Investigation on hydrogen production by catalytic steam reforming of maize stalk fast pyrolysis bio-oil

Hydrogen production via catalytic steam reforming of maize stalk fast pyrolysis bio-oil over the nickel/alumina supported catalysts promoted with cerium was studied using a laboratory scale fixed bed coupled with Fourier transform infrared spectroscopy/thermal conductivity detection analysis (FTIR/TCD). The effects of nickel loading, reaction temperature, water to carbon molar ratio (WCMR) and bio-oil weight hourly space velocity (W_bHSV) on hydrogen production were investigated. The highest hydrogen yield of 71.4% was obtained over the 14.9%Ni-2.0%Ce/A1₂O₃ catalyst under the reforming conditions of temperature = 900 °C, WCMR = 6 and W_bHSV = 12 h⁻¹. Increasing reaction temperature from 600 to 900 °C resulted in the significant increase of hydrogen yield. The hydrogen yield was significantly enhanced by increasing the WCMR from 1 to 3, whereas it increased slightly by further increasing WCMR. The hydrogen yield decreased with the increase of W_bHSV. Meanwhile, the coke deposition percentage changed little with increasing W_bHSV up to 12 h⁻¹ and then it increased by 4.5% with the further increase of W_bHSV from 12 to 24 h⁻¹.     

Catalysts of Ni/α-Al2O3 and Ni/La2O3-αAl2O3 for hydrogen production by steam reforming of bio-oil aqueous fraction with pyrolytic lignin retention

This paper reports on the steam reforming, in continuous regime, of the aqueous fraction of bio-oil obtained by flash pyrolysis of lignocellulosic biomass (sawdust). The reaction system is provided with two steps in series: i) thermal step at 200 °C, for the pyrolytic lignin retention, and ii) reforming in-line of the treated bio-oil in a fluidized bed reactor, in the range 600–800 °C, with space-time between 0.10 and 0.45 g_catalyst h (g_bio-oil)⁻¹. The benefits of incorporating La₂O₃ to the Ni/α-Al₂O₃ catalyst on the kinetic behavior (bio-oil conversion, yield and selectivity of hydrogen) and deactivation were determined. The significant role of temperature in gasifying coke precursors was also analyzed. Complete conversion of bio-oil is achieved with the Ni/La₂O₃-αAl₂O₃ catalyst, at 700 °C and space-time of 0.22 g_catalyst h (g_bio-oil)⁻¹. The catalyst deactivation is low and the hydrogen yield and selectivity achieved are 96% and 70%, respectively.     

Hydrogen production via catalytic steam reforming of the aqueous fraction of bio-oil using nickel-based coprecipitated catalysts

Hydrogen production was studied in the catalytic steam reforming of a synthetic and a real aqueous fraction of bio-oil. Ni/Al coprecipitated catalysts with varying nickel content (23, 28 and 33 relative atomic %) were prepared by an increasing pH technique and tested during 2 h under different experimental conditions in a small bench scale fixed bed setup. The 28% Ni catalyst yielded a more stable performance over time (steam-to-carbon molar ratio, S/C = 5.58) at 650 °C and a catalyst weight/organic flow rate (W/m_org) ratio of 1.7 g catalyst min/g organic. Using the synthetic aqueous fraction as feed, almost complete overall carbon conversion to gas and hydrogen yields close to equilibrium could be obtained with the 28% Ni catalyst throughout. Up to 63% of overall carbon conversion to gas and an overall hydrogen yield of 0.09 g/g organic could be achieved when using the real aqueous fraction of bio-oil, but the catalyst performance showed a decay with time after 20 min of reaction due to severe coke deposition. Increasing the W/m_org ratio up to 5 g catalyst min/g organic yielded a more stable catalyst performance throughout, but overall carbon conversion to gas did not surpass 83% and the overall hydrogen yield was only ca. 77% of the thermodynamic equilibrium. Increasing reaction temperatures (600–800 °C) up to 750 °C enhanced the overall carbon conversion to gas and the overall yield to hydrogen. However, at 800 °C the catalyst performance was slightly worse, as a result of an increase in thermal cracking reactions leading to an increased formation of carbon deposits.     

