Effect of gasification reactions on biomass char conversion under pulverized fuel combustion conditions

The effect of gasification reactions on biomass char conversion under pulverized fuel combustion conditions was studied by single particle experiments and modelling. Experiments of pine and beech wood char conversion were carried out in a single particle combustor under conditions of 1473-1723 K, 0.0-10.5% O₂, and 25-42% H₂O. A comprehensive progressive char conversion model, including heterogeneous reactions (char oxidation and char gasification with CO₂ and H₂O), homogeneous reactions (CO oxidation, water-gas shift reaction, and H₂ oxidation) in the particle boundary layer, particle shrinkage, and external and internal heat and mass transfer, was developed. The modelling results are in good agreement with both experimental char conversion time and particle size evolution in the presence of oxygen, while larger deviations are found for the gasification experiments. The modelling results show that the char oxidation is limited by mass transfer, while the char gasification is controlled by both mass transfer and gasification kinetics at the investigated conditions. A sensitivity analysis shows that the CO oxidation in the boundary layer and the gasification kinetics influence significantly the char conversion time, while the water-gas shift reaction and H₂ oxidation have only a small effect. Analysis of the sensitive parameters on the char conversion process under a typical pulverized biomass combustion condition (4% O₂, 13% CO₂, 13% H₂O), shows that the char gasification reactions contribute significantly to char conversion, especially for millimeter-sized biomass char particles at high temperatures.     

A reduced mechanism for primary reactions of coal volatiles in a plug flow reactor

In the present paper, the authors study the primary reactions of coal volatiles and a detailed mechanism has been made for three different environments: thermal decomposition (pyrolysis), partial oxidation (O₂) and O₂/CO₂ gasification in a plug flow reactor to analyze the combustion component. The computed results have similar trend for three different environments with the experimental data. A systematically reduced mechanism for O₂/CO₂ gasification has also been derived by examination of Rate of Production (ROP) analysis from the detailed mechanism (255 species and 1095 reactions). The reduced mechanism shows similar result and has been validated by comparing the calculated concentrations of H₂, CH₄, H₂O, CO, CO₂ and polycyclic aromatic hydrocarbon (PAH) with those of the detailed mechanism in a wide range of operating conditions. The authors also predicted the concentration profiles of H₂, CO, CO₂ and PAH at high temperature and high pressure.     

Review of proton conductors for hydrogen separation

There is a global push to develop a range of hydrogen technologies for timely adoption of the hydrogen economy. This is critical in view of the depleting oil reserves and looming transport fuel shortage, global warming, and increasing pollution. Molecular hydrogen (H₂) can be generated by a number of renewable and fossil-fuel-based resources. However, given the high cost of H₂ generation by renewable energy at this stage, fossil or carbon fuels are likely to meet the short- to medium-term demand for hydrogen. In view of this, effective technologies are required for the separation of H₂ from a gas feed (by-products of coal or bio-mass gasification plants, or gases from fossil fuel partial oxidation or reforming) consisting mainly of H₂ and CO₂ with small quantities of other gases such as CH₄, CO, H₂O, and traces of sulphur compounds. Several technologies are under development for hydrogen separation. One such technology is based on ion transport membranes, which conduct protons or both protons and electrons. Although these materials have been considered for other applications, such as gas sensors, fuel cells and water electrolysis, the interest in their use as gas separation membranes has developed only recently. In this paper, various classes of proton-conducting materials have been reviewed with specific emphasis on their potential use as H₂ separation membranes in the industrial processes of coal gasification, natural gas reforming, methanol reforming and the water–gas shift (WGS) reaction. Key material requirements for their use in these applications have been discussed.     

Multi-species laser absorption sensors for in situ monitoring of syngas composition

Tunable diode laser absorption spectroscopy sensors for detection of CO, CO₂, CH₄ and H₂O at elevated pressures in mixtures of synthesis gas (syngas: products of coal and/or biomass gasification) were developed and tested. Wavelength modulation spectroscopy (WMS) with 1f-normalized 2f detection was employed. Fiber-coupled DFB diode lasers operating at 2325, 2017, 2290 and 1352 nm were used for simultaneously measuring CO, CO₂, CH₄ and H₂O, respectively. Criteria for the selection of transitions were developed, and transitions were selected to optimize the signal and minimize interference from other species. For quantitative WMS measurements, the collision-broadening coefficients of the selected transitions were determined for collisions with possible syngas components, namely CO, CO₂, CH₄, H₂O, N₂ and H₂. Sample measurements were performed for each species in gas cells at a temperature of 25 °C up to pressures of 20 atm. To validate the sensor performance, the composition of synthetic syngas was determined by the absorption sensor and compared with the known values. A method of estimating the lower heating value and Wobbe index of the syngas mixture from these measurements was also demonstrated.     

