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Papermaking Chemistry –
Mini-Course Version
Today’s Topics
First 90-minute session
Introduction
Group exercise: Thinking about cost items
Different kinds of costs
Using paper chemicals cost-effectively
Break (30 minutes)
Second 90-minute session
“Rising retention aid costs” case study
Key concepts from the textbook
Discussion of “question card” issues
1
PaperCon 2011 Page 2772
Costs at “ACME Paper Co.”
are too high!
2
PaperCon 2011 Page 2773
“Dear cost-savings task
group, please consider…”:
4. Inefficient use of functional additives
(higher than necessary costs for
sizing, dry strength, wet strength,
opacity, retention aids, etc.)
3
PaperCon 2011 Page 2774
A Simple Way to Look at It
Receipts Price X
Production rate
X Fraction of uptime
4
PaperCon 2011 Page 2775
Let’s review how “ACME” is
doing…
Three paper machines / product areas:
5
PaperCon 2011 Page 2776
Recent Production Summary
Machine: 1
6
PaperCon 2011 Page 2777
Recent Production Summary
Machine: 3
7
PaperCon 2011 Page 2778
Things to Focus on during Group Work
PM#1 PM#2 PM#3
Fine printing Light-wt coated Paperboard
50-100% bl. kraft 80-100% TMP 50-100% OCC
0-50% DIP MOW Gap former, 0-30% MOW, etc.
Hybrid; size press 40-55 lb/3300 ft2 0-10% bl. kraft
Short runs (colors) On-machine ctd Multi-cylinder
Uptime: 79% Long runs Off-machine coat
Saleable: 90% Uptime: 79% Uptime: 96%
Limit: Drying Saleable: 98% Saleable: 95%
Issues: Transition Limit: Drives Limit: Drainage
Time, opticals Breaks, picking Strength, coverage
Examples:
• Administration
• Property taxes Also called…
• Insurance
• Debt “Indirect
costs”
8
PaperCon 2011 Page 2779
Definition: “Direct Costs”
Variable
Semivariable
Semivariable
Manufacturing labor
9
PaperCon 2011 Page 2780
Now it’s your turn; please suggest
categories for the following items:
DIRECT COSTS INDIRECT
Variable Semi-V. (Fixed)
Purchased pulp
Maintenance
Pension fund
Insurance
Water treatment
Social security
Depreciation
10
PaperCon 2011 Page 2781
Sales
Annual Cash Flow
Gross return (example)
Total cost
Fixed
Semi-
variable
Variable
expenses
11
PaperCon 2011 Page 2782
The Solution: Achieve
Specifications at Lower Cost
“That’s easy
for YOU to
say…”
Depreciation
Linear: An attempt to estimate the loss
in value of equipment
12
PaperCon 2011 Page 2783
Maintenance
costs
Cost
Depreciation on
capital “Life” of the
equipment
“Life” of the
equipment
Cost
TOTAL
Depreciation
Maintenance
13
PaperCon 2011 Page 2784
Today’s Topics
First 90-minute session
Introduction
Group exercise: Thinking about cost items
Different kinds of costs
Using paper chemicals cost-effectively
Break (30 minutes)
Second 90-minute session
“Rising retention aid costs” case study
Key concepts from the textbook
Discussion of “question card” issues
14
PaperCon 2011 Page 2785
Reasons Why Sizing Can Be
Inefficient CH OH 2
H
[
Water-loving O
nature of the O H
]
fibers
HO H O
OH
H
High surface
area of
fillers, etc.
of the size O R
O-
O O
O O-
AKD breaks down too, but not as fast. ASA hydrolyzate
Surface-
active agents
Oil-loving
Water-loving
15
PaperCon 2011 Page 2786
ASA Hydrolysis vs. pH
100
Active ASA Remaining (%)
pH = 3.5
90
pH = 5.0
80
pH=6
pH=8 pH=7
70
0 1 2 3 4
Time (hr)
Wasser, J. Pulp Paper Sci. 13 (1): J29 (1987), adap.
100 25 oC
80
60
35 oC
40
55 oC 45 oC
20
pH 3.5
0
0 1 2 3 4 5 6
Time of Exposure (hours)
Wasser, J. Pulp Paper Sci. 13 (1): J29 (1987), adap.
16
PaperCon 2011 Page 2787
Reasons Why Sizing Can Be
Inefficient
17
PaperCon 2011 Page 2788
Incident
light
Fiber
Filler Transmitted
particle light
18
PaperCon 2011 Page 2789
160
100 CaCO3
80
60
Filler Clay
40
20
0 5 10 15 20 25 30
Filler Content (%)
Middleton et al., J. Pulp Paper Sci. 20 (8): J231 (1994), redrawn.
