On extracting and application of noble metal fission product alloy … on... · 2017-10-20 · LOGO...

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On extracting and application of

noble metal fission product alloy

particles from spent fuel as

catalysts

Daqing Cui

Team: Y. Ouyang, S. Xiao, T. Li, L.Wang & G.Ye

China Institute of Atomic Energy

2017 10 17-19, IAEA Vienna

CIAE

www.themegallery.com Company Logo

Content

Introduction 1

FP alloy particles charaterization, composition, size & structure

2

Charaterization of catalytical effect & β radiation 3

As electrolysis catalysts 4

As photo catalysts 5

Optimizing FP noble metal extracting methods

6

SNP generated per year in China t/a SNP accumulated in China, t

in the World

1. Direct disposal

2. Monorecycling Pu

3. Multirecycling Pu

4. Multirecycling Pu & An

5. Improved option4 with

separation of Cs, Sr

6. Transmutation of long

lived fission products

Nuclear Fuel Cycle Options

The best cleaner is who can both clean the house and sell the waste at a good price

SNF

reprocessing

Waste

U & Pu

SNF

reprocessing

Waste

U & Pu

FP alloy Particles as H2

catalysts

Sr +Cs

Minor An

235U + n → 138Ba + 95Mo + 3n + 6β- : 7.8 x 107KJ/g

• What are noble FP metals ?

1/ How much will be created in a spent fuel ?

2/ How will be their radio activities & toxicities ?

• How to Separate and Utilize?

a) Extracting FP noble metals from high level liquid Waste, by electro deposition

M. Ozawa, JAEA as Electrode catalysts for H2 production

b) Directly extracting as original particles

as catalysts for photocatalyst or electrolyse/fuel cell catalysts

2

RE, Y: 24% Mo，Ru, Tc, Rh, Pd: 29% Kr, Xe: 15% Zr, Nb: 14% Cs, Rb, I, Te: 11% Ba, Sr: 7%

Fission product yield from normal LWR 29%x6.5g/130g = 1.45% Particles / solid solution in UO2?

11

Periodic Table of the Elements

Group**

Period 1

IA

1A

18

VIIIA

8A

1

1

H1.008

2

IIA

2A

13

IIIA

3A

14

IVA

4A

15

VA

5A

16

VIA

6A

17

VIIA

7A

2

He4.003

2

3

Li6.941

4

Be9.012

5

B10.81

6

C12.01

7

N14.01

8

O16.00

9

F19.00

10

Ne20.18

8 9 10

311

Na22.99

12

Mg24.31

3

IIIB3B

4

IVB4B

5

VB5B

6

VIB6B

7

VIIB

7B

------- VIII -----

--

------- 8 -------

11

IB1B

12

IIB2B

13

Al26.98

14

Si28.09

15

P30.97

16

S32.07

17

Cl35.45

18

Ar39.95

419

K39.10

20

Ca40.08

21

Sc44.96

22

Ti47.88

23

V50.94

24

Cr52.00

25

Mn54.94

26

Fe55.85

27

Co58.47

28

Ni58.69

29

Cu63.55

30

Zn65.39

31

Ga69.72

32

Ge72.59

33

As74.92

34

Se78.96

35

Br79.90

36

Kr83.80

5

37

Rb85.47

38

Sr87.62

39

Y88.91

40

Zr91.22

41

Nb92.91

42

Mo95.94

43

Tc(98)

44

Ru101.1

45

Rh102.9

46

Pd106.4

47

Ag107.9

48

Cd112.4

49

In114.8

50

Sn118.7

51

Sb121.8

52

Te127.6

53

I126.9

54

Xe131.3

655

Cs132.9

56

Ba137.3

57

La*138.9

72

Hf178.5

73

Ta180.9

74

W183.9

75

Re186.2

76

Os190.2

77

Ir190.2

78

Pt195.1

79

Au197.0

80

Hg200.5

81

Tl204.4

82

Pb207.2

83

Bi209.0

84

Po(210)

85

At(210)

86

Rn(222)

787

Fr(223)

88

Ra(226)

89

Ac~(227)

104

Rf(257)

105

Db(260)

106

Sg(263)

107

Bh(262)

108

Hs(265)

109

Mt(266)

110

---()

111

---()

112

---()

114

---()

116

---()

118

---()

