Formation of NOx precursors during wheat straw pyrolysis and gasification with O2 and CO2

The release behavior tests of NO_x precursors from wheat straw during pyrolysis in argon and gasification in 5%O₂/95%Ar and 5%CO₂/95%Ar were performed using a thermogravimetric analyzer (TGA) coupled with a Fourier transform infrared (FTIR) spectrometer. The results show that heating rate and particle size have substantial effects on the selectivity of N-conversion due to the selectivity of cracking of cyclic amides and the secondary reaction influencing the formation of NH₃, HCN and HNCO. The atmosphere influences the N-selectivity to HCN, NH₃, NO and HNCO. The formation of HCN and NH₃ in 5%O₂/95%Ar is a result of competition among the opposing effects of O₂. The presence of O₂ promotes the yields of HCN and HNCO evidently, and HNCO seems to be a favourable product from biomass-N compared in Ar atmosphere although HCN yield is a little bigger than that of HNCO. The use of CO₂ reduces the formation of HCN, the yield of NH₃ keeps essentially constant compared in Ar, and the emission of HNCO is suppressed. NH₃ seems to be a favourable product from biomass-N in 5%CO₂/95%Ar.     

The effect of O2 enrichment on NOx formation in biomass co-fired pulverised coal combustion

Oxygen enrichment of the combustion air in pulverised coal combustion for power plant is seen as a possible retrofit measure to improve CO₂ scrubbing and capture. This technique produces a reduced volume of flue gas with higher CO₂ concentration than normal air combustion that will contributes to the enhancement of amine scrubbing plant efficiencies. We report in this article the results of a study at the small pilot scale into the effect of these combustion modifications on the formation of NO_x and associated carbon burnout changes. Experiments were performed using a Russian coal, typical of that used in some UK power stations with shea meal and Pakistani cotton stalk as biomass fuels co-fired at a fraction of 15%th. The down-fired pulverised coal combustor was operated at 20 kWth under air-staged conditions for NO_x control and the secondary and over-fire air flows were both enriched by up to 79% (100% O₂) for a range of splits giving a 35% overall O₂ concentration for full enrichment. When the same enrichment process was applied to biomass/coal combustion different behaviour was observed with respect to NO_x formation. We have shown that oxygen enrichment can achieve benefits of improved carbon burnout with a positive impact on NO_x emissions over and above the primary aim of increasing CO₂ concentration in the flue gas for enhanced capture efficiencies. With all other conditions of overall stoichiometry, OFA levels and O₂ enrichment levels remaining the same, NO_x levels at 22% OFA initially increased over the range of secondary air enrichment, particularly for shea meal/coal co-firing. At 31% OFA the trends were to lower NO_x at high enrichment levels. However, co-firing with shea meal initially showed an increase in NO_x emission at lower levels of enrichment (up to 40% O₂) followed by overall lower NOx emissions at 100% O₂ in the secondary air. The results show that NO_x emissions can either increase or decrease depending on the operating conditions. The differences in behaviour are attributed, not only to the effects of enrichment on the stoichiometry of the near-burner zone, but also on the flame dynamics and intensity of combustion related to the associated reductions in gas velocity and swirl intensity by the transition from air to pure O₂ in the secondary oxidant stream.     

Formation of NOx precursors during the pyrolysis of coal and biomass. Part VIII. Effects of pressure on the formation of NH3 and HCN during the pyrolysis and gasification of Victorian brown coal in steam

Effects of pressure on the formation of HCN and NH₃ during the pyrolysis and gasification of Loy Yang brown coal in steam were investigated using a pressurised drop-tube/fixed-bed reactor. The NH₃ yield increased with increasing pressure during both pyrolysis and gasification. Increasing pressure selectively favours the formation of NH₃ at the expenses of other N-containing species. The changes in the yield of NH₃ with increasing pressure were mainly observed in the feeding periods both during pyrolysis and gasification and were closely related to the formation and subsequent cracking of soot both as a result of intensified thermal cracking of volatile precursors inside the particles and as a result of volatile-char interactions after the release of volatiles. While the corresponding HCN yield during pyrolysis showed little sensitivity to changes in pressure, the HCN yield during gasification in steam showed some increases with increasing pressure. Our data indicate that the direct hydrogenation of char-N by H radicals, favoured by the presence of steam, is the main route of NH₃ formation during pyrolysis and gasification. The direct conversion, either through hydrogenation or hydrolysis, of HCN into NH₃ on char surface during the pyrolysis and gasification of brown coal is not an important route of NH₃ formation.     

