EUROCORR 2001

The High Temperature Corrosion Behaviour of Incoloy 800HT in Simulated Coal Gasification Atmospheres and HCM2S in Simulated Combustion Atmospheres.

D.D. Gohil, M. U. Sheriff and S. R. J. Saunders. Materials Centre. National Physical Laboratory. UK. Date: 2-Oct 2001

Combustion Atmospheres
Mass change and metal loss measurements as a function of time.

INCOLOY 800HT:
Simulated coal gasification atmospheres 400 - 600 oC With / without gasifier coal char deposit, 0.7 wt% Cl

HCM2S:
Simulated low NOx combustion atmospeheres 400 - 640 oC With / without deposits

Samples Details and Metal Loss Measurements

Samples: 600 grit SiC surface finish, major faces plane parallel to within 2 microns

Transverse sections prepared by mounting samples flat in Bakelite and polishing to a 6 micron diamond finish.

Between 10 and 24 measurements of scale thickness and final metal thickness.

Furnace

Gate Valve Push-rod

Three-Zone Furnace

(
Quartz Tube Gas Mixture Out Ar - jacket Samples

Gas Mixture In (heated gas line)

Incoloy 800HT
Nominal Composition / wt%

Fe Cr Bal. 21

Ni 33

C Si Mn 0.07 0.5-1 1.5

Al Ti 0.4 0.4

Gas Composition

Gas-1 Gas-2

CO 23.4 23.4

CO2 3.7 3.7

Composition / vol% H2 H2S HCl 250 ppm 19.8 300 ppm 600 ppm 19.8 300 ppm

H2O 3 and 6.3 3 and 6.3

N2 Bal. Bal.

15 wt% HCl (aq) at 43 oC: 300 ppm HCl and 6.3% H2O 17.6 wt% HCl (aq) at 31 oC: 300 ppm HCl and 3% H2O

Incoloy 800HT
Calculated equilibrium partial pressures for O2, S2 and Cl2, (MTDATA) Carbon dumping predicted but not observed under any conditions
-5

-10

600 ppm H 2S 250 ppm H 2S

S2

-15

log10(px / atm)

Cl2
-20

-25

O2

-30

-35 650 700 750 800 850 900

T/K

Incoloy 800HT
Mass changes at 400 oC, 6.3% H2O
Mass changes small Some confusion caused by scale spallation and deposit interaction

Incoloy 800HT
Mass changes at 500 oC, 6.3% H2O

Incoloy 800HT
Mass changes at 600 oC, 6.3% H2O

Incoloy 800HT
Average metal loss, e.g. 600 oC, 250 ppm H2S, 6.3% H2O, no char deposit Extrapolation to 9000 hours Annual metal loss rate.

Incoloy 800HT
At 400 and 500 oC, S-rich scales formed.
>Fe, Ni, S >Cr, Fe, S

Cr-rich oxide scale formed at 600 oC. On further exposures sulphide rich zones began to develop Sulphides: duplex microstructure Outer: (Fe + Ni)-rich Inner: (Cr + Fe)-rich

500 oC, 600 ppm H2S, 300 ppm HCl, +DEPOSIT

Incoloy 800HT
Annual metal loss rates against temperature for gases containing: 6.3% H2O. Char absent: Rates at 400 and 500 oC were similar for both H2S levels. At 600 oC, the metal loss rate was higher in the presence of 600 ppm H2S in gas mixture. Char present: Metal loss rates higher, especially in the presence of 600 ppm H2S in gas mixture.

Incoloy 800HT
Annual metal loss rates against temperature for gases containing: 3% H2O. Char absent: Increase in metal loss rates cf. to when 6.3% H2O was present in the gas mixtures. Char present: No clear trend when 600 ppm H2S present.

Incoloy 800HT
Tentative metal loss (corrosion) maps produced using Microcal OriginTM Char absent

400 oC

500 oC

600 oC

HCM2S
W-strengthened ferritic steel, (low cost, high strength) Alloy Composition / wt%
C - 0.06, Si - 0.28, Mn - 0.43, P - 0.022, Cr - 2.09, Mo - 0.16, V - 0.27, W - 1.48, Fe - Bal. Deposit Composition 60 wt% (FeS) + 40 wt% (Fe3O4). Gas mixture compositions were based on actual measurements carried out using sniffer ports mounted inside operating industrial boilers.

HCM2S
Low NOx combustion gas atmosphere, 400 640 oC Gas Composition / vol%
O2 0, 0.5 and 1 CO 3.98 CO2 0.97 H2 1.39 H2S H2O HCl 100 ppm N2 Bal. 410 3 ppm 15 wt% HCl (aq) at 30 oC: 100 ppm HCl and 3% H2O

Eqm. partial pressures of O 2, S 2 and Cl2 with carbon dumping, for 0% O 2 mixture. (NPL MTDATA SYSTEM)
1E-8 1E-10 1E-12 1E-14 1E-16 1E-18

Eqm. partial pressures of O2, S2 and Cl2 with carbon dumping, for 1% O2 mixture. (NPL MTDATA SYSTEM)
1E-8 1E-10 1E-12 1E-14 1E-16

S2

S2

px / atm

1E-20 1E-22 1E-24 1E-26 1E-28 1E-30 1E-32

px / atm

Cl2

1E-18 1E-20 1E-22 1E-24 1E-26

Cl2

O2
700 750 800 850 900

O2
820 840 860 880 900 920

1E-28 800

T/K

T/K

HCM2S

Mass changes large under all conditions, scale spallation occurred frequently Mixed oxide-sulphide corrosion scales indicating non-equilibrium gas mixtures Outer: Fe-rich oxide and / or sulphide Inner: (Fe + Cr)-rich oxide and / or sulphide

HCM2S
Mass spectroscopy of gas mixture with 1% O2 present.

2CO + O2

2CO2

reaction did not utilise all available O2 in gas mixture, i.e. free O2 present in some of the gas mixtures.

HCM2S

0% O2

0.5% O2

Annual metal loss rates against temperature for HCM2S. All rates were very high.
1% O2

Most severe attack occurred in the gas mixture containing 0% O2. Deposit reduced rate of attack in this gas mixture.

HCM2S
Tentative metal loss (corrosion) map produced using Microcal OriginTM

Deposit absent. Temperature is the major factor controlling metal wastage.

Summary.
Incoloy 800HT: For practical purposes annual metal wastage rates were small under the simulated coal gasification atmospheres investgated in this work. Spallation of scale and gradual growth of sulphidised zones observed. HCM2S: This alloy was severely attacked under all simluated combustion conditions investigated in this work. Scale cracking / spallation occurred more readily at temperatures higher than 500 oC. Tentative corrosion maps (deposit absent) showing metal degradation behaviour in conditions local to those used in the laboratory studies have been produced.