EPA-R2-73-184 Environmental Protection Technology Series
APRIL 1973
State-of-the-Art Review of Pulp
and Paper Waste Treatment
Office of Research and Monitoring
U.S. Environmental Protection Agency
Washington, D.C. 20460
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RESEARCH REPORTING SERIES
Research reports of the Office of Research and
Monitoring, Environmental Protection Agency, have
been grouped into five series. These five broad
categories were established to facilitate further
development and application of environmental
technology. Elimination of traditional grouping
was consciously planned to foster technology
transfer and a maximum interface in related
fields. The five series are:
1. Environmental Health Effects Research
2. Environmental Protection Technology
3. Ecological Research
4. Environmental Monitoring
5. Socioeconomic Environmental Studies
This report has been assigned to the ENVIRONMENTAL
PROTECTION TECHNOLOGY series. This series
describes research performed to develop and
demonstrate instrumentation, equipment and
methodology to repair or prevent environmental
degradation from point and non-point sources of
pollution. This work provides the new or improved
technology required for the control and treatment
of pollution sources to meet environmental quality
standards.
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April 1973
STATE-OF-THE-ART REVIEW
OF
PULP AND PAPER WASTE TREATMENT
By
Dr. Harry Gehm
Contract No. 68-01-0012
Projects 12040 GLV
12040 HAR
Project Officer
Ralph H. Scott
Pacific Northwest Environmental Research Lab,
EPA - NERC
Corvallis, Oregon 97330
Prepared for
OFFICE OF RESEARCH AND MONITORING
U.S. ENVIRONMENTAL PROTECTION AGENCY
WASHINGTON, D.C. 20460
For sale by the Superintendent of Documents, U.S. Government Printing Office, Washington, D.C. 20402
Price $2.86 domestic postpaid or $2.50 GPO Bookstore
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EPA Review Notice
This report has been reviewed by the Environmental
Protection Agency and approved for publication.
Approval does not signify that the contents
necessarily reflect the views and policies of the
Environmental Protection Agency, nor does mention
of trade names or commercial products constitute
endorsement or recommendation for use.
n
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ABSTRACT
This report sets forth the state of the art in the treatment of pulp
and paper mill wastewater as it stands in 1971. In order to lay a
background for the sections on treatment, a review of both the general
economic position of the industry as a whole and the major production
processes is included. Such a background is needed since a considerable
degree of loss control is practiced within the processes and water
recycling is an almost universal practice in this industry.
Included also is a review of the water quality problems which the applied
treatment processes are designed to rectify. Performance data for treat-
ment processes and systems are presented together with a review of the
applicability of common analytical methods to the measurement of waste
characteristics and treatment effectiveness. The techniques used to
monitor waste fTowages for control purposes and as means of recording
treatment efficiency are included.
Finally, the remaining problems relative to control and treatment of
pulp and paper mill spent process waters are pointed out. Research and
development needs directed toward solving these problems are defined in
the light of such programs which are currently underway.
This report was submitted in fulfillment of Contract No. 68-01-0012 under
the partial sponsorship of the U. S. Environmental Protection Agency.
Questions concerning this report should be directed to Dr. Harry Gehm,
WAPORA, Inc., 6900 Wisconsin Ave. NW, Washington D. C., 20015.
n i
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CONTENTS
Section Page
I RECOMMENDATIONS AND CONCLUSIONS .... 1
II INTRODUCTION 7
III PRODUCTIVITY AND ECONOMICS OF THE INDUSTRY ...... 9
IV WATER QUALITY PROBLEMS OF THE INDUSTRY 25
V GENERAL PROCESSES EMPLOYED FOR EFFLUENT
MANAGEMENT AND TREATMENT 35
VI ADVANCED WASTF TREATMENT 53
VII WATER REUSE AND RECLAMATION 67
VIII THE HANDLING, TREATMENT, AND DISPOSAL OF SLUDGE ... 75
IX TREATMENT IN PUBLIC FACILITIES 95
X ORIGIN OF SPECIFIC MILL EFFLUENTS AND RESULTS
OBTAINED BY TREATMENT 99
Wood Preparation 99
Groundwood Pulping 110
Neutral Sulfite Semi-Chemical Pulping 116
Kraft and Soda Pulping 124
Acid Sulfite Pulping 132
Pre-Hydrolysis 139
Kraft and Sulfite Pulp Bleaching 141
Chemicals Used in Cooking Wood and Bleaching
Chemical Pulp 144
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CONTENTS (Cont'd)
Section
Deinking Pulp 150
Manufacture of Paper '.'.'.'.'.'. 154
Waste Paperboard Mills '..'... 160
Building Products . . . . 165
Miscellaneous Pulps ....'.... 168
Other Mill Effluents , 176
XI COST OF TREATMENT 177
XII EVALUATION OF COMMON TESTING PROCEDURES FOR
PULP AND PAPER MILL EFFLUENTS . 181
XIII EFFLUENT MONITORING . 187
XIV ACKNOWLEDGMENTS 195
XV REFERENCES 197
XVI APPENDICES 223
'--
1. Paper and Paperboard Products, Imports,
Exports, and New Supply . . . 224,
2. Apparent Consumption of Paper and Board
by Grade, 1920-66 225
3. Apparent Consumption of Wood Pulp.
by Type, 1920-66 226
i • ' , ~ ' >
4. Year-End Paper and Paperboard Capacity,
1970-74, Summary by £roup 227
5. Paper and Paperboard, Additions 1956-71,
Additions (committed & tentative), 1972-74 ... 228
6. Paper and Paperboard .Capacity by Census
Divisions . . . 229
7. U.S. Paper and Board Per Capita Consumption ... 230
8. Paper and Allied Products Industry,
Profit and Loss Data 231
9. List of Mills by Product and State 233
vi
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FIGURES
PAGE
1 PERCENT TOTAL SUSPENDED SOLIDS REDUCTION
EFFECTED BY SETTLING 39
2 BOD RATES OF SUSPENDED AND DISSOLVED ORGANIC MATTER ... 41
3 BOD5 REDUCTION EFFECTED BY SETTLING 42
4 STATISTICAL COMPARISON OF PRIMARY TREATMENT
PERFORMANCE—BOD REMOVAL . 43
5 EFFECT OF STORAGE TIME ON BOD REDUCTION 45
6 EFFECT OF TEMPERATURE ON BOD REDUCTION IN AERATED
STABILIZATION BASINS 48
7 STATISTICAL COMPARISON OF SECONDARY TREATMENT
EFFICIENCY—BOD REMOVAL 50
8 INTERSTATE CONTAINER CORPORATION COLOR
REMOVAL PROCESS 58
9 MASSIVE LIME PROCESS FOR COLOR REMOVAL 60
10 CONTINENTAL CAN CO., INC., COLOR REMOVAL PROCESS 61
11 LIME MUD PROCESS FOR COLOR REMOVAL 62
12 ADVANCED WASTE TREATMENT SYSTEM EMBRACING COLOR
REDUCTION AT A LINERBOARD MILL 63
13 TREATED WASTE COLOR VS. LIME CONCENTRATION 64
14 TREATED WASTE COLOR-PPM ALPHA UNITS COD & BOD 66
15 THICKENING CURVES FOR VARIOUS SLUDGES 78
16 EFFECT OF ACTIVATED SLUDGE ON DEWATERING
BOARDMILL SLUDGE ....... 85
17 SLUDGE CAKE CONDITIONS REQUIRED TO SUPPORT COMBUSTION . . 92
18 MULTI-PATH DIAGRAM OF MECHANICAL THICKENING,
DEWATERING, AND DISPOSAL OF SLUDGES 93
vii
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FIGURES (Cont'd)
PAGE
19 LONG-TERM BOD OF BARKER EFFLUENT (AFTER FINE SCREENS) . . 105
20 WET BARKING PROCESS DIAGRAM 107
21 SETTLING RATE OF BARKER SCREENING EFFLUENT 108
22 TREATMENT OF WET BARKING EFFLUENTS 109
23 GROUNDWOOD PULPING PROCESS DIAGRAM Ill
24 REFINER GROUNDWOOD PROCESS DIAGRAM 114
25 NEUTRAL SULFITE SEMI-CHEMICAL PULP PROCESS DIAGRAM .... 117
26 BOD LOAD OF NSSC PULPING 118
27 SUSPENDED SOLIDS LOSSES FROM NSSC PULPING 119
28 WATER RECYCLE IN AN NSSC MILL 121
29 RELATIONSHIP BETWEEN TOTAL SOLUBLE SOLIDS, BOD,
CONDUCTANCE, AND LIGHT ABSORPTION IN KRAFT
PULPING DECKER FILTRATE EFFLUENT 126
30 KRAFT PULPING PROCESS DIAGRAM 130
31 KRAFT RECOVERY SYSTEM PROCESS FLOW DIAGRAM 131
32 ACID SULFITE PULPING PROCESS DIAGRAM (CALCIUM
OR AMMONIA BASE) 136
33 MAGNESIUM BASE SULFITE RECOVERY SYSTEM PROCESS DIAGRAM . . 137
34 FOUR-STAGE PULP BLEACHING PROCESS DIAGRAM 142
35 DEINKING WASTE PAPER PROCESS DIAGRAM 152
36 FOURDRINIER PAPER MACHINE PROCESS DIAGRAM 156
37 WASTE PAPER BOARD MILL PROCESS DIAGRAM 161
38 INSULATING BOARD, BUILDING BOARD, AND HARDBOARD
PROCESS DIAGRAM 169
39 SPECIALTY PULP MILL 172
vm
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FIGURES (Cont'd)
PAGE
40 RELATION BETWEEN TOTAL DISSOLVED SOLIDS AND BOD,
IN DECKER SEAL PIT WATER 7 188
41 BOD, IN RELATION TO LIGHT ABSORBENCE KRAFT MILL
DECKER SEAL PIT WATER 189
42 BOD, IN RELATION TO LIGHT ABSORPTION OF NSSC
WHITE WATER 190
43 RELATIONSHIP BETWEEN BOD, AND LIGHT ABSORBENCE
OF EVAPORATOR JET CONDENSER WATER 191
44 RELATIONSHIP OF TOTAL DISSOLVED SOLIDS TO CONDUCTANCE
OF KRAFT DECKER SEAL PIT WATER 193
ix
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TABLES
Page
1 Waste Paper Requirements . 19
2 Per Capita Consumption of Paper and Board 21
.3s Sales vs. Profits of Major U.S. Paper Manufacturers ... 24
4 Values for Color Discharges from Various Pulping
Processes 54
5 Unit Process Flow and Color Distribution in
Individual Kraft Pulping Effluents 54
6 Typical Physical and Performance Data for a Tubular
Reverse Osmosis Unit Operating on Wastewater from an
NSSC Pulp and Paperboard Mill 72
7 Performance of Mill Installations of Gravity Thickeners . 79
8 Thickener Loading Parameters 80
9 Continuous Vacuum Filtration 83
10 Centrifuge Installations 88
11 Mechanical Pressing of Sludge Cake 89
12 Mills Discharging to Public Sewage Treatment
Facilities 96
13 Mills Considering Discharge to Public Facilities 97
14 Oxygen Demand After Seven Days Contact with Wood 100
15 Wood Washing 100
16 Analysis of Wet Drum Barking Effluents 102
17 Analysis of Hydraulic Barking Effluents 104
18 Sewer Losses from Wet Barking Effluents 110
19 Effluent Characteristics of Stone Groundwood
Pulp Mills 112
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TABLES (Cont'd)
Page
20 Effluent Characteristics of Refiner Groundwood
Pulp Mills 112
21 Effluent Characteristics of Cold Soda and Chemi-
Groundwood Pulps 113
22 Neutral Sulfite Corrugating Boardmi11 Effluent
Characteristics .......... 122
23 Methods of Handling NSSC Spent Liquor in the U.S 123
24 Effluent Flow and Pollution Loads from Calcium Base
Acid Sulfite Pulp Mills (without liquor recovery) .... 135
25 Effluent Flow and Pollution Loads from Soluble
Base Acid Sulfite Pulp Mills (with liquor recovery) ... 138
26 Biological Treatment of Ammonia Base Acid Sulfite
Pulp Mill Effluents 139
27 Volume and Characteristics of Kraft and Sulfite Bleaching
Wastes 143
28 Chemical Composition at Various Points in
Causticizing 146
29 Southern Pine Kraft Liquor 147
30 Range of Caustic Soda Dosage in Relation to the
Alpha Cellulose Content of the Bleached Chemical Pulps . . 148
31 Deinking Mill Effluent Characteristics 151
32 Biological Oxidation of Deinking Wastes 154
33 Losses from Coarse Paper Manufacture 155
34 Losses from Fine Paper Manufacture ...... 157
35 Losses from Tissue Paper Manufacture 159
36 Waste Paperboard Mill Waste Loadings .... 162
37 Analysis of Waste Paperboard Mill Effluents 164
xi
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TABLES (Cont'd)
38
39
40
41
42
Treatment of Waste Paperboard Mill Waste
Results of Treatment of Building Board Mill Effluents . .
Load Distribution in Cook Liquors and Progressive
Page
166
170
173
174
175
xii
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ILLUSTRATIONS
Clarifier at Paper Mill 38
Vacuum Filter Recovering Fiber 82
Sludge Centrifuge Installations at a Pulp Mill,
Sharpies Corp 86
Sludge Incinerator, Reitz Manufacturing Co 90
Continuous Pulp Digester at a Kraft Pulp Mill,
Kamyr, Inc 125
Lime Kiln at a Kraft Mill, Allis-Chalmers 128
Integrated Kraft Pulp and Paper Mill and Effluent
Treatment Facilities, Boise Cascade Corp 133
Magnesium Base Sulfite Pulp Mill with Effluent
Treatment Plant, Weyerhaeuser Co 140
xi ii
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SECTION I
RECOMMENDATIONS AND CONCLUSIONS
A review of the body of this report combined with the author's intimate
contact with mill personnel leads to the following recommendations and
conclusions on the immediate situation of the pulp and paper industry
in maintaining and improving the quality of receiving waters with the
aid of the available technology.
Receiving Waters
Satisfactory methods are available for handling the problems accessory
to waste treatment and discharge, such as the removal of trash and the
control of foam from pulp and paper mill effluents. While biological
treatment can generally reduce the taste- and odor-producing capacity of
pulping wastes in receiving waters, this area is receiving additonal
attention by industry research groups. Since these tastes can be absorbed
by the skin of fish it is desirable to eliminate the substances which
create them. However, these substances rarely cause a problem in downstream
water supplies that cannot be controlled by available potable water
treatment techniques. When chemicals, such as hydrocarbons, used for
foam control, are responsible, the problem can be solved by changing the
foam control agent to one having a low taste and odor level and which
is not absorbed by aquatic organisms.
As pointed out by Gel 1 man and Blosser of the National Council for Air
and Stream Improvement, Inc. (NCASI), the bulk of the industry's effort
in pollution control has been directed toward the protection of fishing
resources, and water quality standards are to a large degree keyed to
the successful propagation, migration, growth, and harvesting of fish.
Because of control activities, the industry's wastes have played no
significant role in the annually-compiled fish kill statistics. Also,
control measures have largely eliminated slime growths on commercially
important fishing streams, and instances of the restoration of fisheries
through cooperative programs of fish ladder reconstruction, river stocking,
and effluent treatment have evidenced cooperative use of surface waters
for both manufacturing and fishing. Research on the all important
matter of aquatic productivity is well underway and is supported by both
the federal government and the industry. Extension of such studies could
shorten to some degree the time in which answers to the relationships
between effluent quality and productivity are better established.
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Analyses
The matter of bacterial quality of waters receiving pulp and paper mill
effluent is a very complex matter as pointed out in the body of this
report. It is not possible to judge potable quality of such waters by
even the confirmed E. coli index, and existing disinfection methods are
not satisfactory for pulp mill effluents and attempts to use them could
give rise to tastes and odors. It appears that complete segregation
and treatment of sanitary wastewaters from process sewers represents
the best method of protecting receiving waters from contamination by
pathogenic organisms.
In any program involving effluent standards, the importance of the method
of analysis to be employed for judging effluent quality parameters
arises. It has been pointed out frequently, by both the pulp and
paper industry and state regulatory agencies, that some of the techniques
set forth in "Standard Methods for the Analysis of Water and Waste Waters,
which are commonly used for effluent analysis, are unsuitable for use
in analyzing pulp and paper mill wastes. This applies particularly to
the determination of solids. In order to overcome these difficulties, various
organizations involved in effluent control have developed special techniques
which they believe provide more precise measurements than "Standard Methods"
for general use or for application to particular wastes. It is strongly
recommended that a survey be made of the methods employed throughout the
country for determining the various classes of solids present in pulp
and paper mill wastes. A critical examination could lead either to a
selection of specific existing methods or recommendations on the development
of superior techniques through a research program involving intensive
industry participation.
Clarification
Satisfactory methods are available for removing the bulk of the suspended
solids from most pulp and paper mill effluents. However, some wastes,
such as those from the production of filled and coated papers and from
waste paper reclamation, contain finely dispersed pigments and debris
which in very low concentration impart opalescence to receiving waters.
Present treatment methods are not adequate to handle this problem. Even
where applied, chemical coagulation fails to cope with it since this
process cannot produce the practically 100 percent reduction in suspended
matter required to remove the opalescence. A similar haze in the effluent
can remain after biological treatment. In other cases coagulants do not
function well at all or require excessive dosage.
Fine suspended matter of both organic and inorganic nature remains in
dispersion and affects the light absorption capacity of the water adversely
even at very low total suspended solids levels. The effect these effluents
have on receiving streams is strictly one of aesthetics and depends upon
the initial appearance of the receiving stream, light, and bottom conditions
as well as general surroundings such as vegetation along banks. The ordinary
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methods for measurement of turbidity and color do not yield results which
can be considered a reliable index of appearance.
t>
From the above observations it appears that there is a need for finding
means for clarifying some pulp and paper mill effluent to an extremely
high degree without excessive capital or operating cost. Techniques
applied to date, such as diatonite filtration and rapid sand filtration,
failed for one reason or another and the polyelectrolyte coagulants have
not provided an answer to this problem.
Color
Another problem associated with aesthetics is that of color of pulping
and bleaching effluents. While the industry and EPA are carrying on
an extensive program on the removal of color, little is being done to
clarify the interpretation of progressive stream standards which take
cognizance of the natural color of particular receiving waters. Color
consists largely of non-degradable substances but represents only
a part of this class of materials present in pulping and bleaching
wastes. A clarification of the significance of such substances in relation
to water uses is urgently needed so that future water quality standards
and treatment needs can be established intelligently.
This also has bearing on water reclamation for mill reuse so that
waste treatment costs can be optimized. Greater knowledge of the
water quality requirements for the various processes of pulp and paper
manufacturing, particularly for bleaching, is needed for proper assessment
of approaches to reclamation.
BOD Reduction
This industry has developed and applied biological treatment to a high
degree and methods for its application are well advanced. There appears
to be no problem in obtaining BOD reductions of 85 percent during
the critical seasons by these methods. Higher degrees of removal have
been observed periodically but are not well documented. It appears that
special measures may need to be taken to retain the fine biological floe
lost to the effluent if BOD reduction values on the order of 95 percent
are to be obtained consistently, as may be desirable in some circumstances.
These losses are due to bulking problems in the activated sludge process
and dispersed growth in the case of aerated stabilization basins.
Treatment and Disposal of Residues
The primary problem in treating liquid wastes from the pulp and paper
industry is the processing and ultimate disposal of residues resulting
from treatment processes. At present these are largely sludges of
various types. These will be joined more and more by raffinates and
brines as higher degrees of waste treatment and water reclamation are
practiced in the future. Frequently, the choice of treatment methods
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to be employed at a particular installation is predicated upon the
teasibility of handling the residues of treatment and, in some instances,
the obtainable degree of purification is predicated upon the existence
of adequate means for sludge handling. Even where successful and acceptable
methods for handling these residues are available, the cost of doing so
runs as high as 50 percent of the entire cost of treatment.
One of the major problems in residue handling is that of the failure
of some sludges to thicken to a degree that they can be dewatered to
the extent necessary for further processing and ultimate disposal.
Examples of sludges which do not thicken mechanically to a practical
degree are biolgical sludges resulting from activated sludge treatment
of the wastes, water treatment plant sludges, groundwood pulping fines,
lignin residues, and slurries obtained on clarification of some white
paper mill effluents. Some of these will not thicken mechanically to
more than 2 percent solids. Lacking a free draining sludge to blend
with these, thus rendering them dewaterable by common techniques, there is
no adequate or economically feasible method for disposing of them.
Stabilization methods, such as digestion, heat treatment, or direct to
land disposal, have been proven inadequate or are obviously too costly
to warrant consideration.
Also included in this category are sludges from some paper recycle
operations. These sludges are true hydrogels and the problem of removal
of water of imbibition from these colloidal systems has been the
subject of considerable study by Zettlemoyer and many others. It appears
obvious, however, that unless means are found for releasing a substantial
portion of the water of imbibition from such hydrogels, at a cost
compatible with those required for treatment of the particular waste
under consideration, a major problem will continue to exist. An adequate
solution to the hydrogel problem presumes that the energy requirement
involved, whether it be applied in the form of heat or chemicals, be within
reasonable bounds and not give rise to serious secondary problems.
The need for more intensive basic surface chemistry studies in this area
cannot be overemphasized, since until the thermodynamics of the problem
are better defined it is unlikely that any appreciable progress will be
made toward its solution. Edisonian research and revival of long dormant
techniques incorporating refinements in machinery and conditioning
agents have not shown signs of achieving a solution, and the research
efforts presently being expended in this area are deemed highly inadequate.
A second class of residue which presents major difficulties are those
which are dewaterable by commonly applied methods but which produce
cakes high in ash content which cannot be incinerated. These can be
calcined, but the costs and problems accessory to this process are
prohibitive. NCASI is funding a research and development program directed
toward developing improved disposal methods for these sludges, particularly
land reclamation.
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A third type of treatment residues which will undoubtedly become a
major future problem are those consisting mainly of dissolved salts
and organics. These result from demineralizing water, ash from
incineration of spent process liquors (such as pulping wastes), and
from water softening and effluent treatment in the reclamation of spent
process waters. If the elimination of discharge of materials to surface
waters is ever to be achieved, better means for disposing of these
residues is mandatory.
The magnitude of the problems set forth above are exemplified in the
recycling of waste paper. This frequently results in sewer losses
approximating 50 percent of the bale weight of the waste reclaimed and
the suspended solids losses from large integrated pulp and paper mills
frequently approach 60 tons of dry solids daily. With the increasing
interest in recycling of waste materials, the urgency of the problem
becomes very evident.
While there has been, and presently is, considerable research and developm
effort by EPA, its predecessor agencies, and industry directed toward
the solution of these problems, it appears that it is inadequate
considering the proportions of their increasing magnitude and the
interdependence of water quality improvement on residue handling and
disposal. Further, there has not been a coordinated effort involving
the several facets of the residue problem. Thus it appears of major
importance that all current studies be tabulated and examined as to
their adequacy of approach to the overall problem so that the desirability
of specific areas of research, both basic and applied, can be established.
This could be followed by a designation of a major research area by EPA
and of specific projects to fill in the gaps in the present fragmented
program. Coordination with interested industry and qualified contractors
would assist in determining the best means of cooperative program
implementation.
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SECTION II
INTRODUCTION
The Environmental Protection Agency retained WAPORA, Inc. late in 1970
to prepare a state-of-the-art document dealing with the treatment of
liquid effluents produced from the manufacture of pulp, paper, and
related products such as building boards and felts of wood origin. This
project was designated as contract number 68-01-0012.
Because of the large number of processes and products involved, together
with the fact that day-to-day process variations frequently occur at any
single mill, no attempt has been made to cover all products separately.
Rather than attempt this insurmountable task, products have been classified
into recognized groups, and ranges of effluent characteristics set forth
for these.
Since the response to unit treatment processes of the spent process
waters from the manufacture of these classes of product is similar, a
section covering general treatment methods and their performance is
included in addition to the information presented on the response of
specific wastes to treatment as indicated by field performance data.
Since sludge handling and disposal are accessory to treatment, a section
on these practices is included. Similarly, as some paper and paperboard
mills employ public sewage systems to dispose of their process wastewaters,
this matter is also discussed and the exclusiveness of this practice
pointed out.
Cooperation of the industry and its associations in supplying information
and critical review of sections of this report was obtained and was
indispensable to the project. Data were also made available by state
pollution control regulatory agencies as well as the EPA.
A special attempt was made to annotate the report and a very extensive
bibliography is included. While this is by no means complete, it does
include for the most part the most pertinent references on each subject.
Some of these in themselves are summary reports and are thoroughly
referenced and others are critical reviews of the literature.
It is believed that this report will prove helpful to the industry in
selecting waste treatment systems which will enable it to meet water
quality standards. It will also point out to regulatory agencies what
can be accomplished by waste treatment and control as well as the
limitations of various types of treatment. In the recommendations and
conclusions the authors have stated what they believe to be the areas
of research and development most needed to improve water quality
through effluent treatment. Recommendations on problems accessory to
treatment such as sludge handling and disposal are included.
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SECTION III
PRODUCTIVITY AND ECONOMICS OF THE INDUSTRY
Growth trends in the paper and allied products industry as projected by
the Economics Department of the American Paper Institute (API), the
U.S. Forest Service, and the Bureau of Domestic Commerce (BDC) are set
forth below. It is to be noted, however, that the Forest Service fore-
casts were made in 1967 and those of the BDC in 1970. These are the
latest available to the contractor, although revisions are in progress
in both agencies for 1972 publication.
The trends projected by API Economics Department were obtained from
the various papers presented to industry groups and to the Food and
Agriculture Organization (FAO) of the United Nations during 1971 (1).
They are, however, subject to interpretation and qualification as
discussed in References (2,3,4).
Because of the current economic cloudiness surrounding the growth rate
of all U.S. industry, and particularly the pulp and paper segment of it,
the contractor will not attempt to pass judgment on the present reliability
of these projections.
They are, of course, pertinent to a state-of-the-art review of the
industry's waste treatment as an indicator of the quantity and kinds of
wastes to be treated and water requirements in the coming decade and
beyond. Their usefulness is limited, however, by the fact that they
do not, as is the case in any such forecasts, reflect future process
changes and improved treatment practices. Nor do they take into
account future legislative requirements.
Paper and Paperboard
Another factor to be noted in the following tables is that the BDC
projections of growth are expressed in value of shipments (5), the Forest
Service in apparent consumption which includes imports (6), and the API
in the U.S. production alone.
U. S. FOREST SERVICE (6)
Apparent Consumption
Million Tons
Board Total
1970 32.0 28.3 60.3
1975 37.7 34.4 72.1
1980 44.4 41.5 85.9
1985 51.7 49.8 101.5
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BUREAU OF DOMESTIC COMMERCE (5)
Industry 19701
1 Raoer Mi 11 s
< Paperboard 4,400
1 Building paper and board
Sanitary paper products- 1,562
Quantity shipped
(000 short tons) 3,298
(000
Percent
Increase
1969-70
1
6
2
short tons)
Percent
_, Increase
1971' 1970-71
9,800 4
1 ,687 8
3,513 7
Percent
n Increase
19751 1970-752 198C1
12,000 5 15,500
%.
2,294.4 8 3,349.9
4,189 6.5 5,22&
Percent
Increase
1970-802
5.1
7.9
6.5
^Estimated by BDC. ^Compound annual rate of growth.
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ECONOMICS DEPARTMENT. AMERICAN PAPER INSTITUTE (2)
Production
1,000 Short Tons
1970
1975
1980
1985
1990
Paper
23,220
29,704
36,035
43,260
52,700
Paper-board
24,940
31,873
38,590
46,300
55,700
Other Grades
4,297
5,634
6,745
8,115
9,850
Total
i
52,457
67,211
81,370
97,675
118,250
(See Appendix 1 for production figures from 1947; this table
also shows data on exports and imports.)
11
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The following 1975 and 1980 projections of growth in the production of various paper grades were
prepared by the API for the FAO (1). The categories used therein do not coincide precisely with
federal usage. Therefore, in the table on Page 18 (2) showing forecasts for the various paper grades
in 1985, the categories used are somewhat different.
Production
1969 1975 1980
TOTAL PAPER AND PAPERBOARD, Total: 51,180 64,027 77,490
Newsprint 3,163 3,620 3,780
Other printing and writing paper (includes bristols; excludes
thin and file folder) 10,562 13,678 17,030
Other paper and paperboard, total: 37,455 46,729 56,680
Household and sanitary paper plus special thin 3,931 5,259 6,615
Fluting paper and paperboard 4,244 5,544 7,020
Kraft paper and paperboard, total: 14,232 18,785 23,455
Kraft liner 10,986 14,762 18,620
Other kraft paper and paperboard 3,246 4,023 4,835
Folding boxboard and foodboard 5,908 6,726 7,570
Other paper and paperboard, not elsewhere specified, total": 9,140 10,415 12,020
Paper, n.c.s. 4,259 4,878 5,560
Paperboard, n.c.s. 4,747 5,387 6,290
Wet Machine Board 134 150 170
-------
PRODUCTION
Newsprint
Other,Printing and.Writing Papers
Packaging and Industrial Converting
Tissue Papers
TOTAL PAPER
1969 1985F
(million tons)
3.3
11.2
5.5
3.5
23.5
5
22
'-43
Unbleached Kraft Paperboard 11.6
Bleached Packaging and Industrial
Converting Paperboard 3.5
Semi-Chemical Paperboard 3.6
Combination Paperboard 7.3
TOTAL PAPERBOARD 26.0
Construction and Other Grades- 4.5
TOTAL PAPER AND BOARD 54.0
18
5-1/2
5-1/2
V7
46
8 .
98
13
-------
Following are the Forest Service projections of demand for paper and
board by grade through 1985:
(Millions of tons)
1970 ]975_ 1980 1985
Newsprint 9.7 11.0 12.5 14.3
Groundwood paper 1.2 1.3 1-4 1.5
Book paper (total) 6.3 7.8 9.5 11-4
Coated 3.8 5.0 6.3 7.8
Uncoated 2.5 2.8 3.2 3.6
Fine Paper 3.1 3.7 4.6 5.6
Coarse and Industrial Paper 6.3 7.4 8.6 9.8
Sanitary and Tissue Paper 3.7 4.7 5.9 7.1
Construction Paper 1.7 1.8 1.9 2.0
Container Board 14.6 18.2 22.4 27.4
Bending Board (total) 7.1 8.4 9.9 11.6
Special Food Board 3.0 3.7 4.6 5.6
Folding Box Board 4.1 4.7 5.3 6-0
Building Board (total) 3.2 3.9 4.7 5.6
Insulating Board1 1.4 1.6 1.8 2.0
Hardboard 1.8 2.3 2.9 3.6
Other Board 3.4 3.9 4.5 5.2
(A table showing apparent-consumption of paper and board by grade from
1920-1966 prepared by the Forest Service is presented in Appendix 2.)
The by-grade forecasts indicate that the largest growth in paper grades
may be expected in coated, writing, and tissue papers. Since the board
categories vary between the two forecasts, a comparison would be inexact,
14
-------
Mood Pulp
Projections for total wood pulp are as follows:
1,000 Short Tons
1970
1975
1980
1985
1990
API
(Production)
43,201
51,630
59,463
67,000
75,000
Forest Service
(Demand)
46,400
57,500
71,300
86,400
In its report to the FAO the API presented the following breakdown on
pulp production by type:
1,000 Short Tons
Production
TOTAL PULP
Wood pulp for making paper and
paperboard, totals
Mechanical
Semi - chemi ca1 (including chemi -
mechanical)
Chemical totals
Unbleached sulphite
Bleached sulphite
Unbleached sulphate R
Actua.1
1969
40,301
37,706
4,241
3,376
30,089
390
1,948
15,571
Estimated
1975
50,627
47,401
5,470
4,181
37,750
395
1 ,981
18,565
1980
58,366
54,449
6,942
4,815
42,692
389
1,958
20,165
Bleached and semi bleached
Sulphate
Other fibre pulp for making paper and
paperboard, total:
Dissolving pulp (wood and other fiber
raw materials)
11,991 16,809 20,180
894 1,072 1,296
1,701 2,154 2,621
-------
The Forest Service projections of demand for wood pulp by type are as
follows:
(Million Tons)
1970 1975 1980 1990
Dissolving and Special Alpha* 1.5 1.7 2.0 2.2
Sulfite 3.3 3.5 3.7 3.8
Sulfate 30.1 38.0 47.8 59.0
Soda .2 .2 .2 .2
Groundwood 4.8 5.7 6.7 7.7
Semi chemical 4.7 6.4 8.6 10.9
Defibrated, exploded, and
screenings 1.8 2.0 2.3 2.6
*Includes a number of highly purified types of wood pulp obtained from
the sulfite and sulfate pulping processes.
(Historical data of the Forest Service on pulp consumption may be
found in Appendix 3. Production data by grade as compiled by the
U.S. Bureau of Census are published by the API in "The Statistics
of Paper" (7).
Although the numbers in the above are somewhat divergent, the author
feels certain trends are evident. The use of groundwood pulp is expected
to expand on a rather steady incline, as is NSSC pulping. Kraft pulping
will continue a steady growth pattern but not at as rapid a pace as in
the past ten years. Sulfite pulping in its present form, as discussed in
other sections of this report, will probably hold steady at the 1972
production level.
Secondary Fiber Pulping
Since World War II the percentage of waste paper in terms in total raw
material used in papermaking has remained rather steady at about ten
million tons a year (8). The total reported for 1969 indicated that
approximately 20 percent of our paper consumption was recycled during
that year, continuing the trend of decline. However, a recent study
by the Institute of Paper Chemistry indicates that the 1969 amount was
actually 22.3 percent of total fiber furnish, and that of 1970 was
22.5 percent (9). Current API reports are very similar (2). Therefore,
the downward trend has apparently been reverse.
16
-------
The most economical use for recycled fiber is, of course, board production
which has consumed 70 percent of the waste paper processed. The
balance is used about equally for pulp substitute grades and deinking
mills.
There are numerous factors, however, wnich have made it uneconomic for
integrated mills to produce more pulp from waste paper or for non-
integrated paper mills to buy more deinked pulp. The following are among
the more significant (10,11,12,2):
(1) The quality of waste paper has been deteriorating and labor
costs for sorting are prohibitive. Pre-sorting at the point
of origin is seen as an economic necessity to stimulate
increased use.
(2) Waste paper collection is more erratic than pulp production
and prices fluctuate more.
(3) Improved management of company-owned forests has increased
tree crops and mechanical harvesting and wood-handling
equipment are reducing costs.
(4) Chemical pulping yields have been improved.
(5) The use of waste paper can result in costly effluent treatment
and sludge disposal requirements. The deinking of some waste
papers results in sewer losses of as high as 50 percent of the
bale weight of the waste, producing an effluent high in suspended
solids, turbidity, and BOD. The sludge produced on treatment
is generally almost half ash, due to filler and coating materials
washed from the old papers, and connot be incinerated by the
usual equipment. Treatment and sludge disposal costs can
readily destroy any financial advantage obtained by reclaiming
fiber and also limit mill locations which can consider this
practice. This is because land disposal is the most common,
satisfactory, and economical method available for disposing
of the sludge produced on effluent treatment, hence, the
availability and proximity of sufficient suitable land can be a
decisive factor. Land cost, is, of course, an added consideration,
A number of mills, including combination board mills, which have been
utilizing a very high proportion of waste paper have been closed because
of low margins of profit and uneconomic operating levels. The combination
board mills were, however, primarily smaller and older mills which could
not withstand the impact of the slowdown in demand. Nevertheless,
and even though no immediate shortage of pulp wood is predicted, there
are pressures building which will undoubtedly engender increased recycling.
As the population and pounds per capita consumption increase, and the
cutting rate of timber exceeds the growth rate (now predicted at just
17
-------
beyond 1980), the use of waste paper will become more economically
attractive. Normal inflationary trends can be, expected to increase
the price of pulpwood as well as the necessity for harvesting remote
areas and increasing competition from other wood-using industries (10).
Additionally, recycling has come into focus as a partial solution to
the problems of solid waste disposal. Paper and paperboard account
for nearly half of all municipal solid waste, although only about 12
percent of the total (2). This has led the U. S. Government and various
state and local governments to revise procurement specifications for
paper purchases to require varying percentages of recycled paper. The
Resources Recovery Act of 1970 and the recommendations of the National
Commission on Materials Policy are likely to further intensify the
pressures toward recycling paper which will require the industry to
develop the technology to utilize increased quantities efficiently,
particularly for printing and writing papers.
In 1969, 1.9 million tons of waste paper were used in the production
of 23.5 million tons of paper, 8.4 million tons in the production of
approximately 26 million tons of paperboard, and 1.23 million tons in
the production of 4.5 million tons of construction and wet machine
board (2).
Projecting the ratios of waste paper use to production for each sector,
the API has computed the waste paper demand in 1985 as illustrated in
Table 1.
Estimated waste paper requirements through 1990 are as follows (2):
1,000 tons
1975 13,670
1980 19,520
1985 27,930
1990 39,000
The National Academy of Science has projected 35 percent recycled paper
by 1985 (13).
Not the least of the imponderables which will determine the rate of
increase in reusing paper is the character of public demand. Up
until the recent surge of environmental concern, industrial and other
buyers preferred virgin fiber products. If, however, the current
ecological motivation continues, it will increase the pressure on the
industry to develop not only the technology for more efficient use of
waste paper, but improved technology to control the attendant increase
in water contaminants.
18
-------
Table 1
WASTE PAPER REQUIREMENTS
1969 1985F
—(million tons)---
Paper Production 23.5 43.3
Waste Paper Used 1.86 5.2
Waste Paper % Production 7.8% 12.0%
Paperboard Production 26.0 46.3
Waste Paper Used 8.69 19.5
Waste Paper % Production 33.4% 42.0%
Construction and Wet Machine Board Production 4.5 8.1
Waste Paper Used 1.22 3.25
Waste Paper % Production 27.1% 40.0%
Total Paper and Paperboard Production 54.0 97.7
Waste Paper Used 11.77 27.9
Waste Paper % Production 21.8% 28.5%
Waste Paper used for Molded Pulp and Miscellaneous .206
Waste Paper Exports .408
F - Forecast projection by API.
19
-------
The General Services Administration has included wood residues in its
definition of waste products, as well as the use of broke, trim, and
other relatively clean mill waste. However, of the 35 percent total
waste product content required in Federal Specifications for corrugated
fiberboard, ten percent must be consumer-used waste paper. Percentages
for minimum waste content of other paper grades are contained in a
Fact Sheet issued by the General Services Administration in September
1971 (14).
Capacity
Presently a readjustment in production facilities is underway in the
industry. Old, high production-cost mills, particularly those facing
large expenditures for refurbishing and water pollution control, are
being abandoned; 19 fine paper mills and 22 paperboard mills have
closed down. Since 1962, 21 mills producing sulfite pulp have
been permanently closed, as have 3 old kraft mills and 2 NSSC operations.
The number of kraft mills has increased from 89 in 1964 to 121 in
1971. The number of such mills with a capacity of less thanJOOjOOO
tons of annual capacity has decreased from-19 in 1964 to 14 in 1971,
however, those manufacturing between 100,000 and 200,000 tons have
increased from 19 to 35 and those in the 200,000 to 300,000 range
remained constant. Those whose capacity is in excess of 300,000
tons have increased since 1964 from 20 to 41 in number.
These data indicate that a considerable number of mills having difficult
pollution problems have ceased to exist. The products they manufactured
are now produced in large modern mills provided, in most cases, with
modern waste treatment facilities. Tables showing growth trends in
industry capacity through 1974 appear in Appendices 4 and 5 (18,19).
Total capacity by geographic region is presented in Appendix 6 (333).
Per Capita Consumption
The United States continues its world leadership in per capita consumption
of paper and paperboard although 1970 consumption declined slightly over
1969—from 576 pounds to 556 (363). This reflected factors influenced
by the general downward trend in the.economy, such as the drop in
newspaper advertising space.
Sweden and Canada, the second and third ranking leaders in per
capita consumption, continued their upward trend but the increase from
1969 to 1970 was, in both cases, only a fraction of that experienced
from 1968 to 1969—approximately one-fourth and one-sixth, respectively.
Table 2 illustrates the per capita consumption of the 20 world leaders
in 1968, 1969, and 1970.
Appendix 7 presents statistics for the United States for most years from
1899 through 1970. It is interesting to note that each year in which
per capita consumption declined from the previous year represented a
20
-------
Table 2
PER CAPITA CONSUMPTION OF PAPER AND BOARD
1968
1. United States
2. Sweden
3. Canada
4. Switzerland
5. Denmark
6. United Kingdom
7. Netherlands
8. Australia
9. Fed. Rep. of Germany
10. Norway
11. New Zealand
12. Finland
13. Japan
14. Belgium
15. France
16. Ireland
17. Iceland
18. Austria
19. Dem. Rep. of Germany
20. Italy
Ibs/yr
551
370
368
294
272
270
265
249
244
238 10.
228 11.
214 12.
213 13.
206 14.
179 15.
148 16.
147 17.
146 18.
135 19.
128 20.
1.
2.
3.
4.
5.
6.
7.
8.
9.
1969*
United States
Sweden
Canada
Switzerland
Denmark
Netherlands
United Kingdom
Fed. Rep. of Germany
Australia
Norway
New Zealand
Japan
Belgium
Finland
France
Ireland
Austria
Iceland
Italy
Dem. Rep. of Germany
Ibs/yr
1.
2.
3.
4.
5.
6.
7.
8.
9.
576
410
393
317
313
298
282
270
260
255 10.
246 11.
243 12.
236 13.
230 14.
203 15.
173 16.
161 17.
148 18.
144 19.
143 20.
1970
Ibs/yr**
United States 556
Sweden 420
Canada 397
Switzerland 339
Denmark 326
Netherlands 304
United Kingdom 284
Fed. Rep. of Germany 275
Japan 267
Norway 264
Finland 252
New Zealand 252
Belgium - Luxemburg 248
France 208
Austria 175
Ireland 173
Hong Kong 165
Dem. Rep. of Germany 165
Panama 145
Costa Rica 144
* Does not include British Honduras (250) and Panama (145).
** Rounded
SOURCE: Pulp & Paper
-------
period of economic uncertainly, ranging from the depression year of 1934,
to what might be termed a slack economy, to actual repression in later .
years. These years are indicated by asterisks in Appendix 7.
Employment
The paper and allied products industry is a large employer. Total
employment (excluding the building paper industry) reached a record
high of 716,000 in 1969, a gain of 114,000 from 1960. However, the
total dropped to 710,000 in 1970 (7).
Although wages have been rising in line with the general increase in
wage rates, labor costs as a percentage of sales have remained relatively
stable due to technological improvements which have reduced the man-hours
required per unit of output. According to the Bureau of Domestic
Commerce, between 1963 and 1970 average output increased 25 percent
from 235 to 293 tons of paper and board per production worker. In
1968, each ton of output required 7.7 man-hours, a decrease of 18
percent from the requirement of 9.4 man-hours per ton in 1963 (5,15).
The BDC reports payroll costs for 1970 at a level equivalent to 21
percent of the value of shipments in its profile of paper, paperboard,
and building paper and building board mills (5). For 1969, the API
reported an average of 20.2 percent for 21 non-integrated paper companies
and 24.3 percent for 32 integrated companies (16).
The 1970 average hourly earnings for the paper and allied products
industry was reported at $3.44 by the Bureau of Labor Statistics--
$3.80 for paper and pulp employees, $3.86 in the paperboard industry,
$3.12 converted paper and paperboard products, and $3.18 in paper-
board containers and boxes (17).
Profits
Profits of the paper and allied products industry are marginal, partly
because of the very high capital investment required. Profits after
taxes in this industry, in relation to net worth, have been consistently
below the ratio for all manufacturing industries and in recent years
the ratio of profits to sales has also been somewhat lower.
