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Department of Chemical Engineering & Chemical Technology, Imperial College of Science, Technology and
Medicine, Prince Consort Road, London SW7 2BY, United Kingdom
This paper describes a new process for the recovery of aromatic, cyclic, and aliphatic amines
from aqueous streams, the membrane aromatic recovery system (MARS). The process comprises
a stripping vessel, where the amines are extracted through nonporous membranes and
concentrated into an HCl solution as hydrochloride salts, and a two-phase separator in which
the solution from the stripping vessel is separated into an aniline-rich phase and an aqueous
phase by adjusting the pH to caustic conditions with NaOH. In this study, aniline was recovered
from a synthetic wastewater using silicone rubber tubing as the membrane. The stripping-
solution temperature was 50 °C, and the HCl concentration was 10.45 wt %. After recovery, an
organic-rich product phase containing 96.5 wt % aniline and 3.5 wt % water was obtained. The
overall mass-transfer coefficients (OMTCs) for a range of amines were also investigated to
demonstrate the wide potential application of MARS technology.
Publication Date (Web): May 7, 2002 | doi: 10.1021/ie010746l
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Theoretical Background
Acid-Base Equilibrium. Amines are weak bases.
Acid-base reversible reactions in water are proton-
transfer reactions, described as Brönsted equilibria
Publication Date (Web): May 7, 2002 | doi: 10.1021/ie010746l
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[R-NH3][H3O+]
Ka ) (1)
[R-NH4+]
preliminary calculations show that membrane resis- romethane containing chlorobenzene as the internal
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tance of the relatively thick (500 µm) silicone rubber standard. One microliter of this extracted solution was
tube dominates Kov, and eq 5 can be simplified to injected onto the GC the column. The program ran for
2 min at 60 °C, followed by an increase of temperature
ro ro to 240 °C at a rate of 20 °C min-1. The coefficient of
ri ln
ri ln
1 ri ri variation of this assay (from five independent measure-
) ) (6) ments) was less than 5% at a concentration of 300 mg
Kov DK P
L-1. TOC was measured using a TOC-5050 analyzer
(Shimadzu Corporation, Kyoto, Japan). The coefficient
This assumption is borne out for the conditions
of variation of this assay (from three independent
employed by subsequent experimental data. In the case
measurements) for each sample was less than 2%. The
analyzed, the wastewater flows inside the membrane
water concentration in the recovered aniline phase was
tubes in plug flow, and a well-mixed stripping solution
measured using Karl Fisher titration. Each sample (2.5
is present on the outside of the tubes. Using eq 4 at
µL) was injected in a Mettler DL37 KF Coulometer
steady state, a differential mass balance can be derived,
machine. The coefficient of variation of this assay (from
which, upon integration along the membrane tube,
five independent measurements on each sample) was
yields
less than 5%.
( )
Membrane Material. The commercially available
Cout - CN
s 2πri silicone rubber membrane used in this study is com-
ln )- K L (7)
Cin - CN Fw ov posed of 30 wt % fumed silica and 70 wt % poly-
s
(dimethylsiloxane) (PDMS). The membrane was sup-
( )
Substituting eq 3 into eq 7 gives plied as a tube of 3-mm internal diameter and 0.5-mm
wall thickness by Silex Ltd U.K. The addition of the
CTs fumed silica to the silicone rubber tubing is necessary
Cout - to impart mechanical strength to the membrane.
Fw 1 + 10-pH/Ka MARS Operation. The process was run with an
Kov ) - ln (8) aniline-containing synthetic wastewater. Figure 3 shows
2πriL CTs a schematic diagram of the experimental setup. Table
Cin -
1 + 10-pH/Ka 1 summarizes the main parameters of the system. Using
a peristaltic pump, the wastewater was pumped in a
Materials and Methods single pass though the membrane tube at a constant
flow rate of either 3.4 or 5.5 L day-1, corresponding to
Chemicals and Assays. Organic amines were sup- Reynolds numbers of 30 and 50, respectively. The
plied by Aldrich, U.K., and Lancaster Synthesis, U.K. membrane tube was coiled around a support and
HCl solution (37 wt %) was supplied by BDH Labora- submerged in the stripping solution. Temperature con-
tories, U.K., and NaOH (50 wt %) solution was supplied trol and well-mixed conditions in the stripping solution
by Solutia (U.K.) Ltd. K2HPO4, KH2PO4, and NaCl, were were achieved by connecting a stirred magnetic hot
supplied by Rose Chemicals, U.K. Deionized water was plate to a temperature controller and a temperature
used in all dilutions and solution preparations. Syn- probe. The stripping-solution pH was kept constant via
thetic wastewaters of most of the amines, including a feedback loop. HCl solution was pumped from a
aniline, were prepared by dissolving pure amine in measuring cylinder as required to maintain the pH
deionized water. value in the stripping solution. An overflow outlet in
Organic compound concentrations were assayed using the side wall of the stripping vessel kept the volume
gas chromatography (GC) and total organic carbon inside this vessel constant.
