STATISTICAL THERMODYNAMIC ANALYSIS ON THE SORPTION SELECTIVITY FOR A BINARY LIQUID MIXTURE ON THE SOLID SURFACE

The nonideal concentration dependent sorption selectivity for the liquid-solid interface was analyzed by introducing the admolecular interaction in the statistical thermodynamic approach. The quasi-chemical and Bragg-Williams approximations together with the maximum term condition result in the desired expression for the adsorption isotherm. Experiments were carried out for the adsorption of the binary (xylene/toluene) mixture on the Y-zeolite as a nonideal system. The derived isotherms were correlated with both the ideal system reported by Sircar and Myers and the present nonideal adsorption data.     

Sorption of caesium by complex hexacyanoferrates. v. a comparison of some cyanoferrates

The properties of copper cyanoferrates and potassium cobalt ferrocyanide prepared at Imperial College and similar commercial products for caesium sorption have been investigated. Copper and cobalt based cyanoferrates have different chemical compositions and appear to be good adsorbers for the removal of caesium in aqueous solutions. Different caesium sorption mechanisms were observed for these cyanoferrates. A conventional ion exchange reaction, physical adsorption and a combination of the two processes were observed. The difference in caesium sorption mechanism also reflects the kinetics of the sorption process. Potassium copper ferrocyanide has the highest effective capacity but the caesium sorption rate is the slowest, whilst potassium cobalt ferrocyanide possesses faster kinetics but considerably lower effective capacity. Copper ferrocyanide tends to have better mechanical stability and moderate sorption kinetics and caesium uptake.     

Application of compression test in analysis of mechanical and color changes in grapefruit juice powder as related to glass transition and water activity

Physicochemical and structural properties of grapefruit juice powder were studied as affected by water activity. Powdered juice was obtained by freeze-drying and equilibrated at different water vapor pressure atmospheres in order to give samples with water activity in the range of 0-0.84. The mechanical properties of the powder were measured by confined compression tests and the compressed samples, which presented uniform surface and thickness, were subjected to color analysis. The maximum force attained during the compression tests and the color coordinates could be quantified with good reproducibility. The results were related to water activity and to glass transition temperature. The occurrence of mechanical changes in the powder was shown to precede significant color changes with increasing water activity. Considering the susceptibility to stickiness, the stability limit was observed at T−T_g ≈ 2 °C, with a high degree of mechanical changes being detected at T−T_g ≈ 16 °C, whereas for significant color changes this critical temperature difference was around 32 °C.     

Quantifying phosphine penetration through the bark of pine (Pinus radiata D.Don) logs

Phosphine (PH₃) is used as an in-transit phytosanitary treatment (10-d fumigation period) for pine (Pinus radiata D.Don) logs exported from New Zealand to China. The ability of PH₃ to penetrate through the bark of the logs is not well known. We designed equipment to accurately quantify PH₃ penetration into the bark of wooden blocks (100 × 100 × 50 mm; n = 12) cut from the upper and lower trunk of recently harvested pine trees fumigated at 15 or 25 °C. Fumigations simulated commercial conditions consisting of two phases; phase I with 2.0 g m⁻³ of PH₃ for the first 5 days (1–120 h) and 1.5 g m⁻³ of PH₃ in phase II for the next 5 days (121–240 h). During the 10-d schedule, we achieved the required commercial CT (concentration × time) of ≥48,000 ppm h at both temperatures. Bark thickness (i.e., trunk location) did not significantly affect fumigant penetration. Phosphine penetration through the bark of the wooden blocks was greatest after each application, then the penetrated concentrations diminished over time. Greater penetration occurred at 15 °C than at 25 °C. Further studies are required to better understand the dynamics of PH₃ penetration particularly at lower temperatures and through insect-infested blocks.     

The operation types and operation window for high-purity hydrogen production for the sorption enhanced steam methane reforming in a fixed-bed reactor

The operation types and operation window for high-purity H₂ production for the sorption enhanced steam methane reforming (SE-SMR) with Ni/Al₂O₃ catalyst and CaO sorbent in a fixed-bed reactor are investigated by an experimentally verified 2D numerical method. Four chemical reactions including steam reforming, water gas shift, global steam reforming, and CO₂ sorption are considered. The operation window is defined as the H₂ and CO molar fractions at outlet satisfying both y_H2,out ≥ 90% and y_CO,out ≤ y_CO,allow (= 1%, 2% or 3%) in dry base. Under the conditions of y_H2,out and y_CO,allow, there are six operation types, of which 2 types are within the operation window and 4 types are not within the operation window as the temperature, weight hourly space velocity (WHSV) and steam to methane (S/C) molar ratio vary. For a common case of S/C = 3, the operation windows for y_CO,allow = 3% at WHSV = 8.5 h^?1 and 42.5 h^?1 are located at 570–670 °C and 640–690 °C respectively, based on the parameters in this work. The operation window of temperature is wider with decreasing WHSV, and it becomes wider remarkably as the S/C ratio increases. The lowest temperature inside the operation window is 550 °C. The effects of the temperature, WHSV and S/C ratio on the operating types, y_H2,out and y_CO,out are also presented and discussed in details.     

