Journal of Process Control 58 (2017) 46–62

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Journal of Process Control

journal homepage: www.elsevier.com/locate/jprocont

Research Paper

Design and plantwide control of n-butyl acrylate production process

Mihai Daniel Moraru a,b , Costin Sorin Bildea b,∗
a
Department of Process Technology and Development, Hexion, Seattleweg 17, 3195 ND Pernis, Rotterdam, The Netherlands
b
Department of Chemical and Biochemical Engineering, University POLITEHNICA of Bucharest, str. Gh. Polizu 1-7, 011061, Bucharest, Romania

a r t i c l e i n f o a b s t r a c t

Article history: n-Butyl acrylate is commercially produced from acrylic acid and n-butanol using strong acidic homoge-
Received 2 October 2016 neous catalysts. To overcome problems related to corrosion, catalyst removal from product and catalyst
Received in revised form 21 May 2017 disposal after neutralization, research based on solid catalysis received increased attention in the recent
Accepted 28 August 2017
years. However, design and control studies of an entire plant are rare. In this paper, the design and con-
trol of two reaction-separation-recycle process alternatives are developed. Both use a fixed-bed reactor
Keywords:
with Amberlyst 131 catalyst. The separation of n-butyl acrylate from the mixture with n-butanol and
n-Butyl acrylate
acrylic acid is difficult. One of the process alternatives achieves the separation by distillation at pressure
Esterification
Process design
above atmospheric, while the other conveniently employs extractive distillation with ethylene glycol.
Plantwide control Both processes are controllable, the control system showing robustness when increase or decrease in
Reaction-separation-recycle production capacity is required, or operating conditions change. Aspen Plus and Aspen Plus Dynamics
Dynamic simulation are used as efficient Computer-Aided Process Engineering tools.
© 2017 Elsevier Ltd. All rights reserved.

1. Introduction
n-Butyl acrylate (n-BA) is an important bulk chemical used as
precursor in the production of acrylic polymers. Its end-use appli-
cations are in water-based paints [1], production of varnishes,
adhesive, finishes of papers and textiles [2], and cleaning products,
atmospheric surfactants, aqueous resins and elastomers [3]. n-BA
is growing in demand [4]. In 2013, 43.7% of global demand came
from coatings, followed by 17% production of polyethylene, 17%
adhesives, 10% textiles, 4.7% pulp/paper, 3.8% in polish/stabilizers,
2% in printing/dying, and 1.8% in other uses [3]. The same reference
estimates that the global capacity in 2013 was 3.45 million metric
tons per year, while the global demand growth is forecasted at 5.5%
yearly to 2018. Thus, the global demand in 2018 is estimated at 4.5
million metric tons.
n-BA is produced in the equilibrium esterification reaction
between acrylic acid (AA) and n-butanol (n-BuOH), catalysed by
homogeneous or heterogeneous catalysts. Water is obtained as
by-product. At commercial scale, n-BA is manufactured in a homo-
geneously catalysed multi-stage process using two reactors with a
total residence time of approximately three hours, as mentioned
by Niesbach et al. [5]. Similar to this, reference [1] describes a pro-
cess for higher alkyl acrylates, which are preferably carried out
∗ Corresponding author.
E-mail address: s bildea@upb.ro (C.S. Bildea).
batchwise with three to five hours reaction times. Some homo-
geneous catalysts used in these processes are sulphuric acid and
p-toluenesulfonic acid [1].
The homogeneous process is both challenging and cost inten-
sive [5]. Some key disadvantages of the sulphuric acid catalysed
process are corrosion, purification of product, and acid neutraliza-
tion which creates problems with waste disposal. Usually, these
lead to increased energy requirements and maintenance costs, and
a continuously increasing difficulty to comply with environmental
regulations. Hypothetically, the future plants designed to use the
strong acidic homogeneous catalysis would require higher invest-
ment costs due to special material of construction when compared
to the heterogeneous catalysed processes.
Recent studies focus on solid catalysis using various ion
exchangers ([6–9]) and homogeneous catalysis using green sol-
vents as reaction media [10]. Despite its wide use as a large bulk
chemical, there are only a few papers regarding processes develop-
ment for n-BA production. With focus on the application of process
intensification techniques for new processes, reference [2] presents
the design and control of a reactive distillation column. In reference
[11], a pilot scale reactive distillation using a solid catalyst is inves-
tigated based on which an industrial scale system is proposed [5].
Another reference [12] presents experimental results on a hybrid
reactive-separation system coupling reaction and pervaporation. In
a recent study [13], modelling and analysis of a simulated moving
bed reactor is performed for a pilot and plant scale process. The lit-
erature devoted to design, dynamics and control of n-BA processes

http://dx.doi.org/10.1016/j.jprocont.2017.08.008
0959-1524/© 2017 Elsevier Ltd. All rights reserved.
 M.D. Moraru, C.S. Bildea / Journal of Process Control 58 (2017) 46–62
based on solid catalysts is scarce. The goal of this paper is to partially
fill this gap.
In this study, the conceptual design and plantwide control of
a conventional reactor-separation-recycle (RSR) system for n-BA
production is developed. Neither process optimization nor any
economic calculations are attempted. Aspen Plus and Aspen Plus
Dynamics are used as efficient Computer-Aided Process Engi-
neering tools to conduct the analyses. The study starts with the
description of reaction kinetics and basic thermodynamic prop-
erties. Based on a kinetic reactor model, a black-box separation
section and recycle of unconverted reactants, a preliminary analy-
sis decides on the range of the separation targets. Considering that
the RSR system has one or two recycles, a plantwide control struc-
ture is proposed for each system, and the steady state behaviour is
analysed using bifurcation diagrams. Based on these, a robust oper-
ating point is selected. After developing the separation system and
sizing the relevant equipment, the dynamic behaviour of the plant
is analysed when subjected to various perturbations. The focus is
on the plantwide control rather than on the control at the unit level.
The analysis ends with general conclusions on these designs. The
design proposes a plant with a capacity of 20,500 t/yr (∼2.5 t/h)
of n-BA, assuming 8000 operational hours per year. The product
specifications (mass based) are ≥99.5% n-BA, ≤0.05% water, and
≤0.01% AA, while the rest is n-BuOH, which accounts as well for
other impurities.
2. Reaction kinetics and thermodynamics
2.1. Reaction kinetics
This study considers that n-BA is produced by the esterifica-
tion Reaction (1) between n-BuOH and AA, obtaining water as
by-product, and that this is the only reaction that takes place in
the system.
catalyst
AA + n-BuOH  n-BA + Water
This is an equilibrium - limited reaction that can be per-
formed in liquid phase using solid catalysts. Based on laboratory
experiments using Amberlyst 131 and assuming the Langmuir-
Hinshelwood-Hougen-Watson (LHHW) mechanism, the following
kinetic equation and its parameters describe the formation of n-BA
[7]:
 
ccat kf Kacid Kalcohol aacid aalcohol − (1/Keq )aester awater
r=
(1 + Kacid aacid + Kalcohol aalcohol + Kester aester + Kwater awater )2
 E 
kf = k0 exp −
A
RT
 
