2.

Refractory
Metalurgi Umum
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 MATERI PERKULIAHAN
1. Pendahuluan
2. Refractory
3. Slag
4. Aglomeration, Drying, Calcination
5. Roasting, Reduction (Carbo- / Metalothermic)
6. Smelting
7. Refining
8. Ekstraksi Nikel dengan Jalur Pirometalurgi
9. Ujian Tengah Semester
10. Pengantar Hidro-Elektrometalurgi
11. Teknik-Teknik Pelindian dan Pemisahan Solid Liquid
12. Pemurnian dan Recovery Logam dari Larutan Hasil Pelindian
13. Ekstraksi Nikel Laterit dengan Jalur Hidrometalurgi
14. Ekstraksi Bijih Emas
15. Pemurnian Bauksit Menjadi Alumina
16. Ujian Akhir Semester
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 REFRACTORY

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 REFRACTORY

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 REFRACTORY: FLASH FURNACE

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 REFRACTORY: ISASMELT AND AUSMELT

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 REFRACTORY: REVERBERATORY FURNACE

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 REFRACTORY: MITSUBISHI PROCESS

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 REFRACTORY
Refractory merupakan material utama yang digunakan sebagai pelindung dalam (internal lining)
dari furnace.
Refractory dapat bertahan hingga temperatur 600-2000⁰C

Refractory

mechanic

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 Refractory and industrial materials melting
point chart
4500
Graphite, C, pure 3482
4000 Thoria, ThO2, pure sintered 2998
Magnesia, MgO, pure sintered 2798
3500 Zirconia, ZrO2, pure sintered 2698
Beryllia, BeO, pure sintered 2548
3000 Silicon Carbide, SiC pure 2248
Melting Point (°C)

Magnesia, 90-95% 2193

Chromite, FeO-Cr2O3 2182
2500
Chromium Oxide 2137
Alumina, Al2O3, pure sintered 2048
2000 Chromite, 38% Cr2O3 1971
1455 1538 Alumina, fused bauxite 1871
1500 Silicon Carbide 1871
1082 Fire clay 1871
1000 Kaolin, Al2O3-SiO2 1815
660
419
500 327
231

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Key Industrial Materials

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 Refractory is expensive
Artinya: kerusakan refractory akan menyebabkan kehilangan waktu produksi yang cukup lama,
peralatan, dan kadang-kadang kehilangan produk itu sendiri.
Jenis refractory akan mempengaruhi konsumsi energi dan kualitas produk.

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 Refractory Forms
Refarctory diproduksi dalam 2 bentuk utama yaitu:
1. Preshaped / preformed objects: bricks / shapes.
2. Unformed products (specialties / monolithics): castables, pourables, spray mixes, gunning mixes.

bricks / shapes bricks / shapes

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 Monolithics
Castables, or refractory concretes, are predominately dry, granular refractory mixes designed to be
mixed on site with water and capable of curing to a stable dimensional form. Castables are
particularly suited to the molding of special shapes and parts at the installation site. They can be used
for forming complete furnace linings, and other unique shapes.
Gunning mixes comprise a variety of specialty refractory compositions that develop a solid shape by air
drying or heat curing. The principal requirements are that they can be blown into position by air
pressure through a lance or nozzle, but must adhere on impact and build up to the desired lining
thickness. They are used for repairs, especially inside empty, hot furnaces.

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 Gunning Mix

Alumina for Gunning Mix

Magnesia for Gunning Mix

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 LD Converter (repair zones)

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 Monolithic: Anchor

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 Three classes of refractory (base on chemical
composition)
• Acid (SiO2)
should not be used in contact with basic slags, gases or fumes
• Basic (CaO, MgO)
used with basic chemical environment
• Neutral (Al2O3, Cr2O3)

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 Base Material for Refractory
Chemical Name Abbreviation Chemical Formula Melting Point, °C

Magnesium Oxide M MgO 2825

Aluminium Oxide A Al2O3 2050

Graphite - C > 3500

Silicon Oxide S SiO2 1610

Calcium Oxide C CaO 2614

Chromium Oxide - Cr2O3 2266

Zirconium Oxide - ZrO2 2715

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 Magnesia

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 Magnesia
1. MgO : rumus kimia untuk magnesium
oksida murni

2. Magnesia : nama kimia yang

digunakan untuk magnesium oksida

3. Periclase : nama mineral magnesium oksida (mineral ini jarang

ditemukan di alam; dead burned magnesium oxide
products, mengandung pengotor >10%).

