Daido
Daido
Daido
,Ltd
Eth yle n e , e tc
Furnace Temp. 1100-1200 Coil Temp.(TMT 1080-1120 (Quencher)
Introduction
History of radiant coils for ethylene pyrolysis furnace material: A constant struggle for longer life & run length at higher temperature & severity
2007 18Cr-8Ni (304) 25Cr-20 (310)
DAIDO STEEL CO., LTD.
25Cr-35Ni (HP)
Our Solution: EST (Ethylene Super Tube) = PPW (Plasma Powder Weld) Overlaid Tube Base Tube
-Material: Conventional (HK, HP-Nb, 35Cr-45Ni, etc.) Centrifugally cast (Daido)
PPW layer
- Material: 45Cr-50Ni-1Mo Gas atomized & PPWd (Daido) - Thickness: 1 - 3 mm
Main Benefits
- Anti Catalytic Coke - Anti Carburization
DAIDO STEEL CO., LTD.
Machine finished
Anti-Carburization
The PPW layer stops carburization into the base tube by the Dam-Effect.
- Green colored surface is recognized. (same as the sample after 24 months) - No-erosion or damage is observed.
DAIDO STEEL CO., LTD.
[C]
[Ni]
[O]
[Cr]
[Fe]
[C]
[Cr]
[Fe]
[Ni]
EST
onset of graphite formation)
[C]%
4
C (4 years)
2
(Carburization)
2 0
(original)
PPW overlay Base tube Japan plant (48 months)
ID
OD
ID
OD
Mechanism of Dam-effect
Base tube: HPmod HP mod. (total C = 0.4%): Original C in metal matrix = 0.02%
0.35
C C
PPW overlay
HPmod composition
HPmod
PPW
PPW HP HPmod -M
3% Carburization progresses when C in metal matrix ( exceeds 0.02%
Metal matrix
Cr carbides
4 6 Total C (%)
10
Dam-effect can only be expected in the clad tubes, not in solid tubes.
Lack of carburization in EST can prevent physical distortion and help maintain stable operation.
Coke Resistance
Laboratory screening
Metal coupons in hot gas stream accumulate coke as experiment proceeds. Coupon EST is prepared by PPW process
192hrs 500hrs
Inconel690
Ni
35Cr-45Ni
DAIDO STEEL CO., LTD.
Furnace B: TMT
(Flat means less coke formation)
2000 1080 1060 1950
Coil A (35Cr-45Ni)
960 940 04/15/05 05/15/05 06/14/05 07/14/05 08/13/05 Date
DAIDO STEEL CO., LTD.
Coil B (35Cr-45Ni)
09/12/05
10/12/05
11/11/05
12/11/05
TMT (deg.F)
1900
(HK4M)
36 days
34 days
29 days
35 days
34 days
Furnace C (EST)
52 days
0.00 0 20 40 60
52 days
80 100 Days 120
68 days
140 160 180 200
Lower pressure increase continue through years by Self Healing Effect of EST
2 years
0.19000 0.17000 0.15000 0.13000 0.11000 0.09000 0.07000 0.05000 2005/12/14 2006/3/24 2006/7/2 2006/10/10 2007/1/18 2007/4/28 2007/8/6 2007/11/14
D e lta Pre s
300B 300A
FurnaceC : EST
100mm
[Ni]
[Mo]
[C] [O]
DAIDO STEEL CO., LTD.
[Nb]
100mm
[Cr]
[Fe]
[Ni]
[Si]
[Mn]
[Mo]
[O]
[C]
Mechanism of Self-healing
Cr2O3 HPmod As the alloy is carburized, Cr in metal matrix will be depleted (forming Cr-carbides) and lose the ability to form surface Cr2O3. 45 C C Cr% in Matrix 40 35 30 25 20 15 10 5 0 0 2 4 Total C% 6
EST(EU) 13 months EST(Japan) 14 months 48 months 6 years
EST HPmod
HPmod will lose Cr in matrix quickly to the level where enough Cr2O3 cannot be made. PPWs Cr in matrix stays high, enough to re-create Cr2O3 after each decoking cycle.
