Thermal decomposition of ammonium hexafluoroaluminate and preparation of aluminum fluoride

The thermal decomposition process of （NH4）3AlF6 was studied by DTA-TGA method and the related thermodynamic data were obtained. The results show that AlF3 is obtained after three-step decomposition reaction of （NH4）3AlF6, and the solid products of the first two decomposition reactions are NH4AlF4 and AlF3（NH4F）0.69, respectively. The three reactions occur at 194.9, 222.5 and 258.4 ℃, respectively. Gibbs free energy changes of pertinent materials at the reaction temperatures were calculated. Enthalpy and entropy changes of the three reactions were analyzed by DSC method. Anhydrous aluminum fluoride was prepared. The XRD analysis and mass loss calculation show that AlF3 with high purity can be obtained by heating （NH4）3AlF6 at 400 ℃ for 3 h.

Distribution of Aluminum and Fluoride in Tea Plant and Soil of Tea Garden in Central and Southwest China

The distribution of Al and F contents and the relationship between Al and F in tea plants and soils of 12 tea gardens in Central and Southwest China were investigated from October 31 to November 14, 2006. The results show that there were differences in pH, CEC, the contents of organic matter （OM）, Al and F in the different soils of the tea gardens. The Al content ranged from 1196 to 7976mg/kg for old leaf, 370 to 2681mg/kg for young leaf and 285 to 525mg/kg for stem, whereas the content of F ranged from 221 to 1504mg/kg for old leaf, 49 to 602mg/kg for young leaf and 13.5 to 77.5mg/kg for stem. The concentrations of labile Al varied obviously in the different soils, but the distribution law of labile Al content for the same garden was Alexchangeable≈AlFe.Mn oxide〉Alorganic〉mlwater.soluble. The contents of different labile F fractions varied slightly in the different soils and the different soil layers, though the exchangeable F content was lowest among the labile F in the soils. The concentrations of Al and F in tea plants increased with increasing amount of water-soluble Al or F, especially the amount of water-soluble fractions in the soil layer of 0-20cm. The correlation between Al content and F content in the tea leaf was more significant than that in the tea stem. Furthermore, the correlation between Al content and F content in whole tea plant was strongly significant （r=0.8763, p〈0.01, n=36）. There were evident tendency that Al concentration increased with the increase of F concentration in different soil layers. The correlation of water-soluble Al with water-soluble F in all soils was also strongly significant （r=0.7029, p〈0.01, n=34）. The results may provide a proof that Al and F are jointly taken up by tea plants to some extent in natural tea gardens.

The characteristics of dissolution of fluoride and aluminum from brick tea

Four experiments have been done on the influence of times of infusion, temperature, time and ratio of tea to water on the dissolving characteristics of fluoride and aluminum in brick tea. According to the results, the behaviors of F and Al which found their way into tea liquor were analyzed and the conclusions have been drawn: the dissolution of F and Al is not synchronous and after the elements find their way into tea liquor respectively, they will be reset to form complexes of F and Al.

Adsorption of Fluoride from Water Using Aluminum Coated Sand: Kinetics, Equilibrium, Effect of pH, and Coexisting Ions

An aluminum coated sand (AlCS) was evaluated as a metal oxide adsorbent for adsorption and removal of fluoride from water using a low-cost adsorbent with potential application in continuous flow adsorber systems. Surface characterization of the AlCS sorbent was performed using TEM, SEM/EDX, XRD and BET. The AlCS sorbent contained mostly amorphous aluminum oxides based on adsorbent characterization results. Favorable adsorption of fluoride onto the AlCS sorbent occurred according to the Langmuir and Freundlich adsorption equations, while physical adsorption of fluoride onto the AlCS sorbent was observed based on results from the Dubinin-Radushkevich equation. Fluoride adsorption onto the AlCS sorbent followed pseudo-second order kinetics, while surface charge analysis indicated a pHPZC of 7.1 for the AlCS sorbent. Effective fluoride removal occurred over a broad pH range from 3 to 11 with a maximum fluoride removal observed at pH 4 to 5. The effect of co-existing ions in water resulted in a decrease in fluoride uptake in the presence of bicarbonate, while resulting in an increase in fluoride uptake in the presence of calcium. The AlCS sorbent was a low-cost and sustainable adsorbent for effective adsorption and rapid removal of fluoride from water within an hour.

