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    C.m. Schillmoller is a consultant in the United States to The Nickel Development Institute. He provides an overview of the technical requirements and development of specialty furnaces. HP-Modified alloys have almost entirely displaced the formerly accepted HK-40 alloy.

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    C.m. Schillmoller is a consultant in the United States to The Nickel Development Institute. He provides an overview of the technical requirements and development of specialty furnaces. HP-Modified alloys have almost entirely displaced the formerly accepted HK-40 alloy.

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    417 views11 pages

    10058

    Uploaded by

    biswanathsaha77
    C.m. Schillmoller is a consultant in the United States to The Nickel Development Institute. He provides an overview of the technical requirements and development of specialty furnaces. HP-Modified alloys have almost entirely displaced the formerly accepted HK-40 alloy.

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    1 |B) Nc Peas Poet HP-Modified furnace tubes yar rime lates ru mec Cie y by C. M. Schillmoller NiDI Technical Series, N° 10 058 The material presented in this publication has been prepared for the general information of the reader and should not be used or relied on for specific applications without first securing competent advice. ‘The Nickel Development Institute, its members, staff and consultants do not — represent or warrant its ©. M. Schillmotter | suitably for any general or is a consultant specific use and assume no inthe United States tothe | liability or responsibility of Nickel Development Institute any kind in connection with the information herein, HP-Modified furnace tubes for steam reformers and steam crackers C. M. Schillmoller Cast tubulars with high-stress rupture properties offer the highest reliability in steam methane reformers, while for ethylene pyrolysis furnaces high carburization resistance and creep strength optimize performance. It is not unusual for engineers to associate all process furnaces with those routinely encountered in petroleum refin- eries, and to overlook two of the largest applications of specialty furnaces for steam methane reformers and ethylene pyrolysis. These furnaces help supply hydrogen for clean-up of the atmosphere, nitrogen fertilizers for our crops, and raw ‘materials for upgraded fuels and plastics. In today’s high-investment technology, materials that pro- vide efficient and reliable performance, with minimum main- tenance over the lifespan of a furnace, are the correct and desirable selections. Unnecessary shut-downs can no longer be tolerated asthe cost of downtime, loss of profitand possible loss of life far overshadow the initial extra cost of the right alloy in the right place. Cost effective answers are available today ‘An overview is provided of the technical requirements and development of these specialty furnaces and the reasons Why the HP-Modified, HP-Mod, alloys in a period of intense com- petitive development, have almost entirely displaced the formerly accepted HK-40 alloy. ‘The technology has been tested. HP-Mod alloys have had a direct impact on operating margins. ‘Although in the reformer business HP-Mod is generally understood to mean 25Cr/35Ni/INb/0.4C, in the ethylene ‘market it is used to describe a range of HP-Mod alloys, which are basically American Society for Testing and Materials, ASTM, A297 (HP) alloys, witha restricted carbon range and additions of niobium, niobium and tungsten, tungsten, and ‘molybdenum, ‘The following system of alloy designation is therefore used in this paper: HP-40 Mod Nb; HP-40 Mod Nb W; HP-40 Mod W; etcetera. HP-45 reflects the mid-carbon range of certain specifications. Some HP-10 Mod Nb is increasingly used in the ethylene market foritsexcellentbalance of strength and ductility Centrifugally cast tubes: HK-40 versus HP-Mod In the 1960s, when furnace designs using vertical tubing were adopted, a major switch took place from wrought alloys to cast HK-40, 25Cr/20Ni, for reformers and crackers. HK-40, twice as strong as the comparable wrought alloys previously used in horizontal furnaces, became the workhorse ofthe industry and has served well. The industry learned to live with ts limitations in stress