Ind. Eng. Chem. Res., Vol. 41, No. 11, 2002 2769
Figure 3. Diagram of experimental setup: 1, stripping vessel; 2, pH probe; 3, temperature probe; 4, peristaltic pump; 5, pH controller;
Publication Date (Web): May 7, 2002 | doi: 10.1021/ie010746l
6, tank for HCl solution; 7, temperature controller; 8, collector; 9, magnetic stirrer hotplate; 10, magnetic bar; 11, membrane tube; 12,
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tank for wastewater containing dissolved aniline; 13, tank for clean water; 14, peristaltic pump.
The stripping-solution overflow was collected in a reach a steady state at a value 43.6 times higher than
measuring cylinder. It was periodically removed to a that at the wastewater inlet (218.5 vs 5 g L-1), allowing
separating funnel, where the pH was adjusted to for high recovery efficiencies. The value of 218.5 g L-1
alkaline conditions using 50 wt % NaOH, and the is the average value of the aniline concentrations in the
resulting two-phase mixture was allowed to stand stripping solution at steady state over the last 51 days
overnight to separate. The aniline-rich organic phase of experiment (with a coefficient of variation of 2.3%
was recovered, and the aqueous-phase underlayer was over 47 points). The outlet concentration showed a
recycled in batches to the untreated-wastewater con- significant effect of stripping-solution pH on the mass-
tainer (number 12 in Figure 3) and passed through the transfer rate. An aniline mass balance on the stripping
membrane to extract any residual dissolved aniline. process was struck for each sampling period, as ex-
Mass-Transfer Tests. A similar apparatus was built pressed below
to measure the OMTCs for a range of amines. Three
independent noncoiled (randomly spaced) membrane Fw∆t(Cin - Cout) ) Vs∆CTs + CTs ∆Vout (9)
tubes were submerged in a single stripping-solution
vessel. The pH was kept below 1 using HCl solution. This mass balance (plotted in Figure 5) compares the
Under these conditions, the un-ionized amine concen- mass of aniline removed from the wastewater to the
tration in the stripping solution was assumed to be zero. mass of aniline accumulating in the stripping solution
In each run, three amines were tested, with a solution and leaving the system via the stripping-solution over-
of each amine being pumped through one of the three flow. The data in Figure 5 show good agreement with a
membrane tubes using a multichannel peristaltic pump deviation below (10%. The organic phase obtained after
regulated to a flow of 5 L day-1. This corresponded to a recovery was composed of 96.5 wt % aniline and 3.5 wt
Reynolds number of 45 inside each 18-m-long tube. % water. No other organic compound was detected by
Mutual Solubility Tests. To study the effect of ionic GC analyses of the recovered organic phase.
strength on the mutual solubility of aniline and water, Effect of pH in the Stripping Solution. The pH
five flasks of 100 mL of aqueous solutions with different in the stripping solution was controlled at value of 1
NaCl concentrations and 20 g of aniline each were during the first 88 days of the experiment. After
prepared. The solutions were mixed overnight at 30 °C. operating at steady state for 32 days, i.e., at a constant
Then, each mixture was transferred to a separating concentration of total aniline in the stripping solution,
funnel, where it was left overnight to phase separate. the pH was then controlled at 2.4 and then at 2, and
The water concentration in the organic phase and the then HCl addition was finally ceased.
aniline concentration in the aqueous phase were then The effect of pH on the mass-transfer rate is shown
measured, and the Na+ and Cl- concentrations in the in Figure 4. It can be seen that an increase of pH in the
aqueous phase were measured by ion chromatography. stripping solution clearly corresponds to an increase in
outlet aniline concentration. According to Figure 2, the
Results and Discussion concentrations of un-ionized aniline in the stripping
solution at pH 1, 2, and 2.4 are 0.05, 0.51, and 0.59 g
Overview of MARS Performance. Figure 4 shows L-1, respectively. Therefore, as stripping-solution pH
the inlet and outlet concentrations in the wastewater increases, the driving force decreases, and the mass-
and the total concentration of aniline in the stripping transfer rate decreases, resulting in the increase in the
solution over 107 days of experiment. The total aniline aniline outlet concentration shown in Figure 4 and
concentration in the stripping solution took 56 days to predicted by eq 7.
