inInvestigation

Refractory Linings
G. Sukul*, P.V. Balaramakrishna*
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Alkaline of Process Hydrolysis
Plants:
Investigation
in
AMonographs
Ceramic Case Refractory of Alkaline
Linings of Process Plants: Hydrolysis
3.3.3.5 Study Investigation of Alkaline Hydrolysis in Refractory Linings G. Sukul, P.V. Balaramakrishna
inARefractory Linings
Case Studyof Alkaline Hydrolysis
G. Sukul*, P.V. Balaramakrishna*
of Process Plants: Aof
Case StudyProcess Plants:

Investigation

HANDBOOK OF CERAMICS
CERAMIC MONOGRAPHS
A Case 7+($87+25 Study $%675$&7 .(<:25'6

in Refractory
G. Sukul*, P.V. Balaramakrishna*
7+($87+25 Linings $%675$&7 of Process Plants: .(<:25'6
The corresponding author, In view of the ever-increasing energy needs in the process industry, effi- refractory, lining design,

A Case 7+($87+25 Study

Gunjan Sukul, has been work- ciency enhancements assume critical importance. Refractory linings play engineering, alkaline
The $%675$&7
corresponding author,a pivotal
In view of in
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ever-increasing energy needs in the process industry,
equip-effi-hydrolysis,
refractory, lining design,

Investigation of Alkaline Hydrolysis in Refractory Linings of Process

ing in the Research and Devel- role reducing the energy consumption of the process carbonation,
opment Gunjan Sukul, has of
department been L&T work-mentciency
alongenhancements
with ensuring safe assume andcritical
reliableimportance.
operation ofRefractorya plant. Owing linings toplayfailureengineering, alkaline
The ingcorresponding
Hydrocarbon in the Research
Engineering author,
and for In view
Devel-the of thecomplexities
aproject
pivotal ever-increasing
role in reducing energy
andthe energy needs
installation in the process
consumption
schedules, industry,
processeffi-
ofrefractory-lined
the refractory,
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hydrolysis,
64 design,
carbonation,
(2015) [4-5]

Plants: A Case Study

Gunjan
the pastSukul,
opment has been
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years. He has work- ciency
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ment enhancements
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are with assumeat
oftenensuring
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oftimes,
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ing in 7+($87+25
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non-performance complexities
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installation ofof
One schedules,
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reasons for hydrolysis, carbonation,
INTERCERAM 64 (2015) [4-5]
opment the department
past 10 years. of He L&Thas ament along
equipments with ensuring
are often safe
stored and at reliable
project
Science from California Insti- such failure, especially for plants in the vicinity of a seacoast, is alkaline operation
sites for of a
prolongedplant. Owing
times, to
leading failure
tute of Technology, The
Hydrocarbon
and corresponding
Master’s Engineering
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a Bachelor’s inauthor,
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Materials In view
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in hydrolysis of the
project ever-increasing
or complexities
non-performance
carbonation and and
of energy
premature
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installation in
failures.
linings. the Inprocess
schedules,
One of the
this industry,
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paper, effi- forINTERCERAM
reasons
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(2015) [4-5]
Ceramic Engineering Gunjan
the pastthe
Science
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He has
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equipments
Insti-
of such enhancements
are
theoften
failure, assume
stored
especially
advent and ABSTRACT
foratcritical
project
plants
nature importance.
in
of sites
the Refractory
for prolonged
vicinity
alkaline inlinings
times,
of a seacoast,
hydrolysis is play
alkalineengineering, alkaline
leading
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failures.
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measures One ofof
linings.
were successfully Inthe
the main
thisprocess
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paper,
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industry,
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project
especially
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and
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or complexities
degradation the and
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andrefractory
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alkaline
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refractory linings.
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Max Technology,
Planck Institute and
hasin also a Bachelor’s
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In this techniques
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ficiency enhancements
Ceramic
nent Engineering
international the assume
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Indian
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Institute
such has as a
of theRefractory
equipments
investigated
prevent linings
are
the often
further advent In this
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and
refractory
Institute of Technology, Sweden. He has contrib- can be applied to the design, engineering and installation stages of up- at paper,
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nature
degradationwe
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alkaline
and investigated
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Materials
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Max of Technology,
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process developedofprevent
to refractory
guidelines thislinings. In this techniques
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problem. paper, we have that
Owingious to
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Young Royal
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Institute
bodies
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E-Mail: ofrefractories
Year Technology,
award for and
gunjan_sukul@Lntenc.com Sweden.
his ceramics.
outstandingHe has He contrib-
is a re- can be applied to the design, engineering and installation stages of up-
contributions
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cipient ofnumerous
the international
Petrotech-2014
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Young Executiveand of coming process plants to prevent this problem.
5$0²5()5$&725,(60$18$/,,
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the E-Mail:
Year award gunjan_sukul@Lntenc.com
outstanding contributions
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1. Introduction
bodies on
E-Mail:
cipient
refractories and ceramics. He is a re-
gunjan_sukul@Lntenc.com
Introduction
of the Petrotech-2014 Young Executive of (5)
2KOH + CO2 A K2CO3 + H2O (4)
Alkaline hydrolysis
the Year
Alkaline award isforahis
hydrolysis
phenomenon
isoutstanding
a phenomenon
observed
contributions in insulating refractory
observed in insulating refrac- K2CO3 + CaO·Al2O3·nH2O A CaCO3 + K2O·Al2O3 +
liningsto having
the
tory
high
1 Introduction
hydrocarbon
linings
porosity
havingindustry.
when they are left exposed to atmosphere
high porosity when they are left exposed to at- KOH + nH2O
2KOH + CO2 A K2CO3 + H2O
(5)
(4)
for a long period of time without being dried out. This process is severe
Alkaline
E-Mail: hydrolysis
gunjan_sukul@Lntenc.com is a phenomenon observed in insulating refrac- K 2 CO 3 + CaO·Al 2 O 3 ·nH 2 O A CaCO 3 + K 2 O·Al 2 O3 +

Alkaline Hydrolysis
mosphere for a long period of time without being dried out. This
1 Introduction K2O·Al2+
2KOH OCO
3 + 2nH
A2O A 2KOH
K2CO + 2Al(OH)3
3 + H 2O (6)
(4)
hu- (6)K CO + CaO·Al O ·nH O A CaCO + K O·Al O +
tory linings
in anprocess
environment having
with high porosityandwhen they areand leftisexposed to at- KOH + nH O
in high temperature humidity, further (5) 2
Alkaline ishydrolysis
severe an
is aenvironment
phenomenon with high temperature
observed inbeing
insulating and
refrac-
mosphere
accelerated byand for
exposure a long
tohigh
rain.period of time
The mainwhen
cause without
for alkaline dried
hydrolysis out. This
is at- As K O·Al O + nH O A 2KOH + 2Al(OH) 2
2(6)3
2 3
2 3
2
2 3 2
3
2 3

ingscarbonation
of Process Plants:
midity,
toryprocess
linings is further accelerated by exposureare to rain. The to
main is evident from the above reactions, there is regeneration of alkali
ishaving
severe
of alkaline
alumina in anporosity
cement environment
(CA) present
they
inwith high
refractory
left exposed
temperature
materials and hu-KOH + nH O
[1].
(5) 2
cause for
mosphere for a hydrolysis
long period is
ofcarbonation
time of
without alumina
being cement
dried out. (CA)
This hydroxide
K O·Al which can
Abe carbonated once more and thereby create(4) a
1 Introduction
midity, and is further accelerated by exposure to rain. The main2KOH As is+Oevident
+ nH
CO O
A from
K CO 2KOH
+
the HO + 2Al(OH)
above reactions, there is regeneration of(6)
2 alkali 2 3 2 3
Depending
presentupon the curing
in refractory
process temperature,
materials alumina cement
[1]. Depending upon the mixed
curingwith
tem- cyclic disintegration process. In most areas affected by alkaline hy-
2 2 3 2

