Predicting the classification characteristics of coal. Part 3. Gross calorific value of dry,ash-free coal

For 63 samples of Ukrainian, Russian, and imported coal, equations for predicting the gross calorific value Q_s^daf on the basis of the following coal characteristics are developed: W^a, O_d^daf, Q_s^af, and C_ar. The error is within the standard tolerances (σ ≤ 0.3 MJ/kg). With sufficient accuracy, Q_s^daf may be predicted from equations based on petrographic characteristics such as the vitrinite reflectance, the content of liptinitegroup minerals, and the sum of lean macerals (I + 2Sv/3). In these equations, the coefficients correspond to the heat of combustion of the vitrinite components at different metamorphic stages, the liptinite, and the lean macerals.     

IR Spectroscopy in Rank and Group Assignment of Coal

The possibility of express determination of the characteristics V _IR ^daf , R_{o, IR}, y_IR, ΣLC_IR, and A _IR ^d used in the ranking of coal on the basis of IR spectroscopy is assessed for a specific example: Kuznetsk coals of different maceral composition and metamorphic development. The IR characteristics are compared with values obtained by standard methods (V^daf, R_{o, r, y}, ΣLC, and A^d).     

Composition and properties of coals from the Yurty coal occurrence

Coals from the Yurty coal occurrence were studied. It was found that the samples were brown non-coking coals with low sulfur contents (to 1%) and high yields of volatile substances (V ^daf to 53.4%). The high heat value of coals Q _s ^daf was 20.6–27.7 MJ/kg. The humic acid content varied from 5.45 to 77.62%. The mineral matter mainly consisted of kaolinite, α-quartz, and microcline. The concentration of toxic elements did not reach hazardous values.     

Predicting the classification characteristics of coal. Part 2. Maximum moisture content

Analysis of 63 samples of coal concentrates (from Ukraine, Russia, the United States, Canada, Australia, and Poland) currently employed at Ukrainian coke plants indicates that the prediction of the maximum moisture content of coal may expediently be based on R _o and Q _s ^daf , determined, respectively, in plant laboratories and in power-station laboratories. The maximum moisture content of metamorphically distinct coals does not depend on their ash content (in the range 3.7–35.3%) nor on the chemical composition of the ash, expressed by the basicity index B _b (in the range 1.24–27.18) and the base/acid ratio I _b (in the range 0.198–1.832). Although the oxidation of coal also increases the maximum moisture content, this change is less than the error in its determination (0.5%). The oxidation of practically 30% of the coal’s organic mass increases the maximum moisture content by no more than 0.4%     

Effects of co-ion initial concentration ratio on removal of Pb<Superscript>2+</Superscript> from aqueous solution by modified sugarcane bagasse

A modified sugarcane bagasse (SCB) fixed bed column was used to remove Pb²⁺ from aqueous solution. To determine the optimal condition for Pb²⁺ separation, Ca²⁺ was chosen as the model interfering ion, and effects of Ca²⁺ and Pb²⁺ initial concentration ratio (C ₀ ^Ca : C ₀ ^Pb ) on the adsorption of Pb²⁺ were investigated. Results showed that adsorption amount ratio of Ca²⁺ and Pb²⁺ (q _e ^Ca : q _e ^Pb ) had a good linear relationship with C ₀ ^Ca : C ₀ ^Pb . Mass ratio of Pb²⁺ absorbed on the modified SCB was higher than 95% at C ₀ ^Ca : C ₀ ^Pb <1.95, illustrating that Pb²⁺ could be selectively removed from aqueous solution. To verify that, simulated waste water containing co-ions of K⁺, Na⁺, Cd²⁺ and Ca²⁺ was treated, and results showed that the equilibrium amount of Pb²⁺, K⁺, Na⁺, Cd²⁺ and Ca²⁺ adsorbed was 134.14, 0.083, 0.058, 1.28, and 1.28mg g^?1, respectively, demonstrating that the modified SCB could be used to remove Pb²⁺ from aqueous solution in the investigated range.     

