I

lIII

t rs
I
111I

ocessing conditions for ammonia
urea are highly corrosive; using
Hurgical advancements can
gate such forces
P. Sukurrt€u'an Nair, Travancore Cochin
nric.als Ltd., Cochin, India.
n the hydrocarbon processing industry {HPI), the
manufacture of ammonia and urea holds a
prominent role. These petrochemicals have
. ed the growth of agricultural production >\'ith
technologies and processes. This industry uses
different feedstocks such as coal, liquid petroleum,
gas, and refinery residues. These feeds are
sed under extreme pressure and temperatures in
y corrosive en "ironment.
ite these processing challenges, large-scale fer-
plants are built worldwide to meet the gro\'\ing
lizer demand. A major factor contributing to this
I ts
achievement is the industry's success in combating cor-
rosion. Adopting modern corrosion-abatement tech-
niques and applying new generation/improved mate-
rials of construction have effectively mitigated process
corrosion factors.
Betler materials of const:nK;tion. Over the past two
decades, the ammonia and urea industry have wit-
nessed spectacular metallurgical developments for pro-
cess equipment. For example, stainless steels, modi-
fied with special materials, can improve high-
temperature creep rupture resistance. Using duplex
stainless steels and modern corrosion abatement tech-
niques are other methods that improve plant-operat-
ing performance.
Urea or carbamid~ source of nitrogen-is the major
fertilizer material and is produced from ammonia (NH3)
and carbon dioxide (C02), Current global production is
approximately 100 million tpy. Urea manufacture con-
sumes nearly 90% of all ammonia produced.
Ammonia is produced by the synthesis of elemental
hydrogen and nitrogen; it is an energy-intensive pro-
 $efA:mdary .efotli1er. In this unit, air is added to the
2,100
Effect of increasing temperature and
process stream at operating conditions of 28--30bar and~
pressure on lrfe of HK-4-0 aHoy tubing in
1,100
957-1,025~C. The refractory-lined vessel has an outBr~
2,000
st""Ea..!T'l-methane reformer furnace service 100 shell ofa low-alloysteel conta.ining0.5 Mo.A typical phe-:
9 nomenon-metal dusting-occurs in the secondary~
! reforrneroutlet sections.With hot gases conta.i.ni.Tlg
higher;
1,000<3

i
E
{!.
CO content, strong carburizing reactions occur,and car-)
bon will diffuse into the Fe-Cr-Nialloy.This phenomeuOllf
can lead to local mechanical fracturing of surface layera,
and, subsequent failures, by pitting.,
<t,

Material such as SS 304 and Alloy800 are very much;

susceptible to metal dusting (Fig. 6) in the temperature
1,500 ,i range of500-800°C. Besides temperature, carbon activo
0.1 1.0 10 ity (ratio of CO/C02 in the gas) and gas partial pressure{t
Furnace tubing life, years also affect metal dusting. Severe attacks occur when the'
carbon activity is in the range of3-10. Recirculating
Fig. 4, Overheating shortens tube service life. into the primary reformer along with feedstockcan
tain a low CO/C02 ratio and avoid the severity of
attack. Other mitigation efforts are maintaining a
oxidizingpotential ofthe gas (steamlh.ydrogenratio)
properly controlling temperatures.
Hydrogen embrittlement is another important co
rosion problem that is encountered in reformed-g
pipelines. Usually, the piping material, used dow
stream of the feed-water heaters where the gas te
perature is less than 400°C, is a low-alloy steel. lnt
nal carburization and fissuring of steel is caused
hydrogen permeating the steel and forming meth
The formed methane cannot diffuse out and accu
lates in voids formed at the grain boundaries. This c
dition contributes to high stresses that ultimately -
~ sure and crack the metal.
o
The Nelson curves (Fig. 7) list the operating Ii '
§ 0.3 I'
to avoid de-carburization and fissuring for steel
E !
:5 0.2 :, i hydrogen service. Consider these conditions wh
~ III1I
selecting metallurgy for equipment and pipelines do
0.1 ill stream of the reformed-gas boiler and the low-te
1,4000 1,6000 1,800· 2,OOO·F perature converter.
I t I 1
700· 800· 900· 1,000· 1,100·C
CO conversion. The high-temperature convert
Temperature
where CO in the gas stream is converted to CO2 by t
water-shift reaction, operates at 25-28-bar presS
Fig. 5. Generalized comparison of allowable creep-rupture stress for
HK-40, HP-Nb and HP-Mod micro alloys.
and 350-450°C temperature. Usually, low-alloy ste
vvith lCr-0.5Mo is used as the material of constructi
In converted gas pipelines, acid gas (C02 and H2S)
dissolved in the steam condensate, 9..11d
often contri
to corrosion. This condition can be avoided by using
Air
From 304 material.
prtmary Steam
reformer
CO2 removal. Choosing the metallurgy in the C
removal system depends on the solvent used in the
cess. SS 304 and SS 316 are the preferred material
Steam
super
construction. Carbon steel, fully stress relieved
heater metalworking, is also used for piping and equip
in this section. Iron in the circulating solution can c
Steam
erosion corrosion in pipeline bends, pump impell
pump casings, etc. In plants where amines are us
absorb CO2, formation of amine carbamate add
also contribute to corrosion.
Metal dusting
With modern alkanolamines-methyl dietha
Waste-heat occurred amine (MDEA)--the carbamate adducts are less
boiler stable and, thus, do not accumulate in solution.Addi
in the solution render the carbamate harmless by
Continued on pag
r-·-·---·~·_-----·"""""'-··--~-~-·~-~-"":---~·-·--·-~---·--~-"'--"'---.
! .'.---- ..' ..--"---~~"--'-
I
h:

