Separation of propionaldehyde in a conversion process of glycerol

to 1-propanol
Anton Plsson
Department of Chemical Engineering, Lund University, P. O. Box 124, SE-221 00 Lund, Sweden

Abstract

In this master thesis, a separation step needed in the processes to convert glycerol to 1-
propanol is going to be developed. The purpose of the separation step is to produce an
anhydrous propionaldehyde stream. A number of different setups containing heat ex-
changers, flash tanks and in some cases a distillation column have been simulated. The
simulation showed that the setup with a distillation column have a mass recovery of
propionaldehyde of 99.9 wt % and a water content in the product stream between 5-6
wt %. The setup without a distillation column have a mass recovery of propionaldehyde
of 95 wt % and a water content in the product stream of 4 wt %. To eliminate the re-
maining water, investigations of using adsorption on zeolite has been performed
through a number of experiments in lab scale. The experiments show that it was possi-
ble to, through gas adsorption on zeolites, receive a propionaldehyde product containing
less than 0.01 wt % water from a starting concentration of 5 wt % water. Data from the
experimental unit was also used to calculate a scale up of the adsorption unit to fit the
real system. The scale up gave a cycle time of 58 minutes respectively 96 minutes for
the two most promising cases with a height restriction of the adsorption column of 3 m.

Introduction mixture of propionaldehyde, water, acetic acid,

hydroxyacetone, propionic acid, propylene glycol
As the oil price and the environment awareness and hydrogen. The third reaction step in the process
are increasing, the request for biofuels is increasing is a hydrogenation reaction where propionaldehyde
in the world. One of these biofuels is biodiesel, is converted to 1-propanol.[1][2]
which is produced through a transesterification of For conversion of glycerol to 1-propanol, the re-
triglycerides with methanol in the presence of a action equations are 1, 2 and 3. Reaction 2 and 3 are
strong base or acid. The alcohol reacts with the fatty exothermic and reaction 1 is endothermic.
acids to form mono-alkyl ester (or biodiesel) and
crude glycerol as a by-product. Glycerol is a com-
(1)
mon feedstock in the synthesis of various chemicals,
used in the pharmaceutical and food industry. An
increasing demand of biodiesel, and therefore a gain
in production, has led to a glut in the glycerol market (2)
and hence a drastic price drop of glycerol on the
world market. This leads to adversely impact on the
economics of biodiesel production. Research and
development of processes to convert glycerol to (3)
more profitable chemicals is done at Biofuel-
Solution in Malm. They have, amongst other
The goal with the process is to produce pure
things, developed a method for producing mono-
1-propanol and therefore a separation step is needed
hydric alcohol from glycerol.
to separate propionaldehyde from the other compo-
nents. Otherwise the product stream containing 1-
The first step in the process is a gas phase dehy-
propanol has to be purified. The reasons not to wait
dration step over a suitable heterogeneous catalyst.
to purify the stream until after the last hydrogenation
The dehydration reaction converts the glycerol,
are because if its not purified, a larger stream has to
glycols, and other (poly)ols present in the feed
pass through the last reactor and therefore a larger
stream, primarily to acrolein, hydroxy-acetone, al-
reactor needed. Another reason is that water forms
dehydes and alcohols. The second step is a selective
an azeotrope with 1-propanol at about 58 wt % water
hydrogenation of acrolein to propionaldehyde. The
and that makes it hard to generate an anhydrous
product stream from the second reactor contains a
product.[3]

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The gas stream that is leaving the first hydro-
genation step has a temperature of 260C, at a pres-
sure of 5 atmospheres and contains the following
components, showed in table 1.
other models was that it predicts an azeotrope be-
tween propionaldehyde/water close to published
experimental data. The condenser and reboiler that
were used in the simulations were a Partial-Vapor
condenser and a kettle reboiler. All of the systems
were simulated at a pressure of 5 atm.

