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Separation and Purication Technology 145 (2015) 3949

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Separation and Purication Technology


journal homepage: www.elsevier.com/locate/seppur

Experimental and theoretical study on the adsorptive drying of primary


alcohols in a xed bed adsorber
Bernd Burrichter a,, Christoph Pasel a, Michael Luckas a, Dieter Bathen a,b
a
Chair of Thermal Process Engineering, University of Duisburg-Essen, Lotharstrae 1, D-47057 Duisburg, Germany
b
Institute for Energy and Environmental Technology e.V. (IUTA), Bliersheimer Str. 60, D-47229 Duisburg, Germany

a r t i c l e i n f o a b s t r a c t

Article history: In this paper systematic investigations on the adsorptive drying of primary alcohols from methanol to 1-
Received 23 September 2014 hexanol on 3A and 4A zeolites are presented. The focus of the work is laid on the superdrying of these
Received in revised form 6 February 2015 polar solvents in the ppmw-region. In addition to equilibrium data gained in shaker bottle experiments
Accepted 21 February 2015
information regarding the dynamic drying behavior was obtained by breakthrough experiments. The
Available online 6 March 2015
water content in these experiments was monitored online by a transmission photometer. Based on the
experimental data a physical model was developed in order to predict the dynamic drying behavior in
Keywords:
a xed bed adsorber. Most of the investigated systems could be well described by this model.
Adsorptive drying
Adsorption isotherm
Furthermore pore diffusivities of water could be obtained by tting the model to the experimental data.
Fixed bed adsorber The results of this study reveal a clear dependency of the dynamic drying behavior of primary alcohols
Zeolite from the solvent to be dried and the type of zeolite. Small alcohol molecules show signicantly faster dry-
Modeling ing rates than long-chain alcohols and the drying kinetics on a 3A zeolite is much faster than on a 4A zeo-
Alcohols lite. The experimental results were correlated to the molecular dimensions of adsorptives and the size of
the pore openings of the zeolites as well as to the interactions between adsorptive, solvent and adsorbent.
2015 Elsevier B.V. All rights reserved.

1. Introduction on the adsorptive drying of non-polar solvents, like toluene or ben-


zene, in the lower ppm-region [37]. These solvents are easy to dry
Due to technological innovations and more challenging due to their non-polar character and their poor solubility for water.
environmental restrictions there are increasing requirements on On the other hand many publications deal with the drying of polar
raw and operating materials in several industries. In this context solvents, like alcohols, in the percent-region [817]. But up to now
the water content of organic solvents is a critical factor for many there is almost no work done on the adsorptive drying of polar
processes. In new generations of high-compressing engines already organic solvents in the trace humidity region, although superdry-
a few ppm of water lead to an inhomogeneous combustion and an ing is one of the key strengths of adsorptive drying on zeolites.
inefcient operation of the engine. Another example of the dis- Only Goto et al. published adsorption isotherms of ethanol on a
turbing inuence of trace water is the poisoning of Grignard 4A zeolite with water concentrations from 0 to 3000 ppmw [18].
reagents or ZieglerNatta catalysts in multiple chemical reactions This lack of investigations might be a consequence of the high
[1]. An efcient way to remove water from liquids and gases to less experimental effort, which is necessary to do reliable measure-
than 1 ppm is a treatment with oxidic adsorbents like zeolites, sili- ments with highly polar solvents in the trace humidity region.
cas and aluminas. Especially drying on synthetic type A zeolites is For a more detailed literature review it is referred to an earlier pub-
often used in industrial applications. In contrast to its industrial lication of the authors [19].
spreading there are only few publications on the adsorptive drying Therefore systematic investigations on the drying of polar
of organic solvents and no systematic overview on dominant organic solvents on a 3A and 4A zeolite were conducted. In a rst
parameters exists [2]. All published work can mainly be separated step adsorption equilibria for the drying of several primary and
in two categories. On the one hand there are a lot of investigations secondary alcohols as well as acetates were determined in shaker
bottle experiments [20]. Afterwards a laboratory plant for continu-
ous breakthrough experiments was build up in order to study the
Corresponding author. Tel.: +49 203 379 1731; fax: +49 203 379 3119.
kinetic behavior of the drying process in a xed bed. First experi-
E-mail addresses: bernd.burrichter@uni-due.de (B. Burrichter), christoph.pasel@
uni-due.de (C. Pasel), michael.luckas@uni-due.de (M. Luckas), dieter.bathen@ ments to determine optimal operation parameters and to identify
uni-due.de (D. Bathen). dominant parameters of inuence were carried out with the model

http://dx.doi.org/10.1016/j.seppur.2015.02.033
1383-5866/ 2015 Elsevier B.V. All rights reserved.
40 B. Burrichter et al. / Separation and Purication Technology 145 (2015) 3949

Nomenclature

b parameter of the Langmuir equation Rfilm mass transfer resistance in the lm (s)
ci concentration (mgH2O/kgsolution) Rpore mass transfer resistance in the particle (s)
ci;0 inlet concentration (mgH2O/kgsolution) t time (s)
ci;eq equilibrium concentration (mgH2O/kgsolution) uLR supercial velocity (m/s)
D12 molecular diffusion coefcient (m2/s) V_ solu volume ow of solution (m3/s)
DAX axial dispersion coefcient (m2/s) xH2 O mass fraction of water in uid phase
dp bead size of the particles (m) yH2 O mass fraction of water in gas phase
DPore diffusion coefcient in the pores (m2/s) z axial dimension (m)
k overall mass transfer coefcient (s1)
kf lm mass transfer coefcient (m/s) Greek symbols
mADS mass of adsorbent (kg) c1 activity coefcient of water in solvent
H2 O
msolu mass of solution (kg) L void fraction of the bed
p pressure (bar) P void fraction of the particle
ps;H2 O saturation vapor pressure of water (bar) qAds;b bulk density of the adsorbent (kg/m3)
q loading of the adsorbent (gH2O/gadsorbent) qAds;w skeletal density of the adsorbent (kg/m3)
qeq equilibrium loading of the adsorbent (gH2O/gadsorbent) qfluid density of the solvent (kg/m3)
qmon monomolecular loading (gH2O/gadsorbent)

