Potassium catalytic hydrogen production in sorption enhanced gasification of biomass with steam

Sorption enhanced gasification (SEG) of biomass with steam was investigated in a fixed-bed reactor to elucidate the effects of temperature, catalyst type and loading on hydrogen production. K₂CO₃, CH₃COOK and KCl were chosen as potassium catalyst precursors to improve carbon conversion efficiency in gasification process. It was indicated that from 600 °C to 700 °C, the addition of K₂CO₃ or CH₃COOK catalyzed the gasification for hydrogen production, and hydrogen yield and carbon conversion increased with increasing catalyst loadings of K₂CO₃ or CH₃COOK. However, the hydrogen yield and carbon conversion decreased as the amount of KCl was increased due to inhibition of KCl on gasification. The maximum carbon conversion efficiency (88.0%) was obtained at 700 °C corresponding to hydrogen yield of 73.0 vol.% when K₂CO₃ of 20 wt.% K loading was used. In particular, discrepant catalytic performance was observed between K₂CO₃ and CH₃COOK at different temperatures and the corresponding mechanism was also discussed.     

生物质水蒸气气化制氢模拟研究

利用ASPEN PLUS软件建立了生物质水蒸气气化制氢模型,对各种影响因素进行了深入分析。结果表明:随着碳转化率的增加,H2浓度略有降低,H2产量大幅增加,在碳转化率为1时达到最大值142.54 g/kg;随着水蒸气/生物质质量比的增加,H2浓度和产量大幅增加,而后趋于稳定,水蒸气/生物质质量比取2比较适宜。适当的升温和低压对制备H2有利,在加压条件下,H2浓度与产量达到最大值的温度升高。     

Simulation and economic evaluation of biomass gasification with sets for heating,cooling and power production

In this work, syngas was used directly as fuel source for the renewable CCHP system, which can be producted through biomass gasification process. The advantages and limitation of entrained flow gasifier are compared, followed by discussion on the key parameters that are critical for the optimum production of syngas. Gasification agent of 450 °C temperature and 30 atm pressure has been proposed as a optical solution to a entrained flow gasifier using air as gasification agent at 0.27 ER (oxygen equivalence ratio), in that it provides a syngas of 5.665 MJ/m³ LHV and up to 77% gasification efficiency. Depending on the key parameters of gasification process, the properties of syngas produced can be varied. It is thus essential to thoroughly understand the cogeneration system to identify the suitable methods for a renewable CCHP system. These process was simulated using Aspen Plus to perform the rigorous material and energy balances. The results obtained from simulation and experiment agreed well. This paper later focused on economic evaluation of the entire process, as well as the environmental benefits. The renewable CCHP system could able to attain lower CO₂ and SO₂ emission with total energy efficiency and gas yield of 75.43% and 2.476 m³/kg respectively.     

A novel process simulation model for hydrogen production via reforming of biomass gasification tar

Process modeling and simulation are very important for new designs and estimation of operating variables. This study describes a new process for the production of hydrogen from lignocellulosic biomass gasification tars. The main focus of this research is to increase hydrogen production and improve the overall energy efficiency of the process. In this study, Aspen HYSYS software was used for simulation. The integration structure presented in this research includes sections like tar reforming and ash separation (Ash), combined heat and power cycle (CHP), hydrogen sulfide removal unit (HRU), water-gas shift (WGS) reactor, and gas compression as well as hydrogen separation from a mixture of gases in pressure swing adsorption (PSA). It was found that the addition of CHP cycle and the use of the plug flow reactor (PFR) model, firstly, increased the overall energy efficiency of the process by 63% compared to 29.2% of the base process. Secondly it increased the amount of hydrogen production by 0.518 kmol (H2)/kmol Tar as compared with 0.475 of the base process. Process analysis also demonstrated that the integrated process of hydrogen production from biomass gasification tars is carbon neutral.     

