Waste Management 84 (2019) 166–172

Contents lists available at ScienceDirect

Waste Management
journal homepage: www.elsevier.com/locate/wasman

Alkaline recovery of phosphorous from sewage sludge and stabilisation

of sewage sludge residue
Thabo Falayi
Department of Civil Engineering Science, University of Johannesburg, P.O. Box 524, Auckland Park 2006, Johannesburg, South Africa

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

Article history: The alkaline leaching of Phosphorous (P) from sewage sludge (SS) using either NaOH or KOH was inves-
Received 26 March 2018 tigated. The effect of type and concentration of alkali, solid liquid loading and leaching temperature were
Revised 13 November 2018 also investigated. The possibility to stabilise the leached SS residue via geopolymerisation was also
Accepted 25 November 2018
explored. The results showed that KOH leached more P than NaOH. The leaching conditions yielding
Available online 30 November 2018
the highest P recovery were 8 M KOH, 4% m/v solid to liquid loading, a leaching time of 2 h and a leaching
temperature of 95 °C resulting in a 85% P leached from SS. The leaching kinetics followed modified Jander
Keywords:
kinetics with the leaching process at 95 °C being controlled by diffusion of reactants through a porous
Phosphorous
Geopolymer
layer of reaction products, whilst at 80 °C and 70 °C was controlled by diffusion of reactants through a
Modified Jander kinetics dense layer of reaction products. A 10% replacement of gold mine tailings (GMT) with the leached SS resi-
Toxicity characteristic leaching procedure due yielded a geopolymer which met the minimum requirements for construction materials with regards
Sewage sludge to ASTM C67/14 and C129/14a. The geopolymer was cured at 100 °C for 5 days yielding a geopolymer
with strength of 14.2 MPa and an open porosity of 0.38. The geopolymer also met the minimum statutory
requirements for metal leachability. This study presents an opportunity for the increased alkaline recov-
ery of P from SS and the stabilisation of the SS residue thereby creating a no solid waste process.
Ó 2018 Elsevier Ltd. All rights reserved.

1. Introduction
An estimated increase of 1.8% in crop production up to the year
2050 (FAO, 2015), will inevitable result in an increase for phospho-
rous (P) based fertilisers. It is a well-known fact that the world
reserves of P are dwindling (Vaccari and Strigul, 2011) hence it is
imperative to come up with alternative sources of P. It has been
shown that more than 80% of available phosphate rock now con-
tains very low levels of P and high levels of radioactive elements
like uranium (Cieslik and Konieczka, 2017). This then calls for
research into alternative sources of P like sewage sludge (SS). The
city of Johannesburg in South Africa produces over 100,000 tons
of SS annually (Shiba and Ntuli, 2017). It has been shown that sew-
age sludge contains the second highest amount of inorganic P apart
from P rock (Cieslik and Konieczka, 2017). P is a component of DNA
and hence essential to life (Oelkers and Valsami-Jones, 2008). The
most common recovery of P from SS is the leaching of SS using
acids and followed by precipitation of P as struvite, hydroxyap-
atites or calcium phosphates (Shiba and Ntuli, 2017). One of the
disadvantages of acid leaching is the co-leaching of heavy metals
resulting in the need for heavy metals removal from the leachate
E-mail address: tfalayi@gmail.com
(Shiba and Ntuli, 2017) using either adsorption, sequential precip-
itation, nano filtration or ion exchange. In addition the Al and Fe in
the leachate have to be separated so that the P precipitation step
can be efficient (Petzet et al., 2012). This ultimately makes the pro-
cess expensive. Residual SS after P recovery can become a sec-
ondary waste whose effects on the environment have not
received much attention in research. Stabilisation of sewage sludge
ash or sewage sludge to make construction materials is a well-
researched topic (Yamaguchi and Ikeda, 2010; Vouk et al., 2017)
but the stabilisation of SS residue from P extraction is less studied.
It is with this in mind that the stabilisation of the SS residue was
investigated. This approach also satisfies the ‘no solid waste gener-
ation’ concept (Cieslik and Konieczka, 2017). Though the objective
of this paper was to deal with the solid waste, future studies of this
project will need to investigate the effluent generated and its pos-
sible uses in geopolymerisation processes.
Geopolymerisation is an alternative way to stabilise waste
materials and reduce heavy metal leachability in these materials
(Zhang et al., 2009; Ahmari and Zhang, 2013). SS has been sta-
bilised with Portland cement (Zhan and Poon, 2015; Cry et al.,
2012) yet the use of SS in geopolymeric reactions offers a more sus-
tainable way in its stabilisation (Yamaguchi and Ikeda, 2010;
Chakraborty et al., 2017). Due to poor hydration qualities, SS
has been mixed with several pozzolanic materials in order to