Lanthanide

Series*

58

Ce140.1

59

Pr140.9

60

Nd144.2

61

Pm(147)

62

Sm150.4

63

Eu152.0

64

Gd157.3

65

Tb158.9

66

Dy162.5

67

Ho164.9

68

Er167.3

69

Tm168.9

70

Yb173.0

71

Lu175.0

Actinide Series~

90

Th232.0

91

Pa(231)

92

U(238)

93

Np(237)

94

Pu(242)

95

Am(243)

96

Cm(247)

97

Bk(247)

98

Cf(249)

99

Es(254)

100

Fm(253)

101

Md(256)

102

No(254)

103

Lr(257)

Classification (Kleykamp, 1975)

1) Dissolved in the matrix: Rb, Sr, Y,

Zr, Nb, Te, Cs, Ba, La, Ce, Pr, Nd,

Pm, Sm, Eu

2) Partly precipitated at grain

boundaries (oxides): Rb, Sr, Zr,

Nb, Mo, Te, Cs, Ba

3) Metallic precipitates: Mo, Tc, Ru,

Rh, Pd, Ag, Cd, In, Sn, Sb, Te

4) Volatiles: Br, Kr, Rb, I, Xe, Cs

Particle size bigger in central part due to better diffusion at higher temrature. Contents differ due to Pu/U vary

Mo-Ru-Tc-Pd-Rh FP alloy particles formed in nuclear fuel

Results of North American palladium Ltd in Canada

1,4266,9886171,900～4,1502.4～7.4Pd

Estimate from PGM production results in main mine

6,6522,5431,527578～949(0.4～0.6)Rh

45

1.4

36

1.4

Ratio

(-)

634～842

102～251

4,021～6,059

50～98

Conc.(ppm)

LWR

113

5.8

84

7.1

Ratio

(-)

Remark

FBR

Metal

Estimated from Cu ore in Russia UGMK

(2004)1,840(3.6～29)Te

Results of Galmony mine in Ireland and Dikulushi mine in Congo

71546～201Ag

Results of Erdenet mine in Mongolia8,966140Mo


(2004)140(12～92)Se

Conc.(ppm)

Contents(ppm)

Results of North American palladium Ltd in Canada

1,4266,9886171,900～4,1502.4～7.4Pd

Estimate from PGM production results in main mine

6,6522,5431,527578～949(0.4～0.6)Rh

45

1.4

36

1.4

Ratio

(-)

634～842

102～251

4,021～6,059

50～98

Conc.(ppm)

LWR

113

5.8

84

7.1

Ratio

(-)

Remark

FBR

Metal


(2004)1,840(3.6～29)Te

Results of Galmony mine in Ireland and Dikulushi mine in Congo

71546～201Ag

Results of Erdenet mine in Mongolia8,966140Mo


(2004)140(12～92)Se

Conc.(ppm)

Contents(ppm)

Spent Fuel as “ Nuclear Ore”

Richest ore

The mass of NRM generated in SNF worldwide is similar with the total production, Rh is even more, 2.5 time higher National Demands of PGM in Japan (FY2006)；Ru:3.7t, Rh:2.7t, Pd:50.6t Ozawa: In estimating nuclear fuel cycle capacity in Japan can cover ca.100% of Ru, ca.40% of Rh and ca.7% of Pd against the demands.

Repository NRM particles H2 catalyst


1. D. Cui* , J. Low, K. Spahiu, Environmental behaviors of spent nuclear fuel and canister materials, Energy & Environmental Science 2011, 4, 2537-2545, DOI:10.1039/C0EE00582G

2. D. Cui, V.V. Rondinella, J. A. Fortner, A. J. Kropf , D. J. Wronkiewicz and K. Spahiu, “Charactorisation of alloy particles extracted from spent nuclear fuel”, Journal of Nuclear Materials 420, 1-3 (2012)328-33.

