experience and prospect on resource management of metals ......basic oxygen furnace: bof (converter)...

Japan's experience and prospect on resource management of metals:

policies, strategies, and technologies

K. Matsubae and T. NagasakaTohoku University, Sendai, Japan

Tetsu NagasakaDate of birth: Oct. 1957

Graduated Tohoku Univ. in 1980Ph.D at Tohoku in 1985

Assist. Prof. at Tohoku 1985Res. Assoc. at Carnegie Mellon Univ. USA in 1993

Prof. of Environmental Studies in 2001Now Prof. Graduate School of Engineering

MajorPhysical‐chemistry on iron‐ and steelmaking

MFA and LCA

Question

“Are metals, such as aluminum, copper, steel, etc., well recycled in our society?”

Answer

In the view point of quantity, YES.

But

In the view point of quality, NO

What I want to tell you today is

1.“Metals used in our society are

mostly in the form of alloy rather than pure metals”

Exceptionscopper wirealuminum foilCP‐Ti (commercially pure titanium)other very minor products for special use

What I want to tell you today is

2.“Suppliers of primary metal

resources (natural ore) are quite limited”

Mineral resource majors in the worldVale (Brazil: iron ore)Rio Tinto (UK, AUS: iron ore, coal, aluminum, copper)BHP Billiton (AUS, UK: iron ore, coal, aluminum, copper)Inco etc.

Solution

“A country which does not have

enough natural metal resources should recycle metal products with keeping their quality”

It is easy to say so but not easy to do so.

The Basic Environment Law

The Basic Law for Establishing the Recycling‐based Society

Law Concerning Waste Disposal and Scavenging (Waste Disposal Law)Law for Promotion of Effective Utilization of Resources

Construction Material Recycling Law Law for Promotion of Sorted Collection and Recycling of Containers and PackagingLaw for Promotion of Recycling and Related Activities for Treatment of Cyclical Food

Resources Law for the Recycling of Specified Kinds of Home Appliances

Law for the Recycling of End‐of‐Life Vehicles Law on Promoting Green Purchasing)

http://www.env.go.jp/en/laws/

Structure of environment related regulations in Japan

Metal resources related laws

Target products

Air conditioner

CRT (TV with Cathode‐ray tube)

Refrigerator, Freezer

Washing machine

* Flat panel display

* Clothes dryer

* from 2009

Law for the Recycling of Specified Kinds of Home Appliances

Law for the Recycling of Specified Kinds of Home Appliances

Dismantling

Shredding

Separation

RecoveryPartsFreonetc.

plastics

For example, East Japan Recycling Systems Corp.http://www.ejrs.co.jp/index.html

metals others

Law for the Recycling of End-of-Life Vehicles (ELV)

Dismantling

Pressing

RecoveryPartsFreonAir bagCu wireEngineetc.

Steel scrap

Iron and steel cycle in Japan (2003) source:JISF

Accumulation1263

Consumption127

Exp. steel products35

Domestic scrap46

Crude steel83

Obsolete scrap34

Exp. commodity 22

Imp. scrap6

Imp. commodity 4

Imp. steel products4

Blast furnace: BF(ironmaking)

Electric arc furnace: EAF(steelmaking)

Basic oxygen furnace: BOF(Converter)(steelmaking)

Refining(composition control)

Continuous casting: CC(solidification)

Rolling (shaping andMicrostructure control)

Iron oreCokeLime

Steelscrap

1400oC

1600oC

1600oC

1600oC

1000oC

Iron and steelmaking process

Human economicactivities

We should know

“Steel is not pure iron.

Steel is alloy of iron (Fe) with other various kinds of metals. Big steel company produces more than 1000 kinds of steel products which have different shape and composition ”