Keq = exp 2134/T − 1.799
ln (Ki ) = Ai + Bi /T
Where r is the reaction rate in kmol/(m3 s) and ccat is the cata-
lyst concentration in kg/m3 of reactor. ai , (i = acid, alcohol, ester,
water), are the liquid phase activities, while Keq is the equilib-
rium constant. In the Arrhenius equation, the pre-exponential
factor and the activation energy are k0 = 2.275 × 105 kmol/(kg s) and
EA = 57421 kJ/kmol, respectively. The adsorption constants Ki of the
four components are derived from the experimental data presented
in the same reference [7]. Assuming that the adsorption step is tem-
perature dependent following the form of Eq. (5), the regressed
parameters A and B/[K] are: −6.4719 and 2235.8, for AA; −4.4473
and 1498.1, for n-BuOH; −4.4937 and 1107.0, for n-BA; −2.0325
and 1340.6, for water [14].
47
Fig. 1. Ternary diagram of the n-BuOH – BA – Water mixture (1.2 bar).
2.2. Thermodynamics
Physical properties of all pure components are available
in Aspen Plus databanks. For AA and n-BA, the vapour
pressure is described by the three-parameters Antoine equa-
tion: Pvap,i /[bar] = exp(C1,i + C2,i /(C3,i + T/[◦ C])). The parameters are
regressed from experimental data retrieved from Refs. [1] and [15],
for AA and n-BA, respectively. The regression is made using Aspen
Plus, selecting the maximum-likelihood as objective function and
using the default settings and calculation algorithm. The regressed
parameters C1 , C2 /[◦ C] and C3 /[◦ C] are: 9.75005, −3624.1 and 233.2
for AA; 8.25679, −2605.0 and 167.7 for n-BA [14].
The UNIversal QUAsi Chemical – Hayden-O’Connell (UNIQUAC-
HOC) model and the two sets of binary interaction parameters
(1) as given in reference [5] are used. One set describes the vapour-
liquid, while the other the liquid–liquid equilibrium. This system
presents multiple azeotropes and complex vapour-liquid–liquid
equilibrium, and the UNIQUAC-HOC model can fairly well describe
its complexity [5]. One of the design alternatives developed here
makes use of ethylene glycol (EG). The binary interaction param-
eters n-BuOH/EG and water/EG are available in Aspen (e.g. APV84
VLE-LIT databank) while AA/EG and n-BA/EG pairs are estimated
from group contributions using the UNIQUAC Functional-group
Activity Coefficients – Liquid–Liquid (UNIFAC-LL) method.
(2)
Fig. 1 presents the ternary diagram of the n-BuOH – n-BA –
Water mixture. At 1.2 bar, the system shows several low-boiling
(3) heterogeneous azeotropes which contain water. This suggests that
water separation should be an easy task: the azeotropic mixture is
obtained as distillate; after cooling and phase splitting, the aqueous
(4)
phase is withdrawn as product, while the organic phase is returned
(5) as reflux.
Fig. 2 presents the residue curves maps of the AA – n-BA – EG
and AA – n-BuOH – EG mixtures. In both diagrams, the iso-volatility
lines cross the EG-AA edge, therefore EG is a suitable solvent for
recovering AA from AA – n-BA and AA – n-BuOH high-boiling
azeotropic mixtures.
3. Reactor design
3.1. Reaction-Separation-Recycle system
The reactor is designed considering the complete plant struc-
ture, and not as standalone equipment. Fig. 3 presents the
Reaction-Separation-Recycle (RSR) structure of the plant. The fresh
48 M.D. Moraru, C.S. Bildea / Journal of Process Control 58 (2017) 46–62

Fig. 2. Residue curves maps of the AA – n-BA – EG and AA – n-BuOH – EG mixtures (0.1 bar).

Fig. 3. Reactor-Separation-Recycle structure.

Fig. 4. Left: Amount of catalyst and recycle flow rate versus conversion. Right: influence of recycle composition on the amount of catalyst needed, at 50% conversion.

feeds of n-BuOH (Fn-BuOH,0 ) and AA (FAA,0 ), together with the recycle
streams of unconverted reactants, are fed to the catalytic, multi-
tubular reactor which is operated adiabatically. The reactor effluent
is sent to a separation section where product n-BA, by-product
water and the recycle streams are obtained.
A steady state simulation model of the plant is developed using
Aspen Plus. The reactor is represented by the RPLUG model, which
assumes perfect radial mixing and neglects the axial mixing. Given
the reactor sizing elements (length, number of tubes, tube diame-
ter), the operating policy (adiabatic), the reaction kinetics and the
inlet stream (temperature, pressure, flow rate and composition),
the RPLUG model solves rigorous mass, energy and momentum bal-
ance equations, together with phase-equilibrium relationships to
calculate the condition of the outlet stream. The SEP model used for
the separation section simply distributes the components present
in the inlet stream to several outlet streams (recycles and products),
accordingly to component-specific separation factors. The MIXER
model performs the mass balance of mixing of several streams
(recycles and fresh feeds). Optionally, the condition of the outlet
stream (temperature, pressure) can be specified.
It is known that both AA and n-BA polymerise in this system.
Polymerization can be reduced when using efficient inhibitors as
phenothiazine [16], for example. However, it can also be reduced
when the reactor is operated at higher n-BuOH to AA ratios and
lower temperatures [9]. In this study, the plant is operated such
that the n-BuOH to AA ratio at the reactor inlet is at least 3.
3.2. Preliminary analysis
This analysis investigates the influence of recycle composition
on reactor design, namely on the amount of catalyst necessary to
achieve a certain conversion.
 M.D. Moraru, C.S. Bildea / Journal of Process Control 58 (2017) 46–62
Fig. 5. CS1 for one-recycle system; FAA,0 and F1 /FAA,0 ratio fixed; Fn-BuOH,0 on level control.
Fig. 6. XAA versus FAA,0 /mcat ratio bifurcation diagram for CS1, at different values of
the F1 /FAA,0 set-point.
The plant operates at 20 kmol/h fresh AA, setting the production
capacity. The stream at the reactor inlet has 85 ◦ C and a mole ratio
n-BuOH to AA of 3. The separation section is specified using the
separation factors (ˇ) for products outlets and reactants recycle.
The separation factor is component specific, and is defined as the
ratio between the flow rate leaving the plant as product and the
flow rate in the stream entering the separation section. A separation
factor of 1 means complete removal from the plant, while 0 means
complete recycle of component.
Fig. 4 (left) presents the mass of catalyst (mcat ) and the recycle
flow rate versus the AA conversion, if the reactants are com-
pletely recycled (ˇn-BuOH = 0, ˇAA = 0, both product streams leaving
the system are free of reactants), while the products are com-
pletely removed (ˇwater = 1, ˇn-BA = 1, recycle is free of products).
As expected, more catalyst is needed to achieve higher conversion,
with the benefit of lower recycle flow rate. Clearly, a trade-off exists.
To find the optimal conversion value, the reactor and separation
costs (both investment and operation) are needed, but these costs
are difficult to estimate at this preliminary stage of design. How-
ever, it is evident that a conversion of about 50% ensures that small
recycle is achieved with a reasonable amount of catalyst.
Fig. 4 (right) presents the mass of catalyst (mcat ) required to
achieve 50% AA conversion, as function of the separation factor
(ˇwater or ˇn-BA ), while n-BuOH and AA are completely recycled.
As the separation factor decreases, the required amount of catalyst
increases. It is observed that the amount of catalyst significantly
increases in the case of water recycle, while in the case of n-BA
there is only a slight effect. Thus, n-BA is afforded to be recycled
without tight specifications.
More details about the contribution of different factors to the
total annual cost can be found in our previous paper [14].
49
3.3. Sensitivity analysis
3.3.1. Basis of analysis
The reactor design makes use of the sensitivity analysis to select
a robust operating point. Depending on the separation choice, one
or two recycle streams can be present (see Sections 4.1 and 4.2 for
details). Thus, two distinct processes are developed. For each pro-
cess, a different control structure is proposed: CS1 for the system
with one recycle and CS2 for the system with two recycles.
Again, Aspen Plus is used to model the two systems, using the
procedure outlined in Section 3.2. The reactor is modelled based
on the kinetic model presented in Section 2.1, while the separator
is modelled as a black-box at given component separation factors
ˇ. For the first system ˇn-BuOH = 0, ˇAA = 0, ˇWater = 0.9, ˇn-BA = 0.25,
while for the second ˇn-BuOH = 0, ˇAA = 0, ˇWater = 0.9, ˇn-BA = 0.75.
Since the second system has two recycles, the recycled fraction (1-
ˇ) of n-BA is equally split: 0.125 goes with one recycle, and 0.125
with the other; since water is the lightest component, it is recy-
cled with the light reactant, n-BuOH (Recycle-2, in Fig. 3). One can
note the large difference between the recycled fractions of n-BA
(1-ˇn-BA ) of the two systems.
The justification for all selected values is as follows. Either pure
or less pure, in most of the cases it is fair to assume that all reactants
are separated from products and recycled to the reaction section.
The ternary heterogeneous azeotrope with a high content of water
(74.49% water, 22.73% n-BuOH, and 2.78% n-BA – molar based), hav-
ing the lowest boiling point (92.3 ◦ C at 1.013 bar) among all singular
points in this system, suggests that water can be easily removed.
Thus, only a small fraction of 0.1 is recycled to the reactor. The ther-
modynamic analysis of this system shows that the split between AA
and n-BA is particularly difficult. In the system with one recycle, the
n-BA has the highest boiling point (219.4 ◦ C at 5 bar). Thus, it is sep-
arated from the n-BuOH/AA/n-BA mixture by simple distillation as
bottom product, while both reactants are recycled together as dis-
tillate. However, the relative volatility of AA and n-BA is very small,
suggesting a difficult separation. Therefore, a large fraction of n-BA
is expected to be recycled. Thus, a fraction of 0.75 is selected. It is
worth noting that each of these fractions, water and n-BA, brings
roughly the same penalty on the amount of catalyst required to
achieve 50% AA conversion (Fig. 4). In the system with two recy-
cles, the split AA/n-BA is achieved by extractive distillation and the
reactants are recycled separately. Here, a sharper separation is sug-
gested and so a smaller fraction on n-BA is expected to be recycled.
Thus, a fraction of 0.25 is selected.
Although the selected separation factors may be debatable, this
analysis provides a good basis for a first estimate of the separation
targets and operating point. This analysis is intended to help the
design. It is not the intent to underdesign or overdesign the system,
but to help in selecting a robust operating point that gives flexibility
in throughput, rejects disturbances, and ensures safe operation.
To develop feasible control structures, we follow Altimari and
Bildea [17] and write the mole balance equations governing the
50 M.D. Moraru, C.S. Bildea / Journal of Process Control 58 (2017) 46–62