3. D. Cui, V.V. Rondinella, J. Low and K. Spahiu, Hydrogen catalytic effects of nanostructured alloy particles in spent fuel on radionuclide immobilization, Applied Catalysis B: Environmental 94 (2010) 173–178

4. Daqing Cui, Jeanett Low, C. Janzon, Kastriot Spahiu, Leaching of Spent Fuel Mo-Ru-Tc-Pd- Rh Aggregates under Anoxic Conditions Radiochimica Acta 92(551-555) (2004)

5. Daqing Cui, Trygve Eriksen and Ulla-Britt Eklund. On metal aggregates in spent fuel, synthesis and leaching of Mo-Ru-Pd-Rh Alloy, Material Research Society Symp. Proc Vol 663, Scientific Basis for Nuclear Waste Management XXXIV (2001)

6. D. Cui H. Yang,Y. Zhong, Y. Yun, W. Wan, S. Hovmöller, L. Eriksson, K. Spahiu On fission product alloy nanoparticles, important energy and environmental catalysts, Manuscript to JNM,2017

Previous work


1. D. Cui* , J. Low, K. Spahiu, Environmental behaviors of spent nuclear fuel and canister materials, Energy & Environmental Science 2011, 4, 2537-2545, DOI:10.1039/C0EE00582G

2. D. Cui, V.V. Rondinella, J. A. Fortner, A. J. Kropf , D. J. Wronkiewicz and K. Spahiu, “Charactorisation of alloy particles extracted from spent nuclear fuel”, Journal of Nuclear Materials 420, 1-3 (2012)328-33.

3. D. Cui, V.V. Rondinella, J. Low and K. Spahiu, Hydrogen catalytic effects of nanostructured alloy particles in spent fuel on radionuclide immobilization, Applied Catalysis B: Environmental 94 (2010) 173–178

4. Daqing Cui, Jeanett Low, C. Janzon, Kastriot Spahiu, Leaching of Spent Fuel Mo-Ru-Tc-Pd- Rh Aggregates under Anoxic Conditions Radiochimica Acta 92(551-555) (2004)

5. Daqing Cui, Trygve Eriksen and Ulla-Britt Eklund. On metal aggregates in spent fuel, synthesis and leaching of Mo-Ru-Pd-Rh Alloy, Material Research Society Symp. Proc Vol 663, Scientific Basis for Nuclear Waste Management XXXIV (2001)

6. D. Cui H. Yang,Y. Zhong, Y. Yun, W. Wan, S. Hovmöller, L. Eriksson, K. Spahiu On fission product alloy nanoparticles, important energy and environmental catalysts, Submitted to JNM,2015

Un Oxic extraction

Normal Reprocessing, oxic HNO3

oxidative corrosion of alloy particles

Conditions: UO2 soluble，but NRM alloy particles stable?

0

200

400

600

800

1000

1200

0 200 400 600 800 1000 1200 1400 1600 1800

pp

b

hours

Mo-100

Pd-105

Rh-103

1. Similar alloy without Tc

46Mo-29-Ru-21-Pd-4Rh.

~1800oC melte， Aging in Ar,

1511oC, 4oC/min.

2. Test (6 g, 4 cm2/g) in 25

mL .under gental conditions

in that UO2 dissolved easily

In deoxygenated H3PO4 113oC

Ru, Pd, Rh ≈0.5 ppb, Mo= 900ppb stabilized

BWR 23 MWd/KgU, rumped SNF

Dissolving

SNP in H3PO4 at 113 oC

(glass-fiber filter)

filterate

ICP-MS

Residue

wash & dry

Charaterising

-spectrometry

XRD

SEM-WDS

TEM-EDS-diffraction

EXAFS

Testing as catalyst

flashing Ar/Ar+10%H2

H2- U(VI) Np(V) Pu(V)

Se(IV)

pH3 and pH8.5

vs. 合成合金, Fe(0)

5nm —

TEM

50nm _____

24

Single crystal ED on nano-crystals

Rotation electron diffraction(RED)

Eward sphere

Reciprocal space

24 Zhang et al. Z. Kristallogr., 2010, 225, 94

Wan, et al. J. Appl. Cryst., 2013, 46, 1863

TEM - RED

Diffraction patterns from a 10 nm sized particle. D(Å)

calculated from distances

Scanning of XRD film, 0.5 mg alloy residue

(*trace UO2)

XRD on alloy residue

TEM-diffraction on a

nanoparticle

d(Å) Intensity d(Å) values measured

2.095 100 2.11, 2.09, 2.07, 2.05

2.38 20 2.39, 2.38

2.210 20 2.28, 2.24, 2.21, 2.18

1.168 20 1.16, 1.18, 1.19

1.149* 10

2.49 5 2.48, 2.49

1.045* 5

1.000* 5

a , nm c, nm

1) Residues nondestructicely, with

hexagonal symmetry

extracted from SF MoRuTcRhPaTe

0.2749 0.4386

2) Tc element 0.2740 0.4395

3)Ru element 0.2700 0.4277

4)synthesized Mo40Ru50Pd10 epsilon

alloy phase[Park 2000]

Park et al Korean Chem. Soc. 2000, 21, 1187-1192

0.2757 0.4427

TEM-diffraction

•0.5-0.7 mm particles + clusters (composed by

~10 nm sized nanoparticles):

•TEM-EDS & SEM-WDS: similar sized particles

have similar composition.