Improving the quality of fast pyrolysis bio-oil by reduced pressure distillation

In the present study, reduced pressure distillation was performed to obtain distilled bio-oil from fast pyrolysis bio-oil. The experiments were completed at temperature 80 °C with a residual pressure of 15 mmHg. The distilled bio-oil yields of 61 wt% from reduced pressure distillation of fast pyrolysis bio-oil were obtained. The oxygen contents of the distilled bio-oil is 9.2 wt% and the distilled bio-oil has lower content of oxygen than the fast pyrolysis bio-oil. For this reason, compared with the fast pyrolysis bio-oil, the distilled bio-oil has higher heating value, lower corrosivity and better stability. The heating value of distilled bio-oil is 34.2 MJ/kg, which is about 2 times of that of fast pyrolysis bio-oil. It is found that the distilled bio-oil stored at 60 °C results in a weight loss of about 0.3% for mild steel and the distilled bio-oil’s viscosity hardly increases during storage. These properties of distilled bio-oil make it more suitable for fuel oil use or as a source of chemicals than fast pyrolysis bio-oil.     

Catalytic pyrolysis of distillers dried grain with solubles: An attempt towards obtaining value-added products

Catalytic pyrolysis of distillers dried grain with solubles by nickel-based catalysts was performed. The effects of pyrolysis temperature, catalytic carrier and components on the products were investigated. The catalysts were characterized with NH₃-TPD, XPS, H₂-TPR. The average higher heating value (HHV) of the bio-oil was about 61% of the HHV of gasoline. GC/MS analysis indicated that the bio-oil contained some value-added compounds such as 2-furaldehyde, 2-furanmethanol, 3-pyridinol, dodecane, etc. The pyrolysis gas rich in hydrogen was obtained under the direct catalysis of nickel-based catalysts. For Ni–Pd-γ-Al₂O₃, the volume percentage of hydrogen in gas reached 55.6 vol.% at 500 °C, revealing that there was a strong synergistic effect between Ni and Pd. According to the experimental results the possible mechanism was proposed. It was considered that the metal species over catalyst was the most important factor for its performance, and the influence from its Lewis acidity could not be ignored.     

Production of hydrogen rich bio-oil derived syngas from co-gasification of bio-oil and waste engine oil as feedstock for lower alcohols synthesis in two-stage bed reactor

High efficient production of lower alcohols (C₁–C₅ mixed alcohols) from hydrogen rich bio-oil derived syngas was achieved in this work. A non-catalytic partial oxidation (NPOX) gasification technology was successfully applied in the production and conditioning of bio-oil derived syngas using bio-oil (BO) and emulsifying waste engine oil (EWEO) as feedstock. The effects of water addition and feedstock composition on the gasification performances were investigated. When the BO₂₀ and EWEO₃₀ was mixed with mass ratio of 1: 0.33, the maximum hydrogen yield of 93.7% with carbon conversion of 96.7% was obtained, and the hydrogen rich bio-oil derived syngas was effectively produced. Furthermore, a two-stage bed reactor was applied in the downstream process of lower alcohols synthesis from hydrogen rich bio-oil derived syngas (H₂/CO/CO₂/CH₄/N₂ = 52.2/19.5/3.0/9.4/15.9, v/v). The highest carbon conversion of 42.5% and the maximum alcohol yield of 0.18 kg/kg_cat h with selectivity of 53.8 wt% were obtained over the Cu/ZnO/Al₂O₃(2.5)//Cu₂₅Fe₂₂Co₃K₃/SiO₂(2.5) catalyst combination system. The mechanism and evaluation for lower alcohols synthesis from model bio-oil derived syngas and model mixture gas were also discussed. The integrative process of hydrogen rich bio-oil derived syngas production and downstream lower alcohols synthesis, potentially providing a promising route for the conversion of organic wastes into high performance fuels and high value-added chemicals.     

Hydrogen production from lignite via supercritical water in flow-type reactor

A supercritical water reactor with throughput of 10  kg/h was set up, which was operated with continuous feeding of coal water slurry. The effects of reaction temperature (500–650 °C), pressure (20.0–30.0 MPa), Ca/C molar ratio (0–0.45) and O/C molar ratio (0–0.35) on the hydrogen generation characteristics were investigated. It is found that there is a notable increase in the hydrogen content and yield with the increase of reaction temperature. The hydrogen yield increases from 24.67 ml/g to 135.73 ml/g when the temperature increases from 500 °C to 650 °C. The contents of CO₂ in gas product decrease, while that of hydrogen increases with the increase of Ca/C molar ratio. At Ca/C molar ratio of 0.45, nearly all CO₂ is fixed. Correspondingly, the content of hydrogen in gas is 73.29%, and the yield of hydrogen is 348.30 ml/g compared to 135.42 ml/g in the absent of CaO. Moreover, both of CaO and KOH catalyze gasification and water-shift reaction. The formation of hydrogen and the carbon gasification efficiency are improved by the added H₂O₂ when O/C ratio is less than 0.3.     

