Bio-a oma ics: Re olu ionizing he in eg a ed biomass and plas ic was e
alo iza ion o high- alue a oma ic hyd oca bons ia bi unc ional
ca aly ic pa hways o bio-syngas con e sion
Ma ia Sai , Rub´
en Blay-Roge , Muhammad Asi Nawaz
*
, Luis F. Bobadilla,
Tomas Rami ez-Reina , J.A. Od iozola
**
Depa men o Ino ganic Chemis y and Ma e ials Sciences Ins i u e, Uni e si y o Se ille-CSIC, 41092, Se ille, Spain
ARTICLE INFO
Keywo ds:
Bio-a oma ics
Biomass-de i ed syngas
Co-gasi ica ion
Tandem ca alysis
Bi unc ional ca aly ic pa hways
ABSTRACT
A oma ic hyd oca bons play a pi o al ole in a ious indus ial applica ions, se ing as essen ial building blocks
o p oduce polyme s, esins, and special y chemicals. T adi ionally, hei syn hesis has been elian on ossil
uels, aising conce ns abou en i onmen al sus ainabili y and esou ce deple ion. Howe e , ecen ad ance-
men s in he ield ha e pa ed he way o a pa adigm shi , wi h a ocus on biomass-de i ed syn hesis gas as a
enewable and en i onmen ally iendly eeds ock. This e iew explo es inno a i e sho cu s in he syn hesis o
a oma ic hyd oca bons, a key a ea o esea ch ha holds p omise o a mo e sus ainable and e icien u u e. As
we del e in o he in icacies o biomass-de i ed syn hesis gas con e sion, we will examine b eak h oughs in
ca alys de elopmen , p ocess op imiza ion, and in eg a ed app oaches. By sc u inizing hese ad ancemen s, we
aim o p o ide a comp ehensi e o e iew o he cu en s a e o he a , highligh ing bo h challenges and op-
po uni ies o u he explo a ion. The u gency o add essing en i onmen al conce ns and he g owing demand
o enewable al e na i es unde sco e he impo ance o ee alua ing he me hodologies. The unique cha ac-
e is ics o biomass-de i ed syn hesis gas coupled wi h co-gasi ica ion p ocesses p esen an in iguing a enue o
ede ining he landscape o a oma ic hyd oca bon syn hesis. Th ough his explo a ion, we seek o un a el he
complexi ies o hese inno a i e sho cu s, o e ing insigh s ha may con ibu e o a mo e sus ainable and
g eene u u e o he chemical indus y.
1. In oduc ion
A oma ics, cha ac e ized by hei benzene ing s uc u es, a e key
componen s in nume ous indus ial applica ions, ex ensi ely u ilized in
he p oduc ion o syn he ic ma e ials, ine chemicals, pes icides, ene gy,
and o he indus ies [1]. The mode n wo ld’s esou ce challenges and
he apid ad ancemen o he global echno-economic landscape ha e
signi ican ly ampli ied he demand o a oma ics [2–4]. Whe e he key
p oduc s wi hin he a oma ic sec o include benzene, oluene, and
xylene (BTX), ollowed by e hylbenzene, s y ene, and cumene.
Va ious ecen epo s highligh he signi ican g ow h in global
consump ion and demand o BTX, p ojec ing he ma ke size o each
165.65 million ons by 2029, wi h a cu en Compound Annual G ow h
Ra e (CAGR) o o e 4 %. As Fig. 1 p esen s he global ma ke size
o ecas o BTX om 2022 o 2032, highligh ing a s eady Compound
Annual G ow h Ra e (CAGR) o 3.80 %. The ma ke demand is p ojec ed
o inc ease om 128,619.10 kilo ons (k ) in 2022 o app oxima ely
179,920.91 k by 2031, indica ing ising consump ion d i en by he
expanding pe ochemical and indus ial sec o s. The upwa d ajec o y
unde sco es BTX’s c i ical ole in p oducing essen ial chemicals, uels,
and syn he ic ma e ials, making i a key segmen in he global ene gy
and manu ac u ing indus ies. Howe e , i s supply hea ily depends on
impo s, unde sco ing he need o explo e new p oduc ion ou es o
a oma ic hyd oca bons, especially BTX [4–6]. His o ically, he syn hesis
o hese i al componen s has been hea ily dependen on ossil uels,
which ypically in ol e ca aly ic e o ming o naph ha, py olysis o
gasoline in e hylene plan s, and oluene disp opo iona ion. Howe e ,
hese con en ional me hods ha e aised signi ican conce ns abou he
This a icle is pa o a special issue en i led: Ra ael Bilbao published in Biomass and Bioene gy.
* Co esponding au ho .
** Co esponding au ho .
E-mail add esses: [email p o ec ed] (M.A. Nawaz), [email p o ec ed] (J.A. Od iozola).
Con en s lis s a ailable a ScienceDi ec
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h ps://doi.o g/10.1016/j.biombioe.2025.107736
Recei ed 31 Decembe 2024; Recei ed in e ised o m 18 Feb ua y 2025; Accep ed 19 Feb ua y 2025
Biomass and Bioene gy 196 (2025) 107736
A ailable online 23 Feb ua y 2025
0961-9534/© 2025 The Au ho s. Published by Else ie L d. This is an open access a icle unde he CC BY license ( h p://c ea i ecommons.o g/licenses/by/4.0/ ).
deple ion o ini e esou ces and he eliance on ola ile pe oleum im-
po s, d i en by luc ua ing pe ochemical p ices. While he u gency o
add essing en i onmen al conce ns and he accele a ing ecen cam-
paigns o was e alo iza ion p esen a model o enewable ene gy e-
sou ces in p oducing a oma ic hyd oca bons, aligning wi h he global
na a i e o a ca bon- ee en i onmen . In his conce n, he ecen ad-
ancemen s in g een chemis y ha e ca alyzed a ans o ma i e shi
owa ds u ilizing biomass-de i ed syn hesis gas (syngas) as a enewable
and eco- iendly eeds ock o a oma ic hyd oca bon p oduc ion. The
unique cha ac e is ics o biomass-de i ed syngas o e an in iguing
a enue o ede ining he landscape o a oma ic hyd oca bon syn hesis.
This explo a ion aims o un a el he complexi ies o hese inno a i e
pa hways, o e ing insigh s ha con ibu e o a mo e sus ainable and
g eene u u e o he chemical indus y. In his con ex , in eg a ing
biomass and plas ic was e as eeds ocks o e s a p omising solu ion o
p oducing aluable a oma ic compounds, add essing en i onmen al is-
sues, and educing eliance on ossil uels. Biomass, being
ca bon-neu al, and plas ic was e, ich in ca bon and hyd ogen, com-
plemen each o he , enhancing he p oduc ion o high- alue a oma ics.
Using ca aly ic p ocesses in his con ex enhances selec i i y owa d
a oma ic compounds, esul ing in highe yields. The high
hyd ogen- o-ca bon a io o plas ics complemen s he high
oxygen- o-ca bon a io o biomass, imp o ing p oduc uni o mi y and
minimizing coke deposi ion. This in eg a ion makes biomass a
cos -e ec i e eeds ock o syngas p oduc ion.
Fo ins ance, syngas p oduced in co-gasi ica ion o biomass and
plas ic was e can be ou ed o syngas-based p oduc ion o a oma ics ia
Fische T opsch Syn hesis (FTS), Re e se-Wa e -Gas-Shi (RWGS) o
Me hanol Syn hesis (MTS) ia indi ec ( wo-s ep) o di ec (one-s ep)
p ocesses [7–19]. Whe e he wo-s ep me hod in ol es con e ing syn-
gas (CO +H
2
) in o me hanol/ole ins/pa a ins using a me al oxide
ca alys , ollowed by a oma iza ion on a molecula sie e ( ypically
zeoli e) [20–24]. While he one-s ep (o en ega ded as andem o
di ec ) ou e employs an in eg a ed ca alys o di ec ly con e syngas
in o a oma ics using a modi ied me al-oxide/zeoli e composi e ca alys
[25,26]. Recen de elopmen s in he ca aly ic p ocesses, syn hesis
ou es, and design app oaches o a oma ic hyd oca bons om syngas
ha e shown signi ican p omise, pa icula ly u ilizing FTS and MTS
andem ou es in conjunc ion wi h HZSM-5 zeoli es [27]. Inno a ions in
ca alys design, especially he in eg a ion o HZSM-5, ha e enhanced he
selec i i y and yield o a oma ic compounds. The FTS p ocess, adi-
ionally known o con e ing syngas in o a ange o lowe ole inic hy-
d oca bons, has been op imized by inco po a ing HZSM-5, o inc ease
he p oduc ion o desi ed lowe a oma ic hyd oca bons (such as BTX).
Concu en ly, MTS om syngas ollowed by me hanol- o-a oma ics
(MTA) con e sion using HZSM-5 has eme ged as a obus al e na i e
o acili a e he a oma iza ion p ocess majo ly owa ds e ame hyl
benzene. Howe e , ecen s udies ha e ocused on imp o ing he s a-
bili y and ac i i y o hese ca alys s unde ope a ing condi ions,
add essing challenges such as ca alys deac i a ion and p ocess in e-
g a ion. Fu he mo e, ad ances in p ocess op imiza ion, including
eac o design and ope a ional pa ame e s, ha e con ibu ed o highe
e iciency and lowe ene gy consump ion [28]. These de elopmen s
collec i ely unde sco e he po en ial o u ilizing syngas de i ed om
biomass and plas ic was e o p oduce high- alue a oma ic hyd oca -
bons, pa ing he way o mo e sus ainable and e icien chemical
manu ac u ing p ocesses.
In summa y, in eg a ing biomass and plas ic was e-de i ed syngas
o a oma ics p oduc ion ep esen s a c ucial s ep owa d a sus ainable
chemical indus y. This e iew explo es he Bio-Tandem A oma ic (BTA)
p ocess, ocusing on co-gasi ica ion/py olysis, syngas cleaning, and
FTS/MTS-media ed ou es, while highligh ing ecen ad ancemen s and
ongoing challenges. By b idging key gaps in ca alysis, p ocess engi-
nee ing, and was e managemen , his wo k emphasizes he syne gy
be ween biomass and plas ic was e co-p ocessing, ad ances in bi unc-
ional ca aly ic pa hways, and inno a ions in eac o design o enhance
selec i i y, s abili y, and e iciency. Addi ionally, i e alua es co-
gasi ica ion s a egies, ca alys pe o mance, and p ocess in eg a ion,
linking undamen al esea ch wi h indus ial easibili y. By add essing
bo h echnical and sus ainabili y challenges, his e iew p o ides alu-
able insigh s in o op imizing bio-a oma ic p oduc ion, p omo ing a
g eene and mo e esou ce-e icien u u e o chemical manu ac u ing.
Fig. 1. Global BTX ma ke o e iew and p ojec ed CAGR alue du ing he o ecas pe iod o 2023–2031. Sou ce: S ai s esea ch BTX ma ke epo 2023. No e: K
=kilo ons.
M. Sai e al.
Biomass and Bioene gy 196 (2025) 107736
2
2. En i onmen al Impe a i e o sus ainable and Renewable
Socie y
Fossil uels like pe oleum, coal, and na u al gas cu en ly domina e
global p ima y ene gy consump ion, accoun ing o abou 75 %, wi h
nuclea powe , hyd opowe , and biomass comp ising he emaining 25
% [29]. Howe e , dwindling c ude oil ese es, inc easing uel de-
mands, clima e conce ns, and poli ical commi men s ha e in ensi ied
he ocus on enewable ene gy sou ces. Fig. 2 highligh s he u gen need
o a sus ainable and enewable ene gy ansi ion by illus a ing he
en i onmen al impac o ossil uel ex ac ion, e ining, and CO
2
emis-
sions. The p essing issue o ai pollu ion and g eenhouse gas emissions,
ein o ce he necessi y o ca bon cap u e and con e sion echnologies
o mi iga e clima e change. While he dominance o ossil uels o global
ene gy consump ion, he deple ing c ude oil ese es and he g owing
demand o al e na i e uels, necessi a es he c i ical ole o al e na i e
sus ainable p ocesses in ans o ming hose was e s eams in o sus ain-
able uels, pa ing he way o a cleane , mo e esilien ene gy u u e.
Among hese, biomass and biowas es, de i ed h ough pho osyn hesis,
seques e CO
2
and H
2
O in o ca bon- ich solids, making hem an
a ac i e enewable al e na i e. Thei apid p oduc ion a e and
ca bon-neu al na u e allow hem o be con e ed in o aluable p od-
uc s such as syngas, gaseous me hane, liquid bioe hanol, biodiesel,
biodeg adable plas ics, solid b ique es, and biochemical p oduc s, o -
e ing simila unc ionali y o hose de i ed om ossil uels [30]. Bio-
ene gy s ands ou among enewable ene gy sou ces due o i s unique
abili y o be collec ed, s o ed, and anspo ed, making i sui able o
on-demand use [31,32]. Biomass esou ces a e di e se, encompassing
ag icul u al esidues (e.g., s aw, s alks, and co n cobs), o es y was es
(e.g. sh ubs, b anches, and lea es), ene gy c ops (e.g., algae, swi ch-
g ass, and ja opha seeds,), ood indus y byp oduc s (e.g., co ee shells),
human was e om municipal plan s and sewage, and animal a ming
byp oduc s (e.g., manu e and a ) [33]. Solid biomass is p edominan ly
u ilized o hea and elec ici y p oduc ion, ep esen ing he la ges
sha e o i s usage. I s abundan a ailabili y and ca bon-neu al p o ile
also posi ion biomass as a p omising eeds ock o bio uels and aluable
chemicals, wi h signi ican ly lowe g eenhouse gas emissions han ossil
uels. Among a ious ypes o biomass, lignocellulosic biomass, p i-
ma ily sou ced om ag icul u al and o es y was es, is pa icula ly
no able. O e 100 billion me ic ons o lignocellulosic biomass a e
gene a ed annually, including 3.7–5.1 billion me ic ons o ag icul u al
esidues disca ded each yea . Whe e, 0.8–10.6 EJ (EJ) o ene gy can be
p oduced annually h ough o es y was e by 2050. In he Eu opean
Union, o es y was e al eady con ibu es o hal o i s enewable ene gy
po olio. On he o he hand, global municipal solid was e gene a ion is
escala ing, wi h 1.3 billion ons p oduced annually and p ojec ions
eaching 2.2 billion ons by 2025 [34]. Plas ics, a majo componen o
his was e, ha e su ged in popula i y due o hei low cos , ligh weigh
na u e, du abili y, and esis ance o en i onmen al deg ada ion [35].
Howe e , hei poo deg adabili y poses signi ican en i onmen al
challenges [36]. Plas ic was e has inc eased om 1.7 million ons in
1950 o 322 million ons in 2015, wi h an es ima ed 12 billion me ic
ons expec ed in land ills by 2050 [37]. Con en ional disposal me hods
like land illing and incine a ion exace ba e en i onmen al issues,
b eaking down plas ics in o mic oplas ics ha pollu e ecosys ems and
oceans, h ea ening ma ine li e and ecosys ems [38–42].
3. The mochemical p ocesses o was e alo iza ion
Biomass o plas ic alo iza ion ia he mochemical p ocesses o
encompassing he con e sion o o ganic/plas ic was e ma e ials in o
highe - alue p oduc s (such as uels, chemicals, o ene gy applica ions)
can play a c ucial ole in ackling he g owing challenges o was e
managemen o align wi h p inciples o sus ainabili y and ci cula
economy. Among he majo he mochemical p ocesses (combus ion,
incine a ion, py olysis, o gasi ica ion), combus ion o incine a ion
Fig. 2. En i onmen al impe a i e o enewable socie y o educe he eliance on adi ional ossil uel esou ces and mi iga e CO
2
oo p in s.
