nace jubail technical meetingnace-jubail.org/meetings/daido.pdf · daido’s new materials for...

ＮＡＣＥＪｕｂａｉｌ

ＴｅｃｈｎｉｃａｌＭｅｅｔｉｎｇ

05-01-2010

Daido Steel Co.,Ltd

Daido’s New Materials for

Petrochemical industry

And Energy industry

1.1.ESTEST (Ethylene (Ethylene Super Tube)Tube)

2.2.BSTBST (Boiler Super Tube)(Boiler Super Tube)

3.3.DSA760DSA760 ((NiNi--38Cr38Cr--3.8Al 3.8Al ))

DAIDO STEEL CO., LTD.

EST (Ethylene Super Tube)

FeedNaphtha

E thane

C3,C4Steam（500-600℃）

(Quencher)

OutletTemp.(COT)800-850℃

（Furnace)

Furnace Temp.1100-1200℃

Coil Temp.(TMT）1080-1120℃

Frac tionation

Radian t Co ils(EST)

Ethylene , etc

Ethylene Furnace


2007

25Cr-35Ni(HP)

25Cr-35Ni-Nb(HP-Nb)35Cr-45Ni

25Cr-20Ni(HK)

INCO 800

18Cr-8Ni(304)

25Cr-20(310)

History of radiant coils for ethylene pyrolysis furnace material:

A constant struggle for longer life & run length at higher temperature & severity

Introduction

?


Base Tube-Material: Conventional (HK, HP-Nb,

35Cr-45Ni, etc.)Centrifugally cast (Daido)

PPW layer

Our Solution: EST (Ethylene Super Tube)= PPW (Plasma Powder Weld) Overlaid Tube

- Material: 45Cr-50Ni-1MoGas atomized & PPW’d (Daido)

- Thickness: 1 - 3 mm


- Anti Catalytic Coke- Anti Carburization

Main Benefits

PPW (Plasma Powder Welding)

Base Metal

PPW layer

Base Metal

PPW layer

As weld overlaid Machine finished

Gas atomized 45Cr-50Ni-1Mo powder


Anti-Carburization

The PPW layer stopscarburization into the base tube

by the “Dam-Effect”.

Coils with EST have been used since 2000.

Furnace A: Naphtha FeedSamples taken after 9 years of operation


Appearance of EST (After 9 years)

- Green colored surface is recognized. (same as the sample after 24 months)- No-erosion or damage is observed.


Cross Section Composition AnalysisHP-Nb, after 2 years of operation

[O][C]

[Cr]

[Ni]

[Fe]

HP-Nb

- Fully carburized.- [C]: 4.7% (ID), 1.1% (OD)

Cross section composition analysisEST, after 6 years of operation

PPW Layer

Base metal

Weld by 35Cr-45NiWeld by 45Cr-54Ni-1Mo- Carburization stops at the PPW layer

- No-carburization in the base tube

High Cr% is kept in the PPW layer

EPMA (Electron Probe Microanalysis)DAIDO STEEL CO., LTD.

[C]

[Cr]

[Ni]

[Fe]

0

1

2

3

Japan Plant (14 months)

Japan plant (48 months)

EU Plant (6 years)

Japan plant (9 years)D (2 years)

A (4 years)

C (4 years)

0

2

4

[C]%

ID OD

(original)

EST

0

2

4

[C]%

ID OD

(original)

7%

PPW overlay

onset of graphite formation)

Base tube

HP-Nb

(onset of graphite formation)

(Carburization)(original)

PPW overlay

(Carburization)

Actual Carburization Comparison

Dam-Effect by the PPW layer

Onset of carburization into the base tube


PPW overlayHPmod composition

0

0.05

0.1

0.15

0.2

0.25

0.3

0.35

0 2 4 6 8 10

C%

in m

atrix

PPWHP-M

(0

0.05

0.1

0.15

0.2

0.25

0.3

0.35

0 2 4 6 8 10Total C (%)

C%

in m

atrix

PPWHPmod

Carburization progresses when C in metal matrix exceeds 0.02%

Mechanism of Dam-effect

“Dam-effect” can only be expected in the clad tubes, not in solid tubes.

Cr carbides

Metal matrix

HP mod. (total C = 0.4%): Original C in metal matrix = 0.02%

0.4% 3%

Base tube: HPmod

HPmod PPW

C C

Lack of carburization in EST can prevent physical distortion and help maintain stable operation.


