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。     

The Solvent Extraction of Boron with Synthesized Aliphatic 1,3‐Diols: Stripping and Extraction Behavior of Boron by 2,2,5‐Trimethyl‐1,3‐hexanediol

Abstract

A variety of aliphatic 1,3‐diols (4a–c, 5a–c, 6a–c) was synthesized from β‐hydroxy carbonyl compounds (1–3) for potential use in the solvent extraction of boron. Primary‐secondary and primary‐tertiary alcohol structures of 1,3‐diols substituted with isopropyl, isobutyl, and isopentyl groups have been demonstrated to be very efficient for the solvent extraction of boric acid from aqueous solutions. The extraction ability of 2,2,5‐trimethyl‐1,3‐hexanediol (5b) was investigated as a function of 5b concentration, solution pH, solvent properties, and stripping conditions. Extraction efficiency increased with increasing concentration of 5b, and the best extraction of boron (96.8%) was found to be at an equilibrium pH of 2 with 0.5 M of 5b. Chloroform, toluene, chlorobenzene, 2‐octanol, and n‐amyl alcohol were found to be suitable solvents for the solvent extraction of boron. The boron complex can be recovered from the organic phase by treatment with an aqueous solution of sodium hydroxide. The highest ratio (96.7%) of boron was recovered by 0.1 M of sodium hydroxide solution.     

环戊烷萃取精馏脱硫实验动态研究

提出了氢氧化钠溶液作为萃取剂对环戊烷进行萃取精馏脱硫的方法。考察了碱液浓度、剂油比、回流比及助溶剂对脱硫效果的影响。实验结果表明其最佳脱硫条件为:有提馏段,以4%的氢氧化钠溶液作萃取剂,剂油比为4∶3,回流比为1∶5,环戊烷的硫含量最低为0.13mg/L,脱硫率最高可达到97.8%。     

Separation and Recovery of Light Rare-Earths from Chloride Solutions using Organophosphorus based Extractants

In this paper, separation possibilities of light rare-earths (LREs), Ce, La, Nd, and Pr with three acidic organophosphorus extractants such as TOPS 99 (an equivalent of di-2-ethylhexyl phosphoric acid, D2EHPA), PC 88A(2-ethylhexylphosphonic acid mono-2-ethylhexyl ester), and Cyanex 272 (Bis(2,4,4-trimethylpentyl)phosphinic acid) from synthetic chloride solutions of monazite at three initial pH values has been investigated. The composition of synthetic leach liquor is Ce ? 5.4 g/L, La ? 3.12 g/L, Nd ?1.35 g/L, and Pr ? 0.475 g/L at pH 2.0. Using sodium hypochlorite and sodium hydroxide, cerium was precipitated as ceric hydroxide quantitatively. Among the three investigated extractants, TOPS 99 showed better separation factors towards LREs. Therefore, 0.7 mol/L TOPS 99 has been employed for the separation of Nd, and Pr from La in 3-stages at an aqueous to organic phase ratio of 4:1 and pH 2.0. Raffinate contains 2120 mg/L La, 41 mg/L of Nd, and 17 mg/L of Pr corresponding to an extraction efficiency of 32.1%, 96.4%, and 96.2%, respectively. La from loaded organic phase was scrubbed with 9182 mg/L Nd solution and achieved a scrubbing efficiency of 98.2%. 1 mol/L HCl is used for quantitative stripping. A process flowsheet for the separation and recovery of LREs was presented.     

Solvent Extraction of Gold(I) from Alkaline Cyanide Solution with Furfuryl Thioalcohol

A facile approach was designed to extract gold(I) from alkaline cyanide solution via a hydrometallurgy method. The performances of gold(I) extraction with furfuryl thioalcohol were investigated. The results revealed that gold(I) extraction increased with increasing extractant concentration and phase ratio but decreased with increase of pH value and god(I) concentration. The transfer speed of gold(I) between two phases was rather fast, and the extraction equilibrium could be established within 2 min. The extraction of gold(I) reached 92.7% with 15% (V/V) extractant. Gold(I) loaded in organic phase was stripped by NaOH solution, and stripping of gold(I) reached 90.2% with 0.08 mol · L^?1.     

