HP-MODIFIED

FURNACE TUBES FOR

STEAM REFORMERS
AND STEAM CRACKERS
C.M. SCHILLMOLLER
NO 10058

Distributed by
NICKEL
INSTITUTE
HP-MODIFIED FURNACE TUBES
FOR STEAM REFORMERS
AND STEAM CRACKERS

NO 10058

By C.M. Schillmoller, Mar 1991.

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 Institute, its members, staff, and consultants do not

represent or warrant its suitability for any general or specific use
and assume no liability or responsibility of any kind in connection
with the information herein.
 HP-Modified
furnace tubes
for steam reformers
and steam crackers
C. M. Schi//mo//er

Cast tubulars with high-stress rupture properties offer the An overview is provided of the technical requirements and
highest reliability in steam methane reformers, while for development of these specialty furnaces and the reasons why
ethylene pyrolysis furnaces high carburization resistance and the HP-Modified, HP-Mod, alloys in a period of intense com-
creep strength optimize performance. petitive development, have almost entirely displaced the
It is not unusual for engineers to associate all process formerly accepted HK-40 alloy. The technology has been
furnaces with those routinely encountered in petroleum refin- tested. HP-Mod alloys have had a direct impact on operating
eries, and to overlook two of the largest applications of margins.
specialty furnaces for steam methane reformers and ethylene Although in the reformer business HP-Mod is generally
pyrolysis. These furnaces help supply hydrogen for clean-up understood to mean 25Cr/35N1/1Nb/0.4C, in the ethylene
of the atmosphere, nitrogen fertilizers for our crops, and raw market it is used to describe a range of HP-Mod alloys, which
materials for upgraded fuels and plastics. are basically American Society for Testing and Materials,
In today's high-investment technology, materials that pro- ASTM, A297 (HP) alloys, with a restricted carbon range and
vide efficient and reliable performance, with minimum main- additions of niobium, niobium and tungsten, tungsten, and
tenance over the lifespan of a furnace, are the correct and molybdenum.
desirable selections. Unnecessary shut-downs can no longer The following system of alloy designation is therefore used in
be tolerated as the cost of downtime, loss of profit and possible this paper: HP-40 Mod Nb; HP-40 Mod Nb W; HP-40 Mod W;
loss of life far overshadow the initial extra cost of the right etcetera. HP-45 reflects the mid-carbon range of certain
alloy in the right place. Cost effective answers are available specifications. Some HP-lO Mod Nb is increasingly used in the
today. ethylene marketforits excellentbalance ofstrength and ductility.

1
 Centrifugally cast tubes: HK-40 versus HP-Mod
In the 1960s, when furnace designs using vertical tubing were _ 10 000 "E
Cl) E
adopted, a major switch took place from wrought alloys to cast " Z
HK-40, 25Cr/20Ni, for reformers and crackers. HK-40, twice as CD
^ U)

- 27.2 2^
strong as the comparable wrought alloys previously used in m.
a
-C
5000 -
.E
horizontal furnaces, became the workhorse of the industry and D
C:} D
D C3
has served well. The industry learned to live with its limitations c5 CJ
in stress rupture properties, temperature gradients, low-cycle
fatigue, lack of ductility during shutdown, and limited carburi-
$2
.E
2000 —
25 Cr/35 Ni + Nb
— 13.6 C)
"
:
n
zation resistance. ASTM designations A351 and A608 were 2 HP-Mod 2

adopted, as well as a Deutsches Institut fiir Normung, DIN, :J

g 1000 - - 6.8 g :J
designation — DIN 17006 material number 1.4848 — to tie
down the chemical composition and mechanical properties.
m.
O
~
U) ~
L
O

# 25 Cr/20 Ni #
Two alloy modifications were introduced to HK-40: the addi- E 500 - HK-40 - 3.4 g
tion of 1.5 to 2.0% silicon to improve the carburization resist- E U)
ance in cracking furnaces; and the addition of Nb — 24Cr/24Ni/ Z E

1.5Nb — to improve its strength in reformers. This alloy was

E
C "E:J
E

developed by Inco Limited in the early 1970s. :S 200 I I I I I I I 1.36 E

850 900 950 1000 1050 1100 1150 OC
Also pull-bar boring — the inside-diameter machining of the 1 I I 1 1 1
full length of tubing to remove the internal zone of shrinkage 1500 1600 1700 1800 1900 2000 2100 oF
porosity — has reduced catalystvoids and carbon pick-up which Design tube metal temperature
would lead to localized overheating, high thermal gradients and
longitudinal rupture. Boring of tubes provided for extra catalyst Figure 1 Average stress data plot minimum creep-
volume with reduced pressure drop and better heat transfer; it rupture stress in 100,000 hrs, PSI VS YMT,
°C/°F.
Table I Typical vendors with HP-Mod analysis.

