褐煤的化学族组成研究方法及应用

利用化学族组成研究方法对褐煤进行分子水平研究。介绍褐煤化学族组成研究的思路,六组分的定义和划分,并建立了褐煤的六组分分离法,为褐煤生产腐植酸、褐煤转化过程的反应历程、反应机理以及反应动力学研究提供了一种新思路。     

Removal of polycyclic aromatic hydrocarbons from soil using surfactant and the white rot fungus Phanerochaete chrysosporium

The bioremediation of soil contaminated with polycyclic aromatic hydrocarbons (PAH) is often limited by a low bioavailability of the contaminants. Non‐ionic surfactants, such as Tween 80, when above their critical micelle concentration (CMC), can efficiently enhance the bioavailability of PAHs in contaminated soil by increasing solubility and dissolution rates. However, disposing of this micelle‐contaminated spent washwater can be a major problem. The aim of this study was to combine surfactant soil washing techniques using Tween 80 with the versatile lignin‐degrading system of the white rot fungus, Phanerochaete chrysosporium, to bioremediate PAH‐contaminated soil. Approximately 85% (w/w) of a total of nine PAHs in an aged (1 month) contaminated soil (total PAH concentration = 403.61 µg g⁻¹) could be solubilized in a 2.5% (w/v) Tween 80 solution at a soil/water ratio of 1:10. The washwater was then catabolized by a 3‐day‐old culture of P chrysosporium under a stationary condition. The disappearance of most PAHs tested (molecular weight ≥ 178) correlated well with their ionization potentials and 66.4% (w/w) of the total PAHs in washwater with 2.5% (w/v) Tween 80 was catabolized after 11 days of culture. The catabolism was enhanced to 86% (w/w) using a lower concentration of 0.5% (w/v) Tween 80. The initial oxidation rate of total PAHs based on the first 4 days of culture remained almost constant at approximately 1.88 µg cm⁻³day⁻¹ when the Tween 80 concentration in washwater was increased from 0.5% to 2.5% (w/v). The combination of soil washing and white rot fungus catabolization of PAH using 2.5% (w/v) Tween 80 eliminated the total PAH concentration in the contaminated soil by 56.4% (w/w) after 11 days. The results suggest that PAH‐contaminated soil may be cleansed by using a combination of surfactant soil washing and white rot fungus catabolism. © 2000 Society of Chemical Industry     

Solubilization of Neyveli lignite by oxidative degradation: A potential source of carbochemicals

The recent and possible future shortages of petroleum-derived hydrocarbons for use as starting materials for the synthesis of organic chemicals/products have stimulated renewed interest in the use of coal as raw material for chemical production. Oxidatively solubilized coal and or lignite (OSC) in alcohol is a potential substitute for value added carbo-chemicals of the future. Phenomenal increase in the solubility of lignite in organic solvent consequent on treatment with dilute nitric acid under mild conditions was considered to be an expedient pathway for its direct utilization. The primary requirements for the solubilization are generation of functional groups like free carboxyl groups and size degradation. For the desired product the reaction should also be guided in such a manner, so that the aromatic/hydroaromatic moieties of the coal/lignite are preserved. The present study aims at the selection of the required reaction parameters for the conversion of lignite to such a product. Characterization of the original lignite and the products have been done chemically and spectroscopically. FT-IR, ¹³C (solid state) and ¹H NMR spectra have shown that substances posses both aromatic and aliphatic characteristics. The dominant functional groups which contribute to the reactivity of the substances are phenolic and carboxylic acids.     

胜利褐煤超临界醇解反应行为研究

对胜利褐煤在甲醇、碱体系中的超临界反应行为进行了研究,考察了反应温度、反应时间和碱的种类分别对胜利褐煤转化率、产物收率和分布规律的影响.结果表明,反应温度显著影响褐煤的转化率和产物收率,产物主要为四氢呋喃可溶组分(占67%～85%)和甲苯可溶组分(占8%～22%);300℃时,胜利褐煤在甲醇-NaOH体系中转化率和收率最高(99%左右);反应时间显著影响褐煤的转化率和产物收率,80 min后褐煤的转化率和产物收率分别为99%和100%;反应过程中四氢呋喃可溶组分可转化为甲苯可溶组分、正己烷可溶组分和水溶性组分;碱的种类对褐煤超临界醇解转化率和产物收率有显著影响.     

