Conversion of rice husk ash to zeolite beta

White rice husk ash (RHA), an agriculture waste containing crystalline tridymite and alpha-cristobalite, was used as a silica source for zeolite Beta synthesis. The crystallization of zeolite Beta from RHA at 150 degrees C in the presence of tetraethylammonium hydroxide was monitored by XRD, FTIR and (29)Si MAS NMR techniques. It was found that zeolite Beta started to form after 12h and the complete crystallization of zeolite Beta phase was achieved after 2d. XRD, (29)Si MAS NMR and solid yield studies indicate that the transformation mechanism of silica present in RHA to zeolite Beta involves dissolution of the ash, formation of an amorphous aluminosilicate after 6h of crystallization, followed by dissolution in the mother liquor and final transformation to pure zeolite Beta crystals.     

从含铬铝泥中回收铝的新工艺

采用"打浆水洗除Cr(Ⅵ)—电渗析除Cr(Ⅵ)—碱浸提铝—碳酸化分解法精制Al_2O_3"的新工艺处理含铬铝泥(以下简称铝泥),并回收Al_2O_3。实验结果表明:铝泥在70℃下经3次打浆水洗后,w(Na_2CrO_4)(以干铝泥计)降至5.0%;采用电渗析除Cr(Ⅵ)工艺可有效去除铝泥中以结合态和结晶态形式存在的Na_2CrO_4,在55 V直流电压下电渗析6h后铝泥中的w(Na_2CrO_4)降至0.98%;在碱浸温度为100℃、碱浸时间为3 h、NaOH质量浓度为150 g/L的优化碱浸条件下,铝浸出率(以Al_2O_3计)高达90.0%;经3次碳酸化分解处理后,Al_2O_3产品的纯度达98.65%,满足GB/T 24487-2009《氧化铝》中的一级标准,Al_2O_3回收率为96.37%。     

Abiotic hydrogen production in fresh and altered MSWI-residues: Texture and microstructure investigation

Long-term hydrogen generation was observed in a Bavarian mono-landfill for municipal solid waste incineration (MSWI) residues. Hydration reactions of non-noble metals, especially aluminum, predominantly produce hydrogen at alkaline reaction conditions. Microscopic investigations show that aluminum metal may occur in different forms: as larger single grains, as small particles embedded in a vitrified matrix or less frequently in blowholes together with metallic silica.Four types of corrosion texture were observed, indicating different reaction mechanisms: aluminum hydroxide rims caused by hydration reactions at alkaline reaction conditions (reaction type 1) and multiphase rims with ettringite and hydrocalumite due to the reaction of aluminum hydroxide with sulfate and chloride ions which are solved in the pore water (reaction type 2). Galvanic corrosion textures due to the electric potential difference between aluminum and embedded intermetallic Fe- or Cu-rich exsolution phases lead to two further corrosion textures: Strong hydration effects of aluminum except a border of aluminum remnant directly beside the Fe- or Cu-rich segregations were only observed in fresh samples (reaction type 3). The reaction type 4 shows a network of Al-hydroxide veins occurring along the embedded intermetallic Fe- or Cu-rich exsolution segregation pattern within the metallic aluminum grain. Metal particles enclosed in vitrified particles offers the potential for future corrosion processes.The occurrence of corrosion types 1, 2 and 3 in fresh bottom ashes indicates that these reaction mechanisms predominate during the first reaction period in the presence of chlorine in an alkaline solution. Corrosion type 4, however, was additionally observed in aged samples. Here aluminum acts as sacrificed anode implying electrochemical reaction due to electrolytic pore water. Chloride in the system keeps the reaction alive as Al-hydroxide is solved which normally builds a protection shield around the aluminum metal particles.Due to field observations and experimental results we have reasonable indications that after an initial strong formation of hydrogen the reaction time for hydrogen production in the landfill is lengthened for several decades by the presence of chloride in the alkaline pore water.     