C Cr Si Mn Nb Ni Fe

(Manaurite 36X) .4 23/27 1.5 1.5 1.5 33/35 Balance

Fonderies et Aciers max max max
de Manoir
(KHR - 35C) .45 24/28 2.0 2.0 1.5 34/37 Balance
Kubota Ltd. max max
(H39W) .4 25 1.5 1.0 1.5 35 Balance
Lake & Elliot max max
Paramount Ltd.
(25-35 Nb) .4 25 2.0 1.5 1.5 35 Balance
Kobe Steel max max max
(G-4852) .4 25 1.5 1.5 1.5 35 Balance
Schmidt & max max max
Clemens
(Wiscalloy .4 23/27 1.5 1.5 1.6 32/35 Balance
25-35 Nb) max max max
Wisconsin Centrifugal
(F 25-35 Nb) .4 24/27 1.5 1.5 1.5 33/36 Balance
Kubota Meta! Corp. max max max
Fahramet Div. KMF
(Mo-Re 10) .4 23/27 2.5 1.5 1.5 33/37 Balance
Duraloy max max max
(KT-196) .4 24/27 1.5 1.5 1.5 34/36 Balance
Kokomo max max max
(Pyrotherm .4 25 1.5 1.5 1.5 35 Balance
G 25/35 Nb) max max max
Pose. Marre
(Thermalloy 63W) .45 25 1.5 1.0 36 Balance
ABEX max max other: 5\N

2
was good insurance for longer, trouble-free service in the 36X, 25Cr/35Ni/1Nb/1.5Si. Since then, many other manufac-
furnace. Today, most centrifugally cast tubes are being ma- turers, Table I, have produced a similar HP-40 Modified alloy.
chined to 125 RMS, root mean square. Table /1 provides the properties for a number of HP-Mod
Published values of HK-40'S stress-to-rupture have declined compositions. No two are alike. The APl attempted to prepare
over the years with the availability of more long-term test data, a single standard creep rupture curve for the HP-40 Mod Nb for
and the American Petroleum Institute, API, Recommended inclusion in the API RP530, but was not successful. Figure 1
Practice 530 HK-40 data should be used as a design guide. shows the average stress curve for HP-40 Mod Nb that might be
In 1975, Fonderies et Aciers dc Manoir, FAM, began mar- used for preliminary design, as well as the API RP530 values
keting its proprietary HP-Modified alloy, Manaurite for HK-40.

Table II Comparative properties of selected high temperature alloys. Source McNab, reference 9.

These data are strictly comparative, and not to be used for desi¢l11 Mean sttess to tupt, in Mean stress to tupt, in
100,000 h 10,000h
Group C Si hhn Ci Ni Nb 0thei Alloy 16007 1800°F 20007 16007 18007 2000°F

HK-40 0,2-0,6 <2,0 <2,0 24-28 18-22 Abex Thenal!oy 47 2700 1200 450 4200 1900 830
0,3Ti,0,5W Abex Thenax 47 3831
i: 11 11 I! i:

. 1479 440 5500 2600 1000

0,1Ti,0,5W Abex TMA 4700
11 11 I! 11 I!
0,25 4925 2183 546 6700 3200 1200
0,4 1,3 1,0 25 20 . <0,5 Mo APV Paralloy H20 25E2 877 232 4379 1595 400
0,35-0,45 <1,5 <1,75 23-27 19-22 FAN khanaurite 20 3100 1250 - 4600 2250 870
0.39-0.41 0,98 1,05 25,4 20,0 Kubota HK 40 2600 950 - 4260 1800 670
0,4-0,45 <1,0 <1,0 23-25 21-23 . Kobelco Mod HK 2701 1137 - 4120 1849 782
0,4 <1,5 <1,5 25 20 - S&C G4848 2830 1170 - 4060 1950