Fig. 7. CS2 for two-recycle system; F1A and F1B /FAA,0 ratio fixed; both FAA,0 and Fn-BuOH,0 on level control.

steady state behaviour of the RSR system (Fig. 3) as follows:

 
Fi,1 − Fi,0 − 1 − ˇi · i = 0 for i = AA, n-BuOH, n -BA, Water

(6)

where Fi,j are component molar flow rates at plant inlet (j = 0)

and reactor inlet (j = 1). ␤i are given separation factors, while i
are functions describing the dependence of the reactor-outlet flow
rates on the reactor-inlet flow rates.
Four unknowns can be determined from these equations. As
the flow rates of reaction products in the fresh feed streams are
Fn-BA,0 = FWater,0 = 0, two additional consistent specifications must
be provided. It should be noted that, accordingly to the reaction
stoichiometry, equal amounts of AA and n-BuOH are consumed in
the reactor:

Fn−BuOH,1 − ˚n−BuOH = FAA,1 − ˚AA (7) Fig. 8. Bifurcation diagram showing the dependence of XAA and FAA,0 versus F1A /mcat
ratio, for CS2, at different values of the F1B /F1A set-point.
Eq. (7) restricts the allowable specification. In particular, for com-
plete reactants recovery and recycle (ˇn-BuOH = 0, ˇAA = 0), the two
reactants balance equations reduce to:
CS2 FAA,1 = m; Fn−BuOH,1 = p · m (10)
FAA,0 = Fn−BuOH,0 (8)

This prohibits the simultaneous specification of fresh reactants
flows (FAA,0 = m, Fn-BuOH,0 = p), case when the plant model has either
infinitely many solutions (m = p, impossible to be achieved due to
unavoidable measurement uncertainty and control action imple-
mentation errors) or no solution at all (m = / p).
In practice, instead of fixed separation factors, the separation
section ensures that the concentration of the reactants (AA, n-
BuOH) in the product streams satisfy certain quality requirements.
Although the mathematical analysis is more involved [18], the pre-
vious conclusion remains true [19].
The two needed specifications could be achieved by either flow
or concentration control loops. Since concentration measurements
are expensive, setting flow rates is the preferred option. For this
reason, we consider two control strategies which can be applied
without using concentration measurements [20], corresponding to
the following two sets of specifications, which will be detailed in
the next Sections (3.3.2 and 3.3.3, respectively):
CS1 FAA,0 = m; Fn−BuOH,0 + ˚n−BuOH + ˚AA = p · m
3.3.2. Control structure CS1
This control structure, shown in Fig. 5, can be applied to systems
involving two reactants that are recycled together. It fixes FAA,0 = m
and the F1 /FAA,0 = p ratio at the reactor inlet. Since FAA,0 is added on
flow control, Fn-BuOH,0 is fed on level control to maintain the inven-
tory. The dependence of the state variable XAA (conversion of AA)
versus the model parameter FAA,0 /mcat , for different values of the
ratio set-point F1 /FAA,0 , is shown in Fig. 6 (also known as bifurcation
diagram). This control structure presents two steady states at low
FAA,0 values, or no steady state beyond a critical FAA,0 value. This
critical value, where the number of steady state changes, repre-
sents a bifurcation point of the model equations. At the bifurcation
point, the Jacobian of the model equations is singular, therefore
usual solution techniques fail. For this reason, diagrams presented
in Fig. 6 are computed using the following algorithm: in Aspen Plus,
the state variable (XAA ) is specified and the required value of the
model parameter (FAA,0 /mcat ) is calculated by means of a Design
Specification block; once a solution is found, then a new value of XAA
(9) is specified and the corresponding value of FAA,0 /mcat is computed.
 M.D. Moraru, C.S. Bildea / Journal of Process Control 58 (2017) 46–62
Fig. 9. Process flow diagram and plantwide control of the system with one recycle.
This procedure is similar to the local-parametrization continuation
algorithm as described by Seydel and Hlavacek [21].
To explain the observed behaviour, we note that the amount of
catalyst sets a constraint on the rate at which reactants are trans-
formed into products. Thus, if the flow rate of fresh reactant (FAA,0 )
exceeds the reactor capacity, reactants accumulation occurs and no
steady state can be reached. Moreover, the same transformation
rate can be achieved in two different ways, namely at low AA/high
n-BA, or at high AA/high n-BA concentrations, corresponding to two
steady states of high or low AA conversion, respectively.
Larger flexibility on FAA,0 processing is achieved as the F1 /FAA,0
ratio increases. The operation at high conversion on the stable
branch [18] and far enough from the bifurcation point (high sen-
sitivity region) is desired. Marquardt and Mönnigmann [22] and
the references cited therein provide several examples of a more
rigorous approach for achieving robustness of nonlinear process
systems.
Consider a reactor designed with a catalyst mass of 2000 kg, pro-
cessing a nominal fresh feed FAA,0 of 20 kmol/h (or FAA,0 /mcat = 10
kmol/h/tcat ) and operated at a ratio set-point F1 /FAA,0 of 10. Would
the separation system allow, the fresh feed could potentially be
increased even with 50% (to FAA,0 /mcat = 15 kmol/h/tcat ). The reac-
tor would process the fresh feed, and still operate far enough from
the bifurcation point, while the conversion remains satisfactory.
3.3.3. Control structure CS2
This structure, shown in Fig. 7, can be applied to systems involv-
ing two reactants which are distinctly recycled. It fixes F1A = m and
the ratio of reactants at the reactor inlet, F1B /F1A = p. F1A and F1B are
the combined recycle and fresh feeds of AA and n-BuOH, respec-
tively. The fresh reactants, Fn-BuOH,0 and FAA,0 , are fed on level
control. In this way, the control structure ensures that the amounts
51
of reactants brought in the process matches the amounts of reac-
tants consumed in the reactor. Therefore, if the separation section
does not impose any limitation, a steady state exists irrespective of
the reactor operating conditions.
The dependence of the reaction conversion XAA and plant capac-
ity FAA,0 /mcat versus the control parameter F1A /mcat is shown in
Fig. 8. A unique steady state exists. Compared to CS1, when CS2 is
applied the plant can process larger changes in the fresh feed flow
rates.
Note that a similar strategy can also be implemented for the
single-recycle process, if concentration measurements are used.
Thus, one can measure the total flowrate and reactants concen-
tration at the reactor inlet, calculate the component flow rates and
bring the fresh feeds as make-up streams to keep the reactor-inlet
component flow rates at some prescribed values.
3.3.4. Operating points
The corresponding nominal operating points are marked by
the dots presented in their respective figures. The fresh AA feed
(FAA,0 = 20 kmol/h) is selected to meet the required n-BA production
capacity. The AA conversion (XAA = 55%) is selected to keep a balance
between reactor size (amount of catalyst) and recycle (unconverted
reactants) as shown in Fig. 4 (left).
The selection of the ratio set-points (F1 /FAA,0 = 10 for CS1, and
F1B /F1A = 3 for CS2) ensures a molar ratio n-BuOH: AA at the reactor
inlet of 3.1 for CS1, and 4.5 for CS2. Given the nominal flow rate, con-
version and ratio set-points, the amount of catalyst (mcat = 2000 kg)
is determined. This has enough capacity to convert all fresh reac-
tants, enough flexibility at changes in fresh AA feeds, operating far
enough from the unfeasibility region.
52 M.D. Moraru, C.S. Bildea / Journal of Process Control 58 (2017) 46–62