causeishydrolysis
Alkaline severe
for alkalinein an aenvironment
ishydrolysis
phenomenon with
observed
is carbonation high temperature
ofinalumina
insulating and
cement hu-
refrac- (CA)K2CO 3 + CaO·Al 2O3·nH can2O beA CaCO3 + K 2O·Al 2O3 +
waterperature,
forms
midity, various
andalumina
is hydrates,
furthercement including
mixed
accelerated CAH
withby 10
water (<21
exposure °C),
forms to C 2 AH
various
rain. 8 and AH
hydrates,
The 3
main isishydroxide
Asdrolysis,
evident from
fibrous
which
thetheabove
efflorescence
carbonated
reactions,
is seen on
once
there more
the isouter
and thereby create a
isregeneration
refractoryofof alkali
surface,
torypresent
liningsinhaving refractory highmaterialsporosity [1]. when they are left
Depending upon exposed
the curingto at- tem-As KOH evident
cyclic+ nH 2O
from
disintegration above
process.reactions,
In most there areas regeneration
affected by alkaline alkali
(5) hy-
(21–35cause °C),
including
mosphere and
for C
CAH 3 AH
alkaline
foralumina6 and
(<21 AH
hydrolysis
a long period °C),
3
cementof
(>35
C is AH °C) [2].
and
carbonation
timewith When
AH
without of these
(21–35
alumina
waterbeing
hydrates
°C),
formsdried
and
cement come
C AH
(CA)
out.hydrates, hydroxide
This K2O·Al consisting
hydroxide which mainly
which can
nH2O A beof
can carbonated
CaCO
be once
powder
carbonated more
once[5]. and
It
more may thereby
and also becreate
thereby a
accompa- cy-
create (6)a
2O3 +fibrous 2KOH + 2Al(OH)
10 2 8 3 3 6 3
perature, mixed various drolysis, efflorescence is seen on 3 the outer refractory surface,
in contact
and
present
process AHwith 3in atmospheric
is(>35 °C)in[2].
refractory
severe an CO
When
materials 2,°C),
a these
environment carbonation
[1]. hydrates
Depending
with reaction
come
AHupon
occurs:
in contact
the°C),
curingwith tem-at- clicnied
C3AH6cyclic
disintegration scalingprocess.
bydisintegration or peeling-off
mainlyprocess.
In mostInof areasanyaffected
most refractory by alkaline
areas affected surfaces hydrolysis,
in contact
by alkaline hy-
including CAH (<21 C2AH 8 andhigh 3temperature
(21–35 and hu- consisting of CaCO 3 powder [5]. It may also be accompa-
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alumina , a
10
carbonation
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with occurs:
water forms .(<:25'6
various hydrates, fibrous
with efflorescence
drolysis, the atmosphere.
fibrous is seen
efflorescence on
Alkaline the
is outer
hydrolysis
seen on refractory
the causes
outer surface, consisting
disintegration
refractory surface,of
midity, and is 2further accelerated by exposure to rain. The main As
and AH3 (>35 °C) [2]. When these hydrates come in contact with at- nied by scaling or peeling-off of any refractory surfaces in contact is evident from the above reactions, there is regeneration of alkali
(1) cause
including
of the ever-increasing
CAH
for alkaline
mospheric
energy needs
(<21
10 hydrolysis
CO °C), C AH
processisindustry,
, a carbonation
in 2the
and
2 carbonation AH
8 reaction 3of
effi- occurs:
(21–35 °C),
alumina cement and C AH
(CA)
3 6 mainly
the of CaCO
refractory
consisting
hydroxide
with themainlypowder
binder
3 atmosphere.
which of
can be [5].carbonated
CaCO ItAlkaline
structure,3may also
powdereventuallybe accompanied
[5].
once
hydrolysis It damaging
may
morecauses also
and therebyby
the
be scaling
complete
accompa-
create
disintegration or a of
CAH
and AH10 +3in CO
(>35 2 +°C)xH [2]. A
2Omaterials
When CaCO 3 + Al
these 2O3·yH2come
hydrates Orefractory,
+upon
(10+x–y)H
in contact
lining design,
2Owith at- peeling-off
(1) lining.
nied of any refractory
Therefore,
bydisintegration
scaling orin project
peeling-off surfaces
sites ineventually
with
Inofmostany contact
high humidity
refractory with thebyand
surfaces atmosphere.
intempera-
enhancements assume presentcritical refractory
importance. Refractory[1]. Depending
linings play engineering, the curing
alkaline tem- cyclicthe refractory binderprocess.structure, areas affected
damaging thecontact
alkaline hy-
complete
2O (2) Alkaline hydrolysis causes indisintegration of the refractory binder struc-
C 2AH
mospheric 8 + 2CO 2+ xH 2O of Athe 2CaCO + equip-
Alwater
2O 3·yH O + (8+x–y)H ture, ittheisfibrous
imperative toAlkaline
give due consideration to refractory
proper refractory
al role in reducing the energy
perature,
CAH +CO CO 2, a
consumption
10alumina
carbonation
2 +cement
xH 2O A CaCO reaction
process
mixed 3with
3 + Al
occurs:
2O3·yH
2hydrolysis,
forms2O +various
carbonation,
(10+x–y)H hydrates,
2O (1)with
drolysis,
lining. atmosphere.
Therefore, efflorescence project hydrolysis
is seen
sites on
with causes
thehighouter disintegration
humidity andsurface, of
tempera-
C AH + 3CO + xH O A 3CaCO + Al O ·yH O + (6+x–y)H O (3) handling
ture, eventually duringdamagingthe project design
thetocomplete and execution stages.
ong with ensuring safe 3 and
including 6
C2AH8 + reliable
CAH 2
2CO operation
102(<21
+ xH°C),
2 of
2O A
a plant.
C22CaCO
AH8 and
3 Owing
3 + AH
2 to3
Al2O failure
3 (21–35
3·yH2O °C),
2 and C3AH
+ (8+x–y)H 2 the
2O 6 (2)consisting
refractory
ture, it is mainly binder
imperative of CaCOstructure, due lining.
3 powder
give eventually [5]. It Therefore,
consideration damaging
may also toinproper
project
the
be sites
complete
accompa-
refractory
(2)
oject complexities CAH
ents are often stored
and 10installation
andCAH 3AH +3 CO
at projectCAH
(>35
6 + +°C)
23CO
sites
xH schedules,
2
for
+2O
[2].xH A When
prolonged2 OCaCO
A
refractory-lined
3 + Al
these
3CaCO 2O
3
times,+leading
+ 3·yH
hydrates Al 2
2come
O 3
INTERCERAM
O·yH + (10+x–y)H
2in
O
64 (2015)
contact
+ (6+x–y)H2Owith2O
[4-5]
at-with
(1) (3)
2
high
lining.
nied handling
Case
humidity
byTherefore,
scaling during orand temperature,
inpeeling-off
project
the project sites it
with
ofdesign
any is imperative
high
refractory
and humidity
execution to
surfacesgive
andin
stages. due con-
tempera-
contact
Moreover,
C 2AH8 + 2CO
mospheric
performance and premature CO
failures.
2 +,10a
2 One
xHand 2OC
carbonationA 2AH 8 are 3metastable.
2CaCO
of the mainreaction reasons for
3·yHUnder
Al2Ooccurs: 2O + (8+x–y)Hthe influence 2O (2) of sideration
ture,
with itthe tostudy
is imperative
proper refractory
atmosphere. toAlkaline
givehandling
duehydrolysis
consideration
duringcauses the toproject
proper refractory
design
disintegration andof
temperature
C AH + 3CO and + other
xH O Afactors
3CaCO these + hexagonal
Al O ·yH O hydrates
+ (6+x–y)H convert O to
(3)a As arefractory
handling case duringstudybinder for
the alkaline
project hydrolysis
design and investigation
execution stages.and remedia-
3
lure, especially for plantsMoreover,
6 2
in the vicinity CAH10 ofand
2 C2AH8 is
a seacoast, metastable. Under the influenceexecution
arealkaline
3 2 3 2 2 of 2 Case
the stages.study structure, eventually damaging the complete
sis or carbonationcubic hydrate+(C
of refractory
CAH 10 + CO2 linings.
temperature xH 3AH
and In6A
2Oother
)this
[3].
CaCO This
paper,
factors
leads
we
3 + these
Al 2O have to an
3·yH
increase in porosity,
2O + (10+x–y)H
hexagonal hydrates 2convertO (1)to ation, lining. consider a fresh
As aTherefore,
case studyinfor
feed preheater
projectalkaline withinhigh
siteshydrolysis the reactor-regenerator
humidity andand
investigation tempera- cir-
remedia-
ated the advent and thereby
Moreover,
nature accelerating
CAH
of alkaline and the C alkaline
hydrolysisAH are
in hydrolysis
ametastable.
refinery process
Under [4].
the influence of cuit
2 Case of a fluid
study catalytic cracking unit. The preheater is a direct-fired
(3) Iftemperature
C2AH cubic8 + 2CO hydrate2 + xH
10 (COAH
2 3 A62CaCO
2 ) [3].8
3 + Alleads
This 2O3·yH to2Oan+ increase
(8+x–y)Hin2Oporosity, (2) ture,tion, it isconsider
imperative to give
a fresh feeddue consideration
preheater to proper refractorycir-
in the reactor-regenerator
nnovative remedial measures
C3alkali
further refractoryter,
AH 6 + 3CO
thereby
degradation
cubic environment
hydrate
were
compounds
and successfully
accelerating
and(C
other
2 + xH2O A
salvage
orAH
(specifically
cement, )
factors
the
already
[3].
implemented
3CaCO these
alkaline
then
This
potassium)
affected
the
leads
to
Al2O3·yH2are
hexagonal
3 + hydrolysis
lin-
reaction
to an
+present
hydrates
Oprocess(6+x–y)H
isincrease
cyclic and
[4].
in
in the
convert
the
2O (3)
alkali lar
porosity,
2. Case study
to a heater
wa- As acuit
handling having
case
convection
tion,
of
consider
study
during
a
vertical
fluid
a
for
the
catalytic
section
fresh
radiantdesign
alkaline
project box-type
hydrolysis
cracking
and mounted
feed preheater
and
unit.
configuration
stack.
in
investigation
execution
the
The
The
stages.
preheater
with
and
860 °C flue gas tem-
reactor-regenerator
a modu-
is aremedia-
direct-fired
cir-
e have also developedIfguidelines
acts
thereby as
alkali compounds
a catalyst
accelerating
3
and proactive
in the the
6 (specifically
techniquespotassium)
degradation
alkaline
that
mechanism:
hydrolysis process
are present in the wa-
[4].
As perature
a case
cuit
heater
of
study
a of
having
fluidthefor alkaline
vertical
heater
catalytic is hydrolysis
radiant
used
cracking to warm
unit.
investigation
box-type
The the vacuum
preheater
andisgas
configuration remediation,
a
with
oil
a modu-
(VGO)
direct-fired
Moreover,
applied to the design, ter, CAHand
environment
engineering 10 and orCcement,
installation 2AH8 are metastable.
then
stages oftheup- reaction Under the influence
is cyclic and the of alkali 2 Case
consider study
laraconvection
fresh feed preheater
section andinmounted
theit reactor-regenerator
stack. The 860 °C circuit
flue ofgasatem-
If
process plants to prevent alkali
temperature thiscompounds
problem.
and other (specifically
factors these potassium)
hexagonal are presentconvert
hydrates in the wa- to a feed
heater
As a from
casehavingthe
study hydrotreater
vertical
for radiant
alkaline before
box-type
hydrolysis is injected
configurationinto thewith
investigation reactor
and a oil riser.
modu-
remedia-
Moreover, acts as
CAH a catalyst
and C in
AH the degradation
are metastable. mechanism:
Under the influence of fluid perature
catalytic of
cracking the heater
unit. The is used
preheater to warm
is a the vacuum
direct-fired heatergas having(VGO)
ter, environment 10 2 8 The VGO feed is heated from 280 to 390 °C in the vertical coils of
cubic hydrate (Cor cement, then the reaction is cyclic and the alkali lar
3AH6) [3]. This leads to an increase in porosity,
convection
tion, feedconsider
from asection
the fresh and mounted
feed
hydrotreater preheater
before stack.
in
it the
is The 860into °C flue
reactor-regenerator
injected the gas tem-
reactor cir-riser.
temperature
acts as a and
catalystotherinfactorsthe these hexagonal
degradation mechanism: hydrates convert to a vertical the
perature radiant
preheater. of box-type
the heater configuration
is used to with the
warm a modular
vacuum convection
gas oil sec-
(VGO)
thereby accelerating the alkaline hydrolysis process [4]. cuitThe of aVGO fluid feedcatalytic cracking
is heated fromunit. 280The to 390 preheater
°C in the is avertical
direct-firedcoils of
cubic hydrate (C3AH6) [3]. This leads to an increase in porosity, thereby tionThe andradiantmounted sectionstack.ofThe the860heater °C flue isgas
isitlined temperature
primarily intoby ofreactor
theabout the heater
If alkali compounds (specifically potassium) are present in the wa- feed heater from
the havingthe
preheater. hydrotreater
vertical radiant before
box-type injected
configuration with a100 modu-t of
riser.
accelerating the alkaline hydrolysis process [4].
ter, environment or cement, then the reaction is cyclic and the alkali lar convection
is used
The to
dual-layer
VGO warm feed the
castable is vacuum
refractory,
heated gas
from oil
with
280 (VGO)
tothe 390 feed
lining
°C from
inhaving
the the hydrotreater
a total
vertical thick-
coils of t of
The radiantsection sectionand of the mounted
heater isstack. linedThe 860 °C by
primarily flue gas tem-
about 100
If alkali
* L&Tcompounds
Hydrocarbon Engineering (specifically
acts as a catalyst in the degradation mechanism:
potassium)
Limited, Research are present
and Development, in the water,
Mumbai (India) before ness
the itofis injected
200
preheater.
perature
dual-layer
mm. into
of thecastable the
Refractory reactor
heater refractory, riser.
materials
is used to warm The VGO
were
with the
feed
selected
thelining
vacuum is heated
for the
gas oil
having
from 280
applica-
(VGO)
a total thick-
environment or cement, then the reaction is cyclic and the alkali acts as to 390
* L&T Hydrocarbon Engineering Limited, Research and Development, Mumbai (India)feedness
The°C from in of
radiant thethe
200
vertical
section
hydrotreatercoilstheofheater
mm.ofRefractory
the preheater.
before isitlined The
primarily
is injected
materials
radiant
were into by
selectedthesection
about
reactor
for the
of riser.
100 the
t of
applica-
a catalyst in the degradation mechanism: heater
TheisVGO linedfeed primarily by aboutfrom100 280t of dual-layer castable refractory,
EXPERT FACHMEDIEN GMBH