HP-45& 0,45 1,0 0,5 25 35 . Abex Thenalloy 63 2700 1500 580 3900 2250 900
HP-hhod C,45 1,0 0,5 25 36 SW Abex Thenalloy 63W 4000 1750 - 5820 2650
0,50 1,6 0,7 26 35 - SW, 15Co Ahex Supedhen 5200 2800 970 7400 4000 1550
(63WC)
0,45 1,0 0,5 26 36 - 0,3Ti,0,5W Abex Thenax 63 4610 2105 624 6300 3200 1400
!1 11 i:
:i 11
0,25 0,1Ti,0,5W Abex TMA 6300 5500 2730 675 7300 3900 1500
0,4 0,75-2,0 1,0 25 35 0,7-1.5 AN Para!loy H39W 4490 1895 - 6500 2586
0.1 1,3 1.0 25 35 1,2 APV Paralloy CR39W 3200 1075 280 4300 1750 520
0.5 1,7 0,5 25 35|tCo) SW APV Paralloy H34Ct 3300 1225 375 5050 2480 770
0,35-0,45 <1,5 <1,5 23-27 32-35 <1,5 FAM Manaurlte 36X 4300 1750 460 620C 4500 2900
0,35-0.45 <2,0 <2,0 24-27 32-35 1-2 1-2W FAN hhanaurite 36XS 4200 1450 420 6000 4500 2500
0,37-0,47 <1,5 <1,5 24-28 34-37 . Kubota KHR-35H 3128 1166 - 4550 2100 670
0,4-0,5 <2,0 <0,5 24-28 34-37 0,6-1.5 Kubota KHR-35C 4806 2000 640 6542 3128 1100
I! ft 11 11 !1
" 3,5-4,5W Kubota KHR-35W 4400 1850 500 5200 2400 824
:J i: : : :i " 0,5-1,5W
I! fl i: 11 11
1,1-1,7 0,3-0,8Mo Kubota KHR-35CW 4123 1500 426 5545 2560 780
WthhotNbts3.0
0,45-0,55 1,6-2,0 <1,5 23-27 34-37 Kohelco HiSl HP 3128 1137 - 4692 2130 853
0.45-0,55 <1,5 <1.5 24-29 36-37 Kobelco HIS) HP 3200 890 - 4612 2275
0,4-0.5 <1,5 1-2 24-26 34-36 |-1,5 Kobleco 25-35 Nb 3555 1136 - 4977 2417 853
C,4 1,5 1,5 25 35 S&C G4857 2900 1200 360 4350 2100 800
0,4 1,5 1,5 25 35 1,5 S&C G4852 4400 1950 510 6090 3210 750
0,40-0.50 <1.5 <1,25 25-28 35-38 1,6W Dura)oy MO-RE-I - 1500 550 6000 2800 1100
0,40-0,50 <2,0 <2,0 24-28 33-37 1,0Mo Duraloy MO-RE-B 3400 1150 500 5200 2210
0,35-0,45 <2,0 <2,0 24-28 33-37 1,0 Duraloy MO-RE-ID 4742 1840 550 5250 2300 900
0,40-0,50 <2,0 <2,0 24-28 33-37 1,5 1,5W Duraloy MO-RE-30 - 1860 575 - 2700 1075
0.40-0.50 <2,0 <2,0 24-28 33-37 1,5 3,5W Duraloy MO-RE-31 5500 1940 610 - 3000 1280
0,10kh <2,0 <2,0 24-28 33-37 1,5 Duraloy MO-RE-21 3100 900 260 4300 1650 380

28'48W
0,25-0,50 <1,5 <1.25 24-27 44-47 - 3,6W,3,6MO,3,6CO Duraloy HOM-3 - - - 2500 940
0,15-0,25 < ,3 < ,3 32-34 48-52 16,0W Dura)oy MO-RE-2 · - - 2700 1310
0,40-0.60 <1.75 <1,5 26-30 46-50 - 5.0W,3,6CO Duraloy S-22H 5100 2400 - - 2900 1200
0,5 1,5 0,8 28 48 - SW APV Pardloy H48T 1235 375 - 2260 780
0,45-0,55 <1,5 <1,5 26-30 46-50 4-6W Kohelco HV 4550 1635 398 7110 2700 995
0,45 1,5 1,5 28 48 5W S&C G4879 1834 550 - 2780 1160

