control of hazardous elements for sustainability in non...

Control of hazardous elements for Sustainability in Non-ferrous

Industry

T.Nakamura

Institute of Multidisciplinary Research for Advanced Materials,

Tohoku University

Please contact to [email protected]

OUT LINE

• Introduction

• Environmental Issues of Extractive Metallurgy

• Important role of control heavy metals in Recycling

• How to control hazardous elements for Sustainability - regulation -

• Conclusions

What happen in the Erath/World? Climate Change?

Shortage of all resources Food, Water, Energy and Mineral Resources ?

or financial instability??

Erath is

so beautiful

How to keep

a Sustainability

for Human Beings

and Nature also

What we have made from old time? History of Artifacts

Human beings can’t live without artifacts

Stone

Steel Carbon Composite

+ all materials

Wood Concrete + Steel

All materials

Weather Sustainable society

“Nature” “Artifacts ”

We are required to take responsibility for the

situation that we have created.

We can forecast but not control any means of altering tomorrow’s weather.

We can prepare for earthquakes and typhoons but we cannot stop them.

Weather

Sustainable society

We all talk about it as a very important issue.

We are at a loss when we try to decide how to achieve it.

Deference between Nature and sustainable society

Classification from aview point of Environmental Issue

Energy Issue （CO２ Emission）

Fe, Al, Ti, Mg, Mn

Cr

Zn

RE

W, Mo,

Ta, Nb,

Ga

Cu, Pb

Sb,Ni

Hazudous Issue

Hg, As, Cd, Tl, Be,Se,B,

I,F,Br

Short Resource

Issue

Au, Ag, PGM,

Bi, Co, In

Climate Change

Resource

Constraint Ecological

Effect

OUT LINE

• Introduction




• Conclusions

Aerial views of the alien landscapes of Rio Tinto in Spain, by

Francisco Mingorance

Times published the rating of the most polluted cities in the world.

Let‘s see what has changed. 10. Kabwe (Zambia)

http://www.earthobserver.org/category/General.aspx

La Oroya (Peru)


Tianying(China)

The smelting of lead (the largest production in China).

Result: The lead content in air is 10 times greater than national standards.

140 000 people constantly exposed to the high content of lead in the

environment.


Emission from Uncontrolled Metal Industrial Sectors

SOx , NOx

Acid rain

POPs like Dioxins

Diffusion of very small toxicity substances

Heavy metals : Hg,As,Cd,Pb

We have to stop the emissions of them

Typical Open Mining of Copper

Cu content becomes less 1% in Copper ore.

We have to through away 2/3 of ore in a

mineral dressing process as tails.

Then, ｗe have a large Amount of Ecological

Rucksack to get Primary Resources

We have to handle and treat more than 99%

residue when we produce metallic copper

from Cooper Ore.

Full-scale operation began in

April 1982, and has been

continuous since then,

neutralizing and treating large

volumes of mine wastewater at

around

New neutralization and treatment facility at the abandoned Matsuo Mine

Located in the middle of Hachimantai, 1,000 meters above sea level, the

abandoned Matsuo Mine is the largest sulfur mine in the Far East. The mine site

was discovered as a large outcrop of a sulfur ore deposit in 1882. In its most

prolific period, as many as 15,000 people lived nearby, and the prosperity of the

mine peaked. From the 1960s, however, mine operations worsened due to the

market debut of sulfur recovered cheaply through desulfurization of heavy oil in

response to regulations on pollution; in 1972 the mine was closed. Even after the

mine was closed, however, large volumes of strongly acidic water continued to

flow from the mine and empty into the Red River nearby.

http://www.jogmec.go.jp/english/activities/pollutioncontrol/neutralizationplant.html

In case of Japan

Japanese Mineral Resources in old time

• 1000 years old, iron sward was one of main export goods from Japan

• About 400 years old , main export goods are

Copper, Silver and Gold

Now there is only one gold mine in Japan,

where is located Hishikari, south Kyusyu

Japanese serious pollution disasters on GDP growth

Year

SO2

Hg

As

PCB

DXN

1880-1900

Cd

?

