Sorption charateristics of methane among various rank coals: impact of moisture

Enhanced coalbed methane (ECBM) in deep coal seams is being actively investigated around the world. Since the in situ coal seams are always saturated with water, methane sorption behavior on coal in the presence of water can help accurately assess the amount of recoverable methane. Thus, methane sorption isotherms have been measured on a high-rank anthracite, a low-volatile bituminous, a middle-volatile bituminous and a high-volatile bituminous coal with the manometric technology at 30 °C under six different moisture contents. The Dubinin–Astakhov (D–A) equation was used to fit the experimental sorption isotherm data. In all cases, the moisturized coals exhibited lower sorption capacity than the corresponding dry materials and moisture has a significant effect on CH₄ sorption capacity. The maximum sorption capacity, V ₀, displays a linear decline with the moisture content for the Changcun and Malan samples, but it is nonlinear for the other two coal samples. The net heat of CH₄ sorption, βE, is also reduced by the presence of water, but varies only slightly between a relatively small span of about 8.8 and 10.0 kJ mol^?1 for the dry samples studied, despite the difference in coal rank. In addition, the maximum sorption capacity of CH₄ in dry coals presents the typical “U-shape” trend with coal rank. Moisture has a greater impact on the sorption capacity in low-rank coals than that in high-rank coals. The mechanisms responsible for the effect of moisture on CH₄ sorption among various rank coals are also presented. The pore-blocking effect is the main influencing factor for high-rank anthracite, whereas, the competition sorption is dominant for low-rank coals.     

Active sites of the functionalized coals and carbons for oxygen reduction reaction in a fuel cell

The active sites of the coals and carbons functionalized with added nitrogen, oxygen and iron were studied for the oxygen reduction reaction (ORR) in a fuel cell. The catalysts were characterized based on the XPS, Raman, TEM, XRD and N₂ adsorption measurements. The ORR activity was promoted by the addition of iron and aluminum as the inorganic components of the ash to the ash-free brown coal. The ORR activity of the ash-components added to the ash-free brown coal was correlated to the I _D/I _G ratio (deficient carbon degree) and the pyridinic nitrogen based on the Raman and XPS analyses, respectively. The active sites of the brown coal were formed at the pyridinic nitrogen on parts of the defective carbons associated with iron on the alumina. On the other hand, for the nitrogen-doped carbons without iron, the ORR activity was related to the pyrrolic-NH, pyridinic nitrogen species and the defective carbon degree. Based on these results, the active sites of the iron-added and nitrogen-doped coals and carbons were the iron sites coordinated with the pyridinic nitrogen, while the active sites of the iron-free and nitrogen-doped carbons without iron were the pyrrolic-NH and pyridinic-NH⁺ sites of parts of the defective carbons. The difference between the active sites of the nitrogen-doped coals and carbons in the presence of iron and those in the absence of iron was discussed. These results suggested that the pyridinic N as a base site transformed into pyridinic-NH⁺ as an acid site by attack of the proton from the anode.     

Trace impurities in Canadian oil-sands,coals and petroleum products and their fate during extraction,up-grading and combustion