Separation and recovery of copper from waste printed circuit boards leach solution using solvent extraction with Acorga M5640 as extractant

Waste printed circuit boards (WPCBs) have received extensive attention in recent years because of its harmfulness and resource. In this work, two-step leaching process was carried out by using steel pickling waste liquor (SPWL) as the leaching agent. The leaching solution contains a variety of metals, especially iron, which will have an effect on the recovery of copper. Acorga M5640 (M5640) extractant with a kerosene diluent was used to recover copper from WPCBs leach solution, and the separation factor is adopted to analyze the effects of these metal ions. The effect of different parameters such as pH of aqueous phase, phase ratio (O/A), M5640 concentration, contact time as well as the concentration of H₂SO₄ as stripping reagent were investigated. Over 90.0% copper was extracted with pH 1.1, phase ratio (O/A) 1/1, M5640 concentration 16%, contact time 3 min at room temperature. For the stripping process, the 60 s contact time and 2.5 mol/L H₂SO₄ concentration are suitable with 90.0% stripping percentage of copper. Copper extraction isotherm accords with Langmuir isotherm equation and the results show that iron is the most influential metal ion for copper extraction, which will reduce the theoretical saturation of the extractant. The extractant M5640 has excellent reuse performance and can be recycled more than 10 times, which demonstrated M5640 has the industrial application value in the extraction of copper from WPCBs leach solution.     

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。     

β-二酮和5-壬基水杨醛肟从氨性溶液萃取铜的研究

对β-二酮,5-壬基水杨醛肟和它们的混和物萃取氨性溶液中的铜的性能做了研究,结果表明:在铜离子初始浓度为2.5g/L,氨浓度为56g/L,β-二酮与5-壬基水杨醛肟的体积比为1∶2时,铜回收率达到85.10%,饱和萃铜容量为6.0g/L。最佳萃取和反萃条件为:初始水相pH10,温度30℃,硫酸浓度为180g/L。并把β-二酮和5-壬基水杨醛肟与β-二酮的体积比为1∶2的混和物应用于模拟印制电路板蚀刻废液中铜的回收,经过单级萃取,混合物的铜回收率比β-二酮提高2.7%。     

Use of Calix[4]-bis-2,3-naphthocrown-6 for Separation of Cesium from Pressurized Heavy Water Reactor Simulated High Level Waste Solutions (PHWR-SHLW)

Abstract

Distribution studies on Cs(I) were carried out from pressurized heavy water reactor (PHWR) simulated high level waste (SHLW) solution using calix[4]-bis-2,3-naphtho-crown-6 as the ligand. A mixture of 1:1 nitrobenzene and toluene was evaluated as a suitable diluent. The distribution ratio of Cs(I) increased with the aqueous feed acidity upto 3 M HNO₃ and decreased thereafter due to extraction of hydronium ions. The maximum D_Cs value at ～3 M HNO₃ suggested the possible application of the system for the recovery of radio-cesium from high level waste solution. The addition of 0.4% (v/v) Alamine 336 (a tertiary amine) facilitated the quantitative stripping of Cs(I) with distilled water. Quantitative extraction of Cs(I) from SHLW containing 0.32 g/L of Cs was observed in five contacts at O/A = 1/2 with 2.5 × 10^?3 M calix[4]-bis-2,3-naphtho-crown-6. Similarly, quantitative stripping of Cs(I) from the loaded organic phase was achieved in two contacts with distilled water at a volume ratio (O/A) of 2. Selectivity studies carried out using several radiotracers such as ¹⁴³Ce, ¹⁴⁰La, ¹⁴⁰Ba, ¹³⁷Cs, ¹⁰³Ru, ⁹⁹Mo, ^99mTc, ⁹⁷Zr, ⁹¹Sr, etc. indicated excellent selectivity for Cs. The reagent exhibited excellent chemical stability up to a period of six months.     

