Combustion and Pollutant Emission Characteristics of Lignite Dried by Low Temperature Air

Lignite is a kind of coal that has high moisture content and needs to be dried before being utilized. In this article, a Chinese lignite was dried in air at 120–180°C and the changes in its physical and chemical structures after drying were investigated. The results showed that the pore volume and specific surface area of the lignite decreased after drying. Some of the methylene and methyl groups were oxidized by the oxygen in the drying air, resulting in an increase in oxygen functional groups. The combustion characteristics of the dried coals and parent coal (dry basis) were studied via thermogravimetric analysis. The total volatile yields of the dried coals increased compared to the parent coal. The burnout temperatures of the dried coals were higher than the parent coal, whereas the ignition temperatures stayed almost unchanged. An entrained flow system was set up to study the release of nitrogenous gas products during rapid pyrolysis and combustion. The HCN yields of the dried coals during pyrolysis were higher than that of the parent coal, and a similar trend was found for the NO yield during combustion. The mechanism changes of combustion and pollutant emission characteristics were discussed according to the results of the physical and chemical structure analyses.     

Ambient-pressure thermogravimetric characterization of four different coals and their chars

Ambient-pressure thermogravimetric characterization of four different coals and their chars was performed to obtain fundamental information on pyrolysis and coal and char reactivity for these materials. Using a Perkin-Elmer TGS-1 thermobalance, weight loss as a function of temperature was systematically determined for each coal heated in helium at 40 and 160 °C/min under various experimental conditions, and for its derived char heated in air over a temperature range of 20 to 1000 °C. The results indicate that the temperature of maximum rate of devolatilization increases with increasing heating rate for all four coals. However, heating rate does not have a significant effect on the ultimate yield of total volatiles upon heating in helium to 1000 °C; furthermore, coupled with previous data⁹ for identical coal samples, this conclusion extends over a wide range of heating rate from 0.7 to 1.5 × 10⁴ °C/s. Using the temperature of maximum rate of devolatilization as an indication of relative reactivity, the devolatilization reactivity differences among the four coals tested that were suggested by this criterion are not large. For combustion in air, the overall coal/char reactivity sequence as determined by comparison of sample ignition temperature is: N. Dakota lignite coal ≈ Montana lignite coal > North Dakota lignite char > III. No. 6 bituminous coal ≈ Pittsburgh Seam bituminous coal > Montana lignite char > III. No. 6 bituminous char > Pittsburgh Seam bituminous char. The reactivity differences are significantly larger than those for devolatilization. The reactivity results obtained suggest that coal type appears to be the most important determinant of coal and char reactivity in air. The weight loss data were fitted to a distributed-activation-energy model for coal pyrolysis; the kinetic parameters so computed are consistent with the view that coal pyrolysis involves numerous parallel first-order organic decomposition reactions.     

A reactivity study of chars obtained at different temperatures in relation to their petrographic characteristics

This study reports on the reactivity of chars obtained at 1000°C and 1300°C (within the range of temperatures reached by coal particles in the near-burner zone of pulverised fuel boilers) from three different coals. The coals were selected according to petrographic criteria: two of them are high volatile bituminous coals differing in maceral composition and the third one is a vitrinite-rich low volatile bituminous coal.The morphology and optical texture of the chars were studied by optical microscopy. The kinetic parameters for the combustion of the high temperature chars under Regime I (combustion controlled by chemical kinetics) have been obtained and related to the optical texture and reflectance of the chars. The intrinsic reactivity of the high temperature chars was found to be lower than that of the low temperature chars, whereas the enhanced porosity observed in the high temperature chars had a positive effect on their combustion reactivity under Regime II (combustion controlled by oxygen pore diffusion). The intrinsic reactivities of the chars decreased following the sequence: vitrinite-rich low rank char>inertinite-rich char>vitrinite-rich high rank char. As the combustion temperature increases, the reactivity of the inertinite-rich char approaches that of the low rank vitrinite-rich char, which justifies the good performance observed for high volatile bituminous inertinite-rich coals in power plants.     