dual-layer castable refractory,

is heated with tothe 390 lining
°C inhaving a total
the vertical thick-
coils of
DÜSSELDORF – GERMANY

* L&T Hydrocarbon Engineering Limited, Research and Development, Mumbai (India) with thethe
ness oflining
200 mm.
preheater. havingRefractory
a total thickness materials of 200 weremm. Refractory
selected for the materials
applica-
(4) were selected
The radiantfor the application
section based
of the heater on the
is lined processbylicensor’s
primarily about 100 basic
t of
2KOH + CO2 A K2CO3 + H2O (4) design requirements.
dual-layer castableThe most important
refractory, with theproperties of the ahottotal
lining having facethick-
and
ulating refrac- K* 2CO A CaCO
+ CaO·Al O3·nH2O Limited,
L&T 3Hydrocarbon 2Engineering 3 + Kand
Research 2O·Al 2O3 +
Development, Mumbai (India) back-up refractory
ness of 200 mm. layers are summarised
Refractory materialsinwere
Tableselected
1. The hydraulic bond-
for the applica-
xposed to at- KOH + nH2O (5) ed castable materials were mixed with specified quantities of water and
ried out. This K2O·Al2O3 + nH2O A 2KOH + 2Al(OH)3 (6) installed using convectional pouring techniques. After installation,
ature and hu-* L&T Hydrocarbon Engineering Limited, Research and Development, Mumbai (India)
curing (wet and air) was carried out for 48 h.
in. The main As is evident from the above reactions, there is regeneration of alkali
cement (CA) hydroxide which can be carbonated once more and thereby create a
e curing tem- cyclic disintegration process. In most areas affected by alkaline hy-
ious hydrates,
), and C3AH©6 2017
drolysis,
Ceramic fibrous
Monographs
consisting
efflorescence
– Handbook
mainlyGmbH
Expert Fachmedien
is seen on the outer refractory surface,
of Ceramics
of CaCO3 powder [5]. It may also be accompa-
Supplement to Interceram 66 (2017) [1–2] 01
ntact with at- nied by scaling or peeling-off of any refractory surfaces in contact
 Ceramic Monographs 3.3.3.5 Investigation of Alkaline Hydrolysis in Refractory Linings
,17(5&(5$0²5()5$&725,(60$18$/,, G. Sukul, P.V. Balaramakrishna
,17(5&(5$0²5()5$&725,(60$18$/,,
,17(5&(5$0²5()5$&725,(60$18$/,,
of Process Plants: A Case Study 
HANDBOOK OF CERAMICS
CERAMIC MONOGRAPHS

