Stamicarbon Safurex
Stamicarbon Safurex
Stamicarbon Safurex
Authors:
Maria Hugosson, Sandvik Materials Technology
Jo Eijkenboom, Stamicarbon
June 2004
1.
Table of Contents
Page:
1. Preface.............................................................................................................................. 2
2. Abstract ............................................................................................................................. 3
3. Introduction ....................................................................................................................... 4
4. Development of several Duplex grades ending in Safurexâ ............................................... 5
5. Quality requirements ......................................................................................................... 6
6. Mechanical properties ....................................................................................................... 8
7. 475°C embrittlement.......................................................................................................... 9
7.1 Base Materials .................................................................................................. 9
7.2 Weld deposits ................................................................................................... 9
8. Safurexâ welding ..............................................................................................................10
9. Design consequences ......................................................................................................11
9.1 Liners .............................................................................................................. 11
9.2 Heat Exchanger tubes..................................................................................... 12
9.2.1. HP Stripper, HP Carbamate Condenser and HP Scrubber tubes............ 13
9.2.2 Heat exchanger tubes for Pool condenser / Pool reactor ......................... 14
10. Side effects when using SafurexÒ ...................................................................................16
10.1.Tubesheet thickness ..................................................................................... 16
10.2. Bellows design ............................................................................................. 16
11. HP piping........................................................................................................................17
12. Miscellaneous products ..................................................................................................19
12.1 Forgings ........................................................................................................ 19
12.2 Plates ............................................................................................................ 19
12.3 HP Piping bends ........................................................................................... 19
12.4. HP Pipe flanges ........................................................................................... 20
12.5 Valves and accessories ................................................................................ 21
13. In plant test results of Safurexâ .....................................................................................22
13.1 HP Carbamate Condenser in the El Delta Urea Plant................................... 22
13.2 The HP Carbamate Condenser in the Police Urea Plant, Poland. ................ 22
13.3 Safurex® in HP Strippers............................................................................... 22
13.3.1. HP Stripper in the UF-2 DSM Urea plant............................................... 23
13.3.2. Liquid distributors in Ultrafertil, Brazil Stripper....................................... 23
14. Practical experience with equipment fabricated in Safurexâ ..........................................24
15. Safurexâ in oxygen free carbamate solution ..................................................................25
16. Safurexâ in oxygen reduced carbamate solutions..........................................................26
16.1 Shiraz Urea Plant, Iran.................................................................................. 26
16.2 Profertil’s urea plant, Argentina..................................................................... 26
16.3 HP Stripper in the Shiraz Urea plant ............................................................. 28
16.4 Exposure test of SafurexÒ in a Snamprogetti designed plant........................ 28
17. Future developments......................................................................................................29
18. Economical consequences .............................................................................................30
19. Conclusions....................................................................................................................31
1.
1. Preface
All technical and other information contained herein is based on general Stamicarbon/DSM experience and within
this limit is accurate to the best of our knowledge. However, no liability is accepted therefor and no warranty or
guarantee is to be inferred.
2.
2. Abstract
In 1992 Stamicarbon and Sandvik met to discuss a new material to be developed for use in
urea plants. Following goals were set:
10 years later, after successful research and development and elaborate experiments and in
plant experiences, the conclusion is that all goals have been realized and that this material
has even gone beyond our expectations. SafurexÒ (Stamicarbon A-4 18005 type BE.06) is a
duplex stainless steel grade exclusively developed by Sandvik for the Stamicarbon urea and
melamine process.
This paper reviews the development and shows the success of SafurexÒ. Since 1997 several
SafurexÒ HP heat exchangers have been fabricated successfully. At this moment a plant is
under construction whereby the complete synthesis is made from SafurexÒ.
3.
3. Introduction
In 1992, both Stamicarbon and Sandvik met for their annual meeting in which ongoing
developments with respect to material, weld deposits and corrosion aspects in the field of
urea were discussed and experiences were exchanged.
In that particular meeting, the idea to use a duplex as alloy protection was discussed.
Stamicarbon indicated that it should be possible to design a urea plant that could run without
oxygen using duplex material as alloy protection.