rupture properties, temperature gradients, low-cycle fatigue, lack of ductility during shutdown, and limited carburi- zation resistance, ASTM designations A351 and A608 were adopted, as well as a Deutsches Institut fir Normung, DIN, designation — DIN 17006 material number 1.4848 — to tie down the chemical composition and mechanical properties. ‘Two alloy modifications were introduced to HK-40: the addi- tion of 1.5 to 2.0% silicon to improve the carburization resist- ance in cracking furnaces; and the addition of Nb— 24Cr/24Niy 1.5Nb — to improve its strength in reformers. This alloy was developed by Inco Limited in the early 1970s. ‘Also pull-bar boring — the inside-diameter machining of the full length of tubing to remove the internal zone of shrinkage porosity —hasreducedcatalyst voidsand carbon pick-up which ‘would lead to localized overheating, high thermal gradients and longitudinal rupture. Boring of tubes provided forextra catalyst volume with reduced pressure drop and better heat transfer; it 10009 oq 25.61/35 Ni + No HPsos Minimum stress to rupture in 100,000 hours, PSI Minimum stress to rupture in 100,000 hours, Nimm* +009 ee 25Cr20Ni soo K-40 a4 20 1.96 1809 1600 1700 1800 1900 2000 7100 Design tube metal temperature Figure 1 Average stress data plot minimum creep- rupture stress in 100,000 hrs, PS! VS YMT, “CPF. Table | Typical vendors with HP-Mod analysis. c cr Si Mn ND NI Fe (Manaurite 36x) 4 23107 15 15 15 30/85 Balance Fonderies et Aciers max max max de Manoir (SHR -35¢) 45 (28/28 20 20 15. 34/87 Balance Kubota Lid max max (430) 4 25 15 10 15 35 Balance Lake & Eliot max max Paramount Lid (25-35 Nb) 4 25 20 18 15 35 Balance Kobe Stee! max max max (G-4852) 4 25 15 15 15 35 Balance Schmidt & max max max Clemens (Wiscalloy 4 2aie7 15 15 16 8295 Balance 25-35 Nb) max max max Wisconsin Centrifugal (F 25:35 No) 4 2arer 15 15 15 39/96 Balance Kubota Metal Corp. max max max Fahramet Div. KMF (Mo-Re 10) 4 2are7 25 15 15 8387 Balance Duraloy max max max (kT-196) 4 2aer 15 18 18 34/96 Balance Kokomo max max max (Pyrothern 4 25 15 15 15 35 Balance G 25/35 Nb) max max max Pose. Mare (Thermalloy 63) 45 25 15 10 36 Balance ‘BEX max max other: SW was good insurance for longer, trouble-free service in the furnace. Today, most centrifugally cast tubes are being ma- chined to 125 RMS, root mean square. Published values of HK-40's stress-to-rupture have declined over the years with the availability of more long-term estdata, and the American Petroleum Institute, API, Recommended Practice 530 HK-40 data should be used as a design guide. In 1975, Fonderies et Aciers de Manoir, FAM, began mar- keting its proprietary HP-Modified alloy, Manaurite 36X, 25Cr/3SNi/INb/L.SSi. Since then, many othermanufac- turers, Table I, have produced a similar HP-40 Modified alloy. Table II provides the properties for a number of HP-Mod compositions. No two arealike. The APLattempted to prepare single standard creep rupture curve for the HP-40 Mod Nb for inclusion in the API RP530, but was not successful. Figure I shows the average stress curve for HP-40 Mod No that might be used for preliminary design, as well as the API RP530 values for HK-40, Table Il Comparative properties of selected high temperature alloys. Source: McNab, reference 9. ‘Testa iy compar, and at nb sad cen han ses gti an ss tog ‘mon ‘wath Gop ctr Moy tae UF OOF OFF OF ia 02a aka a en Oe Poe ommgsy Acta Dam) 0% amhosu TMT Sm “on mw ea 45h PiPaya a 008 ts am am 182 Fuse 3010 am ages oe at aD ion mt mom 40s ad ad ae ne Nordea HT ™ woe “ods as ow soca im “0 wes 0s 0 OB ox Temas) zm] Wis 05 008 SU AecTamaby N00 TD ses ® 6 0 BS a a ee ee) ‘en ws 0 0 Bs osmosy Ahem Sw] ne ee ) oom 1 OMS evPyiou 450 es ou 0 eB oR Ce 0 7 05 By SN RiPady i SSD] as06 a5 RS as Fim w]e] as06 20 RS Flores tH] mY arag as ua eos est 3885 ee en) 40s ao ua ee ee ee a0 ; SSN am OR OS) wD as 1M? 0308le ine ORSSCW a) Welles th 20 casos 1620 8 TA ei WS 3th mw tos 15 os MD BT oe 2S wos 151 en 55511 oom us ' 8 8 sco a ee ee er a s 6 BO soe maw won 45 45 Be SB ava NORE Se ee ee wom 20 co me aT Ce a en ee ee ee) usas 29 0 me mT 1 ee a ee ee) toon 20 nm MT 1S Day UOAESD 5 mm wom 29 0 ae TSW ty MOREY D8] sm am 20 20 ae BTS wap WORE ama aan tom ts ae aw aave3602 Dusky HONS a) isos <3 <3 RR BR ‘aoa woe m™ 0 (wom a8 4s BO ee SuNV3Bt0 Duay Sz sD a) 6 1 oe sv) Pady HT we om mt osos as 4s BO em sah ea ee wo 