Nippon Steel

Jätemuovi – haitallisesta hiilipohjaisesta materiaalista arvokkaaksi metallurgisen

koksin, koksaamokaasun, vedyn ja hiilivetypohjaisen öljyn raaka-aineeksi

TkT Jyrki Heino

LABORATORY OF PROCESS METALLURGY

DEPARTMENT OF PROCESS AND ENVIRONMENTAL ENGINEERING

The history of Harjavalta industrial area

1944 Copper factory is moved from Imatra to Harjavalta.

1945 The start up of the Outokumpu copper factory

The history of Harjavalta industrial area

1945 The start up of the Outokumpu copper factory

1947 The start up of the Kemira sulphuric acid plant

Year 1950

1949 Start up of first Outokumpu copper flash smelter

1956 First licensed Outokumpu copper flash smelter

starts up in Ashio, Japan

1959 Start up of first Outokumpu nickel flash smelter

1995 Start up of AGA hydrogen plant

1995 Start up of Direct Outokumpu Nickel (DON)

process

1999 Outokumpu out sources industrial maintenance,

transport, sanitation, industrial sanitation and

guarding to partnership companies

WHB EP

Concentrate, silica sand

Feed mixture

Oxygenand air

Flue dust

Slag

FLOW SHEET OF COPPER SMELTER

SLAG COOLING

Silica sand, coke, reverts

Air and oxygen

SCREENING AND

GRINDING

SLAG GRINDING

SLAGCONCENTRATOR

Waste slag

Acidplant

Bagfilter

Propane, air

Matte

Bagfilter

Bag

filter

WHB

FLASH SMELTINGFURNACE

CONCENTRATEDRYINGSteam

THICKENER

Blister

HEATEXCHANGER

PRESSURE

FILTER

Scrap, anode scrap

EP

CONVERTER

ANODEFURNACE

Ni drying

Ni Electric furnace bins

ANODE CASTING

Cu-ANODE

Slag concentrate

Type II industrial system

= More

than 55 licences in five continent

Outotec 2012

The first ever copper flash smelting process

started in Harjavalta, Finland at 1949

Boliden Harjavalta Oy 16.12.2013 7

Copper and nickel flash smelters as an important part of

Harjavalta industrial eco-park

MAINTENANCE

Mainpartner Oy

Insta Automation Oy

ABB Oy Services

GAS PRODUCTION

Air Liquide Finland Oy

Oy AGA Ab

POWER SUPPLY

Suomen Teollisuuden

Energiapalvelut STEP Oy

PLANNING AND PROJECTS

Outotec (Finland) Oy

Insta Automation Oy

INTERNAL

TRANSPORTATION

Valtasiirto Oy

INDUSTRIAL

CLEANING

Lassila & Tikanoja Oyj

CLEANING OF

FACILITIES

SOL Palvelut Oy

CANTEEN

Amiga and Fazer

SECURITY

ISS Security Oy

BOLIDEN

HARJAVALTA OY

NORILSK NICKEL

HARJAVALTA OY

YARA SUOMI OY

KEMIRA OYJ

LUVATA PORI OY

OUTOTEC (FINLAND) OY

VR CARGO

THE PORI PORT

OY HACKLIN LTD

WASTE WATER

TREATMENT

Aquflow Oy Oy

Boliden Harjavalta Oy 2012)

YEAR COMPANY PRODUCTS

1945 Outokumpu Anode copper

2013

Boliden Harjavalta Oy

Norilsk Nickel Harjavalta Oy

SP Minerals Oy

Kemira Oyj

YARA

AGA

STEP Oy

Anode copper, nickel matte, sulphuric acid, and sulphuric dioxide in smelters of Harjavalta plant. Cathode copper, gold, silver, platinum and palladium concentrate, copper sulphate, nickel sulphate, copper telluride, and selenium in electrolysis of Pori plant

Nickel cathodes, nickel briquettes, nickel powders, nickel fine powder, nickel solutions, nickel chemicals, ammonium sulphate, copper sulphide, and cobalt sulphate solution

Screened granulated nickel slag for sand blasting and roofing felt production

Aluminium sulphate

Urea phosphate, different kinds of fertilizers, urea

Gaseous oxygen, hydrogen and nitrogen, liquid oxygen, nitrogen, and argon

Process steam, high temperature steam, process energy, district heating energy, raw water, salt-free and precipitated water, electric energy, and compressed air