National energy programs for the next two decades entail increased total consumption of fossil fuels in general and, in particular of portable fuels extracted from oil sands and shales and from lower quality coals. Improved fuel-upgrading and combustion technologies are recognized to be vital for minimizing environmental degradation caused by continental and global acid-rain precipitation from fossil-fuel impurities. A further consideration, however, is the fate of those trace-element co-contaminants of acid-rain such as heavy metals, which are present at lower concentrations (10⁻⁴–10⁻⁷) but may also be of environmental significance when 10⁷ to 10⁹ tons·y⁻¹ are utilized on several continents. In this laboratory, INAA procedures have been adapted for the determination of 25–30 trace impurities in a variety of fuels and extracts including: S, V and Al, As, Ba, Br, Ca, Ce, Cl, Co, Cr, Dy, Eu, Fe, Hf, K, La, Mn, Na, Rb, Sb, Sc, Sm, Th, Ti, U. Samples were obtained of typical Canadian pumped crudes, and from several Canadian oil-sands and coal deposits (mostly bituminous and subbituminous) both in their natural states and after stages of extraction and upgrading. Also analyzed were fuels derived from them and the residues resulting from their refining and combustion. InAA of all fossil fuel extracts including light oils, viscous bitumen and such organic fluids could be performed under the same conditions as the parent substances: crude oils, oil-sands and coals, without any special sample preparation. Although no standard samples are routinely required because of the 1–2% long-term flux stability of the reactor, accuracy checks were performed periodically by reference to NBS-1632A standard coal and atomic absorption standard dilute solutions. Results obtained for the NBS coal SRM and the BAM flyash sample (1978) are also given. A wide range of trace impurities determined in the Canadian fossil fuels included some of those which are of particular significance in Canadian coals and their ashes (a STM standard ashing method). The ‘inorganic’ traces can also be grouped according to their fate during static combustion at 750°C. The research reported here was supported with funds from a Natural Sciences and Engineering Research Council of Canada Strategic energy grant (G 0017), 1978–80, “Trace Contaminants of Environmental Importance in Present and Future Fossil Fuels”.     

Investigation of pyrolysis of chinese coals using thermal analysis/mass spectrometry

TA/MS (thermal analysis coupled with mass spectrometry) was applied to the pyrolysis of Chinese coals with different ranks. A total of 13 Chinese coals were investigated. The samples were deliberately chosen to represent the 13 types of Chinese coals according to the Chinese coal classification system. The experiments were carried out in an argon atmosphere with a flow rate of 150 ml min^-1. The samples were heated from 40 up to 1200°C with a constant heating rate of 10 k min^-1. The main evolved pyrolysis products were identified through the on-line recorded mass spectra. The thermal and evolution behavior was compared between the coals. The results showed a strong thermal and evaluation behavior dependence on the coal rank. Different aliphatic fragments and also some aromatic substances, which are of environmental concern (BTX, PAHs), were found to be released depending on the different types of coal. This revised version was published online in July 2006 with corrections to the Cover Date.     

Nondestructive neutron activation analysis of rare earth elements in hot spring water samples in Kusatsu-shirane area,Japan

Hot spring water samples have been analyzed for their rare earth elements (REE's) determination by the nondestructive neutron activation method. Five REE's, La, Ce, Sm, Eu and Yb, have consequently been detected and determined with satisfactory precision. The method has been found to be simple and suited for the simultaneous analyses of several samples. To determine all the REE's, however, some pretreatment of the samples will be necessary.     

Rare earth element patterns in lake sediments as studied by neutron activation analysis

Using instrumental neutron activation analysis, the vertical distribution of La, Ce, Nd, Sm, Eu, Tb, Yb and Lu was determined in 3 well dated sedimentary cores collected from Laguna Mar Chiquita, Argentina. Validation of the methodology was done using the Soil 7 (IAEA) reference material. The REE contents vary according to core location and lithological units, depending on the proportion of fluvial terrigenous components in the lake sediments. Lithologies with higher proportion of terrigenous components show higher REE concentrations, suggesting that the dominant REE carrier phase might be a detrital mineral. There is a consistent value of about 1.2 for (La/Yb)_N and (LREE/HREE)_N ratios for all sediments at the three sites, indicating a slight LREE enrichment in relation to the average shale NASC. Ce/Ce* values are close to 1.0, meaning that Ce behaves similarly to other light REE's.     

Determination of rare earth elements in hot spring and crater lake waters by epithermal neutron activation analysis

Determination of the rare earth elements (REE's) in acidic hot spring and crater lake waters by neutron activation analysis (NAA), in which activation was performed mostly by epithermal neutrons (epithermal NAA) was investigated. Nine REE's, La, Ce, Sm, Eu, Tb, Ho, Tm, Yb and Lu, out of fourteen naturally existing REE's were determined at ppb levels with satisfactory precision. The epithermal NAA was found to be more effective in the determination of Sm, Tb, Ho and Yb than normal NAA, in which activation was performed mainly by thermal neutrons. Combined use of the epithermal and normal NAA's enabled the determination of eleven REE's, La, Ce, Sm, Eu, Gd, Tb, Dy, Ho, Tm, Yb and Lu.     