Copper

smelter

Chemical

Industry

Zinc smelter

As mine

oil

Incineration

fly ash

SO2

New air regulation

And water regulation

Law concerning Special

Measures against Dioxins

-4 -3 -2 -1 0 1 2 3 4 5 6 0

1

2

3

4

5

6

7

8

9

10

log K (ppm)

log

T (p

rod

uct

ion

. to

n /

yea

r)

Ⅰ Chalcophile group Ⅱ Siderophile group Ⅲ Lithophile group

group Ⅰ T = 10 5 K

group Ⅱ T = 10 4 K

group Ⅲ T = 2.5x10 2 K

S = M/T = 30 years

S = M/T = 300 years

S = M/T = 1.5x10 4 years

Ⅰ Ⅱ

Ⅲ

Te Pt

Au Se

Hg

Bi

Cd

Sb As

Mo

In

Tl

Be

Ga

Ta Y

Li V Nb

Co W

Sn Ni

Zr

Mg

Al Ca

Ti

Fe

S Cu Zn

Pb Cr

Relationship between Annual Production Amounts and Clarke’s Numbers

How can Metal Production be continued from

Primary Resources

REE

Essence of Separation Technologies

• Two ways are available : Physical Separation

Chemical Separation

• Physical Separation: Mainly solid state separation

Milling, Gravity separation ,Magnetic separation and so on. Good for pre treatments before finial materializing

• Chemical Separation: Using chemical reactions to remove impurities which are contaminated in atomic level to achieve a fine separation.

Leaching, Roasting, Smelting, Electro-Winning and so on

• Best mix of Physical Separation and Chemical Separation

is necessary for high efficient separation

Extraction Process of Copper

（Exploration）（Mining）（Crushing・Milling）

（Concentration）（Concentrate）

（Leaching）

（Solvent Extraction－

Electrowinning）（Electrolytic Copper）

（Smelting）（Refining）（Electrolytic Copper）

Mining

Smelting

→ Residue

↓ Residue

（Tailing ）

↓ Residue

（slag, dust ）

↓ Flue gas

（ Sulfuric acid ）

Iron Precipitation

Method

Advantages Disadvantages

Jarosite Process ■Technology widely used

and tested

■Technology for

Immobilization available

■Sulphate control

■High volume of residue,

owing to the resulting low Fe

content

■Long residence time in the

precipitation tanks

■Environmentally unstable

■High cost of residue

disposal

■Environmental concerns

with entrained toxic

contaminants in residues

Goethite process ■Amount of residue lower

than for the Jarosite

process

■Environmentally stable

■Yield of silver lower than

for the jarosite process

■Environmental concerns

with entrained toxic

contaminants in residues

Hematite process ■Residues are of

commercial value if pure

(gypsum and hematite)

■No landfill space required

if residues can be sold

■High cost equipment

■Complex and yet un-

economical technology

Pressure acid leaching ■Simplified iron removal ■High cost equipment

■Complex technology

Solvent extraction ■Very pure cell house

electrolyte

■Simplified neutral

leaching control

■Limited ability for ferric

iron control in SX

(organic tolerates only

low levels of ferric iron)

Comparison of Iron Control Process in Hydro-Processes

• When Copper , Zinc or Lead is collected,

Arsenic accompanies at the same time.

•Non-ferrous smelters can not neglect

Arsenic treatment.

•Copper concentrate was imported into Japan about

3-million MT/year.

•Assuming that average Arsenic content is 1000ppm,

3000MT/year of Arsenic could be brought into

Japan

Why Arsenic ？

Base Metals and Minor Metals recovered from Primary and Secondary Resources in Non-Ferrous Industry

Copper Smelting

Zinc Smelting Lead Smelting

Cu,Au,Ag,PGM. Ni,Co,Cd,As,Se,Te

Pb,Sn,Bi,Sb

Zn,In,Ga

Pb

Cu

Pb

Zn

Zn

Cu

Zinc concentrate

EAF dust

Copper concentrate

Shredder dust

Lead concentrate

Waste lead battery

Fly ash

Sulfuric acid？

More than 20 metals can be recovered except RE,W,Mo,Mn,Cr,Nb,Ta and Li

OUT LINE

• Introduction




• Conclusions

Recycling Copper Production of Copper in Japan :1.2 million tons Consumption of Copper in Japan : 0.8 million tons Scrap Copper in Japan 0.5 million tons Recycling Copper in Japan : 0.3 million tons Recycling Ratio to Scrap Copper : 60％ Where Is other Copper Scrap? Mostly scrap copper is shipped to foreign country Partly Landfill, If Copper Content is around ３％ in Shredder Dust, 45,000 tons of Copper are land-filled.

Shredder dust treatment process in Onahama Smelter

Key Point: Halogens in flue gas are not put into a main acid plant but put into plaster(CaSO4) plant.

