Waste Management 105 (2020) 566–574

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

Energy and phosphorous recovery through hydrothermal carbonization

of digested sewage sludge
J.D. Marin-Batista, A.F. Mohedano, J.J. Rodríguez, M.A. de la Rubia ⇑
Chemical Engineering Department, Universidad Autonoma de Madrid, Campus de Cantoblanco, 28049 Madrid, Spain

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

Article history: This work evaluates the potential of hydrothermal carbonization (HTC) to valorize the digestate derived
Received 16 November 2019 from the anaerobic digestion of sewage sludge into useful materials for P and energy recovery. The
Revised 14 January 2020 hydrothermal treatment of digestate at 180–240 °C did not lead to high-rank hydrochars. On the other
Accepted 2 March 2020
hand, inorganic P concentration did not change with the temperature, while as the carbonization temper-
ature increased, the organic P retention yield in hydrochar became lower, increasing the total P in the
process water obtained at the highest temperature, up to 25.3%. P recovery from acid leaching of the
Keywords:
hydrochar obtained at 180 °C, via precipitation with CaO at pH up to 9, led to a brown solid precipitate
Anaerobic digestion
Digestate
with total P content close to 42 mg g
1, in the range of low grade phosphorus ores. Moreover, acid leach-
Hydrothermal carbonization ing reduced by 50% the ash content, yielding lignite-like upgraded hydrochars with higher heating values
Phosphorus recovery in the range of 20.5–23.1 MJ kg
1, fairly interesting as solid fuels. Anaerobic digestion of the process
water enabled additional energy recovery in form of biogas (325 and 279 mL CH4 g
1 VS -at standard
temperature and pressure; STP- from the process water resulting at 180 and 210 °C, respectively).
Ó 2020 Elsevier Ltd. All rights reserved.

1. Introduction both practices no longer suitable (Wang et al., 2019). Heavy metals,
along with other undesirable substances (e.g., inorganic nitrogen,
Anaerobic digestion (AD) is often implemented in wastewater toxic organic compounds or endocrine disruptors) limit the use
treatment plants (WWTP) for sewage sludge stabilization due to of digestate for land-application to rates below 6 ton ha
1 year
1
the added-value of energy recovery in the form of biogas (Dragicevic et al., 2018). Even, some European countries (e.g.
(Kacprzak et al., 2017). Depending on the size and configuration Netherlands, Romania, and Slovakia) have banished this practice
of the WWTP, the recovered energy can offset 40–75% of the total since the long-term impact of heavy metals on plant yields and soil
power consumed on-site (Silvestre et al., 2015). Thus, in 2016 more biological activity is still unknown (Kacprzak et al., 2017). On the
than 2,800 WWTPs contributed with almost 1.4 Mtoe ( 16.3106 other hand, incineration turns digestate nutrients and heavy met-
MWh) to the European Union (EU) electricity production, about als into ashes that agglomerate in combustion chambers to an
400 ktoe ( 4.6106 MWh) higher than the 2009 figure (EBA, extent of depleting thermal efficiency (Kratzeisen et al., 2010).
2017; EurObserv’ER, 2017). However, the suitability of AD relies Moreover, ashes from incineration are disposed in landfills, ignor-
on the ability of the WWTPs operators to manage the digested ing their significant potential to be used as a secondary source of P
sewage sludge (digestate) (Aragón-Briceño et al., 2017). (8.9–35.9% of P2O5, within the range of phosphate ores) for the
Digestate landfilling is being less and less used owing to more manufacture of fertilizers and phosphoric acid (Mar and Okazaki,
stringent EU environmental regulation (Kacprzak et al., 2017). 2018; Wang et al., 2018).
From the circular economy perspective (European Commission, Separation of desirable from undesirable substances in diges-
2018), digestate is managed via two major routes: nutrient recla- tate is therefore of high interest and technologies are developing
mation by composting and energy recovery by incineration fast, especially for P recovery (Becker et al., 2019). In this context,
(Kleemann et al., 2017; Vardanyan et al., 2018). However, the high hydrothermal carbonization (HTC) is a thermochemical process
content of heavy metals (e.g., Al, Cr, As, Ni, and Hg) would make able to treat wet biomass within the temperature range of 180–
250 °C and the corresponding equilibrium pressure (2–10 MPa)
(Zhao et al., 2018), yielding a solid so-called hydrochar and a pro-
⇑ Corresponding author. cess water (PW) of high organic load. HTC has evolved as an envi-
E-mail address: [email protected] (M.A. de la Rubia). ronmentally friendly and energy-efficient sustainable technology

https://doi.org/10.1016/j.wasman.2020.03.004
0956-053X/Ó 2020 Elsevier Ltd. All rights reserved.
 J.D. Marin-Batista et al. / Waste Management 105 (2020) 566–574 567

