Conversion of Mixed Low-Density Polyethylene Wastes into Liquid Fuel by Novel CaO/SiO<Subscript>2</Subscript> Catalyst

Plastic wastes disposal can be done by various methods such as landfill, incineration, mechanical and chemical recycling but these are restricted due to some environmental, economic and political problems. Conversion of these plastic wastes into valuable products by degradation is the best option. In the present work waste low density polyethylene was degraded by catalytic process using CaO/SiO₂ as mixed catalyst. The conditions for catalytic degradation were optimized for the production of maximum liquid fuel. It was found that the yield of liquid product was up to 69.10 wt% at optimum condition of temperature (350 °C), time (90 min) and catalyst feed ratio (1:0.4). Liquid fuels obtained from the catalytic degradation were further separated into various fractions by fractional distillation. Composition of liquid fuels was analyzed by FTIR spectroscopy, which showed that the liquid fuels mostly consist of paraffinic and naphthenic hydrocarbons. Different fuel properties such as density, specific gravity, American petroleum institute gravity (API gravity), viscosity, kinematic viscosity, refractive index, refractive intercept and flash point of both the parents and various fractional fuels were determined. All the properties of the obtained fuels are in close agreement with the fuel properties of gasoline, kerosene and diesel. It was found that our catalyst is very much efficient in terms of time, degradation temperature and amount of catalyst.     

Study on desulfurization performance of MnO<Subscript>2</Subscript>-based activated carbon from waste coconut shell for diesel emissions control

Increasing concern about the air pollution caused by sulfur dioxide (SO₂) from diesel exhaust has resulted in the improvement of low-temperature desulfurization materials for the combined SO₂ trap. In this study, coconut shell activated carbon (AC) is pretreated by nitric acid to prepare MnO₂-based activated carbon materials for SO₂ removal. The prepared materials are characterized intensively by SEM, TEM, BET, XRD, FTIR, and XPS. The SO₂ capture capacity of these materials are measured at low temperature by thermogravimetry, and the SO₂ equilibrium adsorption characteristic is also investigated. The results show that the concentrations of nitric acid do not significantly change the textural properties of MnO₂-based AC materials. The content of surface-oxygenated groups (carbonyl carbon and transition) initially increases with the HNO₃ concentration rising and reaches the maximum value when the HNO₃ concentration is 10 mol/L, resulting in the enhancement of the SO₂ capture capacity. SO₂ capture capacity of MnO₂-based activated carbon decreases after regeneration and keeps stable after several cycles of thermal regeneration. The experimental data for SO₂ adsorption on MnO₂-based AC composite can fit the Freundlich model well in comparison with Langmuir model.     

Optimization of the food waste water incineration with respect to CO and NO<Subscript>x</Subscript> emission characteristics

The incineration of food waste water in conjunction with the domestic waste is getting attention as a food waste water treatment method, due to its low treatment cost and high efficiency. Many studies verified that the ammonia in the food waste water served as a reducing agent to suppress the generation of NO_x when the food waste water was injected and incinerated. However, they have not revealed the correlation between the change in the concentration of the CO and NO_x by the influence of the solid matters contained in the food waste water on the incineration of the wastes. The purpose of this study is to determine the optimum amount of the food waste water injected through four nozzles in the primary and secondary incineration chambers and to assess the correlation between the concentration of CO and NO_x in accordance with the food waste water injection in each chamber of the incinerator. For the study, four food waste water injection nozzles were installed; two (A and B) at the top of the primary incineration chamber and the other two (C and D) in the secondary incineration chamber. The correlation between the change in the concentration of CO and NO_x was studied adjusting the amount of the food waste water injected through the nozzles. From the result, Case II showed the concentration of CO and NO_x as 1.8–10 and 14–26 ppm, respectively, while Case I showed that of CO and NO_x as 15–30 and 9–18 ppm, respectively. Those levels are well below the Korean emission criteria, 50 ppm for CO and 80 ppm for NO_x. Based on the results, it is evident there is a certain trade-off between emission of CO and NO_x, and Case II which has relatively low concentration of CO is easier and cheaper to control.     

