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MATERIAL SELECTION FOR NITROGEN BASED
FERTILIZERS PLANTS
Author
Prem Baboo
Sr. Manager (Prod)
National Fertilizers Ltd., Vijaipur, India
INTRODUCTION
Materials plays very important role in any industry .Selection of material is vital at design stage
itself. Wrong selection of material may lead to catastrophic failures and outage of plants & even loss
of Human lives. Right selection of material leads to long life of plant. Fertilizer Plants employ
various corrosive, hazardous and abrasive fluids and chemicals. The temperatures involved range
from cryogenic (-330C) in ammonia storage to 10000C in reformer. The pressure are as high as 175-
350kg/cm2 in ammonia converter and in urea plant reactor pressure 150-250 kg/cm2.Once
equipment has been selected, the materials for its construction must be established. Although a
process Engineer is not expected to be knowledgeable as a metallurgist, the engineer should have a
general idea of what materials are compatible with the process. Therefore, this topic presents some
general guidelines in the selection of material for process equipment. In all ammonia, Urea Plants
worldwide the problem of severe erosion and corrosion of high pressure vessel has been a common
phenomenon.
In Ammonia Plants, past experience has shown that duplex stainless steels can successfully
replace carbon steel and stainless steel in most heat exchangers at temperatures below 3000C.The
improved corrosion resistance gives longer service life and what is more important, fewer
standstills. High alloyed duplex stainless steels can even be used for seawater-cooled heat
exchangers. In urea plants the stripping technology has called for special care in the choice of
materials. A wider use of special alloys has resulted in lower maintenance costs and longer service
life. When considering the new materials of construction, one most remember that it takes time to
build up a comprehensive portfolio of corrosion data and case studies supporting their successful
use. For this reason, corrosion-resistant alloys first introduced in the early 1980s are still
considered to be newer.
STAINLESS STEEL
‱ “Steel that has 12% or more chromium is considered stainless steel.”
‱ “Another criterion defining a stainless steel is its Passivity.”
2
‱ PASSIVITY - “Passivity is the ability of a metal to form an impervious surface coating which inhibits
corrosion resulting from the electrochemical reaction of the metal with the surrounding
environment.”
‱ “Stainless Steels exhibit passivity in oxidizing environment.”
To ensure that carbon do not migrate to welding joints (because temperature between 5500C-8500C
during welding this cause depletion of chromium as carbon form) Cr23C6 at grain boundaries in
region adjacent to welds. There is quit serious depletion of chromium and have a weakening of
passivity. Following may be done.
I. Either keep carbon less than 0.03%
II. Add Ti four times of carbon content
III. Niobium eight times of carbon content
Corrosion as function of Chromium
“Following figure No.1 shows the corrosion rate as function chromium content in an iron
chromium alloy.” It might be assumed that increasing the chromium contents without limit would
improve corrosion resistance. This does not happen Figure No.-2 shown the phase diagram for
iron and chromium in all proportions. With Chromium contents between 20 & 70%, the Sigma
microstructure is formed.
Figure No.1
3
IRON-CHROMIUM PHASE DIAGRAM
‱ Following figure No.2 shows the phase diagram for iron chromium in all proportions.
‱ With chromium contents between 20 and 70%, the “sigma” microstructure is formed.
SIGMA MICROSTRUCTURE.- “This microstructure is hard, brittle and poor
corrosion resistance.”
Figure No.2
TYPES OF STAINLESS STEEL
There are three general types of stainless steel of interest to the process engineer.
1. FERRITIC STAINLESS STEEL
2. AUSTENITIC STAINLESS STEEL
3. MARTENSITIC STAINLESS STEEL
FERRITIC STAINLESS STEEL
‱ Ferritic stainless steel has a carbon content of 0.2% or less. Fig. No.3
‱ Chromium content 11-18% .
4
‱ Although it can not be heat treated and has poor tensile and impact strength, it better
corrosion resistance than martensitic stainless steel.
‱ Highly resistant to stress corrosion cracking show an increases as result of cold work
‱ They are magnetic, have good ductility readily weldable, non-magnetic
‱ Welding is difficult
‱ SS 430(17% Cr) USED FOR AUTOMOTIVE TRIMS
FERRITIC STAINLESS STEEL (Chemical Requirements)
Table No.1
AISI
430
C Mn P S Si Cr
0.12 1.0 0.04 0.03 1 14-18
‱ It is suitable for use with strong oxidizing acids such as Nitric acid.
Figure No.-3
5
MARTENSITIC STAINLESS STEEL
‱ Farritic stainless steel has a Carbon.-1.2% or less. And Chromium.-12-18%. Fig.No.4
‱ It has better hardenability and strength than does ferritic stainless steel.
‱ It is used as cladding to carbon steel for some process vessels.
IRON –CHROMIUM PHASE DIAGRAM FOR 1.0% CARBON
Figure No.-4
MARTENSITIC STAINLESS STEEL
(Chemical Requirements)
Table No.2
AISI C Mn P S Si Cr
410 0.15 1.0 0.04 0.03 1.0 11.5-13.5
420 0.15 1.0 0.04 0.03 1.0 12-14
6
AUSTENITIC STAINLESS STEEL
‱ “Austenitic stainless steel is a more complex material because the addition of NICKEL (3.5 to
22%) allows it to retain its austenitic microstructure at all temperature
‱ It has a high tensile strength and best impact strength, ductility and corrosion resistance of
all the stainless steel over a very wide range of temperatures.
‱ All stainless steels are susceptible to pitting from exposure to high chloride concentration.
However, austenitic steel with high Molybdenum content (1 to 3 %) has improved
resistance to pitting.
‱ The austenitic alloys have a face centered cubic structure which has a better corrosion
resistance compared to the ferritic steels. The austenitic structure is normally not stable in
irons below 7000 C, but adding nickel to the steel makes the austenitic phase stable down to
room temperature
‱ These alloys are basically chromium nickel steels. Chromium is used in these alloys to make
the steel corrosion resistant, whereas nickel stabilizes the even more corrosion resistant
austenitic structure. Silicon and aluminum are added to increase the oxidation resistance.
Titanium and niobium, as well as boron, nitrogen, tungsten, vanadium and cobalt can be
added to increase the creep strength due to precipitation strengthening. Manganese can be
used to substitute nickel as an austenite former. Fig. No.5
Fe-Cr-Ni Ternary diagram for an 18% Cr alloy with the austenitic
Stainless Steel.
