Extraction of Caffeine with Annular Centrifugal Contactors

Abstract

An extraction process for caffeine has been developed with annular centrifugal contactors. The caffeine distribution ratio in the mother solution effluent‐chloroform system was measured to be about 18.6. Both the pilot tests and the plant tests have been completed with Φ20 mm and Φ230 mm annular centrifugal contactors, respectively. The extraction rate higher than 99% was achieved in the pilot tests, when the rotor speed was 3000‐4500 r/min, the total flow was 20‐80 mL/min, and the flow ratio (A/O) was 2/1. When the rotor speed was 1800 r/min, the mother solution flow was 2000 L/h, and the chloroform flow was 1000 L/h; the extraction rate was also more than 99% in the plant tests.     

Extraction of Hydrocortisone from the Fermentation Liquor with Annular Centrifugal Contactors

Abstract

A continuous countercurrent extraction process for the recovery of hydrocortisone from the fermentation liquor has been developed with annular centrifugal contactors. When the hydrocortisone was extracted from the fermentation liquor with the butyl acetate, the distribution ratio increased with increase of the hydrocortisone concentration in the equilibrium aqueous phase. Both the laboratory tests and the plant tests have been finished with Φ20 mm and Φ230 mm annular centrifugal contactors respectively. In the laboratory tests, when the rotor speed was 3400～4200 r/min, the fermentation liquor flow was 30～50 mL/min and the phase ratio (V_O/V_A) was 0.36～0.50, the percent recovery of hydrocortisone was higher than 92%. In the plant tests, when the rotor speed was 2000 r/min, the fermentation liquor flow was 2000 L/h and the butyl acetate flow was 1000 L/h, the percent recovery of hydrocortisone was about 96.5～98%.     

Separation of Ionic Liquid Dispersions in Centrifugal Solvent Extraction Contactors

Abstract

Separations of dispersions formed by mixing immiscible organic room‐temperature ionic liquids (IL)/hydrocarbon/and aqueous systems using a centrifugal solvent‐extraction contactor have been successfully demonstrated in proof‐of‐concept testing. This accomplishment is significant in that physical property factors that are typical of ionic liquid systems (e.g., similar densities of the bulk phases, low interfacial tensions, and high viscosities) are typically unfavorable for dispersion separation, particularly in continuous processes. Efficient separation of dispersions containing ionic liquid solvents is essential for utilization of these compounds in liquid‐liquid extraction applications to maximize both solute transfer efficiency and solvent recovery. Efficient solvent recovery is of particular concern in IL applications because of the high cost of most IL solvents.

This paper presents the results of initial experiments with three hydrophobic ionic liquids to determine how their physical properties affect phase mixing and phase disengagement in contact with an aqueous solution using a centrifugal contactor. While the results of the reported work are promising, additional work is needed to optimize existing mathematical models of contactor hydraulics to address special considerations involved in IL‐based processes and to optimize the equipment itself for IL applications.     

环隙式离心萃取器界面半径的测定与关联

采用“快速放液法”测定转筒内的存留量，并用合适的相分布模型计算出相应的界面半径，即实验值。系统研究了转速、流比、重相堰直径、流量、两相密度差和粘度６个参数对环隙式离心萃取器界面半径的影响。用多元回归关联了６个自变量，拟合了界面半径的经验公式。计算值与实验值吻合较好，平均误差３．０３％，可用来确定２０ｍｍ环隙式离心萃取器最佳工作条件。     

Demonstration of an Improved Total Partitioning Process for High Level Liquid Waste Using Annular Centrifugal Contactors

High level liquid waste (HLLW) produced from the reprocessing of the spent nuclear fuel still contains moderate amounts of uranium, transuranium (TRU) actinides, ⁹⁰Sr, ¹³⁷Cs, etc., and thus constitutes a permanent hazard to the environment. The partitioning and transmutation (P&T) strategy has increasingly attracted interest for the safe treatment and disposal of HLLW, in which the partitioning of HLLW is one of the critical technical issues. An improved total partitioning process, including a TRPO (tri-alkylphosphine oxide) process for the removal of actinides, a CESE (crown ether strontium extraction) process for the removal of Sr, and a calixcrown ether extraction process for the removal of Cs, has been developed to treat Chinese HLLW at the Institute of Nuclear and New Energy Technology (INET), Tsinghua University, China. A demonstration test of the improved total partitioning process was carried out using 74-stage 10-mm-dia annular centrifugal contactors and simulated HLLW. The test results showed that the decontamination factors were >1.2 × 10⁶, 4600, and 7500 for Nd, Sr, and Cs, respectively. In the test, Nd was used to simulate Am. During the test, 74-stage 10-mm-dia annular centrifugal contactors worked stable continuously with no stage failing or interruption of the operation.     

