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Design and Control of an Integrated 1,4-

Butanediol Dehydrogenation and Furfural
Hydrogenation Plant

Article in Chemical Engineering & Technology · September 2014

DOI: 10.1002/ceat.201400210

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 Research Article 1515

Ahtesham Javaid
Costin S. Bildea
Department of Chemical and
Biochemical Engineering,
University Politehnica of
Bucharest, Bucharest, Romania.
Design and Control of an Integrated
1,4-Butanediol Dehydrogenation and
Furfural Hydrogenation Plant
The design and plantwide control of an integrated plant, where the endothermic
dehydrogenation of 1,4-butanediol leading to g-butyrolactone and the exothermic
hydrogenation of furfural leading to furfural alcohol and 2-methyl furan are
simultaneously performed in a single reactor, is presented. Analysis of the reactor-
separation-recycle system shows that the reactions can be carried out using small
hydrogen excess, in an adiabatic reactor, with reduced parameter sensitivity. The
plant is flexible, allowing different production rates and a wide range of ratios
between the furfural alcohol and 2-methyl furan products. The additional separa-
tion of g-butyrolactone from the reaction mixture is easy. The conclusions are
supported by rigorous steady-state and dynamic simulations performed in Aspen-
Plus and AspenDynamics.

Keywords: Butanediol dehydrogenation, Design, Furfural hydrogenation, Plantwide control,

Reaction coupling
Received: April 01, 2014; revised: May 15, 2014; accepted: May 27, 2014
DOI: 10.1002/ceat.201400210

1 Introduction Eq. (2) shows the selective hydrogenation of furfural (furan-

g-Butyrolactone (dihydroxyfuran-2(3H)-one, GBL, C4H6O2),
furfural alcohol (furan-2-yl methanol, FOL, C5H6O2), and
2-methylfuran (2-MF, C5H6O) are important intermediate
chemicals. GBL is a versatile solvent and a raw material for the
synthesis of pyrrolidone, n-methylpyrrolidone, n-vinylpyrroli-
done, herbicides, and rubber additives [1]. GBL is manufac-
tured via two methods: hydrogenation of maleic anhydride and
dehydrogenative cyclization of 1,4-butanediol (1-butane-1,4-
diol, BDO, C4H10O2) performed in multitubular fixed-bed re-
actors. In particular, the dehydrogenation of BDO is dominant
in commercial applications [2]. Several research groups investi-
gated the dehydrogenative cyclization of BDO to GBL in ho-
mogeneous [3] and heterogeneous catalyst systems [4]. The
catalytic dehydrogenation of BDO to GBL shown as Eq. (1) is
an endothermic process requiring 52.05 kJ mol–1. The hydrogen
released in the reaction cannot be used effectively.
0
C4 H10 O2 fi C4 H6 O2 þ 2H2 DH523 ¼ 52:05 kJ mol1 ;
DG0298 ¼ 7:282 kJ mol1
(1)
– tion in one system has been suggested as a suitable way to solve
Correspondence: Prof. Costin Sorin Bildea (s_bildea@upb.ro), Univer-
sity Politehnica of Bucharest, Department of Chemical and Biochemi-
cal Engineering, Str. Gh. Polizu 1–7, 011061 Bucharest, Romania.
2-carbaldehyde, FAL, C5H4O2) yielding FOL, which is used in
the production of dark thermostatic resins resistant to acids,
bases, and various solvents [5].
0
C5 H4 O2 þH2 fi C5 H6 O2 DH523 ¼ 62:02 kJ mol1 ;
DG0298 ¼ 29:17 kJ mol1
(2)
2-MF is produced from catalytic hydrogenation of FAL in the
vapor phase [6], shown as Eqs. (2) and (3), releasing 169.2 kJ
mol–1 of heat. 2-MF is mainly used for the synthesis of crysan-
themate pesticides, perfume intermediates, and chloroquine
lateral chains in medical intermediates [7].
0
C5 H6 O2 þ H2 fi C5 H6 O þ H2 O DH523 ¼ 107:25 kJ mol1 ;
DG0298 ¼ 96:92 kJ mol1
(3)
Due to the strongly exothermic nature of these reactions,
temperature control of this process is very difficult, which leads
to apparent hot spots [6]. The non-uniform temperature pro-
file in the reactors lowers the yield of 2-MF [8]. In addition, a
supply of hydrogen to the system is needed.
The coupling of BDO dehydrogenation and FAL hydrogena-
the deficiencies in the individual processes, namely poor hy-
drogen utilization and difficult control of the reaction tempera-
ture [7–10]. In the new coupled process, the heat released by

