Article

Cite This: Ind. Eng. Chem. Res. 2019, 58, 13767−13779 pubs.acs.org/IECR

Analysis of Experimental Conditions, Measurement Strategies, and

Model Identification Approaches on Parameter Estimation in Plug
Flow Reactors
Manokaran V,† Tirthankar Sengupta,†,‡ Sridharakumar Narasimhan,*,†,‡ and Nirav Bhatt*,¶,‡
†
Department of Chemical Engineering, Indian Institute of Technology Madras, Chennai, India 600036
‡
Robert Bosch Centre for Data Science and Artificial Intelligence, Indian Institute of Technology Madras, Chennai, India 600036
¶
Department of Biotechnology, Indian Institute of Technology Madras, Chennai, India 600036
*
S Supporting Information
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ABSTRACT: Continuous flow reactors such as plug flow

reactors (PFRs) have been used in the identification of
reaction systems (Moore, J. S.; Jensen, K. F. Angew. Chem.
2014, 126, 480−483). It is important to understand the
impact of operating conditions, measurement strategies, and
kinetic model identification methods on the identification of
reaction systems in a PFR. Typically, for kinetic model
identification using the simultaneous identification approach,
concentrations are measured as a function of residence time
under isothermal operating conditions in a PFR. On the other
hand, concentrations and temperature are required to be
measured as a function of residence time under non-
isothermal conditions for kinetic model identification of
multiple reaction systems in a PFR. In this work, we extend the incremental method for identification of kinetic and heat
transport models using measurements from non-isothermal steady-state PFRs. This work investigates the role of experimental
conditions, measurement strategies and identification methods on the quality of estimations of parameters from concentrations
and/or temperature measurements. Further, this paper compares (i) the minimum number of species to be measured for
parameter estimation, (ii) isothermal and non-isothermal experimental conditions, (iii) different levels of spatial distribution of
concentration and temperature measurements, and (iv) simultaneous and incremental identification approaches with respect to
the quality of estimated parameters. The last three aspects are investigated through carefully designed numerical studies.

1. INTRODUCTION temperatures instead of analysis at only one single isothermal

Model-based analysis of experimental data is important for
better understanding of the underlying reaction system, rapid
process development, and model-based control and optimiza-
tion in production.1 Traditionally, tank reactors operating in
the batch or semibatch mode have been used for generating
experimental data and developing reliable kinetic and transport
models. Typically, identification of reliable kinetic and
transport models involves determining stoichiometry or
reaction mechanism, kinetic and mass-transfer rate laws, and
corresponding parameters such as kinetic rate constants and
mass-transfer coefficients. Methods for identifying kinetic and
transport models from experimental data can be broadly
classified into two categories: (i) simultaneous identification
approach and (ii) incremental identification approaches.2,3
Typically, these methods use concentrations of species
measured under isothermal operating conditions to identify
models and corresponding parameters such as the pre-
exponential factor and the activation energy in the Arrhenius
equation. The parameter estimation problem can be improved
upon by scanning the parameter space over a range of
temperature. Thus, a set of isothermal experiments at different
temperatures are performed. In contrast to isothermal
operation, the non-isothermal operation has also been used
to identify a kinetic model.4 It has been shown that
temperature measurements are sufficient for the identification
of single reaction systems under non-isothermal conditions.4 In
the case of reaction systems with multiple reactions, both
concentration and temperature measurements are required.
Although the non-isothermal mode of operation of batch
reactors can generate informative experimental data, such an
operation may lead to catastrophic effects such as thermal
runaway due to poor mixing. Hence, traditionally, most of the
Special Issue: Dominique Bonvin Festschrift
Received: January 15, 2019
Revised: April 24, 2019
Accepted: April 28, 2019
Published: April 29, 2019

© 2019 American Chemical Society 13767 DOI: 10.1021/acs.iecr.9b00266

Ind. Eng. Chem. Res. 2019, 58, 13767−13779
Industrial & Engineering Chemistry Research
experimental studies in batch reactors are carried out under
isothermal conditions.
The field of identification of reaction systems has witnessed
a paradigm shift in the recent past. Of late, micro- and
millireactor technology are being used in chemical synthesis
owing to superior heat and mass transfer characteristics of
these reactors and safer handling of hazardous reagents.5
Furthermore, as a consequence of small channel dimensions,
the reagent volume hold-up per unit volume of the reactor is
lower for microreactors. Hence, microreactors consume
smaller amounts of reagents in comparison to traditional
batch reactors. Thus, the characteristics of microreactors make
them highly suitable for use in experiments aimed at the
identification of reaction systems.5−7 Moreover, online
automated microreactor systems have been designed for
performing several experiments at specified predefined
conditions.8 Microreactors have also been integrated with
online/inline analytical techniques such as infrared spectros-
copy (IR) and high-performance liquid chromatography
(HPLC) for rapid acquisition of kinetic data and subsequent
determination of kinetic models, under both isothermal and
non-isothermal operating conditions.9,10
Microreactors do not exhibit any significant gradients in a
direction perpendicular to the flow of reagents, owing to
extremely small channel dimensions. Gradients, however, do
exist along the axial direction, i.e., in the direction of flow.
Hence, under the ideal conditions, microreactors can, there-
fore, be modeled as a plug flow reactor (PFR). In a PFR, the
flow is in the turbulent regime with instantaneous radial
diffusion with minimal axial mixing. Traditionally, these
reactors have been mainly used for studying gas phase
reactions, such as steam pyrolysis, thermal cracking of
hydrocarbons, and also for heterogeneous reactions, such as
catalytic cracking, oxidation of sulfur dioxide to sulfur trioxide,
etc.11 In the literature, studies have been reported where PFRs
operating at steady states have been used for identification of
kinetic models from species concentrations at different
residence times.12 A temperature scanning PFR has been
developed to collect isothermal kinetic data for catalytic
reactions operating at an unsteady state.13,14 Kolkowski et al.15
performed simulations to study how heat transfer affects the
estimation of reaction rates. The study was done on
heterogeneous reactions using a temperature scanning PFR
(TSPFR). Mozharov et al.7 proposed a flow manipulation
technique which allows computing location specific kinetic
data along the flow path using inline measurements at the end
of a microreactor. Jensen and co-workers16,17 extended the
flow manipulation technique to generate online kinetic data by
applying a controlled ramp in the flow rate and the
temperature along the axial direction of a microreactor.
These kinetic data were used to estimate the pre-exponential
factor and the activation energy of a Paal−Knorr reaction using
the simultaneous identification approach.
In contrast to the simultaneous model identification, another
class of identification techniques referred to as incremental
identification decompose the identification task into various
subproblems.2,3,18 The subproblems include identification of
the stoichiometric matrix and rate laws and estimation of
corresponding kinetic parameters and mass transfer coeffi-
cients. The rate-based incremental identification approach
involves the computation of reaction fluxes using concen-
tration measurements. From the estimated reaction fluxes,
parameters of reaction rate models are calculated, separately
13768
Article
for each reaction.2,19 Since the estimation of reaction fluxes is
obtained by numerical differentiation of data, the above-
mentioned procedure introduces a bias in the estimation
process. Bhatt et al.20 proposed an extent-based incremental
identification approach by utilizing the concept of the extent of
reaction and mass-transfer. The extent of reaction is tradition-
ally defined for batch systems and has been extended to open
reaction systems.3 On similar lines, we define the extent of
heating for non-isothermal modes of operation. Further, we
specify the conditions under which the extents can be
computed. Using these conditions, we extend the extent-
based incremental approach to non-isothermal steady-state
PFRs for identifying kinetic models and heat-transfer rates
from concentration and temperature measurements in this
work.
Although the isothermal and non-isothermal operations have
been used for kinetic modeling, there has been no systematic
comparison between these conditions from a parameter
estimation viewpoint. Further, in non-isothermal conditions,
concentration and temperature can be used to identify reaction
systems. Often, it is relatively easy to measure temperature
along the length of a reactor in comparison to concentrations.
Hence, it may be possible to combine fewer concentrations
with more spatially distributed temperature for effective
estimation of parameters. The objective of this work is to
compare the two experimental conditions, viz., isothermal and
non-isothermal conditions and study the effect of experimental
conditions on the quality of parameter estimates using
simulations. Further, we will provide the conditions for the
minimal number of species to be measured under different
experimental conditions. Moreover, we will investigate the
impact of combining more spatially distributed temperature
with fewer concentrations.
In summary, the main contribution of this work is 2-fold: (i)
extension of the incremental identification approach to non-
isothermal steady-state PFRs and (ii) analysis of the effect of
experimental conditions, measurement strategies, and estima-
tion methods on the quality of parameter estimates in PFRs.
This is done using theoretical analysis and the concept of the
extent of heat transfer, development of methods to compute
the same, and extensive numerical studies. This paper is
organized as follows. The general model equations for PFRs
such as mass, energy, and momentum balance are discussed
first. This is followed by a discussion on extent-based models
for PFR. Thereafter, different methods of data collection along
with the subsequent parameter estimation procedure are
discussed for simultaneous and extent-based incremental
identification approaches. Subsequently, for the purpose of
illustration, simulations and the results of parameter estimation
are discussed to assess the impact of various experimental
conditions, measurement strategies, and identification methods
on parameter estimation. This is followed by the Results and
Discussion section. The last section concludes the work.
2. MODEL EQUATIONS IN CONCENTRATION
DOMAIN
Plug flow reactors (PFRs) are differential reactors in which
concentration, temperature, and pressure vary along the length
of the reactor. In this section, model equations for steady-state
PFRs are discussed. We consider a steady-state PFR, in which
R independent reactions involving S species are taking place
and there exists one inlet and one outlet stream.
DOI: 10.1021/acs.iecr.9b00266
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Industrial & Engineering Chemistry Research Article

