Technological Challenges in Manufacturing of Heavy Reactors using new generation 2.25Cr-1Mo-0.

25V steel
Pallav Chattopadhyay Larsen & Toubro Limited Hazira Manufacturing Complex; Surat Abstract:
In oil refineries, conventional 2.25Cr-1Mo steel was the standard material being used for high temperature hydrogen application in Hydroprocessing reactors. The possibility of using synthetic fuel processes led to increase in design temperature and hydrogen pressure. To meet stringent design requirements at such a high temperature of 482C, a new generation V modified Cr-Mo steel known as 2.25Cr-1Mo-0.25V steel was developed in early 90s. This new material has got distinct advantages over conventional 2.25Cr-1Mo steel in terms of: Higher tensile strength at room & design temperature thereby allowing higher allowable stress, which results in to thinner wall thickness & lighter weight of the reactor Better elevated temperature properties, Better hydrogen embrittlement and hydrogen attack resistance Better hydrogen disbonding resistance of SS 347 weld overlay on this material Better Temper Embrittlement resistance. Though the weldability of this material is comparable to other Cr-Mo & Cr-Mo-V materials, it is extremely sensitive to welding parameters / heat input, preheat and interpass temperatures, Dehydrogenation Treatment / Intermediate Stress Relieving, Final Post Weld Heat Treatment.. Manufacturing of the first commercial reactor using this material was started in Europe in late 90s. Only a few fabricators in Europe & Japan were having the technical know-how of welding and fabrication of this material. Larsen & Toubro Limited was the first Indian company to start working on this material. An extensive development program was taken up at L&T in late 90s and the first Cr-Mo-V reactor was delivered in 2001. Subsequently 10 more heavy reactors/ converters were manufactured at L&T. Presently, L&T is in the process of manufacturing more than 38 reactors most of which are ~300mmm thick and weigh between 500-1500MT. This paper deals in details about the material properties of 2.25Cr-1Mo-0.25V steel, its comparison with other materials, criticality involved in fabrication & welding of this material.

1.0

INTRODUCTION

Hydroprocessing reactors for refineries are constructed of Cr-Mo / Cr-Mo-V base material with inside cladding / weld overlay of SS321 / 347. The base material being used normally was conventional 2.25Cr-1Mo steel till early 80s. The possibility of using synthetic fuel processes led to increase in operating temperature & pressure, which will call for bigger and heavier reactors if made of conventional 2.25Cr-1Mo steel. Bigger and heavier reactors will be more expensive and difficult to handle. Development of 3Cr-1Mo-V-Ti-B and 3Cr-1Mo-V-Cb-Ca materials in mid 80s could solve the problem to some extent by reducing the design thickness and reactor weight, but ASME restricts use of these materials up to a maximum design temperature of 454C. In early 90s, a new generation

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material 2.25Cr-1Mo-0.25V steel was developed which could solve the dual problem of reducing the design wall thickness as well as application at high temperature i.e. up to 482C. After carrying out several trials / mock-ups, the first commercial reactor fabrication using this material started in late 90s. So far, only a handful number of fabricators in the world are having experience and technical know-how of fabrication using 2.25Cr-1Mo-0.25V material. Larsen & Toubro Limited - Hazira works started working on this material in Dec. 1999. A special developmental program was taken up to carry out mandatory qualification work, welding & testing of special mock-ups and finally fabrication of a reactor using this material. 2.0 2.25Cr-1Mo-0.25V Material & its Weldability

