Synthesis,characterization and electrochemical evaluation of anticorrosion property of a tetrapolymer for carbon steel in strong acid media

A novel tetrapolymer(TP) consisting of carboxylate, sulphonate, phosphonate and sulfur dioxide based comonomers was synthesized using Butler cyclopoymerization technique. The synthesized tetrapolymer was characterized using FTIR,1 H-NMR,~(13)CNMR and elemental analysis. The performance of the tetrapolymer as a corrosion inhibitor for St37 carbon steel in 15% HCl and 15% H_2SO_4 acid media was assessed using electrochemical impedance spectroscopy(EIS), linear polarization resistance(LPR), potentiodynamic polarization(PDP) and electrochemical frequency modulation(EFM) techniques. The influence of addition of a small amount of KI on the corrosion inhibition efficiency of TP was also assessed. Results obtained showed that the tetrapolymer moderately inhibited the corrosion of St37 steel in the acid media with protection efficiency of 79.5% and 61.1% at the optimum concentration of 1000 mg·L~(-1) studied in HCl and H_2SO_4 media respectively. On addition of 5 mmol·L~(-1) KI to the optimum tetrapolymer concentration, the protection efficiency was upgraded to 90.6% and 93.5% in HCl and H_2SO_4 environment, respectively. The enhanced performance of the polymer in the presence of KI is due to synergistic action deduced from synergism parameter(S1) which was found to be greater than unity.The tetrapolymer afforded the corrosion inhibition of St37 steel in the acid media by virtue of adsorption of the polymer molecules on the steel surface which was confirmed by ATR-FTIR analysis of the adsorbed film extracted from the steel surface. TP + KI formed complex with St37 steel surface in H_2SO_4 solution but not in HCl solution.     

A novel green inhibitor for C-steel corrosion in 2.0 mol·L~(-1) hydrochloric acid solution

The corrosion inhibition characteristics of aqueous extract of seeds of Melia azedarach L.(MA) have been studied as eco-friendly green inhibitor for corrosion control of C-steel in 2 mol·L~(-1) HCl solution by gravimetric and electrochemical methods. The results depict that, the extract inhibits efficiently the corrosion of carbon steel in hydrochloric acid. The efficiency of extract is increased with increasing the extract concentration but independent on the studied temperature. The adsorption of the extract components onto the steel surface was found to be spontaneous, and follows Langmuir adsorption isotherm. The surface morphology of C-steel, in the absence and presence of MA extract in 2.0 mol·L~(-1) hydrochloric acid solution, was studied using scanning electron microscopy(SEM).     

Hierarchical pore structure of activated carbon fabricated by CO2/microwave for volatile organic compounds adsorption

An activated carbon pore-expanding technique was achieved through innovative reactivation by CO_2/microwave.The original and modified activated carbons were characterized by nitrogen adsorption–desorption,scanning electron microscopy,transmission electron microcopy,and Fourier transform infrared spectroscopy.The mesopore volume increased from 0.122 cm~3·g~(-1) to 0.270 cm~3·g~(-1),and a hierarchical pore structure was formed.A gradual decrease in the phenolic hydroxyl and carboxyl groups on the surface of activated carbon enhanced the surface inertia of granular activated carbon(GAC).The toluene desorption rate of the modified sample increased by 8.81% compared with that of the original GAC.Adsorption isotherm fittings revealed that the Langmuir model was applicable for the original and modified activated carbons.The isosteric adsorption heat of toluene on the activated carbon decreased by approximately 50%,which endowed the modified sample with excellent stability in application.The modified samples showed an enhanced desorption performance of toluene,thereby opening a way to extend the cycle life and improve the economic performance of carbon adsorbent in practical engineering applications.     