Two-stage thermochemical conversion of solid fuel in a setup with steam ejection

The paper presents a set of tests with a setup using steam supply into ejector instead of compressed air. Experi-ments measured the gas analysis data — volumetric concentrations O₂, CO, CO₂, C _n H _m , NO _x , H₂ at different propor-tions of air and steam. The data are compared with calculations for thermodynamic equilibrium compositions for the reacting mixture С+Н₂О+air performed by “Terra” computer code including the case of air excess (α ≤ 1). The cal-culations were also compared with available data on gasification output at a high content of ballasting gas. It was demonstrated that in these operation modes, the steam was an inert dilution agent, which did not exclude the outcome of coal gas production with high Н₂/СО and СО/СО₂ ratios corresponding to different modes of gasification.     

生物油及生物质炭电催化制氢

报道了以生物质热裂解产物-生物油和生物质炭为原料,利用双固定床反应器和电催化水蒸气重整方法高效制氢过程研究．获得的最大绝对氢产率达到110.9 g H₂/1 kg干生物质,气相产物包括72%H₂、26%CO₂、1.9%CO和痕量的CH₄．研究了添加生物质炭对生物油制氢效果的影响,以及重整反应温度、通入催化床的电流等反应条件对生物油和生物质炭制氢效果的影响．结果表明,生物质炭的添加使绝对氢产率增加了大约20%～45%,提     

Sequential hydrothermal gasification of biomass to hydrogen

A new technology, in which a renewable biomass is used to produce hydrogen fuel, is described. This hydrogen can be used as a feed for fuel cells to generate electricity or in other energy-producing processes. Degradation and gasification of cellulose-based biomass in compressed water was studied in the 100–400 °C temperature range. Phase behavior of the cellulose in subcritical water was studied in a diamond-anvil cell, coupled with optical microscopy, at heating rates of 1 and 5 °C/s. Homogeneous conditions of a single water-cellulose phase were established. Complete dissolution of the cellulose was achieved at 333 °C. The evolution mechanism based on a rapid hydrolysis of the cellulose to oligomers and glucose is suggested. Glucose was then used as a model compound to characterize the chemistry of biomass gasification. A 0.1-M glucose solution was fed into a continuous-flow reactor at a pressure of 100 bar using an HPLC pump. Catalytic effects of Pt/Al₂O₃ on the gasification temperature were determined. Gas product composition was analyzed using online GC-TCD. A mixture of H₂, CO₂, and CH₄ gas was produced. Quantitative analysis of the total organic carbon in the liquid residue indicated 67% carbon gasification efficiency at 330 °C. Qualitative analyses of liquid residues showed that the main decomposition products in the liquid phase were alcohols and carboxylic acids. It was shown that the hydrogen fuel could be efficiently generated from biomass.     

Effect of pyrolysis conditions on the char gasification with mixtures of CO2 and H2O

Two kinds of char were prepared from a lignite by fast pyrolysis using a drop tube furnace and by slow pyrolysis using a fixed-bed furnace at the temperature of 1273 K. Scanning electron microscopy, X-ray diffractometry and the BET method were employed to characterize char properties. The chars were gasified with CO₂, H₂O and their mixtures in a thermogravimetric analyzer (TGA) system to investigate gasification kinetics and derive the rate expression. To validate the gasification rate equation derived from TGA, a fluidized-bed gasification experiment was also carried out. The results showed that both fast-char and slow-char were mainly composed of dense char. The shrinking core model was applicable to predict both gasification of fast-char and slow-char. It was found that the char gasification rate in the mixtures of CO₂ and H₂O was obviously lower than the sum of the two rates of the char independently reacting with CO₂ and H₂O but higher than the rate of each independent reaction, for both the fast-char gasification and slow-char gasification. Both of the results from the TGA and the fluidized-bed reactor showed that char-H₂O reaction was independent on char-CO₂ reaction, while char-CO₂ reaction was inhibited by char-H₂O reaction.     