New generation 2.25Cr-1Mo-0.25V steel has got various advantages over other conventional Cr-Mo materials (e.g. 2.25Cr-1Mo, Enhanced 2.25Cr-1Mo & 3Cr-1Mo steel) and Cr-Mo-V materials (e.g. 3Cr-1Mo-V-Ti-B & 3Cr-1Mo-V-Cb-Ca) as shown in Table-1. The table shows that 2.25Cr-1Mo-0.25V material has the following advantages: Higher tensile strength at room temperature and design temperature thereby reducing the required design wall thickness for any specific design application; Maximum allowable design pressure as per ASME Sec VIII, Div.2; Maximum allowable H2 partial pressure & temperature as per Nelson curve; In addition to the above, this material offers better elevated temperature properties and superior resistance to Temper embrittlement at service temperature range H2 embrittlement, H2 attack at high temperature and H2 disbonding in the fusion zone for SS weld overlay on it as discussed below. The requirements of base material, weld metal and design data for 2.25Cr-1Mo-0.25V steel first appeared as ASME Code case: 2098 in 1991. The material was incorporated in ASME Sec II Part-A in Edition 1998 as SA336 F22V forging, SA542 Type-D Class 4a plate etc. This material was assigned P-number 5C in ASME Sec IX- 1998 Edition, Addenda 1999. In the same Addenda 1999 of 1998 edition, the design and welding requirements have been incorporated as mandatory additional requirements in ASME Sec VIII, Div-1 Appendix-31 and ASME Sec VIII, Div.2 Appendix-26. Welding consumables are included with G classification in ASME Sec II Part-C. 2.1 Chemical Analysis & Mechanical Properties : Typical mechanical properties of 2.25Cr-1Mo-0.25V base material and weld metal are summarised in Table-2. Over and above ASME requirements, tramp elements are restricted to a very low level for this base metal and weld metal to improve the resistance to Temper Embrittlement phenomenon. Most of the process licensor specifications restrict the upper limit of elements like P, Sn, As, Sb, Mn & Si through following requirements: : 100 max For Base material: J-factor: (P+Sn) X (Mn+Si) X 104 For Base material & Weld metal: X- factor: (10P+5Sb+4Sn+As) /100 ppm: 15max. ASME code calls for Tensile testing of each heat of base material, each batch of welding consumables and welding procedures after minimum
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predicted Post Weld Heat Treatment (PWHT) as well as maximum predicted PWHT. Impact testing is required at (-)30deg C after both this PWHT condition and the required values are 54J average of three specimens with a single minimum value of 48J. To meet these stringent requirements, PWHT soaking temperature and soaking time need to be selected judiciously by the fabricators based on the inputs from steel manufacturers, welding consumable suppliers and their own trials, experiments & developments . Tempering of the base material and weld metal shall be such that it is able to meet impact properties as well as tensile properties after two extreme heat treatment conditions (i.e. minimum & maximum PWHT). Inadequate tempering of various forms of Vanadium Carbides will lead to poor impact properties. 2.25Cr-1Mo-0.25V steel has got excellent Elevated temperature properties (high temperature and creep rupture strength). When the design temperature is more than 875F, ASME Sec VIII Div.2 calls for high temperature Stress Rupture testing of all batches of welding consumables used in Category A welds (both all weld metal and transverse to weld metal specimens) at 1000F & 30ksi stress. The time to failure shall be at least 900 hrs. 2.2 Temper Embrittlement Resistance Temper embrittlement is a phenomenon in which an alloy becomes brittle at room temperature or lower temperature while exposed to the embrittlement temperature range of 370~565C during service for a longer duration. This is reflected in the increase of ductile brittle transition temperature (DBTT). All Cr-Mo & Cr-Mo-V materials having Cr in excess of 2% are susceptible to this degradation phenomenon while in actual service for a longer period. This phenomenon occurs only in the presence of tramp elements like P, Sn, As & Sb, which segregate in the prior austenite grain boundaries resulting in to grain boundary embrittlement. Susceptibility to temper embrittlement can be reduced in two ways: By using base metal & weld metal with controlled chemistry. The amount of tramp elements P, Sn, As & Sb to be kept in the minimum. This is ensured by putting restriction on maximum allowed limits of J factor & X-factor as described above. By restricting shift in DBTT (for 54J impact energy) after subjecting the material to a special heat treatment known as Step Cooling treatment (Refer Fig.1 for details of Step cooling treatment). In this technique, S curve is generated for heat-treated (minimum and maximum predicted PWHT) base material, weld metal and HAZ by plotting Average Impact Energy against various test temperatures for at least six temperatures (Refer Fig.2). DBTT for 54J impact energy is determined from this curve as TT54. Subsequently, all these base material, HAZ and weld metal are subjected to 11 days long step cooling heat treatment cycle. Another S curve is generated in similar fashion for Impact energy versus Temperature and superimposed on the first curve. DBTT for 54J impact energy is determined after step cooling as TT54sc. The shift in DBTT for 54J impact energy is calculated as TT54sc - TT54. The shift in DBTT shall meet the following formula:
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TT54 + 3. (TT54sc - TT54) 0C for Weld, HAZ & Base Material One typical example is shown in Fig.2. This method correlates fairly well with the actual service condition of the reactor and being widely used for this type of application to determine the susceptibility of base material, weld & HAZ to temper embrittlement. 2.3 Hydrogen Attack Resistance & Hydrogen Embrittlement: Since the reactors in H2 service operate under very high H2 partial pressure and H2 concentration, they are extremely susceptible to two types of H2 attack (i) High temperature H2 attack & (ii) Low temperature H2 embrittlement . (i) High Temperature H2 attack : At high operating temperature of reactors, reaction takes place between hydrogen and the carbon of carbides to form Methane (CH4) bubbles. This results in decarburization of the base material and loss of mechanical properties. These methane bubbles also initiate cavity formation. Since 0.25%V present in this material result in to stable carbide formation, both decarburization and increase in methane partial pressure are restricted. Thereby, 2.25Cr-1Mo-0.25V material has got much better resistance to hot hydrogen attack as compared to conventional 2.25Cr1Mo material. (ii) H2 Embrittlement: Low temperature H2 embrittlement can occur in the weldment during fabrication of reactor as well as in actual service during shutdown for this high strength material. During welding, while the molten weld pool solidifies, the diffusivity of hydrogen reduces drastically at low temperature. This leads to entrapment of hydrogen in the weld metal at the sites with high stress raisers and initiation of microcracks. Due to high strength of this material and brittleness at room temperature after solidification, these microcracks can propagate and result in failures. Low temperature DHT (Dehydrogenation Treatment) at 350~400C or ISR (Intermediate Stress Relieving) at 650~690C is necessary immediately after welding before cooling down to room temperature to allow all the hydrogen to escape out of the weld metal thereby reducing chances of hydrogen cracking. 2.25Cr-1Mo-0.25V steel weld metal can get affected by hydrogen attack if proper DHT/ ISR is not performed on the weld joints. H2 embrittlement can also occur during shut down of reactors in operation at a temperature below 150C. Hydrogen diffuses into the base material wall and hydrogen partial pressure builds up thereby accelerating the propagation of any microcrack / fissure, already present inside. Slow cooling rate and proper outgassing reduce any chance of such embrittlement. V-modified steels show better resistance to hydrogen embrittlement as compared to conventional Cr-Mo steels. 2.4 SS Weld Overlay Hydrogen Disbonding Resistance:

