PROJECT 2: Parameter Estimation of kinetic rate constants

Propanediol (PD) is a potentially attractive monomer for the polymerization of polypropylene

and terephthalate. It is a product of the hydrogenation of 3-Hydopropanal (HPA) over
Ni/SiO2/Al2O3 catalyst powder. A reaction scheme and a mathematical model that depicts the
consumption of HPA and production of PD and acrolein (AC) are governed by the following
model:
dCHPA
= [1 + 2 ] [3 + 4 3 ]
dt

Eq 1

= [1 2 ]

Eq 2

= 3 4 3

Eq 3

where Ck is the catalysts mass concentration (g/L).

The kinetic expressions for the reaction rates, which complement the model, are presented next:
1 =

2 =

1
3

1 0.5
[1+(
) + 2 ]

2
1 0.5
1+(
) + 2

3 = 3
3 = 3
4 = 4

Eq 4

Eq 5

Eq 6

Eq 7

Eq 8

In the above equations, kj (j=1, 2, 3,-3, 4) are the rate constants (L/ (mol min g)), K1 and K2 are
the adsorption equilibrium constants (L/mol) for H2 and HPA respectively; P is the hydrogen
pressure (MPa) in the reactor and H is the Henry's law constant with a value equal to 137.9 (L
MPa/mol) at 298 K. Components concentrations are in mol/L. In this example, only the data
gathered at one isotherm (318 K) and three pressures 2.6, 4.0 and 5.15 MPa are considered. Ck is

constant at 10g/L in all three experiments. The initial conditions in all experiments are: CHPA (0)
=1.34953 mol/L, CPD (0) = 0 mol/L, CAc (0) = 0 mol/L.
The data measured for the HPA hydrogenation at 318K and pressures 2.6, 4.0 and 5.15 MPa are
presented in Table 1. Ck is kept constant at 10g/L for all experiments.
Table 1: Experimental Data of the HPA Hydrogenation at 318K and three different pressures: 2.6, 4.0
and 5.15 MPa.

Pressure (MPa)

2.6

5.15

Time (min)

CHPA (mol/L)

CPD (mol/L)

10
20
30
40
50
60
80
100
120
140
160
180
200
10
20
30
40
50
60
80
100
120
140
160
180
200
10
20
30
40
50
60
80
100

1.3740
1.2582
1.1871
1.1329
1.0356
0.9613
0.7344
0.5646
0.3744
0.2148
0.1010
0.0364
0.0053
1.3295
1.3116
1.2283
1.0870
0.9945
0.8118
0.6010
0.3863
0.2042
0.0782
0.0278
0.0032
0.0021
1.3632
1.2588
1.1792
0.9721
0.8252
0.6971
0.4215
0.2323

0
0.0197
0.0643
0.1364
0.2386
0.3046
0.4924
0.7323
0.8873
1.0428
1.1731
1.2577
1.2603
0.0026
0.0526
0.1207
0.2414
0.3849
0.4682
0.7732
0.9908
1.1495
1.2800
1.2900
1.3000
1.3000
0.0026
0.0700
0.1844
0.3540
0.4698
0.6074
0.8524
1.0354

120
140
160

0.1281
0.0290
0.0096

1.1641
1.3005
1.3197

Use Matlab to estimate the seven parameters, k1, k2, k3, k-3, k4, K1 and K2, based on the
concentrations of HPA and PD versus time shown in Table 1. It is estimated that the ratio of K1
to K2 is ~40 and that of k4 to k-3 is ~73.
Hint. Start with an initial guess of 10^-3 for all rate constants.

Deliverables:
1- Technical report showing summary, problem definition, results and discussion,
conclusion in Hard Copy.
2- All Matlab files.