Acer Paper
Acer Paper
Acer Paper
Jens Decker, Tom Atkins, David Mintz – Stellar Materials, Boca Raton, USA
Karel Hoeksma, Roy Ovink – Corus Research, IJmuiden, The Netherlands
1. Introduction
Major industrial processes require combustion in different forms. The burner is the
device that is used to combust fuels with an oxidizer and to control the heat transfer into
a furnace in which these processes take place. An essential part of a burner is the
refractory burner tile either made of ceramic fiber or refractory pre-fabricated shapes.
A burner tile is a complex functional refractory product and inaccurate operation can
cause downtime costs which exceeds the costs for the burner equipment by far.
Environmental aspects and more stringent regulations have changed the philosophy of
burner design in the last 20 years. Burner design is now a compromise between
efficient mixing of fuel and oxidizer and the necessity to reduce the total fuel
consumption and pollutant emissions, which requires moderate low flame temperatures
in order to reduce NOx. These designs have led to the development of tailor made
solutions for certain applications and to highly sophisticated burner designs with tiles of
complex shapes. (Picture 1).
This paper discusses the technical requirements of refractory materials for burner tile
applications and evaluation methods in order to generate thermo- mechanical data as an
engineering tool for the design of burner tiles. Furthermore the influence of two different
binder systems will be described in this context.
Regarding the burner design, the combustion engineer has to consider the characteristic
of the ceramic burner tile material in order to obtain stable combustion process
conditions.
Picture 1.0 shows a low emission flat flame burner of complicated tile shape with sharp
edges and additional fuel jets in order to reduce NOx. The purpose of the geometry is to
control a precise oxidizing process of the fuel (1) The wall thickness is not uniform and
the jets probably keep parts of the tile cold. This is an example for a burner with a critical
tile design.
3. Specific evaluation and testing criteria of refractory materials for burner tiles.
Material testing should also reflect the different dynamic temperature stages to
determine suitable materials. A burner tile is exposed to one or more temperature cycles
during the lifetime. A temperature cycle can be divided in different stages which are
important for the material requirements. These are:
a.) Heat up b.) Steady heat flow at operating temperature c) Thermal cycling
caused by burner control and operation d.) Cool-down.
Hence the temperature dependent stress – strain behavior of the refractory material
must be defined.
The ISO standard 13705 specifies the required chemical composition of burner tiles for
certain applications:
Table 1 shows as an example the chemical analysis of a sample taken from a burner tile
of an oil fired ship boiler burner. The tile failed after 6 months in operation because of
surface spalling after cool down. The table shows the quantity of impurities picked-up
during operation.
Table 1
V2O5 + 2,7%
NiO + 2,0%
Na2O + 1,3%
The mineral composition also plays an important role in the internal thermo-chemical
and mineralogical reactions. A high mullite content is favorable for good thermal shock
properties due to the low reversible expansion. The alkali and alkali earth metal oxide
content has an influence on the modulus of elasticity, the resulting thermal shock
properties and phase transitions that lead to stresses due to expansion or shrinkage.
Furthermore a long term attack occurs from particles of combustion air. Silica and alkali
containing particles melt in the flame, and due to recirculation of combustion products,
attack the tile. Due to this, burner tiles can show severe surface cracking after years in
service.
3.3. Thermomechanical Considerations
During high temperature service, burner tiles are required to conduct heat and they may
be subjected to rapid temperature variations. This takes place during adjustments of the
burner, fuel changes and shut down conditions when cooling down and heating up the
burner again. The non-linear temperature gradient during rapid heat up and cool down
develops thermal stresses or thermal expansion forces that may fracture the refractory.
The refractory structure should resist tensile and compressive strains through a wide
temperature range from a rigid solid state at low temperatures to a more viscous state at
high temperatures. Cracking from these stresses can have an impact on the flame
pattern and in a worst case scenario cause the flame to be in contact with the tile
causing problems like hot spots and total destruction of the tile and burner casing.(2)
R1 = (1- ) / ( E)
A rapid thermal shock leads to thermal gradient on the surface of a material. R1 is the
maximum allowable temperature difference in body under conditions of steady heat flow.