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SS weld overlay disbonding can occur at the base metal SS weld overlay interface area having carbide saturated Martensitic zone while under high H2 partial pressure. This can occur when hydrogen concentration builds up in this sensitive area due to faster cooling rate during shut down. Autoclave hydrogen disbonding test is one tool of evaluating hydrogen disbonding resistance by simulating condition which is much more severe than actual shut down condition. All project specifications for hydroprocessing reactors call for weld overlay procedures with satisfactory Autoclave hydrogen disbonding test result for a given hydrogen charging condition. Presence of V in the form of fine Vanadium carbides in 2.25Cr-1Mo-0.25V steel result in trapping of hydrogen, thereby reducing hydrogen diffusivity. This steel shows much improved hydrogen disbonding resistance than conventional Cr-Mo steels due to this reason. 2.5 Fabrication and Weldability of 2.25Cr-1Mo-0.25V steel: Fabrication and welding of 2.25Cr-1Mo-0.25V steel material require special care in the following areas: Cutting & Forming operations Fabricators require to develop various parameters for these operations like Preheating temperature, Rolling temperature, Amount of strain etc. before going for the fabrication of actual job. None of these operations is allowed in cold condition at Room temperature. Welding - The salient features on welding are: Mainly SMAW and SAW consumables are being used. As on today, there are only a few welding consumable manufacturers in the World. Welding requires precise control on preheat temperature, welding parameters (Current, Voltage and Welding speed), heat input, interpass temperature etc. Welding must be followed with either DHT or ISR depending upon the type of joint. Very good result obtained for Narrow gap & Tandem SAW also in terms of Weldability, Mechanical properties & Non destructive tests. However, due to very poor as welded toughness, any lax in maintaining preheat temperature or inadequate Dehydrogenation treatment / ISR would invariably result in massive cracking. Post Weld Heat Treatment (PWHT) PWHT temperature and time are required to be controlled very precisely for this material. Since V bearing steels contain various types of Vanadium carbides, sufficient tempering of weld metal must be done to achieve desired impact properties. Therefore, although ASME requires lesser soaking time, consumable manufacturers recommend minimum 8 to 10hrs of soaking at 695~715C for any thickness of base material. 3.0 Development Work at Larsen & Toubro Limited

