Materials Letters 220 (2018) 238–240

Contents lists available at ScienceDirect

Materials Letters
journal homepage: www.elsevier.com/locate/mlblue

Activated carbon production: Recycling KOH to minimize waste

Vicente Montes, Josephine M. Hill ⇑
Department of Chemical and Petroleum Engineering, University of Calgary, 2500 University Dr NW, Calgary, Alberta T2N 1N4, Canada

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

Article history: Synthesis of activated carbon by chemical activation results in materials with high surfaces areas and
Received 11 November 2017 pore volumes (e.g., >1800 m2/g and >1 cm3/g). The main problems are the large amount of chemical
Received in revised form 7 February 2018 required and the waste water created. To solve these problems, we have studied the recycle of KOH,
Accepted 3 March 2018
focusing on the impacts of impurities originating in the starting materials and transferring to the solution
used for washing the product. After activation of petroleum coke and carbon black, potassium was
recovered in an aqueous solution including mainly KOH and K2CO3. The higher the fraction of the more
Keywords:
active form of potassium (i.e., KOH), the higher the level of activation in subsequent experiments. The
Activated carbon
KOH
presence of sulphur increased the fraction of KOH recovered. Full recovery of potassium was achieved
Recycle using HNO3 in the washing solution, but this acid also dissolved others species, such as Si and Al, that
Petroleum coke were detrimental for carbon activation.
Carbon black Ó 2018 Elsevier B.V. All rights reserved.

1. Introduction in a ceramic boat within a horizontal tube into a furnace. With a N2

Over 200 publications per year (Scopus) report the synthesis of
activated carbon (AC) through chemical activation methods, most
commonly using KOH. Some authors suggest the possibility of
recycling the chemical but KOH is transformed during the activa-
tion process and recovered as carbonate, K2CO3, which is normally
a less effective activation agent [6]. Yuan et al. [8] reported that
activation at higher temperatures led to a higher recovery of
KOH while Nowrouzi et al. [4] were able to recycle the washing
water from waste tissue activation and produce AC with consistent
properties but they did not clarify if activation of their char with
K2CO3 was as effective as KOH. For non-porous materials such as
coal and coke, K2CO3 is not an effective activation agent. Thus, in
this letter we have focused on the KOH/K2CO3 ratio in the recov-
ered solutions, and the accumulation of impurities.
2. Material and methods
Two carbonaceous materials with different ash contents were
chosen: delayed petroleum coke (petcoke or P, Suncor Energy
Inc., Alberta, Canada) and carbon black (CB, Carbon Black Monarch
120, Cabot Corp., Massachusetts, USA). The feeds were ground and
sieved to a size range of 150–63 mm, then mixed with aqueous
flow of 250 cm3/min, the temperature was increased at 5 K/min
until 1023 K, and held for 30 min (detailed description in [5]). After
returning to room temperature, the AC was washed six times with
deionized water, while the ceramic boat and surrounding tube
were washed once. The used water (500 cm3 total) was combined
for use in subsequent experiments. Then the AC was washed with
50 cm3 of 0.1 M HNO3 solution to fully recover the potassium [2,4].
The recycling studies were done by impregnating fresh feeds using
water (or water plus acid) obtained from washing AC activated
with KOH.
N2 physisorption (TriStar 3000, Micromeritics Instrument,
Norcross, USA) at 77 K was used to calculate pore volume at a rel-
ative pressure of 0.99. Before analysis, all samples were degassed
at 423 K for 5 h. Ash content was determined with a thermogravi-
metric analyzer (TGA, SDT Q600, TA Instruments, Delaware, USA).
Typically 20 mg of sample was heated to 1073 K at 10 K/min in
flowing (100 cm3/min) synthetic air. Elemental analyses were done
with scanning electron microscopy equipped with an energy
dispersive spectrometer, (SEM-EDX, Phenom ProX, Eindhoven,
Netherlands). An inductively coupled plasma optical emission
spectrometer (ICP-OES ThermoFisher Scientific IRIS Intrepid II
XDL, Waltham, USA) was used to confirm the EDX analysis values
for selected samples. Determination of [OH
]/[CO2
3 ] ratios was

solutions containing KOH, K2CO3, or a recycled solution with a done by titration of 10 cm3 of the recycled solution with 1 M HCl
molar K/C ratio of 0.11, 0.21, 0.43, or 0.63. The mixture was placed using phenolphthalein and methyl orange as indicators.

