Evaluation of a novel sorbent for recovery of radio-nuclides a comparison of batch and column operation

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Abstract
Environmental pollution by heavy metals and radionuclides originated from mines and mining operations can become a very important source of contamination both in soil and water. In the present study, an approach is made for uptake of heavy metals and radionuclides from contaminated sites using a polymeric sorbent having chelating functional groups, known as hydroxamic acid. This sorbent is used for uptake of uranium in spiked uranium and manganese (1:10 wt. ratio) solutions. The uptake performance and break through of the sorbent has been evaluated by equilibrating a known weight of dry sorbent in contact with uranium solution both in batch and column mode. Later on, the sorbent has been applied for the uptake and recovery of metal ions in uranium mining effluent samples where the actual concentration of interfering element, e.g. manganese is present in concentration 10% higher than the desired element and hence confirms the selectivity for uranium in presence of other impurities. Key Words:- Sorbent, uranium, impurities, recovery, selectivity

Introduction
Ion exchange resins are successfully employed for the concentration and recovery of uranium for experimental analysis and even for pre-concentration. The sorbents are highly selective as well as efficient. Depending on this factors they become expensive e.g. calixarenes and crown ethers. Therefore to employ this type of sorbent for recovery of uranium from secondary waste for safe disposal of nuclear waste is a challenging criterion. Previously also we have employed the sorbent for initial investigation to see its sorption properties for several nuclear secondary wastes (S. Mishra et al, 2008, Sangita Pal et al, 2008). During disposal the

actual effluents are in the neutral range therefore in each case the studies has been conducted at pH 7 to avoid any conflicts. The research presented here concerned the usefulness of the polymeric chelator for targeting uranium from a very low (ppb) concentration with respect to the presence of higher concentration of manganese. Our investigations carried out in terms of batch and column operation of the effluent. Batch experiment has been carried out in both actual and synthetic solution where as column has been operated with synthetic solution. This synthetic solution has been prepared targeting the inlet of a uranium mine effluent treatment plant.

Experimental
1. Resin Preparation of the resin has been described by initial solution polymerization method

and later on by conversion of the functional moieties as described in our previous paper (S. Mishra et al, 2008). Prior to the experiment, the resin was washed with 0.1(N) HCl to eradicate un-reacted materials and to see the compatibility of the resin in that condition and after that thoroughly rinsed with de-ionized water.
2. Feed solution- The feed solutions were prepared to stimulate the same quantity of uranium

and manganese present in the actual effluent. The pH of the solutions was adjusted with HCl and NaOH.
3. Eluent - 25 ml of 1(N) HCl solution was used for elution of 1 gm of sorbent. 4. Sample Collection and procedures for the batch experiment:- For the application of this

polymer in field conditions, the effluent treatment plant inlet sample and uranium tailings samples disposed in tailings pond were collected from Jaduguda. These samples were containing high concentration of Mn, U as well as other radionuclides and stable elements. Uptake studies were carried out by adding 0.5 gm of dried polymer in about 25 ml of treated effluent and tailings leachate sample in neutral pH, and also with the synthetic solution of uranium and potassium permanganate, whereas elution of the loaded sorbent completed with 1 (N) HCl.
5. Immobilisation factor - Metal

ion Immobilisation of a resin is the act of limiting

movement or making incapable of movement of the metal ions by trapping or rather chelating it with the functional groups of resin, can be caluclated as immobilisation factor = (1- Elution factor)

6. Uranium loading - Resin (0.5 gm) was packed in a glass column of 1 inch ID, resulting in a

bed height of 28 ml after equilibration with the desired synthetic solution. The spiked solution was adjusted to neutral pH. The spiked solution of uranium (60 ng/ml) and manganese (60 ug/ml) down flowed at the rate of 4 ml/min at 40 ml effluent intervals and U and Mn concentration in the effluent was analyzed to determine break through point.
7. Instrumentation and sample analysis- The estimation of manganese and uranium in the

original feed sample ( i.e., before the sorption experiment), the filtrate and eluent obtained after the experiments were carried out by flame atomic absorption spectrophotometry using GBCAvanta atomic absorption spectro-photometer and voltammeter, respectively. differential pulse adsorptive strripping

