生物油中络合萃取乙酸的研究

采用三正辛胺（TOA）作为络合剂,异辛醇和煤油分别作为助溶剂和稀释剂,对生物油中的乙酸进行了络合萃取研究。考察了TOA体积分数、异辛醇浓度、萃取剂与生物油轻馏分体积比以及温度对乙酸萃取率的影响,结果表明：温度为0 ℃,萃取体系为40%TOA+40%异辛醇+20%煤油(各组分浓度均为体积分数,下同),萃取剂与生物油轻馏分体积比为3∶1时,乙酸的一次萃取率较高,可达74.6%。     

Recovery of copper from ammoniacal/ammonium sulfate medium by LIX 54

The extraction‐stripping reaction of Cu(II) by LIX 54 in Iberfluid from aqueous ammonium sulfate medium at pH 8.5 has been investigated. The effects of pH, metal ion, extractant concentration as well as the loading capacity of the reagent were studied. The extraction equilibrium constant for copper was determined numerically to be 7 × 10⁻⁷. Experimental data can be explained assuming the formation of CuR₂ species in the organic phase (R represents the extractant). Copper stripping was studied using typical spent copper electrowinning solutions as stripping medium. The number of stages required for the extraction and stripping of copper was also evaluated. The results were used to asses the conditions for purification of industrial waste solutions (eg spent etchants) containing copper through counter‐current extraction‐stripping. © 1999 Society of Chemical Industry     

溶剂萃取法从提锂后盐湖卤水中提硼的工艺研究

以青海东台吉乃尔盐湖提锂后卤水为原料,用2-乙基-1,3-己二醇分别与异辛醇、异戊醇组合的混合醇从卤水中萃取硼,从萃取剂体积分数、酸度、相比、萃取时间、萃取温度、饱和萃取容量、反萃剂浓度、反萃时间等方面加以实验,获得了混合醇从卤水中萃取提硼的最佳工艺条件:萃取剂体积分数30% ,水相pH为3,相比1:1,萃取时间10 min,最大饱和容量61.4 g/L(B2O3).并与一元醇进行了比较,得出混合醇的萃取效果远好于一元醇.     

Recovery of copper from sulphate medium by Lix-84 in kerosene

The extraction–stripping reaction of Cu(II) by Lix-84 in kerosene from aqueous sulphate medium of pH 2·5 has been investigated. The effects of pH, metal ion, extractant and strip solution concentrations as well as the loading capacity of the extractant were investigated. The number of stages required for the extraction and stripping of copper was also evaluated. The results are used to assess the conditions for purification of industrial waste solutions containing copper through counter-current extraction in a horizontal mixer-settler.     

络合萃取法提取发酵液中丁二酸盐的研究

为提高微生物发酵法生产丁二酸的产品提取收率,研究利用三辛胺/正辛醇体系对发酵液进行络合萃取。比较硫酸和阳离子交换树脂两种前处理发酵液方式对络合萃取丁二酸的影响,以及用氨水反萃制备丁二酸铵。结果表明：通过阳离子交换树脂前处理发酵液,三辛胺/正辛醇体系对丁二酸的萃取率高于硫酸前处理,可达到91.3%;氨水是一种优良反萃剂,萃取剂重复使用5次,平均萃取率为90.4%,平均反萃率为94.9%,且萃取率和反萃率未见明显下降。     

Solvent Extraction of Cyclohexanecarboxylic Acid From Waste Fluid by Using a Mixture of Toluene and 1-Octanol