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1516 Research Article

FAL hydrogenation can be used for BDO dehydrogenation, 4 Reactor Design

and H2 released by the dehydrogenation of BDO can be utilized
for the hydrogenation of FAL, with the result of much easier
temperature control, better hydrogen mass balance, and im-
proved yield of FAL hydrogenation. In practice, this combined
process can be carried out on the basis of the fact that the
hydrogen transfer from BDO (hydrogen donor) to FAL (hydro-
gen acceptor) occurs over the same Cu–Zn catalyst and under
similar reaction conditions [11, 12]. Compared to the individu-
al reactions, the coupled reactions can be conducted at much
lower temperature (temperature difference 10–20 °C), using
less excess of hydrogen, in reactors that are simpler from the
constructive point of view (small specific heat transfer area or
adiabatically operated), while keeping the same efficiency [9].
Extensive reviews of different catalytic reactors used for
coupling exothermic and endothermic reactions, in particular
hydrogenation and dehydrogenation, have been provided by
Rahimpour et al. [13] and Pramod et al. [14], respectively.
4.1 Kinetics
The hydrogenation of BDO to GBL is a two-step reaction. In
the first step, BDO is hydrogenated to 2-hydroxytetrahydrofur-
an, which is further hydrogenated to GBL. The first step is rate
limiting and the product is unstable and very reactive. The sec-
ond step is very fast, resulting in high selectivity (> 99 %) to
GBL. The overall reaction is (virtually) irreversible and endo-
thermic. For a pure BDO feed, the adiabatic temperature rise is
–380 °C; thus, constant heating is required. The kinetic para-
meters for BDO hydrogenation to GBL, on a CuO/Al2O3-ZnO-
ZrO2 catalyst, were found by fitting the experimental data
obtained in the range of 200–300 °C and at different reactant
ratios, taken from [18]:
rBDO ¼ kcBDO (4)

2 Problem Statement
 
11525 kcal=kmol
k ¼ 468 exp  m3 kg1
cat s
1
(5)
RT
The previous cited studies demonstrated the possibility of cou-
pling BDO dehydrogenation and FAL hydrogenation in a sin- For FAL hydrogenation, the experimental data reported in
gle reactor. However, the complete design of the entire plant is the literature [19] was used in order to develop the reaction
missing. Due to material recycling, the interaction between the rate expression. The experimental study [19] was performed at
adiabatic reactor carrying out the coupled reactions and the different temperatures (230, 270, 290 °C), using Cu/SiO2 as cat-
separation section may be a source of undesired nonlinear phe- alyst. The flow rates of liquid FAL and H2 were 0.5 and
nomena (such as instability and parametric sensitivity [15]), 3600 mL h–1 respectively. The assumed mechanism considers
leading to controllability problems. This article presents the de- that the reaction takes place on one active site, that the adsorp-
sign of an integrated plant for the production of GBL, FOL, tion constants are independent of temperature, and that the ad-
and 2-MF. Moreover, the control of the plant is addressed, sorption of hydrogen can be neglected. The rate-limiting steps
proving by rigorous steady-state and dynamic simulations that are the reversible hydrogenation of adsorbed FAL (Eq. (7)) and
the proposed plant is flexible to be operated in different scenar- the irreversible hydrogenation of adsorbed FOL (reaction 9).
ios: Adsorption of FAL (Eq. (6)) and desorption of FOL and MF
– changing production rates of GBL and FOL/2-MF (Eqs. (8) and (10)) are assumed to be at equilibrium. The con-
– maintaining constant production rates but allowing changes centration of free active sites is negligible. Due to the high con-
in product distribution centration of hydrogen, its effect is included in the reaction rate
Therefore, this is the first instance of studying this coupled constants. For this reason, the kinetic expressions cannot be
system in a complete plant. extended to small hydrogen concentrations.
K FAL
FAL + X FAL - X (6)
3 Solution Method
k1
A series of steps were followed to solve the problem: FAL - X + H 2 k−1
FOL - X ( rate limiting ) (7)
– The possibility of carrying out, simultaneously, the two reac-
tions in a stand-alone adiabatic reactor was appraised.
1/K FOL
– The results obtained from the stand-alone reactor were FOL - X FOL + X (8)
re-evaluated by considering its operation in a reactor-separa-
tion-recycle (R-S-R) system.
– A detailed design of an integrated plant was performed, in- FOL - X + H 2 ⎯k⎯
2
→ MF - X+ H 2O ( rate limiting ) (9)
cluding sensitivity analysis.
– The coupled plant was assessed in steady state using Aspen-
1/K MF
Plus [16] and analyzed dynamically using AspenDynamics MF - X MF + X (10)
[17].
Under these assumptions, the following Langmuir-Hinshel-
wood-Hougen-Watson (LHHW) rate expressions are derived.

