Fermentative hydrogen production from macroalgae Laminaria japonica pretreated by microwave irradiation

Pretreatment is an essential procedure to enhance the biodegradability when algae biomass is used as substrate for fermentative hydrogen production, In this study the potential of microwave pretreatment for enhancing the hydrogen production from macroalgae biomass Laminaria japonica was investigated. Microwave pretreatment at different temperatures (100–180 °C, 30 min) was explored, algae biomass disruption increased with increasing temperature, while highest hydrogen yield of 15.8 mL/g TS_added was obtained from 160 °C microwave treated algae biomass. Hydrogen production can be indicated by the dehydrogenase activity. After the microwave treatment, hydrogen production process altered from butyrate-type to acetate-type fermentation. Maximum hydrogen yield was enhanced by 1.9 fold compared with the control test. Indicating microwave treatment can be a good candidate in enhancing the hydrogen production from macroalgae biomass.     

Hydrothermal carbonization: Fate of inorganics

Hydrothermal carbonization (HTC) is a pretreatment process for making a homogenized, carbon rich, and energy-dense solid fuel, called biochar, from lignocellulosic biomass. Corn stover, miscanthus, switch grass, and rice hulls were treated with hot compressed water at 200, 230, and 260 °C for 5 min. Mass yield is as low as 41% of the raw biomass, and decreases with increasing HTC temperature. Higher heating values (HHV) increase up to 55% with HTC pretreatment temperature. Up to 90% of calcium, magnesium, sulfur, phosphorus, and potassium were removed with HTC treatment possibly due to hemicellulose removal. At a HTC temperature of 260 °C, some structural Si was removed. All heavy metals were reduced by HTC treatment. The slagging and fouling indices are reduced with HTC treatment relative to that of untreated biomass. Chlorine content, a concern only for raw and HTC 200 switch grass, was reduced to a low slagging range at 230 °C, and 260 °C. Alkali index was medium for raw biomass but decreased by HTC.     

Effect of aluminium sulphate-catalysed hydrolysis process on furfural yield and cellulose degradation of Cannabis sativa L. shives

Commercially, furfural is produced from pentosan-rich biomass using mineral acids as homogeneous catalysts. This study investigated a novel hydrolysis method that allows to obtain furfural from hemp shives with high yield and also to preserve the cellulose in the remaining biomass for other bioconversion processes. To date, hemp shives have not been investigated for furfural production. Cannabis sativa L. (“Bialobrzeskie” variety) shives were used as a feedstock due to the high content of pentosan (17.6% of oven-dried biomass). It means that the theoretically possible amount of furfural was 12.8% of oven-dried hemp shives. The effect of temperature (140–180 °C), the amount of catalyst (3–7% of oven-dried biomass) and the treatment time (10–90 min) on the furfural formation were studied. Whereas, the effect of the same temperature and the amount of catalyst on the changes of lignocellulose were studied after 90 min treatment time. Al₂(SO₄)₃*18H₂O was used as a catalyst for the conversion of C5-sugars to furfural. To show the catalytic properties of Al₂(SO₄)₃*18H₂O, autocatalysis was performed as a reference process using the same parameters. The highest yield of furfural, 73.7% of the theoretical yield, was obtained at 180 °C, 5% Al₂(SO₄)₃*18H₂O of oven-dried mass and 90 min. From the biorefinery perspective, the optimal hydrolysis parameters were 160 °C, 5% Al₂(SO₄)₃*18H₂O of oven-dried mass and 90 min. With these parameters, the yield of furfural was 62.7% of the theoretical yield, 99.2% of hemicelluloses were removed and 95.8% of cellulose was preserved and slightly depolymerized.     

