Progress of Yara`s tasks

Hydromet project meeting

October 5, 2016

Alessio Vascon

Alexander Krivokapic

5 October 2016 Slide 2Hydromet project meeting

Outline

• The Odda process: challenges and possible solutions

• KELEX 100: continuation of studies

• APDC and elemental S: trials

• CYANEX 301: solvent extraction studies

• CYANEX 301: chemical stability studies

• CYANEX 301: stripping studies

• Possible future alternatives

• Summary

Slide 3Hydromet project meeting

The Odda process

DigestionCa5(PO4)3F (s) + 10HNO3 (aq) → 5Ca(NO3)2 (aq) + 3H3PO4 (aq) + HF (g)

Ca5(PO4)3F

(apatite)HNO3

Crystallization

Insolubles

Cooling Ca(NO3)2·4H2O

NeutralizationNH3 gas

Evaporation &

ParticulationPotassium

salt

NPK fertilizer products

5 October 2016

15 June 2016 Slide 4Hydromet project meeting

Presence of toxic contaminants: which ones to remove and from where?

Cd (<10 ppm)

DigestionCa5(PO4)3F

(apatite)HNO3

Crystallization

Insolubles

Cooling Ca(NO3)2·4H2O

NeutralizationNH3 gas

Evaporation &

ParticulationPotassium

salt

NPK fertilizer products

Crystallization Neutralization

pH ~ 0.5

(or pH ~ 1.8 with dilution 1/13)

Slide 5Hydromet project meeting

How to remove Cd?

Magnetic particles(particles with a magnetic core coated with a surface coating and

functional groups chosen for the specific application)

Functional groups

for Cd removal?

Solvent extraction

studies

5 October 2016

Slide 6Hydromet project meeting

KELEX 100 reference

0.3 M HNO3/H3PO4 _ 1h

0.3 M HNO3/H3PO4 _ 72h

3 M HNO3/H3PO4 _ 1h

3 M HNO3/H3PO4 _ 72h

KELEX 100

«nitro» KELEX 100

«nitro» KELEX 100

«nitro» KELEX 100

«nitro» KELEX 100

KELEX 100: previously…

KELEX 100 in acidic HNO3/H3PO4 environments:

5 October 2016

5 October 2016 Slide 7Hydromet project meeting

KELEX 100: previously…

KELEX 100 in acidic HNO3/H3PO4 environments:

N

OH

NO2

N+

OH

NO2

O-

chemically unstable

N

OH

5,0 5,5 6,0 6,5 7,0 7,5 8,0 8,5 9,0

0

10

20

30

40

50

60

70

80

90

100 Average of 3 parallels

Cd e

xtr

action (

%)

Equilibrium pH

0,0 0,5 1,0 1,5 2,0 2,5 3,00

1

2

3

4

5

Average of 3 parallels

Cd e

xtr

action (

%)

Equilibrium pH

(HNO3/H3PO4 solution)

(HNO3/H3PO4 solution)

0,5 1,0 1,5 2,0 2,5 3,00

1

2

3

4

5

Average of 3 parallels

Cd e

xtr

action (

%)

Equilibrium pH

(H3PO4 solution)

5 October 2016 Slide 8Hydromet project meeting

KELEX 100: previously…

Z. Marczenko, M. Balcerzak, Separation, Preconcentration and Spectrophotometry

in Inorganic Analysis (2000), 1st ed., Elsevier

Cd extraction with «nitro» KELEX 100

1000 rpm

Aqueous phase: 0.3 M HNO3/H3PO4 (pH theor. ~ 0.5)

Organic phase: KELEX 100 (0.02 M) in decane/1-decanol (10% vol)

Heating

90 °C / 6 h

centrifugation &

separation

5 October 2016 Slide 9Hydromet project meeting

N

OH

NO2

N+

OH

NO2

O-

N

OH+

5 October 2016 Slide 10Hydromet project meeting

Cd extraction with «nitro» KELEX 100

O: KELEX 100 (0.02 M)

in decane/1-decanol (10% vol)

A: H3PO4 sol. and HNO3/H3PO4 sol.