substance isopropanol [19]. In this paper the results of a complete the alcohol and therefore for the interactions of the alcohol mole-
experimental series on the adsorptive drying of primary alcohols cules with the polar type A zeolites. Activity coefcients of water in
from methanol to 1-hexanol on 3A and 4A zeolites in a xed bed the alcohols were determined using the UNIFAC activity coefcient
are presented. model. Molecular dimensions of the alcohols were estimated by
applying an approach of Gounaris and Helmich [2123]. The most
likely coordinates of all atomic nuclei of a molecule were deter-
2. Experimental
mined by an energy optimization of the molecule conguration.
This optimization was done by quantum mechanical calculations
2.1. Materials and methods
using the MM2 method [24]. The coordinates of the molecule were
rotated around its three axes, until the smallest projection is found.
In this study 3A and 4A zeolites supplied by Zeochem AG
The diameter of this projection is the molecular diameter which is
(Uetikon, Switzerland) were used. The material was provided as
relevant for the crossing of the pore openings of a zeolite. The
spherical pellets with a bead size of 1.02.0 mm. More physical
results of these calculations are in good accordance with other
properties are presented in Table 1.
published data [2529].
All alcohols used were of reagent grade and the water, which
The water concentration of the alcohols was measured by a
was given to the storage container to modify the water concentra-
coulometric Karl-Fischer-Titrator (Schott Instruments) in shaker
tion of the solvent, was ultra-puried. In Table 2 basic physical
bottle experiments and by a transmission photometer (Pier
properties of alcohols and the adsorptive water are presented.
Electronic) in dynamic experiments. Additionally the titration was
The relative permittivity is used as a measure for the polarity of
used as reference method for calibration of the transmission pho-
tometer. The accuracy of the Karl-Fischer-Titrator was regularly
Table 1 checked with certied water-standards supplied by Hydranal.
Basic physical properties of the adsorbents.

3A 4A 2.2. Equilibrium experiments


Commercial name Zeochem Z3-01 Zeochem Z4-01
Pore opening () 3.2 3.8 Equilibrium data for the adsorptive drying of organic solvents
Cation K+ Na+ were gained in static shaker bottle experiments. A dened amount
Ionic radius 1.38 1.02 of solvent with a known quantity of water and a dened mass of
dp (mm) 1.02.0 1.02.0
qAds;b (kg/m3)a 0.70 0.69
adsorbent were given to a ask and shaken under constant condi-
L ()* 0.4 0.4 tions (25 C and 150 rph) for up to 7 days until adsorption equilib-
P () 0.55 0.55 rium was reached. Afterwards the water content of the solvent was
a measured again and the loading of the adsorbent was calculated by
Data refers to an adsorber column with an inner diameter of 16 mm.
following mass balance:

Table 2
Basic physical properties of water and alcohols.

Name Molecular formula Relative permittivity Activity coefcient () Molecular diameter ()


20 C () [30]
Water H2O 80.1 1 3.0
Methanol CH4O 33.0 1.761 4.3
Ethanol C2H6O 25.3 2.660 4.7
1-Propanol C3H8O 20.8 3.141 5.2
1-Butanol C4H10O 17.8 3.564 5.2
1-Pentanol C5H12O 15.1 (25 C) 3.934 5.2
1-Hexanol C6H14O 13.0 4.256 5.2
B. Burrichter et al. / Separation and Purication Technology 145 (2015) 3949 41

msolu  ci;0  ci;eq  106 breakthrough experiment can be calculated by integrating the dif-
q 1 ference between the inlet and outlet concentration of the adsorp-
mADS
tive water as a function of time (see Eq. (4)).
During these experiments all work was carried out in a glove-
Z teq
box purged with dry nitrogen to prevent contamination of the V_ solu  qfluid  106
samples by ambient humidity. For an adsorption isotherm approx. q  ci;0  ci dt 4
mADS t0
1520 equilibrium points were determined for each adsorbent/sol-
vent combination. The Langmuir equation was tted to experimen- A comparison of equilibrium points obtained from shaker bottle
tal data by a non-linear regression [31]. and dynamic experiments shows very good accordance between
both methods [19]. However, the shaker bottle method enables
b  ci the determination of equilibrium data with considerably less
q qmon  2
1 b  ci experimental effort. Therefore equilibrium data were mainly deter-
The gas phase concentrations of water were calculated from the mined in shaker bottle experiments.
liquid phase concentrations by extended Raoults law (see Eq. (3)).
By this means a comparison of the drying isotherms of alcohols 2.4. Experimental errors
with the corresponding water vapor isotherm is enabled. The
water vapor isotherms represent the maximum adsorption capac- The experimental error of the equilibrium data from shaker bot-
ity of an adsorbent for the adsorptive water under optimal condi- tle experiments (Eq. (1)) was calculated by Gaussian error prop-
tions with no competitive adsorptive molecules. So by the agation. The relative standard deviation for the loading of the
comparison the extent of unused drying capacity can be quantied adsorbent is between 3% and 6%. It mainly depends on the differ-
and the efciency of drying can be assessed. ence between initial and equilibrium concentration of the adsorp-
tive water.
yH2 O  p
rel:Humidity xH2 O  c1
H2 O 3 The error of the concentration measurements by the Karl-
ps;H2 O
Fischer-Titrator results from the concentration tolerance of the
A comprehensive overview of the experimental procedures for water calibration standard which is given as 3%. The accuracy of
the uptake of equilibrium data is given in earlier papers [19,20,32]. the experimental breakthrough curves is dened by the accuracy
of the photometer. Since the transmission photometer is calibrated
2.3. Kinetic experiments against the titrator, the relative error of the photometer is about 3%
as well.
Information regarding the kinetic behavior of the adsorptive
drying of alcohols has been obtained from dynamic experiments 3. Physical model
in a xed bed adsorber. Solvent with a known water concentration
is pumped through a stainless steel adsorber (inner diameter: In addition to the experimental work a physical model was
0.016 m/maximum height: 0.25 m) lled with zeolite with a vol- developed to simulate the dynamic behavior of the adsorptive dry-
ume ow of 0.16 l/h. After leaving the adsorber the uid enters ing in the xed bed adsorber. A Dispersed Plug Flow (DPF) model
the measuring cell of the transmission photometer, where the based on the mass balances in the solid and uid phase was used.
water concentration of the efuent is continuously monitored. The corresponding energy balances were neglected due to the
Samples for the Karl-Fischer-Titration can be drawn by a syringe. insignicance of the heat of adsorption when adsorbing traces of
All experiments were carried out at a temperature of 25 C and water from a liquid. The mass transfer through the surrounding
ambient pressure. A process ow chart and a photo of the experi- lm of the adsorbent particle and in the pores of the zeolite was
mental plant are shown in Fig. 1. simplied by using a Linear Driving Force (LDF) approach.
Beside kinetic information equilibrium data can be gained from Additional assumptions were a homogeneous liquid and solid
dynamic experiments as well. The mass of adsorbed water during a phase, no radial gradients inside the column and the absence of

