Process optimization of reaction of acid leaching residue of asbestos tailing and sodium hydroxide aqueous solution

Silica is the major component of the acid leaching residue of asbestos tailing. The waterglass solution can be prepared by the reaction of the residue with sodium hydroxide aqueous solution. Compared to the high temperature reaction method, this process is environmental friendly and low cost. In this paper, the reaction process of the residue and the sodium hydroxide aqueous solution is optimized. The optimum reaction process parameters are as follows: the usage of sodium hydroxide is 26.4 g/100 g acid leaching residue, the reaction temperature is 90℃, the reaction time is 1 h, and the ratio of the liquid/solid is 2.0. The significance sequence of the process parameters to the alkali leaching reaction effect is the usage of sodium hydroxide > the ratio of the liquid/solid > the reaction time > the reaction temperature. The significance sequence to the leaching ratio of SiO2 is the ratio of the liquid/solid > the usage of sodium hydroxide > the reaction time > the reaction temperature. The significance sequence to the modulus of the sodium silicate is the ratio of the liquid/solid > the usage of sodium hydroxide > the reaction time > the reaction temperature. Under the optimum conditions, the leaching ratio of the SiO2 is 77.5%, and the modulus of the sodium silicate is 3.15. The XRD analysis result indicates that the major components of the alkali leaching residue are serpentine, talc, quartz and some albite.     

法桐树叶衍生生物质炭吸附含镍废水研究

以法桐树叶为原材料制备KOH改性的生物质炭吸附剂,对其表面性质进行表征,并研究其对含Ni(Ⅱ)废水的吸附性能。通过扫描电镜、比表面积分析仪及傅里叶红外光谱仪对制备的生物质炭表征分析证明,生物质炭呈现以微孔为主的多孔结构,比表面积为1 733.01 m2/g,表面存在一定量的羟基、羧基等酸性表面官能团,有利于对Ni(Ⅱ)的吸附。25℃下,生物质炭对Ni(Ⅱ)的饱和吸附量为12.35 mg/g。通过对吸附实验数据拟合可知,其吸附行为符合准二级动力学模型,等温吸附过程符合Langmuir模型。生物质炭对Ni(Ⅱ)的吸附主要表现为单分子层化学吸附,同时伴有自发的吸热反应。     

用于Pb2+、Hg2+离子选择性固相萃取的微流控芯片

为实现微流控芯片对重金属Pb~(2+)、Hg~(2+)离子的选择性固相萃取,首先采用3-氯丙基三甲氧基硅烷和5-甲基苯并三氮唑对纳米二氧化硅进行硅烷偶联改性,随后以改性纳米二氧化硅为基础,设计并制备了可更换吸附剂的一体化填充式固相萃取芯片.测试结果表明:改性后不仅吸附剂的团聚现象得到明显改善,且当pH=5时,对Pb~(2+)的吸附率可达99.1%,对Hg~(2+)的吸附率可达98.9%,而对Cr~(3+)的吸附率为20.4%,对Mn~(2+)的吸附率仅为13.2%.即使样品中混有干扰离子(K~+、Na~+或Mn~(2+))时,对Pb~(2+)、Hg~(2+)离子的吸附率仍均可达97%以上.当进样流速≤1.5 mL/min时,微流控芯片对Pb~(2+)或Hg~(2+)的吸附率可达98%以上;以0.5 mol/L的盐酸和2%的硫代尿素为洗脱液,控制流速在0.20.3 mL/min范围内时,芯片对Pb~(2+)或Hg~(2+)的洗脱率均达到92%以上.用于Pb~(2+)、Hg~(2+)离子的选择性固相萃取芯片的成功制备,有助于微流控技术在重金属污染监测领域的应用和推广.     

