A perspective on three sustainable hydrogen production technologies with a focus on technology readiness level, cost of production and life cycle environmental impacts.

Hydrogen will play an indispensable role as both an energy vector and as a molecule in essential products in the transition to climate neutrality. However, the optimal sustainable hydrogen production system is not definitive due to challenges in energy conversion efficiency, economic cost, and associated marginal abatement cost. This review summarises and contrasts different sustainable hydrogen production technologies including for their development, potential for improvement, barriers to large-scale industrial application, capital and operating cost, and life-cycle environmental impact. Polymer electrolyte membrane water electrolysis technology shows significant potential for large-scale application in the near-term, with a higher technology readiness level (expected to be 9 by 2030) and a levelized cost of hydrogen expected to be 4.15-6 €/kg H2 in 2030; this equates to a 50% decrease as compared to 2020. The four-step copper-chlorine (Cu-Cl) water thermochemical cycle can perform better in terms of life cycle environmental impact than the three- and five-step Cu-Cl cycle, however, due to system complexity and high capital expenditure, the thermochemical cycle is more suitable for long-term application should the technology develop. Biological conversion technologies (such as photo/dark fermentation) are at a lower technology readiness level, and the system efficiency of some of these pathways such as biophotolysis is low (less than 10%). Biomass gasification may be a more mature technology than some biological conversion pathways owing to its higher system efficiency (40%-50%). Biological conversion systems also have higher costs and as such require significant development to be comparable to hydrogen produced via electrolysis.

Design, Construction, and Concept Validation of a Laboratory-Scale Two-phase Reactor to Valorize Whiskey Distillery By-products.

The by-products generated from the whiskey distillation process consist of organic liquids with a high chemical oxygen demand (COD) and residues with a high solid content. Low-carbon strategies that repurpose and valorize such by-products are now imperative to reduce the carbon footprint of the food and beverage industries. The operation of a two-phase anaerobic digester to produce volatile fatty acids (VFAs) and biogas may enable distilleries to transition toward a low-carbon bioeconomy. An example of such a system is a leach bed reactor connected to an expanded granular sludge bed (LBR-EGSB) which was designed, commissioned, and conceptually validated in this paper. Several design improvements progress the LBR-EGSB beyond previous reactor designs. An external gas-liquid-solid separator in the EGSB was used to capture any residual gases produced by the effluent and may reduce the amount of methane slippage and biomass washout. The implementation of a siphon-actuated leachate cup is a low-cost alternative that is less prone to actuation malfunction as compared to electrically actuated solenoid valves in previous reactor designs. Furthermore, replacing fresh water with distillery's liquid by-products as leachate promotes a circular repurpose and reuse philosophy. The system proved to be effective in generating VFAs (10.3 g VFAs L-1Leachate), in EGSB COD removal (96%), and in producing methane-rich biogas (75%vol), which is higher than the values achieved by traditional anaerobic digestion systems. The LBR-EGSB could ultimately provide more by-product valorization and decarbonization opportunities than traditional anaerobic digestion systems for a whiskey distillery.

Demand-driven biogas production from Upflow Anaerobic Sludge Blanket (UASB) reactors to balance the power grid.

Future energy systems necessitate dispatchable renewable energy to balance electrical grids with high shares of intermittent renewables. Biogas from anaerobic digestion (AD) can generate electricity on-demand. High-rate methanogenic reactors, such as the Upflow Anaerobic Sludge Blanket (UASB), can react quicker to variations in feeding as compared to traditional AD systems. In this study, experimental trials validated the feasibility of operating the UASB in a demand-driven manner. The UASB was operated with leachate produced from a hydrolysis reactor treating grass silage. The UASB demonstrated a high degree of flexibility in responding to variable feeding regimes. The intra-day biogas production rate could be increased by up to 123% under 4 hours in demand-driven operation, without significant deterioration in performance. A model based on kinetic analysis was developed to help align demand-driven operation with the grid. The findings suggest significant opportunities for UASBs to provide positive and negative balance to the power grid.

Two-phase anaerobic digestion for enhanced valorisation of whiskey distillery by-products.

