Sustainable aviation fuel production via the methanol pathway: a technical review

Ali Elwalily^ab, Emma Verkama^a, Franz Mantei^a, Adiya Kaliyeva^a, Andrew Pounder^a, Jörg Sauer^b and Florian Nestler*^a
aFraunhofer Institute for Solar Energy Systems ISE, Hydrogen Technolgoies, Heidenhofstr. 2, 79110 Freiburg, Germany. E-mail: florian.nestler@ise.fraunhofer.de
^bKarlsruhe Institute of Technology (KIT), Hermann-von-Helmholtz-Platz 1, D-76344 Eggenstein-Leopoldshafen, Germany

First published on 27th May 2025

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1 Introduction

With an estimated total emission of 0.8 Gt_CO2, the aviation sector accounted for over 2% of the global anthropogenic carbon dioxide (CO₂) emissions in 2022.^1,2 These emissions are projected to triple by the year 2050, provided that no counter measures are taken.^3,4 The primary source of these emissions is the combustion of fossil-based jet fuel during flight operations accounting to about 2.5 kg of CO₂ per litre of jet fuel.⁵ Despite the global decrease of fuel consumption per passenger of 23% between 2005 and 2017, i.e. from 4.4 L per 100 km to 3.4 L per 100 km, this efficiency gain is counterbalanced by the projected annual growth in passenger numbers of 4.3%.^6,7 In addition to CO₂, significant emissions from global aviation include nitrogen oxides (NO_x), water vapor, soot, sulfate aerosols, and increased cloudiness due to contrail formation.^8,9 Both CO₂ and non-CO₂ emissions contribute to net surface warming and anthropogenic climate changes,¹⁰ with approximately one-third of the radiative forcing attributed to CO₂ and the other two-thirds caused by particulate emissions and water vapor forming contrail cirrus clouds.^11,12

The climate impact of aviation could be mitigated by adopting new technologies, such as electric or hydrogen (H₂) fuelled aircrafts.¹³ However, electrification of aviation faces significant challenges due to the low energy-density of batteries. Currently, 50 kg of batteries are needed to supply the same amount of energy as 1 kg of jet fuel, complicating their adaption for long-distance flights.¹⁴ Due to its low volumetric energy density and difficult handling, hydrogen fuelled aircrafts also require further research and development to address challenges regarding onboard storage of hydrogen, restricted flight ranges, as well as comprehensive updates to aviation infrastructure and aircraft designs.¹⁵ Given the current state of the aviation industry and the operational fleet, it is hardly possible to find alternatives to liquid jet fuels, possessing high energy densities and a short implementation interval.¹⁶

Sustainable aviation fuels (SAFs) are commonly referred to as kerosene-type fuels that can be produced from renewable energy sources.¹⁷ SAFs are identified as viable drop-in replacements and blendstocks for fossil-based jet fuel, capable of mitigating the environmental impact by decreasing fossil CO₂ and other GHG emissions. Indeed, the International Air Transport Association (IATA) has recognized SAF production as the most promising short-term strategy to reduce CO₂ emissions in the aviation sector.¹⁸ Additionally, the production of SAF could contribute to meeting the increasing global demand for jet fuel while enhancing energy security and reducing reliance on fossil fuels.¹⁹

SAF can be categorized based on their production routes and 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 certified by the ASTM D7566 Standard Specification for Aviation Turbine Fuel Containing Synthesized Hydrocarbons, set by the American Society for Testing and Materials (ASTM).²⁰ The qualification process for new candidates of non-petroleum alternative jet fuels is specified by ASTM D4054 Standard Practice for Evaluation of New Aviation Turbine Fuels and Fuel Additives.^21,22 Once an alternative jet fuel production route is qualified, the standard specification for that jet fuel would be added as an annex to ASTM D7566. These ASTM standards ensure that the produced SAF possess compatible characteristics with the commercially available fossil-based jet fuels (Jet A/Jet A-1), specified in ASTM D1655 Standard Specification for Aviation Turbine Fuels.²³

Table 1 compares selected ASTM property requirements for Jet A and a selection of alternative jet fuel routes. Notably, stricter requirements for alternative fuels have been implemented due to various concerns about the specific distinctions between synthetic chemical blends with petroleum distillates.²⁴ To date, no 100% drop-in SAF process routes have been approved by ASTM and most approved production routes have a 50% maximum blending limit. This can be attributed to the significantly reduced aromatics content in the SAF produced, which could affect the seal compatibility of aircraft engines.²⁵ The aviation industry aims to progress towards the use of 100% SAF that comply with safety and operability requirements of the ASTM qualification process.²⁶