Precipitation of antimony from the solution of sodium thioantimonite by air oxidation in the presence of catalytic agents

The behavior of antimony oxidation in the solution of sodium thioantimonite was studied in the presence of catalytic agents. The catalytic effects of the respective addition of cupric sulfate, sodium tartrate, potassium permanganate, phenol, 1,2-dihydroxybenzene and their combination on the oxidation of sodium thioantimonite were investigated. A pilot test was carried out. The results show that the respective use of sodium tartrate, cupric sulfate, potassium permanganate, phenol and 1,2-dihydroxybenzene have little catalytic effect on the oxidation of sodium thioantimonite. However there exists obvious catalytic oxidation by the combination of 0.25 g/L 1,2-dihydroxybenzene, 0.5 g/L potassium permanganate and 1.0 g/L phenol. Moreover, high blast intensity, the increase of temperature and NaOH concentration favor the oxidation of antimony. The oxidation process of antimony has such advantages as quick reaction and low operation costs. The results of the pilot test are consistent with those of laboratory experiments.     

Preparation of calcium stannate by modified wet chemical method

A modified wet chemical route for low-temperature synthesis of the calcium stannate CaSnO3, a potential material for dielectric applications is reported. Firstly, a precursor CaSn(OH)6 was prepared using tin tetrachloride, calcium chloride and sodium hydroxide at room temperature. Then the precursor was annealed at relatively low temperature of 600 ℃ to obtain CaSnO3. The phase identification, thermal behavior and surface morphology of the samples were characterized by element analysis, X-ray diffraction (XRD) , thermo-gravimetric (TG) analysis and derivative thermo-gravimetric (DTG) analysis, Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM) in detail. The results show that CaSnO3 obtained by this method possesses a cubic perovskite structure with average grain size of 5μm.     

梧桐叶生物质炭的制备及吸附性能研究

以梧桐树叶为原材料,KOH为活化剂,采用一步法制备生物质炭,并研究其吸附性能。通过扫描电子显微镜、比表面积及孔径分析仪观察到所制备的生物质炭存在丰富的孔隙结构,比表面积为1 795.36 m~2·g~(-1),总孔体积为0.94 cm~3·g~(-1)。25℃下,生物质炭对亚甲基蓝呈现出优良的吸附性能,饱和吸附量为832.50 mg·g~(-1)。拟合结果得知,生物质炭对亚甲基蓝的吸附过程符合准二级动力学模型和Langmuir模型。本研究为废弃生物质的资源化利用提供了一种技术手段,具有理论意义和实用价值。     

生物炭负载零价纳米铁对溶液中的 Cr6+ 去除的研究

生物炭(biochar, BC)作为载体,负载纳米零价铁(nano zero valent iron, nZVI)形成复合吸附材料,利用电子扫描显微镜(SEM)和X射线衍射仪(XRD)表征材料的结构特征。研究了不同材料、初始溶液初始p H、不同初始浓度、去除剂的投加量对BC负载nZVI (nZVI-BC)去除含Cr~(6+)废水的影响。结果表明:BC的加入提高了nZVI的分散性和抗氧化性,同时提升稳定性,对于水中Cr~(6+)的去除具有较好的效果;当Cr~(6+)的初始浓度为15 mg/L,去除剂的投加量为2.5 g/L, pH=4的条件下,其去除率达到了98%; nZVI-BC去除含Cr~(6+)废水的过程符合Langmuir吸附等温式和准一级动力学方程,其中最大吸附量为209.93 mg/g。     

Road performances of mesoporous nano-silica modified asphalt binders

The objective of this paper was to find new modifier to improve the aging resistance and low temperature cracking resistance of asphalt. To investigate the aging resistance of modified asphalt binders, mesoporous nano-silica(doping Ti~(4+)) was used as a asphalt modifier. Some physical properties including penetration, ductility, and softening point of asphalt were analyzed with RTFO(Rotating thin film oven) aging and ultraviolet aging. Moreover, the performances of high and low temperature of modified asphalt binders with pressure aging were tested by dynamic shear rheometer(DSR) test and bending beam rheometer(BBR) test. These results showed that the penetration decreased, low temperature ductility, and softening point increased when adding mesoporous nano-silica to base asphalt. After ultraviolet radiation aging, the penetration loss and ductility loss of modified asphalt decreased than that of original asphalt, the increase of softening point was also significantly reduced than that of base asphalt. Furthermore, The test results of DSR and BBR showed that the G*sinδ and creep modulus‘s' of pressure aged asphalt decreased, but the creep rate ‘m' increased. It can be concluded that the aging resistance and cracking resistance of modified asphalt are improved by adding mesoporous nano-silica, especially the doping of Ti~(4+) could improve the aging resistance obviously.     