2.1. Material Balance. The material balance equation for a dimensional vector of molecular weights. The Fanning friction
steady-state PFR is given by11,21 factor f for laminar flow through empty tubes is given by f =
16/Re, where Re is the Reynolds number. In the turbulent flow
dF F
= NTr(c), F(0) = F0 , with c= regime, the friction factor f is given by f = 0.046 Re−0.2. For
dV ν (1) ideal gas systems, the volumetric flow rate ν(z) as a function of
where F is the S-dimensional vector of molar flow rates, N is reactor length is given by
the stoichiometric matrix of dimension R × S, r is the R- Ft (z)R gT (z)
dimensional reaction rate vector, c is the S-dimensional vector ν(z) =
of concentrations, V is the volume of reactor, F0 is the S- P(z) (5)
dimensional inlet molar flow rate vector, and ν is the where the total molar flow rate Ft = 1TS F
and 1S is the S-
volumetric flow rate. If the cross sectional area Ac of the dimensional vector containing 1. The model equations can be
reactor is assumed to be constant, the material balance adapted to different experimental conditions, modeling
equation is written in terms of molar flux rate Fr as a function assumptions, and specialized forms of the same are
of reactor length z as follows: summarized in Table S1 of the Supporting Information.
dFr
= NTr(c(z)), Fr (0) = Fr0 , with 3. MODEL EQUATIONS IN EXTENT DOMAIN
dz
F (z )A c In the literature, the concept of the extent of a reaction is
c(z ) = r widely used in modeling reactors. The main advantage of
ν(z) (2) modeling reactors in terms of extents of reaction is the
In the above equation, Fr0 is the S-dimensional vector of decoupling of the contribution of a particular reaction from
that of other reactions. In batch reactors, the only contribution
initial molar flux rates of the species involved in the reaction to change in number of moles of species is from reactions, as
system. there are no inlet and outlet streams. Therefore, for a batch
2.2. Energy Balance. The steady-state energy balance reactor, the change in extent of ith reaction xr,i (i = 1,...,R) can
equation for a PFR, exchanging heat with the surroundings, be expressed as
can be obtained in terms of the temperature of the reaction
mixture (T) and the reactor pressure (P), under the dxr, i
assumptions of negligible kinetic and potential energies and = rV
i , xr, i(0) = 0
dt (6)
also no shaft work, as follows:11 22
Recently, Armhein et al. proposed an orthogonal linear
νρCp̂
dT
+ ν(1 − αT )
dP
= −ΔHTR r transformation for a flow reactor system where the objective
dV dV was to decouple the contributions of inlet and outlet streams
+ UA from reaction variants. The decoupled reaction variants
̅ ext (Ta − T ), T (0) = T0 (3)
represented the true extents of reaction xr and could therefore
where ρ is the density of the reaction mixture, Cp̂ is the specific be used for kinetic modeling studies. The concept of the extent
of a reaction has been extended to steady-state PFRs. Note that
heat capacity of the reaction mixture, α corresponds to the
the change in number of moles of species in a PFR is only due
coefficient of expansion of the reaction mixture, ΔHR is the R-
to reaction, and the extents of reaction xr vary along the length
dimensional vector pertaining to the heat of R reactions, Aext is
of the reactor z. Assuming cross-sectional area Ac to be
the external surface area per unit volume of the reactor
constant, the change in the extent of the ith reaction xr,i (in
necessary for heat exchange, U̅ is the overall heat transfer
mol m−2 s−1) (For flow reactors, the extent is typically defined
coefficient, Ta is the ambient temperature, and T0 is the
as mol s−1.11 For easy representation in terms of spatial
temperature of reactants at the inlet.
measurements, the extent of reaction xr is denoted in terms of
2.3. Momentum Balance. At steady state, neglecting the
mol m−2 s−1) in a steady-state PFR can be expressed as
effect of body forces (gravitational force), the momentum
balance equation reduces to the pressure drop equation. For dxr, i
gas phase or liquid phase mixtures, the pressure drop in a PFR, = ri , xr, i(0) = 0
dz (7)
having an inner diameter di, can be modeled using the density
of the reaction mixture ρ as We now define a transformation that allows us to write the
model equation in terms of extents of reaction xr and molar
dP 2fu ̅ 2ρ flux rates. Since the species molar fluxes and the temperature
− = , P(0) = P0 change along the length of the reactor z, it is easier to frame
dz di (4)
the material balance in terms of molar flux Fr rather than the
where f is the Fanning friction factor and u ̅ = A is the
ν(z) molar flow rate F. Using eq 2, a linear transformation of the
c molar flux vector Fr into extents of reaction xr and reaction
average velocity of the reaction mixture at location z. For liquid invariants xiv can be defined for an isothermal steady-state PFR

ÄÅ x ÉÑ ÄÅÅ T † ÉÑÑ
phase systems, the average density of the reaction mixture can as follows:
ÅÅ r ÑÑ ÅÅ N ÑÑ
ÅÅ ÑÑ = ÅÅ Ñ
be calculated, assuming that the mixture behaves as an ideal

ÅÅ x iv ÑÑ ÅÅ T ÑÑÑ(Fr − Fr0)
ÅÇ ÑÖ ÅÅÇ P ÑÑÖ
1
solution, as ρ = T , where x = [x1,x2,...,xS]T and ρM =
x ρM
[ρ1,ρ2,...,ρS]T are the S-dimensional mass fraction and mass (8)
density vectors, respectively. Similarly, for a gas phase reaction where xr is the R-dimensional vector of the extents of reaction,
system behaving as an ideal gas, ρ can be calculated as xiv is the (S−R)-dimensional vector of reaction invariants. The
P(x T M)
ρ= R gT
, where Rg is the ideal gas constant, and M is the S- superscript † denotes the Moore−Penrose pseudo inverse of a
13769 DOI: 10.1021/acs.iecr.9b00266
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Industrial & Engineering Chemistry Research Article

matrix. The S × (S−R)-dimensional matrix P corresponds to As a result of the above transformation, the augmented
molar flux vector F̃ r lies in a lower dimensional affine space:
ÄÅ ÉÑ
the null space of the matrix N, i.e., NP = 0. The model