PSEUDO STEADY STATE RECEDING CORE MODEL FOR DRYING WITH SHRINKAGE OF LOW RANKED COALS

A simple pseudo steady-state receding core model was used to analyze the data from this study as well as data available from the literature. The model showed that particle shrinkage during drying had little affect on the dimensionless drying curves provided that shrinkage did not cause the particle to fragment or to limit mass transfer. The model was in agreement with drying data using Mississippi lignite, Australian brown coal and Montana subituminous coal.     

Depolymerization of Turkish lignites. I. Effect of substituted phenols

A lignite (C, 67.4 wt%) was depolymerized with phenol, p-nitrophenol and o-chlorophenol using sulphuric acid as catalyst. The solubility of the lignite was enhanced by these treatments, with phenol being the most reactive reagent whereas p-nitrophenol was the least reactive. The distribution of nitro- and chloro-groups in the solubilized products was investigated by infrared spectrometry and it was found that these groups were redistributed among the pyridine- and methanol-soluble materials. It is suggested that benzene-soluble material is produced by self-depolymerization of coal or by degradation of pyridine- and methanol-soluble material.     

Studies on slag deposit formation in pulverized-coal combustors. 4. Comparison of sticking behaviour of minerals and low-temperature and ASTM high-temperature coal ash on medium carbon steel substrates

Sticking test results indicate that high-temperature melts containing iron sulphide (pyrrhotite) spread well over an oxidized mild steel surface and the adhesion forces are comparatively high even at low metal temperatures. This sulphide phase originates in the coal as pyrite. Alkalis substituted in the clay structure of both illite and montmorillonite led to the formation of lower-melting slag drops compared to kaolinite. Potassium and chlorine present in the slag drops, formed from the low-temperature ash (LTA) of a Wilcox belt Texas lignite, also led to enhanced sticking properties. The sticking behaviour of slag drops formed by the rapid melting of coal minerals, either LTA residue or synthetic mineral combinations, differed from that of the ASTM ash or synthetic metal oxide mixtures. Any tests, including the sticking test using the bulk minerals or ash composition of a specific coal, may not correlate with slag deposit formation in a utility boiler, as indicated by non-agreement between the test results with the Upper Freeport ash residues and operating experience at Keystone Generating Station.     

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.     

Changes of chemical properties of humic acids from crude and fungal transformed lignite

The development of biological processes for fossil energy utilization has received increasing attention in recent years. There are abundance of lignite resources in China and the lignite, a low-grade coal, can be transformed by a Penicillium sp. After fungal transformation, the contents of humic acid and water-soluble humic material increased from 38.6% to 55.1%, and from less than 4.0% to 28.2%, respectively. The differences in chemical properties of crude lignite humic acid (aHA), fungal transformed lignite humic acid (bHA) and water-soluble humic material from fungal transformed lignite (WS) were studied. Elemental analysis and size exclusion chromatography showed that the N content of bHA increased by 47.36% compared with aHA, and the molecular mass of bHA was smaller than aHA. And the WS with the smallest molecular mass contained most content of N. The ¹³C NMR and FT-IR spectra of aHA and bHA showed that aHA contained more aromatic structure than bHA.     

褐煤热解提质技术与多联产构想

以原褐煤质量为分类依据,根据褐煤原料的不同灰分含量,提出了不同的褐煤热解提质技术产品方案。主要介绍了国内外典型的褐煤热解提质技术,包括俄罗斯3TX(ETCh)-175、德国LR、美国LFC、中国多段回转炉、中国的BT、中国的DG等工艺。对褐煤热解技术与煤制甲烷、煤间接制油、煤制腐植酸和合成化工技术多联产进行了构想,为我国褐煤的洁净高效利用提供了参考和借鉴。     

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.     