At this writing the profit situation is still feeling the effects of
lower demand in 1970, and increased costs. According to the Paper
Trade Journal, industry sales for the first half of 1971 are up 2.9
percent and net profit down 26.9 percent, before extraordinary items,
from the first six months of 1970.
Comparing the years 1969 and 1970 in terms of sales and profits, of
the 40 companies responsible for the bulk of the tonnage in this
country, 28 showed an increase in sales and 11 a decrease (324).
Profits increased for only 6 operations and declined for 34. The
22
-------
extent of the decline in profits was in most cases appreciable despite,
in many instances, an increase in sales. Three companies which had a
profitable year in 1969 suffered a substantial loss in 1970 and
companies which had a small loss in 1969 suffered triple that loss in
1970. Only five companies showed an increase in profits in 1970 over
1969. Of the 20 companies having increased sales and lower profits in
1970, seven declined less than ten percent, five between 10 and 20
percent, six between 20 and 30 percent and two in excess of 30 percent.
Table 3 presents a comparison of 1969 sales and profits with those of
1970 for 30 of the largest United States paper producers as published
by "Paper Processing."
Profit and loss data for the paper and allied products industry for the
years 1947,,through 1970 appear in Appendix 8.
23
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Table 3
SALES VS. PROFITS OF MAJOR U.S. PAPER MANUFACTURERS
ro
-pa.
Company
1970 Sales
(Thousands of dollars)
1969 Sales 1970 Profits
1969 Profits
International Paper Company
Boise Cascade Corporation
U.S. Plywood- Champ ion Papers, Inc.
Weyerhaeuser Company
Georgia-Pacific Corporation
Mead Corporation
Crown Zellerbach Corporation
Kimberly-Clark Corporation
St. Regis Paper Company
Scott Paper Company
Diamond International Corporation
Union Camp Corporation
Westvaco Corporation
Great Northern-Nekoosa Corporation
Hammermill Paper Company
Potlatch Forests, Inc.
Hoerner- Waldorf Corporation
Brown Company
Inland Container Corporation
Fibreboard Corporation
Southwest Forest Industries, inc.
Federal Paperboard Company, Inc.
Consolidated Papers, Inc.
Longview Fibre Company
Sonoco Products Company
$1,840,832
1,716,860
1,355,944
1,233,423
1,194,430
1,038,000
955,288
868,742
857,431
755,700
505,046
462,200
420,344
355,291
352,413
319,270
250,372
216,828
197,196
169,722
162,786
133,000
131,988
127,345
125,907
$1,777,251
1,738,690
1,492,590
1,199,046
1,160,160
1,031,000
919,282
834,714
867,827
731 ,500
498,094
449,537
419,598
344,139
353,272
340,435
237,202
195,675
191,716
181,820
139,302
132,659
127,746
129,573
125,180
$82,477
36,560
- 37,809
124,207
79,220
19,900
41 ,905
38,315
35,764
49,100
34,606
30,777
17,130
16,480
9,364
10,980
13,845
1,381
7,031
1,154
4,768
3,893
3,349
11,195
6,331
$115,614
81,210
68,265
131,362
91,760
35,900
53,963
49,930
41,196
60,000
35,671
30,383
21 ,864
20,252
14,076
14,541
12,176
1,693
9,504
9,301
6,475
4,181
5,251
13,244
6,719
-------
SECTION IV,
WATER QUALITY PROBLEMS OF THE INDUSTRY
The pulp and paper industry employs an estimated 1800 billion gallons of
water annually (20) and since losses from evaporation, etc., amount
generally to less than ten percent, most of this finds its way into
surface waters. Both process water and water for accessory uses such
as cooling and power generation are included in this figure. Over
60 percent of the total is process water (21) which comes into contact
with the raw materials and product and retains a small percentage of
them. Examples are its use for washing and debarking wood, grinding,
defibrinating, and cook-raw materials as well as a furnish carrier in
pulp bleaching and in the papermaking system. The quantity used in
a particular mill varies considerably with the products manufactured
as well as the specific equipment used and its arrangement. Quality
requirements also vary widely depending upon the quality of the product.
For example, coarse papers such as wrapping and board products can
use water of much lower quality than that needed for fine papers (22,23)
in which cleanliness and brightness are basic requirements.
Water reuse has long been practiced in the industry (24) for several
reasons. One is to reduce water costs and a second is to reduce fiber
and filler losses which, up to a point, decline with the degree of
recirculation (25). Others are the conservation of heat and chemical
additives such as si zings. Haynes (26) estimated that by 1966 process
water was recycled 2.5 times in -the southern kraft industry, which is
responsible for a very large percentage of the total pulp and paper
tonnage in the country.
Spent process waters resulting from raw material handling, pulp and
paper manufacture, and chemical recovery are classified as organic
wastes since most of them are high in this type of compound which can
be present both in suspension and solution (27). Dissolved organics
consist of such substances as lignins, tannins, sugars, and cellulose
degradation products leached or cooked from wood or other raw materials.
They can also consist of adhesives and sizing materials such as starches
and resinates added in the papermaking process. Suspended organic
matter can consist of bark, bark and fly ash and wood fines, fiber,
fiber debris, and suspended papermaking additives.
The organic fraction contains both biodegradable and refractory substances.
Examples of the former are wood sugars and cellulose degradation products
such as fatty and hydroxy acids, alcohols, and ketones. The latter is
exemplified by the lignins, most of which, as they appear in pulping wastes
are not biodegradable as demonstrated by Lawrance (28) and others..
25
-------
Pulp and paper mill effluents are notoriously low in phosphorus and nitrogen,
most containing insufficient concentration of these elements to support the
optimum rate of biological oxidation. For this reason nutrient supplements
have to be added when the wastes are treated by methods involving microbiai
activity.
Inorganic materials are also present in both suspension and solution. The
suspended materials consist of silt washed from logs, chemical recovery
residues such as grits and dregs, process water treatment sludges, and
paper filler and coating materials such as clay, talc, and calcium carbonate.
Dissolved inorganics consist of sizing chemicals and salts from chemical
recovery system wash water and from bleaching operations.
Receiving Water Problems Caused by Pulp and Paper Mill Wastes
Suspended organic matter can have several effects on receiving bodies
of water. The settleable variety, such as bark and wood fines, as well
as all coarser fibers, are inclined to settle to the bottom where they
decompose. When such deposits blanket the bottom they interfere with
the normal development and livelihood of benthal-dwelling organisms
upon which fish feed (29). If the dissolved oxygen is depleted
altogether, anaerobic decomposition of the residual organic matter takes
place. This can create gases such as hydrogen sulfide and methane
which give rise to offensive odors and unsightly gas-floated islands
of fibrous sludge. Anaerobic decomposition is also accompanied by a
blackening of the water and solubles formed by the process, such as
fatty acids and alcohols, can exert a considerable oxygen demand on
the overlying water as pointed out by several investigators (30,31,32).
This situation can also retard the self-purification process in surface
waters to a marked degree.
Biodegradable dissolved and dispersed organics also deplete dissolved
oxygen in water (33) and may create anaerobic conditions.
Biological imbalance in streams resulting in slime infestations has
resulted from the discharge of oxidizable pulping solubles (34). A
critical review of the literature on the subject by Harrison (35) was
presented in 1957 and was followed by extensive studies of the problem
by Amberg (36), Cauley (37), and others (38,39). This phenomenon
can be caused by wood sugars and cellulose degradation products such
as fatty acids which stimulate the growth of Sphaerotilus natans and
similar organisms. Growth can occur on suspended wood particles such
as groundwood rejects or grow freely or attached to rocks, tree branches,
or logs floating in the stream. They also grow upon or are collected by
fishing nets. The resulting clogging shortens fishing time and poses
a difficult cleaning operation which in time shortens net life. They
can also clog water inlet screens rapidly and cannot be cleaned from the
screens effectively by usual methods.
26
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These slimes absorb nutrients from the water and the extent of their
proliferation appears to be determined by the quantity of suitable
nutrient passing a particular slime mass in a given period of time,
rather than the concentration. Their growth has been controlled by
intermittent discharge of wastewaters whereby periodic starvation
causes a dying off of the organisms. Treatment to remove the nutrients
has proven to be a more effective means for controlling this problem.
Those slime problems arising from growth on suspended wood particles
are being controlled simply by preventing their discharge. The practice
of storing logs in water, which can involve the slime problem, is being
solved by land storage.
Refractive organic matter contains, among other things, color bodies
which can impart an undesirable appearance to surface waters. The
cost of removing color at downstream water treatment plants can be
raised by these materials as pointed out by Herbert (40). The nature
of these substances in kraft bleaching effluents is described in Lunar
and Dance (41,42). They consist mainly of carboxylic acids in the
case of caustic extraction effluent, and chlorine containing unsaturated
acidic fragments of lignins in the case of chlorination-stage wash
water.
Inorganic materials in solution are rarely considered to contribute to
water quality problems since the discharge of acids and alkalies is
largely under control and the remainder consists largely of sulfates
and chlorides of sodium and calcium from pulping and bleaching operations.
Under the conditions of insufficient dilution, however, the addition
of these salts can raise the total solids and chloride content of
receiving waters above the levels stipulated by prevailing standards, or
required for downstream uses such as irrigation or some industrial
processes. The suspended inorganics consisting of silt, clays, talc,
calcium carbonate, and titanium dioxide can cause turbidity and unsightly
opalescence in receiving waters or can form bottom deposits which
blanket benthal deposits or inhibit biological activity through preventing
light penetration.
Van Horn (43) investigated the causes of tastes and odors imparted to
receiving waters and their inhabitants by kraft pulping effluents. The
responsible compounds were found to be sulfides and organic sulfur
compounds, resin acids, and turpines. The sulfides as a rule are rapidly
oxidized in surface waters while the latter are more persistent. Van
Horn also demonstrated that the skin, rather than the flesh of fish,
picked up odorous substances, a taste panel being unable to detect any
off taste in fish which had been skinned and cooked. Tokar and Owens (44)
also studied this effect. Their findings showed that water containing
1.5 percent by volume of unbleached kraft effluent imparted a taste to
salmon. Treatment of this waste altered this percentage to 2.9.
In most instances reported, fish taste downstream of kraft mills has
been found to result from kerosene used in foara control. A change in
foam control agent to a type that does not impart taste and odor to
either water or fish has been found to correct this condition.
27
-------
The taste and odor producing potential of chlorinated phenolic bodies
present in pulping wastes are discussed by Dence (45). It was concluded
that forming odiferous chlor-phenol compounds and their tendency to do
so should be investigated.
Fiber Leaching
It has been demonstrated that oxygen uptake from physically stable
cellulosic bottom deposits was proportional to their surface area.
Depth influenced the demand only up to one foot, past which it proved
an insignificant factor. Mixing and turbulence increase the oxygen
demand of the deposit since these conditions cause soluble materials
to be leached from the sludge mass.
Stagnant flow conditions produced oxygen demands of 0.2 grams of oxygen
per square meter per day. The demand increased to 2.7 grams under
eddying conditions and to 4.4 grams under slight scour. Covering of
such deposits with silt caused radical decrease of the oxygen demand
and fresh deposits are considerably more active than old ones.
The degree of leaching from bark, according to McKeown (46), in terms
of BOD5, COD, color, Kjeldahl nitrogen, and phosphorus, decreases with
time of storage in bark piles. Aging in underwater deposits decreased the
leaching potential faster than it decreases through storage in log
piles. Concentrations of the Teachings increase with contact time
approaching limiting values, the time required to reach the limit
depending upon the age of the bark and conditions of water contact.
The total amount leached increases with the water volume involved.
With the exception of phosphorus, the degree of leaching was very much
lower in salt water than in fresh water and leaching rates under stagnant
conditions are lower than they are in water that is mixed. Sulfide
production is higher in saline water, presumably because of its high
sulfate cbntent. The deoxygenation rate constant for fresh bark
extract is similar to that of most raw pulping process wastewaters
(0125 day'1, base 10).
Bioassay experiments employing fresh hardwood and softwood barks from
Northeastern species exhibit a TLra of 42 percent with chinook salmon as
the test organism.
Aquatic Biology
Pulping effluents have long been associated with damage to aquatic
and marine life as a result of fish kills downstream of mills and
alleged damage to shellfish cultivation waters. Many publications
have appeared in the literature dealing with specific situations which
must be judged on an individual basis. However, a large amount of
experimental work has been done on problem definition and control. These
studies have provided solutions to some of the problems and are leading
to the solution of others. This is reflected by the fact that pulp mill
28
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related fish kills are now rarities as indicated by the federal census
of such occurrences over a period of eight years (276).
The reduction has resulted from the addition and improvement of spent
liquor recovery systems, effluent control and treatment, and the
prevention of spills of potentially toxic liquors and wastewaters. Recent
investigations have been directed toward determining the more subtle
effects which pulp and paper mill wastes might have on the reproduction
and productivity of aquatic life. These areas are defined by Warren
(126) in considerable detail.
Van Horn (277,278,279) has critically reviewed the literature on
the effects of pulp and paper mills on aquatic biology. Many of the
problems have resulted from oxygen depletion. The effect this factor
has on various species of fish and fish eggs has been studied in detail
by Warren, Duoderoff, Scott, and others and the findings were summarized
by Fry (280) and Duoderoff (281).
Dissolved oxygen levels of the same order as is presently required by
state-federal stream standards were recommended. These standards are
believed by many investigators to be on the high side particularly for
warm waters. The concentration allowing fish survival is considerably
lower than that required for the eggs and fry of some species, and that
needed to support their normal level of activity.
In any event, one cannot look for any final answer to the matter of
dissolved oxygen requirements under all conditions. This appears to be
interdependent on the concentration of other gases such as carbon dioxide
as demonstrated by Warren (282).
Van Horn (283,284,269,285) and others (286,287,288,289,290) identified
substances present in kraft pulping effluents that are toxic to aquatic
life. While many compounds having toxic properties can be extracted
from kraft effluents the common offenders appear to be sulfides,
mercaptans, resin acids, and terpines. In the case of high kraft liquor
losses, alkali can be a factor as well. However, the above-named
materials are toxic at the part per million level and are probably the
substances involved in any obscure aquatic problems that might arise.
Some of these substances such as the sulfur compounds are removed by
short-period storage, probably as a result of oxidation (288).
Biological treatment and self-purification are very effective in
destroying and removing the toxic components from kraft effluents as
demonstrated by Warren (291), O'Neal (292), and others (239). High degree
treatment can destroy it entirely as evidenced by the fact that treated
effluent will frequently in itself support fish life, i.e., the presence
and multiplication of fish in long-term storage oxidation basins handling
both bleached and unbleached kraft pulping effluents. Field bioassay
tests have also shown that effluents from aerated stabilization basims
and activated sludge plants treating both bleached and unbleached kraft
effluents exhibited no toxicity to common species of fish.
29
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The fact that a large segment of the kraft pulping industry is already
practicing or is committed to biological treatment indicates that the
acute toxicity problem of this group is a problem of the past.
Servizi et al (294,295) and Das (296) investigated the toxicity of
bleached kraft chlorination waste to young salmon. They believe that
chlorinated catchecol compounds were responsible for the problem, 'but-
found that treatment is effective in destroying the toxicity of this
wastewater.
Methods for the detection and quantitative measurement of minute
concentrations of sulfide mercaptans and resin acids were published by
Van Horn (277). The technique for determining resin acids was later
improved by Carpenter (270).
The effluent from sulfite mills not practicing liquor recovery has been
shown to be toxic to salmon (297,298). However, most of the problems '
relative to the discharge of spent sulfite liquor have been due to
oxygen depletion. Since recovery or other disposition of spent sulfite
liquor will be universal practice in this country within the next few
years, concern is with the effect of the residual sulfite mill effluents
rather than the spent liquor itself. These do not contain acutely toxic
substances as does kraft pulping effluents but have a higher demand for
dissolved oxygen. These can be readily destroyed by biological oxidation
since they contain mainly fatty acids (299,300,152). The residual,
consisting of lignosulfonates and other refractory organics, represents
only a very small percentage of the original concentration present in
the spent liquor.
Studies have been made on the effect of kraft mill effluents on the
migration and spawning of alewives and striped bass. Van Horn (301)
determined that bleached kraft effluent did not influence alewife runs
in the lower Roanoke River. The same author reviewed with Brandt and
Hassler (302) studies covering four years of investigation of the
spawning habits of striped bass in the Roanoke River. Spawning was
demonstrated to take place throughout the river and did not appear to
be influenced adversely either along the river or in the estuary. Dimick
(303) studied avoidance reactions of salmonoids to kraft effluents in
laboratory streams. While demonstrating that such a reaction could
take place, the value of such tests in evaluating conditions prevailing
during actual fish runs appeared doubtful.
The question of aquatic productivity appears to be one of great moment
and is discussed in detail by Warren (277). Should pulping effluents
not affect productivity adversely there is little cause for concern
for the aquatic environment because of their discharge. Warren and
others (304) conducted extensive experiments on production and food
relations of young Chinook salmon in laboratory streams receiving
untreated and treated kraft pulp mill effluent. Results obtained were
inconclusive due to the difficulty in maintaining a balanced population
of food organisms although no marked diminution in productivity was
30
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recorded in the streams receiving the wastewaters. Presently, a similar
project is being carried on in artificial streams with the cooperation
of the industry. This is a long-term study and should provide the
desired information.
Warren and others (305) demonstrated that enrichment of an experimental
stream with small quantities of sucrose caused a decided increase in
trout productivity. This indicates the possibility that the productivity
of some streams could be enhanced by the addition of low concentrations
of wastes containing carbohydrates, such as pulping effluents.
Extensive research has been conducted to determine the effect of kraft
and sulfite pulping effluents on bivalves, particularly oysters and
their larvae, both in this country C306) and in Japan (307). Some of
these studies have been concerned with the development of a test using
oyster larvae to determine if an effluent is inimical to the organisms.
Several tests have been developed to date but investigators disagree on
details of the tests and their interpretations. Both kraft and sulfite
pulping effluents exhibit toxicity to bivalves but the concentration
at which this is the case is not clearly established since captive
tests leave mich to be desired and their validity is repeatedly questioned.
Field tests in recent years yielded a clear relationship between pulp
mill discharges and oyster bed productivity. As a result, the practice
of discharging spent sulfite liquor to coastal waters is being rapidly
eliminated and kraft mills do not appear to be at all involved in the
situation.
The subject of the effects of wood fibers on aquatic life were investi-
gated further in recent years by Smith and his associates. Kramer and
Smith (308) studied the effect of aspen and conifer groundwood on walleye
eggs and found no significant effect of fiber concentrations of 60 and
120 rog/1 on survival. McLeod and Smith (309) found that fiber concentrations
in the 100 to 800 mg/1 range could decrease swimming endurance of walleyes
when the dissolved oxygen concentration was low (2.5 mg/1). Increased
fiber concentration leads to marked increase in gill-cleaning reflexes
which appears to raise the energy requirement for maintenance. These
phenomena were interpreted to indicate stress which could decrease
survival and production of fish in natural habitats high in fiber content.
Smith et al (215) determined that 150 mg/1 fiber concentration raised
the metabolic rate 18 percent and lowered the hematocrit count of walleyes.
This increase could be inimical at high temperatures and low dissolved
oxygen levels.
It should be noted that the fiber concentration levels employed in these
studies are extremely high. They are equal to or above those which would
be expected in the untreated effluent of a modern mill and very much higher
than concentrations appearing in effluents receiving primary treatment.
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Heavy Metals
Widespread publicity associating pulp mills with the discharge of
mercury was not directed toward pulp and paper manufacture primarily,
but rather to chlorine-caustic operations carried on at mill sites. It
was feared that chemicals produced at the several mercury cell chlorine-
caustic plants might find their way into pulp and paper effluents. However,
any such conditions that once existed have been corrected and this is now
a most unlikely possibility.
On the whole, heavy metals which might be present in pulping effluents
originate from one or more of three sources, i.e., (1) chemicals used
in pulp processing, (2) additives used in papermaking, or (3) products
of equipment corrosion. Pulp processing chemicals, mainly sulfur, salt
cake, limestone, sodiurn-hydrosulfite, chlorine and chlorine compounds,
and caustic soda, are normally low in heavy metals and their use is
such that those present would likely be precipitated in the process and
be discharged with solid residues.
The only heavy metal that has been identified with pulp mill effluents
is zinc since the hydrosulfite salt is used at a few mills for bleaching
groundwood. The quantity used is sufficiently low so that zinc probably
does not reach toxic levels in the waters receiving these wastes.
Few heavy metals or their salts are employed in papermaking other than
as insolubles such as completely inert oxide pigments.
While corrosive chemicals are handled and some corrosion takes place
in pulp and papermaking equipment, metal losses of an order that would
cause appreciable concentrations of metals like nickel and chromium to
appear in effluents is unlikely because of the high resistance to corrosion
of the materials of construction now employed throughout the industry.
It might be anticipated that metals such as iron might appear in low
concentration due to corrosion from refiners, beaters, and similar equipment.
It can be concluded from the above observations that it is most unlikely
that heavy metals of toxic nature reach critical levels in pulp and paper
mill effluents and the absence of any history of difficulties arising from
these bears this out. While little is known about their presence, detailed
investigations in this area, at present, do not seem justifiable in the light
of the identifiable and pressing problems needing attention with respect
to these wastewaters.
Sewer Losses of Inorganic Chemicals
Although the chemicals used for pulping and bleaching are inorganic
in nature, their ions leaving the processes are frequently associated
to a substantial degree with organic molecules (45,41,42,223). For example,
in the sulfite processes, the base cation forms a lignosulfonate salt, and
in kraft soda pulping, the soda ion becomes associated with lignins, resin,
and fatty acids to form their salts. In bleaching, a portion of the chlorine
becomes attached to organics as does the caustic employed in the extraction
stages.
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However, all kraft and modern sulfite mills lose some of the inorganic
reagents as used or formed in the process. They find their way into
the mill effluent, either in their original state or in a modified form,
and, as previously pointed put, can have undesirable effects on the use
of surface water.
}
Sulfite mill effluents can contain sulfurous and sulfuric acids as well as
the sulfate, or sulfite, bisulfite, or thiosulfate of the particular base
employed. Sodium sulfate and some sodium carbonate as well as sodium
chloride, calcium sulfate and carbonate appear in kraft mill effluents.
Sodium and calcium chloride as well as hydrochloric acids appear in
appreciable amounts in bleaching effluents and chemical preparation can
account for some inorganic sewer losses.
In addition to the inorganic constitutents contributed to pulping and
bleaching spent process waters, inorganics are also contributed by the
wood. The ash content of common species of pulp wood ranges from 0.3
to 1.2 percent on the air-dried basis. Hence, a ton of wood will contribute
from 6 to 24 pounds of inorganic matter to the pulping system. On a pulp
yield basis of 50 percent, these figures double.
A water containing 100 mg/1 of total inorganic solids will contribute
16 pounds to the system assuming a water usage of 20,000 gallons per
ton of pulp. This contribution will increase in direct proportion to
the salt concentration in the process water.
Insoluble inorganics are discharged from the alkaline pulping recovery
processes in the form of dregs settled out from the green liquor and
grits removed from the slaking operation (211). These materials are
seldom discharged to the outfall and are generally lagooned. However,
a small amount of them find their way into the mill sewer system. They
consist mainly of silica, alumina, iron, magnesium, and calcium compounds
of an insoluble nature together with traces of sodium carbonate, sulfide,
sulfate, and calcium hydroxide.
There are also some minor intermittent sources of inorganics contained
in liquor filter backwash, hypoehlorite, and acid tower wash-up. These
constitute very minor sources.
Sulfite, bisulfite, and neutral sulfite pulping effluents from mills
practicing recovery employ magnesium, ammonia, or sodium as a base
(204,205,175). It is anticipated that calcium base pulping will practically
disappear in this country within the next few years since calcium base
recovery systems are not economical here and present several technical
difficulties not shared by the more soluble base systems. Because of this,
attention is given herein to the inorganic constitutents of soluble base
mills equipped with modern recovery systems.
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Magnesium base sulfite and magnefite pulp mills discharge magnesium salts
as the-sulfite, sulfate, and hydroxide in low concentrations. A recovery
of cooking chemicals in excess of 98 percent is not uncommon for these
operations. Hence, an effluent containing less than 25#/AD ton of pulp
of MgO can be anticipated. In fact, the latter should be lower because
of the high solubility of the base.
It should be pointed out here that data regarding direct effluent analyses
for inorganic ions are not abundant in the literature. One reason is that
in the past these have not resulted in serious receiving water use probeims
Additionally, specialized analytical methods must be used to determine
the quantity of the ions attached to organic matter and of those that are
not. Such analyses are generally complex and have been limited to the
research area by both the industry and government. The ash content of the
total solids content of an effluent (as commonly measured) yields a result
inclusive of both the free and combined inorganic ions present in the
system. Hence, very little information is available regarding the
concentration of inorganic compounds as such in pulp mill or bleach plant
effluents.
The same is true of the effluents from paper mills, but for a different
reason (288). A large percentage of many of the additives such as
sizing chemicals and adhesives are incorporated in the paper and do not
find their way into effluents. Little in the way of investigation of
the soluble inorganics in paper mill effluents has been made; however,
the losses of insoluble filler, coating materials, and pigments, some
of which are not retained in the sheet, have been explored to a
considerable degree. This has been particularly the case since special
reagents are now commonly employed to increase their retention. Because
of the extremely wide range of products manufactured and similar range
of these materials used in the operations, the sewer losses of these
cover a range estimated to be from 5 to 30 pounds per ton of product.
These consist of calcium carbonate, clay, talc, titanium dioxide, and
other materials of similar physical properties (345,346).
Reprocessing of paper and broke leads to the discharge of large quantities
of inorganics in the effluent when these contain fillers or pigments
or are coated (224,225). These processes are the major source of such
materials in many white paper manufacturing operations and in the case
of deinking produce effluents higher in these substances than any other
paper manufacturing effluent.
As stated elsewhere in this report, wood is low in phosphorus and
nitrogen and the discharge of most effluents from its pulping do not
result in effluents which promote eutrophication. Exceptions can exist
due to use of ammonia in pulping and phosphates as detergents, pigment
dispersants, or for water treatment. Nutrients are added to some wastes
in the form of ammonia and phosphoric acid at a low level (12). It is
unlikely that sufficient of these nutrients appear in the effluent to be
an important factor in promoting eutrophication because of their low
initial level and the fact that they are adsorbed to a degree in the
biomass of the treatment system (168).
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SECTION V
GENERAL PROCESSES EMPLOYED FOR EFFLUENT MANAGEMENT AND TREATMENT
While some pulp and paper mill effluents are controlled individually
or pretreated before joining the general stream, in most cases the
entire combined effluent receives final treatment with the exception
of uncontaminated cooling waters and at times some very weak wastes.
Since the effluents from most modern mills are as relatively weak as
sanitary sewage, they are treatable by similar methods. However,
modification of such systems are generally necessary because of
differences in waste characteristics. The following section describes
the methods commonly employed and presents generally well-established
performance data for unit processes of treatment and sludge handling.
Seweri ng
In most modern pulp mills sewer segregation is common to the extent
that wastes low in suspended solids and those that are high in them
are sewered separately (47). If bleaching is practiced, a separate
acid proof sewer—generally of polyvinyl chloride or fiberglass
construction—is provided to carry the chlorination effluent so that
it can be neutralized before joining the common effluent stream. This
is good practice because direct mixing of this bleaching wash water
with that from alkaline extraction can cause a serious foaming problem.
Bleaching waste is often low in suspended solids and BOD5 and is sometimes
by-passed around the clarification system.
Some mills are equipped with a waste holding basin to which the sewer
carrying pulping wastes, tank overflows, and apron and floor drains can
be diverted when liquor losses are high for one reason or another. The
basin contents are then metered into the overall discharge at a suitable
controlled rate when the effluent strength is normal. Some of these
systems are equipped with conductivity recorders which activate diversion
valves automatically when high losses are indicated, sending the flow
to storage basins.
Where small volumes of strong wastes are involved, such as the exploded
wood hardboard process, these are segregated for separate handling such
as land disposal and incineration. In general, however, all dilute
wastes from most mills are ultimately combined for external treatment.
Screening
In addition to the screening procedures commonly used in wood preparation,
it is standard practice to screen total mill effluents through bar racks
having one-half inch openings (48). It is well to protect following units
from large objects such as logs, tools, etc., which get into sewers from
time to time. This is done by placing a manually-cleaned bar rack with
35
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openings of two inches or more in the channel ahead of the fine screen.
In large mills the finer screens are mechanically operated and screenings
are taken to a dump or incinerated since they contain mainly combustible
matter such as paper, bark, and wood chips or slivers. It is extremely
important that the screening operation be efficiently carried out since
the nature of the materials removed is such that they can cause serious
trouble in succeeding treatment equipment.
Ordinarily grit chambers are not employed nor do they appear to be necessary
since little coarse detritus matter normally finds its way into the process
sewers. In the case of waste paper mills, such materials are removed in the
process itself and dumped with the trash removed from hydropulpers.
In larger mills, flow-measuring flumes are frequently installed in the
channels following the screening operation and small mills usually
employ weirs for flow measurement (49). In some cases the flow of the
final effluent is measured rather than the treatment plant influent.
Neutralization
In the case of effluents from acid sulfite pulping, acid sulfite liquor
recovery systems, and the acid stages of bleaching, neutralization is
required unless these are mixed with other wastes containing sufficient
alkalinity to accomplish this. Neutralization is achieved, in practice,
by either adding caustic soda, lime, or limestone in controlled dosage.
This can also be accomplished by passing the waste through a limestone
bed as discussed by Lott (50) who developed a mathematical model for
the design of these devices.
Clarification
While sedimentation, flotation, and filtration are all used to remove
fiber and other suspended matter from mill process waters internally (25),
external clarification is almost universally achieved by sedimentation
(51) but in some instances flotation is also effectively employed (25).
Sedimentation is accomplished in mechanical clarifiers, alternating
basins, or, in the case of very large storage oxidation installations, in
the inlet section of the large impoundment areas used for this purpose.
The trend in the industry is strongly toward the mechanical clarifier (52).
These have been found to be effective in removing over 95 percent of the
settleable suspended solids from all the effluents produced if properly
designed and installed. They are generally equipped with a skimmer and,
for effluents containing entrained air, a de-aerating device. Clarifier
design has been discussed by Knapp et al (53) and the application of
mathematical models to such treatment by Morean (54) and Edde (55).
A NCASI survey (56) of practice at southern mills covers the performance
of settling for treating these wastes. The literature is also replete
with descriptions and performance data for the various specific types of
36
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wastes and individual installations, examples being those by Nemerow (57),
Palladino (58), Fuller, Williams, and Moultar (59), and Linsey, Sullins,
and Fluharty (60).
i
Presently more than 75 of the 118 kraft pulp mills in the U.S. are
equipped with mechanical clarifiers and 21 with settling basins. The
waste from 15 of the 38 acid sulfite mills and 25 of the 39 neutral sulfite
mills are treated in clarifiers. While most waste paperboard mills
discharge into public sewers, at least 30 of these are equipped with
their own clarifiers as are five of the six large deinking operations;
the remaining employ alternating settling basins. Most large groundwood
operations are associated with kraft and sulfite pulping and newsprint
manufacture and the effluent is combined for treatment with the effluent
from all operations. The sewers are for the most part served by mechanical
clarifiers.
A clear distinction must be made between total suspended solids and
settleable solids. The total suspended solids are all the solids
suspended in an effluent. In laboratory tests particularly, all of these
are removed by filtration through a gooch crucible or fine filter paper,
both of which are used to measure them. The settleable fraction of
these is that which separates from the liquid on one hour's quiescent
settling in a laboratory vessel. Hence, the true measure of performance
of a settling device is the percentage of the settleable fraction that
the device will remove, since it cannot be expected to separate those
which will not settle under the most favorable conditions.
The performance of clarifiers in terms of removal of total suspended
solids reduction is presented in Figure 1. These data were obtained
from a detailed industry survey of practice and performance (53) and
are representative of results obtained in actual installations. It
will be noted that removals of total suspended solids averaged greater
than 80 percent for all except deinking mill effluent which averaged
just under 70 percent. This is due to the relatively large percentage
of inorganic fines in the form of fillers and ink that are highly dispersed
in the waste due to peptizing agents employed in the deinking process.
Depsite the high percentage reduction obtained on settling, wastes
containing pigments and fillers are inclined to be quite turbid after
the bulk of the suspended matter is settled out. Such material as
titanium dioxide, carbon black, iron oxides, and other highly optically
active materials are responsible for this. Decoating wastes behave
in much the same manner with some inorganic materials remaining in
dispersion due to the peptizing action of starches used in the coating
process.
Since at least a portion of the settleable solids present in pulp and
paper mill effluents is biodegradable, clarification results in some
reduction in the BOD value. The magnitude of this reduction is high
in the case of effluents containing mainly suspended organics and
small quantities of dissolved organic matter. For example, some
37
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Clarifier at Paper Mill
-------
FIGURE 1
PERCENT TOTAL SUSPENDED SOLIDS
REDUCTION EFFECTED BY SETTLING
01
o
00
O
o
DEINKING MILLS
BLEACHED KRAFT MILLS
LINERBOARD MILLS
WASTE PAPERBOARD MILLS
FINE PAPER MILLS
INSULATING BOARD MILLS
TISSUE MILLS
NEWSPRINT MILLS
WRAPPING PAPER MILLS
SPECIALTY BOARD MILLS
39
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specialty board effluents contain little but fiber fines, hence their
removal produces a BOD reduction exceeding 90 percent. Conversely,
waste paperboard mill effluents contain a considerable quantity of
organic materials dissolved from the old papers. Hence, even when
clarified to crystal clarity, they can retain as much as a third of
their originial BOD value. This is also true of effluents containing
pulping and bleaching solubles.
Another factor involved is the fact that the oxygen uptake rate of
fiber is slower than that of dissolved materials, since it must first
be liquified by microbial decomposition before oxidation can take place.
This effect is illustrated in Figure 2 which compares the BOD rate curves
of dissolved materials with that of fiber. It will be noted that the
oxygen demand of the solubles was largely satisfied in 5 days, while the
fiber continued to consume oxygen over the 20-day period of incubation.
Thus, the mere fact that the BOD is a five-day test stresses, in the
results obtained with settling, the presence of dissolved oxygen-consuming
materials and limits the demand figure assigned to the settleable organics.
Results obtained on tabulation of BOD data for a number of mills
producing various products is presented in Figure 3. It is obvious from
these results that effluents from tissue and fine paper mills, which
were low in dissolved organic matter, showed high BOD reductions on
settling. Pulp mill and waste paper operations yielded low BOD reductions
since they contain appreciable organic matter in solution.
Treatment plant performance data from an integrated mill was treated
statistically by Burns and Eckenfelder (61). Their statistical comparison
of primary clarifier performance in terms of suspended solids and BOD
reduction is presented in Figure 4.
A variation of ±5 percent occurred in suspended solids removal and about
the same for BOD^ reduction.
BOD Reduction
Biochemical oxygen demanding materials can be precipitated from most
pulp and paper mill wastes by the use of coagulating chemicals. However,
the percentage reduction obtained in this manner is small as compared
to that obtainable by biological treatment. Hence, the latter method
is the most widely practiced. It also affords a flexibility in the
degree of BOD reduction obtained since systems can be tailored to
receiving streams' requirements relative to dissolved oxygen resources
and consumption rate.
All pulp and paper mill wastes can be oxidized biologically. Some need
to be diluted and/or neutralized and most, being low in nitrogen and
phosphorus, require addition of these nutrients when higher rate processes
are applied. Their amenability to such treatment is evidenced in the
references presented in the annual reviews of the literature published
40
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FIGURE 2
BOD RATES OF SUSPENDED
AND DISSOLVED ORGANIC MATTER
100
80
z 60
o
H
O
O
UJ
cc
d°
o
CD
40
IV^DISSOLVED
/ SOLIDS
SUSPENDED
SOLIDS
20
10
\5
20
TIME IN DAYS
41
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RGURE 3
BOD5 REDUCTION EFFECTED BY SETTLING
% BOD5 REDUCTION
0)
o
00
o
o
o
T
LINER
NEWS
BL. KRAFT
WASTE PAPERBOARC
DEINKING MILLS
INTEGRATED MILLS
WHITE PAPER MILLS
INSULATING BOARD
TISSUE MILLS
WRAPPING PAPER MILLS
SPECIALITY BOARD MILLS
T
T
42
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FIGURE
STATISTICAL COMPARISON OF PRIMARY
TREATMENT PERFORMANCE - BOD REMOVAL
30
O
yj
cc
o
o
00
AUG. 1960-PRESENT
JUN. 1959-JUL. I960
BEFORE JUN. 1959
35 10
I I I 1 I I I I J 1 I I I I i
2 5 10 20 30 40 50 60 70 80 90 95 98 99
FREQUENCY OF OCCURRENCE
43
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by the WPCF, in the bibliography of biological treatment of pulp and
paper mill effluents, and in a manual on the subject published by the
NCASI (62,63).
Through the years, all forms of biological treatment have been explored
extensively. Of these, three have become established and widely applied
These are storage oxidation, aerated stabilization, and activated sludge.
There are also modifications such as contact stabilization and extended
aeration. Very intensive investigation of trickling filters has not
led to their adoption except for special purposes. There is only one
large unit in operation and it is a pre-treatment device. These filters
have the ability to remove a fraction of the BOD5 from a large volume of
waste, but if a high percentage reduction is required filter size
becomes disproportionately large, and therefore, costly (64). Small
plastic media filters are sometimes used in pre-cooling towers and as
such remove some BOD as pointed out by Burns and Eckenfelder (65, 66).
They have also been applied to in-mill cooling and treatment of
kraft mill condensates on an experimental basis by Estridge (67). In
this capacity they act not only as biological treatment units, but stripping
devices as well since the constituents of the condensates responsible
for the BOD are volatile organics such as methanol. The use of log
and chip piles as biological filters has been a subject of investigation
(68,69) although adoption of this technique is most unlikely since it
disrupts the raw material flow of the mill.
Storage Oxidation:
Storage oxidation was the first type of biological treatment adopted in
the industry. This was first used by, and is still most prevalent in the
southern kraft industry, where a number of mills were able to procure
large areas of land having suitable topography remote from dwellings for
this purpose. The high ambient temperatures of the south allow maximum
oxidation rates to be realized throughout the entire dry season in most
cases. Berger (70) summarized results obtained at a number of these
mills. Heustis (71,72), Bodenheimer (73), Webster (74), and Chapman (75)
report on results obtained with both deep and shallow storage oxidation
basins. BOD loadings for which these basins are designed are from
50 to 60 pounds per acre of surface area per day. Reductions obtained
in relation to time are presented in Figure 5.
It is imperative that settleable solids be effectively removed ahead
of such basins since if deposited therein they will liquify on
decomposition adding more BOD than was contained in the wastewater
itself. Under these conditions the effluent can deteriorate to a point
where its BOD is higher than the influent. Nutrients do not accelerate the
slow oxidation occurring under these conditions so are not employed.
Retention time ranges from 20 to over 300 days producing BOD reductions
from about 50 to in excess of 95 percent.
This method of treatment enjoys the advantage of being capable of
handling accidental discharges of strong waste without upset and
performs well on a continuous basis since no mechanical devices are
44
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FIGURE 5
EFFECT OF STORAGE TIME
ON BOD REDUCTION
100
2 80
O
H
O
60
o
UJ
o
o
CO
UJ 40
ft:
UJ
QL
20
/ /
/
/•^SHALLOW
/ BASIN
10 20 30
STORAGE TIME - DAYS
V.DEEP
BASIN
40
50
45
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involved which can get out of order. Twenty-one large kraft mills in
the U.S. employ this type of treatment, as pointed out by Gehm and
Gove (76), as does one large deinking mill described by Ross (77).
A number of very small mills also use these basins although use of
this method is limited to weak wastes because of odor problems. Porges
(78), in a survey of the application of storage oxidation in industry,
lists most of these installations, and their design is discussed by
Hermann and Gloyna (79), Blosser (63), and Edde (80).
In some cases these basins are also used for discharge regulation when
mills are located below peak load hydro-power stations, in semi-arid
regions, or where stream flows reach;extremely low levels.
Activated Sludge Treatment:
As a result of experimental work started in 1950 (81), the activated
sludge process was adapted to treating pulp and paper mill wastes.
Early experiments were followed by pilot plant investigation by Palladino
(82), Gehm (83), Bishop (84), and Kniskern (85). Trials on modifications
of the process were later carried on by Weston and Rice (86) and its
adaptation to other specific wastes by Nylander and Rennerfelt (87),
Shnidler (88), Sullins (89), and 1/Jaldmeyer (90).
Design and operation of the first large plant to be built were described
by Moore and Kass (91) and its operation by Pearman and Burns (92).
This plant, treating waste from a bleached kraft and linerboard mill,
was followed by others treating kraft pulp mill newsprint and fine
paper wastewaters as well as waste paperboard effluent in this country,
and similar wastes in Europe (93,94,95).
This process operates successfully at over ten mills in this country.
It has been found capable of removing in excess of 80 percent of the
BOD5 from effluents to which nutrients have been added. Because of the
nature and temperature of these wastes, high oxidation rates are possible
so that loadings in excess of 100 pounds of BOD per 1000 cubic feet per
day of aeration capacity are obtainable, allowing the use of relatively
small aeration tanks. Mechanical surface aerators are most commonly
employed although diffused air has been used at two plants. The major
difficulty relative to their operation is the dewatering and
disposal of the waste activated sludge. This material is extremely
slimy and must be mixed with more free materials to be successfully
dewatered; primary sludge, bark, and fly ash being examples of these.
In one instance it has been disposed of on plowed land. Experimental
work employing centrifugal thickening and heat treatment is now underway
in the hope of finding a solution to this problem.
Three mills employ modifications of the activated sludge process, one
using contact stabilization (96) and two extended aeration plants (96,
97), and one treating strong wastes from a magnesium base bleach
sulfite pulp mill.
46
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Design and operation of a number of these plants are described in NCASI
Technical Bulletin #220 (97) and #214 (80), and others by Coughlan (98),
Billings and Narutn (99), and Butler (100).
Aerated Stabilization Basins:
The long period of time required to produce a relatively high degree of
BOD reduction on storage is due to the low rate of natural reaeration.
This time can be reduced substantially by induced aeration as pointed
out by Amberg (101), Eckenfelder (102), and a number of others (103,
104,105,106,107). In order for the potential of this method of treatment
to be fully realized, it is necessary to add nutrients since most pulp
and paper effluents are deficient in these elements. These additions
are usually made in the form of ammonia and phosphoric acid. The longer
the retention period of the waste undergoing biological oxidation, the
lower the nutrient requirement. In some instances no addition is required
since the small quantity contributed by sanitary sewage, boiler blow down,
and detergents suffices. The effect of nutrients on the oxidation rate of
pulp and paper wastes is discussed by Nowacki (108,109) and Tracy (110)
in detail.
Aeration is generally induced by mechanical surface aerators which are
capable of dissolving on the order of 50 pounds of oxygen per horsepower
day (111,112,113). Diffused air can be employed but is less efficient.
Recently a downflow bubble aerator has been developed for use in
deep basins (114).
Eckenfelder (115) and Edde (116) discuss the design of these basins
including configuration, power requirement, and aerator placement,.
These basins are generally designed for from five to ten days retention
time since this provides a sufficient period to produce a 8005 reduction
on the order of more than 80 percent and allows stabilization of the
biomass by means of autogenous respiration as well as dispersion of
most of the resulting debris. Some sludge accumulates in the bottom
of these basins but is relatively inert and readily removed periodically.
If BODg removal in excess of 90 percent is required, the retention
period is about ten days. At some mills a settling basin follows the
aeration unit in order to improve effluent clarity. Gellman (117,118)
and Gehm and Gellman (119) discussed the performance of aerated basins
treating various types of pulping and papermaking wastes finding them
all responsive to this treatment.
