STEAM GASIFICATION OF BALMER COAL IN THE PRESENCE OF LIGNITE ASH

Steam gasification of blends prepared from Balraer coal and the ash from combustion of Onakawana lignite was performed in a fixed bed reactor. The blends were prepared by co-slurrying followed by drying. In the presence of 20 wt % ash the gasification rate doubled at 830° and 930°C. Direct blending of coal and lignite resulted In an overall increase in carbon conversion at 830°C but had no effect at 930°C.     

EFFECT OF SOLVOLYTIC EXTRACTION AND PYROLYSIS PRETREATMENTS ON THE TOEMPRATURE STEAM GASIFICATION REACTTVITY OF COAL AND REDUCTION OF TAR FORMATION IN PRODUCT GASES

ABSTRACT

Pre-extraction of Talcher coal ( a bituminous coal) in anthracene oil was found to be a beneficial treatment for enhancing the reactivity for steam gasification of coal. Similarly, anthracene oil followed by liquid paraffin extraction of coal was also found to be a-better pretreatment for the steam gasification of coal. Anthracene oil extraction at 270°Cand steaming of coal at 650°C had almost equal effect on steam gasification of coal. Pyrolysis in steam of pre-extracted coals was found to further enhance the reactivity of coal for steam gasification. The studies were further confirmed by carrying out thermogravimetric analysis of pretreated coals in steam atmosphere. Degree of cross-linking in pretreated coals was studied by measurement of swelling of coal in quinoline. The formation of tar in gaseous product was reduced as a result of pre-extraction and steam pyrolysis of coal prior to their gasification in steam.     

THERMAL ANALYSIS OF DIFFERENT FOSSIL FUELS

ABSTRACT

In this study DTA and TGA were applied to some fossil fuels. Peat, lignite, bituminous coal, anthracite, oil shale and asphaltite were heated at a constant 15 °C/min up to 1000 °C under nitrogen atmosphere. The DTG curves of the samples were derived using the TG curves. The results are compared and discussed.     

LIQUEFACTION OF BEYPAZARI LIGNITE USING NiCl2-KCl-LiCl CATALYSTS. 1. DIFFERENCE IN SOLID AND MOLTEN SALT CATALYSIS

ABSTRACT

Liquefaction of Beypazan lignite in tetralin using NiCl₂-KCl-LiCl (14:36:50 molar percentages) as catalyst was investigated. Effects of the catalyst/lignite ratio and temperature were determined in experiments done at 275°C, 300°C and 360°C. Liquid products were separated into oils, asphaltenes and asphaltols by a solvent extraction method. Yield of liquefaction increased with temperature in all experiments, the highest yield was observed in experiments performed at the eutectic temperature of the catalyst mixture. The highest yields of oils were 20% and 30% with a catalyst/coal ratio of 0.5 at 275°C and 300°C, respectively. The activity of the catalyst increased in experiments in which the catalyst was molten. The yield of asphaltenes were not affected with increases in the catalyst/coal ratio in the experiments done at 275°C or 300°C in which the catalyst mixtures were in solid state. Asphaltene yields decreased from 25% to less than 5% with increasing values of catalyst/coal ratio and the asphaltol yields remained constant at 10% between catalyst/coal ratios of 0.25 and 1.00 and suddenly increased to 30% and 40% for catalyst/coal ratios of 1.50 and 2.00, respectively, at 360°C. The molecular weights of the oils decreased from 340 to a minimum value of 245 as the catalyst/coal ratio was increased from 0 to 1.00 in experiments done at 360°C where the catalyst was molten. As the catalyst/coal ratio was further increased from 1.00 to 2.00 the molecular weight increased to 310.It seemed that the N1Cl₂-KCl-LiCl catalyst mixture in all catalyst/coal ratios was more efficient in molten phase than it was used as a solid mixture.     

