New Extraction Process of Precious Metals from Scrap by Chemical Vapor Treatment

Chihiro Ohkawa Toru H. Okabe

Institute of Industrial Science The University of Tokyo, Tokyo, Japan

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New Extraction Process of Precious Metals from Scrap by Chemical Vapor Treatment
1. Introduction Background Previous research Purpose of this study 2. New process using Mg and FeCl3 vapor 3. New process using Li vapor and Cl2 gas 4. Summary
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Precious metals
Chemical industry
(Pt, Pd, Ru, Au, etc.) Textile industry
VIIIA IB IIB IIIB IVB VB VIBVIIB 0 IA IIA IIIA IVA VA VIA VIIA 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18
1 2

Jewelry
(Au, Pt, Ag, Rh, etc.)

1 H
3 4 5 6 7 8 9

He
10

2 Li Be
11 12

B C N O F Ne
13 14 15 16 17 18

3 NaMg
19 20 21 22 23 24 25 26 27 28 29 30

Al Si P S Cl Ar
31 32 32 34 35 36

4 K Ca Sc Ti
37 38 39 40

V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
41 42 43 44 45 46 47 48 49 50 51 52 53 54 73 74 75 76 77 78 79 80 81 82 83 84 85 86

http://www.ginzatanaka.co.jp/

5 Rb Sr Y
55 56 57~71

Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
72

http://www.nippon-nz.com/japanese/jigyo/pdct_220.html

6 Cs Ba *
87 88 89~103

Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
104 105 106 107 108 109

Thermocouples

7 Fr Ra ** Unq Unp Unh Uns UnoUne

* Lanthanoid ** Actinoid

Laboratory instruments
(Pt, Ir, Au, etc.)

Electronic Catalysts (Pt, Pd, Rh, etc.) components, Automotive exhaust catalyst Semiconductors
http://www.ishifuku.co.jp/Products/Industrial/intro7.htm

(Au, Ag, Pd, Ru, etc.)

http://www.inter-g7.or.jp/tanaka/products/products.html

Infusible electrodes Petrochemical industry

Dental alloys
(Au, Pt, Pd, etc.)

http://www.ishifuku.co.jp/Products/Industrial/intro7.htm

http://www.kkmisuzu.co.jp/

http://www.ne-chemcat.co.jp/kagaku/noblemetal/index.html

http://www.tokuriki-kanda.co.jp/shika/index.html

Fig. Periodic table and applications of precious metals.

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Supply and demand

Demand
Chemicals: 10 t (4%) Other Electricals: 9 t (4%) Jewelry: 68 t (30%) Other North america: 12 t (5%) Russia: 26 t (12%)

Supply
Recovery from autocatalysts: 22 t (10%)

Pt 227 t
Autocatalysts: 109 t (48%) Chemicals: 1.3 t (5%) Other

Pt 224 t
South Africa: 157 t (70%)

Net producer hedging: 442 t (11%)

Recovery from autocatalysts: 4 t (16%)

Recovery from scrap: 828 t (22%)

South Africa: 343 t (9%)

Rh 27 t
Autocatalysts: 24 t (89%)

Other

Au
3,851 t

Russia: 3 t (12%) Rh

27 t

Jewelry: 2,610 t (68%) Electricals: 261 t (7%)

Other

South Africa: 18 t (67%)

Au Other: Official 3,851 t 1,601 t sectors: (42%) 478 t (12%)

Australia: 258 t (7%) America: 262 t (7%)

Fig. Supply and demand of precious metals in the world (2004).

*Johnson Matthey PLc: Platinum 2005 (2005). **Gold Fields Mineral Services Ltd.: Gold Survey 2005 (2005).

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Transition and prediction of Pt demand

600 500 400 300 200 100 0 1900

Estimate

World demand, w / ton

Total production of Pt since recorded history 5,000 t Current world production of Pt 200 t / year

1920

1940

1960

1980

2000

2020

Fig. Transition and prediction of the world demand of platinum from 1900 to 2030. The demand for Pt is increasing because of tightening environmental regulations. It is extremely important to develop a new recovery process for precious metals.
*Johnson Matthey PLc: Platinum 2005 (2005). **U.S. Bureau of Mines: Minerals yearbook. etc

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Typical recovery process for precious metals

Scrap containing precious metals (M) Pretreatment (Crushing, etc.)