Separation of NaOH by Solvent Extraction Using Weak Hydroxy Acids

Abstract

Separation of sodium hydroxide from aqueous salt solutions at elevated pH may be accomplished by use of solvent extraction with weak hydroxy acids. A series of lipophilic weak hydroxy acids, including alkyl phenols and fluorinated alcohols, has been characterized with regard to their ability to extract sodium into 1‐octanol as a function of temperature and extractant concentration. Isotherms are presented at 10, 25, and 60°C, employing extractant concentrations up to 1 M and aqueous NaOH concentrations up to 7 M. Near stoichiometric loading of all compounds tested may be achieved in a process postulated to be simple cation exchange. Extraction strength increases with the expected acidity of the hydroxy acids. Strongest extraction was observed with two alkyl phenols and 4‐n‐octyl‐α,α‐bis(trifluoromethyl)benzyl alcohol. Essentially complete removal of free hydroxide from a solution containing sodium hydroxide, nitrate, and aluminate was accomplished using 1 M 4‐tert‐octylphenol in 1‐octanol at 60°C. Consequently, as the pH of the solution was lowered, aluminum was observed to precipitate as the Bayerite form of Al(OH)₃. Contacting the loaded solvent with water released NaOH into the strip solution, and good selectivity for hydroxide vs. nitrate and aluminate was obtained. Since hydroxide equivalents rather than the hydroxide ion itself are believed to be extracted by the weak hydroxy acids, the process is referred to as pseudo‐hydroxide extraction. Application of this concept to sodium removal and caustic recycle in the treatment of alkaline nuclear waste appears feasible.     

Study on Streptomycin Sulfate Recovery by Batch Foam Separation

The feasibility of foam separation as a technique was assessed for the recovery of streptomycin sulfate from the waste solution by using an anionic surfactant sodium dodecyl sulfate (SDS). The experimental parameters examined were SDS concentration, superficial gas velocity, initial pH, and liquid loading volume. The results showed that sodium dodecyl sulfate as the surfactant for foam separation had good foaming quality and could effectively concentrate streptomycin sulfate of the aqueous solution by technology of foam separation. The enrichment ratio and the recovery rate of streptomycin sulfate were 4.0 and 85%, respectively under the best operating conditions of sodium dodecyl sulfate concentration 0.4 g/L, superficial gas velocity 300 mL/min, liquid loading volume 300 mL and initial pH 6.0 when streptomycin sulfate concentration was 0.5 g/L.     

磷酸三丁酯/煤油支撑液膜体系中苯酚的传质分离

研究了苯酚在以多孔聚丙烯平板膜(Celgard2500)为支撑体、磷酸三丁酯(TBP)为膜载体和煤油为膜溶剂的支撑液膜体系中的传质过程;用传统萃取法测定了TBP/煤油体系中苯酚络合物摩尔比为1∶1,同时得到25.0℃萃取平衡常数为96.72;考察了原料相pH值、初始质量浓度、膜二侧转速、载体浓度和反萃取相碱浓度对苯酚传质的影响,确定了该体系分离苯酚的最佳条件:原料相pH<9,苯酚初始质量浓度<1 000 mg/L,膜二侧转速>300 r/m in,载体浓度为0.55 mol/L,反萃取相碱浓度0.10 mol/L;根据双膜理论提出苯酚的传质动力学方程,采用直线斜率法计算了苯酚在TBP/煤油支撑液膜体系中的扩散层厚度和膜内扩散系数,计算结果表明动力学方程计算值能较好地与实验值吻合,平均相对误差在2%以内。     

Separation of radioactive metal ions by hollow fiber-supported liquid membrane and permeability analysis