M. Sai e al.
Biomass and Bioene gy 196 (2025) 107736
3
in ol es bu ning plas ics a high empe a u es in he p esence o excess
oxygen, esul ing in he con e sion o was e in o ca bon dioxide, wa e
apo , and ene gy. While his me hod signi ican ly educes was e ol-
ume and gene a es ene gy, i also aises en i onmen al conce ns due o
he emission o oxic pollu an s and g eenhouse gases. E en hough,
ad anced incine a ion echnologies equipped wi h s ingen emission
con ol can minimize hese issues, o e ing a mo e sus ainable app oach
[43]. Since, despi e hei bene i s o high was e educ ion and ene gy
eco e y, incine a ion can elease haza dous subs ances, including
phosgene, dioxins, and hea y me als, which pose se ious en i onmen al
and heal h isks o nea by communi ies [44,45]. Fu he mo e, he need
o ex ensi e lue-gas cleaning inc eases ope a ional cos s, which can
nega i ely impac he e iciency and sus ainabili y o he p ocess [46].
In his con ex , he mochemical p ocesses like gasi ica ion and py olysis
ha e eme ged as p omising solu ions o con e ing was e in o aluable
ene gy and chemical p oduc s [47,48]. Py olysis, a he mal decompo-
si ion p ocess conduc ed a empe a u es be ween 300 ◦C and 900 ◦C in
an oxygen- ee en i onmen , ans o ms o ganic ma e ials in o aluable
p oduc s: liquid bio-oil, solid biocha , and non-condensable syngas. The
yield and composi ion o hese p oduc s a e shaped by key ac o s,
including empe a u e, esidence ime, and he cha ac e is ics o he
eeds ock. Fas py olysis, conduc ed a mode a e empe a u es wi h
sho eac ion imes, has gained a en ion o i s abili y o selec i ely
p oduce bio-oil [49]. Ca aly ic py olysis, using ca alys s like zeoli e
(ZSM-5), ac i a ed ca bon, and a ious me al oxides and chlo ides, en-
hances eac ion e iciency by p o iding ac i e si es o c acking, dehy-
d ogena ion, and a oma iza ion, imp o ing he yield and selec i i y o
desi able liquid p oduc s. Despi e he challenges o con en ional py-
olysis, such as long p ocessing imes and low bio-oil yields wi h high
oxygen con en , ad ancemen s like mic owa e py olysis ha e signi i-
can ly imp o ed he p ocess, majo ly yield py oly ic oil and some syngas
ac ions wi h enhanced H
2
con en and calo i ic alue, esul ing in
imp o ed oil p ope ies. Howe e , scalabili y issues emain, including
eedline clogging due o he high iscosi y o mel ed plas ics and coking
in eac o s, which can cause ope a ional di icul ies [49].
On he o he hand, gasi ica ion is an ad anced he mochemical
p ocess ha con e s was e o ganic ma e ials in o high-quali y syngas a
high empe a u es, ypically anging om 800 ◦C o 1200 ◦C. This
p ocess occu s in a con olled en i onmen wi h a limi ed supply o
oxygen o s eam in he p esence o a gasi ying agen such as CO
2
, s eam,
O
2
, o ai . The es ic ed oxygen supply p e en s comple e combus ion,
leading o he b eakdown o complex ca bonaceous ma e ials in o
simple molecules like ca bon monoxide (CO), hyd ogen (H
2
), ca bon
dioxide (CO
2
), and me hane (CH
4
). The esul ing syngas, which a e ich
in hyd ogen and ca bon monoxide, se e as a aluable eeds ock o
elec ici y gene a ion, syn he ic uel p oduc ion, and a ious chemical
p ocesses. Gasi ica ion occu s in ou key s ages: d ying, py olysis,
oxida ion, and educ ion. The d ying s age (100–200 ◦C) in ol es he
emo al o mois u e wi hou al e ing he chemical composi ion o he
eeds ock. Py olysis, o de ola iliza ion, b eaks down biomass in o non-
condensable gases, condensable liquids ( a s), and solid cha . Du ing
oxida ion, he in e media e p oduc s eac wi h ai , in luencing he inal
composi ion o he gas. In he educ ion and gasi ica ion s age, a ious
e o ming, c acking, and he e ogeneous cha eac ions ake place, ul i-
ma ely leading o he p oduc ion o syngas.
3.1. In eg a ion o he mochemical p ocesses by employing dual
unc ionali y
Co-p ocessing o plas ic was e and biomass by in eg a ing (py olysis
& gasi ica ion) has eme ged as an e ec i e solu ion o was e manage-
men , o e ing syne gis ic economic bene i s and add essing was e
mixing issues while op imizing esou ce eco e y and minimizing
en i onmen al impac s [50]. Such in eg a ed app oaches no only
di e si y he eeds ock base bu also con ibu e o a mo e esilien and
sus ainable was e managemen and ene gy p oduc ion sys em.
Ex ensi e esea ch in his conce n has demons a ed he syne gis ic e -
ec s o combining eeds ocks, enhancing gas yields and educing a
o ma ion [51]. When biomass and plas ic was e unde go co-p ocessing,
signi ican inc ease in gas olume, quali y o liquid uels and dec ease in
a o ma ion a e obse ed, le e aging he complemen a y cha ac e is-
ics o bo h ma e ials. Plas ics ha e a high hyd ogen- o-ca bon (H/C)
a io and low oxygen- o-ca bon (O/C) a io, which complemen bio-
mass’s high O/C and low H/C a io, hus e icien way o imp o ing
p oduc uni o mi y and minimizing coke deposi ion [52–54]. The
ele a ed hyd ogen con en in plas ic was e enhances he ene gy densi y
o biomass, posi ioning i as an economical and e icien eeds ock o
syngas p oduc ion.
The co-gasi ica ion p ocess in ol es complex eac ion dynamics
in luenced by ac o s such as empe a u e, gasi ying agen s, and eed-
s ock composi ion. E en hough, su icien wo k has been a ibu ed o
he mochemical co-p ocessing o ossil uel eplacemen and he p o-
duc ion o essen ial chemicals, he eby imp o ing ene gy secu i y,
howe e , he complex in e ac ions be ween plas ics and biomass equi e
u he esea ch o op imize he p ocess [55]. As b ie ly discussed in he
p e ious sec ion, se e al impo an chemical eac ions go e n he
gasi ica ion o co-gasi ica ion p ocess, s a ing wi h he mal decompo-
si ion (py olysis) eac ions, which b eak down biomass and plas ics in o
ola ile gases, a , and cha . Biomass py olysis ypically p oduces CO,
CO
2
, H
2
, CH
4
, a , and solid cha , while plas ic py olysis p ima ily
gene a es hyd oca bons such as e hylene, me hane, and p opane. These
ola ile compounds hen unde go p ima y gas-phase eac ions, whe e
ca bonaceous ma e ials eac wi h s eam, CO
2
, o oxygen o o m syn-
gas. The majo chemical eac ions in ol ed in gasi ica ion can be ca e-
go ized in o ola iliza ion, cha gasi ica ion, oxida ion, and seconda y
gas-phase eac ions. Vola iliza ion occu s h ough immedia e chemical
eac ion:
Biomass → H
2
+CO +CO
2
+Ta +C
n
H
m
+Cha (Eq. 1)
Cha gasi ica ion p ima ily in ol es wo key eac ions: he wa e -gas
eac ion and he Boudoua d eac ion. These a e ep esen ed by he
ollowing equa ions:
C +H
2
O ⇔ CO +H
2
(ΔH = +131 kJ/mol) P ima y wa e -gas eac ion
(Eq. 2)
C +CO
2
⇔ 2CO (ΔH = +173 kJ/mol) - Boudoua d eac ion (Eq. 3)
Seconda y gas-phase eac ions u he in luence he composi ion o
syngas. One o he mos impo an o hese is he wa e –gas shi
eac ion:
CO +H
2
O ⇔ CO
2
+H
2
(ΔH = − 42 kJ/mol) – Wa e –gas shi eac ion
(Eq. 4)
Oxida ion eac ions, which a e exo he mic, con ibu e o he o e all
ene gy balance o he gasi ica ion p ocess. The key oxida ion eac ions
include:
C +½ O
2
⇔ CO (ΔH = − 111 kJ/mol) – Comple e oxida ion (Eq. 5)
CO +½ O
2
⇔ CO
2
(ΔH = − 283 kJ/mol) – Pa ial oxida ion (Eq. 6)
CH
4
+2O
2
⇔ CO
2
+2H
2
O (ΔH = − 803 kJ/mol) (Eq. 7)
H
2
+½ O
2
⇔ H
2
O (ΔH = − 242 kJ/mol) (Eq. 8)
Se e al e o ming and c acking eac ions also play a c ucial ole in
gasi ica ion. These include s eam e o ming, d y e o ming, and hy-
d oca bon c acking, which in luence he inal gas composi ion:
CH
4
+H
2
O ⇔ CO +3H
2
(ΔH =206 kJ/mol) – S eam e o ming(Eq. 9)
CH
4
+CO
2
⇔ 2CO +2H
2
(ΔH =247 kJ/mol) – D y e o ming(Eq. 10)
M. Sai e al.
Biomass and Bioene gy 196 (2025) 107736
4
C +2H
2
⇔ CH
4
(ΔH = − 75 kJ/mol) – Hyd ogasi ica ion o me hana ion
(Eq. 11)
C
n
H
m
+2nH
2
O ⇔ (2n +m/2)H
2
+nCO
2
(ΔH <0) – S eam e o ming
o hyd oca bons (Eq. 12)
Ta → H
2
+CH
4
+CO +CO
2
+C
n
H
m
(ΔH <0) – Ta c acking(Eq. 13)
The e iciency o co-gasi ica ion and he quali y o syngas depend on
mul iple ac o s, including eeds ock composi ion, gasi ica ion echnol-
ogy, and ope a ing condi ions [56]. Whe e, unde s anding he dis inc
p ope ies o biomass and was e plas ics is essen ial o op imizing
gasi ica ion and o he con e sion echnologies. Table 1 and Fig. 3 shows
he s uc u e and elemen al composi ion o biomass, was e plas ics, and
municipal solid was e (MSW) signi ican ly in luences syngas p oduc ion,
pa icula ly hei ca bon, hyd ogen, and oxygen con en . A highe ca -
bon con en inc eases he calo i ic alue o syngas since ca bon se es as
he p ima y ene gy sou ce in combus ion and gasi ica ion. Since he
Lowe Hea ing Value (LHV) o syngas is di ec ly in luenced by he
elemen al composi ion o ca bon and hyd ogen. Ca bon and hyd ogen
a e p ima y con ibu o s o he ene gy con en o he syngas, while
oxygen educes he LHV as i dilu es he combus ible elemen s. Whe e,
ca bon con ibu es o he ene gy densi y by oxidizing o CO and CO
2
du ing combus ion o gasi ica ion. The highe he ca bon con en in he
eeds ock, he g ea e he calo i ic alue o he p oduced syngas. While
Hyd ogen signi ican ly enhances LHV because o i s high calo i ic alue.
Hyd ogen- ich plas ics, o example, a e equen ly used as hyd ogen
dono s in co-gasi ica ion p ocesses o imp o e he ene gy yield o he
syngas. The LHV o syngas can be app oxima ed as:
LHV (MJ/kg) =10.8 ×X
H2
+12.6 ×X
CO
+3.5 ×X
CH4
Whe e “X” ep esen s he mole ac ions o hyd ogen, ca bon monoxide,
and me hane in he syngas. Since inc easing he hyd ogen ac ion en-
hances LHV due o i s high ene gy densi y. While ca bon con ibu es by
o ming CO and CH
4
, bo h o which inc ease he syngas’ hea ing alue.
Biomass gene ally con ains 35–50 % ca bon, while plas ics like poly-
e hylene and polyp opylene ha e a signi ican ly highe ola ile ma e
con en (o e 85 %) and e y low ash con en (less han 1 %), making
hem highly e ec i e con ibu o s o syngas hea ing alue. MSW com-
ponen s wi h a highe ca bon concen a ion, such as plas ics, con ibu e
subs an ially o syngas ene gy densi y,wh ee hyd ogen plays a c ucial
ole in de e mining he hea ing alue and composi ion o syngas. Was e
plas ics, wi h 7–15 % hyd ogen con en , ac as hyd ogen dono s in co-
gasi ica ion, inc easing hyd ogen yield and boos ing syngas calo i ic
alue. In co-gasi ica ion scena ios, hyd ogen- ich plas ics help balance
he H
2
/CO a io, making he syngas mo e sui able o downs eam ap-
plica ions like FTS. Oxygen , on he o he hand, a ec s he e iciency o
gasi ica ion eac ions by in luencing oxida ion p ocesses. Biomass
ypically con ains 40–50 % oxygen, which can lowe syngas hea ing
alue compa ed o plas ics, which ha e minimal oxygen con en . The
high oxygen con en in biomass leads o a lowe e ec i e hyd ogen- o-
ca bon a io compa ed o plas ics, impac ing syngas composi ion and
sui abili y o speci ic applica ions. Biomass, p ima ily composed o
cellulose (40–50 %), hemicellulose (15–30 %), and lignin (15–30 %),
exhibi s a ying ola ile ma e and ash con en , bo h o which in luence
i s calo i ic alue and con e sion e iciency [57,58]. Woody biomass
and nu shell-de i ed eeds ocks gene ally ha e highe ca bon and
hyd ogen con en , leading o imp o ed syngas quali y and enhanced
hyd ogen- o-ca bon a ios. This a o s he p oduc ion o a oma ic
hyd oca bon- ich liquid uels h ough py olysis. Cellulosic biomass has
70–90 % ola ile ma e , 10–20 % ixed ca bon, and a ying ash con-
en . He baceous biomass, in pa icula , has a highe ash con en , wi h
alkali and alkaline ea h me als in he ash ac ing as ca alys s du ing
py olysis. These mine als p omo e seconda y c acking o ola iles,
educing bio-oil yield while inc easing gas and cha p oduc ion [59].
Was e plas ics encompass a ious ypes wi h dis inc chemical s uc-
u es, including polye hylene (PE), polyp opylene (PP), polys y ene
(PS), poly inyl chlo ide (PVC), and polye hylene e eph hala e (PET).
Among hem, PE and PP a e he mos abundan , accoun ing o abou 50
% o global plas ic was e. These plas ics p ima ily consis o 80–93 %
ca bon and 7–15 % hyd ogen, wi h an e ec i e hyd ogen- o-ca bon
a io o 1–2, which is signi ican ly highe han biomass’s 0–0.3 a io.
Table 1
Composi ion and cha ac e is ics o lignocellulosic biomass, was e plas ics and ypical MSW.
Sample Lignocellulosic biomass
Ul ima e Analysis w % P oxima e Analysis w %
C H O N S Cl V FC A H/C
e
Q
HHV
/MJ⋅kg
−1
Woody biomass, pine wood 49.33 6.06 44.57 0.04 0.00 0.0 73.40 16.70 0.50 0.12 19.80
Woody biomass, i wood 49.07 6.70 44.18 0.02 0.03 0.0 81.93 17.75 0.32 0.29 20.29
Woody biomass, popla wood 47.21 6.04 46.74 0.01 0.00 0.0 87.95 10.93 1.12 0.05 18.58
He baceous biomass, whea s aw 38.34 5.47 55.22 0.60 0.37 0.0 83.08 10.29 6.63 −0.45 13.96
He baceous biomass, ice s aw 36.07 5.20 57.83 0.64 0.26 0.0 78.07 6.93 15.00 −0.67 12.53
F ui shell biomass, walnu shell 47.30 6.10 42.00 0.50 0.10 0.0 76.60 19.40 4.00 0.22 19.11
F ui shell biomass, palm ke nel shell 48.44 6.23 44.99 0.31 0.03 0.0 71.72 25.21 3.07 0.15 20.30
Plas ics Was e
Ul ima e Analysis w % P oxima e Analysis w %
Sample C H O N S Cl V FC A H/C
e
Q
HHV
/MJ⋅kg
−1
Polye hylene (PE) 85.50 14.5 0.00 0.00 0.00 0.0 99.96 0.04 0.00 2.04 46.01
Low densi y polye hylene (LDPE) 84.21 14.2 1.47 0.03 0.00 0.0 99.79 0.21 0.00 2.01 48.83
High densi y polye hylene (HDPE) 85.16 14.4 0.31 0.02 0.03 0.0 99.85 0.06 0.09 2.03 49.63
Linea low-densi y polye hylene (LLDPE) 85.61 14.2 0.02 0.05 0.03 0.0 99.85 0.07 0.05 2.00 46.17
Polys y ene (PS) 92.20 7.80 0.00 0.00 0.00 0.0 99.50 0.50 0.00 1.02 40.49
Polyp opylene (PP) 84.70 15.3 0.00 0.00 2.10 0.0 96.90 0.00 1.00 2.17 45.23
Polye hylene e eph hala e (PET) 64.10 3.70 34.20 0.00 0.00 0.0 84.10 13.90 0.00 −0.01 24.15
Poly inyl chlo ide (PVC) 38.70 4.80 0.00 0.00 0.00 56 95.80 4.20 0.00 1.49 19.30
Municipal Was e
Componen Mois u e Ul ima e Analysis LHV
W % C H O N S Ash MJ/Kg
Tex iles 10.0 48.0 6.4 40.0 2.2 0.2 3.2 17.08
Wood 1.3 49.6 6.0 42.6 0.2 0.1 1.5 18.28
Plas ics 1.2 60.0 7.2 22.8 0.0 0.0 10.0 29.0
Pape 10.2 43.4 5.8 44.3 0.3 0.2 6.0 13.43
Food Was e 70.0 48.0 6.4 37.6 2.6 0.4 5.0 3.90
No e: C ep esen s ca bon, H hyd ogen, O oxygen, N ni ogen, S sul u , Cl chlo ine, V ola ile, FC ixed ca bon, A o ash, and H/C
e
is hyd ogen- o-ca bon e ec i e
a io. Whe e he in o ma ion on ul ima e analysis, mois u e con en s and LHV a e acqui ed om e e ences [61–64].