⇑ Corresponding author.
E-mail address: jhill@ucalgary.ca (J.M. Hill).

https://doi.org/10.1016/j.matlet.2018.03.019
0167-577X/Ó 2018 Elsevier B.V. All rights reserved.
 V. Montes, J.M. Hill / Materials Letters 220 (2018) 238–240 239

0.9 0.8 16
a)
0.8 a) 0.7 14

Pore Volume (cm3/g)

Impurities (wt%)
Pore Volume (cm3/g) 0.6 12
0.7
0.6 0.5 10
0.5 0.4 8
0.4 0.3 6
0.3 0.2 4
0.2 0.1 2
0.1 0.0 0
0 1 2 3 4 5 6 7
0 Cycle number
0.0 0.2 0.4 0.6 0.8 16
Molar ratio K/C 0.7 b) 14

Pore Volume (cm3/g)

Impurities (wt%)
3.0 1.0 0.6 12
2.7 b) 0.9 0.5 10
2.4 0.8 0.4 8
2.1 0.7
Impurities (wt%)

0.3 6
[OH-]/[CO32-]

1.8 0.6 0.2 4

1.5 0.5 0.1 2
1.2 0.4
0 0
0.9 0.3 0 1 2 3 4 5 6 7
0.6 0.2 Cycle number
0.3 0.1 0.8 16
0.0 0.0 c)
0.7 14

Pore Volume (cm3/g)

0.0 0.2 0.4 0.6

Impurities (wt%)
0.6 12
Molar ratio K/C
0.5 10
Fig. 1. Influence of K/C molar ratio on a) pore volume developed in petcoke with 0.4 8
KOH (j), K2CO3 (h), or recycled (water wash only) solutions (N), and b) [OH
]/
0.3 6
[CO2

3 ] ((), right axis) ratio and impurity (sulphur (d) and silicon plus aluminium
(s), left axis) content of recycled solutions. 0.2 4
0.1 2
0.0 0
3. Results and discussion 0 1 2 3 4 5 6 7
Cycle number
Fig. 1a illustrates the pore volumes obtained by mixing petcoke
Fig. 2. Pore volume developed and impurity content as a function of the cycle
with fresh solutions of KOH or K2CO3, or with recycled solutions number for a) carbon black, and b), c) petcoke using recycled solutions from
from washing with water, at different K/C molar ratios. All pro- washing with water (N), or water and acid (4); pore volumes obtained by activation
duced materials were over 90% microporous (see [5] for more with KOH (j) or K2CO3 (h) are added for comparison; the impurities measured:
sulphur (d) and silicon plus aluminium (s).
details) with surface areas from 32 to 1960 m2/g. The pore volumes
were highest for activation with KOH, and increased with the rel-
ative amount of chemical agent used. Activation with K2CO3 was
significantly less effective, with the produced AC having a pore vol- when removed by washing, leave pores in the carbon while react-
ume of 0.22 cm3/g regardless of the amount of chemical agent ing with the water to form KOH. The pore volumes achieved are
used. Use of the recycled solution resulted in AC with similar pore consistent with the higher [OH]/[CO2
3 ] ratio in the recycled solu-
volumes to that produced with K2CO3 at the lower two ratios, and tion than in the K2CO3 solution and with this ratio increasing with
between that obtained with KOH and K2CO3 at the higher two the K/C ratio used (Fig. 1b). The concentrations (wt %) of S, Si and Al
ratios. The resulting pore volume increased with increasing ratios in the recycled solutions were similar regardless of K/C ratio used.
of K/C, suggesting a higher amount of K and K2O was formed dur- Washing with water resulted in only partial recovery of potas-
ing activation, species that intercalate into the carbon matrix, and sium and dissolution of the majority of sulphur (6.5 wt% to 0.6 wt

Table 1
Main impurities and surface areas of feed and select AC samples.

Component (wt%)2 Surface Area (m2/g)

Sample C S Ash K Si Al
Feed
Petcoke 84 6.4 3.7 0.1 0.6 0.5 <1
Carbon Black 99 0 0 0 0 0 32
Activated carbon1
P0.21KOH-1-W 89 0.6 4.3 1 0.8 0.6 945
P0.21KOH-1-W + A 89 0.5 1.1 0.1 0.3 0.1 922
1
AC produced from petcoke with KOH using 0.21 K/C molar ratio, washed with water (P0.21KOH-1-W) or water and acid (P0.21KOH-1-W + A).
2
Mass balance does not include oxygen or trace impurities.
240 V. Montes, J.M. Hill / Materials Letters 220 (2018) 238–240

0.8 washing process likely to H2S (gas). The sulphur remaining in the
a) recycled solution likely existed as SO2

