Comparison of coal hydroliquefaction catalysed by ZnCl2-MCln (CuCl,CrCl3 and MoCl5) and ZnCl2 melts

Hydrogenation of four bituminous coals impregnated with 5 wt% of either mixtures of ZnCl₂-MCl_n (CuCl, CrCl₃ and MoCl₅) systems or ZnCl₂ was carried out using a batch autoclave system at 400° for 3 h at 9.8 MPa of initial hydrogen pressure. The ZnCl₂-MoCl₅ system showed the highest yield of the hexane-soluble (HS) fraction compared with the other systems irrespective of the coal used. The difference between the yields of HS fractions using the ZnCl₂-MoCl₅ and other systems was most marked for coals of fairly low volatile matter content, though the conversion was relatively low (47–66%), whilst for coals of high volatile matter content HS yields with the binary melt systems were high (86–91% conversion). Elemental analyses of the HS fractions indicated that the ZnCl₂-MoCl₅ system is most favourable in decreasing the average molecular weight and the heteroatom content of HS, this characteristic trend being confirmed also with five HS fractions separated by Chromatographic techniques. Both elemental analyses and molecular weights of asphaltene (benzene-soluble materials, BS) indicated that the ZnCl₂-MoCl₅ system is also most effective in cracking coal structure.     

Hydrocracking of Athabasca asphaltene over ZnCl2-KCl-NaCl melts with or without an additive of some transition metal chlorides

Hydrocracking of Athabasca asphaltene over molten salts has been studied at 400 °C for 1 h at an initial hydrogen pressure of 9.8 M Pa. The hydrocracking over ZnCl₂-KCl-NaCl produced 57.0 wt% of pentanesolubles (PS), 4.7 wt% of benzene-solubles (BS) and 22.7 wt% of gases together with 15.6 wt% of coke. These melts containing NiCl₂ and CuCl, respectively, were examined, the former exerting a little better influence on reducing the coke yield. A small amount of coke (3.7%) and a higher conversion attained with ZnCl₂-KCl-NaCl-MoCl₅ suggested excellent properties of MoCl₅ for the hydrocracking of asphaltene. The sulphur contents of the PS and BS were lowest with melt catalysts containing MoCl₅. A compound-type separation of each pentane-soluble showed that in the presence of melt catalyst, monoaromatic and diaromatic contents increased greatly at the expense of polyaromatics and polar materials. The trend of catalytic activity of each melt for hydrocracking of asphaltene was found to be quite different from that for the decomposition reaction of tetrahydrothiophene in a continuous flow system.     

emf Studies of zinc halides ln concentrated aqueous NH4NO3CA(NO3)2 solutions

The formation constants of the species ZnC⁺, ZnCl₂, ZnBr⁺ and ZnBr₂ were determined from emf measurements in suitable concentration cells. Mixtures of NH₄NO₃Ca(NO₃)₂ with a molar ratio 0.844/0.156 containing variable amounts of water (from 0 to 1.2 moles per mol of salt) were used as a solvent. The bromide complexes were found to be more stable than the chloride complexes in the anhydrous melt, while the opposite was found in the concentrated aqueous solutions. The results are discussed on the basis of models for chemical equilibria in molten salts and aqueous melts.     

Hydrogenation of Yūbari coal coated with ZnCl2-MCln (CuCl,CrCl3 and MoCl5) catalyst melts

Hydrogenation of Yūbari coal coated with 5 wt% of ZnCl₂-MCl_n (CuCl, CrCl₃ and MoCl₅) was carried out at 400 °C for 3 h with an initial hydrogen pressure of 9.8 MPa. The binary melt catalysts showed relatively higher activity in increasing the yield of hexane-solubles than did ZnCl₂ alone. The ZnCl₂-MoCl₅ catalyst melt was best in view of its highest conversion (90.9 wt%), the highest yield of hexane-soluble material (50.5 wt%) and the smallest hydrogen consumption. In terms of yield of monoaromatics of the hexane-soluble material relative to polar materials, ZnCl₂-CrCl₃ catalyst was superior to ZnCl₂-MoCl₅ although its hydrogen consumption was high. The roles of CuCl, CrCl₃ and MoCl₅ in association with ZnCl₂ in coal-hydrogenation are discussed.     

