炼油废水体系中超滤膜表面污染物的剖析

分别采用扫描电子显微镜和能量色散谱仪对炼油废水体系中超滤膜表面污染物进行了形貌观测和元素组分含量分析,并研究了炼油废水中Fe、Si和Al含量对超滤膜表面形态和污染物组成的影响.实验结果表明:超滤膜表面的主要污染物为Ca,Fe,Si,Al,Mg的化合物形成的凝胶,元素含量大小顺序为Fe＞ Ca＞ Si＞ Mg＞ Al;随...     

The disposal of radioactive ferric floc

An iron hydroxide floc is used as treatment for adsorbing low amounts of actinides during nuclear fuel re-processing. This waste is cemented only after pre-treatment with Ca(OH)(2). Characterisation of all simulant material has been undertaken using XRD, TGA and SEM/EDS. The floc is a moderately alkaline colloidal slurry containing approximately 15wt% solids, with the main particulate being an amorphous hydrated iron oxide. The main phase formed during pre-treatment appears to be an X-ray amorphous hydrated calcium-ferrate phase. Embedded within this are small amounts of crystalline Ca(OH)(2), calcite, Fe(6)(OH)(12)(CO(3)), Ca(6)Fe(2)(SO(4))(3)(OH)(12).26H(2)O and Ca(3)B(2)O(6), and can form depending on concentrations of Ca(OH)(2) and time. Apart from Ca(OH)(2) and calcite, none of the crystalline phases detected during pre-treatment are detected when the floc is encapsulated in an OPC/PFA composite cement hydrated for 90 days. The main crystalline phase detected in the hardened wasteform is a solid solution hydrogarnet, Ca(3)AlFe(SiO(4))(OH)(8), known as C(3)(A,F)SH(4) in cement chemistry nomenclature.     

Catalytic degradation of PP with an Fe/activated carbon catalyst

We investigated the function of Fe and activated carbon (AC) as a catalyst by comparing Fe/AC with Fe/SiO₂ or AC, and also the effect of H₂ as a reaction gas on the product distribution in the catalytic degradation of polypropylene. Supported Fe promotes H₂ consumption to decompose solid residues, and AC support degrades heavy oil to produce light oil. As a result, using Fe/AC as a catalyst gives the maximum yield of the liquid product. For the reaction conditions, with a high reaction temperature or a long reaction time, the product distribution is more influenced by the thermal degradation than by the catalytic degradation. For the amount of Fe to load, 5wt% is the optimum condition in our reaction system. We demonstrated the mechanism of the degradation of polyolefins with hydrogen-capping catalysts.     

Ceramic processing of incinerator bottom ash

The <8 mm fraction of aged incinerator bottom ash from a commercial incinerator (energy from waste) plant has been collected at regular intervals, characterised and processed to form ceramic materials. Ashes were sieved, wet ball milled, dried, compacted and sintered at temperatures between 1080 and 1115 degrees C. Variations in the chemical composition and mineralogy of the milled ash, and the mineralogy, physical properties and leaching of sintered products have been assessed. Milling produces a raw material with consistent chemical and mineralogical composition with quartz (SiO(2)), calcite (CaCO(3)), gehlenite (Ca(2)Al(AlSi)O(7)) and hematite (Fe(2)O(3)) being the major crystalline phases present. Different batches also milled to give consistent particle size distributions. Sintering milled incinerator bottom ash at 1110 degrees C produced ceramics with densities between 2.43 and 2.64 g/cm(-3) and major crystalline phases of wollastonite (CaSiO(3)) and diopside (CaMgSi(2)O(6)). The sintered ceramics had reduced acid neutralisation capacity compared to the as-received ash and exhibited reduced leaching of Ca, Mg, Na and K under all pH conditions. The leaching of heavy metals was also significantly reduced due to encapsulation and incorporation into glassy and crystalline phases, with Cu and Al showing greatly reduced leaching under alkali conditions.     