(Zhao et al., 2014). In general, hydrochars derived from digestate reclamation by acid leaching of hydrochar and (ii) energy recovery
show fairly interesting higher heating values (HHVs) in the range by coupling combustion of leached hydrochars and anaerobic
of 14–16 MJ kg
1, which make them attractive for coal co-firing digestion of PW.
(Aragón-Briceño et al., 2017). Moreover, HTC improves signifi-
cantly the dewaterability of the resulting solid (Kim et al., 2014), 2. Material and methods
remove harmful substances (endocrine disruptors, pathogens and
other microorganism) (Wang et al., 2019) and convert organic 2.1. Hydrothermal carbonization of digestate
pollutants through typical carbonization reactions (hydrolysis,
decarboxylation, dehydration, polymerization, and condensation) Dewatered digestate (83.5 ± 5% moisture content), containing
(Rodriguez Correa et al., 2017). Process conditions (temperature, 165 ± 1.2 g kg
1 of total solids (TS), 103 ± 3 g kg
1 of volatile solids
retention time and pH) can be conveniently managed to optimise (VS), and 852 ± 8 g O2 kg
1 of total COD (TCOD), was collected from
the hydrochar solid-fuel properties and nutrients retention a WWTP, located in central Spain, processing sewage sludge in a
(P-PO3
+
4 and N-NH4), being the optimal conditions for carboniza- mesophilic anaerobic reactor.
tion and nutrient recovery divergent in terms of temperature and HTC tests were performed at 180, 210 and 240 °C in an electri-
pH (Stutzenstein et al., 2018). cally heated 4 L ZipperClaveÒ pressure vessel. The vessel was
Hydrochar can generally retain over 60% of C, 80% of P, and 40% loaded with 2 kg of digestate on wet basis. The operating temper-
of N present in the feedstock (Wang et al., 2017). P is usually in ature for the HTC runs was reached at a heating rate of 3 °C min
1
inorganic form (apatite and non-apatite orthophosphate) and its and then held for 1 h. The reaction was quenched by cooling with
speciation is strongly related with the presence of Ca, Fe and Al an internal heat exchanger using tap water. The slurry (hydrochar
in the feedstock (Xu et al., 2018). Digestate usually contains high and PW) was separated by vacuum filtration (0.90 lm), then the
concentrations of Al and Fe due to the use of iron or aluminium sul- supernatant was filtered (0.45 lm) and the PW obtained was
phate across WWTP to precipitate phosphate in the water line and stored (4 °C) for using as substrate in the AD tests.
sludge thickening/dewatering systems (Dragicevic et al., 2018; The hydrochar (HC) was oven-dried overnight at 105 °C, and
Silvestre et al., 2015). Therefore, inorganic P tends to stay, even then ground and sieved. A Filtra No. 38,373 sieve was used to
under acidic hydrothermal conditions, in these very stable metal separate the hydrochar into three fractions, namely: £ >
associations and is fixed in the hydrochar along with a large 0.5 mm; 0.25 < £ < 0.5 mm and £ < 0.25 mm, being the smallest
amount of other heavy metals (Becker et al., 2019). Finally, both one used for characterization. The hydrochars obtained were
P and heavy metals can be removed from hydrochars by acid leach- labelled as HC180, HC210, and HC240, related to the HTC temper-
ing, being P further reclaimed from leachate by precipitation ature used. Thereafter, acid leaching of hydrochars (particle size,
(Becker et al., 2019; Zhao et al., 2018). £ < 0.25 mm) was carried out in order to remove inorganic com-
On the other hand, the PW obtained by HTC of sewage sludge ponents. The acid leaching was performed with 1 N HCl (50 mL g
1
has shown high values of chemical oxygen demand (COD; 90– hydrochar) in a Soxhlet extractor for 2 h and repeated two more
110 g L
1), including volatile fatty acids (VFAs), furan compounds, times (total extraction time, 6 h) (Marin-Batista et al., 2019). The
phenols, N-containing species (e.g., ammonia, pyrazines, amines, leached hydrochars, from now onwards called upgraded hydro-
and pyrroles), among other components (Villamil et al., 2019, chars (UHC), were washed with deionized water until neutral
2018). Taking into account the biodegradability of many of the pH and then oven-dried overnight at 105 °C. The resulting
components of this fraction, it can be valorised by AD to obtain upgraded hydrochars were labelled as UHC180, UHC210, and
additional energy in form of biogas (De la Rubia et al., 2018a). UHC240.
AD allows around 44–61% removal of the initial COD in PW, and
almost complete removal of furans and phenols (De la Rubia 2.2. Phosphorus speciation and reclamation
et al., 2018b). Meanwhile, N-containing species can influence the
anaerobic biodegradability of PW (Chen et al., 2019). The P species in solid phase, digestate and hydrochars, were
Despite the apparent advantages of HTC as a post-treatment for analysed according to the Standards in Measurements and Testing
digestate, so far many research works have focused on the hydro- (SMT) extraction protocol (Zhao et al., 2018). The extraction proto-
char and PW characteristics regarding potential use as energy and col enabled to identify:
nutrients source, while only few studies have tried to define valori-
sation routes addressed to the integral exploitation of HTC within (a) Inorganic P (IP), extracted by mixing 0.2 g solid sample with
the EU circular economy. Aragón-Briceño et al. (2017) suggested a 20 mL of 1 N HCl under continuous stirring for 16 h at 25 °C.
cascade process for the valorisation of sewage sludge comprising (b) Organic P (OP), obtained by calcination of the residual solid
AD followed by HTC as a post-treatment to recover energy from after IP extraction at 450 °C for 3 h, and then treating ashes
digestate. The energy associated to the hydrochar plus the biogas with 20 mL of 1 N HCl under continuous stirring for 16 h at
produced from PW (10.8–12.7 MJ kg
1 feedstock) was significantly 25 °C.
higher than the overall energy recovered from the conventional AD (c) Non-apatite IP (NAIP), the P associated with Al, Fe, Mg, and
of the sewage sludge pre-treated by thermal hydrolysis (7.1 MJ kg
1 Mn oxides and hydroxides, extracted by mixing 0.2 g solid
feedstock). Regarding to nutrients recovery, phosphorus can be sample with 20 mL of 1 N NaOH under continuous stirring
extracted from the ashes after hydrochar combustion and recycled for 16 h at 25 °C. Thereafter, 10 mL of extract was mixed
for its added-value, since the sole use of hydrochar as energy with 4 mL of 3.5 N HCl for 16 h at 25 °C without stirring.
source implies wasting nutrients. Becker et al. (2019) suggested a (d) Apatite P (AP), the P species associated with Ca. Extracted by
nutrient recovery approach from digestate HTC implying acid mixing 0.2 g solid sample with 20 mL of 1 N NaOH under
leaching of hydrochars for P recovery (up to 82.5 wt%) after stru- continuous stirring for 16 h at 25 °C. Thereafter, the solid
vite precipitation and further use of PW as ammonia source residue was treated with 20 mL of 1 N HCl under continuous
(107–291 mmol L
1 NH+4). stirring for 16 h at 25 °C.
The aim of this study is evaluating the potential of hydrother-
mal carbonization to convert digestate derived from sewage sludge Therefore, total P was calculated as follows:
into valuable materials for phosphorus and energy recovery. The
suggested valorisation route implied two stages (i) phosphorus Total PðTP Þ ¼ IP þ OP; where IP ¼ NAIP þ AP
568 J.D. Marin-Batista et al. / Waste Management 105 (2020) 566–574

Phosphate was determined from the supernatant solutions fol- Methane production was monitored daily and calculated by sub-
lowing spectrophotometric method based on the formation of tracting the amount of methane produced by the blank controls
vanadium-molybdenum phosphate (APHA, 2005). The concentra- from the methane production of each fed reactor. In addition, trip-
tions of phosphate species were expressed in terms of phosphorus licate control experiments with starch (Panreac) as only substrate
retention yield (g PO3

4 per 100 g TP feedstock) given by Eq. (1): were also conducted to verify the inoculum activity.
 