https://doi.org/10.1016/j.wasman.2018.11.041
0956-053X/Ó 2018 Elsevier Ltd. All rights reserved.
 T. Falayi / Waste Management 84 (2019) 166–172 167

synthesise geopolymers. These materials include fly ash, metakao-

800
lin, blast furnace slag (Chakraborty et al., 2017; Istuque et al., 2016;
Q
Yamaguchi and Ikeda, 2010).
700
In order to avoid co leaching of metals during the recovery of P,
this research looked at establishing the effect of type of alkali
600
(NaOH and KOH) on the leaching of P from SS. It is worth noting
that direct alkaline leaching of P from SS yields low quantities of

Intensity
P (Petzet et al., 2012), yet this research looked into the effect of 500

temperature on the leachability of P from SS. The leaching kinetics

and thermodynamic parameters of the P leaching were also deter- 400

mined. The SS residue was then stabilised with gold mine tailings CP

(GMT) via alkaline activation. GMT and SS residue were the only 300

precursor for the geopolymer. The SS residue would be used as a CP

200 A
replacement of GMT in the geopolymerisation process. The effect S
of quantity of SS residue and curing process on the durability of
the geopolymer synthesised was also investigated. 100

0 10 20 30 40 50 60 70 80 90
2. Materials and methods 2 theta

2.1. Materials Fig. 1. XRD analysis of SS (CP = Calcium Phosphate oxide, Q = Quartz, A = Albite)
Operating conditions (Voltage 40 kV, Current 30 mA and scan speed 1.0000°/min).

KOH, NaOH, Ammonium molybdate, antimony potassium tar-

trate, ascorbic acid solution, sulfuric acid, sodium bisulfite, ammo-
was measured using a UV–Vis spectrophotometer (PG Instruments
nium persulfate and potassium dihydrogen phosphate were
T60).
supplied by Rochelle Chemicals South Africa. All chemicals were
analytical grade. SS was supplied by East Rand Water Care Associ-
2.3. Methods
ation (ERWAT). The treatment process of the SS is given in the
research by Shiba and Ntuli (2017). The SS was dried at 105 °C
2.3.1. Leaching of P
for 24 h and milled to less than 100 mm. Table 1 shows the X-ray
P leaching was optimised parametrically by varying concentra-
fluorescence (XRF) analysis of the SS and SS Residue (KOH based).
tion of alkali (KOH/NaOH) from 2 to 10 M, solid to liquid loading (S/
SS contained 14.6% P2O5 which made the sludge a good source
L) from 2% to 8% m/v, leaching time from 30 to 180 min, leaching
of P (Shiba and Ntuli, 2017). The relatively low content of CaO
temperature from 50 °C to 95 °C (95 °C being the temperature at
made the SS to be a good candidate for alkaline leaching (Petzet
reflux). Optimisation was done by varying one parameter at a time
et al., 2012). The relatively high alumina content may be due to
whilst the rest were kept constant.
use of Al compounds in the sewage water treatment. The XRF anal-
ysis did not show the presence oxyanions as most probably they
2.3.2. Determination of P
were below the detection limit. Fig. 1 shows the X-ray diffraction
EPA method 365.3 was used to determine the P content in the
(XRD) analysis of the SS. The mineralogy of the SS was dominated
leachate. Ammonium molybdate and antimony potassium tartrate
by silica. The leaching of P using KOH resulted in metal enrichment
react in an acid medium with dilute solutions of phosphorus to
in the SS residue. The amorphous content of the SS was evidenced
form an antimony-phospho-molybdate complex. This complex is
by the ‘hump’ centered on 22° in the XRD diffractogram (Fig. 1).
reduced to an intensely blue-coloured complex by ascorbic acid.
The color is proportional to the phosphorus concentration and is
2.2. Equipment
measured using a UV Vis spectrophotometer at a wavelength of
650 nm.
A reflux condenser was used for alkaline leaching of P from the
SS. X-ray fluorescence (Rigaku ZSX primus II) was used for the
2.3.3. Precipitation of P
determination of metal oxide content of the SS. Mineralogical
0.5–8 g of Ca(OH)2 was added to 100 ml of the P rich KOH lea-
structure was determined using an X-ray diffraction technique
chate. The slurry was thoroughly mixed for 24 h and allowed to age
(Ultima IV Rigaku XRD) using the PDxL programme whilst the
for a further 24 h, before being filtered and dried in an oven.
quantification of mineral structures was done using the Reference
Internal Ratio (RIR). The reference was silica. Total P in the leachate
2.3.4. Bioavailability of P
10 g of the precipitated P (Ca-P) was dissolved in 100 ml of 2%
Table 1 citric acid to determine bioavailability.
XRF analysis of SS and SS Residue.

