A metal-OH group modification strategy to prepare highly-hydrophobic MIL-53-Al for efficient acetone capture under humid conditions

A series of highly-hydrophobic MIL-53-Al (MIL = Materials of Institut Lavoisier) frameworks synthesized via decoration of the Al-OH groups by alkyl phosphonic acid were developed as adsorbents for removing acetone from humid gas streams. The newly prepared materials were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), scanning electron microscope (SEM), N₂ adsorption-desorption and thermogravimetric analysis (TGA). Their adsorption behaviors toward acetone vapor under dry and wet conditions were studied subsequently. Results showed that alkyl phosphonic acid was successfully grafted into MIL-53-Al skeleton through coordinating interaction with Al³⁺ generating [email protected]_x (x = 12, 14, 18). The [email protected]_x exhibited similar crystal structure and thermal stability to parent MIL-53-Al. Furthermore, the modified materials showed significantly enhanced hydrophobicity. The water vapor uptake of [email protected]₁₄ decreased by 72.55% at 75% relative humidity (RH). Dynamic adsorption experiments demonstrated that water vapor had almost no effect on the acetone adsorption performance of [email protected]₁₄. Under the condition of 90% RH, the acetone adsorption capacity of [email protected]₁₄ was 102.98% higher than that of MIL-53-Al. Notably, [email protected]₁₄ presented excellent adsorption reversibility and regeneration performance in 10 adsorption-desorption cycles. Taken together, the strategy of metal-OH group modification is an attractive way to improve the acetone adsorption performance over metal-organic frameworks (MOFs) under humid conditions. Besides, [email protected]₁₄ would be deemed as a promising candidate for capturing acetone in high moisture environment.     

烷基酚装置过滤工序改造设计

在兰州炼油化工添加剂厂烷基酚装置过滤工序改造设计中 ,通过优化流程、更新设备、改善计量等措施 ,达到了消除装置瓶颈、提高生产能力、节能降耗、保证安全及解决环境污染的目的 ,取得了良好的效果。     

Degradation and plant uptake of nonylphenol (NP) and nonylphenol-12-ethoxylate (NP12EO) in four contrasting agricultural soils

Nonylphenol polyethoxylates (NPEOs) are surfactants found ubiquitously in the environment due to widespread industrial and domestic use. Biodegradation of NPEOs produces nonylphenol (NP), an endocrine disruptor. Sewage sludge application introduces NPEOs and NP into soils, potentially leading to accumulation in soils and crops. We examined degradation of NP and nonylphenol-12-ethoxylate (NP12EO) in four soils. NP12EO degraded rapidly (initial half time 0.3-5 days). Concentrations became undetectable within 70-90 days, with a small increase in NP concentrations after 30 days. NP initially degraded quickly (mean half time 11.5 days), but in three soils a recalcitrant fraction of 26-35% remained: the non-degrading fraction may consist of branched isomers, resistant to biodegradation. Uptake of NP by bean plants was also examined. Mean bioconcentration factors for shoots and seeds were 0.71 and 0.58, respectively. Removal of NP from the soil by plant uptake was negligible (0.01-0.02% of initial NP). Root concentrations were substantially higher than shoot and seed concentrations.     

The effect of alkyl chain length on the degradation of alkylimidazolium- and pyridinium-type ionic liquids in a Fenton-like system