Chemical changes in different types of coal ash during prolonged,large scale,contact with seawater

In this study, we followed the chemical changes occurring in coal ash exposed to prolonged (300 days), large scale, contact with running seawater. Four major components (Al, Ca, Mg, Fe) and seven minor and trace elements (Cd, Cr, Cu, Mn, Zn, Pb, Hg) were measured in four coal ash types: fly and bottom ash freshly obtained from coal-fired power plant, and old ash (crushed and blocks) recovered from the sea after 3-5 years contact with seawater. Changes occurred in the chemical composition of the coal ash along the experiment: Fe increased in fresh ash, Al increased in old ash and Ca increased in all ash types except old ash blocks. Cu and Hg decreased in fresh fly ash while Cr increased, Cd decreased in all ash types except bottom ash, and Mn decreased in bottom ash. Most of the changes occurred in the fresh fly ash, and not in the old ash, indicating equilibrium after prior exposure to seawater. In addition, more changes occurred in fresh fly ash than in bottom ash, emphasizing the differences between the two ash types. While the changes in the concentrations of the major elements may be an indication of the integrity of the ash matrix, the only elements of environmental significance released to the environment were Hg and Cd. However, calculated seawater concentrations were much lower than seawater quality criteria and therefore the coal ash was considered suitable for marine applications concerning seawater quality.     

Cement-clay pastes for stabilization/solidification of 2-chloroaniline

Immobilization of a model liquid organic pollutant, i.e. the 2-chloroaniline (2-CA), into a cement matrix using organoclays as pre-sorbent agents was investigated. Five cement-clay pastes were prepared with different nominal water-to-cement ratios (w/c=0.40, 0.25 and 0.15 wt/wt) and various amounts of waste (waste-to-cement o/c=0.20, 0.60 and 1.00 wt/wt); for comparison, a neat cement paste was also prepared. Dynamic leach tests were performed on solidified monoliths in order to assess the successful immobilization of the 2-CA. In monoliths at constant w/c ratio (0.40) the total amount of pollutant released increases with its initial content, and ranges from 15 to 35% with respect to it. By lowering w/c from 0.40 to 0.15 at constant o/c, the performances improved (<25% released). The microstructure of the hardened cement-clay pastes was characterized by quantitative X-ray diffraction (QXRD) and electronic microscopy (SEM-EDS) techniques; hydration degree was estimated by means of thermogravimetric analysis (TGA) in addition to QXRD. No evidence of any chemical reaction between 2-CA and cement phases was found. Moreover, it was shown that the most important factors affecting the cement hydration process were the total water content, i.e. the one taking also into account the water contained in the wet polluted clay, and the amount of 2-CA not firmly sorbed by the organoclay, and then freely dispersed in the paste.     

Photochemical oxidation of p-chlorophenol by UV/H2O2 and photo-Fenton process. A comparative study

In this study, photochemical advanced oxidation processes (AOPs) utilizing the combinations of UV/H2O2 and the photo-Fenton reaction (UV + classical Fenton reaction) were investigated in lab-scale experiments for the degradation of p-chlorophenol. The study showed that the photo-Fenton process, (a mixture of hydrogen peroxide and ferrous or ferric ion), was the most effective treatment process under acidic conditions and produced a higher rate of degradation of p-chlorophenol at a very short radiation time. It accelerated the oxidation rate by 5-9 times the rate for the UV/H2O2 process. The reaction was found to follow the first order, the reaction was influenced by the pH, the input concentration of H2O2 and the amount of the iron catalyst and the type of iron salt. The experimental results showed that the optimum conditions were obtained at a pH value of 3, with 0.03 mol/l H2O2, and 1 mmol/l Fe(II) for the UV/H2O2/Fe(II) system and 0.01 mol/l H2O2 and, 0.4 mmol/l Fe(III) for the UV/H2O2/Fe(III) system. The reactions were accompanied by the generation of Cl- which reached its maximum value at a short reaction time when using the photo-Fenton process. Finally a rough comparison of the specific energy consumption shows that photo-Fenton process reduced the energy consumption by at least 73 to 83% compared with the UV/H2O2 process.     

Influences of chemical activators on incinerator bottom ash

This research has applied different chemical activators to mechanically and thermally treated fine fraction (<14 mm) of incinerator bottom ash (IBA), in order to investigate the influences of chemical activators on this new pozzolanic material. IBA has been milled and thermally treated at 800 degrees C (TIBA). The TIBA produced was blended with Ca(OH)(2) and evaluated for setting time, reactivity and compressive strength after the addition of 0.0565 mole of Na(2)SO(4), K(2)SO(4), Na(2)CO(3), K(2)CO(3), NaOH, KOH and CaCl(2) into 100g of binder (TIBA+Ca(OH)(2)). The microstructures of activated IBA and hydrated samples have been characterized by X-ray diffraction (XRD) and thermogravimetry (TG) analysis. Thermal treatment is found to produce gehlenite (Ca(2)Al(2)SiO(7)), wollastonite (CaSiO(3)) and mayenite (Ca(12)Al(14)O(33)) phases. The thermally treated IBA samples are significantly more reactive than the milled IBA. The addition of Na(2)CO(3) can increase the compressive strength and calcium hydroxide consumption at 28-day curing ages. However, the addition of Na(2)SO(4), K(2)SO(4), K(2)CO(3), NaOH and KOH reduces the strength and hydration reaction. Moreover, these chemicals produce more porous samples due to increased generation of hydrogen gas. The addition of CaCl(2) has a negative effect on the hydration of TIBA samples. Calcium aluminium oxide carbonate sulphide hydrate (Ca(4)Al(2)O(6)(CO(3))(0.67)(SO(3))(0.33)(H(2)O)(11)) is the main hydration product in the samples with activated IBA, except for the sample containing CaCl(2).     

