Steam reforming of technical bioethanol for hydrogen production

Essentially all work on ethanol steam reforming so far has been carried out using simulated bioethanol feedstocks, which means pure ethanol mixed with water. However, technical bioethanol consists of a lot of different components including sugars, which cannot be easily vaporized and steam reformed. For ethanol steam reforming to be of practical interest, it is important to avoid the energy-intensive purification steps to fuel grade ethanol. Therefore, it is imperative to analyze how technical bioethanol, with the relevant impurities, reacts during the steam reforming process. We show how three different distillation fractions of technical 2nd generation bioethanol, produced in a pilot plant, influence the performance of nickel- and ruthenium-based catalysts during steam reforming, and we discuss what is required to obtain high activity and long catalyst lifetime. We conclude that the use of technical bioethanol will result in a faster catalyst deactivation than what is observed when using pure ethanol–water mixtures because of contaminants remaining in the feed. However, the initial activity of the catalysts are not affected by this, hence it is important to not only focus on catalyst activity but rather on the lifetime of the catalyst.     

Cooperative role of cobalt and gallium under the ethanol steam reforming on Co/CeGaOx

The performance of gallium promoted cobalt-ceria catalysts for ethanol steam reforming (ESR) was studied using H₂O/C₂H₅OH = 6/1 mol/mol at 500 °C. The catalysts were synthetized via cerium-gallium co-precipitation and wetness impregnation of cobalt. A detailed characterization by N₂-physisorption, XRD, H₂-TPR and TEM allowed the normalization of contact time and rationalization of the role of each catalysts component for ESR. The gallium promoted catalyst, Co/Ce₉₀Ga₁₀O_x, was more efficient for the ethanol conversion to H₂ and CO₂, and the production of oxygenated by-products (such as, acetaldehyde and acetone) than Co/CeO₂. The catalytic performance is explained assuming that: (i) bare ceria is able to dehydrogenate ethanol to ethylene; (ii) Ce–O–Ga interface catalyzes ethanol reforming; (iii) both Ce–O–Co and Ce–O–Ga interfaces takes part in acetone production; and (iv) cobalt sites further allow C–C scission. It is suggested that a cooperative role between Co and Ce–O–Ga sites enhance the H₂ and CO₂ yields under ESR conditions.     

Hydrogen,ethylene and power production from bioethanol: Ready for the renewable market?

The economic sustainability of renewable based sources is a matter of debate and the technology is changing very fast. We here considered three examples of exploitation of bioethanol as renewable source: a) centralised hydrogen prodution; b) heat and power cogeneration (residential scale); c) ethylene production. Bioethanol can be a suitable starting material for the production of H₂, as fuel or chemical, or syngas. After designing the process and the implementation of kinetic expressions based on experimental data collected in our lab or derived from the literature, an economic evaluation and sensitivity analysis allowed to assess the economic sustainability of hydrogen production and purification by the steam reforming of bioethanol. The attention was mainly put on diluted bioethanol solutions, easy to purify and cost effective. The centralised hydrogen production from bioethanol was considered cost effective at least starting from diluted bioethanol from first generation crops. When dowscaling the hydrogen production and purification unit to feed a 5 kW fuel cell, the most undetermined item was the fuel cell cost, since no acclarate market price is still available.Finally, ethylene market is steadily increasing by ca. 4% each year due to economic growth. The demand for renewable ethylene, as well as the increasing oil price experienced in the recent past, suggested the development of alternative routes to ethylene. Based on the increasing availability of ethanol form renewable biomass, bioethanol-to-bioethylene processes have been recently designed, finding economic sustainability, at the moment, in Brazil.     

Production of anhydrous ethanol using oil palm empty fruit bunch in a pilot plant

