氢燃料电池汽车用氢气中痕量硫化物的分析进展

氢燃料电池汽车(FCV)用氢气中的痕量硫化物会导致催化剂中毒,使电池的性能显著下降。各标准组织均对氢燃料电池用氢气中的硫含量做了严格的限值,要求硫化物的含量(以H_(2)S或S_(1)计)低于0.004μmol/mol,这对硫化物的分析提出了很高的要求。本文介绍了气体分析领域中各种痕量硫分析的方法和原理,比较了它们的优缺点,并对它们在FCV用氢中痕量硫分析的应用进行了探讨。

热脱附-气相色谱法定量检测氢气中痕量硫化物

使用气相色谱搭载火焰光度检测器(FPD),以Heysep N作为吸附剂,在含硫标准气体的吸附脱附过程中,实现对硫化物的富集,从而直接对标准气体中的硫化物进行定量分析。测量结果线性、方法稳定性都较好,检测限可达到1×10-9(体积分数),解决了火焰光度法检测硫化物检测限低的问题,完全实现了新能源领域对硫化物的质量控制。

工业废水中痕量硫化物的示波极谱测定

本文着重介绍用硫化氢发生装置分离提纯硫化氢气体及在碱性硼酸钠底液中用导数示波极谱测定工业废水中痕量硫化物的新方法。该法与目前的标准法比较,具有简便、快速、节省人力、物力等优点,且准确度和精密度对某些样品的测定还优于标准法。适应浓度范围在0.005～5mg/L之间。能满足一般工业废水中痕(微)量硫化物测定的要求。

微量硫化物的在线测量方法和色谱FPD法应用

化肥生产过程中,痕量硫化物的在线监测是净化脱硫工段的重要控制指标之一,正常工况下痕量硫化物的体积分数低于0.1μL/L,有较强吸附性和腐蚀性。传统的在线分析方法主要是采用醋酸铅纸带法,与醋酸铅纸带法比较,色谱FPD法不仅能够多点多组分分析,而且具有检测灵敏度高,选择性、重复性、稳定性好,维护量少、运行费用低的优点。

硫化氢对Pd/C催化剂在环戊二烯加氢反应中性能的影响

本文用固定床反应器考察了Pd/C催化剂硫化前后 ,在环戊二烯加氢反应中的性能。结果表明环戊二烯的转化率从 86 4%上升到 98 2 % ,环戊烯的选择性从 86 9%上升到 98 8%。确定了最佳硫化条件。

Measurement of Concentration of Sorbent Particles and Water Droplets in Hydration Desulfurization Reactor with PIV

Vortexing limestone injection into furnace combined with calcium lime hydration in the downstream is the most promising technology for controlling SO 2 emission. Particle imaging velocimetry (PIV) is used to measure the gas liquid solid three phase flow field in a reactor. By image processing based on newly developed software, the number concentrations of sorbent particles and water droplets are presented. The measuring results are very helpful for better understanding the desulfurization mechanism and optimizing configurational and operational parameters in the hydration reactor.

Rational design of ternary NiS/CQDs/ZnIn_2S_4 nanocomposites as efficient noble-metal-free photocatalyst for hydrogen evolution under visible light