Anti Catalytic Coke

An Fe free, Cr-oxide film on the PPW layer

reduces catalytic coke formationwith “Self Healing Effect”.

Coke ResistanceLaboratory screening

0

500

1000

1500

2000

2500

45Cr-50Ni-1Mo35Cr-45Ni

25Cr-35Ni Inconel690 Ni

Material

Cok

e P

rodu

ctio

n (m

g/m

2/hr

)

96hrs 192hrs 500hrs

Simulated process gas environment

Metal coupons in hot gas stream accumulate coke as experiment proceeds. Coupon EST is prepared by PPW process


Furnace B: Gas Feed

35Cr-45Ni

TLE No.2 TLE No.1

Coils with EST(2 out of 10 passes )

Tube Metal Temperature


Furnace B: TMT (Flat means less coke formation)


940

960

980

1000

1020

1040

1060

1080

04/15/05 05/15/05 06/14/05 07/14/05 08/13/05 09/12/05 10/12/05 11/11/05 12/11/05

Date

TMT

(deg

.C)

Coil A (35Cr-45Ni)

Coil B (35Cr-45Ni)

Coil C (EST)

Coil D (EST)1750

1800

1850

1900

1950

2000

TMT

(deg

.F)

(EST) (35Cr-45Ni)

(35Cr-45Ni) (HK4M)

Furnace C:

EST used for 50% of full coil

Furnace C/D: Gas Feed

Furnace D:

Identical furnace with 35Cr-45Ni


Furnace C/D: Pressure Drop (Flat means less coke formation)

0.00

0.05

0.10

0.15

0.20

0 20 40 60 80 100 120 140 160 180 200

Days

Del

ta P

(MP

a)

Furnace D (Conventional)

36 days 34 days 29 days 35 days 34 days

0.00

0.05

0.10

0.15

0.20

0 20 40 60 80 100 120 140 160 180 200

Days

Del

ta P

(MP

a)

Furnace C (EST)

52 days 52 days 68 days


0.05000

0.07000

0.09000

0.11000

0.13000

0.15000

0.17000

0.19000

2005/12/14 2006/3/24 2006/7/2 2006/10/10 2007/1/18 2007/4/28 2007/8/6 2007/11/14

300B

300A

De lta Pres

Lower pressure increase continue through years by “Self Healing Effect”

of EST2 years

FurnaceD : 35Cr – 45NiFurnaceC : EST

Surface composition mapping of 35Cr/45Ni after 3.3 yearsNear ID surface


35-45 surface oxides contain Fe or Fe-oxide (catalyst for coke formation)

100µm [Ni]

[[Fe]Fe]

[Si] [Mo]

[Cr]

[O]

[Mn]

[Nb][C]

Surface composition mapping of EST after 9 years

EPMA (Electron Probe Microanalysis)

EST surface is covered by pure Cr-oxide, same as after 2 years

100µm [Ni][Fe]

[Si]

[O]

[[Cr]Cr]

[C]

[Mn] [Mo]

Near ID surface


Mechanism of Self-healing

Due to high Cr in the PPW layer, surface Cr2O3 can be re-created and reinforced after each decoking cycle: “Self-healing effect”

Cr carbides

Metal matrix

HPmod

HPmod PPW

C C

05

1015202530354045

0 2 4 6 8 10

Total C%

Cr%

in M

atrix

ESTHPmod

HPmod (EU) 2, 4 years

EST(Japan)14 months48 months

6 years

EST(EU)13 months

As the alloy is carburized, Cr in metal matrix will be depleted (forming Cr-carbides) and lose the ability to form surface Cr2O3.Cr2O3

HPmod will lose Cr in matrix quickly to the level where enough Cr2O3 cannot be made.

PPW’s Cr in matrix stays high, enough to re-create Cr2O3 after each decoking cycle.

Summary

• Extremely high carburization resistanceà Extended tube life (Twice or more)à Ability to run at higher severityà Maintained ductility (can survive emergency shutdowns)

• Suppression of catalytic coke formationà Extended run length (Twice in ethane furnace)

EST has,


Higher pricing than conventional tubes, but Pay back In a year can be expected.

(EST is in operation at over 10 commercial plants)

Outer surface overlay Overlay and bending

Waste to Energy plant

BST (Boiler Super Tube)

Plasma Powder Welding

BST Production Line

“Boiler Super Tube”

Higher steam temperature forHigher efficiency of

power generation

Benefits of BST (Boiler Super Tube)Original metal powder

Anti-corrosion to corrosive fired gas in high temperature

History of BST (Boiler Super Tube)

1960-1964 Union Carbide Co. in USA developed welding application of plasma energy and powder metallurgy.

