Vivek Patil | CHEN 6970 | Project-1 | Due: 03/09/2018

Methanol from Municipal Solid Waste: a Chemical Engineer’s perspective

Enerkem, a Canada-based company has made a claim that it can manufacture methanol from municipal solid
waste [1]. In this review, we will explore whether their claim holds true with the Chemical Engineering point-of-
view.

Methanol production, uses, catalysts:

Methanol is considered an energy carrier, as syngas from renewable resources can be turned into liquid
methanol, enabling an effective storage and transportation of energy. The hydrogen required from this process
can be produced using renewable resources, such as biomass with solar or wind energy [5]. Cu-based catalysts
were able to bring the pressure requirement for this process down to 40-100 atm (at 260°C), with about 97%
conversion of reactants [2].
CO + 2H2 ⇌ CH3OH (ΔH298K= -21.7 kcal/mol) | CO2 + 3H2 ⇌ CH3OH + H2O (ΔH298K=-11.9 kcal/mol)
Methanol has diverse applications, such as manufacture of formaldehyde, acetic acid, blending with gasoline,
dimethyl ether, ‘methanol to olefins’ [3] etc.

Municipal Solid Waste (MSW) to methanol: claim

Enerkem claims that they are capable of converting 100,000 dry tons/year of MSW into methanol at their
Alberta (Canada) facility [1]. They describe their process as a thermochemical route, where MSW is converted to
syngas (CO and H2), from which methanol is produced [1]. Their methanol production demonstration unit
(Westbury, Canada) was installed after laboratory and pilot scale testing at the University of Sherbrooke
(Quebec, Canada).

How feasible is MSW to methanol?

The conversion of syngas from MSW is conventionally converted into liquid methanol using Cu/Zn/Al2O3
catalysts. However, these catalysts cannot stop the reverse water –gas shift (RWGS) reaction that occurs while
producing methanol. The existing catalyst was not effective in the important role of diverting the CO to
methanol. Hence, a better catalyst was needed. CO 2 + H2 ⇌ CO+H2O (ΔH298K= 9.8 kcal/mol)
Recently a research group at Stanford discovered Ni-Ga intermediate compounds as stable catalysts that have
shown a potential to stop RWGS reaction in favor of methanol production [4]. Particularly, Ni5Ga3 was found to
be selective and active [4]. Also, it was regenerated by reduction with H2 at 350°C for 2h. In the end, the process
using this catalyst produces only methanol and water, producing an effective fuel for a fuel cell [4]. The other
limitations that need to be explored is the poisoning of catalyst- during the reduction with H2, methane capable
of poisoning 10% surface area of catalyst was generated. However, with this catalyst, the syngas to methanol
conversion route becomes worthy of consideration [4].

Fig. 1 CO-free selectivity of methanol and Dimethyl Ether (DME), Comparison of CO to methanol in
the products with Ni-Ga and conventional CuZnO catalyst.[4]

Now, the conversion of MSW to syngas via gasification has certain limitations as well. The process involves
partial oxidation of carbon in MSW to produce CO and H 2, to be used as a feedstock for methanol production.
However, due to often-additional O2 and the presence of moisture in MSW, CO2 and H2O are produced as
byproducts, reducing the efficiency of the process. Here, use of steam instead of additional O 2 to increase the
reactor temperature can help with decomposition of CO 2 and H2O and increased CO and H2 production [6].
Hence, for this document we can consider that this step in the current methanol production route is achievable.

How sustainable is MSW to methanol?

About 1300 Gt MSW, generated every year throughout the world can be diverted from landfills to produce
methanol via the syngas route, creating sustainable alternative fuels. To assess the potential of methanol from
solid waste, methanol to 'refuse-derived fuel' ratio (MRR) can be used: MRR= 8*mH2/mRDF. The study which
mentioned this ratio also reported that it is maximum (0.67) when recycled steam and about 1/3 rd oxygen was
supplied for producing syngas at ~800°C [5]. Altogether, MSW is a potentially sustainable source for methanol
production.
How true is the claim of Enerkem?
The methanol production cost has a relatively large component for 'reformer' that produces syngas and 'O 2
manufacturing', for the processes where additionally partial oxidation is used [7]. The process of Enerkem
involves a feedstock that is available for almost free of cost. However, the cost for reformer and oxygen
synthesis clearly offset the cheaper feedstock. Improving the stoichiometry of syngas will add to the
improvement [7]: taking ideal syngas ratio as (H2–CO2) /(CO+CO2) = 2 instead of H2/CO=2. Also, recycling of
unconverted feed can help a bit. A totally different route had also been taken to avoid the RWGS reaction can
be to eliminate CO and H2 in the process altogether [7]. This is achievable particularly in the case of MSW and it
will involve its anaerobic digestion to get methane. This methane can then be converted to methanol via other
intermediates such as methyl chloride (CH3Cl) or methyl bisulphate (CH3OSO3H).

Fig.2 A different route for methanol, via methane [7]

Conclusion
My view: I have worked on gasification project before and a few things from that process- the syngas often
have large impurities of CO2 that are difficult to separate, immediate conversion of syngas to liquid methanol
with either conventional or the new Ni-Ga catalysts can help avoid the problem of tar condensation in gasifier
outlet.
For the claim of Enerkem, their process of conversion of syngas into methanol should be running continuously
without catalyst poisoning (due to catalyst reactivation) for a long time. Also, without having an innovative
catalyst for methanol production, the facility is very likely to be found looking for alternate uses of syngas
produced from MSW. Either by using the route of methane formation from MSW, or by the use of highly
effective novel catalyst for methanol production, the claim of a sustainable methanol production from MSW is
more likely to be successful.
References:
[1] Marie-Hélène Labrie, Waste-to-methanol: a commercial reality with Enerkem, 2015 European Methanol Policy Forum Brussels
(2015)
[2] Essentialchemicalindustry.org
[3] IHS Markit (2015)
[4] Felix Studt et al., Nature Chemistry, Vol. 6 (2014) 320-324
[5] Seyed Hosseini et al., Renewable and Sustainable Energy Reviews, Vol. 57(2016) 850-866
[6] Acta Chimica Slovaca, Volume 10 (2017), Issue 2, Pages 107–114, ISSN (Online) 1337-978X
[7] J.-P. Lange / Catalysis Today 64 (2001) 3–8