Kinetic studies of char gasification by steam and CO2 in the presence of H2 and CO

Char-CO₂ gasification reactions in the presence of CO and char-steam gasification reactions in the presence of H₂ were studied at the atmospheric condition using a thermogravimetric apparatus (TGA) at various reactant partial pressures and within a temperature range of 1123 K-1223 K. The char was prepared from a lignite coal. The partial pressure of H₂ and CO varied from 0.05 to 0.3 atm. The experimental results showed that Langmuir-Hinshelwood (L-H) kinetic equation was applicable to describe the inhibition effects of CO and H₂. The kinetic parameters in L-H equations were obtained. Interactions of char gasification by steam and CO₂ in the presence of H₂ and CO were discussed. It was found that the kinetic parameters determined from pure or binary gas mixtures can be used to predict multi-component gasification rates. The results confirmed that the char-steam and char-CO₂ reactions proceed on separate active sites rather than common active sites.     

Photocatalytic reactions of imazamox at TiO2, H2O2 and TiO2/H2O2 in water interfaces: Kinetic and photoproducts study

The photocatalytic transformation of imazamox, a herbicide of imidazolinone family, is investigated in aqueous solution containing titanium dioxide, hydrogen peroxide or the combination of TiO₂/H₂O₂ under simulated sunlight irradiation. The effect of parameters such as the amount of catalysts, the concentration of herbicide, and the pH were investigated by measurement of the rate constant of degradation. Experimental data obtained under different conditions describe the dependency of degradation rate on the above mentioned parameters. Consequently, kinetic parameters were experimentally determined and a pseudo-first-order kinetic was observed. Mulliken charge distributions calculated by the DFT method B3LYP/6–31+G(d) level of theory for key cationic, anionic and neutral structures of imazamox give interpretation for the dependency of photodegradation rate constant on pH. The degradation rate constants were always higher for the heterogeneous catalysis in reactions (TiO₂/UV, TiO₂/UV/H₂O₂) compared to the homogeneous systems (UV alone, H₂O₂/UV). In parallel, five photoproducts could be tentatively identified using Electrospray ionization Fourier transform ion cyclotron resonance mass spectroscopy based on precise chemical formula assignments.     

Modeling char conversion under suspension fired conditions in O2/N2 and O2/CO2 atmospheres

The aim of this investigation has been to model combustion under suspension fired conditions in O₂/N₂ and O₂/CO₂ mixtures. Experiments used for model validation have been carried out in an electrically heated Entrained Flow Reactor (EFR) at temperatures between 1173 K and 1673 K with inlet O₂ concentrations between 5 and 28 vol.%. The COal COmbustion MOdel, COCOMO, includes the three char morphologies: cenospheric char, network char and dense char each divided between six discrete particle sizes. Both combustion and gasification with CO₂ are accounted for and reaction rates include thermal char deactivation, which was found to be important for combustion at high reactor temperatures and high O₂ concentrations. COCOMO show in general good agreement with experimental char conversion profiles at conditions covering zone I-III. From the experimental profiles no effect of CO₂ gasification on char conversion has been found. COCOMO does however suggest that CO₂ gasification in oxy-fuel combustion at low O₂ concentrations can account for as much as 70% of the overall char consumption rate during combustion in zone III.     

Coal devolatilization and char conversion under suspension fired conditions in O2/N2 and O2/CO2 atmospheres

The aim of the present investigation is to examine differences between O₂/N₂ and O₂/CO₂ atmospheres during devolatilization and char conversion of a bituminous coal at conditions covering temperatures between 1173 K and 1673 K and inlet oxygen concentrations between 5 and 28 vol.%. The experiments have been carried out in an electrically heated entrained flow reactor that is designed to simulate the conditions in a suspension fired boiler. Coal devolatilized in N₂ and CO₂ atmospheres provided similar results regarding char morphology, char N₂-BET surface area and volatile yield. This strongly indicates that a shift from air to oxy-fuel combustion does not influence the devolatilization process significantly. Char combustion experiments yielded similar char conversion profiles when N₂ was replaced with CO₂ under conditions where combustion was primarily controlled by chemical kinetics. When char was burned at 1573 K and 1673 K a faster conversion was found in N₂ suggesting that the lower molecular diffusion coefficient of O₂ in CO₂ lowers the char conversion rate when external mass transfer influences combustion. The reaction of char with CO₂ was not observed to have an influence on char conversion rates at the applied experimental conditions.     