Structure of a biologically active binuclear palladium complex in the compound bis(bis[(μ<Subscript>2</Subscript>-2-chloroethylammonium) (1,10-phenanthroline)-palladium(I)]) · octanitrates · dihydrates

The structure of a biologically active binuclear palladium complex, namely, [(1,10-phenanthroline) Pd(μ₂-2-chloroethylammonium) ₂ ⁴⁺ · 4NO ₃ ^? · H₂O, has been determined using X-ray diffraction analysis. The compound crystallizes in the monoclinic system, space group of symmetry Cc, with the unit cell parameters a = 24.527(3) Å, b = 13.097(1) Å, c = 22.651(3) Å, β = 104.23(1)°, V = 7052(2) ų, Z = 8, and ρ = 1.88 g/cm³. The final discrepancy factor is R1 = 0.0316 for 15581 symmetrically nonequivalent reflections with I ≥ 2σ(I), wR2 = 0.0513, and GooF = 1.047. The palladium atoms reside in the oxidation state of 1+, which is rarely encountered in organometallic compounds. The asymmetric part of the unit cell contains two chemically equivalent but crystallographically independent positively charged binuclear palladium complexes, eight NO ₃ ^? anions, and two water molecules. The π-π stacking interaction between the nearest 1,10-phenanthroline rings of the neighboring layers takes place. Moreover, the interlayer and intralayer interactions occur through electrostatic interaction forces and a complex three-dimensional system of hydrogen bonds, which are formed by water molecules and N ₃ ⁺ groups.     

Assessing the technological value of coal in coking

Coking coal of the same rank from different countries and fields may be distinguished in terms of use value by rating on the basis of seven technological and petrographic characteristics that determine the coke yield and properties: the ash content A^d; the total sulfur content S_t^d; the yield of volatiles V^daf; the plastic-layer thickness y; the vitrinite reflection coefficient R_o; the content of vitrinite-group macerals Vt; and the basicity index B_b. A range of values and a rating (on a scale from 1 to 10) are established for each of these parameters. Each rating corresponds to a particular score (from 0.1 to 1.0). Ranges of A^d, S_t^d, Vt, and B_b are established for the whole metamorphic series, while ranges of V^daf, y, and R_o are established for individual ranks and groups of ranks. Altogether, 105 coking coals from Ukraine, Russia, the United States, Australia, and Canada that are used at Ukrainian coke plants are investigated. The range of rating scores and their mean values are determined for individual coal ranks and groups. As an example, three bituminous coals from Ukraine, the United States, and Australia are compared by the proposed method. This method permits objective assessment of the technological value of coal within a single rank and the selection of the best purchase option.     

Properties of the solid thermolysis products of brown coal impregnated with an alkali

The mechanism of formation of a porous active carbon framework is considered, and the properties of the solid thermolysis products of brown coal (Aleksandriisk deposit, Ukraine) with potassium hydroxide are studied. The yields of the solid thermolysis products (Y _STP, %) and potassium humates, the rate of the interaction of the solid thermolysis products with KOH at 700–900°C, the specific surface areas (S _BET, m²/g), the adsorption capacities for methylene blue (A _MB, mg/g) and iodine (A _I, mg/g), and the specific activities of surface areas A _MB ^′ = A _MB/S _BET and A _I ^′ = A _I/S _BET (mg/m²) are determined under variation of the KOH/coal ratio (R _KOH < 18 mol/kg) and temperature (110–900°C).     