Pretreatment and fractionation of barley straw using steam explosion at low severity factor

Agricultural residues represent an abundant, readily available, and inexpensive source of renewable lignocellulosic biomass. However, biomass has complex structural formation that binds cellulose and hemicellulose. This necessitates the initial breakdown of the lignocellulosic matrix. Steam explosion pretreatment was performed on barley straw grind to assist in the deconstruction and disaggregation of the matrix, so as to have access to the cellulose and hemicellulose. The following process and material variables were used: temperature (140–180 °C), corresponding saturated pressure (500–1100 kPa), retention time (5–10 min), and mass fraction of water 8–50%. The effect of the pretreatment was assessed through chemical composition analysis. The severity factor R_o, which combines the temperature and time of the hydrolytic process into a single reaction ordinate was determined. To further provide detailed chemical composition of the steam exploded and non-treated biomass, ultimate analysis was performed to quantify the elemental components. Data show that steam explosion resulted in the breakdown of biomass matrix with increase in acid soluble lignin. However, there was a considerable thermal degradation of cellulose and hemicellulose with increase in acid insoluble lignin content. The high degradation of the hemicellulose can be accounted for by its amorphous nature which is easily disrupted by external influences unlike the well-arranged crystalline cellulose. The carbon content of the solid steam exploded product increased at higher temperature and longer residence time, while the hydrogen and oxygen content decreased, and the higher heating value (HHV) increased.     

Effect of sodium sulfite on acid pretreatment of wheat straw with respect to its final conversion to ethanol

A pretreatment process that combines dilute acid and sodium sulfite has been applied to wheat straw to study the effect of temperature (120–180 °C) and sodium sulfite concentration (0–3%) on the yield of glucose in subsequent enzymatic hydrolysis and ethanol production by fermentation. The results were compared with both dilute acid pretreatment (without Na₂SO₃ addition) and hot water pretreatment. Formation of furfural and hydroxymethylfurural, which can inhibit ethanol-producing microorganisms, were measured and the ethanol yield in a subsequent fermentation was evaluated. The results indicate that a combination of 180 °C, 30 min, 1% H₂SO₄ and 2.4% Na₂SO₃ during pretreatment produced the highest ethanol yield; 17.3 g/100 g dry weight of initial biomass, which corresponds to 75% of the theoretical yield from glucose. 28 mg of furan inhibitors (sum of furfural and hydroxymethylfurfural) per gram dry weight of initial wheat straw were generated under this condition. Increasing sulfite loading up to 2.4% decreased inhibitor formation, leading to increased delignification and preservation of cellulose from dissolution. On the other hand, an elevated temperature in combination with low pH reduced the amount of solid phase after pretreatment, increased the level of inhibitors and reduced the concentration of ethanol produced by fermentation.     

Delignification of rapeseed straw using innovative chemo-physical pretreatments

Rapeseed straws are recoverable lignocellulosic biomass for second generation bioethanol production. Therefore, a pretreatment step is recommended in order to increase accessibility of enzymes to sugars. As a pretreatment step in this study, several innovative technologies have been performed in order to investigate their efficiency for delignification and enzymatic hydrolysis purposes: microwaves (MW), high voltage electrical discharges (HVED) and ultrasounds (US). As a key processing parameter, different levels of energy input were studied MW (1832–7328 kJ/kg), US (916–3664 kJ/kg) and HVED (204–814 kJ/kg) corresponding to a treatment duration range of 10–40 min. Treatment temperature (60–90 °C) and medium alkalinity (0.125–0.5 M) impact was also investigated and optimized based on sugar and soluble lignin contents in black liquor, and lignin removal yields. Delignification yields increased from 28.3%, 28.6% and 31.2% for 10 min of treatment to 38.4%, 41.5% and 42.3% for 40 min of treatment, respectively for MW, US and HVED. However, in order to achieve the same efficiency the energy required by HVED is 9 times and 4.5 times less than that required by MW and US respectively. Treatment temperature also revealed to be important as sugars yields increased by 41.6% when temperature increased from 60 °C to 90 °C for HVED and the optimal medium alkalinity was found to be 0.3 M. Finally, better enzymatic hydrolysis yields were obtained and correlated to better delignification performances improving material accessibility.     