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In 2024, SAF represented only 0.3% of global jet fuel produced.²⁷ Large-scale production of SAF faces significant challenges, primarily due to their production costs which are estimated to be 1.2 to 7 times higher than the market price of conventional fossil jet fuel.^28,29 The EU council recently adopted the RefuelEU aviation initiative designed to stimulate large-scale production of SAF and reduce production costs with increasing technological maturity.^28,29 This initiative includes a new regulation mandating a gradual increase of the minimum SAF share in jet fuel blends at EU airports from 2% in 2025 to 70% by 2050.³⁰ Moreover, it sets targets for renewable fuels of non-biological origin (RFNBO), starting at 0.7% in 2030, with an increase to 35% by 2050. This increase is anticipated to enhance the development of synthetic jet fuels, including e-fuels produced via Power-to-Liquid (PTL) processes.

Projected jet fuel demand at EU airports is anticipated to reach approximately 46 Mt per a by 2030.³¹ Currently, the annual production capacity of SAF in the EU stands at just over 1 Mt per a.³² With the inclusion of facilities currently under construction, the estimated SAF production capacity for 2030 in the EU is projected to be between 3.5 and 3.8 Mt per a,^32,33 potentially aligning with the mandated SAF demand of 6% by that year. However, to meet the more ambitious targets of 34% by 2040 and 70% by 2050, significant increases in production capacity will be necessary.

The major SAF production routes have been analysed in several recent reviews,^{6,13,18,29,34–37} evaluating the interaction between policy framework, economic considerations, commercialization status, and technical performance. Reviewing the market for ASTM certified SAF routes of biofuels and e-fuels, Detsios et al. concluded that currently feedstocks of biological origins dominate among the various SAF production pathways.¹⁸ A more extensive review by Khanal et al. provides a detailed analysis of SAF production via various biofuel routes.³⁶

Among ASTM approved SAF production routes, the hydroprocessed esters and fatty acids (HEFA) process, currently dominates the SAF market with more than 90% of the total share.^29,38 HEFA jet fuel and HVO diesel are produced via hydrotreatment and subsequent isomerization of fats, oils, and greases (FOG), or other bio-oils.³⁹ Recent commercial developments were made with regard to industrial scale production of bio-jet fuel from the Alcohol-to-Jet fuel (ATJ) route with a wide range of biogenic feedstocks,⁴⁰ with a recent demonstration plant by Lanzajet at a production scale of 30000 t/a.⁴¹ Additionally, the ATJ process has been demonstrated using isobutanol derived from cellulosic non-edible crops biomass.⁴² Up to date, the ASTM D7566 refers to ATJ that uses ethanol or isobutanol as feedstock, while methanol as a feedstock is not included in the ATJ classification.²⁰

Within Europe, the production of SAF from biological origins is strictly regulated, as the feedstock use of food and food crops in aviation is limited by EU regulation 2023/2405.^6,43 Additionally, the expansion in bio-based jet fuel frequently prompts concerns regarding food versus fuel and land-use change.¹⁸ This underscores the need for further development of jet fuel as RFNBO.

PTL routes, which can lead to the production of electro-sustainable aviation fuels (eSAF), a type of synthetic aviation fuel produced using renewable electricity, offer compelling advantages over biofuels due to a greater potential for greenhouse gas reduction, as well as a lower land and water demand.^44–46 Currently, the economic viability of these processes is hindered due to the high production costs of green H₂.⁴⁷ However, it is expected that these costs will decrease with the improvement of the major electrolysis technologies.⁴⁸ The main PTL routes for jet fuel production being discussed today are the FT pathway as well as the methanol-to-jet fuel (MTJ) pathway.^49,50 While SAF derived from the FT process has already been certified as a drop-in aviation fuel according to ASTM D7566 standards, MTJ-based SAF is currently in the process of obtaining approval through ASTM D4054.¹⁷

With availability of FOG feedstocks being a limiting factor, the ATJ route and the Fischer–Tropsch (FT) route are expected to produce a significant amount of bio-based jet fuel in the future.⁵¹ The FT process, originally developed in Germany for producing liquid transport fuels from coal, is capable of transforming synthesis gas, i.e. here a mixture of carbon monoxide (CO) and H₂, into liquid fuels such as SAF.⁵² Synthesis gas can either be produced from biological or non-biological origin.^53,54 The bio-based FT process entails gasification of biomass into synthesis gas before converting it into liquid fuels. Nonetheless, the need for extensive conditioning and cleaning of the synthesis gas from biomass gasification can limit the efficiency and commercial feasibility of bio-based FT synthesis.^55,56

