SO2活化改性石油焦吸附剂的汞吸附特性

利用SO₂气体对石化工业副产物石油焦进行活化改性以制成富硫高活性脱汞吸附剂（SAPC）。在固定床实验装置上进行SAPC吸附脱除汞的实验研究,考察吸附温度、入口Hg⁰浓度、烟气成分以及热再生等因素对脱汞特性的影响规律,同时结合比表面积及孔隙度分析、元素分析和X射线光电子能谱（XPS）等表征手段深入分析SAPC的汞吸附机理。结果表明,SO₂活化改性石油焦的物理和化学特性得到极大改善,羰基、酯基以及非氧化态硫是Hg⁰的主要活性吸附位。吸附温度的升高会抑制对Hg⁰的吸附脱除,烟气中较高的Hg⁰浓度会降低汞脱除效率,但对其汞吸附速率有促进作用。SO₂对SAPC的脱汞性能影响较小,O₂易将Hg⁰氧化成为更容易与含氧、含硫官能团结合的氧化态汞,从而促进对Hg⁰的脱除。热再生时吸附态汞化合物受热分解的过程伴随着吸附剂表面化学活性位的损失,导致再生后汞吸附性能大幅下降。     

SO2改性高硫石油焦脱汞实验研究

以SO₂为活性气体对3种不同的原始高硫石油焦进行活化形成高硫石油焦样品。采用比表面积及孔隙度分析仪、X射线光电子能谱分析和元素分析等仪器和方法研究样品的物理化学性质,在固定床实验装置上对样品的脱汞能力进行实验研究。结果表明,用SO₂气体改性石油焦的过程是一个有效的载硫过程;经过SO₂改性后的高硫石油焦表面负载有大量有机硫（噻吩）,具有较强的脱汞能力;高硫石油焦表面的含硫量和硫形态对其吸附脱汞能力有很大影响,高硫石油焦表面的微孔结构和微观形貌也在一定程度上影响其脱汞能力;在一定温度范围内随着吸附温度的降低,改性高硫石油焦的Hg⁰穿透率呈下降趋势,即汞脱除性能不断增强。     

Investigation of aromatic carbon sites in materials derived from petroleum and coal using 13C n.m.r. methods

Aromatic C and CH carbon sites in a variety of petroleum and coal derived materials have been investigated using a ¹³C n.m.r. technique termed spin echo broad band off-resonance decoupling (SEBBORD). Only resonances due to non-protonated aromatic carbon sites are observed in SEBBORD spectra such that comparison with conventional ¹³C n.m.r. spectra enables differentiation between aromatic C and CH group resonances. Relative abundances of non-protonated aromatic carbon sites calculated from SEBBORD data are in good agreement with values derived from a combination of conventional¹H n.m.r., ¹³C n.m.r. and elemental analysis data. The occurrence of significant proportions of aromatic C intensity to high field of 129–130 ppm and of aromatic CH intensity to low field of 129–130 ppm has been found to be quite common. Consequently attempts to determine aromatic C and CH group abundances by partitioning conventional ¹³C n.m.r. spectra in the vicinity of 129–130 ppm can lead to considerable quantitative errors. SEBBORD provides more detailed information about aromatic carbon sites than can be obtained from conventional ¹³C n.m.r. spectra.     

热聚法合成深色石油树脂

乙烯裂解副产物C9芳烃馏分经过精馏分离提取220℃之前馏分,残余的重馏分与溶剂油按-定比例混配在-定温度和压力的条件下通过自由基聚合反应得到深色石油树脂.研究了反应温度、反应压力、改性剂含量等因素对深色石油树脂软化点、黏度及正庚烷值等指标的影响规律;确定了深色石油树脂热聚合温度、压力、恒温时间等工艺条件.     