Constituent Sewage Sludge Sewage Sludge 2.3.5. Geopolymerisation of SS residue and GMT
(% m/m) Residue (% m/m) The SS residue was stabilised via geopolymerisation with gold
P2O5 14.6 2.83 mine tailings (GMT) using KOH as a solvent and potassium alumi-
SiO2 40.4 30.45 nate as an activator. The SS residue was added to GMT at 10%, 20%
CaO 6.51 8.46 and 30% m/m to make the precursor mixture. The SS residue and
Fe2O3 10.2 15.66
the GMT were thoroughly mixed with potassium aluminate (KA).
SO3 5.42 7.87
Al2O3 15.4 8.44 A workable paste (that could easily be poured into the mould)
MgO 1.25 2.44 was then made by adding 10 M KOH to the dry solids. The liquid
K2O 1.96 17.44 to solid ratio of the paste was 0.26. The paste was cast into a
MnO 0.84 2.15 100
100
100 mm mould. The cast moulds were cured at room
TiO2 0.92 1.96
temperature for 90 days and at 100 °C for five days respectively.
168 T. Falayi / Waste Management 84 (2019) 166–172
The above procedure was repeated with pure GMT (GMT-0). This
was based on the previous research work done by the authors
(Falayi et al., 2018). The Unconfined compressive strength (UCS)
test was conducted with the aid of a stress controlled compression
machine with a stress rate of 0.25 MPa/s. The reported UCS was an
average of 3 samples. Toxicity characteristic leaching procedure
(TCLP) was done in accordance with the method used by
Anastasiadou et al. (2012). The modified ASTM C373-14a method
was used to determine open porosity. The cured geopolymer was
soaked in water for 24 h. After 24 h the geopolymers were removed
from water and visible water on the composite was wiped using
soft cloth. The wet geopolymers were weighed within 5 min of
being removed from water. Open porosity, f, was then calculated as
f ¼ W s  W d =V a
where Ws is the mass of the soaked geopolymer, Wd was the mass of
the dry geopolymer, V was the volume of the geopolymer and a was
the density of water. Water absorption rate was determined using
ASTM C373-14a.
2.4. Statistical analysis
All reported results are an average of three test specimens. The
error bars in all graphs at 95% confidence interval. Analysis of vari-
ance (ANOVA) using Microsoft Excel was used to determine signif-
icance of difference in results.
3. Results and discussion
3.1. Leaching experiments
There was an increase in P yield with an increase in the solid to
liquid loading up to 4% m/v as shown in Fig. 2. This was due to an
increase in P available from the SS. There was a decrease in P yield
from 6 to 8%, this might have been caused by reduction in mass
transfer efficiency due to more solid being available for a fixed
quantity of alkali (reagent starvation) (Nosrati et al., 2013; Li
et al., 2012; Hosseini et al., 2017). The ANOVA two factor with
replication analysis showed that the difference in P leaching
between NaOH and KOH was statistically significant
(p = 0.004 < 0.05). P leaching was also dependent on solid loading
as the ANOVA single factor analysis yielded a p value of 0.001.
On average KOH yielded more P than NaOH due to that KOH has
higher alkalinity as compared to NaOH. Alkalinity is important in
the leaching of P as shown in Eq. (2) (Takahashi et al., 2001). The
4% m/v solid to liquid loading was then chosen for the rest of the
experiments.
35
30
25
% P leached
20
15
10
5
0 0
2 4 6 8
Solid to liquid loading (%m/v)
Fig. 2. Variation in P yield with alkali type and solid loading (Time 120 min, alkali
concentration 2 M, leaching temperature 95 °C).
 
