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Residual Life Assessment of Refinery CRU Ammonia Reformer Tubes Creep High Temperature Corrosion PDF
Residual Life Assessment of Refinery CRU Ammonia Reformer Tubes Creep High Temperature Corrosion PDF
,India
Bashisth SINGH
Proprietor / Engg. Consultant [QA/QC]:
M/s Premier Inspection & Certification Bureau
Navi-Mumbai 400614,Maharashtra ,INDIA
Emai: picbmumbai@gmail.com
M] 9892598235/ 7506242436
Abstract
Reformer Tubes are Pressure vessels in tubular form, which are subjected to stringent operating
conditions namely high pressures [17 to 21 Kg/cm2g ] & high temperatures [8800C to 9800C ].
These conditions demand use of special materials to withstand high temperatures and pressures.
The operation is kept ceaseless for prolonged period to achieve maximum rate of reaction
between the reactants in presence of catalyst for synthesis of NH3 & Reforming of Hydrogen.
This paper discusses about Creep strain as primary cause of Reformer Tube failure amongst all
other causes. Under this case of investigation, same set Reformer Tubes were examined and
tested annually for seven years in continuation. The results have been presented in this paper.
The Reformer Tubes materials put up in service were HK- 40 [25 nos.] & HP Modified [05 nos.]
out of total 30 Tubes. The observations were made in respect of its physical condition, OD
measurements [as representative of Circumferential Creep Strain], Bowing of Tubes (as
representative of Axial Creep Strain), Ultrasonic Flaw detection using Through Transmission
Technique [Degree of Energy Attenuation for detection & assessment of internal defects]. The
use of HP-Modified material found to increase the Mean Reformer Life owing to its favorable
metallurgical properties.
The data obtained showed that circumferential creep strain in Reformer Tubes on account of
Hoop Stress goes on increasing at much faster pace & led to creation of internal voids as
represented by complete loss of Ultrasonic incident energy. The Circumferential Creep strain
has been assessed to be more harmful with respect to the Axial Creep Strain.
Key Words: Reformer Tubes, Creep Strain, Through Transmission Technique, Energy Attenuation, Mean Reformer
Life.
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1.0 INTRODUCTION
Reformer tubes are Pressure vessels having large L/D ratio, arranged in large numbers in rows &
columns in furnace .These tubes are subjected to severe operating conditions namely high
pressures [17 to 21 Bars] & temperatures [8800C to 9800C ]. These conditions demand use of
special materials to be able to withstand stringent conditions for reforming reaction to take place.
In addition to this, the operation is required to be ceaseless for months together to achieve
maximum rate of reaction between the reactants in presence of catalyst for synthesis of
Ammonia and reforming of Hydrogen to result higher yield of desired product. The reformer
tubes are high Cr, high Ni, Fe alloys and are centrifugally cast to yield preferred metallurgical
structure to meet demanding material properties. The continued reaction of reforming under high
pressures & high temperatures make reformer tubes prone to failures after certain interval of
time.
The tubes were examined and tested in respect of its physical condition, tube OD increments (as
representative of Circumferential Creep Strain), bowing measurements (as representative of
Longitudinal Creep Strain), Ultrasonic Flaw Detection using Through Transmission Technique
for detection of internal defects like voids, cracks, micro-fissures, Hardness tests in vicinity of
the weld joints & DP examination of weld Joints for detection of cracks in weld metal, HAZ and
parent metal. Inspection and testing of tubes were done year after year in continuation for seven
years during scheduled plant shut downs with no change in operating parameters and conditions.
Reformer unit is set up in Fertilizer and Chemical industries wherever the plant activity requires
production of Hydrogen gas and Ammonia gas. The Reformer tubes are important constituents of
reformer unit. A large number of these tubes are vertically positioned in rows and columns.
Creep failure of Reformer Tubes is one of the major issues being faced in Reformer Unit
operation.