Laser-induced molecular ion formation and gas-phase ion formation from polycyclic aromatic hydrocarbons,coals and coal products detected by Fourier transform mass spectrometry

The results from the laser-ablation Fourier transform mass spectrometric examination of a variety of polyaromatic hydrocarbons (PAHs), coals and other geochemically related materials are presented. Both molecular and quasi-molecular ions have been detected from different ring-sized PAHs. A relationship between the ease of sodium-adduct ion formation and the size of the aromatic array is observed. Nevertheless, suppression of [M + Na]⁺ ion formation in PAHs can be achieved by the addition of coal. In addition, distributions of low-mass positive- and negative-ion carbon clusters (C_n ⁺, 14 ? n ? 27 and C_n, ^?, 4 ? n ? 30), high-mass positive-ion carbon clusters (C_n⁺, 60 ? n ? 260) and low relative molecular mass organic compounds (< 600 daltons) have been observed from the coals. It appears that the ease of C formation may be used as an indicator of coal rank. Irradiance conditions also influence the observed distribution of high-mass positive-ion carbon clusters. Furthermore, distributions of the high-mass positive-ion carbon clusters at different irradiances supports an earlier proposal that their formation is kinetically controlled.     

Thermogravimetric studies in prediction of coal behaviour during coal liquefaction

Different chemical and petrographical methods were earlier proposed for the prediction of coal liquefaction. Thermogravimetric studies (DTG, TG) of coals were now performed and the same coals were liquefied. A good correlation was found between ΔA _max (the main decomposition area during the maximum rate of decomposition in DTG) andSk (the degree of conversion of organic substances during coal liquefaction). ΔA _max measurement may be a good, quick and quite reliable method for the prediction of coal liquefaction, which needs to be standardized.     

溶剂萃取预处理对低阶煤大分子结构的影响

为了研究溶剂预处理对低阶煤的固有大分子结构的影响,本研究对锡林郭勒褐煤（XLL）和神府次烟煤（SFC）分别进行了四氢呋喃（THF）索氏抽提、二硫化碳/N-甲基-2-吡咯烷酮（CS₂/NMP）混合溶剂抽提及热溶处理,并对所得抽余煤进行了傅里叶红外漫反射光谱分析（DRIFT）、热重分析（TGA）、压汞法分析（MI）和溶胀度测定。结果表明,溶剂抽提导致煤大分子结构重排和再缔合。其中,THF索式抽提和CS₂/NMP混合溶剂抽提可以改变非共价键交联作用,特别是氢键作用分布,从而不同程度地松弛煤大分子结构。然而,高温溶剂热溶处理主要促进了煤大分子的共价键交联,尤其是对锡林郭勒褐煤（XLL）。所有抽取煤的溶胀都受Fickian扩散控制,且所有抽取煤的溶胀活化能都低于原煤。     

Composition of extraction products from alkylated high-sulphur coals

Products of reductive and non-reductive methylation of two high-sulphur coals (Mequinenza and Illinois No. 6) have been extracted by dichloromethane. It has been established that the efficiency of the transformation of coal to the products soluble in CH₂Cl₂ is higher for coals subjected to non-reductive methylation by the Liotta method than for those after reduction in the potassium/liquid ammonia system. The extracts and the extraction residues were subjected to elemental analysis, IR spectroscopy, and AP-TPR (Atmospheric Pressure-Temperature Programmed Reduction) measurements. It has been shown that the main species undergoing extraction by CH₂Cl₂ are aliphatic compounds or aromatic structures of low degree of condensation. The effect of the extraction on the sulphur groups in coal has been discussed.     