喷雾快冷制备SbSn金属间化合物用于石油脱硫

使用自制管式炉,采用喷雾快冷工艺制备得到SbSn金属间化合物,将其作为功能材料进行石油脱硫实验。考察了材料制备温度、处理时间、石油乳化液配制条件等因素对脱硫效果的影响。结果表明,SbSn金属间化合物材料制备温度为950℃,脱硫的过程以16 h为宜;使用SbSn金属间化合物材料,在常温常压条件下对油包水型石油乳化液有明显的脱硫效果,该石油乳化液较佳的配比为:表面活性剂的质量分数0.25%,水的质量分数40%。在以上适宜的条件下,对石油的脱硫率最大可达到30.4%。     

Acid—base characteristics of petroleum asphaltenes as studied by non-aqueous potentiometric titrations

This Paper describes the determination of acids and bases present in petroleum asphaltenes by differential non-aqueous potentiometric titrations. The acids and bases are split into differing pKa's by addition of model compounds. Structural information about the nature of the groups titrated was obtained from the study of many model systems. The strong, medium and weak acids titrated are due to the presence of carboxylic, phenolic and indolic functionality, respectively, whereas the strong bases titrated are due to pyridine groups, the medium strength bases due to pyrazines and sulphoxides and the very weak bases due to indoles and amides.     

Chemical structures and photoelectric properties of carbonaceous materials prepared by solvent-extraction of petroleum pitch

The effects of aromatic molecular size on the electronic properties of carbonaceous materials were studied using materials extracted from a petroleum pitch. Structural analysis using the combined data of elemental analysis and ¹H-NMR revealed that the solvent-extraction technique successfully gave fractions with different size of aromatic systems. Optical band gaps calculated from the absorption spectra of the extracted carbonaceous materials showed a strong correlation with the aromatic molecular size. Junctions between the materials and n-type silicon were prepared by a spin-coating technique of pyridine solutions of the components. They were subjected to photocurrent measurement with infrared light (λ = 940 nm). The following results were obtained: (1) the photocurrent depended on the thickness of the extracted carbonaceous film on the n-Si substrate, (2) the junction with a closer optical band-gap energy to the photon energy showed a large photocurrent, (3) no photocurrent was observed for junctions made with silicon pre-cleaned by hydrofluoric acid. Photocarrier generation was concluded to take place near the interface between the film and the n-Si substrate. Carbonaceous film/oxide/n-Si was essential for the photoresponse of those junctions. The solvent-extraction technique is a promising way to obtain carbon-based material with suitable electronic properties.     

Analysis of polycyclic aromatic sulfur heterocycles in Egyptian petroleum condensate and volatile oils by gas chromatography with atomic emission detection

Eight Egyptian petroleum condensates and two volatile oils were analyzed by gas chromatography. The condensate oils range in color from colorless to yellow and brown. The samples are composed mainly of saturates hydrocarbons (C₃ to C₃₅). The polycyclic aromatic sulfur heterocycles (PASH) were isolated through use of a silica bonded palladium(II)-complex and their distribution investigated by gas chromatography (GC) with atomic emission detection (AED) in the sulfur-selective mode. The condensate oils show distinctly different distributions of the PASHs, some containing mainly benzothiophenes, and others both benzo- and dibenzothiophenes and a third group in which the dibenzothiophenes strongly dominate. The alkyl substituted sulfur compounds are quantified. The distribution patterns of the PASHs are correlated to the type of reservoir source rocks.     

Reduction of petroleum hydrocarbons content from an engine oil refinery wastewater using a continuous stirred tank reactor monitored by spectrometry tools

