D
LT
REVIEW OF COLOR WASTE LOADS
AND COLOR TECHNOLOGIES FOR
BLEACHED KRAFT MILLS
PREPARED FOR THE
U.S. ENVIRONMENTAL
PROTECTION AGENCY
EFFLUENT GUIDELINES DIVISION
BY THE
EDWARD C. JORDAN CO., INC.
PORTLAND, MAINE
CONTRACT NO- 68-01--3287
DECEMBER 1978
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NOTICE
The attached document is a DRAFT REPORT. It includes technical in-
formation and recommendations submitted by the Contractor (E.G. Jordan
Company) to the United States Environmental Protection Agency ("EPA")
regarding the subject industry. It is being distributed for review and
comment only. The report is not an official EPA publication and it has
not been reviewed by the Agency.
The report, including the recommendations, will be undergoing extensive
review by EPA, Federal and State agencies, public interest organizations
and other interested groups and persons during the coming weeks. The
report, and in particular the contractor's recommended effluent limita-
tions, guidelines and standards of performance, is subject to change in
any and all respects.
The regulations to be published by EPA under Sections 301, 304 (b) and
306 of the Federal Water Pollution Control Act, as amended, will be
based to a large extent on the report and the comments received on it.
However, pursuant to Sections 301, 304 (b) and 306 of the Act, EPA will
also consider additional pertinent technical and economic information
which is developed in the course of review of this report by the public
and within EPA. Upon completion of the review process, and prior to
final promulgation of regulations, an EPA report will be issued setting
forth EPA's conclusions concerning the subject industry, effluent limit-
ations, guidelines and standards of performance applicable to such
industry. Judgments necessary to promulgation of regulations under
Sections 301, 304 (b) and 306 of the Act, of course, remain the res-
ponsibility of EPA. Subject to these limitations, EPA is making this
draft contractor's report available in order to encourage the widest
possible participation of interested persons in the decision-making
process at the earliest possible time.
The report shall have standing in any EPA proceeding or court proceeding
only to the extent that it represents the views of the Contractor who
studied the subject industry and prepared the information and recom-
mendations. It cannot be cited, referenced or represented in any res-
pect in any such proceedings as a statement of EPA's views regarding the
subject industry.
U.S. Environmental Protection Agency
Office of Water Planning and Standards
Effluent Guidelines Division
Washington, DC 20460
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ABSTRACT
In an effort to improve the information and data base on color waste
loads from bleached kraft and soda paper mills, the U.S. Environmental
Protection Agency contracted with the Edward C. Jordan Co., Inc. to
perform the following tasks:
1. Review available information and data regarding technology for the
control of color;
2. Obtain color waste load data through sampling and analysis programs
at 26 bleached kraft and soda mills;
3. Review and analyze the color measurement analytical techniques used
by some of the mills through use of a split sampling program;
4. Update the proposed Best Available Technology Economically Achiev-
able (BATEA) effluent color limitations for the bleached kraft and
soda subcategories based upon (1) identification of a color re-
duction technology representing BATEA, and (2) the color waste load
data collected during the sampling surveys, updated literature
reviews, equipment manufacturer's data, and historical mill data;
5. Calculate costs and energy requirements of application of the BATEA
technology for model mills.
This report presents the results of the work done on the above tasks
since September, 1975. Based upon the data gathered during the project
from the sources previously mentioned, BATEA effluent color discharge
for the average day conditions are presented and a color reduction
technology representing BATEA is identified.
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Three subcategories for color effluent limitations were recommended as
follows:
1. Bleached kraft (fine kraft, market kraft, and BCT kraft);
2. Dissolving kraft; and
3. Soda.
The report also recommends use of bleached pulp production for cal-
culating a mill's total color load.
The color control technology identified consists of a minimum lime
treatment process applied on the first caustic extraction effluent.
Supportive data and the data analysis for development of the average day
effluent discharge, and identifying and costing the BATEA color reduction
technology are contained in this report.
-ii-
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TABLE OF CONTENTS
Section Title Page No.
I. CONCLUSIONS AND RECOMMENDATIONS 1-1
A. SUMMARY OF CONCLUSIONS 1-1
B. SUMMARY OF RECOMMENDATIONS 1-9
1. BATEA Color Reduction Technology. . . . 1-9
2. BATEA Effluent Color Discharge
(Average Day) 1-11
II. INTRODUCTION II-l
A. PROJECT OBJECTIVES II-l
B. METHODS USED FOR.DATA COLLECTION II-l
C. METHODS USED FOR PROCESSING DATA ....... II-5
III. DATA SUMMARY AND ANALYSIS III-l
A. HISTORICAL MILL DATA VERSUS COLOR
SURVEY DATA III-3
B. DOMINANT WAVELENGTH III-9
C. SPLIT SAMPLE ANALYSIS 111-13
1. Introduction 111-13
2. Presentation of Results 111-16
3. Summary 111-36
D. RESULTS FROM MILL COLOR SURVEYS 111-39
E. COLOR LOAD BASED ON BLEACH PLANT
PRODUCTION 111-39
F. BLEACH KRAFT MILL COLOR ORIGIN 111-66
G. DATA COMPARISON 3Y SUBCATEGORY AND
WOOD SPECIE 111-99
1. Fine Kraft Subcategory. . 111-99
2. Fine and Market Kraft Mills III-101
3. Market Kraft Subcategory III-103
4. BCT Kraft Subcategory III-104
5. BCT and Market Kraft Mills III-106
6. Dissolving Kraft III-107
7. Soda III-108
8. Mills Utilizing Multiple Pulping and
Mixed Products III-109
9. Summary III-109
H. WOOD SPECIE III-112
1. Wood Specie's Effect on Color from
Bleach Plant III-112
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TABLE OF CONTENTS
(Continued)
Section Title Page No.
2. Wood Specie's Effect on Total Color at
the Secondary Treatment Influent. . . III-119
I. ANALYSIS OF BLEACHING SEQUENCES III-123
1. Rationale for Categorization III-125
2. Bleaching Factors Investigation .... III-125
a. Bleaching Sequence within
Group B III-126
b. Chlorine Application III-126
c. Hypochlorite Application III-127
3. Discussion of Sequence Variables. . . . III-127
a. Bleaching Sequence
Discussion . . III-128
b. Chlorine Application
Discussion III-129
c. Hypochlorite Application
Discussion III-132
J. INTERNAL PARAMETERS COMPARISON ....... III-135
1. Selection of Variables III-135
a. Wood Species III-136
b. Degree of Pulping ("K" or
KAPPA Numbers) III-136
c. Brown Stock Washing Efficiency
(Overall) III-136
d. White Liquor Sulfidity III-137
e. Bleaching Sequence and
Application III-137
f. Chlorine Application III-138
g. Bleach Extraction Stage ("K" or
KAPPA Numbers) III-138
h. Type of Chlorine Dioxide
Generation III-138
i. Type of Hypochlorite Used III-138
j. Final Pulp Brightness III-139
2. Data Collection III-139
3. Discussion of Relationship
Investigations III-139
a. Wood Species III-140
b. Degree of Pulping III-142
c. Brown Stock Washing III-145
d. White Liquor Sulfidity III-148
e. Bleaching Sequence III-151
f. Chlorine Application ....... III-151
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TABLE OF CONTENTS
(Continued)
Section Title Page No.
g. Bleach Plant Control (As Caustic
Stage "K" Number) III-151
h. Type of Chlorine Dioxide
Generation III-153
i. Type of Hypochlorite III-153
j. Final Pulp Brightness III-155
K. SUMMARY OF CONCLUSIONS III-155
1. Historical Mill Data III-157
2. Dominant Wavelength III-157
3. Split Sample Analysis III-157
4. Color Load Based on Bleach Plant
Production III-158
5. Bleached Kraft Mill Color Origin. . . . III-158
6. Data Comparison by Subcategory and
Wood Specie III-159
7. Wood Species III-159
8. Analysis of Bleaching Sequences .... III-160
9. Internal Parameters Comparison III-160
IV. LITERATURE AND EQUIPMENT MANUFACTURING
INFORMATION IV-1
A. LITERATURE SUMMARY IV-1
1. Coagulation and Precipitation IV-1
2. Activated Carbon Adsorption IV-26
3. Activated Alumina Adsorption IV-30
4. Resin Separation and Ion Exchange
Processes IV-34
5. Membrane Processes IV-40
6. Flotation Process IV-54
7. Ozone Treatment IV-67
8. Amine Treatment Process IV-75
9. Additional Color Reduction
Techniques IV-82
B. EQUIPMENT MANUFACTURING DATA IV-86
V. IDENTIFICATION OF THE COLOR REDUCTION TECHNOLOGY
REPRESENTING BATEA V-l
A. PRELIMINARY EVALUATION V-l
1. Minimum Lime V-l
2. Lime and Ferric Chloride V-6
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TABLE OF CONTENTS
(Continued)
Section Title Page No.
3. Lime - Magnesia Process V-7
4. Chemicals Studied to Replace Lime . . . V-7
5. Activated Carbon Adsorption V-8
6. Activated Alumina Adsorption V-9
7. Resin Separation and Ion Exchange
Processes V-9
8. Membrane Processes V-ll
9. Alum Coagulation and Recovery V-12
10. Flotation Processes V-12
11. Ozone Treatment V-13
12. Amine Treatment Process V-13
13. Other Color Reduction Techniques. . . . V-15
B. FINAL EVALUATION - IDENTIFICATION OF A TECH-
NOLOGY REPRESENTING BATEA V-15
1. Stage of Color Reduction Technology
Development V-18
2. Operational Problems Experienced. . . . V-19
3. Total Operating Cost V-20
4. Wastewater Streams Treated V-22
5. Color Reduction Efficiency V-23
C. BATEA TECHNOLOGY V-24
VI. RECOMMENDED BATEA EFFLUENT COLOR DISCHARGE -
AVERAGE DAY . . VI-1
A. LOGIC FOR PAPERGRADE SINGLE BLEACHED KRAFT
COLOR LIMITATIONS VI-4
B. RATIO: 100 PERCENT SOFTWOOD TO 100 HARD-
WOOD PULP BLEACHED VI-8
C. METHOD USED TO CALCULATE BATEA EFFLUENT
COLOR DISCHARGE (AVERAGE DAY) VI-10
D. BLEACHED KRAFT SUBCATEGORY VI-12
E. DISSOLVING KRAFT SUBCATEGORY VI-16
F. SODA SUBCATEGORY VI-21
G. SUMMARY VI-24
VII. COST FOR COLOR REDUCTION AT MODEL MILLS -
BATEA VII-1
A. BASIS FOR MINIMUM LIME TREATMENT COSTS . . . VII-2
B. MODEL MILLS VII-4
C. AVERAGE FLOWS VII-5
D. CAPITAL COSTS VII-7
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TABLE OF CONTENTS
(Continued)
Section
Title
Page No.
VIII.
IX.
X.
E. ANNUAL OPERATION COSTS VII-9
1. Operator and Maintenance Labor VII-9
2. Energy Requirements VII-10
3. Chemical Cost VII-12
F. SUMMARY VII-14
REFERENCES VIII-1
BIBLIOGRAPHY IX-1
ACKNOWLEDGEMENTS X-l
APPENDICES
I. FIELD DATA RECORDING SHEETS
II. ENVIRONMENTAL PROTECTION AGENCY EFFLUENT
GUIDELINES COLOR SURVEY FORM
III. PRODUCTION DATA SUMMARY FORM
IV. COLOR DATA SUMMARY FORM
V. SPLIT SAMPLE RESULTS FORM
VI. EPA COLOR SURVEY SUPPLEMENTAL DATA
QUESTIONNAIRE
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LIST OF TABLES
Table Title Page No.
1 COMPARISON OF MILL PRODUCTION FOR DATA YEAR
WITH COLOR SURVEY PERIOD III-4
2 DOMINANT WAVELENGTHS 111-10
3 MILL COLOR ANALYSIS PROCEDURES 111-18
4 SUMMARY COMPUTER PROGRAM RESULTS FOR SPLIT
SAMPLES 111-19
5 SUMMARY COMPUTER PROGRAM RESULTS FOR SELECTED
SPLIT SAMPLES 111-37
6 MILL LOCATION CODE FOR REPORTING COLOR SURVEY
DATA 111-40
7 COLOR BY NCASI METHOD AT ALL SAMPLE LOCATIONS 111-42
8 COLOR LOAD BY SAMPLE LOCATION (kkg/day-lbs/day) .... 111-48
9 COLOR LOAD BY SAMPLE LOCATION (kg/kkg-lbs/ton) 111-56
10 PERCENT OF TOTAL COLOR LOAD IDENTIFIED BY SOURCE. . . . 111-97
11 COLOR LOAD AT SECONDARY TREATMENT INFLUENT -
FINE KRAFT III-100
12 COLOR LOAD AT SECONDARY TREATMENT INFLUENT -
FINE AND MARKET KRAFT III-102
13 COLOR LOAD AT SECONDARY TREATMENT INFLUENT -
MARKET KRAFT III-104
14 COLOR LOAD AT SECONDARY TREATMENT INFLUENT -
BCT KRAFT III-105
15 COLOR LOAD AT SECONDARY TREATMENT INFLUENT -
BCT AND MARKET KRAFT III-107
16 COLOR LOAD AT SECONDARY TREATMENT INFLUENT -
DISSOLVING KRAFT III-108
17 COLOR LOAD AT SECONDARY TREATMENT INFLUENT - SODA . . . III-108
18 COLOR LOAD AT SECONDARY TREATMENT INFLUENT -
MULTIPLE PULPING, MIXED PRODUCTS III-109
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LIST OF TABLES
(Continued)
Table Title Page No.
v
19 GROUP B BLEACHING SEQUENCES III-124
20 DISTRIBUTION OF SPECIES PULPED III-141
21 REQUIRED COAGULANT DOSAGE IV-4
22 COST OF COAGULATION IV-5
23 TREATMENT OF KRAFT EFFLUENTS WITH DIVALENT IONS VS.
TREATMENT OF KRAFT EFFLUENTS WITH TRIVALENT IONS. . . IV-10
24 LIME TREATMENT OF KRAFT BLEACH CAUSTIC EXTRACT IN
THE PRESENCE OF METAL ION IV-12
25 REMOVAL OF BOD, COD, AND PHOSPHATE AT SELECTED
LIME-MAGNESIA LEVELS IV-14
26 ANNUAL COSTS OF LIME AND LIME-MAGNESIA TREATMENT. . . . IV-17
27 ANNUAL COSTS OF LIME AND LIME-MAGNESIA TREATMENT
(SUPPORTING DATA FOR TABLE 26) IV-18
28 SUMMARY OF EXPERIMENTAL RESULTS IV-20
29 ANALYSIS OF TREATED AND FINAL EFFLUENTS IV-27
30 REVERSE OSMOSIS OF BLEACH PLANT EFFLUENT IV-47
31 EXTRAPOLATED OPERATING COSTS IV-67
32 FINAL EFFLUENT PROPERTIES ACHIEVED AT MILL A IV-69
33 EFFLUENT PROPERTIES ACHIEVED AT MILL B IV-71
34 EFFLUENT PROPERTIES ACHIEVED AT MILL C IV-71
35 EFFLUENT PROPERTIES AT RECYCLED BOARD MILL IV-72
36 DAILY OZONE REQUIREMENTS IV-72
37 DAILY OPERATING, CAPITAL INVESTMENT, AND
TREATMENT COSTS, 1974 IV-74
38 OZONE REQUIREMENTS FOR COLOR REDUCTION OF
SELECTED PULP AND PAPER MILL EFFLUENTS IV-74
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LIST OF TABLES
(Continued)
Table Title Page No.
39 EFFLUENT IRRADIATIONS WITH LIME AND HYPOCHLORITE
TREATMENTS IV-85
40 INVENTORY OF EXTERNAL COLOR REDUCTION
TECHNOLOGIES V-2
41 COMPARISON OF COLOR REDUCTION TECHNOLOGY COSTS V-21
42 SUMMARY OF BATEA COLOR REDUCTION TECHNOLOGY
ANALYSIS V-25
43 RATIO: 100 PERCENT SOFTWOOD TO 100 PERCENT HARDWOOD
PULP BLEACHED VI-9
44 RAW WASTE BOD DETERMINATIONS VI-11
45 DETERMINATION OF AVERAGE COLOR LOAD AT SECONDARY
TREATMENT INFLUENT BLEACHED KRAFT VI-13
46 BLEACHED KRAFT PERCENT SOFTWOOD PULP VI-14
47 BATEA EFFLUENT COLOR DISCHARGE (AVERAGE DAY)
BLEACHED KRAFT VI-17
48 CALCULATED BATEA EFFLUENT COLOR DISCHARGE (AVERAGE
DAY) BLEACHED KRAFT MILLS SURVEYED VI-18
49 BATEA EFFLUENT COLOR DISCHARGE (AVERAGE DAY)
DISSOLVING KRAFT VI-22
50 SUMMARY BATEA EFFLUENT COLOR DISCHARGE (AVERAGE
DAY) VI-25
51 AVERAGE FLOW DETERMINATION VII-6
52 COST SUMMARY FOR MODEL MILLS VII-16
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LIST OF FIGURES
Figure Title Page No.
1 DOMINANT WAVELENGTH PROBABILITY CURVE
SECONDARY INFLUENT III-ll
2 DOMINANT WAVELENGTH PROBABILITY CURVE
FINAL EFFLUENT 111-12
3 SPLIT SAMPLE REGRESSION LINES, MILL 102 111-20
4 SPLIT SAMPLE REGRESSION LINES, MILL 103 111-21
5 SPLIT SAMPLE REGRESSION LINES, MILL 107 111-22
6 SPLIT SAMPLE REGRESSION LINES, MILL 108 111-23
7 SPLIT SAMPLE REGRESSION LINES, MILL 110 111-24
8 SPLIT SAMPLE REGRESSION LINES, MILL 114 111-25
9 SPLIT SAMPLE REGRESSION LINES, MILL 117 111-26
10 SPLIT SAMPLE REGRESSION LINES, MILL 119 111-27
11 SPLIT SAMPLE REGRESSION LINES, MILL 121 111-28
12 SPLIT SAMPLE REGRESSION LINES, MILL 125 111-29
13 SPLIT SAMPLE REGRESSION LINES, MILL 127 111-30
14 SPLIT SAMPLE REGRESSION LINES, MILL 134 111-31
15 SPLIT SAMPLE REGRESSION LINES, MILL 136 111-32
16 SPLIT SAMPLE REGRESSION LINES, MILL 140 111-33
17 SPLIT SAMPLE REGRESSION LINES, MILL 152 111-34
18 COLOR SOURCES, LOAD (#/DAY),* AND % OF TOTAL
COLOR MILL NUMBER 100 111-69
19 COLOR SOURCES, LOAD (///DAY),* AND % OF TOTAL
COLOR MILL NUMBER 101 111-70
20 COLOR SOURCES, LOAD (#/DAY),* AND % OF TOTAL
COLOR MILL NUMBER 102 111-71
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LIST OF FIGURES
(Continued)
Figure Title Page No.
21 COLOR SOURCES, LOAD (///DAY),* % OF TOTAL
COLOR MILL NUMBER 103 111-72
22 COLOR SOURCES, LOAD (///DAY),* % OF TOTAL
COLOR MILL NUMBER 105 111-73
23 COLOR SOURCES, LOAD (///DAY),* % OF TOTAL
COLOR MILL NUMBER 106 111-74
24 COLOR SOURCES, LOAD (///DAY),* % OF TOTAL
COLOR MILL NUMBER 107 111-75
25 COLOR SOURCES, LOAD (///DAY),* % OF TOTAL
COLOR MILL NUMBER 108 111-76
26 COLOR SOURCES, LOAD (///DAY),* % OF TOTAL
COLOR MILL NUMBER 110 111-77
27 COLOR SOURCES, LOAD (///DAY),* % OF TOTAL
COLOR MILL NUMBER 111* 111-78
28 COLOR SOURCES, LOAD (///DAY),* % OF TOTAL
COLOR MILL NUMBER 113 111-79
29 COLOR SOURCES, LOAD (///DAY),* % OF TOTAL
COLOR MILL NUMBER 114 111-80
30 COLOR SOURCES, LOAD (///DAY),* % OF TOTAL
COLOR MILL NUMBER 117 111-81
31 COLOR SOURCES, LOAD (///DAY),* % QF TOTAL
COLOR MILL NUMBER 118 111-82
32 COLOR SOURCES, LOAD (///DAY),* % OF TOTAL
COLOR MILL NUMBER 119 111-83
33 COLOR SOURCES, LOAD (///DAY),* % OF TOTAL
COLOR MILL NUMBER 121 111-84
34 COLOR SOURCES, LOAD (///DAY),* % OF TOTAL
COLOR MILL NUMBER 122 111-85
35 COLOR SOURCES, LOAD (///DAY),* % OF TOTAL
COLOR MILL NUMBER 125 111-86
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LIST OF FIGURES
(Continued)
Figure Title Page No.
36 COLOR SOURCES, LOAD (///DAY),* AND % OF TOTAL
COLOR MILL NUMBER 126 111-87
37 COLOR SOURCES, LOAD (///DAY),* AND % OF TOTAL
COLOR MILL NUMBER 127 111-88
38 COLOR SOURCES, LOAD (///DAY),* AND % OF TOTAL
COLOR MILL NUMBER 134 111-89
39 COLOR SOURCES, LOAD (///DAY),* AND % OF TOTAL
COLOR MILL NUMBER 136 111-90
40 COLOR SOURCES, LOAD (///DAY),* AND % OF TOTAL
COLOR MILL NUMBER 140 111-91
41 COLOR SOURCES, LOAD (///DAY),* AND % OF TOTAL
COLOR MILL NUMBER 152 111-92
42 COLOR SOURCES, LOAD (///DAY),* AND % OF TOTAL
COLOR MILL NUMBER 161 111-93
43 COLOR SOURCES, LOAD (///DAY),* AND % OF TOTAL
COLOR MILL NUMBER 187 111-94
44 COMPARISON OF SUBCATEGORIES III-110
45 SOFTWOOD VERSUS HARDWOOD AT THE FIRST CHLORINATION
STAGE FILTRATE III-113
46 FIRST CHLORINATION STAGE FILTRATE III-115
47 SOFTWOOD VERSUS HARDWOOD AT THE FIRST CAUSTIC
EXTRACT STAGE III-116
48 FIRST CAUSTIC EXTRACT STAGE III-117
49 SOFTWOOD VERSUS HARDWOOD FOR COMBINED FIRST
CHLORINATION AND CAUSTIC EXTRACT STAGES III-118
50 COMBINED FIRST CHLORINATION AND FIRST CAUSTIC
EXTRACT STAGES III-120
51 SECONDARY TREATMENT INFLUENT III-121
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LIST OF FIGURES
(Continued)
Figure . Title Page No.
52 SOFTWOOD VERSUS HARDWOOD AT THE SECONDARY
TREATMENT INFLUENT III-122
53 BLEACH PLANT COLOR BLEACHING GROUP A II1-130
54 BLEACH PLANT COLOR BLEACHING GROUP B III-131
55 BLEACH PLANT COLOR VS. C12 USAGE III-133
56 BLEACHING GROUP B BLEACH PLANT COLOR VS. %
HYPOCHLORITE USED III-134
57 PULPING ("K" NUMBER) VS. TOTAL COLOR III-143
58 SCREEN ROOM OR DECKER COLOR VS. PULPING K# III-144
59 BROWN STOCK WASHER LOSSES VS. SCREEN ROOM OR
DECKER COLOR (BASED ON BLEACH PLANT PRODUCTION) . . . III-146
60 SCREEN ROOM OR DECKER COLOR (HARDWOOD AND
SOFTWOOD) III-147
61 SCREEN ROOM OR DECKER COLOR VS. SULFIDITY OF
COOKING LIQUOR III-149
62 BROWN STOCK WASHER LOSSES VS. COOKING LIQUOR
SULFIDITY III-150
63 BLEACH PLANT COLOR VS. BLEACH PLANT CONTROL
(AS CAUSTIC STAGE "K" NUMBER) III-152
64 BLEACH PLANT COLOR VS. TYPE OF HYPOCHLORITE
USED BLEACHING GROUPS A&B III-154
65 FINAL BRIGHTNESS VS. BLEACH PLANT COLOR III-156
66 A PROPOSED SCHEME FOR LIME-MAGNESIA TREATMENT
OF COMBINED KRAFT EFFLUENT IV-15
67 DIAGRAMS OF DIRECT AND INDIRECT ELECTROLYTIC
PROCESSES IV-21
68 EXPERIMENTAL ELECTROLYTIC CELL IV-22
69 SCHEMATIC OF PILOT PLANT IV-25
70 SCHEMATIC DIAGRAM OF THE GRANULAR ACTIVATED
ALUMINA PROCESS FOR COLOR REMOVAL IV-33
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LIST OF FIGURES
(Continued)
Figure Title Page No.
71 ROHM AND HAAS RESIN PROCESS IV-35
72 UDDEHOLM-KAMYR RESIN PROCESS IV-37
73 DOW CHEMICAL COLOR REDUCTION MINI-PILOT PLANT
UNIT IV-39
74 ULTRAFILTRATION FLOW DIAGRAM IV-42
75 ULTRAFILTRATION PILOT PLANT FLOW DIAGRAM IV-44
76 REVERSE OSMOSIS OF SIMULATED BROWN STOCK WASH
EFFLUENT IV-48
77 PLANNED WATER RE-USE SCHEMATIC IV-50
78 TYPICAL REVERSE OSMOSIS PROCESS FOR A 400 TPD
PULP MILL IV-53
79 SCHEMATIC OF DISPERSED AIR FLOTATION
"MINI-PLANT" IV-55
80 SCHEMATIC DIAGRAM OF THE ION FLOTATION EXPERIMENTAL
APPARATUS IV-58
81 EFFECTS OF pH ON COLOR REMOVAL (FINE SPARGER) IV-59
82 EFFECTS OF pH ON COLOR REMOVAL (MEDIUM SPARGER) .... IV-60
83 PERCENT COLOR REMOVAL VS. SURFACTANT DOSAGE IV-62
84 DOSAGE VS. PERCENT FLOTATION RECOVERY IV-63
85 PERCENT FLOTATION RECOVERY VS. AIRFLOW IV-64
86 PROPOSED ION FLOTATION FOR KRAFT MILL
EFFLUENT DECOLORIZATION . . IV-66
87 OZONE GENERATION SYSTEMS IV-68
88 LABORATORY OZONIZATION APPARATUS IV-70
89 TYPICAL DECOLORIZATION TEST RESULTS WITH T-1902D
(IN SOLTROL 170) USED AS THE TREATMENT AGENT IV-78
90 PROCESS FLOW DIAGRAM FOR A TYPICAL AMINE TREATMENT
PROCESS AT A 500 ADT/DAY PULP MILL IV-80
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LIST OF FIGURES
(Continued)
Figure Title Page No.
91 DECOLORIZATION OF KRAFT DECKER EFFLUENT IN THE
PRESENCE OF SODIUM HYPOCHLORITE IV-84
92 BLEACHED KRAFT BATEA EFFLUENT COLOR
DISCHARGE (AVERAGE DAY) VI-19
93 DISSOLVING KRAFT BATEA EFFLUENT COLOR
DISCHARGE (AVERAGE DAY) VI-23
94 BATEA EFFLUENT COLOR DISCHARGE (AVERAGE DAY) VI-26
95 COST FOR TREATING BLEACH PLANT CAUSTIC EXTRACT
FILTRATE WITH MINIMUM LIME SYSTEM VII-8
96 MINIMUM LIME TREATMENT OPERATION AND MAINTENANCE. . . . VII-11
97 MINIMUM LIME TREATMENT ENERGY REQUIREMENTS VII-13
98 MINIMUM LIME TREATMENT CHEMICAL COST. . VII-15
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SECTION I
CONCLUSIONS AND RECOMMENDATIONS
A summary of the conclusions reached during the course of the color
surveys and data evaluation will be listed in this section. After the
conclusions have been summarized the specific recommendations, such as
the BATEA average day color discharge, the color reduction technology
with the cost of that technology as well as other recommendations which
have been made as a result of this study will be presented.
A. SUMMARY OF CONCLUSIONS
The conclusions which were reached as a result of the data evaluation
will be listed in the order in which they appear in the report. Ad-
ditionally, the conclusions will be presented by the particular section
in the report they appear. The following specific conclusions have been
made as a result of this study:
Section III, Data Summary and Analysis
1. A. Historical Mill Data Versus Color Survey Data
As a result of a comparison of wood species pulped, bleach
plant production and the final production between the data
year and the 3 day survey period it was concluded that the
color surveys were generally conducted during a period of
normally anticipated mill operation levels.
1-1
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2. B. Dominant Wavelength
The dominant wavelengths determined for the secondary treat-
ment system influent and the final effluent were evaluated to
check the standard solutions of potassium chloroplatinate/cobaltous
chloride as the basis for establishing the color of mill
wastewaters. The range of wavelengths encountered during the
surveys were found to be consistent with those measured for
the standard employed. This assisted in providing further
acceptance of the potassium chloroplatinate/cobaltous chloride
solution as a color standard.
3. C. Split Sample Analysis
An evaluation of the split samples for the color surveys was
performed to determine a level of confidence associated with
these split sample results. It was concluded that adjusting
the pH to 7.6 prior to analysis versus not adjusting the pH,
which some mills that split samples did not do, was one of the
primary factors inducing variances between the mill and
contractor color values on the same samples. It was determined
that comparable results could be obtained as long as the
analytical techniques employed are equivalent. A statistical
correlation, based on the split sample, was determined for the
final effluent and applied to the 26 mills' final effluent
1-2
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color concentration and then compared with the E.G. Jordan
Company's results. It was found that for the average value
only a 1 percent difference resulted (10 mg/1). Therefore, it
was concluded that normally a good comparison of results was
attained at the final effluent during the color surveys.
4. F. Bleached Kraft Mill Color Origin
An evaluation of the origin of the total color discharged to
the secondary treatment system at each of the 26 mills was
performed to determine which specific process within the mills
contributed the majority of the color in the wastewater. With
the exception of six mills (100, 111, 113, 114, 119 and 140)
the percent of the total color identified by process was 70
percent or higher.
The highest contributor to the color load in the wastewater
was determined to be the first stage caustic extraction in the
bleach plant with an average of 45 percent of the total color.
The decker filtrate or screen room in the pulping process was
the second highest contributor with an average of 24 percent
of the total color load.
5. G. Data Comparison by Subcategory and Wood Specie
The preliminary evaluation of the effect that wood specie had
on color load discharged from the 26 mills resulted in the
1-3
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conclusion that mills pulping and bleaching softwood species
had the largest color loads.
6. H. Wood Specie
Based upon the determination made in the preliminary evalu-
ation that the wood specie did effect the color load a more
detailed analysis was undertaken to determine if the proposed
color limitations should provide for a wood specie allowance.
An analysis of softwood versus hardwood use was performed on
the first chlorination and first caustic extraction stages of
bleaching, and on the total color load at the secondary
treatment system influent. In all cases the average color
load increased as the total percentage of softwood increased.
The average color load at the secondary treatment influent for
a 100 percent softwood operation was 561 Ibs/ton of pulp
bleached, while a 100 percent hardwood operation had an
average of 302 Ibs/ton (approximately a 2:1 ratio).
It was concluded from this analysis that the color limitations
should provide for a wood specie allowance.
7. I. Analysis of Bleaching Sequences
Initial evaluations of the color analysis results concluded
that significant variation in color load from bleach plant to
1-4
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bleach plant where similar species were bleached to corres-
ponding final brightnessses had taken place. In an attempt to
identify the factors causing these variations bleaching variables
were examined for their potential to influence color generation.
Two bleaching sequence groups were established: Group A,
which did not utilize any hypochlorite bleaching, and Group B
which did use hypochlorite in bleaching. Hypochlorite was
selected because its use had been reported to result in
reduced color loads from the bleach plant.
Group A bleaching sequences were evaluated with no significant
conclusions reached other than the fact that a wide variation
of color was found within the group under similar operating
and geographic conditions.
Group B bleaching sequence evaluation concluded that no one
sequence showed any trend toward lower color generation.
However, Group B did show a lower average color load per ton
than Group A (237 Ibs/ton versus 452 Ibs/ton). Therefore, it
can be concluded that bleaching sequences using hypochlorite
bleach will result in less color than sequences using no
hypochlorite, all other major parameters being similar.
The evaluation of the amount of chlorine usage per ton of
product in the first bleaching stage was performed to deter-
1-5
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mine if this had any effect upon the color load generated. No
reliable statistical relationship existed between chlorine
usage and the bleach plant effluent color.
The amount of hypochlorite used, related to color load, was
then evaluated. It was concluded that use of hypochlorite in
the bleach sequence did result in a decreased color load. The
percent hypochlorite used, however, was not shown to have any
reliable relationship to the bleach plant color. It was
concluded that too many other factors existed at the mills to
verify the expected decreased color load with increased
hypochlorite use.
8. J. Internal Parameters Comparison
In an attempt to identify the operating parameters that would
cause color load variations within the same subcategory the
following operating parameters were examined:
(1) Wood Species
(2) Degree of pulping ("K" or KAPPA numbers)
(3) Brown stock washing efficiency (overall)
(4) White liquor sulfidity
(5) Bleaching sequence and application
(6) Chlorine application
1-6
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(7) Bleach extraction stage ("K" or KAPPA numbers)
(8) Type of chlorine dioxide generation
(9) Type of hypochlorite used
(10) Final pulp brightness
Insufficient data from the color surveys on the specific wood
species (i.e., oak, gum, pine, etc.) processed was obtained to
make any conclusions on the various species. However, as was
detailed earlier the hardwood versus softwood pulp did have
enough data to perform evaluations.
Statistical analysis of the data for the degree of pulping
(cooking) and color generation showed no apparent relation-
ship. The brown stock washing effluent showed a trend toward
higher color load per ton of pulp as washer chemical losses
increased.
White liquor sulfidity was compared with screen room or decker
color load to determine if soluble organic sulfur compounds
formed during the cooking process had a significant effect on
color load. The relationship between color from the screen
room or decker and the sulfidity was not judged to be sig-
nificant.
No trend was seen between bleach plant extraction stage "K"
numbers and bleach plant color.
1-7
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An evaluation of the type of chlorine dioxide generation
process used and the bleach plant color did not show a trend
toward reduced color with any particular process.
Evaluation of calcium hypochlorite versus sodium hypochlorite
versus no hypochlorite showed, as described earlier, a sig-
nificant decrease in color load from the bleach plant if
hypochlorite was used. Additionally, it was determined that
calcium hypochlorite reduced the bleach plant color more
effectively than sodium hypochlorite.
The pulp brightness was evaluated against bleach plant color
load statistically. No reliable statistical relationship was
found, but the data did seem to indicate a trend toward higher
color load at higher brightness. More data would be needed,
however, to examine this relationship in more detail.
Based upon the conclusions (presented earlier) reached through the data
evaluation and the literature available on color reduction technologies,
specific recommendations were made on the color reduction technology
presently representing BATEA and its cost, and finally the BATEA ef-
fluent color discharge loads for the average day condition.
1-8
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B. SUMMARY OF RECOMMENDATIONS
The specific recommendations contained in this report dealt with either
the BATEA color reduction technology, or the BATEA effluent color
limitations. The recommendations for these two items will be presented
separately.
1. BATEA Color Reduction Technology
Identification of a color reduction technology representing BATEA
involved an evaluation of all of the external color reduction
technologies tested to date. The evaluation included an analysis
of the color reduction efficiency of the technology; operational
problems experienced; stage of technology development; wastewater
stream or streams treated; total cost of treatment; and an analysis
of any full scale color reduction technology in use.
As a result of this evaluation minimum lime and alum coagulation
were determined to be the top two technologies presently representing
BATEA. Minimum lime treatment of the first stage caustic extraction
was recommended as the BATEA color reduction technology because it
has a more technically advanced recovery system than the alum coagu-
lation process. However, it was also recommended that many of the
reduction technologies be closely monitored by the EPA. Some of
1-9
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these systems appeared to be applicable if technological develop-
ment could achieve the necessary refinement in the systems.
Section VII presented the cost analysis for the minimum lime
system. The costs were capital and total annual cost. The total
annual cost was the sum of the annual cost (depreciation and
interest), operator and maintenance labor, energy and chemical
costs.
A minimum lime treatment system to reduce the color of the first
caustic stage extraction effluent was sized and estimated for a 670
TPD model mill. The minimum lime treatment system for which cost
estimates were made represents an entirely independent system from
the existing mill processes and external treatment. Costs for
other model mills were developed from the cost calculated for the
670 TPD facility.
A total annual cost range with the model mills of $2.50 to $3.50
per ton of production resulted from the cost calculations. The
lower cost was for those model mills producing the greatest amount
of product (1300 TPD), while the higher cost was for the mills with
the lowest level of production (250 TPD). The cost for the 670 TPD
model mill was calculated to be $2.85 per ton of production.
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2. BATEA Effluent Color Discharge - Average Day
The calculation of the average day BATEA color discharge load was
based upon a color control process concluded to be technologically
feasible at the present time. Optimizing color reduction would
require treatment of all the color contributing wastewater streams
from a bleached kraft mill. However, as determined in Section V,
development of a color reduction technology to achieve this opti-
mized condition has not reached the stage of actual application as
a feasible process. The basis for calculating the BATEA effluent
color discharge for the average day was the minimum lime color
reduction of the first stage caustic extraction effluent. The
first stage caustic extraction effluent was determined to be the
major source of color at the majority of the 26 pulp and paper
mills surveyed. In addition to the minimum lime treatment of the.
first stage caustic extraction effluent the reduction in total
effluent color caused by reducing or eliminating the wastewater
discharge from the pulp mill decker/screen room was evaluated.
Reducing or eliminating the amount of wastewater from this phase of
the pulping operation is a BATEA internal color and as such must be
evaluated to determine the total color with this process discharge
reduced or eliminated in volume.
Two points were calculated to determine a range of values for
reductions in the color load from the decker/screen room of 50 and
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100 percent. The specific color load contributed by this process
was calculated at 24 percent of the total color load at the se-
condary treatment system influent. As described earlier this
percentage represents the average color load contributed from the
decker/screen room during the color surveys.
Because the scope of the study did not specify the evaluation of
daily color load variability over a long term (13 months or more),
there were no variability factors between annual average day and
maximum 30 day average and maximum day calculated. Therefore,
without these variability factors or an annual average day color
load the normal color limitations of maximum 30 day average and
maximum day could not be calculated. It was determined that the
average day color loads for the survey periods at the mills would
be used instead. It was, however, recommended that the EPA obtain,
or monitor and determine, the daily color load at a few of the
average bleached kraft mills surveyed in this study over at least a
13 month period. With this data the average day color load de-
termined in this study can be verified or revised, and the maximum
30 day average and maximum day variability factors can be determined
and the revised limitations calculated.
It was also recommended that the color load determinations for
bleach kraft mills be based on the bleach plant production rather
than the final production, which is presently used. Using the
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bleach plant production would eliminate the inaccuracies caused at
mills which utilize large amounts of fillers for their paper
production, purchased pulp, and/or other types of pulp in the
manufacture of their finished product. The bleach plant has been
determined to be the process responsible for over half of the total
color load at a bleach kraft mill and as such the bleach plant
production should be used to calculate color loads. The BATEA
effluent color discharge for the average day calculated in this
report were done using the bleach kraft production.
It was also recommended that color limitations should be for a
single bleached kraft subcategory (includes market kraft, fine
kraft, and BCT kraft), a dissolving kraft subcategory and a soda
subcategory. Additionally, it was determined that the wood specie
allowance would depend upon the percentage of softwood pulp bleached
by a specific facility.
The mills used to calculate the BATEA effluent color discharge
(average day) were those mills surveyed which had raw waste BOD
values at, or below the BATEA raw waste BOD load. The rationale
supporting this procedure was that mills which met the BATEA BOD
raw waste load had eliminated that portion of their color load to
the wastewater treatment system that results from insufficient
internal controls. Therefore, the color load from these mills (as
defined by the raw waste BOD) would approximate the color loads .
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from the entire industry with tighter internal controls adopted on
an industry-wide basis. The recommended BATEA effluent color
discharge (average day) for the bleached kraft dissolving kraft and
soda subcategories are as follows:
100 Percent 100 Percent
Softwood Pulp Hardwood Pulp
Kg/Kkg (Ibs/Ton) Kg/Kkg (Ibs/Ton)
Bleach Kraft
@50% Color Reduction From
The Decker/Screen Room
@100% Color Reduction From
The Decker/Screen Room
89.5 (179)
60.5 (121)
45
30
(89.5)
(60.5)
Dissolving Kraft
i
@50% Color Reduction From
The Decker/Screen Room
@100% Color Reduction From
The Decker/Screen Room
114.5 (229)
67
(134)
57 (114.5)
33.5 (67)
Soda
@50% Color Reduction From 130 (259)
The Decker/Screen Room
(§100% Color Reduction From 96 (192)
The Decker/Screen Room
65 (129.5)
48
(96)
Mills pulping a percentage of softwood pulp less than 100 percent
would have a BATEA effluent color discharge (average day) calculated
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on the basis of the actual percentage. The discharge load would be
somewhere between the 100 percent softwood and 100 percent hardwood
values listed.
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SECTION II
INTRODUCTION
A. PROJECT OBJECTIVES
i
A color sampling and analysis program was performed at 25 bleached kraft
mills and one soda mill to improve the information and data base for
substantiating or modifying the BATEA effluent color limitations listed
in the "Development Document for Advanced Notice of Proposed or Promul-
gated Rule Making for Effluent Limitations Guidelines and New Source
Performance Standards for the Bleached Kraft, Groundwood, Sulfite, Soda,
Deink, and Non-Integrated Paper Mills Segment of the Pulp, Paper, and
Paperboard Mills Point Source Category" dated August 1975.
In addition to the data collected from the 26 mill surveys, a review of
the literature pertaining to color and color reduction technologies
along with a summary of data available from manufacturers of treatment
systems for color reduction were undertaken. A color reduction tech-
nology which presently represents BATEA was identified and costs for
model mills to utilize this color reduction technology to meet BATEA
effluent color limitations were calculated.
B. METHODS USED FOR DATA COLLECTION
Process and wastewater color measurement surveys were arranged at 25
bleached kraft mills and one soda mill. Attempts were made to schedule
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these surveys during periods of normal mill operation. This was done so
that sampling and subsequent color determinations would be representative
of typical mill operations. Every attempt was made to obtain data which
accurately reflected average color levels in mill effluents and internal
process streams.
The actual sampling and testing program was preceded by a one-day meet-
ing between mill personnel and a project engineer. In this preliminary
meeting specifics of the color survey and how this program relates to
the effluent limitations work in general were discussed. The "EPA Ef-
fluent Guidelines Color Survey Form" was reviewed and completed at this
meeting (see Appendix II). The project engineer was also responsible
for establishing the sampling program within the mill prior to sampling
and testing. Specific sample points, means of sample collection,
laboratory arrangments and other details were covered during the pre-
liminary visit.
Information was also obtained pertaining to the brownstock washing,
bleaching, and any other processes which might have a significant effect
on color levels. Bleaching sequence, recycle schemes and modifications
to or deviations from conventional pulp production techniques were
recorded at this time.
The color survey team usually consisted of two persons, but in a few
mills, circumstances warranted the use of three people. Sampling was
conducted for a period of 72 consecutive hours during which three 24-
hour composite samples were obtained at each sampling point. Sampling
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points were selected to identify the main sources of color generation
within the mill. Additional sampling locations were included before and
throughout the waste treatment system for the purpose of observing how
various waste treatment systems affect color levels. In many instances,
automatic composite sampling equipment existing at normal mill sample
points was used to obtain the composite samples. In the absence of
these devices, samples were manually collected and composited. The
samples were refrigerated during the 24-hour collection period prior to
conducting the color determination.
It was the specific intent of this study to measure the true color form
present in the composite samples rather than the apparent color. Two
techniques of color determination were employed in this study: the
NCASI procedure and the EPA procedure. Both of these techniques are
discussed below. The survey team conducted color analysis at the end of
each 24-hour sampling period using equipment supplied by the contractor.
Mill personnel made laboratory space available for conducting the tests
and also supplied additional equipment and chemical solutions as needed.
The NCASI procedure involved first measuring and recording the pH of the
composite sample. The pH was then adjusted to 7.6 using sulfuric acid
or sodium hydroxide (NaOH). In some cases hydrochloric acid
used in place of sulfuric acid. Comparison tests were per-
formed which indicated no significant differences in color levels resul-
ting from pH adjustment by! HC;L instead of 112804. Sample volume increase
V
resulting from pH adjustment was limited to one percent. The pH adjusted
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sample was next filtered through a 0.8 micron filter which had been
prerinsed with distilled water. The filtered sample was transferred to
a 10 nm path length test tube and brought to room temperature. The
Bausch and Lomb Spectronic 70 spectrophotometer was set at 465 nm and
referenced to 100 percent transmittance with a distilled water blank.
The sample was then inserted into the spectrophotometer and the percent
transmittance was recorded at 465 nm. Since the spectrophotometer
calibration curve is more accurate above 25 percent transmittance, some
samples were diluted with distilled water so that the percent trans-
mittance would be approximately 25 percent or greater at 465 nm. Dilu-
tion factors were recorded on the data sheet along with percent trans-
mittance (see the Appendix for a copy of the data recording sheets). A
more detailed description of the NCASI procedure can be found in NCASI
Bulletin 253.
The EPA Procedure was based on the spectrophotometric color method
presented in Part 206A of Standard Methods for the Examination of Water
and Wastewater, 13th edition. The samples were first adjusted to a pH
of 7.6 using H^SO, or NaOH. A 0.8 micron filter was precoated with a
slurry of diatomaceous earth and distilled water. A small amount of
diatomaceous earth was also added to the pH adjusted sample and the
mixture was then filtered through the precoated filter. The filtered
sample was next transferred to a spectrophotometer test tube and brought
to room temperature. Percent transmittance was measured and recorded at
30 different wave lengths using the spectrophotometer. (See the Appendix
for the specific wave lengths used). Each wave length was referenced to
100 percent transmittance with a distilled water blank.
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In addition to collecting color data, production and process wastewater
flow data were collected for the sampling period. More specifically,
these items included:
1. Schematic flow diagram of waste treatment system and mill
processes.
2. Mill production during the 72-hour color survey.
3. Mill production and wastewater data for the year July 1, 1974
to June 30, 1975.
4. Flow measurements or estimates at each point of sample col-
lection during the 72-hour color survey.
5. Data on waste stream parameters measured on mill effluent
during the 72-hour survey.
From time to time additional information was requested from mill per-
sonnel when said information appeared to be relevant to the purposes of
this study.
C. METHODS USED FOR PROCESSING DATA
A computer program was devised to assist in calculation of the three
trichromatic coefficients (EPA procedure) and color units (NCASI pro-
II-5
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cedure) present for each day's sample points. Output was by sample and
listed mill number, mill name, mill location, sample name, and unadjusted
and adjusted pH values.
The computer printout sheets for the "EPA Color Procedure" listed measured
wave lengths in nanometers (nm) and corresponding percent transmittance
for each ordinate X, Y, and Z. Tristimulus values were calculated by
summing each ordinate and multiplying the total by the appropriate
factor. Tristimulus values X, Y, and Z were listed below their ordinate
columns, where Z was the percent luminance. Trichromatic coefficients x
and y were calculated from the tristimulus values. The location of (x
and y) on a chromaticity diagram gave dominant wavelength and excitation
purity. Hue was obtained by comparison of dominant wavelength with a
table of hue vs wave length range.
A portion of the computer printout sheets for the "NCASI Color Proce-
dure" listed the results of that computation. Percent transmittance at
465 nm is directly related to the amount of color present and, with the
proper calibration curve established from color standards for each
instrument, a measure of the color units present was obtained.
The resulting color units were then used to calculate color loads for
each day of the color survey at all the sample points.
Each mill's color survey data was assembled upon completion of the color
survey. This data consisted of the following:
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1. EPA Effluent Guidelines Color Survey Form (see Appendix II);
2. Process diagrams of both the mill and its treatment system;
3. Production Data Summary Sheet (see Appendix III);
4. Color Data Summary Sheet (included NCASI color survey pro-
cedure results with the color load in pounds per day and
pounds per ton calculated, and the EPA color survey procedure
summarized for each sample point, see Appendix IV);
5. Split Sample Results Form (see Appendix V); and
6. Computer sheet of color determinations.
The color survey data were submitted to the mill for review and comments
prior to evaluation.
Additional general operating parameters for the pulping and bleaching
processes were requested from each mill for the purpose of aiding in the
data evaluation. The form listing the 11 items of additional data re-
quested is shown in the Appendix.
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SECTION III
DATA SUMMARY AND ANALYSIS
This section presents a summary of the historical mill data collected
during the color surveys as well as the color results from the sampling
and analysis done at the 26 mills.
Initially, a comparison of the average bleach plant and final production
along with the wood species (softwood and/or hardwood) bleached for a
specific one-year period prior to the color surveys and the same average
parameters for the three-day color survey period was performed. The
purpose of the comparison was to determine if the 26 mills were opera-
ting at or near normal capacity, and bleaching their normal mix of
softwood and hardwood.
The next phase of the analysis was to check the validity of the potas-
sium chloroplatinate/cobaltous chloride solutions as an acceptable
standard for the measurement of color in pulp and paper mill effluents.
The procedure used was to evaluate the range in dominant wavelengths
determined during the color surveys.
Split samples which were undertaken at 15 of the 26 mills were then
analyzed. This evaluation was done by developing a correlation between
the mill and the Edward C. Jordan Co., Inc.'s results so that an in-
III-l
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dication of the level of confidence associated with the derived cor-
relations could be made.
The remainder of the evaluations dealt with the results of the NCASI
color procedure sampling and analysis work done at the 26 pulp and paper
mills. The results are presented by mill for each sample point on a
daily basis along with the average for each sample point. This pre-
sentation shows the results in mg/1, thousand kilograms of color per day
(thousand pounds per day), and finally in terms of kilograms of color
per thousand kilograms (pounds per ton) of bleach plant production. The
reason for calculating the color load based on the bleach plant pro-
duction and not final production are given later in this Section.
Utilizing the color load determinations, an evaluation of the origin of
color within the mill processes was undertaken to determine the major
color contributors at each mill. Block diagrams showing the color load
and percent of the total color load contributed by the process waste-
water streams sampled is shown along with the approximate sewer loca-
tions and points of discharge to the wastewater treatment system. The
percent of the total color load at each mill which was identified during
the color surveys is presented and the major sources of color are
identified.
Evaluation by subcategory, wood species, and several pulping and bleaching
parameters (i.e., kappa numbers, brightness, saltcake losses, and
sulfidity), were performed. These evaluations were done for the purpose
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of trying to establish valid relationships between color load produced
and the internal pulping and bleaching operations which may have caused
the color.
Finally, a summary of the conclusions which resulted from the eval-
uations performed is presented.
A. HISTORICAL MILL. DATA VERSUS COLOR SURVEY DATA
The initial phase of data analysis attempted to determine whether each
mill was operating at or near normal in terms of both production and
wood species pulped and bleached. The basis for this determination was
a comparison of the average daily production figures reported by each
mill on the "EPA Color Survey Form," or the data year production figures
submitted, with the average daily production levels encountered during
the three-day color survey. Table 1 shows the comparison of softwood
versus hardwood, bleach plant production, and finished production
during the two periods of concern.
Sixteen of the 26 mills surveyed were bleaching approximately the same
softwood/hardwood mix during the survey period as was bleached during
the data year reported. Mill 102 normally bleaches approximately 74
percent softwood pulp, however, it bleached only 39 percent softwood
pulp during the color survey. As discussed later in this section,
processing softwood pulp generally results in higher color levels in a
mill's wastewater; therefore, it can be theorized that the color level
found at Mill 102 was less than that normally experienced. Six other
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TABLE 1
COMPARISON OF MILL PRODUCTION FOR DATA YEAR WITH COLOR SURVEY PERIOD
Wood Specie Pulped (%)
Average Daily Bleach Plant
Production Thousand
Kilograms/Day (Tons/Day)
Average Daily Production
Thousand Kilograms/Day (Tons/Day)
Mill
Mill No. Subcategory Specie
100 Coarse & Market Pulp Softwood
Hardwood
101 Fine & Market Pulp Softwood
Hardwood
102 Miltiple Pulping Softwood
Mixed Products Hardwood
103 Fine 6, Market Pulp Softwood
Hardwood
105 Coarse Board & Tissue Softwood
Hardwood
106 Fine & Market Pulp Softwood
Hardwood
107 Fine & Market Pulp Softwood
Data
Year
55%
45%
56%
44%
74%
26%
54%
46%
57%
43%
83%
17%
100%
Color
Survey
54%
46%
40%1
56%
39%
61%
31%
69%
53%
47%
60%
40%
100%
Data Color
Year Survey Product
894.4 (985) 690.1 (760) Tissue & Toweling
Food Board
Cup Stock
Pulp Dryer
TOTAL
521.2 (574) 614.7 (677) Coated & Uncoated Paper
Market Pulp
TOTAL
522.1 (575) 561.1 (618) Bleached Board
472.2 (520) 434.0 (478) Paper
Market Pulp
TOTAL
821.7 (905) 796.3 (877) Paper
Foodboard
Tissue
Market Pulp
TOTAL
484.0 (533) 396.8 (437) Paper
Market Pulp
TOTAL
131.7 (145) 146.2 (161) Coated Paper
Uncoated Paper
Market Pulp
TOTAL
Data
Year
363.2
349.6
136.2
45.4
894.4
257.9
252.4
510.3
413.3
227.0
236.1
463.1
390.4
345.0
231.5
54.5
1021.5
238.8
280.6
519.4
173.4
20.0
45.4
238.8
(400)
(385)
(150)
(50)
(985)
(284)
(278)
(562)
(475)
(250)
(260)
(510)
(430)
(380)
(255)
(60)
(1125)
(263)
(309)
(572)
(191)
(22)
(50)
(263)
Color
Survey
296.0
448.6
82.6
827.2
408.6
136.2
544.8
466.7
210.7
263.3
474.0
386.0
347.8
221.6
76.3
1030.6
327.8
69.9
397.7
266.0
266.0
(326)
(494)
(91)
(911)
(450)
(150)
(600)
(514)
(232)
(290)
(522)
(424)
(393)
(244)
(84)
(1135)
(361)
(77)
(438)
(293)
(293)
4% of bleached pulp was reported as transition pulp during the color survey period.
