lndian J. Fert., Vol. 6 {8), pp.

52-55 (4 pages)
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RefGrsFIGtr Tuhes Failures in

Ammglnla Plants affid lts
G{llttrol !AGase$tudy
R.P.Sharma
6. Fla t-24, R" C. E
Ope- K Bloch- Colool
Chembur Mumboi-400074

Frimnry r*f*rmqr im th* nr**t *riti**l xnd l"':ighty strs*s*d

*q*ip:nr*nt in nr: mntrn*niw plant" lt **n*i*t* *f *m?*lyxt fi{l*e$
t*hsx *rrmng*d in *ing$* *r d*xhi* r*w int* tw* r*dimnt
*hmr:"rh*rs" Th* **nvi** iif** *f ;"wf*l'rn*n tr:hrys *f typ:i*nl n:mtmrial
im *mtirncet*d tc bs sb**t 1,**,*** h**rs i,;r:**r r:*rrsiaf

*p*r';xting **r:eJiti*n*. i-{*e*'vmvrur, th*mm tuh** *6:*n*t* v*r5r

*i*xx t* th* *3**r*tin6 iir:r*t* *f t*rnp*raYur* seri* 5:r*nx*r*x *r:*
x s!r*$ m**i*i*ntmi *xp*m*r* fr:wy*n* th* r:*rn'lml **nditimr:$ *&rx
*ra*ti*ally mffe*t tir* tnh:m $i{*. Yhlm mr{i*l* **m!* with *:p*ra*ti*n
*f r*fmrr:"1*r, *if* *f rmf*rm*r tl:h**, typ** *f r*f*rnn*r tu*m
{ecili.ir** xr:*i th*tr sx**lranixry:. & *mn* ntu#y nn r*fc}rrx*r t*h**
{silur** lrss b*sn r*p*rt*S" N*tv **v*l*pr**r:tm in r*{mrrx*r
?xb*s rv:mt*n$sls haev* ais* h**n fq:*rnh**$ *p*n.

*ffi**
n Ammonia Plants, prim ary The steam reforming process of
ffi reformer is known as the heart hydrocarbons rnay be described by the
ffi of the plant becayse it is used to
...i$iiti*generate hydrogen rich
Steam Reforming Process
synthesis gas frorn petroleum oil co4o + 2tIrO 5 Cn_r H-_z* COz+ 3H2

(Naphtha) or hydrocarbon feed stock cH+ + 2kI,rO 5 COz+ 4H2

like natural gas etc. Hydrogen rich
synthesis gas is the main raw coz+ Hz 5 CO + FI2O
materiatr used f,or the production of
ammonia. CO+HrO 5 COz+9.9 Kcal.

i$ iil t.F iilt i:t '':t,'iil:

The other hydrocarbon reforming
{ru iN, ,t ,i,.:"$ ii*;i.. ,i}ii i\i,.$"

i j,:i .., r.,1 'rl i ', r;.,,

reactions which are taking place along
i,. ,i, 1,.

with the steam in the reformer are as

,,,, ,,

given below:
Primary reformer is one of the most
highly stressed equipment of the cH4 + H2o s co + 3H2 att298oc : *165 KJ/Mole
Ammonia Ptrant front ond where cHo + 2H?o s co2 + 3H2 aHzgSoc : *165 KJ/Mole
reforming reaction takes plaee and
converts the hydrocarbon feed stock The reforming reaction is endothermic
into hydrogen and carbon oxides by and the required quantity of heat is
the addition of super heated steam supplied from outside by externallv
over a nickel catatryst filled in tubes. heating the reformer tubes.The rate of
 E
$

i
j
t

%%
chemical reactions depend on
the Thble I- Theoreticar life span of reformer
partial pressure of each reactant fubes
or in
furn depends on their concentration 6f,o.

as well as. total system pressure

9n
along with energetic state of
molecules.

The risein temperature of the

reformer will ln increasing ihe
kinetic rate ofl.lp chimical reactiJn of
reactants by raising the proportion
of
molecules passinglhe energy for
the
reaction known as actlatrJn .n.rgy
or as a thumb rule the rate of reaction
utilization of the high alloy tube
ls approximately doubled fo, ,u..y like manurite 36x etc.
matenal and extended catalyst life
l0 deg. C rise in temperature of the
time due to very aceurate temperature
system. ii ,li ffi'tf:F$;fl iv,:ft".,ri$;*''jg.,
control and optim rzed, shape of g,.i #:+:$iil i.{..,_'p,'gii,.g,:

_
$,* i$c .$ijq_F$,{ j$+,,.,4
catalyst. The heat required for
fi+jii-rAi,|l.'*;

$, iru d":; g:s;g'*.

