氟石膏中氟的分布及固氟脱酸改性

以工业副产物氟石膏为研究对象,通过筛分进行粒度分析,得到不同粒径pH值、水溶性氟以及总氟含量的变化规律;重点研究了掺入2种碱性工业副产物作为改性剂对氟石膏化学改性固氟脱酸的效果,从而确定改性剂的最佳掺量。结果表明,氟石膏中氟的分布有一定规律;掺加5%的电厂干法脱硫灰或2%钢铁厂烧结烟气脱硫灰能很好的起到固氟脱酸的效果。     

包裹块石煤固氟燃料制备工艺研究

石灰或烧制白云岩与粘土、低氟无烟煤粉作为包裹材料，通过正交试验方法，对陕西省紫阳县蒿坪镇高氟块状石煤进行了固氟效果研究。结果表明，影响包裹石煤固氟效果的主要因素是无烟煤粉和石灰，影响顺序是无烟煤粉〉石灰〉粘土。最佳制备工艺条件为石煤块：无烟煤粉：石灰：粘土=70：10：10：5，固氟率达91．9％。     

包裹块石煤固氟燃料制备工艺研究

以石灰或烧制白云岩与粘土、低氟无烟煤粉作为包裹材料,通过正交试验方法,对陕西省紫阳县蒿坪镇高氟块状石煤进行了固氟效果研究。结果表明,影响包裹石煤固氟效果的主要因素是无烟煤粉和石灰,影响顺序是无烟煤粉>石灰>粘土。最佳制备工艺条件为石煤块∶无烟煤粉∶石灰∶粘土=70∶10∶10∶5,固氟率达91.9%。     

载铁活化天然沸石处理高氟地下水

采用氯化铁改性天然沸石进行地下水除氟效果的研究,考察了地下水中4种阴离子Cl-、HCO3-、SO24-和PO34-对该改性沸石除氟效果的影响,并分析了其除氟机理和表面成分。研究结果表明,对于初始氟浓度不同的水样,随着阴离子浓度的增加,吸附剂对氟的去除率逐渐下降。Cl-对吸附剂除氟效果影响较小,氟去除率降低较慢;随着HCO3-浓度的增大(由100 mg/L到1 000 mg/L),水样pH由8.42缓慢升高到9.52,而氟去除率则由70.36%缓慢下降到56.73%(2mg/L);SO24-及PO34-对改性沸石除氟效果影响较大,氟去除率降低较快,且PO34-的影响大于SO24-。可以得到载铁活化天然沸石对4种阴离子的吸附顺序为:PO34->SO24->HCO3->Cl-。     

杭州市半山地区氟在水土系统中迁移转化的试验研究

半山地区位于杭州市北郊,是该市重工业区,分布有杭州钢铁厂、玻璃厂、汽轮机厂、重型机械厂及火电厂等大中型工厂。该区已不同程度地受到工业氟污染。由于大气中的氟污染,使树木的叶片含氟量明显地高于风景区,还影响了蚕桑业的发展;土壤中含氟量较高,使局部地区的浅层地下水受到污染,影响了当地居民的健康。因此,对该地区氟污染的研究具有较大的理论和实际意义。本研究着重通过多种试验对该区氟在水土系统中的迁移转化进行探讨。     

诱导结晶法处理高氟水的试验研究

提出了利用方解石部分代替氟磷酸钙作为诱导结晶法的晶种处理100mL氟离子质量浓度15.000mg/L高氟废水,以降低成本。通过单因素试验及正交试验获得最优反应条件:方解石质量分数为20%、晶种投加量为0.6g、磷酸三钠和氯化钙投加量分别为氟离子摩尔浓度的6、12倍,此时氟离子去除率可达到93.45%,氟离子质量浓度降至1mg/L以下,满足《生活饮用水卫生标准》(GB 5749—2006)中氟化物的限值要求。     

pH对铝盐絮凝剂形态分布与混凝除氟性能的影响

对比研究了AlC13和3种不同碱化度的聚合氯化铝(PACl)在不同pH与投量下除氟效果,并对不同形态铝盐除氟机理进行了初步探讨.结果表明,pH对絮凝剂水解后铝形态分布及其除氟效果有重要影响.pH 5 ～6时,Al3+和Al2、Al3等低聚态铝为AlCl3主要形态,且AlCl3更易水解生成可将溶解态氟转化为颗粒态氟的Al(OH)3,从而较PACl具有更佳除氟效果.pH ＞7时,PACl较AlCl3具有更佳除氟效果,且增大PACl碱化度可促进氟的去除,这主要是由于具有较高Al13含量的PACl更容易与电负性F-结合所致;且絮凝剂混凝除氟絮体ζ电位越高,越利于F-在絮体表面吸附.     

