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Bioresource Technology
journal homepage: www.elsevier.com/locate/biortech
AkzoNobel Research, Development & Innovation, Process Technology ECG, Velperweg 76, 6824 BM, Arnhem, The Netherlands
University Politehnica of Bucharest, Centre for Technology Transfer in Process Industries, Polizu 1-7, 011061 Bucharest, Romania
a r t i c l e
i n f o
Article history:
Received 6 May 2010
Received in revised form 13 August 2010
Accepted 22 August 2010
Available online 25 August 2010
Keywords:
Reactive absorption
Plantwide control
Energy integration
Green catalyst
Biofuel
a b s t r a c t
Reactive separations using green catalysts offer great opportunities for manufacturing fatty esters,
involved in specialty chemicals and biodiesel production. Integrating reaction and separation into one
unit provides key benets such as: simplied operation, no waste, reduced capital investment and low
operating costs.
This work presents a novel heat-integrated reactive absorption process that eliminates all conventional
catalyst related operations, efciently uses the raw materials and equipment, and considerably reduces
the energy requirements for biodiesel production 85% lower as compared to the base case. Rigorous
simulations based on experimental results were carried out using Aspen Plus and Dynamics. Despite
the high degree of integration, the process is well controllable using an efcient control structure proposed in this work. The main results are provided for a plant producing 10 ktpy fatty acid methyl esters
from methanol and waste vegetable oil with high free fatty acids content, using sulfated zirconia as solid
acid catalyst.
2010 Elsevier Ltd. All rights reserved.
1. Introduction
1.1. Background
Fatty esters are important chemicals used mainly in cosmetics,
pharmaceuticals, cleaning products and in the food industry. However, in the last decade the main interest has shifted to the large
scale production of biodiesel hence the stronger market drive
for more innovative and efcient processes. Biodiesel is a biodegradable and renewable alternative fuel with properties similar
to petroleum diesel (Bowman et al., 2006; Balat and Balat, 2008).
Typically, it is produced from green sources such as vegetable oils,
animal fat or even waste cooking-oils from the food industry (Encinar et al., 2005; Kulkarni and Dalai, 2006).
Nowadays, employing waste and non-edible raw materials is
mandatory to comply with the economical, ecological and also ethical requirements for biofuels. Basically, the food versus fuel competition can be easily avoided when the raw materials are waste
vegetable oils, non-food crops such as Jatropha (Kumar and Sharma, 2005) and Mahua (Puhan et al., 2005) or castor oil (Canoira
et al., 2010). However, waste raw materials can contain a substantial amount of free fatty acids (FFA), up to 100%. Consequently, an
efcient continuous biodiesel process is required that uses a solid
catalyst in order to suppress the costly downstream processing
steps and waste treatment.
Corresponding author. Tel.: +31 26 366 1714; fax: +31 26 366 5871.
E-mail addresses: Tony.Kiss@akzonobel.com, tonykiss@gmail.com (A.A. Kiss).
0960-8524/$ - see front matter 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.biortech.2010.08.066
Unlike petroleum diesel that is mixture of hydrocarbons, biodiesel consists of fatty acid methyl esters (FAME). Fatty esters are
currently produced by acid/base catalyzed trans-esterication, followed by several neutralization and product purication steps
(Hanna et al., 2005; Meher et al., 2006). Nevertheless, all conventional methods suffer from problems related to the use of liquid
catalysts, leading to severe economical and environmental penalties. Obviously, this has to change considering the impact of the
large scale production.
At present, the most common manufacturing technologies employ homogeneous catalysts, in batch or continuous processes
where both reaction and separation steps can create bottlenecks.
The literature overview reveals several processes currently in use
at pilot or industrial scale:
Batch processes allow better exibility with respect to composition of the feedstock. The trans-esterication is performed using an
acid or base catalyst, but the equipment productivity is low and
operating costs are high (Hanna et al., 2005; Lotero et al., 2005).