2770 Ind. Eng. Chem. Res., Vol. 41, No. 11, 2002
Figure 4. Evolution of aniline concentrations in the inlet, outlet, and stripping solution over time in the MARS process.
Publication Date (Web): May 7, 2002 | doi: 10.1021/ie010746l
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Cin - Cout
ηRemv (%) ) × 100 (10)
Cin
after recovery.
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Effect of HCl Concentration. Acid-base reaction on the OMTCs in the range studied. This is further
stoichiometry requires 1 mol of HCl for each mole of evidence that the OMTC is dominated by membrane
aniline removed from the wastewater. On the basis of resistance. This high membrane resistance for amines
mass balances for aniline and HCl the following equa- is mainly due to the use of a thick membrane (500 µm)
tion can be obtained at steady state and to the fact that hydrophilic amines have relatively
low partition coefficients between the hydrophobic
1000 silicone rubber membrane and aqueous solution,29 e.g.,
CTs (g L-1) ) (12) aniline has a value of 1.8.
1 100 MWHCl
+ Effect of Temperature on Permeability. Aniline,
FAniline CHCl (%) MWAniline 4-chloroaniline, and dimethylamine were selected to
investigate the effect of temperature on the OMTC. The
where FAniline is 1.02 kg L-1, MWHCl is 36.45 g mol-1, OMTCs for these three amines across a 500 µm thick-
and MWAniline is 93.13 g mol-1. ness silicone membrane were measured at 30, 50, 70,
A HCl solution of 10.45 wt % was added into the and 90 °C, and the permeabilities were calculated using
stripping vessel in this study. The total aniline concen- eq 6. For rubbery polymers above their glass transition
tration of 211.5 g L-1 at steady state was calculated temperatures, the effect of temperature on permeability
from eq 12 and showed a good agreement with the can be described by the van’t Hoff-Arrhenius relation-
average observed value of 218.5 g L-1, as shown in ship30
Figure 4.
As shown in eq 12, the higher the HCl concentration
(CHCl), the higher the total aniline concentration in the
stripping solution (CTs ) at steady state. However, as
P ) Ao exp ( )
-Ea
RT
(13)
shown in eq 3, for a given pH, the higher the total It was observed that permeability increases with
aniline concentration (CTs ), the higher the un-ionized temperature, which can lead to significant reductions
aniline concentration (CN s ). A higher un-ionized aniline in membrane area. This is mainly due to the effect of
concentration in the stripping solution (CN s ) reduces temperature on the polymer chains, increasing their
the driving force for mass transfer. On the other hand, movement and membrane-free volume and promoting
the higher the total aniline concentration in the strip- the diffusion of the molecules in the polymer. The
ping solution, the higher the recovery efficiency in the activation energy and preexponential factor were esti-
next stage because of the increased NaCl concentration mated as shown in Figure 10.
and enhanced salting-out after neutralization. There- The activation energy for dimethylamine is twice
fore, the HCl concentration in the HCl solution is a key those for aniline and chloroaniline. The penetration of
parameter for the removal and recovery of aniline, and a penetrant molecule in the membrane depends on
there is an optimum HCl concentration for use in this several factors such as the size and shape of the
process. molecule and the interaction between the membrane
Effect of Hydrodynamic Conditions on Mass material and the molecule. Although dimethylamine is
Transfer. In overall mass-transfer tests, the stripping- a smaller molecule than the aromatic amines, its
solution pH was kept below 1, and the solution was permeability is lower than those of aromatic amines
regularly replaced by fresh HCl solution, so that un- because dimethylamine is more polar (see its water
ionized amine concentration in the stripping solution solubility in Table 2). Although the size of the molecule
was effectively zero. Three compounds were selected to is one of the important factors, in this case, it seems
investigate the effect of film resistance on the waste- that the polymer-penetrant interaction plays the de-
water side, as shown in Figure 9. It can be seen that cisive role.30
Ind. Eng. Chem. Res., Vol. 41, No. 11, 2002 2773
Applicability of MARS to Other Amines. To verify consequently the removal efficiency of aniline from the
the application of MARS to the recovery of other amines, wastewater. Anilinium in the stripping solution was
OMTCs were measured for aniline, 4-chloroaniline, 2,4- accumulated to a high concentration without back-
dichloroaniline, 4-nitroaniline, 4-fluoroaniline, 2,4-dif- extraction to the wastewater side. At steady state, the
luoroaniline, benzyldimethylamine, triethylamine, di- total aniline concentration in the stripping solution was
methylamine, 2,4,6-tris(dimethylaminomethyl)phenol, 6 times higher than the aniline solubility in water and
and dicyclohexylamine. The OMTCs, solubilities, and 43.6 times higher than the aniline concentration in the
acid dissociation constants of these amines in water are wastewater used in this study. These values illustrate
shown in Table 2. Permeability values in silicone the potential of MARS as a concentrating process.