FT technology can be integrated into PTL production route, where synthesis gas is generated from CO₂, electricity, and water instead of biogenic feedstocks. However, FT synthesis faces some challenges regarding syngas generation due to the high energy intensity of CO₂-to-CO-conversion by reverse water gas shift reaction (rWGS) or the low TRL of co-electrolysis.^57,58 Moreover, its high exothermic heat and complex reaction kinetics present a challenge for direct coupling of the process to fluctuating renewable power.^59,60

While many review articles dealing with the characteristics of FT synthesis for SAF production are available today,^52,53,61,62 knowledge regarding the MTJ process chain is still limited. This review examines the current state of science across each subprocess of the MTJ process chain, focusing on the reaction systems, the different catalysts used in each synthesis step and the variables that impact the jet fuel yield, emphasizing areas for future research that can be done by the scientific community. It highlights the necessity to develop an integrated process concept that not only achieves high yields of SAF, but also is economically viable. Based on a systematic analysis of various process configurations, concepts for an integrated process are proposed. The review identifies key challenges and poses research questions critical for the future technological development of the MTJ pathway. Finally, challenges in process integration are outlined, offering a perspective for further research and development in this field.

2 SAF production via methanol

The production of SAF from H₂ and CO₂ via the methanol pathway involves four main subprocesses: methanol synthesis, methanol-to-olefins (MTO) conversion, oligomerization, and hydrogenation.^19,63,64

A simplified schematic of the MTJ process chain is shown in Fig. 2, together with a rough range of the respective process conditions applied and used catalyst types. In a first step, H₂ and CO_x obtained from carbon neutral sources, such as biomass or air, are converted into methanol and water over Cu-based catalyst in an exothermic reaction in a temperature and pressure range of 220–280 °C and 30–80 bar, respectively.⁵⁸ Subsequently, the purified methanol is converted into light olefins during the MTO synthesis step over Zeotype catalyst at process conditions of 400–500 °C and 1–3 bar.⁶⁵ The product stream of the MTO synthesis is quenched, and water is separated and partially recycled to the MTO reactor. C₂–C₆ olefins are separated from lighter and heavier components using fractionation columns.^66–68 In the subsequent oligomerization step, the chain length of the olefins (C₂–C₆) is increased over solid acid catalyst at synthesis conditions of 200–250 °C and 30–50 bar.⁶⁹ Along the process chain, the olefin oligomerization is a critical step to obtain hydrocarbons with the desirable combustion properties in the synthetic jet fuel-range. The oligomerization mechanism of ethylene and higher olefins differs, which confers complexity to the oligomerization process. This will be discussed further in Section 2.3. The oligomerized product is mixed with H₂ and hydrogenated over a reduced metal catalyst at 100–250 °C and 20–50 bar to saturate the olefinic double bonds.⁶⁹ The product is cooled and the excess H₂ is recycled back to the fixed-bed hydrogenation reactor.⁷⁰ Finally, the jet fuel product, with a typical carbon range of mainly C₈–C₁₆, is separated from lighter and heavier hydrocarbons using fractionation columns.⁷¹

Especially in the context of PTL, MTJ shows potential for SAF production regarding the following aspects:

(1) As methanol can be produced from both CO and CO₂, CO₂ can be utilized directly without the need of a reverse water gas shift stage or co-electrolysis.⁷²

(2) The possibility of dynamic methanol synthesis operation enables a direct link of renewable energy to jet fuel production.^73–77

(3) The exothermic heat of jet fuel production can be integrated into the process chain to allow reduced heat demands.

(4) MTJ can produce jet fuel at high yields with low levels of byproduct formation.^17,71 This is an advantage over FT, where the formation of light hydrocarbons, such as, methane can be significant.

