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THE USE OF HYDROGEN PEROXIDE IN THE USE OF HYDROGEN PEROXIDE IN THE BLEACHING OF CHEMICAL PULPTHE BLEACHING OF CHEMICAL PULP
Ross Anderson
Kemira Chemicals
Southeastern TAPPI and TAPPI Bleaching Committee
Joint Meeting
St. Augustine, FL - June 13, 2002
AgendaAgenda
• Introduction• Safety and Handling• Chemistry• Process Control• Bleaching Applications• New Developments
AgendaAgenda
• Introduction• Safety and Handling• Chemistry• Process Control• Bleaching Applications• New Developments
Overcoming Bleach Plant LimitationsOvercoming Bleach Plant Limitations
• short sequences• eliminate hypochlorite• prevent dioxin formation• extend ClO2 capacity to more pulp prod’n• ECF
• decrease cost• increase brightness• increase pulp production
• TCF
Evolution in Hydrogen Peroxide UseEvolution in Hydrogen Peroxide Use
Add to existing bleaching stages
Intensify process conditions to get more effect
Add pretreatment to get more focused effect
Add specialized process stages and equipment
Modify chemistry to get different effect
Hydrogen Peroxide ManufactureHydrogen Peroxide ManufactureAnthraquinone Anthraquinone ProcessProcess
OC2H5
O
OHC2H5
OH
H2 O2
H2O2
circulatingworksolution
Hydrogen Peroxide ManufactureHydrogen Peroxide Manufacture
Purification
HydrogenPlant
Hydrogenation
Stabilization
Storage
Oxidation &Extraction
Concentration
PropertiesProperties
• clear, colorless liquid• low vapor pressure• sp.gr. (50% solution) = 1.19 at 4°C• freezes at -52°C (50% solution)• boils at 114°C (50% solution)• pH 0.5 - 3.5
-60
-50
-40
-30
-20
-10
0
0 10 20 30 40 45 50 60 80 90 100
Freezing Point of Hydrogen PeroxideFreezing Point of Hydrogen Peroxide
H2O2 concentration, wt%
Tem
pera
ture
, oC
POINT A
H20 COOLINGWATER
H20 DILUTION
UNLOADINGSTATION
INDOOR
P1
P3
P2
H2O2 TODILUTION
REMOTE SETPOINTFROM PROCESS
LIALIA
TIATIA
H
HL
H
H
LIRSA
LLL
HHH
TIA
H
A A
FIC
DOSINGTANK2-4 M3
H2O2-STORAGE TANKMIN 60 M3
Storage System for Hydrogen PeroxideStorage System for Hydrogen Peroxide
• Introduction• Safety and Handling• Chemistry• Process Control• Bleaching Applications• New Developments
Personal Protective EquipmentPersonal Protective Equipment
• Splash-proof goggles (and face shield)
• Rubber gloves and boots
• Acid suit
Hazard of CombustionHazard of Combustion
• Peroxide, itself, does not burn• Decomposition reaction is exothermic
• produces heat and oxygen• Remove combustible materials• Water removes heat and decreases
reactivity
Hazard of PressurizationHazard of Pressurization
• Decomposition in pump
• Decomposition in storage tank
• Non-pulp & paper: Submarine Kursk
Hazard of PressurizationHazard of Pressurization
• Decomposes continuously at slow rate• Pressure increase in “closed” systems
• storage tank vents• piping PRVs• ball valves drilled on upstream side
• Design systems to limit potential for contamination
• Use approved materials only• Passivate process contact surfaces
Volume of Oxygen Released atVolume of Oxygen Released atDecomposition of HDecomposition of H22OO22
050
100150200250300350400450500
0 10 20 30 40 50 60 70 80 90 100
H2O2 concentration, wt%
liter
O2
/ lit
erH
2O
2
HYDROGEN PEROXIDE H2O2
Stainless Steel Ball ValvesStainless Steel Ball Valves
SMALLOPENING
FLOW
TO TANK
Vent hole is required to prevent entrapment in the cavity of the valve body
Pumps for Hydrogen PeroxidePumps for Hydrogen Peroxide
CENTRIFUGAL
SS 316 or 304 wetted parts
• Process flush single mechanical seals: only seals of silicon carbide with Kal-Rez “O” Rings.• Ease of operation and maintenance• Requires recirculation line for assured minimum flow• Greater range of control of flow with flow meter and flow control valve (most common in industry)• Allows multiple application from one header
METERING OR POSITIVE DISPLACEMENT
SS 316 or 304 Teflon® wetted components.
