METHODS FOR UTILIZATION OF RED MUD

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METHODS FOR UTILIZATION

OF RED MUD

Attila Lengyel [email protected]

János Lakatos [email protected] University of Miskolc, Institute of

Chemistry

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KEYWORDS

Red mud or bauxite residue

Difficulties of utilization Difficulties of utilization Possibilities of utilization Possibilities of utilization Selectivity Selectivity Complexity Complexity Perspectivable methods Perspectivable methods

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3

Motto

ICEMT, Veszprém, 25.05.2011

„

„FFor a long time know that red mudor a long time know that red mud could be processed could be processed for

for the last grain of sand - said engineer George Baksathe last grain of sand - said engineer George Baksa, , who

who worked atworked at the Hungalu the Hungalu for for decades, and also led decades, and also led the company for a long time. But there are serious

the company for a long time. But there are serious

doubts that this can be done economically. Huge

multinational companies dominate the world

multinational companies dominate the world’’s s aluminum

aluminum industry industry, but so far none of them got involved , but so far none of them got involved into this work. But if

into this work. But if it it would would be be big business big business they didn’t they didn’t put off doing it.”

put off doing it.”

In a reports after the red mud cunami, Kolontár

Stored: 2,7 billion tons

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PRACTICAL DIFFICULTIES OF

UTILIZATION

Components and minerals Empirical formula

Al2O3:16-18%

Gibbsite (hidrargrillit) Al(OH)₃

Böhmite γ-AlO(OH)

Diaspore α-AlO(OH)

Alumogoethite (goethite-diaspore) α-Fe(Al)O(OH) Sodium-aluminum-silicates

(sodalite, cancrinite), SAS

3(Na₂O.Al₂O₃.2SiO₂).Na₂X.yH₂O X anions depend on conditions of digestion: CO₃2-, SO₄2-, 2Cl-, 2OH-, 2[Al(OH)₄]

-Calcium-aluminum-silikates (CAS) 3CaO.Al₂O₃.xSiO₂.(6-2x)H₂O Tricalcium-aluminate 3CaO.Al₂O₃.6H₂O 2Al(OH)₃Al₂O₃+ 3H₂O H₂O H₂O H₂O F re e an d b o u n d ed w at er

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5 ICEMT, Veszprém, 25.05.2011 -15 -10 -5 0 5 10 0 200 400 600 800 1000 1200 temperature, oC TG/100 DTA/100*25 DTG/100*25 PRACTICAL DIFFICULTIES OF PRACTICAL DIFFICULTIES OF UTILIZATION UTILIZATION DERIVATOGRAM

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Fe₂O₃: 33-48%

Hematite α-Fe₂O₃

Goethite α-FeO(OH)

Maghemite γ-Fe2O3

Pyrite or Marcasite FeS₂

SiO₂: 9-15%

Kvarc SiO₂

Sodalite, cancrinite (SAS) 3(Na₂O.Al₂O₃.2SiO₂).Na₂X.yH₂O Calcium-aluminum-silikate (CAS) 3CaO.Al₂O₃.xSiO₂.(6-2x)H₂O

TiO₂: 4-6%

Sodium-titanates Na₂O.xTiO₂ (x=3 or 4 or 6) Calcium-titanate CaO.TiO₂

Rutile or Anatase TiO₂

ICEMT, Veszprém, 25.05.2011 H₂O

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7 TiO₂: 4-6% MgO: 0,3-1% CaO: 0,5-3,5% V₂O₅ :0,2-0,3% P₂O₅: 0,5-1,0% CO₂: 2-3% S: 0,10-0,3% F: 0,10-0,15% MnO: 0,2-0,3%; Ga: 0,003%; Cr₂O₃: 0,1%; Ce: 0,04%; La:0,02%; Nd:0,02%; Gd:0,015%; Y: 0.01%; Sc: 0,005%; Sm: 0,002%; Pr: 0,001% ZrO₂: 0,1%; Na2O: 8-12%

Sodalite, cancrinite (SAS) 3(Na2O.Al2O3.2SiO2).Na2X.yH2O

Sodium-titanates Na2O.xTiO2 (x=3 or 4 or 6) Others ICEMT, Veszprém, 25.05.2011

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Synthesis and structure of perrhenate sodalite Shas V. Mattigod a,*, B. Peter McGrail a, David E. McCready b, Li-Quong Wang c,

Kent E. Parker a, James S. Young b

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What does „red mud” mean?

What does „bauxite residue” mean?

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Possibilities of utilization of red

mud



Civil and building applications



Cement production



Aggregats

_Light-weight_Light-weight _Low-stength_Low-stength

_{Sand substitution}_{Sand substitution}



Bricks, blocks and other elements

_{Kiln fired}_{Kiln fired} _{Not kiln fired}_{Not kiln fired}



Geopolymers



Chemical applications



Catalysts supporters, adsorbents



Ceramics, coatings



Fillers of plastics



Pigments

R

a

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Q U A L I T Y

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11 ICEMT, Veszprém, 25.05.2011



Environmental applications



Treatment of waste water and acidic mine

water



Decontamination of soils



Treatment of abgases and flue gases



Adsorption of SO

₂₂



Absorption/adsorption of CO

₂₂



Agronomic applications



Treatment of acidic soils (general soil

amendment



Phosphate retention



Decontamination of soils

mud

R

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

Metallurgical applications



Al-extraction



Steel making



Extraction of minor elements



Ti



V, Ga, Ge



RFF

Possibilities of utilization of red

mud

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Statistics of patent activities; world

wide; -2008

34% 13% 12% 12% 9% 7% 4%

4% 2% 3% Civil and buildingconstruction

Catalysts/adsorbents Ceramics, coatings, pigments

Water treatment Recovery of major

componets (Fe, Al, Ti, Na) Steel making and fluxing Soil amendment

Fuel gas purification Recovery of minor elements

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THE EXPECTATIONS for

METALLURGICAL UTILIZATION

1.

