catalysts

Article
Sub-Pilot-Scale Autocatalytic Pyrolysis of Wastewater
Biosolids for Enhanced Energy Recovery
Zhongzhe Liu 1 , Simcha Singer 2 , Daniel Zitomer 1 and Patrick McNamara 1, *
1 Department of Civil, Construction and Environmental Engineering, Marquette University,
Milwaukee, WI 53233, USA; zhongzhe.liu@marquette.edu (Z.L.); daniel.zitomer@marquette.edu (D.Z.)
2 Department of Mechanical Engineering, Marquette University, Milwaukee, WI 53233, USA;
simcha.singer@marquette.edu
* Correspondence: patrick.mcnamara@marquette.edu; Tel.: +1-414-288-2188




Received: 30 September 2018; Accepted: 5 November 2018; Published: 7 November 2018


Abstract: Improving onsite energy generation and recovering value-added products are common
goals for sustainable used water reclamation. A new process called autocatalytic pyrolysis was
developed at bench scale in our previous work by using biochar produced from the biosolids pyrolysis
process itself as the catalyst to enhance energy recovery from wastewater biosolids. The large-scale
investigation of this process was used to increase the technical readiness level. A sub-pilot-scale
catalytic pyrolytic system was constructed for this scaled-up study. The effects of configuration
changes in both pyrolytic and catalytic reactors were investigated as well as the effect of vapor-catalyst
contact types (i.e., downstream, in-situ) on product yield and quality. The sub-pilot-scale test with
downstream catalysis resulted in higher py-gas yields and lower bio-oil yields when compared
to results from a previous batch, bench-scale process. In particular, the py-gas yields increased
2.5-fold and the energy contained in the py-gas approximately quadrupled compared to the control
test without autocatalysis. Biochar addition to the feed biosolids before pyrolysis (in-situ catalysis)
resulted in increased py-gas production, but the increase was limited. It was expected that using a
higher input pyrolyzer with a better mixing condition would further improve the py-gas yield.

Keywords: wastewater sludge; bio-oil; tar cracking; py-gas; biochar; auger reactor; catalyst; in-situ
catalysis; downstream catalysis

1. Introduction
Water resource recovery facilities (WRRFs) are currently facing many challenges including increased
energy generation, nutrient recovery and pollutant removal [1–4]. Sustainable WRRFs need to
produce more onsite energy generation and recover more value-added products. Wastewater biosolids
(i.e., treated wastewater sludge) are a major byproduct of WRRFs, and over 8 million dry tons are produced
in the United States every year, of which 55% are land applied due to their beneficial soil conditioner
properties [5]. For example, heat dried biosolids (Milorganite® ) produced by Milwaukee Metropolitan
Sewerage District (MMSD) are an established soil conditioner. Over 45,000 tons of Milorganite® are
produced annually and are applied to golf courses, turf farms and home lawns. Biosolids are treated
using processes such as anaerobic digestion, but their residual energy is refractory and is not fully
recovered before biosolids land application [6]. Additionally, organic contaminants of emerging concern
in biosolids such as triclosan are potential issues as well [7–11]. Hence, post-treatment techniques to
improve energy and resource recovery and reduce adverse environmental impacts are crucial to achieving
sustainable WRRFs.
Thermochemical processing of biosolids is an acknowledged technology for energy and resource
recovery, such as incineration, gasification, and pyrolysis [12–17]. Pyrolysis is considered a

Catalysts 2018, 8, 524; doi:10.3390/catal8110524 www.mdpi.com/journal/catalysts

Catalysts 2018, 8, 524 2 of 11

promising low-waste solution to biosolids handling in terms of energy recovery, resource recovery,
and contaminant removal [18]. Pyrolysis is a process that decomposes carbonaceous materials
(e.g., biosolids) upon heating in an oxygen deficient or free environment. The resulting products
are biochar, pyrolysis gas (py-gas), and pyrolysis condensate (bio-oil or py-oil) that may contain
multiple aqueous and nonaqueous phases. Biochar is usually used as a precursor for activated
carbon production or as a valuable soil amendment, which improves plant growth. Py-gas and the
nonaqueous phase of bio-oil can both be used as fuels after conditioning. Additionally, biosolids
pyrolysis removes recalcitrant contaminants including triclosan and triclocarban, antibiotic resistance
genes, as well as reduces total estrogenicity of the resulting biochar [19–21]. However, bio-oil from
conventional slow pyrolysis of biosolids (biochar is the target product with heating rate below
100 ◦ C/min, hereafter referred to as pyrolysis) normally accounts for at least 40% of the total product
mass [17] and requires costly pretreatment due to its corrosive and unstable properties before it can
be used as a clean fuel [22]. In contrast, py-gas can be more easily burned in gas engines for energy
recovery. Therefore, cost-efficient catalyst is of great interest to reduce bio-oil yield and increase py-gas
yield during biosolids pyrolysis.
A new process called autocatalytic pyrolysis was developed in our previous batch,
bench-scale work by using biosolids biochar from the process itself as the catalyst to enhance energy
recovery from biosolids (Figure S1) [23]. The energy analysis also showed that the new process can
be energy neutral by partially using py-gas energy [24]. In the autocatalytic pyrolysis process, the
dried biosolids is pyrolyzed in the pyrolytic reactor to generate biosolids biochar and pyrolysis vapor
(py-gas and uncondensed bio-oil). The biochar is immediately conveyed to the downstream reactor
as the catalyst (or mixed with the dried biosolids at the feeding end). Both py-gas and bio-oil are
upgraded via autocatalysis to produce high yield py-gas and low yield bio-oil condensate because
biosolids biochar contains high calcium and iron contents [23]. The spent biochar is still considered
as an activated carbon precursor or a soil amendment. The bench-scale study showed that biosolids
biochar increased the py-gas yield by nearly 2-fold. The catalyzed bio-oil contained fewer hydrocarbon
constituents. The energy shifted from bio-oil to py-gas, indicating the potential for easier on-site energy
recovery using the relatively clean py-gas [23,25].
In the development of a new process, after the concept is validated in a laboratory environment,
a prototype demonstration such as a sub-pilot scale test is needed to increase the technical readiness
level. Some biosolids pyrolysis technologies have been evaluated at a large scale. Chang et al. (2016)
studied the effectiveness of sewage sludge pyrolysis using pilot-scale pyrolysis systems to promote
the engineering application of municipal sludge pyrolysis technology [26]. They found that the
optimal operating conditions and product characteristics were in accordance with those of the bench
experiment. Lin et al. (2012) scaled up a microwave-heating process to develop the industrial
application of sludge-based adsorbents with bio-oil production [27,28]. In addition, sludge was
pyrolyzed in a pilot plant with manure to evaluate the performance of synergistic treatment [29].
As for large-scale catalytic pyrolysis, commercial hydroprocessing catalyst and ZSM-5 catalyst have
been investigated to produce infrastructure-compatible biofuels and petrochemical intermediates from
biomass (e.g., sugarcane bagasse and pinewood) at a pilot-scale [30,31]. However, catalytic biosolids
pyrolysis has been rarely studied at large scale. Because of the good performance of the bench-scale
autocatalytic biosolids pyrolysis, a scaled-up study (i.e., sub-pilot scale) was needed.
The overarching goal of this study was to evaluate the large-scale autocatalytic performance
during biosolids pyrolysis using a continuous pyrolytic system. The effect of the configuration
changes in both pyrolytic and catalytic reactors as well as the effect of vapor-catalyst contact types
(i.e., downstream, in-situ) on the product yield and quality were investigated. This research was
conducted to determine whether biosolids biochar catalyst (BBC) particles can be directly added
to the reactor for in-situ catalysis or whether a downstream catalytic reactor (i.e., downstream
catalysis) is required. Our sub-pilot-scale test revealed that the downstream catalysis had better
catalytic performance with higher py-gas yield and lower bio-oil yield when compared to the previous
Catalysts 2018, 8, 524 3 of 11

Catalysts 2018, 8, x FOR PEER REVIEW 3 of 11

bench-scale results. Furthermore, in-situ catalysis resulted in increased py-gas production, but the
increase was limited.
was limited. It was expected
It was expected thata using
that using higherainput
higher input pyrolyzer
pyrolyzer withmixing
with a better a bettercondition
mixing condition
would
would further
further improve
improve the py-gas
the py-gas yield. yield.

