磷酸二（2-乙基己基）酯的合成与应用研究

研究了磷酸二(2-乙基己基)酯的特性,概述了磷酸二(2-乙基己基)酯的合成方法,详细介绍了磷酸二(2-乙基己基)酯作为萃取剂、阻垢剂、阻燃剂、阻燃偶联剂、抗静电剂、渗透剂、分散剂、表面活性剂、有机合成中间体等方面的应用。磷酸二(2-乙基己基)酯有着广阔的应用和发展前景。     

用溶剂萃取法分离提纯碱土金属

用溶剂萃取可以直接有效地进行碱土金属离子间的分离,从而能使产品纯度和原料利用率大幅度提高,根治污染。并用生产适合新技术领域要求的高纯产品。分别考察了二（２－乙基己基）磷酸、２－乙基己基磷酸２－乙基己基酯、二（２,４,４－三甲基戊基）膦酸的煤油体系对碱土金属离子的萃取行为。     

化学镀镍废液中镍的萃取及综合利用

利用二－（２－乙基己基）磷酸作为萃取剂萃取化学镀镍废液中的镍，萃余液用硫酸反萃取，生产工业组硫酸镍，达到治理环境，废物利用的目的。     

化学镀镍废液中镍的萃取及综合利用

利用二－ （２－ 乙基己基）磷酸作为萃取剂萃取化学镀镍废液中的镍,萃余液用硫酸反萃取,生产工业级硫酸镍,达到治理环境,废物利用的目的。     

二(2-乙基己基)磷酸萃取L-苯丙氨酸

以二（2-乙基己基）磷酸（D2EHPA）-正辛烷萃取L-苯丙氨酸为对象,研究了D2EHPA浓度、L-苯丙氨酸初始浓度以及pH值对萃取平衡分配系数的影响。不同pH值下负载有机相的红外谱图分析表明,D2EHPA与L-苯丙氨酸形成的萃合物结构与pH值无关。提出了在萃取过程中同时存在着离子交换反应和质子转移反应的观点。1个氨基酸分子与2个二（2-乙基己基）磷酸二聚体相结合。本文建立的萃取平衡分配系数关联式,拟合精度令人满意。     

2-[3-(二乙基氨基)丙基]-5-乙基吡啶的合成

由2－甲基－5－乙基吡啶在金属钠作用下，与（（C2H5）2N（CH2）2Cl作用，发生的侧镀金属化及烃基化反应，合成了2－[3－（二乙基氨基）丙基]－5－乙基吡啶，其结构经元素分析、MS、1HNMR、IR、UV分析确证。     

溶剂萃取法提取亮氨酸和异亮氨酸

研究了用二（２－乙基己基）磷酸（Ｐ２０４）作萃取剂,从毛发水解生产胱氨酸的二次母液中提取亮氨酸和异亮氨酸的方法和条件。研究表明,在常温条件下,水相初始ｐＨ为４．０时,用３０％的Ｐ２０４（体积分数）正庚烷溶液,萃取相比为１,可萃取出水相中近７０％的亮氨酸和异亮氨酸。     

海水萃取除钙,镁的研究初探

研究了用「二（２－乙基己基）磷酸」（Ｐ２０４）－苯萃取除海水中的钙、镁离子的机理，探讨了用萃取法除海水中钙、镁离子制取制碱化盐用沙工业循环用水的可能。     

溴化铜作溴化剂合成3-氯- α-溴-苯基乙基酮

以间氯苯基乙基酮和溴化铜为原料，用乙酸乙酯与氯仿组成的混合液作溶剂合成了3－氯－α－溴－苯基乙基酮。考察了影响溴代收率的因素，最佳合成条件：溴化铜：间氯苯基乙基酮（摩尔比）为2.1∶1，反应在回流温度下进行，反应时间2.5h，收率可达91.9％。     

二（2—乙基己基）磷酸萃取L—异亮氨酸的研究

以二（２－乙基己基）磷酸（Ｄ２ＥＨＰＡ）－正辛烷及Ｄ２ＥＨＰＡ－正辛醇萃取Ｌ－异亮氨酸为对象,研究了Ｄ２ＥＨＰＡ浓度、Ｌ－异亮氨酸初始浓度以及ｐＨ值对萃取平衡分配系数的影响。结果表明,在实验研究涉及的ｐＨ值范围内,分配系数先随ｐＨ的增加而增大,在３．５〈ｐＨ〈５区域,ｐＨ值对分配系数的影响较小。分配系数还随Ｄ２ＥＨＰＡ浓度的增加而增大。正辛醇加入有机相,萃取分配系数增大。Ｄ２ＥＨＰＡ与Ｌ－异亮氨酸     

