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Survey of Worldwide Experience with

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,

Henrik Stahl and Seren Gyde Thomsen


Haldor Topsee NS, DK-2800 Lyngby, Denmark

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

AMMONIA TECHNICAL MANUAL

experienced (Figures 2a and 2b).


The mechanism behind metal dusting is not fully
understood. It is therefore not possible to explain satisfactorily why sometimes, but not always, metal dustmg occurs.
Topsee has performed tests on different materials
with respect to sensitivity to metal dusting in a realistic environment. Based on this research and information gathered from ammonia plants all over the world,
the following can be recorded:
-Some materials are more prone to metal dusting
than others. Alloy SOO/SOOH has frequently been used
for service in the critical temperature range, and Alloy
SOO/SOOH is one of the materials most prone to metal
dusting.
-As the tendency toward metal dusting to a large
extent depends on the quality of the oxide layer, it is
important to select materials that form a good amorphous oxide, which is highly self-healing in the case
of cracks. Owing to its content of aluminum, Alloy
601 is considered such a material.
The compositions of Alloy SOO/SOOH and Alloy 601
180

1996

r-.

at i
Iy
ox
be
ho
tYr
Th
sid
nu

no

all
al1
n:
n

ro
th
c(

Table1.Summaryof Resultsfrom TestswithlnconelFamilyof Materials


Alloy

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

cycles.Colwell(1992)hasrcporteda detailedexaminationof anAlloy 800 linerfrom an intemalbypassin


a wasteheat boiler downstreamof a hydrogen
reformer.The liner was removedfrom a wasteheat
ofseveremetalloss.Richardson(1993)
boilerbecause
the conditionsin termsof gascarbonpotenindicates
tial andtemperaturefor sometencasesof metaldustingof austeniticalloyswhichhaveoccunedin relation
to steamreforming.A numberof severeproblems
causedby metal dustingattackwere reportedin the
1995AICLE AmmoniaPlant SafetyManual. ln all
cases,the metal dustingconosiontook placewithin
thetemperaturerangeof 450"C-700'Cand in gases
witha highcarbonpotential.
Relativelyfew fundamentalstudiesof metaldusting
havebeenreported.Someearly sfudieswere summarizedby Hochman(1977).More recently,Grabkeand
coworkers(1993,1994)havereporteda numberof
studiesof metaldustingexperimentswith
fundamental
alloys.General
low-alloysteelsand high-tcmperature
conclusions
basedon thesestudiesare that all alloys
containingiron or nickel are sensitiveto metal dusting.
Basedon fundamentalstudiesof the reactionof singl+crystalfilms of iron in CO,Hochman(1977)sugfor metal dusting:(a)
gestedthe following mechanism
dissolutionof carbon;(b) precipitationof Fe3C
(cementite);and (c) decompositionof cementite
accordingto

181

FeeC-r 3Fe+ C

Table2. IndustrialCases
of MetalDusting
Phnt

hoduct Ircation of Attsck

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

450- 60trc 55rC

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

Alloy800H 60tr- 900 c 60r - 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

- 90trc 60f - gqrc


Alloy600 60cr"
Alloy800H

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

Table2. Industrial Casesof MetalDusting (continued)


Plant

It!duct

t!

Synthesis . Ferrulesof WHB

Locrtion of Attack

Meterial

Btima.ed
Fdimated
MeasurcsagainstMetal Dusling
TemperaturcTIryeiriure
PrccessGrs MetalSurface

Alloy 800 9500c

60(r- 95f c

Gu

Donz:
Fenule t)?e changedto Inconel 600
Rault:
Unknown

NH,

o Tubesof ssH

AlloyE00 600"- 750c 600- 75(rc

NH,

. Tubesof SSH

Alloy 8fi)

Alloy 600
Synlhesis . Transfer line
betweer primary and
Gas
secondaryreformer
. WHB bypassvdves
. Tubesof SSH
Y22

600"- 75{rc 60f - 75trC


300"- 75r c 580.62ffC

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!

r Shelllinerof WHB ss310


(watertubetype)