5()5$&725,(6)2580
5()5$&725,(6)2580
5()5$&725,(6)2580

1
111 2
2
2
2

Fig. 1 • Degradation of refractory lining in side walls Fig. 2 • Degradation was severe in damp areas
Fig.
Fig.1 • Degradation
Degradationof refractory
refractorylining
liningin side
sidewalls Fig.
Fig.2 • Degradation
Degradation was
was severe
severe in
in damp
damp areas
Fig. 1 1• •Degradation ofofrefractory lining ininside walls
walls Fig. 22••Degradation was severe in damp areas
areas

3
333 4
4
4
4

/ mW/g
// mass-%
mass-%

flow/ mW/g
Weight/ mass-%

Heatflow
Weight
Weight

Heat
Temperature(C°)
Temperature
Temperature / °C
(C°)
Temperature (C°)

Fig.
Fig.333•••Peep
Fig. Peep doors
doorsclosed
Peepdoors leading
closed
closed tototo
leading
leading insufficient ventilation
insufficient
insufficient ventilation
ventilation Fig.
Fig.444•••TGA/DSC
Fig.
TGA/DSC thermograph
thermographof
TGA/DSC thermograph ofrefractory
of refractory
refractory
powder
powder
powder
Fig. 3 • Peep doors closed leading to insufficient ventilation Fig. 4 • TGA/DSC thermograph of refractory powder

tionbased
basedon on theprocess
processlicensor’s
licensor’sbasic basic designrequirements.
requirements.The The 3–5 mm layer layer of refractory
refractory had started started to peel off and loss of mate-
tion
In the
tion based on the
original theplan, dry-out
process licensor’s basic design
of the preheater refractory
design lining wasThe
requirements. to 3–5
3–5 mmmmTablelayer1of of· Properties
refractory had of insulating
had started to peel refractory
off andlining
loss of mate-
most
most important
important properties
properties of
of the hot face and back-up refractory rial was observed at various locations as seen in Fig. 1.
be completed
most important during of the
the hot
plant commissioning.
properties hot face and
and back-up
However,
face refractory
due to unforeseen
back-up refractory rial
rial was
was observed
observed at at various
various locations
locations as seen in Fig. 1.
layersare
layers are summarisedininTable Table1.1.The Thehydraulic
hydraulic bondedbonded castable
castable Lining
The propertywas most
degradation most severe in in Hot face Back-upsuf-
layers are summarised
circumstances, the commissioning
summarised in Table activity
1. The of the plantbonded
hydraulic was delayed. The
castable The
The degradation
degradation was was most severe severe in damp damp areas
areas which
which werewere not
not suf-
materialswere weremixedmixedwith withspecified
specified quantities
quantities ofof waterwater andand in- ficientlyventilated,
ventilated, as
materials
condition
materials of the
were refractory
mixed with lining was
specified checked periodically
quantities with
of water and in-
visual as
in- ficiently
Thickness
ficiently / mm as is evident in Fig. 2. The75integrity of the
ventilated,
as isis evident
evident in in Fig.
Fig. 2.
2. The
The integrity
integrity of of the
125lining
the lining
lining
stalledusing
stalled usingconvectional
convectional pouringpouring techniques.
techniques. After After installation,
installation, wastested
was testedby bystriking
striking itit with
with aa ball
ball point point machinist
machinist hammer
hammer at at regu-
well
stalledas sound
using inspection
convectional techniques
pouring [6]. About
techniques.a year after
After installation,
installation, was
BD tested
/ kg/m by
3 striking it with105 a ball °C point machinist
1380 hammer660 at regu-
regu-
curing(wet
curing (wetandand air)was wascarried
carriedout out for48 48h.h. lar intervals.The The sound indicatedindicated that the the lining hadhad started to to lose
fibrous
curing powder
(wet andonair)thewas
air) exposed
carried out for
refractory surface
for 48 h. was present in most lar
lar intervals.
intervals. The sound sound indicated that that the lining
lining had started
started to lose
lose
InInthe
areas
In
theoriginal
the
originalplan,plan,dry-out
of the sideduring
original
dry-outofofthe
walls. Moreover,
plan, dry-out of
thepreheater
preheaterrefractory
a thin 3–5 mm
the preheater
refractorylining
layer of due
refractory
lining wasto
lining was
refractorywashad
to
to
itsinherent
its inherentstrength.
itsCCS
inherent
strength.However,
strength.
However,
However, 105ititit°Cstill
still had
still had 70 residual
had sufficient
sufficient
sufficient
residual 13
residual
strength
strength
strength
bebecompleted
completed during plantcommissioning.
plant commissioning. However,
However, due tounfore-
to unfore- / kg/cm2 process conditions.
to withstand
to conditions.
started to peelduring
off and plant
loss ofcommissioning
material was observed to withstand
withstand process 815 as °C less than 1050% of the initial 10 lining
activityatof
be completed commissioning. However,various
due tolocations
unfore- process conditions.
seencircumstances,
seen circumstances, thecommissioning
the activity of the
the plant
plant was was Loss
Loss of material
material was was measured
measured
asdelayed.
seenseen in TheFig. 1.condition
circumstances, The degradation
the was most lining
commissioning severewas
activity in damp
of the areasperiodi-
plant which
was Loss of material was measured as
of as lessless than
than 10 10 %
% of of the
the initial
initial lining
delayed. The condition ofof the refractory checked PLC / % No
thickness. Noprotective
protective coating 815 °C
coating was observed
observed –0.5
on the –0.5lining
the refractory
refractory sur-
were
delayed.not
callywith
with sufficiently
The condition
visual aswell
wellofasthe
ventilated,
the refractory
sound
lining
as isinspection
refractoryevident
was checked
intechniques
lining Fig.
was2. The [6].
checked periodi-
integrity
Aboutofa
periodi- thickness.
thickness.
face and No
the protective
atmosphere coating
inside
was
was
the observed
heater was
on
on
hot the
and refractory
humid.
sur-
sur-
Most
cally
the
callylining
with visual as
wasinstallation,
as
tested by striking
visual as well as sound
sound inspection
it with a ballon
inspection techniques
point machinist
techniques [6]. About
Aboutataa
hammer
[6]. face
face and
and the
the atmosphere
atmosphere Al
inside
inside Othe
2 the heater was35hot and
3 heater was hot and humid. Mosthumid.34 Most
year
year after
after installation, fibrous
fibrous powder
powder on the
the exposed
exposed refractory
refractory ofChemical
of the peepanalysis
thepeep doors were
doors
doors were
/ closed, closed, as
were closed,
as seenseen in Fig.
seen in
Fig. 3, and
in Fig. 33,
and there was
3, and there
was negli-
negli-
regular
year
surface
surface
intervals.
after was
was
Thein
installation,
present
present
sound
inmost
most indicated
fibrous areas
areas of ofthat
powder the
sidelining
on
theside
the
thewalls.
walls.
had
exposed started
Moreover,
Moreover,
toaathin
lose
refractorythin of theair
mass-%
gible
gible
peep
air circulation.
circulation.
Fe as
2 O 3 there was 10 negli-
its inherent strength. However, it still had sufficient residual strength
surface was present in most areas of the side walls. Moreover, a thinto gible
Basedair
Based oncirculation.
on visualinspection,
visual CaO
inspection, itit appeared
appeared that 16 degradation
that the degradation25 was due
withstand that the
the degradation was
was due
Table11• process conditions. Based on visual inspection, it appeared due
EXPERT FACHMEDIEN GMBH