烟气脱硝低温选择性催化还原金属氧化物催化剂的研究进展

低温选择性催化还原(SCR)技术具有很高的脱硝效率。概述了低温SCR金属氧化物催化剂的制备方法和性能,分析了催化剂的失活原因和再生方法,探讨了催化反应的机理,并介绍了低温SCR技术在工业烟气脱硝中的应用案例。SCR催化剂未来的发展不仅要以低温下的高活性和高选择性为主要目的,还要考虑到催化剂的抗失活性能(如抗硫性和抗水稳定性)和操作温度范围,使其可广泛应用于不同的工况中,以满足我国日益提高的环保要求。     

Synthesis,Characterization and NH<Subscript>3</Subscript>/N<Subscript>2</Subscript> Gas Permeation Study of Nanocomposite Membranes

Carbon nanotubes have exceptional mechanical properties which make them very attractive for the development of composite membranes. In this research, NH₃/N₂ gas permeation behavior of flat sheet composite membranes was examined. The cellulose acetate-multiwalled carbon nanotubes composite membranes were synthesized using solution casting method. The morphology and dispersion of carbon nanotubes were observed through SEM. However, the composite membranes were also characterized using several analytical techniques such as X-ray diffraction analysis, tensile testing analysis, and thermal gravimetric analysis. Characterization of these membranes depicted that carboxylic group functionalized MWCNTs are extremely compatible with CA. The permeation experiments were performed with NH₃ and N₂ to explore the host–guest interaction of MWCNTs with chosen gases. The permeability of NH₃ was found pronounced compared to N₂. The NH₃/N₂ selectivity up to 90 was documented.     

Preparation and characterization of mesoporous γ-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> recovered from aluminum cans waste and its use in the dehydration of methanol to dimethyl ether

The present study includes synthesis of two γ-Al₂O₃ samples from waste aluminum cans using a simple precipitation method. Precipitation was carried out using two different precipitating agents (i.e. NaOH and NH₄OH). The two prepared alumina samples were characterized by means of X-ray diffraction (XRD) and N₂ adsorption–desorption techniques. Surface acidity of γ-Al₂O₃ samples was measured by adsorption of two different probe molecules (i.e. pyridine and dimethyl pyridine) followed by desorption measurements using thermogravimetry (TG) and differential scanning calorimetry (DSC) techniques. Catalytic activity of the two prepared alumina samples towards the dehydration of methanol (to dimethyl ether) was studied in a fixed bed reactor at 300 °C. For comparison reasons, commercial γ-Al₂O₃ sample was, also, tested for the same catalytic reaction under the same conditions. Results showed that the alumina sample prepared using NaOH as a precipitating agent exhibited a better catalytic activity and stability compared with that prepared using NH₄OH and showed a similar activity as the commercial γ-Al₂O₃ sample.     

Green Synthesis of Fe<Subscript>3</Subscript>O<Subscript>4</Subscript>/Cellulose/Polyvinyl Alcohol Hybride Aerogel and Its Application for Dye Removal

A novel Fe₃O₄/cellulose–polyvinyl alcohol (PVA) aerogel was successfully synthesized by an eco-friendly and facile method in this work. Cellulose/PVA matrix was prepared through an environmental friendly physical cross-linking process and further in-situ decorated with Fe₃O₄. Series of Fe₃O₄ decorated aerogels were prepared and the effects of Fe₃O₄ nanoparticles (NPs) on the aerogels were systematic investigated. As-prepared aerogels exhibited desirable properties including nanostructure, relatively high porosity, improved mechanical and superparamagnetism. The TEM results showed that Fe₃O₄ NPs were integrated in the three-dimensional matrix of cellulose/PVA with a diameter of 9–12 nm. Furthermore, the mechanical strength of the aerogels was significantly enhanced after the introduction of Fe₃O₄ NPs. Meanwhile, the obtained Fe₃O₄/cellulose/PVA aerogel exhibited excellent adsorption performance toward methyl blue dye, and can be reused through fenton-like catalysts oxidative degradation of organic dye in H₂O₂ solution. Therefore, they will have a great potential application as eco-friendly and economical adsorbents.     

