磷酸三丁酯和异丁基十二烷基亚砜萃取铀（Ⅳ）的研究

研究了以甲苯作稀释剂时，磷酸三丁酯(TBP)和异丁基十二烷基亚砜(BDSO)萃取铀(Ⅳ)的机理。考察了硝酸浓度、温度对分配比的影响，求得萃取反应的热力学函数。考察了萃取剂浓度对协萃系数的影响．发现TBP和BDSO具有协萃效应，最大协萃系数在TBP：BDSO=1：1处。     

二（2-乙基己基）磷酸/磷酸三丁酯复合萃取剂协萃对氨基苯甲酸

为强化两性官能团化合物的萃取分离性能,以对氨基苯甲酸（PABA）为被分离溶质,二（2-乙基己基）磷酸（D2EHPA）/磷酸三丁酯（TBP）/正庚烷的混合物为萃取剂进行了萃取平衡特性的研究,考察了溶液的pH值、D2EHPA浓度、TBP浓度对于萃取平衡的影响,建立了复合萃取剂协同萃取PABA的萃取平衡分配系数的表达式.结果表明,D2EHPA/TBP/正庚烷复合萃取剂萃取PABA具有明显的协萃效应,协萃机理为D2EHPA及TBP分别与PABA的Lewis碱性官能团（—NH2）和Lewis酸性官能团（—COOH）缔合形成亲油性更强的萃合物,且D2EHPA与TBP的浓度差异越小,协萃效应越明显.根据萃取平衡分配系数表达式拟合求取了表观萃取平衡常数,复合萃取剂的值远大于D2EHPA、TBP单独作为萃取剂的值,进一步证明了本文提出的协萃机理.     

磷酸三丁酯/丁酸乙酯体系协同萃取提锂的研究

以磷酸三丁酯(TBP)为萃取剂、丁酸乙酯(EB)和FeCl_3为协萃剂,煤油为稀释剂,从盐湖卤水中进行了萃取提锂的实验研究。系统考察了卤水酸度、萃取剂浓度、铁锂摩尔比、相比等因素对锂萃取率的影响。体系的最佳工艺条件为:TBP、EB、煤油的体积分数分别为40%、20%和40%;卤水酸度为0.05 mol/L;Fe/Li摩尔比为1.5;相比为O/A=2/1;反萃剂为2 mol/L的HCl,反萃相比O/A=1/1。在最佳萃取条件下,锂的单级萃取率最高可达87.12%。应用稀盐酸对负载有机相进行反萃,锂的单级反萃率超过90%。本文的研究结果表明:TBP/EB/FeCl_3/煤油体系对从盐湖卤水中分离锂具有较好的应用前景。     

盐酸胍与溴化十六烷基吡啶从碱性氰化液中萃取Au(Ⅰ)

以正戊醇为稀释剂,考察了盐酸胍与溴化十六烷基吡啶总浓度为0.06 mol/L时,体系对Au(Ⅰ)的协萃效应.结果表明,在整个浓度组成范围内均有协萃效应(协萃效应系数R>1),且有机相中盐酸胍与溴化十六烷基吡啶的浓度分别为0.05和0.01 mol/L时,Au(Ⅰ)的协萃系数为13.98.考察了平衡时间、相比、待萃液pH值及Au(Ⅰ)浓度对Au(Ⅰ)协同萃取性能的影响.对盐酸胍与溴化十六烷基吡啶萃取Au(Ⅰ)的可能机理进行了分析.分别用Na2SO3和KSCN为反萃剂反萃Au(Ⅰ),KSCN的反萃性能明显比Na2SO3好,KSCN浓度为12 g/L、反萃时间30 min、相比.A/O=1时,Au(Ⅰ)的反萃率为98.5%.     