•Properties
Properties ofinsulating
insulatingrefractory
refractorylining
lining to alkaline hydrolysis of the castable refractory lining. Representa-
DÜSSELDORF – GERMANY

Table of to alkaline hydrolysis of the castable refractory lining. Representa-

Loss
Table of
1 material was
• Properties
Liningproperty
property measured as
of insulatingless than
refractory10 % of
lining
Hotface the initial
face lining
Back-up
to alkaline
tivesamples
tive samplesof hydrolysis
of powder of
powder material the castable
material and refractory
and peeled
peeled off lining.
off refractory Representa-
refractory layer
layer from
from
Lining Hot Back-up tive samples of powder material and peeledinvestigation.
off Laboratory
refractoryLaboratory
layer from
thickness. No
Lining property
Thickness/ /mm
protective
mm
coating was observed on
Hotthe
75
refractory
face surface
Back-up
125
surface
the
the were
surface
surface collected
were
were for
collected
collected detailed
for
for investigation.
detailed
detailed investigation. character-
Laboratory
Thickness 75 125 the surface
ization were
and thermaland collected
design for
analysis detailed investigation.
were analysis
conductedwere Laboratory
to understand
and BD
the
Thickness
/
atmosphere
kg/m3
/3mm inside the heater was hot and75humid. Most
105 °C 1380
125of the
660 characterization
characterization and thermal
thermal design
design analysis were conductedthe
conducted to
to
BD / doors
BD / kg/m3were closed, as seen in105
peep kg/m Fig. °C
3, and 1380was negligible
there 660 air characterization
probable
understand causes theand and thermal
mechanisms
probable causesdesign
ofand analysis lining
the mechanisms
and refractory
mechanisms were conducted
of degradation.
the refractoryto
105
105°C°C
°C 1380
70 660
13 understand the probable causes of the refractory
circulation.
CCS/ /kg/cm
kg/cm 2 105 70 13 understand
lining the probable causes and mechanisms of the refractory
degradation.
CCS 2 105 °C 70 13 lining
CCS / kg/cm2 815 °C
815 °Cthat the 50
Based on visual inspection, it appeared
50
degradation
10
10
was lining degradation.
degradation.
815 °C 50 10 due
PLC
toPLC
PLC /%
/ %
alkaline
/ % hydrolysis of the castable 815
815AlO
°C
815refractory
°C
°C
2O3
–0.5
–0.5
35
–0.5
lining. Representative
–0.5 –0.5
–0.5
34
3. Result and discussion
3
3
3 Result
Result and
Result
and discussion
and
discussion
discussion
samples of powder material and peeled Al2O3 off refractory
Al 2 3
35 layer from
35
34 the
34 Scanning electron
Scanning
Scanning electron
electron microscopy
microscopy(SEM),
microscopy (SEM),
(SEM),energy dispersive
energy
energy dispersiveX-ray
X-rayanalysis
anal-
Chemicalanalysis
Chemical analysis/ /mass-%
mass-% FeFeO2O3
33 10
10 Scanning
ysis electron
(EDAX), microscopy
differential (SEM),
scanning energy dispersive
calorimetrydispersive
(DSC)
X-ray
X-ray
and
anal-
anal-
thermo-
Chemical analysis / mass-% FeCaO
2 O3
2 3
316 10
25 ysis
ysis (EDAX),
(EDAX), differential
differential scanning
scanning calorimetry
calorimetry (DSC)
(DSC) and
and thermo-
thermo-
CaO 16 25 gravimetric analysis (TGA)
gravimetric (TGA) were carried
carried out
out on the
the samples
samples collect-
02 CaO
Supplement to Interceram 66 (2017) [1–2] 16 25 gravimetric analysis
analysis (TGA) were
wereCeramic
carried out on
Monographs samplesof collect-
– Handbook
on the Ceramics
collect-
© 2017 Expert Fachmedien GmbH

 ,17(5&(5$0²5()5$&725,(60$18$/,,
,17(5&(5$0²5()5$&725,(60$18$/,,

5()5$&725,(6)2580
5()5$&725,(6)2580
 Ceramic Monographs 3.3.3.5 Investigation of Alkaline Hydrolysis in Refractory Linings
,17(5&(5$0²5()5$&725,(60$18$/,, G. Sukul, P.V. Balaramakrishna
of Process Plants: A Case Study

HANDBOOK OF CERAMICS
CERAMIC MONOGRAPHS
5()5$&725,(6)2580
5
5 6
6

55 6
6

Fig. 55 •• EDAX
Fig. EDAX spectrograph
spectrograph of
of refractory
refractory powder
powder

