ADVANCED

CENTRIFUGAL CASTING ALLOYS

FOR DRI PROCESSES

Mr. Luis Humberto Quaranta

HIGH TEMPERATURE ALLOYS FOR DIRECT

REDUCTION PROCESSES

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Table of Contents
• Products for HyL® Process: Centralloy® HT E
– HyL III applications
– HyL ZR applications
• Products for Midrex® Process: Centralloy® 60HTD
– Previous References
– S+C Pilot Plant
– Nu-Iron Experience
– Future trend for DRI Reformer Tubes

PRODUCTS FOR HYL® PROCESS

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HyL III - Centralloy® G4852 Micro R GX45NiCrSiNbTi35-25
Element Mass Average Stress to Rupture vs. Temperature

composition * 100

Carbon 0.45
Silicon 0.80
Manganese 1.00

Stress, MPa
10
Chromium 25.00
Nickel 35.00
Niobium 1.50 Centralloy® G4852 Micro R
Centralloy® G4852 Micro

Titanium Additions 1
800 850 900 950 1000 1050
Iron Balance Temperature, ºC
Time to rupture = 100,000 hours

(*) This is a typical composition which may be slightly modified according to the application.

HyL III - PGH Gas Composition

Gas Flow rate 464000 Nm3/h
Inlet temperature 280 ºC
Gas Composition HyL III
Outlet Temperature 950 ºC
H2 59.9%
Inlet pressure 8.9 Bar
CO 12.4%
Outlet pressure 7.7 Bar
CO2 3.3%

CH4 16.0%
Carbon Deposition Reactions
N2 5.3%
CO + H2 → C + H2O Beggs
H2 O 2.0%
2 CO → C + CO2 Bouduart
CH4 → C + 2 H2 Cracking
C4 +Hn → C + H2 Cracking

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HyL III - Centralloy® ET 45 Micro GX45NiCrSiNb45-35
Element Mass HyL Design Conditions Mass Change Variation on HyL Metal Dusting Conditions
H2, vol% 76
composition * CO, vol% 18
0,4

CO2, vol% 4 0,35

Carbon 0.45 H2O, vol% 2 0,3
p, bar 9
Silicon 1.60 T, ºC
ac CO reduction
600
294
0,25

0,2
ac Boudouard 60
Manganese 1.00 0,15

0,1
Chromium 35.00

M ass Loss, g
0,05

Iron 16.00 0

-0,05
Niobium 1.00 500 100 1500
Centralloy® ET-45 Micro -0,001 -0,001 -0,002
Ti, Zr Additions Centralloy® G 4852 Micro 0,055 0,191 0,347
Centralloy® ET 45 LC -0,001 -0,001 -0,012

Rare Earth elements Additions Exposure time, h

Nickel Bal (45.0)

(*) This is a typical composition which may be slightly modified according to the application.

HyL ZR - PGH Gas Composition

Gas Composition HyL III HyL ZR
Gas Flow rate 435000 Nm3/h
H2 59.9% 44.6%
Inlet temperature 97 ºC
CO 12.4% 9.4%
Outlet Temperature 970 ºC
CO2 3.3% 2.3%
Inlet pressure 9.1 Bar
CH4 16.0% 29.0%
Outlet pressure 8.8 Bar
N2 5.3% 6.3%

H2 O 2.0% 8.0%
Carbon Deposition Reactions
CO + H2 → C + H2O Beggs
2 CO → C + CO2 Bouduart
CH4 → C + 2 H2 Cracking
C4 +Hn → C + H2 Cracking

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HyL ZR - PGH Coil Material Requirements
Bulk HT Alloy
• High Creep Strength
Inner Surface • Carburisation Resistance
• Coking Resistance
• Ductility / Ageing Properties
• Erosion Resistance
• Ductility / Ageing Properties

High carbon
activity mixture
Outer Tube Surface
• Oxidation Resistance

Centrifugally cast High alloy tube

HyL ZR - Material Selection for Coil Configuration

Description Chemical Composition
Trade Mark Approximate values in wt%

Centralloy® C Si Mn Cr Ni Nb W Others

ET 45 Micro 0.45 1.60 1.00 35.00 45.00 1.00 - +Add.

ET 45 LC 0.13 0.80 1.50 35.00 45.00 0.80 - +Add.