AlPO4 þ 4MOH ! 4M þ þ PO3
4 þ AlðOHÞ4 ð2Þ
There was an increase in P recovery with an increase in the con-
centration of alkali as shown in Fig. 3. This showed that P leaching
was alkali concentration dependent as the single factor ANOVA for
KOH gave a p value of 1.06
1010. The highest recovery was at
10 M KOH though the result at 8 M KOH was within the error limits
of the analysis and hence the difference between 8 and 10 M KOH
was statistically insignificant, therefore 8 M KOH was chosen to
determine the effect of temperature on P leaching
(p = 0.05961 > 0.05). There was a slight decrease in P yield as NaOH
concentration was increased from 4 to 10 M. The decrease was
within error limits of the analysis although the NaOH
(p = 0.0789 > 0.05) slurries became more viscous with an increase
ð1Þ in concentration leading to reduced leaching efficiencies. 4 M
NaOH was chosen for the determination of the effect of tempera-
ture on P leaching.
The increase in P yield with temperature was because at higher
temperatures, the rate of reaction increases as more particles col-
lide (Li et al., 2017) (Fig. 4). A single factor ANOVA for temperature
dependent leaching of P showed that temperature was a significant
factor in P leaching (p = 1.41
1024 < 0.05). Leaching by refluxing
yielded the best conditions as it resulted in 85 and 67% P leached
using KOH and NaOH respectively. This is in agreement with
Petzet et al., 2012, that direct alkaline leaching at low tempera-
tures yield less P. The refluxing temperature was chosen as the
one which gave the highest P yield.
There was an increase in P yield with time due to the increased
interaction between the SS and the alkali solution resulting in fur-
ther leaching of P (Fig. 5). P leaching was time dependent from
30 min to 120 min (p = 2.01
1014 < 0.05 using single factor
ANOVA) whilst from 120 min to 180 min the increase in P leached
was statistically insignificant (p = 0.23 > 0.05). After 180 min the P
yield was 85.9 and 68% for KOH and NaOH based leaching respec-
tively as compared to 75% yield for the Japanese waste water treat-
ment plants (Nakagaw and Gotou, 2010) and less than 50% for raw
sewage sludge (Schaum et al., 2007) with both using NaOH.
3.2. Leaching kinetics and thermodynamics
The KOH based leaching was studied further to establish the
kinetics and thermodynamics of the reactions involved. The leach-
ing outcome fitted the modified Jander kinetics. The linear equa-
tion for the modified Jander equation is shown in Eq. (3)
lnð1  ð1  X ÞÞ1=3 ¼ 1=NlnK N þ 1=Nlnt ð3Þ
where t was the leaching time, X was the fraction of P leached, K has
the dimensions of a diffusion coefficient. The value of N is explained
100
90
80
70 KOH
% P leached
60
NaOH
50
KOH
40
NaOH
30
20
10
2 4 6 8 10
Alkali concentraon (M)
Fig. 3. Variation in the yield of P with alkali concentration (Time 120 min, S/L 4% m/
v and leaching temperature 95 °C).
 T. Falayi / Waste Management 84 (2019) 166–172 169

100 ln t
0
90
0 1 2 3 4 5 6
80 -0.2
95°C
70 -0.4
80°C
y = 0.5479x - 2.8862
% P leached

60 -0.6 70°C R² = 0.9825 (95ºC)

ln (1-(1-X))1/3
50
KOH -0.8
40
NaOH -1
30
y = 0.4796x - 2.7911
20 -1.2
R² = 0.9794 (80ºC)
10 -1.4
0 -1.6 y = 0.4382x - 3.1223
50 60 70 80 95 R² = 0.9395 (70ºC)
-1.8
Temperature (ºC)
Fig. 6. Modified Jander plots (Alkali concentration 8 M KOH, S/L 4% m/v and
Fig. 4. Effect of leaching temperature on P yield (Time 120 min, alkali concentration
leaching time 180 min).
8 M KOH and 4 M NaOH and S/L 4% m/v).

