Oil Shale ash, a hazardous waste or co-product and valuable material for different applications Uuve Kirso National Institute of Chemical Physics and

Oil Shale ash, a hazardous waste or co-product and valuable material

for different applications

Uuve Kirso

National Institute of Chemical Physics and Biophysics,

Akadeemia tee 23, 12618 Tallinn

U. Kirso, 27. 04.2010 “Innovaatilised lahendused ja säästvad tehnoloogiad”, Jõhvi, Ida-Virumaa

Outlines


1. Oil Shale processing in Estonia, past, present and future scenarios

2. Recycling - wastes of fossil fuel processing, dynamics and current practice

5. Acknowledgements (in-house, local, international)

4. Role of legislation in recycling of wastes

3. Recent developments of R&D activity for recycling of oil shale ash

IntroductionOil shale as a fossil fuel• Huge resources worldwide

• Represent a viable energy alternative for several countries

Why the oil shale shale is not widely used?• Low calorific value, e.g. high mineral content and vaste

quantities of solid wastes

• Geographical, economical and political aspects influence consumption of any fuel, including oil shale

• As result of changing world, the position of oil shale in global scale is changed


Current practice of oil shale processing

Estonia:• Commercial use from 1916• Innovative approach: new technologies for combustion

and oil production were developed

What about the by-products?• A large quantity of ash is formed, mainly deposited • There are both, economical and ecological needs to

convert the enormous quantities of oil shale ash into a

resource U. Kirso, 27. 04.2010 “Innovaatilised lahendused ja säästvad tehnoloogiad”, Jõhvi, Ida-Virumaa

Future scenarios if the ash is deposited

New landscape in Ida-Virumaa will be formed


Outlines







Current practice of ash utilization (per cents, from ash generated)

0 20 40 60 80 100

Germany

Denmark

United Kingdom

France

Poland

China

USA

India

Estonia

per cents

Coal

Oil shale


Kasutatud tuha osakaal (protsentides tuha koguhulgast) eri riikides

Recycling dynamics of coal by-products during the last decades

0

5

10

15

20

25

30

35

40

45

50

1966

1968

1970

1972

1974

1976

1978

1980

1982

1984

1986

1988

1990

1992

1994

1996

1998

2000

2002

2004

2006

Aasta

Söe p

õle

mis

saaduste

kasuta

min

e, %


U. Kirso. (2008). Põlevkivituhk kui kasulik kõrvalsaadus. Keskkonnatehnika.Nr. 5.

Recycling of coal ash in USA 2005Main areas (per cents) based on data from ACAA

http://acaa.affiniscape.com/associations/8003/files/2005%20CCP%20Survey%20(09-19-06)Corrected-11-09-07.pdf


Outlines







Recycling of oil shale wastes I(R&D activity)

Australia: spent shale as adsorbent (Zhu et al., 1988).

Brazil: spent shale as fertilizer (Mangrich et al., 2001), for synthesis of zeolites (Machado and Miotto, 2005), as an adsorbent (Pimentel et al., 2008).

China: oil shale ash in building materials (Jiang et al., 2007) for cement (Feng et al., 1997, 2007), for synthesis of silica nanoparticles (Gao et al., 2008).

Israel: oil shale ash in building materials (Bentur et al., 1981; Baum et al., 1985, 1986; Freidin, 1998, 1999, 2002, 2004).

Jordan: oil shale ash in building materials (Khedaywi et al., 1990), in Portland cement concrete (Smadi and Haddad, 2003; Al-Otoom, 2006), for synthsis of zeolites (Shawabkeh et al., 2004), as an adsorbent (Al-Qodah 2000; Al-Qodah et al., 2007).

Russia: oil shale ash in road building, in building materials, as lime fertilizer, in Portland cement (Strizhakova, Usova, 2007) in glass ceramics (Gorokhovsky et al., 2002).

UK, Scotland: spent oil shale in road construction, in earthwork construction (Winter, 2001).

USA: Recent development, see ACS meeting San Francisco, March 2010.