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2.2 TUBES ARE FED WITH HYDRO CARBON & STEAM MIXTURE
The catalyst synthesizes ammonia by chemically combining hydrogen and nitrogen under
pressure. Catalytic reaction of steam & hydro carbon mixture at elevated temperature supplies
Hydrogen for reaction.
Cn Hm + nH2O = nCO + [m/2 + n] H2. ----------------- 1
CO + H2O = CO2 + H2 ---------------- 2
Since the number of moles of product exceeds the number of moles of reactants, this is an
endothermic reaction and requires energy input from external source [by burning natural gas or
naptha] in order to sustain the reaction.
The material HK 40 is being used for years. Now-a-days HP-Modified is being used with 1.5%
Nb due to its improved temperature properties. HP-Modified is being used for reforming
pressure of 40 bars @ tube wall temperatures of 9000C. Commonly used for replacements and
new Plants.
Use of micro alloys Ti & Zr are another improvement. These micro alloys, permits, the use of
low thickness tubes while maintaining the same tube life of 100000 hrs or even more .
By installing the tubes with lesser wall thickness and / or wider diameters the capacity of the
front end of the NH3 plant can be increased significantly.
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The use of micro alloyed reformer tubes with minimum wall thickness can increase the catalyst
volume, increase the firing temperature and lower pressure drop.
The reformer tubes [high Cr, high Ni ,Fe alloys], austenitic in phase and are centrifugally cast to
yield preferred metallurgical structure to meet the demanding material properties though the
chemistry & metallurgy of reformer tube materials are adjusted to make them resistant to creep
strain, resistant to high temperatures and resistant to oxide formation on the external surfaces of
tubes with contaminants in furnace atmosphere, the continued reaction of reforming under
high pressures and temperatures make reformer tubes prone to failures after certain interval of
time.
3.1 TYPE & SIZE OF REFORMER TUBES UNDER OUR RLA STUDY
The tube materials : HK-40 (25 nos.) & HP-Modified (05 nos.). Total 30 Tubes.
Tube dimensions : 10000 mm (L)x O/D 202 mm x Wall thickness 11 mm, I/D 182 mm .
The Reformer Tubes are centrifugally cast to obtain favorable metallurgical structure, to
enhance temperature resistance, Creep resistance at high temperature & High resistance to
deformation.
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3.2 REFORMER TUBE SET UP
The reformer tubes are positioned vertically. The topside of tubes is welded with reducers &
flanges, connected with inlet lines. The bottom side is connected with Header and Pig tails, out
let lines for the product.
Fig. 3 : Schematic Diagram of Reformer Tube representing inlet /out let lines & Catalyst inside
The total number of hours of reformer unit operation is limited to 7200 hours per year. With this
level of operation, Reformer Life achieved is approx 14 years using normal grade reformer tube
material (HK-40). In some cases saving is done through proper maintenance work and sound
engineering practices and able to save an additional 15 days in a year out against total down time
of 65 days of per year. This in turn, results in increase in efficiency of 210 days working days in
14 years of service, this may be considered equivalent to a year. Taking all these operational
factors into account the reformer tube is assumed to have maximum life span of 15 years with
best possible up keep of reformer unit. Through use of modified grade material, the mean life of
reformer unit achievable is up to 18 years or more which results in to gain of 20 % against
normal grade material.
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[with improved maintenance, reducing down period time ]
v) Average running hours for reformer unit : 7380 hrs. per year
vi) Maximum reformer run hours /year under
best possible conditions of reformer operation : 7500 hours/year
vii) Minimum reformer run hours/year [taking in to
account various hurdles & MNT problems] : 7000 hours/year
Note: For all calculations & evaluation of residual life of reformer tubes, run of approximate
7200 hours/year is taken into account.
4.1.2 By reducing operating temperature and pressure of reformer tubes and ensuring that the
temperature distribution is uniform throughout the furnace. The temperature gradient must
be kept between 500C.
4.1.3 Carrying out periodic checks of reformer unit components inclusive of tubes, headers,
firing nozzles, maintaining proper refractory bricks condition of furnace, appearance of hot
spots, avoiding temperature shoot outs during operation.