Flame structure studies of rich ethylene-oxygen-argon mixtures doped with CO2, or with NH3, or with H2O

Structures of several premixed ethylene-oxygen-argon rich flat flames burning at 50 mbar have been established by using molecular beam mass spectrometry in order to investigate the effect of CO₂, or NH₃, or H₂O addition on species concentration profiles. The aim of this study is to examine the eventual changes of profiles of detected hydrocarbon intermediates which could be considered as soot precursors (C₂H₂, C₄H₂, C₅H₄, C₅H₆, C₆H₂, C₆H₄, C₆H₆, C₇H₈, C₆H₆O, C₈H₆, C₈H₈, C₉H₈ and C₁₀H₈). The comparative study has been achieved on four flames with an equivalence ratio (f) of 2.50: one without any additive (F2.50), one with 15% of CO₂ replacing the same quantity of argon (F2.50C), one with 3.3% of NH₃ in partial replacement of argon (F2.50N) and one with 13% of H₂O in replacement of the same quantity of argon (F2.50H). The four flat flames have similar final flame temperatures (1800 K).CO₂, or NH₃, or H₂O addition to the fresh gas inlet causes a shift downstream of the flame front and thus flame inhibition. Endothermic processes CO₂ + H = CO + OH and H₂O + H = H₂ + OH are responsible of the reduction of the hydrocarbon intermediates in the CO₂ and H₂O added flames through the supplementary formation of hydroxyl radicals. It has been demonstrated that such processes begin to play at the end of the flame front and becomes more efficient in the burnt gases region.The replacement of some Ar by NH₃ is responsible only for a slight decrease of the maximum mole fraction of C₂H₂, but NH₃ becomes much more efficient for C₄H₂ and C₅ to C₁₀ species. Moreover, the efficiency of NH₃ as a reducing agent of C₅ to C₁₀ intermediates is larger than that of CO₂ and H₂O for equal quantities added.     

Density-dependent magnetic shielding in gas phase 13C N.M.R.

Density-dependent ¹³C nuclear magnetic shielding has been found for each of the pure gases CH₄, C₂H₆, C₂H₄, CO and CO₂, and for several binary mixtures of gases. For methane gas the density dependence is greater at higher temperatures in contrast to expectation and the observed temperature dependence of the shielding at zero density is attributable to nuclear motion. ¹³C magnetic shielding is considerably higher in the gas phase than in the liquid phase and the difference varies for chemically non-equivalent ¹³C nuclei by amounts which are well above the level of experimental error.     

A Raman system for multi-gas-species analysis in power transformer

We have built a complete Raman detection system for multi-trace-gas diagnosis, which is suitable for analyzing the dissolved gases in electric power system. In the system, a high-sensitivity CCD device connected to a spectrometer is used as the detection unit of the Raman system. A near-confocal cavity is used for improving the detection sensitivity of the system. In the effective spectral range of about 570–710 nm, Raman spectra of eight typical gases are achieved by using this Raman system. The detection limits for different gases have been obtained: 126 ppm for CO₂, 21 ppm for CH₄, 63 ppm for C₂H₄, 42 ppm for C₂H₂, 96.6 ppm for H₂. The detectability of the system satisfies the requirements of gas diagnosis in power transformer.     

Isomers of OCS and their reaction with H2O on singlet potential energy surface

The isomers of the carbonyl sulfide (OCS) molecule are investigated in detail at CCSD(T)/cc-pVTZ//MP2/6-311++G(2d,2p) level of theory. One cyclic isomer was identified along with three different linear minima of the OCS molecule. Three interconversion transition states were also located between cyclic and linear forms of OCS. Among these four isomers, the singlet potential energy surface (PES) for the molecule–molecule reaction between the three most energetically favoured isomers of OCS and H₂O has been explored theoretically at the CCSD(T)/cc-pVTZ//MP2/6-311++G(2d,2p) level. This singlet PES comprises of three paths. Path 1 is the reaction of linear OCS molecule with water producing the major product P1 (CO₂?+?H₂S), minor product P2 (S?+?HCOOH) and two isomers via 14 minima and 15 transition states. The Path 2 is an isomerization process in which cyclic isomer of OCS reacts with water molecule via another initial barrierless aduct producing five isomers of the OCS–H₂O system through five interconversion transition states. The reaction of linear COS isomer with water is shown in Path 3. This path produces the radicals SH and COOH from another COS–H₂O complex via a transition state. Among these three products, the product P1 is energetically most favoured. The overall exothermicity of the product channels for the formation of major product P1 on PES is calculated to be about 10.60?kcal/mol possessing initial high entrance barriers of 45.48 and 55.47?kcal/mol in two possible pathways. As the process is favoured thermodynamically but not kinetically, the reaction is expected to be very slow.     

