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Sustainable aviation fuel production via the
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Cite this: DOI: 10.1039/d5se00231a
methanol pathway: a technical review
Open Access Article. Published on 27 May 2025. Downloaded on 7/9/2025 10:26:08 AM.
Ali Elwalily, ab Emma Verkama, a Franz Mantei, a Adiya Kaliyeva,a
Andrew Pounder,a Jörg Sauer b and Florian Nestler *a
Due to the compatibility towards today's aviation infrastructure, sustainable aviation fuels (SAF) are expected
to contribute to a significant reduction of this sector's CO2 emissions. The methanol pathway represents
a synthesis-based route for producing SAF that can utilize various feedstocks, including electrolytically
produced H2 and atmospheric CO2 through a power-to-liquid (PtL) process, which can be implemented
at large-scale. The process is considered advantageous compared to other routes, primarily in terms of
yield and low levels of byproduct formation, and is projected to efficiently produce jet fuel (C8–C16). This
review analyzes the state of science for the entire process chain consisting of methanol synthesis,
Received 14th February 2025
Accepted 23rd May 2025
methanol-to-olefin conversion, oligomerization, and hydrogenation. Here, special attention is drawn to
the respective feedstocks, reaction systems, reactor design and process layouts to highlight technology-
DOI: 10.1039/d5se00231a
specific challenges to be considered. After individually reviewing the sub-processes, their interfaces are
rsc.li/sustainable-energy analyzed to derive research demands on the process side.
Currently, 50 kg of batteries are needed to supply the same
1 Introduction amount of energy as 1 kg of jet fuel, complicating their adaption
With an estimated total emission of 0.8 GtCO2, the aviation for long-distance ights.14 Due to its low volumetric energy
sector accounted for over 2% of the global anthropogenic density and difficult handling, hydrogen fuelled aircras also
carbon dioxide (CO2) emissions in 2022.1,2 These emissions are require further research and development to address challenges
projected to triple by the year 2050, provided that no counter regarding onboard storage of hydrogen, restricted ight ranges,
measures are taken.3,4 The primary source of these emissions is as well as comprehensive updates to aviation infrastructure and
the combustion of fossil-based jet fuel during ight operations aircra designs.15 Given the current state of the aviation
accounting to about 2.5 kg of CO2 per litre of jet fuel.5 Despite industry and the operational eet, it is hardly possible to nd
the global decrease of fuel consumption per passenger of 23% alternatives to liquid jet fuels, possessing high energy densities
between 2005 and 2017, i.e. from 4.4 L per 100 km to 3.4 L per and a short implementation interval.16
100 km, this efficiency gain is counterbalanced by the projected Sustainable aviation fuels (SAFs) are commonly referred to as
annual growth in passenger numbers of 4.3%.6,7 In addition to kerosene-type fuels that can be produced from renewable
CO2, signicant emissions from global aviation include energy sources.17 SAFs are identied as viable drop-in replace-
nitrogen oxides (NOx), water vapor, soot, sulfate aerosols, and ments and blendstocks for fossil-based jet fuel, capable of
increased cloudiness due to contrail formation.8,9 Both CO2 and mitigating the environmental impact by decreasing fossil CO2
non-CO2 emissions contribute to net surface warming and and other GHG emissions. Indeed, the International Air
anthropogenic climate changes,10 with approximately one-third Transport Association (IATA) has recognized SAF production as
of the radiative forcing attributed to CO2 and the other two- the most promising short-term strategy to reduce CO2 emis-
thirds caused by particulate emissions and water vapor form- sions in the aviation sector.18 Additionally, the production of
ing contrail cirrus clouds.11,12 SAF could contribute to meeting the increasing global demand
The climate impact of aviation could be mitigated by for jet fuel while enhancing energy security and reducing reli-
adopting new technologies, such as electric or hydrogen (H2) ance on fossil fuels.19
fuelled aircras.13 However, electrication of aviation faces SAF can be categorized based on their production routes and
signicant challenges due to the low energy-density of batteries. the type of feedstocks with the primary distinction between
biological and non-biological origin, as shown in Fig. 1. For SAF
to be commercially permitted for usage, it must be certied by
a
Fraunhofer Institute for Solar Energy Systems ISE, Hydrogen Technolgoies, the ASTM D7566 Standard Specication for Aviation Turbine
Heidenhofstr. 2, 79110 Freiburg, Germany. E-mail: [email protected] Fuel Containing Synthesized Hydrocarbons, set by the Amer-
b
Karlsruhe Institute of Technology (KIT), Hermann-von-Helmholtz-Platz 1, D-76344 ican Society for Testing and Materials (ASTM).20 The
Eggenstein-Leopoldshafen, Germany
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Fig. 1 Main production routes for synthetic jet fuel production.19
qualication process for new candidates of non-petroleum a 50% maximum blending limit. This can be attributed to the
alternative jet fuels is specied by ASTM D4054 Standard signicantly reduced aromatics content in the SAF produced,
Practice for Evaluation of New Aviation Turbine Fuels and Fuel which could affect the seal compatibility of aircra engines.25
Additives.21,22 Once an alternative jet fuel production route is The aviation industry aims to progress towards the use of 100%
qualied, the standard specication for that jet fuel would be SAF that comply with safety and operability requirements of the
added as an annex to ASTM D7566. These ASTM standards ASTM qualication process.26
ensure that the produced SAF possess compatible characteris- In 2024, SAF represented only 0.3% of global jet fuel
tics with the commercially available fossil-based jet fuels (Jet A/ produced.27 Large-scale production of SAF faces signicant
Jet A-1), specied in ASTM D1655 Standard Specication for challenges, primarily due to their production costs which are
Aviation Turbine Fuels.23 estimated to be 1.2 to 7 times higher than the market price of
Table 1 compares selected ASTM property requirements for conventional fossil jet fuel.28,29 The EU council recently adopted
Jet A and a selection of alternative jet fuel routes. Notably, the RefuelEU aviation initiative designed to stimulate large-
stricter requirements for alternative fuels have been imple- scale production of SAF and reduce production costs with
mented due to various concerns about the specic distinctions increasing technological maturity.28,29 This initiative includes
between synthetic chemical blends with petroleum distillates.24 a new regulation mandating a gradual increase of the minimum
To date, no 100% drop-in SAF process routes have been SAF share in jet fuel blends at EU airports from 2% in 2025 to
approved by ASTM and most approved production routes have 70% by 2050.30 Moreover, it sets targets for renewable fuels of
Table 1 Selected ASTM properties of Jet A/A-1 and SPK of FT, HEFA and ATJ20,23
Property requirement Jet A SAF (FT-SPK/HEFA-SPK/ATJ-SPK)
Acidity (total mg KOH per g) <0.1 <0.015
Distillation, 10% recovered (°C) <205 <205
Distillation, nal boiling point (°C) <300 <300
Flash point (°C) >38 >38
Freezing point (°C) <−40 <−40
Viscosity at −20 °C (mm2 s−1) <8 <8
Density at 15 °C (kg m−3) 775 to 840 730 to 770
Aromatics 8–25 vol% <0.5 wt%
Sulfur (wt%) 0.3 0.0015
Metals (mg per kg metal)
(Al, Ca, Co, Cr, Cu, Fe, K, Li, Mg, Mn, Mo, Na, Ni, P, Pb, Pd, Pt, Sn, Sr, Ti, V, Zn), mg kg−1 No requirement 0.1
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non-biological origin (RFNBO), starting at 0.7% in 2030, with an pathway.49,50 While SAF derived from the FT process has already
increase to 35% by 2050. This increase is anticipated to enhance been certied as a drop-in aviation fuel according to ASTM
the development of synthetic jet fuels, including e-fuels D7566 standards, MTJ-based SAF is currently in the process of
produced via Power-to-Liquid (PTL) processes. obtaining approval through ASTM D4054.17
Projected jet fuel demand at EU airports is anticipated to With availability of FOG feedstocks being a limiting factor,
reach approximately 46 Mt per a by 2030.31 Currently, the the ATJ route and the Fischer–Tropsch (FT) route are expected
annual production capacity of SAF in the EU stands at just over to produce a signicant amount of bio-based jet fuel in the
1 Mt per a.32 With the inclusion of facilities currently under future.51 The FT process, originally developed in Germany for
construction, the estimated SAF production capacity for 2030 in producing liquid transport fuels from coal, is capable of
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the EU is projected to be between 3.5 and 3.8 Mt per a,32,33 transforming synthesis gas, i.e. here a mixture of carbon
potentially aligning with the mandated SAF demand of 6% by monoxide (CO) and H2, into liquid fuels such as SAF.52 Synthesis
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that year. However, to meet the more ambitious targets of 34% gas can either be produced from biological or non-biological
by 2040 and 70% by 2050, signicant increases in production origin.53,54 The bio-based FT process entails gasication of
capacity will be necessary. biomass into synthesis gas before converting it into liquid fuels.