$:,b,{:" H* f:i f5;i
heating the reactants in the f**un..
i, Theoretically the service life of
added by the combustion of the
The steam reforming process of fuel reformer tubes made of alloy
gas in side fired burners alranged Hf_+O
hydro carbons in un u*Loniaplant
is seven horizontal rows on eachside
in or other alloy material is aiout
divided in two discreate stages-_ oF 10,0000 hours i.e. more than
the radiant chamber. Each burner f O V.uru
is under nonnal controlled temperaiur.
designed to liberate 2,17,500 Kcal/hr.
A) Primary Reforming _ In this of maximum heat and 1,74,00t0 operating conditions.
process the heat required for
Kcal/hr ofnormal heat.
the reaction is supplied from an Reformer tubes are made of special
external source by firing fuel htgh temperature chrom.-ni.t .t
gas etc. in reformer burneis. Jh. hydrocarbon feed and super
heated steam mixed gas is fed to
alloys and operate very close to the
B) SecondaryReforming_In this reformer tubes by ,,INLET
the limits of temperature urrA pressur.
,o
process the heat is generated even a short accidental ixcursions
PIGTAILS" on the top oithe refonner
within the systems by the furnance and the bottom oi tt
beyond the normal op.ruiing
combustion of the oxygen of .
reformer tubes arc connected to the
conditions can drastic afiy urr.ot
the
the process air. tube_life, particularly if tire furnanc.
reformed gas main header by has been designed to a very tight
"OUTLET PIGTAILS.', The pigrails
ffi $,*'
i ,q:$ specification. Based on operating
$$ $ .&t$,&,fr#. $d: F$, &# '*$e of reformer tubes allow for" the conditions it has been experienced
expansion of the tubes. In prtmary
Primary Reformers are classified that some tubes have given ?t .
nf. of
reformer sensible heat and the heat
based on burn er arrangements in of 60,000 hours i.e. abiut g years
the reaction are transferred by radiation or
following four systems _ some have failed in six months
only.
from a number of wall burners to the
catalyst tubes.
A) Top fired Based on literature survey the
B) Bottom fired theoretical life span of HK_40
c)
Th: designers have used a great catalyst tube at varlous temperature
Side fired (Radiant type)
variety of support systems basel on
D) Terraced wall type and pressure are given in Tabie l.
springs and counter weights to reduce
unacceptable stress on the tubes by
The service life of refofiner tube
frimary reformer is an induced draft introducing flexibility.The most is
brick lined rectangular box heater in typically designec to be r 0'hou^
commonly used matenal for reformer ut u
which alloy steef tubes filled with
fubes up to 1980 was centrifugally
ce rtain design temperature and,
nickel caialyst are suspended cast HK -40 containing 2J pressure. a
()
vertically. The tubes are instalred % V)
chromiuffi, 20 % nickel and O.: 5 o/o to
either in single or in double row in rf"1,'+. $:]i1i'.$iild .{"} fl,r' -qi€-.#i,$J'{:$ $;,$.r:ffi$.,i.F$ 'rfl'$,j
0.4 % carbon. HK-40 tube materral #i$'$ri;
c.)
two radiant chambers. ,#ftFj#",fi";,#teH fr.
was used in all Ammo nia and +r
Methanol plants up to 19g0.Nro* utt The service life of alloy steel
Side fired (Radiant type) ref,ormers 6d

the refoffner tubes ire being chang.C

are designed on the side fired furnace reformer tube is 1,00,000 hou.,
*ilh- newly developed more stronger at
concept and ensures optirnum controlled design temperature and
and heat resistance or stable mate iiut 63
pressure but in actual practice the rc

