Communications

References
[1] [2] [3] [4] [5] [6] [7] Berg, F., Technische Flaschenbetriebskontrolle, Brauwelt 108 (1968) No. 45/46, pp. 833838. Commault, C.; Semery, A., Taking into Account Delays in Buffers for Analytical Performance Evaluation of Transfer Lines, IIE Transactions 22 (1990) No. 2, pp. 133142. DIN 40 041, Zuverlssigkeit, Beuth, Berlin 1989. Dallery, Y.; David, R.; Xie, X., An Efficient Algorithm for Analysis of Transfer Lines with Unreliable Machines and Finite Buffers, IEEE Transactions on Automatic Control 34 (1989) No. 9, pp. 943953. Gershwin, S. B., Manufacturing Systems Engineering, Prentice Hall, Englewood Cliffs 1994. Glassey, C. R.; Hong, Y., Analysis of Behavior of an Unreliable n-Stage Transfer Line with (n-1) Interstage Storage Buffers, Int. J. of Prod. Res. 31 (1993) No. 3, pp. 519530. Rdler, T., Modellierung und Simulation von Abfllinien, VDI, Dsseldorf 1999, Ph. D. Thesis, TU Mnchen.

Table 1. Inorganic contents of the used model solution, pH: 4.757.10. Element Calcium Magnesium Iron Cadmium Lead Chromium Copper Nickel Zinc Concentration in lg/l 100000 20000 10000 100 1000 10000 2000 1000 10000 Legal Limits [2] in lg/l 100 500 500 500 500 2000

This paper was also published in German in Chem. Ing. Tech. 72 (2000) No. 6, pp. 627630.

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Separation of Heavy Metals from Landfill Leachate by Reactive Liquid-Liquid Extraction*

By Wulfhard Mickler**

The objective of our work is the simultaneous separation of heavy metals from alkaline earth metals and iron in order to obtain a leachate which we can lead back to the landfill. The reactive extraction [3] as a separation process offers the possibility of a selective separation of cations, that is, the separation of toxic from unproblematic components, and also includes the possibility of electrolysis or further winning processes to obtain the desired metals. For the realization of extraction processes, several commercial extractants and technical equipments [4] are available.

2 Experimental
2.1 Extractants

1 Problem
Based on a study of the German Ministry of Research and Technology in 1990 [1] every year about 2.5 t of heavy metals are released per hectare of landfill by aqueous leaching. This leachate contains approximately 2000 t of heavy metals per year. Their decontaminations in accordance with the legal requirements represent an enormous potential for easing the burden on the environment. On the other hand, this potential opens new possibilities in the production and recycling of selected compounds. In Tab. 1 the composition of a model solution is given. Its composition corresponds to a landfill leachate resulting from a municipal dump leachate produced by an average German city. The legal limits for the landfill leachate after the wastewater regulations Abwasser-Verwaltungsvorschrift are indicated in the third [2] column. Really, these values often are exceeded. Actually, in most cases, a decontamination of such solutions occurs by the transfer of the problematic cations into insoluble compounds usually done by precipitation. The result of the procedure is an unspecific separation of all liquid components and the cycle of waste (landfill leaching deposition) begins anew, certainly on a higher level.
[*] Revised lecture presented at the 4th GVC Abwasserkongress, Bremen, Sept. 69, 1999. [**] Dr. W. Mickler, Universitt Potsdam, Institut fr Anorganische Chemie und Didaktik der Chemie, Postfach 601553, D-14415 Potsdam, Germany; e-mail: wmickler@rz.uni-potsdam.de

As extractants we have selected especially commercial compounds in order to compare their extraction behavior with that of our own -diketones. 2.1.1 Alkylphosphoric Acid

di-(2-ethylhexyl)phosphoric acid (Bayer)

di-(2-ethylhexylmonothio)phoshoric acid (Bayer)