Fig. 1. Flow chart (left) and photograph (right) of the laboratory plant.
42 B. Burrichter et al. / Separation and Purication Technology 145 (2015) 3949

competitive adsorptives. Considering all these simplications the All isotherms are measured in the concentration range from 0 to
mass balances in the liquid and solid phase can be expressed as fol- 2200 ppmw in the liquid phase. Due to the conversion of the water
lows [33,34]: concentration to relative humidity (Eq. (3)) with different activity
coefcients (see Table 2) the concentration range covered on the
@ci @ 2 ci uLR abscissa is different for different alcohols. For this reason in the
Liquid phase : DAX  2 
@t @z L 1  L  P case of methanol drying all equilibrium points are between a rela-
6 tive humidity of 00.7%, while the experimental data for the drying
@ci k  1  L  1  P  qAds;w  10
  of 1-hexanol go up to a relative humidity of 4%. However a conver-
@z L 1  L  P  qfluid
sion of the water concentration only stretches the isotherms and
 qeq  q 5 has no impact on the relative position of the isotherms and the
gap to the water vapor isotherm. Equilibrium data for alcohol dry-
@q ing on 4A zeolites are displayed in the same way in Fig. 3. Langmuir
Solid phase : k  qeq  q 6 parameters and correlation coefcients of the tting are summar-
@t
ized in Table 5.
The overall mass transfer coefcient k of the LDF approach can All adsorption isotherms of water from primary alcohols show
be written in the form of a series connection of the resistances in almost rectangular shapes. The plateau of the isotherm is already
the surrounding lm and in the pores of the zeolite, the latter fol- reached at relative humidities around 0.5%. But with respect to
lowing the approach of Glueckauf [35]. the maximum drying capacity there are signicant differences
2 between the six primary alcohols. Whilst the three long-chain
1 dp dp alcohols 1-butanol, 1-pentanol and 1-hexanol show very high dry-
7
k 6kf 60p  DPore ing capacities of approx. 1516 wt.%, the three short-chain alcohols
exhibit a clearly reduced drying capacity on the 3A zeolite. The
The physical parameters used in this model, the axial dispersion
comparison to the water vapor isotherm illustrates that 1-hexanol
coefcient DAX [36], the lm mass transfer coefcient kf [37] and
and 1-pentanol show no co-adsorption on a 3A zeolite. The drying
the molecular diffusion coefcient of water in the alcohol D12
capacities of these two alcohols almost reach the level of the water
[38], which is necessary to calculate kf , were determined mathe-
vapor isotherm. The uptake capacity for water from 1-butanol is
matically by well-known correlations. In case of the diffusion
slightly reduced. In contrast to the long-chain alcohols the three
coefcient of the water in the pores of the zeolite DPore there is
short-chain alcohols show a signicant gap to the water vapor iso-
no reliable correlation. Therefore the diffusivity of water in the
therm. This clearly proves that primary alcohols up to a chain
pores is used to t the simulations to the experimental results.
length of at least three carbon atoms are able to enter the microp-
For more detailed information regarding the simplifying
ores of a 3A zeolite and to co-adsorb. This nding contradicts the
assumptions, the calculation methods for the parameters and the
published and calculated sizes of alcohol molecules and pore open-
initial and boundary conditions it is referred to [19].
ings of the zeolites [2529]. Those data seem to indicate that alco-
hol molecules are substantially bigger than the pore opening of a
4. Results and discussion 3A zeolite and therefore should be excluded from the micropores
of the zeolite. From the experiments it is evident that data for
4.1. Equilibrium data molecule sizes and pore openings cannot be used to precisely pre-
dict co-adsorption in type A zeolites.
Adsorption equilibria of the drying of primary alcohols from In case of a 4A zeolite the drying isotherms of the four primary
methanol to 1-hexanol on a 3A zeolite are displayed in Fig. 2. alcohols from 1-propanol to 1-hexanol show very similar shapes.
Additionally the water vapor isotherm on a 3A zeolite is shown. The slope at low water concentrations is slightly smaller than on
Experimental data are presented as lled symbols while the tted the 3A zeolite and maximum capacities of approx. 17 wt.% are
Langmuir isotherms are shown as lines. reached. In contrast, ethanol and methanol drying exhibit atter

20

3A
water vapor
loading of the adsorbent [g/100g]

16 1-pentanol
1-hexanol
1-butanol

12

1-propanol
8
ethanol

methanol

0
0 1 2 3 4
relative humidity [%]

Fig. 2. Adsorption isotherms of water from different alcohols on a 3A zeolite.


