China’s Refractories

doi:10.19691/j.cnki.1004-4493.2021.02.005

High Quality Doloma Refractories —

Essential for Stainless Steel Production
Hilmar SCHULZE-BERGKAMEN1*, Eric LIU2, Clemens EBNER3
1 RHI Magnesita, Dalian 116600, China
2 RHI Magnesita, Chizhou 247000, China
3 RHI Magnesita, Leoben 8700, Austria

Hilmar Schulze-Bergkamen is Head of R&D China/East Asia at RHI Magnesita located in Dalian, P. R.
China. He obtained his PhD in Germany, based on a thesis about sol-gel manufactured thin PZT films and
joined the Tokyo Institute of Technology as a postdoctoral researcher. Since then, he has taken up various
roles as QA and R&D Manager within the glass and refractory industry.

Abstract
Since early 2020 RHI Magnesita has been running a fully integrated dolomite plant in Chizhou, Anhui Province, P. R.
China. The current operation consists of a world-class dolomite mine including a state-of-the art sinter plant equipped with
rotary kiln plus a plant where shaped and unshaped doloma products are being manufactured. As raw dolomite has been a
technically usable carbonate rock for decades the article describes the way from raw dolomite stone to doloma production.
Key words：dolomite; doloma refractories; stainless steel

1 Introduction
Dolomite is one of the most widely distributed minerals in
the earth’s crust and its deposits were formed by diagenetic
processes in the upper earth strata 500-600 million years
ago[1]. It is a sedimentary rock formed in warm shallow marine
environments from shell, bone, coral deposits which initially
form calcium carbonate mud (CaCO 3/limestone). The calcite
was modified to dolomite by magnesium-rich groundwater
via a chemical change known as dolomitization. How far
the dolomitization proceeded determines the dolomite’s
composition. Deposits worldwide range from dolomitic
limestone to dolomitic magnesite. This can be also written as a
sequence of minerals with increasing share of MgCO 3: Calcite–
Mg-Calcite–Proto-Dolomite–Ca-Dolomite–Mg-Dolomite.
Doloma refractories are widely used in the steel and cement
industry[2-8]. Advantages of doloma and magnesia refractories
are their compatibility with chemically basic environments
when in contact with basic slags, cement and lime, their high
melting points (high refractoriness) of pure components CaO
and MgO, their excellent coating behaviour in cement kilns and
steel ladles. Under certain circumstances, doloma refractories
react with silica in a favourable way to form stable mineral
phases with high melting points. However, the application of
doloma refractories is restricted as they are susceptible to
hydration (their lime component is readily attacked by water
vapour to form calcium hydroxide) and they also have a poor
resistance to chemical interactions with chlorine, sulphur
oxides, CO 2 plus trivalent oxides R 2O 3 like alumina that flux
them easily. Additionally, doloma refractories show on the
one hand high thermal expansion and conductivity thus poor
thermal shock resistance, and their modulus of elasticity (MOE)
is relatively high which is on the other hand counteracted by
their ability to creep without failure and their plasticity at high
temperatures.
While magnesia variants are also susceptible to hydration,
doloma is far more sensitive due to the presence of lime in
the doloma grain. The hydration reaction of doloma is an
expansive reaction, which means mass (hydroxide) is added
to the grain from water. This enlarges or swells the grains and
cracks the bricks. It is critical to heat doloma bricks as quickly
as possible to 580 °C to reduce the time allowed for this
chemical reaction to occur as the brick interacts with water
from ambient air humidity (kiln draft) and combustion products
(moisture from burning natural gas). However, if the heating
occurs too fast, it results in cracks from binder burnout during
firing.
Carbonate rocks predominantly consist of calcite (CaCO3)
and dolomite (CaMg(CO3)2). They contain silicates like quartz,
feldspar, mica and clay as minor components.
*Corresponding e-mail: hilmar.schulze_bergkamen@rhimagnesita.com