The product and company diversity progress 1945 - 2013

ADVANTAGES

Environmental and recycling benefits

Better energy efficiency

Better product diversity when different

companies can concentrate to their

own core know-how areas

Marketing and logistic benefits

Improved safety activity

Imago factors

Positive co-operation factor based on

cultural differences

Material and energy

change of Harjavalta

Industrial Eco Park

NN YARA

NN = Norilsk

Nickel

STEP

In ferrous industry main raw materials are oxide ores and in nonferrous

industry sulphide ores

Earlier sulphur dioxide was main problem in nonferrous metal manufacture;

now the main problem is a huge amount of unutilised solid wastes

High electric energy demand in electrolysis of copper, nickel and zinc and

ferrochromium and stainless steel manufacture

The main problem of ore based ferrous industry is CO2 emissions

Specific CO2 emissions (tons per produced ton of steel) of Finnish steel

industry are one of the lowest in the world

The major problem when using more steel scrap as a raw material will be the

contamination of steel by tramp elements

Utilisation of some dusts, slimes and sludge from ferrous industry is waiting

for economical solutions

Environmental load of Finnish ferrous and nonferrous metallurgical industry – Future challenges

Harjavalta industrial park as

an example of an industrial

ecosystem when developing

environmental friendliness of

carbon steel

Basic principle: “The primary production

chain of the ore based steel making is

not disturbed (Pöyliö et al. 2002)”

=> So, there is ahead a mega jump in

technological, economic and ecological

efficiency by totally eliminating waste

streams and fully exploiting synergies

with other related industrial technologies.

(Szekely 1996)

Heino 2006

More efficient use of own iron residues (dusts, scales and sludge = waste oxides)

Use of secondary or bio based energy sources and reducing agents (Plastics, tar, heavy oil, tyres, wood, etc.)

More efficient use of slags in cement industry, in road construction and agriculture to replace virgin raw materials

Low heat energy utilization in district heating, in greenhouses or somewhere else in the surrounding community.

Coke oven gas can be converted into H2, which can be fed into fuel cell battery for automobile or chemical industry

Better energy efficiency with the aid of energy integration included pinch technology, etc.

Utilisation of carbon monoxide as a raw material of formic acid manufacture

Use of iron residues from other industries (Scrap, slags, roasting residues)

Industrial ecology applied to carbon steel manufacture

INTRODUCTION

Natural reserves of coking coal are limited and the standards for blast furnace iron

making are becoming increasingly strict, encouraging steel producers to implement

environmentally friendly and economical processes.

The production of high quality coke requires a better control of its properties (e.g.,

reactivity and strength) as well as sustainable and economic management of coke

oven gases (H2 ~ 58.5% and CH4 ~ 23.8% as a main utilisable components).

Because of the limited source of coking coal, it must be found new ways to

substitute the virgin raw material with other appropriate renewable or secondary

organic compounds.

Without large investments costs to extra treatment plant twaste plastics charged in

coke ovens can be used as a secondary source of hydrogen, a fuel, a reductant, a

carburization agent and a structural support used in a BF thus substituting virgin coal

and thus decreasing carbon dioxide emissions.

EFFICIENT FUEL FOR A BLAST FURNACE (EFBF) 01.09.2011 - 31.08.2015

T. Fabritius, S. Gornostayev, J. Heino., S. Huttunen, T. Kokkonen, and R. Mattila

LABORATORY of PROCESS METALLURGY

DEPARTMENT of PROCESS and ENVIRONMENTAL ENGINEERING

INTRODUCTION TO PLASTIC COKE RESEARCH IN EFBF

Without large investments costs to extra treatment plant waste

plastic can be processed in coke ovens to be used in blast furnace as

structural support, carbon based reductant, carburization agent, and

fuel for the hot iron metal.

By-products of coking process (H2, hydrocarbon oil, and CH4) can be

used in other more valuable purposes.

Virgin coal will be substituted and CO2 emissions reduced.

PLASTIC COKE RESEARCH

To study how coking process proceeds when coking coal without and

with varying amounts of plastics.

To investigate coking process when changing the amount of the

plastics among the coking coal.

To produce different type of plastic-free and plastic-bearing coke for

analysing and testing.

To investigate how plastics and their amount affect the porosity and

strength of the coke and to define is there any maximum limit to the

amount of the plastics.

To measure the coke gas composition when coking coal without and

with varying amounts of plastics.

The heat is transferred from the heated brick walls into

the coal charge with the following consequences:

1. From about 375°C to 475°C, the coal decomposes

to form plastic layers near each wall.