Å 0S ÑÑÑÑ Ä É ÅÄ ÑÉ
ÄÅ ÉÑ ÅÅÅÅ N
equations for an isothermal steady-state PFR in terms of the

ÅÅ Fr ÑÑ Å ÑÑ ÅÅÅ x r ÑÑÑ ÅÅÅ Fr0 ÑÑÑ

Fr̃ = ÅÅÅÅ ÑÑÑÑ = ÅÅÅÅ −ΔHTR A c ÑÑ ÅÅ ÑÑ + ÅÅ ÑÑ
extents of reaction and reaction invariants are T

ÑÑ ÅÅ x ÑÑ ÅÅ ÑÑ
ÅÅÇ T ÑÑÖ ÅÅ Å ÑÑ ÅÅÇ q ÑÑÖ ÅÅ T0 ÑÑ
ÅÅ νρĈ ÑÑ Ç Ö
dxr, i

pÑ
A
Å Ñ
´ÅÇÖÖÖÖÖÖÖÖÖÖÖÖÖÖÖÖÖÖÖÖÖÖÖ≠TÖÖÖÖÖÖÖÖÖÖÖÖÖÖÖÖÖÖÖÖÖÖÑÖÖÆ
= ri , ∀ i = 1, ..., R c
dz νρ C ̂
p
dxiv, j
= 0, ∀ j = 1, ..., S − R Naug (15)
dz (9)
Note that the reconstruction of the molar fluxes Fr requires
The molar fluxes Fr can be reconstructed from the extents xr only information related to the extents of reaction while the
as follows: same for the temperature T requires information on the extents
Fr (z) = NTx r(z) + Fr0 of reaction xr and the extent of heat transfer xq. Hence, it is
(10)
demonstrated that the linear transformation in eq 8 can be
Next, we extend the concept of extents to a non-isothermal applied to the material balance equation in a non-isothermal
steady-state PFR. Under the assumptions of constant PFR, independent of the energy balance equation. This result
thermochemical properties, constant pressure, and the reagents will be used in kinetic modeling of reaction systems, for the
behaving as an ideal mixture, eq 3 can be written as purpose of parameter estimation, using the incremental
ij −ΔHT r Q yz
= jjjj + ext zzzzAc ,
identification approach, in Section 6.

j νρCp̂ νρCp̂ z
dT If only a subset of species concentrations (Sa) is measured,

k {
R
T (0) = T0 cν
dz (11)
the respective fluxes Fr,a can be calculated as Fr, a = Aa . The
c

extents can be calculated if the following linear equations have

In the above equation, Qext corresponds to the amount of
ÄÅ ÉÑ
a unique solution.

Å 0Sa ÑÑÑÑ Ä É ÅÄ
ÄÅ ÉÑ ÅÅÅÅ Na
heat transferred to the surroundings which is expressed by Qext
É
ÑÑ ÅÅ x r ÑÑ ÅÅ Fr, a ÑÑÑ
= U̅ Aext(Ta − T). Considering Qext as a pseudo reaction, eqs 2
ÅÅ Fr, a ÑÑ ÅÅ ÑÑ ÅÅ ÑÑ ÅÅ 0 ÑÑ
Å Ñ
T

ÄÅ ÉÑ Ä Å Ñ Å
ÅÅÅ dFr ÑÑÑ ÅÅÅÅ NT ÑÉ Fr, a = ÅÅ ÑÑ = ÅÅ −ΔH A A c ÑÑÑ ÅÅÅÅ xq ÑÑÑÑ + ÅÅÅ ÑÑ
and 11 are combined to get the following equation:

0S ÑÑÑÑ Ä ÄÅ ÉÑ ÅÅÇ T ÑÑÖ ÅÅÅ ÑÑ ÅÇ ÑÖ ÅÅÇ T0 ÑÑÑÖ

Å
Å Ñ ÅÅ
Ñ Ñ ÅÅÅ r ÉÑÑÑ ÅÅ νρĈ Ñ
ÅÅÅ Fr0 ÑÑÑ
̃
ÅÅ dz ÑÑ ÅÅ νρĈ p ÑÑ
T

Ñ Å
= ÅÅÅÅ ÑÑ = ÅÅ Ñ
Ac ÑÑÑÑ ÅÅÅÅQ ÑÑÑÑ , Fr̃ (0) = ÅÅÅÅ ÑÑÑÑ ´ÅÇÖÖÖÖÖÖÖÖÖÖÖÖÖÖÖÖÖÖÖÖÖÖÖT≠ÖÖÖÖÖÖÖÖÖÖÖÖÖÖÖÖÖÖÖÖÖÖÑÖÖÆ
R c

ÑÑ ÅÅ −ΔHTR Ac
ÅÅ dT ÑÑ ÅÅ Ñ Å ext Ñ ÅÅÇ T0 ÑÑÖ
dFr̃

ÅÅÅ ÑÑÑ ÅÅÅ νρCp̂ ̂ ÑÑÑÑ ´ÅÇÖÖÖÖÖÖ≠ÖÖÖÖÖÖÑÖÆ

p

ÅÅÇ dz ÑÑÖ ´ÅÇÖÖÖÖÖÖÖÖÖÖÖÖÖÖÖÖÖÖÖÖÖÖ≠ÖÖÖÖÖÖÖÖÖÖÖÖÖÖÖÖÖÖÖÖÖÖÑÖÆ r ̃

dz Na, aug (16)
νρ C p
Naug T where NTa is the stoichiometric matrix corresponding to the Sa
(12)
measured species. The unmeasured fluxes Fr,u can be calculated
as follows: Fr, u = NTu x r + Fr, u 0 . For different experimental
where F̃ r is the S + 1-dimensional vector augmented molar flux
vector, NTaug is the (R + 1) × (S + 1) augmented stoichiometric conditions (isothermal or non-isothermal), the minimum

ÄÅ x ÉÑ
Å Ñ
vector. We define x̃ r = ÅÅÅ xqr ÑÑÑ as the R + 1-dimensional extent
matrix, and r̃ is the R + 1-dimensional augmented reaction rate number of components to be measured is determined from

ÅÇ ÑÖ
eq 16 as follows:
Isothermal Operation. Clearly, a necessary and sufficient
vector with R states (xr) corresponding to the extent of R condition for the above equations to have a unique solution is
reactions and the last state (xq) corresponding to the extent of that NTa,aug should have rank R + 1. This implies Sa ≥ R and
heat transfer (in W m−2). Equation 12 is of the form of eq 2, rank NTa is R.
and the linear transformation in eq 8 can be extended to eq 12 Adiabatic Operation. In this case, xq is identically 0.