THERMAL REACTIVITIES OF SOME TURKISH LIGNITES

Abstract

A DTA study has been made to investigate the thermal reactivities of five Turkish lignites (Elbistan, Ilgin, Karliova, Xangal, Yatagan) in an air atmosphere. The coal samples exhibited thermal reactivity at temperatures starting from 20 °C and continuing up to 671 °C. Endothermic peaks were observed at the lower end of the temperature range, the highest endothermic peak temperature being 146°C for Elbistan lignite. Exothermic peaks appeared at around 260, 360 and 600 °C. These temperatures are considered to signify the release and combustion of single benzene ring structures and combustion of condensed aromatic rings respectively. Corresponding stages are observed in the TGA traces. After correcting for differences in methodology, the overall heat effects measured by DTA are within greater than 90% of the calorific values of the coal samples determined by bomb calorimetry.     

HYDROLIQUEFACTION OF TEXAS LIGNITE IN COAL- AND PETROLEUM-DERIVED SLURRY OILS

ABSTRACT

Hydroliquefaction of Texas lignite (68.5%. C daf) was conducted in a batch autoclave under hydrogen in a coal–derived slurry oil at 90 bar initial pressure for temperatures of 380–460^° C and residence time of 15–60 minutes, or a vacuum distillate from petroleum at 435^° C for 60 minutes and initial H₂–pressure of 60–150 bar, or a vacuum residue from the same petroleum at 435 and 460^° C for 60 minutes and initial H₂–pressure of 90–150 bar or tetralin at 435^°C, 60 minutes and 90 bar initial H₂–pressure. Red mud plus sodium sulfide were added as a catalyst for all experiments. Lignite conversion ranged from 50 to 83%. The products were separated into gases, residue, asphaltenes, oils B,P. above 200^° C, oils B.P. below 200^° C. Total liquid products from coal reached 57% in coal-derived slurry-oil, 56% in vacuum distillate and 64% in vacuum residue at optimum conditions with 32% of product oil B.P. below 200^° C in vacuum distillate and 24% in vacuum residue. When coprocessing lignite with vacuum residue at 120 bar initial pressure, 435^°C and 60 minutes residence time the total mass balance presented an oil yield of 73%. with 32% boiling below 200^°C.     

EFFECTS OF COAL SURFACE CHARGE ON THE ADSORPTION AND GASIFICATION ACTIVITIES OF CALCIUM AND POTASSIUM

ABSTRACT

The electrokinetic properties of lignite, subbituminous and bituminous coal particles and their demineralized derivatives have been measured as a function of pH. Compared to the raw coals, demineTalization generally increased the net negative surface charge densities on the coals. Calcium or potassium adsorption (by ion-exchange) onto the demineralized coals was strongly dependent on pH and the surface charge properties of the coals. Metals uptake was very low (0,1-0.4% wt.) in strongly acidic media (～pHl) but increased dramatically as the net negative charge on the coals was increased by increasing the pHs of the coal suspensions to pH 6 or 10. The reactivities of the calcium- ot potassium-loaded chars in carbon dioxide at 800^°C were similarly dependent upon the pHs at which the catalysts were ion-exchanged onto the coals. For the calcium-containing chars, the reactivities increased in the order: pH 6 > “pH 10 > pH 1 while the variation of the gasification rates with potassium loading pH was: pH 6 ～ pH 10 ? pH I. These findings are attributed to differences in the extent of electrostatic interaction between the calcium or potassium ions and the charged coal surface during catalyst loading from solution.     