(10 ppm Cd) eq. pH 0.5-8.5

0 1 2 3 4 5 6 7 8 91E-3

0,01

0,1

1

10

100 "Nitro" KELEX 100 in H3PO4

"Nitro" KELEX 100 in HNO3 / H3PO4

Cd d

istr

ibution r

atio (

DC

d)

Equilibrium pH

0 1 2 3 4 5 6 7 8 9

0

20

40

60

80

100 "Nitro" KELEX 100 in H3PO4

"Nitro" KELEX 100 in HNO3 / H3PO4

Cd e

xtr

action (

%)

Equilibrium pH

O:A = 1:1

Cd extraction with «nitro» KELEX 100

5 October 2016 Slide 11Hydromet project meeting

ΔpH0.5 ~ 1.5

0 1 2 3 4 5 6 7 8 91E-3

0,01

0,1

1

10

100 "Nitro" KELEX 100 in H3PO4

"Nitro" KELEX 100 in HNO3 / H3PO4

KELEX 100

Cd

dis

trib

utio

n r

atio

(D

Cd)

Equilibrium pH

0 1 2 3 4 5 6 7 8 9

0

20

40

60

80

100 "Nitro" KELEX 100 in H3PO4

"Nitro" KELEX 100 in HNO3 / H3PO4

KELEX 100

Cd

extr

actio

n (

%)

Equilibrium pH

5 October 2016 Slide 12Hydromet project meeting

Cd extraction with «nitro» KELEX 100

N

OH

NO2

N+

OH

NO2

O-

N

OH

or

NO2 = strongly electron withdrawing group → more acidic KELEX 100 (pKa ↓)

5-chloro-8-quinolinol 5,7-dichloro-8-quinolinol

chemical instability can be helpful !!

Cd extraction with APDC: previously…

5 October 2016 Slide 13Hydromet project meeting

Ammonium pyrrolidine dithiocarbamate

(APDC)

+Methyl

isobutyl ketone

(MIBK)

Organic phase Aqueous phase

HNO3 sol.

(0-6 M)

R. Brooks et al., Analytica Chimica Acta 217 (1989) 165-170

5 October 2016 Slide 14Hydromet project meeting

Cd extraction with APDC: trials

O: methyl isobutyl ketone

(MIBK)

A: HNO3/H3PO4 sol., 0.02 M APDC

(10 ppm Cd) eq. pH 0.5-8.5

APDC in 0.3 M HNO3 / H3PO4APDC APDC in H2O(to be stored at + 4°C)

O:A = 1:1

Variations in Extraction Efficiency of Aqueous Cadmium (II) Using the APDC-MIBK Procedure, L.W. Newland, R.G. Clements.

Cd extraction with APDC: trials

Slide 15Hydromet project meeting5 October 2016

APDC 99% (Sigma-Aldrich) → 25 g ~ 3000 NOK

Cd extraction with elemental S: trials

Cd-rich

cake

Cd-free

filtrate

0.3 M HNO3 / H3PO4

10 ppm Cd + 109Cd tracer

Slide 16Hydromet project meeting5 October 2016

0 100 200 300 400 500 600

0

500

1000

1500

2000

Counts

Channel

Before S8 test (starting sol.)

After S8 test (filtrate)

Cd extraction with CYANEX 301

Slide 17Hydromet project meeting5 October 2016

+Kerosene

(ASOL D80)

Organic phase Aqueous phase

HNO3/H3PO4 sol.

(pH 0.5-2)

Cyanex 301

di-(2,4,4-trimethyl pentyl)phosphinic acid

K.C. Sole et al., Solvent Extraction and Ion Exchange 11 (1993) 783-796

P. Marc et al., Industrial & engineering chemistry research 51 (2012) 13238-13244

+ Stripping (?)