Surface modification of polypiperazine-amide membrane by self-assembled method for dye wastewater treatment☆

Polypiperazine-amide membranes were modified with poly(ethyleneimine) (PEI) by self-assembled method, through which PEI molecules were fixed on the membrane surface by ionic interaction. In the experiments, the PEI concentration ranged from 50 to 2000 mg·L?1 while the depositing time was fixed at 20 min. The results showed that low PEI concentration resulted in a slight increase of pure water flux, which was attributed to the enhanced membrane surface hydrophilicity. The PEI adsorption on membrane surface had less effect on the re-jections to neutral PEG and sucrose, but improved the rejections to divalent cationic ions and methylene blue as the result of reversion of the membrane surface charge from negative to positive according to the XPS analysis and zeta potential measurements. The membrane modified at PEI=1500 mg·L?1 exhibited high rejection to methylene blue (MB) and is potential to be applied in the treatment of effluents containing positively charged dyes.     

表面偏析法制备用于乙醇渗透蒸发脱水的整体PVA-PES复合膜(英文)

A facile surface segregation method was utilized to fabricate poly(vinyl alcohol)-polyethersulfone (PVA-PES) composite membranes. PVA and PES were first dissolved in dimethyl sulfoxide (DMSO), then casted on a glass plate and immersed in a coagulation bath. During the phase inversion process in coagulation bath, PVA spontaneously segregated to the polymer solution/coagulation bath interface. The enriched PVA on the surface was further crosslinked by glutaraldehyde. Scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS) and energy dispersive spectrometer (EDS) confirmed the integral and asymmetric membrane structure with a dense PVA-enriched surface and a porous PES-enriched support, as well as the surface enrichment of PVA. The coverage fraction of the membrane surface by PVA reached up to 86.8% when the PVA content in the membrane recipe was 16.7% (by mass). The water contact angle decreased with the increase of PVA content. The effect of co-agulation bath type on membrane structure was analyzed. The membrane pervaporation performance was evaluated by varying the PVA content, the annealing temperature, feed concentration and operation temperature. The mem-brane exhibited a fairly good ethanol dehydration capacity and long-term operational stability.     

侧光光纤引导的内源可见光催化降解亚甲基蓝(英文)

The side-glowing optical fibers (SOFs) were chosen as the conducting medium of endogenous light; and 20 mg·L-1 methylene blue was chosen as the target to be degraded. The SOF is made up of quartz core with a silicon cladding, which can emit light through side surface more uniformly and transmit light for longer distance to avoid attenuation of light by liquid medium. The filament lamp was chosen as visible light source. Different reaction conditions, such as the presence of optical fiber or not, the quantity of SOF, light irradiation intensity were tested by measuring the methylene blue degradation of methylene blue. The results show that suitable reaction conditions were 1.167 g·L-1 Ag + /TiO 2 with 7% (by mass) of Ag + doped in TiO 2 , and 500 roots of SOF (30 cm length in solution). The photocatalytic degradation efficiency under 300W lamp irradiation for 8h was about 97%. And the photocatalytic degradation efficiency of methylene blue degradation was proportional to SOF quantity, light irradiation intensity and catalytic dosage within a certain range. Compared with general UV and visible light SOFs could save a huge amount of energy and cost, in the potential applications in dealing with organic pollutants on a large scale.     

聚乙烯-碳纳米管串晶的高效制备(英文)

We report a novel method to prepare nanohybrid shish-kebab (NHSK) structure of polyethylene (PE) and carbon nanotube (CNT). Pristine CNTs without surface modification with high concentration was effectively dispersed in xylene solution by a simple shearing method, which induces the quick crystallization of PE in xylene to form a novel NHSK structure with more dense and smaller PE kebab on CNT axis. The flocculated NHSK product was transferred quickly from the xylene solution to the ethanol solution, in order to shorten the preparation time. The freeze-drying method was used in vacuum instead of high-temperature drying to avoid the aggregation of NHSK product. These improvements allow the formation of NHSK with an absolute yield of 200 mg·h-1 , which is 2000 folds of that reported previously. It is favorable to apply this structured material in high performance nanocomposite, by improving the compatibility of CNTs in polymer and the interfacial force between CNTs and polymer.     