Phenol cogeneration with electricity by using in situ generated H2O2 in a H2–O2 PEMFC reactor

In the present work, direct hydroxylation of benzene to phenol by using in situ generated H₂O₂ with electricity cogeneration was carried out in a proton exchange membrane fuel cell (PEMFC) reactor. Phenol was produced only when there was current through the external circuit. No other organic products were detected during this electrochemical process. A rotating ring-disc electrode (RRDE) technique was used to quantitatively detect the intermediate H₂O₂ in an acid electrolyte solution at different potentials and temperatures. The RRDE studies showed that the in situ generated H₂O₂ may play a crucial role during the formation of phenol. The formation rate of phenol could be controlled by adjusting the current or cell potential.     

Oxidative leaching kinetics of molybdenum-uranium ore in H2SO4 using H2O2 as an oxidizing agent

The processing of molybdenum-uranium ore in a sulfuric acid solution using hydrogen peroxide as an oxidant has been investigated. The leaching temperature, hydrogen peroxide concentration, sulfuric acid concentration, leaching time, particle size, liquid-to-solid ratio and agitation speed all have significant effects on the process. The optimum process operating parameters were: temperature: 95°C; H₂O₂ concentration: 0.5 M; sulfuric acid concentration: 2.5 M; time: 2 h; particle size: 74 μm, liquid-to-solid ratio: 14 ∶ 1 and agitation speed: 600 rpm. Under these experimental conditions, the extraction efficiency of molybdenum was about 98.4%, and the uranium extraction efficiency was about 98.7%. The leaching kinetics of molybdenum showed that the reaction rate of the leaching process is controlled by the chemical reaction at the particle surface. The leaching process follows the kinetic model 1 ? (1?X)^1/3 = kt with an apparent activation energy of 40.40 kJ/mole. The temperature, concentrations of H₂O₂ and H₂SO₄ and the mesh size are the main factors that influence the leaching rate. The reaction order in H₂SO₄ was 1.0012 and in H₂O₂ it was 1.2544.     

Catalytic pyrolysis of naphtha on the KVO3-based catalyst

The catalytic pyrolysis of naphtha has been performed in a quartz reactor to produce the light olefins at high yields. The catalytic pyrolysis leads to 10 and 5% higher values in the yields of ethylene and propylene, respectively, compared to the thermal pyrolysis at the same operation condition. The enhancement of olefin yield in the presence of catalyst comes from the better heat transfer through the catalyst particles. KVO₃ plays role of a catalyst to accelerate the gasification of coke deposited on the catalyst surface and its optimum range is found to be more than 10 wt.%. An addition of B₂O₃ into KVO₃-based catalyst causes a strong interaction between metal oxide (KVO₃) and -Al₂O₃ support, which decreases the loss by an evaporation of active phase.     

Kinetics of tire derived fuel (TDF) char oxidation and accompanying changes in surface area

The oxidation behavior of tire-derived fuel (TDF) char has recently been studied by several groups. In the present study, TDF char oxidation has been examined between 670 and 825 K, at oxygen partial pressures ranging from 2 to 19.8 kPa. The order of reaction with respect to oxygen varied with burnoff, and was in the range 0.72-0.86. The activation energy of reaction ranged with burnoff from 138 to 150 kJ/mol. The reaction rate does not correlate well with BET surface area, but did correlate well with the surface area in pores ranging in size from 1.2 to roughly 7 nm in width. Pores smaller than 1.2 nm exist in the char, but appear not to be used or developed by the oxidation reaction. Results for chars that have been acid washed to remove some inorganic matter show lowered reactivity, and a distinctly different pattern of pore development with burnoff. This is, in turn, reflected in a very different pattern of reactivity change with burnoff for such materials.     