2.1.2 Chelate-Forming Extractants LIX 54 (Henkel KGaA)

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Communications Mixture of at least four isomers of 1-phenyl-3-isoheptyl-1,3propanediones [5] used especially for the separation of copper from ammoniacal solutions [6]. 4-Acyl-5-pyrazolone The produced compounds correspond to the general formula: tration was generally in the range of 104 mol L1, at an ion strength of I = 0.1 mol L1 (KNO3). All chemicals were of p.a. quality. The metal stock solutions were prepared by dilution of a Merck standard solution with bidistilled water. As solvent for the extractants, kerosene (b.p.: 100140 C) was used with n-octanol as modifier. Generally, the concentration of the ligands was adjusted in the range of 103 ... 102 mol L1 in a phase ratio to the model solution of 1 + 1 (20 mL). The commercial extractants were used as received apart from the separation of the diluent. In the case of the extraction from the model landfill leachate the concentration of die ligands was adjusted at 10 % by volume. Each extraction cycle was performed by a mechanical shaker within 10 minutes. The composition of the model solution of the landfill leachate corresponds to Tab. 1. The pH adjustment was done by adding HNO3 or NaOH, respectively. For the measurements a pH meter MP 230 (Mettler-Toledo, Germany) with glass electrode (Schott, Germany) was used. After reextraction from the organic phase the metal concentration was determined by AAS (AAS 1100 B, Perkin Elmer). Corresponding to the overall reaction for chelate-forming extractants1) Mn+(w) + n HL(o) , MLn(o) + n H+(w) and alkylphosphoric acids Mn+(w) + m(HL)2(o) , MLn(HL)m-n + n H+(w), (2) (1)

4-acyl group -butanoyl -octanoyl -stearoyl -(2-ethylhexanoyl) -octadecenoyl

R -(CH2)2-CH3 -(CH2)6-CH3 -(CH2)16-CH3 -CH(C2H5)-(CH2)3-CH3 -(CH2)7-CH=CH-(CH2)7-CH3

The 4-acyl-5-pyrazolones were synthesized according to the Jensen method [7] by the reaction of 1-phenyl-3-methyl-5pyrazolone with the corresponding acid chloride. The extraction behavior of the compounds was reported in [8]. Hydroxyoxime

which exists in the dimeric form (2 HL (HL)2), the distribution coefficient D = cMn+(o)/cMn+(w) The commercial extractant LIX 84 (2-hydroxy-5-nonylacetophenone-oxime/Henkel) is used for the hydrometallurgical production and extractive separation of nickel and copper. (3)

was calculated from the metal concentration in the aqueous phase before extraction and from the organic phase after re-extraction with sulfuric acid. The extraction yield (E%) can be calculated using the relation E% = D/(D + 1) 100 % The slope n of the function log D = n pH + log Kex + n log cHL(o) (5) (4)

2.1.3 Alkylphosphonic Acid

corresponds to the composition of the extracted compounds. By the trade name IRONEX [9] BASF and Preussag Co. presented a new amino-methylenephosphonic acid (AMPS). It seems likely to test it for the separation problem because of the reported good selectivity relating to iron [10]. For the extraction constant Kex, the equation log Kex/n = pH + log cHL is valid. Distribution coefficient and extraction constant are connected by relation (5).
1) List of symbols at the end of the paper. 0930-7516/01/0505-0471 $ 17.50+.50/0

(6)

2.2 Experimental Conditions The extractions were performed as single experiments in separation funnels at room temperature. The metal concenChem. Eng. Technol. 24 (2001) 5,

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Communications Finally, from the extraction data the stability constants = cMLn/(cM n+ cL-n) of the extracted species could be derived. (7) alkyl-substituted -diketone, at least consisting of four isomeric compounds, mainly developed for the extraction of copper from ammoniacal solutions.

3 Results
Fig. 1 shows the results of the simultaneous extraction of a model landfill leaching with alkylphosphoric acid. The equilibrium of the extraction is reached after five minutes. It can be seen that the extraction process is unspecific and especially by natural conditions the extractant can be blocked because of the expected high concentration of calcium and magnesium in the leachate. Generally, the purification of a leachate followed by its trickling on the landfill is possible at a pH about 5 with the help of D2EHTPA. In this case all problematic cations can be extracted but iron remains in the leachate because of kinetic reasons.