Extensive development work was undertaken in the year 1999-2000 to establish fabrication and welding capabilities on 2.25Cr-1Mo-0.25V steel in a number of stages:

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3.1

Consumable Qualification: Before starting welding on the actual base material, consumable testing from various European & Japanese suppliers was taken up first. Welding parameters were established after carrying out exhaustive trials. All chemical and mechanical tests required for the job were performed like Tensile testing at room temperature and high temperature, Impact test, Hardness survey, Temper embrittlement screening test, Chemical analysis etc. These tests were carried out after both minimum and maximum predicted PWHT.

3.2

Procedure Qualification on 230mm thick base material: SAW and SMAW qualifications were taken up for 230mm thick base material, which qualified us up to 305mm thick vessels. The SAW procedure has been successfully completed. These two procedures involved testing of a mammoth 56 Transverse tensile specimens, 25 All weld & Hot tensile specimens, 32 side bend specimens, 1050 impact specimens apart from Chemical analysis and hardness test specimens after subjecting them to minimum and maximum predicted PWHT. Weld consumables were guaranteed for impact testing at -18 degC during late 90s. Lately procedures have been qualified with cleaner & improved version of weld consumable and impact testing is met at -30 deg C.

3.3

Welding of Mock-ups for Nozzle # Shell Joint & Circumferential seam: In addition to welding procedure qualifications as described above for 2.25Cr-1Mo-0.25V base material, mock-ups of 230mm thick joints were carried out for Nozzle # Shell joint and Circumferential seam welding in highly restrained condition to simulate actual job conditions. These mock-ups were subsequently subjected to rigorous non destructive tests like Radiography using LINAC, UT using Normal and angle probes, MPT by wet fluorescent method after 4 days of completion of welding. All these tests showed fully satisfactory result and absence of any crack. Mechanical tests like Transverse tensile, Side bend & Impact tests for Weld & HAZ were carried out by taking specimens from the circumferential seam mock-up after subjecting them to minimum and maximum predicted PWHT. For Nozzle # Shell mock-ups, other than carrying out NDT, macro & micro sections were cut, polished and etched in order to study the micro structure and presence of any micro crack.