3
 How can the superior properties of the HP-Mod alloys
benefit the petrochemical user?
For steam reformers the answer is the profitable combination 2.8
of longer life and higher performance using thinner wall 1E/8 Ni3ke|
E 2.4
tubes! The higher strength of HP-Mod, compared to HK-40, (D
·18/12 Mo /
provides substantially longer stress-to-rupture life. And, HP- O Nickel + 1%Si
03 2.0 /
Mod permits operation with a thinner metal wall, which gives CL
20/10 20/1E
Nickel + 2%Si
improvements in the rate of heat transfer and provides energy ^ 25/20
E 1.6
savings. .Q
C
18/8Si
25/20
Alternatively, in new designs, one can utilize fewer tubes of O
D" 1.2 I 15/35
30/2bsi~ < 20/32
a larger diameter and save in tubing cost and furnace size. aj
For steam crackers the answer is the profitable combination S 0.8 25/35
of higher efficiency and production rates at higher tempera- 30/30Si ,
tures. The increase in nickel content is particularly important a
O 0.4 Carborized at 50/50a
" 1000°C/1832"F for 200 hours
here in stabilizing the austenitic structure and substantially in Carbon Granulate
improving the carburization resistance of the alloy, either on I 1
0
its own merits but, as Figure 2 shows, especially in conjunc- 0 2010 30 40 50
tion with silicon. Aluminum also improves carburization Nickel content, per cent
resistance. Figure 2 Effect of nickel on the resistance of Cr-Ni
The higher nickel content improves the cyclic behaviour, alloys to carburization.
the adherence of protective oxide films, and the thermal
fatigue properties due to changes in the stability of the oxide improve the creep strength in the high-temperature range.
films and diffusion process. The HP-Mod alloys can offer the most desirable combinations
Typically these HP-Mod alloys contain between 0.40% and of high-temperature mechanical- and corrosion-resisting prop-
0.50% carbon. This is an important element, as it forms erties for operation in petrochemical furnaces. Even though
chromium carbides which oppose metal deformation at high steam methane reformers and steam cracking furnaces share
temperature. Above 1000°C (1830°F) these carbides coa- many fundamental characteristics, and utilize almost identical
lesce quickly and therefore decrease the creep rupture strength materials of construction, their process functions differ widely,
sharply. Addition of carbide-forming elements such as nio- and this must be taken into account in the design of these units
bium, titanium, tungsten and molybdenum is required to and the use of the HP-Mod alloys.

Steam methane reformer furnaces

In most reformer applications — such as in ammonia, metha- the design chemically, thermally and mechanically. There are
nol and hydrogen production — reliability is an overriding many approaches in satisfying the process and operational
requirement. requirements. One of the most dramatic improvements in
In most plants, methane is used as feedstock. It reacts with reformer cost has been the increased application of stronger,
steam in catalyst-packed tubes at high temperature. The proprietary tube materials such as HP-Mod alloys.
process is highly endothermic. The tubes have inside diam- In new reformer design, the HP-Mod alloys have allowed the
eters of 60-120mm (2-5 in.) and are 10-14m (33-46 ft.) long. size of the reformer tube to increase, particularly those de-
The pressure is 15-30 bar (218-435 psi) and the temperature signed for the high-pressure ammonia process. With the HK-
between 900 to 1000°C (1652-1832°F). Tube wall thickness 40 alloy the reformer tube diameter was limited by tube wall
ranges from 8 to 20mm (.31-.79 in.) depending on tube thickness. Excessively thick tubes are candidates for acceler-
diameter, temperature and pressure. Excess steam is used to ated creep damage resulting from large temperature differ-
reduce the formation of carbon. The reforming reactions are ences across the thick tube wall. The use of HP-40 Mod Nb has
favored by high temperature but retarded by high pressure. A allowed the internal volume of tubes to grow dramatically,
typical steam methane reformer for hydrogen and methanol without increase in tube wall thickness, producing capacity
production is shown in Figure 3. increases of 30% to 40% for the same tube count, with only
When synthesis gas is used in the production of ammonia the marginally higher cost.
conditions are considerably different. Nitrogen is provided by In retrofit or revamp design, the HP-40 Mod Nb allows two
the injection of air into the primary reformer effluent and a possibilities. First, with the outside diameter fixed because of
secondary reforming step is carried out in a separate catalyst- existing inlet and outlet manifolds, make the tubes thinner.
filled vessel. Because of the balanced load between the two This improves the rate of heat transfer and increases catalyst
reformers, the temperature in the primary reformer tends to be volume and hydrogen production capacity. The second op-
lower, 815°C (1500°F) and the pressure between 15-40 bar tion is to keep the same tube diameter and thickness and raise
(218-580 psi). the design tube metal temperature by 60°C (108°F).
Since the catalyst tube assembly can amount to 25% of the Many failures of HK-40 have occurred in risers, manifolds,
total cost of the furnace, there is a great incentive to optimize transfer headers and other components due to stresses from

