以粉煤灰为原料制备高纯度NaP型分子筛

以工业固体废弃物粉煤灰为原料,经分级处理后提取其中的硅铝元素(Na_2SiO_3和NaAlO_2),通过水热合成法制备高纯度NaP型分子筛。考察了硅铝比、水硅比、晶化时间和晶化温度对NaP型分子筛制备的影响,采用XRD、SEM、FTIR和DTA-TG对NaP型分子筛的晶型、形貌、热稳定性进行分析表征,并考察了NaP分子筛对Cu~(2+)的吸附性能。实验结果表明,当H_2O/Si为120、Si/Al为1.0,晶化温度为115℃、晶化时间9h时,可得到高纯度NaP型分子筛。合成的NaP型分子筛可有效地吸附Cu~(2+),温度升高有助于分子筛吸附能力的提升,当吸附温度为45℃,吸附120min时,Cu~(2+)的最大去除率可达98.3%。     

晶种及晶型助长剂对磷石膏制备硫酸钙晶须的影响

实验以磷石膏为原料,硫酸钙为晶种,镁盐为晶型助长剂,采用水热法制备硫酸钙晶须。实验详细考察了晶种的用量,镁盐晶型助长剂种类及用量,晶种、晶型助长剂、结晶稳定剂三者的协同效应等对硫酸钙晶须形态的影响。用偏光显微镜和扫描电镜(SEM)及X射线衍射分析了硫酸钙晶须的形貌和相组成。结果表明在硫酸镁作为晶型助长剂,晶种∶晶型助长剂∶结晶稳定剂的用量为1∶3∶4时制备出的硫酸钙晶须产品优,其光滑,反应完全,长度最长可达150μm左右,直径细度可细达0.5μm。     

掺Ni2+的TiO2颗粒光催化性能的研究

通过溶胶-凝胶法制备掺杂Ni2 的纳米TiO2,并用XRD和TEM进行了表征,发现Ni2 的掺杂减小了TiO2颗粒的粒径,Ni2 /TiO2晶型为锐钛型.通过对目标物罗丹明B的光催化降解实验,发现Ni2 的掺杂提高了TiO2的光催化活性,其降解罗丹明B的反应遵从一级反应动力学方程,Ni2 惨杂量为1.2%时的光催化活性最高.     

钯/铝双金属体系对3-氯酚的脱氯降解

研究了钯/铝双金属体系对水相中3-氯酚的催化脱氯降解效果,通过置换沉积制备了钯/铝双金属颗粒,考察了该双金属颗粒的稳定性以及溶液pH和钯负载量对脱氯效果的影响。结果表明,pH在4.0以下的酸性条件,钯负载量在1.43%时,可实现水相中3-氯酚的有效脱氯,反应30 min后0.389 mmol/L的3-氯酚转化率可达99%以上,产物主要为苯酚,而钯/铝颗粒在重复测试中能保持较好的稳定性,这与铝基材表面自发形成的氧化膜有关。钯/铝材料表征的结果表明,钯颗粒高度分散在铝基材表面,并极大地提高了铝基材的表面积,从而有助于后续的脱氯反应。     

盐酸酸洗废液制备纳米氧化铁

探索了一种盐酸酸洗废液资源化处理的新工艺,采用"负压蒸发+纳米氧化铁制备"组合模式,实现了废液中盐酸的回收及铁盐的综合利用。采用正交实验考察了真空度、反应温度和蒸发量对负压蒸发工艺的影响;然后在最佳负压蒸发工艺操作条件下进行纳米氧化铁的制备,并采用正交实验考察了氨水浓度、Fe~(2+)浓度、反应温度、搅拌速率和煅烧温度等因素对α-Fe_2O_3制备的影响。     

