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ABSTRACT: An environmentally friendly removal method based on a membrane process for the purication of aqueous amine
solution for use in carbon dioxide absorption was analyzed. Two kinds of commercial solvent resistant nanoltration (SRNF)
membranes (Desal-DL and SR100, polymeric) were chosen, and their capabilities in removing three common contaminants from
diethanolamine (DEA) solution were examined. These contaminants that caused foaming of DEA solution include sodium
chloride, sodium sulte, and acetic acid. From the two tested solvent resistant nanoltration (SRNF) membranes, it had been
found that Desal-DL membrane provided promising results and performance that can be an alternative to conventional
separation, including distillation, for purication of amine solution. Experiments were also conducted to test the foaming
tendency and stability of the untreated and treated amine solution. The untreated DEA with sodium sulte had the highest
foaming tendency. However, after NF treatment, there was substantial decrease of the foaming tendency. The results obtained
conrmed the potential of using SRNF-membranes to reduce foaming tendency and stability in DEA solution.
1. INTRODUCTION oxidized fragments (e.g., acetic acid and formic acid), amine
The enhanced levels of anthropogenic CO2 emissions in the degradation products, chemical additives, such as antifoaming
environment during the previous decades are one major agents and a corrosion inhibitor, and some inorganic
contributor to global warming.1 For the last several years, compounds from water.8,9
aqueous amine solution treatments have the technology Systematic studies indicating the foaming behavior of
intended for the removal of acid gas produced by the gas aqueous amine solution have been published. Pauley reported
sweetening industries. Therefore, they can be readily that organic acid and other contaminants increased the foaming
implemented on large-scale in existing industries for the tendency and stability of DEA, monoethanolamine (MEA),
capture of carbon dioxide.2 Aqueous diethanolamine (DEA) methyldiethanolamine (MDEA), and formulated methyldietha-
solutions (usually 25 wt %) are referral solvents intended for nol-amine in amine solution with all contaminants.10 McCarthy
use in many processes.3 The industrial application of this et al.11 observed that organic acid, antifoam, corrosion
solution has encountered several environmental and technical inhibitors, and other contaminants caused the foaming
challenges. Signicant solvent losses take place during the tendency of the DEA solution to increase with increased
absorption and stripping processes. Amines are relatively temperature and pressure. Thitakamol et al.7 systematically
volatile solvents that can change phase from liquid to gas, studied using MDEA, MEA, 2-amino-2-methyl-propanol-1
and subsequently react to yield hazardous compounds in the (AMP), and their combinations to examine the results of
atmosphere.4 Furthermore, one key problem in using amine process parameters on their foaming tendency. Calculating the
solutions is the accumulation of degradation products caused foaminess coecient indicates the gas ow rate and solutions
by irreversible reactions in solvent during the process, as well as volumes. The gas ow rate and the concentration of
the reduction in active DEA content.2 Surface active contaminants used in this study were based on the
degradation products could cause an increase in the foaming recommendations of Thitakamol et al.
problem.5 The current approaches used to overcome the foaming
Foaming is widely encountered in gas sweetening industries phenomena include mechanical ltration, ion exchange,
and typically contributes to critical consequences, including electrodialysis, distillation (solution reclamation), and addition
decreased eciency and area of mass transfer, carryover of of antifoaming agent.2 Filtration is normally performed through
solutions with high absorption further downstream in the plant, a bed of activated carbon, which requires a large amount of
loss (amine solution) of absorption upon increased operation carbon for each ton of carbon dioxide. It also wastes a large
costs, and ooding before the proper time. Foaming takes place amount of the amine solution.1 The use of ion exchange is
during plant start-up and over operation in the absorption and suitable, since degradation product accumulation remains low,
stripping processes.6,7 Foaming can be caused by numerous
chemical contaminants that enter the processing plants with gas Received: July 20, 2015
from feed, water in makeup, or a cooling water leak during the Revised: November 11, 2015
amine solution degradation reactions. These contaminants were Accepted: November 16, 2015
dissolved in hydrocarbon and organic acid from solution- Published: November 16, 2015
Table 1. Solvent Resistant Nanoltration Membranes and Membrane Characteristics Used in the Experiments
Pore Size, MWCOa Membrane property (contact angle, Membrane
Membrane Manufacturer (Da) ) Type of polymer class
Desal-DL GE Osmonics 150300 Hydrophilic (42.8 2.24) Polyamide NF, Dense
TF (Thin Film)
TFC-SR100 Koch Membranes System 200 Hydrophilic (48.3 3.49) TF (Thin Film) composite NF, Dense
polyamide
a
Aqueous solutions.