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 Research Article 1517

4.2 The Integrated Reactor

!
1 pFOL pH2
k1 *pFAL 1 
Keq pFAL
r1 ¼ (11) In order to assess the feasibility of simultaneously performing
KFOL K BDO dehydrogenation and FAL hydrogenation, an adiabatic re-
pFAL þ p þ MF p
KFAL FOL KFAL MF actor was considered. The reactor is fed with 10 kmol h–1 FAL,
20 kmol h–1 BDO, and 150 kmol h–1 H2, at 1.5 bar and 250 °C.
The reactant ratio was chosen to approximately match the theo-
k2 *pFOL
r2 ¼ (12) retical value of 10:23, for which the heats of reaction perfectly
KFAL K
pFAL þ pFOL þ MF pMF balance each other. The pressure and temperature values were
KFOL KFOL set according to the experimental conditions [18, 19], from
which the kinetic expressions (4), (5), and (11)–(14) were ob-
KFAL k1 tained. Moreover, the large hydrogen excess ensures the validity
where Keq ¼ . of the kinetic expressions. The reactor uses a total of 8000 kg of
KFOL k1
catalyst, in which the BDO dehydrogenation and FAL hydroge-
nation catalysts are mixed in equal proportions. Note that the
The following kinetic parameters were found by fitting the ratio between the catalysts could be used to tune the ratio be-
experimental data [19]. tween the rates of the dehydrogenation and hydrogenation pro-
cesses. The reactor volume is 4 m3, estimated by assuming that
the bulk catalyst density is 2000 kg m–3 (corresponding to the
  
1 1
k1 * ¼ 4:395 · 106 exp 4049  ; kmol kg1
cat s
1
T 543 Al2O3 support with 0.5 void fraction). The reactor diameter
(13) (3.25 m) and length (0.5 m) correspond to a superficial velocity
of 2.5 m s–1. Although larger reactors could produce more 2-MF
   and less FOL, the same results can be obtained by separation
1 1 and recycling of FOL from the reactor outlet. Therefore, in
k2 * ¼ 1:488 · 107 exp 4255  ; kmol kg1
cat s
1
T 543 order to ensure maximum flexibility with respect to product
(14) distribution (FOL and 2-MF), the quantity of catalyst leading to
the maximum amount of FOL was chosen.
It should be remarked that one can anticipate the need of a
KFOL KMF compressor to increase the system pressure from 1.5 to 10 bar,
Keq ¼ 8:12 · 103 Pa; ¼ 0:744; ¼ 2:28
KFAL KFAL in order to perform the gas-liquid separation of the reactor out-
let stream in such a way that the volatile 2-MF remains in the
liquid phase. We acknowledge the anonymous reviewer who
For illustration purposes, Fig. 1 compares the calculated re- pointed out that the compressor could be placed in front of the
action profiles with two sets of experimental data [19]. reactor, with the additional benefit of reduced reactor size. This
The equilibrium constant is in agreement with the value ob- solution was not adopted here because it seemed dangerous to
tained from the AspenPlus thermodynamic data. It should be extrapolate the reaction kinetics to 10 bar while it was deter-
remarked that FAL hydrogenation is a highly exothermic pro- mined from experiments performed at atmospheric pressure.
cess. The reaction can be carried out safely at temperatures of Fig. 2 shows the concentration and temperature profiles
up to 290 °C. Thus, for a H2-to-FAL ratio of 10:1, the adiabatic along the reactor and the effects of changing the reactor inlet
temperature rise is 104 °C for partial hydrogenation to FOL temperature and the hydrogen-to-furfural ratio on the temper-
and 287 °C for complete hydrogenation to 2-MF. Consequently, ature. For each reaction, the conversion of reactants into prod-
the reaction is conventionally carried out in expensive multi- ucts is distributed along the reactor length. BDO reacts faster
tubular reactors with cooling. In addition to a large heat trans- than FAL, which creates a local imbalance in heat consumption
fer area, a large amount of excess hydrogen is used (up to and generation. The reduced reactor sensitivity with respect to
100:1). Nevertheless, there is still a high risk of runaway. these disturbances should be noted.

