Metal Dusting
Metaldusting can cause severe problems inthe operation of ammonia, methanolandsynthesis gas
plants. Worldwide qata on the causes ofmetal dusting do notsufficiently explain why metal dusting
occurs in some cases while it does not in others. Further research is needed on this phenomenon, as
well as the methodof avoidingmetal dusting by properprocess and equipmentdesign and material
selection.
typ
Si,
1.5
w
etal dusting is a high-temperature corrosion
phenomenon well known by the process
industry, especially in connection with COrich gases at temperatures between 700C and S50C.
Methanol plants in particular have experienced metal
dusting downstream of reformers. However, due to
incidents experienced overthe last couple of years, the
lower temperature range for metal dusting has to be
revised to start at 450C. Furthermore, not only
methanol, but also ammonia process gases are known
to causemetal dusting.
Metal dusting is closely connected to the carbon
potential of the process gas and is often characterized
as catastrophic carburization, because parts, when
attacked, mightbe totally damaged within weeks.
In ammonia plants, metal dusting has usually been
observed as an attack on ferrules (Figure I) and
bypass liner in the waste heat boiler downstream the
secondary reformer. For the last couple of years, however, severe damage to boiler bypass arrangements
and superheaters downstream of the boiler and to the
channels between boiler and superheater have been
1996
r-.
at i
Iy
ox
be
ho
tYr
Th
sid
nu
no
all
al1
n:
n
ro
th
c(
Weight
Surface
Temperature Increase
Vo
"C
617 620
Inconel
I nco n e l 6 l T 660
Inconel6UI 660
0.06
0.8
().0
Formation
of CarburizationPits
of Metal
Methane
Lrttle
Little
Moderate
Consrderable
Lrttle
None
Minor
Manysmall
Verysmall
H2 49.3Vo,
H2029'5Vo,COl6'6Vo,CO2 5.67o
Gascomposition:
34.4barz
Pressure:
typicallyareasfollows:
,Altay 800/800H:
3lVo Ni,20VoCt,4l%oFe,,0.4Vo
Ti and<0.174C.
Si,0.5IaN:1,0.5ok
.Alloy 601: 617oNi, 237oCr, l4%oFe,<0.5V0Si'
C.
0.05Va
1.51oAl.O.2VoTi.
Whatis MetalDusting?
Metals exposedto gaseswith a highcarbonpotential
(450-85trC)arefrequenttemperatures
at intermediate
ly observedto disintegrateinto fine metaland metal
oxide particlesmixed with carbon.Thepowdermay
awayby gasleavingpits,grooves,and
be transported
holes in the metalsurface.For obviousreasons,this
is usuallycalled"metaldusting."
type of corrosion.
of the attackedmaterialmay vary conThe appearance
siderablyfrom an almostperfect surfacewith a small
numberof tiny pits (Figure3a) to a veryrough,cauliflower-like surface(Figure 3b). Thisdependson ths
alloy, the processingof the material,the temperature,
and the gascomposition.More thanonemechanism
most of the
may be involved.In very severecas&s,
a
few
within
days.
materialmaydisappenr
of rnetaldusting
observation
cases
of
industrial
Few
havebeenreportedin detail in literature.Grabkeet al'
(1984) have reporteda casewherea hood made of
austeniticFeNiCr steelfor batchannealingof coldrolled steel coils at 700'C was sevedy conoded' In
this casethecorrosionoccuneduponchangingthe gas
compositionandthe temperatureduringannealing
MANUAL
TECHNICAL
AMMONIA
181
FeeC-r 3Fe+ C
Table2. IndustrialCases
of MetalDusting
Phnt
NHr
Material
. Channels
between Alloy 800H
WHBandSSH
. lntemalshellin SSH
. Baffles,tie rods
andsoacors
in SSH
Frtimatd Estimated
Meesurts agaird Mctal Dusting
TmpratureTernpenturc
hocessGrs Marl Surfact
Done:
Channelsbetwsl WHB andSSH lined with platsi!
ss 304.