h
f

II'

I
I

tEi
rE'

eontaL~ng l'
Table 3, Urea-grade steels by composition and process gas from the secondlan.d~ are 1,
reformer. It generates high-press-matftnal-2
Name,% C{max) Cr Ni Mo Mn P
316 0.08 16-18 10-14 2-3 2 0.045
s- Si--1 steam in specially designed boil(.ai~/are us'
0.03 1 These boilers and steam sup~ndtempen
316L 0.03 16-18 10-14 2-32 0.045 0,03 1 heaters operate under very high bt.hso),'bed by:
316L(urea-grade) SO.03 16,5-17 13-15 >2.3 2 0,045 0.03 1 flux on the one side and corrostal'~p..in thl;
water on the other. ConsequeJ)h~decarbl.:i
meticulous care is needed to al"'}? i
failures. Proper material seleetiiAnt"J·cnia s
verting them into carbonates. In potassium carbonate and stringent water quality are two proactive losSf~~11-213"
processes,arsenic a..'ldvanadium salts are used to sup- venti on methods. Various material grades of SA Z~l}n mal
press corrosion. A passive layer of magnetite on steel ASTMA312,ASTMA335and ASTMA351 provide:;ttm~~:re or ~i
surfaces is maintained by adding small amount of air. ful service life in this section..beriC) stara!
In the CO2-removal system, sce is caused by the The coolerpart of the combustion air preheater majorprobler
combinedeffects of tensile stress and corrosion. It is a tail end ofthe flue-gas-heat-recoverytrain--more jj};~f~ydrou"
major problem. The caustic environment for carbon to corrodedue to sulfur dioxide(802) condensing froI1l~U!pment.<:
steel and the presence of chlorides for austenitic stain- flue gas. In this area, cast iron or glass ",ill resist'~~eleft OVerI
less steel both aggravate sec. This combined action of acid attack. Carbon steel preheater tubes, joined ;f-t~rialand,
tensile stress and COlTodantresult in either trans- 1.5 to 2 m of S8 304 tubes at the cold end of the tl aggrava
granular or intergranular cracking of the metal or sheet, can ensure reasonable senice life, Typically,. .~ithout l::

both. The overall stress corrosion process is initiated ·~·~{O . '

flue-gastemperature to the stack is maintained above~''''4 •.2%)~!
by corrosion damage; these cracks propagate due to dew point of802 to prevent condensation.During star .•"',,~mpera!
joint electrochemicalmechanical action and ultimately and shutdown, condens<;>.tion of 802 ",ill occw', f@~~tanceto I

