Carbon. Vol. 30, No. 5, pp. 767-771, Printed in Great Britain.

1992

OQO8-6223/92 $5.00 + .oO Copyright 0 1992 Pergamon Press Ltd.

BEHAVIOR OF PERTECHNETATE ION ADSORPTION FROM AQUEOUS SOLUTIONS SHOWN BY ACTIVATED CARBONS DERIVED FROM DIFFERENT SOURCES
KATSUO ITOand AKIRA YACHIDATE* Research Institute of Mineral Dressing and Metallurgy, Tohoku University, Katahira-2, Aoba-ku. Sendai 980, Japan
(Received I Ocioher 199

I ; accepted in revised.fbrm 2 January I99 1)

Abstract-Pertechnetate ion (TcO,) adsorption from aqueous solutions is compared between activated carbons derived from different sources, by reference to the distribution coefficient Kd of Tc between adsorbent and solution. Adsorption runs made in systems containing HCI and HN03, with pH parametrically varied by NaOH addition, proved Kd to rise with lowering pH in the acidic region in the case of activated carbon samples derived from coconut shell, from oil pitch, and from saw dust, but not in the case ofthose derived from coal or bone. In certain systems containing high concentrations of acidic radical, the rise of Kd in the acidic region was followed by a decline toward higher acidities. Also, in a certain range of acidic radical concentration, when the adsorption was left to equilibrate beyond several hours, the TcOk once adsorbed tended to desorb again, displaced by a coexisting other anion, which caused Kd to relapse with further progress ofequilibration time. The desorption behavior differed with the kind ofactivated carbon, and with the kind and concentration of the acid contained in the system. Pretreatment of the adsorbent with acid devoid of Tc04 resulted in lowering of the adsorption performance. Key Words-Activated ment. carbon, carbon sources, pertechnetate ion. adsorption, desorption by displace-

1. INTRODUCIION

Technetium-99 is counted among isotopes presenting the promise of useful applications in the near future, and this calls for the establishment of a practical method for extracting Tc from its source, which is high-level liquid waste (HLLW) discharged from nuclear installations[ I]. For practical application, the beta-decay half-life of 99Tc amounting to 2 10,000 y could be found inexpediently long, but this nuclide can be converted by nuclear reaction into other isotopes of much shorter life[2]. A requirement of importance equal to extracting Tc for use is to prevent TcO; from leaching out into the underground water in contact with solidified HLLW that has been disposed of after solidification in glass, since the security of this practice would depend on the availability of a reliable means of protecting against uncontrolled release of this longlived nuclide into the surrounding subterranean environment. Such protection can be ensured by adsorbing onto activated carbon the TcO; contained in the HLLW before solidification, and also after disposal ofthe solidified HLLW, by collecting the TcO, that leaches into the soil. Activated carbon can be derived from various organic sources, and the choice of source material will influence the capacity of the product-activated carbon-to serve its purpose of adsorbing TcO;.

The present study is aimed at obtaining basic information to serve in selecting the activated carbon to be used, and in optimizing the conditions for the separation of Tc from HLLW, and for the collection of Tc that has leached into underground water.
2. EXPERIMENTAL

2.1 Preparation of 9SmT~ was Technetium-95m produced by 95Mo(d,2n)95mTc reaction, using a cyclotron of the Cyclotron and Radioisotope Center, Tohoku University. Carrier-free 95mT~0; was extracted from tetraphenylarsonium chloride-chloroform solution. This 95mT~O; was stripped into 8 M HNOX; the resulting solution was divested of HNOj by evaporation[3], and the residue was dissolved in water. The experiment was performed in batches, on small quantities ofthis solution. The radioactivity of 95mT~ was determined by means of a Capintec Inc. CRC- 12 radioisotope calibrator.

2.2 Materials
Five samples of carbonaceous materials-listed in the upper half of Table l-were examined for their adsorbability of TcO;. They were of the commercially marketed grade that is commonly used as fuel. The material was ground and sieved to 0.59-2.00 mm size, then decanted with distilled water, followed by drying overnight at 120C. The activated carbon taken up for study consisted of five samples derived from different sources (listed in the lower half of Table 1). They were of the com-

*Subsequently transferred to Nissho lwai Corporation, Tokyo.

