A preliminary study of a novel catalyst Al2O3·Na2O·xH2O/NaOH/Al(OH)3 for production of hydrogen and hydrogen-rich gas by steam gasification from cellulose

The new catalyst, Al₂O₃·Na₂O·xH₂O/NaOH/Al(OH)₃, was made by means of hydrolyzation and hydration of sodium aluminum oxide (Al₂O₃·Na₂O). Hydrogen and hydrogen-rich gas were produced through the reaction of cellulose with the catalyst and steam. In order to avoid production of tar, the gasification temperature is controlled at ≤673 K. The temperature of producing hydrogen is controlled at about 473–623 K. The conversion degree of hydrogen from cellulose at about 473–673 K could come up to 59.63%. The production of hydrogen-rich gas was set at about 673 K. The gasification residue could be used as material for combustion. Al₂O₃·Na₂O could be regenerated from the byproducts Al₂O₃ and Na₂CO₃ produced in the combustion process. The catalyst could be re-prepared from the regenerative Al₂O₃·Na₂O.     

Characteristics of tar,NOx precursors and their absorption performance with different scrubbing solvents during the pyrolysis of sewage sludge

Recently thermal utilizations of sewage sludge, especially pyrolysis and gasification, are regarded as promising technologies due to efficient utilization of fuel gas. In this study, characteristics of tar and NOx precursors were investigated during the pyrolysis of sewage sludge. Moreover, absorption performance for tar and NOx precursors were also studied by using four kinds of scrubbing mediums: cooking oil, diesel oil, BDF and water. The results showed that nitrogenous light PAHs were the major components of nitrogenous tar produced from the pyrolysis of sewage sludge. As for gravimetric tar and major nitrogenous tar compounds removal, cooking oil was the most suitable absorbent. With respect to NOx precursors, it was concluded that HCN, sharing of about 39.5% of total nitrogen of the sewage sludge, was the main NOx precursor gas whereas NH₃ content could be neglected. Absorption capacity of hydrophobic scrubbing mediums against NOx precursor gases could be arranged as followed: diesel oil > cooking oil > BDF.     

Syngas yield during pyrolysis and steam gasification of paper

Main characteristics of gaseous yield from steam gasification have been investigated experimentally. Results of steam gasification have been compared to that of pyrolysis. The temperature range investigated were 600–1000 °C in steps of 100 °C. Results have been obtained under pyrolysis conditions at same temperatures. For steam gasification runs, steam flow rate was kept constant at 8.0 g/min. Investigated characteristics were evolution of syngas flow rate with time, hydrogen flow rate and chemical composition of syngas, energy yield and apparent thermal efficiency. Residuals from both processes were quantified and compared as well. Material destruction, hydrogen yield and energy yield is better with gasification as compared to pyrolysis. This advantage of the gasification process is attributed mainly to char gasification process. Char gasification is found to be more sensitive to the reactor temperature than pyrolysis. Pyrolysis can start at low temperatures of 400 °C; however char gasification starts at 700 °C. A partial overlap between gasification and pyrolysis exists and is presented here. This partial overlap increases with increase in temperature. As an example, at reactor temperature 800 °C this overlap represents around 27% of the char gasification process and almost 95% at reactor temperature 1000 °C.     

Hydrogen-rich gas from catalytic steam gasification of biomass in a fixed bed reactor: Influence of particle size on gasification performance

The catalytic steam gasification of biomass was carried out in a lab-scale fixed bed reactor in order to evaluate the effects of particle size at different bed temperatures on the gasification performance. The bed temperature was varied from 600 to 900 °C and the biomass was separated into five different size fractions (below 0.075 mm, 0.075–0.15 mm, 0.15–0.3 mm, 0.3–0.6 mm and 0.6–1.2 mm). The results show that with decreasing particle size, the dry gas yield, carbon conversion efficiency and H₂ yield increased, and the content of char and tar decreased. And the differences due to particle sizes in gasification performance practically disappear as the higher temperature bound is approached. Hydrogen and carbon monoxide contents in the produced gas increase with decreasing particle size at 900 °C, reaching to 51.2% and 22.4%, respectively.     