M. Sai e al.
Biomass and Bioene gy 196 (2025) 107736
5
Howe e , some plas ics con ain speci ic elemen s ha impac hei
p ocessing. Fo example, PVC con ains 56.5 % chlo ine, which poses
en i onmen al conce ns, while PET con ains 34.2 % oxygen, in luencing
i s gasi ica ion beha io [60]. The e o e, he long pe sis ence o plas ics
in he en i onmen is a majo global conce n, pa icula ly in ma ine
ecosys ems, whe e plas ic pollu ion h ea ens biodi e si y. Conse-
quen ly, alo izing was e plas ics in o enewable ene gy sou ces is
essen ial o achie ing sus ainabili y. Since co-p ocessing plas ics wi h
biomass p esen s an e ec i e s a egy o mi iga e ope a ional challenges
ela ed o plas ic was e while enhancing syngas p oduc ion and o e all
p ocess e iciency. Whe e, he in eg a ion o ad anced cleaning and
condi ioning sys ems u he enhances he pu i y o syngas, making
biomass gasi ica ion a p omising and sus ainable app oach o mee ing
ene gy demands and educing eliance on ossil uels.
Zhao e al. explo ed he syne gis ic e ec s o co-py olysis and co-
gasi ica ion, e ealing dis inc gas composi ions. Fo co-py olysis, he
gases comp ised H
2
(32–38 %), CH
4
(14–15 %), and CO (29–30 %),
while co-gasi ica ion yielded H
2
(47 %), CH
4
(6–8%), and CO (26–31 %)
[66]. D´
epa ois e al. documen ed imp essi e syngas p oduc ion a es,
achie ing app oxima ely 3.6–4.8 g/min du ing co-py olysis and an
enhanced ou pu o 5.9–8.1 g/min o co-gasi ica ion [67]. Hyd ogen
p oduc ion a es eached app oxima ely 0.17–0.19 g/min o
co-py olysis and 0.09–0.13 g/min o co-gasi ica ion, wi h ene gy yields
o a ound 1.7–2.3 g/min and 1.6–2.4 g/min, espec i ely, showcasing
he e iciency o bo h p ocesses. Such as Block e al. [68] p o ided a
comp ehensi e e iew o co-py o gasi ica ion o biomass and plas ic
was e, ocusing on p oduc dis ibu ion, ope a ional condi ions, eed-
s ock cha ac e is ics, p ocess pa hways, and syne gis ic e ec s. Uzoe-
jinwa e al. [69] emphasized he ad an ages o co-py olysis, pa icula ly
i s enhanced ope a ional con ol mechanisms and imp o ed p oduc
yield. Wong e al. [37] del ed in o he echnical in icacies o con e ing
plas ics in o uel ia he mal and ca aly ic py olysis, while also
explo ing he co-py olysis o biomass and plas ic was e, highligh ing i s
po en ial o sus ainable uel p oduc ion. Inaya e al. [70] in es iga ed
he in luence o ca aly ic co-gasi ica ion on enhancing syngas pe o -
mance and quali y de i ed om a ious blended uel sou ces, high-
ligh ing i s ole in op imizing ene gy ou pu s. Mish a e al. [51] and
Ramos e al. [71] examined he bene icial impac o solid was e
co-gasi ica ion on inal p oduc yields, wi h a ocus on he la es ad-
ancemen s in gasi ica ion and co-gasi ica ion echnologies o e icien
was e- o-ene gy con e sion. B achi e al. emphasize ha combining
plas ics wi h biomass e ec i ely mi iga es he challenges and ope a-
ional issues associa ed wi h using plas ic eeds ock alone [72]. They
u he highligh ha co-gasi ying biomass and PET esul s in a p oduc
gas composi ion ha elimina es he need o addi ional condi ioning in a
wa e -gas shi eac o o me hanol p oduc ion, s eamlining he p o-
cess. Robinson e al. ad oca e o he co-gasi ica ion o plas ic was e,
such as ood con aine s and plas ic bo les, wi h biomass as an e ec i e
solu ion o di e was e om land ills, pa icula ly in small and emo e
communi ies [73]. These s udies sugges ha each echnique has i s
s eng hs and weaknesses, making i challenging o de ini i ely choose
he mo e e icien me hod. Howe e , i is c ucial o e alua e he ad-
an ages o bo h echniques (co-py olysis and co-gasi ica ion) o de e -
mine he mos e ec i e me hod ha would simul aneously deal wi h all
he associa ed p oblems while e alua ing he e iciency o hese
echniques.
One o he main challenges in co-p ocessing is ob aining and sepa-
a ing was e plas ics in o pu e componen s due o inadequa e in a-
s uc u e and eliance on manual so ing, consequen ly, plas ic was e is
o en mixed wi h o he ma e ials. De eloping co-py olysis can mode a e
he need o ex ensi e was e sepa a ion and alle ia e ope a ional issues
associa ed wi h pu e plas ic was e con e sion, majo ly p oducing bio-oil
and biocha along wi h some ac ion o syngas. Co-gasi ica ion, how-
e e , has ga ne ed in e es due o i s po en ial o eplace ossil-based
uels wi h pa icula ly hyd ogen- ich syngas, o e ing en i onmen al
bene i s and enhanced syngas quali y. Since i is usually ega ded ha
he py olysis o biomass and plas ics enhances he hyd ogen con en and
calo i ic alue o bio-oil, he syngas ypically con ains mo e impu i ies
and has lowe hyd ogen con en compa ed o gasi ica ion. Fo pack-
aging was e ha is challenging o sepa a e om ma e ials like ca d-
boa d, pape , o wood, co-gasi ica ion o e s a p ac ical solu ion. I
becomes especially appealing o mixed was e p ocessing by minimizing
he need o ex ensi e was e sepa a ion [74]. The eac ions in ol ed in
single eeds ock gasi ica ion a e simila o hose in co-gasi ica ion;
howe e , co-gasi ying biomass and plas ic was e boos s bo h he quan-
i y and composi ion o syngas, pa icula ly inc easing H
2
le els [68].
Fig. 3. Chemical composi ion o solid was e con aining polyole in (e.g., PE and PP), polyes e (e.g., PLA and PET), polye he , polyamide, p o ein, lipid, and
lignocellulose (i.e., cellulose, hemicellulose, and lignin), ep in ed wi h he pe mission o e . [65]. Copy igh 2023 Royal Socie y o Chemis y.
M. Sai e al.
Biomass and Bioene gy 196 (2025) 107736
6
The wa e -gas shi (WGS) eac ion and s eam me hane e o ming (SMR)
a e highly e ec i e in gene a ing hyd ogen- ich s eams, while c acking
eac ions u he con ibu e by b eaking down hea y hyd oca bons in o
ligh e molecules, unlocking hyd ogen om a . Simila ly, when used as
a gasi ica ion agen , wa e gene a es ee adicals du ing he e o ming
s age. These adicals a e abso bed by he ca alys , p omo ing he
b eakdown o a in o hyd ogen (H
2
) and ca bon monoxide . Chai e al.
[75] ound ha gas p oduc ion, including H
2
, ini ially inc eases wi h he
plas ic pe cen age in he eeds ock bu declines a e a ce ain concen-
a ion, sugges ing a limi o he syne gis ic e ec be ween plas ics and
biomass. Plas ics p o ide H adicals ha p omo e H
2
p oduc ion and
in e ac wi h biomass adicals o b eak down complex hyd oca bons
in o CO and ligh e hyd oca bons. Inco po a ing H
2
O in o he p ocess
boos s gas p oduc ion by eac ing wi h CO and ligh e hyd oca bons,
inc easing hyd ogen yield. While, a biomass- o-plas ics a io o 7:3, wi h
plas ic con en kep below 30 % in he eed, is ecommended o op imal
esul s [75]. The esul ing syngas holds immense e sa ili y, se ing
applica ions such as elec ici y gene a ion, chemicals, H
2
p oduc ion,
FTS/MTS liquid uels, and dime hyl e he (DME) syn hesis [76]. How-
e e , u he esea ch is essen ial o op imizing and unlocking hese
p ocesses o sus ainable ene gy solu ions h ough ad anced was e
managemen pla o ms. A schema ic diag am o biomass and plas ic
was e co-gasi ica ion o p oduce syngas is shown in Fig. 4, illus a ing
he in eg a ed co-py olysis and co-gasi ica ion p ocess o con e ing
plas ic and biomass was e in o aluable ene gy p oduc s. Whe e, he
co-py olysis pa hway, conduc ed a 700 ◦C wi h a Ni-La/Al
2
O
3
-CaO-C
ca alys unde a ni ogen low o 100 ml/min, p oduces in e media e
p oduc s such as gas, bio-oil, and cha . These in e media es unde go
u he ca aly ic ea men s, including e o ming, hyd odeoxygena ion,
and ca aly ic e o ming, o gene a e hyd ogen, ligh ole ins (BTX),
gasoline, and diesel. Simul aneously, co-gasi ica ion a 800 ◦C, acili-
a ed by a CaO ca alys and a s eam- o- eed a io o 0.75, yields syngas
en iched in hyd ogen (up o 70 ol%) which unde goes ca aly ic syn-
hesis and wa e gas shi eac ions o p oduce me hanol, uels, and
addi ional hyd ogen. This in eg a ed app oach op imizes hyd ogen
p oduc ion (up o 55.45 ol% om py olysis) while enhancing o e all
p ocess e iciency and educing plas ic was e impac .
3.2. Co-gasi ica ion ope a ing pa ame e s
As discussed be o e, he gasi ica ion p ocess un olds h ough ou
essen ial s ages: d ying, py olysis, oxida ion, and educ ion, whe e hese
s ages encompass key mechanisms such as e o ming and c acking e-
ac ions in he gaseous phase, along wi h he gasi ica ion o he e oge-
neous cha . In he ini ial d ying s age, eeds ock is subjec ed o
empe a u es be ween 100 ◦C and 200 ◦C, esul ing in mois u e emo al
while main aining he chemical composi ion o he ma e ial la gely
unchanged. Following he d ying p ocess, he subsequen ini ial py ol-
ysis o de ola iliza ion in ol es he he mal decomposi ion o biomass,
yielding h ee p ima y componen s: solid esidue, condensable liquids
( a s), and non-condensable gases. These p oduc s can u he be clas-
si ied in o ola ile ma e (gases and liquids) and cha , which a e
exposed o ai du ing oxida ion. The deg ee o oxida ion depends on he
ai - o-solid eed a io which dic a es whe he pa ial o comple e
Fig. 4. Flow Diag am o he Co Gasi ica ion Biomass and plas ic was e. Rep oduced wi h he pe mission o e . [77]. Copy igh 2023 Else ie .
M. Sai e al.
Biomass and Bioene gy 196 (2025) 107736
7
oxida ion eac ions occu . This s age is c i ical o he gasi ica ion p o-
cess, as i de e mines he composi ion o he esul ing p oduc s and in-
luences he subsequen eac ions wi hin he sys em [77]. While, he
inal s ages o he gasi ica ion p ocess, educ ion/gasi ica ion eac ions,
a e he slowes ye c i ical s eps in he sys em. Key ac o s such as
gasi ica ion agen s, empe a u e, p essu e, ca alys o bed ma e ials, and
esidence ime play a pi o al ole in de e mining p oduce gas yield, gas
quali y, a o ma ion, and o e all ca bon con e sion e iciency [68,78].
Since, unde s anding hese pa ame e s is essen ial o op imizing gasi-
ica ion e iciency and examining he in e ac ions be ween biomass and
he moplas ics.
Reac ion Tempe a u e: The gasi ica ion empe a u e is a c i ical
and highly in luen ial ac o in he co-gasi ica ion p ocess o biomass
and plas ic was e. I signi ican ly impac s he yield and composi ion o
syngas by in luencing chemical eac ions and hei equilib ia. In he e,
empe a u e plays a c ucial ole in co-gasi ica ion, as highe empe a-
u es p omo e he b eakdown o complex polyme s ound in bo h
biomass and plas ics. Inc eased empe a u es a o endo he mic e-
ac ions, leading o he o ma ion o hyd ogen and ca bon monoxide
while educing a o ma ion. Howe e , excessi ely high empe a u es
may cause equipmen deg ada ion and excessi e ca bon deposi ion.
Gene ally, s eam gasi ica ion ope a es e icien ly be ween 800 and
1000 ◦C, oxygen gasi ica ion a 900–1200 ◦C, and CO
2
gasi ica ion a
750–950 ◦C. Choosing he igh empe a u e ange is essen ial o
maximizing syngas p oduc ion and a oiding ope a ional challenges.
Highe empe a u es a o endo he mic eac ions, inc easing gas yield
due o enhanced py olysis, c acking, gasi ica ion, and s eam e o ming
p ocesses [79]. Lahijani e al. [80] demons a ed ha in an ai -blown
luidized bed o wo wood was e ypes, inc easing he empe a u e
om 650 o 1050 ◦C inc eased syngas yield om 1.36 o 2.10 Nm
3
/kg
and om 1.28 o 1.95 Nm
3
/kg, espec i ely [81]. These indings un-
de sco e he impo ance o empe a u e op imiza ion o maximizing
syngas p oduc ion. Mo eo e , highe gasi ica ion empe a u es educe
a con en and imp o e ca bon con e sion e iciency. This is pa icu-
la ly c i ical o biomass and plas ic was e, whe e a o ma ion can
hinde p ocess e iciency and downs eam applica ions. Fo example,
highe empe a u es enhance s eam e o ming and WGS eac ions,
inc easing H
2
con en while dec easing CH
4
con en . Gonz´
alez e al. [82]
obse ed inc eased H
2
and CO concen a ions wi h dec eased CH
4
and
CO
2
concen a ions when he empe a u e was aised om 700 o 900 ◦C
du ing ai gasi ica ion. The CO/CO
2
a io inc eased om 0.85 o 2.7,
indica ing a no able imp o emen in syngas quali y. A empe a u es
abo e 750–800 ◦C, WGS and he s eam e o ming eac ions become
mo e p onounced, con ibu ing o highe H
2
p oduc ion. While a
u he highe empe a u es (abo e 850–900 ◦C), he Boudoua d eac-
ion inc eases CO con en [83]. He n´
andez e al. [84] compa ed
di e en gasi ying agen s and ound ha ai gasi ica ion p ima ily
boos s CO and H
2
concen a ions h ough he Boudoua d and s eam
e o ming eac ions. The Boudoua d eac ion (2CO → C +CO
2
) is a key
equilib ium in syngas chemis y, in luencing ca alys s abili y, coke
o ma ion, and o e all p ocess e iciency in biomass-de i ed a oma ic
hyd oca bon syn hesis. This eac ion is pa icula ly ele an in
co-gasi ica ion and andem ca aly ic pa hways whe e syngas is used as
eeds ock. Recen s udies ha e highligh ed he impac o he Boudoua d
eac ion on he e iciency and longe i y o ca alys s used in biomass and
plas ic was e co-gasi ica ion. The in e play be ween gasi ica ion em-
pe a u e, syngas composi ion, and ca alys p ope ies de e mines he
ex en o ca bon deposi ion and i s subsequen emo al.