Continuous processes combine the esterication and trans-esterication steps, allowing higher productivity. Nonetheless, most of
these processes are still plagued by the disadvantages of using
homogeneous catalysts although solid catalysts emerged in the last
decade (Dale, 2003; Kiss et al., 2006a). Several reactive-distillation
processes were reported (He et al., 2006; Kiss et al., 2006b), along
with the ESTERFIP-H process developed by the French Institute of
Petroleum. The latter uses a solid catalyst based on Zn and Al
oxides, requiring high temperature (210250 C) and pressure
(3050 bar).
491
492
Fig. 2 shows the composite curves and the yearly cost as function of the minimum delta T. This conrms the heuristics ndings,
as there is just a minimal need for an external hot utility to preheat the fatty acid feed stream.
2.2. Process simulation
Process simulations embedding experimental results were performed using Aspen Plus (AspenTech, 2009). The RA column was
simulated using the rigorous RADFRAC unit with RateSep (ratebased) model enabled, and explicitly considering three phase balances. The physical properties required for the simulation and
the binary interaction parameters for the methanolwater and
acid-ester pairs were available in the Aspen Plus database of pure
components, while the other interaction parameters were estimated using the UNIFAC Dortmund modied group contribution
method (AspenTech, 2009). Using other state-of-the art estimation
methods, such as UNIFAC and UNIFAC Lyngby modied, leads to
similar results.
As phase splitting may occur (Kiss, 2009), the RA column is
modeled using VLLE data. Phase splitting must be accounted for
as the free water phase can deactivate the solid acid catalyst. Nevertheless, as revealed latter by the column composition proles,
the liquid molar fraction of water does not exceed 0.1 on any given
stage. Therefore, the catalyst deactivation does not occur here, under the designed process conditions.
The fatty components were conveniently lumped into one
fatty acid and its fatty ester according to the reaction:
R COOH CH3 OH $ R COO CH3 H2 O. Dodecanoic (lauric)
acid/ester was selected as lumped component due to the availability of experimental results, kinetics and VLLE parameters for this
Fig. 1. Synthesis of fatty esters by reactive absorption base case owsheet (a) and
heat-integrated process (b).
can be changed to ensure the required temperature of the columninlet acid stream (F-ACID). The hot liquid product of the FLASH, a
mixture of fatty esters, is used to pre-heat and vaporize the alcohol
feed stream. If changes of the production are expected, the nominal
design should include a bypass of the hot stream (dashed line in
Fig. 1b) which can be used for control purposes.
Fig. 2. Composite curve (a) and yearly cost versus minimum delta T (b).
493
Table 2
Design parameters for simulating the reactive absorption column.
Parameter
Value
Units
15
10 (from 3 to 12)
0.4
0.6
VLL
18
6.5
1050
>99.99
1167
188
1250
19.2
m
m
L
kg
kg/m3
%
kg/h
kg/h
kg/h
kg FAME/kg cat/h
where k1 and k2 are the kinetic constants for the direct (esterication) and reverse (hydrolysis) reactions, Wcat is the weight amount
of catalyst, and CComponent is the molar concentration of the components present in the system. Note that by changing the weight
amount of catalyst used (Wcat) the reaction rate can be similar for
different catalysts. As water is continuously removed from the system, the reverse hydrolysis reaction is extremely slow hence the
second term of the reaction rate can be neglected. Therefore, a simple kinetic expression can be used:
methyl esters (FAME) from methanol and waste vegetable oil with
highest free fatty acids (FFA) content, using solid acids as green
catalysts. Table 1 presents the complete mass balance of the process, while Table 2 lists the main design parameters, such as column size, catalyst loading, and feed condition.
High conversion of the reactants is achieved, with the productivity of the RA unit exceeding 19 kg fatty ester/kg catalyst/h. The
purity specication is higher than 99.9%wt for the nal biodiesel
product (FAME stream). Note that the total amount of the optional
recycle streams (REC-BTM) is not signicant representing less than
0.9% of the biodiesel production rate.