An experimental study on air gasification of biomass micron fuel (BMF) in a cyclone gasifier

Biomass micron fuel (BMF) produced from feedstock (energy crops, agricultural wastes, forestry residues and so on) through an efficient crushing process is a kind of powdery biomass fuel with particle size of less than 250 μm. Based on the properties of BMF, a cyclone gasifier concept has been considered in our laboratory for biomass gasification. The concept combines and integrates partial oxidation, fast pyrolysis, gasification, and tar cracking, as well as a shift reaction, with the purpose of producing a high quality of gas. In this paper, characteristics of BMF air gasification were studied in the gasifier. Without outer heat energy input, the whole process is supplied with energy produced by partial combustion of BMF in the gasifier using a hypostoichiometric amount of air. The effects of equivalence ratio (ER) and biomass particle size on gasification temperature, gas composition, gas yield, low-heating value (LHV), carbon conversion and gasification efficiency were studied. The results showed that higher ER led to higher gasification temperature and contributed to high H₂-content, but too high ER lowered fuel gas content and degraded fuel gas quality. A smaller particle was more favorable for higher gas yield, LHV, carbon conversion and gasification efficiency. And the BMF air gasification in the cyclone gasifier with the energy self-sufficiency is reliable.     

Experimental and kinetic modeling study of 2,5-dimethylfuran pyrolysis at various pressures

The pyrolysis of 2,5-dimethylfuran (DMF) in a flow reactor was investigated at various pressures (30, 150 and 760 Torr) by synchrotron vacuum ultraviolet photoionization mass spectrometry (SVUV-PIMS). Dozens of pyrolysis products, especially a series of radicals and aromatics, were identified from the measurement of photoionization efficiency spectra; and their mole fraction profiles were measured at 780–1470 K. Phenol, 1,3-cyclopentadiene, 2-methylfuran, vinylacetylene and 1,3-butadiene were observed with high concentrations in the decomposition of DMF. The pressure-dependent rate constants of the major unimolecular decomposition reactions of DMF were theoretically calculated, and was adopted in the pyrolysis model of DMF with 285 species and 1173 reactions developed in the present work. The model was validated against the species profiles measured in both the present work and the previous pyrolysis studies of DMF. Based on the rate of production and sensitivity analyses, main pathways in the decomposition of DMF and the growth of aromatics were determined. The unimolecular decomposition to produce CH₃CHCCH and acetyl radicals, H-atom abstraction to produce 5-methyl-2-furanylmethyl radical, ipso substitution by H-atom to produce 2-methylfuran and H-atom attack to produce 1,3-butadiene and acetyl radical were concluded to dominate the primary decomposition of DMF. Further decomposition of 5-methyl-2-furanylmethyl radical leads to great production of phenol and 1,3-cyclopentadiene which can be readily converted to precursors of large aromatics such as cyclopentadienyl radical, phenyl radical and benzene. As a result, the formation of aromatics in the pyrolysis of DMF is promoted compared with the pyrolysis of cyclohexane and methylcyclohexane under very close conditions. This observation implies the potentially high sooting tendency of DMF, and emphasizes the necessity to investigate the sooting behavior and soot formation mechanism in DMF combustion for the potential application of DMF as an alternative engine fuel.     