Effect of CO2 gasification reaction on oxy-combustion of pulverized coal char

For oxy-combustion with flue gas recirculation, as is commonly employed, it is recognized that elevated CO₂ levels affect radiant transport, the heat capacity of the gas, and other gas transport properties. A topic of widespread speculation has concerned the effect of the CO₂ gasification reaction with coal char on the char burning rate. To give clarity to the likely impact of this reaction on the oxy-fuel combustion of pulverized coal char, the Surface Kinetics in Porous Particles (SKIPPY) code was employed for a range of potential CO₂ reaction rates for a high-volatile bituminous coal char particle (130 μm diameter) reacting in several O₂ concentration environments. The effects of boundary layer chemistry are also examined in this analysis. Under oxygen-enriched conditions, boundary layer reactions (converting CO to CO₂, with concomitant heat release) are shown to increase the char particle temperature and burning rate, while decreasing the O₂ concentration at the particle surface. The CO₂ gasification reaction acts to reduce the char particle temperature (because of the reaction endothermicity) and thereby reduces the rate of char oxidation. Interestingly, the presence of the CO₂ gasification reaction increases the char conversion rate for combustion at low O₂ concentrations, but decreases char conversion for combustion at high O₂ concentrations. These calculations give new insight into the complexity of the effects from the CO₂ gasification reaction and should help improve the understanding of experimentally measured oxy-fuel char combustion and burnout trends in the literature.     

An analysis of the transient combustion and burnout time of carbon particles

The various coupled and transient processes controlling the gasification mechanism and burnout time of carbon particles were analyzed, with emphasis on the influence of the initial particle size for the size range that is relevant to the firing of pulverized solid fuels. The formulation recognizes the suppression of the envelop gas-phase CO flame because of the small particle size, and allows for the three surface reactions of C + O₂, C + CO₂, and C + H₂O, as well as radiation heat transfer because of the potential high temperature attainable by the carbon particle. Results show that while the particle temperature continuously increases during the combustion of sufficiently large particles, the gasification actually consists of three phases: namely an initial particle heating period, an activation period for the surface reactions, and a diffusion-controlled, d²-law gasification period characterized by perpetually maximized surface reaction rates in spite of the continuously decreasing particle size. Radiation heat transfer is shown to have the same magnitude as those of reaction heat release and conduction, and actively affects the particle gasification response. For smaller particles, activation of the surface reactions is either substantially delayed subsequent to the initial heating period, or is completely suppressed, which respectively leads to either long burnout times or incomplete particle gasification. Influences due to the ambient oxygen concentration and the presence of CO₂ and H₂O as the oxidizer were also studied. Comparisons with literature experimental data show adequate agreement.     

CO2 laser CVD of a-Si:H: in situ gas analysis and model calculations

4 and disilane Si₂H₆ induced by continuous wave CO₂ laser irradiation has been investigated under the conditions of chemical vapor deposition (CVD) of amorphous hydrogenated silicon a-Si:H. At the very position of depositing the thin film the stationary chemical composition of the processing gas is probed in situ by an effusive molecular beam which passes through a differential pumping stage into a quadrupole mass spectrometer (QMS). With SiH₄ as educt and SF₆ as a sensitizer, SiH₄ and Si₂H₆ are found in the processing gas while Si₃H₈ or higher silanes are lacking. Si₂H₆ and SF₆ lead to SiH₄, Si₂H₆, and Si₃H₈, but higher silanes are missing. The experimentally determined composition of the processing gas is semi-quantitatively reproduced by model calculations based on the assumption of stationary local equilibrium conditions and applying thermodynamic and spectroscopic data (molecular statistics). The mass balance of the processing gas entering and leaving the CVD chamber states an atomic ratio Si:H of 1:2 for the gas phase species forming the solid deposit on the reactor walls. This finding together with theoretical considerations indicates the intermediate Si₂H₄ to be the dominating gas phase species forming the a-Si:H thin films. Received: 17 July 1998/Accepted: 20 July 1998     

A study of the relative brönsted acidities of surface complexes on Ag(110)