The Extraction and Separation of Ho,Y, and Er(III) with the Mixtures of Cyanex 302 and Another Organic Extractant

Abstract

The extraction and separation of Ho, Y, and Er(III) with the mixtures of bis(2,4,4‐trimetylpentyl)monothiophosphinic acid (Cyanex 302) and another organic extractant, such as acidic organic extractant (di‐2‐ethylhexyl phosphoric acid P204, 2‐ethylhexyl phosphoric acid mono‐2‐ethylhexyl ester P507, di‐2‐ethylhexyl phosphinic acid P229, and sec‐nonylphenoxy acetic acid CA‐100), neutral organic extractant (tri‐n‐butyl phosphate TBP, di‐(1‐metylheptyl)metyl phosphate P350, and branched trialkylphosphinic oxide Cyanex 925) or primary amine N1923, has been investigated in this paper. The extractability and separation ability for the Ho, Y, and Er with the mixtures of Cyanex 302 and organic extractants has been compared. The synergistic effect of the Ho, Y, and Er extraction with the mixtures of Cyanex 302 and P229, Cyanex 925, CA‐100, or N1923 has been explored and the synergistic enhancement coefficients have been calculated. At last, the Y³⁺ synergistic extraction with the mixtures of Cyanex 302 and CA‐100 has been determined and the extracted complex has been deduced.     

Modellierung des Stoffübergangs von Zinkionen an überströmten formstabilen Phasengrenzen

The inadequacy of the usually used film theory is shown by fitting experimental data of the zinc extraction with di(2‐ethylhexyl)phosphoric acid in the presence of a planar interface. It is explained why it is necessary to model the mass transfer carried out by an unsteady diffusion process. By introducing the flow‐dependent number of phase contacts as a function of the Reynolds number the phase contact time is described theoretically. In this way the approximation of the penetration model and the film penetration model are solved analytically. Subsequently, the model equations are validated by using experimental data.     

Micellar Extraction of Zinc with Di(2‐ethylhexyl)phosphoric Acid and the Addition of the Cationic Surfactant Cetyltrimethylammonium Bromide

The addition of surfactants can influence extraction processes. In cases where the surfactant concentration is above the critical micelle concentration, the mass transfer rate increases due to the formation of inverse micelles and, thus, through the mechanism of micellar extraction of zinc. The influence of the added surfactant cetyltrimethylammonium bromide on zinc extraction with the cation exchanger di(2‐ethylhexyl)phosphoric acid was analyzed based on extraction equilibrium and mass transfer experiments. The observed experimental results are explained phenomenologically.     

Mizellare Extraktion von Zink mit Di(2‐ethylhexyl)phosphorsäure in Gegenwart des Tensids Cetyltrimethylammoniumbromid

Addition of surfactants can influence extraction processes. In the case were the surfactant concentration is above the critical micelles concentration the mass transfer rate increases by the formation of inverse micelles and therefore the micellar extraction mechanism of zinc. The influence of the added surfactant cetyltrimethylammonium bromide (CTAB) on zinc extraction with the cation exchanger di(2‐ethylhexyl)phosphoric acid (D₂EHPA) is analysed based on extraction equilibriums and mass transfer experiments. The observed experimental results are explained phenomenologically.     

Enantioselective Extraction of Racemic Mandelic Acid by Di(2‐ethylhexyl) Phosphoric Acid and Tartaric Acid Derivatives as Mixed Complex Chiral Selectors

The distribution behavior of mandelic acid (MA) enantiomers was examined in a two‐phase system containing di(2‐ethylhexyl) phosphoric acid (D2EHPA) with two tartaric acid derivatives as complex chiral selectors in n‐octanol. Factors affecting the extraction were investigated, including the structure and concentration of tartaric acid as well as the concentration of D2EHPA and D,L‐MA. The results showed that both the distribution ratio and enantioselectivity were greatly improved by using a complex chiral selector rather than using the tartaric acid derivative by itself. Finally, it was found that the formation of mixed complex chiral selectors by mixing two tartaric acid derivatives with D2EHPA can improve the capacity of enantioselective extraction.     