BACKROUND: Hydrocarbon contamination of groundwater resources has become a major environmental and human health concern in many parts of the world. Microbial degradation of hydrocarbons, through either naturally occurring processes or engineered systems, has been successfully used to reduce concentrations of these pollutants. In order to develop an aerobic bioreactor tailored for this purpose, the present study aims to investigate petroleum contaminated wastewater remediation and toxicity reduction by acclimated microbial consortium enriched in a continuous stirred tank bioreactor (CSTR). Characterization and quantification of refinery wastewater components were performed by gas chromatography mass spectrometry (GC/MS) and Fourier transform infrared (FTIR) spectroscopy. RESULTS: The petroleum hydrocarbons were significantly degraded (97%) by the microbial consortium. After continuous aerobic treatment in the CSTR, the COD_effluent and BOD_5effluent average removals were high reaching 97% and 78%, respectively. Also, strong degradation of C10? C35 n‐alkanes was observed. The concomitant use of GC/MS and FTIR proved to be a useful complementary tool to assess the impact of treatment strategies on hydrocarbon‐contaminated wastewater. In addition, the toxicity of the contaminated wastewater decreased drastically after bioremediation. CONCLUSION: This work shows the ability of this consortium to degrade hydrocarbons and reduce toxicity, which makes them useful candidates for environmental restoration applications at other hydrocarbon‐contaminated environments. Copyright © 2011 Society of Chemical Industry     

Significant decreased dielectric constant and loss of polystyrene–clay nanocomposite materials by using long‐chain intercalation agent

Polystyrene–clay nanocomposite (PsCN) materials have been prepared by a free radical polymerization process. Montmorillonite (MMT), modified by two different organics, was investigated: one contains a short chain and three benzyl groups on the ammonium ion (DAETPB), while the other contains a long chain (HTAC). The organic modification determines the extent of exfoliation or intercalation of the materials. Exfoliation is more likely to occur using HTAC, as then the gallery of clay has been opened more due to the long chain structure. Exfoliation of MMT in polystyrene (PS) matrix was revealed by X‐ray diffraction (XRD) and transmission electron microscopy (TEM). Differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) were employed to confirm the increased thermal stability of these PsCN materials. Dielectric properties of polystyrene‐clay nanocomposites, in the form of film with clay loading from 1.0 to 5.0 wt %, were measured under frequencies of 100 Hz～1 MHz at 25～70°C. Decreased dielectric constant and low dielectric loss were observed for PsCN materials. Especially, the decrease of dielectric constant was found to be related to the extent of exfoliation of clay. It is recognized that the confinement effect of clay results in the suppression of the dielectric response of the nanocomposite materials at low frequency. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2402–2410, 2004     

Improvement in the flame retardancy of cotton fabric by admicellar polymerization of 2‐acryloyloxyethyl diethyl phosphate using an anionic surfactant

The phosphorus‐containing acrylate monomer, 2‐acryloyloxyethyl diethyl phosphate (ADEP), was synthesized and applied to cotton fabric by using admicellar polymerization. Sodium dodecylbenzene sulfonate was used as the anionic surfactant. The film of polymerized monomer (PADEP) formed on the cotton surface was characterized by FTIR‐ATR spectroscopy and SEM. Thermal and flame retardant properties of PADEP‐coated cotton were investigated by TGA and flammability tests. Results showed that PADEP polymer film was successfully formed on the cotton fabric. The TGA and DTG analyses showed that the phosphorus‐containing PADEP lowered the decomposition temperature of the treated fabric resulting in a higher char yield than in the case of untreated cotton. The flammability tests showed that the treated cotton had much improved flame retardancy property after the treatment. The treated fabric also retained its good pliability and soft touch with good air permeability. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Kinetic,isotherm, and thermodynamic studies of Cr(VI) removal from aqueous solution using mesoporous silica materials prepared by fly ash

A series of mesoporous silica materials (FMD, FMT, and FMC were synthesized with DTAB, TTAB, and CTAB as template, respectively) have been prepared using fly ash as a silica resource. The as-synthesized materials were characterized by BET, XRF, FTIR, and XPS. The results confirmed the mesoporous structure and nitrogen content to act as potential adsorbents. The adsorption properties of these materials were also investigated by batch adsorption experiments. The FMC exhibited the highest effective removal of Cr(VI) (99%). The Cr(VI) adsorption process over FMC follows the pseudo-second-order kinetic and Langmuir model. Thermodynamic studies revealed that the Cr(VI) adsorption by FMC was spontaneous and endothermic. The study of the adsorption mechanism showed that the removal of Cr (VI) by FMC is through electrostatic attraction and chemical reduction. The coexisting ions experiment showed that FMC had high selectivity for Cr(VI). After three regeneration cycles, the Cr(VI) removal rate of FMC adsorbent still remained about 80%. Thus, this inexpensive adsorbent (FMC) is suitable for removing Cr(VI) from discharged industrial water.     

