Investigation of uranium sorption laws in solution by gamma-spectrometric method with natural and modified zeolites in static condition

(1)

Institute of Radiation Problems

Azerbaijan National Academy of Sciences

Laboratory of Radiochemistry

ANKARA - 2008

INVESTIGATION OF URANIUM SORPTION LAWS IN

SOLUTION BY GAMMA-SPECTROMETRIC METHOD

WITH NATURAL AND MODIFIED ZEOLITES IN

STATIC CONDITION

Garibov A.A., Mehdiyeva R.N., Naghiyev J.A.

Firudin Aghayev str. 9, Phone: (+994 12)

510 05 92, 439 33 89

(2)

Determination of uranyl ion concentration in solution

according to activities of U

235 and Pa

234 m

radionuclides







₁₈₆

186 ₁₈₆

235 kev

U

S

A













1001

234 keV

Pa

S

A

235 235 235 235 235 235

1

2 ln 2

U

A

U

m

A

N

T

M











238 238 238 238 238 238

1

2 ln 2

U

A

U

m

A

N

T

M











238 238 238 238 235 235 235 235

1

2

1

U U U U U U U

U

A

M

T

m

A

M

T







(3)

(4)

(5)

Influence of pH on uranyl-ion sorption

in solution by natural zeolite

pH

1

2

3

4

5

6

7

8

9

10

11

12

13

14 Ao

Bk/L

20.0±1.0 20.0±1.0 20.0±1.0 20.0±1.0 20.0±1.0 20.0±1.0 20.0±1.0 20.0±1.0 20.0±1.0 20.0±1.0 20.0±1.0 20.0±1.0 20.0±1.0 20.0±1.0

A

Bk/L

19.5±1.5 21.3±1.0 18.5±1. 1 18.8±1. 3 17.1±1. 0 17.9±1. 2 17.2±0. 9 10.7±1. 9 5.3±2.0 4.1±3.6 4.4±4.0 5.0±4.4 4.7±4.6 3.3±2.7

Co

mq/L

96±5

C

mq/L

94.1±7.2 102.3±4.8 89.2±5.3 90.3±6.3 82.5±4.8 86.3±5.8 83.2±4.3 51.7±9.1 25.6±9.6 19.8±17.4 21.2±20.3 24.1±21.2 22.7±22.2 15.9±13.0

Co-C

mq/L

1.9 -6.3

6.8

5.7

13.5

9.7

12.8

44.3

70.4

76.2

74.8

71.9

73.3

80.1 SST

mq/q

0.6 -2.1

2.3

1.9

4.5

3.2

4.3

14.8

23.5

25.4

24.9

24.0

24.4

26.7 R

%

2.0 -6.6

7.1

5.9 14.1 10.1 13.3 46.1 73.3 79.4

77.9

74.9

76.4

83.4

(6)

Dependence of sorption of U

235 _{uranyl solutions with 20Bq/L activity}

by 150 mg natural zeolite on pH

m

_sor

=150mg, sorbent mass

R - sorption degree of natural zeolite %

Vsob=50 ml –capacity of sorption solution

t=24 hour –sorption time

(7)

Investigation of uranyl solution sorption of

different concentration by 150mg natural

zeolite on optimal pH (pH=7)

Ao

Bk/L

1.00±0.05 2.0±0.1 3.0±0.1 5.0±0.1 8.0±0.1 10.0±0.₅ 15.0±0.₅ 20.0±1.₀ 25.0±1.0 30.0±1.0 40.0±1.0 50.0±1.0 75.0±1.0 100.0±1.0

A

Bk/L

0.06±0.05 0.10±0.05 0.08±0.05 0.25±0.₁ 3.4±0.2 5.3±0.6 10.1±0.₅ 17.8±1.₁ 24.6±1.5 31.0±1.2 38.7±1.3 50.5±1.0 74.5±4.8 101.3±4.2

Co

mq/L

4.8±0.2 9.6±0.4 14.5±0.4 24.1±0.₄ 38.6±0.₄ 48.0±2.₄ 72.3±2.₄ 96.0±4.₈ 120.6±4.8 144.7±4.8 192.0±4.8 241.2±4.8 361.7±24.1 480±24.1

C

mq/L

0.3±0.2 0.48±0.20 0.4±0.2 2.4±0.4 16.4±0.₈ 25.6±2.₉ 48.9±2.₄ 85.9±5.₃ 118.7±7.2 149.5±5.9 186.7±6.5 243.6±4.8 359.3±23.2 488.6±20.7

Co-C

mq/L

4.50

9.12

14.10

21.7

22.2

22.4

23.4

10.1

1.9

5.2

5.3

1.4

2.4 -8.6

SST

mq/q

1.5

3.0

4.7

7.2

7.4

7.5

7.8

3.4

0.6

1.7

1.8

0.5

0.8 -2.9

R

%

93.8

95.0

97.2

90.0

57.5

46.7

32.4

10.5

1.6

3.6

2.8

0.6

0.7 -1.8

(8)