盐酸胍与溴化十六烷基吡啶从碱性氰化液中萃取Au(I)

以正戊醇为稀释剂,考察了盐酸胍与溴化十六烷基吡啶总浓度为0.06 mol/L时,体系对Au(I)的协萃效应. 结果表明,在整个浓度组成范围内均有协萃效应(协萃效应系数R>1),且有机相中盐酸胍与溴化十六烷基吡啶的浓度分别为0.05和0.01 mol/L时,Au(I)的协萃系数为13.98. 考察了平衡时间、相比、待萃液pH值及Au(I)浓度对Au(I)协同萃取性能的影响. 对盐酸胍与溴化十六烷基吡啶萃取Au(I)的可能机理进行了分析. 分别用Na2SO3和KSCN为反萃剂反萃Au(I),KSCN的反萃性能明显比Na2SO3好,KSCN浓度为12 g/L、反萃时间30 min、相比A/O=1时,Au(I)的反萃率为98.5%.     

TBP对LIX84由Cu2+-NH3-Cl——H2O系萃取铜及氨的影响

以Cu2+-NH3-Cl--H2O氨性溶液为被萃水相,在LIX84中添加磷酸三丁酯(TBP),考察了有机相中TBP浓度、被萃水相铜离子浓度、总氨浓度和pH值及相比、LIX84浓度对铜萃取率、共萃氨量的影响. 结果表明,随LIX84中TBP浓度升高,铜萃取率变化不大,负载有机相的共萃氨量明显降低. 有机相中TBP浓度为0.1 mol/L、LIX84浓度为40%、被萃水相铜离子浓度25 g/L、总氨浓度3 mol/L及pH值9.1、相比1:1、萃取时间30 min时,铜萃取率约为81%,与未添加TBP时基本一致,而负载有机相的共萃氨量由未添加TBP时的260 mg/L降至添加TBP后的85 mg/L.     

盐酸介质中磷酸三丁酯萃取分离铬(Ⅵ)

为了深入研究在盐酸介质中TBP萃取Cr(Ⅵ )的萃取行为 ,分别以煤油、四氯化碳、二甲苯为稀释剂 ,进行萃取平衡特性研究 ,考察了酸度、铬的初始浓度、有机相TBP含量以及温度对萃取平衡的影响。实验结果表明 :温度和稀释剂种类对萃取分配比的影响较小 ,酸度、TBP浓度和铬初始浓度对分配比影响较大。萃取过程所形成的萃合物为HCrO3 Cl·2TBP和HCrO3 Cl·3TBP。TBP在盐酸介质中萃取铬为吸热过程 ,其过程热为17.99kJ/mol。     

粉煤灰酸浸溶液中铁铝离子的萃取分离

采用N503和TBP、正辛醇、煤油组成的复合萃取体系,对粉煤灰酸浸溶液中的铝与铁进行萃取分离,考察盐酸浓度、氯离子浓度、萃取剂比例对Fe3+萃取率的影响,以低浓度HCl溶液反萃负载铁有机相,并通过逆流实验确定最佳工艺条件. 结果表明,采用N503:TBP:正辛醇:煤油=3:1:1:5(j)的萃取体系,在初始铁浓度为0.96 mol/L、铝浓度为0.22 mol/L、萃取相比O/A=2:1条件下,经5级逆流萃取,Fe3+的萃取率大于99.8%,铝几乎没有损失. 用0.01 mol/L HCl溶液作反萃剂,反萃相比O/A=2.5:1,经6级逆流反萃,反萃液中铁浓度达1.8 mol/L. 分析了有机相负载铁前后官能团的红外光谱图.     