Vamvakias et al (120) investigated the effect of temperature on the
efficiency of the process under carefully controlled laboratory conditions
as did Weston and Rice (86). They found that while efficiency decreased
with the temperature, this effect was not as severe as anticipated and
that good BODc reductions were obtained in five days at 2°C. The
adverse effect of low temperature is minimized with increased retention
time as shown in Figure 6. Bailey (96) reporting on basin performance
at sub-freezing ambient temperatures indicated that operation under
these conditions was satisfactory.
47
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FIGURE 6
EFFECT OF TEMPERATURE ON BOD REDUCTION
IN AERATED STABILIZATION BASINS
90
80
z
O 70
O
LJ
OC
§° 60
CD
50
TEMP °C
2.5
T
5.0
7.5
10.0
AERATION TIME (DAYS)
43
-------
However, the effect of temperature for aerated stabilization basins is
not too well established. Initial temperature of the waste, basin
configuration, and depth all affect the operating temperature during cold
weather. Some winter decline in efficiency can be anticipated for basins
of this type.
Operation of a number of these basins at large kraft mills is reported
in the literature, i.e., papers by .Bailey (121), White (122), and Ebersole
(123). Canadian operations are reviewed by Voege and Stanley (124). Some
30 installations of this kind have been made at pulp and paper mills in
the U.S. They provide a high degree of BOD reduction without very
extensive land use and at capital and operating costs lower than those
for highly accelerated oxidation processes. The advantage of this method
is that it does not-produce a slimy waste sludge, difficult to dewater
and dispose of. Effluents produced at reasonably high BOD reductions
are not conducive to slime production in receiving waters.
Burns and Eckenfelder (125) prepared statistical analyses of activated
sludge plant performance and Weston and Rice (86) did likewise for aerated
stabilization basins. Typical data from the activated sludge study is
shown in Figure 7: Overall performance in terms of BOD reduction was
found to range from about 70 to 85 percent with 80 percent reduction being
achieved 80 percent of the time.
Biological Treatment Summary:
It can be concluded that biological treatment in its several forms is
now extensively employed in the pulp and paper industry for reducing the
BOD of spent process waters. When properly preconditioned all of the weak
wastes of the industry are responsive to such treatment, with the degree
of reduction depending upon the extensiveness of the facilities, provided.
The selection of the specific method at a particular mill frequently depends
upon land availability since the methods requiring a considerable area are
the least expensive and often the most reliable. Within limits, the level
of BOD reduction can be adjusted by design and operation to meet local
requirements. Natural performance limits have been established by statistical
analysis of the performance of such plants over long periods of time by
Burns and Eckenfelder (125) and Weston and Rice (86).
Added benefits obtainable from biological treatment are the destruction of
toxicity to aquatic life (126), reduction in foaming tendencies (127), and
reduction of turbidity-producing inorganic coating additives. High degree
treatment also eliminates the tendency of pulping effluents to stimulate
slime production in receiving waters (128).
The shortcomings of biological treatment are its failure to remove color
to a high degree and the production by high rate processes of a waste
sludge of an extremely slimy nature (129). Color bodies are not oxidized
(28) and at best only a fraction of them absorbed into the biomass. The
use of these processes will be limited until better solutions than those
presently available are found to solve the sludge disposal problem.
49
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FIGURE
STATISTICAL COMPARISON OF SECONDARY
TREATMENT EFFICIENCY-BOD REMOVAL
100
90
80
O
yj
a:
a
o
CD
70 —
60
50
I I I I I I I I I
J_J_ L
10 20 30 40 50 60 70 80 90 95 98
FREQUENCY OF OCCURRENCE
50
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Irrigation and Land Disposal
Irrigation:
Although extensive field studies of the disposal of mill effluents by
irrigation have been made by large kraft producers (130,131,132,133),
actual use of this technique has been made only by small paper mills.
This is because of the limited amount of effluent that can be applied
per acre in relation to the volume of mill discharge. It had been hoped
that irrigation of southern woodlands would lead to an increase in wood
yield that would justify the extensive irrigation systems required. Experi-
ments left considerable doubt that the increased yields realized could
justify the cost (133,134), hence, no large-scale project of this kind was
developed. However, rice, vegetables, peanuts, and fodder crops were all
successfully grown at high yields using kraft mill effluents as irrigation
water.
A number of small mills employ irrigation as both a means of secondary
treatment and as a seasonal supplement to secondary treatment. There
are descriptions of some of these applications in the literature (135,
136,137,138,139,140). Wastes from fine paper, tissue, corrugated board,
waste paperboard, and hardboard production are all treated in this fashion,
mainly by small mills located on streams having very low seasonal flow.
Extensive investigations conducted by NCASI and reported in several
technical bulletions (141,142,143) and by Gellman (144) have established
the parameters and good practice requirements for this form of treatment.
Percolation through the soil is extremely effective and, during dry weather,
color bodies present in pulping wastes are inclined to leach out when the
soil is washed with rain water. From 10 to 20 thousand gallons per acre
per day of weak wastewaters can be successfully disposed of in this manner.
With stronger wastes the BOD or organic solids determine the allowable
application rate. Blosser and Caron (138) recommend that BOD loadings
be held to less than 200 pounds per acre per day. Parsons (137) reports
that total solids application of as high as 500 pounds per acre per day
have been applied in irrigating with fiberboard wastewater having a
solids content of two percent.
While spray disposal started as a summer dry weather procedure, it has been
used at some locations recently the year round with a measure of success
(140).
Land Disposal:
Soil percolation is employed for the disposal of spent acid and neutral
sulfite liquors at small mills. Experience with this method of disposal
has been reported by Billings (145), Guerri (146), and Wisniewski et al
(147). One mill recently reported on disposing of 200,000 gallons of
NSSC liquor containing ten per cent solids from a 250 ton dry mill. An
average of one-sixteenth inch per day is applied, three-eighths to
seven-sixteenths inch being sprayed on in a day and a six-day resting
51
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period allowed. The liquor solids are absorbed and decomposed in the
soil and do not reach adjacent surface water or wells. This method is
applicable only at small mills having especially suitable land which is
not in the proximity of dwellings.
Foam Control
Effluent foaming in receiving waters is a problem experienced by pulp
mills since alkaline liquors have a strong propensity to impart this
quality to water. Other waste constituents can do likewise but these
are the most common offenders in both treatment plants and receiving
streams. Some paper mill wastes can also cause this effect due to
residual amounts of additives present in the white water discharged, as
can coating-kitchen wash waters.
There is relatively little literature on the measurement of foaming
capacity or its control in pulp and paper effluents despite the fact
that control methods are well established, widely used, and quite
effective. Carpenter (127) developed a method for comparing foaming
potential based upon methods employed in the detergent industry which
appears to be the only technique presently available to measure this
factor in pulp and paper effluents.
Foaming problems are common within mills themselves and these difficulties
are frequently the cause of the problem in effluents, foam or black liquor
being carried directly into sewers. In-mill sewering arrangements can
give rise to foaming. This can be avoided by correction of the sewer
system to prevent direct admixture of alkaline and acid wastewaters within
them and correcting arrangements and pumping systems which give rise to
air entrapment, a major cause of foaming in itself. Maximum control of
black liquor losses is mandatory if foaming is to be kept at a reasonable
level both during effluent treatment and in discharge.
Since some biological treatment processes depend upon aeration of the
waste, foam is bound to develop. Under normal conditions with most
wastes this can be maintained at a minimum level by in-plant control
or by the use of surface sprays installed in treatment basins. In most
instances with good mill loss control, foam levels will stabilize in
treatment units and not become unmanageable. Biological treatment is
effective in itself in reducing foaming tendencies.
52
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SECTION VI
ADVANCED WASTE TREATMENT
With some qualifications, satisfactory methods are available both for
clarifying pulp and paper mill effluents and reducing their content of
biologically oxidizable matter responsible for deoxygenization and
slime growth in receiving waters. Such treatment appears to be effective
in destroying potentially aquatically toxic components present in kraft
mill effluents but also those materials adversely affecting fish
productivity.
The remaining difficulties in clarification are the removal, to the
extremely high degree desirable, of pigments used in papermaking--such
as titanium dioxide and carbon black which are exceptionally optically
active. Through light reflectance and absorption they can, in infinitesimal
concentration, affect the appearance of surface waters to an undesirable
degree.
The major problem attendant to the reduction of biologically active
substances is disposition of the zoogleal matter formed as a result of
its decomposition. Separation of this from final effluents and its dewatering
and disposal are the subject of considerable research and development which,
if pursued, should provide answers to this problem in the not too distant
future.
A third problem is the disposal of sludges high in ash content which
are not responsive to incineration. The industry has been investigating
advanced land disposal methods for sludge and is seeking assistance from
the Office of Solid Wastes Management Programs in extending these
investigations.
The major remaining problem involves the biologically refractive fraction
of pulping wastes largely responsible for color. An examination of
the literature and number of private communications established the
values for color discharged from various pulping processes shown in
Table 4. Wood species, age, and processing variables all affect these
values but the ranges shown reflect the usual situation.
The individual process distribution of color from the kraft process in
a linerboard mill is shown in Table 5.
This is subject to great variation from mill to mill and from time to
time since it depends upon both equipment capacity and momentary functioning
efficiency of each unit process.
Research and development work on color reduction started over 30 years
ago in the United States. These studies were stimulated by complaints
of discoloration of small streams by mills located on them rather than
53
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by specific governmental regulation. Today, as federal and state
standards are being set which contain color limitations, the industry
is fortunate in having an appreciable background in this area, and
has been able to respond with large-scale process demonstrations
which can be expected to lead to workable systems of practical economy.
Table 4
VALUES FOR COLOR DISCHARGED FROM VARIOUS PULPING PROCESSES
Effluent
Kraft Pulping
Kraft Papermaking
Kraft Bleaching
NSSC Pulping (Recovery)
Sulfite Pulping (Recovery)
Sulfite Bleaching
Pounds of Color Units per Ton of Product
50 to 300
3 to 8
200 to 300
200 to 250
30 to 200
50 to 300
Table 5
UNIT PROCESS FLOW AND COLOR DISTRIBUTION
IN INDIVIDUAL KRAFT PULPING EFFLUENTS
Paper Mill
Pulp Mill
Evaporators
Recovery
Caustic House
Flow Thous. Gal/Ton
11.4
0.9
0.1
0.2
.8
Color Units
10
520
3760
20
20
54
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Research and development studies carried on by NCASI, individual pulp
and paper companies,-and universities supported in part by Federal grants
included the following:
1. Improved methods for the measurement of color in effluents
and receiving waters.
2. The physical and chemical characteristics of color bodies
contained in pulping and bleaching effluents.
3. Effect of biological oxidation on color.
4. Possible application of the foam separation process to
color removal.
5. Adsorption of color by activated carbon, resins, various
• minerals, and by the soil, together with adsorbent recovery
for reuse.
6. Application of membrane processes for color removal.
7. The effectiveness of bleaching process changes on effluent
color.
8. The effectiveness of chemical reagents for reducing the
color of water together with their recovery for reuse.
Data obtained from,a review of these studies are set forth briefly
below, together with some conclusions which can be drawn:
The measurement of color is affected by the pH of the wastes. Hence,
for comparative purposes, and to better reflect the effect on receiving
waters in terms of color, measurement is made near neutrality (pH 7.6).
The optimum wavelength for spectrophbtometer measurement appears to be
465 mym for all the common pulping and bleaching effluents (159, 160).
Color bodies present in these wastes pass, to a large degree, through
submicron filters, hence are probably molecular in nature rather than
colloidal sols. Bennett et al (161) have shown conclusively that the
solids contained in spent caustic extract consist of comparatively low
molecular weight chlorine-substituted acidic material displaying little
phenolic character and that their precipitation by lime and other reagents
is a chemical reaction rather than physical in nature.
Even extended biological oxidation both in treatment systems and in
surface water has relatively little effect on waste color, particularly
that originating from bleaching. Activated sludge treatment can remove
up to one-third of the color from kraft pulping effluents. It is
not as effective when bleachery wastes are present. This observed
reduction is probably due to adsorption of some of the color by the
sludge matrix. A darkening has been observed on storage oxidation
55
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which is probably caused by iron tannate formed by reaction of tannins
with soil ingredients.
/
Attempts to remove appreciable percentages of the color from pulping
and bleaching wastes by the foam separation process failed ,to achieve
results (162). A separation could be obtained on addition of a relatively
large dosage of a surfactant but economics ruled out its use. Recently,
experiments along the same line have been conducted in France (163) yielding
similar results.
The most effective adsorbent for color bodies has been found to be
activated carbon (164, 165). Most other adsorbents were found to be
of little practical value. Present research deals with the manufacture
of a low cost and effective carbon that can be used once and burned, as
well as development of satisfactory thermal and chemical carbon recovery
processes. Regeneration is presently a basic requirement for the efficient
application of carbon adsorption (311).
On percolation of color bodies through the soil, they are adsorbed
to a high degree by most soils during the dry season and leach out
during wet periods when rain water passes through the soil at a
relatively high rate (166).
A large paper company which has considerable research and development
capability in recovery processes has received a large federal grant to
help finance a process for manufacturing low cost carbon from black
liquor and applying it to effluent reclamation. Some preliminary results
have been reported by Timpe et al (167) on the adsorption properties of
such materials for which high loadings were observed. One resin manufacturer
reports the development of a new group of synthetic adsorbents that will
be laboratory tested for pulping and bleaching wastes shortly (168).
An extensive research and development program on the use of reverse
osmosis for concentrating the dissolved solids present in weak sulfite
wastes and reclaiming process water was conducted jointly by the former
Pulp Manufacturer's Research League and the Environmental Protection
Agency (EPA) (169). After extensive laboratory work with the process,
a portable reverse osmosis pilot plant was assembled and operated
at several mills of different types including acid sulfite and NSSC plants.
In additon to concentrating solids for introduction into recovery or
incineration systems and reclaiming water, the separation of acetic acid
and sugars having unique properties was attempted. While the reports
covering these investigations have not as yet been published, it has
been pointed out by the participants (312) that flux rates obtained were
undesirably low and the membrane life fell short of that required for
commercial practicability. These observations were confirmed by other
investigators (313). Very extensive effort is being expended by membrane
manufacturers and others supplying hardware for these systems and it is
anticipated that these shortcomings will be overcome to some degree in
the not too distant future.
56
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As an outgrowth of these studies, a Wisconsin paper company, which
manufactures NSSC pulp and corrugating medium, has agreed to join in
a project with EPA-OWP to conduct comparative pilot plant tests of
various proprietary reverse osmosis systems for concentrating weak
pulping wastes to a degree that they can be introduced into the existing
fluidized bed burner handling the spent liquor. If results obtained
with the most efficient unit tested appear favorable, plans call for
the installation of a demonstration unit at the mill. The company is
attracted to the process because it removes both BOD and color and
could possibly lead to a closed system.
While there is considerable interest in oxygen bleaching and the Rapson
process for improving the discharge from bleacheries, neither of these
processes have as yet been operated in the United States (233).
However, five mills are now employing a change in bleaching sequence to
reduce effluent color. By employing a C-H-H-D sequence, caustic extraction
is eliminated, resulting in a color reduction of about 90 percent. The
cost of this procedure is between 50 cents and a dollar per ton of
pulp bleached. Its use is limited to production of book and similar
papers because of the resultant low pulp strength.
Biological treatment removes, at best, only about one-third of the color
from bleaching effluents and is more effective for unbleached mills.
Sanks (171) experimented with ion exchange resins for reducing color
as has Walker (168). This work is still in the early stages and has
been plagued by irregularity of results.
Chemical precipitation processes nave been a major subject of interest
for 30 years and many reagents and combinations thereof were tried for
removing color bodies. Of those tested, interest remains in lime
and, to a much lesser degree, in alum. Extended research by the NCASI
in collaboration, with mills and university investigators has demonstrated
the general effectiveness of this process in a comparatively large number
of mill situations and opens up the possibility of its incorporation
into the kraft recovery system. Today, five large full-scale operations
of this kind are underway either employing the basic procedure of effluent
control or determining its feasibility.
The first large-scale installation was made at a new 400 ton per day
linerboard mill located at the upper end of a "dead" estuary where a
high degree of suspended solids, BOD, and color removal is required.
The process employed has been described in detail by Davis (72) and a
flow sheet of it is presented in Figure 8. The waste treatment
facilities were a joint venture of the company and EPA.
This system employs between 30 and 40 tons per day of calcium oxide
which is produced from limestone in the mill's recovery system kiln
which was sized to handle this load in addition to the normal requirement
of the causticizing system. It is the minimum dosage required for
57
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en
CO
FIGURE 8
INTERSTATE CONTAINER CORPORATION COLOR REMQVAL PROCESS
STEAM
SLAKED
LIME
STORAGE
00
HI-LINE
MIXER
FLOCCULATOR
EFFLUENT
WATER
SLAKER
/\
LIME
STORAGE!
TANK
EMERGENCY
DIVERSION
BOX
TO OXIDATION POND
SUPERNATANT
SLUDGE LAGOON
-------
maximum color reduction since the hydrous sludge produced by the
precipitated color bodies and suspended matter in the mill waste is
disposed of in lagoons. The average raw waste color value of 750 units
is reduced to between 50 and 100 units and is accompanied by a BOD5 reduction
ranging from 25 to 35 percent. Further treatment is provided by storage
oxidation. Experiments are now being conducted at this mill on
recarbonation of the effluent from lime treatment using kiln off-gas
as the source of carbon dioxide.
The second installation to be put into operation is the NCASI "massive
lime" process as described by Berger and Gehm (173). It is integrated
with the recovery system of the bleached kraft mill where it is installed
as illustrated in Figure 9. It is designed to handle a portion of the
caustic extract of sufficient size so that operating and recovery problems
which might arise from its use can be identified. This installation
has been in operation for too short a period to permit a report and
is also an industry-EPA undertaking.
A third joint project of this type is under construction by a combined
kraft and semi-chemical pulp mill, the flow diagram for which is shown
in Figure 10. The process employs a minimum lime dosage to obtain
good precipitation of color bodies and uses the lime mud from causticizing
as a filter-aid to permit its handling on the mud filter. Operation
of this unit is anticipated in the near future, treating a mixture of
unbleached kraft and NSSC pulping effluents.
A similar process has been employed by one company to treat a mixture
of caustic extract and hydraulic barker waste at one mill and caustic
extract alone at another site, both of which are full-scale operations.
The process appears at present operable although some problems have appeared
in dewatering the organic-laden mud.
Berger (174) suggests still another process which ,is diagrammed in
Figure 11. In this the lime mud, which contains some free Ca(OH)2,
is added to the colored effluent together with supplementary hydrate.
Precipitates obtained are dewatered on a filter together and the cake
is returned to the kiln. This process is still in the laboratory stage
and may not prove to have any advantage over the other system employing
lime mud.
Both acid and neutral sulfite pulping effluents respond to lime treatment
as reported by Sutemeister (175) and by Vilbrant (176). Their work dealt
with strong spent liquors, the former being directed toward separation
of liquor sulfonates for by-product manufacture.
Detailed performance data of an advanced waste treatment system embracing
color reduction at a linerboard mill is reported by Davis (177). A simplified
flow diagram of the system is presented in Figure 12. The data showed
that effluent color values of from 50 to 180 units were obtained when
treating a feed ranging from 460 to 2120 units. Beyond a certain level no
further color reduction resulted from an increase in the lime dosage
59
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FIGURE 9
MASSIVE LIME PROCESS FOR COLOR REMOVAL
LIME
MAKE-UP
UNDERFLOW
VACUUM
FILTER
SLAKER
^^
I
£HERY EFFLUENT
^
P O
r \J
CLA
FILTRATE
•GREEN LIQUOR
! CO
I LIME RECLAIMER
u
WHITE LIQUOR
CLARIFIER
CAUSTIC I ZING
DECOLORIZED
EFFLUENT
LIME MUD
TO KILN
MUD
WASHER
-------
FIGURE 10 CONTINENTAL CAN CO. INC.,COLOR REMOVAL PROCESS
cr>
REACTION
BASIN
LIME
STORAGE
PRIMARY
CLARIFIER
CARBONATOR
CAUSTICIZING LIME MUD
LIME MUD TO KILN
LJ
CLARIFIER
PH
ADJUSTMENT
TREATED
WATER
VACUUM FILTER
-------
FIGURE 11
LIME MUD PROCESS FOR COLOR REMOVAL
MUD FROM
WASHER
NEW MUD
FILTER
1
FILTRATE TO
WASHER
MUD
BLEACHERY
EFFLUENT
MIX TANK
EXISTING
MUD FILTER
STACK GAS TO
CARBONATOR __
KILN
LI ME-ORGAN 1C SLUfiGE
CLARIFIER
SMALL
SLAKER
SLAKED LIME
PROCESS
LIME
DECOLORIZED
EFFLUENT
CARBONATOR
-------
FIGURE 12
TO RECEIVING STEAM
AERATOR
ADVANCED WASTE TREATMENT SYSTEM EMBRACING
COLOR REDUCTION AT A LINER BOARD MILL
EFFLUENT OXIDATION POND
LIFT PUMPS
cr>
CO
SLAKED LIME
IN-LINE
MIXER
FLOG
MIX
TANK
SLUDGE
,, PUMPS
SCUM
PUMP
rilLL
EFFLUENT
<**
C
\-s
DECANT PUM
<~
SLUDGE LAGOON
SUMP
SLUDGE LAGOON
-------
at any feed color values, indicating that a constant fraction of
non-precipi table color is present in this waste. This is demonstrated
by Figure 13 which was reproduced from Davis1 paper.
Average BOD and COD reductions have amounted to 34 and 46 percent,
respectively. The lower values observed were 190 mg/1 for BOD and
400 mg/1 for COD. These values in relation to residual color are
shown in Figure 14 reproduced from the same paper.
Subsequent treatment of the effluent is by sto age oxidation which
represents no problem in the large basins provided, the effluent containing
between one and two pounds of BODs per ton of product. However,
about one-sixth of the capacity is consumed in neutralization of
the caustic effluent through reaction with atmospheric carbon dioxide
before biological oxidation can commence.
Continuing studies have been directed toward neutralization and lime
recovery by reaction with lime kiln off-gas before discharge to the
basin. Such treatment might also serve to minimize the leaching of
color from the basin bottom which now occurs and reduces the effectiveness
of color reduction treatment markedly. The organic content of the
soil in the swampy area in which these basins are constructed is responsible
for this condition.
The final effluent from the basin is raised to near dissolved oxygen
saturation in a small basin containing a mechanical aerator.
This experience has indicated that color reduction costs for lime
precipitation are very high for the simplest type of full chemical
pulping and papermaking operation with the most efficient recovery
system available, the major cost being for lime. As pointed out by
Davis, the percent increases in color reduction above the 1000 ppm
Ca(OHJ2 level costs $38 per million gallons of waste treated or
about 50 cents per ton of product. Thus it is obvious that a process
involving lime recovery is needed to make the lime precipitation process
acceptable to widespread application.
It can be concluded from this review that substantial work is being
carried on in the United States in the area of color reduction from
pulping and bleaching wastes. These studies have a further impact
since in the process of removing color a very substantial portion of
the total organic matter present in the wastes is also removed. This
makes the processes attractive from the standpoint of water reclamation
whether it is practiced in-mill or on downstream water.
The willingness of the federal government to contribute substantially
to the industry effort in this area bears witness to the importance
currrently attached to the problems at the regulatory level.
64
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FIGURE 13
TREATED WASTE COLOR VS LIME CONCENTRATION
2OO
en
tn
X
IL
OL
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I
oc
o
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o
u
UJ
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IOO
50
AV6. COLOR (UNITS)
(2120)
(1610)
g ^
T
_L
I
I
I
I
I
_L
1000
1200 1400 1600 I8OO
CALCIUM HYDROXIDE CONCENTRATION-PPM
2000
22OO
-------
FIGURE 14
TREATED WASTE COLOR VS. -COO AND BOD
IOOO
o
O
<-> 800
600
O
8:
•
o
z
IU
UJ
2
X
o
5 4OO
ui
i
200
CD
m
S
O
X
m
z
o
m
z
o
I
m
o
o
56
IOO ISO 2OO 250
TREATED WASTE COLOR-PPM APHA UNITS
300
-------
SECTION VII
WATER REUSE AND RECLAMATION
Throughout the years, the chemical pulping recovery processes have
been improved to a very high degree as has water reuse both within
the pulping and recovery systems themselves and by acceptance of
paper mill wastewaters for use in pulping (20). Recovery improve-
ments in kraft pulping are illustrated by the fact that sewer losses
of soda in terms of Na20 have been reduced from as high as 300 pounds
per ton of product to fess than 35 for modern units. This has been
accompanied by similar reductions in suspended solids, BOD, COD, and
color as pointed out elsewhere in this report. A TAPPI survey re-
ported by Haynes (26) in 1965 revealed that the average use of fresh
process water for a number of Kraft mills examined was two and one-half
times before discharge and that in some mills this value was exceeded
substantially (23, 188, 244, 348).
Water recycle in bleach plants has advanced remarkably in the last ten
years, dropping as low as 15,000 gallons per ton for three-stage semi-
bleaching. However, no reduction in pollution load accompanies water
economy in bleaching since a given amount of material must be removed
from the pulp. This is not recoverable because of its dilute nature
and its high chloride content which is corrosive to recovery systems
and which, in high concentration in the smelt, can cause explosions.
Less information on sulfite mills practicing recovery is available,
partly because of their relatively small number and recent erection.
However, since these are modern installations, they employ liquor
separation and chemical recovery systems of similar inherent efficiency
as kraft although the effluent from them differ in character and pollu-
tion load.
The major sources of sewer losses in kraft pulping are the filtrate
from the final washing of the pulp on the deckers and the condensates
from the digesters and evaporators. While there have been hypothetical
plans for eliminating the decker filtrate by providing greater washing
capacity (210), it has been pointed out by computations made by the
Association of Swedish Steam Users (210), that this procedure, if
carried too far, succumbs to the law of diminishing returns so that
beyond a given range, the recovered liquor is diluted to a point
where evaporation capacity and the attending heat requirement exceed
the benefits derived. This limit is reached when soda loss amounts
to 15 to 20 pounds per ton of pulp.
67
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Reuse of condensates, which are responsible for the second largest
sewer loss, has to some degree aided in reducing sewer losses (352,
214). Steam stripping, which has recently been installed at several
mills, reduces BODj- loss in the condensate by stripping aliphatic
compounds, mainly methanol, from them (22, 356). Since methanol
is readily oxidized by biological oxidation, there is a valid question
as to whether it is more economical to remove it by stripping or in
the effluent treatment plant. It is likely that the answer to this
question is different for particular mills and varies with consideration
of the other materials removed.
Air stripping combined with biological treatment in packed towers has
been tested on a large scale (67). While effective in achieving a measureable
BODc reduction, it releases odorous substances into the atmosphere,
hence can represent a potential air pollution problem. It appears unlikely
that a completely closed pulp mill water system can be achieved as
has been suggested by some (350, 354).
The reduction in sewer losses from sulfite pulping by recovery systems
is less effective than those of kraft because of the large quantity
of acetates and formates appearing in the condensates. This formation
is inherent to acid and neutral cooking of wood. Recovery of acetic
and formic acid has been practiced by one NSSC mill (338) and a method
for its recovery from acid sulfite pulp mills was developed by Lang,
Clark, and DeHaas (299). However, the market for these acids is such
that it does not represent a dependable means of solving the problem
of its discharge on a continuous basis for more than an occasional mill.
Closed water systems in paper mills and paperboard mills have been an
industry dream for many years. In a few cases this dream has been
realized or approached (353). These have been mills manufacturing
small quantities of special products from select furnishes in which
extenuating circumstances necessitated and justified excessive costs
attendant to very high degrees of recycling. While water recycling,
fiber and filler recovery, and improved retention of raw materials in
the paper have been achieved (25, 360, 337), there appears to be
some fairly well-defined limits beyond which successful operation is
either impossible, uneconomical, or fraught with serious operating
problems. The increase in quality requirements by customers and con-
sumers and the desire and effort to recycle more waste paper mitigate
against reducing in-mill losses. It is true that increased water
recycling results in lower fiber and chemical losses to a point.
Beyond a certain level, it is not done since the build up of fines or dirt
in the system by practicing recycling to too high a degree can lead
to greater than normal loss of fiber, filler, and other papermaking
chemicals.
Another factor involved in closing up the water cycle is the con-
centration of substances brought into the process as impurities in
the water supply and the raw materials. Evaporation from the dryers
causes these to accumulate rapidly to a point where they can affect
sheet formation, machine speed, cause corrosion and scaling, or a
host of other problems. This is particularly true in waste paper-
board and deinking mills which receive sizing materials, adhesives,
fillers, and other materials unsuitable for recycle.
68
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In pulping, bleaching, paper-making, and attending operations, such as
process water treatment, steam generation, chemical preparation, and
by-products handling and rectification, a miscellany of wastes are
produced in variable quantity and often at indeterminable frequence.
Furnish cleaning as well as equipment wash-ups add to the wastewater
stream as do leaks, equipment failures, and accidents occurring in
mill operation. While the control of spills occurring from the latter
are under good control at most mills, the residual streams require
treatment and the chance of eliminating them is non-existent. On
careful consideration of the above factors, it appears most unlikely
that pulp and paper mills of the future will operate with completely
closed water systems and with the need for effluent treatment eliminated.
It is more likely that further progress and application will take place
in mill recycling and treatment of effluent streams to a degree
where their reuse is feasible.
Considerable progress in treating kraft pulping and bleaching
effluents for reuse has been made by Berger, Thibodeaux, Smith, and
others (349, 360, 361, 105). The former investigators present
effluent quality data for removal of suspended solids, BOD, COD,
color, and chlorides from pulping and bleaching effluents demon-
strating that it is possible to produce waters that appear acceptable
for some in-mill uses when judged by the quality requirements set
forth by TAPPI (22) and Walter (23).
Berger and others (360, 365) reported on laboratory and pilot plant
trials in which unbleached kraft pulping effluent was treated by lime
precipitation, neutralization, biological oxidation, and filtration
through activated carbon. Effluents were produced by the entire
treatment sequence that contained less than ten mg/1 of BODg, COD, and
color. Total dissolved solids reductions were in the order of 65 per-
cent and consisted almost entirely of salts, mainly sodium sulfate.
These effluents also compared favorably with the characterization of
the range of water quality suggested as desirable for kraft pulping by
TAPPI (22) and Walter (23). Assuming that the lime and activated
carbon could be recovered; that no additional unit processes, such as
filtration prior to carbon treatment, would be required to make the
process function on continuous basis; or that no insurmountable prob-
lems such as carbon sliming occurred, it was computed that water
reusable for all process water or other uses could be produced at a
cost of 14.5 cents per thousand gallons as 6f 1966. This figure
compared with the 10 cents per thousand gallons then costing some mills
for finished process water. It was pointed out that, considering
effluent treatment cost, a substantial saving in overall water cost might be
achieved by increasing the degree of treatment and drastically reducing
the quantity of process water treated. This procedure would also
reduce the pollution load substantially since the quantity of effluent
would be reduced and its quality improved. It must be taken into
account, however, that on repeated recycling a build-up of electrolytes
and other substances will occur in the water within the system. This
will determine the degree of recycle possible, the amount of make-up
needed, and the quantity and quality of the treated effluent discharged.
69
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Carbon filtration of kraft pulping effluent which has removed the bulk
of the color and BOD on a demonstration basis appears worth pursuing-
Such a development study should include reuse of a substantial quantity
of the water in the mill, possibly at a selected point of introduction
into the process. The cost estimate for achieving this ran in the
range of 25 cents per thousand gallons (1967) for a two-MGD installa-
tion. Adding the cost of pretreatment a total of 40 to 45 cents per
thousand gallons of water treated was estimated.
Considerable background information on carbon filtration is available
upon which to base such a demonstration (365, 164, 362, 365). Tempe
(167) reported high adsorption activity for carbon formed on the
pyrolysis of kraft black liquor after a series of preliminary experi-
ments. Rimer e_t. al. (368) conducted trials and proposed the use of
activated carbon filtration for the treatment of specialty and white
paper mill wastes with municipal sewage. Pilot plant treatment results
on the mill waste above indicated that the BODg and COD after settling
could be reduced as follows by one, two, and tnree stages of treatment:
Raw
Stage Waste 1 i 1
Contact Time (min) 5.8 7.2 9.9
BOD, mg/1 13.2 7.6 2.6 1.7
CODbmg/l 53.4 29.2 11.9 6.8
The low efficiency of this treatment for paper mill waste is evident
from the small amount of BOD,, and COD removed. This limits its use to
the area of water reclamation, the cost being prohibitive on the waste
treatment basis alone.
Interest has been expressed by EPA research and engineering specialists
in this area (21).
Thibodeaux and Berger (349) experimented with advanced methods for
removing the chloride ions from bleachery wastes treated for BOD, COD,
and color removal, since it is this ion which limits reuse of such
water in the process and disposal of concentrated waste obtained on
recycle from introduction into the recovery system. This practice
would result in severe corrosion of process equipment as well as
giving rise to possible smelt tank explosions; as noted previously.
Using a process developed by Kunin using weak electrolyte ion exchange
resins and starting with treated effluent containing chlorides in the
order of 500 to 1,200 mg/1, they were able to produce a water contain-
ing from 120 to 460 mg/1. Repeated regeneration was demonstrated
without serious loss in capacity.
Sanks (171) and Walker (168) reported on liberating tests employing
resinous zeolites in the treatment of kraft pulp mill wastes. They
were concerned mainly with color reduction but state that they observed
a high potential for the use of the resins for demineralizing pulping
and bleaching effluents.
70
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It must be pointed out that with ion exchange processes, the ions
removed are not ultimately withheld from the plant effluent nor are
the regenerating chemicals. Ions detrimental to the process are se-
questered from the recycled stream and removed from the resin in a lower
volume of water than that in which they originally were dissolved. Hence,
such treatment will only permit a higher degree recycle when some means
can be found for disposing of the spent regenerant and wash water other
than the mill outfall.
Membrane processes have been the subject of a considerable amount of re-
search and development work relative to pulp mill wastes over the last
few years. Voelker (347) enumerated the advantages of such processes as
the possibility of their eliminating effluents, producing very acceptable
fresh process water, and possible recycling by-products. He sets forth
the major disadvantage as the cost which he computes to amount to $1.17
per thousand gallons of water reclaimed by the reverse osmosis process at
a daily ,inflow rate of 500,000 gallons.
\
Extensive laboratory and pilot plant investigation of membrane processes,
including reverse osmosis and ultrafiltration, were conducted by Wiley
et. al. (169,361, 369) both at the Institute of Paper Chemistry and with
a portable unit operated at various types of mills.
Conclusions reached from these studies were that reverse osmosis and
ultrafiltration processes had a possible application for processes
producing relatively concentrated effluents, such as NSSC pulp and
corrugating board mills practicing a high degree of recycle and
producing a wastewater in the Border of 0.5 to 1.0 percent solids. It
was also concluded that improvement in membrane life, elimination of
clogging problems, and improved support structures as well as increased
flux rate were required to render these systems operable and practical
cost-wise.
Nelson (362) and Leitner (366) report on the development of reverse
osmosis for NSSC corrugating waste at a Wisconsin mill. This mill
employs press washing evaporation and spent liquor incineration in a
fluidized bed unit. The sodium sulfate produced by the fluid!zed bed
is sold to a neighboring kraft mill for liquor system make-up. Very
high degree of recirculation is practiced in the paper mill which runs
at a very high temperature (140°C.). It was found possible to con-
centrate the waste stream, which amounted to close to ten percent
solids. This was suitable for incorporation in the evaporator input
for incineration of the organics and recovery of the chemical. Voelker
(347) points out that reverse osmosis is feasible for carrying on this
step in waste concentration, holding a decided cost edge over evapora-
tion. He presents performance data for a tubular reverse osmosis unit
that was successfully operated for a four-month period which is pre-
sented in Table 6. Beder and Gillespie (313) attempted to remove
chlorides as well as color from bleaching wastes by ultrafiltration.
The low flux rates obtained as well as the chloride in bleed-through
led them to conclude that in its present state the process is not
applicable for either water reclamation or solids concentration.
71
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Table 6
TYPICAL PHYSICAL AND PERFORMANCE DATA FOR A TUBLULAR REVERSED
OSMOSIS UNIT OPERATING ON WASTE HATER FROM A NSSC PULP AND
PAPERBOARD MILL
Number of 36 tube modules (first stage) 24
Normal operating pressure, psi 650
Inlet flow rate, gal/day 14,200
Permeate rate, gal/day 6,800
Concentrate rate, gal/day 7,400
Percent rejection total solids 99.5
Inlet concentration, % solids 1.47
Exit concentration, % solids 2.71
Percent rejection of BOD 99.5
Percent rejection of Color 99.8
Temperature of feed, °F. 95
pH of Feed 7.1
2
Flux rate, gal/ft. /day 7.94
Pressure loss, first stage, psig 110
Note: Unit arranged for self-powered backflush 15 minutes every
two hours at operation. ,
72
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It can be concluded that, in their present state, the application of
the membrane processes to pulp mill effluents is at best very limited
since most of the wastes are too dilute to make the cost of such
treatment in any way practical.assuming that the mechanical problems
associated with them are solved. The three wastes to which these
processes could apply are semi-chemical corrugated board waste, sulfite
pulping recovery plant condensates, and caustic extraction waste from
some bleach plants. In the first case a severe in-mill problem is
involved in reducing th« waste volume to the required level, hence
obtaining a suitable waste solids concentration. The application to
sulfite condensates necessitates a market for the acetic acid produced
and its use for concentrating caustic extract is limited by the chloride
content of the concentrate which can be undesirable for admission to a
liquor recovery system.
Relatively complete process changes such as oxygen bleaching give
promise of reducing kraft mill effluent losses especially with respect
to color bodies and inorganic materials, particularly chlorides. Three
references (258, 359, 351) indicate that the wash water from the
oxygen bleaching stages can be introduced into the kraft recovery
system without immediate untoward effects, since they are relatively
free of chlorides. However, magnesia is added in this process and
it could result in accumulative problems in the liquor system. If
successful, this process could go far in reducing the color and to
a lesser degree the BOD of bleachery effluents. How rapidly it might
replace the present bleaching systems is a most difficult question,
since its use involves high capital investment and the replacement
of an established heavy chemical (chlorine). Also the large-scale
production of another chemical (oxygen) largely on location must be
undertaken. Since other bleaching stages continue to utilize chlorine
compounds, all bleach plant effluent and attending sewer losses are
not eliminated by it.
Rapson and Reeve (350, 357, 233) maintain that countercurrent
washing—both in the bleaching steps and when washing brown stock--
can make unnecessary the addition of any make-up water other than that
needed to replace losses through evaporation to the atmosphere. In
their proposed system, condensate from the evaporation, after steam
stripping or chlorination to deodorize them, could be used to wash the
bleached pulp. Bleach plant effluent would then be sent to the chemical
recovery system modified in such a manner that it could extract sodium
chloride from the liquor for sale or captive use in preparing bleaching
chemicals. Rapson (350), in preliminary estimates, indicates that a
capital cost of close to $4 million would be required to convert a 1,000-
ton-per-day mill to the process but that such conversion could result in
savings of as high as $5.80 per ton of bleached pulp. Such a change,
however, involves a very considerable risk, since its success depends
upon fractional crystallization, which to date no company has undertaken.
Such changes in process are generally evolutional rather than radical.
However, improvements will result from the investigations and proposals
evolved. These can result in considerably lower losses from bleaching
operations.
73
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SECTION VIII
THE HANDLING, TREATMENT, AND DISPOSAL OF SLUDGE
Introduction
The disposal of sludges obtained from the clarification of pulp and
papermaking effluents is still a major problem despite many years of
research, development work, field studies, and applications. In fact,
the problem is of greater magnitude than ever, not only because of
increased production but also because an increasingly larger percentage
of this material, formerly discharged to surface waters, is now removed
from the effluents. The great progress made during the last 30 years
in water recirculation and fiber and filler recovery began to make it
appear as though the immemorial dream of the completely closed paper
machine system would eventually come true. However, these practices
were found to reach a critical level beyond which a number of opera-
tional problems were encountered. Among them are:
1. Foaming in stock system
2. Sheet formation troubles
3. Slowing of the stock
4. Dirt in the sheet
5. Decreased felt life
6. Accentuated slime control problems
7. Difficulties with water.clarification systems
The causes of these troubles were found to be primarily the accumula-
tion of dissolved and colloidal substances entering the system with
the furnish, or produced during the mechanical processing or chemical
treatment of the fibers. The use of the many new paper additives, as
well as the high quality and cleanliness standards required at the pre-
sent time, have not improved this situation. Many mills operating with
close to the maximum of water recirculation have found it necessary to
reduce this practice somewhat, since one way or another the concentra-
tion of the offending substances must be kept below a tolerable level
within the machine system. Hence, it can be reasonably concluded that
some water will have to leave the system to carry the undesirable
materials off, and with them is bound to come some fiber sizing, filler,
and other additive materials.
As improved effluent quality was required, it was believed that filtra-
tion, sedimentation, or flotation devices would alone suffice to remove
suspended solids, if properly designed and with the aid of coagulant
addition. Indeed, in some instances where process water was in short
supply or costly, it was believed that the expanded use of the cleaner
75
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recirculated water would justify the added cost of clarification. This
conclusion was based on the assumption that the reclaimed material
could be used back in the system quite as readily as that returned from
a simple save-all arrangement, despite the finer division of fiber.
This is where real difficulties arose and where the returned slurry
gained the name of sludge rather than furnish.
The characteristics of such material changed altogether in that it was
no longer free-draining but gelatinous in nature. More remarkable was
the fact that on addition of a small proportion to a relatively free
furnish, it was able to transmit its water-holding capacity to the
entire fiber mass of the furnish to a very appreciable degree. Care-
ful examination of the fibers revealed, that the fines, frequently-aided
by coagulants, paper additives, and in the case of wastepaper furnishes,
adhesive materials, plated out on the long fibers changing their physi-
cal characteristics (51).
The National Council for Air and Stream Improvement has published ex-
tensive literature on the various types of sludges. Reports have been
made on sludges varying from 95-98 percent volatile solids for groundwood,
to deinking and roofing mill sludges with ash contents varying from 40"to
70 percent. Between these extremes runs the whole gamut of kraft, sul-
fite, groundwood papers, and various specialties, so that it is almost
impossible to generalize the type sludge to be encountered. Gehm (51)
has given a summary of the complex nature of paper industry sludges.
Activated sludge produced from the,treatment of pulp and paper mill
wastes is of similar hydrous nature to that of activated sludge de-
rived from sanitary sewage. While that obtained from treating paper
wastes high in inerts dewaters rapidly, that from treating mechanical
pulping and board mill wastes has very different properties.
The handling of all types of sludges produced by treatment of pulp and
paper mill wastes is described in detail in the NCASI Manual of Prac-
tice (148) and a variety of installations are described in NCASI Tech-
nical Bulletin #209 (60).
Grayi ty Thi ckening
There is probably no one single factor which affects the feasibility
and end results of sludge dewatering, regardless of the method chosen,
more than the degree of preconcentration of the sludge. With rare
exception, it can be said that the higher the feed sludge solids con-
tent, the more efficient the dewatering operation, from thesperformance,
operation^ and economic standpoints.
Pulp and paper mill sludge can be thickened in the primary clarifier.
However, in some cases, particularly when clarifier capacity is limited,
the sludge cannot be thickened to a desirable consistency without creat-
ing problems. When this is true, the sludge is removed from the primary
clarifier and thickened in a gravity thickener, two types of which are
in common use. These are the conical tank and the "picket fence"/mechani-
cal unit.