Exergy analysis of biomass staged-gasification for hydrogen-rich syngas

Using Aspen Plus simulations, exergy analyses of hydrogen-rich syngas production via biomass staged-gasification are carried out for three configurations, namely, staged-gasification with pyrolysis gas combustion and char gasification (C-1), staged-gasification with pyrolysis gas reforming and char gasification (C-2), and staged-gasification with pyrolysis gas reforming and char combustion (C-3). The results show that, for the gasification and reforming processes, the exergy loss of pyrolysis gas with tar reforming is less than that of char gasification. As for the system, it is conducive to generating hydrogen by making full use of the hydrogen element (H) in biomass instead of the H in water. The benefits of C-1 are that it removes tar and produces higher yield and concentration of hydrogen. However, C-2 is capable of obtaining higher exergy efficiency and lower exergy loss per mole of H₂ production. C-3 theoretically has greater process performances, but it has disadvantages in tar conversion in practical applications. The appropriate gasification temperature (T_G) are in the range of 700–750 °C and the appropriate mass ratio of steam to biomass (S/B) are in the range of 0.6–0.8 for C-1 and C-3; the corresponding parameters for C-2 are in the ranges of 650–700 °C and 0.7–0.8, respectively.     

A coordinated investigation of the combustion chemistry of diisopropyl ketone,a prototype for biofuels produced by endophytic fungi

Several classes of endophytic fungi have been recently identified that convert cellulosic biomass to a range of ketones and other oxygenated molecules, which are potentially viable as biofuels, but whose oxidation chemistry is not yet well understood. In this work, we present a predictive kinetics model describing the pyrolysis and oxidation of diisopropyl ketone (DIPK) that was generated automatically using the Reaction Mechanism Generator (RMG) software package. The model predictions are evaluated against three experiments that cover a range of temperatures, pressures, and oxygen concentrations: (1) Synchrotron photoionization mass spectrometry (PIMS) measurements of pyrolysis in the range 800–1340 K at 30 Torr and 760 Torr; (2) Synchrotron PIMS measurements of laser photolytic Cl-initiated oxidation from 550 K to 700 K at 8 Torr; and (3) Rapid-compression machine measurements of ignition delay between 591 K and 720 K near 10 bar. Improvements made to the model parameters, particularly in the areas of hydrogen abstraction from the initial DIPK molecule and low-temperature peroxy chemistry, are discussed. Our ability to automatically generate this model and systematically improve its parameters without fitting to the experimental results demonstrates the usefulness of the predictive chemical kinetics paradigm.     

Pressurized chemical-looping combustion of coal with an iron ore-based oxygen carrier

Chemical-looping combustion (CLC) is a new combustion technology with inherent separation of CO₂. Most of the previous investigations on CLC of solid fuels were conducted under atmospheric pressure. A pressurized CLC combined cycle (PCLC-CC) system is proposed as a promising coal combustion technology with potential higher system efficiency, higher fuel conversion, and lower cost for CO₂ sequestration. In this study pressurized CLC of coal with Companhia Valedo Rio Doce (CVRD) iron ore was investigated in a laboratory fixed bed reactor. CVRD iron ore particles were exposed alternately to reduction by 0.4 g of Chinese Xuzhou bituminous coal gasified with 87.2% steam/N₂ mixture and oxidation with 5% O₂ in N₂ at 970 °C. The operating pressure was varied between 0.1 MPa and 0.6 MPa. First, control experiments of steam coal gasification over quartz sand were performed. H₂ and CO₂ are the major components of the gasification products, and the operating pressure influences the gas composition. Higher concentrations of CO₂ and lower fractions of CO, CH₄, and H₂ during the reduction process with CVRD iron ore was achieved under higher pressures. The effects of pressure on the coal gasification rate in the presence of the oxygen carrier were different for pyrolysis and char gasification. The pressurized condition suppresses the initial coal pyrolysis process while it also enhances coal char gasification and reduction with iron ore in steam, and thus improves the overall reaction rate of CLC. The oxidation rates and variation of oxygen carrier conversion are higher at elevated pressures reflecting higher reduction level in the previous reduction period. Scanning electron microscope and energy-dispersive X-ray spectroscopy (SEM-EDX) analyses show that particles become porous after experiments but maintain structure and size after several cycles. Agglomeration was not observed in this study. An EDX analysis demonstrates that there is very little coal ash deposited on the oxygen carrier particles but no appreciable crystalline phases change as verified by X-ray diffraction (XRD) analysis. Overall, the limited pressurized CLC experiments carried out in the present work suggest that PCLC of coal is promising and further investigations are necessary.     

