Lesson3

1
 Sewage sludge valorization

Y. Fan et al. Biomass and Bioenergy 165 (2022) 106570

Fig. 2. Potential sewage sludge to resource and energy recovery routes [1,8].

extraction, incineration, anaerobic digestion (AD), as well as thermo- contain high water contents. Water is utilized as a reaction medium,
Sewage sludge: composition
 Valorization technologies
T.E. Seiple et al. Journal of Environmental Management 270 (2020) 110852

Fig. 1. As-modeled layout of HTL (1a) and AD (1b) sludge conversion pathways.

substitution. alphanumeric treatment configuration identifiers, listed in Supple-

In total, 46 liquid-solid process identifiers were assigned to charac-
terize existing biological treatment configurations for the entire fleet of
WWTPs. Identifiers were manually assigned for all facilities with
influent flow !37.8 ML/d (10 Mgal/d) based on facility and regulatory
documentation and expert knowledge. Facilities within the flow range of
mental Table S1, are used as a key to query modeled chemical oxygen
demand (COD), and dry weight total suspended solids magnitudes by
waste phase from the WRF model with the same key. COD values are
converted from a mass to energy basis assuming 13.9 kJ/g COD, the
maximum heat energy possible from methanogenic wastewater treat-
Hydrothermal liquefaction: a promising route to convert biomass into valuable fuels & chemicals

4
Water properties: hydrothermal liquefaction
Hydrothermal liquefaction: a promising route to convert biomass into valuable fuels & chemicals

HTL

O (%)
+
partial up-grading

Up-grading

6
0031, China
e and Engineering, Central South University, Changsha 410083, China
twa, Central Mining Institute, Plac Gwarków 1, 40-166 Katowice, Poland
HTL of sewage sludge
S G R A P H I C A L A B S T R A C T

process conditions on
unicipal sludge.
ilizations of each
f municipal sludge

f heavy metals in the

municipal sludge.
the industrial appli-
unicipal sludge.

F O A B S T R A C T

Hydrothermal liquefaction (HTL) is an effective medium-temperature, high-pressure thermochemical process to

dispose municipal sludge (MS), and biocrude (a crude bio-oil) is its main product. Many efforts are continued
 Reaction mechanisms
H. Shahbeik et al. Renewable and Sustainable Energy Reviews 189 (2024) 113976

Fig. 4. Potential reaction pathway of the biomass macromolecules to various end-products via HTL process as a function of temperature [59]. Reproduced with
 content of biocrude oil in the presence of hydrogen at temperatures leading to a lowered O/C atomic ratio in the upgraded biocrude oil
rotreating, catalytic cracking offers a broader spectrum of products,
between 500 and 550 ◦ C [260]. This process converts heavier hydro-
cost, making it less feasible for large-scale commercial implementation.
(Fig. 22B). It is worth noting that the emulsification upgrading route,
tercarbons
compatibility with
into lighter various feedstocks,
constituents by breakingand C–Cyields
bonds.aCompared
higher pro-to Additionally,
while this method
effective, poses may
challenges due not
to itssignificantly remove certain
high energy consumption and unde-
ionhydrotreating,
of end products. However,
catalytic crackingit offers
does have its drawbacks,
a broader spectrum ofincluding
products, sirable
cost, compounds
making from for
it less feasible biocrude oil, commercial
large-scale as indicated in Fig. 22B.
implementation.
er greater
carbon compatibility
recovery yield
hydrotreating,
portion of end the
and
with
catalytic
products.
swiftfeedstocks,
various
cracking
However, process
it does Biocrude quality
catalyst deactivation
and yields a [261].
results
have its
Un-
higher pro-
in low-energy
drawbacks, including
Other upgrading
Additionally,
on thecompounds
sirable
this method
physicochemical
methods may
may not be used atremove
significantly
characteristics
from biocrude
different
of the biocrude
oil, as indicated
stages,
certain depending
unde-
oil and the nature
in Fig. 22B.
uellower
due tocarbon recoveryin
a reduction yield
the and swiftatoms
carbon catalyst
ofdeactivation
biocrude oil. [261]. Un- and Other upgradingofmethods
properties may beupgrading
the desired used at different stages,ordepending
biofuels chemicals. For
Dueliketohydrotreating, the catalytic
the limitations cracking process
of hydrotreating and results in low-energy
catalytic cracking on the physicochemical
example, hydrogen can characteristics
be generated of the biocrude
through oil and the
catalytic nature
steam reforming
biofuel
hods, due to
they area reduction in the carbon atoms
often synergistically of biocrude
combined inoil.practical and properties
(800–900 ◦
C) ofusing
the desired
nickel, upgrading biofuels or chemicals.
whereas value-added biochemical For species
Heteroatoms: O, N, S problem for utilization= need of up-grading
Due to the limitations of hydrotreating and catalytic cracking example, hydrogen can be generated through catalytic steam reforming
can be extracted from biocrude oil under mild conditions via distillation,
methods, they are often synergistically combined in practical (800–900 C) using nickel, whereas value-added biochemical species
◦