Table 1 Components in the product stream from the The simulated system is shown in figure 1 and 2.
first hydrogenation reactor.
Component Boiling point (1atm) Mass Flow (kg/h) C2 C3

H2O 100 C 87 HT2

CONDENS
CH3CH2CHO 46-50 C 10 HT3 G2 D2

C3H6O2 145 C 1
CH3CH2COOH 141 C 1 C1 D1
FL2

CH3COHCHOH 188.2C 1 G1

H2 -252.9C 1.74-3.47 FL1

The problem with the separation is that water L2

DIST

and propionaldehyde forms a homogenous

L1
azeotrope. REBOILER

And the water content is increasing with an in- FEEDR2 2 FD

crease in pressure. In table 2 the water content in the HT1 B1

propionaldehyde water azeotrope at different pres-

sures is presented.
Table 2 shows the water content in the propionalde-
hyde water azeotrope at different pressures. [4]
Pressure
wt% Water
Vapor Temperature
(atm) (C)
1 2.4 48
2 3.2 69
4 5.0 94
6 6.9 111
Similar problems with a water azeotrope and an
organic compound are found in the production of
bioethanol. In the bioethanol process the problem
has been solved by first run a regular distillation
receiving the azeotrope composition. The wa-
ter/ethanol azeotrope is then passed through a mo-
lecular sieve, containing zeolites, which are natural
or synthetic aluminosilicates with a very regular,
fine pore structure. The zeolites adsorb water mole-
cules and allow ethanol molecules to pass through.
The product stream from the molecular sieve then
contains ethanol with very low water content.[5] This
setup is used as template for the system design . The
first step is to receive the propionaldehyde/water
Figure 1 schematic figure of the whole system used in the
simulation for case V and VI.
The system consists of three heat exchangers,
two flash tanks and one distillation column. All the
heat exchangers with both cold and hot input have a
minimum temperature difference of 10 C, between
the hot and cold side. Stream FEEDR2 in figure 1
and 2 is the product stream from the second reactor.
In figure 1 this stream is running the reboiler in the
distillation column. The reboiler is simulated as a
separate heat exchanger (REBOILER) and the calcu-
lated heat duty in the distillation column should be
approximately 70 % of the received duty in heat
exchanger REBOILER. Some of the cooling demand
in the condenser in the distillation column is pro-
vided in heat exchanger CONDENS.
The setup in case III and IV is similar to case V
and VI, with the difference that case III and IV have
only one flash tank.
HT1
C2 4
HT2

azeotrope and the second step is to remove the re- D2

maining water creating anhydrous propionaldehyde. C1 MF

G1 FL2
FL1
G4

R1
L2
FEEDR2
Simulations
A number of different setups containing heat ex- L1 HT4

changers, flash tanks and in some case a distillation FL4

G3
column have been simulated. The system has been HT3
FL3
simulated in Aspen Plus. The UNIFAC-model was
used to describe the liquid-vapor interactions. The L3
L4 B1

reason of choosing the UNIFAC-model instead of

Figure 2 schematic figure of the whole system used in the
simulation for case VII and VIII.

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The setup for these cases is a bit different from
the previous cases. The big difference is that these
cases have no distillation column; instead there are
four flash tanks.
Adsorption
The product stream from the first separation step,
which was simulated in the previous section, is
leaves the system as a gas and it would be beneficial
if it could leave the adsorption step in the same con-
dition since the second hydrogenation reactor re-
quires a gas feed.
The remaining water in the product stream is go-
ing to be removed by adsorption on zeolite. The
anhydrous product stream is then fed to the second
hydrogenation reactor.
The main purpose of the experiment is to inves-
tigate if anhydrous propionaldehyde is possible to
produce through gas adsorption on zeolites. Further
if anhydrous propionaldehyde is received, a concen-
tration profile and breakthrough curve is going to be
retrieved. Information from the breakthrough curve
is then going to be used to estimate the size of the
adsorption column needed in the process.
Materials and Methods
The propionaldehyde solution has to be evapo-
rated and then led through the adsorption bed. After
that the gas has to be condensed and collected before
it could be analysed. The setup that was used is
explained and shown in figure 3.
with nitrogen. The nitrogen is used as a carrier gas
which will secure an even flow of gas through the
zeolite bed. Evaporated propionaldehyde and nitro-
gen is feed to an adsorption column packed with
zeolite. The zeolite used in the experiment was de-
veloped and produced by Rohm and Haas, originally
intended to produce anhydrous ethanol. The adsorp-
tion column is a glass cylinder with an inner diame-
ter of 22 mm surrounded by a mantel, where tem-
pered water is circulated to keep the adsorption
column at a constant temperature. The temperature
in the adsorption column was set to 52C. When the
gas has passed through the zeolite bed, it was led
through a condenser where propionaldehyde con-
denses and the liquid product is then collected. The
space velocity through the zeolite bed was set to be
1 cms-1 containing a 50/50 volume relation between
the sweep gas (nitrogen) and evaporated propional-
dehyde. The collected samples were analysed using
a gas chromatograph (Varian 3800).
Results
Simulation
The simulated systems are evaluated based on
their efficiency to separate propionaldehyde both on
mass and concentration. The efficiency is defined as
shown in equation (1) and (2)
CH 3CH 2 CHOmass
mass = (1)
EnergyOutput
CH 3CH 2CHOconc
conc = (2)
EnergyOutput

The product stream from the simulation for each

case and their efficiency is presented in table 3.