Hydrogen production from catalytic steam reforming of bio-oil aqueous fraction over Ni/CeO2–ZrO2 catalysts

A series of composite catalysts Ni/CeO₂–ZrO₂ were prepared via impregnation method with Ni as the active metal. A laboratory-scale fixed-bed reactor was employed to investigate the catalyst performance during hydrogen production by steam reforming bio-oil aqueous fraction. Effects of water-to-bio-oil ratio (W/B), reaction temperature, and the loaded weight of Ni and Ce on the hydrogen production performance of Ni/CeO₂–ZrO₂ catalysts were examined. The obtained results were compared with commercial nickel-based catalysts (Z417). The best performance of Ni/CeO₂–ZrO₂ catalyst was observed when the Ni and Ce loaded weight were 12% and 7.5% respectively. At W/B = 4.9, T = 800 °C, H₂ yield reaches the highest of 69.7% and H₂ content of 61.8% were obtained. Under the same condition, H₂ yield and H₂ content were higher than commercial nickel-based catalysts (Z417).     

Optimization of batch dilute-acid hydrolysis for biohydrogen production from red algal biomass

Marine algae are promising alternative sources for bioenergy including hydrogen. Their polymeric structure, however, requires a pretreatment such as dilute-acid hydrolysis prior to fermentation. This study aimed to optimize the control variables of batch dilute-acid hydrolysis for dark hydrogen fermentation of algal biomass. The powder of Gelidium amansii was hydrolyzed at temperatures of 120–180 °C, solid/liquid (S/L) ratios of 5–15% (w/v), and H₂SO₄ concentrations of 0.5–1.5% (w/w), and then fed to batch hydrogen fermentation. Among the three control variables, hydrolysis temperature was the most significant for hydrogen production as well as for hydrolysis efficiency. The maximum hydrogen production performance of 0.51 L H₂/L/hr and 37.0 mL H₂/g dry biomass was found at 161–164 °C hydrolysis temperature, 12.7–14.1% S/L ratio, and 0.50% H₂SO₄. The optimized dilute-acid hydrolysis would enhance the feasibility of the red algal biomass as a suitable substrate for hydrogen fermentation.     

Optimization of two bio-oil steam reforming processes for hydrogen production based on thermodynamic analysis

Thermodynamics of hydrogen production from conventional steam reforming (C-SR) and sorption-enhanced steam reforming (SE-SR) of bio-oil was performed under different conditions including reforming temperature, S/C ratio (the mole ratio of steam to carbon in the bio-oil), operating pressure and CaO/C ratio (the mole ratio of CaO to carbon in the bio-oil). Increasing temperature and S/C ratio, and decreasing the operating pressure were favorable to improve the hydrogen yield. Compared to C-SR, SE-SR had the significant advantage of higher hydrogen yield at lower desirable temperature, and showed a significant suppression for carbon formation. However excess CaO (CaO/C > 1) almost had no additional contribution to hydrogen production. Aimed to achieve the maximum utilization of bio-oil with as little energy consumption as possible, the influences of temperature and S/C ratio on the reforming performance (energy requirements and bio-oil consumption per unit volume of hydrogen produced, Q_D/H2 (kJ/Nm³) and Y_Bio-oil/H2 (kg/Nm³)) were comprehensively evaluated using matrix analysis while ensuring the highest hydrogen yield as possible. The optimal operating parameters were confirmed at 650 °C, S/C = 2 for C-SR; and 550 °C, S/C = 2 for SE-SR. Under their respective optimal conditions, the Y_Bio-oil/H2 of SE-SR is significant decreased, by 18.50% compared to that of C-SR, although the Q_D/H2 was slightly increased, just by 7.55%.     