蜂窝煤燃烧氟污染的控制

以碳酸钙为固氟添加剂,以炉渣及粉煤灰等低氟材料取代全部或部分粘土作为粘结剂来制作蜂窝煤,进行了燃煤降氟的试验研究.结果表明,添加碳酸钙能有效降低蜂窝煤燃烧时候的氟排放,当煤:粘土:CaCO3的质量比为70:17:13时,碳酸钙的固氟效果最佳,氟的排放率可降低64.1%.以炉渣为粘结剂制作蜂窝煤能够显著降低燃烧时向外界排放的氟化物量,当煤:炉渣:CaCO3为80:8:12时,蜂窝煤燃烧排氟量较小且趋于稳定.已拌有一定剂量粉煤灰粘结剂的煤中添加15%的粘土后碳酸钙的固氟效果明显改善,当煤:粘土:粉煤灰:CaCO3为70:15:9:6时固氟效果最佳,此时蜂窝煤氟逸出率仅为18.2%,氟的减排率达到77.9%,显著优于未添加粘土时碳酸钙的固氟效果,蜂窝煤添加碳酸钙固氟剂进行高效固氟时,需同时适当增加粉煤灰加入量,以稳定固氟剂的高温固氟效果.     

萍乡地区土壤氟的地质分布特征

地质调查表明,萍乡地区属半湿润富铁铝地球化学环境,中性酸性土壤氟聚集区.区内二迭系小江边组原岩经风化作用后,形成的亚粘土、腐殖土中氟含量最高,次为小江边组原岩本身。再次是三迭系大冶组土壤.从岩性上看,高氟主要出现在钙镁质泥岩及泥灰岩上.钙镁质泥岩是萍乡地区烧制砖、瓦的坯土,是烧窑过程中环境氟升高的一个重要来源.     

铁铝盐基离子对土壤中水溶性氟环境效应的影响

氧化物或粘土矿物可吸附氟离子,但磷酸根离子与氟离子存在竞争吸附效应,造成氟的环境存在量、存在形态及生物效应更加复杂,影响了环境中氟污染的治理.试验选用典型贵州黄壤和石灰土,通过向模拟高氟污染土壤中添加铁铝盐基离子和磷酸盐,采用两因素最优设计,研究外源物质对土壤中水溶性氟的影响.结果表明,FeCl3·6H2O或AlCl3·6H2O都能降低土壤中水溶性氟,而KH2PO4使土壤中水溶性氟增加,对黄壤和石灰土中水溶性氟影响效果大小依次为FeCl3·6H2O(AlCl3·6H2O)、KH2PO4.同时表明,采用铁铝盐基离子改变黄壤性质,达到降氟效果仍有很大潜力,而石灰土环境在高添加铁铝盐基离子水平下继续添加FeCl3·6H2O或AlCl3·6H2O降低土壤中水溶性氟的作用较弱.从土壤pH看,黄壤水溶性氟受试验因子影响复杂,土壤pH低水溶性氟不一定低,pH在4～6时,氟元素的形态及有效性尤其复杂,而石灰土中水溶性氟基本随pH降低而降低.     

诱导结晶法去除地下水中氟离子简

针对现行高氟地下水处理工艺中存在的工艺复杂、运行管理困难等问题，提出采用诱导结晶法除氟。其技术核心是在高氟水中投加氟磷灰石作为晶种，并投加磷酸盐和钙盐使水中氟离子在晶种表面生成氟磷酸钙（Ca₁₀（PO₄） ₆F₂）结晶。通过单因素实验得出最佳工艺条件：投加8g/L氟磷灰石，并投加NaH₂PO₄和CaCl₂，使钙离子、磷酸根离子和氟离子的摩尔比为10：5：1，搅拌速度为100 r/min，反应时间1 h。反应中磷酸根离子和钙离子的利用率分别达到98%和25%以上。电子扫描显微镜（SEM）表征晶种在参与反应后，表面有结晶生成。研究表明，采用诱导结晶法可将水中氟离子浓度从5~10 mg/L降至1 mg/L以下，达到饮用水水质标准。     

Study on fluoride emission from soils at high temperature related to brick-making process

Characteristics of fluoride emission from 12 soils at temperatures of 400-1,100 degrees C related to the brick-making process were studied. The results obtained in this study indicate that fluoride emission as gaseous HF and SiF4 was related to the firing temperature, soil total fluoride content, soil composition and calcium compounds added to soils. Soils began to release fluoride at temperatures between 500 and 700 degrees C. Marked increases of the average fluoride mission rate from 57.2% to 85.4% of soil total fluoride were noticed as the heating temperature was increased from 700 to 1,100 degrees C. It was found that the major proportion (over 50%) of the soil total fluoride was emitted from soils at approximate 800 degrees C. The amount of fluoride released into the atmosphere when heated depended on the total fluoride contents in the soils. Correlation analysis showed that the soil composition, such as cation exchange capacity, exchangeable calcium and CaCO3, had some influence on fluoride emission below 900 degrees C, but had no influence at temperatures above 900 degrees C. Addition of four calcium compounds (CaO, CaCO3, Ca(OH)2, and CaSO4) at 1.5% by weight raised the temperature at which fluoride began to be released to 700 degrees C. The greatest decrease in fluoride emission among the four calcium compound treatments was found with CaCO3.     