768

K. ITO and A. YACHIDATE Table 1. Surface area and pore size of activated carbons, and distribution coefficient Kd of TcO; on carbonaceous materials and activated carbons Source material Particle size (mm) 0.495-1.981 0.495-I .98 I 0.495-l .98 1 0.495-1.981 0.59-2.00 Surface area (m*/g) Pore size (nm) -

Sample

pH 8.7 7.9 7.3

Kd

Coke A B Coal Anthmcite Charcoal Activated carbon A Activated carbon B

Oil coalpitch

952

-1.5

L3 014 2.5 3640.4

Coconut shell

;*: 918

Activated carbon C Activated carbon D Activated carbon E

Oil pitch Coal Saw dust Bone

0.35-0.70 0.5 i-2.00 -0.04 0.04-0.07

810 880 1150 81

1.5 2.3 2.5 12.4

10.5 8.0 9.1 8.2

447 208 73 16

50 ml TcO; solution containing 0.16 M (H,Na)N03, 2 g carbonaceous material.

mercially marketed grade commonly treatment.

used for water

2.3 Procedure
A known quantity of the adsorbent sample was equilibrated with solutions of various acids and of their sodium salts containing IO-l2 M (mol.dm-3, TcO;. Series of runs were performed in a system containing the prescribed acid in the prescribed total acidic radical concentration, and the system pH was paramet~cally varied by the addition of NaOH. For ~uilibmtion, the solution and activated carbon sample were placed in a polyethylene bottle, capped, and shaken at a speed of 50 strokes min- for 24 h at 25C. The pH of the supernatant was measured, and 2 ml of this solution was then submitted to y radioactivity counting with an NaI(T1) scintillation detector. The surface area of activated carbon was determined by means of a MICROMERITICS ASAP2400 Automatic Surface Area and Pore Size Analyzer, after degassing for 1 h at 200C. 3. RESULTS AND DISCUSSION The distribution coefficient Kd of Tc between adsorbent and solution is calculated using the formula

the activated carbons compared with the carbonaceous materials. These first adsorption equilibrium experiments on activated carbon were carried out in systems containing solutions of HCl and HN03 and their sodium salts. Figures la and 1b compare the four activated carbon samples. In the case of activated carbon A (open square symbols in Fig. la), the acidic region toward the left is marked by a rise in &with decreasing

Kd=T----*-Q m
where Q is the fraction of Tc adsorbed, V the volume of liquid phase, and m the weight of adsorbent. In the figures that follow, the results obtained for Kd are plotted against pH varied by NaOH addition, or against time elapsed in equilibration. The acid and the total acidic radical concentration in the system adopted for each series of runs are indicated in the relevant figure legends. The adsorption experiments were first carried out for comparing the performance between the different carbonaceous materials and activated carbons used as adsorbent. As indicated in Table 1, jncompambly better TcO; adsorption ~~ormance is provided by jiD I 2 4 6 P
Fig. I. Distribution coefficient &of Tc compared between activated carbon samples derived from different sources and in systems containing different acids adjusted to different acidic radical concentrations-related to pH of solution adjusted by NaOH addition. 50 ml TeOr solution, 0.1 g activated carbon: (a) 1 M (H,Na)CI system: 0: activated carbon A, a: activated carbon B, a: activated carbon C, A: activated carbon D, 0:activated carbon E, (b} 1 M (H,Na)N03 system: 0: activated carbon A, A: activated carbon 8, Ed activated carbon C, 0: activated carbon E.

8 t

10 t

12

14 1

Pertechnetate ion adsorption from aqueous solutions

769

pH. This behavior is attributable to quickened removal of TcO; in the acidic region[4], with the adsorption onto activated carbon supplemented by TcO: reaction with oxonium ions[5,6,7] generated by interaction of H+ with the functional groups ofactivated carbon. Imm~iately adjoining this acidic region toward the right is a stretch around neutral pH 7 that forms a level stage, created by the balance of competition for adsorption onto activated carbon between TcO: and the relevant anion; this is followed further toward the right by the basic region of declining &, where TcO: adsorption starts to be outdone in its com~tition with OH-. The rise of Kd with increasing acidity noted above for activated carbon A has been similarly observed in other runs made with activated carbons B and D (open and closed triangles), but in the case of activated carbons C and E (closed and open circles), the plots failed to rise in this region. With activated carbon D, the closed triangle plots are seen to attain in the acidic region a level that closely approaches the open squares of activated carbon A. The irrelevantly low Kdvalues for activated carbons indicated in Table I can be imputed to a difference in the conditions under which the data were obtained, including the ratio of liquid volume to quantity of adsorbent. The data of Fig. la were obtained in a I M (H, Na)Cl system; in Fig. lb a similar difference in adsorption behavior between the different activated carbon samples is also noted in a 1 M (H, Na)N03 system. The foregoing findings would indicate that the activated carbons A and B would be superior to