-------
TABLE 1
(Continued)
Average Daily Bleach Plant
Production Thousand Average Daily Production
Wood Specie Pulped (%) Kilograms/Day (Tons/Day) Thousand Kilograms/Day (Tons/Day)
Mill No.
108
110
111
113
114
117
118
Mill
Subcategory Specie
Dissolving Softwood
Hardwood
Fine 4 Market Pulp Softwood
Hardwood
Coarse Board & Tissue Softwood
Hardwood
Coarse & Market Pulp Softwood
Hardwood
Market Pulp Softwood
Hardwood
Coarse & Market Pulp Softwood
Fine Paper Softwood
Hardwood
Data
Year
83%
17%
32%
68%
53%
47%
50%
50%
100%
27%
73%
Color
Survey
72%
28%
30%
70%
63%
37%
51%
49%
25%
75%
100%
25%
75%
Data Color
Year Survey Product
992.4 (1093) 112.3 (1225) Bleached Market Kraft
Dissolving Kraft
TOTAL
590.2 (650) 622.9 (686) Coated Paper
Market Pulp
TOTAL
601.1 (662) 483.1 (532) Bleached Paper
Unbleached Paper
Bleach Kraft Board
Bleached Coated Paper
TOTAL
1089.6 (1200) 926.2 (1020) Coated Board
Uncoated Board
Market Pulp
TOTAL
668.3 (736) 699.2 (770) Market Pulp
317.8 (350) 306.9 (338) Paper
Market Pulp
TOTAL
168.0 (185) 149.8 (165) Paper
Market Pulp
TOTAL
Data
Year
301
691
992
658
340
998
79
1
454
148
682
658
113
317
1089
668
213
104
317
158
18
177
.5
.0
.4
.3
.5
.8
.0
.8
.0
.0
.8
.3
.5
.8
.6
.3
.4
.4
.8
.9
.2
.1
(332)
(761)
(1093)
(725)
(375)
(1100)
(87)
(2)
(500)
(163)
(752)
(725)
(125)
(350)
(1200)
(736)
(235)
(115)
(350)
(175)
(20)
(195)
Color
Survey
799
312
1112
634
292
927
90
458
150
700
759
379
1138
699
194
83
277
178
178
.9
.4
.3
.7
.4
.1
.8
.5
.7
.1
.1
.5
.6
.2
.3
.5
.8
.9
.9
(881)
(344)
(1225)
(699)
(322)
(1021)
(100)
(505)
(166)
(771)
(836)
(418)
(1254)
(770)
(214)
(92)
(306)
(197)
(197)
-------
Wood Specie Pulped (%)
Mill No
119
121
122
125
126
127
134
136
Mill
Subcategory Specie
Fine Paper Softwood
Hardwood
Coarse Board & Tissue Softwood
Hardwood
Coarse & Market Pulp Softwood
Mixed Products Hardwood
Miltlple Pulping & Softwood
Mixed Products Hardwood
Market Pulp Softwood
Dissolving Softwood
Fine Paper Softwood
Hardwood
Fine Paper Softwood
Hardwood
Data
Year
40%
60%
76%
24%
69%
31%
94%
6%
100%
100%
30%
70%
63%
37%
Color
Survey
42%
58%
56%
44%
81%
19%
92%
8%
100%
100%
35%
65%
60%
40%
TABLE 1
(Continued)
Average Daily Bleach Plant
Production Thousand Average Daily Production
Kilograms/Day (Tons/Day) Thousand Kilograms/Day (Tons/Day)
Data Color
Year Survey Product
435.8 (480) 480.3 (529) Book Paper
Fine Paper
TOTAL
1042.4 (1148) 1110.5 (1223) Paperboard
Nodular Pulp
Market Pulp
TOTAL
Uncoated Board
952.5 (1049) 887.1 (977) Newsprint
Coated & Uncoated
Market Pulp
Data
Year
338
182
521
928
38
216
1182
»-512
518
259
574
TOTAL 1352
490.3 (540) 457.6 (504) Market Pulp 490
Production was Normal Production was Normal
635.6 (700) 599.3 (660) Coated Paper 871
Uncoated Paper 36
TOTAL
1162.2 (1280) 1263.0 (1391) Uncoated Paper
Uncoated Board
Coated Board
Market Pulp
TOTAL
908
691
572
25
58
1347
.7
.5
.2
.0
.1
.1
.2
.1
.5
.7
.8
.9
.3
.7
.3
.0
.0
.9
.4
.1
.5
(373)
(201)
(574)
(1022)
(42)
(238)
(1302)
(564)
(571)
(286)
(633)
(1490)
(540)
(960)
(40)
(1000)
(761)
(631)
(28)
(64)
(1484)
, Color
Survey
353.2 (389)
189.8 (209)
543
692
45
378
1116
548
770
614
1384
456
808
808
800
543
173
1518
.0
.8
.4
.6
.8
.4
.0
.7
.7
.7
.1
.1
.9
.0
.3
.2
(598)
(763)
(50)
(417)
(1230)
(604)
(848)
(677)
(1525)
(503)
(890)
(890)
(882)
(598)
(192)
(1672)
-------
TABLE 1
(Continued)
Wood Specie Pulped (%)
Mill
Mill No. Subcategory
140 Market Pulp
152 Soda
161 Coarse Board 6 Tissue
Specie
Hardwood
Softwood
Hardwood
Softwood
Hardwood
Data
Year
100%
4-5%
95-96%
52%
48%
Color
Survey
100%
4-5%
95-96%
45%
55%
Average Daily
Production
Kilograms /Day
Data
Year
285.1 (314)
219.7 (242)2
645.6 (711)
Bleach Plant
Thousand Average Daily Production
(Tons/Day) Thousand Kilograms/Day (Tons/Day)
Color
Survey Product
316.9 (349) Market Pulp
263.3 (290)2 Paper
816.3 (899) Paper
Market Pulp
TOTAL
Data
Year
285.1 (314)
555.7 (612)
637.4 (702)
127.1 (140)
764.5 (842)
Color
Survey
316.9 (349)
597.5 (658)
799.0 (880)
112.6 (124)
911.6 (1004)
187
Market Pulp
Hardwood 100%
100%
635.6 (700) 706.4 (778) Market Pulp
635.6 (700) 665.6 (733)
Bleached Soda Pulp
-------
mills also bleached less softwood than normal. Mills 101, 103, 106, 108,
121, and 161 bleached 16, 23, 23, 11, 20, and 7 percent less softwood
pulp than average, respectively.
Two mills bleached a higher proportion of softwood pulp than their daily
average for the data year. Mills 111 and 122 had an increase in percent
softwood pulp bleached of 10 and 12 percent, respectively.
The second data comparison was the bleach plant production. Analysis of
the bleach plant production during the survey period showed 20 of the 26
mills bleached within plus or minus 15 percent of their average daily
pulp production levels for the data year. Of the remaining six mills,
three bleached 23, 18, and 20 percent less than average (Mills 100, 106,
and 111, respectively), and three bleached 25, 20, and 26 percent more
pulp than their reported average daily production (Mills 122, 152, and
161, respectively).
Comparison of the average daily production levels showed 24 of the 26
mills produced finished products during the color survey within 15 per-
cent of their data year's average daily levels. Mills 161 and 106 pro-
duced 19 percent more and 23 percent less, respectively.
The preceding comparisons indicate that the color surveys at the 26
mills were generally conducted during normally anticipated mill oper-
ational levels. The relative importance of each of the three criteria,
III-8
-------
wood specie, bleach plant production, and final production, to the color
load from bleached kraft mills is discussed later in this Section.
B. DOMINANT WAVELENGTH
The utilization of standard solutions of potassium chloroplatinate/
cobaltous chloride as the basis for establishing the color of mill
wastewaters was of concern because of possible differences in dominant
wavelengths. The dominant wavelength of a solution is indicative of the
color perceived by the human eye and encompasses the range of 400 to 700
nm.
The method employed to establish dominant wavelengths was the ten or-
dinate spectrophotometric procedures presented in the 13th Edition of
Standard Methods for the Examination of Water and Wastewater. Analysis
of the color standards yielded a dominant wavelength in the range of
575-576 nm, which is equivalent to a yellow hue. Secondary treatment
influent and final effluent samples from the 26 mills surveyed were
analyzed to establish their dominant wavelengths. Secondary treatment
influent sample dominant wavelengths ranged from 572 to 580 nm and
averaged 576.5 nm. Final effluent sample dominant wavelengths ranged
from 571 to 580 nm and averaged 576.8 nm. The survey data is presented
in Table 2 and graphically depicted on the frequency of occurrence
functions presented in Figures 1 and 2.
The range in dominant wavelengths encountered during the surveys are
consistent with that measured for the standards employed, and thus
III-9
-------
TABLE 2
DOMINANT WAVELENGTHS
Dominant Wavelength Dominant Wavelength Dominant Wavelength Dominant Wavelength
Mill Secondary Final Mill Secondary Final Mill Secondary Final Mill Secondary Final
No. Influent Effluent No. Influent Effluent No. Influent Effluent No. Influent Effluent
100
575
574
577
575
577
577
108
577
578
577
576-577 119
577-578
577-577
575
576
575
571 136
575
574
577
577
577
576
576
576
101 576 110 578 578 121 576 577 140 577 577
576 578 577 576 577 577 577
577 578 577 575 575 576 577
M
M
V 102 577 111 576 576 122 579 577 152 576 576
o 576 576 577 578 579 576 576
577 577 578 580 577 574 576
103 576 577 113 576 578 125 579 578 161
579 580 577 579 579 578
578 578 579 579 579 577
105 579 580 114 576 579 126 580 580 187 578 579
577 579 576 578 580 580 578 579
578 577 579 579 580 578 579
106 573 579 117 578 127 578 579
577 579 576 578 577
577 579 576 578 578
107 579 118 574 578 134 575 575
579 572 572 576 575
575 576 575 575
-------
FIGURE I
DOMINANT WAVELENGTH PROBABILITY CURVE
SECONDARY INFLUENT
980
579
578
SECONDARY INFLUENT
E
c
„
I
h-
O
z
UJ
O
O
577
576
575
574
573
572
J_
99.99 99.9 99 8 99 98 95 90 80 7O 6O 5O 4O 30 20
PERCENT GREATER
10
I O.5 O.2 O.I O.O5
O.OI
-------
FIGURE: 2
DOMINANT WAVELENGTH PROBABILITY CURVE
FINAL EFFLUENT
580r
FINAL EFFLUENT
70 60 50 40 30
PERCENT .GREATER
0.05 0.01
-------
further leads to the acceptance of potassium chloroplatinate/cobaltous
chloride solutions as an acceptable standard for the measurement of
color in mill wastewater.
C. SPLIT SAMPLE ANALYSIS
1. Introduction
Color measurement analytical techniques employed at the mills surveyed
were reviewed and analyzed. For those mills which split samples for
independent color determinations, correlations between mill and con-
tractor results were to be established including an indication of the
level of confidence associated with the derived correlations.
The analytical determination of color is based on the measurement of
light transmittance through a sample and comparison of the results
obtained with light transmittance through color standards of various
concentrations measured under similar conditions. Color concentration
ideally follows Beer's law which states that the logarithm of the trans-
mittance of a monochromatic light beam through a sample is directly
proportional to the concentration of the absorbing substance in the
sample and to the path length of the light through the sample. Solu-
tions of potassium chloroplatinate, hued with cobaltous chloride, are
used as color standards and the monochromatic light wavelength employed
in the color determination is 465 nm. This wavelength is employed
because the spectral transmittance curves of standard color solutions
111-13
-------
and kraft mill wastewater samples parallel each other in this region of
the visible spectrum. Under normal laboratory conditions, standard
solutions up to approximately 2,500 mg/1 (color units) can be prepared.
Above this concentration the standard solution becomes supersaturated
and thus cannot be used. Theoretically, color concentrations up to
approximately 8,000 mg/1 can be measured with spectrophotometric equip-
ment. However, usual practice assumes Beer's Law does not hold true at
transmittances less than 20-25 percent (color concentrations greater
than approximately 2,500 mg/1) and, as a result, sample dilutions with
deionized water were made to bring the color of the sample within the
range of the standards (1). The color of the diluted sample is deter-
mined and multiplication by the appropriate dilution factor results in
the actual sample color concentration (2).
Many factors affect both the accuracy and precision with which the true
color of a sample may be analytically determined. Two primary influencing
factors include the pH of the sample and the presence of turbidity in
the sample. Color varies with pH and, in general, increases with in-
creasing pH. The pH of samples must therefore be adjusted to a discrete
value prior to analysis and the value that has been selected is a pH=7.6.
Dilution of a sample with acid or base, as required for pH adjustment,
must not induce a volumetric change greater than one percent. The
method of turbidity removal employed also has a significant effect on
the resultant color value. Two principal techniques are used for tur-
bidity removal: centrifugation or filtration. Centrifugation has been
found to be capable of removing turbidity but not true color. In general,
111-14
-------
however, this technique is not employed because turbidity removal varies
with the size and speed of the centrifuge employed. In addition, par-
ticles less dense than the suspending medium tend to float or remain in
solution during centrifugation thus yielding incomplete removal and
subsequent erroneous results. Filtration of samples through 0.45 micron
filter paper was found by NCASI to be unacceptable because the fil-
trate's color was dependent on the volume of sample subjected to fil-
tration. Use of 0.8 micron filter paper, on the other hand, was found
to alleviate the above and still yield a turbidity-free filtrate. The
success of turbidity removal by filtration is still, however, greatly
dependent upon the analyst's technique. During the filtration of a
sample, a rapid reduction in the rate of sample throughput indicates
that filter plugging is occurring. If the above is noted, filtration
should be stopped immediately since further filtration may result in the
removal of the true color bodies and thus the overall color of the
filtrate.
Other factors affecting the precision and accuracy of color determin-
ations are oriented mainly toward the analytical instrument employed.
Certain of these factors include:
1. use of instrument allowing wide incident bandwidths;
2. voltage fluctuations;
3. stray radiation;
4. varied scattering and reflection losses of the incident light
beam;
5. changes in light path length;
111-15
-------
6. variation in optical properties of absorption cells;
7. cleanliness of absorption cells; and
8. loss of wavelength calibration through improper or incon-
sistent operation of the analytical instrument.
To provide a basis for comparison of results sample pretreatment and
analysis procedures developed by the NCASI were used. These are pre-
sented in NCASI Technical Bulletin No. 253 ("An Investigation of Improved
Procedures for Measurement of Mill Effluent and Receiving Water Color,"
dated December 1971). A Bausch and Lomb Spectronic 70, with an 8 nm
spectral bandwidth, was the spectrophotometer used for the measurement
of light transmittance through both the color standards and the mill
wastewater samples in question.
2. Presentation of Results
The process and wastewater streams subjected to color analysis in this
survey included such items as decker filtrate, first stage chlorination
effluent, first stage caustic extract effluent, primary clarifier in-
fluent/effluent, acid sewer, secondary influent, and final effluent.
The color concentration in these various streams ranged from approx-
imately 50 mg/1 to in excess of 18,000 mg/1.
All samples at each mill were collected in sufficient volume so that
color determinations could be made by the Edward C. Jordan Co., Inc. and
the mill's personnel. Seven of the 15 mills that analyzed samples used
111-16
-------
the NCASI method of color determination or some modification thereof.
The remaining 8 mills that analyzed samples used various alternate color
determination procedures including Standard Methods, color meters, and
visual comparisons. Sample pH was not adjusted to 7.6 at 4 of the 8
mills using the alternative procedures. Table 3 lists the mills that
conducted color analyses and the procedures used.
A computer program was used to calculate a 99.99% confidence least
squares regression function which compared mill and Edward C. Jordan
Co., Inc. analytical results. The program output listed for each mill
surveyed the slope and intercept of the regression line and the data
2
correlation coefficient, R . Perfect agreement is shown by a line
2
through the origin with a slope of 1.000 and an R =1.000. A summary of
the computer analysis is presented in Table 4.
Data correlations for each mill are presented in Figures 3 through 17.
The dashed line labeled "All Samples" on each figure represents the re-
gression line derived by incorporating the data points from all 15
mills. The solid line labeled "Mill N" represents the regression line
derived from the data specific to "Mill N" only. For purposes of
clarity, all data points are not always shown.
As can be seen from Table 4, the "All Samples Regression Line" reflects
variations from perfect data agreement resulting from the incorporation
of data derived from "non-standard" analysis procedures. For this
reason, certain data were deleted and new regression lines calculated.
111-17
-------
TABLE 3
MILL COLOR ANALYSIS PROCEDURES
Mill No. Procedure
102 Sample centrifuged and pH adjusted to 7.0, color measured
with a Hach Meter
103 Hach test kit, no pH adjustment
107 No pH adjustment, sample centrifuged and color estab-
lished by comparison with color standards in Nessler
tubes
108 Standard Methods
110 Modification of NCASI, using Reeve Angle 934 AH Filter
114 NCASI, Spectronic 20 used for determining color
117 Oregon DEQ procedure
119 NCASI, 2 Whatman No. 5 filter papers used for filtering,
and readings were done at 455 nm.
121 pH not adjusted, color measured with a Beckman DB
Spectrophotometer at 465 nm and compared to potassium
chloroplatinate standard
125 NCASI, Beckman Model B Spectrophotometer used to deter-
mine color
127 NCASI
134 NCASI
136 NCASI
140 Standard Methods, pH adjusted to 7.6, Hach dr/2 Spectro-
photometer is used to do readings
152 Standard Methods, true color
111-18
-------
TABLE 4
SUMMARY COMPUTER PROGRAM RESULTS FOR SPLIT SAMPLES
Mill No.
102
103
107
108
110
114
117
119
121
125
127
134
136
140
152
All Samples Re-
gression Line
Arithmetic Mean
7 NCASI Mills
Arithmetic Mean
8 Non-NCASI Mills
Ideal Regression
Line
Slope
0.993
0.716
1.02
0.986
0.790
1.17
0.394
0.991
0.873
1.01
1.02
0.481
0.909
1.08
0.810
0.896
0.910
0.859
1.00
Intercept
308
1,610
-86
125
97
-146
420
6
96
196
219
377
719
1
62
293
210
317
0
R
0.832
0.303
0.981
0.988
0.998
0.986
0.426
0.977
0.988
0.994
0.862
0.977
0.883
0.335
0.906
0.884
0.954
0.720
1.00
111-19
-------
FIGURE 3
SPLIT SAMPLE REGRESSION LINES, MILL IO2
ISOOi—
en
E
_l 1000
CO
2
o
o:
u
h-
LJ
Q
cr 500
o
_i
o
o
MILL 102
Y = 0.993X + 308
R2 = 0.832
ALL SAMPLES
Y=0.896X + 293
R2 = 0.884
I I
I I I I II
I
till
500 1000
COLOR DETERMINATION BY CONTRACTOR mg/l
1500
-------
FIGURE 4
SPLIT SAMPLE REGRESSION LINES, MILL IO3
7500
E 5QQ.Q
m
2
O
tt:
UJ 250Q
h-
LU
Q
ft
O
_J
O
O
MILL 103
,Y= 0.7I6X + 1610
R2= 0.303
SAMPLES
Y= 0.896X 293
R2= 0.884
I
i I
25QO 50QO
COLOR DETERMINATION BY CONTRACTOR mg/l
7500
-------
FIGURE 5
SPLIT SAMPLE REGRESSION LINES, MILL IO7
7500 I—
5000
m
2
O
o:
HJ
I-
UJ
Q
CK
O
_l
O
o
2500
MILL 107
Y= I.O2X-86
R*= 0.981 //
ALL SAMPLES
Y= 0.896X-I-293
R2= 0.884
2500 5000
COLOR DETERMINATION BY CONTRACTOR mg/l
7500
-------
FIGURE S
SPLIT SAMPLE REGRESSION LINES, MILL IO8
1500 i—
1000 —
CD
h-
<
5
o:
UJ
I-
UJ
o
tr
a
_i
o
o
Y= O.896X+ 293
R2=0.884
500 —
500 1000
COLOR DETERMINATION BX CONTRACTOR mg/l
I5OO
-------
FIGURE 7
SPLIT SAMPLE REGRESSION LINES, MILL MO
7500 i—
^5000
>
CD
\-
<
or
2500
LU
Q
cc
O
_l
O
O
ALL
Y= 0.896X-
R = 0.884
MILL 110
Y = O.790X + 97
R2= 0.998
25OO 5000
COLOR DETERMINATION BY CONTRACTOR mg/l
7500
-------
FIGURE 8
SPLIT SAMPLE REGRESSION LINES, MILL
7500r—
en
5000
I-
<
5
QC
UJ 2500
Ct
O
_l
O
O
MILL 114
Y= I.I7X-I46
R2= 0. 986
ALL SAMPLES
Y= 0.896X^293
R2= 0. 884
j i I
2500 5000
COLOR DETERMINATION BY CONTRACTOR mg/l
7500
-------
FIGURE 9
SPLIT SAMPLE REGRESSION LINES, MILL 117
15000 i—
jjfioooo
00
o
o:
UJ 5000
h-
UJ
Q
O
O
0
ALL SAMPLES
Y= 0. 896X+293
R2= 0.884
MILL 117
Y = O.394 + 42O
R2= O.426
I
500O IOOOO
COLOR DETERMINATION BY CONTRACTOR mg/l
15000
-------
FIGURE 10
BPLIT SAMPLE REGRESSION LINES, MILL 119
3000 —
m
20OO —
a:
u
h-
LJ
Q
o:
o
o
o
1000 —
MILL 119
Y| 0.99IX-I-6
R = 0.977
j i
o.
Y= 0.896X+293
R= 0.884
1000 2000 30OO
(COLOR DETERMINATION BY CONTRACTOR mg/l
-------
FIGURE II
SPLIT SAMPLE REGRESSION LINES, MILL 121
7500 r—
5000
>-
CD
o
<
2
i
o:
2500
UJ
Q
O
o
ALL SAMPLES
Y=0. 896X + 293
R2=0.884
MILL 121
Y = 0. 873X + 96
R2= 0.988
250O 5000
COLOR DETERMINATION BY CONTRACTOR
I
7500
-------
FIGURE 12
SPLIT SAMPLE REGRESSION LINES, MILL 125
15000 r—
10000
m
z
o
h-
z
I
o:
5000
UJ
Q
o:
o
_i
o
o
I i
MILL 125
Y= I.
R2= 0.994
ALL SAMPLES
= 0.896X+293
R= 0.884
1
I
5000 10000
COLOR DETERMINATION BY CONTRACTOR mg/l
I50OO
-------
FIGURE 13
SPLIT SAMPLE REGRESSION LINES, MILL 127
15000
glOOOO
>-
CO
o:
5000
u
o
o:
O
_i
O
o
MILL 127
Y= I.02X+
R =0.862
ALL SAMPLES
Y= 0.896+293
R2= 0.884
5000 IOOOO
COLOR DETERMINATION BY CONTRACTOR mg/l
15000
-------
FIGURE 14
SPLIT SAMPLE REGRESSION LINES, MILL 134
15000 I—
10000
>-
ffl
or
5000
UJ
Q
££
O
_l
O
O
ALL SAMPLES
Y= 0. 896X+293
R2= 0.884
MILL 134
Y=0. 48IX+377
R*= 0.977
5000 10000
COLOR DETERMINATION BY CONTRACTOR mg/l
I500O
-------
FIGURE 15
SPLIT SAMPLE REGRESSION LINES, MILL 136
15000 i—
5" 10000
00
2
o
o:
UJ 5000
H
UJ
Q
<£
O
_l
O
o
MILL 136
Y=0.909X +719
R2= 0. 883
ALL SAMPLES
Y = 0.896X4-293
R2= 0.884
5000 10000
COLOR DETERMINATION BY CONTRACTOR mg/l
15000
-------
FIGURE 16
SPLIT SAMPLE REGRESSION LINES, MILL I4O
3000
o>
E
>-
CD
o
<
cc
UJ
h-
UJ
Q
cr
o
2000
O 1000
MILL 140
Y= I.08X+I
R2= 0. 335
ALL SAMPLES
Y=0.896+293
R2= 0.884
i i i i i
i i i
IOOO 2OOO 3OOO
JC.OLOR DETERMINATION Y CONTRACTOR mg/l
-------
FIGURE 17
SPLIT SAMPLE REGRESSION LINES, MILL 152
7500.—
5000
5
m
z
o
z
i
o:
2500
UJ
Q
CE
o
_)
o
o
ALL SAMPLES
Y=0. 896X-I-293
R2= 0. 884
MILL 152
Y = 0.8IOX+62
R2= 0. 906
, I
i i
2500 5000
COLOR DETERMINATION BY CONTRACTOR mg/l
7500
-------
For example, pH adjustment was previously noted as having an effect on
the color of a sample. As a result, a new regression analysis was per-
formed using the data from all samples that had been subjected to a pH
adjustment to 7.6. The outcome is presented below:
Samples at all pH values
Y = 0.896X + 293 with R2 = 0.884
Samples at pH = 7.6 only
Y = 0.969X + 52 with R2 = 0.864
where Y = color as measured by mill personnel (in mg/1)
X = color as measured by contractor (in mg/1).
As can be seen from the above, pH adjustment to 7.6 had a significant
impact on the correlation of mill to contractor measurement with the
slope of the line more closely approximating unity and the intercept
approaching zero. Adjustment of pH, however, had a relatively minor
2
effect on the data correlation coefficient, R , adjusting it from 0.884
to 0.864.
Another variable of concern was the utilization of color data above
2,500 mg/1 resulting from either taking transmittance readings of less
than 25 percent or from applying appropriate multiplication factors to
samples that had been diluted with deionized water prior to measuring
light transmittance. Linear regression analyses were thus undertaken
encompassing data between zero and 2,500 mg/1 color with the results as
follows:
111-35
-------
2
Slope Intercept R
Using NCASI Procedure
Samples at all color con-
centrations 0.910 210 0.954
Samples with less than
2,500 mg/1 in color 0.863 148 0.869
Using Non-NCASI Procedure
Samples at all color con-
centrations 0.859 317 0.720
Samples with less than
2,500 mg/1 color 0.938 196 0.761
From the above, the only obvious consistent alteration induced by lim-
iting the color concentration used in the analysis is a decrease in the
intercepts of the linear functions. Depending on the procedure employed
for color measurement by each mill, both the slope of the functions and
the data correlation coefficients were subject to either positive or
negative changes. The above data are presented in Table 5.
3. Summary
The accuracy and precision of color measurements are known to be a
function of the analytical techniques and equipment employed. To es-
tablish correlations between results obtained by mill personnel and the
contractor, various statistical analyses were performed.
Adjusting a sample's pH to 7.6 prior to color measurement was found to
be one of the primary factors inducing variances between mill and con-
tractor color values on the same sample. If mill personnel adjusted the
111-36
-------
TABLE 5
SUMMARY COMPUTER PROGRAM RESULTS FOR SELECTED SPLIT SAMPLES
Mill No.
102
103
107
108
110
114
117
119
121
125
127
134
136
140
152
Sample Regression
Line
7 NCASI Mills
8 Non-NCASI Mills
Ideal Regression
Slope
0.993
0.718
1.05
0.963
0.668
1.01
1.04
. 0.774
0.912
0.793
1.08
0.890
0.823
0.925
0.897
0.969
0.863
0.938
1.00
Intercept
308
888
-99
144
212
30
57
163
88
415
-42
76
181
160
22
52
148
196
0
R
0.832
0.577
0.845
0.851
0.936
0.993
0.925
0.664
0.993
0.750
0.950
0.858
0.931
0.285
0.776
0.864
0.869
0.761
1.00
Remarks
Color <_ 2,500
Color <_ 2,500
Color <_ 2,500
Color <_ 2,500
Color <_ 2,500
Color <_ 2,500
Color <_ 2,500
Color <_ 2,500
Color <_ 2,500
Color <_ 2,500
Color <_ 2,500
Color <_ 2,500
Color <_ 2,500
Color <_ 2,500
Color <_ 2,500
Calculated without
mills that did not
adjust pH included
Line
111-37
-------
pH of their portion of a sample to the above value, the following cor-
relation prevailed:
Y = 0.969 X + 52 with R2 = 0.864
where X = color as measured by the Edward C. Jordan Co., Inc.
(mg/1)
Y = color as measured by mill personnel (mg/1)
2
R = data correlation coefficient
Twenty-six (26) mills were surveyed during the course of this study.
For comparative purposes, the above correlation has been applied to the
final effluent color concentrations encountered at these 26 mills and is
presented below:
Color, mg/1
Minimum Average Maximum
Determined by the Edward C. Jordan Co.,
Inc. 310 1,330 2,260
Calculated Mill Value 350 1,340 2,240
Difference +40 +10 -20
Percent Difference +13% +1% -1%
The resulting 10 mg/1 difference between the mill and the Edward C. Jordan
Co., Inc. color concentration at average conditions indicates the nor-
mally good comparison of results attained at the final effluent during the
color surveys.
In summary, comparable results can be obtained independently as long as
the analytical techniques employed are equivalent.
111-38
-------
D. RESULTS FROM MILL COLOR SURVEYS
The results of the NCASI procedure for determining color are presented
on Table 7. The color, in mg/1, at each sample location for each day of
the color survey at all the mills, and the average color concentration
at the sample locations are presented. The use of mg/1 in place of
color units was done in previous EPA color determinations, and to
provide a basis for comparing the results of that earlier work with the
results from this study the procedure was also followed in this report.
To help simplify the data presentation it was necessary to code each
sample location with a letter or footnote number. Table 6 shows the
identification for each letter code used on Tables 7, 8, and 9. Foot-
note numbers used to identify sample locations are given at the bottom
of the page upon which they appear.
The NCASI color procedure color results, in mg/1, were then used to
determine the color load in kilograms per day (pounds per day) at each
sample location. Table 8 shows the results of these calculations. The
same letter code was utilized for color load presentation at each sample
location (see Table 6).
E. COLOR LOAD BASED ON BLEACH PLANT PRODUCTION
Environmental Protection Agency limitations, presently proposed for
color, use the mill's finished production for determining the allowable
color load kg/kkg (Ibs/ton) for each subcategory. During the project
comments were made by mill personnel that this procedure should be
revised from use of the finished product tonnage to the pulp or bleach
111-39
-------
TABLE 6
MILL LOCATION
CODE FOR REPORTING COLOR SURVEY DATA
Code Mill Location Sampled
D Decker Filtrate (Hardwood and Softwood)
DS Decker Filtrate (Softwood)
DH Decker Filtrate (Hardwood)
S Screen Room Sewer
B Bleach Plant Sewer (Hardwood and Softwood)
BA Bleach Plant Acid Sewer
BC Bleach Plant Caustic Sewer
C First Stage Cl- Filtrate (Hardwood and Softwood)
CS First Stage Cl_ Filtrate (Softwood)
CH First Stage Cl_ Filtrate (Hardwood)
E First Stage Caustic Extract Filtrate (Hardwood and Softwood)
ES First Stage Caustic Extract Filtrate (Softwood)
EH First Stage Caustic Extract Filtrate (Hardwood)
E- Second Stage Caustic Extract Filtrate
A Acid Sewer
AS Acid Sewer (Softwood)
AH Acid Sewer (Hardwood)
Al Alkaline Sewer (Caustic Sewer)
A1S Alkaline Sewer (Softwood)
A1H Alkaline Sewer (Hardwood)
W Woodyard Sewer
H Hypochlorite Filtrate (Hardwood and Softwood)
111-40
-------
TABLE 6
(Continued)
Code Mill Location Sampled
HS Hypochlorite Filtrate (Softwood)
HH Hypochlorite Filtrate (Hardwood)
CD Chlorine Dioxide (Hardwood and Softwood)
CD2 Chlorine Dioxide (Second Stage)
PaM Paper Mill Sewer
PM Pulp Mill Sewer
R&E Recovery and Evaporator Sewer
PI Primary Treatment Influent
PE Primary Treatment Effluent
SI Secondary Treatment Influent
SE Secondary Treatment Effluent
FE Final Effluent
111-41
-------
TABI.K 7
COI.OK liY NCASf METHOD AT Ai,L .SAMPLE LOCATIONS
(Refer to Table 6 for Sample (.ocnLion Code Ident i f ication)
lil eai:hiil|; Day of Wood Spm: i-U M.I.H Location Sampler!
Mill. No .
100
101
102
10313
Sequence Survey
A-Unc 1
CEHDII 2
H-l.ine 3
CEIII) Average
CKIIDII 1
2
3
Average
CEDED 1
2
3
Average
CEIIEI) I
2
3
Average
Soft
56%
54%
54%
54%
HA
3%
65%
92%
40%
38%
39%
40%
39%
0%
68%
20%
31%
Hard
44%
46%
46%
46%
96%^
30%
7%''
56%'
62%
61%
60%
61%
100%
32%
80%
69%
Color (m^/1)
BA
1. , 500
1 ,060
910
1,160
8
9,060
3,730
1,340
4,710
BUa
590
580
560
580
D
3,830
3,170
4,350
3,780
BC
3,810
4,210
2,620
3,550
C
990
810
1 , 360
1,050
B
970
1,190
980
1,050
B
960
990
990
980
A
1,440
1 , 060
1 ,310
1,270
E
7,300
15,300
22,280
14,960
W
100
93
58
84
R&E
1,360
510
320
730
PM
1 ,0]0
880
1,220
1 ,040
A
1,720
1,500
1,560
1,590
PI
145
230
230
200
PaM
16
49
66
44
PI
1,010
850
1,010
960
PI
'8909
1,7709
.1 , 900
.1,480
PE
130
185
230
180
PE
1,020
960
560
850
PE
1 ,060
1,170
1,380
1 , 200
SE
1,200
1 ,180
1,220
1,200
11.
120
110
100
110
14
1,060
1,340
1,340
1,250
SI
1,040
1,180
1,070
1,100
FE
1,220
1 , 1 80
1,180
1,190
12
220
310
400
310
SE
1,360
.1,950
1,310
1,540
SE FE
1,330 1,340
1,290 1,290
1,060 1,290
1,230 1,310
10
640
620
560
610
FE
1,750
2,250
1,720
1,910
1 2
33 740
8 280
16 320
19 450
1. Ash pond decant 10. Spill pond effluent
2. Sludge 1,'igoon decant: lla. One recovery boiler out of three was down. Decker color might
be higher than normal.
J. Six percent, transition pulp from softwood to
hardwood 11. Oxidation pond effluent
4. One percent transition pulp from hardwood to 12. Spillway
softwood
13. Mill had a major spill upon startup after 1975 holidays. Due
5. Five percent transition puip from softwood to this problem, color measurements taken of treated effluent
to hardwood during sampling period will be higher than normal
6. One percent transition pulp from hardwood to 14. Intermediate aeration effluent
softwood
7. Four percent transition pul p
8. tJrown stock sewer
9. Gampler ma I function, grab sample was analyzed
-------
Mill No.
105
108
Bl earh i il};
Si'qnem-e
Softwood
CKIIHKI)
Ha rdwood
CEIini)
CEDED
CEDE/ III)
CIIEDED
3-l,ines
Mi) Is A,B&C
l):iy of
Su rvey
1
2
3
Average
1
2
3
Average
1
2
3
Average
1
2
3
Average
1
2
3
Average
I
2
3
Average
Wood _Sj»ur ie
Soft Hard
522
542
537.
537,
522
542
537,
532
412
1002
397,
607,
1 002
1002
1002
1002
732
712
722
722
732
712
72%
722
4 HZ
462
472
472
487.
462
472
472
592
07
61%
402
02
02
02
02
272
297,
282
282
272
292
282
282
mi
2,920
2,460
2.58015
2,650
SE
2 , 320
-
2,360
2,340
D
1 ,350
920
:i , 030
1,100
OS
3,450
3,790
2,770
3,340
Mill A-
Mill B-
MI11 C-
B
890
1,630
1,170
1,230
I)S
2,160
1,720
85015'
1,940
FE
1,950
_
2,580
2,260
C
480
850
690
670
CS
530
650
590
590
C
390
49
823
NA
PF.
740
620
485
620
TAIiLli 7
(Continued)
CM
440
16 235
16 1 50
279
K
2,770
7,530
5 , 1 00
3,130
ES
6,040
6,220
6,040
6,100
II
6,230
310
-
NA
ST.
1,310
1,420
1,630
1,450
CS
530
390
215
380
A
205
470
360
345
BA
495
620
485
530
20
-
-
11,330
NA
FE.
1,170
1,330
1 , 310
1,270
Mil 1
I'll
840
61.0
400
620
Al
2,950
8,750
5,560
5,750
BC
3,340
3,670
3,450
3,490
E
4,560
570
-
NA
FE,,
1,250
1,310
1 ,250
1,270
Location Sampled
Color (nig/ 1 )
K.S
1 6 , 01 0
1 6 , 01 0
1 1,090
14,370
PF.
_ 1 /
1 ,010
810
910
SE
1 , 090
820
910
940
CD
49
41
530
NA
21
22,020
26,390
25,980
24,800
A W
1,220
1 ,180 2,250
940 1,330
1,110 1,790
SI FE
56018 ])830
L.410 1,780
1,170 1,640
1,050 1,750
FE
1,420
1,310
-
1,420
E, CD.,
'0 24
49 16
550 0
NA NA
VI SI
2,130 1,900
1,120 1,240
2,250 1,510
1,830 1,550
19
910
-
-
910
15. Pulp mill, was down for 2 of the 12 samples
16. Decker was at 0 to half flow from 12:00 AM to
6:00 AM, or 4 of the 12 samples (3rd day's
data @ this point was discarded).
17. Primary clarifier down, sample taken at bypass ditch
18. Low color at the secondary influent probably related to
primary clari fier being bypassed. Ad j ustment in secon-
dary influent will be made by adding the first day's
bypass ditch color load to that of the secondary influent
19. Primary clarifier bypass ditch
20. Hypochlorite plus caustic extract filtrate, Mill C
21. Strong waste pond effluent
-------
I 14
BU'ai-liing
Sequence
CEDED
A- Line
CEIII)
li-l.ine
CEMDUD
Softwood
Ha rdwood
CIIDED
CEIII) El)
Day of
1
3
Average
1
2
3
Average
1
2
3
Average
1
2
3
Average
1
2
3
Average
1
2
3
Average
Wood t
S.Tf t
17%
79%
0%
30%
54%
61%
76%
63%
46%
61%
487.
51%
25%
26%
24%
25%
100%
1 00%
100%
100%
1007.
100%
100%
1.00%
ipeeu'
lla rd
83%
21%
1 00%
70%
46%
39%
24%
37%
54%
39%
52%
49%
75%
74%
76%
75%
0%
0%
0%
0%
0%
0%
0%
0%
TABU! 7
(Cont Inued)
I)
360
1 , 800
600
920
CH
610
460
470
510
Dil
10,380
8,670
8,850
9,300
D
3,650
4,530
4,960
4,380
CS
1,240
1 , 000
1 , 160
1 , 1 30
23
240
240
C
320
570
450
CS
590
860
680
710
DS
4 , 330
2,390
1,720
2,810
C
330
320
360
340
ES
4,290
5,810
7,900
6,000
24
1,210
1,210
E
5,900
11,160
4 , 2.1 0
7,090
EH
11 ,160
13,970
7,330
10,820
CH
170
210
165
180
E
2,930
3,440
2,930
3,100
BS
405
900
920
740
PI
1,750
650
1 , 080
ES
9,630
17,370
20,220
15,740
CS
850
1,020
1,020
960
A
250
290
300
280
R6.E
330
76
140
180
Mill
Ci
FT
950"
1,650
740
1,110
PI
1,800
1 ,090
1,020
1,300
ES
12,580
1.2,530
9,880
11,660
FT
1,430
2,050
1 ,450
1,640
A
1,240
1,060
1 , 1 20
1,140
Location Sampled
>lor (mg/1)
SI
850
1,480
1 ,040
1,120
SI
1 ,400
1,250
1,090
1,250
1111
540
590
740
620
SI
1,040 '
1,210
1 ,010
1,090
22
7
0
4
4
SE
1,060
1 ,090
1 , 1.00
1 ,080
FE
1 , 250
1,440
1 ,650
1,450
PI
.1,150
1,230
2,080
1,490
FE
2 , 160
2,130
1,930
2,070
PaM
76
33
175
90
FE
1,060
1,020
1 ,020
1,030
PE
1,140
1,120
1,590
1,280
PI
490
425
500
470
FE
1,540
1,630
1,520
1,560
PE
250
500
510
420
FE
740
670
820
740
22. RecanstJclzing Sewer
23. Digester condensate
24. Combined evaporator condensate
25. Mi.] I 117 adds hypochlor i te to the first stage caustic extraction filtrate
being sewered to minimi 7,e color
-------
> :ILL: 3072835 rBorrower: SLA :ReqDate: 19990826 :NeedBefore: 19990925
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> :CALLNO: EPAX 9205-0092 f
^ :TITLE: Review of color waste loads and color technologies for bleached
kraft mills / f
> :IMPRINT: [Washington, D.C.] : U.S. Environmental Protection Agency, 1978. I
> :VERIFIED: OCLC I
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^ -.RETURN VIA: First class mail f
-------
Mill No.
Sequence __ Su rv
liny of Wood Specie
Su rve-y So f t_ Ha rd
I 25
I 19
121 Bleach Plant I
CEIIEU
Bleach Plant 2
CEDED
CEDED
Newsprint-CKII
Coaled Paper
CE1III
I 25% 75%
2 25% 75%
3 2_5% 75%
Average 25% 75%
I 42% 58%
2 42% 58%
3 42% 58%
Average 42% 58%
57% 43%
58% 42%
52% 48%
56% 44%
L 69% 31%
2 79% 21%
3 100% 0%
Average 81% 18%
100%
100%
92%
0%
15%
0%
14%
8%
TABLE 7
(Cout inued)
C
570
530
820
640
CS
980
1,010
780
920
S
4,500
4,370
2,690
3,850
A
740
850
610
730
n
2,460
2,560
1,110
2,040
E
3,000
4,910
3,170
3,690
HS
3,900
4,040
3,670
3,870
CS
1,020
1,070
680
920
Al
10,580
4,640
6,540
7,250
C
1,030
1,310
1,140
1,160
PI
790
770
960
840
CH
640
670
370
560
ES
8,690
8,690
5,330
7,570
R&E
6,890
6,420
1,220
4,840
F.
7,540
12,130
7,780
9,150
SI
960
1 ,060
1,070
1,030
till
2,930
3,140
2,500
2,860
CM
560
1 ,270
590
810
1'E
4,300
4,510
4,660
4,490
AT
4,400
5,850
5,100
Mill Location Sampled
Color (nig/1)
I'M
940
1,180
1 ,250
1 , 1.20
PI
870
810
660
780
Ell
5,470
7,920
4,110
5,830
SI
2,370
3,380
2,040
2,600
W
6,620
11,330
8,980
27
.100
230
320
220
PE
1,080
880
690
880
B
1,040
1 , 300
1,070
1,140
SE
1,910
2,160
1,270
1 ,780
PE
2,340
3,290
2,800
2,810
28
1,620
2,220
850
1,560
SK
490
540
480
500
PK SI
980 1,460
660 1 , 380
780 1,090
810 1,310
FE
1 ,660
1 ,830
1,160
1,550
SI SE
1,800 1,590
2,040 1,520
2,190 1,660
2,010 1,590
FE
1,530
1,470
1 , 500
1 , 500
FE
.1,450
1,440
1 ,460
NoL'es: 26. Sodium hypochl or i te is added to the extraction stajje tower
27. No. 2 Lagoon Influent
28. No. 2 Lagoon Effluent
-------
Itlca.-liinj;
Sei|(IUlK-e
CEDED
CEIIDEI)
Mill 1= 1
Mill 2=2
Suf twooci
CElin
Ha rdwood
CEII
A-Pine
C Mil III!
C-l'iiu-
CEIIEI)
l)-ll;i rdwood
cnr.iin
Day of
Survey
1
2
3
Average
1
2
:)
Average
1
2
3
Average
I.
2
n 3
Average
1
2
3
Avern ye
Wood Spec ie
Soft
1007.
100%
100%
[007,
1007.
100Z
100%
100%
IOOZ
1002
1002
100%
34%
372
34%
35%
58%
61%
6.1 1
60%
Hard
0%
0%
oz
0%
oz
oz
0%
0%
02
02
02
0%
662
632
662
652
42%
39%
39%
402
I)S
1,330
1 , 330
1 ,070
1 ,240
UjS
455
33
240
31
680
1 , 280
1,850
1,270
S
1,500
.1 , 250
1 , 330
1,360
I,34
14,510
13,840
11,740
.1 3 , 360
CS
990
1 , 360
2 , 1 60
1,500
PS
590
480
455
410
32
100
240
120
150
CS
1,120
1,040
680
950
A35
2,110
1,970
1 ,660
1,910
TAUI.K 7
(Continued)
ES
1:1 ,670
13,800
11,670
12,380
C1S
540
640
590
33
145
2,700
2,840
1,900
ES
17,190
17,910
16,470
17,190
ES-A
12,110
16,450
15,790
14,780
«c29
AS
660
920
1 ,120
900
C?S
395
730
380
500
PI
2,040
2,840
2,840
2,570
CH
600
820
490
640
ES-C
24,490
17 , 320
17,890
19,900
Mil 1 1
C
-------
llluai:hing Day of
Mill No. Sequence Survey
140 CEIIEI) 1
2
3
Average
1 52 CEIl 1
with soait.' pulp 2
blearhed in 4th 3
stage "P" Average
161 Softwood 1
CEIII)-'7 2
. Hardwood 3
CEIII) Average
Io7 CEDE/HI) 1
2
3
Average
Wood
Soft
0%
0%
0%
0%
4-5%
4-5%
4-5%
4-5%
41%
46%
48%
45%
0%
0%
0%
0%
Spec ie
lla'rd
1 00%
100%
100%
100%
95-96%
95-96%
95-96%
95-96%
59%
54%
52%
55%
100%
1 00%
100%
100%
TAIII.E 7
(Continued)
1)11
1 ,270
1 ,630
1,700
1 , 530
1)11
5 , 600
5,740
5,500
5,610
I)S
4 , IIO^8
4 , 790
7,970
5,690
Cll
1 , 180
990
960
1,040
Cll
950
1,120
1,090
1,050
Cll
650
350
460
490
Dll
4,590."
3,790
5,350
4,580
Ell
4,310
6,070
5,820
5,400
EH
1,720
2,070
1 ,980
1,920
Ell
6,700
4,550
5,740
5,700
CS
_40
910^1
1,040
980
W
770
-
370
570
PI:
1,040
.1,220
1 ,360
1,210
PI
930
850
650
810
ES
11 ,350'H
9,640
12,1 60
1 1 , 050
K&E
960
3,670
1,150
1,930
Mill Location Sampled
Color (ing/1)
SI
1 ,180
1,360
1,270
1 ,270
PE
810
470
550
610
Cll
690
400
850
650
PI
1,340
2,390
2,820
2,180
SE36
1 ,040
1 ,170
1,070
1,090
I'K
650
640
590
630
42
Ell
4,780
3,520
4 , 940
4,410
ST.
2,010
2,320
2,040
2,120
43 44
Al A10
3,560 950
3,950 530
4,480 960
4,000 810
FE
1,920
1,850
2,010
1,930
A
320
465
710
500
NULUS: 36. Mill Wiis clown for L7 clays approximately 3 weeks before
sainpl Jn^. There fore, final effluent samples could
luive been a f feu ted.
37. P.'trL of nuirkct pulp goes through CEII bleaching only
38. So I twoiKi h I enc'h p 1 ant down for" 5 of 12 samp] es
39. One of 12 samples not taken because of samp]ing problem
40. Unable to get sample at first stage softwood Cl?
filtrate
41. Two of 12 samp 1es not co11ected
A2. Some samples at the fi rst stage hardwood caustic extract
were not collected because sample point was not ac-
cessible. Day I - 2 of 1.2 samples; Day 2 - 3 of 12,
and Day 3 - 0 of 12
43. Alkali ne pulp mill sewer
44. Alkaline paper mill sewer
-------
TABLE 8
COLOR LOAD BY SAMPLE LOCATION
Mill N.I
1.02
Day of
Survey
1
2
3
Average
1
2
3
Average
1
2
3
4
Average
1
2
3
A
Average
1
2
3
Average
1
2
3
Average
Flow contim
L
ISA
23.02 (50.70)
1.6.06 (3.r).38)
13.79 (30.38)
17.63 (38.83)
SI*
1.61.36(355.42)
.187.77(413.58)
166.21(366. 10)
171.84(378.50)
71
102.98(226.82)
56.53(12/1.51)
22.85 (50.32)
60.78(133.88)
FE1
114.63(252.49)
114.00(251.11)
131.44(298.51)
120.02(264.37)
,,3
6.26 (13.79)
6.15 (13.55)
5.94 (13.08)
6.12 (13.47)
103
14.84 (32.68)
19.61 (43.20)
24.70 (54.41)
19.72 (43.43)
lously recorded
Co lor Load -Thou sand
BCA
2.89 (6.36)
3.19 (7.03)
1.98 (4.37)
2.69 (5.92)
SE*
206.59(455.05)
205.27(452.13)
164.65(362.67)
192.17(423.28)
C*
10.05 (22.14)
8.84 (19.47)
15.05 (33.14)
.11.31 (24.92)
83
1.21 (2.67)
1.18 (2.59)
1.06 (2.34)
1.15 (2.53)
B'
55.12(12.1.42)
70.33(154.92)
57.55(126.76)
61.00(134.37)
6. Sludge lagoon
Mill Location Sampled
Kilograms Par Day (Thousand
A4
32.73 (72.10)
24.09 (53.07)
29.78 (65.59)
28.87 (63.59)
FEV
187.84(413.75)
122.19(269.13)
215.04(473.66)
175.02(385.51)
E*
35.13 (77.37)
78.26(172.37)
102.14(224.98)
71.84(158.24)
w3
0.76 (1.67)
0.70 (1.55)
0.44 (0.97)
0.64 (1.40)
decant
Pounds Per Day)
PM*
37.50 (82.60)
32.69 (71 .97)
45.30 (99.77)
38.49 (84.78)
53
0.50 (1.1.0)
0.12 (0.27)
0.24 (0.53)
0.30 (0.65)
A1
26.07 (57.42)
23.87 (52.57)
25.41 (55.98)
25.12 (55.32)
PI3
10.77 (23.72)
17.08 (37.62)
17.08 (37.62)
14.98 (32.99)
PI4
137.75(303.42)
119.15(262.45)
137.75(303.42)
131.55(289.76)
t,"
2.81 (6.18)
1.06 (2.34)
1.2.1 (2.67)
1.69 (3.73)
PI4
82.96(182.73)
65.75(144.83)
126.74(279.17)
135.33(298.09)
102.70(226.21)
PE3
9.65 (21.26)
13.37 (29.44)
17.08 (37.62)
13.37 (29.44)
PE4
140.56(309.60)
159.58(351.49)
182.99(403.06)
161.04(354.72)
SEA
91.39(201.29)
105.95(233.38)
107.24(236.21)
101.53(223.63)
91
8.09 (17.83)
6.96 (15.33)
6.17 (13.60)
7.08 (15.59)
3. Flow estimated by the mill 7. Brown stock sewer
4. Flow calculated by the mi.ll 8. Spill pond effluent
5. Ash pond decant 9. Oxidation pond effluent
10. Spillway
-------
Mill No.
103
105
106
Day ol~
Survey
1
2
3
Average
1
2
3
Average
L
2
3
Average
1
2
3
Average
1.
2
3
Average
1
2
3
Average
,/'
30.03 (66. 16)
27.26 (60.05)
37.58 (82.77)
31.63 (69.66)
sir1
81.77(180. 11)
119.39(262.97)
77.43(170.54)
92.86(204.54)
n,,4
9.40 (20.71)
7.92 (17.45)
8.31 (18.30)
8.54 (18.82)
A1
105. 16(231 .62)
104.88(231.01)
77.46(170.61)
95.83(211.08)
I:
D
33.25 (73.23)
2H.23 (62.19)
28.88 (63.61)
30. 12 (66.34)
SI*
56.44(124.31)
U5. 31 (320. 06)
130.33(287.06)
110.69(243.81)
Color Load Thousand
B1
28.23 (62.17)
29.10 (64.11)
27.27 (60.06)
28.20 (62.11)
FE1
105.22(231.76)
137.75(303.42)
91.49(201.52)
111.49(245.57)
DS*
7.69 (16.94)
6.12 (13.49)
3.03 (6.67)
5.62 (12.37)
w1
6.05 (13.33)
5.90 (12.99)
5.97 (13.16)
C" .
