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Membrane-Assisted Methanol Synthesis Processes and the Required Permselectivity

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Membrane-Assisted Methanol Synthesis Processes and the Required Permselectivity membranes Article Membrane-Assisted Methanol Synthesis Processes and the Required Permselectivity Homa Hamedi , Torsten Brinkmann * and Sergey Shishatskiy Department of Process Engineering, Institute of Membrane Research, Helmholtz-Zentrum Hereon, Max-Planck-Straße P1, 21502 Geesthacht, Germany; [email protected] (H.H.); [email protected] (S.S.) * Correspondence: [email protected] Abstract: Water-selective membrane reactors are proposed in the literature to improve methanol yield for a standalone reactor. However, the methanol productivity is not a precise metric to show the system improvement since, with this approach, we do not consider the amount of energy loss through the undesirable co-permeation of H2, which could otherwise remain on the reaction side at high pressure. In other words, the effectiveness of this new technology should be evaluated at a process flowsheet level to assess its advantages and disadvantages on the overall system performance and, more importantly, to identify the minimum required properties of the membrane. Therefore, an equation-based model for a membrane reactor, developed in Aspen Custom Modeler, was incorporated within the process flowsheet of the methanol plant to develop an integrated process framework to conduct the investigation. We determined the upper limit of the power-saving at 32% by exploring the favorable conditions wherein a conceptual water selective membrane reactor proves more effective. Using these suboptimal conditions, we realized that the minimum required H2O/H2 selectivity is 190 and 970 based on the exergy analysis and overall power requirement, respectively. According to our results, the permselectivity of membranes synthesized for this application in Citation: Hamedi, H.; Brinkmann, T.; the literature, showing improvements in the one-pass conversion, is well below the minimum Shishatskiy, S. Membrane-Assisted requirement when the overall methanol synthesis process flowsheet comes into consideration. Methanol Synthesis Processes and the Required Permselectivity. Membranes Keywords: methanol synthesis; CO2 hydrogenation; membrane reactor; synthetic fuel; carbon 2021, 11, 596. https://doi.org/ capture; Aspen Custom Modeler; green fuel; carbon utilization 10.3390/membranes11080596 Academic Editor: Adolfo Iulianelli 1. Introduction Received: 7 June 2021 Carbon capture and utilization (CCU) is an economically and ecologically attractive Accepted: 3 August 2021 Published: 6 August 2021 solution to unravel the two contemporary global challenges, i.e., rapid climate change and future energy dilemma. However, the CCU cycle cannot be fully composed, unless Publisher’s Note: MDPI stays neutral the captured CO2 consolidates itself as major building blocks for the production of di- with regard to jurisdictional claims in verse high-demand CO2-based fuels, such as methane, methanol, and liquid hydrocarbon published maps and institutional affil- transportation fuels (LHTF), as well as chemicals. With almost 99 Mt global demand in iations. 2020, methanol is identified as a pivotal intermediate for production of manifold chem- icals (dimethyl ether, formaldehyde, formic acid, lower olefins, acetic acid, and higher alcohols), and LHTFs via the so-called methanol-to-gasoline (MTG) and Mobil olefins-to- gasoline-and-distillate (MOGD) technologies, instead of the traditional Fischer–Tropsch (FT) synthesis approach, as shown in Figure1[ 1–4]. Based on the premises, green methanol Copyright: © 2021 by the authors. Licensee MDPI, Basel, Switzerland. has substantial potential to shortly emerge as one of the key pieces of the carbon cycle This article is an open access article puzzle; however, its production via CO2 hydrogenation is limited by equilibrium conver- distributed under the terms and sion under relevant process conditions and suffers from a high amount of water produced, conditions of the Creative Commons which causes catalyst thermal deactivation. The in situ removal of water from the reaction Attribution (CC BY) license (https:// system not only mitigates the two aforesaid problems but also intensifies the reaction rate creativecommons.org/licenses/by/ and offers a unique opportunity to merge reaction and separation into one single piece of 4.0/). equipment with potential savings in capital and operating expenditures. This tactic can be Membranes 2021, 11, 596. https://doi.org/10.3390/membranes11080596 https://www.mdpi.com/journal/membranes Membranes 2021, 11, x 2 of 16 Membranes 2021, 11, 596 2 of 15 fies the reaction rate and offers a unique opportunity to merge reaction and separation into one single piece of equipment with potential savings in capital and operating ex- penditures.carried out throughThis tactic the can incorporation be carried ofout membrane through separationthe incorporation technology of membrane into the reaction sepa- rationsystem. technology into the reaction system. TheThe first first membrane membrane reactor reactor (MR) (MR) for for methan methanolol synthesis synthesis was was proposed proposed by byStruis Struis et al.et al.