activated carbon C for adsorbing Tc from HLLW solutions. With systems containing 3 M (H, Na)Cl (triangular plots in Fig. 2a) and 2 M or higher (H, Na)NO, (ah plots except square, for 1 M (H, Na)NO,), a drop in K, value is seen to occur with increasing acidity. In the instance of 2 M (H, Na) NO3 fopen circle plots in Fig. Zb), Kd distinctly falls beyond a peak that is attained at around pH 1, which would thus be indicated as the optimum acidity for adsorbing Tc from a nitric acid system. In practice, HLLW normally takes the form of an HNOX solution of around 3 M con~ntmtion[8]. This concentration could be lowered down to the above optimum level of pH 1 by denitration to decompose part of the NO;, or else by partially neutralizing the HN03. In underground water, a variety of mineral ions are present in minute amounts, but such ions would appear to exert no influence on the Tc adsorption behavior of activated carbon[4]. The present experiment has been conducted on systems containing large amounts of acids, and their presence should have to be taken into account in comparing the adsorption ~rfo~ance between different activated carbon samples. A simple test should be required to distinguish Tc adsorption between activated carbon samples. The variation of Kd with progress of equilibration time is shown in Fig. 3 for Tc adsorption on different activated carbon samples. The plots for 0.5 M H,SO,---from a previous study[4]-reveal a conspicuous relapse of Kd beyond 4 h, which can be attributed to the adsorbed TcO; being displaced by the more strongly adsorbed and more profusely present sulfate anions[9], deriving from the sulfuric acid that was added. Compared with activated carbon C, activated carbons A and B are seen to have produced higher peak

1oalo2 y y 102 1111111,IIII 543201 234567891011121314 CHbJQJt PH II

Fig. 2. Distribution coefficient Kd of Tc on activated carbon A in systems containing different acids adjusted to different acidic radical concent~tions-relate to acidic concentration and to pH of solution adjusted by NaOH addition. 50 ml TcOL solution, 0.1 g activated carbon A: (a) HCI system: a: I M (H, Na)CI solution, o: 2 M (H, Na)CI solution, A: 3 M (H, Na)CI solution;(b) HNOx system: o: I M (H, Na)NOs, 0: 2 M (H, Na)NOj, CI:3 M (H, Na)N03, A: 4 M (H, Na)Nq.

loos
Time f h

10"

Fig. 3. Time dependence ofdistribution coefficient KdofTc adsorbed by various activated carbons in 0.5 M f&SO,, solution. IO ml TcO; solution, 0. I g activated carbon A: A: activated carbon A, O: activated carbon B, 0: activated carbon C.

770

K.I~oand

A. YACHIDATE

values of I&, which occur at around 4 h of equilibration: at 100 h, the difference in Kd between the activated carbon samples is seen to have diminished to a small range. Beyond 100 h, Kdhas tended to rise again in the case of activated carbons A and B, but not with activated carbon C. The distinctive divergence of the curves in Fig. 3 between this activated carbon C and the other two samples cannot be attributed solely to the disparities in surface area and in pore size that are indicated in Table I. This freedom from relapse of Tc adsorption performance that characterizes activated carbon C could be turned to account by its application in prolonged service calling for stable performance, such as for the collection of Tc leaching out of solidified HLLW stored underground. For activated carbon A, the relapse of K-attributed to desorption of TcOi, displaced by other anions deriving from the added acid-has also been noted on adsorption curves obtained in systems of 0.1 M HNO,, 0.5 M HCl, and with HCIO, solutions of acidity above 0.1 M (Figs. 4a-c). On the other

hand, runs made in a phosphoric acid system (Fig. 4d) have presented no indication of such relapse through 24 h of equilibration; it is only beyond 30 h that a small drop in Kd can be discerned. The foregoing phenomenon of TcO; desorption by displacement was observed only with acidic solutions of pH below 1. The effect of pretreating the adsorbent with acid devoid of TcO; is revealed in Fig. 5, which presents-as in Fig. 4-the time dependence of &, for activated carbon A in systems containing either HNOj or HzS04. In the case of the H2S04 system, pretreatment of the activated carbon A with 10 M HZSOd solution is seen to have impaired adsorption performance, as evidenced by the closed plots in Fig. Sa. Pa~i~ularly in the case of adsorption from 0.5 M H2S04 system (closed symbols), which was a case noted in Fig. 4a to be subject to TcO; desorption by displacement, the relapse of Kddue to this phenomenon is seen to have been distinctly accentuated and prolonged by the pretreatment.