2. At about 475°C to 600°C, there is a marked

evolution of tar, and aromatic hydrocarbon

compounds, followed by resolidification of the

plastic mass into semi-coke.

3. At 600°C to 1100°C, the coke stabilization phase

begins. This is characterized by contraction of coke

mass, structural development of coke and final

hydrogen evolution.

4. When the plastic layers have met at the center of

the oven, the entire mass has been carbonized.

The coal-to-coke transformation takes place as follows:

Source: Shelton Iron and Steel Co

Source: Kawasaki Steel

Source: Nippon Steel

Plastic as a secondary raw material of coke

Source: Nippon Steel

EXPERIMENTAL

Metallurgical coke was prepared in laboratory scale coke ovens by coking three

common coals (RI, EV and BU) without and with most widely used plastic -

polyethylene (HDPE, (C2H4)n).

Plastics and coals were grinded to < 5 mm.

In mini coking process samples were warmed up to 1200 ºC.

Coke compression strength was measured by Zwick 100 kN Tensile test machine.

Image analysis by optical microscopy was performed to study textures and

porosity of coke.

ASAP 2020 Pore size analyser was used to measure porosity and surface area

(BET) of coke

Laboratory scale coke oven battery with nine coke ovens

Optical microscopy and image analysis

Recognition of textures (mosaic, isotropic, banded) and pores.

Tools and methods for advanced studies of coke

Digital

camera

Mattila O., Salmi P. Wavelet-based image analysis method to study the

properties of coke (2008) Scanmet III Conf., Sweden, p. 237-244.

Cold compression strength (kN/m2) of coke as a function of PE plastic 0 – 12,5 % addition in RI coal

RESEARCH RESULTS

No significant changes were observed in the cold strength results from 0 up

to 5% of HDPE plastics addition to the three different coals BU, EV and RI.

Below 5% HDPE plastics addition in RI coal the increase of mosaic texture at

the expense of isotropic texture compensates for the weakening effect of

increased porosity. Also rounded macro pores observed in texture analysis,

decrease the weakening effect.

Mosaic carbon texture in coke is usually less reactive with carbon dioxide

compared to isotropic carbon texture, thus improving the CRI and CSR

values of coke to be used in blast furnace.

The cold compression strength results of coke manufactured by adding the

most common plastic (HDPE) to Riverside coal were very encouraging.

Estimations are both coal-specific and plastic-specific and should be made

separately for any given coal type and plastic type.

(Heino et al. 2012 & Heino et al. 2013)

Mäkinen 2006 and Outotec 2012

Eco-efficient features of Finnish metallurgical industry

Conservation of energy and intelligent use of non-fossile energy

sources and minimizing the impact on the environment; air, water, soil

ASM Historical Landmark Award for the Outokumpu Flash Smelting

Process in 2002

About 50 % of the World copper and 30 % of nickel is produced by

Flash Smelting method developed in Harjavalta Finland by

Outokumpu (nowadays Outotec)

13 BAT´s = Best Available Technologies developed by Outotec rated

by the EU to their energy-efficiency and low emissions

Ruukki as a leader in the Dow Jones Sustainability index among

carbon steel manufactures (Cleantechfinland 2011)

Outokumpu Tornio Stainless steel plant having the lowest carbon

footprint of world stainless steel manufactures (Outokumpu 2010)

Pekka Tervonen, TkT, eMBA

Johtaja

Puh: +358 40 6739519

pekka.tervonen@oulu.fi

1. CEE:n toiminnan painopisteet ovat ilma, vesi, energia ja resurssitehokkuus

sekä edellisiä poikkileikkaavana teemana mittaustekniikka.

2. Visiona on olla ekoinnovatiivisten ratkaisujen haluttu yhteistyökumppani.

3. Strategiana on kehittää ympäristö- ja energia-alaa yhdistävä

osaamiskeskittymä, joka yhdistää nopeasti alan huippuosaamisen tutkimus-,

kehitys- ja innovaatiotoiminnan hankkeisiin, yhteistyöverkostot ja

rahoituskanavat.

4. CEE yhdistää läpinäkyvästi valitun alan huippututkimuksen ja yritysosaamisen

Oulussa ja yhteistyöverkkojen kautta valtakunnallisesti ja kansainvälisesti.

Tämä luo kestävän pohjan tutkimus- ja yritysyhteistyölle.

5. Toimintafilosofia on ohjelmapohjainen verkostomalli, mikä mahdollistaa

nopean ja proaktiivisen tutkimusyhteisöjen ja yritysten yhteistyön.