Integrated catalytic adsorption (ICA) steam gasification system for enhanced hydrogen production using palm kernel shell

This paper investigates the integrated catalytic adsorption (ICA) steam gasification of palm kernel shell for hydrogen rich gas production using pilot scale fluidized bed gasifier under atmospheric condition. The effect of temperature (600–750 °C) and steam to biomass ratio (1.5–2.5 wt/wt) on hydrogen (H₂) yield, product gas composition, gas yield, char yield, gasification and carbon conversion efficiency, and lower heating values are studied. The results show that H₂ hydrogen composition of 82.11 vol% is achieved at temperature of 675 °C, and negligible carbon dioxide (CO₂) composition is observed at 600 °C and 675 °C at a constant steam to biomass ratio of 2.0 wt/wt. In addition, maximum H₂ yield of 150 g/kg biomass is observed at 750 °C and at steam to biomass ratio of 2.0 wt/wt. A good heating value of product gas which is 14.37 MJ/Nm³ is obtained at 600 °C and steam to biomass ratio of 2.0 wt/wt. Temperature and steam to biomass ratio both enhanced H₂ yield but temperature is the most influential factor. Utilization of adsorbent and catalyst produced higher H₂ composition, yield and gas heating values as demonstrated by biomass catalytic steam gasification and steam gasification with in situ CO₂ adsorbent.     

Upgrading of the liquid fuel from fast pyrolysis of biomass over MoNi/γ-Al2O3 catalysts

The hydrotreatment of bio-oil, which obtained from fast pyrolysis of pine sawdust, was investigated over MoNi/γ-Al₂O₃ catalyst under mild conditions (373 K, 3 MPa hydrogen pressure). Acetic acid was taken as a model compound to investigate the effects of Mo promoter contents and reducing temperatures of catalysts on the catalysts activity under the condition of 473 K and 3 MPa hydrogen pressure. X-ray diffraction and temperature programmed reduction showed that the addition of Mo promoter benefited the uniformity of nickel species and inhibited the formation of NiAl₂O₄ spinel in the catalysts. The GC spectrum of liquid products showed the mechanism of the model reaction. The maximum conversion of acetic acid (33.20%) was attained over 0.06MoNi/γ-Al₂O₃ catalysts being reduced at 873 K. This catalyst was chosen for the upgrading of raw bio-oil. After the upgrading process, the pH value of the bio-oil increased from 2.33 to 2.77. The water content increased from 35.52 wt.% to 41.55 wt.% and the gross calorific value increased from 13.96 MJ/kg to 14.17 MJ/kg. The hydrogen content in the bio-oil increased from 6.25 wt.% to 6.95 wt.%. The product properties of the upgraded bio-oil, particularly the hydrogen content and the acidity were considerably improved. The results of gas chromatography–mass spectrometry analysis showed that both hydrotreatment and esterification had happened over 0.06MoNi/γ-Al₂O₃ (873) catalyst during the upgrading process.     

Hydrogen production from catalytic reforming of the aqueous fraction of pyrolysis bio-oil with modified Ni–Al catalysts

Hydrogen production from renewable resources has received extensive attention recently for a sustainable and renewable future. In this study, hydrogen was produced from catalytic steam reforming of the aqueous fraction of crude bio-oil, which was obtained from pyrolysis of biomass. Five Ni–Al catalysts modified with Ca, Ce, Mg, Mn and Zn were investigated using a fixed-bed reactor. Optimized process conditions were obtained with a steam reforming temperature of 800 °C and a steam to carbon ratio of 3.54. The life time of the catalysts in terms of stability of hydrogen production and prohibition of coke formation on the surface of the catalyst were carried out with continuous feeding of raw materials for 4 h. The results showed that the Ni–Mg–Al catalyst exhibited the highest stability of hydrogen production (56.46%) among the studied catalysts. In addition, the life-time test of catalytic experiments showed that all the catalysts suffered deactivation at the beginning of the experiment (reduction of hydrogen production), except for the Ni–Mg–Al catalyst; it is suggested that the observation of abundant amorphous carbon formed on the surface of reacted catalysts (temperature programmed oxidation results) may be responsible for the initial reduction of hydrogen production. In addition, the Ni–Ca–Al catalyst showed the lowest hydrogen production (46.58%) at both the early and stabilized stage of catalytic steam reforming of bio-oil.     

A novel integrated process for hydrogen production from biomass

A novel process, which integrated with biomass pyrolysis, gas–solid simultaneous gasification and catalytic reforming processes, was utilized to produce hydrogen. The effects of gasification temperature and reforming temperature on hydrogen yield and carbon conversion efficiency were investigated. The results showed that both higher gasification temperature and reforming temperature led to higher hydrogen yield and carbon conversion efficiency. Compared with the two-stage pyrolysis-catalytic reforming process, hydrogen yield and carbon conversion efficiency were greatly increased from 43.58 to 75.96 g H₂/kg biomass and 66.18%–82.20% in the integrated process.     

