Hydrogenation of canola oil in the presence of nickel and the methyl benzoate-chrome carbonyl complex

Canola oil was hydrogenated using a mixture of homogeneous methyl benzoate-Cr(CO)₃ and heterogeneous nickel catalysts. The effect of the methyl benzoate-Cr(CO)₃_to-nickel ratio on the activity, specific isomerization index, linoleate and linolenate selectivities, and fatty acid composition was evaluated, and the results compared with those obtained with commercial nickel catalyst and methyl benzoate-Cr(CO)₃ used individually. At higher chromium-to-nickel ratios the activity of nickel was inhibited and the system behaved essentially like the pure chrome complex, while at low chromium-to-nickel ratios the characteristics of the nickel predominated. In a short transition zone relatively high reaction rates were obtained with significantly reducedtrans-isomer levels in the product. In a broader sense, it may be possible to combine a homogeneous and heterogeneous catalyst while retaining the advantages of both. We may thus be able to design catalyst systems for specific applications.     

CSAa黏弹性表面活性剂压裂液的研制

用化学试荆长链烷基季铵盐CSAa制备了两种VES压裂液并研究了相关性能，其组成（CSAa／水杨酸钠／氯化钾／正丁醇，以g／dL为单位）如下：1．0／0．3／1．0／0．2；2．0／0．6／0．5／0．1。在耐温性测定中，1．0g／dL CSAa压裂液的黏度由30℃时的75．0mPa·s降至50℃时的37．5mPa·s；2．0g／dL CSAa压裂液的黏度由40℃时的225mPa·s逐渐降至55℃时的110mPa·s，再降至60℃时的65．0mPa·s.在1701／s剪切2h后，剪切温度为42℃时1．0g／dL CSAa压裂液的黏度下降26％，剪切温度为53℃时2．0g／dL CSAa压裂液黏度下降9％。陶粒沉降速度测定结果表明，40℃、42℃时的1．0g／dL CSAa压裂液（黏度分别为60和54mPa·s）和50℃、53℃时的2．0g／dLCSAa压裂液（黏度分别为180和145mPa·s）携砂性能良好，而45℃、50℃时的1．0g／dLCSAa压裂液和55℃、60℃时的2．0g／dL CSAa压裂液，携砂性能则较差或很差。认为VES压裂液的携砂性能来源于棒状胶束网络，并不全由压裂液黏度决定。还考察了VES压裂液的破胶性能。图1表2参5。     

Recovery of Sb(V) using a functional-ligand-containing porous hollow-fiber membrane prepared by radiation-induced graft polymerization

A ligand-containing porous membrane was prepared by radiation-induced graft polymerization of an epoxy-group-containing monomer of glycidyl methacrylate onto a polyethylene porous hollow-fiber membrane and by subsequent conversion of the epoxy group to an N-methylglucamino (NMG) group at a density of 0.78 mmol/g of the membrane. Sb(V) solution was permeated through the NMG-ligand-containing porous hollow-fiber membrane. Optimum pH for Sb(V) recovery was 3.0. Breakthrough curves of Sb (V) overlapped irrespective of residence times of Sb (V) in the membrane, due to negligible diffusional mass-transfer resistance. Maximum amount of Sb (V) adsorbed was 130 mg/g-membrane, which was equivalent to 1.3 binding molar ratio. Repeated usage of the membrane for adsorption and elution was possible.     

HPLC–MS analysis of the green food colorant sodium copper chlorophyllin

Five commercial samples of sodium copper chlorophyllin, a green food colorant, were analysed by high-performance liquid chromatography (HPLC) using diode-array detection (DAD) and mass spectrometry (MS). Some of the constituents were identified using authentic standards, whereas others were identified tentatively based on their absorption spectra and mass data. The composition of three of the samples was very similar, whereas the other two were quite different. In the three former samples, the three largest peaks could be assigned to Cu chlorin e₆, Cu chlorin p₆, and Cu isochlorin e₄. In one of the two other samples, these three compounds were also among the largest peaks, whereas Cu chlorin e₆ was a small peak in the last sample and Cu chlorin p₆ was absent altogether. Porphyrins were also present in the samples, while except in one of the samples chlorins derived from chlorophyll b were largely absent.Industrial relevanceSodium copper chlorophyllin is a green food colorant made from chlorophyll. Sodium copper chlorophyllin is made by saponifying chlorophyll and coppering the resulting product. This processing leads to a complex mixture of compounds. An analytical method was developed that can be used to identify many of these compounds and show the extent of coppering and degradation of sodium copper chlorophyllin, which may be used industrially to optimize the production of sodium copper chlorophyllin.     

Reductive acid leaching of manganese dioxide with glucose: Identification of oxidation derivatives of glucose

The oxidation of glucose during the reductive leaching of pure MnO₂ and manganese ore in sulphuric acid at 90 °C MnO₂ was investigated. The aim was to identify the derivatives and the chemical pathway of glucose oxidation. Organic derivatives were monitored by HPLC using an Aminex HPX-78H column and UV detection. Chromatographic patterns of leaching solutions showed that major compound formed was formic acid. Minor quantities of glycolic, glyceric and traces of gluconic acids were identified. Results suggest that during the leaching reaction, the carbon chain of glucose is shortened by detachment of one carbon atom as formic acid.     

