Influence of the Calcination Technique of Silica on the Properties and Performance of Ni/SiO2 Catalysts for Synthesis of Hydrogen via Methane Cracking Reaction.

Deactivation of catalysts due to rapid blocking of active surfaces and pores is a major problem for methane cracking. The removal of the template using different calcination methods contributes to the different characteristics of catalyst support. Therefore, silica supports were prepared with the sol-gel method, where sodium silicate and chitosan are a silica source and a template, respectively. Calcination using a microwave muffle furnace (MWF) was preferred over the conventional electric muffle furnace at the heating rates of 2 and 17 °C/min (CEF2 and CEF17, respectively) in order to remove the chitosan template. A nickel nitrate precursor was loaded onto the obtained silica supports by the incipient wetness impregnation method. The properties of the silica support and the Ni/SiO2 catalysts were characterized by means of N2-sorption, X-ray diffraction, scanning electron microscopy-energy-dispersive X-ray, field emission transmission electron microscopy, and H2 temperature-programmed reduction. The catalytic activity was evaluated using a fixed-bed reactor at 550 °C with a CH4/N2 ratio of 1:4 in the feed. The amount and the allotropes of carbon deposited on the spent catalysts were investigated using thermogravimetric/differential thermal analysis. The results showed that the SiO2-MWF support had a higher surface area and a larger pore volume of a mesoporous structure with larger interparticle channels than that of the SiO2-CEF supports. This leads to the higher dispersion of Ni metal particles over and inside the interparticle channels of the SiO2-MWF support. This provided a higher metal-support interaction, resulting in lower rates of methane conversion and carbon deposition on the catalyst surface than those of Ni/SiO2-CEF catalysts. However, it displayed a lower bed pressure. It was found that the carbon fibers deposited on all the catalysts were multiwalled carbon nanotubes (MWCNTs). Additionally, the base-growth mechanism of MWCNTs was only exhibited by the Ni/SiO2-MWF catalyst.

Determination of potassium, sodium, and total alkalies in portland cement, fly ash, admixtures, and water of concrete by a simple flow injection flame photometric system.

A simple flow injection with flame photometric detection has been developed for determination of sodium, potassium, and total alkalies in portland cement, fly ash, admixtures, and water of concrete. A liquid sample or a digest of solid sample was injected into a water carrier stream which flowed to a flame photometer. A change in emission intensity at a selected wavelength was recorded as a peak. An amplifier circuit was fabricated, which helped improve sensitivity of the flame photometer. Calibration graphs in the range of 0.05-1.0 mg L(-1) and 1.0-20.0 mg L(-1) were obtained with a detection limit of 0.02 mg L(-1), for both potassium and sodium determination. Relative standard deviations for 11 replicates of injecting of 10 mg L(-1) potassium and sodium solutions were 1.69 and 1.79%, respectively. Sample throughput of 120 h(-1) was achieved. The proposed method was successfully applied to portland cement, fly ash, admixtures, and water samples validated by the ASTM standard method and certified reference materials of portland cement.

Determination of available phosphorus in soils by using a new extraction procedure and a flow injection amperometric system.

A new extraction procedure based on an off-line extraction column was proposed for extracting of available phosphorus from soils. The column was fabricated from a plastic syringe fitted at the bottom with a cotton wool and a piece of filter paper to support a soil sample. An aliquot (50 mL) of extracting solution (0.05 M HCl+0.0125 M H(2)SO(4)) was used to extract the sample under gravity flow and the eluate was collected in a polyethylene bottle. The extract was then analyzed for phosphorus contents by a simple flow injection amperometric system, employing a set of three-way solenoid valves as an injection valve. The method is based on the electrochemical reduction of 12-molybdophosphate which is produced on-line by the reaction of orthophosphate with acidic molybdate and the electrical current produced was directly proportional to the concentration of phosphate in range of 0.1-10.0 mg L(-1) PO(4)-P, with a detection limit of 0.02 mg L(-1). Relative standard for 11 replicate injections of 5 mg L(-1) PO(4)-P was 0.5%. A sample through put of 35 h(-1) was achieved, with consumption of 14 mg KCl, 10mg ammonium molybdate and 0.05 mL H(2)SO(4) per analysis. The detection system does not suffer from the interferences that are encountered in the photometric method such as colored substances, colloids, metal ions, silicate and refractive index effect (Schlieren effect). The results obtained by the column extraction procedure were well correlated with those obtained by the steady-state extraction procedure, but showed slightly higher extraction efficiency.