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Dolomite is a major natural raw material to produce refractories
(Fig. 1). The process usually starts with the calcination of
natural dolomite mineral.
CaCO3 · MgCO3 → CaO · MgO+2CO2
The calcination requires temperatures between 1 000–1 100
°C, the sintering for producing doloma sinter temperatures
between 1 800–2 000 °C. Both processes may happen as a
single step in a shaft or rotary kiln. Impurities as expressed as
∑(Al2O3+Fe2O3+SiO2) should be generally lower than 2.5 mass%
in content for fired brick production. The chemical nature of
doloma refractories is basic. Under the microscope sintered
doloma appears as a continuous matrix of CaO with idiomorphic
MgO embedded in this matrix (Fig. 2). At room temperature there
is very low CaO in solution with the MgO.
Fig. 1 Dolomite rock © RHI Magnesita
Fig. 2 Schematic view of doloma with idiomorphic
periclase (MgO, black) within a continuous matrix of CaO
(lime, light grey) © RHI Magnesita
Pure calcined doloma has according to the system MgO-
CaO an eutectic melting point of 2 370 °C (Fig. 3).
Doloma based products are characterized by relatively
high thermal expansion. Even more unique to them is their
high level of plastic deformation they can undergo without
failure at high temperatures. Fired, ceramically bonded bricks
based on 100% doloma can deform/compress by about 10%
of their length without cracking. Magnesia bricks in the same
test do not compress more than 1% and they typically crack.
It is thought that the continuous lime phase attributes to this
behaviour. If more flux material such as iron oxide or alumina
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China’s Refractories
is present in fired doloma bricks even more deformation can
take place. However, as more magnesia is added to the bricks
its thermal coefficient of expansion of the product increases.
Fig. 3 Phase diagram of MgO and CaO[9]
Doloma is the refractory of choice for the stainless-
steel industry. Stainless steel is the name given to a group of
corrosion resistant steels that must satisfy 2 criteria. It must
contain a minimum of 10.5% chromium with at least 50%
iron. It must resist corrosive attack from normal atmospheric
exposure. Both criteria must be met for it to be classed as
stainless. A minimum of 10.5% chromium in iron makes
the surface chemically passive by forming an extremely thin
invisible and adherent chrome oxide film, when exposed to
oxygen. When it is damaged it has the unusual ability to heal
itself in the presence of oxygen.
Stainless steel refining uses highly basic lime rich slags
which in most cases have been deoxidised (killed, reduced)
using silicon. This strongly favours using doloma over magnesia
refractories. About 80% of the world’s stainless-steel production
has a very low final carbon specification (<0.05%) which
demands a low carbon refractory [1]. Fired dolomite which is
carbon-free, and low carbon-containing carbon-bonded doloma
refractories perfectly meet these requirements. Figure 4 shows
different furnaces that are widely used in global secondary
stainless-steel making.
When it comes to applications in the steel industry
doloma refractories are also used because of their low oxygen
resupply to steel i.e. clean steel (CaO and MgO are both stable
oxides), their high stability under vacuum and in reducing
conditions, their compatibility to basic CaO rich low FeO
slags used for making steels with very low sulphur and oxygen
contents. However, doloma refractories have a low resistance
to acidic slags and are susceptible to spalling if thermally
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China’s Refractories

Fig. 4 Secondary stainless-steel production[1]

Modified after © RJ Choulet

cycled. Doloma as of today is preferred over fired magnesia

refractories because stainless steel refining uses highly
basic lime rich slags which in 90% of the cases have been
deoxidised (killed/reduced) using silicon. The solubility of
MgO in silica-based slags is high. This strongly favours using
fired doloma over fired magnesia-based refractory materials.
The primary requirement for slags in contact with doloma
refractories in order to reduce corrosion is that they are
saturated with respect to CaO. However, adding MgO causes
benefits to the refractories’ lifetime. Adding MgO lowers the
saturation point of CaO and reduces chemical erosion, because
it lowers CaO saturation levels on almost a one to one basis (up
to 17% MgO addition) (Fig. 5).
Alumina containing slags are difficult to handle with
respect to refractories when they fall into the range between
15%-25% Al 2O 3 since this is the region the amount of CaO
required for saturation rises sharply. The solubility of CaO in
Al2O3 slags is higher than that in silicate slags (for a similar
MgO content). After the slag is saturated with respect to CaO,
there is no intermediate high melting Ca-aluminate phase such Fig. 5 Effects of adding magnesia to doloma bricks—
as Ca2SiO4 or Ca3SiO5. The extent of slag penetration for alumina schematic view © RHI Magnesita