Complexity

Coupled utilisation: combine the extraction of the

minor elements to the utilisation of the main

components.

components. Results:

Results:

• no waste remains,_{no waste remains,}

• the operating costs of extraction of minor _{the operating costs of extraction of minor}

elements has shared by the main

elements.

2.

Utilisation of the

main components

:

iron and aluminum

iron and aluminum recycle by the known recycle by the known

metallurgical

metallurgical processprocess ( (aluminum inaluminum in the the Bayer Bayer process, iron in

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3.

Basic material of complex utilization will be

the

the original sludge

original sludge

(no dry material),

4.

T

he recovery include

s

the presence of small

the presence of

small

amounts of metals

(Ti, rare and rare earth

metals),

5.

Produced as a result of the processing

intermediates (e

.

g

.

ferroalloys) could

ferroalloys)

could

be

processed more, economically

6.

During processing, avoid

During processing,

avoid

the formation of

hazardous wastes.

THE EXPECTATIONS for

METALLURGICAL UTILIZATION

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SELECTIVITY

0 1000 2000 3000 4000 5000 6000 F e k o n c en tr á c ió a k iv o n a tb a n , m g d m -3 Bauxit Vörösiszap Deszt.víz 1 M MgCl2 1 M HAc NH2OH-1 MHAc H2O2-HNO3 Királyviz HF LiBO2 0 200 400 600 800 1000 1200 1400 1600 1800 A l k o n ce n tr á c ió , m g d m -3

H2O 1 M MgCl2 1 M HAc NH2OH-1 M HAc H2O2- HNO3 LiBO2

Kivonószerek

Fe

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EXTRACTION assisted by MICROVAWE EXTRACTION assisted by MICROVAWE

S:L = 1:20; 300 W, 1 h, 140 oC ICEMT, Veszprém, 25.05.2011 Al Ca Fe Mg P Cr Mn mother liguore 1388,6 5 5 3,5 0,53 0,46 0,02 mother liguore + sample 2869,8 5 5 3,2 0,43 0,86 0,02 2 m H2SO4 4296 435,3 5695 232,7 62,5 10,9 116,94 0,5 m H₂SO₄ 490,4 418,8 85,5 233,5 17,6 1,42 92,3 2 m HCl 4506 2548 6027 249 18,27 5,9 75,2 0,5 m HCl 1893,3 2488 70 178 5,11 2,45 74,5 V Ti Zr Ga Ce La Nd mother liguore 2,47 0,1 0,01 2,66 0,01 0,01 0,01 mother liguore + sample 9 0,1 0,01 3,31 0,01 0,01 0,01 2 m H2SO4 9,17 970,5 12,38 1,202 7,66 4,02 3,39 0,5 m H₂SO₄ 1,62 1,5 0,6 0,07 0,41 0,16 0,12 2 m HCl 4,87 102,8 0,36 0,57 6,1 2,7 2,51 0,5 m HCl 1,45 1,1 0,038 0,07 8,9 4,42 4,79 mg/L sample

Lengyel Attila, Lakatos Janos: Vörösiszap hasznosítása mikrohullámú feltárással, VII. Kárpát-medencei környezettudományi konferencia. Kolozsvár, 2011. március 24-27. I-II. kötet

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SUGGESTED METALLURGICAL

METHODS

ICEMT, Veszprém, 25.05.2011 BAUXITE RESIDUE WET MIXING Reduction Sintering 800-1000 o_C WATER LEACHNG S/L SEPARATION To Bayer Process

MAGNETIC SEPARATION ACID LEACHING

HYDROLISYS SMELTING PIG IRON SLAG GYPSUM TiO₂ RFF

PIGA, L; POCHETTI, F; STOPPA, L: Recovering metals from red mud generated during alumina production, JOM-JOURNAL OF THE MINERALS METALS & MATERIALS SOCIETY,

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SUGGESTED METHODS

Complex utilization Szépvölgyi, AKKI Bauxite RED MUD Flue gas Na free sludge BAYER-process Na-discharge Calcination Ox. chlorination Red. Chlorination Condensation Decomposition Decomposition _{Decomposition} Leaching Separation Purification

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Knowledge gap

Expected activity

A lot of processes heve been proposed without implemen-tation for metallurgical reco-very of the major from red

mud? What are BAT?

Choose the most usable ones!! What means: „zero waste” objective?

Risks of red mud depositions Rise the assurence of red mud landfields

Market potencial and permit-ted condition at construction and agriculture application

Make standards; NORM; OUALITY Essurance!

PRIORITIES IN THE RESEARC and

INNOVATION

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INNOVATION

Knowledge gap

Expected activity

Economy of the processes

for utilization Expect publication of capi-tal and operation costs of

the processes compared with the cost of deposition. Technical possibilities of

the complex utilization

(from operation on

land-fields to metallurgy/making products/agronomy

applications)

Govermental encourage for developing new complex utilization technologies linking known and

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Knowledge gap

Expected activity

What are the impacts of

usage of red mud? Make standards and technical specification of

process and products in which red mud are used.

Are there any receptivity for

red mud usage by

international and domestic owned firms?

Make a survay!

PRIORITIES IN THE RESEARC and

INNOVATION

HUNGARY

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Knowledge gap

Expected activity

Is it worth to install a complex technological system?

Classify the patented and

published processes!

Research work to base

the development of

complex technologie(s) for dry Bayer process’ mud and historical storaged materials

Make a pilot plan

PRIORITIES IN THE RESEARC and

INNOVATION

HUNGARY

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THANK YOU

VERY MUCH

FOR YOUR KIND

ATTENTION!