4. Magnesite : nama mineral magnesium carbonate, MgCO3, dan

merupakan salah satu sumber magnesium oksida yang digunakan dalam
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 Definition
Magnesia refractory yang didefiniskan oleh ASTM sebagai dead-burned
merupakan material refractory yang banyak mengandung crystalline
magnesium oxide.
Dead burned: menyatakan material dasar refractory yang dihasilkan dari
proses pemanasan yang menghasilkan produk yang tahan terhadap hidrasi
atmosfir atau combination dengan gas carbon dioxide.

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 Magnesia Heat Treatment
• Calcined : heat treatment is mild (~ 900 – 1300°C).
• Sintered : heat treatment in the range of ~1500 – 2200°C (dead burned materials are in this
group)
• Fused : temperature > 2800°C

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 Magnesium Oxide
Magnesium oxide memiliki titik leleh yang sangat tinggi (sekitar 2800°C).

Titik leleh tinggi, tahan terhadap slag yang bersifat basa, biaya sedang, proses
metalurgi seperti produksi logam, semen dan glass.

Limitation: memiliki thermal

expansion and thermal conductivity
yang tinggi

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 Thermal Expansion and Thermal Conductivity

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 Thermal Expansion and Thermal Conductivity

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 Source of Magnesia
Source of Magnesium oxide: MgCO3, (MgO = 47.6%)
MgCO3 = MgO + CO2

The other source of magnesias are

seawater, brines or salt deposits.

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 Composition of Seawater

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http://www.seafriends.org.nz/oceano/seawater.htm
 Source of Magnesia (cont.)
Magnesium hydroxide, Mg(OH)2, is precipitated by reaction with calcined dolomite or limestone.
2 CaO + MgSO4.MgCl2 + 2 H2O = 2 Mg(OH)2 + (CaSO4 + CaCl2)
2(CaO +MgO) + MgSO4.MgCl2 + 4 H2O = 4 Mg(OH)2 + (CaSO4 + CaCl2)
Magnesium hydroxide slurry is filtered to increase its solids content.

The filter cake can then be fed directly to a rotary kiln or multiple-hearth furnaces at about
900–1300°C to convert the magnesium hydroxide to magnesia.
This calcined magnesia is then sintered for firing into dense refractory-grade magnesia, usually
in shaft kilns which reach temperatures around 2000°C (dead burned). The end product is
sintered magnesia.
Fused magnesia is produced by melting a refractory grade magnesia or other magnesia
precursor in an electric arc furnace.
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 Effect of firing temperature on the densification,
crystal size and hydration of low B2O3 (0.03%)
pelletized magnesia

Firing temperature, Density, Crystal size, ASTM hydration

°C (1 h at temp.) g/cm3 mm tendency, %

1600 3.11 14 91
1650 3.19 17 68
1700 3.26 23 41
1750 3.32 26 27
1800 3.37 30 21
1850 3.40 40 16

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 Magnesia Refractory
• High purity is quite important because MgO has high refractoriness and good resistance to
basic slags.(for converters / ladles, impurities < 2.5%, CaO/SiO2 >3, SiO2+Al2O3+Fe2O3
<0.2%, B2O3 < 0.02%)
• High density reduces infiltration and dissociation of magnesia grain by slag. True
density of periclase is 3.58. Lower density increases total porosity. Densest body offers
the best resistance to corrosion by slags and is the strongest to resist abrasion.
Desired commercial MgO grains for converters and ladle > 3.4.

