Intensified reactive extraction of 4-hydroxypyridine with di(2-ethylhexyl) phosphoric acid in 1-octanol by using tributyl phosphate

The efficient separation of amphoteric organic compounds from dilute solutions is of great importance in the industrial field. In the present work, the reactive extractions of 4-hydroxypyridine(4-HP) with tributyl phosphate(TBP), di(2-ethylhexyl) phosphoric acid(D2EHPA) and TBP + D2EHPA dissolved in 1-octanol were investigated, respectively. The influences of the initial concentrations of TBP, D2EHPA and TBP + D2EHPA on distribution ratio(D) were discussed, as well as the reactive extraction mechanism were proposed. The obvious intensification effect was observed when the mixture of TBP and D2EHPA was used as extractant. The best extraction conditions were found to be of the molar ratio of D2EHPA and TBP at 2:1 and the equilibrium aqueous pH at 3.50-4.50. D values increased with the increase of the total concentration of TBP and D2EHPA in 1-octanol. Especially, the analysis on the extraction mechanisms clearly indicate(i) TBP in 1-octanol shows negligible reactive extraction toward 4-HP,(ii) D2EHPA in 1-octanol exhibits moderate extraction effect by forming 4-HP:D2EHPA(1:1) and 4-HP:2D2EHPA(1:2) type complexes, while(iii) D2EHPA in TBP/1-octanol demonstrates the maximum distribution ratio with the 4-HP:D2EHPA(1:1) type complex domination. The discussion provides new insights on the mechanism and opens a new way for the intensified extraction of amphoteric organic compounds by using the mixture of multiple extractants in the diluent.

Synergistic extraction of rare earth by mixtures of 2-ethylhexyl phosphoric acid mono-2-ethylhexyl ester and di-(2-ethylhexyl) phosphoric acid from sulfuric acid medium

The extraction of Nd^3＋ and Sm^3＋, including the extraction and stripping capability as well as the separation effect of Nd^3＋ or Sm^3＋, from a sulfuric acid medium, by mixtures of di-（2-ethylhexyl） phosphoric acid （HDEHP, H2A2（0）） and 2-ethylhexyl phosphoric acid mono-2-ethylhexyl ester （HEH/EHP, H2L2（0）） were studied. The distribution ratios and synergistic coefficients of Nd^3＋ and Sm^3＋ in different acidities were also determined. A synergistic extractive effect was found when HDEHP and HEH/EHP were used as mixed extractants for Sm^3＋ or Nd^3＋. The chemical compositions of the extracted complex were determined as Nd.（HA2）2-HL2 and Sm.（HA2）2-HL2. The extraction equilibrium constants, enthalpy change, and entropy change of the extraction reaction were also determined.

Adsorption by Liquid-Liquid Extraction of Hg(II) from Aqueous Solutions Using the 2-Butyl-imidazolium Di-(2-ethylhexyl) Phosphate as Ionic Liquid

In this work, a novel room temperature ionic liquid (2-butyl-imidazolium di-(2-ethylhexyl) phosphate) ([C4mim] [D2EHPA]) was synthesized and tested as extractant in the mercury(II) liquid-liquid extraction. The effects of parameters such as aqueous to organic phase’s volume ratio, metal concentration IL concentration, pH levels, ionic strength, and temperature were reported. For the extraction of metal, [C4mim]3[R.HR]3[HgCl2]org and [C4mim]3[R.HR]3 [HgClOH]org species were formed where (H2R2) was D2EHPA. In the case of ionic strength, the results showed that the addition of sodium acetate at 0.302 mmol·L?1 to the aqueous phase strongly increased the mercury extraction yield (R = 100%). The extracted species were investigated by a calculation program using CHEAQS V. L20.1 inorder to determine the relation between the percentages of the extracted species and the extraction yield. The results showed that the extracted species in the best conditions were HgCl2 and HgClOH with respective percentages 80.66% and 18.29%.

Combination of on-line preconcentration by di(2-ethylhexyl) phosphoric acid resin in the presence of complexing agent with microwave plasma-atomic emission spectrometry for the determination of rare earths

The adsorption of rare earths,lanthanum,cerium,neodymium,and yttri um by di(2-ethylhexyl) phosphoric acid(D2EHPA) resin in the presence of a compl exing agent,EDTA,was investigated. Flow injection was selected as the injectin g method. Various parameters,sample pH,sample loading time,sample flow rate,EDTA concentration,EDTA flow rate,eluent concentration,and eluent flow rate,were studied and optimized. Under the optimum conditions,the method allowed the determination of rare earths with detection limits of 1.09 μg/L(lanthanum),3 .31 μg/L(cerium),2.05 μg/L(neodymium),and 1.25 μg/L(yttrium) . High repea tabilities were obtained for all the four rare earths(RSD【5%) . The proposed met hod was applied to the determination of the rare earths in water samples with a recovery range of 95.8%-103.3%.