Development of a Solvent Extraction Model for Process Tests in Short Residence Time Centrifugal Contactors

A computer program has been developed for optimization and modelling of counter–current solvent extraction processes. The distribution between the phases is calculated by either D-ratio functions or by a novel kinetic model for the transfer between the phases. The kinetic model is important to use when slow extraction kinetics yields D-ratios far from equilibrium. Transfer rate data was investigated in a single stage centrifugal contactor, modified for internal recirculation of the phases. Using this methodology a demonstration process for the recovery of minor actinides in a counter–current centrifugal contactor system using CyMe₄-BTBP was modelled with excellent agreement towards the experimental values.     

Annular Centrifugal Contactors for Solvent Extraction

Abstract

Annular centrifugal contactors suitable for laboratory use in solvent extraction work have been designed and tested for both hydraulic performance and mass-transfer efficiency. The 2-cm contactors have nominal flow rates of 80 mL/min and mass-transfer efficiencies of at least 85% as measured by the extraction of uranium. These contactors work well for organic-to-aqueous (O/A) flow ratios greater than 0.8. Multistage units allow proposed flow sheets to be tested on a continuous basis in the laboratory. Scale-up to larger plant-size units is straightforward.     

Cloud Point Extraction of Acetic Acid from Aqueous Solution

Abstract

A new acetic acid separation method was developed through a successful combination of cloud point extraction and complex extraction technology (CPE-SE), where an acetic acid complex compound formed and was solubilized in a surfactant micelle solution, instead of an organic solvent, and then concentrated into one phase by a phase separation process of the CPE technology. Since no organic solvent diluents were used, the new process was environmentally friendly and with a lower cost; meanwhile, the high selectivity of the complex extraction based on chemical complexation and high efficiency of CPE were also inherited as advantages over conventional solvent extraction process. In consideration of the compatibility and the related CPE characteristics, tributyl phosphate and PEG/PPG-18/18 Dimethicone were selected as complexing agent and surfactant of the CPE-SE system, respectively, and the extraction system was optimized by studying the effect of the main process parameters, including surfactant and complexing agent concentration, temperatures for the stirring and incubation steps, on the recovery and the distribution coefficient. A relative high recovery of 71.4% and a distribution coefficient of 1.4 were achieved simultaneously with the optimized process in the treatment of 0.1 M acetic acid solution. Based on its competitive extractability, high efficiency, low-cost, and environment friendlyness, the CPE-SE process was expected to be a potential separation method for a dilute acetic acid solution.     

Application of Annular Centrifugal Contactor on Separating Indium from Iron

Abstract

It is hard to separate indium from iron in sulfuric acid leachate without reducing Fe³⁺ to Fe²⁺ with di(2-ethylhexyl) phosphoric acid (HDEHP) by the equilibrium extraction process. A nonequilibrium extraction process with annular centrifugal contactors is studied through the extraction kinetics difference between In and Fe. The mass transfer velocities of In and Fe were determined. Laboratory- and industry-scale extraction tests with miniature and industry scale annular centrifugal contactors, respectively, were conducted. The results indicate the mass transfer velocity of In is much faster than that of Fe, the contact time between the two phases is very short in the contactor, and the In can be well separated from Fe in the nonequilibrium extraction process with annular centrifugal contactors.     

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%。     

Water Content of Organic Solvents and their Relationship to Extraction of Nitric and Acetic Acid from UREX+ Streams

This study investigates the equilibrium absorption of water in various solvents and solvent-mixtures being considered for the counter-current solvent extraction of acetic acid from improved Uranium Extraction (UREX+) process solutions. It then seeks to determine if there is any correlation between the equilibrium water content of these solvents and their equilibrium extraction of 0.25 M nitric and 0.025 M acetic acid. The UREX+ process is a proliferation resistant version of the Plutonium Uranium Extraction (PUREX) process. The solvents studied were n-Dodecane (nDD), 1,2 Dichloroethane (DCE), and Phenyltrifluoromethyl Sulfone (FS-13), and mixtures of these solvents with Tributyl Phosphate (TBP). After studying both pure water and acidified aqueous systems, it seems the water absorption mechanism is independent of the diluent used and remains constant with the addition of the 0.25 M nitric and 0.025 M acetic acid.     