Catalytic activities of binary molten salts composed of ZnCl2 and metal chlorides for hydrocracking of phenanthrene

Phenanthrene, a coal model compound, was hydrocracked in a batch autoclave at 400 °C for 3 h with an initial hydrogen pressure of 9.8 MPa and equimolar concentrations of molten salts. Binary salts composed of ZnCl₂ and metal chlorides, such as CuCl, MoCl₅CrCl₃, NiCl₂, and PdCl₂, etc., showed superior catalytic activity to pure ZnCl₂ (MCI_x/ZnCl₂ molar ratio was fixed to $\text{1}\text{4}$). The isomerization of cyclohexene and H₂?D₂ exchange reactions were also examined to estimate acid-catalytic and hydrogen-activation abilities, respectively. Both activities were found to increase with the addition of metal chloride to ZnCl₂, indicating synergistic catalytic activity. Phenanthrene conversions (as a measure of hydrocracking activities of the salts) over some catalysts correlated rectilinearly with yields of isomerized products of cyclohexane.     

Hydrogenolysis reaction of coal-derived asphaltene using molten salt catalysts

Hydrogenolysis of benzene-soluble, hexane-insoluble material (asphaltene) derived from Chinese Tatung coal was carried out using molten metal halide catalysts. Molten salts such as SnCl₂-containing mixtures, showing low ratios of iso-butane to normal butane in the gaseous products, were found to accelerate the conversion of asphaltene to hexane solubles (HS) and suppress the production of gases. The conversion reaction of asphaltene to oil with this catalyst system is always accompanied by the elimination of phenolic hydroxyl groups bonded to aromatic rings. The ZnCl₂CuCl system, of strong acidity as indicated by a high ratio of iso-butane to normal butane, exhibited a high activity in hydrogenolysis, the degradation proceeding to gasification. The systems containing KCl, giving relatively low ratios of iso-butane to normal butane, allowed high yields of HS with large amounts of hydroxyl groups. The reactions involved in the conversion are discussed.     

Pyrolysis of kraft lignin in molten ZNCL2-KCL media with tetralin vapor addition

Kraft lignin was pyrolyzed in molten salt media of ZnCl₂-KCl mixture with tetralin vapor added in 0.4 and 4 mol% diluted with N₂ in the temperature range of 400 to 700°C. The gas chromatographic analyses of pyrolysis products revealed that the yield of H₂ was not increased by tetralin vapor addition. This fact implies that the hydrogen radical produced from tetralin is consumed in the formation of phenolic compounds and light liquids but not in the formation of H₂. p-Cresol was the most abundant phenolic compound. The yield of total phenolic compounds with 4 mol% tetralin vapor added was increased by ca. 80% as compared to that in neat pyrolysis of Kraft lignin.     

Physicochemical properties of ZnCl2-NaCl-KCl eutectic melt

Physicochemical properties of ZnCl₂-NaCl-KCl eutectic melt were studied at 200-300 °C for the first time. Firstly, it was reconfirmed that the eutectic composition is ZnCl₂:NaCl:KCl = 0.6:0.2:0.2 in mole fraction, and that the eutectic temperature is 203 °C. Then, the density, viscosity, and ionic conductivity of the ZnCl₂-NaCl-KCl eutectic melt were measured at 200-300 °C. At 250 °C, the density was 2.43 g cm⁻³, the viscosity was 42.0 cP and the ionic conductivity was 8.53 S m⁻¹. The temperature dependencies of density and ionic conductivity were well fitted by the VTF equations with the same ideal glass transition temperature of 283 K (10 °C). It was found that the melt obeys the fractional Walden's rule which is explained by the decoupling effect. The electrochemical window of the melt was determined to be 1.7 V at 250 °C with the cathode limit being zinc metal deposition and the anode limit being chlorine gas evolution.     