400"- 45f c 37tr- 425.C

Doru:
Linersrcmoved
andrefractorylefi bare
Result:
cood

NH,

. Shelllioer of WHB Alloy800


(watertubetyps)

MANUAL
TECHNICAL
AMMONIA
li

I
i

100trc

lmtrc

183

Table2. IndustrialCases
of MetalDusting(continued)
Plant Product Locationof Atte*

o
P

NHr

Msterial

r Shelllinerof WIIB SUS3IOS ?uP-8ffiC


(walertubetypc)

of

lMonitoring tire mehj surfacetempeaturc

500.- 6m c 5{Xr- 60ff C

NH,

o Fem-rlesof WIIB
o Bypassva.lveof
WHB

700"-800c nxr - 65(rc

NHI

r Ferrulesof WHB Alloy800 50tr- 700c 500- 65trC


. Bypasslinerof
WHB
(2 compaflme0ts)

ss310

deta

mtr- 70sC lDonc:

. Ferrulesof WHB Alloy 8ff)


. Bypasslinerof
WHB
r Bypass
valveboxof
WHB
I B)?assassanbly
of
SSH

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

lsynthesisr Tubesand slrcas

lcas

Alloy 600
YZz

65(r- 700c 650 - 700.C


50cP
c
50trc

refo
ss316
Alloy800

I
[,

cont
950"
dust
Iem

of AllonizedAlloy 800 tubes.


.Ox, coalingof tubesheet.
ofSS310replaced
by paru ofSS 321A.
of quenchtemperaturc.
Increaseof stfamto cafton ratio.

(ryp
. Ferrulesof WHB
r Bypass
linerof
WHB

teml
Alloy800H l70f c
Alloy800H t950.
c

- 700'c

15ff - 950 C

ispr
per:
Bou

inspectedanddanaged fenules rcplaced.


pffts of bypassliner replaced.
l(ktedal typeremainsAlloy 800H)

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

of cemenThe iron particlesfrom the decomposition


The
reaction.
accelerating
the
lite act as catalysts
kineticsnrdiesby Grabkeandcoworkerscondetailed
For alloyswith a highcontent
firmedthismechanism.
of nickeltheyobservedanothermodeof deterioration,
Nickel
involvinggraphitegrowth on grainboundaries.
conmetal
observed
at
dusting
has
never
been
carbide
ditions.In thenickelcaseit is mostlikely thatcarbon
of nickel
formationgoesthrough(a) supersaturation
to
grainsby carbonfollowedby (b)carbonsegregation
par(c)
of
nickel
boundaries
causing
detachment
grain
ticlesfromthealloy,and(d) growthof long carbonfilcatalyzedby nickel particlesin accordance
arirentS
(Alstrup,1988)for
with the well-knownmechanism
carbonfilamentgrowthon nickelcatalysts(Figure4).

