Effect of Coal Type and Residence Time on the Submicron Aerosol Distribution from Pulverized Coal Combustion

Three types of pulverized coal were burned in a laboratory furnace under various combustion configurations. Pulverized samples of Utah bituminous, Beulah (North Dakota) lignite, and Texas lignite coals were burned at a rate of 2.5 kg/hr in a laboratory furnace. Aerosol size distributions were measured at various positions within the convection section, and temperature and gas compositions were measured throughout. The evolution of the submicron particle size distribution within the convection section for the three coals was similar, although the location of the initial particle mode at the convection section inlet varied with coal type. While staged combustion of Utah bituminous coal had a variable effect on the volume of submicron aerosol produced, staged combustion of the lignites caused a definite increase in the submicron aerosol volume. Vapor enhancement due to a localized reducing atmosphere, which would effect coals of higher ash volatility, is thought to explain this behavior.     

Filtration in coal liquefaction: filtration of digest prepared from lignite

The filtration characteristics of digests prepared from bituminous coals and lignites are compared. In the case of bituminous coals the filtration rate is sensitive to the presence of gel-like material formed during the early stages of digestion; with lignite the formation of a gel intermediate is undetectable, and it may not form at all. The impact of this difference in dissolution mechanism upon reactor design is considered.     

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.     

煤快速热解固相和气相产物生成规律

利用能有效避免二次转化反应的高频炉热解装置对3种不同变质程度的煤进行了600～1200℃条件下的快速热解,考察了在煤热解最初阶段焦产率、焦-C产率、热解气产率、热解气4种主要组分H₂、CO、CH₄和CO₂的比例以及热解气热值随煤阶和热解温度的变化规律。结果表明,焦的产率和焦-C的产率均随煤阶的升高而升高,热解气的产率随煤阶的升高而降低;热解温度的提高能显著降低煤焦和焦-C的产率并提高热解气的产率。热解气组分以H₂相似文献   

Extraction of coals with CS2-N-methyl-2-pyrrolidinone mixed solvent at room temperature Effect of coal rank and synergism of the mixed solvent

Coals (from lignite to anthracite) were extracted at room temperature with CS₂-N-methyl-2-pyrrolidinone (MP) mixed solvent (1:1 by volume), which was found to be a very efficient solvent for the extraction of bituminous coals in a previous study. High yields of 30–66% (daf) were obtained for 29 of the 49 bituminous coals (C%76.9–90.6% daf) examined. The anthracite, subbituminous coals and lignites did not give high yields. The results of the characterization of the raw coals, extracts and residues suggest that reactions between the coals and the solvents do not occur to a significant extent during the extraction. The synergistic effect, i.e. the large increase in yield and rate for the mixed solvent compared with those for CS₂ and MP alone has been explained by increasing solubility and diffusibility of the extracts and increasing swelling of the coals, in the mixed solvent. The mixed solvents of CS₂ with quinoline, pyridine and THF gave lower extraction yields than the CS₂-MP mixed solvent.     

Fate of aliphatic groups in low-rank coals during extraction and pyrolysis processes

Information on the nature of aliphatic groups in some bituminous coals and lignites was obtained by determining their fate during extraction and pyrolysis processes of differing severity. Aromatics (neutral oils) and asphaltenes from supercritical gas and hydrogen-donor solvent extracts and from pyrolysis and hydropyrolysis tars have been characterized by an n.m.r.-based structural analysis method which identifies hydroaromatic, methyl and long alkyl (?C₈) groups. The results indicate that methyl and other alkyls account for about half of the aliphatic carbon, long alkyl chains being the major aliphatic group in the lignites. There is evidence to suggest that some of the long alkyl chains are joined to aromatic structures. Hydroaromatic groups are small consisting of only 1–2 rings and account for less of the aliphatic carbon in bituminous coals than previously thought. Their concentrations and those of long alkyl chains in the aromatics and asphaltenes generally decrease with increasing process severity.     