DIRECT HYDROGENATION OF A SPANISH LOW RANK COAL. THE EFFECT OF PROCESS VARIABLES

ABSTRACT

The effect of operating conditions on the liquefaction behaviour of a Spanish lignite was studied using a 250 ml stirred autoclave, and the following operating conditions (except otherwise specified): 400 °C, 1 hour, 3.5 MPa initial (cold) H₂ pressure, 400 rpm and 40 g/10 g tetralin/coal charge. The liquefaction products were fractionated into oils, asphaltenes, preasphaltenes and solid residue using pentane, toluene and THF as extractive solvents

The influence of temperature was explored in the 300–475 °C range, observing little further improvement in liquefaction yields over 400 °C, and retrogressive reactions over 450 °C. The effect of time was studied from 0 to 180 minutes and was concluded that 1 hour is an appropriate period for liquefying a black lignite, since there is little further conversion for longer times. The influence of pressure and gas type was studied using 0, 3.5 and 7.0 MPa initial (cold) pressure of H₂ and of N₂, and the effect of stirring using 0 and 400 rpm. Little influence of these variables was observed, which is attributed to the strong H-donor solvent, high solvent/coal ratio and long reaction time used.     

SUPERCRITICAL EXTRACTION AND DESULPHURIZATION OF BEYPAZARI LIGNITE BY ETHYL ALCOHOL/NaOH TREATMENT 1. EFFECT OF ETHYL ALCOHOL/COAL RATIO AND NaOH

ABSTRACT

The solubilization and desulphurization of Beypazari lignite with supercritical ethyl alcohol/NaOH was investigated. Supercritical experiments of 60?minutes were done in microreactors of 15?ml at 245°C by changing the ethyl alcohol/coal ratio from 3 to 20 under a nitrogen atmosphere. As the ethyl alcohol/coal ratio was increased the yield of solubilization and desulphurization also increased. Higher yields of extraction in the case of ethyl alcohol/NaOH experiments may be due to the fact that alcohols can transfer hydrogen more easily in the presence of bases. The average molecular weights of liquid products obtained in experiments with ethylalcohol/coal ratios of 3,6 and 20 were 430,450 and 465, respectively. In experiments with ethylalcohol/NaOH system as the ethylalcohol/coal ratio was increased from 3 to 20 the sulphur content of the coal decreased to 0·75%. In experiments with greater ethylalcohol/coal ratios mercaptane type sulphur chemicals have been extracted,disulphides were missing in these extracts.     

KINETICS OF CORN COB CHAR GASIFICATION IN CARBON DIOXIDE

ABSTRACT

The Reactivity of corn cob char in CO₂ has been studied on a thermogravimetric balance to develop a rate equation for the design of biomass gasifiers operating on corn cob char. Experiments in the range of 650-1000^°C were conducted with cylindrical shaped pellets of 1 cm diameter having L/D=l. The average porosity of the pellets was 0.5. It was observed that the rate of the CO₂/char reaction decreased with increase in temperature from 650-750^°C and then increased with temperature upto 1000^°C.

The data obtained at temperatures 750^°C and above has been used to determine a rate equation for char gasification. It has been found that the reaction proceeds according to the Sharp Interface Model (SIM) with a first order chemical reaction as the rate controlling step. The activation energy is found to be 40 Kcal/mole with frequency factor being 1.2 × 10⁷ mm/sec. Analysis of the data obtained for the decreasing reaction rate regime (650-750^°C) indicates that the change in the ash structure result in this kind of behavior.     

化学链气化过程中昭通褐煤灰对锰矿石载氧体的影响

为探究化学链气化过程中煤灰及其组分对锰矿石载氧体的影响及作用机理,制备了昭通褐煤煤灰,以煤灰中主要组分Fe₂O₃、CaO和MgO等氧化物颗粒配制单一及混合组分的模拟煤灰,在高温流化床反应器中以水蒸气为气化剂进行了系列研究。结果表明：添加5%(质量分数)褐煤煤灰后,合成气产量升高而碳转化率降低,且随着煤灰添加量的继续增多,合成气产量呈先降低后升高趋势,而碳转化率则呈现先升高后降低趋势,在煤灰添加质量分数为15%时,出现最高的碳转化率79.7%和最低的合成气产量0.702 L。Fe₂O₃组分明显提高了碳转化率和合成气产量;CaO与Mn₂O₃高温反应生成了Ca₂Mn₂O₅,提高了载氧体选择性,使得合成气产量增大;MgO显著降低了碳转化率和合成气产量。双组分及MgO-Fe₂O₃-CaO三组分模拟煤灰的研究发现,MgO对气化反应进程抑制作用强于Fe₂O₃和CaO的促进作用,相比于Fe₂O₃-MgO双组分模拟煤灰,CaO-MgO模拟煤灰对载氧体气化活性的抑制作用影响最大。     