Chemical looping glycerol reforming for hydrogen production by Ni@ZrO2 nanocomposite oxygen carriers

The research describes the synthesis of nanocomposite Ni@ZrO₂ oxygen carriers (OCs) and lanthanide doping effect on maintaining the platelet-structure of the nanocomposite OCs. The prepared OCs were tested in chemical looping reforming of glycerol (CLR) process and sorption enhanced chemical looping reforming of glycerol (SE-CLR) process. A series of characterization techniques including N₂ adsorption-desorption, X-ray diffraction (XRD), inductively coupled plasma optical emission spectrometry (ICP-OES), high resolution transmission electron microscopy (HRTEM), H₂ temperature-programmed reduction (H₂-TPR), H₂ pulse chemisorption and O₂ temperature-programmed desorption (O₂-TPD) were used to investigate the physical properties of the fresh and used OCs. The results show that the platelet-stack structure of nanocomposite OCs could significantly improve the metal support interaction (MSI), thus enhancing the sintering resistance. The effect of lanthanide promotion on maintaining this platelet-stack structure increased with the lanthanide radius, namely, La³⁺ > Ce³⁺ > Pr³⁺ > Yb³⁺. Additionally, the oxygen mobility was also enhanced because of the coordination of oxygen transfer channel size by doping small radius lanthanide ions. The CeNi@ZrO₂ showed a moderate ‘dead time’ of 220 s, a high H₂ selectivity of 94% and a nearly complete glycerol conversion throughout a 50-cycle CLR test. In a 50-cycle SE-CLR stability test, the CeNi@ZrO₂CaO showed high H₂ purity of 96.3%, and an average CaCO₃ decomposition percentage of 53% without external heating was achieved.     

High capacity potassium-promoted hydrotalcite for CO2 capture in H2 production

This paper presents an experimental study for a newly modified K₂CO₃-promoted hydrotalcite material as a novel high capacity sorbent for in-situ CO₂ capture. The sorbent is employed in the sorption enhanced steam reforming process for an efficient H₂ production at low temperature (400–500 ^°C). A new set of adsorption data is reported for CO₂ adsorption over K-hydrotalcite at 400 °C. The equilibrium sorption data obtained from a column apparatus can be adequately described by a Freundlich isotherm. The sorbent shows fast adsorption rates and attains a relatively high sorption capacity of 0.95 mol/kg on the fresh sorbent. CO₂ desorption experiments are conducted to examine the effect of humidity content in the gas purge and the regeneration time on CO₂ desorption rates. A large portion of CO₂ is easily recovered in the first few minutes of a desorption cycle due to a fast desorption step, which is associated with a physi/chemisorption step on the monolayer surface of the fresh sorbent. The complete recovery of CO₂ was then achieved in a slower desorption step associated with a reversible chemisorption in a multi-layer surface of the sorbent. The sorbent shows a loss of 8% of its fresh capacity due to an irreversible chemisorption, however, it preserves a stable working capacity of about 0.89 mol/kg, suggesting a reversible chemisorption process. The sorbent also presents a good cyclic thermal stability in the temperature range of 400–500 °C.     

凹凸棒石粘土对中低放核素Sr、Cs的吸附研究

通过实验研究 ,讨论了经不同方法改性处理的凹凸棒石粘土对锶铯的吸附作用。研究表明凹凸棒石粘土对铯的吸附能力优于锶。特别是经改性剂处理的凹凸棒石粘土 ,在碱性、氧化条件下对锶铯的吸附更为显著     

Thickening of molten white chocolates during storage

When white chocolates are kept molten in storage tanks, problems can arise due to uncontrolled thickening and solidifying of the chocolate mass. The thickening of molten white chocolate was simulated on a laboratory scale using a rotational rheometer under static conditions, interrupted by short shear periods to measure the increasing viscosity. Several chocolates having different dairy components and fat contents were investigated for their tendency to thicken. In addition, sorption isotherms for white chocolates were obtained using dynamic vapour sorption at different temperatures. The sorption isotherms showed the presence of amorphous lactose in all the chocolates that were manufactured from milk powders. Moisture that is released during the crystallization of amorphous lactose causes stickiness and agglomeration of the neighbouring particles and starts the thickening process. This process is highly temperature-dependent. On elevating the temperature the lactose crystallization occurs at lower relative humidities. In order to reduce the tendency of white chocolate to thicken, a high free-fat level should be maintained, based on a high total fat content and on the use of high free-fat milk powders, preferably roller-dried whole milk powders or the combination of skimmed milk powder and anhydrous milk fat.