Extraction and stripping of uranium ions from nitrate media using a hollow fiber liquid membrane contactor was studied. In this study, tri-butyl phosphate (TBP) diluted in kerosene was used as extractant and sodium hydroxide was applied as a stripping solution. Uranium ions were extracted using TBP 5%(v/v) by rejecting thorium ions into raffinate with a maximum percentage of extraction for the uranium being 67%. The mathematical model was focused on the extraction side of the liquid membrane system. The permeability for each concentration of HNO₃ was investigated by mass transfer theory. When the concentration of HNO₃ increased, more uranium ions were extracted; however, when the concentration of uranium and thorium in the feed solution was increased, the percentage of extraction and stripping slightly decreased because the permeability decreases when the concentration of the feed solution increases due to membrane fouling and concentration polarization.     

Recovery of Fumaric Acid from Industrial Wastewater by Chemical Extraction and Stripping

Abstract

The study on chemical extraction and stripping for the recovery of fumaric acid from low concentration organic acid wastewater has been carried out. The parameters influencing the extraction efficiency were investigated, including extractant concentration, the initial pH, the volume ratio of water to oil (W/O), the extraction temperature, and the concentration of n‐octanol. The heat effect of the extraction process, the formation of acid‐amine complexes, and the corresponding equilibrium constant were determined. In the optimum condition that kerosene/N₇₃₀₁/n‐octanol was 2:2:1, pH was 0.5, W/O was 1:1, and the temperature was 303K, through chemical extraction and stripping, the COD_cr value of fumaric acid wastewater decreased from 71040 mg/l to 8411 mg/l, and the overall COD_cr removal rate reached 88.16%, and the extraction efficiency of fumaric acid was 70.67%. The extractant was regenerated by a stripping process with 2% NaOH, and the stripping rate almost arrived at 100%. The regenerated extractant was cycled seven times without decreasing extraction efficiency and the stripping rate. And fumaric acid was obtained by adjusting the pH of the salt from stripping. After extraction, the fumaric acid wastewater can be further treated by oxidation or biodegradation to environmentally acceptable levels.     

Performance of hollow fiber supported liquid membrane on the extraction of mercury(II) ions

The extraction and recovery or stripping of mercury ions from chloride media using microporous hydrophobic hollow fiber supported liquid membranes (HFSLM) has been studied. Tri-n-octylamine (TOA) dissolved in kerosene was used as an extractant. Sodium hydroxide was used as a stripping solution. The transport system was studied as a function of several variables: the concentration of hydrochloric acid in the feed solution, the concentration of TOA in the liquid membrane, the concentration of sodium hydroxide in the stripping solution, the concentration of mercury ions in the feed solution and the flow rates of both feed and stripping solutions. The results indicated that the maximum percentages of the extraction and recovery of mercury ions of 100% and 97% were achieved at the concentration of hydrochloric acid in the feed solution of 0.1 mol/l, the concentration of TOA at 3% v/v, the concentration of sodium hydroxide at 0.5 mol/l and the flow rates of the feed and stripping solutions of 100 ml/min. However, the concentration of mercury ions from 1–100 ppm in the feed solution had no effect on the percentages of extraction and recovery of mercury ions. Thus, these results have identified that the hollow fiber supported liquid membrane process has high efficiency on both the extraction and recovery of mercury (II) ions. Moreover, the mass transfer coefficients of the aqueous phase (k _i ) and membrane or organic phase (k _m ) were calculated. The mass transfer coefficients of the aqueous phase and organic phase are 0.42 and 1.67 cm/s, respectively. The mass transfer coefficient of the organic phase is higher than that of the aqueous phase. Therefore, the mass transfer controlling step is the diffusion of the mercury ions through the film layer between the feed solution and the liquid membrane.     

