Electrochemical Wastewater Refining: A Vision for Circular Chemical Manufacturing.
Journal of the American Chemical Society
Wastewater is an underleveraged resource; it contains pollutants that can be transformed into valuable high-purity products. Innovations in chemistry and chemical engineering will play critical roles in valorizing wastewater to remediate environmental pollution, provide equitable access to chemical resources and services, and secure critical materials from diminishing feedstock availability. This perspective envisions electrochemical wastewater refining─the use of electrochemical processes to tune and recover specific products from wastewaters─as the necessary framework to accelerate wastewater-based electrochemistry to widespread practice. We define and prescribe a use-informed approach that simultaneously serves specific wastewater-pollutant-product triads and uncovers a mechanistic understanding generalizable to broad use cases. We use this approach to evaluate research needs in specific case studies of electrocatalysis, stoichiometric electrochemical conversions, and electrochemical separations. Finally, we provide rationale and guidance for intentionally expanding the electrochemical wastewater refining product portfolio. Wastewater refining will require a coordinated effort from multiple expertise areas to meet the urgent need of extracting maximal value from complex, variable, diverse, and abundant wastewater resources.
View details for DOI 10.1021/jacs.3c01142
View details for PubMedID 37642501
- Reports from the Frontier: Electrifying Chemical Transformations and Separations to Valorize Wastewater Nitrogen ELECTROCHEMICAL SOCIETY INTERFACE 2023; 32 (2): 29-31
- Reactive Separation of Ammonia from Wastewater Nitrate via Molecular Electrocatalysis ENVIRONMENTAL SCIENCE & TECHNOLOGY LETTERS 2023; 10 (5): 458-463
- Mass Transport Modifies the Interfacial Electrolyte to Influence Electrochemical Nitrate Reduction ACS SUSTAINABLE CHEMISTRY & ENGINEERING 2023
Electrified Ion Exchange Enabled by Water Dissociation in Bipolar Membranes for Nitrogen Recovery from Source-Separated Urine.
Environmental science & technology
Ion exchange (IX) is a promising technology for selective nitrogen recovery from urine; however, IX requires chemical-intensive regeneration that escalates energy consumption and carbon emissions. To overcome this barrier, we demonstrated and investigated a novel electrified IX stripping process (EXS) enabling electrochemical in situ IX regeneration with simultaneous ammonia stripping. EXS combines a weak acid cation exchange resin (WAC) to concentrate ammonia, a bipolar membrane to produce protons for WAC regeneration, and membrane stripping to recover the eluted ammonium from WAC. We observed over 80% regeneration (elution from resin) and recovery (membrane stripping) efficiencies during multiple adsorption-recovery cycles with synthetic and real urine. Comparing WAC with a strong acid cation exchange resin illustrated the critical role of the proton affinity of resin moieties in regulating resin regenerability and conductivity in EXS, which we distinguished from the rationale for material choice in electrodeionization. Compared to other electrochemical recovery methods using unamended wastewater as an electrolyte, EXS enabled control of electrolyte composition during recovery by separating and equalizing influent ammonium via WAC-mediated removal. This electrolyte engineering facilitated tunable EXS energy efficiency (100-300 MJ/kg N). This study informs the design of electrified, intensified systems that enable decentralized nitrogen recovery from urine.
View details for DOI 10.1021/acs.est.2c03771
View details for PubMedID 36223185
Recovery of Clean Water and Ammonia from Domestic Wastewater: Impacts on Embodied Energy and Greenhouse Gas Emissions.