Determination of cadmium, lead, copper and zinc in the acetic acid extract of glazed ceramic surfaces by anodic stripping voltammetric method.

An anodic stripping voltammetric method has been developed for determination of cadmium, lead, copper and zinc in acetic acid extract of glazed ceramic surfaces. An aliquot of 4% (v/v) acetic acid solution was kept in a ceramic ware for 24h in the dark, then 10 mL of the extracted solution was placed in a voltammetric cell. The solution was purged with oxygen free nitrogen gas for 3 min before deposition of the metals was carried out by applying a constant potential of -1.20 V versus Ag/AgCl to the hanging mercury drop electrode (HMDE) for 45 s. A square wave waveform was scanned from -1.20 to 0.15 V and a voltammogram was recorded. A standard addition procedure was used for quantification. Detection limits of 0.25, 0.07, 2.7 and 0.5 microg L(-1) for cadmium, lead copper and zinc, respectively, were obtained. Relative standard deviations for 11 replicate determinations of 100 microg L(-1) each of all the metals were in the range of 2.8-3.6%. Percentage recoveries obtained by spiking 50 microg L(-1) of each metal to the sample solution were in the range of 105-113%. The method was successfully applied to ceramic wares producing in Lampang province of Thailand. It was found that the contents of cadmium, lead, copper and zinc released from the samples were in the range of <0.01-0.16, 0.02-0.45, <0.14 and 0.28-10.36 microg dm(-2), respectively, which are lower than the regulated values of the Thai industrial standard. The proposed method is simpler, more convenient and more sensitive than the standard method based on FAAS.

Flow injection conductometric system with gas diffusion separation for the determination of Kjeldahl nitrogen in milk and chicken meat.

A simple flow injection (FI) conductometric system with gas diffusion separation was developed for the determination of Kjeldahl nitrogen (or proteins) in milk and chicken meat. The sample was digested according to the Kjeldahl standard method and the digest was diluted and directly injected into the donor stream consisting of 4M NaOH. In alkaline medium, ammonium was converted to ammonia, which diffused through the PTFE membrane to dissolve in an acceptor stream (water). Dissociation of ammonia caused a change in conductance of the acceptor solution, which was linearly proportional to the concentration of ammonium originally present in the injected solution. A conductometric flow through cell and an amplifier circuit was fabricated, which helped improve sensitivity of the conductometric detection system. With using a plumbing Teflon tape as a gas diffusion membrane and without thermostating control of the system, a linear calibration graph in range of 10-100mgL(-1) N-NH(4) was obtained, with detection limit of 1mgL(-1) and good precision (relative standard deviation of 0.3% for 11 replicate injections of 50mgL(-1) N-NH(4)). The developed method was validated by the standard Kjeldahl distillation/titration method for the analysis of milk and chicken meat samples. The proposed system had sample throughput of 35h(-1) and consumed much smaller amounts of chemical than the standard method (275mg vs 17.5g of NaOH per analysis, respectively).

Determination of chloride in admixtures and aggregates for cement by a simple flow injection potentiometric system.

A simple flow injection system using three 3-way solenoid valves as an electric control injection valve and with a simple home-made chloride ion selective electrode based on Ag/AgCl wire as a sensor for determination of water soluble chloride in admixtures and aggregates for cement has been developed. A liquid sample or an extract was injected into a water carrier stream which was then merged with 0.1M KNO(3) stream and flowed through a flow cell where the solution will be in contact with the sensor, producing a potential change recorded as a peak. A calibration graph in range of 10-100 mg L(-1) was obtained with a detection limit of 2 mg L(-1). Relative standard deviations for 7 replicates injecting of 20, 60 and 90 mg L(-1) chloride solutions were 1.0, 1.2 and 0.6%, respectively. Sample throughput of 60 h(-1) was achieved with the consumption of 1 mL each of electrolyte solution and water carrier. The developed method was validated by the British Standard methods.