The NiS/CQDs nanocomposite (CQDs represents carbon quantum dots), with a mass ratio of NiS/CQDs to be 1.19:1 based on the ICP result, was obtained via a facile hydrothermal method from a mixture of CQDs, Ni(OAc)2 and Na2S. The self-assembly of ZnIn2S4 microspheres on the surface of NiS/CQDs was realized under microwave conditions to obtain a ternary NiS/CQDs/ZnIn2S4 nanocomposite. The as-obtained NiS/CQDs/ZnIn2S4 nanocomposite was fully characterized, and its photocatalytic hydrogen evolution under visible light irradiation was investigated. The ternary NiS/CQDs/ZnIn2S4 nanocomposite showed superior photocatalytic activity for hydrogen evolution than ternary CQDs/NiS/ZnIn2S4, which was obtained by deposition of NiS in the preformed CQDs/ZnIn2S4. The superior photocatalytic performance of ternary NiS/CQDs/ZnIn2S4 is ascribed to the introduction of CQDs, which act as a bridge to promote the vectorial transfer of photo-generated electrons from ZnIn2S4 to NiS. This result suggests that the rational design and fabrication of ternary CQDs-based systems are important for the efficient photocatalytic hydrogen evolution. This study provides a strategy for developing highly efficient noble-metal-free photocatalysts for hydrogen evolution using CQDs as a bridge to promote the charge transfer in the nanocomposite.

A Survey of Novel Processes to Produce Ultra Low Sulfur Gasoline

The restriction on sulfur level in gasoline has been increasingly tightened. The U.S.Tier 22222 regulation requires a reduction from average 340ppm to 30ppm from 2004 to 2008. Recently significant progress has been made in effective high sulfur removal, such as post treatment of FCC gasoline by selective hydrotreating, S Zorb sulfur removal technology, OATS process etc. The sulfur content of FCC gasoline can be deceased to less than 10ppm. With regard to gasoline pool composition in China, it is very important to look for effective desulfurization processes that are simple, straightforward, with less hydrogen consumption. Post-treatment of FCC gasoline is a preferred option. From the point of view of comprehensive utilization, alkylation, polymerization, isomerisation etc. can be added to desulfurization process to meet the requirement of ultra low sulfur, premium.

MIP Technology for Pruduction of Euro Ⅳ Clean Gasoline Ⅱ. Correlation Model of Sulfur Content of MIP Naphtha and Its Application

On the basis of the reaction rules and its influencing factors of sulfur compounds in MIP naphtha, a correlation model for describing the correlation between mass fraction of sulfur in MIP naphtha, mass fraction of sulfur in feedstock and volume fraction of olefin in naphtha was developed and the model＇s parameters were estimated. The residual error distribution and statistical study showed that the developed model was reasonable and reliable and able to predict the mass fraction of sulfur compounds in naphtha. The correlation model can provide theoretical guidance and operation base for adjusting process parameters to produce EURO IV gasoline by the MIP units. The model was validated by its application on the MIP unit of Qingdao Refining ＆ Chemical Company. On this unit, the tail oil with low sulfur content obtained via hydrotreating gas oil was used as the feedstock and the olefin content of naphtha was reduced by promoting hydrogen transfer reaction through adjustment of process parameters. Thus, EURO IV clean gasoline was manufactured by this MIP unit.

Influence of dioxin reduction on chemical composition of sintering exhaust gas with adding urea

With the addition of urea as an inhibitor, four groups of reducing dioxin emission experiments in sintering pot were conducted. The results show that, adding 0.05%, 0.1% and 0.5% （mass fraction） urea, the emission concentrations of dioxin are 0.287 0.258 and 0.217 ng-TEQ/m3, respectively. The dioxin emission rates drop substantially compared to 0.777 ng-TEQ/m3 flee of urea. With an increase of the urea content, the concentration of SO2 emission reduces sharply. （NH4）2SO4, formed by the reaction of SO2 and NH3, goes into the dust and part of NH3 is released before reaction with the emission of exhaust gas. The NO~ emission presents an increasing trend because the reaction of NH3 and 02 at high temperature produces NOx. Based on the consideration of factors such as the effect of reducing dioxin emission, and the chemical composition of exhaust gas, 0.05% is the optimum adding content of urea.