用协萃体系从多金属废水中萃取Ni~(2+)和Co~(2+)（英文）

用协同萃取体系LIX 63和Versatic 10添加/不添加TBP从模拟多金属废水中萃取Ni~(2+)和Co~(2+),并去除杂质离子Mn~(2+),Mg~(2+)和Ca~(2+).向LIX 63/Versatic 10协同萃取体系中加入TBP用于加快Ni~(2+)的反萃,考察了萃取、反萃条件对Ni~(2+)和Co~(2+)萃取率、杂质去除率的影响.结果表明,Lix63,Versatic10和TBP浓度分别为0.6,0.4,0.8 mol/L时,Ni~(2+)和Co~(2+)的协萃系数达到最大,分别为33.29和8.23,且30 min内Ni~(2+)的反萃率达到90%.确定较优萃取操作条件为:萃取温度40±0.5℃、萃取平衡p H=4.5、萃取相比A/O 1:1、皂化率40%;反萃过程用1 mol/L H2SO4为反萃剂,根据Mc Cabe–Thiele图,在萃取相比A/O 1:1的条件下,经过三级逆流萃取,Ni~(2+)和Co~(2+)的萃取率分别达98.6%和99.9%,在反萃相比A/O为1:10的条件下,经三级逆流反萃,负载反萃水相含88.12 g/L Ni~(2+),4.52 g/L Co~(2+),1.21 g/L Mn~(2+),0.27 g/L Mg~(2+),Ca~(2+)低于0.2 mg/L.     

用磷酸三丁酯萃取分离硫酸铵母液中的HCN

研究了磷酸三丁酯(TBP)-磺化煤油体系从重庆某企业甘氨酸生产副产物硫酸铵母液中萃取分离HCN的工艺,考察了萃取体系、TBP体积分数、母液初始pH值、相比(Vorg∶Vaq)对萃取HCN的影响以及氢氧化钠浓度、相比(Vaq∶Vorg)和平衡pH值对HCN反萃的影响。结果表明:选用TBP作为萃取剂能够对硫酸铵母液中的HCN进行快速有效的萃取;TBP体积分数、母液初始pH值及相比对HCN萃取率影响显著;以含体积分数35%TBP的有机相作萃取剂,在相比(Vorg∶Vaq)为2∶1的条件下,pH值为2.92的含氰1.71 g/L的硫酸铵母液经3级错流萃取,萃余液中含氰低于0.5 mg/L,氰的萃取率接近100%;在相比(Vaq∶Vorg)为1∶1条件下,以0.6 mol/L的氢氧化钠为反萃液,控制反萃液平衡pH值大于13.0,氰的单级反萃率大于96%;含氰0.78 g/L的有机相在相比为1∶1条件下,经过2级错流反萃,氰基本上被反萃完全,贫有机相不经过处理可循环使用。     

络合萃取法对煤制气高浓度含酚废水的资源化处理

用磷酸三丁酯(TBP)为萃取剂和煤油为稀释剂,对煤制气过程中产生的高浓度含酚废水进行了络合萃取处理,并用氢氧化钠溶液为反萃取剂对负载有机相进行了反萃取。分别研究了废水pH、TBP体积分数对萃取及氢氧化钠溶液浓度对反萃取的影响,并对萃取和反萃取过程中有机相的重复使用问题进行了探讨。结果表明,当废水的pH为3～6时,萃取率可达90%以上,CODCr去除率达到80%以上;当氢氧化钠质量分数为4%～10%时,反萃取率可达80%以上;TBP-煤油有机相可在萃取和反萃的过程中多次重复使用。     

磷酸三丁酯萃取体系从盐湖卤水提取锂

选取磷酸三丁酯（TBP）为萃取剂,磺化煤油为稀释剂,氯化铁（FeCl₃•6H₂O）为共萃取剂从盐湖提钾老卤萃取锂。考察了不同因素对萃取率的影响,结果发现,相比（O/A）对萃取率的影响最大,铁锂物质的量比次之,TBP含量（体积分数）影响最小;由单因素实验及正交实验的研究分析得出萃取锂的最优工艺条件：φ（TBP）=80%、相比（O/A）为2.0、n(Fe)∶n(Li)=1.5、c(H⁺)=0.05 mol/L、振荡时间为5 min;该工艺萃取效率高,单级萃取率可达91.4%,且具有良好的稳定性和重现性,可为工业扩大化生产提供可靠的参考依据。     