4
Figure 3 Steam methane reformer, typical for hydrogen production

f 'uel gas '< A

(g BFW m air
< I t (9 "°""""
150°C
(300°F)
C\) I) 540-620°C ( ) < 7
)
('000-"50°') L

ED. fan
7
m"h" rjv \/C M M "
I.D. fan

840°C
(1550°F) CB Methane HP steam
>
0 O F)
CB Steam 400-51 0°C (750-95
45-100 bar (650-15 00 psig)

V t"^J >
'<>' Synthesis gas

345°C (650°F)
17-25 bar (250-350 psig)

thermal cycling. These stresses occur chiefly during startup HP-40 Mod Nb
and shutdown. The HP-Mod alloys can cope substantially 1.4 " m m - - - - HK-40 alloy
better with thermal stresses. Figure 4 shows the effect of wall One-half
thickness on the life of HP-40 Mod Nb and HK-40. It also shows 1 .2 — times
the reduction or increase in life resulting from an above or normal
below normal number of thermal cycles and the reduction in S? 1.0 _ Normal
life caused by operating 28°C (50°F) above normal operating
temperature. Note that for the same wall thickness the relative (D
.d 1 Two times
2 0.8 — normal
life of HP-40 Mod Nb is about three times that of HK-40, while (D
if the alloys are designed for the same strength, only twice the > _ i Normal
E 0.6 2 " " " " " " " " " I , +28°C
life can be expected. CD +50°F
CL
In addition, the good ductility and weldability of HP-40 Mod I
0.4 — 1 i . Normal
Nb deserve mention. It has, in the as-cast condition, about 8%
" " " " " " " i " "e "0 "B "J m m m
elongation. After prolonged service this drops to about 4%. If
field repairs are required on HP-40 Mod Nb after aging, a 0.2 — i e" : Normal
ePet m - m +28°C
je vm m ml m mm m
solution anneal for about two hours is recommended, which
will restore much of the elongation. W ? m : " " "I I I +50°F
0 0.25 0.50 0.75 1.0
The requirements of a cost-effective reformer design are
maximum reliability, operating stability and high thermal Wall thickness, in.
efficiency. The materials used must have a high creep strength Figure 4 Wall thickness and amount of thermal cycling
[Link] good strain relaxation, good weldability, ex- are important considerations in tube life.
cellent oxidation resistance and, after aging, good ductility
and good weldability. The HP-40 Mod Nb alloys meet most of Finally, consider the relative cost of HP-40 Mod Nb versus HK-
these requirements. 40. With the thinner wall, the cost per foot of catalyst tubing is
Lighter tubing also allows lighter tube supports. Thinner comparable, and in some cases even less than HK-40, even
walls result in better heat transfer and increase the resistance though the costof HP-40 Mod Nb alloy by weightis substantially
to thermal cycling. Consequently, running and maintenance higher. Dismissing the use of HP-40 Mod Nb alloy castings
costs are lowered and service life extended. because of their perceived expense could be a costly mistake.

5
 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
300°F 150°C
philosophy and the design of its quench systems. Thermal |.0. fan
" ~
cracking is a noncatalytic process carried out above 1100°C
( T HP BFW
(2012°F) and a few bar pressure. The destruction of saturated €) 250°F 120"C
290 345°C 550 - 850°F I) ZP· 51, bar
hydrocarbons results in unsaturated lightweight molecules of 0.7 - 1 bar 10 - 15 psig 75 psiq HC feed
ethylene and propylene. The feedstock type controls the yield <
Quenched q 1
>" A €) Dilution
€) s'eam
of primary products and byproducts. The cracking severity effluent v * (30 - 100% he by wt)
controls feedstock conversion. Selectivity is extremely im- <7 > HP steam
I 400 - 510'C 750 - 950°F
portant and is maximized by short residence time. There has 815 - 900°C < = 102 bar 1500 psig
1500 - 1650"F
been a continued evolution of designs to produce the optimum 2000-2300"f Convection section
1093-1 265°C
furnace.
Unlike reforming, pyrolysis does not employ huge amounts
of process steam, and therefore produces coke which Cracking
accumulates in the reactor and must be removed in an off-line coil 6 Radiant
section
operation. Between five and 15 furnaces are required to
maintain uniform plant production rates, so that one or more
furnaces can be off-line for decoking. The number of furnaces
depends on plant capacity and the feedstock. Energy-efficient
cracking furnaces are essential in today's plant.
Many geometrical configurations have been applied to Fuel
pyrolysis in recent years to achieve the optimum cracking
furnace. Historically, ethylene yield improvements were
obtained by raising the temperature and reducing the contact Figure 5 Process layout typical steam cracker.

