You are on page 1of 6

20th European Symposium on Computer Aided Process Engineering – ESCAPE20

S. Pierucci and G. Buzzi Ferraris (Editors)
© 2010 Elsevier B.V. All rights reserved.

Conceptual design of glycerol hydrogenolysis plant
Costin Sorin Bildea, Elena Zaharia, Grigore Bozga, Gheorghe Soare
University Politehnica Bucharest, Department of Chemical Engineering, Polizu 1-7,
011061 Bucharest, Romania. Email : s_bildea@upb.ro

Abstract
This paper presents evaluation of two different plants performing gas phase glycerol
hydrogenolysis. The study is based on experimental data obtained in our laboratory.
Information about the glycerol conversion and selectivity towards several interesting
products was obtained by experiments performed in a pressure range of 10 - 30 bars, a
temperature range of 180 – 250 ºC and various values of the hydrogen : glycerol ratio.
The main products are propanediols and ethylene glycols. By-products such as acetol
and acrolein and degradation products like propanol and methanol were observed.
Several catalysts were tested, the most promising one (in terms of conversion and
selectivity) being the copper chromite. Two sets of operating conditions were selected
for further evaluation: a) reaction at 220 ºC, 10 bar and high hydrogen : glycerol ratio,
leading to 25% conversion and 85% selectivity towards propanediols and b) reaction at
250 ºC, 10 bar, and low hydrogen : glycerol ratio, leading to 80% conversion but only
40% selectivity. For each set of operating conditions, the design of a glycerol
hydrogenolysis plant was performed in AspenPlus. The main conclusion is that high
selectivity can be achieved only when a very large amount of hydrogen is recycled.
Moreover, the energy consumption is high due to the use of a diluted glycerol solution.
For these reasons and despite the multitude of by-products, the low-selectivity operating
conditions are favorable from an economic point of view.

Keywords: Glycerol, hydrogenolysis, conceptual design, evaluation

1. Introduction
In biodiesel production, an amount of glycerol equivalent to about 10 % wt. of the total
product is obtained. As a result of the increasing availability, the market price of
glycerol has dropped rapidly. Therefore, new uses for glycerol need to be found. Several
publications and patents (Dasari et al., 2005; Miyazawa et al., 2007; Maris and Davis,
2007) present multiple schemes for hydrogenating glycerol to propanediols and ethylene
glycol in the presence of metallic catalysts (Figure 1). These compounds are major
commodity chemicals, with typical uses in unsaturated polyester resins, antifreeze, de-
icing and heat transfer fluids, pharmaceuticals, foods, cosmetics, detergents, paints, etc.
In spite of several research efforts, the study of this potentially important reaction was
limited to laboratory scale. In this contribution, we report and evaluate the conceptual
design of a glycerol hydrogenolysis plant. Thus, several catalysts were experimentally
tested and two sets of operating conditions were selected for further evaluation. For
each set, the design of a glycerol hydrogenolysis plant was performed, using AspenPlus
as a CAPE tool. The results show that high selectivity can be achieved only when a very
large amount of hydrogen is recycled and at the expense of high energy consumption
due to the use of a diluted glycerol solution. For these reasons and despite the multitude
of by-products, the low-selectivity operating conditions are favorable from an economic
point of view.
C.S. Bildea et al.

OH
H3C C CH3 + H2O
H
OH O OH OH 2-PO
+H2
H2C C CH3 H2C C CH3 +H2
H
Acetol
1,2-PD OH H
-H2O 2
H2C C CH3 + H2O
OH OH OH O OH H OH
H2 +H2 2 1-PO
H2C C CH2 HC C CH2 H2C C CH2 +H2 OH
H -H2O
OH 1,3-PD H2C CH3 + CH3OH
G +H2 HPA EtOH MeOH
OH OH
OH OH H2 H2
H2C CH2 + CH3OH H2C C O C CH2
DEG
EG MeOH

O OH OH O OH O OH OH
HC C CH2 HC CH2 + CH2 H2C CH2 + CH3OH CH4 + H2O
H
GA FA EG MeOH
GlyA

Figure 1. Chemical reactions occurring during glycerol hydrogenolysis

2. Experimental study
The reaction of glycerol hydrogenolysis was carried in gas phase, in a tubular stainless
steel reactor (Figure 2) of 0.5 m length and 25 mm diameter.