•nm particles outside cluster differ in

composition

•SEM-WDS on the biggest particles,0.5-

0.7µm

•TEM-EDS analysis on nanoparticles

•Calculated inventories, 23 MWd/kgU

•Literature data for comparison

fission products Mo Ru Tc Pd Rh Te

SEM_WDS average of 8

submicroparticles

± s

32.7

±1.9

40.5

±1.7

7.0

±0.8

11.7

±1.6

4.2

±0.4

3.8

±1.4

TEM-EDS average of 9

clustered nanoparticles

± s

26,5

±

4,4

32,7

±5,4

7,6

±3,0

23,1

±3,0

6,3

±3,9

4,9

±3,4

nanoparticle analysed

by TEM diffraction 23,2 38,9 4,26 19,2 7,49 6,85

particles from HNO3 SF

reprocessing 20

50–

60

0.5-

5.0 10 10 --

calculated fission yield

[Origen] 42.9 26.0 10.1 10.9 5.9 4.3

s= standard deviation

normalized at.%

Characterization of metal alloy particles

Spectral edges (Mo, Tc and Ru).

synthetic

particles

EXAFS : Mo in the residue is very well coordinated with other metals

EXAFS of 4d-metal particles

Fourier transform modulus

EXAFS: all elements are in similar conditions hemogenoius (true) alloy

Particles

extracted from

spent fuel

fine structure

Test NRM alloy particles: catalyst in 10 % H2 to reduce U(VI) Np(V) Pu(VI)?

25 mL 10NaCl 2mM NaHCO3 solution with U(VI) Pu(VI), Np(V) Tc(VII) Se(VI), flashing Ar+0.03%CO2+10% H2 mixture

pH3 (non sorption） & pH8.5

Study the fates of nuclides in following batch test,

• 5.5 mg NRM particles

• 1 cm2 similar synth alloy, but no Tc

• 1 cm2 similar synth alloy, 0.1 mm source (90Sr 370kBq) effects

• 1 cm2 iron metal，disposal canister material

0,10

1,00

10,00

100,00

1000,00

10000,00

0,00 5,00 10,00 15,00 20,00 25,00 30,00

day

pp

b

U

0,01

0,10

1,00

10,00

100,00

1000,00

0,00 5,00 10,00 15,00 20,00 25,00 30,00

daysp

pb

Pu

Np

0,01

0,10

1,00

10,00

100,00

1000,00

0,00 5,00 10,00 15,00 20,00 25,00 30,00days

pp

b

Experiments at pH 3.0, 5%H2: U(VI), Pu(VI), Np(V)

• H2 has no reducing effects • Synt alloy has some effect • Synt alloy + β much bigger

effects • Extracted alloy has highest

effcts

β radioisotopes in FP alloy particles


Green energy, H2 & fuel cell need catalysts

Photocatalysis H2 from 4Gen. NPP Photolyzer, calalysis

Hydrogen made by the electrolysis of water is now cost-competitive and gives us another building block for the low-carbon economy July 05, 2017 , https://www.carboncommentary.com More competitive if the low cost high efficient radcatalysts can be developed.

Wind power is over built night day

https://www.carboncommentary.com/

Electro-deposition of NRM in S-HLLW; HCl vs. HNO3 media (Masaki Ozawa)

16

HNO3-S-HLLW

HCl-S-HLLW

Electrolysis; Catholyte: 50cm3, 50℃, Cathode: Ptsmooth, 2cm2, Ic: 2.5mA/cm2(1hr)→75(2hr)→100(4hr), ICP Atomic Emission Spectrometry