Photofermentive production of biohydrogen from oil palm waste hydrolysate

Oil palm empty fruit bunch (OPEFB) was hydrolyzed with dilute sulfuric acid (6% v/v; 8 mL acid per g dry OPEFB) at 120 °C for 15-min to release the fermentable sugars. The hydrolysate contained xylose (23.51 g/L), acetic acid (2.44 g/L) and glucose (1.80 g/L) as the major carbon components. This hydrolysate was used as the sole carbon source for photofermentive production of hydrogen using a newly identified photosynthetic bacterium Rhodobacter sphaeroides S10. A Plackett–Burman experimental design was used to examine the influence of the following on hydrogen production: yeast extract concentration, molybdenum concentration, magnesium concentration, EDTA concentration and iron concentration. These factors influenced hydrogen production in the following decreasing order: yeast extract concentration > molybdenum concentration > magnesium concentration > EDTA concentration > iron concentration. Under the conditions used (35 °C, 14.6 W/m² illumination, initial pH of 7.0), the optimal composition of the culture medium was (per L): mixed carbon in OPEFB hydrolysate 3.87 g, K₂HPO₄ 0.9 g, KH₂PO₄ 0.6 g, CaCl₂⋅2H₂O 75 mg, l-glutamic acid 795.6 mg, FeSO₄⋅7H₂O 11 mg, Na₂MoO₂⋅2H₂O 1.45 mg, MgSO₄⋅7H₂O 2.46 g, EDTA 0.02 g, yeast extract 0.3 g). With this medium, the lag period of hydrogen production was 7.65 h, the volumetric production rate was 22.4 mL H₂/L medium per hour and the specific hydrogen production rate was 7.0 mL H₂/g (xylose + glucose + acetic acid) per hour during a 90 h batch culture of the bacterium. Under optimal conditions the conversion efficiency of the mixed carbon substrate to hydrogen was nearly 29%.     

Production of a hydrogen-rich gas from fast pyrolysis bio-oils: Comparison between homogeneous and catalytic steam reforming routes

The aim of the present work is to produce hydrogen from biomass through bio-oil. Two possible upgrading routes are compared: catalytic and non-catalytic steam reforming of bio-oils. The main originality of the paper is to cover all the steps involved in both routes: the fast pyrolysis step to produce the bio-oils, the water extraction for obtaining the bio-oil aqueous fractions and the final steam reforming of the liquids. Two reactors were used in the first pyrolysis step to produce bio-oils from the same wood feedstock: a fluidized bed and a spouted bed. The mass balances and the compositions of both batches of bio-oils and aqueous fractions were in good agreement between both processes. Carboxylic acids, alcohols, aldehydes, ketones, furans, sugars and aromatics were the main compounds detected and quantified. In the steam reforming experiments, catalytic and non-catalytic processes were tested and compared to produce a hydrogen-rich gas from the bio-oils and the aqueous fractions. Moreover, two different catalytic reactors were tested in the catalytic process (a fixed and a fluidized bed). Under the experimental conditions tested, the H₂ yields were as follows: catalytic steam reforming of the aqueous fractions in fixed bed (0.17 g H₂/g organics) > non-catalytic steam reforming of the bio-oils (0.14 g H₂/g organics) > non-catalytic steam reforming of the aqueous fractions (0.13 g H₂/g organics) > catalytic steam reforming of the aqueous fractions in fluidized bed (0.07 g H₂/g organics). These different H₂ yields are a consequence of the different temperatures used in the reforming processes (650 °C and 1400 °C for the catalytic and the non-catalytic, respectively) as well as the high spatial velocity employed in the catalytic tests, which was not sufficiently low to reach equilibrium in the fluidized bed reactor.     

Fermentative production of hydrogen and soluble metabolites from crude glycerol of biodiesel plant by the newly isolated thermotolerant Klebsiella pneumoniae TR17

A thermotolerant fermentative hydrogen-producing strain was isolated from crude glycerol contaminated soil and identified as Klebsiella pneumoniae on the basis of the 16S rRNA gene analysis as well as physiological and biochemical characteristics. The selected strain, designated as K. pneumoniae TR17, gave good hydrogen production from crude glycerol. Culture conditions influencing the hydrogen production were investigated. The strain produced hydrogen within a wide range of temperature (30–50 °C), initial pH (4.0–9.0) and crude glycerol concentration (20–100 g/L) with yeast extract as a favorable nitrogen source. In batch cultivation, the optimal conditions for hydrogen production were: cultivation temperature at 40 °C, initial pH at 8.0, 20 g/L crude glycerol and 2 g/L yeast extract. This resulted in the maximum cumulative hydrogen production of 27.7 mmol H₂/L and hydrogen yield of 0.25 mol H₂/mol glycerol. In addition, the main soluble metabolites were 1,3-propanediol, 2,3-butanediol and ethanol corresponding to the production of 3.52, 2.06 and 3.95 g/L, respectively.     