Development and Commercial Application of RFCC Catalyst for Reducing Sulfur Content in Gasoline

The sulfur-reducing functional component the Lewis acid-base pair compound and associated active zeolite component were developed to prepare the RFCC catalyst DOS for reducing sulfur content in gasoline. The results of catalyst evaluation have revealed that the Lewis acid-base pair compound developed hereby could enhance the conversion of macromolecular sulfur compounds by the catalyst to promote the proceeding of desulfurization reactions, and the synergetic action of the selected zeolite and the Lewis acid-base pair compound could definitely reduce the olefins and sulfur contents in gasoline. The heavy oil conversion capability of the catalyst DOS thus developed was higher coupled with an enhanced resistance to heavy metals contamination to reduce the sulfur content in gasoline by over 20%. The commercial application of this catalyst at the SINOPEC Jiujiang Branch Company has revealed that compared to the GRV-C catalyst the oil slurry yield obtained by the catalyst DOS was reduced along with an improved coke selectivity, an increased total liquid yield, and a decreased olefin content in gasoline. The ratio of sulfur in gasoline/sulfur in feed oil could be reduced by 20.3 m%.

Mathematical model for coupled reactive flow and solute transport during heap bioleaching of copper sulfide

Based on the momentum and mass conservation equations, a comprehensive model of heap bioleaching process is developed to investigate the interaction between chemical reactions, solution flow, gas flow, and solute transport within the leaching system. The governing equations are solved numerically using the COMSOL Multiphysics software for the coupled reactive flow and solute transport at micro-scale, meso-scale and macro-scale levels. At or near the surface of ore particle, the acid concentration is relatively higher than that in the central area, while the concentration gradient decreases after 72 d of leaching. The flow simulation between ore particles by combining X-ray CT technology shows that the highest velocity in narrow pore reaches 0.375 m/s. The air velocity within the dump shows that the velocity near the top and side surface is relatively high, which leads to the high oxygen concentration in that area. The coupled heat transfer and liquid flow process shows that the solution can act as an effective remover from the heap, dropping the highest temperature from 60 to 38 ℃. The reagent transfer coupled with solution flow is also analyzed. The results obtained allow us to obtain a better understanding of the fundamental physical phenomenon of the bioleaching process.

Diallyl sulfide protects against N-nitrosodiethylamine-induced liver tumorigenesis:Role of aldose reductase

AIM: To evaluate the protective effect of diallyl sulfide (DAS) against N-nitrosodiethylamine (NDEA)-induced liver carcinogenesis.METHODS: Male Wistar rats received either NDEA or NDEA together with DAS as protection.Liver energy metabolism was assessed in terms of lactate,pyruvate,lactate/pyruvate,ATP levels,lactate dehydrogenase (LDH) and glucose-6-phosphate dehydrogenase (G6PD) activities.In addition,membrane disintegration of the liver cells was evaluated by measuring lipid-peroxidation products,measured as malondialdehyde (MDA); nitric oxide (NO) levels; glucose-6-phosphatase (G6Pase),catalase (CAT) and superoxide dismutase (SOD) activities.Liver DNA level,glutathione-S-transferase (GST) and cytochrome c oxidase activities were used as DNA fragmentation indices.Aldose reductase (AR) activity was measured as an index for cancer cells resistant to chemotherapy and histopathological examination was performed on liver sections from different groups.RESULTS: NDEA significantly disturbed liver functions and most of the aforementioned indices.Treatment with DAS significantly restored liver functions and hepatocellular integrity; improved parameters of energy metabolism and suppressed free-radical generation.CONCLUSION: We provide evidence that DAS exerts a protective role on liver functions and tissue integrity in face of enhanced tumorigenesis caused by NDEA,as well as improving cancer-cell sensitivity to chemotherapy.This is mediated through combating oxidative stress of free radicals,improving the energy metabolic state of the cell,and enhancing the activity of G6Pase,GST and AR enzymes.