Ä É
ÄÅ ÉÑ ÅÅÅ NT † ÑÑÑ
as follows: Hence, it is possible to compute the extents if at least R − 1

ÅÅ x̃ r ÑÑ ÅÅ aug ÑÑ ij NT yz
ÅÅ ÑÑ = ÅÅ Ñ
species and T are measured or if at least R species are

ÅÅ x ÑÑ ÅÅ T ÑÑÑ(Fr̃ − Fr̃ 0) jj zz
j z
ÅÅÇ iv ÑÑÖ ÅÅ P ÑÑ
ÅÅÇ aug ÑÑÖ measured such that rank jjj −ΔHR zzz = R .
jj Ac zz
a

jj νρĈ zz
T

k {
(13)
p
Paug is the null space of Naug, and it can be constructed using
Non-isothermal, Non-adiabatic Operation. A necessary
the relationship Naug Paug = 0. In this case, the model equations
and sufficient condition for the above equations to have a
in terms of the extents are given by
unique solution is that NTa,aug should have rank R + 1. This
dxr , i implies that at least R species and T have to be measured such
= ri , ∀ i = 1, ..., R that rank NTa is R.
dz
Table 1 summarizes the minimum number of component
dxq measurements to compute the extents of reaction xr for various
= Q ext
dz operating conditions in a PFR. If densities and other
dxiv, j thermochemical properties change, volumetric flow rate or
= 0, ∀ j = 1, ..., S − R equivalently average molecular weight or molar density has to
dz (14) be additionally measured.
13770 DOI: 10.1021/acs.iecr.9b00266
Ind. Eng. Chem. Res. 2019, 58, 13767−13779
Industrial & Engineering Chemistry Research
Table 1. Minimum Number of Components to Be Measured
for Calculating Extents under Various Experimental
Conditions in PFR
minimum number of measurements
experimental condition required
isothermal R species
adiabatic R species or R − 1 species and T
non-isothermal PFR with heat R species and T
loss
4. IDENTIFICATION OF MODEL PARAMETERS IN A
PFR
Typically, the process of building a kinetic model using a PFR
consists of two steps:
• Generation of experimental data: Experiments are
performed to collect concentration and/or temperature
data at different residence times.
• Identification of kinetic model: In this step, the
stoichiometric matrix and the model structure, i.e., rate
laws and corresponding parameters, are estimated from
experimental data collected in the first step.
In this section, we briefly describe the above-mentioned
steps for identification of a kinetic model using concentration
and temperature measurements obtained from steady-state
PFRs. First, different conditions pertaining to the operation of
reactors and measurement strategies will be described.
Thereafter, two approaches for the identification of reaction
systems, namely, the simultaneous and incremental ap-
proaches, are discussed.
4.1. Experimental Data Generation. We describe here
different types of experiments that can be performed in a PFR
to generate experimental data for the purpose of identification
of reaction systems. Typically, experiments in PFRs can be
performed under isothermal or non-isothermal conditions.
• Isothermal experiments can be performed in a PFR if
there is a provision of exchanging heat with the external
surroundings. The setup is similar to an annular pipe
where a heat transfer fluid is circulated in the outer pipe
and the reaction mixture flows through the inner pipe.
• Two types of non-isothermal experiments can be
performed in a PFR as follows:
 Adiabatic operation is realized in a PFR without
any coolant fluid being circulated and the reactor being
insulated in a way such that the heat of reaction ΔHR is
not transferred to the surroundings.
 Non-isothermal reactions involving heat exchange
with a coolant fluid can be performed such that the outer
pipe is insulated thereby ensuring that the heat from the
Figure 1. Two approaches for data collection in steady-state PFRs.
13771
Article
heat exchange fluid does not get transferred to the
surroundings.
In both the cases, the temperature is measured along the
length of the reactor, as described in Figure 1, and will be used
for kinetic model identification.
The model equations for different experimental scenarios are
presented in Table S1 of the Supporting Information. In a
PFR, experimental data can be collected as shown in Figure 1.
In the first approach, as shown in Figure 1a, the concentrations
of species and temperature are measured along the length of
the reactor. The residence time τ(z) at each measurement
location is calculated using the velocity u̅(z) at the location. In
the second approach, as shown in Figure 1b, the volumetric
flow rates are changed such that ν1 > ν2 > ... > νn, for the same
inlet species concentrations, and the corresponding outlet
concentrations c1, c2, ..., cn are measured. The concentrations
(cτ1,cτ2, ... ,cτn) are then arranged in a manner such that the
residence times τ(τ1 < τ2 < ... τn) are in increasing order. The
temperature of the reaction mixture can be measured along the
length of the reactor at each location z.
4.2. Parameter Estimation. Once, experimental data has
been collected via a carefully designed experiment, the next
step is to estimate the unknown rate laws and corresponding
parameters. The rate expression is a function of concentrations
and temperature. Particularly, the temperature dependence of
rate constant, k(T) is usually expressed using the Arrhenius
expression k(T ) = k 0 e−Ea / R gT . Then, for given rate laws, the
objective of parameter estimation is to estimate the k0 and the
Ea corresponding to each reaction. In this section, we discuss
two approaches to identify parameters: (i) simultaneous
method and (ii) incremental method. For a reaction system,
it is often not possible to measure the concentrations of all
species along the length. The minimum number of species to
be measured for identifiability is given in Table 1. Thus, only a
subset of species concentration needs to be measured such that
rank(Na), where Na is the stoichiometric matrix associated
with the measured species, is equal to the rank of the
stoichiometric matrix N. Further, the temperature is also
measured along the length of the reactor.
Since the objective of this paper is to analyze different
measurement strategies of temperature and concentration
measurements on parameter estimation, the following
assumptions are made during identification of a kinetic
model: (i) Stoichiometric matrix N and reaction rate
r(c,T,θ) model structure are known, (ii) Inlet concentrations
c0 of all the species and inlet temperature are known, (iii)
Sufficient number of sampling locations for concentration and
temperature measurements are available along the length of the
reactor, and (iv) Volumetric flow rate ν(z) and temperature
are measured along the length of the reactor.
DOI: 10.1021/acs.iecr.9b00266
Ind. Eng. Chem. Res. 2019, 58, 13767−13779
Industrial & Engineering Chemistry Research Article

4.3. Simultaneous Approach. The simultaneous identi- measured fluxes and temperature are augmented. Thereafter,

ÄÅ É
ÅÅ x r(z)ÑÑÑ
fication approach allows the estimation of all k0s and Eas the extents of reaction and heating can be computed as

ÅÅ ÑÑ
ÅÅ Ñ
pertaining to the underlying reaction system. Depending on

ÅÅ x (z) ÑÑÑ = Naug, a(F r, aug (z) − F r, aug (0))

ÅÅÇ q ÑÑÖ
the type of experiment, experimental data may be obtained via T† a a
single or multiple experiments. Since we perform multiple

ÄÅ T ÉÑ
experiments at different flow rates (or residence times), the
ÄÅ É
(20)

ÅÅ N
ÅÅ a
ÑÑ
ÑÑ ÅÅ ca(z)ν(z) ÑÑÑ
ÅÅ ÑÑ
objective function in the simultaneous model identification
ÅÅ ÑÑ ÅÅ ÑÑ
Å
= ÅÅÅ −ΔHR Ac ÑÑ = ÅÅÅ ÑÑ
approach uses all of the available experimental data to estimate 0
ÑÑ ÑÑ
ÅÅ ÑÑÑ ÅÅÅ ÑÑ
parameters. The objective function is formulated using a
ÅÅ ÅÅT (z) ÑÑ
ÄÅ νρCp̂ ÑÑÑ
T
Far, aug Ac
ÅÅ νρCp̂
Naug T and
A
ÅÅ Nexp R L (c ÅÇ ÑÖ
weighted least-squares approach as follows: ,a

ÅÇ ÑÖ
c

ÅÅ
Å
=minÅÅ∑ ∑ ∑
2

θ Å
expijk − cmodel(θ)ijk )

ÅÅ k = 1 j = 1 i = 1
ÅÇ
ÉÑ
σ 2C, ijk The unmeasured concentrations can be obtained using eq