Bioethanol production from lignocellulosic biomass for use as an alternative energy resource has attracted increasing interest, but short-term commercialization will require several technologies such as low cost feedstock. The huge amount of oil palm empty fruit bunches (EFB) generated from palm oil industries can be used as a raw material for cheap, renewable feedstock for further commercial exploitation. Using a pilot-scale bioethanol plant, this study investigated the possibility of utilizing oil palm empty fruit bunches as a renewable resource. All bioethanol production processes such as pretreatment, hydrolysis, fermentation, and purification were constructed as automatically controlled integrated processes. The mass balance was calculated from operational results. Changhae ethanol multiexplosion pretreatment with sodium hydroxide was conducted to improve the enzymatic hydrolysis process, and a separate hydrolysis and fermentation process was used for producing bioethanol at an 83.6% ethanol conversion rate. In order to purify the ethanol, a distillation and dehydration facility was operated. Distillation and dehydration efficiencies were 98.9% and 99.2%, respectively. The material balance could be calculated using results obtained from the operation of the pilot-scale bioethanol plant. As a result, it was possible to produce 144.4 kg anhydrous ethanol (99.7 wt%) from 1000 kg EFB. This result constitutes a significant contribution to the feasibility of bioethanol production from lignocellulosic biomass and justifies the pilot plant's scale-up to a commercial-scale plant.     

Synergistic catalysis of bi-metals in the reforming of biomass-derived hydrocarbons: A review

Biomass such as ethanol and glycerol has emerged as an alternative feedstock for hydrogen (H₂) production in recent years. Ethanol, which is high in H_2, can easily be derived from renewable biomass sources, whereas; glycerol is a by-product of biodiesel expected to be surplus in the coming years. Several catalytic reforming routes involving biomass such as steam, CO₂, auto thermal, partial oxidation and aqueous-phase reforming can produce syngas or H₂. Bimetallic catalysis is one of the potential solutions to reduce carbon formation and catalysts deactivation in reforming processes since it can produce more stable catalysts from the synergistic effect of the combined metals. There are many reviews on catalyst designs and reaction pathways reported in the literature; nevertheless, comparative literature is lacking on the metal configuration of bimetallic catalyst in biomass reforming particularly for ethanol and glycerol reforming reactions. Therefore, studies linked with the synergistic effects of various bi-metal combinations of catalysts used in biomass reforming processes have been reviewed in the paper. Moreover, the study provides data for the application of bimetallic catalyst for industrial biomass processes.     

A techno-economic evaluation of the hydrogen production for energy generation using an ethanol fuel processor

The techno-economic analysis of a process to convert ethanol into H₂ to be used as a fuel for PEM fuel cells of H₂-powered cars was done. A plant for H₂ production was simulated using experimental results obtained on monolith reactors for ethanol steam reforming and WGS steps. The steam reforming (Rh/CeSiO₂) and WGS (Pt/ZrO₂) monolith catalysts remained quite stable during long-term startup/shut down cycles, with no carbon deposition. The H₂ production cost was significantly affected by the ethanol price. The monolith catalyst costs contribution was lower than that of conventional reactors. The H₂ production cost obtained using the expensive Brazilian ethanol price (0.81 US$/L ethanol) was US$ 8.87/kg H₂, which is lower than the current market prices (US$ 13.44/kg H₂) practiced at H₂ refueling stations in California. This result showed that this process is economically feasible to provide H₂ as a fuel for H₂-powered cars at competitive costs in refueling stations.     

High performance Ni exsolved and Cu added La0.8Ce0.2Mn0.6Ni0.4O3-based perovskites for ethanol steam reforming

La_0.8Ce_0.2Mn_0.6Ni_0.4O₃ with (LCMN@CuO) and without (LCMN) CuO addition are prepared by solution methods, followed by reduction in 5% H₂–N₂ stream at 650 °C to form Ni exsolved and CuO reduced catalysts, LCMN@Ni and LCMN@Ni/Cu, for ethanol (EtOH) steam reforming (ESR). The catalysts are characterized by X-ray diffraction (XRD), scanning and transmission electron microscopies (SEM and TEM), temperature programmed reduction (H₂-TPR), X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy etc., and are evaluated for ESR with a steam/carbon ratio of 3 and a weight hourly space velocity (WHSV) of 4 h⁻¹ at temperatures between 500 and 700 °C. Ni exsolution and CuO reduction are confirmed on the substrates in LCMN@Ni and LCMN@Ni/Cu. Both the catalysts demonstrate a complete conversion of EtOH, forming mainly H₂, CO₂, CO and CH₄. And increasing temperature to 700 °C increases the yields of H₂ and CO to the levels about 90% and 40%, respectively, at the cost of CH₄; and such performance remains unchanged for 30 h. These results indicate that both LCMN@Ni and LCMN@Ni/Cu are promising catalysts for ESR, the main difference between them is that the latter is more chemically stable and more resistant to carbon deposition under ESR conditions.     