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2

4

6

8

10

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濃度（mass%）

鋼種

110

1001,000

10,000

100,00

1,00

10

生産量（ｔ）

110

1001,000

10,000100,000

1,000,00010,000,000

100,000,000

amount in products (t)

concentration (mass%)

steel grade

Stainless steel austeniticHeat‐resisting steel bars austenitic

High manganese steel castings

average percent in steel products

Mn

Stainless steelHeat‐resisting steel bars

Carbon tool steelｓ

general processing steel

steel for building structure

general structure steel

Mn

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材

一般

加工

用鋼

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容器

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建築

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用鋼

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用途

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0

2

4

6

8

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濃度（mass%）

鋼種

110

1001,000

10,000

100,00

1,00

10

生産量（ｔ）

110

1001,000

10,000100,000

1,000,00010,000,000

100,000,000

amount in products (t)

concentration (mass%)

steel grade

Stainless steel austenitic

Heat‐resisting

steel bars austenitic High speed tool steels

average percent in steel products

Mo

Stainless steelHeat‐resisting steel bars

Heat‐resisting steel

plates and sheets

austenitic

Corrosion‐resisting and heat‐resisting superalloy bars, plates and sheets

general processing steel

steel pipes

special purpose

steel pipes

High manganese steel castingsteel for building structure

Mo

Steelmaking, casting

CokeP, Si

LimeP

Iron ore Mn, P, Si

Steel scrapAl, B, Cu, Cr, Co, Mn, Mo, Nb, Ni, P,

Si, Sn, V, W, Zn

Blast furnace(ironmaking)

BOF

Non-ferrousmetal

Al, Cr, Sn, Zn


Ferro-alloyB, Cr, Mn, Mo, Nb, Ni, Si, V, W

SlagMn

WasteAl, Si, W

SlagMn, P, Si

Non-ferrous industry

Ordinary steel products

Special steel products

Rods and barsPipe and tube

Sheet and coil

Surface-coated products

Heavy plates

Cast steel productsPiles and shapes

Dust, sludgeZn

DRIMn, P, Si

CIF EAF

major flow


CokeP, Si

LimeP

Iron ore Mn, P, Si


Si, Sn, V, W, Zn


BOF

Non-ferrousmetal

Al, Cr, Sn, Zn



SlagMn

WasteAl, Si, W

SlagMn, P, Si





Sheet and coil


Heavy plates





Sheet and coil


Heavy plates


Dust, sludgeZn

DRIMn, P, Si

CIF EAF

major flow

Rare metals in the life‐cycle of steel products

We have three major concerns for the sustainable steel recycling

1) Contamination by or loss of alloying elements, which are mostly important resources, in the usage of steel scrap as iron resource

2) Significant loss of valuable elements into slag during steel refining processes

3) unefficient intermediate process for dust treatment

Development of “scrap soating system based on composition”

Development of “slag‐making technology” to recover P, Mn and Cr

Development of “dust‐making technology” to recover Zn

Classification of rare metals used in steel

type Element

Well-used ＦｅＣ

Passed through ＳｉＰＳ

One way diffusion ＭｎＭｏＮｂＶ

Partial circulation ＣｒＮｉ

Waste accepted ＷＡｌ* Ｚｎ

MFA is done in Tohoku＊ including dross

Red：concentrated one in steel industry

T. Nagasaka: Study on global flow of Metals- An example of material recycling -, Report of ISIJ （2008）

Non-ferrous metal consumption (Al, Cu are not included)

0

200

400

600

800

1,000

1,200

1,400

1,600

1,800

Mn

Dom

estic

dem

and

of ra

re m

etal

s (k

t)

Domestic input

Cr

Ni

Mo, Co, W etc...

For steel industries

Fig. The demand of rare metals for steel industries(2008)

・These metals are used to produce special steel material as alloying elements

Steel industry use huge amount of other metals

20

0

500

1000

1500

2000

2500

3000

3500

4000

Tool steel Carbonsteel formachine

parts

Alloysteel forstructure

FreeCuttingSteel

Springsteel

Bearingsteel

StainlessSteel

Pianowire rods

HighTensile

StrengthSteel

The

amou

nts

of th

e sp

ecia

l ste

el(k

t)

Classification of the special steel

ConstructionIndustrial machineryAutomobileOthers

Special steel consumption

Fig. The amounts of the special steel consumption by industries(2008)

・Automobile industry is the largest user of special steel products, indicating that ELVs contain a significant amount of non-ferrous metals

21

Demand of rare metals in the world

(a)Ni, Consumption(World) : 1,253 ×103 Ni-t (2004)

others: 46%China: 12%

America: 11%

Korea: 8%Germany: 8%

Japan: 15%


Kazakhstan: 12%

SouthAfrica: 14%

Germany: 6%Japan: 11%


Ukraine: 14%India: 8%

Japan: 6%

SouthAfrica: 9%

others: 18%

China: 13%

America: 21%

EU: 33%

Japan: 15%

(b)Cr, Consumption(World) : 4,695 ×103 Cr-t (2003)

(c)Mo, Consumption(World) : 175 ×103 Mo-t (2004)

(d)Mn, Consumption(World) : 19,630 ×103 t (2001)

Large amount of rare metals are consumed in Japan. On the other hand, it is expected to increase consumptionsof rare metals in other Asian countries (China, Korea…) with industrial development.

