改性成都粘土预处理垃圾渗滤液的吸附热力学和动力学研究

本文采用十六烷基三甲基溴化铵(HDTMA)对成都粘土进行改性,将改性粘土用于垃圾渗滤液处理,对处理过程的吸附热力学和动力学进行研究。研究表明,分别在303.15K、313.15K和333.15K下,粘土吸附渗滤液中氨氮和有机物的平衡时间为50min左右,改性后的粘土吸附效果比原土提高了大约2～3倍;改性粘土对氨氮的吸附既符合Langmuir等温吸附,也符合Freundlich等温模型,对有机物的吸附更符合Freundlich等温模型;此反应过程均属自发的放热过程,其吸附动力学数据符合准二级动力学方程和粒子内扩散方程。     

铈改性活性炭对苯酚的吸附行为研究

采用浸渍法制备铈改性活性炭(Ce/AC),研究活性炭改性前后对苯酚的去除率,考察pH值及Ce/AC投加量对苯酚去除率的影响,采用吸附等温线模型、热力学模型及动力学模型对Ce/AC吸附苯酚过程进行拟合,研究其吸附特性及机理。结果表明,同等条件下,Ce/AC对苯酚的吸附量为56.9mg/g,是改性前的4倍;在25℃,不调节pH值,Ce/AC的投加量为6g/L时,Ce/AC对苯酚去除率达到95.4%;Langmuir吸附等温线可较好地描述Ce/AC吸附苯酚过程,热力学计算结果表明,Ce/AC吸附苯酚过程为自发吸热熵值增大的过程,吸附动力学符合拟二级动力学模型,Ce/AC吸附苯酚过程存在亲(疏)水作用、氢键作用及软硬酸碱作用。     

乙二胺改性木屑对As(V)的吸附研究

以乙二胺对木屑进行改性作为重金属离子的吸附剂,研究了其对水溶液中砷离子[As(Ⅴ)]的吸附行为。采用红外光谱(FT-IR)对改性木屑进行了表征。研究表明,乙二胺改性木屑对As(Ⅴ)的吸附符合Freundlich等温吸附模型,在p H值为6.5、温度为298.15K、投加量为2g/L、As(Ⅴ)溶液初始浓度为500mg/L时,改性木屑对As(Ⅴ)的吸附量为148.76mg/g。动态吸附实验表明,乙二胺改性木屑对As(Ⅴ)的吸附动力学可以用准二级动力学方程描述,说明它的吸附机理是一个物理与化学吸附相结合的过程。     

改性蔗髓重金属吸附剂去除水中Cr(Ⅵ)的动力学研究

对甘蔗渣预处理后以Na OH和二硫化碳改性转型合成重金属吸附剂。实验结果表明,改性后蔗髓纤维(MSCB)投加量为4 g/L,对50 mg/L Cr(Ⅵ)的最大吸附量为9.8 mg/g,平衡时间为30~60 min,去除率达98.05%,出水浓度0.78 mg/L,比改性前蔗髓纤维对Cr(Ⅵ)的吸附率(23.7%)提高了74.35%。MSCB对Cr(Ⅵ)的吸附进行Langmuir与Freundlich等温吸附方程拟合,更符合Langmuir单分子化学吸附;对吸附动力学拟合模型分析,吸附过程更符合准二级速率方程;吸附热力学模型显示该吸附为自发进行的吸热反应且是熵增过程。     

改性核桃壳生物炭对模拟水样中Pb(Ⅱ)的吸附性能研究

该文利用改性核桃壳生物炭对水中Pb(Ⅱ)进行吸附研究,探究了吸附剂投加量、pH值、接触时间、金属离子初始浓度和温度对吸附性能的影响,并对改性前后核桃壳的吸附性能进行了比较.Pb(Ⅱ)初始浓度为100mg/L时,在298K下,当pH值为5.0、投加量为7g/L、以180r/min振荡吸附2h,改性吸附剂CMBC的平衡吸附...     

有机改性凹凸棒土对腐殖酸的吸附性能研究

合成了十六烷基三甲基氯化铵(CTAC)改性的凹凸棒土吸附剂,并研究了其对水中腐殖酸的吸附行为。通过FTIR、TG对改性前后凹凸棒土进行表征。结果表明,十六烷基三甲基氯化铵成功结合到凹凸棒土表面,结合到凹凸棒土表面的量为9.78%。在25℃时,腐殖酸在吸附剂上吸附行为符合Freundlich方程,吸附动力学符合拟二级动力学方程,初始浓度为54.60~200.20mg/L时,ATP-CTAC对腐殖酸的最大吸附量为253mg/g;温度对吸附行为影响不大;改性后的凹凸棒土对腐殖酸的吸附随pH的增大而降低;改性后的凹凸棒土显著地提高了对腐殖酸的吸附量。     

含钛高炉渣对水中氨氮的吸附特性

选用含钛高炉渣作为吸附剂,研究渣的投加量、粒径大小、温度以及溶液初始pH等因素对含钛高炉渣吸附水中氨氮的影响及吸附特性。动力学数据分析表明,准二级动力学模型能更好地描述含钛高炉渣对氨氮的吸附;颗粒内扩散方程拟合结果发现,含钛高炉渣对氨氮的吸附包括表面吸附和颗粒内扩散两个阶段。吸附等温线拟合表明Langmiur方程能够更好地模拟含钛高炉渣对氨氮的吸附过程。在20℃、反应时间4h的条件下,对于100mL浓度为100mg/L的氨氮溶液,8g粒径为80~120目的含钛高炉渣对氨氮的去除率可以达到32%;随着温度的升高,去除率基本呈上升趋势;溶液初始pH对氨氮的去除有一定的影响,在碱性条件下有较好的去除效果。     

