The characteristics of syngas production from bio-oil dry reforming utilizing the waste heat of granulated blast furnace slag

A two-stage utilization of the waste heat of granulated blast furnace slag (BFS) was proposed, and the characteristics of bio-oil dry reforming under different conditions were investigated. For the bio-oil dry reforming utilizing granulated BFS as the heat carrier, when the temperature was higher than 800 °C, changes in the characteristics as bio-oil conversion and lower heating value (LHV) were not pronounced in response to the increasing temperature. The bio-oil conversion reached its maximum value with a CO₂/C (molar ratio of CO₂ to carbon in bio-oil) of 0.85. When the liquid hourly space velocity (LHSV) was higher than 0.45 h^?1, the bio-oil conversion and LHV dropped quickly as the LHSV increased. At the optimal condition with a temperature of 800 °C, a CO₂/C of 0.85 and an LHSV of 0.45 h^?1, the bio-oil conversion and LHV reached 90.15% and 511.02 kJ per mole of bio-oil, respectively. Granulated BFS could be beneficial for the bio-oil dry reforming process. Combining biomass pyrolysis and bio-oil dry reforming, a feasible industry application utilizing the waste heat of granulated BFS was presented systematically.     

Thermodynamic characteristics of reactants and energy conversion in steam reforming of calcium carbide furnace off-gas to produce hydrogen

In this study, to reveal the thermodynamic reaction mechanism and the conversion characteristics of material and energy for the steam reforming of multi-component materials, a chemical equilibrium model was constructed, and the reaction mechanism of the steam reforming of calcium carbide furnace off-gas (CCFG) was also identified. The conversion characteristics of material and energy were ascertained by assessing four independent reactions and their reverse reactions. And the effects of temperature, pressure and steam-to-gas ratio on the conversion ratios of CO and CH₄, the yield of H₂ and the reaction heat were investigated. In addition, a method for determining the process parameters of steam reforming based on the follow-up utilization scheme of CCFG was proposed; the method involves using a four-panel diagram that plots parameters of the steam reforming process. Thus, the range of H₂/CO mole ratio that could be obtained from the equilibrium system of steam reforming of CCFG was determined.     

Kinetic and experimental characterizations of biomass pyrolysis in granulated blast furnace slag

With the objective of abating the energy crisis and greenhouse gas emissions, biomass pyrolysis to recover waste heat from granulated blast furnace (BF) slag was investigated via thermogravimetric and continuous fixed-bed experiments. The results showed that the mass conversion of biomass pyrolysis increased with the increasing heating rate. At the same time, a higher gas yield and lower heating value (LHV) and concentrations of H₂ and CO were obtained with the increasing temperature. Granulated BF slag can promote the pyrolysis and reforming of biomass tar, increasing the gas yield and LHV and H₂ concentration. Thus, granulated BF slag not only provided heat for the pyrolysis reaction but also promoted the pyrolysis and reforming of biomass tar, which might block and corrode pipes in practical production. The shrinking core model (R2) selected using a two-step calculation method interpreted the biomass pyrolysis in granulated BF slag. The reaction activation energy ranged from 60.743 kJ/mol to 65.963 kJ/mol as the heating rate decreased from 40 K/min to 10 K/min.     

Thermodynamic analysis of combined unit of biomass gasifier and tar steam reformer for hydrogen production and tar removal

A combined unit of biomass gasifier and tar steam reformer (CGR) was proposed in this study to achieve simultaneous tar removal and increased hydrogen production. Tar steam reforming calculations based on thermodynamic equilibrium were carried out by using Aspen Plus software. Thermodynamic analysis reveals that when selecting appropriate operating conditions, exothermic heat available from the gasifier could sufficiently supply to the heat-demanding units including feed preheaters, steam generator and reformer. The effects of gasification temperature (T_gs), reforming temperature (T_ref) and steam-to-biomass ratio (S:BM) on percentages of tar removal and improvement of H₂ production were investigated. It was reported that the CGR system can completely remove tar and increase H₂ production (1.6 times) under thermally self-sufficient condition. The increase of H₂ production is mainly via the water–gas shift reaction.     