Determination of Boron Trifluoride in Boron Trifluoride Complex by Fluoride Ion Selective Electrode

A method was proposed to determine boron trifluoride in boron trifluoride complex using fluoride ion selective electrode(ISE). Hydroxide was chosen to mask aluminum for the determination of 0.01—0.1 mol/L of fluoride. The simulation indicated that the permissible aluminum masked at a certain p H value was limited and hardly related to F-concentration and boric acid. It is better to control p H value below 11.5 and the aluminum concentration within 0.025 mol/L to minimize the interference of hydroxide to the fluoride ISE. The decomposition conditions of boron trifluoride by aluminum chloride were investigated. It is found that the F-detection ratio will approach 1.0 if the Al/F molar ratio is 0.3—0.7 and aluminum concentration is no more than 0.02 mol/L when heated at 80 ℃ for 10 min. In one word, hydroxide is quite fit to mask aluminum for samples which contain high content of fluoride and aluminum and the BF3 content can be successfully determined by this method.

Fluoride removal from coal mining water using novel polymeric aluminum modified activated carbon prepared through mechanochemical process

Defluoridation of coal mining water is of great significance for sustainable development of coal industry in western China.A novel one-step mechanochemical method was developed to prepare polymeric aluminum modified powder activated carbon(PAC)for effective fluoride removal from coal mining water.Aluminum was stably loaded on the PAC through facile solid-phase reaction between polymeric aluminum(polyaluminum chloride(PACl)or polyaluminum ferric chloride(PAFC))and PAC(1:15 W/W).Fluoride adsorption on PACl and PAFC modified PAC(C-PACl and C-PAFC)all reached equilibrium within 5 min,at rate of 2.56 g mg^(-1)sec^(-1)and 1.31 g mg^(-1)sec^(-1)respectively.Larger increase of binding energy of Al on C-PACl(Al–F bond:76.64 eV and Al–FOH bond:77.70 eV)relative to that of Al on C-PAFC(Al–F bond:76.52 eV)explained higher fluoride uptake capacity of C-PACl.Less chloride was released from C-PACl than that from C-PAFC due to its higher proportion of covalent chlorine and lower proportion of ionic chlorine.The elements mapping and atomic composition proved the stability of Al loaded on the PAC as well as the enrichment of fluoride on both CPACl and C-PAFC.The Bader charge,formation energy and bond length obtained from DFT computational results explained the fluoride adsorption mechanism further.The carbon emission was 7.73 kg CO_(2)-eq/kg adsorbent prepared through mechanochemical process,which was as low as 1:82.3 to 1:8.07×10^(4)compared with the ones prepared by conventional hydrothermal methods.

Footprint of harmful substances in spent pot lining of aluminum reduction cell

Spent pot lining(SPL) from aluminum reduction cells is considered to be hazardous materials due to containing a large amount of soluble fluoride salts and trace toxic cyanides. The distribution of fluorides and cyanide in a 350 kA cell operated for 2396 days was analyzed and the footprint and corrosion mechanism of the harmful substances in SPL were also studied. It is found that the fluorides are mainly concentrated in the cathode carbon block and the layer of dry barrier under the cathodes, which is closely related to permeability of the cathodes and dry barrier the fluorides penetrate in. Cyanide has a low concentration in the cell center and a high concentration in the sidewall, which is positively related to the air amount entering into the areas in the cells.