Background, aim, and scope  Ionic liquids are regarded as essentially “green” chemicals because of their insignificant vapor pressure and, hence, are a good alternative to the emissions of toxic conventional volatile solvents. Not only because of their attractive industrial applications, but also due to their very high stability, ionic liquids could soon become persistent contaminants of technological wastewaters and, moreover, break through into natural waters following classical treatment systems. The removal of harmful organic pollutants has forced the development of new methodologies known as advanced oxidation processes (AOPs). Among them, the Fenton and Fenton-like reactions are usually modified by the use of a higher hydrogen peroxide concentration and through different catalysts. The aim of this study was to assess the effect of hydrogen peroxide concentration on degradation rates in a Fenton-like system of alkylimidazolium ionic liquids with alkyl chains of varying length and 3-methyl-N-butylpyridinium chloride. Materials and methods  The ionic liquids were oxidized in dilute aqueous solution in the presence of two different concentrations of hydrogen peroxide. All reactions were performed in the dark to prevent photoreduction of Fe(III). The concentrations of ionic liquids during the process were monitored with high-performance liquid chromatography. Preliminary degradation pathways were studied with the aid of ¹H NMR. Results  Degradation of ionic liquids in this system was quite effective. Increasing the H₂O₂ concentration from 100 to 400 mM improved ionic liquid degradation from 57–84% to 87–100% after 60 min reaction time. Resistance to degradation was weaker, the shorter the alkyl chain. Discussion  The compound omimCl was more resistant to oxidation then other compounds, which suggests that the oxidation rates of imidazolium ionic liquids by OH· are structure-dependent and are correlated with the n-alkyl chain length substituted at the N-1-position. The level of degradation was dependent on the type of head group. Replacing the imidazolium head group with pyridinium increased resistance to degradation. Nonetheless, lengthening the alkyl chain from four to eight carbons lowered the rate of ionic liquid degradation to a greater extent than changing the head group from imidazolium to pyridinium. 1H-NMR spectra show, in the first stage of degradation, that it is likely that radical attack is nonspecific, with any one of the carbon atoms in the ring and the n-alkyl chain being susceptible to attack. Conclusions  The proposed method has proven to be an efficient and reliable method for the degradation of imidazolium ionic liquids by a Fenton-like reagent deteriorated with lengthening n-alkyl substituents and by replacing the imidazolium head group with pyridinium. The enhanced resistance of 1-butyl-3-methylpyridinium chloride when the resistance of imidazolium ionic liquids decreases with increasing H₂O₂ concentration is probably indicative of a change in the degradation mechanism in a vigorous Fenton-like system. H-NMR spectra showed, in the first stage of degradation, that radical attack is nonspecific, with any one of the carbon atoms in the ring and the n-alkyl chain being susceptible to attack. Recommendations and perspectives  Since ionic liquids are now one of the most promising alternative chemicals of the future, the degradation and waste management studies should be integrated into a general development research of these chemicals. In the case of imidazolium and pyridinium ionic liquids that are known to be resistant to bio- or thermal degradation, studies in the field of AOPs should assist the future structural design as well as tailor the technological process of these chemicals     

The Kinetics of Interesterfication on Waste Cooking Oil (Sunflower Oil) for the Production of Fatty Acid Alkyl Esters using a Whole Cell Biocatalyst (Rhizopus oryzae) and Pure Lipase Enzyme

Recent research and technology have provided promising outcomes to rely on biodiesel as the alternative and conventional source of fuel. The use of renewable sources constitutes the main stream of research. Waste Cooking Oil (WCO) was used for biodiesel production in this study. Lipase enzyme producing fungi Rhizopus oryzae 262 and commercially available pure lipase enzyme were used for comparative study in the production of FAAE. The whole cell biocatalyst and pure enzyme were immobilized using calcium alginate beads. It was prepared by optimizing with different molar ratios of calcium chloride and different percent sodium alginate. Entrapment immobilization was done for whole cell biocatalyst. PE was also immobilized by entrapment for the transesterification reaction. Four different solvents methanol, ethanol, n-propanol, n-butanol were used as the acyl acceptors. The reaction parameters like temperature, molar ratio, reaction time, and amount of enzyme to be used were also optimized for methanol alone. The same parameters were adopted for the other acyl acceptors too. Among the different acyl acceptors, methanol whose reaction parameters were optimized showed maximum conversion of triglycerides to FAAE - 94% with PE and 84% with WCB. On the whole, PE showed better catalytic converting ability with all the acyl acceptor compared to WCB, further study, it was observed that three consecutive and reversible reactions occurred in the interesterification of triglycerides. So, a kinetic model based on Michaelis-Menten equation with competitive substrate inhibition was used to find the maximum reaction rate V_i for the four solvents using pure enzyme and WCB.     