10.91 (24.03)
21.26 (46.82)
18.04 (39.73)
16.73 (36.86)
FE3
152.53(335.98)
148.37(326.80)
136.70(301.10)
145.87(321.29)
TABLE 8
(Continued)
Mill Location Sampled
Kilograms Per Day (Thou
R&EA
26.69 (58.78)
10.57 (23.28)
6.8L (15.01)
14.69 (32.36)
CH4
7.03 (15.49)
3.76 (8.28)
2.40 (5.28)
4.39 (9.68)
PI1
171.73(378.25)
92.42(203.56)
195.63(430.91)
153.26(337.57)
E*
37.78 (83.22)
102.70(226.22)
69.56(153.22)
70.02(154.22)
123
49.99(110.12)
49.99(110.12)
sand Pounds Per Day)
PaM1
0.18 (0.39)
0.54 (1.19)
0.68 (1.49)
0.46 (1.02)
cs<
11.99 (26.40)
8.82 (19.43)
4.86 (10.71)
8.56 (18.85)
SI*
276.57(609.19)
186.65(411.12)
227.28(500.62)
230.11(506.85)
A3
6.99 (15.40)
16.03 (35.30)
12.28 (27.04)
LI. 76 (25.91)
PEA
31 .34 (69.03)
30.55 (67.29)
17.65 (38.88)
26.51 (58.40)
EH4
3.95 (8.69)
2.86 (6.31)
1.88 (4.14)
2.90 (6.38)
SE*
397.55(875.67)
410.13(903.37)
403.84(889.52)
. Al3
40.24 (88.63)
119.35(262.88)
75.84(167.04)
78.47(172.85)
II3
63.73(140.38)
82.04(180.70)
79.20(174.44)
74.99(165.17)
ES*
106.15(233.81)
106'. 15(233. 81)
73.53(161.96)
95.28(209.86)
FE2
334.15(736.02)
448.37(987.59)
391.26(861.80)
PE<
55.87(123.06)
51.56(113.56)
53.71(118.31)
.1. Flow continuously recorded
2. Flow measured and calculated
3. Flow estimated by the mill.
4. Flow calculated by the mill
1.1. Intermediate aeration effluent
12. Primary cJarifier by-pass ditch
-------
Mill No.
107
108
Day of
Survey
1
2
3
Average
1
2
3
Average
1
2
3
Average
1
2
3
Average
1
2
3
Average
1
2
3
Average
:i
2
3
Average
/:
I)S
J2.03 (26.49)
16.51 (36.37)
9.'J7 (21.96)
12.83 (28.27)
FEJ
76.36(1.68.20)
65.81(144.96)
71.09(156.58)
Mi 1 1
A
IS
C
Mill
A
11
C
Bl
84.30(185.68)
156.86(345.50)
124.11(273.38)
121.84(268.38)
D3
2.05 (4.51)
10.23 (22.53)
3.41 (7.51)
5.23 (11.51)
SK3
112.45(247.69)
119.76(263.79)
129.19(284.57)
1.20.47(265.35)
Color Load-Thousand
CS<
6.08 (13.40)
9.33 (20.56)
6.95 (15.31.)
7.45 (.16.42)
C*
4.05 (8.92)
0.96 (2.12)
0.71 (1.56)
NA
O
0.21 (0.46)
0.39 (0.87)
NA
PE1
124.76(274.81)
107.11(235.93)
88.57(195.08)
106.82(235.28)
c3
9.70 (21.36)
17.27 (38.05)
13.48 (29.70)
KE1
108.43(238.84)
108.21(238.34)
115.94(255.37)
110.86(244.18)
TABLE 8
(Cout.inued)
Mil. 1. Local: i.un Sampled
Kilograms Per Day (Thousand
ES4
64.53(142.14)
83.19(183.23)
66.36(146.18)
71.36(157.18)
,1*
37.76 (83.18)
2.47 (5.44)
NA
CD,*
0.10 '(0.21)
0.09 (0.20)
NA
si1
347.91(766.33)
387.35(853.20)
474.89(1046.02)
403.40(888.55)
E3
67.06(147.71)
.126.85(279.40)
47.87(105.40)
80.59(177.50)
Pounds Per Day)
BA*
5.68 (12.52)
8.90 (19.61)
5.72 (12.59)
6.77 (14.91)
43*
57.10(125.75)
NA
FE1
75.35(165.98)
85.66(188.68)
79.41(174.91)
80.14(176.53)
PI.2
34.49 175.97)
73.66(162.25)
25.44 (56.03)
44.53 (98.08)
BC4
18.60 (40.97)
25.58 (56.35)
19.74 (43.47)
21.31 (46.93)
E*
12.09 (26.64)
1.61 (3.56)
NA
PE,1
242.39(533.90)
272.97(601.26)
288.41(635.26)
270.96(596.83)
Pip2
65.92(145.20)
121.53(267.68)
52.74(116.16)
80.06(176.35)
SE*
47.62(104.88)
36.27 (79.90)
39.75 (87.56)
41.06 (90.45)
CD4
0.19 (0.42)
0.16 (0.36)
1.77 (3.89)
NA
141
45.88(101.06)
99.98(220.22)
67.92(149.60)
71.26(156.97)
SI*
94.29(207.69)
171.30(377.32)
114.82(252.91)
126.74(279.17)
Notes: 1. FJow continuously recorded 4. Flow calculated by the mill
2. Flow measured and calculated 13. Hypochlorite plus caustic extract filtrate, Mill C
3. Flow estimated by the mill 14. Strong waste pond effluent
-------
Day 11 f
Survey
Cok
114
I
2
3
Average
3
Average
Average
I
2
3
Average
I
2
3
Average
o.m (2.oo)
£._52 (I. 14)
0:99 "(2.17)
130.24(286.87)
132.03(290.82)
163.79(360.77)
142.02(31.2.82)
1)11
,3
55.06(121.27)
45.99(.IOI .30)
46.94(103.40)
49.33(108.66)
PI
189.53(417.47)
198.53(437.28)
338.08(744.67)
242.05(533.14)
I)3
12.44 (27.41)
15.45 (34.02)
16.91 (37.25)
14.94 (32.90)
VE
267.60(589.42)
249.35(549.24)
204.74(450.96)
240.56(529.87)
TAISI.E 8
(Conl inued)
Mill Location Samp.led
r Load Thousand Kilograms Per Day (Thousand Pounds Per Day)
..
CS
1.05 (2.31)
1.63 (3.59)
1.42 (3.12)
1.37 (3.01)
DS3
22.97 (50.59)
12.68 (27.94)
9.13 (20.10)
14.92 (32.87)
PE3
187.88(413.84)
180.77(398.17)
258.43(569.24)
209.03(460.42)
c3
14.76 (32.50)
14.31 (31.51)
16.09 (35.45)
15.05 (33.15)
3
Ell
16.49 (36.32)
16.41 (36.14)
5.00 (11.01)
12.63 (27.82)
CH3
2.64 (5.82)
3.26 (7.19)
2.57 (5.65)
2.82 (6.22)
FE*
239.22(526.92)
247.64(545.47)
293.71(646.93)
260.19(573.11)
E3
42.85 (94.38)
50.30(110.8])
42.85 (94.38)
45.34 (99.86)
3
KS
17.15 (37.77)
36.20 (79.73)
42.14 (92.81)
31 .83 (70.10)
cs3
12.23 (26.96)
14.69 (32.35)
14.69 (32.35)
L3.87 (30.55)
A2
14.96 (32.96)
.17.25 (37.99)
17.73 (39.05)
16.65 (36.67)
3
PI
187.54(413.09)
99.94(220.13)
101.25(223.02)
129.88(286.08)
ES3
33.36 (73.49)
33.23 (73.20)
26.20 (57.72)
30.94 (68.14)
PI2
109.71(241.65)
132.49(291.82)
85.15(187.55)
109.12(240.35)
1
SI
145.87(321.29)
114.61(252.45)
108.20(238.33)
122.89(270.69)
HH3
1.43 (3.15)
1.57 (3.45)
1.96 (4.32)
1.65 (3.64)
SI1
131.60(289.87)
154.95(341.29)
125.51(276.45)
137.35(302.54)
1. Flow continuously recorded
2. Flow measured and calculated
3. Flow estimated by the. mill
4. Flow calculated by the mill
-------
Day of
Mill No. Survey
117 1
Average
1
2
3
Average
1 18 1
2
3
Average
1
2
3
Average
119 1
2
3
Average
1
2
3
Average
cs3
7.05 (15.
5.6H (12.
6.59 (14.
6.44 (14.
0.88 (1.
0.35 (0.
1 . 92 (4 .
1.05 (2.
c3
4.97 (10.
4.62 (10.
7.1.5 (1.5.
5.58 (12.
193
0.55 (1.
0.76 (1.
0.29 (0.
0.54 (1.
c:s3
5.57 (L2.
5.74 (12.
4.43 (9.
5.25 (11.
SEA
21.91 (48.
23.2.3 (53.
21.28 (46.
22.41 (49.
Co
52)
52)
52)
19)
93)
77)
24)
31)
94)
17)
74)
28)
.22)
,67)
64)
,18)
27)
64)
76)
,56)
.25)
.17)
.87)
.36)
TABI.K 8
(Cone i nued)
Mill Location Sampled
lor Load-Thousand Kilograms Per Day (Thousand Founds Per Day)
ES
16.25
22.01
29.93
22.73
PI
23.04
19.58
22.42
21.65
E
10.23
16.74
L0.81
3
(35.80)
(48.48)
(65.93)
(50.07)
1
(50.75)
(43.13)
(49.39)
(47.69)
3
(22.53)
(36.88)
(23.81)
1.2.59 (27.74)
HS3
6.06
6.27
5.70
6.01
(13.34)
(.13.82)
(12.56)
(13.24)
BS
4.15
9.21
9.41
7.59
1'E
1.1.75
23.04
22.78
19.19
PI
.12.27
11 . 38
1.8.19
13.95
CM
4.85
5.08
2.81.
4.24
3
(9.13)
(20.28)
(20.73)
(16.71)
I
(25.89)
(50.74)
(50. 18)
(42.27)
4
(27.03)
(25.06)
(40.06)
(30.72)
3
(10.68)
(11.18)
(6.18)
(9.35)
0,
0,
0
0.
44
41
50
45,
14
15
20
16
4
4
3
4
R&E
.86 (1.90)
.20 (0.44)
.54 (.1.1.8)
.53 (1.17)
KE1
.46 (97.94)
.07 (90.46)
.76(1 11 .81)
.46(100.13)
si1
.91 (32.85)
.66 (34.50)
.27 (44.65)
.95 (37.33)
llll3
.55 (10.02)
.88 (10.74)
.88 (8.55)
.44 (9.78)
16.
13.
15.
15.
0.
0.
16,
19,
26.
20.
45.
39,
32,
38,
A1
25 (35.80)
.53 (29.81)
,23 (33.55)
01 (33.06)
163
,02 (0.04)
,02 (0.04)
FE*
.38 (36.09)
.66 (43.30)
,05 (57.37)
.70 (45.60)
PI1
.52 (93.66)
.59 (87.20)
.01 (70.50)
.04 (83.79)
15
1
Neg.
Neg.
Nee.
Neg.
1.73
4.52
4.52
18
0.04
0.08
0.11
0.07
PE
(9.96)
(9.96)
3
(0.08)
(0.17)
(0.24)
(0.16)
4
48.28(106.35)
39.34 (86.65)
30.59 (67.37)
39.40
(86.79)
.1. Plow continuously recorded 16. Digester condensate
3. Flow estimated by the mill 17. Combined evaporator condensate
4. Flow calculated by the mill J8. No. 2 Lagoon influent
15. R'jcausticizing sewer 19. No. 2 Lagoon decant
-------
125
Day of
1
2
3
Average
1
2
3
Average
1
2
3
Average
TABLE 8
(Continued)
Mill Location Sampled
Color Load-Thousand Kilograms Per Day (Thousand founds Per Day)
s3
85.25(187.77)
82. 78(182. 34)
50.96(112.24)
72.99(160.78)
PC1
66.83(147.21)
47.01(103.55)
51.42(1 13.26)
55.09(121.34)
A1
9.81 (21.61)
11.37 (25.04)
7.81 (17.21)
9.67 (21.29)
cs3
25.12 (55.33)
26.35 (58.04)
16.74 (36.89)
22.74 (50.09)
si3
265.52(584.84)
255.15(562.01)
.195.75(431.17)
238.81(526.01)
Al1
175.57(386.72)
79.29(174.64)
11.2.25(247.24)
122.37(269.53)
ES3
82.31(181.30)
82.31(181.30)
50.48(111.20)
71 .70(157.93)
FE1
300.86(662.68)
286.27(630.55)
292.68(644.67)
293.27(645.97)
R&E3
5.22 (11.50)
4.87 (10.72)
0.93 (2.04)
3.67 (8.08)
CH3
8.70 (19.16)
26.46 (58.29)
12.29 (27.08)
15.82 (34.84)
PE1
91.72(202.03)
89.54(197.22)
109.82(241 .89)
97.02(213.71)
E,,3
22.80 (50.21)
45.01 (99.14)
23.36 (51.45)
30.38 (66.93)
SI1
169.26(372.82)
238.83(526.06)
150.49(331.47)
186.19(410.12)
B3
118.21(260.37)
147.76(325.47)
121.62(267.88)
129.19(284.57)
SE1
136.41(300.46)
152.63(336.18)
93.68(206.35)
127.57(281.00)
I
2
3
Average
I.
2
3
4
Average
1
2
3
4
Average
.,20
D
6.71 (14.78)
6.98 (15.38)
3.03 (6.67)
5.58 (12.28)
SI
218.03(480.24)
250.11(550.91)
264.19(581.91)
244.11(537.69)
27.51 (60.60)
34.74 (76.52)
37.27 (82.10)
33.18 (73.08)
192.59(424.21)
186.36(410.48)
200.25(441.09)
193.07(425.26)
184.82(407.10)
262.87(579.01)
192.18(423.30)
213.30(469.82)
FE1
232.71(512.57)
247.77(545.74)
211.69(466.27)
230.72(508.19)
Al3
83.20(183.27)
72.35(159.36)
96.19(211.88)
83.92(184.84)
102.84(226.51)
176.00(387.66)
139.42(307.09)
FE
135.64(298.77)
157.06(345.95)
133.98(295.11)
144.23(313.28)
I. Flow continuously recorded
3. Klow estimated by the mill
4. Flow calculated by the mill
20. Mill was not discharging to the river during color survey
-------
Mill No.
.134
136
Notes:
3
Aver.ige
3
Average
1
2
3
Average
1
2
3
Average
1
2
3
Average
IIS
10.08 (22.20)
10.08 (22.20)
8. 1.1 (17.86)
9.42 (20.75)
153.94(339.07)
162.61(358.18)
125.49(276.40)
147.35(324.55)
1.14 (2.50)
1.09 (2.40)
1.26 (2.77)
1.16 (2.56)
I'M
51. 14(125.85)
66.20(145.81)
62.43(137.51)
61.92(136.39)
O3
98.95(217.96)
94.39(207.90)
80.06(176.35)
91.14(200.74)
Pi
183.05(403.19)
201.49(443.80)
213.84(471.01)
199.46(439.33)
TABI.K 8
(Cont inued)
M L.l 1 Location Sampl ed
Co lor Load -Thou sand Ki 1 ograms Per Day (Thousand Pounds Per Day)
cs3
16.88 (37.18)
23.19 (51.07)
36.83 (81.12)
25.63 (56.46)
FE1
1.70.10(374.66)
183.30(403.75)
161 .40(355.51)
171.60(377.97)
CS*
8.95 (19.72)
9.30 (20.48)
7.70 (16.97)
8.65 (19.06)
PI1
56.16(123.71)
75.07(164.36)
57.33(126.28)
62.86(138.45)
A3
18.39 (40.50)
17.17 (37.81)
14.46 (31.86)
16.67 (35.72)
PFA
197.99(436.11)
191.98(422.87)
213.84(471.01)
201.27(443.33)
ES3
212.32(467.67)
250.97(552.79)
212.23(467.47)
225.17(495.98)
Es4
26.05 (57.38)
30.54 (67.26)
35.57 (78.34)
30.72 (67.66)
PE1
61.96(136.48)
55.98(123.30)
59.07(130.12)
59.01 (129.97)
ES3
39.46 (86.91)
53.60(118.06)
51.45(113.32)
48.17(106.10)
FE4
149.43(329.14)
172.97(381.00)
166.75(367.30)
163.05(359.15)
AS2
20.00 (44.06)
33.11 (72.94)
30.98 (68.23)
28.03 (61 .74)
CH*
5.55 (12.22)
8.48 (18.68)
5.42 (11. 94)
6.48 (14.28)
FE1
45.38 (99.96)
44.89 (98.87)
45.27 (99.72)
45.18 (99.52)
ESc3
26.9I"(59.27)
19.03 (41.92)
19.66 (43.30)
21.86 (48.16)
PI2
251.99(555.05)
117.98(259.87)
87.35(192.40)
152.44(335.77)
EH4
1.91 (4.20)
1.99 (4.38)
2.30 (5.07)
2.07 (4.55)
HH4
3.80 (8.38)
2.34 (5.16)
2.95 (6.50)
3.03 (6.68)
si*
169.40(373.12)
173.83(382.88)
146.70(323.13)
163.31(359.71)
PaM4
2.30 (5.06)
0.69 (1.52)
1.49 (3.29)
RiE3
7.80 (17.19)
2.06 (4.54)
4.93 (10.86)
1. Flow continuously recorded
2. Flow measured and calculated
3. Flow estimated by trlie mill
4. Flow calculated by the mill
21. MiJl requested that color, in pounds per day, be deleted because data was of a confidential nature and should not be made
public. Informat Lon was nonetheless used in all evaluation procedures^
-------
Mill No
140
152
187
Day of
Survey
1
2
3
Average
1
•)
3
Average
1
2
3
Average
1
2
•J
Average
1
2
')
Average
1
2
3
Average
Co
im3
3.46 (7.63)
4.44 (9.79)
4.63 (1.0. 21.)
4.18 (9.21)
D*
31.83 (71). 10)
28.27 (62.67)
31. .26 (fi8.86)
30.45 (67.07)
us3
34.29 (75.53)
38. 1 1. (8:t.95)
63. 4.1 (J 19. 68)
42.26 (99.70)
V
147.02(323.83)
163. 12(359.31)
J69. 74(373. 87)
.159.94(352.29)
CM3
24.59 (54.16)
20.68 (45.44)
20.00 (44.06)
21.74 (47.89)
FEJ
154.22(339.69)
148.59(327.30)
.150.02(330.45)
150.95(332.48)
TA1II.H 8
(Cont i lined)
Mill l.ocaLion Sampled
lor Load-Thousand Kilograms Per Day (Thousand Pounds Per Day)
<:,,3
4.1.4 (9.1.2)
4.88 (10.75)
4.75 (10.46)
4.59 (10.11)
c"
6.40 (14.10)
2.65 (5.84)
4.53 (9.98)
4.53 (9.97)
,),,3
40.00 (88.10)
33.03 (72.75)
46.62(102.69)
39.88 (87.85)
A1,A
17.92 t39.48)
10.42 (22.96)
17.53 (38.62)
15.30 (33.71)
EH3
57.1,5(125.89)
80.49(177.30)
77.18(169.99)
71.61(157.73)
K,,3
6.51. (14.35)
7.84 (17.27)
7.50 (16.52)
7.29 (16.05)
^
24.12 (53.12)
13.24 (29.17)
20.66 (45.51)
19.34 (42.60)
cs*
10.34 (22.78)
12.34 (27.17)
.11.31 (24.91)
A4
9.70 (21.36)
14.97 (32.98)
21.52 (47.40)
15.33 (33.76)
w3
2.92 (6.43)
1.40 (3.09)
2.16 (4.76)
PI*
25.22 (55.54)
29.12 (64.14)
31.94 (70.36)
28.76 (63.35)
pr1
53.59(118.05)
45.12 (99.38)
47.26(104.10)
48.66(107.18)
KS«
30.97 (68.22)
26.30 (57.92)
33.17 (73.06)
30.14 (66.39)
R(,E3
14.55 (32.05)
55.62(122.51)
17.43 (38.39)
29.20 (64.32)
SI1
28.61 (63.02)
32.46 (71.50)
29.83 (65.71)
30.30 (66.74)
PE*
46.68(102.81)
24.95 (54.95)
39.99 (88.08)
37.31 (81.95)
CH*
8.52 (18.77)
5.11 (11.25)
10.89 (23.98)
8.19 (18.04)
PI3
66.00(145.38)
117.72(259.29)
138.90(305.94)
107.54(236.87)
SE<
25.22 (55.54)
29.93 (61.51)
25.13 (55.36)
26.09 (57.47)
FE*
37.46 (82.51)
33.97 (74.83)
42.90 (94.49)
38.11 (83.94)
EH4
13.04 (28.72)
9.60 (21.15)
13.47 (29.68)
12.04 (26.51)
SI3
144.69(318.71)
167.01(367.86)
146.85(323.46)
152.85(336.68)
Notes: 1. Flow continuously recorded
3. V.low estimated by the mill
4. Flow calculated by the mill
-------
TABLE 9
COLOR LOAD BY SAMPLE LOCATION
(Uofer t.o Table (> for Sample Location Code: Idenci flea t ion)
Day of
Mill No. Survey
1 00 1
3
Average
1
')
3
Average
101 1
2
3
Average
1
2
3
4
Average
102 .1
2
3
Average
1
2
3
Average
I1A
32.0
24.0
20.0
20.5
SI
224
284
243
250
3
170.0
96.0
35.5
1.00.5
FK
190
193
203
195
n
12.0
10.5
10.5
11.0
6
28.5
33.5
43.0
35.0
(64)
(48)
(40)
(51)
(448)
(567)
(485)
(500)
(340)
(192)
(71)
(201)
(379)
(386)
(406)
(390)
(24)
(21)
(21)
(22)
(57)
(67)
(86)
(70)
HC
4.0
5.0
3.0
4.0
SE
287
310
240
279
C
16.5
15.0
23.0
18.0
4
2.0
2.0
1.5
2.0
B
106
120
1.01
109
Color
(8)
(10)
(6)
(8)
(573)
(619)
(480)
(557)
(33)
(30)
(46)
(36)
(4)
(4)
(3)
(4)
(211)
(239)
(201)
(217)
Mill LouaLion Sampled
Load - Kilograms/Thousand Kilograms (Pounds/Ton)
A
40.5
36.5
43.5
42.0
FE
261
185
314
253
E
58
133
.158
116
W
1.5
1.0
1.0
1.0
(91)
(73)
(87)
(84)
(521)
(369)
(627)
(506)
(116)
(265)
(316)
(232)
(3)
(2)
(2)
(2)
52.0
49.5
66.0
56.0
0.7
0.2
. 0.4
0.5
43.0
40.5
39.5
41.0
20.5
29.0
30.0
26.5
I'M
(104)
(99)
(132)
(112)
1
(1.4)
(0.4)
(0.7)
(1.0)
A
(86)
(81)
(79)
(82)
PI
(41)
(58)
(60)
(53)
191
180
201
191
4.0
1.5
2.0
2.5
137
112
196
294
185
18.5
22.5
30.0
23.5
PI
(382)
(360)
(402)
(381)
2
(8)
(3)
(4)
(5)
PI
(274)
(223)
(392)
(588)
(369)
PE
(37)
(45)
(60)
(47)
195
24.1
267
234
151
180
166
166
15.0
12.0
11.0
13.0
PE
(390)
(481)
(534)
(468)
SE
(302)
(359)
(331)
(331)
5
(31)
(24)
(22)
(26)
Ash pond.
S1 ndge 1 ijgoon decant.
Brown stock sewer.
Spill pond effluent.
Oxidation pond.
Spillway.
-------
TAIII.E 9
(Cont i nuetl)
llay of
Mill No
I irj
105
106
1
2
3
Average
3
Average
Average
1
2
3
Average
65. 5
57.0
103.0
(131)
(I U)
(206)
75.0
(150)
si;
178 (356)
250 (500)
213 (425)
214
23.0
20.5
25.5
23.0
(427)
(46)
(41)
(51)
120
90.5
70.0
69.0
76.5
290
360
31 1
320
(46)
1.24 (247)
124 (247)
1.13 (225)
(240)
(181)
(140)
(138)
(153)
SI
(579)
(719)
(621)
Mill. Location Sampled
Color Load - Kj logranis/Thou.sand Kilograms (Pounds/Ton)
(640)
61.5
61 .0
75.0
66.0
229
289
252
257
17.5
13.5
8.5
13.0
7.0
8.5
8.0
29.5
52.5
43.0
41.5
415
367
326
370
H
(1.23)
U22)
(150)
(132)
FE
(458)
(577)
(503)
(513)
DS
(35)
(27)
(17)
(26)
W
(14)
(17)
(16)
C
(59)
(105)
(86)
(83)
FE
(830)
(734)
(652)
(739)
58.0
22.0
18.5
33.0
17.0
9.5
7.5
11 . 5
202
109
284
198
103
254
166
.174
136
136
R&E
(116)
(44)
(37)
(66)
Cll
(34)
(19)
(15)
(23)
PI
(403)
(128)
(568)
(396)
E
(205)
(508)
(332)
(348)
8
(272)
(272)
0.4
1 .0
2.0
1 .0
27.0
19.0
13.5
20.0
325
220
329
292
19.0
39.5
29.5
29.5
I'aM
(0.8)
(2.0)
(4.0)
(2.0)
cs
(54)
(38)
(27)
(40)
SI
(649)
(440)
(659)
(583)
A
(38)
(79)
(59)
(59)
68.0
64.0
48.5
60.0
9.5
7.5
6.0
7.5
467
484
475
110
296
1.81
196
PF.
(136)
(128)
(97)
(120)
Ell
(19)
(15)
(12)
(15)
SE
(933)
(967)
(950)
Al
(219)
(591)
(362)
(391)
114
172
218
176
241
230
202
224
392
529
461
139
123
131
7
(227)
(344)
(435)
(352)
ES
(481)
(459)
(403)
(448)
FE
(784)
(1,057)
(921)
PE
(277)
(246)
(262)
Fntermedlate aeration
8
Primary clari.fier by-pass di.tch.
-------
TAHI.K 9
(Continued)
M i I I No
1.07
3
Average
I
2
3
Average
'I
Average
I
2
3
Average
457
Hi II
A
li
C
Mill
77.5
135.0
115.0
(155)
(270)
(229)
Mi I.I Locution Sampled
Color Load - Ki lograms/'i'liousand Kilograms (Pounds/Ton)
I)S CS
77
107
78
87
489
424
(IV.)
(213)
(156)
(174)
KE
(978)
(848)
39.0
60.0
54.5
51.0
(78)
(120)
(109)
(102)
413
536
518
489
ES
(826)
(1,072)
(1,037)
(978)
BA
36.5
57.5
44.5
46.0
(7.3)
(115)
(89)
(92)
BC
1 1.9
165
154
146
(238)
(329)
(308)
(292)
SE
305
23.1
311
282
(610)
(461)
(621)
(564)
3.5 (7)
1.0 (2)
0.5 (I)
NA
E
0
0.2
0.4
11.5
92.0
81.5
(0)
(0.4)
(0.7)
NA
109.0
(218)
(23)
(184)
(163)
61.5
(123)
34.5 (69)
2.0 (4)
NA
CD,.
~67I
0.1
0
(0.2)
(0.2)
(0)
NA
SI
319
334
438
364
(638)
(667)
(875)
(727)
52.5
69.0
73.5
73.0
11.0
1.5
(105)
(22)
(3)
NA
(138)
(147)
(146)
231
235
266
72.0
(144)
(461)
(470)
(532)
244
(488)
0.2
0.2
1.5
CD
42.0
86.0
62.5
63.5
(0.3)
(0.3)
(3 )
NA
10
(84)
(172)
(125)
(127)
llypochlori le plus caustic extract filtrate, Mill C.
Strong waste ponil effluent.
-------
I ID
I II
3
Avuraj
3.0
18.0
5. 5
9.0
(6)
(36)
(II)
(18)
167
213
204
(334)
(425)
(408)
195
(389)
6.5
5.0
5.0
5.5'
(13)
(10)
-_Ci°J_
(11)
14.5
30.5
-
22.5
161
192
183
179
3.5
5.5
4.5
4.5
Co l.o r
C
(29)
(61)
-
(45)
FE
(322)
(384)
(366)
(357)
CS
(7)
(11)
(9)
(9)
TAIil.K 9
(Continued)
MiJI. Location Sampled
Load - Kilograms/Thousand K:i l.ograms (Pounds/Ton)
99.5
226.0
75.5
133.5
69.0
87.5
47.0
68.0
E
(199)
(451)
(151)
(267)
EH
(138)
(175)
(94)
(136)
IMA
51
131
40
74
ES
60.5
121.0
127.0
102.5
PIB
(102)
(262)
(80)
(148)
(121)
(242)
(253)
(205)
98.0
216.0
83.5
132.5
359
207
231
266
(196)
(432)
(167)
(265)
PI
(718)
. (414)
(461)
(531)
140
305
182
209
280
235
246
254
• si
(279)
(609)
(363)
(417)
SI
(559)
(470)
(492)
(507)
250
271
T7JL
298
(499)
(542)
(745)
(595)
98.5
152.0
93. 5
114.5
(197)
(303)
(187)
(229)
US
48.5"
26.5
19.5
31.5
(97)
(53)
(39)
(63)
CH
4.5
11.0
5.0
7.0
(9)
(22)
(10)
(14)
26.0
31 .0
31.5
29.5
(52)
(62)
(63)
(59)
ES
70.5
70.0
66.0
65.5
(141)
(140)
(112)
(131)
2.5
5.0
4.0
4.0
HI!
(5)
(10)
(8)
(8)
PI.
PE
1
2
3
Average
184
255
349
263
(367)
(510)
(698)
(525)
182
233
257
227
(364)
(465)
(533)
(454)
232
318
303
284
(463)
(636)
(606)
(568)
-------
Ml I l_Jo
I 14
117
Day .if
Su rvey
1
•i
•)
Average
1
2
3
Average
1
2
3
Average
1
2
3
Average
r>
18.5
22.0
23.0
21.0
FK
401
359
279
346
CS
23.0
19.0
20.5
21.0
PaM
3.0
1.0
6.0
3.5
(37)
(44)
(A 6)
(A 2)
(HOI)
(718)
(557)
(692)
(A6)
(38)
(Al)
(A2)
(6)
(2)
(12)
(7)
C
22.0
20.5
22.0
21.5
ES
53.5
74.0
94. 0
7A.O
PL
75.5
65.5
70.0
70.5
Color
(AA)
(Al)
(AA)
(43)
(1.07)
(148)
(188)
(148)
(151)
(131)
(140)
(141)
TAHI.K 9
(Continued)
Mill Location Sampled
Load - Kilograms/Thousand Kilograms (Pounds/Ton)
64.0
72.5
58.5
65.0
13.5
31 .0
29.5
24.5
38.5
77.5
71.5
62.5
E
(128)
(1A5)
(117)
(130)
BS
(27)
(62)
(59)
(49)
PR
(77)
(155)
(143)
(125)
A
22.5
25.0
2A.O
2A.O
R6.K
3.0
0.5
1 .5
1.5
FE
147
138
160
148
(45)
(50)
(48)
(A8)
(f>)
(1)
(3)
(3)
(293)
(276)
(319)
(296)
PI
164
196
116
157
A
53.5
A5.5
A8.0
A9.0
12
-
-
0.05
0.05
(328)
(381)
(231)
(313)
(107)
(91)
(96)
(98)
-
-
(0.1)
(0.1)
SI
197 (39A)
223 (AA6)
171 (3A2)
197 (394)
11
0 0
0 0
0 0
0 0
13
-
-
14.0 (28)
.14.0 (28)
Kecaust it: i zing area.
12 .
Di guster concent:rate.
Kvaporator concentratt;
-------
TAIII.K y
(Continued)
Day D|"
Survey
3
Avu rage
Mill Locution Sampled
Color Load - Kilograms/Thousand Kilograms (Pounds/Ton)
c
3(>.0
1)8.0
37.5
37.0
(72)
(76)
(75)
(74)
74
139
57
90
1?
(148)
(277)
(114)
(180)
89
94
96
93
PI
(1.78)
(188)
(192)
(186)
108
1.30
107
115
SI
(216)
(259)
(214)
(230)
1 19
163
137
140
PE
(237)
(326)
(274)
(279)
0.3
0.5
0.5
0.4
14
(0.5)
(1.0)
(J.O)
(0.8)
3
Averse
3
Average
27.0
28.5
22.0
26.0
(54)
(57)
(44)
(52)
29.5
31.5
28.5
IIS
30.0
(59)
(63)
(57)
(60)
.17.5
1.8.0
10.0
15.0
CH
(35)
(36)
(20)
(30)
16.0
17.5
14.0
16.0
(32)
(35)
(28)
(32)
87.5
82.0
67.5
76.0
(175)
(1.64)
(135)
(158)
99.5
81.5
64.5
82.0
PE
(199)
(163)
(129)
(164)
15
No. 2 lagoon influent.
No. 2 lagoon decant.
45.0
50.0
45.0
(90)
(100)
(90)
46.5
(93)
I
2
3
Average
76.0
70.5
49.5
65.5
(152)
(141)
(99)
(131)
CS
39.0
38.5
31.5
36.5
(78)
(77)
(63)
(73)
ES
123.0
121 .0
94.5
114.5
(255)
(242)
(189)
(229)
18.0
53.5
24.5
32.0
(36)
(107)
(49)
(64)
47.5
90.5
47.0
61.5
Ell
(95)
(181)
(94)
(123)
105
126
118
116
(210)
(251)
(236)
(232)
I
2
3
Average
59.5
40.0
50.0
50.0
PE
(119)
(80)
(100)
(100)
236
217
190
215
SI
(472)
(434)
(380)
(429)
268
244
284
265
(535)
(487)
(567)
(530)
-------
TABLE 9
(CunLlniiutl)
Day of
Sn rvc
125
1
2
3
Average
1
9
3
Average
1
2
3
4
Average
1
2
3
4
Average
1
2
3
Average
]
2
3
Average
15.0
19.0
14.5
16.0
207
254
175
212
-
7.5
8.5
3.5
6.5
238
277
313
-
276
24.0
20.5
17.5
20.5
366
335
270
324
A
(30)
(38)
(29)
(32)
SK
(414)
(509)
(350)
(424)
n
-
(15)
(17)
(7)
(13)
SI
(476)
(554)
(626)
-
(552)
(48)
(41)
(35)
(41)
SE
(732)
(669)
(539)
(647)
Al
Mill Location Sampled
Color Load - Kilograms/Thousand Kilograms (Pounds/Ton)
267 (533)
132 (264)
210 (420)
203
(406)
FK
c
30.5
41.0
43.0
38.0
SE
211
206
237
218
CS
40.0
47.5
79.0
55.5
FE
405
378
347
376
(61)
(82)
(86)
(76)
(421)
(413)
(474)
(436)
(80)
(95)
(158)
(111)
(809)
(755)
(693)
(752)
8.0
8.0
1 .5
(16)
(16)
(3)
6.0
(12)
E
205 (4.10)
312 (623)
217 (434)
245
(489)
KE
255
275
251
(509)
(549)
(501)
260
(520)
ES
505 (1,010)
517 (1,033)
456 (911)
493
(985)
139
149
206
1.65
91
80
114
95
47.5
68.0
66.5
60.5
SI
(278)
(298)
(411)
(329)
257 (514)
398 (796)
282 (563)
312
(624)
Al
PE
(182)
(160)
(228)
114
209
(228)
(417)
(190)
167
(323)
151 (301)
186 (372)
155 (310)
164 (328)
PI
SI
(95)
(136)
(133)
(1-21)
600 (1,199)
243 (486)
188 (375)
403 (806)
358 (716)
315 (630)
344
(687)
359
(717)
-------
TAHI.K 9
(Con Li lined)
Mill No.
127
l=Mill I
2=MiI I 2
134
Hay
Su I'v
3
Average
3
Average
(2)
T2T
7.0
3.0
(14)
(ft)
(7)
(9)
19
-1.0 (2)
31.0 (62)
19.0 (38)
1.7.0 (3/0
(4)
(4)
(4)
(4)
I'M
107.5 (215)
111.5 (223)
93.0 (186)
Mill Location Sampled
Color Load - Kilograms/Thousand Kilograms (Pounds/Ton)
1 04.0
(208)
6
12
9
9
2.1 .
34.
26.
28.
234
361
296
297
50
42
34
42
1.05.
1.26.
85,
106.
n.,s
' (12)
(24)
(18)
(18)
AS
.0 (42)
.0 (68)
.0 (52)
.0 (56)
PI
(467)
(721)
(591)
(593)
CS
(100)
(84)
(68)
(84)
PI
.5 (211)
.5 (253)
.5 (171)
.0 (212)
C S
25.5
29.0
27.0
W
1.0
1.5
1.0
1.0
SI
333
401
374
369
KS
145
138
158
147
PE
116.5
94.5
88.0
99.5
(51)
(58)
(54)
(2)
(3)
(2)
(2)
(665)
(802)
(747)
(738)
(290)
(276)
(315)
(294)
(233)
(189)
(176)
(199)
C..S
7.0 '
20.0
7.5
11.5
16
7.5
8.5
4.5
7.0
FT.
348
406
359
371
Cll
16
23
12
17
I'K
85.5
75.5
67.5
76.0
(14)
(40)
(1.5)
(23)
(15)
(1.7)
(!»)
(14)
(695)
(81.2)
(718)
(742)
(32)
(46)
(24)
(34)
(171)
(151)
(135)
(152)
303
276
280
286
2.0
2.5
0.4
1.5
5.5
5.5
5.0
5.5
E S
(605)
(550)
(560)
(572)
17
(4)
(5)
(0.8)
(3)
EH
(11)
(11)
(10)
(11)
105
207
152
154
4.5
6.0
3.0
4.5
4.0
1.0
1.5
E0S
' (209)
(413)
(304)
(309)
18
(9)
(12)
(6)
(9)
PaM
(8)
(2)
(3)
No. ') riua I box s idu strc;im.
17
KIIOLS and slii ves.
1.8
1'ower house midillt; U-drain.
Power house south U-drain.
-------
TA11I.E 9
(Con tinned)
l):iy of
Sn rvey
3
Average
Average
I
2
3
Average
Mill Location Sampled
ilor Load - Kilograms/Thousand Kilograms (Pounds/Ton
1
2
3
Average
1
2
3
Average
78. 5
74.5
63.5
72.0
IT
146
159
1.69
1.58
1)11
10.0
16.0
14.0
13.5
1)
107
141
107
119
115
97
153
122
Al
200
193
196
196
(157)
(149)
(127)
(1.44)
(291)
(318)
(338)
(316)
(20)
(32)
(28)
(27)
(214)
(282)
(214)
(237)
(230)
(194)
(306)
(243)
(400)
(386)
(391)
(392)
14.5
.13.5
11.5
13.0
158
152
169
160
.12.0
17.5
14.5
14.5
21.5
13.0
15.5
16.5
26.5
30.0
28.0
24.5
12.5
20.5
19.0
A
(29)
(27)
(23)
(26)
PE
(315)
(303)
(338)
(319)
CH
(24)
(35)
(29)
(29)
C
(43)
(26)
(31)
(33)
cs
(53)
(60)
(56)
" (49)
(25)
(41)
(38)
ES-A2" ES-O
54.0
69.5
67.0
63.5
FE
1.19
137
132
129
EH
19.0
28.0
22.5
23.0
E
8.1.0
66.0
71.0
72.5
ES
104.0
67.0
80.0
83.5
A
13.0
17.5
24.5
18.5
(108)
(139)
(134)
(127)
(238)
(273)
(264)
(258)
(38)
(56)
(45)
(46)
(162)
(132)
(142)
(145)
(207)
(134)
(160)
(167)
(26)
(35)
(49)
(37)
36.5
24.5
25.5
29.0
I'T
74.5
104.0
96.5
9.1.5
I'T
180
225
162
189
1)11
92
73
103
89
!'l
(73)
(49)
(51)
(58)
(149)
(208)
(193)
(183)
(360)
(450)
(324)
(378)
(184)
(146)
(205)
(178)
1111
7.5
4.5
6.0
6.0
SI
84.5
116.0
90.0
96.5
PE
157
325
137
140
CH
19.5
11.5
24.0
18.5
RiE
(15)
(9)
(12)
(12)
(169)
(231)
(180)
(193)
(313)
(249)
(274)
(279)
(39)
(23)
(48)
(37)
6.0
1.5
3.8
74.5
99.5
76.0
83.5
126
170
147
148
30.0
2.1.0
29.5
27.0
(12)
(3)
(7.5)
SE
(149)
(199)
(152)
(167)
FE
(252)
(339)
(294)
(295)
EH
(60)
(42)
(59)
(54)
?.o,.
Caustic extract JMltr.-ite bleach J i nu A.
Cause ic extract I: i 1 crate bleach line H.
-------
Day of
Mill No. Survey
187 1
2
3
AVCI.IKI;
1
9
3
Average
37.5
28.5
27.0
31.0
234
205
204
214
Cll
(75)
(57)
(54)
(62)
(468)
(409)
(408)
(428)
87
1 II
105
101
Co lor
KH
(174)
(222)
(210)
(202)
TABLE y
(Continued)
Mill Location Sampled
Load - Ki lo^rams/Thousand Kilograms (Pounds/Ton)
W
4.5 (9) 22.
76.
2.0 (4) 23
3.3 (6.5) 40.
R&E
.0
.5
.5
.5
(44)
(153)
(47)
(81)
101
162
189
151
PI
(201)
(324)
(378)
(301)
220
230
200
216
SI
(440)
(460)
(400)
(433)
-------
pulp production (3, 4, 5). The main reason for this suggested change was
that it would more accurately reflect the color load from a mill.
Previous studies have concluded that the pulping and bleaching processes
are responsible for the largest percentage of the color contributed to a
bleached kraft pulp and paper mill's total wastewater. Using the bleach
plant production would eliminate inaccuracies caused at mills which
utilize large amounts of fillers, purchased pulp, and/or other types of
pulp in the manufacture of their finished product. For these reasons
the determination of color load in kg/kkg (Ibs/ton) of production was
based on the bleach plant production. For those mills which utilize
separate bleach plants for hardwood and softwood the determination of
color load for sample locations within these separate bleach plants
utilized only the production for that bleach plant (i.e., softwood
production only is used to calculate color load in the softwood bleach
plant). The results of the color load determinations in kilograms per
thousand kilograms (pounds per ton) for each sample location on each
day, as well as the three-day average for each sample location are shown
on Table 9. Refer to Table 6 for the letter code identifications used
for the sample locations.
F. BLEACHED KRAFT MILL COLOR ORIGIN
Several treatment technologies which have been proposed by researchers
for the reduction of color in bleached kraft pulp and paper mill ef-
fluents are for treatment of the first stage caustic extraction filtrate
and/or the total bleach plant process wastewater stream only. The basis
for this was the assumption that a large portion of the color load from
111-66
-------
a bleached kraft mill originates in the bleach plant, and that it is
less expensive to treat these highly colored streams utilizing specific
treatment technologies.
Therefore, the percent color at the various sample locations within a
mill's process based upon the total color load at the treatment system
was determined. This was done to determine if the percent color re-
duction, which has been claimed by the manufacturers of these tech-
nologies, would reduce the color load enough to meet the proposed BATEA
limitations.
Prior to the calculation of the percent color at sample locations within
a mill's process, it was necessary to select the total mill color load
at a location in the treatment system which would provide the most
accurate total color load from each mill for the period of the survey.
The total color load at the final effluent was eliminated because in
twenty-two of the twenty-six mills surveyed, detention times were great-
er than the 3-day survey period and therefore would not reflect any
changes in wastewater characteristics caused by process changes which
might have occurred during the survey period. In many of the mills the
acid portion of the mill's wastewater stream bypasses the primary clar-
ifier and combines with the remainder of the mill's wastewater at the
influent to the secondary treatment system. The time for the wastewater
to flow from its source within the individual mill processes to the
influent to the secondary treatment system was normally a relatively
short time period. Therefore, changes within a process which would
affect the color level from the mill would normally be reflected at the
111-67
-------
secondary treatment system influent within a few hours. Additionally,
selection of a sample location at the influent to the secondary treat-
ment system eliminated any possible color increases or decreases that
might occur through the secondary treatment system and any holding
lagoons which might be utilized by a mill. It should be noted that
because of the short duration of the color surveys (3 days) at each mill
it could not be determined if any color increases due to detention time
in earthen lagoons had occurred. For the preceding reasons the influent
to the secondary treatment system was used as the location for estab-
lishing total mill color loads and for determining the percent color at.
each sample location.
Figures 18 through 43 are block diagrams of the basic sewer system
utilized to transport wastewater to the treatment system for each mill.
The color load identified, in kilograms (pounds) per day, along with the
percent of the total color for the sample locations indicated are shown
for each of the 26 mills surveyed.
The accuracy of the color origin determinations depends upon the proper
sampling and analysis procedures in the field, as well as the method of
flow rate determination at each sample location. The flow rate is used
in calculating the color load in kilograms (pounds) per day. Attempts
were made to utilize the most accurate method available for determining
flow rates. In some instances it was necessary to utilize estimates of
the flow rate as provided by mill personnel. These estimates of flow
were often based on average mill experience or on pumping performance
111-68
-------
FIGURE 18
COLOR SOURCES, LOAD (4*/DAY)t AND %
MILL NUMBER IOO
OF TOTAL COLOR
PULP MILL
38,490
(84,780)
22%
SCREEN ROOM
OR
DECKER
BLEACH PLANT
Acid
Caustic
2,688
(5,920)
2%
PAPER MILL
1
llogram per day units appear
above English units.
WOODYARD
CAUSTICIZING
RECOVERY & EVAPORATOR
PRIMARY
TREATMENT
131,551
(289,760)
77%
ACID SEWER
28,870
(63,590)
17%
CHEMICAL AREA
TOTAL COLOR
@
SECONDARY
INFLUENT
171,840
(378,500)
ASH POND AND SLUDGE
LAGOON DECANT
1,998
(4,400)
1%
111-69
-------
FIGURE 19
COLOR SOURCES, LOAD (*t/DAY),* AND % OF TOTAL COLOR
MILL NUMBER IOI
PULP MILL
60,780
(133,880)
48%
-»T*
SCREEN ROOM
OR
DECKER
BLEACH PLANT
1st Cl2
11,310
(24,920)
9%
1st Caustic
71,840
(158,240)
56%
PAPER MACHINES
AND
PULP DRYER
I
WOODYARD
Jilogram per day units appear
above English units.
*=Hrimary Influent plus Acid
Wewer.
PRIMARY
TREATMENT
102,700
(226,210)
80%
EVAPORATORS
ACID SEWER
25,120
(55,320)
20%
CHEMICAL AREA,
LIME KILN, AND
RECOVERY
1,150
(2,530)
1%
TOTAL COLOR @
SECONDARY
INFLUENT**
127,810
(281,530)
111-70
-------
FIGURE 20
COLOR SOURCES, LOAD (4t/DAY),* AND % OF TOTAL COLOR
MILL NUMBER IO2
DIGESTERS
DECKER
6,120
(13,470)
8%
BLEACH PLANT
61,000
(134,370)
81%
PAPER MILL
*Kilograms per day units
appear above English units.
**Secondary Influent was
assumed to be primary
effluent, bleach plant,
and woodyard.
_S\_
WOODYARD
640
(1,400)
1%
RECOVERY AND
CAUSTICIZING
PRIMARY
TREATMENT
13,370
(29,440)
18%
TOTAL COLOR @
SECONDARY
INFLUENT**
75,010
(165,210)
111-71
-------
FIGURE 21
COLOR SOURCES, LOAD (#/DAY),* AND % OF TOTAL COLOR
MILL NUMBER IO3
DIGESTERS
DECKER
31,630
(69,660)
42%
BLEACH PLANT
Acid
28,200
(62,110)
38%
Caustic
PAPER MILL
460
(1,020)
1%
*Kilogram per day units
appear above English units.
^Secondary Influent was the
sum of the Primary Effluent
plus the Bleach Plant Sewer,
_S\_
PRIMARY
TREATMENT
26,500
(58,400)
35%
WOODYARD
RECOVERY &
EVAPORATOR
14,690
(32,360)
20%
PULP DRYER
TOTAL COLOR @
SECONDARY
INFLUENT**
74,990
(165,170)
111-72
-------
FIGURE 22
COLOR SOURCES, LOAD (#/ DAY),* AND % OF TOTAL COLOR
MILL NUMBER IO5
DIGESTERS &
WASHERS
DECKER
Softwood
5,620
(12,370)
2%
Hardwood
8,540
(18,820)
4%
BLEACH PLANTS
1st C12
Softwood
8,560
(18,850)
4%
Hardwood
4,390
(9,680)
2%
BLEACH PLANTS
1st Caustic
Softwood
95,280
(209,860)
41%
Hardwood
2,900
(6,380)
1%
WOODYARD
5,970
(13,160)
3%
Kilogram per day units
appear above English units,
PRIMARY
TREATMENT
153,260
(337,570)
67%
RECOVERY & EVAPORATOR
PAPER MILL
ACID SEWER
95,830
(211,080)
42%
TOTAL COLOR @
SECONDARY
INFLUENT
230,110
(506,850)
111-73
-------
FIGURE 23
COLOR SOURCES, LOAD (4*/DAY),* AND % OF TOTAL COLOR
MILL NUMBER IO6
DIGESTERS
DECKER
30,120
(66,340)
24%
BLEACH PLANT
1st Cl2
16,730
(36,860)
13%
1st Caustic
70,020
(154,220)
55%
PAPER MILL &
PULP DRYER
Kilogram per day units
appear above English units.
WOODYARD
EVAPORATORS
CAUSTICIZING &
LIME RECOVERY
CAUSTIC SEWER
78,470
(172,850)
62%
ACID SEWER
11,760
(25,910)
9%
POWER HOUSE
PRIMARY
TREATMENT
53,710
(118,310)
42%
i'
TOTAL COLOR @
SECONDARY
INFLUENT
127,360
(280,520)
111-74
-------
FIGURE 24-
COLOR SOURCES, LOAD (#/DAY),*AND % OF TOTAL COLOR
MILL NUMBER IO7
DIGESTER
DECKER
12,830
(28,270)
31%
BLEACH PLANT
1st Cl2**
7,450
(16,420)
1st Caustic**
71,360
.(157,180)
PAPER MILL
^Kilogram per day units ]
appear above English units.
§A portion of the 1st stage
Cl2 and caustic filtrates are
sent to odor abatement
facilities.
*B:Secondary influent was
• assumed to be effluent from
ASB#1 (Detention Time 1.4
days).
WOQDYARD
(Purchased Chips)
RECOVERY
CAUSTIC SEWER
21,310
(46,930)
52%
ACID SEWER
6,770
(14,910)
16%
PRIMARY
TREATMENT
TOTAL COLOR @
SECONDARY
INFLUENT***
41,060
(90,450)
111-75
-------
FIGURE 25
COLOR SOURCES, LOAD (^/DAY),*AND % OF TOTAL COLOR
MILL NUMBER IO8
DIGESTER & WASHING
SCREEN ROOM
BLEACH PLANT
121,760
(268,190)
30%
PULP DRYER
*Kilogram per day units
appear above English unit.
WOODYARD
EVAPORATOR & RECOVERY
STRONG LIQUOR LAGOON
71,260
(156,970)
18%
CAUSTICIZING &
LIME RECOVERY
3-3
PRIMARY
TREATMENT
106,820
(235,280)
26%
CHEMICAL AREA
TOTAL COLOR @
SECONDARY
INFLUENT
403,400
(888,550)
111-76
-------
FIGURE 26
COLOR SOURCES, LOAD (4t/DAY),*AND % OF TOTAL COLOR
MILL NUMBER MO
PULP MILL
DECKER
5,230
(11,520)
4%
BLEACH PLANT
1st C12
13,480
(29,700)
11%
1st Caustic
80,590
(177,500)
64%
PAPER MILL
EVAPORATORS & RECOVERY
CAUSTICIZING &
LIME
kilogram per day units
appear above English units.
PRIMARY
TREATMENT
124,590
(274,430)
98%
COLOR TOTAL @
SECONDARY
INFLUENT
126,740
(279,170)
111-77
-------
FIGURE 27
COLOR SOURCES, LOAD (#/DAY),*AND % OF TOTAL COLOR
MILL NUMBER III
PULP MILL
Softwood
Hardwood
BLEACH PLANT
1st Cl?
Softwood
1,370
(3,010)
1%
Hardwood
990
(2,170)
1%
BLEACH PLANT
1st Caustic
Softwood
31,830
(70,100)
26%
Hardwood
12,630
(27,820)
10%
PAPER MILL
RECOVERY
^Kilogram per day units
appear above English units.
PRIMARY
TREATMENT
129,880
(286,080)
106%
TOTAL COLOR @
SECONDARY
INFLUENT
122,890
(270,690)
111-78
-------
FIGURE 28
COLOR SOURCES, LOAD (#/DAY),*AND % OF TOTAL COLOR
MILL NUMBER 113
DECKER
Softwood
14,920
(32,870)
7%
Hardwood
49,330
(108,660)
24%
BLEACH PLANT
1st C12
Softwood
13,870
(30,550)
7%
Hardwood
2,820
(6,220)
1%
BLEACH PLANT
1st Caustic
Softwood
30,940
(68,140)
15%
1st Hypo
Hardwood
1,650
(3,640)
1%
PAPER MILL
AND
PULP DRYER
WOODYARD
DIGESTER
RECOVERY
AND
CAUSTICIZING
*Kilogram per day appear
above English units.