Pluggingof the SS!{-tsbcs,damagedby mnoded tefftes
(52 out of 300).
SS 304 tuber inscrtrdbetweencxchangertubesto
substitutethe bafflesfor $ppon of te rubes,
Addilional stcam$pply (12 t/h) ro secondaryreformcr.
Result:
Good
Planned:
Changeog SSH-nrbe
bundlcmalerialto be Alloy 601H.
Additional stearnsupplycut ofi
NHr
. WHBoutletcone
. Channels
between
WHBandSSH
NH!
. ByPass
valve in
WHB
800H
^ 900"c
-90trc
Planncd:
Changematerials
of chatnelsbetwenWHB andSSH
from Alloy 800H ro Alloy 601.
Dotlz:
someparls replaccdwith new pans in malerial
HastelloyC-276.
Ruult:
Uncertain
Planrcd:
Follow thecourscof conosionandreplaccpansu rey
are damaged.
rr
MeOH
NH,
o Ferrules
r Bjrpass
linerin
WHB
. Bypassvalve
in
WHB
ss310
a Channels
betwen A[oy 8m H 400 - 600'c 400-600c
WHBard.SSH
. Cbannels
betwen
twoSSH's
AMMONIATECHNICALMANUAL
Dotu:
Changeof materials.
Charge of operationpanmeters
Result:
6ood
It!duct
t!
Locrtion of Attack
Meterial
Btima.ed
Fdimated
MeasurcsagainstMetal Dusling
TemperaturcTIryeiriure
PrccessGrs MetalSurface
60(r- 95f c
Gu
Donz:
Fenule t)?e changedto Inconel 600
Rault:
Unknown
NH,
o Tubesof ssH
NH,
. Tubesof SSH
Alloy 8fi)
Alloy 600
Synlhesis . Transfer line
betweer primary and
Gas
secondaryreformer
. WHB bypassvdves
. Tubesof SSH
Y22
Done:
to Alloy 800H
Change
of material
Sulphuraddition
500P
c
fisJn t'
500c
Goodfor thetrursferline
WHBbypass
still a problem
r Ferrulesof WHB
800
(-
- 900"c
to SS304L
of material
NHj
r Ferrulesof WHB
Alloy800
90(rc
550- 65trC
Dona:
Changeof materielto AISI 446
Resuk:
No metal dustingbut s?riols embrittleme{t in fenuks
. Tubesof WHB
Alloy800 90f c
400- 60trc
Donc:
l stallationof tubebundlein I tl Cr riMo withceramic
coatint
Resak:
Good
NI!
Doru:
Linersrcmoved
andrefractorylefi bare
Result:
cood
NH,
MANUAL
TECHNICAL
AMMONIA
li
I
i
100trc
lmtrc
183
Table2. IndustrialCases
of MetalDusting(continued)
Plant Product Locationof Atte*
o
P
NHr
Msterial
of
NH,
o Fem-rlesof WIIB
o Bypassva.lveof
WHB
NHI
ss310
deta
NHt
The
trte
Estirnatd Estimated
a3ainstMetslDusting
lMeasurcs
Tempersl$rr Temperature I
kocess Gns MetalSurface I
Done:
Replacemcnt
of all attaclad materialswith Alloy 600
Result:
Good
ticl
ame
wirh
lDone:
of fenulesandbypasssleevewith rhesame,
lReplacemclt
naterial.
in
ss
316
lbut
llncreateinlet temperatur10secondcmpartmentfrom
c to6strC.
l55r
I
lResult:
lCodd
ll'
I
MeOH
r Ferrulesof WHB
r Bpass ralvcof
WHB
lcas
Alloy 600
YZz
refo
ss316
Alloy800
I
[,
cont
950"
dust
Iem
(ryp
. Ferrulesof WHB
r Bypass
linerof
WHB
teml
Alloy800H l70f c
Alloy800H t950.
c
- 700'c
15ff - 950 C
ispr
per:
Bou
Resuk:
Unknom
Planned:
Rcplacemart
ofall ferrules
to ferrules
of Allov601.