★

★Pd; must be higher

Micro NRM Deposits by CEE of S-HLLWHCl-0.5M

Mixture of Dendrite and Coagulated fine sphere particles

Metal ; Ru,Pd,Rh, Oxide ; ReO3, TcO2, MoO2 Ru, Rh, Re > Pd, Mo・・・ by 17

SEM/EDS Analysis

S-HLLW-0.5M HCl

S-HLLW-0.5M HNO3-

Pdadded

-0.8

-0.6

-0.4

-0.2

0

0.2

0.4

0.6

0.8

1

-1.5 -1 -0.5 0 0.5 1 1.5

Pd:Ru:Rh:Re=3.5:4:1:1 *1 Pd:Ru:Rh:Re=1:1:1:1

Pd:Ru:Rh:Re=3.5:4:1:1 *2 Pd

Rh Pd-Ru

Pd-Rh Pd-Re

Ru-Rh

S-HLLW-0.5M

HNO3

Had →H+ + e-

H+ + e- →Had

CV on NRM-deposit

Electrodes

Catalytic Activity of various NRM deposits

for Electrolytic H2 Production in 1M NaOH soln.

19

1) Highest catalytic reactivity has been assigned to the quaternary deposit (Pd-Ru-Rh-

Re (3.5:4:1:1)) electrode, in electrolysis either in NaOH or artificial sea water

(Global2007).

2) Noblest φHinit. (>-1.05V) was observed on NRM deposit electrodes from S-HLLW

(HCl, HNO3)

3) Energy consumption of such electrodes on H2 production was about half of smooth

Pt electrode, specifically in artificial sea water (ibid.).

4) Those (including the deposit from S-HLLW) reactivity, better that of Pt-black

electrode as well as smooth Pt (ibid.).

5) A high reactivity would attribute to higher numbers of Ru and Rh atoms at the

surface (Global2007, 2009). Higher adsorption sites for H+ by them was responsible.

6) Tc showed higher reactivity than that of Re, in/off the combination with Rh (ibid.)

Due to its beta?

Utilization of NRM-deposit Electrodes (Masaki Ozawa)

• In reprocessing, FP alloy particles partly exist as residue in filters or filtrates

called as ”black shit” , often stop filter, or cause short cut during vatrification of HLW, deposite in glass. How to extract FP alloy particles?

H2 produced

• 3G NPP, the electrolzse water to H2 +O2 during nights, high cost catalyst?

H2 used by car or convert to electricity during the day.

• Sunshine photolyse water

Radioactive (Mo-Ru-Tc-Pd-Rh) - TiO2 ，combined photocatalyst

Study the machenism, how much and why beta radioactivity can

enhance the calalyst properties

3.2eV，λ<387nm ultra violet light


Alloy catalyst Rh:Pd combined effect?

β accelerator

Experimental set up

Light

β accelerator

H2 gas analysis

• On quantitative structure-activity relationships between hydrazine derivatives and β irradiation，,Nuclear Science and Technology, 2017

• Quantitative Comparative Kinetics of hydrazine decomposition on platinum under the effect of β radiolysis，Manuskript to ACS catalysis

• Zeolite Y Encapsulated Cu(II) and Zn(II)-Imidazole-Salen Catalysis for Benzyl Alcohol oxidation，Journal of Catalysis，accepted

• Synthesis of amidoxime-grafted activated carbon fibers for efficient removal of uranium(VI) from aqueous solution，Chemical Engineering Journal, accpeted

Some positive effects of beta radiation On redox catalysed reactions by our group at CIAE

Control temperature and TiO2 structure

TiO2

coated NRM particles

Futural optimization of FP particle extraction

1)Extract nano particles from SNF reprocessing residue on the

filters, purification by HNO3 HF or H3PO4

in hot HNO3 FP alloy particles can be oxidatively dissolved

2) Electrodeposition noble metal elements from HLW

3) High temp., (release/collect I, Cs, enlarge FP alloy particles),

crush SNF, high voltage puls fragmentation of SNP to grain

size in water and separate FP alloy particles

The nonaqueous methods developed for reprocessing spent fuel: fluoride, molybdate, in melts of metals and chlorides, electrochemical, ,,,, A. V. Bychkov, O. V. Skiba, Review of Non-Aqueous Nuclear Fuel Reprocessing and Separation Methods, Chemical Separation Technologies and Related Methods of Nuclear Waste Management pp 71-98|

All nonaqueous method expensive and lack of knowledge

On extracting and application of noble metal fission product alloy … on... · 2017-10-20 · LOGO...

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