Experimental study of the oxidative steam reforming of fuel grade bioethanol over Pt–Ni metallic foam structured catalysts

In this work, Pt–Ni/CeO₂ catalysts have been used for the oxidative steam reforming of fuel grade bioethanol. To transfer the above formulation on structured carriers, due to the requirement of a washcoat (wc) deposition, it was mandatory to carry out a preliminary study on the catalysts in the form of powder. An initial experimental campaign was performed to optimise the ceria loading (between 25 and 45 wt%) as well as the Pt content (between 2 and 5 wt%): stability tests were carried out for 24 h at 500 °C, WHSV = 12.3 h⁻¹, H₂O/C₂H₅OH ratio of 4, O₂/C₂H₅OH of 0.5. The highest activity, selectivity and durability was recorded over the 3Pt–10Ni/35CeO₂/wc, which assured an ethanol conversion of almost 98% at the end of the test with a corresponding H₂ yield of 50%. This interesting formulation was transferred on a Ni–Fe substrate, made of an open cell foam, which was tested under the same operative conditions described above: the structured catalyst, due to the very good heat management within the catalytic bed and the improved mass transport, displayed a more stable behaviour compared to the corresponding powder, even in the presence of the typical bioethanol impurities; moreover, the formation of unwanted by-products was negligible throughout the whole investigated interval.     

Combined ethanol and methane production from switchgrass (Panicum virgatum L.) impregnated with lime prior to steam explosion

Pretreatments are crucial to achieve efficient conversion of lignocellulosic biomass to soluble sugars. In this light, switchgrass was subjected to 13 pretreatments including steam explosion alone (195 °C for 5, 10 and 15 min) and after impregnation with the following catalysts: Ca(OH)₂ at low (0.4%) and high (0.7%) concentration; Ca(OH)₂ at high concentration and higher temperature (205 °C for 5, 10 and 15 min); H₂SO₄ (0.2% at 195 °C for 10 min) as reference acid catalyst before steam explosion. Enzymatic hydrolysis was carried out to assess pretreatment efficiency in both solid and liquid fraction. Thereafter, in selected pretreatments the solid fraction was subjected to simultaneous saccharification and fermentation (SSF), while the liquid fraction underwent anaerobic digestion (AD). Lignin removal was lowest (12%) and highest (35%) with steam alone and 0.7% lime, respectively. In general, higher cellulose degradation and lower hemicellulose hydrolysis were observed in this study compared to others, depending on lower biomass hydration during steam explosion. Mild lime addition (0.4% at 195 °C) enhanced ethanol in SSF (+28% than steam alone), while H₂SO₄ boosted methane in AD (+110%). However, methane represented a lesser component in combined energy yield (ethanol, methane and energy content of residual solid). Mild lime addition was also shown less aggressive and secured more residual solid after SSF, resulting in higher energy yield per unit raw biomass. Decreased water consumption, avoidance of toxic compounds in downstream effluents, and post process recovery of Ca(OH)₂ as CaCO₃ represent further advantages of pretreatments involving mild lime addition before steam explosion.     

Multi-size distributed Ni catalyst embedded in SiCxOy film by inverse microemulsion-precipitation method for ethanol steam reforming

Ni/SiC_xO_y catalysts with multi-size distribution of Ni particles, were prepared and supported on porous SiC ceramics by a combination of inverse microemulsion and precipitation methods, as reaction microchannels for ethanol steam reforming (ESR). The microstructure, phase composition, reduction performance, hydrogen production performance of ESR, and the type and growth of carbon deposition were investigated for Ni/SiC_xO_y catalysts. The Ni catalysts embedded in SiC_xO_y film with the appropriate amount of precipitant exhibited multi-size distribution and minimal particle size. The initial ethanol conversion rate and H₂ selectivity of Ni/SiC_xO_y catalysts during ESR reaction were 100% and 75%, respectively, remaining 95% and 69.2% after 20 h, respectively. Raman and SEM results indicate that Ni/SiC_xO_y catalysts with appropriate amounts of precipitant tended to grow more loosely arranged carbon nanowires. The combination of inverse microemulsion and precipitation methods produced smaller and multi-size distributed Ni/SiC_xO_y catalysts with superior durability and hydrogen production performance in ESR reaction.     

