HYL Process HYL III HYL ZR HYL Process Gas Heater alloys optimization

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2 OVERVIEW HYL Process HYL III HYL ZR HYL Process Gas Heater alloys optimization Midrex Process Midrex Reformer performance with the New Alloy Catalyst performance Reformer optimization

3 Products for HyL & SynGAS Process

4 HYL III PG HEATER CONFIGURATION Carbon Deposition Reactions CO + H 2 C + H 2 O Beggs 2 CO C + CO 2 Bouduard CH 4 C + 2 H 2 Cracking H 2 S Injection PGH Gas Composition HyL III H % CO 12.4% CO 2 3.3% CH % C 4 +H n C + H 2 Cracking N 2 5.3% H 2 O 2.0%

5 HYL III - Centralloy ET 45 Micro (GX45NiCrSiNb45-35) Element Mass composition * Carbon 0.45 Silicon 1.60 Manganese 1.00 Chromium Iron Niobium 1.00 Ti, Zr Rare Earth elements Additions Additions HyL Design Conditions H 2, vol% 76 CO, vol% 18 CO 2, vol% 4 H 2 O, vol% 2 p, bar 9 T, ºC 600 a c CO reduction 294 a c Boudouard 60 Mass Loss, g 0,4 0,35 0,3 0,25 0,2 0,15 0,1 0,05 0-0,05 Mass Change Variation on HyL Metal Dusting Conditions Centralloy ET-45 Micro -0,001-0,001-0,002 Centralloy G 4852 Micro 0,055 0,191 0,347 Centralloy ET 45 LC -0,001-0,001-0,012 Exposure time, h Nickel Bal (45.0) (*) This is a typical composition which may be slightly modified according to the application.

6 HYL ZR PGH Gas Composition Carbon Deposition Reactions CO + H 2 C + H 2 O Beggs 2 CO C + CO 2 Bouduard CH 4 C + 2 H 2 C 4 +H n C + H 2 Cracking Cracking PGH HyL III HyL ZR H 2 59% 44% CO 12% 9% CO 2 3% 2% CH 4 16% 29% H 2 S Injection N 2 5% 6% H 2 O 2% 8%

7 HT Family Formation of Protective Oxide Scales Ni-Cr-Si Standard Alloys Ni-Cr-Al HT Family Alloys Resistance at T < 1150 C Resistance at T > 1200 C

8 HyL ZR - Material Selection for Coil Configuration Description Trade Mark Chemical Composition Approximate values in wt% Centralloy C Si Mn Cr Ni Nb W Others ET 45 Micro Add. ET 45 LC Add. HT E Fe, Al, + Add

9 SYNGAS Processes - HYL & Midrex Syngas HYL Syngas Midrex Reducing gases H 2 +CO H 2 S Injection

10 HYL ZR - PGH Best material configuration Centralloy HT E ALLOY FOR HIGH TEMPERATURE APPLICATION IN HyL PROCESS GAS HEATERS: Best configuration for the Coils. High carburization resistance / Oxidation Resistance Excellent creep strength Improve the PGH mechanical design, PROCESS OPTIMIZATION HT-Alloys family is introduced in HyL Plants & Syngas DR Process

11 Centralloy 60 HT D tube Performance in Midrex reformers

12 Market Situation and Trends High steel demand requires high DRI production Plant operates the reformer at the temperature limit With the actual materials used in the reformer tubes, the limit of the reformer roof temperature is 1150 C. How to increase Reformer's Capacity Increasing the number of reformer tubes Increasing the diameter of the reformer tubes Increasing the reformer s temperature

13 Oxide Mix A TG TC RGC Flare FC GR A Flue Gas GND GCO Reduction Furnace BG FC GND TO BG Reformer CGS FC A FC DRI FC GND TO CG GPS TGS GTF CGC PGC1stA PGC1stB PGC2st FC HY GFE HI FI GND TO REFORMING Midrex Plant Process & Cooling Gas System FC A RECUP FC AC GND TO BUSTLE

14 Centralloy G 4852 Micro Centralloy G 4879 Micro Centralloy G 4879 Micro Centrlloy 60 HT D HP Centralloy G 4852 Centralloy G 4852 Micro Centralloy G 4879 Theoretical Reformer Capacity 288 (8 ID) (10 ID) 80 s 90 s HP 2001 HP 2007 HP-MICRO 1100ºC 1140ºC 1140ºC 1185ºC Initial Design 67 tn/h Centralloy G 4852 Centralloy G 4852 HP HP 87 tn/h HV HP NEW S+C PIONEERING DEVELOP- MENTS 100 tn/h with O 2 Inject. HV-MICRO HP-MICRO tn/h Centralloy 60 HT D HV-MICRO HP-MICRO

15 Tube Test & Pilot Plant Since 2004, S+C has installed TEST TUBES with the improved 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.

16 Pilot Plant Trials at 1200ºC TMT Thermocouples Type S (Pt/PtRd) welded to the tubes Roof temperature: 1191ºC Tw 1 temperature: 1130 ºC Tw 2 temperature: 1126 ºC

17 Tube Elongation in Operation since 2004

18 MegaModule New alloy tube installation 60 HT D ID = 10.5 Inches Standard Alloys Reduction to 10 Inches 510 Reformer tubes

19 Tubes Performance & Plant Productivity since 2012 Reformer Flue Gas temperature 1165 ºC Max Ref Box temp 1150 ºC Ref Trip Point 1175 ºC Tubes elongation average 0.25 mm per month Module Production increased from 200 to 225 ton/hr Module in operation since 15 th Feb. 2012