The liquid and vapor composition proles along the reactive
absorption column are plotted in Fig. 3a and b, respectively. The
concentration of fatty ester and methanol increases from the top
to bottom, while the concentration of the fatty acid and water increases from the bottom to the top of the column. Therefore, the
top product of the reactive separation column is water vapors with
small amounts of fatty acids, while the bottom liquid stream is the
fatty esters product (biodiesel) with a limited amount of methanol.
In particular cases, the concentration of methanol in the liquid
phase could be further increased by working at higher pressure.
Fig. 3c plots the temperature and reaction rate proles in the
reactive column. The RA column is operated in the temperature
range of 135165 C, at ambient pressure. The reaction rate exhibits a maximum in the middle, where the reactive zone is placed.
Table 1
Mass balance of a 10 ktpy FAME process based on integrated reactive-absorption.
Temperature/(C)
Pressure/(bar)
Vapor fraction
Mole Flow/(kmol/h)
Mass ow/(kg/h)
Mass ow/(kg/h)
Methanol
Acid
Water
Fame
Mass fraction
Methanol
Acid
Water
Fame
Mole fraction
Methanol
Acid
Water
FAME
F-ACID
F-ALCO
BTM
REC-BTM
REC-TOP
TOP
WATER
FAME
160
1.05
0
5.824
1166.7
65.4
1.05
1
5.876
188.3
136.2
1.03
0
6.125
1261.3
146.2
1.216
1
0.252
11.3
51.8
1
0
0.059
9.369
162.1
1
1
5.886
114.4
51.8
1
0
5.828
105.06
30
0.203
0
5.873
1250
0
116.74
0
0
188.3
0
0
0
9.125
Trace
Trace
1252.2
7.544
Trace
Trace
3.764
0.002
9.218
0.24
0.846
0.103
9.233
105.2
0.846
0.101
0.016
104.93
Trace
1.581
Trace
Trace
1248.4
0
1
0
0
1
0
0
0
0.007
Trace
Trace
0.993
0.667
Trace
10 ppb
0.333
172 ppm
0.894
0.023
0.082
894 ppm
0.08
0.912
0.007
965 ppm
148 ppm
0.999
513 ppb
0.001
Trace
Trace
0.999
0
1
0
0
1
0
0
0
0.046
Trace
Trace
0.954
0.931
Trace
26 ppb
0.069
873 ppm
0.726
0.211
0.062
546 ppm
0.008
0.992
670 ppm
0.001
13 ppm
0.999
43 ppb
0.008
Trace
Trace
0.992
0.2
0.6
0.8
Water
3
Stage
0.4
100%
Purity / [wt%]
494
90%
Acid
Water
FAME
80%
70%
9
12
Methanol
60%
0.8
Ester
0.9
1.1
1.2
0.4
0.6
0.8
0.4
0.6
0.8
Acid
3
Stage
0.2
Water
80
FEHE2
0.6
Tacid = 180 C
40
0.4
160 C
20
0.2
140 C
HEX1
0
0.8
0
0.9
1.1
1.2
c
Ester
0.2
Methanol
0.4
0.6
0.8
140
150
160
170
12
1
0.8
140 C
60
15
Split
160 C
FEHE1
180 C
0.5
Recycle Bottom
140 C
0.4
Water
160 C
0.3
180 C
0.2
6
FAME
180 C
0.1
160 C
Recycle Top
140 C
4
0.8
0
0.9
1.1
100
Split fraction
15
1.2
Stage
Fig. 4. Purity of top (water) and bottom (FAME) products (a), duty of heat
exchangers (b), product and recycle ow rates (c) versus molar reactants ratio
(alcohol:acid).
Reaction rate
12
Temperature
15
0.5
1 1.5 2 2.5
Ester formation / kmol/hr
Fig. 3. Composition, temperature and reaction rate proles along the column.