• Can provide very small flow control.
• Requires pulsation damper for uniform flow and pressure regulating device for proper operation.
• Can achieve high pressure discharge.
• Has a tendency to vapor lock if shut down..
• Built in check valve can be a problem.
Most Common Materials Compatible with Most Common Materials Compatible with Hydrogen Peroxide in Concentrations of Hydrogen Peroxide in Concentrations of
70%, 50% and 5%70%, 50% and 5%
Compatible Incompatible
Storage Tanks - wetted parts only Exterior StructuralAluminum 5254 Aluminum 6061TStainless Steel 316L, 304L High carbon content SS
Piping Stainless Steel 316L, 304L Carbon SteelWetted Parts Pumps All other Metals
Valves ASTM A- 312 and Hoses Stainless Steel 316, 304, 321, Carbon Steel, Brass andand Teflon® most other materials
Pump Seals Carbon and most other materials- Silicon Carbide, Glass filledTeflon® on 316SS Asbestos Graphite and most Kal-Rez “O” Rings, Viton ® other materials
Gaskets Teflon®, Gylon ®, Tygon®, Teflon® envelope BrassPressure Gauges 316 Stainless Steel Silicone, mineral oil and most other fluids
Liquid pressure gauges316 Stainless Steel filled with ABS, Brass, Flurolube® or Krytox ® Copper, Lead, Mercury
Lab SuppliesGlass, Stainless Steel 316, 304, Tygon®, Polyethylene, PVC, Teflon®
Materials of ConstructionMaterials of Construction
Acceptable:
• 316L (304,304L) stainless steel • 5254 aluminum
• carbon steel• brass• copper• zinc
Not Acceptable:
Materials of ConstructionMaterials of ConstructionTitaniumTitanium
• high “Handbook” corrosion rate• significant corrosion potential at:
• > 0.2% H2O2 in solution ( 2% on pulp @10% Cs)
• > pH 11• > 90°C
• corrosion inhibited by Ca and Mg• corrosion has not been an issue in refit
TCF sequences
• Introduction• Safety and Handling• Chemistry• Process Control• Bleaching Applications• New Developments
ChemistryChemistryRadicalsRadicals
H2O2 + Mn+ ⌫ •OH + M(n+1)+ + OH-
M(n+1)+ + OOH- ⌫ Mn+ + •O2- +
H+
Assay MethodsAssay Methods
• Density
• KI-Thio titration
• 2° titration with Ceric Sulphate• peroxide-specific Ti4+ indicator• Peroxidase analytical sticks
Pure solution
Process residual
Differentiation from ClO2
• Introduction• Safety and Handling• Chemistry• Process Control• Bleaching Applications• New Developments
• Introduction• Safety and Handling• Chemistry• Process Control• Bleaching Applications• New Developments
Effectiveness of ApplicationsEffectiveness of Applications
• Consumption in non-bleaching reactions• chemical carryover• organic carryover• metals
• Optimized process conditions
• Mixing
PeroxidePeroxide--Reinforced E1Reinforced E1--StageStage
• Decrease colour• eliminate dioxin in CD Eop D E D• decrease AOX in DC Eop D E D• decrease cost and increase
brightness in D Eop D E D
PeroxidePeroxide--Reinforced E2Reinforced E2--StageStage
• higher ClO2 replacement ratio (>2:1)
• limited H2O2 consumption (<2 kg/tp)
• lower pH target than for Eop-stage
Peroxide in Bleached Pulp StoragePeroxide in Bleached Pulp Storage