Uranium Solvent Extraction and Separation From Vanadium in Alkaline Solutions

Quaternary amine could be used to extract uranium from alkaline leach solutions, but third phase formation prevented its application. In this paper, isodecanol was used as the modifier for Aliquat 336 in Shellsol D70 to extract uranium from a carbonate leach solution. The formation of third phase was eliminated. More than 98% of uranium was extracted using 3% (w/v) Aliquat 336 and 3% (w/v) isodecanol in Shellsol D70 from a carbonate leach solution containing 95 mg/L U and 25 mg/L V at pH 10.3 and room temperature in a single contact. The separation factor of uranium over vanadium increased with increasing pH of the auqueous solution and reached 280 at pH 11, indicating a good separation of the two metals. The co-extracted vanadium was scrubbed from the loaded organic solution at pH 11 using a solution containing 50 g/L Na₂CO₃. Over 90% of uranium was stripped from the loaded organic soluiton using an acidic solution containing 150 g/L ammonium sulphate in a single contact. It was also found that to obtain high uranium extraction, the chloride concentration should be controlled to less than 1 g/L in the aqueous phase.     

Recovery of Zinc by LIX 984N‐C from Electroplating Rinse Bath Solution

The development of a complete solvent extraction process at the laboratory scale for recovering zinc from the zinc electroplating first rinse bath solution (alkali solution) containing ～1.9 g/L zinc (ZEFRBS) by a solvent extraction route using LIX 984N‐C, which is a new SX reagent developed by Cognis, and dissolved in commercial kerosene was investigated. By using LIX 984N‐C, an electrolyte from ZEFRBS with ～12 g/L zinc content, which was addable to the alkali zinc electroplating bath, was generated by 10 vol.% LIX 984N‐C in commercial kerosene at the O/A ratio of 1/4 and equilibrium pH value of 8.00 ± 0.05 with a two‐stage countercurrent extraction, and stripping of the loaded organic by a strip solution with 150 g/L sulfuric acid and with the O/A ratio of 1.5 at a two‐stage countercurrent stripping process. A new complete flow sheet of 10 vol.% LIX 984N‐C process for the recovery of zinc from ZEFRBS has been demonstrated.     

Phenol Removal from Aqueous System by Bis(2-ethylhexyl) Sulfoxide Extraction

Solvent extraction is generally considered as one of the important and effective techniques to remove toxic phenol from wastewater. This paper explores the solvent extraction of phenol from wastewater using bis(2-ethylhexyl) sulfoxide (BESO) as extractant. Various parameters such as equilibrium time, the volume percentage of BESO, pH value, and ionic strength of the aqueous solution on the phenol extraction were investigated. The results indicated that BESO exhibited excellent performance of phenol extraction. The extraction percentage increased from 97.26% to 99.47%, varying the BESO concentration from 10% (v/v) to 30% (v/v). The extraction percentage decreased with increasing temperature in the range of 298-343 K. FTIR spectra of fresh and phenol loaded BESO organic phase indicated the existence of the hydrogen bonding interactions between S=O groups and phenol molecules. The relationship between log D and log [BESO] suggested the stoichiometry of the extracted species was a 1:1 complex, namely, [PhOH]·[BESO]. Phenol stripping from the loaded organic phase by sodium hydroxide was feasible, and more than 99% of phenol could be stripped when the NaOH concentration was 0.5 mol L^?1. The results obtained established that BESO/kerosene extraction system has potential for practical application in the phenol removal and recovery.     

P507从酸性硫脲浸金液中回收金

研究了用P507的煤油溶液作为萃取剂，从酸性硫脲(TU)浸金液中回收金的性能. 用浓度为1.65 mol/L的P507萃取剂在料液[H2SO4]＝0.335 mol/L, 相比O/A=1:1，两相接触时间5 min的条件下萃取金，得到金的一级萃取率达99.80%；用50 g/L的Na2SO3溶液反萃，一级反萃率达82.45%，同时达到金、铁的分离.