4.2.2 Efficiency can also be increased by operating reformer unit at higher temperature &
higher internal pressure. It is observed that reformer tubes have been designed to operate at
pressure of 30 to 35 bars and temperature of 9200C to 9800C. However, the risk of failures
increases under these limiting conditions.
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6.0 DEFECTS ENCOUNTERED AND THEIR CAUSES
6.1. BOWING IN REFORMER TUBES, CAUSES & REMEDIES
The reformer tubes remain in almost straight condition up to 55000 hrs to 60000 hrs of running
(8 years+). After 8 years of service aging in tubes starts & bowing in tubes gets visual. The top
and bottom ends of reformer tubes are connected to other components in reformer unit and they
are rigid bodies. On these counts, the tubes experience constraints in regards to their axial
expansion. The longitudinal creep strain sets in reformer tubes in form of axial creep strain.
Since the two ends are almost rigidly fixed, the tubes have no room left to take care of
increments in length in axial direction, thereby giving way for deformation of tubes in horizontal
direction rather than vertical. The pattern of bowing in tubes is non uniform and takes place in
random directions at any level and to any degree. Bowing in reformer tubes found to occur as
much as up to 125 to 150 mm.
Fig-3 Reformer Tubes Original condition Fig: 4 Reformer Tubes condition @ 110000 hrs
Creep failure in reformer tubes is the primary cause among all failures. Basically two types of
creep occur in reformer tubes. Creep failures are characterized by: increments in OD, by
appearance of Bulging /Hot-Spots/Blisters, thick-edged fractures often with very little ductility
and longitudinal "stress cracks" in tubes either on ID or OD, oxide scales on external/internal,
surfaces and mid wall cracking in tubes.
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7.2.1 LONGITUDINAL CREEP IN TUBES
The high temperature causes axial stress in body of tube leading to longitudinal creep, which gets
reflected in form of bowing of tubes, once top & bottom ends of tubes get restricted. In physical
form, this longitudinal creep in tubes is reflected in form of Bowing of Tubes after prolonged
working hours. This creep also leads to longitudinal stress cracks.
7.2.2 CIRCUMFERENTIAL CREEP IN TUBES
High pressures in tube create Hoop Stress, there by developing circumferential creep. This creep
results in form of increased OD of reformer rubes after large number of working hours. The
visible change in diameter of tubes is noticed only after 10 years of reformer operation. High
temperatures and high pressures in reformer rubes generate huge internal stresses, one in form of
longitudinal stress and the other in form of circumferential stress, this results is in form of
Longitudinal Creep strain & Circumferential creep strain. These two types of strains are the
main causes for reducing the life of reformer tubes. The longitudinal creep strain is acceptable to
a great extent so far as direct damage to reformer tubes is concerned. However the
circumferential creep strain is not acceptable due to the fact that increase in diameter of tubes
results in creation of internal voids in the tube material, particularly in the mid wall region. In
this case the term true OD has been used for evaluation purposes. True OD of tube refers to an
imaginary circumferential line diameter of tube mid wall. For assessment of Reformer tube
material degradation, True OD value is taken into consideration because the mid wall tube
material experiences an average temperature and pressure. The mid wall of tube is the true
representative of being exposed to actual temperature and pressure conditions prevailing in the
tubes.
