ESTIMATION OF THE IMPACT OF

10-100% H2 ADMIXTURES IN
NATURAL GAS FUEL ON THE
LIFETIME OF INDUSTRIAL KILNS
Thierry POIRIER (*), Lucio TADDEO
CETIAT, 25 rue des Arts, BP 52042, 69603 VILLEURBANNE, France, [email protected]

Stéphane HODY
GRDF, Direction Prospective et Expertise Usages, 6 rue Condorcet, 75009 Paris, France,
[email protected]
(*)
presenting author

Abstract
Hydrogen (H2) is a possible solution for industrial end users that use natural gas as a fuel, helping
to reduce their carbon footprint. However, many of them only consider it as a medium or long-term
solution, for many of them worry about the practical consequences of the use of hydrogen on the
characteristics of their final products and on the lifetime of their equipment, particularly the kilns. As a
matter of fact, industrial kilns renovating or upgrading is generally realized every 5 to 20 years depending
on the process and on the material which has to be fired, and this operation comes at a very significant
cost. Thus, this time lapse and the lack of fully documented information make some end users
contemplate adding hydrogen only after 2030-35 in their decarbonating roadmaps. However, some
answers could be given earlier to the following question: « Does an addition of 10-20% vol. H2 to natural
gas, or even its complete replacement with H2, enhance the attack mechanisms on refractory
materials? ». Some end users and their refractory providers are working to determine or confirm what
could happen, at laboratory scale or at a semi-industrial demonstrator scale. While these recent studies
are being implemented, the objective of this paper is to give practical perspective for the end users, based
on some recent experimental feedback and scientific literature. The main attack mechanisms are studied
on up to 11 refractory material categories, taking into account several industries and their respective
kilns, such as metallurgy, cement, ceramics, tile and bricks, and glass industry. Because of the different
exhaust gas composition and flow rate (iso-energy configuration), both hydrogen air-combustion and oxy-
combustion are taken into account. Moreover, some typical anomalies that may occur in the lifetime of a
natural gas kiln are considered, to determine whether adding hydrogen might increase the respective
damage or not. Results suggest little or no increase in the reduction issues that commonly take place
with small air factors (damage by Boudouard reaction, creeping by iron oxide reduction, necrosis of
oxides), whereas the effect of higher water amount in the combustion products should be a point of
vigilance in some industrial kilns, particularly in the glass industry.

@igrc2024 IGRC2024 igrc2024.org

 1. Introduction: the good question about hydrogen as a fuel
Many European industries have established ambitious carbon neutrality targets. The first step (until
2030) involves high yield readily options, such as improving the thermal efficiency, waste heat recovery,
using biogas and renewable energies, decarbonated raw materials (ex: cullet in glasses), among others.
The second stage (2030-2050) includes hydrogen as a fuel resource. This stage was postponed by many
industrials because the availability of green hydrogen raised questions, as well as the involved cost and
readiness of suitable burners, skids and sensors. At the same time, the offer of completely equipped
furnaces with hydrogen burners remains relatively confidential. Moreover, the ability to produce the very
same products with a different fuel was to be confirmed. Thus, several companies have chosen a wait-
and-see position. For other companies, such as some glass producers, an active planification consisted
in synchronizing the time for kiln revamping or replacement (the lifespan of many industrial furnaces is
5-20 years) with the decision of partial or complete switching to hydrogen and/or hybrid solutions.
Meanwhile, several tests have already started with hydrogen as a fuel, at laboratory or industrial
scale, such as in steelmaking and aluminum melting (ladle preheating, scrap melting, reheating: VON
SCHEELE, 2022), glass melting (MILLS, 2023 a,b,c; MORRIS 2022) or tiles and bricks firing (COUSINS,
2022), with temporary (5-10 days) or permanent additions of 10-100% hydrogen. These experiments led
by Linde, NSG Pilkington, Saverglass, Maison Française du Verre, Schott, among others, successfully
allowed to confirm that, with a few adjustments, the quality of the products would be maintained. Thus, a
first fundamental question is being answered and, since 2022, the number of industrial demonstrators
has been significantly increasing.
However, one crucial question goes unnoticed: the impact of using hydrogen on the behavior of
refractory materials, and subsequently, on the lifespan of the kilns.
During their lifespan, the linings, crown, superstructures, bottom, burners, chimney and other parts
of a kiln are more or less prone to react with the ambient atmosphere and with solid/liquid materials during
firing. Thermochemical, physical and kinetic phenomena give place to several kinds of damage to the
refractory parts, depending on the working conditions and on the quality of those refractories
(microstructure, impurities).
Indeed, the attack on refractories already exists in any kiln that uses natural gas (NG) with air or
oxygen as a comburant. Therefore, the good question for industrials would be now: « Would an addition
of 10-100% vol. H2 to natural gas enhance the attack mechanisms on refractory materials? »

