processes

Article
Optimization and Control of Propylene Production by
Metathesis of 2-Butene
Andrei Maxim Andrei and Costin Sorin Bildea *

Department of Chemical and Biochemical Engineering, University Politehnica of Bucharest, str. Gh. Polizu 1-7,
011061 Bucharest, Romania; [email protected]
* Correspondence: [email protected]; Tel.: +40-21-402-3903

Abstract: This article considers the design and control of the 2-butene metathesis process. The process
transforms a low-value feedstock derived from a fluid catalytic cracking unit into more valuable
products. The economical optimization is applied to the preheat–reaction and separation sections,
with the objective of minimizing the total annual cost. The dynamic response and control of the
plant are evaluated for feed flow perturbations. Although the process control system acts as a first
line of defense against potential hazards, other independent safety layers are discussed with safety
limits specific to the critical equipment of the 2-butene metathesis unit. The results prove that the
metathesis reaction of 2-butene over a mesoporous tungsten catalyst is economically attractive. For a
5.7 t/h feed rate consisting of 2-butene (70% molar) and n-butane (30% molar), a reaction–separation
plant (without recycle) requires 6570 × 103 $ investment and has a profitability of 2300 × 103 $/year.

Keywords: olefin metathesis; propylene production; process design; process control; flowsheeting;
dynamic simulation; safety

1. Introduction
Propylene is mainly supplied by naphtha steam crackers and fluid catalytic cracking
units. Relatively small amounts are obtained from other olefin processes, which is the reason
for the increasing interest in alternative technologies, such as propane dehydrogenation [1],
Citation: Andrei, A.M.; Bildea, C.S. olefin metathesis, the conversion of methanol to propylene, and the cracking of low-value
Optimization and Control of olefins. Studies of 1-butene self-metathesis over a molybdenum catalyst supported on
Propylene Production by Metathesis modified silica reported high yields of propylene and ethylene [2]. Investigations were
of 2-Butene. Processes 2023, 11, 1325. conducted for olefin metathesis using various supported metal oxides, both industrial-type
https://doi.org/10.3390/pr11051325 and organometallic complexes [3–5]. Olefin metathesis is applied in industrial processes
Academic Editors: Máté Petrik, Gábor such as the Shell Higher Olefin Process (SHOP) and Philips triolefin process [6].
L. Szepesi and Zoltán Szamosi The fluid catalytic cracking unit (FCCU) is a versatile and complex unit. After the
cracking process is performed, the products are separated in a train of distillation columns
Received: 30 March 2023 according to their boiling points. The C4 fraction is separated into a light fraction (denoted
Revised: 13 April 2023
as iBB), comprising of isobutene and isobutane, and a heavy fraction (denoted as nBB),
Accepted: 20 April 2023
which contains mainly 2-butene (about 70%) and n-butane (30%). The latter is a low-value
Published: 25 April 2023
by-product, typically routed to the LPG pool for blending with other components. However,
2-butene can be processed as a reactant in isomerization–metathesis reactions, leading to
more cost-attractive olefins, such as ethylene, propylene, and higher olefins.
Copyright: © 2023 by the authors.
This work considers the design and control of an olefin metathesis process, in which
Licensee MDPI, Basel, Switzerland. 2-butene is upgraded to more cost-attractive products, such as propylene. The basis of
This article is an open access article the design related to feed characterization, stoichiometry, reaction kinetics, and thermody-
distributed under the terms and namics is considered. On this ground, several process flowsheets of 2-butene metathesis
conditions of the Creative Commons for propylene production, with or without recycling, were assessed using a hierarchical
Attribution (CC BY) license (https:// approach [7]. In the present work, the design of the main flowsheet equipment is based
creativecommons.org/licenses/by/ on engineering guidelines and best practices. Economic optimization is carried out con-
4.0/). sidering the total annual cost (TAC) as the objective function. Firstly, the reaction section

Processes 2023, 11, 1325. https://doi.org/10.3390/pr11051325 https://www.mdpi.com/journal/processes

Processes 2023, 11, 1325 2 of 15

(feed-effluent heat exchanger, furnace, and reactor) is considered. The optimization aims
to find the optimal amount of heat to be saved by a process–process exchange. Secondly,
the separation section, consisting of a series of four distillation columns, is considered.
The decision variables are column pressure, the number of trays, and feed location. The
dynamic control of the 2-butene metathesis plant is studied in Aspen Dynamic, with the
response of the process with respect to feed-rate disturbances being evaluated. The safety
analysis of critical equipment is discussed to highlight the importance of independent
protection layers for preventing hazards or undesirable incidents.

2. Basis of Design
In the presence of a tungsten oxide catalyst, the metathesis reaction can be carried
out, converting butenes to valuable olefin products, ranging from C2 to C6, predominantly
propylene [8]. The design of the industrial process follows a hierarchical methodology [7,9].
Reaction chemistry, kinetics, and thermodynamic properties of the species involved are
the basis of the design. After flowsheet development, computer simulation using the
commercial software Aspen Plus v.10 is used for sizing the main units, optimizing the plant,
and performing control studies.

2.1. Chemistry
Reference [8] presents the chemistry of the process. Isomerization (1), cross-metathesis
(2), and self-metathesis (3) are the main reactions, which are considered to be reversible.
Additionally, cracking (4) occurs. For the purpose of process simulation, pentene and
hexene isomers are lumped as 2-pentene and 3-hexene, respectively. The production
of paraffins, isobutene, and aromatic products is negligible. Secondary metathesis and
oligomerization reactions are not considered.

2-Butene (A)  1-Butene (B) (1)

2-Butene (A) + 1-Butene (B)  Propylene (C) + 2-Pentene (D) (2)

1-Butene (B) + 1-Butene (B)  Ethylene (E) + 3-Hexene (F) (3)

2-Butene (A) → Ethylene (E) + 2 Propylene (C) (4)

2.2. Thermodynamics
The physical properties of all species are accessible in the Aspen Plus pure component
database. Such properties are boiling points, enthalpies of formation, ideal gas heat capac-
ities, Antoine parameters, molar density, etc. In this case, as non-polar chemical species
are involved in the process, the behavior of the liquid phase is assumed ideal. One key
element in designing the separation section for multiple components is the temperature
dependence of vapor pressures since this determines the operating pressure and, ultimately,
the choice of the cooling agent. Thus, at 50 ◦ C, the relative volatilities with respect to
n-butane are 0.12 (2-hexene), 0.32 (2-pentene), 0.9 (2-butene), 1.2 (1-butene), 4.12 (propy-
lene), and 21.65 (ethylene). The separation seems to be rather easy, except for the split of
the 1-butene/n-butane/2-butene mixture. Consequently, high pressure is required for the
separation of light gases (ethylene and propylene) through distillations to allow the use
of cooling water or sometimes refrigerant in the condensers. Thus, the Peng–Robinson
equation of state is used to model the non-ideality of the vapor phase.
The isomerization and self-metathesis reactions are slightly endothermal, while the
cross-metathesis is slightly exothermal. The chemical equilibrium is weakly dependent on
temperature. At 500 ◦ C, the equilibrium constants (Keq,i i = 1 . . . 3) are 3.17, 5.29, and 5.48,
respectively. The cracking reaction is endothermal.
Processes 2023, 11, 1325 3 of 15

2.3. Kinetics
The reaction rates can be described by power-law expressions. The kinetic parameters
(Table 1) were previously determined [10] by fitting the experimental data from the 2-butene
metathesis [8] to the model of an isothermal plug-flow reactor.