Reaction behavior between the oxide film of LY12 aluminum alloy and the flux

In this paper, the brazing mechanism of LY12 aluminum alloy at middle range temperature was presented. The CsF-AlF_3 non-corrosive flux was utilized to remove the complex oxide film on the surface of LY12 aluminum alloy. The results revealed that the oxide film was removed by the improved CsF-AlF_3 flux accompanied with the occurrence of reaction as well as dissolution and the compounds CsF played an important role to remove the oxide film. Actually, the high activity of flux, say, the ability to remove the oxide film, was due to the presence of the compounds, such as NH_4F,NH_4AlF_4 and composite molten salt. The production of HF was the key issue to accelerate the reaction and enhance to eliminate the oxide film by dissolution. It was found that the rare earth element La at small percentage was not enriched at the interface. Moreover, the rare earth fluoride enhanced the dissolution behavior.

黄河流域典型煤矿矿井水协同除浊除氟药剂的制备及应用

黄河流域是我国煤炭潜力最大的区域,矿井水涌水量大但资源利用率不高,尤其在干旱和半干旱的高氟地区,矿井水中氟离子超标已成为制约提高矿井水资源利用率的主要因素之一。采用正交试验筛选出高效除氟药剂的5种组分[聚合氯化铝(PAC)、聚合硅酸铝、硝酸镁、聚合氯化铁、羧甲基淀粉钠],采用单因素试验探讨了不同制备条件和反应条件对除氟效果的影响,并通过X射线能谱分析(EDS)、X射线光电子能谱(XPS)和傅里叶变换红外光谱(FT-IR)表征探讨了除氟机理。结果表明:在金属总量M/Si、Al/Mg、Al/Fe的摩尔比分别为43、40、40条件下研制的除氟药剂,均可将含氟废水中氟离子浓度由20mg/L降至1.0 mg/L以下,达到GB 3838—2002《地表水环境质量标准》Ⅲ类中氟化物浓度限值要求(1.0 mg/L);当除氟药剂投加量为1.25 g/L,初始p H为2~12,悬浮物浓度为100~2000 mg/L,聚丙烯酰胺(PAM)投加量为0.4 mg/L时,处理后上清液剩余氟离子浓度均可控制在1.0 mg/L以下,氟离子去除率达95%以上;除氟药剂中Al、Si元素起到重要的除氟作用,主要通过形成Al—F—Al等金属络合物沉淀被去除;将除氟药剂应用于黄河流域某煤矿含氟矿井水的处理,在除氟药剂投加量为400 mg/L、PAM投加量为0.2 mg/L时,氟离子浓度从5.6 mg/L降至0.85 mg/L,并协同将矿井水浊度从500 NTU降至4.59 NTU,吨水处理药剂成本为1.602元。该除氟药剂在黄河流域含氟矿井水处理中具有较好的应用潜力。

电解铝材料生产中氟化物污染特征及形态

云南省电解铝材料产业近年发展迅猛,其氟化物排放引起的环境污染问题一直备受关注。就某电解铝材料厂为研究对象,对电解铝材料生产各环节固废中氟化物的含量和存在形态进行检测,并对生产过程中原料、产品、固废等进行了统计,结合实际开展了氟化物平衡计算。电解铝材料生产过程中,99.6%的氟化物由固废带出,0.4%的氟化物以有组织烟气、无组织天窗废气逸散的形式进入外环境,可通过增设高效脱硫协同脱氟设施和提高电解槽集气效率等措施,减缓氟化物对环境的污染。经检测分析,固废中氟化物以Na 5 Al 3 F 14、NaAlF 4、Na 3 AlF 6、K 2 SiF 6、CaF 2和AlF 3等难溶或微溶于水的化合物形态存在,土壤中水溶性氟化物含量占总氟化物的比例不足1%,表明氟化物排放和土壤环境污染之间存在一定的关联性。氟化物在土壤中累积效应较为明显,在第一类用地和第二类用地条件下,电解铝厂周围区域表层土壤中氟化物的总危害指数分别为0.794和0.09,周围土壤健康风险评估结果为可接受。