HT E 0.45 0.50 - 30.00 45.00 0.50 - Fe, Al, + Add

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HyL ZR - Centralloy ® HT E Production

HyL ZR - PGH Applications

Centralloy ® HTE ALLOY FOR HIGH TEMPERATURE APPLICATION IN
HyL® PROCESS GAS HEATERS:
• Best configuration for the Coils.
• High carburization resistance / Oxidation Resistance
• Excellent creep strength

• Inhibit the catalytic coke formation,

• Combined with the best alloys configuration for the coil

G 4852 Micro / ET 45 Micro / HTE. for high temperatures

A new generation of “HT-Alloys” family is introduced in HyL® Plants

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 REFORMER TUBES FOR MIDREX® PROCESS

Reformer Tube Design & Alloy Selection

• The design of the tube and its material are conditioned by:
• Operating temperatures
• Gas inlet temperatures
• Heat Flux
• Pressures
• Tube Wall Thickness
• Internal Surface finish “Pull Bored”
• Operation performance and Thermal Reversal

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Market situation and Trends
Higher steel demand requires higher DRI production
Plant operates the reformer at temperature limits.
With the actual materials used in the reformer tubes, the reformer
roof temperature is limited to 1150 °C.

How to increase the Reformer´s Capacity

• Increasing the number of reformer tubes
• Increasing the diameter of the reformer tubes
• Increasing the reformer tubes temperature

Target for a new tube material

S+C goal is the use in the reformer tubes of special

alloy that allows the plants to operate the reformer at
higher temperature

Increase the Reformer Capacity with the same number

of tubes

Increase Tube lifetime in case actual temperatures

remain unchanged

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Previous DR Plants with 60HTD tubes installed
Qty Country ID (inch.) Year Materials
4 Iran 8’’ 2004 60 HTD/CA4879M
4 Argentina 10’’ 2004 60 HTD/CA4852M
11 Venezuela 10.3’’ 2004 60 HTD/CA4879M /CA 4852M
3 Mexico 10’’ 2004 60 HTD/CA4852M
6 Venezuela 10’’ 2008 60 HTD/CA4879M/CA4879M
2 Argentina 10’’ 2008 60 HTD/CA4879M/CA4879M

Tube Elongation in Operation

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Pilot Plant - Needs
• Since 2004, S+C has installed TEST TUBES with the
innovative alloy Centralloy® 60HT D in 6 different Midrex®
Reformers.
• However, all these test tubes had been operating at the
standard temperature of 1140º C.
• Therefore, the need to test the new alloy at the
MAXIMUM TARGET TEMPERATURE of 1200ºC.

• S+C DEVELOPED A PIONEER PILOT PLANT TO

EXPOSE THE NEW TUBES TO THIS LEVEL OF
TEMPERATURE.

Pilot Plant - Operation Summary – TWT

Test Start on 23.06.08 at 8:00 a.m.

Reformer Roof temperature: 1200ºC
Tw 1 temperature: 1130 ºC
Tw 2 temperature: 1126 ºC

Test End on 19.12.08 at 9:15 a.m.

~ 4.400 hours in operation

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Pilot Plant- Creep elongation results
e, mm

HP-HP HP-HV MICRO 60 HTD

New DR Plants with 60HTD tubes installed

Qty Country ID (inch.) Year Materials
4 Iran 8’’ 2004 60 HTD/CA4879M
4 Argentina 10’’ 2004 60 HTD/CA4852M
11 Venezuela 10.3’’ 2004 60 HTD/CA4879M /CA 4852M
3 Mexico 10’’ 2004 60 HTD/CA4852M
6 Venezuela 10’’ 2008 60 HTD/CA4879M/CA4879M
2 Argentina 10’’ 2008 60 HTD/CA4879M/CA4879M
510 Trinidad 10.5’’ 2012 60 HTD/CA4879M/CA4852M
432 Venezuela 8’’ 2013 60 HTD/CA4879M/CA4852M
288 Russia 8’’ 2013 60 HTD/CA4879M/CA4852M
40 Egypt 8’’ 2013 60 HTD/CA4879M/CA4852M

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Conclusions
• Process Improvements by Using New Alloy Materials
– Centralloy® 60 HT D has shown excellent performance at 1200ºC
– Reformer capacity increment with same tube quantity
– Reduction of specific consumption
– Reduction of oxygen consumption
– Less H2S effect on the catalyst
– Low investment cost
– Operation Flexibility

More Production and/or Longer Life of the Tubes

Centralloy® 60 HTD

Operation Flexibility

New concept of DR Plants !!

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