3.4

SS Weld Overlay Procedures on 2.25Cr-1Mo-0.25V Steel: Since inside of all the hydroprocessing reactors are covered with either SS347 or other SS weld overlay, procedures for SS weld overlay were also qualified along with base material welding procedure qualification. Procedures were successfully qualified under for SMAW, FCAW & Electro Slag Strip Cladding (Both single & double layer with strip size up to 120mm width) processes in various positions. The tests included Autoclave

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Hydrogen disbonding test under severe hydrogen charging condition apart from Side bend, Chemical analysis, Ferrite check and Hardness survey. 4.0 Fabrication of 2.25Cr-1Mo-0.25V Reactors in India After successful qualification of procedures (SAW & SMAW) and welding of mockups, the first commercial reactor for IOCL- Digboi was started in July 2000 at Larsen & Toubro Limited Hazira Manufacturing Complex. The 150MT reactor was delivered in 2001 symbolizing Indias entry into the era of new generation Cr-Mo-V reactor fabrication. The salient features in the reactor fabrication were: Almost 95% of the total 2.25Cr-1Mo-0.25V base material welding has been carried out by mechanised Narrow Gap SAW process. Indigenously made SAW nozzle welder was used to weld all the nozzles on shell & head. Special shape welding technique was used to carry out rectangular Support ring (Nub) weld build-up. SS309L+SS347 weld overlay was carried out by ESSC, FCAW & SMAW processes. Subsequent to this, in the year 2006, L&T manufactured four multi-wall (4-layered) Ammonia Converters of 169mm thickness for various fertilizer plants in India. These were the first multi-wall vessels made out of Cr-Mo-V material. L&T mastered the technique of shrink-fitting for such a critical material. In the year 2007, L&T manufactured one of the worlds largest (6.3m ID & 900MT weight) Cr-Mo-V reactors for an Indian Refinery. The reactor involved welding of CrMo-V plates up to 176mm thickness and the inside of the reactor was completely weld overlaid by single layer SS347. Between 2007 & 2008, L&T supplied five thick Cr-Mo-V reactors for three Indian refineries. Three of these reactors were made out of forged shells up to 170mm thickness. Remaining two reactors were made out of plates. Since plate rolling for these reactors was made by hot rolling process, the shell cans were subsequently required to be subjected to quality heat treatment i.e. Quenching & Tempering. Know-how was developed for in-house quenching & tempering of Cr-Mo-V shell cans. Total nine shell cans were quenched & tempered successfully. Each charge was accompanied by material test coupons which were subjected to extensive testing after minimum & maximum anticipated PWHT. The tests included Room temperature & Hot tensile tests, Impact tests at (-) 30deg C, Temper Embrittlement resistance impact tests to generate DBTT curves in as supplied as well as after step cooling heat treatment. All the five reactors were internally covered by SS347 weld overlay which was deposited by ESSC process. Presently, L&T is in the process of completing two huge Cr-Mo-V reactors of 1000MT each, which are of 5m ID and 300mm thickness. Manufacturing technology has been successfully developed for welding of such heavy thickness forged shell cans by Narrow Gap SAW and all the nozzles on shell cans as well as heads are being welded by automatic SAW nozzle welding machine. Critical controlling parameters have been established for cutting, welding as well as heat treatments i.e. Intermediate Stress Relieving & PWHT. As on date, L&T is going to manufacture 38 more heavy thickness reactors in the coming two years - most of which are ~300mm thick and weighing between 500Page 7 of 10

1500MT. So far, L&T is the only qualified heavy fabricator in India to manufacture reactors / converters using Cr-Mo-V material. 5.0 Conclusion New generation 2.25Cr-1Mo-0.25V material is the most attractive material at present to designers for construction of hydroprocessing reactors due to its distinct advantages over other Cr-Mo & Cr-Mo-V materials in terms of reactor size & weight and other superior mechanical properties. Stringent control is required for all fabrication operations on this material. This includes cutting, forming, welding and heat treatment. As welded strength is very high (>1000MPa) and as welded toughness is equally poor (Less than 10J at room temperature), thereby making the weld highly sensitive to various modes of weld cracking if necessary care is not taken. Welding and Fabrication technique for new generation 2.25Cr-1Mo-0.25V materials have been successfully developed at Larsen & Toubro Limited. L&T is the first & only Indian company who is among the top league of heavy fabricators worldwide engaged in Cr-Mo-V fabrication.