Sucl
atta
allc
shr
I
ina
coll
g2\
D_'
SUfr
bar
pro
AMMONIATECHNICALMANUAL
184
1996
reformedgas.
T h r o u g h o uat l l t h e e x p e r i m e n t sf o
, r m a t i o no f
consehasbeenobserved
as a characteristic
methane
quence
of metaldusting.
experimentsperformedin this
For ferritic materials,
test
rig
showed
that alloys like T9l were
laboratory
heavilyattackedevenat temperatures
aslow as620'C,
Kanthal
could
not
be
attacked.
For austenitic
whereas
materialswe found that Alloy 800H wasattacked
within a few hours,asseenfor instancein-Figure5.
work by
Importantresultsfrom the experimental
Topsoeareshownin Tablel.
with MetalDusting
WorldwideExperience
185
1996
Figure1.Ilpical metaldustingattackonferrules.
SteamSupe.ieder
t[lut
\\ 1)
llll**
F=={- | I --Tl\
tl
6oo.C I Gorc F|
Figure2a.Wasteheatboilersystemwith bypass.
AMMONIA
TECHNICAL
MANUAL
186
1996
Figure3b,Cauliflowerlikesurface.
testcouponin Alloy800H'
Figure5.Exposed
MANUAL
TECHNICAL
AMMONIA
187
1996
alum
film.
a tig
--*{la-dTh
I
tbL-l#-r
trrN. fftq-r-ffi
---J-.n-\
self
the
.l-'-*r
|la--f---.--r-H-/'
Fi-ijil
\-IClilSwF
--------{i-F Eq a R r..,r.r.i F
rs;N\
l#ri'.\
uffi-J
I
I__
i
i
ii
rr *
- r |- . .!\{ \
4m.i__l
-ftFfirR\
\
i
Nic
atm
but
ltLit
ni,
ex
Figure 6. Wasteheatboiler with ferrules,bypass
Iiner and bypassvalve.
controlledin sucha way that the critical temperature the gasis cooledto the temperature
below which
rangeis avoided.Thesecondway is by materialselec- metaldusting
tcndsto occur.
tion to avoid or minimizethe risk of attackor to hampertherateof conosion.Thethird way is to selectcer- Material selection
tainprocessconditions.
Grabkeet al. performedtestswith a numberof
The alloys
Design of equipment
alloysof interestfor industrialapplication.
testedincludeda rangeof commonlow-alloy steels
is
shown
in
(Grabkeand Krajak, 1994) andhigh-temperature
A wasteheatboilerwith internalbypass
Figure6. Metal dustingfrequentlyoccursin the feralloys(NavaPazandGrabke,1993).In addition,sperules,the liner of fhe bypasspipe, andthe bypass cially prepared
Fe-Mn alloys(Grabkeet al., 1993)
valve system.Figure7 showsanotherdesignof a
were tested.Small amountsof Mn were expectedto
wasteheatboilerfor thesameservice.
metaldustingbecause
of the stability of the
suppress
rings. (Fe,MnhCcarbides.However,after some selective
First,tle inlet femrlesarereplacedby ceramic
the criticaltempera- oxidationunderMnO formation,the surfacewas
Hence,no metalpartsexperience
ture as the inlet channelis refractoryJined,andthe depletedof Mn, andunstablecarbidewasformed,iniboiler tubes are effectivelycooled by the boiling tiatingmetaldusting.From theresultsof thesestudies
water.
that all knownalloyswith suitable
they concluded
Secondly,thebypassis avoided.Instead,thetemper- rnechanical
propertiescan be attacked
by metal dustatureis controlledby a splitof the gasflow in two par- ing if thegasis sufficientlyaggressive
and if the surallel tube bundleswith slightly differentcooling faceprotection
layeris insufficient.
capacity.One bundleis cooling too muchandthe
A protectivesurfacelayer maybe formed either by
othertoo little. A valvesystemat the coldendof the oxidationor by coating.Alloys containingchromium,
In both tubebundles
boiler controlsthe temperature.