PRIMARY
TREATMENT
242,050
(533,140)
115%
TOTAL COLOR @
SECONDARY
INFLUENT
209,030
(460,420)
111-79
-------
FIGURE 29
COLOR SOURCES, LOAD (#/DAY),*AND % OF TOTAL COLOR
MILL NUMBER 114-
PULP MILL
DECKER
14,940
(32,900)
11%
BLEACH PLANT
1st Cl?
15,050
(33,150)
11%
1st Caustic
45,340
(99,860)
33%
RECOVERY
*Kilogram per day units
appear above English units.
PRIMARY
TREATMENT
109,120
(240,350)
79%
CAUSTICIZING
AND
LIME
ACID SEWER
16,650
(36,670)
12%
TOTAL COLOR @
SECONDARY
INFLUENT
137,360
(302,550)
111-80
-------
FIGURE 3O
COLOR SOURCES, LOAD (#/ DAY),* AND % OF TOTAL COLOR
MILL NUMBER 117
DIGESTERS,
WASHERS. AND SCREENS
BLEACH PLANT
1st Cl?
6,440
(14,190)
18%
1st Caustic**
22,730
(50,070)
66%
PULP DRYER
PAPER MILL
1,050
(2,310)
3%
EVAPORATORS AND
RECOVERY
530
(1,170)
2%
BLEACH FILTRATES
7,590
(16,710)
22%
RECAUSTICIZING AND
LIME RECOVERY
Negligible
'wLlogram per day units appear
above English units.
**"ypochlorite is added to the
tustic filtrate being
Sewered for color reduction.
**S_econdary influent was the sum
the Primary Effluent and
.d Sewer.
PRIMARY
TREATMENT
21,650
(47,690)
63%
ACID SEWER
15,010
(33,060)
44%
TOTAL COLOR @
SECONDARY
INFLUENT***
34,200
(75,330)
111-81
-------
FIGURE 31
COLOR SOURCES, LOAD (4*/DAY), AND % OF TOTAL COLOR
MILL NUMBER IIS
PULP MILL
540
(1,180)
3%
DECKER
BLEACH PLANT
1st Cl?
5,580
(12,280)
32%
1st Caustic
12,590
(27,740)
72%
PAPER MILL
WOODYARD
RECOVERY
I
ilogram per day units appear
above English units.
econdary Influent was the sum
f the Primary Effluent and
No. 2 Lagoon Decant.
PRIMARY
TREATMENT
13,950
(30,720)
82%
TOTAL COLOR@
SECONDARY
INFLUENT**
17,480
(38,510)
111-82
-------
FIGURE 32
COLOR SOURCES, LOAD (#/ DAY),* AND % OF TOTAL CQLOR
MILL NUMBER 119
BATCH DIGESTERS
BLEACH PLANT
1st Cl2
Softwood
5,250
(11,560)
13%
Hardwood
4,240
(9,350)
11%
BLEACH PLANT
1st Hypo
Softwood
6,010
(13,240)
15%
Hardwood
4,440
(9,780)
11%
PAPER MILL
I
CIO2 GENERATING
PLANT
CAUSTICIZING
AREA
ilogram per day units appear
English units.
PRIMARY
TREATMENT
38,040
(83,790)
97%
TOTAL COLOR @
SECONDARY
INFLUENT
39,400
(86,790)
111-83
-------
FIGURE ^33
COLOR SOURCES, LOAD (#/DAY),*AND % OF TOTAL COLOR
MILL NUMBER 121
PULP MILL
SCREEN ROOM
72,990
(160,780)
31%
BLEACH PLANTS
1st Cl2
Softwood
22,740
(50,090)
9%
Hardwood
15,820
(34,840)
7%
BLEACH PLANTS
1st Caustic
Softwood
71,700
(157,930)
30%
Hardwood
30,390
(66,930)
13%
kilogram per day units appear
above English units.
PAPER MILL
RECOVERY
BLEACH PLANT
129,190
(284,570)
54%
PRIMARY
TREATMENT
55,090
(121,340)
23%
TOTAL COLOR
SECONDARY
INFLUENT
238,810
(526,010)
111-84
-------
FIGURE 34
COLOR SOURCES, LOAD (4t/DAY),*AND % OF TOTAL COLOR
MILL NUMBER 122
PULP MILL
BLEACH PLANT
Acid
9,670
(21,290)
5%
Caustic
122,370
(269,530)
66%
PAPER MILL
kilogram per day units appear
above English units.
PRIMARY
TREATMENT
97,020
(213,710)
52%
WOODWASH
EVAPORATOR
3,670
(8,080)
2%
CAUSTICIZING
TOTAL COLOR @
SECONDARY
INFLUENT
186,190
(410,120)
111-85
-------
FIGURE 35
COLOR SOURCES, LOAD (4t/DAY),*AND % OF TOTAL COLOR
MILL NUMBER 125
DIGESTERS AND
WASHING
BLEACH PLANT
1st Cl?
33,180
(73,080)
14%
1st Caustic
213,300
(469,820)
87%
WOODYARD
139,420
(307,090)
54%
*wLlogram per day units appear
above English units.
CAUSTICIZING
PAPER MILL
ALKALINE SEWER
83,920
(184,840)
34%
SCREEN ROOM
PRIMARY
TREATMENT
142,230
(313,280)
58%
TOTAL COLOR @
SECONDARY
INFLUENT
244,110
(537,690)
111-86
-------
FIGURE 36
COLOR SOURCES, LOAD (#/DAY),*AND % OF TOTAL COLOR
MILL NUMBER 126
PULP MILL
DECKER
9,420
(20,750)
6%
BLEACH PLANT
1st Cl
25,63(
(56,460)
16%
1st Caustic
225,170
(495,980)
138%
I
Kilogram per day units
appear above English units.
WOODYARD
RECOVERY
ACID SEWER
28,030
(61,740)
17%
PRIMARY
TREATMENT
152,440
(335,770)
93%
TOTAL COLOR @
SECONDARY
INFLUENT
163,310
(359,710)
111-87
-------
FIGURE 37
COLOR SOURCES, LOAD (4*/DAY),* AND % OF TOTAL COLOR
MILL NUMBER 127
PULP MILL
2%
DECKER
Mill #1
Negligible
Mill n
1%
BLEACH PLANT
1st Cl?
Mill #1
Mill 92
1%
BLEACH PLANT
1st Caustic
Mill #1
39%
Mill 92
20%
«ill requested color load
(///day) be kept confidential.
WOODYARD
Negligible
CAUSTICIZING
EVAPORATOR
1%
ACID SEWER
7%
PRIMARY
TREATMENT
80%
POWER HOUSE
6%
TOTAL COLOR @
SECONDARY
INFLUENT
111-88
-------
FIGURE 38
COLOR SOURCES, LOAD (#/DAY),*AND % OF TOTAL COLOR
MILL NUMBER 134-
SCREEN ROOM
1,160
(2,560)
2%
*r*-
BLEACH PLANT
1st Cl2
Softwood
8,650
(19,060)
15%
Hardwood
6,480
(14,280)
11%
BLEACH PLANT
1st Caustic
Softwood
30,720
(67,660)
52%
Hardwood
2,070
(4,550)
4%
PAPER MILL
1,490
(3,290)
3%
^Kilogram per day units
appear above English units.
RECOVERY
PRIMARY
TREATMENT
62,860
(138,450)
107%
TOTAL COLOR @
SECONDARY
INFLUENT
59,010
(129,970)
111-89
-------
FIGURE 39
COLOR SOURCES, LOAD (#/DAY),*AND % OF TOTAL COLOR
MILL NUMBER 136
DECKER FILTRATES
COLLECTION TANK
91,140
(200,740)
45%
BLEACH PLANTS
1st Cl2 Collection
Tank
16,670
(36,720)
8%
BLEACH PLANTS
1st Caustic
A-Pine
48,170
(106,100)
24%
C-Pine
21,860
(48,160)
11%
BLEACH PLANT
1st Hypochlorite
3,030
(6,680)
2%
I
ilogram per day units
ppear above English units.
EVAPORATORS AND
RECOVERY
4,930
(10,860)
2%
PAPER MILL
PRIMARY
TREATMENT
199,460
(439,330)
99%
TOTAL COLOR @
SECONDARY
INFLUENT
201,270
(443,330)
111-90
-------
FIGURE 40
COLOR SOURCES, LOAD (4t/DAY),*AND % OF TOTAL COLOR
MILL NUMBER I4O
SCREEN ROOM AND
DECKER
4,180
(9,210)
14%
BLEACH PLANT
1st Cl?
4,590
(10,110)
15%
1st Caustic
7,290
(16,050)
24%
PULP CLEANERS
AND PULP MACHINE
EVAPORATORS
''Kilogram per day units appear
above English units.
PRIMARY
TREATMENT
28,760
(63,350)
95%
TOTAL COLOR @
SECONDARY
INFLUENT
30,300
(66,740)
111-91
-------
FIGURE 4-1
COLOR SOURCES, LOAD (4*/DAY),*AND % OF TOTAL COLOR
MILL NUMBER 152
SCREEN ROOM
DECKER
30,450
(67,070)
63%
BLEACH PLANT
1st Cl2
4,530
(9,970)
9%
1st Caustic
19,340
(42,600)
40%
PAPER MILL
^ilgoram per day units appear
above English units.
trimary influent was used to
alculate the percent color of
rocess sample locations
because flow was recorder at
Bhat location.
PRIMARY
TREATMENT**
48,660
(107,180)
TOTAL COLOR @
SECONDARY
INFLUENT
111-92
-------
FIGURE 42
COLOR SOURCES, LOAD (4*/DAY),* AND % OF TOTAL CQLOR
MILL NUMBER 161
DIGESTERS
DECKERS
Softwood
45,260
(99,700)
24%
Hardwood
39,880
(87,850)
21%
BLEACH PLANTS
1st C12
Softwood
11,310
(24,910)
6%
Hardwood
8,190
(18,040)
4%
BLEACH PLANTS
1st Caustic
Softwood
30,140
(66,390)
16%
Hardwood
12,040
(26,510)
6%
kilogram per day units
Appear above English units.
icondary Influent.
EVAPORATORS
ALKALINE SEWER
15,300
(33,710)
8%
PAPER MILL
INFLUENT TO
PRIMARY CLARIFIER
175,240
(386,000)
92%
111-93
CAUSTICIZING
CHEMICAL AREA
INFLUENT TO
POND //4
15,330
(33,760)
8%
190,570**
(419,760)
-------
FIGURE 43
COLOR SOURCES, LOAD (4t/DAY)f* AND % OF TOTAL COLOR
MILL NUMBER 187
DIGESTER AND SCREEN
AREA
BLEACH PLANT
1st Cl?
21,470
(47,890)
14%
1st Caustic
71,610
(157,730)
47%
PULP MACHINE
WOODYARD
2,160
(4,760)
1%
RECOVERY AND
EVAPORATOR
29,200
(64,320)
19%
Kilogram per day units
appear above English units.
PRIMARY
TREATMENT
107,540
(236,870)
70%
CAUSTIC PLANT
TOTAL COLOR @
SECONDARY
INFLUENT .
152,850
(336,680)
111-94
-------
data. Table 8, showing the color load determination in thousand kilo-
grams (pounds) per day, lists each sample location with a footnote
signifying the method of flow determination used during the color sur-
vey. Each sample location's flow rate was determined through one of the
four methods indicated:
1. flow was continuously recorded using mill flow recorders,
2. flow was measured at a parshall flume by the sampling team
when each sample was taken and the daily flow rate was cal-
culated,
3. mill personnel provided estimated flow rates, and/or
4. mill personnel provided calculated flow rate based on pro-
duction levels or measurements by the mill personnel.
Most of the mill surveys required at least two of the four methods of
flow rate determination. Many of the estimated flow rates were at
sample locations in the bleach plant or pulping area. Therefore, the
accuracy of the color load and the color origin determinations shown on
Figures 18 through 43, for each sample location, will depend upon the
exact method used to determine the flow rate at the location. However,
despite the possible inaccuracies introduced by estimated flows, the
determination of color origin does provide a general indication of the
sources of color within a mill.
111-95
-------
The first analysis performed utilizing the color origin determination
was to evaluate the total percent color level identified by source at
each mill. Figures 18 through 43 provide the sample locations used
during^the color survey, as well as those areas in the mill that were
not sampled but do discharge to the wastewater treatment system. Table
10 summarizes the total color load at the secondary treatment influent,
the cumulative color load identified by source, and the percent of the
total color load that these identified sources represent for each mill
surveyed.
Seven of the 26 mills had 90 to 110 percent of the total color iden-
tified by source, while 12 of the 26 mills had 80 to 120 percent.
Twenty of the 26 mills were in a range from 70 to 125 percent of the
total color identified by source. The remaining six mills were in a
range from 38 to 56 percent. Mills, which have greater than 100 percent
of the color accounted for, resulted because estimated sewer flows had
to be used on many of the process sewers. The accuracy of the estimates
varied and a precise calculation of the actual color load at the sample
location was not possible.
When the possible inaccuracies which arise from estimated flows are
taken into account, the percent of the total color identified by source
was concluded to have been generally good, except for the six mills
mentioned above (mills 100, 111, 113, 114, 119, and 140).
The second analysis performed was to determine the major sources of
color from the twenty-six mills. The color data from the 20 mills which
were in the range of 70 to 125 percent of the color load identified by
source, indicated that the major source of color is the bleach plant.
111-96
-------
TABLE 10
PERCENT OF TOTAL COLOR IDENTIFIED BY SOURCE
Mill
Number
100
101
102
103
105
106
107
108
110
111
113
114
117
118
119
121
122
125
126
127
134
136
140
152
161
187
Total Color @
Secondary Treatment Influent
kg/day (Ib/day) '
171,840
127,810
75,010
74,990
230,110
127,360
41,060
403,400
126,740
122,890
209,030
137,360
34,200
17,480
39,400
238,810
186,190
244,110
163,310
-
59,010
201,270
30,300
48,660
190,570
152,850
(378,500)
(281,530)
(165,210)
(165,170)
(506,850)
(280,520)
( 90,450)
(888,550)
(279,170)
(270,690)
(460,420)
(302,550)
( 75,330)
( 38,510)
( 86,790)
(526,010)
(410,120)
(537,690)
(359,710)
-
(129,970)
(443,330)
( 66,740)
(107,180)
(419,760)
(336,680)
Color Load Percent of
Identified By Source Total Color
kg /day (Ib/day)
72,050
157,740
67,750
74,980
214,140
120,360
40,910
299,840
99,300
46,810
113,540
76,920
24,180
18,700
19,940
184,280
135,700
175,410
180,470
-
50,580
185,800
16,060
54,320
157,960
124,710
(158,690)
(347,440)
(149,240)
(165,150)
(471,670)
(265,100)
( 90,110) '
(660,440)
(218,720)
(103,100)
(250,080)
(169,430)
( 53,250)
( 41,200)
( 43,930)
(405,910)
(298,900)
(386,360)
(397,510)
-
(111,400)
(409,260)
( 35,370)
(119,640)
(347,920)
(274,700)
42
124
90
100
93
95
100
74
78
38
54
56
71
107
51
77
73
72
111
77
86
92
53
112
83
82
111-97
-------
Fourteen of these 20 mills had at least 50 percent of their total color
load at the secondary treatment influent contributed by the bleaching
process. The average for these 14 mills was 76 percent. The other six
mills were in a range from 30 to 49 percent of the total color to the
wastewater treatment system contributed by the bleaching process. The
average for these six mills was 40 percent.
The six mills which had less than 70 percent of their total color iden-
tified by source had an average color contribution from their bleaching
process of approximately 36 percent. The average color contribution
from the bleaching process for all 26 mills was 59 percent. Approx-
imately 45 percent was contributed by the first stage caustic extract
filtrate from the bleaching process.
The second largest color source identified at the 26 mills was the
screen room or decker filtrate. Sixteen mills were sampled at this
process location. The average percent of the total color load con-
tributed by the screen room or decker filtrate at these 16 mills was
approximately \24\percent. Mill 152 (soda mill) had 63 percent of its
total color load contributed by the decker filtrate. Mills 103, 107,
113, 121, 136, and 161 had 42, 3,1, 31, 31, 45, and 45 percent of their
total color load contributed by the screen room or decker filtrate,
respectively.
The pulping, bleaching, and evaporator and recovery processes were
responsible for an average of approximately 79 percent of the total
color load at the 26 mills surveyed. Eighteen of the 26 mills surveyed
111-98
-------
had 70 percent or more of their total color load contributed by these
processes with an average of approximately 90 percent.
The preceding evaluations are utilized in Sections V and VI to provide a
basis for selection of a BATEA color control technology, and to es-
tablish updated BATEA effluent color limitations.
G. DATA COMPARISON BY SUBCATEGORY AND WOOD SPECIE
The 26 mills surveyed were separated into their respective subcategories
to determine if a correlation existed between mill subcategory (product
manufactured) and the resulting color load to the mill's wastewater
treatment system. The color load at the influent to the secondary
treatment system based upon the bleach plant production was used to make
the comparison. Also included in each comparison was the proportion of
softwood used during the color survey, the bleaching sequence, and the
flow in kiloliters per thousand kilograms, kl/kkg (thousands of gallons
per ton, kgal/ton) of bleach plant production. An average color load
and flow per ton of bleach plant production was also calculated for each
subcategory.
1. Fine Kraft Subcategory
Four bleached kraft mills in the fine kraft subcategory were visited
during the color survey project. Three of the mills were located in the
Northeastern section of the United States and one in the South.
111-99
-------
The proportion of softwood pulp bleached at these four mills ranged from
25 to 60 percent of their total bleached pulp. The average color load
ranged from a high at Mill 136 of 159.5 kg/kkg (319 Ibs/ton) to a low of
82 kg/kkg (164 Ibs/ton) at Mill 119. The average color load for the
four mills was 114 kg/kkg (228 Ibs/ton).
Table 11 shows the results of the comparison for the four mills in the
fine kraft subcategory.
TABLE 11
COLOR LOAD AT SECONDARY TREATMENT INFLUENT - FINE KRAFT
Mill
No.
118
119
134
136
Day of Percent
Survey Softwood
1
2
3
Average
1
2
3
Average
1
2
3
Average
1
2
3
Average
25
25
25
25
42
42
42
42
34
37
34
35
58
61
61
60
Color Load
kg/kkg (Ibs/ton)
108.0
129.5
107.0
115.0
99.5
81.5
64.5
82.0
116.5
94.5
88.0
99.5
157.5
151.5
169.0
159.5
(216)
(259)
(214)
(230)
(199)
(163)
(129)
(164)
(233)
(189)
(176)
(199)
(315)
(303)
(338)
(319)
Bleaching Flow
Sequence kl/kkg (kgal/ton)
CEHD 112.6 (27.0)
122.2 (29.3)
99.7 (23.9)
111.5
CH H D 88.0
L l 92.6
93.4
91.3
CEDE-^ 157.6
CEH— ' 145.1
129.3
144.0
CEHED 148.5
CEHDH 150.1
CHEHD 155.0
151.2
(26.7)
(21.1)
(22.2)
(22.4)
(22.2)
(37.8)
(34.8)
(31.0)
(34.5)
(35.6)
(36.0)
(37.2)
(36.3)
Subcategory Average
114.0
(228)
125.0
(29.9)
The wood specie bleached and bleaching sequence appeared to have played
a role in the amount of color resulting at the secondary influent for
III-100
-------
the fine kraft subcategory mills. Mill 136 had the highest color load
at the secondary treatment influent, and also the highest percentage of
softwood pulp bleached. Mill 119 had the lowest color load, but it did
not have the lowest percentage of softwood pulp bleached. However, it
should be noted that the bleaching sequence at Mill 119 was CH H_D.
The hypochlorite second stage of this bleaching sequence results in a
lower color level over those experienced at the other three mills in the
fine kraft subcategory, which utilize caustic for lignin extraction in
the second bleaching stage. The hypochlorite is known for its color
reduction capabilities, and some of the mills surveyed were utilizing
hypochlorite second stage bleaching for this purpose. Mill 117 used a
CEHH bleaching sequence; however, hypochlorite was added to the sewered
caustic extraction filtrate, for the purpose of color reduction (5a).
2. Fine and Market Kraft Mills
Five bleached kraft mills producing fine paper and market pulp were
surveyed. Three of the mills were located in the South, one in the Mid-
west, and one on the West Coast.
The average amount of softwood pulp bleached during the color survey at
the five mills ranged from 30 to 100 percent of the total, while the
average color load ranged from 176 to 320 kg/kkg (352 to 640 Ibs/ton) of
bleach plant production. The average color load for the fine and market
kraft mills surveyed was 235 kg/kkg (470 Ibs/ton). Table 12 shows the
comparison for the five bleached kraft fine and market kraft mills which
III-101
-------
were surveyed.
TABLE 12
COLOR LOAD AT SECONDARY TREATMENT INFLUENT-
FINE AND MARKET KRAFT
Mill Day of Percent
No. Survey Softwood
Color Load
kg/kkg (Ibs/ton)
101
103
106
107
110
1
2
3
Average
1
2
3
Average
1
2
3
Average
1
2
3
Average
1
2
3
Average
11
3
65_
40
0
68
12
31
41
100
39
60
100
100
100
100
17
79
_0
30
180.0
152.0
235.5
189.0
138,
172.
Average
217.5
176.0
289.5
359.5
310.5
320.0
305.0
230.5
310.5
282.0
139.5
304.5
181.5
208.5
235.0
(360)
(304)
(471)
(378)
(277)
(344)
(435)
(352)
(579)
(719)
(621)
(640)
(610)
(461)
(621)
(564)
(279)
(609)
(363)
(417)
(470)
Bleaching
Sequence
CEHDH
Flow
kl/kkg (kgal/ton)
CEHED
CEDED
CEDHD
CEDED
125.5
152.2
135.5
137.7
130.9
128.0
162.2
140.4
274.0
254.8
265.2
264.7
279.4
281.1
341.1
300.5
164.3
205.6
174.3
181.4
205.6
(30.1)
(36.5)
(32.5)
(33.0)
(31.4)
(30.7)
(38.9)
(33.7)
(65.7)
(61.1)
(63.6)
(63.5)
(67.0)
(67.4)
(81.8)
(72.1)
(39.4)
(49.3)
(41.8)
(43.5)
(49.2)
All five mills utilized a chlorination first stage and a caustic extrac-
tion second stage in their bleaching sequence. Mills 106 and 107 had
the highest color loads at 320 and 232 kg/kkg (640 and 564 Ibs/ton),
respectively. These two mills also bleached a higher percentage of
softwood pulp than Mills 101, 103, and 110. Mill 106 bleached 60 percent
III-102
-------
softwood while Mill 107 bleached 100 percent softwood pulp during the
color survey.
3. Market Kraft Subcategory
Four market kraft mills were surveyed, three in the South and one in the
Midwest. All four mills bleached pulp with a chlorination and caustic
extract as the first two stages of their bleaching sequences. There was
a considerable range in the color load at the secondary treatment in-
fluent at these four mills. Mill 140, located in the Midwest, had the
lowest average color load at 96.5 kg/kkg (193 Ibs/ton), while Mill 126
had the highest average color load, 358.5 kg/kkg (717 Ibs/ton). Mill
114 and 187 had average color loads of 197 and 216.5 kg/kkg (394 and 433
Ibs/ton), respectively. The average color load for the four market
kraft mills was 217 kg/kkg (434 Ibs/ton).
Mill 126, which had the highest color load, was the only market kraft
mill surveyed that bleached 100 percent softwood pulp. Twenty-five
percent softwood was bleached 'at Mill 114, while Mills 140 and 187
bleached 100 percent hardwood.
Table 13 shows the comparison for the four market kraft mills surveyed.
III-103
-------
TABLE 13
COLOR LOAD AT SECONDARY TREATMENT INFLUENT
MARKET KRAFT
Mill
No.
114
126
140
187
Day of
Survey
1
2
3
Average
1
2
3
Average
1
2
3
Average
1
2
3
Average
Percent
Softwood
25
26
24
25
100
100
100
100
0
0
0
0
0
0
0
0
Color
kg/kkg
197.0
223.0
171.0
197.0
403.0
358.0
315.0
358.5
84.5
115.5
90.0
96.5
220.0
230.0
200.0
216.5
Load
(Ibs/ton)
(394)
(446)
(342)
(394)
(806)
(716)
(630)
(717)
(169)
(231)
(180)
(193)
(440)
(460)
(400)
(433)
Bleaching
Sequence kl/kkg
CEHDED 189.3
184.2
168.9
180.8
CEDED 153.0
144.3
130.1
142.6
CEHED 71.3
85.1
70.9
75.8
CEDED 109.3
99.2
98.0
102.2
Flow
_ (kgal/ton)
(45.4)
(44.2)
(40.5)
(43.4)
(36.7)
(34.6)
(31.2)
(34.2)
(17.1)
(20.4)
(17.0)
(18.2)
(26.2)
(23.8)
(23.5)
(24.5)
Subcategory Average
217.0
(434)
125.8
(30.1)
4. BCT Kraft Subcategory
Five BCT kraft mills were surveyed, four in the South and one in the
West. The four Southern mills had average color loads in a range from
214.5 kg/kkg (429 Ibs/ton) to 291.5 kg/kkg (583 Ibs/ton). Mill 117,
located in the West, had an average color load of 111.5 kg/kkg (223
Ibs/ton) of bleach plant production. It should be noted once again
however, that Mill 117 added hypochlorite to their second bleaching
stage caustic extraction filtrate that was being sewered for the purpose
of reducing the color load from this wastewater stream. The average
III-104
-------
color load for the five BCT kraft mills was 221 kg/kkg (442 Ibs/ton).
Mill 121 utilized a CHED bleaching sequence, while the other four mills
used CEH as their first three bleaching stages. The comparison of the
five BCT kraft mills is shown on Table 14.
TABLE 14
COLOR LOAD AT SECONDARY TREATMENT INFLUENT - BCT KRAFT
Mill Day of Percent
No. Survey Softwood
105 1 52
2 54
3 _53
Average 53
111 1 54
2 61
3 J76
Average 63
117 1 100
2 100
3 100
Average 100
121 1 57
2 58
3 52!
Average 56
161 1 41
2 46
3 4£
Average 45
Subcategory Average
Color Load
kg/kkg (Ibs/ton)
324.5
220.0
329.5
291.5
279.5
235.0
246.0
253.5
92.0
123.0
119.5
111.5
221.0
(649)
(440)
(659)
(583)
(559)
(470)
(492)
(507)
(184)
(246)
(239)
(223)
(472)
(434)
(380)
(429)
(475)
(446)
(481)
(467)
(442)
Bleaching
Sequence
Softwood
CEHDED
Hardwood
CEHDD
Softwood
CEHDHED
Hardwood
CEHED
CHEHH
Flow
kl/kkg (kgal/ton)
CHED
CEHD
170.6
177.2
218.1
188.6
199.3
188.1
225.6
204.3
197.7
197.2
182.6
192.5
161.8
157.2
173.9
164.3
123.0
110.1
99.7
110.9
172.6
(40.9)
(42.5)
(52.3)
(45.2)
(47.8)
(45.1)
(54.1)
(49.0)
(47.4)
(47.3)
(43.8)
(46.2)
(38.8)
(37.7)
(41.7)
(39.4)
(29.5)
(26.4)
(23.9)
(26.6)
(41.3)
III-105
-------
5. BCT and Market Kraft Mills
Three mills producing BCT papers and market pulp, located in the South,
were visited during the color surveys. All three mills bleached at
least 51 percent softwood pulp during the survey period and all three
utilized CEH bleaching for the first three stages of their bleaching
sequence (Mill 113 used CHD on their hardwood pulp). The average color
load was 268 kg/kkg (526 Ibs/ton) for the three mills.
The percentage of softwood pulp bleached appeared to be a major factor
in contributing to the relative color load from these mills. Mill 122
bleached the highest percentage of softwood pulp, 81 percent, and had
the highest color load, 312 kg/kkg (624 Ibs/ton). Mill 113 had the
lowest percentage of softwood pulp bleached, 51 percent, and had the
lowest color load 227 kg/kkg (454 Ibs/ton). Table 15 shows the com-
parison for the three BCT and market kraft mills.
III-106
-------
TABLE 15
COLOR LOAD AT SECONDARY TREATMENT INFLUENT
BCT AND MARKET KRAFT
Mill
No.
100
113
122
Day of
Survey
1
2
3
Average
1
2
3
Average
1
2
3
Average
Percent
Softwood
56
54
54
54
46
61
48
51
69
79
100
81
Color
kg/kkg
224.0
283.5
242.5
250.0
182.0
232.5
266.5
227.0
257.0
398.0
281.5
312.0
Load
(Ibs/ton)
(448)
(567)
(485)
(500)
(364)
(465)
(533)
(454)
(514)
(796)
(563)
(624)
Bleaching
Sequence
Softwood
CEHD
Hardwood
CEHDH
Softwood
CEHDEDD
Hardwood
CHDED
CEHD
kl/kkg
215.2
239.8
226.4
227.1
159.7
207.2
167.6
178.2
108.4
117.6
138.0
121.3
Flow
(kgal/ton)
(51.6)
(57.5)
(54.3)
(54.5)
(26.0)
(49.7)
(40.2)
(42.7)
(26.0)
(28.2)
(33.1)
(39.1)
Average
268.0
(526)
176.0
(42.1)
6. Dissolving Kraft
Two dissolving kraft mills, both located in the South, were visited
during the color survey project. The average color load at the influent
to the secondary wastewater treatment plant at the mills was 363.5
kg/kkg (727 Ibs/ton) at Mill 108 and 369 kg/kkg (738 Ibs/ton) at Mill
127. Mill 127 bleached 100 percent softwood pulp, while Mill 108
bleached 72 percent softwood pulp during the color survey. Table 16
shows the comparison of the color survey results at these two dissolving
kraft mills.
III-107
-------
TABLE 16
COLOR LOAD AT SECONDARY TREATMENT INFLUENT - DISSOLVING KRAFT
Mill
No.
108
127
Day of
Survey
1
2
3
Average
1
2
3
Average
Percent
Softwood
73
71
72
72
100
100
100
100
Color
kg/kkg
319.0
333.5
437.5
363.5
332.5
401.0
373.5
369.0
Load
(Ibs/ton)
(638)
(667)
(875)
(727)
(665)
(802)
(738)
(738)
Bleaching
Sequence
CHEDED
CEHDED
kl/kkg
243.5
234.4
268.8
248.8
217.3
247.3
209.8
224.8
Flow
(kgal/ton)
(58.4)
(56.2)
(64.4)
(59.7)
(52.1)
(59.3)
(50.3)
(53.9)
Subcategory Average
336.0
(732)
237.4
(56.8)
7.
Soda
One of the two operating soda mills in the United States was visited
during the color survey project. The results of the survey at the mill
are shown on Table 17.
TABLE 17
COLOR LOAD AT SECONDARY TREATMENT INFLUENT - SODA
Mill
No.
152
Day of
Survey
1
2
3
Average
Percent
Softwood
4-5
4-5
4-5
4-5
Color Load
kg/kkg (Ibs/ton)
156.5 (313)
124.5 (249)
137.0 (274)
139.5 (279)
Bleaching
Sequence
JL
CEH j k
— P
Flow
kl/kkg (kgal/ton)
193.5 (46.4)
274.4 (63.4)
248.9 (59.7)
235.6 (56.5)
*Bleach Plant uses a CEH sequence with a portion of the bleached pulp sent
to a fourth stage peroxide bleaching.
III-108
-------
8. Mills Utilizing Multiple Pulping and Mixed Products
Mills 102 and 125 manufacture various products utilizing two or more
kinds of pulp. Mill 102 manufactures bleached and unbleached board,
while Mill 125 manufactures bleached kraft and groundwood pulp for the
production of newsprint, market kraft, and coated and uncoated papers.
Table 18 shows the results of the color survey at each of the two mills.
TABLE 18
COLOR LOAD AT SECONDARY TREATMENT INFLUENT -
MULTIPLE PULPING, MIXED PRODUCTS
Mill
No.
102
125
Day of
Survey
1
2
3
Average
1
2
3
Average
Percent
Softwood
38
, 39
40
39
100
85
100
94
Color
kg/kkg
125.5
143.0
131.5
133.3
238.0
277.0
313.0
276.0
Load
(Ibs/ton)
(251)
(286)
(263)
(267)
(476)
(554)
(626)
(552)
Bleaching
Sequence
CEDED
CEHED
kl/kkg
264.8
239.4
245.6
249.9
126.3
135.9
142.6
139.3
Flow
(kgal/ton)
(63.5)
(57.4)
(58.9)
(59.9)
(30.3)
(32.6)
(34.2)
(32.4)
Average
205.0
(410)
193.1
(46.2)
9. Summary
A bar graph was used to compare all the subcategories and indicate the
general conclusions which were made during this evaluation phase of the
color project. Figure 44 shows the bar graph comparison by subcategory.
III-109
-------
FIGURE
COMPARISON OF> SUBCATEGORIES-
c
o
a>
FINE
KRAFT
SODA
MULTIPLE. PULPING,
MIXED PRODUCTS
MARKET
KRAFT
BUT
FINEStMARKET
KRAFT
KRAFT
PERCENT SOFTWOOD
COA-RSE
8MARKET
KRAFT
DISSOLVING
KRAFT
81%
100%
0 (0)
MILL NUMBER
AVERAGE FORSUBCATEGORY
-------
Each subcategory was presented-so that the mill with the lowest average
color load at the influent to the secondary treatment was shown first,
and the remaining mills shown in order of increasing average color load.
The average color load for the subcategory was shown as a dashed line
through the mill bar graphs in that subcategory. Also shown on the
Figure was the average percent softwood pulp bleached during the color
survey for each mill.
As was mentioned in the preceding portions of this section, there was a
definite indication that mills bleaching softwood pulp would have higher
color load than a similar mill bleaching hardwood pulp. This has been
reported in previous studies done by others on color from bleached kraft
mills. The mill with the highest average color load in 5 of the 7 sub-
categories surveye'd (Mill 152 not included) also bleached the highest
percent softwood pulp. In one of the 2 subcategories where this was not
the case, BCT kraft, the mill bleaching the highest percent softwood
pulp, Mill 117, used hypochlorite on their caustic extraction filtrate
which was sewered to reduce their color load. In the other subcategory,
fine and market kraft, 2 mills of the 5 mills surveyed bleached 60 and
100 percent softwood, while the other 3 mills were in a range from 30 to
40 percent softwood pulp bleached. Mill 106 and 107 had an average
color load of 301 kg/kkg (602 Ibs/day), while the 3 mills which bleached
the lower percent 'softwood pulp had an average color load of 191 kg/kkg
(382 Ibs/ton). A more detailed evaluation of softwood versus hardwood
bleached pulp, and the resulting color load will follow.
Ill-Ill
-------
H. WOOD SPECIE
After evaluating the comparison by subcategory it was determined that an
analysis of the color load versus the wood specie bleached should be
undertaken. The approximate effect upon color load that results from
the percent of softwood or hardwood pulp bleached was calculated for
various sample locations. The intent of the evaluation was to establish
whether sufficient data existed for providing BATEA effluent color
limitations which would depend upon the wood species pulped. The
evaluation by subcategory had indicated that mills which bleached higher
percentages of softwood pulp had greater color loads than those ex-
perienced at mills which bleached higher percentages of hardwood pulp.
1. Wood Specie's Effect on Color From Bleach Plant
The effect that the percent softwood or hardwood pulp bleached had upon
the color load in the first chlorinatiori stage effluent was evaluated
(see Figure 45). Data from mixed hardwood and softwood bleach plants
showed a general trend of increasing color load with increasing percent
softwood pulp bleached. The average color load for the samples at the
first chlorination stage when 100 percent softwood pulp was bleached was
28.5 kg/kkg (57 Ibs/ton). The average color load for those samples
taken at the first chlorination stage when 100 percent hardwood pulp was
bleached was 17 kg/kkg (34 Ibs/ton).
III-112
-------
FIGURE 45
SOFTWOOD VERSUS. HARDWOOD
AT THE FIRST CHLORINATIQN
STAGE FILTRATE
80(160)
r (160) 80
I
70(140) -
60(120) <
(
<
"c 50(1 00) -<
o
X (
in
-Q
f
1
)
1
)
>
1
C 0 0
1
o> (
£ 40 (80) •
o>
" i
Q
O 30 (60) '
-1 AVERAGE (
I
8 <
o
0 ° 0
(
I
0? • f
-1 ik ° <
O ffi CJD <
•(140) 70
-(120) 60
>
o
-(100)50 o
r
o
^n
r~
O
- (80) 40 ' o
) "
yr
i
> i
0 20(40)-! ° Jy (40)20
I 0 f* — AVERAGE
1 OR
1 ° ° 1
i i
10 (20) H » (20)10
« ,«, 1 <5>
!
ln\ n
0 10 20 30 40 50 60
% HARDWOOD
100 90 80 70 60 50 40
% SOFTWOOD
70 80 90 100
30 20 10
O SINGLE POINT
• MULTIPLE POINT
-------
A probability curve showing the color loads at the first stage chlorina-
tion effluent and the percent of the values which were less than or
equal to a specific color load was also plotted (see Figure 46).
The first caustic extract stage was then evaluated. The population
distribution function of the first caustic extract stage showed that
most had color loads less than 150 kg/kkg (300 Ibs/ton) of bleach plant
production, but color loads ranged as high as 550 kg/kkg (1100 Ibs/ton).
The color loads for 100 percent softwood pulp bleached reflected this
wide range: the average 168 kg/kkg (336 Ibs/ton) was significantly
greater than the median 120 kg/kkg (240 Ibs/ton). Color loads for
bleaching 100 percent hardwood averaged 45.5 kg/kkg (91 Ibs/ton) and had
a median of 30 kg/kkg (60 Ibs/ton). A marked increase in color load was
observed with increasing softwood pulp bleached.
I
Figure 47 shows a graph with the first caustic extract stage data plot-
ted. A probability curve for the first caustic extract stage data was
plotted and is shown on Figure 48.
The first chlorination and caustic extract stages were then added and a
graph showing 100 percent softwood, 100 percent hardwood, and various
points representing fractions of softwood and hardwood pulp bleached
were plotted. Figure 49 shows the plot of these data points.
The color loads for the 100 percent softwood pulp bleached reflected the
wide range of values determined. Color loads for the 100 percent soft-
wood pulp bleached averaged 222 kg/kkg (444 Ibs/ton) which was well
III-114
-------
c
o
O
<
o
O
o
90(180)
80 (160)
70(140)
60(120)
50(100)
40 (80)
30 (60)
20 (40)
10 (20)
0 (0)
0.01
FIGURE: 46
FIRST CHLORINATION STAGE FILTRATE
I
j I
0.05 0.1 0.2 0.5 I
10 20 30 40 50 60 70 80 90
% OF THE TIME < GIVEN VALUE
95
98 99
99.8 99.9
99.99
-------
c
o
X
in
O>
en
O
O
cr
O
O
O
FIGURE 47 .
SOFTWOOD VERSUS HARDWOOD
AT THE FIRST CAUSTIC EXTRACT STAGE
550 (1100) -i
<
<
i
500(1000)-
450 (900)-
<
400(800)-
350 (700)-
(
300 (600)-
250 (500)-
i
<
200 (400)J
<
150 (300)-<
1
>
)
\
t
>
)
)
)
1
5 0
0
1
0
) 0
)
i ° °
100 (200)-i ° 0
T (
-(1100)550
- (1000)500
- (900)450
- (800)400
O
- (700)350 0
O
r
o
- (600) 300 0
(O
JT
- (500)250 ^
CT
(A
O
3
- (400) 200
- (300)150
>
I °° A
I §0 0 T
50 (IOO)-T 4(100)50
i j^-AVERAGE
A m
0 (0)-
c
'
0 ,
f\ i
1)1111111
) 10 20 30 40 50 60 70 80 90 1C
L (0) 0
)0
SINGLE POINT
MULTIPLE POINT
% HARDWOOD
100 90 80
70 60 50 40 30 20
% SOFTWOOD
10
-------
FIGURE 48
FIRST CAUSTIC EXTRACT STAGE;
600 (1200)
o 500 (1000)
\
in
cn
40O (800)
300 (600)
CC
O
_l
3 200 (4pO)
100 (200)
0 (0)
0.01 0.05 O.I 0.2 0.5 I 2
10 20 30 40 50 60 70 80 90 95 98 99 99.8 99.9 99.99
% OF THE TIME < GIVEN VALUE
-------
FIGURE 49
SOFTWOOD VERSUS HARDWOOD.
FOR COMBINED FIRST CHLORINATION
AND CAUSTIC EXTRACT STAGES
600(1200) r -| (1200) 600
I
I
2 5.5.0 (1 1 00) (
o 1
X
.a 500 (1000)
j* 450 (900) (
o>
•* 400 (800)
Q"
0 350 (700) '
0 300 (600) '
-
-
"
-
-
0
0 250 (500) A- °
rt v r rr ft r* r M
MV t K AvJ C ^1
200 (400) T- °
MEDIAN »J ° °
150 (300)?- ° -,
a o
8 o '
9 O
100 (200) |-
T "
50 (100) '
0 (0)
o
(1100) 550
(1000)500
(900) 450
(800) 400
(700) 350
(600) 300
(500) 250
(400) 200
(300) 150
(200) 100
O
O
f—
0
33
0
0
y,.
(O
£
I
o
•3
< AVFRARF
""(1 00) 50
1 Id 1 1 II 1 1 T (0) 0
_..._Q. 10 20 30 40 50 60 70 80 90 100
„ .. % HARDWOOD
... LOQ....9JD-. 8.0 70 60 .50 .40 3.0 20 ..10 0
MEDIAN
% SOFTWOOD
SINGLE POINT
• MULTIPLE POINT
-------
above the median value of 167.5 kg/kkg (335 Ibs/ton) of bleach plant
i
production. The 100 percent hardwood pulp data points indicated a much
smaller spread. The color loads averaged 64 kg/kkg (128 Ibs/ton) and
the median was 52.5 kg/kkg (105 Ibs/ton).
Three probability curves were plotted for the combined first chlor-
ination and first caustic extract stages. The curves-represented a plot
of the color load resulting from 100 percent softwood, 100 percent
hardwood, and mixed hardwood and softwood points. Also shown was a plot
of all sample points (see Figure 50). The plot of all the sample points
reflected the skewing tendency which resulted with increasing percent
softwood pulp bleached.
2. Wood Specie's Effect on Total Color at the Secondary Treatment Influent
The total color at the influent to the secondary treatment system had
been used in most of the previous evaluations of the data collected
during the pulp and paper mill color surveys. For the purpose of deter-
mining BATEA effluent color limitations based upon wood species pulped,
the secondary treatment influent provides the best sample location for
making this determination.
Figure 51 shows the color load population distribution functions for
three cases at the secondary treatment influent. Points representing
color load resulting from 100 percent softwood, 100 percent hardwood,
and mixed hardwood and softwood samples were plotted. Figure 52 shows a
III-119
-------
FIGURE 5O
COMBINED FIRST CHLORINATION AND
FIRST CAUSTIC EXTRACT STAGES
i 600(1200)
c
o
o>
500 (1000)
400 (800)
o>
Q" 300 (600)
O
_l
a:
_J
O
o
200 (400)
100 (200)
(0)
O ALL POINTS
A 100% SW
O 100% HW
D MIXED HW.SW
O.OI O.O5 O.I 0.2 0.5 I
10
20 30 40 50 60 70 SO
90 95
98 99
99.8 99.9
99.99
% OF THE TIME
-------
c
o
450(900)
400(800)
350 (700)
cr>
300(600)
o>
.it
Q
<
O 250 (500)
_l
cr
o
_i
° 200(400)
150 (300)
100 (200)
50 (100)
0.01
FIGURE 51
SECONDARY TREATMENT INFLUENT
A 100 % sw
O 100% HW
D MIXED HW, SW
I
\ I
0.05 O.I 0.2 0.5 I
10 20 30 40 50 60 70 80 90
% OF THE TIME < GIVEN VALUE
95
98 99
99.8 99.9
99.99
-------
FIGURE 52
SOFTWOOD VERSUS HARDWOOD
AT THE SECONDARY TREATMENT INFLUENT
*£
o
X
It)
CT.
_^
\
o>
Q
O
o:
o
o
o
450 (900)
400 (800)*
<
350 (700)
<
MEDIAN ^
300 (600)
AVERAGE »•
250 (500)
(
200 (400)
150 (300)
(
(
100 (200)
<
50 (100)
O (01
i-
O
»• o
1
-
0 0
0
o
L o
o
o
0 0
o
0 0
0 8°
o°o
o •<
0
0 0
0 °
_ O o <
O u 0 -
o ,
\
> 0 ° 0 " <
o ,
o
o -
' ° {
0 '
o
• —
1 1 1 1 1 1 1 1 1
(900) 450
(800)400
(700)350
(600) 300
(500) 250
>
J
X400) 200
•^ AVERAGE
1300)150
JM fui r n i A M
^ MtUIMN
)
3
(200) 100
5
(100) 50
(Ol O
0 10 20 30 40 50 60 70 80 90 100
% HARDWOOD
100 90 80 70 60 50 40 30 20 10 0
% SOFTWOOD
o
O
r'
0
r
0
^
0
y.
(O
3T
Id
CT
U)
O
3
^-'
-------
plot of the sample data points at the secondary treatment influent on
the basis of percent softwood and hardwood pulp bleached versus color •
load. The color loads resulting from bleaching 100 percent hardwood
pulp showed a range from approximately 82 kg/kkg (165 Ibs/ton) to 250
kg/kkg (500 Ibs per ton)". The color loads resulting from bleaching 100
percent softwood pulp ranged from 100 to 425 kg/kkg (200 to 850 Ibs/ton),
Color loads resulting from bleaching mixed softwood and hardwood pulps
had ranged from 75 to 450 kg/kkg (150 to 900 Ibs/ton). The average
color load for 100 percent softwood pulp bleached was 281 kg/kkg (561
Ibs/ton), which was slightly less than the 313 kg/kkg (626 Ibs/ton)
median value. The median value being higher than the average reflected
the scattering of points in the lower color load range. The 100 percent
hardwood pulp bleached averaged 151 kg/kkg (302 Ibs/ton) with a median
of 137 kg/kkg (274 Ibs/ton). Color loadings from the bleaching of mixed
softwood and hardwood pulps tended to increase with increasing levels of
softwood pulp bleached.
The preceding evaluations showed the need for providing limits which
would vary depending upon the proportion of softwood or hardwood pulped
and bleached. Section VI will therefore determine BATEA effluent color
limitations based upon the percent softwood pulped and bleached.
I. ANALYSIS OF BLEACHING SEQUENCES
As shown by data presented previously in this Section, there is a sig-
nificant variation in color load from bleach plant to bleach plant where
III-123
-------
similar species are bleached to corresponding final brightnesses. In an
attempt to identify the factors causing these variations bleaching
variables were examined for their relative potential to influence color
generation.
To facilitate this analysis, the mills surveyed were separated into two
general bleaching categories based on sequence used. Group A involved 5
mills: numbers 102, 106, 121, 126, and 187 all using the CEDED sequence.
Group B involved 18 mills and 26 bleach plants: numbers 100, 101, 103,
105, 107, 108, 111, 113, 114, 118, 119, 121, 122, 125, 127, 136, 140,
and 161 all using a significant amount of hypochlorite in their sequences
along with chlorine dioxide in various configurations.
•N
The number of stages in Group B varied from 4 to 7 with a wide variety
of combinations as shown in Table 19.
TABLE 19
GROUP B BLEACHING SEQUENCES
Sequence Number
CEHD 6
CEHDH 3
CEHED 5
CEHDED 4
CEHDD 1
CHEDED 1
CEHDEDD ' 1
CHDED 1
CHHD 2
CHEHD 1
CE-DHD 1
Code: C = Chlorination
E = Caustic Extraction
H = Hypochlorite (sodium or calcium)
D = Chlorine .dioxide
III-124
-------
Two unusual sequences were not placed in any specific group for data
analysis. They were Mill 117 with its CEHH sequence and Mill 152 with
its CEHP, where the "P" indicates hydrogen peroxide bleach solution
being used on the last step for a portion of its bleached pulp.
1. Rationale for Categorization
The selection of the two general bleaching categories indicated as Group
A and Group B is based on a very simple factor, namely, the use of
hypochlorite.bleach in Group B and the absence of its use in Group A.
Chlorine and chlorine dioxide are common to both groups. Hypochlorite
bleach was selected as it has been reported that its use has a sig-
nificant effect on reduction of bleach plant color. In the subsequent
analysis of variables within each sequence, the effects are further
investigated on the basis of wood species category.
2. Bleaching Factors Investigated
The following bleaching factors were determined to be potentially sig-
nificant in regard to color generation versus sequence grouping:
1. Bleaching sequence (within Group B)
2. Chlorine application
I
3. Hypochlorite .application
Further analysis of bleaching is discussed later in this report. The
thrust of this particular section is to analyze the effect of the overall
III-125
-------
bleaching sequence on color generation rather than investigating oper-
ating parameters to a great degree.
a. Bleaching Sequence within Group B. Group A bleaching sequences are
all the same, namely CEDED; thus no analysis of sequence variation is
necessary. However, in Group B there are 11 different variations of
sequences using chlorine, hypochlorite, and chlorine dioxide, in most
cases in conjunction with sodium hydroxide stages. Although the bleach
plant is recognized as a complex chemical process with many variables
which could theoretically have an effect on color of the final bleach
plant effluent, claims have been made for improved color from sequence
variation. Ideally, to investigate the effect of this particular item,
a single bleach plant bleaching a uniform species to a uniform final
brightness should be investigated using the different sequence var-
iations. However, this was not a practical approach; thus, it was
considered worthwhile to attempt an analysis based on the survey data as
well as some additional data obtained in a follow-up discussion of
internal operating conditions with the subject mills.
b. Chlorine Application. Both main sequence groups utilize chlorine
in the first stage of each bleach plant surveyed, which is the case in
the majority of bleach plants throughout the industry. The only variation
is where chlorine dioxide is substituted for chlorine in the first stage
in various percentages up to nearly 100%. None of the mills in this
survey utilized chlorine dioxide in the first bleaching stage, although
suppliers' data indicated that its use can reduce bleach plant color
III-126
-------
(i.e., Rapson and Reeves). Thus, there is no survey data to allow
analysis of the effect of chlorine dioxide and the task becomes one of
comparing the effects of the amount of chlorine used per ton of pulp
versus color generation.
c. Hypochlorite Application. Several sources identified the sub-
stitution of chlorine dioxide with hypochlorite bleach as a method for
reducing bleach plant color. All bleach plants in Group B utilized
hypochlorite for bleaching in addition to chlorine dioxide. Thus, it
would be expected that the various ratios of chlorine dioxide to hypo-
chlorite might show a relationship to color generation within a given
species category.
3. Discussion of Sequence Variables
There are many variables, both controlled and uncontrolled, which have a
potential to affect color generation from the bleaching process. The
complexity of the process and interaction of operating variables would
require monitoring of numerous simultaneous events in order to determine
the causes of subtle changes in effluent color. This study did not go
to that degree of effort and as a practical necessity limited itself to
analysis of items judged to be apparent without extensive variable
monitoring.
The following discussions of the effects of bleaching sequences on color
of bleach plant effluent are based on analysis of data obtained during
the mill survey phase of the study.
III-127
-------
a. Bleaching Sequence Discussion. Group A bleach sequence was CEDED
with a range of color in the bleach plant effluent from 217 Ibs/ton to
1,096 Ibs/ton. Mill No. 102 showed the lowest figure and bleached both
hardwood and softwood to a brightness of 87+ points G.E. Mill No. 126
showed the highest per ton color and it bleached only softwood to a
brightness of 87+ points.
All mills in Group A bleached to a brightness in excess of 87 points
with Mill No. 187 bleaching as high as 92 points during the survey
period.
All mills in Group A that produced data used in this analysis are
located in the South, thus similar wood species were used in each.
Nothing significant can be noted from Group A bleaching sequence other
than the fact that a wide variation of color can be found within the
group under similar operating and geographic conditions.
Group B which consisted of 11 variations of use of the bleaching agents
chlorine, chlorine dioxide and hypochlorite, showed a bleach plant ef-
fluent color range of from 38 Ibs/ton to 1,080 Ibs/ton. Mill No. 103
showed the lowest color while bleaching hardwood to a brightness of 85
points while Mill No. 107 had the highest figure and bleached only
I
softwood to a brightness in excess of 87 points.
The CEHD sequence was the most popular with CEHED and CEHDED also being
used extensively throughout the 26 bleach plants in the group. The
III-128
-------
three sequences accounted for 58 percent of the plants surveyed. No one
sequence showed any trend toward lower color generation within Group B;
however, Group B did show a lower average per ton color load than Group
A (237 Ibs/ton versus 452 Ibs/ton).
Group B generally bleached to a lower brightness than Group A; however,
that was not considered to be a significant factor due to the fact that
the great majority of color is generated early in the bleaching sequence
regardless of final brightness. The significance of brightness is more
fully explored later in this report.