1
r1 = k1 ·(C A − CB ) (5)
Keq,1

1
r2 = k2 ·(C A ·CB − C · CD ) (6)
Keq,2 C

1
r3 = k2 ·(CB2 − CE · C F ) (7)
Keq,3

r4 = k4 ·C2A (8)

 
Ea,i  1 1
k i = k i ( T0 ) exp − − (9)
R T T0
Bi
ln Keq,i = Ai + (10)
T

Table 1. Parameters of the kinetic model.

Pre-Exponential Factor Activation Energy

Reaction Ai Bi (K)
k(T 0 ) (m3 /kmol/s) Ea (kJ/kmol)
1 0.0287 25.12821 4.662791 −1154.68
2 6.802 102.0203 5.480296 −144.335
3 3.815 187.0776 9.544931 −3139.28
4 0.123 84.56967 20.7 0

2.4. Process Design

2.4.1. Flowsheet Alternatives and Preliminary Mass Balance
The price of the nBB feed is assumed to be 388.8 $/tonne. Among the products,
propylene has the highest price (648 $/tonne), followed by ethylene (540 $/tonne) and
higher olefins (pentene, hexene—486 $/tonne). The isomerization of 2-butene to 1-butene
does not bring any benefit, as the resulting C4 mix (388 $/tonne) is also used in the LPG
pool. However, the separation of n-butane (452 $/tonne) to be used as raw material in
alkylation or dehydrogenation processes can be beneficial.
The input–output analysis revealed that the olefin metathesis process can be profitable
for a production capacity of 5.7 t/h. Thus, 1 tonne of raw material costs 388.8 $ and contains
700 kg of 2-butene and 300 kg of n-butane. In an ideal process, the entire amount of 2-butene
is converted to propylene, giving 700 kg × 0.648 $/kg = 453.6 $. The high-purity n-butane
gives 300 kg × 0.452 $/kg = 135.6 $. The economic potential can be 9175 × 103 $/year, or
about 52% of the raw material costs. Note that these calculations assume the ideal case
of 100% 2-butene conversion and 100% selectivity toward the most expensive product
(propylene). Moreover, investment and operating costs are not taken into account.
Andrei and Bildea [10] evaluated several process alternatives. By performing sensitiv-
ity studies, they showed that the most profitable alternative consists of a reaction section
followed by product separation, without reactant recycling. This happens because of the
close boiling points of butenes and n-butane, which make their separation very costly.
In the present article, we present the optimization of the reaction–separation plant for
the metathesis of 2-butene. Figure 1 shows the dependence of the economic potential EP
versus the 2-butene conversion, calculated at different levels of detail. Thus, EP1 takes into
account only the difference between product sales revenue and raw material cost. EP2a
Processes 2023, 11, x FOR PEER REVIEW 4 of 16

Processes 2023, 11, 1325 4 of 15

versus the 2-butene conversion, calculated at different levels of detail. Thus, EP1 takes into
account only the difference between product sales revenue and raw material cost. EP2a
takes
takes into
into account
accountthe
theinvestment
investmentandandoperating
operatingcosts
costsassociated
associatedwith
withthe
thereaction.
reaction.Finally,
Finally,
EP2
EP2 incorporates the costs of separation, including the distillation columns(column
incorporates the costs of separation, including the distillation columns (columnand
and
reflux
reflux drum,
drum, condenser,
condenser, reboiler,
reboiler, internals),
internals), cooling
coolingof ofthe
thecondenser,
condenser,and
andheating
heatingofofthe
the
reboiler.
reboiler. This
This preliminary
preliminary analysis
analysisallows
allowsforforfinding
findingthetheoptimal
optimalvalue
valuefor
forconversion,
conversion,
which
which isis the
the basis
basis of
of aa preliminary
preliminary mass
mass balance.
balance.

6000

5000 EP1
Economic potential /

4000
[k$/year]

EP2a
3000
EP2
2000

1000

0
0.2 0.4 0.6 0.8 1
Conversion of 2-butene
Figure 1.
Figure Economic potential
1. Economic potential vs.
vs. conversion
conversionof
of2-butene
2-butenefor
forolefin
olefinmetathesis
metathesisunit.
unit.

In the present article, the total annual cost (TAC) is used as the objective function.
In the present article, the total annual cost (TAC) is used as the objective function.
This approach, which conveniently combines capital expenditure (CAPEX) and operating
This approach, which conveniently combines capital expenditure (CAPEX) and operating
expenditure (OPEX), has been used in many design and control studies [11–13]. These ref-
expenditure (OPEX), has been used in many design and control studies [11–13]. These
erences also present the equations that can be used to estimate the installed equipment cost
references also present the equations that can be used to estimate the installed equipment
and give values for utility prices (high-pressure steam, 9.88 $/GJ; medium-pressure steam,
cost
8.22 and
$/GJ;give values for utility
low-pressure steam,prices (high-pressure
7.78 $/GJ; electricity, steam, 9.88 cooling
16.8 $/GJ; $/GJ; medium-pressure
water, 0.72 $/GJ;
steam, 8.22 $/GJ; low-pressure
◦ steam, 7.78 $/GJ; electricity,
◦ 16.8 $/GJ; cooling
refrigerant at −20 C, 7.89 $/GJ, refrigerant at −50 C, 13.11 $/GJ). The restrictions water,of0.72
the
$/GJ; refrigerant at −20 °C, 7.89 $/GJ, refrigerant at −50 °C, 13.11 $/GJ). The restrictions
optimization problem are represented by the mass and energy balance of the plant, together of
the
withoptimization problem
the equilibrium are represented
and kinetic conditions,byasthe mass and energy
implemented balancePlus
in the Aspen of the plant,of
models
together with the equilibrium and kinetic conditions, as implemented
the unit operation. The decision variables are described in the next sections. in the Aspen Plus
models of the unit operation. The decision variables are described in the next sections.
2.4.2. Reaction Section
2.4.2.The
Reaction Section
reaction takes place in a fixed-bed, vapor-phase tubular reactor, which is operated
The reaction
adiabatically. takes
This typeplace in a fixed-bed,
of reactor was chosenvapor-phase
because tubular reactor,
it is suitable forwhich is oper-
housing large
ated
amounts of catalyst and it is easy to operate. The reactor diameter was determinedlarge
adiabatically. This type of reactor was chosen because it is suitable for housing for a
amounts of catalyst
pressure drop of 0.01and it is (the
bar/m easytypical
to operate.
valueThe reactor diameter
for single-phase was determined
fixed-bed for a
catalytic reactors)
pressure drop of 0.01 bar/m
and the corresponding (the typicalarea.
cross-sectional valueAfor single-phase
simulation of thefixed-bed
chemicalcatalytic
reactor, reactors)
using the
and
RPLUGthe Aspen
corresponding cross-sectional
Plus model, (Bedford, MA area. A simulation
01730, USA) allowedof theforchemical
the findingreactor,
of the using
length
the RPLUGtoAspen
necessary achieve Plus
themodel,
required (Bedford, MA 01730, USA) allowed for the finding of the
conversion.
length necessary to achieve the required conversion.
2.4.3. Separation Section
2.4.3.The
Separation
columnsSection
were sized using the DSTWU shortcut distillation model from Aspen Plus.
The recoveries
The columnsof the lightsized
were and heavy
using key
the components
DSTWU shortcutwere specified,
distillationtogether
modelwithfromthe reflux
Aspen
ratio being
Plus. 1.2 times of
The recoveries thethe
minimum
light and value.
heavy The
keyDSTWU modelwere
components determined thetogether
specified, data required
with
by the
the RADFRAC
reflux rigorous
ratio being model
1.2 times the(the numbervalue.
minimum of trays NT,DSTWU
The reflux ratio
modelR, feed tray location
determined the
data required by the RADFRAC rigorous model (the number of trays NT, refluxused.
NF, distillate-to-feed ratio D:F). For all columns, two design specifications were ratioThe
R,
mole fraction of the heavy key component in the distillate was set to 0.1 mole%. The ratio
between the light and the sum of light and heavy key components in the bottom was set to a
target of 0.5 mole%. This ensured that, in the subsequent distillation column, it was possible
Processes 2023, 11, 1325 5 of 15