6 8 « ay SHR ow me How can the superior properties of the HP-Mod alloys benefit the petrochemical user? For steam reformers the answer is the profitable combination of longer life and higher performance using thinner wall tubes! The higher strength of HP-Mod, compared to HK-40, provides substantially longer stress-to-rupture life. And, HP. ‘Mod permits operation with a thinner metal wall, which gives improvements inthe rate of heat transfer and provides energy savings. Alternatively, in new designs, one can utilize fewer tubes of a larger diameter and save in tubing cost and furnace size, For steam crackers the answer isthe profitable combination of higher efficiency and production rates at higher tempera- tures. The increase in nickel content is particularly important here in stabilizing the austenitic structure and substantially improving the carburization resistance of the alloy, either on its own merits but, as Figure 2 shows, especially in conjunc- tion with silicon.” Aluminum also improves carburization resistance. ‘The higher nickel content improves the cyclic behaviour, the adherence of protective oxide films, and the thermal fatigue properties due to changes in the stability ofthe oxide films and diffusion process ‘Typically these HP-Mod alloys contain between 0.40% and 0.50% carbon, This is an important element, as it forms. chromium carbides which oppose metal deformation at high temperature. Above 1000°C (1830°F) these carbides coa- lesce quickly and therefore decrease the creep rupture strength sharply. Addition of carbide-forming elements such as nio- bium, titanium, tungsten and molybdenum is required 10 28 he pet fe = ae we 2.07 —san a —PESSe LSB ron = ReSNenes an 0300 Nel conten, percent Figure 2 Effect of nickel on the resistance of Cr-Ni alloys to carburization. Caron absorbed, per cent improve the creep strength in the high-temperature range. ‘The HP-Mod alloys can offer the most desirable combinations of high-temperature mechanical- and corrosion-resisting prop- erties for operation in petrochemical furnaces. Even though steam methane reformers and steam cracking furnaces share ‘many fundamental characteristics, and utilize almost identical ‘materials of construction, their process functions differ widely, and this must be taken into account in the design ofthese units and the use of the HP-Mod alloys. Steam methane reformer furnaces In most reformer applications —such as in ammonia, metha- nol and hydrogen production — reliability is an overriding requirement. In most plants, methane is used as feedstock. It reacts with, steam in catalyst-packed tubes at high temperature. The process is highly endothermic. The tubes have inside diam- eters of 60-120mm (2-5 in.) and are 10-14m (33-46 ft.) long. ‘The pressure is 15-30 bar (218-435 psi) and the temperature between 900 to 1000°C (1652-1832°F). Tube wall thickness ranges from 8 to 20mm (31-.79 in.) depending on tube diameter, temperature and pressure. Excess steam is used t0 reduce the formation of carbon. The reforming reactions are favored by high temperature but retarded by high pressure. A typical steam methane reformer for hydrogen and methanol production is shown in Figure 3. ‘When synthesis gas is used in the production of ammonia the conditions are considerably different. Nitrogenis provided by the injection of air into the primary reformer effluent and a secondary reforming step is carried out in a separate catalyst- filled vessel. Because of the balanced load between the two reformers, the temperature in the primary reformer tends tobe lower, 815°C (1500°F) and the pressure between 15-40 bar (218-580 psi). ‘Since the catalyst tube assembly can amount to 25% of the total cost ofthe furnace, there isa great incentive to optimize the design chemically, thermally and mechanically. There are ‘many approaches in satisfying the process and operational requirements. One of the most dramatic improvements in reformer cost has been the increased application of stronger, proprietary tube materials such as HP-Mod alloys. In new reformer design, the HP-Mod alloys have allowed the size of the reformer tube to increase, particularly those de- signed for the high-pressure ammonia process. With the HK: 40 alloy the reformer tube diameter was limited by tube wall thickness. Excessively thick tubes are candidates for acceler- ated creep