Preparation of Co–Mo/B2O3/Al2O3 catalysts for hydrodesulfurization: Effect of citric acid addition

The effect of citric acid (CA) addition was studied on the HDS of thiophene over Co–Mo/(B)/Al₂O₃ catalysts. The catalysts were characterized by means of LRS, Mo K-edge EXAFS, NO adsorption capacity measurements, and UV–vis spectra. The catalysts were subjected to a chemical vapor deposition (CVD) technique using Co(CO)₃NO as a precursor of Co in order to get deeper insights into the effect of citric acid addition. It was shown that the HDS activity was enhanced by the citric acid addition up to the CA/Mo mole ratio of around 1 and leveled off with further addition. The amount of Co anchored by the CVD was increased by the addition of citric acid, suggesting an increase in the dispersion of MoS₂ particles on the catalyst by the simultaneous presence of Co, Mo and citric acid, in conformity with the increase in the NO adsorption capacity. In contrast to Co–Mo catalysts, the edge dispersion of MoS₂ particles in Mo/B/Al₂O₃ was not affected by the addition of citric acid. The LRS, UV–vis spectra and Mo K-edge EXAFS showed that Co–CA and Mo–CA surface complexes are formed by the addition of citric acid. The Co–CA surface complex is more preferentially formed on CoMo/Al than on CoMo/B/Al, in agreement with a greater promoting effect of citric acid at a lower CA/Mo mole ratio for CoMo/Al than for CoMo/B/Al.     

Formation Mechanism of Hydrous-Zirconia Particles Produced by Hydrolysis of ZrOCl2 Solutions: II

The primary and secondary particle sizes of monoclinic hydrous-ZrO₂ particles produced by the hydrolysis of various ZrOCl₂ solutions, with and without the addition of NaCl, CaCl₂, or AlCl₃, were measured using X-ray diffraction and transmission electron microscopy in order to clarify the formation mechanisms of primary and secondary particles. The primary particle size of hydrous ZrO₂, under a constant ZrOCl₂ concentration, decreased monotonously with increasing Cl⁻-ion concentration. On the contrary, the secondary particle size increased monotonously with increasing Cl⁻-ion concentration. The present experimental results revealed that the primary and secondary particle sizes of hydrous ZrO₂ are controlled primarily by the concentrations of H⁺ and Cl⁻ ions produced during hydrolysis, and are independent of the type of added metal ions. The formation mechanisms of the primary and secondary particles of hydrous ZrO₂ were determined on the basis of the present experimental results.     

Synthesis of stable and soluble one-handed helical poly(substituted acetylene)s without chiral pendant groups via polymer reaction in membrane state

A soluble and stable one-handed helical conjugated polymer without the coexistence of any other chiral moieties was successfully synthesized by asymmetric-induced polymerization of a chiral monomer having two hydroxyl groups followed by desubstitution of the chiral groups in a solid membrane state. The reason for the success was the polymer reaction was carried out in the membrane state. This is an alternative method to obtain such a unique chiral polymer which was obtained only by the helix-sense-selective polymerization (HSSP) we reported before. In addition the efficiency of the chiral induction was higher than that of the HSSP. It is interesting that the “Membrane state” acted like as if a protecting group.     

Grafting of poly(ethylene oxide) onto C60 fullerene using macroazo initiators

In order to improve the solubility of C₆₀ fullerene in conventional solvents, grafting of hydrophilic poly(ethylene oxide) (PEO) by utilizing the radical-trapping nature of C₆₀ fullerene was investigated. Macroazo initiators containing a poly(ethylene oxide) unit, known as Azo-PEO, were prepared at various molecular weights by the reaction of 4,4′-azobis(4-cyanopentanoyl chloride) with poly(ethylene glycol) methyl ether. PEO radicals formed by thermal decomposition of Azo-PEO were successfully trapped by C₆₀ fullerene to give PEO-grafted C₆₀ fullerene. Their structures were confirmed by FT-IR spectroscopy, size exclusion chromatography, UV-vis spectroscopy, and differential scanning calorimetry. When Azo-PEO with low-molecular weight was reacted with C₆₀ fullerene, a bis-adduct, C₆₀-(PEO)₂, and a tetrakis-adduct, C₆₀-(PEO)₄, were formed. In contrast, in reactions with Azo-PEO of higher molecular weight, only the bis-adduct was formed, and no formation of the tetrakis-adduct was observed. The structure of bis-adduct was found to be 1,4-type. The solubility of C₆₀ fullerene in water, THF, methanol, and other conventional organic solvents was remarkably improved by grafting of PEO. In addition, the thermal stability of PEO was dramatically increased by grafting onto C₆₀ fullerene.     