The major SAF production routes have been analysed in Nonetheless, the need for extensive conditioning and cleaning
several recent reviews,6,13,18,29,34–37 evaluating the interaction of the synthesis gas from biomass gasication can limit the
between policy framework, economic considerations, commer- efficiency and commercial feasibility of bio-based FT
cialization status, and technical performance. Reviewing the synthesis.55,56
market for ASTM certied SAF routes of biofuels and e-fuels, FT technology can be integrated into PTL production route,
Detsios et al. concluded that currently feedstocks of biological where synthesis gas is generated from CO2, electricity, and
origins dominate among the various SAF production path- water instead of biogenic feedstocks. However, FT synthesis
ways.18 A more extensive review by Khanal et al. provides faces some challenges regarding syngas generation due to the
a detailed analysis of SAF production via various biofuel high energy intensity of CO2-to-CO-conversion by reverse water
routes.36 gas shi reaction (rWGS) or the low TRL of co-electrolysis.57,58
Among ASTM approved SAF production routes, the hydro- Moreover, its high exothermic heat and complex reaction
processed esters and fatty acids (HEFA) process, currently kinetics present a challenge for direct coupling of the process to
dominates the SAF market with more than 90% of the total uctuating renewable power.59,60
share.29,38 HEFA jet fuel and HVO diesel are produced via While many review articles dealing with the characteristics
hydrotreatment and subsequent isomerization of fats, oils, and of FT synthesis for SAF production are available today,52,53,61,62
greases (FOG), or other bio-oils.39 Recent commercial develop- knowledge regarding the MTJ process chain is still limited. This
ments were made with regard to industrial scale production of review examines the current state of science across each
bio-jet fuel from the Alcohol-to-Jet fuel (ATJ) route with a wide subprocess of the MTJ process chain, focusing on the reaction
range of biogenic feedstocks,40 with a recent demonstration systems, the different catalysts used in each synthesis step and
plant by Lanzajet at a production scale of 30 000 t/a.41 Addi- the variables that impact the jet fuel yield, emphasizing areas
tionally, the ATJ process has been demonstrated using iso- for future research that can be done by the scientic commu-
butanol derived from cellulosic non-edible crops biomass.42 Up nity. It highlights the necessity to develop an integrated process
to date, the ASTM D7566 refers to ATJ that uses ethanol or concept that not only achieves high yields of SAF, but also is
isobutanol as feedstock, while methanol as a feedstock is not economically viable. Based on a systematic analysis of various
included in the ATJ classication.20 process congurations, concepts for an integrated process are
Within Europe, the production of SAF from biological proposed. The review identies key challenges and poses
origins is strictly regulated, as the feedstock use of food and research questions critical for the future technological devel-
food crops in aviation is limited by EU regulation 2023/2405.6,43 opment of the MTJ pathway. Finally, challenges in process
Additionally, the expansion in bio-based jet fuel frequently integration are outlined, offering a perspective for further
prompts concerns regarding food versus fuel and land-use research and development in this eld.
change.18 This underscores the need for further development
of jet fuel as RFNBO. 2 SAF production via methanol
PTL routes, which can lead to the production of electro-
sustainable aviation fuels (eSAF), a type of synthetic aviation The production of SAF from H2 and CO2 via the methanol
fuel produced using renewable electricity, offer compelling pathway involves four main subprocesses: methanol synthesis,
advantages over biofuels due to a greater potential for green- methanol-to-olens (MTO) conversion, oligomerization, and
house gas reduction, as well as a lower land and water hydrogenation.19,63,64
demand.44–46 Currently, the economic viability of these A simplied schematic of the MTJ process chain is shown in
processes is hindered due to the high production costs of green Fig. 2, together with a rough range of the respective process
H2.47 However, it is expected that these costs will decrease with conditions applied and used catalyst types. In a rst step, H2
the improvement of the major electrolysis technologies.48 The and COx obtained from carbon neutral sources, such as
main PTL routes for jet fuel production being discussed today biomass or air, are converted into methanol and water over Cu-
are the FT pathway as well as the methanol-to-jet fuel (MTJ) based catalyst in an exothermic reaction in a temperature and
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Fig. 2Sustainable aviation fuel production from hydrogen and carbon source via the methanol pathway. The grey streams represent potential
by-products that may occur in the process.18,56,57
pressure range of 220–280 °C and 30–80 bar, respectively.58 (5) By optimizing the synthesis conditions, jet fuel derived
Subsequently, the puried methanol is converted into light from methanol could be produced with low levels of aromatic
olens during the MTO synthesis step over Zeotype catalyst at compounds compared to fossil jet fuel, which contributes to
process conditions of 400–500 °C and 1–3 bar.65 The product reduced contrail formation and lessens the adverse climate
stream of the MTO synthesis is quenched, and water is sepa- effects of aviation emissions.78,79
rated and partially recycled to the MTO reactor. C2–C6 olens Each of the individual subprocesses of the MTJ process chain
are separated from lighter and heavier components using are currently operational on industrial scale in various plants
fractionation columns.66–68 In the subsequent oligomerization and reneries.80–82 However, to date, there have been no
step, the chain length of the olens (C2–C6) is increased over commercial scale implementations of specic concepts inte-
solid acid catalyst at synthesis conditions of 200–250 °C and 30– grating the various subprocesses of the MTJ pathway, reecting
50 bar.69 Along the process chain, the olen oligomerization is the relatively low TRL of an integrated MTJ process.17,71
a critical step to obtain hydrocarbons with the desirable Various companies and institutions are working on the
combustion properties in the synthetic jet fuel-range. The process development of MTJ, such as ExxonMobil, UOP and
oligomerization mechanism of ethylene and higher olens Topsoe.83–85 Several research projects are investigating this
differs, which confers complexity to the oligomerization topic, such as SAFari and M2SAF.86,87 Moreover, several techno-
process. This will be discussed further in Section 2.3. The oli- economic analyses have investigated the MTJ process, although
gomerized product is mixed with H2 and hydrogenated over the optimization towards jet fuel mainly includes strong
a reduced metal catalyst at 100–250 °C and 20–50 bar to saturate simplications.49,88–91 A detailed process optimization was
the olenic double bonds.69 The product is cooled and the published by Bube et al., focusing on new modelling approach
excess H2 is recycled back to the xed-bed hydrogenation for the oligomerization of short-chain olens within the
reactor.70 Finally, the jet fuel product, with a typical carbon framework of MTJ.17,90 Scientic studies conducted by Bube
range of mainly C8–C16, is separated from lighter and heavier et al., Saad et al., and Eyberg et al. estimate the production costs
hydrocarbons using fractionation columns.71 of eSAF via the MTJ process between 4.2 and 9.45 EUR per
Especially in the context of PTL, MTJ shows potential for SAF kg.88–90 Eyberg et al. compared the levelized cost of production
production regarding the following aspects: (LCOP) at optimal energy efficiency cases for the FT process and
(1) As methanol can be produced from both CO and CO2, the MTJ process, estimating it to be 8.78 EUR per kg and 9.45
CO2 can be utilized directly without the need of a reverse water EUR per kg, respectively. However, both estimates corresponds
gas shi stage or co-electrolysis.72 to a value of 0.81 EUR per kWh, reecting differences in the
(2) The possibility of dynamic methanol synthesis operation lower heating value (LHV) associated with the respective jet fuel
enables a direct link of renewable energy to jet fuel compositions obtained.89 The Project SkyPower initiative, rep-
production.73–77 resenting multiple stakeholders in the eSAF sector, estimates
(3) The exothermic heat of jet fuel production can be inte- that production costs for eSAF in Europe will range between 5
grated into the process chain to allow reduced heat demands. and 8 EUR per kg by 2030.92 Overall, the estimated production
(4) MTJ can produce jet fuel at high yields with low levels of costs are subjected to varying assumptions regarding feedstock
byproduct formation.17,71 This is an advantage over FT, where costs, plant capacity and the boundary conditions, with water
the formation of light hydrocarbons, such as, methane can be electrolysis and CO2 capture accounting to 74–79%.88–90 More-
signicant. over, it is important to note that these studies underly
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systematic uncertainties caused by technical assumptions, such a high similarity to conventional syngas with an optional
as conversions, selectivities and chain growth probability.17,90 addition of surplus electrolytic H2.72,104–106 Thus, this process is
The following sections review the feedstock, catalyst, reac- advantageous with regard to the supply of existing methanol
tion networks, process layouts and products of each subprocess synthesis plants.98 When the gasication is performed with pure
within the MTJ route, with the objective of enhancing the O2 instead of air, the N2 content in the syngas can be reduced,
selectivity towards jet fuel range hydrocarbons. offering an advantageously low inert gas content.107
By application of various reforming technologies, a CO and
H2 containing syngas can be produced from
2.1 Methanol synthesis biomethane.103,108–111 Biogenic CO2 can be captured via amine
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With a global production capacity of nearly 140 Mt per a in 2022, wash from fermentation processes or combustion processes.112
thermochemical methanol synthesis, implemented by BASF in However, in this case surplus H2 must be supplied to obtain
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1923, is today one of the most important chemical production a syngas suitable for methanol synthesis. In any case, bio-based
processes.93,94 Methanol is used as a platform molecule to syngas contains catalyst poisons such as chlorine or sulfur-
produce fuels and chemicals, with the main consumption containing compounds.72,110,113 Thus, these trace compounds
driven by China.95 Besides traditional derivatives like formal- need to be removed from the syngas before entering the
dehyde, methyl tert-butyl ether (MTBE) or acetic acid, methanol synthesis process.
