PaperCon 2011 Rethink Paper – Lean and GreenpEffective Paper Machine Slime Control and No Vapor Phase Corrosion
Jim AndersonJim AndersonGuilherme Fernando Cortinovi
Bruno Bolduc
PaperCon 2011 Page 2284
“Evolution” of Effective PM Slime ControlAlkaline Fine Paper (North America)Alkaline Fine Paper (North America)• The evolution of using oxidizing biocides • What are the current issues/problems?• What are the current issues/problems?• A “new” technology to address the current and
“old” issuesold issues
PaperCon 2011 2
PaperCon 2011 Page 2285
“Evolution” of Effective PM Slime ControlAlkaline Fine Paper (North America)Alkaline Fine Paper (North America)
1985-2000
“Strong” Oxidizers
1995-2005
“Mild” Oxidizers
2000-Present
“Mild” Oxidizers
1980-1990
Non Oxidizing Oxidizers
w/ BiocideOxidizers w/ Biocide
Oxidizers w/o Biocide
Oxidizing Biocide(s)
a) Performance Issues:
a) Cost
Issues:• Cost• Performance
Issues:• Ox Control• Interactions
Issues:• Cost• Performance
Issues:• Cost• Vapor phasea) Cost
b) Performance
Performance Interactions• Performance
Performance Vapor phasecorrosion
PaperCon 2011 3
PaperCon 2011 Page 2286
“Evolution” of Effective PM Slime ControlAlkaline Fine Paper (North America)Alkaline Fine Paper (North America)
1985-2000
“Strong” Oxidizers
1995-2005
“Mild” Oxidizers
2000-Present
“Mild” Oxidizers
1980-1990
Non Oxidizing Oxidizers
w/ BiocideOxidizers w/ Biocide
Oxidizers w/o Biocide
Oxidizing Biocide(s)
Issues:
a) Ox Control
Issues:
a) Cost
Issues:• Cost• Performance
Issues:• Ox Control• Interactions
Issues:• Cost• Performance
Issues:• Cost• Vapor phasea) Ox Control
b) Interactions
c) Performance
a) Cost
b) Performance
Performance Interactions• Performance
Performance Vapor phasecorrosion
PaperCon 2011 4
PaperCon 2011 Page 2287
Eka Purate® CIO2
• It is a blend of sodium chlorate (NaClO3) & peroxide (H2O2)• Patented ClO2 method 2
• Chemical generation reaction:(2NaClO3 + H2O2) + H2SO4 2ClO2 + O2 + Na2SO4 + 2H2O(2NaClO3 + H2O2) + H2SO4 2ClO2 + O2 + Na2SO4 + 2H2O
(Chlorate + peroxide) plus (acid) (chlorine dioxide)• Lowest cost for small scale generation of CIO• Lowest cost for small scale generation of CIO2
• State of the art control • Generation of chlorine dioxide (efficiency and simplicity)( y p y)• Application for disinfection & slime control
PaperCon 2011 5
PaperCon 2011 Page 2288
CIO2 Generation
H2SO4 EPI PlatformChlorate/Peroxide
Blend
EPI Platform(Eka Process Information)
GeneratorFresh Water
Process Water flow
0.5-3.0 g/l
0.5-3.0 g/l
PaperCon 2011 6
PaperCon 2011 Page 2289
The Benefits of Using CIO2
• Widely used in Europe (Paper & Water) & North America (Water)
• Cost effective• Improved runnability
• Less web breaks • Better retention – filler, sizing agents
PaperCon 2011 8
PaperCon 2011 Page 2291
The Benefits of Using CIO2
• Improved paper quality• Less holes and spotsp• Less biofilm in pipes and towers
• Increased ORP• Reduced Odors (No H2S smell)• Increased pH/less dissolved Ca++ level
L d d f d h• Lower demand for wet end starch• Reduced potential for vapor phase corrosion
PaperCon 2011 9
PaperCon 2011 Page 2292
Corrosion with OxidizerHypo Chloramines and ClO2Hypo, Chloramines, and ClO2• Liquid phase
• SS is resistant• No issues reported
• SS pitting due to chlorides• Chloride levels are normally a problem• No issues reportedV h• Vapor phase• Corrosion in wet end mist area (cat walks, ceiling,
frame etc )frame, etc.)• Corrosion in dryer section (dryer can surface, dryer
section ventilation, dryer felt carrying rolls, etc.)