edFig.
ed from the heater
5 • the
EDAX heater
spectrographside walls
walls
of to understand
refractoryunderstand
powder the type of degradation Fig.
Fig.666•••SEM
SEM micrograph
SEMmicrograph of
micrograph of refractoryflakes
of refractory flakes
Fig.from5 • EDAX spectrograph side to
of refractory powder the type of degradation Fig. refractory flakes
and detect
and detect the the presence
presence of of potassium,
potassium, which which can can act act as as aa catalyst
catalyst in in
the alkaline
the alkaline hydrolysis
hydrolysis reaction. reaction. 7
7
ed from the
Differential
(EDAX),
Differential
and detect
heater side
scanning
differential
scanning
the presence
scanning wallscalorimetry
calorimetry
calorimetry
of
to understand
potassium,
and (DSC)the
and thermogravimetric
which
andtype
thermogravimetric
can
of degradation
thermogravimetric
act as a
analysis
analysis
catalyst
7
Fig. 6 • SEM micrograph of refractory flakes
were
were performed on the sample in inert
analysis (TGA) were carried out on the samples collected from thewith
performed on the sample in inert argon
argon atmosphere
atmosphere with
heater aain
purge
the rate
alkaline
rate of
of 100
hydrolysis
100 ml/min
ml/min and
reaction. a heating
side walls to understand the type of degradation and detect the pres-
purge and a heating rate
rate of
of 5
5 °K/min.
°K/min. The
The re-
re- 7
sults,
Differential
enceshown
sults, shown in
of potassium,
in Fig. which
scanning
Fig. 4, indicate
4, indicate
calorimetry
can act theaspresence
the presence
aand ofincalcium
calcium
thermogravimetric
catalyst of the alkaline carbonate
carbonate analysis
hydrolysis in
in
the
were
the powder
reaction.
powderperformed sample.
sample. on the sample in inert argon atmosphere with a
The
purge
The EDAX rate analysis
of
Differential scanning
EDAX analysis100 results
ml/min in
calorimetry
results in Fig.
andFig. a and55 show
heatingshow the presence
rate
thermogravimetric
the presence
of 5 °K/min. of calcium
analysis
of calcium
The werere-
and
sults,
and potassium
potassium in
in the
the samples.
indicate
samples. The
the
The calcium
performed on the sample in inert argon atmosphere with a purge rate ofin
shown in Fig. 4, presence
calcium of may
maycalcium be
be partly
carbonate
partly in
in the
the
form
the
form100powder of calcium
ml/min
of calciumsample. carbonate,
and acarbonate,
heating rate which is seen
of 5 °K/min.
which is seen The through
throughresults,lossloss
shown on ignition
on ignition
in Fig. 4,
(LOI)
The when
EDAX samples are heated to 900 °C. The presence of potassi-
indicate
(LOI) when theanalysis
presenceresults
samples of calcium
are heated in Fig.
carbonate
to 900 5 show°C.inThe thepowder
the presence
presence ofofpotassi-
sample. calcium
um
andThe suggests
potassium thatin it may
may
the act asas aa catalyst
samples. catalyst
The in an
calcium an alkaline
alkaline
may be hydrolysis
partly re-
inre-the
um EDAX analysis results in Fig. 5 show the presence of calcium and
suggests that it act in hydrolysis po-
action.
form ofHowever,
calcium since the
carbonate, percentage
which is of
seenpotassium
through is low,
loss onthe extent
ignition
tassium in the samples. The calcium may be partly in the form of calcium
action. However, since the percentage of potassium is low, the extent
of
(LOI)the reaction
reaction
whenwhich may be
samples beare limited.
heatedloss to 900 °C. The(LOI) presence of potassi-
of carbonate,
the may is seen through
limited. on ignition when samples are
Scanning
um suggests electron
that it microscopy
may act as awas
catalystcarried in outalkaline
an on both both the flakes
hydrolysis flakes
heated to 900 °C. The presence of potassium suggests that it may act
Scanning electron microscopy was carried out on the asre- a
and the However,
powder collectedcollected from the exposed
exposed refractoryislining
action.
and catalyst
the in an alkaline
powder sincehydrolysis
the percentage
from reaction.
the ofHowever,
potassium
refractory sincelininglow, thesurface.
the percentage extent
surface.
The
ofofthe SEM micrograph
reaction of refractory flakes flakes is shown shown in in Fig.
Fig. 66 and and aa
The potassium
SEM is may
micrograph low, thebeof limited.
extent of the reactionismay
refractory be limited.
refractory
Scanning powder image is displayed in Fig. 7. The micrographs
Scanningelectron
refractory electronimage
powder microscopy
microscopy wascarried
was
is displayed carried
in Fig.outout on on
bothboth
7. The the flakes
the flakes
micrographs and
indicate
and the the presence
powder presence collectedof calcite
calcite
from crystals
the exposed and refractory
the absence
absence of calcium
lining calcium
surface.
the powder collected from the exposed refractory lining surface.
indicate the of crystals and the of The Fig.777•••SEM
Fig.
Fig. SEMmicrograph
SEM micrograph of
micrograph of refractory
of refractorypowder
refractory powder
powder
hydroxide,
The ettringite and and un-hydrated cement grains. Porosity isa
SEMSEM
hydroxide, micrograph
micrograph
ettringite of refractory
of refractory flakes is flakes
un-hydrated shown cementisinshown
Fig. 6 and
grains. in Porosity
Fig. 6 andis
a refractory
unchanged
refractory
unchanged or
powder
or lower
lower in
image the carbonated
is Fig.
in the carbonated displayed zone.
in Fig. 7. The micrographs
powder image is displayed in 7. Thezone. micrographs indicate the pres-
The
indicate
The characterizations
characterizationspresence confirm
of
confirm calcitethatcrystals
that the refractory
the refractory
ence of calcite crystals and the absence of calcium hydroxide,ofettringite
the and the degradation
absence
degradation iscalcium
is due to
due to ••» Because
Because of
Since
of constraints
constraints on
commissioning was
on structural
structural changes
expectedpowder
changes and the
to be furtherand
the availability
delayed,availability
an innova-
carbonation of the castable’s cement phase, and the alkaline hydrolysis Fig.
of 7utilities,
• SEM micrograph
the of
combustion refractory
conditions and flue gas routing were were
hydroxide,
carbonation
and un-hydrated ettringite
of the cement andgrains.
castable’s un-hydrated
cement phase,iscement
Porosity and grains.
the alkaline
unchanged Porosity
or lowerhydrolysisin theis oftive
utilities,
pre-dryout the scheme
combustion conditions
was developed usingandexternal
flue gas routing
burners and hot
isunchanged
is further aggravated
further aggravated
or lower by
byin presence
the
presence of low
carbonated
of low concentrations
concentrations
zone. of potassium.
of potassium. carefully
carefully modelled to ensure effective and
modelled to ensure effective and safe dry-out operation. safe dry-out operation.
carbonated zone. study on the residual lining was also performed to gas generators.
AAThethermal
thermal
The
design study
characterizations
design
characterizations confirm
on the that
confirm the
residual
that the refractory
lining wasdegradation
refractory also performed
degradation isis due
dueto toto ••» The
• TheBecause
Because
radiant
radiant and convection
ofofcoil
constraints
and
constraints
convection
onon
coils were
structural
coils
structural
werechanges
changes
designed
and and
designed the
forthe
for 530
530 °C and
°C
availability
and
availability
of
verify
carbonation
verify operational
operational of the compliance
castable’s
compliance of its
cement
of its shell
shell
phase, temperature.
and
temperature.the alkalineThe calculat-
The calculat-
hydrolysis the
theof steam
utilities,
steam the
coil was designed
combustion
was designed for
for and450
conditions
450flue °C. and
°C.gas Due
Due flueto gasunavailability
routing
to unavailability were
carbonation of thetemperatures
castable’s cement phase, andtothefallalkaline hydrolysis utilities,
ofcarefully
the combustion conditions routing were careful-
ed
ed outsideaggravated
isisfurther
outside
further
casing temperatures
casing
aggravated by
by presence
presence
were
of
were
of low
low
observed
concentrations
observed
concentrationsto fall withinwithin
of
API de-
ofpotassium.
potassium.
API de-
A of aa cooling
cooling
ly modelled
medium
modelled
tomedium
for
ensuretoeffective
ensure
for the effective
the and
coils, dry-out
coils, dry-out
and safe
safetodry-out
was
was restricted
dry-out
restricted
operation.
to aa
operation.
to
sign
A limits
thermal [7].
design The condition
study on the of the
residual refractory
lining was lining
also in terms
performed ofto maximum
•» maximum
The radiant temperature
and convection of 250 °C
coils were have a
designed sufficient
for 530 safety
°C and
signthermal
thickness
limitsdesign[7]. The
and strength
study
strength
condition
on the
of hot
of the
residual
hot face
face
refractory
lining
refractory
was also lining
was adequate
performed
adequate
in terms
and
to of
verify
with-
The radiant temperature
margin.
and convectionofcoils 250were °C to have afor
designed sufficient
530 °C and safety
the
verify
thickness
operational operational
and compliance compliance
of of alkaline of refractory
its shell its shell temperature.
temperature. was The calculatedThe and calculat-
with-
outside the
margin. steam
steamdry-out coil
coil wascircuit was
designed designed
for 450 °C. forDue450 °C. Due
to unavailability to unavailability
of a cooling
in
ed acceptable
incasing outside
acceptable limits.
casing
limits. Since
temperatures
Since
temperatures
were alkaline
observed werehydrolysis
observed
hydrolysis
tocannot
fall within
is an
to
is an irreversible
fall within
APIirreversible
designAppropri-
limits
proc-
API
proc-de-
[7]. •• The
Theof adry-out
medium cooling
for the medium
circuit
coils,
included
for the
included
dry-out was
the
the radiant
coils,
radiant
restricted dry-out
to
chamber,
chamber,
a maximum
convection
was restricted
convection
tempera- to a
ess,
sign
ess, any
any loss [7].
limits
loss of material
of material
The and
condition
and strength
of
strength the refractory
cannot be reversed.
be reversed.
lining in terms
Appropri- of entry
maximum
entry duct, and
duct, and the transition
temperature
the transition of regions
250
regions °C between
to
betweenhave the
a
the convection,safety
sufficient
convection, air
air
ateThemeasures
conditionwould of the refractory
need to bebelining
taken in terms
for any any of thickness
further and strength
reduction in ture of 250and
preheater °C toby-pass
have a ducts.
sufficientPart safety
of the
the margin.
stack waswas also
also included
included to to
ate measures
thickness
of hotthickness.
lining
and would
strength need of to
hot facetaken
refractoryfor
face refractory was adequate and within acceptable limits. Since was further
adequate reduction
and in
with- » preheater
margin.
The
create dry-out andcircuit
a draft
draft in
by-pass
incircuit
ducts.the
included
the circuit.
circuit.
Part of
radiant stack
chamber, convection entry
lining
inalkaline thickness.
acceptable limits.isSince alkaline hydrolysis is an irreversible proc- • create
The a
dry-out
duct, andwith the
the transition included
regions the radiant chamber, convection
To
Toess, prevent
prevent
any
hydrolysis
loss further
further
of material
an irreversible
deterioration,
deterioration,
and strength the
the
process,
following
following
cannot
any
be
loss of material
corrective
corrective
reversed. actions
actions
Appropri-
and
•• Burners
Burners
entry withducts.
duct, and aa 22them long
m long ductbetween
duct
transition were
were
regions
the convection,
installed
installed
between bythe
by
air preheater
dismantling
dismantling
convection, theair
the
strength cannot be reversed. Appropriate measures would lining: be
need to and by-pass Part of the stack was also included to create aofdraft
EXPERT FACHMEDIEN GMBH

were implemented to need

ventilate and dry out out the refractory existing main burners inducts.
the radiant
radiant floor and ininwasthealso
entries theto
DÜSSELDORF – GERMANY