3.5 3.5
Carburized at 1000°C/1832°F Carburized at 1000°C/1832°F
for 520 h in granular carbon for 520 h in granular carbon

'° ".¥:'1||"ti?t:iz 3.0 —

,, !." ' '"i):^-': l, gi'., , *

2.5 — {
cjj_
9h¢"

u 0

C" ZJ:,
2r Y';"t',., ,,S, °%, O '"U e:"

i '·° - ·i!j:|
! '"°"
e
"::::S::'
4, "k;·:S'<i'j-.,
E

daj
E "_
.u>};··j_

..,fji !-'
::2'!t
"g;'
t 1.5 - '"g!"i :S-«.

" ,, ,::,:%)!2 i~!,! ; " 1.0 —

; y°"'
U'
'E;""'
25/'° ,i^tS'
05 25/35Nb-. r±Si'?g" :
0.5 _ r:dyy':i':'^' ,8/48j

0 , , _b"?.';"::::;.!M " ^' "" :5/35WNb

950 1000 1050 1100 1150 qC
0 1 2 3 4 J
Distance from surface, mm 1800 1900 2000 2100 oF
Temperature
Figure 6 Carbon absorption in Cr-Ni Alloys: Figure 7 Rate of carbonization roughly doubles for
Beneficial role of Ni Cr and W is evident. every 55°C (100°F) increase in temperature.

6
time and pressure drop in the cracking coils. It is said that a The HP-Mod alloys have received wide recognition because of
100°C (212°F) increase in cracking temperature can increase their good carburization resistance and oxidation resistance.
the ethylene output by as much as 50%. Synergistic additions of tungsten, titanium and niobium greatly
Pyrolysis requires materials with high temperature strength improve resistance to carburization.
and resistance to carburization. Carburization reduces ductil- While carburization is a major factor, final failures are
ity, making the tube much more susceptible to stress damage generally caused by creep rupture. Creep can affect coil
from either thermal cycles or bending moments. The stressing systems by relaxing induced stresses, by distorting the piping
of aged HK-40 components has resulted in many premature configuration, and by causing creep rupture. Stress relaxation
failures. Tube-to-tube interaction is caused by temperature by creep is beneficial because it prolongs service life. If creep
changes and thermal expansion. Initially, HK-40 was the most causes distortion in the furnace tubing configuration, how-
common tube material used in low-severity furnaces, with ever, it can have a deleterious effect since it can upset the
1000°C (1832°F) frequently considered the upper limit. Many balance between the support forces and pipe weight.
problems arose because of lack of ductility, carburization, and A desirable balance between creep rupture strength and
low-cycle fatigue. creep ductility should be sought. Adequate in-service ductil-
In the high-severity furnaces of today, tube skin tempera- ity means a capability of handling thermal shock and thermal
tures of 1025°C-ll50°C (1877-2102°F) are reached. The fatigue as a result of aging and cycling between pyrolysis
best chance to succeed is by the use of a high-strength alloy cracking and decoking operations, and as a result of startup
with excellent carburization resistance (plus the ability to and shutdown.
regenerate its protective oxide film during decoking), good The HP-Mod alloys are successfully used for operations up to
creep-rupture properties without extensive creep and distor- 1150°C (2102°F) and the modified 28/48W alloys up to
tion (lengthening and bowing of tubes) and ability to handle 1200°C (2192°F). While Supertherm in Table 2 is included as
the cyclic conditions (low cycle fatigue). There are a number an HP alloy based on its Cr-Ni ratio, this composition could
of the HP-Mod alloys capable of meeting these requirements. well belong in the 28/48W group, since cobalt is a nickel
As strength at these very high temperatures is limited for equivalent. For millisecond furnaces, long-length, small-
all alloys, resistance of an alloy is related in part to the nickel diameter reactor tubes, 25 to 33 mm (.099 to 1.2 in.) inside
and silicon contents. Figure 6 ranks a number of alloys with diameter, are required; they were thought to be beyond the
regard to carbon absorption. Figure 7 shows how carburiza- capability of centrifugal casting but are now being developed
tion rates roughly double for every 38°C (100°F) rise in tem- as a centrifugal-cast product. Wrought alloy 800H, 20Cr/
perature and can become very severe above 1050°C (1922°F). 32Ni, has been used with success in this application.