100
1/T (K-1)
90
0
80
0.0027 0.00275 0.0028 0.00285 0.0029 0.00295
70 -0.1
60 -0.2
%P

50 -0.3
KOH
40
NaOH -0.4
30
ln k

y = -1129.6x + 2.4672
20 -0.5 R² = 0.9998
10 -0.6
0 -0.7
30 60 90 120 150 180
-0.8
Time (mins)
-0.9
Fig. 5. Effect of time on P yield (Alkali concentration 8 M KOH and 4 M NaOH, S/L
4% m/v and leaching temperature 95 °C). Fig. 7. P leaching Arrhenius plot. (Alkali concentration 8 M KOH, S/L 4% m/v and
leaching time 180 min).

as follows (Chen et al., 2011): N  1: The process is controlled by a

chemical reaction at the surface or by dissolution of reactants or
precipitation of reaction products, 1 < N  2, the process is con-
trolled by diffusion of reactants through a porous layer of reaction
products and N > 2, the process is controlled by diffusion of reac-
tants through a dense layer of reaction products. From Fig. 6 it
can be noted that the correlation coefficient decreases with a
decrease with temperature, which is an indication of a reduction
in leaching efficiency. This phenomenon further supports that alka-
line leaching of P is favoured by high temperatures. The calculated
N values for the P leaching were 1.83, 2.09 and 2.28 at 95, 80 and
70 °C respectively. This meant that the leaching of P at 95 °C was
controlled by diffusion of reactants through a porous layer of reac-
tion products, whilst at 80 and 70 °C was controlled by diffusion of
reactants through a dense layer of reaction products. This could
then explain why there was a reduction in P yield with a decrease
in temperature due to the dense layer of reaction products which
were not removed quickly due to lower thermal energy.
The Arrhenius equation can be used to calculate the activation
energy for leaching using Eq. (4)
lnk ¼ lnA  EA =RT ð4Þ
where k is the reaction rate constant, A the pre-exponential factor,
EA the reaction activation energy, J/mol, R the mole gas constant, J/
(molK); and T the thermodynamic temperature, K. A plot of ln k vs
1/T should be linear with –E/R being the slope. The natural loga-
rithm of the apparent constant at each temperature was plotted
against the inverse of temperature in order to calculate the activa-
tion energy of leaching of P with KOH. The Arrhenius plot (Fig. 7)
showed a good correlation of 0.9998 with the activation energy of
P leaching using KOH calculated to 9.4 kJ/mol. This therefore shows
that the leaching of P from SS using KOH was an inner diffusion con-
trolled processes (Hua, 2004) which further supports the kinetic
modified Jander kinetic model.

Table 2
XRF of Ca-P precipitates.

Precipitate g Ca(OH)2/100 ml leachate 0.5 1 2 4 8

Component (% m/m)
P2O5 34.33 41.65 33.78 23.89 19.25
SiO2 10.25 5.621 5.25 5.12 4.12
CaO 34.33 39.66 42.16 50.67 61.77
K2O 10.45 5.66 8.44 10.34 4.87
Al2O3 9.44 5.45 8.44 8.34 8.28
170 T. Falayi / Waste Management 84 (2019) 166–172

2500 20
TCP 18
16
2000 14

UCs (MPa)
12
10
1500 8
6
TCP
Intensity

4
TCP
1000 2
TCP
0
GMT-0 GMT-10 GMT-20 GMT-30
KP Geopolymer
500 Q Q
KP KP
Q A
Q Q
Q TCA TCA Fig. 9. Variation of UCS with SS residue content (Curing at 100 °C for 5 days, using
10 M KOH, L/S ratio of 0.26 and KA:KOH = 2.8, KA is potassium aluminate).
0

0 10 20 30 40 50 60 70 80 90 10
2 theta 9
8
Fig. 8. XRD of Ca-P precipitate TCP-Tricalcium Phosphate, Q = Quartz, KP = Potas-
7
sium Phosphate, TCA tricalcium aluminate, A = Albite.
6