PaperCon 2011 10
PaperCon 2011 Page 2293
Vapor Phase Corrosion TestingHypo Chloramines and ClO2Hypo, Chloramines, and ClO2• Lab studies to simulate WW evaporation and
condensation – measuring the condensed vapor components
• Lab studies to document the impact of the WW vapors have on corrosion couponshave on corrosion coupons
• Paper Machine testing for the components in the condensed vapor from the first section of drying
PaperCon 2011 11
PaperCon 2011 Page 2294
Evaporation & Condensation Lab Apparatus
Cooling WaterCondenser
Condensed Vaporsfrom WW
WhiteWater
PaperCon 2011 12
PaperCon 2011 Page 2295
Evaporation & Condensation Lab Apparatus
WW VaporCooling Water WW VaporWater
Heated WW200 mlCondensed
WW VaporsHeat
WW Vapors~40 mls __
Untreated, Hypo, Chloramines (MCA or BAC),& ClO2Hypo, BAC, MCA , & ClO2 @ varying ppms
pH ORP Total Cl2 ClO2 ConductivityWW X X X X XWW after test X X X X X
PaperCon 2011 13
Condensed WW Vapors X X X X X
PaperCon 2011 Page 2296
Lab Study – Condensed Vapors
450
ORP Trend – Condensed Vapors – Mill A
mv
400
450
OR
P -m
350HypoAmBr - BACVa
pors
250
300 AmBr BACClO2
dens
ed
2000.0 1.0 2.0 3.0 4.0 5.0
D f O idi
Con
d
PaperCon 2011 14
Dosage of Oxidizer - ppm
PaperCon 2011 Page 2297
Lab Study – Condensed Vapors
0 5
Total Cl2 – Condensed Vapors – Mill A
ppm
0.4
0.5
tal C
l 2 -
0.3HypoAmBr - BACpo
rs T
o
0.1
0.2 AmBr BACClO2
nsed
Va
00.0 1.0 2.0 3.0 4.0 5.0
D f O idi
Con
den
PaperCon 2011 15
Dosage of Oxidizer - ppm
PaperCon 2011 Page 2298
Lab Study – Condensed Vapors
400
ORP Trend – Condensed Vapors – Mill B
mv
350
400
OR
P -m
300 HypoAmBr - BACVa
pors
200
250 ClO2AmSO4-MCA
dens
ed
1500.0 1.0 2.0 3.0 4.0 5.0
D f O idi
Con
d
PaperCon 2011 16
Dosage of Oxidizer - ppm
PaperCon 2011 Page 2299
Lab Study – Condensed Vapors
6
Total Cl2 – Condensed Vapors – Mill B
ppm
5
6
tal C
l 2 -
3
4HypoAmBr - BACpo
rs T
o
1
2ClO2AmSO4-MCA
nsed
Va
00.0 1.0 2.0 3.0 4.0 5.0
D f O idi
Con
den
PaperCon 2011 17
Dosage of Oxidizer - ppm
PaperCon 2011 Page 2300
Mill Study – Condensed Vapors
Dryer Section Ice Chest
Hose to collect vaporsfrom above the paper web
Vacuum Pump
PaperCon 2011 18
from above the paper web
PaperCon 2011 Page 2301
Mill Study– Condensed Vapors
Mill Data – Total Chlorine in VaporsAlkaline Fine Paper
2.25
2 00
2.50
AC
H D
PD
Alkaline Fine Paper
1.50
1.251.50
2.00
(ppm
) HA
Headbox
C d d
0.56
0.89
0.22
0.85
0.50
1.00
Chl
orin
e Condensed Vapors
0.02 0.03 0.000.00
AmSO4(MCA)
AmBr(BAC)
ClO2PM1
ClO2PM2
ClO2PM4
Tota
l
PaperCon 2011 19
PaperCon 2011 Page 2302
Mill Study– Condensed VaporsIncreased ClO2Increased ClO2
Mill Data – Total Chlorine in VaporsAlkaline Fine Paper
0.80 0.71
AC
H D
PD
Alkaline Fine Paper
0 40
0.600.41
(ppm
) HA
Headbox
Condensed