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 China’s Refractories
slags is among others like the wetting angle, the viscosity,
etc. also controlled by the thermal gradient of the brick. Al2O3
based slags tend to have lower viscosities than silicate-based
slags. When an alumina-based slag penetrates a doloma
refractory it will—as with silica-based slags—react with
brick inherent CaO and MgO of the matrix to become CaO and
MgO saturated (Fig. 6). Lowering the CaO saturation point
means that it is much easier and therefore likely that slags are
saturated with respect to CaO. Although increasing the MgO
Fig. 8 Coating formation of doloma bricks when exposed to
content up to 17% will progressively lower the CaO solubility,
slags © RHI Magnesita
most steel plants limit the MgO content to 12% because higher
levels will reduce the dissolved CaO in the slag to a point at When a silica-based slag penetrates doloma refractories,
which the slag’s sulphide capacity will be affected. it will initially react with the CaO and MgO-components of the
brick to become CaO and MgO saturated. The penetrated slag
will further react with CaO in the brick to form Ca2SiO4. As the
amount of Ca2SiO 4 in the slag increases the viscosity of the
slag increases so that the slag penetration stops. The thermal
gradient effect, in combination with the Ca2SiO4 precipitation,
limits the extent of slag penetration into the brick.
The performance of doloma can be increased by blending
it with MgO thus significantly improving on the bricks’ volume
stability i. e. reducing the bricks’ permanent shrinkage. The
addition also reduces cobble-stoning due to thermal cycling in
AOD-converter application, when the converter is empty (Fig. 9).
Fig. 6 Slag penetration in doloma bricks
© RHI Magnesita
In alumina-based slags the solubility of MgO decreases
and that of CaO increases. Adding MgO to dolomite bricks
therefore increases the corrosion resistance to alumina
containing slags (Fig. 7).

Fig. 9 Dilatation curve of a fired doloma brick compared to a

Fig. 7 Solubility of MgO and CaO in alumina slags [1]
The coating of doloma bricks in contact with different kinds
of slags is shown in Fig. 8.
MgO-enriched doloma brick
The addition of MgO typically ranges between 10% to a
maximum of 60% MgO depending on the CaO-content of the
raw material (total MgO content equals 75%). Above 75% MgO
addition it becomes impossible to retain the continuous matrix
of CaO (Fig. 10).

Fig. 10 Continuous matrix of CaO (light grey) depending on MgO (black) addition © RHI Magnesita

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China’s Refractories
The two areas in AODs suffering from highest wear load are
the tuyere and trunnion zones. For reducing wear in the tuyere
zones, steelmakers need to establish a good knurdle control
(mushroom) and ensure that the slag is compatible with the
refractory in order to minimise chemical wear. Consequently,
if the slag is not compatible with the refractory then tuyere
wear rates will be increased. No AOD has ever obtained low
tuyere wear rates when the slag chemistry was not compatible
with the lining regardless of how good the knurdle control
was. On all AODs similar to the tuyeres the trunnion area is a
high wear zone because the metal flow patterns created by the
Fig. 11 AOD process[10] © R. McVinnie/RHI Magnesita
Main applications of unshaped doloma products are
general loose fill applications, ladle backfill, bottom levelling,
block ramming, bottom joints, plug and well block (Fig. 12).
The bonding strength of unshaped doloma products develops
over heating (Fig. 13).
Fig. 12 Application of unshaped doloma products
©RHI Magnesita
2 Production of Doloma and Doloma Products
As doloma products are in high demand, the usage of
high quality doloma raw material as well as the application of
sophisticated processing methods for shaped and unshaped
doloma products is mandatory. Their manufacturing process is
described by the example of RHI Magnesita’s production site
Chizhou in Anhui Province, P. R. China.
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submerged side tuyeres preferentially drive the solid chrome
oxide saturated slag plus suspended metallic additions i. e. in
contact with the refractory walls at the trunnion. Additionally,
the trunnion represents the so-called slag cross point i. e.
whatever the position the AOD is rotated into the trunnion/slag
cross is always in contact with the slag. The most damaging
stage to the refractory is the first 1-2 min of the reduction
stage before the CaO has had chance to neutralize the SiO 2
and Al2O3 generated. Figure 11 shows the AOD process in a
schematic way.
2.1 Mine
The dolomite mine has about 60 million tons of dolomite
reserve left (Fig. 14). In general, quarrying of any mineral
requires an understanding of the spatial distribution and
chemical composition. This is obtained by creating a chemical
block model based on drillings in predefined grids and depths.
Fig. 13 Bonding strength development of unshaped doloma
products
Based on average chemical analysis results a potential
mineral composition after firing of the dolomite was obtained
by also considering the fuel ash that is adding components
to the future doloma sinter. It was taken into consideration
that impurities like alumina, iron oxide and silica react with
lime to tricalciumsilicate (3CaO · SiO2), tricalciumaluminate
(3CaO · Al 2O 3), brownmillerite (4CaO · Al 2O 3 · Fe 2O 3), and
dicalciumferrite (2CaO · Fe2O3).
 China’s Refractories
properties as compared to the raw material used in former
times. This gives additional benefits for hydration resistance,
firing shrinkage and product performance.
The rotary kiln is fed with crushed and sieved pure raw
dolomite for firing. The calcination of raw dolomite starts
at about 400 °C and is mostly completed at around 850 °C
from which on its sintering begins. In dependence of its
natural chemical composition and added flux agents sintering
temperatures of above 1 800 °C are required to obtain grain
densities of greater 3.20 g · cm-3.
Due to high purity levels of the available raw dolomite
reserve, top-grade sintered doloma was obtained after firing
in the rotary kiln (Fig. 15). The sintering of dolomite resulted
in the evolution of material in terms of its density, reduced
porosity under thermal effect, accompanied by an increase of
crystal size. The below micrograph of elemental distribution
shows low accounts of impurities within the sintered doloma
matrix (Fig. 16).

