Ethylenediamine tetramethylenephosphonic acid as a selective collector for the improved separation of chalcopyrite against pyrite at low alkalinity

Chalcopyrite is the main Cu-containing mineral and cannot be separated well from pyrite using traditional xanthate collectors with large amounts of lime depressant, resulting in difficulties of the tailing treatment and associated precious metals recovery. Therefore, in this study, the green and odourless ethylenediamine tetramethylenephosphonic acid(EDTMPA) was introduced as a novel chalcopyrite collector. Flotation results from the binary mineral mixture and real ore demonstrated that EDTMPA could realize the selective separation of chalcopyrite from pyrite relative to ethyl xanthate(EX) without any depressants within the wide p H range of 6.0–11.0, and might replace the traditional high-alkaline lime process. Electrochemical and Fourier transform infrared spectra measurements indicated that the difference in adsorption performance of EDTMPA on chalcopyrite and pyrite was larger than that of EX, suggesting a better selectivity for EDTMPA. Density functional theory calculations demonstrated that there were stronger chemical bonds between P—O groups of EDTMPA and the Fe/Cu atoms on chalcopyrite in the form of a stable six-membered ring. Crystal chemistry calculations further revealed that the activity of metal atoms of chalcopyrite was higher than that of pyrite. Therefore, these basic theoretical results and practical application provide a guidance for the industrial application of EDTMPA in chalcopyrite flotation.

STUDIES OF THE INITIATION MECHANISM OF VINYL POLYMERIZATION WITH THE SYSTEM PERSULFATE/N-ALKYL SUBSTITUTED ETHYLENEDIAMINE DERIVATIVES

Effects of N-alkyi substituted ethylenediamine derivatives on vinyl polymerization using persulfate as initiator were studied. The apparent kinetic equations and overall activation energies of acrylamide polymerization were determined using the above mentioned system as initiator. The promoting activities of different diamine derivatives on vinyl polymerization are in the order of tertiary diamine>secondary diamine>primary diamine. Diamines having methyl groups as the substituent on their nitrogen atom possess higher promoting activity than that of having larger alkyl groups. The initial free radicals produced through the redox reaction of persuifate and diamines were studied by spin strapping technique and ESR spectroscopy. The results obtained confirm the fact that the initial free radicals of the diamine species can initiate vinyl polymerization and become the amino end group of the resulting polymers.

α-Oxoketene Cyclic S, S-cetals Chemistry-Substitution Reaction of α,α'-Dicinnamoyl Ketene Cyclic S, S-Acetals with Ethylenediamine

α,α'-Dicinnamoyl ketene cyclic S, S-acetals 4 were reacted with ethylenediamine to afford α,α'-dicinnamoyl ketene cyclic N,N-acetals 5. This process provides a new method for thesynthesis of 5 in high yield under mild conditions.

Synthesis,Crystal Structure and Antimicrobial Study of N,N,N'-Tris(3-aminopropyl)ethylenediamine Copper(Ⅱ) Diperchlorate

The title compound [Cu（C11H29N5）]（ClO4）2 was synthesized and characterized by elemental analysis, IR and X-ray single-crystal diffraction. The compound crystallizes in the monoclinic system, space group P21/n with α = 9.405（2）, b = 14.495（3）, c = 14.715（3） A, β= 90.262（3）°, V=2006.1（7） A^3,M,=493.83,Z=4,F）（000）= 1028,Dc= 1.635 g/cm^3, T= 298（2） K,μ= 1.403 mm^-1 and = 0.71073 A. The was refined to R = 0.0508 and wR = 0. 1250 for 2293 observed reflections with I 〉 2σ（I）. The Cu（Ⅱ） atom possesses a five-coordtinate CuN5 environment which shows a slightly distorted square-pyramidal geonetry. Antimicrobial activity study found that the complex is active against Salmonella species, Staphylococcus aureu, Bacillus pumilus and Bacillus coliforms.