4.3 R-S-R System

Once it was confirmed that the re-

action can be performed in a single
adiabatic reactor, with reduced sen-
sitivity with respect to feed distur-
bances, the next step was to analyze
a complete R-S-R system. The mix-
ture of products, by-product, and
unconverted reactants from the
reactor outlet required multiple
Figure 1. Comparison of the (*) experimental and (–) fitted data.

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1518 Research Article

tion. As the combined 2-MF + FOL rate equals the fresh FAL,
this is a convenient way to adjust the product distribution. The
separation details will be discussed in the next section.
Fig. 4 shows the mole fraction and temperature profiles along
the reactor. The conversion of reactants into products is uni-
formly distributed along the reactor length. Similar to the
stand-alone reactor, the reactor inlet and outlet have about the
same temperature.
Fig. 5 a shows the influence of the amount of FOL product
on the maximum reaction temperature. Decreasing the amount
of product results in higher temperatures, but without exceed-
ing the upper limit of 290 °C. Fig. 5 b shows the effects on the
reactor inlet/outlet. As more FOL is recycled, the conversion of
FAL decreases, resulting in larger recycles but still reasonable
values. The vital conclusion that can be drawn is that the reac-
tor can be integrated in an R-S-R system. So, we proceed with
the design of the separation system.

Figure 2. Integrated, stand-alone reactor. (a) Mole fraction pro-

files. Temperature profiles for (b) different reactor inlet tempera-
tures, and (c) different hydrogen/FAL ratios.

separation units. As a first step, the R-S-R system is studied by

assuming perfect separation.
The R-S-R system is shown in Fig. 3. The reactor feed (1)
consists of fresh feed (0) mixed with recycle stream (3). The
separation section removes the products H2, 2-MF, GBL, and
H2O, which are lumped in stream (5). A certain amount of
FOL is removed in stream (4), according to the desired produc-

Figure 4. Integrated R-S-R system. (a) Mole fraction profiles.

Temperature profiles for (b) different reactor inlet temperatures,
Figure 3. R-S-R system. and (c) different hydrogen/FAL ratios (F4,FOL = 6 kmol h–1).

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 Research Article 1519

distillation is required to separate FOL from FAL. The required

amount of high-purity FOL is taken out as bottom product and
the remaining mixture of FAL and FOL is recycled. If the re-
quired product is only 2-MF, then there is no need to separate
the FAL/FOL mixture, eliminating one distillation unit.
The design of the integrated processes was achieved by using
AspenPlus as an efficient process simulation tool. To design the
distillation columns, the DSTWU short-cut model calculates
the minimum number of trays Nmin1) and the minimum reflux
ratio Rmin starting from the recovery of light key and heavy key
components. The number of trays was set as 2 Nmin and the
corresponding reflux ratio R was calculated, together with the
feed tray and the distillate-to-feed ratio D/F. Then, these
specifications were used in the rigorous distillation model
RADFRAC. By means of the Design Specification option pro-
vided by the simulator, small adjustments of R and D/F were
made such that the required distillate and bottom purities (or
recoveries) were achieved. The simulation also provides the
condenser and reboiler duties. The mixers, vapor-liquid or
vapor-liquid-liquid separators were designed assuming 10 min
of residence time and a height-to-diameter ratio of 2:1. The
simulation convergence can be greatly accelerated if Design
Specification blocks are used, in which specified values of the
reactor inlet flow rates are achieved by changing the plant inlet
flows of fresh reactants.