Table 3 shows the composition of the product stream

and the cooling demand for each case.
Case III IV V VI VII VIII
Temperature
91.5 90.7 91 90 46 36
(C)
Hydrogen (kg) 1.74 3.47 1.74 3.47 1.74 3.47
Water (kg) 0.59 0.65 0.54 0.53 0.36 0.39
Propionaldehyde
9.99 9.99 10.0 10.0 9.42 9.43
(kg)
Propionaldehyde
94.4 93.9 94.9 94.9 96.3 96.1
(wt %)
EnergyOutput
56.20 57.11 56.25 56.53 59.55 61.21
(kW)
mass 0.1778 0.1749 0.1778 0.1769 0.1582 0.1540
Figure 3 schematic figure of the adsorption arrangement
that were used in the adsorption experiment. conc 0.0168 0.0164 0.0169 0.0168 0.0162 0.0157
The evaluation showed that case V has the high-
With one 50 ml syringe pump (kD Scientific) est efficiency for the cases with a distillation column
and one flow regulator (Brooks 5850), the flow of and case VII for the cases without a distillation col-
propionaldehyde/water and nitrogen were controlled. umn. A higher hydrogen flow in the feed has very
The flow regulator was controlled by a voltaic box. little impact on the system. The cases with a distilla-
The liquid stream is fed to an evaporator, but be- tion column have none or very small loss of product
fore the stream enters the evaporator, it is mixed in the waste stream while the cases with only flash

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tanks have a loss of about 5.5 wt % of ingoing prod- be equal for all experiments. An average number of
uct. N is chosen N=7.9 which gives a k=1.58 s.
The adsorption isotherm is plotted in figure 5.
Table 4 Result from the breakthrough curve adjust-
ment for each experiment
Langmuir isotherm
Start Conc. 0,1
Exp. Zeolite(g) t1/2(min) N
(wt % H2O)
1 0.111 23.6 55.4 5.8 0,08

2 0.07 23.6 80.5 8.5

q (kg/kg)
0,06

3 0.13 23.6 72.1 6.6

0,04
4 0.07 11.4 54.5 7.6
0,02
5 0.06 11.4 60.4 8.5

6 0.03 11.4 81.3 10.5 0

0 2 4 6 8 10

PH2O (kPa)

Adsorption Figure 5 Langmuir isotherm

A number of experiments with different water
content in the feed and different bed sizes of the
zeolite were performed.
The results from each experiment were plotted The adsorption isotherm is described by equation
and the result from experiment 1 is present in figure 5, which is a Langmuir isotherm.[7]
4. K PH O
2 (5)
q = qmax
1 + K PH O
23.6 g Zeolite, 11.1 wt % water vapor 2
1
The adjustment gave a K=0.49(kPa)-1 and a
qmax= 0.1; qmax is assumed to be constant in the cur-
0,8 rent temperature interval and the K constant tem-
perature dependence is adjusted with vant Hoffs
0,6 equation 6.[8]
0
C/C

H
(6)
0,4 RT

K = K0 e
0,2 The experiment is performed at 52 C and H is
the evaporation enthalpy of water at the current
0 pressure. This generates a K0=1.44.10-4(Pa)-1. When
0 20 40 60 80 100 120
this constant is known it is possible to make a rough
t (min)
estimate of a scale up from lab scale. An important
Figure 4 An adjusted breakthrough curve for experiment thing to take into account when estimating a scale
1 with experimental data
up, is the pressure drop over the bed and this is done
using Erguns equation which is shown in equation
The breakthrough curve adjustment is made us- 7.[9]
ing equation 3 a first order lumped model; used as
an approximation of the dispersion model.[6] 150
fp = + 1.75 (7)
Re p
y t (3) where fp and Rep are defined as
ln = N 1
1 y t1 p D p 3 D pVs
2 fp = Re p =
L Vs2 1 (1 )m
and
Where
k V0 With this information from the experiment a
N= (4) rough size estimate of the adsorption column needed
Dp in case V and VII is performed. To make the optimi-
The results from the curve fit for each experi- sation easier, some restrictions are taken into ac-
ment is shown in table 4. count to find a suitable setup for the adsorption
k in equation 4 is a constant and because the ex- columns. The restrictions are a maximal pressure
periments are performed with the same space veloc- drop at 0.02 bar, a maximal height at 3 m and a
ity (V0) and the diameter (Dp) of the zeolite, N water concentration lower than 0.01 wt %. An opti-
which is the number of mass transfers units, should