with concentrations staying in the ppm range. Higher ow rates polarities on the separation performance of the STARMEM
and concentrations have increased the cost and scale of membrane. The membrane showed a rejection rate of about
equipment.12 The energy consumption of ion exchange is lower 72% for the separation of acetic acid. Yang et al.22 studied the
than that of electrodialysis. Numerous electrodialysis mem- stability and retention of organic solvents (Safranine O, Orange
branes have been created with pH values between 2 and 9, II) and aqueous solvents on Desal-DK and Desal-DL
which is problematic, since the normal pH of amine is between membranes, and they showed that retention in aqueous solvent
9 and 11.13 Ion exchange and electrodialysis cannot eliminate was higher than that in organic solvent. In this study, our goal
nonionic impurities and require activated carbon to remove was to analyze and select commercially available SRNF-
contaminants. More waste results from electrodialysis than membranes for the removal of three common contaminants
from distillation. One signicant drawback of distillation is that (organic and ionic) from an amine solution. The separation
a large amount of waste generated means that it is not performance associated with two SRNF-membranes has been
sustainable and is expensive.2 The addition of antifoam does evaluated to have potential for the purication of this solution.
not physically remove the contaminants and, therefore, does Furthermore, the acquired results were used to examine and
not permanently treat the foaming problem.10 compare the foaming tendency and foaming stability of treated
Treatment technologies for amine solutions are generally not and untreated amine solutions to further study the eect of
sustainable or economical. Therefore, there is potential for a foaming on capturing carbon dioxide.
membrane process to be an alternative to the conventional
method. A signicant decrease in energy consumption can be 2. MATERIALS AND METHODS
achieved by using a properly selected membrane, while
2.1. Membrane and Chemicals. Laboratory grade DEA
simultaneously decreasing the waste volume through recovery
(99% purity, Sigma-Aldrich Inc., Malaysia) was used for all
of waste, ne particulates, and the nal product. Another
experiments. Acetic acid (99.7% purity, Sigma-Aldrich Inc.,
advantage of the membrane process is that it can be performed
Malaysia), sodium sulte (98% purity, Sigma-Aldrich Inc.,
at mild temperatures, where conditions should be generally
Malaysia), and sodium chloride (98% purity, Sigma-Aldrich
temperature mild, and the tendencies of acid gas and oxidative
Inc., Malaysia) were added in parts per million (ppm)
degradation paths to be scaled down to produce charged
concentrations to an aqueous DEA solution to simulate
particles,14 decreasing greenhouse gas emission and increasing
degraded DEA solutions. The aqueous amine solution was
safety in comparison to traditional separation processes,
prepared by DEA in deionized water followed by sparging of
including distillation.
99.99% CO2 into the solutions. Two kinds of polymeric SRNF-
The solvent resistant nanoltration (SRNF) membrane has
membranes (GE Osmonics and Kosh Manufactures) were
interesting potential for waste solution reduction, recovery from
tested. The related properties of both membranes supplied in
the solution during the process,15 environmental and economic
dried forms are listed in Table 1.