In practice, it was already proven that duplex alloys in urea application showed good
corrosion resistance and that it should in theory be possible to develop a Duplex Stainless
Steel that would meet that demand.
A fore cast of the needed alloying elements was indicated and goals were set. The
development of the material should finally result in a material that would show following
objectives:
4.
4. Development of several Duplex grades ending in Safurexâ
In order to find the right material composition and to ensure the reproducibility of the material
some 20 different heats were made in a laboratory high frequency furnace. The first
discrimination was done on bar and tube samples.
In first instance, it was agreed to check the quality from corrosion point of view with the Huey
test and the Streicher test.
· The heats that had a homogeneous microstructure and a low level of impurities
exhibited good corrosion resistance in the Huey test, the Streicher test and in field
tests
· Samples, selectively attacked in the Streicher test also showed selective attack in the
field test. The Huey test was not showing any selective attack in parallel samples.
These observations were for us reason to use the Streicher test as the quality test.
· Stress corrosion cracking experiments showed superior resistance to all other duplex
material.
· A field test in a HP Stripper of a urea plant indicated that the corrosion performance
of SafurexÒ is at least comparable with that of BC.05 material.
· The structure stability was tested and confirmed to be stable under critical conditions.
Out of the test results, the optimum alloy composition was selected; this material was named
SafurexÒ. In the subsequent years only slight improvements in the composition were made.
To date, SafurexÒ does not differ from the heat produced in first instance. The first produced
commercial SafurexÒ heat is now present in urea equipment and proves to be of excellent
quality in urea/carbamate solutions.
5.
5. Quality requirements
The use of a Ferrite scope appears not to be practical. Unreliable figures will appear. The
philosophy is that in case of base materials Point counting will be done and when welding,
the Ferrite content of the Procedure Qualification Welding (PQR) will be checked for its ferrite
content by Point Counting and in the mean time also the correct microstructure will be
ensured.
Subsequent, welding should be done in accordance with the weld parameters as used in the
procedure qualification welding.
It was learned that the execution of the standard ASTM Streicher test gave rise to many
discussions. For that reason, we have developed our own Specification for Streicher testing.
In order to have comparable results, the test should only be executed as per this
specification. The quality of the various SafurexÒ products proves to be very stable.
6.
The material is recognized in the ASME system under UNS 32906 and applied as per ASME
Code Case 2295.
7.
6. Mechanical properties
The mechanical properties are unambiguously better than any other alloy protection in use in
urea plants so far.
8.
7. 475°C embrittlement
At 100°C, the toughness is on the low side while at operating conditions the ductility is
secured as can be learned from figure 2; the toughness is fully OK using 27 Joule is applied
as the lower limit.
Besides the mechanical aspects, also the corrosion resistance is of importance.
Investigations show that the corrosion resistance of Safurex® decreases if the material is
exposed to temperatures of 4000 C for more than 15hours.
9.
8. Safurexâ welding
The experience with the first ever Pool Condenser in SafurexÒ welded confirms this
statement. This Pool condenser has 1,202 U-tubes. In total 2,404 IBW weld were made, after
some initial fine tuning, the number of repairs did not differ from IBW welds made in BC.05
materials.
It is also important to recognize that, in spite of the fact that this was the first time that
SafurexÒ IBW welds were made in production, the welding was completed in 41 days. This
figure is in line with IBW welds in BC.05 material.
10.
9. Design consequences
The use of Safurex® as construction material has a positive impact on the design of the
equipment. Due to the lower corrosion rates and the higher mechanical properties the
following main items have been changed in detail but with large consequences.
9.1 Liners
Liners in Stamicarbon Urea plants were typically specified in A4-18005 BC.01
(316 L Urea Grade) material. Since the liner is not part of the pressure vessel, its thickness
should be enough to obtain a reasonable life time and to operate the equipment in a practical
way. Stamicarbon specifies that the limitation with respect to the lifetime of the liner is the
risk for buckling (as a result of difference in thermal expansion between the construction
materials used) in combination with the overall corrosion during operations.