Potential aspect of rice husk biomass in Australia for nanocrystalline cellulose production

Nanocrystalline cellulose(NCC) was produced from rice husk biomass(Oryza sativa) by a chemical extraction process to explore the potential aspect of agro-waste biomass in Australia. In this work, the delignified rice husk pulp(D-RHP) was produced by alkaline delignification of raw rice husk biomass(R-RHB) using 4 mol·L~(-1) alkali solutions(Na OH) in a jacketed glass reactor under specific experimental conditions. D-RHP was bleached using 15% sodium hypochlorite, and the bleached rice husk pulp was coded as B-RHP. Finally,raw suspension of NCC was produced by the acid hydrolysis of B-RHP using 4 mol·L~(-1) sulphuric acid. The raw suspension of NCC was neutralized by a buffer solution and analyzed by TAPPI, FT-IR, XRD, SEM, AFM, and TEM. FT-IR spectra of NCC are different to R-RHB but similar with B-RHP and D-RHP. From XRD results, the crystallinity of NCC was found to be approximately 65%. In AFM analysis particle thicknesses have been confirmed to be in the range of(25 ± 15.14) nm or(27 ± 15.14) nm which is almost the same. From TEM analysis particle dimensions have been confirmed to be in the range of(50 ± 29.38) nm width and(550 ± 302.75) nm length with the aspect ratio ~ 11:1(length/diameter) at a 500 nm scale bar. On the other hand, at a 200 nm scale bar the particle dimensions have been confirmed to be in the range of(35 ± 17) nm width and(275 ± 151.38)nm length with the aspect ratio ~ 8:1. The aspect ratio of individual crystalline domain was determined in TEM analysis which is 10:1(100/10). Therefore the aspect ratios and dimensions of nanoparticles in NCC suspension are almost the same and in nano-meter scale, as confirmed from both AFM and TEM results. The yield of NCC from B-RHP was found to be approximately 95%, and the recovery of cellulose from R-RHB is about 90%.     

Lysozyme adsorption to cation exchanger derivatized by sequential modification of poly(ethylenimine)-Sepharose with succinic anhydride and ethanolamine: Effect of pH and ionic strength

In our previous work, a series of polyethylenimine(PEI)-derived cation exchangers were synthesized using PEIgrafted resin FF-PEI-L740(ionic capacity, 740 mmol·L~(-1)) as the basic resin to study lysozyme adsorption and chromatographic behavior. It was found that the resin with an ionic capacity of 630 mmol·L~(-1)(FF-PEI-CR630)possessed high adsorption performance towards lysozyme at 0–100 mmol·L~(-1) Na Cl. Therefore, in this work,FF-PEI-CR630 was selected to study the influences of pH and ionic strength(IS) on protein adsorption and chromatographic behavior towards lysozyme. The increase of lysozyme adsorption capacity in the pH range of 6 to 10 was observed. However, the uptake rate decreased in the pH range of 6 to 8 and then remained essentially unchanged from pH 8 to pH 10. Increasing IS led to decreased protein adsorption capacity and increased uptake rate in different pH ranges. Besides, FF-PEI-CR630 maintained dynamic binding capacity as high as over150 mg·ml~(-1) at pH 8–10 without NaCl. The research has thus provided insight into the selection of proper pH and IS conditions for protein purification by using FF-PEI-CR630.     

Simultaneous recovery of phosphorus and nitrogen from liquid digestate by vacuum membrane distillation with permeate fractional condensation

A vacuum membrane distillation(VMD) process with permeate fractional condensation on membrane downstream has been developed for simultaneous recovery of phosphorus and nitrogen from liquid digestate. The polytetrafluoroethylene(PTFE) membrane flux could reach 6000 g·m~(-2)·h~(-1) with the rejection efficiency of total phosphorus(TP) over 0.99, under the condition of flowrate being 120 L·h~(-1) and temperature being 40°C. Membrane fouling occurred with a film of organics and microorganism deposited on the surface of the membrane. Membrane flux could be reversed after the membrane was rinsed by water. Higher feed temperature and flowrate could improve the membrane flux, while hardly affect the rejection efficiency of total phosphorus. The concentration of TP could reach 1600 mg·L~(-1) after membrane distillation, which is about 5 times of that in initial liquid digestate. On the downstream of the membrane, some of the permeate vapor was condensed under the vacuum condition and most of water was collected here. The remaining vapor enriched with total nitrogen(TN) was compressed and pumped to the atmospheric condition to condense. The TN concentration in atmospheric condensate was as high as 7000 mg·L~(-1) with the process separation factor for ammonia being enhanced to 114.     