76
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Conical Thickening Tank:
The conical tank has generally been replaced by the picket fence thick-
ener. However, it still has application, particularly for small in-
stallations. The conical thickener is frequently a fill and draw, or
batch operation, but can be designed for continuous operation. Side
slope of these units should exceed 60° so that sludge accumulation on
the sides does not occur. In batch operation the tank is filled with
sludge over a period of time and the sludge is allowed to settle for
several hours. The liquid above the sludge (supernatant) is drawn off
with a swing tube. The thickened sludge is then withdrawn. The tank
is then refilled to start another cycle. For continuous operation,
this type of thickener is equipped with a feed well and overflow weir
similar to that of a clarifier.
Mechanical Thickener:
The mechanical, or picket fence, thickener is a continuous-feed opera-
tion. Sludge is fed continuously and thickened sludge removed from
the unit continuously. The tank, rake mechanism, and other appurten-
ances are similar to those used in clarifiers, the difference being
that a series of vertical vanes resembling a picket fence are attached
to the rake mechanism. These serve to accelerate separation of water
from the solids.
Figure 15 shows gravity thickening curves from three different types of
paper mill sludges. It can be seen that these sludges approach their
ultimate compaction in four to six hours. However, at the end of a
thickening period of 12 hours, widely divergent solids contents of 2.6
percent in the groundwood sludge, 4.2 percent in the boardmill sludge,
and 9.4 percent in the deinking sludge exist. This is due to variation
in the degree of hydration and inorganic content, as illustrated in
Table 7. '
Thickener Installations:
There are not many thickener installations within the industry due to
the fact that sludges are generally thickened in the primary clarifier.
They are most frequently found at large mills having activated sludge
treatment. Table 8 shows data obtained from some of those in use. It
appears from these data and laboratory studies that detention times of
four to six hours with solid loadings of 200-800 sq. ft./ton/day and
hydraulic loadings of 200-400 gpd/sq. ft. will give good results. As
can be seen from the wide loading ranges given, laboratory thickening
tests must be made with many samples of the sludge to obtain the best
design parameters for a given installation.
Both dissolved air flotation and vertical disc-type centrifuges have
been applied to dewatering hydrous sludges by individual mills. The
first of these methods is described by Katz (149) and a NCASI research
report (150), Woodruff et al (151), Gehm (51), and Barton et al (152)
77
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FIGURE 15
THICKENING CURVES FOR VARIOUS SLUDGES
OEINKING SLUDGE
BOARD MILL SLUDGE
GROUNDWOOD SLUDGE
6 8
TIME (HOURS)
78
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Table 7
IO
Type Waste
Deinking
Glassine
PERFORMANCE OF MILL INSTALLATIONS OF SPWTY THICKENERS
Feed Consistency Loading Detention Thickened
Sludge
% gpd/ft2 Sq. Ft. /ton/day Hr. Consistency
%
1 360 910 5.6 3-5
0.5 50 1000 48 3-4
Biological Waste
Seed Sludge
1.6
480
150
3-4
-------
Table 8
co
o
Papermill (Low ash)
Papermill (High ash)
Boardmill (Waste paper)
Activated Sludge
Primary Sanitary Sewage
THICKENER LOADING PARAMETERS
Loading
600-800
400-600
300-450
100-250
85-200
Thickened Sludge
Consistency
1-3
5-9
3-5
1-2
3-7
-------
discuss the centrifuge application. Use of these methods is confined
to very slimy sludges such as those high in groundwood fines or of
biological origin. Dissolved air flotation produces overflows up to
4.5 percent concentration while the centrifuge cake ranges from 7 to
12 percent depending upon the feed rate and initial consistency.
Vacuum Filters
The continuous rotary vacuum filter is widely used for dewatering
sludge and is similar to the drum filters used as pulp washers. It
consists of a drum covered with filter cloth, wire mesh, or a series
of endless coil springs and is arranged to rotate partially submerged
in a vat of slurry. The periphery of the drum is divided into a number
of compartments which are underdrained beneath the filter media and
individually piped to a rotating valve located at one end of the drum.
Hence, each compartment is an individual filter being sealed from its
neighbor by division strips and functioning through its own drainage
system as controlled by the filter valve. As the drum rotates, indi-
vidual filter segments become submerged in the slurry at which point
the valve connects this segment to the vacuum source. A cake of wet
solids is then formed on the surface of the media as filtrate is re-
moved through the underdrain system to the valve which in turn directs
it to a receiving tank. The segment remains under vacuum after emerg-
ing from the slurry and until it reaches the top point of the drum's
rotation where the vacuum is cut off by the rotating valve. During
this stage air displaces more water from the cake.
As the segment no longer under vacuum descends in it* rotation toward
the vat the cake is removed in one of several ways. Compressed air
can be admitted to each segment in turn just above the discharge point
to loosen the cake from the media or the cake can be scraped from the
drum with a doctor blade.
In the string discharge type, continuous strings run around the drum
and over the media at intervals of about 3/4 inch. These are lifted
from the drum above the discharge point passing over an external guide
roll carrying the cake with them and discharging it as the strings pass
around the guide roll. The strings return to the cloth on the drum to
begin another cycle.
In the most advanced filters, the entire media (cloth, wire mesh, or
coil spring) is lifted from the drum, unloaded, and washed by a high
pressure shower and returned to the drum through a guide roll system.
This type has been used on all recent installations in the pulp and
paper industry for sludge dewatering.
Operation data and results obtained in dewatering a variety of sludges
by vacuum filtration are shown in Table 9. It will be noted that the
loading range varies widely for most of these sludges, the percentage
of fiber present in them at any particular time being the determinant-
the higher the fiber content the higher the loading.
81
-------
00
ro
Vacuum Filter Recovering Fiber
-------
Table 9
00
CO
CONTINUOUS VACUUM FILTRATION
Sludge Type
Feed Solids %
% Ash
Drum Speed RPM
Filter Cake & Solids
Loading Rate
#/ft2/hr.
Ave. Filtrate
Suspended Solids
#/1000 gal.
% Settleable
Solids in filtrate
Filter Media
White Water
1.33-4.70
15.0-42.0
1.66-8.25
23.3-33.0
1.7-13.4
3.99
86.9
70 x 56 mesh
f ourdrinier
Decoating
& W. W.
5.85-10.02
49.0-58.3
1.23-6.66
34.6-42.9
2.13-10.95
26.1
70 x 56
f ourdrinier
Boardmill
0.87-2.36
1.22-3.33
26.1-30.7
1.22-5.75
4.68
86.6
Fourdrinier
wire
Deinking
& W. W.
5.89-7.15
45.6-51.9
1.50-5.00
31.4-36.4
3.09-10.00
22.5
94.1
Stainless
steel
Felt
Mill
5.20-5.27
1.5-3.08
21.4-25.8
3.71-5.92
Stainless
steel
wire
-------
It will also be observed that the filtrates produced varied in suspended
solids content but that these were largely settleable. Since filtrates
are returned to the system ahead of the clarifier these solids are re-
captured.
The addition of activated sludge to clarifier underflows has a decidedly
adverse effect on dewatering. (This is shown in Figure 16.) A recent
installation employs bark as a filter aid. The effect of other additives
such as fiber and fly ash and coal was studied (153) and none of these,
with the exception of fiber, showed much promise of improving vacuum de-
watering. Some sludges respond to conditioning with chemicals such as
lime, ferric chloride, alum, or polymers. However, the response of a
particular sludge is unpredictable. Precoating of filters with fly ash
was tested with some success on hydrous sludges but the quality of ash
was found to vary widely in respect to usefulness for this purpose.
Recently, interest has developed in heat conditioning and partial wet
air oxidation as methods of sludge conditioning.
Centrifugal Dewatering
The critical review of literature on the dewatering of hydrogels con-
ducted by Beck (154) at the University of Syracuse in 1954 indicated
that centrifuging offered one of the best possibilities for mechanical
dewatering of hydrous slurries obtained from the clarification of some
white waters. This led to the evaluation of two bench-scale unfits and
the experience and data obtained from them indicated that large-scale
equipment of both types should be tested on various paper industry pri-
mary underflows. Field work conducted in cooperation with mills and
equipment manufacturers resulted in the development of a suitable type
of centrifuge for this job--a horizontal conveyor-type machine.
A horizontal conveyor-type centrifuge is essentially a settling device
which induces an increased force of gravity. Dewatering is a function
of the gravitational force applied and the detention time in the unit.
The slurry is introduced into the bowl by means of a feed tube located
in the hollow center shift. It is acted upon by centrifugal force, the
solids being deposited against the wall of the bowl. The liquid, having
a lower specific gravity, forms a concentric inner layer in the bowl.
Inside the rotating bowl is a helical screw conveyor which rotates in
the same direction, but at a slightly different speed than that of the
bowl. This conveyor is pitched so that the solids, which are deposited
against the bowl wall, are conveyed to one end of the bowl where they
are discharged from suitably located discharge ports.
As in gravity settling, the liquid near the surface of the liquid
layer has the greatest clarity. This clarified liquid continuously
overflows adjustable weirs at the liquid discharge end of the bowl.
Suitable partitions in the machine case form compartments for receiv-
ing discharge effluent and solids, guiding them into their respective
hoppers.
84
-------
FIGURE
EFFECT OF ACTIVATED SLUDGE ON
DE WATER ING BOARDMILL SLUDGE
4.5
4.0
e
X
3
QC
UJ
K
35
. */
3.0
2.5
10 20
% ACTIVATED SLUDGE
30
85
-------
-
Sludge Centrifuge Installation at a Pulp Mill, Sharpies Corp.
-------
Results of these tests indicated that the horizontal conveyor machine
appeared capable of producing a cake of 25 to 35 percent solids at re-
coveries in excess of 85 percent.
Subsequent to these investigations the dewatering of sludges by cen-
trifugation has become a common practice. Installations have provided
the opportunity to evaluate this form of dewatering and establish some
of the factors which affect solids content of the cake and solids re-
covery.
Feed consistency, rate of application, and slurry character all affect
performance of these machines. Solids recovery efficiency must be main-
tained at a high level or fines build up in the clarifier to which the
concentrate is returned. This was studied by Linsey et al (60) who
concluded that this problem did not occur when recovery efficiency ex-
ceeded 85 percent. Description and performance data appear in NCASI
Technical Bulletin #238 (155) covering a number of recent installations
and are summarized in Table 10.
Pressing
After experiments had shown that additional water could be removed
from vacuum filter and centrifuge sludge cakes by pressing (156), de-
velopment work proceeded with commercial presses of different types
in order to allow the application of this technique. Data, such as
that presented in Table 11, indicated that cakes approaching 50 per-
cent solicfe could be obtained. However, a wide variation in sludges
and press performance was observed and a considerable amount of press
development!work was involved in applying them.
h
Their application to vacuum filter cake from pulp mill sludges is de-
scribed by Bing (155), Fuller (59), Coogan and Stovall (310), and
Linsey (60). In pressing sludges consisting primarily of fibrous
organics, Bing, Fuller, and Coogan report operations producing press
cake in excess of 40 percent dry solids. Linsey, however, handling
a slurry containing variable quantities of lime, other inorganics,
and some non-fibrous organics obtained very erratic and frequently
unsatisfactory results.
Recently pressing has been successfully applied by Stovall and Berry
(157) to clarffier underflows containing substantial fiber. Problems
could develop with this procedure, however, due to fines which pass
the press accumulating in the clarifier, hence, it must be applied
with care.
Incineration
Three types of incineration are practiced in paper mill sludge dis-
posal. These are: (1) burning in an incinerator designed specifically
to handle sludge as described by Coogan and Stovall (156); (2) in a
bark boiler as indicated by Stovall and Berry (157) and others (155)
87
-------
Table 10
CENTRIFUGE INSTALLATIONS
MILL
1
2
3
4
5
6
7
8
9
10
11
12
13
14
SLUDGE
TYPE
Fine Paper
Bl. Kraft
Fine Paper
Tissue
Bl. Kraft
Fine Paper
Tissue
Hard Board
Tissue
Tissue & Bark
Kraft
Book
Board
Kraft
SPEED
rpm
1000
1000
2400
2250
1200
1300
4000
2000
1000
1000
3000
3000
2600
1200
(..__
RATE
gpm
80-120
95-194
60-62
25
240-320
56
20-22
43
60-85
100-150
300
150
97
120
— : FEED
CONSISTENCY
%
5-10
3.5-4.5
3.5
2-3
1.0-2.2
8-12
2-3
2
1-4
3-5
1-2
5-12
4-6
1-2
I
ASH CONT.
%
50-70
60-70
5-10
45
10-15
10-30
5-10
60-70
30-40
20-25
SOLIDS
CAPTURE %
85-95
80-92
95
80-85
80-85
80
88
85
65-90
86-93
88-95
85-92
88-95
90
CAKE
MOISTURE %
65-80
82-85
76-84
78-79
80
70-80
58-66
65-70
78
82
60-75
55-60
52-65
76-80
-------
Table 11
MECHANICAL PRESSING OF SLUDGE
Applied Grams of Water
Pressure^ Removed per
psi
CAKE
Final
Solid
Kilogram of sludge
Pressing time, min.
100
300
500
700
900
1
65
75
81
84
97
5
Board
123
180
191
207
246
10
Mill Filter Cake
191
234
268
270
293
. Pressed Cake
Is Consistency
Pressing time, min.
1
27.5
28.5
29.1
29.4
30.7
5
33.3
39.0
40.1
41.7
45.6
10
40.1
44.4
47.8
48.0
50.3
Beinking Filter Cake
100
300
500
700
900
85
103
108
135
150
190
231
265
285
300
235
280
310
335
344
38.5
40.0
40.6
43.3
45.0
49.0
53.2
56.4
58.5
60.0
53.3
58.0
61.0
63.0
64.3
89
-------
Sludge Incinerator, Reitz Manufacturing Co.
90
-------
(158); and (3) incineration in a power boiler burning fossil fuel.
All these methods are successful. However, the high costs involved
relative to land disposal at most mill sites have limited their use.
Incineration is also limited to low ash sludges not only because of
their low fuel value but due to technical problems with incinerators.
Figure 17 is a curve showing the relation between moisture and organic
content of sludge necessary to support combustion.
A number of other types of combustion have been tried including multiple
hearth and kiln type units as well as wet air oxidation and the fluid-
ized bed. Of these only the fluidized bed system appears promising of
considerable application.
Summary
Figure 18 is a multi-path flow diagram showing the common mechanical
methods of thickening, dewatering, and disposal of sludge from clari-
fier underflows. Which pieces of equipment are chosen for a particular
installation and how they are arranged depends on the character of the
particular sludge handled. The response of the sludge to these unit
processes varies from day to day as pointed out by Linsey (60). Hence,
careful pilot studies generally precede design of these systems.
91
-------
FIGURE 17
ro
tn
Q
o
UJ
o
o
80
f- 65
ui
o
oc
UJ
Q.
50
35
20
SLUDGE CAKE CONDITIONS
REQUIRED TO SUPPORT COMBUSTION
I
I
15 30 45 60
SLUDGE CAKE -PERCENT ORGANIC
75
90
-------
FIGURE 18
MULTI-PATH DIAGRAM OF MECHANICAL
THICKENING, DEWATERING AND DISPOSAL OF SLUDGES
vo
CO
CENTRATE •*
CLAF
UNDE
r -*•••
SCROLL
CENTRIFUGE
•
GRAVITY, DAF
OR CENTRIFUGAL
THICKENER
*•
PRESS
* VACUUM
FILTER
i !
1 . .
1
• FILTRATE
•••PRESS WATER
!~
1
INCINERATOR
1
*
BARK
BOILER
|
T
POWER
BOILER
i
_L
r
i
LAND
DISPOSAL
SLUDGE
CAKE
LEGEND
r ASH
RETURN
-------
SECTION IX
TREATMENT IN PUBLIC FACILITIES
Sewage treatment plants encounter no problems in treating a reasonable
proportion of pulp and paper-making wastes if they are adequately designed
to handle the load imposed as pointed out by Pirnie and Quirk (178,182),
Gehm (179), Faulkender (180), Opferkuch (181), and others. In some cases
pretreatment is required as discussed by Swets et al (183). This is
particularly the case where suspended solids loads are high. In any
event, it is necessary for connected mills to practice good loss control
since surge loads of spent liquors or fiber can disrupt operations at
sewage treatment plants in a number of ways. Normal variations in process
losses, however, have less impact on combined facilities than they would
on a mill effluent treatment system because of equalization occurring in
sewerage systems, and sanitary sewage provides nutrients needed in
biological treatment frequently lacking in paper mill wastes.
Although few pulp mills are involved in public treatment projects, many
waste paperboard mills in or close to large communities which serve as
their source of raw material have for years been utilizing public
facilities with satisfactory results. This is true of other small
papermaking plants. The NCASI reports on this practice as follows:
i
"It can be concluded that the trend toward treatment of the
effluent from small mills in community sewage treatment works
will continue and both small and large mills in metropolitan
areas will probably join with the municipality and industries
in joint treatment. However, the large outlying pulp mill
will continue to provide its own waste handling facilities."
In 1968 NCASI published a study (184) dealing with treatment of pulp
and paper mill wastes in public sewerage system. The data, summarized
in Table 12, showed that 123 mills then discharged to sewage treatment
works which represented 16 percent of the total number of mills operating
at the time. About half of these were clustered in metropolitan areas.
The total discharge represented 11 percent of the paper manufactured
in this country. About half of the mills produced less than 100 tons
daily, this being the median capacity. Only 12 mills exceeded 300 tons
daily in capacity and 40 produced less than 50 tons. Eighty of the
connected mills produced waste paperboard or building felts, thirty-
nine fine papers, and only four were classed as integrated mills.
Treatment Received and Costs Allocation
Of the total, 59, or slightly less than half, received primary treatment.
Treatment charges were reported as 20 cents to 65 cents per pound per ton
for primary and secondary treatment for the waste paperboard mill, and
30 cents to 80 cents per pound per ton for all the mills surveyed. Three
95
-------
Table 12
MILLS DISCHARGING TO PUBLIC SEWAGE TREATMENT FACILITIES.
Number of Mills
Capacity 106 TPD
123 of 753 or 16%
5.5 of 50 or
Major Locations and Number
Los Angeles County
Northern Metropolitan
New Jersey
Philadelphia Area
Neenah-Menasha
Kalamazoo
Cincinnati
Chicago
Total
Distribution by Size
13
19
6
6
5
5
4
i^«^^**p^«mmB^™
58 of 123 or 47%
Distribution of Type
TPD
0-50
51-100
101-300
301-500
>500
41
21
53
5
3
Waste Paperboard
Building Felts
Fine Paper Grades
Integrated Mills
No. Mills
64
16
39
4
96
-------
methods for computing sewer service charges enjoyed approximately equal
use. These were ad valorem property taxation, and rates based on flow
alone, or flow plus effluent strength. Specially negotiated contracts
accounted for only 7 percent of the rates, while each of the more
prevalent systems were in use at approximately 30 percent of the mills.
Mills Considering Discharge to Public Facilities
This broad category covers mills known to have recently completed
arrangements for public treatment, those where feasibility and rate
schedule studies are still in progress, .and some where such studies
have led to a decision to proceed with independent treatment. The
survey data presented in Table 13 shows that the entire group includes
91 mills, or 12 percent of those now operating. Their annual capacity
totals 5.5 million tons, or 11 percent of the total for the industry.
When this group is added to those already'discharging to public facilities
we find that use of public treatment facilities is, more than an academic
question for 28 percent of the industry's mills, accounting for 22 percent
of its production capacity.
Table 13
MILLS CONSIDERING DISCHARGE TO PUBLIC FACILITIES
Distribution by Size Distribution by Type
TPD Number Number
0-100 44 Coarse Paper Grades 38
101 - 200 57 Waste Paperboard ' 32
201 - 500 23 Roofing Felt .6
>500 5 Fine Paper Grades '38
Integrated Pulp & Paper 15
Median Size 1UO TPD
The largest concentrations of mills now considering public treatment
are located in three states: New York, Massachusetts, and Maine. They
account for 55 mills or 60 percent of the total. These are states
where effluent treatment has only recently gathered momentum after
extended periods of stream classification and development of abatement
programs for both municipalities and industries, and where planning
funds have been allocated by the legislatures to assist regional
treatment feasibility studies.
!-
The size distribution profile of these mills is similar to that for
mills already in public systems. Nearly 25 percent are smaller than
50 tpd, and the median size is 100 tpd. The coarse paper grades account
for a lesser fraction of the mills, being equalled in number by those
producing fine grades. We also see a significant increase in the
number of integrated pulp and paper mills involved in such studies This
is particularly true in Maine and New York. Most of the feasibility and
97
-------
rate studies are not far enough along to permit an analysis as to
projected costs or financing procedures. The bulk, however, are predicated
on providing secondary treatment in line with actual needs or regulatory
policy.
98
-------
SECTION X
ORIGIN OF SPECIFIC MILL EFFLUENTS AND RESULTS OBTAINED BY TREATMENT
Wood Preparation
Wood, the raw material for most of the pulps produced in this country,
is received at the mills in various forms and for this reason must be
handled in a number of different ways (185). Some mills receive chips
from saw mills, or receive barked logs which can be chipped directly.
In these instances little, if any, water is employed in preparation
of the wood and no effluent is produced. Most mills receive round wood
in short lengths with the bark remaining on it, and, since the bark
interferes with both the pulping process and product quality, it must
be removed.
Underwater Log Storage:
Some pulp mills store their wood supply in the water, and others spray
log piles with water to prevent deterioration and maintain a uniform
moisture content. The latter practice has taken precedence over the
former because of its much lower cost.
The leaching effects of underwater storage were studied by Schaumburg
(186) and Graham (187). In their experiments unbarked and barked logs
were submerged for seven days in water containing sufficient mercuric
chloride to prevent biodegradation of the leached substances. Data
obtained for three species of wood are shown in Table 14 which gives
the BOD 5 leached from each square foot of log surface exposed. From
these data it was computed that a cord of unbarked wood will add from
0.5 to 7.0 pounds of BOD and 0.8 to 23 pounds of COD to the water in
which it is stored, the species as well as the season of cutting
determining the magnitude of these figures.
When roundwood is stored unbarked under water, wood solubles, silt, and
bark debris are transferred to the water. As much as ten pounds of BOD5
per cord of wood stored can be contributed depending upon the length
of the storage period. Since the same water is usually used repeatedly
with only make-up being added, the water can accumulate a high BOD
value and require treatment prior to its discharge. Hence, rather than
discharging during a short interval coinciding with basin cleaning, it is
good practice to bleed the storage basin to the waste treatment facility
on a continuous basis in order to prevent the overload that slug discharge
would ordinarily produce, and make up evaporation and out-carriage water
losses continuously or at frequent intervals.
Log Washing:
Logs are frequently washed before dry or wet barking by a water shower
in order to remove silt (188). In most installations the water shower
99
-------
TABLE 14
OXYGEN DEMAND
WOOD SPECIES
Douglas Fir
Ponderosa Pine
Hemlock
OF WATER AFTER SEVEN DAYS CONTACT WITH WOOD
BARK BOD5 GM/FT2 COD GM/FT.2
+ 0.9 3.2
0.9 3.2
+ 0.8 4;2
1.4 2.8
+ 0.3 1.8
0.9 2.0
TABLE 15
WOOD WASHING
Effluent Flow
100 to 300 Gal./Ton/Prod.
BOD 5
1 to 8 #/Ton/Prod.
Total Suspended Solids
5 to 55 #/Ton/Prod.
Color
< 50 Units
100
-------
is activated by the log itself while on the conveyer so that a minimum
of water is used. The.actual quantity discharged per unit of wood
handled or pulp produced is most difficult to ascertain because of the
wide weight variation in stick size and the fact that all the wood
barked at some installations is not pulped, a portion going to lumber.
However, the limited data available indicate that this flowage amounts
to about 100 to 300 gallons per cord of wood washed.
It is established that this effluent is very low in color and BOD (189)
and that its suspended solids content is largely silt. Hence, it is
generally disposed of on the land together with grits and dregs from
the pulp mill and/or ashes from the boiler plants, or combined with the
general flowage to the treatment works. Storage oxidation and seepage
account for considerable reduction in residual BOD when this waste is
lagooned and the solids settle rapidly and do not decompose. Effluent
flowage and range of losses from such operations are shown in Table 15.
Barking:
Most of the pulpwood used in the United States is small in diameter
and it is barked dry in drums. However, when large diameter or long
wood is used, wet barking is commonly employed. The latter operation
is pretty much limited to northern mills and its use is presently declining.
Wet barking of logs is accomplished by one of three methods: by drums,
pocket barkers, or hydraulic barkers as described in Volume I of "Pulp
and Paper Manufacture" (185) and by Kronis and Holder (190). Slabs
are generally handled by hydraulic units as is the larger diameter and
long roundwood.
The wet drum barker consists of a slotted drum equipped with internal
staves which knock the bark from the wood as the drum rotates in a pool
of water. The bark falls through the slots and is removed with the
overflow of water. These units handle from 7 to 45 cords of wood daily.
Frequently the water supplied to them is spent process water and recycling
within the barking,unit itself is often practiced. Barkers of this type
contribute from 15 to 20 pounds of BOD per ton of wood barked, and from
30 to 100 pounds of suspended solids. Examples of the BOD5 and suspended
solids concentration of this wastewater with the barkers using fresh
process water are shown in Table 16.
Wet pocket barkers are stationary machines which abrade bark from timber
by jostling and gradually rotating a confined wood stack against an
endless chainbelt equipped with projections called "dogs" which raise
the wood pile allowing bark to pass between the chains. Water is
sprayed through apertures in the side of the pocket at rates of between
330 and 600 gpm for pockets of 2.8 and 5.7 cords per hour, respectively.
The use of this process is rapidly declining in the United States.
Hydraulic barkers employ high-pressure water jets to blow the bark
from the timber which is either conveyed past them or rotated under
a moving jet which traverses the log. The volume of water employed
is generally from 5000 to 12,000 gallons per cord of wood barked
depending upon log diameter.
101
-------
TABLE 16
ANALYSIS OF WET DRUM DEBARKING EFFLUENTS
o
ro
MILL
1
2
3
TOTAL SUSPENDED
SOLIDS
mg/1
2017
3171
2875
NON-SET
SOLIDS
mg/1
69
57
80
% ASH
OF
S. S.
—
21
18
BOD 5
rng/1
480
605
987
COLOR
UNITS
20
50
50
-------
Water discharged from all three types of wet barking is generally
combined with pre-wash water from sprays, which give the logs a
preparatory cleaning, and then coarse screens are used to remove
the large pieces of bark and wood slivers which are conveyed away
continuously. The flowage then passes to fine screens. These are
of the drum, fixed vertical, or horizontal vibrating type, having
wire mesh or perforated plate media with openings in the range of
0.05 to 0.10 inches. Screenings are conveyed away and mixed with
the coarse materials from the initial screenings, the mixture being
dewatered in a press prior to burning in the bark boiler. Press
water, which is combined with the fine screen effluent, is very
minor in volume. The total waste flow, which amounts to about
5000 to 7000 gallons a cord, generally carries from one to ten
pounds of BOD5 and 6 to 55 pounds of suspended solids per ton
of product.
The combined discharge contains bark fines and silt, the latter varying
greatly in quantity since its presence is due mainly to soil adhering
to the logs. In dry weather the percentage of silt in relation to bark
fines is low as is the case when logs are stored in or transported by
water. However, attachment of mud in wet weather can make this material
a major percentage of the total suspended matter passing the fine
screens.
Fine screen effluent following hydraulic barkers has been analyzed by
several investigators (191,192,193,194) and examples are shown
in Table 17. It can be concluded from the data included in these
publications that these effluents have a total suspended solids
content ranging from 521 to 2350 mg/1 with the ash content running
from 11 to 27 percent. The latter is generally below 15 percent for
clean logs. BOD5 values range between 56 and 250 mg/1. These low values
are due to the fact that the contact of the water with the bark is
short and no grinding action on the wood takes place. Hence leaching
of wood and bark solubles are minimized. The water originally employed
is all fresh process water, since the close clearances of the high
pressure pumping systems supplying water to the jets will not tolerate
the presence of suspended solids in the water.
Such low values are not the case with drum and pocket grinding where
attrition in contact with water over an appreciable period of time
takes place. Also, spent pulping and bleaching process waters already
high in BOD and color are not infrequently used for these barking
processes which raise further the ultimate level of organics in the
screened effluent. While wet drum and pocket barker fine screen discharge
is not greatly different from that of hydraulic barkers in suspended
solids content, the BOD5 can be considerably higher (195,189,191).
BOD values are also greatly affected by the species of wood barked and
the season in which the wood was cut since wood juices and water
extractables are responsible for it. That contributed by the suspended
matter present is a minor fraction of the total BOD. Curves presented
by Blosser (192), as shown in Figure 19, indicate that the 15-day values
are about twice those of the 5 day with little further demand exerted
103
-------
TABLE 17
ANALYSIS OF HYDRAULIC BARKING EFFLUENTS
MILL
1
2
3
4
5
6
7
8
TOTAL SUSPENDED
SOLIDS
mg/1
2362
889
1391
550
521
2017
2000
600
NON-SET
SOLIDS
mg/1
141
101
180
66
53
69
'< 200
41
% ASH
OF
S.S.
27
14
17
11
13
21
19
10
BOD s
mg/1
85
101
64
99
121
56
97
250
COLOR
UNITS
< 50
< 50
' < 50
< 50
< 50
< 50
—
35
-------
120
100
FIGURE 19
LONG TERM BOD OF BARKER EFFLUENT
( AFTER FINE SCREENS)
FILTERED
10 15
DAYS INCUBATION
25
105
-------
after this period. The oxygen demand rate over five days was demonstrated
to be similar to that of paper mil] wastes (190). A process flow
diagram of wet barking operations is presented in Figure 20.
Treatment:
Settling will remove from 70 to 90 percent of the total suspended
solids present in barker wastewater and is essentially complete
in 30 to 60 minutes.
Settling curves were published by Draper and Mercier (191) and Blosser
(192) and a typical one is presented in Figure 21. Because of the
good settling characteristics of the screened effluent, sedimentation
is employed for clarification. Also, because of this attribute,
coagulants are not needed (196). Settling is sometimes accomplished
in alternating earth embanked basins from which the settlings, which
compact well, are dredged.
More modern practice is the use of circular, heavy-duty type clarifiers
or thickeners. These are designed for a rise rate of 1000 to 1200
gal/ft2/day of surface area and to provide a retention period of
about two hours. They are equipped and piped to handle dense sludge
such as that produced when considerable silt is present in the underflow,
as well as a skimmer to collect the ever-present floating materials.
The underflow is removed by means of diaphragm, plunger, or screw
pumps and transferred to drying beds or to a vacuum filter for dewatering.
Filters can be of the disc or drum type, and because of the freeness
of the solids can operate at high submergence producing a thick cake.
Drum speed is variable so that variations in cake freeness can be
accommodated and a vacuum of about 15 inches is desirable. Filter
media frequently consist of 120-mesh stainless steel wire cloth.
Filter cake produced contains about 30 percent solids and loadings
range from 10 to 12 #/ft*/hr of dry solids. Such cakes are either
disposed of on the land or sold as mulch. A diagram of the treatment
process is presented in Figure 22.
Effluents from clarifiers are not treated further separately but combined
with pulp mill and other wastes for biological treatment when this process
is practiced. As can be judged from the BOD rate curve, their treatment
by biological means presents no problems.
Pennsylvania established raw waste standards for wet barker effluents in the
early 1950's (195). These allowed 50 to 70 pounds of total suspended solids
and 15 to 20 pounds of BOD5 in the effluent from fine screens. The State
of Washington, however, has set an effluent standard of less than 200 mg/1
of volatile suspended matter (197), a value which can only be met by
clarification installations of good design and operation.
It is difficult, because of the many variables involved, to set a fixed
number for the volume, pounds of BOD5, and total suspended solids
discharged per ton of pulp produced. However, a single hydraulic
barker of the usual size operating on common sizes of logs can generally
service a 200 to 300 ton per day pulping operation and employs between
900 and 1200 gpm of water. Effluent flowage as well as BOD5 and
total suspended solids losses per ton of pulp produced are presented
in Table 18.
106
-------
FIGURE 20
PROCESS
WATER
1
WET BARKING PROCESS DIAGRAM
LOG
STORAGE
— »
por>rpec
BACK WATER
1
•
i
•
LOG
WASHER
L_
•
*
i
i —
>
1
•1
1 I
WET DRUM
POCKET OR
HYDRAULIC BARKER
I
DEBARKED
LOGS
OFF GASES
*
*
•
CYCLONE
COARSE
SCREENING
BARK
PRESS
FINE
SCREENING
BARK
BOILER
4
+
I
ASH TO LAND
DISPOSAL
L I
DIVERSION
BOX
I
EFFLUENT
PRODUCT 8
RAW MAT'L.
PROCESS WATER
BACK WATER
GASES
BARK, ASH
RESIDUE •*"*'
EFFLUENT
-------
FIGURE 21
SETTLING RATE OF
BARKER SCREENING EFFLUENT
100
90
z
o
O
UJ
a:
80
70
O
UJ
o
UJ
I 60
50
20
40 60 80
RETENTION TIME (MINUTES)
100
i
I
I
I
3240 1620 1000 810 648
CLARIFIER SURFACE LOADING-GAL./FT.2/DAY
108
-------
FIGURE 22
TREATMENT OF WET BARKING EFFLUENTS
FINE
SCREEN
EFFLUENTS
EFFLUENTS
SLUDGE
——— FILTRATE
CLARIFIER
DISC
FILTER
4 I
t:
OVERFLOW
TO TREATMENT
PLANT OR LAGOON
I
I
I
JL
FILTER CAKE
TO LAND
DISPOSAL
FINAL EFFLUENTS
109
-------
TABLE 18
SEWER LOSSES FROM WET BARKING OPERATIONS
Mill # Eff. Flow BOD5 Total Susp. Solids
Thous. Gal./Ton Prod. I/Ton Prod. #/Ton Product
1 2.7 1.2 6.4
2 2.4 1.8 7.6
3 3.5 12.0 5.5
4 6.0 6.0 30.0
5 3.0 2.5 22.8
6 1.0 2.0 10.0
7 5.6 19.0 18.0
8 1.0 11.5 30.0
9 7.5 20.1 34.0
Groundwood Pulping
Groundwood pulp is employed mainly in the manufacture of newsprint,
toweling, tissue, wallpaper, and coated specialty papers such as that
used for some illustrated magazines (185). Since it contains practically
all the wood substance, yields generally exceed 90 percent. Most of it
is produced by the large newsprint mills in the South from southern pines.
In all, about 60 mills with a daily capacity of approximately 14,000
short tons, produce this type of pulp in the United States, of which
about 20 are large operations. This is distinct from pulps produced
by other mechanical processes which are generally employed for building
or molded products.
Groundwood pulp is produced from both roundwood and chips. In the
older process roundwood is pressed against large rotating grindstones
by hydraulic rams while water is sprayed on the stone (198). On
discharge from the grinder the pulp is screened free of wood slivers
and other coarse debris and thickened on deckers. The thickened
pulp is then discharged to a stock chest for use in the paper mill
or lapped for shipment. After clarification by sedimentation, filtration,
or flotation, the filtrate from the deckers is largely returned to
the process but a portion is sewered to prevent the buildup of solubles
in the system with attending slime problems. The overflow rarely
exceeds 10,000 gallons per ton of bone-dry pulp and in some instances
is as low as 2000 gallons (199,27,188). A flow sheet of this process
is shown in Figure 23.
In some modern newsprint mills the groundwood operation is completely
closed, all effluent appearing in the paper machine effluent. In
this event, the raw waste load is the sum of typical losses from
both the groundwood pulping and papermaking.
110
-------
FIGURE 23
GROUNDWOOD PULPING
PROCESS DIAGRAM
WHITE WATER
TANK
FLOOR DRAINS
WASHOUTS
OVERFLOWS
GRINDERS
r-
EFFLUENT
n
DEBARKED
WOOD
STORAGE
COARSE
SCREENS
FINE
SCREENS
REJECT
REFINER
CENTRI-
CLEANERS
SAVE-ALL
DECKER
PROCESS
WATER
UNBLEACHED
PROD.
BLEACH
CHEMICALS
STOCK
CHEST
BLEACHING
BLEACHED
<• PROD.
LEGEND
PRODUCT a RAW MAT'L
CHEM.a LIQUORS
PROCESS WATER
BACK WATER
REJECTS***
EFFLUENT
111
-------
TABLE 19
Mill
1
2
3
4
5
6
7
8
EFFLUENT CHARACTERISTICS OF STONE
Eff. Flow
Thous. Gal. /Ton, Prod.
6.3
1.9
4.4
5.4
8.3
2.7
2.2
2.6
GROUND WOOD
BOD5
#/Ton
11
8
11
9
18
19
4
14
PULP MILLS
T.S.S.
#/Ton
16
14
ii
12
11
16
42
21
TABLE 20
Mill
1
2
3
4
5
6
7
EFFLUENT CHARACTERISTICS OF REFINER
Eff. Flow
Thous. Gal ./Ton Prod.
2.6
4.3
5.8
6.7
4.4
1-7
5.9
GROUNDWOOD PULP
BOD5
#/Ton
26
120
15
18
15
32
30
MILLS
T.S.S.
#/Ton
105
100
110
59
30
35
35
112
-------
In recent years a considerable amount of groundwood has been produced
by passing wood chips through refiners of the disc type (185). Two
stages of refining are employed in the pulp mill, a third taking place
as part of the papermaking operation. The refiners contain fixed and
rotating discs between which the chips pass together with a stream of
water. The pulp is discharged as a thick slurry, after which it is
handled in a manner similar to stone groundwood. Generally less water
is required with refiners. Figure 24 represents the process diagram
of a typical refiner groundwood operation. Effluent volume, BOD5, and
suspended solids losses for all groundwood pulping are shown in Tables
19 and 20.
Chemi-groundwood and Cold Soda Pulps:
Some groundwood-type pulps are produced by first soaking barked logs
or wood chips in dilute chemical solutions which soften the wood, thus
reducing the power required for grinding. When caustic soda is employed
as the chemical the pulp is referred to as "cold soda" pulp and when
sodium is used the product is called "chemi-groundwood" pulp. Both
products are manufactured by both stone and refiner grinding. Chemical
treatment results in higher BOD5 losses than occur in ordinary groundwood
operation as indicated in Table 21.
TABLE 21
EFFLUENT CHARACTERISTICS OF COLD SODA AND CHEMI-GROUNDWOOD PULPS
Eff. Flow BOD 5 T.S.S.
Thous. Gal./Ton Prod. f/Ton #/Ton
Cold Soda Pulping
1 2.0 73 15
2 3.7 92 26
3 5.5 101 32
Chemi-Groundwood
1 2.4 81 24
2 3.3 69 37
Bleaching of Groundwood Pulp:
Groundwood pulp is generally bleached with hydrogen or sodium peroxide,
sodium or zinc hydrosulfite, or sodium sulfite (200,201). Interest
has recently developed in the use of peracetic add, sodium borohydnde,
and amine borides for this purpose, but their use has not become established
practice (202).
113
-------
FIGURE 24
REFINER GROUNDWOOD
PROCESS DIAGRAM
WHITE WATER
TANK
L/^X—
T'
CHIP
WASHER
T\-..—<*K—--
I-
FLOOR DRAINS
WASHOUTS
OVERFLOWS
PRIMARY
REFINER
1— »
FEED
CONVEYOR
•
U
i
SECONDARY
REFINER
SAWMILL
CHIPS
CHIP
STORAGE
CHIPPER
DEBARKED
WOOD
EFFLUENT
PROCESS
WATER
i-
LI
e» A \ ic
-S
-^
•ALL
'
I
\
BLEACH
CHEMICALS
«, L.
i
4
t
4
*+* + •+•
FINE
SCREENS
<
CENTRI-
CLEANERS
DECKER
*
BLEACHING
(
BLEACHED
PROD.
STOCK
CHEST
i
UNBLEACHED
PROD.
LEGEND
PRODUCT & RAW MATL
CHEM.S LIQUORS
PROCESS WATER
WATER
REJECTS
EFFLUENT
114
-------
In practice, the pH is generally adjusted to between 4.5 and 7.0 depending
upon the bleaching agent and sometimes complex!ng chemicals are added to
overcome the effect of heavy metals, such as iron and manganese, that may
be present. Buffers and catalytic agents in trace quantities are also
sometimes used. Since groundwood can be bleached at high consistency,
it is frequently accomplished at stock chest levels without washing.
Hence, the residues of bleaching appear in the white water of the paper
machine'.system.
Since the zinc content of effluents from the zinc hydrosulfite process
is generally less than 10 mg/1 it does not cause a problem when diluted
with other effluents and receiving waters.
treatment:
The large integrated mills, as well as paper mills alone, treat the
groundwood effluent in combination with the total discharge. Thirty-
eight mills which manufacture 9,750 tons daily provide treatment. Of
these, 12, representing a daily production of 5,000 tons of groundwood,
provide secondary treatment. Storage oxidation basins, aerated lagoons,
and activated sludge are all employed.
The effluent from groundwood pulping can be clarified to a high degree
by settling, particularly if other effluents containing fiber and fillers
are combined with it, since 90 percent of the suspended solids present are
settleable. However, the sludge produced is extremely hydrous, often
averaging only 0.5 percent consistency and is most resistant to dewatering.
It can be dewatered only on combination with other less hydrous waste
slurries. Flotation is equally as effective as settling or clarification.
Groundwood mill effluent is responsive to biological treatment both alone
and in combination with other pulping wastes. Lower oxidation rates have
been observed for it than for chemical pulping effluents according to
Bishop and Wilson (84), but when combined with kraft pulping effluent
the rate becomes normal.
Some modern newsprint mills clarify the groundwood pulping effluent
and employ it for dilution on the paper machine. Hence, losses from
both pulping and papermaking are contained in a single discharge
which is then mixed with other pulp mill waste prior to treatment.
Cold soda and chemi-groundwood effluents present no problem when combined
for treatment with other mill effluents (71) for as previously pointed
out, they represent a higher BOD5 loading than ordinary groundwood.
The settling characteristics of the suspended solids contained in them are
very similar to those of groundwood.
Since there is presently no case where groundwood effluent is treated
separately, data for this category are not available. However, data
for kraft newsprint waste treatment are presented in the section on
kraft pulping.
115
-------
Neutral Sulfite Semi-chemical Pulping
Approximately 12,000 tons of NSSC pulp are produced in the United
States daily. A two-stage process is employed in which the wood
chips are softened by a short cook with a neutral sodium or ammonium
sulfite solution, then defibrated in a refiner (185). Pulp yields
from the wood range from 60 to 80 percent on a bone-dry basis for use
in a variety of products. Most, however, goes to the coarser products
such as corrugating board which consumes 75 percent. The bleaching of
this type of pulp will soon come to an end in this country.
While some mills buy the cooking chemical, most prepare liquor by
burning sulfur and absorbing it in soda ash or ammonia. This part of
the process produces little liquid wastes other than floor drainings,
equipment wash-up, and cooling waters which can frequently be used as
process water.
Chips are cooked in either batch or continuous digesters and passed
through disc refiners prior to washing. Digester-relief and blow
gases £re condensed, and in some mills the condensate is used for
pulp washing. Pulp wash water together with drainings from the blow
tank are delivered to the recovery or liquor burning system. Since
many of these mills are adjunct to kraft pulp mills the spent liquor
is recovered in the kraft recovery system, the organics cooked from
the wood being burned in the furnace, and the residual chemicals
supplying chemical make-up for the kraft mill.
From the washers the pulp is conveyed to an agitated chest where it is
diluted with white water from the paper mill to the desired consistency
for feed to the secondary refiners serving the papermaking operation.
In making corrugating board a small percentage of repulped waste paper
is added to give the product the desired charactertisties. Other than
spent liquor, the pulping and washing operations discharge little
wastewater since the small amount of residual liquor solids present
in pulp is carried through the machine system passing out with the
overflow white water (203). Figure 25 is a process diagram of a modern
operation.
