Membrane processing of used frying oils

Studies were conducted with used frying oils in a flat membrane batch cell using five different types of polymeric membranes to decrease the soluble degradation products. During membrane processing, triglycerides permeated preferentially compared to the majority of the polar compounds including oxidation products, polymers, and color compounds. Two of the composite membranes, NTGS-AX and NTGS-2200, selectively rejected polar compounds and oxidation products to the extent of 25–48% and 24–44% respectively. The reduction in Lovibond color values (5R+Y) was in the range of 83–93%. The viscosity of the used frying oil was reduced to the extent of 22%. The composite membranes were effective in reducing the soluble impurities, as well as insoluble particulates, without causing any undesirable changes to the oil. The membrane process appears to improve the life of used frying oils and does not have the disadvantages associated with the active filtration systems, however, for commercial application the permeate flux needs to be improved considerably.     

The alkylation of biphenyl over three-dimensional large pore zeolites: The influence of zeolite structure and alkylating agent on the selectivity for 4,4′-dialkylbiphenyl

Catalytic properties of three-dimensional zeolites, Y (FAU), Beta (BEA), and CIT-1 (CON) zeolites were examined in the alkylation, isopropylation, sec-butylation, and tert-butylation, of biphenyl (BP), and compared to those of H-mordenite (MOR). The selectivities for 4,4′-dialkylbiphenyl (4,4′-DABP) varied with the types of zeolite and of alkylating agent. FAU, BEA, and CON gave only low selectivities for 4,4′-diisopropylbiphenyl (4,4′-DIPB) in the isopropylation, and predominant isomers were bulky and thermodynamically unstable 2,x′-DIPB (2,2′-, 2,3′-, and 2,4′-) at lower temperatures, and bulky and thermodynamically stable 3,4′- and 3,3′-DIPB at higher temperatures: this is quite different from catalytic features over MOR, which gave 4,4′-DIPB with high selectivities at moderate temperatures. These results suggest that FAU, BEA, and CON have no shape-selective nature in the isopropylation, and that the reaction is principally controlled kinetically at lower temperatures, and thermodynamically at higher temperatures. The sec-butylation gave similar results to the isopropylation. Although the selectivities for 4,4′-di-sec-butylbiphenyl (4,4′-DSBB) were higher than those in the isopropylation, predominant isomers were 2,x′-DSBB (2,2′-, 2,3′-, and 2,4′-) at lower temperatures, and 3,4′- and 3,3′-DSBB at higher temperatures. The tert-butylation gave 4,4′-di-tert-butylbiphenyl (4,4′-DTBB) in moderate to high selectivities over all zeolites at moderate temperatures: the selectivity for 4,4′-DTBB was higher than 80% over BEA and CON; however, it still remained at 50% over FAU. FAU channels with super cages are too large for selective formation of 4,4′-DTBB.

From these results, it is concluded that the selectivity for 4,4′-DABP in the alkylation over MOR, FAU, BEA, and CON is determined by the exclusion of bulky isomers at their transition states, and that the exclusion is caused by the steric restriction at the transition states of bulky isomers by the zeolite channels.     

Evaluation of surfactant-aided degumming of vegetable oils by membrane technology

The first step in the process of vegetable oil refining is degumming, in which phospholipids and mucilaginous gums are removed that otherwise result in a low-grade oil. A membrane process is remarkably simple yet potentially offers many advantages in degumming. Studies were conducted on surfactant-aided membrane degumming with soybean and rapeseed oils in a magnetically stirred flat membrane batch cell with different types of microfiltration membranes. The reduction of phospholipids in soybean oil was in the range of 85.8–92.8% during the membrane process. The phosphorus content of membrane permeates of soybean oil was in the range of 20–58 mg/kg. Crude rapeseed oil contained higher amount of nonhydratable phospholipids and hence resulted in lower reduction in phospholipids, in the range of 66.4–83.2%. Addition of hydratable phospholipids could improve the efficiency of degumming in the membrane process without using any electrolyte, resulting in improvement of quality as well as quantity of the phospholipids.     

MiR-10a in Pancreatic Juice as a Biomarker for Invasive Intraductal Papillary Mucinous Neoplasm by miRNA Sequencing

New biomarkers are needed to further stratify the risk of malignancy in intraductal papillary mucinous neoplasm (IPMN). Although microRNAs (miRNAs) are expected to be stable biomarkers, they can vary owing to a lack of definite internal controls. To identify universal biomarkers for invasive IPMN, we performed miRNA sequencing using tumor-normal paired samples. A total of 19 resected tissues and 13 pancreatic juice samples from 32 IPMN patients were analyzed for miRNA expression by next-generation sequencing with a two-step normalization of miRNA sequence data. The miRNAs involved in IPMN associated with invasive carcinoma were identified from this tissue analysis and further verified with the pancreatic juice samples. From the tumor-normal paired tissue analysis of the expression levels of 2792 miRNAs, 20 upregulated and 17 downregulated miRNAs were identified. In IPMN associated with invasive carcinoma (INV), miR-10a-5p and miR-221-3p were upregulated and miR-148a-3p was downregulated when compared with noninvasive IPMN. When these findings were further validated with pancreatic juice samples, miR-10a-5p was found to be elevated in INV (p = 0.002). Therefore, three differentially expressed miRNAs were identified in tissues with INV, and the expression of miR-10a-5p was also elevated in pancreatic juice samples with INV. MiR-10a-5p is a promising additional biomarker for invasive IPMN.     