The valorisation of whiskey by-products was assessed and compared in three anaerobic digestion systems. The systems produced similar methane yields, which could satisfy up to 44% of the thermal energy demand at a distillery. Using methane generated from by-products would displace natural gas and reduce the distillery's carbon footprint. Two-phase systems had higher methane content (ca. 75 %vol) than the traditional system (54 %vol) and furthermore, unlocked opportunities for volatile fatty acid production. The potential value that could be generated from the extraction of butyric acid and caproic acid was approximately €6.76 million for a 50 million litre alcohol facility (0.14 € per litre of whiskey). All three anaerobic digestion systems showed the potential to valorise whiskey by-products and convert current linear distillery production processes into circular repurpose and reuse production processes.

Decarbonising distilled spirits: An assessment of the potential associated with anaerobic digestion of by-products at nine operational distilleries.

This work aims to assess the potential biogas resource of by-products from the production of distilled spirits at 9 operational distilleries in 7 countries. An additional objective was the calculation of the energy resource and Scope 1 greenhouse gas (GHG) emission savings from the use of 21 by-products from the distilleries as a feedstock for anaerobic digestion (AD). To present a holistic perspective on the integration of AD with distilleries, an overview of additional criteria to be considered was provided. The biochemical methane potential (BMP) of the by-products associated with a selection of distilled spirits was experimentally determined. The BMP ranged from 161 L methane per kg volatile solid (LCH4/kgVS) to 589 LCH4/kgVS with an average value of 332 LCH4/kgVS. Biogas could reduce distillery fossil fuel demand by 49% when produced from un-processed by-products, by 66% when produced from a mixture of separated by-products, by 16% when produced from concentrated by-products and by 13% when produced from liquid by-products. The average Scope 1 GHG emission saving when using un-processed by-products was 52%, a mix of separated by-products allowed for a reduction of 66%, liquid by-products achieved an average reduction of 14%, and the use of concentrated by-products reduced GHG emissions by 17% on average. When evaluating which distilleries are "of most interest" for the integration of AD, other criteria to be considered include: by-product properties, the size of the AD facility required, the quantity of digestate produced, and the location of the distilleries in terms of both land availability to construct the AD facility and the proximity to land on which to spread digestate.

A comparison of digestate management options at a large anaerobic digestion plant.

Increased biogas production from increasing numbers of anaerobic digestion (AD) facilities has increased the mass of digestate applied to agricultural land close to AD plants and has led to an oversupply in some regions. This necessitates long distance digestate transportation accompanied by economic, environmental, and social drawbacks. This work assesses the performance of three different digestate management options (MOs); land application of whole digestate (MO1), digestate separation (MO2), and digestate separation and evaporation (MO3), combined with centralised or decentralised digestate storage. All MOs required the same landbank area, whilst MO2 and MO3 reduced digestate management costs by 9% and 37% (if recovered heat is used) respectively. GHG emissions from MO2 were 41% lower than MO1 if renewable electricity was used. MO3 reduced GHG emissions by 63% compared to MO1, if renewable electricity and recovered heat were used. MO2 required the same centralised digestate storage volume as MO1 while MO3 required 44% of the centralised storage volume. Centralised digestate storage required a maximum of 79 days for digestate transportation (33 trucks/day, 20 m3 capacity) to land for MO1 and MO2, and 35 days for MO3. Decentralised digestate storage required 63 storage tanks and 15 trucks/day for MO1, 69 tanks and 15 trucks/day for MO2, and 68 tanks and 7 trucks/day for MO3. Tank size ranged from 500 m3 to 20,000 m3. MO3 combined with decentralised storage could reduce the cost and GHG emissions (if recovered energy is used), vehicle movements, and the number of storage tanks required for digestate management.

An assessment of how the properties of pyrochar and process thermodynamics impact pyrochar mediated microbial chain elongation in steering the production of medium-chain fatty acids towards n-caproate.

Microbial chain elongation fermentation is an alternative technology for medium-chain fatty acid (MCFA) production. This paper proposed the addition of pyrochar and graphene in chain elongation to improve MCFA production using ethanol and acetate as substrates. Results showed that the yield of, and selectivity towards, C6 n-caproate were significantly enhanced with pyrochar addition. At the optimal mass ratio of pyrochar to substrate of 2 g/g, the maximum n-caproate yield of 13.67 g chemical oxygen demand/L and the corresponding selectivity of 56.8% were obtained; this represents an increase of 115% and 128% respectively as compared with no pyrochar addition. Such improvements were postulated as due to the high electrical conductivity and surface redox groups of pyrochar. The optimal ethanol to acetate molar ratio of 2 mol/mol achieved the highest MCFA yield under pyrochar mediated chain elongation conditions. Thermodynamic calculations modelled an energy benefit of 93.50 kJ/mol reaction for pyrochar mediated n-caproate production.