B. Burrichter et al. / Separation and Purication Technology 145 (2015) 3949 43

20
water vapor
4A
1-butanol

loading of the adsorbent [g/100g]


16 1-pentanol
1-hexanol
1-propanol

12

8
ethanol

methanol

0
0 1 2 3 4
relative humidity [%]

Fig. 3. Adsorption isotherms of water from different alcohols on a 4A zeolite.

isotherms with a signicantly lower uptake capacity for the to 3A zeolite due to a strong interaction between sodium and
adsorptive water. Especially methanol drying on a 4A zeolite yields water.
very poor results. Even with large amounts of adsorbent water con-
tents below 350 ppmw cannot be achieved. Due to this behavior a
description of the drying equilibrium of methanol by a Langmuir-
4.2. Adsorptive drying of primary alcohols in a xed bed adsorber
type isotherm is not possible, wherefore no t can be seen in Fig. 3.
Comparing the drying isotherms of 1-propanol on 3A and 4A
4.2.1. Drying on a 3A zeolite
zeolites reveals the inuence of molecular size and polarity of
Optimal operation conditions were determined in a parameter
the solvent molecules on the adsorption equilibrium. The isotherm
study on the adsorptive drying of isopropanol [19]. According to
of water from 1-propanol on a 3A zeolite clearly proves the
the outcomes of this study a supercial velocity of 0.8 m/h and a
accessibility of the micropores of type A zeolites for 1-propanol
bed height of 12.4 cm were chosen for the 3A zeolite. These set-
molecules. However, since no signicant co-adsorption of 1-propa-
tings result in retention times of the solvent in the xed bed of
nol on the 4A zeolite can be found, the polarity of the solvent must
approx. 3.5 min. The operating conditions of all dynamic runs are
have a dominant inuence on the adsorption equilibrium. The
listed in Table 6.
absence of co-adsorption in case of the 4A zeolite is due to stronger
interactions of the polar water molecule with the sites of the more
(a) Concentration dependency
polar 4A zeolite compared to the 3A zeolite. Sodium ions in the
cages of the 4A zeolite have a higher charge density than potas-
All primary alcohols were dried with varying inlet concentra-
sium ions in the 3A zeolite due to a smaller ionic radius (see
tion of water. Exemplary the drying of the short-chain alcohol
Table 1). This change seems to favor interactions between water
ethanol and the long-chain alcohol 1-hexanol are shown in the fol-
and zeolite to a higher degree than interactions between alcohol
lowing gures. Fig. 4 displays the drying of ethanol and Fig. 5
and zeolite and prevent co-adsorption of the alcohol 1-propanol.
depicts the drying of 1-hexanol. Experimentally determined
Another interpretation could be that there are stronger interac-
tions between 1-propanol and 3A zeolite than between 1-propanol
and 4A zeolite. It cannot be clearly decided at this moment which
2000
argument is more relevant. In any case we conclude that molecular
3A
experiment 2000ppmw
simulation 2000ppmw
size determines whether co-adsorption is possible or not, while
experiment 1500ppmw
water concentration [ppm w]

interactions between adsorbent and adsorptive/solvent specify simulation 1500ppmw


the extent of co-adsorption. 1500
experiment 1000ppmw
With regard to the initial slope water adsorption isotherms simulation 1000ppmw

from alcohols on 3A and 4A zeolite exhibit a complex behavior. experiment 500ppmw


simulation 500ppmw
At low concentrations the 3A isotherm is steeper while at higher 1000
concentration the 4A isotherm shows a higher plateau. There are
several theories for this behavior which cannot be discussed in
every detail in this place. The most convincing argument for the
500
steep initial slope on 3A zeolite may be the smaller window aper-
ture decelerating the rate determining step of alcohol adsorption
[20]. Another valid argument to explain the steeper initial slope
may be multi cationguest interactions between the larger potas- 0
0 500 1000 1500 2000
sium ion and water. At higher water concentration water displaces
time [min]
alcohol on the adsorbent which is favored on 4A zeolite compared
Fig. 4. BTCs of water from ethanol on a 3A zeolite with varying inlet concentration.
44 B. Burrichter et al. / Separation and Purication Technology 145 (2015) 3949

2000 reveals that lm diffusion has no relevant impact on the overall


3A
experiment 2000ppmw
simulation 2000ppmw mass transfer coefcient in our liquid adsorption system. Similar
results have already been obtained in previous works [6,17,40].
water concentration [ppmw ]

experiment 1500ppmw
simulation 1500ppmw

1500 experiment 1000ppmw


simulation 1000ppmw (b) Solvent dependency
experiment 500ppmw
simulation 500ppmw
The BTCs of water from all six primary alcohols with inlet con-
1000
centrations of 2000 ppmw water are displayed in the following dia-
grams. In Fig. 6 the experimental data of the dynamic drying of
methanol, ethanol and 1-propanol as well as the results of the
500 theoretical modeling are presented. The drying of the three long-
chain alcohols in a xed bed adsorber is shown in Fig. 7.
Drying of short-chain primary alcohols on a 3A zeolite reveals
0 very steep BTCs with low uptake capacities for the adsorptive
0 500 1000 1500 2000 2500 3000 3500 4000 4500 water. The 12.4 cm long xed bed enables complete drying of the
time [min] alcohols just for a few minutes before the water content of the
efuent rises. In addition the slope of the BTCs shows a clear
Fig. 5. BTCs of water from 1-hexanol on a 3A zeolite with varying inlet
dependency from the solvent to be dried. The length of the MTZ
concentration.
constantly increases with growing chain length of the primary
breakthrough curves (BTC) are shown by symbols, while the lines alcohol. This proves that the drying kinetics decelerates with grow-
represent the results of the simulation. ing molecular dimension of the primary alcohol to be dried. This
Drying of both alcohols reveal longer mass transfer zones (MTZ) nding can be underpinned by pore diffusivities of water in the
and therefore steeper BTCs for higher water concentrations. Similar pores of the zeolite as well. While water in methanol shows a pore
results can be found for the drying of the other four primary alco- diffusivity of 2.0  1011 m2/s diffusivities in ethanol
hols. This proves that the dynamics of the adsorptive drying of (9.0  10 12
m /s) and 1-propanol (4.2  1012 m2/s) decrease con-
2

alcohols in the trace humidity region depends on the adsorptive stantly (see Table 1).
concentration. This nding can be quantied by the results of the
simulation. Diffusivities of water in the pores of the zeolite DPore
increase with growing inlet concentration of the adsorptive (see 2000
Table 6). In addition pore diffusivities are in the area of
water concentration [ppm w ]