20 DR Plants with 60 HT D tubes installed ASSEMBLIES QUANTITY DR PLANTS CUSTOMER/COUNTRY PROCESS DELIVERY DATE ALLOY SUPPLIED 4 IRAN Midrex HTD/CA4879M 4 ARGENTINA Midrex HTD/CA4852M 11 VENEZUELA Midrex HTD/CA4879M /CA 4852M 3 MEXICO Midrex HTD/CA4852M 6 VENEZUELA Midrex HTD/CA4879M/CA4879M 2 ARGENTINA Midrex HTD/CA4879M/CA4879M 510 TRINIDAD Midrex HTD/CA4879M/CA4852M 432 VENEZUELA Midrex HTD/CA4879M/CA4852M 288 RUSSIA Midrex HTD/CA4879M/CA4852M 40 EGYPT Midrex HTD/CA4879M/CA4852M 510 RUSSIA Midrex HTD/CA4879M/CA4852M 12 MALAYSIA Midrex HTD/CA4879M/CA4852M 288 RUSSIA Midrex HTD/CA4879M/CA4852M 15 TRINIDAD Midrex HTD/CA4879M/CA4852M 540 IRAN Midrex HTD/CA4879M/CA4852M 468 EGYPT Midrex HTD/CA4879M/CA4852M ADDITIONAL REMARK. S+C has been the only supplier to develop the micro version of standard and 60HT D alloys for DR, with extremely high improvements in creep and temperature resistances

21 New Alloy ID increase - Module Improvement Less Reformer Dp -5% More Process Gas Flow % Higher Reformer Box Temperature More Reforming of Natural gas Higher life of the catalyst Larger tube life Higher Productivity Less H 2 S effects, since can operate with 20 ppm

22 Reforming Reactions CH 4 + H 2 O CO + 3 H 2 (1) CH 4 + CO 2 2CO + 2 H 2 (2) CO + H2O CO 2 + H 2 (3) CH > C + 2 H 2 Cracking C 4 +H n ----> C + H 2 Cracking CO + H > C + H 2 O Beggs 2 CO -----> C + CO 2 Bouduard H 2 S + Ni -----> SNi

23 Temperature Gas Diffusion - Reaction Rate - CH 4 Conversion H 2 formation CO formation High temperature will drive the reaction forward, this is why the reaction rate is higher at higher temperatures.

24 Theoretical Reformer Capacity Increase Increasing the temperature of the Reformer Roof by 10 C = % Production. Suitable for a temperature range from 1145 C to 1195 C, that is, an increase of 50 C. It is equal to an Increase in the Reformed Gas Capacity of 18 %. This translates into a 20-25% increase in the production of the DRI plant.

25 Midrex Reformer H 2 S Reformed Feed Gas Catalyst Deactivation Midrex Reformer Max H 2 S in FG 10 ppm Each 1 ppmv additional of H 2 S (between 6 10 ppmv) in the FG decrease the Module production 1.8 % due to Catalyst Deactivation. The sensitivity of the reforming catalyst to poisoning increases at lower operating temperatures. Using the alloy 60 HT D Midrex Reformer can work with 20 ppm of H 2 S in the fee gas, operating the reformer at high temperature.

26 Feed Gas H 2 S vs Process Gas Flow

27 Suphur can totally deactivate the reforming catalyst Box Temp. 1145ºC TMT: 1077ºC RG CH 4 slippage increases 1 to 2 % RG temperature drops < 900 ºC 7 ppm Less Reforming reaction CH 4 + H 2 O -----> CO + 3 H 2 + CH 4 + CO > 2CO + 2 H 2 + CH 4 CO 2 2 % 3.5 %

28 Conversion of CH 4 increases with temperature 945 ºC Box Temp. 1185ºC H 2 O 20 to 40 ppm TMT: 1100ºC CH 4 Conversion of CH 4 increases with the increase of temperature CO H 2 CO 2 Steam reforming reaction CH 4 + H 2 O -----> CO + 3 H 2 CO 2 & methane reaction CH 4 + CO > 2CO + 2 H 2

29 More Catalyst life & reforming with high SH 2 Catalyst Poisoning Reversible Sequence H 2 S + Ni SNi 20 to 40 ppm Reformer & Tubes Alloy Steam Reformer Midrex Std Alloy Midrex 60 HTD Reformer Temp H 2 S MAX ppm 1050 ºC ºC ºC 20 Midrex 60 HTD 1185 ºC 40 Sulfur poisoning is in equilibrium with the H 2 S gas concentration and the amount required for Catalyst saturation depends on temperature

30 Midrex Module improvements Venezuela 288 tubes change 8 to 9 inches Std Alloy Dp dropped from 300 mbar to 260 mbar PG flow increased 26 % Standard alloy Ref temperature 1145 ºC Production increased from 84 to 105 tn/h Venezuela 432 tubes 8 inches New Alloy Operate the plant at max temperature 1145 ºC Expected tubes life 14 to 15 years Catalyst life 7 years Russia 288 tubes 8 inches New Alloy H 2 S in R Feed Gas 20 ppm More Reformer temperature 1165 ºC Production increased from 70 to 84 tn/h Trinidad 510 tubes change 10 to 10,5 inches - New Alloy Dp dropped 10 % PG Flow increased 15 % - Ref Temperature 1165 ºC More production from 200 to 225 tn/h

31 DRI = MONEY

32 Conclusions Process Improvements by Using New Alloy Materials Centralloy 60 HT D allows the DR Midrex reformer operate at 1185 ºC with excellent performance Reformer capacity increment with same tube quantity Reduction of oxygen consumption Less H 2 S effect on the catalyst More catalyst life More tube life Low investment cost Operation Flexibility More Productivity More Production and/or Longer Life of the Tubes

33 Centralloy 60 HTD IMPROVE PLANT PRODUCTIVITY New concept of DR Plants