铝电解废旧阴极酸浸液除氟回收锂工艺研究

铝电解废旧阴极经过硫酸浸出得到了含有Na、Li、Al、F等有价元素的浸出液,具有回收价值的同时伴随着严重的二次污染。采用冰晶石结晶法两次除氟,除氟后回收锂。实验结果表明:当反应pH=9、n(Al):n(F)=1∶6、反应温度为50℃、反应时间为90 min、晶种添加量为0.8 g/L时,溶液中残氟浓度为48 mg/L,一次除氟率为98.15%,锂除去率为1.38%;经过二次除氟后,溶液中氟的浓度为49 mg/L,二次除氟率为85.12%,锂除去率为2.13%;经过两次除氟后,氟总除去率为99.38%,锂总除去率为1.31%;制备出的Li_(2)CO_(3)纯度大于99.5%。

二次铝灰湿法除氟工艺及氟化物的转化行为研究

为了研究湿法除氟因素(液固比、时间、温度、溶液种类、溶液浓度)对二次铝灰湿法处理过程中氟化物浸出效率及底渣氟化物浸出的影响规律,分别采用单因素实验测定湿法浸出前后底渣及其浸出液氟化物含量,同时对二次铝灰原样及湿法处理后的底渣进行XRD、SEM-EDS表征。结果表明,两种浸出介质条件下,以上5种因素均对氟化物浸出效率产生影响,常温湿法浸出条件下,NaOH溶液碱浸去除氟化物效果优于去离子水。去离子水浸出氟化物的最佳工艺参数:液固比(体积质量比,mL/g,下同)为30、水解时间为4 h、水解温度为90℃,此时氟化物浸出率为12.98%。常温条件下NaOH溶液浸出氟化物的最佳工艺参数:液固比为10、NaOH溶液浓度为1.5 mol/L、水解时间为30 min,此时氟化物浸出率为65.85%。XRD表征结果反映出湿法处理后二次铝灰中AlN含量有不同程度的减少,SEM-EDS表征结果反映出湿法处理后底渣中氟化物含量均相应减少,上述研究结果为二次铝灰湿法处理过程中氟化物去除提供科学依据。

核壳式球形铁基磁性磨料的制备及其抛光性能

[目的]混合式和镶嵌式磁性磨料的尺寸效应,以及磨粒出刃高度不一致所引起的抛光硬冲击问题亟待解决。[方法]将不规则铝粉与球形羰基铁粉均匀混合,通过加热扩散在接触界面生成金属间化合物并均匀分布在球形羰基铁粉表面,从而形成铁/铝核壳式球形磁性磨料,随后用它对氟化钙基片进行抛光。[结果]通过单因素试验优选出制备该核壳式铁基磁性磨料的最佳工艺参数为:反应时间4 h,反应温度770℃,Al含量质量分数12%。X射线衍射(XRD)、扫描电镜(SEM)观察、能谱(EDS)分析和磁化强度测试表明所得磁性磨料以羰基铁粉为内核,Fe Al、Fe_(3)Al、Fe_(0.4)Al_(0.6)等金属间化合物为壳,粒度符合正态分布,磨料相外壳分布均匀且出刃高度较为一致。氟化钙晶体经铁/铝核壳式磁性磨料抛光后表面变得光滑、平坦,粗糙度均方根值由初始的1.102μm下降到33 nm。[结论]所制备的核壳式球形铁基磁性磨料可用于软脆材料的磁力抛光。

固体核磁共振在氟化铝催化剂研究中的应用进展

氢氟烯烃(HFOs)作为重要的精细化工中间体,其制备关系着我国在应对全球气候变暖、优化能源结构方面的重大战略需求。高比表面积的AlF_(3)因其环境友好、耐HF特性和丰富的酸性中心成为绿色合成HFOs路径的核心催化剂,然而追求高比表面积的同时也为其物理化学特性的研究带来挑战。固体核磁共振(ssNMR)是鉴定材料组成结构、阐释材料合成机理、辨别酸性特征的强有力工具。通过总结近年来利用多种先进的多维多核固体核磁技术如^(27)Al、^(19)F、^(1)H、^(13)C等在高比表面积AlF_(3)的组成结构、合成机理以及酸性位点识别和定量上的杰出工作,系统剖析AlF_(3)催化剂的理化性能,这将为优异性能AlF_(3)的合成提供一定的理论指导。