to obtain the distillate with high purity. The variables adjusted to reach the specifications were
the reflux and the distillate-to-feed ratios, R and D:F, respectively. Then, the location of the
feed stage NF was changed in order to find the value leading to minimum reboiler duty, and
the total annual cost TAC was evaluated. The procedure was repeated for a different number
of stages NT until a minimum value of the TAC was obtained.
Column height was determined considering the number of actual stages calculated
with the typical value of tray spacing 0.6 m and allowing for the equivalent of four trays
of vapor disengaging at the top of the column and a residence time in the bottom of the
column equivalent to three trays. The column diameter was determined using the tray
sizing facility available in Aspen Plus. The vessels were sized based on a residence time
to allow sufficient time to reject process perturbation and to ensure enough net positive
suction head for the reflux pump.
The operating pressure for distillation columns was selected to allow the use of cooling
water in the condenser (except for the first column, where refrigerant is used). Two levels of
steam were used as a heating agent in the reboilers, super-heated medium-pressure steam
(MPS) at 12 barg and 220 ◦ C and low-pressure steam (LPS) at 3 barg and 140 ◦ C, respectively.

2.4.4. Heat Exchangers

The heat exchangers were sized considering a minimum temperature approach of
15 ◦ C for the shell and tube exchangers and a typical value of 200 W/m2 /K for the overall
heat transfer coefficient. The log mean temperature difference was calculated from the
energy balance and, hence, the heat transfer area.

2.4.5. Process Control

The dynamics and control of the plant were assessed using Aspen Dynamics v.10 flow-
driven dynamic simulation. Some basic controllers were automatically added by the Aspen
software. The control structure follows standard industry practice and is described in the Re-
sults section. The flow, temperature, pressure, and composition controllers were conventional
PI-type. The level controllers (reflux drums, the sumps of the columns, and feed vessels) were
P-type. For most controllers, the gain was set to 1 (%OP range/% PV range), and the integral
time was chosen as an estimation of the loop time constant [7]. Composition controllers were
tuned by running a relay-feedback test with the Tyreus–Luyben tuning rule.

3. Results and Discussion

3.1. Process Description
The olefin metathesis unit is a reactor-separation flowsheet consisting of preheat,
heating, reaction, and separation sections (Figure 2). The low-value product nBB of the
fluid catalytic cracking unit (FCCU) is pumped to the olefin metathesis unit from feed
surge drum V-1. The feed consists of a mixture of 2-butene (70 mol%) as the reactant and
n-butane (30 mol%) acting as inert. The feed surge drum (V-1) is sized to ensure sufficient
holdup volume in case of an inadvertent pump trip and is operated at 8 bar(g) to ensure the
feed mixture is kept in a liquid state. The fresh feed is routed to the feed-effluent exchanger
(FEHE) and then to the furnace (H-1). The reaction section consists of an adiabatic tubular
reactor operating at P = 1 bar and inlet temperature T = 550 ◦ C with a tungsten oxide
catalyst supported on silica. The reaction is conducted in the vapor phase and is slightly
endothermic. The reactor effluent passes through the feed-effluent exchanger (FEHE)
and is cooled in the air cooler (AC-1) and water cooler (HE-1) to ensure an acceptable
temperature at the inlet of the compressor (K-1), typically below 50 ◦ C. Prior to entering
the separation section, the pressure of the reactor effluent is increased by the compressor
(K-1). Moreover, heat can be recovered by using the hot, compressed stream S6/1 as a
heat source in one distillation column reboiler (HE-10). The distillation section consists
of four distillation columns separating ethylene C2 (99 mol%), propylene C3 (99 mol%),
the C4 mixture of n-butane, 1-butene, 2-butene (99 mol%), pentene C5 (99 mol%), and
hexene C6 (99 mol%). The direct sequence was chosen because it leads to the lowest energy
 (FEHE) and is cooled in the air cooler (AC-1) and water cooler (HE-1) to ensure an ac-
ceptable temperature at the inlet of the compressor (K-1), typically below 50 °C. Prior to
entering the separation section, the pressure of the reactor effluent is increased by the
compressor (K-1). Moreover, heat can be recovered by using the hot, compressed stream
S6/1 as a heat source in one distillation column reboiler (HE-10). The distillation section
Processes 2023, 11, 1325 consists of four distillation columns separating ethylene C2 (99 mol%), propylene C3 6(99 of 15
mol%), the C4 mixture of n-butane, 1-butene, 2-butene (99 mol%), pentene C5 (99 mol%),
and hexene C6 (99 mol%). The direct sequence was chosen because it leads to the lowest
energy requirements.
requirements. Moreover,Moreover, other heuristics
other heuristics [7,9]
[7,9] (such as (such as “remove
“remove first the compo-
first the component in high
nent in high amount” or “perform last the difficult separation”) do
amount” or “perform last the difficult separation”) do not apply here. not apply here.

Figure 2. Olefin metathesis of 2-butene flowsheet.

Figure 2. Olefin metathesis of 2-butene flowsheet.