Burning zone

Oil Burner

Shredder dust

Copper concentrate

Oxygen enriched air

Smelting zone Settling zone

slag

matte

Boiler Flue gas Treatment

Oxygen plant

Power plant

steam

Recycling of Zinc

Recycling Ratio: 25%

Process :

Zinc melt after Plating

Re-melting in NaOH Flux and Filtration

EAF Dust

Many Dust Treatments Processes are available

Finally Crude ZnO is reduced in ISF process

Technical Problems

①Complicated Recovery Processes

②High Energy Consumption

③Registrated as Industrial Waste

④Dioxins

⑤Low Pries of Zinc

Core-competence of Non-Ferrous Industry for Dust Recycling

* Separation Techniques for heavy metals like Cu,Zn and Pb

* Keep facilities and place to treat dust Short risk communication at the beginning of

commercial operation of Fly Ash, Shredder Dust Treatments

0.1 mass%

Fly Ash

1 mass%

Secondary Fly Ash

10 mass%

Municipal

waste Incinerator

Fly Ash

Bottom

Ash

Smelting

Furnace Secondary

Fly Ash

Zinc

Refinery

Municipal waste

Enrichment Route of Zn from Municipal Waste

Combine Fly Ash treatment with EAF dust treatment

Coal Silica Raw Materials

Dryer

Rod Mill

Briquette

Machine

MF

Boiler Gas Cooler Bag Filter

Removal of Halogen

Filter Press

Aging Bins

Slag

Crude Zinc Oxide

Power Plant

Sell Out Steam

EAF Dust Other Materials

Binder

Fly Ash

Leaching Tank

Thickener

Filter Press

<Cl elimination>

Process flow for recycling fly ash in Miike Smelter

conveyor

by-pass duct

coking zone

hot air

settler

tuyere

smelting zone

boiler

water wall tube

Schematic Illustration of MF Furnace

The Law Concerning Special Measures Against Dioxins

Promulgated on July 16, 1999 and Enforced on January 15,

2000

A unique low in the world specialized for protection of the

environment by controlling the dioxin emissions from waste

incinerators and several industrial processes, i.e.,

Electric arc furnace (EAF) for steelmaking

Sintering plant for iron ores

Secondary zinc production from EAF dust

Secondary aluminum alloy production

In the law:

Tolerable Daily Intake (TDI) is set at 4 pg-TEQ/(kg-body・d)

Co-planar PCB is included in dioxins as well as PCDD/Fs

Countermeasures for dioxins emissions in the specified metallurgical processes

Electric arc furnace Iron ore sintering

process

Secondary Zn

production

Secondary Al

production

Dioxins emissions

In 2007

49 g-TEQ/y

20 g-TEQ/y

1.8 g-TEQ/y

13.4 g-TEQ/y

Typical conc. of waste gas

In 2000

0.03～76 ng-TEQ/Nm3

(n=60)

0.012～1.7 ng-TEQ/Nm3

(n=16)

0.55～72 ng-TEQ/Nm3

(n=8)

0.05～5.9 ng-TEQ/Nm3

(n=17)

Annual production

About 30 mil. ton/year

About 100 mil. ton/year

About 60,000 ton/year

About 1.2 mil ton/year

Major counter-measures

* Pre-removals of Cl-bearing materials * Waste gas treatments

* Control of chlorine in the secondary raw materials * Waste gas treatment

* Pretreatment of EAF dust (de-Cl, dioxins) * Waste gas treatment

* Selective removal of organic Cl * Cl-less flux *Waste gas treatment

Regulation of the emissions

Previous: 5 ng-TEQ/Nm3

New: 0.5 ng-TEQ/Nm3


New: 0.1 ng-TEQ/Nm3


New: 1 ng-TEQ/Nm3


New: 1 ng-TEQ/Nm3

OUT LINE

• Introduction




• Conclusions

Legal agreements for the protection of the Carpathian-Danube region has been

signed by 11 central and eastern European countries in 2001, committing them to

develop national policies to decrease pollution in the Danube.