0.51

I I I I 051 10 30 Time/h

1 10

1 102

Fig. 4. Time dependence of distribution coefficient Kd of Tc adsorbed by activated carbon A in systems containing HN03, HCI, HC104, and H3P0, adjusted to different acidic concentrations. 10 ml TcO; solution, 0.1 g activated carbon A: (a) 0: 0.05 M HN03 solution, l: 0. I M HNOJ solution, qI:0.5 M HNO, solution, A: 1 M HN03 solution; (b) o: 0. I M HCI solution, o: 0.5 M HCl solution, A: I M HCI solution, CI:5 M HCI solution, V: 10M HCI solution; (c)o: 0.01 M HCIO, solution, A 0.1 M HCIO, solution, OI0.5 M HC104 solution, i: 1 M HCIO, sotution; (d) o: 0.1 M HJPOd solution, IX 0.5 M H,POa solution, A: 1 M H3POh solution, 7: 1.5M H3P04 solution, V: 2 M H3POI solution, 0 : 4 M H$O, solution.

Pertechnetate ion adsorption from aqueous solutions

111

10 Time/h

0.5 1

10

10

lo3

Fig. 5. Effect of pretreating adsorbent with acid devoid of TcOr on time dependence of dist~bution coefficient Kd of Tc adsorbed by activated carbon A in systems containing HN03 and H2S04 adjusted to different acidic concentrations. 10 ml TcO; solution, 0.1 g activated carbon A: Open symbois= no pretreatment; closed symbols=pretreated with 10 M Hz!304(diagram (a)), and 10 M HNO, (diagram (b)), both devoid of TcO;. (a) AA: Adsorption from 0.1 M HrS04, m: Adsorption from 0.5 M H$SOa. (b) AA: Adsorption from 0.05 M HN03, m Adsorption from 0. I M HNOs. With the HNQ system also, pretreatment with 10 M acid altered the adsorption performance, but as seen in Fig. Sb, the symptom of desorption by displacement-discernible in the plots for 0.1 M HN03 (open circles)-is not accentuated but conversely effaced by the pretreatment, and instead, an overall lowering of the iu, curve is noted (closed circles), as was the case with 0.1 M H,SO, (closed triangles of Fig. Sa) and with 0.05 M HN03 (closed triangles of Fig. 5b), both of which were not subject to desorption by displacement. for his collaboration in determining the specific surface area and pore size of activated carbons. Grateful acknowledgement is also due to Prof. K. Akiba of the Research Institute of Mineral Dressing and Metallurgy, Tohoku University, for his valuable discussions provided throughout the course of this study. M. Yoshida kindly edited the present text for grammatical conformity.

REFERENCES

4. CONCLUSION Activated carbon derived from coconut shell or from oil pitch would appear to be the most suitable for adsorbing Tc from high-level liquid waste. Activated carbon derived from coal could, on the other hand, be considered to excel others for prolonged service, for its stable performance with little variation due to desorption of TcO; from displacement by other anions. This kind of activated carbon should therefore be suitable for use in backfill material for pits bored for disposal of high-level liquid waste. The TcO; adsorption behavior of activated carbon will vary with lapse of equilibrium time, as well as with the kind and concentration of the mineral acids contained in the system.
A~~non,led~~rnmr-The authors wish to thank Y. Onodera of the Government Industrial Research Institute, Tohoku,

Discharges into the Environment, In Technetium in the Environment (Edited by G. Desmet and C. Myttenaere), pp. 2 I-28. Elsvier Applied Sci., London and New York (1984). 2. CURE: Clean Use of Reactor Energy, WHC-EP-0268, Westinghouse Hanford Company, Richland, Washington (1990). 3. K. Ito and T. Kanno, J. Nucl. Sci. Technol. 23,37 (1986). 4. K. Ito and K. Akiba, J: Rudioanul. Nwl. Chm. Articles
152,381(1991}.

1. F. Luykx, Technetium

5. H. P. Boehm and M. Volt, Cu~~~~~ 8,227 (1970). 6. V. A. Garten and D. E. Weiss, Ausi. J. Chem., 10, 309
(1957).

7. 1-I. Yoshida and K. Kameoka, In Carbon Muterialsfitr

High Technology (in Japanese) (Edited by K. Kobayashi and H. Honda) pp. 165-187. Kogyo Cyosakai, Tokyo ( 1987).

8. S. Tachimori, S. Sakurai, and S. Usuda, Fr~)~~~~~j~~~?ft~?~~ Third ~nti~r~at~~~na~ Cot@ence on ~~11~1~~~ Fud Reptw wssing and WasreMunugemrnf, April 16, 199 1, Sendai, Japan, pp. 6 I I-6 16. Atomic Energy Sot. Japan, Tokyo (1991). 9. K. Bratzler, Adsorption von Gasen und Dtimnpfkn in Laboraforirrm ~md Technik, Theodor Steinkopff, Dresden (1944) (Japanese Edition, pp. 55-58).