Py
Phosphorus retention yield ¼ Y HC;UHC;PW   100 ð1Þ
TP feedstock
2.4. Quantification of the net energy production
where, Py represents each specie of the four P fractions (IP, OP, AP
and NAIP) measured for each HC. TPfeedstock corresponds to the TP The values of specific methane yield (SMY) obtained in the
concentration in digestate. YHC,UH,PW corresponds to HTC-product anaerobic tests were converted into HHV by Eq. (3):
mass yields calculated according to Eq. (2). The mass yields of  
hydrochar (YHC) and upgraded hydrochar (YUHC) were defined as
VS
HHV PW MJ kg
1 ¼ 39:8  SMY  ð3Þ
the respective weight ratio of recovered hydrochar (WHC) and TS
upgraded hydrochar (WUHC) to digestate (WD) fed into the HTC reac-
tor, on a TS basis. Similarly, process water mass yield (YPW) is the where, SMY refers to the specific methane yield. The VS to TS ratio
weight ratio between of recovered PW (WPW) to digestate (WD) corresponds to the substrate added into the anaerobic reactor,
fed, also on a TS basis. and 39.8 is the higher heating value of pure methane in MJ Nm
3.
  The total energy associated to HTC products was calculated by
W HC;UHC;PW
Y HC;UHC;PW ð%Þ ¼  100 ð2Þ Eq. (4):
WD
After acid leaching of HC180, HC210, and HC240, the resulting
1
Energy produced ðMJ kg feedstock Þ
leachates were used for P recovery via precipitation with CaO.
The procedure involves addition of 0.5 M CaO to 25 mL of acid lea- ¼ HHV HC;UHC  Y HC;UHC þ HHV PW  Y PW ð4Þ
chate (previously filtered through a 0.22 lm membrane) in 250 mL
Erlenmeyer flasks, until reaching a pH of 5, 7, and 9. The mixtures where, HHVHC,UHC corresponds to the HHV (MJ kg
1) of hydrochars
were stirred at 80 rpm in a thermostatic shaker at room tempera- and upgraded hydrochars, respectively.
ture. Addition of CaO to the acid leachate caused precipitation of a
brown solid. The corresponding solids were separated by filtration
through a 0.22 lm membrane, washed with deionized water and 2.5. Analytical methods
characterized by inductively coupled plasma atomic emission
spectroscopy (ICP-MS). The dried solid samples (digestate, hydrochars, and upgraded
hydrochars) were analysed by elemental composition determined
2.3. Anaerobic digestion experiments with a CHNS analyser (LECO CHNS-932, Model 601-800-500),
using the manufacturer’s standard procedures. Proximate analysis
Anaerobic digestion runs of PW and digestate were carried out (ash, fixed carbon (FC) and volatile matter (VM)) was done by ther-
batchwise in 120 mL glass serum vials. The initial inoculum con- mogravimetric analysis (TGA) according to ASTM D7582 (ASTM,
centration was set at 15 g VS L
1 and the inoculum-to-substrate 2015). The HHV of solid samples were determined by using an
ratio (ISR) at 2:1 on a VS basis. The inoculum used was a granular IKA C2000 bomb calorimeter according to technical specification
anaerobic sludge from an industrial digester processing brewery EN 15400 (EN 15400:2011, 2011). Major elements in ashes were
wastewater under mesophilic conditions (35 °C), and was selected analysed by ICP-MS with an Elan 6000 Sciex instrument (Perkin
based on the results obtained comparing different inocula in the Elmer).
anaerobic digestión of PW from HTC process (de la Rubia et al., The raw digestate, PWs and the inoculum were characterized by
2018b). The inoculum showed the following characteristics: pH measuring pH with a Crison 20 Basic pH-meter; TS and VS accord-
7.2 ± 0.2; 80.7 ± 2.1 g TS L
1; 70.9 ± 1.5 g VS L
1 and 70.7 ± 1.7 g ing to standard methods 2540B and 2540E, respectively (APHA,
O2 L
1 of TCOD. A basal medium containing macro- and micronu- 2005) and total organic carbon (TOC) in a Shimadzu TOC–VCPN
trients prepared and dosed as described elsewhere (Villamil et al., auto analyser. Total Kjeldahl nitrogen (TKN) was determined as
2018) was added, after which the reaction volume was made up to described elsewhere (Villamil et al., 2018) and the TCOD according
60 mL with deionized water. The vials were sealed with rubber to Raposo et al. (2008). PWs and sacrificed samples from the AD
stoppers and metallic crimps and then the unfilled space of the vial tests (centrifuged and filtered through a filter of 0.45 lm pore size)
(60 mL) was purged with N2 for 3 min to ensure anaerobic condi- were analysed as follows: Soluble COD (SCOD) according to stan-
tions. Finally, the vials were held in a thermostatic shaking water dard method 5220D (APHA, 2005); carbohydrates by colorimetric
bath at 80 rpm equivalent stirring and mesophilic temperature method (Dubois et al., 1956); proteins by the Lowry method
(35 ± 1 °C). (Lowry et al, 1951); total alkalinity (TA) by titration to pH 4.3 with
The time course of AD was followed by using ten vials for each 0.02 N H2SO4 and total ammonia nitrogen (TAN) by distillation and
of the PW samples obtained at the three HTC temperatures tested titration according to standard methods 2320B and 4500-NH3,
(PW180, PW210, PW240) and for the digestate. Seven of them respectively (APHA, 2005). The concentrations of individual vola-
were sacrificed: two during the first three days and then every tile fatty acids (VFAs) from acetic to heptanoic, iso-forms included,
week. The remaining three vials were used for tracking the were determined by gas chromatography (GC) in a Varian 430-GC
methane production. Triplicate blank samples with no substrate instrument equipped with a flame ionization detector (FID) and a
were run to determine the background methane from the capillary column filled with Nukol (nitroterephthalic acid-
inoculum. The methane released was measured by volume dis- modified polyethylene glycol) (De la Rubia et al., 2018b). Chemical
placement (the carbon dioxide was removed previously by flushing species were identified in a GC–MS CP-3800/Saturn 2200 instru-
the gas through a 2 N NaOH solution) and expressed at standard ment equipped with a Varian CP-8200 autosampler injector (De
temperature and pressure (STP; 273.14 K, 1 bar) conditions. la Rubia et al., 2018a).
 J.D. Marin-Batista et al. / Waste Management 105 (2020) 566–574 569