赤泥制备含钛聚硅酸铝铁及亚甲基蓝溶液的混凝脱色

以拜耳法赤泥为原料、Na Cl为助溶剂,采用酸浸法溶出赤泥中的铁、铝元素,再与硅酸钠、硫酸氧钛反应制备出高效混凝剂含钛聚硅酸铝铁(T-PSAF),并将其用于模拟亚甲基蓝印染废水的脱色。实验结果表明:在硫酸浓度为8 mol/L、液固比(硫酸体积与干赤泥质量之比)为14 m L/g、酸浸温度为80℃、酸浸时间为80 min、Na Cl加入量为0.10 g/g(以干赤泥计)的优化酸浸条件下,铁、铝的浸出率分别为88.25%和73.21%;在n(Fe+Al)∶n(Ti)∶n(Si)=0.3∶0.3∶1、熟化p H为4~5、熟化时间为2 h、混凝剂加入量为25 m L/L的优化混凝条件下,初始亚甲基蓝质量浓度为10 mg/L的废水的脱色率可达87.1%,而当初始亚甲基蓝质量浓度增至150~200 mg/L时废水脱色率可达99%以上。     

高炉渣制备聚硅酸硫酸铝铁混凝剂

以高炉渣为原料,分别采用酸浸及碱浸-酸化工艺得到铁、铝离子及聚硅酸,再将铁、铝离子引入聚硅酸制得聚硅酸硫酸铝铁(PSAFS)混凝剂。考察了PSAFS的聚合条件对焦化废水混凝效果的影响,并与市售混凝剂进行了对比。实验结果表明:PSAFS的最佳制备条件为n(Al+Fe)∶n(Si)=0.53,混凝剂p H=1,熟化时间0.5 h,熟化温度60℃;PSAFS加入量为4 m L/L时,混凝效果最好,对焦化废水的浊度和COD的去除率分别达到98.9%和74.5%;PSAFS的性能优于市售的3种混凝剂。     

Microbial influenced degradation of solidified waste binder

Ordinary cement pastes with water/cement (w/c) ratios of 0.2, 0.4 and 0.5 were used to examine the chemical and physical effects of microbial influenced degradation (MID). Samples were exposed to an active culture of Thiobacillus thiooxidans or to sterile media containing sulphuric acid using an intermittent immersion technique. Acid consumption and Ca, Al and Fe releases are presented for an exposure period of 90 days. Exposed samples were also sectioned and analysed by scanning electron microscopy (SEM) and energy dispersive X-ray (EDX). All cement paste samples were subject to significant degradation in either sterile acid media or the T. thiooxidans lixiviant. Corrosion depths observed from SEM examination of exposed samples were affected by the w/c ratio of the cement. The extent and rate of degradation were not apparent from the calculated rate of hydrogen ion consumption, or the leaching rates of Ca, Al and Fe. It was not possible to distinguish differences in corrosion due to the chemical and microbial influenced degradation from the results obtained to date and further work is focusing on modified procedures to address this.     

Evaluation of chemical stability of heavy metals in industrial waste slag by infrared spectroscopy

Our aim was to clarify the chemical bonding type and stability of heavy metals in industrial waste slag (IWS) by using Fourier transform infrared (FT-IR) spectroscopy. The chemical composition of the IWS sample used in this study was an Al/Si ratio of 0.50 with Fe, Pb, and other minor heavy metals present. The IR peak position of the Si-OSi( M) band (M: Al, Pb, or Fe) was lower for IWS (971 cm⁻¹) than for synthetic Si-Al glass with an Al/Si ratio of 0.5 (1029 cm⁻¹). This implies the formation of covalent Si-O-Pb and Si-O-Fe bonds in the IWS, which caused a shift in the peak position toward a lower wavenumber. FT-IR spectra of synthetic Si-Al-Pb and Si-Al-Fe glasses with various Pb/Si and Fe/Si ratios with a constant Al/Si ratio of 0.5 showed that the peak position of the Si-O-Si(M) band continuously shifted toward lower wavenumbers with increasing Pb/Si and Fe/Si ratios. This suggests that covalent Si-O-Pb and Si-O-Fe bonds are formed in IWS. The comparison of peak positions of the Si-O-Si(M) band between IWS and Si-Al-Fe glass indicated that not only Pb but also other minor heavy metals such as Cu and Cr were included by covalent bonds into the structure of IWS. Therefore, we concluded that most of the heavy metals in IWS formed covalent Si-O-M bodings and were chemically stable.     