H. Shahbeikcan be extracted from biocrude oil under mild conditions via distillation,
et al. Renewable and Sustainable Energy Reviews 189 (2024) 113976

solvent extraction, or chemical modification [258]. However, these

methods still require further development of cheaper and simpler
equipment and refining techniques. Overall, to meet the standards for
specific fuels, the large molecules and oxygenated compounds in bio-
crude oil, including phenols (i.e., cresols, anisole, guaiacols catechols,
and syringols), aldehydes, carboxylic acids, alcohols, and carbohy-
drates, must be typically degraded into shorter molecules in cracking
processing units (i.e., hydro-cracker, catalytic cracker, and thermal
cracker). Furthermore, heteroatoms must be removed by hydrotreating,
and where necessary, isomerization and alkylation are applied to ach-
ieve a high atom economy [279,280].

2.4.3. Fractional distillation of biocrude oil

The biocrude mixture obtained from HTL is a diverse and hetero-
geneous blend comprising numerous compounds suitable for use as
drop-in biofuels and as feedstock for fine chemicals. However, the
complex composition of biocrude presents many obstacles to upgrading
processes. Fractional distillation, a mature separation technology, uses
gas-liquid separation to separate complex liquid mixtures based on their
Fig. 20. Heteroatoms contents of raw lignocellulosic and non-lignocellulosic
20. Heteroatoms
biomass contents
feedstocks of raw lignocellulosic
(Lignocellulosic and[139]
biomass: red circle non-lignocellulosic
and blue boiling
circle point range
Fig. 21. into the
Increasing different groups
heteroatom containing
contents of biocrudesimilar chemicals
oil by increasing yield
mass[137];
feedstocks (Lignocellulosic
non-lignocellulosic biomass:
biomass: red [80]
red square circle [139]
and and blue
blue square circle
[86]).
structures. Fig.
(Data 21. Increasing
obtained
This fromand
flexible the
Refs. heteroatom contents
[80,86,137,139]).
straightforward of biocrude
technique is anoileconomi-
by increasing yield
]; non-lignocellulosic biomass: red square [80] and blue square [86]). (Data obtained from Refs. [80,86,137,139]).
cally viable upgrading process because of its potential to be integrated
24
with the existing oil refineries [281]. Fractional distillation process can
24
upgrade complex biocrude oil without requiring catalysts owing to high
heat and mass transfer rates and excellent thermodynamic efficiency.
This technique can physically reduce the oxygenated compounds, den-
sity, and viscosity of biocrude oil while improving its heating value and
miscibility with petroleum-derived fuels [282].
 cracking hydroxyl, and ketone), which hinders the heteroatoms removal step yields of light olefins while enhancing the economic viability of the
because of the triggered complex reactions. process [306].
thermal
Following oxygen removal, biocrude oil may be co-processed with Table 5 overviews pivotal studies involving co-refining biocrude oil
otreating, crude oil in a fluid catalytic cracking unit to split large molecules and with crude oil. Notably, the fluid catalytic cracking step stands out for its
ed to ach- produce propylene and gasoline [300,301]. More specifically, olefins economic advantage, as it does not require external hydrogen. Hydro-
Up- Grading Process are produced by cracking larger hydrocarbons, followed by cleaving
alkyl chains with more than two carbons from aromatic rings [302]. The
treating is the the second commonly studied process because of its
capability to remove heteroatom efficiently. However, this process re-
most widely used catalysts for this step are alumina- or silica-supported quires high temperatures, pressures, and specialized bifunctional cata-
zeolites, which can be continuously regenerated in situ by burning coke lysts. It is worth noting that even though biocrude oil can be co-
d hetero- deposits in the regenerator unit [279]. Coke formation is because of processed with crude oil at levels up to 50 wt% in small-scale opera-
or use as secondary polymerization and condensation reactions [279]. The heat tions, a preferred ratio of 10 wt% biocrude oil is recommended in
generated during catalyst regeneration can be recycled for refinery commercial-scale operations. This ratio helps mitigate the potentially
ever, the
upgrading
ogy, uses
d on their
chemicals
economi-
ntegrated
ocess can
ng to high
fficiency.
nds, den-
value and

ess to up-
published
ated into
alcohols,
avy (con-
r residue)
from im-
rude also
formance
de oil re-
matically
Fig. 22. H/C vs. O/C atomic ratio for (A) raw biomass, raw biocrude oil, and Fig. 23. Schematic illustration of a typical biocrude oil refinery plant producing renewable fuels and chemicals.
hydrogen upgraded biocrude oil compared to kerosene, petroleum crude oil, and diesel
ir oxygen (B) different upgrading techniques. Notably, the hydrodeoxygenation process is 26

ctions has a type of hydrotreating technique specifically used to remove oxygen from raw
a gradual biocrude oil. The hydrotreating technique eliminates all oxygen, nitrogen, and
sulfur contents of raw biocrude oil (Data obtained from Refs. [61,76,88,89,95,
chain un-
97,115,233,240,250,262–278]).
mperature
than light
ic/acyclic investment. Through this strategy, drop-in biofuel (i.e., gasoline, diesel,
is higher and jet fuel) can be derived via co-processing a blend of biocrude oil with
Biofuels vs. Petroleum fuels
Renewable and Sustainable Energy Reviews 189 (2024) 113976