The percentage of hardwood and softwood bleached in each group was
almost identical. Group A averaged 49% hardwood and 51% softwood, while
Group B averaged 48% hardwood and 52% softwood. Thus, species effect on
average color of the sequence groups was not a factor.
It would appear from the survey data that there is significant reason to
expect the sequences utilizing hypochlorite bleach to produce an ef-
fluent with less color than sequences using no hypochlorite, all other
major process parameters being similar.
Figures 53 and 54 show the relative color contribution from bleach
plants in each bleaching group.
b. Chlorine Application Discussion. An attempt was made to determine
the effect of chlorination degree on color loading in bleach plant
III-129
-------
100
101
102
103
105
106
107
108
110
FIGURE 53
BLEACH PLANT COLOR
BLEACHING GROUP A
113
0 H4
-I
2
117
118
119
121
122
125
126
127
134
136
140
152
161
187
(0)
0
1109
(100)
50
(200)
100
1
(300)
150
i
(400)
200
i
(500)
250
i
(600)
300
"I
(700)
350
TOTAL BLEACH PLANT COLOR kg/kkg (Ibs/ton)
-------
FIGURE 54 .
BLEACH PLANT COLOR
BLEACHING GROUP B
(0)
o
(100)
50
(200)
100
(300)
150
(400)
200
(500)
250
(600)
300
(700)
350
TOTAL BLEACH PLANT COLOR kg/kkg (Ibs/ton)
-------
effluent. Figure 55 shows points plotted for the bleach plants in Group
B with hardwood and softwood plotted separately due to their different
chlorine requirements.
No reliable statistical relationship was seen to exist between chlorine
usage and bleach plant effluent color in Ibs/ton, based on the survey
data.
c. Hypochlorite Application Discussion. An attempt was also made to
determine the effect of the amount of hypochlorite used per ton of
bleached pulp, on color loading in bleach plant effluent. As the
sequence group comparison-indicated that the use of hypochlorite re-
sulted in lower color generation, it was reasonable to expect the amount
of hypochlorite used to be a predictable factor. Figure 56 shows
hypochlorite percentage plotted aginst bleach plant color in Ibs/ton
with hardwood and softwood being plotted separately.
Statistical analysis of the survey data does not show any reliable
relationship to exist between percent hypochlorite and bleach plant
color. Although this relationship has been shown in laboratory work,
apparently too many other factors were present in the survey data to
verify the expected results.
III-132
-------
FIGURE 55
BLEACH PLANT COLOR VS.
USAGE
200-i(400)
o
150
o
o
o. 100-
x
o
m
50-
(300)'
O'2I
(200)
Ol52
O161
Ol36
(100)
O 140
QII3
Qll9
O 100
O HARDWOOD
A SOFTWOOD
D COMBINED
n
A no
g
117
121
A114
A161
A 134
Al36
113
A 125
I03A
A'oo
A I 19
-------
FIGURE 56
BLEACHING GROUP B
BLEACH PLANT COLOR VS. % HYPOCHLORITE USED
400-,(800)
350 -
~ 300
o
250-
cc
o
o
o
x
u
HI
_1
m
200-
150-
100-
50-
(700)
(600)
(500)
(400)
(300)
(200)
(100)
I03Q
Ql40
D
QII4
O152
O161
IOOQ
"19
125
O HARDWOOD
A SOFTWOOD
D COMBINED
A114
136 A
n
A 125
Q|36
O134
A
119
I
1.0
2.0
3.0
I7A
4.0
TOTAL HYPOCHLORITE (%)
-------
J. INTERNAL PARAMETERS COMPARISON
As noted in preceding sections, there were variations in color gen-
eration in pounds per ton of bleached pulp within the subcategories. In
an attempt to identify factors causing these variations, kraft pulping
and bleaching variables were examined for their relative potential to
influence color generation. The following variables were determined to
be potentially significant:
1. Wood Species
2. Degree of pulping ("K" or KAPPA numbers)
3. Brown stock washing efficiency (overall)
4. White liquor sulfidity
5. Bleaching sequence and application
6. Chlorine application
7. Bleach extraction stage ("K" or KAPPA numbers)
8. Type of chlorine dioxide generation
9. Type of hypochlorite used
10. Final pulp brightness
Liquor spills and leaks certainly would have an effect on color var-
iations and the sample teams were kept appraised of any such occurrence
by mill management during their sampling periods.
1. Selection of Variables
The rationale for selection of these variables is as follows:
III-135
-------
a. Wood Species. The effect of wood species on color and the data to
support the supposition is included in a previous section. That section
deals only with the two general species categories of hardwood and
softwood. No attempt was made to identify the relative contributions of
any one type of wood within a general category as data was not available
from the mill sampling selected.
b. Degree of Pulping ("K" or KAPPA Numbers). The thoroughness of
delignification of pulp is traditionally measured by the "K" number or
the KAPPA number test. The two are similar and result in an indirect
measurement of the amount of lignin left in the pulp after cooking. As
the reacted lignin is known to be a major color contributor, it follows
that an analysis of degree of pulping in a general species category
might explain color variations.
c. Brown Stock Washing Efficiency (Overall). The solubilized wood ~\
constituents which make up the majority of kraft mill color potential
are separated from the fiber mass on brown stock washers and the major
portion is subjected to evaporation and burning for chemical and heat
recovery. However, the washing system is not 100 percent efficient and
efficiency varies from mill to mill depending on a number of factors
such as system capacity and washer design, as well as operating pro-
cedures.
The "black liquor" not washed out of the pulp mass follows the pulp
through the process and ultimately finds its way to the effluent stream.
III-136
-------
Where it exits depends on system design with the (a) screen room ef-
fluent (2) brown stock decker effluent (c) bleach plant effluent; all
being sources of discharge. In some plants, the screen room system is
closed to a high degree and decker water is recycled back to the brown
stock washers. This, in effect, adds an additional stage of washing and
the brown stock washer soda losses are not an accurate measurement of
what finally reaches the effluent. In such systems the pulp leaving the
screening system for bleaching contains the color causing material which
will exit at the bleach plant in a reacted form.
Brown stock washer soda losses, as well as brown stock screened pulp
decker soda losses, were candidates for investigation.
d. White Liquor Sulfidity. The kraft pulping process involves the
formation of soluble organic sulfur compounds which have been identified
as having color causing potential. The amount of sodium sulfide in
kraft cooking liquor or "white liquor" is measured and expressed in
terms of percent sulfidity. This test is an indicator of the amount of
sulfide available for reaction during the cooking process. It follows
that if the soluble organic sulfur compounds have a significant impact
on effluent color then the amount of sulfur used in the cooking process
is worthy of investigation.
e. Bleaching Sequence and Application. The bleach plant is recognized
as a significant source of effluent color and the reasons for variability
of this source are worthy of investigation. This was covered in a
previous section.
III-137
-------
f. Chlorine Application. The effect of excess chlorine and ultimately
chlorine in the bleach plant effluent was discussed as part of the
previous section.
g. Bleach Extraction Stage ("K" or KAPPA Numbers). Bleaching is now
thought of by the industry as an extension of the pulping process in
that it involves the further purification of cellulose by removal of
colored materials, primarily lignin. One of the control techniques used
in most bleach plants is a measurement of lignin removal after the
second or caustic extraction stage of bleaching. This test is a "K"
number or KAPPA number as used in the cooking phase and indicates the
solubilization of lignin and its subsequent removal to the bleach plant
effluent. An attempt was made to correlate bleach plant color and this
test.
h. Type of Chlorine Dioxide Generation. Although the type of C1CL
generator used is not considered to be a significant process variable as
far as bleaching effluent color is concerned, there is the possibility
of an effect on final effluent color. If the spent acid from the
generation process is not recovered and is sewered it has the potential
to affect final effluent color and for that reason was investigated.
i. Type of Hypochlorite Used. Those mills using hypochlorite as a
bleaching agent use two types: namely sodium and calcium. The chemical
suppliers have indicated that a reduction in effluent color has been
noted from the use of calcium hypochlorite as compared to sodium hypo-
chlorite. An attempt was made to verify this contention in the mills
surveyed.
III-138
-------
j. Final Pulp Brightness. As previously discussed, bleaching is no
more than an extension of pulping where cellulose purification is the
objective. Considering brightness of the bleached pulp as a measurement
of the degree of purification then it may be possible to establish a
relationship between brightness and effluent color for a given species
mix. Data collected were analyzed for this relationship.
2. Data Collection
To acquire data to evaluate the potential color source relationships, it
was necessary to request additional information from the survey mills.
This was accomplished by developing a questionnaire which was completed
primarily by telephone communications. The data requested was concerned
with process variables and conditions existing within the plant at the
time of the sampling procedure.
A sample of the form used to collect the additional data is shown in
Appendix VI.
3. Discussion of Relationship Investigations
Before attempting to discuss the potential relationships between the
particular process variables and color variation, it is necessary to
comment on the complexity of the kraft process.
III-139
-------
There are many variables, both controlled and uncontrolled, which have a
potential effect on effluent color from the kraft process. The general
categories are:
1. Short-term variations in raw materials
2. Seasonal variations in wood supply
3. Production rate changes
4. Product type variations
5. Intentional operating changes
6. Unintentional operating changes
7. Liquor spills and leaks
To determine subtle changes in color as a result of one specific var-
iable involves the' monitoring of literally hundreds of operating events
and analysis of a substantial amount of data. This was beyond the scope
of this investigation and analysis was of necessity limited to those
relationships which were significant enough to be apparent without
extensive monitoring of other variables.
The following discussions, of each process item investigated as having a
potentially significant effect on color in kraft effluent, are based on
data accumulated from the supplementary questionnaire.
a. Wood Species^ As previously mentioned, insufficient data was
available from the surveys to allow quantification of the color po-
tential of individual species of wood within the general classes of
hardwood and softwood.
III-140
-------
Of those mills responding to the questionnaire, the following species
were pulped (see Table 20).
TABLE 20
DISTRIBUTION OF SPECIES PULPED
Hardwood Mills Using
Oak 19
Gum 13
Maple 5
Beech 2
Poplar 2
Hickory 1
Aspen 1
Birch 1
Sycamore 1
Pecan 1
Ash 1
Elm 1
Softwood
Pine (mixed) 15
Loblolly Pine 9
Douglas Fir 2
Cedar 1
Jack Pine 1
Hemlock 1
It can be seen from Table 20 that the predominant woods pulped by the
mills responding were those growing in the south, namely, oak and gum in
the hardwood category, and loblolly pine and mixed pine species in the
softwood category.
A comparison of the relative color contribution of the general cate-
gories of hardwood and softwood is discussed earlier in this report.
III-141
-------
b. Degree of Pulping. All kraft categories process their wood chips
to produce pulp in essentially the same manner, with the exceptions of
dissolving kraft pulp mills Nos. 108 and 127. Figure 57 shows plots of
the two general species categories with degree of cooking as measured by
"K" number versus primary clarifier influent color. It should be noted
that hardwood and softwood are not "cooked" to the same target "K"
number, thus the separation of species is evident in Figure 57.
Statistical analysis of the data points indicates that no apparent
relationship exists between degree of "cooking" and color generation in
either species category, or if such a relationship exists it is not
significant within the general bleached kraft category. It should be
noted that the "K" number range within each species category was not
very great due to the common requirements of final pulp.
Of primary concern in the analysis of primary clarifier influent color
is the fact that only three of the mills plotted were 100 percent one
specie. Mill Nos. 187 and 152 were all hardwood and mill No. 126 was
all softwood, thus the analysis had to take into account the relative
percentage of hardwood and softwood in the mills cooking both simul-
taneously.
An attempt was also made to correlate degree of pulping with color in
the screen room effluent as shown in Figure 58. However, again no
significant relationship exists. A relationship that did exist would
most probably be overwhelmed by the effect brown stock washing efficien-
cy has on screen room or decker color loading.
III-142
-------
FIGURE 57
PULPING ("K" NUMBER) VS. TOTAL COLOR
350 -i (700)
300-
K 250-
o
2
* 200 H
c
o
J1 I50H
Jt
^
o>
JC
X
o
o
o 100-
50-
(600)
0,,,
(500)
(400)
100
101
136
(300)
187
(200)
O"9
(100)
Quo
•152
II8
l40
O'°2
10
i i I i
12 13 14 15
O HARDWOOD
A SOFTWOOD
A126
113
A ioi
H4A A 136
A100
A 134
A118
A 119
A 102
T i i i i r riii
16 17 18 19 20 21 22 23 24 25
HARDWOOD K AND SOFTWOOD
-------
FIGURE 58
SCREEN ROOM OR.DECKER COLOR
VS-
PULPING K*
240 -i (480)
210-4(^20)
in
J3
- 180 -
or
o
o
o
o:
o
LU
O
-------
c. Brown Stock Washing. An evaluation of the potential relationship
between brown stock washer losses in the form of sodium chemicals, and
color in the effluent stream from the screening and deckering section of
the kraft process was attempted. The relationship was plotted in Figure
59 with no distinction between species as shown by the data points. It
was not possible to develop a hardwood-softwood relationship with this
effluent stream due to the factor that both species were screened and
deckered simultaneously. In the majority of mills surveyed, due to
potential color concentration at this point in the process, distinction
would not be considered practical.
The plot shows a trend toward higher color load per ton of pulp in the
screen room or decker effluent as the brown stock washer chemical losses
increase.
Figure 60 shows the random nature of screen room or decker color load in
kg/kkg (Ibs/ton) from the mills reporting this data. No specie or
subcategory trend can be noted although it can be seen that a signi-
ficant amount of color load comes from this source in a large percentage
of the mills surveyed.
Mill No. 152 showed 63 percent of its total color load from the decker
and Mill No. 136 had 45 percent of its total from the same source. Six
other mills had from 31 to 40 percent of their total color from the
screen room area.
III-145
-------
FIGUjRE 59
BROWN STOCK WASHER LOSSES VS.
SCREEN ROOM OR. DECKER COLOR
(BASED ON BLEACH PLANT PRODUCTION)
120 i
c
o
in
^ 90 H
o>
JL
-------
FIGURE 6O
BCREEN ROOM OR. DECKER COLOR
(HARDWOOD AND SOFTWOOD)
o
z
100
101
102
103
105
106
107
108
110
III
113
114
117
118
119
121
122
125
126
127
134
136
140
152
161
187
Illllllllllll HARDWOOD
SOFTWOOD
IIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIII
(0)
0
(50)
25
(100)
50
(150)
75
(200)
100
(250)
125
(300)
150
(350)
I 75
SCREEN ROOM OR DECKER COLOR kg/kkg (Ibs/ton)
-------
The screen room or decker area is the second most significant color
contributor in the mills surveyed with five mills having it as their
major source (Mills Nos. 103, 113, 136, 152 and 161).
d. White Liquor Sulfidity. Comparison of white liquor sulfidity with
screen room or decker color load was done to determine if soluble or-
ganic sulfur compounds formed during the cooking process have a sig-
nificant effect on color. This relationship was analyzed making the
assumption that the three governing factors affecting formation of these
compounds were reasonably uniform in all mills plotted. The factors
are:
1. Actual cooking time
2. Cooking temperature
i
3. Total alkali to wood ratio
It was assumed that the three cooking variables were changed to any
significant degree only when species were different. Hardwood does not
require the severity of "cook" needed to produce softwood pulp.
Figure 61 shows plotted points which appear to show a trend to increased
color with increased sulfidity. Further investigation of this rela-
tionship by plotting sulfidity against brown stock washer losses re-
vealed a similar trend as shown in Figure 62. This secondary rela-
tionship was judged to be coincidental based on an analysis of factors
affecting brown stock washer losses. However, it helps to explain the
trend shown in Figure 61 as Figure 59 shows that a good correlation
III-148
-------
FIGURE 61
(SCREEN ROOM OR DECKER COLOR VS,
SULFIDITY OF COOKING L
150 -i (300)
o
\
en
0>
je
jf
100 H
o
o
o
UJ
IT
O
2
O
O
ir
cc
o
50 H
(200)
[100)
Al40
A 107
D 103
114
D110
D'34
O HARDWOOD
A SOFTWOOD
D COMBINED
A161
QIGI
All3
15 16 17 18 19 20 21
D 102
22 23 24 25 26 27 28 29 30
SULFIDITY (%)
-------
FIGURE 62
BROWNSTOCK WASHER LOSSES VS.
COOKING LIQUOR SULFIDITY
40-1 (80)
35-
(70)
c
o
to
a
_ 30-
(60)
O>
Jt
V)
LJ
UJ
X
v>
o
o
en
o
tr
25-
(50)
20-
(40)
15-
(30)
10-
(20)
5-
(10)
A 161
D 101
a
A I 34
D 126
134 Q
Quo
A
A
D
no ioo
II7
R"8
ZSioo
All9
114
D H4
O 100
O HARDWOOD
A SOFTWOOD
D COMBINED
U '87
Dl25
15
20 25
SULFIDITY (%)
i
30
i
35
1
40
-------
exists between brown stock washer losses and screen room or decker
color. Thus, the relationship between sulfidity and screen room or
decker color was not judged to be significant.
e. Bleaching Sequence. This item was covered in a previous section.
f. Chlorine Application. This item was covered in a previous section.
g. Bleach Plant Control (As Caustic Stage "K" Number). The signi-
ficance of bleach plant chemical activity as measured by "K" number test
after the first caustic extraction stage and compared to bleach plant
color loading was investigated as shown in Figure 63.
The plot shows a wide scattering of data points with no indication of a
trend. Hardwood and softwood are usually bleached to different "K"
number targets as with "cooking," and the separation can be noted with
the softwood points plotted at higher "K" number.
A large number of the mills surveyed did not separate hardwood and
softwood bleach plant effluent and those are plotted as "combined" data
points. Mill Nos. 103, 114, 121, 101, 110, and 106 are in this cate-
gory. Mill Nos. 113-, 134, 187, and 140 bleached hardwood and kept the
effluent separate while Mill Nos. 113, 136 and 134 bleached softwood and
also had the effluent isolated to allow sampling for color content.
Mill Nos. 118 and 125 report that they mixed species prior to bleaching.
III-151
-------
FIGURE 63 ,
' !••
BLEACH PLANT COLOR VS.
;BLEACH PLANT CONTROL
,{AS CAUSTIC STAGE "K" NUMBER)
i (600)
250-
O
200-
I03
(100)
O110
O140
O 134
O 101
O"2I
n 125
Aioe
D
113
121
O HARDWOOD
A SOFTWOOD
n HARDWOOD AND
SOFTWOOD MIXED
A 134
O l87
A114
A 103
A no
A
101
A '36
2.5
3.5
4.5
5.5
BLEACH PLANT K
-------
h. Type of Chlorine Dioxide Generation. Chlorine dioxide was gener-
ated by five different processes in the mills surveyed. The processes
used were:
1. R-2
2. Matheson
3. Solvay
4. Hooker SVP
5. R-3
The R-2 process was the most prevalent and only one mill reported that
it was not recovering its waste acid from chlorine dioxide generation.
That mill had low bleach plant color due to large usage of hypochlorite
so no color effect'could be determined from sewering of the acid.
The survey data did not show a trend toward reduced bleach plant color
from any particular chlorine dioxide generating system.
i. Type of Hypochlorite. Figure 64 is a bar chart showing color
contributions from mills using no hypochlorite, mills using sodium
hypochlorite and mills using calcium hypochlorite as a main bleaching
chemical.
The average color from each of the three categories plotted in kg/kkg
(Ibs/ton) was as follows:
III-153
-------
(0)
0
FIGURE 64
BLEACH PLANT COLOR
TYPE OF HYPOCHLORITE USED
BLEACHING GROUPS A B ^
GROUP A
GROUP B
(1109)
(100)
50
(200) (300) (400) (500) (600)
100 150 200 250 300
TOTAL BLEACH PLANT COLOR kg/kkg (Ibs/ton)
(700)
350
-------
No hypochlorite 433
Sodium hypochlorite 220
Calcium hypochlorite 125
The data shows hypochlorite to have a significant effect on reducing
bleach plant color contribution as was discussed in a previous section;
however it also shows calcium hypochlorite to have an apparent advantage
over sodium hypochlorite.
Thus, the type of hypochlorite bleach used appears to be a significant
color reducing item. Of the four mills using only calcium hypochlorite
(Mill No. 117 not included), all bleached both hardwood and softwood.
j. Final Pulp Brightness. Figure 65 shows a plot of data points
relating final bleached pulp brightness in TAPPI standard units 'to
bleach color in kg/kkg (Ibs/ton).
Statistical analysis of the data does not show a reliable relationship
to exist with a correlation of 0.26, a slope coefficient of 1.93 and a
confidence factor of 83 percent. A trend does seem to be indicated
showing increasing brightness but not enough data was collected to
establish a significant relationship in any of the two species groups.
K. SUMMARY OF CONCLUSIONS
Section III has presented the data gathered during the color surveys at
the 26 bleached kraft and soda mills, and the analyses which were done
III-155
-------
FIGURE 65
FINAL BRIGHTNESS VS.
BLEACH PLANT COLOR
300 -i (600)
o 250-
o>
je
cr
o
_i
o
o
200-
150-
X
o
111
_l
m
100 -
50-
[500)
(400)
(300)
1200)
(100)
O HARDWOOD
A SOFTWOOD
D COMBINED
105
D'22
D 127
D 106
n
n
Ano
Due
O110
n
|36Q A136 161 D
100 n n,19
D 134
nio3
n !|3
140 n n 125
Dl87
n IDS
QII4
ii'i\IIrr^i i iIiiII
75 76 77 78 79 80 81 82 83 84 85 86 87 88 89 90 91 92
FINAL BRIGHTNESS
-------
with the data. This portion of the Section will summarize the con-
clusions which were made.
1. Historical Mill Data
It was concluded that the color surveys were generally conducted during
normal anticipated mill operational levels. This conclusion was based
on the comparison of operating production levels during the survey to
the historical mill data.
2. Dominant Wavelength
The range in dominant wavelengths encountered during the surveys were
consistent with those measured for the standards employed. Therefore,
the acceptance of potassium chlorop^atinate/cobaltous chloride solutions
as an acceptable standard for the measurement of color in mill waste-
water was further enhanced.
3. Split Sample Analysis
As demonstrated by the level of confidence experienced by the split
sampling and analysis conducted during these studies, comparable results
can be obtained independently as long as the analytical techniques
employed are equivalent.
III-157
-------
4. Color Load Based on Bleach Plant Production
To eliminate the possibility of inaccurate color load data, which could
be calculated when using the finished mill's production, the bleach
plant was selected as the basis for calculating color load in terms of
kg/kkg (Ibs/ton) of production. The pulping and bleaching operations
were found to contribute the largest percentage of the total color load
at the 26 pulp and paper mills surveyed. It therefore was concluded
that basing the color load on the kkg (tons) of pulp bleached per day
would be the method used to calculate color load. Mills which utilize
fillers, purchased pulp, and/or other types of pulp in the manufacture
of their finished product would have a more representative color load
determination through use of the bleach plant production.
5. Bleached Kraft Mill Color Origin
The evaluation of the color load identified by source for the 26 bleached
kraft and soda mills resulted in 20 of the 26 mills having 70 to 125
percent of their total color load identified by internal process source.
It was also determined that the major source of color at the 26 mills
was the bleach plant, which contributed an average of 59 percent of the
total mill color. Of the 59 percent, 80 percent was determined to be
contributed by the first caustic stage extraction in the bleach plant.
III-158
-------
The second major source of color was determined to be the screen room or
t
decker process. Approximately 24 percent of the total mill color was
determined to originate at this point in the mill's process.
The pulping, bleaching, and evaporator and recovery processes were
determined to be responsible for an average of 79 percent of the total
color load for the 26 mills surveyed.
6. Data Comparison by Subcategory and Wood Specie
The evaluation by subcategory and wood specie identified the fact that
pulping and bleaching higher amounts of softwood would increase the
color load produced by a mill. This was found to be true in 5 of the 7
subcategories. The two subcategories which did not show this trend were
found to have process differences which altered this pattern. It was
concluded that without these changes in the normal operations these two
subcategories would have also experienced this result.
7. Wood Species
As a result of the findings made in the subcategory analysis a more
detailed evaluation of wood specie pulped and bleached versus color load
was undertaken. The first chlorination, first caustic, and combined
first chlorination and first caustic effluents were evaluated along with
the color load and percent softwood pulp bleached at the secondary
III-159
-------
wastewater treatment influent. The preliminary findings were substan-
tiated and it was concluded that BATEA effluent color limitations based
upon the wood species pulped and bleached would be calculated.
8. Analysis of Bleaching Sequences
The data evaluated has shown a significant variation in color load
between different bleach plants where similar species were bleached to
corresponding final brightnesses. An attempt was made to identify these
variations by analyzing bleaching variables for their relative potential
to influence color generation.
Two major bleaching groups were identified, Group A, bleaching with the
CEDED sequence, and Group B which utilized hypochlorite in the bleaching
process.
It was determined that the Group B mills did experience less color than
Group A; however, a statistical analysis of the survey data did not show
any reliable relationship between percent hypochlorite and bleach plant
color.
9. Internal Parameters Comparison
An evaluation of 10 different internal process parameters was done in an
attempt to identify factors which might cause variations in color
generated.
III-160
-------
No substantive correlations between color load generated and the in-
ternal parameters examined were found after a statistical analysis of
all parameters had been performed, although screen room or decker color
load was identified as one of the two major color contributors in the
bleached kraft area, with a trend toward increased color with increased
washer losses.
III-161
-------
SECTION IV
LITERATURE AND EQUIPMENT MANUFACTURING INFORMATION
The following section will present a literature review on external color
reduction techniques. Additionally, a discussion of equipment manu-
facturing data from manufacturers of external color control techniques
developed or being developed will be presented.
The information reported in this section will form the basis for iden-
tifying a color control technology representing BATEA in Section V.
A. LITERATURE SUMMARY
I
lo Coagulation and Precipitation
Numerous chemicals have been evaluated by researchers for the coagu-
lation of pulp and paper wastewaters to achieve color reduction.
f
Among the chemical coagulants evaluated have been lime, alum, iron
salts, and fly ash. With the exception of lime, most of the research
has been done at the laboratory level to determine optimum pH, chemical
dosage, and the,resulting sludge handling characteristics. In a very
limited number of cases, coagulant addition has been done full scale at
pulp and paper mill treatment systems or in pilot plants. Iron and
aluminum based precipitants have been employed more extensively in
IV-1
-------
Europe, the U.S.S.R., and Japan than in North America where lime has
been the chief coagulant used.
Two treatment systems utilizing an alum color reduction stage (Baikal,
U.S.S.R. and Gulf States Paper in Tuscaloosa, Alabama) were reported in
an earlier EPA document (6). Raw wastewater color levels at the Baikal
mill averaged 1000 units and the treated effluent 101 units. Thus, the
overall color reduction approached 90 percent. Alum dosage (A1203) was
30 mg/1 and a flocculant (polyacrylamide) was fed at a rate of 1 mg/1 to
aid sedimentation. The Gulf States system included an alum recovery
process which has a projected recovery of approximately 94 percent. A
Gulf States spokesman has pointed out that the system is still in the
research and development stage until it performs over a sufficient
period to prove its complete practicality. However, initial results
have shown effluent color levels well below the presently proposed
EPA guidelines for BATEA (1983). Operating costs, based on 454 thousand
kilograms (kkg) per day or 500 tons/day of production, for the color
reduction portion of the Gulf States' treatment system has been estimated
to be $108.58 total and $68.37 operating cost per million gallons of
effluent treated. This equals $2.61 total and $1.64 operating cost per
ton of production (7).
Another full scale alum color removal study has been carried out at a
paper mill in British Columbia, Canada (8). Early trials resulted in
IV-2
-------
numerous problems in the process control. In addition, Freyschuss
reported on one unbleached kraft mill in Sweden which has achieved 90%
color removal with alum dosage of 120 mg/1 (8). The Degremont Company
of France is developing an alum treatment system similar to the one
being used in Tuscaloosa, Alabama by Gulf States Paper.
Olthof and Eckenfelder used ferric sulfate, lime, and alum to perform
laboratory studies on primary clarifier influent samples from three pulp
and paper mills (9, 10). Mill I and II produced bleached kraft and
groundwood pulps for the manufacture of newsprint, and Mill III was an
unbleached kraft paperboard mill. The study sought to determine three
things: 1) optimum pH; 2) optimum chemical dosage; and 3) character-
istics of the resultant sludge.
The optimum pH levels determined were 3.5 to 4.5 on the influent at Mill
I and II using ferric sulfate and 4.5 to 5.5 for Mill III. The optimum
pH when using alum was determined to be one-half unit higher in each
case, while the optimum pH using lime was 12.0 to 12.5 for all three
mills. The optimum dosage for each chemical at the three pulp and paper
mills is listed along with the respective percent color reductions on
Table 21.
IV-3
-------
TABLE 21
REQUIRED COAGULANT DOSAGE
Ferric Sulfate Alum Lime
Mill
I
II
III
Dosage
(mg/1)
500
275
250
Percent
Color
Removal
92
91
95
Dosage
(mg/1)
400
250
250
Percent
Color
Removal
92
93
91
Dosage
(mg/1)
1,500
1,000
1,000
Percent
Color
Removal
92
85
85
Evaluation of the various sludge characteristics indicated that lime
sludge resulted in higher allowable filter loading rates (at least four
to five times higher) and higher percent solids in the filter cake.
However, the advantages of using lime are partially offset by the
i
resulting larger quantity of sludge to be dewatered relative to the
amounts generated using ferric sulfate and alum.
The authors performed an economic evaluation based upon the results of
the laboratory experiments on the wastewater from the three mills. The
cost estimated included a solids contact clarifier, vacuum filter, and
the chemicals (polymer and coagulants) required to operate in the optimum
pH range. Costs were calculated for treatment systems of 1, 5, and 20
million gallons per day. The results of their cost determination are
shown on Table 22.
IV-4
-------
TABLE 22
COST OF COAGULATION
Effluent
Flow
(mgd)
1
5
20
1
5
20
1
5
20
Ferric
Sulfate
(c/1000 gal)
30.6
24.3
21.9
23.5
17.4
15.2
17.6
13.0
11.2
MILL I
MILL II
MILL III
Alum
(C/1000 gal)
29.2
22.7
20.4
24.8
17.7
15.8
18.4
13.7
12.1
Lime
(C/1000 gal)
28.4
21.8
19.2
24.3
17.8
15.3
19.8
16.0
14.3
It should be noted that the costs are based on 1973 prices, including
capital, operating, and maintenance. Chemical costs were $50.00 per ton
for ferric sulfate, $52.25 for alum, and $20.00 per ton for lime.
It was concluded that ferric sulfate used for color removal of pulp and
paper mill wastewaters can be an attractive alternative to lime treat-
ment. The main reason for this conclusion was that the required optimum
dosage of ferric sulfate was 25 to 33 percent that of the optimum lime
dosage. Another reason which was discussed was the effluent quality
which results when using lime. Lime treatment results in a high pH and
IV-5
-------
a great deal of calcium in solution. Common practice is to use an
additional treatment step, recarbonation, which will reduce the pH and
recover the calcium as CaC03. The use of ferric sulfate and alum,
however, does not require this additional treatment step, and depending
upon the buffering capacity of the biological treatment, may not require
any neutralization. Berov studied the need for neutralization of kraft
mill effluents which were treated with alum for color removal (11). He
concluded that if the chemically treated process effluent pH did not
fall below 5.8, neutralization was not needed. As indicated above,
however, this is dependent upon the buffering capacity of the biological
treatment in each case.
Jensen and Meloni studied coagulation with aluminum sulfate, ferrous
sulfate, and fly ash on three wastewater streams from a kraft mill in
Finland (12). The wastewater streams studied were the pine barking
effluent, screen room effluent, and the alkaline extract from the
bleachery. The purpose of the study was to test the suitability of
chemical treatment of these wastes to meet effluent guidelines. Addi-
tionally, the intent was to find a chemical that could be used most
economically.
The color reduction results on all three wastewater streams were in the
range of 80 to 90+ percent. The range of chemical dosage used for fly
ash was 1,000 to 20,000 mg/1 on all three wastewater streams. The
IV-6
-------
aluminum sulfate dosages were 100 to 500 mg/1 on the barking effluent,
50 to 600 mg/1 for the screening effluent, and 500 to 2,500 mg/1 for the
bleachery effluent. Ferrous sulfate dosages were 100 to 700 mg/1 for
the barking effluent, 300 to 1,100 mg/1 for the screening effluent, and
1,000 to 3,000 mg/1 for the bleachery effluent.
Optimum chemical dosages for the bleachery effluent with respect to
color removal were over 5,000 mg/1 for fly ash, 1,500 mg/1 for aluminum
sulfate, and 2,500 mg/1 for ferrous sulfate. These chemical dosages
reduced color to the 2,500 mg/1 level from influent color levels which
were 14,000 to 20,000 mg/1. This represented color reduction effici-
encies of over 80 percent. Color reduction over 90 percent was achieved,
but the increase chemical dosage to achieve the additional 10+ percent
removal was significantly higher than the previously mentioned dosages.
Fly ash dosage required went from 5,000 mg/1 for 87 percent reduction to
20,000 mg/1 for 97 percent reduction. Alum dosage required went from
1,500 mg/1 for 82 percent reduction to 2,000 mg/1 for 96 percent re-
duction. The ferrous sulfate dosages required went from 2,500 mg/1 for
87 percent reduction to 3,000 mg/1 for 97 percent reduction. One of the
conclusions arrived at from the study was that fly ash was comparable or
superior to lime as a treatment chemical.
Nasr, Gillies, Bakhshi, and Macdonald performed laboratory studies
i
utilizing the waste products from a coal-burning electric generating
plant (hydrochloric acid and fly ash) for color removal from a pulp mill
effluent (13).
IV-7
-------
The fly ash used in the study had as its major component silica.
Aluminum and calcium were the most abundant cations. Caustic extraction
filtrate from a bleached kraft pulp mill was the wastewater stream
investigated. The average color concentration was 12,000 units with pH
of 8.5. Initial laboratory experiments were performed using untreated
fly ash. A dosage of 1,000 gm/1 of fly ash was needed to achieve a 51
percent color reduction with the pH increasing to 9.4.
Experiments were then performed to see if the components of fly ash
could be released into solution by treatment with HC1. The main purpose
of this treatment was to release calcium into solution because of its
effectiveness in chemical precipitation for color removal. The tests
indicated that 20 mg equivalents of HC1 were required to completely
acidify one gram of fly ash. Two hours of stirring was required for the
completion of acidification reactions.
An optimum pH of 5 was determined for color removal. The optimum acidi-
fied fly ash requirement was found to be 1,900 mg/1 which resulted in a
color removal of 98 percent. Most of the color removal was attributed
to precipitation of colored material by reaction with metal ions released
from the acidified fly ash. Sludge was found to be voluminous and slow
to settle. After 12 hours of settling, the sludge occupied 15 percent
of the volume of the effluent.
IV-8
-------
The study concluded that due to the quantity of fly ash, dried sludge,
and HC1 needed for acidification purposes, a fairly large materials
handling problem would exist if this treatment were to be utilized on a
full-scale basis.
Dugal, Church, Leekley, and Swanson performed laboratory studies on
color reduction with a combined ferric chloride and lime treatment
system (14). This study sought to establish conditions for improving
the lime treatment systems by using multivalent ions with the lime for
color precipitation. Earlier investigations of the lime precipitation
treatment system showed that removal of color using only lime was 85 to
90 percent and that the remaining color bodies had an apparent weight
average molecular weight of less than 400. Preliminary studies with
multivalent ions and lime showed almost total color removal.
Tests were run in the laboratory on the decker filtrate and caustic
extraction discharge from International Paper Company's mill at Spring-
hill, Louisiana. Various salts such as barium chloride, ferric chloride,
magnesium hydroxide, and zinc chloride were used in the initial experi-
ments. Based on data from these initial experiments ferric chloride was
selected for futher analysis. In general it was determined that tri-
valent ions are 'more effective color removing agents than divalent ions
(See Table 23). '
Twenty-four experiments were run using ferric chloride and/or lime at
various concentrations. Color removal up to 98.7 percent was attained,
IV-9
-------
TABLE 23
TREATMENT OK KRAFT EFKLUKNTS WITH DIVALENT IONS
TREATMENT OK KRAFT EFFLUENTS WITH TR1VALENT IONS (14)
Decker Effluent
Caustic Exrract
Decker Effluent
Sa 1 t
concen-
t ration
_J5B/J__ -
Mg (Oil) 2
0
100
200
250
300
350
400
600
0
J.OO
200
250
'100
350
400
600
0
100
200
250
300
350
400
600
800
1000
Ca(OH)2
0
100
200
250
300
350
400
600
nal
ill
7
7
7
7
8
8
8
8
7
6
6
6
6
6
6
6
7
7
7
7
7
6
6
(,
6
5
-
-
-
-
-
-
-
.2
.4
.5
.8
.0
.0
.1
.0
^ 2
.9
.5
-.5
.4
.3
.2
.0
.2
.3
.2
.1
.0
.9
.7
.4
.2
.7
—
—
—
—
—
—
—
Color
Remova 1 ,
0
2
5
2
2
7
7
_
2
5
7
12
17
22
45
—
5
16
21
23
26
28
41
42
61
-
-
-
-
-
-
-
.5
.0
.5
.5
.5
.5
—
.5
.0
.5
.5
.5a
.5
.4
_
.0
.7
.7
.3
.7
.3
.2
.5
.2
—
—
—
—
—
—
—
Final
a.
a.
8.
8.
9.
9.
9.
9.
a.
6,
6.
6
6.
6
6.
6.
7.
6.
6,
6
6.
6
6
7
7
7
8
10
11
11
1 ]
11
11
12
.2
4
7
9
.0
0
,1
,2
.1
.9
.7
.7
.7
.7
.7
.7
.1
.9
.5
.5
.6
.8
.9
.0
. 1
.1
.6
.3
.3
.6
.7
.8
.9
.1
Color
Remova 1 ,
0
6.
11.
11.
11.
12.
22.
0
3.
3.
13.
13.
22.
44.
0
0
0
+1.
4.
1.
23.
35.
45.
20.
22.
22.
25.
32.
62.
72.
a
4
4
4
0
a
9
9
6
4
9
0
3
1
1
7
9
2
0
5
5
0
5
5
5
Sa 1 1
concen-
tration
mg/1
Alum (Alj
0
100
200
250
300
350
400
600
Fed -,-pll
0
100
200
250
300
350
400
600
FeCi3-PH
0
100
200
250
300
350
400
600
Color
Final Removal ,
j>H %
!
-------
and it was concluded that a synergistic effect between lime and ferric
chloride existed. Table 24 shows the results of these 24 experiments.
Another flocculation and precipitation process is in full scale opera-
tion in Japan, and being investigated through laboratory studies in
Sweden. The process involves using iron salts and lime to obtain color
removals in the range of 85 to 95 percent (8). Chlorination and
caustic extraction stage effluents are treated. Iron metal is first
dissolved in the chlorination stage effluent. Retention times of 1.5 to
2 hours and temperatures near 50°C are needed to dissolve a sufficient
amount of the metallic iron. The resulting solution is then combined
with the caustic extract and the pH adjusted within the range of 9 to 10
with lime. No chemical dosages were listed for the lime required or the
i
amount of iron metal consumed.
Vincent studied the decolorization of biologically treated pulp and
paper mill effluents by lime and lime - magnesia additions (15). Re-
sultant estimated costs were compared with those of conventional lime
treatment. Studies were conducted in a laboratory on effluents from
three kraft mills, one sulfite mill, and one NSSC mill. All except one
of the kraft mills had. been subjected to biological treatment before
chemical treatment.
Separate testing with lime and magnesia showed 1,000 mg/1 lime removed
approximately 90 percent of the color; however, magnesia alone proved to
IV-11
-------
TABLE 24
LIME TREATMENT OF KRAFT BLEACH CAUSTIC EXTRACT IN THE PRESENCE OF METAL IONa (14)
FeCls
mg/1
0
25
50
100
200
300
500
800
0
25
50
100
200
300
500
800
0
25
50
100
200
300
500
800
Lime,
ml
1000
1000
1000
1000
1000
1000
1000
1000
2000
2000
2000
2000
2000
2000
2000
2000
18,000
18,000
18,000
18,000
18,000
18,000
18,000
18,000
Sludge
vol.b
mg/1
6.2
8.2
8.2
8.5
13.3
14.4
22.0
30.1
6.2
7.0
7.3
9.7
14.1
19.1
33.5
62.0
8.9
8.7
9.0
9.4
11.2
12.2
14.3
16.8
Final
PH
11.58
11.50
11.42
11.42
11.49
11.50
11.40
11.32
11.79
11.70
11.70
11.70
11.70
11.71
11.78
11.73
11.98
11.99
11.98
12.00
12.01
12.01
12.01
12.00
Color
Removal ,
%
81.4
81.7
85.7
90.0
91.4
91.6
95.8
95.5
87.2
88.0
89.5
91.8
93.6
95.2
96.8
97.5
93.4
94.9
95.0
95.9
96.3
97.3
98.2
98.7
TOC
Removal ,
%
66.6
66.0
71.0
78.0
76.4
74.3
81.0
83.2
68.6
75.4
73.0
75.2
79.6
81.6
86.0
87.3
80.4
79.5
77.6
81.7
84.0
81.5
87.7
88.7
BOD
Removal
%
6.5
4.3
0.0
12.8
23.5
27.7
36.2
40.5
23.5
23.5
25.5
29.8
34.0
36.2
44.7
51.0
32.0
32.0
38.4
36.2
36.2
46.8
46.8
51.0
aUntreated caustic extract had a pH of 8.83, a color of 4400 units,
TOC of 220 mg/liter, and BOD of 47 mg/liter.
°Total volume of kraft bleach caustic extract after lime and FeCl3
addition was 100 ml. Sludge volumes were measured after a 15-minute
settling time.
IV-12
-------
be ineffective at moderate doses and required 4,000 mg/1 to get approxi-
mately 50 percent color reduction. Magnesia alone, therefore, could not
be justified because the amount of magnesia had little effect on color
removal. However, magnesium hydroxide freshly formed in situ was highly
effective when in combination with lime.
The magnesium was added as a soluble salt prior to the lime slurry. A
dosage of 50 to 100 mg/1 magnesia prior to 500 mg/1 lime gave the same
color removal as 1000 mg/1 of lime alone. Additionally, the volume of
sludge was less with the lime - magnesia process. Table 25 shows some
typical results of the lime - magnesia process for removing color, BOD,
COD, and phosphate for the five mills.
Recovery techniques were suggested but none were investigated in con-
nection with this study. This would indicate additional testing would
have to be done to prove the feasibility of this lime - magnesia re-
covery process before attempting it on a larger scale. Figure 66 shows
a schematic of the proposed process.
An evaluation concluded that the system is costly, but the benefits
might favor its use. Costs were estimated for a lime and lime-magnesia
process at a 500 ton per day kraft mill treating a combined effluent of
approximately 24 mgd. The costs were estimated assuming 1) no recovery,
IV-13
-------
TAIILE 25
REMOVAL OF 1101), COD, AND 1MIUSPI1ATI! AT SELECTED LIME - MAGNESIA LEVELS (L5)
I'reatmeiU Tri-a( mc-Ml Before Tro:i tinen t After Treatment Removal
II II
A
B
C
EfflmMir- -
CaO MgO
Kraft, combined effluent, 500 100
80% bleached biological
t rea tnu'iiL
Kraft, hi|;h
nnb leached ,
t rea tment
Kraft, conibi
biological L
KOI) stream, 500 100
not biological
ned effluent, 500 100
rea tment
Color BOO1- COD2 Phosphate3 Color BOD COD - -Phosphate Color BOD COf)
2,570 - 420 1.05 137 16 100 -iO.Ol 94.7 - 76
(560)
1,070 130 340 0.7 78 105 580 0.07 92.7 19
(560) 1,310
2,620 60 500 3.0 185 30 100 0.06 92.9 50 80
(720)
Phosphate
99.0
90.0
98.0
0 SnlfLtii, NH-j base, combined 2,000 400 1,790 60 2,430 0.8 298 67 460 0.07 83.4 - 81 91.3
effluent, biological (1,300)
treatment.
E NSSO, combined biological 6,000 3,000 36,300 525 8,640 31.5 12,800 320 1,040 0.80 64.7 39 88 97.5
L rea Linen t (4,960)
BOD determined after i" i ..Lr ration through Reeve-Angel glass filter papers, and subsequent adjustmen; to pH 7.
^COI) after fi I tral: i on through Keevo-Angf 1 gifts:; filter papers. Bracketed values are for unf i leered effluents.
Phoypbate anal ys J s (vn lues in mg/1 of I*) by modi f icd ascorbic acid method.
-------
FIGURE 66
A PROPOSED SCHEME FOR
LIME-MAGNESIA TREATMENT OF
COMBINED KRAFT EFFLUENT,
USING BOO mg/l LIME AND IOO mg/l MAGNESIA,
BASED ON IOOO GAL. OF UNTREATED EFFLUENT (15)
Combined Effluent
(1000 gal.)
MgS04
Soln.
10 gal.
(1 Ib. MgO)
Clarifier
1510 gal.
Filter or
Centrifuge
Ca(OH)2 soln.
500 gal.
(5 Ib. CaO)
Decolorized Effluent
1510 gal.
Sludge
(12.7 Ib. day)
Sludge Kiln
C02
CaO (4.83 Ib.)
MgO (1.02 Ib.)
Slaker
(leach tank)
500 gal.
Effluent for
disposal or
further treatment
(may be carbonatei
to lower pH if
required)
1010 gal.
CaO make-up if required
Filter or
Centrifuge
MgS04
tank
H2S04, water, 10 gal.
Mg(OH)2 make-up, if
required
-------
and 2) recovery of chemicals. The chemical dosages used to estimate the
cost were 1000 mg/1 of lime for the lime process and 500 mg/1 lime and
50 mg/1 magnesia for the lime - magnesia process. Tables 26 and 27 give
the cost breakdown.
Electrically induced coagulation has been discussed and studied by
researchers (10, 17). The theory described by Olthof for utilizing
electrolytic coagulation was that color consists of two fractions, A and
B (10). Fraction A is composed of large polymers which are amenable to
coagulation, and fraction B consists of smaller lignin degradation
products which are more easily oxidized and thus reduced in color by
chemical means. Therefore, it was concluded that an electrolytic cell
capable of producing both chlorine and polyvalent metal ions might be
effective in removing color from kraft pulp mill wastewaters. The
|
reasoning behind this proposal was that the chlorine would be useful in
reducing color in fraction B and that the polyvalent metal ions would
aid in the coagulation of fraction A.
Herer and Woodward conducted laboratory studies of this electrolytic
coagulation process (17). The removal mechanisms were found to be
coagulation by hydrated aluminum ions which were brought into solution
by electrolytic dissolution of the aluminum anode. Bleaching of small
i
color-causing polymers by chlorine formed by oxidation of chloride ions
at the anode was shown to be improbable. However, hydrogen bubbles
formed at the cathode aided removal of coagulated polymers by flotation
IV-16
-------
TABLE 26
ANNUAL COSTS OF LIME AND LIME-MAGNESIA TREATMENT (15)
(costs in thousands of dollars - 1974)
CaO (1000 mg/1)
No Recovery Recovery of CaO
from sludge
and effluent
(1) (2)
CaO-MgO (500-50 mg/1)
No Recovery Recovery of CaO-MgO
from sludge
(3)
(4)
M
1
H-1
^J
Equipment Capital
Chemical Cost
Direct Operating
Cost
Period Costs
Total Operating
Costs
Direct Operating
Cost per T. pulp
Total Operating
Cost per T. pulp
325
1163
1443
40
1483
8.25
8.47
3500
0
667
444
1111
3.81
6.35
325
866
1096
40
1136
6.26
6.49 '
3500
156
675
444
1119
3.
6.
86
39
-------
TABLE 27
ANNUAL COSTS OF LIME AND LIME-MAGNESIA TREATMENT (15)
(costs in thousands of dollars - 1974)
Supporting Data for Table 26
CaO - (1000 mg/1)
No Recovery ^
Total
Operating Costs
CaO - (1000 mg/1)
Recovery from sludge
and Effluent
CaO-MgO (500-50 mg/1)
No Recovery
CaO-MgO (500-50) mg/1)
Recovery from sludge
Chemicals
Sludge Disposal
Maintenance
f Utilities
M
OO
Labor
Indirect Labor
Total Direct
Costs
Depreciation
Insurance
Overhead
Total Period
Costs
1163
260
20
0
0
0
1443
33
7
0
40
0
0
210
373
60
24
667
350
70
24
444
866
210
20
0
0
0
1096
33
7
0
40
156
0
210
225
60
24
675
350
70
24
444
1483
1111
1136
1119
-------
action. Color removal efficiencies of 92 and 99 percent were observed
for chlorination and caustic effluents, respectively. These removal
rates were attained with an aluminum concentration of 143 mg/1 at a pH
of 4.3 and 230 mg/1 at a pH of 5.1 respectively. Table 28 shows the
results of the experiments.
An evaluation of the feasibility of the electrocoagulation process
determined that direct electrolytic treatment of kraft bleachery waste
is impractical. Whether or not an indirect electrocoagulation process
can be made practical depends upon the development of: 1) an electro-
lytic cell capable of energy efficiencies in excess of 50 percent and/or
2) the realization of beneficial reactions or activities which result in
a significantly better quality effluent than can be achieved with conven-
tional coagulation systems. Figure 67 is a schematic diagram of the
direct and indirect electrolytic processes. Figure 68 is a diagram of
the electrolytic cell used in the experiments.
Use of lime for coagulation and precipitation has been thoroughly
covered in prior Development Documents and for this reason was not
included except as it related to the studies described. Other studies
have also dealt with improving the existing lime treatment method of
color reduction.
Nicolle, Shamash, Nayak, and Histed have analyzed ways of improving the
settling characteristics of sludge from lime treatment of first extrac-
IV-19
-------
TABLE 28
SUMMARY OF EXPERIMENTAL RESULTS (17)
ro
o
Al concen-
Waste tration, mg/1
Chlorination
(17)
Chlorination
(previously reported)
Caustic extraction
(17)
Caustic extraction
(previously reported)
20
38
77
143
27
39
53
106
23
63
129
230
256
29
59
88
118
pH Range
for min.
color
3.0-4.0
4.5-5.5
4.0-5.5
4.5-5.5
4.5-5.5
4.5-5.5
4.8-5.5
5.5-6.0
3.8-4.8
3.5-4.5
4.3-5.3
4.5-5.5
5.5-6.5
3.5-4.5
3.8-4.8
4.0-5.0
4.0-5.0
Max. color
removal %
25
82
86
92
69
82
85
87
38
86
97
99
99
22
65
90
98
pH Range
for min.
carbon
3.5-4.0
5.0-6.0
5.0-6.0
4.5-6.0
4.5-5.5
5.0-5.5
4.8-5.5
5.5-6.0
4.5-5.5
3.5-4.5
4.5-5.5
4.5-5.5
4.5-6.0
3.0-4.0
4.0-4.5
4.5-5.0
4.5-5.5
Max. carbon
removal %
26
59
62
69
32
38
42
52
28
59
85
89
88
25
62
80
85
-------
FIGURE 67
DIAGRAMS OF DIRECT AND
INDIRECT ELECTROLYTIC PROCESSES (17)
Al Metal
Waste
Electrolyte
Electrical -
energy
Al Metal
Electrolyte'
Electrical
energy
Cell
Flocculation
tank
Settling
tank
*• Treated waste
•^Sludge
PROCESS I-DIRECT ELECTROLYTIC PROCESS
Waste
Cell
Mixing
tank
Flocculation
tank
Settling
tank
*-Treated waste
*-Sludge
PROCESS 2-INDIRECT ELECTROLYTIC PROCESS
-------
FIGURE 68
EXPERIMENTAL ELECTROLYTIC CELL (17)
Aluminum
Cathode
Alternating Current
Voltage Source
Variable Isolation
Transformer
Full Wave
Rectifier and
Filter Capacitors
Voltmeter
Ammeter
Aluminum
Anode
-------
tion stage kraft bleachery effluent which presently requires massive
doses of lime or addition of fiber to promote settling (18). It was
found that first extraction stage effluent loses its dispersant charac-
teristics if soluble calcium salts are added before the lime. The in-
vestigators discovered that lime dissolved in first stage chlorination
filtrate provides the necessary soluble calcium salts to promote fast
settling of sludge at low lime dosages.
The investigation was divided into two phases. The first phase objec-
tives were to determine the feasibility of a one clarification stage
lime treatment process and the manner in which it should be carried out.
The objectives of the second phase were to obtain data on the proposed
lime treatment process under continuous operating conditions using mill
effluents to obtain more realistic information on the process and its
actual feasibility.
The results showed that the lime treated waste settled rapidly resulting
in a clear supernatant only when sufficient calcium ions were present in
the system as described above. Two methods of providing the calcium
ions were analyzed.
First, dissolving some lime in the chlorination effluent prior to the
addition of extraction effluent followed by the bulk lime, or second, by
adding recycled sludge with the fresh lime to the combined CD and E]_
effluents. On the basis of the investigations it was recommended that
IV-23
-------
the first method be utilized rather than sludge recycle. The utiliza-
tion of a sludge return process resulted in approximately a 30 percent
color reduction and 40 percent COD reduction.