微波辅助Al@PVDF⁃OH复合燃料的制备及其燃烧性能

聚偏氟乙烯(PVDF)等氟聚物可有效抑制铝粉的团聚并提高铝粉的反应活性。但氟聚物与被氧化铝覆盖的Al颗粒表面之间亲和性较差,氟聚物直接包覆在Al表面对团聚的抑制效果并不理想。为增强氟聚物与铝粉间的相互作用,改善铝粉燃烧性能,研究采用微波辅助反应的方法得到了羟基化改性的PVDF-OH,利用溶剂/非溶剂法将PVDF-OH包覆在铝粉表面得到了Al@PVDF-OH复合燃料,并进一步制备了复合固体推进剂。采用红外光谱、X射线衍射仪对PVDF-OH的分子结构与元素组成进行了研究;采用扫描电子显微镜、差示扫描量热仪、高速摄像机和氧弹量热仪等设备对Al@PVDF-OH复合燃料的微观结构组成及其燃烧性能进行了研究。结果表明,微波辅助制备得到的PVDF-OH有着较高的羟基含量,微波功率240 W下处理1 min时制备得到的PVDF-OH最佳。Al@PVDF-OH复合燃料的燃烧性能优于包覆PVDF的Al@PVDF复合燃料与加热改性处理PVDF-OH(H)的Al@PVDF-OH(H)复合燃料,在PVDF-OH含量为15%时最佳。与纯Al相比,PVDF-OH含量为15%的Al@PVDF-OH复合燃料的燃烧热值由19140 kJ·kg^(-1)增加到24912 kJ·kg^(-1);与AP混合后的燃烧测试结果表明,Al@PVDF-OH复合燃料燃烧性能相较于Al有明显改善,点火延迟时间由77 ms缩短至70 ms,燃速由195.7 mm·s^(-1)提高到225.7 mm·s^(-1)。基于Al@PVDF-OH复合燃料的固体推进剂与铝基固体推进剂相比,其燃烧热值由13281 kJ·kg^(-1)增加到14020 kJ·kg^(-1);燃速由1.281 mm·s^(-1)提高到1.915 mm·s^(-1),凝聚相燃烧产物D90由74.324μm降至52.749μm。

聚硅酸铝絮凝剂除氟除浊效能研究

随着半导体及光伏产业的发展,产生的含氟废水越来越多,含氟废水的处理也成为人们重点关注的问题。以聚硅酸铝絮凝剂(PSA)为除氟除浊药剂,研究了PSA的除氟除浊效果,并与硫酸铝、聚合氯化铝进行了除氟除浊效能对比。结果表明:PSA除氟除浊的最佳混凝条件为:水样pH=7、投加量4×10^(-4) mol/L、快搅速度260 r/min、快搅时间2 min、慢搅速度20 r/min、慢搅时间20 min、沉淀时间30 min,此时除氟率可达67.99%,剩余氟含量为1.60 mg/L,除浊率为98.67%。PSA的除氟除浊效果优于硫酸铝、聚合氯化铝。

Mechanism of aluminum complexation in oxidative activity of leaching bacteria in a fluoride-containing bioleaching system

Accumulation of toxic ions in leachate is one factor limiting bioleaching applications. The effect of fluoride ions on the growth of bioleaching microorganisms has been extensively emphasized. In this study, HF is found to be the toxic form of fluoride that affects the bacterial activity under acidic conditions. The added aluminum could compete with H^+ to complex with F-, thus significantly decrease the concentration of HF and finally reduce the toxicity of fluoride to bacteria. When F^-/Al^(3+)concentration ratio is 0.5:1.0, Fe^(2+) oxidation rate could reach 0.167 g·L^(-1)·h^(-1), close to that of the biotic control group(0.195 g·L^(-1)·h^(-1)). The competitive complexation mechanism of fluoride by AlF_n^(3-n) results in stability constants of AlF_n^(3-n) complex(7.00) that are larger than those of HF(3.18). The F^-/Al^(3+) concentration ratio in the medium could affect the speciation of AlF_n^(3-n) complex.With the decrease in F^-/Al^(3+) concentration ratio, the coordination numbers of AlF_n^(3-n) decrease. Finally, the feasibility of fluoride detoxification by aluminum ion is verified. This work has meaningful implications for fluoride-containing bacterial bioleaching systems.