CYANEX 301: solvent extraction studies

Slide 18Hydromet project meeting5 October 2016

Equilibrium kinetics study

O: CYANEX 301 (0.02 M)

in ASOL D80

A: HNO3/H3PO4 sol.

eq. pH 1.7±0.1

10 20 30 40 50 600

20

40

60

80

100

Average of 3 parallels

Cd e

xtr

action (

%)

Shaking time (min)

O:A = 1:1

CYANEX 301: solvent extraction studies

Slide 19Hydromet project meeting5 October 2016

O: CYANEX 301 (0.02 M)

in ASOL D80

A: HNO3/H3PO4 sol.

eq. pH 0-5

0 1 2 3 4 50,1

1

10

100

1000

Average of 3 parallels

Cd

dis

trib

utio

n r

atio

(D

Cd)

Equilibrium pH

0 1 2 3 4 50

20

40

60

80

100 Average of 3 parallels

Cd

extr

actio

n (

%)

Equilibrium pH

O:A = 1:1

pH 0-1.5 O:A = 1:1; n = 1 → DCd ~ 135 / Ecd ~ 99.3%

Slide 20Hydromet project meeting5 October 2016

CYANEX 301: solvent extraction studies

1,5 2,0 2,5 3,0 3,5 4,0 4,5 5,00,1

1

10

100

1000

Average of 3 parallels

Linear fitting

Cd

dis

trib

utio

n r

atio

(D

Cd)

Equilibrium pH

Equation y = a + b*x

Weight Instrumental

Residual Sum of Squares

179,75456

Pearson's r -0,9899

Adj. R-Square 0,95982

Value Standard Error

D ratioIntercept 3,70201 0,42203

Slope -0,99651 0,14269

CYANEX 301: chemical stability studies

Slide 21Hydromet project meeting5 October 2016

1000 rpm

Aqueous phase: 0.3 M HNO3/H3PO4 (pH theor. ~ 0.5)

Organic phase: CYANEX 301 (0.02 M) in ASOL D80

3 M HNO3/H3PO4 (pH theor. ~ -5)

Heating

90 °C / 7 h

centrifugation &

separation

0,0 0,2 0,4 0,6 0,8 1,0 1,2 1,4 1,61E-3

0,01

0,1

1

10

100

1000

"Nitro" CYANEX 301 (0.3M / 7h)

CYANEX 301

"Nitro" CYANEX 301 (3M / 7h)

Cd d

istr

ibution r

atio (

DC

d)

Equilibrium pH

0,0 0,2 0,4 0,6 0,8 1,0 1,2 1,4 1,6

0

20

40

60

80

100

"Nitro" CYANEX 301 (0.3M / 7h)

CYANEX 301

"Nitro" CYANEX 301 (3M / 7h)

Cd e

xtr

action (

%)

Equilibrium pH

CYANEX 301: chemical stability studies

Slide 22Hydromet project meeting5 October 2016

1000 rpm

Aqueous phase: 0.3 M HNO3/H3PO4 (pH theor. ~ 0.5)

Organic phase: CYANEX 301 (0.02 M) in ASOL D80

Heating

90 °C / 24 h

centrifugation &

separation

0,0 0,2 0,4 0,6 0,8 1,0 1,2 1,4 1,6 1,8 2,01E-3

0,01

0,1

1

10

100

1000

"Nitro" CYANEX 301 (0.3M / 24h)

CYANEX 301

Cd d

istr

ibution r

atio (

DC

d)

Equilibirum pH

0,0 0,2 0,4 0,6 0,8 1,0 1,2 1,4 1,6 1,8 2,0

0

20

40

60

80

100

"Nitro" CYANEX 301 (0.3M / 24h)

CYANEX 301

Cd e

xtr

action (

%)

Equilibirum pH

CYANEX 301: stripping studies

Slide 23Hydromet project meeting5 October 2016

B. Ramachandra Reddy et al., Separation and Purification Technology 50 (2006) 161-166

CYANEX 301: stripping studies

Slide 24Hydromet project meeting5 October 2016

0 20 40 60 80 100 1201E-3

0,01

0,1

1

Average of 3 parallels

Cd d

istr

ibution r

atio (

DC

d)