Effect of sulfate on Cu(Ⅱ) sorption to polymer-supported nano-hydrated ferric oxides: Experimental and modeling studies

Incorporating of hydrous ferric oxide(HFO) inside porous supports with large sizes has become an effective way to decontaminate the water from heavy metals. Ubiquitous anions like sulfate are usually present in high concentrations in water, and might greatly affect adsorption behavior of hybrid HFO. Here, a polymer-based HFO-CPS was fabricated by encapsulating nano-HFO inside a chloromethylated polystyrene polymer(CPS) and the reactivity of HFO-CPS with Cu(Ⅱ) was evaluated in the presence of sulfate ions.Surface complexation theory was firstly employed to describe the effect of sulfate on Cu(Ⅱ) adsorption edges of hybrid HFO-CPS, where constant capacitance model(CCM) was adopted. The available weak adsorption site Fe_((2))OH of hybrid HFO-CPS was found to decrease from 20% Fe to 5% Fe, which might be caused by the pore plugging effect after HFO encapsulation. With the assumption that a ternary complex was formed, the effect of sulfate on Cu(Ⅱ) adsorption by HFO-CPS were successfully described by CCM using the optimized Fe_((2))OH site under different sulfate concentrations(1 or 10 mmol·L~(-1)) and Cu/Fe ratios(0.0042 or 0.0252). It is confirmed that the formation of Fe OHCu SO_4 ternary surface complexes played an important role in enhancing Cu(Ⅱ) adsorption on HFO-CPS in the presence of sulfate.     

铜基催化剂上甲醇合成的动态反应动力学

Adsorption, surface reaction and process dynamics on the surface of a commercial copper-based cata-lyst for methanol synthesis from CO/CO2/H2 were systematically studied by means of temperature programmed desorption (TPD), temperature programmed surface reaction (TPSR), in-situ Fourier transform-inferred spectroecopy(FTIR) and stimulus-response techniques. As a part of results, an elementary step sequence was suggested and a group of ordinary differential equations (ODEs) for describing transient conversations relevant to all species on the catalyst surface and in the gas phase in a micro-fixed-bed reactor was derived. The values of the parameters referred to dynamic kinetics were estimated by fitting the solution of the ODEs with the transient response data obtained by the stimulus-response technique with a FTIR analyzer as an on-line detector.     

Production and characterization of exopolysaccharides in mycelial culture of Cordyceps sinensis fungus Cs-HK1 with different carbon sources

The effects of different carbon sources(sugars) on the production and molecular properties of exopolysaccharides(EPS) were evaluated in the mycelial liquid culture of a medicinal fungus Cordyceps sinensis Cs-HK1. Galactose or mannose was used(at 5 g·L~(-1)) as a secondary carbon source with glucose(35 g·L~(-1)) at the mass ratio of 1:7. Mannose was consumed notably since the first day of culture, but galactose was not even after glucose was exhausted.The volumetric yield of EPS in culture was increased slightly with the addition of galactose and decreased with mannose. The monosaccharide composition of EPS was also different, e.g., on day 8, the glucose contents of EPS were 76%with the addition of mannose, 59% with galactose, compared with 62% with glucose only. The molecular weight distribution of EPS was also affected by the secondary carbon source, being generally lower compared with that with glucose only. The results suggested that the addition of galactose improved the total yield of EPS in culture while mannose can improve the yield of glucan constituent of EPS.     