53
August 2010
 reformer tubes are generally failing
within six months, 1 to 2 years or
some tubes even in 3 to 4 years. The
causes of tube failure are studied in
detail and can be listed as follows -
i) Longitudinal creep rupture.
ii) Corrosion.
iii) Casting defect.
iv) Thermal shock.
v)
Carburization.
vi) Oxidation.
vii) Poor activity of catalyst.
viii) Malfunction in process and
operating conditions.
ix) Over firing at start up.
x) Condensation.
xi) Pressure cycling during start
up and shutdown.
xii) Poor burner maintenance.
MHtrHTANTSMS SS'
Rffi $'#R]hHffi R Y{JBffi SBgS"Uffiffi
During plant start up and shutdown
special eare has to be taken for
controlling temperature and pressure
to avoid tube failure because reformer
catalyst tubes are the most critically
stressed tubes. Reformer tubes are
made of special high temperature
chrome- nickel alloy and can operate
very close to the limits of temperature
and pressure for these materials
without failure.
Generally, it has been experienced
that reformer tubes expand in length
by 10- 15 cms when they are heated to
norrnal temperature from cold during
plant startup and this expansion of
tubes is to be absorbed by the tube
suspension systems. Otherwise it
willlead to damage oftube"
Catalyst tubes fail mainly due to
creep-rupture. Although the tube
material is solid at the normal
operating temperature but, its
ductility increases leading to plastic
deformation under stress.
Operating the furnance at just 20 deg.
C above design temperature can
reduce the expected tube life by half.
There are other occasional factors
which can accelerate tube failure by
Table 2 - Failure analysis of reformer tubes
$ff
rj#tiiriiii'i'
T ffi 1
€.r'ed$ntni Ov: heatihs,
I
n:
a"a
:
ffi I F,r,Ad-ffi*e CasfinErdefect
3.ii ffi I O,fro,oe$.oi O-vm,rhe"ating
4t L?ilit I €,,ieg lit Ufuo
6,:$.ffi z tnti$
e..o"Pti" Udknown
6l,l $i2-tiii 6: ,0'o.#d,sddd"o
Tt, i4$ 2 t$"b.$-'ot Over:heati#
8o 1#8ru 4
'o,6{fi
9i 6ffi 1 O,f'$dp"'.0i O. m he*inE
,T 6'0u I e'fig, llut
Ovet,heating
aggravating creak. Few factors are fracfure in due course of time. The
as follows : rate at which this process occurs is
a) Condensation Process fluid temperature dependent and stress
condensation takes place in the top dependent but the actual dam age does
and bottom of tubes which are outside not go in linearway.
the furnace box. If steam comes into
contact with them at or below its dew RHpmRMmRw[rffiffi s'a[H"ffimffi :a
point during start up or shutdowfl, it ffAsffi i$g{Jffiy
can lead to stress corrosion cracking.
b) Thermal and pre,r,rare cycling After commissioning of the ammonia
During plant start up and shutdown plants the primary reformer was
the thermal and pressurisation running normal. Constant watch and
system damage the thick reformer control was kept on all the operating
tubes with ODAD ratio greater than parameters i.e. tube skin temperafure
1.35. reformer pressure, steam pressure and
c) Poor burnerfiring/Main tenance - quantity, gas pressure and quality etc.
A well designed furnance having In due course of time reformer had to
poorly maintained burners can lead to be stopped due to the following
uneven heating or if the flame emergency conditions.
actually impinges on a reformer tube,
it will result in damage to the tube. i) Failure of steam.
d) Over firing - During startup over ii) Failure ofnatural gas supply.
firing of the reformer takes place iii) Failure of steam drum BFW
leading to tube failure due to over control system.
heating. In nonnal practice, refoffiner iv) Failure ofpower.
tubes should not be heated at more v) After attending all the above
than 50 deg. C per hour but in practice problems, reformer was started
it goes high at local points leading to and found to have red hot tubes.
tube failure. In due course of time some tubes
e) Blowing - The tubes by uneven started leaking and these tubes
heating or as a result of some have been blanked and reformer
obstruction to free longitudinal was kept running.
expansion are subjected to stress
which when added to other normal At the end of five years, it become
stresses (pressure, tension) exceeds absolutely essential to replace all the
the maximum total allowable stress reformer tubes. Hence all the
leading to damage. reformer tubes were replaced with
/)?ltermal shock * Entrained liquid newly developed stronger tube
water, when enters the fube causes material manurite 36 x tube
severe cracking or craztng of the containing 35 % nickel, 27%
inner surface of the tubes leading to chromium along with 1.5 % Nb
premature failure oftubes. (Niobium).
The high temperature materials As such there is no experience of tube
undergo creep, which is an service life but these tubes have also
irreversible process and leads to failed in almost one or two years due
 to disturbance or maloperation in Table-3 New developments in reformer tube materials
process. #s trN5'1.9'p.A .L Hgff Containing 24% c'hromium, , 24i;Yt Nickel , l.60/o
Niobiumand0;3%Carbon..''''.'.]:i'i......'.'
PARALLOY H39 Cdndinsi26l.%,,C dffiidffi .i
Failure Analysis of Reformer
'lB.i
ff iir€.oHidiini$Ha,:llo.$L,I.F.+.ffiE

Thbes ffi a'ag.THF, C o ntaining3 3 - 3 7 t/oN i ckel,

to 0.7So/s Carbon,,,"' '
2 4= 8 7o Chro,mium and 0. 3 5

'Eri" tu{ANAURI'.TB36X €drtdlfi $$8.:3'6i,%.N,i,efi

A11 the reformer tubes were inspected N.,iobii ..a diiOn

and tested for failure analysis. The Fj* MANA.UKIT .X'M S.mall amount Ti, L;n & Zr are added along with
.of
aboveco.mposition..'.........'..
failure analysis of the tubes is given GiJ MANAU.RITE.X$ Containa 43'48 %o Nic-kel, 35-37 o Chromium ,'l.5 oh

in Table 2. Niobium. 0.40 to'045 Vo Carbonuiotte wtth fi,I-n & Zr.