Interaction between coal and liquefaction catalysts studied by high temperature electron spin resonance

The high temperature electron spin resonance technique has been used to obtain in situ information on the behaviour of liquefaction catalysts during coal pyrolysis. The spin concentration in coal was induced in the presence of a catalyst at the pyrolysis temperature. ZnCl₂ drastically increased the spin concentration of coal. The order of activity of the catalysts with respect to the increase in spin concentration was: ZnCl₂ (impregnated) ?ZnCl₂ (dispersed) >ZnCl₂/KCl>SnCl₂ > SbCl₃≈AlCl₃ ≈CaCl₂ > coal alone.     

Electrodeposition of Sb, Bi, Te, and their alloys in AlCl3-NaCl-KCl molten salt

The Electrochemistry of Sb, Bi, and Te in AlCl₃-NaCl-KCl molten salt containing SbCl₃, BiCl₃, and/or TeCl₄ at 423 K was investigated by voltammetry, and electrodeposition of the three metals was performed under constant potential control in the melt. The voltammogram on a glassy carbon (GC) electrode in a melt containing 0.025 mol dm⁻³ [M] SbCl₃ showed a couple of redox peak corresponding to the Sb/Sb(III) redox reaction, and a stable layer of pure Sb was deposited under the constant potential control. The voltammograms in the melt containing 0.025 M BiCl₃ or 0.025 M TeCl₄ showed several redox couples. Stable deposit layers of pure Bi and Te were not obtained under the constant potential control, as the deposited layers detached from the electrode and immediately dissolved into the molten salt. Binary alloy deposition was possible in a melt containing BiCl₃ and SbCl₃, and also with BiCl₃ and TeCl₄. A stable Bi-Sb alloy deposit of metallic Sb and Bi-Sb solid solution was obtained at 0.8 and 0.9 V versus Al/Al(III) in the melt containing BiCl₃ and SbCl₃. The atomic ratio of Bi in the deposit was 37% at 0.9 V and 57% at 0.8 V. A stable Bi-Te alloy deposit was also obtained with the molten salt containing BiCl₃ and TeCl₄. The deposited Bi-Te alloy consisted of a mixture of Bi₂Te₃, BiTe, and Bi₂Te. The alloy deposit had good crystallinity and the preferential orientation was the (1 1 0) plane.     

Synthesis of ZnNb2O6 powder with rod-like particle morphologies

A ZnNb₂O₆ powder was synthesized through the molten salt method. The XRD and SEM results indicated that the crystal ZnNb₂O₆ powder with rod-like particle morphologies could be obtained via this method at temperature of 600 °C, which is significantly lower than that required by solid-state reaction, where a calcining temperature of 800 °C was needed and the obtained ZnNb₂O₆ particles were equiaxial. The heat treatment temperature scarcely affected the ZnNb₂O₆ particle morphologies in the molten salt synthesis process.     

Calciothermic reduction of NiO by molten salt electrolysis of CaO in CaCl2 melt

Metallic nickel powders with low and uniform residual oxygen content were produced from NiO using the molten salt electrolysis of CaO in CaCl₂ melt. Suitable amount of CaO for the reduction was in the range of 0.5–3.0 mol% CaO.The electrical isolation of NiO from both electrodes could produce metallic Ni in CaCl₂ melt. Separating the metal oxides from the cathode confirmed the mechanism of calciothermic reduction that the electrolysis of dissolved CaO in CaCl₂ melt produces Ca, and that the dissolved Ca in molten CaCl₂ successfully reduces NiO to metallic Ni. An average of about 600 ppm oxygen in Ni sample was achieved directly from oxide, when NiO was detached from the cathode.     