( T in °K)
R2 = R1
Considering a constant heat transfer on the surface - R2 is the maximum allowable heat
flux through body under conditions of steady heat flow (W/m)
R3 = R1 a
R3 is the maximum allowable rate of surface heating.
= tensile strengths
= Poisson ratio (transversal contraction index)
= linear thermal expansion
E = Young’s modulus (static: determined as V-modulus)
= thermal conductivity
a = / (cp ) = thermal diffusivity
Based on the stress parameter, an ideal thermal shock resistant material should
possess the following thermo-mechanical properties:
- low thermal expansion
- high thermal conductivity
- high strengths under consideration of the stress/strain relationship. (A high / E
ratio leads to good thermal shock properties)
Castable materials have been traditionally used for burner tiles because of the
advantage in minimizing costs when manufacturing complex shapes of limited quantities.
Placement of castables, when compared to pressed- or rammed products, is easier and
the bodies show a more isotropic structure which is advantageous in relation to thermal
shock properties.
One difference between fired products and castable refractories is the higher shrinkage
of castables at elevated temperatures which affects the geometry of the body at service
temperature. Thus the interaction between permanent linear change and thermal
expansion needs to be considered as an important factor for the design of burner tiles.
High alumina cement CA, CA2, C12A7 etc.) +additives + water calcium aluminate
hydrates (CAH10, C3AH6, C2AH8, etc.) +additives + water + heat + residual water. (9)
Due to the high quantity of water and the low permeability of cement bonded materials, a
rapid temperature increase may result in explosive spalling or steam explosion. Factors
that can contribute to explosive spalling include curing conditions, heating and dry-out
method, and physical properties of the material (10). Due to these factors pre-cast
burner tiles require accurate dry out or pre-firing before the installation.
- heat setting
- cold setting + setting additive
- one component dry material with water addition
- two component mix with phosphoric acid solution or monoaluminium phosphate
solution + dry component
The chemical compositions of cold setting phosphate bonded castables are based on
the system Al2O3-SiO2-P2O5-MxO (MxO is alkali- or alkali earth oxide). Heat setting
phosphate bonded castables are based on the system Al2O3-SiO2-P2O5. The P2O5
content ranges from approximately 3% – 6% and the MxO content from approximately
0.5% - 6%.
A great number of works have been reported about the reaction between alumina and
phosphoric acid (12,13,14) Alumina reacts with phosphoric acid above 127°C (260°F) to
aluminium phosphate and shows considerable strengths above 350°C (660°F). The
most often applied phosphate binder in the refractory industry is mono-
aluminiumphosphate (MAP) in liquid or spray-dried form.
If setting properties at ambient temperature are desired an additional setting agent is
needed. This can be an alkali- or alkali earth metal oxide component (MxO) like sodium,
magnesia, calcium or compounds thereof.
The disadvantage of a spray dried MAP additive in a single component material is the
poor shelf life due to the strong hygroscopic behavior. Alternatively, phosphoric acid can
be used as a liquid in a two component product. Depending on the reactivity both MAP
and phosphoric acid need to be diluted to slow down the exothermic reactions.
Phosphoric acid is a tri-basic acid and reacts with different metal oxides to form salts.
Some of these salts function as a refractory binder. In an aqueous solution the
phosphoric acid reacts in three stages according the molar ratio MxO / P2O5 of 1:1, 2:1 or
3:1.
Table 2 shows as an example the reactions between magnesia and phosphoric acid and
the resulting three different stages. Magnesia and magnesium hydroxide are widely used
as setting additives for phosphate containing formulations. The reaction type 1 and type
2 are exothermic. However, reaction 1 is much stronger than 2 whereas reaction 3
doesn’t show cold setting properties.
Table 2.
The phosphates being formed at ambient show dehydration of chemically bonded water
at elevated temperatures. This condensation process is described in Table 3.