Dependence of degree of sorption by 150 mg natural zeolite on initial activity in uranyl

solutions of different activities on optimal pH (pH=7)

Dependence of concentration diffrence by 150 mg natural

zeolite on initial activity in uranyl solutions of different

activities on optimal pH (pH=7)

Dependence of absorption capacity by 150 mg natural

zeolite on initial activity in uranyl solutions of different

(9)

Investigation of uranyl solution sorption on

optimal pH and optimal concentration

depending on sorbent mass:

M

s mg

10

25

50

75

100

125

150

175

200

225

250

300

350 Ao

Bk/L

15.0±0.5 15.0±0.5 15.0±0.5 15.0±0.5 15.0±0.5 15.0±0.5 15.0±0.5 15.0±0.5 15.0±0.5 15.0±0.5 15.0±0.5 15.0±0.5 15.0±0.5

A

Bk/L

14.3±0.5 14.0±0.5 13.5±0.5 13.0±0.5 12.2±0.5 11.6±0.5 10.1±0.5

9.2±1.0

8.4±1.1

6.0±1.0

3.7±1.3

2.2±1.5

1.7±1.4

Co

Bg/L

72.3±2.4 72.3±2.4 72.3±2.4 72.3±2.4 72.3±2.4 72.3±2.4 72.3±2.4 72.3±2.4 72.3±2.4 72.3±2.4 72.3±2.4 72.3±2.5 72.3±2.6

Co

Bg/L

69.0±2.4 67.5±2.4 65.1±2.4 62.7±2.4 58.8±2.4 56.0±2.4 48.7±2.4 44.4±4.8 40.5±5.2 28.9±4.8 17.8±6.3 10.6±7.2

8.2±6.6

Co-C

mg/L

3.30

4.80

7.20

9.60

13.50

16.30

23.60

27.90

31.80

43.40

54.50

61.70

64.10 SST

mg/g

16.5

9.6

7.2

6.4

6.8

6.5

7.9

8.0

9.6

10.9

10.3

9.2 R %

68.8

50.0

49.7

39.8 35.0 34.0

32.6

29.1

26.4

30.0

28.4

32.1

33.4

(10)

Dependence of sorbent mass on sorption degree in uranyl

solutions on optimal pH and optimal concentration:

M

sorbent -

sorbent mass

R

-

sorption degree of natural zeolite

%

V

sob=50 ml –capacity of sorption solution

t=24 hour –sorption time

(11)

Factors of desorption of zeolite sorbed uranyl ion in HNO

₃

acid

with different concentrations:

ω %

0

5

10

15

20

25

30

35

40

45

50 A

Bk/L

0.7±0.5

3.4±0.6

9.8±0.5

10.4±0.4

10.7±0.3

5.6±0.7

5.1±0.8

4.6±0.9

2.0±1.0

1.1±1.0

0.8±0.7

C

mg/L

3.4±2.4

16.4±2.9

47.3±2.4

50.2±1.9

51.6±1.4

27.0±3.4

24.6±3.9

22.2±4.3

9.6±4.8

5.3±4.8

3.9±3.4

R

%

4.7

22.7

65.3

69.3

71.3

37.3

34.0

30.7

13.3

7.3

5.3 m

s=450 mq -desorbsiya olunan sorbentin kütləsi

V

des=50 ml -desorbsiya gedən məhlulun həcmi

t

=24 hour –desorption time

t

=25

ºC

ω

- HNO

3

concentration %

A

-activity of uranyl solution after desorption, Bg/L

C

-concentration of uranyl solution after desorption,

mg/L

R

- desorption degree of natural zeolite %

(12)

Factors of desorption of zeolite sorbed uranyl ion in HCl acid with

different concentration:

m

s=450 mg –desorbed sorbent mass

V

des=50 ml –capacity of desorption solution

t

=24 hour –desorption time

t

=25

ºC

ω

- HCl concentration %

A

-activity of uranyl solution after desorption, Bg/L

C

-concentration of uranyl solution after desorption,

mg/L

R

- desorption degree of natural zeolite %

Diagram of desorption of natural zeolite by HCl

ω

%

0

5

10

15

20

25

30 A

Bk/L

_0.7±0.5

_3.4±0.5

_11.9±0.5

_13.8±0.5

_15.2±0.5

12.8±0.5

10.1±0.5

C

mq/L

3.4±2.4

16.4±2.4

57.4±2.4

66.6±2.4

73.3±2.4

61.7±2.4

48.7±2.4

R

%

4.7

22.7

79.3

92.0

101.3

85.3

67.3

0.0

20.0

40.0

60.0

80.0

100.0

0

5

10

15

20

25

30

35 ω %

R

%

(13)

