Effect of Metal Compounds and Experimental Conditions on Distribution of Products from PVC Pyrolysis

Effects of heating rate, gas flow rate, and type of metal compounds on the amount of hydrogen chloride, liquid, gas, and solid pyrolyzate obtained from the pyrolysis of poly(vinyl chloride) (PVC) were investigated. The pyrolysis experiments were carried out in both a thermogravimetric analysis (TGA) instrument and a fixed-bed reactor. Products from the fixed-bed reactor were collected and analyzed by using Fourier transform infrared spectroscopy (FTIR), gas chromatography-mass spectroscopy (GC-MS), titration technique, and gravimetry. It was found that heating rate in the TGA experiments did not affect the amount of released hydrogen chloride. However, the TGA profiles significantly changed with the rate. The onset of dehydrochlorination increased with the rate. In addition, as the heating rate was increased from 10 to 20°C/min, there was no solid residue left. The amount of liquid pyrolyzate obtained from the fixed-bed reactor can be either increased or decreased with the heating rate, depending on the gas flow rate and the actual residence time in the reactor. FTIR and GC-MS analysis indicated that the liquid pyrolyzates were mainly benzene, toluene, and styrene. By comparing the efficiency of various metal compounds in trapping the HCl, it was found that Ca(OH)₂ was more efficient than Mg(OH)₂, and that CaO was more efficient than MgO. These results are discussed in light of the reaction mechanism between HCl and the metal compounds.     

MnOx/TiO2催化剂催化燃烧去除废气中的正己烷

采用溶胶-凝胶法制备了MnOx/TiO2催化剂,考察了n(Mn):n(Ti)、催化剂载体、气体流量对催化燃烧去除废气中正己烷效果的影响.实验结果表明:随着n(Mn):n(Ti)的增加,正己烷去除率先增加后减小,气体流量减小正己烷去除率增大;当n (Mn):n(Ti)为7.85％、气体流量为100 mL/min时,在240℃时正己烷的去除率为90％,MnOx/TiO2催化活性最大;MnOx/TiO2的催化活性优于MnOx/SiO2;SEM和XRD表征结果表明,所制备的MnOx/TiO2是一种活性物种MnOx高度分散的纳米结构催化剂.     

锐钛矿-金红石混合晶型TiO2降解气相苯

用溶胶-凝胶法并通过控制煅烧温度合成不同晶相比的混合晶型纳米TiO_2,在紫外光光照下降解气相苯。考察了苯初始质量浓度、紫外灯光照强度和催化剂加入量对苯去除率的影响;探究了光催化降解气相苯的动力学特征。结果表明:450℃煅烧制备的催化剂降解苯效率最高,此催化剂金红石相质量分数为6.30%;在苯初始质量浓度为74.39 mg/m~3、催化剂加入量为7 g、光照强度为2.18 klux的最佳条件下反应84 min,苯去除率达99.73%;光催化降解率与光照强度之间符合0.5级动力学特征;当催化剂加入量为3 g时,单位时间单位质量催化剂降解苯的质量最多;苯的光催化降解反应均符合一级动力学方程。     

Production of hydrogen by steam gasification of dehydrochlorinated poly(vinyl chloride) or activated carbon in the presence of various alkali compounds

Steam gasification of dehydrochlorinated poly(vinyl chloride) (PVC) or activated carbon was carried out in the presence of various alkali compounds at 3.0 MPa and 560°C–660°C in a batch reactor or in a semi-batch reactor with a flow of nitrogen and steam. Hydrogen and sodium carbonate were the main products, and methane and carbon dioxide were the minor products. Yields of hydrogen were high in the presence of sodium hydroxide and potassium hydroxide. The acceleration effect of the alkali compounds on the gasification reaction was as follows: KOH > NaOH > Ca(OH)₂ > Na₂CO₃. The rate of gasification increased with increasing partial steam pressure and NaOH/C molar ratio. However, the rate became saturated at a molar ratio of NaOH/C greater than 2.0.     

A chemox treatment for urea‐ and ammonium‐contaminated groundwater

In a pilot project performed at a fertilizer manufacturing facility, a one‐step chemical oxidation technique successfully treated urea‐ and ammonium‐contaminated groundwater. The oxidation reaction occurred in an 1,100‐gallon batch reactor. The contaminated inflow was buffered by the metered addition of sodium bicarbonate solution and subsequently treated with sodium hypochlorite in an 8:1 weight ratio of Cl₂:N. In an instantaneous reaction, the urea and ammo‐nium‐N were completely oxidized to nitrogen gas that was vented to the atmosphere during mixing. The pH of the reactor discharge was ?6.5. Sodium sulfite was used to reduce residual hypochlorite in the reactor effluent to chloride to provide process water with characteristics suitable for discharge. Oxidation rates were similar with different strengths of hypochlorite; however, a 5 to 6 percent sodium hypochlorite (as Cl₂) solution was the most stable. © 2005 Wiley Periodicals, Inc.     