2. Method to answer the good question about kiln lifespan

A first study was undertaken by the French gas distribution system operator GRDF in 2021-22 with
the hypothesis of adding 2-20% H2 to the natural gas grid. A second study (2023), still sponsored by
GRDF, considered the hypothesis of 100% H2, both in air-gas and oxy-gas combustion cases, trying to
maintain the same firing power with 100%H2. The approach consisted in (1) Estimating the atmosphere
with added hydrogen, using the GasEq® software for equilibrium calculations and comparing the H2/H2O
and CO/CO2 ratios (effect on the reduction of ceramic oxides) between NG and NG-H2 blends.
(2) Synthetizing the scientific literature review. (3) Collecting the feedback from several laboratories and
over 20 kiln builders, end users and refractory manufacturers. (4) Considering several mechanisms of
attack, industrial applications, as well as refractory materials: (a) silica, (b) fireclay/low alumina and low
bio-persistence fibers, (c) cordierite (kiln furnitures), (d) mullite/andalousite, (e) high alumina, (f) zirconia
derived products, (g) SiC/SiAlON, (h) forsterite/spinel products, (i) MgO and (j) doloma products, (k)
refractory cements. (5) Considering their use in specific parts of the furnaces (6) Attributing qualitative
color scores (fig. 1) to the identified risk supplement when adding hydrogen, with respect to using pure
NG.

(FMECA) severity / likelihood of additional risks for refractories when adding H2

clear and short-term increased risk of damage
Air-gas
low likelihood and severity, possible risk on the long term
Oxy-gas no additional risk of damage

Fig. 1: Assessment scale of additional risks for refractories when partial or total replacing of NG with H2

3. Evolution of the kiln atmosphere when adding H2

The atmosphere within the kilns is estimated as %H2 increases in several cases. Fig.2 suggests that the
amount of water vapor increases by 84% in air-gas blends and 50% in oxy-gas, for oxidant atmospheres.
Those changes are quite significant and make it useful to study the impact on refractory lifespan.
However, it is to note that the “air-gas to air-H2” transition would imply less increase in water vapor than
the “air-gas to oxy-gas” transition that has already taken place in many furnaces, such as in glass
industry. This implied refractory adaptations that gave interesting information for the present study.
Reducing atmospheres may take place in industrial furnaces, by technical design or by malfunction of a
burner. In such cases, fig. 3 suggests that the H2/H2O and CO/CO2 ratios should not significantly change.
This means, based on Ellingham thermochemical equilibrium diagrams, that the oxides within the
refractories should be reduced the same way in NG blends as when H2 is added, both in air and oxy
combustion. In the case of malfunctioning burners, the atmosphere still maintains at least 10% H2O,
which limits the reducing trend of unburnt hydrogen or NG (CARPENTIER, 2022).
It is to note that to obtain the same firing power, the flow rate of H2 must be 3.3 times larger than NG and
that, considering air-gas combustion, this will lead to a decrease of flue gas by 15%, whereas an increase
by 10% will take place in oxy-combustion (NICICKY, 2023).