Optimization of Settling Behavior for an Efficient Solvent‐Extraction Process for Biobased Components

Extraction is a downstream process option in biobased processes. Because knowledge of phase‐separation behavior is essential for designing efficient separation processes, this study investigates the settling and coalescence behavior of biobased extraction systems by using a standard laboratory‐scale settling cell. The influence of different buffer media and Escherichia coli cells on coalescence was determined for the reactive extraction of hexane‐1,6‐diamine with isostearic acid and di(2‐ethylhexyl)phosphoric acid by using kerosene and oleyl alcohol as diluents. As a result, an increasing pH value of the buffer significantly increases the settling time. The presence of E. coli cells hinders phase separation of the investigated systems, in particular, with dispersed organic phases.     

Separation of cadmium(II) from spent nickel/cadmium battery by emulsion liquid membrane

Experiments were conducted to investigate the separation of cadmium(II) from spent nickel/cadmium battery by emulsion liquid membrane. Liquid membrane mainly consisted of a diluent (kerosene), a surfactant (Span 80), a carrier (di(2‐ethylhexyl) phosphoric acid, D2EHPA) and an internal phase (sulfuric acid). Main research effort was focused on the identification of optimal parameters affecting the separation process, such as D2EHPA (4.4 vol%), Span 80 (6.6 vol%), pH in the external phase (3.0), treat ratio (0.4), agitation time (10 min), and sulfuric acid concentration (1500 mol / m³). With the selected emulsion liquid membrane to separate cadmium(II) from the leaching solution of spent nickel/cadmium battery, the fraction extracted of cadmium(II) ions (0.963) was much more than that of nickel(II) ions (0.026). The organic membrane phase after demulsification was re‐mulsification and recycled up to eight times.     

The adjustable synergistic effects between acid–base coupling bifunctional ionic liquid extractants for rare earth separation

Two of the most widely used industrial extractants for rare earth elements (REEs), that is, di(2‐ethylhexyl)phosphoric acid (HDEHP) and 2‐ethyl(hexyl) phosphonic acid mono‐2‐ethylhexyl ester (HEH[EHP]) were developed into [DEHP]^? type acid–base coupling bifunctionalized ionic liquids (ABC‐BILs) and [EHEHP]^? type ABC‐BILs, respectively. The combinations of ABC‐BIL extractants revealed synergistic effects for REEs. Seven different combinations of ABC‐BILs and five kinds of REEs confirmed the novel synergistic extraction. Some synergy coefficients of the combined ABC‐BILs were bigger than those of mixed HDEHP and HEH[EHP] by two orders of magnitude. The first synergistic extraction produced by ionic liquid extractants in the field of solvent extraction was reported in this article. The novel synergistic extraction from combined ABC‐BILs extractants revealed highly efficient and environmentally friendly potential in both of academic research and industrial application for REEs separation. © 2014 American Institute of Chemical Engineers AIChE J, 60: 3859–3868, 2014     

酸式磷酸二辛酯的合成及其在膨胀型阻燃聚丙烯中的偶联作用

以三氯氧磷、异辛醇为原料合成的酸式磷酸二辛酯是一种含磷阻燃偶联剂 ,作者研究了其对膨胀型阻燃剂 (IFR) /聚丙烯 (PP)共混材料的偶联作用。力学性能、阻燃性能测试和SEM结果表明 :酸式磷酸二辛酯是体系有效的偶联剂 ,在不损害原有阻燃性能的条件下 ,提高了共混材料的力学性能 ,明显改善共混体系的形貌结构 ,是一种可选的阻燃偶联剂。经酸式磷酸二辛酯偶联的IFR/PP拉伸强度、抗冲击强度和水平燃烧性能分别为 2 5 4MPa、4 0 2kJ·m-2 和GB 2 40 8—80II- 0 5mm ,离火 36s自熄 ,未加偶联剂的对应值为 2 2 5 7MPa、3 2 7kJ·m-2 和GB 2 40 8— 80II- 1mm ,离火 39s自熄。