无有机模板剂制备ZSM-5分子筛及其环己烯水合应用

以硫酸铝、水玻璃为主要原料,无有机模板剂条件下采用两步水热晶化法合成ZSM-5分子筛。系统研究钠硅比、水硅比和晶化时间等因素对ZSM-5分子筛结晶度和晶粒尺寸的影响。采用XRD和SEM对制备的ZSM-5分子筛进行结构表征,并考察ZSM-5分子筛在环己烯水合反应中的催化性能。结果表明,在一定钠硅物质的量比和水硅物质的量比范围,ZSM-5分子筛结晶度随钠硅物质的量比的增加与水硅物质的量比的减小而升高。无有机模板剂条件下制备ZSM-5分子筛,不仅降低生产成本,减少对环境的危害,而且在环己烯水合反应中表现出较好的催化活性,随着ZSM-5分子筛晶体尺寸减小,环己烯转化率提高。     

Corrosion inhibition of mild steel in sulfamic acid solution by S-containing amino acids

R_p, potentiodynamic polarization curves and EIS techniques were applied to study the effect of five S-containing amino acids on the corrosion of mild steel in 5% sulfamic acid solution at 40 °C. The compounds are effective inhibitors and the inhibition efficiency follow the order: N-acetylcysteine (ACC) > cysteine (RSH) > S-benzylcysteine (BzC) > cystine (RSSR) ≅ methionine (CH₃SR). The inhibitors affect the anodic dissolution of steel by blocking the anodic sites of the surface. EIS measurements indicated that charge transfer is the rate determining step in the absence and presence of the inhibitors and the steel/solution interface can be represented by the equivalent circuit R_s(R_ctQ_dl). Adsorption of RSH, CH₃SR and RSSR follows the Langmuir model while the Temkin isotherm describes the adsorption of ACC and BzC. From the application of the Flory–Huggins isotherm, the number of water molecules displaced by the adsorbing inhibitor molecules was estimated. The potential of zero charge pzc of mild steel without and with the inhibitors is calculated and the mechanism of corrosion inhibition is discussed in the light of the molecular structure.     

In-situ synthesis and catalytic activity of ZSM-5 zeolite

ZSM-5 zeolite has been hydrothermally synthesized in-situ on the external surface of calcined kaolinite in the presence of n-butylamine. This supported zeolite was characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier transform infrared (FT-IR) spectroscopy and N₂ adsorption. Several synthesis variables were systematically investigated, including SiO₂ to Al₂O₃ ratio, pH, crystallization time, and crystallization temperature. After mixing the ZSM-5 with a Fluid Catalytic Cracking (FCC) catalyst, catalytic performance was evaluated by cracking vacuum gas oil (VGO) in a micro-fixed bed reactor. ZSM-5 addition was favorable for the production of light olefins by catalytic cracking of VGO.     

Corrosion inhibition of mild steel by aerobic biofilm

Mild steel electrodes were incubated in phosphate-buffered basal salt solution (BSS) having two different aerobic bacteria, viz. Pseudomonas alcaligenes and Pseudomonas cichorii. In the medium containing P. cichorii, significant reduction in the corrosion rate was observed due to the surface reaction leading to the formation of corrosion inhibiting bacterial biofilm. With a view to understand the mechanism of microbially influenced corrosion/corrosion inhibition, electrochemical and biological experiments such as electrochemical impedance spectroscopy (EIS) measurements and biochemical analysis were made. The exposed surfaces were examined using scanning electron micrographs (SEM), energy dispersive spectroscopy (EDS) and electron spectroscopy for chemical analysis (ESCA). The scraped surface film was also examined using FT-IR spectroscopy. The results suggested that mild steel surface contained iron oxide-phosphate layer covered with bacteria and exo polymeric substance (EPS)/iron-EPS complex for P. cichorii and iron oxides and iron phosphate for P. alcaligenes.     

Electron conducting organic coating of mild steel by electropolymerization

The aim was to coat mild steel with an electron conducting polymer in order to replace any possible electrochemical corrosion of the metal by another electrochemical reaction occurring on top of the film. In view of potential industrialization, electropolymerization of a water soluble monomer was studied. In most cases, this was achieved by oxidation, and the substrate had to be passivated. Polyaniline, was obtained in nitric acid solution. Films had a good structure but were brittle and powdery on the surface. Except on tin free steel, they were insulating. Polypyrrole was a better candidate. Prepared from a Na₂SO₄ solution, films were conductive, ensured good corrosion resistance of the substrate but they were brittle and adhesion to the substrate was not high. Furance, thiophene and iron substituted vinylpyridine complex were tried without success. Further, research should consider copolymerization of pyrrole with other monomers.     