Shaking time (min)

0 20 40 60 80 100 1200

20

40

60

80

100

Average of 3 parallelsC

d s

trip

pin

g (

%)

Shaking time (min)

O: CYANEX 301 (0.02 M)

in ASOL D80

A: HCl (6 M)O:A = 1:1

Fast kinetics O:A = 1:1; n = 1 → DCd ~ 8·10-3 / Ecd(aq) ~ 99.2%

Possible alternatives…

Slide 25Hydromet project meeting5 October 2016

+ 1,2-dichloroethane

Organic phase Aqueous phase

HNO3 sol.

(0-7 M)

(diphenylphosphinylmethyl)phenylphosphinic acids -HA-

Possible alternatives…

Slide 26Hydromet project meeting5 October 2016

Log D ~ 0.5 → E ~ 75%

Log D ~ 0.75 → E ~ 85%

Log D ~ -0.4 → E ~ 30%

Log -0.5 M = 0.3 M

Possible alternatives…

Slide 27Hydromet project meeting5 October 2016

E ~ 99.9%

E ~ 99%

E ~ 90%

Summary

• KELEX 100 studies → chemical instability of the molecule can be helpful

• APDC and elemental S studies → unsuccessful

• CYANEX 301 → ECd > 99% @ pH 0.5 with O:A = 1:1

• CYANEX 301 → precarious chemical stability in HNO3/H3PO4 environments

• CYANEX 301 → Ecd(aq) > 99% with HCl 6 M and O:A = 1:1

• (diphenylphosphinylmethyl)phenylphosphinic acids → a possible future

alternative for Cd removal and REEs extraction ?

Slide 28Hydromet project meeting5 October 2016

Acknowledgements

Thank you for your attention!

Slide 29Hydromet project meeting5 October 2016

Discussion points...

Slide 30Hydromet project meeting5 October 2016

• Are the chemical stability studies representative of the industrial conditions?

• Can CYANEX 301 considered to be ok for the development of the studies?

• Are lower HCl concentrations to be sought for stripping of CYANEX 301?

• What about (diphenylphosphinylmethyl)phenylphosphinic acids? Could they

be of any interest?

Slide 31Hydromet project meeting

KELEX 100: solvent extraction studies

+KELEX 100 (0.02 M)

in decane/1-decanol (10% vol)

HNO3/H3PO4 or H3PO4 solutions

(containing 10 ppm Cd)

at different pH values

109Cd in

0.05 M HNO3 =O/A: 1/1

shaking

(according to proper

equilibrium kinetics study)centrifugation

aqueous

organic

liquid scintillation counting

(after proper efficiency calibration)

0 100 200 300 400 500

0

200

400

600

800

1000

Counts

Channel

5 October 2016

Slide 32Hydromet project meeting

KELEX 100: solvent extraction studies

pH measurement

-50 0 50 100 150 200 250 300 350

1

2

3

4

5

6

7

pH

Voltage (mV)

Equation y = a + b*x

Weight No Weighting

Residual Sum of Squares

0,013

Pearson's r -0,99964

Adj. R-Square 0,99856

Value Standard Error

pHIntercept 6,5068 0,09413

Slope -0,01763 4,73902E-4

-150 -100 -50 0 50 100 150 200

4

5

6

7

8

9

pH

Voltage (mV)

Equation y = a + b*x

Weight No Weighting

Residual Sum of Squares

0,01954

Pearson's r -0,99923

Adj. R-Square 0,9969

Value Standard Error

pHIntercept 6,62549 0,08073

Slope -0,01734 6,83113E-4

5 October 2016

Slide 33Hydromet project meeting

KELEX 100 chemical stability studies: LC-ESI-MS results

C:\Xcalibur\...\Alex\Alex-Relex-t=0 06/01/16 14:09:30

RT: 0.00 - 30.01 SM: 7B

0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30

Time (min)