Pretreatment methods to obtain pumpable high solid loading wood–water slurries for continuous hydrothermal liquefaction systems

Feedstock pretreatment is a prerequisite step for continuous processing of lignocellulosic biomass through HTL, in order to facilitate the pumpability of biomass aqueous slurries. Until now, HTL feedstock pumpability could only be achieved at solid mass content below 15%. In this work, two pretreatment methods to obtain wood-based slurries with more than 20% solid mass content, for continuous processing in HTL systems, are proposed. The effect of biomass particle size and pretreatment method on the feedstock pumpability is analyzed. The experimental results show that pumpable wood-based slurries containing 20% solids can be prepared using recycle HTL biocrude as carrier fluid, if particles smaller than 0.125 mm are used. The recycle biocrude concentration used for slurry make-up is strongly affected by the sawdust size distribution. A second pretreatment option is feedstock thermal treatment with alkalis. This method is less sensitive to particle size or wood type. 1 mm particles of either softwood or hardwood could be converted into pumpable liquid feedstock by thermal treatment with NaOH at 180 °C. Wood-water-biocrude slurries viscosity is reduced from 100 to 1000 Pa s to about 1 Pa s, when thermal treatment is applied.     

TGA and kinetic study of different torrefaction conditions of wood biomass under air and oxy-fuel combustion atmospheres

Combustion and oxy-fuel combustion characteristics of torrefied pine wood chips were investigated by Thermogravimetric Analysis (TGA). Three torrefaction temperatures (250, 300, and 350 °C) and two residence times (15 and 30 min) were considered. Experiments were carried out at three heating rates of 10, 20, and 40 °C/min. The isoconversional kinetic methods of FWO, KAS, and Friedman were employed to estimate the activation energies. The assessment of uncertainty in obtaining the activation energy values was also considered. The obtained results indicated that due to torrefaction, the O/C and H/C atomic ratios decreased, resulting the 300ºC-30 min and 350ºC-15 min torrefied biomass to be completely embedded in lignite region in van-Krevelen's diagram. Oxy-fuel combustion affected the decomposition of cellulose and lignin components of biomass while the impact on the hemicellulose component was negligible. The kinetic analysis revealed that with the evolution of conversion degree, the activation energy values increased during hemicellulose degradation, remained approximately constant during cellulose decomposition and showed a sharp decrease for lignin decomposition. The activation energy trends were comparable in both air and oxy-fuel combustion conditions, however slight changes in activation energy values were noticed. The highest activation energy value was obtained for 250ºC-30 min torrefied biomass at 183.40 kJ/mol and the lowest value was 72.93 kJ/mol for 350ºC-15 min biomass. The uncertainty values related to FWO method were lower than KAS and Friedman methods. The uncertainty values for FWO and KAS methods were at the range of 5–15%.     

Microwave-assisted conversion of biomass derived hemicelluloses into xylo-oligosaccharides by novel sulfonated bamboo-based catalysts

Hemicelluloses are the major constituent of biomass and their hydrolysis products xylo-oligosaccharides (XOS) are of great importance to the food, chemical and pharmaceutical industries. In this work, catalytic conversion of bamboo hemicelluloses into XOS was developed using novel solid acid catalysts of sulfonated bamboo-based carbon material (BCS). The Fourier Transform Infrared Spectroscopy characterization of BCS confirmed the successful introduction of acid groups (including –SO₃H, –COOH and phenolic –OH) onto its surface. The effects of reaction temperature, residence time and solid acid-to-water ratio on the performance of catalytic conversion were investigated. The maximum XOS yield of 54.7 wt% based on xylan content was obtained at 150 °C for 45 min with a solid acid to water mass ratio of 1:200. The use of water solvent with BCS provides a green and efficient process for hemicellulose conversion.     