10
BC.05
8
4
Safurex®
2
0
1,000 1,500 2,000 2,500 3,000 3,500 4,000 4,500
Diameter [mm]
On top of the strength calculation, a corrosion allowance of 2-mm was added in order to
obtain an acceptable lifetime of a BC.01 liner. Finally, the thickness was adapted to
commercial available thicknesses.
Subjecting SafurexÒ to the design criteria, taking in mind the high mechanical properties in
combination with the good corrosion resistance of Safurex® and the fact that the thermal
expansion coefficient of SafurexÒ is identical to that of Carbon steel, allowed us to specify a
liner thickness of 4-mm for all conditions resulting in a corrosion allowance of plus 3-mm.
Table 4 shows the difference in liner thickness comparing two materials.
11.
A corrosion rate of 0.1-mm per year on stream for BC.01 liner while for the SafurexÒ liner a
corrosion rate of 0.05-mm was taken into account.
The diameter of the reactor in this example was 3,000-mm.
Expected
Thickness inclusive
Minimum required Thickness liner
Materials corrosion allowance,
thickness, mm advised, mm life time,
mm
years
6.63 8.63 9 34
BC.01
0.34 4 4 > 50
Safurexâ
The consequence is a reduction in material cost for the liner of some 35%, while the lifetime
of the liner is more than doubled. This is made visible in figure 4.
4
BC.01 BE.06
3
Over thickness liner, mm
0
Year
11
14
17
20
23
26
29
32
35
38
41
44
47
50
53
56
59
2
-1
-2
-3
Year Onstream
12.
9.2.1. HP Stripper, HP Carbamate Condenser and HP Scrubber tubes.
Was in the past a wall thickness of nominal 3-mm for a HP Stripper and nominal
2.5-mm for a HP Carbamate Condenser and HP Scrubber specified, with the arrival of
SafurexÒ the thickness of the Stripper tubes has been adapted. The use of SafurexÒ has
serious but positive consequences for the life time of the heat exchangers .
For plant operations the minimum design wall thickness is not of interest. Important are the
actual operating pressure and temperature in order to determine when a tube should be
plugged.
Such calculation method has however to be accepted by the local authorities. This method
can only be used if, in its lifetime no pressure test conditions based on design conditions are
mandatory by the authorities.
Table 2. Miminum tube wall thickness in relation to the materials and tube
dimensions as per ASME VIII, div.1, Pressure 160 bar.
Material
Outer diameter
BC.01, mm BC.05, mm Safurex® , mm
na 1.71 1.00
31-mm, T 2250C
For plant operations a different wall thickness is conclusive. The advised minimum allowable
wall thickness of the heat exchanger tubes when checked by eddy current, based on
operating conditions can be learned from table 3.
Table 3. Minimum tube wall thickness in relation to the materials and tube
dimensions under operating conditions, pressure 145 bar.
Material
Outer diameter
BC.01, mm BC.05, mm Safurex® , mm
na 1.45 0.70
31-mm, T 2140C
The high mechanical properties of SafurexÒ result in a low minimum wall thickness, this in
combination with the allowance enables the use of HP Stripper tubes, with a wall thickness of
nominal 2.5-mm compared to 3-mm in BC.05 material.
13.
The net effect of the reduction in wall thickness of 0.5-mm compared to the wall thickness
specified in BC.05 material is a longer lifetime as shown in figure 5.
An additional advantage is that the reduction in tube wall thickness results in a larger inner
diameter of the heat exchanger tube improving the heat exchange performance and in turn
having an impact on the dimensions and finally on the weight of the equipment.
2 .5
2 B C.05 B E.06
1 .5
Extra wall thickness, m
0 .5
0
Year
11
23
32
41
44
2
14
17
20
26
29
35
38
47
-0 .5
-1
-1 .5
-2
-2 .5
-3
Years On strea m
14.
Table 4. Wall thickness U-tubes
Material
Wall thickness
BC.05, mm Safurex® , mm
1.45 0.70
31-mm, T 2140C
1.00 0.50
25-mm, T 1870C
15.