Crystal Structures of Co(Ⅱ) and Cu(Ⅱ) Complexes and Ammonium Salt Involving Ethylenediamine

The Co（II） complex I and ammonium salt II were synthesized from the direct reaction of 1,2-ethylenediamine and cobaltous acetate tetrahydrate and manganese acetate tetrahydrate in anhydrous ethanol. Treatment of N,N＇-bis（salicylidene）ethylenediamine with Cu（OAc）2·H2O results in the formation of Cu（II） complex III. C14H37CoNaO8 （I）： triclinic, space group P1, a = 8.6296（12）, b = 12.0291（17）, c = 12.1108（17） A, α = 75.335（2）, β = 69.991（2）, γ = 72.248（2）°, V= 1109.4（3） A3, Z = 2, ρcaloa = 1.342 g/cm3, the final R= 0.0342 for 4817 observed reflections with I 〉 2σ（I） and Rw = 0.1263 for all data. C6H16N204 （II）： space group P1, a = 5.5513（10）, b = 5.5589（11）, c = 7.4437（14） A, α = 94.332（4）, β = 104.497（4）, γ = 103.487（4）°,V= 214.06（7） A3, Z = 1, ρcalcd = 1.398 g/cm3, the final R = 0.0431 for 829 observed reflections with I〉 2σ（I） and Rw = 0.1263 for all data. C14H37CuN40 （III）, space group P21/n, a = 9.050（9）, b = 18.434（17）, c = 11.659（11） A, β = 107.134（19）°, V= 1859（3） A3, Z = 4, ρcalcd =1.443 g/cm3, the final R = 0.0616 for 3308 observed reflections （O 〉 2σ（I）） and Rw = 0.1229 for all data. Their structures were all determined by X-ray diffraction, elemental analysis and IR.

Effect of butanol on flotation separation of quartz from hematite with N-dodecyl ethylenediamine

In order to investigate the effect of butanol on quartz flotation when N-dodecyl ethylenediamine(ND)was used as collector, single mineral flotation and artificial mixed mineral(hematite and quartz were mixed at a mass ratio of 3:2) separation were conducted in the laboratory. Experimental results indicated that addition of butanol could improve the collecting performance of ND on quartz and enhance the floatability of quartz. Best flotation recovery of quartz was obtained when butanol was mixed with ND at a mass ratio of 1:1. Moreover, the molecular structure of alcohols had a significant effect on mineral recovery. Best separation efficiency could be obtained when tert-butanol was added as it had the largest cross-sectional area. Zeta potential measurements indicated that alcohols could strengthen electrostatic adsorption between quartz and collector. Molecular dynamic simulations revealed that co-adsorption of alcohols along with ND had taken place on the quartz surface, and ND/tert-butyl combinations were more easily absorbed on the quartz surface.

Thermodynamics of solubility of Cu_2(OH)_2CO_3 in ammonia-ammonium chloride-ethylenediamine(En)-water system

In order to decrease the evaporating rate of ammonia and increase the solubility of copper in the solution,ethylenediamine was added into the ammonia-ammonium chloride system to leach the copper-containing oxide ores.The thermodynamic model was constructed and the solubility of malachite Cu2(OH)2CO3 in the ammonia-ammonium chloride-ethylenediamine(En)-water system was calculated using the exponential computation method based on both mass balance and charge balance.It is found that the solubility of copper can be increased and the free ammonia concentration can be decreased by submitting partial ammonia with ethylenediamine.The lower free ammonia concentration in the solution is a guarantee to the lower evaporating rate of ammonia.The conditions of malachite Cu2(OH)2CO3 converting to atacamite Cu(OH)1.5Cl0.5 were also studied.A group of experiments were designed to validate the veracity of the results of the thermodynamic calculation.It is found that the thermodynamic model is reliable and it can guide the leaching process.