磷酸三丁酯和二异丙醚溶剂萃取 体系净化湿法磷酸的研究

以磷酸三丁酯（TBP）与二异丙醚为溶剂,采用溶剂萃取法净化湿法磷酸。研究了萃取剂中TBP体积分数、相比、萃取时间、搅拌转速、反萃取剂加入量对湿法磷酸净化效果的影响,确定了TBP与二异丙醚混合溶剂体系净化湿法磷酸的工艺条件。适宜工艺条件：萃取剂组成为TBP与二异丙醚体积比为1∶1,有机相与水相的体积比为 4∶1,萃取时间为25 min,搅拌转速为300 r/min,反萃取剂加入量为萃取相体积的20%。在此条件下,TBP与二异丙醚萃取体系对金属阳离子和氟离子有较好的分离能力。     

SOLVENT EXTRACTION OF COBALT(II) WITH TRI-n-BUTYL PHOSPHATE FROM AQUEOUS-ORGANIC SOLUTIONS

Cobalt(II) has been extracted by 50% (v/v) TBP solution in benzene from HC1, HBr, and LiC1 solutions containing water miscible alcohols and nonbesic and basic aprotic solvents. All solvents used caused the distribution ratio of Co(II) to increase due to diminished water activity and shifts in equilibria of cobalt(II) complexes in solutions. Hexamethylphosphor-triamide (HMPTA) has been found to behave exceptionally in that it extracted Co(II) from LiC1 solutions into neat benzene and in the presence of TBP induced a weak synergism caused by extraction of at least two mixed solvates.     

THE EXTRACTION OF Am(III) FROM NITRIC ACID BY OCTYL(PHENYL)-N,N-DIISOBUTYLCARBAMOYLMETHYLPHOSPHINE OXIDE - TRI-n-BUTYL PHOSPHATE MIXTURES

Abstract

The extraction behavior of Am(III) from nitric acid by octy1(phenyl)-N,N-diisobutylcarbamoyl methyphosphine oxides, OØD[IB]CMPO, in the presence of tributylphosphate, TBP, has been studied using diethylbenzene, decalin, and normal aliphatic hydrocarbon diluents. Relative to ØD[IB]CMPO alone, mixtures of TBP and OØD[IB]CMPO show a slight enhancement in the extraction of Am(III) from nitric acid solution above 2 M and a moderate decrease in extraction for lower acid concentrations. The net effect of TBP addition to OØD[IB]CMPO (as well as other selected carbamoyl methylphosphoryl extractants) is a relative insensitivity of the distribution ratio of Am(III) to HNO₃ concentration in the range of 0.5 M to 6 M and facilitated stripping of Am(III) with dilute acid. Since a continuous variation study of Am(III) extraction using mixtures of ØOD[IB]CMPO and TBP at a fixed total concentration revealed no evidence of a mixed complex, the TBP appears to be behaving primarily as a phase modifier

The most significant benefit gained from addition of TBP to ØD[IB]CMPO is the increased metal ion loading capacity and extractant compatibility with alicyclic and aliphatic diluents. The use of TBP to overcome phase compatibility with other bifunctional extractants of the carbamoylmethylphosphoryl type and the use of other phase modifiers with ØD[IB]CMPO have also been investigated.     

THE EXTRACTION OF Eu(III) FROM ACIDIC MEDIA BY OCTYL(PHENYL)-N,N-DIISOBUTYL CARBAMOYLMETHYLPHOSPHINE OXIDE.

The extraction behavior of Eu(III) from nitric and hydrochloric acid By solutions of CMPO with and without TBP has been studied using mesitylene and dodecane as diluents. Compared to CMPO alone, the CMPO-TBP mixture shows a slight enhancement in the extraction of Eu(III) from nitric acid above 2M and lower DEu’ s from low acidity. The distribution ratios measured for Eu(III) between HN03 and CMPO-TBP in dodecane are higher than the corresponding values in mesitylene.Extractant dependency studies in the presence and absence of TBP show that at low HN03 concentrations, the extractant dependency curve obtained in the presence of TBP lies below the curve obtained in the absence of TBP. At high acidity, the opposite is observed. The extraction of Eu(III) from hydrochloric acid by CMPO-TBP in dodecane is much lower than from nitric acid. A comparison between CMPO and D2EHPA for Eu(III) extraction has been carried out.     