Table 22 presents
Table presents the
the mass
mass balance
balanceof
ofthe
theprocess.
process.The
The2-butene
2-buteneconversion is 90.4%.
conversion is 90.4%.
The product yields are (in kg product/100 kg C4 feed) 5.94 (ethylene), 19.72 (propylene),
The product yields are (in kg product/100 kg C4 feed) 5.94 (ethylene), 19.72 (propylene),
33.5 (C4
33.5 (C4 hydrocarbons),
hydrocarbons), 26.8
26.8 (pentene),
(pentene),and
and14.0
14.0(hexene).
(hexene).

Table 2.
Table 2. Mass
Mass balance
balance for
for the
the olefin
olefin metathesis
metathesisflowsheet.
flowsheet.
Stream U.M S1 S2 S3 S4 S5 S6 S6-1 S6-2 S6-3 S7
Stream U.M S1 S2 S3 S4 S5 S6 S6-1 S6-2 S6-3 S7
Temperature °C 40 450 550 511.7 149.7 50 114 115.1 89.6 108.6
Temperature ◦ C
Pressure bar40 450
7 550
1.1 511.7
1 0.895149.7
0.845 50
0.745 114
3.5 14115.1 89.6
13.9 108.6
34
Pressure
Vapor Frac bar 7 01.1 11 0.895
1 1 0.8451 0.745
1 13.5 1 14 113.9 1 34
Vapor FracFlow
Mole 0
kmol/h 100 1 1001 1001 102.5 1102.5 1
102.5 1
102.5 97.8 1 97.81 1.341
MoleMass
FlowFlowkmol/h kg/h100 100
5671 100
5671 102.5 5671 102.5
5671 5671 102.5
5671 102.5
5671 97.8
5346 97.8
5346 1.34
53.2
Mass Flow kg/h 5671 5671 5671 5671 5671 5671 5671 5346 5346 53.2
Mole Fraction
Mole Fraction
2-Butene 0.7 0.7 0.7 0.065 0.065 0.065 0.065 0.065 0.065 0.026
2-Butene 0.7 0.7 0.7 0.065 0.065 0.065 0.065 0.065 0.065 0.026
1-Butene 0.042 0.021 0.021 0.021 0.042 0.042 0.021
1-Butene 0.042 0.021 0.021 0.021 0.042 0.042 0.021
Propylene
Propylene 0.242 0.2420.259
0.259 0.259
0.259 0.259
0.259 0.2420.242 0.242
0.242 0.259
0.259
2-Pentene
2-Pentene 0.191 0.191 0.209
0.209 0.209
0.209 0.209
0.209 0.1910.191 0.191
0.191 0.209
0.209
Ethylene
Ethylene 0.1 0.1 0.117
0.117 0.117
0.117 0.117
0.117 0.1 0.1 0.10.1 0.117
0.117
3-Hexene
3-Hexene 0.07 0.07 0.092
0.092 0.092
0.092 0.092
0.092 0.070.07 0.07
0.07 0.092
0.092
n-Butane
n-Butane 0.3 0.3
0.3 0.3
0.3 0.3
0.29 0.29 0.29 0.29 0.29
0.29 0.29
0.29 0.290.29 0.29
0.29 0.133
0.133
Stream
Stream U.M U.M S8 S8
S9 S9
S10 S10 S11 S11 S12
S12 S13
S13 S14S14 S15S15 S16S16
Temperature ◦ °C 55 −15 140 40 154 40 112.7 40 40
Temperature
Pressure C bar55 −15
32.9 140
32 34.2 40 25.5 154
25.5 6.540 7.5112.7 2.540 3.540
Pressure bar 32.9 32 34.2 25.5 25.5 6.5 7.5 2.5 3.5
Vapor Frac 0 0 0 0 0 0 0 0 0
Vapor Frac 0 0 0 0 0 0 0 0 0
Mole Flow kmol/h 102.5 12.0 90.5 26.5 64 32.8 31.2 21.74 9.42
Mass Flow kg/h 5671 337 5334 1118.2 4215.3 1901.3 2314 1520.9 793.1
Mole Fraction
2-Butene 0.065 0.01 0.01 0.01 0.014 0.019 0.01 0.01 0.01
1-Butene 0.021 0.01 0.024 0.01 0.034 0.067 0.01 0.01 0.01
Propylene 0.259 0.01 0.294 0.99 0.01 0.01 0.01 0.01 0.01
2-Pentene 0.209 0.01 0.236 0.01 0.335 0.01 0.687 0.99 0.01
Ethylene 0.117 0.99 <0.01 0.01 0.01 0.01 0.01 0.01 0.01
3-Hexene 0.092 0.01 0.104 0.01 0.147 0.01 0.303 0.01 0.99
n-Butane 0.29 0.01 0.331 0.01 0.469 0.913 0.01 0.01 0.01
Processes 2023, 11, 1325 7 of 15

3.2. Reaction Section

The olefin metathesis takes place in the vapor phase in a fixed-bed tubular reactor.
The reactor is operated adiabatically at an atmospheric pressure of P = 1 bar. The inlet and
outlet temperatures are 550 and 512.5 ◦ C, respectively. The reactor diameter and length are
D = 3 m and L = 9 m, for a total volume of 81 m3 (34 s residence time). The reactor employs
56.7 tonnes of catalysts. The reactor sizing results are shown in Table 3.

Table 3. Reactor design results.

Reactor Tag R-1

Reactor type Adiabatic tubular reactor
Inlet temperature (◦ C) 550
Outlet temperature (◦ C) 512.5
Inlet pressure (bar) 1
Diameter (m) 3
Length (m) 9
Volume (m3 ) 81
Residence time (s) 34
Pressure drop (bar) 0.105

Figure 3 presents the results of optimizing the feed preheat section. As expected, the
operating expenditure (OPEX) decreases with the furnace inlet temperature (because more
heat is recovered). The capital expenditure (CAPEX) shows an opposite trend, as a more
expensive feed-effluent heat exchanger is required for heat recovery. It turns out that the
best solution is to preheat the fresh feed from 40 to 450 ◦ C using the heat of the reactor
effluent (512.5 to 150.9 ◦ C) in a feed-effluent heat exchanger (1511.9 kW, 179 m2 , log mean
temperature difference 84.5 ◦ C) and then to bring the mixture at the reaction temperature
Processes 2023, 11, x FOR PEER REVIEW 8 of 16
in a furnace (450 to 555 ◦ C, 488 kW). The investment and operating costs are 205 × 103 $
and 100 × 103 $ /year, respectively.

450 400
350
CAPEX
300 CAPEX, OPEX / [k$/year]
TAC / [k$/year]

400
250
OPEX
200
150
350
100
50
TAC
300 0
350 400 450 500
Inlet Furnace Temperature / [⁰C]
Figure 3.
Figure Feed preheat
3. Feed preheat section:
section: TAC,
TAC, OPEX,
OPEX, CAPEX
CAPEX versus
versus furnace
furnace inlet
inlet temperature.
temperature.