USA-Canada Great Lakes Water Quality Agreement (1978 )

Basel Convention on the Control of Transboundary Movements of hazardous

Wastes and their

disposal (1992)

Rotterdam Convention on the Prior Informed Consent Procedure for Certain

Hazardous

Chemicals and Pesticides in International Trade (voluntary since 1980, in force - 2004)

Stockholm Convention on POPs (2004)

UNECE Water Convention on the Protection and Use of Transboudary Waters and

International lakes (1996)

UNECE Convention on the Trans boundary effects of Industrial Accidents (2000)

Legal Agreements at International Level

Main Directives on water pollution control:

Directive on Pollution caused by discharges of certain Dangerous substances

DSC 76/464/EC with ‘daughter directives’

Water Framework Directive WFD 2000/60/EC

Directive on Integrated Pollution Prevention and Control IPPC 96/61/EC

Urban Waste Water Treatment Directive UWWTD 91/271/EC

Fish Water Directive and Shell Water Directive 78/659/EC

Bathing Water Directive 76/160/EC

Drinking Water Directive 80/778/EC

Nitrates from Agricultural Sources Directive 91/676/EC

European

Union

Legal Agreements at National Level

USA Clean Water Act (CWA) (1972, with subsequent enactments in 1981, 1987)

http://upload.wikimedia.org/wikipedia/commons/6/6d/European_flag.svg

Established under the Basic Environment Law, are target levels for water quality that are to be

achieved and maintained in public waters, to achieve two major goals:

protection of human health

- uniform national standards applicable to all public waters

- a total of 23 substances including cadmium and total cyanide

conservation of the living environment

- met by classifying rivers, lakes, reservoirs, and coastal waters; established

for each

class on base of water usage

- established for pH, BOD, COD, DO, total coliform, SS, and nitrates and

phosphorus

to prevent eutrophication

In addition, twenty-five other items were also selected for precautionary monitoring in

water environments. In 1997, EQS for groundwater pollution were also established.

Provisional guideline values have also been set for sediments contaminated by mercury

and polychlorinated biphenyl compounds (PCBs).

Japan Environmental Quality Standards (WQS)

http://upload.wikimedia.org/wikipedia/commons/9/9e/Flag_of_Japan.svg

Item

Standard Values

cadmium

0.01 mg/liter or less

total cyanide


lead


chromium (VI)


arsenic


total mercury


alkyl mercury

not detectable

selenium


Standard values are the annual

mean. However, the value

for total CN is the maximum

value.

Source: Environment Agency

Environmental Quality

Standards

for Human Health in Japan

Environmental Quality Standards for Soil Pollution in Japan

Substance

Target level of soil quality examined through leaching

and content tests

cadmium

0.01 mg/l in sample solution and less than 1 mg/kg in rice for agricultural land

total cyanide

not detectable in sample solution

organic

phosphorus


lead

0.01 mg/l or less in sample solution

chromium

(VI)


arsenic

0.01 mg/l or less in sample solution, and less than 15 mg/kg in soil for agricultural

land (paddy fields only)

total

mercury


alkyl

mercury


Items related to the protection of the living environment in Japan

Living Environment Items

Permissible Limits

hydrogen ion activity (pH)

Non-marine 5-8-8.6

Marine 5.0-9.0

Biochemical Oxygen Demand (BOD)

160 mg/l

(Daily Average 120 mg/l)

Chemical Oxygen Demand (COD)

160 mg/l


suspended solids (SS)

200 mg/l


n-hexane extracts (mineral oil)

5 mg/l

n-hexane extracts (animal and vegetable fats)

30 mg/l

phenols

5 mg/l

Items related to the protection of the living environment in Japan

copper

3 mg/l

zinc

5 mg/l

dissolved iron

10 mg/l

dissolved manganese

10mg/l

chromium

2 mg/l

Fluorine

8 mg/l

number of coliform groups

Daily Average 3000/cm3

nitrogen

120 mg/l


phosphorus

160 mg/l


Item

Elusion

Standards

Content

Standards

Cd

>0.01mg/l

>150mg/kg

Pb

>0.01mg/l

>150mg/kg

Cr(6+)

>0.05mg/l

>250mg/kg

As

>0.01mg/l

>150mg/kg

Total Hg

>0.00005mg/l

>15mg/kg

Se

>0.01mg/l

>150mg/kg

Elusion Standards and Content Standards for slag in Japan

Comparison of Elusion Test

country Test method size pH S/L

ratio

mixing unit

Japan

Notification No13 Under 5mm 5.8～6.3 10 Vibration 6hrs mg/L

Notification No46 Under 2mm 5.8～6.3 10 Vibration 6hrs mg/L

Recycling law 20～50mm CO２ Sat.

