新型硅胶-聚合胺树脂从氯化钴电解液中深度净化除铜

SP-C是一种新型硅胶-聚合胺复合材料树脂,对铜具有较好的选择吸附性能.本文研究了该树脂在模拟氯化钴电解液中深度净化除铜工艺.在Co2 ～80g/L,Cu2 0.5g/L～2.0g/L、pH2～4、温度20℃～60℃的氯化钴电解液中,考察了该树脂对铜的吸附性能.结果表明,随料液pH增大以及温度升高,铜的交换容量增大:料液Cu2 浓度对交换容量影响较小;最佳吸附条件为:料液pH 4、接触时间30min,温度60℃.对比研究了盐酸、硫酸两种解析液,硫酸显示出更好的解析效果,最佳解析条件为H2SO42mol/L、解析接触时间40min.最佳工艺条件下,每毫升湿树脂对铜的工作交换容量及饱和交换容量分别为0.439mol和0.508mol,铜的解析液峰值浓度为28g/L.     

D315大孔阴离子交换树脂对Au(Ⅲ)的吸附性能研究

研究了D315大孔阴离子交换树脂从酸性含金氯化溶液中吸附金的性能,考察了吸附时间,pH值,温度,阴离子浓度等因素对树脂吸附金的影响.结果表明,在pH=2时树脂的吸附效果最佳,静态饱和吸附容量可达到228.80mg/g(Au/干树脂),温度越高越有利于吸附,吸附反应热焓△H=11.30kJ/mol.吸附平衡服从Freundish吸附等温式.用8%硫脲-1mol/L硫酸可以将树脂上的金完全解析.     

离子交换树脂的选择及柠檬酸溶液循环使用研究

用离子交换树脂法吸附柠檬酸溶液中的金属离子,苯乙烯系阳离子交换树脂的吸附性能较好,它对镍、铝离子的吸附容量均较大,且吸附前后柠檬酸溶液的浓度变化较小.静态条件下树脂对镍的吸附容量为16.83mg Ni/g干树脂,对铝为21.36mg Al/g干树脂;动态条件下树脂对镍的吸附容量为6.78mg Ni/g干树脂,对铝为31.8mgAl/g干树脂,吸附液流速为1m/h～3m/h.吸附后的柠檬酸溶液可循环使用.当用1mol/L硫酸解吸时,树脂对镍铝的解吸率可达90%以上.当硫酸中Ni2 为1.70mmol/L,Al3 为7.40mmol/L时,树脂的解吸率仍可达80%以上.     

L-苯丙氨酸树脂对Cu2+络合性能的研究

研究了经聚苯乙烯氯乙酰树脂(PS-Ace-Cl)制得的PS手性苯丙氨酸树脂(PS-Ace-Phe)对Cu2 的吸附性能,即通过pH、时间、Cu2 浓度等条件的改变,研究了PS-Ace-Phe对Cu2 的吸附,得到了Cu2 的最佳吸附条件:Cu2 溶液浓度为100 mmol/L,pH为6.0～8.5,吸附时间5h,此时吸附效率可达98%,树脂的最高吸附量为2.03 mmol/g,且不同Phe担载量的树脂对Cu2 的吸附率都可大于90%,PS-Ace-Phe对Cu2 的吸附可达近1∶1,说明PS-Ace-Phe对Cu2 的吸附属络合作用.同时得到吸附树脂的稳定存在条件:Cu2 溶液浓度为10mmol/L,pH为2.0～8.0时,该树脂对Cu2 的吸附稳定性可达24h.     

双变性淀粉吸附剂的合成及吸附性能研究

以环氧氯丙烷、交联化淀粉和丙烯腈为原料,水为溶剂,硝酸铈铵为引发剂,通过接枝反应合成了双变性淀粉吸附剂。其最佳制备工艺条件是交联化淀粉2g,硝酸铈铵浓度0.004mol/L,丙烯腈浓度0.3774mol/L,接枝温度35℃,接枝时间240min,料液比1:10(W/V)。对制得的双变性淀粉进行金属离子吸附性能评价,发现Cr6 吸附时使溶液处于中性或微酸性环境下,Cu2 吸附时使溶液处于弱碱性环境下,Cu2 的吸附率达到86.3%,Cr6 吸附率达78.2%,Cu2 吸附效果大于Cr6 。     

A222型阴离子交换树脂脱除HPP水溶液中SO_4~(2-)的研究

论文研究了A222树脂在N,N'-二(2-羟丙基)哌嗪(HPP)脱硫胺液中对SO42-的离子交换性能,优化条件为振荡温度50℃、交换时间2h,HPP浓度0.5mol/L、SO42-浓度0.3mol/L、p H值5.1、固液比80g/L,此条件下,树脂的交换量达163.57mg/g。在HPP-SO42-中,A222树脂具有优良的稳定性和脱盐效果,在循环交换-解吸过程中,对SO42-的平均交换量为136.25mg/g、平均交换率51.37%、平均脱附率96.48%、室温下的动态交换量可达196.90mg/g。FT-IR和TG研究结果表明,HPP能通过物理吸附作用附着在A222树脂上,而树脂对SO42-的离子交换过程中有化学键生成。树脂对SO42-的吸附过程更好地遵循Freundlich等温吸附规律。     