1012 m2/s. These small values indicate surface diffusion as the


dominant mass transfer mechanism [19]. Similar results have
1500
already been published by Yamamoto et al. and Goto et al. [17,18].
There are different reasons for this behavior. Firstly the adsorp-
tion equilibrium in case of a concave isotherm and an increasing
1000 3A
concentration gradient has a steepening effect on the BTC.
experiment methanol
Furthermore the adsorption enthalpy decreases at high surface simulation methanol
loadings [33,39] which has a positive impact on the mobility of experiment ethanol
500
the adsorptive molecules. At higher water concentrations high sur- simulation ethanol

face loadings are reached earlier. Therefore the enhanced mobility experiment 1-propanol
simulation 1-propanol
of water molecules leads to increasing diffusivities at higher inlet
0
concentrations of the adsorptive. Although this behavior has not
0 500 1000 1500 2000
yet been seen for the adsorptive drying of organic solvents on zeo-
lites, Kmmel and Worch have already made similar observations time [min]
for the adsorption on mesoporous systems [39]. Fig. 6. Drying of short-chain primary alcohols on a 3A zeolite.
In addition a quantitative analysis of the transport resistances
d
in the surrounding lm of the particle Rfilm 6kp and in the inner
f

d2p
of the zeolite Rpore 60p DPore has been executed in order to demon-
2000
strate the dominating inuence of the mass transfer resistance in
the pores of the zeolite (see Table 3).
water concentration [ppmw ]

Assuming an average particle diameter of 0.015 m and a super-


1500
cial velocity of 0.8 m/h, which result in Reynolds numbers
between 0.2 and 2, the mass transfer resistance in the particle is
at least 100 times higher than in the surrounding lm. This clearly
1000 3A
experiment 1-butanol
Table 3 simulation 1-butanol
Comparison of mass transfer resistances in and around the particle.
500 experiment 1-pentanol
simulation 1-pentanol
Name Rfilm (s) Rpore (s) Rpore =Rfilm ()
experiment 1-hexanol
Methanol 25 2679 108 simulation 1-hexanol

Ethanol 39 5952 153 0


1-Propanol 57 12,755 224 0 500 1000 1500 2000
1-Butanol 67 13,393 200
1-Pentanol 84 17,857 213 time [min]
1-Hexanol 97 20,604 212
Fig. 7. Drying of long-chain primary alcohols on a 3A zeolite.
B. Burrichter et al. / Separation and Purication Technology 145 (2015) 3949 45

Simulations of the BTCs of water from methanol and ethanol are Since no other parameter has been changed in these experi-
in good accordance with the experimental results. In contrast there ments, the reason for the decreased kinetics of alcohol drying must
are huge differences between experiment and simulation in case of be a hindrance of water diffusion by solvent molecules blocking
1-propanol drying. These deviations are a consequence of a signi- the narrow pores of the 3A zeolite. From equilibrium data it can
cant overshoot of the water concentration at the end of the adsor- be seen that small alcohols can pass the pore openings of the 3A
ber. After approx. 1000 min the water concentration of the efuent zeolite. With increasing molecular size the probability increases
exceeds the inlet concentration by about 120 ppmw due to a subse- that a solvent molecule blocks a pore opening. This reduces the
quent displacement of adsorbed water through alcohol molecules. velocity of water diffusion considerably. Both methanol and etha-
Since the theoretical model assumes a single component adsorp- nol are small enough to move almost freely through the narrow
tion with no competing adsorptives a sufcient modeling of this pores of a 3A zeolite. Therefore they do not hinder water diffusion
effect is not possible. The subsequent displacement of water will markedly. This is the reason for signicantly higher pore diffusivi-
be discussed more detailed later on. ties of water in case of methanol and ethanol drying.
The BTCs of water from the three long-chain primary alcohols Long-chain primary alcohols, like 1-pentanol or 1-hexanol,
on a 3A zeolite exhibit a similar pattern. The drying capacity is show almost no co-adsorption on a 3A zeolite. This leads to the
nearly equal in all three cases and much higher than for short- assumption, that water removal from these solvents should be
chain primary alcohols. This nding is in line with the results of much faster due to the absence of alcohol molecules in the microp-
the shaker bottle experiments. In the rst 4 h the efuent concen- ores of the zeolite. However, water diffusion in case of drying these
tration remains almost constant at approx. 50 ppmw. Humidities non-adsorbing alcohols is further decelerated. This nding sug-
below 50 ppmw cannot be achieved due to marginal short circuit gests that already a hindrance of water diffusion through compet-
ows in the small xed bed with a length of 12.4 cm. The incom- ing alcohol molecules at the entrance of the microporous system of
plete drying at the beginning of the experiment is also the reason the type A zeolites is responsible for the reduced kinetics of the
for small deviations from the simulation, which predicts a com- process.
plete drying for the rst liquid passing the adsorber. In order to learn more about the behavior of solvent molecules
Regarding the kinetic behavior there are only small differences in the inner area of type A zeolites gravimetric uptake measure-
between the three long-chain alcohols. However, the trend toward ments of pure ethanol and 1-hexanol vapors on 3A and 4A zeolites
faster kinetics in case of smaller solvents molecules can be con- were executed. Ethanol and 1-hexanol were chosen as representa-
rmed by the BTCs. The MTZ of 1-butanol drying is slightly shorter tive of short-chain and long-chain alcohols, respectively. Results of
than in case of 1-pentanol, which is again steeper than the MTZ of these experiments are shown in Fig. 9.
water from 1-hexanol. Pore diffusivities obtained from the sim- Sorption isotherms of ethanol exhibit a sharp increase at low
ulation conrm this nding (see Table 6), although the dependency partial pressures and a relative at plateau at 9 resp. 11 wt.% for
is much weaker than in case of the three short-chain primary 4A and 3A zeolites. High uptake capacities at low partial pressures
alcohols. clearly prove a lling of the micropores of the type A zeolites. In
Although there are deviations between simulations and experi- contrast to ethanol 1-hexanol shows very poor adsorption rates
mental results in some cases the simulations still reect the gen- at low relative saturations. At relative saturations between 0%
eral shape of the BTCs satisfactory. Therefore the comparison of and 55% only 12 g alcohol adsorb per 100 g of zeolite. The uptake
different simulations and pore diffusivities is considered to be jus- of 1-hexanol rises rapidly at a relative saturation of 60%, what indi-
tied. In Fig. 8 the modeled BTCs of all six primary alcohols on a 3A cates capillary condensation of 1-hexanol in the meso- and
zeolite are shown in one diagram. By this gure the dependency of macropores of the zeolites. This is clear evidence that at higher
the dynamic drying behavior from the solvent becomes obvious. alcohol concentrations at least the supply pores of the zeolite
Besides the uptake capacity for water the length of the MTZ, which and the entrances to the microporous part of the zeolite are lled
is characteristic for the kinetics of the drying, is clearly depending with solvent molecules, even in case of big, non-adsorbing sol-
on the solvent. With every additional methyl group of the primary vents. The interpretation of the small amount of adsorbed alcohol
alcohol the BTC of water from the particular alcohol becomes shal- at low concentrations is difcult. On the one hand the small alcohol
lower, what indicates a slower kinetics of the drying process. uptake could show few molecules which were able to enter the