(5) By optimizing the synthesis conditions, jet fuel derived from methanol could be produced with low levels of aromatic compounds compared to fossil jet fuel, which contributes to reduced contrail formation and lessens the adverse climate effects of aviation emissions.^78,79

Each of the individual subprocesses of the MTJ process chain are currently operational on industrial scale in various plants and refineries.^80–82 However, to date, there have been no commercial scale implementations of specific concepts integrating the various subprocesses of the MTJ pathway, reflecting the relatively low TRL of an integrated MTJ process.^17,71

Various companies and institutions are working on the process development of MTJ, such as ExxonMobil, UOP and Topsoe.^83–85 Several research projects are investigating this topic, such as SAFari and M2SAF.^86,87 Moreover, several techno-economic analyses have investigated the MTJ process, although the optimization towards jet fuel mainly includes strong simplifications.^49,88–91 A detailed process optimization was published by Bube et al., focusing on new modelling approach for the oligomerization of short-chain olefins within the framework of MTJ.^17,90 Scientific studies conducted by Bube et al., Saad et al., and Eyberg et al. estimate the production costs of eSAF via the MTJ process between 4.2 and 9.45 EUR per kg.^88–90 Eyberg et al. compared the levelized cost of production (LCOP) at optimal energy efficiency cases for the FT process and the MTJ process, estimating it to be 8.78 EUR per kg and 9.45 EUR per kg, respectively. However, both estimates corresponds to a value of 0.81 EUR per kWh, reflecting differences in the lower heating value (LHV) associated with the respective jet fuel compositions obtained.⁸⁹ The Project SkyPower initiative, representing multiple stakeholders in the eSAF sector, estimates that production costs for eSAF in Europe will range between 5 and 8 EUR per kg by 2030.⁹² Overall, the estimated production costs are subjected to varying assumptions regarding feedstock costs, plant capacity and the boundary conditions, with water electrolysis and CO₂ capture accounting to 74–79%.^88–90 Moreover, it is important to note that these studies underly systematic uncertainties caused by technical assumptions, such as conversions, selectivities and chain growth probability.^17,90

The following sections review the feedstock, catalyst, reaction networks, process layouts and products of each subprocess within the MTJ route, with the objective of enhancing the selectivity towards jet fuel range hydrocarbons.

2.1 Methanol synthesis

With a global production capacity of nearly 140 Mt per a in 2022, thermochemical methanol synthesis, implemented by BASF in 1923, is today one of the most important chemical production processes.^93,94 Methanol is used as a platform molecule to produce fuels and chemicals, with the main consumption driven by China.⁹⁵ Besides traditional derivatives like formaldehyde, methyl tert-butyl ether (MTBE) or acetic acid, methanol is today widely used for the production of olefins and propylene by MTO or methanol-to-propylene (MTP).^96,97 Due to the fixed demand for RFNBO by the EU, an additional path of utilization for carbon neutrally produced methanol is expected to emerge by the MTJ process.⁴³ Thus, this technology will be reviewed in the next subsections to point out obstacles to be addressed by the scientific community to ensure a reliable scale up of thermo-chemical SAF production via methanol.

2.2 Methanol-to-olefins conversion

The methanol-to-hydrocarbons (MTH) process was first developed by Mobil Oil Corporation (today ExxonMobil) in the 1970s.²⁰⁶ They claimed that a feed of lower alcohol and/or ether, such as methanol, dimethyl ether, or an equilibrium mixture of both, can be converted into a mixture of C₂–C₅ light olefins when contacted over a shape selective aluminosilicate ZSM-5 zeolite catalyst in a fixed-bed reactor. These light olefins can further react to produce paraffins, aromatics, naphthenes and higher olefins, as illustrated in Fig. 4.²⁰⁷

This discovery opened the possibility to produce a range of synthetic hydrocarbons through various processes classified by their targeted product. Thus, MTH process can be subdivided into methanol-to-gasoline (MTG),²⁰⁸ methanol-to-aromatics (MTA),²⁰⁹ MTP,²¹⁰ and MTO processes.²¹¹ Reviewing the MTO synthesis within the MTJ route is crucial for optimal coupling of the subprocess for a maximized jet fuel yield. By examining the state-of-science of the MTO process, opportunities for innovation and efficiency improvements in SAF production can be identified.

2.3 Oligomerization

The oligomerization process involves increasing the olefin chain length by coupling of light olefin monomers.²⁹² Within the MTJ process, the light olefins produced in the MTO unit, predominantly ethylene, propylene, and butylene, are converted into longer-chain hydrocarbon (C₈–C₁₆) suited for jet fuel production.^293–295 On the industrial scale, oligomerization of light olefins is already established for the production of petrochemicals and various fuels, including polymeric gasoline (C₅–C₁₀) and diesel (C₁₀–C₂₀).^296,297 Despite being a mature technology, oligomerization processes are constantly advancing through ongoing research aimed at enhancing catalyst selectivity and lifetime, investigating new feedstocks, and improving both material and energetic efficiency.²⁹⁴ However, research targeting to improve the selectivity of the oligomerization of mixed light olefins towards jet fuel is still scarce.