3. Results and discussion herein obtained, alkaline metals might actively interact with Al,
Si, and Fe giving rise to eutectic mixtures lowering the ash melting
3.1. Characteristics of digestate and hydrochars temperature (Yang et al., 2019). Thus, ash removal would not only
increase the heating value of the hydrochars but also reduce the
Representative analyses of digestate, HCs, and UHCs are shown problems derived from slagging in the combustor.
in Table 1. As can be seen from the elemental composition of the After acid washing, all HCs showed a mass loss of around 15%,
virgin hydrochars (HC samples), the hydrothermal treatment did due to ash leaching. This led to recovery yields of 64.4, 57.3, and
not lead to significant carbonization. The higher relative C content 44.3% for UHC180, UHC210, and UHC240, respectively (Table 1).
of the UHC results from partial removal of the inorganic fraction The reduction of ash content was about 50% for all the HCs, conse-
(ash) by acid leaching. Only at the highest HTC temperature some quently leading to higher values of fuel ratio (FC/VM) in the UHCs,
moderate carbonization took place, as can be concluded from the which were around double than those of the corresponding virgin
comparison of the C content of the starting digestate and the HCs. This increase of the fuel ratio represents an improvement of
HC240 hydrochar on ash-free basis (55.3 and 62.8%, respectively). fuel quality since higher FC values help to control the heat loss
The main issues with ash are potential risks for slagging and caused by an unstable flame, typically exhibited by solid fuels with
fouling in the furnace upon combustion, which is related to ash high VM content (Marin-Batista et al., 2019). FC increased along
composition rather than its amount (Kratzeisen et al., 2010). Most with carbon content by a factor of approximately 2.5, which aug-
furnaces are designed to remove ash as a powdery residue and mented around 1.5-fold the HHVs initially obtained from hydro-
then, having ash with high melting-temperature is desirable. Alka- chars untreated with HCl. In addition, oxygen content decreased
line metals, potassium and sodium, reduce the ash melting tem- due to dissolution of certain O-containing species into the acid
perature, while magnesium and calcium have the opposite effect washing solution, like hydroxides, organic acids or phenols from
(Smith et al., 2018). During the HTC process, alkaline metals the hydrochar (Zhao et al., 2018). Consequently, H/C and O/C molar
responsible for fouling are generally dissolved into the PW (Yang ratios comparable to those of lignite were achieved.
et al., 2019). These elements seem to have high affinity with the
PW (Wang et al., 2019), but this is not the case for the digestate 3.2. Phosphorus reclamation
herein studied because the content of alkaline metals and even
magnesium in HCs scantly varied respect to digestate, as can be During the hydrothermal treatment, the TP of digestate
seen in Table 2, which discloses the major elements in the ash frac- (45.8 mg g
1, Table 2) was split into the HTC fractions (HC and
tion. The most abundant elements in the digestate ash correspond PW). Fig. 1 shows the changes in P species (NAIP, AIP, and OP) upon
to P, Al, Ca, Si, and Fe, which accumulate in the HCs in higher extent the hydrothermal treatment.
at increasing HTC temperature (Table 2). This can be associated As the HTC temperature increased, the TP retention yield in PW
with the interaction of P–PO3
4 with dissolved metallic cations became higher, reaching percent values of 11.1 (PW180), 18.2
and ammonia in PW to form precipitated phosphate salts onto (PW210), and 25.3 (PW240). This is due to higher dissolution of
the hydrochar surface (Becker et al., 2019). The higher amount of organic matter to the PW. Oppositely, OP retention yields in diges-
carboxylic groups on the hydrochar surface at increasing HTC tem- tate (48.8%) declined until 30.6 (HC180), 22.7 (HC210), and 17.9%
perature can theoretically enhance the cation exchange capacity (HC240). This finding draw the conclusion that under HTC condi-
(Kim et al., 2014). However, the diversity of metal species in the tions the OP of digestate was released into the PW as ortho-
HCs can provoke some problems. During combustion of the HCs phosphate, wherein most likely reacted with Mg2+, Al3+, and

Table 1
Characteristics of digestate, hydrochars, and upgraded hydrochars (dry basis).

Digestate HC180 HC210 HC240 UHC180 UHC210 UHC240

C (%) 32.7 30.8 31.8 32.6 50.1 52.5 55.8
H (%) 4.9 4.3 4.3 4.1 5.9 5.9 6.0
N (%) 5.1 4.2 4.1 4.1 5.2 5.0 4.7
S (%) 1.0 1.0 1.0 1.1 1.4 1.5 1.5
O (%)* 15.4 16.8 14.9 10.0 14.7 15.3 5.2
VM (%) 54.7 50.9 48.3 44.0 60.9 59.4 55.3
FC (%) 4.4 6.2 7.8 7.9 16.4 20.8 17.9
Ash (%) 40.9 42.9 43.9 48.1 22.7 19.8 26.8
HHV (MJ kg
1) 14.9 14.7 14.9 15.1 20.5 21.6 23.1
Yield (%) – 74.2 67.8 51.8 64.4 57.3 44.3

Note: Each data showed a standard deviation  0.2.

*
By difference.

Table 2
Major elements in the ash fraction of digestate, hydrochars, and upgraded hydrochars (dry wt. %).

Element Digestate HC180 HC210 HC240 UHC180 UHC210 UHC240

K 0.28 0.27 0.26 0.35 0.16 0.14 0.13
Na 0.16 0.14 0.14 0.18 0.01 0.01 0.01
Mg 0.32 0.33 0.34 0.45 0.09 0.04 0.01
Ca 3.02 3.28 3.23 3.98 0.02 0.01 0.01
Si 1.94 1.85 2.24 2.68 0.03 0.02 0.01
Fe 1.58 1.74 1.78 2.21 0.38 0.33 0.30
Al 4.19 3.84 4.14 5.57 0.97 0.89 0.91
P 4.58 5.28 5.32 6.30 0.06 0.03 0.02

Note: Each data showed a standard deviation below ±0.01.

570 J.D. Marin-Batista et al. / Waste Management 105 (2020) 566–574

species could precipitate due to calcium base neutralisation. From

a thermodynamic point of view, hydroxyapatite (Ca10(PO4)6(OH)2,
Ca/P of 1.67) precipitation should dominate since it is the most
stable bonding form of calcium and orthophosphate ions (Cichy
et al., 2019). However, a Ca/P molar ratio of 0.60 was barely
achieved in the pH range of 7 to 9. Possible phosphate precipitates
are heptacalcium phosphate (Ca7(P5O16)2; Ca/P of 0.70), tetracal-
cium dihydrogen phosphate (Ca4H2P6O2; Ca/P of 0.67), monocal-
cium phosphate monohydrate (Ca(H2PO4)2H20; Ca/P of 0.50),
and calcium metaphosphate (Ca(PO3)2; Ca/P of 0.50). The leaching
conditions (i.e., pH, mixing time) and stoichiometric relation
between P and metal ions (Al3+, Fe2+/3+, Mg2+, K+, and Na+) in lea-
chates, may lead to precipitation of different phosphate salts that
Fig. 1. Distribution of the initial P of digestate into the hydrochars and process
water from HTC. somewhat interfere with the formation of apatite species. Despite
the conditions for hydroxyapatite precipitation were not optimal,
the side reactions of phosphate with the metal ions in the leachate
Fe3+/2+ to increase NAIP retention yield in the solid from 26.8% (di- implied lower needs of calcium to achieve complete recovery of P
gestate) to around 33% for the hydrochars obtained at different from the acid leachates. The phosphate species in brown solids
temperatures. Meanwhile, digestate AIP retention yield of 24.5% have a very low solubility which impedes direct use as fertilizer,
scarcely varied during the hydrothermal treatment (Fig. 1), but that solid product can be used for phosphoric acid production.
because a Ca/P molar ratio of 0.5 kept constant regardless the
HTC temperature (Table 2). Interestingly, very diverse findings
3.3. Characteristics of the process water
have been reported in literature. For instance, Zhao et al. (2018)
concluded that HTC partially turns OP and NAIP from lignocellu-
The characteristics of the PWs obtained by digestate HTC are
losic digestate into AIP in the PW, likely through a sequential
collected in Table 3. Increasing the HTC temperature leads to
reaction including the hydrolysis of OP, the dissolution of NAIP
higher dissolution of total and volatile solids from the starting
and the precipitation of phosphate with Ca2+ and/or hydroxyl
digestate. This fact could be perceived as a subsequent increase
groups. However, Wang et al. (2017) stated that an acidic reaction
of SCOD in the PW. However, the SCOD showed a downward trend
environment promotes the transformation of AIP to NAIP, while an
from 61.5 to 53.9 g L
1 after increasing the HTC temperature from
alkaline environment provokes the opposite. Certainly, HTC
210 to 240 °C. This reduction in SCOD can be related to the signif-
promoted the transformation of digestate OP into IP, and IP speci-
icant decomposition of proteins and carbohydrates at higher HTC
ation during HTC may be linked to the amount and composition of
temperature. It has been reported that dehydration is the major
inorganic elements in the feedstock.
reaction during HTC of sewage sludge, while deamination and
Nonetheless, the vast majority of TP content of HC was released
hydrolysis occur significantly at higher HTC temperature or longer
by acid leaching along with a large fraction of multivalent and
residence time. Particularly, proteins are hydrolysed to peptides
monovalent metals, as can be concluded from Table 2. Despite P
and amino acids, which in turn are oxidatively degraded to fatty
and metals content varied among acid leachates (data not shown),
acids and ammonia, leading to increased alkalinity (Chen et al.,
close to 100% of dissolved TP was precipitated in form of brown
2019). Significantly high content of proteins were found in
solids by addition of CaO. Fig. 2 shows the content of major ele-
PW180, but decreased as the HTC temperature increased. The same
ments in brown solids precipitated from HC180 acid leachate. As
trend was observed for total VFA (TVFA). Thus, ammonia, TA, and
pH increases upon CaO addition, P content in the brown solids
pH of PW increased with HTC temperature.
increased from  10.5 mg g
1 at pH 5 to  42 mg g
1 at pH 9,
The carbon balance based on elemental analysis (solid phase)
which is comparable to the P content of low grade phosphate ores
and total organic carbon (liquid phase) matched within 80.2%
(26.5–163.5 mg g
1) (Mar and Okazaki, 2018). Considering that dif-
(240 °C) and 92.8% (180 °C). Carbon content in the gaseous stream
ferent phosphorus chemical species (e.g., H2PO
2
3