Experimental study on coal multi-generation in dual fluidized beds

An atmospheric test system of dual fluidized beds for coal multi-generation was built.One bubbling fluidized bedis for gasification and a circulating fluidized bed for combustion.The two beds are combined with two valves:one valve to send high temperature ash from combustion bed to the gasification bed and another valve to sendchar and ash from gasification bed to combustion bed.Experiments on Shenhua coal multi-generation were madeat temperatures from 1112 K to 1191 K in the dual fluidized beds.The temperatures of the combustor are stableand the char combustion efficiency is about 98%.Increasing air/coal ratio to the fluidized bed leads to theincrease of temperature and gasification efficiency.The maximum gasification efficiency is 36.7% and thecalorific value of fuel gas is 10.7 MJ/Nm3.The tar yield in this work is 1.5%,much lower than that of pyrolysis.Carbon conversion efficiency to fuel gas and flue gas is about 90%.     

Co-utilization of biomass and natural gas in combined cycles through primary steam reforming of the natural gas

Power production from biomass can occur through external combustion (e.g. steam cycles, organic Rankine cycles, Stirling engines), or internal combustion after gasification or pyrolysis (e.g. gas engines, IGCC). External combustion has the disadvantage of delivering limited conversion efficiencies (max 30–35%). Internal combustion has the potential of high efficiencies, but it always needs a severe and mostly problematic gas cleaning.     

Hydrogen-rich gas from catalytic steam gasification of municipal solid waste (MSW): Influence of catalyst and temperature on yield and product composition

In the present study the catalytic steam gasification of MSW to produce hydrogen-rich gas or syngas (H₂ + CO) with calcined dolomite as a catalyst in a bench-scale downstream fixed bed reactor was investigated. The influence of the catalyst and reactor temperature on yield and product composition was studied at the temperature range of 750–950 °C, with a steam to MSW ratio of 0.77, for weight hourly space velocity of 1.29 h⁻¹. Over the ranges of experimental conditions examined, calcined dolomite revealed better catalytic performance, at the presence of steam, tar was completely decomposed as temperature increases from 850 to 950 °C. Higher temperature resulted in more H₂ and CO production, higher carbon conversion efficiency and dry gas yield. The highest H₂ content of 53.29 mol%, and the highest H₂ yield of 38.60 mol H₂/kg MSW were observed at the highest temperature level of 950 °C, while, the maximum H₂ yield potential reached 70.14 mol H₂/kg dry MSW at 900 °C. Syngas produced by catalytic steam gasification of MSW varied in the range of 36.35–70.21 mol%. The char had a highest ash content of 84.01% at 950 °C, and negligible hydrogen, nitrogen and sulphur contents.     

Impact of nitrogen oxides (NO,NO2, N2O) on the formation of soot

The emission of both nitrogen oxides and soot from combustion processes is still a matter of concern. When a flue gas recirculation (FGR) technique is applied, the presence of a given nitrogen oxide in the recirculated mixture can affect the emissions of other pollutants, such as soot, and be used for its control in a combustion process. In this context, the present work is focused on the identification of the effect of the main nitrogen oxides (NO, NO₂ and N₂O) present in combustion systems on soot and main product gases formation from the pyrolysis of ethylene, at atmospheric pressure and in the 975–1475 K temperature range. The experimental results are examined to assess the effectiveness of each nitrogen oxide in suppressing or boosting soot formation, to achieve the possible nitrogen oxides reduction, and to identify the elementary steps involved in the nitrogen oxides and ethylene conversion as function of the different nitrogen oxides. This analysis is supported on model calculations.     