萃取、共沸精馏技术联用回收废液中的醋酸

针对化工生产过程中产生的稀醋酸溶液难以回收高纯度醋酸的问题,首先采用乙酸乙酯和苯的混合溶剂萃取浓缩稀醋酸溶液;再通过精馏蒸出溶液中的萃取剂和部分水;最后采用乙酸丁酯作为挟带剂,用共沸精馏法分离得到醋酸。得到的醋酸质量分数达96.84%,回收率达84.97%。对工业化回收稀醋酸溶液中的醋酸有一定的实用价值。     

Radioactive Tracer Tests of Two Improved TRPO Processes for High-Level Liquid Waste Using Annular Centrifugal Contactors

High-level liquid waste (HLLW) produced from the reprocessing of the spent nuclear fuel still contains moderate amounts of uranium, transuranium (TRU) actinides, and fission products, and thus constitutes a permanent hazard to the environment. The partitioning and transmutation (P&T) strategy has increasingly attracted interest for the safe treatment and disposal of HLLW, in which the partitioning of HLLW is one of the critical technical issues. Two improved trialkylphosphine oxide (TRPO) processes for the removal of actinides have been developed to treat Chinese HLLW, based on the original TRPO process. In one improved process N,N-diethylhydroxylamine as a reducing agent was used for reducing Np(V) and Np(VI) to Np(IV) in order to improve the extraction efficiency of Np. In the other improved process, ammonium vanadate as an oxidizing agent was used for oxidizing Np(V) and Np(IV) to Np(VI) in order to improve the extraction efficiency of Np. Radioactive tracer tests of two improved TRPO processes were carried out using 30-stage 10-mm-diam annular centrifugal contactors and simulated HLLW containing U, Np, Pu, and Am. The test results showed that the decontamination factor of total α activity was >1 × 10⁵. During the test, 30-stage 10-mm-diam annular centrifugal contactors worked in a stable manner continuously, with no stage failing or any interruption of the operation.     

Thirty Stage Annular Centrifugal Contactor Thermal Profile Measurements

A thirty stage 5 cm annular centrifugal contactor cascade was assembled and tested to obtain thermal profiles during both ambient and heated input conditions of operation. Thermocouples were installed on every stage as well as feed inputs, and real-time data was taken during experiments lasting from two to eight hours at total flow rates of 0.5 to 1.4 liters per minute. Ambient temperature profile results show that only a small amount of heat is generated by the mechanical energy of the contactors. Steady state temperature profiles mimic the ambient temperature of the lab but are higher toward the middle of the cascade. Heated inlet solutions gave temperature profiles with smaller temperature gradients, more driven by the temperature of the inlet solutions than ambient lab temperature. Temperature effects of solution mixing, even at rotor speeds of 4000 rpm, were not measurable.     

醋酸制备乙醇用催化剂研究

综述了国内外醋酸制备乙醇催化剂的研究现状、技术特点、反应机理及最新进展,指出了醋酸制备乙醇催化剂的研究方向。     

一种以乙酸为原料制备丙烯酸的方法

本文介绍了一种以乙酸和甲醛进行羟醛缩合反应制备丙烯酸的方法,该方法以煤为起始原料生产丙烯酸,克服了目前工业丙烯氧化法生产丙烯酸原料来源不足的问题。     

仲辛基苯氧乙酸萃取Zn(II)的性能

研究了一种新型萃取剂仲辛基苯氧乙酸(CA–12)的皂化以及从盐酸介质中萃取Zn(II)的性能. 考察了萃取温度、平衡水相酸度、萃取剂浓度等因素对萃取的影响. 氨水皂化CA–12的最佳条件是使用含有1.0 mol/L NaCl的稀氨水制皂、皂化率为80%；分配比随平衡水相酸度的增加而减小，且lgD与pH呈线性关系，其斜率约为2；分配比随萃取剂初始浓度的增大而增大；初始酸度pH=6.0~6.5、萃取剂初始浓度CHA>0.10 mol/L时，水相中0.01 mol/L Zn(II)几乎被定量萃取. 计算得到了CA–12从盐酸介质中萃取Zn(II)的过程热效应DH=3.28 kJ/mol.     

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⁺.     

Separation of Acetic Acid from Acetic Acid-Water Mixture by Crystallization

Separation of acetic acid from acetic acid and water mixture was carried out by melt crystallization. The effect of the cooling rate, the amount of seeds, the seeding temperature, the sweating rate, and the sweating fraction on the distribution coefficient was investigated. The acetic acid was successfully separated by single-stage melt crystallization. As the sweating fraction is increased, the crystalline layers grown at lower cooling rates are purified more highly. Eventually, the crystallization rate is much more important than the sweating rate. The effective distribution coefficient ranges from 0.01 to 0.25 for the crystal growth rates of 1.2 × 10^?6 m/s to 4 × 10^?6 m/s.     

溶剂萃取法从乙二醛水溶液中回收醋酸

溶剂萃取法从乙二醛水溶液中回收醋酸李玉安田恒水路秀林（华东理工大学化学工程系，上海２００２３７）关键词萃取乙二醛醋酸１前言乙醛硝酸氧化法制乙二醛的水溶液中含有乙二醛约９％（ｗｔ），醋酸约９％（ｗｔ），硝酸约１％（ｗｔ）及少量草酸、乙醛酸。要得到高质...