Results and Discussion

The capacity of the resin for the actual effluent has been presented in Table 1. Uranium and manganese in initial feed solution has been determined. The experiments have been conducted in duplicate and in static condition with actual (A) and synthetic solution (B) to achieve a comparative study. From the tabulated results (Table -1 and Table -2) it has been seen that initial uranium concentration is in ppb level for both the solutions (A) and (B), whereas manganese is present in ppm level. Sorption study was carried out contacting 25 ml of solution with 0.5 gm of resin in duplicate. The respective filtrates were tested. The filtrate containing negligible amount of uranium (Table -1) compared to manganese indicates the inlet of ETP after treating with sorbent can be disposed safely, as seawater having 3ppb level of uranium complex content on average. Table 2 also indicates a good percentage of sorption preferably uranium in the actual effluent, having a high distribution factor of 1450 ml/gm for uranium compared to manganese (Kd = 111.64
ml/gm). Even synthetic solution treatment showed a 6 times greater value of uranium distribution factor compared to manganese. The elution results (Table -2) show efficient recovery for both (A) and

(B) solution. It is indicative of the fact that not only it can be entrapped but all trapped uranium can be recovered, therefore a possibility of efficient reuse of the sorbent for scale up. When we have contacted the sorbent in column mode a good separation has been found, which supports the above fact, the sorbent in column rapidly chelated with uranium, still manganese remained that indicates time efficiency.

Conclusions
The experimental studies revealed that the sorbent is useful for the uptake of uranium from the inlet of uranium mine effluent treatment plant very selectively and although present in very low concentration compared to manganese but still has the ability to form the chelates and can be recovered efficiently for uranium recovery and out let effluent of the treated sorbent can be safely disposed. Similarly we have experimented in column mode and have found 2 hrs are approximately sufficient to reach the desired pick up, although a thorough investigation is required to set up in pilot scale.

Acknowledgement
For procurement and preparation of resin material, help from Mr. Chunu Soren (DD) and for analytical sample preparation and analysis Mr. Dilip Kumar Chaudhary (EAD) is acknowledged.

References
1. S. Mishra, Sangita Pal, G. G.Pandit, P. K.Tewari and V. D. Puranik, 2008. Use of

Polymeric Sorbent for the Uptake of Heavy Metals and Radionuclides from Different Effluents. Proceedings of the Sixteenth National Symposium on Environment on Groundwater Resources: Conservation and Management. pp 161-165. 2. Sangita Pal, S. Mishra, G.G.Pandit, K.L. Thalor, P. K.Tewari and V. D. Puranik, 2008. Potentiality of polymeric sorbent for immobilization and recovery aspect of contaminants from nuclear efluents. In Chemcon-2008, under Safety and Hazards Control, Index no ST 35, page. 355 Table 1 Uptake and elution characteristics of uranium and manganese in the inlet of Effluent treatment plant (ETP) and synthetic ETP effluent during batch experiment

Sample

Element

Initial conc.(C0)

Amount of total uranium present (g) in 25 ml solution 2.43 0.15 g

Metal content in the filtrate (g) 0.081 0.008 (almost same for i. and ii.) i. 425 g ii. 413 g

Amount of metal ion in the elute (g) i. 2.18 0.1 g ii. 2.39 0.09 g i. 899 g

ETP inlet Actual solution

97.22 6.2 (ng/ml) 54.96 (g/ml) 60 (ng/ml)

(A)
ETP inlet Synthetic solution

Mn

1374 g

ii. 919.5 g i. 1.33 0.1 g ii. 1.06 0.07 g

1.5 g

NIL

(B)

Mn

60 (g/ml)

1500 g

i. 7.05 g ii. 5.19 g

i. 1150 g ii. 1088.5 g

Table 2 The characteristic factors of uranium and manganese in the inlet of effluent treatment plant (ETP) and synthetic ETP effluent during batch experiments
Sample Time Mn (min) (ppm) 10 16.4 ETP inlet Actual 10.7 solution 20 (A) 30 9.6 40 7.5 ETP inlet synthetic 50 6.4 solution (B) 60 3.83 70 2 80 90 100 110 120 130 140 150 160 1.415 1.37 0.0798 0.829 0.828 0.912 1.04 1.33 1.45 Element U (ppb) 12.1 U 6.3 Mn4.1 1.6 U 0.5 0.08 Mn 0.08 0.08 0.08 0.08 0.24 0.56 1.2 1.6 1.8 2.5 Absorption % (Co-Ce)/Co . 100 96.67 69.07 99.93 99.53 Kd (Co-Ce)/Ce . V/m 1450 111.64 74950 10588.3 92.8 94.7 88.725 77.03 Elution % Immobilization factor 0.072 0.053 0.113 0.23

170

7.8

8.8

70 60 50 Concentration 40 30 20 10 0
90 11 0 13 0 15 0 17 0 19 0 21 0 23 0 25 0 10 50 70 30
Mn (ppm) U (ppb)

180 190 200 210 220 230 240 250 260

15.6 20.6 35.3 42.3 48.5 57.8 58.2 58.6 59.1

21.2 24.7 36.5 39.8 45.5 55.3 57.9 58.6 59.5

Time in minutes

Figure 1 Column study of the sorbent with synthetic effluents