Pyrometallurgical process
High efficiency High speed High energy cost Large-scale facilities required

Directly dissolved in acid

Cu, Pb, Fe, etc. Extraction by collector metals Collector metal containing M

Hydrometallurgical process
Low energy cost Easy handling Long processing time Generation of a large amount of waste solution

Dissolution in acid Separation and purification Recovered precious metals

Fig. Typical recovery process for precious metals from scrap.

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Dissolution rate of precious metals

3000 Metal conc. in leached solution / ppm 2500 2000 1500 1000 500 0 0 30 60 90 120 Time / min

Pd Au

Dissolution of precious metals is very difficult, even by aqua regia. Hydrometallurgical process requires a large amount of acid with a strong oxidant and involves a long processing time. If dissolution efficiency of precious metals is increased, hydrometallurgical process is expected to transform into a new energy saving process. Leaching rate of Pt is extremely low.

Ag Pt
150

Fig. Dissolution behaviors of Au, Ag, Pt, and Pd with aqua regia as a function of time.
(Solution volume: 300 cm3, Sample form: 10 x 10 x 0.5 mm (1.07 g), Leaching temperature: RT)

*J. Shibata et al., Kagaku Kogaku Ronbunsyu, 27 (2001), pp. 367372.

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Previous research
New extraction process for platinum group metals (PGMs) from waste materials by using reactive metal vapor
Metal vapor is supplied to PGMs dispersed on an oxide substrate.
Platinum group metals (PGMs)
Mg3Pt MgPt MgPt3 Ca5Pt3 Ca3Pt2 CaPt2 CaPt5 Li5Pt Li2Pt LiPt LiPt2 Fe3Pt FePt FePt3

R-PGM alloys are formed selectively.

R-PGM compounds

Surface area of PGMs is enlarged by selective dissolution of R.

A. R. Miedema et al.: Cohesion in Metals (1989).

This enables PGMs to react with acid effectively, and they dissolve faster than in their pure form.

60 Hcalcfor / kJ(mol of atoms)1

20

40

80

Fig. Calculated enthalpy of formation of binary Pt compounds.

Fig. Concept of the metal vapor treatment of PGMs.

*T. H. Okabe et al., Journal of Materials Research, 18, No. 8 (2003), pp. 19601967. **T. H. Okabe et al., Materials Transactions, JIM, 44, No. 7 (2003), pp. 13861393. ***Y. Kayanuma et al., Journal of Alloys and Compounds, 365 (2004), pp. 211220.

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Previous research
New extraction process for platinum group metals (PGMs) from waste materials by using reactive metal vapor
Pt
Mass% of dissolved Pt R: Mg R: Ca

100 50 0

Mass of sample: 0.05 - 0.1 g Leaching time: 1 - 4 h Temperature: RT

Mg or Ca treatment of pure Pt or Rh was effective in enhancing the dissolution rate of Pt and Rh in aqua regia.
R-Pt

Pt

Rh
Mass% of dissolved Rh

R: Mg

R: Ca

100 50 0
Mass of sample: 0.05 - 0.1 g Leaching time: 1 h Temperature: 323 - 333 K

However, there still remains a problem: the generation of a large amount of waste solution containing heavy metals and strong acids.

Rh

R-Rh

Fig. Results of dissolution experiments of R-Pt and R-Rh samples using aqua regia.
*T. H. Okabe et al., Journal of Materials Research, 18, No. 8 (2003), pp. 19601967. **T. H. Okabe et al., Materials Transactions, JIM, 44, No. 7 (2003), pp. 13861393. ***Y. Kayanuma et al., Journal of Alloys and Compounds, 365 (2004), pp. 211220.

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E-pH diagram
(a) Pt-H2O system (aCl = 0)
1.5

(b) Pt-H2O-Cl system (aCl = 0.48)

1.5

Potential, E / V

Pt2+
1.0

Potential, E / V

PtO3 PtO2

1.0

[PtCl6]2

PtO3

0.5

Pt H2

O2 PtO

PtO2
0.5

O2 PtO

H2
0.0 0

Pt
4 8 12

0.0 0 4 8 12

pH

pH

Fig. E-pH diagram of (a) Pt-H2O and (b) Pt-H2O-Cl systems at 298 K. Oxidizing agent is required for the dissolution of precious metals. However, when chloride compound is formed, it is possible to dissolve precious metals in acid without using an oxidant.
*M. Pourbaix: Atlas of Electrochemical Equilibria in Aqueous Solution (1966).