Biodegradable Polyester-Based Blend Reinforced with Curauá Fiber: Thermal,Mechanical and Biodegradation Behaviour

Biodegradable composites can be produced by the combination of biodegradable polymers (BP) as matrix and vegetal fibers as reinforcement. Composites of a commercial biodegradable polymer blend and curauá fibers (loaded at 5, 15 and 20 wt%) were prepared by melt mixing in a twin-screw extruder. Chemical treatments such as alkali treatment of the fiber and addition of maleic anhydride grafted polypropylene (MA-g-PP) as coupling agent were performed to promote polymer/fiber interfacial adhesion so that mechanical performance can be improved. The resulting composites were evaluated through hardness, melt flow index and tensile, flexural and impact strengths as well as water absorption. Thermal analysis and Fourier transform infrared spectroscopy were also employed to characterize the composites. The polymer/fiber interface was investigated through scanning electron microscopy analysis. The biodegradability of composites was evaluated by compost-soil burial test. The addition of curauá fiber promoted an increase in the mechanical strengths and composites treated with 2 wt% MA-g-PP with 20 wt% curauá fiber showed an increase of nearly 75% in tensile and 56% in flexural strengths besides an improvement in impact strength with respect to neat polymer blend. Nevertheless, treated composites showed an increase in water absorption and biodegradation tests showed that the addition of fiber retards degradation time. The retained mass of BP/20 wt% fiber composite with MA-g-PP and neat BP was 68 and 26%, respectively, after 210 days of degradation test.     

PSAF-DMDAAC复合絮凝剂的制备及含铊废水的处理

将自制聚硅酸铝铁（PSAF）与二甲基二烯丙基氯化铵（DMDAAC）复配,制备了复合高分子絮凝剂PSAF-DMDAAC,并将其用于含铊废水的处理。表征结果显示：PSAF与DMDAAC先利用氢键形成聚合体后脱水,然后DMDAAC链上的烯基双键与PSAF中的聚铁、聚铝基团发生桥联反应,以配位键形式将基团引入DMDAAC链,形成一种新型复合絮凝剂。实验结果表明：复合絮凝剂制备的最优条件为（Al+Fe）与Si的摩尔比2∶1、Al与Fe的摩尔比1∶2、60%（w）DMDAAC溶液加入量0.8%（w）;废水处理的最优条件为絮凝剂投加量0.8 g/L、废水pH 9.5、沉降时间10 min;在上述优化条件下,废水的色度、浊度、铊的去除率分别达到95.0%,96.4%,95.6%,处理后废水的色度、浊度、铊质量浓度分别为10度、6 NTU、13 μg/L。     

Leaching from MSWI bottom ash: evaluation of non-equilibrium in column percolation experiments

Impacts of non-equilibrium on results of percolation experiments on municipal solid waste incineration (MSWI) bottom ash were investigated. Three parallel column experiments were performed: two columns with undisturbed percolation and one column with two sets of 1-month-long flow interruptions applied at liquid-to-solid (L/S) ratios of L/S 2L/kg and 12L/kg, respectively. Concentrations of Na, K, Cl(-), Ca, Si, SO(4)(2-), Al, Cu, Ni, Mo, Ba, Pb, Zn, and dissolved organic carbon (DOC) were monitored throughout the entire leaching period; geochemical modeling was used to identify non-equilibrium-induced changes in the solubility control. Despite both physical and chemical non-equilibrium, the columns were found to provide adequate information for readily soluble compounds (i.e., Na, Cl(-), and K) and solubility-controlled elements (i.e., Ca, SO(4)(2-), Ba, Si, Al, Zn, and Pb). The leaching of Cu and Ni was shown to depend strongly on DOC leaching, which was likely affected by physical non-equilibrium during flow interruptions. Consequently, the leaching of Cu and Ni in the undisturbed columns was shown to be by about one order of magnitude lower compared with the interrupted column. The results indicate that the leaching of DOC-related metals in laboratory column experiments may be considerably underestimated compared with full-scale scenarios in which the impacts from non-equilibrium may be significantly lower. The leaching of Mo (or MoO(4)(2-)) may be controlled solely by its availability in the mobile zone, which in turn appeared to be controlled by diffusion from the stagnant zone; no Mo controlling minerals were predicted by the geochemical modeling.     

Solid waste from aluminum recycling process: characterization and reuse of its economically valuable constituents

Due to economic advantages, many companies in Brazil recover Al from the process of crushing and water-leaching of secondary aluminum dross. Wastes from this process (non-metallic products and salts) are usually landfilled or disposed without treatment, causing many environmental damages. The purpose of this work is to investigate, in a recycling company sited in Sao Paulo metropolitan area (Brazil), the potential use of the non-metallic product (NMP) in the production of concrete blocks and to evaluate the presence of important chemical compounds that may be useful for other applications. Chemical and mineralogical analyses revealed that NMP is composed of refractory and abrasive oxides (alpha-Al2O3, MgAl2O4, SiO2) and an important source of transition alumina: alpha-Al(OH)3. Concrete blocks were made by adding two parts of NMP to one part of cement and four parts of sand. The blocks were tested according to the Brazilian standard (NBR7173/1982) and they passed dimension, humidity and absorption tests but not compressive strength tests. However, particular NMP constituents have accelerated the strength rate development of the blocks, thus decreasing working time. The commercial use of NMP can reduce the amount of discarded wastes contributing to environmental preservation.     