7
Figure No.-5
AUSTENETIC STAINLESS STEEL
(Chemical Requirements)
Table No.3
Sr.No. AISI C Mn Si Cr Ni Mo
1 304 0.08 2.0 1.0 18-20 8-10.5 -
2 304L 0.03 2.0 1.0 18-20 8-10.5 -
3 309 0.2 2.0 1.0 22-24 12-15 -
4 310 0.2 2.0 1.0 24-26 19-22 -
5 316 0.08 2.0 1.0 16-18 10-14 2-3
6 316L 0.08 2.0 1.0 16-18 10-14 2-3
7 321 0.08 2.0 1.0 17-19 9-12 TI≄5×C
8 347 0.08 2.0 1.0 17-19 9-12 Nb≄5×C
8
STAINLESS STEEL
Table No.-4
Sr.No
.
MEDIA TYPE OF STEEL
13% Cr steel 18/8 Austenitic 18/10+Mo
1 Nitric acid Resist all strength
cold attacked by
strong boiling acid
Attacked only by boiling
concentrated acid
As 18/8
2 Phosphoric
Acid
Attacked by all
strength but less so
in 60-90 range
Resists most strength
point. Slight attack by
boiling 40% and hot 60-
90% attacked by
80%and at 110%
Resist to all
strength up to
boiling point but
attacked by 80%
acid at 1000C
3 Sulphuric
Acid
Attacked by all
concentrations
Slightly attacked by cold
5-10% and by hot &
cold 85-95% acid.
Attacked by hot or cold
15-75% acid
Resistant to hot
and cold 5-10%
acid and to
cold15, 85 & 95%
acid. Slightly
attacked by hot
15.85 & 95% acid
attacked by hot
20% and cold40-
70% acid
4 ammonia Resist all strength
hot or cold
Resist all strength hot
or cold
Resist all strength
hot or cold
5 Caustic
Soda
Resist up to 30% hot
or cold slightly
attacked by hot 30-
50% and by molten
salt at 3700C
Resist up to 30-50%
solution slightly
attacked by molten salt
at 3700C
As 18/8
6 Caustic
potash
Resists 25% solution
up to boiling point
Resist 25% solution up
to boiling point slightly
attacked by 50% at
boiling point attacked
by molten salt at 3600C
As 18/8
9
MATERIALS FOR CARBAMATE SERVICE
Carbamate is highly corrosive in nature at high pressure & temperature.
All over the world licensers of urea plants are searching or cost effective & better corrosion
resistant materials.
MATERIALS FOR CARBAMATE SERVICE
TITANIUM
ZIRCONIUM
316l MOD OR 316L UG OR 3RE60
2RE69 OR 25Cr.-22Ni.-2Mo. (UNS S31050)
DUPLEX STEEL
TITANIUM
Titanium is used in the relatively pure state .It has excellent corrosion resistance but is one
of the more costly and difficult alloy to weld. Titanium corrosion resistance is due to the
impervious oxide film i.e.100% TiO2 film on surface. Titanium is resistant to stress-
corrosion cracking and erosion corrosion, but it is susceptible to crevice corrosion in
stagnant chloride solutions.
Used for lining & tube material of ammonia stripper in Snamprogetti’s urea plants.
Commercially pure Titanium exhibits a high resistance to pitting attack.
Used for lining of urea reactors of TOYO plants MTC Process and corrosion resistance of
Titanium is because of formation of oxide layer In Reactor oxygen is fed with CO2.
ADVANTAGES :
Passivation air is less required as compared other stainless steel.
Stripper bottom temperature in Urea Plant can be kept up to 210 0 C while in 2 RE 69
temperature cannot be raised beyond 2070C.
DISADVANTAGES
Titanium is not maintenance friendly the difficult in welding Titanium is due to high affinity
for Hydrogen, Nitrogen and oxygen in the molten state. Therefore, it must be welded by
such inert-gas welding method as the TIG or MIG process. After a weld has been made, the
inert-gas protection must be maintained until the welding joint cool below 6500C,
10
otherwise, the Titanium will react with the oxygen, Nitrogen and moisture in the air,
resulting in weld embrittlement.
Erosion of tubes ends resulting in bypassing in stripper due to tube end over ferrules badly
eroded by carbamate solution.
Figure No.-6
HCP-(hexagonal closed packed) HCP metal are not ductile as FCC metal
e.g.-Be,Mg,Zn,Cd,Co,Tl,Zr. Etc
The HCP cell consists three layers of atom The top and bottom layers contain six
atom at the corner of the hexagonal and one atom at the centre of each hexagonal.
The middle layer contains three atoms nestled between the atom of the top &
bottom layers hence the name close packed ,figure No-6.
316L MOD & 2 RE 69
These are Tailor made grades of austenitic stainless steel to suit required specifications of
purchaser
USES OF 316L MOD & 2RE69
USES OF 316L MOD & 2RE69
Table No-5
Sr.No. 316 Mod 2 Re 69
1 Reactor Lining Ammonia stripper Lining
2 Carbamate Separator Lining Carbamate Separator Lining & Tubes
3 H.P Section Piping Pool Reactor & Pool Condenser
4 Stamicarbon Reactor Carbamate mixture
11
CHEMICAL COMPOSITION 316L MOD & 2 RE 69
Table No.6
Sr.No. Constituents 316LMod 2 RE 69
1 Carbon ≀0.02 ≀0.02
2 Chromium 18 24-26
3 Nickel >13 21-23
4 Molybdenum 2-2.6 2-2.6
5 Manganese 1.5-2 1.5-2
6 Silicon 0.4 0.4
7 Sulphur 0.01 0.015
8 Phosphorus 0.01 0.02
9 Nitrogen(max) 0.10 0.1-0.15
METALLOGRAPHIC PROPERTIES:
Material in contact with process fluid shall have austenitic structure
Ferrite content shall not exceed 0.6% except for manual welds, for which 1% is allowed
“SIGMA PHASE SHALL BE ABSENT”
Chromium carbides may be present in minimum amount only
Material shall pass Huey Test & shall be performed according to ASTM A 262 practice ‘C’
and maximum corrosion rate allowed shall be:
Table No.-7
S.No. Type of Material Corrosion rate
mm/yr
Depth of attack
micron
1 316L mod 0.6 90
2 2 RE 69(25/22/2) 0.3 70
12
Rate of Corrosion as per Huey Test
Table No-8
S.No. Material Corrosion rate( mm/yr.)
1 ZIRCONIUM 0.005
2 TITANIUM 0.06
3 2 RE 69(25/22/20 0.3
4 316 L MOD 0.6
HUEY TEST-
“Metal sample is boiled in 65% HNO3 for 48 Hrs (5times) to estimate corrosion rate.”