2. Results and
2. Results Discussion
and Discussion

2.1.2.1.
Validation of of
Validation thetheSub-Pilot-Scale
Sub-Pilot-ScalePyrolysis
PyrolysisSystem
System
The newly
The newly constructed
constructedsub-pilot-scale
sub-pilot-scale pyrolytic system required
pyrolytic system requiredaavalidation
validationtesttestinin comparison
comparison
with
withthethebench-scale
bench-scaletest.
test.All
Allthe
theunits
unitsof ofthe
the system
system functioned
functioned wellwellduring
duringthethevalidation
validation test
test andand
thethe
sub-pilot-scale
sub-pilot-scaleresults
resultswere
wereininaccordance
accordance with with the bench-scale
bench-scaleresultsresults(Figure
(FigureS2). S2).The
The biochar
biochar
mass
mass fraction
fractionwaswasapproximately
approximately50% 50% for
for both
both scales. Thebio-oil
scales. The bio-oilandandpy-gas
py-gasyields
yields were
were similar,
similar,
which
which werewere approximately
approximately 35%35% and
and 15%,15%, respectively.InInaddition,
respectively. addition,the thebiochar
biocharproducts
productslook looksimilar
similar by
by appearance.
appearance. As forAsthe
forbio-oil
the bio-oil optical
optical property,
property, both both condensates
condensates contained
contained a light
a light non-aqueous
non-aqueous phase
andphase and an phase
an aqueous aqueousthatphase that water
contained containedand water
solubleand solubleindicating
organics, organics, that
indicating that the
the condensation
condensation
performance wasperformance was acceptable.
acceptable. Hence, the system Hence, the system
was qualified forwas qualified for
the following the followingresearch.
sub-pilot-scale sub-
pilot-scale research.
2.2. Product Yields and Properties
2.2. Product Yields and Properties
The downstream catalysis process greatly increased the py-gas yield while the in-situ catalysis
processThe onlydownstream catalysisthe
slightly increased process
py-gasgreatly increased
yield (Figure 1).the
Forpy-gas yield while the
the downstream in-situprocess,
catalysis catalysisthe
only slightly increased the py-gas yield (Figure 1). For the downstream catalysis,
increase of catalyst to biosolids mass ratio resulted in a higher py-gas yield and lower bio-oil yield. the increase of In
catalyst to biosolids mass ratio resulted in a higher py-gas yield and lower bio-oil yield. In particular,
particular, at 800 ◦ C with a catalyst to biosolids mass ratio of 1, the mass fraction of bio-oil decreased
at 800 °C with a catalyst to biosolids mass ratio of 1, the mass fraction of bio-oil decreased from 36%
from 36% to 4% of all products by mass. Meanwhile, the py-gas yield increased by 2.5-fold (from 23%
to 4% of all products by mass. Meanwhile, the py-gas yield increased by 2.5-fold (from 23% to 57%).
to 57%). When compared with the bench-scale autocatalytic results, the py-gas yield was much higher
When compared with the bench-scale autocatalytic results, the py-gas yield was much higher and
and the bio-oil yield was much lower. With a catalyst to biosolids mass ratio of 1, the bio-oil yield
the bio-oil yield was much lower. With a catalyst to biosolids mass ratio of 1, the bio-oil yield was
was below 5% for the sub-pilot-scale test while the bio-oil yield was 20% for the bench-scale test [23].
below 5% for the sub-pilot-scale test while the bio-oil yield was 20% for the bench-scale test [23]. The
Theexcellent
excellent sub-pilot-scale
sub-pilot-scale autocatalytic
autocatalytic effect
effect withwith downstream
downstream catalysis
catalysis waswas
mostmost likely
likely duedueto to
thethe
enlarged size of the downstream catalyst bed (7 cm inner diameter and 30 cm
enlarged size of the downstream catalyst bed (7 cm inner diameter and 30 cm long for sub-pilot-scale long for sub-pilot-scale
versus
versus 0.79 cmcm
0.79 inner
innerdiameter
diameterand and27.9
27.9cmcm long
long for
for bench-scale), whichprovided
bench-scale), which providedmore more surface
surface area
area
andandlonger
longerinside
insideretention
retentiontime
timetotoimprove
improvethe the pyrolysis
pyrolysis vapor decompositionand
vapor decomposition andupgrading.
upgrading.

