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Protective

ProtectiveShell
ShellCorrosion
Corrosion

Preventive protection of
Metallic Anchors and
other Components
2006

Protective
ProtectiveShell
ShellCorrosion
Corrosion
Content
1. General contemplation
Corrosion Products
Alkali Circulation
Temperature Profile
Heat flow & salt penetration
2. Metallic Alkali Compounds
Alkali Sulfates
Alkali Chlorines
3. Mechanism of corrosion in cement plants
High Temperature Chlorine Corrosion
Oxidation & Acid Corrosion
4. Preventive shell protection
Process Solutions
Various Lining Solutions for changing the Dew Point Area
Protective coatings

Protective
ProtectiveShell
ShellCorrosion
Corrosion
1.General contemplation

Corrosion Products

Protective
ProtectiveShell
ShellCorrosion
Corrosion
1. General contemplation

Raw Meal

The Salt Circulation

Input Raw Meal:

Alkali:

0,5 2,6%

Sulfur:

0,3%

Chlorine:

0,1%

Alkali Circuit
Sulfur Circuit

Input Fuel:
Fuel

Alkali

Sulfur

Chlorine

Oil

---

1-7%

---

Coal

0,8%

0,3-5%

0,4%

Alt. Fuel

7%

15%

30%

Waste Gas

Protective
ProtectiveShell
ShellCorrosion
Corrosion
1. General contemplation

Temperature Profile / Rotary Kiln

3,632
3,272
2,912
2,552

1,832
1,472
1,112
752
392
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Bauxite
ACID

Magnesia

Magnesia

Magnesia

NEUTRAL ... ALKALINE


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Bauxite

Fireclay
ACID

[0F]

2,192

Protective
ProtectiveShell
ShellCorrosion
Corrosion
1. General contemplation
Heat flow & salt penetration
1.40000C / 2,55200F

1.38000C / 2,51600F

1.00000C / 1,83200F

O2, SO2

Na+, K+, Ca2+, Mg2+

30000C / 57200F

H2O
Cl-, SO4-, S2-

29500C / 56300F

Protective
ProtectiveShell
ShellCorrosion
Corrosion
2. Metallic Alkali Compounds

Alkali Sulfate

Sulfur (Fuel)
(Fuel)

Combustion

Sulfur Oxide (vaporous)


(vaporous)

Alkalis (volatile)
(volatile)

Reaction

Alkali Sulfate (vaporous)


(vaporous)

Condensing
Clinker

Refractory Material

Protective
ProtectiveShell
ShellCorrosion
Corrosion
2. Metallic Alkali Compounds

Alkali Chlorines

Chlorine (Raw
(Raw Mix)
Mix)
Alkali Chlorine (vaporous)
(vaporous)

Reaction

Alkalis (volatile)
(volatile)
Condensing

Alkali Chlorine (vaporous)


(vaporous)

Sintering

Raw Meal

Protective
ProtectiveShell
ShellCorrosion
Corrosion
2. Alkali Compounds
Compounds

Melting Point or
Decomposition
[0C]
[0F]

KOH

361

682

KCl

768

K2CO3

Compounds

Melting Point or
Decomposition
[0C]
[0F]

NaOH

319

606

1,414

NaCl

801

1,474

894

1,641

Na2CO3

850

1,565

K2SO4

1.074

1,965

Na2SO4

884

1,623

KNO3

337

639

NaNO3

307

584

K2S2O7

>300

>572

Li2SO4

860

1,580

NH4Cl

350

662

NH4NO3

170

338

(NH4)S2O8

120

248

(NH4)2S2O3

150

302

NH4SO3-NH2

131

268

Protective
ProtectiveShell
ShellCorrosion
Corrosion
2. Alkali Compounds
Compounds

Eutectic Reaction
Temperature
[0C]
[0F]

KCL - LiCl

355

671

KCl - NaCl

657

KCl - K2SO4

Compounds

Eutectic Reaction
Temperature
[0C]
[0F]

NaNO3 - Na2SO4

120

248

1,215

NaNO3 - NaCl

298

568

690

1,274

FeCl2 - AlCl3 - FeCl3

197

387

LiCl - Li2SO4

480

896

NaAlCl4 - KAlCl4

129

264

K2SO4 - Na2SO4

428

802

KCl NaCl AlCl3

90

194

Li2SO4 - Na2SO4

591

1,096

110

230

KNO3 - NaNO3

221

430

LiCl AlCl3

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Protective
ProtectiveShell
ShellCorrosion
Corrosion
3. Mechanism of Corrosion in Cement Plants
1. High Temperature Chlorine Corrosion