An investigation into steam gasification of biomass for hydrogen enriched gas production in presence of CaO

Biomass steam gasification could be an attractive option for sustainable hydrogen production. Biomass, regarded as carbon neutral emitter, could be claimed as carbon negative emitter if carbon dioxide produced is captured and not allowed to emit to the environment during the process. Thus here an experimental study is carried out to find out the potential of hydrogen production from steam gasification of biomass in presence of sorbent CaO and effect of different operating parameters (steam to biomass ratio, temperature, and CaO/biomass ratio). Product gas with hydrogen concentration up to 54.43% is obtained at steam/biomass = 0.83, CaO/biomass = 2 and T = 670 °C. A drop of 93.33% in carbon dioxide concentration was found at CaO/biomass = 2 as compared to the gasification without CaO. Mathematical model based on Gibbs free energy minimization has been developed and is compared with the experimental results.     

Comparative analysis on sorption enhanced steam reforming and conventional steam reforming of hydroxyacetone for hydrogen production: Thermodynamic modeling

The chemical thermodynamics of sorption enhanced steam reforming (SESR) of hydroxyacetone for hydrogen production were investigated and contrasted with hydroxyacetone steam reforming (SR) by means of Gibbs free energy minimization principle and response reactions (RERs) method. Hydrogen is mainly derived methane steam reforming reaction from and water gas shift reaction. The former reaction contributes more than the latter one to hydrogen production below 550 °C and at higher temperature the latter one tends to dominate. The maximum hydrogen concentration is 70% in SR, which is far below hydrogen purities required by fuel cells. In SESR, hydrogen purities are over 99% in 525–550 °C with a WHMR greater than 8 and a CHMR of 6. The optimum temperature for SESR is approximately 125 °C lower than that for SR. In comparison with SR, SESR has the advantage of almost complete inhibition of coke formation in 200–1200 °C for WHMR ≥ 3.     

Modelling of H2 production via sorption enhanced steam methane reforming at reduced pressures for small scale applications

The production of H₂ via sorption enhanced steam reforming (SE-SMR) of CH₄ using 18 wt % Ni/Al₂O₃ catalyst and CaO as a CO₂-sorbent was simulated for an adiabatic packed bed reactor at the reduced pressures typical of small and medium scale gas producers and H₂ end users. To investigate the behaviour of reactor model along the axial direction, the mass, energy and momentum balance equations were incorporated in the gPROMS modelbuilder^®. The effect of operating conditions such as temperature, pressure, steam to carbon ration (S/C) and gas mass flow velocity (G_s) was studied under the low-pressure conditions (2–7 bar). Independent equilibrium based software, chemical equilibrium with application (CEA), was used to compare the simulation results with the equilibrium data. A good agreement was obtained in terms of CH₄ conversion, H₂ yield (wt. % of CH₄ feed), purity of H₂ and CO₂ capture for the lowest (G_s) representing conditions close to equilibrium under a range of operating temperatures pressures, feed steam to carbon ratio. At G_s of 3.5 kg m⁻²s⁻¹, 3 bar, 923 K and S/C of 3, CH₄ conversion and H₂ purity were up to 89% and 86% respectively compared to 44% and 63% in the conventional reforming process.     

Hydrogen production via CaO sorption enhanced anaerobic gasification of sawdust in a bubbling fluidized bed

This paper presents the experimental results of CaO sorption enhanced anaerobic gasification of biomass in a self-design bubbling fluidized bed reactor, aiming to investigate the influences of operation variables such as CaO to carbon mole ratio (CaO/C), H₂O to carbon mole ratio (H₂O/C) and reaction temperature (T) on hydrogen (H₂) production. Results showed that, over the ranges examined in this study (CaO/C: 0-2; H₂O/C: 1.2-2.18, T: 489-740 °C), the increase of CaO/C, H₂O/C and T were all favorable for promoting the H₂ production. The investigated operation variables presented different influences on the H₂ production under fluidized bed conditions from those obtained in thermodynamic equilibrium analysis or fixed bed experiments. The comparison with previous studies on fluidized bed biomass gasification reveals that this method has the advantage of being capable to produce a syngas with high H₂ concentration and low CO₂ concentration.     