Environmental science & technology
Treatment of domestic wastewater can recover valuable resources, including clean water, energy, and ammonia. Important metrics for these systems are greenhouse gas (GHG) emissions and embodied energy, both of which are location- and technology-dependent. Here, we determine the embodied energy and GHG emissions resulting from a conventional process train, and we compare them to a nonconventional process train. The conventional train assumes freshwater conveyance from a pristine source that requires energy for pumping (US average of 0.29 kWh/m3), aerobic secondary treatment with N removal as N2, and Haber-Bosch synthesis of ammonia. Overall, we find that this process train has an embodied energy of 1.02 kWh/m3 and a GHG emission of 0.77 kg-CO2eq/m3. We compare these metrics to those of a nonconventional process train that features anaerobic secondary treatment technology followed by further purification of the effluent by reverse osmosis and air stripping for ammonia recovery. This "short-cut" process train reduces embodied energy to 0.88 kWh/m3 and GHG emissions to 0.42 kg-CO2eq/m3, while offsetting demand for ammonia from the Haber-Bosch process and decreasing reliance upon water transported over long distances. Finally, to assess the potential impacts of nonconventional nitrogen removal technology, we compared the embodied energy and GHG emissions resulting from partial nitritation/anammox coupled to anaerobic secondary treatment. The resulting process train enabled a lower embodied energy but increased GHG emissions, largely due to emissions of N2O, a potent greenhouse gas.
View details for DOI 10.1021/acs.est.1c07992
View details for PubMedID 35656915
Catalytic Performance and Near-Surface X-ray Characterization of Titanium Hydride Electrodes for the Electrochemical Nitrate Reduction Reaction.
Journal of the American Chemical Society
The electrochemical nitrate reduction reaction (NO3RR) on titanium introduces significant surface reconstruction and forms titanium hydride (TiHx, 0 < x ≤ 2). With ex situ grazing-incidence X-ray diffraction (GIXRD) and X-ray absorption spectroscopy (XAS), we demonstrated near-surface TiH2 enrichment with increasing NO3RR applied potential and duration. This quantitative relationship facilitated electrochemical treatment of Ti to form TiH2/Ti electrodes for use in NO3RR, thereby decoupling hydride formation from NO3RR performance. A wide range of NO3RR activity and selectivity on TiH2/Ti electrodes between -0.4 and -1.0 VRHE was observed and analyzed with density functional theory (DFT) calculations on TiH2(111). This work underscores the importance of relating NO3RR performance with near-surface electrode structure to advance catalyst design and operation.
View details for DOI 10.1021/jacs.2c01274
View details for PubMedID 35315649
The role of intraparticle diffusion path length during electro-assisted regeneration of ion exchange resins: implications for selective adsorbent design and reverse osmosis pretreatment
Chemical Engineering Journal
View details for DOI 10.1016/j.cej.2020.127821
Building an operational framework for selective nitrogen recovery via electrochemical stripping.
2019; 169: 115226
Recovering nitrogen from wastewater can simultaneously fulfill the roles of traditional removal technologies such as nitrification-denitrification and fertilizer production processes such as Haber-Bosch. We have recently demonstrated a proof-of-concept for selective recovery of the fertilizer ammonium sulfate via electrochemical stripping, a combination of electrodialysis and membrane stripping. In this study, we furthered electrochemical stripping from concept to informed practice by investigating the effects of influent concentration (30, 300, and 3000 mg N/L), catholyte temperature (15, 23, and 35 °C), and gas permeable membrane choice on electrochemical nitrogen removal and recovery. We also proposed and validated a nitrogen mass transport model for the experimental results, providing mechanistic rationale behind observed effects of varying operating parameters. While changing operating parameters did affect performance, electrochemical stripping exhibited robust performance over a range of realistic ambient temperatures, three gas permeable membranes, and three orders of magnitude of influent concentrations. Practically, these results demonstrate that electrochemical stripping is viable across a range of waste streams and resilient to fluctuations in temperature and nitrogen concentration; they also establish operational trade-offs between residence time and energy consumption. As a result of this work, electrochemical stripping continues to mature from concept to practice and provides lessons for developing other resource recovery technologies.