Du ing biomass and plas ic was e co-gasi ica ion, he eac ion con-
di ions ( empe a u e, p essu e, and gas composi ion) de e mine whe he
he Boudoua d eac ion a o s ca bon deposi ion o ca bon emo al. A
empe a u es below 700 ◦C, he eac ion ends o o m solid ca bon
(coke), leading o ca alys deac i a ion. In con as , a highe empe a-
u es (>900 ◦C), CO o ma ion is a o ed, educing ca bon buildup.
Ca bon o ma ion om he Boudoua d eac ion can block ac i e si es o
me al/zeoli e ca alys s, dec easing eac ion e iciency. The eac ion
equilib ium can shi depending on CO concen a ion, impac ing
downs eam eac ions such as FTS o me hanol- o-a oma ics con e sion.
A mode a e empe a u es (700–900 ◦C), ca bon deposi ion ia he
Boudoua d eac ion is signi ican , leading o ca alys ouling and eac o
clogging. S udies ha e shown ha inc easing he empe a u e beyond
900 ◦C shi s he equilib ium owa ds CO o ma ion, he eby educing
ca bon buildup. Highe p essu es end o a o solid ca bon o ma ion,
exace ba ing ca alys deac i a ion. Howe e , in oducing CO as a co-
eac an can coun e ac his by p omo ing ca bon gasi ica ion. CO- ich
syngas enhances ca bon deposi ion, necessi a ing he use o ca alys s
wi h highe coke esis ance. Gasi ie ype also plays a ole: luidized-bed
eac o s end o ha e lowe ca bon buildup due o be e mixing, while
ixed-bed eac o s may expe ience localized ca bon deposi s ha hinde
pe o mance.
In con as , mixed s eam/ai gasi ica ion, wi h a signi ican p opo -
ion o s eam (56.4 ol%), p ima ily enhances H
2
p oduc ion ia cha -
s eam e o ming and he WGS eac ion, al hough i also inc eases CH
4
con en . While inc easing gasi ica ion empe a u e gene ally imp o es
syngas quali y by aising CO and H
2
concen a ions, which a e essen ial
o he LHV o syngas and i s sui abili y o a ious applica ions he e a e
limi a ions. Excessi ely high empe a u es can lead o educed ene gy
e iciency and ope a ional challenges, such as ash sin e ing and
agglome a ion [81,85]. These issues highligh he need o a balanced
app oach in selec ing he op imal gasi ica ion empe a u e. Since he
gasi ica ion empe a u e plays a pi o al ole in de e mining he e i-
ciency and quali y o syngas p oduc ion in he co-gasi ica ion o biomass
and plas ic was e. A ho ough unde s anding o he empe a u e’s e ec s
on chemical eac ions, syngas composi ion, and ope a ional cons ain s
is essen ial o op imizing he p ocess and ensu ing i s sus ainabili y.
The Boudoua d eac ion acili a es he con e sion o CO
2
gene a ed
du ing gasi ica ion back in o CO, which is a aluable componen o
syngas, hus imp o ing o e all e iciency (Kaydouh & Hassan, 2022).
The Boudoua d eac ion is in eg al o p ocess modeling and op imiza-
ion e o s, as i a ec s he he modynamic equilib ium and he o e all
pe o mance o he gasi ie (Aen ung e al., 2024) (Kaydouh & Hassan,
2022). Mul i-objec i e op imiza ion echniques, such as gene ic algo-
i hms, conside he Boudoua d eac ion’s impac o achie e op imal
gasi ica ion condi ions and maximize syngas p oduc ion (Aen ung e al.,
2024). While he Boudoua d eac ion is bene icial in enhancing syngas
quali y and gasi ica ion e iciency, i is impo an o conside he po-
en ial challenges i may pose, such as he need o p ecise con ol o
eac ion condi ions o p e en undesi able by-p oduc s. Addi ionally,
he choice o gasi ying agen s and eeds ock composi ion can signi i-
can ly in luence he eac ion’s e ec i eness, necessi a ing ca e ul op i-
miza ion o achie e he desi ed ou comes in co-gasi ica ion p ocesses.
Gasi ying Agen s and Feeds ock Composi ion: The choice o
gasi ying agen plays a pi o al ole in de e mining he e iciency, eac-
ion pa hways, syngas composi ion, en i onmen al impac , and eco-
nomic iabili y o he co-gasi ica ion p ocess, pa icula ly when
add essing biomass and plas ic was es. Recen s udies ha e del ed in o
he in luence o gasi ying agen s on syngas yield, hea ing alues, and gas
composi ions, p o iding aluable insigh s o op imizing hese p ocesses
[86]. Whe e, di e en gasi ying agen s (include ai , s eam, oxygen, and
hei mix u es wi h ai ) a e adop ed o imp o ing he p oduce gas
yield and quali y o he mos economical choices [87]. S eam (H
2
O) is
commonly used o enhance hyd ogen p oduc ion h ough s eam
e o ming and he wa e -gas shi eac ion, leading o hyd ogen- ich
syngas. Oxygen (O
2
), on he o he hand, suppo s pa ial oxida ion e-
ac ions, p o iding addi ional ene gy o d i e endo he mic gasi ica ion
eac ions. Ca bon dioxide plays a unique ole in p omo ing he Bou-
doua d eac ion (C +CO
2
→ 2CO), which enhances CO o ma ion. The
choice and combina ion o gasi ying agen s de e mine he balance be-
ween hyd ogen, ca bon monoxide, and ca bon dioxide in he inal
syngas p oduc . U ilizing CO
2
as a gasi ying agen can enhance ca bon
con e sion a es, especially when combined wi h s eam, which is shown
o be he mos e ec i e gasi ying agen (Kaydouh & Hassan, 2022). The
M. Sai e al.
Biomass and Bioene gy 196 (2025) 107736
8
in eg a ion o he Boudoua d eac ion in co-gasi ica ion p ocesses can
lead o a mo e sus ainable was e managemen app oach by educing
g eenhouse gas emissions and imp o ing he quali y o he p oduced
syngas ("Co-gasi ica ion o Was e Biomass and Plas ic o Syngas P o-
duc ion wi h CO
2
Cap u e and U iliza ion: The modynamic In es iga-
ion," 2023) (Dai e al., 2021). While he Boudoua d eac ion o e s
signi ican ad an ages in co-gasi ica ion, challenges emain, such as he
need o e icien ca alys s and op imized p ocess condi ions o maxi-
mize CO
2
con e sion a es and syngas quali y.
While a ious ypes o gasi ie s a e also u ilized depending on he
gasi ying agen , such as oxygen-blown, ai -blown, and s eam gasi ie s
[88–90]. Ai -blown gasi ie s, o ins ance, a e a common choice due o
hei simplici y and cos -e ec i eness. Howe e , he esul ing syngas
ypically has a low hea ing alue (3.5–7 MJ/m
3
) because o ni ogen
dilu ion, which also educes hyd ogen con en . Despi e i s limi a ions,
ai -blown gasi ica ion emains sui able o ce ain applica ions, pa ic-
ula ly whe e he cos cons ain s ou weigh he need o high-quali y
syngas [81,91]. On he o he hand, s eam gasi ica ion o e s signi i-
can ad an ages by p oducing syngas wi h a highe hea ing alue
(11–20 MJ/m
3
) and a g ea e hyd ogen con en , la gely a ibu ed o he
s eam e o ming eac ions ha enhance H
2
p oduc ion [87,92]. The
addi ion o s eam o ai -blown sys ems u he inc eases H
2
and CH
4
concen a ions in he syngas, bu s eam also necessi a es highe ene gy
inpu due o he endo he mic na u e o he eac ions, which can educe
he o e all empe a u e. While, he s eam- o-biomass a io (SBR) is a
c i ical pa ame e in s eam gasi ica ion, wi h op imal SBR alues
anging om 0.3 o 1.0 shown o imp o e hyd ogen p oduc ion, educe
a o ma ion, and enhance ca bon con e sion e iciency and cold gas
e iciency [71]. While, highe SBR alues (1.35–4.04), as no ed by
Pindo ia e al. [93], boos H
2
and CO
2
p oduc ion while educing he
concen a ions o hyd oca bons such as C
2
H
2
, CH
4
, and CO, sugges ing
ha s eam- ich en i onmen s a o hyd ogen p oduc ion and a
educ ion bu may lowe he calo i ic alue due o he inc eased p o-
duc ion o CO
2
. Excessi e un eac ed s eam, howe e , can lead o he -
mal ine iciencies and educed syngas quali y. While, oxygen-blown
gasi ie s elimina e ni ogen dilu ion, esul ing in syngas wi h highe
hea ing alues and a cleane composi ion, hough he highe cos o pu e
oxygen and he ele a ed ac i a ion ene gies associa ed wi h i s use can
limi i s applicabili y [84]. S udies ha e demons a ed ha inc easing
oxygen concen a ion enhances eac ion a es and ac i a ion ene gies,
al e ing he dis ibu ion and composi ion o he ou pu s. Fo example,
Guo e al. [94] obse ed ha highe oxygen le els educe H
2
ac i a ion
ene gy, al hough oxygen-based sys ems gene ally exhibi highe ac i-
a ion ene gies compa ed o ine en i onmen s. Combining s eam and
ai in op imal p opo ions o e s a balanced app oach o imp o ing gas
quali y and uel con e sion while minimizing ene gy equi emen s [95].
Howe e , he selec ion and op imiza ion o gasi ying agen s a e c i ical
o achie ing e icien co-gasi ica ion o biomass and plas ic was es.
Balancing ene gy inpu s is also essen ial, as he endo he mic na u e o
s eam gasi ica ion demands ca e ul ene gy managemen o main ain
sys em e iciency while maximizing syngas quali y. Tailo ing gasi ie
designs o align wi h speci ic eeds ock composi ions and desi ed syngas
cha ac e is ics, and adjus ing ope a ing pa ame e s such as empe a u e,
p essu e, esidence ime, and ca alys o bed ma e ial, a e equally
impo an o enhancing ca bon con e sion e iciency, educing a
o ma ion, and imp o ing syngas yield. While signi ican p og ess has
been made in unde s anding he ole o gasi ying agen s, u he
esea ch is needed o op imize he s eam- o-ai a ios o a ious eed-
s ock combina ions, de elop cos -e ec i e me hods o in eg a ing pu e
oxygen wi hou p ohibi i e expenses, enhance gasi ie designs o
accommoda e di e se eeds ocks including challenging plas ic was es,
and ad ance ca alys echnologies o imp o e eac ion a es and syngas
quali y. By add essing hese challenges, he co-gasi ica ion p ocess can
become a mo e iable and sus ainable solu ion o managing biomass
and plas ic was es while p oducing aluable syngas o ene gy and
chemical applica ions. Feeds ock composi ion is ano he c i ical ac o
in co-gasi ica ion. The biomass- o-plas ic a io di ec ly a ec s syngas
composi ion and o e all p ocess e iciency. As discussed be o e, plas ics,
being hyd oca bon- ich, con ibu e o highe concen a ions o
hyd ogen and ca bon monoxide, leading o a syngas wi h a highe
hea ing alue. In con as , biomass con ains oxygena ed compounds,
which can esul in inc eased CO
2
and H
2
O p oduc ion. An op imal
blend o biomass and plas ic can le e age syne gis ic e ec s, imp o ing
o e all gasi ica ion e iciency while mi iga ing issues like excessi e a
o ma ion and ca bon deposi ion. The p esence o plas ics, such as
low-densi y polye hylene (LDPE) and polyp opylene, in he eeds ock,
enhances he Boudoua d eac ion, leading o imp o ed syngas quali y
and highe hea ing alues (Ishak e al., 2024) (Kaydouh & Hassan,
2022). The eac ion aids in inc easing he ca bon con e sion e iciency
(CCE) and cold gas e iciency (CGE) o he co-gasi ica ion p ocess, as i
acili a es he con e sion o ca bon- ich ma e ials in o gaseous p oduc s
(Aen ung e al., 2024) (Kaydouh & Hassan, 2022). Op imizing he
plas ic- o-biomass a io and gasi ying agen s, such as s eam, can u he
enhance he e iciency o he Boudoua d eac ion, leading o be e gas
yields and ene gy eco e y (Reguei o, 2022) (Kaydouh & Hassan, 2022).
Reac ion P essu e: The eac ion p essu e plays a signi ican ole in
he co-gasi ica ion o plas ic was e and biomass, di ec ly in luencing he
syngas composi ion and he highe hea ing alue (HHV) o he p oduc
gas [96]. Recen s udies ha e p o ided insigh s in o how a ia ions in
gasi ica ion p essu e a ec he concen a ions o key syngas compo-
nen s, including hyd ogen (H
2
), ca bon monoxide , ca bon dioxide , and
me hane (CH
4
) [97,98]. A comp ehensi e e alua ion o biomass gasi-
ica ion and i s downs eam ope a ions sugges s ha highe gasi ica ion
p essu es can enhance he o e all e iciency o he p ocess. Howe e , he
speci ic e ec s on syngas composi ion depend on a ious ac o s,
including he ype o biomass used and he gasi ica ion echnology
employed. Di e en s udies highligh he s ong dependence o syngas
composi ion on biomass condi ions, ype o gasi ie , and ope a ing pa-
ame e s such as p essu e and empe a u e, indica ing ha e en wi h he
same ype o biomass and gasi ie , a ia ions in p essu e can lead o
signi ican disc epancies in he inal syngas composi ion [99]. Ele a ed
p essu es can al e he equilib ium o gasi ica ion eac ions, po en ially
a ec ing he concen a ions o H
2
and CO in he syngas. Fo ins ance, in
ce ain gasi ica ion scena ios, inc easing he p essu e om a mosphe ic
le els o highe alues has been obse ed o in luence he H
2
/CO a io,
which is c i ical o downs eam applica ions like FTS. Highe p essu es
end o a o he o ma ion o me hane and o he highe hyd oca bons
due o enhanced me hana ion eac ions. This can lead o an inc ease in
he calo i ic alue o he syngas bu may equi e addi ional p ocessing
s eps o adjus he syngas composi ion o speci ic applica ions. While
speci ic nume ical da a can a y depending on he eeds ock and gasi-
ica ion echnology used, s udies ha e shown ha : Inc easing he p es-
su e om 1 a m (a m) o app oxima ely 1.75 a m can lead o an op imal
balance be ween syngas yield and cold gas e iciency (CGE). A his
p essu e, a syngas yield o a ound 58 % has been epo ed, wi h a CGE
nea 80 %. Howe e , u he inc eases in p essu e may esul in
diminishing e u ns o e en nega i e e ec s on syngas quali y. In sum-
ma y, while inc easing gasi ica ion p essu e can imp o e syngas yield
and modi y i s composi ion, he speci ic ou comes a e in luenced by a
combina ion o ac o s, including biomass ype, gasi ie design, and
o he ope a ing condi ions. The e o e, op imizing gasi ica ion p essu e
equi es a comp ehensi e unde s anding o hese in e ela ed pa ame-
e s o achie e he desi ed syngas quali y and yield.