3.3. Separation Section

3.3. Separation Section
The design of the distillation columns is summarized in Table 4. The ethylene column
The design of the distillation columns is summarized in Table 4. The ethylene column
operates at 32 bar to allow the use of a refrigerant in the condenser. The operating pressures
operates
are loweratfor
32 bar to allowC4,
propylene, the and
use of a refrigerant
pentene in the
columns, condenser.
which The operating
use cooling water in pres-
their
sures are lower for propylene, C4, and pentene columns, which use cooling water in their
condensers. The total annual costs are in the range of 417–610 × 103 $/year. Note that the
optimization procedure resulted in a 220 × 103 $/year (about 9.6%) reduction of the TAC
compared to the base case design (based on the Underwood–Fenske shortcut method).
Processes 2023, 11, 1325 8 of 15

condensers. The total annual costs are in the range of 417–610 × 103 $/year. Note that the
optimization procedure resulted in a 220 × 103 $/year (about 9.6%) reduction of the TAC
compared to the base case design (based on the Underwood–Fenske shortcut method).

Table 4. Design of the distillation columns.

Processes 2023, 11, x FOR PEER REVIEW

COL-1 COL-2 COL-3 COL-4 9 of 16
Column description Ethylene column Propylene column C4-column Pentene column
Top pressure (bar) 32 17 3.9 1.15
Top temperature (◦ C) −10.7
In the distillation section, each40.8
column is equipped with 40 a pressure controller40 on the
Reflux ratio, RR condenser and 3.72 4.7 sump and reflux drums.
level controllers for the 1.34 1.13 and col-
All reflux drums
Number of stages, NTT
umn sump are30sized to provide sufficient 38
holdup when the 30 28
level is 50% full. The pressure
Feed location, NF 13 15 15 16
Reboiler duty, QR (kW) is controlled by
444.3the condenser duty. The
353.2 liquid holdups are
339.2 maintained via244.3 product
the
◦
Reboiler temperature ( C) flow rates. This
137 approach for level control
125 is best suited for
92 relatively small reflux
77 ratios
Steam type (L/D) and boil-up
MPS ratios (V/B) [14]. MPS LPS LPS
Condenser duty, Qc (kW) The first−distillation
87.8 column is−501.5
designed to separate−544.8
the ethylene from the −295.6
reactor ef-
OPEX (103 $/year) 185 140 95 60.6
fluent on the overhead. The specification of the ethylene product is kept by indirect com-
CAPEX/Payback (1000 $/year) position 421 via a temperature controller
control 440 provided on438 357
Tray 7, which manipulates the
TAC (103 $/year) 607 580 533 417.6
reflux rate. It should be noted that the location for all temperature-control trays is based
on the “sensitivity criterion”, where the largest change in temperature for a change in the
3.4. Process Control
manipulated variables (either reflux ratio or reboiler duty) is observed [15].
3.4.1.Since
Basicthere
ProcessareControl
four distillations columns in series and each distillate requires a rela-
tivelyFigure
high-purity product,
4 presents it is imperative
the plantwide to of
control prevent the lightmetathesis
the 2-butene product carryover
process. in the
After
bottom flow.
passing A cascade of
the feed-effluent composition
heat exchangercontrol
(FEHE),(XC) and temperature
the temperature of thecontrol (TC) is
feed stream atem-
the
ployed. inlet
reactor Similar to industrial
is controlled bypractice, the composition
the furnace duty. Beforecontrol loops involve
being compressed a 10sent
and mintosam-
the
separation
pling period section,
and 10the temperature
min measurement of the reactor-outlet
dead time, whilemixture is controlled
the temperature by the
control duty
loop is
of the heat
much exchanger HE-1.
faster.

Figure 4. Metathesis process of 2-butene—flowsheet and plantwide control.

Figure 4. Metathesis process of 2-butene—flowsheet and plantwide control.

Figure
In 5 presents section,
the distillation dynamiceach
simulation
columnresults for feed
is equipped flow
with rate disturbances.
a pressure controllerThe
on
simulation
the condenserstarts
and from
levela steady state,for
controllers which is maintained
the sump and refluxfordrums.
1 h. Then, the feed
All reflux flow and
drums rate
(FF) is increased
column sump are (left
sizeddiagrams)
to provideorsufficient
decreased (rightwhen
holdup diagrams) byis10%.
the level 50%The
full.top
Thediagrams
pressure
show
is the performance
controlled of reactor-inlet
by the condenser duty. The temperature control,
liquid holdups arewhich succeeds
maintained via in
themaintain-
product
ing the temperature at the required value. The middle row shows the feed
flow rates. This approach for level control is best suited for relatively small reflux ratios(FF—total,
F2B,in—2-butene),
(L/D) and boil-uppropylene product
ratios (V/B) [14]. (FC3), and unreacted 2-butene (F2B,out) reactor-outlet
flow rates. The bottom row shows the change in 2-butene conversion and propylene yield.
Lower/higher values of the residence times (due to a higher/lower flow rate) lead to an
increase/decrease in the conversion. Note that the product formation rate is given by the
feed rate × conversion. Among the two factors, the feed rate has the biggest influence.
Processes 2023, 11, 1325 9 of 15

The first distillation column is designed to separate the ethylene from the reactor
effluent on the overhead. The specification of the ethylene product is kept by indirect
composition control via a temperature controller provided on Tray 7, which manipulates
the reflux rate. It should be noted that the location for all temperature-control trays is based
on the “sensitivity criterion”, where the largest change in temperature for a change in the
manipulated variables (either reflux ratio or reboiler duty) is observed [15].
Since there are four distillations columns in series and each distillate requires a rel-
atively high-purity product, it is imperative to prevent the light product carryover in
the bottom flow. A cascade of composition control (XC) and temperature control (TC) is
employed. Similar to industrial practice, the composition control loops involve a 10 min
sampling period and 10 min measurement dead time, while the temperature control loop
is much faster.
Figure 5 presents dynamic simulation results for feed flow rate disturbances. The
simulation starts from a steady state, which is maintained for 1 h. Then, the feed flow rate
(FF) is increased (left diagrams) or decreased (right diagrams) by 10%. The top diagrams
show the performance of reactor-inlet temperature control, which succeeds in maintaining
the temperature at the required value. The middle row shows the feed (FF—total, F2B,in —
2-butene), propylene product (FC3 ), and unreacted 2-butene (F2B,out ) reactor-outlet flow
rates. The bottom row shows the change in 2-butene conversion and propylene yield.
Lower/higher values of the residence times (due to a higher/lower flow rate) lead to an
increase/decrease in the conversion. Note that the product formation rate is given by the
feed rate × conversion. Among the two factors, the feed rate has the biggest influence.
Thus, higher feed rates lead to more product being obtained. Note that the dynamics of the
reaction section is fast because of low inventory.
Figure 6 shows the dynamics of the ethylene column when the plant inlet flow rate
increases (solid lines) or decreases (dashed lines). The distillate (D1) purity is practically
not affected by the disturbance, but it takes several hours and a slight overshoot until the
new production rate is reached. This can be explained by the rather large inventory of
the reflux drum, which dampens the disturbances. Regarding the bottom stream (B1), the
amount of ethylene lost here is limited, and the flow change is much faster.
Figure 7 presents the performance of the propylene and C4 columns. The propylene
purity (xD2 ) is practically unchanged, but the distillate rate (D2) transient regime lasts for
several hours. The number of light olefins (ethylene and propylene, xD3 ) lost in the stream
of C4 hydrocarbons (D3) is limited.
The dynamics of pentene (D4) and hexene (B4) products are shown in Figure 8.
Similar to the other columns, the control system is able to keep the product purities
close to their setpoints while the flow rates reach a new stationary value according to the
increase/decrease in the fresh feed rate.
 Processes 2023, 11, 1325 10 of 15
Processes 2023, 11, x FOR PEER REVIEW 10 of 16