Iron ore

scrap

Ferro alloy

Blast Furnace Converter


Scraps are put into electric arc furnace to produce steel

Steel is first produced from iron oreIron and steel cycling

Fig. Schematic diagram of Iron and steel cycling in Japan

Electric Arc Furnace

Steel products return to steel industry as a scrap

・Steel products produced from scrap account for about 30%


CokeP, Si

LimeP

Iron ore Mn, P, Si


Si, Sn, V, W, Zn


BOF

Non-ferrousmetal

Al, Cr, Sn, Zn



SlagMn

WasteAl, Si, W

SlagMn, P, Si





Sheet and coil


Heavy plates


Dust, sludgeZn

DRIMn, P, Si

CIF EAF

major flow


CokeP, Si

LimeP

Iron ore Mn, P, Si


Si, Sn, V, W, Zn


BOF

Non-ferrousmetal

Al, Cr, Sn, Zn



SlagMn

WasteAl, Si, W

SlagMn, P, Si





Sheet and coil


Heavy plates





Sheet and coil


Heavy plates


Dust, sludgeZn

DRIMn, P, Si

CIF EAF

major flow

Rare metals in the life‐cycle of steel products

What about “scrap-sorting”?

Present situation of steel recycling

Quality of regenerated steel becomes worse!

Rare metals （Cr+Mn+Zn) balance in EAF process

Average of three steel works which produce about 1000 k‐ton/year

Scrap 1050

Cr+Mn: 9.1Zn: 4.2

Dust: 18

Cr+Mn: 0.15Zn: 4.05

Slag 115.5

Cr+Mn: 6.3

Ferro‐alloy

Cr+Mn: 10.85

Steel products: 1000

Cr+Mn: 13.5

EAF

Unit: k‐tonMatsubae, Nakajima, Nakamura, Nagasaka et al.: Ferrum., (2009)

EAF processMelting reactor for steel scrap Reactor for

zinc recovery

Reactor for mixing metals

0 5 10 15 20 25 30

1000 seriesAl‐Cu alloy (2000 series)Al‐Mn alloy (3000 series)

30033004

other 3000 seriesAl‐Si alloy (4000 series)

Al‐Mg alloy (5000 series)50525182

other 5000 seriesAl‐Mg‐Si alloy (6000 series)

60616063

other 6000 seriesAl‐Zn‐Mg alloy (7000 series)

8000 series

Al‐Cu alloyAl‐Cu‐Si alloy

Al‐Si alloyAl‐Si‐Mg alloyAl‐Si‐Cu alloy

Al‐Si‐Cu‐Mg alloyAl‐Cu‐Ni‐Mg alloy

Al‐Mg alloyAl‐Si‐Ni‐Cu‐Mg alloyAl‐Si‐Cu‐Mg‐Ni alloy

Al‐Si alloyAl‐Si‐Mg alloyAl‐Mg alloy

Al‐Si‐Cu alloyAl‐Si‐Cu‐Mg alloy

Si Fe Cu Mn

Mg Cr Zn Ti

Industrial standardOf aluminum products

Die‐casting alloy

Casting alloy

Wrought alloy

Content of alloying elements, weight %

Si

CuFe

Mn Mg

We have similar problem in the recycling of other metals

1000 series

Al‐Cu alloy

Al‐Mn alloy

Al‐Si alloy

Al‐Mg alloy

Al‐Mg‐Si alloy

Al‐Zn‐Mg alloy

Others

Casting

Die‐casting

Foil

Fabricated metal

Body

End/tab

General machinery

Electric Electronic Equipment

Automobile

Heat exchanger

Engine

Others

Construction

Beverage can

Other products

Export

4.40

0.22

4.97

0.28

3.82

8.89

0.37

1.14

3.93

8.70

アルミのカスケード利用形態Units: ×105 ton

Nakajima, Nagasaka et al.: Env. Sci. Tech., (2010)

Can we control alloying elements

in the recycling (remelting) process?