Removal of Reactive Blue 19 dye from synthetic wastewater using UV/H2O2 and UV/Cl advanced oxidation processes

The textile and dyeing industries are among the largest water-consuming and polluting industries in the world. The most important feature of the textile dyeing industry wastewater is its color, due to the use of colored materials. Most of these dye compounds are resistant to conventional purification methods and their biodegradation is very low through secondary purification processes, resulting in incomplete removal. Therefore, selecting the optimal method to remove these color compounds is essential. In this study, we studied the removal of an organic dye contaminant (Reactive Blue dye 19 [RB19]) using advanced oxidation processes (AOPs). For this purpose, ultraviolet (UV) mercury lamps with a wavelength of 254 nm and a voltage of W16 inside a reactor were used as an energy source. The experiments were performed in a collimated beam reactor inside a dark chamber. Two oxidizers, sodium hypochlorite (NaOCl) and hydrogen peroxide (H₂O₂), were used to remove RB19 from the artificial sewage stream. Removal of RB19 with a concentration of 20 mg/L with variable pH (5, 7, and 9), oxidant concentrations (5, 10, and 20 mg/L), and time (5, 10, 15, and 30 min) were investigated during the processes of photolysis, chemical oxidation (by H₂O₂ and NaOCl), and UV/NaOCl and UV/H₂O₂ AOPs. The photolysis process did not remove the RB19. The highest removal efficiencies of RB19 by chemical oxidation processes with NaOCl and H₂O₂, UV/NaOCl, and UV/H₂O₂ at optimal conditions (pH = 5, [oxidant] = 20 mg/L, RB19 = 20 mg/L, and radiation intensity of 1005 mJ/cm²) were 64.49%, 0.88%, 99.7%, and 13.31%, respectively. These results indicate that the hydroxyl radical was produced, under optimum conditions, more in the acidic medium; thus, the RB19 removal efficiency was higher in the acidic medium. The combination of UV rays with oxidants resulted in the production of more hydroxyl radicals and increased removal efficiency.     

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.     

膜法解吸CO_2吸收富液

采用中空纤维膜接触器(FMC)作为解吸装置,对吸收了CO_2的N-甲基二乙醇胺(MDEA)溶液(富液)进行膜法解吸实验。考察了CO_2负荷、解吸温度、解吸压力、富液流速和N_2吹扫流量对CO_2解吸率的影响。结果表明,富液中CO_2负荷越大、解吸温度越高、解吸压力越低、富液流速越大、N_2吹扫流量越大,则CO_2解吸率越高。综合考虑,本实验优选的工艺条件为解吸温度45~65℃,解吸压力10~30 k Pa,富液流速0.08 m/s,N_2吹扫流量200 m L/min。     

Recovery of benzene-rich oil from the degradation of metal- and metal oxide-containing poly(ethylene terephthalate) composites

Pure poly(ethylene terephthalate) (PET) resin and metal-/metal oxide-containing PET composites were thermally decomposed in the presence of Ca(OH)₂ using a tube reactor. The effects of batch and continuous processing, the presence of Ca(OH)₂, and PET size on benzene production were investigated. A maximum benzene yield and purity of 82.9 % and 78.8 wt%, respectively, were obtained at 700 °C in the presence of Ca(OH)₂ when using small PET particles; further, a continuous feed reactor was favored over a batch reactor. Effective contact between PET and Ca(OH)₂ was important in the PET degradation, which promoted hydrolysis of PET and decarboxylation of terephthalic acid, whereas pyrolysis was suppressed. Furthermore, the results of thermal decomposition of PET-based waste—PET-based X-ray films, magnetic tape, and prepaid cards—indicated that the metal and metal oxides contained in the waste had no significant catalytic effect on PET degradation or on the recovery of benzene-rich oil in the presence of Ca(OH)₂.     

Kinetic and Mechanistic Studies of NO X Selective Catalytic Reduction Over In/Al2O3 and N2O Decomposition Over Ru/Al2O3

Detailed kinetic studies are presented for two reactions: the nitric oxide (NO) selective catalytic reduction (SCR) by propene over indium/alumina (In/Al₂O₃) and the nitrous oxide (N₂O) reduction over ruthenium/alumina (Ru/Al₂O₃). Both reactions were studied in the presence of excess oxygen (O₂) to simulate the composition of flue gases. Apparent activation energies and apparent orders of reaction were calculated in experiments performed under differential reaction conditions. We used our experimental results to propose the reaction mechanism that leads to nitrogen formation over the two catalysts. The NO reduction proceeds through the initial formation of C _X H _Y O _Z N, a reaction intermediate that reacts with activated nitrogen oxides (NO _X ). Nitrous oxide is catalytically decomposed to nitrogen (N₂) over Ru/Al₂O₃.     

