Professional Documents
Culture Documents
article info
abstract
Article history:
(GAC) from two municipal drinking water facilities was compared with bench-scale elec-
19 May 2012
evaluated using aqueous natural organic material (NOM) adsorption, iodine number
analysis, and surface area analysis. In contrast to the large electrochemical regeneration
efficiencies reported in the literature for GAC loaded with phenolics and other individual
organic compounds, the electrochemical reactor tested was only able to regenerate 8e15%
Keywords:
of the NOM adsorption capacity of the field spent GAC. In contrast, thermal reactivation
Activated carbon
Electrochemical regeneration
NOM
continuous-flow columns and not batch rectors. The iodine number analysis yielded
higher efficiency values, however it did not give an accurate estimate of the regeneration
efficiency. The small changes in GAC pore size distribution were consistent with the low
electrochemical regeneration efficiencies. These low efficiencies appear to be related to the
low reversibility of NOM adsorption and to pH-induced adsorbate desorption being the
primary mechanism for this type of electrochemical regeneration system.
2012 Elsevier Ltd. All rights reserved.
1.
Introduction
* Corresponding author. Tel.: 1 613 562 5800x6142; fax: 1 613 562 5173.
E-mail address: narbaitz@uottawa.ca (R.M. Narbaitz).
0043-1354/$ e see front matter 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.watres.2012.05.046
w a t e r r e s e a r c h 4 6 ( 2 0 1 2 ) 4 8 5 2 e4 8 6 0
I#virgin
K
M
qe
qr
V
1/n
4853
2.
Experimental
2.1.
Materials
This study utilized water samples and GAC (virgin, spent and
field-thermally regenerated) obtained from the Buffalo Pound
Water Treatment Plant, Regina, Sask., and the Richard Miller
Water Treatment Plant, Cincinnati, OH. Both of these facilities
use GAC within post-filtration adsorber columns and have onsite thermal regeneration. Note that the spent (i.e., field
loaded) GAC at both locations was collected at the end of an
operational cycle (i.e., prior to regeneration) and at the
beginning of the cycles the adsorbers were filled with GAC that
had been regenerated (one or more times) plus make-up virgin
GAC. Depending on the rate of attrition GAC particle may last
approximately 7e12 regeneration cycles. At the time of this
study the Buffalo Pound Water Treatment Plant utilized
a combination of Calgon F-400 GAC and Norit 830 GAC
(denoted as Regina GAC) while the Richard Miller Water
Treatment Plant utilized Jacobi brand GAC (denoted as Cincinnati GAC). GAC samples were kept under refrigeration until
used. Thermally regenerated and virgin GAC samples were
rinsed to remove fine material; oven dried at 105 C, cooled in
a desiccator then sealed in airtight containers until they were
used. The adsorbates utilized in this study were water
samples collected after granular media filtration and prior to
GAC adsorption (pre-GAC) at the Buffalo Pound Water Treatment Plant (denoted as Regina water) and at the Richard Miller
Water Treatment Plant (denoted as Cincinnati water). The
water samples from the two plants were shipped in foodgrade high-density polyethylene barrels and kept in a refrigerator at 2 C until used. All the reagents used were ACS grade.
Ultrapure water for the desorption tests and reagent preparation was prepared by passing distilled water through a MilliQ water treatment system (Millipore, Bedford, MA) which
incorporates mixed bed ion exchange, activated carbon
adsorption, organic scavenging resins and an ultrafiltration
membrane.
4854
2.2.
w a t e r r e s e a r c h 4 6 ( 2 0 1 2 ) 4 8 5 2 e4 8 6 0
Methods
Total organic carbon (TOC) was used to quantify the NOM, and
its concentrations were determined using an UV-persulfate
oxidation based TOC analyser (DC-180, Dohrmann Division
Rosemount Analytical Inc., Santa Clara, CA). TOC concentrations of Regina and Cincinnati waters were 3.5 and 1.5 mg/L,
respectively. All the other chemical analysis was performed
following Standard Methods (1995).
2.3.
2.4.