4-叔丁基-2-(α-甲基苄基)苯酚—二-(2-乙基己基)磷酸协同体系萃取盐湖卤水中的铯

铯是重要的战略资源。溶剂萃取法因效率高、成本低、处理量大等优点被广泛应用于铯的分离提取。使用4-(叔丁基)-2-(α-甲基苄基)苯酚(t-BAMBP)萃取体系分离提取铯时会有强碱性萃取尾液产生,这使得该萃取体系的使用将面临着破坏生态、提高成本等诸多困难,尤其对盐湖生态而言,更是极大的挑战。文章采用4(-叔丁基)-2(-α-甲基苄基)苯酚(t-BAMBP)/二(-2-乙基己基)磷酸(P204)协同萃取体系对盐湖卤水中低品位铯的分离提取工艺开展了研究,考察并优化了萃取、反萃工艺条件。实验结果表明,使用1 mol·L^(-1)的t-BAMBP和0.05 mol·L^(-1)的P204组成的有机相在相比为1/4的条件下三级逆流串级萃取卤水,铯的萃取率可达92.62%;使用0.5 mol·L^(-1)的盐酸在15/1相比的条件下三级逆流串级反萃铯的反萃率可达97.27%,铯浓度可初步富集至2.16 g·L^(-1)。本研究为盐湖卤水中的低品位铯的富集提供了新的工艺方法,拓展了溶剂萃取法提取分离铯的应用领域,对低品位铯资源的开发利用及保障我国战略资源安全具有重要意义。

叶酸对邻苯二甲酸二(2-乙基己基)酯(DEHP)暴露导致小鼠胆汁淤积型肝损伤的保护作用

目的探讨叶酸对邻苯二甲酸二(2-乙基己基)酯(DEHP)暴露诱发小鼠胆汁淤积型肝损伤的保护作用及其机制。方法将ICR小鼠随机分为对照(Control)组、叶酸高剂量(H-FA)组、DEHP组、DEHP+叶酸低剂量(DEHP+L-FA)组、DEHP+叶酸高剂量(DEHP+H-FA)组,每组6只。H-FA组、DEHP+L-FA组和DEHP+H-FA组给予相应剂量的叶酸灌胃,Control组和DEHP组灌胃等量的PBS溶液。2 h后,DEHP组、DEHP+L-FA组和DEHP+H-FA组给予含200 mg/kg DEHP的玉米油,Control组和H-FA组灌胃等量的纯玉米油,共灌胃4周。记录小鼠每天的体质量和摄食量,收集血液和肝组织。生化仪检测血清总胆汁酸(TBA)和碱性磷酸酶(ALP)水平;HE染色观察肝组织病理变化;试剂盒检测肝组织丙二醛(MDA)和超氧化物歧化酶(SOD)含量;LC-MS/MS检测小鼠血清胆汁酸谱;Western Blot法检测肝脏胆汁酸代谢相关蛋白的表达水平。计量资料多组间比较采用单因素方差分析,进一步两两比较采用LSD-t检验。结果与对照组相比,DEHP组小鼠每日摄食量明显下降,体质量从第10天开始显著降低(P值均<0.05);与DEHP组相比,DEHP+L-FA组与DEHP+H-FA组小鼠的体质量和摄食量基本不变(P值均>0.05)。与对照组相比,DEHP组小鼠肝质量指数、血清TBA及ALP均显著升高(P值均<0.05),肝组织可见汇管区扩大,胆管变形增生及少量炎性细胞浸润;与DEHP组相比,DEHP+L-FA组与DEHP+H-FA组小鼠肝质量指数均明显下降(P值均<0.01),DEHP+H-FA组的血清TBA和ALP均显著下降(P值均<0.05),叶酸干预后小鼠肝组织形态结构明显改善。与对照组相比,DEHP组小鼠肝脏SOD含量明显下降(P<0.05),肝脏MDA含量明显增加(P<0.01);与DEHP组相比,MDA和SOD含量在DEHP+H-FA组均显著回调(P值均<0.05)。与对照组相比,DEHP组小鼠血清中α-鼠胆酸(α-MCA)、β-鼠胆酸(β-MCA)、去氧胆酸(DCA)、石胆酸(LCA)、牛磺胆酸(TCA)、牛磺去氧胆酸(TDCA)、牛磺熊去氧胆酸(TUDCA)、牛磺-β-鼠胆酸(T-β-MCA)、牛磺-α-鼠胆酸(T-α-MCA)、牛磺猪去氧胆酸(THDCA)、牛磺石胆酸(TLCA)均明显升高(P值均<0.05),熊去氧胆酸(UDCA)明显降低(P<0.05);与DEHP组相比,血清中DCA、LCA、TCA、TDCA、TUDCA、T-β-MCA、T-α-MCA、THDCA、TLCA在DEHP+H-FA组均明显回调(P值均<0.05)。与对照组相比,DEHP组小鼠肝脏FXR和CYP3A11蛋白表达量均明显增加(P值均<0.01),CYP7A1和MRP2蛋白表达量显著降低(P值均<0.01);与DEHP组相比,肝脏FXR和CYP3A11蛋白表达量在DEHP+L-FA组和DEHP+H-FA组中均明显下调(P值均<0.05);MRP2蛋白表达量在DEHP+L-FA组DEHP+H-FA组中均显著上调(P值均<0.05);CYP7A1蛋白表达量在DEHP+H-FA组中显著上调(P<0.05)。结论叶酸对DEHP暴露导致的小鼠胆汁淤积型肝损伤有保护作用,其机制可能是调节胆汁酸合成、代谢与转运从而维持胆汁酸稳态。