4 , HPO4 , and PO4 )
increased with carbonization temperature. This gaseous phase
occur within a pH range of 5 to 9 (Vardanyan et al., 2018) and due
contains mainly CO2 (>90%) and small amounts of CH4, H2, and
to the abundance of Ca in brown solids (Fig. 2), different apatite
CO (Cha et al., 2016; Basso et al., 2016). In the case of nitrogen
content, analyzed by elemental analysis (solid phase) and total
Kjeldahl nitrogen (process water), the same trend was observed.
Mass nitrogen balance closure was from 99.2% (180 °C) to 90.8%

Table 3
Analysis of the process water from HTC of digestate at different temperature.

PW180 PW210 PW240

Total solids (g L
1) 52.2 (0.2) 46.3 (0.9) 30.1 (0.5)
Total volatile solids (g L
1) 50.3 (0.1) 44.6 (0.1) 28.9 (0.1)
Soluble chemical oxygen demand (g L
1) 56.2 (0.8) 61.5 (0.3) 53.9 (0.2)
pH 7.4 (0.1) 7.9 (0.2) 8.9 (0.1)
Total alkalinity (g CaCO3 L
1) 1.1 (0.1) 2.6 (0.1) 3.2 (0.1)
Total organic carbon (g L
1) 28.8 (0.2) 28.3 (0.1) 25.9 (0.1)
Total Kjeldahl nitrogen (g L
1) 8.1 (0.2) 9.0 (0.1) 9.7 (0.2)
Total carbohydrates (g L
1) 7.6 (0.1) 2.8 (0.1) 0.6 (0.1)
Total proteins (g L
1) 11.7 (0.2) 11.0 (0.1) 9.8 (0.4)
Total ammonia nitrogen (g L
1) 4.9 (0.2) 5.2 (0.1) 6.3 (0.2)
Total volatile fatty acids (g L
1) 3.5 (0.2) 3.4 (0.3) 2.0 (0.3)
Fig. 2. Content of major elements in the brown solid precipitated from HC180 acid
leachate. Note: Standard deviation in parentheses.
 J.D. Marin-Batista et al. / Waste Management 105 (2020) 566–574 571

(240 °C). Taking into account the nitrite and mainly nitrate forma-
tion the nitrogen mass balance matched within 99.5% at least.

3.4. Anaerobic digestion of process water and digestate

Fig. 3 shows the time course of the methane yield upon AD of

the digestate and PWs resulting from digestate HTC. An initial
lag-phase of 3 days was observed in all cases, indicative that the
inoculum required some time to adapt to the substrate (De la
Rubia et al., 2018b). Then, the methane production reached
325 ± 11 STP mL CH4 g
1 VS for PW180 and a lower value
(279 ± 9 STP mL CH4 g
1 VS) for PW210. These values were signif-
icantly higher than the observed for the digestate (150 ± 1 STP mL
CH4 g
1 VS). The increase in carbonization temperature showed a
negative effect on the anaerobic biodegradability of the resulting
PW, which was dramatic for the PW generated at 240 °C where
methane production barely took place. The results are useful
regarding the possibility to recirculate the HTC process water
inside the digester. The ratio between the mass of input entering
the digester and the mass of HTC process water should be estab-
lished in long-term experiments, and the possible remaining pro-
cess water could be treated with the wastewater entering in the
treatment plant.
Methanogenic microorganisms use SCOD in the form of VFA,
specifically as acetic acid, for methane production. Therefore, the
time course of individual VFA (Fig. 4) can provide useful informa-
tion on the performance of the acidogenesis and methanogenesis
stages of AD. In the early stages acetic acid (C2) was by far the
major VFA produced, while longer chain VFAs such as valeric
(C5) and iso-valeric (i-C5) were present in low concentrations
(<100 mg acetic acid L
1). A similar VFA profile was observed by
Chen et al. (2019) in the anaerobic digestion of the PW derived
from sewage sludge HTC. VFA are easily-biodegradable compounds
and the metabolic pathway of individual VFA was influenced by
the HTC temperature (Fig. 4). During the AD of PW180 and
PW210, the concentration of C3 and i-C5 gradually decreased
due to the effective acidogenic–acetogenic stage, wherein VFAs Fig. 4. Time course of the relative distribution of individual components of the total
volatile fatty acids fraction (expressed as equivalent acetic acid) upon AD of PWs.
are turned into C2. Remarkably, C4 and i-C4 were rapidly con-
verted into C2 during the first week, confirming that C4 and i-C4
conversion is favoured within the VFA metabolic pathway. At the
end of the experiment, the TVFA concentration (expressed as mg methane from acetate was fairly rapid after the lag period. In con-
acetic acid L
1) in the cases of PW180 and PW210 was, respec- trast, the early inhibition of methanogens during the AD of PW240
tively, 316 ± 7 mg L
1 (accounting for TVFA reduction of 70%) led to accumulation of C2 along the digestion time (increasing from
and 376 ± 20 mg L
1 (accounting for TVFA reduction of 60%). This the initial concentration of 612 mg C2 L
1 to 1266 mg C2 L
1 at the
notable reduction of the VFAs concentration demonstrates that the end of the experiment). Herein, C4 and i-C4 were rapidly converted
methanogenic stage was not disturbed and the formation of into C2 while methanogens were unable to remove C2 fast enough.
This imbalance in acetate production/uptake reaction rates some-
how affected to C3 and i-C5 metabolic pathway, leading to accu-
mulation of these species. Thus, TVFA concentration rose up to
1900 mg acetic L
1, comprising mainly 67.1% C2, 12.1% C3, and
17.8% i-C5. Therefore, there should be some inhibiting compounds
in the PWs that substantially contributed to inhibition of methano-
genesis and low methane yields in the case of PW240.
TVFA evolution (Fig. 4) and significant AD variables such as pH,
TA, and TAN allow evaluating the AD process (De la Rubia et al.,
2011). For each PW the pH slightly varied (from 8.0–8.5 to 7.8–
7.6) because the alkalinity of the system prevents higher pH drops,
associated to VFA accumulations during AD. TA was initially  1.
5 mg CaCO3 L
1 in all cases but increased up to 6.0 g CaCO3 L
1
for PW180 and PW210 and 3.8 g CaCO3 L
1 for PW240, anyway
providing enough buffer capacity (Villamil et al., 2020). PW240
showed the lowest final TA values because part of the alkalinity
was likely consumed to neutralise VFA accumulation. Besides,
the early inhibition in the case of PW240 lowered down the
Fig. 3. Time course of cumulative methane yield from AD of process waters and
digestate. hydrolysis rate of proteins to an extent that TAN was released to
572 J.D. Marin-Batista et al. / Waste Management 105 (2020) 566–574