滇池烷基苯磺酸钠的分布,降解及对鲤鱼的危害效应

研究表明滇池水中ＬＡＳ含量为０．０１８～０．０２９ｍｇ／ｌ，局部水域达０．２～０．７ｍｇ／ｌ；ＡＢＳ强烈地吸附在底质中，以湖体呈曲线分布，平均含量高达０．４３ｍｇ／ｋｇ，１６ｈ内ＬＡＳ动态降解率比静态降解率高２．２倍，不同浓度的ＬＡＳ对滇池鲤鱼的结果表明，５～３５ｍｇ／ｌ浓度水中，溶解氧下降，ｐＨ值升高，产生急性危害效应，半致死浓度４８ＴＬ５０为３．０ｍｇ／ｌ，完全浓度为０．３ｍｇ／ｌ。当ＬＡＳ含     

苯砜基环烷酸酯类化合物的结构与急性毒性关系的密度泛函理论研究

用密度泛函理论方法,在B3LYP／LANL2DZ水平上,计算了28个苯砜基环烷酸酯类化合物的结构参数;将结构参数作为理论描述符,导出苯砜基环烷酸酯类化合物的分子结构参数(α、εa、q^-和μ)与对发光菌毒性(EC50和LC50)的定量关系方程,并用交叉验证法验证,r^2分别为0.9509和0.9320,q^2分别为0．9318和0．9025,其结果优于AM1、CoMFA和CoMSIA方法的计算结果．     

有机烷酚类化合物致突变性研究

采用鼠伤寒沙门氏菌致突变试验(AmesTest)菌株TA97,TA98,TA100,TA102,对环境中潜在内分泌激素干扰污染物甲基苯酚等12种烷酚类有机物的致突变性进行研究。结果表明,除2,4-二氯苯酚外,烷酚类化合物对Ames试验中TA98菌株的平皿掺入试验,均诱发显示阳性反应;其中对壬基酚、2,6-二甲基苯酚、4-辛基酚等烷基酚类化合物呈强阳性反应,怀疑这几种化合物具有强致突变性,且以碱基移码型突变为主。      

Effect of an eco-friendly o/w emulsion stabilized with amphiphilic sodium alginate derivatives on lambda-cyhalothrin adsorption–desorption on natural soil minerals

The effects of amphiphilic O/W emulsions,stabilized by the alkyl polyglycoside(APG)or cholesterol-grafted sodium alginate(CSAD)/APG systems,on lambda-cyhalothrin adsorption/desorption mechanisms on natural soil minerals(i.e.,illite and kaolinite)were investigated.Sorption and desorption of lambda-cyhalothrin onto soil minerals was studied via batch equilibration to give insight into the adsorption equilibrium,kinetics,and thermodynamics of lambda-cyhalothrin adsorption onto minerals.The results indicate the following:(i)The adsorption processes for the APG system and CSAD/APG system include:rapid adsorption,slow adsorption,and adsorption equilibrium.The adsorption kinetics of pesticide on illite and kaolinite are in accordance with the Ho and McKay model,and the adsorption isotherm conforms to the Freundlich model.In addition,the adsorption processes of pesticide for the two systems on minerals were spontaneous and feasible(ΔG~00),endothermic(ΔH~00),and mainly involved chemical bonding(ΔH~060).(ii)The equilibrium adsorption percentages of the pesticide on illite for the APG system and CSAD/APG system were 42.4%and 64.8%,and the corresponding equilibrium adsorption percentages on kaolinite were 40.8%and 61.8%,respectively.Moreover,the pesticide adsorption rate K_(2-CSAD/APG)was faster than K_(2-APG),and its adsorption capacity K_(f-CSAD/APG )was greater than K_(f-APG).Meanwhile,the pesticide desorption K_(fd)in the CSAD/APG system was smaller than that in the APG system.As a result,this eco-friendly O/W emulsion based on amphiphilic sodium alginate derivatives might provide a green pesticide formulation,since it could reduce the amount of lambda-cyhalothrin entering aquatic systems to threaten non-target fish and invertebrate species.