Char and char-supported nickel catalysts for secondary syngas cleanup and conditioning

Tars in biomass gasification systems need to be removed to avoid damaging and clogging downstream pipes or equipment. In this study, Ni-based catalysts were made by mechanically mixing NiO and char particles at various ratios. Catalytic performance of the Ni/char catalysts was studied and compared with performance of wood char and coal char without Ni for syngas cleanup in a laboratory-scale updraft biomass gasifier. Reforming parameters investigated were reaction temperature (650–850 °C), NiO loading (5–20% of the weight of char support), and gas residence time (0.1–1.2 s). The Ni/coalchar and Ni/woodchar catalysts removed more than 97% of tars in syngas at 800 °C reforming temperature, 15% NiO loading, and 0.3 s gas residence time. Analysis of syngas composition indicated that concentrations of H₂ and CO in syngas significantly. Furthermore, performance of the Ni/coalchar catalyst was continuously tested for 8 h. There was slight deactivation of the catalyst in the early stage of tar/syngas reforming; however, the catalyst was able to stabilize soon after. It was concluded that chars especially coal char can be an effective and inexpensive support of NiO for biomass gasification tar removal and syngas conditioning.     

The impact of steam and current density on carbon formation from biomass gasification tar on Ni/YSZ, and Ni/CGO solid oxide fuel cell anodes

The combination of solid oxide fuel cells (SOFCs) and biomass gasification has the potential to become an attractive technology for the production of clean renewable energy. However the impact of tars, formed during biomass gasification, on the performance and durability of SOFC anodes has not been well established experimentally. This paper reports an experimental study on the mitigation of carbon formation arising from the exposure of the commonly used Ni/YSZ (yttria stabilized zirconia) and Ni/CGO (gadolinium-doped ceria) SOFC anodes to biomass gasification tars. Carbon formation and cell degradation was reduced through means of steam reforming of the tar over the nickel anode, and partial oxidation of benzene model tar via the transport of oxygen ions to the anode while operating the fuel cell under load. Thermodynamic calculations suggest that a threshold current density of 365 mA cm⁻² was required to suppress carbon formation in dry conditions, which was consistent with the results of experiments conducted in this study. The importance of both anode microstructure and composition towards carbon deposition was seen in the comparison of Ni/YSZ and Ni/CGO anodes exposed to the biomass gasification tar. Under steam concentrations greater than the thermodynamic threshold for carbon deposition, Ni/YSZ anodes still exhibited cell degradation, as shown by increased polarization resistances, and carbon formation was seen using SEM imaging. Ni/CGO anodes were found to be more resilient to carbon formation than Ni/YSZ anodes, and displayed increased performance after each subsequent exposure to tar, likely due to continued reforming of condensed tar on the anode.     

Thermodynamic optimization of biomass gasification for decentralized power generation and Fischer–Tropsch synthesis

In recent years, biomass gasification has emerged as a viable option for decentralized power generation, especially in developing countries. Another potential use of producer gas from biomass gasification is in terms of feedstock for Fischer–Tropsch (FT) synthesis – a process for manufacture of synthetic gasoline and diesel. This paper reports optimization of biomass gasification process for these two applications. Using the non–stoichometric equilibrium model (SOLGASMIX), we have assessed the outcome of gasification process for different combinations of operating conditions. Four key parameters have been used for optimization, viz. biomass type (saw dust, rice husk, bamboo dust), air or equivalence ratio (AR = 0, 0.2, 0.4, 0.6, 0.8 and 1), temperature of gasification (T = 400, 500, 600, 700, 800, 900 and 1000 °C), and gasification medium (air, air–steam 10% mole/mole mixture, air–steam 30%mole/mole mixture). Performance of the gasification process has been assessed with four measures, viz. molar content of H₂ and CO in the producer gas, H₂/CO molar ratio, LHV of producer gas and overall efficiency of gasifier. The optimum sets of operating conditions for gasifier for FT synthesis are: AR = 0.2–0.4, Temp = 800–1000 °C, and gasification medium as air. The optimum sets of operating conditions for decentralized power generation are: AR = 0.3–0.4, Temp = 700–800 °C with gasification medium being air. The thermodynamic model and methodology presented in this work also presents a general framework, which could be extended for optimization of biomass gasification for any other application.     