is today widely used for the production of olens and propylene Alternatively to biomass, CO2 can be obtained from the
by MTO or methanol-to-propylene (MTP).96,97 Due to the xed atmosphere or sea water by direct air capture (DAC) or direct
demand for RFNBO by the EU, an additional path of utilization ocean capture (DOC), respectively.114–118 While these technolo-
for carbon neutrally produced methanol is expected to emerge gies still need to be scaled up to reach reasonable costs, they
by the MTJ process.43 Thus, this technology will be reviewed in offer the potential of providing CO2 at any location.116
the next subsections to point out obstacles to be addressed by In the context of carbon capture and utilization (CCU),
the scientic community to ensure a reliable scale up of thermo- carbon oxides for methanol synthesis can also be obtained from
chemical SAF production via methanol. fossil or mineral sources, e.g. from cement plants,119,120 steel
2.1.1 Feedstocks. Methanol can be formed from synthesis mills121–124 or waste incineration plants.125,126 While these carbon
gases (syngases) containing H2, CO and CO2 covering a wide oxides are comparatively easy to exploit due to their high
concentration range.98 Importantly, the CO/CO2 ratio in the availability and concentration at the respective point source,
syngas as one of the most relevant parameters for the descrip- their utilization has to be evaluated carefully with regard to
tion of methanol synthesis is directly related to the feedstock international emission reduction targets.102
and its processing method.72,98 If H2 cannot be obtained by thermochemical methods,
Today, the main feedstocks for methanol production are current state of the art involves electrochemical H2 production
natural gas and coal, providing a CO-rich synthesis gas for by electrolysis with four major technologies being proton
methanol synthesis by either reforming or gasication tech- exchange membrane electrolysis (PEMEL), anion exchange
nologies.93 Depending on the feedstock applied, these processes membrane electrolysis (AEM), alkaline electrolysis (AEL) or
generate cradle-to-gate CO2 emissions between 0.85 tCO2,eq/ high-temperature electrolysis (HTE).127,128
tMeOH and 2.97 tCO2,eq/tMeOH for a basic natural gas or coal based 2.1.2 Catalyst and reaction network. Aer advanced gas
process, respectively.99,100 Assuming thermal treatment of cleaning techniques for the removal of sulfur species from the
methanol end-of-life additional 1.38 tCO2,eq/tMeOH would be syngas were implemented in the 1960s, Cu/ZnO/Al2O3 catalysts
emitted through a stoichiometric oxidation. Thus, to decrease were enabled for their industrial application.129 Despite ongoing
the CO2 emissions caused by methanol production and utili- research for more stable and active catalysts based on different
zation, carbon neutral production routes including carbon metals such as indium or noble metals,130–132 this catalyst
cycles need to be established.101 Biogenic or atmospheric carbon system remains the industrial standard today.133,134
oxides reacted with carbon-neutrally produced H2 by water Methanol synthesis on conventional catalysts can be
electrolysis is currently seen as a promising pathway to satisfy described macroscopically by CO hydrogenation, CO2 hydro-
the methanol world market in the future.102 Whilst these Power- genation and water–gas-shi reaction (WGS):
to-Methanol (PTM) processes offer the potential of carbon
neutrally produced methanol, the partial or entire replacement CO2(g) + 3H2(g) % CH3OH(g) + H2O(g) DH0R = −50 kJ mol−1
of CO by CO2 in the syngas entails disadvantages originating
from the high chemical stability of CO2 in comparison to CO CO(g) + H2O(g) % CO2(g) + H2(g) DH0R = −41 kJ mol−1
and the formation of water as by-product (see Section 2.1.2 for
CO(g) + 2H2(g) % CH3OH(g) DH0R = −91 kJ mol−1
more details).
Due to the high feedstock availability, biomass has a large
potential for the production of green fuels and chemicals.93,103 In this reaction network, CO hydrogenation can be dened
Depending on the way of processing, biomass can deliver both, as the combination of CO2 hydrogenation and WGS. Currently,
pure CO2, e.g. in case of fermentation, or a syngas containing this combination is considered as the main source of methanol
CO2, CO, H2 and nitrogen (N2), e.g. in case of gasication. In over conventional Cu/ZnO/Al2O3 methanol synthesis catalysts
case of a biomass gasication, the syngas produced can offer
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by various studies,135–138 while the actual mechanistic nature of either by interstage absorption,175 adsorption176,177 or
methanol synthesis is still debated.139–141 Due the equimolar condensation122,178–183 were identied as promising pathways.
formation of water, equilibrium conversion of CO2 hydrogena- Recently, in situ removal of the products inside the reactor by
tion is lower compared to CO hydrogenation.142,143 Moreover, sorption or membrane separation has gained attention in this
water was shown to be responsible for inhibited methanol context.184–189 However, these technologies have not yet been
reaction kinetics144 and accelerated deactivation of the demonstrated on a larger scale. Another way to tackle the
catalyst.145–147 As increased CO2 contents in the synthesis gas thermodynamic and catalytic challenges of CO2-based meth-
enhance water formation along the reactor by both CO2 anol synthesis is the so-called CAMERE process coupling an
hydrogenation and reverse WGS (rWGS), many studies have upstream rWGS stage with subsequent methanol synthesis
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dealt with enhancement of the catalyst for CO2-based methanol from CO enriched syngas as proposed by Joo and coworkers in
synthesis.148–151 Switching from the Al2O3-support towards ZrO2 1999.190,191 Similar approaches were considered as an option
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or Ga2O3 is most widely applied to stabilize the Cu species on within patent literature.192,193 However, when stable catalysts for
the catalytic surface.152–154 CO2-based methanol synthesis become industrially available,
For the kinetic description of methanol synthesis, plenty these concepts could become obsolete.
different kinetic models have been proposed in scientic Another important point differing between fossil and
literature155–161 among which the model by Vanden Bussche “green” methanol synthesis relates to the process dynamics.
et al.155 and Graaf et al.156 have gained most popularity in the While a fossil-based synthesis is usually operated at steady
scientic community. However, due to different reaction state,111,194–196 coupling of uctuating renewable energy sources
conditions, catalysts and mechanistic assumptions which these to methanol synthesis can lead to the demand for dynamic
models are based on, they were proven to show strong devia- process operation. Here, one main challenge lies in balancing
tions with regard to product formation and the axial tempera- the increased equipment cost and possible difficulties
ture prole inside the reactor.162–166 regarding heat integration for the dynamic methanol plant with
2.1.3 Process layout and reactors. Regarding reactor design the advantages of decreased H2 buffers and an improved utili-
for conventional methanol synthesis, multiple approaches are zation of renewable power.58,73–76,113
known in literature.58,167–169 Among the common reactor types, 2.1.4 Products. With the effects of WGS and rWGS, i.e. CO2
the adiabatic multi bed reactor with intercooler or quench and CO formation, respectively, excluded, commercial Cu/ZnO/
injection of fresh syngas as well as the steam cooled tubular Al2O3 catalysts show a carbon selectivity towards methanol
reactor and the gas-gas-cooled reactor are most widely >99%.72,197,198 Industrially, methanol purity is classied by
applied.143 Fig. 3 shows a simplied process ow diagram of chemical grades199,200 usually achieved by distillation of raw
methanol synthesis process including a single stage crude methanol.58,113,201 However, in case of directly linked down-
methanol distillation and a light gas recovery to decrease losses stream processes utilizing methanol, the degree of necessary
of dissolved gases.170 purication needs to be dened individually since the removal
Depending on plant size, syngas composition and econom- of water might not be necessary or can be implemented more
ical aspects, many combinations of different reactor types were efficiently in downstream process equipment.202
studied in both, scientic and patent literature.171–174 To over- The main side products documented in literature are
come the thermodynamic limitation of CO2 hydrogenation, dimethyl ether (DME), formic acid, methyl formate, methyl
removal of water and/or methanol from the reaction mixture acetate, higher alcohols (predominantly ethanol), ketones and
paraffins.171,201,203,204 In a recent study, Nestler et al. analysed the
side products present in liquid crude methanol samples
produced from a variety of different process conditions, and
compared those to literature data.204 In this work, the CO/CO2
ratio in the reactor feed was identied as the main parameter
determining side product formation, with an overall tendency
to decrease as CO2 content increases. From the experimental
data obtained, a simplied correlation was derived between the
CO/CO2 ratio and the amount of side products. However, the
authors indicated further research demand in this eld to
obtain a better understanding of the formation mechanisms for
different side products, as these could affect the downstream
process.
In the context of the MTJ route, the degree of purity neces-
sary for a stable operation of the downstream process, i.e. MTO
synthesis, should be investigated further, as a simplication in
methanol purication can decrease the energy demand of the
process chain and offer the potential to for new integrated
process schemes.205
Fig. 3 Simplified process flow diagram of the methanol synthesis.145
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2.2 Methanol-to-olens conversion pure methanol and DME as feedstocks, and concluded that
DME feed results in a higher catalytic activity as well as lower
The methanol-to-hydrocarbons (MTH) process was rst devel-
selectivity for aromatic products and ethylene.218 Additionally,
oped by Mobil Oil Corporation (today ExxonMobil) in the
Cordero-Lanzac and co-workers found that the DTO process
1970s.206 They claimed that a feed of lower alcohol and/or ether,
produces less water and is less exothermic compared to the
such as methanol, dimethyl ether, or an equilibrium mixture of
MTO process.219 Due to these promising ndings, the kinetic
both, can be converted into a mixture of C2–C5 light olens
and technical impacts of DME cofeeding to olen synthesis
when contacted over a shape selective aluminosilicate ZSM-5
zeolite catalyst in a xed-bed reactor. These light olens can should be evaluated in the context of SAF production in future
work.