0

50

100

0

50

100

0

50

100

Re

lative

Ab

un

da

nce

0

50

1007.97

1.82 7.32 19.937.13 23.528.27 22.97 23.7310.11 14.6610.39 18.77 21.5413.3812.09 15.18 18.56 24.83 25.97 27.551.61 28.413.39 3.85 6.305.31

15.39

22.9722.55 23.1024.1817.80

25.41 26.4317.1213.80 18.56 27.49 28.4919.179.95

15.96

1.77 11.327.876.66

7.67 9.749.94 16.86

14.8827.35

29.446.61

NL: 1.17E10

TIC F: FTMS + p ESI Full ms [100.00-1000.00] MS Alex-Relex-t=0

NL: 1.16E7

m/z= 300.22719-300.23719 F: FTMS + p ESI Full ms [100.00-1000.00] MS Alex-Relex-t=0

NL: 2.96E4

m/z= 345.21226-345.22226 F: FTMS + p ESI Full ms [100.00-1000.00] MS Alex-Relex-t=0

NL: 1.36E4

m/z= 361.20718-361.21718 F: FTMS + p ESI Full ms [100.00-1000.00] MS Alex-Relex-t=0

Alex-Relex-t=0 #2629 RT: 15.38 AV: 1 NL: 1.07E7T: FTMS + p ESI Full ms [100.00-1000.00]

299.2 299.4 299.6 299.8 300.0 300.2 300.4 300.6 300.8 301.0 301.2 301.4

m/z

0

10

20

30

40

50

60

70

80

90

100

Re

lative

Ab

un

da

nce

300.23074

C 20 H30 O N

301.23410

299.30420299.21872300.28830

C 18 H38 O 2 N 300.91885299.91125

Reference organic phase: KELEX 100 (0.02 M) in decane/1-decanol (10% vol)

N

OH

Molecular Formula = C20H29NO

Formula Weight = 299.45036

5 October 2016

Slide 34Hydromet project meeting

KELEX 100 chemical stability studies: LC-ESI-MS results

Organic phase after reaction with 0.3 M HNO3/H3PO4 solution for 1h at 90 °C

C:\Xcalibur\...\Alex-Relex-0_3M-1hour 06/01/16 14:51:29

RT: 0.00 - 30.01 SM: 7B

0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30

Time (min)

0

50

100

0

50

100

0

50

100

Re

lative

Ab

un

da

nce

0

50

1008.08

17.31 17.4617.20 19.917.411.81 20.037.12 18.10 23.3323.0014.55 23.7814.1112.778.54 14.9711.55 24.769.49 26.431.62 27.25 28.532.37 3.40 5.794.30

17.31

17.62

17.84

18.63 19.21 20.56 22.05 22.87 23.61 25.1516.32 26.33 27.4115.57 28.4714.3913.5112.3711.3310.29

20.69

17.48

16.131.61 14.8213.11 27.52

16.88

20.641.80

20.721.75 16.959.84 26.7716.77 27.42

NL: 9.33E9

TIC F: FTMS + p ESI Full ms [100.00-1000.00] MS Alex-Relex-0_3M-1hour

NL: 3.24E9

m/z= 300.22719-300.23719 F: FTMS + p ESI Full ms [100.00-1000.00] MS Alex-Relex-0_3M-1hour

NL: 1.76E6

m/z= 345.21226-345.22226 F: FTMS + p ESI Full ms [100.00-1000.00] MS Alex-Relex-0_3M-1hour

NL: 3.45E4

m/z= 361.20718-361.21718 F: FTMS + p ESI Full ms [100.00-1000.00] MS Alex-Relex-0_3M-1hour

Alex-Relex-0_3M-1hour #3636 RT: 20.68 AV: 1 NL: 1.50E6T: FTMS + p ESI Full ms [100.00-1000.00]