Computer simulation of a biomass gasification-solid oxide fuel cell power system using Aspen Plus

The operation and performance of a SOFC (solid oxide fuel cell) stack on biomass syn-gas from a biomass gasification CHP (combined heat and power) plant is investigated. The objective of this work is to develop a model of a biomass-SOFC system capable of predicting performance under diverse operating conditions. The tubular SOFC technology is selected. The SOFC stack model, equilibrium type based on Gibbs free energy minimisation, is developed using Aspen Plus. The model performs heat and mass balances and considers ohmic, activation and concentration losses for the voltage calculation. The model is validated against data available in the literature for operation on natural gas. Operating parameters are varied; parameters such as fuel utilisation factor (U_f), current density (j) and STCR (steam to carbon ratio) have significant influence. The results indicate that there must be a trade-off between voltage, efficiency and power with respect to j and the stack should be operated at low STCR and high U_f. Operation on biomass syn-gas is compared to natural gas operation and as expected performance degrades. The realistic design operating conditions with regard to performance are identified. High efficiencies are predicted making these systems very attractive.     

Effects of biochemical composition on hydrogen production by biomass gasification

Gasification of cellulose, hemicellulose, lignin and three types of real biomass was conducted using an updraft fixed-bed reactor to investigate the effects of temperature (in the range of 920–1220 °C) on the yield and chemical composition of the produced syngas. The experimental results showed that the gasification products of cellulose and hemicellulose were similar to each other, but they were different from those of lignin; it is likely due to the difference in volatile compounds. Cellulose and hemicellulose can be gasified more rapidly producing more CO and CH₄ and less H₂ and CO₂ than lignin, and the real biomass fell in between. Biomass with more lignin produced more hydrogen than others. These differences were resulted from the relative amount of lignin, hemicellulose, and cellulose in the biomass. Linear superposition method was used to simulate the gasification characteristics of real biomass and it showed a certain linear correlation between the simulation and experimental data.     

The operation types and operation window for high-purity hydrogen production for the sorption enhanced steam methane reforming in a fixed-bed reactor

The operation types and operation window for high-purity H₂ production for the sorption enhanced steam methane reforming (SE-SMR) with Ni/Al₂O₃ catalyst and CaO sorbent in a fixed-bed reactor are investigated by an experimentally verified 2D numerical method. Four chemical reactions including steam reforming, water gas shift, global steam reforming, and CO₂ sorption are considered. The operation window is defined as the H₂ and CO molar fractions at outlet satisfying both y_H2,out ≥ 90% and y_CO,out ≤ y_CO,allow (= 1%, 2% or 3%) in dry base. Under the conditions of y_H2,out and y_CO,allow, there are six operation types, of which 2 types are within the operation window and 4 types are not within the operation window as the temperature, weight hourly space velocity (WHSV) and steam to methane (S/C) molar ratio vary. For a common case of S/C = 3, the operation windows for y_CO,allow = 3% at WHSV = 8.5 h^?1 and 42.5 h^?1 are located at 570–670 °C and 640–690 °C respectively, based on the parameters in this work. The operation window of temperature is wider with decreasing WHSV, and it becomes wider remarkably as the S/C ratio increases. The lowest temperature inside the operation window is 550 °C. The effects of the temperature, WHSV and S/C ratio on the operating types, y_H2,out and y_CO,out are also presented and discussed in details.     

Techno-economic analysis and life cycle assessment of hydrogen production from different biomass gasification processes

The paper presents techno-economic analyses and life cycle assessments (LCA) of the two major gasification processes for producing hydrogen from biomass: fluidized bed (FB) gasification, and entrained flow (EF) gasification. Results indicate that the thermal efficiency of the EF-based option (56%, LHV) is 11% higher than that of the FB-based option (45%), and the minimum hydrogen selling price of the FB-based option is $0.3 per kg H₂ lower than that of the EF-based option. When a carbon capture and liquefaction system is incorporated, the efficiencies of the EF- and FB-based processes decrease to 50% and 41%, respectively. The techno-economic analysis shows that at a biomass price of $100 per tonne, either a minimum price of $115/tonne CO_2e or a minimum natural gas price of $5/GJ is required to make the minimum hydrogen selling price of biomass-based plants equivalent to that of commercial natural gas-based steam methane reforming plants. Furthermore, the LCA shows that, biomass as a carbon-neutral feedstock, negative life cycle GHG emissions are achievable in all biomass-based options.     