Fig. 14 Dolomite mine reserve in Anhui Province, P. R.

China © RHI Magnesita
2.2 Sintered Doloma Production
While in the past, the raw stone from the dolomite mine
was fired in a sophisticated and rather expensive two-step
firing process, the main target for the new raw material plant
was to use a one-step rotary kiln process. Fig. 15 Sinter plant in Anhui Province, P. R. China
In general, the sintering of doloma is difficult due to low © RHI Magnesita
diffusion coefficients of Ca2+ in MgO and Mg2+ in CaO (low
mobility) and the high sinter porosity after decomposition.
Impurities as shown below may help for sintering as they build
up liquid phase as can be derived from the oxide melting
points in Table 1.
Table 1 Oxide melting points of mineral phases
Mineral phase Formula Melting point/℃
Periclase MgO 2 820
Lime CaO 2 630
Tricalcium silicate 3CaO · SiO2 2 120
Tricalcium aluminate 3CaO · Al2O3 1 535
Dicalcium ferrite 2CaO · Fe2O3 1 445
Brownmillerite 4CaO · Al2O3 · Fe2O3 1 385
Fig. 16 Microscopic view of sintered doloma from Chizhou
plant (CaO (lime): light, MgO (periclase): dark)
Laboratory tests were initiated in order to get a basic
© RHI Magnesita
understanding of decarbonisation, decrepitation, influences of
flux and ash as well as overall sinter ability of the raw stone. With the new optimized process route an average grain
Preceded by these lab trials, three industrial firing trials with density of 3.25 g · cm-3 in relation to the former raw material
several thousand tons of raw dolomite were performed in with an average density of 3.15 g · cm-3 was reached.
different rotary kilns around the world employing different 2.3 Doloma Products-binder Types
parameters and fuel types. After kiln start-up and continuous Generally, binders used for all types of doloma-based
optimization of the kiln parameters the resulting sintered products need to be water-free or have a very low water content.
doloma was found to have significantly improved physical Binders for fired doloma bricks contain refined paraffins and wax