fail. 8ee can be prevented by: better material selec-
tion, reduced stress of the metal by proper heat treat-
ment, eliminate chloride solutions, remove oxygen
from chloride-containing solutions, apply corrosion
inhibitors, etc. Ferritic and duplex (austinitic/ferritic)
type ofstainless steel show marked resistance to stress
corrosion cracking
Waste~heat r-ecovery. The waste-heat-recovery system
is associated with flue gas from the reformer furnace
90 HYDROCARBON PROCESSING JA.'\TARY 2001
The high-pressure, feedwater heaters al'e prone cor'
leaks at the tube-to-tube sheet joints. Lining or of~1}fs st
laying the tube sheet with material, such as, Alloy' ,
and using tube materials with 1 Cr-O.5 Mo can plan,Plant.:
gate this risk considerably. ~41f1t;:;rmed'
. ".onofNRs al
Ammonia synthesis. If the synthesis gas con ty of eli
tra~es of c~bon oxides,upon mixing.withthe ~"1{:3~-.nd. first
recIrculatmg gas from the synthesIs loop, ammoll'fea~nc,entr
carbamate will form, and clog and/or corrode doY . r liner,:
 e uipment. To a:oid this co~dition, consider
f~1in~ the c~rbon oXIdeslevel WJthfresh makeup
less than b ppm.
lea fro
_ mpressor interstage coolers are usually con-
e ~oof carbon steel and use water as the cooling
~teu Low-velocityareas in the water passage are
the lea r in
't'
lu.tn·"caling an d un der-depOSl,mJCro b'1a1corrOSIOn.
.
tD- - 'b il .
factorsmay le,:,d~ tu e fa ures ..Improved design t bo aetlinery
hangers can ehmmate low-velocItyareas; proper
",_watertreatment program can control under-
""microbial corrosion.
cont It
Compressor Controls Corporation worldwide turboma·
up heaters-electrical or direct-fired types-
to heat synthesis gas for the converter during chiner}' seminars are courses based on our years of
experience in the turbomachinery control industry.
up. Hydrogen-ind~ce~ tracks, overheating and Seminars are presente.: at our world headquarters in the
impingement, thmnmg at the bends, furnace United States and othe- iocations around the globe. Our
Dsions, etc., are several problems encountered instructors will present complex t8cimical concepts in an
litis equipment piece. NOffi1ally,SS 321 is used for
easy-to-understand manner.
uP heater coils and downstream pipeline.