Figure 5. Integrated R-S-R system. (a) Reactor outlet tempera-

ture, and (b) reactor inlet/outlet flow rates versus FOL produc-
4.5 Integrated BDO Dehydrogenation-FAL
tion rate. F0,BDO = 20 kmol h–1, F1;H2 = 150 kmol h–1. Hydrogenation Plant

Fig. 6 presents the flowsheet of the combined BDO dehydrogen-

ation-FAL hydrogenation process. The reactants (20 kmol h–1
4.4 Design of the Separation Section BDO, 10 kmol h–1 FAL, and 150 kmol h–1 hydrogen) are mixed
and brought to reaction temperature (250 °C). The reactions
Tab. 1 presents the main physical properties of the chemical take place in a catalytic reactor (3.25 m in diameter, 0.5 m in
species involved in the combined GBL/FOL/2-MF process. length), which is operated adiabatically. Total conversion of
According to the physical properties, hydrogen is separated BDO and high conversion (up to 85 %) of FAL in the reactor is
from the rest of the mixture in a vapor-liquid separator, and re- achieved, depending on the amount of 2-MF product.
cycled. The first distillation setup is required to separate 2-MF The reactor outlet is compressed to 10 bar and cooled to
and water from the mixture. The solubility of 2-MF in water is 5 °C, and vapor-liquid separation is performed. The hydrogen
negligible; so, these two components get separated by simple is recycled, while the organic phase is separated, in a series of
liquid-liquid split. GBL is separated from the FAL and FOL distillation columns, taking 2-MF, FOL, and GBL as products.
mixture by the second distillation, as bottom product. A third The first column, operated at 1.5 bar, separates 2-MF and water
from the mixture as top product. It has 8
Table 1. Physical properties of the chemical species. stages and the required reflux ratio is 0.73.
The condenser and reboiler duties are 0.15
Reactor outlet Boiling point Solubility in water Destination Separation and 0.44 MW, respectively. Liquid distillate
species [°C] [g L–1] (2-MF and water) is sent to the liquid-liq-
uid separator. As a result of separation,
Hydrogen, H2 –253 – recycle 2-MF is recovered at about 95 % purity.
V-L split
2-MF, C5H6O 66 3 product The mixture of FOL, GBL, and unreacted
L-L split FAL is fed to the second column, which is
Water, H2O 100 – product
distillation operated at 1 bar and has 35 stages, and the
FAL, C5H4O2 162 83 recycle required reflux ratio is 3.06. The condenser
distillation and reboiler duties are 0.29 and 0.42 MW,
FOL, C5H6O2 170 miscible product/recycle
distillation
GBL, C4H6O2 204 miscible product

BDO, C5H10O2 235 miscible traces

–
1) List of symbols at the end of the paper.

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1520 Research Article

Figure 6. Integrated BDO dehydrogenation-FAL hydrogenation.

respectively. GBL is obtained as a bottom product at the rate of actor and separation sections, for maximum FOL production
19.9 kmol h–1 with 99.95 % purity. From the top, FOL with un- (6 kmol h–1), are shown in Tabs. 3 and 4, respectively.
reacted FAL is fed to the third distillation column. The primary
function of this column is to separate FOL from the mixture in
such a manner that the production of FOL can be manipulated. 4.6 Plantwide Control
The column has 22 stages and is operated at 0.8 bar pressure,
with condenser and reboiler duties of 0.57 and 0.44 MW, re- Dynamic simulation is a convenient method for analyzing the
spectively. FOL is obtained as a bottom product with 99.5 % performance of a process control system. The dynamics of
purity. Despite the close boiling points of FAL and FOL, this the plant must be considered in order to prove the stability of
separation is easy because the FOL product is obtained at high the operating point and the resiliency with respect to distur-
purity but low recovery. The design of the distillation columns bances. The main task of a plantwide control system is to
is summarized in Tab. 2. control the inventory of reactants, products, and impurities.
It should be noted that, in theory, the plant could be Controlling the inventory of reactants within the plant can be
designed such that there is no need of hydrogen feed and no performed in two ways [20]: (a) by evaluating, directly or
hydrogen production. However, perfect balancing of hydrogen indirectly, the inventory of each reactant and controlling it by
consumption/generation in the two reactions is impossible feedback using the corresponding fresh feed as manipulated
in practice. Therefore, the fresh and purge hydrogen streams variable; (b) by fixing the fresh feed rate and using the
are provided for control purposes. The stream details of the re- self-regulation property of the mass balances [21].
We use the second strategy by fixing the
flow rates of FAL and BDO at the plant inlet.
The advantage of this control structure is
Table 2. Summary of the distillation column design.
that the production rate can be achieved by
changing the flow rates of the fresh reac-
Column 1 Column 2 Column 3
tants. The results of the steady-state simula-
Total stages 8 35 22 tions (Fig. 5 b) indicate the value of the FOL
recycle that leads to a given FOL-to-2-MF
Feed stage 3 19 14
ratio. Therefore, the desired distribution
Reflux ratio 0.73 3.06 6.42 between FOL and 2-MF is achieved, in a
D/F 0.152 0.276 0.2078 feedforward manner, by adjusting the
amount of FOL recycle.The control of the
Pressure [bar] 1.5 1 0.8 vapor-liquid and liquid-liquid separators
Condenser type partial vapor-liquid partial vapor total and that of the distillation columns is
standard. Thus, the liquid and vapor inven-
Condenser temperature [°C] 15 – – tories (levels and pressures) are typically
Design specifications controlled by manipulating the unit outlet
flow rates. For the distillation columns,
Recovery 99.8 % water in top 99.99 % GBL 5–75 % FOL quality control is achieved by keeping the
99.5 % FOL in bottom – – temperature in the top and bottom sections
constant, by means of the reflux and re-
Purity – 99.95 % GBL 99.5 % FOL
boiler duty, respectively. It was found that,
Condenser duty [MW] –0.15 –0.29 –0.57 with only the temperature control, the pu-
rity of the GBL product stream occasionally
Reboiler duty [MW] 0.44 0.42 0.44
deviates by a significant amount from the