磷酸三丁酯和二异丙醚溶剂萃取体系脱除湿法磷酸中氟的研究

以磷酸三丁酯与二异丙醚为溶剂,采用溶剂萃取法脱除湿法磷酸中的氟。研究了萃取剂中TBP的体积分率、相比、萃取时间、搅拌转速、反萃剂加入量对氟的净化效果的影响,确定了磷酸三丁酯与二异丙醚混合溶剂体系脱氟的工艺条件。结果表明:萃取剂组成为TBP与二异丙醚体积比为1∶1;相比4∶1、萃取时间为5min、搅拌转速为300r/min、反萃剂加入量为萃取相体积的10%,在此条件下,磷酸三丁酯与二异丙醚萃取体系对氟离子有较好的分离能力。     

磷酸三丁酯萃取分离钛铁矿亚熔盐反应产物酸解液中Fe3+及金红石型TiO2的制备

在盐酸介质中以磷酸三丁酯(TBP)为萃取剂、磺化煤油为稀释剂,从钛铁矿与氢氧化钾亚熔盐反应产物的酸解液中萃取分离Fe3+,并利用萃取后的含钛液水解制备二氧化钛. 考察了萃取剂浓度、盐酸浓度、有机相和水相体积比(O/A)和萃取时间对铁萃取率的影响. 结果表明,钾系亚熔盐法分解钛铁矿的分解率在96%以上. 萃取率随着TBP浓度及盐酸浓度的增加和O/A值的减小而增大;通过调节萃取条件,萃取率可以达到99%以上. 用1.0 mol/L的NaCl溶液进行反萃,反萃率可达98%以上. 萃取后含钛液经水解可以制得纯度高于98%的金红石型TiO2球状颗粒.     

Extraction and Stripping Behavior of Iron (III) from Phosphoric Acid Medium by D2EHPA Alone and Its Mixtures with TBP/TOPO

In the present study an attempt has been made to understand the extraction and stripping behavior of iron (III) with D2EHPA alone and its mixture with TBP or TOPO in phosphoric acid medium. Effect of variables such as concentrations of iron (III), phosphoric acid, and phosphate in the aqueous phase, D2EHPA, TBP, and TOPO concentrations in the organic phase and temperature on the extraction process has been studied. The extraction of iron (III) decreased with increase in phosphoric acid concentration. The increase in D2EHPA concentration increased the extraction of iron (III). The presence of TOPO or TBP with D2EHPA showed antagonism. The increase in temperature decreased the extraction of iron (III) with D2EHPA alone and its mixture with either TOPO or TBP showing the exothermic nature of the extraction reaction. The stripping of iron (III) by various reagents followed the order: oxalic acid > phosphoric acid > hydrochloric acid > sulphuric acid > mixture of sulphuric and hydrofluoric acids > ascorbic acid > citric acid irrespective of extraction systems. Higher temperature favors the stripping. The effect of diluents on iron (III) extraction has also been studied. The mechanism of extraction has been explained in the light of the results obtained.     

EXTRACTION OF NITRIC AND PHOSPHORIC ACIDS WITH TRIBUTYL PHOSPHATE

The extraction of nitric acid and phosphoric acid by tributyl phosphate (TBP), from solutions containing acid mixture and in the presence of nitrate salts, has been studied. The effect of the temperature on acid extraction has been also investigated. It is found that TBP extracts nitric acid preferentially to phosphoric acid, especially in the presence of nitrate salts. The coextraction of nitric acid suppresses the extraction of phosphoric acid. These results were interpreted in terms of common ion effect and variation of the activity coefficients variation in both phases. The simultaneous effects of the salts and acids on the extraction of both acids is also studied

Some tests were carried out, using process solution, to evaluate the extraction of acids. Both batch experiments and continuous tests (using mixer settler) were performed. Some flowsheets were tested in order to improve the extractivity and the selectivity of phosphoric acid. The results show the limitation of TBP for the extraction of phosphoric acid. TBP can be used to selectively extract nitric acid.