10. Side effects when using SafurexÒ
When using SafurexÒ, additional savings in the design of equipment are possible,
10.1.Tubesheet thickness
The higher mechanical properties of the heat exchanger tube leads also to a reduction in
tubesheet thickness. When calculating these tubesheets in accordance with the Standards of
the Tubular Exchanger Manufacturers Association TEMA, a reduction of some 25 % in
thickness is achieved.
16.
11. HP piping
The use of a lower schedule has a big impact on the weight of the HP Piping as can be
learned from table 5.
Not only the schedule will be different, but also the pipe size can be down scaled. This is
possible at sizes of 12” and more.
17.
The inner diameter of the tubes changes dramatically; then, one pipe size less can be used
and still having the same internal pipe surface as can be learned from table 6.
These tables are typical pipe sizing for a 3,250 mtpd tons Pool condenser Urea plant.
All these advantages are having a large consequence on the HP Piping. For a typical 3,250
mtpd plant, the consequences have been listed in tables 7 & 8.
From these tables it is obvious that a weight saving of more than 50% is achieved and that
the costs as a consequence thereof are reduced by a factor 2.5.
Also the other piping components have the same type of savings.
18.
12. Miscellaneous products
The fact that Stamicarbon designs a full SafurexÒ Synthesis leads to the request to Sandvik
to deliver product shapes that are not in the delivery program of Sandvik.
For that reason other specialized fabricators were approached to deliver product forms
needed. Sandvik has exclusive supply agreements with these companies. In order to ensure
the quality of these products, Sandvik does market these products and tests these materials
as per the Stamicarbon specifications.
12.1 Forgings
The availability of forgings required to
manufacture in an economical way
products has been guaranteed in that
several forging mills have an agreement
with Sandvik to forge for them the
requested shapes. All however under
strict control and via Sandvik.
Photo 6. Forging
12.2 Plates
Since 1998 plates in SafurexÒ have been produced. These plates are fabricated by
Industeel. The responsibility and quality assurance and Quality Control is in hands of
Sandvik
19.
12.4. HP Pipe flanges
With the use of SafurexÒ the possibility is there to simplify the flange connections in HP
piping. This new design is not only cheaper but makes also the bolting of these flanges
easier and less sensitive for leaks and crevice corrosion.
A joint research programme between Sandvik, LTS and Stamicarbon has led to the
development of a for the urea industry new type flange connection, the TECHLOCK clamp
type connector. This connector is well proven in the oil industry and can be used in the urea
field only if made of SafurexÒ. Photo 9 shows the difference between a conventional flange
connection and a TECHLOCK connector.
The cost for the connectors in a typical 3,250 mtpd tons urea plant is only some 55%
compared with ANSI flanges with Lens ring joints
A 4” pipe connector was installed in the outlet pipe line of the HP carbamate pump of a
Stamicarbon urea plant. After 6 months in service the connector was opened and inspected.
An inspection after dismantling showed the connector as being not used at all. No corrosion
was found at the SafurexÒ mating faces of the flanges and seal ring. The seal ring has been
replaced by a new one and the used seal ring is now with Stamicarbon.
20.
The advantage of this joint is cost savings but of more in importance is the savings on
maintenance costs and the reliability of this joint.
spindle can be made from a normal 22.05 (BE.03) duplex material. The consequence of this
will be that maintenance in the future will be such that only the stem has to be replaced.
21.
13. In plant test results of Safurexâ
Inspections have been performed of Safurex® equipment installed in commercial plants. The
inspections performed, confirm the results of the previously performed laboratory tests; the
corrosion rates are low, comparable and or lower than the rates found when using BC.05
material.
· The Safurex® overlay and liner reveal a perfect corrosion behavior, no sign of any
corrosion was observed.
· The remote field eddy current measurements (RFT) did not show any corrosion in the
tubes; the findings matched those of the base line measurements executed when
building the equipment.
22.
13.3.1. HP Stripper in the UF-2 DSM Urea plant
The DSM stripper was build when Safurex® was still in full development. In spite of the fact
that SafurexÒ was not yet approved, three tubes from the first ever made Safurex® heat were
installed in this Stripper.