Recycling nickel from spent catalyst of Phu My fertilizer plant as a precursor for exhaust gas treatment catalysts preparation

In this study, a very promising way of treating and recycling spent nickel catalysts of fertilizer plants in Vietnam was proposed. Firstly, nickel was recovered from spent catalyst using HNO₃—leaching process. Results show that nickel recovery of over 90% with a purity of over 90% can be achieved with HNO₃ 2.1–2.5 M at 100?°C in 75 min. The residue after leaching is not considered as a hazardous waste according to the Vietnamese regulations. Then, the leachate solution was used as a precursor to prepare a model catalyst for exhaust gas (CO, HC, NO_x) treatment. In comparison with the catalyst prepared from the commercial nickel nitrate solution, the catalyst synthesized from recovered nickel exhibits similar properties and activities. The influence of Ni loading of Ni/alumina catalyst as well as the modification of active phase by some metals addition (Mn, Ba, Ce) was also investigated. It is feasible to modify active phase by transition metals such as Mn, Ba, and Ce for complete oxidation of CO and HC at 270?°C and a reduction of NO_x below 350?°C at high volumetric flow condition (GHSV?=?110.000 h^?1).     

Reductive decomposition of waste gypsum with SiO<Subscript>2</Subscript>, Al<Subscript>2</Subscript>O<Subscript>3</Subscript>, and Fe<Subscript>2</Subscript>O<Subscript>3</Subscript> additives

From the point of view of a sustainable and environment-friendly society based on the recycling of material resources, it is preferable to utilize waste gypsum as a substitute for lime, which is currently produced by the calcination of limestone. In the present work, the reductive decomposition of CaSO₄ was investigated under an atmosphere of CO: 2 vol%, CO₂: 30 vol%, with N₂ as a carrier gas without and with the addition of SiO₂, Al₂O₃, or Fe₂O₃. It was found that the decomposition temperature of CaSO₄ was significantly reduced from 1673 K to 1223 K when only 5 wt% Fe₂O₃ was added to CaSO₄. In the case of the addition of SiO₂ or Al₂O₃ to CaSO₄, the decomposition temperature was reduced from 1673 K to 1623 K. This was due to the formation of composite oxides (calcium ferrite, calcium silicate, or calcium aluminate) during the reaction of CaSO₄ with the additives at a lower temperature. In addition, the formation of unfavorable product CaS was inhibited in the presence of 5 wt% Fe₂O₃, and this inhibition effect further increased as the addition of Fe₂O₃ was increased. In contrast, no significant effect on the inhibition of CaS formation was observed on the addition of SiO₂ or Al₂O₃.     

Preparation of Water-Insoluble Antibacterial Materials with Surface-Grafted Material PSt/SiO<Subscript>2</Subscript> and Their Antibacterial Activity

Styrene (St) was graft-polymerized onto the surfaces of micro-sized silica gel particles, and the surface-grafted composite particles PSt/SiO₂ were obtained. With the surface-grafted composite particles PSt/SiO₂ as a starting material, water-insoluble antibacterial materials with quaternary ‘onium’ salt-type were synthesized via two polymer reaction steps. The grafted polystyrene was first chloromethylated, resulting in grafted particles CMPS/SiO₂, and then quaterisation (QN) and quaternary phosphonium reaction (QP) were conducted with triethylamine, tri-n-butylamine and triphenyl phosphine as reagents, respectively. Two kinds of water-insoluble antibacterial materials, QN-PSt/SiO₂ and QP-PSt/SiO₂ were prepared. Their antibacterial property was mainly investigated by using Escherichia coli (E. coli) as a model bacterium and by adopting colony count method. The relationship between the chemical structure of the antibacterial group and antimicrobial activity for the water-insoluble antibacterial materials was studied in detail, and their antibacterial mechanism was investigated by TTC-dehydrogenase activity determination and extracellular DNA and RNA measurement methods. The experimental results show that QN-PSt/SiO₂ and QP-PSt/SiO₂ possess strong antibacterial activity. The main factors affecting the antibacterial ability of the water-insoluble materials are the chemical structure of the antibacterial groups, the bound density of the antibacterial groups on the surface of the water-insoluble antibacterial materials as well as the pH value of the medium. QP-PSt/SiO₂ has stronger antibacterial activity than QN-PSt/SiO₂; the QN-PSt/SiO₂ prepared with tri-n-butylamine has stronger antibacterial activity than that prepared with triethylamine; the water-insoluble material with higher bound density of the antibacterial groups has stronger antibacterial ability; as the pH value of the medium is over the isoelectric point of E. coli, the antibacterial ability is strengthened with the increase of pH value.     