RD
HIRD
RA
HIRA
136
95
8
72
136
0
0
72
n/a
108
65
n/a
n/a
27
0
n/a
6
141
0
0.6
10
3/10
0.4
0.10
0.12
20.4
191.2
6
38
0
0.6
10
3/10
0.4
0.10
0.12
20.4
108.8
77
78
0
0.6
10
1/15
0.4
n/a
n/a
19.2
138.4
0
14
0
0.6
10
1/15
0.4
n/a
n/a
19.2
21.6
295
168
214
34
separations can be easily controlled by PID controllers in a multiloop framework (Dimian et al., 2009; van Diggelen et al., 2010)
or by using more advanced techniques such as model predictive
control (Nagy et al., 2007).
Fig. 4b shows the duty of heat exchangers versus the molar
reactants ratio (alcohol:acid), for different temperatures of the acid
feed. Vaporization of an increasing ow rate of alcohol requires
more energy to be exchanged in FEHE2, which is realized by
increasing the amount of hot liquid that passes through the heat
exchanger. This can be accomplished if in the base case design
only a certain fraction of the hot stream (80% in our base case design, variable Split dashed line in Fig. 4b) is used for alcohol
vaporization. The fraction of hot liquid that is necessary for alcohol
vaporization increases to almost 100% when the alcohol ow rate
495
Fig. 5. Plantwide control structure: concentration of acid in bottom stream is controlled by manipulating the alcohol ow rate. The temperature of the column-inlet acid
stream is manipulated by a methanol concentration controller.
496
Table 4
Controller tuning parameters.
Controller
Control
action
Range of manipulated
variable
Range of controlled
variable
Setpoint
Bias
Gain
[%/%]
Integral time
[min]
Direct
Direct
Direct
Reverse
Direct
Direct
Direct
Reverse
Reverse
Direct
Reverse
Direct
Reverse
02350 kg/h
040 kg/h
0210 kg/h
0400 kg/h
02500 kg/h
02490 kg/h
012 kmol/h
01.22 kmol/h
00.2 GJ/h
140180 C
0.51
28 kmol/h
00.1 GJ/h
01 m
01 m
01 m
02
01.75 m
01 m
0.951.05 bar
0.180.22 bar
140180 C
15 103
48 kmol/h
12 103
130140 C
0.5 m
0.5 m
0.45 m
1
0.875 m
0.5 m
1 bar
0.2 bar
Output of CC1
3 103
Output of CC2
1 103
137 C
1180 kg/h
14.2 kg/h
105 kg/h
197 kg/h
1259 kg/h
1245
5.91 kmol/h
0.29 kmol/h
0.12 GJ/h
167.6 C
0.9
6.15 kmol/h
0.01 GJ/h
1
1
1
1
10
1
1
1
1
0.1
1
0.2
1
60
12
12
20
40
20
40
20
1500
FAME
1250
Acid
1000
300
4. Conclusions
250
200
Alcohol
750
500
150
100
Water
250
50
0
0
497
0
10
Time / [h]
0.98
2000
0.96
1500
0.94
1000
500
0.92
Acid in FAME
FAME
Water
0.9
Acknowledgements
2500
0
10
Time / [h]
1500
FAME
300
1250
Acid
250
1000
200
Alcohol
750
150
500
100
Water
250
50
0
0
10
1
0.96
3500
FAME
3000
2500
0.92
2000
Water
1500
0.88
1000
0.84
Acid in FAME
0.8
0
500
d
Mass fraction / [-]
Time / [h]
0
10
Time / [h]
Fig. 6. Dynamic simulation results for the owsheet with (a, b) and without (c, d)
methanol recycle: Acid ow rate disturbance of +10% at 1 h, and 10% at 5 h.
Production rate changes are easily achieved and the products purity is maintained
at high values.
streams are taken into account (Fig. 6d). Therefore, the alternative
with methanol recycle is preferable.
498
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