Hydrolysis of Japanese beech by batch and semi-flow water under subcritical temperatures and pressures

Hydrolysis of lignocellulosic biomass by hot-compressed water is creating an opportunity to obtain saccharides from both hemicelluloses and cellulose for biofuel production as well as saccharides production. In this work, the hydrolysis of Japanese beech (Fagus crenata) by batch and semi-flow hot-compressed water was investigated. After the treatments, the monosaccharides, oligosaccharides and decomposition products in water-soluble portion were determined, while the structural variation as well as chemical composition of residue was analyzed. The results demonstrated that the production of total saccharides increased with the temperature for both batch and semi-flow hot-compressed water treatments. The maximum yield of total saccharides was achieved at 250 °C when treated by semi-flow hot-compressed water, which was higher than the corresponding maximum production of saccharides obtained at 190 °C when treated by batch hot-compressed water. The xylooligosaccharides which came from hemicelluloses were produced until the temperature was higher than 230 °C when treated by batch hot-compressed water, while they were produced until 270 °C when treated by semi-flow hot-compressed water. On the other hand, the cellooligosaccharides which came from cellulose began to produce from 170 °C when treated by batch hot-compressed water, while they were not produced below 210 °C when treated by semi-flow hot-compressed water. In conclusion, both batch and semi-flow hot-compressed water can be used to hydrolyze hemicelluloses though at different optimal temperature, while semi-flow hot-compressed water was better than batch hot-compressed water for hydrolysis of cellulose.     

Optimization of oxalic and sulphuric acid pretreatment conditions to produce bio-hydrogen from olive tree biomass

This study investigated the best pretreatment conditions for olive tree biomass (OTB) to produce bio-hydrogen. The pretreatment conditions were optimized with response surface methodology for the dark fermentative hydrogen production to achieve maximum reducing sugar recovery and the independent variables were residence time (30–90min), temperature (100–140 °C), and acid concentration (0.5–3 %w/w for sulfuric and 5–10 %w/w for oxalic acid). Maximum reducing sugar obtained after sulfuric acid pretreatment and oxalic acid pretreatment at optimal pretreatment conditions were 37 g/L and 28 g/L, respectively. An approximately 20-fold increase in sugar concentration was achieved in pretreatment with sulfuric acid compared to the untreated control. The highest hydrogen yield was 0.83 and 0.91 mol H₂/mol reducing sugar for oxalic acid pretreatment and sulfuric acid pretreatment, respectively. The results show that OTB has the potential to be used in bioenergy production.     

Catalytic supercritical water gasification of black liquor along with lignocellulosic biomass

Supercritical water gasification (SCWG) is a novel technology for environmental pollution management and hydrogen production from biomass and wastes. In this study, the SCWG of black liquor (BL) which is high-potential biomass and rich in alkalis was investigated. The experiments were conducted in a batch reactor at 350–400 °C, reaction time of 1–60 min, and constant concentration of 9 wt% of BL in the absence and presence of heterogeneous catalysts (3–5 wt%), lignocellulosic biomass, and formic acid (5 and 7 wt %) in three parts. First, the SCWG of BL was performed without any additive. The experimental results showed that the maximum production of H₂, CO₂, and CH₄ was obtained at the highest temperature and reaction time; 400 °C and 60 min. The hydrogen yield was also enhanced by increasing the temperature, and reached 3.51 mol H₂/kg dry ash free-black liquor (DAF-BL) at 400 °C. Reaction time increment improved the gas product and gasification efficiency up to 28.03 mmol and 21.73%, respectively. Subsequently, three heterogeneous catalysts (MnO₂, CuO, and TiO₂) were used, however 5 wt% of MnO₂ was the best catalyst, significantly improving the hydrogen yield compared to the same condition of BL gasification without a catalyst. Hydrogen yield reached 5.09 mol H₂/kg (DAF-BL) at 400 °C and the reaction time of 10 min. Finally, BL with poplar wood residue as a lignocellulosic biomass and formic acid was gasified separately and the highest hydrogen yield was obtained in the case of 5 wt% of formic acid (10.79 mol H₂/kg (DAF-BL)). Overally, SCWG dramatically reduced the chemical oxygen demand of BL to 76% using 5 wt% of formic acid.     