Bio-oil catalytic reforming without steam addition: Application to hydrogen production and studies on its mechanism

A novel process for hydrogen production via bio-oil catalytic reforming without steam addition was proposed. The liquid feedstock was a distillation fraction from crude bio-oil molecular distillation. The fraction obtained was enriched with the low-molecular-weight organics (acids, aldehydes, and ketones), and contained nearly all of the water from crude bio-oil. The highest catalytic performance, with a carbon conversion of 95% and a H₂ yield of 135 mg g⁻¹ organics, was obtained by processing the distillate over Ni/Al₂O₃ catalyst at 700 °C. The steam involved in the reforming reaction was derived entirely from the water in the crude bio-oil. The fresh and spent catalysts were characterized by N₂-physisorption, thermogravimetric analysis, and high-resolution transmission electron microscopy. To further understand the reaction mechanisms, symmetric density functional theory calculations for decomposition were performed on four model compounds in bio-oil (acetic acid, hydroxyacetone, furfural, and phenol) over the Ni(111) surface. In addition, the decomposition of H₂O∗ to OH∗ and O∗ and their subsequent steam reforming reactions with carbon precursors (CH∗ and CH₃C∗) were also examined.     

国内外熔融高炉渣显热回收方法

分析了熔融高炉渣显热回收的必要性。因为熔渣的物理性质和高炉出渣不连续性,导致熔渣显热回收存在困难。介绍了滚筒法、搅拌法、风淬法、连铸法、离心粒化和反应热法显热回收工艺,并指出甲烷-二氧化碳重整法有很好的发展前途。     

Simultaneous production of two types of synthesis gas by steam and tri‐reforming of methane using an integrated thermally coupled reactor: mathematical modeling

In this work, tri‐reforming and steam reforming processes have been coupled thermally together in a reactor for production of two types of synthesis gases. A multitubular reactor with 184 two‐concentric‐tubes has been proposed for coupling reactions of tri‐reforming and steam reforming of methane. Tri‐reforming reactions occur in outer tube side of the two‐concentric‐tube reactor and generate the needed energy for inner tube side, where steam reforming process is taking place. The cocurrent mode is investigated, and the simulation results of steam reforming side of the reactor are compared with corresponding predictions for thermally coupled steam reformer and also conventional fixed‐bed steam reformer reactor operated at the same feed conditions. This reactor produces two types of syngas with different H₂/CO ratios. Results revealed that H₂/CO ratio at the output of steam and tri‐reforming sides reached to 1.1 and 9.2, respectively. In this configuration, steam reforming reaction is proceeded by excess generated heat from tri‐reforming reaction instead of huge fired‐furnace in conventional steam reformer. Elimination of a low performance fired‐furnace and replacing it with a high performance reactor causes a reduction in full consumption with production of a new type of synthesis gas. The reactor performance is analyzed on the basis of methane conversion and hydrogen yield in both sides and is investigated numerically for various inlet temperature and molar flow rate of tri‐reforming side. A mathematical heterogeneous model is used to simulate both sides of the reactor. The optimum operating parameters for tri‐reforming side in thermally coupled tri‐reformer and steam reformer reactor are methane feed rate and temperature equal to 9264.4 kmol h^?1 and 1100 K, respectively. By increasing the feed flow rate of tri‐reforming side from 28,120 to 140,600 kmol h^?1, methane conversion and H₂ yield at the output of steam reforming side enhanced about 63.4% and 55.2%, respectively. Also by increasing the inlet temperature of tri‐reforming side from 900 to 1300 K, CH₄ conversion and H₂ yield at the output of steam reforming side enhanced about 82.5% and 71.5%, respectively. The results showed that methane conversion at the output of steam and tri‐reforming sides reached to 26.5% and 94%, respectively with the feed temperature of 1100 K of tri‐reforming side. Copyright © 2013 John Wiley & Sons, Ltd.     