Figure 2. a) Experimental setup for gas-phase glycerol hydrogenolysis. R – catalytic bed reactor;
V1, V2 – liquid feed vessels; P – isocratic pump; S – gas-liquid separator; Rc – shell-and-tube heat
exchanger; D – gas flow-meter; Q – gas meter. b) Schematics of the hydrogenolysis reactor. 1, 2
- Thermocouple measure/control of temperature in upper/bottom side of reactor; 3 - Gliding
thermocouples inside catalytic bed; 4, 5 – Upper/bottom lid of the reactor; 6 - Mixing chamber; 7
- Heating jacket; 8 – Upper inert layer (glass spheres); 9 – Bottom inert layer (glass spheres); 10,
11 - Electrical heating elements for upper/bottom side of reactor; 12 - Catalytic bed; 13 - Central
thermocouple.
Several catalysts, such as nickel, copper, ruthenium, barium, and copper-chromite in the
form of metallic powders or metal oxides impregnated on activated carbon, alumina or
zeolites were tested. The catalyst was loaded between two layers of glass sphere (2.5÷5
Conceptual design of glycerol hydrogenolysis plant

mm diameter), the upper layer promoting the vaporization of the liquid feed. Hydrogen
and aqueous solution of glycerol were fed from high pressure storage and by means of
an isocratic pump, respectively. The reactor effluent was cooled, and sent to a gas-liquid
separator. Liquid samples were taken and analyzed by gas-chromatography. The feed
flow rates of reactants, the pressure and the temperature at several locations inside the
catalytic bed were monitored and controlled.
The vapor-liquid equilibrium in the glycerol-water-hydrogen system was studied using
AspenPlus. The NRTL model was used to represent the behavior of the liquid phase,
while hydrogen was modeled as a Henry component. Figure 3 presents a summary of
the results. The dependence of the dew point versus pressure was obtained for various
ratios between the flow rates of hydrogen and aqueous glycerol solution. The two
diagrams differ with respect to the mass fraction of glycerol in the solution feed. The
diagrams were used to choose the conditions which guarantee that the reaction mixture
is completely vaporized and therefore the reaction takes place is gas phase.
300 300
F H/F S / [ l/ml ] = 1
275 275 2
vapour 3
250 vapour F H/F S / [ l/ml ] = 1 250 5
2
T / [ºC]

T / [ºC]
3 10
225 5 225
10
200 200

175 175 vapour + liquid
vapour + liquid X Gly = 0.25 X Gly = 0.75
150 150
1 10 1 10
p / [bar] p / [bar]

Figure 3. Vapor – Liquid equilibrium in glycerol - water – hydrogen system.

Thus, the hydrogenolysis experiments covered a pressure range of 2-30 bars and a
temperature range of 195-250°C. The liquid and gas flow varied between 1·10-3-10·10-3
L/min and 0.5-3.7 L/min, respectively. Glycerol solutions of 33%, 50% and 75%
(weight) were used. Best results were obtained when copper chromite was used as
catalyst. Table 1 presents two experiments. Experiment A was performed at 220 ºC, a
relatively low temperature. Large hydrogen flow rate and diluted glycerol solution were
necessary in order to bring the mixture in gas phase. The glycerol conversion was low,
but the conversion toward propanediols was quite high. In contrast, experiment B was
performed at 250 ºC, with a smaller hydrogen flow rate and more concentrated glycerol
solution. The conversion exceeded 80%, but the selectivity was rather poor. Byproduct
such as acetol, ethylene glycol and diethylene glycol were identified.

Table 1. Summary of experimental results
Process Experiment A Experiment B
Temperature, °C 220 250
Pressure, bar 10 10
Liquid flow, mL/min 1 1
Gas flow (normal conditions), L/min 3.6 0.5
Concentration of glycerol solution (%wt) 50 50
Glycol conversion 0.254 0.812
Selectivity for propanediol 0.832 0.438
C.S. Bildea et al.

Conditions similar to these two experiments were chosen to design two different plants
performing glycerol hydrogenolysis at an industrial scale. The results will be reported in
the next section.