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Purpose of this study

Development of a new method for dissolving precious metals by reactive metal treatment followed by chlorination
(a) Conventional leaching process
pCl , pO
2 2

Chemical potential of chlorine (or oxygen)

Oxidation Dissolution PtCl62

Processing time, tprocess

Pt

Long duration time

Long processing time and considerable amount of acids with strong oxidants are required for the dissolution. A large amount of waste solution containing heavy metals and strong acids is generated.
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Purpose of this study

Development of a new method for dissolving precious metals by reactive metal treatment followed by chlorination
(b) Reactive metal treatment followed by chlorination (or oxidation)
pCl , pO
2 2

Chemical potential of chlorine (or oxygen)

Chlorination (or oxidation) Higher dissolution efficiency RPtxCly (or RPtxOy) Lower amount of acids used for dissolution High-speed dissolution Oxidation Dissolution PtCl62

Pt

Processing time, tprocess

Short duration time

R-Pt Compound formation under reduced atmosphere Pretreatment for selective and efficient dissolution of PGMs

Discharge volume of waste solution can be reduced and chloride waste (e.g., FeCl3) can be utilized.
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New Extraction Process of Precious Metals from Scrap by Chemical Vapor Treatment
1. Introduction 2. New process using Mg and FeCl3 vapor Flowchart of this part Synthesis of Mg-M compounds Chlorination of Mg-M compounds using FeCl3 Results 3. New process using Li vapor and Cl2 gas 4. Summary
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Flowchart of this study

Scrap containing precious metals (M)
(M: Pt, Rh, Au, etc.)

Reactive metal (R)

(R: Mg, Li, etc.)

R vapor treatment R-M compounds Chlorination (or oxidation) RMxCly (or RMxOy) compounds Dissolution Solution containing precious metals Precious metal recovery Pure precious metals Residue Efficient dissolution Pretreatment shortens the dissolution time

Chlorination agent
(or O2)

HCl aq.

Fig. Precious metal recovery through the formation of complex chlorides (or oxides) by chloride vapor treatment.
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Selection of alloy former and chlorination agent

Temperature, T / K
1400 0 1200 1000 800 600

Supplying extraction medium in vapor form Reactants can be supplied to the entire quantity of scrap, irrespective of its complicated structure. Precious metals (M)
(M: Pt, Rh, and Au)

Li Vapor pressure, log pi (atm)

-5

ZnCl2 AlCl3 Zn FeCl3 Mg FeCl2

NaCl MgCl2
-10

Ca KCl LiCl

Mg

Alloy formation R-M compounds

Cu
-15

CaCl2

Au Pt Rh

FeCl3 vapor

Chlorination RMxCly compounds

-20 0.8 1.0 1.2 1.4 1.6

Acids

Dissolution

Residue

Reciprocal temperature, 1000 T1 / K1

Fig. Vapor pressure of selected metals and chlorides.

*I. Barin: Thermochemical Data of Pure Substances, 3rd edition (1995).

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Synthesis of Mg-M compounds

TIG welding Stainless steel reaction vessel Stainless steel cover Mg Precious metal (Pt, Rh, or Au) Ta crucible Stainless steel plate Sponge Ti

Fig. Schematic illustration of the experimental apparatus for the synthesis of Mg-M compounds. Pure precious metals were reacted with molten Mg at 1173 K for 12 h. XRD analysis: Mg-M compounds were formed (but their phases were not identified). SEM/EDS analysis: Homogeneous compounds were obtained.
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Chlorination of Mg-M compounds using FeCl3

Stainless steel reaction vessel Stainless steel crucible Quartz tube Quartz crucible Heater

Ar/ vacuum

Stainless steel sample holder M powder FeCl3 Powder of Mg-M compound (M = Pt, Rh, or Au)

Fig. Schematic illustration of the experimental apparatus for the chlorination of Mg-M compounds. Mg-M compounds were reacted with FeCl3 vapor at 673 K for 3 h. Mass change: The increase in the mass of Mg-M compounds after chlorination was greater than that of pure precious metals. XRD analysis: Identification of the phases in the samples was difficult due to the absence of relevant reference data.
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Results of dissolution experiment

Mass% of dissolved Pt
100 50 0

Pt
T = RT t = 1 h Pt Mg-Pt Chlorinated Chlorinated Mg-Pt Pt

Dissolved in aqueous HCl solution Dissolved in aqua regia (HCl + HNO3) Not dissolved after leaching

Mass% of dissolved Rh

100 50 0

Rh
T = 323333 K t = 1 h

Dissolution efficiencies of Pt and Rh in aqua regia after alloy formation and chlorination were significantly enhanced.
Chlorinated Chlorinated Mg-Rh Rh

Rh

Mg-Rh

Mass% of dissolved Au

100 50 0

Au
T = RT t = 1 h Au Mg-Au Chlorinated Chlorinated Mg-Au Au

Fig. Percentage of dissolved precious metals after the leaching experiment.