Investigation of optimal pH of U

235 uranyl solutions’

sorption with 20 Bq/L activity by 150mg natural zeolite

activated by HNO

₃

with different concentration

pH

1

2

3

4

5

6

7

8 Ao Bk/L

20.0±1.0

A Bk/L

20.9±1.0

19.3±1.0

17.1±1.0

13.4±1.0

13.7±1.0

9.1±1.0

6.9±1.0

Sedimentation

begins

R %

-4.5

3.5

14.5

33.0

31.5

54.5

65.5 pH

1

2

3

4

5

6

7

8 Ao Bk/L

20.0±1.0

A Bk/L

20.5±1.5

18.3±1.0

12.1±1.0

10.4±1.0

10.6±1.0

6.0±1.0

4.3±1.0

Sedimentation

begins

R %

-2.5

8.5

39.5

48.0

47.0

70.0

78.5 pH

1

2

3

4

5

6

7

8 Ao Bk/L

20.0±1.0

A Bk/L

19.5±1.0

18.9±1.0

15.5±1.0

14.2±1.0

8.1±1.0

9.6±1.0

Sedimentation

begins

R %

2.5

5.5

22.5

29.0

59.5

52.0 ω

HNO3

=5

%

ω

HNO3

=

10 %

ω

HNO3

=

15 %

(14)

Investigation of optimal pH of U

235 _{uranyl solutions’ sorption}

with 20 Bq/L activity by 150mg natural zeolite activated by

HNO

₃

with different concentration

pH

1

2

3

4

5

6

7

8 Ao Bk/L

20.0±1.0

A Bk/L

19.9±1.0

21.8±1.0

18.1±1.0

11.7±1.0

11.5±1.0

10.4±1.0

10.6±1.0

Sedimentatio

begins

R %

0.5 -9.0

9.5

41.5

42.0

48.0

47.0 pH

1

2

3

4

5

6

7

8 Ao Bk/L

20.0±1.0

A Bk/L

20.5±1.5

18.3±1.0

19.1±1.0

18.7±1.0

15.9±1.0

15.1±1.0

15.3±1.0

Sedimentation

begins

R %

-2.5

8.5

4.5

6.5

20.5

24.5

23.5 ω

HNO3

=

20 %

ω

HNO3

=

25 %

ω

HNO3

=

30 %

pH

1

2

3

4

5

6

7

8 Ao Bk/L

20.0±1.0

A Bk/L

19.5±1.0

20.8±1.0

18.9±1.0

17.6±1.0

17.2±1.0

16.5±1.0

15.2±1.0

Sedimentation

begins

R %

2.5 -4.0

5.5

12.0

14.0

17.5

24.0

(15)

Dependence of U

235 uranyl solutions’ sorption with

20 Bq/L activity by 150mg natural zeolite

activated by HNO

₃

with

different concentration on

pH

(16)

Investigation of uranyl solution sorption of different concentration by

150mg natural zeolite activated by 5%

HNO3

on optimal pH

(pH=7)

Ao Bk/L

1.0

0 ±

0.0

5

2.0 ±

0.1

3.0 ±

0.1

5.0 ±

0.1

8.0 ±

0.1

10 .0

±

0.5

15 .0

±

0.5

20 .0

±

1.0

25 .0

±

1.0

30 .0

±

1.0

40 .0

±

1.0

50 .0

±

1.0

75 .0

±

1.0

10

0.0 ±

1.0 A Bk/L

0.0

5 ±

0.0

5

0.0

5 ±

0.0

6

0.0

6 ±

0.0

5

0.1

5 ±

0.0

5

0.7

5 ±

0.0

5

1.3 ±

0.1

2.1 ±

0.2

4.3 ±

0.5

6.6 ±

1.0

13 .0

±

1.0

19 .7

±

1.0

48 .5

±

1.0

75 .5

±

1.0

99 .3

±

1.2 Co

mg/L

4.8 ±

0.2

9.6 ±

0.4

14 .5

±

0.4

24 .1

±

0.4

38 .6

±

0.4

48 .0

±

2.4

72 .3

±

2.4

96 .0

±

4.8

12

0.6 ±

4.8

14

4.7 ±

4.8

19

2.0 ±

4.8

24

1.2 ±

4.8

36

1.7 ±

24 .1

48

0 ±

24 .1

C

mg/L

0.2 ±

0.2

0.2 ±

0.3

0.3 ±

0.2

0.7 ±

0.2

3.6 ±

0.2

6.3 ±

0.4

10 .1

±

0.8

20 .7

±

2.4

31 .8

±

4.8

62 .7

±

4.8

95 .0

±

4.8

23

3.9 ±

4.8

36

4.1 ±

4.8

47

8.9 ±

5.8 Co-C

mg/L

4.60

9.4

14.2

23.4

35.0

41.7

62.2

75.3

88.8

82.0

97.0

7.3 -2.4

1.1 SST

mg/g

1.5

3.1

4.7

7.8

11.7 13.9 20.7 25.1

29.6

27.3

32.3

2.4 -0.8

0.4 95.8 97.9 97.9 97.1 90.7

56.7 50.5

3.0 -0.7

0.2

(17)

Dependence of sorption degree of uranyl solution with different activity by 150mg zeolite

activated by 5% HNO3 on optimal pH (pH=7) on initial activity

Dependence of sorption capacity of uranyl solution with different activity by 150mg zeolite