3. Conceptual design
In the following, the hierarchical procedure to conceptual design (Douglas, 1988,
Dimian and Bildea, 2008) will be applied. Two different designs will be considered, in
parallel. Design A attempts to achieve a high selectivity for the transformation of
glycerol to propanediols, σ = 0.75. This can be accomplished by operating the chemical
reactor at low-conversion conditions, X = 0.25, similarly to experiment A in the
previous section. In contrast, Design B, similarly to experiment B, achieves a high
glycerol conversion, X = 0.8, at the expense of low selectivity, σ = 0.75.
3.1. The input-output analysis
The design will start from a feed stream of 5000 kg/h aqueous solution of glycerol,
having the concentration of 50% wt. The potential outlet streams were grouped into
products (propanediols) and by-products (alcohols and aldehides as aqueous solutions,
ethyleneglycol and heavies). A simple mass balance gives the flow rates of products
(1528 kg/h for design A, 924 kg/h for design B) and by-products (795 kg/h for design A
and 1888 kg/h for design B).
3.2. The reactor-separation recycle structure of the flowsheet
In this step of the procedure, details concerning the reactor are introduced, while the
separation section is still considered as a black-box. The phase equilibrium discussed in
section 2 allows determining the reactor inlet flow rates which guarantee that the
reaction occurs in gas-phase. Then, flow rates of various recycle streams can be
calculated. Moreover, if the residence time is assumed to be similar to experimental
conditions, the reactor volume can be approximated. A summary of the results is
presented in Figure 4. Design A appears less attractive because very large quantities of
hydrogen and water must be recycled. This happens because the relatively low reaction
temperature requires that a diluted glycerol solution and a large excess of hydrogen are
fed to the reactor. This effect is amplified by the large recycle of glycerol. Moreover, in
design A the reactor volume V = 160 m3 is more than 10 times larger compared to
design B (V = 13.6 m3).
(b)
(a)
Hydrogen recycle: 1838 kg/h Purge: 6 kg/h
Hydrogen recycle: 25514 kg/h Purge: 54 kg/h
Gases: 7 kg/h
Water recycle: 27500 kg/h Water: 2723 kg/h
Water: 2214 kg/h
Gases: 8 kg/h

By-products By-products
Hydrogen Reactor Hydrogen 1878 kg/h Reactor
795 kg/h 1888 kg/h
10 kg/h 40 kg/h X= 0.80
X= 0.25 Water: 226 kg/h Water: 697 kg/h
Water Separation Separation
σ= 0.75 Water
σ= 0.45
2500 kg/h 30000 kg/h 2500 kg/h
Glycerol t = 220°C Propanediols t = 250°C Propanediols
Glycerol 3125 kg/h
2500 kg/h 10000 kg/h V =160 m3 1528 kg/h V= 13.6 m3 924 kg/h
2500 kg/h

Glycerol recycle: 7500 kg/h Glycerol recycle: 625 kg/h

Figure 4. Mass balance for the reactor – separation – recycle structure of glycerol hydrogenolysis
plant.

3.3. Design of the separation section
To design the separation section, the species found in the reactor effluent were ordered
by boiling points. First, a flash was used to separate gases (mainly hydrogen) from the
liquid products and products. The hydrogen was recycled, a purge being necessary in
order to avoid the build up of inert species (mainly methane). Distillation was chosen as
Conceptual design of glycerol hydrogenolysis plant

separation method for the liquid products. First column separates the light components
(water, alcohols, aldehides) from the heavy ones (propanediols, ethyleneglycol, heavies,
glycerol). The light components are separated following the “lights out first” heuristic.
Glycerol is the first component removed from the mixture of high-boiling species
because its high boiling point requires vacuum conditions. The other species are
separated following the same “lights out first” heuristic. The details of the separation
section are presented in Figure 5.

Lights separation

B16
Water
WATER
30
FSPLIT

Hydrogen
GAZE2

2 B4 GAZE1

PURJA
HYDROGEN B5

10
APA-REC
Alcohols
H2 ALCOOLI
B1
8 B11
B11

B2 B3 B6
B3 B6
1 B13
B13
Aldehides
9

21
11
29
B15 ALDEHI DE 1,2 PD
Glycerol
GLY
12PDIOL
B14
Reactor G-L
4

B8
GLY CEROL B8

22 B12
6
B9
B9 EG
EG

17
B7 1,3 PD
B7
B10
Heavies / lights 13
B10 13PDIOL

GLY -REC
ACETOL

Glycerol column
Heavies separation Acetol

Figure 5. Flowsheet of the glycerol hydrogenolysis plant.