D406螯合树脂对硫酸锌溶液中氟的吸附和解吸性能及动力学研究

研究了D406螯合树脂对硫酸锌溶液中氟的吸附和解吸性能,考察了影响氟吸附和解吸的因素以及该树脂吸附和解吸氟的动力学参数。结果表明,在25℃、pH=2、硫酸锌浓度为1.50mol/L、氟离子浓度为200mg/L条件下,D406螯合树脂对氟的吸附量为5.55mg/g。D406螯合树脂对氟的吸附符合Freundlich吸附模型。吸附和解吸的动力学符合Boyd液膜扩散方程,吸附反应活化能Ea=12.14kJ/mol,解吸反应活化能Ea=19.54kJ/mol。     

邻菲咯啉改性膨润土吸附水中镉离子的研究

通过邻菲咯啉改性膨润土,对水中镉离子进行吸附性能的研究.探讨了投加量、pH值、接触时间、温度等影响因素对改性膨润土吸附镉离子的影响.实验结果表明:在25℃,250 r/min,pH 5.5,NaNO3浓度0.01 mol/L,投加量为5.0 g/L,镉离子质量浓度100 mg/L的条件下,未改性膨润土对水中镉离子的吸附...     

生物质竹炭对水中Cd~(2+)的吸附行为研究

以竹炭和经化学改性竹炭作为吸附剂,研究其对水溶液中Cd2+的吸附特性,探讨了竹炭对Cd2+的吸附热力学和吸附动力学性质,通过单因子优化实验探讨了温度、竹炭投加量和p H值对吸附效果的影响。结果表明:竹炭及改性竹炭对Cd2+的吸附动力学过程符合准二级动力学模型,在18h可达到平衡;其等温吸附曲线符合Langmuir方程,最大吸附量分别为10.18mg/g和16.71mg/g;两者对Cd2+的吸附受温度的影响较小;竹炭及改性竹炭的最佳投加量分别为0.8g、0.6g;p H对竹炭及改性竹炭吸附Cd2+的影响较大,在p H 2~6范围时,竹炭及改性竹炭对Cd2+的吸附量随p H的增加而增加。     

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%.     

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.     

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.     

Copper catalyzed/mediated synthetic methodology for ebselen and related isoselenazolones

Scope of the copper catalyzed/mediated selenium-nitrogen coupling reaction has been studied for the synthesis of isoselenazolones. It is noticed that the 2-chloro, 2-bromo-, and 2-iodo-aryl amides substrates can be exploited in the selenium-nitrogen coupling reaction by employing 25-100 mol % of CuI/1,10-phenanthroline (L) and potassium carbonate as a base in DMF. Furthermore, electron rich 2-chloro-arylamides also underwent selenium-nitrogen coupling reaction to give biologically important selenium-nitrogen heterocycles. Also, copper-catalyzed selenium-nitrogen coupling reaction has been meticulously applied for the synthesis of diaryl diselenides having methoxy, amine, and amide functionality from respective aryl iodides in the presence of stoichiometric amount of succinimide as an external Se-N coupling partner.     

Knoevenagel condensation catalyzed by novel Nmm-based ionic liquids in water

A series of novel N-methyl morpholine (Nmm) based ionic liquids with 1,2-propanediol group were synthesized and used as catalysts for Knoevenagel condensation at room temperature in water. Under the effect of the catalyst, various aldehydes or aliphatic ketones could react with a wide range of activated methylene compounds well, including malononitrile, alkyl cyanoacetate, cyanoacetamide, β-diketone, barbituric acid, 2-arylacetonitrile and thiazolidinedione. Furthermore, most of the products could be separated just by filtrating and washing with water. Additionally, the catalyst is recyclable and applicable for the large-scale synthesis.     

Construction of polyheterocyclic spirotetrahydrothiophene derivatives via sulfa-Michael/aldol cascade reaction

A series of polyheterocyclic spirotetrahydrothiophene derivatives were obtained in moderate to excellent yields via a catalyst-free sulfa-Michael/aldol cascade reaction of chalcones 1 and commercially available 1,4-dithiane-2,5-diol 2 under mild conditions. We also present the first asymmetric sulfa-Michael/aldol cascade reaction of chalcones 1 and commercially available 1,4-dithiane-2,5-diol 2 with moderate to good enantioselectivities catalyzed by readily available chiral phase-transfer catalysts (PTCs).     

Suzuki-Miyaura reactions of the soluble guanylate cyclase inhibitor NS2028: a non-product specific route to C-8 substituted analogues

Both soluble guanylate cyclase (sGC) inhibitors ODQ 1 and NS2028 2 are synthesized via improved protocols. In the former case treating 3,4-dihydroquinoxalin-2(1H)-one oxime 8, which can be prepared in two steps from 1,2-benzenediamine, with 1,1′-carbonyldiimidazole (CDI) gives the dihydro-ODQ 10 that in the presence of KMnO₄ oxidises to give ODQ 1 in an overall yield of 46% starting from 1,2-benzenediamine. In the latter case, the synthesis affords NS2028 2 from 2-amino-4-bromophenol 3 in three steps with an overall yield of 85% and avoids the need for chromatography. Furthermore, Suzuki-Miyaura reaction conditions are described that enable the preparation of 8-aryl and 8-heteroaryl derivatives of NS2028 directly from NS2028 2. Finally, demethylation of the 8-(methoxyphenyl) substituted analogues afforded the 8-(hydroxyphenyl) derivatives 40-42. All new products are fully characterised.