342 343 344 345 346 347 348 349 350 351 352

m/z

0

10

20

30

40

50

60

70

80

90

100

Re

lative

Ab

un

da

nce

345.21567

C 20 H29 O 3 N2

346.21890

C 24 H28 O N

344.22650

C 24 H28 N2 350.33612

N

OH

NO2

Molecular Formula = C20H28N2O3

Formula Weight = 344.44792

5 October 2016

Slide 35Hydromet project meeting

KELEX 100 chemical stability studies: LC-ESI-MS results

Organic phase after reaction with 0.3 M HNO3/H3PO4 solution for 72h at 90 °C

C:\Xcalibur\...\Alex-Relex-0_3M-72hours 06/01/16 15:33:20

RT: 0.00 - 30.01 SM: 7B

0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30

Time (min)

0

50

100

0

50

100

0

50

100

Re

lative

Ab

un

da

nce

0

50

1008.06

16.19 17.28

18.527.291.82 15.627.02 19.458.47 23.3212.74 13.3711.92 23.8820.37 23.168.99 24.632.04 26.80 27.421.64 28.662.62 4.75

17.1217.38

17.5017.0418.5216.21

18.76 20.9815.94 21.2715.23 22.86 23.8114.20 24.8612.62 25.97 27.0511.62 28.1710.549.331.63 8.585.094.50 5.62

15.54

16.08 16.86

18.2918.4315.40

13.75

16.20

15.52 18.9718.6514.959.83

NL: 8.76E9

TIC F: FTMS + p ESI Full ms [100.00-1000.00] MS Alex-Relex-0_3M-72hours

NL: 3.05E9

m/z= 300.23069-300.23369 F: FTMS + p ESI Full ms [100.00-1000.00] MS Alex-Relex-0_3M-72hours

NL: 1.53E5

m/z= 345.21553-345.21899 F: FTMS + p ESI Full ms [100.00-1000.00] MS Alex-Relex-0_3M-72hours

NL: 8.84E5

m/z= 361.21037-361.21399 F: FTMS + p ESI Full ms [100.00-1000.00] MS Alex-Relex-0_3M-72hours

Alex-Relex-0_3M-72hours #2780 RT: 16.23 AV: 1 NL: 9.03E5T: FTMS + p ESI Full ms [100.00-1000.00]

359.5 360.0 360.5 361.0 361.5 362.0 362.5 363.0 363.5 364.0 364.5 365.0

m/z

0

10

20

30

40

50

60

70

80

90

100

Re

lative

Ab

un

da

nce

362.26807

C 25 H34 N2

361.21088

C 20 H29 O 4 N2

360.19839

N+

OH

NO2

O-

Molecular Formula = C20H28N2O4

Formula Weight = 360.44732

5 October 2016

Slide 36Hydromet project meeting

KELEX 100 chemical stability studies: LC-ESI-MS results

Organic phase after reaction with 3 M HNO3/H3PO4 solution for 1h at 90 °C

C:\Xcalibur\...\Alex\Alex-Relex-3M-1hour 06/01/16 16:15:12

RT: 0.00 - 30.01 SM: 7B

0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30

Time (min)

0

50

100

0

50

100

0

50

100

Re

lative

Ab

un

da

nce

0

50

1008.07

7.297.181.81 17.268.34 19.45 23.0122.89 23.3611.37 17.14 19.248.84 24.51 26.02 26.9715.8011.83 20.49 28.0513.42 29.132.12 2.66 4.61 5.24

17.2716.20

16.0415.67 17.50

19.4414.62 20.52 22.1014.21 22.4213.19 23.5011.68 24.91 25.9510.35 27.119.27 28.148.611.72 3.95 5.013.26 6.10 6.51

18.26

22.4421.2021.08 23.36 23.7618.94 20.31

24.4317.53 25.1217.02

17.58

17.47

17.04 18.919.74 16.12

NL: 7.87E9

TIC F: FTMS + p ESI Full ms [100.00-1000.00] MS Alex-Relex-3M-1hour

NL: 4.03E8

m/z= 300.23069-300.23369 F: FTMS + p ESI Full ms [100.00-1000.00] MS Alex-Relex-3M-1hour

NL: 2.14E5

m/z= 345.21553-345.21899 F: FTMS + p ESI Full ms [100.00-1000.00] MS Alex-Relex-3M-1hour