advantages, a wide pH range, and great separation perform-
2.2. Permeation Experimental Setup. Permeability
ance.16 Researchers have been successful in introducing new
experiments were done in a stirred cell (Sterlitech HP4750,
developments in and generation of a nanoltration (NF)
Sterlitech, USA) that containing a cylindrical stainless steel with
process, as well as improving the performance and stability of
detachable end plates (Figure 1). A membrane disk with a
NF membranes, which can be stable in the solvent throughout
diameter of 0.049 m was placed at the end of this cell,
membrane manufacturing, thus solving certain problems (e.g.,
supported by porous stainless steel. The active area of the
disintegration and dissolution of the membranes).17 Many
studies have concentrated on the development of modications
about the thin layers of SRNF-membranes in order to develop
and increase their morphology and performance. During the
polymerization, the most eective approaches to increase the
specic characteristics of the very thin layers would be to add
suitable various additives in the very thin layer matrix.18 These
membranes have numerous potentials for continuous oper-
ations during several months within renery plants.19 SRNF-
membranes have been developed and have various Molecular
Weight Cut-Os (MWCOs). For instance, Desal-DL and
Desal-DK are used in organic solvent separation. Othman et
al.20 reported the application of Desal-Dl, Desal-DK, and six
types of SRNF-membranes to separate biodiesels. Darvishma-
nesh et al.21 reported the eect of organic solvents (methanol,
acetic acid, acetone, n-hexane, and toluene) with dierent Figure 1. Dead-end ltration setup.
membrane was 15.2 cm2. The maximum solution feed volume Table 2. Concentration of Feed and Permeate
to the cell was 0.3 L, and the maximum operating pressure was
Sulte Chloride Acetic acid
69 bar. The solutions were stirred using a Teon-coated (mg L1) (mg L1) (mg L1)
magnetic bar placed 3 mm above the sheet membranes. These
Feed 56.23 211 123
membranes were pretreated/presoaked in the ltration solution
Desal-DL 9.01 55.24 70
overnight prior to the separation experiments. All permeation (permeate)
experiments were performed at ambient temperatures with SR100 (permeate) 18.14 132.5 22
pressures ranging from 2 to 14 bar. This stirred cell was
pressurized by compressed N2 gas. The volume of the feed
solutions was 0.2 L, and the volumes of permeates were
measured using a graduated cylinder. The stirring speed was
maintained at 1000 rpm by a Teon-coated magnetic bar.
The solvent uxes were determined by measuring the
ltration time dierence t (in s) and collecting data on the
permeate volume V (in mL). The ux of solvent is given as22
v
J=
At
The eective area of the membrane is A (in m2). The SRNF-
membrane was used for all of the experiments, and
uncontaminated aqueous DEA solutions were used as the
base case. The aqueous DEA solution was also added with the
following contaminants: sodium chloride (1000 ppm), sodium Figure 2. Schematic representation of foaming experimental setup.
sulte (1000 ppm), and acetic acid (100 ppm). The permeate
samples were collected using a 200 mL measuring cylinder until diuser (average pore diameter 80 m), a drying column, and a
the ltration volume reached 100 mL. The permeates of the gas ow meter. Commercial grade N2 was used instead of air as
solutions were used in the foaming experiments. a distributed N2 to bubble solution and to avoid oxidative
The concentrations of permeate and feed were analyzed by degradation that aects the foaming results.
ion chromatography. The performance of the SRNF-membrane 2.5. Foaming Study. 2.5.1. Foaming Experimental
was reported as the rejection rate, which was calculated as Procedure. A 0.001 m3 graduated cylinder containing 0.0001
follows:23 m3 of the test solution was placed in a water bath and heated to
40 C prior to each experiment. The diuser was submerged
C into the test solution, and the system thermal equilibrium was
R = 1 P 100 (%)
CF permitted to be attained for approximately 20 min. The initial
volume of the solution prior to each test was recorded. Before
where CF is the feed concentration and CP is the permeate entering into the ow meter (xed ow rate of 2 103 m/s),
concentration. The standard deviation errors were up to 5% in the N2 gas was dried to remove wetting by the drying-column.
all cases. This gas entered the graduated cylinder and traveled through
2.3. Chemical Analysis and FESEM. The surface the gas diuser. The duration of bubbling was measured with a
morphologies and cross sections of the SRNF-membrane stopwatch. pH was determined before and after each
samples were analyzed before and after ltration by eld experiment, as was the conductivity due to the alkanolamine
emission scanning electron microscopy (FESEM) using a degradation that changes the constituents of the solution.