Table 1
Equipment operating parameters – system with one recycle.

Heat Exchangers COND-1 COND-2 HX COOL-2

Pressure/[bar] 1.22 1.01 1.50 4.99
Inlet temperature/[◦ C] 98.2 132.6 129.8 220.3
Outlet temperature/[◦ C] 30.0 94.5 85.0 30.0
Heat duty/[kW] −557 −427 −674 −319

Vessels MIX VL-SEP LL-SEP

Pressure/[bar] 1.5 1.0 1.5
Outlet temperature/[◦ C] 134.7 96.9 30.0
Vapour fraction 0.13 0.10 0
Heat duty/[kW] 0 56 0
First liquid/total liquid 0.44

Columns C-1 C-2

Number of stages 15 100
Feed stage 3 3
Top stage pressure/[atm] 1.2 3.9
Molar bottoms to feed ratio 0.899 0.101
Molar reflux ratio 0.56 2.0
Molar boilup ratio 0.53 35.94
Condenser – total
Condenser/top stage heat duty/[kW] 0 −5719
Reboiler kettle kettle
Reboiler pressure/[bar] 1.36 4.99
Reboiler temperature/[◦ C] 135.8 220.3
Reboiler heat duty/[kW] 1259 6400

Reactor PFR
Mass of catalyst/[kg] 2000
Number of tubes 29
Length/[m] 3
Tube diameter/[m] 0.2
Heat duty/[kW] 0 (adiabatic)
Inlet temperature/[◦ C] 85.0
Outlet temperature/[◦ C] 82.7
Residence time/[min] 3.3

Table 2
Mass balance of the RSR system with one recycle.

Stream FAA,0 Fn-BuOH,0 F1 R-IN R-OUT Bottoms C-1 Recycle n-BuOH & Water Recycle n-BuOH & AA n-BA Water

Temperature/[◦ C] 25 25 135 85 83 136 97 175 30 97

Pressure/[bar] 2.00 2.00 1.50 1.50 1.43 1.36 1.01 4.00 4.99 1.01
Volume Flow/[m3 /h] 1.38 1.83 24.69 24.40 24.25 25.79 66.12 24.12 2.86 0.40
Mole Flow/[kmol/h] 20.0 19.9 200.0 220.0 220.0 197.8 2.2 177.9 20.0 19.9
Mass Flow/[kg/h] 1441 1478 18462 19903 19903 19484 54 16930 2553 366

Mole Fraction
Water 0.013 0.011 0.102 0.003 0.891 0.003 trace 0.994
n-BuOH 1 0.536 0.487 0.397 0.440 0.108 0.489 trace 0.006
AA 1 0.098 0.180 0.090 0.100 12 PPM 0.110 0.009 20 PPM
n-BA 0.353 0.321 0.411 0.457 0.001 0.397 0.991 12 PPM

Mass Fraction
Water 0.002 0.002 0.020 500 PPM 0.663 575 PPM trace 0.977
n-BuOH 1 0.430 0.399 0.326 0.331 0.330 0.381 trace 0.023
AA 1 0.077 0.143 0.072 0.073 37 PPM 0.083 0.005 80 PPM
n-BA 0.490 0.455 0.583 0.595 0.007 0.535 0.995 81 PPM

4. Design of the separation system
Depending on the components properties and choice of sep-
aration, one or two recycle streams can be present. Aspen is
conveniently used to calculate the azeotropes and construct phase
diagrams, based on which the structure of the separation system is
developed.
4.1. One-recycle system
Analysing the boiling points of pure components and
azeotropes, development of a separation section leading to one
recycle stream appears feasible. Water is separated first, by exploit-
ing the heterogeneity of its azeotropes (one ternary with n-BuOH
and n-BA, and two binary with n-BuOH, and n-BA, respectively).
Reactants n-BuOH and AA are intermediates, thus they are recycled
together after the separation from the product n-BA. The homoge-
neous binary azeotrope AA/n-BA, the highest boiler in this system,
can be avoided by separation at increased pressure, where this
azeotrope disappears.
The analysis performed in Section 3.3.2 provides a preliminary
mass balance, from which the design of the separation system can
start. The complete process flow diagram is presented in Fig. 9.
Although two recycle streams are apparent, the “Recycle n-BuOH
& Water” stream is very small (see Table 2), while reactants are
still mixed in the “Recycle n-BuOH & AA” stream. Therefore, the
flowsheet conceptually belongs to the one-recycle system previ-
ously described. Water is removed in a reboiled stripping column
(C-1) where the ternary azeotrope is obtained as top vapour. After
vapour condensation (COND-1) and liquid–liquid phase separation
 M.D. Moraru, C.S. Bildea / Journal of Process Control 58 (2017) 46–62 53

Table 3
Equipment operating parameters – system with two recycles.

Heat Exchangers COND-1 COND-2 HX COOL-2 COOL-3

Pressure/[bar] 1.2 1.0 1.5 1.2 1.0
Inlet temperature/[◦ C] 97.6 97.6 96.8 154.6 154.3
Outlet temperature/[◦ C] 30 80.4 85 30 30
Heat duty/[kW] −592 −27 −110 −201 −341

Vessels VL-SEP LL-SEP MIX-1 MIX-2 MIX-3

Pressure/[bar] 1 1.5 1.5 1.5 1.5
Outlet temperature/[◦ C] 96.4 30 101.1 48.3 30.0
Vapour fraction 0.1
Heat duty/[kW] 56
First liquid/total liquid 0.47

Columns C-1 C-2 C-3 C-4

Number of stages 15 20 15 15
Feed(s) stage 3 12 8-feed 6
4-solvent
Molar bottoms to feed ratio 0.853 0.180 0.418 0.776
Molar reflux ratio 0.59 2.25 2.00 39.55
Molar boilup ratio 0.64 8.67 3.57 6.82
Condenser – total total total
Top stage pressure/[bar] 1.2 1 0.1 0.1
Reboiler kettle kettle kettle kettle
Condenser/top stage heat duty/[kW] 0 −3551 −4522 −6769
Reboiler pressure/[bar] 1.34 1.20 0.24 0.24
Reboiler temperature/[◦ C] 131.2 154.6 145.2 154.3
Reboiler heat duty/[kW] 987 4019 4329 6743