(Texp − Tmodel(θ)ik )2 ÑÑÑÑ

19 such that rank(Na) = R. If the assumption of constant

ÑÑ
ÑÑ
Nexp L thermochemical properties is not valid, then we cannot apply

ÑÑ
ÑÖ
+ ∑∑ ik
2
k=1 i=1 σ T, ik
(17)
s.t. material, energy, and momentum balance equations are
from Table S1
θ ∈ [θ L , θU ] , θ ≥ 0
where Nexp corresponds to the number of experiments carried
out at different steady states, L is the number of observations
made for each flow rate, R corresponds to number of species
measured at every steady state, and σT,ik and σC,ijk are the
standard deviations of the temperature and concentration
measurements. The kinetic parameters θ are constrained to be
non-negative and to be within the limits θL and θU. The
nonlinear optimization problem mentioned in eq 17 is solved
using the solvers such as fmincon in MATLAB.
4.4. Incremental Approach. The extent-based incremen-
tal model identification approach decomposes the task of
identification into two steps: (i) computation of extents from
the measured concentrations and/or temperature and (ii)
parameter estimation from the computed extents. Next, these
steps will be described.
4.4.1. Computation of Extents. Depending on the
experimental conditions (isothermal or non-isothermal), we
need to compute the extents of reaction xr and/or the extent of
heating xq. Since R concentration measurements (ca) are
assumed to be available, the extent of reaction at the location
(z) can be computed as
x r(z) = NaT †(Fr, a − Fr, a(0))
ij c (z)ν(z) c (0)ν(0) yzz
the previously mentioned approach. We now propose a two
step method to compute both xr and xq from the data.
1. The extents of reaction xr are computed using eq 18.
2. Extent of heating xq can be computed using temperature
measurements and the extents of reaction as follows:
xq(z) = TI(z) − ( −ΔHTR )x r(z) (21)
z νρCp̂
where TI(z) = ∫ dT . The term TI(z) needs to be
0 Ac
computed numerically. In this case, the unmeasured
concentrations cu are computed from extents of reaction
using eq 19.
4.4.2. Parameter Estimation Using Computed Extents. In
this step, the individual computed extents are used to estimate
parameters pertaining to the known rate structures, i.e., rate
laws. Note that this step in the incremental identification can
be used for model discrimination as well. However, in this
work, it is assumed that the kinetic rate law for each reaction is
known. For isothermal and adiabatic reaction systems, the
extents of the ith reaction xr,i is calculated using eqs 8−13. Let
θri be the set of parameters that appear in the rate law for the
ith reaction. Let x̂r,i be the predicted extents of ith reaction
obtained by integrating the dynamic model equation of extents
described in eq 9. Since the extents are decoupled in nature,
the parameters corresponding to each reaction are estimated
separately using the least-squares approach:
dxr,̂ i(θri)
θr*i = arg min(xr, i − xr,̂ i(θri))2 s.t. = ri(θri),
dz
θri

= NaT †jjj a zz
j z
θri ∈ [θriL , θrUi ] , i = 1, ..., R (22)

k {
− a
Ac Ac (18) For a PFR operating under non-isothermal conditions with
heat loss to surroundings, the extent of heat transfer xq is
The unmeasured concentrations cu(z) can be obtained from computed using eq 20 or eq 21 depending on whether the
the computed extents of reaction as follows: thermochemical properties are constant or varying. θri, i =
Fr, u(z) 1,...,R are estimated by solving R separate optimization
c u (z ) = Ac problems as in eq 22. Let θq denote the set of parameters
ν(z) involved in heat transfer (e.g., heat transfer coefficient) and is
(NTu x r(z) + Fr, u(0)) estimated by solving the following additional optimization
= Ac problem:
ν(z) (19)
dxq̂
where cu (z) is the (S−R)-dimensional vector of the θq* = arg min(xq − xq̂ )2 s.t. = Q ext , θq ∈ [θqL , θqU ]
θq dz
unmeasured concentrations, and Nu is the stoichiometric
matrix of the unmeasured species. For non-isothermal reaction (23)
systems with constant thermochemical properties, concen- The kinetic parameters and heat transfer coefficient θ are
trations at unmeasured locations are interpolated and then the constrained to be non-negative and to be within the limits θL
13772 DOI: 10.1021/acs.iecr.9b00266
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Industrial & Engineering Chemistry Research Article

and θU. The optimization problem mentioned in eqs 22 and 23 corresponding to the reaction system with

ÄÅ É
is solved using the solvers in MATLAB. F = [FP , FCl 2 , FA , FHCl , FD]T is given by

5. SIMULATION STUDIES
5.1. Description of Reaction System. A reaction system
involving the production of allyl chloride (A) by the
chlorination of propylene (P) along with a side reaction
leading to the formation of dichloropropane (D) is used for
numerical studies. 11 We describe here particulars for
generating experimental data in silico for the reaction system.
The reactions are assumed to be carried out in a PFR having a
length l = 8 m and diameter di = 0.05 m. The inlet feed
contains propylene (P) and chlorine (Cl2) with the molar ratio
of P to Cl2 (FP/FCl 2) being 4:1. Also, the reactor is set to
operate at 2.02 × 105 Pa pressure. The model equations for
different scenarios are given in Table S1 of the Supporting
Information. We now describe the reaction scheme, kinetic
model, and the associated kinetic parameter values. These are
available in the literature.
Reaction Scheme:
k1
C3H6 + Cl 2 → C3H5Cl + HCl, r1 = k1PPPCl 2
k2
C3H6 + Cl 2 → C3H5Cl 2, r2 = k 2PPPCl 2
where PP and PCl2 are the partial pressure of components P and
Cl2, respectively. The unit of the reaction rates, r1 and r2, is in
mol m−3 s−1. The rate constants, k1 and k2 (in mol m−3 s−1
Pa−2), are given by
ij −63 267.20 yz
ÅÅ− 1 − 1 1 1 0 ÑÑÑ
N = ÅÅ Å ÑÑ
ÅÅÇ− 1 − 1 0 0 1 ÑÑÑÖ
(25)
For the above-mentioned reaction system, spatial concen-
tration and/or temperature measurements pertaining to several
measurement strategies under different experimental condi-
tions (non-isothermal or isothermal) are considered. These are
discussed in the following section.
5.2. Spatial Concentration and Temperature Meas-
urement Strategies for Experimental Data Generation.
We now discuss various concentration and temperature
measurement strategies in PFRs operating under isothermal
and non-isothermal conditions. First, considering non-iso-
thermal (including adiabatic) operating conditions, the
following cases are considered for spatial concentration and
temperature measurements:
Base case 1: Steady-state temperature and concentrations are
measured along the length of the reactor (25 locations) for 3
flow rates.
Case 1: Steady-state temperature and concentrations are
measured only at the end for 3 flow rates.
Case 2: Temperature is measured along the length of the
reactor (25 locations), and concentrations are measured only
at the end for 3 flow rates.
Case 3: Temperature is measured along the length of the
reactor (25 locations), and concentrations are measured at 5
locations for 3 flow rates.
Considering isothermal operating conditions, the spatial

k1 = 9.02 × 10−5 expjjjj zz

zz
concentration measurement strategies are
j z
k {
Base case 2: Steady-state concentrations are measured along
R gT the length of the reactor (25 locations) at 15 different
ij −15 956.36 yz
k 2 = 5.12 × 10−9 expjjjj zz
operating conditions, viz., 5 temperatures each at 3 flow rates.
zz
j z
Case 4: Concentrations are measured only at the end of the