新型铝硅复合絮凝剂的制备及其絮凝性能研究

以高稳定性的有机硅(TEOS)代替聚硅酸(HS)加入到聚合铝(PAC)中,初步制备了一种新型铝硅复合絮凝剂(TEOS—PAC)。研究了制备过程中的滴碱速度、Si与Al摩尔比和碱化度等因素对该复合絮凝剂絮凝性能的影响,对比了TEOS—PAC与HS—PAC的絮凝效果。研究结果表明,制备TEOS—PAC时滴碱速度要控制适当(流量刻度定位40);随着Si与A1摩尔比的提高,TEOS—PAC复合絮凝剂的絮凝性能明显增强,最佳Si与A1摩尔比为0．2,最佳碱化度为2．5;在相同条件下,TEOS—PAC的最佳投药量低于HS—PAC,且TEOS—PAC在絮凝过程中形成的絮体沉降性能优于HS—PAC形成的絮体。     

纳米Al_2O_3固定化红平红球菌菌球的制备及其对苯酚的降解

以海藻酸铝为主要包埋材料、纳米Al_2O_3为添加剂,包埋固定红平红球菌,制得纳米Al_2O_3固定化红平红球菌菌球,并将其用于苯酚的降解。表征结果显示:菌球内部包含丰富的菌丝体;内部孔径以中孔居多。实验结果表明:菌球的最优制备方案为0.05 g纳米Al_2O_3加入3 m L海藻酸钠溶液中、海藻酸钠质量分数6%、微生物包埋量0.5 m L/m L(以海藻酸钠溶液计)、Al_2(SO_4)_3质量分数3%;在初始苯酚质量浓度为400 mg/L、反应时间为24h、菌球加入量为8 g/L、反应p H为8.0、反应温度为30℃的条件下,菌球首次使用时可使苯酚完全降解,使用5次后的苯酚降解率仍达93%以上,具有良好的循环使用性。     

Photocatalytic Degradation of Poly(Vinyl Alcohol) on Pt/TiO<Subscript>2</Subscript> with Fenton Reagent

In this research Fenton reagent (Fe²⁺/H₂O₂) was investigated as oxidants to degrade poly (vinyl alcohol) (PVA). The role of nano-TiO₂ photocatalyst was discussed as an additive in Fenton reagent (Fe²⁺/H₂O₂). Pt/TiO₂ composites were also synthesized by photo-reaction to be used as additive in Fenton reagent. The rapid degradation of PVA was obtained when Pt/TiO₂ composites served as photocatalyst. The different photocatalytic efficiency of Pt/TiO₂- Fenton reagent (Fe²⁺/H₂O₂) was studied compared with TiO₂- Fenton reagent (Fe²⁺/H₂O₂) during the degradation of PVA.     

Aluminum in-use stocks in China: a bottom-up study

Characterization of the in-use stocks of a resource provides a perspective on the relationship between the amount of materials providing services and the state of development of a country or region. In this regard, we have performed what we believe to be the first aluminum in-use stock study for a developing country: China in 2000 and 2005. We found the in-use stocks to be 29 Tg Al (2000) and 49 Tg Al (2005), or 23 kg Al/capita (2000) and 37 kg Al/ capita (2005). These are lower limits because data were not available for all aluminum-containing products. The 2005 per-capita figure is roughly half that of the global average in-use aluminum stock, and about one-tenth that of highly developed countries such as Japan and the United States.     

Degradation Mechanism of CF/EP Composites in Supercritical <Emphasis Type="Italic">n</Emphasis>-Butanol with Alkali Additives

CF/EP (carbon fibre/epoxy resin) composites were degraded by supercritical n-butanol with alkali additive KOH in a batch reactor. The catalytic degradation mechanism of the composites was investigated based on the analysis of liquid phase products by GC–MS and solid phase products by FTIR. The results indicate that alkali additive (KOH) can promote Guerbet reaction and increase hydrogen donor capability of supercritical n-butanol. The H^· can combine promptly with the free radical formed by the scission of linear and crosslinked chains in epoxy resin to generate the liquid products, including phenol, 4-isopropylphenol, 4-(2-methylallyl)phenol and other derivatives of benzene and phenol. The combination of supercritical n-butanol with alkali additive is an effective way to degrade and recycle CF/EP composites.     