In March 1999 after one year of production and in 2001 after some three years of production,
the HP Stripper was inspected. During these inspections each time a Safurex® heat
exchanger tube was removed for further investigations. The tubes were removed after an
Remote Field Eddy Current wall thickness test
The tubes have been extensively examined by both Stamicarbon and Sandvik. The results of
this investigation can be summarized as follows,
Metallurgical examination.
After the Remote Field Eddy Current measurements, the Safurex® heat exchanger tubes
were metallurgical examined. The protruded tube ends showed a smooth surface. The area
influenced by corrosion is identical with the area as found for the BC.05 tubes. (Upper 3
meter of the heat exchanger tube). It was also observed that the overall corrosion proceeds
via the austenite phase. The wall thicknesses as measured by RFT technique were
confirmed.
23.
14. Practical experience with equipment fabricated in Safurexâ
1997
• HP Scrubber: DSM Holland
1998
• HP Carbamate Condenser: El Delta, Egypt
• HP Carbamate Condenser: Police, Poland
1999
• HP Stripper: Agrium, Canada
• HP Carbamate Condenser: Petfurdo, Hungary
2000
• High efficiency reactor trays: Shiraz, Iran
2001
• HP Stripper: Shiraz, Iran
• HP Carbamate Condenser: Razi, Iran
• Siphon Jet reactor trays: SKW, Piesteritz Germany
• HP Carbamate Condenser: El Delta, Egypt
• HP Carbamate Condenser: Dneproazot, Ukraine
2002
• Siphon Jet reactor trays: SKW, Piesteritz Germany
• HP carbamate Condenser ABF, Malaysia
• HP Stripper ABF, Malaysia
• HE-trays: ABF, Malaysia
• Several (control) valves Agrium, Canada
• HP Control valve ABF, Malaysia
• HP pipe lines Agrium, Canada
• HP Stripper Asaluyeh, Iran
• Poolcondenser Asaluyeh, Iran
• Reactor Asaluyeh, Iran
• HP Scrubber Asaluyeh, Iran
2003
• Siphon Jet reactor trays: SKW, Piesteritz Germany
• HP Stripper SAFCO, Saudi Arabia
• Poolcondenser SAFCO, Saudi Arabia
• Reactor SAFCO, Saudi Arabia
• HP Scrubber SAFCO, Saudi Arabia
• HP Piping SAFCO, Saudi Arabia
• Valves & accessoiries SAFCO, Saudi Arabia
• Siphon Jet Reactor trays: ABF, Malaysia
• HP Piping ABF, Malaysia
• HP Piping Reactor- HP Scrubber Agrium, Canada
2004
• Reactor: QAFCO, Qatar
• Siphon Jet reactor trays QAFCO, Qatar
• HP Stripper SAMAD, Saudi Arabia
• PoolReactor NINGXIA, P.R. China
• HP Stripper NINGXIA, P.R. China
24.
15. Safurexâ in oxygen free carbamate solution
The most challenging goal is to produce urea in an oxygen free urea plant by using Safurex®.
Numerous tests conducted under laboratory conditions show indeed that Safurex® remains
passive under oxygen free conditions.
The tests have been conducted with carbamate solutions at Urea reactor conditions
temperature 1830C and up. The results of this test are shown in table 9..
Safurexâ 0.03 5
The behavior of different materials which can be used in the HP Synthesis when using
oxygen to passify and the effect when reducing the oxygen content can be learned from
figure 6. It shows clearly that all known materials so far cannot maintain their passivity and
high (and active or transpassive) corrosion is the result. Only Safurex® shows no reaction
when lowering the oxygen content. The corrosion rate remains constant.
100
BC.01
BC.05
SAF 2205
Safurex®
Corrosion mm/year
10
1
0.0 0.1 0.5 1.0 10.0 100.0
0.1
0.01
PPM Oxygen
25.