Cement paste column for simultaneous removal of fluoride, phosphate, and nitrate in acidic wastewater

Cement paste, a cured mixture of cement and water, was reported to have considerable capacity for fluoride removal. In this study, heavily mixed fluoric acid wastewater from a semiconductor fabrication plant was applied to a column packed with cement paste granules to evaluate its capacity for the removal of fluoride and three other contaminants, phosphate, nitrate, and sulfate, as well as to investigate the interactions between these contaminants and cement components. The column reduced fluoride to remarkably low levels since fluorite was formed at highly elevated concentrations of calcium and the residual fluoride was further sorbed into the amorphous calcium phosphate that precipitated the entire amount of phosphate until breakthrough. The simultaneous removal of sulfate in the earlier stage was followed by significant removal of nitrate in exchange with the gradual release of sulfate. This behavior was explained by the co-precipitation of sulfate with calcium phosphate or calcium aluminate solids and the subsequent substitution of nitrate for the interlayer sulfate of monosulfate. However, the overall removal capacity of cement paste was reduced due to the high effluent loss of calcium and competition for calcium between fluoride and phosphate.     

Response of Tomato Fruiting to Hydrogen Fluoride as Influenced by Calcium Nutrition

Two varieties of tomatoes grown at 40 to 200 ppm calcium were continuously fumigated with HF throughout flowering and fruit development. Fruit size was directly related to the level of calcium nutrition, and within each calcium treatment the fruits on plants subjected to HF at about 6 μg F/m³ were smaller than those on unfumigated plants. The smaller fruit size was associated with partial or complete seedlessness, suggesting that calcium plays an essential role in fertilization with which fluoride may interfere. Fluoride injury to the tomato foliage was most severe at the lowest calcium level. Treatment with HF at about 8 μg F/m³ produced some injury to tomato foliage but had no apparent effect on fruiting. Evidently fluoride can affect plant fruiting, but considering the severity of the HF treatments required, effects on tomato fruiting probably are of little practical significance. The relationship between fluoride injury and calcium nutrition suggests interference with calcium metabolism as a mechanism of fluoride injury to plants.     

Active biomonitoring of airborne fluoride near an HF producing factory using standardised grass cultures

In order to study the pollution gradient in the vicinity of an HF producing factory, a biomonitoring programme was performed employing VDI standardised grass cultures. Specimen plants of Lolium multiflorum cv. Lema were exposed at 11 sites over five monthly periods and the biomass produced was used for subsequent F-analyses. Meteorological data from the study region confirmed that wind direction accounted for changes in the pollution pattern over periods of time. Fluoride concentrations in the grass cultures, however, were unrelated to temperature and precipitation sums during the exposures. The biomass production of the grass cultures proved to be unrelated to these parameters as well but, with the enhanced growth of the plants, the fluoride concentrations were lower due to the dilution of the element with higher biomass accumulation. Because the contribution of particulate fluoride was unknown, both the washed grass cultures and the washing water were analysed in order to determine the amount of external fluoride. Washing reduced the fluoride concentrations by 22% on average, indicating that most of the element was internal fluoride stemming from stomatal uptake. Larger amounts of fluoride, however, could be washed off from grass cultures exposed at sites close to the factory indicating that dust emissions played a greater role at these locations. Because particulate emissions were supposed to arise from CaF₂ and the waste-product anhydrite, grass cultures were also analysed for calcium and sulphur. While calcium concentrations were generally high but unrelated to fluoride, sulphur concentrations showed a slight relationship to the F-concentrations determined in the unwashed plants. Latter findings indicate the co-deposition of the two elements as surface bound, external loads, but bioindication could not clarify to what extent both elements were partitioned in the gas-to-particle phase. We therefore recommend using the grass culture method in air quality programmes to identify any exceedances of European feeding stuff standards in the vicinity of large emitters.     