560 650 560 650

Reactor Inlet T Reactor Inlet T
550 600 550 600

Heater Duty QH / [kW]

Heater Duty QH/ [kW]
Temperature / [⁰C]

Temperature / [⁰C]
540 Heater duty, QH 550 540 550

530 500 530 500

520 450 520 Heater duty, QH 450

510 400 510 400

Reactor Outlet T Reactor Outlet T
500 350 500 350
0 1 2 3 0 1 2 3
Time / [hours] Time /[hours]
120 36 120 36

Molar Flowrate / [kmol/hr]

Molar Flowrate / [kmol/hr]

Molar Flowrate / [kmol/hr]

FF FF
Molar Flowrate / [kmol/hr]

100 FC3 100

27 27
80 80 FC3

60 F2B,in 18 60 F2B,in 18

40 F2B,out 40
9 F2B,out 9
20 20

0 0 0 0
0 1 2 3 0 1 2 3
Time / [hours] Time / [hours]
100% 40% 100% 40%

Propene Yield ηC3/2B / [%]

Propene Yield ηC3/2B / [%]

95% 95%
Conversion X2B/P / [%]

Conversion X2B/P / [%]

Conversion 38% Conversion 38%

90% 90%

85% 35% 85% Propene Yield 35%

Propene Yield
80% 80%
33% 33%
75% 75%

70% 30% 70% 30%

0 1 2 3 0 1 2 3
Time / [hours] Time / [hours]

Figure
Figure5.5. Reactor
Reactordynamic
dynamicstream
streamresults
resultsand
andperformance
performancefor
forfeed
feedflow
flowdisturbance
disturbance(solid
(solidlines
lines
indicate
indicate+10%
+10%FF,FF,and
anddashed
dashedlines
linesindicate
indicate−10%FF).
−10%FF).

Figure 6 shows the dynamics of the ethylene column when the plant inlet flow rate
increases (solid lines) or decreases (dashed lines). The distillate (D1) purity is practically
not affected by the disturbance, but it takes several hours and a slight overshoot until the
new production rate is reached. This can be explained by the rather large inventory of the
reflux drum, which dampens the disturbances. Regarding the bottom stream (B1), the
amount of ethylene lost here is limited, and the flow change is much faster.
Processes 2023, 11, x FOR PEER REVIEW 11 of 16

100.0% 20
Processes 2023, 11, 1325 18 11 of 15
Processes 2023, 11, x FOR PEER REVIEW 11 of 16
99.9% 16
xD1 / [%mol/mol]xD1 / [%mol/mol]

14

D1 / [kmol/h]
99.8% 12
100.0% 10
20
99.7% 188
99.9% 166
99.6% 144

D1 / [kmol/h]
99.8% 122
99.5% 100
99.7% 0 2 4 6 8 10 12 14 16 18 20 8 0 2 4 6 8 10 12 14 16 18 20
Time / [hours] Time / [hours]
6
99.6%
0.35% 4
140
2
130
0.30%
99.5% 0
120
xB1 / [%mass/mass]

0.25%0 2 4 6 8 10 12 14 16 18 20 1100 2 4 6 8 10 12 14 16 18 20

B1 / [kmol/h]
Time / [hours] 100 Time / [hours]
0.20%
0.35% 90
140
0.15% 80
130
0.30% 70
0.10% 120
xB1 / [%mass/mass]

0.25% 60
110

B1 / [kmol/h]
0.05% 50
100
0.20% 40
0.00% 90
0.15% 0 2 4 6 8 10 12 14 16 18 20 80 0 2 4 6 8 10 12 14 16 18 20
Time / [hours] Time / [hours]
70
0.10%
60
0.05% Figure 6. Feed disturbances for COL-1 with feed step changes (solid lines +10%; dashed line −10%).
50
40
0.00%
Figure 7 presents the performance of0the2propylene4 6 and 8 10 C4 columns.
12 14 16The 18propylene
20
0 2 4 6 8 10 12 14 16 18 20
purity
Time (xD2) is practically unchanged, but the distillate rate
/ [hours] Time / [hours]
(D2) transient regime lasts for
several hours. The number of light olefins (ethylene and propylene, xD3) lost in the stream
Figure 6.
6. Feed
Feeddisturbances
disturbancesfor COL-1
COL-1with
withfeed step changes (solid lines +10%; dashed lineline
−10%).
−10%).
Figure
of C4 hydrocarbons (D3) for
is limited. feed step changes (solid lines +10%; dashed

100.0%
Figure 7 presents the performance 50of the propylene and C4 columns. The propylene
purity (xD2) is practically unchanged, but
45 the distillate rate (D2) transient regime lasts for
40 (ethylene and propylene, xD3) lost in the stream
several hours. The number of light olefins
99.5%
xD2 / [%mol/mol]xD2 / [%mol/mol]

35
D2 / [kmol/h]

of C4 hydrocarbons (D3) is limited.

30
99.0% 25
100.0% 50
20
45
15
98.5% 40
99.5% 10
35
D2 / [kmol/h]

5
30
98.0% 0
99.0% 0 2 4 6 8 10 12 14 16 18 20 25 0 2 4 6 8 10 12 14 16 18 20
Time / [hours] 20 Time / [hours]
15
98.5%
0.65% 70
10
0.60% 5
60
98.0% 0
xD3 / [% mol/mol]xD3 / [% mol/mol]

0.55% 0 2 4 6 8 10 12 14 16 18 20 50 0 2 4 6 8 10 12 14 16 18 20
D3 / [kmol/h]

Time / [hours] Time / [hours]

0.50% 40
0.65% 70
0.45% 30
0.60% 60
0.40% 20
D3 / [kmol/h]

0.55% 50
0.35% 10
0.50% 0 2 4 6 8 10 12 14 16 18 20 40 0 2 4 6 8 10 12 14 16 18 20
0.45% Time / [hours] 30 Time / [hours]

0.40% Figure 7.
Figure 7. Feed
Feed disturbances
disturbances for
for COL-3 20 COL-4
COL-3 and
and COL-4 with
with feed step changes
feed step changes (solid
(solid lines
lines are
are +10%;
+10%;
dashed lines are −10%).
dashed lines are −10%).
0.35% 10
0 2 4 6 8 10 12 14 16 18 20 0 2 4 6 8 10 12 14 16 18 20
Time / [hours] Time / [hours]

Figure 7. Feed disturbances for COL-3 and COL-4 with feed step changes (solid lines are +10%;
dashed lines are −10%).
Processes 2023, 11, x FOR PEER REVIEW 12 of 16

The dynamics of pentene (D4) and hexene (B4) products are shown in Figure 8. Sim-
Processes 2023, 11, 1325
ilar to the other columns, the control system is able to keep the product purities close to
12 of 15
their setpoints while the flow rates reach a new stationary value according to the in-
crease/decrease in the fresh feed rate.