Spent liquor is commonly fed to triple-effect evaporators after which
it is burned with bark in the bark boiler, in a fluidized bed unit, or
in a special furnace if chemical recovery is practiced (204,205). The
latter practice, however, is limited to a few large mills. The fluidized
bed units produce sodium sulfate suitable for use in kraft mill liquor
systems. One mill produces acetic and formic acids from the liquor
and sends the residual raffinate to a kraft mill for makeup since it
contains a substantial amount of sodium sulfate (103).
The final effluent from NSSC mills is low in volume because of the
high degree of recirculation commonly practiced. For the same reason
it is usually high in BOD 5 ranging from 1500 to 5000 mg/1 with a
suspended solids content of from 400 to 600 mg/1. The color and COD
content are correspondingly high (176). Overall process losses in
BOD5 and total suspended solids without recovery in relation to pulp
yield are shown in Figures 26 and 27.
116
-------
FIGURE 25
NEUTRAL SULFITE. SEMI-CHEMICAL
PULP PROCESS DIAGRAM
t
CHIP
STORAGE
TO ATMOSPHERE
rl
i
i
i
STACK
GASES
SOt.- COt
4
I
.J
SEAL
PIT
M-
*—
EVAPORATOR
i—
~l
LIQUOR
RECOVERY OR
BURNING
FLOOR DRAINS
WASHOUTS
OVERFLOWS
UJ
PRODUCT 8 RAW MATL.
CHEM. & LIQUORS
PROCESS WATER
i
BLOW
TANK
i
REFINERS
i
WASHER
i
SHREDDER
I
PRODUCT
EFFLUENT
COOKING
LIQUOR
STEAM
"*
r\ i f~c OT^O
LMotoTOR
ABSORBER
SULFUR
DIOXIDE
T
l»
I
SODIUM
CARBONATE
STOCK
PREP.
L-
WHITE
WATER TANK
r
I
PAPER MACH.
SAVE-ALL
PROCESS
WATER
1
EVAP. COND.
COOLING HZ0
BACK WATER
STEAM & GASES
EFFLUENT
n
117
-------
FIGURE 26
BOD LOAD OF NSSC PULPING
700
600
a.
_i
Q.
a:
Q
Ul
500
400
^f^m
P.
cc
UJ
Q.
m
Q
300
200
100
55
60
65
70
75
80
PERCENT PULP YIELD
118
-------
FIGURE 27 SUSPENDED SOLIDS LOSSES FROM NSSC PULPING
120
PERCENT YIELD
119
-------
In corrugating board NSSC mills the white water system can be closed
to a very high degree. Lowe (206) demonstrated that satisfactory operation
was possible at an effluent flow of less than 2000 gallons per ton of
product. The mill white water flow pattern employed by him is presented
in Figure 28. Recently this practice has been followed successfully at
other mills.
Data regarding effluent volume as well as BOD5 and suspended solids
losses for 13 NSSC corrugating board mills having liquor handling
facilities are shown in Table 22. The methods employed for handling
NSSC wastes by mills in the United States are tabulated in Table 23.
Treatment:
Dilute NSSC wastes are treated in aerated stabilization basins at six
mills in combination with unbleached and bleached kraft effluents.
Another employs the activated sludge process to handle the combination
wastes (92). Two mills treat this effluent alone by aerated stabilization
basins (206). No difficulties have arisen in oxidizing these wastes
biologically either alone or in combination with others since both the
rates and degrees of oxidation observed are normal when they are neutralized
and nutrients added. The only effect it has had on treatment systems
in general is to increase the quantity of primary sludge collected and
decrease dewaterability. This is due to the high suspended solids
loss in the form of fines attendant to the manufacture of this pulp.
Biological treatment of dilute NSSC effluents, especially where these
are mixed with kraft wastewaters, is expected to increase considerably
using conventional methods whose effectiveness are well established.
Production of this type of pulp is showing a linear expansion as a
result of the addition of new mills and expanded production at existing
ones.
Land disposal of weak NSSC wastes, which is practiced by two mills, can
be successful if properly laid out and well managed (138,207). However,
a large area of suitable land is required (146). Even for small operations
one-sixteenth inch of waste per day is the maximum quantity that can be
applied. Crops are not grown on these disposal areas.
Extensive research and development work on other methods for reduction
of the pollution load after recovery is underway in the States.
As was discussed in the Advanced Waste Treatment section of this report,
considerable attention has been given to the use of activated carbon
for treating dilute NSSC mill wastes since this material can adsorb most
of the color and a part of the BOD (208). However, its application to
neutral sulfite wastewaters is likely to be limited because of its
relatively low capacity for adsorbing materials responsible for the BOD in
relation of its high affinity for color bodies.
On the other hand, reverse osmosis processes show promise for both BOD
and color removal. A study of their application for concentrating the
dissolved solids in weak sulfite wastes is discussed on Page 56 .
120
-------
FIGURE 28
WATER RECYCLE IN A NSSC MILL
I
PAPER MACHINE
TO
PULP MILL
NO 2
PAPER MACHINE
i
SUMP
COOLING
WATER
VAC.
WATER
•txH
T
TO
R&PER MILL
SUMP
Q
O
WHITE
WATER
CHEST
T
1—i
FRESH WATER —
RECYCLE WATER
•
i
DISC
FILTER
METER
OVERFLOW
TO
RIVER
i
AERATED
STABILIZATION
BASIN
HOLDING
POND
121
-------
TABLE 22
NEUTRAL SULFITE CORRUGATING BOARDMILL EFFLUENT CHARACTERISTICS
(Mills with Liquor Recovery)
Mill #
1
2
3
4
5
6
7
8
9
10
11
12
13
Effluent Volume
Thous. Gal. /Ton
9.1
4.8
7.2
6.0
1.7
11.3
10.0
10.4
25.6
20.0
7.0
10.3
24.0
BODS
#/Ton
30
64
43
27
57
71
90
42
47
69
43
22
150
T.S.S.
#/Ton
15
12
9
17
8
43
28
33
23
46
100
37
40
122
-------
TABLE 23
METHODS OF HANDLING NSSC SPENT LIQUOR IN THE UNITED STATES
Method of Handling
Cross recovery
Recovery
Incinerate (Fluidized bed or
bark boiler)
By-Product Mfg.
To Sewage Plants
Land Disposal
None
Total
No. of Mills
17
3
6
2
3
2
2
35
Cap. T/D
4,880
1,375
1,650
625
615
475
320
9,940
Total Burning Liquor (All methods) 26
7,800
123
-------
Opferkuch (181) and others (209) demonstrated both in the laboratory
and in pilot plant operations that NSSC wastes could be treated to a
high degree in conjunction with sanitary sewage. In reaching this
conclusion it is assumed that adequate plant capacity is provided to
handle the combined fTowage and loadings. As with other pulping wastes,
such treatment does not remove color to a high degree.
Kraft and Soda Pulping
About 80 percent of the chemical pulp produced in this country is
manufactured by alkaline pulping methods, namely kraft or sulfate
and soda processes. In alkaline pulping the wood chips are cooked
in either batch or continuous digesters with, in the case of kraft
pulping, a mixture of caustic soda and sodium sulfide, and in soda
pulping, caustic soda alone. Because of the high cost of these
chemicals and the high concentration required, a chemical recovery
system has always been inherent to the processes (185).
Recovery necessitates separating the spent liquor from the pulp to
a high degree after digestion, and in as high a solids concentration
as possible (185,210) in order to minimize evaporation heat requirements
(211,212). The separation is accomplished by counter-current washing
on vacuum drum washers or continuous diffusers. In some recent
installations a combination of the two is employed (211). Some continuous
digesters contain liquor separation and diffuser washing zones within
the digester body. Three stages of washing are common but in some
cases four are used. The pulp is then diluted, screened, and used
directly for paper production or deckered to high consistency for
bleaching, storage, or lapping for shipment. The separated spent
cooking liquor, known as weak black liquor, has a consistency of 12 to
20 percent solids and is collected in tanks for recovery.
Effluent from the separation stage consists mainly of decker filtrate
water which accounts for about one-third of the BOD5 load from most
alkaline pulp mills (314). Relationships between solids concentration
of this wastewater and BOD 5, light absorbence, and conductivity were
reported by South (213). These relationships are shown in Figure 29.
It is obvious that the relationship of dissolved solids to the three
other parameters of waste strength is linear and of very similar slope.
From this it can be concluded that effluent strength as measured by
these parameters is a direct function of pulp washing efficiency and
that conductivity can be employed as an accurate monitoring index for
the pulp washing operation. (See Page 187.) The magnitude of this
relationship can be disturbed somewhat by loss of liquor to the vacuum
system or to floor drains due to foaming on the washers.
Weak black liquor is concentrated to about 40 to 45 percent solids in
long-tube multiple-effect evaporators and is then known as strong black
liquor. In the case of fatty woods, tall oil soap is skimmed from the
tanks holding this strong black liquor prior to oxidation (if this
operation is practiced). The liquor is then concentrated further and
124
-------
Continuous Pulp Digester at a Kraft Pulp Mill, Kamyr, Inc.
125
-------
ui
to
20-
1.6-
1.2
0.8
0.4
tu
p ^
o w
2i
§1
O 35
3^000 1,000
2500
2POO
FIGURE' 29
10 _
Q ^
O o.
CD E
800
600
IjSOO- 4OO
IpOO- 200
RELATIONSHIP BETWEEN TOTAL
SOLUBLE SOLIDS, BOD, CONDUCTANCE
a LIGHT ABSORPTION IN KRAFT
PULPING DECKER FILTRATE EFFLUENT
IPOO 2POO 3pOO
TOTAL SOLUBLE SOLIDS, (mg/l)
4POO
-------
the skimmings sold as soap or first acidified to produce tall oil it-
self. Spent acid from the latter procedure consists mainly of a solu-
tion of sodium sulfate and is returned to the recovery system as chemi-
cal make-up.
Relief condensate from the digesters is condensed and the turpentine
recovered from it by decantation is sold. The residual water from this
operation is sewered. Blow and evaporation condensates are contaminated
mainly with methanol, and, together with the decantation water, normally
account for another third of the process losses in terms of BOD5 (214).
When surface condensers are employed on the evaporators, the volume
of this stream is low and its BOD5 can be reduced by air stripping
in a cooling tower (67) or by steam stripping (314). In the former
case, methanol and other volatiles are lost to the air and in the latter
case separated and burned. These condensates are frequently reused
for pulp washing and in the caustic room.
In addition to condensates, the other significant wastes involved in
the pulping operation are knots, floor drainage, and tank overflows.
Knots are recooked, sold as a fiber source for coarse paper products,
or disposed of on the land. Floor drains and tank overflows are frequently
collected, stored, and fed back into the sewer at controlled rates
so as to prevent slugs of strong waste or spent liquor from reaching
the treatment system periodically.
Strong black liquor is concentrated further to a consistency of 65 to
70 percent in a recovery furnace stack evaporator or in a concentrator
after which make-up chemicals in the form of new or recovered sodium
sulfate or a residue high in content of this salt is added. Acid sludge
from oil treatment, raffinate from by-product production, from NSSC liquor,
and ash from Incineration of this liquor are examples of such residues.
Salts captured from the recovery furnace stack are also reintroduced into
the system. Sulfur and caustic soda are sometimes used to adjust the
sulfidity in the cooking liquor.
The heavy liquor is then burned and the heat recovered in a specially
designed boiler. During burning, the organic sodium compounds are converted
to soda ash and sulfates to sulfides in the reducing section of the
furnace. The molten ash or smelt is dissolved in water to form green
liquor. This is clarified by sedimentation, the settled residue
washed free of salts and discharged to a land disposal area. The
clarified green liquor is then causticized with lime to convert the
soda ash present to caustic soda, after which treatment it is known
as white liquor. This is settled and sometimes filtered through
anthrafilt pressure filters, adjusted to the desired strength for
cooking with weak black liquor, and stored for use in the pulping
process.
The lime mud (calcium carbonate) obtained on settling this white
liquor is washed and dewatered on rotary vaccuum filters or centrifuges
and burned in rotary or fluidized kilns to form quick lime. This
is hydrated with green liquor in slakers. The residual grits from
this operation are washed and disposed of on the land with the dregs.
127
-------
ro
CO
i
Lime Kiln at a Kraft Pulp Mill, Allis-Chalmers
-------
The following equations described the chemical recovery process.
Reduction:
NaaSO^ + 2C -»• Na2S + C02
Na2 + C02 •*• Na2C03
Causticizing:
Na2C03 + Ca(OH)2 * 2NaOH
Reburning:
CaC03 -»• CaO + C02
Slaking:
CaO + H20 -»• Ca(OH)
Chemical recovery together with other minor losses constitutes the
last third of the BOD5 loss from kraft pulping. It should be noted
that the designation of loss proportions presented here are those
from modern mills operating at nominal production capacity. Operat-
ing abnormalities such as washer foaming or evaporation carry-over
can seriously upset this balance.
Losses per ton of product from kraft pulping itself are difficult
to determine because of the common practice of reusing water from
integrated papermaking operations in the pulp mill. Such reuse is
described by Haynes (26).
The best pulp mill loss evaluation can be obtained from linerboard
operations in which kraft pulp is produced and the integrated paper-
making involves a minimum of additives resulting in low paper mill
losses. Data from fourteen mills indicate the following losses:
BOD5 Total Susp. Solids
#/Ton Prod. I/Ton Prod.
Max. 101 Max. 139
Min. 18 Min. 12
50 12 30 7
35 9 50 8
Avg. 41 Avg. 45
Since about five pounds of BOD can be attributed to the papermaking
operation itself, these values are a bit lower for pulping alone.
Figure 30 is the process flow diagram of a kraft pulp mill and re-
covery system. Figure 31 shows the recovery system alone.
129
-------
FIGURE 30
KRAFT PULPING PROCESS DIAGRAM
LEGEND
CHEM. & LIQUORS
PROCESS WATER
BACK WATER
EFFLUENT
STEAM a GASES
REJECTS
BY-PRODUCTS
p*JEFFLUENT
f
• I DREGS*
1
»••*
SCRUBBER
130
-------
FIGURE 31
KRAFT RECOVERYSYSTEM
PROCESS FLOW DIAGRAM
RTF AM
STRONG ^
BLACK
LIQUOR *
STORAGE
ELECTROSTATIC
PRECIPITATOR
'T !
RECOVERY
FURNACE
i
SALT! _ |
CAKE J i *
OFF
GASES
i
j . _. ! w&
r-J WATER |WA<
I i
'* i
SCRUBBER ~j § |Mp
j GRITS ! J
i t » f - r
i
i
•
•
[
SLAKER ._ £ _^
*
LIME KILN
4
FRESH
WATER
DQOn
LIME
MUD — J
FILTER
^m 1 I •
..J ' LUNDERfLp^
1
f
SEWER
i irr
DISSOLVING
TANK
I
*K JL
1
*_ JSALT CAKE
[^ L WflJER
'i
i
5H i i i
GREEN
LIQUOR
CLARIFIER
DREGS
W^HER
. - ' ' *
CAUSTICIZING
1
*
WHITE
LIQUOR
CLARIFIER
i i
«.! !
1
DREGS
WHITE
^ LIQUOR
* STORAGE
WATER
CHEMICALS
STEAM
131
-------
Soda pulping is carried out in the same manner as kraft except that the
wood is cooked with caustic soda alone which is recovered by dissolving
and cauticizing the smelt from the recovery boiler. Only a minor quantity
of this pulp is manufactured at three mills in this country. Effluent
characteristics are also similar to those of kraft.
Combined kraft mill effluent generally ranges between 150 and 300 mg/1
BOD5 and contains a similar concentration of suspended solids together
with 750 to 1500 mg/1 of color. Total solids run normally from 1200 to
2070 mg/1; the inorganic portion consists mainly of sodium and calcium
sulfates. The effluent under normal operating conditions is slightly
alkaline and the COD ranges between 350 and 500 mg/1 (188).
Treatment:
Most kraft pulp mills treat the total mill effluent by sedimentation in
mechanically-cleaned clarifiers. This treatment removes from 80 to 85
percent of the total suspended solids yielding an effluent averaging
around 25 mg/1 of total suspended solids, the settleable solids removal
exceeding 95 percent. Accompanying BOD5 reduction ranges from 10 to 20
percent. This number Is highly variable due to the constantly changing
suspended solids and dissolved solids content of the raw waste. Settled
effluents from linerboard operations normally range from 100 to 300 mg/1
BODs and average from 20 to 40 pounds of BOD5 per ton of product.
BOD reduction in these effluents is commonly obtained by the use
of holding lagoons or aerated stabilization basins. One soda mill is
installing a plastic media trickling filter designed for high rate
operations and one linerboard mill has a similar roughing filter ahead
of aerated stabilization basins. The degree of BOD5 reduction obtained
depends upon the basin detention period. The period ranges, in the
case of holding lagoons, from 2 to 12 months and, for aerated lagoons,
from 5 to 12 days. Data from four mills employing holding lagoons
indicate effluent BOD5 values of from two to seven pounds per ton
of product with a total suspended solids content of from 0.4 to 7
pounds. Ten aerated stabilization basins at linerboard mills produce
effluent BOD5 values of from 2 to 28 pounds per ton of product at
a suspended solids content of from 1 to 20 pounds, the former depending
upon the retention time and the temperature of the waste under treatment
(117, 118).
One linerboard mill removes color, which ranges from 460 to 2120 units,
with an average of about 750 units, from the wastewater. This is accomplished
by lime precipitation (111) and reduction amounts to over 90 percent. This
process is described in detail in the Advanced Waste Treatment section of
this report.
Acid Sulfite Pulping
Acid sulfite mills in the United States have the capacity to produce in
the neighborhood of 10,000 tons of pulp daily. Manufacture of this
type of pulp has been declining because of the depletion in supply of
132
-------
o
o
Integrated Kraft Pulp and Paper Mill and Effluent Treatment Facilities, Boise Cascade Corp.
-------
suitable wood species, the age and small size of many of the mills
producing it, and the severity of stream pollution problems arising
from discharge of the wastes.
Since recovery of calcium base spent sulfite liquor is both difficult
and uneconomical, it has been frequently discharged directly to the
stream and imposed a very large load as compared to processes employing
recovery systems for the spent liquor. As new processes have been developed
employing bases other than calcium, sulfite mills have been confronted with
alternative courses of action. Recovery was not practical for the small
old mill and these are rapidly being dismantled. Larger mills have either
shifted to the kraft process or have installed recovery systems, or are
in the process of doing so.
At present about two-thirds of the tonnage is produced by mills employing
soluble base recovery systems, half of which are magnesium base, one soda
base, and the remainder ammonia. It is anticipated that within the next
five years practically all the spent liquor will be burned (216). The
remaining five to ten percent is used to produce drilling mud, additives,
adhesives, and chemicals, such as ethanol and vanillin, as described by
Pearl (217) and others (218).
The pollution load in terms of BOD5 and total suspended solids of a number
of calcium mills not burning liquor are compared in Table 24. Process
losses vary widely with the species of wood cooked, the season in which it
is cut, and the degree of cooking employed. The latter is determined by
the pulp characteristics required. The yield from acid sulfite pulping
is low, ranging from 35 to 45 percent.
In this process, cooking acid is made by reacting the base with sulfur
dioxide, which is usually produced by burning sulfur. The finished acid
is cooled, filtered, and adjusted to suitable strength for use in cooking
the chips. Practically all the water leaving this step is cooling water
which can be reused elsewhere. The remainder comes from floor drainage,
filter backwash, and other equipment cleaning operations, and the impurities
contained therein are largely inorganic in nature.
After cooking, the pulp is blown to a tank or blow pit and washed either
in the pit itself or counter-currently on drum washers. In some calcium
base mills where the spent liquor is utilized, countercurrent washing is
practiced in the blow pit which necessitates the addition of weak and
strong liquor storage tanks and accessory pumping equipment. Final wash
water is sewered together with relief and blow condensates when the latter
are collected. The combined weak wastes account for about one-third the
total BOD5 lost from the process (180).
Spent liquor, called red liquor, is evaporated in multiple-effect longtube
evaporators and subsequently in a contact evaporator. Condensates from the
evaporation step are high in acetic acid and account for over 50 percent
of the BOD5 of the combined mill discharge.
134
-------
TABLE 24
EFFLUENT FLOW AND POLLUTION LOADS
FROM
CALCIUM BASE ACID SULFITE PULP MILLS
(Without Liquor Recovery)
Mill # Eff. Flow Thous. Gal. /Ton BOD5 #/Ton T.S.S. I/Ton
1 79 465 12
2 67 620 87
3 66 1130 176
4 69 1150 86
5 87 1240 50
6 90 1003 46
7 61 1290 75
The liquor is burned for its fuel value in special furnaces and, in the
case of magesium and sodium, the chemicals are recovered from the ash
or smelt. Sulfur dioxide recovered from the off -gases is employed in
liquor preparation.
The total effluent from acid sulfite pulp mills employing liquor
separation and burning range from 1000 to 2000 mg/1 in BOD 5 and from four
to five times this value in COD. Disposition of the BOD 5 load within a
modern ammonia base mill is shown in the table below:
BOD.; #/Ton Prod.
From Digester 700
Collected in Liquor 595
Burned in Boiler 475
Condensates 12°
Uncoil ected Liquor 105
In sewer Effluent 220
vacuum pulp washing is employed. Typical losses rrom s u
'1 33
the magnesium base recovery process.
135
-------
TABLE 25
EFFLUENT FLOW AND POLLUTION LOADS
FROM
SOLUBLE BASE ACID SULFITE PULP MILLS
(With Liquor Recovery)
i
Mill # Eff. Flow Thous. Gal/Ton BOD 5 #/Ton T.S.S. #/Ton
1 70 195 20
2 65 225 32
3 59 237 51
4 80 287 49
The solubles contained in sulfite pulp mill effluent consist of organics
and inorganics, the former group containing both biodegradable and
refractory substances. Examples of the degradable type are wood sugars,
fatty acids, alcohols, and ketones and of the refractory, lignins and
tannins. Tyler and Gunter (219) give the following table of constitutents
of spent sulfite liquor:
gm/1
i Formic Acid 0.63
Acetic Acid 4.68
Methanol 1.26
Ethanol 0.17
Acetone 0.13
Furfural 0.29
i
! Pentose 2.55
Hexose 17.50
i
Lignin 61.50
Miscellaneous 29.30
136
-------
FIGURE 32
ACID SULFITE PULPING
PROCESS DIAGRAM
(CALCIUM OR AMMONIA BASE)
r
AMMONIA !
LIMESTONE
SULFUR
STORAGE
~H
SULFUR
BURNER
PROCESS
WATER
ABSORBTION
TOWER
COOKING ACID
STORAGE
I,
i
ACID
COOLER
STEAM
WOOD CHiP
STORAGE
DIGESTER
RED
LIQUOR
OFF
GASES
H
BLOW
PIT
OFF GASES
*
1
EVAPORATION
& INCINERATION
r
*
BY-
PROD.
T
BLOW»REUEF
_.f__G_ASES_
SCRUBBER
RECOVERED
PULP
STORAGE
EFFLUENT
WASH WATER
•J
T
i
EFFLUENT
LEGEND
PRODUCT 8 RAW MAT'L
BACK WATER
M ^^J ^^J ^ ^^V * * * * »™ »•-" ^ - — l"
CHEM.8 LIQUORS STEAM aGASES
PROCESS WATER EFFLUENT
137
-------
FIGURE 33
MAGNESIUM BASE SULFITE RECOVERY SYSTEM
PROCESS DIAGRAM
WEAK RED
LIQUOR STORAGE
I
I
EVAPORATORS
PROCESS
WATER
STRONG RED
LIQUOR
DIRECT CONTACT
EVAPORATOR
I
1
t
1
PROCESS
STEAM
MAGNESIA
COLLECTOR
L
RECOVERY
FURNACE
S02
RECOVERY
r«
"I
I
• OFF
I GASES
-» I—
MAGNESIA
MAKE-UP
SULFUR
STORAGE
FORTIFICATION
TOWER
ACID
FILTER
i
*
SULFUR
BURNER
TO
DIGESTER
COOKING
ACID STORAGE
EFFLUENT
LEGEND
CHEM. a LIQUORS -
PROCESS WATER
STEAM a GASES
EFFLUENT
138
-------
Lawrance and Fukui (28) studied the decomposition of calcium lignosulfonate
establishing its biorefractory nature in the presence of actively decomposing
carbohydrates. 3
Treatment:
Fifteen acid sulfite mills, representing about half the total United States
tonnage, now provide treatment to remove suspended solids from their
effluents. These systems handle bleaching and paper mill effluents as
well since these wastes are combined before treatment. Three mills provide
biological treatment (152, 97, 220, 221); two of which are ammonia base
mills. The third, a magnesium base, treats a mixture of bleaching wastes
and condensates alone. One of the ammonia base mills uses the activated
sludge process (152) and the second aerated stabilization basins (221).
The magnesium base mill provides extended aeration treatment (97) with seed
sludge return. Results obtained with the ammonia base effluents are presented
in Table 26. These indicate BOD5 reductions in excess of 80 percent with
the volatile suspended solids content in the effluent in the order of 30 mg/1.
TABLE 26
BIOLOGICAL TREATMENT OF AMMONIA BASE ACID SULFITE PULP MILL EFFLUENTS
Type Effluent BOD5 #/Ton TSS #/Ton
Treatment Volume M6D Inf. Eff. Eff.
1 Activated 2.5 235 35 30
Sludge
2 Aerated 4.0 160 28 21 (Volatile)
Lagoon
Pre-hydrolysis
X
In order to obtain a bleaching pulp more easily from the chemical pulping
processes, the chips are sometimes steamed in the digester for a short
period prior to the addition of the cooking liquor (198, 185). This serves
to remove readily soluble materials from the wood which have a detrimental
effect on the cooking process. After steaming the chips the digester is
relieved and drained. Pre-hydrolysis is frequently practiced in the
manufacture of dissolving pulps, the degree depending upon the grade of
pulp produced.
The condensates and drainings contain wood solubles with a BOD5 value of
from 60 to 120 pounds per ton for softwoods and 180 to 200 for hardwoods
and amount to approximately 300 gallons per ton in volume (222). They
contain little in the way of suspended solids. Frequently this procedure
is coupled with a "soft" cook which reduces bleachery losses since more
organic matter goes to the recovery furnace with the spent cooking liquor.
In some instances the pre-hydrolysate is added to the weak black liquor as
a means of disposal. Because of the low solids content of the hydrolysate,
this is a relatively high cost practice and requires that higher than normal
evaporator capacity be provided.
139
-------
Magnesium Base Sulfite Pulp Mill with Effluent Treatment Plant, Weyerhaeuser Company
-------
Kraft and Sulfite Pulp Bleaching
The most important bleaching operations from the effluent standpoint are
those applied to kraft and sulfite pulps (201, 185). This is because a
considerable amount of organic material, both oxidizable and refractory,
is removed from the pulp in the process and a substantial quantity of
inorganic matter is discharged because of the addition of bleaching reagents.
These are most commonly chlorine, chlorine dioxide, and calcium or sodium
hypochlorite. Because of the dilute nature of these wastes and their
chloride content they cannot be introduced into the recovery systems.
Ordinarily no control of bleach plant losses can be exercised other than
external treatment. An exception is that a C-H-H-D sequence is used by a
few mills for reducing color of this effluent. Not only is this process more
costly than the usual bleaching sequence, but its use is limited because of
the low-strength pulp produced. Suspended solids content is generally low
with the exception of effluents produced on high-degree bleaching of hardwood
pulps. Concentration of the wastes is a function of water use and reuse in
the bleachery. It is becoming common practice to recycle the latter-stage wash
waters to the rigorous initial stages which are chlorination and caustic
extractions.
Sulfite pulps are more readily bleached than kraft and the effluent is much
lower in both BOD and color. However, the degree of bleaching of all pulps
affects the pollution load generated. Since treatment of pulp to produce
alpha cellulose involves the most extensive bleaching procedures, the very
high losses incurred in producing these pulps are reflected in the effluent
values. Shrinkage in pulp weight in the production of these grades is in
the order of 25 percent as compared to around five percent for other paper-
making grades and sewer losses are correspondingly high. This is particularly
the case for the oxygen demand values since considerable hydrolysis of
cellulosic material takes place when shrinkage is high.
While there can be many process steps in a bleach plant, the important
ones from an effluent standpoint are the chlorination and alkaline extraction
stages (40). The finishing steps such as those involving hypochlorite and
chlorine dioxide usually produce a wash water that can be recycled to the
chlorination and extraction stages, but if discharged make up a minor part
of the BOD and color load. This is particularly true of chlorine dioxide
stages with regard to color since this chemical either bleaches out or
produces materials lower in color than do other bleaching chemicals. A
process diagram of a four-stage bleachery employing recycle of the finishing
stage wash waters is depicted in Figure 34.
Effluent volume, pH, color, BOD 5> and suspended solids ranges for kraft
and sulfite pulping are presented in Table 27. Chloride losses can be computed
from the quantity of chlorine and related compounds added and the chloride
content of the raw water.
These wastes are commonly treated together with pulping and paper-making
effluents for the reduction of suspended solids and BOD and their response to
such treatment is satisfactory. Neutralization of the acid stage effluent
is sometimes necessary. This is accomplished with caustic soda, calcium
hydVate, or carbonate obtained from the chemical recovery system of the mill
in the case of kraft pulping operations.
141
-------
FIGURE 34
FOUR STAGE PULP BLEACHERY
PROCESS DIAGRAM
FRESH
WATER
I
PROCESS
WATER
I
SEAL
PIT
BROWN
STOCK
I
CHLORINATION
STAGE
WASHER
CAUSTIC
EXTRACTION
WASHER
HYPO-
STAGE
WASHER
CI02
STAGE
SULFUR
DIOXIDE
WASHER
BLEACHED
PULP
PRODUCT a RAW MAT'L.
CHEM. & LIQUORS -
^» ^^ ^^^
CHLORINE
SEAL
PIT
CAUSTIC
SODA
SEAL
PIT
HYPO-
CHLORITE
CHLORINE
DIOXIDE
ACID
EFFLUENT
CAUSTIC
EFFLUENT
SEAL
PIT
_l
LEGEND
PROCESS WATER
BACKWATER
EFFLUENT
142
-------
TABLE 27
VOLUME AND CHARACTERISTICS OF KRAFT AND SULFITE BLEACHERY WASTES
Kraft Bleaching
Semi -Bleaching
High-Bleaching
Dissolving Pulp (Soft Wood)
Dissolving Pulp (Hard Wood)
Sulfite Bleaching
Paper Grades
Dissolving Pulp
Effluent
Vol ume
1000 gal /Ton Prod.
18-25
25-35
50-60
55-70
15-20
45-60
BOD
#/Ton Prod.
30-35
40-60
120-150
500-700
10-18
200-450
Total Susp.
Solids
#/Ton Prod.
15-20
20-30
130-150
190-200
8-10
100-200
Color
mg/1
2500-3000
4000-6000
> 5000
> 5000
1000-2000
> 3000
PH
Range
4-5
3-4
2-3
2-3
2-3
1-3
CO
-------
Chemicals Used in Cooking Wood and Bleaching Chemical Pulp
Sulfite and Bisulfite Pulping:
Sulfite and bisulfite pulping liquors are prepared by contacting
sulfur dioxide—produced by burning sulfur or delivered to the
mill in tank cars in liquified form—with a base such as calcium or
magnesium oxide, ammonia, sodium carbonate, bicarbonate, or hydroxide (223).
In the case of sulfite liquors, the amount of base used is insufficient to
neutralize the quantity of sulfur dioxide introduced into the absorption
system so that an excess of sulfur dioxide remains in the cooking liquor.
The following table gives the range of ratios of free-to-combined sulfur
dioxide present in sulfite liquors of the four common bases and the
quantities of chemical required:
Free-to-Combined # Chemical per Ton AD pulp
Sulfur Dioxide
Sulfur Base
Calcium 5 to 1 200-300 260-370 as CaO
Ammonium 3 to 5 120-170 100-175 as NH3
Magnesium 1 to 4 175-250 180-270 as MgO
Sodium 1.2 to 7 140-200 170-250 as Na20
In the case of bisulfite liquors, all the sulfur dioxide is reacted to
form the salt and the cooking liquor consists of the bisulfite of the
base rather than a mixture of this with sulfurous acid.
The reactions involved are as follows:
CaO + 2 H2 SOa -»• Ca (HSOb )2 + H20
MgO + 2 H2 SOb •»• Mg (HSOa )2 + H20
NH3 + H2 S03 + NH* HS03
Na2 C03 + 2 HzSOs * 2 NaH SOs + H2C03
NaOH + H2S03 -> Na HSOs + H20
NaHC03 + H2S03 -»• NaH S03 + H2COa
Neutral sulfite semi-chemical liquors are prepared in the same manner as
sulfite liquors (204, 205). Sodium carbonate or bicarbonate is the usual
base although ammonia has been used. The quantity of chemical varies
144
-------
widely depending upon the quality of product required and affects the pulp
yield inversely. Yield ranges from 70 to 85 percent on the oven-dried
wood basis and from 300 to 500 pounds of chemical is used per ton of AD
pulp. In general, the base is completely neutralized but in some cases a
small excess of alkali is carried in the cooking liquor. This amounts
to 60 to 110 pounds of sodium and 180 to 380 pounds of sulfur per ton
of air-dried pulp.
Calcium base acid is produced by passing pre-cooled gas through a
bed of crushed limestone contained in an absorption tower. Liquor
strength is controlled by the flow of water into the tower and sulfur
dioxide through it. Overflow from the tower is cooled and adjusted
to the desired strength for cooking. In another system, milk of
lime is used to absorb the gas as it passes upward through a bubble-
cap absorption-type tower. A similar system is employed for preparing
magnesium base liquor. The MgO used is initially in the form of
a dry powder, most of it coming from the chemical recovery system.
It is slurried and passed to the absorption towers. The liquor is
sometimes fortified with process off-gases.
Because of the high solubility of ammonia and sodium salts and their rapid
reaction rate with sulfur dioxide, liquors haying these bases are readily
prepared. In the case of ammonia, it is received either as the hydroxide
or anhydrous form in tankers. In the latter case, it is dissolved on
delivery to the absorption towers. Sodium salts are in the form of dissolved
smelt from mill recovery systems or a caustic soda solution delivered in
tankers. Sodium carbonate and bicarbonate are delivered dry and must be
dissolved for use.
Kraft Pulping:
The chemicals used in the kraft pulping system are essentially caustic soda
and sodium sulfide (211). These chemicals are continuously reconstituted,
their losses restored, and recycled through the pulping process. The make-
up chemicals employed are sodium sulfate, caustic soda, calcium carbonate,
and, in some cases, elemental sulfur, these being converted to the desirable
end-products within the system. For example, the lime kiln converts the
make-up calcium carbonate to calcium oxide used to convert sodium carbonate
to hydroxide in the causticizing system. Sodium sulfite is reduced to
sulfide in the recovery furnace and sulfur reacts with caustic soda to
form the same compound. Table 28 shows the typical chemical content of the
various streams involved in terms of the major constituents.
The analysis of cooking liquor commonly employed for pulping pine is
presented in Table 29.
145
-------
TABLE 28
CHEMICAL COMPOSITION AT VARIOUS POINTS IN CAUSTICIZING
Chemical content, ib/AD ton of pulp
Description CaO CaC03
Green liquor from smelt-
dissolving tank
Clarified green liquor
White liquor and mud 746
Clarified white liquor
to digesters
Lime to slaker 418
Mud 746
Weak wash
Washed mud 746
Thick mud to kiln 746
Wash water
Wash water
Filtrate
Dregs from green-
liquor clarifier
Wash water
Dregs to waste
Recovered soda
Reburned lime 418
Lime kiln stack gas
Inert
2
46
46
46
46
46
2
2
46
CO, Total
Na.O
f*
944
919
924
758
5
166
185
10
5
5
25
1
24
5
304
The following as Na20
NaOH
97
94
565
463
3
102
100
8
5
3
3
Tr.
3
5
Ma2S
211
206
208
170
2
38
43
2
Tr.
2
5
Tr.
5
. Tr.
Na2C03
629
612
144
119
Tr.
25
41
Tr.
Tr.
Tr.
17
1
16
Tr.
Na.2SO.»
7
7
7
6
Tr.
1
Tr.
Tr.
Tr.
Tr.
Tr.
Tr.
Tr.
Tr.
Volume
ft3
114
111
111
91
Solids
20
105
15
8
9
44
16
3
29
2
40
Solids
Vapor
-------
TABLE 29
SOUTHERN PINE KRAFT LIOUOR
Consistency of stock, % 3.03
Liquor solids, % 22*9
Liquor Baume' at 60°, °B6 igle
pH of liquor ij-j'g
Na2S, as Na?0, g/liter 3^7
NaOH, as Na20, g/liter 5.26
Na2C03, as Na20, g/liter 32.66
Na2S04, as Na?0, g/liter 0.88
NaCl, g/liter 0.17
Na2SOo, as Na20, g/liter o.OO
NapSjOj, as NapO, g/liter 5.42
TotaT titratable alkali, g/liter 41.79
Active alkali, g/liter 9.13
Total sodium, spectro, g/liter 68.73
Total sulphur, HC104 oxidation, g/liter 11.42
Miscellaneous Pulps:
In cooking rags, from 25 to 50 pounds of sodium hydroxide per ton of rags
is employed and discharged with the cooking liquor as carbonate, bicarbonate,
or combined with organic matter (175). Cold soda pulping employs
from 20 to 100 pounds of sodium per ton of oven-dried wood. Chemi-
groundwood employs a treating liquor containing 60 to 180 pounds
of Na20 with a sodium sulfite to sodium carbonate ratio of from 6:1
to 3:1 (223).
Straw and other grass and agricultural residue pulps are cooked with
either caustic soda, sodium sulfite, or mixtures thereof. A range
in sodium quantity employed in cooking these pulps is generally from
120 to 150 pounds per ton of air-dried raw material.
Bleaching:
The chemicals commonly used in bleaching chemical pulps are chlorine,
caustic soda, calcium and sodium hypochlorites, chlorine dioxide, calcium
bydroxide, and peroxide (201). The first bleaching stage is almost
invariably chlorination which normally employs from 40 to 110 pounds
of chlorine per ton of air-dried sulfite and kraft pulps (201). The
gas is, delivered directly to the chlori nation towers from tank cars.
Evaporators and regulating equipment are installed in the gas lines.
A few mills produce their own chlorine in electrolytic cells.
147
-------
Chiorination is generally followed by an alkaline extraction stage
in which sodium hydroxide or calcium hydroxide are employed to dissolve
out reaction products formed in the chlorination step. The quantity
of alkali used depends upon the wood source, the type of chemical pulp
and how it was cooked, and upon the degree of chlorination in the first
bleaching stage. The range of caustic soda dosage in relation to the
alpha cellulose content of the bleached chemical pulps is presented
in Table 30.
TABLE 30
RANGE OF CAUSTIC SODA DOSAGE IN RELATION TO
THE ALPHA CELLULOSE CONTENT OF THE BLEACHED
CHEMICAL PULPS
% Alpha Cellulose Pounds of KaOH per
in Bleached Pulp Ton AD Pulp Treated
89 10 to 40
92 50 to 120
96 150 to 300
Caustic soda is delivered in liquid form in tank cars or trucks, stored,
and diluted for use in the mills.
Calcium hydroxide is occasionally used for semi-bleached pulp, its effectiveness
and application being limited by its low solubility. The quantity of CaO
applied in this process amounts to 75 to 100 pounds per ton of air-dried
pulp. In kraft mills, the lime used is obtained from the chemical recovery
process.
Hypochlorites of sodium and calcium are very commonly used in the finishing
stages of bleaching. An equivalent of five to six pounds of chlorine is
used for the intermediate stages and two to four pounds for finishing
stages. Sulfamic acid (NH2S03H) amounting to two to six percent of the
active chlorine dosage is sometimes used to accelerate the process The
chemical applied frequently contains residual alkali over that required
to react with the chlorine for pH control purposes.
Sodium and calcium hypochlorites are frequently prepared at the mills by
reacting a solution or suspension of the base with gaseous chlorine in
reaction towers to process specifications, stored, and diluted for use
148
-------
Chlorine dioxide (C102) has cotne into contnon use in recent years as a
bleaching agent because of its specific reaction with lignins and lack of
adverse reaction with cellulosic materials. It is generally substituted
for one or more of the hypochlorite stages and between 0.3 and 1.2 percent
chlorine dioxide is employed per stage. This amounts to 6 to 12 pounds
of C102 per ton of air-dried pulps of the usual types. Its use is
indispensable for the production of dissolving grade pulps from kraft
pulp.
This chemical is ordinarily produced at the mills because of its explosive
properties when compressed or liquified. The production units deliver a
10 g/i solution for storage and use. This high dilution of the gas
is due to its low solubility in water. It is manufactured by several
processes, all of which produce wastes (consisting largely of sulfuric
acid and sodium sulfate) which demand effluent utilization processes.
Fortunately, these chemicals can be used as make-up in the kraft process.
These and their disposition are described in a bulletin on the subject (335).
Hydrogen peroxide is sometimes used in one of the latter stages in bleaching
kraft pulp. The quantity employed is small, ranging from two to five
pounds per ton of air-dried pulp (223).
Caustic soda, sodium silicate, and magnesium sulfate are sometimes used
in the preparation of a peroxide bleaching reagent to control pH value
and the reaction rate. A typical reagent dosage per ton of air-dried pulp
would contain three pounds of hydrogen peroxide, six pounds of caustic
soda, 20 to 40 pounds of sodium silicate, and 0.2 pounds of magnesium
sulfate.
Acidification is sometimes practiced after the last bleaching stage and
most bleach plants are equipped to accomplish this (223, 201). The purpose
is to remove traces of metal ions such as calcium, magnesium, iron, copper,
and manganese originating in the wood or water or dissolved from the equipment.
Sulfurous, sulfuric, or hydrochloric acid is used but sulfurous is preferred
because of its reducing properties and volatility which mitigates against
overdosing. Five to ten pounds of sulfur dioxide on the air-dried pulp
basis is commonly sufficient to accomplish the desired purposes.
Sulfur dioxide in sulfite mills is drawn from the pulp cooking liquor
preparation system and in kraft mills is supplied from tank cars of the
liquified gas. At some mills the gas is used in this form to supply
the chlorine dioxide manufacturing plant.
Additional sources of the data presented in this section are contained in
references (336, 198, 200, 233) from which further details regarding
cooking and bleaching liquor preparation can be obtained. These also
contain detailed process flow diagrams for the various steps in the kraft,
sulfite, and bisulfite chemical recovery processes.
149
-------
Deinking Pulp
Waste papers are deinked for recovery of their fiber content primarily at
ten large mills in the United States. Seven of these deink magazine,
ledger, and other various grades of raw stocks and three mills deink
newsprint only. A large number of small mills deink a variety of waste
papers on a small scale and frequently on an intermittent basis. Some
board and tissue mills do likewise, either to provide liner fiber or
supplement virgin pulp in the furnish. Some mills also reclaim pulp
from trimmings, broke, and other unused waste papers derived from the
manufacturing process itself (223).
The deinking process involves cooking the papers in an alkaline solution.
Soda ash, caustic soda, sodium silicate, and, at times sodium peroxide,
are used. Some employ dispersing agents as well (224, 225, 226). The
chemicals saponify the ink vehicles and solubilize coating adhesives
allowing the ink, coatings, and fillers to be subsequently washed from
the pulp. In the case of newsprint, which consists only of fiber and
ink, a detergent is used to separate the ink so that it can be washed out
(227).
Washing is accomplished on Lancaster washers, in beaters, and in the case
of some small operations, on side-hill screens. With some magazine stocks
as much as 40 percent of the bale weight of the paper is lost to the
sewer in the washing operation (228).
