Design, Optimization, and Retrofit of the Formic Acid Process II: Reactive Distillation and Reactive Dividing-Wall Column Retrofits

Cunha, Sérgio da; Rangaiah, Gade Pandu; Hidajat, K.

doi:10.1021/acs.iecr.8b03031

Cited by 20 publications

(16 citation statements)

References 30 publications

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“…The major costs come from the solvent recovery units (i.e., distillation and stripping), which is typical for extraction processes. Recently, Hidajat et al − estimated the economics of the BASF and the Kemira–Leonard process for formic acid production. The cost of FA separation for the BASF process, which is also based on liquid–liquid extraction, was estimated to be around $115/ton.…”

Section: Resultsmentioning

confidence: 99%

High-Pressure Electrochemical Reduction of CO₂ to Formic Acid/Formate: Effect of pH on the Downstream Separation Process and Economics

Ramdin

Morrison

Groen³

et al. 2019

Ind. Eng. Chem. Res.

113

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We use a high-pressure semicontinuous batch electrochemical reactor with a tin-based cathode to demonstrate that it is possible to efficiently convert CO 2 to formic acid (FA) in low-pH (i.e., pH < pK a ) electrolyte solutions. The effects of CO 2 pressure (up to 50 bar), bipolar membranes, and electrolyte (K 2 SO 4 ) concentration on the current density (CD) and the Faraday efficiency (FE) of formic acid were investigated. The highest FE (∼80%) of FA was achieved at a pressure of around 50 bar at a cell potential of 3.5 V and a CD of ∼30 mA/cm 2 . To suppress the hydrogen evolution reaction (HER), the electrochemical reduction of CO 2 in aqueous media is typically performed at alkaline conditions. The consequence of this is that products like formic acid, which has a pK a of 3.75, will almost completely dissociate into the formate form. The pH of the electrolyte solution has a strong influence not only on the electrochemical reduction process of CO 2 but also on the downstream separation of (dilute) acid products like formic acid. The selection of separation processes depends on the dissociation state of the acids. A review of separation technologies for formic acid/formate removal from aqueous dilute streams is provided. By applying common separation heuristics, we have selected liquid−liquid extraction and electrodialysis for formic acid and formate separation, respectively. An economic evaluation of both separation processes shows that the formic acid route is more attractive than the formate one. These results urge for a better design of (1) CO 2 electrocatalysts that can operate at low pH without affecting the selectivity of the desired products and (2) technologies for efficient separation of dilute products from (photo)electrochemical reactors.

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Section: Resultsmentioning

confidence: 99%

High-Pressure Electrochemical Reduction of CO₂ to Formic Acid/Formate: Effect of pH on the Downstream Separation Process and Economics

Ramdin

Morrison

Groen³

et al. 2019

Ind. Eng. Chem. Res.

113

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“…For 85 wt % FA, the costs should be multiplied by 0.85. Recently, da Cunha et al 29,30 and Chua et al 31 estimated the costs of the BASF and Kemira− Leonard process for FA production, respectively. These authors estimated the costs of FA separation for the BASF process at $115/ton and around $145/ton for the Kemira− Leonard process.…”

Section: ■ Resultsmentioning

confidence: 99%

“…For 85 wt % FA, the costs should be multiplied by 0.85. Recently, da Cunha et al , and Chua et al . estimated the costs of the BASF and Kemira–Leonard process for FA production, respectively.…”

Section: Resultsmentioning

confidence: 99%

Liquid–Liquid Extraction of Formic Acid with 2-Methyltetrahydrofuran: Experiments, Process Modeling, and Economics

Laitinen

Parsana

Jauhiainen

et al. 2021

Ind. Eng. Chem. Res.

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Formic acid (FA) is an interesting hydrogen (H 2 ) and carbon monoxide (CO) carrier that can be produced by the electrochemical reduction of carbon dioxide (CO 2 ) using renewable energy. The separation of FA from water is challenging due to the strong (cross)association of the components and the presence of a high boiling azeotrope. For the separation of dilute FA solutions, liquid–liquid extraction is preferred over conventional distillation because distilling large amounts of water is very energy-intensive. In this study, we use 2-methyltetrahydrofuran (2-MTHF) to extract FA from the CO 2 electrolysis process, which typically contains <20 wt % of FA. Vapor–liquid equilibrium (VLE) data of the binary system 2-MTHF–FA and liquid–liquid equilibrium (LLE) data of the ternary system 2-MTHF–FA–water are obtained. Continuous extraction and distillation experiments are performed to test the extraction power and recovery of 2-MTHF from the extract. The VLE and LLE data are used to design a hybrid extraction and distillation process to produce a commercial grade product (85 wt % of FA). A detailed economic analysis of this hybrid extraction–distillation process is presented and compared with the existing FA separation methods. It is shown that 2-MTHF is a cost-effective solvent for FA extraction from dilute streams (<20 wt % FA).