The mini pilot lime unit (see Figure 69) was then used in further
studies. Thirty runs were used in these additional tests. In runs one
through sixteen, two-thirds of the chlorination effluent and all the
caustic extraction effluent were treated. Lime additions ranged from
30.4 to 82.6 kg (67 to 182 pounds) of lime per air dried ton of pulp
bleached with four levels of sludge recycle: 0, 32, 50, and 68 percent.
During those runs with zero sludge recycle 13.6 kg (30 pounds) of lime
per air dried ton was added to the chlorination effluent prior to blen-
ding with the extraction effluent and the final dosage of lime. The
remaining one-third of the chlorination effluent was added to the
treated effluent leaving the clarification unit to reduce its alkalinity.
In runs 17 through 28, one-third of the chlorination effluent was treated
with the extraction effluent added to this treated chlorination effluent.
Lime addition ranged from 34.5 to 87.2 kg (76 to 192 pounds) of lime per
air dried ton and three levels of sludge recycle (Q-j 32, and 68 pjercent)
were studied. Lime was added to the chlorination effluent when no
sludge was recycled.
IV-24
-------
FIGURE 69
SCHEMATIC OF PILOT PLANT (18)
Cd(OH)2
Ca(OH)
Water
Lime
Slurry
Tank
g
ob
1
2
>
i
r^
20 l/hr ^
n
1
f
^
i
X 1
1
Heating 1
Unit .
1
1
i
A
Sludge Recycle
2.12 l/hr
Sludge
Bleed
DASHED LINES INDICATE OPTIONS
-------
In run 29, no lime was added to the chlorination effluent prior to the
addition of the extraction effluent, and no sludge was recycled. Two-
thirds of the chlorination effluent and all the caustic extraction
effluent were treated, and the remaining one-third chlorination effluent
added to the treated effluent. The lime addition was 56.3 kg (124
pounds) of lime per air dried ton of pulp.
In run 30, only the caustic extraction effluent was treated with lime,
and all the chlorination effluent was added to the treated effluent. No
sludge was recycled. The lime addition was 56.3 kg (124 pounds) per air
dried ton.
Data on some of the 30 runs that were made are shown on Table 29.
2. Activated Carbon Adsorption
Activated carbon treatment for color reduction has been reported in
previous EPA work. Many of these studies investigated activated carbon
as an additional treatment step to a mill's existing treatment system.
Some of the more recent work has involved investigations of activated
carbon for treating the more concentrated bleach plant effluent.
The NCASI studied the carbon adsorption of spent chlorination and
caustic extraction stage liquor color and organics on activated carbon
IV-2 6
-------
TABLE 29
ANALYSIS OF TREATED AND FINAL EFFLUENTS (18)
Run Number
Proportion CD Treated
Lime Added to CD Effluent, Ib/T
Total Lime Addition, Ib/T
Sludge Recycle Proportion
Mixing Tank Samples
Initial Settling Velocity, mm/min
Final Effluent Analysis
PH
Color, CPPA Method H5-P, Pt, mg/1
Color Removal, Pt, mg/1
% Color Reduction
COD, mg/1
% COD Reduction
Suspended Solids, mg/1
Alkalinity as NaOH, mg/1
Acidity as NaOH, mg/1
Total Carbon, mg/1
Total Organic Carbon, mg/1
Sludge Samples Analysis
Initial Settling Velocity, mm/min
Specific Resistance, 1()9 m/kg
1
2/3
30
68.1
0
19.4
10.54
1050
3280
75.7
973
36.5
52.0
116.0
N.A.
-
—
0.906
30.4
13
2/3
30
153.8
0
13.4
11.31
542
3790
87.5
875
42.9
111.3
-
N.A.
321
286
0.114
19.2
14
2/3
0
152.4
0.32
23.0
10.71
782
3550
82.0
885
42.2
71.3
144.0
N.A.
372
308
2.08
18.4
17
1/3
0
76.2
0.32
14.5
3.77
1650
2680
61.9
1011
34.0
68.7
N.A.
140.0
404
349
1.09
19.1
19
1/3
30
106.2
0
10.6
4.52
1410
2920
67.4
1010
34.1
48.7
N.A.
64.0
372
315
1.43
24.5
26
1/3
0
161.9
0.32
17.7
6.87
1470
2860
66.0
963
37.1
40.0
N.A.
2.0
377
323
2.09
10.4
28
1/3
30
191.9
0
17.3
6.73
1350
2990
68.9
902
41.1
38.7
N.A.
3.2
365
294
2.83
15.4
29
2/3
0
123.8
0
35.4
11.07
920
3420
78.8
913
40.4
144.0
188
N.A.
-
—
2.00
20.0
3.39
3010
1330
30.6
1336
12.8
84.7
N.A.
208.0
-------
(19). The purpose of the study was twofold: first, to determine the
reaction mechanisms of colored organic matter separation; second, to
determine those factors controlling color reduction efficiency and
chemically identifying the constituents removed and remaining after
treatment. A variety of activated carbons were investigated.
One of the findings was that removal of color was aided by a reduction
in the pH of the wastewater being treated. It was stated that this was
caused by reduced ionization of the colored weak organic acids present
which enhanced their adsorption on the activated carbon. It was also
found that molecular weight of the organics present was the second major
factor influencing the degree of color reduction. Color reduction was
found to be associated with removal of the high molecular weight materials.
However, the adsorption capacity of activated carbon displayed a pre-
ferential capacity for the low molecular weight fraction. Increased
removal of the higher molecular weight fraction could be achieved by
increasing the activated carbon dosage. Additional findings included
the observation that chemical factors were not decisive in controlling
the overall process of color reduction as was previously concluded. It
was also observed that when the spent chlorination liquor was in large
excess during the adsorption process or when the liquor was in contact
for a short duration with the activated carbon, a temporary color in-
crease occurred. This effect was traced to iron and other heavy metals
in the liquor. The carbon itself was a primary source of metals which
were released during treatment with acid liquors.
IV-2 8
-------
Rankin and Benedek tested several powdered and granular activated car-
bons for TOG and color removal using Indulin as a lignin model compound
(20). They determined that carbon pore size, relative to the molecular
weight of the color bodies, had the major effect on adsorption rate and
capacity. They concluded that the selection of the type and size of the
carbon was very important in maximizing color removal efficiency.
Gibney wrote a state-of-the-art paper on granular activated carbon
treatment (21). For a typical adsorption system the wastewater contacts
the carbon bed for 30-60 minutes at flow rates which vary between 0.082 -
0.303 cubic meters per minute per square meter (2-8 gallons per minute
per square foot). The thermal regeneration technique is better than
nonthermal reactivation of carbon. Optimal performance of an adsorption
i
system will depend upon proper pH adjustment and flow equalization.
Pretreatment should be performed if wastewaters containing suspended
solids in amounts exceeding 50 mg/1, or oils and greases in concentra-
tions above 10 mg/1 are present. Reuse of industrial process water
could make the carbon adsorption treatment process stage economically
justifiable. In a treatment system designed to produce reusable process
water the carbon adsorption stage would be a polishing step after the
bulk of the impurities have been removed by other treatment.
An EPA-supported pilot plant at Pensacola, Florida has evaluated both
the column granular carbon approach and a multi-stage countercurrent
fine-activated-carbon process (22, 23, 8). A major objective of this
IV-29
-------
pilot plant work has been production of reusable water from unbleached
kraft mill effluent. An effluent with color levels less than 100 units
and capable of being reused has been attained using dosages of 2.0 kg
(4.5 pounds) of lime and 1.1 kg (2.5 pounds) of carbon per 3.8 cubic
meters (1,000 gallons) of mill effluent. The effluent initially con-
tained 1,000 color units and 250 mg/1 TOG and BOD. The treatment system
tested in the four-year pilot plant study was primary clarification,
bio-oxidation, lime treatment, and carbon adsorption in various con-
figurations. The most economical process was found to involve a low
lime addition followed by carbon adsorption in downflow granular carbon
beds.
Capital costs were estimated for a 37,850 cubic meters per day (10 mgd)
flow from an 726.4 thousand kilogram (800-ton) per day mill in 1974
dollars at $7,000,000, with estimated operating costs of 30c per 3.8
cubic meters (1,000 gallons) or $3.85 per thousand kilograms (2,200
pounds) of production which included credit for reused water (22).
J3. Activated Alumina Adsorption
A calcium sulfite pulp and board mill located on the Lake of Constance
in Germany was faced with extremely tight discharge requirements (24).
In 1971, the mill started to evaluate all known processes for wastewater
treatment to meet these requirements. The mill employed research insti-
tutes and consultants experienced in wastewater treatment to evaluate
the various processes. The following methods of treatment were examined:
IV-30
-------
1. Single and multi-stage biological purification.
2. Coagulation with calcium, iron, and aluminum salts, alone and
in combination.
3. Catalytic oxidation (Katox process).
4. Ultrafiltration with tubular and sheet membranes.
5. Electrochemical processes.
6. Radioactive irradiation.
7. Ozonization.
8. Adsorption on activated carbon.
Methods 2 through 8 were employed following biological treatment. These
methods were also evaluated at the pilot plant level. After three years
of research it was concluded that all of the above processes were imprac-
ticable for this application. The reasons included poor performance,
processes which resulted in other difficulties (i.e., sludge production),
or in excessive projected cost.
The mill personnel involved in the research had evaluated numerous
adsorbants, mostly inorganic, in earlier investigations. Activated
alumina (aluminum oxide) had exhibited excellent adsorbance. The ad-
sorbant was tested with effluent from the pulp mill (dilute sulfite
liquor), effluent from the chlorination stage, and the combined effluent
from the bleach plant. The following results were observed:
1. The lignin components in the effluent were quantitatively
IV-31
-------
adsorbed by the activated alumina so that the treated water
had no detectable lignin.
2. The treated effluent was completely colorless.
3. After adsorption the foaming tendency of the effluent was
destroyed.
4. The materials present in the effluents which were not adsorbed
were readily destroyed biologically. They behaved like low
molecular weight compounds, similar to carbohydrates.
Regeneration of the activated alumina was then studied. It was deter-
mined that a thermal regeneration by heating the A1203 to 500-600°C in
the presence of air was the process to utilize. When the bleach plant
effluent pH was adjusted to 2.5 with HC1 before the adsorption step, a
reuse of about 89 times without suffering much loss in adsbrbant capa-
city was achieved.
The ratio of A1203 to effluent (weight/volume) is still uncertain;
however, 10-12 kg A1203 per cubic meter (0.085 to 0.102 pounds per
gallon) of effluent appeared to be the average. The researchers de-
veloped a laboratory test system which utilized five reactors in series
(four operating, one being regenerated). To alleviate the problem of
clogging of the activated alumina columns by suspended solids in the
wastewater being treated an upflow "swirling bed" reactor was developed.
Figure 70 is a schematic diagram of the process. Research into this
process is continuing and a full scale swirling bed reactor has already
been built.
IV-3 2
-------
SCHEMATIC
ALUMINA
FIGURE. 70
DIAGRAM OF THE GRANULAR ACTIVATED
PROCESS FOF$ COLOR REMOVAL (8)
BLEACHERY
EFFLUENT
SETTLING
UP FLOW COLUMN IN SERIES
TREATED
I
1
I
f
'
'
EFFLUENT "
ROTARY
DRUM
FILTER
INDIRECT HEATED
ROTARY KILN
(500°C)
REGENERATED
ALUMINA FOR
RECYCLE
-------
No attempt was made during the initial studies to estimate a cost for
this treatment process. Further research will, however, be directed at
establishing the technical requirements of this treatment process for
use in developing a preliminary cost estimate.
The latest reports on the small pilot scale studies being carried out
indicate that almost 100 percent of the color is eliminated with a
requirement of 7 kg ^263 per cubic meter of effluent (8). Flow rates
of 2-10 cubic meters per square meter per hour (0.8 to 4.1 gpm/sf) are
being attained. The optimum pH for operation of the columns is approxi-
mately 2.5. Further evaluations of this process are planned in Germany
and Canada.
4. Resin Separation and Ion Exchange Processes
The use of adsorption and ion exchange resins for color reduction of
kraft bleachery effluents has undergone extensive research over the past
few years. Several specialized resins recently developed have offered
improved results over those initially used. Included among these are
the processes developed by Rohn and Haas, Uddeholm-Kamyr and Dow Chemical.
An estimate of the cost (1974) for the Rohm and Haas process (Figure 71)
at a 635.6 thousand kilogram (700 ton) per day mill for a full scale
system was $1,495,000 in capital cost with an operating cost of $0.77
per thousand kilograms (2,203 pounds) of paper produced (8). Rock has
IV-34
-------
FIGURE 71
ROHM AND HAAS RESIN PROCESS
(25)
HIGHLY COLOURED
SPENT
BLEACHING
LIQUOR
TO PAPER MACHINES
WHITE
PULP
BLEACHING
FILTRATION
PROCESS
BROWN
PULP
BORROWED CAUSTIC
REGENERANT
, AMBERLITE
/ XAD-8
WOOD
CHIPS
PULPING
PROCESS
HIGHLY COLOURED
SPENT
REGENERANT
DECOLOURIZING
PROCESS
ORGANIC- LADEN
BLACK LIQUOR
RECOVERED
MOLTEN
CAUSTIC
DISCHARGE TO STREAM
CAUSTIC
RECOVERY
FURNACE
85 % DECOLOURIZED
BOD. REMOVED
BURNED
ORGANICS
DISCHARGE TO AIR
CARBON DIOXIDE & WATER
DECOLOURIZED
BLEACHING
LIQUOR
-------
estimated the capital cost in December 1973 dollars at $940,000 for a
full scale process at a 635.6 thousand kilogram (700 ton) per day mill
(25). More recent cost estimates (1975) for an 726.4 thousand kilograms
(800 ton) per day mill were $900,000 for capital cost and $0.72 per
thousand kilograms (2,203 pounds) of pulp for the operating cost.
Two methods for regeneration have been proposed for the Rohm and Haas
process. First, using the mill white liquor stream no soda loss would
result, but 1.3 to 5 percent additional evaporator capacity would be
required. Second, regeneration using the weak wash stream would require
no increase in the evaporator capacity, but soda make-up would be required.
White liquor regeneration is the more economical process (25). Two
potential disadvantages of the Rhom and Haas process are that low pH
(2.5) is required for optimum efficiency and a buildup of chloride in
the pulping process water could occur. Chloride accumulation, however,
is claimed to be at sufficiently low levels to produce no pulping and/or
recovery system problems. The process treats a combined caustic extract-
chlorination bleaching effluent.
The Uddeholm-Kamyr process (Figure 72) which is in full scale operation
at a 272.4 thousand kilogram (300 ton per day) mill in Sweden and also
in Japan, is apparently based upon a weak anionic type resin which
appears to utilize adsorption and ion exchange mechanisms for color
removal. The first caustic extraction stage is the stream treated.
Kamyr, Inc. in the United States is presently using a 76.0 liters (20
IV-36
-------
FIGURE 72
UDDEHOLM- KAMYR RAISIN PROCESS
(27)
BLEACHERY
EFFLUENT
FILTRATION
FOR
SUSPENDED
SOLIDS
REMOVAL
REGENERANT
(4-8% NaOH)
ION
EXCHANGER
RECOVERY
FURNACE
EVAPORATOR
ELUATE ON
REGENERATION
BLACK
LIQUOR
DECOLOURIZED
EFFLUENT
-------
gallon) per minute mobile pilot plant to collect operational data on the
system at several North American mills. Chloride buildup and a required
2 to 3 percent increase in evaporator capacity are the potential draw-
backs related to this process. No capital costs are available, but an
estimated operating cost of $0.99 per thousand kilograms ($0.90 per ton)
of pulp based upon the experience with the Swedish process has been.made
(8).
Komori studied color removal using activated carbon and 5 polymeric
adsorbants (26). He found that the polymers were equal or superior to
activated carbon for color removal. Regeneration was done using alka-
line solutions.
Chamberlin, Kolb, Brown, and Philp with Dow Chemical Company reported on
a polymeric resin process for reducing the color in bleach plant first
chlorination and caustic stage filtrates (28). The technology has been
field tested at a 590.2 kkg/day (650 TPD) bleached kraft softwood mill
utilizing a mini-pilot plant consisting of two columns, one-half cubic
foot per column. A diagram of the unit is shown on Figure 73. Recently
a new group of polymeric resins which are able to function over a wide
pH range have been developed by Dow Chemical Company and field tested at
the mini-pilot plant (29).
The influent wastewater streams to the mini-pilot plant contained color
levels in a range from 9,000 to 12,000 mg/1 with the average being
IV-38
-------
FIGURE 73
DOW CHEMICAL COLOR REDUCTION
MINI- PILOT PLANT UNIT
(28)
Caustic
Sewer
NOTE- INFLUENT PASSED THROUGH SAND FILTERS
AND A CHARCOAL BED
COLUMNS ALTERNATE BETWEEN SORPTION
AND REGENERATION MODES
-------
10,500 mg/1. After three hours, at a flow rate of 7.5 bed volumes per
hour, 85, 92, and 84 percent total accumulated color reduction was
observed for pH's of 7.0, 5.4, and 4.0, respectively. No costs for the
system were developed.
5. Membrane Processes
Ultrafiltration, reverse osmosis, dialysis, and electrodialysis are all
processes utilizing membranes to accomplish wastewater treatment. The
basic differences between the processes are membrane permeability and
driving force. Dialysis and electrodialysis utilize membranes which are
mainly permeable to ions. The driving force through the membrane for
the dialysis process is the difference in concentration of ions across
the membrane, while the driving force for the electrodialysis process is
an electrical potential difference.
Dialysis requires a solution downstream of the membrane to be much more
dilute than the influent stream being treated. Therefore, dialysis is
not used to any great extent for treating pulp and paper process streams
and effluents where large flow rates of solutions have to be processed
(30).
Ultrafiltration and reverse osmosis (hyperfiltration) rely on an external
pressure to provide the driving force. Both of these processes can
utilize membranes which are permeable to molecules of a specific size.
IV-40
-------
Ultrafiltration has been the subject of pilot plant studies at Champion
International Corporation in North Carolina. Effluent streams treated
included decker and pine bleachery caustic extraction filtrates.
Results of these studies and others have been reported in an earlier
EPA document (6). A flow diagram of the process used in these studies
appears in Figure 74. Plugging of the membrane cartridges by residual
particles and membrane cartridge life have been the two major problems
identified through these studies.
Investigation of a related system was carried out by International Paper
Company in cooperation with the Oak Ridge National Laboratory and with
EPA support (32). Dynamically formed membranes composed of zirconium,
silicone oxides, and polyoculate were investigated for possible color
removal from caustic extraction and pulp washing effluents. It was
determined that dynamically formed membranes decreased the plugging
problem and lengthened the life of the membrane. The salt reduction is
also improved when using dynamically formed membranes. Laboratory
tests, primarily on kraft effluents, were performed with these new
membranes. It was determined that ultrafiltration was probably a better
alernative than reverse osmosis when using dynamically formed membranes
for treating bleach plant effluents. The organic concentrate would be
directed to the recovery system and the inorganic-rich stream discharged
or treated to recover process chemicals. Observed color removal effic-
iencies were generally above 95 percent.
The researchers concluded that although the results of the laboratory
tests were good, more work would be necessary to establish the technical
IV-41
-------
FIGURE 74
ULTRAFILTRATION FLOW DIAGRAM (3D
Reusable
Permeate
Effluent Stream
O-« pH Adjustment
Filter
Polishing
Fifter
Feed
Reservoir
Ultrafiltration
Cells
r
Solids Disposal
Incinerator
Vent to
Atmosphere
Gas
Scrubber
-------
feasibility of applying dynamic membrane filtration techniques to kraft
wastewater. Preliminary cost estimates were performed based on the
laboratory work and previous cost estimates from a desalinization pro-
cess. It was estimated (1974) that the treatment cost would be 5.3
-------
FIGURE 75
ULTRAFILTRATION PILOT PLANT
FLOW DIAGRAM (33)
Alkaline extraction effluent
from filter drum
Screen
100 mesh
Rejects
PRV
•IX-
150 gallon
Feed tank
Heating coil
•ex-
FRV
Pump
Drain valves
Ultra-
filter
Permeate sewered
LEGEND
PI = Pressure indicator
PRV = Pressure regulation valve
FRV = Flow regulation valve
-------
Initial trials with the pilot plant encountered difficulties in the form
of coating or fouling of the membrane surface. High velocities for
eliminating or minimizing these problems were attempted; however, resi-
dual fouling was still encountered. The use of a daily wash became the
final solution to the problem. The contents of the wash water required
was not specified. Results from the pilot plant work were similar to
those levels of removal attained in the laboratory work. It was also
shown that the sodium and chloride rejection measured was negligible,
which is important when considering recycling the concentrate to the
recovery plant.
An improved polymeric membrane, which has increased resistance to
chemicals and temperature, has been developed for use in future pilot
plant work. The researchers feel that color removal should reach 80
percent without a decrease in flow rate when the new membrane is tested.
Pels, et. al. studied ultrafiltration at the laboratory level (34).
Prefiltered bleach kraft mill effluent was used along with five dif-
ferent sized molecular weight cutoff membranes. The membranes were made
of cellulose acetate. It was concluded that ultrafiltration provided
good removal of color, COD, and BOD. A molecular weight cutoff of
10,000 appeared to be the most effective in terms of removal efficiencies.
A preliminary cost estimate based upon this laboratory work indicated
relatively high costs for the ultrafiltration process. A capital invest-
ment in the range of $20 to $50 million for a 454 thousand kilograms
IV-45
-------
(500 ton) per day mill with an operating cost of about $0.26 per cubic
meter (264.2 gallons). Exactly what was included in the estimated costs
did not appear in the referenced article.
Studies of reverse osmosis for color removal have been reported in an
earlier EPA document (6). Reverse osmosis utilizes membranes which
reject lower molecular weight solutes; however, lower flux rates occur
along with a need for higher operating pressure differences across the
membrane than those experienced with ultrafiltration.
The research at the Oak Ridge National Laboratory, described previously,
also evaluated reverse osmosis (hyperfiltration) treatment of brown-
stock washer, decker, and screen-room effluents as well as bleach plant
effluents (32).
The reverse osmosis process utilized a dual-layer membrane, prepared by
exposing a hydrous oxide sublayer to a solution containing poly (acrylic
acid) at low pH. This type of membrane, which has rejection properties
expected of a polyacrylate cation-exchange membrane, has appeared promising
for desalination of brackish water.
Initial tests were carried out on the brown-stock decker effluent to see
if reverse osmosis could effectively concentrate the effluent to make
recovery by evaporation, or reuse of the filter practical. The reverse
osmosis treatment of the simulated brown-stock water was carried to
IV-46
-------
approximately 85 percent water recovery. The permeate which resulted
appeared adequate for reuse for example, in the bleach plant. It was
also noted that the concentrate approached the concentration necessary
for returning to the evaporator, along with the weak black liquor, for
eventual chemical recovery. Figure 76 shows the rejection (percent),
flux rate, and the concentration of contaminants in the permeate which
resulted from the tests on the brown-stock water. The tests were
conducted at a pressure of 950 psig, a temperature of 43°C, and a pH of
7.7 to 8.6.
The reverse osmosis process was then used to treat a caustic extraction-
stage effluent, adjusted to the experimental pH values with chlorination
stage bleach plant effluent and with mixed bleach plant effluents. The
membranes produced a permeate suitable for recycle; however, the concen-
trate contained so much chloride that its introduction into the kraft
recovery system would be impractical. Table 30 shows the percent rejec-
tion, concentrate, and permeate levels which resulted from these tests.
TABLE 30
REVERSE OSMOSIS OF BLEACH PLANT EFFLUENT (32)
Observed Rejection % Concentrate Product
Color 99.9 9000-45,000 5-35
Pt-Co Units
Total Carbon 94-97 775-3200 25-100
mg/1
Chloride 80-90 1000-5000 150-1000
mg/1
IV-47
-------
FIGURE 76
REVERSE OSMOSIS OF SIMULATED
BROWN-STOCK WASH EFFLUENT
(32)
Z
o
o
UJ
a:
a
UJ
>
o:
UJ
en
m
O
o
•a
«w _.
o
01
20
40
60
80
100
WATER RECOVERY, %
20 40 60 80 100
WATER RECOVERY, %
Legend
o 0.27#m Selos tube at I9ft/sec
A 0.45 /4m Acropor at 15 ft/sec
-------
A preliminary estimate of the treatment cost per 3.8 cubic meters (1,000
gallons) for a 3,785 cubic meters (10" gallon) per day reverse osmosis
unit was $0.30.
Timpe and Lang (paper presented in May?1973) concluded in a comparison
of various techniques for removal of color from kraft mill effluents
that reverse osmosis was uneconomical (35). However, development of new
types of membranes and other technical improvements have made the reverse
osmosis process more feasible.
Nelson, Walraven, and Morris reported on the installation of a reverse
osmosis process at a neutral sulfite semi-chemical pulp and paperboard
mill in Green Bay, Wisconsin, which produces about 267.9 thousand kilo-
grams (295 tons) of paperboard daily (36). The reverse osmosis process
was incorporated as a balancing control function in the total mill reuse
system (see Figure 77). The operation was designed to maintain the
total volume of the recirculating excess white water within the limits
of system volume by the removal of high quality permeate. Forty-five
days operating data indicates a color removal over 99 percent and 8005
removal over 98 percent. The permeate quality has exceeded the level
called for in the specifications. Twenty-four modules failed during the
period with two-thirds of the failures blamed on manufacturing problems
and not on the design or exposure to the feed stream. It was concluded
that the problems with the modules could be resolved.
IV-49
-------
FIGURE: 77
PLANNED WATER RE-,USE SCHEMATIC (36)
Unclarified Water From Machine
•iiiiiiiin Unclarified Water Re-Use
Unclarified Water Spill Storage Loop
Clarified Water
-To Machine Showers
Re-Use-
Permeate
Water
Surge
Spill
Storage
Surge
-^
I
Filter
(Thickener)
Returned Solids
iiiiiiiiiiiitiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiini
iniikiiiiiiiiiiiiiiiiiiiiiiiit-
-------
Bansal reported on an improved design membrane called the "sand matrix"
module which was developed by Westinghouse Electric Corporation (37).
The membrane, which is a proprietary formulation with a cellulose
acetate base plus several chemical modifiers, is drop-cast into the
support tubes as a liquid, then cured to the design characteristics. It
is stated that the membrane support structure can stand much higher
elevated temperatures of 55°C to 65°C and pressures of 750 psig to 900
psig.
Two basic types of laboratory experiments were conducted with this
membrane. First, the performance of the membrane when using a fixed
feed composition produced by the continuous recycle of both permeate and
concentrate to the feed tank was investigated. Second, the effect of
variations in feed composition on the performance of the system by
recycling only the concentrate to the feed tank was evaluated. The
study was made to determine if reverse osmosis could be used to purify
the caustic extraction effluent from a bleached kraft mill using a CEDED
bleaching sequence. The purpose of the study was twofold: 1) to recover
90 percent of the water with a 75 percent or higher recovery of sodium
chloride in the reverse osmosis concentrate; and 2) to recycle the
reverse osmosis permeate to the bleach plant. The pH of the feed liquor
was not adjusted prior to the reverse osmosis system and it varied
between 7.1 and 9.6. The overall flux rates averaged 26.5 and 31.6
gallons per day per square foot at 750 psig and 900 psig, respectively,
for the two trials.
IV-51
-------
The final permeate was colorless and it was stated that it could be
considered of excellent quality for recycle to the bleach plant. It was
also noted that reverse osmosis techniques appeared to offer a feasible
approach to closing up kraft bleach plants, but that there are practical
limitations to the degree to which permeate recycle could be practiced.
This was because of a build-up of adverse temperature, pH, viscosity,
and the concentration of suspended solids, soluble components, pitch,
fearners, colors, etc. Recovery of sodium chloride from the reverse
osmosis concentrate is possible through one of two methods: 1) freeze
concentration, or 2) vacuum evaporation. A flow sheet for a reverse
osmosis process treating caustic extraction kraft bleach effluent at an
assumed typical 362.8 thousand kilograms (400 ton) per day bleached
kraft mill using 7571 cubic meters (2 million gallons) per day of water
appears on Figure 78.
The report concluded by pointing out that the economics of the process
are dependent to a large extent upon the life expectancy of the membrane
modules, as well as upon the membrane performance in terms of flux rates
and solute rejection. It was noted that newer type membrane modules may
be close to reaching the life expectancies and throughput rates required
for continuous commercial operations.
Gellman observed that a tentative cost estimate for a reverse osmosis
process of $0.82 per 3,785 liters (1,000 gallons) of water treated
(1972) from caustic bleach effluent had been reported (38). He noted,
IV-52
-------
FIGUR,E 78
TYPICAL REVERSE OSMOSIS PROCESS
FOR A 4OO TPD PULP MILL (37)
Pulp Mill
400 tpd
0.0125 mgd Fresh-
Water Makeup
2.0 mgd
Bleach Plant Recycle Loop
Recycle at 5000 gal/ton Pulp
Recycle 1.0 to 1.5 mgd
at 0.5- 1.0% Dissolved Solids
0.5 - 1.0 mgd
1.0-0.5% Solids
i
Reverse Osmosis
0.05 - 0.10 mgd
10-5% Solids
Vacuum Evaporation
or Freeze
Concentration
0.0125 mgd
40% Solids
0.45-0.90 mgd
Clean Water
0.037-0.087 mgd
Clean Water
Disposal or Recovery
of Salts and Organics
T
25 tpd
40 - 60% NaCI
-------
however, that the process costs were apparently quite sensitive to
membrane module replacement and maintenance charges, to membrane permea-
tion rates, and to increases in osmotic pressure as concentration
increases.
Balhar studied reverse osmosis for treating pulp and paper effluents and
determined that pressures from 570 to 1,200 psi would be needed to con-
centrate effluents containing liquors and bleachery effluents (39).
6. Flotation Process
Flotation processes, sometimes called adsorptive bubble separation
processes, include microflotation, precipitate flotation, and ion
flotation.
Haye and Munroe studied a dispersed air flotation process for color
removal utilizing alum and polyelectrolytes (40). Tests were conducted
using a laboratory scale "mini-plant" capable of operating on a con-
tinuous flow basis (see Figure 79). The retention time in the "mini-
plant" was 56 minutes. Chemical dosages were 300 mg/1 for alum and 0.6
to 3 mg/1 of a synthetic, high molecular weight, cationic polyelec-
trolyte. The optimum pH was found to be between 6.5 and 7.0, which
resulted in color reductions ranging from 83.5 to 95.5 percent.
Preliminary costs were estimated (1974) for treating the total effluent
from a 681 thousand kilograms (750 tons) per day mill (25 mgd) with 300
IV-54
-------
FIGURE 79
SCHEMATIC OF DISPERSED AIR FLOTATION "MINI - PLANT"(4O)
Air
Sludge
Draw- off
Feed
Polyelectrolyte *
-------
mg/1 of alum and 2 mg/1 of a polyelectrolyte. The chemical cost esti-
mate was $4.30 per ton of production. Development of an alum recovery
system would reduce the chemical cost and improve the feasibility of
this process.
The researchers recommended that a pilot plant be constructed and
operated to obtain more data, and that the pilot plant work should
evaluate the following:
1. Economic factors: plant cost, chemical costs, and manpower.
2. The efficiency of the dispersed air flotation system compared
to partially pressurized dissolved air system.
3. Design parameters: cell types, lamillar inserts, controls,
and residence time.
Das investigated floating of the precipitate formed by using amine (up
to 500 mg/1 dosage) with dispersed air flotation (41). He found color
removal difficult to achieve with this process.
Ion flotation has been found to offer a more attractive process for
color removal. The process consists of adding a cationic surfactant to
the effluent containing the soluble anionic lignin. An isoluble pre-
cipitate is formed and is transported to the surface by the passage of
air through the solution. The resulting froth layer is then removed.
Initial research conducted by Herschmiller showed that 95+ percent color
IV-56
-------
removal could be attained (42). Chan, Herschmiller, and Manolescu
continued the research to establish whether or not a technical basis
existed for further development of the process, and to develop pre-
liminary costs (43).
The effluent tested was combined bleach plant effluent which contained
approximately 2,000 Pt-Co color units. The bleaching sequence employed
at the kraft mill was CEDED. A schematic diagram of the laboratory
experimental appartus is shown in Figure 80.
Experiments were also run using the caustic extraction stage effluent
only. This effluent contained over 20,000 color units. Solution pH was
adjusted to 3.0 and 5.0 with hydrochloric acid prior to the flotation
experiments. Surfactant dosages of 1.20 and 2.80 grams per liter at pH
of 3.0 resulted in color removals of 56 and 86 percent, respectively. A
dosage of 4.00 grams per liter yielded only 52 percent color removed at
pH 5.0.
Initial experiments on the combined effluent dealt with pH and air
sparger size and their effect on color removal. Figures 81 and 82 show
the results of these initial experiments. The results indicate that
using a fine air sparger at a pH from 2.0 to 5.0 would result in color
removal of 95+ percent.
Tests were then conducted to determine the effect of pH and time on the
percent flotation recovery. The volume of the experimental ion flotation
IV-57
-------
FIGURE 8O
SCHEMATIC DIAG.RAM. OF THE ION
FLOTATION EXPERIMENTAL APPARATUS (43)
Speed
Controller
Vacuum Train
Pressure
Regulator
Compressed
Air
Cylinder
Funnel
Rotameter
Pressure
Regulator
V
X Valve
Manometer
Motor
LAJ
Stirrer
Flotation
Cell
Diffuser
Rubber
Bung
— DX
Sample
Line
-------
FIGURE 81
EFFECTS OF pH ON COLOR REMOVAL. (43)
100
80
CD
o>
tc.
o
o
O
0)
o
I
60
40
Dosage = 0.442gm/l
Fine Sparger
20
2.0
3.0
4.0 5.0
pH
6.0
7.0
-------
FIGURE 82
EFFECTS OF pH ON COLOR REMOVAL (43)
o
O
0)
100
80
60
40
20
Dosage = 0.480gm/l
Medium Sparger
2.0
3.0
4.0
5.0
6.0
7.0
8.0
pH
-------
apparatus was 2.5 liters. A surfactant dosage of 0.4 grams per liter at
an air flow of 2.5 ml per second and a fine air sparger were used during
the tests. It was determined that a pH of 5 and 40 minutes retention
resulted in an optimum flotation recovery of 95+ percent.
The experiments then sought to determine the optimum surfactant dosage
at a pH of 5.0. The optimum dosage was found to be 0.52 grams per liter
with a resulting color reduction of 98 percent (see Figure 83). It was
also determined that flotation recovery exceeded 90 percent in 10 minutes
producing a treated effluent of less than 100 color units. The optimum
dosage at pH of 3.0 and 5.0 for flotation recovery was then determined
to be approximately 0.5 to 0.55 with a resulting recovery of 95+ percent
(see Figure 84).
The optimum air flow rate for color removal and flotation recovery was
then determined. This optimum air flow rate was found to be 2.5 ml per
second at 20°C and 1 atm. Air flow rates below this level were insuf-
ficient to effectively float the suspended solids; above this rate,
excess turbulence hindered the flotation operation (see Figure 85).
Based upon color reduction of the bleach plant first caustic extraction
stage effluent of a 681 thousand kilogram (750 tons) per day mill, pre-
liminary chemical cost estimates were calculated to be approximately $30
per 908 kilograms (ton) of production (based upon surfactant Aliquat
221). This high cost made it extremely important to determine a surfac-
tant recovery process to make the ion flotation economically feasible.
IV-61
-------
FIGURE 83
PERCENT COLOR REMOVAL. VS. SURFACTANT DOSAGE (-43)
100
80
(0
o
i
o
o
U
0)
o
I
60 —
40
20 —
.1
pH
.3 .4
gm/ I
.5
.6
-------
FIGURE 84
DOSAGE VS. PERCENT FLOTATION RECOVERV (43)i
100
80
o
o
d>
JO
"a
75
ul
1
o
60
40
20 —
I
I
0.2 0.4
Dosage (gm / I)
0.6
0.8
O pH = 5
Airflow '
2.5 ml /sec.
A pH =3
Airflow = 1.5 ml/sec.
Fine Sparger
-------
FIGURE 85
PERCENT FLOTATION RECOVERY VS. AIRFLOW (43)
100
o>
cc
CO
35
u.
0)
S
0)
0.
80
60
40
20
A-A-
2.0 4.0 6.0
Airflow (ml/sec.)
8.0
O Flotation Recovery
/\ Colour Removal
pH = 5.0
Dosage = 0.4gm/l
Fine Sparger
-------
Studies into a recovery process within the time frame of this investi-
gation were inconclusive; however, it was concluded that most of the
chromophoric compounds in kraft pulp mill effluents can be removed by a
flotation process using cationic surfactants as collecting agents. The
major process variables of ion flotation were found to be surfactant
dosage, pH, sparger porosity, air sparger rate, and temperature. Aliquat
221, a commercial surfactant, available in bulk quantity at compara-
tively low cost from General Mills Chemicals, Inc., was found to be very
effective for color removal.
Optimum conditions for flotation using this surfactant was found to be a
dosage of 500 mg/1 and a 3.0 - 5.0 pH range. Under these conditions a
95+ percent color reduction is possible with residual colors less than
100 Pt-Co units and very little turbidity.
The researchers proposed a possible ion flotation scheme for color
reduction of the kraft mill effluent. Figure 86 is a diagram of this
proposed ion flotation process.
Further investigations to develop an economical surfactant recovery
process or formulate a very inexpensive surfactant were recommended. It
was also recommended that the possibility of utilizing ion flotation for
both effluent color and suspended solids removal be investigated.
IV- 6 5
-------
FIGURE
PROPOSED ION FLOTATION FOR
KRAFT MILL EFFLUENT DECOLORIZATION . (43)
Surfactant
Effluent
Scum
Flotation
Cell
Decolourized Effluent
Colorized
Caustic
Surfactant
Storage
Solvent
Separator
n
o
-------
7. Ozone Treatment
Pilot plant studies on ozone application for color reduction undertaken
by Bauman and Lutz (44) were reported in a previous EPA document (6).
Operating costs listed in that document to achieve a specific range of
color in the effluent were based on $0.25 per pound of ozone applied.
Table 31 shows these estimated operating costs.
TABLE 31
EXTRAPOLATED OPERATING COSTS (44)
Color of Ozone Operating Costs
Ozonated Effluent
300 - 450
250 - 350
150 - 200
125 - 175
Applied (mg/1)
10
20
30
40
Yearly
$121,500
$243,000
$364,500
$486,000
Per Ton of Pulp
$0.675
$1.35
$2.03
$2.70
Nebel, Gottschling and O'Neill all with Welsbach Ozone Systems Corpora-
tion conducted laboratory studies of color removal with ozone on four
different effluents (45). Two effluents were from kraft pulp and paper
mills (Mills A and B) producing fine papers, one was from a bleached
board mill (Mill C), and one was from a paperboard mill using 100 percent
wastepaper (Mill D).
The investigators briefly reviewed the three types of ozone generation
systems available. These three systems are shown on Figure 87.
IV-67
-------
FIGURE 87
OZONE GENERATION SYSTEMS (45)
Air
All
1 »P
>x
( } t-
^r 1
fc ,i
L
i — i
j
^
I
I
Air
S*\ A *
u + A i r
To Process
Filter Compressor Coolers
Driers
Ozonator
OZONE FROM AIR
uxygen From
Liquefaction
Plant
o3*o
Reaction
Vessel
02 To
Other
Process
Ozonator
OZONE FROM ONCE-THROUGH OXYGEN
Catalytic
Combustion Unit
Heater
il xHeat Exchanger
Water Seal
02
From Process
d
1
1
I
°t*
k
°3+02 ,
To Process
Compressor Coolers
Driers
Make-up
00
Ozonator
OZONE FROM RECYCLED OXYGEN
-------
The effluent levels desired were 100 color units for Mill A, 200 color
units for Mills B and C, and 50 color units for Mill D. Figure 88 shows
the laboratory equipment used in the investigations. Mill A required 70
mg/1 of ozone to accomplish the desired color level in the effluent.
Table 32 shows the effluent properties before and after ozone treatment
for Mill A.
TABLE 32
FINAL EFFLUENT PROPERTIES ACHIEVED AT MILL A (45)
Effluent Properties Removal
Before After
Color, APHA units
COD, mg/1
Total bacteria count
per 100 ml
Total coliform bacteria
count per 100 ml
PH
520
298
240,000
24,000
5.0
100
188
4,900
1,600
6.7
81
37
98
93
Mill B required 81 mg/1 on ozone to accomplish the desired color level
in the effluent. Table 33 shows the effluent properties before and
after ozone treatment for Mill B.
IV-69
-------
FIGURE 88 ...
LABORATORY OZONIZATION APPARATUS (45)
Effluent In
Effluent
Plexiglas Column
(15 Gal. Cap. Approx)
o
o o o
o
o
Ozone
Generator
•Ozone Line
Off Gas
Vent
K I Trap
T Sample
=t>V Valve
Porous
/"Diffuser
Drain
, Valve
-------
TABLE 33
EFFLUENT PROPERTIES ACHIEVED AT MILL B (45)
Effluent Properties Removal
Before
900
950
248
After
200
479
176
(%)
78
50
29
Color, APHA units
Turbidity, JTU
COD, mg/1
Mill C required 143 mg/1 of ozone to achieve the desired color level in
the effluent. Table 34 gives the effluent properties for Mill C before
and after ozone treatment.
TABLE 34
EFFLUENT PROPERTIES ACHIEVED AT MILL C (45)
Effluent Properties Removal
Before After
Color APHA units 1,600 200 88
Turbidity, JTU 620 207 67
COD, mg/1 275 217 21
BOD, mg/1 147 124 16
Total bacterial count
per 100 ml 130,000,000 1,180,000 99
Fecal streptococci bac-
teria count per 100 ml 40 0 100
IV-71
-------
The.recycled board mill (Mill D) required 29 mg/1 of ozone to achieve
the desired color level in the effluent. Table 35 shows the effluent
properties before and after ozone treatment at Mill D.
TABLE 35
EFFLUENT PROPERTIES AT RECYCLED BOARD MILL (45)
t
Effluent Properties Removal
Color, APHA units
Turbidity, JTU
COD, mg/1
Total coliform bacteria
count per 100 mg
Before
170
230
67
After
50
85
33
(%)
71
63
51
20,700
99.9
Based upon these laboratory studies and the results shown on Tables 32
through 35, daily ozone requirements were calculated for each of the
four mills. The kilograms of ozone per day required at each of the
mills is shown on Table 36.
TABLE 36
DAILY OZONE REQUIREMENTS (45)
Effluent Flow Daily Ozone
Initial Color Color Desired 03 Dosage Rate Requirements
Mill APHA Units APHA Units Required (mg/1) m^/d (mgd) kg (Ibs)
A
B
C
D
520
900
1,600
170
100
200
200
50
70
81
143
29
57,000
60,800
95,000
9,500
(15) 3,973 (8,750)
(16) 4,903 (10,800)
(25) 13,520 (29,780)
275
(605)
IV-72
-------
Preliminary estimated operating and capital investment costs were then
calculated for each mill. Then the actual treatment cost for 3.8 cubic
meters (1,000 gallons) of effluent treated was calculated. The actual
treatment cost included the sum of capital expenditures, installation
cost, debt-retirement cost, and the daily operating expenditure. The
installation cost was estimated to be 20 percent of the capital expen-
diture. This installed cost was then amortized over a 20-year period on
a sliding depreciation basis at a 6 percent interest level. Operating
costs are based on ozone generation, producing oxygen, and the cost of
recycling unused oxygen back to the ozone generator. The costs are
shown on Table 37.
The NCASI conducted studies at the laboratory level on 12 different
classes of mill effluents (46). The effluents treated included the
total mill effluent, bleachery effluents, and lime reduced color ef-
fluents. A small laboratory ozonator was used. Table 38 shows the
ozone requirements for selected effluents.
The study concluded that 15 to 50 color units were removed per mg of
ozone applied for bleachery effluents, 4 to 5 units per mg of ozone in
the total kraft mill effluents, and less than 1 unit per mg of ozone
in the lime treated effluent. In a draft report on effluent color reduc-
tion covering the technologies under investigation the NCASI concluded
that the cost of producing ozone is not encouraging for commercialization
of the ozone color reduction process (38).
IV-73
-------
TABLE 37
DAILY OPERATING, CAPITAL INVESTMENT AND TREATMENT COSTS, 1974 (45)
Mill A
Mill B
Mill C
Mill D
Daily ozone requirements (Ib)
Feed gas to ozone generators
Daily operating expense ($)
Number of ozone generators
Capital Investment for
ozone generators ($)
Installed cost ($)
Annual debt retirement
Cost per 100 gallons ($)
8,750
Oxygen
393.75
4
10,800
Oxygen
486.00
5
29,780
Oxygen
340.10
14
605
Air
48.40
1
315,000 372,000 976,000' 95,000
378,000 446,400 1,173,000 114,000
30,200 36,370 96,180 7,706
, 0.031 0.032 0.064 0.028
TABLE 38
OZONE REQUIREMENTS FOR COLOR REDUCTION OF
SELECTED PULP AND PAPER MILL EFFLUENTS (46)
Stream
Lime color reduced
hardwood caustic bleach
extract effluent
Kraft mill total
secondary treated
effluent
NSSC total mill
effluent sodium
Initial
Color (APHA)
425
540
7,500
Ozone Required For 75%
Color Reduction (mg/1)
100
85
850
IV-7 4
-------
Buley stated, in a report on ozone treatment for color reduction, that
from an economic point of view ozone treatment should be used after
other.treatment processes have removed the greatest portion of the waste
contaminants (47). He stated further that additional experimentation
may reduce the ozone dosage required for color reduction to 50 mg/1 or
less.
Ozone demand is mostly dependent upon the initial BOD or COD of the
wastewater being treated. Therefore, utilizing ozonation as a polishing
step subsequent to biological treatment may be the most feasible alter-
native.
8. Amine Treatment Process
The amine treatment process was developed by P. Monzie of Centre Tech-
nique de 1'Industrie des Papiers, Catons et Celluloses (CTP), Grenoble,
France, while he was working on the use of ion exchange resins as a
means of quantitatively recovering organic acids from pulp mill ef-
fluents. According to the basic process, a pulp mill effluent is first
acidified and then contacted with a dilute organic solution of a high
molecular weight amine. The color bodies present in the effluent react
with the amine to form an organophilic precipitate. The effluent is
reduced in color through phase separation, the color bodies collect in
the upper (organic) phase. The organic phase is then mixed with a
controlled (low) volume of alkaline solution to regenerate the amine for
IV-75
-------
reuse. The color bodies are thus concentrated in the alkaline solution.
In practice, for a kraft mill, the alkaline solution could be, for
example, white liquor. The "spent" white liquor would then be returned
for pulping use in the digesters. The colored organic compounds would
thus eventually be burned in the recovery furnace.
Based upon Monzie's earlier investigations extensive research by the
Pulp and Paper Research Institute of Canada, under a program sponsored
by the Department of Environment in cooperation with the Canadian Pulp
and Paper Industry, was undertaken using high molecular weight amines
(48, 49).
The amine treatment process was evaluated in a two-part study program
for the purpose of determining its applicability, and to make improve-
ments in the technical performance as well as to determine the economic
feasibility of the process in North America.
The first part of the program was performed through "batch type" labora-
tory studies to improve upon the Amberlite LA-2/kerosene system used by
Monzie in Grenoble, France during the initial research and development
work.
The results of the studies included finding a new combination amine
(Kemamine T-1902D) and solvent (Soltrol 170) which improved on the
Amberlite LA-2/kerosene system by reducing turbidity and residual odor
IV-7 6
-------
in the treated effluent, and slowing hardening of amine-complexed color
bodies.. Additionally, the new amine resulted in lower solubility in
water, and lower chemical costs. Color removals of 90 to 99 percent
from kraft mill effluents along with 10 to 74 percent BOD and 36 to 78
percent of COD removals were attained.
A small continuous operating laboratory "micro-pilot" unit was developed
for further laboratory testing. Color, BOD, and COD removals with the
"micro-pilot" unit were comparable to those obtained from the batch
testing in the laboratory. Figure 89 shows the degree of color reduc-
tion attained for the various samples tested.
A relatively low cost amine regeneration stage for the treatment of the
third-phase emulsion which forms during the process was developed. The
regeneration stage is a thermal treatment method in which amine, which
would otherwise be lost, is recovered by heating the centrifuged third-
phase emulsion in the presence of excess solvent (Soltrol 170) to about
120°C for several minutes. It is estimated that a recovery of about 98
percent of the amine from the third-phase emulsion could be accomplished
with this regeneration method.
Costs based on a preliminary engineering design of the amine process
treating alkaline bleach effluent from a 500 ADT per day bleached kraft
pulp mill was calculated. The capital cost of the amine treatment
process was estimated to be $564,000 with an annual operating cost of
IV-7 7
-------
FIGURE 89
TYPICAL DECOLORIZATION TEST RESULTS WITH T-1902D
(IN SOLTROL 170) USED AS THE TREATING AGENT (49 )
pH (after acid-
ification) of
effluent sample
to be treated
% Color Removal* @ 68 F (based
on filtered samples)
0
20
40
60
80 100
1. Bleached kraft mill
effluents
(a) Softwood
(i) bleach plant
caustic extraction
(ii) brown stock wash
(iii) bleach plant
chlorination wash
(iv) combined pulp mill
(b) Hardwood
(i) bleach plant
caustic extraction
(ii) brown stock wash
(iii) combined pulp mill
2. Unbleached kraft mill
effluents (softwood)
(i) combined pulp mill
3. Low-yield sulphite
mill effluent (hardwood)
(i) bleach plant
caustic extraction
4. Spent sulphite liquor
(softwood)
(i) sodium base
10% liquor in H2
-------
$1.41 per ADT. Figure 90 is a flow diagram of the amine process for
treating the caustic extraction effluent from a 500 TPD pulp mill.
The second part of the study consisted of mill-site tests at a bleached
kraft mill in Quebec (49).
Acidification of the effluent at the mill was done by using C102 gene-
rator waste acid prior to the amine treatment. The amine concentration
ranged from 10,000 to 20,000 mg/1. The ratio of solution of amine to
effluent was regulated in the range of 1:4 to 1:2 (by volume). Tests
were run on the caustic extraction effluent, caustic extraction plus
chlorination effluent, caustic extraction plus brown stock decker fil-
trate, woodroom debarking, and other combined mill effluents.
Color removal efficiencies were equal to or greater than those results
obtained in the laboratory batch and "micro-pilot" tests. Conclusions
made from the tests at the mill included the following:
1. For caustic extraction effluent, color removal was virtually
unaffected by wood species (i.e., hardwood versus softwood).
2. For a given effluent, the initial color had little effect on
the degree of color removal achieved.
3. An initial pH of 3.0 to 3.3 was required to achieve 95+ per-
cent efficiency of color removal.
IV-79
-------
FIGURE 90
.PROCESS FLOW DIAGRAM FOR A TYPICAL
AMINE. TREATMENT PROCESS ATA BOO ADT/DAY
PULP MILL (48)
From Bleach Plant
Caustic Extraction
Stage Seal Tank
I050USGPM
L-0~f
Amine Solution 200-500 USGPM
From Mill White
J Liquor Storage
Recycling of Spent Caustic Solution
Separator I
156,000 USG
Gravity
Separator II
I5.60O USG
Exchanger
one.
Amine
Soln. Storage
5OOUSG
Hydro-
cyclone
Liq-Liq
Centrifu
30O
Treated Effluent
Mix Tank
2O USG
Spent
Caustic
Solution
1-5
USGPM
To Mill White
Liquor System
Cone.
Sulphuric Acid
Storage 6,250 62, 500 USG
USG
-GT
Amine Solution
Storage. 125,OOO USG
CENTRIFU6ED THIRD PHASE
-------
4. The test results confirmed that color reduction of caustic
extraction effluent would provide the minimum cost solution to
the effluent color problem.
Additionally, the impact upon the existing mill operation was estimated
to be minimal, requiring 2 to 6 percent increase in black liquor evapora-
tion and lime production capacities.
Original cost estimates were updated and a cost comparison between an
amine and a lime treatment process for color reduction of the caustic
extraction bleachery effluent was calculated. The capital cost (1974)
for the amine treatment process at a 500 ADT per day bleached kraft
mill was revised to $596,000 and an operating cost of $1.47 per ADT of
pulp. The total annual cost comparison between amine and lime treatment
was based on a 500 ADT per day kraft mill with a volume of 3,000 gallons
per ADT of caustic extraction effluent. The after taxes total annual
cost for the amine process was estimated to be $1.10 per ADT of pulp
while the lime treatment process was estimated at $1.24 to $1.43 per ADT
of pulp.
The study recommended that additional research into the exact toxic
effects on amine treated effluent be performed as well as extended con-
tinuous operation of a pilot plant on one type of effluent (i.e., caustic
extraction effluent) to determine more reliable estimates of amine
losses and chemical costs. The average amine loss estimated from this
IV-81
-------
study was 1.04 pounds per ADT, but it was noted that these losses were
found to be very sensitive to small analytical and experimental errors.
9. Additional Color Reduction Techniques
There is a wide diversity of color reduction approaches which have been
studied. The stage of development of most of these processes is either
at the laboratory or pilot plant level. Most of the techniques have
been summarized; however, there are a few others which have yet to be
reviewed. This section of the report will cover these additional tech-
niques which have been investigated and reported on.