damage resulting from large temperature differ- fences across the thick tube wall. The use of HP-40 Mod Nb has allowed the internal volume of tubes to grow dramatically, ‘without inerease in tube wall thickness, producing capacity increases of 30% to 40% for the same tube count, with only ‘marginally higher cost. In retrofit or revamp design, the HP-40 Mod Nb allows two possibilities. First, with the outside diameter fixed because of existing inlet and outlet manifolds, make the tubes thinner. This improves the rate of heat transfer and increases catalyst volume and hydrogen production capacity. ‘The second op- tion isto keep the same tube diameter and thickness and raise the design tube metal temperature by 60°C (108°F) Many failures of HK-40 have occurred in risers, manifolds, transfer headers and other components due to stresses from Figure 3 Steam methane reformer, typical for hydrogen prod juction Fuel gas 540-620" (1000-1150°F) 240°C. (1580°F) @wetane ase Combustion air 150°C (@00°F) 1. fan HP steam ——_> 400-510°C (750-950°F) ‘45-100 bar (650-1500 psig) ‘Synthesis gas 345°C (650°F) 17-28 bar (250-350 psig) thermal cycling. These stresses occur chiefly during startup, and shutdown. The HP-Mod alloys can cope substantially better with thermal stresses. Figure 4 shows the effect of wall thickness on the life of HP-40 Mod Nband HK-40. Italso shows the reduction or increase in life resulting from an above or ‘below normal number of thermal cycles and the reduction in life caused by operating 28°C (50°F) above normal operating temperature, Note that for the same wall thickness the relative life of HP-40 Mod Nb is about three times that of HK-40, while if'the alloys are designed for the same strength, only twice the life can be expected. In addition, the good ductility and weldability of HP-40 Mod Nodeserve mention. It has, in the as-cast condition, about 8% elongation. After prolonged service this dropstoabout 4%. If field repairs are required on HP-40 Mod Nb after aging, a solution anneal for about two hours is recommended, which will restore much of the elongation. ‘The requirements of a cost-effective reformer design are ‘maximum reliability, operating stability and high thermal efficiency. The materials sed musthave ahigh creep strength combined with good strain relaxation, good weldability, ex- cellent oxidation resistance and, after aging, good ductility and good weldability. The HP-40 Mod Nb alloys meet most of these requirements Lighter tubing also allows lighter tube supports. Thinner walls result in better heat transfer and inerease the resistance to thermal cycling. Consequently, running and maintenance costs are lowered and service life extended, a HK.40 alloy : Bos! o 0.50 ‘Wall thickness, in. 075 Figure 4 Wall thickness and amount of thermal cycling are important considerations in tube life. Finally, consider the relative cost of HP-40 Mod Nb versus HK- 40, With the thinner wall, the cost per foot of catalyst tubing is ‘comparable, and in some cases even less than HK-40, even though the cost of HP-40 ModNballoy by weightissubstantally higher. Dismissing the use of HP-#0 Mod Nb alloy castings because of their perceived expense could be a costly mistake, Steam cracking furnaces Most cracking furnaces have a configuration similar to that shown in Figure 5. Pyrolysis chemistry is aggressive and dictates not only the reactor design, but also its operating philosophy and the design ofits quench systems. ‘Thermal cracking is a noncatalytic process carried out above 1100°C (2012°F) and a few bar pressure. The destruction of saturated hydrocarbons results in unsaturated lightweight molecules of ethylene and propylene. The feedstock type controls the yield of primary products and byproducts. The cracking severity controls feedstock conversion. Selectivity is extremely im- portant and is maximized by short residence time, There has been a continued evolution of designs to produce the optimum. furnace. Unlike reforming, pyrolysis does not employ huge amounts of process steam, and therefore produces coke which accumulates in the reactor and must be removed in an off-line operation, Between five and 15 furnaces are required 10 maintain uniform plant production rates, so that one or more furnacescan be off-line for decoking. The number of furnaces

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