Two 1-D europium coordination polymers: synthesis,crystal structure and fluorescence

Two new complexes {[Eu(2, 4-DFBA)₃ · (H₂O)₂] · H₂O} _n (1) and [Eu(2-BrBA)₃ · H₂O] _n (2) (2, 4-DFBA = 2, 4-difluorobenzoate, 2-BrBA = 2-bromobenzoate) have been synthesized and characterized by single crystal X-ray diffraction. 1 has a 1-D chain structure, in which Eu(III) ions are bridged by single COO^? groups and a 2-D supramolecular network is formed by hydrogen bond interactions. In 1, each Eu(III) is eight-coordinate with six oxygens from four 2,4-DFBA ligands and two waters. 2 has a 1-D chain structure, in which Eu(III) ions are bridged by bridging-chelating-bridging COO^? groups. In 2, each Eu(III) ion is nine-coordinate with eight oxygens from five 2-BrBA ligands and one water. The two complexes exhibit intense luminescence at room temperature. The ⁵D₀ → ⁷F _j (j = 0–4) transition emissions of Eu(III) have been observed.     

Insights into sorption species of Eu(III) on γ-Al2O3 and bentonite under different pH: Studies at macro- and micro-scales

The sorption species of Eu(III) on γ-Al₂O₃ and bentonite was investigated by batch, surface complexation model (SCM), and X-ray absorption spectroscopy (XAS). The results showed that sorption edges of Eu(III) on γ-Al₂O₃ and bentonite were as expected shifted forward high pH with the increasing in Eu(III) concentration, and sorption of Eu(III) was strongly dependent on pH. In γ-Al₂O₃ system, sorption of Eu(III) was decreased above pH 8.5 at low concentration of Eu(III) because of water soluble carbonate species of Eu(III), however the decline did not appear at high concentration of Eu(III) possibly due to a offset effect of surface precipitation. Actually, the sorption species of Eu(III) on bentonite mainly referred to at least four kinds of species including ion exchange (>X₃Eu⁰) at low pH, inner-sphere complexes (>AlOEu²⁺ and >SiOEu²⁺) at neutral condition, and hydrolysis species (>SiOEu(OH) ₂ ⁰ ) at alkaline condition. Linear combination fitting (LCF) in k space testified that hydrolysis of Eu(OH)₃(s) and oxide of Eu₂O₃ species were major for Eu(III) sorption on γ-Al₂O₃, whereas Eu³⁺(aq) and hydrolysis species comprised sorption species on bentonite. Extended X-ray absorption fine structure (EXAFS) analysis further confirmed the prediction from SCM and LCF. In addition, the typical shells of Eu–Al in R range of 3.0–3.4 Å and Eu–Si at ~4.0 Å were found in radial structure functions, which was possibly identified to edge-shared bidentate of Eu(III) on Al₂O₃ and bentonite.     

Physical Properties of Superbulky Lanthanide Metallocenes: Synthesis and Extraordinary Luminescence of [EuII(CpBIG)2] (CpBIG=(4‐nBu‐C6H4)5‐Cyclopentadienyl)