were
ate
taken implemented
measures
for any would
further to ventilate
reduction to be and
in dry
taken
lining for the
thickness.anyrefractory
further reduction lining: in existing
preheater main
in the circuit. and burners
by-pass in the Part offloor
the and
stack the entries of
included the
••lining
All pathways
All pathways
thickness. were immediately
were immediately opened opened to to enable
enable air air circulation
circulation ducts.
ducts.
create Figure
Figure
a draft 88 inshows
shows
the the burner
the
circuit.burner deployment
deployment in in the
the flue
flue gas
gas duct
duct
Toand prevent
prevent furtherhumiditydeterioration,
and dampness the following
dampness in corrective actions were
the heater.
heater. » ofBurners with a 2 m long duct were installed by dismantling the exist-
the heater.
heater.
To and prevent
prevent humidity
further and
deterioration, dry outthe thebyin the
following corrective actions • ofingthe
Burners
mainareas with a 2in m
burners long ductfloorwere installed by dismantling ducts.the
implemented
••were
Forced
Forced air to ventilate
circulation
air circulation
implemented to
andarranged
was
was arranged
ventilate and dry byout
refractory
placing
placing
the
lining:
blowers
blowers
refractory at
at regular
regular
lining: •• Unlined
Unlined
existing areas
main in
in thethe
the
burners
radiant
drying
drying
in the circuit
circuit
radiant
and
were
were
ininsulated
floor
the entries
insulated
and in with
the
of the
with multiple
multiple
entries of the
» intervals,
All pathways ensuring were thatimmediately
the humidityopenedlevels to enable
inside airthecirculation
heater and
were Figure 8 ceramic
layered shows thefibre burner deployment
blankets. inother
the flue
Alldeployment gas ductwere
openings of theclosed
heat-
• intervals, ensuring that the humidity layered ceramic8 shows fibre blankets. All other openings were closed
All pathways
prevent
sufficiently humidity
low.
wereand immediately
dampness thelevels
inopened heater.toinside
enabletheairheater circulationwere ducts. Figure
er. insulated dummy plates.
with
the burner in the flue gas duct
with insulated dummy plates.
» sufficiently
andForced prevent low.humiditywas
air circulation andarranged
dampness by in the heater.
placing blowers at regular in- of
» Dry-out the
Unlined areasheater. in the drying circuit were insulated withofmultiple lay-
••• Since
Since commissioning
commissioning was
was expected
expected toby
to be
be further
further delayed, an inno- •• • Dry-out was
was started
started immediately,
immediately, as continuation
as continuation the alkaline
of with
the alkaline
Forced
tervals,
vative
air circulation
ensuring that
pre-dryout scheme
was arranged
the humidity
was
placing
levels inside
developed using thedelayed,
blowers
heater were
external
an inno-
at regular
burnerssuffi- Unlined
ered
hydrolysis ceramic areasfibre
process
inblankets.
the
would
drying
have
circuit
All other
led to
were insulated
openings
further were closed
deterioration withmultiple
insu-
of the
vative
intervals, pre-dryout
ensuringscheme that thewas developed
humidity levels usinginside external
the heater burners were hydrolysis
layered process fibre
ceramic wouldblankets.
have led All to further deterioration
other openings wereofclosed
the
and ciently
hot gaslow.
gas generators.
generators. lated
structure dummy and plates.
eventually result in dismantling and relining the en-
and hot
sufficiently low. structure
with insulated and eventually
dummy result plates.in dismantling and relining the en-
• Since commissioning was expected to be further delayed, an inno- • Dry-out was started immediately, as continuation of the alkaline
Ceramic
vativeMonographs
©and
2017hot
pre-dryout
Expert
– Handbook
schemeof Ceramics
was developed using external burners hydrolysis process would Supplement
have led toto Interceram
further deterioration 03the
66 (2017) [1–2] of
gasFachmedien GmbH
generators. structure and eventually result in dismantling and relining the en-
 ,17(5&(5$0²5()5$&725,(60$18$/,, 
Ceramic Monographs 3.3.3.5 Investigation of Alkaline Hydrolysis in Refractory Linings
,17(5&(5$0²5()5$&725,(60$18$/,, G. Sukul, P.V. Balaramakrishna
of Process Plants: A Case Study
5()5$&725,(6)2580
HANDBOOK OF CERAMICS
CERAMIC MONOGRAPHS

5()5$&725,(6)2580

88 99
8 9

Temperature / °C
Temperature / °C
Fig. 8 • Refractory dry-out with external burner arrangement Time
Fig. 8 •8 Refractory
Fig. dry-out
• Refractory dry-outwith
withexternal
externalburner
burnerarrangement
arrangement Time/ /hh