Steric requirements for coal swelling by amine bases

A set of six coals ranging in rank from lignite to hvA bituminous was swollen with a series of alkyl-substituted pyridines and a smaller set of 4-alkylanilines. The size and branching of the alkyl groups was varied and the effect of this variation on the dissolution of the amines in the coal and the resulting coal swelling was measured volumetrically. In a few cases, substituents which hindered the amine nitrogen were studied. The lignite and subbituminous coal have a much higher tolerance to branched, bulky groups than do the bituminous coals. The presence of tertiary groups in a solute strongly inhibits their dissolution in bituminous coals. Bituminous coals behave as if extensive parallel packing of structures occurs. Often, they can accept very large planar groups but have a low capacity for branched groups.     

Modeling the influence of changes in aliphatic structure on char surface area during coal pyrolysis

The influence of changes in aliphatic structure on char surface area during coal pyrolysis was modeled, and the effect was introduced to a previous char surface area model for lignite pyrolysis established based on the chemical percolation devolatilization (CPD) model. The modified model can predict not only the N₂ and CO₂ char surface area during rapid pyrolysis of three lignites but also the CO₂ char surface area of two high-volatile bituminous coals; the agreement of the modified model with experiments is improved at high temperatures. The decrease in aliphatic chain length can reduce adsorption positions around aromatic core, and decrease char surface area. When mass release is more than 55% at about 1,100 K, the predicted N₂ char surface area starts to decrease with further generation of volatiles, and the increase of predicted CO₂ char surface area with increasing generation of volatiles also become slow at the end of mass release.     

Laboratory gasification of five Canadian coals

Results of a gasification study of five Canadian coals in a 100g laboratory fixed-bed gasifier are reported. The coals were three bituminous coals (Byron Creek, Prince and Devco) and two lignites (Coronach and Bienfait). When gasified in an equal mixture of nitrogen and oxygen at 850 °C, the lignites reacted more rapidly and produced more liquid and gaseous products than the bituminous coals, whereas the bituminous coals produced more methane but less carbon monoxide. Overall rates for both the gasification and combustion processes were 3.20, 2.80, 1.84, 1.70 and 1.25 wt% carbon conversion per min for Coronach, Bienfait, Prince, Byron Creek and Devco coals, respectively.     

Mutagenicity of eluent by hot water extraction of various coals: Effect of chlorination

Six kinds of powdery coals (two bituminous coals, two sub-bituminous coals, and two lignites) were extracted by hot water, and the eluents obtained were analyzed for total organic carbon (TOC), absorbance at 260 nm (A₂₆₀), and pH. The TOC in the eluents decreased in the order, lignites > sub-bituminous coals > bituminous coals. The eluents of lignite gave high A₂₆₀/TOC values and fairly low pH compared to other coals. Chemical structure of the organic matter eluted from coals was discussed with the aid of FTIR analysis. The coal eluents were analyzed by the Ames mutagenicity assay using Salmonella typhimurium TA100 and TA98 strains, and no mutagenicity was observed for all of the six coals. However, especially for the lignites, chlorination of the eluents produced an appreciable mutagenicity, and the expression of mutagenicity was dependent upon the type of coal. The mutagenicity was extinguished when metabolic activation (rat liver homogenate, +S9) was applied.     

停留时间对低阶煤快速热解产物分布、组成及结构的影响

利用自由落下床反应器,研究了快速热解过程中颗粒停留时间对神木烟煤和内蒙古褐煤热解过程的影响,并进一步延长快速热解新生半焦停留时间考察了半焦的二次热解过程。结果表明,快速热解过程中颗粒停留时间的增加促进了挥发分的析出,神木烟煤热解焦油产率持续增加,内蒙古褐煤热解焦油产率先增加后降低。停留时间对焦油品质有明显影响,随时间的增加,两种煤快速热解轻质油中苯类和苯酚类单环化合物含量均先增加后降低,进一步延长停留时间,多环芳烃化合物含量显著增加。快速热解半焦的二次热解主要促进了气体的生成,焦油产率和组成无明显变化,挥发分的进一步析出促进了半焦微孔的发展,神木烟煤和内蒙古褐煤半焦比表面积均显著增加。这表明,在以高品质焦油为目标产品时,采用较低的反应温度、较适宜的煤粒停留时间的快速热解工艺条件是可取的。     