改性玉米秸秆对铜离子的吸附性能

为提高玉米秸秆吸附重金属的能力,以次磷酸钠为催化剂,通过柠檬酸对秸秆改性制备金属离子吸附剂,并采用红外吸收光谱与扫描电子显微镜对其化学结构和微观结构进行了表征。对比研究玉米秸秆改性前后对Cu~(2+)的吸附性能,考察了pH、初始浓度、吸附温度和吸附时间等因素对Cu~(2+)吸附量的影响。研究结果表明,当Cu~(2+)溶液初始质量浓度为30mg/L、秸秆投加量为1.0g/L、pH为5.5、吸附温度为25℃、吸附时间为30min时,柠檬酸改性玉米秸秆对Cu~(2+)的吸附效果最好,最大平衡吸附量可达26.5mg/g,相比未改性玉米秸秆提高了1.9倍,Cu~(2+)去除率可达89%。吸附动力学研究表明,改性秸秆对Cu~(2+)吸附动力学符合准二级动力学模型。     

酸改性高岭土对含Cd~(2+)和Pb~(2+)废水的吸附研究

采用酸改性高岭土进行SEM和FTIR表征,考察其对含Cd~(2+)、Pb~(2+)废水的吸附特性及机理。结果表明:与原矿高岭土对比发现,酸改性高岭土片层状结构变薄变小,表面基团组成发生明显的变化;对于20 m L初始浓度为40 mg·L~(-1)的Cd~(2+)、Pb~(2+)溶液,当p H为5.8,酸改性高岭土投加量50 g·L~(-1)时,吸附效果最好;利用Freundlich和Langmuir方程对吸附等温线进行拟合,Langmuir方程拟合效果更优,表明其吸附过程为单分子层吸附;吸附机理服从准二级动力学方程,其计算吸附量与实验测量值仅偏差2.87%。     

还原剂改性生物炭吸附法去除对苯醌的试验研究

选用Na_2SO_3、FeSO_4两种还原剂制备改性麦秸秆生物炭,以对苯醌为目标污染物,通过试验研究生物炭制备过程中还原剂浸渍时间及浓度、生物炭热解温度及投加量对其吸附去除对苯醌的影响,同时进行热力学分析。结果表明,还原剂浸渍时间宜为2 h、最佳物质的量浓度为0.001 mol/L,生物炭最佳热解温度为600℃、最佳投加量为20 mg。另外,FeSO_4改性麦秸秆生物炭吸附去除对苯醌的效果比Na_2SO_3改性麦秸秆生物炭好。     

Extraction and reaction mechanism of potassium from associated phosphorus and potassium ore

Potassium and phosphate were extracted at low temperature by acid hydrolysis process to decompose a new type of associated phosphorus and potassium ore. The main factors affecting the dissolution rate were investigated, such as grinding fineness, the amount of sulfuric acid and fluoride salt, reaction time and temperature, etc. Meanwhile, the effects of various factors on the formation of soluble potassium and phosphate were also discussed. The reaction products and residues were determined by X-ray diffraction(XRD), scanning electron microscopic(SEM) analysis and other means. The results showed that the dissolution rates of potassium and phosphorus were 70wt% and 93.7wt%, respectively, under the conditions of a grain size of 95.64wt% lessthan 0.074 mm, 9.78 g·g~(-1) sulfuric acid, 0.5 g·g~(-1) ammonium fluoride, 160 ℃ and a reaction time of 2h. The thermodynamic and chemical reaction mechanism was revealed that the primary reaction could be completed spontaneously in a temperature range of 298-433 K. The increase of reaction temperature had an important influence on ion exchange reaction, which was more conducive to the spontaneous process. The research will open up a new way for efficient use of potassium ore resources.     