Hydrogen production from steam reforming of bioethanol using Cu/Ni/K/γ-Al2O3 catalysts. Effect of Ni

Hydrogen to be used as a raw material in fuel cells or even as a direct fuel can be obtained from steam reforming of bioethanol. The key aim of this process is to maximize hydrogen production, discouraging at the same time those reactions leading to undesirable products, such as methane, acetaldehyde, diethyl ether or acetic acid, that compete with H₂ for the hydrogen atoms. Cu–Ni–K/γ-Al₂O₃ catalysts are suitable for this reaction since they are able to produce acceptable amounts of hydrogen working at atmospheric pressure and a temperature of 300°C. The effect of nickel content in the catalyst on the steam-reforming reaction was analyzed. Nickel addition enhances ethanol gasification, increasing the gas yield and reducing acetaldehyde and acetic acid production.     

Direction of glucose fermentation towards hydrogen or ethanol production through on-line pH control

The present study investigated the production of hydrogen (H₂) and ethanol from glucose in an Anaerobic Continuous Stirred Tank Reactor (ACSTR). Effects of hydraulic retention time (HRT) and pH on the preference of producing H₂ and/or ethanol and other soluble metabolic products in an open anaerobic enriched culture were studied. Production rates of H₂ and ethanol increased with the increase of biomass concentration. Open anaerobic fermentation was directed and managed through on-line pH control for the production of H₂ or ethanol. Hydrogen was produced by ethanol and acetate-butyrate type fermentations. pH has strong effect on the H₂ or ethanol production by changing fermentation pathways. ACSTR produced mainly ethanol at over pH 5.5 whereas highest H₂ production was obtained at pH 5.0. pH 4.9 favored the lactate production and accumulation of lactate inhibited the biomass concentration in the reactor and the production of H₂ and ethanol. The microbial community structure quickly responded to pH changes and the Clostridia dominated in ACSTR during the study. H₂ production was maintained mainly by Clostridium butyricum whereas in the presence of Bacillus coagulans glucose oxidation was directed to lactate production.     

Effect of La2O3 and CeO2 loadings on formation of nickel-phyllosilicate precursor during preparation of Ni/SBA-15 for hydrogen-rich gas production from ethanol steam reforming

The importance of La₂O₃ or both La₂O₃ and CeO₂ promoters on the formation of nickel phyllosilicate (Ni₃Si₄O₁₂H₂) as a precursor of Ni/SBA-15 for ethanol steam reforming (ESR) was investigated. The catalyst was made by a one-step modified conventional triblock copolymer synthesis method (pH-Adjustment with ammonium hydroxide). The prepared catalysts were characterized by N₂ adsorption/desorption isotherms, XRD, H₂-TPR, SEM-EDS and TGA-DSC techniques. The N₂ adsorption/desorption isotherms identified the mesoporous nature of the catalysts and the XRD patterns of the calcined catalysts confirmed the formation of nickel-phyllosilicate structure. The H₂-TPR analysis revealed that the La₂O₃ loading considerably increased the interaction between nickel and silica frame work of SBA-15 support. The ability of these catalysts for hydrogen production from ethanol steam reforming (ESR) was evaluated in a packed bed reactor at 650 °C. In the case of Ni/SBA-15 catalysts without and with La₂O₃ promoter, the ESR experiments experienced metal sintering and coke formation. Meanwhile, the catalytic activity of both La₂O₃ and CeO₂ promoted Ni/SBA-15 catalyst (Ni-La₂O₃-CeO₂/SBA-15) remained stable with time on stream in terms of GPR and hydrogen selectivity. The stable performance of this catalyst was explained by the strong interaction of nickel with SBA-15 promoted by La₂O₃ and the suppression of coke formation by CeO₂.     

Hydrogen production from raw bioethanol steam reforming: Optimization of catalyst composition with improved stability against various impurities