16

2000
loading of the adsorbent [g/100g]
water concentration [ppmw ]

12
1500 3A
methanol

ethanol 8
1000
1-propanol

1-butanol ethanol 3A
4
500 1-pentanol
ethanol 4A

1-hexanol 3A
1-hexanol
1-hexanol 4A
0 0
0 500 1000 1500 2000 0 10 20 30 40 50 60 70 80 90 100
time [min] relative saturation [%]

Fig. 8. Comparison of the adsorptive drying of all six primary alcohols on a 3A Fig. 9. Adsorption isotherms of pure ethanol and 1-hexanol vapors on 3A and 4A
zeolite. zeolites.
46 B. Burrichter et al. / Separation and Purication Technology 145 (2015) 3949

entrances of the micropores of the zeolite. Another explanation than in the nal state of equilibrium. Due to the absence of the
could be a monolayer in the mesopores of the zeolite. slowly diffusing 1-propanol molecules the temporary equilibrium
For ethanol as well as for 1-hexanol uptake capacities on the 3A is very close to the water vapor isotherm (see Fig. 10). After a cer-
zeolite are approx. 20% higher than on the 4A zeolite. This nding tain time 1-propanol molecules reach the adsorption sites as well
is surprising, because both zeolites consist of the same zeolite and replace water molecules according to the nal state of equi-
structure and just the monovalent cations are changed from librium. This leads to the characteristic overshot of the water con-
sodium (4A) to potassium (3A). Therefore the 4A zeolite should centration in the efuent in case of 1-propanol drying.
exhibit a slightly higher uptake capacity due to the higher charge Bigger alcohol molecules, e.g. 1-butanol, diffuse even more
density of the sodium ions (see the water vapor isotherms). This slowly in the microporous part of the zeolite than 1-propanol.
issue could not be properly answered within this work. However, But in contrast to 1-propanol, these alcohols are not able to co-ad-
experimental artifacts can be excluded due to reproduction mea- sorb on the zeolite in a noticeable amount. They are not polar
surements. Knowing the pore size distribution would be helpful enough to displace water molecules from their adsorption sites
to better understand these ndings. However volumetric measure- even though their concentration is much higher than the water
ments of nitrogen sorption in a BET apparatus to calculate a pore concentration. Therefore the temporary equilibrium in the xed
size distribution of 3A and 4A zeolites are a challenging problem bed is next to the nal state of equilibrium and no subsequent dis-
because of very slow kinetics in the microporous system at 77 K. placement occurs.
Nevertheless the results of the alcohol sorption experiments Smaller alcohol molecules, like ethanol, are polar enough to
underline the explanation for the slower drying kinetics of primary occupy a signicant amount of the adsorption capacity. However,
alcohols with increasing chain length. Alcohol molecules blocking these molecules are sufciently small and mobile to diffuse almost
the narrow pores of the zeolite may hinder water diffusion, leading as fast as water and reach the adsorption sites at the same time as
to smaller pore diffusivities of the water and slower drying rates. In water molecules. For this reason even in xed beds with very short
addition the drying of long-chain, non-adsorbing alcohols indicate contact times a temporary equilibrium is achieved which is similar
that already a hindrance of water diffusion through alcohol mole- to the nal equilibrium.
cules at the entrances to the micropores of the zeolite may be deci- Subsequent displacement of adsorbed water molecules through
sive for the velocity of the whole drying process. 1-propanol molecules is enabled by a large excess of solvent mole-
cules, a relatively high polarity of the solvent and a signicantly
(c) Displacement of adsorbed water through alcohol molecules slower diffusion of the solvent compared to the water in the nar-
row pores of the zeolite.
Subsequent displacement of adsorbed water molecules through
alcohol molecules in case of 1-propanol drying is at rst unex- 4.2.2. Drying on a 4A zeolite
pected due to the much higher polarity of the water compared to Results for the dynamic drying of primary alcohols on a 4A zeo-
1-propanol (see relative permittivity in Table 2). However, since lite are displayed in the following diagrams. Fig. 11 shows experi-
there are only traces of water in the alcohol, 1-propanol is able mental results and simulations for the drying of the three short-
to occupy approx. half of the uptake capacity of the zeolite in state chain alcohols. The drying of 1-butanol, 1-pentanol and 1-hexanol
of equilibrium (see Fig. 2). Furthermore it has to be considered that is presented in Fig. 12. The dynamic runs were carried out in the
in case of contact times of 3.5 min in a 12.4 cm long xed bed same experimental plant as in case of 3A drying. Compared to 3A
adsorber water breakthrough curves at the end of the adsorber dis- zeolite measuring of complete BTCs required a longer bed length
play just a temporary equilibrium. Equilibrium state in the xed of 23.7 cm.
bed is not attained until the inlet and outlet concentrations of In contrast to the drying on a 3A zeolite a subsequent displace-
the adsorptive water are equal for a longer period of time. ment of adsorbed water by ethanol can be seen. Displacement of
If contact times in the xed bed are very short, diffusion veloci- water by 1-propanol on a 4A zeolite is not possible because 1-pro-
ties of the participating substances will be crucial for the tempor- panol shows no co-adsorption on the 4A zeolite and hence no tem-
ary equilibrium. In contrast to small and mobile water molecules porary equilibrium occurs (see Fig. 3). For this reason a description
long-chain alcohol molecules are more bulky. Hence they show of the BTC of water from ethanol by the physical model is not suc-
signicantly slower diffusion rates in the narrow pores of type A cessful, while drying of methanol and 1-propanol is in good agree-
zeolites. As a consequence 1-propanol molecules need much more ment with the model.
time to reach the adsorption sites than fast diffusing water mole- Displacement of water by ethanol molecules seems to be a con-
cules and all adsorption sites are captured by water molecules at sequence of signicantly decelerated ethanol diffusion in compar-
rst. In this temporary equilibrium much more water is adsorbed ison to the 3A zeolite. In addition water diffusion must be less