AIR-GAS COMBUSTION (λ=1,10) OXY-GAS COMBUSTION (λ=1,03)

CO2 H2O N2 O2 CO2 H2O N2 O2

0 8,71 17,43 72,12 1,74 0 32,68 65,36 0,00

1,96

10 8,46 17,86 71,95 1,74 10 31,52 66,54 0,00

1,94

20 8,16 18,36 71,75 1,73 20 30,18 67,90 0,00

1,92
H2 CONTENT (%)
H2 CONTENT (%)

30 7,80 18,95 71,51 1,73 30 28,61 69,49 0,00

1,90

40 7,38 19,67 71,24 1,72 40 26,76 71,36 0,00

1,87

50 6,85 20,55 70,88 1,71 50 24,54 73,62 0,00

1,84

60 6,19 21,67 70,44 1,70 60 21,82 76,36 0,00

1,80

70 5,33 23,11 69,87 1,69 70 18,42 79,83 0,00

1,75

80 4,17 25,05 69,11 1,67 80 14,04 84,27 0,00

1,69

90 2,53 27,81 68,01 1,64 90 8,20 90,20 0,00

1,60

100 0,00 32,06 66,34 1,60 100 0,00 98,52 0,00

1,48

FLUE GAS CONTENT (%) FLUE GAS CONTENT (%)

Fig. 2: evolution of the flue gas as the H2 content increases. %H2O increases from 17.43 to 32.06%
(+84%) in air-gas and from 65.36 to 98.52% (+50%) in oxy-gas when 100%H2 is used (NICICKY, 2023)
 H2/H2O & CO/CO2 in air-gas blends H2/H2O & CO/CO2 in oxy-gas blends
3,0
3,0
H2/H2O in NG-air H2/H2O in NG/O2
2,5
H2/H2O in NG+20%H2-air 2,5
H2/H2O in H2-O2

H2/H2O & CO/CO2

CO/CO2 in NG-air
H2/H2O & CO/CO2

2,0 2,0 CO/CO2 in NG/O2

CO/CO2 in NG+20%H2-air
CO/CO2 in H2-O2
1,5 1,5

1,0 1,0

0,5
0,5

0,0
0,0 0,6 0,7 0,8 0,9 1 1,1 1,2 1,3
0,6 0,7 0,8 0,9 1 1,1 1,2 1,3 air factor : λ
air factor λ

Fig. 3: evolution of the H2/H2O and CO/CO2 ratios at several air factors (λ) in (a) 100%NG vs
NG+20%H2 air blends and (b) oxy-gas with 100%NG and 100%H2. The reducing trend does not
change at low %H2. Pure H2-O2 blends do not produce significant changes in the reducing behavior

4. Hydrogen and refractory damage under reducing conditions

Boudouard reaction: the attack on refractories may occur in reducing atmosphere in presence of iron
oxide that catalyzes the following reaction within the pores of refractory linings: 2CO  C + CO2 (400-
1000°C). Hard carbon is produced and produces cracks. It happens within the thickness of linings, even
if the inner kiln temperature is higher than 1000°C. H2 amplifies this effect, giving a more aggressive,
worm-like microstructure to hard carbon (Fig. 4), which increases the damage (BOST, 2016a). Thus,
H2+NG could generate more damage while CO is present. This sometimes occurs in cowpers
(steelmaking), although small amounts of NG are used and H2 is already present. Thus, the
manufacturers already have implemented ASTM C288 standard-compliant refractories with low free iron
content (KRAUSE, 2007) that could resist a modified fuel on medium-term. When pure H2 is used as a
fuel, no carbon gives place to this reaction. In coke ovens, traces of sulphur stop the Boudouard reaction
(KADOK, 2016).