Irradiation for treating kraft and sulfite mill effluents was initially
studied by Lenz and Robbins (50). They observed that both kraft and
NSSC effluents using gamma radiation, both with and without supplemental
treatment by an oxidizing gas (62, air, chlorine), appeared to com-
pletely destroy color bodies. A study of a radiation enhanced oxidation
•
process for color reduction of pulp mill effluents was undertaken at the
Oak Ridge .National Laboratory sponsored by NCASI (51). It was shown
that exposure to 10^ Roentgens in the presence of 500 psi of oxygen
could achieve 90 percent color reduction. It has also been noted by
NCASI that attempts to commercialize this process are currently under
way (38).
Another study of the irradiation process for color reduction was done by
McKelvey and Dugal (52). Their initial investigations were carried out
IV-82
-------
with a medium pressure mercury lamp in the presence of oxygen using un-
bleached kraft decker effluent, caustic extract from kraft bleaching,
and neutral sulfite semi-chemical pulp washings in a laboratory.
It was felt that the irradiation times were excessively long, and there-
fore additives were used in an attempt to shorten the reaction time.
The kraft decker effluent was used in these investigations. Sodium
hypochlorite was determined to be the best additive based upon its
effectiveness and cost. An alkaline pH was also found to be best for
this treatment process.
Irradiation time at various dosages of sodium hypochlorite versus color
levels was determined and the results are shown on Figure 91. The
researchers concluded that since this process is capable of 100 percent
color removal, the economics might make it more feasible to use the
process for removal of residual color after pretreatment by another
method. Therefore, the treatment was tried on an effluent that had been
treated with lime for initial color removal. It was determined that the
irradiation time was reduced significantly on this pretreated effluent,
as Table 39 indicates.
The researchers concluded that additional investigations would be re-
quired before the^ economics of this process could be determined, but
they did point out that no chemical recovery or sludge handling problems
are associated with the process.
IV-83
-------
FIGURE 91
DECOLORIZATION OF KRAFT DECKER EFFLUENT
IN THE PRESENCE OF SODIUM HYPOCHLORITE
;(52) .
?
c
O
CM
z
o
z.
<
CE
too
90
80
70
60
50
40
30
20
0% NaOCI
15
30
45
60
75
RRADIATION TIME, min
-------
TABLE 39
EFFLUENT IRRADIATIONS WITH LIME AND
HYPOCHLORITE TREATMENTS (51)
Sample Concentration Irradiation Initial Final
Pretreatment Volume (ml) NaOCl (%) Time (min)
None
None
None
None
Lime
Lime
Lime
2802
2802
2802
2,8003
2802
2,8003
2.8003
0.2
0.1
0.04
0.1
0.05
0.017
0.035
12
18
36
15
5
5
8
27
23
26
26
71
80
80
98
96
95
88
96
91
98
Percent transmission at 520 nm.
^Optical path ca. 1.0 cm.
^Optical path ca. 6 cm.
A study was conducted by the Nova Scotia Research Foundation for the
Canadian Department of the Environment on the use of fungi for reducing
color, BOD, and suspended solids in pulp mill effluents (53). Effluent
from a kraft pulp mill was treated in aerated reactors in which the
fungi were grown on submerged screens without additional nutrients. A
wide range of pH (3 to 7.5) and temperatures (6°C to 20°C) was covered
in the experiments.
It was found that the maximum color reduction was about 50 percent at pH
5.0 and 7.5. Higher color removals would require nutrients. No color
reduction was observed at pH of 3.0. BOD reduction varied between 70
and 90 percent depending on temperature, pH , and fungus used. Removal
of suspended solids was also 75+ percent.
IV-85
-------
It was concluded that for high performance at a low pH and temperature,
the fungal method appeared to be an atractive alternative biological
method for the reduction of BOD and suspended solids from pulp mill ef-
fluents. However, more research was recommended before the ability of
fungi to remove color could be fully evaluated.
The fungal degradation of lignin that has been modified during pulping
has been studied by scientists at the Forest Products Laboratory of the
U.S. Department of Agriculture, Madison, Wisconsin (54). Data showed
that the organisms converted over 40 percent of lignin's aromatic carbon
from both kraft and bleached-kraft pulping into carbon dioxide.
B. EQUIPMENT MANUFACTURING DATA
In an attempt to gain more current pilot and/or full-scale data on color
reduction technologies, manufacturers of such systems were contacted.
Of concern were systems utilizing alum coagulation, polymeric adsorption,
ultrafiltration, ion exchange, and chemical precipitation. Information
sought included system application(s), performance based on field test
results, and both capital and operating costs.
The response of the manufacturers led to no substantive increase in
materials gleaned from the review of current and/or historic literature.
In all cases there was either no response, no additional material avail-
able, or, if there was, it was not available for public disclosure.
IV-86
-------
SECTION V
IDENTIFICATION OF THE COLOR REDUCTION TECHNOLOGY
REPRESENTING BATEA
Identification of a color reduction technology representing BATEA in-
volved an evaluation of all of the external color reduction technologies
previously discussed in Section IV. The evaluation included an analysis
of the color reduction efficiency of the technology; operational prob-
lems experienced; stage of technology development; wastewater stream or
streams treated; total cost of treatment; and an analysis of any full
scale color reduction technology in use. An inventory of external color
reduction technologies is shown on Table 40. The technologies shown are
either full scale operating plants; full scale but presently not oper-
ating; full scale testing or developmental stage; or pilot plants. The
evaluation of each of the technologies previously discussed is presented
on the next few pages along with the summary of the evaluations and the
identification of the color reduction technology presently representing
BATEA.
A. PRELIMINARY EVALUATION
1. Minimum Lime'
The minimum lime process has been reported in earlier EPA documents. The
process has been used for color reduction of the first caustic extrac-
tion filtrate at two bleached kraft pulp and paper mills which were
V-l
-------
TAHLK 40
INVKN'i'OKY OK KXTKUNAL COLOR REDUCTION TliCllNOMiCIES
Reported
Technology
Mi u iuium Lime
Mi n iiinini Li me
M i n iiniini L hue
Mini mum L i me
Massive Lime
Modified Lime
(l.jme Mud)
Li mtt
Lime - Magnesia
Domta r Ltd .
1 ron-Li me
Luc a tion
Cforgia Pacific
Woodland, Maine
Georgia Pacific
Crossett , Arkansas
Interstate Paper
U i ceboro, (!eo rgia
Co nt i nenta I Can
Hodge, Lou Lsiana
Springhill, LA
In ternn t i.oiui 1 Paper
Springhill, LA
Ca 1 cas len Paper
Kl Uabeth, 1A
SenneviJ. le, (Quebec ,
Canada
O j 1 Paper C'o. ,
Japan
Stage of Devel opment
Kul I scale (Down at
t ime of report)
I'u 1 1 seal e
Intermittent Use
Kull scale
continuous
Kull scale
Continuous
pi ant has been
d i stiiant 1 ed
Large scale pilot
plant has been
dismant.l ed
Kull scale
testing
Laboratory studies
with pilot plant
proposed
Kull scale
continuous
Waste Streams Treated Color Reduction
Alkaline bleach 4.3 MGD 80-85
Color 8,000-10,000 CU
Lime dosage .1,500-3,000
Caust if: ext ract
Lime dosage 2,000 mg/l
Unbleached kraft eff. 85-90
10 MCI)
Color 1 ,200 CU
Lime dosage 1,500 mg/1
Unbleached kraft and 85-90
NSSC boardmlll eff.
13 MOD
Color 2,000 CU
Lime dosage 1,000 mg/1
Caustic extract and >90
unbleached decker
effluent
unbleached decker
. effluent
Kraft effluent No information
Iliologically treated =90
kraft mi.1.1 effluent
Kraft bleachery effluent No information
Capital Operating
$7M,000 $1.37/ton
Excluding lime
kiln
Similar to G-l' Mill
in Woodland, Maine
$355,100
Excluding c.larifier
and lagoons
$1,761,561 $0.77/ton
Included all
effluent
treatment
$1 .807 ton
Amortized cost
availabl e
$6.35 - $8.47/ton
total operating cost
ava liable
Remarks
Cost - 1973
550 TPD Mill
Cost - 1968
400 TPD Mill
Cost - 1973
620 TPD Mill
Cost - 1973
Cost - 1974
500 TPD Mill
Lime-Si-'awa ter
Nova Scot la Pilot sealc
Kfsearch Konndat ion testi ng
Kraft mill effluent
5 - 10% seawater
Lime dosage £_ 250 mg/1
80
No information available
-------
A 1 I Mil
A turn
Alum
Art i vat oil
Ca rbon
(Irunular
Ca rbon
PPRIC
Carbon
Ai_-t ivatud
A) iiiii 1 na
™\
Mil del 10 Im-Kamyr
Ikidelio Im-Kamyr
TAUI.K M>
(Continued)
Reported
l.oc;it it'll Staj;c of Development Waste Streams Treated Co 1 or Reduction
C.u 1 f Scat:*.- I'.iper Pu.l 1 sra 1 e llnox- treated unbleached >90
TM sea loosa , A I ahaina devel opmenta 1 staj-e kraft effluent , 12 MOD
Color 800-1,200 API1A
units
Uike llalkal, I'u 1 1 scale Effluent from production <90
IISSR cont i nnous of ti re cord cellulose
and krafL pulp, 76 MGD
Color I., 000 units
Alum 30 nig/]
i'o 1 yac ry 1 amide f 1 occii l.ant
1- mg/l
Mi My in Sweden Ku 1 1 sc;ile Report on one mill: 'JO
funtiniiuiis UnhJeuchecl kraft effluent
Alum 120 rag/]
St. Kej-is 1'nper '-"rye s»j;il.e testing Affluent Crom a multiple 90
reiisacola , Florida pulping process mill.
Color 1000 C.U.
Miraiiuchi Timher Pilot I'l.ant Combined bleach kraft 50-60
Newcastle, N.B. effluent
Color 2,500 C.U.
Scott Martimes 7'ilot Plant Combined bleach kraft 75-85
Abercombie PC. effluent.
N.S. Color 2,000-4,000 C.U.
Inike of Constance Pilot Plant Biologically treated ''95
Clerinatiy effluent from a calcium
sulfite pulp mill.
Daishowa Paper Co. i'u 11 scale Alkaline bleaching ~95
Iwanuma, Japan continuous
IMdeholn] Pull scale Alkaline bleaching 90-95
Skoghall, Sweden continuous 8 m /MT
Color 14,000 C.U.
'
Cost
Capital Operating Remarks
Total amortized cost = $2.61 Cost - 1974
per ton, operating cost 500 TPD
= $1.64 per ton mill
No information available
No information available
$7,000,000 $3.50/ton Cost - 1974
800 TPD
mill
No information available
No information available
No information available
No information available
$500,000 $0.90 ton Cost - 1974
300 TPl)
mill
-------
Technology
Uddeholm-Kamyi-
Kohm and Haas
Dow Chemi ca )
Corp.
Ami ne Kxt racL ion
UI t r;i 1" i It rat ion
U I tra f i 1 trat ion
Rhone Pou l.enc
Reverse osmosis
Local ion
MI t Is in North
America
Several mi 1 Is in
North America
Quebec
Champ ion Inter-
nat ion a "I , Canton
NC
1 ml . , Cl oquet ,
M inn.
Creen Hay
Packaging,
Creen Bay, WI
TAI1LK 40
(Continued)
Reported
SLa&e ol; Development Waste Streams Treated Color Reduction
Mobile pilot plant: First caustic extract
Mob tie p i 1 ot plant Fi rst caustic extract 90
and Cl- off l.uents
and Cl . ef f 1 uents
Color 9,000-12,000
Pilot plant Caustic extraction 90-99
Pilot plant Pine caustic extract 90-92
Color 3000 CU
Pilot plant Caustic extraction 60-70
ef fluent
ef f 1 uent
Color 6000 CU
La rj;e sen 1 e NSSC pulp and paperboard
testing mi 1 1 wa s t e wa t er
Cost
Capi tal Operating Remarks
-
$1,495,000 $0.70/ton Cost - 1974
700 TPD mill
$ 596,000 $1.47/ton Cost - 1974
500 ADT mill
$0.06-$] .00/1000 gal. Cost - 1974
amort ized cost
No information available
-
-------
required to reduce color during periods of low flow in their receiving
stream. One of the keys to operation of the system is a properly de-
signed solids contact clarifier discharging sludge at 10-15 percent
solids. Additionally, the minimum lime process has been successfully
operated at two unbleached kraft mills. The total effluent from these
two mills is treated with color reductions of 85 to 93 percent reported.
The main operational consideration to be addressed with the minimum lime
process is enchancing the relatively slow settling rate of the lime
sludge. Section IV discussed various laboratory and pilot plant
studies which have dealt with perfecting this aspect of the minimum lime
process. The minimum lime processes in full scale use have also ad-
dressed this question. Fiber fines in the paper mill effluent at one of
the unbleached kraft mills was found to enhance color reduction with
lime additions well below the solubility of calcium hydroxide. The same
unbleached kraft mill experimented with ferric hydroxide, calcium carbon-
ate, starches, polyelectrolytes, and recausticizing sludge with only
marginal results.
The process developed at the two bleached kraft mills utilizes reuse of
the first caustic effluent in the woodroom prior to color reduction.
This provides the necessary source of fiber which aids in the settling
and dewatering of the lime sludge which results from the minimum lime
color reduction process. An operating cost of the minimum lime process
at one of the two bleached kraft mills was reported to be $1.37 per ton
of product in 1972. The minimum lime process has proven to be tech-
V-5
-------
nologically feasible for color reduction at bleached kraft mills. Oper-
ational problems such as slow lime sludge settling, sludge handling,
scaling, and foaming must be addressed when designing a full scale
minimum lime process. Section IV described continuing research into
improving the performance of the lime process through elimination of
these operational problems. Pilot plant and laboratory results on the
lime process in combination with other chemicals has been promising. A
brief review of the lime process in combination with these other chem-
icals will be performed.
Another study dealt with using only lime, but with a variation in the
method of application for the purpose of improving the settling rate of
the lime sludge. The process involved adding a portion of the lime in
the first chlorination effluent prior to addition of the caustic ex-
traction effluent and the remaining lime. Color reduction up to 87.5
percent was achieved.
2. Lime and Ferric Chloride
The lime and ferric chloride system was investigated because it was
found that minimum lime reduced color by 85 to 90 percent and that the
remaining color bodies had an apparent average molecular weight of less
than 400. It was theorized that addition of multivalent ions to remove
the lower molecular weight color bodies, and lime would result in almost
total color reduction. Laboratory experiments on caustic extraction
stage effluent determined the total color reduction to be 95.8 percent
V-6
-------
when 500 mg/1 of ferric chloride and 1,000 mg/1 of lime was added. Also
mentioned earlier was the color reduction technique used in a Japanese
mill. Iron metal is dissolved in the first chlorination effluent using
a 1.5 to 2 hour retention time, and then mixed with the first caustic
effluent and lime. No chemical dosages or costs for this system were
provided, but the process is achieving 85 to 95 percent color reduction.
3. Lime - Magnesia Process
This process was analyzed and found to provide good color reduction, but
at this time additional testing on a larger scale is needed and a
recovery system must be developed. Because of the early stage of
development of this process and the technical aspects still left un-
resolved it has been eliminated, at this time, from consideration as a
BATEA color reduction technology.
4. Chemicals Studied to Replace Lime
Numerous studies reported on in Section IV evaluated various other
chemicals for color reduction in place of lime. Some of the chemicals
evaluated for this purpose were ferric sulfate, alum, fly ash, aluminum
sulfate and ferrous sulfate. Alum will be discussed in detail later in
this section.
Ferric sulfate was concluded to offer an attractive alternative to lime
treatment, but additional studies are needed to establish the economic
V-7
-------
feasibility of ferric sulfate in place of lime. Technically its ad-
vantages are a decreased optimum dosage when compared to lime, and
elimination of the recarbonation step needed in lime treatment. Ad-
justment of pH after color reduction treatment and prior to effluent
discharge may also be eliminated when using ferric sulfate. However,
this would depend upon the buffering capacity of the biological treat-
ment system.
Fly ash proved equal or superior to lime treatment, but the amount of
sludge generated would result in a major solids handling problem. The
sludge was found to be voluminous and slow to settle.
The remaining chemicals mentioned were not as effective as the lime
treatment process for color reduction.
5. Activated Carbon Adsorption
Technically activated carbon adsorption has been proven to reduce color.
However, at this time the economics of the process appear to relegate
its use to that of a polishing stage treatment after the bulk of the
impurities have been reduced by other treatment steps. It does offer
the possibility of producing reusable industrial process water which in
certain situations might make the economics of the system feasible.
Carbon adsorption in continuous countercurrent stirred contactors is
believed to have promise of providing treatment at lower operating costs
V-8
-------
and substantially lower capital costs. A capital cost estimate for a 10
MGD treatment system for an 800 TPD mill was $7 million (1974). The
operating cost was estimated at $3.50 per ton of production which in-
cluded a credit for reused water.
Ruling this treatment out of consideration because of its high cost is
not within the framework of this report. Results from pilot plant work
were good, and therefore it was included in the final selection of a
BATEA color reduction technology.
6. Activated Alumina Adsorption
This process has been in the development stages at a calcium sulfite
pulp mill in Germany. The results of the technology development have
been encouraging thus far; however, further research is planned in
Germany and Canada to establish the specific technical requirements of
the process for use in developing a preliminary cost estimate.
The technology will not be included in the final selection of a BATEA
technology because it is at a relatively early stage of development.
However, it should be included in any future color reduction technology
reviews because of the promising results of tests done thus far.
7. Resin Separation and Ion Exchange Processes
Three processes have been developed to at least the pilot plant stage
V-9
-------
under this color reduction technology. These are the Rohm and Haas
granular resin separation process, the Uddeholm-Kamyr adsorption and ion
exchange process, and a polymeric resin process developed by Dow Chem-
ical.
Only the Uddeholm-Kamyr process is presently used on a full scale
operation. Two bleached kraft mills, one in Sweden and one in Japan,
are utilizing this color reduction technology on their alkaline bleach
effluent. Color reductions of 90 to 95 percent have been reported with
an operating cost of $0.90 per ton reported for the 300 TPD Swedish mill
(1974). Both mills have had to replace resin beds as a result of de-
activation problems.
The Rohm and Haas and Dow Chemical color reduction technologies are both
at the pilot stage of development. Rohm and Haas claims 90 percent
color reduction as a result of pilot work. Cost estimates developed
from the testing was $1,495,000 for a capital cost and an operating cost
of $1.70 per ton of production (1974) based upon a 700 TPD bleached
kraft mill treating the first chlorination and caustic effluents. The
Dow Chemical process claims 84+ percent color reuction of the same
wastewater streams; however, no cost estimates were available.
Both the Rohm and Haas and Dow Chemical color reduction technologies
have not been included in the final selection process of a BATEA tech-
nology because the processes need to be evaluated on a larger scale
basis to determine chemical regenerant requirements and the ability to
V-10
-------
recycle treated water back into various mill chemical systems. The
Uddeholm-Kamyr process will be included in the final selection at the
end of this section.
8. Membrane Processes
Ultrafiltration and hyperfiltration (reverse osmosis) have been under-
going continuous development for the past few years. Membrane fouling
and related problems have been the major drawback to both of these
processes. Prefiltration has until recently been necessary to attempt
to limit the membrane plugging problem. However, Rhone Poulenc has
developed a polymeric membrane which requires no pretreatment. Color
reductions of 60 to 70 percent were achieved in initial studies of this
new membrane.
Dynamically formed membranes are also being developed and tested which
are reported to decrease the plugging problem and lengthen the life of
the membrane. Initial laboratory tests of the dynamically formed mem-
branes for hyperfiltration and ultrafiltration were good, but the
researchers indicated more testing was necessary to establish the tech-
nical feasibility of applying these filtration techniques to kraft
wastewater.
Although the development of new membranes has resulted in improved
operations of ultrafiltration and reverse osmosis neither technology is
at the stage of its development to be considered in the final BATEA
V-ll
-------
technology selection. They do, however, warrant continued monitoring to
assess the effect of new breakthroughs in their technological develop-
ment.
90 Alum Coagulation and Recovery
Alum coagulation is presently in use in a bleached kraft mill in the
USSR, unbleached kraft mills in Sweden, and an unbleached kraft mill in
Alabama. Color reductions of 90+ percent have been reported at these
mills. Alum sludge handling problems have also been reported. The alum
color reduction process in Alabama has experienced operational problems
with the alum recovery process which is a part of their system.
Alum has proven to be capable of effluent color reduction in bleached
kraft mills, and as has been discussed above, is in full scale use for
this purpose. For these reasons alum will be included in the final
selection of a'BATEA technology.
10. Flotation Processes
Recently studies of dissolved air flotation and ion flotation for color
reduction of bleach plant effluents have been carried out at the lab-
oratory level. Ion flotation, seems to offer the more attractive process
for color reduction. However, the researchers pointed out that because
of the high cost for treatment, the feasibility of this color reduction
process depends upon development of a surfactant recovery process or a
V-12
-------
low cost surfactant.
Both of the flotation processes are at an early stage in their devel-
opment with technical and economic problems and questions still to be
resolved. For these reasons they were not included in the final selec-
tion of a BATEA technology.
11. Ozone Treatment
Ozone has been shown through laboratory tests to be capable of color
reduction of kraft mill wastewater. However, ozone demand for color
reduction has been found to depend upon the initial BOD or COD of the
wastewater being treated. Additionally, the cost for ozone generation
and color reduction is high. Therefore, it is felt that utilizing
ozonation as a polishing step subsequent to biological treatment may be
the most feasible alternative.
Development of a less expensive method of generating ozone is needed to
make this color reduction technique feasible. For the reason of ex-
tremely high cost and a lack of any extensive pilot plant operating
results ozone has not been included in the final selection of a BATEA
technology.
y
12. Amine Treatment Process
The Pulp and Paper Research Institute of Canada has been studying the
V-13
-------
possibility of utilizing high molecular weight amines for color re-
duction of the alkaline bleach plant effluent. The testing has pro-
ceeded from the initial laboratory analysis to the pilot plant stage.
The results of the pilot plant testing showed that color reduction of
the caustic extraction effluent would provide the minimum cost amine
treatment process solution to the effluent color problem. It was also
estimated that the impact upon existing mill operations would be min-
imal, with 2 to 6 percent more black liquor evaporation and lime pro-
duction capacities required. A preliminary cost estimate was developed
for a 500 ADT per day bleached kraft mill reducing the color in the
caustic extraction bleachery effluent. A capital cost of $596,000 was
estimated and an operating cost of $1.47 per ADT of pulp.
The researchers recommended more extended continuous operation of a
pilot plant as well as research into the toxic effects of the amine
treated effluent be performed to determine more reliable data on the
system.
Because of the preliminary stage of development of the amine treatment
process and the questions left to be resolved it was not included in the
final selection of a BATEA color reduction technology. However, any
future research should be monitored so that future updates of the color
reduction technologies can report on the development of the amine
process.
V-14
-------
13. Other Color Reduction Techniques
Other color reduction techniques reported on, irradiation and fungal
degradation, are both at early phases in their development. Specific
operating data is not available for use in adequately assessing the
ability of each process to provide an economic, technically sound color
reduction technique. Therefore, the processes have not been included in
the final selection of a BATEA color reduction technology.
B. FINAL EVALUATION - IDENTIFICATION OF A TECHNOLOGY REPRESENTING BATEA
The following technologies were selected for the final evaluation in the
identification of a technology representing BATEA:
#
1. Minimum lime;
2. Activated carbon adsorption;
3. Uddeholm-Kamyr ion exchange; and
4. Alum coagulation and recovery.
At the beginning of this section it was stated that the evaluation of
BATEA color reduction technologies would be based upon: (1) stage of
development of the process (full scale, pilot plant, etc.); (2) oper-
ational problems experienced; (3) total operating cost; (4) the waste-
water streams that can be treated; and (5) the color reduction efficien-
cy of the process. The four technologies selected after the preliminary
evaluation will be evaluated in a more detailed manner.
V-15
-------
The stage of development of the color reduction technology was selected
as the most important factor in the selection of a technology represen-
ting BATEA. Many of the technologies achieved excellent color reduction
efficiencies. However, if the technology is only at the laboratory or
pilot plant stage in its development, then the value of the data re-
ported must be evaluated with this in mind. Operational problems and
cost data cannot be adequately assessed at this early stage of devel-
opment, and the problems which do occur when technologies are scaled up
cannot and normally have not been identified.
The factor that was selected next was operational problems experienced
by the technology at the specific stages of its development. A tech-
nology must be able to operate on a continuous basis with a minimal
amount of operational downtime to be considered an effective and useful
color reduction technology. Total operating cost was selected as the
next evaluation factor. Cost of treatment, as has been covered earlier,
does affect a treatment technique's value as a feasible color reduction
technology.
The specific wastewater streams within the bleached kraft mill which can
be treated by the technology was selected as the fourth evaluation fac-
tor. Many technologies can achieve optimum efficiency and treatment
operation through treating only one specific wastewater stream. The
value of this type of technology at a mill whose color originates at
another wastewater stream is obviously minimal, and selection of a
different color reduction technology must be made.
V-16
-------
The factor selected as least important was the color reduction efficien-
cy. For the four technologies being evaluated there is very little
difference in color reduction efficiency. All are reported to achieve
at least 80 percent color reduction efficiency. For this reason, the
efficiency of the color reduction technologies is of minimal importance.
The resulting point values assigned to the five evaluation phases are
presented below:
Stage of color reduction technology development = 5
Operational problems experienced = 4
Total operating cost = 3
Wastewater streams treated = 2
Color reduction efficiency = 1
Each of the five evaluation factors will be presented below with the
four color reduction technologies evaluated and rated within each of the
five phases. A point value of four will be assigned the best technology
for the evaluation factor being analyzed, and a point value of one
assigned to the technology considered to be less advantageous under that
evaluation phase.
It should be noted before the evaluation factors are assigned point
values that the selection of most important to least important was done
on a general overall basis. Individual mills may rank the evaluation
factors in a different sequence and thereby achieve a different BATEA
V-17
-------
technology. However, on a general basis it was concluded that the
ranking of the evaluation factors should be as presented in this section.
1. Stage of Color Reduction Technology Development
Minimum lime and alum coagulation have been developed to the full scale
operational stage at more pulp mills than the ion exchange technology or
activated carbon. Minimum lime, or a lime process, for color reduction
is in full scale operation or available for full scale operation at six
pulp and paper mills. Alum coagulation is used at a bleached kraft mill
in the USSR, unbleached kraft mills in Sweden, and one in Alabama.
Minimum lime and alum can be considered to be at about the same stage of
development except for their respective recovery systems. Minimum lime
has a recovery system which has been operational, while an alum recovery
system is still being developed. For this reason, minimum lime was
rated as the most advanced color reduction technology, with alum second.
The Uddeholm-Kamyr process is being used at a bleach kraft mill in
Sweden and Japan, while the activated carbon adsorption process is not
in full scale operation at any pulp and paper mill for the purpose of
color reduction. It has undergone pilot plant testing. The resulting
point values given to each of the four technologies for this evaluation
phase is shown below:
Minimum lime = 4.0
Alum coagulation and recovery = 3.0
V-18
-------
Uddeholm-Kamyr (ion exchange) = 2
Activated carbon adsorption = 1
2. Operational Problems Experienced
From the data available at this time it was concluded that the activated
carbon adsorption process experienced the fewest operational problems.
However, it should be noted that no full scale activated carbon ad-
sorption color reduction process is in use on a full scale basis.
Minimum lime treatment was selected as the next technology with fewer
operational problems. The decision was based on a comparison with an
alum coagulation and recovery system. Sludge handling problems are
common to both processes. Dewatering aids, such as fiber for the lime
process, are used to improve the sludge handling. The lime recovery
system has been tried and proven, but the alum recovery process is a
technology still being developed.
Ranked last in this evaluation phase was the Uddeholm-Kamyr ion exchange
process. Resin beds have required replacing at both of the kraft mills
using the process because of deactivation problems.
The results of the point values for each of the color reduction tech-
nologies under this evaluation phase are listed below:
V-19
-------
Activated carbon adsorption - 4
Minimum lime =. 3
Alum coagulation and recovery = 2
Uddeholm-Kamyr (ion exchange) = 1
3. Total Operating Cost
The cost comparison between the four color reduction technologies was
based upon actual operating systems or pilot plant work done at a mill
site. Table 40 presented both capital and operating costs for the color
reduction technologies. Detailed capital cost estimates for these
technologies on a model mill situation was not required, therefore, it
was necessary to base the capital cost assessment on the data provided
on Table 40.
Activated carbon would require the highest expenditure of capital. It
is much more difficult to compare the remaining three technologies
from a capital expenditure standpoint, but alum coagulation and recovery,
minimum lime and ion exchange would all be at least less than half the
capital cost of an activated carbon system.
Based on the available operation and maintenance cost of the four tech-
nologies the Uddeholm-Kamyr (ion exchange system) is the least costly
to operate, followed by minimum lime, alum coagulation, and activated
V-20
-------
carbon. It should be pointed out that both the alum and activated
carbon systems were based on color reduction at unbleached kraft mills,
and as such the cost for similar treatment at a bleached kraft mill can
be expected to be higher in terms of operating cost. Costs, and their
source, for the four technologies are presented on Table 41.
TABLE 41
COMPARISON OF COLOR REDUCTION TECHNOLOGY COSTS
Technology Cost Information
Minimum Lime Capital cost $843,000
Total operating cost $1.55/ton
Alum coagulation and re- Total operating cost $2.61/ton
covery
3
Activated Carbon Capital cost $7,000,000
Operating cost $3.50/ton
UddeholmrKamyr (ion ex- Capital cost $500,000
change)
Operating cost $0.90/ton
Costs were based on G-P bleached kraft mill, Woodland, Maine (1972-625 TPD)
Costs were adjusted to 1974 by ENR index ration 1995/1761.
2
Costs are based on Gulf States unbleached kraft mill in Tuscaloosa,
Alabama (1974-500 TPD).
Costs are based on pilot plant work at St. Regis, Pensacola, Florida
(1974-800 TPD)
A
Costs are based on bleached kraft mill in Skoghall, Sweden (1974-300 TPD).
V-21
-------
The point values assigned to the color reduction technologies for this
evaluation phase are shown below:
Uddeholm-Kamyr (ion exchange) = 4
Minimum Lime = 3
Alum coagulation and recovery = 2
Activated carbon adsorption = 1
4. Wastewater Streams Treated
Alum coagulation and activated carbon adsorption can both treat the
entire wastewater effluent from a bleached kraft mill. However, ac-
tivated carbon would be more likely used as a polishing stage to the
treatment system rather than the actual treatment. Therefore, alum was
the technology determined to handle more wastewater streams than the
other three technologies.
Activated carbon was determined to be next followed by minimum lime and
the ion exchange process which handles only the alkaline bleach ef-
fluent. Recent studies into the minimum lime process have shown that it
can be used to treat other streams in combination with the alkaline
bleach effluent.
The point values assigned to the color reduction technologies for this
evaluation phase are shown below:
V-22
-------
Alum coagulation and recovery = 4
Activated carbon adsorption = 3
Minimum lime = 2
Uddeholm-Kamyr (ion exchange) = 1
5. Color Reduction Efficiency
The Uddeholm-Kamyr process was reported to achieve 90 to 95 percent
color reduction at the bleached kraft mill in Sweden while activated
carbon was reported to achieve 90 percent at the pilot plant tests of
the system. Alum coagulation achieved a little less than 90 percent
color reduction at the bleached kraft mill in the USSR and lime achieved
approximately 80 percent at the two bleached kraft mills discussed
earlier.
Based on these efficiencies the following point values were assigned to
the color reduction technologies in this evaluation phase:
Uddeholm-Kamyr (ion exchange) = 4
Activated carbon adsorption = 3
Alum coagulation and recovery = 2
Minimum lime = 1
The point value assigned each color reduction technology under the
respective evaluation phases was then multiplied by the point value
V-23
-------
assigned for the specific evaluation phase. The calculation of the
total point values for each color reduction technology under each eval-
uation phase is shown on Table 42.
C. BATEA TECHNOLOGY
Based upon the preceding evaluation minimum lime and alum coagulation
were determined to be the top two technologies presently representing
BATEA. Minimum lime has the main advantage of a proven recovery system.
Alum coagulation will perform as well as lime, but the recovery system
for alum must still be developed. Therefore, minimum lime was selected
as presently representing the best available technology. Further de-
velopments in any of the technologies described in this report could
change this determination, and an update at some point in the future
should be done to verify or revise the selection of minimum lime as the
color reduction technology representing BATEA.
V-24
-------
BATEA
Color Reduction
Technology
Minimum Lime
Activated Carbon
Ud d e hoIm-Ka myr
Alum Coagulation
Minimum Lime
Activated Carbon
Uddeholm-Kamyr
Alum Coagulation
TABLE 42
SUMMARY OF BATEA COLOR REDUCTION TECHNOLOGY ANALYSIS
Evaluation Phase
Stage Operational Total Wastewater Color
of Problems Operating Streams Reduction
Development Experienced Cost Treated Efficiency
Point
5 4
Point Value
4 3
1 4
2 1
3 2
Value Assigned
3
Assigned Color
3
1
4
2
Calculated Point Value
20 12
5 16
10 4
15 8
Total
nimum Lime 46
urn Coagulation 39
tivated Carbon 33
deholm-Kamyr 32
9
3
12
6
Point Value for
Evaluation Phase
2
Reduction Technology
2
3
1
4
for Color Reduction Technology
4
6
2
8
Color Reduction Technology
1
1
3
4
2
1
3
4
2
-------
SECTION VI
RECOMMENDED BATEA EFFLUENT COLOR DISCHARGE -
AVERAGE DAY
This section of the report presents the calculation of the BATEA
effluent color discharge for the average day condition. The calculation
of the BATEA average day color discharge has been based upon a color
control process concluded to be technologically feasible at the present
time. Optimizing color reduction would require treatment of all the
color contributing wastewater streams from a bleached kraft mill.
However, as determined in Section V, development of a color reduction
technology to achieve this optimized condition has not reached the stage
of actual application as a feasible process. As discussed earlier the
continuing research into further development of these color reduction
technologies should be monitored by the EPA. Further research could
achieve a feasible color reduction process capable of color reduction of
a greater portion of the color contributing streams than is possible
with the minimum lime process.
The basis for calculating the BATEA effluent color discharge for average
day will be the minimum lime color reduction of the first stage caustic
extraction effluent. The first stage caustic extraction effluent was
determined to be the major source of color at the majority of the 26
pulp and paper mills surveyed. In addition to the minimum lime treat-
ment of the first stage caustic extraction effluent the reduction in
total effluent color caused by reducing or eliminating the wastewater
VI-1
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discharge from the pulp mill decker or screen room will be evaluated.
Reducing or eliminating the amount of wastewater from this phase of
the pulping operation is a BATEA internal control and as such must
be evaluated as to its effect upon the total color discharged from a
bleached kraft operation. This particular process was determined to
have contributed an average of 24 percent of the total mill color load
at the bleached kraft mills sampled' for decker/screen room color.
The minimum lime process was selected in Section V as the color reduc-
tion technology presently representing BATEA. Two bleached kraft pulp
and paper mills presently have a minimum lime process for color reduc-
tion of the first caustic extraction effluent. The process is used only
t
during low flow conditions in the mill's effluent receiving stream.
Color reduction efficiencies of approximately 80 percent have been
achieved at both mills. Calculation of BATEA effluent color discharge
loads were done with an 80 percent reduction efficiency used to deter-
mine the color load which can be removed from the first stage caustic
extraction effluent.
The effect of reducing or eliminating the decker/screen room discharge
will be evaluated on the basis of the percent discharge (color load)
eliminated. A minimum of 50 percent reduction in flow (color load)
will be used along with 100 percent reduction in decker/screen room
flow (color load)„
VI-2
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The total mill color load, which was used to calculate the BATEA ef-
fluent color discharge for average day, was determined from the color
measured at the influent to the secondary wastewater treatment system
and the total bleach plant production. Section III has already presented
the reasons for the selection of these two parameters versus use of the
final effluent and the final mill production presently used. Most
pulp and paper mills do keep records on daily bleach plant production,
including a breakdown by softwood and hardwood.
One item of particular importance in establishing BATEA effluent color
limitations is determining the variability factors necessary for cal-
culating the maximum 30 day average and maximum day limitations,,
Normally, these variability factors are determined by statistically
evaluating at least a 13-month period of daily wastewater loads to
determine the annual average day load, the maximum 30 day average
load, and the maximum day load. The variability factors are then
calculated by dividing the maximum 30-day average load by the average
day load, and the maximum day load by the average day. These factors
are then used to calculate the maximum 30-day average and maximum day
limitations.
The scope of this study did not include an evaluation of the color load
variability over a long-term period (at least 13 months). Therefore,
BATEA effluent color limitations of maximum 30 day average and maximum
day were not calculated. Instead the average day for the color survey
period was determined and the annual average day color discharge was
VI-3
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calculated using this value. It is recommended that daily color loads
at a few of the average bleached kraft mills examined in this study be
obtained, or monitored and determined (if not available) for at least a
13 month period. Using this information the average color load deter-
mined in this study would be verified or revised if required. Then
the maximum 30 day average and maximum day color loads can be deter-
mined, and with the annual average day color load the variability
factors for calculating the BATEA effluent color limitations can be
obtained.
After evaluation of the data gathered at the 23 papergrade bleached
kraft mills, it was determined that all of the bleached kraft subcate-
gories, except for dissolving kraft and soda mills, would be included in
one subcategory for calculating the BATEA color limitations. The sub-
category is called bleached kraft. The following subsection will
describe the basis for this determination.
A. LOGIC FOR PAPERGRADE SINGLE BLEACHED KRAFT COLOR LIMITATIONS
Kraft pulping and bleaching operations account for the large majority of
color generated by the mills surveyed, while only a small portion is
generated by the paper mill operation. Spot checks were made on paper
mill effluents during the sampling phase to verify this assumption and
the data showed from 3 percent of total color measured at the secondary
treatment influent in Mill No. 134 to 3 percent of the total color in
Mill No. 161 measured at this sample point.
VI-4
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With this basic premise verified (the paper making operation in an
integrated pulp and paper manufacturing operation generates insignif-
icant color when compared to the total), the pulping and bleaching
phases were then considered.
Pulping and bleaching both are accomplished by processes designed to do
essentially the same task, to remove the color causing material (primarily
lignin) and purify the cellulose fiber. This purification is accom-
plished in nearly all cases in such a way as to maintain maximum fiber
integrity and strength. The exception being dissolving kraft which will
be dealt with as a separate subcategory for that reason.
All the bleached kraft subcategories use similar pulping operations
with variations in operating parameters to accommodate differences in
wood types and final product requirements. The end uses are so similar,
whether the pulp is being produced for market or for internal use to
directly produce paper, that the only significant variation within a
species group is final pulp brightness. Strength variations are not
intentional and result from wood characteristics and individual mill
process differences.
Figure 57 shows that pulping targets are essentially the same within
each species group. It has been shown in this report that the large
majority of color generation in overall pulp mill effluent comes from
two sources. In the pulping area, the screen or decker effluent is by
VI-5
-------
far the major contributor, and in the bleaching area, the first two
bleaching stages account for the large majority of color from that
system and the largest single source of color in the entire mill complex.
Because the pulping phase is essentially the same in all subcategories
only the bleaching operation varies. A review of bleaching shows that
the process is an extension of pulping in that it continues the lignin
removal and cellulose purification action. Chlorine in the first
bleaching stage, followed by extraction of the chlorinated organic
materials in the second stage using sodium hydroxide, removes nearly all
of the impurities left in the cellulose mass. What remains is reacted
with the agents used to complete the bleaching process in subsequent
stages, primarily chlorine dioxide and hypochlorite.
All mills surveyed bleached to final brightness between 82.0 and 90.0
TAPPI points. The amount of lignin left in the pulp in this brightness
range is extremely small and variations are not accurately measurable by
a normal "K" number test used in pulping and bleaching. Because this
material is the primary source of color, it was concluded that final
brightness and final product subcategory have an insignificant effect on
bleach plant color contribution in the bleached kraft subcategories
surveyed. This conclusion was verified by the random scattering of
points in Figure 65.
Based on the above logic and survey results, it was decided that no
sound basis existed for different color limits within the bleached kraft
VI-6
-------
subcategory in the scope of this report. Only dissolving kraft and soda
pulping were considered as separate subcategories requiring limitations
based on process and product differences.
The only variation from this single subcategory concept of any sig-
nificance in the survey data was the color load from the mills which
produced only fine paper. Lower color loads at these three mills were
noted. These low figures are explained as resulting from the selection
of mills to be sampled. Hardwood was the predominent specie at these
three mills and hardwood is shown to contribute less color in Ibs/ton
than softwood. The three bleached kraft fine paper mills surveyed use
hypochlorite bleach which is shown to reduce color load, with one of the
mills adding extra hypochlorite for color reduction.
It was also noted that the mills surveyed which produced fine paper and
market pulp had essentially the same average color per ton as mills
producing only market pulp. This would indicate that the production of
fine paper at a mill is not sufficient basis to expect lower color
generation in its effluent.
Thus, a single color standard is developed to include the following
subcategories:
Bleached Kraft - Market Pulp
Bleached Kraft - BCT Papers
Bleached Kraft - Fine Papers
VI-7
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B. RATIO; 100 PERCENT SOFTWOOD TO 100 PERCENT HARDWOOD PULP BLEACHED
Section III of this report evaluated the specific effect that bleaching
softwood pulp versus bleaching hardwood pulp had on the color load at
the 26 pulp and paper mills surveyed. It was determined that because of
the obviously higher color load which results when bleaching softwood
pulp the BATEA effluent color limitations would be determined on the
basis of the wood species pulped. The method selected was a BATEA
effluent color limitation (average day) with the lowest limit at 100
percent hardwood pulp and progressing at a linear relationship to the
highest limit at 100 percent softwood pulp. Determination of the
specific effluent color limitation at any bleached kraft, dissolving
kraft, or soda mill would then be determined by the percent softwood
pulp bleached. The specific ratio of 100 percent softwood to 100
percent hardwood will now be determined.
The ratio of 100 percent softwood to 100 percent hardwood pulp bleached
was determined by adding the daily color load at the influent to the
secondary wastewater treatment system for each of the mills surveyed
that bleached either 100 percent softwood or hardwood pulp and deter-
mining an average color load for both. The average color load at the
100 percent softwood pulp mills was then divided by the average color
load at the secondary influent for 100 percent hardwood pulp. The
resulting value is the approximate ratio to be used in calculating the
BATEA effluent color limitations.
VI-8
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Mills 107, 126, 117, and 127 bleached 100 percent softwood pulp while
mills 140 and 187 bleached 100 percent hardwood pulp. Mill 127 was not
used in the ratio determination because it is a dissolving kraft mill
and not a bleached kraft mill as are the other four mills. Mill 117 was
also not included in the ratio determination because it was utilizing
hypochlorite on the first caustic extraction effluent for the purpose of
color reduction of that wastewater stream.
Table 43 shows the calculation of the 100 percent softwood pulp to the
100 percent hardwood pulp ratio.
TABLE 43
RATIO: 100 PERCENT SOFTWOOD TO 100 PERCENT HARDWOOD PULP BLEACHED
100 Percent Softwood
Color Load at
Mill Secondary Influent
No. kg/kkg (Ibs/ton)
107 305 (610)
231 (461)
310 (621)
126 403 (806)
385 (716)
315 (630)
Total 1,922 (3,844)
Average 320 (641)
Ratio 100 Percent Softwood
100 Percent Hardwood
Mill
No.
140
187
100 Percent Hardwood
Color Load at
Secondary Influent
kg/kkg (Ibs/ton)
84
116
90
220
230
200
(169)
(231)
(180)
(440)
(460)
(400)
641
313
940 (1,880)
157 (313)
2.05
VI-9
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Based upon the ratio calculated on Table 43, a ratio of 2:1 was used in
the calculation of the BATEA effluent color discharge (average day).
C. METHOD USED TO CALCULATE BATEA EFFLUENT COLOR DISCHARGE
(AVERAGE DAY)
The average day BATEA effluent color discharge loads were calculated
on the basis of the BOD raw waste load reported by each mill during
the color survey. Only those mills surveyed which were at, or below,
the BATEA BOD raw waste load criteria during the color survey were
used in calculating the discharge loads for color. The rationale sup-
porting this procedure is that the mills which met the BOD raw waste
load for BATEA had eliminated that portion of their color load, which
results from insufficient internal controls, to the wastewater treat-
ment system. Therefore, the color load from these mills (as defined
by the raw waste BOD) would approximate the color loads from the
entire industry with tighter internal controls adopted on an
industry-wide basis.
Based upon the flow and wastewater BOD values submitted by each of the
mills BOD raw waste loads were calculated. The resulting BOD loads
along with the BATEA raw waste BOD load for each of the 26 mills sur-
veyed appears on Table 44. It should be noted that when the BOD was
measured at the ASB influent a 15 percent BOD reduction through the
primary clarifier was used.
VI-10
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TABLE 44
RAW WASTE BOD DETERMINATIONS
Average Raw Waste
BOD for Color Survey
kg/kkg (Ibs/ton)
BATEA Raw Waste
BOD
kg/kkg (Ibs/ton)
100
101
102
103
105
106
107
108
110
111
113
114
117
118
119
121
122
125
126
127
134
136
140
152
161
187
39.4
22.7
49.7
37.6
32.1
75.5
38.3
33.2
26.8
31.7
41.2
40.1
9.7
35.5
21.5
33.2
39.3
25.6
30.4
31.0
18.6
35.5
29.5
19.7
Not
24.7
(78.8)
(45.3)
(99.3)
(75ol)l
(64.1)2
(150. 9)1
(76=6)3
(66. 3)1
(53.5)
(63.3)
(82.1)
(80.2)
(19. 4)1
(71. O)4
(44. 7)5
(66.1)1
(78.5)
(51. 2)6
(60. 7)1
(62. O)7
(37.2)
(70. 9)8
(58. 9)1
(39.3)
Included in BATEA Mill
(49. 3)1
26.5
23.5
26.5
23.5
26.0
23.5
23.5
37.5
23.5
26.0
26.5
26.5
26.0
23.5
23.5
26.5
26.5
26.5
26.5
37.5
23.5
23.5
26.5
30.0
Selection^
26.5
(53.0)
(47.0)
(53.0)
(57.0)
(52.0)
(47.0)
(47.0)
(75.0)
(47.0)
(52.0)
(53.0)
(53.0)
(52.0)
(47.0)
(47.0)
(53.0)
(53.0)
(53.0)
(53.0)
(75.0)
(47.0)
(47.0)
(53.0)
(60.0)
(53.0)
1. BOD was measured at the primary effluent, therefore, 15 percent
was added to the measured values.
2. Only one day of the color survey was used to calculate BOD load.
3. BOD was measured at the ASB influent for only the 1st and 3rd day
of the color survey. 15% was added to this measured value.
4. Day one and three of the color survey was used to determine BOD load.
5. BOD data for period 7/74 through 6/75 was used to calculate BOD load.
6. BOD was measured at the ASB influent on the 2nd and 3rd day of the
color survey. 15% was added to the measured value.
7. BOD was measured at the ASB influent on the 1st and 2nd day of the
color survey. 15% was added to measured value.
8. BOD data for 1/75 through 6/75 was used to calucate the BOD load.
9. Mill's wastewater treatment system is shared with two other paper mills.
Therefore, BOD data could not be used.
VI-11
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Nine mills were determined to be at, or below, the BATEA BOD raw waste
load. Six bleached kraft mills (Mills 101, 117, 119, 125, 134, and
187), two dissolving kraft mills (Mill 108 and 127) and the one soda
mill (Mill 152) were included in the 9 mills. These mills will be used
in calculating the average day BATEA effluent color discharge loads.
D. BLEACHED KRAFT SUBCATEGORY
Table 45 shows the average color load at the first stage caustic ex-
traction effluent, color load reduction through application of the
minimum lime process, and the average color load at the secondary treat-
ment influent before and after minimum lime treatment at the 6 bleached
kraft mills representing BATEA. Also shown is the total average color
load after treatment of 88 Kg/KKg (175 Ibs/ton). The percent softwood
pulp bleached by the 6 mills was then determined. Table 46 shows the
determination of the percent softwood pulp bleached to be 49 percent.
, f
The final step in .calculating the average day BATEA effluent color dis-
charge was to apply the effect that reducing or eliminating the dis-
charge from the second largest source of color in a bleached kraft
mill the decker/screen room. This internal control is a BATEA control
and as such must be evaluated to determine what effect it will have
upon the color load discharged by bleached kraft mills. Because it
may not be possible for all bleached kraft operations to totally
eliminate the color load contributed by the decker/screen room process
VI-12
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TABLE 45
DETERMINATION OF AVERAGE COLOR LOAD AT SECONDARY TREATMENT INFLUENT
BLEACHED KRAFT
I
M
OJ
Average Color Load @ First
Mill Caustic Extraction Effluent
No. kg/kkg (Ibs/ton)
101
117
119
125
134
187
Total
Average
95
-
46
258
37
101
(190) L
-
(92)
(517)
(74)
(202)
•;/?
Color Reduction
Achieved
kg/kkg (Ibs/ton)
Average Total Color Load @ Secondary
Treatment Influent
76
37
196
30
81
(152)
(74)
(391)
(59)
(162)
Before Treatment
kg/kkg (Ibs/ton)
189
82
245
100
217
(378)
(164)
(590)
(199)
(433)
After Treatment
kg/kkg (Ibs/ton)
113
62
45
100
70
136
526
88
(226)
(125)2
(90)
(199)
(140)
(271)
(1,051)
(175)
1. Day 2 and 3 of color survey was used to calculate average.
2. Hypochlorite is used by Mill 117 for color removal; therefore, the color measured at the
secondary treatment influent was used as the after treatment color load.
-------
TABLE 46
BLEACHED KRAFT PERCENT SOFTWOOD PULP
Mill
No.
101
117
119
125
134
187
Average
kkg
221
307
. 202
804
209
-
Softwood Pulp Average Hardwood Pulp Percent
(tons)
(243)
(338)
(222)
(885)
(230)
-
kkg
380
-
279
70
• 390
706
(tons)
(418)
-
(307)
(77)
(429)
(778)
Softwood
37
100
42
92
35
0
Total 1,743 (1,918)
Total pulp bleached
Average percent softwood
1,825 (2,009)
3,568 kkg (3,927 tons)
1,743/3,568 (1,918/3,927) x 100 = 49 percent
VI-14
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a range included a 50 percent reduction in decker/screen room color load
and a 100 percent reduction. Many of the mills evaluated may have to
achieve a significant, if not total, reduction in the color load from
the decker/screening operation to be able to meet the BATEA effluent
color limitation.
The specific color load used to establish the range for color reduction
from the 50 and 100 percent reduction of color from the decker/screen
room was determined on the basis of the 24 percent average of the total
color load at the secondary treatment influent for this process, which
was calculated in Section III under the bleached kraft mill color
origin.
The average day color load at the influent to the secondary treatment
system for the six mills (only five used to calculate average, mill 117
not used) was 176.5 Kg/KKg (353 Ibs/ton). Based upon the average of
24 percent of this total color load being contributed by the decker/
screen room, a color load of 42.5 Kg/KKG (85 Ibs/ton) contributed from
this process was calculated. Therefore, the 50 and 100 percent
reduction in color load from this process would mean an additional
21 Kg/KKG (42 Ibs/ton) and a 42 Kg/KKg (85 Ibs/ton) reduction in the
after minimum lime treatment color load calculated on Table 45.
This would result in average day BATEA effluent color discharge of
67 Kg/KKg (133 Ibs/ton) and 46 Kg/KKg (90 Ibs/ton) with the 50 and
VI-15
-------
100 percent color reduction at the decker/screen room subtracted, res-
pectively. These discharge loads are for the 49 percent softwood
point of the BATEA effluent color discharge (average day). Table 47
lists the BATEA effluent color discharge (average day) for mills
pulping 100 percent softwood and also mills pulping 100 percent hard-
wood with a 50 and 100 percent color load reduction from the decker/
screen room accounted for. Mills processing a mixture of softwood
and hardwood pulp will have BATEA effluent color limitation (average
day) at a value between those listed for 100 percent softwood and 100
percent hardwood.
Table 48 lists the BATEA effluent color discharge (average day) for
the 23 bleached kraft mills included in this study. These discharge
loads were calculated on the basis of the percent softwood pulp used
by each of the facilities during the color survey period (listed on
Table 1). Figure 92 shows the plot of the BATEA effluent color dis-
charge (average day) for the bleached kraft subcategory with 50 and
100 percent of the decker/screen room color load removed.
E. DISSOLVING KRAFT SUBCATEGORY
Two dissolving kraft mills, Mill 127 and 108, were surveyed during the
pulp and paper mill color project. Mill 127 and 108 both had BOD raw
waste loads, during the color survey, below the BATEA BOD raw waste
load.