k {
R gT reactor at 15 different operating conditions, viz., 5 temper-
atures each at 3 flow rates.
where Rg is the gas constant in J mol −1 K −1 and T is in K. The Case 5: Concentrations are measured at 5 locations at 15
heat capacity Cpj of the jth species in J mol −1 K −1 can be different operating conditions, viz., 5 temperatures each at 3
flow rates.
computed as follows: For adiabatic operation of PFR, the reaction system is
C p = aj + (bjT ) + (cjT 2) + (djT 3), j = 1, ..., S simulated for three different molar flow-rates, viz., 385, 430,
j (24) and 450 mol h−1 with the inlet feed temperature being 473 K.
To account for the fact that measurements are noisy,
The coefficients a, b, c, and d for all the species are listed in
experimental data is generated in silico by adding the Gaussian
Table 2 considering the temperature to be in K. Table 2 also
noise to the raw simulated data without noise, for all the three
lists the heat of formation of species.
molar flow-rates. For concentration data, the Gaussian noise
Under the ideal gas assumption, the relationship between
the concentration and the partial pressure of the jth species with mean μ = 0 and standard deviation σj= αcmax,j, where j =
cj 1,...,S, is added. Similarly, for temperature data, the Gaussian
(Pj) is as follows: Pj = R T . The stoichiometric matrix N noise added has mean μ = 0 and standard deviation σ = αTmax.
g
Here, the parameter α takes the values of 2% and 5%.
Table 2. Coefficients to Calculate the Heat Capacity and Considering isothermal operating conditions, the reaction
Enthalpy of Formation of Species Involved in the system is simulated at the same three molar flow-rates as in the
Chlorination of Propylene Reaction System case of non-isothermal operation. For each molar flow-rate,
simulations are performed at the isothermal temperatures 473,
component a b (×102) c (×105) d (×109) H298K
f (J mol−1) 523, 573, 623, and 673 K, to obtain the noise-free
Cl2 26.91 3.38 −3.87 15.46 0 concentrations. As in non-isothermal operation, the noisy-
P 3.62 23.44 −11.59 22.03 20096.64 concentration data is generated by adding the Gaussian noise
A 2.52 30.44 −22.77 72.88 −628.02 with mean μ = 0 and standard deviation σj = αcmax,j, where j =
HCl 30.27 −0.72 1.24 −3.92 −92360.80 1,...,S with α = 2% and 5% for each combination of molar flow
D 10.44 36.52 −26.02 77.36 −165797.28 rates and temperature.
13773 DOI: 10.1021/acs.iecr.9b00266
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Industrial & Engineering Chemistry Research Article

6. RESULTS AND DISCUSSION Table 4. Parameter Estimates along with 95% Confidence
We present here important results, obtained after applying the Intervals Obtained Using the Simultaneous Identification
Approach for Isothermal Operation with 2% Noise
spatial concentration and temperature measurement strategies
discussed in section 5.2 to the reaction system described in scenario parameter mean confidence interval
section 5.1. The results are discussed in the context of effect of Base case 2 k1,0 8.93 × 10 −5
8.93 × 10−5 ± 1.24 × 10−6
experimental conditions, measurement strategies, and model k2,0 5.05 × 10−9 5.05 × 10−9 ± 1.31 × 10−10
identification techniques on the parameter estimation problem. Ea1 62296.30 62296.30 ± 4237.76
6.1. System Theoretic Analysis. Before going into Ea2 15514.70 15514.70 ± 341.22
detailed analysis of results, we first consider the minimum
number of species that need to be measured for the purpose of Case 4 k1,0 8.93 × 10−5 8.93 × 10−5 ± 1.52 × 10−6
identification of a reaction system. As discussed before, only R k2,0 5.05 × 10−9 5.05 × 10−9 ± 2.19 × 10−10
species concentrations need to be measured such that Ea1 64432.20 64432.20 ± 1959.18
rank(Na) = R, where Na corresponds to the stoichiometric Ea2 15567.15 15567.15 ± 562
matrix of the measured species for isothermal operating
conditions. For the reaction system described in section 5.1,
Case 5 k1,0 8.93 × 10−5 8.93 × 10−5 ± 1.52 × 10−6
rank(N) = 2, implying two species need to be measured. In k2,0 5.05 × 10−9 5.05 × 10−9 ± 1.80 × 10−10
particular, we measure the concentration of species A and Cl2, Ea1 63340.56 63340.56 ± 3275.61
since this choice satisfies the condition rank(Na) = rank(N) =
Ea2 15530.26 15530.26 ± 482.04
2. In addition, temperature is measured along the length of the
reactor in the non-isothermal mode of operation.
6.2. Experimental Condition: Non-isothermal vs isothermal operations are presented in Tables S2 and S3 in the
Isothermal. We discuss here the results obtained from Supporting Information.
parameter estimation using the simultaneous identification Comparing the results for Case 3 and Case 5 for isothermal
approach for both non-isothermal and isothermal operating and non-isothermal operations, which involve concentration
conditions in a PFR. The parameters measurements at 5 spatial locations, it is observed that the
(θ = [k1,0 , Ea1 , k 2,0 , Ea 2 ]T ) are estimated using the method- mean and confidence intervals of the parameters are
comparable. A similar conclusion holds true for Case 1 and
ology discussed in section 4.2. The confidence intervals for the Case 4 which involve measuring concentrations only at the exit
parameters are estimated using standard bootstrapping of the reactor. This shows that non-isothermal operation of
technique. For different spatial measurement scenarios as PFR yields comparable results with fewer experiments (Nexp =
discussed in section 5.2, the results are presented for non- 3) when compared to isothermal operation (Nexp = 15).
isothermal and isothermal operating conditions in Tables 3 6.3. Measurement Strategies. In this section, results of
and 4 for experimental data with 2% noise. The results for different measurement strategies applied to non-isothermal and
experimental data with 5% noise for non-isothermal and isothermal operations are discussed. From Table 3, it is found
that the results for Case 3 are comparable to those for Base
Table 3. Parameter Estimates along with 95% Confidence case 1, in which concentrations and temperature are measured
Intervals Obtained Using Simultaneous Identification at 25 locations. This shows that fewer concentration
Approach for Non-isothermal (Adiabatic) Operation with measurements are sufficient for yielding proper results under
2% Noise non-isothermal operating conditions in a PFR. The concen-
trations (A and Cl2) and temperature profiles obtained for
scenario parameter mean confidence interval Case 3 along with true and noisy measurements are depicted in
Base case 1 k1,0 9.02 × 10−5 9.02 × 10−5 ± 8.81 × 10−7 Figure 2, for an inlet molar feed rate of 385 mol h−1. It is found
k2,0 4.98 × 10−9 4.98 × 10−9 ± 2.54 × 10−10 that the predicted concentrations for the measured and
Ea1 64912.10 64912.10 ± 829.92 unmeasured species and the predicted temperature match
Ea2 15777.21 15777.21 ± 608.57
closely with the true measurements. The concentration and
temperature profiles for Cases 2 and 3, with the flow rate being
450 mol h−1, are depicted in Figures S1 and S2 of the
Case 1 k1,0 8.89 × 10−5 8.89 × 10−5 ± 2.25 × 10−6
Supporting Information.
k2,0 4.92 × 10−9 4.92 × 10−9 ± 1.66 × 10−10
Similar results are obtained for isothermal operation of PFR.
Ea1 64731.14 64731.14 ± 1583.44
From Table 4, it is seen that the parameters estimated for Base
Ea2 16070.52 16070.52 ± 268.32 case 2 and Case 5 are comparable. The concentration profiles
for Case 4 and Case 5 of measured and unmeasured species are
Case 2 k1,0 8.94 × 10−5 8.94 × 10−5 ± 1.86 × 10−6 presented in Figures 3 and 4. Figure 3a corresponds to the
k2,0 4.98 × 10−9 4.98 × 10−9 ± 2.36 × 10−10 simulated concentration profiles of species A and Cl2 for Case
Ea1 64729.78 64729.78 ± 2494.26 4.
Ea2 16072.22 16072.22 ± 234.25 It is observed that the concentration profiles of measured
and unmeasured species do not agree well with the true
Case 3 k1,0 8.85 × 10−5 8.85 × 10−5 ± 1.96 × 10−6 profiles for Case 4. This is due to fewer number of
k2,0 5 × 10−9 5 × 10−9 ± 2.58 × 10−10 concentration measurements (only at the exit of the reactor).
Ea1 64615.86 64615.86 ± 2847.86 The fit can be improved by conducting more experiments at
several steady-state flow rates with the concentration being
Ea2 15841.34 15841.34 ± 618.43
measured only at the exit of the reactor. On the other hand, it
13774 DOI: 10.1021/acs.iecr.9b00266
Ind. Eng. Chem. Res. 2019, 58, 13767−13779
Industrial & Engineering Chemistry Research Article

Figure 2. Comparison of true and predicted concentration and temperature profiles at inlet molar flow rate of 385 mol h−1 and inlet temperature of
473 K for Case 3 (adiabatic operation) with 2% noise: (a) concentration profiles of measured species, (b) concentration profiles of unmeasured
species, and (c) temperature profile.