MANUAL
TECHNICAL
AMMONIA
188
1996
tic
rh
m
)h
lf
rs
ls
'e
))
o
e
only in rarecasesis it
aluminum,or siliconmay form a protectiveoxide normallynotapplicablebecause
againstpoisoning
alloyshaveCr concentrations possibleto take properprecautions
film. High-temperarure
("I" in Table
case
In
one
downstream
catalysts.
rangingfrom 12-30wt. 7o.Underoxidizingconditions of the
successfully.
a tight, protectiveCr2O3film is formed.However, 2), sulfurinjectionhasbeenintroduced
decreases
the carratio
the steam/carbon
Increasing
crackscaneasilyoccurin the oxidelayers.Therefore,
possibleto prebonpotentiaiof thegas.It is tlrerefore
protectioncanbe maintainedonly if theoxidefilm is
steam.
dusting
by
sufficient
adding
vent metal
ieli-healing,whichis the caseif the Cr diffusivity in
However,in practicethis maynot be an economic
the alloy surfaceis high enough.In thebulk alloy
solution.
materialthediffusivityof Cr is too low atthetemperaturesin question.
of the oxide film may be Gonclusions
The imperviousness
destroyedby reductionif it containsnickelor iron.
Metaidustingcausesseveredamageundercertain
Nickel and iron may migrateinto the oxide if the
which may
is oxidizingnot only towardchromium conditionsin ammoniaplants.The theory
atmosphere
is notsufficientlydeveloped
thephenomenon
important describe
butalsotowardnickelor iron. It is therefore
occursin somecases
that the oxide film shouldbe withoutnickeland iron to explainwhy metaldustlng
occurin othercases.Researchis still
from the beginningandthat the surfaceshouldnot be whileit doesnot
which is oxidizingtoward neededto explain this andto achieveknowledgeof
exposedto an atmosphere
how to avoid metaldustingby properprocessandlor
nickel or iron at any time during the reaction.It is
designandmaterialselection.
expectedthat metalduiting can be avoidedif these equipment
apply:
Today,thefollowingobservations
conditionsarefulfilled.
.MetaldustingmayoccurwhenCO-richgasesunder
suchas Si andAl enhancethe
Alloying elements
A content pressureare in contactwith metal-alloy surfacesat
material'sability to form chromia(Cr2O3).
between45ffC and850"C.
temperatures
the Cr
of I.5Voor moreof theseelementsincreases
.Alloy 800Happearsto be highlysensitiveto metal
promotestheCr2O3fordiffusivity andconsequently
dusting.
mation.
.Alloy 601 is considered
to be an advisablechoice,
In the fenitic gtoupof materialswe havefound that whenmetaldustingmaybeexpected.
Fe-Cr-Al alloyscontainingabout570of Al form a
.Whenmetaldustinghasbeenobserved,increasing
oxide,andno signsof metaldusting thesteamcontentof the process
strongprotective
gasmay improvethe
were seenafter a prolongedtest underseverecondi- situation.
propertiesof
thepoor mechanical
tions.Unfortunately,
.Process
plant equipmentfor Co-rich gasesshould
thesealloys makethem unsuitableas construction preferablybe designedto avoidmetatsurfacetempermaterialsin steamreformingplants.
aturesbelween450'C and85fC.
Among the austeniticmaterials with reasonable
mechanicalpropertieswe found that Alloy 601 perLiteratureCited
formsbest.Weascribethis to the 1.57oAl content'
Processconditions
to
poison
thatsulfuris a veryheavy
It is wellknown
189
(1992\.
1996
lnI
Grabke,H.J.,C.B.Bracho-Troconis,
andE.M. MtillerLorenz,"MetalDustingof t owAlloy Steels,"
Werkstoffe
undKorrosion,45,215(1994).
Hochman,R.F.,Proceedings
of theSymposium
on
Propertiesof High-Temperatur-e
Alloyswith
Emphasis
on Environrnental
Effects,Z.A. Foroulis
andF.S.Pettit,eds.,The Elechochemical
Society,
pp.715-732
(1977).