Thermodynamic analysis of hydrogen production via autothermal steam reforming of selected components of aqueous bio-oil fraction

From a technical and economic point of view, autothermal steam reforming offers many advantages, as it minimizes heat load demand in the reformer. Bio-oil, the liquid product of biomass pyrolysis, can be effectively converted to a hydrogen-rich stream. Autothermal steam reforming of selected compounds of bio-oil was investigated using thermodynamic analysis. Equilibrium calculations employing Gibbs free energy minimization were performed for acetic acid, acetone and ethylene glycol in a broad range of temperature (400–1300 K), steam to fuel ratio (1–9) and pressure (1–20 atm) values. The optimal O₂/fuel ratio to achieve thermoneutral conditions was calculated under all operating conditions. Hydrogen-rich gas is produced at temperatures higher than 700 K with the maximum yield attained at 900 K. The ratio of steam to fuel and the pressure determine to a great extent the equilibrium hydrogen concentration. The heat demand of the reformer, as expressed by the required amount of oxygen, varies with temperature, steam to fuel ratio and pressure, as well as the type of oxygenate compound used. When the required oxygen enters the system at the reforming temperature, autothermal steam reforming results in hydrogen yield around 20% lower than the yield by steam reforming because part of the organic feed is consumed in the combustion reaction. Autothermicity was also calculated for the whole cycle, including preheating of the organic feed to the reactor temperature and the reforming reaction itself. The oxygen demand in such a case is much higher, while the amount of hydrogen produced is drastically reduced.     

旋转杯粒化高炉渣显热回收工艺综述

分析了利用旋转杯粒化高炉渣回收热量的工艺优势,此工艺不仅可以回收炉渣显热,而且粒化后的高炉渣还可以做水泥材料。同时介绍了相关不同工艺的技术路线,对比后得出旋转杯粒化高炉渣与化学反应回收熔渣余热工艺相结合的工艺由于能量形式转换次数少,回收率高,且在实际中更具可操作性,因此被认为是一种更具发展前景的工艺。     

Hydrogen-rich gas production from biomass catalytic gasification using hot blast furnace slag as heat carrier and catalyst in moving-bed reactor

A new concept that a heat recovery system from blast furnace (BF) slag which would generate hydrogen-rich gas was proposed and a continuous moving-bed biomass gasification reactor was designed to evaluate the feasibility. The influences of temperature and particle size of BF slag on gasification product distribution and gas characterization were discussed. The results show that BF slag demonstrated better catalytic performance in improving tar cracking, enhancing char gasification and reforming of hydrocarbons; higher BF slag temperature and smaller particles size can produce more light gases, less char and condensate; as temperature of BF slag being 1200 °C and its size below 2 mm, gas yield and H₂ content achieved the maximum being 1.28 N m³/kg and 46.54%, respectively.     

Hydrogen production from bio-oil: A thermodynamic analysis of sorption-enhanced chemical looping steam reforming

The steam reforming of pyrolysis bio-oil is one proposed route to low carbon hydrogen production, which may be enhanced by combination with advanced steam reforming techniques. The advanced reforming of bio-oil is investigated via a thermodynamic analysis based on the minimisation of Gibbs Energy. Conventional steam reforming (C-SR) is assessed alongside sorption-enhanced steam reforming (SE-SR), chemical looping steam reforming (CLSR) and sorption-enhanced chemical looping steam reforming (SE-CLSR). The selected CO₂ sorbent is CaO(s) and oxygen transfer material (OTM) is Ni/NiO. PEFB bio-oil is modelled as a surrogate mixture and two common model compounds, acetic acid and furfural, are also considered. A process comparison highlights the advantages of sorption-enhancement and chemical looping, including improved purity and yield, and reductions in carbon deposition and process net energy balance.The operating regime of SE-CLSR is evaluated in order to assess the impact of S/C ratio, NiO/C ratio, CaO/C ratio and temperature. Autothermal operation can be achieved for S/C ratios between 1 and 3. In autothermal operation at 30 bar, S/C ratio of 2 gives a yield of 11.8 wt%, and hydrogen purity of 96.9 mol%. Alternatively, if autothermal operation is not a priority, the yield can be improved by reducing the quantity of OTM. The thermodynamic analysis highlights the role of advanced reforming techniques in enhancing the potential of bio-oil as a source of hydrogen.     