Preparation and characterization of high surface area activated carbon from pine wood sawdust by fast activation with H<Subscript>3</Subscript>PO<Subscript>4</Subscript> in a spouted bed

Activated carbons were produced from waste pine wood sawdust using fast activation with H₃PO₄ in a spouted bed. In this study, activation temperature was set as 800 °C, and activation time ranged from 1 to 15 min. Experimental results show that sawdust impregnated with higher mass ratio of H₃PO₄ would be agglomerated in spouted bed, and difficult to fluidize. Therefore, an amount of quartz sand was added to assist for good fluidization. Fluidization of particle can improve the BET surface area or micropore volume of activated carbons. High BET surface area activated carbons can be obtained with activation time of only 1–5 min by combining the fluidization and H₃PO₄ fast activation. The obtained activated carbons contained developed pore structure and abundant surface functional groups (carboxyl, carbonyl and P-containing groups) by SEM–EDS, FTIR and XPS techniques. The particles of impregnation ratio of 1:1 can achieve fluidization without adding the quartz sand, which was convenient for experimental operation and even industrial production, and the BET surface area can reach more than 1000 m²/g in activation time of only 5 min.     

Photochemical Degradation of Aqueous Polyvinyl Alcohol in a Continuous UV/H<Subscript>2</Subscript>O<Subscript>2</Subscript> Process: Experimental and Statistical Analysis

Polyvinyl alcohol (PVA), being a dominant contributor of total organic carbon (TOC) in textile wastewater, is not easily degradable by conventional methods of wastewater treatment. This study investigates the degradation of aqueous PVA in a continuous UV/H₂O₂ photoreactor since the feeding strategy of hydrogen peroxide proves to have considerable effects on the process performance. Response surface methodology involving the Box–Behnken method is adopted for the experimental design to study the effects of operating parameters on the process performance. Experimental analysis shows that the TOC removal varies from 16.11 to 42.70 % along with a reduction of the PVA molecular weights from 56.7 to 95.3 %. The TOC removal is significantly lower than the molecular weight reduction due to the generation of the intermediate products during oxidation. Operating the UV/H₂O₂ process in a continuous mode facilitates the degradation of highly concentrated polymeric solutions using a relatively small hydrogen peroxide concentration in the feed with a small residence time ranges from 6.13 to 18.4 min.     

Absorption behavior of chlorine and sulfur by Ca(OH)<Subscript>2</Subscript> under simulated conditions with a fluidized bed combustor

This study was carried out to investigate the absorption reaction of chlorine and sulfur with Ca(OH)₂ under simulated conditions related to the co-combustion of refuse-derived fuel and sewage sludge in the fluidized bed combustor, such as high temperature, moisture and a mixing of samples. The combustion experiments were carried out in an electrical furnace with PVC and sulfur powders as the waste samples. High-purity slaked lime powder was used to capture the chlorine and sulfur. The experimental results showed that the removal efficiencies of both chlorine and sulfur were over 90% when the mole ratios of Ca on Cl and S were over 2.5. Furthermore, simultaneous absorption was helpful in improving the removal efficiency of chlorine and sulfur. The presence of chlorine markedly increased the removal efficiency of sulfur. The removal efficiency of chlorine was the highest at 700°C in both independent and simultaneous absorption. The removal efficiency of sulfur increased as the temperature increased, but the removal efficiency of chlorine sharply decreased from 95 to 83% when the moisture content in gases increased from 0 to 20 vol%. These results were confirmed by the combustion test of granular CaCl₂.     