Study on coal chars combustion under O2/CO2 atmosphere with fractal random pore model

When predicting the variation of pore structure during O₂/CO₂ combustion of coal chars using the random pore model (RPM), it is impossible to calculate exactly the structure parameter ψ from the pore characteristics. The values of structure parameter ψ, which were calculated based on its fractal feature at various carbon conversions, should be almost constant. However, this investigation exhibited a drastic increase of ψ at the end of combustion reaction. In this work, structure parameter ψ of the RPM was modified according to the experimental analysis and a new model, fractal random pore model (FRPM), was constructed. Compared with other models such as RPM, discrete random pore model (DRPM), the Struis model (Model I) and the Liu model (Model II), it was found that fractal random pore model was more accurate to describe coal chars combustion, especially at higher conversions. Using the FRPM, O₂/CO₂ isotherm combustion of coal chars were analyzed at different temperatures.     

Formation of NOx precursors during the pyrolysis of coal and biomass. Part VII. Pyrolysis and gasification of cane trash with steam

Biomass-nitrogen conversion during the pyrolysis and gasification of a cane trash in steam was investigated using a fluidised-bed/fixed-bed reactor and a fluidised-bed/tubular reactor. Our results indicate that the thermal cracking of volatile-N is the main route of HCN formation although the thermal cracking of char-N also contributes to the formation of HCN. There are three major routes of NH₃ formation: ‘hydrolysis’ of N-containing structures in the solid phase during the primary pyrolysis, thermal cracking and gasification of solid nascent char as well as the thermal cracking and reforming of volatile-N. Under the current experimental conditions, the hydrolysis of HCN does not appear to be an important route of NH₃/HNCO formation.     

Changes in pore structure of anthracite coal associated with CO2 sequestration process

Pore structure changing of coal during the CO₂ geo-sequestration is one of the key issues that affect the sequestration process significantly. To address this problem, the CO₂ sequestration process in an anthracite coal was replicated using a supercritical CO₂ (ScCO₂) reactor. Different coal grain sizes were exposed to ScCO₂ and water at around 40 °C and 9.8 MPa for 72 h. Helium pycnometer and mercury porosimetry provide the density, pore size distribution and porosity of the coal before and after the ScCO₂ treatment. The results show that after exposure to the ScCO₂-H₂O reaction, part of the carbonate minerals were dissolved and flushed away by water which made the true density increased as well as total pore volume and porosity most importantly in the micro-pore range. Hysteresis between mercury intrusion and extrusion was observed. Ink bottle shaped pores can be either damaged or created compared with the ScCO₂ treated coal samples. This suggests that the ScCO₂ treatment most likely increase the volumes of pores in anthracite coal, which also contributed to the increase in porosity of the treated samples. Therefore the CO₂ sequestration into coal appears to have the potential to increase significantly the anthracite microporosity which is very advantageous for CO₂ storage.     

Formation of NOx precursors during the pyrolysis of coal and biomass. Part VI. Effects of gas atmosphere on the formation of NH3 and HCN

Our results indicate that the gas atmosphere surrounding coal/char particles can greatly affect the formation of NH₃ and HCN through its influence on the availability of H radicals. Based on our results, it is believed that the chemisorption of CO₂ on the nascent char surface can consume H radicals or block the access of N-sites by H radicals for the formation of NH₃ and HCN. For the chars whose thermal cracking generates little H radicals, the gasification of char by CO₂ can also generate additional H radicals, enhancing the formation of NH₃. However, even gasification of char in CO₂ at 950 °C does not lead to the formation of HCN. The oxidation of coal with 4% O₂ at low temperatures (400-600 °C) leads to the formation of HCN as well as NH₃ due to the enhanced formation of (H) radicals. The gasification of coal with 15% H₂O drastically enhances the formation of NH₃ due to the greatly enhanced availability of H as an intermediate between the reactions of H₂O and char. These results support our reaction mechanisms proposed previously, emphasising the importance of H on the formation of NH₃ and HCN during pyrolysis, which can also be extended to the conversion of coal-N during gasification.     