Structure of a biologically active binuclear palladium complex in the compound (bis[(μ<Subscript>2</Subscript>-2-chloroethylammonium)(1,10-phenanthroline)-palladium(I)]) · tetranitrates · hydrate

The structure of a biologically active palladium complex [(1,10-phenanthroline)Pd(μ₂-2-chloroethylammoniu)] ₂ ⁴⁺ · 4NO ₃ ^? · H₂O has been determined from the diffractometric data. The compound crystallizes in the triclinic crystal system, space group of symmetry P \(\bar 1\), with the unit cell parameters a = 12.8352(8) Å, b = 14.4040(8) Å, c = 12.1668(9) Å, α = 116.16(1)°, β = 115.72(1)°, γ = 91.09(1)°, V = 1756.3 ų, Z = 2, and ρ = 1.892 g/cm³. The final reliability factor is R ₁ = 0.0351 for 7357 nonequivalent reflections with I ≥ 2σ(I), wR ₂ = 0.0970, and S = 1.044. The asymmetric part of the unit cell contains one positively charged binuclear palladium complex, four NO ₃ ^?1 anions, and one water molecule. The nanocomplexes are involved in the stacking π-π interaction by pairs: each complex forms a stacking with only one adjacent complex. The interaction between layers and inside each layer occurs through the van der Waals interactions and a three-dimensional system of hydrogen bonds, which are formed by the N ₃ ⁺ groups and water molecules.     

Oxidation of coke with petroleum-based coking additives

The properties of coking batch may be stabilized by means of DK coking additive based on the products of petroleum pyrolysis, characterized by low ash content (A^d = 0.4%), high sulfur content (S_t^d= 4.1%), and high yield of volatiles (V^daf = 17.2%) relative to coal concentrates. Individual coking of DK coking additive yields a product (particle size >40 mm) with postreactive strength CSR = 77–79%, reactivity CRI = 18–22%, and density 1200–1400 kg/m³. Differential scanning calorimetry of experimental coke samples reveals six stages in their heat treatment in air: preliminary heating, intense oxidation, gasification of carbon, surface combustion of the gaseous products, their flare combustion, and oxidation of the residue. The use of DK coking additive in the coking batch shifts the oxidation process to higher temperatures and ensures the largest interval of heat liberation at elevated heating rate, with up to 50% DK additive. With increase in the content of DK additive from 30 to 50%, the activation energy is increased by 4.56 kJ/mol for each additional 10%. In that case, the supply of atmospheric oxygen to the combustion zone must be improved     

Properties of adsorbents prepared by the alkali activation of Aleksandriisk brown coal

Highly microporous adsorbents (micropore fraction of ～70%) were prepared by the alkali activation-thermolysis (800°C, 1 h) of brown coal (C ^daf = 70.4%) in the presence of potassium hydroxide at the KOH/coal weight ratio R _KOH ≤ 2.0 g/g. The dependences of the specific surface areas and adsorption capacities of the adsorbents for methylene blue (A_MB, mg/g), iodine (A_I, mg/g), and hydrogen (\(A_{H_2 } \), wt %) on R _KOH were determined. The adsorbents obtained at R _KOH ≥ 1.0 g/g exhibited developed specific surface areas and good adsorption characteristics (A_I = 1000–1200 mg/g, A_MB = 200–250 mg/g, and \(A_{H_2 } \) ≤ 3.16 wt % at 0.33 MPa). The high capacity for hydrogen allowed us to consider brown coal adsorbents as promising materials for use as hydrogen accumulators.     

A Comprehensive Study on the Synthesis and Micellization of Disymmetric Gemini Imidazolium Surfactants