Chemical reduction of sulphur dioxide to free sulphur with lignite and coal. 2. Kinetics and proposed mechanism

The reactivity of lignite and different ranks of coal with sulphur dioxide has been investigated in a corrosive-gas, thermogravimetric reactor system. With all coals, the reaction occurred in two distinct stages. A rapid initial stage was controlled primarily by the devolatilization rate of the coal. The second stage limited the overall rate and was controlled by surface properties of the coal char. The portion of lignite associated with the second stage of reaction exhibited a much higher rate of SO₂ reduction than the corresponding material from all other coals. Correlation of the data showed an inverse relation between the reactivity of coal chars and the relative rank of the parent coal. Activation energies associated with the reduction of SO₂ by the coal chars increased slightly from 134 kJ mol^?1 for lignite char to 150 kJ mol^?1 for HVB bituminous coal char. The higher reactivity of lignite or lower-rank coals was due in part to entropy factors or available catalytic sites on the surface of coal. Formation of a thermally stable CS complex on the surface of coal appeared to poison the surface and thus limit further reaction. Alkali and alkaline earth metals in lignite served as active sites for catalysing the reaction of SO₂ with the CS complex and thus enhanced the rate of SO₂ reduction with lignite.     

Influence of mineral matter in coal on decomposition of NO over coal chars and emission of NO during char combustion

NO-char reaction and char combustion in the presence and absence of mineral matter were studied in a quartz fixed bed reactor. Eight chars were prepared in a fluidized bed at 950 °C from four Chinese coals that were directly carbonized without pretreatment or were first deashed before carbonization. The decomposition of NO over these coal-derived chars was studied in Ar, CO/Ar and O₂/Ar atmospheres, respectively. The results show that NO is more easily reduced on chars from the raw coals than on their corresponding deashed coal chars. Mineral matter affects the enhancement both of CO and O₂ on the reduction of NO over coal chars. Alkali metal Na in mineral matter remarkably catalyzes NO-char reaction, while Fe promotes NO reduction with CO significantly. The effect of mineral matter on the emission of NO during char combustion was also investigated. The results show that the mineral constituents with catalytic activities for NO-char reaction result in the decrease of NO emission, whereas mineral constituents without catalytic activities lead to the increase of NO emission. Correlation between the effects of mineral matter on NO-char reaction and NO emission during char combustion was also discussed.     

Thermogravimetric determination of the carbon dioxide reactivity of char from some New Zealand coals and its association with the inorganic geochemistry of the parent coal

Thermogravimetrically-determined carbon dioxide reactivities of chars formed from New Zealand coals, ranging in rank from lignite to high volatile bituminous, vary from 0.12 to 10.63 mg/h/mg on a dry, ash-free basis. The lowest rank subbituminous coal chars have similar reactivities to the lignite coal chars. Calcium content of the char shows the strongest correlation with reactivity, which increases as the calcium content increases. High calcium per se does not directly imply a high char reactivity. Organically-bound calcium catalyses the conversion of carbon to carbon monoxide in the presence of carbon dioxide, whereas calcium present as discrete minerals in the coal matrix, e.g., calcite, fails to significantly affect reactivity. Catalytic effects of magnesium, iron, sodium and phosphorous are not as obvious, but can be recognised for individual chars. The thermogravimetric technique provides a fast, reliable analysis that is able to distinguish char reactivity differences between coals, which may be due to any of the above effects.     

Reactivities of 34 coals under steam gasification

The reactivities of 34 coal chars of varying rank with H₂O have been determined to examine the effect of coal rank on the gasification rate of coal char. The reactivities of chars derived from caking coals and anthracites (carbon content > 78 wt%, daf) were very small compared with those from non-caking (lower-rank) coals. The reactivities of low-rank chars do not correlate with the carbon content of the parent coals. To clarify which factor is more important in determining the reactivity, the evolution of CO and CO₂ from char, the moisture content of char and the amount of exchangeable cations were determined for these low-rank coals or their chars. These values were considered to represent the amount of active carbon sties, the porosity and the catalysis by inherent mineral matters, respectively. It was concluded that the amount of surface active sites and/or the amount of exchangeable Ca and Na control the reactivity of low-rank chars in H₂O.     

A comparative reactivity and kinetic study on the combustion of coal-biomass char blends

The combustion behavior and kinetics of various biomass chars, a lignite and a hard coal char and their blends were investigated. Pure fuel chars were compared to blended chars with respect to their performance during combustion. Non-isothermal thermogravimetry experiments were performed in air atmosphere, over a temperature range of 25-850 °C and at a heating rate of 10 °C/min. Kinetic evaluation was performed using a power law model. Reaction kinetic parameters were obtained by modeling the combustion of biomass and coal chars as a single reaction, with the exception of lignite and olive kernel chars, the combustion of which was modeled by two partial reactions. A single reaction model was used in the case of coal-wood char blends, while for the lignite-biomass char blends two partial reactions were used. Reactivity was assessed using the specific reaction rate, as a function of conversion. Biomass chars were generally more reactive than those of hard coal and lignite. The combustion behavior of the blends was greatly influenced by the rank of each coal (hard coal or lignite) and the proportion of each component in the blend. Combustion performance of the blends showed some deviation from the expected weighted average of the constituent chars. An attempt was made to estimate the kinetics of the blends using, as a basis, the parameters estimated for the individual components. In this case, because of the interactions between the components of the blends, the kinetic parameters needed to be slightly modified. Alteration in reactivity was more pronounced in the case of lignite-biomass chars than coal-wood chars.     