Biodegradability of degradable plastic waste.

Plastic waste constitutes the third largest waste volume in Malaysian municipal solid waste (MSW), next to putrescible waste and paper. The plastic component in MSW from Kuala Lumpur averages 24% (by weight), whereas the national mean is about 15%. The 144 waste dumps in the country receive about 95% of the MSW, including plastic waste. The useful life of the landfills is fast diminishing as the plastic waste stays un-degraded for more than 50 years. In this study the compostability of polyethylene and pro-oxidant additive-based environmentally degradable plastics (EDP) was investigated. Linear low-density polyethylene (LLDPE) samples exposed hydrolytically or oxidatively at 60 degrees C showed that the abiotic degradation path was oxidative rather than hydrolytic. There was a weight loss of 8% and the plastic has been oxidized as shown by the additional carbonyl group exhibited in the Fourier transform infra red (FTIR) Spectrum. Oxidation rate seemed to be influenced by the amount of pro-oxidant additive, the chemical structure and morphology of the plastic samples, and the surface area. Composting studies during a 45-day experiment showed that the percentage elongation (reduction) was 20% for McD samples [high-density polyethylene, (HDPE) with 3% additive] and LL samples (LLDPE with 7% additive) and 18% reduction for totally degradable plastic (TDP) samples (HDPE with 3% additive). Lastly, microbial experiments using Pseudomonas aeroginosa on carbon-free media with degradable plastic samples as the sole carbon source, showed confirmatory results. A positive bacterial growth and a weight loss of 2.2% for degraded polyethylene samples were evident to show that the degradable plastic is biodegradable.     

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.     

Biodegradability of blends of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) with cellulose acetate esters in activated sludge

Blends of the bacterially produced polyester poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) with cellulose acetate esters (CAE) further substituted with propionyl or butyryl groups (degree of substitution: 2.60 propionyl and 0.36 acetyl or 2.59 butyryl and 0.36 acetyl, respectively) were exposed for 4 months to activated sludge to determine their biodegradability. Samples of such blends made by solution-mixing and solvent-casting had complex morphologies in which both individual components as well as a miscible blend phase were present. Additionally, the two opposite surfaces of solvent-cast films showed both physical and chemical differences. After 2 months, samples of pure PHBV had degraded by more than 98% (15 mg/cm² of surface area), whereas a pure CAE sample had degraded less than 1% (<0.2 mg/cm²). Samples containing 25% CAE lost less than 40% of their initial weights (6 mg/cm²) over the total 4-month period. Samples with 50% CAE lost up to 16% weight (2 mg/cm²), whereas those containing 75% CAE lost only slightly more weight than corresponding sterile control samples (1 mg/cm²). NMR results confirm that weight loss from samples containing 25% CAE resulted only from degradation of PHBV and that the surface of samples became enriched in CAE. Solvent-cast film samples containing equal amounts of PHBV and CAE degraded preferentially on the surface which formed at the polymer-air interface. Scanning electron microscopy and attenuated total reflectance infrared spectroscopy revealed this surface to have a rougher texture and a greater PHBV content.     

用Fe3+掺杂锐钛矿型TiO2光催化剂降解孔雀石绿

以硫酸钛为原料,用水热法制备了Fe3+掺杂锐钛矿型TiO2(Fe3+ - TiO2)粉末,用扫描电子显微镜测定了试样的形貌.研究了自制的Fe3+ - TiO,光催化剂对孔雀石绿的光催化降解作用.实验结果表明,在孔雀石绿溶液质量浓度为2 mg/L、Fe3+ - TiO2加入量为1.616 g/L、Fe3+-TiO2中Fe...     