Effect of calcium based catalyst on production of synthesis gas in gasification of waste bamboo chopsticks

This study investigated the effects of calcium based catalyst (calcium oxide) on variation of gas composition in catalytic gasification reaction stages by controlling the gasification temperature between 600 °C and 900 °C whilst varying a catalyst/biomass ratio from 0 to 0.2 w/w. The tested biomass generated from used bamboo chopsticks were used as the feedstock. To assess the gas composition variation, the ratio of H₂/CO, H₂/CO₂, CO/CO₂, and 3H₂/CH₄ are four important factors that affect the performance of catalytic gasification process. The maximum ratio of H₂/CO increased from 0.23 to 0.72 in the gasification temperature range between 600 °C and 900 °C and 0%–20% calcium based catalyst addition ratio. This is due to enhanced H₂ production as a result of the facilitated water–gas shift reaction. The ratios of CO/CO₂ and 3H₂/CH₄ increased significantly from 0.9 to 2.1 and from 2.6 to 4.1, respectively, when the gasification temperature increased from 600 °C to 900 °C and 20% catalyst addition ratio. Obviously, the high temperature and catalyst addition are favorable for production of CO and H₂ during gasification of tested biomass. In conclusion, the tested mineral calcium based catalyst (CaO) can help facilitating the reaction rate of partial oxidation and water–gas shift reaction, enhancing the quality of synthesis gas, and reduction of the gasification reaction time. This catalyst has potential application in gasification of waste bamboo chopsticks in the future.     

Production of hydrogen by methane catalytic decomposition over Ni–Cu–Fe/Al2O3 catalyst

Catalysts with high nickel concentrations 75%Ni–12%Cu/Al₂O₃, 70%Ni–10%Cu–10%Fe/Al₂O₃ were prepared by mechanochemical activation and their catalytic properties were studied in methane decomposition. It was shown that modification of the 75%Ni–12%Cu/Al₂O₃ catalyst with iron made it possible to increase optimal operating temperatures to 700–750 °C while maintaining excellent catalyst stability. The formation of finely dispersed Ni–Cu–Fe alloy particles makes the catalysts stable and capable of operating at 700–750 °C in methane decomposition to hydrogen and carbon nanofibers. The yield of carbon nanofibers on the modified 70%Ni–10%Cu–10%Fe/Al₂O₃ catalyst at 700–750 °C was 150–160 g/g. The developed hydrogen production method is also efficient when natural gas is used as the feedstock. An installation with a rotating reactor was developed for production of hydrogen and carbon nanofibers from natural gas. It was shown that the 70%Ni–10%Cu–10%Fe/Al₂O₃ catalyst could operate in this installation for a prolonged period of time. The hydrogen concentration at the reactor outlet exceeded 70 mol%.     

Comparative techno-economic analysis of biohydrogen production via bio-oil gasification and bio-oil reforming

This paper evaluates the economic feasibility of biohydrogen production via two bio-oil processing pathways: bio-oil gasification and bio-oil reforming. Both pathways employ fast pyrolysis to produce bio-oil from biomass stock. The two pathways are modeled using Aspen Plus^® for a 2000 t d⁻¹ facility. Equipment sizing and cost calculations are based on Aspen Economic Evaluation® software. Biohydrogen production capacity at the facility is 147 t d⁻¹ for the bio-oil gasification pathway and 160 t d⁻¹ for the bio-oil reforming pathway. The biomass-to-fuel energy efficiencies are 47% and 84% for the bio-oil gasification and bio-oil reforming pathways, respectively. Total capital investment (TCI) is 435 million dollars for the bio-oil gasification pathway and is 333 million dollars for the bio-oil reforming pathway. Internal rates of return (IRR) are 8.4% and 18.6% for facilities employing the bio-oil gasification and bio-oil reforming pathways, respectively. Sensitivity analysis demonstrates that biohydrogen price, biohydrogen yield, fixed capital investment (FCI), bio-oil yield, and biomass cost have the greatest impacts on facility IRR. Monte-Carlo analysis shows that bio-oil reforming is more economically attractive than bio-oil gasification for biohydrogen production.