稻壳炭对Pb2+吸附效果影响因素研究

稻壳炭对重金属Pb2+的吸附量受吸附时间、吸附剂投加量、温度、pH、稻壳炭理化性质等因素影响。实验通过单因素分析法研究了上述各影响因素对吸附效果的影响,并设计正交试验探讨了常温下稻壳炭吸附Pb2+的最佳吸附条件,采用扫描电镜(SEM)对吸附前后稻壳炭样品进行了表征分析。实验发现:吸附过程前30min为快速吸附阶段,60min后吸附过程基本完成,120min后吸附量达到最大值;相同浓度条件下,稻壳炭对Pb2+的吸附量存在一个最佳投加量;温度方面20℃时对吸附较为有利,温度高于25℃或低于15℃时不利于吸附;pH对吸附效果影响较大,pH 5-7条件下对吸附最为有利,过酸过碱均不利于吸附进行;对稻壳炭进行活化改性是提高其吸附能力的一种有效途径。     

Performance of a combined capacitor based on ultrafine nickel oxide／carbon nanotubes composite electrodes

A new sol-gel process for the preparation of ultrafine nickel hydroxide electrode materials was developed. The composite electrodes consisting of carbon nanotubes and Ni(OH)2 were developed by mixing the hydroxide and carbon nanotubes together in different mass ratios. In order to enhance energy density, a combined type pseudocapacitor/electric double layer capacitor was considered and its electrochemical properties were characterized by cyclic voltammetry and dc charge/discharge test. The combined capacitor shows excellent capacitor behavior with an operating voltage up to 1.6 V in KOH aqueous electrolyte. Stable charge/discharge behaviors were observed with much higher specific capacitance values of 24 F/g compared with that of EDLC (12 F/g) by introducing 60% Ni(OH)2 in the anode material. By using the modified anode of a Ni(OH)E/Carbon nanotubes composite electrode, the specific capacitance of the cell was less sensitive to discharge current density compared with that of the capacitor employing pure nickel hydroxide as anode. The combined capacitor in this study exhibits high energy density and stable power characteristics.     

A Modified Co-precipitation Method to Prepare Cu/ZnO/Al_2O_3 Catalyst and Its Application in Low Temperature Water-gas Shift(LT-WGS) Reaction

A modified co-precipitation method for the production of Cu/ZnO/Al_2O_3 complex was studied. The modification was that part of Al was introduced by adding Al~(3+) into Cu~(2+)/Zn~(2+) solution, and the rest of Al was added after co-precipitation step in the form of pseudo-boehmite. The prepared samples were characterized by different techniques such as X-ray diffraction, N_2 adsorption, H_2-N_2O titration, temperature programmed reduction and scanning electron microscopy. X-ray diffraction characterizations revealed that Al~(3+) can be doped in aurichalcite lattice, and the maximum doping amount of Al~(3+) was 5.0% of total Cu and Zn atoms. The Cu/ZnO/Al_2O_3 sample produced by the modified method, in which co-precipitated Al~(3+) was 2.5% of total Cu and Zn atoms showed much better activity and stability in water-gas shift reaction than commercial sample. The high Cu surface area(26.1 m~2/g) obtained by decompositon of doped aurichalcite is believed to be responsible for the activity enhancement. The stability was enhanced mainly because of the support effect of γ-Al_2O_3, which was decomposed from pseudo-boehmite in the calcination step.     

Offgas analysis and pyrolysis mechanism of activated carbon from bamboo sawdust by chemical activation with KOH

Bamboo sawdust was used as the precursor for the multipurpose use of waste. Offgases released during the activation process of bamboo by KOH were investigated quantitatively and qualitatively by a gas analyzer. TG/DTG curves during the pyrolysis process with different impregnation weight ratios (KOH to bamboo) were obtained by a thermogravimetric analyzer. Pyrolysis mechanism of bamboo was proposed. The results showed that the offgases were composed of CO, NO, SO2 and hydrocarbon with the concentration of 1 372, 37, 86, 215 mg/L, respectively. Thermogravimetric analysis indicated that the pyrolytic process mainly experienced two steps. The first was the low temperature activation step (lower than 300 ℃), which was the pre-activation and induction period. The second was the high temperature activation step(higher than 550 ℃), which was a radial activation followed by pore production. The second process was the key to control the pore distribution of the final product.     