Figure 2. Simultaneous extraction of heavy metals from landfill leachate (model solution) with LIX 54 and 1-phenyl-3-methyl-4-(2-ethylhexanoyl)-5-pyrazolone (pH = 4.97).

Figure 1. Simultaneous extraction of heavy metals from landfill leachate (model solution) with alkylphosphoric acids (pH = 4.79).

Thiophilic elements, like copper, zinc, cadmium, are better extracted with D2EHTPA whereas D2EHPA prefers the harder elements. Corresponding to (5), the slope of the function log D = f (pH) gives an information about the transfer of protons during the formation of the transferred complexes. For the two-valued elements the slope n is equal two and we found n equal three for the three-valued elements, such as iron(III) or chromium(III). From the function log D = f(cL) a transfer of ligand molecules can be derived. Under the selected experimental conditions the slope for these elements was found to be n = 1 and this means the formation of a 1:1 complex with the coordination of the corresponding number of dimeric acid molecules.

3.1 -Diketones The extraction behavior of the commercially available diketone LIX 54 and comparable with that the more acidic 4-acylpyrazolone is shown in Fig. 2. LIX 54 (Henkel) is an 472
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Among the synthesized 4-acylpyrazolones, especially the 2-ethylhexanoyl-substituted derivative shows the best solubility in organic diluents. Therefore, it was selected for the extraction experiments. The diagram shows the extraction of typical contents of a landfill leachate with 2-ethylhexanoyl-pyrazolone. In the neutral pH region, a nearly complete separation of copper, iron, and zinc occurs whereas the alkaline metals are extracted only incompletely. Nickel and cadmium are only slightly included in this region. It is unfavorable for the whole process that the alkaline earth metals are extracted likewise excellently from the solution particularly as they were expected in the natural water in a relatively high concentration (relative to the heavy metals). In that case the hazard exists of blocking of the extractant or of problems during the reextraction, respectively. Anomalies were also observed in the extraction behavior of magnesium and calcium. In the case of magnesium a 1:2 complex is extracted whereas the calcium complex has been found in the composition of 1:1. The higher affinity of calcium to water may be discussed as a reason for that behavior so that the ligand exchange at the interface is hindered. For the discussion of the separation problem, LIX 54 was used comparatively as representative of a commercial extractant. The course of the curves has expected promising results for the extraction of heavy metals up to the pH range of the landfill leachate. The separation of alkaline earth metals should be expected only at higher pH values. The composition of the extracted species may be derived from the slope of the function log D = f (cL). LIX 54 as well as 2-ethylhexanoylpyrazolone form 1:2 complexes with iron(II). With iron(III) the expected 1:3 complexes were found. In the cases of the iron(III) extraction with LIX 54 and the pyrazolone, the nearly identical rise of the curves has not been expected.
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Communications These results are contrary to the findings at the alkylphosphoric acids where 1:1 complexes had been found each. Generally, significant differences in the extraction behavior of cations occur during the extraction of a modeled landfill leachate with 2-ethylhexanoyl-5-pyrazolone whose concentration is 10 % by volume in kerosene. In the almost neutral pH region, the heavy metals are extracted nearly completely whereas the alkaline earth metals are less concerned. It is also interesting that only 10 % of calcium was extracted although it is present in the solution in an excess to magnesium of 1:5. The magnesium extraction is not influenced by calcium ions. Beside a steric hindrance of the calcium extraction also the higher enthalpy of formation of the calcium hydroxide in comparison with the magnesium compound may come into consideration for explanation of this behavior. The higher stability of the calcium species makes the exchange reaction of the ligand at the interface and consequently the extraction more difficult. We found a similar behavior in the case of the simultaneous extraction of heavy metals from a model solution by LIX 54. All the interesting heavy metals are extracted in a good yield and it is favorable that calcium is only to 6 % and magnesium to 23 % coextracted. The extraction of cadmium is seriously interfered although the mass relation in our model solution between cadmium and magnesium is only 1:200 and to calcium 1:1000. The varying structure of the complexes is certainly an important reason for these differences. We found an octahedral structure for the 1:2 complex of cadmium. That means, in the case of the extraction from an aqueous media we assume that two water molecules are coordinated to the complex and therefore the phase transfer is probably hindered. 3.2 Hydroxyoxime LIX 84 (2-hydroxy-5-nonylacetophenonoxime) has been tested as a further representative of a chelate-forming extractant well known for a long time in the hydrometallurgy for the production of copper and nickel [6]. Fig. 3 shows the result of the simultaneous extraction of the interesting metals with LIX 84 at different pH. The results are in fact satisfactory only at the first look. Among the selected conditions the alkaline earth metals are separated only slightly. But in the case of zinc we observed problems in the separation process. However, in this case the relatively high starting concentration should be considered (20 % of 10000 lg/l). The extraction behavior of chromium and cadmium seems to be more problematic. We suppose here a hindered complex formation reaction, e.g., by competition reactions, hydrolysis or especially in the neutral pH region, kinetically stable favored hydroxy compounds of the chromium in the aqueous phase respectively. 3.3 Aminomethylphosphonic Acid (IRONEX) Fig. 4 shows the plot of the log D/pH function for the extraction of different II- and III-valent cations. The differences in the separation behavior between the two groups are clearly distinguishable. The III-valent cations indium, gallium and iron are separated in the stronger acid media whereas the II-valent ions are separated only at medium or higher pH value. As the reasons should be certainly discussed differences in the mechanism of the complex formation and in the case of cadmium and nickel the hindered complex formation and therefore also the extraction rate.

