40 50 60 70 80 90
t, hr T, oC
Fig.3: Temperature profile Fig.4: Temperature-concentration phase plane

Fig.4 shows the phase plane of reactor temperature and propylene oxide concentration for an
initial reactor temperature (T0 = 25oC) and different initial concentrations of propylene oxide
(CA0 = 0, CA0 = 4, CA0 = 7). It can be seen that if reactor is started at an initial temperature of
25oC and an initial concentration of CA0 = 0 and CA0 = 4 kmol/m3, the reactor approached its
steady state values (T = 56.48oC, CA = 1.079 kmol/m3) without exceeding practical stability
limit of 82oC. But if reactor is started at an initial temperature of 25oC and an initial
concentration of CA0 = 7 kmol/m3, the practical stability limit would be exceeded as the
reactor approached the steady state values.

During the startup of reactor, often approach to steady state is more important than reaching it
particularly when it is required to control operating parameter such as temperature beyond
certain limit. Concentration-temperature trajectories have been obtained for different initial
concentration of propylene oxide. During this sensitivity test, it was found that with some
initial conditions the reactor temperature exceeded practical stability limit while approaching
its steady state value. Such initial conditions can be anticipated and avoided in order to
minimize the side reactions and maximize the propylene glycol production. Future work to
the present study is to add a control system in the modeling to make adjustments to the
reaction system that will minimize or eliminate the effects of the upsets.

CA, CB, CC, CM Concentrations of A, B, C and M respectively, kmol/m3
CA0 CB0 CC0 CM0 Initial concentrations of A, B, C and M respectively, kmol/m3
NA, NB, NC, NM Moles of A, B, C and M respectively
FA0 FB0 FM0 Molar feed rates of A, B, C and M respectively, kmol/hr
MA, MB, MM Molecular weights of A, B, C and M respectively
CPA , CPB , CPC , CPM Heat capacities of A, B, C and M respectively, J/mol-K
ρ A0 , ρ B0 , ρ M0 Densities of A, B, C and M respectively, g/cc
∆H Rx Heat of reaction, J/mol
U Overall heat transfer coefficient, MJ/m2-hr-K

Chan Arthur, Seider Warren D. (July 2004), “Batch Manufacture of Propylene Glycol”,
Department of Chemical and Biomolecular Engineering, University of Pennsylvania,
Philadelphia, PA 19104-6393

Dasaria M. A. et al. (2005), “Low-pressure hydrogenolysis of glycerol to propylene glycol”,

Applied Catalysis A: General 281, 225–231.

Fogler H. Scott (2004), Elements of Chemical Reaction Engineering, 3rd edition, Prentice-
Hall of India Pvt. Ltd., New Delhi.

Ramirez W. Fred (1997), Computational Methods for Process Simulation, 2nd edition,
Butter Worth-Heinemann, Reed Educational and Professional Publishing Ltd.

Ullmann’s Encyclopedia of Industrial Chemistry, 5th edition, Vol. 30, Page No. 199–207,

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