A perspective on the combination of alkali pre-treatment with bioaugmentation to improve biogas production from lignocellulose biomass.

Anaerobic digestion (AD) is a bioprocess technology that integrates into circular economy systems, which produce renewable energy and biofertilizer whilst reducing greenhouse gas emissions. However, improvements in biogas production efficiency are needed in dealing with lignocellulosic biomass. The state-of-the-art of AD technology is discussed, with emphasis on feedstock digestibility and operational difficulty. Solutions to these challenges including for pre-treatment and bioaugmentation are reviewed. This article proposes an innovative integrated system combining alkali pre-treatment, temperature-phased AD and bioaugmentation techniques. The integrated system as modelled has a targeted potential to achieve a biodegradability index of 90% while increasing methane production by 47% compared to conventional AD. The methane productivity may also be improved by a target reduction in retention time from 30 to 20 days. This, if realized has the potential to lower energy production cost and the levelized cost of abatement to facilitate an increased resource of sustainable commercially viable biomethane.

Emerging bioelectrochemical technologies for biogas production and upgrading in cascading circular bioenergy systems.

Biomethane is suggested as an advanced biofuel for the hard-to-abate sectors such as heavy transport. However, future systems that optimize the resource and production of biomethane have yet to be definitively defined. This paper assesses the opportunity of integrating anaerobic digestion (AD) with three emerging bioelectrochemical technologies in a circular cascading bioeconomy, including for power-to-gas AD (P2G-AD), microbial electrolysis cell AD (MEC-AD), and AD microbial electrosynthesis (AD-MES). The mass and energy flow of the three bioelectrochemical systems are compared with the conventional AD amine scrubber system depending on the availability of renewable electricity. An energy balance assessment indicates that P2G-AD, MEC-AD, and AD-MES circular cascading bioelectrochemical systems gain positive energy outputs by using electricity that would have been curtailed or constrained (equivalent to a primary energy factor of zero). This analysis of technological innovation, aids in the design of future cascading circular biosystems to produce sustainable advanced biofuels.

How can ethanol enhance direct interspecies electron transfer in anaerobic digestion?

Anaerobic digestion (AD) of organic waste to produce biogas is a mature biotechnology commercialised for decades. However, the relatively recent discovery of direct interspecies electron transfer (DIET) brings a new opportunity to improve the efficiency of biogas technology. DIET may replace mediated interspecies electron transfer (MIET) by efficient electron transfer between exoelectrogens and electrotrophic methanogens, thereby enhancing yields and rates of biogas production. Ethanol, as the initial electron donor in the discovery of the DIET pathway, is now a "hot topic" in the literature. Recent studies have indicated that ethanol in AD functions not only as the substrate, but also as the precursor to stimulate DIET by enriching exoelectrogens and electrotrophic methanogens for co-digesting complex organic wastes. This review aims to highlight the state of the art and recent advances in ethanol-based DIET in AD. The DIET associated reactions of ethanol oxidation and carbon dioxide reduction are assessed by thermodynamic analysis to reveal the extent of the potential for improvement of the AD processes that utilizes DIET pathways. Three ethanol-based DIET strategies are discussed: (1) ethanol as the sole substrate supplemented with conductive materials in AD, (2) ethanol co-digestion with complex substrates and (3) ethanol-type fermentation prior to AD. This review aims to chart the pathways for improved AD performance by utilizing ethanol-based DIET in specific treatments of biological wastes.

Design, Commissioning, and Performance Assessment of a Lab-Scale Bubble Column Reactor for Photosynthetic Biogas Upgrading with Spirulina platensis.

The two-step bubble column-photobioreactor photosynthetic biogas upgrading system can enable simultaneous production of biomethane and value-added products from microalgae. However, due to the influence of a large number of variables, including downstream processes and the presence of microalgae, no unanimity has been reached regarding the performance of bubble column reactors in photosynthetic biogas upgrading. To investigate this further, the present work documents in detail, the design and commissioning of a lab-scale bubble column reactor capable of treating up to 16.3 L/h of biogas while being scalable. The performance of the bubble column was assessed at a pH of 9.35 with different algal densities of Spirulina platensis at 20 °C in the presence of light (3-5 klux or 40.5-67.5 µmol m-2 s-1). A liquid/gas flow (L/G) ratio of 0.5 allowed consistent CO2 removal of over 98% irrespective of the algal density or its photosynthetic activity. For lower concentrations of algae, the volumetric O2 concentration in the upgraded biomethane varied between 0.05 and 0.52%, thus providing grid quality biomethane. However, for higher algal concentrations, increased oxygen content in the upgraded biomethane due to both enhanced O2 stripping and the photosynthetic activity of the microalgae as well as clogging and foaming posed severe operational challenges.