NL: 6.34E4

m/z= 361.21037-361.21399 F: FTMS + p ESI Full ms [100.00-1000.00] MS Alex-Relex-3M-1hour

Alex-Relex-3M-1hour #1 RT: 1.57 AV: 1 NL: 3.39E7T: FTMS + p ESI Full ms [100.00-1000.00]

200 250 300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000

m/z

0

10

20

30

40

50

60

70

80

90

100

Re

lative

Ab

un

da

nce

201.11108

C 8 H15 O 3 N3

218.13757

C 8 H18 O 3 N4

391.28217

C 20 H35 O 2 N6257.24606

C 14 H31 O N3

593.15448

C 17 H25 O 14 N10

667.17218

C 26 H35 O 20

445.11743

C 12 H17 O 9 N10

519.13611

C 8 H25 O 17 N9

743.19049

C 30 H31 O 15 N8 867.20728 930.35315809.56683

5 October 2016

Slide 37Hydromet project meeting

KELEX 100 chemical stability studies: LC-ESI-MS results

Organic phase after reaction with 3 M HNO3/H3PO4 solution for 72h at 90 °C

C:\Xcalibur\...\Alex-Relex-3M-72hours 06/01/16 16:57:01

RT: 0.00 - 30.01 SM: 7B

0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30

Time (min)

0

50

100

0

50

100

0

50

100

Re

lative

Ab

un

da

nce

0

50

1008.09

1.79 7.337.20 18.15 18.2517.94 19.858.44 12.83 14.4412.0011.23 16.18 23.759.68 24.5123.54 28.2325.05 28.7820.80 26.112.22 3.12 4.84 5.801.67

16.15 16.29

17.27

15.96 17.6015.28 20.7318.22 20.8514.27 22.3513.16 23.1311.87 24.52 25.7410.50 26.71 28.119.40 29.304.82

16.26 16.4515.97

20.17 22.4215.80 17.62 22.5621.7815.39

14.74 23.9324.4713.96 25.58

20.31

20.21 20.5518.97

21.2716.81 21.4416.287.03 18.6113.47 23.90

NL: 6.80E9

TIC F: FTMS + p ESI Full ms [100.00-1000.00] MS Alex-Relex-3M-72hours

NL: 5.44E7

m/z= 300.23069-300.23369 F: FTMS + p ESI Full ms [100.00-1000.00] MS Alex-Relex-3M-72hours

NL: 3.41E5

m/z= 345.21553-345.21899 F: FTMS + p ESI Full ms [100.00-1000.00] MS Alex-Relex-3M-72hours

NL: 1.80E5

m/z= 361.21037-361.21399 F: FTMS + p ESI Full ms [100.00-1000.00] MS Alex-Relex-3M-72hours

Alex-Relex-3M-72hours #3292 RT: 19.00 AV: 1 NL: 1.01E5T: FTMS + p ESI Full ms [100.00-1000.00]

360.5 361.0 361.5 362.0 362.5 363.0 363.5 364.0 364.5 365.0

m/z

0

10

20

30

40

50

60

70

80

90

100

Re

lative

Ab

un

da

nce

361.21063

C 20 H29 O 4 N2

363.30881

362.19452

364.34149

C 23 H44 O N2

360.30951

N+

OH

NO2

O-

Molecular Formula = C20H28N2O4

Formula Weight = 360.44732

5 October 2016

Slide 38Hydromet project meeting

New bibliographic results: KELEX 100

KELEX 100

7-(4-ethyl-1-methyloctyl)-8-hydroxyquinoline

+kerosene

with (10% vol)

n-decanol

Organic phase Aqueous phase

H3PO4 sol.

(pH 0.5-4)

A. Mellah et al., Hydrometallurgy 81 (2006) 100-103

5 October 2016

Slide 39Hydromet project meeting

Future steps: a possible alternative…

Cd free

Cd

Elemental sulphur: waste of the oil industry

SEPARATION, e.g., FILTRATION

5 October 2016