Solvent extraction studies have been carried out for the recovery of cyclohexanecarboxylic acid (CCA) from simulated waste fluid. Influences of various parameters including extractant types, pH of the solution, equilibration time, and initial concentrations of CCA, etc., were studied. A mixture of toluene and 1-octanol (90:10, v/v) was found suitable for the extraction. The results showed that solution pH had a great effect on the distribution ratio, and CCA could be efficiently extracted when the pH was lower than 3.5. The extraction was found quite rapidly. The distribution ratio decreased as the initial concentration of CCA increased. The stripping rate of CCA using sodium hydroxide as stripping agent was found to be increased with the increase of alkali concentration. After back extraction once, more than 98% stripping efficiency was achieved with 0.8 mol/L sodium hydroxide solution at aqueous to organic phase (A/O) ratio 1:1 when CCA concentration was lower than 38.3 g/L. The practical extraction process was carried out for the waste fluid (concentration of CCA 36.5 g/L) discharged in the production of caprolactam from toluene. After four extraction stages at A/O ratio 1:1, the cumulative extraction recovery reached 99.3%. The practical stripping efficiency from loaded organic phase reached 98.2% in one single stage.     

络合萃取法提取发酵液中丁二酸铵

为提高微生物发酵法生产丁二酸的产品提取收率,用三辛胺/正辛醇体系对发酵液进行络合萃取。比较硫酸和阳离子交换树脂两种前处理发酵液方式对络合萃取丁二酸的影响以及用氨水反萃制备丁二酸铵。结果表明,通过阳离子交换树脂前处理发酵液,三辛胺/正辛醇体系对丁二酸的萃取率高于硫酸前处理,达到91.3%;氨水是一种优良反萃剂;萃取剂重复使用5次,平均萃取率为90.4%,平均反萃率为94.9%,且萃取率和反萃率未见明显下降。     

ANAEROBIC EXTRACTION OF COBALT IN A PULSE COLUMN

The effects of excluding air (oxygen) from a cobalt solvent extraction circuit were studied for LIX 64N extractant. After solvent extraction of divalent cobalt from ammoniacal solutions with chelating extractants such as LIX 64N, the loaded Co-chelate is believed to oxidize to a stable trivalent complex which resists subsequent stripping with mineral acids. To Improve stripping efficiency, cobalt was extracted and stripped in the absence of oxygen in pulsed, perforated-plate columns that were designed and constructed by the Bureau of Mines. When the ammoniacal cobalt(II) sulfate and LIX 64N solutions were purged, blanketed, and pulsed with argon, cobalt extraction exceeded 99%, and stripping with 1 vol % H₂SO₂ reached 98.5%. The stripped extractant was recycled to the extraction column with no loss of extraction efficiency in six passes through the circuit.     

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.     

A ROBUST ALKALINE-SIDE CSEX SOLVENT SUITABLE FOR REMOVING CESIUM FROM SAVANNAH RIVER HIGH LEVEL WASTE#

ABSTRACT

A robust solvent suitable for extracting cesium from alkaline nitrate media like that of the high-level liquid waste stored at the U.S. Department of Energy Savannah River Site has been developed. The solvent is composed of the cesium extractant calix[4]arene-bis-(tert-octylbenzo-crown-6) (“BOBCalixC6”) at 0.01 M, the modifier l-(2,2,3,3-tetrafluoropropoxy)-3-(4-sec-butylphenoxy)-2-propanol (“Cs-7SBT”) at 0.50 M, trioctylamine (“TOA”) at 0.001 M, and the aliphatic diluent Isopar® L. The solvent holds up exceptionally well under various stresses, such as sustained contact with waste simulant and dilute nitric acid; repeated extraction, scrubbing, and stripping cycles; and excessive loading. The behavior of the solvent in batch-equilibrium flowsheet tests conducted at 15, 25, and 45 °C is presented. Flowsheet calculations show that the Savannah River Site requirements for a decontamination factor of 40,000 and a cesium concentration factor of 12 could be met in a 22-stage bank of 25-cm centrifugal contactors at 25 °C with conservative assumptions regarding hydrodynamics and stage efficiency. Exploiting the temperature dependence of extraction and stripping could reduce the number of stages to 18.     