Field scale N2O flux measurements from grassland using eddy covariance

In order to assess nitrous oxide (N₂O) emissions from typical intensively managed grassland in northern Britain fluxes were measured by eddy covariance using tuneable diode laser absorption spectroscopy from June 2002 to June 2003 for a total period of 4000 h. With micrometeorological techniques it is possible to obtain a very detailed picture of the fluxes of N₂O at field scale (10³–10⁴ m²), which are valuable for extrapolation to regional scales. In this paper three of the four fertilizer applications were investigated in detail. N₂O emissions did not always show a clear response. Hourly fluxes were very large immediately after the June 2002 nitrogen fertilizer application, peaking at 2.5 mg N₂O–N m^–2 s^–1. Daily fluxes were averaging about 300 ng N₂O m^–2 s^–1 over the 4 days following fertilizer application. The response of N₂O emissions was less evident after the August fertilization, although 2 days after fertilizer application an hourly maximum flux of 554 ng N₂O–N m^–2 s^–1 was registered. For the rest of August the flux was undetectable. The differences between fertilization events can be explained by different environmental conditions, such as soil temperature and rainfall. A fertiliser-induced N₂O emission was not observed after fertilizer application in March 2003, due to lack of rainfall. The total N₂O flux from June 2002 to June 2003 was 5.5 kg N₂O–N ha^–1y^–1, which is 2.8% of the total annual N fertilizer input.     

循环式超声强化光催化降解双酚A

设计了一种循环式超声强化光催化反应器,以TiO2作为光催化剂,研究了超声功率、TiO2加入量、循环液流速和空气流量对双酚A(BPA)降解效果的影响。实验结果表明:超声与光催化过程在循环式超声强化光催化反应器中实现了较好的协同效应;在初始BPA质量浓度为20.0mg/L、超声功率为600W、TiO2加入量为7g/L、循环液流速为4.05×10-2m/s、空气流量为200mL/min的条件下,反应150min后,BPA降解率可达90.5%,溶液中剩余BPA质量浓度仅为1.8mg/L,反应240min后TOC去除率可达84.5%。     

O_3-H_2O_2催化氧化技术深度处理石化含盐废水

采用O_3-H_2O_2-催化剂氧化体系对某石化企业含盐废水的二级生化出水进行处理,考察了不同反应体系下的反应时间、O_3流量、H_2O_2投加量对COD去除效果的影响。实验结果表明:O_3-H_2O_2-催化剂氧化体系对石化含盐废水的处理效果最好;在臭氧流量为40 m L/min、H_2O_2投加量为50 mg/L、催化剂投加量为300 g/L、反应时间为60 min的条件下,COD去除率为51.4%,出水COD为52.0 mg/L,达到GB31570—2015《石油炼制工业污染物排放标准》的要求。     

High efficiency chlorine removal from polyvinyl chloride (PVC) pyrolysis with a gas–liquid fluidized bed reactor

In this research a gas–liquid fluidized bed reactor was developed for removing chlorine (Cl) from polyvinyl chloride (PVC) to favor its pyrolysis treatment. In order to efficiently remove Cl within a limited time before extensive generation of hydrocarbon products, the gas–liquid fluidized bed reactor was running at 280–320 °C, where hot N₂ was used as fluidizing gas to fluidize the molten polymer, letting the molten polymer contact well with N₂ to release Cl in form of HCl. Experimental results showed that dechlorination efficiency is mainly temperature dependent and 300 °C is a proper reaction temperature for efficient dechlorination within a limited time duration and for prevention of extensive pyrolysis; under this temperature 99.5% of Cl removal efficiency can be obtained within reaction time around 1 min after melting is completed as the flow rate of N₂ gas was set around 0.47–0.85 Nm³ kg^?1 for the molten PVC. Larger N₂ flow rate and additives in PVC would enhance HCl release but did not change the final dechlorination efficiency; and excessive N₂ flow rate should be avoided for prevention of polymer entrainment. HCl is emitted from PVC granules or scraps at the mean time they started to melt and the melting stage should be taken into consideration when design the gas–liquid fluidized bed reactor for dechlorination.     