UCS (MPa)
GMT-0
3.3. Precipitation of calcium phosphate (CaP) 5
GMT-10
4
GMT-20
The equation detailing the precipitation of P with Ca(OH)2 can 3
be written as (Petzet et al., 2012) 2 GMT-30
1
3Ca2þ þ 2PO3
4 ! Ca3 ðPO4 Þ2 ð5Þ 0
14 21 28 56 90
None of the precipitates did show heavy metals (Table 2) anal-
Curing Time (days)
ysis which is one of the advantages of direct alkaline leaching as
compared to acidic leaching (Shiba and Ntuli, 2017). The Ca-P pre- Fig. 10. Variation of UCS with curing time (Curing at room temperature, using 10 M
cipitate synthesised with 1 g of Ca(OH)2 had the highest P2O5 con- KOH, L/S ratio of 0.26 and KA:KOH = 2.8).
tent. The objective was to obtain a precipitate with the highest
quantity of P2O5. At levels greater than 1% Ca(OH)2 there was a nate (1.2388%), Albite (0.7324%) and Quartz (6.1829%). The Ca-P
reduction in the overall content of P2O5 because the solids were precipitate was bioavailable to plants as it had a 92.7% dissolution
dominated by Ca(OH)2 hence an increase in the CaO content of in citric acid.
the precipitates. The silica and alumina were present in the precip-
itate because they both dissolve in KOH.
The mineralogical structure of the Ca-P precipitate was domi- 3.4. Stabilisation of SS residue
nated by tri-calcium phosphate (TCP) and potassium phosphate
(KP) (Fig. 8). The PDxL quantification showed that the precipitate GMT-0 was a geopolymer synthesised with pure acidic gold
constituted of TCP (78.5125%), KP (12.6835%), Tricalcium alumi- mine tailings, whilst GMT-10, GMT-20 and GMT-30 represented

Table 3
Physical properties of various geopolymers (Curing at 100 °C for 5 days, using 10 M KOH, S/L ratio of 0.26 and KA:KOH = 2.8, KA is potassium aluminate).

GMT GMT-10 GMT-20 GMT-30

Mass of geopolymer (g) 2245 1963 1924 1876
Mass of geopolymer after a 24 h soak (g) 2389 2344 2468 2433
UCS before soaking (MPa) 18.1 14.2 8.65 4.25
UCS after soaking (MPa) 16.24 11.32 2.35 1.24
% Water absorption 6.41 19.41 28.27 29.69
% reduction in UCS 10.28 20.28 72.83 70.82
Open porosity 0.14 0.38 0.54 0.56

Table 4
Geopolymer TCLP (Curing at 100 °C for 5 days, using 10 M KOH, S/L ratio of 0.26 and KA:KOH = 2.8, KA is potassium aluminate).

Parameter GMT (ppm) SS Residue GMT-0 GMT-10 GMT-20 GMT-30 Statutory limits (ppm)
(South African water
Guideline, 1996)
Fe 12.75 6.45 1.8 2.52 4.87 5.67 5
Ni 4.51 2.46 0.23 0.34 0.41 0.42 0.4
Cu 2.69 0.45 0.13 0.18 0.32 0.34 2
Mn 3.51 1.32 0.5 0.23 0.26 0.45 10
Zn 2.62 ND ND ND ND ND 4
Sulphates 10,387 1288 2340 2376 2386 2365 6000
pH 3.84 11.45 10.8 11.1 11.2 11.3 –
 T. Falayi / Waste Management 84 (2019) 166–172 171

1600 geopolymers synthesised with 10, 20 and 30% replacement of gold

Q mine tailings (GMT).
1500
1400 Elevated temperature curing (Fig. 9) yielded a GMT geopolymer
1300 with a UCS of 18.1 MPa, whilst addition of SS residue resulted in
1200 reduction of UCS. A 76.5% reduction in the UCS was observed for
Q
1100 P M Q GMT-30. This might be due to that SS residue is weaker filler as
P P GMT-10
Relative Intensity

1000 the specific gravity of GMT was 2.99 as compared to 1.03 for SS
900 residue. The addition of SS residue to GMT significantly changed
800 the UCS of the geopolymers (p = 2.8
1011 < 0.05 using single fac-
700 tor ANOVA). Room temperature curing (Fig. 10) yielded geopoly-
600 mers with lower UCS due less thermal energy available for the
500 dissolution of silica and alumina. The geopolymerisation was slow
400 GMT with setting/hardening of the geopolymer paste happening after
300
5 days. Maximum strength was achieved after 56 days. GMT
200
CP replacement with 30% SS residue resulted in 84.6% reduction in
100 SSR
UCS as compared to the GMT-0 geopolymer.
0
0 10 20 30 40 50 60 70 80 90
3.4.1. Wet UCS durability
2 theta
An increase in SS residue content resulted in increase in water
Fig. 11. XRD of GMT-10 geopolymer (SSR-sewage sludge residue, CP calcium absorption accompanied by a reduction in durability (Table 3).
Phosphate, S = quartz, P = Pyrite, M = Haematite) Curing at 100 °C for 5 days, using GMT-30 geopolymer recorded over 70% reduction in UCS indicat-
10 M KOH, L/S ratio of 0.26 and KA:KOH = 2.8, KA is potassium aluminate. ing that it was not durable. The minimum water absorption
required for a construction material is 25% (ASTM C67/14,