Pyrolysis of Mississippi lignite in a fixed bed

The lignite deposits in Mississippi make up approximately 25 percent of the Gulf Coast deposit. To date, the limited number of studies on this lignite have chiefly been by Phillips Coal [1] and investigators in Mississippi [2,3]. This lignite, which is high in ash and moisture, was pyrolyzed in a 2.54 cm (1 in.) diameter fixed bed pyrolyzer under a helium atmosphere at temperatures ranging from 400°C to 950°C. The loss of volatile matter increased with increasing ultimate temperature producing weight losses 20–25% greater than the proximate analysis at 900°C. The yield of tar was found to decrease with temperature while volumetric gas production increased with the ultimate temperature. Hydrogen and carbon monoxide yields increased dramatically above 750°C. The maximum yield of gas was 375 ml/g daf lignite and was achieved at and above 815°C.     

Small angle neutron scattering study of structural aspects of nonionic surfactants (Tween 20 and Tween 80) in the presence of polyethylene glycols and triblock polymers

Small angle neutron scattering (SANS) technique has been used to study the micellar behavior of nonionic surfactants, Tween 20 and Tween 80 with additives like polyethylene glycols (PEG with molecular mass 400, 6000, and 15,000) and triblock polymers (TBPs) of varying composition. Surfactant‐additive interactions have been explained on the basis of parameters like aggregation number (N_agg), core radius (R_c), hard sphere radius (R_hs), volume fraction (ϕ) and axial ratio (b/a). The SANS analysis indicate the reduction in values of N_agg of Tween on addition of PEG additive. Shape of Tweens (3 wt %) micelles in the presence of PEG (10 wt %) is found to oblate ellipsoidal. Similarly, the shape of Tween (3 wt %) micelles is oblate ellipsoidal at low concentration of TBPs (1 wt %); however, they become spherical as the concentration of TBP increases to 10 wt %. The shape of micelles of pure TBPs also comes out to be spherical. Results reflects that at low concentration of TBP shape is controlled by surfactant (Tween 20 and Tween 80) while at high concentration of TBP shape of mixed micelle is controlled by TBP. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Pyrolysis by thermogravimetric analysis of blends of peat with coals of different characteristics and biomass

In this study, an investigation was carried out into the thermal behaviours of peat, reed, lignite, bituminous coal and blends of these with peat. The blends were prepared in 20:80, 40:60, 60:40, 80:20. The samples were pyrolysed in a TG analyzer in a nitrogen atmosphere (50 mL/min) at temperatures ranging from 25 to 900 °C. Using TG/DTG graphs, variations were investigated, which occurred in reaction intervals, percent of weight loss, peak temperatures and maximum devolatilization rate. The activation energy (E) and pre-exponential constant (A) were calculated using the Arrhenius type kinetic model.     

Chromatographic separation of alkylated depolymerized Neyveli lignite

The study of macromolecular structure of coal has been subjected to intense research. Neyveli lignite was depolymerized using phenol and phosphotungstic acid and the resultant product was subsequently alkylated. The t-butylated depolymerized lignite exhibited enhanced extractability in organic solvents. The t-butylated depolymerized lignite was fractionated into different components using column chromatography (CC). Three major compounds were isolated and were characterized by FTIR, ¹H NMR and Mass spectral techniques.     