Zirconium
Zirconium is being used in Chemical Industries contains up to 2% Hafnium but does not
affect chemical properties of Zirconium. Zirconium has good mechanical properties at room
temperature, but retains strength at elevated temperatures only if highly
alloyed.Apperance –Steel Grey.
Corrosion resistance because of ZrO2 layer. Zirconium is more expensive than Titanium
(roughly twice that of Titanium)
“DUPLEX” STAINLESS STEEL”
‱ “DULEX steel is characterized by a microstructure containing both Ferritic phase with a BCC
crystallographic structure and an Austenitic phase with a FCC structure.”
‱ The Ferritic phase is normally 40-60%, mainly introduced in the wrought alloys by a careful
balance of the critical alloying elements.
‱ Mixture of Austenite & Ferrite
‱ Higher strength & better resistance to Chlorides
‱ Cr: 18-27%, Ni: 4-7%, Mo: 2-4%
‱ BCC.-Body centered cubic “High strength low ductility.”
‱ e.g.-Ferrite(α-iron),Cr,V,Mo,W etc.
‱ FCC-(Body centered cubic). “Low strength high ductility.”
‱ e.g. Austenite( γ-iron),Al,Cu,Pb,Ag,Au,Ni,Pt etc.
13
‱ Stress Corrosion Cracking
‱ A particular problem for the common austenitic grades (e.g. 304 and 316) is stress
corrosion cracking (SCC). Like pitting corrosion this occurs in chloride environments, but it
is possible for SCC to take place with only traces of chlorides, so long as the temperature is
over about 60°C, and so long as a tensile stress is present in the steel, which is very
common. The ferritic grades are virtually immune from this form of attack, and the duplex
grades are highly resistant. If SCC is likely to be a problem it would be prudent to specify a
grade from these branches of the stainless family tree.
Advantages of Duplex Stainless Steel
‱ Good resistance to “chloride stress corrosion cracking.”(CSCC).
‱ The duplex stainless steel also offers resistance to general and pitting corrosion.
‱ Good resistance to erosion and abrasion.
‱ There are numerous cases where plant equipment properly fabricated from duplex SS has
operated with full immunity in chloride containing environment where types 304,304L,
316,316Lhave failed due to stress corrosion cracking.
NEW DEVELOPMENT IN DUPLEX
‱ First generation duplex.-
The first generation duplex containing.-
Cr-25 %., Ni-5 %, and Mo-1.5 % and Nitrogen ---Nil
There is no Nitrogen. Because Carbon Content up to 0.2%.There is a considerable loss in
corrosion resistance during welding Therefore, a post weld heat treatment is required to
assure good prosperities.
SECOND GENRATION DUPLEX
The second generation duplexes have low carbon levels, assuring resistance to irregular
attack (IGA) the nitrogen contents are usually more than 0.1%.in addition to improving
pitting and crevice corrosion.
Cr. -25 %, Ni.—5 %, Mo.-1.5 %.N- 0.1%.
THIRD GENERATION DUPLEX
‱ The third generation duplex contains about 0.2% copper.Cr.-25 % Ni.-4.0 % Mo-Nil. Cu.-
0.2%
‱ “A third generation developed in SWEDON, has recently been introduced Alloy 2304.” and
SAFUREX.
14
‱ HVD-1 is also 3rd generation Duplex S.S. and developed by Snampogetti(Italy).
SUPERFERRITIES
These are highly resistant to chloride pitting and crevice corrosion. They have found extensive
applications as tubing for power plant condensers, and heat exchanger handling chloride solution,
such as Sea water. Having a ferrite microstructure. They have a very high resistance to CSCC. In
addition they are suitable for use in organic acids, dilute reducing acids.
SAFUREX (STAMICARBON)
Safurex is jointly developed by SANDVIK & STAMICARBON and designated SafurexTM.can allow
lower Oxygen content for passivation. Safurex has become a well established material in the Urea
world and has contributed to the improved design, maintenance and operation of urea plants in
many countries. Numbers of H.P. stripper in Stamicarbon plant have been replaced by Safurex.
Chemical composition and PRE No for various Duplex & Stainless Steel
Table No.9
S.No. Grade Cr Ni Mo N PRE Microstructure
1 2RE 60(UG) 18.5 4.9 2.7 0.07 28 Duplex
2
SAF 2304 23 4.5 - 0.1 24 Duplex
3
SAF 2205 22 5.5 3.2 0.18 35 Duplex
4
SAF 2507 25 7 4 0.3 43 Duplex
5
AISI 304L 18.5 10 - - 18 Austenitic
6
AISI 316L 17.5 13 2.1 - 24 Austenitic
7
Sanicro 28 27 31 3.5 - 38 Austenitic
HOW TO GAUGE RESISTANCE TO PITTING
The resistance of a particular grade of stainless steel to pitting and crevice corrosion is indicated by
its Pitting Resistance Equivalent number or PRE, as shown in table. The PRE can be calculated from
the composition as:
PRE = %Cr + 3.3 %Mo + 16 %N
PRE is also known as LCR-Localized Corrosion Resistance
15
“Selection for Fabrication”
Again it is usually the case that grades are selected for corrosion resistance and then consideration
is given to how the product can be fabricated. Fabrication should be considered as early as possible
in the grade selection process, as it greatly influences the economics of the product. Table lists
some common grades and compares their relative fabrication characteristics. These comparisons
are on arbitrary 1 to 10 scales, with 10 indicating excellent fabrication by the particular method.
Common Grades and Their Relative Fabrication Characteristics
Table No 10
S.No. Grade Formability Machinability Weldability
1 303 1 8 * 1
2 304 8 5* 8
3 316 8 5* 8
4 416 1 10 1
5 430 4 6 2
6 430 4 6 2
7 2205 5 4 5
8 3CR12 5 6 6
* Improved Machinability versions of these grades offer higher machinabilities in some
products.
A higher PRE value, however, cannot be used as a direct selection criterion. For selection of
material in chloride-containing solution a diagram showing the critical pitting temperature. Has to
be used.
PITTING CORROSION-The pitting resistance equivalent is a simplified way of comparing the
resistance to pitting corrosion for different grade. A higher PRE-value generally means a better
resistance. The PRE-value, however, cannot be used as direct selection criteria. For the selection of
material in chloride containing solution a diagram showing the critical pitting temperature (CPI)
has to be used. As long as the service conditions are below the curve for the considered grade,
pitting will not occur. Figure No. 7 shows the pitting resistance curve for various grades.