Recycling of combined coal-biomass ash from electric power plant waste as a cementitious material: characteristics and improvement

Combined coal-biomass ash has an enormous impact on environmental quality near electric power plants. This paper describes an alternative to disposal in which the ash is used to produce cementitious materials. Ash was obtained from combustion of coal and biomass containing four mass ratios of anthracite, bitumen, rice husks, and eucalyptus bark. The cement-forming properties were systematically characterized including compressive strength development, durability, and expansion in water. The ash samples were ground to increase the specific surface area, and then used to partially replace ASTM Type I Portland cement in mixtures containing 15, 30, or 45 % ash by mass. The water-binder material's (Portland cement with or without combined coal-biomass ash) ratios (w/c) were held constant at 45, 55, or 65 % by mass. Types A, B, and D ash behaved similarly, while the properties of type C ash were slightly different. Increasing the ash fraction in Portland cement mixtures increased the water requirement and resulted in lower compressive strength. Thorough mechanical grinding reduced the porosity and significantly enhanced the material properties.     

Contribution to closing the loop on waste materials: valorization of bottom ash from waste-to-energy plants under a life cycle approach

Incineration has undergone several technology improvements, reducing air emissions and increasing the efficiency of energy and material recovery; however, there is still a long way to go. To analyze the environmental impacts of waste incineration, this study assessed 15 waste fractions that compose municipal waste in Spain, which are grouped as non-inert materials (plastics, paper, cardboard and organic matter), unburned materials (glass and Al) and ferrous materials. Additionally, this paper evaluates the valorization of bottom ash (BA) to produce steel, aluminum and cement in these recycled/recoverable waste fractions. The results depend on the input waste composition and the heating value (HHV) and showed that ferrous and unburned materials had the worst environmental performance due to the null HHV. The valorization of BA in steel, Al and cement production significantly reduced the environmental impact and the consumption of resources. BA recycling for secondary steel and Al production would improve the environmental performance of the combustion of unburned materials and ferrous materials, whereas the use of BA in cement production diminished the consumption of NR for non-inert materials. This is of great interest for organic matter and PC, waste with a low energy production and high heavy metal and sulfur content.     

The fixation and leaching of cement stabilized arsenic

The solidification/stabilization of sodium arsenite, sodium arsenate, arsenic trioxide and arsenic pentoxide at dosages of approximately 10% has been investigated using sequential batch leaching tests. The leaching of arsenic, which was found to be diffusion based, was clearly least effective for those formulations containing additional iron(II). Calcium was found to influence the leaching of cement immobilized arsenic: those formulations containing the greatest Ca:As mole ratios were generally the most successful. Analysis using both FTIR and SEM revealed substantial changes to the cement matrices of those formulations to which the ferrous sulfate had been added. Ettringite was identified in the cement+ferrous sulfate formulations.     

Biodegradation of Injection Molded Starch-Poly (3-hydroxybutyrate-co-3-hydroxyvalerate) Blends in a Natural Compost Environment

Injection molded specimens were prepared by blending poly (hydroxybutyrate-co-valerate) (PHBV) with cornstarch. Blended formulations incorporated 30% or 50% starch in the presence or absence of poly-(ethylene oxide) (PEO), which enhances the adherence of starch granules to PHBV. These formulations were evaluated for their biodegradability in natural compost by measuring changes in physical and chemical properties over a period of 125 days. The degradation of plastic material, as evidenced by weight loss and deterioration in tensile properties, correlated with the amount of starch present in the blends (neat PHBV < 30% starch < 50% starch). Incorporation of PEO into starch-PHBV blends had little or no effect on the rate of weight loss. Starch in blends degraded faster than PHBV and it accelerated PHBV degradation. Also, PHBV did not retard starch degradation. After 125 days of exposure to compost, neat PHBV lost 7% of its weight (0.056% weight loss/day), while the PHBV component of a 50% starch blend lost 41% of its weight (0.328% weight loss/day). PHB and PHV moieties within the copolymer degraded at similar rates, regardless of the presence of starch, as determined by ¹H-NMR spectroscopy. GPC analyses revealed that, while the number average molecular weight (Mn) of PHBV in all exposed samples decreased, there was no significant difference in this decrease between neat PHBV as opposed to PHBV blended with starch. SEM showed homogeneously distributed starch granules embedded in a PHBV matrix, typical of a filler material. Starch granules were rapidly depleted during exposure to compost, increasing the surface area of the PHBV matrix.     

Utilization of gold tailings as an additive in Portland cement.