Probing the influence of K2CO3- and Na2CO3-addition on the flash pyrolysis of a lignite and a bituminous coal with Curie-point pyrolysis techniques

The effect of K₂CO₃- or Na₂CO₃- addition on the composition of volatiles generated during the flash pyrolysis of a lignite and a medium-volatile bituminous coal was studied by means of analytical Curie-point pyrolysis mass spectrometry, g.c. and g.c.-m.s. At 358 °C no pyrolysis of the coal samples took place but there was desorption or evaporation of trapped components. Pyrolysis of the lignite occurred at a lower temperature than the medium-volatile bituminous coal, confirming that the bonds within the bituminous coal matrix are stronger as compared with the lignite. Alkali-carbonate addition suppressed the evolution of phenolic compounds originating from structures in the coal matrix with -OH and -COOH functional groups. No difference was observed between K₂CO₃ and Na₂CO₃. For the lignite the formation of o-methoxyphenol was not influenced by addition of alkali-carbonate because it is thought to derive from a structure in the lignitic coal matrix which does not contain an -OH functional group but is bonded within the coal matrix via an ether linkage. The phenolic compounds produced during flash pyrolysis of the medium-volatile bituminous coal are not reduced in abundance by the additives, indicating that this coal hardly contains hydroxyl functional groups and a major part of the oxygen is present in the form of ether linkages.     

Effect of Tween 80 on morphology and performance of poly(L‐lactic acid) ultrafiltration membranes

Poly(L‐lactic acid) (PLLA) ultrafiltration (UF) membrane was fabricated by immersion precipitation method using Tween 80 as an additive. Membrane structure was characterized by scanning electron microscopy (SEM), porosity and pore size measurement, and atomic force microscopy (AFM). Membrane performance was evaluated by pure water flux, molecular weight cut‐off, and tensile test. It was found that the addition of Tween 80 into the casting solution significantly increased the permeability and molecular weight cut‐off of membrane. Tensile test confirmed that the as‐prepared PLLA membranes exhibited acceptable mechanical properties for ultrafiltration. Further, the role of Tween 80 in the process of membrane formation was analyzed and proposed. The addition of Tween 80 favored the formation of larger pores by interrupting the polymer chain entanglement and improving the miscibility between solvent and coagulant. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44428.     

Action of aerobic microorganisms on the macromolecular fraction of lignite

Microorganisms able to utilize untreated Morwell lignite and the fraction insoluble in tetrahydrofuran (THF) as their sole carbon and energy source were isolated by enrichment from coal exposures in Victoria. Most isolates can use a variety of long-chain aliphatic and single-ring aromatic compounds but not more complex aromatic substrates, indicating that their growth on whole lignite is due to use of the low-molecular-weight compounds constituting the mobile phase and bound aliphatic moieties which can be cleaved from the macromolecular coal matrix. Organisms able to utilize THF-insoluble lignite are less abundant than those able to use whole coal. Amongst these are isolates able to utilize diaryl compounds and anthraquinones, compounds with structures analogous to components of the macromolecular matrix of lignite. Two fungal isolates, CJ2 and CJ4, were found to alter the elution profile of alkali-solubilized Morwell lignite in size-exclusion chromatography. When incubated with these fungi in growth medium, the apparent molecular weight of the lignite increased by 10000. However, when polyvalent metal ions were removed, the apparent molecular weight was lower than that of uninoculated coal, indicating attack on the macromolecular matrix of the lignite.     

原料煤对流化床气化的影响

介绍了恩德炉流化床气化所用原料褐煤的一些性质和组分,指出这些性质和组分在气化过程中所产生的不良效果,认为应选择适合恩德炉的气化用煤。     

Devolatilization of large coal particles in fluidized beds

Analysis of devolatilization of predried large coal particles in fluidized beds requires consideration of both the chemical kinetics of coal decomposition and transport processes. Models available either assume the devolatilization particle to be isothermal (whereas it may be shown that, in general, large temperature gradients may exist within the particle) or require extensive numerical integration procedures. This Paper describes a model which permits formulation of analytical and easy-to-use equations for the estimation of the devolatilization history of a large predried coal particle in a fluidized bed. The model predictions are compared with experimental data collected for Mississippi lignite. A correlation is proposed for the estimation of the total devolatilization time. The analytical solutions presented may be used with ease in coupling the devolatilization process to the other phenomena, such as drying and/or combustion of volatiles and residual char, occuring during fluidized bed combustion of coal.