Optimizational production of phenyllactic acid by a Lactobacillus buchneri strain via uniform design with overlay sampling methodology

A Lactobacillus buchneri GBS3 strain isolated from the traditional Chinese pickles was used for the production of 3-phenyllactic acid(PLA), an important compound with antimicrobial activities against a wide species of grampositive and gram-negative bacteria and some fungi. The growth performance of this strain in the de Man, Rogosa and Sharpe(MRS) medium, the production of metabolites of valuable organic acids, and the biosynthesis of PLA using this strain as the whole-cell biocatalyst and phenylpyruvic acid(PPA) as the precursor, were investigated experimentally. The uniform design method with overlay sampling was developed for the optimization of the biotransformation conditions. The results showed that although it produced naturally lactic acid with the maximum concentration of 1.84 g·L~(-1) and PLA with the concentration of 0.015 g·L~(-1) after 66 to 72 h cultivation in MRS broth by fermentation, the present strain displayed an effective utilization ability by transforming PPA to PLA. By the uniform design method with overlay sampling for the design and optimization of transformation conditions, a maximum yield of 10.93 g·L~(-1) PLA with the mole conversion ratio of 83.07% from PPA to PLA was achieved under the optimized condition, i.e., 20 g·L~(-1) glucose, 270 g·L~(-1) cells, 13 g·L~(-1) PPA, pH 8.0 and the reaction time of 15 h, indicating that Lactobacillus buchneri GBS3 was an interesting strain for the biosynthesis of PLA via the microbial transformation. The prediction of PLA yield under different conditions was achieved successfully based on the limited information of only a small number of experiments by the uniform design with overlay sampling. Therefore, the present methodology is effective and helpful for the optimization of the biosynthesis processes of PLA.     

油酸修饰纳米CaCO3对PP结晶行为和力学性能的影响

Oleic acid (OA)-modified CaCO3 nanoparticles were prepared using surface modification method. Infrared spectroscopy (IR) was used to investigate the structure of the modified CaCO3 nanoparticles, and the result showed that OA attached to the surface of CaCO3 nanoparticles with the ionic bond. Effect of OA concentration on the dispersion stability of CaCO3 in heptane was also studied, and the result indicated that modified CaCO3 nanoparticles dispersed in heptane more stably than unmodified ones. The optimal proportion of OA to CaCO3 was established. The effect of modified CaCO3 nanoparticles on crystallization behavior of polypropylene (PP) was studied by means of DSC. It was found that CaCO3 significantly increased the crystallization temperature, crystal-lization degree and crystallization rate of PP, and the addition of modified CaCO3 nanoparticles can lead to the for-mation of β-crystal PP. Effect of the modified CaCO3 content on mechanical properties of PP/CaCO3 nanocompo-sites was also studied. The results showed that the modified CaCO3 can effectively improve the mechanical proper-ties of PP. In comparison with PP, the impact strength of PP/CaCO3 nanocomposites increased by about 65% and the flexural strength increased by about 20%.     

Regulation of isobutane/1-butene adsorption behaviors on the acidic ionic liquids-functionalized MCM-22 zeolite

The adsorption ratio of isobutane/1-butene on the catalyst surface is one of the most important factors for the C4 alkylation process.Regulation of isobutane/1-butene adsorption ratio on the zeolite-supported acid catalyst is a big challenge for catalyst preparation.To regulate the isobutane/1-butene adsorption ratio,four types of ionic liquid (i.e.,IL) with different alkyl chain lengths and different acid group numbers were synthesized and were subsequently immobilized onto the MCM-22 zeolite.The as-synthesized IL-immobilized MCM-22 (i.e.,MCM-22-IL) was characterized by FTIR,TGA,BET,XPS and XRD,and their adsorption capacities and adsorption molar ratios of isobutane to 1-butene (I/O) were investigated to correlate with surface features of MCM-22-IL Results showed that the immobilization of ILs led to a decrease of specific surface area and pore volume.But the surface density of acid groups was increased and the adsorption molar ratio of isobutane/1-butene (I/O) was significantly improved by the immobilization of ionic liquids.The adsorption molar ratio of I/O is substantially improved from 0.75 to above 0.9 at 300 kPa upon immobilizing ILs.Although the alkyl chain length of ILs was found to have little effect on the adsorption molar ratio of I/O,the increase of acid group numbers led to a dramatic decrease in the adsorption I/O ratio.The results illustrated that immobilizing ionic liquids is an effective way to modify the textural,chemical and morphological properties of MCM-22.Accordingly,the immobilization of ionic liquids provides a novel and a feasible way to regulate the adsorption I/O ratio on an adsorbent or a solid catalyst.     