1973-1991 Daido Steel developed automatic Plasma Powder Welding(PPW) equipment for engine valves.Plasma arc generator, gas controller, powder metal feeder,and particle size control were patented by Daido.

1992- More than 150 PPW equipment for engine valves have been shipped to automotive engine valve manufacturers.

1994- Daido developed Boiler tubes with PPW overlay for thewaste to energy plant through a Japanese National Project.

1998- Daido started commercial manufacturing of boiler tubes with PPW overlay as 1st Generation Boiler Super Tube"BST276，BST625" for Japanese waste to energy plants.Daido developed new process for PPW overlay on theinner surface.

2009- Daido developed New "BST1" for higher temperature operation.

1st generation "BST 276 and BST 625"(Steam Temperature: ~400oC)

C Si Mn Ni Cr Mo Co W Fe

BST276 0.01 0.8 0.2 Bal. 20.8 13.2 2.2 3.1 1.0

BST625 0.01 0.2 0.1 Bal. 21.8 9.2 2.0 - 1.2

Chemistry of Weld overlay (typical)

0 2 4 6

STBA24

SUS347H

30Cr-40Ni

Alloy625

BST625

BST276

Corrosion Depth (mm)

Max.

Ave.

(550oC x 6000 hrs)PPW overlaid

Boiler Tube

(Ref.) Mechanical PropertiesActual corrosion depth in the waste to energy plant of Boiler tubes

STB340 + H-276M(PPW)R.T.

T/S ElBase tube 620 28.8With PPW 601 41.2(Base 5m/m + PPW 2m/m)

(wt%)

Applications of “BST625 and BST276“ in Japan

Base tubeSize

OD: φ38.1 - 114.3 mm, Thickness: 3.5 - 6.0 mm,L (shipping length): 0.9 - 7.4 m

Grade STB340, STB410, SUS310J1

PPW

overlay

Thickness 2 - 2.5 mm

Grade 276 modified, Inco625, 625modified

Installation24 Waste to Energy Plants in Japan(Locations: Tokyo, Osaka, Nagoya, Hokkaido, Tochigi,Kyoto, Kagawa, Toyama, Chiba, etc)

RemarksOver 8000 pcs are in operation now.Maximum years in operation is 9 years. (2009)

New generation "BST1"for higher temperatures and longer tube life

(Steam Temperature: over 400oC)(1) Chemistry of PPW overlay

(2) Concept of BST1

- Chemistry of BST1 is originally developed and applied for commercialAir-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.

3

-

Ad.

W

21

22

27

Cr

13

9

-

Mo

BST276

BST625

BST1

0.01

0.01

Ad.

C

0.2

0.8

Ad.

Si

Bal.

Bal.

Bal.

Ni

2

Ad.-

2

AlCo

(wt%)

100 hourstime1,4721,112752oF800600400oC

12.853FeCl2

12.62Fe2O3

28.153PbCl2

16.83Na2SO4

20.63K2SO4

3.952NaCl

5.052KCl

Wt. %Mol. %

JIS Z 2293 Methods for high temperature corrosion test of metallic materials

by dipping and embedding in molten salts

Salts Dipping temperature and time

Results of Corrosion Test

Weight loss

Appearance after the test

BST625

BST276

400oC x 100 h

BST1

Weight loss of BST105 at 800oC is remarkably smaller than BST276 or 625

600oC x 100 h 800oC x 100 h

Almost no corrosion of BST1 even at 800oC

0

0.5

1

1.5

2

2.5

3

BST1 BST625 BST276

(g)

400℃ 600℃ 800℃

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.

Characteristics

- High hardness in AG condition by precipitation of αCr and γ’ 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

DSA760 ( Ni-38Cr-3.8Al)

Development History of DSA760

1972 (Japan)Ni-40Cr-4Al (mass%) was developed by Toshiba for gas turbineparts, which had high hardness and good corrosion resistance.

1974 (Russia)Ni-40Cr-3.8Al was introduced as high hardness and non-magnetic permeability alloy in a Russian paper.

1990 (UK)Ni-40Cr-3.8Al was introduced again as the Russian Ni alloy and applied to a non-magnetic pressure cylinder.