Hydraulic and Mass-Transfer Performance of a 20-Mm-Diameter Annular Centrifugal Contactor for the Solvent Extraction of Cesium by Bis(2-Propyloxy)Calix[4]-Crown-6 in n-Octanol

A calixcrown extraction process using bis(2-propyloxy)calix[4]-crown-6 (iPr-C[4]C-6) as extractant and n-octanol as diluent for the separation of cesium from Chinese High Level Liquid Waste (HLLW) has been developed at INET. Chinese HLLW is acidic defense waste with high salt content, which is now stored in underground stainless steel tanks. The intention is to use a process to extract cesium from HLLW conducted on multistage 20-mm-diameter annular centrifugal contactors (ACCs), so it is necessary to study the hydraulic and mass-transfer performance of a 20-mm-diameter ACC for the extraction system. In this work, the effects of the parameters such as the rotor speed, the diameter of heavy weir, and the acid concentration on the hydraulic performance were investigated. An operational envelope of the 20-mm-diameter ACC for the n-octanol/aqueous solution system was identified. The mass-transfer efficiency of the single stage 20-mm-diameter ACC for the extraction and stripping of cesium with iPr-C[4]C-6 in n-octanol was studied by varying several parameters, such as the rotor speed, the total flow rate, and the flow ratio. The extraction stage efficiency is greater than 95% at suitable operating conditions for extracting Cs⁺ with 0.025 mol/L of iPr-C[4]C-6 in n-octanol from HNO₃ solution containing Cs⁺. The stripping stage efficiency of Cs⁺ (< 90%) is lower than the extraction stage efficiency of Cs⁺.     

Alternatives to Nitric Acid Stripping in the Caustic‐Side Solvent Extraction (CSSX) Process for Cesium Removal from Alkaline High‐Level Waste

Effective alternatives to nitric acid stripping in the Caustic‐Side Solvent Extraction (CSSX) solvent have been demonstrated in this work. The CSSX solvent employs calix[4]arene‐bis(tert‐octylbenzo‐18‐crown‐6) (BOBCalixC6) as the cesium extractant in a modified alkane diluent for decontamination of alkaline high‐level wastes, such as those found at the Savannah River and Hanford sites. Results reported in this paper support the idea that replacement of the nitrate anion by a much more hydrophilic anion like borate can substantially lower cesium distribution ratios on stripping. Without any other change in the CSSX flowsheet, however, the use of a boric acid stripping solution in place of the 1 mM nitric acid solution used in the CSSX process marginally, though perhaps still usefully, improves stripping. The less‐than‐expected improvement was explained by the carryover of nitrate from scrubbing into stripping. Accordingly, more effective stripping is obtained after a scrub of the solvent with 0.1 M sodium hydroxide. Functional alternatives to boric acid include sodium bicarbonate or cesium hydroxide as strip solutions. Profound stripping improvement is achieved when trioctylamine, one of the components of the CSSX solvent, is replaced with a commercial guanidine reagent (LIX^® 79). The more basic guanidine affords greater latitude in the selection of aqueous conditions in that it becomes protonated even at mildly alkaline pH values. Under process‐relevant conditions, cesium distribution ratios on stripping are approximately 100‐fold lower compared with the current CSSX performance. The tolerance to surfactants is good, and the extraction properties of the solvent remain unchanged over three successive extract‐scrub‐strip cycles. From the point of view of compatibility with downstream processing, boric acid represents an attractive stripping agent, as it is also a potentially ideal feed for borosilicate vitrification of the separated ¹³⁷Cs product stream. The possibilities for use of these results toward a dramatically better next‐generation CSSX process, possibly one employing the more soluble cesium extractant calix[4]arene‐bis(2‐ethylhexylbenzo‐18‐crown‐6) (BEHBCalixC6) are discussed.     

Recovery of carboxylic acids C1?C3 with organophosphine oxide solvating extractants