• improved brightness stability
• complicated process control
• decreased bleach plant operating flexibility
Final Peroxide Brightening StageFinal Peroxide Brightening Stage
• high pressure, high temperature
• low metals content
• Mg/Mn > 100
• Introduction• Safety and Handling• Chemistry• Process Control• Bleaching Applications• New Developments
TCF BleachingTCF BleachingHardwood
H2O2 5 kg/tNaOH 10 kg/tMgSO4 1 kg/t
Final pH: 5 Final pH: 9.8H2O2 residual: 1 kg/t
PAA 4-5 kg/t H2O2 19 kg/tNaOH 11 kg/t
Final pH: 5.8 Final pH: 9.6H2O2 residual: 5.2 kg/t
Op POPAAQ2Q1
EDTA 0.8 - 1.3 kg/t EDTA 1.3 kg/t
TCF TCF BleachingBleachingHardwood
O2 Stage
Brightness: 88.7 %ISOKappa: 4.8Viscosity: 818 dm3/kg
Op PO
Brightness: 59.3 %ISOKappa: 9Viscosity: 1025 dm3/kg
Brightness: 76.3 %ISOKappa: 7.4Viscosity: 976 dm3/kg
Brightness: 79.4 %ISOKappa: 5.8Viscosity: 954 dm3/kg
PAAQ2Q1
Modify Peroxide ChemistryModify Peroxide Chemistry
• Peroxide Bleaching Enhancers
• Peracids• in situ formation• distilled Peracetic Acid, PAA
• Metal Catalysis, mP
Oxidation Potentials of Oxidation Potentials of Bleaching ChemicalsBleaching Chemicals
Oxidation Reaction Oxidation Potential, eV
O3 + 2H+ + 2e- ⌫ O2 + H2O 2.07
HClO2 + 3H+ + 4e- ⌫ Cl- + 2H2O 1.56
HOCl + H+ + 2e- ⌫ Cl- + H2O 1.49
Cl2 + 2e- ⌫ 2Cl- 1.36
ClO2 + H+ + e- ⌫ HClO2 1.15
CH3CO3H + 2H+ + 2e- ⌫ CH3CO2H + H2O 1.06
ClO- + H2O + 2e- ⌫ Cl- + 2OH- 0.90
HOO- + H2O + 2e- ⌫ 3OH- 0.87
ClO2- + 2H2O + 4e- ⌫ Cl- + 4OH- 0.78
O2 + 2H2O + 4e- ⌫ 4OH- 0.40
Production of Production of Peracetic Peracetic AcidAcid
CO
OHCH3 + H2O2 C
O
OCH3
OH+ H2O
catalyst
hydrogenperoxide
peraceticacid
acetic acid water
Production of Distilled Production of Distilled Peracetic Peracetic AcidAcid
Aceticacid
Hydrogenperoxide
Productstorage
dPAA
Water
Productstorage
ePAA
Catalyst
Stabilizator
Generation of Generation of Caro’s Caro’s AcidAcid
Effect of Molar Ratio and Concentration of Feed Chemicals
0
10
20
30
40
50
60
70
80
90
100
0.00 0.25 0.50 0.75 1.00 1.25 1.50 1.75 2.00 2.25 2.50 2.75 3.00
98% H2SO4/H2O2 Molar Ratio
Pero
xide
Con
vers
ion,
%
65% Oleum 70% H2O2
50% H2O2
Chemical Impact of Chemical Impact of Peracid Peracid AdditionAddition
Need of neutralisation & side products
dPAA ePAA PFA Caro's acidPeracid, kg/tp * 10 10 7.9 15NaOH Demand, kg/tp ** 1 4 26 20By-Product acetic acid CH3COONa HCOONa Na2SO4
Na, kg/tp negligible 4.6 29.9 23S, kg/tp n/a n/a n/a 9.9
* amount needed for delignification of 3 kappa units** amount of NaOH needed for adjusting the pH to 5
PAA in Final DPAA in Final D--StageStageSoftwoodSoftwood
0 2 4 6 8 10858687888990919293
Brig
htne
ss, %
ISO
ClO2 + 2 kg Paa/tp
ClO2 alone
ClO2, kg/tp (act. Cl)
Effect of ClO2 Dosage
PAA PostPAA Post--BleachingBleachingProcess ConditionsProcess Conditions
• Temperature: 40 - 70°C• pH: 4 - 7• PAA charge: < 3 kg/tp
• Fast reaction…even at low consistency
PAA PostPAA Post--BleachingBleachingBenefits at Pulp MillBenefits at Pulp Mill