一种通过重组大肠杆菌和重组恶臭假单胞菌生产3-羟基癸酸的新方法

3-hydroxydecanoic acid (3HD) is an interesting intermediate for chemical synthesis of many valuable compounds. A novel method to produce 3HD by recombinant bacteria was constructed in Escherichia coli HB101 and Pseudomonas putida GPp104, respectively. Simultaneous expression of both phaG encoding (R)-3-hydroxydecanoyl-ACP:CoA transacylase and tesB encoding thioesterase Ⅱ in E. coli HB101 increased 3HD production approximate 1.7-folds compared with the expression of phaG gene alone under identical conditions. In addition, when the tesB gene was introduced into the strain, the polyhydroxyalkanoate synthase negative strain P. putida GPpl04 produced extracellular 3HD. Thus, a novel pathway to produce 3HD by recombinant Pseudomonas was constructed. It was also found that the ratio of carbon source to nitrogen source affected the production of 3HD by recombinant P.putida harboring tesB gene. Nitrogen limitation seemed to promote the extracellular 3HD production.     

污泥含炭吸附剂的制备及其吸附模拟烟气中汞蒸汽的应用(英文)

The carbonaceous adsorbent was prepared from mixtures of dewatered sludge and sawdust with enhanced ZnCl2 chemical activation.Characteristics of the adsorbent were studied using scanning electron microscope(SEM) ,Fourier transform infrared spectroscopy(FT-IR) ,and adsorption of nitrogen.The surface analysis showed that the carbonaceous adsorbent had good specific surface and porosity(394 m 2 ·g-1of BET surface,0.12 and 0.10 ml·g-1of microporous and mesoporous volume,respectively) .The oxygen functional groups such as OH,C O and C O were found on the surface by FTIR and XPS(X-ray photoelectron spectroscopy) .The adsorption of elemental mercury(Hg0) on the carbonaceous adsorbent was studied in a fixed bed reactor.The dynamic adsorption capacity of carbonaceous adsorbent increased with influent mercury concentration,from 23.6μg·g-1at 12.58μg·m-3to 87.9μg·g-1at 72.50μg·m-3,and decreased as the adsorption temperature increased,from 246 μg·g-1 at 25°C to 61.3μg·g-1 at 140°C,when dry nitrogen was used as the carrier gas.The carbonaceous adsorbent presented higher dynamic adsorption capacity than activated carbon,which was 81.2μg·g-1and 53.8μg·g-1respectively.The adsorption data were fitted to the Langmuir adsorption model.The physical and chemical adsorption were identified on the adsorbent.     

Synthesis of activated carbon from spent tea leaves for aspirin removal

Adsorption capacity of activated carbon prepared from spent tea leaves(STL-AC) for the removal of aspirin from aqueous solution was investigated in this study. Preliminary studies have shown that treatment with phosphoric acid(H_3PO_4) increased removal efficiency of STL-AC. Characterizations on STL-AC revealed excellent textural properties(1200 m~2·g~(-1), 51% mesoporosity), as well as distinctive surface chemistry(1.08 mmol·g~(-1) and 0.54 mmol·g~(-1) for acidic and basic oxygenated groups, pH_(pzc)= 2.02). Maximum removal efficiency of aspirin observed was 94.28% after 60 min when the initial concentration was 100 mg·L~(-1), 0.5 g of adsorbent used,pH 3 and at a temperature of 30 ℃. The adsorption data were well fitted to the Freundlich isotherm model and obeyed the pseudo-second order kinetics model. The adsorption of aspirin onto STL-AC was exothermic in nature(ΔH~Θ=~(-1)3.808 k J·mol~(-1)) and had a negative entropy change, ΔS~Θ(-41.444 J·mol~(-1)). A negative Gibbs free energy, ΔG~Θ was obtained indicating feasibility and spontaneity of the adsorption process. The adsorption capacity of AC-STL(178.57 mg·g~(-1)) is considerably high compared to most adsorbents synthesized from various sources, due to the well-defined textural properties coupled with surface chemistry of STL-AC which favors aspirin adsorption. The results demonstrate the potential of STL-AC as aspirin adsorbent.