Production of Bio-alkanes from Biomass and CO2.

Bioelectrochemical technologies such as electro-fermentation and microbial CO2 electrosynthesis are emerging interdisciplinary technologies that can produce renewable fuels and chemicals (such as carboxylic acids). The benefits of electrically driven bioprocesses include improved production rate, selectivity, and carbon conversion efficiency. However, the accumulation of products can lead to inhibition of biocatalysts, necessitating further effort in separating products. The recent discovery of a new photoenzyme, capable of converting carboxylic acids to bio-alkanes, has offered an opportunity for system integration, providing a promising approach for simultaneous product separation and valorisation. Combining the strengths of photo/bio/electrochemical catalysis, we discuss an innovative circular cascading system that converts biomass and CO2 to value-added bio-alkanes (CnH2n+2, n = 2 to 5) whilst achieving carbon circularity.

Effects of foam nickel supplementation on anaerobic digestion: Direct interspecies electron transfer.

Stimulating direct interspecies electron transfer with conductive materials is a promising strategy to overcome the limitation of electron transfer efficiency in syntrophic methanogenesis of industrial wastewater. This paper assessed the impact of conductive foam nickel (FN) supplementation on syntrophic methanogenesis and found that addition of 2.45 g/L FN in anaerobic digestion increased the maximum methane production rate by 27.4 % (on day 3) while decreasing the peak production time by 33 % as compared to the control with no FN. Cumulative methane production from day 2 to 6 was 14.5 % higher with addition of 2.45 g/L FN than in the control. Levels of FN in excess of 2.45 g/L did not show benefits. Cyclic voltammetry results indicated that the biofilm formed on the FN could generate electrons. The dominant bacterial genera in suspended sludge were Dechlorobacter and Rikenellaceae DMER64, whereas that in the FN biofilm was Clostridium sensu stricto 11. The dominant archaea Methanosaeta in the FN biofilm was enriched by 14.1 % as compared to the control.

A perspective on novel cascading algal biomethane biorefinery systems.

Synergistic opportunities to combine biomethane production via anaerobic digestion whilst cultivating microalgae have been previously suggested in literature. While biomethane is a promising and flexible renewable energy vector, microalgae are increasingly gaining importance as an alternate source of food and/or feed, chemicals and energy for advanced biofuels. However, simultaneously achieving, grid quality biomethane, effective microalgal digestate treatment, high microalgae growth rate, and the most sustainable use of the algal biomass is a major challenge. In this regard, the present paper proposes multiple configurations of an innovative Cascading Algal Biomethane-Biorefinery System (CABBS) using a novel two-step bubble column-photobioreactor photosynthetic biogas upgrading technology. To overcome the limitations in choice of microalgae for optimal system operation, a microalgae composition based biorefinery decision tree has also been conceptualised to maximise profitability. Techno-economic, environmental and practical aspects have been discussed to provide a comprehensive perspective of the proposed systems.

Biological hydrogen methanation systems - an overview of design and efficiency.

The rise in intermittent renewable electricity production presents a global requirement for energy storage. Biological hydrogen methanation (BHM) facilitates wind and solar energy through the storage of otherwise curtailed or constrained electricity in the form of the gaseous energy vector biomethane. Biological methanation in the circular economy involves the reaction of hydrogen - produced during electrolysis - with carbon dioxide in biogas to produce methane (4H2 + CO2 = CH4 + 2H2), typically increasing the methane output of the biogas system by 70%. In this paper, several BHM systems were researched and a compilation of such systems was synthesized, facilitating comparison of key parameters such as methane evolution rate (MER) and retention time. Increased retention times were suggested to be related to less efficient systems with long travel paths for gases through reactors. A significant lack of information on gas-liquid transfer co-efficient was identified.

How to optimise photosynthetic biogas upgrading: a perspective on system design and microalgae selection.