Table 3.
Phosphate bonded products with a binder system of a two component mono- and a
single component di- phosphate are commercially available. The advantage of a two
component mono- phosphate bond is the faster setting and faster heat up time.
Flame impingement experiments with both kinds of materials have shown that mono-
phosphates are less susceptible to explosive spalling than di- phosphate bonded
materials.
Possible explanations for this are:
- The mono-phosphate formation is highly exothermic, which cause dehydration
during setting.
- The quantity of chemically combined water in the mono- phosphate is higher than
in di- phosphates. This can have an influence on the steam pressure in the
capillary system of the material during bake out.
- The water in mono-phosphate evaporates at 150 C with max 5 bar steam
pressure. For di- phosphate the water is released at 213 C and the steam
pressure of 20 bars may exceed the strength of the material.
- Two component products use a molar excess of H3PO4 compared to MxO. The
vapor pressure of phosphoric acid and monoaluminium-phosphate solutions are
lower than water. Thus, they are less explosive than other (water containing)
castable refractories during heat up (15)
It should be noted that the whole dehydration process of phosphate bonded castable
refractories hasn’t been properly evaluated yet.
Above 900°C (1650ºF) first melting of the MxO- phosphate compounds of the binder
system occurs. Depending on the raw materials, heat setting phosphate bonded
materials behave similar because of a reaction of phosphates with MxO impurities. Thus,
phosphate bonded castables with alkali additions can show lower hot modulus of rupture
and refractoriness under load numbers compared to cement formulations. Depending on
the quantity and kind of alkali additive, this melt phase is of a temporary nature and
further reacts with alumina to melts of higher viscosity. In many burner tile applications a
certain quantity of melt phase at service temperature reduces the stiffness of the
material and improves the thermal shock properties, which is desired.
Between 900°C (1650ºF) and 1600°C (2900ºF) amorphous phosphates and phosphate
melts are being formed. Depending on the kind of MxO- phosphate and quantity thereof,
occurring melts can attack the aggregates of the raw materials at process temperatures
above 1350°C (2460ºF). Resulting volume changes are due to the formation of
additional melt (shrinkage) or formation of new compounds like Mg-spinel and mullite
(expansion). Above 1600°C (2900°F)aluminium-phosphate starts to decompose to
aluminium-oxide and P205 which is volatile at this stage.
There is some evidence that occurring phosphate melts are temporary in nature and
change at increased temperatures to different compounds. Some test methods,
however, do not reflect this materials characteristic. Critical tests are:
The results obtained from these tests can be significantly influenced by the occurring
melt phase at test temperature. For instance samples pre fired at 1100°C (2000°F) with
a holding time of 24 hours showed 10% HotMOR increase and with a holding time of
168 hours an increase of 65% at 1100°C (2000°F). Typically, published data references
test results after only a five hour holding time.
Another example is thermal expansion under load. Due to the load, plastic flow and the
coefficient of thermal expansion are mixed and resulting high permanent linear change is
then overstated.
The next example shows the conversion from calcium phosphate to Anorthit.
This reaction is evident from XRD analysis. Calcium-monophosphate as part of the
binder component is being formed at ambient temperatures by the reaction of
phosphoric acid and calcium oxide. During heat up this monophosphate converts into
calcium - metaphosphate as shown in Table 3. Calcium metaphosphate has a melting
point of 975°C (1800°F).
After firing at 1600°C (2900°F) with 10hours holding time the XRD diagram (Figure 1)
shows that all phosphate has been converted to AlPO4. Calcium oxide on the other
hand has been reacted with mullite and converted into Anorthite with a melting point of
1550°C (2800°F)
Figure 1 XRD analysis Formula 6B – 1600 C/10h (2900°F)
5. Numerical studies
Comparative FEM analysis of two burner tiles made of commercially available cement
bonded- and phosphate bonded castables have been conducted in order to determine
the thermo-mechanical behavior of the different materials during the critical heat up. The
tile used for the modeling is a burner tile of an annealing furnace.