Sintering Kinetics at Constant Rates of Heating: Effect of Al2O3 on the Initial Sintering Stage of Fine Zirconia Powder

The sinterabilities of fine zirconia powders including 5 mass% Y₂O₃ were investigated, with emphasis on the effect of Al₂O₃ at the initial sintering stage. The shrinkage of powder compact was measured under constant rates of heating (CRH). The powder compact including a small amount of Al₂O₃ increased the densification rate with elevating temperature. The activation energies at the initial stage of sintering were determined by analyzing the densification curves. The activation energy of powder compact including Al₂O₃ was lower than that of a powder compact without Al₂O₃. The diffusion mechanisms at the initial sintering stage were determined using the new analytical equation applied for CRH techniques. This analysis exhibited that Al₂O₃ included in a powder compact changed the diffusion mechanism from grain boundary to volume diffusions (VD). Therefore, it is concluded that the effect of Al₂O₃ enhanced the densification rate because of decrease in the activation energy of VD at the initial sintering stage.     

Ca-α SiAlON hollow spheres prepared by carbothermal reduction–nitridation from different SiO2 powders

The formation process of hollow spheres composed of nanosized Ca-α SiAlON particles was investigated using SiO₂ starting powders with different characteristics in particle size, shape and crystalline state. TEM observations showed Ca-α SiAlON hollow spheres composed of a large number of nanosized particles in the products prepared at 1450 °C for 120 min in nitrogen. In all systems, the Ca-α SiAlON hollow spheres were always produced through an intermediate Si–Al–Ca–O liquid phase in the same mechanism, regardless of the characteristics of SiO₂ starting powders used. Spherical solid particles consisted of amorphous phase containing Si, Al, Ca, O and a small amount of N were generated at the initial stage of carbothermal reduction–nitridation. These spherical solid particles changed into hollow particles with the progression of the reaction from the liquid phase to the crystalline Ca-α SiAlON with increasing temperature.     

Stereocomplex crystallization and spherulite growth behavior of poly(l-lactide)-b-poly(d-lactide) stereodiblock copolymers

The non-isothermally and isothermally crystallized stereodiblock copolymers of poly(l-lactide) (PLLA) and poly(d-lactide) (PDLA) with equimolar l-lactyl and d-lactyl units and different number-average molecular weights (M_n) of 3.9 × 10³, 9.3 × 10³, and 1.1 × 10⁴ g mol⁻¹, which are abbreviated as PLLA-b-PDLA copolymers, contained only stereocomplex crystallites as crystalline species, causing higher melting temperatures of the PLLA-b-PDLA copolymers compared to those of PLLA homopolymers. In the case of non-isothermal crystallization, the cold crystallization temperatures of the PLLA-b-PDLA copolymers during heating and cooling were respectively lower and higher than those of PLLA homopolymers, indicating accelerated crystallization of PLLA-b-PDLA copolymers. In the case of isothermal crystallization, in the crystallizable temperature range, the crystallinity (X_c) values of the PLLA-b-PDLA copolymers were lower than those of the PLLA homopolymers, and were susceptible to the effect of crystallization temperature in contrast to that of homopolymers. The radial growth rate of the spherulites (G) of the PLLA-b-PDLA copolymers was the highest at the middle M_n of 9.3 × 10³ g mol⁻¹. This trend is different from that of the PLLA homopolymers where the G values increased monotonically with a decrease in M_n, but seems to be caused by the upper critical M_n values of PLLA and PDLA chains as in the case of PLLA/PDLA blends (in other papers), above which homo-crystallites are formed in addition to stereocomplex crystallites. The disturbed crystallization of PLLA-b-PDLA copolymers compared to that of the PLLA/PDLA blend is attributable to the segmental connection between the PLLA and PDLA chains, which interrupted the free movement of those chains of the PLLA-b-PDLA copolymers during crystallization. The crystallite growth mechanism of the PLLA-b-PDLA copolymers was different from that of the PLLA/PDLA blend.     