邻苯二甲酸二(2-乙基己基)酯(DEHP)诱发小鼠胆汁淤积和肝损伤的作用机制

目的探讨邻苯二甲酸二(2-乙基己基)酯(DEHP)诱发小鼠胆汁淤积和肝损伤机制研究。方法体内实验:将成年雌性ICR小鼠随机分为对照组(玉米油)、DEHP组(200 mg·kg^(−1)·d^(−1)),共灌胃4周,建立胆汁淤积模型。收集所有小鼠血液与肝组织,生化仪检测血清、肝脏总胆汁酸(TBA)水平,酶标仪检测ALP、GGT;HE染色观察肝组织病理变化;实时定量PCR检测肝脏炎症因子IL-1β、IL-6和TNF-α的表达水平;液相色谱-三重四级杆质谱仪(LC-MS/MS)检测小鼠肝脏胆汁酸谱。体外实验:培养小鼠肝细胞AML-12,使用DEHP(250μmol/L)以及去氧胆酸(DCA)(125μmol/L)和鹅去氧胆酸(CDCA)(125μmol/L)处理细胞24 h,实时定量PCR检测细胞炎性因子IL-1β、IL-6和TNF-α的mRNA水平。计量资料两组间比较采用成组t检验,多组间比较采用单因素方差分析,进一步两两比较采用LSD-t检验。结果体内实验显示:与对照组相比,DEHP组小鼠肝体比,血清TBA、ALP、GGT及肝脏TBA均显著升高(t值分别为−4.396、−5.109、−8.504、−3.792和−7.974,P值均<0.05)。与对照组相比,肝脏胆汁酸谱中胆酸(CA)、CDCA、牛磺鹅去氧胆酸(TCDCA)、DCA及熊去氧胆酸(UDCA)均显著升高(t值分别为−2.802、−3.177、−2.633、−2.874和−2.311,P值均<0.05)。DEHP组小鼠肝脏HE染色显示为汇管区扩大、胆管变形、胆管周围伴有炎性细胞浸润,且肝脏炎症因子IL-1β、IL-6和TNF-αmRNA水平均显著升高(t值分别为−2.539、−2.823和−4.636,P值均<0.05)。体外实验显示:0~1000μmol/L DEHP处理后肝细胞活力实际数值相差不超过15%,分别使用125、250以及500μmol/L的DEHP刺激后,肝细胞的炎症因子IL-1β、IL-6和TNF-αmRNA水平均明显升高(P值均<0.05)。与单独使用DEHP刺激相比,CDCA联合DEHP刺激上调了细胞炎症因子IL-1βmRNA水平(P<0.01);DCA与DEHP联合刺激可显著增加细胞炎症因子IL-1β和IL-6的mRNA水平(P值均<0.01)。结论DEHP暴露导致小鼠胆汁淤积肝病的发生并诱发肝脏炎症,这可能与其促进有毒胆汁酸的产生进而加剧炎性因子分泌有关。

Tb(III) Transport in Dispersion Supported Liquid Membrane System with D2EHPA as Carrier in Kerosene