16
Figure No.-7
REFORMER TUBES
MATERIAL OF CONSTRUCTION :- The Primary reformer is at the heart of any ammonia plant and
represents the largest capital expenditure unit operation and also is the largest energy user on the
plant.As is well known, primary reformer tubes have a finite life and will start to fail after a period
of time. It is therefore usual to replace the reformer tubes at this point and this offers an
opportunity to conduct a fundamental change in the performance of the primary reformer by
changing the metallurgy, inside diameter and thickness of the tubes. When changing the
reformer tubes, there is also an opportunity to re-optimize the catalyst loading to generate
further process benefits. The materials used for the reformer are critical as their performance
directly impacts the technical andeconomic viability of the technology.researchers are
investigateting the behavior of a number of metal and refractory of a number of metal and
refractory material in system that simulates the conditions in a pulse enhance steam reformer.these
test will help to identify those material that perform will in the corrosive,high temperature
environments encountered in the reformer.one of very important aspect to be considered at the
design stage of a reformer,is the materil of construction, as this affects the throughout and the
energy consumption in a fertilser plant.conventianally,the HK40 or IN 519 or equivalmnt material
were being used.
Tube Design
Types of tube metallurgy
There has been a great deal of development in the area of tube metallurgy in the last 50 years,
first with the introduction of centrifugally cast tubes in the 1950s,moving through to the
17
introduction of HK40 in the early 1960s and then on to the HP modified tubes in the mid-1970s
and finally the HP micro-alloys in the mid-1980’s. The following table illustrates the
development of the metallurgy with time.
Metallurgy developments
Table No. –11
Date Common
name
Cr Ni Nb Others Relative
strength
1960s HK 40 25 20 1.0
1970s IN 51 25 24 1 1.4
Mid
1970s
HP mod. 25 35 1 1.9
Mid
1980s
HP micro
alloys
25 35 1 Ti,Zr,W,Cs 2.2
The real key to re-tubes is the significant improvement in strength that can be achieved by
moving to a more modern alloy. The following graph illustrates the maximum allowable stress
data for a variety of materials.
Figure No.-8
The additional strength of modern alloys allows a reduction in the tube wall thickness and a
consequent increase in the reformer tube inside diameter. This in turn leads to significant
reductions in reformer pressure drop and hence plant rate increases. The latest trendis to utilise
micro-alloys,which have a higher creep resistance.These modified HPNb material stablished with
micro-alloys.Typically Chromium-25, Nickel -35%, Niobium -1.5% and, Titanium –Traces.
These material have high stability of carbide,increased creep strength, higher durability and
oxidation resistance compared to the conventional material.Tha advantage of using these micro-
alloys are-
0
5
10
15
20
25
30
35
HK40 IN519 HP Nb Mod HP Micro-alloy
Rupture Stress for generic tube
materials(N/mm2)
18
1. Possibility of operation of the reformer of higher temperature & pressure.
2. Reduced reformer wall thickness.
3. Increased quality of catalyst packing in the same space-this aspect has been utilised
advantageously, for increasing the capacity of existing reformers.
Tube design principles
To appreciate fully the key aspects of reformer tube management, it is important that the
fundamental principles of the reformer tube design are understood. When designing
reformer tubes, either for a new plant or for a re-tube of an existing primary reformer, the
first key choices are what material, tube thickness and inside diameter will be selected. The
highest value and most critical asset in many plants, the steam reformer, host the components most
likely to experience material failure - reformer tubes. Reformer reliability, availability and
utilization (as measured by reformer tube reliability and condition) affect plant production, outage
risk and potential production loss due to protracted downtime. Plant health, safety and
profitability can be directly improved and unexpected tube failures can be avoided, with confident
predictions of reformer remaining life. However, recognized industry standards for remaining life
evaluation such as API 579-1, do not address reformer tubes. Moreover, the API 579-1 Section 10
Omega method for creep assessment was not designed to consider the unique performance
characteristics of modern HP alloys, which make up most reformer tubes currently in service. The
next stage is to conduct a detailed simulation of the reformer to determine the pressure
and temperature profiles axially along the tube. From this information, the stress being
applied to the tube can be calculated and then, using the allowable stress-temperature data
for the chosen material, the design temperature for the tube can be calculated. This is
Normally illustrated by a Larsen-Miller plot which is a plot of stress against temperature. A typical
Larsen-Miller plot is shown in figure No.9.
19
Figure No.-9
If the design temperature is less than the maximum operating temperature, then the design
procedure needs to be repeated with a thicker wall tube; the converse is also true. Since the
Larsen-Miller curves have been generated using a statistical analysis of tubes lives, there will
be some tubes that fail before the expected tube life (typically 100,000 hours). It is normally
expected that 2% of tubes will fail prior to achieving the expected life.
Latest Omega Bond Tubing Technology HP Urea Stripper by M/S Saipem.
Omega BondÂź Advanced Tubing -- A Superior Solution to Combat Corrosion
Omega BondÂź Tubing is a robust, advanced tubing design for use in corrosive chemical processes
and other applications. Omega BondÂź Tubing technology can be applied to the extremely corrosive
urea process. The new tubing designs enable the application of multiple and/or dissimilar metals in
a single tube. Allowing you to put the right alloy where you need it most.
The advantages of this new material technology are a solution to corrosion and erosion issues
observed in urea stripper equipment. Advantages of Omega BondÂź Tubing technology includes:
‱ Superior corrosion resistance of the zirconium inner-liner (zero corrosion rate)
‱ Directly wieldable into a titanium clad tube sheet without affecting the tube liner bond
strength
‱ No passivation air requirements
‱ Useful in existing titanium-tube units
‱ Eliminates urea solution seepage between the liner and tube because of the extrusion
(metallurgic ally) bonded zirconium inner-liner
20
CONCLUSION –Corrosion problems may vary from plant to plant because of local service condition.
When they became frequent, there is a need to select better materials. The initial cost for a better
material may be higher, but a later change to corrosion resistant material is always more expensive.
A number of applications in the production of ammonia, urea and nitric acid have been reviewed
with respect to potential corrosion problem. In many case the cost effective duplex stainless can be
successfully applied in view of past performance.2RE10 is recommended for nitric acid service and
for urea service 2RE 69. The tube metallurgy was upgraded a HP modified micro alloy and this
allowed for an increase in the inside tube diameter. The outside diameter was left unchanged. This
change reduced the pressure drop across the primary reformer by 40% and reduced the natural gas
fuel usage by 3.1%. Both of these effects allowed for an improvement in plant efficiency.