[5]. [ 5The]. The authors authors reported reported that that the thereactor reactor equipped equipped with with a Nafion a Nafion membrane membrane outper- out- formsperforms conventional conventional reactors reactors (CR) (CR) with with a a2.5% 2.5% improvement improvement in in one-pass one-pass conversion. conversion. However,However, thethe membranemembrane material material was was not not sufficiently sufficiently resistant resistant to the to temperatures the temperatures at which at whichthe commonly the commonly used catalyst used catalyst is active. is Aactive theoretical. A theoretical study of study zeolite-based of zeolite-based MRs with MRs two withhypothetical two hypothetical sets of species’ sets permeancesof species’ permea was performednces was by performed Barbieri et by al. Barbieri [6]. The methanolet al. [6]. Theyield methanol increased yield from increased 5.8% to 13.7%from 5.8% in the to best13.7% scenario in the best of the scenario MR system. of the MR A theoretical system. A theoreticaland experimental and experimental investigation investigation was performed was performed by Chen and by YuanChen [7and]. They Yuan developed [7]. They developedan isothermal an isothermal MR for methanol MR for synthesis methanol utilizing synthesis a siliconeutilizing rubber/ceramic a silicone rubber/ceramic composite compositemembrane. membrane. They claimed They a 22%claimed enhancement a 22% en inhancement the reaction in conversion.the reaction Gallucci conversion. et al. Gallucciexploited et zeolite al. exploited membranes zeolite to experimentallymembranes to studyexperimentally their impact study on the their isothermal impact reactoron the isothermalperformance reactor [8]. Theperformance results showed [8]. The improvements results showed in improvements both selectivity in andboth conversion. selectivity andRaso conversion. et al. studied Raso various et al. studied zeolite membranesvarious zeolite (zeolite membranes A, mordenite, (zeolite zeolite A, mordenite, T, chabazite ze- oliteand T, Ti-chabazite) chabazite and for Ti-chabazite) the methanol for production the methanol application production [9]. application Zeolite A was[9]. Zeolite reported A wasas the reported best choice as the for best this choice application. for this The application. experimental The resultsexperimental revealed results that while revealed this thattype while of membrane this type increasesof membrane the CO increases2 conversion, the CO it2 conversion, decreases the it decreases methanol the selectivity. methanol A selectivity.bifunctional A catalyticbifunctional MR basedcatalytic on MR a zeolite based LTA on a was zeolite proposed LTA was by Yeu proposed et al. [10 by]. Yeu Recently, et al. [10].a polymer–ceramic Recently, a polymer–ceramic composite membrane composite was me suggestedmbrane was by Juarezsuggested et al. by as Juarez an alternative et al. as ancandidate alternative for candidate this application for this [ 11application]. Due to the[11]. envisaged Due to the advantages envisaged advantages of MR, it has of beenMR, itapplied has been to severalappliedother to several CO2 conversionother CO2 conversion routes presented routes inpresented Figure1[ 12in –Figure15]. 1 [12–15]. Figure 1. Carbon utilization pathways viavia thermocatalyticthermocatalytic conversion conversion with with Technology Technology Readiness Readiness Levels Levels (TRLs) (TRLs) (blurred (blurred to tosharp sharp fonts fonts denote denote low low to to high high TRLs). TRLs). AlthoughAlthough several researchersresearchers havehave already already investigated investigated the the feasibility feasibility of of using using MRs MRs in inthe the methanol methanol synthesis synthesis application application and and unanimously unanimously concurred concurred that that MRs MRs improve improve the sys-the systemtem performance, performance, the the scope scope of theirof their investigations investigations was was limited limited to laboratory-scale to laboratory-scale devices de- with an exclusive emphasis on the standalone reactor’s performance rather than the overall vices with an exclusive emphasis on the standalone reactor’s performance rather than the methanol process. While it was not clear if and to what extent these two metrics can repre- overall methanol process. While it was not clear if and to what extent these two metrics sent the overall process performance enhancement, the one-pass reactor conversion
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