Figure 4. Extraction of selected cations with aminomethylphosphonic acid, log D = f (pH); l Fe3+, s In3+, Ga3+, * Cu2+, n Ni2+, Y Cd2+.

Figure 3. Simultaneous extraction of heavy metals from landfill leachate (model solution) with LIX 84. Chem. Eng. Technol. 24 (2001) 5,

The composition of the extracted species could be found from the plot of the function log D = f(cL). Nearly as expected, three ligands are coordinated by the III-valent iron, indium and gallium whereas the II-valent ions form 1:2 complexes. Tab. 2 gives the extraction parameters. From the extraction data, the favorable qualities of the extractant can be recognized clearly for the separation of III-valent cations towards the II-valent ones. Especially the high extraction coefficient for the extraction of iron is obvious. Comparing the influence of different diluents on the extraction equilibrium, surprisingly the best results were obtained by aromatic solvents towards the halogenated and aliphatic hydrocarbons.
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Table 2. Parameters of the extraction with AMPS (tex = 30 minutes). Metallion In Fe Ga Cu Zn Cd Ni pH1/2 - 1.10 - 0.80 - 0.10 3.35 6.57 7.25 7.85 lg Kex 9.48 10.64 6.30 - 1.35 - 3.45 - 2.08 - 3.38

equilibrium is clearly displaced to the ammine complexes and the ligand exchange with AMPS is possible. Otherwise, in the case of small ammonia concentration, the formation of less soluble hydroxy compounds is favored. Fig. 5 shows the order of magnitude of the extraction isotherms of the copper extraction with different commercial extractants and a more acidic 4-acylpyrazolone. At comparable conditions only slight advantages of LIX 54 could be observed.