The use of raw bioethanol is of major importance for a cost effective industrial application. Raw bioethanol contains higher alcohols as the main impurities and also aldehydes, amines, acids and esters. The effect of these impurities on the catalytic performances for ethanol steam reforming (ESR) has been studied, using a reference catalyst, Rh/MgAl₂O₄. It was shown that the aldehyde, the amine and methanol have no negative effect on the catalytic performances, contrary to the ester, acid and higher alcohols. The deactivation is mainly explained by coke formation favored by the presence of these impurities in the feed. In order to improve the stability of the catalyst and its performances in the presence of these deactivating impurities, the catalyst formulation, i.e. the composition of the support and of the metallic phase, was modified. The addition of rare earth elements instead of magnesium to the alumina support leads to a decrease of the strong and medium acid sites and to an increase of the basicity. On these modified supports, the dehydration reaction, leading to olefins, which are coke precursors, is disfavored, the ethanol conversion and the hydrogen yield are increased. The best catalytic performances were obtained with Rh/Y-Al₂O₃. Then, the metallic phase was also modified by adding a second metal (Ni, Pt or Pd). The Rh-Ni/Y-Al₂O₃ catalyst leads to the highest hydrogen yield. This catalyst, tested in the presence of raw bioethanol during 24 h was very stable compared to the reference catalyst Rh/MgAl₂O₄, which was strongly deactivated after 2 h of time-on –stream.     

Bioethanol steam reforming over monoliths washcoated with RhPt/CeO2–SiO2: The use of residual biomass to stably produce syngas

Ethanol steam reforming of synthetic bioethanol (i.e., anhydrous ethanol plus water), as well as bioethanol obtained from glucose standards and sugarcane press-mud was evaluated on monoliths washcoated with RhPt/CeO₂–SiO₂. Tests with synthetic bioethanol indicated that the lower pressure drop favors higher ethanol conversion in the monoliths with respect to the powder samples. Also, two monoliths in series with 0.08 g_cat/cm³ improved H₂ yield compared to just one monolith with 0.16 g_cat/cm³. Similarly, a decrease in the amount of carrier gas contributes to diffusion limitations in the monoliths, reducing the H₂/CO ratio. Monoliths stability was also evaluated with “real” bioethanol samples (from glucose standards and sugarcane press-mud-SPM). In all cases, a syngas with >60% of H₂ was produced. For SPM-bioethanol, 3.1 ± 0.2 mol H₂/mol EtOH were obtained without evidence of deactivation for 120 h, at a cost of 6.9 $/kgH₂, becoming a promising way to develop a technology for sustainable energy production.     

Key prospects and major development of hydrogen and bioethanol production

Cheap Production of bioethanol from renewable lignocellulosic waste has the imperative potential to economically cut burgeoning world dependency on fossils while reducing net emission of carbon dioxide (CO₂), a principal greenhouse gas (GHGs). This paper highlights key benefits and status of bioethanol production technologies, aiming mainly on recent developments and its key potentials in Pakistan. Most sector of Pakistan economy heavily rely on the energy and power that is being produced using traditional approaches like from oil and hydel. However, the sedimentation in dams cut-down the energy generation and overwhelmed severe energy crisis that are witnessed since last decade. Thus, Pakistan must go to avail alternative sources of energy like hydro, biomass and solar so that energy security can be ensured to recover the tremendous loss of economy. Renewable biomass is abundantly available in Pakistan which can be used to produce bioethanol and electricity. Currently, 22 distilleries are producing the ethanol from sugar cane bagasse and out of these only 8 distillation units are producing motor fuel grade ethanol. The current bioethanol production of country is about 403,500 tons/year along with 2423 tons of biodegradable waste available in major cities. In addition, Pakistan produces 6.57, 0.5, 0.66, and 2.66 million tons of sugarcane, corn, rice, and wheat straw per annum, respectively. This biomass can produce 1.6 million liters of bioethanol which can produce approximately 38% of Pakistan's electricity annually. Despite having large potential, Pakistan is still producing a few volumes of ethanol from sugarcane bagasse. The production of bioethanol can be boosted using (I) pretreatment of agricultural biomass by alkali (II) enzymatic and bacteria-based hydrolysis of the biomass (III) post-hydrolysis using pressurized steam above 100 °C (IV) Fermentation of the biomass@ 7–10 h and (V) and (VI) distillation of bioethanol. This study recommends (1) increase R&D capacities mainly in the west and central regions of Pakistan, (2) initiate mega-projects to promote integrated bio-ethanol production at agriculture farms by providing 1/3 subsides, (3) purchase of bioethanol directly from the major agricultural farms, (4) produce bioethanol related manpower from the key research institutes as specified in this study.     