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

It is known that in a significantnumberof cases


by ToPsoe
Research
Experimental
metaldusting hascausedsevereproblemsin operation
of ammonia,methanoland synthesisgasplants.
in
Two differenttypesof testshavebeenperformedby Recentcasesknownto Tops6eare summarized
Topsge.
Table2. It is obviousthatAlloy 800Hhasfailedin
The first test seriestook placeat the outlet of a manyplantsover a widerangeof processconditions.
of
because
reformerpilot unit. The reformedprocessgas was EventhoughAlloy 800Hhasbeenselected
(13-mm)
under
temperature
properties
good
in
the
temperature
passing
a
ll?-in.
tube
mechanical
over
its
rangingfrom rangein question,it appearsthat this specificalloy is
controlgiving tube wall temperatures
thatmetal verysensitive
to metaldusting.
950"Cto 500'C.It washerebydemonstrated
dusting will take placein a windowof intermediate In somecases,if metalpartshavebeenusedasliner
temperatures
betweenthe Boudouardtemperature for protectionof refractory,the liner hassimplybeen
(typically800'C)being the upperlimit and a lower removedand the refractoryleft bare.In othercases,it
(typically 650"C).The lower temperature has been decidedto replacethe attackedparts and
temperature
is probabtyimpactedkinetically.The Boudouardtem- makeno changein materials.Finally,therearecases
peratureis the equilibrium temperaturefor the whereparts havebeenchangedto materialsthat are
Boudouard
procesS:
supposedto be lesssensitiveto metaldusting,Alloy
to be sucha material.
601hasbeenconsidered
-r
2CO CO2+ C
Processconditions,e.g.,an increasein the steamto
carbonratio, havebeenchangedin a few casesas a
However,in mostcasesthis may
Suchmaterialsas SS304andAlloy 800H were easily temporarymeasure.
production
economics.
favorable
to
less
lead
attackedwhereasalloys like Haynes214, Kanthal,
allonizedmaterials,nickel, andAlloy 600 did not
Howto Oealwith MetalDustingin Design
showanysignof metaldusting.
in
our
place
laboratories
Thesecondtestseriestook
Phase
in a testrig especiallyequippodfor this purpose.A test
canbe
by a jet of process In thedesignphasethreedifferentapproaches
coupon(Figure5) was approached
and pres- pursuedwhen metaldustingis considered
a potential
gasof a selectedcomposition,temperature
between1 and40 problem.The first and most importantprecautionis
could be adjusted
sure.Thepressure
120
between and 80ffC. The theequipmentdesign.By properlayout,temperatures
bar andthe temperature
of a typical' of metal partsin contactwith the processgascan be
process
gaswasmixedto thecomposition
MANUAL
AMMONIA
TECHNICAL

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

Figure2b. Wasteheatrecoverysystemwith bypass

186

1996

l-igure3a.Pitsona pieceof tube.

Figure3b,Cauliflowerlikesurface.

Figure4. Carbonlilamentgrowingon nickelcrys'


tals.

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.

Figure7. Wasteheat boiler with doubletutre


bundle.

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

'the nickel and iron catalyzedcarbonformationreactions.This cenbeutilizedto preventmetaldustingby


addingsmall amountsof H2Sto the gasandthereby
poison the catalyticsites responsiblefor the carbon
has
formationstepof metaldusting.Thisprocedure
beentestedandfoundto work well, butthesolution is
MANUAL
TECHNICAL
AMMONIA

Alstrup,I., "ANew ModelExplainingCarbon


FilamentGrowth on Nickel,Iron andNi-Cu Alloy
109,241.1(1988).
l. Catalysis,
Catalysts,"
Amwnia TechnicalManual,Yol.35,AIChE' New
York (1995).
Conosionof a Heat-Resistant
Colwelt,R.L.,"Gaseous
Handbookof Case
(Metal
Dusting),"'w
Alloy
Historiesin FailureArulysis1,ASM International

189

(1992\.
1996

lnI

Grabke,H. J., R. Krajak,andE.M. Miilter-Lorenz,


"Metal Dustingof HighTemperature
Alloys,"
Werkstoffe
undKorrosion,44,89 (1993).
Grabke,H.J.,R. Krajak,andJ.C.NavaPaz,"Onthe
Mechanismof Catastrophic
Carburization:'Metal
dusting,"'CorrosionScr.,
35, 1141(1993).
Grabke,H.J.,J. Hemptenmacher,
andA. Munker
"Hochtemperafurkonosion
von
Schutzgasgltihhauben"
Werkstffi und Korrcsion,
'
3 5 , 5 4 3( t 9 8 4 ) .
Grabke,H.J.,andR. Krajak,"Metal Dusting- eine
konosiveAufkohlung,"
HTM, 49,150(l994).

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

contentthat is affectingthe stablesurfaceformedthesearetheoxides.Westartedup with 600andwithiin six monthswe'rehavingfailuresall overthe plant'


Wereplacedit with 800H,and sincethenhavedonea
numberof testsandfound that 601 andsomeof the
nicrofersareactuallybetterthan the 800Hin our specific situation.Sinceinstallingthe 800Hwe'vebeen
runningfor l8-20 monthsin the differentapplications
andhavefounda metallossof 0.2 mmoverthattime

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.

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MANUAL
TECHNICAL
AMMONIA

191

1996

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