Electrochemical regeneration
better than several other salts when regenerating phenolloaded GAC, and that higher concentrations of NaCl did not
improve the regeneration efficiency. Based on the results of
Karimi-Jashni and Narbaitz (2005a) electrolyte mixing was not
incorporated into the reactor operation. All electrochemical
regeneration tests were conducted by placing the field-spent
GAC on the platinum wire mesh cathode, as several
researchers have shown that cathodic regeneration is generally more effective than anodic regeneration. A cation
exchange membrane (Raipore PTFE RF4010, Electrosynthesis,
Lancaster, NY) was placed in between the electrodes to
separate the reactor into cation and anion compartments and
to control the movement of ions between the two compartments. The cation exchange membrane allows the movement
of cations from the anodic compartment to the cathodic
compartment, while preventing anions from travelling from
the cathodic compartment to the anodic compartment. This
allows increases in the pH within the cathodic compartment
(where the GAC is placed) since the hydroxide ions generated
there cannot diffuse into the other compartment. One gram of
GAC was regenerated in each experiment, which resulted in
a monolayer of GAC particles on the electrode, there is
therefore an average of 0.022 g GAC per cm2 of electrode area.
So as to not change the cell voltage, gas bubbles that accumulated under the ion exchange membrane were periodically
removed through the gas removal port using a small Teflon
tube and syringe. This study used a 5 h reactivation period as
Narbaitz and Cen (1994) found that for phenol-loaded GAC the
slightly higher regeneration efficiencies achieved with longer
regeneration periods could not justify the significant associated increases in energy consumption. The reactor was
operated galvanostatically, the power was supplied using
a controller (model 410, Electrosynthesis, Buffalo, NY) with an
accessory power supply (Model 420A, Electrosynthesis,
4855
w a t e r r e s e a r c h 4 6 ( 2 0 1 2 ) 4 8 5 2 e4 8 6 0
2.5.
qr
100%
qe
(1)
Co Ce V=M
KCe1=n
100
(2)
Where I#reg and I#virgin are the iodine numbers of the regenerated and virgin GAC, respectively. The impact of the electrochemical regeneration was further assessed by analysing
the surface chemistry, surface area and pore size distribution.
The pore volume distribution of virgin, thermally regenerated and electrochemically regenerated GAC samples from
both Regina and Cincinnati were measured at the National
Research Council of Canada (NRCC) Laboratories via a N2
adsorption BET surface area and pore size distribution analyser (ASAP 2000, Micromeritics, Norcross, GA). For more
detailed information on the experimental procedure refer to
McEwen (2004).
3.
3.1.
3.2.
Impact of pH on desorption
Regina
Cincinnati
164
182
7.04
460
108
108
7.02
110
3.0
1.5
0.2
0.23
4856
w a t e r r e s e a r c h 4 6 ( 2 0 1 2 ) 4 8 5 2 e4 8 6 0
18.0
16.0
14.0
12.0
10.0
8.0
6.0
4.0
2.0
0.0
1.05
6.95
13.15
DW
pH of desorption Solution
Fig. 2 e Adsorption isotherms for Regina and Cincinnati
GAC.
3.3.
K [(mg/g)$(L/g)1/n]
1/n
R2
8.86 1.86
8.07 1.53
1.26 0.19
0.86 0.19
0.97
0.95
w a t e r r e s e a r c h 4 6 ( 2 0 1 2 ) 4 8 5 2 e4 8 6 0
4857
3.4.
4858
w a t e r r e s e a r c h 4 6 ( 2 0 1 2 ) 4 8 5 2 e4 8 6 0
Fig. 7 compares the NOM adsorption regeneration efficiency with iodine number regeneration efficiency, for fieldloaded GAC from Regina. As the current was increased the
iodine RE increased from 57 to 63%, while the NOM adsorption RE varies from 8 to 20%. Thus, calculating the regeneration efficiency according to the iodine number can greatly
overestimate the NOM-based regeneration efficiency. This is
not surprising given that the iodine number generally
correlates well with the surface area available for the
adsorption of small molecules (Snoeyink and Summers, 1999)
while NOM molecules are significantly larger. Thus, the
assessment of regeneration efficiency based on the iodine
number is not recommended for water treatment
applications.
3.5.
4.
Conclusions
w a t e r r e s e a r c h 4 6 ( 2 0 1 2 ) 4 8 5 2 e4 8 6 0
much higher regeneration efficiencies than that for fieldloaded GAC. Thus, for more realistic assessments of the
effectiveness of electrochemical regeneration of GAC from
water treatment plants, loading and reloading to assess
regeneration efficiency should be conducted via column
tests and not batch tests.
3. Iodine number was not a good indicator of the electrochemical regeneration efficiency.
4. The pore size analysis of the electrochemically regenerated
field-loaded GAC was consistent with the low NOM regeneration efficiencies observed.