model Zeiss supra 55vp (Germany) at a voltage of 3 kV. The The interface between the foam and liquid was dicult to
cross sections of the nanoltration membrane were immersed measure for the majority of the test solution cases during the
in liquid nitrogen to break the dry membranes. foaming test. The volumes of the liquid and the foam, instead
The DEA solutions concentrations before and after ltration of just the foam volume, in the cylinder were measured every
in both membranes were measured by UV absorption with the minute. Each foaming experiment was run for 25 min. A stable
wavelength at 210 nm using UVvis spectroscopy (with a UV- state after almost 5 min was reached in most foaming tests.
1650 PC, Shimadzu instrument). The DEA concentration Therefore, the data reading was reported as a steady state value.
before ltration were 3.4775, and those after ltration were An uncontaminated amine solution was operated at a
3.4735 for the SR100 membrane and 3.4750 for the Desal-DL baseline prior to the foaming test of the contaminated amine
membrane. Anion concentrations were measured by ion solution. Considering that the result for uncontaminated
chromatography (IC 850 Fessional, Metrohm) with a 1:50 solutions cannot be found to be similar each time, normalized
dilution ratio and 0.2 mM NaOH, including formaldehyde (for foaminess was reported for comparing before and after SRNF
stabilization of the sulte). The acetic acid concentration was ltration and also for dierent contaminants.
determined by acidbase titration using the standard solution 2.5.2. Data Analysis. The foaminess was calculated by
(NaOH with phenolphthalein) as a reagent. Table 2 shows the subtracting the initial volume of the liquid from the total
concentrations of the permeates and the feeds. volume of the graduated cylinder that yields the volume of the
2.4. Foaming Experimental Setup. Foaming tests were total gas involved in the foam and dividing by supercial gas
performed using a method modied from the standard ASTM velocity (in m2s):23,24
D892 protocol by Thitakamol. 7 Figure 2 shows the Vg
experimental setup consisting of a 0.001 m3 graduated cylinder, Vt Vi
F= =
a temperature controller immersed in a water bath, a gas G G
12137 DOI: 10.1021/acs.iecr.5b02642
Ind. Eng. Chem. Res. 2015, 54, 1213512142
Industrial & Engineering Chemistry Research Article
Figure 5. Flux of three contaminants in DEA solution versus time through (a) SR100 membrane or (b) Desal-DL membrane.
Figure 6. FESEM micrographs of the surface morphologies and cross section of the two membranes: (a) before Desal-DL ltration, (a,c) after
Desal-DL ltration, (b) before SR100 ltration, (b,d) after SR100 ltration.
(Lf inal) by the initial permeability (Linitial) yielded the up to 1, and the membrane has compaction factor closest to 1.
compaction factor (); values of the compaction factor are 0 It is the highest level of resistance for the operating pressure.32
12139 DOI: 10.1021/acs.iecr.5b02642
Ind. Eng. Chem. Res. 2015, 54, 1213512142
Industrial & Engineering Chemistry Research Article
DEA with sodium sulte after both SRNF-membranes declined
dramatically to almost 80%. Thitakamol et al.8 showed that the AUTHOR INFORMATION
foaming tendency of sodium sulte in amine solution was high
Corresponding Author
as a result of the anionic surfactants formation in the form of
*Tel.: +60 3 89216410. Fax: +60 3 89216148. E-mail:
sulfonate (SO3).
wahabm@eng.ukm.my.
3.2.3. Acetic Acid. Acetic acid is an organic acid that was
examined to determine its foaming tendency in an amine Notes
The authors declare no competing nancial interest.
solution system that was suggested by previous studies for some
plants.10,36,7 Figure 10 shows the results of acetic acid on the
ACKNOWLEDGMENTS
This work was supported by Universiti Kebangsaan Malaysia
through grant number UKM-KK-2013-023.
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