Direct formation of H2O2 from H2 and O2 and decomposition/hydrogenation of H2O2 in aqueous acidic reaction medium over halide-containing Pd/SiO2 catalytic system

Formation of H₂O₂ from H₂ and O₂ and decomposition/hydrogenation of H₂O₂ have been studied in aqueous acidic medium over Pd/SiO₂ catalyst in presence of different halide ions (viz. F⁻, Cl⁻ and Br⁻). The halide ions were introduced in the catalytic system via incorporating them in the catalyst or by adding into the reaction medium. The nature of the halide ions present in the catalytic system showed profound influence on the H₂O₂ formation selectivity in the H₂ to H₂O₂ oxidation over the catalyst. The H₂O₂ destruction via catalytic decomposition and by hydrogenation (in presence of hydrogen) was also found to be strongly dependent upon the nature of the halide ions present in the catalytic system. Among the different halides, Br⁻ was found to selectivity promote the conversion of H₂ to H₂O₂ by significantly reducing the H₂O₂ decomposition and hydrogenation over the catalyst. The other halides, on the other hand, showed a negative influence on the H₂O₂ formation by promoting the H₂ combustion to water and/or by increasing the rate of decomposition/hydrogenation of H₂O₂ over the catalyst. An optimum concentration of Br⁻ ions in the reaction medium or in the catalyst was found to be crucial for obtaining the higher H₂O₂ yield in the direct synthesis.     

Char gasification in mixtures of CO2 and H2O: Competition and inhibition

Our understanding of char gasification reaction kinetics at high pressures is generally limited to analyses of data generated using pure reactants, or reactants diluted with inert gases. This paper presents data generated for the reaction of coal chars with mixtures of CO₂ and H₂O at high pressures, to determine how existing pure-gas rate data can be applied to more realistic gasification systems. The data presented here show that the rate of reaction in a mixture of CO₂ and H₂O is not the sum of the two pure-gas reaction rates; rather, it is a complex combination of the two that appears to be dependant on the blocking of reaction sites by the relatively slow C–CO₂ reaction. Analysis of the results using a Langmuir–Hinshelwood (LH) style of rate equation with the assumption that both reactions compete for the same active surface, produces a model that explains the experimental data. This model allows reaction rates in mixtures of CO₂ and H₂O to be estimated based on existing, measured pure-gas reactivity data or from ‘first principles’ using knowledge of the rate constants for the LH equation.     

Deep desulfurization of fuels catalyzed by surfactant-type decatungstates using H2O2 as oxidant

Oxidation of dibenzothiphene (DBT) in model oil with H₂O₂ using surfactant-type decatungstates Q₄W₁₀O₃₂ (Q = (CH₃)₃NC₁₆H₃₃, (CH₃)₃NC₁₄H₂₉, (CH₃)₃NC₁₂H₂₅ and (CH₃)₃NC₁₀H₂₁) as catalysts was studied. The surfactant-type decatungstates were synthesized and characterized. The suitable reaction condition of deep desulfurization was suggested: n(DBT):n(catalyst):n(H₂O₂) = 1:0.01:3, 60 °C for 0.5 h, under which the DBT conversion can reach 99.6% with [(CH₃)₃NC₁₆H₃₃]₄W₁₀O₃₂ as catalyst. The length of carbon chains of quaternary ammonium cations played a vital role in the catalytic activity of surfactant-type decatungstates, that is, the longer the carbon chain of quaternary ammonium cation of a catalyst was, the better the activity of this catalyst showed. [(CH₃)₃NC₁₆H₃₃]₄W₁₀O₃₂ exhibited the best catalytic performance and can be recycled for six times without significant decrease in catalytic activity. Using benzothiphene (BT) and 4,6-dimethyldibenzothiphene (4,6-DMDBT) as substrates in model oil, surfactant-type decatungstates also showed high catalytic activity. During desulfurization process, BT conversion can reach 99.6% at 3.25 h, while 99.4% of 4,6-DMDBT conversion reached at 1.25 h, with the temperature of 60 °C under atmospheric pressure. The sulfone can be separated from the oil using N,N-dimethylformamide (DMF) as an extractant, and the sulfur content can be lowered from 1000 to 4 ppm. For real diesel, the sulfur removal can reach 93.5% after five times extraction.     

Evolution of biomass char structure during oxidation in O2 as revealed with FT-Raman spectroscopy

FT-Raman spectroscopy has been used to identify structural features and evaluate the structural evolution of biomass chars during gasification with air. Chars prepared from the pyrolysis of a cane trash sample with a fast particle heating rate in a novel fluidised-bed/fixed-bed reactor at 500, 700 and 900 °C were oxidised at 400 °C in air in a TGA. The data derived from the spectral deconvolution of Fourier Transform — Raman spectra suggest that the 500 °C char showed very different structural features after pyrolysis and during oxidation from the 700 and 900 °C chars, while the differences between the latter two chars were small. Preferential consumption by O₂ of smaller aromatic rings and structures of somewhat aliphatic characteristics left the char more enriched with larger aromatic ring systems. The changes in char structure are in agreement with the observed reactivity measured in O₂ in a thermogravimetric analyser.     