The transport of Tb（III） in dispersion supported liquid membrane（DSLM） with polyvinylidene fluoride membrane（PVDF） as the support and dispersion solution including HCl solution as the stripping solution and di（2-ethylhexyl） phosphoric acid（D2EHPA） dissolved in kerosene as the membrane solution, has been studied. The effects of pH value, initial concentration of Tb（III） and different ionic strength in the feed phase, volume ratio of membrane solution to stripping solution, concentration of HCl solution, concentration of carrier, different stripping agents in the dispersion phase on the transport of Tb（III） have also been investigated, respectively. As a result, the optimum transport conditions of Tb（III） were obtained, i.e., the concentration of HCl solution was 4.0 mol/L, the concentration of D2EHPA was 0.16 mol/L, the volume ratio of membrane solution to stripping solution was 30：30 in the dispersion phase and pH value was 4.5 in the feed phase. Ionic strength had no obvious effect on the transport of Tb（III）. Under the optimum conditions, the transport percentage of Tb（III） was up to 96.1% in a transport time of 35 min when the initial concentration of Tb（IIl） was 1.0× 10 -4 mol/L. The diffusion coefficient of Tb（III） in the membrane and the thickness of diffusion layer between feed phase and membrane phase were obtained and the values were 1.82×10 -8 m2/s and 5.61 um, respectively. The calculated results were in good agreement with the literature data.

Structure and aggregation behavior of cobalt-di(2-ethylhexy1)-phosphoric acid complexes in solvent extraction systems

Structure and aggregates formed from cobalt di(2 ethylhexyl)phosphoric acid (Co HDEHP) complexes in solvent extraction systems were investigated by FT IR, UV Vis and photon correlation spectroscopic (PCS) techniques. Results showed that the Co HDEHP complex displayed a dehydrated tetrahedral coordination structure of the chelate type in n heptane and the aggregates were rather small. The addition of co surfactant to the solvent produced a series of effect on the physicochemical nature of the molecular aggregates. In the presence of 2 octanol, a partially hydrated octahedral coordination structure was formed in equilibrium with the dehydrated tetrahedral structure for the Co HDEHP aggregates in the organic phase and the equilibrium was found to be affected by the ionic strength of the aqueous phase. Furthermore, the FT IR results showed that Co HDEHP complex in the presence of 2 octanol displayed a bridge coordination between the cobalt and the extractant molecules.

P204-Cyanex923混合溶剂萃取铟

研究了 P2 0 4、P50 7、Cyanex 92 3及 P2 0 4单一体系与 3种中性有机磷萃取剂 (Cyanex 92 3、TRPO、TBP)组成的混合体系对 In( )、Fe( )的萃取和反萃性能 .发现在 P2 0 4中加入 Cyanex92 3使 In( )的萃取率略有下降 ,反萃率提高 .红外光谱分析证明 P2 0 4与 Cyanex 92 3存在缔合作用 ,抑制 P2 0 4与 In( )和 Fe( )的离子交换反应 ,可以提高过程的反萃率 .

二-(2-乙基己基)磷酸P204与三烷基叔胺N235协同萃取钼

研究了P204(二-(2-乙基己基)磷酸,HA)和N235(三烷基叔胺,R3N)二元体系在HC l介质中对金属钼的萃取。结果表明,P204和N235混合萃取剂在萃取钼时存在协同效应,并且在N235摩尔分数为0.7时协萃系数为2.24;考察了溶液酸度、P204或N235浓度及温度对萃取钼的影响,确定了协萃络合物为(R3NH)3.HMo8O26.(HA)2,并比较了负载前后有机相的红外光谱。

二-(2-乙基己基)磷酸与仲壬基苯氧基取代乙酸混合体系对稀土元素的萃取

考察了二-(2-乙基己基)磷酸(D2EHPA,H2A2)和仲壬基苯氧基取代乙酸(CA100,H2B2)混合体系在HCl介质中对15种镧系元素(除钷)及钇的萃取性能,计算了稀土元素间的分离系数,并比较了混合萃取体系与D2EHPA单独萃取体系对稀土元素的分离能力。研究了D2EHPA-CA100混合体系对镧的协同萃取机理,用斜率法和恒摩尔法探讨了萃取反应方程式,考察了酸度、萃取剂浓度及温度对萃取性能的影响。结果表明:D2EHPA-CA100混合体系对镧系元素的协同效应随原子序数的增加而减弱。在适当的萃取剂配比下,此混合体系对某些稀土元素的分离能力优于D2EHPA,可用于这些稀土元素的分离。D2EHPA-CA100混合体系协同萃取镧的萃合物组成为LaH5A6B2,反应为吸热反应。