Figure 3. Comparison of true and predicted concentration profiles at inlet molar flow rate of 385 mol h−1 and isothermal temperature of 673 K for
Case 4 with 2% noise: (a) concentration profiles of measured species and (b) concentration profiles of unmeasured species.

13775 DOI: 10.1021/acs.iecr.9b00266

Ind. Eng. Chem. Res. 2019, 58, 13767−13779
Industrial & Engineering Chemistry Research Article

Figure 4. Comparison of true and predicted concentration profiles at inlet molar flow rate of 385 mol h−1 and isothermal temperature of 673 K for
Case 5 with 2% noise: (a) concentration profiles of measured species and (b) concentration profiles of unmeasured species.

can be seen from Figure 4 that the agreement is better for Case Table 5. Parameter Estimates along with 95% Confidence
5, where more concentration measurements are available. Intervals Obtained Using the Extent-Based Incremental
From the estimated parameters values, the concentration Identification Method under Isothermal Operation with 2%
profiles for species A and Cl2 and the unmeasured species are Noise
simulated for the three molar flow-rates at the isothermal
scenario parameter mean confidence interval
temperature of 673 K for Case 5. The predicted concentrations −5
along with the true and noisy concentrations are depicted in Base case 2 k1,0 9.06 × 10 9.06 × 10−5 ± 7.88 × 10−6
Figure 4. The concentration profiles for Cases 4 and 5, at a k2,0 4.11 × 10−9 4.11 × 10−9 ± 1.09 × 10−9
63158.64 ± 391.76
flow rate of 450 mol h−1, can be found in Figures S3 and S4 of Ea1 63158.64
the Supporting Information. Thus, spatial concentration and Ea2 15818.19 15818.19 ± 1211.70
temperature measurements for different steady states under
non-isothermal operation can provide more information for Case 5 k1,0 6.90 × 10−5 6.90 × 10−5 ± 1.02 × 10−5
the identification of reaction systems when compared to k2,0 3.23 × 10−9 3.23 × 10−9 ± 1.65 × 10−10
isothermal operation. Ea1 61990.52 61990.52 ± 665.33
6.4. Model Identification Techniques. This section Ea2 14685.44 14685.44 ± 2290.27
compares the results of parameter estimation between the
simultaneous and incremental model identification approaches.
For the reaction system mentioned in section 5.1, the extent- under isothermal operating conditions, the confidence intervals
based incremental identification is used to estimate the of the parameters broaden. This shows that more measure-
parameters pertaining to the system, for non-isothermal and ments are required in the case of isothermal experiments when
isothermal operations in a PFR. compared to non-isothermal experiments.
We present results from applying the incremental approach In Figure 5, the extents of reaction, xr, true, computed, and
to the experimental data for cases in which the concentrations predicted, are plotted against length of reactor z for Case 3.
of species A and Cl2 are measured less frequently along the The extents are calculated considering adiabatic operation of
length of reactor z when compared to temperature T(z). The PFR. The results for experimental data with 5% noise
results for adiabatic operation of PFR are presented for Base (adiabatic and isothermal operation) are reported in Tables
case 1 and Case 3 with 2% noise in Table 6. Also, the results S4 and S5 of the Supporting Information.
for the isothermal operation of PFR are presented for Base case It should be noted that, the parameters θ estimated using the
2 and Case 5 in Table 5. The confidence intervals of the extent-based incremental identification are biased in nature as
parameters, for both the non-isothermal and isothermal discussed in Bhatt et al.20 This is due to the computation of
operating conditions, are estimated using Monte Carlo reaction extents xr from noisy measurements of concentrations
simulations. and temperature. This is also clear from Figure 5a where the
From Table 6, it is observed that the mean and confidence predicted extent of reaction 1 diverges from the true extents,
interval of the parameters are comparable for the two cases of especially at higher z. In order to get statistically optimal
non-isothermal operation of PFR. This is mainly due to estimates, the estimated parameters using the incremental
interpolation of unmeasured concentration data used to approach can be used as initial guess for the simultaneous
compute the extents of reaction xr causing the available identification and the parameters re-estimated. Since the
measurements to be similar for both Base case 1 and Case 3. incremental approach deals with decoupled extents, the
For isothermal operation, since only concentration measure- identification step involves less computational time compared
ments are available, the overall rate constants are estimated at to the simultaneous model identification approach. The extent-
each isothermal temperature. Thereafter, the pre exponential based incremental identification approach is also demonstrated
factors k0 and the activation energies Ea are obtained by a for a liquid phase reaction system in PFR operating in adiabatic
linear regression between ln(k) and 1/T. From Table 5, it is mode. The details and results of the above-mentioned system
found that as the number of spatial measurements decrease, can be found in the Supporting Information.
13776 DOI: 10.1021/acs.iecr.9b00266
Ind. Eng. Chem. Res. 2019, 58, 13767−13779
Industrial & Engineering Chemistry Research Article

Table 6. Parameter Estimates along with 95% Confidence Intervals Obtained Using the Extent-Based Incremental
Identification Approach on Adiabatic and Non-isothermal PFR with Heat Loss Experimental Data with 2% Noise
adiabatic non-isothermal PFR with heat loss
scenario parameter mean confidence interval mean confidence interval
Base case 1 k1,0 7.27 × 10−5 7.27 × 10−5 ± 2.65 × 10−7 7.33 × 10−5 7.33 × 10−5 ± 6.41 × 10−8
k2,0 7.41 × 10−9 7.41 × 10−9 ± 1.47 × 10−9 4.51 × 10−9 4.51 × 10−9 ± 8.25 × 10−11
Ea1 64349.39 64349.39 ± 621.10 62664.90 62664.90 ± 362.57
Ea2 15480.04 15480.04 ± 1072.54 14937.31 14937.31 ± 176.20
U̅ 33.65 33.65 ± 3

Case 3 k1,0 7.27 × 10−5 7.27 × 10−5 ± 2.68 × 10−7 7.33 × 10−5 7.33 × 10−5 ± 7.33 × 10−8
k2,0 7.07 × 10−9 7.07 × 10−9 ± 1.89 × 10−9 4.54 × 10−9 4.54 × 10−9 ± 2.14 × 10−10
Ea1 64366.63 64366.63 ± 624.27 62664.78 62664.78 ± 357.10
Ea2 15224.15 15224.15 ± 1377.98 14977.57 14977.57 ± 264.96
U̅ 33.58 33.58 ± 3.22

Figure 5. Comparison of true and predicted extents of reaction xr at an inlet molar flow rate of 385 mol h−1 and inlet temperature of 473 K for Case
3 (adiabatic operation) with 2% noise: (a) extent of reaction 1 and (b) extent of reaction 2.