不同沸石粉对Cu~(2+)的吸附特性试验研究

为了研究沸石粉对重金属铜的吸附效果,采用室内试验方法,选取天然沸石粉、4A沸石粉以及在天然沸石粉的基础上添加粉煤灰经高温焙烧制成的改性沸石粉作为吸附剂对重金属Cu~(2+)进行静态吸附试验,为了对比验证水泥吸附去除Cu~(2+)的能力,添加了水泥作为吸附剂。通过室内静态吸附试验发现,四者吸附Cu~(2+)能力大小为4A沸石粉≈改性沸石粉天然沸石粉水泥;考虑到制备工艺及经济因素,改性沸石粉是吸附去除Cu~(2+)的最佳选择;改性沸石粉去除Cu~(2+)的最佳掺量为2 g:100 mg/L;p H值在5~8之间沸石粉吸附Cu~(2+)的效果较好。     

盐酸羟胺改性柚皮吸附剂的制备及对Cu~(2+)吸附性的研究

用盐酸羟胺改性柚子皮制备一种新型的生物质吸附剂,通过模拟废水吸附试验研究了其对Cu~(2+)的去除效果。从模拟废水的pH、吸附时间、吸附剂用量和反应温度4个方面分别考察了改性柚子皮吸附剂对铜离子去除的影响。以溶液的吸光度和电导率来表征吸附性能。实验结果表明:吸附反应时间、吸附剂加入量、反应温度和模拟废水的pH等4个因素对吸附剂性能均有明显影响,其中当Cu~(2+)的初始质量浓度为100mg/L,温度为35℃,溶液pH=4,吸附剂质量为吸附剂/吸附质质量的15%,吸附时间为25min时,吸附率最高。     

Ferronickel preparation using Ni-Fe co-deposition process

Nucleation mechanism and technological process for Ni-Fe co-deposition with a relatively high Fe~(2+)concentration surrounded were described,and the effects of Fe~(2+) concentration,solution pH,temperature,and sodium dodecyl sulfonate concentration were investigated.Electrochemical experiments demonstrate that iron's electrodeposition plays a leading role in the Ni-Fe co-deposition process,and the co-deposition nucleation mechanism accords with a progressive nucleation.Temperature increase does favor in increasing nickel content in the ferronickel(Ni-Fe co-deposition products),while Fe~(2+) concentration increase does not.When solution pH is higher than 3.5,nickel content in the ferronickel decreases with pH because of the hydrolysis of Fe~(2+).With the current density of 180 A/m~2,Na_2SO_4 concentration of 100 g/L and Ni~(2+) concentration of 60 g/L,a smooth ferronickel deposit containing 96.21% Ni can be obtained under the conditions of temperature of 60 °C,Fe~(2+) concentration of 0.3 g/L,solution pH of 3 and sodium dodecyl sulfonate concentration of 40 mg/L.     

煤基活性多孔碳制备及其对CO_2/CH_4的吸附分离研究

为了分离煤层气中的CO_2和提高煤层气利用率,通过调控KOH对无烟煤的活化比例,制备一系列煤基活性多孔碳(APC-1,APC-2和APC-4)。通过扫描电镜表征可知,KOH活化对无烟煤的表面具有雕蚀作用,可形成发达的孔隙结构。通过氮气等温吸附测试可知,煤基活性多孔碳具有较高的比表面积(993～1 615 cm~2/g)和孔体积(0.48～0.8 cm~3/g)。在温度298 K和压力100 kPa条件下,APC-2对CO_2和CH_4的吸附量分别高达3.49,1.59 mmol/g。通过理想吸附溶液理论预测,APC-4对等物质量的二元混合气体CO_2/CH_4吸附选择性可达4.57。本文制备方法合成工艺简单,适用于煤基活性多孔炭的制备,在吸附分离煤层气中CO_2和提高煤层气利用率方面具有广阔的应用前景。