Product distribution and selectivity of the oligomerization process are significantly influenced by the feed composition. Oligomerization of various olefinic feedstocks has been investigated in literature, each exhibiting distinct oligomerization pathways and selectivity.^{293,298–301} This section focuses on the oligomerization of olefin fractions ranging from C₂ to C₆, which are relevant to the MTJ pathway due to their prevalence in the MTO product.

2.4 Hydrogenation

Olefins are highly reactive compounds capable to form deposits in jet engines.⁷¹ Therefore, the hydrogenation of the olefins produced from the oligomerization process to paraffins is a crucial step within the MTJ route to enhance the stability and performance of jet fuel.^355–357 The hydrogenation process involves the addition of H₂ to unsaturated olefins:

CnH2n + H2 → CnH2n+2

The reaction is catalysed by reduced metals, such as Ni, Pd or Pt supported on alumina or activated carbon.^358–360 The exothermic reaction is usually carried out in a fixed-bed reactor at temperature and pressure ranges between 50 °C and 370 °C as well as 5 bar and 50 bar, respectively.^{69,70,357,361} Specific hydrogenation conditions depend on the active metal, feedstock and targeted product. The H₂ gas is fed in stoichiometric excess to achieve an approximately complete conversion of olefins to paraffins. Excess H₂ is recovered downstream the reactor by a gas/liquid separator and recycled to the reactor inlet (see Fig. 10).^24,358 Downstream the separator, hydrocarbons are fractionated to segregate light hydrocarbons (<C₈), jet fuel range hydrocarbons (approximately C₈–C₁₆), and heavier hydrocarbons. An isomerization unit is not required, as acid-catalysed olefin oligomerization within the MTJ process produces branched olefins.⁷¹ Meeting the final jet fuel properties, such as flashpoint, freezing point and distillation curve, the final separation after hydrogenation shall be defined by the ASTM standard for MTJ.²⁰

3 Potential for process integration and intensification

Process intensification 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 on the overall jet fuel yield and process efficiency. The previous sections illustrated several state-of-the-art process layouts for the subprocesses involved in the MTJ route, highlighting the potential for further research and development regarding process integration and intensification. 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 intensification concepts significantly influencing the future implementation of the MTJ process. A simplified block diagram is shown in Fig. 11 to illustrate different recycle possibilities and process configurations discussed in this section.

A key aspect with significant potential for overall energy efficiency improvements in the MTJ process is related to the feedstock of the MTO process. On the one hand, distillation of crude methanol within the methanol synthesis subprocess 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 Therefore, directly using crude methanol as feedstock for the MTO process can save energy and costs associated with distillation.⁷¹ Additionally, the reaction heat generated during methanol synthesis could potentially be utilized elsewhere in the process, enhancing the overall MTJ process efficiency. It is crucial to consider that the presence of impurities in crude methanol may influence the initiation of the olefinic cycle and the subsequent MTO conversion process. Oxygenates with carbon–carbon (C–C) bonds may accelerate the MTO conversion, and higher alcohols are expected to dehydrate into their respective olefins.³⁶⁷ Consequently, future research is needed to investigate the impact of these impurities on MTO conversion and their potential effects on catalyst deactivation. However, implementing this strategy would require for methanol synthesis and MTO subprocesses being located geographically close to each other.

Particularly important is optimizing the yield of the MTO subprocess towards C₂ and C₃–C₆ olefins, as this significantly affects the subsequent reaction mechanisms and product distribution in the oligomerization subprocess and can impact the overall yield of the jet fuel product. Feeding DME into the MTO subprocess could improve olefins yield.^218,219 To enhance energy efficiency and decrease equipment cost of the additional conversion step from methanol to DME, integrated concepts are currently under investigation which could be applied in this context.^368–370 Further research should be carried out to investigate the impact of the MTO feed, particularly crude methanol and/or DME, on the reaction mechanism, selectivity, reaction kinetics, and catalyst stability, in order to optimize the feedstock of MTO processes for SAF production.