Maninde ji e al. [100] demons a ed ha inc easing eac ion
p essu e leads o a educ ion in he amoun s o hyd ogen and ca bon
monoxide in syngas. I was u he in e p e ed ha he e ec o p essu e
on syngas composi ion, he H
2
/CO a io, and he highe hea ing alue
(HHV) o he p oduc gas was signi ican in biomass-polyme co-gasi i-
ca ion. This phenomenon occu s because highe p essu e condi ions
a o eac ions ha p oduce ewe gas moles. Speci ically, ele a ed
p essu es p omo e me hana ion eac ions, which con e CO and H
2
in o
me hane, while inhibi ing s eam me hane e o ming, which p oduces H
2
M. Sai e al.
Biomass and Bioene gy 196 (2025) 107736
9
and ac i i y is key o imp o ing CO
2
hyd ogena ion o me hanol. A
ecen s udy explo es he e ec o di e en syn hesis condi ions on he
s uc u e and pe o mance o ZnZ O
x
ca alys s (Fig. 7) [157]. The igu e
illus a es a sys ema ic app oach o syn hesizing ZnZ O
x
ca alys s wi h
unable p ope ies by a ying key syn hesis pa ame e s such as d ying
me hods, calcina ion empe a u es, and addi i e inco po a ion. S a ing
wi h cop ecipi a ion, ca alys s a e subjec ed o di e en d ying ech-
niques, including eeze-d ying (c yogel), he mal d ying (xe ogel), and
sol en exchange (ambigel), each in luencing po osi y and s uc u al
cha ac e is ics. Addi ionally, calcina ion empe a u es (450–600 ◦C) a e
adjus ed o modi y he ca aly ic pe o mance. Fu he uning is achie ed
h ough pos -syn hesis ball-milling, con olling ca alys mo phology o
applica ions equi ing ine powde s. To enhance po osi y, PVA-assis ed
cop ecipi a ion and a ha d- empla ing me hod using ca bon black a e
employed, leading o ca alys s wi h unique ex u al p ope ies. This
di e se syn hesis s a egy allows p ecise con ol o e ca alys s uc u e
and pe o mance, op imizing ZnZ O
x
o applica ions such as me hanol
syn hesis and CO
2
con e sion. I has been demons a ed ha by
adjus ing ac o s like d ying me hods, calcina ion empe a u e,
ball-milling ime, and addi i es, hey de eloped ca alys s wi h a ied
su ace a eas (4.5–106 m
2
/g) and oxygen con en [O/(Zn +Z ) =
1.60–2.04]. The indings e eal ha MTS is s uc u e-sensi i e, wi h
oxygen- ich su aces c ucial o H
2
ac i a ion, he a e-limi ing s ep.
Ca alys s wi h high su ace oxygen con en showed enhanced ac i i y,
making oxygen- ich su aces he p ima y ac i e si es o CO
2
hyd oge-
na ion, highligh ing he o e looked impo ance o su ace oxygen in
ca aly ic pe o mance and sugges ing ha designing oxygen- ich ZnZ O
x
ca alys s wi h high su ace a eas can signi ican ly boos me hanol p o-
duc ion, o e ing a new pa hway o ca alys de elopmen . On he o he
hand, when a mix u e o MTS ca alys (usually Cu o Zn based) and
a oma iza ion ca alys (Zeoli e usually HZSM-5) is employed o syn-
hesize a oma ic hyd oca bons, wi h me hanol as an in e media e
p oduc . Whe e he design and de elopmen o ca alys s wi h high
selec i i y, excep ional ac i i y, and ou s anding s abili y a e c i ical o
ad ancing syn hesis gas o me hanol echnology. Usually, he
coppe -based ca alys s mixed wi h MoCoK-ZSM-5 and MoNiK-ZSM-5
illus a ed ha he composi e ca alys has highe eac ion ac i i y, he
CO con e sion a e has inc eased om 25 % o 90 %, whe e he highe
eac ion empe a u e was conduci e o he o ma ion o a oma ics and
he ca aly ic e ec s o composi e ca alys s [160]. O he ca alys s include
Zn, Z , Co, and Mo-based ca alys s, e c. [161–165], can be combined
wi h HZSM-5 o a highe a oma ics selec i i y in he liquid phase
p oduc , and a good ca alys s abili y. Mos amous bi unc ional ca alys
by Wang Ye’s g oup combining ZnO-Z O
2
ae ogel and zeoli e H-ZSM-5
o e s a b eak h ough in CO
2
hyd ogena ion, con e ing CO
2
o a o-
ma ics wi h 76 % selec i i y and minimal CH
4
o ma ion (<1 %) [166].
Despi e CO
2
’s ine na u e and he high ene gy ba ie o C-C coupling,
his ca alys achie es 16 % CO
2
con e sion and a high space- ime yield
o 0.24 g goxide
−1
h
−1
a 340 ◦C and 40 ba , ou pe o ming con en ional
Fische -T opsch sys ems. The key o i s success lies in he ZnO-Z O
2
ae ogel’s la ge su ace a ea and oxygen acancies, making i highly
e icien in me hanol o ma ion. Simila ly, in ano he s udy hey e-
po ed o achie e a g ea p omise o comme cial CO
2
- o-chemical
con e sion applica ions wi h a CO con e sion a e o 20 %, while
main aining a s able pe o mance o 1000h wi hou signi ican d op in
ac i i y unde indus ial condi ions [25]. In ano he s udy o a highly
dispe sed ZnZ me al oxide ca alys syn hesized by Xu e al. o CO
2
hyd ogena ion o me hanol [167], e ealed ha he o de ed s uc u e o
ZnZ O
x
solid solu ion could keep he high me hanol selec i i y. Whe e i
was u he demons a ed ha he s a egy can also be applied o Pd o
P doping o ZnZ O
x
by hyd ogen spillo e echnique. A small amoun o
ca alys s can ca y ou he ca aly ic eac ion, which is economical and
en i onmen ally iendly, and can be e icien ly indus ialized. A salan
e al. p epa ed nano ZnC
2
O
4
o he syn hesis gas o a oma ics, whe e
he a oma ics selec i i y eached 70 % a 250
o
C by op imizing he
s uc u e and pa icle size o he ca alys and p e en ing he
o e sa u a ion o ca bon pool species [168]. Mohan y e al. [169]
in es iga ed he ca aly ic ac i i y o ZnCoC -ZSM-5 o he syn hesis o
a oma ics om syngas, and he in luence o p ocess condi ions on he
eac ion esul s was s udied, including eac ion empe a u e, eac ion
p essu e, space eloci y and eed gas a io. The esul s showed ha
unde he condi ions o 275
o
C and 3.8 MPa, he CO con e sion a e
eached he highes (72 %), wi h he highes a oma ic selec i i y.
Inc easing empe a u e and p essu e is conduci e o he con e sion o
CO, while lowe H
2
/CO mole a io is conduci e o he o ma ion o a -
oma ics. A wide a ie y o MTS ca alys s combined wi h HZSM-5 ha e
been ex ensi ely s udied o syn hesizing a oma ics om syngas,
demons a ing high selec i i y o a oma ics. Howe e , hese ca alys s
o en exhibi lowe con e sion a es and p oduce signi ican amoun s o
byp oduc s [26,165,170–186].
4.3. FTS ou e
FT syn hesis is a he e ogeneous ca aly ic hyd ogena ion p ocess wi h
ca bon monoxide (adop ed om coal, na u al gas, biomass, and o he
ca bon- ich sou ces) o p oduce a di e se ange o aluable liquid uels
and pe ochemical eeds ocks h ough a non-selec i e polyme iza ion
eac ion [187]. These p oduc s o m a mix u e encompassing linea al-
kanes, alkenes, alcohols, aldehydes, ke ones, ca boxylic acids, and
wa e . Whe e, he p ima y a ge p oduc s o FT syn hesis a e ole ins
and pa a ins, which a e c ucial componen s o p oduce anspo a ion
uels such as diesel and gasoline, as well as a ious pe ochemical de-
i a i es [153,188–194]. While, ecen e o s ocus on scaling
biomass- o-liquid (BTL) echnologies using FT syn hesis o p oduce
sus ainable liquid uels, including bio uels and sus ainable a ia ion uel
(SAF) [195]. Since i s incep ion in 1923, FTS has been go e ned by h ee
p ima y eac ion pa hways: pa a in o ma ion, ole in o ma ion, and
he WGS eac ion [196,197]. Two main mechanisms unde pin FTS: he
ca bide mechanism and he CO-inse ion mechanism (Fig. 8). In he
ca bide mechanism, me al ca bides eac wi h H
2
o o m CH
2
* species,
which ac as chain g ow h monome s [198]. Chain e mina ion p o-
duces ole ins, pa a ins, and oxygena es. Va ia ions o his mechanism
p opose al e na i e in e media es, such as C* and CH*, o sugges
g owing chains like alkylidynes (RC*) ins ead o alkyls (RCH
2
*)
[199–201]. Con e sely, he CO-inse ion mechanism in ol es CO ac ing
as a monome , inse ing in o he g owing chain be o e hyd ogena ion
and C–O bond clea age. This mechanism eadily explains oxygena e
o ma ion. The p ima y di e ence be ween he wo lies in he sequence
o bond o ma ion: in CO inse ion, he C–C bond o ms i s , whe eas in
he ca bide pa hway, he C-O bond clea es i s . The CO-inse ion
mechanism, inspi ed by homogeneous ca alysis, was ini ially p oposed
by Pichle and Schulz and la e suppo ed by Schweiche ’s e al. [202],
expe imen s and Zhuo’s e al. [203] heo e ical s udies. On cobal ca -
alys s, such as Co(111) and Co(0001), he ene gy ba ie o CO inse -
ion is lowe han o di ec CO dissocia ion [202,204,205]. Ano he
p oposed pa hway, he hyd oxyca bene mechanism, in ol es he poly-
me iza ion o HCOH* wi h a g owing RCOH* chain, hough expe i-
men al suppo o his mechanism emains limi ed [206].
FTS ollows a su ace polyme iza ion model go e ned by he
Ande son–Schulz–Flo y (ASF) dis ibu ion, which p edic s hyd oca bon
p oduc dis ibu ion based on he chain-g ow h p obabili y (
α
). While
high
α
- alues (
α
>0.9) a o hea y hyd oca bons (C
21
+
), expe imen al
de ia ions o en occu , including excessi e me hane o ma ion and
a ia ions in ole in- o-pa a in a ios due o seconda y eac ions like
ole in e-adso p ion and hyd oc acking [207,208]. Since, he ASF model
inhe en ly limi s di ec selec i i y o middle-dis illa e uels (C
5
–C
20
),
equi ing addi ional hyd oc acking s eps o e ining O e coming hese
cons ain s in ol es p ecise ca alys design, such as suppo modi ica-
ions, noble me al inco po a ion, and ailo ed syn hesis me hods o
con ol eac ion kine ics and minimize me hane o ma ion. While he
dis ibu ion be ween pa a ins and ole ins depends on he H
2
/CO a io in
he syngas and he ca alys employed. High H
2
/CO a ios and s ong
M. Sai e al.
Biomass and Bioene gy 196 (2025) 107736
16
hyd ogena ing ca alys s a o pa a in p oduc ion, while lowe a ios
and weake hyd ogena ing ca alys s p omo e ole in o ma ion. Wa e ,
an ine i able byp oduc o FTS, signi ican ly impac s syngas con e sion,
hyd oca bon selec i i y, and ca alys pe o mance. Excess wa e can
deac i a e i on ca alys s h ough oxida ion, he eby educing p ocess
e iciency. Despi e ex ensi e s udies, he lack o a comp ehensi e mo-
lecula depic ion o FTS has spa ked ongoing deba e and explo a ion
using su ace science, compu a ional me hods, and mic okine ic models
[206,209,210]. Since, add essing en i onmen al conce ns and he need
o educe ossil uel dependency, he e is a g owing shi owa d
biomass-based and CO
2
-d i en FTS p ocesses [128]. These app oaches
eplace CO wi h CO
2
, o en coupled wi h sus ainable hyd ogen sou ces
such as blue o g een hyd ogen. These challenges unde sco e he
impo ance o bi unc ional ca alysis, whe e me al si es acili a e CO
ac i a ion and chain g ow h, while acidic o edox si es egula e sec-
onda y ans o ma ions like isome iza ion and hyd oc acking. The
in eg a ion o bi unc ional ca alys s such as Co o Fe wi h zeoli es, me al
oxides, o ca bides enables g ea e selec i i y con ol, o e coming ASF
cons ain s and enhancing middle-dis illa e p oduc ion wi hou addi-
ional e ining s eps. Mo eo e , comme cial High-Tempe a u e Fische
T opch (HTFT) and Low-Tempe a u e Fische T opch (LTFT) eac o s,
including ixed-bed, luidized-bed, and slu y-phase con igu a ions,
each in oduce unique mass and hea ans e challenges ha in luence
ca alys pe o mance and selec i i y. The op imiza ion o eac o design,
alongside bi unc ional ca alys ad ancemen s, emains key o achie ing
mo e e icien , cos -e ec i e, and selec i e FT p ocesses, pa icula ly o
sus ainable uel applica ions (Table 5) [211,212]. This pe spec i e
aligns wi h he ongoing shi owa d bio-based FTS and ca bon-neu al
uels, ein o cing bi unc ional ca aly ic ou es as a c ucial s a egy o
nex -gene a ion syn he ic uel p oduc ion [213,214]. Resea che s a e
also explo ing in eg a ed echnologies like andem ca alysis and
wo-s age p ocesses ha combine elec ochemical syngas p oduc ion
wi h con en ional FTS. These inno a ions aim o enhance sus ainabili y
and e iciency, aligning FTS wi h global e o s o ansi ion o cleane
ene gy sys ems [215].
4.4. Ca alys choice, p omo e s ole and hei e ec on p oduc
dis ibu ion in FTS ou e
In FTS, CO dissocia ion on G oup VIII me al su aces is c ucial [217],
in luenced by he elec onic s uc u es o ansi ion me als. Me als wi h
ewe occupied d-o bi als [218] bind dissocia ed C and O a oms mo e
s ongly, enhancing CO dissocia ion and a o ing longe -chain hyd o-
ca bons. Ru, Co, and Fe a e ideal o FT syn hesis, wi h Ru being he
mos ac i e bu cos ly and sca ce. Co ca alys s o e high ac i i y and
selec i i y o long-chain hyd oca bons, especially wax and diesel, wi h
esis ance o wa e deac i a ion. Fe ca alys s, while cheape , a e e -
sa ile o e wide condi ions and bene icial o he WGS eac ion, hough
Fig. 8. Majo h ee mechanis ic pa hways o me al oxide ca alys s o CO hyd ogena ion eac ion ia FTS. Rep oduced wi h he pe mission om he e [196].
Copy igh 2023 Ame ican Chemical Socie y.
Table 5
Compa ison o Co- and Fe-based FT ca alys s.
Fea u e Co-based Ca alys s Fe-based Ca alys s
CO Dissocia ion Lowe abili y compa ed
o Fe
Highe abili y
Hyd oca bon
Selec i i y
Highe selec i i y o
long-chain hyd oca bons
B oad p oduc dis ibu ion
including ligh ole ins and hea y
hyd oca bons
Ca alys Li e ime Gene ally, longe Sho e , wi h mo e deac i a ion
issues
Resis ance o
Deac i a ion
Be e a mode a e CO
con e sion le els
Deac i a es as e a high CO
con e sion le els
E ec o
P omo e s
Enhanced wi h noble
me als like P , Ru, Pd
Enhanced wi h alkali me als like
K, Na, ansi ion me als like Mn,
Cu
Suppo Ma e ials Typically used wi h
SiO
2
, Al
2
O
3
, TiO
2
SiO
2
, Al
2
O
3
, MgO, molecula
sie es, ac i a ed ca bon
WGS Ac i i y Low High
Ope a ing
Tempe a u e
Typically lowe Highe
Ca bu iza ion Less impo an C ucial o o ming ac i e phases
like FexC
Ac i e phase Me allic Co Fe Ca bides
Ca bon Sou ce Na u al Gas Biomass & Coal
H
2
/CO a io 2 0.5–2.5
Me hane
Selec i i y
High Low
Sul u Tole ance Ve y Sensi i e Sensi i e
Compa ison o selec ed FT Ca alys s [216,300].
M. Sai e al.
Biomass and Bioene gy 196 (2025) 107736
17
hey equi e signi ican modi ica ions and ace apid deac i a ion.
Table 5 p o ides a concise compa ison o he main cha ac e is ics and
di e ences be ween Co- and Fe-based FTS ca alys s [217]. Fo Co-based
ca alys s, me allic cobal (Co
0
) is he ac i e phase o CO hyd ogena ion,
p ima ily p oducing pa a ins wi h some ole ins and alcohols. Deac i-
a ion occu s due o oxida ion and ca bu iza ion, o ming cobal oxides
(CoO
x
) and ca bides (Co
2
C), which inc ease me hane selec i i y and
lowe ac i i y. Co
2
C is e ec i e o he Fische -T opsch o Ole ins (FTO)
p ocess, especially when sodium (Na) is added, o ming Co
2
C nano-
p isms ha enhance C
2–
C
4
=
selec i i y and educe me hane selec i i y.