100.0% 35
30
99.5%
xD4 / [%mol/mol]

25

D4 / [kmol/h]
20
99.0%
15

98.5% 10
5
98.0% 0
0 2 4 6 8 10 12 14 16 18 20 0 2 4 6 8 10 12 14 16 18 20
Time / [hours] Time / [hours]
100.0% 16.0
14.0
99.0%
12.0
xB4 / [%mol/mol]

B4 / [kmol/h]
98.0% 10.0
8.0
97.0% 6.0
4.0
96.0%
2.0
95.0% 0.0
0 2 4 6 8 10 12 14 16 18 20 0 2 4 6 8 10 12 14 16 18 20
Time / [hours] Time / [hours]

Figure 8. Feed disturbancesforfor

Feed disturbances COL-4
COL-4 with
with feedfeed
stepstep changes
changes (solid(solid lines
lines are are dashed
+10%; +10%; dashed
lines arelines
−10%).
are −10%).
3.4.2. Safety Analysis
3.4.2.In
Safety Analysis
the design phase, it is necessary to investigate and include the safety aspects con-
cerning the unit as early asitpossible.
In the design phase, is necessaryOneto such safeguard
investigate andis represented
include the by the independent
safety aspects con-
protection layers (IPLs), which operate on demand (during normal or
cerning the unit as early as possible. One such safeguard is represented by the independ- abnormal events)
and protection
ent prevent or mitigate the riskwhich
layers (IPLs), of a hazard.
operateTypically,
on demand the failure of one
(during independent
normal layer
or abnormal
should not
events) andaffect
preventtheor
next safety the
mitigate barrier.
risk The
of a IPLs are Typically,
hazard. classified based on two
the failure of important
one inde-
functions:layer
pendent prevention
shouldandnot mitigation.
affect the next Several well-established
safety barrier. The IPLs methods for quantifying
are classified basedrisk
on
assessment in a plant are available in the literature. Companies have
two important functions: prevention and mitigation. Several well-established methods developed theirfor
in-
house procedures and protocols for applying these methods within their
quantifying risk assessment in a plant are available in the literature. Companies have de- risk management
systems their
veloped (e.g., in-house
LOPA, HAZOP),
procedureswhich andare discussed
protocols forin this work.
applying these methods within their
The intention of this section is to provide the
risk management systems (e.g., LOPA, HAZOP), which are discussedreader with basic guidelines pertaining
in this work.
to theThe
safety aspectsofapplied
intention for industrial
this section is to provide equipment within
the reader withthe design
basic phase, specifically,
guidelines pertaining
in this case, for the olefin metathesis plant.
to the safety aspects applied for industrial equipment within the design phase, specifi-
Process control is the first line of defense that prevents injury to personnel, protects
cally, in this case, for the olefin metathesis plant.
the environment, and ultimately prevents damage to company assets. It is followed by
Process control is the first line of defense that prevents injury to personnel, protects
a process alarm with operator intervention, an emergency shutdown system (automatic
the environment, and ultimately prevents damage to company assets. It is followed by a
valves for safety close/release of hydrocarbons), an active protection layer (safety valves or
process alarm with operator intervention, an emergency shutdown system (automatic
rupture disks), passive protection (dikes, fire extinguisher, monitors, fire and gas system),
valves for safety close/release of hydrocarbons), an active protection layer (safety valves
and, finally, the refinery emergency for evacuation.
or rupture disks), passive protection (dikes, fire extinguisher, monitors, fire and gas sys-
The alarms have the primary function of alerting the operator that a variable has
tem), and, finally, the refinery emergency for evacuation.
passed a predetermined critical limit, leading to a potentially dangerous situation. Some
The alarms have the primary function of alerting the operator that a variable has
basic principles when configuring an alarm system should be considered, such as not
passed a predetermined critical limit, leading to a potentially dangerous situation. Some
overwhelming the operator with too many notifications (leading to overstressing and
basic principles
eventually whenthe
silencing configuring
alarm) andanallowing
alarm system
enough should
time to betake
considered,
corrective such as not
measures
overwhelming
(typically 60–120 s) from when the variable passes the normal operating range (e.g., and
the operator with too many notifications (leading to overstressing low,
normal, high levels), typically referred to as an operating window or envelope. The alarm
sensor should be independent of the process control sensor, undoubtedly, if the reliability
of the sensor is expected to be a weak point. Proper operator supervision and manual
intervention, with periodical training sessions to increase the awareness of such situations
Processes 2023, 11, 1325 13 of 15

and correct comprehension of process manuals and procedures, act as decisive factors in
the development of experienced and well-trained operators in view of these possible events.
Practically, an alarm sensor can be configured for each variable of a piece of equipment,
given that there are available instruments to measure that specific variable (e.g., pressure,
flow, temperature, level). Such alarms may operate in both directions, high deviation or
low deviation, e.g., low pressure or high temperature.
In case the alarm system layer fails to prevent the propagation of the hazard, then the
next independent protection layers should be available, namely the emergency shutdown
(ESD) system.
The ESD system is represented by a well-established sequence of corrective measures
(effects) initiated by a trigger or cause (represented by a process variable deviation/limit
or operator pushbutton), which responds automatically to drive the process to a safe state
when the deviation occurs and has not been corrected by the previous protection layers.
Typical actions undertaken by an emergency shutdown system are the shutdown of certain
equipment or sections of the process, hydrocarbon inventories isolation, the stopping
of hydrocarbon flow, and, ultimately, depressurization and/or blow-down. Emergency
shutdown systems can also be classified based on the actions undertaken and company
standards. Most important is that these ESD systems have dedicated logic controllers,
sensors, and actuators, separate from process control systems, to avoid the simultaneous
failure of both protection layers. The architecture of such systems and safety functions
is widely available and well-documented in the literature; however, several examples
pertaining to the unit olefin metathesis are provided.
In case these prevention layers (process control, alarm system, and ESD) fail to propa-
gate the hazard, then the next protection layer is available, specifically, the relief system
designed to reduce or mitigate the risks of the hazard. The relief system consists in me-
chanical devices that open at a defined set pressure to protect equipment from exceeding
allowable pressure levels by means of discharging gas, liquid, or vapor to a safe and reliable
exit. The design pressure is calculated based on the maximum operating pressure of the
equipment, system, or part of the unit, plus some additional margin in order to account for
any errors in the calculation. The release can be achieved through dedicated mechanical
devices designed and manufactured for equipment under pressure, e.g., pressure safety
valves or rupture disks. These mechanical devices are positioned on pressure vessels or
pipelines. The pressure of the relief device, i.e., the safety valve, is typically set at 10%
above the normal operating pressure of the protected pressure equipment. However, other
conditions may apply depending on the specific situation. In order to determine the ca-
pacity (flow) of the relief system, several scenarios are investigated, and the worst-case
scenario is the one that returns the maximum flow of the mechanical device.
Typically, the release of hydrocarbons is collected in a flare header, represented by a
series of sub-headers and headers, directed via a knock-out drum to separate the gases
from the carryover liquid hydrocarbons, and finally, they are safely disposed of by means
of combustion into a stack with a flare tip, also referred as a flare.
In case the release of hydrocarbons is imminent, then another (passive) protection
layer is available to limit the spread of the hazard, such as a dike or fire and gas equipment
(detectors, extinguishers, etc.), that ceases or reduces the amplitude of the hazard.
The final and least desirable protection layer is the plant emergency alarm and subse-
quent evacuation of personnel with the alert of a fire-fighting team.
Specifically, for the olefin metathesis unit, only the critical equipment is studied,
e.g., reactor R-1, heater H-1, and compressor K-1, with regards to the alarm system and
emergency shutdown (ESD) system (Table 5). The relief system is very equipment-specific
and requires unit partitioning and thus is not investigated.
Processes 2023, 11, 1325 14 of 15