Fig. 27. Comparison of minimum fuel selling prices and life cycle GHG emis-
sions of the biofuels derived from biocrude oil with conventional petroleum
fuels, including gasoline (blue square [340]), diesel (yellow square [340]), jet
fuel (purple square [341]), heavy crude (red square [342]), and liquefied pe-
troleum gas (Green square [340]). (The data obtained for biocrude oil-derived
 Type of HTL reactors

www.sciencedirect.com
Table 2

Parameter comparison of different continuous HTL reactors.

Approximated Temperature !
(C) Pressure Oil yield (wt.%) Time (min) Oil HHV (MJ/kg) Highest solid Feedstock Reactor size (L) Reactor type Reference
scale (L/h) (bar) content (wt.%)

0.18–0.42 300–340 165 12.1–21.9 7–17 34.9 5.0 Wastewater algae 0.05 Vertical [46]
double tube
0.6 350 200 42.6–54.8 15 35.8–37.3 18.2 Microalgae 0.19 CSTR [47]
1.44 350 250 38.90 15 35.3 20.0 Dried distillers grain 0.68 PFR [48]
1.5 350 200 58.8 40 NA 21.7 Macroalgae 1 PFR [49]
1.5–2.2 350 200 38–62.6 27–60 NA 35.0 Algae 1 PFR [44]
2.1 350 200 50–56 29 38.8–39.3 17.0 Grapes pomace 1 PFR [41]
2.5 350 185 39.7, 36.8 1.4, 5.8 32.9, 36.1 10.0 Microalgae 0.098 PFR [30]
3–7.5 300–400 270 48.2–60.9 12–30 35.8–37.2 4.0 Fungi 1.5 PFR [50]
4.5 325–350 180 NA 3–9 NA 5 Wastewater algae 0.5 PFR [51]
9&14 kg/h 400 300 20–33 ~50 34.3 16.9 Aspen wood 10 PFR [52]
45 260–280 110–124 NA 30–120 34.1–40.4 10–15 Swine manure, food 35 PFR [2,22]
Current Opinion in Environmental Science & Health

processing waste
60 350 220 25–33 20 26.8–33.2 16.0 Energy grass, sewage sludge 20 PFR [42]

Hydrothermal processing of sewage sludge C

90 300–350 120–200 25 3–5 NA 5.0 Macroalgae 4.5–7.5 PFR [10]
NA 350 240 30–40 15 34–37 5 Microalgae NA CSTR [53]
0.9–2.1 300–350 200 30–50 20–47a 21–23 3 Lignin 0.7 CSTR [54]

HHV, higher heating value; HTL, hydrothermal liquefaction; NA, not available; PFR, plug flow reactor; CSTR, continuous stirred-tank reactor.
a
Space time instead of residence time.
 HTL: processi continui (PNNL)
HTL continuous plant
D.C. Elliott et al. / Bioresource Technology 178 (2015) 147–156

Fig. 1. PNNL HTL laboratory reactor system.

corn stover. They examined the influence of process conditions

(temperatures and residence time) and the recycle of aqueous
product to increase biocrude oil yields and decrease wastewater
generation. Hydrotreating of the biocrude product was also tested
to construct material balances and to evaluate upgraded fuel qual-
ity. R&D was done initiated in a 1-L continuous stirred-tank reactor
operating in full continuous mode. To transition the process
towards a more scalable design, a reactor configuration that com-
bined a small CSTR with plug flow components was used for the
latter part of the NABC test work. In this configuration, shown in
Fig. 1, the CSTR was used to provide good mixing in the critical
temperature range from 160 !C to 300 !C.
The results of the NABC work (NABC, 2014) demonstrated that:
Fig. 2. Carbon balance in the HTL-to-fuel process.
! The only feed preparation required was grinding for slurry
preparation.
! Liquefaction did Fig. not require
1. PNNL a reducing
HTL laboratory gas environment.
reactor system. bility, reducing capital costs by moving away from a continuous
! Water recycle led to improvement in biocrude quality, carbon stirred-tank reactor configuration to a scalable plug-flow reactor
yields, and reduced water consumption/wastewater disposal. configuration, and understanding appropriate materials of con-
stover. They examined the ! Biocrude was
influence of stable
process in an accelerated aging test (There was less
conditions struction for process design.
peratures and residence time)thanand the change
a 2% recycle of in aqueous
biocrude viscosity during the course of the Upgrading provided the critical step to determine the quality
uct to increase biocrude oil yields and decrease wastewater
test (24 h@353 K)). and economic value of the biocrude generated from HTL. Multi-
ration. Hydrotreating of the biocrude product was also tested
! Reduced
nstruct material balances and reaction
to evaluate upgradedseverity
fuel qual-led to lower quality biocrude. liter quantities of biocrude from bench-scale HTL testing were