Mine tailings are formed as an industrial waste during coal and ore mining and processing. In the investigated process, following the extraction of gold from the ore, the remaining tailings are subjected to a two-stage chemical treatment in order to destroy the free cyanide and to stabilize and coagulate heavy metals prior to discharge into the tailings pond. The aim of this study was the investigation of the feasibility of utilization of the tailings as an additive material in Portland cement production. For this purpose, the effects of the tailings on the compressive strength properties of the ordinary Portland cement were investigated. Chemical and physical properties, mineralogical composition, particle size distribution and microstructure of the tailings were determined by Fourier transform infrared spectroscopy (FTIR), X-ray diffractometry (XRD), particle size analyzer (Mastersizer) and scanning electron microscope (SEM). Following the characterization of the tailings, cement mortars were prepared by intergrinding Portland cement with dried tailings. Composition of the cement clinkers were adjusted to contain 5, 15, 25% (wt/wt) dried tailings and also silica fume and fly ash samples (C and F type) were added to clinker in different ratios. The mortars produced with different amounts of tailings, silica fume, fly ashes and also mixtures of them were tested for compressive strength values after 2, 7, 28 and 56 days according to the European Standard (EN 196-1). The results indicated that gold tailings up to 25% in clinker could be beneficially used as an additive in Portland cement production. It is suggested that the gold tailings used in the cement are blended with silica fume and C-type fly ash to obtain higher compressive strength values.     

Molecular Weight Changes and Polymeric Matrix Changes Correlated with the Formation of Degradation Products in Biodegraded Polyethylene

The molecular weight changes in abiotically and biotically degraded LDPE and LDPE modified with starch and/or prooxidant were compared with the formation of degradation products. The samples were thermooxidized for 6 days at 100°C to initiate degradation and then either inoculated with Arthobacter paraffineus or kept sterile. After 3.5 years homologous series of mono- and dicarboxylic acids and ketoacids were identified by GC-MS in abiotic samples, while complete disappearance of these acids was observed in biotic environments. The molecular weights of the biotically aged samples were slightly higher than the molecular weights of the corresponding abiotically aged samples, which is exemplified by the increase in from 5200 g/mol for a sterile sample with the highest amount of prooxidant to 6000 g/mol for the corresponding biodegraded sample. The higher molecular weight in the biotic environment is explained by the assimilation of carboxylic acids and low molecular weight polyethylene chains by microorganisms. Assimilation of the low molecular weight products is further confirmed by the absence of carboxylic acids in the biotic samples. Fewer carbonyls and more double bonds were seen by FTIR in the biodegraded samples, which is in agreement with the biodegradation mechanism of polyethylene.     

Kinetics of biochemically driven metal precipitation in synthetic landfill leachate

This study investigates the effectiveness of using metal sulphide and carbonate precipitation mechanisms combined with a landfill‐derived mixed bacterial population. The study was conducted under controlled substrate conditions in anaerobic batch reactors. High chemical oxygen demand (COD):sulphate ratios, butyrate, propionate, and acetate were used anaerobically by bacteria for growth with associated sulphate reduction as well as sulphide and carbonate generation. Propionate and butyrate degradation occurred during sulphate reduction by sulphate‐reducing bacteria while acetate degradation was associated with methanogenesis by methanogenic bacteria. Using low COD, sulphate ratios showed limited acetate utilization, but sulphate reduction still occurred. Precipitation of Cd, Cu, Zn, Ni, and Fe sulphides occurred quickly and was completed in 15 to 30 days, while Ca, Mn, and Mg carbonates formed after 40 to 50 days and some soluble metal remained even after 120 days. The rate of metal precipitation was in the order of Cd>Cu>Zn>Ni>Fe>Mn>Mg>Ca. Bacterially mediated metal precipitation occurred slower than that recognized for chemical precipitation. These findings suggest that contaminant transport models based on chemical equilibrium metal behaviors may over‐predict metal removal by bio‐precipitation. © 2002 Wiley Periodicals, Inc.     

加压酸浸法提取粉煤灰中的Al2O3和Fe2O3

采用加压酸浸法提取粉煤灰中的A12O3和Fe2O3.实验研究了粉煤灰粒径、硫酸质量分数、反应时间、反应温度对粉煤灰中Al2O3和Fe2O3浸取率的影响,并通过SEM对粉煤灰酸浸前后的形貌进行了分析.实验结果表明,当粉煤灰粒径为75μm、硫酸质量分数为50％、反应温度为180℃、反应时间为4h时,粉煤灰中的Al2O3浸取率可达82.4％,Fe2O3浸取率为76.1％,经酸浸后粉煤灰的剩余率为72.4％.