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“…53 At the same time, reactive distillation provides an alternative approach for separation of multicomponent azeotropic mixtures. 54 By changing substance properties through chemical reaction with appropriate reactants, thermodynamic limitations like azeotrope formation can be avoided, but still requires significant energy. Therefore, the revenue generated by FA will not be able to compensate for the additional operating cost due to glycerol feed and separation of products.…”

Section: Hr 4 Hrmentioning

confidence: 99%

Electrochemical Reduction of CO2 to Ethylene with 32% Lower Energy at 80% Lower Cost via Coproduction of Glycolic Acid

Khan¹,

Nabil²,

Al‐Attas³

et al. 2020

Preprint

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We are in a race against time to implement technologies for carbon capture, conversion, and utilization (CCU) to create a closed anthropogenic carbon cycle. Renewable energy powered electrochemical CO2 reduction (eCO2R) to fuels and chemicals is an attractive technology in this context. Here, we demonstrate a strategy to drive economic feasibility of eCO2R to ethylene (C2H4), the largest produced organic chemical, by coupling with glycerol oxidation on anode. Our gold nano-dendrite anode catalyst demonstrated very high activity (J ~377 mA/cm2 at 1.2 V vs reversible hydrogen electrode) and selectivity (~50% to glycolic acid (GA)) for glycerol oxidation. The co-electrolysis process demonstrated record high selectivity of ~60% for C2H4 production at a very low cell voltage of ~ 1.7 V, translating to 32% reduction in required energy compared to conventional eCO2R with water oxidation reaction on anode. The experimental results were complemented with a detailed technoeconomic analysis that indicated economic feasibility will depend on several factors such as price of organic feed, selectivity of anode electrode, market value of chemicals produced and most importantly cost of separation and purification. Our results indicate that C2H4 produced via conventional eCO2R would require electricity price to plummet to <1 cents/kWh to be cost-competitive, while a co-electrolysis process to produce C2H4 and GA will help reduce C2H4 production cost by ~ 80% to ~1.08 $/kg, reaching cost parity at electricity price of 5 cents/kWh. This study may trigger research efforts for design of electrochemical processes with low electricity requirement using cheap industrial waste streams.

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Design, Optimization, and Retrofit of the Formic Acid Process II: Reactive Distillation and Reactive Dividing-Wall Column Retrofits

Cited by 20 publications

References 30 publications

High-Pressure Electrochemical Reduction of CO₂ to Formic Acid/Formate: Effect of pH on the Downstream Separation Process and Economics

High-Pressure Electrochemical Reduction of CO₂ to Formic Acid/Formate: Effect of pH on the Downstream Separation Process and Economics

Liquid–Liquid Extraction of Formic Acid with 2-Methyltetrahydrofuran: Experiments, Process Modeling, and Economics

Electrochemical Reduction of CO2 to Ethylene with 32% Lower Energy at 80% Lower Cost via Coproduction of Glycolic Acid

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Design, Optimization, and Retrofit of the Formic Acid Process II: Reactive Distillation and Reactive Dividing-Wall Column Retrofits

Cited by 20 publications

References 30 publications

High-Pressure Electrochemical Reduction of CO2 to Formic Acid/Formate: Effect of pH on the Downstream Separation Process and Economics

High-Pressure Electrochemical Reduction of CO2 to Formic Acid/Formate: Effect of pH on the Downstream Separation Process and Economics

Liquid–Liquid Extraction of Formic Acid with 2-Methyltetrahydrofuran: Experiments, Process Modeling, and Economics

Electrochemical Reduction of CO2 to Ethylene with 32% Lower Energy at 80% Lower Cost via Coproduction of Glycolic Acid

Contact Info

Product

Resources

About

High-Pressure Electrochemical Reduction of CO₂ to Formic Acid/Formate: Effect of pH on the Downstream Separation Process and Economics

High-Pressure Electrochemical Reduction of CO₂ to Formic Acid/Formate: Effect of pH on the Downstream Separation Process and Economics