Absorption of iodine by coal and lignite

The vapor pressure of iodine over mixtures of iodine and various coals has been measured at temperatures of 65–95°C. Lignite and bituminous coals exhibit similar behavior in their absorption of iodine whereas the behavior of anthracite coal is different. A region of constant vapor pressure occurs in the reaction between iodine and the bituminous coals and lignite. Complex formation between the iodine and coal is postulated.     

钙基添加剂对不同煤种解耦燃烧下硫释放的影响

煤燃烧后排放的硫氧化物导致的环境污染问题已经引起人们的日益关注。基于一段式和两段式卧式炉,本文探究在传统燃烧和解耦燃烧条件下,温度、煤种以及CaO对燃煤释放SO₂规律的影响。试验结果表明：不同煤种的SO₂释放规律存在差异。随着温度的升高,不同煤种燃烧SO₂的释放量均不断增加,硫的动态析出曲线逐渐由单峰分布转化为双峰分布。传统燃烧模式下,添加的CaO对烟煤、无烟煤和褐煤脱硫效率可以达到70%以上,高氯煤脱硫效率则较低,仅有12.09%～20.45%;随温度升高,烟煤、褐煤和高氯煤的脱硫效率呈现先略微下降,后升高再下降的趋势,烟煤脱硫效率则逐渐降低。解耦燃烧模式下,CaO对烟煤、无烟煤脱硫效率在42.35%～76.23%,褐煤在21.35%～52.63%,高氯煤脱硫效率仍然较低,在8.93%～10.57%;随温度升高,烟煤、褐煤和高氯煤的脱硫效率呈现先增加后降低的趋势,烟煤脱硫效率逐渐降低。解耦燃烧模式下,不同煤种SO₂的总释放量大于传统燃烧模式,添加CaO后脱硫效率小于传统燃烧模式。     

Effect of demineralization process on the liquefaction of Turkish coals in tetralin with microwave energy: Determination of particle size distribution and surface area

The effects of solvent/coal (S/C) ratio and demineralization on the solubilization of Turkish coals (Tunçbilek, Muğla-Yatağan, Beypazarı lignites and Zonguldak bituminous coal) in tetralin by microwave energy have been investigated. Particle size distributions and the surface area of the coals decreased with demineralization. For the investigation of the effect of the S/C ratios with values of 8/1, 10/1 and 12/1, the coal samples were heated by microwave energy for 20 min. The result indicated that the optimum S/C ratio was 8/1. The effect of microwave heating period was investigated at this value and the heating period was changed from 5 to 20 min at 5-min intervals. It was found that THF solubles yields of original coals were higher than those for demineralized coal except for Muğla-Yatağan lignite.     

Sulfur removal from original and acid treated lignites by pyrolysis

Six original, three hydrochloric acid treated and three demineralized lignite samples were pyrolysed at seven different temperatures between 350 and 950 °C for 7 min under evolved gas atmosphere. All samples and their chars were analysed quantitatively for their total sulfur content and pyritic, sulfate and organic sulfur forms. The alkaline oxide contents of original lignites and their hydrochloric acid treated counterparts were determined. The results clearly indicate that calcium and sulfurous compounds in the parent lignites undergo various chemical changes during pyrolysis. The pyrolysis temperature, types of sulfur and calcium compounds, all affect the behaviour of sulfur during pyrolysis. Higher pyrolysis temperatures favour total sulfur removal for all lignites, reaching 30-54% around 850 and 950 °C. HCl treatment and demineralization decreases calcium contents, hence, increases quantitative sulfur removal from the lignites by pyrolysis. The maximum total sulfur removal from acid treated lignites is observed as 77%. The ratios of the total sulfur to heating value decreases with increases of pyrolysis temperature up to around 600 °C for acid treated lignites and no major changes are observed at higher pyrolysis temperatures; no common behaviour is observed for original lignites.     