Oxygen

Refining by oxidation (Flux treatment or slagging)

M

Solvent metal such as steel

MOn

Oxide phase such as stag

??

vacuum

Refining by evaporation (vacuum treatment)

M

Solvent metal such as steel

M gasOxide phase such as stag

??

2/n

OMM

MOMO2/n

OM

MO1 )/()/(

2

nn

2

n

oo ppxγxγ

ppaa

K

Thermodynamic discussion on the removability of alloying element

Metal - Oxide

Metal phase

Slag phase

n2 MOO2nM

n

n

MO

2/n

M

MO/

γ

ppγK

xx 2OM

M

MOslag/metal n

xx

L

Where is impurity element, M ??

・・・・・

-Equilibrium constant of oxidation

-Activity coefficient of M and its oxide

-Partial pressure of oxygen

M???

Molar fraction of M’s oxide

Molar fraction of M in metal

Distribution between oxide/metal

)g(MM

0M

MM

M

M

M pxγp

ap'K

MM0MM γ xpp

Metal - Gas

Mg

Mgas/metal

ppL

Metal phase

Gas phase

・・・・・

Where is alloying element,M ??

-Equilibrium constant of evaporation

-Activity coefficient of M

-Partial pressure of M

M???

Base metal(Al, Mg, Ti)

Partial pressure of M

Partial pressure of base metal

Thermodynamic discussion on the removability of alloying element

Distribution between gas/metal

-20

-10

0

10

20

-20 -15 -10 -5 0 5 10

Distribution model for Cu converterxM = 0.01 (mol fraction) pO2 = 10-1 PapCu = 8 x 10-1 PaT = 1500 K

Cu

Ag

Au

Pd

Pt

PbNi

W

FeGa

Zn

Cr

Mn

Mg

Al

Sn

In

Hg

Bi

B

Re

Rh

Ge

Sr

Cd

Te

Se

Sb

Gas phase

Slag phase

Metal phase

Element distribution during remelting of copper scraplo

g(Ls/

m)

log(Lg/m)

Alloying elementsRecoverable elements

Nakajima, Matsubae, Takeda, Miki, Nagasaka: Env. Sci. Tech., （2011）

-4

-2

0

2

4

6

8

10

12

14

-15 -10 -5 0 5 10

Distribution model for Fe converterxM = 0.01 (mol fraction) pO2 = 1.9x10-5 PapFe = 8.5 PaT = 1873 K

Mg

Sr

Pb

Ca

Zn

Ag

Mn

Cu

Fe

U

Si

Ti

V

Ce

La

CoNi

Al

Sn

Cr

Ta

W

Nb

Zr

Mo

B

Gas phase

Slag phase

Metal phase

log(

Ls/m

)

log(Lg/m)

Deoxidation agents

Alloying elementsRecoverable elements

Nakajima, Matsubae, Takeda, Miki, Nagasaka: Env. Sci. Tech., （2011）Element distribution during remelting of steel scrap

gasmetal

slag

metal

1073K

MgCaBe

-70

-60

-50

-40

-30

-20

-10

0

10

-30 -25 -20 -15 -10 -5 0 5 10 15

log L gas/metal

log L

slag

/met

al

Zn

Cd

Hg

MnCuSiFe

Pt

Ir

WTa

Nb

Zr

Bi

Pb

Au

La

YCa

V Gd

Ti

Ho Dy

Ni

B

Co

CrGe

SbAsIn

SnAg

Ga

YbSr

Li

Nakajima, Matsubae, Takeda, Miki, Nagasaka: Env. Sci. Tech., （2009)Element distribution during remelting of aluminum scrap

-50

-40

-30

-20

-10

0

10

-25 -20 -15 -10 -5 0 5

log L gas/metal

log L

slag

/met

al

Ge

Cu

Ni

AlCe

LaZr

YCa

ZnNaMn

Li(37.0)

Si

Sr

Ag

Fe

BiSn

slag

metal

gasmetal

Sb

973K

Tl

Hg

Pu

Gd

Yb(42.2)

Hiraki, Nakajima, Takeda, Matsubae, Nakamura, Nagasaka: Sci. Tech. Adv. Mater., （2011）