• Large crystallite size (best achieved in fused magnesias)

provides less surface area for slag attack. (current crystallite
size: 100-200 mm. When best corrosion resistance is needed,
some fused MgO is used, the size can be measured in several
mm)

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 Magnesia Refractory (cont.)
• Carbon plays a vital role in minimizing the penetration of FeO containing
slag into the magnesia carbon refractory.

• (+) In the presence carbon in MgO-C refractory, iron

oxide reacts carbon from refractory. Carbon oxidation
tended to inhibit the slag penetration.

• (+) Carbon is nonwetting.

• (-) Following reaction takes place at temperature

1600°C and lower pressure of CO (e.g. in
vacuum):
MgO + C = Mg + CO
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 Application of MgO: Electric Arc Furnace (EAF)

Refractory:
MgO
HOT SPOT
Refractory:
Slag line and MgO - 14% C
walls
Refractory:
MgO - C

Burnt MgO for

safety lining

MgO
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 Magnesia Chrome

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 Magnesia Chrome
Chrome ores, or chromites, often called chrome enriched spinels, are naturally occurring
members of the spinel mineral group. These materials are all characterized by relatively high
melting points, good temperature stability (particularly in thermal union with magnesite) and
moderate thermal expansion characteristics.

Chrome ores are covered by the formula (Fe,Mg)(Fe,Cr,Al)2O4 where magnesium can
substitute for iron, and aluminum for chromium.
Cr2O3: Min.30%-45%
•SiO2: Max. 5-7%
•Fe2O3: 13-15 %
•Al2O3: 17-19%
•MgO: 8-9%
•P: Max. 0.1%
•S: Max. 0.1%
•Moisture: Max.8 %.
PT. Daya Sekawan Abadi •CR/FE ratio: min.2.50
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 Magnesia Chrome
Pure Cr2O3 chemically separated from chromite can be used in combination with lower cost oxides to
produce specific refractory properties.
Direct Bonding: chrome ore and magnesia are joined predominantly by a solid state diffusion
mechanism at temperature up to 1800°C.

+ =

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 Typical Data of Magnesite Chrome
Source UK South Africa Canada / US
Co sintered Fused Mag. Fused Mag.
Chrome Chrome
Silica (SiO2) 1.15 1-60 1.20
Alumina (Al2O3) 5.70 7.20 6.10
Titania (TiO2) 0.20 0.20 0.30
Iron Oxide (Fe2O3) 12.50 10.70 13.00
Lime (CaO) 0.80 0.60 0.40
Magnesia (MgO) 61.50 59.90 60.10
Chromic Oxide (Cr2O3) 18.00 18.80 18.60

Bulk density (g/cm3) 3.53 3.75 3.8

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 Magnesia Chrom
Chrome oxide has good resistance to slag attack. In combination with magnesia, the magnesia-chrome
products have excellent refractoriness and spalling resistance.
Soluble hexavalent chromium compounds could be formed are formed, leading to an environmetally
unfriendly product disposal problems due to its potentially carcinogenic characteristic.

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 Thermal Expansion and Thermal Conductivity

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 Application of Magnesite Chrome
• Applications of magnesite chrome are similar to magnesia

• Pay attention:
- magnesia does not increase (pick-up) magnesium content in metal
- chrome containing refractories can lead to a serious chromium pick-up in steel and discoloration
of glass

• Magnesia-chrome is applied for submerged arc furnaces (SAF), smelting furnaces for ferro alloys,
copper converters, AOD lining, VOD-ladle lining, RH plant.

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 AOD Converter

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 Lime

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 REFRACTORY
CaO has a melting point approaching 2600°C and shows a fairly high resistance to basic slags.
Reaction DG at 1600°C (kcal / mole O2)
2 Ca + O2 = CaO -205
4/3 Al + O2 = 2/3 Al2O3 -175
2 Mg + O2 = 2 MgO -170
Si + O2 = SiO2 -140
4/3 Cr + O2 = Cr2O3 -110

It may well be asked, why this readily available material is not uses as a principal refractory?
The answer one word is hydration. It is readily attacked by water form calcium hydroxide.

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Terima Kasih