Steam reforming of hot gas from gasified wood types and miscanthus biomass

The reforming of hot gas generated from biomass gasification and high temperature gas filtration was studied in order to reach the goal of the CHRISGAS project: a 60% of synthesis gas (as x(H₂)+ x(CO) on a N₂ and dry basis) in the exit gas, which can be converted either into H₂ or fuels. A Ni-MgAl₂O₄ commercial-like catalyst was tested downstream the gasification of clean wood made of saw dust, waste wood and miscanthus as herbaceous biomass. The effect of the temperature and contact time on the hydrocarbon conversion as well as the characterization of the used catalysts was studied. Low (<600 °C), medium (750°C–900 °C) and high temperature (900°C–1050 °C) tests were carried out in order to study, respectively, the tar cracking, the lowest operating reformer temperature for clean biomass, the methane conversion achievable as function of the temperature and the catalyst deactivation. The results demonstrate the possibility to produce an enriched syngas by the upgrading of the gasification stream of woody biomass with low sulphur content. However, for miscanthusthe development of catalysts with an enhanced resistance to sulphur poison will be the key point in the process development.     

Application of an empirical model in CFD simulations to predict the local high temperature corrosion potential in biomass fired boilers

To gain reliable data for the development of an empirical model for the prediction of the local high temperature corrosion potential in biomass fired boilers, online corrosion probe measurements have been carried out. The measurements have been performed in a specially designed fixed bed/drop tube reactor in order to simulate a superheater boiler tube under well-controlled conditions. The investigated boiler steel 13CrMo4-5 is commonly used as steel for superheater tube bundles in biomass fired boilers. Within the test runs the flue gas temperature at the corrosion probe has been varied between 625 °C and 880 °C, while the steel temperature has been varied between 450 °C and 550 °C to simulate typical current and future live steam temperatures of biomass fired steam boilers. To investigate the dependence on the flue gas velocity, variations from 2 m·s⁻¹ to 8 m·s⁻¹ have been considered. The empirical model developed fits the measured data sufficiently well. Therefore, the model has been applied within a Computational Fluid Dynamics (CFD) simulation of flue gas flow and heat transfer to estimate the local corrosion potential of a wood chips fired 38 MW steam boiler. Additionally to the actual state analysis two further simulations have been carried out to investigate the influence of enhanced steam temperatures and a change of the flow direction of the final superheater tube bundle from parallel to counter-flow on the local corrosion potential.     

Effect of a mild torrefaction for production of eucalypt wood briquettes under different compression pressures

The heat treatment of wood (i.e. torrefaction) followed by densification of wood particles (e.g. by briquetting) may be used as a process to improve homogeneity and energy properties of wood for use as a solid fuel. The wood of Eucalyptus grandis and Eucalyptus spp. were treated at 180, 200 and 220 °C for 60 min under a nitrogen atmosphere. Briquettes were produced with untreated and heat-treated wood particles using 120 °C, for 7 min pressing and 6 min cooling time, under pressures of 6.9, 10.3 and 13.8 MPa. The briquetting compacting pressure showed no significant influence on the briquettes properties. Briquettes density was similar for all cases presenting 1.14 g cm⁻³ for Eucalyptus spp. and 1.06 g cm⁻³ for Eucalyptus grandis wood. A mild torrefaction of the wood at 200–220 °C increased the potential energy of the particles and briquettes, showing an improvement in their density, dimensional stability and hygroscopicity. Briquettes produced from heat-treated Eucalyptus spp. wood presented higher energy density (24.79 GJ m⁻³) at 200°C-treatment when compared with untreated wood (20.76 GJ m⁻³). Regarding E. grandis, briquettes produced with heat-treated (200 °C) particles showed only a marginal higher energy content than with untreated wood, 21.70 GJ m⁻³ and 21.38 GJ m⁻³, respectively. The two eucalypt woods showed differences regarding the heat treatment and briquetting, pointing out that the optimization of these processes should be specific for each species. However, a mild torrefaction of the wood particles decreased the differences between materials which might be useful as a process to increase feedstock homogeneity when using mixed raw-materials.     