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further react to produce paraffins, aromatics, naphthenes and
2.2.2 Catalyst and reaction network. Microporous zeolites
higher olens, as illustrated in Fig. 4.207
or zeotype catalysts containing Brønsted acidic sites are used in
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This discovery opened the possibility to produce a range of
the MTO synthesis with H-ZSM-5 and the SAPO-34 being the two
synthetic hydrocarbons through various processes classied by
most prominent catalysts due to their light olen selectivity.220
their targeted product. Thus, MTH process can be subdivided
The topology and acidity of the zeolite catalyst signicantly
into methanol-to-gasoline (MTG),208 methanol-to-aromatics
inuence the selectivity of MTO synthesis.221–223 Besides H-ZSM-
(MTA),209 MTP,210 and MTO processes.211 Reviewing the MTO
synthesis within the MTJ route is crucial for optimal coupling of 5 and SAPO-34, other catalysts that have been studied for MTO
the subprocess for a maximized jet fuel yield. By examining the synthesis include H-ZSM-11, H-ZSM-22 and H-ZSM-48.224
Notably, a high selectivity to C3+ olens has been reported in
state-of-science of the MTO process, opportunities for innova-
MTO over 1-D framework zeolites, such as H-ZSM-48 and H-
tion and efficiency improvements in SAF production can be
ZSM-22.223,225 High C3+ olen yields are particularly advanta-
identied.
geous for maximizing the jet fuel selectivity within the MTJ
2.2.1 Feedstock. Coupled with state of the art upstream
route. For further details on each zeolite topology, readers can
processes, MTH processes offer a versatile method to produce
refer to the International Zeolite Association (IZA) database.226
hydrocarbons from a wide range of carbon sources, e.g. natural
gas, coal, or biomass.82 Thus, the MTH synthesis can also be Along with topology, the product selectivity of the zeolite
applied to produce renewable synthetic fuel when “green” catalyst in MTO is inuenced by concentration, distribution
and strength of both Brønsted acid sites (BAS) and Lewis acid
methanol is used as a feedstock.80 Aside from methanol, water
sites (LAS).227 BAS density affects the catalytic activity and
can be fed into the reactor to reduce the temperature increase
catalyst lifetime.228 It is determined by the framework
caused by the exothermic MTO synthesis, which in turn inu-
aluminium content of the zeolite and can, thus, be increased by
ences product selectivity and catalyst activity.212 High water
decreasing the Si/Al ratio. A high BAS density confers a high
contents of e.g. 74–80 mol% in the feed are known to increase
activity, but facilitates successive reactions along the diffusion
olen selectivity, decrease formation of aromatics and paraf-
ns, as well as reduce coke formation on the catalyst pathway, promoting aromatization and coking, whereas lower
surface.213–215 Thus, these results indicate that the utilization of BAS densities favour methylation and cracking reactions.229 In
addition to BAS density, the distribution of the BAS within the
crude methanol could be a promising option to decrease the
framework inuences the reaction pathway and the deactiva-
aromatic content in SAF produced via the MTJ pathway.
tion by coke formation, thereby affecting olen selectivity and
DME formed as an intermediate product in the MTO
catalyst lifetime.230 Hydrogen transfer reactions can be sup-
synthesis can be converted to hydrocarbons in the DME-to-
pressed by reducing the Brønsted acidity of the ZSM-5 zeolite,
Olens (DTO) process.216,217 Martinez-Espin et al. compared
e.g., by incorporating a Ca promoter.231 Alkaline earth metal-
promoted ZSM-5 zeolites, such as Ca-ZSM-5, can exhibit
a lower activity, but a considerably enhanced catalyst lifetime,
increased propylene selectivity and decreased aromatics selec-
tivity in MTO, compared to unpromoted zeolites.221,227,231–233 The
promotion with alkaline earth metals decreases the BAS
concentration and results in the formation of LAS, which can
explain the difference in activity and selectivity. With LAS
impacting the reactant adsorption and the stability of transition
states on vicinal BAS, the decreased aromatics selectivity can be
attributed to a difference in the reactivity of the BAS, in addition
to a decreased BAS concentration.221 As described by Bailleul
et al.,221 the LAS strength is decisive for the reactivity of the
neighbouring BAS, with Ca and Mg promoted zeolites offering
a compromise between activity and selectivity. In addition to
modifying the acid properties of the zeolite, Ca promotion alters
Fig. 4 Formation and consumption of the species involved into MTO the effective pore geometry and decreases the micropore
synthesis over residence time (reproduced from ref. 181 with volume, which has been suggested to contribute to the
permission from Elsevier, copyright 1999). composition of the hydrocarbon pool.232,233 In conclusion,
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selection of a zeolite with an appropriate topology and tuning 8% of the methanol feed, reduces the turnover capacity of the
the ratio, strength, concentration, and distribution of BAS and catalyst, and necessitates high-temperature regeneration,
LAS in the MTO catalyst is crucial to maximize the desired light leading to a permanent structural degradation of the
olen yield (C3–C6) and catalyst lifetime. catalyst.253–256 H-ZSM-5 demonstrates a higher resistance to
Despite more than 40 years of research on MTO synthesis, coking compared to SAPO-34.245 Unlike deactivation caused by
more than 20 different models for the reaction mechanism have zeolite material degradation or dealumination, deactivation
been proposed.207,234–241 Modelling of the MTO reaction mech- due to coke deposits can be reversed by subjecting the catalyst
anism remains challenging due to the complex stoichiometry to a thermal treatment at temperatures between 500 °C and
and the large number of elementary reactions. Reaction 600 °C and an atmosphere with a low oxygen concentration, to
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conditions signicantly inuence the product distribution and restore the accessibility of the active sites.257 The deactivation
catalyst lifetime in MTO synthesis, as each elementary reaction model by Janssens et al. assumes that the deactivation rate is
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may have varying orders and activation energies.242–244 Today, directly proportional to methanol conversion and that the
the dual-cycle mechanism (DCM) is the most widely accepted reaction between methanol and aromatic species results in coke
for the mechanistic description of the MTH reaction.245,246 As formation.257 The model demonstrates that the catalyst's active
schematically shown in Fig. 5, it suggests an autocatalytic sites gradually become covered with hydrocarbon pool species,
olenic and aromatic cycle to run in parallel.247 The DCM leading to subsequent coke deposition. According to Paunović
involves six key categories of chemical reactions, i.e., methyla- et al., the rate of coke formation also depends on the concen-
tion and cracking of olens, methylation and dealkylation of tration and nature of Brønsted acid sites (BAS), as well as the
aromatics, cyclization and hydrogen transfer, with their presence of Lewis acid sites (LAS) and framework defects.253
respective rates determining the product distribution of the Despite being present in low concentrations during MTO
overall synthesis.247,248 It has been demonstrated that one of the synthesis, formaldehyde contributes to the coke-induced deac-
two cycles can be promoted while suppressing the other one by tivation of the zeolite catalyst.218 Liu et al. showed that formal-
co-feeding species participating in the respective autocatalytic dehyde is predominantly formed at the induction period and
cycle. According to Sun et al., co-feeding of olens (such as exerts a detrimental inuence on the catalyst lifetime, by facil-
propylene, butylene, pentene and hexene) or aromatics (such as itating the formation of non-olenic products as dienes, poly-
benzene, toluene and xylenes) promotes either the olenic or enes and aromatics, which act as coke precursors.258 To extend
aromatic cycle.249,250 A small olen recycle to the MTO unit could catalyst lifetime, it is relevant to develop strategies to effectively
therefore be benecial within the MTJ process chain. reduce the concentration of formaldehyde by inhibiting its
Catalyst coking is a key challenge in MTO synthesis, as coke formation or facilitating its rapid decomposition. Such strate-
deposition on the outer surface and internal channels of the gies include MeOH dilution,259 olen co-feeding,250 products
zeolite is the primary cause for deactivation in MTO back-mixing,256 and substituting MeOH feedstock by DME.218
synthesis.251,252 Moreover, coke formation can consume up to
Fig. 5 Dual cycle mechanism of the MTO synthesis (reproduced from ref. 244 with permission from American Chemical Society, copyright
2013).
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Kinetic modelling of MTO synthesis is challenging due to the 2.2.3 Process layout and reactors. ExxonMobil combined
complex reaction network involved. Several studies have inves- the MTO process with Mobil's Olens to Gasoline and Distillate
tigated MTO synthesis and kinetic modelling using different (MOGD) process. Both processes use the medium pore zeolite
feedstocks, such as pure methanol or methanol co-fed with H-ZSM-5 catalyst, to convert methanol into gasoline and other
olens, over different catalysts and process distillate fuels, including jet fuel and diesel.270 Commissioning
conditions.64,79,218,247–264 of a plant in New Zealand with an annual production capacity of
Table 2 summarizes the parameter ranges related to feed 600 000 tons of gasoline utilizing this process marked the
composition, synthesis conditions, and catalysts in selected beginning of the commercial use of methanol for fuel produc-
experimental and kinetic investigations. Quantitative data on tion in 1985.81 Topsoe (previously Haldor Topsøe) developed
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selectivity and yield are excluded, as these studies were not a process integrating gasoline production with the synthesis of
conducted within the framework of the MTJ process, thus methanol and DME from a feedstock of syngas within a single
Open Access Article. Published on 27 May 2025. Downloaded on 7/9/2025 10:26:08 AM.
avoiding misinterpretation. Most published kinetic models on synthesis loop, in a process called Topsøe Integrated Gasoline
MTO synthesis are based on simplied assumptions or are Synthesis (TIGAS Process).271 These two processes focus on
targeting selective propylene production, which is not the a high yield of gasoline, while for the MTJ process, a high yield
primary focus of the MTO synthesis within the MTJ route. A of light olens is desired in the MTO subprocess.