氧化锆基除氟剂协同无定形氢氧化铝除氟实验研究

对某企业酸性浸出废水进行了一段氧化锆除氟、二段无定形氢氧化铝除氟实验研究。一段氧化锆除氟实验考察了反应温度、反应时间和氧化锆除氟剂加入量对废水除氟效果的影响,结果表明,升高温度、延长反应时间都能促进除氟剂除氟率提高;反应温度75℃、除氟剂加入量50 g/L、反应时间50 min时,除氟率达到96%,废水中氟质量浓度由600 mg/L降至25 mg/L。一段除氟后废水进行二段无定形氢氧化铝除氟,反应温度70℃、反应时间60 min、氢氧化铝加入量5 g/L时,废水氟质量浓度由25 mg/L降至6.5 mg/L;除氟渣晶型良好、衍射峰明显,XRD检测结果显示Na_(3)AlF_(6)是除氟渣中主要成分。

铝工业危废铝灰的高效处置新技术

针对当前铝工业中危废铝灰处置所面临的能耗高、效率低等突出问题,通过工艺和技术创新,在热力学分析的基础上提出采用磨细、微波场、惰性大颗粒辅助强化等新型处置技术,分别以氯气、氯化硅、氯气-氯化硅为氯化剂,研发了5条铝灰高效氯化加工新工艺(以氯气为氯化剂的铝灰高效利用方法,以氯气为氯化剂的二次铝灰高值化利用方法,以氯气为氯化剂的铝灰高效制备氮化铝方法,以氯化硅为氯化剂的铝灰高效制备氟化铝方法,以氯气-氯化硅为氯化剂的铝灰制备氟化铝方法)。这5种工艺可有效提升了铝灰的资源利用率、处置效率,实现铝灰深度高值化利用(制备氮化铝、氟化铝),具有显著的经济效益和社会效益。

Effects of fluoride on the removal of cadmium and phosphate by aluminum coagulation

This study focuses on the effects of p H and fluoride at different molar ratios of fluoride to Al（R F：Al） on the removal of cadmium（Cd^（2＋）） and phosphate by Al coagulation. Fluoride at R F：Al≥ 3：1 inhibits the removal of Cd over wide Al dose ranges from 5 to 10 mg/L as Al. The removal of phosphate decreases significantly at high R F：Al of 10：1 whereas at lowered R F：Al（i.e., ≤ 6：1）, an adverse effect is observed only at insufficient Al doses below 2 mg/L. Fluoride shows inhibitive effects towards the removal of Cd at p H 7 and 8 and that of phosphate at p H 6. Fluoride decreases the ζ-potential in both systems, and the decreasing extent is positively correlated to the elevated R F：Al. The Al fluoride interactions include the formation of Al-F complexes and the adsorption of fluoride onto Al（OH）3 precipitates, i.e., the formation of Al（OH）n F m. Al-F complex formation inhibits Al hydrolysis and increases residual Al levels, and a more significant increase was observed at lower p H. Al-F complexes at high R F：Al complicate the coagulation behavior of Al towards both negative and positive ionic species. Moreover, fluoride at low R F：Al shows little effect on Al coagulation behavior towards Cd^2＋and phosphate, and the spent defluoridation adsorbent,i.e., aluminum（Al） hydro（oxide） with adsorbed fluoride at R F：Al of below 0.1：1, may be reclaimed as a coagulant after being dissolved.