4 [8], which can be carboth-
0.7
ermally reduced to S2
at the activation temperature (1073 K) [7],
Pore Volume (cm3/g)
0.6 and subsequently react to form K2S. In contact with water during
0.5 the washing process at room temperature, K2S forms KOH and
H2S (gas) [3]. Thus, the presence of sulphur increased the amount
0.4
of potassium in the form of KOH for subsequent activation cycles.
0.3 Fig. 3. shows the relationship between the [OH
]/[CO2
3 ] ratios
0.2 (representative of the KOH/K2CO3 ratio) in the recovered solutions
and the resulting pore volumes developed. For carbon black,
0.1
Fig. 3a the ratio did not vary much (0.25–0.35) nor did the pore
0 volume achieved. For petcoke, Fig. 3b, higher [OH
]/[CO2
3 ] ratios
0.00 0.25 0.50 0.75 1.00 and pore volumes were obtained using recycled solutions from
[OH-]/[CO32-] washing with water only (i.e., no acid) despite a lower recovery
of K. The presence of acid may have neutralized the anions, and
0.8 dissolved Si and Al species, leading to deactivation of the K [1].
0.7 b)
Pore Volume (cm3/g)

0.6 4. Conclusion

0.5
0.4
0.3
0.2
0.1
0 removed Si and Al, which deactivated the potassium and/or inter-
0.00 0.25 0.50 0.75 1.00
[OH-]/[CO32-]
Fig. 3. Impact of the [OH
]/[CO2

3 ] ratio in recycled solutions from washing with
water (N), and water and acid (4) on pore volume developed in a) carbon black and
b) petcoke. The line connects the points for KOH and K2CO3 and is only a guide.
%) from the AC, P0.21K-W (Table 1). Although washing with an
acidic solution fully recovered the potassium, this procedure also
dissolved the majority of the main ash components (sample
P0.21K-W + A, Table 1) and these components may interfere with
subsequent activation cycles if accumulated in the solution.
The effectiveness of the recycled solutions for activation of both
feeds was determined with a fixed K/C molar ratio of 0.43. For the
activation of the impurity-free carbon black, (Table 1) the pore vol-
ume developed with the recycled solution from washing with
water remained constant at 0.26 cm3/g regardless of the cycle
number, Fig. 2a. This pore volume was between that developed
with K2CO3 and KOH, suggesting there was a mixture of these
two species in the recycled solution. For the activation of petcoke,
the pore volume increased with the cycle number and was higher
for solutions from washing with water than solutions from wash-
ing with water and acid (Fig. 2b and c). At the same time, sulphur
accumulated in solution, regardless of the washing process. Some
researchers suggest that sulphur in petcoke is transformed to
mainly K2S [3]. Sulphur increased from 2 wt% (3.1 mmol of 5.4
mmol present in the petcoke) after the first cycle to 4 wt% after
the fifth cycle. Accounting for the sulphur loss in the produced
AC, some sulphur was released during the reaction and/or the
We have demonstrated that KOH can be recovered and recycled
for the activation of petcoke and carbon black. During the process,
the less active species, K2CO3, will form but the presence of sulphur
(a component of petcoke) resulted in more of the potassium recov-
ered as KOH. Washing with acid was required to recover all of the
added potassium from the activated petcoke but the acid also
fered with activation in subsequent cycles.
Acknowledgements
The authors acknowledge the financial support of the Natural
Sciences and Engineering Research Council of Canada (NSERC)
through a Strategic Grant, Shell Canada for financial and technical
support in this project and University of Calgary for Eyes High Post-
doctoral Scholar Award (VM).
References
[1] G. Bruno, M. Buroni, L. Carvani, G.D. Piero, G. Passoni, Water-insoluble
compounds formed by reaction between potassium and mineral matter in
catalytic coal gasification, Fuel 67 (1988) 67–72.
[2] M.J. Illán-Gómez, A. García-García, C. Salinas-Martínez de Lecea, A. Linares-
Solano, Activated carbons from spanish coals. 2. Chemical activation, Energy
Fuels 10 (1996) 1108–1114.
[3] S.H. Lee, C.S. Choi, Chemical activation of high sulfur petroleum cokes by alkali
metal compounds, Fuel Process. Technol. 64 (2000) 141–153.
[4] M. Nowrouzi, J. Behin, H. Younesi, N. Bahramifar, P.A. Charpentier, S. Rohani, An
enhanced counter-current approach towards activated carbon from waste
tissue with zero liquid discharge, Chem. Eng. J. 326 (2017) 934–944.
[5] L.D. Virla, V. Montes, J. Wu, S.F. Ketep, J.M. Hill, Synthesis of porous carbon from
petroleum coke using steam, potassium and sodium: combining treatments to
create mesoporosity, Micropor. Mesopor. Mater. 234 (2016) 239–247.
[6] J. Wang, S. Kaskel, KOH activation of carbon-based materials for energy storage,
J. Mater. Chem. 22 (2012) 23710–23725.
[7] J.F.M. White, A.H. White, Manufacture of sodiym sulfide: reduction of sodium
sulfate to sodium sulfide at temperatures below 800deg; C, Indus. Eng. Chem.
28 (1936) 244–246.
[8] M. Yuan, Y. Kim, C.Q. Jia, Feasibility of recycling KOH in chemical activation of
oil-sands petroleum coke, Can. J. Chem. Eng. 90 (2012) 1472–1478.