This study was aimed at examining the use of the organophosphine oxides Cyanex^®921 and Cyanex^®923 for the extraction of formic, acetic and propionic acids from aqueous solutions. The stripping of monocarboxylic acids with water from the loaded extractants was also examined. The studies were aimed at determining the equilibrium conditions for extraction and stripping. Overall, the effect of the kind of extractant was not significant although Cyanex^®921 extracted carboxylic acids slightly better than Cyanex^®923 with 1:1 complexes being formed by both extractants with the acids during extraction. The efficiency of extraction depended on temperature, acid concentration and solvent, with toluene a better diluent for the extractants than octane or Exxsol^®D 220/230. Extraction efficiency increased as the concentration of acid in the feed decreased and, also, as the temperature increased, the amount of acid extracted decreased. The extraction and stripping isotherms were determined. The apparent enthalpy and entropy of the extraction reaction were determined. Distribution data for the transfer of carboxylic acids from aqueous (NaCl) solutions to organic solvents in the presence of trialkylphosphine oxide were determined at 293 K with the distribution ratios increasing as the concentration of NaCl increased. Copyright © 2005 Society of Chemical Industry     

Solvent Extraction Studies of Rare Earths from Thiocyanate Medium with N,N,N´,N´-tetra(2-ethylhexyl) diglycolamide

The extraction behavior of rare earth (RE) elements from thiocyanate medium by N,N,N^’,N^’-tetra(2-ethylhexyl) diglycolamide (TEHDGA), a neutral extractant, has been investigated and the optimum conditions for their separations were determined. Isodecyl alcohol was used as phase modifier and a concentration of 5%(v/v) was found sufficient to mitigate third phase formation under our experimental conditions. The extraction mechanism of RE with TEHDGA was established by analyzing distribution data with slope analysis technique and showed the formation of a neutral species, RE(SCN)₃.2TEHDGA, in the organic phase. The extraction of rare earth decreased with increase in temperature indicating exothermic nature and the enthalpy change (ΔH) obtained for Y(III) was ?14.27 kJ/mol. Among various stripping agents studied, oxalic acid was found to be efficient in quantitative stripping of rare earths from TEHDGA. The extraction efficiency for all the rare earths by TEHDGA was also investigated. High separation factor of 6.4 for Er/Y pair at 0.03 M thiocyanate has indicated the feasibility of using TEHDGA as extractant to separate Y from heavy rare earths, in particular Er, from thiocyanate medium.     

EXTRACTION EQUILIBRIUM OF PHENOL BY SULFURIC ACID SALTS OF TRIOCTYLAMINE

An investigation was undertaken involving the extraction equilibrium of phenol from an aqueous solution using trioctylamine sulfate salt (TOA salt)/trioctylamine (TOA) as the extractant. The purpose of using trioctylamine as the organic solvent is to increase the total capability of phenol extraction as well as to avoid the use of other organic solvents. In order to prevent the formation of a second phase from the reaction of trioctylamine and sulfuric acid, 1-octanol in an appropriate amount was added to make the organic solution homogeneous. Equilibrium distribution coefficients (K_d) in the extraction of phenol by TOA salt/TOA were measured for various operating conditions. The equilibrium distribution coefficient of phenol (K_d) between two phases decreased with increasing the initial concentration of phenol, thereby decreasing the initial concentration of sulfuric acid, and subsequently increasing the volume ratio of aqueous phase to organic phase. We recommended that the extraction is carried out at low temperature. A higher value of K_d up to 800 was obtained in using trioctylamine sulfate/trioctylamine as the extractant for equal volume ratio of aqueous phase to organic phase.     

Synergistic effect of various neutral donors in D2EHPA for selective neodymium separation from lanthanide series via HFSLM

The separation of Nd(III) from lanthanide series via hollow fiber supported liquid membrane (HFSLM) using synergistic extractant was investigated. Optimum extraction and stripping obtained were 94.5% and 85.1% using D2EHPA and TOPO mixtures (0.5:0.5 M/M) as the synergistic extractant. Reaction order for both extraction and stripping were first-order with rate constants of 1.444 and 1.338 min⁻¹, respectively. The experimental results were used to correlate with the models. Results showed that the concentration of Nd(III) from the experiment fitted in well with the model results. The average deviation was 1.95% and 2.18% for predictions in both feed and stripping sides, respectively.     