Reactor PFR
Mass of catalyst/[kg] 2000
Number of tubes 29
Length/[m] 3
Tube diameter/[m] 0.2
Heat duty/[kW] 0 (adiabatic)
Inlet temperature/[◦ C] 85
Outlet temperature/[◦ C] 80
Residence time/[min] 5.7

(LL-SEP), the aqueous phase is partially vaporized (VL-SEP) and
liquid water (97.7%wt) is removed from the system. The vapours
containing n-BuOH are recycled to the reaction section. The organic
phase is fed as reflux to the reboiled stripper.
The x-y diagram of n-BuOH/n-BA shows an easy separation.
The binary AA/n-BA however is difficult to split. At atmospheric
pressure, the AA/n-BA azeotrope prevents obtaining n-BA as pure
bottoms product. Moreover, the relative volatility is low. Since this
azeotrope disappears at 4 bar, simple distillation can be used. The
bottom of the reboiled stripper is fed to a distillation column (C-2).
n-BA is obtained as bottoms product (99.5%wt), while a mixture
containing a significant amount of n-BA is recycled to the reaction
section.
Table 1 presents a summary of the equipment operating param-
eters, while a detailed mass balance for selected streams is
presented in Table 2.
Particularly for this process, one can observe that high purity
n-BA is achieved at the expense of a very high number of distil-
lation trays, and a very low per pass n-BA recovery (ˇn-BA = 0.22).
Moreover, due to operation at high pressure, resulting in high tem-
perature (175–220 ◦ C), the risk of AA and n-BA polymerization
increases.
contrast to Fig. 9, each reactant has its own, distinct recycle path.
Since the reactor outlet is a mixture similar to that from the system
with one recycle, the water is removed in the same manner. The
bottom of the reboiled stripper (C-1) is fed to an extractive distil-
lation column (C-3). Ethylene glycol (EG) extracts AA and caries it
in the bottoms while n-BA and n-BuOH are obtained as distillate.
The separation of AA from this ternary mixture is almost complete.
99.5% found in the feed is recovered, separated from the solvent
by distillation (C-4) and then recycled to the reaction section. The
split between AA and EG is easy. The n-BuOH/n-BA mixture can
be easily separated in a distillation column (C-2). n-BA is obtained
as bottoms product, while n-BuOH and some n-BA are obtained as
distillate.
Table 3 presents a summary of the equipment operating param-
eters, while a detailed mass balance for selected streams is
presented in Table 4.
Particularly for this process, one can observe that its separa-
tion system overcomes some drawbacks of the system with one
recycle, making this alternative more attractive. High purity n-BA
is achieved using a lower number of distillation trays (about 65
less, including the trays of the ED column), a higher n-BA recovery
factor, and operation at lower temperatures reducing the risk of
polymerization.

4.2. Two-recycle system

A system with two recycle streams is possible when AA is sep-
arated from the ternary n-BuOH/AA/n-BA mixture, using EG as
separation solvent, followed by the n-BuOH/n-BA split. Thus, AA
and n-BuOH are recycled separately.
As well as for the system with one recycle, the nominal point
provides a preliminary mass balance to start the design of the sep-
aration system. The process flow diagram is presented in Fig. 11. In
5. Plantwide control
The plantwide control preserves the control structures at the
plant level previously proposed by CS1 and CS2, for each of the
two systems. Coupled with the control at the unit level, its pri-
mary objective is to achieve stable operation by keeping the mass
inventory in the plant. In addition, required production rate and
product quality must be achieved, even when the process is sub-
54 M.D. Moraru, C.S. Bildea / Journal of Process Control 58 (2017) 46–62

Table 4
Mass balance of the RSR system with two recycles.

Stream FAA,0 Fn-BuOH,0 F1A F1B R-IN R-OUT Bottoms C-1

Temperature/[◦ C] 25 25 48 101 85 80 131

Pressure/[bar] 2.00 2.00 1.50 1.50 1.50 1.46 1.34
Volume Flow/[m3 /h] 1.38 1.85 2.79 11.55 14.16 14.01 14.71
Mole Flow/[kmol/h] 20.0 20.1 37.9 113.7 151.6 151.6 129.3
Mass Flow/[kg/h] 1441 1492 2820 8489 11309 11309 10887

Mole Fraction
Water trace 0.020 0.015 0.146 0.002
n-BuOH 1 117 PPM 0.949 0.712 0.580 0.677
AA 1 0.956 121 PPB 0.239 0.108 0.126
n-BA 0.042 0.031 0.034 0.165 0.194
EG 0.002 trace 409 PPM 409 PPM 480 PPM

Mass Fraction
Water trace 0.005 0.004 0.035 500 PPM
n-BuOH 1 117 PPM 0.942 0.707 0.577 0.596
AA 1 0.926 117 PPB 0.231 0.104 0.108
n-BA 0.073 0.053 0.058 0.284 0.295
EG 0.001 trace 340 PPM 340 PPM 354 PPM

Stream Recycle Water & n-BuOH Distillate C-3 Bottoms C-3 Recycle AA Recycle n-BuOH n-BA Water
◦
Temperature/[ C] 96 64 145 70 117 30 96
Pressure/[bar] 1.00 0.10 0.24 0.10 1.01 1.20 1.00
Volume Flow/[m3 /h] 67.25 11.98 5.39 1.42 9.69 2.88 0.40
Mole Flow/[kmol/h] 2.2 111.4 80.0 17.9 91.3 20.1 20.0
Mass Flow/[kg/h] 55 9509 5236 1379 6943 2566 368

Mole Fraction
Water 0.885 0.003 trace trace 0.003 trace 0.994
n-BuOH 0.114 0.786 55 PPM 248 PPM 0.958 0.004 0.006
AA 6 PPM 739 PPM 0.205 0.907 trace 0.004 10 PPM
n-BA 0.001 0.210 0.020 0.089 0.038 0.991 10 PPM
EG trace 74 PPM 0.775 0.003 trace 410 PPM 12 PPB

Mass Fraction
Water 0.650 572 PPM trace trace 784 PPM trace 0.975
n-BuOH 0.344 0.683 63 PPM 239 PPM 0.934 0.002 0.025
AA 18 PPM 624 PPM 0.226 0.849 trace 0.002 41 PPM
n-BA 0.005 0.316 0.039 0.148 0.065 0.995 68 PPM
EG trace 54 PPM 0.735 0.003 trace 199 PPM 41 PPB

jected to perturbations. Although possible in theory, design of a 5.2. One-recycle system