Figure
Figure 1. 1.Product
Productmass
mass fractions
fractions of
ofbiosolids
biosolidspyrolysis (“control”
pyrolysis denotes
(“control” the 800
denotes the°C
800 ◦ C non-catalytic
non-catalytic test
with the downstream temperature of 500 ◦
°C; “0.5” and “1” indicate the 800 °C◦ autocatalytic
test with the downstream temperature of 500 C; “0.5” and “1” indicate the 800 C autocatalytic tests tests
performed
performed with
with a catalyst/biosolids mass
a catalyst/biosolids mass ratio
ratio of
of 0.5
0.5 and
and1,1,respectively;
respectively;the
thebench-scale
bench-scaleresults were
results were
from
from ourour previous
previous study[23]).
study [23]).
 Catalysts 2018, 8, 524 4 of 11
Catalysts 2018, 8, x FOR PEER REVIEW
Catalysts 2018, 8, x FOR PEER REVIEW Catalysts 2018, 8, x FOR PEER REVIEW
4 of 11 4 of 11
Catalysts
Catalysts 2018, 8,2018,
x FOR8,PEER
x FORREVIEW
PEER REVIEW 4 of 11 4 of 11
For the
For the in-situ catalysis, thein-situ
For
py-gasthecatalysis,
in-situ
mass fraction the py-gas
catalysis, increased mass
the py-gas 6% fraction
mass
(fromfraction increased
23%For to 6%while
theincreased
29%),
in-situ (from
catalysis,
6%the 23%
(from
bio- theto
23% 29%),
py-gas while
to 29%), mass the
while
fraction the bio-
increased 6%
oil yield decreasedbio-oil
5% (fromyield
oil decreased
36%
yield
For to
the decreased
31%).
in-situ 5% The(from
5% limited
catalysis, 36%
(from the to
autocatalytic
36% 31%).
py-gas to The
31%).
mass limited
oil
effect
The
For the in-situ catalysis, the py-gas mass fraction increased 6% (from 23% to 29%), while the bio- yield
fraction autocatalytic
limited
was decreased
possibly
autocatalytic
increased 5%
6%due effect
(from
to
(from was
effect
the23%36% possibly
was
toto 31%).
possibly
29%), due The
while to
duelimited
the to theautocataly
bio-
ow feeding rate that was
theoil
low restricted
yield low
feeding
oil yieldfeeding
decreased by the
rate
decreased rate
that
5% design
that
was
(from5%was of therestricted
tofeeding
restricted
(from
36% 36%
31%).bytoThebysection.
the the
31%). designdesign
low
The
limited The feeding
of low
of
thethe
limited feeding
feeding
rate that
feeding
autocatalytic autocatalyticrate section.
was
section.
effect resulted
was restricted
Thewas
The
effect
possibly lowby
low feeding
thetodesign
feeding
possibly
due the rate
dueof
rate resulted
tothethefeeding sec
n low capacity occupancy
resulted lowin
in
low feeding with
low
feeding
low poor
capacity
capacity
rate thatcontact
rate was occupancy
that
occupancybetween
was restricted
restricted with
BBC
with
by the poor
and
poor
design pyrolysis
by contact
thecontact
of inbetween
design
the low
between
vapor
of
feeding capacity
theBBC (e.g.,
BBC
feeding
section. occupancy
and vapor
and pyrolysis
section.
pyrolysis
The is light
low with
The vapor
feeding vapor
lowpoor (e.g.,
rate contact
(e.g.,
feeding vapor
resulted vapor
rate between is light
isresulted BBC and p
on the top while BBC inislow
light onheavy
in low capacity occupancy with poor contact between BBC and pyrolysis vapor (e.g., vapor is lightin rate c
on
the the
at
top
capacity the
top
while bottom).
while
occupancyBBC BBC
is If the
heavy
with is heavy
feeding
at
poor the at the
rate
bottom).
contact bottom).
can
between be
If on theincreased
the
If
BBC thetop
feedingandfeeding
while
with
rate
pyrolysis BBC
rate
more
can be can
is BBC
heavy
be
increased
vapor in
increased
(e.g., at the
with
vapor bottom).
with
more
is light more
BBC If the BBCfeeding
in on
the pyrolysis reactor, thethe
the top
improvement
onthe the
pyrolysis while
pyrolysis
top BBC
while
reactor, fromisthe
heavy
reactor,
BBC the at improvement
improvement the bottom).
isautocatalytic
theheavy at the effect
from Ifthethe
from
bottom). could feeding
the the
Ifpyrolysis
be rate can
autocatalytic
the
autocatalytic expected.
feeding be
reactor,
effectSince
rate increased
effect
the
can
could thecould with
improvement
besub-
be morewith
be expected.
increased
expected. BBC
from
Since in
Since
the
more theautocatalytic
the sub-
BBC in effec
pilot-scale downstream the pyrolysis
catalysis
thepilot-scale
sub-pilot-scale reactor,
performed
pyrolysis
downstream the improvement
downstream
reactor, much
catalysis better
catalysis
the improvement from
in
performed the
comparison
performedfrom autocatalytic
much pilot-scale
themuch
with
better effect
in-situ
better
autocatalytic
in could
downstream
in
comparisoncatalysis bewith
comparison
effect expected.
in
catalysis
could this with
be
in-situ Since
performed
in-situ
expected.
catalysisthe sub-catalysis
in much
Since thisthebetterin this in compa
sub-
study, only the py-gas pilot-scale
study, and
only study,
bio-oil
pilot-scale
thedownstream
only
from
py-gas the
downstream
and catalysis
downstream
py-gas
bio-oil and performed
catalysis
from catalysis
bio-oil
downstream much
from
performed better
weredownstream muchinbetter
analyzed
study,
catalysis comparison
only forcatalysis
the
process investigating
in py-gas
comparison
were with
were in-situ
and analyzed
analyzed the catalysis
bio-oil
with for for in
from
in-situ this
investigating
downstream
catalysis
investigating in this the
catalysis w
changes in properties study,
andstudy,
the changes only
energy
changes the
in only py-gas
yields.
in the
properties and
properties
py-gas bio-oil
and energy and
and energyfrom
bio-oil
yields. downstream
yields.
from downstream catalysis
changes incatalysis were
properties analyzed
were for
andanalyzed investigating
energy yields. for investigatingthe the
The py-gas of changes
theThe in properties
sub-pilot-scale
changes
py-gas The inofpy-gas and
properties
the ofenergy
downstream and
sub-pilot-scale yields.
the sub-pilot-scale
autocatalytic
energy yields. downstream
downstream testsautocatalytic
(Figure
The py-gas autocatalytic
2) had of higher
tests the sub-pilot-scale
tests
(Figure H22) (Figure
had higher 2)downstream
hadHhigher 2 autocatalyti
H2
concentration andconcentration
lower CO The py-gas
concentration
2 concentration
The and of
py-gas the
lower and sub-pilot-scale
CO lower
ofcompared
the COto downstream
2 concentration
those ofcompared
sub-pilot-scale the autocatalytic
concentration
control
downstream compared totest. H2and
to tests
those
autocatalytic (Figure
lower
increased ofcontrol
the CO
from
tests 2)
control had
concentration
2 (Figure
higher
test. Hhad
H22)increased H 2
2 increased
compared
higher from Hto2 those of
2 concentration those of the test.
concentration and lower CO2 concentration compared to those of the control test. H2 increased from
26% (control) to above
from 40%
26% 26%
while (control)
concentration
(control) CO2to to above
decreased
and
above lower 40% 40%
from
CO whilewhile
225% CO CO
(control)
concentration2 decreased
decreased
2 to 26%below
compared (control)
from
from 10%. to
25%25% to
The
those above
(control)
H
(control) of
2 % the40%
increase
to to while
below
control
below CO
10%.
test.
10%. 2H decreased
The
The
2 H
increased
H 22 % from
increase
from 25% (contro
26% (control) to above 40% while CO2 decreased from 25% (control) to below 10%. The H2% increase
was possibly a result of multiple
increase 26%was(control)
was possibly
thermochemical
possibly aa result
to resultof
above of
40%reactions
multiple
multiple such
thermochemical
while thermochemical
CO as steam
2 decreased wasmethane possibly
from reactions
25%
reactions reforming
a (control)
result
suchas
such of
assteam
(H
multiple
steam
to 2below methane
O +methane thermochemical
10%. The reforming
reformingH2% increase reactions
(H2O + such as
was possibly a result of multiple thermochemical reactions such as steam methane reforming (H2O +
CH4  3H2 + CO; (H 2H22OO ++wasCH 43H
CH4possibly 4H
3H2 2+++aCO CO;
CO; 2),2H
result 2H
dryof2OO ++ CH4 
reforming
multiple 4H
(CO
4H 2 +2++
thermochemical CO
CO CH CH
22),
),  4 
4 dry
dry 2COreforming
3H2++2H
reactions
reforming CO; 2), (CO
such or
2H
(CO the
as22O +++water
CH
2steam 442CO
CH4 methane 4H2 +++
2CO 2H
CO2H22),2),),or
reforming dry
orthe (Hreforming
water
2O + (CO2
CH4  3H4 2 + CO;2 2H2O + CH2 4  4H2 4+ CO2),2dry reforming (CO2 + CH4  2CO + 2H 2), or the water
gas shift reaction (CO + HCH
the water 2O gas4 
gas shift
CO 3H
shift 2 reaction
+2reaction
+HCO;
2). In2H (CO
(CO 2O++
addition, +HHCH 2O O4 
bio-oil CO4H
CO decomposition
22 ++
+ H CO
H 2 ). In
).
2 gas
), Indry shift
addition, and
addition, reaction
reforming reforming
bio-oil
bio-oil (CO
(CO H
decomposition
(e.g.,
++ CH
decomposition
2 2O Tar
4 
 CO
2CO and
and
2 ++ H reforming
2H ). In
),
reforming
2 2 oraddition,
the (e.g.,
waterTar
bio-oil decom
gas shift reaction (CO + H2O  CO22 + H2). In2addition, 2
bio-oil decomposition and reforming (e.g., Tar
+ H2O  CO, CO2,(e.g.,
and H Tar ) +also
2gas +H H 2O O →
2contributed
shift CO,
reaction CO, CO(COCO2to
, and
2the HH2O
+, and 2)%
Halso
increase
2 )CO contributed
also H[23].
2). InThe
2 + contributed +addition, Oto
Hdecrease
to 2the HtheCO,
%H increase
inCO
2bio-oil 2% CO 2,increase
2and
%[23].
could
decomposition H2)The also
bedecrease
[23]. contributed
and
The reforming in CO
decrease to2% the
in could
(e.g., H2Tar
% beincrease [2
+ H2O  CO, CO2, and H2) also contributed to the H2% increase [23]. The decrease in CO2% could be
a result of the biochar-enhanced
COa2result + aHof
% could result
2O be  dryof
CO,
a the
reforming
CO
result biochar-enhanced
,
2of and the Hand the
2) also relative
dry
contributed
biochar-enhanced reforming
increasea
to
dry
the biochar-enhanced dry reforming and the relative increase of other gas components result
the of
and
H
reforming2other
of
% the
the gas
relative
increasebiochar-enhanced
and components
[23].
the increase
The
relative of
decrease dry
other
increase reforming
in gas
CO
of 2%components
other and
could the
be relative
[32,33]. CO% and CH 4%
gas[32,33].a [32,33].
decreased
componentsresult ofCO%
slightly
the
[32,33]. and CO%
CO% and CH4% decreased slightly CH
during
biochar-enhanced % the
4and decreased
sub-pilot-scale
CH 4 % dry slightly
reforming
decreased [32,33].
downstream
during
slightly and CO%
the the
during and CH
sub-pilot-scale
autocatalytic
relative
the
during the sub-pilot-scale downstream autocatalytic tests. % decreased
increasetests.
downstream
sub-pilot-scale
4 of slightly
other autocatalytic
gas
downstream during
components the tests.
sub-pilot-sca
Even though the concentration
autocatalytic Even
[32,33]. ofthough
each
CO%
tests. Evengas
andthe component
CHconcentration
though
Even though the concentration of each gas component 4% decreased
the was ofdifferent
each
slightly
concentration gasduring
between
ofEven
component
wasthough
each the the
gas sub-pilot-scale
wasthebetween
sub-pilot-scale
component
different different
concentration
was between
the and
downstream
differentof eachthe
sub-pilot-scale sub-pilot-scale
gasand
between component
autocatalytic the tests. and
was differe
the bench-scale tests, the trend
the
Even
sub-pilot-scale bench-scale
during
though
and autocatalysis
the
the tests,
concentration
bench-scale the trend
was
tests,
the bench-scale tests, the trend during autocatalysis was very similar. very
ofduring
each
the similar.
gas
trend autocatalysis
the
component
during bench-scalewas
was
autocatalysis verytests,
different similar.
wasthe trend
between
very during
similar.the autocatalysis
sub-pilot-scale was
and very simi
the bench-scale tests, the trend during autocatalysis was very similar.

