Lecture 1/2: Introduction to chemical pulping

Debarking and Chipping

o Bark can be used as fuel
o Chips must be consistent in size
Between 0.5-1 long
Wood Deterioration
o Wood decay requires oxygen and moisture (>20% MCod)
o Remove both to slow degradation
o <20% is unfeasible
Chip pile degradation
o Tall chip piles
o FIFO (first in first out)
o 1% loss to decay/month
Debris
o Debris can impair the machinery and increase wear on equipment
Screening
o Overs: too big
o Accepts correct
o Fines: chips too small
Chip quality issues: Wood Species
o Softwoods: stronger pulp from longer fibers
High lignin, so low yield unfortunately
o Hardwoods: good printing paper
Smooth surface
Chip moisture
o Cannot be too dry! Or else cooking chemicals cannot penetrate
Chip quality issues
o Chips too thick: undercooked
o Chips too small, it will be overcooked
Wood Density
o Hardwoods more dense than softwoods
Thicker cell walls
o Low density wood produce flexible fibers and give high strength and high paper
density
Juvenile wood
o Is shitty: too much lignin, low density, low cellulose content, more rxn wood
Earlywood versus Latewood
o Earlywood: thin walled, large libers, strong paper
o Latewood: high density, less strength
Heartwood versus sapwood
o Heartwood sucks, lots of lignin and extractives. Dark color is a problem
Reaction wood
o Compression wood sucks (dark color)
o Tension wood: lower strength, higher yield, and brightness
Decayed wood
o More fines, lower density
o Low cellulose, low pulp strength

Batch Digesters
o Large pressure reactors (6-8 on a paper mill)
o Direct heating or indirect heating with forced circulation
Continuous digesters
o Continuous flow with multiple zones
Charging
Impregnation
Heating
Cooking
Basic process steps:
o Digester filled with chips and cooking liquor
Steam packing: more efficient, higher packing density
Presteaming
Improved impregnation
More even liquor distribution
o Cooking (90 minute ramp to 175C)
External heating from circulating liquor from HXC
Turnover rate: 10 minutes
Uniform heating and liquor distribution
Internal Heating
Steam goes from bottom of the digester
Heat transfer through convection
Problem of non uniform temperature gradients
Diffusion limitations
Optimal in water saturated wood
Effective across the grain, short distances
Gas must be released or else non condensable gases will buid
o Cooking maintained for 20-45 min
o Contents discharged to blow tank
Hot blowing
Pressure reduction causes temperature reduction and a rapid
separation of fibers from chips
Cold blowing (most optimal)
Lower steam demand
Pulp viscosity and strength is improved








Lecture 3

Continuous Reactors
o Impregnation Zone
o Cooking Zone
o Washing Zone
Chip and Liquor Charging
o Chips are delivered through a chip meter
Rotating wheel which meters chips
Chips are presteamed for 2-3 minutes at 103-124 kPa
o High Pressure Feeder
Necessary since the digester is under high pressure
Chips are impregnated with white liquor
o Chip and Liquor Charging
Chips/liquor are added through a screw/strainer
Excess liquor is removed
New white liquor is replaced and added at the top of the plug
Impregnation Zone
o 45 minutes
o Temperature is ramped from 105 to 130
Heating Zone
o Rapid heating to 160-170C
Cooking Zone
o 1-2 hours at 160C-170C
o Liquor is constantly being removed through screens and pumped back into system
Washing Zone
o Rapid cooking to 130C using a countercurrent process with black liquor
o Washing takes 1.5 hours
Batch reactors
o More flexible and specific
o Less down time, production loss
o Expandable
o Easier to start/shut down
Continuous reactors
o Less steam requirements = lower power
o Easier to control non-condensable gas buildup
o Compact
o Steady state flow








Lecture 4/5 (must review more, many technical terms)

Definition of terms
o White liquor: NaOH, sodium sulfide
o Black liquor: waste liquor, lots of organics and impurities
o Green liquor: partially recovered kraft liquor
White liquor Digester Black Liquor recovery furnace green liquor lime
kiln white liquor repeat
White liquor: 53% NaOH, 21% sodium sulfide
Black liquor: 36% sodium carbonate, 19% sodium sulfide
Typical composition:
o NaOH, active
o Na2S: active
o Sodium carbonate, inactive, imcomplete caustisizing
o Sodium sulfite, inactive, incomplete reduction
o Sodium sulfate, inactive, incomplete reduction
o Sodium thiosulfate, inactive, oxidation of sulfide
Sulfidity and causticity

Lecture 6/7
Free Phenolic OH Etherified OH
Linkage OH- HS- OH- HS-
B-O-4 No Yes Yes No/Yes
a-O-4 Yes No No No
B-5 No No No No
B-B No No No No
B-1 No No No No
5-5 No No No No
4-0-5 No No No No
Dont forget about condensation reactions with a-5, B-1, and formaldehyde
















Lecture 8:
Carbohydrate reactions
o Same amount as lignin reacts, just slower
Peeling Reaction
o Isomerization
o Enediol formation
o B-alkoxy elimination
o Tautomerization
o Benzylic acid rearrangement
o Yields an isosaccharinic acid
Stopping Reaction
o 1,2-enediol formation
o B-hydroxy elimination
o Tautomerization
o Benzylic acid rearrangement
o Yields a metasaccharinic acid
Cleavage of glycosidic bonds
Glucomannans
o Very unstable to peeling
o Responds very quickly to peeling
Cellulose
o Chain density decreases
Xylans
o Resistant to peeling, losses are due to dissolving
o Two temperature dependent mechanisms
<100C, galacturonic acid units resistant
>100C, glucuronic acid units converted to hexeuronic acids (more
resistant to peeling)
Cellulose/Glucose
o Undergo peeling but only results in small losses
o Glycosidic cleavage is more of a problem
More reducing ends
Loss of chain strength
o Dissolution not an issue












































Lecture 9
Understanding the kinetics of pulping
o Species, source
o Chemical charge
o Temperature
Effect of Wood Species
o Hardwoods are easier to delignify (less lignin content)
Effect of Effective Alkali on Kraft Pulping
o Increasing EA, increase rate/degree of delignification
Increase concentration of EA
Increase volume of White Liquor
o Concentration change may have a larger effect than volume change
o Increasing EA charge will increase delignication, but will have a lower pulp yield
o Initial: Diffusion limited, Bulk: Temperature
o EA effects Kappa
Effect of Increasing EA on Pulp Properties
o Cooking time shortened
o Pulp yield at kappa reduced
o Xylan content of pulp reduced while glucomannan content increased
o Brightness inceased
o Mechnical properties of pulp changed
Glucomannans arent affected by EA
o Peeling reactions arent sensitive to OH concentration
Xylans are stable at the beginning but will quickly undergo
o Hydrolysis
o 2
nd
peeling
Effect of sulfidity
o Sulfidity: zero order in initial delignification
o Important in bulk delignification
o Does not react with carbohydrates
o Sulfidity is great! Except for the smell
Higher pulp yield
Faster reactions
Less carb. Degradation
Faster delignification