NavaPaz,J.C.,andH.J.Grabke,'Meral
Dusting,"
Oxidationof Metals,39,43?( 1993).
Richardson,
J.A."Boudouard
CarbonandMetal
Dustingin SteamReformingPlants,"Nitrogen 1993
49 (1993).
DISCUSSION
Dean Damin, DuPont:Under the generaltopic of
materialselectionto preventor slow downmetaldusting,basedon eithertheinformationyou received
from
the peoplewho sentyou informationor from your
own work, do you haveany commentsregarding
the
useof coatingsystems
to preventmetaldusting?
Stahl: We havereceivedinformationon zirconium
oxidecoatingfrom a Dutchplant.As far asI know it
hasbeensuccessful.
Youcan,of course,enhance
the
protectionby meansof coatingaluminaor zirconium
oxideonto the surface.Thatis anotherwayof making
an oxide; it may be very costly.It is an interesting
aspect,and I know that peopleare thinkingalong
thoselines.
Kanwer Khan, Engro Chemicals..
Curently,we are
operatinga high steamto carbonratio andwehavenot
had any metal dustingproblemswith our ferrules.
\Vith futureexpansions,
we arelookingat thepossibility of reducingthe steamto carbonratio.Doesyour
dataindicatea numberbelow which we shouldnot
go?
Stahl: We have beenaskedabout that a numberof
tlmes-- which steamto carbonratio is safe,and I
think it's impossibleto say.I hopethat we candesign
theequipmentnow in sucha way thatyoucangofor zi
steamto carbonratiowhichis lower than3, maybe
2.6. I would not recommend
increasingthesteamto
carbonratio because
thatincreases
costs;however,
if
you havea problem,thatmight be oneof thewaysto
go until you canmakea repair.I cannotgiveyoua fig-
AMMONIA
TECHNICAL
MANUAL
ure.
Khan: Youtalkedaboutreplacingthefenuleswith the
ceramicring. Is that a provendesign?Has it been
installed
somewhere?
Stahl:Wehaveinstalledit in a boilerin Korea.
Khan:Is it running?
Stahl:Yes,it hasbeenrunningfor yearsnow without
problems.
Luc Guns,B,ASf;Concerningthedesignthat you
show,thewasteheatboilerwasadoubletube bundle.
Is thata provendesign?
Stahl:It is nota provendesign;it is beingbuitt.One
companyis buildingsucha boilerandthe designwill
be provenin a largeunit. It hasnotbeenprovenyet.
Guns: Is thecompanythat built it alsoa boiler after
secondary
reformer,or is it in anotherservice?
Stahl:It is a boileralterthe secondary
reformer.
Rick Strait, M.W. Kellogg Co: Do you have the
streamcompositions
for your surveyof the plants?
Your surveyexcludedany informationon the stream
compositions.
Stahl:Yes,thatis right. I havenotaskedfor that.
Kevin Still, MossCas:\tr'earetheplantthat successfully uses800H.The first reasonfor it, we believe,is
we run it in extremelylow steamto carbonratio. Our
primaryreformeris runningat 2.5 andour overall
steamto carbonratio is runningat 1.25.Secondly,
we've got an olefin contenton the inlet of the secondaryof 2 mol percent.Webelievethatit's the olefin
190
We
our
period.ln our specificinstancewe are quite comfortablewith 800H,which alsooffersa costbenefitto us'
My tastpointis'we startedinjectingsulfur in Marchof
1995.The sulfur we injectedat 0.1 PPM on the inlet
hasan effectof 20 PPB(20 partsper
of thesecondary
That solvesour
billion)on theoutletof the secondary.
we're
hopingthatit
problems.
and
process
condensate
will alsoassistus wifh metaldusting.So, yes,we
injectsulfurat extremelylow levels.
t93
he
en
rut
:le
iil
IE
:?
ts
rr
ll
:I
MANUAL
TECHNICAL
AMMONIA
191
1996