Figure
Figure 2. 2. Py-gas
Py-gas composition
composition of of biosolids
biosolids pyrolysis
pyrolysis (“control”
(“control” denotes
denotes thethe
800800◦ C°C non-catalytic
non-catalytic testtest
with
Figure 2. Py-gas composition
the downstream temperature of 500 C; “0.5” and “1” indicate the 800 C downstream autocatalyticpyrolysis
with Figure
theof biosolids
2. Py-gas
downstream pyrolysis
composition
(“control”
temperature ◦ of of biosolids
500denotes
°C; the
pyrolysis
“0.5” 800
Figure
and °C (“control”
“1”non-catalytic
2. Py-gas
indicate◦ denotes
composition
the test
800 the
°C 800
of °C
biosolids
non-catalytic
downstream test(“control” deno
with the downstream temperature
with
autocatalytic
Figure theof
tests
2. downstream
500 °C;
performed
Py-gas “0.5”
withtemperature
composition aand “1” indicate
of
catalyst/biosolids
of biosolids 500 the
°C;
mass with
pyrolysis 800
“0.5”
ratio the
°C
of and
downstream
downstream
0.5
(“control” and“1”1, indicatetemperature
respectively;
denotes
tests performed with a catalyst/biosolids mass ratio of 0.5 and 1, respectively; the bench-scale results the the
800 800
the
°C °C
bench-of downstream
500
non-catalytic °C; “0.5” and “1” in
test
scale
autocatalytic tests performed
were fromresults
with
with were
ourthe from
autocatalytic
a our
downstream
previous previous
catalyst/biosolids
tests performed
study [23]). study [23]).
temperature of 500 °C; “0.5” and “1” indicate the 800 °C downstream mass ratio of 0
mass with
ratio a
ofcatalyst/biosolids
0.5 and 1, respectively;
autocatalytic
mass ratio
the
tests
bench-
ofperformed
0.5 and 1, respectively;
with a catalyst/biosolids
the bench-
scale results were from our previous
scale results
study
autocatalytic were
[23]).
tests from our previous
performed study [23]).scalemass
with a catalyst/biosolids results were
ratio from
of 0.5 andour1, previous study
respectively; the[23]).
bench-
TheThe sub-pilot-scale
sub-pilot-scale downstream
downstream
scale results were autocatalysis
studyprocess
autocatalysis
from our previous [23]). changed
changedthe thebio-oil
bio-oilchemical
chemical composition
composition
(Figure
The sub-pilot-scale 3).
(Figuredownstream According
3). According to
The sub-pilot-scalegas
autocatalysis chromatography-mass
process
downstream
changed
to gas chromatography-mass spectroscopy
autocatalysis
the bio-oil
Theprocess
spectroscopy chemical (GC-MS)
sub-pilot-scale
(GC-MS) changed
composition
analysis, analysis,
downstream
the
thebio-oil◦
800 Cthe 800 °Ccomposition
chemical
autocatalysis
autocatalytic process change
(Figure 3). Accordingautocatalytic
bio-oiltocontained
gas
(Figure bio-oil
very contained
chromatography-mass
The 3). According
sub-pilot-scale
few tovery
detectable gas few detectable
spectroscopy
downstream
hydrocarbons. hydrocarbons.
chromatography-mass
(GC-MS)
(Figure
autocatalysis
Only 3).
analysis,
process Only
According
spectroscopy
toluene, toluene,
the 800
changed
pyridine, to (GC-MS)
the gas pyridine,
°C ethylbenzene
and and
chromatography-mass
bio-oil analysis,
chemical the 800 °C
composition
had spectroscop
autocatalytic bio-oilethylbenzene
contained
identifiable had
autocatalytic
(Figure very
3). In
peaks. identifiable
fewbio-oil
contrast, peaks.
detectable
According contained
to gas
many In contrast,
hydrocarbons.
very few
hydrocarbon many
peaks hydrocarbon
autocatalytic
detectable
Only
chromatography-mass toluene,
in the peaks
hydrocarbons.
bio-oil
control in
pyridine,
spectroscopy the control
contained
bio-oil and
were Only
(GC-MS) bio-oil
very
toluene,
detected were
fewGC-MS
analysis,
by pyridine,
detectable and
the 800 °C hydrocarbo
ethylbenzene had suchdetected
identifiable by
toluene, GC-MS
ethylbenzene
peaks.
as autocatalytic
pyridine, such
In bio-oil ascontained
contrast,
had toluene,
identifiable
many
ethylbenzene, pyridine,
hydrocarbon
peaks.
very In
styrene,few ethylbenzene,
contrast,
peaks
ethylbenzene
detectable
phenol, inmany styrene,
theindole,
cresol, control
hydrocarbon
hadand phenol,
identifiable
bio-oil
hydrocarbons. cresol,
peaks
were
Only
cuscohygrine.peaks.
in indole,
the In
toluene, andbio-oil
control
contrast, many
pyridine, were
andhydrocarbo
detected by GC-MS cuscohygrine.
such as
detected
toluene,
In ethylbenzene
addition, bypyridine,
the GC-MS
had
color such
ethylbenzene,
identifiable
of the aspeaks.
toluene,
catalyzed Instyrene,
pyridine,
bio-oil detected
contrast,phenol,
became ethylbenzene,
many by cresol,
clearerGC-MS
hydrocarbon
withindole,
styrene,
such
higher and
ascatalyst
peaks phenol,
toluene, tocresol,
pyridine,
in the control indole,
biosolids ethylbenzene,
bio-oil and
were sty
In addition, the color of the catalyzed bio-oil became clearer with higher catalyst to biosolids
cuscohygrine. mass ratio cuscohygrine.
detected
(Figure byS3b).
GC-MS such asbio-oil
The control toluene,
contained cuscohygrine.
pyridine, ethylbenzene,
a thick styrene, phenol,
dark and lighter-phase cresol,
fraction indole, and
(mainly
mass ratio (Figure S3b). The control bio-oil contained a thick dark and lighter-phase fraction (mainly
In addition, the colorcuscohygrine.
of the
In catalyzed
addition, bio-oil
the color
became
of theclearer
catalyzed
withbio-oil
higher
In addition,
became
catalystclearer
the
to biosolids
color
with
of higher
the catalyzed
catalystbio-oil
to biosolids
became clearer
mass ratio (Figure S3b). Themass
control
In ratio
bio-oil
(Figure
addition, contained
theS3b).
colorThe
ofa thick
control
dark
bio-oil
andbio-oil
the catalyzed mass
contained
lighter-phase
ratio a(Figure
became thick
fraction
dark
S3b).(mainly
clearer and
Thelighter-phase
with control catalyst
higher bio-oil
fraction
contained
(mainly
a thick dark
to biosolids
mass ratio (Figure S3b). The control bio-oil contained a thick dark and lighter-phase fraction (mainly
Catalysts 2018, 8, 524 5 of 11
Catalysts 2018, 8, x FOR PEER REVIEW 5 of 11