金属有机骨架材料低温脱硝技术研究进展

金属有机骨架材料（MOFs）因其独特的结构作为催化剂应用于SCR系统表现出较好的低温脱硝效果和较强的抗SO₂、抗H₂O性能。综述了几种较典型的MOFs催化剂及其改性产物的低温催化性能,以及MOFs材料应用于SCR技术的研究进展,指出：对含有两种或两种以上金属的复合MOFs材料的深入研究,是开发稳定性更高、抗SO₂抗H₂O能力更强的MOFs催化剂的重要思路;此外,对有机组成部分进行改性,提高有机配体的热稳定性也是一个重要的研究思路。     

Fabric-filter-supported catalyst for removal of harmful solid and gaseous compounds in municipal waste incinerator exhaust gas: characteristics of NO x reduction

We have investigated a fabric-filter-supported catalyst for removing harmful solid and gaseous compounds simultaneously from municipal incinerator exhaust gas. We studied the ways in which the efficiency of NO _x removal is influenced by filter temperature, gas flow rate, and catalyst content. The reduction of the catalyst content by mechanical reverse washing was investigated, and the state of the catalyst supported in the fabric filter was also observed using a scanning electron microscope. The catalyst supported by the fabric filter showed a removal efficiency above 75% when the filter temperature was 200°C, the gas flow rate was 1 m/min, and the catalyst content of the fabric filter was above 300 g/m². The catalyst was supported uniformly on the fibers of the fabric filter, and fine catalyst particles remained on the fibers after mechanical reverse washing. Received: October 15, 1997 / Accepted: March 19, 1999     

基于TiO2载体的锰铈系低温SCR脱硝催化剂研究进展

开发低温、高活性、高抗硫抗水性能的选择性催化还原(SCR)脱硝催化剂已成为国内外的研究热点。综述了基于TiO2载体的锰铈系低温脱硝催化剂的脱硝性能,探讨了助剂掺杂改性、制备方法、反应条件等对催化剂脱硝性能的影响,总结了现有低温脱硝催化剂的技术难点,指出SCR催化剂的研究需要着重考虑以下几方面:深入研究催化剂的反应机理和中毒机理;研究催化剂的循环再生;探究拓宽催化剂温度窗口,使其适应不同的温度条件。     

The Role of Catalyst Properties on Methanol Oxidation over V2O5–TiO2 Using Ozone

Oxidation of methanol over V₂O₅ catalysts supported on anatase TiO₂ that were prepared using sol-gel formation and impregnation procedures were investigated. The effects of incorporating Mg in sol-gel to influence the properties of the catalyst were also studied. The process provides an alternative low temperature reaction pathway for reducing emissions of hazardous air pollutant (HAPs) such as methanol and total reduced sulfur compounds (TRS) from pulp and paper mills. The bulk and surface composition of the catalysts were determined by XRD and SEM-EDAX, respectively. The X-ray diffraction patterns of the vanadia–titania catalysts showed mainly the anatase phase of TiO₂. Temperature programmed desorption of methanol from the different catalyst showed that the α and β peaks differ significantly with V content and addition of Mg. The combination of gas phase and surface reactions on the V/TiO₂ catalysts reduced the amount of ozone required for high degradation of methanol to mainly CO _x with small quantities of methyl formate. In the absence of ozone the catalysts showed very low activity. It is hypothesized that the ozone is directly influencing the V⁴⁺ and V⁵⁺ redox cycle of the catalyst. Oxidation of methanol is influenced by the operation variables and catalyst properties. The results of this study revealed that the V content has significant influence on the catalyst activity, and the optimum vanadia loading of about 6 wt%. Higher turnover frequencies were observed over sol-gel catalysts than with catalysts prepared by the impregnation method.     

Photochemical Kinetic Modeling of Degradation of Aqueous Polyvinyl Alcohol in a UV/H<Subscript>2</Subscript>O<Subscript>2</Subscript> Photoreactor