1999 - (DAIDO)DSA760 was developed for forging and rolling process

to product many kind of products for every industry by Daido process technology

Manufacturing process was cast due to low hot workability.

<条件>溶液：3.5%NaCl温度：30℃

-400

-200

0

200

400

600

800

0 200 400 600 800

Hardness (HV)

DSA760

440C420

Martensitic SS

Inconel X750316

304

Austenitic SS

Pitti

ng P

oten

tial

(mV

vs S

CE

)

poor

C

orro

sion

Res

ista

nce

exc

elle

nt

Non-magnetic

Magnetic

Hardness and Corrosion Resistance

<condition> 3.5%NaCl 30℃

Ageing Hardness

Ageing Temperature (℃ /16hrAC)

Har

dnes

s (H

V)

200

300

400

500

600

700

800

400 500 600 700ST

ST : 1150 ℃ /0.5hrWQ200

300

400

500

600

700

800

400 500 600 700ST

ST : 1150 ℃ /0.5hrWQ

Mechanical Properties at R.T.

0

500

1000

1500

2000

2500

0

20

40

60

80

100

500 600 700 800 900

Ageing Temperature (T oCx24h/AC)

0.2% PS

TS

EL

RA

Diameter : 7

Gage Length : 28

Screw chuck : M18

0

50

100

150

200

250

30

40

50

60

500 600 700 800 900

Ageing Temperature (T oCx24h/AC)

Charpy specimensSize : 10x1010R notch

Hardness

Impact Value

Tensile properties Charpy Impact Value

Microstructure after ST-AG

1µm

x50,000 x100,000

500nm

αCr

γ’ (Ni3Al)

SEM imagesSolution treatment (ST) : 1150deg.C x over0.5hr / WCAging (AG) : 550deg.C x over16hr / AC

Hard phase consists of lamellar αCr and γ/γ' phases γ' ： Ni3Al

Hot Hardness

2 0 0

4 0 0

6 0 0

8 0 0

0 2 0 0 4 0 0 6 0 0 8 0 0 1 0 0 0温度 [℃ ]Temperature (C)

Har

dnes

s (H

V) DSA760

Nimonic80A

Wear Resistance

<Test condition>Test temperature : RTContact force : 10kgDistance : 10kmRev. speed : 1m/sLubricant : dryPartner disc : AISI 52100

(62HRC)

Disc

Pin

Force Force

Pin-on-disc wear test

DSA760 AISI 440C AISI 521000

0.05

0.1

Pin

(58HRC) (60HRC) (62HRC)

DSA760 Alloy751 AISI 3041x10 -2

1x10 -1

1x10 0

1x10 1

1x10 2

1x10 3

1x10 4

0.12

0.330.16

5%H2

SO4

(RT)

1%HCl(RT)

Immersion time:6hr

.

10 -1

10 0

<0.01 <0.01 <0.01

10 1

10 2

10 3

10 4

10 -2

Acid Corrosion Resistance

Hot Corrosion Resistance

High temperature oxidation

0

2

4

6

8

10

12

700 800 900 1000 1100Temperature (deg.Cx200hr)

DSA760

A286

Alloy625

Alloy751

Alloy80A

DSA760 Alloy80A0

50

100

150S-attack(90%Na2SO4+10%NaCl)

V-attack(85%V2O5+15%NaCl)

800deg.Cx20h

Hot corrosion by salt coating

Hardness and Magnetic Permeability

1x10 -3

1x10 -2

1x10 -1

1x10 0

1x10 1

0 200 400 600 800

Hardness (HV)

AISI 316

AISI 303

AISI 420 AISI 440C

Alloy80A

Titinium alloy

γ type stainless steel (ST)

Ni-based superalloy

AISI 304

AISI 201

γ type stainless steel(Cold worked)

DSA760

Alloy718

Hot die punch

Die tool to make drug

tablets

Examples of Application (Tools)

- High hardness (High temperature)- Excellent corrosion resistance

Base:36HRC

Overlay:55HRC

DAC3

Weld Overlay by DSA760

Examples of Application (Wire, Bearings)

High Strength WiresDot pin, Dental tool

Non-magnetic BearingsMagnetic Resonance Imaging System (MRI)Electromagnetic Clutch

Wire (0.3mm in diameter) Bearings

Thank you so much for your attention

ＡＲＩＧＡＴＯＵＧＯＺＡＩＭＡＳＨＩＴＡ！！

Ｑｕｅｓｔｉｏｎｓ？

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