unsaturated hydrocarbons)
unsaturated hydrocarbons)(Figure
(FigureS3a).
S3a).DueDueto the higher
to the viscosity
higher of theofthick
viscosity the dark
thickphase, the bottom
dark phase, the
bottom aqueous phase (light brown layer) dripped out from the condensing system first (i.e.,left
aqueous phase (light brown layer) dripped out from the condensing system first (i.e., the the two
left
containers
two in Figure
containers S3a mostly
in Figure contained
S3a mostly the aqueous
contained phase).phase).
the aqueous Compared to the control
Compared test, thetest,
to the control masstheof
dark and lighter-phase fraction was greatly reduced via autocatalysis. The test with catalyst
mass of dark and lighter-phase fraction was greatly reduced via autocatalysis. The test with catalyst to biosolids
mass
to ratio of
biosolids 0.5 contained
mass ratio of 0.5acontained
very thin alight
verylayer
thin and
lightthe testand
layer with
thecatalyst
test withto biosolids
catalyst tomass ratio
biosolids
of 1 only
mass ratiohad
of the aqueous
1 only had phase (Figurephase
the aqueous S3b). In particular,
(Figure S3b).theIn optical property
particular, of catalyzed
the optical bio-oil
property of
droplet was almost transparent with catalyst to biosolids mass ratio of 1 (Figure
catalyzed bio-oil droplet was almost transparent with catalyst to biosolids mass ratio of 1 (Figure S3c). Dark bio-oil
color Dark
S3c). indicated the presence
bio-oil of unsaturated
color indicated hydrocarbons
the presence [34]. Hence,
of unsaturated the autocatalysis
hydrocarbons produced
[34]. Hence, thea
cleaner bio-oilproduced
autocatalysis product with fewerbio-oil
a cleaner unsaturated
product hydrocarbons, which couldhydrocarbons,
with fewer unsaturated be beneficial forwhichsubsequent
could
upgrading
be beneficialorfor
disposal.
subsequent upgrading or disposal.

Figure
Figure 3.
3. GC-MS
GC-MS ofof bio-oils
bio-oils from
from the
the sub-pilot-scale
sub-pilot-scale tests
tests (“control”
(“control” denotes
denotes the ◦ C non-catalytic
the 800 °C non-catalytic
test
test with
with the
the downstream
downstream temperature
temperature ofof 500 ◦
500 °C;
C; “1”
“1” indicates
indicates the ◦
the 800 °CC downstream
downstream autocatalytic
autocatalytic
test
test performed
performed with
with aa catalyst/biosolids
catalyst/biosolidsmass
massratio
ratioofof1).
1).

2.3. Product
2.3. Product Energy
Energy Yields
Yields
Similartotothe
Similar thebench-scale
bench-scale results,
results, thethe sub-pilot-scale
sub-pilot-scale catalyzed
catalyzed bio-oil
bio-oil HHVhigher heating
decreased fromvalue
8000
(HHV) decreased from 8000 kJ/kg-bio-oil (control test) to around 2000 kJ/kg-bio-oil
kJ/kg-bio-oil (control test) to around 2000 kJ/kg-bio-oil with the catalyst to biosolids mass ratio of 0.5 with the catalyst
to 1biosolids
or (Figure S4).massThe ratio
HHVof 0.5 or 1 (Figure
decrease S4). The
was possibly HHVofdecrease
because was possibly
the decrease in organicbecause of the
constituents
described above and the formation of water during catalysis [35]. The sub-pilot-scale catalyzed [35].
decrease in organic constituents described above and the formation of water during catalysis py-
The sub-pilot-scale catalyzed py-gas HHV increased slightly with the catalyst
gas HHV increased slightly with the catalyst to biosolids mass ratio of 0.5 while decreased by 3000 to biosolids mass
ratio3 of 0.5the
while decreased by 3000 kJ/m 3 with the catalyst to biosolids mass ratio of 1 (Figure S4).
kJ/m with catalyst to biosolids mass ratio of 1 (Figure S4). The decrease was due to less CH4 and
The decrease was because less CH 4
CO was produced (Figure 2). As for biochar, the and CO wasenergy
produced (Figure
content 2). Asand
for bench forsub-pilot
biochar, the energy
scales was
content for bench and sub-pilot scales
similar, which was approximately 1,1650 kJ/kg. was similar, which was approximately 1,1650 kJ/kg.
The sub-pilot-scale
The sub-pilot-scale downstream
downstream autocatalysis
autocatalysis process
process increased
increased py-gas
py-gas energy
energy yield
yield and
and
decreased bio-oil
decreased bio-oil energy
energy yield
yield (Figure
(Figure4).4).In
Inparticular,
particular,py-gas
py-gasenergy
energyyield
yieldincreased
increased asas
the
thecatalyst
catalyst to
biosolids mass ratio increased. For example, with the catalyst to biosolids mass
to biosolids mass ratio increased. For example, with the catalyst to biosolids mass ratio of 1, the py-ratio of 1, the py-gas
energy
gas increased
energy to 10,000
increased kJ/kg-biosolids-pyrolyzed
to 10,000 kJ/kg-biosolids-pyrolyzed from the the
from 27602760
kJ/kg of the
kJ/kg control
of the test.test.
control In the
In
meantime, due to the greatly reduced yield and energy content in bio-oil, the
the meantime, due to the greatly reduced yield and energy content in bio-oil, the bio-oil energy bio-oil energy decreased
decreased from 3000 kJ/kg-biosolids-pyrolyzed to below 100 kJ/kg. The energies in non-catalyzed
bio-oil and py-gas were almost equal (control test), but the energy shifted greatly from bio-oil to py-
Catalysts 2018, 8, 524 6 of 11

from 3000
Catalysts kJ/kg-biosolids-pyrolyzed
2018, 8, x FOR PEER REVIEW to below 100 kJ/kg. The energies in non-catalyzed bio-oil and
6 of 11
py-gas were almost equal (control test), but the energy shifted greatly from bio-oil to py-gas energy via
gas energy viaAsautocatalysis.
autocatalysis. As aforementioned,
aforementioned, py-gas
py-gas is easier and is easier
cleaner and energy
for on-site cleanerrecovery
for on-site energy
compared
recovery
to bio-oil.compared to bio-oil.

4. Py-gas and bio-oil energy yields (“control” denotes the 800

Figure 4. 800 ◦°C
C non-catalytic test with the
downstream temperature
temperature of of 500 ◦ C; “0.5” and “1” indicate the 800 °C
500 °C; ◦ C downstream autocatalytic tests
performed
performed with
with aa catalyst/biosolids mass ratio
catalyst/biosolids mass ratio of 0.5 and 1, respectively; the bench-scale results were
from our previous study [23]).
previous study [23]).

An
An energy
energy balance
balance analysis
analysis was
was conducted
conducted using
using the
the bench-scale
bench-scale results
results in
in our
our previous
previous study
study
and ◦
and revealed
revealed that
that the
the autocatalytic
autocatalytic process
process was
was endothermic
endothermic atat 800
800 °CC [24]. Since the
[24]. Since the product
product energy
energy
per biosolids pyrolyzed
per biosolids pyrolyzedduring
duringthethesub-pilot-scale
sub-pilot-scale test
test was
was similar
similar to that
to that of bench-scale,
of the the bench-scale, the
the sub-
sub-pilot-scale autocatalytic process could be endothermic as well. However, a fraction
pilot-scale autocatalytic process could be endothermic as well. However, a fraction of the py-gasof the py-gas
could
could be
be used
used to
to supply
supply the
the heat
heat for
for this
this endothermic
endothermic process.
process. AA more
more detailed
detailed large-scale
large-scale energy
energy
balance analysis is needed in the future.
balance analysis is needed in the future.

3. Materials and
3. Materials and Methods
Methods
3.1. Materials
3.1. Materials
Dried biosolids (Milorganite®® ) were collected from the Jones Island water resource reclamation
Dried biosolids (Milorganite ) were collected from the Jones Island water resource reclamation
facility (Milwaukee, WI, USA). Milorganite®® is a blend of waste activated sludge and anaerobically
facility, (Milwaukee, WI, USA). Milorganite is a blend of waste activated sludge and anaerobically
® contains
digested primary solids. Milorganite 66.6% volatile solids, 7.70% fixed carbon, and 25.7%
digested primary solids. Milorganite® contains 66.6% volatile solids, 7.70% fixed carbon, and 25.7% ash
® were
ash (wt%, dry basis). The elements of Milorganite analyzed using Vario Micro Cube (Elementar,
(wt%, dry basis). The elements of Milorganite were analyzed using Vario Micro Cube (Elementar,
®
Hanau, Germany) and X-ray fluorescence (XRF-1800, Shimadzu, Kyoto, Japan). The composition of
Hanau, Germany) and X-ray fluorescence (XRF-1800, Shimadzu, Kyoto, Japan). The composition of
major elements is listed in Table S1. Ethanol (95% purity) was used for cleaning up the downstream
major elements is listed in Table S1. Ethanol (95% purity) was used for cleaning up the downstream
units, including the condensing system by absorbing the remaining bio-oil on the inner wall surface.
units, including the condensing system by absorbing the remaining bio-oil on the inner wall surface.
Ethanol was purchased from Sigma-Aldrich (Milwaukee, WI, USA). Argon was used as the inert gas
Ethanol was purchased from Sigma-Aldrich (Milwaukee, WI, USA). Argon was used as the inert gas
during pyrolysis and the gas tank was obtained from Airgas Inc. (West Allis, WI, USA).
during pyrolysis and the gas tank was obtained from Airgas Inc. (West Allis, WI, USA).