稻壳沸石的合成及其对氨氮的吸附/脱附动力学

以稻壳为原料采用水热合成法制备了沸石,运用XRD、SEM和BET技术表征了合成沸石的结构特性。通过静态实验,研究了合成沸石对氨氮的吸附和脱附机理。结果表明:延长水热合成的晶化时间有利于合成沸石晶核的形成,合成沸石比表面积为28.418 m2·g-1,平均孔径为31.1 nm,孔体积为0.22 m3·g-1,属Na P型微介孔吸附材料。伪二级吸附动力学模型更适合描述合成沸石对氨氮的吸附过程,由伪二级吸附动力学模型拟合得到的平衡吸附量与实测值相差在1.0%以内。颗粒内扩散速率是由膜扩散和内扩散共同控制,颗粒内扩散速率常数kp随初始浓度的增加而提高。MNa OH/AN0.95时,308 K下的脱附率明显高于298 K的脱附率,但随着MNa OH/AN的增大,温度对脱附的促进作用变得越来越小,当MNa OH/AN1.21时,氨氮的脱附率可达92.1%。伪二级脱附动力学模型的拟合结果优于伪一级,碱当量高于临界值之后对提高合成沸石脱附氨氮的效果不大。     

掺Ni^2＋的TiO2颗粒光催化性能的研究

通过溶胶．凝胶法制备掺杂Ni^2＋的纳米TiO2，并用XRD和TEM进行了表征，发现Ni^2＋的掺杂减小了TiO2颗粒的粒径，Ni2＋／TiO2晶型为锐钛型。通过对目标物罗丹明B的光催化降解实验，发现Ni^2＋的掺杂提高了TiO2的光催化活性，其降解罗丹明B的反应遵从一级反应动力学方程，Ni^2＋惨杂量为1．2％时的光催化活性最高。     

Cr(Ⅵ)在Mg-Al型类水滑石上的脱附性能研究

研究了Cr(Ⅵ)在带结构正电荷的Mg-Al型类水滑石(HTlc)上的脱附性质,考察了多种脱附剂的脱附性能,研究了脱附剂种类、浓度、pH值和脱附时间等因素的影响。实验表明,脱附平衡时间比吸附平衡时间稍长,不同的脱附剂脱附效果不一样,对同一种脱附剂来说,随着脱附剂浓度的增大,脱附量增大;随着pH值的升高,脱附量总体呈上升趋势。     

粉煤灰合成NaX型分子筛的表征及其对Fe2+离子的吸附研究

以高温碱熔融处理粉煤灰合成了NaX型沸石分子筛,考察了不同水热晶化温度对产物结果的影响,用粉末XRD、XRF、SEM和FT-IR等手段对产品进行了表征,结果表明,以粉煤灰为原料用水热合成法合成微孔分子筛时,在晶化温度为90℃时能得到晶形较好的NaX型分子筛。同时考察了NaX分子筛的用量、时间和pH值等因素对Fe2+离子...     

二氧化钛光催化剂成型过程中制备条件对活性影响因素研究

通过对TiO2粉体在热处理和成型过程中制备条件的筛选,研制了具有较高机械强度和光催化活性的TiO2光催化剂颗粒,经XRD、XPS、DRS和Zeta电位分析表明,该催化剂主要晶型为锐钛矿型,适量的添加剂使其表面酸性增加,500℃热处理改善了催化剂的表面性质,催化剂颗粒对光的吸收带边红移,扩大了光能利用率.     

铁改性海泡石除锑的影响因素研究

选择廉价海泡石, 用氯化铁对其改性。研究铁改性海泡石对锑的吸附特性。结果表明,氯化铁浓度、吸附时间、初始锑浓度以及温度等因素对锑的吸附影响较大,溶液初始pH影响不明显。在初始锑浓度50 mg/L,pH 6.8,5%氯化铁改性海泡石投加量为2 g/L,吸附90 min, 温度35℃下,吸附量可达21.6 mg/g。海泡石对吸附锑具有缓冲特性,溶液的初始pH值在3.1～10.1范围时,吸附后溶液的最终pH值为8～8.5。IMS吸附锑是放热过程。改性后海泡石比表面积增大,表面羟基数量增加,导致其吸附能力增强。通过XRD谱图并未发现铁晶体的存在。     

Effect of decabromodiphenyl ether and antimony trioxide on controlled pyrolysis of high-impact polystyrene mixed with polyolefins

The controlled pyrolysis of polyethylene/polypropylene/polystyrene mixed with brominated high-impact polystyrene containing decabromodiphenyl ether as a brominated flame-retardant with antimony trioxide as a synergist was performed. The effect of decabromodiphenyl ether and antimony trioxide on the formation of its congeners and their effect on distribution of pyrolysis products were investigated. The controlled pyrolysis significantly affected the decomposition behavior and the formation of products. Analysis with gas chromatograph with electron capture detector confirmed that the bromine content was rich in step 1 (oil 1) liquid products leaving less bromine content in the step 2 (oil 2) liquid products. In the presence of antimony containing samples, the major portion of bromine was observed in the form of antimony bromide and no flame-retardant species were found in oil 1. In the presence of synergist, the step 1 and step 2 oils contain both light and heavy compounds. In the absence of synergist, the heavy compounds in step 1 oil and light compounds in step 2 oils were observed. The presence of antimony bromide was confirmed in the step 1 oils but not in step 2 oils.     