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 Research Article 1521

Table 3. Stream table of the reactor section (FOL production = 6 kmol h–1).

BDO FAL Hyd-In FOL-In RIn ROut Sep-In

Temperature [°C] 25 25 13.2 156.7 250 248.6 5

Pressure [bar] 1.5 1.5 1.5 0.8 1.49 1.39 10.1

Vapor fraction 0 0 1 0 1 1 1
–1
Mole flow [kmol h ] 20 10 150.12 4.53 184.65 214.75 214.75
–1
Mass flow [kg h ] 1802 960 311 440 3514 3514 3514
3 –1
Volume flow [m h ] 1.772 0.833 2383 0.445 5390 6701 491
–1
Mole flow [kmol h ]

Hydrogen 0 0 150 0 150 176.25 176.25

Water 0 0 0.026 0.006 0.032 3.873 3.873

FAL 0 10 0 1.717 11.717 1.816 1.816

FOL 0 0 0 2.807 2.807 8.867 8.867

2-MF 0 0 0.098 0 0.098 3.939 3.939

BDO 20 0 0 0 20 0.002 0.002

GBL 0 0 0.001 0 0.001 19.999 19.999

Table 4. Stream table of the separation section (FOL production = 6 kmol h–1).

Sep-In Hyd-Rec Col1-In Col1-Top Col2-In Col2-Top FOL-In 2-MF GBL FOL Water

Temperature [°C] 5 5 5 15 202.2 167.8 156.7 5 215.3 169.9 5

Pressure [bar] 10.1 10 2 1.5 1.57 1 0.8 1 1.34 1.01 1

Vapor fraction 1 1 0 0 0 1 0 0 0 0 0
–1
Mole flow [kmol h ] 214.75 176.44 38.31 7.69 30.55 10.56 4.53 3.915 19.988 6.03 3.77
–1
Mass flow [kg h ] 3514 372 3142 388 2752 1031 440 318 1720 591 70.27
3 –1
Volume flow [m h ] 491 408 3.35 0.36 2.91 387 0.445 0.29 1.83 0.617 0.069
–1
Mole flow [kmol h ]