煤焦燃烧特性及反应活性探究

中国褐煤资源丰富,然而由于褐煤自身特点使其应用受到了极大的限制。针对中国褐煤应用最广的途径———燃烧,借助热重分析仪对不同热解终温的褐煤半焦及热解终温为1273 K的褐煤半焦与原煤的混合燃料的燃烧特性进行了分析。并利用Coats-Redfern法进行了燃烧动力学的分析,通过求得的表观活化能表征煤焦的燃烧反应活性。研究发现：热解终温越高,煤焦的燃烧特性越差;掺混褐煤有助于提高其半焦的燃烧特性,而掺混燃料的燃烧稳定性几乎和原煤无差别,且随着掺混比例的增加,混合燃料的活化能逐渐增大,越不易点燃,掺混半焦对燃料的燃烧特性和反应活性都有影响。相同制备条件下的烟煤半焦和褐煤半焦的燃烧动力学参数尤其是活化能相差很大,可见煤焦的燃烧反应活性与煤种有关。     

Reactivity of bituminous coal chars during the initial stage of pulverized-coal combustion

The reactivities of pyrolysed and partially burned char particles prepared in an entrained-flow reactor have been investigated. The results indicate that chars collected at the end of the active devolatilization stage are more reactive than those collected before or after this stage. Deactivation of the pyrolysed chars was accompanied by the development of micropores. The chars produced from a liptinite-rich fraction of an HVA bituminous coal showed higher reactivities than those generated from an inertinite-rich fraction. It is suggested that residual volatiles play a more important role in determining char reactivity than the microporosity and the optical anisotropy of the chars. A new expression for TGA reactivity is suggested for use in deriving char combustion kinetics. Relatively constant activation energies of ≈ 125 kJ mol⁻¹ were obtained for chars prepared from a wide range of coal precursors. Calculated char combustion rates at high temperatures extrapolated from such reactivity parameters were in agreement with experimentally determined rates.     

Reactivity of heat-treated coals in air at 500 °C

Twenty one US coals, of widely ranging rank, have been carbonized under controlled conditions to 1000 °C, and the reactivity in air at 500 °C of the resulting chars or cokes has been measured by a gravimetric method. The reactivities lie within a well-defined band when plotted against rank of the parent coal. The lower-rank coal chars are more reactive than those prepared from high-rank coals. In extreme cases, the reactivity found for a Montana lignite char is some 100 times as great as that obtained for a char produced from a Pennsylvania low-volatile coal. Variation of reactivity with heat-treatment temperature (600 to 1000 °C) has been studied for three coals. As heat-treatment temperature increases, there is a decrease in reactivity. Some results are reported on the effects which mineral matter and pore structure have on the reactivity parameter. Chars containing high concentrations of magnesium and calcium impurities are most reactive. The amount of macro and transitional porosity in a char has a marked influence on reactivity.     

Enhancement of lignite char reactivity to steam by cation addition

Chars produced from lignites typically have much higher reactivities to gasification than those produced from bituminous coals. This has been attributed previously to the presence of carboxylate salts of inorganic constituents on the lignites. Upon charring of the lignites, the carboxylate salts decompose leaving behind well dispersed inorganic constituents which act as catalysts for gasification. In this study, a raw lignite has been treated with HCl and HF to demineralize it and to increase its carboxyl content prior to exchanging selected cations with the hydrogen on the carboxyl groups. Up to 2.14 mmol of calcium per g of coal could be added using this procedure. Addition of varying amounts of calcium to the lignite resulted in the production of chars containing calcium contents ranging from 1.1 to 12.9 wt %. Such addition resulted in a rectilinear increase in reactivity of the char to steam with increasing amount of calcium added. Maximum reactivity attained was over ten times the reactivity found for the char produced from the raw lignite. At comparable molar loadings of metal cations onto the acid-treated lignite, the chars subsequently produced had reactivities in steam in the order: K >Na ≈ Ca >Fe >Mg. Char reactivity could also be enhanced by the addition of cations to nitric acid-treated char which had been produced, in turn, from demineralized lignite.     