Valorization of Eucalyptus wood by glycerol-organosolv pretreatment within the biorefinery concept: An integrated and intensified approach

The efficient utilization of lignocellulosic biomass and the reduction of production cost are mandatory to attain a cost-effective lignocellulose-to-ethanol process. The selection of suitable pretreatment that allows an effective fractionation of biomass and the use of pretreated material at high-solid loadings on saccharification and fermentation (SSF) processes are considered promising strategies for that purpose. Eucalyptus globulus wood was fractionated by organosolv process at 200 °C for 69 min using 56% of glycerol-water. A 99% of cellulose remained in pretreated biomass and 65% of lignin was solubilized. Precipitated lignin was characterized for chemical composition and thermal behavior, showing similar features to commercial lignin. In order to produce lignocellulosic ethanol at high-gravity, a full factory design was carried to assess the liquid to solid ratio (3–9 g/g) and enzyme to solid ratio (8–16 FPU/g) on SSF of delignified Eucalyptus. High ethanol concentration (94 g/L) corresponding to 77% of conversion at 16FPU/g and LSR = 3 g/g using an industrial and thermotolerant Saccharomyces cerevisiae strain was successfully produced from pretreated biomass. Process integration of a suitable pretreatment, which allows for whole biomass valorization, with intensified saccharification-fermentation stages was shown to be feasible strategy for the co-production of high ethanol titers, oligosaccharides and lignin paving the way for cost-effective Eucalyptus biorefinery.     

Supercritical water gasification mechanism of polymer-containing oily sludge

In the offshore petroleum industry, polymer-containing oily sludge (PCOS) hinders oil extraction and causes tremendous hazards to the marine ecological environment. In this paper, an effective pretreatment method is proposed to break the adhesive structure of PCOS, and the experiments of supercritical water gasification are carried out under the influencing factors including residence time (5–30 min) and temperature (400–750 °C) in batch reactors. The increase of time and temperature all show great promoting effects on gas production. Polycyclic aromatic hydrocarbons, including naphthalene and phenanthrene, are considered as the main obstacles for a complete gasification. Carbon gasification efficiency (CE) reaches maximum of 95.82% at 750 °C, 23 MPa for 30 min, while naphthalene makes up 70% of the organic compounds in residual liquid products. The highest hydrogen yield of 19.79 (mol H₂/kg of PCOS) is observed in 750 °C for 25 min. A simplified reaction pathway is presented to describe the gaseous products (H₂, CO, CO₂, CH₄). Two intermediates are defined for describing the reaction process bases on the exhaustive study on organic matters in residual liquid products. The results show that the calculated data and the experimental data have a high degree of fit and tar formation reaction is finished within 10 min.     

Comparison of pretreatment protocols for cellulase-mediated saccharification of wood derived from transgenic low-xylan lines of cottonwood (P. trichocarpa)