Photosynthetic biogas upgrading using microalgae provides a promising alternative to commercial upgrading processes as it allows for carbon capture and re-use, improving the sustainability of the process in a circular economy system. A two-step absorption column-photobioreactor system employing alkaline carbonate solution and flat plate photobioreactors is proposed. Together with process optimisation, the choice of microalgae species is vital to ensure continuous performance with optimal efficiency. In this paper, in addition to critically assessing the system design and operation conditions for optimisation, five criteria are selected for choosing optimal microalgae species for biogas upgrading. These include: ability for mixotrophic growth; high pH tolerance; external carbonic anhydrase activity; high CO2 tolerance; and ease of harvesting. Based on such criteria, five common microalgae species were identified as potential candidates. Of these, Spirulina platensis is deemed the most favourable species. An industrial perspective of the technology further reveals the significant challenges for successful commercial application of microalgal upgrading of biogas, including: a significant land footprint; need for decreasing microalgae solution recirculation rate; and selecting preferable microalgae utilisation pathway.

Graphene Facilitates Biomethane Production from Protein-Derived Glycine in Anaerobic Digestion.

Interspecies electron transfer is a fundamental factor determining the efficiency of anaerobic digestion (AD), which involves syntrophy between fermentative bacteria and methanogens. Direct interspecies electron transfer (DIET) induced by conductive materials can optimize this process offering a significant improvement over indirect electron transfer. Herein, conductive graphene was applied in the AD of protein-derived glycine to establish DIET. The electron-producing reaction via DIET is thermodynamically more favorable and exhibits a more negative Gibbs free energy value (-60.0 kJ/mol) than indirect hydrogen transfer (-33.4 kJ/mol). The Gompertz model indicated that the kinetic parameters exhibited linear correlations with graphene addition from 0.25 to 1.0 g/L, leading to the highest increase in peak biomethane production rate of 28%. Sedimentibacter (7.8% in abundance) and archaea Methanobacterium (71.1%) and Methanosarcina (11.3%) might be responsible for DIET. This research can open up DIET to a range of protein-rich substrates, such as algae.

Cascading biomethane energy systems for sustainable green gas production in a circular economy.

Biomethane is a flexible energy vector that can be used as a renewable fuel for both the heat and transport sectors. Recent EU legislation encourages the production and use of advanced, third generation biofuels with improved sustainability for future energy systems. The integration of technologies such as anaerobic digestion, gasification, and power to gas, along with advanced feedstocks such as algae will be at the forefront in meeting future sustainability criteria and achieving a green gas supply for the gas grid. This paper explores the relevant pathways in which an integrated biomethane industry could potentially materialise and identifies and discusses the latest biotechnological advances in the production of renewable gas. Three scenarios of cascading biomethane systems are developed.

Boosting biomethane yield and production rate with graphene: The potential of direct interspecies electron transfer in anaerobic digestion.

Interspecies electron transfer between bacteria and archaea plays a vital role in enhancing energy efficiency of anaerobic digestion (AD). Conductive carbon materials (i.e. graphene nanomaterial and activated charcoal) were assessed to enhance AD of ethanol (a key intermediate product after acidogenesis of algae). The addition of graphene (1.0g/L) resulted in the highest biomethane yield (695.0±9.1mL/g) and production rate (95.7±7.6mL/g/d), corresponding to an enhancement of 25.0% in biomethane yield and 19.5% in production rate. The ethanol degradation constant was accordingly improved by 29.1% in the presence of graphene. Microbial analyses revealed that electrogenic bacteria of Geobacter and Pseudomonas along with archaea Methanobacterium and Methanospirillum might participate in direct interspecies electron transfer (DIET). Theoretical calculations provided evidence that graphene-based DIET can sustained a much higher electron transfer flux than conventional hydrogen transfer.

Study of the performance of a thermophilic biological methanation system.

This study investigated the operation of ex-situ biological methanation at two thermophilic temperatures (55°C and 65°C). Methane composition of 85-88% was obtained and volumetric productivities of 0.45 and 0.4LCH4/Lreactor were observed at 55°C and 65°C after 24h respectively. It is postulated that at 55°C the process operated as a mixed culture as the residual organic substrates in the starting inoculum were still available. These were consumed prior to the assessment at 65°C; thus the methanogens were now dependent on gaseous substrates CO2 and H2. The experiment was repeated at 65°C with fresh inoculum (a mixed culture); methane composition and volumetric productivity of 92% and 0.46LCH4/Lreactor were achieved in 24h. Methanothermobacter species represent likely and resilient candidates for thermophilic biogas upgrading.