An alternative supercritical fluid extraction system for aqueous matrices and its application in pesticides residue analysis

Abstract

Supercritical fluid extraction (SFE) is a rapid and convenient method for the isolation of organic compounds from environmental samples. This paper describes a supercritical carbon dioxide (CO₂) extraction system that uses a newly designed extraction cell to recover organic compounds from an aqueous matrix. Analysis of the extracts by gas chromatography‐electron capture detector (GC‐ECD) indicated that the herbicide trifluralin (2,6‐dinitro‐N,N‐dipropyl‐4‐trifluoromethylaniline) could be quantitatively extracted by using the SFE system proposed with small amounts of sample. The percentage of recovery obtained with the SFE system described was twice as high as the result obtained using a conventional solid‐phase extraction technique. Extraction by SFE was completed in a short period of time using a simple and low‐cost home‐made system that did not require the use of organic solvents.     

Modelling the extraction of soil contaminants with supercritical carbon dioxide

Extractions of volatile organic compounds (VOC’s) in contaminated soil from petroleum site were performed with supercritical carbon dioxide at different temperatures, pressures, extraction times, solvent flow rates, soil moisture contents and soil acidity. Three soil systems were investigated in order to compare the best parameters for extraction. A central composite rotatable design has been used to evaluate the influence of operation conditions on the extraction efficiency to generate model equations representing the types of soil. The results indicate that at least 70-80% of the initial amount of VOC’s can be removed at moderate temperatures even at very high moisture content. Supercritical extraction is best suited to silt type soils which have a low adsorption capacity. VOC’s recoveries from the artificial contaminated soil samples were higher in comparison with real contaminated soils. At moderate temperatures, the extraction efficiency for real soils is low because pollutants bind strongly to the soil.     

Using supercritical fluid extraction to measure the desorption and bioaccessibility of phenanthrene in soils

The aim of this paper was to measure the changing desorbable fraction and bioaccessibility of phenanthrene in two different soils with increasing soil-phenanthrene contact time using supercritical fluid extractions (SFE). Both soils were spiked with 100 mg kg⁻¹ phenanthrene and aged for 28 d. Desorption profiles were measured every 7 d using selective SFE conditions and the results were compared to ¹⁴C-phenanthrene mineralisation assays. Selective SFE showed significant differences in the rates and extents of desorption in the two soils, likely to be due to different organic matter composition. Post-extraction fitting of data yielded consistent SFE extraction times within ageing soils for bioaccessibility prediction.     

钻井废液的超临界水氧化处理及动力学分析

在反应温度为500～600℃、压力为25～30 MPa、停留时间为30～600 s的条件下,在连续式反应器中研究了钻井废液的超临界水氧化反应.结果表明:钻井废液的COD去除率可达90.00%以上;在600℃、停留时间为600 s时,钻井废液氧化后,剩余收集液的COD＜120 mg/L,满足《污水综合排放标准》(GB 8978-1996)中的二级标准.用幂函数方程描述了氧化剂过量时钻井废液超临界水氧化的反应动力学规律,反应速率常数与温度的关系符合Arrhenius公式,随停留时间的增加、温度的升高,有机物的去除率显著增加;反应速率常数随压力升高而增加,但反应速率常数的增幅随压力的升高而减小,反应活化体积不是常数.在25 MPa时,反应活化能和频率因子分别为(17 745.430 40±1 114.983 42)kJ/mol和1.152 3×10-4s-1模型计算值与实验值的误差在±15%以内.     

超临界水氧化活性艳红M-2B染料废水动力学研究

用H2O2作为氧化剂,在595～704 K、18～30 MPa条件下,对活性染料废水进行超临界水氧化反应.实验结果表明,COD去除率随温度、压力、停留时间和氧化剂量的增加而上升,在704 K、28 MPa时,COD去除率可达到98.4%,停留时间小于35 s.COD、H2O2和水的反应级数分别为1、0和0;反应活化能Ea为37.21 kJ/mol;指前因子A为76.69 s-1.     

超临界水氧化法去除废水COD的动力学研究

用超临界水氧化法(SCWO)处理有机废水,去除其COD?在高于水临界点(Tc=647K,Pc=22MPa)的温度和压力(673～813K,28～35MPa)下,用氧气作为氧化剂且过量,对含多元酚类等有机物的废水进行氧化处理?研究了超临界水氧化法处理废水时COD的去除动力学?在实验条件下,废水COD的去除动力学对COD是一级?氧气是零级;其速率常数与温度的关系符合Arrhenius公式;压力也明显地影响速率常数,随压力的升高而增大;反应的活化体积不是一常数?      

超临界二氧化碳中的化学反应

介绍了超临界二氧化碳的性质,总结了超临界二氧化碳中的加氢反应、氢甲酰化反应和氧化反应,并找出存在的问题,提出解决的建议。     

超临界水氧化法处理竹子溶解浆生产废水的实验研究

介绍了利用目前国内最大超临界水氧化中试反应器(2.2L+1.7L)对竹子溶解浆生产废水进行处理的试验,其反应装置处理水量可以达到900~1100L/d。分析了超临界水氧化过程中不同反应温度、时间、压力及其氧气浓度对该废水COD处理效率的影响。实验结果表明:在温度为500℃、压力为24MPa,氧化反应时间为60s时,其COD去除率达到99.2%;氧化反应时间为90s时,其COD去除率达到99.95%。处理后的排水能够达到国家规定的排放标准。同时对超临界水氧化反应过程中出现的反应机理及放热现象进行了探讨。     

超临界水氧化法处理苯胺废水

水样中苯胺的超临界水氧化（SCWO）表明氧化剂过氧化氢的用量,试验温度,压力和停留时间对水中TOC的去除率有显著影响,在500℃,25MPa和K1．1条件下,停留时间为35s,TOC去除率可达99％以上,TOC去除率随起始浓度的增加而提高,这表明SCWO适于处理高TOC值废水。     

Feasibility investigation on a dual waste-plastics recycling system concept

Fiber-reinforced plastics (FRP) were first used as a material for boats and bath tubs about 40 years ago. Because of their great durability, wastes including FRP products are increasing. In addition, since the FRP resin is synthesized from expensive reactants, material recycling is highly desirable. Recycling using supercritical water is one solution; however, the cost of producing the high pressure and temperature needed to produce supercritical water prevents the concept from being realized. Therefore, we proposed a system concept based on dual waste-plastics recycling. A numerical survey of the results confirmed that our concept was feasible and would contribute to resource recycling as we expected. Received: January 6, 1998 / Accepted: July 23, 1999