Steam reforming of propionic acid: Thermodynamic analysis of a model compound for hydrogen production from bio-oil

The thermodynamic equilibrium of steam reforming of propionic acid (HPAc) as a bio-oil model compound was studied over a wide range of reaction conditions (T = 500–900 °C, P = 1–10 bar and H₂O/HPAc = 0–4 mol/mol) using non-stoichiometric equilibrium models. The effect of operating conditions on equilibrium conversion, product composition and coke formation was studied. The equilibrium calculations indicate nearly complete conversion of propionic acid under these conditions. Additionally, carbon and methane formation are unfavorable at high temperatures and high steam to carbon (S/C) ratios. The hydrogen yield versus S/C ratio passes a maximum, the value and position of which depends on temperature. The thermodynamic equilibrium results for HPAc fit favorably with experimental data for real bio-oil steam reforming under same reaction conditions.     

Thermodynamic analysis of steam assisted conversions of bio-oil components to synthesis gas

The aim of this study is to investigate the thermodynamics of steam assisted, high-pressure conversions of model components of bio-oil – isopropyl alcohol, lactic acid and phenol – to synthesis gas (H₂ + CO) and to understand the effects of process variables such as temperature and inlet steam-to-fuel ratio on the product distribution. For this purpose, thermodynamic analyses are performed at a pressure of 30 bar and at ranges of temperature and steam-to-fuel ratio of 600–1200 K and 4–9, respectively. The number of moles of each component in the product stream and the product composition at equilibrium are calculated via Gibbs free energy minimization technique. The resulting optimization problems are solved by using the Sequential quadratic programming method. The results showed that all of the model fuels reached near-complete conversions to H₂, CO, CO₂ and CH₄ within the range of operating conditions. Temperature and steam-to-fuel ratio had positive effects in increasing hydrogen content of the product mixture at different magnitudes. Production of CO increased with temperature, but decreased at high steam-to-fuel ratios. Conversion of model fuels in excess of 1000 K favored molar H₂/CO ratios around 2, the synthesis gas composition required for Fischer–Tropsch and methanol syntheses. It was also possible to adjust the H₂/CO ratios and the amounts of CH₄ and CO₂ in synthesis gas by steam-to-fuel ratio, the value depending on temperature and the fuel type. Product distribution trends indicated the presence of water–gas shift and methanation equilibria as major side reactions running in parallel with the steam reforming of the model hydrocarbons.     

Thermodynamic analysis of hydrogen production via steam reforming of selected components of aqueous bio-oil fraction

This work presents thermodynamics analysis of hydrogen production via steam reforming of bio-oil components. The model compounds, acetic acid, ethylene glycol and acetone, representatives of the major classes of components present in the aqueous fraction of bio-oil were used for the study. The equilibrium product compositions were investigated in a broad range of conditions like temperature (400–1300 K), steam to fuel ratio (1–9) and pressure (1–20 atm). Any of the three model compounds can be fully reformed even at low temperatures producing hydrogen with maximum yield ranging from 80% to 90% at 900 K. Steam to fuel ratio positively affect the hydrogen content over the entire range of temperature studied. Conversely, higher pressure decreases the hydrogen yield. The formation of solid carbon (graphite) does not constitute a problem provided that reforming temperatures higher than 600 K and steam to fuel ratios higher than 4 for acetic acid and ethylene glycol and 6 for acetone are to be used. Thermal decomposition of the bio-oil components is thermodynamically feasible, forming a mixture containing _C(s)${\mathrm{C}}_{(\mathrm{s})}$, CH₄, H₂, CO, CO₂, and H₂O at various proportions depending on the specific nature of the compound and the temperature. Material and energy balances of complete reforming system demonstrated that the production of 1 kmol/s hydrogen from bio-oil steam reforming requires almost the same amount of energy as with natural gas reforming.     