Investigation into the removal of sulfur from tire derived fuel by pyrolysis

There is growing interest in the use of scrap tires as both a fuel and a feed material for petroleum feedstocks due to their abundance and their chemical composition. However, the sulfur content of scrap tires is a potential obstacle to scrap tires utilization as a fuel. In this paper, the partitioning of sulfur was investigated from the two major pyrolytic products from passenger car tires, liquid oils and solid chars, and the potential of producing a low sulfur char for fuel applications. The removal of sulfur during tire pyrolysis offers the greatest potential for the separation of sulfur products from the evolved gases and vapors. The influences of heating rate and pyrolysis temperature were investigated from 325 to 1000 °C, a range where substantial devolatilization occurs. The pyrolysis char and derived oil were analyzed for sulfur, and compared to the original parent sulfur content in tire derived fuel (TDF) samples. The results of sulfur determination verify that the overall desulfurization from the pyrolysis reaction is essentially unaffected by the heating rate but is affected by the ultimate pyrolysis temperature.     

Modeling of H2O2 formation in PEMFCs

A model for H₂O₂ formation, transport, and reaction in PEMFCs is established for the first time. Profiles of oxygen and H₂O₂ concentration inside the fuel cell are simulated using the agglomerate model for the electrode. The predicted concentration of H₂O₂ shows the same trend as experimental data under different conditions, but the level was only of the same magnitude. Low humidity, high temperature, and high oxygen/hydrogen partial pressures were found to increase the concentration of H₂O₂. An increase in membrane thickness or metal ion contaminant level reduces the concentration of H₂O₂ in the membrane. Lowering the oxygen permeability in the ionomer is the most important and effective method to reduce the formation of H₂O₂. The simulation results also show little change in H₂O₂ concentration while operating the fuel cell above 0.6 V. Anodes designed with considerable thickness, high catalyst loadings and active areas can also help to suppress H₂O₂ formation. Finally, recommendations are made to mitigate the effects of H₂O₂ and prolong membrane lifetimes.     

Steam gasification reactivity of char from rapid pyrolysis of bio-oil/char slurry

A slurry of bio-oil and char originating from wood pyrolysis is a promising gasifier feed-stock because of its high energy density. When such a slurry is injected into a high temperature gasifier it undergoes a rapid pyrolysis yielding a char which then reacts with steam. The char produced by pyrolysis of an 80 wt% bio-oil/20 wt% char mixture at heating rates of 100-10,000 °C/s was subjected to steam gasification in a thermogravimetric analyzer. The original wood char from the bio-oil production was also tested. Gasification was conducted with 10-50 mol% steam at temperatures from 800 to 1200 °C. Reactivity of the slurry chars increased with pyrolysis heating rate, but was lower than that of the original chars. Kinetic parameters were established for a power-law rate model of the steam-char reaction, and compared to values from the literature. At temperatures over 1000 °C, the gasification rates appeared to be affected by diffusional resistance.     

Changes in char reactivity and structure during the gasification of a Victorian brown coal: Comparison between gasification in O2 and CO2

Char reactivity is an important factor influencing the efficiency of a gasification process. As a low-rank fuel, Victorian brown coal with high gasification reactivity is especially suitable for use with gasification-based technologies. In this study, a Victorian brown coal was gasified at 800 °C in a fluidised-bed/fixed-bed reactor. Two different gasifying agents were used, which were 4000 ppm O₂ balanced with argon and pure CO₂. The chars produced at different gasification conversion levels were further analysed with a thermogravimetric analyser (TGA) at 400 °C in air for their reactivities. The structural features of these chars were also characterised with FT-Raman/IR spectroscopy. The contents of alkali and alkaline earth metallic species in these chars were quantified. The reactivities of the chars prepared from the gasification in pure CO₂ at 800 °C were of a much higher magnitude than those obtained for the chars prepared from the gasification in 4000 ppm O₂ also at 800 °C. Even though both atmospheres (i.e. 4000 ppm O₂ and pure CO₂) are oxidising conditions, the results indicate that the reaction mechanisms for the gasification of brown coal char at 800 °C in these two gasifying atmospheres are different. FT-Raman/IR results showed that the char structure has been changed drastically during the gasification process.     