New technology trends and challenges

The major companies in the high-alloy steel casting industry During the past 10 years the HP-Mod alloys have been
have positioned themselves to interact and to respond to the perfected. Plasma arc welding was introduced to improve
various needs of the petrochemical industry. These compa- stress rupture strength of welded parts. Wide acceptance has
nies are continuing to develop new alloys and modify existing been obtained for 20/32Nb cast headers, transfer lines and
alloys for the various stringent conditions and environments manifolds. Centrifugally-cast tubing, with diameters as small
found in the application of their products, to meet the desire as 38 mm (1.5 in.) inside diameter, machined — suitable for
for operation at higher temperatures and pressures to improve millisecond and short-residence time furnaces — has been
yield and efficiency, and to meet flexibility in feedstock. produced.
Good quality control starts with argon-oxygen decarburization New challenges include innovations in joining and fabrica-
melting, AOD, to control carbon and trace elements. Careful tion techniques, improved designs for thermowells and burn-
introduction of silicon, niobium, titanium, zirconium, ers, and technical service guiding the industry.
aluminum and other elements will optimize strength, ductility New high-performance furnaces will be based on today's
and weldability. Each alloy can be modified for a specific technology, and alloys play an important role. It is necessary
furnace application — many times producing custom-made to have a clear understanding of the limitations of materials,
alloys for a specific customer, meeting their very detailed and maintain good operational control and uniformity of
specifications to link a proven manufacturing route with the firing. One should select alloys having a high stress-rupture
quality assurance system. Quality control is enhanced by the strength, good ductility, adequate stability and low coefficient
purchase of fabricated components, that often combine the of thermal expansion. Avoid points of stress buildup and
optimum properties of centrifugal as well as static castings, never select an alloy by using temperature as the only guide.
wrought alloy and forgings. Use conservative metallurgy to improve plant reliability,
energy savings, efficiency and onstream time.

7
 Literature cited
1. Materials selection considerations for petrochemical 7. Solving high-temperature problems in oil refineries and
furnace tubes, G.L. Swales, Inco colloquium, Petten, petrochemical plants, C.M. Schillmoller in Chemical
Jan 29-30, 1976. Engineering, Jan 6, 1986. Reprinted as NiDI Technical
Series N° 10 001.
2. Survey of tube experience in ethylene and olefins pyrolysis
furnaces, [Link] and [Link], NACE T-5B-6 8. Consider these alloys for ammonia plant retrofit,
Task Group Report, Apr 1981. C.M. Schillmoller in Hydrocarbon Processing, Sep 1986.

3. Predict reformer furnace tube life, C.E. Jaske and others, 9. Alloys for ethylene cracking furnace tubes, A.J. McNab in
in Hydrocarbon Processing, Jan 1983. Hydrocarbon Processing, Dec 1987.

4. Furnace alloys update, C.M. Schillmoller, and U.W. van 10. Repair welding high- alloy furnace tubes, R.E. Avery, and
den Bruck in Hydrocarbon Processing, Dec 1984. C.M. Schillmoller in Hydrocarbon Processing, Jan 1988.
Reprinted as NiDI Technical Series N" 10 031.
5. Selecting high-performance casting for petrochemical
furnaces, C.M. Schillmoller, and U.W. van den Bruck, 11. Specialty furnace design. Steam reformers and steam
Corrosion '85 paper N" 23, NACE Conference, Boston, crackers, TA. Wells, paper before Gulf Coast Ammonia
MA, Mar 25-29, 1985; NACE, Houston. Producers' meeting, Baton Rouge, LA, Apr 1989.

6. Use these materials to retrofit ethylene furnaces, C.M. 12. Centrifugally-cast tubes: An overview, C.J. Muhlenforth
Schillmoller in Hydrocarbon Processing, Sep 1985. in FINDS, Vol V. Number 1, 1990.