Steam-gasification of biomass with CaO as catalyst for hydrogen-rich syngas production

Biomass is extensively considered as a feed-stock for bio-chemicals and bio-fuels production. Among all options for the utilization of biomass, gasification process is more popular because of its environmental advantages. In this study, biomass gasification with CO₂ removal by CaO sorbent was simulated by using a commercial simulator. The model accuracy was validated with reported results from steam only gasification of biomass in presence of CaO. The system was evaluated through tar yield, carbon conversion, gas quality and H₂ yield by varying the reaction temperature, steam flow rate and CaO flow rate. The hydrogen yield enhanced slightly from 187.32 ml/g to 198.49 ml/g with the increase of CaO/B from 1.0 to 1.5. However, a further enhancement in CaO/B from 1.5 to 2 sharply enhanced the hydrogen yield approximately 1.55 times (from 198.49 ml/g to 308.54 ml/g).     

Absorption-enhanced steam gasification of biomass for hydrogen production: Effect of calcium oxide addition on steam gasification of pyrolytic volatiles

The effect mechanism of calcium oxide (CaO) addition on gasification of pyrolytic volatiles as a key sub-process in the absorption-enhanced steam gasification of biomass (AESGB) for H₂ production at different conditions was investigated using a two-stage fixed-bed pyrolysis–gasification system. The results indicate that CaO functions as a CO₂ absorbent and a catalyst in the volatiles gasification process. CaO triggers the chemical equilibrium shift to produce more H₂ and accelerates volatile cracking and gasification reactions to obtain high volatile conversion rates. Increasing the gasification temperature could improve the reaction rate of cracking and gasification of volatiles as well as the catalytic effect of CaO, which continuously increase H₂ yield. When the gasification temperature exceeds 700 °C, the sharp decrease in CO₂ absorption capability of CaO drastically increases the CO₂ concentration and yield, which significantly decrease H₂ concentration. The appropriate temperature for the absorption-enhanced gasification process should be selected between 600 °C and 700 °C in atmospheric pressure. Increasing the water injection rate (represented as the mass ratio of steam to biomass) could also improve H₂ yield. The type of biomasses is closely associated with H₂ yield, which is closely related to the volatile content of biomass materials.     

Solar receiver/reactor for hydrogen production with biomass gasification in supercritical water

A novel receiver/reactor driven by concentrating solar energy for hydrogen production by supercritical water gasification (SCWG) of biomass was designed, constructed and tested. Model compound (glucose) and real biomass (corncob) were successfully gasified under SCW conditions to generate hydrogen-rich fuel gas in the apparatus. It is found that the receiver/reactor temperature increased with the increment of the direct normal solar irradiation (DNI). Effects of the DNI, the flow rates and concentration of the feedstocks as well as alkali catalysts addition were investigated. The results showed that DNI and flow rates of reactants have prominent effects on the temperature of reactor wall and gasification results. Higher DNI and lower feed concentrations favor the biomass gasification for hydrogen production. The encouraging results indicate a promising approach for hydrogen production with biomass gasification in supercritical water using concentrated solar energy.     

Hydrogen production by sorption enhanced steam reforming of propane: A thermodynamic investigation

Thermodynamic features of hydrogen production by sorption enhanced steam reforming (SESR) of propane have been studied with the method of Gibbs free energy minimization and contrasted with propane steam reforming (SR). The effects of pressure (1-5 atm), temperature (700-1100 K) and water to propane ratio (WPR, 1-18) on equilibrium compositions and carbon formation are investigated. The results suggest that atmospheric pressure and a WPR of 12 are suitable for hydrogen production from both SR and SESR of propane. High WPR is favourable to inhibit carbon formation. The minimum WPR required to eliminate carbon production is 6 in both SR and SESR. The most favourable temperature for propane SR is approximately 950 K at which 1 mol of propane has the capacity to produce 9.1 mol of hydrogen. The optimum temperature for SESR is approximately 825 K, which is over 100 K lower than that for SR. Other key benefits include enhanced hydrogen production of nearly 10 mol (stoichiometric value) of hydrogen per mole of propane at 700 K, increased hydrogen purity (99% compared with 74% in SR) and no CO₂ or CO production with the only impurity being CH₄, all indicating a great potential of SESR of propane for hydrogen production.     

