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THE USE OF CALCIUM ALUMINATE SOLUTIONS IN THE ALUMINIUM INDUSTRY

Christoph Whrmeyer , Nikolaus Kreuels , Christopher Parr, Thomas A. Bier presented at the UNITECR Congress; Berlin, Germany, September 1999.

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Abstract Refractory castables in furnaces of the aluminium industry are usually exposed to temperatures below 1000C. The addition of a flux like fluorspar or barytes enables sintering at low temperatures and also prevents aluminium infiltration. But it can lead to early refractory wear in the case of furnace over-heating. This paper investigates the applicability of calcium aluminate aggregates in refractory castables in the aluminium industry. Sintered as well as fused calcium aluminate cements (CAC) have been chosen as a binder for the concretes investigated. Calcium aluminate aggregates (R50) have been used as well as common refractory aggregates like tabular alumina, bauxite and fireclay. Castables made from R50 with a pure CAC bonding show superior infiltration resistance against aluminium alloys, even without the addition of anti-wetting aids. This makes them applicable up to 1400C.

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Introduction

Mis design of the test castables

different aggregates and

The use of calcium aluminate aggregates combined with calcium aluminate cement as binder, is well known as concrete for floor areas in buildings, where furnaces are placed. These special concretes have excellent resistance against thermal and mechanical shock, moreover, they are characterized by early strength development compared to concrete with Portland cement as binder 1. They show considerable improvement of durability in comparison to other building concretes. Inside the furnaces, calcium aluminate cements are used as binder for refractory castables. They are combined with different aggregates, like tabular alumina, bauxite and fireclay. In contact with aluminium the traditional bauxite-based mixes require anti-wetting additives, that at the same time function as low temperature sintering aids. The temperatures inside the aluminium furnaces are usually below 1000C. If temperatures reach unexpectedly high levels above 1200C, the sintering and anti-wetting additives like BaSO4 or CaF2 can destroy the castable. Calcium Aluminate Aggregates (R50) combined with Calcium Aluminate Cements (CAC) have been investigated to solve the problem of temperature limit of existing castable solutions for aluminium furnaces.

Comparison of binder systems

Table 1 shows the chemistry of the CAC and R50. CAC 50 is a fused calcium aluminate cement with 50% alumina made from bauxite and lime. CAC 70 is a cement manufactured by sintering of alumina and lime; R50 is a clinker produced in a fusion process and crushed into different fractions. This R50 aggregate has, due to the fusion process, nearly zero open porosity. It consists of 53% alumina, combined with 37% lime. From the mineralogical point of view it consists predominantly of calcium monoaluminate and a smaller amount of gehlenite.
Table 1. Chemistry of the tested calcium aluminate cements CAC and calcium aluminate aggregates R50 (wt.%) Al2O3 CAC 50 CAC 70 R50 53 71 53 CaO 37 27 37 SiO2 5 0.4 5 Fe2O3 <2 0.2 <2 TiO2 <4 <0.4 <4 MgO <1 <0.5 <1

Table 2 contains the design of the mixes tested against aluminium alloy at 800C for 72 h in a cup made from the castable. Conventional castables with 15% CAC 70 are mixed with aggregates of R50, tabular alumina and fireclay. A low cement castable with 5% CAC 70 based on R50aggregates without anti-wetting aid is compared with; low cement castable based on bauxite with addition of barium-sulfate. BaSO4 is well known as an anti-wetting aid 3. This mix also contained 5% fumed silica.

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Table 2. Formulation of conventional and low cement castables tested on aluminium resistance (wt.%) Mix No. R50 3-5 mm R50 1-3 mm R50 0-1 mm Tab. Alumina 2.4-6.4 mm Tab. Alumina 1.2-2.4 mm Tab. Alumina 0-0.6 mm Fireclay 2-5 mm Fireclay 0.2-2 mm Fireclay 0-0.5 mm Bauxite 3-6 mm Bauxite 1-3 mm Bauxite 0-1 mm CAC 70 Tab. Alumina 0-0.04 mm BaSO4 powder Microsilica Reactive alumina Darvan 7S Citric acid 1 28 20 27 15 10 2 28 20 27 15 10 3 28 20 27 15 10 6 27 28 20 15 10 4 28 20 27 5 10 5 5 0.1 0.02 5 28 20 27 5 10 10 5 5 0.1 0.02

The physical properties of the mixes The water demand, bulk density, open porosity, strength, and thermal resistance of the tested mixes can be seen in Table 3. Water demand and workability properties are very similar to standard aggregates like tabular alumina, bauxite and fireclay.
Table 3. Properties of the castables tested on aluminium resistance Mix-No. Water demand (%) Bulk density 110C (g/cm3) 800C (g/cm3) Open porosity after heating at 800C, 5 h (vol.%) Cold crushing strength 800C, 5 h (N/mm2) Max. service temperature (C) Aluminium cup test 800C, 72 h, alloy AZ8GU Infiltration depth (mm) 1 8.5 2.55 2.45 20.5 85 1400 0 2 8.5 2.88 2.82 23.0 56 1800 <2 35 1500 12 45 1500 6 3 8.5 2.21 2.14 6 8.5 2.28 2.21 4 5.0 2.53 2.52 12.5 165 1350 0 65 1200 0 5 6.5 2.59 2.59

The conventional castable based on R50aggregate is applicable up to 1400C. The bauxite based LCC containing BaSO4 has an application limit of 1200C.