a rate unable to counteract TA deficits. The final TAN to TKN con- aromatic species were also detected in all PWs (e.g, 1,3-dioxolane,
centration ratio is usually used as a valid index for protein hydrol- 1,2,4,5-tetramethyl-benzene, 4-formyl-benzoic acid, 2-methyl-6-
ysis in AD (Villamil et al., 2019). The concentration of TAN (2-propenyl)-phenol, dichloromethyl-benzene). This is generally
increased along AD, suggesting a growing trend for the hydrolysis attributed to the Maillard reactions involving carbohydrate and
of TKN in all cases. However, the final values of TAN to TKN ratio of amino acids as well as cyclization reactions involving alcohols, alde-
1.08 (PW180), 0.92 (PW210), and 0.74 (PW240) indicate that the hydes, furans, and pyrroles at high HTC temperatures (Chen et al.,
hydrolytic stage was shorter in the AD of PWs obtained at higher 2019). Anaerobic digestion allowed partial removal of the afore-
HTC temperatures. The final TAN ranged 1.3–1.4 g L
1 for PW180 mentioned aromatic species in all PWs as was previously observed
and PW210, much lower than the considered inhibitory value for by Villamil et al. (2019) in AD of PW from sewage sludge HTC. How-
methanogenic microorganisms (1.7 g TAN L
1) (Villamil et al., ever, new recalcitrant aromatic compounds appeared during AD of
2019). Meanwhile, the final TAN in the case of PW240 reached 1. PW180 (2,4,6-trimethoxyacetophenone), PW210 (2,3,5,6-
9 ± 0.1 g L
1, slightly higher than the aforementioned inhibitory tetramethyl-phenol) and PW240 (2,4,6-trimethoxyacetophenone,
value. Moreover, the removal of SCOD upon anaerobic digestion 7-methyl-1H-indole, and 4-methyl-phenol), accounting for nearly
decreased as the temperature of HTC increased (46.2 and 38.1% 60% of normalized composition of each PW. The presence of 7-
for PW180 and PW210, respectively), being this fact much more methyl-1H-indole clearly indicates the process inhibition occurred
significant for PW240, consistently with the accumulation of VFA. for PW240 as a result of poor digestion, taking into account that this
The remaining SCOD can be assigned to refractory compounds compound can be degraded by methanogens and sulphate-
formed during the hydrothermal treatment, as previously found reductive microbial populations (Marin-Batista et al., 2019).
by Villamil et al. (2018) for AD of PW from sewage sludge HTC.
3.6. Energy recovery
3.5. Analysis of refractory compounds
A value of 14.9 ± 0.2 MJ kg
1 (see Table 1) was taken as refer-
Fig. A1 (appendix 1) shows the semi-quantitative composition of ence HHV, corresponding to the energy potentially obtained from
PW180, PW210 and PW240 before and after AD. The species have direct combustion of the digestate feedstock. However, this direct
been gathered in chemical groups and their concentrations are use of digestate as fuel is not recommended (Kratzeisen et al.,
expressed in terms of % GC peak area. Higher HTC temperature led 2010), due to the high amount of energy required to dry the dewa-
to a wider diversity of nitrogen-bearing species in the PW. tered digestate (2.1 MJ kg
1). If the digestate ashes (40.9 ± 0.2%)
The PW180 showed the presence of ring-type structures with were completely removed, the HHV would be significantly
one or two N heteroatoms, such as amines (e.g., trimethylamine, improved (up to 30.2 MJ kg
1), which can give an insight of the
1-butanamine, 1,2-benzenediamine), pyrimidines (4-methyl- maximum amount of energy potentially produced upon combus-
pyrimidine) and pyrazines (2-ethyl-3-methyl-pyrazine, 2,5- tion of the feedstock after in depth upgrading. However, direct
dimethyl-pyrazine, 2,3-diethylpyrazine), which are generally extraction of the digestate ashes would be quite inefficient, since
formed during the HTC process from hydrolysis of proteins and car- most of the inorganic matter is intracellularly stored and/or
bohydrates (De la Rubia et al., 2018a). Increasing HTC temperature entrapped within organic matter (Kleemann et al., 2017).
provoked the disappearance of some amine species (e.g., trimethy- Fig. 5 shows the energy associated to the combustion of HCs
lamine and 1-butanamine) from the PW, due to deamination (Chen and anaerobic digestion of PW, and also the corresponding to
et al., 2019), and the appearance of new pyrimidine species (e.g, 4,6- UHCs. The removal of ashes by acid leaching of UHCs, as has been
dimethyl-pyrimidine at 210 °C and 3-ethyl-4-methyl-pyrimidine at already discussed (see Table 2), allowed a potential way for energy
240 °C), that showed to be refractory to AD. Some anaerobic densification of these carbonaceous materials. Coupling combus-
biodegradable pyrazine species (e.g., 2,5-dimethyl-pyrazine and tion of HC180 with AD of PW180 can provide 14.1 MJ kg
1 dry
2,5-dimethyl-3-propyl-pyrazine) were detected in PW180 and feedstock, somewhat higher than the derived from combustion of
PW240, while some other (e.g., 2-ethyl-3-methyl-pyrazine and HC210 plus AD of PW210 (13.5 MJ kg
1 dry feedstock). These val-
2,3-diethylpyrazine) identified in all the PWs showed to be ues represent an energy recovery of 94.6 and 90.6% of the energy
refractory to AD. Increasing HTC temperature to 240 °C led to the content of the feedstock. On the contrary, the sole combustion of
appearance of nitrogen-bearing aromatic species (1H-pyrrole, HC240 would yield only 7.8 MJ kg
1 dry feedstock, representing
3-ethyl-2,4-dimethyl-ortho-phenylenediamine, 4,5-dimethyl-2- 52.3% of the net amount of energy potentially provided by direct
ethylpiperidine) that were completely removed upon AD. Other digestate combustion. In the case of PW240 there is no