硫酸体系中P507对铟锌锰的萃取分离研究

根据软锰矿和闪锌矿在酸性条件下同槽浸出所得浸出液特点(含铟、锌、锰离子),用P507萃取浸出液中的铟,分离出锌和锰。考察了平衡水相酸度(氢离子浓度)、萃取剂体积分数、萃取温度、有机相与水相体积比、萃取时间等因素对铟萃取率的影响。研究结果表明:在室温下,在平衡水相酸度为2.5 mol/L、P507体积分数为30%(30%P507+70%磺化煤油)、有机相与水相体积比为1∶1、萃取时间为10 min条件下,铟的一级萃取率在99%以上,锌和锰一级萃取率在1.20%以下,铟与锌和锰的分离达到最佳效果;负载有机相经水洗,锌和锰洗涤率为99%,铟洗涤率为0;用2.0 mol/L盐酸进行反萃,铟反萃率在98%以上,达到了富集铟分离锌和锰的目的。     

Extraction of copper from dilute solutions by LIX 64N. Effect of dekalin and tetralin as diluents on the equilibrium and rate of mass transfer

Liquid-liquid equilibrium data and mass transfer rates for the extraction of copper from dilute aqueous sulphate solutions by LIX 64N with dekalin (decahydronaphthalene) and tetralin (1,2,3,4-tetrahydronaphthalene) as diluents are reported. The stripping of copper from the organic phase was also studied. For an initial copper concentration of 1.5 g dm^?3 extraction efficiency decreases as the concentration of tetralin increases in the diluent mixtures of dekalin-tetralin. This behaviour is explained as a result of the formation of oxime aggregates and the interaction between the oxime and the diluent. Initial rates of extraction and stripping were determined by the single drop technique. The linear relation between initial rates of extraction and the difference of interfacial tension between the extractant in the diluent and the diluent itself holds for the system under investigation.     

环保性碱液强化萃取剂处理高含酚量的焦化废水

本工作研究了一种注重于减少二次有机污染的废水高效环保脱酚工艺,采用了一种创新的方法采集含酚焦化废水的样品,通过检测特定参数确定废水样品的化学成分,避免实验误差且增强了水处理效果. 蒸氨废水是一种理想的焦化废水样品,脱酚过程中不会产生酸焦油油膜和硫酸铵沉淀. 相对于蒸氨废水,残余氨水不仅会导致严重的水污染还会消耗更多的酸,导致成本增高. 从环保角度研究萃取剂,除了关注其脱酚效率还需要研究其他影响参数如总氰量、S?含量、氨氮量、Cl?含量、SO42?含量、挥发酚含量、总含盐、污水含油量、总硬度、CODCr、电导率和pH值等. 考察了有机微粒的扩散特征和导致脱酚前后参数变化的原因. 以温度23℃、浓度为3wt%的氢氧化钠溶液反复洗涤用过的BQ络合萃取剂5次可得再生萃取剂,用其处理过后废水挥发酚含量为265.45 mg/L. 这款优良的萃取剂的CODCr,污水含油量,pH,脱酚效率依次分别为3638.34, 188.86, 6.18和83.76%,造成的二次有机污染较少.     

Parametric optimization of green synergistic reactive extraction of lactic acid using trioctylamine,Aliquat336, and butan-2-ol in sunflower oil by response surface methodology

A novel green synergistic reactive extraction technique for the removal of lactic acid (LA) from aqueous solution was explored. Response surface methodology (RSM) was applied to optimize the process variables for LA synergistic reactive extraction using a mixture of trioctylamine and Aliquat336 as extractants. During this present investigation, 2-butanol and sunflower oil were used as organic and green diluent. Systematic investigation has been carried out to obtain the optimum process conditions viz. initial LA concentration, pH of aqueous solution, extractant ratio, extractant concentration, solvent ratio, phase ratio, temperature, stirring speed, and contact time for maximizing the LA distribution coefficient (K_D) and extraction efficiency (%, η). The highest experimentally achievable LA distribution coefficient (K_D) and extraction efficiency (%) at optimized process conditions were found to be in close agreement with those predicted by numerical optimization using RSM. Thus, the results of present finding have been shown a great ability of sunflower oil as an economic and environmentally friendly green solvent for LA extraction.