[Acknowledgement: I wish to thank the L&T management & all the employees of L&T, who have contributed in various ways during execution of these development works and manufacturing of these reactors.] TABLE-1: COMPARISON OF HYDROPROCESSING REACTOR MATERIALS
Conventional 2.25Cr-1Mo
SA336 F22 SA387 Gr22Cl2 ASME Sec VIII Div.2 Max Allowable Temp (Deg.C) Room Temp. UTS (Mpa) Room Temp. YS (Mpa) Design Stress Intensity as per ASME Sec VIII Div.2 (Mpa) Nelson Curve for Max Temp in H2 Service 482 517-689 310 Min 159 @ 454C 117 @ 482C
454C- ppH2>=11.7MPa

Alloy Types
ASME Material Specifications

Enhanced 2.25Cr-1Mo
SA541 Cl22b SA542 Tp-B Cl2 454 585-760 379 Min 164 @ 454C NA @ 482C
454CppH2>=11.7MPa 482C ppH2>=13.8MPa

2.25Cr-1Mo0.25V
SA336 F22V SA542 Tp-D Cl4a 482 585-760 414 Min 169 @ 454C 163 @ 482C

3Cr-1Mo0.25V-Ti-B
SA336 F3V SA542 Tp-C Cl4a 454 585-760 414 Min 164 @ 454C NA @ 482C

3Cr-1Mo-VCb-Ca
SA336 F3V SA542 Tp-C Cl4a 454 585-760 414 Min 164 @ 454C NA @ 482C

510C- ppH2>=12.4MPa 454C- ppH2>=12.4MPa 454C- ppH2>=12.4MPa

482C ppH2>=13.8MPa

338mm @ 454C Typical Vessel Thickness as per ASME Sec VIII, Div-2 for a 1000MT Reactor 442mm @ 482C

307mm @ 454C NA @ 482C

298mm @ 454C 310mm @ 482C

307mm @ 454C NA @ 482C

307mm @ 454C NA @ 482C

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Table-2:

Mechanical Properties of 2.25Cr-1Mo-0.25V Material : 85~110 ksi (585~760 Mpa) : 60 ksi (415 Mpa) minimum : 18% minimum : 40ft-lb (54J) Average with 35ft-lb (48J) Single minimum at (-) 30C

Tensile Strength (UTS) Yield Strength (YS) Elongation in 50mm Impact Energy

** UTS, YS, %Elongation & Impact toughness shall be met after minimum & maximum predicted PWHT

Figure-1:

Step Cooling Heat Treatment Cycle

593C

538C

524C 496C 468C 315C air/ furnace cooling

50 C 1hr (1) 15hr (1) 24hr (1) 60 hr (2) 100 hr (3)

Srl No. (1) (2) (3)

Cooling Rate (C/hr) max. 5.6 2.8 27.5

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Figure-2:

Ductile- Brittle Transition Temperature (DBTT) Curve

TEMPER EMBRITTLEMENT TEST

300 270 240 210 180 150 120 90 60 30 0 -50

ABSORBED ENERGY (J)

TT54= -27C

TT54sc= -22 C

54J -40 -30 -20 -10 0 TEMPERATURE(C) 10 20 30 40

TT54+3(TT54sc-TT54) = [(-)27 + 3(-22+27)] = (-)12C

MIN.PWHT AVG.TW1 MIN.PWHT+ SC AVG.TW2

Figure-3: 900MT reactor made of 2.25Cr-1Mo-0.25V material dispatched to Essar refinery, Gujarat (India) in 2007

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