View details for DOI 10.1016/j.watres.2019.115226
View details for PubMedID 31765946
Aerosol Fragmentation Driven by Coupling of Acid-Base and Free-Radical Chemistry in the Heterogeneous Oxidation of Aqueous Citric Acid by OH Radicals
JOURNAL OF PHYSICAL CHEMISTRY A
2017; 121 (31): 5856–70
A key uncertainty in the heterogeneous oxidation of carboxylic acids by hydroxyl radicals (OH) in aqueous-phase aerosol is how the free-radical reaction pathways might be altered by acid-base chemistry. In particular, if acid-base reactions occur concurrently with acyloxy radical formation and unimolecular decomposition of alkoxy radicals, there is a possibility that differences in reaction pathways impact the partitioning of organic carbon between the gas and aqueous phases. To examine these questions, a kinetic model is developed for the OH-initiated oxidation of citric acid aerosol at high relative humidity. The reaction scheme, containing both free-radical and acid-base elementary reaction steps with physically validated rate coefficients, accurately predicts the experimentally observed molecular composition, particle size, and average elemental composition of the aerosol upon oxidation. The difference between the two reaction channels centers on the reactivity of carboxylic acid groups. Free-radical reactions mainly add functional groups to the carbon skeleton of neutral citric acid, because carboxylic acid moieties deactivate the unimolecular fragmentation of alkoxy radicals. In contrast, the conjugate carboxylate groups originating from acid-base equilibria activate both acyloxy radical formation and carbon-carbon bond scission of alkoxy radicals, leading to the formation of low molecular weight, highly oxidized products such as oxalic and mesoxalic acid. Subsequent hydration of carbonyl groups in the oxidized products increases the aerosol hygroscopicity and accelerates the substantial water uptake and volume growth that accompany oxidation. These results frame the oxidative lifecycle of atmospheric aerosol: it is governed by feedbacks between reactions that first increase the particle oxidation state, then eventually promote water uptake and acid-base chemistry. When coupled to free-radical reactions, acid-base channels lead to formation of low molecular weight gas-phase reaction products and decreasing particle size.
View details for DOI 10.1021/acs.jpca.7b04892
View details for Web of Science ID 000407656100010
View details for PubMedID 28707900
Diffusive confinement of free radical intermediates in the OH radical oxidation of semisolid aerosols
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
2017; 19 (9): 6814–30
Multiphase chemical reactions (gas + solid/liquid) involve a complex interplay between bulk and interface chemistry, diffusion, evaporation, and condensation. Reactions of atmospheric aerosols are an important example of this type of chemistry: the rich array of particle phase states and multiphase transformation pathways produce diverse but poorly understood interactions between chemistry and transport. Their chemistry is of intrinsic interest because of their role in controlling climate. Their characteristics also make them useful models for the study of principles of reactivity of condensed materials under confined conditions. In previous work, we have reported a computational study of the oxidation chemistry of a liquid aliphatic aerosol. In this study, we extend the calculations to investigate nearly the same reactions at a semisolid gas-aerosol interface. A reaction-diffusion model for heterogeneous oxidation of triacontane by hydroxyl radicals (OH) is described, and its predictions are compared to measurements of aerosol size and composition, which evolve continuously during oxidation. These results are also explicitly compared to those obtained for the corresponding liquid system, squalane, to pinpoint salient elements controlling reactivity. The diffusive confinement of the free radical intermediates at the interface results in enhanced importance of a few specific chemical processes such as the involvement of aldehydes in fragmentation and evaporation, and a significant role of radical-radical reactions in product formation. The simulations show that under typical laboratory conditions semisolid aerosols have highly oxidized nanometer-scale interfaces that encapsulate an unreacted core and may confer distinct optical properties and enhanced hygroscopicity. This highly oxidized layer dynamically evolves with reaction, which we propose to result in plasticization. The validated model is used to predict chemistry under atmospheric conditions, where the OH radical concentration is much lower. The oxidation reactions are more strongly influenced by diffusion in the particle, resulting in a more liquid-like character.
View details for DOI 10.1039/c7cp00696a
View details for Web of Science ID 000396031200050
View details for PubMedID 28218326