Centre for Environment and Energy (CEE)

CEE – yritysosaamisen ja huippututkimuksen integraatio

CIRU –platform/CEE (Juha.roininen@oulu.fi)

CIRU – Platform auttaa teollisuusyrityksiä kehittämään prosessejaan ja hyödyntämään

niissä syntyviä sivuainevirtoja.

Asiantuntemuksemme perustuu tieteelliseen tutkimukseen termodynamiikan,

minerologian, kemiallisten analyysien, reaktiokinetiikan ja virtausmallinnuksen alueilla.

Voimavaroinamme on koko tekninen osaaminen ja erityisenä tavoitteenamme on yhdistää

toimintaamme myös tuotteistaminen kaikkine osa-alueineen.

Tässä työssä huomioimme myös yhteiskunnallisen vaikuttamisen, josta esimerkkinä on

muotoilu aspektin tuominen mukaan aliarvostettujen materiaalivirtojen tuotteistamiseen

yhtenä työkaluna hyväksyttävyyden saavuttamiseksi ekologisille toimintamalleille.

Toimintamme peruslähtökohtia on tarpeiden tunnistaminen, avoimuus, yhteistyö sekä

innovaatioiden edistäminen tutkimuksen avulla.

Yhteistyö suurteollisuuden ja julkisten toimijoiden kanssa toimii erinomaisesti

Työmme tavoite on lisätä toimijoiden kannattavuutta ja ekologisuutta korkealaatuisella

tieteellisellä osaamisella ja erityisesti PK sektorin toimijat ovat erittäin toivottuja

osallistumaan tähän yhteistyöhön.

Tule mukaan parantamaan maailmaamme ja ota yhteyttä meihin tulevaisuuden tekijöihin.

Sources of information

CENTRE FOR ENVIRONMENT AND ENERGY (2013) <http://www.oulu.fi/english/CEE>

Cleantechfinland (2011) <http://www.cleantechfinland.com/news/ruukki_achieves_industry leader_position_in_ dow_jones_

sustainability_indexes/>. 21.9.2011

Heino, J. (2006) Harjavalta industrial park as an example of an industrial ecosystem when developing environmental friendliness of carbon steel.

Doctoral dissertation. Acta Universitatis Ouluensis, C Technica 254. 163 p. (In Finnish)

Heino, J., Gornostayev, S., Kokkonen, T. Huttunen, S. Fabritius, T. Waste plastic – From harmful carbon based material to valuable raw material

of metallurgical coke, coke oven gas, hydrogen, and hydrocarbon oil. Annual World Conference on Carbon, 17-22 June, 2012, Krakow, Poland.

Oral presentation and paper in conference proceedings.

Heino, J., Gornostayev, S., Kokkonen, T., Turpeinen, E., Huuhtanen, M., Suopajärvi, H., Huttunen, S. Fabritius, T. & Keiski, R. (2013) Waste

plastic as an additional raw material of metallurgical coke to produce hydrogen as by-product. Poster in 2nd International Symposium of Green

Chemistry 2013 in France.

Kawasaki Steel. <URL:http://www.kawasaki-steel-21st-cf.or.jp/chapter_2/index.html> 24.10.2002

Mäkinen, J. (2006) Eco-efficient Solutions in the Finnish Metallurgical Industry. Challenges of Eco-efficiency seminar.

Outokumpu. (2010) The energy and low-carbon programme. Outokumpu leading the way. <URL:http://www.outokumpu.com/51623.epibrw/> 8 p.

Outotec (2012) <URL:http ://www.outotec.com/pages/Page____40893.aspx?epslanguage=EN>

Nippon Steel news June 2004

Pöyliö, E., Makkonen, H., Laitila, L., Heino, J., Hiltunen, A. & Härkki, J. (2002) Optimal recycling of the iron based steelmaking dusts, scales and

sludge. Recycling and waste treatment in mineral and metal processing: Technical and economic aspects. Luleå, 16.6 – 20.6.2002. Luleå

University of Technology, MEFOS and the Mineral, Metals & Materials Society. Volume 2, pp. 129 –137.

Szekely, J. (1996) Steelmaking and industrial ecology - Is steel a green material? ISIJ International 36(1996)1, pp. 121 - 132.

Yonesawa K. Longitudinal vision of steelmaking industries from an environmental standpoint in Japan through course 50 project. SCANMET III -

3rd International Conference on Process Development in Iron and Steel making, 8-11, June 2008, Luleå, Sweden, vol. 1, pp. 49-58.