Fig.
Fig.999•••Actual
Actualdry-out time-temperature curve
Fig. Actual dry-out
dry-outtime-temperature
time-temperaturecurve forfor
curve pre-dryout
pre-dryout
for pre-dryout
» Dry-out was started immediately, as continuation of the alkaline hy-
drolysis
tire
process would haveThe ledactual
to further deterioration of the struc-
tire100
ture and
t tofofrefractory.
100eventuallyrefractory.
result inThe actualmeasured
dismantling measured
and
time-temperature
reliningtime-temperature
the entire 100 t
mal
mal operational drying
Onceoperational
the initial signs drying arrangements are
of arrangements
alkaline hydrolysis are notnot available due
are available
observed, due
to
to de-
refractory de-
curve
curveduring
duringthe thepre-dryout
pre-dryoutoperation
operationisisshown
shownininFig.
Fig.9.9. layed
layedcommissioning
commissioningor orextended
extendedoff-line off-lineplant plantconditions,
conditions,aa special special
of refractory.
• •Post The actual measured time-temperature curve during the dry-out operations should be carried out as soonmay as possible. If normal
Postdry-out,
dry-out,regular
regularinspections
inspectionsofofthe therefractory
refractorylining
liningwere
were purpose
purposedry-out dry-out with with temporary
temporary burners burners may be be conducted
conducted to
pre-dryout
recommended operation is shown in Fig. 9. operational drying arrangements are not available due to delayed com-to
recommendedevery every10–15
10–15days
daysuntil
untilplant
plantcommissioning.
commissioning. remove
removefree freeand andbonded
bondedmoisture moisturepresent presentin inrefractory
refractory liningslinings [10].[10].
» Post dry-out, regular inspections of the refractory lining were recom- missioning
Dried or extended off-line plant conditions, a special purpose dry-
Driedrefractory
refractorylinings, linings,in in general,
general, have have much much lower lower tendency
tendency of of
mended every
4 Design and10–15 days until plant
engineering commissioning.
considerations out with temporary
undergoing alkaline burners
hydrolysis. may be conducted to remove free and bond-
4 Design and engineering considerations undergoing alkaline hydrolysis.
4.1
4.1Refractory
Refractorydesign design
ed
The moisture
Thepotential
present
potentialfor
inemergency
refractorydry-out
for emergency
linings [10].
dry-out actions
Driedwhen
actions when
refractory
normal linings,
normal safety
in
safety
For project sites having high humidity and atmospheric tempera- general,
and processhave much
control lower tendency
parameters are of undergoing
not in place alkaline
should hydrolysis.
be anticipat-
4. Design and engineering considerations
For project sites having high humidity and atmospheric tempera- and process control parameters are not in place should be anticipat-
tures,
tures,there
thereisisgreater
greaterpossibility
possibilityofofalkaline
alkalinehydrolysis monolithic ed
hydrolysisininmonolithic
Theduring
edduring
potentialthe fororiginal
theoriginal
emergency plant dry-out
plant design design and
actions
and be
when
be carefully
normalplanned
carefully planned
safety and and
and
4.1 Refractory
linings, especially design
for insulating castable materials. Hence,
linings, especially for insulating castable materials. Hence, it may be implemented. it may be process
implemented. control parameters are not in place should be anticipated during
Forpreferable
project to
preferable sites
tohavehaving
have high fibre
ceramic
ceramic humidity
fibremodule and atmospheric
module lining
liningininthe temperatures,
the radiant
radiantsec- sec- the original plant design and be carefully planned and implemented.
there
tion. isDue
tion.Due greater
tototheir possibility
their basic of alkaline
basicnature,
nature, ceramic hydrolysis
ceramic fibres
fibresdo indomonolithic
not
notreact linings,
reactwith
withat- at- 55Conclusions
Conclusions
especially
mospheric
mospheric forconstituents.
insulating castable materials. Hence, it may be preferable Investigation
constituents. Investigationofofthe thealkaline
alkalinehydrolysis hydrolysis mechanism mechanism was was carried
carried out out
toInhave
In ceramic
situations
situations fibremonolithic
where
where module
monolithic lining in the
lining
lining radiant
isisrequired,
required, section.
dual Due
layerto
duallayer refrac-
refrac- 5. Conclusions
their totounderstand
understandthe theextentextent and and effects
effects of of carbonation
carbonation on on refractory
refractory
basic
tory nature,
toryshould
shouldbe ceramic fibreswith
beselected,
selected, do not
with densereactmaterial
dense with atmospheric
material ininthe
thehot
hotconstituents.
face
faceandandan an Investigation
linings.
linings.Preventive of the measures
Preventive alkaline
measures hydrolysis
to
to minimize
minimize mechanism furtherwas
further carried outand
degradation
degradation to
and
In situations
insulating
insulating where layer.
back-up
back-up monolithic
layer.Dense
Dense lining is required,
refractory
refractory dual layer
requires
requires less refractory
lesswater
waterfor for understand
ananinnovative
innovative the dry-out
extent
dry-out and effectswere
process
process of carbonation
were developedon
developed forrefractory
for linings.
aa representative
representative
should
mixing
mixing beandselected,
and has withporosity
haslower
lower dense
porositymaterial
which
which inwould
the
would hotreduce
face and
reduce the anamount
the insulating
amount ofof Preventive
case
casestudystudymeasures ensuretoeffective
totoensure minimizepreservation
effective further degradation
preservation of and anlinings.
of refractory
refractory innovative
linings. De-
De-
back-up
alkaline layer.
alkalinehydrolysis Dense[8].
hydrolysis refractory requires less water for mixing and has dry-out
[8]. sign, process wereand
sign, engineering
engineering developed
and installation
installationfor a representative
guidelines
guidelines were case study
were developed
developedto ensure for
for
lower
Moreover,porosity
Moreover, the which
theselectedwould
selected reduce the
refractory
refractory amount
should
should ofalkaline
bebeofoflow hydrolysis
lowcement
cement [8]. effective
castable,
castable, project
projectsites preservation
sites inincoastal
coastal ofzones
refractory
zones to linings.the
tocontrol
control Design,
the effectsengineering
effects of
of alkaline and
alkaline hydrol- in-
hydrol-
Moreover,
since
sincelow lowCaO the
CaOselected
content
contentwillrefractory
willalso should
alsoreduce bealkaline
reducealkaline of lowhydrolysis
cement castable,
hydrolysis [9].
[9].OfOf stallation
ysis
ysisand guidelines
andensure
ensuresafe safewereand developed
andtrouble-free
trouble-free foroperation
project sites
operation ofin
of coastalplants.
process
process zones to
plants.
since
course, lowthe
course, CaO content selection
thematerial
material will also reduce
selection and alkaline
anddesign
design hydrolysis
choices
choices have
have[9].
totoOf evalu- control the effects of alkaline hydrolysis and ensure safe and trouble-free
bebecourse,
evalu-
the
ated material
ated together
together selection
with and
withallall
thethedesign
other choices have to be evaluated
otherthermo-mechanical
thermo-mechanical design require- operation of process plants.
designtogether
require-
with all the other thermo-mechanical design requirements of the project. References
ments
ments of of the
the project.
project. References
Lastly, for critical equipment installations, adequate provision for car- References
Lastly,
Lastly, for for critical
critical equipment
equipment installations,
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and
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an air-
air- Cao materials. J.1Europ.
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1(1991)
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tight interface
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ing HotGasGasGenerators.
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[3–4]209–212
209–212
tions atmospheric CO 2 and
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phases.
between atmospheric CO2 and the refractory cement cement
phases. phases.
EXPERT FACHMEDIEN GMBH

[6] Sukul,
[7]Sukul, G.,
Sukul,G., Balaramakrishna,
G.,Balaramakrishna, P.V.,
Balaramakrishna,P.V.:Herwadkar,
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Heat Transfer Lining
Transfer Design in Hot Gas Genera-
Design Considera-
Considera-
DÜSSELDORF – GERMANY

[7]
Refractory
Refractory
lining shouldlining lining should be
shouldinspected
be regularly regularly
be regularly inspected
inspected
for initiation for initiation
for initiation
of alkaline ofof
hydrolysis, tors. Internat.
tions
tions
Ceram.
forRefractory
for
Rev. 59 Lining
Refractory (2010) [3–4]Process
209–212 Plants. RAN 16 (2011) [5] 10–15
Lining ininProcess Plants. RAN 16 (2011) [5] 10–15
alkaline
alkaline hydrolysis,
hydrolysis, and if observed,
and ifpreventive
observed,actions immediate
immediate preventive actions [8]Sadik,
Sadik, C., Amrani,I.,I.,Albizane,
Albizane, A.: Recent advances ininsilica-alumina
silica-alumina refractory:
Lining in AA
and if observed, immediate shouldpreventive
be taken. The actions
pre- [7]
[8] Sukul,
review.
G.,C.,
Balaramakrishna,
Amrani,
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P.V.: SteadyA.:
State Heat Transfer
Recent
Soc.22(2014)
Design Considerations
advances for Refractory
refractory:
shouldbebetaken.
should taken.The Thepreventive
preventivemeasures
measuresinclude
includemaintaining
maintainingnat- nat- Process
review. J.J.ofof
Plants. RANAsian
Asian Ceram.
[5] 10–15
Ceram. Soc. (2014)83–9683–96
ventive measures include maintaining natural air circulation through [9]Standard
[9] StandardClassification
Classificationof ofAlumina
Aluminaand andAlumina-Silicate
Alumina-Silicate CastableCastable Refractories,
Refractories,
ural
ural air circulation
air circulation through the lining by opening all air entrance [8] Sadik,
the lining by openingthrough the lining
all air entrance by opening
pathways such as all
peep airand
entrance
access ASTMC.,
ASTM
Ceram.
401
Soc.
Amrani,
401
2
I., Albizane, A.: Recent advances in silica-alumina refractory: A review. J. of Asian
(2000)
(2000)
(2014) 83–96
pathwayssuch
pathways suchasaspeep peepand andaccess
accessdoors.
doors. [10]German
GermanAssociation
Association for for Refractory
Refractory and and Chimney
Chimney Engineering,
Engineering, Engineering,
Engineering,
doors. [10]
Materials,
Standard
[9] Materials, Design,of
Classification Construction. 2ndedition.
edition.Castable
Alumina and Alumina-Silicate Vulkan-Verlag,
Refractories, Essen (2004)
ASTM(2004)
401 (2000) ISBN
Ifnatural
If If natural aircirculation
circulationisisnot notsufficient,
sufficient,forced
forcedair aircirculation
circulationby by Design, Construction. 2nd Vulkan-Verlag, Essen ISBN
natural airairblowers
meansofofblowers
circulation is notrequired.
sufficient,
maybeberequired.
forced
Ifhigh
airhumidity
circulation
highhumidity
by means
isobserved,
observed,
3-8027-3155-7
3-8027-3155-7
[10] German Association for Refractory and Chimney Engineering, Engineering, Materials, Design,
means
ofde-humidifier
blowers may beunits may
required. If high If
humidity is observed, is
de-humidifier Construction. 2nd edition. Vulkan-Verlag, Essen (2004) ISBN 3-8027-3155-7
de-humidifier units may maybebeadded
addedtotoreduce
reducehumidity
humiditylevels.levels.
units
Oncethemay be added
theinitial
initialsignsto reduce humidity
signsofofalkaline levels.
alkalinehydrolysis
hydrolysisare areobserved,
observed,refractory
refractory
Once
dry-outoperations
operationsshould shouldbebecarried
carriedout outasassoon
soonasaspossible.
possible.IfIfnor-
nor- Received:31.07.2015
Received: 31.07.2015
dry-out
04 Supplement to Interceram 66 (2017) [1–2] Ceramic Monographs – Handbook of Ceramics
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