MINERALOGICAL COMPOSITION OF NIGERIAN COALS

ABSTRACT

The results of a study aimed at evaluating the mineral constituents of four Nigerian coals (a Iignite, a subbituminous and two high volatile bituminous coals) are reported in this paper. The low temperature ash (LTA) obtained from the coals was analyzed using scanning electron microscopy (SEM) and x-ray diffraction (XRD).

X-ray fluorescence spectra obtained from SEM showed the presence of silica, alumina, iron- and titanium-containing minerals in smaller amounts, and exchangeable cations (Ca, K, Na) in the four coals. The concentration of exchangeable cations and alumina was found to increase with increase in coal rank. X-ray diffraction results indicated the presence of quartz, kaolinite and pyrite in all four coals; calcite and marcasite only in the lignite; and anorthite only in the bituminous coal; albite and gypsum in all except lignite; and montmorillonite in the low rank coals only.     

PRODUCTS FROM FLASH PYROLYSIS OF A TURKISH LIGNITE IN A FREE-FALL REACTOR UNDER VACUUM

ABSTRACT

Flash pyrolysis of a Turkish lignite under vacuum in a free-fall reactor was examined at a temperature range of 400 - 800 °C. Gaseous products were analysed with an on-line GC equipped with a manuel injection valve. Solvent fractionation was applied to the liquid product to separate preasphaltenes, asphaltenes and oils fractions. Two particle distributions of the lignite were used: ?0.315+0.2 mm and ?0.1 mm. The liquid yield increased with temperature up to 650 °C and, thereafter decreased for the larger particles. The maximum liquid yield, excluding pyroltic water, was found to be 8 % wt (dal) at 650 °C. In the case of the smaller particles the liquid yield increased steadily with temperature and the yield of liquid, excluding pyrolytic water, was 5.9 % wt (da) at 850 °C. The gaseous product yield also increased with temperature for both size fractions, and CO and CO₂ in the gaseous products were present in large amounts.     

THE EFFECT OF ADDED HETEROGENEOUS CATALYSTS ON LOW-SEVERITY COAL LIQUEFACTION

ABSTRACT

Liquefaction data in the presence and absence of added catalysts were obtained for two coals from the Argonne premium Sample Bank (Beulah-Zap lignite and Utah Blind Canyon high volatile bituminous). Experiments were carried out in tubing bomb microautoclave batch reactors over a broad temperature range (310 to 425 ^°C), and THF and hexane conversion profiles were measured at residence times of 5, 10, 15, and 30 minutes in order to elucidate the effect of both time and temperature at reaction conditions ranging from low to high severity. All runs were carried out in a non-donor vehicle (l-methylnaphthalene) using powdered presulfided Shell 324 as the catalyst.

The results generally reflect the expected trends for catalyst on coal conversion, in that the primary influence of catalyst was found to be in terms of promoting conversion of coal to hexane solubles. A hexane selectivity parameter was developed and utilized to provide insight into the role and effect of catalyst.     

DESULPHURIZATION OF A TURKISH LIGNITE BY PYROLYSIS COMPARISION OF SLOW AND FLASH PYROLYSIS

ABSTRACT

To observe the effect of the heating rate on the desulphurization. Bolu- Mengen lignite was desulphurized in the temperature range of 450-750 °C using flash and slow pyrolysis methods. A reduction of 57.6 % and 34.2 % In the total sulphur was obtained for the slow and flash pyrolysis at a pyrolysis temperature of 750 °C. respectively. It was observed that the flash pyrolysis is shifted toward higher temperatures with respect to the slow pyrolysis. The flash pyrolysis having high thermal efficiency has a potential as a desulphurization process.     