板栗壳活性炭对重金属离子吸附性能研究

研究了不同制备条件下,板栗壳活性炭对重金属离子Cu2+和Cd2+的静态吸附性能。以板栗壳为原料,采用ZnCl2活化法制备活性炭,使用X-射线衍射、扫描电镜、氮气吸附等方法对活性炭进行表征;比较了活性炭内部结构对Cu2+和Cd2+的吸附性能影响;同时考察了吸附温度、溶液pH值等对Cd2+和Cu2+的吸附性能的影响。研究结果表明:板栗壳制备活性炭最佳条件为ZnCl2活化浓度30wt%,料液比1:6,炭化温度600℃,炭化时间3h;同时发现板栗壳活性炭是一种具有较多孔隙的无定型炭材料,所制备的活性炭平均孔径为2~6nm,孔容为0.04~0.14cm3/g,比表面积可以达到1500m2/g以上;板栗壳活性炭对重金属离子的吸附性能主要由本身的比表面积和孔容大小决定,且同时受吸附温度和溶液pH值的影响,上述条件制备的活性炭吸附Cu2+的最佳条件为温度25℃,溶液pH值为6.5;吸附Cd2+的最佳条件为温度25℃,溶液pH值为7.5。     

Cu(Ⅱ)印迹壳聚糖交联多孔微球去除水溶液中金属离子

研究了以Cu2+为模板的壳聚糖交联多孔微球(Cu-CSCPM)对溶液中Cu2+的吸附性能,为该材料应用于去除废水、果蔬汁等有毒重金属铜离子提供理论基础。首先制备了Cu2+印迹壳聚糖交联多孔微球,并表征了微球的一些物理化学性质;其次采用静态吸附法研究了该微球对Cu2+的吸附行为。结果发现,制得的微球表面多孔,含有活性-NH2,其含水量为69.59%,树脂骨架密度为1.22g/cm3,孔度值为73.68%,交联度为82.42%。初始浓度为60mmol/L、吸附温度40℃、pH=4.0时,Cu-CSCPM对Cu2+的饱和吸附容量为1.89mmol/g。Cu-CSCPM再生5次对Cu2+仍然具有较高吸附容量。     

交联酚醛型咪唑啉树脂的合成与吸附性能研究

以苯酚及一氯醋酸为原料,合成了新型交联酚醛咪唑啉树脂.合成树脂对Au3 、Pt2 、Cu2 、Ag 、Hg2 、Co2 、Ni2 具有良好的吸附性能,其静态吸附容量分别为2.278mmol/g,1.530mmol/g,2.692mmol/g,2.390mmol/g,1.901mmol/g,1.644mmol/g,1.488mmol/g(25℃).吸附Cu2 、Hg2 、Ag 、Co2 的表观速率常数(k/min)分别为3.2659×10-2,1.7124×10-2,1.9611×10-2,2.8175×10-2.吸附Cu2 ,Ni2 ,Co2 和Ag 的最佳pH值分别为6.0～6.5,6.0～6.5,6.0～6.5和5.5～6.0.     

聚丙烯基强酸性阳离子交换纤维分离富集水体中痕量镓的研究

建立了聚丙烯基强酸性阳离子交换纤维分离富集痕量镓的新方法。当上柱流速为2m L/min时,pH=3,1000m L 0.1μg/m L的镓可被0.1000g聚丙烯基强酸性阳离子交换纤维定量吸附,10m L 1.6mol/L的硝酸溶液能将其定量洗脱,富集倍数达到100倍。随着温度的升高,纤维对镓的吸附速率增大,吸附以液膜扩散为主。经Arrhenius公式计算的表观活化能为38.71k J/mol。离子交换纤维对镓的静态饱和吸附容量为209.4mg/g,交换吸附过程服从Freundlich经验式,吸附容易发生。在最佳吸附及洗脱条件下,对自然河水和自来水中的镓进行分离富集及加标回收试验,结果表明,回收率介于86.3~104.4%之间,相对标准偏差(RSD)介于0.1~1.7%之间,结果令人满意。     

二氧化碳和丙烯直接合成甲基丙烯酸的NiPMo/TiO2催化剂的研究

用溶胶-凝胶法以磷钼酸(MPA)的镍盐溶液水解钛酸四丁酯制备了NiPMo/TiO2催化剂.使用ICP、 XRD、 TG-DTA、 IR、 TPD-MS和微反应技术研究了催化剂的化学组成、热稳定性、化学吸附性质和催化反应性能.杂多钼酸盐与TiO2通过O2-在TiO2表面发生了键合.在623 K下,杂多阴离子仍保持原有的Keggin结构.CO2在Lewis酸位Ni(Ⅱ)和Lewis碱位Ni-O-Mo的桥氧协同作用下生成CO2卧式吸附态Ni(Ⅱ)←O-(CO)←(O--Ni).丙烯有多种吸附态在催化剂上吸附.在563 K、 1 MPa和空速1500 h-1的反应条件下,丙烯的摩尔转化率为3.2%,产物MAA选择性为95%.     