Shellsol AB as representative for an aromatic long-chain hydrocarbon shows similar values as could be found by aliphatic compounds. As a reason we discuss the influence of the branched aliphatic substituent of the ligands having a small dielectric constant in relation to the diluents with higher values (such as toluene or chloroform). The important difference between these DK values cause an unfavorable solubility of the complexes and therefore also unfavorable distribution data. In this connection, the hindered diffusion of the metal complex in the different organic solvents seems to be an important reason for the diversity of the distribution coefficient. However, the influence of the diluent is less dramatic so that for environmental reasons the selection of fewer problematic diluents is justified. The important influence of inorganic, water-soluble compounds on the separation behavior of cations has been tested with the help of the extraction function log D = f (cA-). Especially in the case of the extraction from natural media, such compounds as cyanide, tartrate, ammonia, humic acids and chloride may act as sequestering agents and hinder the separation. Indeed, the extraction of copper as a two-valent cation with AMPS is hindered corresponding to the increasing complex stability in the sequence CN > tartrate > ammonia > chloride. Chloride ions influence the separation only insignificantly whereas cyanide prevents the metal separation starting from an excess of 1:10. The influence of tartaric ions and ammonia could be found in the same order. The extraction is hindered only from an excess of 1:1000. With regard to the mechanism, the very similar stability constants of both the copper complexes should be discussed as the dominating, decisive influence. However, under natural conditions at best the influence of chloride ions is important so that problems are not to be expected. In the case of humic acids which can be regarded as representatives of metal-soil interactions, the stability relations are similar to tartrate. But it should be considered that humic acid was inserted in the system in a size of weight percent (up to 1 %) so that the expected influence by a natural landfill leachate should be very small. Using ammonia as competition ligand in the aqueous phase, the course of the extraction curve shows that only above an ammonia concentration of 1 mol/L the extraction is nearly quantitative. This can be easily understood taking into account that only in a sufficient high excess of ammonia the complex 474
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Figure 5. Extraction isotherms of the copper extraction; & 4-acyl-5-pyrazolone, l AMPS, KELEX 100, Y LIX 54, wHL = 10 % in kerosene/toluene.

Generally, the differences in the amount of extraction are less dramatic. By a 10 % (v/v) organic solution of the ligands, about 11.5 g/L copper could be separated by LIX 54 whereas 10.1 g/L could be found in the case of KELEX 100. With the help of AMPS 10.5 g/L are possible and the more acidic 4-acyl5-pyrazolone can separate 9.2 g/L of copper. Summarizing, Fig. 6 presents the results of the simultaneous reactive extraction of metals from a model landfill leachate. Apart from iron, LIX 54 could be used advantageously for an extraction process unfortunately without any considerable extraction of cadmium. But it is favorable to separate nontoxic alkaline earth metals from problematic heavy metals. Such a complex task as the separation of cations from natural solutions cannot be solved easily in a one-step extraction process. Better results should be obtained by the

Figure 6. Simultaneous extraction of heavy metals from landfill leachate (model solution) with selected extractants (pH = 5.3, wHL = 10 % in kerosene). Chem. Eng. Technol. 24 (2001) 5

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Communications combination of different procedures, e.g., extraction, ionexchange and precipitation.

Acknowledgements
The author wishes to thank Henkel KGaA, Bayer AG, BASF AG and Dt. Shell AG for kindly providing the commercial extractants.
Received: December 19, 2000 [K 2645]

PDA Measurement of Drop Size Distribution for Liquid-Liquid Dispersing in Agitated Tanks
By Martin Wille, Gert Langer and Udo Werner*

1 Introduction
In numerous industrial applications agitated tanks are used for dispersion operations. In the case of liquid-liquid dispersing, which is treated in this paper, the drop size distribution results from a dynamic equilibrium between breakup and coalescence of droplets. Usually dispersion operations in agitated tanks are carried out under turbulent flow conditions. Therefore it is assumed that the impact of turbulent shear stresses (Reynolds stresses) is the decisive mechanism for the breakup of deformable particles like droplets, see e.g. [1]. A review of theoretical and experimental work concerning the hydrodynamic stress on particles in turbulent impeller flows in [2] reveals that a description of dispersion processes based on the maximum turbulent shear stress in an agitated tank only is not sufficient. On the one hand axial-flow impellers like pitched-blade turbine, propeller and MIGimpeller provide better dispersion characteristics than the radial-flow Rushton turbine at the same average specific power and energy input. On the other hand laser-Doppler anemometry (LDA) measurements in [3] show that the Rushton turbine produces much higher maximum turbulent shear stresses than the axial-flow impellers. Langer and Deppe [2] conclude that the specific macroscopic flow field of an impeller has to be considered for a better understanding of the breakup process of droplets in agitated tanks. The influence of elongational flow that provides more effective breakup of droplets than shear flow is especially significant for the resulting drop size distribution [4,5]. It is the purpose of this paper to investigate the dispersion characteristics of different axial- and radial-flow impellers at the same average specific power and energy input. PhaseDoppler anemometry (PDA) is used to measure the drop size distribution. The results obtained are the basis for an extensive assessment of current approaches for liquid-liquid dispersing and the development of new concepts taking into account the macroscopic flow field in agitated tanks discussed previously [2].