control system achieving optimal operation (according to some
economic objective function and certain disturbance scenarios) is
very difficult, involving many discrete variables (such as choice
of controlled variables, manipulated inputs and their pairing) and
continuous variables (such as controllers tuning parameters). As
solving this difficult MINLP problem has not been attempted, the
optimality of the proposed control structures cannot be guaranteed.
5.1. Equipment sizing
Dynamic simulations require that the major holdups are
known: columns trays and sumps, reflux, mixing and flash ves-
sels, decanters and reactors. Thus, based on the material balance
of the steady state simulations, the sizing of this equipment is
achieved. The columns diameters are sized using the facilities of
Aspen Plus. The sumps and reflux vessels are sized based on a
residence time of 10 min. The mixers, flash vessels and decanters
are sized based on 10 min residence time and the half-full crite-
ria. The heat exchangers are considered instantaneous. The reactor
is a multi-tubular heat exchanger-like equipment. The amount of
catalyst in the reactor’s tubes is 2000 kg, having spherical parti-
cles of 0.75 mm in diameter with a density of 1480 kg/m3 . The bed
voidage is 0.5. The amount of catalyst is accommodated in 29 tubes
with diameters of 0.2 m and 3 m length. The main dimensions are
showed, for each process, in Tables 1 and 3, respectively.
After steady state convergence in Aspen Plus, the simulation is
exported in Aspen Plus Dynamics as a flow-driven simulation.
Fig. 9 shows the plantwide control structure for the system with
one recycle. At the plant level, fresh AA is set on flow control. n-
BuOH is added as the stoichiometry requires. Therefore, in order to
maintain the inventory, n-BuOH is fed on level control. The reactor
is set to operate at a fixed F1 to FAA,0 mass ratio of 12.81.
Almost standard control applies at the unit level. The reactor
inlet temperature is controlled at 85 ◦ C by manipulating the duty
of the heat exchanger HX. At column C-1, the bottom tempera-
ture is controlled by manipulating the reboiler duty, sump level
by bottoms flow rate, and top pressure by the vapour flow rate.
LL-SEP has the organic level controlled by the organic flow rate,
aqueous level by aqueous flow rate, while the feed temperature
(condensed vapour of top C-1) is controlled by the duty of the con-
denser. VL-SEP has the liquid level controlled by the water flow
rate, pressure by vapour flow rate, and operates at a fixed duty. The
level in flash/mixing vessel MIX is controlled by the inlet flow rate
of fresh n-BuOH, pressure by vapour flow rate, while temperature of
the return condensed vapour stream is controlled by manipulating
the duty of COND-2.
At column C-2 top, tray-1 temperature is controlled by the reflux
ratio, pressure is maintained by condenser duty, and the level in
reflux vessel by distillate flow rate. As the column operates at
a large boilup ratio, the largest flow (boilup, determined by the
reboiler duty), is used for level control, while the bottoms flow rate
can be used for quality control. During dynamic simulation, it was
observed that manipulating the bottoms-to-feed ratio (0.131 at the
nominal operating point) provides faster rejection of the feed flow
Table 5
Controllers settings of the plantwide control structure for the system with one recycle.

Controllers Process value (PV) Controller output (OP) KC Ti

Value Range Value Range %/% min

MIX & COND-2

X Fresh AA flow rate/kg/h Liquid outlet flow rate/kg/h – –
(F1 /FAA,0 ) F1 = 12.81 × FAA,0
PC Pressure/bar Flow rate/m3 /h 2 12
1.5 1.4. . .1.6 634.7 0 . . . 1269.4
LC Level/m Flow rate/kg/h 10 60
2.7 0. . .5.33 1477.7 0 . . . 1955.4
TC Temperature/◦ C Duty/GJ/h 1 20
94.5 90. . .100 −1.5380 −3.1 . . . 0
PFR & HX
TC Temperature (inlet PFR)/◦ C Duty/GJ/h 1 20
85 60. . .120 −2.4236 −4.9 . . . 0

M.D. Moraru, C.S. Bildea / Journal of Process Control 58 (2017) 46–62

C-1 & COND-1
PC Pressure (tray 1)/bar Flow rate/m3 /h 2 12
1.22 1.1. . .1.3 983.8 0 . . . 1967.6
TC Temperature (tray 11)/◦ C Duty/GJ/h 1 20
125.1 115. . .135 4.5228 0. . .9.1
LC Level/m Flow rate/kg/h 1 60
1.35 0. . .2.7 19485 0 . . . 38970
TC Temperature (condenser)/◦ C Duty/GJ/h 1 20
33.2 28. . .38 −1.9989 −4 . . . 0

C-2 & COOL-2 (including AA concentration sensor and concentration controller)

PC Pressure (condenser)/bar Condenser Duty/GJ/h 2 12
4 3.8. . .4.2 −20.448 −41.2 . . . 0
TC Temperature (tray 1)/◦ C Reflux Ratio/- 1 20
187.5 177. . .197 1.99 0. . .4
I Input = 5.0 × 10-3 Output = 5.0 – –
AA mass fraction/kg/kg AA transf. mass frac./kg/kg
Settings:
Sensor Gain = 1000; Sample interval = 15 min; Dead time = 15 min
XC AA/kg/kg Bottoms to Feed ratio/- 5.62 99
5.0 0. . .10 0.131 0. . .0.2621
X Feed flow rate/kg/h Bottoms flow rate/kg/h – –
(FBottoms /FFeed ) FBottoms = 0.131 × FFeed
LC Level (reflux drum)/m Flow rate/kg/h 1 60
2.725 0. . .5.45 16931 0. . .33864
LC Level (sump)/m Reboiler Duty/GJ/h 1 60
1 0. . .2 22.9 0 . . . 46.1
TC Temperature (n-BA cooling)/◦ C Duty/GJ/h 1 20
30 25. . .35 −1.1498 −2.3 . . . 0
VL-SEP
PC Pressure/bar Flow rate/m3 /h 2 12
1.013 0.9. . .1.1 66.2 0 . . . 132.4
LC Level/m Flow rate/kg/h 1 60
0.675 0. . .1.35 365.5 0 . . . 731.0
FC Duty/GJ/h – – –
0.2009 fixed – –
LL-SEP
LC Level (organic)/m Flow rate/kg/h 1 60
0.325 0. . .0.65 996 0 . . . 2003
LC Level (aqueous)/m Flow rate/kg/h 1 60
0.121 0. . .0.65 419.2 0 . . . 838.4