Recovery of metal values from zinc solder dross

Zinc solder dross containing 14.8% Sn, 16.3% Pb, 0.41% Al and 64.5% Zn was leached with 3% H₂SO₄ at 45°C for 1 h. Zinc and aluminum went into solution, whereas lead and tin remained with the residue. Aluminum was selectively precipitated as calcium aluminum carbonate by treating the sulphate leachate with limestone at pH 4.8. Zinc sulphate solution was either evaporated to obtain zinc sulphate crystals or precipitated as basic zinc carbonate at pH 6.8. The undissolved lead and tin were leached with 5 M hot hydrochloric acid. The major part of lead chloride ( 73%) was separated by cooling the leached products down to room temperature. From the soluble fraction, tin was recovered as hydrated tin oxide by alkylation with caustic soda at pH 2.4, while the remaining lead was separated at pH 8.5 as lead hydroxide. A process flowsheet had been suggested which involved two-stage hydrometallurgical treatment. Parameters affecting the recovery efficiency of the suggested method such as temperature, time, pH and acid: solid stoichiometric ratio were investigated. Results obtained revealed that the optimum leaching conditions were achieved by using 20 ml of 3% H₂SO₄ acid/g dross for 1 h at 45°C. Recovery efficiency of the metal salts was 99.1, 99.4, 99.6 and 99.5% for Zn, Al, Pb and Sn respectively. Recovery efficiency was related to the solubility of the concerned salts under the given experimental conditions.     

Conversion of LDPE into transportation fuels by a two-stage process using Ni/Al-SBA-15 as catalyst

Ni/Al-SBA-15 catalysts with Si/Al atomic ratios within the 20–135 range were prepared by a post synthesis grafting procedure, having nickel contents between 6 and 11 %. The addition of Ni to the Al-SBA-15 support caused a decrease of the BET surface area and pore volume. Additionally, larger Ni particles were attained over the catalysts with higher Si/Al atomic ratios, indicating the existence of some interaction between aluminium species and nickel particles. Ni/Al-SBA-15 catalysts displayed remarkable properties for the preparation of diesel fuels in the hydroreforming of the oils obtained from the LDPE thermal cracking. On increasing the Si/Al atomic ratios of the Ni/Al-SBA-15 catalysts, higher share of light and heavy diesel were attained, the sum reaching a maximum (67.3 %) for Ni/Al-SBA-15(70). This was caused by the higher extent of oligomerization reactions on enhancing the Si/Al atomic ratio. Additionally, around 85–90 % of the starting olefins were successfully hydrogenated and the aromatic content was rather low (below 5 %), without almost any polyaromatic compound (<0.1 %).     

Degradation Kinetics of Biodegradable Fiber Composites

In a composite, fast degradable fibers determine the degradation of the slowly degradable matrix. Such biodegradable composites consisting of degummed hemp fibers and a polyester amide matrix were produced with fiber mass fractions between 0 and 0.48. The hot-pressed plates, 1-mm thick, were incubated in a standard soil. The degradation kinetics was quantified by the measurement of CO₂ production. Furthermore, after termination of experiment, the carbon balance was uncovered. The results were fitted to an exponential law taking into account the degradation of fibers. The increased amount of pores realized by high fiber contents induces pronounced degradation. The degradation is fully characterized by the time constant , which is correlated to the fiber mass fraction. The model allows to predict the degradation kinetics of composites with a few well-defined experiments.     

拜耳法赤泥制备三聚磷酸铝

拜耳法赤泥经石灰石烧结改性、盐酸浸取及碱液处理等工序得到氢氧化铝干胶,再以氢氧化铝干胶和工业磷酸为原料,通过中和反应、缩合反应和水化反应合成三聚磷酸铝.经单因素条件实验和正交实验得到最佳工艺条件为:磷酸体积(mL)与氢氧化铝干胶质量(g)的比3,中和反应温度常温,缩合反应温度290℃,缩合反应时间4h.在最佳工艺条件下合成的试样中,Al2O3和P2O5的含量与工业三聚磷酸铝ATP-200相近,经IR分析,该试样即为三聚磷酸铝.盐雾试验结果表明合成的三聚磷酸铝的防腐性能达到ATP-200的性能指标.