16. Safurexâ in oxygen reduced carbamate solutions
The consequence of this large HP Stripper, operating at current (low) capacity would be that
a uniform liquid distribution could not be achieved (turn down ratio). An irregular distribution
would lead to heavy corrosion of the heat exchanger tubes, resulting in serious damage to
the Stripper if BC.05 heat exchanger tubes would be installed.
This Stripper was never installed in the plant were it was designed for.
Presently this Stripper is operating in the Profertil plant in Argentina. In April 2003, it replaced
the Snamprogetti stripper that failed due to heavy corrosion problems which caused the plant
to shut down very frequently.
With the Stamicarbon Safurex® Stripper the plant is now in operation since beginning May
2003. The stripper runs at the desired load to full satisfaction. The stripper bottom
temperature is 204.5 0C and the total oxygen fed as air to the synthesis is 0.45 % of the CO2
feed to the synthesis. This air is partially fed into the bottom of the HP Stripper.
Stamicarbon performed an inspection of this HP Stripper in March 2004. The results are
impressive as can be learned from the inspection results,
26.
Both the channels are lined, no corrosion could be observed.
An impressive behavior of SafurexÒ was found on the liner of the top cover. Although the
lifting trunnion was not removed and thus causing a large cold spot, no condensation
corrosion was found in the liner below, see photo’s 14 & 15.
Photo 14. Top cover with lifting lug Photo 15. Liner surface of top cover
The tubes in the top tube sheet and the tube-to-tubesheet welds are as new, no sign of any
corrosion could be observed in the tube ends in spite of mal distribution and taking into
consideration that a gap was present between the ferrule and the
tube end, see photo’s
'
In the bottom part of this HP Stripper the most severe conditions are present due to the high
temperature, but also here SafurexÒ behaved quite well.
It can be concluded that, in spite of the higher temperatures and the fact that the liquid
distribution in this HP Stripper which was modified to suit Snamprogetti's process is poor, the
SafurexÒ still shows good corrosion resistance and the overall corrosion rate measured is
more or less identical with the corrosion rate measured after one year of operations in the
DSM HP Stripper viz. 0.08-mm per year.
27.
Photo 18. Bottom tubesheet
Photo 19. BC.05 flange face after leak Photo 20. Safurexâ flange face after leak
When opening the leaking flange it appeared however that even though the 316 serrated
gasket was badly corroded, the Safurex® flange faces did not show any corrosion; after some
slight brushing in order to remove the corrosion product originating from the gasket, a new
gasket could be installed and the plant could be started, see figures 19 & 20.
28.
17. Future developments
It is scheduled that in 2004 a new Stamicarbon Pool condenser plant with a capacity of
3,250 mtpd designed with only HP SafurexÒ equipment will go into production.
The equipment has been fabricated without problems. Here the oxygen content can also be
reduced quite significant.
The ultimate test, to run a commercial urea plant without oxygen is near. At this moment, the
fabrication of the components for a urea plant build all in Safurex® is on going.
This 3,250 mtpd urea plant is build for Safco and is planned to go into production in the
year 2005. This will be the first commercial Urea plant that can operate without the supply of
any oxygen.
29.
18. Economical consequences
30.
19. Conclusions
· SafurexÒ is a proven construction material that has kept all the promises we had on our
list. Many references achieved since 1992 show that the corrosion properties are
supreme.
· All parts that need to be fabricated for a SafurexÒ Urea Plant are proven and also proven
is the fact that the equipment is less expensive. Besides this, maintenance becomes
easier and longer operating period between shut downs are possible. The operation of the
Urea plant is easier and one can operate with less care.
· SafurexÒ contributes to Plant safety and reliability. It will at the end result in lower
production costs.
· Even in existing Urea plants the oxygen content can be lowered. The use of SafurexÒ in
non Stamicarbon urea plants confirm this statement.
· Tests in these plants show also that the limits with respect to maximum operating
temperatures are shifted and are higher than with any other material currently used in
commercial operating Urea plants.
· SafurexÒ will keep the urea world moving and more papers about the success of SafurexÒ
will for sure follow but then about the operational achievements.
· The use of SafurexÒ provides significant process and investment advantages described in
other papers published during this symposium.
31.