The synthesis of methyl lactate and other methyl oxygenates from cellulose

Light oxygenates, such as methyl lactate (MLA), methyl levulinate (MLE), methyl formate (MFO), methyl acetate (MAC), dimethoxymethane (DMM), and methoxyacetaldehyde dimethyl acetal (MADA) were synthesized from cellulose in the presence of promoted SnX₂ (X = Cl⁻, Br⁻, and I⁻) salt catalysts in methanol. The presence of halides in SnX₂-ML_n (ML_n is metal salt) catalysts was found crucial for methyl lactate formation from sugar. The investigation shows that ZnCl₂ is an efficient promoter for SnX₂ catalyst in converting cellulose to light oxygenates. Up to 52.2% of total one-pass oxygenate yield was obtained in the presence of SnCl₂–ZnCl₂ catalyst.     

Analysis of tungsten film electrodeposited from a ZnCl2-NaCl-KCl melt

Microparts for micro-electro-mechanical systems (MEMS) are becoming increasingly important, and the Lithographie Galvanoformung Abformung (LIGA) process for producing such parts is attracting attention [1]. However, as this process requires the step of electroplating in aqueous solution, only copper, nickel and their alloys can be used because of the limit of the potential window of water. We have been attempting to apply the electroplating of refractory metals in molten salts to the LIGA process or to the surface coating of conventional LIGA microparts in order to give higher strength and heat resistance for the microparts. Herein we report the characteristics of a tungsten film electrodeposited from a ZnCl₂-NaCl-KCl melt at 250 °C.     

Atom transfer radical polymerizations of methyl methacrylate catalyzed by EBiB/SnCl2·2H2O(FeCl2·4H2O)/FeCl3·6H2O/MA5-DETA systems

The ATRP of methyl methacrylate (MMA) with the system of FeCl₂·4H₂O, N,N,N′,N″,N″-penta(methyl acylate)diethylenetriamine (MA₅-DETA) and ethyl 2-bromoisobutyrate (EBiB) showed high activity and is not well-controlled. The addition of a certain amount of FeCl₃·6H₂O as the additive into the above system results in the decrease of the polymerization rate and the improvement of the controllability. When SnCl₂·2H₂O was added instead of FeCl₂·4H₂O, a novel catalyst system SnCl₂·2H₂O/FeCl₃·6H₂O/EBiB/MA₅-DETA formed shows better controllability, higher catalytic activity and higher initiating efficiencies (more than 90%) in comparison with the system FeCl₂·2H₂O/FeCl₃·6H₂O/EBiB/MA₅-DETA. The polydispersities of the polymers kept range from M_w/M_n=1.18-1.26. The real active species in the new system is Fe (II) formed from the reaction of FeCl₃·6H₂O with the active radical species produced from the reaction of SnCl₂·2H₂O with EBiB.     

Structural study of hexane-soluble products from hydroliquefaction of three Yallourn brown coal lithotypes over molten salt catalysts

The hexane-soluble fractions of hydroliquefied products from three Yallourn brown coal lithotypes have been separated into five fractions by combined silica-alumina packed column chromatography. Analyses of various fractions by g.c.-m.s. permitted the identification of ≈50 components in the saturate fraction and 40 components in the diaromatic fraction, together with 30 components in the monoaromatics. The components identified were quite similar among hexane-soluble portions of all three lithotypes. A marked predominance of even carbon number alkane (C₂₃-C₂₉) was observed in the hydrocarbon fractions from pale lithotype over $\text{ZnCl}{}_2\text{KCl}$, and medium light lithotype over both pure ZnCl₂ and $\text{ZnCl}{}_2\text{KCl}$. However, medium dark lithotype over both melt catalysts produced a saturate fraction with an odd carbon number(C₂₂-C₂₈) preference. Based on spectral methods, Soxhlet extracts obtained from untreated lithotypes (hexane and benzene solubles) were characterized as complex mixtures of higher molecular weight(300–1000) aliphatic hydrocarbons, which were supposed to be a precursor of the saturates produced from the corresponding lithotype in the catalytic hydroliquefaction.     