Transport of direct dye into cellulose membrane

The dyeing process for a cellulose membrane–direct dye system is analyzed based on a parallel transport mechanism of surface and pore diffusion with Freundlich isotherm. Numerical solutions were obtained in order to clarify how the surface and pore diffusion resistances affect the uptake curve. The numerical solutions were also compared with an analytical solution for surface diffusion control to establish the range where the analytical solution can be considered as an acceptable approximation. The uptake curves in the cellulose membrane-chromophore (C.I. Direct Yellow 12) system in the presence of inorganic electrolyte were measured. The rate of adsorption and the maximum amount of adsorption increased with an increase in the concentration of those electrolytes. The rate of adsorption was approximately controlled by the surface diffusion rather than by pore diffusion. The surface diffusivities of the dye were little affected by either the concentration and or nature of the electrolyte.     

Magnetic Interaction in Insulating Cuprates

We examine two-spin (2S) and cyclic four-spin (4S) magnetic interactions in insulating ladder and two-dimensional (2D) cuprates. By a comparison of eigenstates between d-p and Heisenberg models, we evaluate magnitudes of these interactions. We find that the 4S interaction is 10 % of nearest neighboring 2S interaction, and a diagonal 2S interaction is considerably small. The 4S interaction for a ladder cuprate is larger than that for 2D one, and plays an important role in the low-energy excitation. The Heisenberg ladder with the obtained 2S and 4S interactions reproduces very well the experimental result of the temperature dependence of the magnetic susceptibility.     

Grafting of poly(ethylene-block-ethylene oxide) onto a vapor grown carbon fiber surface by γ-ray radiation grafting

To modify the surface of vapor grown carbon fiber (VGCF), poly(ethylene-block-ethylene oxide) (PE-b-PEO, M_n=1400, PEO content=50 wt%) was successfully grafted onto the surface by using γ-ray irradiation of the PE-b-PEO-adsorbed VGCF in solvent-free system. It is found that the percentage of polymer grafting reached 15.0% when the PE-b-PEO-adsorbed VGCF was irradiated by γ-ray over 40 kGy dose at 110 °C, but at the lower irradiation temperature of 75 °C, the grafting reaction scarcely proceeded. This indicates that polymer radicals formed by γ-ray irradiation were successfully trapped by VGCF surface above melting point of PE-b-PEO. On the other hand, when the dispersion of VGCF in THF solution of PE-b-PEO was irradiated, the percentage of PE-b-PEO grafting was less than 4.0%. It was confirmed by a field-emission scanning electron microscope (FE-SEM) that the surface of the VGCF was uniformly covered by grafted PE-b-PEO. In addition, the surface free energy of ungrafted and PE-b-PEO-grafted VGCF was determined.     

A novel photoreactive amphiphile of nitrophenylazide for immobilization of bioactive proteins

Monolayers of an amphiphilic nitrophenylazide (ANPA) derivative were prepared and their ability to immobilize a protein molecule by a photochemical binding reaction was demonstrated as a novel means to constitute a biofunctional membrane. Molecular orientations and photoreactions in the ANPA monolayers were investigated by Fourier transform IR spectroscopy. Rapid photolysis of ANPA was observed which reflects decomposition of the azide group to a reactive nitrene radical intermediate. As an enzyme, glucose oxidase (GOD) was immobilized on a monomolecular film of ANPA, coated on a substrate, by means of enzyme adsorption at the solid-solution interface and subsequent photolysis of ANPA. Radioisotope labelling experiments revealed that the enzyme was immobilized at a high surface concentration which corresponds to a closely packed monolayer of GOD. The specific activity of the immobilized enzyme was estimated to be high compared with those of other systems involving the adsorption of this enzyme. The usefulness of the present technique for fabricating biofunctional monolayer assemblies is discussed.     

PROGRESSIVE HYDROTREATMENT OF HOKKAIDO COALS (JAPAN)

Hokkaido coals were subjected to benzene extraction and non-catalytic hydrotreatment, alternatively, under progressive increase of temperature from 200 to 400 °C. For Taiheiyo coal the aliphatic materials in the hydrogen-rich part of the coal were converted to benzene soluble products at lower temperatures. With the increasing reaction temperature, aromaticity of the benzene solubles increased gradually. On the other hand, for Ohyubari coal, the structure of the benzene solubles were essentially the same for products obtained under all temperatures. Also, in the case of Taiheiyo coal (C : 76.9 %) the plastic state was not observed up to 400 °C, but for Ohyubari coal (C : 85.6 %) the onset of the plastic state was evident. It was assumed that there was an intimate relationship between the occurrence of plastic state and the structural uniformity of coal.