Improvement of coke resistance of Ni/Al2O3 catalyst in CH4/CO2 reforming by ZrO2 addition

This work investigates the improvement of Ni/Al₂O₃ catalyst stability by ZrO₂ addition for H₂ gas production from CH₄/CO₂ reforming reactions. The initial effect of Ni addition was followed by the effect of increasing operating temperature to 500–700 °C as well as the effect of ZrO₂ loading and the promoted catalyst preparation methods by using a feed gas mixture at a CH₄:CO₂ ratio of 1:1.25. The experimental results showed that a high reaction temperature of 700 °C was favored by an endothermic dry reforming reaction. In this reaction the deactivation of Ni/Al₂O₃ was mainly due to coke deposition. This deactivation was evidently inhibited by ZrO₂, as it enhances dissociation of CO₂ forming oxygen intermediates near the contact between ZrO₂ and nickel where the deposited coke is gasified afterwards. The texture of the catalyst or BET surface area was affected by the catalyst preparation method. The change of the catalyst texture resulted from the formation of ZrO₂–Al₂O₃ composite and the plugging of Al₂O₃ pore by ZrO₂. The 15% Ni/10% ZrO₂/Al₂O₃ co-impregnated catalyst showed a higher BET surface area and catalytic activity than the sequentially impregnated catalyst whereas coke inhibition capability of the promoted catalysts prepared by either method was comparable. Further study on long-term catalyst stability should be made.     

Experimental study of ash formation during pulverized coal combustion in O2/CO2 mixtures

The present paper was addressed to mineral transformations and ash formation during O₂/CO₂ combustion of pulverized coal. Four Chinese thermal coals were burned in a drop tube furnace to generate ashes under various combustion conditions. The ash samples were characterized with XRD analysis and ⁵⁷Fe Mössbauer spectroscopy. The impacts of O₂/CO₂ combustion on mineral transformation and ash formation were explored through comparisons between O₂/CO₂ combustion and O₂/N₂ combustion. It was found that, O₂/CO₂ combustion did not significantly change the mineral phases formed in the residue ashes, but did affect the relative amounts of the mineral phases. The differences observed in the ashes formed in two atmospheres were attributed to the impact of the gas atmosphere on the combustion temperatures of coal char particles, which consequently influenced the ash formation behaviors of included minerals.     

NH3 and HCN formation during the gasification of three rank-ordered coals in steam and oxygen

A Victorian brown coal (68.5% C), a Chinese high-volatile Shenmu bituminous coal (82.3% C) and a Chinese low-volatile Dongshan bituminous coal (90% C) were gasified in a fluidised-bed/fixed-bed reactor at 800 °C in atmospheres containing 15% H₂O, 2000 ppm O₂ or 15% H₂O + 2000 ppm O₂. While the gasification of these coals in 2000 ppm O₂ converted less than 27% of coal-N into NH₃, the introduction of steam played a vital role in converting a large proportion of coal-N into NH₃ by providing H on char surface. The importance of the roles of steam in the formation of NH₃ in atmospheres containing 15% H₂O + 2000 ppm O₂ decreased with increasing coal rank. This is largely due to the slow gasification of high-rank coal chars, resulting in low availability of H on char surface. The gasification of chars from the high-rank coal appears to produce higher yields of HCN than that of lower rank coals, probably as a result of the decomposition of partially hydrogenated/broken/activated char-N structures during gasification at high temperature. The alkali and alkaline earth metallic species in brown coal tend to favour the release of coal-N as tar-N but have limited effects on char-N conversion during gasification.     

Simultaneous easy CO2 recovery and drastic reduction of SOx and NOx in O2/CO2 coal combustion with heat recirculation

Coal combustion with O₂/CO₂ is promising because of its easy CO₂ recovery, extremely low NO_x emission and high desulfurization efficiency. Based on our own fundamental experimental data combined with a sophisticated data analysis, its characteristics were investigated. It was revealed that the conversion ratio from fuel-N to exhausted NO in O₂/CO₂ pulverized coal combustion was only about one fourth of conventional pulverized coal combustion. To decrease exhausted NO further and realize simultaneous easy CO₂ recovery and drastic reduction of SO_x and NO_x, a new scheme, i.e. O₂/CO₂ coal combustion with heat recirculation, was proposed. It was clarified that in O₂/CO₂ coal combustion, with about 40% of heat recirculation, the same coal combustion intensity as that of coal combustion in air could be realized even at an O₂ concentration of as low as 15%. Thus exhausted NO could be decreased further into only one seventh of conventional coal combustion. Simultaneous easy CO₂ recovery and drastic reduction of SO_x and NO_x could be realized with this new scheme.     