3.2. Methods

3.2.1. Sub-Pilot-Scale Pyrolytic System

A sub-pilot-scale pyrolytic system (Figure 5) was used in this study to produce BBC and conduct
autocatalytic tests. The system included a feeding system (feedstock silo, screw feeder), pyrolytic
Catalysts 2018, 8, 524 7 of 11

3.2. Methods

3.2.1. Sub-Pilot-Scale Pyrolytic System

A sub-pilot-scale pyrolytic system (Figure 5) was used in this study to produce BBC and conduct
Catalysts 2018, 8, x FOR PEER REVIEW 7 of 11
autocatalytic tests. The system included a feeding system (feedstock silo, screw feeder), pyrolytic
reactor with a large screw inside, biochar/bio-oil/py-gas collection systems (biochar discharge zone
reactor with a large screw inside, biochar/bio-oil/py-gas collection systems (biochar discharge zone
and collector, bio-oil collector, gas outlet), two heat exchangers, and control systems for both the
and collector, bio-oil collector, gas outlet), two heat exchangers, and control systems for both the
temperature and the screw. In addition, the system was specifically equipped with a downstream
temperature and the screw. In addition, the system was specifically equipped with a downstream
cylindrical reactor, which can be used as a catalytic reactor when filled with catalyst. This system had
cylindrical reactor, which can be used as a catalytic reactor when filled with catalyst. This system had
a solid feeding capacity of 4 kg/h (~0.1 ton/day). The system can be pressurized to 100 psi and both
a solid feeding capacity of 4 kg/h (~0.1 ton/day). The system can be pressurized to 100 psi and both
pyrolytic and catalytic reactors can be heated up to 900 ◦ C.
pyrolytic and catalytic reactors can be heated up to 900 °C.

Figure 5. The rendering of the sub-pilot-scale pyrolytic

pyrolytic system.
system.

3.2.2. Biosolids Non-Catalytic and Autocatalytic Pyrolysis

3.2.2. Biosolids Non-Catalytic and Autocatalytic Pyrolysis
During the pyrolysis test, the feedstock in the silo was fed into the hot pyrolysis reactor by a
During the pyrolysis test, the feedstock in the silo was fed into the hot pyrolysis reactor by a
small screw. Then the feedstock was conveyed to the biochar discharge zone by the big screw in the
small screw. Then the feedstock was conveyed to the biochar discharge zone by the big screw in the
reactor. The feedstock feeding rate and the pyrolysis residence time were controlled by the screw
reactor. The feedstock feeding rate and the pyrolysis residence time were controlled by the screw
rotation speed. The residence time of all the tests were 20 min. The pyrolysis vapor and the resulting
rotation speed. The residence time of all the tests were 20 min. The pyrolysis vapor and the resulting
biochar were separated in the discharge zone. The vapor went through the downstream reactor (with
biochar were separated in the discharge zone. The vapor went through the downstream reactor (with
or without BBC depending on the test requirement) and the biochar dropped into the biochar collector.
or without BBC depending on the test requirement) and the biochar dropped into the biochar
The py-gas and the bio-oil were separated in the condensing system, which has two high-capacity heat
collector. The py-gas and the bio-oil were separated in the condensing system, which has two high-
exchangers in tandem. A very small amount of uncondensed vapor was finally captured by a large
capacity heat exchangers in tandem. A very small amount of uncondensed vapor was finally
activated carbon filter. A gas sampling point was located at the end of the system to collect the gas for
captured by a large activated carbon filter. A gas sampling point was located at the end of the system
a duration using a large Tedlar® bag. The remaining tail gas was extracted to the building roof by a
to collect the gas for a duration using a large Tedlar® bag. The remaining tail gas was extracted to the
ventilation system, including a powered draft fan. The bio-oil was collected in the two condensers.
building roof by a ventilation system, including a powered draft fan. The bio-oil was collected in the
During each test, argon was used to flush the system resulting in an oxygen-deficient environment
two condensers. During each test, argon was used to flush the system resulting in an oxygen-deficient
environment with a flow rate of 100 cc/min. The picture of the sub-pilot-scale pyrolytic system with
key units highlighted is shown in Figure S5.
For the non-catalytic pyrolysis tests, one was performed for system validation at 500 °C and the
other was performed for control at 800 °C in comparison with the autocatalytic pyrolysis. For the
validation test, the pyrolysis reactor was set at 500 °C and the downstream reactor was 500 °C without
any BBC addition. The biosolids was fed into the system at a feeding rate of 0.7 kg/h for an hour. For
Catalysts 2018, 8, 524 8 of 11

with a flow rate of 100 cc/min. The picture of the sub-pilot-scale pyrolytic system with key units
highlighted is shown in Figure S5.
For the non-catalytic pyrolysis tests, one was performed for system validation at 500 ◦ C and the
other was performed for control at 800 ◦ C in comparison with the autocatalytic pyrolysis. For the
validation test, the pyrolysis reactor was set at 500 ◦ C and the downstream reactor was 500 ◦ C without
any BBC addition. The biosolids was fed into the system at a feeding rate of 0.7 kg/h for an hour.
For the control test, the pyrolysis reactor was set at 800 ◦ C and the downstream reactor was 500 ◦ C
without any BBC addition. The biosolids was fed into the system at a feeding rate of 0.9 kg/h for
an hour. The downstream temperature of 500 ◦ C was to minimize the condensation of pyrolysis
vapor constituents during conveyance to the heat exchangers and to minimize the effect of secondary,
homogeneous reactions among vapor components at high temperature [36,37].
For the autocatalytic pyrolysis tests, one scenario was in-situ catalysis and the other scenario
was downstream catalysis. The BBC used in these tests was the original biochar made from the
800 ◦ C control test without further modification or shaping. For in-situ catalysis, the pyrolysis reactor
was set at 800 ◦ C and the downstream reactor was 500 ◦ C without any BBC addition. The BBC was
fully premixed with biosolids in the feeding silo and the mass ratio of catalyst to biosolids was 1.
The biosolids/BBC mixture was fed into the system for an hour with a feeding rate of 0.5 kg/h.
For downstream catalysis, the pyrolysis reactor was set at 800 ◦ C and the downstream reactor was
800 ◦ C with the addition of 0.45 kg of BBC. Corresponding to two different catalyst to biosolids mass
ratios of 1 and 0.5, the biosolids feeding rate was controlled at 0.45 kg/h and 0.9 kg/h, respectively.
The biosolids was supplied to the system for an hour. The detailed experimental design of autocatalytic
and non-catalytic testing is listed in Table 1. All experiments were performed in duplicate.

Table 1. Experimental design of autocatalytic and non-catalytic testing.