2. Oxidation & Acid Corrosion

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Protective
ProtectiveShell
ShellCorrosion
Corrosion

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Protective
ProtectiveShell
ShellCorrosion
Corrosion

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Protective
ProtectiveShell
ShellCorrosion
Corrosion
3.1. Mechanism of Kiln Shell Corrosion
A) Oxidation - O2 is present (during kiln stop)
4Fe + 3O2 2Fe2O3

(Hematite)

3Fe + 2O2 Fe3O4 (Magnetite)


solid and dense Oxide Scale

B) Oxidation - SO2 is present (during kiln operation)


4Fe + 2SO2 Fe3O4 + FeS2 (Pyrite) porous Oxide Scale
T>9000C 2KCl + H2O + SO3 + O2 K2SO4 + 2HCL

(Hydrochloric Acid)

2NaCl + SO2 + H2O + O2 Na2SO4 + 2HCl


T<4000C 2HCL + O2 Cl2 + H2O

(Chloride)

Enhanced Sulphidization if Chlorine is present


FeS + Fe3O4 + 4Cl2 4FeCl2 + SO2 + O2
Direct kiln shell attack
Cl2 + Fe FeCl2

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Protective
ProtectiveShell
ShellCorrosion
Corrosion

3.1. Mechanism of Kiln Shell Corrosion


C) Hot Corrosion (during kiln operation)

800

7720C

Temperature 0C

6770C

600

400

4000C

3850C
2KCl*FeCl2

2900C

200
KCl

3550C

2550C

20

3900C

KCl*FeCl2

40

60
Mol%

Phase Diagram for Hot Corrosion


15

80

FeCl2

Protective
ProtectiveShell
ShellCorrosion
Corrosion

3.1. Mechanism of Kiln Shell Corrosion


d) Costs for Replacing of corroded Kiln Shell Sections
Example for Replacing of a Kiln Shell Section:
Kiln Diameter
Kiln Shell Section

[m]:
[m]:

4.8
10.0

Weight
Costs for Steel
Total kiln Shell
Installation
TOTAL

[Kg]:
[/kg]:
[]:
[]:
[]:

35,000
2.8*
100,000
100,000
200,000

* (06/2006)

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Protective
ProtectiveShell
ShellCorrosion
Corrosion
3.2 High Temperature Chlorine Corrosion
Temperature range at metallic surface 550 8500C / 1,022 1,5620F
Deposit and enrichment of chlorine components on the metallic surface
(Na, K) Cl (gaseous) (Na, K) Cl (solid)
Lack of oxygen underneath the refractory castable / brick (The composition of the
atmosphere is very different at the boundary layer between castable / bricks and metallic
anchors / casing. Deposits and enrichments of condensing chemical components may
occur simultaneously with oxygen reducing reactions)

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Protective
ProtectiveShell
ShellCorrosion
Corrosion
4. Preventive shell protection

Process Solutions

Objectives

Means

Reduction of Chlorine and Sulphur Input -

Fuel, Bypass

Burning Atmosphere with high oxygen


surplus

Burning Condition

Preventive Shell Protection


New Refractory Layouts (Dew Point Avoidance)
Coatings, Paints, Deposit Welding
Welding of Steel Plates on Kiln Shell

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Protective
ProtectiveShell
ShellCorrosion
Corrosion
4. Preventive Shell Protection
New Refractory Layouts (Dew Point Avoidance)
Lining proposal for ENCI lower cyclone stage T cyclone 8000C / 1,4720F
Existing Lining
40

60

6mm

114

64

Proposal 2
35 6mm

114

40

60

6 30 2mm

Dew Point Area

114

Proposal 1

Tcasing/out = 730C

Tcasing/out = 1160C

1630F

2410F

Tcasing = 2230C
4330F
Tout = 630C
1450F

Fireclay A40

CS-Board
1800

CS-Board
1500

Cyclone
Casing
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Ceramic Wool
Plates

Cover

Protective
ProtectiveShell
ShellCorrosion
Corrosion
4. Preventive Shell Protection New Refractory Layouts (Dew Point Avoidance)
Lining proposal for ENCI