Catalysts for H2 production using the ethanol steam reforming (a review)

This review aims to provide an overview of the main catalytic studies of H₂ production by ethanol steam reforming (ESR). The reaction is endothermic and produces H₂, CO₂, CH₄, CO and coke. The conversion and H₂ selectivity of these products depended greatly of the physicochemical properties of the catalysts, active metal, promoters, temperature, long-term reaction, water/ethanol ratio, space velocity, contact time, and presence of O₂. Initial total conversion has been reported in all catalysts evaluated between 300 and 850 °C. The noble catalysts with high selectivity to H₂ (more than 80%) were: Rh, Ru, Pd and Ir and non-noble metal catalysts were: Ni, Co and Cu. The support materials include CeO₂, ZnO, MgO, Al₂O₃, zeolites-Y, TiO₂, SiO₂, La₂O₂CO₃, CeO₂–ZrO₂ and hydrotalcites. The impregnation method produced the best noble metal catalysts in terms of selectivity and conversion. The decrease of coke was related with the presence of basic sites on the support.     

Boosting hydrogen production by ethanol steam reforming on cobalt-modified Ni–Al2O3 catalyst

Ethanol steam reforming (ESR) is one of the most promising reliable and recyclable technologies for hydrogen production. However, the development of robust, efficient Ni-based catalysts that minimize metal sintering and carbon deposition remains a key challenge. The influence of cobalt loading and ESR conditions on H₂ selectivity and catalytic stability is the focus of this study. Ni–Co/Al₂O₃ catalysts with various Co percentages were prepared by the co-impregnation method and complementary characterization tests were performed. Among the catalysts tested, Ni–Co/Al₂O₃ (5 wt% Co) exhibited the smallest metal crystallite size, the highest surface area, and the best catalytic performance. Thereafter, the effects of temperature, LHSV and S:C molar ratio were studied. 100% ethanol conversion and maximum H₂ selectivity (95.14%) were reached at 600 °C, 0.05 L/g_cat.h and S:C molar ratio of 12:1. Furthermore, ethanol turnover frequency (TOF) was computed for each catalyst. TOF results showed that the Ni–Co interaction had an impact on the catalytic activity. Finally, Ni2CoAl was subjected to 50-h stability test and only 6.12 mg_carbon/g_cat.h coke deposition was observed.     

A review on ethanol steam reforming for hydrogen production over Ni/Al2O3 and Ni/CeO2 based catalyst powders

Hydrogen is contemplated as an alternative clean fuel for the future. Ethanol steam reforming (ESR) is a carbon-neutral, sustainable, green hydrogen production method. Low cost Ni/Al₂O₃ and Ni/CeO₂ powder catalysts demonstrate high ESR activity. However, acidic nature of Al₂O₃ and instability of CeO₂ lead to deactivation of the catalysts easily. This article examines the research articles published on the modification of Ni by various noble and non-noble metals and on alteration of the supports by different metal oxides in detail and their effect on ESR all through 2000–2021. The ESR reaction mechanisms on Ni/Al₂O₃ and Ni/CeO₂ powder catalysts and basic thermodynamics for different possible reactions and H₂ yield are explored. Manipulation of catalyst morphology (surface area and particle size) via preparation method, selection of active metal promoter and support modifier are found to be significantly important for H₂ production and minimizing carbon deposition on catalysts.     

Improving fermentative hydrogen and methane production from an algal bloom through hydrothermal/steam acid pretreatment

Algal blooms can be harvested as renewable biomass waste for gaseous biofuel production. However, the rigid cell structure of raw algae may hinder efficient microbial conversion for production of biohydrogen and biomethane. To improve the energy conversion efficiency, biomass from an algal bloom in Dianchi Lake was subjected to a hydrothermal/steam acid pretreatment prior to sequential dark hydrogen fermentation and anaerobic digestion. Results from X-ray diffraction and Fourier transform infrared spectroscopy suggest that hydrothermal acid pretreatment leads to stronger damage of the amorphous structure (including hemicellulose and amorphous cellulose) due to the acid pretreatment, as evidenced by the higher crystallinity index. Scanning electron microscopy analysis showed that smaller fragments (∼5 mm) and wider cell gaps (∼1 μm) on algal cell surfaces occurred after pretreatment. In comparison to steam acid pretreatment, hydrothermal acid pretreatment resulted in a maximum energy conversion efficiency of 44.1% as well as production of 24.96 mL H₂/g total volatile solids (TVS) and 299.88 mL CH₄/g TVS.