Boudouard
reaction

Cowpers
in NG-H2

Coke ovens,
all cases with
100%H2

Fig. 4: hard carbon production (Boudouard) may destroy more refractory concrete (KADOK, 2016) and
porous bricks with more free iron oxide and H2, unless sulphur is present (BOST, 2016b)
Iron Oxide melting by reduction: iron oxide in refractories is present in small amounts (<1%), albeit
sometimes locally concentrated in ceramic grain boundaries, which lowers their melting point by 200-
400°C if Fe2O3 is reduced to FeO. A malfunctioning burner may expose chamotte bricks to accidental
creeping (fig.5). However, fig.3 shows that H2/H2O and CO/CO2 ratios should not change enough to justify
a higher reduction of iron oxide when H2 is added.

Melting by Necrosis by
reduction of reduction
Fe2O3 of oxides
Normal state
(oxidant atm.) Melted aspect
all cases all cases
(reducing atm.)

Fig. 5: example of melting by accidental reducing iron oxides within a chamotte brick
(Courtesy : INISMA-CRIBC)
Necrosis by oxide volatilization under reduction: a well-known phenomenon under reduction is the
reaction SiO2 + H2 SiO(gas) + H2O(gas) . It is quite dangerous for refractories where H2 is used as a
reactant (DRI, bright annealing), since a part of the linings is volatilized (necrosis), although other oxides
such as Al2O3 are less reducible (RIBEIRO, 2024). With H2 as a fuel, the produced H2O hinders this
reaction and the H2/H2O ratio remains very low, even with pure and partially unburnt H2 (fig.3,
CARPENTIER, 2022). This protects the refractories against the necrosis by reduction (HERBELL, 1990).

5. What about water?

Water vapor: The more H2, the more H2O vapor which creates a volatilization reaction in the refractories:
RxOy + m H2O (gas)  x RO(OH)2m (gas) with R= Si, Al, Mg, Zr, etc… The risk is irrelevant in NG-
20%H2 blends (fig.2: +1-2% H2O). However, pure H2 yields much more H2O and volatilization (RO(OH)2m
gas pressure: atm; or recession rate Kw : µg/cm2/h), particularly with hotter, faster oxy-fuel fumes.

(a: constant, E: Activation Energy, T: temperature, v: flow velocity, pH2O : partial pressure, Ptotal : atmospheric pressure, n: 1-2)

This phenomenon is more significant with SiO2 bearing products (fig 6a): in Air-NG, a slow reaction
SiO2 + H2O  SiO(OH)2(gas) begins at 1330°C. In oxy-H2, the medium-term attack starts 150°C lower
(50°C with air-H2), but short-term attack would take place above 1500-1600°C. SiC burners have a thin
SiO2 protective layer that goes off in those same conditions, making them a point of vigilance in oxy-H2.
The less silica, less problem: classical alkaline-earth Low Bio-Persistence (LBP) silicate fibers (> 70%
SiO2) would earn a red score, whereas high temperature LBP fibers (< 33% SiO2, with Al2O3, ZrO2) would
resist much more. Class 23 bricks (45% SiO2) in the preheating zone (<1200°C) of lime furnaces could
be upgraded to class 26 (39%) for a higher lifespan. Cement kilns are not affected since they use no NG.
Mullite (28% SiO2) and Zircon (33%) do not suffer long-term harm in air-H2. However, the shift to oxy-H2
could make them more vulnerable on medium-term above 1300°C (fig. 6b), as suggested by FRITSCH
(2006). The higher the velocity of fumes, the stronger the attack on refractories: classical furnaces yield
green to orange scores, whereas gas turbines and other pieces exposed to high flows yield a red score.