COPROCESSING OF COAL WITH HEAVY PETROLEUM CRUDES AND RESIDUA

ABSTRACT

This work investigates the coprocessing of coal in six different heavy petroleum crudes and residua. Coprocessing reactions of coal and the petroleum solvents are performed under three sets of constant reaction conditions, yielding informative comparative data for processing applications. Definitive comparisons of coal reactivity and solvolysis in the petroleum solvents have been obtained using solvent fractionation which provides a measure of the degree of upgrading achieved by the liquefied coal. Regressive reactions and low coal conversions are observed in coprocessing reactions in N₂ at 400^°C. Higher conversions and a reduction in regressive reactions are observed in H₂ at 400^°C. Catalytic hydrotreatment and higher temperature, 425^°C, result in increased coal conversion and a net production of pentane soluble materials. The amount of product fractions obtained from the upgrading of the coal alone is calculated. The effect of reaction temperature using different solvents and reaction conditions on the product slate is also examined.     

CHARACTERIZATION OF COAL CHARS FROM A FLASH PYROLYSIS PROCESS BY CROSS POLARIZATION/MAGIC ANGLE SPINNING 13C NMR

ABSTRACT

Chars from the Illinois Springfield (No. 5) Coal are prepared by flash pyrolysis at progressively higher charring temperatures. The results of a study of these chars by ¹³C NMR with CP/MAS indicate that the initial stage of heating (300^°C) produces a char with aromatic carbon fraction (f_ar) of 68%, and successive heating gives chars with f_ar of 70% (400^°C), 73% (500^°C), 89% (600^°C), 95% (700^°C), and 96% (800^°C). However, the actual amount of aromatic and aliphatic carbon in the char can be calculated by using the NMR measurements, the organic carbon content of the char, and the weight of the char. The calculated values show that the amount of aromatic carbon in char remains relatively constant at each temperature, but the amount of aliphatic carbon in char is reduced during higher temperature charring. At 600^°C, both a large reduction of the aliphatic carbon content and a maximum weight loss occur. Evidently, the aliphatic-bond carbon in coal is the principal source of volatiles derived from coal. The apparent increase in aromaticity (f_ar) of the char heated to progressively higher temperatures is due to the loss of aliphatic-bond moieties and reduction in volume of materials.     

THE PROPERTIES OF WATER LAYERS ON COAL SURFACES

ABSTRACT

The results of programmed thermodesorption investigations of water from coal surfaces are presented and correlated with the measurements of water adsorption and desorption from the gaseous phase at a temperature of 20^°C. From the data obtained, the activation energies of water molecules were calculated and possible structures of water adsorbed layers on the coal surfaces were suggested. On the basis of the DTA curve, the water adsorption heat on the coal surfaces 20^°C was calculated and presented in the form of dependence on water adsorption value from the gaseous phase.     

GASIFICATION KINETICS OF RESIDUAL COAL PRODUCED FROM SOLVENT EXTRACTION WITH N - METHYLPYRROLIDONE

Abstract

A low-temperature, coal-extraction technique utilizing the solvent N-methyl-2-pyrrolidone has been shown to enhance significantly the rate of gasification of the residual, unextracted portion of the coal as compared to that of the ray coal. Five coal/residue pairs were subjected to gasification in a carbon dioxide atmosphere at temperatures of 1200-1500'K and atmospheric pressure. In all cases, the activation energy (as described by an Arrhenius-type relationship) of the residue was found to be lower than that of the raw coal. In addition, over the temperature range studied, the residues exhibited rate constants as much as four times larger than those for the raw coals. A trend vas found to exist between the extent of extraction and the ratio of the activation energies of the residue and raw coal. It is postulated that this behavior is a manifestation of a complex combination of catalytic and surface area effects. The technique of solvent extraction followed by gasification of the residue may constitute an attractive option for the production of clean fuels from coal.