This study showed that electrochemical regeneration of
commercial GAC field loaded with NOM is not very effective,
however before abandoning it, a few points bear consideration. First, as NOM removal generally is not the primary
objective of water treatment GAC systems, the efficiency of
electrochemical regeneration needs to be evaluated in terms
of the regeneration efficiency of the target compound, such as
a taste and odour compound or pesticide which is being
adsorbed in competition with the NOM. Second, other types of
electrochemical regeneration systems may prove more
effective for the task at hand. For example, some systems are
more adsorbate oxidation-controlled, rather than desorption
controlled like the one in this study (Garca-Oton et al., 2005;
Zhou and Lei, 2006). Third, the adsorption-electrochemical
regeneration system developed by Brown, Roberts and coworkers (Brown et al., 2004; Brown and Roberts, 2007;
Mohammed et al., 2011) may work well because they are based
on a low-porosity high-conductivity carbonaceous adsorbent
that should be less impacted by desorption. Third, the literature seems indicate good results for wastewater-type applications (Weng and Hsu, 2008; Wang and Balasubramanian,
2009). Fourth, due to the early stage of the development of
this technology it is not possible to compare the full-scale
costs of electrochemical and thermal regeneration. The
energy requirements for small flow applications are comparable for both types of systems, but the carbon replacement
costs are less for electrochemical systems. The electrical
energy consumption for the typical electrochemical system
tested (i.e., a mass of GAC 1.0 g, i 0.1 A, V 3.6 V and
time 5 h) was 1800 kWh/tonne of GAC. This is comparable to
the estimated energy usage for thermal regeneration in plants
with flows less than 2000 m3/d (Karimi-Jashni, 2001). Weng
and Hsu (2008) estimated the electrical energy consumption
of their electrochemical regeneration system to be 650 kWh/
tonne of GAC, so its cost is approximately 4% of replacing the
GAC with virgin GAC. In considering costs, one must
remember that thermal regeneration systems may have to
replace up to 20% of the GAC per cycle, which may cost
significantly more than the energy required (Karimi-Jashni,
2001). Thus, electrochemical GAC regeneration shows
promise, but the development of an effective reactor which
regenerates large quantities of GAC remains an important
challenge. Preferably, research should be conducted to optimize the materials and the column configurations for
adsorption and regeneration steps to take place in the same
vessel. This would reduce capital costs and eliminate GAC
transport losses. As direct contact between the GAC particles
and the electrodes was shown to improve regeneration
4859
Acknowledgements
This work was supported by the Natural Science and Engineering Research Council of Canada (NSERC) Discovery Grant
Program. We are greatly indebted to Ben Boots of the Buffalo
Pound Water Treatment Plant, Regina and Morris McCormick
of the Richard Miller Water Treatment Plant, Cincinnati for
their cooperation.
references
Ania, C.O., Parra, J.B., Menendez, J.A., Pis, J.J., 2005. Effect of
microwave and conventional regeneration on the
microporous and mesoporous network and on the adsorptive
capacity of activated carbons. Microporous and Mesoporous
Materials 85 (1e2), 7e15.
ASTM (American Society for Testing and Materials), 1995. Method
D4607e94. Standard Test Method for Determination of Iodine
Number of Activated Carbon. ASTM, Gaithersburg, MD.
Berenguer, R., Marco-Lozar, J.P., Quijada, C., Cazorla-Amoros, D.,
Morallon, E., 2010. Comparison among chemical, thermal, and
electrochemical regeneration of phenol-saturated activated
carbon. Energy & Fuels 24 (6), 3366e3372.
Brown, N.W., Roberts, E.P.L., 2007. Electrochemical pre-treatment
of effluents containing chlorinated compounds using an
adsorbent. Journal of Applied Electrochemistry 37 (11),
1329e1335.
Brown, N.W., Roberts, E.P.L., Chasiotis, A., Cherdron, T.,
Sanghrajka, N., 2004. Atrazine removal using adsorption and
electrochemical regeneration. Water Research 38 (13),
3067e3074.
Carter, M.C., Weber Jr., W.J., Olmstead, K.P., 1992. Effects of
Background dissolved organic matter on TCE adsorption by
GAC. Journal of American Water Works Association 84 (8),
81e91.