Fate of antimony in municipal solid waste incineration

The average antimony concentration in municipal solid waste is estimated to be about 10-60 ppm. Thermodynamical models predict a volatile behavior for antimony compounds, yet literature mass balances show that about 50% of the antimony input remains in the grate ashes. This fact can be explained by the formation of thermally stable antimonates in the fuel bed due to interactions with alkali or earth-alkali metals. Thermogravimetric experiments revealed an increased thermal stability for antimony oxide in presence of oxygen and calcium oxide. Spiking experiments on the test incinerator TAMARA showed that chlorination processes have a strong effect on antimony volatilization whereas high fuel-bed temperatures and addition of antimony oxide only have a moderate effect. In the grate ashes, antimony shows a pH-depending leaching property, which is typical for anionic species. This fact supports the thesis that antimony is present in the grate ashes in an anionic speciation.     

Determination of polybrominated diphenyl ethers and PBDD/Fs during the recycling of high impact polystyrene containing decabromodiphenyl ether and antimony oxide

A high impact polystyrene (HIPS) plastic, flame retarded with decabromodiphenyl ether (DecaBDE) and antimony trioxide (Sb2O3) has been repeatedly processed and the amount of debromination of the flame retardant and possible formation of PBDD/F was monitored. No indications of debromination were found. The reprocessed (recycled) plastic was found to comply with the German Chemicals Banning Ordinance. The concentrations of relevant PBDD/F congeners were at least one order of magnitude below the regulated limit values for PBDD/F (1 ppb for the sum of four congeners, 5 ppb for the sum of all eight regulated congeners).     

Immobilization of antimony waste slag by applying geopolymerization and stabilization/solidification technologies

During the processing of antimony ore by pyrometallurgical methods, a considerable amount of slag is formed. This antimony waste slag is listed by the European Union as absolutely hazardous waste with a European Waste Catalogue code of 10 08 08. Since the levels of antimony and arsenic in the leachate of the antimony waste slag are generally higher than the landfilling limits, it is necessary to treat the slag before landfilling. In this study, stabilization/solidification and geopolymerization technologies were both applied in order to limit the leaching potential of antimony and arsenic. Different combinations of pastes by using Portland cement, fly ash, clay, gypsum, and blast furnace slag were prepared as stabilization/solidification or geopolymer matrixes. Sodium silicate–sodium hydroxide solution and sodium hydroxide solution at 8 M were used as activators for geopolymer samples. Efficiencies of the combinations were evaluated in terms of leaching and unconfined compressive strength. None of the geopolymer samples prepared with the activators yielded arsenic and antimony leaching below the regulatory limit at the same time, although they yielded high unconfined compressive strength levels. On the other hand, the stabilization/solidification samples prepared by using water showed low leaching results meeting the landfilling criteria. Use of gypsum as an additive was found to be successful in immobilizing the arsenic and antimony.

ImplicationsDespite the wide use of antimony for industrial purposes, disposal options for an antimony waste such as slag from thermal processing of antimony ore were not reported in the existing literature. This study aimed to develop a disposal strategy for the hazardous antimony waste slag. The findings of this study would contribute to understand the immobilization mechanisms of antimony and arsenic and will also be of interest to the owners of the antimony ore processing plants and to researchers investigating the efficiency of stabilization/solidification and geopolymerization technologies.     