Downstream
Pyrolysis Downstream Catalyst Feeding Rate Feeding
Temperature Comment
Temperature (◦ C) Loading (kg) (kg/hr) Duration (min)
(◦ C)
downstream catalysis
800 800 0.45 0.45 60 with biosolids feeding
(catalyst/biosolids = 1)
downstream catalysis
Autocatalytic 800 800 0.45 0.9 60 with biosolids feeding
(catalyst/biosolids = 0.5)
in-situ catalysis with
biosolids/biochar
800 500 0 0.5 60
mixture feeding
(catalyst/biosolids = 1)
800 500 0 0.9 60 control test
Non-Catalytic
500 500 0 0.7 60 validation test

3.2.3. Product Analyses

The masses of biochar and bio-oil were measured gravimetrically. In particular, the majority of
bio-oil was from the condensers (~95 wt%). Some sticky bio-oil that was originally attached to the inner
wall of all the downstream units was washed out using ethanol. The weight difference between ethanol
input and eluent output was bio-oil mass from the inner wall. In addition, the mass of the bio-oil that
was captured by the activated carbon filter was obtained based on the filter weight difference before
and after each test. Hence, the bio-oil total mass included the condenser bio-oil mass, inner wall bio-oil
mass, and filter bio-oil mass. The py-gas mass was calculated by difference (i.e., biosolids feeding mass
minus the sum of biochar and bio-oil).
Py-gas composition (H2 , CH4 , CO, and CO2 concentrations) was determined by GC (Agilent
Technologies 7890A, Santa Clara, CA, USA) with a thermal conductivity detector as described
elsewhere [16,17]. Chemical constituents in the bio-oil were characterized by GC-MS (7890B coupled
with 5977A, Agilent Technologies, Santa Clara, CA, USA) for qualitative analysis at Iowa State
University’s Bioeconomy Institute as described by Brown et al. (2015) [38].
Catalysts 2018, 8, 524 9 of 11

The HHV of py-gas was calculated based on each component concentration and corresponding
HHV. The HHVs of bio-oil and biochar were determined using bomb calorimetry (Parr 1341,
Parr Instrument Company, Moline, IL, USA). The product energy per mass of biosolids pyrolyzed
(kJ/kg-biosolids) was calculated by multiplying each pyrolysis product yield with its corresponding
HHV (e.g., py-gas yield multiplied by py-gas HHV).

4. Conclusions and Prospective

This study demonstrated that autocatalytic pyrolysis of biosolids can be feasible on a large scale.
The sub-pilot-scale test with the downstream catalysis had better catalytic performance with higher
py-gas yield and lower bio-oil yield in comparison with the previous bench-scale results. The in-situ
catalysis process showed the potential to increase py-gas yield, but the increase was limited. It was
expected that using a higher input pyrolyzer with a better mixing condition would further improve
the in-situ autocatalytic performance in terms of the py-gas yield. Overall, using biosolids biochar as a
catalyst for biosolids pyrolysis can increase the py-gas yield and energy.
Py-gas is relatively clean for convenient energy recovery when compared to bio-oil, which requires
further conditioning (in particular, many WRRFs already produce and combust anaerobic digester
biogas for on-site energy recovery; it is most likely to co-combust biogas and py-gas using existing
boilers or engines to generate more energy for on-site use). Moreover, biosolids biochar proved to be
an efficient adsorbent for contaminant removal and a good soil amendment for plant growth [39–41].
The biosolids derived bio-oil can also be co-digested anaerobically to produce more renewable fuel
(i.e., biogas) via specific pretreatment or using acclimated biomass [42]. Therefore, the autocatalytic
pyrolysis process can be coupled with other existing technologies and applications to simultaneously
enhance energy recovery, minimize adverse environmental impacts, and generate value-added
products from wastewater [43,44].

5. Patents
Daniel Zitomer, Zhongzhe Liu, Patrick McNamara, Catalysts for pyrolysis. (No. PCT/US2017/038130).

Supplementary Materials: The following are available online at http://www.mdpi.com/2073-4344/8/11/524/s1,

Figure S1: Process diagram of the autocatalytic pyrolysis of biosolids, Figure S2: Product yields and optical
properties of the sub-pilot-scale test and the bench-scale test (500 ◦ C), Figure S3: Bio-oil optical property from the
sub-pilot-scale tests, Figure S4: Bio-oil and py-gas energy contents, Figure S5: The picture of the sub-pilot-scale
pyrolytic system with key units highlighted, Table S1: Elemental analysis of Milorganite® .
Author Contributions: Conceptualization, P.M., Z.L. and S.S.; methodology, Z.L.; formal analysis, Z.L.;
investigation, Z.L.; data curation, Z.L.; writing—original draft preparation, Z.L.; writing—review and editing,
P.M., D.Z. and S.S.; supervision, P.M.; project administration, P.M.; funding acquisition, P.M., Z.L., S.S. and D.Z.
Funding: This large-scale research was funded by MMSD Research Grants M03029P16 and M03029P36, Water
Quality Center at Marquette University, and Marquette University.
Acknowledgments: We are thankful for the mentorship provided throughout the project by Matthew Magruder
from MMSD. Laboratory assistance from Zachary Pederson, Matthew Hughes, and Erik Anderson is greatly
appreciated. We are also grateful to Robert Brown and Patrick Johnston of the Iowa State University Bioeconomy
Institute for providing bio-oil GC-MS analysis.
Conflicts of Interest: The authors declare no conflict of interest. The funders had no role in the design of the
study; in the collection, analyses, or interpretation of data; in the writing of the manuscript. MMSD reviewed the
manuscript prior to submission to ensure that there was no release of confidential information.

References
1. Jhansi, S.C.; Mishra, S.K. Wastewater Treatment and Reuse: Sustainability Options. Cons. J. Sustain. Dev.
2013, 10, 1–15.
2. Eggen, R.I.L.; Hollender, J.; Joss, A.; Schärer, M.; Stamm, C. Reducing the discharge of micropollutants in the
aquatic environment: The benefits of upgrading wastewater treatment plants. Environ. Sci. Technol. 2014, 48,
7683–7689. [CrossRef] [PubMed]
Catalysts 2018, 8, 524 10 of 11

3. Venkatesan, A.K.; Hamdan, A.-H.M.; Chavez, V.M.; Brown, J.D.; Halden, R.U. Mass Balance Model for
Sustainable Phosphorus Recovery in a US Wastewater Treatment Plant. J. Environ. Qual. 2016, 45, 84–89.
[CrossRef] [PubMed]
4. Mo, W.; Zhang, Q. Energy-nutrients-water nexus: Integrated resource recovery in municipal wastewater
treatment plants. J. Environ. Manag. 2013, 127, 255–267. [CrossRef] [PubMed]
5. Gude, V. Energy positive wastewater treatment and sludge management. Edorium J. Waste Manag. 2015, 1,
10–15.
6. Cao, Y.; Pawłowski, A. Sewage sludge-to-energy approaches based on anaerobic digestion and pyrolysis:
Brief overview and energy efficiency assessment. Renew. Sustain. Energy Rev. 2012, 16, 1657–1665. [CrossRef]
7. Xia, K.; Hundal, L.; Kumar, K. Triclocarban, triclosan, polybrominated diphenyl ethers, and 4-nonylphenol
in biosolids and in soil receiving 33-year biosolids application. Environ Toxicol Chem. 2010, 29, 597–605.
[CrossRef] [PubMed]
8. Bright, D.A.; Healey, N. Contaminant risks from biosolids land application. Environ. Pollut. 2003, 126, 39–49.
[CrossRef]
9. Singh, R.P.; Agrawal, M. Potential benefits and risks of land application of sewage sludge. Waste Manag.
2008, 28, 347–358. [CrossRef] [PubMed]
10. Carey, D.E.; Zitomer, D.H.; Hristova, K.R.; Kappell, A.D.; McNamara, P.J. Triclocarban Influences Antibiotic
Resistance and Alters Anaerobic Digester Microbial Community Structure. Environ. Sci. Technol. 2016, 50,
126–134. [CrossRef] [PubMed]
11. Carey, D.; Zitomer, D.H.; Kappell, A.; Choi, M.; Hristova, K.; McNamara, P. Chronic exposure to triclosan
sustains microbial community shifts and alters antibiotic resistance gene levels in anaerobic digesters.
Environ. Sci. Process. Impacts 2016. [CrossRef] [PubMed]
12. Rulkens, W. Sewage sludge as a biomass resource for the production of energy: Overview and assessment of
the various options. Energy Fuels 2008, 22, 9–15. [CrossRef]
13. Chen, D.; Yu, Y.; Zhu, H.; Liu, Z.; Xu, Y. Ferrite process of electroplating sludge and enrichment of copper by
hydrothermal reaction. Sep. Purif. Technol. 2008, 62, 297–303. [CrossRef]
14. Lumley, N.P.G.; Ramey, D.F.; Prieto, A.L.; Braun, R.J.; Cath, T.Y.; Porter, J.M. Techno-economic analysis of
wastewater sludge gasification: A decentralized urban perspective. Bioresour. Technol. 2014, 161, 385–394.
[CrossRef] [PubMed]
15. Bridle, T.; Pritchard, D. Energy and nutrient recovery from sewage sludge via pyrolysis. Water Sci. Technol.
2004, 50, 169–175. [CrossRef] [PubMed]
16. McNamara, P.; Koch, J.; Zitomer, D. Pyrolysis of Wastewater Biosolids: Lab-Scale Experiments and Modeling.
Proc. Water Environ. Fed. 2014, 2014, 1–14. [CrossRef]
17. McNamara, P.J.; Koch, J.D.; Liu, Z.; Zitomer, D.H. Pyrolysis of Dried Wastewater Biosolids Can Be Energy
Positive. Water Environ. Res. 2016, 88, 804–810. [CrossRef] [PubMed]
18. Samolada, M.C.; Zabaniotou, A.A. Comparative assessment of municipal sewage sludge incineration,
gasification and pyrolysis for a sustainable sludge-to-energy management in Greece. Waste Manag. 2014, 34,
411–420. [CrossRef] [PubMed]
19. Ross, J.J.; Zitomer, D.H.; Miller, T.R.; Weirich, C.A.; McNamara, P.J. Emerging investigators series: Pyrolysis
removes common microconstituents triclocarban, triclosan, and nonylphenol from biosolids. Environ. Sci.
Water Res. Technol. 2016, 2, 282–289. [CrossRef]
20. Hoffman, T.C.; Zitomer, D.H.; McNamara, P.J. Pyrolysis of Wastewater Biosolids Significantly Reduces
Estrogenicity. J. Hazard. Mater. 2016. [CrossRef] [PubMed]
21. Kimbell, L.K.; Kappell, A.D.; McNamara, P.J. Effect of pyrolysis on the removal of antibiotic resistance genes
and class I integrons from municipal wastewater biosolids. Environ. Sci. Water Res. Technol. 2018. [CrossRef]
22. Sadaka, S.; Boateng, A. Pyrolysis and Bio-Oil; University of Arkansas System: Little Rock, AR, USA, 2009.
23. Liu, Z.; McNamara, P.; Zitomer, D. Autocatalytic Pyrolysis of Wastewater Biosolids for Product Upgrading.
Environ. Sci. Technol. 2017, 51, 9808–9816. [CrossRef] [PubMed]
24. Liu, Z.; Singer, S.; Zitomer, D.; McNamara, P. Can Autocatalytic Pyrolysis of Wastewater Biosolids be Energy
Neutral and Generate Value-Added Products? Proc. Water Environ. Fed. 2017, 2017, 360–364. [CrossRef]
25. Liu, Z.; McNamara, P.; Zitomer, D. Product Upgrading during Biosolids Pyrolysis by Using a Low-cost
Natural Catalyst. Proc. Water Environ. Fed. 2016, 796–802. [CrossRef]
Catalysts 2018, 8, 524 11 of 11