6.4.1. Non-isothermal PFR with Heat Loss. The reaction
system mentioned in section 5.1 is also simulated for the case
of a non-isothermal operation of PFR with heat loss. The heat
transfer coefficient is assumed to be 28.39 W/m2 K with the
ambient temperature being 473 K.11 The measured compo-
nents are concentrations of species A, Cl2 and temperature T.
This satisfies the minimum measurements conditions required
for identifiability in non-isothermal PFR with heat loss as
discussed in Table 1. The incremental identification results for
non-isothermal operation of PFR with heat loss are presented
for Base case 1 and Case 3 with 2% noise in Table 6. The
parameters to be estimated for non-isothermal operation of
PFR with heat loss (θ = [k1,0,Ea1,k2,0,Ea2,U]T) are obtained by
solving the optimization problem posed in eq 23. The true,
computed, and predicted extents of reaction xr and extents of
heat transfer xq for the non-isothermal PFR with heat loss are
depicted in Figure 6. Similarly, the results for the data with 5%
noise are reported in Table S4 of the Supporting Information.
It should be noted that since the thermochemical properties
are not constant for the above reaction system, the incremental
identification will have two steps as discussed in section 4.4.1.
It should be further noted that the parameters θ estimated
using extent-based incremental identification are also biased in
nature as discussed in Section 6.4. Since the extents are
computed by augmenting the measured and interpolated
concentrations, the effect of the quality of interpolation on
13777
computation of parameters θ based on extent-based
incremental identification will be the subject of future work.
7. CONCLUSIONS
In this work, several measurement strategies for collecting
spatial concentration and temperature data from steady-state
PFRs operating under isothermal as well as non-isothermal
conditions have been discussed. Using the simultaneous
identification approach, the efficacy of the strategies in
estimating model parameters is ascertained by applying the
measurement strategies to the chlorination of the propylene
reaction occurring in a PFR. It has been demonstrated that
under non-isothermal operating conditions, more frequent
temperature measurements combined with less frequent
concentration measurements suffice for reliable estimation of
model parameters pertaining to multiple reaction systems.
Under isothermal operating conditions, however, more
concentration measurements are required for accurate
parameter estimation. Since concentration measurements are
more tedious when compared to temperature measurements,
non-isothermal experiments require less experimental effort
and are more informative toward parameter estimation in
comparison to isothermal experiments.
Model parameter identification has also been done using the
extent-based incremental identification approach applied to
DOI: 10.1021/acs.iecr.9b00266
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Industrial & Engineering Chemistry Research
Figure 6. Comparison of true and predicted extents of reaction xr and extent of heat transfer xq at inlet molar flow rate of 385 mol/h and inlet
temperature of 473 K for Case 3 (non-isothermal operation involving heat loss) with 2% noise: (a) extent of reaction 1, (b) extent of reaction 2,
and (c) extent of heat transfer.
PFRs operating under non-isothermal conditions. In this case,
minimal measurements involving little experimental effort are
sufficient to get good estimates. Also, it should be noted that
the extent-based incremental identification approach deals with
the decoupled extents of reaction for parameter estimation.
Hence, incremental identification is less computationally
intensive in comparison to simultaneous identification.
Another advantage of the incremental approach over the
simultaneous approach is that proper kinetic rate laws for
reactions can be determined, if not available. For this, a set of
candidate rate laws are proposed for each reaction. Thereafter,
the model that represents the reaction system most effectively,
on the basis of some criterion, is selected. Thus, whereas the
simultaneous approach would give poor estimates of
parameters in the case of a model mismatch, the extent-
based approach is robust to such an eventuality. Another
significant contribution in this paper is the proposed two-step
extent-based incremental approach for a non-isothermal PFR
with heat loss for varying thermochemical properties.
Implementation of the proposed method of spatial
concentration and temperature measurements involves meas-
uring concentration by offline analytical equipment and
measuring temperature using integrated temperature sensors
placed along the length of the reactor. This experimental setup
does not require any complex instrumentation unlike flow
manipulation and temperature ramping techniques found in
the existing literature. Also, the proposed methodology
13778
Article
provides reasonably accurate estimates of parameters thereby
making the results comparable to the flow manipulation and
temperature ramping techniques. The results are also
comparable with existing methods in which isothermal
experiments are carried out to generate concentration data at
different temperatures. Further, as the flow behavior in
microreactors are approximated to plug flow conditions, the
proposed methodology can also be used for identification of
reaction systems in microreactors. In the future, we wish to
investigate the effectiveness of various measurement strategies
under different experimental conditions toward model
structure discrimination.
■
*
ASSOCIATED CONTENT
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.iecr.9b00266.
Model equations of PFR for different experimental
scenarios; parameters estimated using the simultaneous
identification for the data with 5% noise for adiabatic
operation; parameters estimated using the simultaneous
identification for the data with 5% noise for isothermal
operation; parameters estimated using extent-based
incremental identification for adiabatic and non-
isothermal PFR with heat loss for the data with 5%
noise; and parameters estimated using extent-based
DOI: 10.1021/acs.iecr.9b00266
Ind. Eng. Chem. Res. 2019, 58, 13767−13779
Industrial & Engineering Chemistry Research Article

incremental identification for adiabatic PFR (liquid complex reactions-Oxidative dehydrogenation of propane as an
phase system) for the data with 2 and 5% noise example. Chem. Eng. J. 2005, 108, 219−226.
(PDF) (15) Kolkowski, M.; Malachowski, J.; Keil, F.; Liebner, C.; Wolf, D.;
Baerns, M. Influences of heat transport on the determination of

■ AUTHOR INFORMATION
Corresponding Authors
reaction rates using the temperature scanning plug flow reactor. Chem.
Eng. Sci. 2003, 58, 4903−4909.
(16) Moore, J. S.; Jensen, K. F. Batch kinetics in flow: online IR
analysis and continuous control. Angew. Chem. 2014, 126, 480−483.
*E-mail: sridharkrn@iitm.ac.in. (17) Aroh, K. C.; Jensen, K. F. Efficient kinetic experiments in
*E-mail: niravbhatt@iitm.ac.in. continuous flow microreactors. React. Chem. Eng. 2018, 3, 94−101.
ORCID (18) Rodrigues, D.; Srinivasan, S.; Billeter, J.; Bonvin, D. Variant and
Sridharakumar Narasimhan: 0000-0002-6215-545X invariant states for chemical reaction systems. Comput. Chem. Eng.
2015, 73, 23−33.
Nirav Bhatt: 0000-0003-0928-6028 (19) Michalik, C.; Brendel, M.; Marquardt, W. Incremental
Notes identification of fluid multi-phase reaction systems. AIChE J. 2009,
The authors declare no competing financial interest. 55, 1009−1022.

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ACKNOWLEDGMENTS
The authors thank the Robert Bosch Center for Data Science
and Artificial Intelligence, IIT Madras, for financial support
under the Project “Online Data Analysis for Rapid
Identification and Monitoring of Reaction Systems Based on
Multi-Sensor and Multi-Scale Data”.
(20) Bhatt, N.; Kerimoglu, N.; Amrhein, M.; Marquardt, W.; Bonvin,
D. Incremental identification of reaction systems-A comparison
between rate-based and extent-based approaches. Chem. Eng. Sci.
2012, 83, 24−38.
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based on Experimental data From Steady-state Plug Flow Reactors.
Comput.-Aided Chem. Eng. 2015, 37, 593−598.
(22) Amrhein, M.; Bhatt, N.; Srinivasan, B.; Bonvin, D. Extents of

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reaction and flow for homogeneous reaction systems with inlet and
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13779 DOI: 10.1021/acs.iecr.9b00266

Ind. Eng. Chem. Res. 2019, 58, 13767−13779