On TiO
2
suppo , oxidized cubic CoO species show highe ac i i y and
selec i i y compa ed o me allic Co on SiO
2
. Ca bon-based suppo s o e
s abili y and acili a e ole in o ma ion. Ad anced ea men s like
hyd ogen and ca bon monoxide ea men s imp o e he ac i i y and
selec i i y o Co
2
C ca alys s. Howe e , in HTFT p ocesses, me hane
o ma ion poses challenges, ha demand some special con inemen e -
ec and inno a i e composi e ca alys designs o o e coming hese
hu dles, imp o ing selec i i y, and educing en i onmen al impac s
[306]. While Fe-based ca alys s ha e ga ne ed signi ican a en ion o
FTS due o hei high ac i i y, cos -e ec i eness, and low me hane
selec i i y [260]. Unlike Co ca alys s, Fe ca alys s can p oduce a b oad
ange o hyd oca bons (C
1
-C
60
). Howe e , iden i ying and con olling
he ac i e i on phases such as Fe
3
O
4
, Fe
2
O
3
,
α
-Fe, and a ious i on
ca bides du ing FTS is challenging. I on ca bides like
ε
′
-Fe
2
C,
χ
-Fe
5
C
2
,
and Θ-Fe
3
C a e key ac i e phases, wi h
χ
-Fe
5
C
2
being pa icula ly s able
and ac i e a mode a e empe a u es [17]. Ad anced cha ac e iza ion
echniques ha e e ealed phase ans o ma ions in i on ca alys s unde
ealis ic condi ions, such as he o ma ion o a Fe
3
O
4
@
χ
-Fe
5
C
2
co e-shell
s uc u e, which exhibi s high ac i i y. Achie ing a balance be ween
i on ca bides and oxides, especially Fe
3
O
4
, is c ucial o op imizing
pe o mance. Despi e ex ensi e esea ch, he mos ac i e phase o FTS
emains deba ed, wi h ac o s like pa icle size, phase mo phology, and
suppo e ec s in luencing he ou comes. Robus unde s anding equi es
syn hesizing pu e Fe-ca bide and p e en ing phase changes du ing e-
ac ions. E o s o syn hesize oxide- ee Fe-ca bides ha e shown p om-
ising esul s. Xu e al. [219] used a apid quenched skele al i on
p ecu so o p epa e a ca alys p ima ily consis ing o
ε
′
-ca bide,
demons a ing excellen LTFT ac i i y. Peng e al. [220] syn hesized
phase-pu e
ε
′
-ca bide using Raney-Fe, achie ing low CO
2
selec i i y in
low- empe a u e FT eac ions. S abilizing
ε
′
-ca bide in o g aphene
laye s enabled high- empe a u e FT eac ions wi hou ans o ming in o
χ
-Fe
5
C
2
. Yang e al. [221] syn hesized single-phase
χ
-Fe
5
C
2
wi h a
b omine agen , and subsequen s udies used mesopo ous silica shells o
p o ec
χ
-Fe
5
C
2
, main aining i s phase and low CO
2
selec i i y. These
app oaches enhance he unde s anding o FT ca alysis using
well-de ined, phase-pu e ca alys s.
P omo e s a e c ucial o enhancing he ac i i y and selec i i y o
FTS ca alys s [207]. They a e ca ego ized in o elec onic p omo e s (e.
g., alkali me als, ansi ion me als, a e ea h me als) and s uc u al
p omo e s (e.g., ino ganic oxides like SiO
2
and Al
2
O
3
). Key p omo e s
o Fe-based FT ca alys s include K, Na, Mn, Cu, and S, whe e alkali
me als like K and Na enhance C-O bond dissocia ion and imp o e i on
oxide educ ion and ca bu iza ion, op imizing p oduc dis ibu ion
[7–19,222–225]. Usually, Mn inc eases ole in selec i i y and ca alys
su ace a ea, while Cu aids Fe-oxide educ ion and ligh ole in o ma ion
[7,12,18,222,226–228]. I can be seen in Fig. 9 ha di e en ca alys
sys ems used in FTS and CO
2
hyd ogena ion, highligh ing he impac o
suppo s and p omo e s on pe o mance and p oduc selec i i y [18,
229–231]. Fig. 9A illus a es a Na-Fe-Mn-Si ca alys wi h a co e-shell
s uc u e, whe e i on-based ac i e si es a e encapsula ed wi hin a sil-
ica amewo k. The inclusion o HZSM-5 zeoli e enhances selec i i y
owa d ligh ole ins and a oma ics, minimizing he p oduc ion o
hea ie hyd oca bons. This dual- unc ion ca alys combines
Fische -T opsch ac i i y wi h seconda y eac ions acili a ed by he
zeoli e, op imizing hyd oca bon dis ibu ion. Fig. 9B compa es
i on-based (Fe
3
O
4
) and cobal -based ca alys s suppo ed on SiC o CO
2
hyd ogena ion, showing ha he Fe
3
O
4
ca alys is e ec i e in he
Fische -T opsch eac ion, p omo ing he o ma ion o long-chain hy-
d oca bons, while he cobal ca alys on SiC p ima ily acili a es
me hana ion, leading o CH
4
p oduc ion. The eac ion mechanism in-
ol es CO
2
hyd ogena ion ia he RWGS eac ion, ollowed by CO
con e sion o hyd oca bons in FTS. The cobal ca alys , howe e , a o s
di ec CO
2
hyd ogena ion o me hane, dis inguishing i om i on-based
sys ems. Fig. 9C ocuses on i on-aluminum oxide (FeAlO
5
) ca alys s,
pa icula ly hei ole in enhancing ligh ole in p oduc ion. This sys em
in ol es ca bona e, bica bona e, and o ma e species ha in luence CO
Fig. 9. A-D) Pe o mance o he di e en ca alys s wi h di e en suppo s and p omo e s on FTS ca alys s, A) Rep oduced wi h he pe mission om e . [18].
Copy igh 2022 Else ie . B) Rep oduced wi h he pe mission om e . [229]. Copy igh 2022 Else ie . C) Rep oduced wi h he pe mission om e . [230]. Copy igh
2020 Ame ican Chemical Socie y. D) Rep oduced wi h he pe mission om e . [231]. Copy igh 2021 Ame ican Chemical Socie y, espec i ely.
M. Sai e al.
Biomass and Bioene gy 196 (2025) 107736
18
ac i a ion while exhibi ing negligible WGS ac i i y, he eby limi ing
CO
2
o ma ion. The ca alys e icien ly p omo es C–C coupling, leading
o selec i e p oduc ion o C
5
+
linea
α
-ole ins. The supp ession o sec-
onda y eac ions ensu es high selec i i y owa ds aluable in-
e media es a he han pa a ins. Fig. 9D, compa es Fe
3
Al and
Fe
6
Zn
1
Al
1
ca alys s, demons a ing how ZnO and Al-based p omo e s
modi y ca aly ic pe o mance. The Fe
3
Al spinel s uc u e a o s CO
ac i a ion and alkane o ma ion, whe eas he Fe
6
Zn
1
Al
1
sys em, wi h
ZnO as a p omo e , enhances CO
2
hyd ogena ion and inc eases
α
-ole in
selec i i y. The ZnO-modi ied ca alys exhibi s supe io con ol o e
p oduc dis ibu ion, making i mo e e icien o ligh hyd oca bon
p oduc ion.
Simila ly, Gong e al. [207] in es iga es he e ec o Cu p omo ion
on Fe-Mn-based ca alys s o he Fische -T opsch o ole ins (FTO) p o-
cess, aiming o high ligh ole in selec i i y wi h low CO
2
emissions
(Fig. 10). A 3.0 w % Cu-loaded Fe-Mn ca alys exhibi ed excep ional
pe o mance, achie ing 96.9 % CO con e sion and 40.1 % selec i i y o
ligh ole ins, while main aining a low CO
2
selec i i y o 23.0 %. As Cu
loading ises (0–3.0 w %), ligh ole in selec i i y imp o es (31.3 %→
40.1 %), while C
5
+
dec eases (32.7 %→9.5 %) due o weake su ace
basici y, educing chain g ow h p obabili y. Cu can also imp o e he
ca alys educibili y and enhance H-assis ed CO dissocia ion by modi-
ying me al-suppo in e ac ions, leading o inc eased ac i i y and a shi
owa d sho -chain hyd oca bons. Cu addi ion o Fe-Mn ca alys s shi o
as e CH
x
deso p ion and limi long-chain o ma ion, while s able hy-
d ogena ion and β-H elimina ion main ain he ole in/pa a in a io. Cu
also boos s CO con e sion by lowe ing he ac i a ion ene gy o CO
dissocia ion. While, Zn and Mg p omo e Fe educ ion, enhance ca alys
dispe sion, and inc ease selec i i y o speci ic hyd oca bons [232]. In
Co-based ca alys s, noble me als like P , Ru, and Pd enhance cobal oxide
educ ion and o e all ac i i y. Bime allic Co-Fe ca alys s ha e also
gained a en ion o hei enhanced FTS pe o mance, whe e adding Co
o Fe-based ca alys s can imp o e CO dissocia ion and boos s FTS ac-
i i y, p omo ing long-chain hyd oca bon p oduc ion [233–260]. These
ca alys s show g ea e s abili y agains deac i a ion han pu e Co ca a-
lys s, al hough hey can s ill deac i a e a high CO con e sion le els due
o inc eased H
2
O pa ial p essu e. The ac i e me al and phase signi i-
can ly in luence he ca aly ic beha io in FTS eac ions. Usually, in bo h
cases, s uc u al suppo s like SiO
2
and Al
2
O
3
imp o e ca alys s abili y,
s eng h, and po osi y. SiO
2
is pa icula ly e ec i e in main aining
ca alys s abili y wi hou sac i icing ac i i y, while Al
2
O
3
enhances
p omo e dispe sion and ligh hyd oca bon selec i i y [261–264].
4.5. Bi unc ionali y o (OX-ZEO) cascade eac ions o a oma ics
Rega ding he upg ading o p oduc s o a oma ics, zeoli es ha e
Fig. 10. Di e en eac ion in e media es, chain g ow h scena ios and pa hways on FeCuMn ca alys o ligh syn hesis ole ins ia FTS ou e. Rep oduced wi h he
pe mission om Re . [207]. Copy igh 2020 Else ie .
M. Sai e al.
Biomass and Bioene gy 196 (2025) 107736
19
es ablished hemsel es as essen ial ca alys s in he chemical indus y o
upg ading p oduc s o a oma ics due o hei cos -e ec i eness, high
pe o mance, and e sa ile design [265]. These po ous c ys alline alu-
minosilica es a e widely used in adso p ion, ion exchange, and ca alysis
because o hei shape-selec i e p ope ies, uni o m po es, adjus able
acidi ies, and high he mal and hyd o he mal s abili y. Zeoli es can be
ei he na u ally occu ing o syn hesized o enhanced pu i y and
unc ionali y, wi h 252 app o ed amewo ks as o May 2020. Thei
di e se channel sys ems, po e openings, and ca i ies allow o p ecise
con ol o e eac ion in e media es and p e en me allic species ag-
g ega ion, making hem e icien and cos -e ec i e ca alys s o hyd o-
ca bon modi ica ion. The acidic p ope ies and high speci ic su ace a ea
(>100 m
2
/g) o zeoli es signi ican ly enhance hei ca aly ic capabil-
i ies, especially in syngas con e sion, which is becoming inc easingly
impo an . The con inemen e ec wi hin zeoli e ca i ies di ec s eac-
ion in e media es, in luencing pa hways and enhancing selec i i y o-
wa d desi ed p oduc s. Tailo ing zeoli e opology op imizes ca aly ic
p ocesses, p omo ing a ge p oduc selec i i y and imp o ing s abili y.
Popula zeoli es like CHA, MFI, *BEA, MOR, and AEI a e pa icula ly
a o ed o selec i e syngas con e sion due o hese ad an ageous
p ope ies. Among hese, ZSM-5 s ands ou o i s medium po e size
(~5.5 Å), which is e ec i e a con olling he o ma ion o
gasoline- ange p oduc molecules (≤C10) and esis ing coke o ma ion.
I excels a c acking, isome izing, oligome izing, and a oma izing
o med in e media es (oxygena es and ole ins) in o speci ic a oma ic
monome s. Thanks o i s mo deni e amewo k in e ed (MFI) opology,
ZSM-5 allows gasoline- ange a oma ic p oduc s o di use h ough linea
channels while in e media e molecules en e h ough sinusoidal chan-
nels wi hou coun e -di usion. The shape-selec i i y o HZSM-5 a o s
he di usion o linea -shaped hyd oca bons o e bulky-shaped mole-
cules, p omo ing he o ma ion o p-xylene isome among
gasoline- ange a oma ics. In con as , la ge-po e H-MOR zeoli e, wi h a
mic opo e size o ~7 Å, signi ican ly al e s a oma ic dis ibu ion and
inc eases me hane ac ion (45 w %). Resea che s ha e ound HZSM-5
o be a highly s able ca alys o a oma ic syn hesis. Fujimo o e al.
[266] sc eened a ious zeoli es, including HZSM-5, H-MOR, Y-zeoli e
(HY), and dealumina ed e sions o H-MOR and HY o me hanol and
syngas con e sion, concluding ha HZSM-5 p e en s coke p ecu so
o ma ion, and i s dealumina ion leads o excellen ca aly ic s abili y
and highe yields o a oma ic monome s compa ed o o he zeoli es
s udied. Since, he ema kable abili y o zeoli es o enhance p oduc
upg ading o a oma ics, coupled wi h hei s uc u al e sa ili y and
s abili y, unde sco es hei i al ole in he chemical indus y [267].
The bi unc ional ca aly ic ou e o a oma ics in FTS add esses he
inhe en selec i i y limi a ions o adi ional FTS by in eg a ing me al
cen e s wi h acidic molecula sie es. In his app oach, ca alys s ac i a e
and dissocia e CO in o ca bon in e media es, which hen unde go C–C
coupling. Howe e , he challenge lies in balancing C–O bond ac i a ion
and C–C coupling, o en leading o a ade-o be ween p oduc selec-
i i y and syngas con e sion a e [187]. The bi unc ional sys em o e -
comes his by combining me al oxides o FTS me als wi h molecula
sie es. This dual unc ionali y allows o ini ial CO ac i a ion and in-
e media e hyd oca bon o ma ion on me al si es, ollowed by selec i e
C–C bond econs uc ion and a oma iza ion on acidic si es. This me hod
e icien ly di ec s he eac ion pa hways owa d he p oduc ion o
high-selec i i y C
2
−C
4
hyd oca bons and a oma ics, b eaking he
adi ional ASF dis ibu ion (Fig. 11). The o e all igu e illus a es
di e en hyb id ca aly ic s a egies o he selec i e con e sion o syn-
gas in o lowe ole ins and a oma ics while b eaking he
Ande son-Schulz-Flo y (ASF) dis ibu ion ule in FTS. The ASF ule
p edic s a b oad dis ibu ion o hyd oca bons wi h a high ac ion o
long-chain p oduc s; howe e , coupling dis inc ca aly ic unc ionali ies
enables selec i i y con ol. The cen al concep p esen ed in he igu e is
hyb id ca alysis, whe e Fe-based ca alys s o me al oxides wo k in syn-
e gy wi h zeoli es (ZSM-5) o achie e ailo ed p oduc selec i i y.