Fig. 10. Displacement of adsorbed water by alcohol molecules in case of a 3A zeolite.


B. Burrichter et al. / Separation and Purication Technology 145 (2015) 3949 47

2000 2000

water concentration [ppm w ]


water concentration [ppm w ]

1500 1500 4A
methanol

1000 4A 1000
ethanol

1-propanol
experiment methanol
simulation methanol
1-butanol

500 experiment ethanol 500


simulation ethanol 1-pentanol

experiment 1-propanol 1-hexanol


simulation 1-propanol

0 0
0 500 1000 1500 2000 2500 3000 3500 0 500 1000 1500 2000 2500 3000 3500
time [min] time [min]

Fig. 11. Drying of the short-chain primary alcohols on a 4A zeolite. Fig. 13. Comparison of the adsorptive drying of all six primary alcohols on a 4A
zeolite.

decelerated compared to the diffusion of ethanol. The variation of longer. The calculated diffusivities of water in the pores of the 4A
the pore opening between 3A and 4A zeolite cannot be the reason zeolite deliver similar results. Pore diffusivities become smaller
for the slower ethanol diffusion, because pore openings become with increasing chain length of the alcohol (see Table 6). The rea-
larger. Therefore changed interactions between adsorptives and son for this behavior is the same as in case of the 3A zeolite.
zeolite due to the modication of cations in the zeolite framework Solvent molecules, which are blocking the micropores of the zeo-
seem to be the cause for this behavior. Both adsorptives (water and lite and their entrances, hinder water diffusion and lead to smaller
alcohol) show slower diffusion rates on the 4A zeolite due to more pore diffusivities. Due to the higher probability that bigger mole-
intensive interactions with the sodium ion with its higher charge cules get stuck in a narrow pore opening the diffusivities of water
density (see also discussion in the next Section 4.2.3). The reason are lower in case of drying long-chain alcohols than for small alco-
why ethanol diffusion is more decelerated than water diffusion is hol molecules.
not yet known.
Again dynamic drying of primary alcohols on a 4A zeolite is 4.2.3. Comparison of 3A and 4A zeolite
dependent on the chain length of the alcohol to be dried. As already The comparison of the adsorptive drying of 1-pentanol on a 3A
observed in the shaker bottle experiments the alcohols from 1-bu- and a 4A zeolite is exemplary displayed in Fig. 14. In order to guar-
tanol to 1-hexanol reveal almost the same high drying capacity, antee a comparability of the BTCs both experiments are carried out
whereas the BTC from 1-propanol is slightly shifted leftwards on in xed bed with a bed height of 23.7 cm.
the x-axis. Ethanol and methanol coadsorb signicantly on the While the mass of adsorbed water from 1-pentanol is almost
4A zeolite as well. In contrast to the adsorption equilibrium the equal for both zeolites there are signicant differences regarding
kinetics shows a reverse dependency. While methanol shows the the shape of the BTCs. On a 3A zeolite a complete drying of the
steepest BTCs, the kinetics of drying is much slower in case of alcohol is achieved for almost 300 min and afterwards a relatively
longer primary alcohols. sharp MTZ follows. In contrast on 4A zeolite 1-pentanol can be
In order to enable a detailed comparison of the dynamic drying dried to water concentrations below 50 ppmw just for a few min-
of all six primary alcohols on a 4A zeolite the simulations of the utes. The MTZ is much atter and takes almost the whole length
drying of all alcohols with an initial water concentration of of the xed bed of 23.7 cm. This proves that the kinetics of drying
2000 ppmw are displayed in Fig. 13. With increasing chain length on the 4A zeolite is much slower than on the 3A zeolite. Similar
the MTZ of the dynamic water removal becomes subsequently results can be observed for the drying of all other alcohols

2000 2000
water concentration [ppmw ]
water concentration [ppmw ]

1500 1500

1000 4A 1000
experiment 1-butanol
simulation 1-butanol
experiment 1-pentanol 3A
500 experiment 1-pentanol
simulation 1-pentanol
500 simulation 1-pentanol 3A

experiment 1-hexanol experiment 1-pentanol 4A


simulation 1-hexanol simulation 1-pentanol 4A

0 0
0 500 1000 1500 2000 2500 3000 3500 0 500 1000 1500 2000 2500 3000 3500
time [min] time [min]