19
PaperCon 2011 Page 2790
Key Cause of Poor Performance
of Strength Additives: Cationic
Polymer Neutralized by “Trash”
Cationic starch
Polyamidoamine-epichlorohydrin (PAAE)
20
PaperCon 2011 Page 2791
Optimize the Charge Demand
Case one: too negative
Strength Anionic
additive Neutralized:
colloids
(cationic) behaves
in pulp
like a filler
Neutralized additive
not efficiently
retained on fibers
Cellulose surface
21
PaperCon 2011 Page 2792
Optimize the Charge Demand
Case two: high charge additive used
22
PaperCon 2011 Page 2793
Starch
Paper wet film
Metering
blade
Starch
solution
Roll,
rubber-
covered
23
PaperCon 2011 Page 2794
A Little Case Study
Conventional Wisdom:
Reduce Starch Viscosity
Runs better at size press
Higher pick-up
24
PaperCon 2011 Page 2795
Enzyme
Viscosity (cPs)
Starch Solution
150
amount
reduced
100
50
0
Starch Pick-Up
(rel., dry basis)
25
PaperCon 2011 Page 2796
Today’s Topics
First 90-minute session
Introduction
Group exercise: Thinking about cost items
Different kinds of costs
Using paper chemicals cost-effectively
Break (30 minutes)
Second 90-minute session
“Rising retention aid costs” case study
Key concepts from the textbook
Discussion of “question card” issues
26
PaperCon 2011 Page 2797
Retention Aid Costs (relative)
3
0
5 4 3 2 1 0
300
Cationic Demand (µeq/L)
200
100
0
5 4 3 2 1 0
27
PaperCon 2011 Page 2798
Things that have Changed
• Speed increases (4 years ago)
• Basis weight decrease (time hard to pin down)
• Increase in brightness requirements (2.5 years ago)
• PCC use (2.5 years ago)
• Peroxide bleaching (2 years ago)
• Fluorescent whitener in the coating color
• Broke content increased about 10%, in relative terms
• Overall increase in the amount of pulp produced
• Cationic demand increased over whole period, apparently
• Fresh water usage reduction (last 13 months)
• No change in retention aid brand, type, or target FPR .
Suggestion
28
PaperCon 2011 Page 2799
Today’s Topics
First 90-minute session
Introduction
Group exercise: Thinking about cost items
Different kinds of costs
Using paper chemicals cost-effectively
Break (30 minutes)
Second 90-minute session
“Rising retention aid costs” case study
Key concepts from the textbook
Discussion of “question card” issues
29
PaperCon 2011 Page 2800
A Simple Way to Look at It
30
PaperCon 2011 Page 2801
Concept of Marginal Costs
“What is the cost of the final 1% of
production?
Sales
Annual Cash Flow
Semi-
variable
Variable
expenses
31
PaperCon 2011 Page 2802
Filled arrows show future Sales
profits, depending on how
Annual Cash Flow successful the “fix” is.
Gross return (current)
Variable
expenses
32
PaperCon 2011 Page 2803
Using a paper machine is
something like renting a car…
Driver labor
Gas materials
Cost of
materials
used (in
receiving) Cost
per unit
Direct labor, time
}
including
fringes
Time
“Use rate”
for facilities
employed
33
PaperCon 2011 Page 2804
Refining and high levels of fines
can result in slow dewatering.
1. Increased effective surface area (S).
dQ 1 (1 – C )3 1
=
dt K S2 C2 µ
34
PaperCon 2011 Page 2805
Canadian Standard Freeness
4 Blank
35
PaperCon 2011 Page 2806
Vacuum Dewatering vs. Polymers
22 News Blank
furnish
0.05% PEI
Dryness (%)
18
0.1% PEI
0.05% PEI &
14 0.025% or
0.05% AnPAM
10
0 126 18 24 30
Time (sec)
Britt & Unbehend, Tappi J. 68 (4): 104 (1985), adapted
M. Hubbe
36
PaperCon 2011 Page 2807
Dewatering vs. Polymer Use
Additive Consistency Consistency
on wire (%) after couch (%)
None 4.4 16.3
PEI copolymer,
2. Create positively charged
patches for electrostatic { poly-DADMAC,
polyamines, etc.
attractions.
Cationic PAM or
3. Bridge with high-mass
retention aids. { dual (high-cationic,
then anionic PAM)
4. Use microparticles (see Colloidal silica,
later discussion).