-4-
misation to find the longest cycle time which fulfil
these restrictions is performed.
The result is shown in table 5.
Table 5 Adsorption column properties from the scale
up estimate for case V and VII.
Case V VII
Volume flow (m3/h) 6.339 5.507
Space velocity (m/s) 0.077 0.119
Temperature (C) 90.7 46
Height (m) 3.003 2.982
Diameter (m) 0.170 0.127
Pressure drop (mbar) 2.54 3.77
Mass zeolite (kg) 16.20 8.96
Wt % propionaldehyde 0.9999 0.9999
Cycle time (min) 58 96
The optimisation showed that with these restric-
tions, the first restriction to get its maximum value
was the height of the adsorption column. The tem-
perature was the major key to receive a long cycle
time.
Conclusion/Future work
To make the biodiesel production more eco-
nomic and increase the competitiveness against
other fuels, some profit has to come from the crude
glycerol. One way of solving this problem is by
using the process developed by Biofuel- Solution in
Malm. The process transforms glycerol to 1-
propanol, which could be sold as a fuel or as an
industrial chemical. Two similar separation systems
needed in the process have been developed which
separate propionaldehyde from the water / organic
mixture. One of the design system have a very low
loss of product, but with a quite more complex and
expensive configuration compare to the other which
has an easier and cheaper configuration but with a
5.5 % loss of product on weight basis. Adsorption on
zeolite is used in both the systems to remove the
remaining water and creating an anhydrous propion-
aldehyde stream. Adsorption of water on zeolite
seems very promising when a high grade of purity is
required. However future investigation about the
adsorption is required to make a more accurate esti-
mate of the required adsorption column. Another
thing that needs to be investigated is the regenera-
tion, which not has been investigated.
V0 Space velocity (ms-1)
Dp Zeolite particle diameter (m)
k Lumped dispersion coefficient (s)
q Adsorption loading (gH2O/gzeolite)
qmax Maximal adsorption loading
MH2O Mole mass water (kgkmol-1)
G Total mole flow (kmols-1)
PH20 Partial pressure water (kPa)
Mzeolite bedTotal mass of the zeolite (kg)
K Adsorption constant ((kPa)-1)
H Evaporation enthalpy water
(kgkmol-1)
T Temperature (K)
R Ideal gas constant (m3PaK1mol1)
bulk Bulk density zeolite bed (kgm-3)
Fluid density (kgm-3)
m Dynamic viscosity (Pa.s)
Vs Gas flow through the adsorption column
(ms-1)
Void fraction Bed porosity
L Length of the bed (m)
p Pressure drop (Pa)
References
[1] WO/2008/144448 GAS PHASE PROCESS FOR
MONOALCOHOL PRODUCTION FROM GLYCE-
ROL
[2] Karan Bansal, Jonathan McCrady, Alan Hansen and
Kaustubh Bhalerao (2008)Thin layer chromatography
and image analysis to detect glycerol in biodiesel
Department of Agricultural and Biological Engineer-
ing, University of Illinois.
[3] J,Gmehling, U,Onken, W,Arlt Vapor-Liquid equilib-
rium Data collection Vol 1 Part 1a
[4] Theodore Q,Eliot, Tulsa, Okla, assignor to Stanolind
Oil and Gas Company, Tulsa, Okla, a corporation of
Delaware (1950), U,S Patent
[5] Nilsson D,, Etanol frn sockerbetor, Frstudie om
mjligheterna till storskalig produktion i
Blekinge, Lnsstyrelsen i Blekinge ln, rapport 7, 2006
[6] Personal communication: Hans T Karlsson, Depart-
ment of chemical engineering University of Lund
[7] Warren L, McCabe, Julian C, Smith and Peter Harriott
(2005) Unit operations of chemical engineering (7th
edition).
[8] Atkins P, De Paula J, Physical Chemistry 2006

[9] R.H. Perry, D.W. Green and J.O Maloney Perrys

Chemical Engineers Handbook (7th edition). 1997
Nomeclature
Received for review March 17, 2009
N Number of mass transfer units
t Cycle time (min)
t1/2 Time when c/c0=0.5
y Quota c/c0

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