The relative acidities of a number of Brönsted acids have been established on the Ag(110) surface under UHV conditions. For acids which react completely with adsorbed oxygen atoms on this surface to form H₂O, relative acidities were determined by means of acid-base titration reactions. Adsorbed species such as carboxylates, alkoxides, etc., were formed by reaction of the parent acids with O(a) and then displaced from the surface by titration with stronger acids. Relative acidities of the acids which did not react to completion with O(a) were established on the basis of their relative extents of reaction. The relative acidity scale on Ag(110), according to the reaction BH(g) + B'(a) B'H(g) + B(a) was found to be HCOOH ≈ CH₃COOH>C₂H₅OH> C₂H₂>CH₃OH>C₃H₆, H₂O>C₂H₄, C₂H₆, H₂. This order is in excellent agreement with the acidity scale for these species in the gas phase according to BH(g)B^?(g) + H⁺ (g); it cannot be explained by aqueous dissociation constants or homolytic bond dissociation energies. This result is in accord with the appreciable anionic character of the adsorbed species, since the electron affinity of the base, B, is a strong thermodynamic factor in the acidity in the gas phase. Both XPS and UPS results for adsorbed species on the Ag(110) surface are consistent with this interpretation.     

TDLAS-based sensors for in situ measurement of syngas composition in a pressurized,oxygen-blown,entrained flow coal gasifier

Tunable diode laser absorption spectroscopy based in situ sensors for CO (2.33 μm), CO₂ (2.02 μm), CH₄ (2.29 μm) and H₂O (1.35 μm) were deployed in a pilot-scale (1 ton/day), high-pressure (up to 18 atm), entrained flow, oxygen-blown, slagging coal gasifier at the University of Utah. Measurements of species mole fraction with 3-s time resolution were taken at the pre- and post-filtration stages of the gasifier synthesis gas (called here syngas) output flow. Although particulate scattering makes pre-filter measurements more difficult, this location avoids the time delay of flow through the filtration devices. With the measured species and known N₂ concentrations, the H₂ content was obtained via balance. The lower heating value and the Wobbe index of the gas mixture were estimated using the measured gas composition. The sensors demonstrated here show promise for monitoring and control of the gasification process.     

Adsorption and diffusion behaviors of H2, H2S,NH3, CO and H2O gases molecules on MoO3 monolayer: A DFT study

Molybdenum trioxide (MoO₃) with α-phase is a promising material for gas sensing because of its high sensitivity, fast response and thermodynamic stability. To probe the mechanism of superior gas detection ability of MoO₃ monolayer, the adsorption and diffusion of H₂, H₂S, NH₃, CO and H₂O molecules on two-dimensional (2D) MoO₃ layer are studied via density functional theory (DFT) calculations. Based on calculated adsorption energies, density of states, charge transfer, diffusion barriers and diffusion coefficient, MoO₃ shows a superior sensitive and fast response to H₂ and H₂S than CO, NH₃, H₂O, which is consistent with experimental conclusions. Moreover, the response of MoO₃ to H₂S and H₂ will be obviously enhanced at high gas concentration, and the incorporation of H₂ and H₂S results in an obvious increasing in DOS near Fermi level. Our analysis provides a conceptual foundation for future design of MoO₃-based gas sensing materials.     

Virial coefficients of the equation of state of a gas of nonspherical molecules: I. Nonpolar molecules

The second and third virial coefficient of a gas of nonspherical molecules of arbitrary symmetry have been calculated for a set of force parameters which has been found suitable to explain the dilute gas viscosity data. The influence of a large number of orientation dependent pair- and three-body nonadditive interactions has been taken into account. The relative contribution of each branch of pair and triplet interactions has been evaluated as a function of temperature. The theoretical results have been compared with the experimental data of N₂, CO, CO₂, CS₂, C₂H₄ and C₆H₆. The agreement between theory and experiment is very satisfactory for all the systems.     

Coordination and solvation of noble metal ions: Infrared spectroscopy of Ag+(H2O)n

Vibrational spectra of mass-selected Ag⁺(H₂O)_n ions are measured by infrared photodissociation spectroscopy and analyzed with the aid of density functional theory calculations. Hydrogen bonding between H₂O molecules is found to be absent for cold Ag⁺(H₂O)₃, but detected for Ag⁺(H₂O)₄ through characteristic changes in the position and intensity of OH-stretching transitions. The third H₂O coordinates directly to Ag⁺, but the fourth H₂O prefers solvation through hydrogen bonding. The preference of the tri-coordinated form is attributed to the inefficient 5s–4d hybridization in Ag⁺, in contrast to the efficient 4s–3d hybridization in Cu⁺. For Ag⁺(H₂O)₄, however, di-coordinated isomers are identified in addition to the tri-coordinated one.