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.     

Differential thermal analysis study of lignite hydrogenation

Several New Zealand lignites and three other coals have been compared by differential thermal analysis in hydrogen at a pressure of 8.0 MPa. Most coals showed two exothermic peaks at ≈350 and 500 °C, but the relative magnitude of the two peaks varied from one coal to another. Ion-exchanging one of the lignites with Zn, Fe, Ni, Pb and Sn reduced the temperature of the peak maximum. Both Fe and Sn are known to catalyse coal hydrogenation. The results show that nickel and lead warrant further investigation as potential catalysts for coal hydroliquefaction, since they reduced the reaction temperatures even more than Fe or Sn. The reaction of lignite with tetrahydronaphthalene, in the absence of hydrogen, has been shown to be endothermic; a factor of interest in the context of donorsolvent hydroliquefaction facilities.     

Pyrolysis and hydropyrolysis of Louisiana lignite

Pyrolysis and hydropyrolysis kinetics of five samples of Louisiana lignite have been studied in an atmospheric pressure TG system as a function of heating rate and atmosphere. Final pyrolysis temperature was always 800 °C. The total volatile yield (dry basis) was 33.5–43.8wt%. For all lignites the volatile yield in hydrogen was greater than that obtained in nitrogen at similar conditions. However, variation in heating rate produced an opposite result in the two atmospheres with volatile yield increasing with heating rate in nitrogen but decreasing in hydrogen. Results have been analysed using the distributed activation energy pyrolysis model and parameters compared to similar studies using North Dakota and Montana lignites.     

Differential scanning calorimetry studies on coal. 1. Pyrolysis in an inert atmosphere

Results of thermal changes involved during the pyrolysis of twelve US coals of various ranks in a helium atmosphere at 5.6 MPa (gauge) and temperatures up to 580 °C are reported. Thermal effects during pyrolysis of coals ranging in rank from anthracite to HVC bituminous are endothermic in nature over the temperature range investigated. Exothermic heats are observed only in the case of sub-bituminous and lignitic coals. The net thermal effects, that is the resultant of endothermic and exothermic heats, go from endothermic to exothermic with increase in carbon content, a transition occurring around 66% carbon and another in the reverse direction at about 75% carbon. A maximum in exothermicity occurs around 71% carbon and in endothermicity at about 81% carbon. Results have been compared with published DTA data on coals. The fallacy in the interpretation of published DTA thermograms of coals, where weight changes accompany thermal effects, is discussed.     

Hydrogen production by methane cracking over different coal chars

Hydrogen production by methane cracking over a bed of different coal chars has been studied using a fixed bed reactor system operating at atmospheric pressure and 1123 K. The chars were prepared by pyrolysing four parent coals of different ranks, namely, Jincheng anthracite, Binxian bituminous coal, Xiaolongtan lignite and Shengli lignite, in nitrogen in the same fixed bed reactor operating at different pyrolysis temperatures and times. Hydrogen was the only gas-phase product detected with a GC during methane cracking. Both methane conversion and hydrogen yield decreased with increasing time on stream and pyrolysis temperature. The lower the coal rank, the greater the catalytic effect of the char. While the Shengli lignite char achieved the highest methane conversion and hydrogen yield in methane cracking amongst all chars prepared at pyrolysis temperature of 1173 K for 30 min, a higher catalytic activity was observed for the Xiaolongtan lignite char prepared at 973 K, indicating the importance of the nature of char surfaces. The catalytic activity of the coal chars were reduced by the carbon deposition. The coal chars had legible faces and sharp apertures before being subjected to methane cracking. The surfaces and pores of coal chars were covered with carbon deposits produced by methane cracking as evident in the SEM images. The results of BET surfaces areas of the coal chars revealed that the presence of micropores in the chars was not an exclusive reason for the catalytic effect of the chars in methane cracking.