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China’s Refractories
plus additives. These binders can be regarded as the most critical peratures between 250 and 300 °C. Once the set temperature
ones due to complex firing processes and large mold sizes. of the kiln is reached, it is held there for a specified amount of
The duration and type of complete binder burn-out is crucial for time for enabling hardening and stabilization reactions. The exact
preventing hydration-, binder- and firing cracks. temperature and time depend on several factors such as the type
For making tempered, C-bonded bricks phenol-formaldehyde of brick/binder and its desired mechanical properties.
resins (e. g. Novolacs plus hardener, resole-type) and synthetic
pitch (derived from coal tar pitch or petroleum and used in hot
mixing process) are being applied. Novolacs are the binder of
choice in unfired doloma bricks as they have a low water content
but need a solvent. Resins in tempered brick production contain
about <3% water.
For mixes, mineral oils, resins and plasticising additives
(plastic mixes) are used. These binders act as sintering and
suspension aid as well as viscosity adjustment tool.
The purpose of binders is to keep components in shape and
hydration at minimum, prevent dust formation and demixing.
They should also yield high carbon residues (unfired bricks) and
supply enough green brick strength, make the mix plastic, hence
facilitate pressing. Requirements for the C-containing bonding
system are good adhesion between ceramic components Fig. 17 Hydraulic press (quadruple cavity)
and carbon carriers, high green strength and protection from © RHI Magnesita
hydration, high strength after tempering, low apparent porosity
after coking and high carbon yield.
2.4 Mixing
Mixing is an important area of the production process for
both fired and resin bonded, tempered doloma production. As
doloma is prone to hydration when in contact with air it is very
important that the grains and fines are all coated with binder to
avoid hydration issues later in the production process. This is
especially the case when humid months of the year coincide
with the high temperatures. High intensity mixers are most
suitable for doloma brick production. Mixing can be affected
Fig. 18 Cross-section of unfired, resin-bonded brick brand
by a variety of variables such as temperature, size of particles, © RHI Magnesita
viscosity of liquid binder, length of dry and wet mixing time and
the sequence in which the materials are added to the mixer. 2.7 Tunnel Kiln
Firing curves of the tunnel kiln in dependence of different
During mixing, friction is generated by the movement of the
products need to be very strictly adhered to. The decomposition
particles against each other and against the steel parts of the
of Ca(OH)2 occurs at 512 °C. This is an important temperature
mixer. This friction causes the temperature of the materials to
rise and the temperature will rise the most during dry mixing. as ambient water is met by water as a by-product of natural gas
Wet mixing generally ensures that all particles are coated combustion.
although the length of time during this operation can vary due to
the type and properties of the materials being used. Conversely,
shortened mixing time will tend of lead to uncoated grains in the
mix and additives may not be evenly distributed and the batches
will appear dry and can result in hydration issues as well as
weak corners and edges on the bricks. It is quite important to
ensure that target temperatures of mixing are achieved, and the
mixing sequence is strictly followed up on.
2.5 Pressing Fig. 19 Tunnel kiln in Chizhou brick plant
In plant Chizhou several hydraulic presses of different sizes ©RHI Magnesita
are in operation and ensure that press density specifications The own doloma sinter is used to manufacture fired
and brick integrity requirements are met (corners and edges). a n d u n f i re d b r i c k s t h a t m e e t i n t e r n a l a n d c u s t o m e r
2.6 Tempering Kiln specifications. The addition of fused doloma and/or magnesia
The tempering of C-bonded bricks is performed at tem- was significantly reducing the shrinkage at high operating
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temperatures. Larger crystal size of fused components with a
higher mass to surface area ratio increased the resistance to
both chemical corrosion and mechanical erosion. High firing
of bricks resulted in a denser, lower porosity product that
had better ceramic bonding and improved volume stability,
resistance to slag penetration, and elevated the brick’s hot
strength.
Fig. 20 Cross-section of fired doloma brick
© RHI Magnesita
2.8 Unloading and Packing
For unloading kiln cars with fired bricks there are three
automated arms plus manual unloading available. Additionally,
a dry room with climate control ensures minimum hydration
risk for doloma products as well as vacuum package.
2.9 Unshaped Doloma Products
The mix portfolio comprises dolorams, rams, slabs,
plastics, mortars and seals. Their flow behaviour is governed by
adjustments of the level and kind of added liquid and binder. In
general, ram/plastics possess large particle and mortar/seals
small particle sizes.
In general, the manufacturing plant has put in place a strict
regime of taking care about all sorts of waste. Waste avoiding
also means reducing raw material and product contamination,
binder agglomeration, hydration, rough edges, segregation,
brick bulging, lamination, cracks (shaled, setter and fired
cracks), bending, deformation and underfiring.
3 Conclusions
There is essential need for doloma based products to produce
high quality steel grades. This requires doloma raw materials
and products out of them produced according to cutting-edge
technologies. Therefore, a modern sinter and brick plant for
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China’s Refractories
manufacturing high-quality doloma sinter and sophisticated
shaped and unshaped doloma products is essential. RHI
Magnesita has significantly invested into a facility in Chizhou,
Anhui Province, P. R. China which is described as example.
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Received in Sept., 2020
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