Proposal 2:
114

40

60

6 30 2mm

0
Refractory
Refractory lining
lining proposal
proposal 22 (Temperature
(Temperature 800
8000C)
C)

Date
Date
Customer
Customer // project
project
Detail
Detail
Done
Done by
by

Ambient
Ambient temperature
temperature
Surface
Surface temperature
temperature
Heat
Heat transition
transition coefficient
coefficient
Calculation
Calculation formula
formula
Wind
Wind velocity
velocity
Irradiation
Irradiation coeffizient
coeffizient
Solar
Solar irradiation
irradiation
Diameter
Diameter
Transient
Transient heat
heat
Transient
Transient heat
heat tube
tube
Temperature
Temperature flow
flow
Material
Material
Fireclay-A40
Fireclay-A40
CS
CS Board
Board 1800
1800
CS
CS Board
Board 1500
1500
Steel
Steel Casing
Casing
Ceramic
Ceramic Wool
Wool Plates
Plates
Air
Air
Steel
Steel Casing
Casing

14.
14. 10.
10. 02
02
ENCI,
Maastricht
ENCI, Maastricht
Cyclone
Cyclone Stage
Stage 11
Olaf
Olaf Kuehne
Kuehne
inside
inside
800
800
814
814
150
150

outside
outside
20
20
67
67
12,20
12,20
JUERGES2
JUERGES2
11
0,60
0,60
00
5.494
6.000
5.494
6.000
625
572
625
572
10.784
10.784

mm
mm
114
114
40
40
60
60
66
30
30
11
22

unit
unit
C
C (input)
(input)
C
C (calculated)
(calculated)
2
W/m
W/m2K
K
m/s
m/s
--2
W/m
W/m2
mm
mm
2
W/m
W/m2
W/m
W/m tube
tube

W/mK
W/mK
1,265
1,265
0,135
0,135
0,105
0,105
48,3
48,3
0,11
0,11
0,03
0,03
53,633
53,633

border
border
813,8
813,8
758,3
758,3
579,3
579,3
223,2
223,2
220,3
220,3
84,3
84,3
67,2
67,2

mean
mean
785,7
785,7
671,1
671,1
415,5
415,5
223,4
223,4
161,3
161,3
75,2
75,2
67,2
67,2

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Tin = 8000C

Tcasing = 2230C
Tout= 630C

Protective
ProtectiveShell
ShellCorrosion
Corrosion
4. Preventive Shell Protection New Refractory Layouts (Dew Point Avoidance)
Insulating Castable or
Calcium Silicate Board
Ceramic Felt (short fiber)
Ceramic Blanket

Metallic Clamp

Ceramic Anchor Brick

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Protective
ProtectiveShell
ShellCorrosion
Corrosion
4. Preventive Shell Protection New Refractory Layouts (Dew Point Avoidance)

Refractory Solutions for avoiding Chimney Effects


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Protective
ProtectiveShell
ShellCorrosion
Corrosion
4. Preventive Shell Protection Coatings, Paints, Deposit Welding
Gas-tight Coatings / Paints
Polyamide Resin
Silicone Resin
Silicone Alkyd Resin
Deposit Welding by Metallic Powder Gunning
Thermal Spraying with Wire
High Speed Thermal Spraying
Electric Arc Spraying
Phosphating (Bondering)
Phosphoric Acid

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Protective
ProtectiveShell
ShellCorrosion
Corrosion
4. Preventive Shell Protection

Protective Coatings (Costs are calculated for Rotary Kiln, diam. 4,4m)
Gas-tight Coatings / Paints (2 layer, approx. 350 ml/m 2) not abrasion resistant
Resin based Coating
Polyamide Resin

refractoriness
Graphite Pigments, 75-85%
3000C / 5720F

Polyamide Resin

Silicone Resin

65% FeO Pigments (approx. 30/m2 500/m)


organic hydrocarbon

7000C / 1,2920F

(V.M. CORPRATION, Mumbai, India or Refratechnik)


Silicone Alkyd Resin

Lead and non-chromate


containing Pigment Coating

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4250C / 7970F

Protective
ProtectiveShell
ShellCorrosion
Corrosion
4. Preventive Shell Protection (Costs are calculated for Rotary Kiln, diam. 4,4m)

Protective Coatings (abrasion resistant)