• Decreased usage of ClO2
• decreased AOX• extra pulp production if ClO2 capacity is a bottleneck
• Improved pulp quality• higher and less variable brightness• improved brightness stability (less yellowing)• less variable pH
• No brightness reversion
• Easy to install and use
PAA in Bleached Pulp Storage TowerPAA in Bleached Pulp Storage Tower
1 1 -- 2 kg/2 kg/ tptp PAA PAA ≈ ≈ + 2 %ISO+ 2 %ISO
pH 5-6
StoragetowerD2-washer
White waterWhite waterWhite water
PAAPAA
pulp outpulp out
Pulp toPulp topapermachinepapermachineT: 55 °C
Effluenttank
Bleached pulpBleached pulpBleached pulp
Pulp fromPulp frompulp plantpulp plant
PAA in Bleached Pulp Storage TowerPAA in Bleached Pulp Storage Tower
Effect of PAA Charge on Brightness
0 1 2 3 4 5PAA, kg/tp
8989,5
9090,5
9191,5
92
Brig
htne
ss, %
ISO
softwood kraft pulp, initial Br. 89.8%ISO, kappa 0.4, viscosity 834 dm3/kg
PAA in Bleached Pulp Storage TowerPAA in Bleached Pulp Storage Tower
Effect of Time and Consistency on Brightness
0 20 40 60 80 100 120Time, min
89
89,5
90
90,5
91
91,5
92
Brig
htne
ss, %
ISO
10% Cs
4% Cs
Softwood kraft pulp, initial Br. 89.8%ISO, PAA @ 1.5 kg/tp
PAA in Bleached Pulp Storage TowerPAA in Bleached Pulp Storage Tower
0123456
Yellowness b* delta E*
swsw-PAAhwhw-PAA
Effect on Yellowness
PAA @ 2 kg/tp, final pH 5, 50°C, 60 min, Cs 10%
b* - yellow/blue axisE* - calculated difference in L,a*,b* space…corresponds to a visually perceived colour difference
PAA in Bleached Pulp Storage TowerPAA in Bleached Pulp Storage TowerMill TrialMill Trial
Stora Enso - Veitsiluoto Pulp Mill, Kemi
SoftwoodPAA @ 2.5 kg/tp avg. Br gain = 1.9 pts, std.dev. decreased by 30%
Brightening with Brightening with Peracetic Peracetic AcidAcidVeitsiluoto Veitsiluoto Pulp Mill TrialPulp Mill Trial
Reference PAA
Tensile index, Nm/g SR 20 SR 30
82.494.6
82.595.1
Tear index, mNm2/g SR 20 SR 30
9.17.9
10.08.6
Viscosity, dm3/kg 718 748
PAA: Effect on Microbial GrowthPAA: Effect on Microbial GrowthPAA added to ECF kraft bleached pulp storage chest
0
5
10
15
20
25
30
0 5 10 15 20 25 30 35 40Time, days
tota
l mic
robe
s, 1
0000
00/m
l
BrokeHeadboxBackwater
Reference period
Test period:PAA in storage chest
After PAA trial
PAA: Effect on Optical BrightenersPAA: Effect on Optical BrightenersImproved light emission at 457 nm
85
90
95
100
105
110
0 1 2 3 4 5 6OB A , k g/ tp (c om m erc ia l product )
R45
7 U
V on
PA A 0 k gPA A 1 k g
pine:birch:euca=20:60:20 8% consistency, 30 min., 40°C, pH 7-7.5Pulp dewatered prior to OBA addition
PAA PostPAA Post--BleachingBleachingBenefits at Fine Paper MachineBenefits at Fine Paper Machine
• Decreased demand for optical brighteners
• Stabilized surface charge on fibres
• Improved AKD/ASA size retention• size retention from 60-70% to 90-95%• decreased AKD content in white water• cleaner press section (fewer breaks, holes, and dirty spots)• decreased hydrolysis of AKD
• decreased formation of ketones• copy machines run more cleanly
• Biocide-free paper production