Element distribution during remelting of magnesium scrap

Element Rader Chart

Sr

TaNb

V

Ag

Sn

CrZr

B

U Mn

CuSi

CoNiW Mo

Ti

PbZn

MgMgCaCa

LaLaCeCe AlAl

Fe(BOF,EAF)

BiHg

Mg

TeCd

Pb Zn

Au

Pt RhPd

Ag

Sn

AlCr

GaGeIn

Mn

Se

Re

Ni

B

Sb

FeSr

W

Cu(Converter)

Au

PtIrTa

WMo

NbZrY

UCeV B

CoNi

PdFeTi

GdHo

SiDy CrGeCu

SnMn As

AgGa

SbIn

BiPbLiSr

HgCdZn

Mg

Ca

Be

Yb

La

Al(Remelting)

Au

Pt

Pd

Ag

Sn

Bi

Hg

Al

Cr

GaIn MnMg

Cu

Ni

W

Fe

Zn&Pb(ISP)

Au

Pt

Pd

Ag SnBi

HgAl

CrGa

In

MnMg

CuNi W

Fe

Zn

Pb(Blast furnace)

CaAl

Zr

Mn SiNiGe

La Ce

ZnSr

Na

Li

Fe

Sn

Cu

Sb

Ag

YGd

Yb

Hg

Tl

Pu to Metal phase

to Slag phase

to Gas phase

Elements that have distributed among the metal phase as a solid or liquid metal

Elements that have distributed among the slag phase as oxide

Elements that have evaporated and distributed among the gas phase .

Recoverable element(as pure metal)Alloying element

Deoxidation agents

Mg(Remelting)

Bi

Life cycle of aluminum products and substance flow of alloying elements

Caustic sodaBauxite (Al ore)Ga

Aluminum scrapBi, Cu, Fe, Mg, Mn, Mo,

Ni, Pb, Sb, Si, Sn, Zn

Bayerprocess


Red mudB, Ba, Co, Cr, Fe, Ga,Mn, P, Pb, Sc, Si, Ti, V

Electrolysis

Aluminum ingot

Alumina(Al2O3)

MetalsBe, Bi, Cu, Fe, Mg, Mn,

Mo, Ni, Pb, Sb, Si, Sn, Zn

Otherindustry

Waste

DrossMg, N

Fluorite,Cryolite

Steel industry

Landfill

By-products(Al(OH)3, Ga)

DustMg

Remelting Fabrication,Machinery

Aluminum products


Sheet and foil


PlatesCasted products

Piles and shapes

Non-ferrousindustry

Target process

Nakajima, Matsubae, Takeda, Nakamura, Nagasaka: Env. Sci. Tech., (2010)

SilicateFe

Copper conc.Ag, As, Au, Bi, Co, Fe, Mo,

Ni, Pb, PGM, Sb, Se, Te

Copper scrapMn, Mo, Ni,

Sn, Zn

Smeltingfurnace

Human economicActivities

SlagCo, Fe, Mo, Zn

Converter(refining)

Refinery(electrolysis)

Anode slimeAg, Au, Bi, Pb, PGM, Sb, Se, Te

Blister copper

Matte

Electrolyticcopper

Hydro/pyro-process(extraction)

MetalsAg, Au, Bi, Pb, PGM, Sb, Se, Te

Otherrefinery

MetalsAs, Cd, Ni, Pb, Zn

wasteCd, Pb, Zn

ElectrolyteAs, Ni

Copper alloysAl, Ag, Ni, Pb, Sn, Zn

Otherindustries

DustCd, Pb, Zn

Waste

Life cycle of aluminum products and substance flow of alloying elements

Nakajima, Matsubae, Takeda, Miki, Nagasaka: Env. Sci. Tech., (2011)

Conclusion

It is generally understood that metals, such as aluminum,

copper, steel, etc., are well recycled in our society.

However, in the view point of quality, the current recycling

system makes the quality of regenerated metals worse

because metal products used in our society are mostly in

the form of alloy rather than pure metals and they are

mixed in the present recycling process.

Conclusion

Therefore, understanding and control of substance flow of alloying element through the life‐cycle of steel products are extremely important.

Scrap sorting based on the composition and slag‐making technology will result in great saving of rare metal consumption in base metals recycling.

Really recycle??

I think we should close the valve first…

Thank you very much for your kind attention!t‐[email protected]

By Prof. Takatsuki

experience and prospect on resource management of metals ......basic oxygen furnace: bof (converter)...

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