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Results of dissolution experiment

Mass% of dissolved Pt
100 50 0

Pt
T = RT t = 1 h Pt Mg-Pt Chlorinated Chlorinated Mg-Pt Pt

Dissolved in aqueous HCl solution Dissolved in aqua regia (HCl + HNO3) Not dissolved after leaching

Mass% of dissolved Rh

100 50 0

Rh
T = 323 333 K t = 1 h

Chlorinated Rh and Mg-Rh compounds were dissolved in HCl aq. although pure Rh barely dissolved in acids.
Chlorinated Chlorinated Mg-Rh Rh

Rh

Mg-Rh

Mass% of dissolved Au

100 50 0

Au
T = RT t = 1 h Au Mg-Au Chlorinated Chlorinated Mg-Au Au

Fig. Percentage of dissolved precious metals after the leaching experiment.

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Results of dissolution experiment

Mass% of dissolved Pt
100 50 0

Pt
T = RT t = 1h Pt Mg-Pt Chlorinated Chlorinated Mg-Pt Pt

Dissolved in aqueous HCl solution Dissolved in aqua regia (HCl + HNO3) Not dissolved after leaching

Mass% of dissolved Rh

100 50 0

Rh
T = 323 333 K t = 1h

Rh

Mg-Rh

Chlorinated Chlorinated Mg-Rh Rh

Dissolution efficiencies of Au obtained from Mg-Au and chlorinated Mg-Au compounds decreased. The reason for these results is under investigation.

Mass% of dissolved Au

100 50 0

Au
T = RT t = 1h Au Mg-Au Chlorinated Chlorinated Mg-Au Au

Fig. Percentage of dissolved precious metals after the leaching experiment.

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SEM analysis
(a) Before leaching
Mg-Pt

(b) After HCl aq. leaching Mg and Fe were dissolved, and their mass ratios became less than 1 mass% after leaching. Grains of precious metals with several microcracks were obtained as residues after leaching in HCl aq.

10 m

10 m

Mg-Rh

10 m

10 m

Mg-Au

Large surface areas of Pt and Rh that formed after/during dissolution of Mg and Fe caused an increase in the dissolution efficiencies of chlorinated Mg-M compounds.

10 m

10 m

Fig. Scanning electron micrograph of Mg-M compounds before and after leaching with HCl aq.
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New Extraction Process of Precious Metals from Scrap by Chemical Vapor Treatment
1. Introduction 2. New process using Mg and FeCl3 vapor 3. New process using Li vapor and Cl2 gas Flowchart of this part Synthesis of Li-M compounds Chlorination of Li-M compounds using Cl2 gas Results 4. Summary
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Selection of alloy former

Temperature, T / K
1400 0 1200 1000 800 600

Li Vapor pressure, log pi (atm)

-5

ZnCl2 AlCl3 Zn FeCl3 Mg FeCl2

Readily-soluble chloride complexes of Li and Pt or Rh were reported. (Li2[PtCl4]6H2O, Li3[RhCl6]12H2O) Li battery scrap can be utilized as Li source. Precious metals (M)
(M: Pt and Rh)

NaCl MgCl2
-10

Ca KCl LiCl

Li vapor

Alloy formation R-M compounds

Cu
-15

CaCl2

Au Pt Rh

Cl2 gas

Chlorination RMxCly compounds

-20 0.8 1.0 1.2 1.4 1.6

Acids

Dissolution

Residue

Reciprocal temperature, 1000 T1 / K1

Fig. Vapor pressure of selected metals and chlorides.

*I. Barin: Thermochemical Data of Pure Substances, 3rd edition (1995).