Fig. 12. SEM micrograph of GMT (A), Sewage sludge residue (B) and GMT-10 (C). Curing at 100 °C for 5 days, using 10 M KOH, L/S ratio of 0.26 and KA:KOH = 2.8, KA is
potassium aluminate.
172 T. Falayi / Waste Management 84 (2019) 166–172
C129/14a), therefore the GMT-10 geopolymer can be used as a con-
struction material in which its properties are not a limitation.
3.4.2. TCLP
At 20% and 30% GMT replacement, geopolymers synthesised did
not meet the minimum statutory requirements for metal leachabil-
ity and therefore cannot be safely used in the environment
(Table 4). The GMT-10 geopolymer with 10% replacement of GMT
met the minimum requirements and can be used a construction
material. The reason for the difference in metal leachability has
to do with the open porosity of the different geopolymers. GMT-
10 had an open porosity of 0.38 as compared to 0.56 for GMT-30
(Table 3). This therefore means the GMT-30 geopolymer could
have more water ingress resulting in the increased metal leachabil-
ity as compared to the GMT and GMT-10 geopolymers.
3.5. Spectroscopic study of the GMT-10 geopolymer
3.5.1. XRD analysis
Phosphorous recovery from sewage sludge resulted in the sig-
nificant reduction of the calcium phosphate peak in the sewage
sludge residue (Figs. 1 and 11). There was not much significant dif-
ference between the XRD of GMT and GMT-10. The only difference
was the increase in amorphous nature of the geopolymer XRD as
compared to the GMT geopolymer. This was evidenced by the ele-
vation of the XRD diffractogram base between 5 and 19° for the
geopolymer which is not present in the purely crystalline GMT.
The elevation of the baseline is evidence of the introduction of
the disordered structure in the material which showed that
geopolymerisation had taken place (Ahmari et al., 2015).
3.5.2. SEM analysis
GMT was composed of massive particles with a shell-like sur-
face (which may indicate very fine grained) coated with nanopar-
ticles (Fig. 12) which confirmed the crystalline nature shown
from XRD diffractogram (Fig. 11). Sewage sludge residue was com-
posed of loosely packed particles. The geopolymer (GMT-10)
(Fig. 12C) was smaller sized particles as compared to the original
GMT particle. Although the dilution of GMT particles was 10% in
GMT-10, geopolymerisation resulted in the breakup of particles
due to the aggressive nature of the curing process.
4. Conclusion
The direct alkaline leaching of P from sewage sludge is alkali,
temperature, time and solid loading dependent. KOH was found
to be a better leachant as compared to NaOH. A 4% (m/v) solid to
liquid loading, concentration of 8 M, a leaching temperature and
time of 95 °C and 2 h respectively resulted in 85% recovery of P.
The leaching process was controlled by diffusion of reactants
through a porous layer of reaction products and followed modified
Jander Kinetics. The activation energy for the leaching was found to
be 9.4 kJ/mol. The alkaline stabilisation of the SSR with GMT was
temperature, time and SS residue content dependent. A maximum
of 10% (m/m) SS residue should be used to replace GMT in the
geopolymer in order to produce a competent geopolymer. Elevated
temperature curing yielded a geopolymer with a higher UCS as
compared to ambient temperature curing. The geopolymer synthe-
sised with 10% replacement of GMT with SS residue could be used
as a construction material where its properties are not an impedi-
ment. The geopolymer met the minimum statutory requirements
for metal leachability and hence can be used safely in the
environment.
Acknowledgements
The author would like to thank Tabea Diseko and Mokgadi
Masetla for assisting with laboratory work. The author would like
also to thank the University of Johannesburg for granting the Glo-
bal Excellence Stature research fund (201323467) to the author.
The author also declares no conflict of interest.
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