0.20
0.400.22
0.00 0.00 0.00Chl
orin
e ( Condensed
Vapors
0.00ClO2
NormalDose
ClO22X Normal
Dose
ClO24X Normal
Dose
Tota
l C
PaperCon 2011 20
Dose Dose Dose
PaperCon 2011 Page 2303
Mill Study– Condensed VaporsVarying Operations and BAC DoseVarying Operations and BAC Dose
Mill Data – Total Chlorine in VaporsAlkaline Fine Paper - 1st Dryer Section
1 401.60
1.60
1.301.20
AC
H D
PD
Alkaline Fine Paper - 1st Dryer Section
0 801.001.201.40
0.61 0 55(ppm
) HA
Headbox
Condensed
0 200.400.600.80
0.40
0.55 0.49
0 03Chl
orin
e ( Condensed
Vapors
0.000.20
July 1normal
operation
July 22normal
operation
Aug 16baled pulp
Sept 9BAC stopped
for 6 hrs
0.03
Tota
l C
PaperCon 2011 21
operation operation for 6 hrs
PaperCon 2011 Page 2304
Vapor Phase Testing – Coupons
2 Coupons suspended in the Heated Vaporsp(30 hrs)
To refill with HB stockHB stock
MaxMin
PaperCon 2011 22
PaperCon 2011 Page 2305
Vapor Phase Testing – Coupons
ClO2Front & Back
AmSO4Front & Back
AmBrFront & Back
PaperCon 2011 23
Front & Back Front & Back Front & Back
PaperCon 2011 Page 2306
Vapor Phase Testing – Coupons
Corrosion Rate ResultMild Steel Coupons Suspended in Vapors 30 hrs
52.050
60
py)
Mild Steel Coupons Suspended in Vapors 30 hrs
23 4 25.7
34.4 33.3
41.3
30
40
n R
ate
(mp
23.4 25.7
10
20
Cor
rosi
on
0
10
ClO2 ClO2 MCA MCA BAC BAC
C
PaperCon 2011 24
PaperCon 2011 Page 2307
Vapor Phase Testing – Coupons
Corrosion Rate ResultMild Steel Coupons Suspended in Vapors 30 hrs
27 6
34.535
40
py)
Mild Steel Coupons Suspended in Vapors 30 hrs
15 3 16 118.8
16 4
24.6 23.227.6
20
25
30
n R
ate
(mp
15.3 16.1 16.4
5
10
15
Cor
rosi
on
0
5
Blank Blank ClO2 ClO2 MCA MCA BAC BAC
C
PaperCon 2011 25
PaperCon 2011 Page 2308
Summary – Condensed Vapor Studies
• Lab Studies – Heating WW and Condensing Vapors• AmBr (BAC) – always detected Total Cl2 in condensed
vapors, varying amount & increased with BAC dose• AmSO4 (MAC) – always detected Total Cl2 in condensed
vapors, varying amount & increased with MCA dosevapors, varying amount & increased with MCA dose• ClO2 – zero to trace amounts of Total Cl2 in
vapors, increased to trace amounts with increased dose of ClOClO2
• Mill Condensed Vapor Studies – agreed with Lab Studies• Corrosion Coupons in the Vapor Phase – the trend agreed
with condensed vapor studies• All agreed with what we see in the “real world
PaperCon 2011 26
PaperCon 2011 Page 2309
Effective Paper Machine Slime Control and No Vapor Phase CorrosionVapor Phase Corrosion • ClO2
• Improved small scale generation of ClO2p g 2
• Improved control with PLC• A “new” technology to address
• The current issues (vapor phase corrosion) and • “Old” issues (control and application)
PaperCon 2011 27
PaperCon 2011 Page 2310