Hydrogen 176.25 176.189 0.065 0.002 0 0 0 0.001 0 0 0

Water 3.873 0.052 3.821 3.813 0.006 0.006 0.006 0.07 0 0 3.744

FAL 1.816 0.001 1.815 0.071 1.745 1.745 1.717 0.046 0 0.028 0.025

FOL 8.867 0.001 8.866 0.052 8.815 8.807 2.807 0.049 0.008 6 0.002

2-MF 3.939 0.196 3.743 3.735 0 0 0 3.733 0 0 0.002

BDO 0.002 0 0.002 0 0.002 0 0 0 0.002 0 0

GBL 19.999 0.001 19.998 0.018 19.98 0.002 0 0.017 19.978 0.002 0.001

required value. Therefore, a composition-temperature cascade
loop was employed. The control structure of the integrated
plant is shown in Fig. 7.
The controllers were tuned by a simplified version of the
direct synthesis method. For each controller, the appropriate
range of the controlled and manipulated variables was specified
(for example, 30 degrees for temperature measurements,
0.2 bar for pressure measurements, twice the nominal value for
flow rate manipulations). The controller gain was set to 1°%/%.
The integral time was set as equal to the time constant of the
process, namely 12 min for pressure and 20 min for the temper-
ature control loops. For the level controllers, a large reset time
ti = 60 min was chosen as no tight control was required.
The dynamic model of the plant was built in AspenDynam-
ics, and the flexibility in obtaining different products was in-
vestigated. The dynamics simulation results are shown in

Chem. Eng. Technol. 2014, 37, No. 9, 1515–1524 ª 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.cet-journal.com
1522
Figure 7. Plantwide control.
Figs. 8–10 for product purity and production. All simulations
started from a steady state corresponding to a GBL production
rate of 20 kmol h–1. Two different operating points were consid-
ered: (a) the plant is operated such that 6 kmol h–1 of FOL and
3.75 kmol h–1 of 2-MF are produced; (b) the plant is operated
such that 1 kmol h–1 of FOL and 8.75 kmol h–1 of 2-MF are
produced. The possibility to change the GBL and FOL/2-MF
production rates was investigated. The last set of simulations
addressed the transition between the operating points (a) and
(b). All changes were introduced at time t = 2 h.
In Fig. 8, the GBL production rate is changed by ±10 % by
changing the flow rate of fresh BDO at two different FOL pro-
duction rates of 6 (top) and 1 kmol h–1 (bottom). The new
production rate is achieved in approximately 4 h. The purities
of GBL, 2-MF, and FOL remain unchanged and the ratio of
FOL/MF is also not affected.
Similarly, the production rates of both FOL and 2-MF are
changed by varying with ±10 % fresh FAL, at two different FOL
production rates of 6 (top) and 1 kmol h–1 (bottom), and the
effect is shown in Fig. 9. After 4 h of operation, a new steady
state is achieved and the changes are like those predicted by the
steady-state simulation in Fig. 5. The disturbances have no
effect on the production rate of GBL, and also the product
purities remain unchanged.
Fig. 10 shows the change in the product distribution from
one extreme (1 kmol h–1 FOL and 8.75 kmol h–1 2-MF) to an-
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Research Article
other (6 kmol h–1 FOL and 3.75 kmol h–1 2-MF). To accomplish
this goal, the flow rate of the recycle stream (FAL + FOL) is de-
creased from 25 to 15 kmol h–1 (values which are known from
the steady-state analysis).
Based on the rigorous dynamic analysis, it can be concluded
that it is possible to independently change the production rates
of GBL and 2-MF/FOL. Moreover, the 2-MF/FOL product ra-
tio can also be changed by changing the operating conditions.
5 Conclusion
An integrated process for the simultaneous production of GBL,
FOL, and 2-MF in a single reactor is presented. The analysis
shows that the reactions can be carried out using small hydro-
gen excess, in an adiabatic reactor with reduced parameter sen-
sitivity. The process is controllable and flexible, allowing differ-
ent production rates and a wide range of ratios between the
FOL and 2-MF products. The additional separation of GBL
from the reaction mixture is easy. The plant robustness conclu-
sions are supported by rigorous steady-state and dynamic sim-
ulations performed in AspenPlus and AspenDynamics.
The authors have declared no conflict of interest.
Chem. Eng. Technol. 2014, 37, No. 9, 1515–1524
 Research Article 1523

Figure 8. Performance of the plantwide control system for GBL production rate changes. Top: Production rates of 6 kmol h–1 FOL, 4 kmol h–1
2-MF. Bottom: Production rates of 1 kmol h–1 FOL, 9 kmol h–1 2-MF.

Figure 9. Performance of the plantwide control system for FOL and 2-MF production rate changes. Top: FOL/2-MF = 6:4. Bottom:
FOL/2-MF = 1:9.

Chem. Eng. Technol. 2014, 37, No. 9, 1515–1524 ª 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.cet-journal.com
1524 Research Article

Figure 10. Performance of the plantwide control system for changing the FOL/2-MF ratio from 1:9 to 6:4.

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