l
h; ammonia-synthesis converter operates at
ZOO bar pressure and around 515°C. Under these
ice conditions, nitriding and hydrogen embrittle-
t can occur. The pressure shell is a multi-layer or
Iti-"I;allcarbon steel vessel. The internal catalyst
• Houston,
Ma illtell ance
Texas, U.S.A. i
2001nar Sc l1edule
for Sem .
kets. contained in the shell, are constructed from February 20-22
321 material. Des Moines, Iowa, U.S.A.
Nitriding of pipes and catalyst-support grids are March 13 -15
countered in ammonia plants. The nitriding effect New Orleans, Louisiana, U.S.A.
roore pronounced in low-alloy steels above 450cC; 17 - 19
April
"tinitic steels 'with a high-Ni content offer consider-
Puerto Va!larta, Mexico
1emore resistance. Alloys of the Cr-Ni-11o-type- May 15-18
ining 12-25% Cr, 5-25o/c Ni, Mo, vanadium (V)
\V--are usually used for the gas side. SA 213, T22 Rio de Janeiro, Brazil
June 12 - 14
aterial-2.25 Cr-1Mo type or their improyed yer-
ns-are used for the boiler. Due to the high pressure Des Moines, Iowa, U.S.A.
d temperature in the reactor, atomic hydrogen is August 14 - 16
rbed by diffusion; the subsequent reaction with Las Vegas, Nevada U.S.A.
bon in the steel results in blistering and cracking September 11 - 13
ill decarburization. Kuala Lumpur, Malaysia
October 16 - 18
mania storage. Carbon steel, such as, BS1515,
1511-213,ASTM A516, etc., are the conventionalcon-
,etian materials for ammonia storage-bullet, Hol'-
ere or atmospheric storage. For refrigerated (atmo- Melbourne, Australia
ric,;storage, low-temperature carbon steel is used. A November 14 - 16 "
Uorproblem encountered in the storage and transport
anhydrous liquid ammonia is SCC of carbon steel CCC is Uniquely Qualified to Answer Your
_uipment.Cracks occur mostly at weld joints where TurDomachinery Control Questions!
Ie left over stress is the greatest. The hardness of the
aterial and presence of impurities and oxygenates in eee can also respond to your individual requests and pro-
vide customized on-site training. To register and receive
H3 aggravate SCC. Complete stresses relief, operat- more information about these seminars or to discuss solu-
g \vithout air contact and adding small quantities of
tions for your specific traininq needs, please contact
'ater(0.2%)as an inhibitor can effectivelymitigate SCC.
w·temperature carbon steels have considerable more ComiU'8SS0r Controls Corporation
istance to SCC than norn1al carbon steels; it is the 4725 121st Street
ferred construction material for large atmospheric Des Moines, iA 50323 U.S.A.
quidNH3 storage tanks, operating at -33°C. Phone: 515~253·3224
Fax: 515-254-2360
rea plant. Corrosion from ammonium carbamate- E-Mail: seminars@cccg!obal.com
intermediate product formed during the conver- www.cccglobal.com
. n ofNH3 and CO2 to urea-is a major problem. The
Intensity of corrosion is greatest in the reaction section "'S€iminar dates i'ite subject to ch"llge.
;and the first recycle, where pressures, temperatures For an up to date seminar Seh",dllll:, please gu to ,
and concentrations are higher than dovmstream. The I't1IflM.GGcgloba!, com.
tf;actQr Ener, pumps, decomposers, strippers and con-
Circle 97
91
densers are more vulnerable to attack by ammonium
carbamate.
The urea reactor is a multilayered vessel of carbon
steel "ith corrosion-resistant interior liner. Reactor-
liner materials are usually SS 316 L (urea grade) 'ivith
a lower ferrite content (::;0.6 % for pipes and < 1% for
forging). SS 316 Land SS 316 L (urea grade) have sig-
nificant difference(Table 3).American Society for Test-
ing and Materials (ASTM) allows a large tolerance
range for composition of 316 L. For example, 316 L-
urea grade-is produced to a well-defined composition,
which enables maximum corrosion resistance.
Titanium and zirconium are used to line urea reac-
tors. The liner is continuously passivated with oxygen
to resist corrosive action by adding air (0.5-0.8%vol
oxygen) in the CO2 feed.
In urea plants, corrosion failures include erosion,
pitting, weld embrittlement and cracking, crevice cor-
rosion and sec. In the reactor, the liquid/vapor inter-
face is a corrosion-prone area. Attaching a sacrificial
plate to the liner can strengthen this section. The multi-
layer vessel may also undergo severe corrosion dam-
age from the reactor contents when the liner becomes
defectivefuld le~\s. Zirconium-linedreactors have good
corrosion resistance and do not require passivation.
Reactor-outlet piping and let-down valve are sub-
jected to erosion corrosion from the pressure reduction
across the valve and high fluid velocities in pipelines.
For the low-pressure downstream equipment, SS 316L
and SS 304 are goodconstruction materials. Aluminum
alloys and piping are quite resistant to the corrosive
Circle 98
attack by urea due to the protective oxide film.
alloys are used in low-pressure piping, floor
hand rails, etc. Dead spots and crevices--where
ment parts are not continuously wetted by
taining liquids--are prone to severe corrosion.
ingly, fabrication of this equipment should be