As the MTO product could consist of up to 30 wt% ethylene,²⁵¹ it emerges as an intermediate product that requires careful management to achieve high jet fuel yields. A main challenge in co-oligomerizing a mixture of ethylene and other light olefins (e.g., propylene and butylene) lies in the differing oligomerization mechanisms and the types of catalysts required.²⁹⁴ Literature discusses three main approaches for the further conversion of ethylene within the MTJ process:

(1) Recycling ethylene back into the MTO reactor²¹³

(2) Direct ethylene oligomerization³²⁵

(3) Two-step oligomerization^319,323,324

While recycling ethylene to the MTO synthesis is feasible only in limited amounts and may not significantly improve overall carbon efficiency, direct ethylene oligomerization into jet fuel range olefins suffers from low selectivity and conversion, necessitating substantial recycling, which makes it an energy-intensive option.^319,324,325 In contrast, the two-step oligomerization could be more efficient, as it allows for a more selective conversion of ethylene to the desired jet fuel range olefins.³²⁵ This method involves oligomerizing the ethylene fraction in a separate reactor with transition metal catalysts to produce higher olefins (primarily in the C₄ and C₆ range).³¹⁹ These higher olefins can then be sent to the second oligomerization reactor loaded with an acid catalyst. In conclusion, the limitations of recycling ethylene back into the MTO process suggest a need for further investigation of alternative strategies, particularly the two-step oligomerization approach, especially when substantial amounts of ethylene are produced in MTO.

The oligomerization reaction mechanism and product distribution are significantly influenced by the distribution of light olefins produced in the MTO process. Theoretically, the oligomerization product mixture could be sent entirely to the hydrogenation subprocess. However, unconverted light olefins are valuable intermediates. Thus, recycling these compounds back to the MTO or oligomerization subprocesses has the potential to significantly improve the overall jet fuel yield. On the one hand, co-feeding small concentrations of light olefins, such as propylene and butylene, with the methanol feedstock into the MTO subprocess enhances the olefinic cycle, leading to a higher yield of the desired light olefin chain lengths of C₃₊.^242,249,250 On the other hand, the co-oligomerization of a mixed olefin feedstock results in a more uniform product distribution and improved overall selectivity towards jet fuel range hydrocarbons.^19,308 This enables multiple options for recycling light olefins (C₂–C₇) that fall short of the jet fuel chain length downstream of oligomerization. Thus, a critical area for further investigation is identified as the evaluation of extent and impact of recycling streams on energy demand, alongside improvements in product distribution and process efficiency.

By integrating and intensifying the oligomerization and hydrogenation processes, efficiency improvements and reductions in equipment requirements can be achieved. As an example, Topsoe introduced a method combining these steps into a single hydro-oligomerization (Hydro-OLI) step.⁸³ The process utilizes a reactor system with stacked catalyst beds, incorporating a hydrogenation metal (e.g., Pd, Rh, Ni) and a zeolite. While this combination produces less heat than higher oligomerization processes and converts olefins into mainly C₈–C₁₆ hydrocarbons, it has the disadvantage of eliminating the possibility to recycle short olefins back to the reactor, as all olefins are saturated into paraffins. Moreover, the integration can reduce separation efforts and enhance energy efficiency. However, such improvements depend on maintaining a comparable jet fuel yield or aiming to produce various hydrocarbon product streams. Additionally, using reactive distillation for combined oligomerization and hydrogenation has been demonstrated in the literature.³⁵⁷ This concept shows the potential to improve the energy and mass efficiency of the process and reduce equipment costs, but requires further research and development within the MTJ process.

Another intensification approach is the one-pot hydrogenation of CO₂ to olefins.³⁷¹ The direct conversion of CO₂ and H₂ into hydrocarbons within a single reactor has the potential to reduce the overall energy demand and simplify the process layout compared to individual synthesis steps.^372,373 This method can be implemented via two primary pathways:

(1) The combination of the RWGS reaction with FT synthesis (CO₂-FT route)

(2) The integration of the methanol synthesis with the MTO synthesis (MeOH-mediated route)

While the limitations and potentials of the CO₂-FT route were already discussed in Section 1 of this article, state of science of the MeOH-mediated pathway will be discussed briefly here. For this route, the methanol and MTO synthesis can be combined using a bifunctional catalyst, consisting of a metal catalyst for methanol synthesis and a zeolite catalyst for the MTO reaction, at operating conditions of 350 °C to 400 °C and 15 bar to 30 bar.³⁷⁴ This route is capable of producing light olefins with a high selectivity due to the metal/zeolite composite catalysts used.³⁷⁵ However, the low C–C coupling activity as well as the formation of the byproduct water enhancing deactivation of the metal catalyst hinder the technical implementation of this pathway.^372,376 Moreover, the direct CO₂ to olefins conversion suffers from lower conversion compared to the established two-step methanol synthesis and MTO processes.^211,377 Given the currently low TRL for the direct CO₂ to olefins conversion, further research focusing on the development of efficient bifunctional and multifunctional catalysts that perform effectively under the required conditions for both methanol and MTO synthesis, while maintaining stability, remains critical for advancing this technology.