Calcination and sintering characteristics of limestone under O2/CO2 combustion atmosphere

The O₂/CO₂ coal combustion technology is an innovative combustion technology that can control CO₂, SO₂ and NO_x emissions simultaneously. Calcination and sintering characteristics of limestone under O₂/CO₂ atmosphere were investigated in this paper. The pore size, the specific pore volume and the specific surface area of CaO calcined were measured by N₂ adsorption method. The grain size of CaO calcined was determined by XRD analysis. The specific pore volume and the specific surface area of CaO calcined in O₂/CO₂ atmosphere are less than that of CaO calcined in air at the same temperature. And the pore diameter of CaO calcined in O₂/CO₂ atmosphere is larger than that in air. The specific pore volume and the specific surface area of CaO calcined in O₂/CO₂ atmosphere increase initially with temperature, and then decline as temperature exceeds 1000 °C. The peaks of the specific pore volume and the specific surface area appear at 1000 °C. The specific surface area decreases with increase in the grain size of CaO calcined. The correlations of the grain size with the specific surface area and the specific pore volume can be expressed as L = 744.67 + 464.64 lg(1 / S) and L = − 608.5 + 1342.42 lg(1 / ε), respectively. Sintering has influence on the pore structure of CaO calcined by means of influencing the grain size of CaO.     

Volatilization behavior of fluorine in coal during fluidized-bed pyrolysis and CO2-gasification

The volatilization behavior of fluorine in five Chinese coals was investigated during fluidized-bed pyrolysis and CO₂-gasification at a temperature range of 500-900 °C. The effect of co-existed and added calcium on fluorine volatility during pyrolysis was also determined. With increasing pyrolysis temperature, the volatility of fluorine increases. However, the volatility is greatly dependent on the fluorine chemical forms occurred in coal. Except for Datong and Zhungeer coal, more than 65% of fluorine in other three coals occurs as the steady forms. Fluorapatite is not the major carrier of fluorine in the coals studied. Fluorine volatility is retarded by coexisting calcium during coal pyrolysis, indicating that at least part of the stable forms of fluorine in coal might occur as calcium fluoride or calcium fluoride with complex compounds which are stable even at high pyrolysis temperature. The addition of CaO and limestone can suppress the release of fluorine during pyrolysis. The effect of CaO is better than that of limestone. The volatility of fluorine of coal during CO₂-gasification depends on not only the occurrence mode of fluorine, but also the gasification reactivity of the coal. Compared with N₂ atmosphere, CO₂ is more favorable to the release of fluorine from coal.     

Partial O2-fired coal power plant with post-combustion CO2 capture: A retrofitting option for CO2 capture ready plants

In the work presented in this paper, an alternative process concept that can be applied as retrofitting option in coal-fired power plants for CO₂ capture is examined. The proposed concept is based on the combination of two fundamental CO₂ capture technologies, the partial oxyfuel mode in the furnace and the post-combustion solvent scrubbing. A 330 MW_el Greek lignite-fired power plant and a typical 600 MW_el hard coal plant have been examined for the process simulations. In a retrofit application of the ECO-Scrub technology, the existing power plant modifications are dominated by techno-economic restrictions regarding the boiler and the steam turbine islands. Heat integration from processes (air separation, CO₂ compression and purification and the flue gas treatment) can result in reduced energy and efficiency penalties. In the context of this work, heat integration options are illustrated and main results from thermodynamic simulations dealing with the most important features of the power plant with CO₂ capture are presented for both reference and retrofit case, providing a comparative view on the power plant net efficiency and energy consumptions for CO₂ capture. The operational characteristics as well as the main figures and diagrams of the plant’s heat balances are included.     

Impact of SO2 concentration on the corrosion rate of X70 steel and iron in water-saturated supercritical CO2 mixed with SO2

The corrosion behavior of X70 steel and iron in water-saturated supercritical CO₂ mixed with SO₂ was investigated using weight-loss measurements. As a comparison, the instantaneous corrosion rate in the early stages for iron in the same corrosion environment was measured by resistance relaxation method. Surface analyzes using SEM/EDS, XRD and XPS were applied to study the morphology and chemical composition of the corroded sample surface. Weight-loss method results showed that the corrosion rate of X70 steel samples increased with SO₂ concentration, while the corrosion rate increased before decreasing with SO₂ concentration for iron sample. Comparing resistance relaxation method results with weight-loss method results, it is found that the instantaneous corrosion rate of iron is much higher than the uniform corrosion rate of the iron tablet specimens which are covered with thick corrosion product films after a long period of corrosion. The corrosion product films were mainly composed of FeSO₄ and FeSO₃ hydrates. The possible reaction mechanism under such environment was also analyzed, and the electrochemical reaction between the dissolved SO₂ in the condensed water film with iron is the critical reaction step.     