Corrosion protection of mild steel by polypyrrole phosphate composite coating

Electrodeposition of polypyrrole phosphate (PPy–P) on mild steel (ST₁₂) was achieved in oxalic acid medium using cyclic voltammetry (CV) technique. Adherent and homogeneous PPy–P films were obtained. The corrosion behavior of mild steel with phosphate (PPy–P) coatings in 3.5% NaCl solutions was investigated through potentiodynamic polarization technique, open circuit potential–time curves, and electrochemical impedance spectroscopy (EIS). Based on a physical model for the corrosion of mild steel composite, the Zview (II) software was applied to the EIS to estimate the parameters of the proposed equivalent circuit. It was found that the PPy–P coatings could provide much better protection than PPy. The effect of phosphate on the morphology and structure of the passive film was investigated by scanning electron microscopy and electron dispersion X-ray analysis (EDX). The results reveal that the PPy–P coated electrode provided a noticeable enhancement of protection against corrosion process.     

Corrosion inhibition of mild steel by natural product compound

Corrosion inhibition of mild steel in H₃PO₄ containing chloride or sulphate ions have been studied using different electrochemical techniques. The corrosion and hydrogen evolution of mild steel alloy in 2 M H₃PO₄ acid containing 0.5 M NaCl can be effectively inhibited by addition of natural product compound, Thymol (IPMP), of different concentrations. However, in 2 M H₃PO₄ containing 0.5 M Na₂SO₄ corrosion cannot be effectively inhibited. The results of electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization measurements confirm the synergistic effects which describe the increase in the effectiveness of a corrosion inhibitor in the presence of Cl⁻ ions in the corrosive medium. At any temperature, an increase in it leads to an increase of the corrosion rate and hydrogen evolution on mild steel. Polarization and EIS results are in good agreement with each other. The obtained results were confirmed by surface examination using scanning electron microscope.     

ZSM-5沸石分子筛膜的制备及脱盐性能研究

淡水资源日益短缺,发展膜法海水淡化技术是满足世界淡水供应需求的重要途径,但是寻找合适的膜材料依然是人类面临的挑战。ZSM-5沸石分子筛膜（简称沸石膜）具有规则的孔道结构、合适的孔径尺寸（0.51~0.56 nm）以及可调变的硅铝比,在有机物脱水分离应用中展示了优异的选择性及良好的渗透性和稳定性。基于其孔径尺寸介于水分子和盐离子之间,其在海水淡化脱盐领域也具有应用潜力。在大孔α-Al₂O₃载体上采用二次生长法制备了ZSM-5沸石膜,考察了晶化时间与合成液的硅铝比对ZSM-5沸石膜成膜和渗透蒸发脱盐性能的影响,并采用XRD、SEM、EDS与水接触角表征了合成膜的相结构与结晶度、骨架组成表面特性等膜的结构性质。结果表明：通过二次水热法采用合成液摩尔配比为n（Al₂O₃）∶n（SiO₂）∶n（Na₂O）∶n（NaF）∶n（H₂O）=0.05∶1∶0.21∶1.01∶55的合成液在175℃下晶化48 h为最佳的合成条件,制备了Si/Al比为10、接触角为17.5°的亲水纯相致密ZSM-5沸石膜,并在75℃下对3.5%（质量）的NaCl水溶液进行了渗透蒸发测试,水的通量和盐离子截留率达到8.35 kg·m^-2·h^-1和99.99%,且性能在60 h的时间依存性测试后依然稳定,表现出了很高的海水淡化工业应用潜力。     

ZSM-5沸石的改性及其在烷基化反应中的应用进展

ZSM-5沸石在石油化工中的应用非常重要。本文对ZSM-5沸石的改性技术的现状及其近年来在烷基化反应中的开发应用的最新进展进行了综合阐述,ZSM-5沸石的应用已取得了一定的成果,为其今后的开发利用提供了新的思路。     

全结晶ZSM-5分子筛催化剂研究及工业应用

制备了全结晶ZSM-5分子筛催化剂,采用XRD、SEM、N2物理吸附-脱附及NH3-TPD等对催化剂进行表征,并考察其用于碳四烯烃催化裂解制丙烯(OCC)反应的催化性能。结果表明,制备的全结晶ZSM-5分子筛催化剂比常规成型的催化剂具有更高的结晶度、更大的比表面积、更丰富的孔结构以及更多的活性中心。高空速有利于反应的进行,提高压力对反应不利,升高温度有利于提高产物丙烯收率。在实验室研究的基础上,将全结晶ZSM-5分子筛催化剂用于OCC工业装置,取得良好的应用效果。     