After washing, the recovered pulp is generally given a light bleach with
a hypochlorite or peroxide. The pulp is washed again after bleaching on
drum washers in large mills, but small ones usually wash in the beaters.
Losses from bleaching are very small as compared to cooking and washing
losses. Since the effluent from bleaching is generally employed for
pulp washing it is included in the sewer loss from the entire washing
operation.
Since the range of losses from the deinking of magazine and ledger type
stocks is so wide and newsprint so constant, separate figures are presented
for each in Table 31. The ash content of the suspended matter contained
in the former is generally high and in the latter low.
The suspended solids concentration of deinking wastes from magazine and
ledger stocks runs from 1000 to 3100 mg/1 of suspended solids and the
BOD5 in the order of 300 to 500 mg/1. Combustibles present in the
suspended solids range from 28 to 61 percent and in the total solids
from 1900 to as high as 10,800 (224). Losses in terms of pounds per ton
of product is shown in Table 31.
Figure 35 shows a deinking of waste paper process flow diagram for a
modern large operation.
150
-------
TABLE 31
DEINKING MILL EFFLUENT CHARACTERISTICS
MILL I EFFLUENT VOL.
THOUS. GAL/TON*
Magazine & Ledger Stock
1 30.7
2 29.2
3 65.0
4 31.3
5 48.7
6 42.2
7 43.3
8 58.7
9 54.0
10 14.7
11 30.0
Newsprint
1 9.7 101 233
*Includes paper mill white water with which it is combined in mill
partially through recycle.
BODs
#/TON
80
41
40
75
44
64
91
114
83
97
101
T.S.S.
I/TON
508
59
237
171
294
366
301
355
152
139
740
151
-------
FIGURE 35
DEINKING WASTE PAPER PROCESS DIAGRAM
WASTE
PAPER
I
COOKING
CHEMICALS
_____ |
REJECTS
BLEACH
CHEMICALS
t
COOK
TANK
ISTEAM|
CHEST
T
i
i
i
i
PAPER
MACHINE
WHITE WATER
CLEANERS
PROCESS
WATER
SCREENS
CENTRI-
CLEANERS
EXTRACTORS
BLEACH
WASHER
BLEACH
CHEST
WASHERS
STOCK
CHEST
T
EFFLUENT
LEGEND
PRODUCT a
RAW MAT'L
CHEMICALS
PROCESS WATER
BACK WATER
STEAM
REJECTS -•—•• — -«--*-
EFFLUENT
152
-------
Treatment:
Sedimentation results in the average removal of close to 70 percent of the
total suspended solids from deinking waste. This figure can fluctuate
widely because of the variety of waste papers deinked and the use of
dispersing agents in the process. Removal of the settleable solids is
generally accompanied by a BOD5 reduction in excess of 40 percent. The
sludge produced from the deinking of coated papers is readily dewatered
mechanically but represents a serious disposal problem because of the
large amount produced and its great wet bulk.
Also sedimentation leaves an overflow which is high in turbidity. Chemical
coagulation has not proven an effective means to date for removing this.
Although some chemical agents have been demonstrated experimentally, cost
of their application is prohibitive. The extent of sludge production can
be visualized from the bale weight loss figure which can run as high as
50 percent.
All newsprint deinking waste is discharged at present to public sewerage
Systems for treatment.
Six white paper mills deink old papers on a large scale and five treat
their wastes for the reduction of BOD. Four have aerated stabilization
basins, one being supplemented by spray disposal on the land. The fifth
uses storage oxidation which is accomplished in two large basins. Treat-
ability of this waste was first determined on a demonstration scale
by Palladino (229) using the activated sludge process. Limitations
of this process led Blosser (230) to experiment with aerated stabilization
basin treatment. This in turn led to the successful applications described
by Laing (231), Haynes (232), and Quirk and Matusky (234). Flower
(235) described land disposal following partial aerated basin treatment
at the storage oxidation installation.
Table 32 summarizes the treatment and performance of the three biological
oxidation installations for which data were available. Two of these are
aerated lagoons and the third a holding basin. Influent figures are on
the basis of settled waste because of the inaccuracies inherent to
sampling raw waste for BOD determinations because of its suspended
solids content. Also, the deinking waste has been combined with paper
machine white water prior to treatment which accounts for its low BOD5
value. It'should be noted that the BOD5 in the effluents averaged
as low as 6 pounds per ton of product for one of the aerated basins
and 36 pounds per ton of product for the storage lagoon. Detention
time is the major determinant of performance and it can be presumed
that results equivalent to those observed for the best installation
in operation can be duplicated.
153
-------
TABLE 32
BIOLOGICAL OXIDATION OF DEINKING HASTE
Mill I TYPE TREATMENT
T Aerated Lagoon
2 Aerated Lagoon
3 Holding Lagoon
FLOW
M.G.D.
7.5
1.2
7.0
BOD 5 #/TON
INF.*
95
71
197
EFF
21
6
36
#/TON
INF.*
523
170
255
EFF.
23
17
26
TOTAL SUS.SOLIDS
*tnfluent data are for settled waste.
suspended solids content of the effluents which were all of the same
Magnitude indicates resistance of the extremely fine suspended matter, such
as titanium dioxide, to removal by settling or coalescence by bacterial
activity in the oxidation lagoons.
Manufacture of Paper
Gdarse Papers:
Newsprint, groundwood specialty papers, and wrapping papers are examples
of coarse paper (228). These are manufactured on fourdrinier machines
primarily from virgin pulps and the production of many of them requires
little in the way of additives other than alum and starch. Because of
this, the effluents from their manufacture contain relatively little
•dissolved BOD, this value being largely determined by the concentration
«f suspended fiber or pulp fines present. Frequently, clarified water
from the paper machines producing these products is used in pulping or
other papermaking operations at the same location. A list of coarse
pafier null effluent flows and their BOD 5 and suspended solids content
is presented in Table 33.
154
-------
TABLE 33
1 2.6 M 21
2 2.2 4 42
3 3-7 19 16
4 10.3 is n
5 5.6 10 12
6 4.1 14 10
7 1.9 8 21
8 6.1 n 17
9 11.5 20 15
10 10.3 21 14
11 14.0 26 19
12 12.5 19 13
13 15.2 24 16
Fine and Book Papers:
Most fine paper and book paper is manufactured on fourdrinier machines (228),
a flow diagram for which is presented in Figure 36. The pulp employed is
refined and cleaned with centrifugal cleaners and the necessary additives
applied ahead of the machine. These consist of sizing materials such as
alum and resins, sodium aluminate, and certain wax emulsions. Synthetics
such as acrylics, isocyanates, alkene ketene dimer, fluocarbons, and others
are sometimes employed to impart special characteristics to the paper
produced. Fillers additives include clays, calcium carbonate and sulfate,
talc, barium sulfate, alumina compounds, and titanium dioxide. When
fillers are employed, retention aids, generally starches or synthetic
resin-type compounds, are added to increase retention of the filler
in the sheet. Fillers add opacity to the paper and improve. They
are added in quantities up to 15 percent by dry weight of the materials
used in the process.
155
-------
FIGURE 3C
FOURDRINIER PAPER MACHINE
PROCESS DIAGRAM
PROCESS
WATER
r
r
FILTERED
WHITE WATER
TANK
SAVE-ALL
J
RICH WHITE
WATER TANK
COUCH PIT
WIRE
PIT
L.
EFFLUENT
PULP
CHEST
REFINERS
MACHINE
CHEST
MACHINE
SCREENS
FOURDRINIER
SECTION
PRESS
SECTION
DRIER
SECTION
PRODUCT
LEGEND
PRODUCT 8 RAW MAT'L
PROCESS WATER
BACK WATER
EFFLUENT
156
-------
Some papers are machine-coated with mixtures of pigments and filler
materials and adhesives such as especially prepared starches, dextrines,
and gums such as mannoglactans and synthetic resins.
All modern mills recycle most of the machine waters and employ a save-all
to capture materials lost through the fourdrinier wire (25). These employ
sedimentation, filtration, and flotation with the separated materials
being returned to the papermaking process and a portion of the clarified
water returned for stock preparation and other uses in the paper machine
system. Effluent volume together with the BOD5 and total suspended
solids content is shown in Table 34.
TABLE 34
Mill #
I
2
3
4
5
6
7
8
9
10
11
12
13
LOSSES FROM FINE
Eff. Vol.
M gal./ ton
70.6
33.3
24.0
11.4
57.0
7.2
38.0
53.7
7.5
22.7
36.3
40.0
18.8
PAPER MANUFACTURE
BOD
#/ton
50
19
17
24
16
7
14
40
45
39
23
97
37
T.S.S.
#/ton
104
66
38
56
25
26
44
187
18
100
208
442
150
157
-------
White water from paper manufactured without fillers produces a machine
overflow water containing from 150 to 300 ppm of suspended matter. The
solids consist mainly of pulp fines and are about 90 percent organic
(199). BOD5 values are in the same range, the demand being due to
the cellulose present as well as organic additives (27).
Filled and coated sheets produce effluents of much higher suspended solids
content than those not containing inorganic additives. About half of the
additional suspended matter consists of these substances, hence their high
ash content, frequently amounting to 40 to 50 percent of the total
suspended solids. BOD values are frequently higher because of the
dispersants and adhesives used to retain the filler or coating in or
on the paper. The inorganic materials impart a high turbidity to these
effluents which is generally in proportion to the percentage of them
used in the furnish. The true color of such effluents is low and the
pH is in the neutral range.
These machine waters respond well to treatment by the usual processes
with the exception of the fact that due to the presence of very fine,
high-brightness inorganics, removal of all opalescence is very difficult.
Tissue Papers and Related Products:
Tissue and toweling papers as well as cellulose wadding are produced on
fourdrinier paper machines from furnishes consisting mainly of bleached
sulfite, kraft, groundwood, and deinked pulps. Resins are sometimes
added to give these products special properties such as high wet
strength. Because of the light weights of these sheets the volume of
water employed is high and the effluents weak ranging in total suspended
solids content of from 15 to 250 mg/1 and BOD values of from 35 to 100 mg/1
(236, 195). These run higher at a few mills which use some deinked pulp
in the furnish. The pH value is substantially neutral and natural color
is very low. Table 35 gives loss data for tissue paper.
Specialty Papers:
Specialty paper mills produce over a thousand kinds of paper which are
made and used in small quantities (225). Some mills produce as little
as two tons daily; many single mills produce as many as one-hundred
different grades. A wide variety of pulps and an almost endless number
of additives are used and both fourdrinier and cylinder machines are
employed. Runs of a particular grade are generally short, so that
changeover losses can be higher than those entailed in continuous operation.
A number of these use cotton 1 inters or textile fibers such as flax, jute,
and some synthetics (237).
Because of the great variation of these operations, it is not possible to
give specific numbers to their sewer losses. However, references (220,
238, 239) will give some idea of their magnitude.
158
-------
TABLE 35
Mill #
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
LOSSES FROM TISSUE
Eff. Flow
M gal/ ton
19.2
15.3
62.2
30.4
28.9
21.5
26.6
10.0
18.0
35.9
52.0
44.5
19.0
38.1
24.0
11.8
15.0
30.2
32.9
9.5
PAPER MANUFACTURE
BOD5
I/ton
12
34
96
32
10
19
53
15
45
74
80
44
17
34
51
12
39
31
22
14
T.S.S.
#/Ton
31
46
64
61
65
48
106
43
83
149
in
156
32
33
39
22
34
10
13
17
159
-------
Waste Paperboard Mills
Waste paper is the primary furnish for most paperboard mills although
a small percentage of virgin pulp and fillers are used as lining or
coating on the product. Some mills also deink white paper to supply
the latter requirements. The paper forming section of the board
machine, or wet end, employed depends on the type of product made.
Both fourdrinier and cylinder machines and some special devices as
well are used (228).
Variations and exceptions occur throughout the industry, although in
general, a fourdrinier is used to make a single-stock sheet
and a cylinder machine a multi-ply sheet or heavy board. During recent
years, cylinder machines have been replaced by variations of the
so-called "dry-vat" principle in order to produce a multi-stock sheet
at higher speeds.
The type of paper machine used has little apparent bearing on the raw
waste load generated per ton of productj This parameter is developed
in the stock preparation area and is mainly a function of the type of
raw materials and additives used. In general, the higher the percentage
of kraft or neutral sulfite waste paper used in the furnish, the higher
the BOD value per ton of product. Conversely, the higher the percentage
of waste newsprint of groundwood origin used in the furnish, the lower
the BOD 5 per ton of product. Mills whose wastes have the higher BOD
value generally include those that employ an asphalt dispersion system
in the stock preparation process in order to melt and disperse the asphalt
found in corrugated waste paper. This system subjects the fiber to a
heat and pressure environment in a press and digester which contributes
to the higher BOD loads. A process flow diagram of a typical waste
paperboard mill is shown in Figure 37.
Numerous types of paper and board for a multitude of uses are produced
in about 145 mills in the United States, ranging from crude products
such as pad backing and egg crate filler through corrugated medium
and testliner to coated folding and foodboards.
Effluent volume, BOD5, and total suspended solids data for 42 mills
have been collected and these data are presented in Table 36. These
were compiled from data collected by the Department of Environmental
Sciences at Rutgers University (240), the Michigan Water Resources
Commission (241), the Wisconsin Water Resources Commission (199), the
Pennsylvania State Health Department (195), and the NCASI (242). The
volume of effluent ranged from 3.3 to 24.0 thousand gallons per ton of
product ar.d it is known that at three mills the effluent has been
virtually eliminated through clarification and water reuse. However,
these mills manufacture a small number of products of coarse grade which
makes this procedure possible. Extended full-scale trials on complete
water reuse after diatomite filtration of the machine water at several
other mills indicated this practice to be unsatisfactory when a variety of
high-quality products were made (243).
160
-------
FIGURE 37
1
WHITE
WATER
CHEST
SAVE-ALL
f
WASTE PAPER BOARD MILL
PROCESS DIAGRAM
MACHINE
SCREENS
L
L
FORMING
SECTION
I
*
MACHINE
PIT
EFFLUENT
m PRF
SECT
1
1
ss
ION
DRIER
SECTION
LEGEND
PROD. 8 RAWMATL
CHEMICALS
PROCESS WATER
BACK WATEF
STEAN
REJECTS
EFFLUENT
^ PRODUCT
; __.__
I -
1 ............
+•*++*• ++
161
-------
TABLE .36
Mill #
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
WASTE PAPERBOARD MILL WASTE
Eff. Vol.
M gal/ ton
11.0
16.3
8.5
14.3
4.0
10.8
21.6
10.0
20.0
9.7
9.5
10.0
9.5
6.7
15.0
12.4
10.3
3.3
11.5
5.8
15.8
12.5
9.3
5.8
13.4
12.7
7.5
19.2
6.6
16.6
13.0
11.4
6.0
.9.5
10.0
10.4
8.6
24.0
10.0
10.4
8.6
12,5
LOADINGS
BOD5
#/ton
36
42
15
22
16
13
14
16
36
20
18
19
75
12
67
23
24
32
12
18
16
42
22
16
10
24
35
29
46
16
36
22
17
14
25
20
12
25
25
20
12
26
T.S.S.
£>jtor_
122
123
87
98
8
20
40
42
28
33
28
18
67
14
106
42
59
21
21
34
27
76
30
18
21
30
33
40
29
65
40
43
68
32
16
14
14
54
70
16
14
18
162
-------
The minimum quantity of water required also depends on whether or not
food packaging grades of board are produced. If they are not, a reduction
of discharge to the three to four thousand gallon per ton level may
be achieved. If they are, reuse is somewhat restricted since taste-
and odor-producing substances tend to accumulate in the system and adversely
affect the product. Slimicide usage is likewise limited since some of these
also impart odors. Hence, the minimum practical discharge for a mill
producing foodboard is generally considered to be about seven to ten thousand
aallons per ton of product. Practically all products can be produced
in this effluent range.
Total suspended solids losses for the 42 mills listed range from 8 to 123
pounds per ton of product; 27 containing 40 pounds per ton or under.
This value depends upon the type of save-all employed for fiber recovery
and the application of the more effective types is contingent upon the
kinds of waste paper used and the products manufactured. All mills of
this type can employ a cylinder-type save-all and, while it is not
the most effective type, it serves to separate usable from unusable fiber
and ordinarily restricts losses to less than 40 pounds per ton. It also
serves to protect effluent treatment systems from slugs of fiber and
clarifiers from flotation problems.
BOD 5 values ranged from 10 to 75 pounds per ton of product, 30 of the
42 being less than or equal to 25 pounds per ton. Over and above that
portion of the BOD imparted to the waste by fibrous organic materials,
residual pulping liquor, starch, and other adhesives, such as glutens,
account for most of it. Hence, there is no in-process control that
can be exercised over the BOD losses other than the reduction of suspended
solids. This accounts for the wide variation observed. Some hydrolysis
of cellulose takes place during the process adding to the dissolved
BOD.
These wastes are generally substantially neutral though for some grades
of board lean toward the acid side due to the large amount of alum
used as sizing. They seldom, however, contain mineral acidity and
can be treated biologically without neutralization. They generally
contain relatively little true color unless such is imparted by the
water supply, but can be quite turbid due to the presence of clay or
titanium dioxide used in the process or entering the system with the
waste paper. They are not toxic, but can have a high bacteria count,
these organisms being largely Enterobacter aerogenes. Concentrations
of suspended solids, BODs, and COD are similar to that of strong sanitary
sewage and they respond well to the treatment methods applied to sewage.
table 37 presents detailed analysis of the effluent from two paperboard
mills surveyed over three different time periods.
Close to one-half of the newsprint and waste paperboard mills discharge
to public sewerage systems and additional ones can be expected to follow
this procedure. These are frequently available since many of these mills
are in or close to large municipalities which serve as their source of
raw materials. In this manner the wastes receive both primary and second-
ary treatment to which they are very responsive when mixed with sanitary
163
-------
TABLE 37
Production-Tons
Flow- Million Gallons
Pounds of B.O.D. (Net)
Pounds of B.O.D. Per Ton Product
Pounds of Dry Solids (Net)
Pounds of Dry Solids Per Ton Product
Pounds of Vol. Solids (Net)
Pounds of Vol. Solids Per Ton Product
Gallons Waste Per Ton Product
Fiber Loss-Percent
Population Equivalent
Production-Tons
Flow-Million Gallons
Pounds of B.O.D. (Net)
Pounds of B.O.D. Per Ton Product
Pounds of Dry Solids (Net)
Pounds of Dry Solids Per Ton Product
Pounds of Vol. Solids (Net)
Pounds of Vol. Solids Per Ton Product
Gallons Waste Per Ton Product
Fiber Loss-Percent
Population Equivalent
TE PAPERBOARD MILL EFFLUENTS
Hill 1
Survey
No. 1
29.25
0.735
349
duct 11.9
524
Product 17.9
328
n Product 11.2
t 15,200
0.59
2,090
Mill 2
43.19
0.54
1,224
duct 28.3
1,857
Product 43.0
1,496
n Product 34.6
Survey
No. 2
35.38
0.729
344
9.7
486
13.7
381
10.8
9,830
0.57
2,060
43.0
0.518
957
22.3
1,080
25.1
880
20.5
Survey
No. 3
30.89
0.820
279
9.0
932
30.2
632
20.5
15,300
1.08
1,670
43.4
0.593
870
20.1
940
21.7
785
18.1
12,500 12,050 13,650
1.82 1.08 0.95
7,330 5,730
5,210
164
-------
sewage as pointed out by Gehm (179) and Edde (80). They represent no
problems for the treatment plant when normal fiber recovery is practiced
at the mill and the proportion of mill waste to sewage is not excessive.
However, a fall-off in efficiency in biological treatment due to
insufficient nutrients can occur and difficulties in anaerobic sludge
digestion can result from too high a cellulose level in the primary sludge
(316). In the case of low nutrient level the condition is readily
corrected but this is not true in the case of digestion problems. However,
qualified sanitary engineers are aware of this latter problem and avoid
recommending combined treatment under untenable circumstances.
Over 30 mills treat their wastewater by coagulation and sedimentation,
flotation, or biological oxidation. Some provide only clarification of
the mill effluent after coarse fiber removal. Mechanical clarifiers
are employed and coagulants sometimes used to increase clarity of the
overflow (317). As previously pointed out, this treatment produces
little additional BOD reduction over settling alone.
Coagulation can remove substantially all the suspended solids and an
additional five to ten percent of the BOD5 over that obtained by sedimentation
alone. According to Rudolfs (240) about 25 percent of the BOD is removed
by settling and 30 percent by coagulation and settling. This is
accompanied by total suspended solids and settleable solids removals of
75 and 95, respectively.
High-degree BOD reduction is practiced by a number of mills. Activated
sludge was the first process to be used as reported by Betts and Weston
(103,318) after trials with storage oxidation failed due to odor
production. Klinger (319,320), Shaw (321,322) as well as Peters (323)
reported on construction and operation of modern well-equipped plants of
this type.
Gellman (118), Amberg (324,325), and Haynes (326,232) discuss the application
of aerated stabilization basins for the treatment of waste paperboard mill
effluent. Two of the most recent installations of this kind have been
put into operation within the last year (327,328).
Both methods of treatment are capable of reducing the BOD5 of this waste
over 80 percent consistently. This will be noted on inspection of the
performance data for such plants presented in Table 38 which follows.
Building Products
Building papers are made on fourdrinier and cylinder machines in
generally the same manner as other coarse papers and paperboard from
waste paper, unbleached kraft, and groundwood pulps and combinations
thereof C228). Some are highly sized with alum and resins. The BOD5
and suspended solids losses from the manufacture of these products depend
upon the particular furnish employed and in-mi 11 fiber recovery practice.
BOD5 content of effluents ranges from 5 to 25 pounds per ton of product
165
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TABLE 38
TREATMENT OF WASTE PAPERBOARD MILL WASTE
Mill
#
1
2
3
4
5
6
7
8
9
10
Pretreatment
Alternating Basins
Clarifier
Alternating Basins
Clarifier
Clarifier
Clarifier
Alternating Basins
Clarifier
Clarifier
Clarifier
Type Biological
Oxidation
Aerated Lagoon
Aerated Lagoon
Aerated Lagoon
Aerated Lagoon
Aerated Sludge
Aerated Lagoon
Aerated Lagoon
Activated Sludge
Activated .Sludge
Aerated Lagoon
Flow
MGD
0.7
2.0
2.7
2.0
3.3
0.3
0.3
2.7
0.6
1.0
BOD 5 #/Ton
INF.
45
26
23
30
15
8
15
14
19
27
EFF.
4
3
2
7
0.2
1
2
0.7
2
4
Total Suspended
Solids #/Ton
INF.
46
51
81
87
7
56
60
56
73
49
EFF.
2
4
0
8 _
0.5
3
4
2
6
—-—
en
-------
and total suspended solids from 10 to 60 pounds per ton (329).
Reasonably good in-mill fiber retention can hold the latter value
to below 20 pounds per ton. The effluent from these operations is
readily treated both alone and in combination with pulping or other mill
effluents by both the common suspended solids removal and biological
oxidation methods (330). Effluents containing less than 1.5 pounds per
ton of product and a similar quantity of suspended solids can be
anticipated from biological treatment of these effluents.
Building felts are produced from single refiner groundwood pulp, waste
paper, and, in some instances, other fibers. They are made on forming
machines and, since the furnish is generally hot, a very high degree
of white water recycle can be practiced without experiencing slime or
formation difficulties. Overflow white water volume frequently runs
less than 1000 gallons per ton of product. Effluent characteristics
are similar to that of waste paperboard except for the fact that some
of these materials are impregnated or sized with bituminous materials
or contain mold proofing or fungicidal materials which can be toxic to
aquatic life.
It has been demonstrated that these wastes can be treated biologically
to some degree; however, much better purification is obtained after
their being incorporated with sanitary sewage (315,250,331). Presently
no plant is treating this waste by itself since most felt mills are
connected to public sewerage systems. Where the capacity to handle
the load is adequate, no difficulty has been reported by sewage plants
receiving this waste in obtaining a high degree of treatment.
Insulating board is produced on fourdrinier-type mold-forming machines
from single refiner groundwood or agricultural residues such as bagasse
(188,185). Some of these mills also produce board products of an inorganic
nature from rock wool and glass fibers, interchangeably. Water recycle
depends to a great degree on the specific product manufactured as does
the suspended solids content of the white water. Low-grade products
allow a high degree of recycle and because of the thick fiber
mat formed on the wire, high fiber retention is achieved. In the case
of some products, however, the retention of fines in the sheet is undesirable
and in these cases fiber losses can be very high. Hence, the suspended
solids concentration of these effluents can run as high as 3500 mg/1
or near 300 pounds per ton of product and the BOD5 in the same magnitude.
Removal of a large percentage of the BODs is accomplished on settling out
the suspended solids (264) and that remaining amounts to between 20 and
30 pounds per ton of product. Most hardboards are produced by adding
binders produced in much the same manner as insulating board and consolidating
it on a wire surface in a hot press (228). This treatment removes all the
moisture and sets the natural binders present in the wood as well as
those added, which can be linseed, tung, tall oil, or pheno-formaldehyde
resins. A typical effluent from such a process amounts to 5300 gallons
per ton of product containing 30 pounds of BOD5 and 39 pounds of total
suspended solids. This effluent responds well to sedimentation and biological
treatment both alone and in combination with sanitary sewage and to land
disposal as well (332).
167
-------
A process diagram of an insulting board-hardboard mill is presented
in Figure 38. : " '
A second process for producing hardboard is the "explosion" or Masonite
process in which wood chips are placed in a "gun" under steam pressure
of about 1000 psig then exploded against a target plate (228). The
material so produced is disc refined, washed, and formed into a wet
lap on a forming machine and pressed between platens of a hydraulic
press having a screen on one side to allow for drainage. When the
water is removed, natural binders formed by. treatment of the wood allow
its bonding into a solid sheet.
The losses of BOD and fines from this process are quite high because
of disintegration of fibers and solubles removed on washing the fiber.
This wash water has a BOD5 ranging from 4000 to 6000 mg/1. Parsons
and Woodruff (244) indicate mean losses of 170 pounds of BOD5 and 80
pounds of total suspended solids for one Masonite hardboard operation.
One mill evaporates and burns the strong liquor (244) and at another
it is disposed of on the land (137). The weaker wastes, including
machine waters, are genrally disposed of on the land (137). One insulating
board mill employs an elaborate land disposal system for disposal of
both weak and strong waste as described by Philipp (245). This employs
a holding basin for the strong waste allowing controlled seasonal discharge
on a 100-acre spray irrigation area, with a hydraulic loading of up
to 0.55 inches per day and over 138 pounds of BOD5 per acre per day.
Results of treatment at four hardboard mills by biological oxidation
with and without land disposal of strong wastes indicate that effluents
ranging from 2 to 13 pounds of BOD5 per ton of product can be obtained
on treatment of building board mill wastes by various means as shown in
Table 39.
Miscellaneous Pulps
Textile Fiber Pulps:
Small quantities of pulps having special qualities are produced from
cotton and linen rags, cotton 1 inters, jute, hemp, flax, and old cordage
(223,175). These pulps are used in the furnish for fine writing papers,
monetary papers, condenser blotting, bristol, tag stock, cigarette,
Bible, and a variety of other speciality papers as well as in electrical
fiber and impregnated products. These pulps have the ability to impart
special properties such as great strength, long life, or fine appearance
to papers in which they are incorporated. At one time rags were the
common source of most textile fiber pulp but because of the synthetic
fiber content of most cotton rags today cotton 1 inters have largely
replaced them. In some instances linters are treated to remove
impurities and bleached at the mill, producing a wastewater, while in
others they are purchased in a prepared form ready for use. The preparation
of linters produces a waste of from 7000 to 20,000 gallons per ton of
168
-------
FIGURE 38
INSULATING BOARD, BUILDING BOARD
AND HARDBOARD PROCESS
DIAGRAM
WOOD CHIPS
STEAM [•
r~
WASTE
PAPER
OEFIBRINATOR
PULPER
STOCK
CHEST
1
BAR
REFINER
CHEST
WHITE
WATER
CHEST
I
SAVE-ALL
SCREEN
FORMING
MACHINE
BUILDING FELT
OR
INS. BOARD
DRIER
EFFLUENT
HYDRAULIC
PRESS
STOCK
CHEST
JORDAN
CHEST
REJECTS
PROCESS
WATER
.J
CHEMICALS
HARDBOARD
LEGEND
PRODUCT a RAW MAT'L
CHEMICALS
PROCESS WATER
BACK WATER
STEAM
REJECTS
EFFLUENT
169
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TABLE 39
RESULTS OF TREATMENT OF BUILDING BOARD MILL EFFLUENTS
Treatment
Save-all, Settling Basins,
Extended Aeration
Neutralization, Clarifier,
Cooling, Activated Sludge
Clarifier, Storage,
Activated Sludge
Neutralization, Settling
Basins, Aerated Lagoon,
Activated Sludge
Settling Basins, Storage
Basin, Aerated Lagoon
BOD j/Ton T.S.S.#/Ton
Inf.
120
193
210
61
98
Eff.
11
2
4
3
13
Inf.
45
20
19
14
28
Eff.
6.0
0.8
0.6
2.8
4.8
170
-------
product containing 250 to 500 pounds of total solids and between 35 and
100 pounds of BODs depending upon the quality of the 1 inters processed
and individual mill practice.. The waste is high in pH, containing both
carbonate and caustic alkalinity due to the caustic soda used in
treating the 1 inters (27).
All textile fibers with the exception of flax are prepared in essentially
the same manner. In many mills a number of raw materials are employed
and specific pulps produced sporadically or intermittently since the
equipment required for all of them is the same, but the paper products
manufactured are of a wide variety, some requiring more than one type of
pulp.
Cooking is conducted in rotating cylindrical or spherical pressure
vessels. The vessel is charged with the raw material and in some cases
this is given a pretreatment with a detergent to remove dirt. In this
case, after steaming and rotating for a short time, the vessel is drained
and the cooking chemicals added. These consist of caustic soda, soda ash,
lime, or a combination of the latter two. Flax is cooked with either a
mixture of caustic soda and sodium sulfide or draft white liquor (NaOH +
Na2S). At the start of the cook, water content is generally adjusted to
2.5 to 3.5 percent of raw materials.
When cooking is completed the contents of the boiler are blown into a
drained pit. At some mills the pressure is gradually relieved and wash
water added to the boiler. The boiler is then rotated to aid the washing
operation, drained, and the contents removed by hand.
Whether or not boiler washing is practiced, the cooked pulp is transferred
to a beater where it is diluted and beaten to the desired degree. After
this, the washing cylinder is lowered and a large volume of wash water
introduced, washings being discharged from the cylinder. On completion
of washing, if bleaching is required, calcium or sodium hypoclorite is
added and the contents of the beater circulated until bleaching is complete.
Most of the textile fibers require less than 0.5 percent chlorine and many
as little as 0.1 percent. A final wash completes the process after
which the pulp is deckered to the desired consistency and delivered to
a stock chest. A process diagram is presented in Figure 39.
It is obvious on examination of this diagram that wastewaters emanating
from the preparation of these pulps can include the following individual
streams:
Scour and blowdown wastes
Boiler wash water
Blow-pit drainings
Beater wash water
Bleach wash water
Decker water
Nemerow (246) and Rudolfs (194) evaluated these wastes in terms of total
suspended solids and BOD content and typical data is shown in Table 40.
171
-------
FIGURE 39
SPECIALITY PULP MILL
RAW
MATERIAL
L-_—~.£i
COOKER
BLOW PIT
BEATER
DECKER
i
SEWER
CHEMICALS
w
STOCK CHEST
PROCESS
WATER
BLEACH
PROC. WATER
CHEMICALS WASTE WATER
172
-------
TABLE 40
POLLUTION LOAD FROM TEXTILE'FIBER PULPING
TYPE WASTE VOL. TOTAL SOLIDS TOTAL SUSP. BOD 5
PULP THOUS. GAL/TON ///TON SOLIDS ///TON ///TON
Jute 65 922 281 316
Rope & Hemp 75 1,360 277 1,213
Rag 80 2,600 474 707
They (247) also determined the load distribution during the washing
operation in terms of BOD5 and total and suspended solids for rag, rope,
and jute pulps as shown in Table 41. Interest has been aroused in improved
washing techniques which can greatly reduce the volume of water required
and contain the liquor solids in a small volume.
Textile fiber pulping and boiler wash liquors are frequently lagooned
because of their small volume and high strength. Also, it is well to
keep them out of the general waste stream if chemical coagulation is
practiced since they interfere with this process (244). The washer and
bleaching wastes are generally combined with the mill white water. The
combined flow can be treated by common sewage treatment processes
such as sedimentation (247), coagulation (248), or biological oxidation
(223,249). Storage oxidation of the combined waste has been the most
common method of treatment but one mill ran a trickling filter for many
years (251). Both pilot and full-scale tests by Nemerow (57) in which
a mixture of jute pulping wastes and white water were settled revealed
that a 78 percent total suspended solids reduction was observed as compared
with a 91 percent reduction for the white water alone. Effluent BOD5
values doubled when the pulping waste was intermixed due to the presence
of solubles as well as the lesser reduction in suspended solids.
Pulping wastes have been treated along with mixtures of alum and calcium
chloride. After settling the sludge is lagooned and the supernatant
discharged into the general waste stream.
Studies have revealed that liquors could be handled by anaerobic digestion
after neutralization and nutrient additives (252).
Agricultural Residue Pulps:
-i . •• • • ,
Small quantities of bagasse, straw, cotton seed hulls, esparto grass,
bamboo, and corn stalks are pulped in this country (185), some on a
continuous full-scale basis and others intermittently. The latter
procedure is either because of periodic shortages of the usual raw
173
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TABLE 41
Load Distribution in Cook Liquors and Progressive Beater Wash Water Wastes
Flow(%)1
Jute
7.4
16.7
25.9
44.5
63
81.3
100
Rope
2.8
10.9
19
35.2
51.5
67.6
83.9
100
Rag
1.8
8.6
14.3
26.9
39.4
51.8
64.3
76.8
89.3
LOO
Washing
Time
(hr.)
O(cook)
1/4
1/2
1
1-1/2
2
2-1/2
3
3-1/2
4
B.O.D.(%)1
Jute
41
74
85
93
96
99
100
Rope
47
68
80
90
94
96
98
100
Rag
65
77
83
92
96
98
99
99+
99+
100
Total Sol. (J5)1 Susp. Sol. (JO1
Jute
34
64
77
88
93
97
100
Rope
61
76
83
90
93
95
98
100
Rag
52
62
70
79
85
89
91
94
96
100
Jute
25
56
71
88
93
97
100
Rope
4
34
54
75
84
87
93
100
Rag
25
33
42
50 "
65
71
77
82
91
100
^Percentage of total accumulation.
-------
material used or is on an experimental basis. Straw once accounted
the effluent obtained In pulping
TABLE 42
TYPICAL ANALYSIS OF STRAHBOARD WASTE
Effluent Flow 35,000 gal /ton
Total Solids 1,050 #/ton
Ash of Total Solids 70%
Total Suspended Solids 490 #/ton
BOD 246 #/ton
Sludges obtained from settling wastes produced from pulping agricultural
residues do not dewater well and are productive of odors (due mainly to
HaS) on lagooning. Storage of either the waste or sludge results in a
considerable BOD reduction because of anaerobic decomposition, but the
odor problem is too severe to permit this practice. The wastes respond
to both aerobic (253) and anaerobic treatment (256,257,258,259), but the
plant capacity requirements were too high to permit their application.
Land disposal was practiced at one mill (260) but the high organic matter
content limited loadings at which the waste could be successfully applied
to the soi1.
It is likely that most textile and agricultural residue pulping operations,
together with the attendant papermaking, will dispose of their effluents
into public sanitary sewerage systems in the future. Their small size as
well as their ability to reduce water consumption, and in some cases, the
waste loading to a considerable degree, and the proximity of most operations
to municipalities makes this course of action most reasonable since they
are readily handled by the sewage treatment processes (220).
175
-------
Other Mill Effluents
In addition to process effluent, many mills discharge water from their
utilities. These consist of filter backwash and sedimentation tank
underflow or clean-out from water treatment, boiler blowdown, and ,
cooling water. In some instances the latter is salt or brackish water.
In addition, mills burning bark and/or coal usually sluice ash to a
ponding area. Frequently the grits and dregs from kraft recovery
systems are combined with this flow. In addition to these effluents,
some mills dispose of process clarifier underflow on landfill areas.
In respect to landfill areas, good practice dictates the return of
overflow water from them to the waste treatment system since it can
be high in both suspended solids and BOD*. The overflow water from ash
sluicing ponds generally carries but a small pollution load which frequently
is discharged only during periods of high precipitation. Hence, it is
diluted with rain water and the receiving stream at relatively high
runoff.
176
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SECTION XI
COST OF TREATMENT
The most recent and complete statistics on pulp and paper industry
expenditures for waste treatment and attendant information on this
activity are contained in the reports of surveys conducted every
two years by the NCASI. These detailed reports for 1968 and 1970
were published by Bolduc (342) and Blosser (370,373). The last
survey was drawn upon extensively for information used in this
section.
At that time, 70 percent of the mills which were responsible for
89 percent of the nation's pulp and paper production reported.
These totaled 414 mills of which 326 provided some form of effluent
treatment or employed specialized disposal methods or ocean outfalls.
Others discharged to municipal systems as discussed in Section IX of
this report. There were 242 mills reported as providing primary
treatment and 112 secondary treatment in the form of storage oxidation,
aerated stabilization, activated sludge, or trickling filters.
Capital Cost
Gross capital expenditures for treatment by type of mill is shown in
the table below reproduced from this report:
Type of Mill Millions of Dollars
Kraft Pulp and Paper 200
Sulfite Pulp and Paper 65
Semi-Chemical Pulp and Paper 39
Mechanical Pulp and Paper 33
Mixed Chemical Pulp and Paper 13
Non-Integrated Paper and Paperboard 30
' TOTAL 38TT
Most of the expenditures for primary treatment ranged from $1,000
per ton of daily production capacity to in excess of $4,000, although
a few ranged between $300 and $1,000 per ton. Most expenditures for
secondary treatment ranged from $1,000 to greater than $6,000 per ton
of daily production capacity with a limited number of mills reporting
values lower than $1,000. The simplest form of secondary treatment,
storage oxidation, accounted for the lower values.
The wide range in capital costs from mill to mill results from variations
in plant size, local labor and materials costs, and land prices,
as well as topography, foundation, and piping requirements. Costs
of individual pieces of equipment are set forth in Volume III of Tne
Cost of Clean Water" (341) published by the Department of the Interior.
This data can be adjusted to present cost levels.
177
-------
Industry trends also have a decided effect on costs. Some of these
are the abandonment of small, old chemical pulp mills which are' no ^
longer profitable; refurbishment and expansion of the older kraft mills;
the large capacity for which the new mills are designed; improved recovery
and other internal sewer loss control techniques; and increased water
recycle.
Operating Costs
The operating costs of primary treatment were reported from 20 cents per
ton of product for earthen settling basins to $2 to $5 per ton where
mechanical clarifiers and dewatering were employed. Biological oxidation
operating costs showed an even wider range running from as low as 20 cents
per ton for an isolated case employing storage oxidation. 'For systems
reducing the BOD5 greater than 70 percent, costs ranged from $1.20 to $7
per ton. The cost for high-rate secondary treatment, including disposal
of the sludge produced, exceeded $2.50 per ton.
Size naturally affects operating costs appreciably, the larger units
being generally more economical to run on a unit basis. Amberg (339)
presents figures showing the wide variations that can occur in
operating costs from mill to mill for both primary and secondary treatment.
Costs for the former at three mills amounted to $6.28, $12.29, and
$35.50 per million gallons treated. Corresponding values for secondary
treatment at the first two mills amounted to $32.00 and $42.60 per
million gallons treated or $1.58 and $1.75 per ton of product. Costs
per pound of BOD5 removed generally run from 2 cents to 7 cents for the
larger mills.
Operating costs for sulfite liquor recovery run from $1 to $10 per
ton and for NSSC between $1 and $5 according to Blosser (373).
Advanced Waste Treatment Costs
Cost of treatment of linerboard mill effluent for color removal with
lime, but without lime recovery, is given for Davis (177,371) as $3.19
per ton of product for a 400-ton-per-day unit. Computations presented
by Herbert (40) indicate that recovery could substantially reduce this
figure. These investigations included lime recovery from effluent
recarbonation as well as that recovered from the precipitate containing
the color bodies from the effluent.
Berger (367) and Thibodeaux (349) calculated that a water of good
quality except for the presence of electrolytes could be produced
from linerboard mill effluent for less than 20 cents per thousand
gallons. However, substantial removal of the electrolytes would add
50 cents per thousand gallons.
Leitner (366) and Voelken (347) indicated that reclaiming reusable
water and obtaining a concentrate suitable for recovery from strong
pulping wastes would cost $1.17 per thousand gallons. Considerable
information on water reclamation unit process costs have been presented
by Hoenig (372) and in other reports covering the U.S. Public Health
178
-------
Service investigation on advanced waste treatment (343). Although these
studies were conducted on pretreated sanitary sewage rather than pulping
effluents, costs appear reasonably comparative for the unit processes
involved. Additional data of this type have been published by Critts
(34ft) for waiter treatment in which the values presented appear comparable.
It remains for present and future demonstration projects to substantiate
computations for reclamation of treated pulp and paper mill wastes of
the various types commonly discharged. The need for more efficient,
reliable, and less costly electrolyte reduction is obvious if anything
approaching closed systems is to be realized. The hope for this lies
in perfection of processes capable of selectively removing such undesirable
tons as chlorine. Such processes are discussed by Reeve and Rapson (233).
tost of Converting Calcium Base Sulfite Mills to Magnefite Pulping
The cost of converting large (400 to 500 tons per day) calcium base
sulfite pulp mills to magnefite pulping runs in the neighborhood of
$16 million, the range in cost per ton being between $30,000 to $40,000.
179
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SECTION XII
EVALUATION OF COMMON TESTING PROCEDURES
FOR PULP AND PAPER MILL EFFLUENTS
Biochemical Oxygen Demand (BOD)
The BOD test serves to measure the biochemical oxygen-consuming capability
of papermaking wastewater and is a good measure of the effect of the
wastes on receiving streams (261). Since this test can be quantified
in terras of quantity of oxygen required, it is one of the fundamental
measurements of wastewater characteristics, and is particularly applicable
to wastewaters of the pulp and papermaking process. The time required
for completion of the normally employed test (five days) is a major
shortcoming and unfortunately rules out the test for process control use.
Attempts to shorten the time interval to less than five days have not
been overly successful (262).
Suspended Solids
Because suspended solids from papermaking operations have differing
properties depending upon their organic or inorganic nature, it is
pertinent to distinguish between or to characterize the nature of the
solids discharged. This is determined by differentiating between
volatile and non-volatile fractions of the solids that are present in
the wastewaters. The method for suspended solids (non-filterable solids)
is specified in the EPA manual, previously cited, and requires filtration
through a glass fiber filter of specified pore size, followed by drying at
103° to 105°C. "Standard Methods" and other publications (261, 263) offer
alternatives in filtration media such as the "asbestos mat" and the
membrane filter. Historical data based on the "Standard Methods" should
be acceptable for this test. However, the "Federal" method should be
specified for future testing.
Chemical Oxygen Demand (COD)
The National Council for Air and Stream Improvement reported on a study
of COD/BOD relationship of raw and biologically treated mill effluents
(188). In concludes:
"Based on the results obtained it does not appear possible to
develop time-automated treatment process and effluent discharge
controls for rapid BOD estimation based on the COD test. Examination
of BOD, COD, and lignin content relationships on 352 samples of
untreated and treated pulp mill effluents showed no fixed
relationship between these values. It is probable that materials
other than lignin which are resistant to biological oxidation are
present in the waste, as well as some lignin materials which do
not decompose. Possibly these latter are functional groups of the
181
-------
large lignin molecule. There is also wide variation in momentary
relative concentration of the various constituents present in these
wastes as discharged. Correcting COD values for oxygen equivalent
of the lignin content of both untreated and treated wastes signifi-
cantly lowers the COD/BOD ratio. However, it does not yield a
ratio sufficiently constant for reliably estimating BOD by this
technique.