Fluoride toxicity to aquatic organisms: a review

Published data on the toxicity of fluoride (F-) to algae, aquatic plants, invertebrates and fishes are reviewed. Aquatic organisms living in soft waters may be more adversely affected by fluoride pollution than those living in hard or seawaters because the bioavailability of fluoride ions is reduced with increasing water hardness. Fluoride can either inhibit or enhance the population growth of algae, depending upon fluoride concentration, exposure time and algal species. Aquatic plants seem to be effective in removing fluoride from contaminated water under laboratory and field conditions. In aquatic animals, fluoride tends to be accumulated in the exoskeleton of invertebrates and in the bone tissue of fishes. The toxic action of fluoride resides in the fact that fluoride ions act as enzymatic poisons, inhibiting enzyme activity and, ultimately, interrupting metabolic processes such as glycolysis and synthesis of proteins. Fluoride toxicity to aquatic invertebrates and fishes increases with increasing fluoride concentration, exposure time and water temperature, and decreases with increasing intraspecific body size and water content of calcium and chloride. Freshwater invertebrates and fishes, especially net-spinning caddisfly larvae and upstream-migrating adult salmons, appear to be more sensitive to fluoride toxicity than estuarine and marine animals. Because, in soft waters with low ionic content, a fluoride concentration as low as 0.5 mg F-/l can adversely affect invertebrates and fishes, safe levels below this fluoride/l concentration are recommended in order to protect freshwater animals from fluoride pollution.     

基于自碳黑的水化硅酸钙制备及其磷回收特性

以白碳黑、硅灰、硅藻土和硅胶筛选硅质原料，并与钙质原料电石渣制备了水化硅酸钙。借助XRF、BET、FT—IR等表征手段，通过多次重复除磷实验，研究了硅质原料特性对水化硅酸钙回收磷性能的影响。结果表明，白碳黑具有极高的反应活性，因此可作为制备具有磷回收特性的水化硅酸钙的硅质原料。结合XRD等表征发现，白碳黑的有效利用率是影响水化硅酸钙回收磷性能的关键，该利用率取决于白碳黑与电石渣的摩尔配比以及水热反应温度。当电石渣与白碳黑的摩尔比为1．6：1，反应温度为170℃时，白碳黑具有最佳的利用效率。该条件制备的水化硅酸钙可作为晶种，在其表面结晶形成羟基磷灰石，从而达到磷回收的目的，磷回收后固体物质中的磷含量为19．05％。     

The Microdetermination of Fluoride in Vegetation

This paper describes a micro method for the determination of the fluoride content of plant materials, particularly the leaves. The samples are dried and ground to a fine powder. Fifty milligram samples are burned in oxygen in 250-ml separatory funnels or in 300-ml Erienmeyer flasks. The gaseous products of the combustion are absorbed in 0.1 N NaOH in the closed funnel or flask and transferred to a small covered plastic dish in which the fluoride is diffused to tiny droplets of 3N sodium hydroxide solution distributed over the lower side of a tight fitting cover. The diffused fluoride is dissolved in water and determined colori-metrically by the SPADNS reagent.     

Aluminium contamination from fluoride assisted dissolution of metallic aluminium

Trace amounts (microg g(-1) quantities) of fluoride ion are found to catalyse the dissolution of metallic aluminium in very slightly acidic or alkaline aqueous media. Possibly hazardous levels of aluminium could get leached from cooking utensils if fluoridated water or fluoride rich foodstuffs are used. The fluoride assisted corrosion of aluminium is most dramatic in oxalic, tartaric acids or sodium bicarbonate. Carbon dioxide also corrodes aluminium in the presence of the fluoride ion, generating colloidal hydrated aluminium oxide which is readily soluble in dilute organic and mineral acids.     

Ageing of chromium(III)-bearing slag and its relation to the atmospheric oxidation of solid chromium(III)-oxide in the presence of calcium oxide

Slag arising in ferrochromium and stainless steel production is known to contain residual levels of trivalent chromium. As the chromium is normally bound in the slag matrix in various silicate or spinel phases, and hence not easily mobilised, utilisation or controlled disposal of such slag is generally considered unproblematic. Experimental test work with a number of slag materials indicates, however, that very gradual oxidation of trivalent to hexavalent chromium does occur when the slag is exposed to atmospheric oxygen, rendering a quantifiable but small portion of chromium in this much more mobile and toxic form. Mechanisms and rates of the oxidation reaction were investigated in a number of long-term studies using both original slag materials and artificial mixes of chromium and calcium oxides. Powders of these materials, some of them rolled into balls, were left to age under different conditions for periods of up to 12 months. In the slag samples, which contained between 1 and 3 wt.% chromium, 1000–10 000 μg Cr(VI) were found per gram of chromium within 6–9 months of exposure to an ambient atmosphere. The rate of the oxidation reaction decreased exponentially, and the reaction could generally be said to have ceased within 12 months. In mixtures of calcium and chromium oxides the oxidation reaction is presumed to occur at the boundaries between chromium oxide and calcium oxide phases through diffusion of oxygen along the grain boundaries and of Cr³⁺ across the boundaries, resulting in the formation of calcium chromate. In the slags, where calcium and chromium oxide can form a solid solution, the oxidation is likely to occur at the exposed surface of grains containing this solution.