Fig. 6: Evolution of volatilization with H2O of (a) SiO2 and (b) silicates and alumina in several
combustion cases (FRITSCH, 2006).
Glass furnaces suffer from the emission of volatile species (NaOH, KOH, HBO2, HCl, HF…) which
increases with √pH2O (+22% and +36% in oxy or air combustion furnaces with H2 instead of NG (including
the effect of fume velocities). Those species usually damage the crown (dissolution), superstructures
(exudation) and regenerators after a given time. However, the variations of their concentration seem to
be higher in NG furnaces (depending on their settings: fig. 7: case studies by VAN LIMPT, 2007) than
the expected order of magnitude of increase when injecting 100%H2 (DIETRICH, 2023). These
considerations, as well as several laboratory tests, suggest that most of the currently used refractories,
especially in oxy-NG furnaces, should stand the H2 shift. However, some changes should be foreseen,
replacing classical silica crowns with low lime (< 0.5%) silica and focusing on low exudation
(<0.2%TiO2+Fe2O3) AZS superstructures, with relatively moderate CAPEX increases.
Volatile NaOH partial pressures in glass furnaces:
theoretical evolution and comparison with oxy-NG industrial cases
50 Oxy-H2
attack SiO2
45
and chemical attack
More water vapor

40 Oxy-NG Crown
35
Air-NG
30
AZS
pNaOH (Pa)

25
Oxy-NG
(super-
20 case 3 structures)
15
Oxy-NG
10 case 2
Other
5 Oxy-NG refractories
case 1
0
1200 1300 1400 1500 1600
Temperature (°C)

Fig. 7: evolution of expected attack on glass refractories by NaOH

Water condensation: the H2 transition should increase the dew point by 11-13°C, which is expected to
increase condensation in all refractory and fibers rear panels and chimneys, with subsequent weight gain
and sagging. Vapor barriers or other architecture changes would be required, as well as Inconel anchors
instead of stainless steel to cope with increased corrosion. Calcium-aluminate cement within the core of
linings is supposed to be totally dehydrated after first heating of furnaces. However, this core may exhibit
residual hydrated species that would be able to rehydrate, swell and crack through water condensation.
This possibility is of current interest for some refractory manufacturers and will be studied.

Anchors,
More water condensation

Fibers
through adding H2

Calcium-
aluminate
cements

Other
refractories

Fig. 8: Increased sagging of fiber blocks might occur with increased condensation
(source: https://www.industrialheating.com/articles/95381-seven-common-causes-of-refractory-failure)

6. Conclusion
The transition from NG to H2 implies up to 50-84% water vapor increase in oxy and air combustion
respectively, and more flow in the fumes in the former case (less in the latter). With partial addition of H2
up to 20%, almost no additional risk is identified for the lifespan of kilns, with respect to using NG.
Reducing conditions should neither be a problem with 100%H2 as a fuel. On the contrary, the strong
increase in emitted water vapor is a point of vigilance. While many refractories should not suffer significant
additional damage, the fact of keeping the same lifespan for some silica bearing materials (including AZS
and Zircon based materials) at high temperature would, at least, require to upgrade them with more pure
compositions, in order to avoid dissolution or exudation. The glass furnaces are an example of this but
the estimated CAPEX increase would remain moderate. Condensation also should be watched: sagging
fibers, corrosion in anchors and possible rehydration in cements could take place with a higher dew point.
Vapor barriers and adapted furnace architecture should be considered. A summary in industrial furnaces
is depicted in fig. 9.
 100% H2 combustion
Refractory Ceramics & Cement Foundry, Steel- Petro-
N° Glass
composition Heavy clay & Lime Non Ferrous making chemistry

1 Silica Crown

Fireclay , Linings Lime Linings Linings

2 Low Alumina,
LBP Fibers Fibers Fibers Cement Fibers Fibers Fibers

3 Cordierite

Mullite, Linings Lime

4 Sillimanite,
Andalousite Others Cement

High Alumina
5 (>90%)
& Alumina-C
Zirconia, Super-
6 Zircon, structures, Coatings
AZS others
SiC, Lime, Burners,
7 Burners
SiAlON Cement Others
Forsterite,
8
Spinel
MgO, MgO-
9
Chromite, MgO-C
Doloma
10
& Doloma-C
Calcium Aluminate
11
Cements

Fig. 9: Risk increase assessment for several refractories and industrial applications,
when replacing NG with 100%H2. Color scores decrease by 1-2 grades when adding 2-20% H2

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