Investigation of the structure of poly(p-chlorophenyl glycidyl ether) by the 13C n.m.r. technique: tacticity and addition isomerism

The p-chlorophenyl glycidyl ether was polymerized in the presence of Al(OiPr)₃, ZnCl₂, SnCl₄, BuOK, KOH and by the Al(OiPr)₃ZnCl₂ 1:1 initiator system. Analysis of the ¹³C n.m.r. spectra of the poly(p-chlorophenyl glycidyl ethers) obtained has made it possible to determine their tacticity and the content of the head-to-tail and head-to-head linkages in the polymer chain.     

Evaluation of hot corrosion behavior of CSZ,CSZ/micro Al2O3 and CSZ/nano Al2O3 plasma sprayed thermal barrier coatings

Hot corrosion is one of the main destructive factors in thermal barrier coatings (TBCs) which come as a result of molten salt effect on the coating–gas interface. Hot corrosion behavior of three types of plasma sprayed TBCs was evaluated: usual CSZ, layer composite of CSZ/Micro Al₂O₃ and layer composite of CSZ/Nano Al₂O₃ in which Al₂O₃ was as a topcoat on CSZ layer. Hot corrosion studies of plasma sprayed thermal barrier coatings (TBCs) were conducted in 45 wt% Na₂SO₄+55 wt% V₂O₅ molten salt at 1050 °C for 40 h. The graded microstructure of the coatings was examined using scanning electron microscope (SEM) and X-ray diffractometer (XRD) before and after hot corrosion test. The results showed that no damage and hot corrosion products was found on the surface of CSZ/Nano Al₂O₃ coating and monoclinic ZrO₂ fraction was lower in CSZ/Micro Al₂O₃ coating in comparison with usual CSZ. reaction of molten salts with stabilizers of zirconia (Y₂O₃ and CeO₂) that accompanied by formation of monoclinic zirconia, irregular shape crystals of YVO₄, CeVO₄ and semi-cubic crystals of CeO₂ as hot corrosion products, caused the degradation of CSZ coating in usual CSZ and CSZ/Micro Al₂O₃ coating.     

Ablation properties of C/C-UHTCs and their preparation by reactive infiltration of K2MeF6 (Me = Zr,Ti) molten salt

Ultra-high temperature ceramic-modified C/C composites (C/C-UHTCs) were prepared by the reactive infiltration of K₂MeF₆ (Me = Zr, Ti) mixed with Si and Zr-Si powders. Molten salt infiltration can be divided into two stages: salt ion melt and Me-Si alloy melt. In the temperature range below 1400 °C, Zr and Si dissolve in the molten salt, are carried by the ion melt, and precipitate at the PyC interface to form carbides. Above 1400 °C, a large amount of molten salt volatilises and thermally decomposes. The Me-Si alloy forms a melt and infiltrates the C/C matrix, and finally forms C/C-ZrC-SiC, C/C-Ti₃SiC₂-SiC, and C/C-ZrC-TiC-SiC composites. The C/C-ZrC-SiC composite with the highest ZrC content exhibited the lowest mass rate (2.6 ± 0.02 mg/s) and linear ablation rate (0.82 ± 0.04 μm/s), which were reduced by 43.5 and 50.8 %, respectively, compared to the unmodified C/C-ZrC-SiC composite.     

Effect of impregnation with ZnCl2 and other catalysts on coal pyrolysis

Similarity of product distributions from the pyrolysis of ZnCl₂-impregnated coals and ZnCl₂-coal admixtures suggests that the catalyst does not distribute itself uniformly within the coal mass upon impregnation from solution. Elemental distribution maps for zinc and chlorine, obtained by electron probe microanalysis, confirm that the catalyst is deposited around the periphery of coal particles upon impregnation. Uniform distribution of the ZnCl₂ within the particles, however, appears to take place on heating to temperatures as low as 160 °C.