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.     

Catalyst modification strategies to enhance the catalyst activity and stability during steam reforming of acetic acid for hydrogen production

A high energy content (∼122 MJ/kg H₂) and presence of hydrogen-bearing compounds abundance in nature make hydrogen forth runner candidate to fulfill future energy requirements. Biomass being abundant and carbon neutral is one of the promising source of hydrogen production. In addition, it also addresses agricultural waste disposal problems and will bring down our dependency on fossil fuel for energy requirements. Biomass-derived bio-oil can be an efficient way for hydrogen production. Acetic acid is the major component of bio-oil and has been extensively studied by the researchers round the globe as a test component of bio-oil for hydrogen generation. Hydrogen can be generated from acetic acid via catalytic steam reforming process which is thermodynamically feasible. A number of nickel-based catalysts have been reported. However, the coke deposition during reforming remains a major challenge. In this review, we have investigated all possible reactions during acetic acid steam reforming (AASR), which can cause coke deposition over the catalyst surface. Different operating parameters such as temperature and steam to carbon feed ratio affect not only the product distribution but also the carbon formation during the reaction. Present review elaborates effects of preparation methods, active metal catalyst including bimetallic catalysts, type of support and microstructure of catalysts on coke resistance behavior and catalyst stability during reforming reactions. The present study also focuses on the effects of a combination of a variety of alkali and alkaline earth metals (AAEM) promoters on coke deposition. Effect of specially designed reactors and the addition of oxygen on carbon deposition during AASR have also been analyzed. This review based on the available literature focuses mainly on the catalyst deactivation because of coke deposition, and possible strategies to minimize catalyst deactivation during AASR.     

Intensified bio-oil steam reforming for high-purity hydrogen production: Numerical simulation and sorption kinetics

This work proposes the production of high-purity hydrogen by an intensified non-isothermal sorption-enhanced bio-oil steam reforming (SEBOSR) process, by combining the bio-oil steam reforming over a Ni/La₂O₃-αAl₂O₃ catalyst and in-situ CO₂ adsorption over Li₂CuO₂. The kinetics of CO₂ adsorption on Li₂CuO₂ was studied experimentally and applied to assess the performance of SEBOSR in a fixed bed reactor via a non-isothermal mathematical model. Model simulations show that the prebreakthrough stage of the SEBOSR process, which corresponds to high purity H₂ production, can be extended by increasing the adsorbent loading and the S/C ratio, as well as by decreasing the inlet gas velocity. Increasing inlet temperature generates longer prebreakthrough step times but leads to a reduction in hydrogen purity. This intensified process allows to diminish the catalyst deactivation, which ultimately only occurs in the inlet region of the packed bed to some extent. In addition, SEBOSR indirectly uses sustainable CO₂-neutral biomass as a source of hydrogen; highly pure and renewable H₂ can be produced in one step (without the need of additional gas purification), via a process with enhanced thermal efficiency.     