REFERENCES- 19th AFA Int’l Fertilizer Technical Conference & Exhibition18- 20 April 2006 Four
Seasons Hotel Doha- Qatar.
www.alokaloys.com
Fertilizer Industry, 1997 page 115-116, energy bulletin on reformer.U.S. Department of Energy,
Energy Efficiency and renewable energy Sept-2004.
******************************************************

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Material selection for nitrogen based fertilizers plants

  • 1. 1 MATERIAL SELECTION FOR NITROGEN BASED FERTILIZERS PLANTS Author Prem Baboo Sr. Manager (Prod) National Fertilizers Ltd., Vijaipur, India INTRODUCTION Materials plays very important role in any industry .Selection of material is vital at design stage itself. Wrong selection of material may lead to catastrophic failures and outage of plants & even loss of Human lives. Right selection of material leads to long life of plant. Fertilizer Plants employ various corrosive, hazardous and abrasive fluids and chemicals. The temperatures involved range from cryogenic (-330C) in ammonia storage to 10000C in reformer. The pressure are as high as 175- 350kg/cm2 in ammonia converter and in urea plant reactor pressure 150-250 kg/cm2.Once equipment has been selected, the materials for its construction must be established. Although a process Engineer is not expected to be knowledgeable as a metallurgist, the engineer should have a general idea of what materials are compatible with the process. Therefore, this topic presents some general guidelines in the selection of material for process equipment. In all ammonia, Urea Plants worldwide the problem of severe erosion and corrosion of high pressure vessel has been a common phenomenon. In Ammonia Plants, past experience has shown that duplex stainless steels can successfully replace carbon steel and stainless steel in most heat exchangers at temperatures below 3000C.The improved corrosion resistance gives longer service life and what is more important, fewer standstills. High alloyed duplex stainless steels can even be used for seawater-cooled heat exchangers. In urea plants the stripping technology has called for special care in the choice of materials. A wider use of special alloys has resulted in lower maintenance costs and longer service life. When considering the new materials of construction, one most remember that it takes time to build up a comprehensive portfolio of corrosion data and case studies supporting their successful use. For this reason, corrosion-resistant alloys first introduced in the early 1980s are still considered to be newer. STAINLESS STEEL ‱ “Steel that has 12% or more chromium is considered stainless steel.” ‱ “Another criterion defining a stainless steel is its Passivity.”
  • 2. 2 ‱ PASSIVITY - “Passivity is the ability of a metal to form an impervious surface coating which inhibits corrosion resulting from the electrochemical reaction of the metal with the surrounding environment.” ‱ “Stainless Steels exhibit passivity in oxidizing environment.” To ensure that carbon do not migrate to welding joints (because temperature between 5500C-8500C during welding this cause depletion of chromium as carbon form) Cr23C6 at grain boundaries in region adjacent to welds. There is quit serious depletion of chromium and have a weakening of passivity. Following may be done. I. Either keep carbon less than 0.03% II. Add Ti four times of carbon content III. Niobium eight times of carbon content Corrosion as function of Chromium “Following figure No.1 shows the corrosion rate as function chromium content in an iron chromium alloy.” It might be assumed that increasing the chromium contents without limit would improve corrosion resistance. This does not happen Figure No.-2 shown the phase diagram for iron and chromium in all proportions. With Chromium contents between 20 & 70%, the Sigma microstructure is formed. Figure No.1
  • 3. 3 IRON-CHROMIUM PHASE DIAGRAM ‱ Following figure No.2 shows the phase diagram for iron chromium in all proportions. ‱ With chromium contents between 20 and 70%, the “sigma” microstructure is formed. SIGMA MICROSTRUCTURE.- “This microstructure is hard, brittle and poor corrosion resistance.” Figure No.2 TYPES OF STAINLESS STEEL There are three general types of stainless steel of interest to the process engineer. 1. FERRITIC STAINLESS STEEL 2. AUSTENITIC STAINLESS STEEL 3. MARTENSITIC STAINLESS STEEL FERRITIC STAINLESS STEEL ‱ Ferritic stainless steel has a carbon content of 0.2% or less. Fig. No.3 ‱ Chromium content 11-18% .
  • 4. 4 ‱ Although it can not be heat treated and has poor tensile and impact strength, it better corrosion resistance than martensitic stainless steel. ‱ Highly resistant to stress corrosion cracking show an increases as result of cold work ‱ They are magnetic, have good ductility readily weldable, non-magnetic ‱ Welding is difficult ‱ SS 430(17% Cr) USED FOR AUTOMOTIVE TRIMS FERRITIC STAINLESS STEEL (Chemical Requirements) Table No.1 AISI 430 C Mn P S Si Cr 0.12 1.0 0.04 0.03 1 14-18 ‱ It is suitable for use with strong oxidizing acids such as Nitric acid. Figure No.-3
  • 5. 5 MARTENSITIC STAINLESS STEEL ‱ Farritic stainless steel has a Carbon.-1.2% or less. And Chromium.-12-18%. Fig.No.4 ‱ It has better hardenability and strength than does ferritic stainless steel. ‱ It is used as cladding to carbon steel for some process vessels. IRON –CHROMIUM PHASE DIAGRAM FOR 1.0% CARBON Figure No.-4 MARTENSITIC STAINLESS STEEL (Chemical Requirements) Table No.2 AISI C Mn P S Si Cr 410 0.15 1.0 0.04 0.03 1.0 11.5-13.5 420 0.15 1.0 0.04 0.03 1.0 12-14
  • 6. 6 AUSTENITIC STAINLESS STEEL ‱ “Austenitic stainless steel is a more complex material because the addition of NICKEL (3.5 to 22%) allows it to retain its austenitic microstructure at all temperature ‱ It has a high tensile strength and best impact strength, ductility and corrosion resistance of all the stainless steel over a very wide range of temperatures. ‱ All stainless steels are susceptible to pitting from exposure to high chloride concentration. However, austenitic steel with high Molybdenum content (1 to 3 %) has improved resistance to pitting. ‱ The austenitic alloys have a face centered cubic structure which has a better corrosion resistance compared to the ferritic steels. The austenitic structure is normally not stable in irons below 7000 C, but adding nickel to the steel makes the austenitic phase stable down to room temperature ‱ These alloys are basically chromium nickel steels. Chromium is used in these alloys to make the steel corrosion resistant, whereas nickel stabilizes the even more corrosion resistant austenitic structure. Silicon and aluminum are added to increase the oxidation resistance. Titanium and niobium, as well as boron, nitrogen, tungsten, vanadium and cobalt can be added to increase the creep strength due to precipitation strengthening. Manganese can be used to substitute nickel as an austenite former. Fig. No.5 Fe-Cr-Ni Ternary diagram for an 18% Cr alloy with the austenitic Stainless Steel.