Analysis of D2 law in case of Shengli lignite drying under inert and uninert environment

Shengli lignite coal, originated from inner Mongolia China, contains significantly high amount of moisture (more than 30%) which can cause spontaneous combustion or other application problems. Thus, it is of interest to understand the heat and mass transfer mechanism of the low-rank lignite drying under different drying environments such as N₂, CO₂, air, argon, and helium. In this study, fundamental drying experiments with different drying agents were performed on coal samples using thermogravimetric analysis (TGA) method. Lignites with size of 0.045–0.075?mm were heated up from ambient temperature to a target temperature of 175°C under different environments at heating rates of 5, 10, 20, 40, and 80 °C/min, respectively. It was found that thermal conductivity of drying media, heating rate, and initial moisture content are three most significant factors affecting lignite drying process. The highest moisture release rate and the lowest T_peak (when maximum moisture release rate occurred) were observed when drying with helium due to its highest evaporation constant (i.e., highest thermal conductivity). Moreover, higher heating rate and moisture content resulted in higher evaporation rate and T_peak. In the meantime, the classical D² law, which is used to simulate the liquid fuel droplet combustion, was further developed to describe the “group effect” of moisture evaporation process of solid fuel during drying. The D² law well explains the experiment results. Finally, the structures of the dried lignite samples under different drying mediums were investigated through scanning electron microscopy studies. It was found that lignite coals shrank and became more compact when dried out, especially with drying agent CO₂.     

NOx generation from the combustion of Australian brown and subbituminous coals

The formation of NO_x during the combustion of pulverized brown and subbituminous coals from Victoria and Queensland respectively was investigated in an entrainment reactor. As no NO₂ was detected, all the NO_x was present in the form of NO. The brown coals exhibited a significantly greater potential for NO emission under fuel-lean conditions than did the subbituminous coal, even though the latter coal had a higher nitrogen content. However, under fuel-rich conditions the conversion of coal nitrogen to NO for the subbituminous coal was higher than for the brown coals. The differences in conversion efficiency may have been related in part to the nature and reactivity of the volatile nitrogen species. Reactivity differences between the chars produced from the brown and subbituminous coals may also have accounted for different extents of removal of NO. There was a significant reduction in the amount of NO emitted when brown coal was added to a combustion gas stream containing an appreciable quantity of NO before coal injection.     

Identification of reaction zones in a commercial Sasol-Lurgi fixed bed dry bottom gasifier operating on North Dakota lignite

The Sasol-Lurgi fixed bed dry bottom gasification technology has the biggest market share in the world with 101 gasifiers in operation. To be able to further improve the technology and also to optimise the operating plants, it is important that the fundamentals of the process are understood. The main objective of this study was to determine the reaction zones occurring in the Sasol-Lurgi fixed bed dry bottom (S-L FBDB) gasifier operating on North Dakota lignite. A Turn-Out sampling method and subsequent chemical analyses of the gasifier fuel bed samples was used to determine the reaction zones occurring in the commercial MK IV, S-L FBDB gasifier operating on North Dakota lignite. The reaction zones were further compared with the same reactor operating on bituminous coal.Based on the results obtained from this study it was found that about two thirds of the gasifier volume was used for drying and de-volatilising the lignite thus leaving only about a third of the reactor volume for gasification and combustion. Nonetheless, due to the high reactivity of the lignite, the char was consumed within a third of the remaining gasifier volume. Clear overlaps between the reaction zones were observed in the gasifiers thus confirming the gradual transition from one reaction zone to another as reported in literature. Due to the high moisture content in the lignite, the pyrolysis zone in the gasifiers operating on North Dakota lignite occurred lower/deeper in the gasifier fuel bed as compared to the same gasifier operating on South African bituminous coal from the Highveld coalfield. All the other reaction zones in the gasifier operating on bituminous coal were also higher in the bed compared to the lignite operation. This can therefore explain the higher gas outlet temperatures for the S-L FBDB gasifiers operating on higher rank coals when compared to the gasifiers operating on lignite. The fact that the entire reactor volume was utilized for drying, de-volatilisation, gasification and combustion with carbon conversion of >98% makes the S-L FBDB gasifier very suitable for lignite gasification.     