avoid such vulnerable spots. The probability
contamination with corrosive agents, such as, S
(through oil in liquid NH3), H2S (along with CO2)
chloride (from coolingwater) should be
Pitting and crevice (.:orrosionoccur by the
action on exposed surfaces and weak points on the
face. In threaded or flanged connections where the
sivating effect of oxygen is low, this phenon-ler:lon~t~~lntain
occur and is aggravated by chlorides and higher
peratures. Pitting resistance index (PREN)--a n-
of comparing con-osion resistance of stainless st
may provide a useful guideline for material sel
in such environments.
Pitting resistance equivalent number (PREN)
or Pitting resistance index lkCr + 3.3XlkM(
==
+ 16X%N
Duplex stainless steel alloys are a mixture
ritic (400 series) and austenitic (300 se
microstructure of approximately equal volume
tion after final water-quenching-heat treatmen
ing metalworking. Using this material has be
popular because of its resistance to stress corr
and fatigue, pitting resistance, suitability for a
temperature range of indust
applications (-50°C to 280°CJ
cost effectiveness. In the
plants, duplex stainless
used to construct strippers, def
posers, condensers and pipe
Cavitation corrosion occu:
pumps where the flow
form bubbles on surface ofimpef
These bubbles, upon formation b;
with enough force to mpture the'
tective film of the stainless steel ~
above
throughsitua~ion can preventsf
deSIgn that be correct.•.
hIe formation, polishing rota'J
SItes to
p~rts.
greaterandcorrosion
by usmg
remove ~ubble alloys ;'•...
formal.·
resistance,
strength. l
Besides selecting corrosiol1-ri
tant materials, chemical agentsf
inhibit the corrosive action illt Big, strc
NH3 process. Different corroi ALS sa~
inhibitors are used for CO2 reUll;' Tou~
boiler and coolingwater, plant:1
ents, petroleum products, etc. qi MDAI
ocu
biocides in cooling-water treatrrt
can control microbiological Orf;>
isms and, thereby, mitigate co- Mil
sion in these units. In the feed\\~; l.se
and boiler svstems. an alkalinE
is maintai~ed to ~inimize CC~
sion. Caustic dosing should be'
 d to maintain boiler pH control and avoid embrit- nia/urea processes have reduced harsh environments.
nt of boiler steels. New generation materials, such as, ceramics, are resis-
..eoxv_resin-basedcoatings are used to protect both tant to the rigors of processing. Life-cycle analysis
Ii;
P and nonmetallic structures. Deaerators, naph- and costing are also gaining acceptability as the basis
of material selection. •
torage, raw-gas pipelines, effluent channels,
l~ngtowers,
,1 .
flooring of bagging
h plants,
t' silos andf
BIBLIOGK"-PHY
veyor gantnes a:-e areas w. ere ex.enSlve usage 0
Dillion, C. P., Corrosion control in. Chemical Process Industries, McGraw Hill, 1986,
v coatings provldes corrOSIOnresIstance. Ghosh, C. P. K., D. K, Guha Sarkar, and V. S. Gupta, "Studies in the improvement ofcoat~
~'-ny issues arise over material selection and cor- ing and. lining for urea pril1ing tower," Fertiliser News, August 1992.
Jaeques, C., and P. O. Ba,yton, "Reducing cost by using duplex stainless ste€Js," Chemical
;i; abatement in modern fertilizer plants. With Processing, November 1996.
,eIopments of metallurgy, and usage of newer cor- Johansen, T., K. S. Reghuraman, and L. A. Hackett, "Trends in hYID'ogen plant design,"
Hydrocarbon Processing, August 1992.
\on_prevention techniques, it is possible to cost- Parks, S. P., and C. M. Schill moller, "1mprove alloy Bf'Jertion for ammonia furnaces,"
etively and, more important, safely operate and HydiOcarbon PrrJCtssing, October 1997.
Redmond, J, D. and K H.Miska, "T.'1e basics ofstainl.ess st~ls." Chemi.ca! Engineering, Ocw~
intain large-scale plants. Changes to the amm~- ber 1982.
Schillmol1er, C, M., "'Solving High temperature problems in oil refineries and petrochem~
leal plants," Chemica! Engineaing, ,January 1986.
Schil1mol1er, C.1!., and V. W. van den Bruck, "Furnac,e alloys update," Hydrocarbon Pro·
M. Po Suirumtt·ron Nair is the managing direc- cessing. December 1984.
tor of the stat&-owned Travancore-Cochin
Chemicals Ltd., Cochin. He was with trJe pro-
cess engineering department of FACT Engi- NOMENCLATURE
neering & Design Organization (FEDO), the C = Carbon
design and consultancy division of the Fertil-
Cr = Chromium
izers and Chemical Travancore (FACT) Ltd. Fe = Iron
Mr. Nair holds BS degrees in chemistry and
Mn = Manganese
t. I chemical engineering and a post-graduate Mo = Molybdenum
_____
---..---.J degree in ecology and environment. Mr. Nair Ni = Nickel
<liso holds an A,lBA from the Indira Gandhi National Open Uni- ~'b = Niobium
~ New Delhi. He joined FACT in 1971 and is 'Nell ~enced N = Nitrogen
1troperation, management, process design and troubleshooting P = Phosphorous
of chemical plants. He is a fellow of the Institution of Engir,eers Si = Silicon
{Jrtdia), a member of the AJCh~ al,d is listed in the Marquis, S = Sulfur
Who's Who In the World. He may be reached by em ail: Ti = Titanium
/'f!Psn@vsnl.com. W = Tungsten
Zr = Zirconium

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Circle 99
93