Fig. 11A&B demons a es ha syngas can be con e ed in o a oma ics
h ough wo di e en pa hways: (i) an ole in-based ou e, whe e
Fe-based ca alys s gene a e lowe ole ins, which a e hen ans o med
in o a oma ics o e ZSM-5, and (ii) a me hanol-media ed pa hway,
whe e Zn-Z O
2
acili a es syngas con e sion o me hanol/dime hyl e he
(DME), ollowed by C
2
-C
4
hyd oca bon o ma ion and subsequen
a oma iza ion o e ZSM-5. The pa hway depic ed in he middle o he
image u he elabo a es on he bi unc ional ca aly ic mechanism,
whe e Zn-Z O
2
ca alyzes he con e sion o H
2
and CO in o me h-
anol/DME, which is hen ans o med in o ligh ole ins (C
2
-C
4
) o e
ZSM-5. The zeoli e’s acidi y plays a c i ical ole in p omo ing oligo-
me iza ion, cycliza ion, and dehyd ogena ion, leading o he selec i e
o ma ion o a oma ics. This hyb id app oach bypasses he ASF dis i-
bu ion limi a ion by p o iding an al e na i e eac ion pa hway a he
han di ec Fische -T opsch polyme iza ion. I also p esen s a selec i i y
compa ison unde di e en CO p essu es, demons a ing ha inc easing
CO p essu e shi s he p oduc dis ibu ion owa ds a oma ics, con-
i ming he e ec i eness o his eac ion coupling. Fig. 11C demons a e
a modi ied FeZnMg ca alys syn hesized ia sol-p ecipi a ion and com-
bined wi h HZSM-5 o di ec a oma ics syn hesis om syngas. Zn
induced elec onic modula ions, o ming ZnFe
2
O
4
e i e enhancing Fe
oxide educ ion, while Mg imp o ed ac i e si e dispe sion and Fe-la ice
uning, boos ing Fe species ca bu iza ion and C–O chemiso p ion. This
syne gy educed CO
2
and C
1
–C
4
pa a ins, achie ing 52 % a oma ic
selec i i y a 97 % CO con e sion. Fig. 11D highligh s he ca alys
design, showcasing a Zn-Z O
2
and H-ZSM-5 bi unc ional sys em, whe e
he me al oxide componen go e ns me hanol o ma ion while he
zeoli e acili a es subsequen hyd oca bon ans o ma ion. The combi-
na ion o hese unc ions leads o high a oma ic selec i i y (>80 %) wi h
ema kable s abili y (>1000 h).
The syne gis ic in e ac ion be ween me al cen e s and acidic si es no
only enhances selec i i y and yield bu also educes he need o cos ly
seconda y ea men s, making his bi unc ional app oach bo h e icien
and economically iable o p oduce a oma ic hyd oca bons. The chal-
lenge lies in achie ing high selec i i y o a oma ics, pa icula ly BTX,
h ough FTS in eg a ed wi h HZSM-5 zeoli e ca alys s. Op imal condi-
ions o FTS and a oma iza ion/isome iza ion eac ions o en do no
align well, hinde ing e icien BTX p oduc ion. Fe-based ca alys s a e
a o ed in single-bed eac o s due o hei abili y o gene a e alkenes
and hei high- empe a u e ole ance, which suppo s a oma ic o ma-
ion and acili a es hea eco e y o s eam gene a ion. Fac o s such as
zeoli e Si/Al a io(acidi y), po e s uc u e, and Fe-based ca alys ype
signi ican ly in luence a oma ic selec i i y and dis ibu ion. Ligh ole-
ins and pa a ins om Fe-based FTS ca alys s a e c ucial o a oma ic
Fig. 11. A-D) Di e en eac ion coupling o selec i e con e sion o syngas in o
lowe ole ins and a oma ics b eaking he ASF dis ibu ion. A) Rep oduced wi h
pe mission om e . [273]. Copy igh 2021 Else ie . B& D) Rep oduced wi h
pe mission om e . [25]. Copy igh , 2017 Else ie . C) Rep oduced wi h he
pe mission om he e . [233]. Copy igh , 2022 Ame ican Chemical Socie y.
M. Sai e al.
Biomass and Bioene gy 196 (2025) 107736
20
o ma ion, wi h ZSM-5 zeoli e p o ing e ec i e due o i s sui able po e
s uc u e and acidi y, c ucial o shape-selec i i y and a oma iza ion.
Indeed, ecen s udies ha e explo ed a ious bi unc ional ca alys sys-
ems o syn hesizing a oma ics di ec ly om syngas. Fo ins ance, Xu
e al. [268] de eloped a Fe/HZSM-5 ca alys , achie ing 90 % CO con-
e sion and 50 % a oma ic selec i i y unde condi ions o 320
◦
C, 2.0
MPa, and 4000 h
−1
. Yi Fu e al. [269] epo ed a composi e Fe/Zn-
C
2
O
4
&H-ZSM-5 ca alys wi h 57.5 % CO con e sion and 74 % a o-
ma ics selec i i y a 653 K and 4.0 MPa, highligh ing he ole o Fe in
enhancing CO con e sion and a oma ics p oduc ion h ough oxygen
acancy and i on ca bide o ma ion. Tang e al. [270] in eg a ed
MnFe
2
O
4
spinel and ZSM-5 zeoli e, achie ing o e 65 % a oma ics
selec i i y in C
5+
p oduc s [116]. Addi ionally, Ma e al. [271] syn he-
sized MgZ O
x
ca alys s combined wi h HZSM-5, demons a ing 66.4 %
a oma ic selec i i y a 400 ◦C and 3 MPa by e icien ly con e ing
me hanol and oxygena es in o a oma ics while minimizing long-chain
hyd oca bon o ma ion. Yang e al. [272] in es iga ed Na-Fe-Z-
O
2
/ZSM-5 andem ca alys s, elucida ing zeoli e’s ole in enhancing CO
hyd ogena ion and ole in ans o ma ion o imp o e a oma ics selec-
i i y. Nawaz e al. [260] s udied Na-FeMnCo/HZSM-5, ea u ing Fe-Co
alloy, achie ing 98 % CO con e sion and enhancing hyd oca bon and
a oma ic ac ions (55 %), wi h educed CO
2
(21 %). Uni o m CoFe
2
O
4
nanopa icles c ucially imp o ed ca aly ic pe o mance h ough unique
Fe subs i u ion in oxygen acancy densi y, i on oxide educibili y, and
su ace adso p ion, highligh ing zeoli e’s ca aly ic enhancemen e ec s.
These s udies unde sco e he di e se s a egies and ca alys combina-
ions aimed a op imizing a oma ics p oduc ion om syngas, empha-
sizing he c i ical ole o ca alys design and syne gis ic e ec s in
enhancing pe o mance.
While he hyd ogena ion o was e CO
2
h ough he e ogeneous
ca alysis has also gained signi ican a en ion due o ad ancemen s in
CO
2
cap u e echnologies and he p oduc ion o enewable hyd ogen as
shown in Fig. 12. In o e all he igu e illus a es wo p ima y ca aly ic
s a egies o he selec i e syn hesis o a oma ics om CO
2
hyd ogena-
ion: modi ied FTS and me hanol-media ed pa hways. These app oaches
in eg a e mul i unc ional ca alys s o enhance selec i i y, su passing he
limi a ions o con en ional FTS. In he modi ied Fische -T opsch ou e
(Fig. 12A), a Na-Fe
3
O
4
/zeoli e bi unc ional ca alys is employed o
con e CO
2
in o a oma ics. The eac ion sequence begins wi h he
RWGS eac ion, whe e CO
2
is educed o CO o e Fe
3
O
4
. The CO hen
unde goes he Fische -T opsch eac ion on Fe
5
C
2
si es, o ming sho -
chain hyd oca bons (C
n
H
m
). These in e media es di use in o he
zeoli e componen , whe e B øns ed acid si es ca alyze oligome iza ion,
isome iza ion, and a oma iza ion, p oducing C
5
-C
11
a oma ic hyd o-
ca bons wi h enhanced selec i i y. The me hanol-media ed pa hway
(Fig. 12B) in ol es CO
2
hyd ogena ion o me hanol o i s in e media es
(HCOO*, H
2
CO*, CH
3
OH*) on a Zn-Z O
2
ca alys , ollowed by con e -
sion o C
2
-C
4
ole ins and a oma ics o e zeoli es. The Zn-Z O
2
si es
p omo e e icien CO
2
ac i a ion and hyd ogena ion, while he zeoli e
ensu es selec i e hyd oca bon ans o ma ion. This bi unc ional sys em
achie es 73 % a oma ic selec i i y, demons a ing i s po en ial o CO
2
u iliza ion in pe ochemical applica ions. Fig. 12C p o ides u he in-
sigh s in o he eac ion mechanism o ZnFeO
x
-Na/HZSM-5 ca alys s.
The Fe
3
O
4
phase enables RWGS, while Fe
5
C
2
acili a es FTS, p oducing
sho -chain ole ins. These in e media es di use o HZSM-5, whe e
B øns ed acid si es ca alyze a oma iza ion, yielding high xylenes (PX)
selec i i y (75 %). This pa hway e ec i ely enhances CO
2
con e sion
(~40 %) while di ec ing selec i i y owa d aluable a oma ics. While
Fig. 12D p esen s a s uc u al op imiza ion s a egy o HZSM-5 o
u he imp o e a oma ic yield. A chain-like HZSM-5 mo phology wi h
enhanced b-axis di usion channels p e en s su ace passi a ion and
acili a es e icien molecula anspo . This esul s in 74.7 % a oma ic
selec i i y, wi h con olled dis ibu ion o pa a-xylene (PX) and e a-
me hylbenzene (TeMB). Since, among he p omising app oaches o
Fig. 12. A-D) The modi ied FTS and me hanol-media ed pa hways o A oma ics syn hesis om CO
2
hyd ogena ion. A) Rep oduced wi h he pe mission om e .
[275]. Copy igh 2017 Na u e. B) Rep oduced wi h he pe mission om e . [180]. Copy igh 2019 Else ie , C) Rep oduced wi h he pe mission om e . [276].
Copy igh 2019 Ame ican Chemical Socie y. D) Rep oduced wi h he pe mission om e . [277]. Copy igh 2021 Else ie , espec i ely.
M. Sai e al.
Biomass and Bioene gy 196 (2025) 107736
21
educe CO
2
emissions and gene a e aluable a oma ic compounds is CO
2
a oma iza ion, which in ol es he same andem ca alys sys em
combining CO
2
hyd ogena ion and in e media e a oma iza ion ca a-
lys s. Whe e he ole inic in e media es om CO
2
hyd ogena ion on he
Fe-based ca alys s ( ia he RWGS eac ion ollowed by FTS ou e), o on
he MTS based me al oxides ( ia me hanol o DME), can be subsequen ly
a oma ized on H-ZSM-5. The composi ion o he ca alys s, he acidi y o
H-ZSM-5, and he in e ac ion be ween componen s play c ucial oles in
de e mining a oma ics selec i i y. Whe e he economic iabili y de-
mands a highe a oma ic yield a leas 46 % o oluene p oduc ion
alongside a ca bon p ice below $340 pe on o CO
2
o compe e wi h
ossil-based al e na i es. This unde sco es he need o con inued
esea ch and op imiza ion o enhance he p ocess’s economic compe i-
i eness. Di ec CO
2
a oma iza ion aces se e al challenges compa ed o
indi ec me hods, which use sepa a e eac o s op imized o each s ep. A
majo limi a ion is he na ow empe a u e ange equi ed o bo h
ca aly ic unc ions o ope a e e ec i ely, es ic ing he use o ce ain
ca alys s o me hanol o ole in syn hesis in di ec p ocesses. Addi ion-
ally, eac ion pa ame e s exhibi complex ade-o s; o ins ance, while
wa e can imp o e e hylene a oma iza ion by compe ing o adso p ion
on H-ZSM-5 acid si es, excess wa e inhibi s CO
2
hyd ogena ion. Despi e
hese hu dles, di ec a oma iza ion o e s ad an ages such as cos and
ene gy sa ings h ough p ocess in ensi ica ion, educed coke o ma ion
due o hyd ogen’s p esence, and po en ial he modynamic bene i s om
he in-si u consump ion o in e media es. Con inued inno a ion is
essen ial o o e come hese challenges, imp o e yields, and es ablish
di ec CO
2
a oma iza ion as a iable and compe i i e me hod o sus-
ainable a oma ic p oduc ion. A ecen s udy on Fe-based ca alys pai ed
wi h a no el winned HZSM-5 (LZ5) zeoli e con aining a high sinusoidal
po e opening a io, claimed he enhanced a oma ics o ma ion a e (40
mmol
CO2gca
−1
h
−1
) wi h highly selec i e pa axylene (PX) p oduc ion om
CO
2
[274]. Ope a ing unde indus ial condi ions, he andem ca alys
eached a 31.5 % CO
2
con e sion wi h PX selec i i y o 34 % among
a oma ics and 90 % wi hin xylene isome s. This enhanced selec i i y
was a ibu ed o LZ5’s unique po e s uc u e, which e icien ly sc eens
xylene isome s, while he p oximi y o ca alys componen s enables
con inuous CO
2
- o-PX con e sion. Simila ly a high-pe o mance iple
composi e ca alys sys em using ZnZ O
x
, Al
2
O
3
, and H-ZSM-5 signi i-
can ly imp o ed he alkyla ion o benzene wi h CO
2
/H
2
o p oduce
oluene and xylene, o e ing a p omising ou e o educe ca bon emis-
sions and upg ade ligh a oma ics [158]. The sys em achie es 97 %
selec i i y o oluene and xylene a 9.7 % benzene con e sion by con-
e ing CO
2
o me hanol, dehyd a ing i o DME, and alkyla ing benzene
wi h DME. This app oach enhanced he alkyla ion ac i i y while mini-
mizing unwan ed eac ions, pa ing he way o mo e e icien CO
2
hy-
d ogena ion p ocesses. Enhancing he syne gy be ween ca alys
componen s, such as using size-con olled P nanopa icles on H-ZSM-5,
has p o en e ec i e, inc easing CO
2
con e sion ac i i y signi ican ly.
MTS based me al oxides o e di e en ad an ages o e Fe-based ca a-
lys s o CO
2
a oma iza ion, no ably exhibi ing signi ican ly lowe CH
4
selec i i y (less han 0.5 %) compa ed o Fe-based/H-ZSM-5 ca alys s
(o e 4 %). Con a ily, he Fe-based/H-ZSM-5 ca alys s main ain CO
selec i i y below 10 %, whe eas MTS-based/H-ZSM-5 ca alys s s uggle
o keep CO selec i i y below ~35 %, as hese me al oxides a e less
e ec i e o CO-FTS eac ions a high empe a u es. Co- eeding CO can
supp ess i s o ma ion by he modynamically in e ening in he RWGS
eac ion, bu op imizing he RWGS eac ion a e h ough ca alys design
is a mo e p ac ical app oach o imp o ing he p ocess. Whe e, op i-
mizing a oma ics selec i i y in ol es adjus ing he design o H-ZSM-5
ca alys s, pa icula ly he ype, in ensi y, and placemen o acid si es.
Fe-based ca alys s pai ed wi h H-ZSM-5 zeoli es excel in CO
2
- o-ole in
con e sion, especially when he zeoli e ea u es a lowe Si/Al a io,
co esponding o highe acid densi y. This enhanced acid unc ionali y
aligns wi h he ca alys s’ need o e ec i e CO
2
con e sion. Modi ying
H-ZSM-5 h ough NaOH ea men s allows ine- uning o acid si e in-
ensi y and ype, bu he in e play be ween B øns ed and Lewis acid si es
emains insu icien ly unde s ood. Fu u e esea ch should p io i ize
educing me hane selec i i y in Fe-based sys ems, op imizing Si/Al a-
ios and acid si e dis ibu ions in H-ZSM-5, and le e aging dual-bed
con igu a ions o imp o e a oma iza ion pe o mance.
Up o now, a mo e ecen de elopmen by Wang e al. g oup ha e
been epo ed o syn hesizing a highly e icien ca aly ic sys em o he
di ec con e sion o syngas o pa a-xylene (PX) and o he a oma ics
using a bi unc ional ca alys composed o CoMnAl and e sa ile HZSM-
5@silicali e-1 zeoli es (Fig. 13) [4]. Unde mild condi ions (280 ◦C, 2
MPa), his sys em achie ed o e 70 % CO con e sion and p oduced 63.5
% a oma ics, wi h PX making up 34.7 % o he o al. Me hane o ma ion
was minimal a jus 2.9 %, while CO
2
selec i i y was kep unde 25.6 %.