  • 7. 7 Figure No.-5 AUSTENETIC STAINLESS STEEL (Chemical Requirements) Table No.3 Sr.No. AISI C Mn Si Cr Ni Mo 1 304 0.08 2.0 1.0 18-20 8-10.5 - 2 304L 0.03 2.0 1.0 18-20 8-10.5 - 3 309 0.2 2.0 1.0 22-24 12-15 - 4 310 0.2 2.0 1.0 24-26 19-22 - 5 316 0.08 2.0 1.0 16-18 10-14 2-3 6 316L 0.08 2.0 1.0 16-18 10-14 2-3 7 321 0.08 2.0 1.0 17-19 9-12 TI≄5×C 8 347 0.08 2.0 1.0 17-19 9-12 Nb≄5×C
  • 8. 8 STAINLESS STEEL Table No.-4 Sr.No . MEDIA TYPE OF STEEL 13% Cr steel 18/8 Austenitic 18/10+Mo 1 Nitric acid Resist all strength cold attacked by strong boiling acid Attacked only by boiling concentrated acid As 18/8 2 Phosphoric Acid Attacked by all strength but less so in 60-90 range Resists most strength point. Slight attack by boiling 40% and hot 60- 90% attacked by 80%and at 110% Resist to all strength up to boiling point but attacked by 80% acid at 1000C 3 Sulphuric Acid Attacked by all concentrations Slightly attacked by cold 5-10% and by hot & cold 85-95% acid. Attacked by hot or cold 15-75% acid Resistant to hot and cold 5-10% acid and to cold15, 85 & 95% acid. Slightly attacked by hot 15.85 & 95% acid attacked by hot 20% and cold40- 70% acid 4 ammonia Resist all strength hot or cold Resist all strength hot or cold Resist all strength hot or cold 5 Caustic Soda Resist up to 30% hot or cold slightly attacked by hot 30- 50% and by molten salt at 3700C Resist up to 30-50% solution slightly attacked by molten salt at 3700C As 18/8 6 Caustic potash Resists 25% solution up to boiling point Resist 25% solution up to boiling point slightly attacked by 50% at boiling point attacked by molten salt at 3600C As 18/8
  • 9. 9 MATERIALS FOR CARBAMATE SERVICE Carbamate is highly corrosive in nature at high pressure & temperature. All over the world licensers of urea plants are searching or cost effective & better corrosion resistant materials. MATERIALS FOR CARBAMATE SERVICE TITANIUM ZIRCONIUM 316l MOD OR 316L UG OR 3RE60 2RE69 OR 25Cr.-22Ni.-2Mo. (UNS S31050) DUPLEX STEEL TITANIUM Titanium is used in the relatively pure state .It has excellent corrosion resistance but is one of the more costly and difficult alloy to weld. Titanium corrosion resistance is due to the impervious oxide film i.e.100% TiO2 film on surface. Titanium is resistant to stress- corrosion cracking and erosion corrosion, but it is susceptible to crevice corrosion in stagnant chloride solutions. Used for lining & tube material of ammonia stripper in Snamprogetti’s urea plants. Commercially pure Titanium exhibits a high resistance to pitting attack. Used for lining of urea reactors of TOYO plants MTC Process and corrosion resistance of Titanium is because of formation of oxide layer In Reactor oxygen is fed with CO2. ADVANTAGES : Passivation air is less required as compared other stainless steel. Stripper bottom temperature in Urea Plant can be kept up to 210 0 C while in 2 RE 69 temperature cannot be raised beyond 2070C. DISADVANTAGES Titanium is not maintenance friendly the difficult in welding Titanium is due to high affinity for Hydrogen, Nitrogen and oxygen in the molten state. Therefore, it must be welded by such inert-gas welding method as the TIG or MIG process. After a weld has been made, the inert-gas protection must be maintained until the welding joint cool below 6500C,
  • 10. 10 otherwise, the Titanium will react with the oxygen, Nitrogen and moisture in the air, resulting in weld embrittlement. Erosion of tubes ends resulting in bypassing in stripper due to tube end over ferrules badly eroded by carbamate solution. Figure No.-6 HCP-(hexagonal closed packed) HCP metal are not ductile as FCC metal e.g.-Be,Mg,Zn,Cd,Co,Tl,Zr. Etc The HCP cell consists three layers of atom The top and bottom layers contain six atom at the corner of the hexagonal and one atom at the centre of each hexagonal. The middle layer contains three atoms nestled between the atom of the top & bottom layers hence the name close packed ,figure No-6. 316L MOD & 2 RE 69 These are Tailor made grades of austenitic stainless steel to suit required specifications of purchaser USES OF 316L MOD & 2RE69 USES OF 316L MOD & 2RE69 Table No-5 Sr.No. 316 Mod 2 Re 69 1 Reactor Lining Ammonia stripper Lining 2 Carbamate Separator Lining Carbamate Separator Lining & Tubes 3 H.P Section Piping Pool Reactor & Pool Condenser 4 Stamicarbon Reactor Carbamate mixture
  • 11. 11 CHEMICAL COMPOSITION 316L MOD & 2 RE 69 Table No.6 Sr.No. Constituents 316LMod 2 RE 69 1 Carbon ≀0.02 ≀0.02 2 Chromium 18 24-26 3 Nickel >13 21-23 4 Molybdenum 2-2.6 2-2.6 5 Manganese 1.5-2 1.5-2 6 Silicon 0.4 0.4 7 Sulphur 0.01 0.015 8 Phosphorus 0.01 0.02 9 Nitrogen(max) 0.10 0.1-0.15 METALLOGRAPHIC PROPERTIES: Material in contact with process fluid shall have austenitic structure Ferrite content shall not exceed 0.6% except for manual welds, for which 1% is allowed “SIGMA PHASE SHALL BE ABSENT” Chromium carbides may be present in minimum amount only Material shall pass Huey Test & shall be performed according to ASTM A 262 practice ‘C’ and maximum corrosion rate allowed shall be: Table No.-7 S.No. Type of Material Corrosion rate mm/yr Depth of attack micron 1 316L mod 0.6 90 2 2 RE 69(25/22/2) 0.3 70
  • 12. 12 Rate of Corrosion as per Huey Test Table No-8 S.No. Material Corrosion rate( mm/yr.) 1 ZIRCONIUM 0.005 2 TITANIUM 0.06 3 2 RE 69(25/22/20 0.3 4 316 L MOD 0.6 HUEY TEST- “Metal sample is boiled in 65% HNO3 for 48 Hrs (5times) to estimate corrosion rate.” Zirconium Zirconium is being used in Chemical Industries contains up to 2% Hafnium but does not affect chemical properties of Zirconium. Zirconium has good mechanical properties at room temperature, but retains strength at elevated temperatures only if highly alloyed.Apperance –Steel Grey. Corrosion resistance because of ZrO2 layer. Zirconium is more expensive than Titanium (roughly twice that of Titanium) “DUPLEX” STAINLESS STEEL” ‱ “DULEX steel is characterized by a microstructure containing both Ferritic phase with a BCC crystallographic structure and an Austenitic phase with a FCC structure.” ‱ The Ferritic phase is normally 40-60%, mainly introduced in the wrought alloys by a careful balance of the critical alloying elements. ‱ Mixture of Austenite & Ferrite ‱ Higher strength & better resistance to Chlorides ‱ Cr: 18-27%, Ni: 4-7%, Mo: 2-4% ‱ BCC.-Body centered cubic “High strength low ductility.” ‱ e.g.-Ferrite(α-iron),Cr,V,Mo,W etc. ‱ FCC-(Body centered cubic). “Low strength high ductility.” ‱ e.g. Austenite( Îł-iron),Al,Cu,Pb,Ag,Au,Ni,Pt etc.