Fig. 12. Drying of the long-chain primary alcohols on a 4A zeolite. Fig. 14. Adsorptive drying of 1-pentanol on 3A and 4A zeolites.
48 B. Burrichter et al. / Separation and Purication Technology 145 (2015) 3949

Table 4 this case two other effects are more important. On the one hand
Comparison of pore diffusivities of water on 3A and 4A zeolite. the sodium ions with their higher charge density compared to
Solvent DPore 3A (m2/s) DPore 4A (m2/s) the potassium ions in the 3A zeolite lead to more intensive interac-
Methanol 11
2.0  10 3.0  1011 tions of the adsorbent with adsorptive molecules. This results in
Ethanol 9.0  1012 6.0  1012a slower diffusion rates of polar molecules on the 4A zeolite in
1-Propanol 4.2  1012a 2.0  1012 general.
1-Butanol 4.0  1012 1.6  1012 On the other hand more solvent molecules are able to enter the
1-Pentanol 3.0  1012 1.2  1012
1-Hexanol 2.6  1012 1.05  1012
micropores of the 4A zeolite due to its bigger pore openings. For
this reason the hindrance of water diffusion through blocking alco-
a
Poor accordance between experiment and simulation due to subsequent dis- hol molecules is slightly increased in comparison to the 3A zeolite.
placement of adsorbed water.
This results in lower pore diffusivities of the water and atter BTCs.
A combination of both effects will be responsible for slower dry-
ing rates on the 4A zeolite. In order to dene the dominant
Table 5 parameter of inuence more detailed investigations on the diffu-
Fitting parameter of Langmuir isotherms. sion of molecules in the inner of type A zeolites would be
Alcohol Zeolite qmon (g/100 g) b (kg/mg) R2 ()
necessary.
Methanol 3A 2.27 0.00542 0.942
Methanol 4A No Langmuir t possible 5. Conclusions
Ethanol 3A 6.97 0.00528 0.985
Ethanol 4A 6.98 0.00232 0.966 This study reveals that adsorption equilibrium and kinetics of
1-Propanol 3A 9.21 0.02849 0.981
the drying of primary alcohols on 3A and 4A zeolites in the lower
1-Propanol 4A 16.31 0.00690 0.976 ppmw-region signicantly depend on the solvent to be dried and
1-Butanol 3A 13.98 0.02853 0.990
the type of zeolite.
1-Butanol 4A 17.61 0.00726 0.965 The drying of short-chain primary alcohols on 3A and 4A zeo-
1-Pentanol 3A 16.70 0.01634 0.982
lites shows considerably steeper BTCs than the drying of primary
1-Pentanol 4A 17.82 0.00709 0.976 alcohols with a longer aliphatic chain. The reason for the slower
1-Hexanol 3A 15.74 0.02407 0.988
kinetics and the smaller pore diffusivities of water are solvent
1-Hexanol 4A 17.78 0.00758 0.994 molecules, which are hindering the water diffusion. Since bigger
solvent molecules are blocking the narrow micropores of type A
zeolites with a higher probability, water diffusion rates decrease
subsequently with increasing chain length of the alcohol.
investigated in this study. Additionally the modeled diffusivities of However, since the kinetics even decelerates for large molecules
water in the pores of the zeolites support this nding. With excep- like 1-hexanol, which are not able to enter the cages of type A zeo-
tion of methanol as the shortest alcohol of the homologous series lites, the main resistance must already be a blocking of the
the pore diffusion of water is always faster in case of the 3A zeolite entrances to the microporous part of the zeolite by solvent mole-
(see Table 4). cules. This nding can be conrmed by sorption experiments of
At rst these results seem to be surprising. Since 4A zeolites pure ethanol and 1-hexanol vapors on 3A and 4A zeolites.
have slightly bigger pore openings than 3A zeolites, a faster diffu- In comparison of both zeolites much faster kinetics can be
sion of the adsorptives would be expected for the 4A zeolite. But in observed for the drying on 3A zeolite. In this case the effect of

Table 6
Overview of experimental parameters of dynamic experiments.

No. Zeolite ci;0 (ppmw) V_ solu (l/h) uLR (m/h) mADS (g) H (cm) DPore (m2/s)

(1) Methanol
Me-3A 3A 1998 0.16 0.796 17.46 12.37 2.0  1011
Me-4A 4A 1974 0.16 0.796 32.99 23.74 3.0  1011
(2) Ethanol
Eth-3A-1 3A 478 0.16 0.796 17.47 12.37 5.0  1012
Eth-3A-2 3A 980 0.16 0.796 17.46 12.37 7.0  1012
Eth-3A-3 3A 1533 0.16 0.796 17.46 12.37 9.0  1012
Eth-3A-4 3A 1969 0.16 0.796 17.47 12.37 9.0  1012
Eth-4A 4A 2017 0.16 0.796 32.98 23.74 6.0  1012
(3) 1-Propanol
Prop-3A 3A 1979 0.16 0.796 17.47 12.37 4.2  1012
Prop-4A 4A 2005 0.16 0.796 32.99 23.74 2.0  1012
(4) 1-Butanol
But-3A 3A 2018 0.16 0.796 17.46 12.37 4.0  1012
But-4A 4A 2008 0.16 0.796 32.99 23.74 1.6  1012
(5) 1-Pentanol
Pent-3A 3A 1983 0.16 0.796 17.46 12.37 3.0  1012
Pent-4A 4A 2012 0.16 0.796 32.99 23.74 1.2  1012
(6) 1-Hexanol
Hex-3A-1 3A 508 0.16 0.796 17.47 12.37 6.5  1013
Hex-3A-2 3A 991 0.16 0.796 17.47 12.37 1.4  1012
Hex-3A-3 3A 1465 0.16 0.796 17.46 12.37 1.8  1012
Hex-3A-4 3A 1952 0.16 0.796 17.46 12.37 2.6  1012
Hex-4A 4A 2014 0.16 0.796 32.99 23.74 1.05  1012
B. Burrichter et al. / Separation and Purication Technology 145 (2015) 3949 49

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