Improvement on the electrochemical characteristics of graphite anodes by coating of the pyrolytic carbon using tumbling chemical vapor deposition

The electrochemical characteristics of graphite coated with pyrolytic carbon materials using tumbling chemical vapor deposition (CVD) process have been studied for the active material of anodes in lithium ion secondary batteries. Coating of pyrolytic carbons on the surface of graphite particles, which tumble in a rotating reactor tube, was performed through the pyrolysis of liquid propane gas (LPG). The surface morphology of these graphite particles coated with pyrolytic carbon has been observed with scanning electron microscopy (SEM). The surface of graphite particles can well be covered with pyrolytic carbon by tumbling CVD. High-resolution transmission electron microscopy (HRTEM) image of these carbon particles shows that the core part is highly ordered carbon, while the shell part is disordered carbon. We have found that the new-type carbon obtained from tumbling CVD has a uniform core (graphite)-shell (pyrolytic carbon) structure. The electrochemical property of the new-type carbons has been examined using a charge-discharge cycler. The coating of pyrolytic carbon on the surface of graphite can effectively reduce the initial irreversible capacity by 47.5%. Cyclability and rate-capability of theses carbons with the core-shell structure are much better than those of bare graphite. From electrochemical impedance spectroscopy (EIS) spectra, it is found that the coating of pyrolytic carbon on the surface of graphite causes the decrease of the contact resistance in the carbon electrodes, which means the formation of solid electrolyte interface (SEI) layer is suppressed. We suggest that coating of pyrolytic carbon by the tumbling CVD is an effective method in improving the electrochemical properties of graphite electrodes for lithium ion secondary batteries.     

Improvement of mechanical performances and characteristics of bulk Bi-2212 materials exposed to Au diffusion and stabilization of durable tetragonal phase by Au

This study centers sensitively on the determination of optimum diffusion annealing temperature (650–850 °C) for the electrical, superconducting, crystal structure, and especially mechanical characteristics of Au surface-layered Bi-2212 superconducting materials with the aid of dc electrical resistivity, powder X-ray diffraction and microhardness measurements. The experimental results show that all the characteristic properties (normal state resistivity, critical transition temperatures, degree of broadening, phase fractions, lattice cell parameters, elastic modulus, yield strength, fracture toughness, brittleness index and flexural strength parameters) improve considerably with the increment in the annealing temperature up to 800 °C as a consequence of the decreased local structural distortions, lattice strains, disorders, defects and grain boundary interaction problems in the Cu-O₂ consecutively stacked layers. After the critical annealing temperature value of 800 °C, the parameters immediately recrudesce towards their global minimum points. Similarly, the highest Bi-2223 phase fraction and c-axis length are observed at the 800 °C annealing temperature due to the best crystallinity and crystal plane alignments. Additionally, the optimum value strengthens the mechanical durability and ideal flexural strength as a result of the stabilization of durable tetragonal phase. Thus, the presence of Au impurities increases the critical stress value so that the crack-producing flaws and cracks propagation divert or slow down rapidly. On the other hand, the excess temperature value such as 850 °C leads to the deleterious effect on the mechanical performances of Au surface-layered Bi-2212 compound because of the increased residual porosity and omnipresent flaws (stress raisers and crack initiation sites). Further, it is at least equally important that the crack propagation or dislocation movement more proceeds through the transgranular regions instead of along the intergranular regions with increasing temperature up to the optimum value beyond which the limited number of operable slip systems enhances noticeably and the intergranular fracture becomes more dominant.