In terms of the geographical distribution of the MTJ process chain, two different approaches are possible: first, producing methanol from CO₂ and H₂ at one site and then transporting the methanol as an intermediate to a location for further jet fuel production; or second, producing jet fuel from CO₂ and H₂ in an integrated process at a single site. The first approach offers flexibility by allowing sourcing “green” methanol from the global market, independent of security of supply limitations. On the other hand, the second approach, would enable improved heat integration opportunities and higher overall process energy efficiency. Additionally, it is crucial to emphasize that the recycling of byproducts (such as fuel gas and processed purge gas) through reforming can only be effectively implemented in plant designs where methanol synthesis and MTJ processes are located at the same site. The extend of the dynamic operation of methanol synthesis to utilize the fluctuating energy supply for both approaches should be investigated in a simulation study.^73–76,378 Furthermore, scenario-specific technoeconomic assessments are recommended to evaluate economic scenarios for global SAF production.

4 Conclusions

The aviation sector faces a pressing need for sustainable alternatives to fossil feedstock-based jet fuel to mitigate its environmental impact. SAFs offer a viable drop-in solution and can be produced from various feedstocks. The MTJ pathway represents a promising route, as it offers high jet fuel yields and low byproduct formation. This review explores the current state-of-the-art of the MTJ process concepts involving the conversion of H₂ and CO_x into jet fuel through methanol synthesis, MTO synthesis, oligomerization, and hydrogenation. The main findings highlight the necessity of an integrated process to achieve high yields of SAF and economic viability.

The MTJ process chain begins with methanol synthesis with the option of dynamic operation to add flexibility to the MTJ process in coupling with fluctuating renewable energies.

Methanol is then converted to light olefins in the MTO synthesis determining jet fuel selectivity and yield. H-ZSM-5 and SAPO-34 are the commonly used catalysts for the MTO subprocess operated in a fixed bed or fluidized-bed reactor, respectively. Among these catalysts, H-ZSM-5 catalyst seems more promising for SAF production as it shows a higher selectivity to C₃–C₆ olefins compatible for the MTJ process, while exhibiting a lower tendency for coke formation and a lower selectivity towards the formation of ethylene. The olefin yield and catalyst lifetime can be improved through various strategies, including catalyst modification, olefin co-feeding, MeOH dilution and product back-mixing. The most widely accepted mechanism for the MTO reaction network is the dual-cycle mechanism, composed of the olefinic cycle and aromatic cycle. However, representative modelling of the reaction mechanism is challenging, due to the complex reaction network and challenges regarding the analytical evaluation of experimental results. Most published kinetic models on MTO synthesis are based on simplified assumptions or target solely for selective propylene production. Further research is required to develop appropriate kinetic models optimized for the process conditions relevant for an MTJ application.

The oligomerization process is used to transform lighter olefins (C₂–C₆) into longer-chain olefins (C₈–C₁₆). Available scientific literature mainly targets ethylene oligomerization over transition metal catalysts and C₃–C₆ olefins oligomerization over acidic catalysts, due to mechanistic differences in the oligomerization of ethylene and higher olefins. Thus, the oligomerization of MTO products comprising both C₂ and C₃–C₆ olefins needs special consideration regarding catalyst and process design. The oligomerization of C₃–C₆ olefins over heterogeneous solid acid catalysts such as zeolites, amorphous silica–alumina, and sulfonic acid polymeric resins has also been explored, with zeolites favoured for their thermal stability and suitable operational temperature range. Optimized reaction conditions, including temperature, reactant partial pressure, and contact time, are crucial for promoting the formation of jet fuel range olefins. The feed composition from the MTO subprocess significantly influences the reaction mechanism, product distribution, and selectivity in the oligomerization subprocess; therefore, both subprocesses should be investigated in an integrated manner. Thus, dedicated kinetic studies on both MTO and oligomerization step within the context of MTJ conversion will be necessary to reduce the uncertainty associated with future techno-economic analyses and process simulations. Industrial processes such as MOGD and COD have integrated oligomerization with other technologies to convert light olefins into gasoline and diesel, demonstrating the potential for jet fuel production through the MTJ process.