26. Chang, F.; Wang, C.; Wang, Q.; Jia, J.; Wang, K. Pilot-scale pyrolysis experiment of municipal sludge and
operational effectiveness evaluation. Energy Sources Part A Recover. Util. Environ. Eff. 2016, 38, 472–477.
[CrossRef]
27. Lin, Q.H.; Cheng, H.; Chen, G.Y. Preparation and characterization of carbonaceous adsorbents from sewage
sludge using a pilot-scale microwave heating equipment. J. Anal. Appl. Pyrolysis 2012, 93, 113–119. [CrossRef]
28. Lin, Q.; Chen, G.; Liu, Y. Scale-up of microwave heating process for the production of bio-oil from sewage
sludge. J. Anal. Appl. Pyrolysis 2012, 94, 114–119. [CrossRef]
29. Sánchez, M.E.; Martínez, O.; Gómez, X.; Morán, A. Pyrolysis of mixtures of sewage sludge and manure:
A comparison of the results obtained in the laboratory (semi-pilot) and in a pilot plant. Waste Manag. 2007,
27, 1328–1334. [CrossRef] [PubMed]
30. Dayton, D.C.; Carpenter, J.R.; Kataria, A.; Peters, J.E.; Barbee, D.; Mante, O.D.; Gupta, R. Design and
operation of a pilot-scale catalytic biomass pyrolysis unit. Green Chem. 2015, 17, 4680–4689. [CrossRef]
31. Mendes, F.L.; Ximenes, V.L.; de Almeida, M.B.B.; Azevedo, D.A.; Tessarolo, N.S.; de Rezende Pinho, A.
Catalytic pyrolysis of sugarcane bagasse and pinewood in a pilot scale unit. J. Anal. Appl. Pyrolysis 2016, 122,
395–404. [CrossRef]
32. Domínguez, A.; Fernández, Y.; Fidalgo, B.; Pis, J.J.; Menéndez, J.A. Biogas to Syngas by Microwave-Assisted
Dry Reforming in the Presence of Char. Energy Fuels 2007, 21, 2066–2071. [CrossRef]
33. Muradov, N.; Fidalgo, B.; Gujar, A.C.; Garceau, N.; T-Raissi, A. Production and characterization of Lemna
minor bio-char and its catalytic application for biogas reforming. Biomass Bioenergy 2012, 42, 123–131.
[CrossRef]
34. Sappok, M.; Wagels, D. Method for Stabilizing Heating Oil or Diesel Oil, Particularly Heating Oil or Diesel Oil
from the Depolymerization of Hydrocarbon-Containing Residues, or Pyrolysis Oil. U.S. Patent No. 8,394,264,
12 March 2013.
35. Ren, S.; Lei, H.; Wang, L.; Bu, Q.; Chen, S.; Wu, J. Hydrocarbon and hydrogen-rich syngas production by
biomass catalytic pyrolysis and bio-oil upgrading over biochar catalysts. RSC Adv. 2014, 4, 10731–10737.
[CrossRef]
36. Sun, Q.; Yu, S.; Wang, F.; Wang, J. Decomposition and gasification of pyrolysis volatiles from pine wood
through a bed of hot char. Fuel 2011, 90, 1041–1048. [CrossRef]
37. Gilbert, P.; Ryu, C.; Sharifi, V.; Swithenbank, J. Tar reduction in pyrolysis vapours from biomass over a hot
char bed. Bioresour. Technol. 2009, 100, 6045–6051. [CrossRef] [PubMed]
38. Rover, M.; Hall, P.; Johnston, P.; Smith, R.; Brown, R. Stabilization of bio-oils using low temperature, low
pressure hydrogenation. Fuel 2015, 153, 224–230. [CrossRef]
39. Tong, Y.; Mayer, B.K.; McNamara, P.J. Triclosan adsorption using wastewater biosolids-derived biochar.
Environ. Sci. Water Res. Technol. 2016, 2, 761–768. [CrossRef]
40. Kimbell, L.K.; Tong, Y.; Mayer, B.K.; McNamara, P.J. Biosolids-Derived Biochar for Triclosan Removal from
Wastewater. Environ. Eng. Sci. 2017, 35, ees.2017.0291. [CrossRef]
41. Carey, D.E.; McNamara, P.J.; Zitomer, D.H. Biochar from Pyrolysis of Biosolids for Nutrient Adsorption and
Turfgrass Cultivation. Water Environ. Res. 2015, 87, 2098–2106. [CrossRef] [PubMed]
42. Seyedi, S. Anaerobic Co-digestion of Aqueous Liquid from Biosolids Pyrolysis. Master’s Thesis, Marquette
University, Milwaukee, WI, USA, 2018.
43. Liu, Z.; Singer, S.; Tong, Y.; Kimbell, L.; Anderson, E.; Hughes, M.; Zitomer, D.; McNamara, P. Characteristics
and applications of biochars derived from wastewater solids. Renew. Sustain. Energy Rev. 2018, 90, 650–664.
[CrossRef]
44. Liu, Z.; Zitomer, D.; McNamara, P.; Mayer, B.; Parolari, A.; McDonald, W. NEWAGE: A system with enhanced
energy recovery and value-added products from wastewater and wastewater biosolids for agriculture and
green. In Abstracts of Papers of the American Chemical Society; American Chemical Society: Washington, DC,
USA, 2017; Volume 254, ISBN 1155 16TH ST.

© 2018 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access
article distributed under the terms and conditions of the Creative Commons Attribution
(CC BY) license (http://creativecommons.org/licenses/by/4.0/).