Fig. 5. Energy recovery through combustion of hydrochars (HCs and UHC) and anaerobic digestion of PWs.
 J.D. Marin-Batista et al. / Waste Management 105 (2020) 566–574 573

contribution of anaerobic digestion since the methane yield is neg- Cha, J.S., Park, S.H., Jung, S.-C., Ryu, C., Jeon, J.-K., Shin, M.-C., Park, Y.-K., 2016.
Production and utilization of biochar: A review. J. Ind. Eng. Chem. 40, 1–15.
ligible. Regarding the upgraded HCs, the combustion of UHC180
https://doi.org/10.1016/j.jiec.2016.06.002.
and UHC210 could provide 13.2 and 12.3 MJ kg
1 dry feedstock, Chen, H., Rao, Y., Cao, L., Shi, Y., Hao, S., Luo, G., Zhang, S., 2019. Hydrothermal
which implies 88.6 and 82.6% energy recovery, respectively. conversion of sewage sludge: Focusing on the characterization of liquid
products and their methane yields. Chem. Eng. J. 357, 367–375. https://doi.
org/10.1016/j.cej.2018.09.180.
4. Conclusions _ zał,
Cichy, B., Kuzd _ E., Krztoń, H., 2019. Phosphorus recovery from acidic wastewater
by hydroxyapatite precipitation. J. Environ. Manage. 232, 421–427. https://doi.
org/10.1016/j.jenvman.2018.11.072.
Hydrothermal carbonization provides an interesting way for De la Rubia, M.A., Raposo, F., Borja, R., 2011. Influence of particle size and chemical
sewage sludge valorisation into solid fuels, also allowing nutrient composition on the performance and kinetics of anaerobic digestion process of
sunflower oil cake in batch mode. Biochem. Eng. J. 59, 162–167. https://doi.org/
recovery. The hydrothermal treatment turns organic P associated
10.1016/j.bej.2011.09.010.
to the volatile matter into inorganic P (mainly non-apatite species) De la Rubia, M.A., Villamil, J.A., Rodriguez, J.J., Borja, R., Mohedano, A.F., 2018a.
from the hydrochars surface. Thus, the vast majority of total P in Mesophilic anaerobic co-digestion of the organic fraction of municipal solid
hydrochars was easily leached out and can be precipitated in form waste with the liquid fraction from hydrothermal carbonization of sewage
sludge. Waste Manag. 76, 315–322. https://doi.org/10.1016/j.
of brown solids (total P content of 41.8 mg g
1, similar to that in a wasman.2018.02.046.
low grade ore) of potential use in the H3PO4 industry. De la Rubia, M.A., Villamil, J.A., Rodriguez, J.J., Mohedano, A.F., 2018b. Effect of
A mild temperature of 180 to 210 °C is recommended for HTC inoculum source and initial concentration on the anaerobic digestion of the
liquid fraction from hydrothermal carbonisation of sewage sludge. Renew.
digestate, in order to obtain hydrochars with attractive HHVs and Energy 127, 697–704. https://doi.org/10.1016/j.renene.2018.05.002.
PWs with relatively low content of refractory compounds to yield Dragicevic, I., Eich-Greatorex, S., Sogn, T.A., Horn, S.J., Krogstad, T., 2018. Use of high
additional energy in form of biogas. The energy content of the metal-containing biogas digestates in cereal production - Mobility of chromium
and aluminium. J. Environ. Manage. 217, 12–22. https://doi.org/10.1016/
hydrochars and the methane produced from anaerobic digestion j.jenvman.2018.03.090.
of process water generated at low HTC temperature (180 °C) allows Dubois, M., Gilles, K.A., Hamilton, J.K., Rebers, P.A., Smith, F., 1956. Colorimetric
~95% potential recovery of the energy content in the digestate method for determination of sugars and related substances. Anal. Chem 28,
350–356.
feedstock. Moreover, this amount of energy in the digestate refers
European Banking Authority, 2017. Annual statistical report of the European biogas
to dry basis and then to be available upon combustion would association. http://european-biogas.eu. Last seen on 12/05/2019.
require the evaporation of high amount of water with the corre- EN 15400:2011, 2011. Solid Recovered Fuels – Determination of Calorific Value.
CEN Eur. CS, Brussels.
sponding thermal energy consumption.
EurObserv’ER, 2017. Biogas Barometer. https://www.eurobserv-er.org/. Last seen on
14/05/2019.
Declaration of Competing Interest European Commission, 2018. Directive (EU) 2018/851 of the European parliament
and of the council of 30 May 2018 amending directive 2008/98/EC on waste.
Off. J. Eur. union, 109–140.
The authors declare that they have no known competing finan- Kacprzak, M., Neczaj, E., Fijałkowski, K., Grobelak, A., Grosser, A., Worwag, M., Rorat,
cial interests or personal relationships that could have appeared A., Brattebo, H., Almås, Å., Singh, B.R., 2017. Sewage sludge disposal strategies
for sustainable development. Environ. Res. 156, 39–46. https://doi.org/10.1016/
to influence the work reported in this paper. j.envres.2017.03.010.
Kim, D., Lee, K., Park, K.Y., 2014. Hydrothermal carbonization of anaerobically
digested sludge for solid fuel production and energy recovery. Fuel 130, 120–
Acknowledgments
125. https://doi.org/10.1016/j.fuel.2014.04.030.
Kleemann, R., Chenoweth, J., Clift, R., Morse, S., Pearce, P., 2017. Comparison of
Authors greatly appreciate funding from Spanish Ministry of phosphorus recovery from incinerated sewage sludge ash (ISSA) and pyrolysed
Economy and Competitiveness (Project CTM2016-76564-R; project sewage sludge char (PSSC). Waste Manag. 60, 201–210. https://doi.org/10.1016/
j.wasman.2016.10.055.
RYC-2013-12549) and Madrid Regional Government (Project Kratzeisen, M., Starcevic, N., Martinov, M., Maurer, C., Müller, J., 2010. Applicability
P2018/EMT-4344). Authors thank to Instituto Colombiano de of biogas digestate as solid fuel. Fuel 89, 2544–2548. https://doi.org/10.1016/
Crédito Educativo y Estudios Técnicos en el Exterior (ICETEX) j.fuel.2010.02.008.
Lowry, O.H., Rosebrough, N.J., Farr, Lewis Farr, A., 1951. Protein measurement with
(Colombia) as part of the grant awarded to José Marin-Batista. the folin phenol reagent. J. Biol. Chem. 193, 265–275. http://www.jbc.
The authors thank C.M. Lazaro for her valuable help. org/content/193/1/265.citation.
Mar, S.S., Okazaki, M., 2018. Investigation of Cd contents in several phosphate rocks
used for the production of fertilizer. Microchem. J. 104, 17–21. https://doi.org/
Appendix A. Supplementary material 10.1016/j.microc.2012.03.020.
Marin-Batista, J., Villamil, J.A., Rodriguez, J.J., Mohedano, A.F., De la Rubia, M.A.,
2019. Valorization of microalgal biomass by hydrothermal carbonization and
Supplementary data to this article can be found online at anaerobic digestion. Bioresour. Technol. 274, 395–402. https://doi.org/10.1016/
https://doi.org/10.1016/j.wasman.2020.03.004. j.biortech.2018.11.103.
Raposo, F., De la Rubia, M.A., Borja, R., Alaiz, M., 2008. Assessment of a modified and
optimised method for determining chemical oxygen demand of solid substrates
References and solutions with high suspended solid content. Talanta 76, 448–453. https://
doi.org/10.1016/j.talanta.2008.03.030.
American Public Health Association, 2005. Standard methods for the examination of Rodriguez Correa, C., Bernardo, M., Ribeiro, R.P.P.L., Esteves, I.A.A.C., Kruse, A., 2017.
water and wastewater, 21st ed. Washington, DC, USA. https://doi.org/30M11/ Evaluation of hydrothermal carbonization as a preliminary step for the
98. production of functional materials from biogas digestate. J. Anal. Appl.
Aragón-Briceño, C., Ross, A.B., Camargo-Valero, M.A., 2017. Evaluation and Pyrolysis 124, 461–474. https://doi.org/10.1016/j.jaap.2017.02.014.
comparison of product yields and bio-methane potential in sewage digestate Silvestre, G., Fernández, B., Bonmatí, A., 2015. Significance of anaerobic digestion as
following hydrothermal treatment. Appl. Energy 208, 1357–1369. https://doi. a source of clean energy in wastewater treatment plants. Energy Convers.
org/10.1016/j.apenergy.2017.09.019. Manag. 101, 255–262. https://doi.org/10.1016/j.enconman.2015.05.033.
American Society for Testing and Materials, 2015. Standard Test Methods for Smith, A.M., Whittaker, C., Shield, I., Ross, A.B., 2018. The potential for production of
Proximate Analysis of Coal and Coke by Macro Thermogravimetric Analysis. high quality bio-coal from early harvested Miscanthus by hydrothermal
Method D7582-15. ASTM Int. Pennsylvania. carbonisation. Fuel 220, 546–557. https://doi.org/10.1016/j.fuel.2018.01.143.
Basso, D., Patuzzi, F., Castello, D., Baratieri, M., Rada, E.C., Weiss-Hortala, E., Fiori, L., Stutzenstein, P., Bacher, M., Rosenau, T., Pfeifer, C., 2018. Optimization of nutrient
2016. Agro-industrial waste to solid biofuel through hydrothermal and carbon recovery from anaerobic digestate via hydrothermal carbonization
carbonization. Waste Manag. 47, 114–121. https://doi.org/10.1016/j. and investigation of the influence of the process parameters. Waste Biomass
wasman.2015.05.013. Valori 9, 1303–1318. https://doi.org/10.1007/s12649-017-9902-4.
Becker, G.C., Wüst, D., Köhler, H., Lautenbach, A., Kruse, A., 2019. Novel approach of Vardanyan, A., Kafa, N., Konstantinidis, V., Gu, S., Vyrides, I., 2018. Phosphorus
phosphate-reclamation as struvite from sewage sludge by utilising dissolution from dewatered anaerobic sludge: Effect of pHs, microorganisms,
hydrothermal carbonization. J. Environ. Manage. 238, 119–125. https://doi. and sequential extraction. Bioresour. Technol. J. 249, 464–472. https://doi.org/
org/10.1016/j.jenvman.2019.02.121. 10.1016/j.biortech.2017.09.188.
574 J.D. Marin-Batista et al. / Waste Management 105 (2020) 566–574