  • 13. 13 ‱ Stress Corrosion Cracking ‱ A particular problem for the common austenitic grades (e.g. 304 and 316) is stress corrosion cracking (SCC). Like pitting corrosion this occurs in chloride environments, but it is possible for SCC to take place with only traces of chlorides, so long as the temperature is over about 60°C, and so long as a tensile stress is present in the steel, which is very common. The ferritic grades are virtually immune from this form of attack, and the duplex grades are highly resistant. If SCC is likely to be a problem it would be prudent to specify a grade from these branches of the stainless family tree. Advantages of Duplex Stainless Steel ‱ Good resistance to “chloride stress corrosion cracking.”(CSCC). ‱ The duplex stainless steel also offers resistance to general and pitting corrosion. ‱ Good resistance to erosion and abrasion. ‱ There are numerous cases where plant equipment properly fabricated from duplex SS has operated with full immunity in chloride containing environment where types 304,304L, 316,316Lhave failed due to stress corrosion cracking. NEW DEVELOPMENT IN DUPLEX ‱ First generation duplex.- The first generation duplex containing.- Cr-25 %., Ni-5 %, and Mo-1.5 % and Nitrogen ---Nil There is no Nitrogen. Because Carbon Content up to 0.2%.There is a considerable loss in corrosion resistance during welding Therefore, a post weld heat treatment is required to assure good prosperities. SECOND GENRATION DUPLEX The second generation duplexes have low carbon levels, assuring resistance to irregular attack (IGA) the nitrogen contents are usually more than 0.1%.in addition to improving pitting and crevice corrosion. Cr. -25 %, Ni.—5 %, Mo.-1.5 %.N- 0.1%. THIRD GENERATION DUPLEX ‱ The third generation duplex contains about 0.2% copper.Cr.-25 % Ni.-4.0 % Mo-Nil. Cu.- 0.2% ‱ “A third generation developed in SWEDON, has recently been introduced Alloy 2304.” and SAFUREX.
  • 14. 14 ‱ HVD-1 is also 3rd generation Duplex S.S. and developed by Snampogetti(Italy). SUPERFERRITIES These are highly resistant to chloride pitting and crevice corrosion. They have found extensive applications as tubing for power plant condensers, and heat exchanger handling chloride solution, such as Sea water. Having a ferrite microstructure. They have a very high resistance to CSCC. In addition they are suitable for use in organic acids, dilute reducing acids. SAFUREX (STAMICARBON) Safurex is jointly developed by SANDVIK & STAMICARBON and designated SafurexTM.can allow lower Oxygen content for passivation. Safurex has become a well established material in the Urea world and has contributed to the improved design, maintenance and operation of urea plants in many countries. Numbers of H.P. stripper in Stamicarbon plant have been replaced by Safurex. Chemical composition and PRE No for various Duplex & Stainless Steel Table No.9 S.No. Grade Cr Ni Mo N PRE Microstructure 1 2RE 60(UG) 18.5 4.9 2.7 0.07 28 Duplex 2 SAF 2304 23 4.5 - 0.1 24 Duplex 3 SAF 2205 22 5.5 3.2 0.18 35 Duplex 4 SAF 2507 25 7 4 0.3 43 Duplex 5 AISI 304L 18.5 10 - - 18 Austenitic 6 AISI 316L 17.5 13 2.1 - 24 Austenitic 7 Sanicro 28 27 31 3.5 - 38 Austenitic HOW TO GAUGE RESISTANCE TO PITTING The resistance of a particular grade of stainless steel to pitting and crevice corrosion is indicated by its Pitting Resistance Equivalent number or PRE, as shown in table. The PRE can be calculated from the composition as: PRE = %Cr + 3.3 %Mo + 16 %N PRE is also known as LCR-Localized Corrosion Resistance
  • 15. 15 “Selection for Fabrication” Again it is usually the case that grades are selected for corrosion resistance and then consideration is given to how the product can be fabricated. Fabrication should be considered as early as possible in the grade selection process, as it greatly influences the economics of the product. Table lists some common grades and compares their relative fabrication characteristics. These comparisons are on arbitrary 1 to 10 scales, with 10 indicating excellent fabrication by the particular method. Common Grades and Their Relative Fabrication Characteristics Table No 10 S.No. Grade Formability Machinability Weldability 1 303 1 8 * 1 2 304 8 5* 8 3 316 8 5* 8 4 416 1 10 1 5 430 4 6 2 6 430 4 6 2 7 2205 5 4 5 8 3CR12 5 6 6 * Improved Machinability versions of these grades offer higher machinabilities in some products. A higher PRE value, however, cannot be used as a direct selection criterion. For selection of material in chloride-containing solution a diagram showing the critical pitting temperature. Has to be used. PITTING CORROSION-The pitting resistance equivalent is a simplified way of comparing the resistance to pitting corrosion for different grade. A higher PRE-value generally means a better resistance. The PRE-value, however, cannot be used as direct selection criteria. For the selection of material in chloride containing solution a diagram showing the critical pitting temperature (CPI) has to be used. As long as the service conditions are below the curve for the considered grade, pitting will not occur. Figure No. 7 shows the pitting resistance curve for various grades.