The superbulky deca‐aryleuropocene [Eu(Cp^BIG)₂], Cp^BIG=(4‐nBu‐C₆H₄)₅‐cyclopentadienyl, was prepared by reaction of [Eu(dmat)₂(thf)₂], DMAT=2‐Me₂N‐α‐Me₃Si‐benzyl, with two equivalents of Cp^BIGH. Recrystallizyation from cold hexane gave the product with a surprisingly bright and efficient orange emission (45 % quantum yield). The crystal structure is isomorphic to those of [M(Cp^BIG)₂] (M=Sm, Yb, Ca, Ba) and shows the typical distortions that arise from Cp^BIG???Cp^BIG attraction as well as excessively large displacement parameter for the heavy Eu atom (U_eq=0.075). In order to gain information on the true oxidation state of the central metal in superbulky metallocenes [M(Cp^BIG)₂] (M=Sm, Eu, Yb), several physical analyses have been applied. Temperature‐dependent magnetic susceptibility data of [Yb(Cp^BIG)₂] show diamagnetism, indicating stable divalent ytterbium. Temperature‐dependent ¹⁵¹Eu Mössbauer effect spectroscopic examination of [Eu(Cp^BIG)₂] was examined over the temperature range 93–215 K and the hyperfine and dynamical properties of the Eu^II species are discussed in detail. The mean square amplitude of vibration of the Eu atom as a function of temperature was determined and compared to the value extracted from the single‐crystal X‐ray data at 203 K. The large difference in these two values was ascribed to the presence of static disorder and/or the presence of low‐frequency torsional and librational modes in [Eu(Cp^BIG)₂]. X‐ray absorbance near edge spectroscopy (XANES) showed that all three [Ln(Cp^BIG)₂] (Ln=Sm, Eu, Yb) compounds are divalent. The XANES white‐line spectra are at 8.3, 7.3, and 7.8 eV, for Sm, Eu, and Yb, respectively, lower than the Ln₂O₃ standards. No XANES temperature dependence was found from room temperature to 100 K. XANES also showed that the [Ln(Cp^BIG)₂] complexes had less trivalent impurity than a [EuI₂(thf)_x] standard. The complex [Eu(Cp^BIG)₂] shows already at room temperature strong orange photoluminescence (quantum yield: 45 %): excitation at 412 nm (24270 cm^?1) gives a symmetrical single band in the emission spectrum at 606 nm (ν_max=16495 cm^?1, FWHM: 2090 cm^?1, Stokes‐shift: 2140 cm^?1), which is assigned to a 4f⁶5d¹→4f⁷ transition of Eu^II. These remarkable values compare well to those for Eu^II‐doped ionic host lattices and are likely caused by the rigidity of the [Eu(Cp^BIG)₂] complex. Sharp emission signals, typical for Eu^III, are not visible.     

Polarographic study of Eu(III)-succinate-ethylenediamine and Eu(III)-malonate-ethylenediamine mixed systems

The mixed complexes of Eu(III) with succinate (succ^2?) and malonate (mal^2?) and ethylenediamine (en) have been studied polarographically at 25°C and at constant ionic strength, μ = 0.1 (NaNO₃) and pH 6. The reduction of the complexes in each case is quasi-reversible and diffusion-controlled. In each system three mixed complexes are formed, viz. [Eu(succ)(en)]⁺, [Eu(succ)(en)2]⁺ and [Eu(succ)₂(en)]^? with stability constants log β₁₁ = 9.2, log β₁₂ = 17.5 and log β₂₁ = 11.7; and [Eu(mal)(en)]⁺, [Eu(mal)₂(en)₂]^? and [Eu(mal)₃(en)]^3? with stability constants log β₁₁ = 11.4, log β₂₂ = 19.08 and log β₃₁ = 13.5 respectively.     

Chiral Sensing Using Circularly Polarized Luminescence of Bis(phenanthroline dicarboxylic acid) EuIII Complex Induced by Allosteric‐type Interaction with Amino Acid Molecules

[Eu(pda)₂]^? and [Eu(bda)₂]^? (pda=1,10‐phenanthroline‐2, 9‐dicarboxylic acid; bda=2,2′ bipyridine 5,5′‐dicarboxylic acid) have an achiral D_2d structure in crystals. These complexes exhibit circularly polarized luminescence (CPL) in water containing chiral amino acids. In this work, induced CPL of [Eu(pda)₂]^? and [Eu(bda)₂]^? in water solutions containing a mixture of d ‐ and l ‐ amino acids were examined. Plots of g_lum values of the induced CPL as a function of mol‐fraction of l ‐ and d ‐ arginine reveal that [Eu(pda)₂]^? favors homo‐association ([Eu(pda)₂]^?‐(l ‐arginine)₂ or [Eu(pda)₂]^?‐(d ‐arginine)₂) over hetero‐association {[Eu(pda)₂]^?‐(l ‐arginine)?(d ‐arginine)}. This suggests that association of an arginine molecule induces a structural change in [Eu(pda)₂]^? to promote chiral selective association to another arginine, i.e., homo‐allosteric association. On the other hand, the system of [Eu(pda)₂]^? with histidine favors hetero‐allosteric association over homo‐association. No allosteric effect is recognized in CPL from [Eu(bda)₂]^?.     