Recycling of oil shale wastes II Estonia :• One fraction of combustion ash used completely

for building industry• R&D activity

The oil shale fly ash has been used for the synthesis of

zeolites and tobermorites, applying hydrothermal

alkaline treatment. The activated oil shale ash was

applied on catalytic lactose isomerisation and CO2 capture


27Al MAS-NMR spectra of treated (top) and non-treated (bottom) ash samples

29Si MAS-NMR spectra of non-treated ash from PF and CFB boilers

29Si MAS NMR spectra of treated PF and CFB ash samples (deconvolution of the spectra by Gaussian lines) J. Reinik, I. Heinmaa, J.-P. Mikkola and U. Kirso (2007). Hydrothermal alkaline treatment of oil shale ash for synthesis of Tobermorites. Fuel, 86, 5-6, 669-676.


SEM photos of non-treated (A) and treated (B, C) oil shale ash

Quartz

Lime

CaSO 4

MgO

Fe 2 O 3

PF

A

B

CJ. Reinik, I. Heinmaa, J.P. Mikkola, U. Kirso (2008). Synthesis and characterization of calcium-alumino-silicate hydrates from oil shale ash – Towards industrial applications. Fuel 87, 1998-2003.


R&D strategy for evaluation of wastes as material for recycling

Disclose:

•The chemical composition of each ash fraction

•The matrix characteristics of ash material

Find the most appropriate method for treatment the raw material

Testing the new material obtained, including risk assessment

The proposed approach provides clear environmental benefits, because an industrial waste-material could be converted to a valuable productJ. Reinik, I. Heinmaa, J.P. Mikkola, U. Kirso.(2008). Synthesis and characterization of calcium-alumino-silicate hydrates from oil shale ash – Towards industrial applications. Fuel 87, 1998-2003.

J. Reinik, I. Heinmaa, J. -P. Mikkola, U. Kirso (2007). Hydrothermal alkaline treatment of oil shale ash for synthesis of tobermorites. Fuel, 86, 5-6, 669-676.

J. Reinik, I. Heinmaa, J.-P. Mikkola, K. Kordás, U. Kirso (2010) Synthesis Of Calcium-Alumino-Silicate Hydrates From Oil Shale Ash In Different Alkaline Media. Oil Shale. 2010, Vol. 27, (1), 47-57


Outlines







Does the existing environmental legislation support recycling of industrial wastes?

Yes, promotion of recycling of by-products via EU Landfill Directive. However, an environmental permit is required for recycling activities!

No, all residues are considered as wastes; the concept of by-product is not recognized

Wastes vers products – conflicting views! J. Sorvari. Waste Management.2008, 28,No 3, 489-501


The recycling target in legislation, how to receive it?

Create separate regulations for by-products (exist already in Netherlands, Denmark, US several states) or Adapt soil and water quality guidelines and limits, with specific attention of the long term leaching potential of material, or Create material specific environmental standards and criteria – a long way to go

Always keep in mind that the main principles of EU policy are:

Sustainable use of natural resources and utilization and recycling of wastes


EUROPEAN ENVIRONMENTAL LAW ENERGY,

CLIMATE CHANGE AND OTHER RECENT

DEVELOPMENTS Trier, 17-18 June 2010

• Energy and environment under the Lisbon Treaty

• The following topics of Community policy in the

field of environment protection will also be

examined:

*Waste prevention and management

*Implementation of REACH


Outlines







Collaboration partners


Prof. R. M. Kamens, Department of Environmental Sciences and Engineering, School of Public Health,

University of North Carolina at Chapel Hill, USA

Prof. A. Kettrup, Dr.. I. Gebefügi, Dr. P. Schmitt-Kopplin, Helmholtz Zentrum München, German Research Center for Environmental Health, Institute of Ecological Chemistry, Neuherberg, Germany

Prof. Eiliv Steinnes, Dept. of Chemistry Norwegian University of Science and Technology, Trondheim, Norway

Dr. Jyri-Pekka Mikkola, Åbo Akademi, Process Chemistry Center, Laboratory of Industrial Chemistry, Åbo/Turku, Finland

Acknowledgement

Estonian Ministry of Education and Science target financing No SF0690001s09 Environmentally friendly utilization strategy of oil shale processing solid wastes, 2009-2014

Estonian Science Foundation Grant No 6828 The investigation of methods of recycling of solid waste of oil shale processing , 2006-2009AS Eesti Energia and AS Narva Elektrijaamad

We also thank Mrs. P. Laas for the technical assistance.


Many thanks for the good job!


Group of Environmental Chemistry and Technology, NICPB

Documents

Oil Shale ash, a hazardous waste or co-product and valuable material for different applications Uuve Kirso National Institute of Chemical Physics and