Water delignification by advanced oxidation processes: Homogeneous and heterogeneous Fenton and H2O2 photo-assisted reactions

The oxidation of lignin in synthetic aqueous solutions as well as in the biologically treated pulp-and-paper mill wastewater with hydrogen peroxide was studied in various methods: hydrogen peroxide UV-photolysis, homogeneous, heterogeneous and UV-assisted heterogeneous Fenton reactions, catalysed by FeZSM-5 zeolite. Contrasting the low-molecular organic contaminants, the oxidation of lignin in aqueous solutions was drastically slowed down in presence of heterogeneous FeZSM-5 zeolite, showing the superior performance of acidic homogeneous Fenton and hydrogen peroxide photolysis. This is explained by steric hindrance in oxidation of lignin with OH radicals on the catalyst surface and possible deactivation of lignin molecules adsorbed on the zeolite. The hydrogen peroxide photolysis among the studied delignification methods appeared to be the most efficient one in a wide range of pH.     

Kinetic modeling of H2O2-enhanced oxidation of flue gas elemental mercury

Mercury emissions from coal-fired power plants account for 40% of the anthropogenic mercury emissions in the U.S. The speciation of mercury largely determines the amount of mercury capture in control equipments. Conversion of insoluble Hg⁰ into more soluble Hg²⁺ facilitates its removal in scrubbers. Past studies suggest that an added supply of OH radicals possibly enhance the mercury oxidation process. This study demonstrates that the application of H₂O₂, as source of OH radicals, accelerates the oxidation of Hg⁰ into Hg²⁺. A detailed kinetic reaction mechanism was compiled and the reaction pathways were established to analyze the effect of H₂O₂ addition. The optimum temperature range for the oxidation was 480–490 °C. The sensitivity analysis of the reaction mechanism indicates that the supply OH radicals increase the formation of atomic Cl, which accelerates the formation of HgCl₂ enhancing the oxidation process. Also, the pathway through HOCl radical, generated by the interactions between chlorine and H₂O₂ was prominent in the oxidation of Hg⁰. The flue gas NO was found to be inhibiting the Hg⁰ oxidation, since it competed for the supplied H₂O₂. Studying the interactions with the other flue gas components and the surface chemistry with particles in the flue gas could be important and may improve the insight into the post combustion transformation of mercury in a comprehensive way.     

Removal of SO2 by activated carbon fibers in the presence of O2 and H2O

This work describes the potential capability of activated carbon fibers (ACFs) in continuously removing SO₂ from inert atmosphere without requiring further regeneration. A tubular reactor packed with ACF was used to study the conversion of SO₂ into H₂SO₄ in the presence of O₂ and H₂O with varying concentrations of SO₂ (3000-10,000 ppm), O₂ (10-20%), and H₂O (10-70%) and temperatures (313-348 K). The experiments were carried out on two precursors (viscose rayon and phenolic resin) based ACFs. The breakthrough data revealed that the steady-state SO₂ concentration levels at the reactor exit increased with increasing inlet SO₂ concentration and decreased with increasing concentration levels of O₂ as well as H₂O. Increase in the reaction temperature was found to moderately enhance the steady-state exit concentration levels of SO₂. The viscose rayon-based ACF exhibited higher SO₂ removal activity in comparison to the phenolic resin-based ACF. A mathematical model was developed to predict the gas concentration profiles in the reactor, incorporating the mass transfer in the bed as well as within the ACF pores, along with the surface reactions on the ACF. The model predictions agreed reasonably well with the data.     

石脑油裂解装置建模与仿真技术

裂解装置提供了石化行业大部分基础原料，石脑油是目前国内外重要的裂解原料。对石脑油裂解反应过程、结焦过程和裂解炉辐射段的建模与仿真进行了综述：目前对分子动力学研究较多，用于离线仿真能够获得较好的效果，但在线应用不多；自由基动力学模型则是深入研究石脑油裂解过程本质的必然途径，在实际应用中越来越显示出其优越性。