Selectively leaching Cu(Ⅱ) and Ni(Ⅱ) from acid mine drainage sludge by using ethylenediamine-ammonium sulfate

A method based on controlling the complexation precipitation equilibrium of metal ions was proposed to selectively recover nickel and copper from hydroxide sludge formed by lime neutralization of acid mine drainage(AMD). Ethylenediamine(EDA) and ammonium sulfate were chosen as complex reagent and precipitating reagent, respectively, to dissolve target metal hydroxides from sludge and limit useless metal ions in the pregnant solution. Results from both synthetic and natural samples show the excellent selectivity for the target metals(copper and nickel) against Fe(Ⅲ), Ca(Ⅱ) and Mg(Ⅱ), 99% recovery of Cu(Ⅱ) and Ni(Ⅱ) and shorter leaching time can be reached by this process, and the resultant solution can be used for direct electrowinning. The optimum operating conditions are: pH=9～11, ρ (EDA)=40 g/L, ammonium sulfate 50 g/L, leaching time 5 h(for natural sample) and 2.5 h(for synthetic sludge), liquid to solid ratio being 4 with mechanical stirring at room temperature.

Synthesis and Characterization of Free and Copper (II) Complex of N,N′-<i>Bis</i>(Salicylidene)Ethylenediamine for Application in Dye Sensitized Solar Cells

Dye sensitized solar cell represents a promising method for the conversion of solar energy to electric energy. In the present work free N,N'-bis(salicyli-dene)ethylenediamine and its copper (II) complex were synthesized, characterized, and investigated for use as dye sensitizers in the fabrication of dye sensitized solar cells. The dyes were characterized using UV-Vis, Steady State Florescence, and Fluorescence Lifetime, Thermogravimetric Analysis, Differential Scanning Calorimetry, and Cyclic Voltammetry. The thermogravimetric analyses of the ligand and the ligand Copper complex demonstrate the stabilizing effect of the copper ion on the ligand complex. Additionally, the copper ion is shown to stabilize the structure, as evidenced by the 150oC increase in the extrapolated onset temperature of the decomposition event. The ligand copper complex is further stabilized by the presence of the copper, which is determined by the 6.34% residue that remained at the end of the thermogravimetric analysis, compared with 0% residue when applying the same condition for the ligand without copper. The current-voltage characteristics of the cells and the electrochemical impedance were determined. The photovoltaic performance of the solar cell devices fabricated using N,N'-bis(salicylidene) ethylenediamine dye was found to be slightly better than those produced from the copper complex. The solar to electric power efficiency of the ligand-based dye sensitized solar cell was 0.14% and that of the copper complex was found to 0.12%. Although the difference in the cell efficiency is quite small, it is obvious that the insertion of Copper into the ligand did not enhance the performance of the solar cells. The photocurrent-photovoltage results are consistent with the absorption spectra that showed a more prominent band for the ligand. The free hydroxyl groups, present in the ligand but absent from the copper complex owing to their coordination with the copper metal, could be responsible for the difference in the performance of the devices. The hydroxyl groups get attached to the TiO2 and facilitate the transfer of electrons.

Cosmetic Lifting Effect of a Formula Combining Tetrahydroxypropyl Ethylenediamine, Ononis Spinosa and Glycerin as Shown by a New 2-D Imaging Method

Facial sagging is a major aging change that affects the overall shape of the face. Sagging can negatively impact self-perception and consequently quality of life. In order to fight against this aging sign, we developed a combination of three active ingredients: Tetrahydroxypropyl Ethylenediamine (THPE), Ononis Spinosa extract and Glycerin. In a clinical study, we assessed the efficacy of this association on facial sagging and wrinkles, with a special focus on immediate and lasting effects. Thirty-nine women applied the tested product daily during an eight-week treatment period. Clinical grading by experts and a new, easy to operate, 2-D imaging method were performed at different time points. The 2-D imaging method measured the upper eyelid lifting effect. The results showed an immediate and significant improvement in sagging and wrinkle parameters;these benefits were still observed seven hours after the first application. Results also showed a significant long-term improvement. The lifting effect calculated from the 2-D pictures was 1.08 mm immediately after application;the same method showed a 1.80 mm lifting effect following the eight-week treatment period. These results suggest that a skin care product combining THPE, Ononis Spinosa and Glycerin properties may be used to reduce sagging as well as wrinkles with both immediate and long term benefits.