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The resistance against different types of aggressive environments

These mixes do not contain anti-wetting additives. An improvement in the fireclay castable (sample no.3) is the replacement of R50 0-1 mm fraction (sample no.6) for the fireclay 0-0.5 mm. Compared with a traditional bauxite-LCC with BaSO4 as anti-wetting additive, the R50-LCC without anti-wetting additive has the same infiltration resistance but does provide increased thermal stability up to 1350C. Reducing atmosphere / CO-gas Several samples, as shown in Table 4, were tested in a CO-gas atmosphere according to BS 1902 at 500C (100 h). Reducing atmospheres can occur in aluminium furnaces but it is a more important factor in other applications like the petrochemical industry. There is a clear correlation between the content of free metallic iron caused by crushing of R50. Starting with a mix, which consists of tabular alumina aggregates, the different fractions were successively replaced by R50 (samples 2, 8, 9, 10). It becomes evident that the amount of metallic iron from crushing significantly influences the CO-resistance. In the case of iron-free crushing, the R50 withstands quite well a COatmosphere. This can clearly be seen by comparing the samples no. 2 and 7. Both are based on tabular alumina aggregates, whereas sample no. 2 contains CAC 70 and no. 7 contains CAC 50. CAC 50 and R50 are similar in chemistry, but CAC 50 is milled in such a way that only a limited amount of free metallic iron is generated. Results show that both calcium aluminate cements, CAC 70 and CAC 50, are resistant against the reducing atmosphere. The CAC 50 contains 1,5% iron oxide, but it has a very low content of free iron metal from milling. Free iron is the most important factor for destruction in a CO-containing atmosphere 4.

Liquid Aluminium alloy Typical interactions in aluminium furnaces between liquid alloys and traditional refractory materials are the infiltration of molten metal and slag into the structure of the bricks or castables. Corundum build-up occurs by reduction of silica or iron oxide. In the case of sodium rich alloys or treatment with alkaline rich salts, beta-alumina formation and spalling can occur with alumina-rich refractories. Cup tests at 800C and 72 h with the alloy AZ8GU show excellent infiltration resistance of all mixes containing the calcium aluminate aggregate R50 in combination with calcium aluminate cement (Figure 1).

Figure 1. Cup tests with aluminium alloy AZ8GU, 72 h at 800C

The mix with tabular alumina shows remarkable infiltration as well as corundum formation. The liquid aluminium was deeply infiltrated into the fireclay-based castable.

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Additional security in the event of heavy CO-gas attack is possible with the use of the CAC 70. Due to the extremely low iron and iron oxide content it shows superior CO-resistance. Therefore, in order to design a castable with high resistance to CO attack, it would be necessary to use R50 that contains low levels of free iron. This could be achieved by avoiding the generation of free iron during crushing and grinding.

Figure 2. Test prisms after CO-attack at 500C, 100 h

Table 4. Formulation of conventional castables tested on CO-gas resistance (wt.%) Mix No. R50 3-5 mm R50 1-3 mm R50 0-1 mm Tab. Alumina 2.4-6.4 mm Tab. Alumina 1.2-2.4 mm Tab. Alumina 0-0.6 mm Tab. Alumina 0.0.04 mm CAC 70 CAC 50 1 28 20 27 10 15 2 28 20 27 10 15 7 28 20 27 10 15 8 28 20 27 10 15 9 20 28 27 10 15 10 27 28 20 10 15 -

Table 5. Properties of the castables tested in CO-gas atmosphere (500C, 100 h) Mix No. Water demand (%) Content of metallic iron (ppm) Resistance against CO-gas according to ASTM-classification 1 8.5 293 C-D 2 8.5 26 A 7 8.5 69 A 8 8.5 113 A-B 9 8.5 78 B 10 8.5 153 B-C

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Summary and outlook

References

This study showed that aggregates made from fused calcium aluminate have an excellent resistance against liquid aluminium alloys. Combining R50 with calcium aluminate cements CAC 70 or CAC 50, castables can be designed which have the same resistance as castables which contain anti-wetting additives like barium sulfate. Castables for the aluminium industry can be made from R50 plus CAC for application temperatures up to 1400C without the need of anti-wetting additives. This limits the risk of early refractory wear as a consequence of over-heating the furnace. Furthermore the R50 could be used in refractory bricks for aluminium furnaces. The CO-resistance of iron free crushed R50 would make that aggregate also applicable in the petrochemical-industry, since it has at the same time an excellent erosion resistance after heating at 800C 1.

1 Whrmeyer, C.; Kreuels, N.; Parr, C.; Vialle, M.; Calciumaluminate: Zemente und neue Zuschlagstoffe fr den Einsatz in der Aluminiumindustrie, 41. International Colloquium on Refractories, Aachen (1998), p. 80- 86 2 Wieland, K.; Weichert, T.; Eschner, A.; Whrmeyer, C.; Feuerbestndiger oder feuerfester Stein als Zinnbad-Bodenstein, European patent application EP 0615959 3 Elstner, I.; Nebe, U.; Santowski, K.; Whrmeyer, C.; Neue Entwicklungen auf dem Feuerfest-Sektor fr den Einsatz in der Aluminiumindustrie. Dritte Duisburger Industrieofentage (1995). 4 Schnabel, M.; Ungeformte feuerfeste Erzeugnisse fr den Einsatz unter CO- und Abriebbeanspruchung, 40. International Colloquium on Refractories, Aachen (1997), p.185-189.

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