Publication Date (Web): May 7, 2002 | doi: 10.1021/ie010746l
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membrane were calculated using eq 6 and are also The HCl concentration is the key parameter that links
shown in Table 2. the two steps of the process. In the removal step, it
The OMTC of aniline in Table 2 is 1.7 times higher controls the concentration of total aniline in the strip-
than the average value obtained by MARS. This is ping solution. In the recovery step, the higher the
probably because, in the mass-transfer test, the mem- concentrations of anilinium submitted to neutralization,
brane was loosely arranged to ensure good contact with the higher the recovery efficiency. However, the higher
the stripping solution, whereas the membrane in the the total aniline in the stripping solution, the higher
MARS process was tightly rolled around a support, the concentration of un-ionized aniline in the stripping
reducing the effective membrane-stripping solution solution, and consequently, the lower the driving force
interfacial area. Judging from the difference between for extraction. This is a parameter that we hope to
the two values, the effective membrane area in the optimize in future work.
MARS runs was 59% of the total. Note that other Ionic strength, resulting from high concentrations of
differences in the experimental conditions could also be NaCl in the aqueous phase after neutralization, has a
the reason for the differences observed, such as ionic positive effect on the phase separation, decreasing the
strength, stripping-solution concentration (200 g L-1 vs water concentration in the organic phase and the aniline
nearly zero anilinium chloride concentrations), and concentration in the aqueous phase. As the ionic strength
aniline concentration in the wastewater (5 vs 2 g L-1). increases, a recovered aniline phase with a higher purity
A more detailed analysis of the mass transfer across the and an aqueous phase containing less dissolved aniline
film layer at the stripping solution-membrane interface are obtained.
and of the effect of the reversible and instantaneous The MARS process couples detoxification and recov-
reaction is the subject of ongoing work. ery. It is capable of achieving high recovery efficiencies,
It can be seen that benzyldimethylamine, dicyclo- and producing a relatively pure stream of recovered
hexylamine, and triethylamine have high OMTCs, so organics. It is simple, stable, and easily operated in a
they can be relatively easily removed from wastewaters continuous configuration because of the use of non-
using MARS. Although aniline and all of the haloge- porous membranes. It has low energy requirements
nated anilines have intermediate mass-transfer rates, because it exploits the basicity of amines to produce a
it could be difficult to recover 4-nitroaniline as it has driving force based on the chemical energy contained
low permeability, and almost impossible to recover in HCl and can be carried out under conditions of
dimethylamine and 2,4,6-tris(dimethylaminomethyl)- pressure and temperature that are near ambient
phenol. throughout all items of equipment. MARS has been
To maintain a high mass-transfer driving force, it is shown to be promising for industrial application to the
necessary to keep the stripping solution at a pH recovery of a wide range of amines beyond aniline.
significantly lower than the pKa. For compounds with
low pKa’s, such as 2,4-dichloroaniline and 4-nitroaniline, Acknowledgment
it might be hard to maintain this condition using This work was funded by the U.K. Engineering and
silicone rubber membranes because of their susceptibil- Physical Sciences Research Council (EPSRC), Grant GR/
ity to acid attack. L93553. F.C.F. acknowledges financial support from
Fundação Para a Ciência e Tecnologia, Grant PRAXIS
Conclusions XXI/BD/21448/99.
MARS has proven to be a successful process for the
removal and recovery of aniline, with a recovered aniline Nomenclature
purity of 96.5 wt %. pH is an important parameter, as Ao ) pre-exponential factor (m s-1)
it controls the driving force across the membrane and C ) concentration of amine (g L-1)
2774 Ind. Eng. Chem. Res., Vol. 41, No. 11, 2002
dx ) short length of membrane tube (m) carbon cathode cell. Part 2: The removal of phenols and related
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Publication Date (Web): May 7, 2002 | doi: 10.1021/ie010746l