Table 2 compares the distillation columns of the two designs. Again, design A appears
less attractive because the energy consumption is almost ten times larger compared to
design B.

Table 2. Comparison of the distillation columns (size and energy requirements)
Design A
Column # B6 B7 B8 B9 B10 B11 B13
Number of stages 11 14 40 40 30 8 15
Column diameter, m 6 1.7 0.94 0.49 0.69 2.77 3.37
Heat duty, 106 kcal/hr
Condenser -46.68 -2.28 -1.41 -0.44 -0.99 -14.33 -8.18
Reboiler 48.01 2.08 1.47 0.44 0.99 16.43 24.53
Design B
Column # B6 B7 B8 B9 B10 B11 B13
Number of stages 11 14 50 40 30 8 15
Column diameter, m 1.8 0.8 0.77 0.56 0.55 0.83 0.88
Heat duty, 106 kcal/hr
Condenser -4.88 -0.55 -0.94 -0.56 -0.62 -1.39 -1.81
Reboiler 5.11 0.51 0.984 0.56 0.62 1.61 1.81
C.S. Bildea et al.

4. Conclusions
This paper considered design of an industrial plant performing gas-phase
hydrogenolysis of glycerol. Starting from experimental data, two sets of operating
conditions were considered.
In design A the chemical reactor is operated at 220 ºC. The result is high selectivity to
propanediols but low glycerol conversion. However, the reaction conditions can be
achieved only when large amounts of hydrogen and water are recycled, which leads to
high energy requirements for the separation section.
In design B the chemical reactor is operated at 250 ºC. The conversion of glycerol is
higher, but larger quantities of by-products are obtained. Compared to the previous case,
the recycles, the size of the reactor and the energy requirements are reduced by more
than one order of magnitude.
The results of this study are valuable in the view of the future experimental
investigations. If gas-phase reaction is desired, the experiments should be conducted at
high temperature and loss of selectivity should be accepted. Moreover, an incentive for
performing the experiments in liquid phase is apparent.

5. Acknowledgements
The authors gratefully acknowledged financial support from the National University
Research Council - CNCSIS (Romania) and National Centre for Programme
Management - CNMP (Romania) through the projects PN-II-ID-PCE-2008-2 no.
1543/2008 & PN2 no. 71-053/2007.

References
Alhanash, A., Kozhevnikova, E.F., Kozhevnikov, I.V., Hydrogenolysis of Glycerol to
Propanediol Over Ru:Polyoxometalate Bifunctional Catalyst, Catal. Lett., 2008, 120, 307–311.
Ullmann’s Encyclopedia of Industrial Chemistry, 5th Ed. Vol A13, VCH, 1985
Chaminand, J., Djakovitch, L., Gallezot, P., Marion, P., Pinel, C., Rosier, C., Glycerol
hydrogenolysis on heterogeneous catalysts, Green Chemistry, 2004 , 6 , 359- 361
Dasari, M.A., Kiatsimkul, P.P., Sutterlin, W., Suppes, G.J., Low-pressure hydrogenolysis of
glycerol to propylene glycol, Applied Catalysis A: General, 2005, 281, 225–231.
Karinen, R.S., Krause, A.O.I., New biocomponents from glycerol, Applied Catalysis A: General,
2006, 306, 128–133.
Soares, R.R., Simonetti, D.A., Dumesic, J.A., Glycerol as a Source for Fuels and Chemicals by
Low-Temperature Catalytic Processing, Angewandte Chemie, 2006, 45(24), 3982-3985.
Miyazawa, T., Koso, S., Kunimori, K., Tomishige, K., Development of a Ru/C catalyst for
glycerol hydrogenolysis in combination with an ion-exchange resin, Applied Catalysis A:
General, 2007, 318, 244–251.
Maris, E.P., Davis, R.J., Hydrogenolysis of glycerol over carbon-supported Ru and Pt catalysts,
Journal of Catalysis, 2007, 249, 328–337.
Douglas, J.M., Conceptual Design of Chemical Processes, Mc-Graw Hill, New York, 1988.
Dimian, A.C., Bildea C.S., Chemical Process Design - Computer-Aided Case Studies, Wiley-
VCH, Weinheim, 2008