signicant shortfall of several kinetic models is the lumping of Today, the UOP/INEOS MTO process and the Lurgi MTP
lower olens into one lump or lumping methanol and DME process are two major technologies dominating the MTO
together, which affects the robustness of the models due to the market, demonstrating a high TRL for the production of light
different formation mechanisms and reactivities of each olens from methanol. A comparison between available data of
component. Another challenge is understanding the interaction the Lurgi MTP and UOP/INEOS MTO processes is shown in
between water and zeolite and its effect on the kinetics, as water Table 3, as they show suitable olen target product for the MTJ
acts both as diluent and a competing adsorptive. Moreover, the process.251
catalytic activity decreases due to deactivation by coke deposi- The UOP/INEOS MTO process, developed in the 1990s by
tion, which should be considered within the MTO kinetics. UOP and Norsk Hydro (now INEOS) and depicted in Fig. 6 uses
Additional research is necessary to develop kinetic models the SAPO-34 catalyst in a uidized bed reactor coupled with
optimized for the MTO process conditions relevant to MTJ a uidized-bed regenerator. The process is capable of using
applications, as extrapolating beyond experimentally investi- crude methanol, grade AA methanol or DME as a feed.272 The
gated conditions could result in unrealistic model predictions. feed is evaporated and introduced into the MTO reactor, oper-
ating in the vapor phase at temperatures between 340 °C and
Table 2 Summary of selected MTO experimental and kinetic investigations in literature at reaction pressure of 1 bar
Temperature WHSV
Feed (°C) Catalyst Si/Al (h−1) Olens yield Objective of study Reference
MeOH 500 Ca-modied 40 8 C2 olens = 14% Aromatic cycle suppression 231
ZSM-5 C3 + C4 olens = 82% in MTO reaction
MeOH 520 Ca-modied 89.8 4.2 C3 olens = 49% Enhance catalytic stability & 260
ZSM-5 propylene selectivity
DME 400 ZSM-5 40.2 6 C2 − C11 olens = 26% Aromatic cycle suppression 261
ZSM-48 73.5 1.5 C2 − C11 olens = 90% in DME to hydrocarbons reaction
ZSM-22 50.4 0.3 C2 − C11 olens = 50%
MeOH 400–550 ZSM-5 25.4 5.8 C2–C4 olens Kinetic modelling (seven lumps) 262
MeOH 300–450 ZSM-5 24 2.7–25 C2–C3 olens Role of water on MTO kinetic 263
modelling
MeOH 360–480 ZSM-5 200 — C2–C8 olens Single event kinetic modelling 264 and
265
MeOH 480 ZSM-5 200 5.3 C3 olens = 81.6% MTP monolithic catalyst 266
MeOH + C4H8 investigation/kinetic modelling
MeOH 420–500 B-modied 180 2.0–9.4 C3 olens Methanol and olens co-feeding 267
MeOH + C4H8 C5H10/ ZSM-5 investigation/kinetic modelling
C6H12
MeOH + C3H6 400–490 ZSM-5 200 — C2–C7 olens Methanol and olens 268
MeOH + C4H8 co-conversion/kinetic modelling
MeOH + C5H10
MeOH + C6H12
MeOH + C3H6 400–490 ZSM-5 200 — — Paraffins and aromatics side 269
MeOH + C4H8 reactions/kinetic modelling
MeOH + C5H10
MeOH + C6H12
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Table 3 Comparison aspects between the industrial process of Lurgi pre-reactor, as shown in Fig. 7.210,279 The resulting mixture of
MTP and UOP/INEOS MTO251 methanol, water, and DME is then sent to the MTP reactor
premixed with steam and recycled olens. The process uses
MTP (Lurgi) MTO (UOP/INEOS)
xed-bed reactors loaded with a H-ZSM-5 catalyst, offering
Catalyst H-ZSM-5 H-SAPO-34 lower investment costs compared to processes using uidized-
Temperature, °C 450 350 bed reactors.280 However, the xed-bed reactors are less effec-
Pressure, bar 1.5 2 tive in managing the heat generated by the highly exothermic
Reactor Fixed bed Fluidized bed
Recycle Water, olens C4+, C2 DME
reaction compared to the uidized-bed reactor.281,282 The MTP
Productsa, wt% process produces propylene, and gasoline as a by-product, with
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Propylene 72 42 a methanol + DME conversion of more than 99%.210 The reac-
Ethylene — 39 tion section consists of three parallel adiabatic quench bed
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C5+ 23 5 reactors to facilitate intermittent catalyst regeneration aer
a
Composition can vary. 500–600 h of time on stream (TOS), with one reactor on standby
for coke removal by introducing air.279 Each reactor is equipped
with ve or six catalyst beds with feed injection between beds to
540 °C and pressure between 1 bar and 3 bar.273 SAPO-34 control reaction temperature.279,283 The process runs slightly
exhibits high selectivity towards ethylene, with the main prod- above atmospheric pressure (1.3 to 1.6 bar), with steam added
ucts of the process being ethylene and propylene at a selectivity to the feed (0.5–1.0 kgsteam kgmethanol−1), and at reactor inlet
up to 80% and nearly complete methanol conversion.274–277 A temperature between 400 °C and 470 °C.65,273 Olens such as C2
portion of the catalyst from the uidized-bed reactor is and C4–C6 are recycled to the reactor to maximize the propylene
continuously regenerated in the regenerator, allowing the ex- yield.284 Solutions for further increasing the propylene selec-
ibility to adjust the operating temperature by recovering heat tivity and prolonging the catalyst lifetime in MTP were proposed
from the exothermic MTO reactor.275 The reactor temperature is by UOP in their MTP patent family centred on moving bed
crucial to adjust the propylene-to-ethylene ratio, as elevated reactor technology.285–287
temperatures favour higher propylene yields and coke forma- In the context of the MTJ process, MTO aims to produce
tion.272 The heat of the exothermic synthesis is removed by a mixture of C2+ olens,17,71,91 in contrast to Fig. 6 and 7, which
steam generation and cooling coils in the uidized bed reactor. reduces purication requirements and simplies the separation
Effluent of the reactor is condensed to separate water. The dried process.
gases are subsequently compressed and processed in a down- Topsoe led four patents related to MTJ in 2021,83,288–290 out
stream fractionation.274 Similar technologies have been devel- of which three directly focus on the MTO subprocess. Separate
oped in China by Dalian and Sinopec using catalysts containing applications were led for MTO synthesis catalysed by zeolites
SAPO-34 in a uidized bed reactor.272,273,278 with 1-D 10-ring pore structures, such as the *MRE, MTT and
Lurgi GmbH developed an MTP process where methanol TON families,289 and by zeolites with 3-D 10-ring pore struc-
feedstock rst is converted into DME and water in an adiabatic tures, such as the MFI family.288 The MTO subprocess outlined
Fig. 6 Simplified process flow diagram of the UOP/INEOS MTO process.243,258
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Fig. 7 Simplified process flow diagram of the Lurgi MTP Process.184,243
by Topsoe is claimed to produce predominantly C4+ olens. The 2.3 Oligomerization
C4+ olen selectivity, which may exceed 80 wt%, can be attrib- The oligomerization process involves increasing the olen
uted to the combination of the catalyst, reactor conguration, chain length by coupling of light olen monomers.292 Within
and reaction conditions.288
the MTJ process, the light olens produced in the MTO unit,
Topsoe's MTO synthesis is preferentially carried out in two
predominantly ethylene, propylene, and butylene, are converted
sets of parallel xed bed reactors, operated at reaction
into longer-chain hydrocarbon (C8–C16) suited for jet fuel
temperatures below 400 °C and pressures up to 25 bar.83,288–290
production.293–295 On the industrial scale, oligomerization of
Hydrogen transfer reactions, typically promoted at elevated
light olens is already established for the production of petro-
pressures, may be mitigated by operating temperatures below
chemicals and various fuels, including polymeric gasoline (C5–
400 °C and by limiting the methanol partial pressure by feed C10) and diesel (C10–C20).296,297 Despite being a mature tech-
dilution to, e.g. 5 or 10 vol%.83,288–290 Furthermore, the relatively nology, oligomerization processes are constantly advancing
mild reaction temperature may suppress monomolecular
through ongoing research aimed at enhancing catalyst selec-
cracking of higher olens.291 Additional factors suggested to
tivity and lifetime, investigating new feedstocks, and improving
contribute to the C4+ olen selectivity include the recycle of C3−
both material and energetic efficiency.294 However, research
olens, and operating the two reactor sets at a WHSV of 6–10
targeting to improve the selectivity of the oligomerization of
h−1.83,288–290 The patents claim that the high-pressure operation
mixed light olens towards jet fuel is still scarce.
of MTO bridges the pressure gap between the MTO and oligo-
Product distribution and selectivity of the oligomerization
merization subprocess (Fig. 2), reducing the intermediate process are signicantly inuenced by the feed composition.
compression demand and results in energy savings and Oligomerization of various olenic feedstocks has been inves-
a simplied process.83,288–290
tigated in literature, each exhibiting distinct oligomerization
2.2.4 Products. In the context of the MTJ route, the MTO
pathways and selectivity.293,298–301 This section focuses on the
synthesis targets to produce a distribution of C3–C6 olens.
oligomerization of olen fractions ranging from C2 to C6, which
Alongside the C3–C6 olens, the ethylene fraction produced
are relevant to the MTJ pathway due to their prevalence in the
could be either partially recycled back to the MTO reactor or
MTO product.
directed to the subsequent oligomerization subprocess. The
2.3.1 Catalyst and reaction network. Table 4 provides an
differences between ethylene oligomerization and C3–C6 olens overview of different experimental oligomerization studies,
oligomerization will be addressed in the following section. The including their respective feedstocks, product distributions,
usage of an H-ZSM-5 catalyst in a xed bed reactor is expected to
catalysts, and synthesis conditions.19,297,302–309 Quantitative data
yield a more favourable distribution of C3–C6 olens compared
on selectivity and yield are excluded, as these studies were not
to the SAPO-34 catalyst in a uidized-bed reactor. To enhance
conducted within the framework of the MTJ process, thus
the jet fuel yield from the MTJ route, it is essential to minimize
avoiding misinterpretation.