The novel low xylan content transgenic cottonwood (P. trichocarpa) was used to elucidate recalcitrance of enzymatic saccharification with or without four different pretreatment methods. The xylan contents of two transgenic samples (8Di3 and 8Di5) were 11.4% and 11.7%, respectively, as compared with the wild type (16.0%). Contrarily, the lignin contents of two transgenic samples were 23.1% and 24.5%, respectively, as compared with the wild type (20.8%). The four pretreatments were dilute acid (0.1% sulfuric acid, 185 °C, 30 min), green liquor (6% total titratable alkali (TTA), 25% sulfidity based on TTA, 185 °C and 15 min), auto hydrolysis (185 °C, 30 min) and ozone delignification (25 °C, 30 min). Following the pretreatment, enzymatic saccharification was carried out using three enzyme charges of 10, 20 and 30 FPU per gram of substrate. The removal of lignin and hemicelluloses varied with the type of pretreatment and with the lignin content of the transgenic trees. High lignin content implied low enzymatic saccharification. Low xylan content native substrates lead to high enzymatic saccharification. High S to V (sryingaldehyde to vanillin) ratio substrates had high delignification during pretreatment. Compared to the wild type, the transgenics were better choice as feed stocks due to higher enzymatic saccharification without pretreatment which mean low the cost of bio-ethanol. Compared to three pretreatment methods, the green liquor pretreatment greatly improves the conversion of polysaccharides in general.     

Biohydrogen production improvement using hot compressed water pretreatment on sake brewery waste

Most hydrogen is derived from fossil fuels. Therefore, more environmentally friendly methods for hydrogen production have been investigated. The present report describes a hot compressed water (HCW) pretreatment to increase hydrogen production using sake lees, which is an industrial waste of sake production. The inoculum is obtained from treated biogas slurry. The temperatures of HCW are 130 (0.3 MPa), 150 (0.5 MPa), and 180 °C (0.8 MPa) for 15–120 min. Gas production was analyzed using gas chromatography; fermentation liquid analyses were performed using HPLC. The modified Gompertz model was used to determine hydrogen potential, lag time, and production rate. Results show an increase in the degradation of sake lees with longer holding time and higher temperature. Total sugar and organic acids also are influenced by HCW pretreatment. The maximum hydrogen yield was obtained at 130 °C for 60 min with the result 112.07 mL H₂/g COD. The HCW pretreatment successfully decreased the lag phase of biohydrogen production and increased the degree of acidification. Clostridium butyricum, C. acetobutylicum, and other Clostridium sp. were identified in all samples, while Pantoea agglomerans was detected in two samples.     

Optimization and modeling of process parameters during hydrothermal gasification of biomass model compounds to generate hydrogen-rich gas products

Hydrothermal gasification in subcritical and supercritical water is gaining attention as an attractive option to produce hydrogen from lignocellulosic biomass. However, for process optimization, it is important to understand the fundamental phenomenon involved in hydrothermal gasification of synthetic biomass or biomass model compounds, namely cellulose, hemicellulose and lignin. In this study, the response surface methodology using the Box-Behnken design was applied for the first time to optimize the process parameters during hydrothermal (subcritical and supercritical water) gasification of cellulose. The process parameters investigated include temperature (300–500 °C), reaction time (30–60 min) and feedstock concentration (10–30 wt%). Temperature was found to be the most significant factor that influenced the yields of hydrogen and total gases. Furthermore, negligible interaction was found between lower temperatures and reaction time while the interaction became dominant at higher temperatures. Hydrogen yield remained at about 0.8 mmol/g with an increase in the reaction time from 30 min to 60 min at the temperature range of 300–400 °C. When the temperature was raised to 500 °C, hydrogen yield started to elevate at longer reaction time. Maximum hydrogen yield of 1.95 mmol/g was obtained from supercritical water gasification of cellulose alone at 500 °C with 12.5 wt% feedstock concentration in 60 min. Using these optimal reaction conditions, a comparative evaluation of the gas yields and product distribution of cellulose, hemicellulose (xylose) and lignin was performed. Among the three model compounds, hydrogen yields increased in the order of lignin (0.73 mmol/g) < cellulose (1.95 mmol/g) < xylose (2.26 mmol/g). Based on the gas yields from these model compounds, a possible reaction pathway of model lignocellulosic biomass decomposition in supercritical water was proposed.