Table No 1 Increments in OD of Reformer Tubes (Creep measurements in terms of Tube Dia)
Reformer Tube mid wall diameter: 193 mm (True OD)
Creep data of tubes from 10th yr up to 16th yr [Original OD of Tubes: 202 mm]
Running Reformer Measured Aveg. Increment % increase % Creep w.r.t Remarks
Year Run hrs OD [ mm] OD in OD in OD mid wall line dia
(% CREEP) True OD of 193 mm
10th Yr 72000 202.15 202.42 0.42 0.848 0.810 From 14th year
202.68 onwards i.e
11th Yr 78500 202.60 202.75 0.75 1.515 1.450 after 95000 hrs
202.90 of run the
growth rate of
12th Yr 86000 202.70 203.05 1.05 2.121 2.026 creep in the
203.40 Reformer
13th Yr 92500 • Complete test could not be performed owing to some process tubes is very
constraints and time limitations fast .This
14th Yr 98000 203.10 203.53 1.53 3.090 2.953 indicates the
203.96 fast aging of
15th Yr 105000 203.82 204.20 2.20 4.444 4.246 reformer tubes
204.58
16th Yr 112000 204..16 204.81 2.81 5.676 5.423
205.46
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7.2.3 CREEP TEST RESULT & SIZING OF INTERNAL DEFECTS
As precise evaluation and sizing of internal defects is not possible in reformer tube materials
owing to its rough surfaces, uneven surface contours, and high degree of energy attenuation
accompanied with simultaneous bowing and existence of ovality in reformer tubes the
estimation of internal defects generated in the tubes are primarily judged on the basis of
circumferential creep strain at its mid wall line diameter (referred to as True OD of Tube) as
direct representation of internal voids. Under the prevailing operating conditions of reformer
tubes, the mid wall region is considered to be the true representative of reformer tubes
metallurgical conditions. The creep test results analyzed in respect of true OD of reformer Tubes
under RLA study. Out of total 30 tubes, 14 tubes exhibited creep exceeding 5% value. An
increase of 5% at mid wall line diameter of 193 mm accounts for 2.81 mm increment which is
equivalent to an increase in circumference length at mid wall location to the order of 8.83 mm.
Assuming that 50% of this increment is consumed for plastic deformation, the remaining 50%
goes for directly creating the voids, cracks/micro cracks to the order of 4.41 mm total cumulative
length of internal defects. This figure can be taken as turning in to void formation. Assuming as
if 4.41 mm incremental length in circumference at mid wall line, if located at random locations at
20 spots along the periphery separately, individual void size is 0.22 mm i.e. 220 microns. The
size of voids / cracks at mid wall location of tube is enough to degrade the reformer tube material
prone to the stage of failure. On the basis of this test result it was suggested to replace all the 14
tubes showing creep exceeding 5%. Almost 50 % of tubes reached the stage of abandonment.
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9.0 ULTRASONIC FLAW DETECTION OF REFORMER TUBES [ UFD
9.1 OBJECTIVE AND TECHNIQUE USED
The actual condition monitoring of reformer tubes is done through Ultrasonic Flaw detection of
tube material using THROUGH TRANSMISSION TECHNIQUE . The damage done due to
high degree of Circumferential Creep Strain is assessed through this technique as it evaluates
the kind of internal damage done in tube material .The loss of ultrasonic energy while passing
through it represents the presence of internal cavities, voids, micro-cracks, porous character &
micro fissures.
Type of scanning : Manual At a time half circumference and vertical movement 1500 mm
The table below indicates the degree of loss of ultrasonic energy while passing through the body
of tube materials .
10th Year 11th year 12th year 14th year 15th year 16th year
Hours of 72000 78500 86000 98000 105000 112000
Service
Energy 40% loss in 50 to 55 % 60 to 65 % 70 to 80 % 80 to 90 % 90to 100% in
loss for 25 % Tube of loss in 40 % loss in 50 % loss in 60 % 60 % of x- 70 % Tube x-
10th year of x-sectional x-sectional x-sectional x-sectional sectional sectional area
Ref. Level. area area area area area
Energy loss Reference 72 to 74 dB 78 - 80 dB 86-90 dB 94- 102 No signal at the
in terms of Scanning dB receiving end
Attenuation dB - 68 All transmitted
energy getting
lost.