Exergy analysis of hydrogen production from steam gasification of biomass: A review

Exergy analysis of hydrogen production from steam gasification of biomass was reviewed in this study. The effects of the main parameters (biomass characteristics, particle size, gasification temperature, steam/biomass ratio, steam flow rate, reaction catalyst, and residence time) on the exergy efficiency were presented and discussed. The results show that the exergy efficiency of hydrogen production from steam gasification of biomass is mainly determined by the H₂ yield and the chemical exergy of biomass. Increases in gasification temperatures improve the exergy efficiency whereas increases in particle sizes generally decrease the exergy efficiency. Generally, both steam/biomass ratio and steam flow rate initially increases and finally decreases the exergy efficiency. A reaction catalyst may have positive, negative or negligible effect on the exergy efficiency, whereas residence time generally has slight effect on the exergy efficiency.     

Advances in the application of active metal-based sorbents and oxygen carriers in chemical looping biomass steam gasification for H2 production

Active metal-based materials (AMMs) as CO₂ sorbents or oxygen carriers (OCs) have been investigated to enhance hydrogen production during various biomass-based chemical looping processes. CaO-based sorbents and Fe-based OCs are widely used in this field; therefore, these two types of materials will be the focus of this review. CaO-based sorbents can promote the water-gas shift reaction towards H₂ generation with in-situ CO₂ removal. OCs partly oxidise biomass, releasing CO – a reactant in the water-gas shift reaction. The use of Fe-based OCs boosts H₂ yield via iron-steam reactions. AMMs possess catalytic activity for tar cracking, generating more H₂. However, these AMMs suffer from sintering over cycles, which hinders their utilisation at industrial scales. The addition of support materials aims to overcome this issue. This review first assesses the impacts of CaO sorbents and OCs on H₂ production, and then examines the material behaviour, cyclic performance and applications in biomass-based chemical looping processes. The mechanism of support materials as a reactivity enhancer and sintering inhibitor is proposed in the review. The effects of operating conditions on H₂ yield are summarised and provided in the Supplementary materials.     

Design and thermodynamic assessment of a biomass gasification plant integrated with Brayton cycle and solid oxide steam electrolyzer for compressed hydrogen production

In this paper, a comprehensive thermodynamic evaluation of an integrated plant with biomass is investigated, according to thermodynamic laws. The modeled multi-generation plant works with biogas produced from demolition wood biomass. The plant mainly consists of a biomass gasifier cycle, clean water production system, hydrogen production, hydrogen compression, gas turbine sub-plant, and Rankine cycle. The useful outputs of this plant are hydrogen, electricity, heating and clean water. The hydrogen generation is obtained from high-temperature steam electrolyzer sub-plant. Moreover, the membrane distillation unit is used for freshwater production, and also, the hydrogen compression unit with two compressors is used for compressed hydrogen storage. On the other hand, energy and exergy analyses, as well as irreversibilities, are examined according to various factors for examining the efficiency of the examined integrated plant and sub-plants. The results demonstrate that the total energy and exergy efficiencies of the designed plant are determined as 52.84% and 46.59%. Furthermore, the whole irreversibility rate of the designed cycle is to be 37,743 kW, and the highest irreversibility rate is determined in the biomass gasification unit with 12,685 kW.     

Effect of CaO hydration and carbonation on the hydrogen production from sorption enhanced water gas shift reaction

Sorption enhanced water gas shift reaction (SEWGS) based on calcium looping is an emerging technology for hydrogen production and CO₂ capture. SEWGS involves mainly two reactions, the catalytic WGS reaction and the bulk carbonation of CaO with CO₂, and the solid product is CaCO₃, and the Ca(OH)₂ may be formed from the reaction of CaO with H₂O with the presence of steam in gas phase. The effect of Ca(OH)₂ and CaCO₃ on the catalytic WGS reaction and carbonation reaction was studied in a fluidized bed reactor. It was found that the hydrated sorbent and CaCO₃ did not show any catalytic reactivity toward WGS reaction at 400 °C. When the temperature was increased to 500 °C and 600 °C, the catalytic reactivity of hydrated sorbent was recovered partially, but this will depend on the steam fraction in gas phase, the recovery of fresh CaO surface from dehydration of Ca(OH)₂ may be the reason of catalytic reactivity recovery. CaCO₃ can catalyze the WGS reaction at the high-temperature (>600 °C), this may due to the CaCO₃ decomposition and recarbonation processes in which the CaO is transiently formed. The possible mechanism was discussed.