the formation of aromatic and paraffinic byproducts during the
Advances in the oligomerization of light olens for synthetic
MTO synthesis. Investigation on the impact of oxygenates,
fuel production have been made since UOP developed the rst
water and aromatics on the oligomerization is still scarce. This industrial catalyst in 1935, i.e. silica-supported solid phosphoric
should be addressed by further research. Co-feeding a portion acid (SPA).297 However, SPA catalyst faced challenges such as
of the light olens product as a recycle stream into the MTO
limited water tolerance, a short catalyst lifetime, and environ-
reactor could suppress the aromatic cycle.249,250
mental concerns for its disposal, in addition to a low
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Table 4 Summary of selected oligomerization experimental investigations in literature
Olen feed Temperature (°C) Pressure (bar) Catalyst Si/Al WHSV (h−1) Target olens products Reference
C2H4 120 50 Ni/SiO2–Al2O3 0.6 8 C6–C12 302
C3H6 270 40 Ni/H-ZSM-5 25 4.03 C6–C18+ 303
C3H6 200–274 1 H-ZSM-5 12–140 — C6–C12+ 304
C3H6 210–250 2.2 H-ZSM-5 13 — C4–C9+ 305
C4H8 175–325 1.5 H-ZSM-5 30–180 5.6–112 C8–C12 306
C2H4 200–450 1 H-ZSM-5 30 — C2–C8 307
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C3H6 H–Na-ZSM-5
C4H8
C2H4 120 16–32 Ni/SiO2–Al2O3 — 4 C6–C13+ 308
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C3H6
C4H8
C3H6 200–250 40 Pristine ZSM-5 18 1–8 C3–C12+ 309
C6H12 Meso-ZSM-5 12.8
C3H6/C3H8 100–200 20–40 Meso-SiO2–Al2O3 — 1–20 — 297
C3H6/C4H8 140–260 13.8 H-ZSM-5 23 1.1 C6–C12+ 19
H–Y 5.2
H-beta 20
Amberlyst-36 —
Purolite-CT275
—
productivity and corrosion issues.310 Regarding current catalyst dimerization and oligomerization mechanisms over nickel-
research, it is observed that studies can be categorized into two based catalysts.293,317 Product selectivity following a Schulz–
main categories: Flory distribution, as well as product spectra deviating from this
(1) Ethylene oligomerization over transition metal distribution, have been reported in literature, depending on the
catalysts.293,311 catalyst and applied process conditions.302,311,316,322 For example,
(2) Oligomerization of higher olens such as propylene and Betz et al. demonstrated that ethylene oligomerization over Ni/
butylene over acidic catalysts.294,312,313 SiO2–Al2O3 catalysts predominantly produces C6, C8, C10 and
The difference is attributed to the distinct oligomerization C12 fractions under conditions of 120 °C and 50 bar ethylene
mechanism operative over the catalyst, namely metal-catalysed partial pressure, and a space velocity of 8 h−1.302
1,2-insertion and Brønsted acid-catalysed oligomerization Oligomerization of the ethylene fraction produced during
involving carbenium intermediates.294 Ethylene oligomerization the MTO process is crucial for enhancing the carbon efficiency
is not favourable over solid acid catalysts due to an unstable and jet fuel selectivity of the overall MTJ process. There are two
primary carbenium intermediate.69 Obtaining jet fuel range main approaches to convert ethylene into jet fuel range olens:
olens via a single-stage oligomerization of ethylene-containing (1) The two step approach based on dimerizing or trimeriz-
olen feedstocks derived from MTO, is therefore challenging. ing ethylene into an intermediate olen, e.g. butylene and
Ethylene oligomerization has been investigated over a range hexene, in a rst reactor, followed by acid-catalysed oligomeri-
of homogenous and heterogenous transition metal zation of the produced C3+ olens to jet fuel range olens in
catalysts.295,314–318 Among catalysts for ethylene oligomerization, a second reactor.319,323,324
nickel-based catalysts have received the most attention in both (2) The direct oligomerization of ethylene which is charac-
academic and industrial applications, due to their activity, terized by a low selectivity and requires substantial recycling
selectivity, stability, and low cost.295 The performance of nickel- streams, making it economically less favourable than the two
based catalysts is largely determined by the number of acces- step approach.325
sible active sites. With the co-existence of several Ni species in Oligomerization of C3–C6 olens has been investigated in
heterogeneous Ni-based catalysts, the exact chemical nature of literature over various heterogenous solid acid catalysts,
the active site is debated in the scientic community.293,317 As including zeolites (e.g., H-ZSM-5, H-beta),299,326 amorphous
discussed by Olivier-Bourbigou et al.,293 experimental evidence silica–alumina (ASA, SiO2–Al2O3),327 sulfonic acid polymeric
has been presented both for Ni(I) species, (coordinatively resins (e.g., Amberlyst),302,328 and SPA.294,329 Among these,
unsaturated) Ni(II) species, as well as Ni(I)/Ni(II) redox shuttles. zeolites and sulfonic resins have been extensively studied for
The acid properties and morphology of the catalyst support converting olens to fuel-range hydrocarbons.19 Zeolites are
is likewise of importance, with factors such as the prevalence, favoured for operations at increased temperatures of about
density and strength of Brønsted acid sites and the porosity 250 °C, facilitating multiple reaction types including oligo-
affecting the structure, carbon number distribution, and the merization, disproportionation, cracking, and isomerization.19
stability of the resulting oligomers.319–321 Reviews by Finiels et al. Notably, the H-ZSM-5 zeolite is commonly used for light olen
and Olivier-Bourbigou et al. provide detailed discussions on the oligomerization due to its higher thermal stability compared to
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polymeric resins and suitable operational temperature range catalysts, such as the mean pore size and pore size distribution,
between 200 °C and 300 °C.292,328 This particular temperature plays a role in oligomerization reactions. A study by Monama
range allows for secondary reactions like disproportionation, et al. on desilicated ZSM-5 reveals that increased mesoporosity
cracking, and isomerization, supporting the production of enhances the accessibility to acid sites, and improves the olig-
branched longer-chain hydrocarbons ideal for jet fuel.19 Saave- omerization activity for 1-hexene and propylene.309 Larger pores
dra Lopez et al. investigated the oligomerization of propylene/ in beta zeolite and desilicated ZSM-5, compared to small-sized
isobutylene over H-Beta zeolite at a temperature range of 140– pores of ZSM-5, improve access to acid sites for larger mole-
260 °C.19 They observed that higher oligomerization tempera- cules and facilitate the desorption and diffusion of reaction
tures result in higher conversion of propylene, but with products.309,335 Thus, mesoporosity not only facilitates the
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a decreased yield of jet fuel distillate due to secondary diffusion of reactants and products, but also promotes the
cyclization/isomerization, hydrogenation, and cracking formation of longer chain hydrocarbons and extends catalyst
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reactions. lifetime.309,336,337 Bickel and Gounder showed that propylene
Mechanistically, Brønsted acid catalysed olen oligomeri- dimerization rates in H-ZSM-5 zeolites decrease with larger
zation is initiated by the protonation of olen by a Brønsted acid crystallite sizes, highlighting the importance of diffusion limi-
site, forming a carbenium intermediate, as described in tations and the impact of internally formed organic phases
Fig. 8.305,330 The carbenium species undergo transformations within micropores.338
like hydride shis, oligomerization (alkylation), methyl shis, Modication of the oligomerization catalyst, by alteration in
and protonated cyclopropane (PCP) branching, and are even- composition, structure, and acidity, can impact the catalyst
tually reverted to olens through deprotonation.331,332 Oligo- performance.339–341 One notable modication involves incorpo-
merization extends the carbenium ion chain. In contrast, b- ration of Ni into the H-ZSM-5 zeolite, which favours the
scission is a cracking mechanism, where the chain length is formation of high molecular weight oligomers, particularly
reduced. The reaction rates depend on the size and stability of benecial for diesel production. A study by Li et al. for propylene
the carbenium ion; larger ions react more slowly than smaller oligomerization revealed that a modied H-ZSM-5 catalyst with
methyl and ethyl ions. Hydrogen transfer within these reactions a Ni content of 2.21 wt% achieved a selectivity of 79% towards
leads to the formation of lighter paraffins.333 diesel compared to a selectivity of 68% for H-ZSM-5.303 The
The shape selectivity and acid properties of the H-ZSM-5 addition of Ni can also confer activity for ethylene oligomeri-
zeolite catalyst enable a high activity for transforming C3–C6 zation, as discussed previously. Additionally, advancements like
olens into gasoline, jet fuel and diesel fractions, while exhib- the dealumination of ZSM-5 zeolites were found to enhance
iting a low deactivation rate.334 The microstructure of the ethylene conversion and favour jet fuel range production.325
Fig. 8 Proposed reactions for propylene oligomerization on acid zeolites (reproduced from ref. 330 with permission from John Wiley and Sons,
copyright 2019).
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Research by Mlinar et al. indicated that a lower Si/Al ratio in oligomerization in the 1970s and 1980s.307,345–348 Integrated with
catalysts enhances selectivity towards dimer formation rather ExxonMobil's MTO process, the MOGD process can convert
than cracking products.304 However, a lower Si/Al ratio with light olens in the C3–C6 range into hydrocarbon products such
increased concentration of Brønsted acid sites could negatively as jet fuel. The specic conditions for oligomerization reported
impact the oligomerization selectivity and increase the in literature are in the range of 200 °C to 300 °C and 40 bar
productivity of aromatics.304,342 applied in a system of four xed-bed reactors, out of which three
Catalytic activity and selectivity are signicantly inuenced are operational and one in regeneration mode.80,270,349 The
by temperature, reactant partial pressure, and contact time MOGD process, shown in Fig. 9, produces high yields of
between the reaction mixture and the acid sites of the cata- distillate fuels (82%), alongside gasoline (15%) and light gases
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lyst.343 A study by Coelho et al. on 1-butylene oligomerization (3%), with the exibility to adjust the distillate/gasoline ratio by
over a H-ZSM-5 catalyst indicates an increase of oligomerization adjusting the olen yield from the MTO process.270,350 The
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selectivity with temperature increased up to a threshold of integration of the MTO and MOGD processes therefore also
200 C, beyond which cracking dominates over oligomeriza- demonstrates the potential of producing jet fuel out of
tion.344 Furthermore, their ndings indicate an increase in methanol.69,349
conversion at higher reactant partial pressure. In their investi- The conversion of olens to distillate (COD) process, devel-
gation of butylene oligomerization to liquid fuels at 1.5 bar and oped by PetroSA in South Africa, converts C3–C6 olens
275 °C on H-ZSM-5 with SiO2/Al2O3 = 30, Dı́az et al. demon- produced in FT synthesis into higher olens, with the purpose
strated that increasing the space time (0.5–10 gcatalyst h molc−1) of producing fuels such as gasoline and diesel.327,351 The COD
results in higher butylene conversion, associated with higher process was investigated over ASA, SPA and H-ZSM-5 cata-
selectivity for C5–C7 and lower selectivity for C8–C12.306 This can lysts.327,352,353 Among those, H-ZSM-5 is notable for producing
be attributed to the cracking of C8–C12 fractions, while the a higher cetane number post hydrogenation reaction.69 The
selectivity for by-products like paraffins remained unchanged. COD oligomerization of FT light olens over H-ZSM-5 is con-
In conclusion, optimizing the conditions of reaction tempera- ducted at operating conditions of 210 °C to 253 °C, 56 bar to 57
ture, partial pressure and contact time is necessary to promote bar, and WHSV 0.5 h−1.353 The FT feedstock in the COD process
the formation of olens with a carbon chain length suitable for consists of over 80% olens and 13% to 17% paraffins. The
jet fuel (C8–C16) and reduce the formation of cracking and propylene conversion within the COD process ranges from 92%
hydrogen transfer products. The ethylene content of the oligo- to 99%.354 In conclusion, insights gained from the MOGD and
merization feed is decisive for the design of the oligomerization COD processes, which are established technologies with a rela-
subprocess within MTJ, as it determines whether a one-stage tively high TRL, could be used within the MTJ process to enable
oligomerization over solid acid catalysts is sufficient for the conversion of C3–C6 olens into jet fuel range hydrocarbons
obtaining a high jet fuel yield. over H-ZSM-5.