Absorption of sulfur dioxide using membrane and enhancement of desorption with ultrasound

The absorption of sulfur dioxide in simulated flue gas by using liquid-containing membrane was investigated.The process of sulfur dioxide desorption from the absorbent of citrate solution was explored.The influence of the gas-phase,and the liquid-phase on absorption efficiency of sulfur dioxide and the influence of ultrasonic frequency,ultrasonic power and stirring speed on desorption efficiency of sulfur dioxide were examined.The results indicate that the absorption efficiency decreases with increasing flow velocity and sulfur dioxide content in gas-phase,and can be improved by increasing the concentration and the pH value of citrate solution.It is concluded that lower ultrasonic frequency results in a better degassing efficiency.The using of ultrasound in desorbing sulfur dioxide from citrate solution improves the desorbing efficiency in the some conditions,without changing the essence of chemical reaction.

Flow-Based Iodometric Extraction Method by the Hollow Fiber Membrane for the Determination of Selenium Sulfide Levels in Cosmeceutical Products

A flow-based iodometric extraction method for the determination of selenium sulfide was developed and applied to cosmeceutical products. Iodine which was generated from the reduction of selenium（IV） ions by iodide ion was on-line extracted using a polypropylene HFM （hollow fiber membrane） liquid extraction technique. The HFM extraction unit was constructed and used to support an organic solvent （hexane） and separate between the organic phase and aqueous phase. The resulting purple extract was carried to a fiber optic spectrophotometric detector for the measurement at 521 nm. Parameters which affected the extraction efficiency, sensitivity and sample throughput such as iodide （selenium molar ratio, extraction time and washing time between the cycles） were investigated and optimized. A linear dynamic range of 80-373 mg.Lt selenium solution was obtained with an extraction time of 60 sec. The total analysis time including washing was about 180 sec which provided a sample throughput of approximately 20 samples＇hr1 and excluded the sample pre-treatment. The recoveries for the determination of selenium in the forms of selenium dioxide and selenium sulfide were in the range of 103%-104% with 1%-3% RSD （relative standard deviation）. The relative errors of this method which was applied for determination of selenium sulfide levels in an anti-dandruff shampoo and a cosmeceutical bead sample were both less than 2.5%.

Methane Dynamics in Northern Peatlands: A Review

Northern peatlands store a large amount of carbon and play a significant role in the global carbon cycle. Owing to the presence of waterlogged and anaerobic conditions, peatlands are typically a source of methane (CH4), a very potent greenhouse gas. This paper reviews the key mechanisms of peatland CH4 production, consumption and transport and the major environmental and biotic controls on peatland CH4 emissions. The advantages and disadvantages of micrometeorological and chamber methods in measuring CH4 fluxes from northern peatlands are also discussed. The magnitude of CH4 flux varies considerably among peatland types (bogs and fens) and microtopographic locations (hummocks and hollows). Some anthropogenic activities including forestry, peat harvesting and industrial emission of sulphur dioxide can cause a reduction in CH4 release from northern peatlands. Further research should be conducted to investigate the in fluence of plant growth forms on CH4 flux from northern peatlands, determine the water table threshold at which plant production in peatlands enhances CH4 release, and quantify peatland CH4 exchange at plant community level with a higher temporal resolution using automatic chambers.

The Effect of Toxic Sulfide Exposure on Oxygen Consumption and Oxidation Products in Urechis unicinctus(Echiura:Urechidae)

To investigate sulfide detoxification in Urech＆ unicinctus, oxygen consumption rate and sulfide detoxification products were analyzed during sulfide exposure under controlled laboratory conditions. The results showed that oxygen consumption rates were elevated significantly during 3 h sulfide exposure compared to the control （P〈0.05）. The concentration of sulfite in body wall and hindgut of experimental worms increased significantly （P〈0.05） when exposed to 50 μmolL^-1 sulfide, reached a maximum at 24 h and then decreased. Similar result was observed in worms exposed to 150 μmolL^-1 sulfide except that sulfite concentration reached a maximum at 12 h. Contents of thiosulfate in body wall and hindgut of U. unicinctus exposed to sulfide were also significantly higher than that of the control without sulfide exposure. In conclusion, during short-time sulfide exposure U. unicinctus may raise oxygen consumption to detoxify toxic sulfide into sulfite and thiosulfate. Sulfide detoxification was restrained when the exposure time was prolonged or sulfide concentration was increased, which was indicated by decrease of sulfite, the intermediate product of sulfide detoxification.