Mobility of antimony in soil and its availability to plants

In a historical mining area residual material has been filled on land and these locations are used today as agricultural soils or house gardens. The antimony concentrations in these soils are up to 500 mg/kg. Antimony transfer into 19 vegetable and crop species was investigated. In grain and other storage organs up to 0.09 mg Sb/kg were found, whereas maximum antimony concentrations in shoots and leaves were determined to be 0.34 mg Sb/kg and 2.2 mg Sb/kg, respectively. Despite the high antimony contamination of the soils, concentrations in the investigated plants in general corresponded to concentrations only reported for uncontaminated soils. NH4NO3 extraction of some of the soils indicated that the mobile fraction of antimony present was only 0.06-0.59%. In contrast, in leaves of spinach grown under controlled conditions in soils with a high mobile antimony content an accumulation of the element could be observed: a maximum value of 399 mg Sb/kg was detected, and a correlation between the mobile fraction in the soils and antimony in leaves was found.     

Distribution of antimony in contaminated grassland: 2--Small mammals and invertebrates

Concentrations of antimony in invertebrates and small mammals from grasslands in the vicinity of an antimony smelter were significantly elevated compared to a control site. Higher concentrations of antimony were recorded in liver, lung and kidney tissue of herbivorous and insectivorous mammals from the contaminated sites. However, there is little evidence of bioaccumulation of antimony in food chains represented by the soil-vegetation-invertebrate-insectivore pathway of the grasslands, and little indication of significant accumulation by herbivorous mammals despite marked contamination of their diet.     

Distribution of antimony in contaminated grassland: 1--Vegetation and soils

Antimony concentrations in surface soils were found to decrease with increasing distance from an antimony smelter. This pattern was also found in moss bags exposed in the same area. At three sites close to the smelter, antimony concentrations in soil and vegetation were much higher than at a rural control site and published background levels. Maximum soil and plant concentrations on a dry weight basis of 1489 mg kg(-1) and 336 mg kg(-1), respectively, were found, compared to background levels of <1 mg kg(-1). Field exposure of grass in pots of uncontaminated soil and a laboratory experiment using soils from near the smelter suggested that the antimony in vegetation was largely due to continued aerial deposition and not to uptake from soil.     

Temporal and spatial distribution of atmospheric antimony emission inventories from coal combustion in China

A multiple-year inventory of atmospheric antimony (Sb) emissions from coal combustion in China for the period of 1980-2007 has been calculated for the first time. Specifically, the emission inventories of Sb from 30 provinces and 4 economic sectors (thermal power, industry, residential use, and others) are evaluated and analyzed in detail. It shows that the total Sb emissions released from coal combustion in China have increased from 133.19 t in 1980 to 546.67 t in 2007, at an annually average growth rate of 5.4%. The antimony emissions are largely emitted by industrial sector and thermal power generation sector, contributing 53.6% and 26.9% of the totals, respectively. At provincial level, the distribution of Sb emissions shows significant variation. Between 2005 and 2007, provinces always rank at the top five largest Sb emissions are: Guizhou, Hunan, Hebei, Shandong, and Anhui.     

Antimony distribution and environmental mobility at an historic antimony smelter site, New Zealand

A historic antimony smelter site at Endeavour Inlet, New Zealand has smelter residues with up to 17 wt.% antimony. Residues include coarse tailings (cm scale particles, poorly sorted), sand tailings (well sorted) and smelter slag (blocks up to 30 cm across). All of this material has oxidised to some degree over the ca. 100 years since the site was abandoned. Oxidation has resulted in acidification of the residues down to pH 2-5. Smelter slag contains pyrrhotite (FeS) and metallic antimony, and oxidation is restricted to surfaces only. The coarse tailings are the most oxidised, and few sulfide grains persist. Unoxidised sand tailings contain 10-20 vol.% stibnite (Sb2S3) containing up to 5% As, with subordinate arsenopyrite (FeAsS), and minor pyrite (FeS2). The sand tailings are variably oxidised on a scale of 2-10 cm, but original depositional layering is preserved during oxidation and formation of senarmontite (Sb2O3). Oxidation of sand tailings has resulted in localised mobility of both Sb and As on the cm scale, resulting in redistribution of these metalloids with iron oxyhydroxide around sand grain boundaries. Experiments demonstrate that Sb mobility decreases with time on a scale of days. Attenuation of both As and Sb occurs due to adsorption on to iron oxyhydroxides which are formed during oxidation of the smelter residues. There is no detectable loss of Sb or As from the smelter site into the adjacent river, <50 m away, which has elevated Sb (ca. 20 microg/l) and As (ca. 7 microg/l) from mineralised rocks upstream. Despite the high concentrations of Sb and As in the smelter residues, these metalloids are not being released into the environment.