In view of the large number of representative samples used and
the well controlled laboratory techniques employed, it appears
that final solution of this problem will depend on the separation
and measurement of those constituents contributing to both
chemical and biochemical oxygen demand."
This is not surprising, nor has there yet been discovered any physical-
chemical procedure that correlates well with the BOD test. However,
this shortcoming—the lack of correlation—is not sufficient to rule
out a test procedure that can provide meaningful information that may
be translated into stream or effluent quality appraisal. The dichromate
procedure for COD (with chloride correction) has been recognized as a
"Standard" method. This method seems to correlate well with filtered
domestic sewage and with wastewaters having characteristics similar to
domestic sewage. A less favorable correlation is experienced with
treated effluents, with the COD/BOD ratio increasing with greater
biological stabilization. This serves to indicate that biologically
stabilized effluents contain organic components that react very slowly
biologically, but retain chemically oxidizable properties. The COD
test is also more easily repeatable than the BOD test since its conditions
are better controlled. On the other hand, there is little established
usage of the COD test in which it is readily quantified. Treatment plant
performance designs are predicated strictly on BOD/suspended solids
criteria, especially through secondary treatment stages. Therefore,
the COD test as currently practiced, provides some useful information
that may be utilized to provide a general classification of the total
oxidizable organic content of a wastewater or its receiving stream,
but the interpretation of COD values, without other qualifying data,
provides very little of value for classifying effluents or the resultant
effects on stream quality.
Color
The need to measure color and to limit its presence in receiving waters
is spelled out in the water quality criteria for aesthetic, water supply,
fish, aquatic and wildlife propagation, and some industrial uses. For
aesthetic purposes, the criteria specify the absence of objectionable
color. For water supply uses, the criteria recommend a limit of 75
color units (cobalt-platinum standard units). This standard permits
water treatment plants to produce a satisfactory finished water with
moderate dosages of coagulants and chemicals. For fish, aquatic life,
and wildlife propagation, the criteria specify that at least ten percent
of incident light must reach the bottom of a desired photosynthetic
zone in order to maintain adequate dissolved oxygen levels. The conversion
182
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of «or 'H J*Sandard C0l°r Un1tS iS not P°Ssible because
a vSS ahnvp S , -1 VT natural and wastewater sources. However,
H ? * -S haS bee" s19"1f1cant in limiting photosynthesis
Jhdeletjrious effect upon aquatic life, particularly phytoplankton
™H th-h h ,
Xnd SSrf h!!S£» ' SOmS SpeClfiC industrial water users, primarily the
food and beverage producers, require raw water color to be limited to
five units. However, industry in general sets no specific limit because
of its varied specific water uses.
The standard method for color measurement is in terms of platinum-cobalt
units of color, as specified in "Standard Methods" for water. Since the
color of the wastewaters from pulp, paper, and paperboard manufacture
have the characteristic brown color very similar to the platinum-cobalt
standard, there is little need to modify this procedure except for those
special processes in which dyes are used to introduce other colors.
Brown (159) suggests, however, that all mill effluent measurements be
made at pH 7.6 because there is a significant pH effect on the color of
pulping and bleaching wastes.
Turbidity
Turbidity and suspended solids parameters are not synonymous. Suspended
solids are filterable parti culates in the fluid; turbidity is the light-
scattering properties of a fluid. Where suspended solids are present,
turbidity is always found. However, sometimes turbidity may be observed
under conditions of extremely fine particle size, which pass through
the standard filters used for the measurement of suspended solids.
Historical data on turbidity of mill process streams is non-existent,
but methodology is well established (261), since dispersed matter has
traditionally been reported as suspended solids. However, the quality
effect on water uses that distinguishes turbidity from suspended solids
requires that effluents be characterized using both parameters. It is
therefore recommended that turbidity be a standard measurement of plant
effluents only, since its usage in the operating mill process flows has
no important significance.
Coli form Organisms
The use of the total col i form test as a quality criterion for natural
waters is rapidly being displaced by the fecal col i form test. This
differentiation is significant to the assessment of natural water
quality for contact recreation purposes and for public water supply
because it is being universally recognized that the protection of the
public health is served better through the elimination of those
organisms that are directly related to human and animal fecal matter.
It has also been amply documented that many of the wastewaters from
this industry have a property of stimulating the multiplication of
co form orgL'sms because of the presence of various carbohydrates
extracted from wood during the pulping process. The resultant high
183
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coliform concentrations may appear significant, but invariably, these
are classified as non-fecal types, with only a very small fraction
testing out as of fecal origin (265). Where mill sanitary sewage is
combined with process wastes, there is, of course, a relatively higher
fecal coliform content. Based on these considerations, the total coliform
tests should no longer be a requirement for effluent bacteriological
quality. It should be replaced by tests that differentiate the presence
of the fecal coliforms. If these are found in appreciable numbers their
sanitary significance should be evaluated for the specific situation.
TL - Medium Tolerance Limit
This is a bioassay procedure used to establish a concentration level of
the substance under test that will result in survival of (or non-injury to)
50 percent of a test population during a specified time interval (266).
A static procedure has been standardized in "Standard Methods" using
fish as the test organism for those instances in which the material
being tested is persistent, non-volatile, and without significant oxygen
demand.
It is well known that process wastewaters from various pulping processes
exert varying degrees of toxic effect upon the ecology of receiving
waters. It is also well known that biological treatment reduces these
toxic effects significantly. Since toxicity tests are not yet recognized
universally as standard tests and they are relatively expensive and
tedious to perform, it would seem logical to suggest that these tests
be required only under those circumstances which would constitute a
sensitive relationship between the use of a body of water for wastewater
disposal and its use for the propagation of valuable fish and food
organisms. In these instances, the test should be performed under
continuous flow-through conditions where feasible. The ultimate purpose
of the test would be its use as a regulator of the discharge rate of the
final effluents from the affected mill.
Alkalinity-Acidity and pH
Little in the way of acidity or alkalinity which could prove detrimental
to treatment efficiency or recovery water conditions results from the
discharge of papermaking effluents. While the pH of some of these may
be high or low they are for the most part poorly buffered and contain
little titratable alkalinity or acidity. Hence, they are readily brought
within an acceptable pH range in the course of usual treatment or dilution
by receiving waters containing some buffering capacity as most do.
Examples of these are kraft and soda pulping effluents from balanced mills
with good effluent control. Such mills normally produce an alkaline
effluent which, while quite high in pH value, contains no caustic alkalinity
and only a small amount of normal carbonate alkalinity, hence is readily
neutralized on treatment or dilution. However, some pulping and
bleaching wastes are more troublesome. Sulfite pulping effluents are
acid due to the presence of sulfurous and sulfuric acids and require
neutralization. Also, bleaching wastewaters from the chlorination and
caustic extraction stages are respectively low and high in pH and can
184
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caustic extraction stages are respectively low and high in pH and can
contain sufficient mineral acidity or caustic alkalinity to require
neutralization before treatment or discharge. On combination with the
pulping effluent some interaction occurs tending to neutralize the mixture
However, when a high degree of bleaching is practiced, the residual
effluent is low in pH and contains sufficient mineral acidity to necessitate
neutralization prior to treatment of discharge.
Since pulp and bleaching wastes contain organic acids which are poorly
ionized, alkalinity and acidity are much better measures of the alkali
and acid content of these wastes than is the pH value outside of the
immediately neutral range (pH 5.5 to 10.5). Also these figures are
required to determine the quantity of neutralizing chemicals required when
this procedure must be used (50).
Alkalinity, acidity, and pH are all measured by the techniques set forth
in "Standard Methods".
Heavy Metals
Low concentrations of chromium, nickel, lead, mercury, and zinc have
been found in process wastewaters of the industry, particularly in
the waters from pulping and bleaching operations. Mercury may be
present in the caustic used in these processes; chromium and nickel
could be picked up as corrosion products along with iron from the
process equipment. Zinc is used in some groundwood bleaching operations
in low concentrations. These metals have know toxic effects on aquatic
life, and their presence in water for human consumption is limited to
very low concentrations. Methods for determining mercury in pulp and
paper and associated wastes are reported by the National Council for
Air and Stream Improvement (267).
Nitrogen and Phosphorus
Excessive concentrations of the nutrient elements phosphorus and
nitrogen, when present in a natural water body, have been implicated
as the causative agents in overfertilization and overgrowth of
undesirable aquatic organisms leading to eutrophication. Sources of
these nutrients are the wastewaters from municipal wastes, some
industrial wastes, and surface drainage. The processes in use by the
pulp, paper, and paperboard industry result in wastewaters that are
usually deficient in one or both of these critical nutrient elements
(268). Therefore, it has been a general practice to add calculated
quantities of nitrogen and phosphorus to the biological treatment
processes in order to optimize treatment. It has been determined that
a ratio of 1:5:100 of phosphorus: nitrogen: BOD should be maintained.
However, actual requirements are frequently lower in practice. Therefore,
it is concluded that there is very little likelihood of excessive
nutrient concentrations being found in the process wastes or wastewaters
from this industry and that no useful purpose would be served to suggest
analysis for these substancees.
185
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Toxic Components
Van Horn (269) published methods for the detection and quantitative
measurement of the major toxic components of alkaline pulping effluents.
Those covered by his studies were sulfides, mercaptans, and resin acids
for which techniques for determination in the fractional mg/1 range
were set forth. An improved method for determining resin acids in a
similar concentration range was developed by Carpenter (270).
Foaming Capacity
An empirical method for evaluating the foaming capacity of mill effluents
was developed by Carpenter (127). The technique advocated was patterned
after those employed in the soap and detergent industry and involves the
persistence as well as degree of foaming.
186
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SECTION XIII
EFFLUENT MONITORING
f
Biochemical oxygen demand (BOD) and total and suspended solids are the
most useful parameters to be employed in monitoring the effluents of
this industry. These three parameters measure the effect of the most
significant components of these wastewaters on receiving waters and
provide the basis for quantitative evaluation of treatment effectiveness,
It has been demonstrated (271) that a linear relationship exists between
total dissolved solids and the BOD5 of unbleached kraft pulping decker
filtrate as illustrated by Figure 40. The efficiency of this relationship
was corroborated by the fact that the total dissolved solids content
of kraft black liquor and BOD5 are similarly related. The same
relationship was shown to exist for NSSC spent liquor. While the
determination of total dissolved solids is infrequently used, it can
be determined in about an hour's time as compared with the BOD5
which requires five days. While attempts have been made to shorten
the period of time required for biochemical oxygen demand determinations
(261), none of the tests proposed to accomplish this have met wide
acceptance. This is probably because those proposed required a day
or more to complete. Hence, attention has been given to quicker tests
and those lending themselves to automation which could be used for
immediate control of sewer losses within a mill. These included the
oxygen consumed and COD tests (272,273), neither of which showed any fixed
relationship to the BODs for kraft or NSSC wastes. Variations in !
momentary relative concentrations of biologically oxidizable and
refractory organics probably account for this lack of correlation between
the determinations.
However, color as measured by light absorption and conductivity exhibits
a linear relationship to the BOD5 value. The observed relationship of
light absorption to BOD5 for kraft mill decker filtrate is presented in
Figure 41 and that for NSSC machine effluent in Figure 42.
A color-BOD5 relationship also exists for evaporator jet condenser
water as shown in Figure 43. This could be expected since the carryover
of black liquor from the evaporators contributes color and BOD5 in
proportion to the concentration.
Control monitoring in pulp mills is accomplished largely by conductivity,
a measurement which can be made continuously and reliably with a minimum
of instrument attention. Multiple-point instruments can be employed to
cover such streams as the decker filtrate overflow for indicating pulp
washing losses and on the sewer carrying evaporator condensate to
187
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FIGURE 40
RELATION BETWEEN TOTAL DISSOLVED SOLIDS
AND BOD5 IN DECKER SEAL PIT WATER
1,000
800
o»
E
600
JP
o
CD
400
200
ipoo 2,000 3,000
TOTAL DISSOLVED SOLIDS (ing/1)
4,000
188
-------
I200r
FIGURE 41
BOD5 IN RELATION TO LIGHT ABSORBENCE
KRAFT MILL DECKER SEAL PIT WATER
00
UD
1,000
800
600
in
o 400
m
200
0.2
0.4
0.6 0.8
ABSORBENCE
1.0
1.4
1.6
-------
FIGURE 42
BODg IN RELATION TO LIGHT ABSORPTION
OF NSSC WHITE WATER
2,000
1,600
N.
O»
E
ID
O
O
CD
1,200
800
400
Q2
F'
0.4 0.6
ABSORBENCE
Q8
1.0
190
-------
FIGURE 43
RELATIONSHIP BETWEEN BOD. AND LIGHT
ABSORBENCE OF EVAPORATOR JET CONDENSER WATER
160
140
120
o»
E
100
10
o
o
CO
80
60
40
0.1
0.2 0.3
ABSORBENCE
0.4
0.5
191
-------
monitor evaporation operation. These instruments can also be equipped
with audible or visual signal devices for informing the operators immediately
if losses are high. Conductivity is sometimes used to activate valves
diverting waste streams to holding ponds during periods of high losses
resulting from operational problems, breakdowns, or accidents within
the miVl. i The linear relationship between conductance and total dissolved
solids is shown in Figure 44.
Level-indicating devices on overflow weirs are frequently used to ;
indicate flowage from unit processes or from segments of a mill. These
serve to call attention to inadvertent discharge from:storage chests
and tanks which can seriously affect sewer losses.
Some work has been done in respect to employing continuous turbidity
and suspended solids content recording for paper mill effluents. The
turbidity measurement operates satisfactorily if maintenance is good,
but maintenance is more urgently needed in this application than is
required in the continuous measurement of process or potable water
turbidity. Color, however, can interfere with this measurement.
t's '/
Ostendorf and Byrd (274) used a total carbon analyzer to estimate the
BOD value of a sulfite mill effluent with satisfactory results and ,
have since applied it to the effluent of another sulfite mill treating
its waste by the activated sludge process. The same authors applied
a new instrument for the continuous measurement of suspended solids
in the effluent. Unlike turbidity measurement devices this instrument
employs both opacity and light scattering and the readings correlate
well, with suspended solids content of effluent in the 100 to 200 mg/1
range. - The authors present correlative curves for both the organic
carbon and suspended solids instruments.
-> .•:-
Dissolved -oxygen content of wastes under treatment and on discharge is
frequently recorded at pulp and paper mills employing a variety of the
instruments marketed for this/purpose. These require routine attention
if reliable results are to be expected.
The pH value, like conductivity, has been used to indicate high pulp
mill losses, but the latter is preferable since it provides a much*
better indication of magnitude. Since some wastes, such as sulfite
pulp wash water and acid bleaching wastes, require neutralization, pH
recorders are used to monitor and control automatically the dosage of
neutralizing chemical required.
Interest has been shown recently in application of selective ion '
electrodes for,monitoring pulp mil 1,.effluents. Schwartz and Light (275)
report on the use of a sulfide ion electrode; others have been
experimenting with a sodium ion/electrode.
192
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3000
FIGURE 44
RELATIONSHIP OF TOTAL DISSOLVED SOLIDS TO
CONDUCTANCE OF KRAFT DECKER SEAL PIT WATER
o
^
(0
o
2500
§ 2000
o
CO
tu
o
o
o
o
o
1500
1000
500
1000
1500 2000 2500 300O
TOTAL DISSOLVED SOLIDS (mg/l)
3500
4OOO
450O
-------
SECTION XIV
ACKNOWLEDGEMENTS
Members of the administration and staff of WAPORA, Inc. who were
associated with the assembly of information and writing of this
"state-of-the-art" report on the nature and treatment of pulp and
paper mill effluents are appreciative for the guidance received from
Mr. George R. Webster and Mr. Ralph H. Scott of EPA throughout its
preparation. They are greatly indebted to individual pulp and paper
manufacturers who granted access to their mills and treatment works,
made operating records available, and whose technical personnel
critically reviewed portions of this text.
Appreciation is extended to the National Council for Air and Stream
Improvement of the paper industry whose extensive research, development.
and survey information covering a period of close to 30 years formed
the framework of this study. Information supplied by the American
Paper Institute and the Institute of Paper Chemistry is also most
appreciated.
The assistance obtained from universities and personnel of state
agencies concerned with water quality is herein recognized.
195
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SECTION XV
REFERENCES
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3. Slatin, B., "The Paper Industry in 1971," Industry Information
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4. Slatin, B., "Paper and Paperboard: 1970-1971," American Paper
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5. U.S. Industrial Outlook, U.S. Department of Commerce, Bureau of
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197
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15. U.S. Industrial Outlook, U.S. Department of Commerce, Business
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198
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199
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46. McKeown, J.J., "An Investigation of the Effects of Bark Leaching
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200
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59. Fuller, H.E., Williams, R., and Moultar, P.W., "New Developments
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201
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128. Edde, H. , "A Critical Review of the Literature on Slime Infesta-
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Aquatic Habitat Requirements," Pulp and Paper Magazine of Canada,
T67, February (1960).
280. Fry, F.E.J., "Requirements of the Aquatic Environment," Pulp and
Paper Magazine of Canada. T61, February (1960).
281. Douderoff, P. and Shumway, D.L., "Dissolved Oxygen Criteria for
the Protection of Fish," American Fisheries Society, Special
Publication #4 (1967).
282. Warren, C.E., "The Influence of Carbon Dioxide and pH on the
Dissolved Oxygen Requirements of Some Fresh Water Fish,"
NCASI Technical Bulletin #123 (1959).
215
-------
283. Van Horn, W.M., "The Toxic Effects of Sulfite Pulp Waste Liquors
on Fish and Other Aquatic Life," NCASI Technical Bulletin (1945).
284. Van Horn, W.M., "The Toxic Effects of Kraft Pulping Wastes on
Typical Fish Food Organisms," NCASI Technical Bulletin #10 (1947).
285. Van Horn, W.M., "The Toxicity of Kraft Pulp Mill Wastes to Important
Fish Food Organisms," NCASI Technical Bulletin #25 (1949).
286. Howard, T.T.,and Walden, C.C., "Pollution and Toxicity Characteris-
tics of Kraft Pulp Mill Effluents," TAPPI 48. 136 (1965).
287. Kawabe, K. ,and Tomirama, T., "On the Nature of Poisonous Substances
in Alkaline Pulp Mill Waste," Report V, Bulletin of the Japanese
Society of Scientific Fisheries 21 (1) 37 (1955).
288. Seppavaara, 0., and Hynninen, P., "On the Toxicity of Sulfate Mill
Cqndensates," Paper and Timber (Finnish) 52, 11 (1970).
289. Webb, W.E., "Preliminary Studies to Determine the Nature of the
Principal Toxic Constituents of Kraft Mill Waste," M.S. Thesis,
Oregon State University (1949).
i
290. Banks, R.C., "Isolation of Certain Toxic Components of Kraft Mill
Waste and Attempts to Determine their Structure," PhD Thesis,
Oregon State University (1969).
291. Warren, C.F., "Some Effects of Unbleached Kraft Mill Effluents
on Salmon. " NCASI Technical Bulletin #217 (1968).
292. O'Neal, G.L., "The Degredation of Kraft Pulping Waste in Esturine
Waters," M.S. Thesis, Oregon State University (1966).
293. "Experiments, Studies, and Expenditures of International Paper
Company, Southern Kraft Division, on It's Waste Disposal Problem "
(1944).
294. Servizi, J.A. et al, "Toxicity of Two Chlorinated Catchecols,"
Progress Report #13, International Pacific Salmon Fisheries
Commission (Canada).
295. Servizi, J.A. et al, "Toxicity and Treatment of Kraft Bleachery
Waste," Progress Report #17, International Pacific Salmon
Commission (Canada) (1966).
296. Das, J.B. et al, "Tetrachloro - binguinone as a Component of
Bleach Kraft Chlorination Effluent Toxic to Young Salmon,"
Journal of the Fisheries Research Board (Canada) 26, 3055 (1969).
297. Warren, C.E., "Bioassay of Spent Sulfite Liquor, Lignosulfonate and
Their Decomposition Products," NCASI Technical Bulletin #171 (1964).
216
-------
298. Williams, R.W., "Toxic Effect of Sulfite Wastes on Young Salmon,"
Washington Department of Fisheries.
299. Lang, C.J., and DeHass, G.G., "Acetic Acid Recovery from Sulfite
Liquor." TAPPI 531L_1094 (1970).
300. Private Communication, Federal Water Quality Administration,
Corvallis Laboratory (Oregon) (1970).
301. Van Horn, W.M., "Factors Affecting the Migration of Fish,"
NCASI Technical Bulletin #3 (1946).
302. Van Horn, W.M., Brandt, B.B., and Hassler, W.W., "An Analysis of
a Four Year Study of the Striped Bass Fishery in the Roanoke
River and Albemarle Sound," NCASI Technical Bulletin #121 (1959).
303. Dimick, R.E.,"
-------
313. Beder, H., and Gillespie, W.J., "The Removal of Solutes from Pulp
and Paper Mill Effluents by Reverse Osmosis," TAPPI Air and Water
Conference (1968).
314. Bergkrist, S., and Foss, E., "Treatment of Contaminated Condensates
in Kraft Pulp Mills," Proceedings International Congress on Industrial
Waste Waters, Stockholm (1970).
315. NCASI Research Reports (1956).
316. Snell, J.R., "Anaerobic Digestion, II Nitrogen Changes," Sewage
Works Journal. 15, 56 (1943).
317. Private Communication, Treatment of Effluent from the Elkhart,
Indiana, Mill of Continental Can Co. (1968).
318. Betts, C.N. et al, "Construction and Early Operation of a One MGD
Bio-Oxidation Pilot Plant," Sonoco Products Corp., Hartsville,
South Carolina (1954).
319. Klinger, L.L., "Whippany Completes Final Link in Tri-Mill Waste
Treatment System." Paper Trade Journal, 36, May (1962).
320. Klinger, L.L., "Whippany Expands Tri-Mill Waste Treatment Complex,"
Water Works and Wastes Engineering. 1, 60 (1964).
321. Shaw, R.F., "Activated Sludge Treatment at the Whippany Mill,"
NCASI Technical Bulletin #220 (1968).
322. Shaw, R.F.private Communication, "Activated Sludge Treatment at the
Whippany Mill," (1968).
323. Peters, J.C., and MacNeal, J.A., "Comprehensive Waste Treatment for
a Paperboard Co.," Public Works. 94, 99 (1963).
324. Amberg, H.R., "Aerated Stabilization of Boardmill White Water,"
Proceedings Purdue University Industrial Waste Conference XX (1965).
325. Amberg, H.R. et al, "Supplemental Aeration of Oxidation Lagoons with
Surface Aerators," TAPPI. 47. 27A (1964).
326. Haynes, F.D., "Three Years Operation of Aerated Stabilization Basins
for Paperboard Mill Effluent," Proceedings Purdue University Industrial
Waste Conference XXIII, 361 (1968).
327. Quirk, T., and Groff, W.R., Private Communications (1971).
328. "National Gypsum Describes Milton Mill Facilities," NCASI Technical
Review, 9 (1970).
329. Private Communication, New Zealand Forest Products, Ltd. (1971).
218
-------
330. Quirk, T.P., "Bio-Oxidation of Concentrated Board Machine Efflu-
ents," Proceedings Purdue University Industrial Waste Conference
XXII (1967).
331. NCASI Research Reports (1960-1965).
332. Nepper, M., "Biological Treatment of Strong Industrial Wastes from
a Fiberboard Factory," Proceedings Purdue University Industrial
Waste Conference XXIII (1968).
333. "U.S. Capacity Survey Shows Small Increase Through 1974," Paper Trade
Journal. Nov. 22 (1971). ™"
334. "The Top 50," Chem 26. 7, 34 (1971).
335. "Alternate Uses and Treatments of Chlorine Dioxide Generator Efflu-
ents," TAPPI CA Report 23 (1972).
*
336. Clark, L. H., and DeHaas, G.G., "Volatile Acid Recovery from Vapors
by Chemical Reaction," TAPPI 52, 1728 (1969).
337. Luety, A.T., "The White Water Problem," Boxboard Research and Develop-
Association, File No. 5 (1970).
338. Biggs, W.A. , Jr. et al, "The Commercial Production of Acetic and For^
mic Acids from NSSC Black Liquor," TAPPI 44, 385 (1961).
339. Amberg, H.R., "Water Pollution Control in the Pulp and Paper Industry,"
Industrial Water Engineering. 26, Nov. (1970).
340. Critts, C.J., "Economic Factors in Water Treatment," Industrial Water
Engineering. 22, Nov. (1971).
341. The Cost of Clean Water. Industrial Waste Profiles No. 3 Paper Mills,
U. W. Department of the Interior, Federal Water Pollution Control Ad<-
ministration, Publication No. 1 - WP - 3 (1967).
342. Bolduc, E.J., Jr., "Results of NCASI Survey of Investment and Cost of
Effluent Treatment," Proceeding of General Meeting of the NCASI (1967).
343. "Advanced Waste Treatment Research - 1," Summary Report, U. S. Depart-?
ment of Health, Education, and Welfare, Public Health Service (1960-61).
344. "Nature of the Chemical Components of Wood," TAPPI Monograph #6 (1948).
345. "Paper Coating Materials," TAPPI Monograph #19 (1958).
346. "Paper Coating Pigments," TAPPI Monograph #30 (1966).
347. Voelker, M.H., "Reverse Osmosis for Waste Treatment," TAPPI 55, 253,,
(1972).
219
-------
348. Adams, P.P., and Clark, M.P., "Bleach Plant Counter-Current Wash-
ing," Proceedings TAPPI Air and Water Conference, 237 (1970).
349. Thibodeaux, L.J., and Berger, H. F., "Laboratory and Pilot Plant
Studies of Water Reclamation," NCASI Technical Bulletin #203 (1967).
350. Rapson, W.H., Pulp and Paper Magazine of Canada 68, 12, T635 (1967).
351. Van DeVeer, P.H., "Oxygen Bleaching," Paper Trade Journal 154, 41
(1970).
352. Bergkrist, S., "Treatment of Contaminated Condensates in Kraft Pulp
Mills."
353. Anon., "The Development and Successful Operation of a Closed White
Water System," NCASI Technical Bulletin #183 (1965).
354. Ullman, P., "Planning a New Inland Kraft Pulp Mill," Proceedings of
the International Congress on Industrial Wastes, Stockholm (1970).
355. Guerrier, J.J., "Bleaching - Is Oxygen Coming Into the Fore?," Pulp
and Paper 64, Aug. (1970).
356. Matteson, M.F., "Steam Stripping of Volatile and Odorous Substances
from Kraft Mill Aqueous Streams - A Pilot Plant Study," Pulp and Paper
Mill Research Laboratory Report No. 71, University of Washington (1960).
357. Staff Report, "Designing Profits in and Costs Out," Chemical Week 40,
Feb. 11 (1970).
358. Rowlandson, G-, "Continuous Oxygen Bleaching in Commercial Production,"
Paper Trade Journal 38. Dec. 21 (1970).
359. "Oxygen Bleaching After Seventeen Months of Operation," Paper Trade
Journal 58, Dec. 13 (1971).
360. Smith, D.R., and Berger, H.F., "A Chemical-Physical Wastewater Reno-
vation Process for Kraft Pulp and Paper Wastes," Journal Water Pollu-
tion Control Federation 40, 1575 (1968).
361. Wiler, A.J., "Progress in Developing Reverse Osmosis for Concentrating
Pulp and Papermill Effluents," International Congress on Industrial
Waste Water Treatment, Stockholm (1970).
362. Nelson, W.R., and Walvaven, GO., "A Role for Reverse Osmosis in a Neu-
tral Sulfite Semichemical Pulp and Paperboard Mill," Proceedings Purdue
University Waste Conference XXIII (1968).
363. Williams, W.C., and Haas, L., "Annual World Review," Pulp and Paper (1971).
364. Kunin, R.C., and Vassilou, B., "New Deionization Techniques Based Upon
Weak Electrolyte Ion Exchange Resins," Industrial and Engineering Chemis-
try Process Design and Development (1964).
220
-------
365. McGlasson, W.G., "The Feasibility of Granulated Activated Carbon Ad-
sorption for Treatment of Pulp and Papermill Effluents," M. S. Thesis,
Chemical Engineering Department, Louisiana State University (1965).
366. Leitner, G.F., "Reverse Osmosis for Waste Water Treatment - What -
When?," TAPPI Air and Water Conference, p. 171 (1971).
367. Berger, H. F., "Evaluating Water Reclamation Against Rising Costs of
Water and Effluent Treatment," TAPPI 49. 79A (1966).
368. Rimer, A.E. et al, "Activated Carbon System for Treatment of Paper-
mill Waste Waters," TAPPI Air and Water Conference, 159 (1971).
369. Wiley, A.J., Dubey, G.A., Holderby, J.M., and Ammerlaan, A.C.F.,
"Concentration of Dilute Pulping Wastes by Reverse Osmosis and Ultra
Filtration," Meeting Water Pollution Control Federation, Dallas,
Texas (1969).
370. Blosser, R.O., "Pulp and Paper Industry Stream Improvement Expendi-
ture and Accomplishment Survey," Procoedings TAPPI Air and Water Con-
ference (1971).
371. Davis, C.L., Jr., "Tertiary Treatment of Kraft Mill Effluent Includ-
ing Chemical Coagulation for Color Removal," TAPPI 52, 11 (1969).
372. Koenig, L., Report to the Advanced Waste Treatment Program, HEW (1960).
373. Blosser, R.O., "A Survey of Pulp and Paper Industry Accomplishments
in Receiving Water Quality Protection Programs, NCASI Special Report
#71-02 (1971).
221
-------
SECTION XVI
APPENDICES
223
-------
APPENDIX I
Economics Department
PAPER AND PAPERBOASD PRODUCTS. IMPORTS. EXPORTS AND SEW SUPPLY
"APER PAPESBOAPJO
Production Imports
1-47
194S
1949
1950
1951
"-9I2
195"
1054
1955
IPS'*
1957
.',953
1959
1?60
!'•£;.
3.5'iZ
1963
19-V--
l?f,5
1-^6
1?67
19-58
156?
1570P
19717
1"727
1973?
,,,--...
,,,,,,, p
,„,,,,
1'1"CF
9,416
9,7<:7
9,!-;'.1
10,63",
11,5-S
10, 8 -?i
11 ''C-C
111 649
12,905
13,91/0
13,581
13..497
15,071
15,399
li,<3::5
15,537
17 s I'OO
•;:.:;::
".0,1C>7
2o|e:.3
20,944
K2,29£
?.j,504
23,220
24.C30
25,315
•"•, ;-• ',
v o-j*
ill, 260
5- 7,,,-.
4,062
4,506
4,680
4,920
3,033
5,104
5,103
5,089
5,263
5,715
5,343
5,017
5,440
5,574
5,621
5,673
5,592
6,139
6,531
7,270
6,897
6,755
7,186
7,045
7,100
7.4CO
£,'70
- 9,310
+11
-J
™ew
Sports Sur->iy
310
241
234
225
347
333
238
378
475
399
448
411
392
427
4S9
439
473
562
556
618
539
641
619
616
615
615
«£
745
.•WO
.*--'
13,167
14,062
13,645
15, '333
16,310
15,620
16,232
16,360
- 17,693
19,306
18,475
18,103
20,118
20,546
20,955
21,770
22,413
23,729
23,152
27,305
27,252
23,522
30,071
29,649
30,545
32,100
37,^6?
45,100
54,260
65,700
Production
9,187
9,356
8,9S7
10,926
11,620
10,772
12,335
12,191
13,367
14,234
14,062
14,150
15,459
15,675
16,535
17,484
18,239
19,605
20,834
22,574
22,035
24.504
26,022
24,940
25,630
27,235
31,873
38,590
46,300
•55,70'!
Imports
27
45
47
54
78
56
97
52
45
31
45
47
44
37
42
46
45
'15
14
57
20
28
23
12
10
15
20
30
-4 ,000
-4.5C9
Exports
114
112
102
111
250
173
203
272
330
338
379 '
406
482
563
635
715
829
1,098
1,178
1,295
1,470
1,957
2,034
2.163
2,100
2,200
2.S05
3,420
CESSES DATA
(000 Tons)
Sew
Supply
9,100
9,299
8,542
10,868
11,449
10,654
12,229
11,970
13,532
13,928
13.72H
13,790
15,021
15,150
15,292
16.816
17,455
18,522
19,670
21,336
20,635
22,575
23,?62
22,789
23,540
25,050
?•>,<*?
35,200
42,300
51,^00
Production
2,499
2,734
2,120
2.S11
2,802
2,748
2,902
3,037
3,407
3,217
3,024
3,176
3.4SS
3.3G9
3.-91
3,519
3,691
;,S46
4,059
3,887
3,897
4,343
4,531
4,297
4,614
4,825
S5-4
6.7*5
8,115
9,850
OTHER" GSADES
Import «t
-i.
31
24
35
39
31
31
49
73
69
83
85
13"
111
115
149
139.
232
255
193
193
266
2S4
211
215
245
330
360
-(400
+450
Exports
50
43
36
36
39
36
34
38
41
44
43
35
30
37
41
39
33
44
34
41
39
42
63
64
65
65
60
60
Kcv
Sup??.?
2,4-';3
1,/T.l
2,107
2,310
2,302
2,743
2,-OCO
3,OM>
Mr!
3,'i>>5
3.2C5
3.K5
3^Vs3
3.MS
S.G^O
3,041
4.133
4,280
4.C39
4,056
4,iaS
4,753
4,443
4.764
5.035
5-8?*
7,045
8,515
10.300
?rodi-ctton
21,102
21.S97
20,315
24,375
26,047
24,413
26.6C5
?i,by&
K.^!>>
.SI .441
25.&J5
3O,S23
34/B5
-3i,W4
35.749
37,541
39,230
41.703
44.CSO
47,113.
'j6,9~6
51.245
T-4,057
52,457
34,3-54
57,375
57.M1
81,370
97,6,5
118,250
Septcaber,
1971
TOTAL
latports
4,122
4.5C2
'=.752
5.003
5,150
5.5.91
5;231
5,150
5.3C5
5.G-.5
5,472
5, '49
S-.C22
3,7=1
5,773
5.SS3
5.82S
5.3S5
6.SC3
7,5'0
7,115
7.CU
7.453
7,238
7,££0
3,5-7
i.0,200
+7
•W
Shorts
tjf-.
-37
372
372
535
5?".
•'; 1- .S
687
245
702
M73
033 _
CH2'
1.G7
1.215
1,193
1.341
1,705
1.773
l,9Si
2.CD7
2.5^5
2.7C3
a,«3
2.7CO
2.S63
3a
4,225
,-sac
,95«
y.ev
Supply
24.749
16,033
24,005
29,012
nt-,561
it9,017
31,360
"1,379
?i,7!.9
25.49S
25,^-53
£5,?.*.9
.r->4725
25,138
40,312
42,216
A3, 715
4C,30/>
49,102
32,<;?.0
-l,"':^
3f.,6'>7
52,754
ss-.asi
3C,C^iO
02,15.-.
77.. SV
«7.34S
!••>> ,075
12, ',200
*•* - i-cr.T.i .t. by ^conowics Depa
P - Jrelir!:™'TV Jit'l Forecast.
,v.!"=rican i'ancr Institute.
-------
APPENDIX 2 .—Apparent consumption of paper and board by grade, 1920- 1966
ro
PO
Year
1920
1925
1930
1985
1940
1945
1950
1955
1960
1961
1962
1963
1964
1965^
1966>
Total
paper and board
Total i
Million
tons
7.7
10.4
12.3
12.8
16.8
19.8
29.1
85.0
89.3
40.5
42.8
43.9
46.6
48.9
52.3
Annual
rate
of in-
crease2
Percent
6.2
3.4
.8
6.6
8.8
8.0
8.8
2.8
8.1
4.4
8.8
6.1
4.9
7.0
Total paper
Total 1
AfiiKon
tans
5.4
7.1
8.4
8.2
10.6
11.0
16.8
19.4
22.1
22.5
28.2
24.0
25.4
26.6
28.4
Annual
rate
of In-
crease1
Percent
6~6
8.4
5.8
.7
8.8
2.9
2.6
1.8
8.6
8.4
6.8
4.7
6.8
Newsprint
Total
Million.
tons
2.2
3.0
8.5
3.4
8.7
8.5
5.9
6.5
7.4
7.4
7.5
7.6
8.1
8.4
9.1
Annual
rate
of in-
crease*
Percent
6.1
8.1
iS
Il76
2.0
2.6
1.4
1.8
6.6
3.7
8.8
GTO^IQQ^TOOQ
paper
Total
Million
tons
0.2
.2
.2
.4
.6
.6
.7
.9
.9
.9
.9
1.0
1.0
1.0
1.1
Annual
rate
of in-
crease '
Percent
14.9
8.4
871
5.2
—
•
lf.1
10.0
Book paper
Total >
MiUion
tana
0.9
1.2
1.4
1.8
1.6
1.5
2.6
3.0
8.8
8.8
4.0
4.3
4.6
6.0
6.6
Annual
rate
of in-
crease *
Percent
5~.9
8.1
472
1L6
2.9
4.8
6.8
7.6
7.0
8.7
10.0
Coated
Million
tone
0.8
1.0
1.8
1.8
2.1
2.2
2.4
2.6
2.8
8.0
Annual
rate
of in-
crease9
Percent
—
2772
6.4
6.7
16.7
4.8
9.1
8.3
7.7
7.1
Uncoated
MiUion
tons
—
1.1
1.6
1.8
1.9
1.7
1.8
1.9
2.0
2.2
25
Annual
rate
of in-
crease2
Percent
—
7~8
2.4
1.1
5.9
5.6
5.3
10.0
13.6
Fine paper
Total
Million
tons
0.4
.6
.7
.6
.7
.9
1.2
1.4
1.7
1.9
2.0
2.1
2.2
2.4
2.6
Annual
rate
of in-
crease2
Percent
4~.6
7.0
s7i
6.2
5.9
3.1
4.0
11.8
5.8
5.0
4.8
9.1
8.3
Coaneand
industrial
paper
Total
Million
tons
1.2
1.4
1.8
1.7
2.6
2.7
8.7
4.2
4.7
4.8
6.0
6.1
6.2
6.6
6.6
Annual
rate
of in-
crease2
Percent
8~.l
5.2
8.9
.8
6.6
2.6
2.3
2.1
4.2
2.0
2.0
6.8
1.8
Sanitary and
tissue paper
Total
Mtilum
tons
0.2
X
.4
.5
.7
1.0
1.4
1.8
2.2
2.3
2.4
2.6
2.7
2.8
3.0
Annual
rate
of in-
crease2
Percent
8~.4
5.9
4.6
7.0
7.4
7.0
6.2
4.1
4.5
4.4
8.3
8.9
8.7
7.1
PROJECTED DEMAND
1970
1975
1980
1985
Year
1920
1926
1930
1936
1940
1945
1950
1955
1960
1961
1962
1963
1964
1966s
1966s
60.3
72.1
85.9
101.5
4.3
8.6
8.6
3.4
Construction
paper
Total
MiUion
tons
0.4
.6
.6
.4
.7
.9
1.4
1.6
1.4
1,4
1.4
1.4
1.5
1.6
1.6
Annual
rate
of in-
crease2
Percent
S.I
lf.8
6.2
9.2
2.7
7.1
6.7
32.0
87.7
44.4
51.7
3.8
3.8
3.8
8.1
Total board
Total «
MiUicm
tone
2.8
8.3
3.9
4.6
6.2
8.8
12.8
16.6
17.2
18.0
19.1
19.9
21.2
22.3
23.9
Annual
rate
of in-
crease *
Percent
7.6
8.4
8.4
6.2
7.8
6.9
4.9
2.0
4.6
6.1
4.2
6.6
6.2
7.2
9.7
11.0
12.5
14.3
2.9
2.5
2.6
2.7
Container board
Total
Million
tons
878
4.1
6.8
7.4
8.2
8.8
9.5
9.8
10.6
11.3
12.6
Annual
rate
of in-
crease2
*^£l*CCJll
4.4
7.2
6.0
2.1
7.8
8.0
8.2
8.2
6.6
10.6
1.2
1.8
1.4
1.5
8.7
1.6
1.6
1.4
6.3
7.8
9.5
11.4
4.7
4.4
4.0
8.7
Bending board
Total 1
Million
tons
1.0
1.1
1.4
2.8
3.1
3.9
4.4
4.5
4.9
4.8
6.2
5.4
6.7
Annual
rate
of in-
crease2
Percent
f.9
4.9
10.4
6.2
4.7
2.4
2.3
2.1
6.7
6.1
8.8
5.6
Special
food
board
Million
• tons
—
0.4
.7
1.2
1.5
1.6
1.7
1.7
1.8
2.1
2.2 -
Annual
rate
of in-
crease2
Percent
-
lf.8
11.4
4.6
6.7
672
6.9
16.7
4.8
3.8
6.0
6.3
7.8
6.8
5.6
4.7
4.4
Folding
box-
board
Million
tons
-
1.9
2.5
2.8
2.9
2.9
3.2
8.1
8.8
8.8
8.5
Annual
rate
of In-'
crease2
Percent
—
5~.6
2.8
.7
8.2
6.9
8.1
671
2.6
2.8
8.2
8.6
2.6
2.8
2.7
2.4
3.1
8.7
4.6
5.6
5.3
8.6
4.4
4.0
6.3
7.4
8.6
9.8
2.8
8.8
3.1
2.6
Building board
Total'
Million
tons
0.1
.1
.1
.2
.9
1.2
1.7
1.9
1.9
2.8
2.1
2.4
2.5
2.4
Annual
rate
of in-
crease3
Percent
-
14.9
35.0
5.9
7.2
2.2
10.5
9.5
4.3
4.2
Insulat-
ing;
board
MiUion
tons
-
0.6
.8
1.1
1.1
1.1
1.1
1.1
1.2
1.8
1.2
Annual
rate
of in-
crease2
Percent
-
6~.9
6.6
97l
8.8
Hard-
board
MiUion
tons
-
0.8
.4
.6
.8
.9
1.0
1.1
1.2
1.2
1.2
Annual
rate
of in-
crease2
Percent
--
6.9
8.4
6.9
12.5
11.1
10.0
9.1
3.7
4.7
5.9
7.1
6.7
4.9
4.7
3.8
Other board
Total
Million
tons
-
1.8
1.6
2.1
2.6
2.7
2.8
2.8
2.9
3.0
8.2
8.8
Annual
rate
of in-
crease2
Percent
-
4.2
5.6
4.4
.8
8.7
876
3.4
6.7
8.1
o
jo
2
90
m
o
5
p
00
-------
FOREST RESOURCE REPORT NO. 18
APPE
Year
1920
A v*rfv
1925
1930
1935
1940
1945
1950
1955
1960
1961
1962
1963
1964
1965s
1966*
Total
wood pulp
Total2
Million
tons
47
5.6
6.4
6.7
9.7
11.8
17.1
22.3
26.6
27.8
29.5
31.5
33.8
35.0
37.4
Annual
rate of
increase
Percent
4.0
2.7
.9
7.7
4.0
7.7
5.5
3.6
4.5
6.1
6.8
7.3
3.6
6.9
NT)TX T.— Apparent consumption of wood pulp by type, 1920- 1966
Dissolving and
special alpha1
Total
Million
tons
0.3
.5
.7
1.0
1.0
1.0
1.1
1.1
1.2
1.2
1.3
Annual
rate of
increase
>
Percent
10.8
7.0
7.4
—
10.0
9~.l
8~3
Sulfite
Total
Million
tont
2.3
2.6
2.3
2.7
2.8
3.2
3.2
3.1
3.1
3.0
3.1
3.1
3.3
3,3
Annual
rate of
increase
3
Percent
2~.5
3~3
.7
2.7
—
3~3
6~5
Sulfate
Total
Million
tons
0.4
.8
1.4
2.1
3.9
4.9
3.4
11.9
15.2
16.1
17.3
18.8
20.9
21.7
23.7
Annual
rate of
increase
s
Percent
14.9
11.8
8.4
13.2
4.7
11.4
7.2
5.0
5.9
7.5
8.7
11.2
3.8
9.2
Soda
Total
Million
tons
0.5
.5
.4
.5
.4
.6
.5
.5
.5
.4
.4
.4
.2
.2
Annual
rate of
increase
>
Percent
4.6
8.4
—
—
Groundwood
Total
Million
tons
1.8
1.9
1.9
1.5
1.8
2.0
2.5
3.0
3.6
3.5
3.7
3.8
3.9
4.3
4.3
Annual
rate of
increase
>
Percent
1.1
___
3.7
2.1
4.6
3.7
3.7
—
5.7
2.7
2.6
10.3
—
Semicbemical
Total
Million.
tons
(«)
0.1
.2
.3
.7
1.4
2.0
2.4
2.5
2.6
2.7
2.9
3.2
Annual
rate of
increase
8
Percent
— —
14.9
! '
8.4
18.5
14.9
7.4
20.1
4.2
4.0
3.8
7.4
10.3
Defibrated,
exploded,
and screenings
Total
V
Million
tons
0.3
.8
1.1
1.3
1.3
1.3
1.4
1.6
1.6
1.5
1.5
Annual
rate of
increase
a
!