Deposit Welding by Metallic Powder Gunning (1 layer, thickness approx. 1.000m)
Power Flame Spray Coating
Thermal Spraying with Wire

refractoriness
approx. 170/m2 2.400/m
Aluminium wit Ni-Al Wire

High Speed Thermal Spraying

approx. 320/m2 4.500/m


special alloy NiCrMoCuBSi
(http://www.frymetals.com/)

Electric Arc Spraying


Arc Welding with Sealing

8500C / 1,5620F

9500C / 1,7420F

refractoriness
approx. 580/m2 8.200/m
Ni-Cr 50/50
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9500C / 1,7420F

Protective
ProtectiveShell
ShellCorrosion
Corrosion
4. Preventive Shell Protection (Costs are calculated for Rotary Kiln, diam. 4,4m)

Protective Coatings (low cost solution not abrasion resistant)


Phosphating (Bondering) (2 layer, approx. 200ml/m2)
Phosphoric Acid (H3PO4 75%)

approx. 8/m2 120/m


Fe2O3 + PO43- FePO4
FeO

+ PO43- Fe3(PO4)2

FeS2 + PO43- Fe3(PO4)2

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refractoriness
3500C / 6620F

Protective
ProtectiveShell
ShellCorrosion
Corrosion
4. Preventive Shell Protection

Protective Coatings (not abrasion resistant not suitable for rotary kiln)
Ceramic Mortar (1 layer, approx. 2kg/m2 or 1kg/75anchors)

refractoriness
1.3000C / 2,3720F

Coro Tex 5009/3810

approx. 45/kg

(Hoganas - Sweden)

Coro Tex 5009 Powder (62% by weight)


Coro Tex 3810 Liquid

(38% by weight)

Pot-life at 200C about 2hrs


Curing Time about 2 3hrs
Density 1.8 kg/dm3
Shelf life:
Coro Tex 5009 - unlimited
Coro Tex 3810 5 months

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Protective
ProtectiveShell
ShellCorrosion
Corrosion

Costs for heat resistant Alloys (1/2006)


1.4828 AISI 309 X15CrNiSi20-12
1.4841 AISI 314 X15CrNiSi25-20
1.4845 AISI 310 X12CrNi25-21

5,00 /kg
6,20 /kg
6,30 /kg

Inconel 625
2.4856 AISI 625 NiCr22Mo9Nb

36 40,00 /kg

Stainless Steel:
1.4301 AISI 304 X5CrNi18-10 (V2A)
1.4571 AISI 316 X6CrNiMoTi17-12-2 (V4A)

3,50 /kg
4,80 /kg

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Protective
ProtectiveShell
ShellCorrosion
Corrosion
4. Preventive Shell Protection

Protective Coatings (not abrasion resistant not suitable for rotary kiln)
Ceramic Mortar (1 layer, approx. 2kg/m2 or 1kg/75anchors)
Coro Tex 5009/3810

refractoriness
1.3000C / 2,3720F

approx. 45/kg

(Hoganas - Sweden)

coated with Coro Tex

not coated

Metallic Components after 1 year of operation (6.500tpd)


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Protective
ProtectiveShell
ShellCorrosion
Corrosion
4. Preventive Shell Protection

Welding of Steel Plates on the Kiln Shell


Mild Steel, Size approx. 2 x 2m, 5 -6mm thick
Service Life of Steel Plate: 1 2 years (depends on Corrosion Progress)

Refractory
Brick

Steel Plate
Refractory
Mortar

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Protective
ProtectiveShell
ShellCorrosion
Corrosion
4. Preventive Shell Protection

Welding of Steel Plates on the Kiln Shell


Stainless Steel, Size approx. 2,44 x 1,22m, 0,79mm thick
Steel grade: V2A (1.4301, AISI 304) or V4A (1.4571, AISI 316)
Service Life of Steel Plate: 1 2 years (depends on Corrosion Progress)

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Protective
ProtectiveShell
ShellCorrosion
Corrosion
4. Preventive Shell Protection

Welding of Steel Plates on the Kiln Shell


Stainless Steel, Size: endless 900mm Steel Roll, 0,38mm thick
Steel grade: V2A (1.4301, AISI 304) or V4A (1.4571, AISI 316)
Service Life of Steel Plate: 1 2 years (depends on Corrosion Progress)

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Protective
ProtectiveShell
ShellCorrosion
Corrosion

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