Exergy analysis of hydrogen production from biomass gasification

For a given set of operating conditions, the hydrogen production from biomass gasification can be improved through optimization of the operating parameters and efficiencies. The present approach can predict hydrogen production via biomass gasification in a range of 10–32 kg/s from biomass (sawdust wood). The biomass is introduced to a gasifier at an operating temperature range of 1000–1500 K. Also, 4.5 kg/s of steam at 500 K is used as gasification medium. Results indicate that improvement in hydrogen production from biomass steam gasification depending on the amount of steam and quantity of biomass feeding to the gasifier as well the operating temperature. Over the range of feeding biomass, the hydrogen yield reaches 80–130 g H₂/kg biomass while in the operating temperature examined, the hydrogen yield reaches 80 g H₂/kg biomass. On mole basis it is found that, in the first range of H₂ varies from 51 to 63% in the studied range of feeding biomass in existing 4.5 kg/s from steam while H₂ gets to 51–53% in existing of 6.3 kg/s from steam.     

Partial oxidative gasification of phenol for hydrogen in supercritical water

The paper reports partial oxidative gasification of phenol for hydrogen in supercritical water (SCW) at lower temperature (<753 K), at which cleavages of aromatic ring occur difficultly and tend to undesirable polymerization. The results showed that O₂ is effective to gasification of phenol in SCW. ∼76% of phenol was gasified and 2.7 mol/mol of hydrogen was produced within 180 s with Na₂CO₃ as catalyst at the selected process conditions, a molar ratio of oxygen-to-phenol, 7.5–1, 723 K, and 24 MPa. It was found that unstable opening-rings products oxalic and maleic acid and stable dimmerization compounds in liquid water were formed during partial oxidation process. The process also indicated phenol was rapidly converted, and some opening-rings products were slowly gasified, which also confirmed oxygen served as effective reactant for ring-opening. Based on the given reaction conditions, a treatment process using a real wastewater from coking industry was performed. The data showed that the present technology provides an effective way to gasification of phenol wastewater for high-value energy utilization.     

On the chemical kinetics of cyclopentadiene oxidation

The cyclopentadiene/cyclopentadienyl system forms a critical part in the oxidation chemistry of aromatic fuel components used in surrogate fuels and the importance of the cyclopentadienyl radical in poly-aromatic hydrocarbon (PAH) growth has also been noted due to its site dependent reactivity. The latter aspect has been subject to a number of studies along with the initial pyrolysis steps. By contrast, few studies have been performed of the corresponding oxidation chemistry under conditions of relevance to combustion applications. Thermochemical data for oxidation reactions featuring the cyclopentadienyl radical with O, OH, HO₂ and O₂ were determined at the G3B3 and G4/G4MP2 levels in combination with an analysis of internal rotations using density functional theory and with the Jahn–Teller effect treated as a pseudo-rotation. The calculated potential energy surfaces were subsequently used in a consistent manner for the determination of pressure dependent reaction rate parameters through the Rice–Ramsperger–Kassel–Marcus/master-equation approach with Eckart quantum tunnelling corrections applied to reactions involving hydrogen transfers. The accuracy of the method was further investigated by comparisons of computed rate parameters for pyrolysis reactions with alternative determinations. The resulting chemistry was incorporated into an evaluation framework for the study of cyclopentadiene oxidation using recent experimental flow reactor data and principal uncertainties in reaction pathways assessed.     

生物质焦油的特性及其净化研究现状

通过分析生物质热解气化过程中焦油的特性和生成机制,以及净化方法研究现状,了解焦油的主要组成和基本特性参数,发现焦油随着反应温度的升高,逐步经过裂解、聚合、缩合反应生成多环芳香烃。而焦油的脱除应当根据不同的生物质气化反应特性,多种方法结合,以减少催化剂损失、提高焦油脱除率和转化率。