55
56 M.D. Moraru, C.S. Bildea / Journal of Process Control 58 (2017) 46–62
rate disturbances. Therefore, the control shown in Fig. 9 proved to
be the most suitable among several alternatives investigated.
To maintain the product purity, a concentration controller that
manipulates the bottoms to feed mass ratio is implemented. 15 min
sampling time and 15 min deadtime arising due to concentration
measurement are taken into account. The concentration controller
has a set-point of 0.5%wt AA so that the n-BA product purity can
be reached (99.5% n-BA by weight); the controller output is the
set-point to the bottoms to feed ratio controller. The action of
the concentration controller is reverse: when the AA concentra-
tion increases, the bottoms to feed ratio is decreased. This leads
to an increase in the sump level which forces the reboiler duty
to increase. Thus, the bottoms temperature increases, more AA is
vaporised, and purer product is obtained.
This is a key controller in maintaining the product at the required
specification. This PI controller is tuned using the closed loop Auto
Tune Variation (ATV) method implemented in Aspen Plus Dynam-
ics. With all the other control loops closed, the ATV method finds the
stability limit using a relay of amplitude 5% of the controller output
range (bottoms to feed ratio). The ultimate gain and ultimate period
are 12.4%/% and 118.8 min, respectively. Using the Ziegler-Nichols
tuning rules, the calculated gain and integral time are 5.62%/% and
99 min, respectively.
The gain and integral time of all controllers are shown in Table 5.
All pressure, temperature and level loops use PI control. The large
reset time of the level controllers brings them close to the common
practice of P-only action.
The performance of the control structure is assessed by intro-
ducing four disturbances, after two hours of steady state run: ±25%
for FAA,0 and ±10 ◦ C for temperature at the reactor inlet. The flow
rate perturbation is introduced as a ramp, time for four hours, while
the temperature perturbation is introduced in a step change, once.
Fig. 10 presents the results of the dynamic simulation. The dia-
grams in the left-hand side (lhs) column show selected flow rates,
in the middle column the product purity, while in the right-hand
side (rhs) column the by-product (water) purity.
The three diagrams in row-1 (top) present the results for
increase of FAA,0 , from 20 to 25 kmol/h (+25%). For this partic-
ular control structure, this action increases the production rate
by 25%. Counting from the start of ramping of the fresh AA, it
takes about 13 h for the production to reach 25 kmol/h. The same
holds for the settling time of all the other stream flow rates:
water product, recycle (water/n-BuOH and n-BuOH/AA) and fresh
n-BuOH (lhs diagram). The transition to the new operating point
is smooth, although the fresh n-BuOH shows some fluctuations
as it tries to cope with the change in fresh AA flow rate. Dur-
ing this time, the product purity (middle diagram) is practically
unaffected, remaining at 99.5 wt%. The water purity drops slightly
(from 97.7 to 96.9 wt%, rhs diagram). Similar behaviour (row-2 dia-
grams) is observed when decreasing the fresh AA from 20 to 15
kmol/h (−25%). The production decreases by 25%, product purity
is not affected (staying at 99.5 wt%), while water purity is slightly
increased (from 97.7 to 98.4 wt%).
When changing the reactor inlet temperature with ±10 ◦ C,
the dynamic behaviour (row-3 and row-4 diagrams) is even less
impacted. Both, the product and water purities remain practically
unchanged, with the observation that water purity shows, imme-
diately after the perturbation, a slight fluctuation.
5.3. Two-recycle system
Fig. 11 shows the plantwide control structure for the system
with two recycles. At the plant level, the control structure fixes
reactor-inlet flow rate of AA (F1A ) and the ratio between F1B (mainly
n-BuOH) and F1A (mainly AA) at the reactor inlet. The reactor is set to
operate at a fixed F1B to F1A mass ratio of 2.74. Both fresh reactants,
n-BuOH and AA, are added on level control of MIX-1 and MIX-2,
as the stoichiometry requires. Note that buffer vessels MIX-1 and
MIX-2 are not essential, as the reactants can also be added as make-
up streams, at appropriate locations which offer a fair image of the
component inventory: the reflux drum of the C-2 column (n-BuOH)
and the reflux drum of the C-4 column (AA).
Again, almost standard control applies at the unit level. The reac-
tor, C-1, LL-SEP and VL-SEP have the same control structures as the
system with one recycle. The column making the split between AA
(bottoms) and AA plus n-BuOH (top), C-3, has the following con-
trol structure: a first ratio controller fixes the solvent to feed flow
mass ratio, while a second one fixes the ratio between reboiler duty
and feed flow rate; the sump level is controlled by the bottoms flow
rate, top pressure by condenser duty and the level in the reflux ves-
sel by the distillate flow rate; temperature at the top of the column
is controlled by manipulating the reflux ratio. The solvent recov-
ery column C-4 has standard control: sump level by bottoms flow
rate, bottoms temperature by reboiler duty, top pressure by con-
denser duty, level in reflux drum by distillate flow rate, and top
temperature by reflux ratio. In practice, the buffer vessel MIX-3
can be operated without level control. This is possible because the
EG make-up rate is almost zero, fresh EG being charged only when
the MIX-3 level falls significantly (say once every six months). Stan-
dard control applies to the n-BA column C-2 as well: fixed reflux
ratio, pressure maintained by condenser duty, the level in reflux
vessel by distillate flow rate, sump level by bottoms flow rate and
bottom temperature by reboiler duty.
Two concentration controllers are implemented to maintain the
product purity: one for AA and another for controlling the n-BuOH
concentration. The first controller output is the set-point of the
top temperature controller of the extractive distillation column
C-3. The output of the second controller represents the set-point
of the bottom temperature controller of C-2. Both controllers are
implemented in a similar way as for the system with one recycle.
An analyser measures the concentration of AA and n-BuOH each
15 min and after another 15 min dead time it sends a signal to
the corresponding concentration controller. The controllers’ out-
puts are the set-points of the temperature controllers. The action of
the AA controller is reverse: when the AA concentration increases,
the temperature set-point needs to decrease, so that less AA leaves
with the distillate of C-3. The action of the n-BuOH controller is
direct: when n-BuOH concentration increases, reboiler duty needs
to increase, so that more n-BuOH is vaporized from the sump of
C-2.
The concentration controllers are PI controllers and are tuned
using the closed loop ATV method. Based on a relay amplitude of 5%
of the output range (temperature), the ultimate gain and ultimate
period are 0.3%/% and 225 min, for the AA controller, and 1.07%/%
and 60 min, for the n-BuOH controller. Using the Ziegler-Nichols
tuning rules, the calculated gain and integral time are 0.134%/% and
187.5 min, for AA controller, and 0.48%/% and 50 min, for n-BuOH
controller. The gain and integral time of all the other controllers are
showed in Table 6.
Again, four perturbations are introduced to assess the per-
formance of the control structure: ±25% for F1A and ±10 ◦ C for
temperature at the reactor inlet. The perturbations are introduced
in the same manner as for the first process alternative. The same
holds for the arrangement of diagrams in Fig. 12, in which the
dynamic simulation results are presented.
The three diagrams in row-1 present the results for increase of
F1A , from 2853 to 3566 kg/h (+25%). This action increases the pro-
duction by roughly 15.6%. Counting from the start of ramping of
F1A , it takes between 15–20 h for the plant to reach the new pro-
duction rate. The same holds for the settling time of all the other
streams: water product, recycles and fresh n-BuOH streams (lhs
diagram). During transition to the new operating point, a slight
Table 6
Controllers settings of the plantwide control structure for the system with two recycles.

Controllers Process value (PV) Controller output (OP) KC Ti

Value Range Value Range %/% min

MIX-1 & MIX-2

X Fresh + Recycle AA flow rate/kg/h Fresh + Recycle n-BuOH flow rate/kg/h – –
(F1B /F1A ) F1B = 2.739 × F1A
LC Level (n-BuOH recycle vessel)/m Flow rate/kg/h 10 60
1.24 0. . .2.48 1542.2 0 . . . 3084.4
LC Level (AA recycle vessel)/m Flow rate/kg/h 10 60
0.83 0. . .1.65 1489.9 0 . . . 2979.8
PFR & HX
TC Temperature (inlet PFR)/◦ C Duty/GJ/h 1 20
85 60. . .120 −0.3750 −2 . . . 2
C-1 & COND-1

M.D. Moraru, C.S. Bildea / Journal of Process Control 58 (2017) 46–62

PC Pressure (tray 1)/bar Flow rate/m3 /h 2 12
1.2 1.1. . .1.3 1075.8 0 . . . 2151.6
TC Temperature (tray 11)/◦ C Duty/GJ/h 1 20
120.8 110. . .130 3.590 0. . .7.1
LC Level/m Flow rate/kg/h 1 60
1.13 0. . .2.25 10976 0 . . . 21993
TC Temperature (condenser)/◦ C Duty/GJ/h 1 20
30 25. . .35 −2.1656 −4.3 . . . 0
C-2 (including AA and n-BuOH concentration sensors and concentration controllers)
PC Pressure (condenser)/bar Condenser Duty/GJ/h 2 12
1.013 0.9. . .1.1 −13.08 −26.2 . . . 0
TC Temperature (tray 17)/◦ C Reboiler Duty/GJ/h 1 20
149.5 139. . .159 14.8 0. . .29.6
I Input = 2.37 × 10−3 Output = 2.37 – –
AA mass fraction/kg/kg AA transf. mass frac./kg/kg
Settings:
Sensor Gain = 1000; Sample interval = 15 min; Dead time = 15 min
XC AA/kg/kg Temperature/◦ C 0.134 186
2.37 0. . .10 66.7 57. . .77
I Input = 2.43 × 10−3 Output = 2.43 – –
n-BuOH mass fraction/kg/kg n-BuOH transf. mass frac./kg/kg
Settings:
Sensor Gain = 1000; Sample interval = 15 min; Dead time = 15 min
XC n-BuOH/kg/kg Temperature/◦ C 0.48 50
2.43 0. . .10 149.5 139. . .159