Hydrogen production from food wastes and gas post-treatment by CO2 adsorption

The production of H₂ by biological means, although still far from being a commercially viable proposition, offers great promise for the future. Purification of the biogas obtained may lead to the production of highly concentrated H₂ streams appropriate for industrial application. This research work evaluates the dark fermentation of food wastes and assesses the possibility of adsorbing CO₂ from the gas stream by means of a low cost biomass-based adsorbent. The reactor used was a completely stirred tank reactor run at different hydraulic retention times (HRTs) while the concentration of solids of the feeding stream was kept constant. The results obtained demonstrate that the H₂ yields from the fermentation of food wastes were affected by modifications in the hydraulic retention time (HRT) due to incomplete hydrolysis. The decrease in the duration of fermentation had a negative effect on the conversion of the substrate into soluble products. This resulted in a lower amount of soluble substrate being available for metabolisation by H₂ producing microflora leading to a reduction in specific H₂ production.Adsorption of CO₂ from a gas stream generated from the dark fermentation process was successfully carried out. The data obtained demonstrate that the column filled with biomass-derived activated carbon resulted in a high degree of hydrogen purification. Co-adsorption of H₂S onto the activated carbon also took place, there being no evidence of H₂S present in the bio-H₂ exiting the column. Nevertheless, the concentration of H₂S was very low, and this co-adsorption did not affect the CO₂ capture capacity of the activated carbon.     

泡沫镍负载La3+-TiO2催化剂对苯的可见光降解

采用溶胶-凝胶法制备了掺杂La³⁺的TiO₂（La³⁺-TiO₂）,并负载于泡沫镍上,制得泡沫镍负载La³⁺-TiO₂催化剂。采用XRD、DSC、荧光发射光谱以及SEM方法进行了表征分析。研究了泡沫镍负载La³⁺-TiO₂催化剂在可见光下对苯的降解效果,并对苯的光催化降解动力学特性进行了分析。实验结果表明：在最佳焙烧温度和焙烧时间分别为400 ℃和1 h的条件下,La³⁺-TiO₂的晶相主要为锐钛矿型;负载后,La³⁺-TiO₂颗粒填充于泡沫镍的空洞中,比表面积增加,光催化活性得以提高;在不同初始苯质量浓度和催化剂使用次数条件下,苯的降解率不同,最高可达92.9 %;光催化降解过程遵循拟一级动力学规律。     

Decomposition of dichloromethane and in situ alkali absorption of resulting halogenated products by a packed-bed non-thermal plasma reactor

For an effective decomposition and removal of organic halogenated compounds, a packed-bed non-thermal plasma reactor with in situ absorption of the resulting halogenated products by alkaline sorbent incorporated was proposed. In the plasma reactor, α-Al₂O₃ particles of 1 and 3 mm (mean particle diameter) were packed as solid dielectric medium to enhance the plasma power density in the reactor. Further, alkaline sorbent of Ca(OH)₂ was doped onto the surface of α-Al₂O₃ particles, in order to remove halogenated products by in situ absorption with Ca(OH)₂. A high-voltage and high-frequency pulsed power of −15 to 15 kV and 1 kHz was applied to the wire electrode of the plasma reactor by means of a DC power source. In the present study, as the sample of an organic halogenated compound that is most popularly used, we selected dichloromethane (CH₂Cl₂), and 500 ppm of the initial concentration of CH₂Cl₂ was fed into the reactor accompanied by air at a fixed flow rate of 500 × 10⁻⁶ m³ min⁻¹ at room temperature. As a result, it was recognized that the amount of CH₂Cl₂ decomposed by non-thermal plasma in an α-Al₂O₃ particle bed increased with an increase in plasma input power. The ratio of decomposition of CH₂Cl₂ was almost 100% at 13 kV of electric power and 1 kHz frequency, and CO₂, CH₃Cl, COCl₂, HCl, and Cl₂ were observed as the major reaction products. On the other hand, when CH₂Cl₂ was introduced into the plasma reactor where α-Al₂O₃ particles doped with Ca(OH)₂ were packed, the ratio of decomposition of CH₂Cl₂ became higher, compared to the case that α-Al₂O₃ particles were not doped with Ca(OH)₂. Moreover, there were no halogenated by-product gases detected in the outlet gas from the reactor. As the solid reaction products, CaClOH and Ca(ClO)₂·4H₂O were detected on Ca(OH)₂ by X-ray diffraction. From these findings, it was recognized that CH₂Cl₂ was decomposed more effectively without producing unwanted harmful halogenated by-products in the proposed non-thermal plasma reactor where α-Al₂O₃ particles doped with Ca(OH)₂ sorbent were packed.     