Symbols used
Kp [C] c [mol/L] c A[] w [%] Mn+ (w) [] HL(o) [] MLn(o) [] D [] E% [] Kex [] pH1/2 [] [] Abbreviations D2EHPA D2EHTPA di-(2-ethylhexyl)phosphoric acid di-(2-ethylhexylmonothio)phosphoric acid boiling point concentration concentration of anions mass fraction cation in the aqueous phase extractant in the organic phase metal complex in the organic phase separation coefficient degree of extraction (in %) extraction constant pH value of 50 % extraction stability constant of the metal complex

References
BMFT-Report, 02-WA 8721/0, Witten 1990. Rahmen-Abwasser-Verwaltungsvorschrift Rahmen-AbwasserVwV, GMBl. 1996, p.729. [3] Thornton, J. D., Science and Practice of Liquid-Liquid Extraction, Oxford University Press, Oxford 1992. [4] Cox, M., in: Principles and Practices of Solvent Extraction (J. Rydberg, C. Musikas, G. R. Choppin, Eds.) Marcel Dekker, Inc., New York, Basel, Hong Kong 1992. [5] Mickler, W.; Uhlemann, E.; Herzschuh, R.; Wenzlawiak, B.; Plaggenborg, L., The Characterization of the Active Components in Commercial -Diketones, Sep. Sci. Technol. 27 (1992) 8/9, pp. 11711179. [6] Henkel-Produktinformation and Reinhardt, H.; Ottertun, H. D., EPA 0 005 415 (1979). [7] Jensen, B. S., The Synthesis of 1-Phenyl-3-methyl-4-acyl-pyrazolones-5, Acta Chem. Scand. 13 (1959) pp. 16681670. [8] Mickler, W.; Reich, A.; Uhlemann, E., Separation of Metals by LiquidLiquid Extraction with -Diketones and 4-Acylpyrazolones, Proc. Int. Solv. Extrac. Conf., Melbourne 1996, pp. 415420. [9] Delmas, F.; Ehle, M.; Koch, R. O.; Nogueira, C.; Oppenlnder, K.; Placenat, C.; Ujma, K. H.; Weigel, V., Development of a Selective Extractant for Iron in Hydrometallurgical Process Solutions, Proc. Int. Solv. Extrac. Conf., Melbourne 1996, PP. 293298. [10] German Patent DE 4421932 (1996) BASF (Invs.: M. Ehle, K. Oppenlnder). This paper was also published in German in Chem. Ing. Tech. 72 (2000) No. 5, pp. 506511. Chem. Eng. Technol. 24 (2001) 5, [1] [2]

[*] Dr.-Ing. M. Wille, Degussa-Hls AG, Corporate Process Technology, P.O. Box 1345, D-63403 Hanau-Wolfgang, Dr.-Ing. G. Langer and Prof. em. Dr.-Ing. U. Werner, Chair of Mechanical Process Engineering, Department of Chemical Engineering, University of Dortmund, D-44221 Dortmund, Germany; e-mail of corresponding author: g.langer@ct.unidortmund.de 0930-7516/01/0505-0475 0930-7516/01/0505-0475 $ $ 17.50+.50/0 17.50+.50/0

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