Corrosion inhibition of steel in concrete by carboxylic acids

Water soluble carboxylic acids have been used as corrosion inhibitors. They remain largely soluble after curing in cement for up to 90d. Corrosion current measurements are presented showing malonic acid, a dicarboxylic acid, to be a very effective corrosion inhibitor even in the presence of 2.5 wt % chloride. Unfortunately, it has an initial retarding effect on the set of Portland cement. The investigation suggests that corrosion inhibitors based on carboxylic acids remain a fruitful field of investigation.     

Chemisorption of alkenes on copper-exchanged ZSM-5 zeolite

On Cu-ZSM-5 zeolite at room temperature, propane is physisorbed, while propene shows characteristics of chemisorption. The chemisorption mode has certain advantages for the catalytic control of automotive emissions. Alkane and alkene adsorption equilibria and kinetics are compared on Cu-ZSM-5 and on ZSM-5 free of alumina. The results are discussed in terms of the Langmuir adsorption isotherm.     

二次水热合成法制备ZSM-5分子筛膜及其渗透汽化性能

采用二次水热合成法在管状多孔莫来石支撑体上制备高耐酸性ZSM-5分子筛膜,系统地研究分子筛晶种和合成溶胶中H₂O/SiO₂摩尔比率对ZSM-5分子筛膜生长与渗透汽化性能的影响,采用X射线衍射、冷场扫描电子显微镜和电子能谱等表征技术分别对制备的ZSM-5分子筛及其ZSM-5分子筛膜的结构、形貌和Si/Al比进行表征。针对分离75℃、90% HAc/H₂O的水溶液,最优化条件下制备的ZSM-5分子筛膜表现出优良的渗透汽化性能,渗透通量和分离因子分别为0.98kg/(m²·h)和890。此外,本研究所采用制备耐酸性ZSM-5分子筛膜的方法表现出良好的重现性,重复制备的12根ZSM-5分子筛膜在75℃下分离90% HAc/H₂O的水溶液时,平均通量和分离系数分别为（0.85±0.15）kg/(m²·h)和650±290。再者,ZSM-5分子筛膜在45～75℃的温度范围内分离50%～95% HAc/H₂O水溶液时都表现出优良的渗透汽化性能。     

Corrosion performance of chemically synthesized poly(aniline-co-o-toluidine) copolymer coating on mild steel

A soluble copolymer from aniline and o-toluidine [poly(aniline-co-o-toluidine)] was synthesized by chemical oxidative copolymerization using ammonium persulphate as an oxidant in hydrochloride aqueous medium. The resultant copolymer was characterized by Fourier Transform Infrared (FTIR) spectroscopy and chemically deposited on mild steel specimens using N-methyl-2-pyrrolidone (NMP) as solvent via solution evaporation method. The anticorrosive properties of copolymer coating was investigated in major corrosive environments, such as 0.1 M HCl, 5% NaCl solution, artificial seawater, distilled water and open atmosphere by conducting various corrosion tests which include: immersion test, open circuit potential (OCP) measurements, potentiodynamic polarization measurements and atmospheric exposure test. The corrosion performance of copolymer coating was also compared separately with polyaniline (PANi) and poly(o-toluidine) (POT) homopolymer coatings. The surface morphologies of polymer coatings were evaluated using scanning electron microscopy (SEM). The synthesized copolymer exhibited excellent protection against mild steel corrosion; the protection efficiency being in the range of 78–94% after 30 days of immersion. The corrosion performance of copolymer in 5% NaCl and artificial seawater was comparable, which was only marginally better than in 0.1 M HCl. In general, the performance of copolymer coating was found to be better than that of homopolymer coatings.     

Corrosion inhibition of mild steel in acidic medium using hydrazide derivatives

The corrosion inhibition characteristics of N′-[(1E)-(4-hydroxy phenyl) methylene] isonicotinohydrazide (HIH) & N′-[(1E)-(4-hydroxyl-3-methoxy phenyl) methylene] isonicotinohydrazide (HMIH) on mild steel corrosion in 1 M hydrochloric acid were investigated by weight loss, potentiodynamic polarization and impedance techniques. The inhibition efficiency increased with increase in inhibitor concentration but decreased with increase in temperature. The thermodynamic functions of dissolution and adsorption processes were evaluated. The polarization measurements indicated that the inhibitors are of mixed type. The adsorption of the compounds was found to obey Langmuir’s adsorption isotherm. Passive film characterization was done by Fourier transform infrared (FTIR) spectra and scanning electron microscopy (SEM).     