Percent
__
. .' ~F
22.1
6.6
,3.4
7.7
14.3
—
1 Includes a number of highly purified types of wood pulp obtained from the sulfite and sulfate pulping processes.
2 Data prior to 1940 may not add to totals because of the inclusion in the totals of wood pulps not shown separately by type. In other
years, figures in columns may not add to totals because of rounding.
1 The average annual rate of increase for 5-year periods ending in the specified years except for the years 1961-66 when annual
changes are shown.
4 Less than 50 thousand tons.
5 Preliminary.
NOTE: Annual data on production, trade, and consumption by type of pulp are shown in the tables in appendix E.
Sources: United States Pulp Producers Association, Inc., op. ctt.; U.S. Department of Commerce, Bureau of the Census. Pvlji, paper
and board; U.S. Department of Commerce, Business and Defense Services Administration, op. cit.; and U. S. Department of Agriculture,
Forest Service.
226
-------
APPENDIX 4
Year End Paper and
Paperboard Capacity
197O—1974.
Summary by Group
PRELIMINARY
PRACTICAL MAXIMUM CAPACITY
THOUSANDS OF TONS
GRADES
TOTAL ALL GRADES PAPER
AND PAPERBOARD
TOTAL PAPER
NEWSPRINT
PRINTING, WRITING
and RELATED
Solid Bleached Brlstols
PACKAGING AND
INDUSTRIAL CONV.
TISSUE
TOTAL PAPERBOARD
UNBLEACHED KRAFT
Kraft Llnerboard
SOLID BLEACHED
SEMI-CHEMICAL
COMBINATION
TOTAL CONSTRUCTION PAPER
AND BOARD
AND WET MACHINE BOARD
1970
58,952
25,806
3,460
12,219
1,112
5,940
4,185
27i619
12,307
11,516
3,472
3,756
8,084
5,527
1971
BhHBBBHHBIHBHiiHi^^^^^^^^H
60,400
26,138
3,472
12,519
1,113
5,886
4,260
28,468
12,770
11,964
3,555
4,058
8,086
5,794
1972
_^^^H^MH^_^^H^_HMM
62,055
26,588
3,481
12,940
1,118
5,828
4,338
29,523
13,420
12,594
3,598
4,329
8,176
5,944
1973
63,47!
27,025
3,564
13,094
1,123
5,875
4,492
30,376
13,708
12,845
3,807
4,594
8,267
6,074
1974
HHBBBHHHHHHHHHIIIHHIBIWIIHItvlllB>vv
64,214
27,398
3,721
13,265
1,132
5,916,
4,497
30,699
13,798
12,904
3,993
4,616
8,291
6,117
227
-------
APPENDIX 5
THOUSANDS OF TONS
PAPER AND PAPERBOARD
TOTAL ALL GRADES
TOTAL PAPER
NEWSPRINT
PRINTING, WRITING &
RELATED
PACKAGING & IND. CONV.
TISSUE
TOTAL PAPERBOARD
UNBL. KRAFT
SOLID BLEACHED
SEMI-CHEMICAL
COMBINATION
TOTAL CONSTRUCTION
PAPER & BOARD &
WET MACHINE BOARD
» r\r"\TrmT^MO
ADDITIONS
1956 - 1971
16 YEAR
INCREASE
27,231
1^,381
Wl
\
6,319
M98
2,422
12,856
8,156
2,232
2,595
(126)
1,994
AVERAGE
ANNUAL
GROWTH
3.8%
4.8
5.2
4.5
2.1
5.4
3.8
6.6
6.4
6.6
(.7)
2.7
CAPACITY
FORECAST
END
1971
60,400
26,138
3,472
12,519
5,886
4,260
28,468
12,770
3,555
4,058
8,086
5,794
ADDITIONS 1972 - 1974
COMMITTED
3 YEAR
INCREASE
3,814
1,260
249
745
30
237
2,231
1,028
439
558
205
323
AVERAGE
ANNUAL
GROWTH
2.1%
1.6
2.3
1.9
.2
1.8
2.5
2.6
4.0
4.4
.8
1.8
COMMITTED AND
TENTATIVE
3 YEAR
INCREASE
4,187
1,413
319
774
30
291
2,451
1,028
439
778
205
323
AVERAGE
ANNUAL
GROWTH
2.3%
1.8
3.0
2.0
.2
2.2
2.8
2.6
4.0
6.0
.8
1.8
—GROWTH TRENDS IN PAPER, PAPERBOARD AND WOOD PULP CAPACITY
Source - Paper Trade Journal 11/22/71
228
-------
APPENDIX 6
PAPER AND PAPERBOARD CAPACITY BY CENSUS DIVISIONS
YEAR END 1969
YEAR END 1972
TOTAL
PAPER: &
CENSUS
DIVISIONS
NEW ENGLAND
MIDDLE ATLANTIC
SOUTH ATLANTIC
EAST SOUTH CENTRAL
WEST SOUTH CENTRAL
EAST NORTH CENTRAL
WEST NORTH CENTRAL
TOTAL WEST (PACIFIC
PLUS MOUNTAIN)
TOTAL U.S.
PAPER
'
3
3
3
2
2
5
3
25
,767
,331
,370
,714
,915
,160
592
,407
,257
PAPER -
BOARD
1,004
2,424
9,661
3,182
2,961
4,131
429
\
4,046
27,837
PAPER-
BOARD*
4
6
13
6
6
10
1
8
58
,975
,637
,580
,677
,756
,087
,630
,030
,372
WOOD
PULP
CHOUSANDS
2
1
14
7
6
3
1
8
45
,897
,510
,287
,155
,450
,212
,000
,744
PAPER
OF TON
4,129
3,713
3,432
3,009
3,201
5,475
641
3,648
,255 27,246
PAPER-
BOARD
•c\______.
s;
1,006
2,521
10,421
3,535
4,162
4,321
442
4,400
30,807
TOTAL
PAPER &
PAPER-
BOARD*
5,343
7,194
14,445
7,330
8 ,266
10,652
1,718
8,680
63,630
WOOD
PULP
1
3,096
1,746
15,299
7,822
8,009
3,513
1,062
9,224
49,770
Details may not add to totals due to rounding.
* Includes Construction and Wet Machine Board Grades.
Source - Monthly Statistical Summary
XLVIII, No. 12, December 1970
Copyright 1970 by American Petroleum Institute
229
-------
APPENDIX 7
U. S. PAPER AND BOARD PER CAPITA CONSUMPTION
CENSUS DATA
Year Lbs./Capita
1899 57,9
1904 73.7
1909 90.8
1914 108.8
1919 119.6
1924 162.6
1929 220.3
*1934 178.6
1939 243.7
1944 281.6
1947 343.4
1948 355.9
*1949 331.0
1950 381.1
1951 394.6
*1952 368.3
1953 391.6
*1954 385.0
1955 418.5
1956 432.2
*1957 410.1
*1958 401.6
1959 435.5
*1960 433.3
1961 439.0
1962 452.7
1963 462.1
1964 483.6
1965 505.6
1966 536.2
*1967 523.0
1968R 554.9
1969R 580.3
*1970P 555.6
P - Preliminary
R - Revised
* Years of economic recession (added by author)
SOURCE: American Paper Institute
230
-------
APPENDIX 8
PAPER AND ALLIED PRODUCTS INDUSTRY. PROFIT & LOSS DATA
CASH INFLOW AND SELECTED
Year Net
19U7
1948
1949
1950
1951
1952
1953
1954
1955
1956
1957
1958
1958
1959
1960
1961
1962
1963
1964
1965*
5,
5
5
6
8
7
8
8
9
10
10
10
10
11
11
12
13
14
14
16
Sales
368
833
!l77
9
9
9
9
9
9
9
,
9
9
9
9
9
9
9
9
9
377
022
688
371
492
847
686
420
256
658
824
764
525
698
050
771
224
Net Profit-
Before Taxes
932
818
547
982
1,417
1,000
1,005
970
1,206
1,283
1,020
899
987
1,204
1,135
1,120
1,212
1,215
1,312
1,488
BALANCE SHEET DATA -
YEARS - 1947 - 1970
Net Profit
After Taxes
Federal Net Profit To Depreci- Cash,
Taxes After Taxes Net Sales ation Inflow
i of Dollaj
359
314
210
424
858
563
554
493
601
626
497
440
FTC
481
585
546
535
584
581
557
619
DATA ADJUSTED BY API
1959
1960
1961
1962
1963
1964
1965
1966
1965R
1966R
1967
1968
1969
1970
SOURCE
11
11
11
12
13
13
15
17
14
16
16
18
20
21
9
9
9
9
,'
323
214
911
998
288
861
217
016
789
541
900
738
607
069
1,075
997
974
1,042
1,033
1,115
1,271
1,544
520
479
464
498
490
463 ,
FTC
517
633
r*c
573
494
338
558
559
437
450
479
604
657
521
460
- SEC - AS
506
619
587
583
628
634
754
869
Gross
Cash Flow
(Per Cent) - - - (Millions of Dollars- - .
10.7
8.5
6.5
8.8
6.9
5.7
5.4
5.6
6.1
6.1
5.0
4.5
PUBLISHED
4.7
5.2
5.0
4.7
, 4.6
4.5
5.1
5.4
FOR CONSISTENCY WITH
555
516
508
544
543
652
-SEC - AS
753
911
4.9
4.6
4.3
4.2
4.1
1.7
PUBLISHED
4.9
5.4
92
112
153
162
183
222
242
268
310
360
376
406
423
459
480
531
583
615
641
671
N.A.
N.A.
491
720
742
659
692
718
914
1,017
897
866
929
1,078
1,067
1,114
1,211
1,249
1,395
1,540
1,
1,
1,
1,
1,
1,
1,
1,
1,
1,
1,
1,
1,
1,
1,
1,
2,
N.A.
N.A.
701
144
600
222
246
211
515
643
394
306
410
663
613
649
795
830
952
159
PRE - 1959 DATA
440
459
506
555
586
602
632
676
DATA ADJUSTED FOR CONSISTENCY WITH 1967 DATA
N. ''-»»»i- c n _
.A
N.A
1,316
1»,534
1,675
1,211
: Yeni'ly data calculated
Exchange
Commission,
.-
FTC
523
645
688
492
/33
889
- SEC - AS
796
889
987
719
J . U
5.4
PUBLISHED
4.7
4.7
4.8
3.4
723
780
821
869 •
995
975
1,014
1,099
1,129
1,254
1,385
1,587
Ni - -
1,519
1,669
1,808
1,588
1,
1,
1,
1,
1,
1,
1,
515
454
478
597
619
717
902
2,220
2,039
2,314
2,496
2,080
by API based on Federal Trade Commission-Securities &
Quarterly
Financial
Report for
Manufacturing
Corporations,
1947 1570
* Estimated by API in terms of 195R-1964 definitions.
R. - 1965 and 1960 data revised by API for consistency with 1967 data.
N.A. Not available.
231
-------
APPENDIX 8. CONTD.
Cash
Dividend
146
166
146
178
200
196
203
227
259
273
270
26S
286
290
312
328
340
348
376
409
265
282
295
299
301
323
350
372
CAS
Retained
Earnings
427
328
192
380
359
241
247
252
345
384
251
195
220
329
275
255
288
286
378
461
290
234
212
245
242
329
403
539
H INFT-nw AND SELECTED BALANCE SHEET DATA -
Total
Assets
3,907
4,316
4,384
5,055
6,005
6,301
6,825
7,085
7,785
8,492
8,407
8,829
9,170
9,721
10,087
11,051
11,670
11,859
12,560
13,850
DATA
9,342
9,640
10,537
11,089
11,206
11,791
13,017
14,621
Property
Plant &
Equipment
Gross
(Millions of
N.A.
N.A.
N.A.
N.A.
N.A.
4,6'J3
5,349
5,694
6,171
7,028
7,502
7,941
FTC
8,200
8,740
9,432
10,447
11,058
11,420
12,380
13,378
Property
Plant &
Equipment
Net
1,660
1,990
2,074
2,285
2,600
2,777
3,273
3,367
3,623
4,213
4,509
4,652
- SEC - AS
4,818
5,062
5,385
5,857
6,062
6,079
6,585
7,321
Net
Worth
'
2,755
3,048
3,228
3,585
3,963
4,298
4,559
4,963
5,403
5,772
5,809
6,089
PUBLISHED
6,341
6,642
6,956
7,612
7,766
7,886
8,304
8,672
YEARS - 1947 - 1970
Long
Term Debt
404
491
500
490
625
784
803
908
1,010
1,286
1,309
1,472
1,500
1,512
1,622
1,719
1,953
1,964
1,967
2,439
Total
Capital
3,159
3,539
3,728
4,075
4,588
5,082
5,362
5,871
6,413
7,058
7,118
7,561
7,841
8,154
8,578
9,331
9,719
9,850
10,271
11,111
Net Profit
After Taxes
To Ket Worth
(Per Cent)
20.8
16.2
10.5
15.6
14.1
10.1
9.9
9.7
11.2
11.4
8.9
7.6
8.0
9.3
8.4
7.6
8.1
8.0
9.1
10.0
ADJUSTED BY API FOR CONSISTENCY WITH FRE - 1959 DATA
8,627
9,246
10,240
10,838
11,160
11,848
FTC
13 , 047
, 14,662
DATA ADJUSTED
391
396
418
430
405
493
569
289
15,645
16,809
18,794
10,679
NA - _
FTC
15,403
16,059
17,,159
18,160
4,965
5,272
5,724
. 5,907
5,899
6,280
- SEC - AS
7,053
8,131
6,367
6,624
7,225
7,327
7,398
7,731
PUBLISHED
8,165
8,710
FOR CONSISTENCY WITH
- SEC - AS
8,579
8,964
9,529
9,969
8,510
PUBLISHED
9,011
9,303
10,212
10,305
1,492
1,491
1,662
1,745
1,894
1,959
2,447
3,104
1967 DATA
N
3,736
4,199
4,267
4,822
7,859
8,115
8,887
9,071
9,299
9,690
10,612
11,814
.A.
12,747
13,502
14,479
15,127
8.7
7.8
7.0
7.4
7.3
8.4
9.2
10.5
10.4
8.8
9.6
9.7
7.0
N.A. Not Available.
232
-------
APPENDIX 9
GROUNDWOOD PULP MILLS IN THE UNITED STATES
Alabama
Arizona
Arkansas
California
Georgia
Louisiana
Maine
Michigan
Minnesota
Missouri
Kimberly-Clark Corp., Coosa Pines
International Paper Co., Mobile
National Gypsum Co., Mobile
Ponderosa Paper Products Inc., Flagstaff
Southwest Forest Industries Inc., Snowflake
International Paper Co., Pine Bluff
Kimberly-Clark Corp., Anderson
Cox Newsprint, Inc. , Augusta
Boise Southern Co., DeRidder
St. Francisville Paper Co., St. Francisville
Statler Tissue Corp., Augusta
Hearst Corp., Brunswick
St. Regis Paper Co., Bucksport
Great Northern Paper Co., East Millinocket
International Paper Co., Jay
International Paper Co., Livermore Falls
Kennebec River Pulp & Paper Co., Madison
Great Northern Paper Co., Millinocket
Oxford Paper Co., Rumford
Keyes Fibre Co., Shawmut
Escanaba Paper Co., Escanaba
Manistique Pulp & Paper Co., Manistique
Scott Paper Co., Menominee
Blandin Paper Co., Grand Rapids
Boise Cascade Corp., International Falls
Henepin Paper Co., Little Falls
St. Regis Paper Co., Sartell
Packaging Corp. of America, North Kansas City
233
-------
Groundwood, contd.
New York
Oregon
South Carolina
Tennessee
Texas
Vermont
Washington
Wisconsin
J. P. Lewis Co., Beaver Palls
International Paper Co., Corinth
St. Regis Paper Co., Deferiet
Stevens & Thompson Paper Co., Greenwich
Kimberly-Clark Corp., Niagara Falls
Publisher's Paper Co., Newberg
Publisher's Paper Co., Oregon City
Crown Ze Her bach Corp., Wanna
Crown Zellerbach Corp., West Linn
Bowaters Carolina Corp., Catawba
Bowaters Carolina Corp., Catawba
Bowaters Southern Paper Corp., Calhoun
Southland Paper Inc., Houston
Southland Paper Inc., Lufkin
United States Plywood-Champion Papers Inc., Pasadena
Standard Packaging Corp., Sheldon Springs
Crown Zellerbach Corp., Camas
Scott Paper Co., Everett
Inland Empire Paper Co., Millwood
Crown Zellerbach Corp., Port Angeles
Boise Cascade Corp., Steilacoom
Keyes Fibre Co., Wenatchee
Combined Paper Mills Inc., Combined Locks
St. Regis Paper Co., Cornell
American Can Co., Green Bay
Charmin Paper Products Co., Green Bay
Kimberly-Clark Corp., Kimberly
Kimberly-Clark Corp., Niagara
Consolidated Papers, Inc., Stevens Point
Consolidated Papers, Inc., Wisconsin Rapids
234
-------
KRAFT PULP MILLS IN THE UNITED STATES
Alabama
Arizona
Arkansas
California
Florida
Container Corp. of America, Brewton
Kimberly-Clark Corp., Coosa Pines
U. S. Plywood-Champion Papers, Inc., Courtland
Gulf States Paper Corp., Demopolis
Allied Paper Inc., Jackson
Georgia Kraft Co., Mahrt
International Paper Co., Mobile
Scott Paper Co., Mobile
American Can Co., Naheola
MacMillan Bloedel-United Inc., Pine Hill
Union Camp Corp., Prattville
Hammermill Paper Co., Selma
Gulf states Paper Corp., Tuscaloosa
Southwest Forest Industries, Inc., Snowflake
Nekoosa-Edwards Paper Co., Ashdown
International Paper Co., Camden
Georgia Pacific Corp., Crossett
Arkansas Kraft Corp., Morrilton
International Paper Co., Pine Bluff
Weyerhaeuser Co., Pine Bluff
Kimberly-Clark Corp., Anderson
Fibreboard Corp., Antioch
Crown Simpson Paper Co., Fairhaven
Georgia Pacific Corp., Samoa
Container Corp. of America, Fernandina Beach
Buckeye Cellulose Corp., Foley
Alton Box Board Co., Jacksonville
St. Regis Paper Co., Jacksonville
Hudson Pulp & Paper Corp., Palatka
International Paper Co., Panama City
St. Regis Paper Co., Pensacola
235
-------
Kraft, contd.
Georgia
Louisiana
Maine
Maryland
Michigan
Minnesota
Mississippi
Montana
Continental Can Co., Inc., Augusta
Brunswick Pulp & Paper Co., Cedar Springs
ITT Rayonier Inc., Jesup
Georgia Kraft Co., Macon
Continental Can Co., Inc., Port Wentworth
Interstate Paper Corp., Riceboro
Georgia Kraft Co., Rome
Gilman Paper Co., St. Mary's
Potlatch Forests Inc., Lewiston
Western Kraft & Corrugated Container Co.,
Hawesville
Westvaco Corp., Wickliffe
International Paper Co., Bastrop
Crown Zellerbach Corp., Bogalusa
Boise-Southern Co., DeRidder
Calcasieu Paper Inc., Elizabeth
Continental Can Co., Hodge
Pineville Kraft Corp., Pineville
Georgia Pacific Corp., Port Hudson
Crown Zellerbach Corp., St. Francisville
International Paper Co., Springhill
International Paper Co., Jay
Premoid Corp., Lincoln
Penobscot Co., Old Town
Oxford Paper Co., Rumford
Georgia Pacific Corp., Woodland
Westvaco Corp., Luke
Mead Corp., Escanaba
Packaging Corp. of America, Filer City
Scott Paper Co., Muskegon
The Northwest Paper Co., Cloquet
Boise Cascade Corp., International Falls
St. Regis Paper Co., Monticello
International Paper Co., Moss Point
International Paper Co., Natchez
International Paper Co., Vicksburg
Hoerner Waldorf Corp., Missoula
236
-------
Kraft, contd.
New Hampshire
New York
North Carolina
Brown Co., Berlin
International Paper Co., Ticonderoga
U. S. Plywood-Champion Papers, Inc., Canton
Weyerhaeuser Co., New Bern
Weyerhaeuser Co., Plymouth
Southwest Industries Corp., Riegelwood
Hoerner Waldorf Corp., Roanoke Rapids
Oklahoma
Oregon
Pennsylvania
South Carolina
Tennessee
Texas
Virginia
Weyerhaeuser Co., Craig
Western Kraft Corp., Albany
International Paper Co., Gardiner
American Can Co., Halsey
Boise Cascade Corp., St. Helens
Weyerhaeuser Co., Springfield
Georgia Pacific Corp., Toledo
Crown Zellerbach Corp., Wanna
Penritech Papers, Inc., Johnsonburg
Combined Paper Mills, Inc., Roaring Springs
P. H. Glatfelter Co., Spring Grove
Bowaters Carolina Corp., Catawba
Westvaco Corp., Charleston
South Carolina Industries, Florence
International Paper Co., Georgetown
Bowaters Southern Paper Corp., Calhoun
U. S. Plywood-Champion Papers, Inc., Cortland
Packaging Corp. of America, Counce
Southland'Paper Mills, Inc., Houston
Southland Paper Mills, Inc., Lufkin
Owens-Illinois, Inc.," Orange
U. S. Plywood-Champion, Pasadena
Eastex Corp., Silsby
International Paper Co., Texarkana
Westvaco Corp., Covington
Union Camp Corp., Franklin
Continental Can Co., Hopewell
Chesapeake Corp. of Virginia, West Point
237
-------
Kraf t, contd,
Washington Crown Zellerbach Corp., Camas
Simpson Lee Paper Co., Everett;
Weyerhaeuser Co., Everett
Loiigview Fibre Co., Longview
Weyerhaeuser Co., Longview
Crown Zellerbach Corp., Port Townsend
St. Regis Paper Co., Tacoma
Boise Cascade Corp., Wallula
Wisconsin Thilmany Pulp & Paper Co., Kaukauna
Mosinee Paper Mills, Mosinee
Nekoosa-Edwards Paper Co., Nekoosa
Consolidated Papers Inc., Wisconsin Rapids
238
-------
SODA PULP MILLS IN THE UNITED STATES
Massachusetts Oxford Paper Co., Lawrence *
New York International Paper Co., North Tonawanda
Hammermill Paper Co., Oswego
* Future uncertain.
239
-------
NEUTRAL SULFITE SEMI-CHEMICAL
PULP MILLS IN THE UNITED STATES
California
Georgia
Indiana
Kentucky
Louisiana
Maine
Michigan
Minnesota
New Hampshire
New York
North Carolina
Ohio
Oregon
South Carolina
Tennessee
Fibreboard Corp., Antioch
Great Northern Paper Co., Cedar Springs
Union Camp Corp., Savannah
Weston Paper & Manufacturing Co., Terre Haute
Wescor Corp., Hawesville
International Paper Co., Bastrop
Crown Zellerbach Corp., Bogalusa
Continental Can Co., Inc., Hodge
Olinkraft, Inc., West Monroe
Georgia Pacific Corp., Woodland
Packaging Corp. of America, Filer City
Hoerner Waldorf Corp., Ontonogon
Menasha Corp., Otsego
Hoerner Waldorf Corp., St. Paul
Brown Co., Berlin
Groveton Papers Co., Groveton
Georgia Pacific Corp., Lyons Falls
Weyerhaeuser Co., Plymouth
Mead Corp., Silva
Container Corp. of America, Circleville
Menasha Corp., North Bend
Sonoco Products Co., Hartsville
Mead Corp., Harriman
Mead Corp., Knoxville
Inland Container Corp., New Johnsonville
240
-------
NSSC, contd.
Virginia Owens-Illinois, Inc., Big Island
Westvaco Corp., Cpvington
Continental Can Co., Inc., Hopewell
Mead Corp., Lynchburg
Washington Longview Fibre Co., Longview
Weyerhaeuser Co., Longview
Boise Cascade Corp., Wallula
Wisconsin Green Bay Packaging Inc., Green Bay
Owens-Illinois Inc., Tomahawk
241
-------
Key
MgO - Magnesium
CaO - Calcium
NA - Sodium
- Ammonia
ACID SULFITE PULP MILLS IN THE UNITED STATES
Alaska
Florida
Maine
NeW Hampshire
New York
Oregon
Washington
Wisconsin
Ketchikan Pulp Co., Ketchikan
Alaska Lumber & Pulp Co., Inc., Sitka
ITT Rayonier, Inc., Fernandina
Statler Tissue Co., Augusta
Great Northern Paper Co., Millinocket
Penobscot Co., Old Town
Scott Paper Co., Winslow
Groveton Papers Co., Groveton
Finch, Pruyn & Co., Inc., Glen Falls
Coos Head Timber Co., Coos Bay
Crown Zellerbach Corp., Lebanon
Publisher's Paper Co., Newberg
Publisher's Paper Co., Oregon City
Boise Cascade Corp., Salem
Scott Paper Co., Anacortes
Georgia Pacific Corp., Bellingham
Crown Zellerbach Corp., Camas
Weyerhaeuser Co., Cosmopolis
Scott Paper Co., Everett
Weyerhaeuser Co., Everett
ITT Rayonier, Inc., Hoquiam
Weyerhaeuser Co., Longview
Inland Empire Paper Co., Millwood
ITT Rayonier, Inc., Port Angeles
Consolidated Papers Inc., Appleton
Wausau Paper Mills Co., Brokaw
American Can Co., Green Bay
Charmin Paper Products Co., Green Bay
Scott Paper Co., Marinette
Scott Paper Co., Oconto Falls
Flambeau Paper Co., Park Falls
Badger Paper Mills, Inc., Peshtigo
Nekoosa-Edwards Paper Co., Port Edward
American Can Co., Rothschild
Base
MgO
MgO
CaO
NH3
MgO
CaO
CaO
NH3
NH3
CaO
NH
MgO
MgO
NH3
NH3
CaO
MgO
MgO
NH3
CaO
Na
MgO
CaO
CaO
CaO
MgO
CaO
NH3
CaO
NH3
CaO
CaO
CaO
CaO
242
-------
DEINKING MILLS IN THE UNITED STATES
New York
Ohio
Wisconsin
Crown Zellerbach Corp., Carthage
Newton Falls Paper Mill, Inc., Newton Falls
Mead Corp., Chillicothe
U. S. Plywood-Champion Papers, Inc., Hamilton
Kimberly-Clark Corp., West Carrellton
Oxford Paper Co*, West Carrellton
Bergstrom Paper Co., Neenah
Riverside Paper Corp., Appleton
California
Illinois
New Jersey
Newsprint Deinking Mills
Garden State Paper Co., Inc., Pomona
F.S.C. Paper Co., Alsip
Garden State Papeir Co., Inc. , Garfield
243
-------
WASTE PAPEREOARD MILLS IN THE UNITED STATES
Alabama
California
Colorado
Connecticut
Delaware
Florida
Georgia
Illinois
National Gypsum Co., Anniston
Stone Container Corp., Mobile
Sonoco Products Co., Los Angeles
Continental Can Co., Los Angeles
Los Angeles Paper Box & Board Mills, Los Angeles
Kaiser Gypsum Corp., San Leandro
Container Corp. of America, Santa Clara
Georgia-Pacific Corp., Santa Clara
U. S. Gypsum Co., South Gate
Fibreboard Corp., Stockton
Fibreboard Corp., Vernon
Packaging Corp. of America, Denver
Colonial Board Co., Manchester
Rpbertson Paper Bpx Co., Inc., Montville
Federal Paper Board Co*, New Haven
Simkins Industries,, Inc., New Haven
Federal Paper Board Co., Inc., Sprague
Federal Paper Board Co., Inc., Versailles *
United Paper Products Corp., Windsor Locks
Container Corp. of America, Wilmington
Simkins Industries, Inc., Miami
Sonoco Products Co., Atlanta
Austell Box Board Corp., Austell
Alton Box Board Co., Alton
Alton Box Board Co., Carlyle
Container Corp. of America, Chicago
Container Corp. of America, Chicago
Prairie State Paper Mills, Joliet
National Biscuit Co., Marselles
* Future uncertain.
244
-------
Waste Paperboard, contd.
Illinois, contd.
Indiana
The Quaker Oats Co., Pekin
Packaging Corp. of America, Quincy
Sonoco Products Co., Rockton
Alton Box Board Co., Lafayette
Weston Paper & Manufacturing Co., Terre Haute
Packaging Corp. of America, Vincennes
Container Corp. of America, Wabash
Iowa
Kans as
Massachusetts
Packaging Corp. of America, Tama
Packaging Corp. of America, Hutchinson
Lawrence Paper Co., Lawrence
Yorktowne Paper Mills of Maine, Inc., Gardiner
Chesapeake Paperboard Co., Baltimore
Simkins Industries, Inc., Ilchester
Federal Paper Board Co., Inc., Whitehall
Continental Can Co., Inc., Haverhill
Sonoco Products Co., Holyoke
Union Box Board Co., Hyde Park
Mead Corp., Lawrence
Continental Can Co., Natick
Michigan
Minnesota
Missouri
New Hampshire
Michigan Carton Co., Battle Creek
Packaging Corp. of America, Grand Rapids
National Gypsum Co., Kalamazoo
Brown Co., Kalamazoo
Consolidated Packaging Corp., Monroe
Time Container Corp., Monroe
Union Camp Corp., Monroe
Hoerner Waldorf Corp., Otsego
B. F. Nelson Manufacturing Co., Minneapolis
Hoerner Waldorf Corp., St. Paul
U. S. Gypsum Co., North Kansas City
Hoague-Sprague Div. of USM Corp., West Hopkinton
245
-------
Waste Paperboard, contd.
New Jersey
New York
North Carolina
Ohio
Macandrews & Forbes Co., Camden
U. S. Gypsum Co., Clark Township
Whippany Paper Board Co., Inc., Clifton
Georgia Pacific Corp., Delair
National Gypsum Co., Garwood
J. F. Boyle Co., Jersey City
Newark Box Board Co., Newark
Simkins Industries Inc., Ridgefield Park *
Whippany Paper Board Co., Inc., Whippany
Sonoco Products Co., Amsterdam
J. P. Lewis Co., Brownville
Climax Manufacturing Co., Carthage
Brown Co., Castleton-on-Hudson
Columbia Corp., Chatham
Upson Co., Lockport
Upson Co., Lockport
National Gypsum Co., Newburgh
Columbia Corp., Walloomsic
U. S. Gypsum Co., Oakfield
Continental Can Co., Inc., Piermont
Warrensburg Board & Paper Corp., Warrensburg
Ravenswood Paper Board Co., Long Island City
Ft. Schyler Paper Board Corp., Utica
Carolina Paper Board Corp., Charlotte
Federal Paper Board Co., Inc., Roanoke Rapids
Crown Zellerbach Corp., Baltimore
Tecumseh Corregated Box Co., Brecksville
Mead Corp., Cincinnati
Stone Container Corp., Coshocton
Stone Container Corp., Franklin
U. S. Gypsum Co., Gypsum!
Loroco Industries, Inc., Lancaster
Chipboard, Inc., Massillon
Massillon Paper Co., Massillon
Diamond-International Corp., Massillon
Sonocd Products Co., Munroe Falls
Packaging Corp. of America, Rittman
Federal Paper Board Co., Inc., Steubenville
Toronto Paperboard Co., Toronto
* Future uncertain.
246
-------
Waste Paperboard, contd,
Oklahoma
Georgia Pacific Corp., Prybr
National Gypsum Co., Pryor
Pennsylvania
South Carolina
Tennessee
West Virginia
Wisconsin
Packaging Corp. of America, Delaware Water Gap
Brandywine Paper Corp., Downingtown
Sonoco Products Co., Downingtown
American Paper Products Co., Lancaster
Container Corp. of America, Philadelphia
Crown Paper Board Co., Philadelphia
Newman i Co., Philadelphia
Federal Paper Board Co., Inc., Reading
interstate Intercorr Corp., Reading
Whippany Paper Board Co., Inc., Riegelsville
St. Regis Paper Co., York
Yorktowne Paper Mills, Inc., York
Sonoeo Products Co., Hartsyille
Carotell Paper Board Corp., Taylors
Container Corp. of America, Chattanooga
Tennessee Paper Mills, Inc., Chattanooga
U.'S. Gypsum Co., Galena Park
Mountain Paper Products Corp., Bellows Falls
Mead Corp., Lynchburg
Federal Paper Board Co., Inc., Richmond
Federal Paper Board Co., Inc., Richmond
Halltowri Paperboard Co., tialltown
Banner Fibrebdard Co., Wellsburg
Beloit Box Board Co., Beloit
U. S. Paper 'Mills Corp., De Pere
John Strange Paper Co., Menasha
St. Regis Paper Co., Milwaukee
247
-------
BUILDING BOARDS AND RELATED PRODUCTS
Wet Machine Board
Connecticut
Illinois
Maine
Massachusetts
Michigan
Mississippi
New Hampshire
New Jersey
New York
Oklahoma
Pennsylvania
Tennessee
Washington
Colonial Board Co., Manchester
Rogers Corp., Manchester
Rogers Corp., Rogers
The Davey Co., Aurora
Colonial Board Co. (Rogers Fibre Div.), Bar Mills
Sherman & Co., Belfast
Colonial Board Co. (Rogers Fibre Div.), E. Portland
Amesbury Fibre Corp., Amesbury
George O. Jenkins, Co., Bridgewater
George O. Jenkins, Co., Bridgewater
Texon, Inc., Russell
Simplex Industries, Inc., Palmyra
Atlas Roofing Manufacturing Co., Inc., Meridian
Milton Leather Board Co., Milton
Spaulding Fibre Co., Inc., Milton
Spaulding Fibre Co., Inc., Milton
Spaulding Fibre Co., Inc., N. Rochester
Penacook Fibre Co., Penacook
The Davey Co., Jersey City
Wood Flong Corp., Hoosick Falls
Endicott-Johnson Corp., Johnson City
Big Chief Roofing Co., Ardmore
The Davey Co., Downingtown
Shyrock Bros., Downingtown
Nicolet Industries, Inc., Norristown
Colonial Board (Shufibre Div.), Covington
Fibers, Inc., Vancouver
248
-------
Building Boards and Related Products, contd.
Building Paper
Alabama
Arkansas
California
Connecticut
Florida
Georgia
Illinois
Indiana
Louisiana
GAF Corp., Mobile
Bear Brand Roofing, Inc. , Bearden
Celotex Corp. (Jim Walter Corp.), Camden
A-R Felt Mills, Inc., Little Rock
Elk Roofing Co., Stephens
Volney Felt Mills (Lloyd A. Fry Roofing Co.), Compton
Celotex Corp. (Jim Walter Corp.), Los Angeles
Johns-Manvilie Products Corp., Pittsburg
Certain-Teed Products Corp., Richmond
Anchor Paper Mills, Inc., South Gate
Tilo Co., Inc., Stratford
Volney Felt Mills (Lloyd A. Fry Roofing Co.),
Jacksonville
National Felt and Paper Corp., Miami
Volney Felt Mills (Lloyd A. Fry Roofing Co.), Miami
Great Northern Paper Co., Cedar Springs
Certain-Teed Products Corp., Savannah
GAF Corp., Savannah
Certain-Teed Products Corp., East St. Louis
GAF Corp., Joliet
Flintkote Co., Mount Carmel
Celotex Corp. (Jim Walter Corp.), Peoria
Volney Felt Mills (Lloyd A. Fry Roofing Co.), Summitt
Johns-Manvilie Products Corp., Waukegan
Philip Carey Corp., Wilmington
Volney Felt Mills (Lloyd A. Fry Roofing Co.),
Brookville
Volney Felt Mills (Lloyd A. Fry Roofing Co.),
Mishawaka
Southern Johns-Manvilie Products Corp., New Orleans
Bird & Son Inc. , Shreveport
Slidell Felt Mills, Inc., Slidell
249
-------
Building Boards and Related Products, contd.
Maryland
Missouri
New Jersey
New York
Ohio
Oklahoma
Oregon
Pennsylvania
Rhode Island
Tennessee
Congoleum Industries, Inc., North Finksburg
Tamko Asphalt Products, Inc., Joplin
OAF Corp., Kansas City
Volney Felt Mills (Lloyd A. Fry Roofing Co.),
North Kansas City
Armstrong Cork Co., Fulton
U. S. Gypsum Co., Jersey City
Philip Carey Corp., Linden
Johns-Manvilie Products Corp., Manville
Philip Carey Corp., Perth Amboy
Trepaco Chem Fibre, Trenton
GAF Corp., Gloucester
Flintkote Co., Lockport
Penn Yan Paper Products Co., Penn Yan
Atlantic Asbestos Corp., Red Hook
Certain-Teed Products Corp., Avery
Philip Carey Corp., Cincinnati
Logan-Long Co., Franklin
Nicolet Industries, Inc., Hamilton
Georgia Pacific Corp., Pryor
Allied Materials Corp., Stroud
Bird & Son Inc., Portland
Herbert Malarkey Paper Co., Portland
Volney Felt Mills (Lloyd A. Fry Roofing Co.),
Portland
Volney Felt Mills (Lloyd A. Fry Roofing Co.),
Emmaus
GAF Corp., Erie
Nicolet Industries, Inc., Norristown
Celotex Corp. (Jim Walter Corp.), Philadelphia
Certain-Teed Products Corp., York
Bird & Son Inc., Phillipsdale
Philip Carey Corp., Memphis
Volney Felt Mills (Lloyd A. Fry Roofing Co.),
Memphis
250
-------
Building Boards and Related Products, contd.
Texas
Wisconsin
GAF Corp., Dallas
Southern Johns-Manvilie Products Corp., Fort Worth
Philip Carey Corp., Houston
Volney Felt Mills (Lloyd A. Fry Roofing Co.),
Houston
Volney Felt Mills (Lloyd A. Fry Roofing Co.),
Irving
Beloit Box Board Co., Beloit
Hardboard
Arkansas
California
Florida
Georgia
Michigan
Minnesota
Mississippi
Missouri
New Jersey
New York
Oklahoma
Oregon
Superwood Corp., Little Rock
Masonite Corp., Ukiah
Abitibi Corp., Blountstown
Armstrong Cork Co., Macon
Abitibi Corp., Alpena
Nu-Ply Corp., Bemidji
Superwood Corp., Duluth
U. S. Gypsum Co., Greenville
National Gypsum Co., St. Louis
National Gypsum Co., Millington
Celotex Corp., Deposit
Weyerhaeuser Co., Craig
Evans Products Co., Corvallis
U. S. Plywood-Champion Papers, Inc., Dee
Forest Fiber Products Co., Forest Grove
Weyerhaeuser Co., Klamath Falls
U. S. Gypsum Co., Pilot Rock
251
-------
Building Boards and Related Products, contd.
Insulating Board
Alabama
Georgia
Iowa
Louisiana
Maine
Michigan
Minnesota
Mississippi
Missouri
New Jersey
Oklahoma
Oregon
Pennsylvania
Rhode Island
Texas
Virginia
National Gypsum Co., Mobile
Armstrong Cork Co., Macon
Celotex Corp., Dubuque
Celotex Corp., Marrero
National Gypsum Co., New Orleans
U. S. Gypsum Co., Libson Falls
Abitibi Corp., Alpena
Celotex Corp., L'Anse
Simpson Lee Paper Co., Vieksburg
Conwed Corp., Cloquet
Boise Cascade Corp., International Falls
U. S. Gypsum Co., Greenville
Flintkote Co., Meridian
Huebert Fiberboard Co., Boonville, Mo.
Homasote Co., Trenton
Weyerhaeuser Co., Craig
U. S. Gypsum Co., Pilot Rock
Kaiser-Gypsum Co., Inc., St. Helens
Nicolet Industries Inc., Ambler
Bird & Son Inc., Phillipsdale
Temple Industries, Inc., Diboll
U. S. Gypsum, Danville
Southern Johns-Manvilie Products Corp., Jarratt
252
*U.S. GOVERNMENT PRINTING OFFICE: 1973 514-154/253 1-3
-------
SELECTED WATER
"RESOURCES ABSTRACTS
INPUT TRANSACTION FORM
1. Report No.
4. Title
STATE-OF-THE-ART REVIEW QF PULP
AND PAPER WASTE TREATMENT
J. Accession No.
w
7. Author(s)
Dr. Harry Gehm
9. Organization
WAPORA, Inc.
6900 Wisconsin Ave. NW
Washington, D.C. 20015
12. Sponsoring Organization
15. Supplementary Notes
5. Report Date
6.
8. Performing Organization
Report No.
10. Project No.
68-01-0012
11. Contract/Grant No.
68-01-0012
13. Type of Report and
Period Covered
Environmental Protection Agency report
number, EPA-R2-73-184, April 1973.
16. Abstract
This report sets forth the state of the art in the treatment of pulp and paper mill
wastewater as it stands in 1971. In order to lay a background for the sections on
treatment, a review of both the general economic position of the industry as a whple
and the major production processes is included. Such a background is needed since
a considerable degree of loss control is practiced within the processes and water
recycling is an almost universal practice in this industry. Included also is a
review of the water quality problems which the applied treatment processes are
designed to rectify. Performance data for treatment processes and systems are
presented together with a review of the applicability of common analytical methods
to the measurement of waste characteristics and treatment effectiveness. The techniqu
used to monitor waste flowages for control purposes and as means of recording treatmen
efficiency are included. Finally, the remaining problems relative to control and
treatment of pulp and paper mill spent process waters are pointed out. Research
and development needs directed toward solving these problems are defined in the
light of such programs which are currently underway.
17a. Descriptors \
*Paper Industry, *Pulp Wastes, *Pulp and Paper Industry, Sulfite liquors, Kraft |
mill wastes, Waste Treatment, Sludge Treatment. !
I
I
17b. Identifiers j
*Pulp and Paper Waste Treatment, *Waste Characteristics, Wood wastes, Sludge disposal,'
Oxidation, Suspended solids sedimentation, Treatment costs.
17c. COWRR Field & Group Q5D
18. Availability
19. Security Class.
(Report)
20. Security Class.
(Page)
21. No. of
Pages
22. Price
Send To :
WATER RESOURCES SCIENTIFIC INFORMATION CENTER
U.S. DEPARTMENT OF THE INTERIOR
WASHINGTON, D. C. 20240
Abstractor
Harrv Gehm
{Institution MAPORA. Inc.
WRSIC102(REV JUNE 1971)
GPO 9t3.8«f
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