{ bentonite,
micro-polymer
37
PaperCon 2011 Page 2808
Highly Cationic Drainage Aids
Fibrillation
Before
Well-
beaten
fiber Dispersed fines
Fibrils collapsed
After to surface
Bound
fines
High-cat.
additive M. Hubbe
M. Hubbe
38
PaperCon 2011 Page 2809
Further Evidence of Patch
Mechanism
M. Hubbe
Flocs form again with ~ same strength.
80
PEI mass =1000-25,000
g/mole
Drainage (oSR)
60
40
PEI mass =
25k to 106 g/mole
20
0 0.02 0.05 0.1 0.2 0.5 1.0
Dosage of mod. PEI (% of dry pulp)
Ström & Kunnas, Nordic Pulp Paper Res. J. 6 (1): 12 (1991), adapted
39
PaperCon 2011 Page 2810
A. Fibrils B.
After cationic
polymer addition
Pores Pores
Fiber Surface Fiber Surface
Colloidal anionic
silica or bentonite
Pressure White-
screens water
High-mass
cationic
PAM copolymer or Thick-
cationic starch stock
40
PaperCon 2011 Page 2811
Microparticle systems differ from
traditional retention aids.
They involve tiny, three-dimensional,
negatively charged particles having strong
interaction with cationic polymers.
Montmorillonite (bentonite)
Colloidal Face
silica Edge
Sol
Gel
Micropolymer
0 20 40 60 80 100 200 nm
Size Scale
41
PaperCon 2011 Page 2812
Silanol
group Dissociated
form
O OH OH
O
Si Si OH
Si
O Si O
O O O Si OH
O
O Si Si
SiO2 Surface O
O
silica
300
0.2% silica
No silica
200
5 010 15 20 25
Cat. Amylose (kg/ton)
Carlson, Proc. 24th EUCEPA Conf., 1990, 161, adapted
42
PaperCon 2011 Page 2813
Facts about Microparticle Systems
145 100
First-Pass Retention (%)
Machine Speed (m/min)
140 95
135 90
130 85
125 80
Blank Hi-Cat.+ Enzyme Enzyme All Three
Ret.Aid + Ret. Aid Additives
Moran, Pulp Paper 70 (9): 119 (1996), redrawn
43
PaperCon 2011 Page 2814
Why Entrained Air Can Slow the
Paper Machine
44
PaperCon 2011 Page 2815
Ways to Judge whether an
Investment is Worthwhile
Payback: How long will it take for the
increased profits to pay for the investment?
Return on investment: What percentage
rate of return will this project earn?
Net present value: Considering the time-
value of money, how much is the whole
project worth when the decision is made?
In summary…
Speeding up usually pays, if you can do
so without hurting your cost situation.
45
PaperCon 2011 Page 2816
Process Additives
“Used to make the machine run better”
{
Retention aids
Examples Biocides
Defoamers
Deposit control aids
Approaches to be Considered
46
PaperCon 2011 Page 2817
Addition Point Locations
Maximize mixing
47
PaperCon 2011 Page 2818
Chemical Feed Calibration
Graduated
cylinder
To feed
point
Supply
tank
Valve Pump
48
PaperCon 2011 Page 2819
Online Process Control
Step 1: There must be a strong, reliable
relationship between the controlled
variable and the monitored variable!
0.7
Reten. Aid flow
0.5 0.6
Tray solids
(%)
0.5
0.4
0 1 2
Time (hours)
Ruetz et al., Wochenblatt Pap. 126 (3): 88 (1998) adapted
49
PaperCon 2011 Page 2820
On-line Control of Tray Solids
White Water Solids (%) 0.12
0.07
S.D. =
Standard 0.016
dev. = 0.10
Start of on-line control
0.02
0 50 100 150 200
Time (days)
Ruetz et al., Wochenblatt Pap. 126 (3): 88 (1998), adapted
50
PaperCon 2011 Page 2821
Tray solids (%)
0.5
Control off
0.4
Set-pt. change
0.3
10 Control on
Reten. aid
flow (rel.)
8
6
4
0 100 200 300
Time (hours)
Artama et al., in Use of Minerals in Papermaking, 1997, adap.
51
PaperCon 2011 Page 2822
Control
Frequency (relative) On
No Control
52
PaperCon 2011 Page 2823
Relative Costs of Water Removal
1000
100
Drying
10
Press
1
Forming
100 10 1 0.1
Parts Water Remaining
Data from: McGregor, Knight, Paper Technol. 37 (8): 31 (1996).
Evaporative drying
Vacuum pumping
53
PaperCon 2011 Page 2824
More subjects are covered in the
textbook:
Solids losses vs. retention aid costs
Downtime avoidance costs
Retention aid efficiency
Reduction in furnish costs
hubbe@ncsu.edu
kasyking@att.net
54
PaperCon 2011 Page 2825