Two groups of disymmetric Gemini imidazolium surfactants, [C₁₄C₄C _m im]Br₂ (m = 10, 12, 14) and [C _m C₄C _n im]Br₂ (m + n = 24, m = 12, 14, 16, 18) surfactants, were synthesized and their structures were confirmed by ¹H NMR and ESI–MS spectroscopy. Their adsorption at the air/water interface, thermodynamic parameters and aggregation behavior were explored by means of surface tension, electrical conductivity and steady-state fluorescence. A series of surface activity parameters, including cmc, γ _cmc, π _cmc, pC ₂₀, cmc/C ₂₀, Γ _max and A _min, were obtained from surface tension measurements. The results revealed that the overall hydrophobic chain length (N _c) for [C₁₄C₄C _m im]Br₂ and the disymmetry (m/n) for [C _m C₄C _n im]Br₂ had a significant effect on the surface activity. The cmc values decreased with an increase of N _c or m/n. The thermodynamic parameters of micellization (ΔG _m ^θ , ΔH _m ^θ , ΔS _m ^θ ) derived from the electrical conductivity indicated that the micellization process of [C₁₄C₄C _m im]Br₂ and [C _m C₄C _n im]Br₂ was entropy-driven at different temperatures, but the contribution of ΔH _m ^θ to ΔG _m ^θ was enhanced by increasing N _c or m/n. The micropolarity and micellar aggregation number (N _agg) were estimated by steady-state fluorescence measurements. The results showed that the surfactant with higher N _c or m/n can form larger micelles, due to a tighter micellar structure.     

Rapid Quality Assessment of Coal

No satisfactory methods are available for rapid and reliable prediction of one or more coal characteristics. The ignition temperature t_ig of coal, determined in assessing the oxidation of coal in accordance with Ukrainian State Standard DSTU 7611:2014, may be regarded as a useful predictor of coal quality. Research shows that t_ig depends on the composition and ordering of the coal’s organic mass. Mathematical and graphical means of predicting the V ^daf and R_o values of coal are developed.     

Structure of a biologically active binuclear palladium complex,bis(bis[(μ<Subscript>2</Subscript>-cysteine)(2,2′-dipyridyl)-palladium(II)]) · hexanitrates · novemhydrates

The structure of a biologically active binuclear palladium complex, namely, [(dipy)Pd(μ-cysH) (μ-cys)Pd(dipy)]³⁺ · 3NO ₃ ^? · 4.5H₂O (dipy = 2,2′-dipyridyl, C₁₀H₈N₂; cys = cysteine, C₃H₇NO₂S), has been determined from X-ray diffractometry data. The compound crystallizes in the triclinic system, symmetry space group P1, with the unit cell parameters a = 13.863(1) Å, b = 13.819(1) Å, c = 12.170(1) Å, α = 122.13(1)°, β = 103.61(1)°, γ = 91.40(1)°, V = 1887.02 ų, Z = 2, and ρ = 1.82 g/cm³. The final discrepancy factor is R1 = 0.0495 for 12884 symmetrically nonequivalent reflections with F ₀ ≥ 4σ(F ₀), wR2 = 0.1071, and GooF = 0.978. The unit cell contains two chemically equivalent but crystallographically independent positively charged binuclear palladium complexes, six NO ₃ ^? anions, and nine water molecules. The π-π stacking interaction between the nearest pyridyl rings of the neighboring layers takes place. Moreover, the interlayer and intralayer interactions occur through van der Waals interactions and a complex three-dimensional system of hydrogen bonds, which are formed by water molecules, NH ₃ ⁺ groups, and carboxyl groups.     

Ignition temperature of coal. 1. Influence of the coal’s composition,structure, and properties

The reactions of coal with the materials used in determining the ignition temperature of unoxidized coal according to Ukrainian State Standard DSTU 7611:2014 are analyzed. First, the ignition temperature of various types of coal from Ukraine, Russia, Canada, Australia, the Czech Republic, Poland, and Indonesia is determined. The influence of the composition, structure, and properties of the coal on its ignition temperature is assessed. The ignition temperature of the unoxidized coal is found to be closely related to the content of organic carbon C^daf and aromatic carbon C_ar, the structural parameter δ characterizing the degree of saturation of the coal’s organic mass, and also the vitrinite reflection coefficient R_o and the yield of volatiles V^daf.     

Composition and Properties of Brown Coal from the Bodonskoe Deposit in Buryatia

The composition and properties of coal from the Bodonskoe deposit were studied. It was shown that this is low-sulfur (S ^d = 0.3–1.0%) and medium-ash grade 1B brown coal with a high yield of volatile substances (V ^daf = 56.1–60.9%). The humic acid content varies from 32.3 to 50.8%. The heat of combustion of coal is Q _s ^daf = 26.0–27.4 MJ/kg. The concentrations of toxic elements in the coal samples are at a background level.     