Villamil, J.A., Mohedano, A.F., Martín, J.S., Rodriguez, J.J., De la Rubia, M.A., 2020. chemical extraction, purification and crystallization. J. Clean. Prod. 181, 717–
Anaerobic co-digestion of the process water from waste activated sludge 725. https://doi.org/10.1016/j.jclepro.2018.01.254.
hydrothermally treated with primary sewage sludge. A new approach for Wang, T., Zhai, Y., Zhu, Y., Peng, C., Wang, Tengfei, Xu, B., Li, C., Zeng, G., 2017.
sewage sludge management. Renew. Energy 146, 435–443. https://doi.org/ Feedwater pH affects phosphorus transformation during hydrothermal
10.1016/j.renene.2019.06.138. carbonization of sewage sludge. Bioresour. Technol. 245, 182–187. https://doi.
Villamil, J.A., Mohedano, A.F., Rodriguez, J.J., De la Rubia, M.A., 2018. Valorisation of org/10.1016/j.biortech.2017.08.114.
the liquid fraction from hydrothermal carbonisation of sewage sludge by Xu, Y., Yang, F., Zhang, L., Wang, X., Sun, Y., Liu, Q., Qian, G., 2018. Migration and
anaerobic digestion. J. Chem. Technol. Biotechnol. 93, 450–456. https://doi.org/ transformation of phosphorus in municipal sludge by the hydrothermal
10.1002/jctb.5375. treatment and its directional adjustment. Waste Manag. 81, 196–201. https://
Villamil, J.A., Mohedano, A.F., Rodriguez, J.J., De Rubia, M.A., 2019. Anaerobic co- doi.org/10.1016/j.wasman.2018.10.011.
digestion of the aqueous phase from hydrothermally treated waste activated Yang, M., Xie, Q., Wang, X., Dong, H., Zhang, H., Li, C., 2019. Lowering ash slagging
sludge with primary sewage sludge. A kinetic study. J. Environ. Manage. 231, and fouling tendency of high-alkali coal by hydrothermal pretreatment. Int. J.
726–733. https://doi.org/10.1016/j.jenvman.2018.10.031. Min. Sci. Technol. 29, 521–525. https://doi.org/10.1016/j.ijmst.2018.05.007.
Wang, L., Chang, Y., Liu, Q., 2019. Fate and distribution of nutrients and heavy Zhao, P., Shen, Y., Ge, S., Yoshikawa, K., 2014. Energy recycling from sewage sludge
metals during hydrothermal carbonization of sewage sludge with implication by producing solid biofuel with hydrothermal carbonization. Energy Convers.
to land application. J. Clean. Prod. 225, 972–983. https://doi.org/10.1016/j. Manag. 78, 815–821. https://doi.org/10.1016/j.enconman.2013.11.026.
jclepro.2019.03.347. Zhao, X., Becker, G.C., Faweya, N., Correa, C.R., Yang, S., Xie, X., 2018. Fertilizer and
Wang, Q., Li, J., Tang, P., Fang, L., Poon, C.S., 2018. Sustainable reclamation of activated carbon production by hydrothermal carbonization of digestate.
phosphorus from incinerated sewage sludge ash as value-added struvite by Biomass Conv. Bioref. 8, 423–436. https://doi.org/10.1007/s13399-017-0291-5.