Pyrolysis of aseptic packages (tetrapak) in a laboratory screw type reactor and secondary thermal/catalytic tar decomposition

Pyrolysis of aseptic packages (tetrapak cartons) in a laboratory apparatus using a flow screw type reactor and a secondary catalytic reactor for tar cracking was studied. The pyrolysis experiments were realized at temperatures ranging from 650 °C to 850 °C aimed at maximizing of the amount of the gas product and reducing its tar content. Distribution of tetrapak into the product yields at different conditions was obtained. The presence of H₂, CO, CH₄, CO₂ and light hydrocarbons, HCx, in the gas product was observed. The Aluminum foil was easily separated from the solid product. The rest part of char was characterized by proximate and elemental analysis and calorimetric measurements. The total organic carbon in the tar product was estimated by elemental analysis of tars. Two types of catalysts (dolomite and red clay marked AFRC) were used for catalytic thermal tar decomposition. Three series of experiments (without catalyst in a secondary cracking reactor, with dolomite and with AFRC) at temperatures of 650, 700, 750, 800 and 850 °C were carried out. Both types of catalysts have significantly affected the content of tars and other components in pyrolytic gases. The effect of catalyst on the tetrapack distribution into the product yield on the composition of gas and on the total organic carbon in the tar product is presented in this work.     

A Geochemical Multi-Methodological Approach in Hazard Assessment of CO2-Rich Gas Emissions at Mt. Amiata Volcano (Tuscany, Central Italy)

The present work aims to assess the hazard for human health related to CO₂ anomalous concentrations in air emitted from dry gas vents located in the NE area of Mt. Amiata volcano (Tuscany, central Italy). A geochemical multi-methodological approach is adopted to determine the composition and the flux rate of the gas discharges in order to establish (1) the origin of the gas vents and (2) the behaviour of the discharged gases in the areas surrounding the emission sites. The gas vents are hosted within sub-circular morphological depressions (??～?10–30 m), which likely originated by the collapse of cavities formed at shallow depth in the ground by dissolution of Triassic anhydrite formations and recent travertine deposits. CaCO₃ and CaSO₄ dissolution is mainly related to the underground circulation of CO₂-rich fluids whose hydrological pattern is regulated by local and regional tectonics. The CO₂-rich (up to 996,070 μmol/mol) gases tend to accumulate within the topographic lows, thus creating a sort of CO₂ ponds, and the knowledge of their evolution in time and space is important to evaluate the related hazard. Consequently, a conceptual model of CO₂ diffusion in air is developed to understand the dynamic of the CO₂ accumulation/dispersion process based on (1) a 24-h continuous measurement of the CO₂ flux from one of the main emission sites and (2) the recording of the main meteoric parameters, i.e. air temperature, wind direction and speed to check their influence. The results indicate that the threshold of CO₂ concentrations considered dangerous for the human health is frequently overcome. Moreover, when meteoric conditions, i.e. low wind and cloudy weather, did not allow a rapid dispersion of the gas phase emitted from the dry vents, CO₂-rich clouds periodically overflowed the morphological depressions for several tens of meters without any significant mixing with air. On the basis of these considerations, the monitoring of the output rate from the main gas emissions, combined with the continuous control of the local meteorological parameters, may be considered an efficient procedure to mitigate the CO₂ hazard deriving from dry gas vents. An improvement of the protocol can be achieved in case of installations of CO₂ sensors located in the most sensitive areas and connected to a telemetry system able to transmit the data in real time to the closest Civil Defence centre. The CO₂ degassing sites can also represent a tourist attraction after the installation of suitable metallic fences and a proper campaign of information about these natural phenomena.     

Electrochemical Degradation of Chitosan Using Ti/Sb–SnO2 Electrode

The electrochemical degradation of chitosan using Ti/Sb–SnO₂ electrode was studied in this work. The experimental results showed that as a non-active electrode with high oxygen potential, Ti/Sb–SnO₂ electrode had a good efficiency for degrading chitosan. The kinetic behavior of electrochemical degradation of chitosan using Ti/Sb–SnO₂ electrode and the function relationship between experimental parameters and degradation rate constant were also investigated. The kinetic analysis revealed that this electrochemical process using Ti/Sb–SnO₂ electrode obeyed the zeroth–order reaction kinetics under the experimental conditions examined. The degradation rate constant at Ti/Sb–SnO₂ electrode had the linear relationship with 1.13 power of current density, ?1.36 power of initial concentration of chitosan and 0.19 power of concentration of acetic acid, The temperature dependences of the degradation rate constant could be expressed by the Arrhenius equation. The concentration of sodium acetate had a negligible influence on the degradation rate constant.