The inno a i e design o nanosized HZSM-5 wi h a hollow s uc u e
enhances ole in di usion, boos ing bo h CO con e sion and a oma ic
selec i i y. The addi ion o a scaly silicali e-1 laye on he HZSM-5
p e en s unwan ed side eac ions, imp o ing ca alys s abili y, wi h
no deac i a ion obse ed o e 726 h. C ucially, oxygen-con aining a -
oma ic compounds like p- olualdehyde play a key ole in he con e sion
p ocess, helping o ans o m syngas in o aluable PX. This b eak-
h ough o e s a p omising indus ial solu ion o e icien and selec i e
PX syn hesis while ad ancing ou unde s anding o syngas- o-a oma ics
eac ion mechanisms. Though, Co-based me al oxides, when pai ed wi h
zeoli es, a e e olu ionizing syngas- o-hyd oca bon echnology by
enhancing pe o mance and selec i i y o C
6
+
hyd oca bons. Key chal-
lenges in designing di ec CO
2
a oma iza ion p ocesses include man-
aging di usion pa h leng hs o in e media es, which impac he
con e sion o desi ed a oma ics and limi unwan ed side eac ions like
isome iza ion and hyd oc acking. Hie a chical zeoli e s uc u es,
c ea ed h ough alkali ea men s, inc ease su ace a ea and educe
di usion limi a ions bu can in oduce he e ogenei y and acid/base
poisoning. Selec i i y o BTX a oma ics emains a c i ical a ea o ocus.
Techniques such as coa ing zeoli es’ ex e nal su aces wi h SiO
2
ha e
shown p omise in imp o ing BTX yields bu also isk na owing po es
and educing in e nal acidi y, which hampe s in e media e con e sion.
Explo ing al e na i e zeoli e s uc u es and ad anced passi a ion s a-
egies could yield signi ican imp o emen s. Theo e ical and compu a-
ional s udies play a pi o al ole in un a eling he complexi ies o
andem ca aly ic sys ems. Fo Fe- and Co-based ca alys s, densi y unc-
ional heo y (DFT) mus accoun o spin-pola iza ion, magne ic p op-
e ies, and dynamic he modynamic phases du ing eac ions.
Mixed-me al oxides and mul i-componen ca alys s add ano he laye
o complexi y due o ambiguous ac i e si es, making a omis ic modeling
pa icula ly challenging. Fo zeoli es, accu a e modeling equi es
inco po a ing long- ange dispe si e in e ac ions and di e se adso p ion
en i onmen s. Ad anced echniques such as kine ic Mon e Ca lo simu-
la ions and co e age-dependen mean- ield models a e essen ial o
simula e high-p essu e, non-ideal eac ion condi ions bu demand sig-
ni ican compu a ional esou ces. Comp ehensi e kine ic s udies a e
i al o mapping he mul is ep eac ion ne wo ks in CO
2
a oma iza ion,
including al e na i e pa hways like ca bon suboxide-mesi ylene syn-
hesis o me hane a oma iza ion. Coupling CO
2
- o-me hanol ca alys s
wi h a oma ics-alkyla ion ca alys s p esen s an in iguing a enue o
p oducing me hyla ed a oma ics, bu achie ing high selec i i y emains
elusi e. In eg a ing kine ic, anspo , and p ocess models is essen ial o
b idge he gap be ween heo e ical p edic ions and expe imen al esul s,
enabling meaning ul e alua ions o selec i i y and yield. Despi e hese
challenges, he di ec con e sion o CO
2
o BTX a oma ics o e s a
ans o ma i e oppo uni y o ca bon cap u e and u iliza ion. Success
hinges on simpli ying complex eac ion ne wo ks in o manageable
models o gain a ounda ional unde s anding. Le e aging da a science
and machine lea ning o analyze expe imen al and compu a ional da a
can accele a e b eak h oughs, o e ing insigh s in o in ica e eac ion
mechanisms and guiding ca alys design. By me ging expe imen al in-
sigh s, ad anced simula ions, and da a-d i en app oaches, esea che s
can o e come he in e disciplina y hu dles and unlock he ull po en ial
o CO
2
- o-a oma ics echnologies.
M. Sai e al.
Biomass and Bioene gy 196 (2025) 107736
22
4.6. Mechanis ic pa hways o bi unc ional ou e o a oma ics
The di ec syn hesis o a oma ic hyd oca bons om syngas in ol es
nume ous complex s eps and aces signi ican challenges, p ima ily due
o limi ed selec i i y o aluable a oma ic monome s like BTX. The
undamen al eac ion mechanisms on bi unc ional he e ogeneous ca a-
lys s a e no ully unde s ood, impeding he op imiza ion o exis ing
ca alys s and he de elopmen o new ones. Unde s anding hese
mechanisms is c ucial o imp o ing ca alys pe o mance and e i-
ciency. The p ocess o STA ypically ollows wo main pa hways: he FTS
ou e and he MTS ou e, bo h in ol ing solid-acid HZSM-5 (Fig. 14).
While he con e sion o CO o ole ins h ough CO hyd ogena ion is well-
documen ed, he subsequen ans o ma ion o ole ins o pa a ins in o
a oma ics o e HZSM-5 is pa icula ly c i ical. These ans o ma ions
equi e highe empe a u es han hose op imal o ole in syn hesis om
syngas. The o e all con e sion p ocess includes a a ie y o eac ions
such as hyd ogena ion, oligome iza ion, c acking, isome iza ion,
me hyla ion, dehyd ogena ion, and hyd ogen ans e . Each o hese
eac ions con ibu es o he complexi y o he p ocess and poses chal-
lenges in achie ing high selec i i y and e iciency. A ho ough
unde s anding o each eac ion mechanism is essen ial o op imizing
he p oduc ion o aluable a oma ic compounds and enhancing he
pe o mance o he ca aly ic sys em. The con e sion o syngas o a o-
ma ic monome s o e bi unc ional ca alys s begins wi h CO being con-
e ed in o ole ins o a ying ca bon leng hs (C
2
–C
5
, C
6
–C
8
, and C
9
+
),
ollowed by he di usion in o he channels o HZSM-5 zeoli e and un-
de going o u he ans o ma ions. Speci ically, C
2
–C
5
ole ins a e i s
oligome ized in o C
6
–C
8
ole ins o e he B øns ed acid si es (BAS) o
HZSM-5. These C
6
–C
8
ole ins hen unde go cycliza ion, hyd ogen
ans e , and/o dehyd ogena ion o o m C
6
–C
8
ligh a oma ics.
Some o hese ligh a oma ics may be alkyla ed in o C
9
+
hea y a o-
ma ics o e he ex e nal acid si es o HZSM-5. Meanwhile, C
6
–C
8
and C
9
+
ole ins can be di ec ly con e ed in o hei co esponding ligh and
hea y a oma ics h ough simila cycliza ion and dehyd ogena ion p o-
cesses. The o ma ion o a oma ics is acili a ed by a syne gis ic e ec
be ween BAS and Lewis acid si es (LAS); o ins ance, cyclic ole ins
gene a ed o e BAS can be con e ed in o cyclic diole ins ia hyd ogen
ans e and dehyd ogena ion o e LAS. Howe e , some o he C
9
+
hea y
a oma ics may unde go o e -dehyd ogena ion, leading o coke o ma-
ion and he e en ual deac i a ion o he HZSM-5 ca alys [4]. The MTA
Fig. 13. Co-based/HZSM-5 bi unc ional ca alys s o unp eceden ed pa a-xylene p oduc ion om CO hyd ogena ion. Rep oduced wi h he pe mission om e . [4].
Copy igh 2022 Else ie .
M. Sai e al.
Biomass and Bioene gy 196 (2025) 107736
23
eac ion in ol es nume ous in e media es and comp ises complex s eps,
such as dehyd a ion, alkyla ion, dealkyla ion, isome iza ion, oligome -
iza ion, cycliza ion, and hyd ide ans e [278]. Ini ially, me hanol un-
de goes dehyd a ion o p oduce dime hyl e he , which can be u he
dehyd a ed o o m e hylene. Subsequen con inuous me hyla ion o
e hylene, along wi h oligome iza ion and cycliza ion, leads o he o -
ma ion o C
6
–C
9
cyclic ole ins. Hyd ogen ans e om hese C
6
–C
9
cy-
clic ole ins o C
2
–C
5
ole ins gene a es C
6
–C
9
a oma ics and C
2
–C
5
alkanes, while hyd ogen ans e o me hanol p oduces C
6
–C
9
a oma ics
and CH
4
. Zn-based oxides play a c ucial ole in his p ocess by sup-
p essing hyd ogen ans e bu acili a ing he dehyd ogena ion o C
6
–C
9
cyclic ole ins, he eby p omo ing he p oduc ion o a oma ics. Conse-
quen ly, oligome iza ion and cycliza ion o low-ca bon ole ins a e
a o ed due o chemical equilib ium. Low-ca bon alkanes also o m
h ough he c acking o C
6
–C
9
+
cyclic ole ins, hough hei a oma iza ion
is challenging a 450 ◦C. Th oughou he eac ion, me hyla ion, deal-
kyla ion, and isome iza ion o in e media es a e p e alen , wi h deal-
kyla ion o C
9+
a oma ics con ibu ing o he inc eased yields o bo h
alkanes and BTX. While an imp essi e mechanis ic illus a ion on
Co-based/HZSM-5 composi e ca alys has been p o ided by Wang e al.
[4], demons a ing ha using CO ins ead o A signi ican ly enhances
ole in con e sion and inc eases selec i i y owa d a oma ics while
educing he p oduc ion o lowe ole ins, whe e CO plays a key ole in
ole in coupling, especially o long-chain ole ins, o o m a oma ics o e
HZSM-5 zeoli e (Fig. 15). I has been demons a ed ha CO can be
adso bed on bo h weak and s ong acid si es, o ming ca bonyl com-
pounds ha eac wi h ole ins o p oduce cyclic oxygena es, which a e
hen con e ed o a oma ics. Whe e, CO dissocia es on he Co
2
C su ace,
leading o he o ma ion o in e media e species ha unde go hyd o-
gena ion and C-C coupling, p omo ing he con e sion o ole ins in o
a oma ics. Key in e media es, such as 2,4-dime hyl-benzaldehyde and
p- olualdehyde, we e iden i ied, indica ing ha hese oxygena ed com-
pounds play a i al ole in a oma ic o ma ion. This pa hway in ol es
CO hyd ogena ion o ole ins, hei coupling wi h CO, and u he
ans o ma ion in o a oma ics h ough eac ions acili a ed by HZSM-5.
Simila ly, he s udy by Tian e al. [279] b ie ly e eals highligh s
how LaFeO
3
pe o ski e enables he selec i e con e sion o CO
2
in o
aluable a oma ics. The p ocess begins wi h CO
2
hyd ogena ion on
Fig. 14. Figu e: Gene al eac ion pa hways o he p oduc ion o a oma ic monome s om syngas o e he FTS, and MTS wi h HZSM-5. Rep oduced wi h he
pe mission om e . [182]. Copy igh 2023 Else ie .
M. Sai e al.
Biomass and Bioene gy 196 (2025) 107736
24
LaFeO
3
, p oducing C1 oxygena es like o ma e and o maldehyde. These
in e media es hen mig a e o he H-ZSM-5 zeoli e, whe e hey unde go
C-C coupling and a oma iza ion. A key ad an age o LaFeO
3
is i s
esis ance o ca bu iza ion, which p e en s unwan ed side eac ions
commonly seen in i on-based ca alys s. This decoupling o CO
2
hyd o-
gena ion om a oma ics o ma ion ensu es high selec i i y and s abili y,
esul ing in a highly e icien CO
2
- o-a oma ics con e sion p ocess.
Unlike con en ional i on-based ca alys s ha o m ca bides and p oduce
a wide ange o p oduc s, LaFeO
3
’s unique su ace chemis y a o s he
o ma ion o p ecise C
1
in e media es, which a e u he ans o med
in o a oma ics in he acidic po es o H-ZSM-5. Th ough ad anced in-si u
spec oscopy and compu a ional analysis, he esea che s iden i ied he
key eac ion pa hways, demons a ing how LaFeO
3
main ains ca aly ic
pe o mance o o e 1000 h wi hou deac i a ion. This inno a i e
pe o ski e-based sys em o e s excep ional s abili y and e iciency,
making i highly p omising o scalable indus ial applica ions. The
andem ca alysis app oach no only con e s CO
2
in o aluable chem-
icals bu also con ibu es o g eenhouse gas educ ion, pa ing he way
o a sus ainable u u e in chemical manu ac u ing. Usually, me hanol
media ed pa hways a e a ac i e owa ds hea y a oma ics such as
du ene, a aluable a oma ic used in polyimide p oduc ion and a ia ion
ke osene addi i es, is adi ionally de i ed om pe oleum, which is
cos ly and unsus ainable. A ecen s udy p esen s e icien me hod o
syn hesizing du ene h ough he me hyla ion o ime hylbenzene
coupled wi h CO
2
hyd ogena ion, achie ing an imp essi e 83.2 %
du ene selec i i y in e ame hylbenzene (Te aMB) and 69.1 % Te -
aMB selec i i y among a oma ics, wi h a 1,2,4- ime hylbenzene con-
e sion o 33.2 % [280]. E en wi h mixed Te aMB eed, du ene
selec i i y emained high a 81.4 %. The 5 % CuZnZ O
x
-HZSM-5 ca alys
demons a ed long- e m s abili y, main aining pe o mance o o e
1100 h. Coppe ’s ole in he ZnZ O
x
composi e was c ucial in gene a ing
ac i e in e media es om CO
2
hyd ogena ion, enhancing he me hyl-
a ion p ocess. This app oach p o ides a sus ainable al e na i e o
du ene syn hesis wi h high e iciency and du abili y. The dis ibu ion o
p oduc s in he STA p ocess is p ima ily con olled by he cha ac e is ics
o acid si es and hei s eng h on he HZSM-5 ca alys . Howe e , i is
c ucial o emphasize ha ha ing a comp ehensi e unde s anding o he
eac ion mechanisms in ol ed in he di ec syn hesis o a oma ics om
syngas is aluable. This unde s anding no only aids in he de elopmen
o new, ad anced he e ogeneous ca alys s bu also con ibu es o en-
hancemen s in exis ing ca aly ic sys ems. By un a eling he in icacies o
he eac ion pa hways, esea che s can op imize ca alys design and
ope a ion, leading o imp o ed selec i i y and e iciency in he p o-
duc ion o a oma ic compounds om syngas.
4.7. Tunning he ca aly ic bi unc ionali y o p oduc upg ada ion and
ele a ion while dic a ing he deac i a ion scena ios
Molecula sie es, pa icula ly HZSM-5, a e highly alued o hei
p ecise acidi y and dis inc i e channel s uc u e, making hem c i ical in
STA eac ions and as ca alys s o a oma iza ion. The dis ibu ion o
s ong and weak acid cen e s in HZSM-5 molecula sie es is essen ial o
alkene cycliza ion, which d i es a oma ic compound o ma ion. Op i-
mizing ca alys pe o mance hinges on unde s anding he in ica e
ela ionship be ween acidi y, po e s uc u e, and a oma ic selec i i y.
Howe e , i s unde s anding he deac i a ion scena ios in bi unc-
ional ca alys is c ucial o main aining a highe ca aly ic ac i i y.
Usually an in eg a ed ca alys (OX-ZEO) composed o wo sepa a e
compa s, me al-based oxides e med as “OX” and he molecula sie e
ca alys usually zeoli e a e e med as ZEO, which encoun e he ca alys
deac i a ion pa hways in di e en manne s. Mainly, he me al oxides
(OX) such as Fe-based ca alys s used in FTS eac ions a e suscep ible o
deac i a ion due o ca alys sin e ing, pa icle agglome a ion, and
a i ion. To p e en physical de e io a ion, a suppo i e ma e ial is
necessa y o dispe se and s abilize he ac i e phase, wi h s ong suppo -
me al in e ac ions inhibi ing sin e ing. S uc u al p omo e s may
enhance hese in e ac ions. Chemical changes in he ca alys , such as
oxida ion o me allic Fe o Fe-ca bide phases, con ibu e o deac i a ion,
pa icula ly a high CO con e sion a es, leading o Fe-oxide o ma ion
and highe CO
2
selec i i y h ough he WGS eac ion. Coke o ma ion
Fig. 15. P oposed eac ion mechanism o he imp o ed p oduc ion o a oma ics om syngas o e he CoMnAl/HZSM-5 bi unc ional ca alys s. Rep oduced wi h he
pe mission om e . [4]. Copy igh 2022 Else ie .
M. Sai e al.
Biomass and Bioene gy 196 (2025) 107736
25
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