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Synthesis of Li-M compounds

(a) Stainless steel container Precious metal (Pt or Rh)
73 mm

(b) TIG welding Stainless steel reaction vessel Stainless steel container (a) Sponge Ti

Mo crucible Stainless steel sheet Li shot Sponge Ti

20 mm

Fig. Schematic illustration of the experimental apparatus for the synthesis of Li-M compounds. Pure Pt and Rh were reacted with Li vapor at 1173 K for 6 h. XRD analysis: Li2Pt was obtained in Li-Pt system, and LiRh was obtained in Li-Rh system. But some peaks were not identified.
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Chlorination of Li-M compounds using Cl2 gas

Heater
Ar

Chlorination reactor

Cl2 gas inlet Cl2 gas generator Dehydrator Powder of Li-M compound or M (M = Pt or Rh) conc. HCl aq. P2O5 Light-proof bubbler conc. KMnO4 aq. H2O KMnO4 aq. H2O Na2S2O3 aq. Gas outlet Cl2 absorber

Fig. Schematic illustration of the experimental apparatus for the chlorination of Li-M compounds. Li-M compounds were reacted with Cl2 gas at 723~773 K for 1h. XRD analysis: RhCl3 was obtained in Li-Rh system. But identification of the phases in other samples was difficult due to the absence of relevant reference data.
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Results of dissolution experiment

Mass% of dissolved Pt

100 50 0

Pt
T = RT t = 1 h Pt Li-Pt Chlorinated Chlorinated Li-Pt Pt

Dissolved in aqueous HCl solution Dissolved in aqua regia (HCl + HNO3) Not dissolved after leaching

Mass% of dissolved Rh

100 50 0

Rh
T = 323333 K t = 1 h

Dissolution efficiencies of Pt in aqua regia after alloy formation and chlorination were significantly enhanced.

Rh

Li-Rh

Chlorinated Chlorinated Li-Rh Rh

Fig. Percentage of dissolved precious metals after the leaching experiment.

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Results of dissolution experiment

Mass% of dissolved Pt

100 50 0

Pt
T = RT t = 1 h Pt Li-Pt Chlorinated Chlorinated Li-Pt Pt

Dissolved in aqueous HCl solution Dissolved in aqua regia (HCl + HNO3) Not dissolved after leaching

Mass% of dissolved Rh

100 50 0

Rh
T = 323333 K t = 1 h

Dissolution efficiency of Rh in aqua regia after alloy formation was slightly increased.

Rh

Li-Rh

Chlorinated Chlorinated Li-Rh Rh

Fig. Percentage of dissolved precious metals after the leaching experiment.

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Results of dissolution experiment

Mass% of dissolved Pt

100 50 0

Pt
T = RT t = 1 h Pt Li-Pt Chlorinated Chlorinated Li-Pt Pt

Dissolved in aqueous HCl solution Dissolved in aqua regia (HCl + HNO3) Not dissolved after leaching

Mass% of dissolved Rh

100 50 0

Rh
T = 323333 K t = 1 h

Rh

Li-Rh

Chlorinated Chlorinated Li-Rh Rh

Dissolution efficiencies of Rh were not improved after chlorination using Cl2 gas. This is due to the formation of RhCl3 which is insoluble in acids.

Fig. Percentage of dissolved precious metals after the leaching experiment.

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SEM analysis
(a) Before leaching Li-Pt (b) After HCl aq. leaching

10 m

10 m

Li-Rh

Fig. Scanning electron micrograph of Li-M compounds before and after leaching with HCl aq.

10 m

10 m

Pt metal comprising micro grains with several cracks was obtained as residues after leaching of Li-Pt and chlorinated Li-Pt compounds by HCl aq. Large surface area of Pt formed after/during dissolution of Li caused an increase in the dissolution efficiencies of Li-Pt and chlorinated Li-Pt compounds. No major change of surface shape was observed in Li-Rh system.
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Summary
1. Reactive metal treatment followed by chlorination was conducted for increasing the dissolution rate of precious metals. 2. Precious metals were reacted with molten Mg at 1173 K for 12 h, and then chlorinated using FeCl3 vapor at 673 K for 3 h. After these treatments, dissolution efficiencies of Pt and Rh in aqua regia were significantly enhanced.
pCl , pO
2 2

Chemical potential of chlorine (or oxygen)

Chlorination (or oxidation) RPtxCly (or RPtxOy) Oxidation Dissolution PtCl62 Short!
Processing time, tprocess

Pt

R-Pt Compound formation

3. Precious metals were reacted with Li vapor at 1173 K for 6 h, and then chlorinated using Cl2 gas at 723~773 K for 1 h. After these treatments, dissolution efficiency of Pt in aqua regia increased. Dissolution efficiency of Rh from Li-Rh compounds was slightly enhanced; however, those of chlorinated samples were not improved because of the formation of RhCl3 which is insoluble in acids. Optimization of chlorination condition is an important issue in the future.
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