Clark, R.M., Lykins Jr., B.W., 1989. Granular Activated Carbon:
Design, Operation and Cost. Lewis Publishers, Inc., Chelsea MI.
Clements, M., Haarhoff, J., 2004. Practical experiences with
granular activated carbon (GAC) at the Rietvlei water
treatment plant. Water SA 30 (1), 89e95.
Garca-Oton, M., Montilla, F., Lillo-Rodenas, M.A., Morallon, E.,
Vazquez, J.L., 2005. Electrochemical regeneration of activated
carbon saturated with toluene. Journal of Applied
Electrochemistry 35 (3), 319e325.
Karimi-Jashni A., 2001. Electrochemical Reactivation of Granular
Activated Carbon. Dissertation (Ph.D.), University of Ottawa,
Ottawa, Canada.
Karimi-Jashni, A., Narbaitz, R.M., 2005a. Electrochemical
reactivation of granular activated carbon: effect of electrolyte
mixing. Journal of Environmental Engineering (ASCE) 131 (3),
443e449.
Karimi-Jashni, A., Narbaitz, R.M., 2005b. Electrochemical
reactivation of granular activated carbon: pH dependence.
Journal of Environmental Engineering Science (NRCC) 4 (3),
187e194.
Karanfil, T., Schlautman, M.A., Kilduff, J.E., Weber Jr., W.J., 1996.
Adsorption of organic macromolecules by granular activated
carbon. 2. Influence of dissolved oxygen. Environmental
Science and Technology 30 (4), 2195e2201.
4860
w a t e r r e s e a r c h 4 6 ( 2 0 1 2 ) 4 8 5 2 e4 8 6 0
Kilduff, J.E., Karanfil, T., Chin, Y., Weber, W.J., 1996. Adsorption of
natural organic polyelectrolytes by activated carbon: a sizeexclusion chromatograph study. Environmental Science and
Technology 30 (4), 1336e1343.
Lim, J.-L., Okada, M., 2005. Regeneration of granular activated
carbon using ultrasound. Ultrasonics Sonochemistry 12 (4),
277e282.
McEwen, J., 2004. Electrochemical Regeneration of Natural
Organic Matter (NOM) Loaded Granular Activated Carbon.
Dissertation (Masters), University of Ottawa, Ottawa, Canada.
Moore, B., Cannon, F.S., Metz, D.H., Demarco, J., 2003. GAC pore
structure in Cincinnati during full-scale treatment/
reactivation. Journal of American Water Works Association 95
(2), 103e112.
Moore, B., Wang, Y., Cannon, F.S., Metz, D.H., Westrick, J., 2010.
Relationships between adsorption mechanisms and pore
structure for adsorption of natural organic matter by virgin
and reactivated granular activated carbons during water
treatment. Environmental Engineering Science 27 (2), 187e198.
Mohammed, F.M., Roberts, E.P.L., Hill, A., Campen, A.K.,
Brown, N.W., 2011. Continuous water treatment by adsorption
and electrochemical regeneration. Water Research 45 (10),
3065e3074.
MWH (Montgomery, Watson and Harza), 2005. Water Treatment:
Principles and Design, second ed. Wiley, New York, NY.
Narbaitz, R.M., 1986. Modeling the Competitive Adsorption of
1,1,2-Trichloroethane with Naturally Occurring Background
Organics onto Activated Carbon, Dissertation (Ph.D.),
McMaster Univ., Hamilton, ON.
Narbaitz, R.M., Cen, J., 1994. Electrochemical regeneration of
granular activated carbon. Water Research 28 (8), 1771e1778.
Narbaitz, R.M., Cen, J., 1997. Alterative methods for determining
the percentage regeneration of activated carbon. Water
Research 31 (10), 2532e2542.
Narbaitz, R.M., Karimi-Jashni, A., 2009. Electrochemical
regeneration of granular activated carbons loaded with phenol
and natural-organic matter. Environmental Technology 30 (1),
27e36.
Narbaitz, R.M., Karimi-Jashni, A., 2012. Electrochemical
reactivation of granular activated carbon: Impact of reactor
configuration. Chemical Engineering Journal 197, 414e423.
Newcombe, G., 1994. Activated carbon and soluble humic
substances: adsorption, desorption and surface charge effects.
Journal of Colloid and Interface Science 164 (2), 452e462.
Newcombe, G., Drikas, M., 1993. Chemical regeneration of
granular activated carbon from an operating water treatment
plant. Water Research 27 (1), 161e165.