The product mixture of the oligomerization process is finally hydrogenated over reduced metal catalysts to enhance the stability and performance of jet fuel. The hydrogenation subprocess is the least challenging, as state-of-the-art technologies can be applied for SAF production.

Key challenges for the practical implementation of the MTJ process chain remain in optimizing the integration and intensification between the subprocesses, particularly in the MTO subprocess and the subsequent oligomerization subprocess, with regard to jet fuel yield. Several process intensification and integration aspects have been highlighted for further research by the scientific community within this review:

(1) The direct use of crude methanol produced from the methanol synthesis process into the MTO reactor could achieve savings in energy and costs associated with methanol distillation. The impact of side products as well as the increased water content within the crude methanol on selectivity should be investigated.

(2) Recycling of C₂–C₇ olefins downstream the oligomerization step that fall short of the jet fuel range either to the MTO reactor or the oligomerization reactor to improve the overall jet fuel yield of the MTJ process should be examined. Here, special attention to the impact of recycle streams towards energy demand, product distribution and process efficiency should be drawn.

(3) The two-step oligomerization approach for managing the 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 hydrogenation within one reactor unit could reduce equipment costs and enhance energy efficiency. However, this depends on maintaining a comparable jet fuel yield or aiming to produce different side products.

Identifying the optimal combination of MTO and oligomerization technology is the key challenge in optimizing the MTJ process. This aspect should be investigated in further research utilizing process simulation studies to accurately evaluate the overall process efficiency. Finally, future research should focus on refining new process integration and intensification strategies to improve the economic feasibility, efficiency, and environmental impact of the MTJ process. Overall MTJ yield and process efficiency could be significantly improved by further optimizing parameters like feedstock composition, operating conditions, and process integration.

Abbreviations

AEL	Alkaline Electrolysis
AEM	Anion Exchange Membrane Electrolysis
ASA	Amorphous Silica–Alumina
ASTM	American Society for Testing and Materials
ATJ	Alcohol-to-Jet
BAS	Brønsted Acid Site
COD	Conversion of Olefins to Distillate
CCU	Carbon Capture and Utilization
DAC	Direct Air Capture
DME	Dimethyl Ether
DOC	Direct Ocean Capture
DTO	DME-to-Olefins
eSAF	Electro Sustainable Aviation Fuel
FT	Fischer–Tropsch
GHG	Greenhouse Gas
HEFA	Hydroprocessed Esters and Fatty Acids
HTE	High-Temperature Electrolysis
IATA	International Air Transport Association
LAS	Lewis Acid Site
LCOP	Levelized Cost of Production LCOP
LHV	Lower Heating Value
MOGD	Mobil Olefins to Gasoline and Distillate
MTA	Methanol-to-Aromatics
MTG	Methanol-to-Gasoline
MTH	Methanol-to-Hydrocarbons
MTJ	Methanol-to-Jet
MTO	Methanol-to-Olefins
MTP	Methanol-to-Propylene
NOx	Nitrogen Oxides
PEMEL	Proton Exchange Membrane Electrolysis
rWGS	Reverse Water Gas Shift
SAF	Sustainable Aviation Fuel
SPA	Solid Phosphoric Acid
TOS	Time on Stream
TRL	Technology Readiness Level

Data availability

No primary research results, software or code have been included and no new data were generated or analysed as part of this review.

Author contributions

Ali Elwalily: conceptualization, methodology, investigation, formal analysis, writing – original draft, writing – review & editing, visualization, Emma Verkama: writing – original draft, writing – review & editing, Franz Mantei: conceptualization, writing – review & editing, project administration, Adiya Kaliyeva: investigation, formal analysis, Andrew Pounder: investigation, formal analysis, Jörg Sauer: conceptualization, writing – review & editing, supervision, Florian Nestler: conceptualization, writing – original draft, writing – review & editing, supervision.

Conflicts of interest

There are no conflicts of interest to declare.

Acknowledgements

The authors gratefully acknowledge funding by the German Federal Ministry of Transport and Digital Infrastructure (BMDV) within the SAFari project (Sustainable Aviation Fuels based on Advanced Reaction and Process Intensification), grant number: 16RK14009A.

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