Hydrogen production by low-temperature reforming of organic compounds in bio-oil over a CNT-promoting Ni catalyst

Present study reports on high catalytic activity of CNTs-supported Ni catalyst (x% Ni-CNTs) synthesized by the homogeneous deposition–precipitation method, which was successfully applied for low-temperature reforming of organic compounds in bio-oil. The optimal Ni-loading content was about 15 wt%. The H₂ yield over the 15 wt% Ni-CNTs catalyst reached about 92.5% at 550 °C. The influences of the reforming temperature (T), the molar ratio of steam to carbon fed (S/C) and the current (I) passing through the catalyst, on the reforming process of the bio-oil over the Ni-CNTs' catalysts were investigated using the stream as the carrier gas in the reforming reactor. The features of the Ni-CNTs' catalysts with different loading contents of Ni were investigated via XRD, XPS, TEM, ICP/AES, H₂-TPD and the N₂ adsorption–desorption isotherms. From these analyses, it was found that the uniform and narrow distribution with smaller Ni particle size as well as higher Ni dispersion was realized for the CNTs-supported Ni catalyst, leading to excellent low-temperature reforming of oxygenated organic compounds in bio-oil.     

Operation of Rh/Ce0.75Zr0.25O2-δ-ƞ-Al2O3/FeCrAl wire mesh honeycomb catalytic modules in diesel steam and autothermal reforming

The Rh/Ce_0·75Zr_0·25O_2–δ-ƞ-Al₂O₃/FeCrAl structured catalytic blocks of length 10, 20, and 60 mm were prepared and tested in the reactions of steam and autothermal reforming of n-hexadecane. It was found in a series of experiments on hexadecane steam reforming with the catalyst heating solely through the reactor wall that the complete conversion of hexadecane at a furnace temperature below 750 °C was not achieved even at GHSV = 10,000 h⁻¹. Under these conditions, the formation of carbon on the catalyst surface was observed. At the reactor wall temperature of 800 °C, the complete conversion of hexadecane was achieved even in the 10 mm long catalytic block (GHSV = 60,000 h⁻¹), accompanied by the formation of various intermediate light hydrocarbons. To achieve complete conversion of these intermediate compounds (mainly 1-alkenes), it is necessary to carry out the steam reforming reaction at GHSV = 10,000 h⁻¹. At hexadecane autothermal reforming, heat is supplied to the reaction zone by exothermic oxidation reaction, which makes this process more efficient. In experiments with the use of additional external heat supply through the reactor wall, complete conversion of hexadecane occurred at GHSV = 120,000 h⁻¹. To convert all by-products (mainly 1-alkenes) and achieve a nearly thermodynamic equilibrium distribution of the main reaction products (H₂, CO, CO₂), the reaction should be carried out at GHSV = 20,000 h⁻¹. Without external heat supply, hexadecane conversion decreased, while the content of light hydrocarbons in the reaction products increased. An increase in the inlet amount of oxygen helps to compensate the heat losses in the reactor and to increase the efficiency of hexadecane autothermal reforming. The performed experiments allow better understanding of the processes which occur during the steam and autothermal reforming of diesel.     

Carbon deposition behavior in steam reforming of bio-oil model compound for hydrogen production

Catalyst deactivation caused by coke formation is a bottleneck in steam reforming of bio-oil for hydrogen production. The investigation of carbon deposition behavior can make a contribution to the improvement of catalyst and the knowledge of reaction mechanism. In this paper, m-cresol (C₇H₈O, one of the organic compounds present in bio-oil) was chosen as model compound. The experiment was carried out on a commercial Ni/MgO catalyst. As a comparative test, m-cresol decomposition showed carbon deposition can be formed more easily under higher temperature. In steam reforming process, for the competition of carbon deposition and carbon elimination, a peak value of coking formation rate was obtained in a broad range of temperature (575–900 °C). The increase of steam to carbon ratio can favor the carbon elimination. Final coking formation rate curve was determined under optimal reaction conditions and the results showed the severity of carbon deposition maintained a very low level during the entire reaction time. Based on the distribution of reforming products, high temperature and sufficient water feeding can favor the carbon conversion from solid and liquid phase to gaseous phase. Unreacted m-cresol is the main organic compound detected in liquid condensate. Some secondary reactions can be deduced through the other compounds detected. The carbon deposition state on catalyst surface can be in the form of nanofiber, but their concrete shapes can be different due to different reaction conditions.