2.3.2 Process layout. The MOGD process introduced the 2.3.3 Products. The oligomerization subprocess within the
idea of using H-ZSM-5 zeolite and similar zeolites as potential MTJ route aims to maximize the yield of hydrocarbons fractions
alternatives to traditional SPA catalysts for olen ranging from C8–C16 while minimizing the formation of
Fig. 9 Simplified process flow diagram of the MOGD process.278
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3 Potential for process integration
and intensification
Process intensication strategies aim to enhance efficiency,
reduce equipment requirements, and decrease environmental
impact of chemical processes by integrating subprocesses or
using innovative equipment.362–364 In the context of SAF
production, these strategies should be evaluated by their impact
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on the overall jet fuel yield and process efficiency. The previous
sections illustrated several state-of-the-art process layouts for
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the subprocesses involved in the MTJ route, highlighting the
potential for further research and development regarding
process integration and intensication. To intensify the process
chain, these subprocesses need to be integrated in terms of
recycle streams and heat integration strategies. This section
discusses key challenges and research questions for process
integration and intensication concepts signicantly inu-
Fig. 10 Simplified process flow diagram of the hydrogenation of the encing the future implementation of the MTJ process. A
oligomerization products.341
simplied block diagram is shown in Fig. 11 to illustrate
different recycle possibilities and process congurations dis-
cussed in this section.
byproducts such as gasoline and diesel. The product distribu- A key aspect with signicant potential for overall energy
tion of oligomerization subprocess and the preferred oligo- efficiency improvements in the MTJ process is related to the
merization strategy depend on the olen distribution produced feedstock of the MTO process. On the one hand, distillation of
in the MTO subprocess, emphasizing the importance of crude methanol within the methanol synthesis subprocess
studying these two subprocesses in an integrated manner. requires substantial heat. On the other hand, co-feeding water
with methanol helps to reduce the catalyst deactivation and
manage the heat of the exothermic MTO synthesis.365,366
2.4 Hydrogenation Therefore, directly using crude methanol as feedstock for the
Olens are highly reactive compounds capable to form deposits MTO process can save energy and costs associated with distil-
in jet engines.71 Therefore, the hydrogenation of the olens lation.71 Additionally, the reaction heat generated during
produced from the oligomerization process to paraffins is methanol synthesis could potentially be utilized elsewhere in
a crucial step within the MTJ route to enhance the stability and the process, enhancing the overall MTJ process efficiency. It is
performance of jet fuel.355–357 The hydrogenation process crucial to consider that the presence of impurities in crude
involves the addition of H2 to unsaturated olens: methanol may inuence the initiation of the olenic cycle and
the subsequent MTO conversion process. Oxygenates with
CnH2n + H2 / CnH2n+2 carbon–carbon (C–C) bonds may accelerate the MTO conver-
sion, and higher alcohols are expected to dehydrate into their
respective olens.367 Consequently, future research is needed to
The reaction is catalysed by reduced metals, such as Ni, Pd or investigate the impact of these impurities on MTO conversion
Pt supported on alumina or activated carbon.358–360 The and their potential effects on catalyst deactivation. However,
exothermic reaction is usually carried out in a xed-bed reactor at implementing this strategy would require for methanol
temperature and pressure ranges between 50 °C and 370 °C as synthesis and MTO subprocesses being located geographically
well as 5 bar and 50 bar, respectively.69,70,357,361 Specic hydroge- close to each other.
nation conditions depend on the active metal, feedstock and Particularly important is optimizing the yield of the MTO
targeted product. The H2 gas is fed in stoichiometric excess to subprocess towards C2 and C3–C6 olens, as this signicantly
achieve an approximately complete conversion of olens to affects the subsequent reaction mechanisms and product
paraffins. Excess H2 is recovered downstream the reactor by a gas/ distribution in the oligomerization subprocess and can impact
liquid separator and recycled to the reactor inlet (see Fig. 10).24,358 the overall yield of the jet fuel product. Feeding DME into the
Downstream the separator, hydrocarbons are fractionated to MTO subprocess could improve olens yield.218,219 To enhance
segregate light hydrocarbons (<C8), jet fuel range hydrocarbons energy efficiency and decrease equipment cost of the additional
(approximately C8–C16), and heavier hydrocarbons. An isomeri- conversion step from methanol to DME, integrated concepts are
zation unit is not required, as acid-catalysed olen oligomeriza- currently under investigation which could be applied in this
tion within the MTJ process produces branched olens.71 Meeting context.368–370 Further research should be carried out to inves-
the nal jet fuel properties, such as ashpoint, freezing point and tigate the impact of the MTO feed, particularly crude methanol
distillation curve, the nal separation aer hydrogenation shall and/or DME, on the reaction mechanism, selectivity, reaction
be dened by the ASTM standard for MTJ.20
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Fig. 11 A simplified block diagram illustrating various recycle options and process configuration discussed in Section 3 regarding the potential for
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process integration and intensification starting from CO2 and H2.
kinetics, and catalyst stability, in order to optimize the feed- a mixed olen feedstock results in a more uniform product
stock of MTO processes for SAF production. distribution and improved overall selectivity towards jet fuel
As the MTO product could consist of up to 30 wt% range hydrocarbons.19,308 This enables multiple options for
ethylene,251 it emerges as an intermediate product that requires recycling light olens (C2–C7) that fall short of the jet fuel chain
careful management to achieve high jet fuel yields. A main length downstream of oligomerization. Thus, a critical area for
challenge in co-oligomerizing a mixture of ethylene and other further investigation is identied as the evaluation of extent and
light olens (e.g., propylene and butylene) lies in the differing impact of recycling streams on energy demand, alongside
oligomerization mechanisms and the types of catalysts improvements in product distribution and process efficiency.
required.294 Literature discusses three main approaches for the By integrating and intensifying the oligomerization and
further conversion of ethylene within the MTJ process: hydrogenation processes, efficiency improvements and reduc-
(1) Recycling ethylene back into the MTO reactor213 tions in equipment requirements can be achieved. As an
(2) Direct ethylene oligomerization325 example, Topsoe introduced a method combining these steps
(3) Two-step oligomerization319,323,324 into a single hydro-oligomerization (Hydro-OLI) step.83 The
While recycling ethylene to the MTO synthesis is feasible process utilizes a reactor system with stacked catalyst beds,
only in limited amounts and may not signicantly improve incorporating a hydrogenation metal (e.g., Pd, Rh, Ni) and
overall carbon efficiency, direct ethylene oligomerization into a zeolite. While this combination produces less heat than
jet fuel range olens suffers from low selectivity and conversion, higher oligomerization processes and converts olens into
necessitating substantial recycling, which makes it an energy- mainly C8–C16 hydrocarbons, it has the disadvantage of elimi-
intensive option.319,324,325 In contrast, the two-step oligomeriza- nating the possibility to recycle short olens back to the reactor,
tion could be more efficient, as it allows for a more selective as all olens are saturated into paraffins. Moreover, the inte-
conversion of ethylene to the desired jet fuel range olens.325 gration can reduce separation efforts and enhance energy effi-
This method involves oligomerizing the ethylene fraction in ciency. However, such improvements depend on maintaining
a separate reactor with transition metal catalysts to produce a comparable jet fuel yield or aiming to produce various
higher olens (primarily in the C4 and C6 range).319 These hydrocarbon product streams. Additionally, using reactive
higher olens can then be sent to the second oligomerization distillation for combined oligomerization and hydrogenation
reactor loaded with an acid catalyst. In conclusion, the limita- has been demonstrated in the literature.357 This concept shows
tions of recycling ethylene back into the MTO process suggest the potential to improve the energy and mass efficiency of the
a need for further investigation of alternative strategies, process and reduce equipment costs, but requires further
particularly the two-step oligomerization approach, especially research and development within the MTJ process.