This study presents a photochemical kinetics model to describe the degradation of water-soluble PVA (Polyvinyl Alcohol) polymer in a UV/H₂O₂ batch reactor. Under the effect of UV light, the photolysis of hydrogen peroxide into hydroxyl radicals can generate a series of polymer scission reactions. For a better understanding and analysis of the UV/H₂O₂ process in the cracking of the PVA macromolecules, a chemical reaction mechanism of the degradation process and a relevant photochemical kinetics model are developed to describe the disintegration of the polymer chains. Taking into account the probabilistic fragmentation of the polymer, the statistical moment approach is used to model the molar population balance of live and dead polymer chains. The model predicts the PVA molecular weight reduction, the acidity of the solution, and hydrogen peroxide residual. In addition to previously published data collected in this laboratory, a new set of experiments were conducted using a 500 mg/L PVA aqueous for different hydrogen peroxide/PVA ratios for model validation. Measurements of average molecular weights of the polymer, hydrogen peroxide concentrations and pH of the PVA solution were determinant factors in constructing a reliable photochemical model of the UV/H₂O₂ process. Experimental data showed a decrease in the PVA molecular weight and a buildup of the solution acidity. The experimental data also served to determine the kinetics rate constants of the PVA photochemical degradation and validate the model whose predictions are in good agreement with data. The model can provide a comprehensive understanding of the impact of the design and operational variables.     

Effect of Nanoscale SiO<Subscript>2</Subscript> and TiO<Subscript>2</Subscript> as the Fillers on the Mechanical Properties and Aging Behavior of Linear Low-Density Polyethylene/Low-Density Polyethylene Blends

Linear low-density polyethylene (LLDPE) was blended with low-density polyethylene (LDPE) at a fixed ratio (80 wt LLDPE and 20 wt %LDPE) and filled with nanoparticles of SiO₂ and TiO₂ at a ratio up to wt 5%, so as to develop the polymeric composites suitable to preparing the agricultural micro-irrigation pipes having good environmental adaptability. These compounds were blended using calcium stearate, polyethylene wax, and titanate coupling agent as the auxiliary dispersants, and ethylene-vinyl acetate copolymer (EVA) as the toughness improver. The LLDPE/LDPE composites filled with the nanoparticles were extruded and injected to prepare the composites specimens for the performance evaluations and micro-irrigation pipe field test. The mechanical properties, thermostability, and processibility of the injected composites were investigated. The effect of heating in an oven and irradiating by ultraviolet on the mechanical properties of the composites was explored. The environmental adaptability of the micro-irrigation pipes made of the filled LLDPE/LDPE composites was evaluated making use of long-term outdoor field test in northwest China where the arid and harsh natural conditions are of great concerns. It was found that the LLDPE/LDPE blend with the LLDPE mass fraction fixed as 80% showed balanced mechanical and thermal properties and flexibility, and was suitable to be used as the basic resin matrix. The incorporation of nano-TiO₂ contributed to effectively improving the resistance to heating and ultraviolet irradiation of the composites. The composite made from 91% basic resin matrix, 6% EVA, and 3% mixed nano-SiO₂ and TiO₂, showed balanced comprehensive properties. The micro-irrigation pipes made of this filled LLDPE/LDPE composite had good environmental adaptability and service behavior in a three-year field test and were suitable to be used in arid area.     

Effect of ZnCl<Subscript>2</Subscript> impregnation ratio on pore structure of activated carbons prepared from cattle manure compost: application of N<Subscript>2</Subscript> adsorption-desorption isotherms

Activated carbons were prepared from cattle manure compost (CMC) by ZnCl₂ activation with various ZnCl₂/CMC mass ratios. Based on the N₂ adsorption-desorption isotherms, mathematical models including the Dubinin-Radushkevich (DR) equation, the α_s plot, and the Horvath-Kawazoe method were used to analyze the pore structural characteristics of the prepared activated carbons. It was found that for carbons possessing both micro-and mesopores, the DR method provided a more accurate estimation than the α_s method for the extent of microporosity. The effect of the ZnCl₂ impregnation ratio on the pore structure was discussed using the DR method. The results revealed that pore evolution involved three distinct regions with increases in the amount of impregnated ZnCl₂: raising the ZnCl₂/CMC mass ratio from 0.00 to 0.50 resulted in a 19-fold increase in micropore volume (V_me ^D) but caused no change in the mesopore volume (V_me ^D); increasing the ZnCl₂/CMC mass ratio from 0.50 to 1.00 led to an increment in V_mi ^D of about 50% and in V_me ^D of 170%; while raising the ratio from 1.50 to 2.50 caused a slight decrease in V_mi ^D but a 200% increment in the value of V_me ^D.