不同干燥程度胜利褐煤燃烧与自燃特性

为了探究高水分褐煤干燥后的燃烧与自燃特性变化,采用一维火焰炉、煤粉着火炉以及自燃试验台对不同干燥程度的胜利褐煤进行了试验研究。试验结果表明,试验样品的着火温度随着干燥程度的增加而降低,随着风煤比的增加而增加,煤粉细度同样会对着火温度产生影响。在燃用干燥褐煤过程中宜采用较高一次风率以提高制粉系统的安全性。胜利褐煤及其干燥褐煤均属于极易燃尽煤种,燃尽率均在99.4%以上,水分的变化对燃尽率影响不大。建议胜利褐煤与20%水分干燥褐煤的运行氧含量控制在3.5%左右。随着干燥程度的加深和粒径的减小,褐煤越容易自燃。胜利褐煤干燥到20%以下可能有自燃的风险。     

The kinetics of coal chars hydrogasification

Hydrogasification reaction of chars produced from two rank coals was investigated in temperature up to 1173 K and pressure up to 8 MPa. The reactivity of the lignite Szczerców char has been found to be slightly higher than of the subbituminous coal Janina char produced at the same conditions. A high value of the char reactivity was observed to certain carbon conversion, above which a sharp drop takes place. It has been shown that to achieve proper carbon conversion the hydrogasification reaction must proceed at temperature above 1200 K. Based on the active centres theory the kinetic equations of the hydrogasification process were developed and the kinetic constants at the maximum reaction rate evaluated for the analyzed chars.     

Combustion behaviour of ultra clean coal obtained by chemical demineralisation

The increasing environmental concern caused by the use of fossil fuels and the concomitant need for improved combustion efficiency is leading to the development of new coal cleaning and utilisation processes. However, the benefits achieved by the removal of most mineral matter from coal either by physical or chemical methods can be annulled if poor coal combustibility characteristics are attained. In this work a high volatile bituminous coal with 6% ash content was subjected to chemical demineralisation via hydrofluoric and nitric acid leaching, the ash content of the clean coal was reduced to 0.3%. The original and treated coals were devolatilised in a drop tube furnace and the structure and morphology of the resultant chars was analysed by optical and scanning electron microscopies. The reactivity characteristics of the chars were studied by isothermal combustion tests in air at different temperatures in a thermogravimetric system. Comparison of the combustion behaviour and pollutant emissions of both coals was conducted in a drop tube furnace operating at 1000 °C. The results of this work indicate that the char obtained from the chemically treated coal presents very different structure, morphology and reactivity behaviour than the char from the original coal. The changes induced by the chemical treatment increased the combustion efficiency determined in the drop tube furnace, in fact higher burnout levels were obtained for the demineralised coal.     

Reactivity of heat-treated coals in steam

Reactivities of seventeen 40 × 100 mesh (U.S.) coals charred to 1000 °C have been measured at 910 °C in 0.1 MPa of a N₂H₂O mixture containing water vapour at a partial pressure of 2.27 kPa. Char reactivity decreases, in general, with increasing rank of the parent coal. The chars show a 250-fold difference in their reactivities. Results suggest that gasification of chars in air, CO₂ and steam involves essentially the same mechanism and that relative gasification rates are controlled by the same intermediate oxygen-transfer step. Removal of inorganic matter from raw coals prior to their charring or from chars produced from raw coals decreases the reactivities of lower-rank chars, whereas reactivities of higher-rank chars increase. Addition of H₂ to steam has a marked retarding effect on char reactivity in most cases. However, in a few cases H₂ acts as an accelerator for gasification. The effect of particle size, reaction temperature and water-vapour pressure on char reactivity is considered.     

Kinetic analysis of NO-Char reaction

Two Chinese coals were used to prepare chars in a flat flame flow reactor which can simulate the temperature and gas composition of a real pulverized coal combustion environment. Acid treatment on the YB and SH chars was applied to obtain demineralized chars. Kinetic characterization of NO-char reaction was performed by isothermal thermogravimetry in the temperature range of 973–1,573 K. Presence of catalytic metal matter can increase the reactivity of chars with NO, which indicates that the catalytic effects of inherent mineral matter play a significant role in the NO-char reaction. The discrete random pore model was applied to describe the NO-char reactions and obtain the intrinsic kinetics. The model can predict the data for all the chars at various temperatures well, but underestimate the reaction rates at high carbon conversions for the raw YB and SH chars, which can be attributed to the accumulation of metal catalyst on char surface. This work was presented at the 7 ^th China-Korea Workshop on Clean Energy Technology held at Taiyuan, Shanxi, China, June 26–28, 2008.