Toward new camptothecins. Part 6: Synthesis of crucial ketones and their use in Friedländer reaction

In the context of the preparation of camptothecin and luotonin A analogs, the synthesis of some key keto-precursors and their use in Friedländer condensation are described. This paper also focuses on the stability of these keto intermediates and emphasizes the major differences between indolizinones and pyrroloquinazolinones series. Noteworthy is also the report of some original structures isolated as by-products of some experiments.     

CoFe2O4自形成磁性液体场致结构化对磁化的影响

The Langevin paramagnetic theory can’t describe the relation between magnetization of ferrofluids and applied magnetic field. The structuralization of ferrofluids, which is considered the main influence factor of the magnetization, is regarded. The part of magnetization works is deposited when the structure is forming. This action influences the magnetization of ferrofluids directly or indirectly. On the base of the “compressing” model, the Langevin function that usually describes the magnetization of ferrofluid is modified, and a well-fitted curve is obtained. An equation of the relation between the equivalent volume fraction after being “compressed” and the intensity of magnetic field is discovered, which approximately describes the process of magnetization. The relation between the approximate initial susceptibility and the volume fraction can be obtained from modified formula.     

Highly regioselective Buchwald–Hartwig amination at C-2 of 2,4-dichloropyridine enabling a novel approach to 2,4-bisanilinopyridine (BAPyd) libraries

The highly regioselective Buchwald–Hartwig amination at C-2 of the cheap and readily accessible reagent, 2,4-dichloropyridine with a range of anilines and heterocyclic amines is described. This new methodology is robust and provides a facile access to 4-chloro-N-phenylpyridin-2-amines on 0.25 mol scale. These intermediates undergo a further Buchwald–Hartwig amination at higher temperature to enable rapid exploration of the chemical space at C-4 and to provide a library of 2,4-bisaminopyridines.     

KMnO4-mediated oxidative CN bond cleavage of tertiary amines: Synthesis of amides and sulfonamides

KMnO₄-mediated oxidative CN bond cleavage of tertiary amines producing secondary amine was introduced, which was trapped by electrophiles (acyl chloride and sulfonyl chloride) to form amides and sulfonamides. The reaction could take place at mild condition, tolerating a wide range of function groups and affording products in moderate to excellent yields.     

Chemistry of heterocyclic compounds at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, over 50 years (Review)

The review contains a concise historical account and information on the most significant researches undertaken by the staff at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences on the Chemistry of Heterocyclic Compounds. Dedicated to Academician of the Russian Academy of Sciences B. A. Trofimov on his 70th jubilee. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1443–1502, October, 2008.     

Sulfur-directed metal-free and regiospecific methyl C(sp3)–H imidation of thioanisoles

Regiospecific and direct imidation of the methyl C(sp³)–H bond of thioanisoles is realized under mild and metal-free conditions with N-fluorobis(benzenesulfonyl)imide as an oxidant and nitrogen source. Proposed mechanism suggests that thionium ion intermediates and a Pummerer-type reaction are involved. The imidation has advantages such as high step-economy, excellent functionality tolerance, and regiospecificity, giving structurally diverse imidation products.     

Selective syntheses of 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones via temperature-dependent Rh(II)-carbenoid-mediated 2H-azirine-ring expansion

The Rh(II)-catalyzed reaction of 2-carbonyl-substituted 2H-azirines with ethyl 2-cyano-2-diazoacetate or 2-diazo-3,3,3-trifluoropropionate provides an easy access to 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones. These compounds can be selectively prepared from the same starting material using temperature as the only varied parameter. The 2-azabuta-1,3-diene intermediate, a common precursor for both heterocyclic products, isomerizes into 2H-1,3-oxazine under kinetic control, while 1H-pyrrol-3(2H)-one is the sole product of the reaction at elevated temperatures. According to DFT-calculations a one-atom oxazine ring contraction involving ring-opening to a 2-azabuta-1,3-diene intermediate, followed by a 1,5- and 1,2-prototropic shift leads to the consecutive formation of imidoylketene and azomethine ylide, which then further undergo cyclization to the pyrrole derivative.     

Synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives

Different approaches for the synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives from simple amino acids have been investigated. A library of 33 precursors for the preparation of N-hydroxy pyrazinones was obtained in moderate to good yields.