STUDY ON THE SYNTHESIS AND PROPERTIES OF MACRORETICULAR IPN POLYACRYLAMIDE—POLY(VINYL—ETHYLENEDIAMINE)CHELATE SORBENTS

A new series of MR-IPN polyacrylamide—poly(vinyl-ethylenediamine)chelate sorbents were prepared by the reaction of ethylenediamine with MR-IPN matrixes.The new chelate sorbent showed good sorption properties for auric and platinic ions.

α-Oxoketene Cyclic S,S-Acetals Chemistry──Reaction of α,α′-Dioxo (ester)ketene Cyclic S,S-Acetals with Ethylenediamine

α, α′ -Dioxo (ester ) ketene cyclic S, S-acetais 2 were reacted withethyleneddriine to chrd α, α′-dioxo (ester)ketene cyclic N, N-acetals 3 Thisprocess provides a new method for the synthesis of 3 in gnd yteld under mildcondition. All products are confirmed with elementai analpeis, IR, 1H NMR and13~C NMR

Electroless copper plating process of N, N, N, N′-tetrakis (2-hydroxypropyl) ethylenediamine system with high plating rate

Electroless copper plating process of N, N, N′, N′-tetrakis (2-hydroxypropyl)ethylenediamine(THPED) chelating agent was researched comprehensively. The results indicate that plating rate decreases with the 3H2O has a bad effect on deposits quality, but 2, 2′-dipyridyl and PEG make deposits quality improve greatly. Low concentration of 2-mercaptobenzothiozole (2-MBT) increases plating rate and improves deposits quality, but decreases plating rate and worsens deposits quality when 2-MBT reaches 5 mg/L. The optimal conditions of this electroless MBT are 16.8 g/L, 16.0 mL/L, 13.3 g/L, 0.5 g/L, 5.0 mg/L and 2.0 mg/L, respectively, pH value is 12.75,bath temperature is 30 ℃. Plating rate reaches 9.54 μm/h plating for 30 min in the bath. The SEM images demonstrate that the surface of copper film is smooth and the crystal is fine.

乙二胺四乙酸-乙酸铵盐交换法测定阳离子交换量方法优化

针对乙二胺四乙酸(EDTA)-乙酸铵交换法测定土壤阳离子交换量耗时长的问题,对方法的搅拌方式、搅拌时间、蒸馏时间进行优化。优化后分析条件为:用磁力搅拌器代替人工橡皮头玻璃棒搅拌,确定搅拌时间为90 s,确定蒸馏时间为6 min。选择4个不同地区不同阳离子交换量的土壤标准物质用优化前、后的方法分别进行7次测定,其检测结果相对标准偏差为1.53%~5.32%;28个实际样品进行成对二样本均值分析,优化前、优化后测定的土壤阳离子交换量结果无显著性差异;对优化前、后28个土壤样品阳离子交换量测定结果进行相关性分析,线性相关显著,相关系数r=0.998。结果表明,EDTA-乙酸铵交换法优化前、后均具有较好的精密度和准确度,结果无显著性差异,EDTA乙酸铵交换法优化后的方法检测时间(1人测定8个样品)由280 min缩短到130 min,提高了检测效率,适合批量石灰性土壤阳离子代换量的测定。