Experimental study on interaction and kinetic characteristics during combustion of blended coals

The combustion behaviors and kinetic parameters of three parent coals (A1, A2, and A3) and their blends (A1/A2 and A2/A3) have been evaluated under oxidizing atmosphere (O₂ and N₂ mixtures), using a non-isothermal thermo-gravimetric analyzer. The aim of this study is to investigate the interaction between the blended components during the process of co-combustion, and the effects of blending ratio and oxygen concentration (10, 15, and 21%) on combustion performance of blended coals. When high reactivity and low reactivity coals are co-combusted, double peaks are observed in the DTG curves, and significant interaction occurs in the temperature range between the two peaks (T _p1 and T _p2). The activation energies obtained by Coats–Redfern method indicate that the activation energies of blended coals are lower than that of parent coals. The combustibility index S is used to evaluate the combustion performance of blended coals, and the results show the non-additive effects of the combustion characteristics of blended coals. The increased oxygen concentration results in a significant improvement of combustion performance of blended coals. In addition, as the blending ratio of high reactivity coal is increased, the oxygen can greatly enhance the combustion stability of blended coals.     

Differential Pulse Voltammetric Study of Complexes of Rare Earth Ion(Eu3+) with Glutarate and 1,2-Diminopropane

Abstract

The mixed complexes of Eu (III) with glutarate (Gluta) and 1,2-diaminopropane (DMPA) have been studied at 25°C, μ=0.12(NaClO₄) by differential pulse voltammetry(DPV). The reduction process in each case appears to be quasi-reversible and diffusion-controlled. The stability constants have been measured by Schaap and McMasters′ method. The stability constants of three mixed complexes formed are logβ₁₁=7. 414 for [Eu(Gluta) (DMPA)]⁺, logβ₂₁ = 8. 506 for [Eu(Gluta)₂ (DMPA)]^? and logβ₁₂ = 9. 984 for [Eu(Gluta) (DMPA)₂]⁺.     

On Acidic Organodiphosphorus Extractants. Part V. Extraction Dependency of Trivalent Europium on the Dielectric Constant of the Organic Phase

Abstract

The extraction of Eu(III) has been carried out from a 1 M (H,Na)Clo₄ solution into different organic solvents at constant total concentration (6.67 × 10^?3 M) of the extractant, di-n-butyl-ethane-(l,2)-diphosphonic acid (H₂B₂-EDP). The distribution coefficient of Eu(III) is influenced quite appreciably by the nature of the organic solvent. We observe that the distribution coefficient can vary by a factor of 10⁶ for two solvents such as chloroform and ieo-octane. The experimental results are compared with those of Dréze¹, who used di-n-butyl-phosphoric acid (HDBP) for the extraction of Eu(lII) into different organic solvents. If we assume that H₂-B₂-EDP remains monomer for a total concentration of 6.67 × 10^?3 M in the solvents used², then we may conclude that the extraction of Eu(III) by the associated HDBP or the monomer H₂B₂EDP is influenced in the same manner in the solvents used.     

应用TG-FTIR联用研究催化剂对煤热解的影响

用TG-FTIR联用技术研究了碱金属、碱土金属和过渡金属对宝日希勒褐煤和包头烟煤热解的催化作用和挥发分析出的影响。结果表明，各种催化剂对褐煤和烟煤热解的催化效果分别为Ni>Fe~Ca>K和Ca~Fe>Ni>K，K2CO3对煤的热解没有明显的催化作用。催化剂使褐煤和烟煤热解转化率增加的最大值分别为10.1％和6.4％。烟煤热解生成的CH4比褐煤的多，不同的催化剂使煤热解挥发产物CO2、H2O、CH4和CO增加的幅度不一样，催化效果与温度和煤的变质程度有关。