二(2-乙基己基)磷酸络合萃取对氨基苯酚

二 (2 -乙基己基 )磷酸 (D2 EHPA)络合萃取对氨基苯酚 (PAP)。研究了稀释剂种类、溶液的初始 p H值等因素对稀溶液分配比 (D)的影响。溶液的初始 p H值 (p H2— 1 1 )对萃取结果影响较大 ,当初始 p H值在p Ka1 和 p Ka2 之间时 ,分配比出现峰值。稀释剂则主要是通过物理萃取实现。在同一浓度下 ,二 (2 -乙基己基 )磷酸的萃取能力随稀释剂的极性增大而提高 ,极性环境明显优于惰性稀释剂环境。红外光谱分析表明 ,络合萃取过程存在离子交换和离子缔合两种反应机制。

二(2-乙基己基)磷酸络合萃取邻氨基苯酚的研究

以二(2-乙基己基)磷酸(D2EHPA)为萃取剂,研究稀释剂种类、萃取剂浓度、溶液的初始pH值、溶液中甲(乙)醇等因素对邻氨基酚(OAP)稀溶液分配比(D)的影响.结果表明:溶液的初始pH值在7左右时,D有最大值;D值随二(2-乙基己基)磷酸浓度的增大而提高,且在极性环境要优于惰性环境;甲(乙)醇是影响萃取结果的主要因素.

P204萃取脱除铜精矿浸出液中铁

从含砷硫化铜精矿浸出液中萃取除铁是后续制备砷酸铜的一道工序,P204可从硫酸介质中选择性地萃取铁离子.实验结果表明,当有机相组成中P204为30%(-),相比1:1,pH≈1时,通过三级萃取,铁的萃取率达93%以上,铜和砷几乎不被萃取,萃余液中残铁含量降至9mg/L以下.

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-异亮氨酸生成萃合比为1∶1或2∶1的萃合物。证实了在D2EHPA萃取L-异亮氨酸的过程中存在着质子转移反应。建立的萃取平衡分配系数关联式的拟合精度是令人满意的。

二(2-乙基己基)磷酸萃取L-精氨酸

The extraction of L-Arginine with di(2-ethylhexyl)phosphoric acid(D2EHPA) has been studied as functions of equilibrium pH, D2EHPA concentration, L-Arginine equilibrium concentration, NH 4Cl concentration and temperature. The beffer extraction results were obtained in condition of pH=5～7, D2EHPA 0.2～0.4 mol/L, NH 4Cl<0.2 mol/L and low temperature. The equilibrium concentration of L-Arg depends on the saturation extraction capacity.

溶剂萃取法提取废旧碱性电池中的有价成分

为回收利用废旧电池 ,进行了溶剂萃取法提取碱性废弃电池中锌、锰金属的试验研究。选择南孚 (AA)碱性废电池为处理样品 ,通过粉碎、水浸、酸浸等步骤 ,获得含锌、锰离子的稀溶液 ,并利用模拟体系得到的萃取结果进行浸出液的萃取性能试验研究。结果表明 ,每个废电池填充物中含锌和锰分别为 0 .2 5g和 0 .36g ,具有可观的回收价值 ;采用完全皂化的二 (2 乙基己基 )磷酸 (D2EHPA) /煤油为萃取剂提取含锌锰的酸浸出液 ,一级萃取就可获得 60 %以上的提取率。

D2EHPA萃取稀土的有机相红外光谱及添加DMHPA的影响

本文研究了部分皂化的二（２－乙基己基）磷酸（Ｄ２ＥＨＰＡ）－正庚烷体系萃取稀土离子Ｙ３＋、Ｐｒ３＋、Ｎｄ３＋、Ｅｕ３＋后有机相的傅里叶变换红外光谱（ＦＴ－ＩＲ）。发现不同稀土离子与萃取剂的配位能力有差异，并且皂化度对萃取有机相中Ｐ＝Ｏ谱带的频率和吸收强度皆有影响。在Ｄ２ＥＨＰＡ中加入二（１－甲基庚基）磷酸（ＤＭＨＰＡ）。

络合萃取法处理二甲胺废水

采用络合萃取法处理二甲胺(DMA)废水,考察了萃取剂的种类和用量、溶液pH值、油与水比对二甲胺萃取效果的影响。实验结果表明,以P204为萃取剂、环己烷为稀释剂时,P204与DMA以1∶1形式络合,萃取是一个放热且快速反应过程,反应热ΔH=-6.50 kJ/mol。在油与水比为1∶4、萃取剂稀释剂体积比为1∶9、废水pH=11.87的条件下,DMA的一级萃取率为93.0%。P204负载DMA的红外谱图研究表明,P204络合萃取二甲胺同时存在离子缔合成盐机制和氢键缔合机制。