LC Level (reflux drum)/m Flow rate/kg/h 1 60

2.19 0. . .4.38 6962 0. . .14041
LC Level (sump)/m Flow rate/kg/h 1 60
1 0. . .2 2652 0 . . . 5131
TC Temperature (n-BA cooling)/◦ C Duty/GJ/h 1 20
30 25. . .35 −0.7495 −1.45 . . . 0
C-3
X Feed flow rate/kg/h Bottoms flow rate/kg/h – –
(FSolvent /FFeed ) FSolvent = 0.354 × FFeed
X Feed flow rate/kg/h Reboiler duty/GJ/h – –
(QReb /FFeed ) QReb = 1.437 × 10−3 × FFeed
PC Pressure (condenser)/bar Condenser Duty/GJ/h 2 12
0.1 0.08. . .0.12 −16.5 −33.0 . . . 0
TC Temperature (tray 1)/◦ C Reflux Ratio/- 1 20

57
 58
Table 6 (Continued)

Controllers Process value (PV) Controller output (OP) KC Ti

Value Range Value Range %/% min

66.7 55. . .77 2 0. . .4

LC Level (reflux drum)/m Flow rate/kg/h 1 60
1.925 0. . .3.85 9614 0. . .19172
LC Level (sump)/m Flow rate/kg/h 1 60

M.D. Moraru, C.S. Bildea / Journal of Process Control 58 (2017) 46–62

0.83 0. . .1.65 5251 0 . . . 10614
C-4 & COOL-3
PC Pressure (condenser)/bar Condenser Duty/GJ/h 20 12
0.1 0.08. . .0.12 −24.6 −48.7 . . . 0
TC Temperature (tray 1)/◦ C Reflux Ratio/- 1 20
81.0 71. . .91 40.1 0. . .77
TC Temperature (tray 12)/◦ C Reboiler Duty/GJ/h 1 20
152 142. . .162 24.3 0. . .48.5
LC Level (reflux drum)/m Flow rate/kg/h 1 60
2.35 0. . .4.7 1363 0. . .2822
LC Level (sump)/m Flow rate/kg/h 1 60
0.71 0. . .1.43 3888 0 . . . 7792
TC Temperature (EG cooling)/◦ C Duty/GJ/h 1 20
30 25. . .35 −1.236 −2.476 . . . 0
MIX-3
LC Level (EG recycle vessel)/m Flow rate/kmol/h 10 60
0.9 0. . .1.8 0.0083 0 . . . 0.021
VL-SEP & COND-2
PC Pressure/bar Flow rate/m3 /h 2 12
1.013 0.9. . .1.1 65.1 0 . . . 130.2
LC Level/m Flow rate/kg/h 1 60
0.675 0. . .1.35 381 0 . . . 736
TC Temperature/◦ C Duty/GJ/h 1 20
80.4 75. . .85 −0.0934 −0.193 . . . 0
FC Duty/GJ/h – – –
0.2012 fixed – –
LL-SEP
LC Level (organic)/m Flow rate/kg/h 1 60
0.325 0. . .0.65 1063 0 . . . 2102
LC Level (aqueous)/m Flow rate/kg/h 1 60
0.121 0. . .0.65 434 0 . . . 845
 M.D. Moraru, C.S. Bildea / Journal of Process Control 58 (2017) 46–62 59

Fig. 10. Dynamic simulation results for the system with one recycle; Left column: molar flow rates, Middle column: product purity, Right column: water purity; Row-1 (top):
+25% FAA,0 , Row-2: −25% FAA,0 , Row-3: +10 ◦ C reactor inlet temperature, Row-4 (bottom): −10 ◦ C reactor inlet temperature.

increase is observed in the product purity: the concentration of n-
BA (middle diagram) increases followed by a decrease back to the
initial value (97.7 wt%). This slight increase takes place in about a
time span of 10 h, from the start of the perturbation. Water purity
is also slightly affected, decreasing from 97.4 to 96.9 wt% (rhs dia-
gram). When decreasing F1A , from 2853 to 2139 kg/h (−25%), the
production decreases by 18.2%. One can observe (row-2 diagrams)
the same fluctuation behaviour: settling time, change in product or
water purities, as in the case of increasing the F1A flow rate. This is a
mirror-like behaviour, and to some extent, the fluctuations ampli-
tude is smaller. While the product purity returns to 99.5 wt%, the
water purity increases from 97.4 to 98.0 wt%.
Increasing the reactor inlet temperature by 10 ◦ C, the produc-
tion rate increases by 19.3% (row-3, lhs diagram), while a decrease
by 10 ◦ C, leads to a decrease in production by 18.4% (row-4, lhs dia-
gram). In both cases, the product purity shows initially some slight
fluctuations, finally settling out to the set-point value (99.4 wt%).
The water purity presents slight changes: at increase in temper-
ature, the purity decreases from 97.4 to 96.8 wt; at decrease in
temperature, the purity increases from 97.4 to 98.0 wt%.
The settling time is larger compared to the one-recycle plant,
which can be explained by the longer response times and greater
sensitivity induced by recycles [23,24]. In addition, but to a less
extent, the plant behaviour also depends on the dynamics of the
units in the recycle loop [24]. Since the extractive distillation
section (C-3, C-4, MIX-3) is part of the second recycle, it also con-
tributes to the overall dynamics.
60 M.D. Moraru, C.S. Bildea / Journal of Process Control 58 (2017) 46–62
Fig. 11. Process flow diagram and plantwide control of the system with two recycles.
6. Conclusions
Large scale production of n-butyl acrylate based on solid catal-
ysis is feasible. Two conventional processes are presented, each
designed for a production capacity of 20,500 t/a.
The integration between conceptual design and plantwide con-
trol, and the use of the sensitivity analysis allows the selection of
a robust operating point based on which the reactor is designed.
Both processes employ a fixed-bed reactor, while the particularly
difficult split between acrylic acid and n-butyl acrylate is achieved
by using conventional distillation, or conveniently by extractive
distillation using ethylene glycol.
The sensitivity analysis provides in the same time feasible
plantwide control structures. Coupled with the control at the unit
level, the dynamic simulations show that these structures are able
to keep the mass inventory in the plant and achieve the required
product purity when changes in throughput and reactor inlet tem-
perature are made.
In the first system, the capacity is set by the fresh flow rate
of acrylic acid, while in the second it can be set in two ways:
(1) by changing the flow rate of (recycle + fresh) acrylic acid at
the reactor inlet, while the (recycle + fresh) n-butanol flow rate
is accordingly adjusted by the ratio controller, and (2) by chang-
ing the temperature at the reactor inlet. Thus, the advantage of
the first control structure is its capability to set the capacity in a
direct manner, while the second structure can only set the capac-
ity indirectly. However, having multiple possibilities to change the
capacity can also be seen as an advantage. In this case, both ways
to change the capacity are achieved in an efficient manner: at
±25% change of (recycle + fresh) acrylic acid, the production capac-
ity modifies by +15.6%/−18.2%, while ±10 ◦ C modifies the capacity
by +19.3%/−18.4%. Other advantages are the capability of process-
ing larger fresh feeds of acrylic acid, and that only one steady state
is present.
A rough comparison of the two processes shows that employing
extractive distillation is to some extent better, overcoming impor-
tant drawbacks of the other process: the distillation columns are
smaller, less n-butyl acrylate is recycled, and the risk of polymer-
ization is lower due to lower temperatures.
 M.D. Moraru, C.S. Bildea / Journal of Process Control 58 (2017) 46–62 61

Fig. 12. Dynamic simulation results for the system with two recycles; Left column: molar flow rates, Middle column: product purity, Right column: water purity; Row-1
(top): +25% F1A , Row-2: −25% F1A , Row-3: +10 ◦ C reactor inlet temperature, Row-4 (bottom): −10 ◦ C reactor inlet temperature.

Acknowledgments
C.S. Bildea gratefully acknowledges the financial support of
the European Commission through the European Regional Devel-
opment Fund and of the Romanian state budget, under the
grant agreement 155/25.11.2016 (Project POC P-37-449, acronym
ASPiRE).
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