Bonelike apatite formation on carbon microspheres

Carbon microspheres with a diameter of 2 μm were prepared by hydrothermal process. The apatite-formation ability of the carbon microspheres was evaluated by soaking them in a simulated body fluid (SBF) for 5 and 10 d and apatite-formation mechanism was also analyzed. The result showed that bonelike apatite was formed on the surface of carbon microspheres. Our study indicates that the carbon microspheres synthesized by this method possess apatite-formation ability and may be used as a bioactive injectable filler for bone tissue regeneration.     

Effect of charge trapping species of cupric ions on the photocatalytic oxidation of resorcinol

The photocatalytic oxidation of resorcinol, a potent endocrine disrupting chemical, in oxygenated aqueous suspensions of pure and cupric ions modified Degussa P25 titanium dioxide has been investigated at pH 3.0 ± 0.5. The initial rate of photocatalytic oxidation of resorcinol increased until an optimum dissolved cupric ions concentration was reached at 1.04 mM. At the optimum concentration of cupric ions, the initial rate of photocatalytic mineralisation and degradation of resorcinol was improved by 400%. The observed beneficial effect of cupric ions on the initial rate of resorcinol oxidation could be attributed to the formation of complex and its participation in the photoredox cyclic reaction.Two of the initial oxidation intermediates detected were 1,2,3-trihydroxybenzene and 1,2,4-trihydroxybenzene. These intermediates were formed via hydroxylation of the aromatic ring of resorcinol. Evidences have revealed that 1,2,4-trihydroxybenzene interacted strongly with cupric ions forming copper(II)-trihydroxybenzoate complexes that possessed good adsorption onto TiO₂ surface. These dual-effects help to draw the metal ions closer to the photocatalyst surface and subsequently trigger the electron trapping mechanism by cupric ions. As a result, this improved the charge carriers’ separation. Furthermore, in the presence of oxygen, reoxidation of photoreduced cupric ions occurred and this eliminated the possibility of copper photodeposition, while inducing a photoredox cyclic reaction to regenerate copper species that may potentially act as co-catalyst for the oxidation of 1,2,4-trihydroxybenzene. In contrast, no obvious complex formation was seen between 1,2,3-trihydroxybenzene and cupric ions. This pointed to an intriguing finding which indicates that the positioning of functional group on benzene ring influences the role of cupric ions.     

Analysis and improvement of fair certified e-mail delivery protocol

Recently, Nenadić et al. proposed a novel fair exchange protocol RSA-CEMD [A. Nenadić, N. Zhang, S. Barton. Fair certified e-mail delivery, Proceedings of the 9th ACM Symposium on Applied Computing (SAC 2004)-Computer Security Track, Nicosia, Cyprus, pp. 391–396, 2004] for certified e-mail delivery with an off-line and transparent trusted third party. The protocol provides non-repudiation of origin and non-repudiation of receipt security service to protect communicating parties from each other's false denials that the e-mail has been sent and received. In this paper, we show that Nenadić's protocol cannot achieve the claimed fairness. In the exchange protocol, the receiver can cheat the sender successfully by sending an invalid verifiable and recoverable encryption of signature (VRES) which can pass all the sender's verifications, as the VRES scheme proposed in [A. Nenadić, N. Zhang, S. Barton. Fair certified e-mail delivery, Proceedings of the 9th ACM Symposium on Applied Computing (SAC 2004)-Computer Security Track, Nicosia, Cyprus, pp. 391–396, 2004] is inherently unrecoverable in some situations. In other words, there is always that the receiver can get the sender's e-mail message while the sender cannot obtain receiver's receipt. Furthermore, we propose a revised version of certified e-mail delivery protocol that preserves strong fairness while remaining optimistic.     

Physicochemical characteristics and leachability of scale and sludge from Bulalo geothermal system, Philippines

Scale and sludge from Bulalo geothermal field, Philippines, have been characterized by whole rock analysis, radioactivity counting, size analysis, light microscopy, scanning electron microscopy, and X-ray diffraction. Their leachability was assessed by regulatory leaching procedures and by sequential extraction. Both scale and sludge consisted mostly of oxides of Si, Al, and Fe with no radionuclides detected. The scale had 10% S content. Sulfides and silicates were important phases in both samples having size ranges from submicron to 2 mm. Geothermal soils at Bulalo have higher than normal soil levels of As, S, Cu, Cr, Zn, and Pb but regulatory leaching tests indicated that these elements are not released. However, the sequential extraction showed that As, Cu, and Zn were leachable under extreme conditions.     

Effect of oxygen flow rate on the structural and electrochemical properties of lithium nickel oxides synthesized by the sol–gel method

The structural and electrochemical properties of LiNiO₂ powders were investigated as a function of the oxygen flow rate employed in the preparation of lithium nickel oxide. It was found that oxygen played an important role in the synthesis of highly crystallized LiNiO₂(R3¯m). In the crystallization process of LiNiO₂, a deficiency of oxygen in the calcination reactor induced the formation of impurities and cubic rock-salt structure (Fm3m) in LiNiO₂ powders. For LiNiO₂ prepared at higher oxygen flow rates, the electrode delivered high discharge capacities with relatively good retention rates. But very low electrode capacity was obtained from LiNiO₂ prepared at lower oxygen flow rates.