  • 16. 16 Figure No.-7 REFORMER TUBES MATERIAL OF CONSTRUCTION :- The Primary reformer is at the heart of any ammonia plant and represents the largest capital expenditure unit operation and also is the largest energy user on the plant.As is well known, primary reformer tubes have a finite life and will start to fail after a period of time. It is therefore usual to replace the reformer tubes at this point and this offers an opportunity to conduct a fundamental change in the performance of the primary reformer by changing the metallurgy, inside diameter and thickness of the tubes. When changing the reformer tubes, there is also an opportunity to re-optimize the catalyst loading to generate further process benefits. The materials used for the reformer are critical as their performance directly impacts the technical andeconomic viability of the technology.researchers are investigateting the behavior of a number of metal and refractory of a number of metal and refractory material in system that simulates the conditions in a pulse enhance steam reformer.these test will help to identify those material that perform will in the corrosive,high temperature environments encountered in the reformer.one of very important aspect to be considered at the design stage of a reformer,is the materil of construction, as this affects the throughout and the energy consumption in a fertilser plant.conventianally,the HK40 or IN 519 or equivalmnt material were being used. Tube Design Types of tube metallurgy There has been a great deal of development in the area of tube metallurgy in the last 50 years, first with the introduction of centrifugally cast tubes in the 1950s,moving through to the
  • 17. 17 introduction of HK40 in the early 1960s and then on to the HP modified tubes in the mid-1970s and finally the HP micro-alloys in the mid-1980’s. The following table illustrates the development of the metallurgy with time. Metallurgy developments Table No. –11 Date Common name Cr Ni Nb Others Relative strength 1960s HK 40 25 20 1.0 1970s IN 51 25 24 1 1.4 Mid 1970s HP mod. 25 35 1 1.9 Mid 1980s HP micro alloys 25 35 1 Ti,Zr,W,Cs 2.2 The real key to re-tubes is the significant improvement in strength that can be achieved by moving to a more modern alloy. The following graph illustrates the maximum allowable stress data for a variety of materials. Figure No.-8 The additional strength of modern alloys allows a reduction in the tube wall thickness and a consequent increase in the reformer tube inside diameter. This in turn leads to significant reductions in reformer pressure drop and hence plant rate increases. The latest trendis to utilise micro-alloys,which have a higher creep resistance.These modified HPNb material stablished with micro-alloys.Typically Chromium-25, Nickel -35%, Niobium -1.5% and, Titanium –Traces. These material have high stability of carbide,increased creep strength, higher durability and oxidation resistance compared to the conventional material.Tha advantage of using these micro- alloys are- 0 5 10 15 20 25 30 35 HK40 IN519 HP Nb Mod HP Micro-alloy Rupture Stress for generic tube materials(N/mm2)
  • 18. 18 1. Possibility of operation of the reformer of higher temperature & pressure. 2. Reduced reformer wall thickness. 3. Increased quality of catalyst packing in the same space-this aspect has been utilised advantageously, for increasing the capacity of existing reformers. Tube design principles To appreciate fully the key aspects of reformer tube management, it is important that the fundamental principles of the reformer tube design are understood. When designing reformer tubes, either for a new plant or for a re-tube of an existing primary reformer, the first key choices are what material, tube thickness and inside diameter will be selected. The highest value and most critical asset in many plants, the steam reformer, host the components most likely to experience material failure - reformer tubes. Reformer reliability, availability and utilization (as measured by reformer tube reliability and condition) affect plant production, outage risk and potential production loss due to protracted downtime. Plant health, safety and profitability can be directly improved and unexpected tube failures can be avoided, with confident predictions of reformer remaining life. However, recognized industry standards for remaining life evaluation such as API 579-1, do not address reformer tubes. Moreover, the API 579-1 Section 10 Omega method for creep assessment was not designed to consider the unique performance characteristics of modern HP alloys, which make up most reformer tubes currently in service. The next stage is to conduct a detailed simulation of the reformer to determine the pressure and temperature profiles axially along the tube. From this information, the stress being applied to the tube can be calculated and then, using the allowable stress-temperature data for the chosen material, the design temperature for the tube can be calculated. This is Normally illustrated by a Larsen-Miller plot which is a plot of stress against temperature. A typical Larsen-Miller plot is shown in figure No.9.
  • 19. 19 Figure No.-9 If the design temperature is less than the maximum operating temperature, then the design procedure needs to be repeated with a thicker wall tube; the converse is also true. Since the Larsen-Miller curves have been generated using a statistical analysis of tubes lives, there will be some tubes that fail before the expected tube life (typically 100,000 hours). It is normally expected that 2% of tubes will fail prior to achieving the expected life. Latest Omega Bond Tubing Technology HP Urea Stripper by M/S Saipem. Omega BondÂź Advanced Tubing -- A Superior Solution to Combat Corrosion Omega BondÂź Tubing is a robust, advanced tubing design for use in corrosive chemical processes and other applications. Omega BondÂź Tubing technology can be applied to the extremely corrosive urea process. The new tubing designs enable the application of multiple and/or dissimilar metals in a single tube. Allowing you to put the right alloy where you need it most. The advantages of this new material technology are a solution to corrosion and erosion issues observed in urea stripper equipment. Advantages of Omega BondÂź Tubing technology includes: ‱ Superior corrosion resistance of the zirconium inner-liner (zero corrosion rate) ‱ Directly wieldable into a titanium clad tube sheet without affecting the tube liner bond strength ‱ No passivation air requirements ‱ Useful in existing titanium-tube units ‱ Eliminates urea solution seepage between the liner and tube because of the extrusion (metallurgic ally) bonded zirconium inner-liner
  • 20. 20 CONCLUSION –Corrosion problems may vary from plant to plant because of local service condition. When they became frequent, there is a need to select better materials. The initial cost for a better material may be higher, but a later change to corrosion resistant material is always more expensive. A number of applications in the production of ammonia, urea and nitric acid have been reviewed with respect to potential corrosion problem. In many case the cost effective duplex stainless can be successfully applied in view of past performance.2RE10 is recommended for nitric acid service and for urea service 2RE 69. The tube metallurgy was upgraded a HP modified micro alloy and this allowed for an increase in the inside tube diameter. The outside diameter was left unchanged. This change reduced the pressure drop across the primary reformer by 40% and reduced the natural gas fuel usage by 3.1%. Both of these effects allowed for an improvement in plant efficiency. REFERENCES- 19th AFA Int’l Fertilizer Technical Conference & Exhibition18- 20 April 2006 Four Seasons Hotel Doha- Qatar. www.alokaloys.com Fertilizer Industry, 1997 page 115-116, energy bulletin on reformer.U.S. Department of Energy, Energy Efficiency and renewable energy Sept-2004. ******************************************************