SSHT Process -a Low Cost Solution for Low Sulfur and Low Aromatics Diesel

The need for cleaner fuels has resulted in a continuing worldwide trend to reduce diesel sulfur and aromatics. There are many approaches to reducing sulfur and aromatics in diesel. Most of them have a common drawback of high cost because of adopting two stages of hydrotreating and using noble-metal catalyst, especially for reducing aromatics. The attempt to resolve this issue has led to the recent development of the Single Stage Hydrotreating (SSHT) process by Research Institute of Petroleum Processing (RIPP), SINOPEC.The SSHT process is a single-stage hydrotreating technology for producing low sulfur and low aromatics diesel. The process uses one or two non-noble-metal catalysts system and operates at moderate pressure. When revamping an existing unit to meet low aromatics diesel specification, the only thing to do is to add a reactor or replace the existing reactor, In pilot plant tests, the SSHT technology has successfully treated SRGO (Straight Run Gas Oil), LCO (Light Cycle Oil) or the blend of them. It is shown that by using the SSHT process diesel with sulfur of 30 ppm and aromatics of 15 m% can be produced from Middle-East SRGO and diesel with aromatics content of 25 m% can be produced from cracked feed, such as FCC-LCO. High diesel yield and cetane number gain (from cracked feed stocks) give the SSHT technology a performance advantage compared to conventional hydrocracking and hydrotreating processes.The lower investment and operating cost is another advantage. The first commercial application of the SSHT technology has been in operation since September 2001.

Microwave-assisted hydroxylation of benzene to phenol with H_2O_2 over FeSO_4/SiO_2

Hydroxyl radicals HO are generated under Fenton-like (Fe2++H2O2→HO?+OH?+Fe3+) catalytic conditions upon microwave irradiation. Liquid-phase direct catalytic oxidation of benzene to phenol was obtained using FeSO4 supported on silica gel as a solid catalyst and hydrogen peroxide as the oxidant. The effects of various parameters, such as the different solvents, the amount of solvent used, the amount of catalyst used, the reaction time, the reaction temperature and the amount of hydrogen peroxide used on the yield of phenol were studied to identify optimum reaction conditions. Conventionally heated reaction gives a phenol yield of 0.6%. A higher phenol yield of 13.9% with a selectivity of 100% is obtained when the reaction mixture was irradiated with micro-wave energy. It is concluded that microwave irradiation offers more effective control of energy input for hydroxyl radical generation that is appropriate for various synthetic reactions.

Estimation of SO_2 emission factors from copper smelting industry in Yunnan Province,China

Copper smelting is a significant source of SO2 emission. It is important to quantify SO2 emissions from combustion sources for regulatory and control purposes in relation to air quality. The characteristics of SO2 emissions from copper smelting industry in Yurman Province, China, were examined. Analysis based on the present situation, material balance and measuring method were used to confirm SO2 emission factors of copper smelting industry. Results show that SO2 emission factors for Isa system, side blown-continuous converting system （SB-CC）, blast furnace-continuous converting systems （B-CC） and blast furnace-converter blowing （B-C） are 11.69-18.64, 62.44--101.4, 19.43-37.88 and 45.48-81.03 kg/t（blister copper）, respectively. The comprehensive emission factor based on all smelting plants is found to be in the range of 23-39.99 kg-SO2/t（blister copper） for Yunnan Province, China. The results are compared with those for discharge coefficients of industrial pollutants in the First National General Survey of Pollution Sources and the emission factor of the total amount of major pollutants. It is observed that there are some differences among emission factors.