Effect of heat transfer conditions on the critical pressure of metal ignition in oxygen

Experimental data on the critical pressure of ignition of titanium alloy fragments in gaseous oxygen are analyzed. The fragments are obtained after fracture of alloy samples in the dynamic mode (p₂^*) and under natural convection conditions (p₁^*). The results are analyzed with allowance for the heat transfer coefficients from material ignition initiators under similar conditions. Based on the shape of the experimental thermograms of plate cooling, the coefficient of heat transfer from microcraters with a juvenile surface formed due to knockout of metal particles from the plate by the high-velocity flow is found: α₂ ≈ 11 kW(m² ·K). The value of α₂ is close to the value of this coefficient calculated with the use of the coefficient α₁ ≈ 5 kW/(m² · K) of heat transfer from titanium rod microfragments (with the size of the order of metal grains) formed during titanium rod fracture in oxygen under conditions of natural convection with allowance for the ratio p₂^*/p₁^*.     

Metamorphic development, degree of reduction, and other characteristics of Donets Basin coal

Analysis of the elementary composition and parameters V ^daf , y, and Q _s ^daf of coal from more than 100 beds in the Donets Basin indicates that the considerable difference in the properties of coal characterized by reduction (in terms of S _t ^d ) and uniform metamorphic development (according to C ^daf ) is due to variation in the ratio of the number of hydrogen and oxygen atoms (H/O_at) in the molecular component of the coal’s organic mass.     

Structure of a catalytically active oxo-centered trinuclear cobalt complex triaqua-(μ<Subscript>3</Subscript>-oxo)-hexa(μ<Subscript>2</Subscript>-pivalato-O,O′)-tricobalt(III)

The structure of a catalytically active oxo-centered trinuclear cobalt complex, namely, [triaqua-(μ₃-oxo)-hexa(μ₂-pivalato-O,O′)-tricobalt(III)]¹⁺ · NO ₃ ^? · 3H₂O, has been determined using X-ray diffraction analysis. The compound crystallizes in the hexagonal crystal system, space group of symmetry P6₃/mmc, with the unit cell parameters a = 12.328(1) Å, c = 22.625(1) Å, V = 2978.1(4) ų, Z = 2, and ρ = 1.075 g/cm³. The final discrepancy factor is R1 = 0.0596 for 589 symmetrically nonequivalent reflections with I ? 2σ(I), wR2 = 0.1612, and GooF = 1.035. The high-symmetry complex [C₃₀H₆₀O₁₆Co₃]¹⁺ with symmetry D _6h and a diameter of ～11 Å is an oxo-centered trinuclear cluster consisting of three symmetrically equivalent Co(III) atoms. Among the oxo-centered trinuclear metal complexes known to date, this complex has the highest symmetry and differs by the presence of two chemically equivalent bridges between the metal atoms. Apart from the two positively charged symmetrically equivalent trinuclear complexes, the unit cell contains two symmetrically equivalent NO ₃ ^? ions (statistically disordered over four positions) and six crystal water molecules.     

On the critical displacement of excited kinetic units in liquids and glasses

The critical displacement of an atom (a group of atoms) in inorganic glasses Δr _m, which corresponds to the maximum of the interatomic attractive force, is calculated using available data on the surface tension and elastic constants. It is found that the critical atomic displacement Δr _m is close in order of magnitude to the linear dimension of the activation volume of atomic excitation v _h ^1/3 for glasses in the As-S and Ge-As-S systems with a chain structure and is considerably less than the value of v _h ^1/3 for alkali silicate glasses and glasses in the Cd-As system with a structure involving ionic sublattices. A relationship for calculating the activation volume of the atomic excitation from data on the glass transition temperature and elastic constants is derived within the model of an excited state.