The analysis given in Table-2 plant startup or shutdown. Following NHW NEYffiINFMffiNT NET

indicates that mostly tubes have corrective measures are suggested RRFSRhf,HRTUBW
failed due to creep rupture which which are to be strictly maintained to M#TERTA,T,fi
occurred by over heating. avoid the failure of reformer tubes.
In recent years, new developments in
It was also observed that in addition i) Feed sulphur free feed to metallurgy, design of reformer,
to the required strength at elevated reformer. design of reformer /burner layout /
temperature the reformer tubes ii) Maintain proper steam to carbon burners, use of highly active
must also have resistance to ratio. optimum shap ed catalyst, reduction

deterioration both from products of iii) Continuously monitor process in steam carbon ratio etc. allowed the
combustion (external) and process steam for quality and quantity process operations to be carried out
gas internal by goS, metal and and if required then take atmore severe conditions. To take
corrosion reactions like carburisation, corrective measures. careof the stress rupture strength
decarburisation, oxidation, irr) Keep reformer tube expansion and creep resistance at high
sulfidation. salt attack, stress system in good workino temperature and pressure new
corrosion. nitriding and inter condition. materials have been developed and
granular attack. Alloy HK-40 tube v) Do not increase reformer tube are given in Table-3.
is an austenitic metal like ferrite. It heating temperature more than
is comptreteXS. non-magnetic as cast, 50 deg. Cihour. The maximum operating temp. for
but n-hen tube is carburtzed then vi) Keep reformer burner in good manaurites in reforming
metallurgical chan-ees takes place working condition. applications are as follows:
and a ne\\' matrir composition vii) Scan the reformer tubes for any
magnetic lrcn-nlckel chromium defect at every long shutdown Manaurite 36X -1050 deg. C
allo-v is tbmne'J. Tilis alloy becomes regularly. Manaurite XM - 1000 deg. C
magnetic as a resunt of chromium viii)Maintain tube skin temperature Manaurite XT -IIl0 deg. C
3!
lb
depletion cs.rrsed b,i oridation or in specified limit
always with Manaurite XTM -1200 deg. C
carburizatlon .-ri br- both. The old by proper control of burner
I

tube \\'es testeC r,o, rttr a magnet and firing. A11 the plant designers are changing
5
founC to tra\ i naglienlsrn nl-hich is a ix) Use proper design of reformer reformer tube materials to manurite
K for getting more stability and life.
sign of rube fa:l;:e and burner system.
BIP

x) Minim rze shutdown and

Process up:r. ;; i:,1"1::ons nlke hr.-gh startup of reformer. CONCLUSION
temperat;:e ; i,:":anrtlrxetlon of xi) Use good quality of catalyst
}e
proce-\s sti,si:. ;
":b
;:i satlon xo$-ers with optimum shape and By the use of highly active optimum
shaped catalyst, newly designed
li,t5
"lll|5

tt,5
the rube l,r:e activity.
"!lb
rii) Maintain proper rate of coolittg reformer tube layout/burner, addition
ffi and heatin g at the time of plant of adiab aticpre-reformer, intro ducti on
h,-s
shutdown or startup. of newly developed CFD software for
[r,.t
-q
riii ) better materials
Use burner firing and the use of reforrner ili,i#l
ri.F{i

of construction like IN519 or tubes ofhigh alloy steel tube material, kj

::44,

{b II{ i,.,.-
\[anurate 36xetc. the life of refoffner tubes has been (t<
O
.,:.,,ri
.',.r,.,

rir") Reduce primary extended beyond the design level. As r-i

tr.:
!G"
, :.i ti
::r'trr.'

Correetir e $fensures reformer load by installing a result the plants are being operated
b'e pre reformer. on steady load and condition without t1 ', :

lso
lan ot rr ) Use software system for very any disturbance of tube failure or C$. ',
hl,e '13 ',*r
-d,'-
il-* l-*.t l.,itt I 'T
i ec curate temperature control. plant shutdown.r * ,',i,tij
H:ill.'',1,'l'i ;