when substantial amounts of ethylene are produced in MTO. Another intensication approach is the one-pot hydrogena-
The oligomerization reaction mechanism and product tion of CO2 to olens.371 The direct conversion of CO2 and H2
distribution are signicantly inuenced by the distribution of into hydrocarbons within a single reactor has the potential to
light olens produced in the MTO process. Theoretically, the reduce the overall energy demand and simplify the process
oligomerization product mixture could be sent entirely to the layout compared to individual synthesis steps.372,373 This
hydrogenation subprocess. However, unconverted light olens method can be implemented via two primary pathways:
are valuable intermediates. Thus, recycling these compounds (1) The combination of the RWGS reaction with FT synthesis
back to the MTO or oligomerization subprocesses has the (CO2-FT route)
potential to signicantly improve the overall jet fuel yield. On (2) The integration of the methanol synthesis with the MTO
the one hand, co-feeding small concentrations of light olens, synthesis (MeOH-mediated route)
such as propylene and butylene, with the methanol feedstock While the limitations and potentials of the CO2-FT route
into the MTO subprocess enhances the olenic cycle, leading to were already discussed in Section 1 of this article, state of
a higher yield of the desired light olen chain lengths of science of the MeOH-mediated pathway will be discussed briey
C3+.242,249,250 On the other hand, the co-oligomerization of here. For this route, the methanol and MTO synthesis can be
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combined using a bifunctional catalyst, consisting of a metal subprocess operated in a xed bed or uidized-bed reactor,
catalyst for methanol synthesis and a zeolite catalyst for the respectively. Among these catalysts, H-ZSM-5 catalyst seems more
MTO reaction, at operating conditions of 350 °C to 400 °C and promising for SAF production as it shows a higher selectivity to
15 bar to 30 bar.374 This route is capable of producing light C3–C6 olens compatible for the MTJ process, while exhibiting
olens with a high selectivity due to the metal/zeolite composite a lower tendency for coke formation and a lower selectivity
catalysts used.375 However, the low C–C coupling activity as well towards the formation of ethylene. The olen yield and catalyst
as the formation of the byproduct water enhancing deactivation lifetime can be improved through various strategies, including
of the metal catalyst hinder the technical implementation of catalyst modication, olen co-feeding, MeOH dilution and
this pathway.372,376 Moreover, the direct CO2 to olens conver- product back-mixing. The most widely accepted mechanism for
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sion suffers from lower conversion compared to the established the MTO reaction network is the dual-cycle mechanism,
two-step methanol synthesis and MTO processes.211,377 Given composed of the olenic cycle and aromatic cycle. However,
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the currently low TRL for the direct CO2 to olens conversion, representative modelling of the reaction mechanism is chal-
further research focusing on the development of efficient lenging, due to the complex reaction network and challenges
bifunctional and multifunctional catalysts that perform effec- regarding the analytical evaluation of experimental results. Most
tively under the required conditions for both methanol and published kinetic models on MTO synthesis are based on
MTO synthesis, while maintaining stability, remains critical for simplied assumptions or target solely for selective propylene
advancing this technology. production. Further research is required to develop appropriate
In terms of the geographical distribution of the MTJ process kinetic models optimized for the process conditions relevant for
chain, two different approaches are possible: rst, producing an MTJ application.
methanol from CO2 and H2 at one site and then transporting The oligomerization process is used to transform lighter
the methanol as an intermediate to a location for further jet fuel olens (C2–C6) into longer-chain olens (C8–C16). Available
production; or second, producing jet fuel from CO2 and H2 in an scientic literature mainly targets ethylene oligomerization over
integrated process at a single site. The rst approach offers transition metal catalysts and C3–C6 olens oligomerization
exibility by allowing sourcing “green” methanol from the over acidic catalysts, due to mechanistic differences in the
global market, independent of security of supply limitations. oligomerization of ethylene and higher olens. Thus, the olig-
On the other hand, the second approach, would enable omerization of MTO products comprising both C2 and C3–C6
improved heat integration opportunities and higher overall olens needs special consideration regarding catalyst and
process energy efficiency. Additionally, it is crucial to emphasize process design. The oligomerization of C3–C6 olens over
that the recycling of byproducts (such as fuel gas and processed heterogeneous solid acid catalysts such as zeolites, amorphous
purge gas) through reforming can only be effectively imple- silica–alumina, and sulfonic acid polymeric resins has also
mented in plant designs where methanol synthesis and MTJ been explored, with zeolites favoured for their thermal stability
processes are located at the same site. The extend of the and suitable operational temperature range. Optimized reac-
dynamic operation of methanol synthesis to utilize the uctu- tion conditions, including temperature, reactant partial pres-
ating energy supply for both approaches should be investigated sure, and contact time, are crucial for promoting the formation
in a simulation study.73–76,378 Furthermore, scenario-specic of jet fuel range olens. The feed composition from the MTO
technoeconomic assessments are recommended to evaluate subprocess signicantly inuences the reaction mechanism,
economic scenarios for global SAF production. product distribution, and selectivity in the oligomerization
subprocess; therefore, both subprocesses should be investi-
4 Conclusions gated in an integrated manner. Thus, dedicated kinetic studies
on both MTO and oligomerization step within the context of
The aviation sector faces a pressing need for sustainable alter- MTJ conversion will be necessary to reduce the uncertainty
natives to fossil feedstock-based jet fuel to mitigate its envi- associated with future techno-economic analyses and process
ronmental impact. SAFs offer a viable drop-in solution and can simulations. Industrial processes such as MOGD and COD have
be produced from various feedstocks. The MTJ pathway repre- integrated oligomerization with other technologies to convert
sents a promising route, as it offers high jet fuel yields and low light olens into gasoline and diesel, demonstrating the
byproduct formation. This review explores the current state-of- potential for jet fuel production through the MTJ process.
the-art of the MTJ process concepts involving the conversion The product mixture of the oligomerization process is nally
of H2 and COx into jet fuel through methanol synthesis, MTO hydrogenated over reduced metal catalysts to enhance the
synthesis, oligomerization, and hydrogenation. The main stability and performance of jet fuel. The hydrogenation
ndings highlight the necessity of an integrated process to subprocess is the least challenging, as state-of-the-art technol-
achieve high yields of SAF and economic viability. ogies can be applied for SAF production.
The MTJ process chain begins with methanol synthesis with Key challenges for the practical implementation of the MTJ
the option of dynamic operation to add exibility to the MTJ process chain remain in optimizing the integration and inten-
process in coupling with uctuating renewable energies. sication between the subprocesses, particularly in the MTO
Methanol is then converted to light olens in the MTO subprocess and the subsequent oligomerization subprocess,
synthesis determining jet fuel selectivity and yield. H-ZSM-5 and with regard to jet fuel yield. Several process intensication and
SAPO-34 are the commonly used catalysts for the MTO
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integration aspects have been highlighted for further research LAS Lewis Acid Site
by the scientic community within this review: LCOP Levelized Cost of Production LCOP
(1) The direct use of crude methanol produced from the LHV Lower Heating Value
methanol synthesis process into the MTO reactor could achieve MOGD Mobil Olens to Gasoline and Distillate
savings in energy and costs associated with methanol distilla- MTA Methanol-to-Aromatics
tion. The impact of side products as well as the increased water MTG Methanol-to-Gasoline
content within the crude methanol on selectivity should be MTH Methanol-to-Hydrocarbons
investigated. MTJ Methanol-to-Jet
(2) Recycling of C2–C7 olens downstream the oligomeriza- MTO Methanol-to-Olens
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tion step that fall short of the jet fuel range either to the MTO MTP Methanol-to-Propylene
reactor or the oligomerization reactor to improve the overall jet NOx Nitrogen Oxides
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fuel yield of the MTJ process should be examined. Here, special PEMEL Proton Exchange Membrane Electrolysis
attention to the impact of recycle streams towards energy rWGS Reverse Water Gas Shi
demand, product distribution and process efficiency should be SAF Sustainable Aviation Fuel
drawn. SPA Solid Phosphoric Acid
TOS Time on Stream
(3) The two-step oligomerization approach for managing the
TRL Technology Readiness Level
ethylene fraction produced within the MTO synthesis presents
a promising area for further investigations to improve the MTJ
yield and process efficiency.
(4) The combination of the oligomerization and hydrogena- Data availability
tion within one reactor unit could reduce equipment costs and No primary research results, soware or code have been
enhance energy efficiency. However, this depends on main- included and no new data were generated or analysed as part of
taining a comparable jet fuel yield or aiming to produce this review.
different side products.
Identifying the optimal combination of MTO and oligomer-
ization technology is the key challenge in optimizing the MTJ
Author contributions
process. This aspect should be investigated in further research Ali Elwalily: conceptualization, methodology, investigation,
utilizing process simulation studies to accurately evaluate the formal analysis, writing – original dra, writing – review &
overall process efficiency. Finally, future research should focus editing, visualization, Emma Verkama: writing – original dra,
on rening new process integration and intensication strate- writing – review & editing, Franz Mantei: conceptualization,
gies to improve the economic feasibility, efficiency, and envi- writing – review & editing, project administration, Adiya
ronmental impact of the MTJ process. Overall MTJ yield and Kaliyeva: investigation, formal analysis, Andrew Pounder:
process efficiency could be signicantly improved by further investigation, formal analysis, Jörg Sauer: conceptualization,
optimizing parameters like feedstock composition, operating writing – review & editing, supervision, Florian Nestler:
conditions, and process integration. conceptualization, writing – original dra, writing – review &
editing, supervision.
Abbreviations
Conflicts of interest
AEL Alkaline Electrolysis There are no conicts of interest to declare.
AEM Anion Exchange Membrane Electrolysis
ASA Amorphous Silica–Alumina Acknowledgements
ASTM American Society for Testing and Materials
ATJ Alcohol-to-Jet The authors gratefully acknowledge funding by the German
BAS Brønsted Acid Site Federal Ministry of Transport and Digital Infrastructure
COD Conversion of Olens to Distillate (BMDV) within the SAFari project (Sustainable Aviation Fuels
CCU Carbon Capture and Utilization based on Advanced Reaction and Process Intensication), grant
DAC Direct Air Capture number: 16RK14009A.
DME Dimethyl Ether
DOC Direct Ocean Capture References
DTO DME-to-Olens
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