Table 5. Alarm and shutdown settings for 2-butene metathesis unit.

Variable Normal Operation Alarm System Trip System (ESD)

Instrument Value (NP) Instrument Value Type Instrument Trip Value Trip Group
Compressor
K-1
102.5 Flow Alarm Low
Molar flow Flow FC-001 FC-002 75% of NP FSLL-001 60 kmol/h IS-1
kmol/h (FAL)
Discharge ◦C ◦C Temperature Alarm ◦C
Temperature TI-001 115 TI-002 125 TSHH-001 135 IS-1
temperature High (TAH)
High level in
Level Alarm High
compressor Level LIC-001 600 mm LIC-002 700 mm LSHH-001 900 mm IS-1
(LAH)
K.O drum
Suction Temperature Alarm
Temperature TI-003 50 ◦ C TI-004 60 ◦ C TSHH-002 110 ◦ C IS-1
temperature High (TAH)
Heater H-1
Outlet Temperature Alarm
Temperature TI-004 550 ◦ C TI-005 560 TSHH-003 570 ◦ C IS-2
temperature High (TAH)
Fuel gas to Pressure Alarm
PDI-001 3.5 barg PDI-002 3.7 barg PSHH-01 5 barg IS-2
main burner Pressure High (PAH)
Pressure Alarm
PDI-003 2.5 barg PSLL-001 2 barg IS-2
High (PAL)
Level in fuel Level Alarm High
Level LIC-003 600 mm LIC-004 700 mm LSHH-002 900 mm IS-2
gas K.O drum (LAL)
Heater H-1
Temperature Alarm
skin Temperature TI-006 600 ◦ C TI-007 620 ◦ C TSHH-004 640 ◦ C IS-2
High (TAH)
temperature
O2 content in Analyzer Alarm
Analyzer GC AI-001 2 vol% AI-002 4 vol% ASLL-001 <0.5 vol% IS-2
furnace, H-1 Low (AAL)
Reactor R-1
Inlet Temperature Alarm
Temperature TI-008 550◦ C TI-009 570 ◦ C TSHH-005 590 ◦ C IS-3
temperature High (TAH)
DP Alarm High
Pressure drop Pressure PDI-003 0.1 bar PDI-004 0.2
(DPAH)

4. Conclusions
This article presents the economical optimization and dynamic control of a reactor
reaction-separation flowsheet of 2-butene metathesis. The once-through configuration of
reactor-separation design is determined as the most cost-effective solution. Low-value
by-product from FCCU, 2-butene, is used as raw material to produce a high-value olefin,
propylene. Two types of flowsheet designs are investigated [10], namely, with and without
recycling. The first decision levels (input–output analysis and reactor selectivity) are not
conclusive enough to select the most economical attractive flowsheet. With the optimal
conversion determined around 90%, further consideration of the investment and operation
costs related to separation equipment reveal that removing the inert from the reactants
is costly because of low relative volatility. Alternatively, recycling substantial amounts
of inert inside the plant contributes to higher capital costs and operating expenditures.
It turns out that a simple reactor–separation flowsheet (without recycling) is the most
attractive economical solution. This was a rather surprising result mostly because (for
the case considered here) the product separation leaves a by-product stream containing
reactants and the inert product, which has a rather high value and does not increase the
additional disposal costs.
In the current work, the flowsheet of reactor separation is optimized economically for two
sections of the unit: preheating and separation. For the preheating section, the decision variable
is the furnace inlet temperature, which determines the energy savings and the heat transfer
areas of the FEHE and furnace. These variables influence both the capital and operating costs.
For the separation section, comprising four distillation columns, the optimization vari-
ables are column pressure, the number of stages, feed location reflux, and distillate-to-feed
ratios. The optimization results show that approximately a 10% reduction can be achieved for
the operating and capital costs, returning a total annual cost of TAC = 2099 × 103 $/k$/year.
The dynamic response of the unit is studied for ±10% feed flow disturbance. The
control system is more than capable of bringing the unit to a new steady state in a couple
of minutes for the reactor section. The control system of the distillation columns succeeds
in keeping the product purities close to their required values at all times. However, the
Processes 2023, 11, 1325 15 of 15

dynamics of the product flow rate is slower, requiring several hours until the new steady
state is reached.
Concerning the safety analysis, the independent protection layers are discussed, with
the objective of highlighting the importance and necessity of setting independent safety
layers in the design of any industrial plant.
The results prove that the metathesis reaction of 2-butene over a mesoporous tungsten
catalyst is a viable opportunity to produce more valuable olefins (such as propylene)
from low-value feedstock (such as 2-butene). The most economical solution is a reaction–
separation plant (without recycling) with a profitability of 2300 × 103 $/year. For a 5.7 t/h
feed rate consisting of 2-butene (70% molar) and n-butane (30% molar), the investment cost
is 6570 × 103 $, giving a return of investment of ROI = 35%.

Author Contributions: Conceptualization, A.M.A. and C.S.B.; methodology, A.M.A. and C.S.B.; software,
A.M.A.; writing—original draft preparation, A.M.A.; writing—review and editing, A.M.A. and C.S.B.;
funding acquisition, C.S.B. All authors have read and agreed to the published version of the manuscript.
Funding: This research was funded by the European Commission through the European Regional
Development Fund and the Romanian state budget, Grant Agreement 155/25.11.2016 (Project POC
P-37-449, acronym ASPiRE). The APC was funded by the University Politehnica of Bucharest.
Data Availability Statement: No new data were created or analyzed in this study. Data sharing is
not applicable to this article.
Conflicts of Interest: The authors declare no conflict of interest. The funders had no role in the design
of the study; in the collection, analyses, or interpretation of data; in the writing of the manuscript; or
in the decision to publish the results.

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