A heat up was considered on this axi-symmetric burner tile as indicated in Figure 2.The
thermal boundary conditions are indicated in Figure 3. A heat up time of 48 hours was
considered.
Figure 2 The axi-symmetric burner geometry.
Andalusite Phosphate
HS Bonded SB
Density 2450 kg/m3 2360 kg/m3
Thermal expansion 6.6e-6 K-1 5.5e-6 K-1
Thermal conductivity 1.4 W/mK 1.7 W/mK
Specific heat 1000 J/kgK 1015 J/kgK
Poisson's ratio 0.3 0.3
Table 6. The temperature dependent yield stress under tensile loading conditions for LCC Andalusite HS.
Table 7 The temperature dependent yield stress under tensile loading conditions for Phosphate bonded SB
Figure 4 Temperature contours after one hour of heat up (°K). A displacement-scaling factor of 50 was used.
Figure 5 Calculated stresses in circumferential direction (Pa)
Figure 6 Calculated plastic strain in circumferential direction (non reversible strain, Epsilon
6. 2 FEM analysis for the Phosphate bonded SB
From this simulation it turned out that no damage occurred within the first hour of heat
up. Figure 7 shows the calculated temperature profile after one hour of heat-up. Figure
8 gives the calculated stresses in the circumferential direction. Compared to Figure 5
the stresses are lower than the yield stress stated in table 6.
Figure 7 Temperature contours after one hour of heat up. A displacement-scaling factor of 50 was used.
Figure 8 Calculated stresses in circumferential direction.
The calculations of the “Hasselmann thermal stress resistance parameters R1-R3” are
shown in Table 8 and 9.
In the critical temperature range up to 850°C (1560°F) R1, R2 and R3 of Phosphate
bonded SB shows better numbers compared to Andalusite HS. Basically this is a
confirmation of the results from FEM analysis and means the phosphate bonded
material allows a higher temperature change; heat flux and temperature increase at the
surface without exceeding the failure stress compared to the cement bonded material.
However, a material ranking based on these results is difficult because above 1100°C
(2000°F) both materials form melted phases and show plastic behavior. Hasselmann
assumes only elastic properties.
Hence the quality of a material choice based on thermal stress resistance parameter
calculations would increase with the data base and comparative FEM analysis.
Conclusion
Comparative FEM analysis of a burner tile made of low cement bonded andalusite and a
phosphate bonded castable have been conducted.
Under given thermal boundary conditions it is likely that the cement bonded material
would show cracking because the calculated stresses (Figure 5) are close to the yield
stress limit (Table 6). It can be concluded that improved properties can be achieved by
using a cement bonded castable of higher cement content in order to lower the stiffness
in this temperature range.
The results of the phosphate bonded material “SB” show a lower V-modulus, higher
thermal conductivity and a lower coefficient of thermal expansion compared to the low
cement bonded andalusite material. The determining low V- modulus is characteristic for
phosphate bonded material and can be explained with the formation of poly- and meta -
phosphate compounds during the condensation process which leads to flexible ring- and
chain structure with a stability up to 800°C (1500 ºF).
Due to this and the properties explained under 4.2.1 mono-phosphate bonded materials
do not require dry-out and therefore it is possible to manufacture burner tiles “just in
time” with an installation right after setting.
Although this FEM analysis is only focused on the heat up process of the tile it shows
the material behavior at a very critical state of the temperature cycle. This is confirmed
by calculations of the thermal stress resistance parameters R1-R3 which show different
results of the two test materials in this temperature range.
Both FEM analysis and the calculation of stress parameter are practicable tools for
materials ranking. A ranking based on stress parameter calculations however depends
on a comprehensive data base. Traditional material testing procedures have shown to
be inaccurate predictors of the performance of phosphate bonded materials in this
application. One has to consider that tests under load conditions show results which are
probably influenced by temporary melt phases with lower viscosity and plastic flow.
Therefore it is recommended to compare results achieved by using varied and extended
holding times.
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