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9.4 ANALYSIS OF ULRASONIC FLAW TEST RESULT:
Ultrasonic energy loss [Attenuation of ultrasonic energy] during transit through reformer tube
material is of very high order. Up to 10 years of service, reformer tubes are young. As the time
passes by, the aging rate in tubes enhances at faster rate day by day and year by year. From 12th
year onwards close examination and health monitoring of reformer unit becomes essential. The
heavy loss of energy is indicates that the tube material has developed voids micro- fissures in
the mid wall region and absorbs transmitted ultrasonic energy to a great extent. The pattern of
the energy loss at the receiving end gives signal about the deteriorating condition of tubes in
respect of its soundness. It also indicates that the material is getting porous inside slowly but
certainly. The complete loss of energy shows that the tube material has turned into an unsound
state and needs its replacement.
10.0 CONCLUSIONS
As a result of visual examination, NDT tests and creep measurements of reformer tubes it was
concluded that up to 72000 hours of running, using HK 40 material did not show any visible
defect in regards to its creep & tube bowing .Creep in tubes up to 10 years service limited to the
order of 0.81 % .With subsequent years after 11th year & 12th year creep values found to
increase .Up to 12th year creep was limited to 2.0 % . The results show that at 14th year creep
found to the order of 2.953 % i.e. almost 3.0 % and this value crossed 4.0 % and then 5.0 % at
the end of 15th & 16th year respectively indicating very fast deterioration of reformer tubes in
terms of developing creep strain.
Significant loss of incident energy under ultrasonic testing using through transmission technique
observed, indicating nucleation and formation of internal micro cracks micro- fissures and voids.
The tubes in initial years of operation up to 10 years the attenuation in reformer tubes was at a
normal level as expected for cast materials. However with passage of time and increased years of
operations, particularly after 90000 years of reformer service the energy attenuations found to be
of alarming proportions. At the age of 16 years i.e. 112000 hrs, more that 50 % of reformer tube
cross sectional areas revealed total loss of the incident energy as shown above in the
corresponding table.
The reformer tubes show excessive bowing, these get de-shaped after 14 years of operation.
Tube bowing noted to the order of 125 mm. These are bent so much that they start touching each
other.
To summarize the results in brief, it may be safely concluded that for reformer tube material of
Gr.HK-40, safe run is possible up to 90000 hrs of service. With increased hours of operation in
the subsequent years, extreme caution is required to be exercised for its proper evaluation of
creep strain, tube bowing and ultrasonic tests for attenuation results. Close control of operational
factors and thorough external examination required is to be performed on an annual basis. The
test results of reformer tubes using HK-40 grade material with 112000 hrs [16 years] of
operation revealed that the condition of almost 50% tubes is un- satisfactory and they had to be
abandoned against use in service to avoid failure during operation and causing any mishap.
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10. REFERENCES
1. ASM Metals handbook Vol.11 , failure investigations
2. Experience of repeated NDT Testing , inspection and evaluation of reformer tubes in various
chemical / petrochemical companie.
3. NDT in predicting of processing furnace remaining life, NDT for Safety 2007, Prague, Czech Republic
4. A comprehensive approach to Insp.& Assessment of H2 reformer tubes, API Insp. Subcommittee,
IESCO
5. Integrity and life assessment of catalytic reformer units, John Brear & John Williamson
6. Reformer furnaces: materials, damage mechanisms & assessment by Tito Luiz da Silveira & Iain
Lemay
7. R.Singh “Metallurgy &Weldability of Steam Hydrocarbon reforming equip.,thesis paper TWI-2000
8. S R Keown, FB Pickering ‘Effect of Niobium carbide on the creep rupture properties of Austenitic
steels“ASM Handbook Service conditions in the chemical industry[Materials Park OH,ASM ]
9. B.M. Patchett, R.W. Skwarok, “Welding and Metallurgy of 20Cr-32Ni-Nb and HP 45 Castings,”
Proc. of Conference by the Metallurgical Society of CIM, 1998.
10. A.Chitty, D. Duval, “Creep Rupture Properties of Tubes for High Temperature Steam Power Plants,”
Proc. of Joint International Conference on Creep, The Institute of Mechanical Engineers, London,1963.
11. Evaluation of reformer tube degradation after long term operation. By J Kabanowski Gadarisk Univ.
of Technology Poland
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