Corrosion inhibition of mild steel by benzotriazole derivatives in acidic medium

Benzotriazole derivatives, namely, N-[1-(benzotriazolo-1-yl)alkyl] aryl amine (BTMA), N-[1-(benzotriazolo-1-yl)aryl] aryl amine (BTBA), and 1-hydroxy methyl benzotriazole (HBTA), were synthesized and their inhibition behaviour on mild steel in 0.5 M H₂SO₄ at room temperature was investigated by various techniques. Preliminary screening of the inhibition efficiency (IE) was carried out using weight-loss measurements. Potentiodynamic polarization and AC impedance studies were used to investigate the inhibitor mechanism. Benzotriazole derivatives were found to act as mixed type inhibitors. Among the compounds studied, HBTA exhibited the best performance giving more than 95% IE in H₂SO₄ solutions. The passive film characterization was done using FTIR spectrum.     

Corrosion inhibition effect of pyrazole derivatives on mild steel in hydrochloric acid solution

Synthesized compounds, namely methyl 5-(4-Chlorobenzoyloxy)-1-phenyl-1H-pyrazole-3-carboxylate (MCPPC) and 5-(4-methoxyphenyl)-3-(4-methylphenyl)4,5-dihydro-1H-pyrazol-1-yl-(pyridin-4-yl)methanone (MMDPPM) were investigated as corrosion inhibitor for mild steel (MS) in 15% HCl solution using weight loss measurement, potentiodynamic polarization, and electrochemical impedance spectroscopy (EIS) methods. Inhibition efficiency was found concentration-dependent and increased by increasing the concentration of MCPPC and MMDPPM. Both of inhibitors were efficient even at a very low concentration of 25 ppm. The inhibitors MCPPC and MMDPPM showed inhibition efficiency of 67.1 and 76.8%, respectively, at 25 ppm, whereas it was 92.0 and 95.9%, respectively, at 250 ppm concentration at 303 K. The potentiodynamic polarization curves showed that MCPPC and MMDPPM act as mixed-type inhibitor in 15% HCl solution. The Nyquist plots showed that charge transfer resistance increased and double-layer capacitance decreased on increasing the concentration of studied inhibitors due to adsorption of inhibitor molecules on MS surface. The adsorption of each inhibitor on MS surface obeys Langmuir adsorption isotherm. On the basis of thermodynamic adsorption parameters, mixed-type adsorption (physisorption and chemisorption) for the studied inhibitors on MS surface was suggested. Scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), and atomic force microscopy (AFM) analyses confirmed the existence of a protective film of the inhibitor on MS surface. The density functional theory was employed for theoretical calculations, and the obtained results were found to be consistent with the experimental findings.     

高岭土及ZSM-5沸石分子筛形貌表征

对高岭土及ZSM-5沸石分子筛扫捕电镜样品制备方法进行研究,用该方法对不同产地高岭土进行表征研究.结果表明.选用合适的分散方法对高岭土及合成分子筛进行处理后制备扫描电镜样品,能够有效提高扫描电镜图片清晰度;不同产地高岭土的呈现不同形貌特征.在某一产地的高岭土微球中合成ZSM-5沸石分子筛,考查不同晶化反应时间对ZSM-...     

超细ZSM-5分子筛的制备及其形貌表征

对比考察了模板剂的种类、晶化温度以及铝含量等影响因素对超细ZSM-5分子筛晶化行为的影响,采用扫描电镜（SEM）、透射电镜（TEM）和X射线衍射光谱（XRD）技术对所制备的超细产物的结构及形貌进行了表征。结果表明,模板剂的种类对分子筛的晶化过程有重要影响,四丙基氢氧化铵是优良的制备超细ZSM-5分子筛的模板剂;以四丙基氢氧化铵为模板剂,适宜采用静态法制备超细ZSM-5分子筛的晶化温度为70～ 120 ℃;凝胶体系中铝的存在抑制ZSM-5分子筛晶核的生长,无铝条件下,分子筛的晶化速度最快;随着铝含量的增加,分子筛的晶化速度变慢,在相同的晶化时间内,生成的分子筛的粒径更小。