羟乙基乙二胺的连续流制备工艺

以乙二胺和环氧乙烷为原料,在具有特殊微结构的连续流微反应器内发生乙氧基化反应合成羟乙基乙二胺。考察了原料物质的量比、乙二胺含水量、反应温度、停留时间对反应的影响。结果表明,在n(乙二胺)∶n(环氧乙烷)=3∶1、乙二胺含水量为0.96%(质量分数)、反应温度为80℃、停留时间为60 s的最佳工艺条件下,环氧乙烷转化率接近100%,羟乙基乙二胺的选择性为87.4%,二羟乙基乙二胺的选择性为9.2%。间歇釜式反应工艺在相同物料比和反应温度条件下,羟乙基乙二胺的选择性为83.5%,二羟乙基乙二胺的选择性为15.9%。连续流微反应器能有效提高羟乙基乙二胺的选择性,降低副反应的发生,同时大大缩短了反应时间,提高了反应效率。

乙二胺盐酸盐与氢氧化钙反应动力学

在双氨基硅烷偶联剂的工业生产过程中会产生大量的乙二胺盐酸盐副产物,该副产物通过与氢氧化钙进行中和反应得到无水乙二胺,可实现乙二胺的循环利用。利用电导率法建立乙二胺盐酸盐转化率和电导率的关系,考察了液固比、盐浓度、温度等因素对乙二胺盐酸盐转化率的影响,并确定了最优工艺条件。实验结果表明,乙二胺盐酸盐的转化率随着液固比及乙二胺盐酸盐浓度的增大而降低。基于缩芯模型,建立乙二胺盐酸盐和氢氧化钙的动力学方程。根据实验数据求出反应过程的活化能,发现乙二胺盐酸盐和氢氧化钙的中和反应主要受内部扩散控制。动力学模型为Kt=1-3(1-x)^(2/3)+2(1-x),活化能为30.89 kJ/mol。该研究为从乙二胺盐酸盐副产物提取无水乙二胺提供了实验依据。

乙二胺–硅烷偶联剂KH792汽液相平衡研究

为给精馏工艺分离乙二胺(EDA)-硅烷偶联剂N-β-(氨乙基)-γ-氨丙基三甲氧基硅烷(KH792)体系提供基础数据,采用Rose汽液平衡釜测定3~12 kPa范围内硅烷偶联剂KH792的饱和蒸气压和8 kPa下EDA-KH792的汽液平衡数据,采用Herington面积积分法检验所测数据的可靠性,在此基础上采用NRTL和Wilson活度系数模型对实验数据进行关联模拟。结果表明:NRTL和Wilson模型关联EDA-KH792体系的气相组成平均偏差分别为0.0055,0.0079,平衡温度平均偏差分别为0.8971,1.1631 K,两模型关联数据的偏差均较小,关联精确均较高,均可用于该体系的汽液平衡计算;但NRTL模型关联数据的偏差更小、精度更高,更适合该体系的汽液平衡计算。

乙二胺改性柚皮粉对甲基橙的吸附机理探究

以柚皮粉为原料,经环氧氯丙烷氯代和乙二胺接枝,成功制备了乙二胺改性柚皮粉吸附剂,并将其用于甲基橙废水处理。实验结果表明,乙二胺改性柚粉对甲基橙的最优吸附条件为pH=5,投加量为0.05 g,4 h后平衡,吸附率为92.77%,同比未改性柚皮粉的吸附率提升了62.91%。其吸附过程符合准二阶动力学方程和Langmuir模型,以化学吸附为主,常温下为自发放热过程。研究结果可为改性农林废弃物对阴离子染料废水处理提供参考。

还原氨化法合成乙二胺研究进展

乙二胺是一类重要的化工原料和精细化工中间体,在医药、农药、材料、电镀工业、石化和助剂等领域广泛应用,发展乙二胺合成技术具有市场应用价值。在乙二胺合成策略中,醇的还原氨化法是最直接和最具有原子经济性的路线,可满足绿色可持续化工的发展。综述了近年来还原氨化法合成乙二胺的研究进展,按不同的乙二胺合成方法介绍了金属催化剂的研究进展及反应机理,并对还原氨化法合成乙二胺的研究趋势进行了展望。