HPmod
PPW
Metal matrix
10
Cr carbides
Due to high Cr in the PPW layer, surface Cr2O3 can be re-created and reinforced after each decoking cycle: Self-healing effect
Summary
EST has, Extremely high carburization resistance Extended tube life (Twice or more) Ability to run at higher severity Maintained ductility (can survive emergency shutdowns) Suppression of catalytic coke formation Extended run length (Twice in ethane furnace) Higher pricing than conventional tubes, but Pay back In a year can be expected. (EST is in operation at over 10 commercial plants)
DAIDO STEEL CO., LTD.
Anti-corrosion to corrosive fired gas in high temperature Higher steam temperature for Higher efficiency of power generation
W 3.1 -
Fe 1.0 1.2
Actual corrosion depth in the waste to energy plant (550oC x 6000 hrs)
PPW overlaid Boiler Tube
BS T2 76 BS T6 25 Alloy6 25 30 Cr-40 Ni S US 347 H S TBA24
(Ref.) Mechanical Properties of Boiler tubes STB340 + H-276M(PPW) R.T. T/S El Base tube 620 28.8 With PPW 601 41.2 (Base 5m/m + PPW 2m/m)
Max. Ave.
Base tube
Installation
24 Waste to Energy Plants in Japan (Locations: Tokyo, Osaka, Nagoya, Hokkaido, Tochigi, Kyoto, Kagawa, Toyama, Chiba, etc)
Remarks
Over 8000 pcs are in operation now. Maximum years in operation is 9 years. (2009)
(wt%)
Al Ad.
(2) Concept of BST1 - Chemistry of BST1 is originally developed and applied for commercial Air-heater for Gasification and Ash Melting System. (Metal temperature: 800oC (1,142oF)) - Higher corrosion resistance with higher Cr than BST625 or BST276. - Higher W than BST276 prevents the formation of Cr-depleted zones. - Added Si, Al prevent corrosion by Cl through grain boundaries. - Adequate C makes fine grains to protect against corrosion through grain boundaries.
400 752
800 1,472
time
Weight loss Weight loss of BST105 at 800oC is remarkably smaller than BST276 or 625 Appearance after the test
400oC x 100 h
(g)
400
600
800
BST1
BST625
BST276
600oC x 100 h
800oC x 100 h
BST1
BST625
BST276
Conclusions
- With higher contents of Cr, W, Al, and Si (with no Mo and Co), a new generation BST1 has been developed. - A high temperature (800oC or 1,472oF) molten salt test revealed higher corrosion resistance of BST1 as compared with BST276 or BST625 against oxide and chloride formations. - BST1 is expected to enable higher steam temperatures with longer tube life, resulting in higher efficiency for waste to energy plant operation.
DSA760 ( Ni-38Cr-3.8Al)
Characteristics - High hardness in AG condition by precipitation of aCr and g phases - Wear resistance comparing with AISI 440C - Corrosion resistance in comparable with AISI 316 - Easy to machine and cold work in ST condition - Non-magnetic
Corrosion Resistance
Austenitic SS
Magnetic
440C
200
600
800
Ageing Hardness
800
700
Hardness (HV)
600
500
400
80
200
1500 1000
0.2% PS
60 40 RA EL
150 100
50
500 0 500
600
700
o
800
0 500
600
700
o
800
30 900
x50,000
x100,000
aCr g (Ni3Al)
1mm
500nm
g' Ni3Al
Hot Hardness
800
600
Hardness (HV)
DSA760
400
Nimonic80A
Wear Resistance
0.1 Pin
<Test condition> Test temperature : RT Contact force : 10kg Distance : 10km Rev. speed : 1m/s Lubricant : dry Partner disc : AISI 52100 (62HRC)
Force Pin Force
0.05
Disc
SO
(RT)
1x10 10
10 1x10
1x10 10
-1
1x10 10
-2
<0.01
<0.01
DSA760
V-attack(85%V2O5+15%NaCl) 800deg.Cx20h
A286
DSA760
Alloy80A
AISI 420
AISI 440C
1x10 -1
1x10
-2
1x10 -3
200
Hardness (HV)
Examples of Application (Tools) - High hardness (High temperature) - Excellent corrosion resistance
Weld Overlay by DSA760
Overlay:55HRC
Base:36HRC DAC3
Bearings