4.0

10 Stirring 24 hrs mg/L

USA/Ca TCLP Under 9.5mm 2.88 or 4.93 20 Vibration hrs 18 hrs mg/L

Germany DEV S4

(DIN38414）

Under 10mm Distillation

water

10 Vibration hrs 24 hrs mg/L

France AF NOR X31-2 10 Under 4mm Distillation

water

10 Vibration 6hrs

16 hrs

mg/kg

Swiss

land

TVA No control CO２

saturation

10 Vibration hrs 24 hrs mg/L

Nether

land

Availability test

(NEN7341）

Under 125μm 7 50 Stirring 3hrs mg/kg

4 50 Stirring 3hrs

Serial batch test

（NEN7343） Under 3mm 4

20×5

times

Vibration hrs 24 hrs

X 5times

mg/L

Column test

（NEN7343） - - -

To achieve

equilibrium

mg/kg

Comparison of Elusion Test Standards （mg/l）

spices

Chile

（compliance

USA TCLP）

Notification No13 by M.EV.

landfill

marine disposal

（Inorganic

sludge）

As 5 0.3 0.01

Cr 5 － 0.2

Hg 0.2 0.005 0.005

Pb 5 0.3 0.01

Se 1 0.3 0.01

Cd 1 0.3 0.01

Ag 5 －－

Cu －－ 0.14

Zn －－ 0.8

Ni －－ 0.12

OUT LINE

• Introduction




• Conclusions

The Mercury Study Report to Congress – EPA prepared this report to

fulfill requirements of the Clean Air Act Amendments of 1990. Published in

1997, it is an eight volume assessment of the magnitude of U.S. mercury

emissions by source; the health and environmental impacts of those

emissions; and the availability and cost of control technologies.

Bibudhendra Sarkar, of The Hospital for Sick Children and the Department of

Biochemistry, University of Toronto, Toronto, Canada,

([email protected]) reviewed the global picture of arsenic

pollution and the methods of monitoring it.

mailto:[email protected]

Process Commercial

Operation Comments

Neutralization with lime-

calcium arsenate/arsenite

Yes

not effective at removing all arsenic from solution

residue not environmentally stable

easily carbonated by atmospheric carbon dioxide,

releasing soluble arsenic

Neutralization with lime plus

ferric iron – arsenical

ferrihydrite

Yes

removes As down to <0.1 mg/L

residue stable if molar Fe/As >4

high iron requirement

high volume, high liquor retention residue

US EPA Best Developed Available technology (BDAT)

Neutralization with lime plus

ferric plus base metals – base

metal arsenical ferrihydrite

Yes

removes As down to <0.1 mg/L

residue stable if molar Fe(+ base metals)/As >4

Pressure oxidation –

scorodite or TypeⅠ/TypeⅡ

mineral

Yes

stable arsenic mineral formed

requires polishing step for <0.1 mg/L As

minimum Fe requirements

requires autoclave

low volume, low liquor retention residue, easily filtered

Summary of Methods for Bulk Removal and Disposal of Arsenic (1)

B.Harris : Hydrometallurgy 2003 – Fifth International Conference in Honor of Professor Ian Ritchie – Volume 2 : Electrometallurgy and Environmental Hydrometallurgy Edited by C.A.Young, et.al. TMS (The Minerals, Metals & Materials Society), 2003

Process Commerci

al

Operation

Comments

Atmospheric scorodite

Pilot only

stable arsenic mineral formed

requires polishing step for <0.1 mg/L As

minimum Fe requirements

low volume, low liquor retention residue,

easily filtered

pressure vessel not required

Arsenic sulphide

Yes

residue formed is unstable at pH > 4

works best with As(Ⅲ)

elemental S formed with As(Ⅴ)

melt with S to form glass

Copper arsenate Yes specialized situations only, diminishing

market required

Arsenic trioxide Yes not environmentally stable

market required

B.Harris : Hydrometallurgy 2003 – Fifth International Conference in Honor of Professor Ian Ritchie – Volume 2 : Electrometallurgy and Environmental Hydrometallurgy Edited by C.A.Young, et.al. TMS (The Minerals, Metals & Materials Society), 2003

Summary of Methods for Bulk Removal and Disposal of Arsenic (2)

Conclusions

• Non-ferrous industry have been accepted hazardous heavy metals like As,Hg and Cd

However, Non-ferrous Industry can control Heavy metals in the process

• We need more effective processes for controlling hazardous heavy metals and new concept to use them in sustainable society.

control of hazardous elements for sustainability in non...

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