Measurement of liquid water content in cathode gas diffusion electrode of polymer electrolyte fuel cell

Water management in cathode gas diffusion electrode (GDE) of polymer electrolyte fuel cell (PEFC) is essential for high performance operation, because liquid water condensed in porous gas diffusion layer (GDL) and catalyst layer (CL) blocks oxygen transport to active reaction sites. In this study, the average liquid water content inside the cathode GDE of a low-temperature PEFC is experimentally and quantitatively estimated by the weight measurement, and the relationship between the water accumulation rate in the cathode GDE and the cell voltage is investigated. The liquid water behavior at the cathode is also visualized using an optical diagnostic, and the effects of operating conditions and GDL structures on the water transport in the cathode GDE are discussed. It is found that the liquid water content in the cathode GDE increases remarkably after starting the fuel cell operation due to the water production at the CL. At a high current density, the cell voltage drops suddenly after starting the operation in spite of a low water content in the cathode GDE. When the GDL thickness is increased, much water accumulates near the cathode CL and the fuel cell shuts down immediately after the operation. In the final section of this paper, the structure of cathode GDL that has several grooves for water removal is proposed to prevent water flooding and improve fuel cell performance. This groove structure is effective to promote the removal of the liquid water accumulated near the active catalyst sites.     

Comparative assessment of CO2 capture technologies for carbon-intensive industrial processes

This article presents a consistent techno-economic assessment and comparison of CO₂ capture technologies for key industrial sectors (iron and steel, cement, petroleum refineries and petrochemicals). The assessment is based on an extensive literature review, covering studies from both industries and academia. Key parameters, e.g., capacity factor (91-97%), energy prices (natural gas: 8 €₂₀₀₇/GJ, coal: 2.5 €₂₀₀₇/GJ, grid electricity: 55 €/MWh), interest rate (10%), economic plant lifetime (20 years), CO₂ compression pressure (110 bar), and grid electricity CO₂ intensity (400 g/kWh), were standardized to enable a fair comparison of technologies. The analysis focuses on the changes in energy, CO₂ emissions and material flows, due to the deployment of CO₂ capture technologies. CO₂ capture technologies are categorized into short-mid term (ST/MT) and long term (LT) technologies. The findings of this study identified a large number of technologies under development, but it is too soon to identify which technologies would become dominant in the future. Moreover, a good integration of industrial plants and power plants is essential for cost-effective CO₂ capture because CO₂ capture may increase the industrial onsite electricity production significantly.For the iron and steel sector, 40-65 €/tCO₂ avoided may be achieved in the ST/MT, depending on the ironmaking process and the CO₂ capture technique. Advanced LT CO₂ capture technologies for the blast furnace based process may not offer significant advantages over conventional ones (30-55 €/tCO₂ avoided). Rather than the performance of CO₂ capture technique itself, low-cost CO₂ emissions reduction comes from good integration of CO₂ capture to the ironmaking process. Advanced smelting reduction with integrated CO₂ capture may enable lower steel production cost and lower CO₂ emissions than the blast furnace based process, i.e., negative CO₂ mitigation cost. For the cement sector, post-combustion capture appears to be the only commercial technology in the ST/MT and the costs are above 65 €/tCO₂ avoided. In the LT, a number of technologies may enable 25-55 €/tCO₂ avoided. The findings also indicate that, in some cases, partial CO₂ capture may have comparative advantages. For the refining and petrochemical sectors, oxyfuel capture was found to be more economical than others at 50-60 €/tCO₂ avoided in ST/MT and about 30 €/tCO₂ avoided in the LT. However, oxyfuel retrofit of furnaces and heaters may be more complicated than that of boilers.Crude estimates of technical potentials for global CO₂ emissions reduction for 2030 were made for the industrial processes investigated with the ST/MT technologies. They amount up to about 4 Gt/yr: 1 Gt/yr for the iron and steel sector, about 2 Gt/yr for the cement sector, and 1 Gt/yr for petroleum refineries. The actual deployment level would be much lower due to various constraints, about 0.8 Gt/yr, in a stringent emissions reduction scenario.     

Highwall Stability due to Punch Mining at Opencut Coal Mines

Conventional highwall mining extracts coal with an auger machine or a continuous miner from exposed seams at the base of opencut or strip operations. However, under poor strata and high stress conditions, highwall mining cannot be conducted due to pillar and roof failures. In such cases, punch highwall mining is more effective than the conventional highwall mining. This paper describes conventional highwall mining and punch highwall mining systems and discusses the stability of the highwall due to punch highwall mining at opencut coal mines.