Pulverized coal combustion in air and in O2/CO2 mixtures with NOx recycle

This paper presents experimental results of a 20 kW vertical combustor equipped with a single pf-burner on pulverised coal combustion in air and O₂/CO₂ mixtures with NO_x recycle. Experimental results on combustion performance and NO_x emissions of seven international bituminous coals in air and in O₂/CO₂ mixtures confirm the previous findings of the authors that the O₂ concentration in the O₂/CO₂ mixture has to be 30% or higher to produce matching temperature profiles to those of coal-air combustion while coal combustion in 30% O₂/70% CO₂ leads to better coal burnout and less NO_x emissions than coal combustion in air. Experimental results with NO_x recycle reveal that the reduction of the recycled NO depends on the combustion media, combustion mode (staging or non-staging) and recycling location. Generally, more NO is reduced with coal combustion in 30% O₂/70% CO₂ than with coal combustion in air. Up to 88 and 92% reductions of the recycled NO can be achieved with coal combustion in air and in 30% O₂/70% CO₂ respectively. More NO is reduced with oxidant staging than without oxidant staging when NO is recycled through the burner. Much more NO is reduced when NO recycled through the burner (from 65 to 92%) than when NO is recycled through the staging tertiary oxidant ports (from 33 to 54%). The concentration of the recycled NO has little influence on the reduction efficiency of the recycled NO with both combustion media—air and 30% O₂/70% CO₂.     

Effect of TiO2 particle size on the photocatalytic reduction of CO2

Pure TiO₂ anatase particles with a crystallite diameters ranging from 4.5 to 29 nm were prepared by precipitation and sol–gel method, characterized by X-ray diffraction (XRD), BET surface area measurement, UV–vis and scanning electron microscopy (SEM) and tested in CO₂ photocatalytic reduction. Methane and methanol were the main reduction products. The optimum particle size corresponding to the highest yields of both products was 14 nm. The observed optimum particle size is a result of competing effects of specific surface area, charge–carrier dynamics and light absorption efficiency.     

The catalytic performance in oxidative coupling of methane and the surface basicity of La2O3, Nd2O3, ZrO2 and Nb2O5

The catalytic performance in oxidative coupling of methane (OCM) of unmodified pure La₂O₃, Nd₂O₃, ZrO₂ and Nb₂O₅ has been investigated under various conditions. The results confirmed that the activity of La₂O₃ and Nd₂O₃ was always much higher than that of the remaining two. The surface basicity/base strength distribution of pure La₂O₃, Nd₂O₃, ZrO₂ and Nb₂O₅ was measured using a test reaction of transformation of 2-butanol and a temperature-programmed desorption of CO₂. Both methods showed that La₂O₃ and Nd₂O₃ had high basicity and contained medium and strong basic sites (lanthanum oxide more and neodymium oxide somewhat less). ZrO₂ had only negligible amount of weak basic sites and Nb₂O₅ was rather acidic. The confrontation of the basicity and catalytic performance indicated that in the case of investigated oxides, the basicity (especially strong basic sites) could be a decisive factor in determination of the catalytic activity in OCM. Only in the case of ZrO₂ it was observed a moderate catalytic performance in spite of negligible basicity. The influence of a gas atmosphere used in the calcination of oxides (flowing oxygen, helium and nitrogen) on their basicity and catalytic activity in OCM had been also investigated. Contrary to earlier observations with MgO, no effect of calcination atmosphere on the catalytic performance of investigated oxides in OCM and on their basicity was observed.     

Thermodynamic performance of O2/CO2 gas turbine cycle with chemical recuperation by CO2-reforming of methane

This paper proposes a novel power cycle system composed of chemical recuperative cycle with CO₂–NG (natural gas) reforming and an ammonia absorption refrigeration cycle. In which, the heat is recovered from the turbine exhaust to drive CO₂–NG reformer firstly, and then lower temperature heat from the turbine exhaust is provided with the ammonia absorption refrigeration system to generate chilled media, which is used to cool the turbine inlet gas except export. In this paper, a detailed thermodynamic analysis is carried out to reveal the performance of the proposed cycle and the influence of key parameters on performance is discussed. Based on 1 kg s⁻¹ of methane feedstock and the turbine inlet temperature of 1573 K, the simulation results shown that the optimized net power generation efficiency of the cycle rises up to 49.6% on the low-heating value and the exergy efficiency 47.9%, the new cycle system reached the net electric-power production 24.799 MW, the export chilled load 0.609 MW and 2.743 kg s⁻¹ liquid CO₂ was captured, achieved the goal of CO₂ and NO_x zero-emission.