VI-16
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TABLE 47
BATEA EFFLUENT COLOR DISCHARGE (AVERAGE DAY)
BLEACHED KRAFT
100% Softwood Pulp 100% Hardwood Pulp
kg/kkg (Ibs/ton) kg/kkg (Ibs/ton)
50% Color Load Reduction
@ Decker/Screen Room 89.5 (179) 45 (89.5)
100% Color Load Reduction
@ Decker/Screen Room 60.5 (121) 30 (60.5)
VI-17
-------
TABLE 48
CALCULATED BATEA EFFLUENT COLOR DISCHARGE (AVERAGE DAY)
BLEACHED KRAFT MILLS SURVEYED
Mill Percent BATEA Effluent Color Discharge (Average Day)
No. Softwood 50% Color Reduction 100% Color Reduction
@ Decker/Screen Room @ Decker/Screen Room
100
101
102
103
105
106
107
110
111
113
114
117
118
119
121
122
125
126
134
136
140
161
187
54
40
39
31
53
60
100
30
63
51
25
100
25
42
56
81
92
100
35
60
0
45
0
kg/kkg
(Ibs/ton)
69
62.5
62
58.5
68.5
71.5
89.5
58
73
67.5
56
89.5
56
63.5
70
81
86
89.5
60.5
71.5
45
65
45
(138)
(125)
(124)
(117)
(137)
(143)
(179)
(116)
(146)
(135)
(112)
(179)
(112)
(127)
(140)
(162)
(172)
(179)
(121)
(143)
(89.5)
(130)
(89.5)
kg/kkg
(Ibs/ton)
46.5
42.5
42
39.5
46.5
48.5
60.5
39.5
49.5
45.5
38
60.5
38
43
47
55
58
60.5
41
43.5
30
44
30
(93)
(85)
(84)
(79)
(93)
(97)
(121)
(79)
(99)
(91)
(76)
(121)
(76)
(86)
(94)
(110)
(116)
(121)
(82)
(97)
(60.5)
(88)
(60.5)
VI-18
-------
FIGURE 92
10
.o
o
<
o
IT
O
_J
O
O
BLEACHED KRAFT BATEA
EFFLUENT COLOR DISCHARGE
(AVERAGE DAY)
350(700)-
300(600)-
7 250(5001-
o
200(400)-
150(300)-
100 (200)-
89.5 (179)
60.5(121 )
50(100) -
0 (0)
126
107
X 106
X 105
v 114
187
DECKER/SCREEN
187
140
I40<
ROOM
AVERAGE DAY WITH IOO% COLOR REDUCTION
DECKER/SCREEN ROOM
r (700) 350
- (600)300
-(500)250
^(400)200
-(300)150
-(200)100
( 100) 50
(89.5) 45
(60.5) 30
[0)0
100
80
60 40
% SOFTWOOD
20
COLOR LOAD AT SECONDARY TREATMENT INFLUENT BEFORE MINIMUM LIME
TREATMENT OF THE FIRST CAUSTIC EXTRACT
COLOR LOAD AT SECONDARY TREATMENT INFLUENT AFTER MINIMUM LIME
TREATMENT OF THE FIRST CAUSTIC EXTRACT
c
o
a
<
o
(X
O
_1
O
o
-------
The average color load at the secondary treatment influent for the two
dissolving kraft mills was 367 kg/kkg (733 Ibs/ton), while the average
color load at the first stage caustic extraction effluent was 271 kg/kkg
(542 Ibs/ton). Applying the 80 percent color reduction efficiency of
the minimum lime treatment system to the average first stage caustic
extraction effluent resulted in 217 kg/kkg (434 Ibs/ton) of color load
removed. Subtracting the color load removed from the average color
load at the secondary treatment influent gave an average day BATEA
effluent color discharge of 150 kg/kkg (300 Ibs/ton). Determination
of the specific point that this average represented involved calcula-
tion of the average percent softwood pulp bleached by the two dissolving
kraft mills during the color survey at the mills. This calculation
resulted in an average of 85 percent softwood pulp bleached at the
mills.
The final step in calculating the BATEA effluent color discharge (average
day) for the dissolving kraft subcategory was to determine the color load
to be subtracted from the after treatment (minimum lime) average day
value determined earlier. The color load contributed by the decker/
screen room was calculated to be 88 kg/kkg (176 Ibs/ton). This value
was calculated by using the color load at the secondary treatment system
times the average color load contributed by the decker/screen room of
24 percent.
VI-20
-------
The 50 and 100 percent discharge reduction from the decker/screen room
was then applied to the average day color load after minimum lime treat-
ment to calculate the BATEA effluent color discharge (average day). The
limitation was determined to be 106 kg/kkg (212 Ibs/ton) and 62 kg/kkg
(124 Ibs/ton) for the 50 and 100 percent reductions, respectively.
By then applying the previously calculated percent softwood determined
the 100 percent softwood and hardwood pulped limitations were calcu-
lated. These discharge loads are shown on Table 49.
Figure 93 is a plot of the color loads calculated versus the percent
softwood pulped. Also included on the plot is the color reduction
achieved at both facilities with minimum lime treatment applied.
F. SODA SUBCATEGORY
Only two soda mills are presently operating in the United States. One
of these mills, Mill 152, was visited during the color surveys. Mill
152 uses basically 100 percent hardwood pulp (approximately 4 to 5
percent of the pulp used at the mill is softwood) in their manufacturing
process. Mill 151, the other soda mill, is also a 100 percent hardwood
mill. Therefore, one limit for average day was calculated on the basis
of the color survey at Mill 152. Mill 152 had an average BOD below the
BATEA raw waste BOD load.
VI-21
-------
TABLE 49
BATEA EFFLUENT COLOR DISCHARGE (AVERAGE DAY)
DISSOLVING KRAFT
100% Softwood Pulp 100% Hardwood Pulp
kg/kkg (Ibs/ton) kg/kkg (Ibs/ton)
50% Color Load Reduction 114.5 (229) 57 (114.5)
@ Decker/Screen Room
100% Color Load Reduction 67 • (134) 33.5 (67)
@ Decker/Screen Room
VI-22
-------
a
<
o
o:
o
FIGURE 93
DISSOLVING KRAFT BATEA
EFFLUENT COLOR DISCHARGE
- (AVERAGE DAY)
350(700)
300(600) -
250(500) -
200(400) -
150 (300)
114.5(229)
100 (200) '
67 (134)
50(100) •
0(0)
127
100
X 108
1 '
108
AVERAGE DAY WITH IOO% COLOR REDUCTION
DECKER/SCREEN ROOM
AVERAGE DAY WITH 5O% COLOR REDUCTION
DECKER/SCREEN ROOM-
80
60 40
% SOFTWOOD
20
COLOR LOAD AT SECONDARY TREATMENT INFLUENT BEFORE MINIMUM LIME
TREATMENT OF THE FIRST CAUSTIC EXTRACT
COLOR LOAD AT SECONDARY TREATMENT INFLUENT AFTER MINIMUM LIME
TREATMENT OF THE FIRST CAUSTIC EXTRACT
[700)350
- (600)300
u (500)250
-(400)200
"(200) 100
(114.5)57
\- (100)50
( 67 )33.5
(0)0
c
o
V.
in
O
<
O
IT
O
-(300)150 o
-------
The average color load at the secondary treatment influent for Mill 152
was 140 kg/kkg (279 Ibs/ton). The average color load contributed by the
first stage caustic extraction effluent was 73 kg/kkg (145 Ibs/ton). A
total of 58 kg/kkg (116 Ibs/ton) of color can be removed with the min-
imum lime process at 80 percent efficiency. The color load at the
secondary treatment influent after minimum lime treatment was 82 kg/kkg
(163 Ibs/ton).
The effect of reducing the decker/screen room discharge by 50 and 100
percent, respectively, was then evaluated. Based upon the average 24
percent of the total color load from bleach kraft mills at the decker/
screen room a total of 17 kg/kkg (33.5 Ibs/ton) and 33.5 kg/kkg (67
Ibs/ton) was subtracted from the color load after minimum lime treatment
to determine the BATEA effluent color discharge.
The average color load for BATEA effluent color discharge was calculated
to be 65 kg/kkg (129.5 Ibs/ton) at 50 percent color load reduction, and
48 kg/kkg (96 Ibs/ton) with a 100 percent color load reduction at the
decker/screen room. These color discharge loads are at the 100 percent
hardwood point.
G. SUMMARY
Table 50 shows the BATEA effluent color discharge (average day) which
were calculated for the bleached kraft, dissolving kraft, and soda
subcategories. The discharge loads were also plotted on Figure 94.
VI-24
-------
TABLE 50
SUMMARY BATEA EFFLUENT COLOR DISCHARGE (AVERAGE DAY)
100% Softwood 100% Hardwood
Subcategory kg/kkg (Ibs/T) kg/kkg (Ibs/T)
@ 50% Color Reduction from Decker/Screen Room
Bleached Kraft 89.5 (179) 45 (89.5)
Dissolving Kraft 114.5 (229) 57 (114.5)
Soda 130 (259) 65 (129.5)
@ 100% Color Reduction from Decker/Screen Room
Bleached Kraft 60.5 (121) 30 (60.5)
Dissolving Kraft 67 (134) 33.5 (67)
Soda 96 (192) 48 (96)
VI-25
-------
a<
JC
JC
a
<
o
ac
o
FIGURE 94
BATEA EFFLUENT COLOR DISCHARGE
(AVERAGE DAY)
150 (300)-
130(259)
1145(229)
100(200)
96(192)
89.5(179)
67(1 34)
60.5(121 )
50 (100)-
0(0)
-(300)150
-(200)100
SODA SUBCATEGORY
DISSOLVING KRAFT SUBCATEGORY
BLEACHED KRAFT SUBCATEGORY
100
80
I
60
40
i
20
(129.5) 65
(114.5) 57
c
o
a
<
o
a:
o
_j
o
o
(89.5) 45
( 67 ) 38.5
( 60.5) 30
0(0)
% SOFTWOOD
AVERAGE DAY WITH 50% COLOR REDUCTION DECKER/SCREEN ROOM
AVERAGE DAY WITH 100% COLOR REDUCTION DECKER/SCREEN ROOM
-------
SECTION VII
• COST FOR COLOR REDUCTION AT MODEL MILLS - BATEA
The total annual costs presented in this report for color reduction of
the first stage caustic extraction effluent utilizing the minimum lime
treatment technology are subdivided into two categories, as follows:
1. Depreciation and interest (annual cost)
2. Operation and maintenance.
Depreciation costs reflect the accounting charges for replacement of the
capital assets over a period of years. Straight-line depreciation has
been assumed in all annual cost calculations. Interest is the financial
charges on the capital expenditures for the color reduction facility.
For purposes of this report, depreciation, interest, insurance, taxes,
and spare parts are assumed to be 15.0 percent of the total capital
expenditure.
The operation and maintenance costs are those costs expended for annual
operation of the color reduction facility. These costs are subdivided
as follows:
1. Operator Labor
2. Maintenance Labor
3. Energy Requirements
VII-1
-------
4. Chemicals
Operator labor costs are based on the annual manhours required to per-
form the tasks for proper operation, overhead and supervision, and
quality control monitoring for the color control treatment facility.
The maintenance costs are the annual manhours required for preventative
maintenance tasks such as lubrication, equipment inspection, minor parts
replacement, and painting. It was assumed that major equipment repair
and/or replacement and miscellaneous yard work would be done by the
existing mill personnel.
Chemical usage is based on estimated quantities required to meet pro-
posed effluent limitations, or as required for proper operation of the
minimum lime system. The energy requirements are based on the addition-
al horsepower and operating times plus the heat energy required for the
minimum lime technology.
The total annual operating costs presented in this report are the sum of
the annual costs for operator labor, maintenance costs, energy require-
ments, and chemicals.
A. BASIS FOR MINIMUM LIME TREATMENT COSTS
A minimum lime treatment system to reduce the color of the first caustic
stage extraction effluent was sized and estimated for a 670 TPD model
VII-2
-------
mill. The minimum lime treatment system for which cost estimates were
made represents an entirely independent system from the existing mill
processes and external treatment. It should be stated that there are
other variations of the minimum lime color control system which are
possible and may be more practical for some mills.
The system would utilize a wastewater transfer pump to transport the
first caustic stage effluent from the bleach plant to the minimum lime
treatment system. A cost for piping to transport the flow to the treat-
ment system was included (4,000 feet of 16 inch pipe for the 670 TPD
mill).
An inline mixer would then be used to combine a lime slurry, with the
first caustic stage effluent.
For the purpose of the cost estimate a lime dosage of 2,250 mg/1 was
used. It may be necessary for some mills to add more or less lime,
but the specific amount will depend upon the amount of fiber in the
system, polyelectrolyte used, and the hydraulics of the clarification
step.
The wastewater then flows to a color reduction clarifier with a poly-
electrolyte metered into the wastewater stream prior to the clarifier to
aid in settling the lime precipitate. Other settling aids such as fiber
fines could also be used at this point in the minimum lime process.
VII-3
-------
Sludge from the clarifier would either be sent to a sludge holding and
mixing tank or pumped directly to the lime mud dewatering system. After
the lime mud has been dewatered to approximately a 60 percent solids
concentration it is transferred to a fluidized bed for drying and cal-
cining. The reburnt lime is then transferred back to the slaker for
reuse in the color control process.
B. MODEL MILLS
The cost for the minimum lime system was developed for a 670 TPD mill.
The costs were then calculated for other size model mills on the basis
of a cost to flow relationship. The size model mills used in the cost
estimate by subcategory are shown below:
Bleached Kraft
Market Kraft 350 and 700 TPD
BCT Kraft 250, 670, and 1300 TPD
Fine Kraft 250, 670, and 1300 TPD
Dissolving Kraft 600 and 1000 TPD
Soda 300 and 700 TPD
The cost summary at the end of this section will present the cost of a
minimum lime treatment system at these model mills.
VII-4
-------
C. AVERAGE FLOWS
The average flow at the influent to the secondary treatment system and
the first stage caustic extraction effluent were determined for use in
sizing the minimum lime treatment system equipment. The flows recorded
during the color surveys were used to determine the average flow. Table
51 shows the determination of these average flows and the percent of the
total flow at the secondary influent represented by the first stage
caustic extraction effluent.
VII-5
-------
TABLE 51
AVERAGE FLOW DETERMINATION
Mill
No.
100
101
102
103
105
106
107
108
110
111
113
114
117
118
119
121
122
125
126
127
134
136
140
152
161
187
Average
Ave. Flow Secondary
Treatment Influent
kl/Kkg
227.35
138.90
187.22
265.28
299.35
249.09
180.58
204.02
176.22
180.95
192.84
109.78
92.98
164.28
120.45
137.15
142.37
224.11
143.05
151.50
75.46
232.59
110.49
102.08
171.17
(Kgal/ton)
(54.39)
(33.23)
—Wr» f- C*amT»l Qrl
(44.79
(63.46)
(71.61)
(59.59)
(43.20)
(48.81)
(42.16)
(43.29)
(46.13)
(26.26)
(39.24)
(39.30)
(28.82)
(32.81)
(34.06)
(53.61)
(34.22)
(36.24)
(18.05)
(55.64)
(26.43)
(24.42)
(40.95)
Ave.
Caustic
kl/Kkg
1.09
7.90
at First
at First
28.59
34.53
23.24
30.93
18.39
12.62
11.91
20.98
12.37
23.70
13.33
26.00
28.63
27.17
40.00
33.77
15.88
21.44
12.04
12.75
13.67
18.85
20.41
Flow 1st
Extract
(Kgal/ton)
(0.26)
(1.89)
Stage Caustic-
Stage Caustic-
(6.84)
(8.26)
(5.56)
(7.40)
(4.40)
(3.02)
(7.85)
(5.02)
(2.96)
(5.67)
(3.19)
(6.22)
(6.85)
(6.50)
(9.57)
(8.08)
(3.80)
(5.13)
(2.88)
(3.05)
(3.27)
(4.51)
(4.88)
Percent of
Total Flow
0.5
5.7
15.3
13.0
7.8
12.4
10.2
6.2
6.6
11.6
6.4
21.6
14.3
15.8
I
23.8
19.8
28.1
15.1
11.1
14.2
16.0
5.5
12.4
18.5
11.9
An average flow of 20.48 kl/Kkg (4.90 Kgal/ton) at the first stage
caustic extraction effluent and 171.38 kl/Kkg (41.00 Kgal/ton) at the
secondary treatment influent was used to size the treatment equipment,
VII-6
-------
D. CAPITAL COSTS
As previously mentioned, the costs were developed on the basis of a 670
TPD mill and a flow relationship was used to calculate costs for the
remaining model mills. The capital cost was based upon the following
equipment:
1. wastewater transfer pump,
2. lime storage, slaker, and feed system,
3. polyelectrolyte system,
4. inline mixers,
5. clarifier (thickener),
6. sludge pumps,
7. sludge holding and mixing tank,
8. lime mud dewatering, and
9. lime mud incineration.
Capital cost and annual cost based upon depreciation and interest at
15.0 percent of the capital cost were calculated for all of the model
mills previously listed. These costs are summarized by model mill on
Table 52 at the end of this section.
A plot of the capital cost and annual cost based upon the first caustic
extraction effluent flow is shown on Figure 95. All capital costs are
based upon February 1978 dollars.
VII-7
-------
FIGURE 95
COST FOR TREATING BLEACH PLANT
CAUSTIC EXTRACT FILTRATE WITH
MINIMUM LIME SYSTEM
10,000
en
-------
E. ANNUAL OPERATION COSTS
As stated in the introduction to this section, the annual operation cost
consists of operator labor, maintenance labor, energy requirements, and
chemicals. Each of these four items of cost will be discussed on the
following pages.
1. Operator and Maintenance Labor
The operator labor is based on the annual manhours required to perform
the tasks for proper operation, overhead and supervision, and quality
control monitoring, while the maintenance labor cost is based on the
annual manhours required for preventative maintenance tasks such as
lubrication, equipment inspection, minor parts replacement, and
i
painting.
Existing mill personnel would be able to handle some of these additional
operation and maintenance tasks required for the minimum lime system.
However, the external color control equipment such as the clarification
unit would require additional manpower expenditures. The number of
additional manhours required is dependent upon the size of the equip-
ment, which in the case of the minimum lime system is dependent upon the
first stage caustic extraction effluent flow. Estimates of the ad-
ditional manhours required were done for the model mills based upon
their respective flows. A man year rate of $22,000 was used to determine
the operator and maintenance labor costs for the minimum lime system.
The average non-supervisory labor rate in pulp and paper production
VII-9
-------
in February 1978 was $71.4 per hour (referenced from the Bureau of Labor
and Statistics). This base rate was then increased by 35 percent for
overhead and benefits and 15 percent for labor supervision. Based on
these factors a yearly rate of $22,000 was used in the cost determina-
tions.
A summary of these operation and maintenance costs by model mill is
shown on Table 52 at the end of this section. Figure 96 shows a plot of
the operation and maintenance cost as a function of the minimum lime
treatment system capacity.
2. Energy Requirements
The energy requirements of the minimum lime treatment system include the
horsepower required to operate the color control processes, and the heat
energy required to dry and recalcine the lime mud after filtration. The
energy requirement for operating the equipment was determined to be 3.91
kilowatt-hours per ton of production (kw-hr/ton) or 794 kw-hr/mgd. The
operating energy costs were then calculated for the model mills using a
cost of $0.03 per kw-hr.
The heat energy was calculated on the basis of fuel oil as the source of
heat for accomplishing the lime sludge drying. A heat production of
approximately 146,000 BTU's per gal of fuel oil was used along with a
VII-10
-------
FIGURE 96
MINIMUM LIME TREATMENT
OPERATION AND MAINTENANCE
1000
100
en
D
O
X
CO
O
o
10
I
0.38
(0.10)
I I I I I I I I
I I I I I I I I
I I
3.78
(1.00)
37.80
(10.00)
378
(100)
FIRST CAUSTIC EXTRACT FLOW kkld (mgd)
-------
cost of $3.50 per million BTU's. Heat energy of 6.5 million BTU per ton
of lime product for incineration was used to calculate heat energy
costs. For the purpose of determining the quantity of lime sludge,
which must be dried per day, a lime recovery rate of 90 percent at the
clarifier was used. This results in 28 tons per day of lime as CaO
recovered at the clarifier for the 670 TPD mill. A solids concentration
of 60 percent after the lime mud filter was also used.
The total energy cost for each model mill is shown on Table 52 at the
end of this section; Figure 97 shows a plot of the total annual energy
cost and the annual operating kilowatt hours required related to the
first caustic extract effluent flow. The kilowatt-hours per year re-
quired was divided into two plots which show the annual equipment oper-
ating energy and the total operating energy (heat energy plus operating
energy). The equipment operating energy represents approximately 4.7
percent of the total energy required.
3. Chemical Cost
The annual chemical cost consists of the lime and polyelectrolyte re-
quired for the minimum lime system.
As mentioned earlier in this section, a lime dosage of 2,250 mg/1 has
been used with a lime recovery in the clarifier of 90 percent. There-
fore, 10 percent of a mill's daily lime requirement must come from
VII-12
-------
FIGURE 97
MINIMUM LIME TREATMENT,
ENERGY REQUIREMENTS
10,000
O 1000
o
o
z
o
I
CO
o
o
-------
purchased makeup lime (CaO). A lime cost of $35.00 per ton of lime was
used.
A polyelectrolyte dosage of 3 mg/1 at a cost of $1.00 per pound of
polyelectrolyte was used to determine the polyelectrolyte chemical cost
for each model mill.
A summary of the total chemical cost for the mills is presented on Table
f
52 at the end pf this section. Figure 98 is a plot of the chemical cost
related to the flow from the first caustic extraction effluent.
F. SUMMARY
The capital cost, annual cost (depreciation and interest), operation
and maintenance labor cost, energy cost, and chemical cost for each of
the model mills is presented on Table 52. The total annual cost (deprecia-
tion and interest plus operation and maintenance labor plus energy plus
chemical cost) is also shown.
A total annual cost range at the model mills of $2.50 to $3.50 per ton
of production resulted from the cost calculations. The lower cost was
for those model mills producing more (1300 TPD) and the higher cost was
for those producing the lowest level (250 TPD). The cost for the 670
TPD mill was calculated at $2.85 per ton of production. Mills that have
10 to 20 percent capacity available in their existing lime systems would
be able to attain significant savings over the cost presented here.
VII-14
-------
FIGURE 98
MINIMUM LIME TREATMENT
CHEMICAL COST
1000
o
o
O
X
o
o
z
z
<
100
I
0.38
(0. 10)
I I
I I
I I
3.78
(1.00)
37.8
(10.0)
378
(100)
FIRST CAUSTIC EXTRACT FLOW kkld (mgd)
-------
TABLE 52
COST SUMMARY FOR MODEL MILLS
MARKET KRAFT
ETC KRAFT
FINE KRAFT
<
M
M
I
Mill
1.
2.
3.
4.
5.
6.
Mill
1.
2.
3.
4.
5.
6.
Size: 350 TPD
$1,273,000
191,000
55,800
133,400
34,400
414,600
Size: 700 TPD
$1,929,000
289,000
84,500
266,700
70,200
710,400
Mill
1.
2.
3.
4.
5.
6.
Mill
1.
2.
3.
4.
5.
6.
Mill
1.
2.
3.
4.
5.
6.
Size: 250 TPD
$1,033,000
155,000
45,300
92,200
24,900
317,400
Size: 670 TPD
$1,895,000
284,000
83,000
257,600
68,000
692,600
Size: 1300 TPD
$2,820,000
423,000
123,500
497,200
131,600
1,175,300
1. Capital Cost
2. Annual Cost (Depreciation and Interest)
3. Operator and Maintenance Labor
4. Energy Cost
5. Chemical Cost
6. Total Annual Cost (2+3+4+5)
Mill
1.
2.
3.
4.
5.
6.
Mill
1.
2.
3.
4.
5.
6.
Mill
1.
2.
3.
4.
5.
6.
Size: 250 TPD
$1,033,000
155,000
45,300
92,200
24,900
317,400
Size: 670 TPD
$1,895,000
284,000
83,000
257,600
68,000
692,600
Size: 1300 TPD
$2,820,000
423,000
123,500
497,200
131,600
1,175,300
DISSOLVING KRAFT
Mill Size: 600 TPD
1.
$1.754.000
2,
3.
4.
5.
6.
263,000
76,800
225,600
59,300
624,700
Mill" Size: 1000 TPD
1.
2."
3.
4.
5.
6.
$2.402,000
360,000
105,000
390,000
101,500
956,800
SODA
Mill Size: 300 TPD
1.
2.
3.
4.
5.
6.
$1,181,000
177,000
51,700
115,300
31,300
375,300
Mill Size: 700 TPD
1.
2."
3.
4.
5.
6.
$1.929,000
289,000
84,500
266,700
70.200
710,400
-------
SECTION VIII
REFERENCES
1. Standard Methods for the Examination of Water and Waste Water.
14th Edition. American Public Health Association, American Water
Works Association, Water Pollution Control Federation, Washington,
D.C., 1976, p. 64-70.
2. CPPA Technical Section, "Color of Pulp Mill Effluents," CPPA Std.
H.5P; 3p. (September, 1974).
3. Correspondence from Mill 152, July 27, 1976.
4. Correspondence from Mill 110, September 1, 1976.
5. Correspondence from Mill,101, May 7, 1976.
5a. Correspondence from Mill 117, May 20, 1976.
6. "Development Document for Interim Final and Proposed Effluent
Limitations Guidelines and Proposed New Source Performance
Standards for the Bleached Kraft, Groundwood, Sulfite, Soda,
Deink, and Non-Integrated Paper Mills, Volume 1, Segment of
the Pulp, Paper and Paperboard, Point Source Category," EPA
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7. Fuller, R.R., "API's 1975 Environmental Awards," Paper Trade Jr.,
159 (22) 41 (1975).
8. Rush, R.J. and Shannon, E.E., "Review of Color Removal Technology
in the Pulp and Paper Industry," Environmental Protection Service,
Environment Canada, Report No. EPS 3-WP-76-5, (April, 1976).
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Removal from Pulp and Paper Waste Waters by Coagulation," TAPPI 57,
No. 8: 55-6 (August, 1974).
10. Olthof, M.G., "Color Removal from Textile and Pulp and Paper Waste
Waters by Coagulation," Vanderbilt Univ., Ph.D. Thesis 1974; 359 p.
(Univ. Microfilms, Ann Arbor, Mich; From; Piss. Abstr. 35, no. 7:
3359B (Jan., 1975).
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Pap. Chem. 46 (2) 1571 (1975).
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Effluent Treatment," Paper, World Res. Devt.-No., 1974: 46, 48-9,
52-4.
13. Nasr, M.S.; Gillies, R.G.; Bakhshi, N.N.; Macdonald, D.G.,
"Lab-Proven Fly Ash Process Removes Bleach Effluent Color,"
Canadian Pulp Paper Industry 28, No. 9: 30-32, 35 (September,
1975).
VIII-1
-------
14. Dugal, H.S.; Church, J.O.; Leekley, R.M.; and Swanson, J.W.,
"Color Removal in a Ferric Chloride-Lime System," TAPPI,
Vol. 59, No. 9 (September, 1976).
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Paper Mill Effluents," Pulp and Paper Pollution Abatement Series,
CPAR Report 210-1, Canadian Forestry Service, Department of the
Environment (March 31, 1974).
16. Soniassy, R.N.; Mueller, J.C.; Walden, C.C. "Effects of Color and
Toxic Constituents of Bleached Kraft Mill Effluent on Algal Growth,"
CPPA Environmental Improvement Conference (Vancouver); 85-91
(October 15-17, 1975).
17. Herer, D.O.; Woodard, F.E., "Electrolytic Coagulations of Lignin
From Kraft Mill Bleach Plant Waste Waters," TAPPI 59, No. 1:
134-136 (January, 1976).
18. Nicolle, F.M.A., Shamash, R., Nayak, K.V., Histed, J.R.,
"Lime Treatment of Bleachery Effluent," presented at 1976 Inter-
national Environmental Conference October 6-8, 1976, CPPA.
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hammer, M., "Studies on the Adsorption of Spent Chlorination and
Spent Caustic Extraction Stage Liquor Color and Organic Carbon
on Activated Carbon," NCASI Stream Improvement Technology Bul-
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20. Rankin, P.R. and Benedek, A., "Lignin Adsorption on Activated
Carbon," Wastewater Research Group Report #73-103-1, Department
of Chemical Engineering, McMaster University (September, 1973).
21. Gibney, L.C., "Inroads to Activated Carbon Treatment," Environ-
mental Science Technology 8, no. 1: 14-15 (January, 1974).
22. Lang, E.W., et al, "Activated Carbon Treatment of Unbleached
Kraft Effluent for Reuse," EPA -660/2-75-004 (April, 1975).
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colorization Problem,", TAPPI 57, no. 9: 69-73 (September, 1974).
24. Ploetz, T., "Purification of the Pulp Industry's Bleachery Ef-
fluents with Alumina," Papier 28, no. 10A: V39-43 (October, 1974).
25. Rock, S.L.; Bruner, A.; Kennedy, D.C., "Decolorize Kraft Bleach Plant
Effluents Effectively with Low-Cost Polymeric Adsorption Method,"
Pulp Paper International 17, no. 3:66-69 (March, 1975).
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ment," NCASI Technical Bulletin No. 284 (February, 1976).
27. Lingberg, S., "Decolorization of Bleach Plant Effluent and
Chloride Handling," Paper Trade Journal, p. 36-37 (December, 1973).
VIII-2
-------
28. Charaberlin, T.A.; Kolb, G.C.; Brown, S.F.; Philip, D.H., "Color
Removal from Bleached Kraft Effluents," TAPPI Environmental
Conference (Denver), Preprints: 34-45 (May 14-16, 1975).
29. Correspondence from Dow Chemical received on March 22, 1976.
30. Burns, C.M., "Review of Membrane Processing of Pulp Mill Ef-
fluents," Pulp and Paper Pollution Abatement CPAR Project Report
124-1, Canadian Forestry Service, Department of the Environment,
March 31, 1973.
31. Martin, L.F., Industrial Water Purification, Noyes Data Corporation,
(Park Ridge, N.J. 07656 & London) c!974: 300 p.
32. Johnson, J.S., Minturn, R.E., and Moore, G.E., "Filtration Tech-
niques for Purification of Kraft Pulp Mill and Bleach Plant
Waste," TAPPI, 57, 1, 134, (1974).
33. Muratore, E.; Pichon, M.; Monzie, P., "Color Removal from Kraft
Effluent by Ultrafiltration with New Polymeric Membranes,"
Svensk Papperstid 78, no. 16: 573-576 (November 10, 1975).
34. Fels, M.; Smith, D.; Miller, C.; Miller, P., "Ultrafiltration Offers
'Good' Removal of Color, COD, BOD," Can. Pulp Paper Ind. 27, no. 9:
50-2 (September, 1974).
35. Timpe, W.G. and Lang, E.W., "Activated Carbon and Other Techniques
for Color Removal from Kraft Mill Effluents," Proc. EUCEPA Conf.,
Rome (May 1973), Abs. Bull. Inst. Paper Chemistry, 45, 2, 1667
(1974).
36. Nelson, W.R.; Walraven, G.O.; Morris, D.C., "NSSC Mill with Waste
Reuse and Reverse Osmosis," TAPPI Environmental Conference (New
Orleans): 63-71 (April 17-19, 1974).
37. Bansal, I., "How to Purify Effluents, Recover By-Products with
Reverse Osmosis," Pulp Paper 49, no. 5: 118-121 (May, 1975).
38. Gellman, Isaiah, "Draft Effluent Decolorization — A Program for
Assessment of its Need, Technological Capability and General
Consequences."
39. Balhar, L., "Prospects of the Application of Reverse Osmosis in
the Pulp and Paper Industry," Papir Celuloza, 2£ (11) 257 (1974)
(Slovak); Abstract Bulletin Institute Paper Chemistry, 45^ (10)
10742 (1975).
40. Haye, E.R., and Munroe, V.G., "Kraft Effluent Color Removal by
Dispersed Air Flotation," Pulp and Paper Mag. Canada, 75, 11,
61, (1974).
VIII-3
-------
41. Das, B.S., Ontario Research Foundation, "Precipitation-Flotation
Method of Treating Pulp Mill Effluents," Pulp and Paper Pollution
Abatement, CPAR Project Report 184-1, Canadian Forestry Service,
Department of the Environment, September 30, 1973.
42. Herschmiller, D.W., "Foam Separation of Kraft Mill Effluents,"
MAS Thesis. University of British Columbia (April, 1972).
43. Chan, A.; Herschmiller, D.W.; and Manolescu, D.R., "Ion Flotation
for Color Removal from Kraft Mill Effluents," Pulp and Paper Pol-
lution Abatement, CPAR Project Report 93-1, Canadian Forestry
Service, Department of the Environment, March 31, 1973.
44. Bauman, H.D.; Lutz, L.R., "Ozonation of a Kraft Mill Effluent,"
TAPPI 57. no. 5: 116-19 (May, 1974).
45. Nebel, C.; Gottschling, R.D.; O'Neill, H.J., "Ozone: A New
Method to Remove Color in Secondary Effluents," Pulp Paper 48,
no. 10: 142-5 (September, 1974).
46. NCASI, "Preliminary Laboratory Studies of the Decolorization and
Bacterial Properties of Ozone in Pulp and Paper Mill Effluents,"
Technical Bulletin No. 269, (January, 1974).
47. Buley, V.F., "Potential Oxygen Application in the Pulp and Paper
Industry," TAPPI, Vol. 56, No. 7 (July, 1973).
48. Prahacs, S.; Wong, A; Jones, H.G., "Amine Treatment Process for
Decolorization of Pulp Mill Effluents. (1) Laboratory Studies,"
A.I.Ch.E. Symp. Ser. 70, no. 139: 11-22 (1974).
49. Wong, A.; Heitner, C.; and Prahacs, S., "The Amine Treatment
Process for the Decolorization of Pulp Mill Effluents. (2) Mill-
Site Studies," Pulp and Paper Research Institute of Canada.
50. Lenz, B.L.; Robbins, E.S.; et al., "The Effect of Gamma Irradiation on
Kraft and Neutral Sulphite Pulp and Paper Mill Aqueous Effluents,"
Pulp and Paper Magazine of Canada, Vol. 72, No. 2, pg. 75-80 (Feb-
ruary, 1971).
51. "A Preliminary Investigation of Radiation Enhanced Oxidation of Pulp
Mill Effluents for Color Reduction," NCASI Technical Bulletin No.
271 (February, 1974).
52. McKelvey, R.D.; Dugal, H.S., "Photochemical Decolorization of Pulp
Mill Effluents." TAPPI 58, no. 2: 130-3 (February, 1975).
53. Nova Scotia Research Foundation, "Biological Treatment Method for
the Removal of Colour, BOD, and Suspended Solids from Pulp Mill
Effluents," Pulp and Paper Pollution Abatement Series, CPAR Report
208-1, Canadian Forestry Service, Department of the Environment
(March 31, 1974).
VIII-4
-------
54. Chemical Engineering, McGraw-Hill, Vol. 83, No. 27, December 20,
1976, pg. 19.
VIII-5
-------
SECTION IX
BIBLIOGRAPHY
Akamatsu, I.; Kobayashi, T.; Kamishiuma, H., "Regeneration of Spent
Granular Activated Carbon Used for Kraft Pulp Waste Treatment;
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Activated Carbon," Japan TAPPI 28, no. 7: 329-33 (July, 1974).
Anderson, L.G.; Lindberg, S., "Uddeholm (Forest Industries, Skoghall
Sweden) Cleans Bleach Effluents and Solves Chloride Removal Question,"
Pulp Paper Intern. 16, no. 6: 46-7, 52 (June, 1974).
Aschim, O.K.; Wiest, K.C., "Bleach Plant Water Reduction," paper
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Improvement Conference, Toronto, Ontario (September 23, 1974).
Atkinson, E.S., "Bleach Plant Pollution Abatement - Where Do We Stand?",
Canadian Pulp Paper Industry 28, no. 9: 22-24 (September, 1975).
Auer-Welsbach, C., "New Methods of Fresh Water Preparation and Ef-
fluent Purification in Pulp and Paper Mills," Wochbl. Papierfabr. 102
no. 8: 293-4, 296 (April 30, 1974).
Basu, A.K., "Advanced and Low-Cost Treatment of Pulp Mill Wastes,"
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no. 371: 419-423 (October, 1974).
Berger, H.F., "Color Loads Associated with Sulfite and Semi-
Chemical Operations," Proceedings of the 1974 NCASI Central-Lake
States and Northeast Regional Meetings, NCASI Special Report No. 76-04
(April, 1976).
, "Investigation of Changes in Treated Effluent Color
Upon Storage," Proceedings of the 1974 NCASI Southern and West
Coast Regional Meetings, NCASI Special Report No. 76-01 (Jan-
uary, 1976).
Black, A.P. and Christman, R.F., J. Am. Water Works Assoc. 55(6): 1963.
Bogoev, S.; Semov, V., "Biological Purification of Effluents From Pulp
and Paper Mills," Tr. Nil Vodosnabdyavane, Kanalizatsiya, Sanit.
Tekh. 7, no. 2: 147 54 (1971).
Brecht, W.; Dalpke, H.L., "Basic Considerations of the Closed Mill
System," Paper 181, no. 8:413, 415-16, 421 (April 17, 1974).
Chou, S.; Sumimoto, M.; Sakai, K.; Kondo, T., "Studies on Magnesium-
Base Semichemical Pulps. (2). Qualities and Treatment of Waste
Liquors," Japan TAPPI 29, no. 2:77-83 (February, 1975).
Clarke, J., "Color and Organic Removal from Kraft Bleachery Effluent
by Coagulation," PhD Thesis, University of South Carolina, 1969.
IX-1
-------
Collin, G., "A Modern Line for Producing Pulp, Taking into Con-
sideration Energy, Environment, and Economics," Papel 36: 41-46
(February, 1975).
Croom, H.C., Owens-Illinois, Inc., "Method of Decolorizing Waste
Process Liquid Discharged by a Paper Mill," U.S. pat. 3,883,463-
Issued Sept. 3, 1974.
Croon, I., "Some Advanced Systems for Reducing Pollution in the
Pulp Industry, Mainly Oxygen Bleaching," Papel 24:50-60 (October,
1973).
Dorica, J.; Berzins, V.; Prahacs, S., "Color Measurement of Pulp
Mill Effluents," CPPA Environmental Improvement Conference (Vancouver):
57-64 (October 1517, 1975).
Dugal, H.S.; Swanson, J.W.; Dickey, E.E.; Buchanan, M.A., "Effect of
Lime Treatment on Molecular Weight Distribution of Color Bodies
From Kraft Linerboard Decker Effluents," TAPPI 58, no. 7: 132135
(July, 1975).
Federal Register, "Pulp, Paper, and Paperboard Point Source Category:
Effluent Guidelines and Standards," Fed. Register 39, no. 104:
18742-52 (May 29, 1974).
Fiehn, G., "Current Status and Trend of Bleaching Processes and
Bleaching Technology," Zellstoff Papier 24, no. 1:6-14 (January, 1975)
Firsov, A.I.; Drozdov, N.P.; Malev, V.P. "Final Purification of Bio-
chemically Treated Effluents from Wood Rosin Plants," Gidroliz.
Lesokhim. Prom, no. 1:6-7 (1974).
Fremont, H.A., "Color Removal from Kraft Mill Effluents by Ultra-
Filtration," Proceedings of the 1974 NCASI Southern and West Coast
Regional Meetings, NCASI Special Report No. 76-01 (January, 1976).
Gellman, I.; Gove, G., "1973 Review of the Literature on Pulp and
Paper Effluent Management," NCASI Stream Improvement Technology
Bulletin no. 275: 72 p. (May, 1974).
Hawthorne, S.H.; Rapson, W.H., "Reduction of Lignin Model Compounds by
Trivalent Uranium," Pulp Paper Mag. Can. 75, no. 6: 82-8 (T234-40)
(June, 1974).
Haynes, D.C., "Water Recycling in the Pulp and Paper Industry," TAPPI
57., no. 4: 45-52 (April, 1974).
Howard, T.E., "Swimming Performance of Juvenile Coho Salmon (Oncor-
phynchus Kisutch) Exposed to Bleached Kraft Pulp Mill Effluent,"
J. Fisheries Res. Board Can. 32, no. 6: 789-793 (June, 1975).
IX-2
-------
_; Walden, C.C., "Measuring Stress in Fish Exposed to
Pulp Mill Effluents," TAPPI 57, no. 2:133-5 (February, 1974).
Hwang, C.P., "Carbon and Color Distribution in Various Size Fractions
of Treated Pulp Mill and Board Mill Waste Effluents" TAPPI 57, no.
12: 148-9 (Dec., 1974).
Kabeya, H.; Fujii, T.; Kimura, Y., "Studies of Renovation and Pulp
Mill Waste Water: Pilot-Plant Test for Granular Activated Carbon
Adsorption of Kraft Mill Waste Water," Japan TAPPI 27, no 11:548-
53 (November, 1973).
Karelin, Ya. A., Salamatov, Yu. P., "Ozonization of Effluents of
a Kraft Pulp Mill," Izv. VUZ, Stroit. Arkhitek. 16, no. 7: 136-141
(1973).
Koseki, M.; Tanaka M., "Advanced Treatment of Chemigroundwood Pulp
Waste Waters," Japan TAPPI 28, no. 3: 132-5 (March, 1974).
; Kimura, Y., "Advanced Treatment of Unbleached
Kraft Pulp Waste Waters," Japan TAPPI 28, no. 4: 145-60 (April, 1974).
Ladmiral, D., "La Cellulose du Pin (France) Reduces Its Sources of
Pollution," Papeterie 96, no. 12:814-822 (December, 1974).
Lexezynski, C.; Zielinski, J., "Effect of Various Technological Factors
on the Color of Pulp Mill Effluents," Pizeglad Papier. 30, no. J3:
290-6 (August, 1974).
McKague, A.B., "Flocculating Agents Derived From Kraft Lignin,"
J. App. Chem. Biotechnol. 24, no. 10: 607-15 (October, 1974).
McKeown, J.J.; Whittemore, R.C., "Color Perception," Proceedings
of the 1974 NCASI Southern and West Coast Regional Meetings,
NCASI Special Report No. 76-01 ( January, 1976).
Maematsu, R., "Water Treatment With Activated Carbon Made From
Sludge and Waste Paper," Japan Pulp Paper 12, no. 3: 53-8 .(October,
1974).
Moy, W.A.; Sharpe, K.; Betz, R.G., "New Bleaching Sequence for SBK
(Semi-Bleached Kraft) Cuts Effluent Color and Toxicity," Pulp
Paper Can. 76, no. 5: 126-129 (T166-169) (May, 1975).
Nagaya, K.; Maeda, K.; Nakata, T., "Production of Powdered Activated
Carbon From Sodium-Base SCP (Semichemical Pulp) Black Liquor (1)
Production From Pyrolysis Residue By Stream Activation. (2). Carbon
Activity and Treatment of Dilute Black Liquor With The Carbon,"
Japan TAPPI 28, no. 10: 501-6; no. 11: 558-63 (October-November,
1974).
IX-3
-------
National Council of the Paper Industry for Air & Stream Improvement,
"Engineering Estimate of the Cost to the Paper Industry of Achieving
Selected EPA National Effluent Limitation Levels," NCASI Stream
Improvement Tech. Bull, no 270: 142 p. (January, 1974).
Nayak, K.V.; Nicolle, P.M.A.; Histed, J.R., "How to Reduce Bleachery
Effluent Color," Pulp and Paper Canada, 76 (4), (April, 1975).
, "Bleachery Effluent Treatment," paper presented
at Canadian Pulp and Paper Assoc. Air and Stream Improvement Con-
ference, Toronto, Ontario (September 23, 1974).
Nebel, C.; Gottschling, R.D.; O'Neill, H.J., "Ozone Decolorization
of Effluents from Secondary Treatment," Paper Trade Journal 158,
no. 4:24-5 (January 28, 1974).
"1974 Review of the Literature on Pulp and Paper Effluent Management,"
NCASI Technical Bulletin No., 280 (April, 1975).
Obiaga, T.I.; Ganczarczyk, J., "Biological Removal of Lignin from
Kraft Mill Effluents: Changes in Molecular Size Distribution,"
TAPPI 57, no. 2: 137-8 (February, 1974).
Olson, Marc; Luoma, Dick; Wallace, A.T.; and Grimestad, Garry,
"Percolating Effluent Into Ground Reduces Color at Missoula
Mill," Pulp and Paper. October 1976.
"Ultrafiltration Looks Feasible for Kraft Effluent Color Removal,"
Paper Trade Journal 158, no 17:26-7 (April 29, 1974).
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Standards at St. Regis," Paperboard Packaging 59, no. 12:24, 26, 28-9
(December, 1974).
Pichon, M.; Muratore, E.; Monzie, P., "Treatment of Alkali Extrac-
tion Effluents by Ultrafiltration," ATIP Rev. 28, no. 1: 9-15 (1974).
Polcin, Jr., "Non-Destructive Bleaching of Highly Lignified Fibrous
Materials. (1) Wood Chromophores and Their Destruction," Vyskum.
Prace Odboru Papiera Calulozy 19, V. 69-73 (1974).
"Proceedings of the 1974 NCASI Southern and West Coast Regional Meetings,"
Special Report No. 76-01 (January 1976).
Pulp and Paper Research Institute of Canada, "Delignification Using
Pressurized Oxygen, Pulp and Paper Pollution Abatement, CPAR Project
Report 3-2, Canadian Forestry Service, Department of the Environment
(September 30, 1971).
Rapson, W.H. and Reeve, D.W., "The Effluent-Free Bleached Kraft Pulp
Mill Part III. The Present State of Development," paper presented at
the Alkaline Pulping Conference of the Technical Association of the
Pulp and Paper Industry, September 11-14, 1972.
IX-4
-------
Rolfe, O.K.; Owens-Illinois, Inc., "Method of Decolorizing Paper
Mill Effluent Liquid," U.S. pat. 3,883,464- Issued September 3, 1974.
Rouba, J., "Processing of Sediments from Coagulation Applied as the
Third Stage of Effluent Purification," Przeglad Wlok. 29, no 9:
452-455 (September, 1975).
Sameshima, K.; Sumimoto, M.; Kondo, T., "Color of Pulp Industry Waste
Liquors. (5) Contribution of Wood Components to the Color of Waste
Liquors from Kraft and Sulfite Pulping," J. Japan Wood Resources
Society (Mokuzai Gakkaishi) 20, no. 6: 284-9 (June 1974)
, "Color of Pulp Industry Waste Liquors. (IV).
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Resources Society (Mokuzai Gakkaishi) 20, no 1: 21-5 (January, 1974).
, "Color of Pulp Industry Waste Liquors. (6)
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(Mokuzai Gakkaishi) 21, no. 3: 188-193 (March, 1975).
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Celulozy 19, V 59-64 (1974).
Sharpe, K.; Moy, W.A.; Styan, G.E., "Modification of Kraft Bleaching
Sequences for Pollution Abatement," CPPA Annual Meeting (Montreal)
61, Preprints Book B:67-71 (1975).
Spruill, E.L., "Color Removal and Sludge Disposal (Process) for Kraft
Mill Effluents," Paper Trade J. 158, no. 33: 24-7 (August 19, 1974).
, "Color Removal and Sludge Disposal Process for Kraft
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, "Long-Term Experience with Continental Can's Color
Removal System," TAPPI Environmental Conference (New Orleans): 19-
24 (April 17-19, 1974).
Stevens, F., "First Pollution-Free Bleached Kraft Mill Gets Green
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Tejera, N.E. and Davis, M.W., Jr., TAPPI 53 (10): 1931 (1970).
Timpe, W.G., "Kraft Bleach Decolorization by a Resin Adsorption Process,"
Proceedings of the 1974 NCASI Southern and West Coast Regional
Meetings, NCASI Special Report No. 76-01 (January, 1976).
Tosaka, K.; Hayashi, J., "Studies of Recovery of Chemicals and
Manufacture of Activated Substances From Pulping Waste Liquor.
(2) Use of Softwood Kraft Pulp Waste Liquor," Japan TAPPI 29,
no. 6: 316-323 (June, 1975).
IX-5
-------
Vogt, C., "Development Document for Effluent Limitations Guidelines
and New Source Performance Standards for the Unbleached Kraft and
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1974).
Warren, C.E.; Seim, W.K.; Blosser, R.O.; Caron, A.L.,; Owens, E.L.,
"Effect of Kraft Effluent on the Growth and Production of Salmonid
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Williams, H.H., "Removal of Kraft Color by Alum Treatment," Proceedings
of the 1974 NCASI Central-Lake States and Northeast Regional Meetings,
NCASI Special Report No. 76-04 (April, 1976).
Wong, A., "Physical-Chemical Treatment," Proceedings of Seminars on
Water Pollution Abatement Technology in the Pulp and Paper Industry,
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(March, 1976).
; Prahous, S., "Treatment of Pulp and Paper Mill Ef-
fluents Using Physical-Chemical Techniques," paper presented at the
1976 International Environmental Conference, October 6-8, 1976,
CPPA.
Wright, R.S.; Oswalt, J.L.; Land, J.G., Jr., "Color Removal From Kraft
Pulp Mill Effluents by Massive Lime Treatment," TAPPI 57. no. 3:
126-30 (March, 1974).
Zielinski, J.; Jurkiewicz, S., "Determination of Lignin Compounds in
Mill Effluents and Surface Waters," Przeglad Papier 30, no. 5: 182-8
(May, 1974).
IX-6
-------
SECTION X
ACKNOWLEDGMENTS
The Edward C. Jordan Co., Inc. wishes to acknowledge the assistance and
guidance of the Effluent Guidelines Division of the Environmental Pro-
tection Agency. Particular appreciation is extended to Mr. Craig Vogt,
Project Officer.
Appreciation is extended to the many companies who granted access to
their mills and treatment facilities, and for providing laboratory space
for the color survey team. The operating records provided by these
mills contributed greatly to the project.
Appreciation is also extended to the many members of the E.G. Jordan
Company staff for their efforts in gathering, compiling, analyzing,
and assimilating the data for this study. These staff members included
Don Cote, John Tarbell, Ralph Oulton, Fred Keenan, Fred Stubbert, Pete
Krauss, and Arthur Condren.
X-l
-------
APPENDIX I
FIELD DATA RECORDING SHEETS
-------
NCASI Color Procedure
Mill:
Date:
Adjust pH to 7.6 and filter through 0.8 ^ filter paper
Original
Sample Description PH % T @ 465.0 tnu
1. i
2.
3.
4.
5.
6.
7.
8.
9.
«
-------
EPA COLOR PROCEDURE-I
Mill:
Date:
pH of Samples at Time of Analysis:_
Sample Description
*
•^
L.
2.
3.
i.
5.
&.
7.
8.
9.
Wavelength, millimicrons
435.5
461.2
544.3
564.1
577.4
.588.7
" ^
599.6
«
610.9
624.2
645.9
%
Sanple
-------
Mill:
EPA COLOR PROCEDURE-it
Date:
pH of Samples at Time of Analysis:_
Sample Description
*
1.
2.
3.
4.
5.
6.
7.
3- . '
9.
Wavelength, millimicrons
4RQ.S
SIS. 2
529.8
541.4
551.8
-
561.9
572.5
\
584.8
600.8
627.3
-------
Mill:
EPA COLOR ?P,OCEDURE-III
Date:
pH of Samples at Time of Analysis:,
Sample Description
*
L.
2.
3.
i.
5.
5.
7.
3.
9.
Wavelength, millimicrons
422.2
432.0
438.6
444.4
450.1
-
.455.9
462.0
\
468.7
477.7
495.2
465.0
'
-------
APPENDIX II
ENVIRONMENTAL PROTECTION AGENCY EFFLUENT
GUIDELINES COLOR SURVEY FORM
-------
Subcategory:
ENVIRONMENTAL PROTECTION AGENCY
EFFLUENT GUIDELINES Agency: _
COLOR SURVEY
I. Company Name: Survey Date: 19_
Address: ZIP:
• *
Phone; / . Survey Team (Leader's Name First);
Mill/Corporate contacts (Use asterisk for person to contact re this survey.)
A. Approx. tons/day of principal and waste-significant raw materials. (Include
wood type, major chemicals, fillers (by major type), dyes (if color-significant)
B. Approx. ton/day of manufactured and purchased pulp:
Tons per day Tons per day
Mfgd. Purch. Mfgd. Purch.
Bleached Kraft ( ) ( ) Deinked(net) (2) ( ) ( )
Unbleached Kraft (1) ( ) ( ) NSSC ( ) ( )
Bleached Sulfite ( ) ( ) Bleached Soda ( ) ( )
TJnbl. Sulfite (1) ( ) ( ) Waste Paper ( ) ( )
(not deinked)
Groundwood (1) ( ) ( ) ( ) ( )
Bleached Groundwood ( ) ( ) ( ) ( )
(1) Do not include bleached, (2) Ave. Shrinkage %. Totals
( ) Percentage moisture Sum of Mfgd. + Purchased L
-------
Location: _ ] _ Page 2 of 10
C. Number of paper machines _ : pulp dryers
Approx. tons/day of principal products (include market pulp) :
Typical Production days/yr:
Total nominal tons/day of paper ; Mkt. pulp: Attach daily tonnage
records from 7/1/74 to 6/30/75 or other year to correspond with waste data below.
Final discharge into _; . (Receiving water or public sewer).
II. Mill Laboratory Testing Procedures (Used in reporting 12-month data).
Temperature; °F or °C
pH: (a) glass electrode? Standardization frequency?
(b) Colorimetric?
Color: (a) NCASI, pH adjusted to ;
(b) Standard Methods
(c) Other: ; . .
Procedure:
Suspended Solids: (a) Glass Fiber (Std. Methods) (b) NCASI
(c) Asbestos Mat (d) Other: ; '
Procedure:
BODS; No. of Dilutions: • Source of seed:
Dilution of water:
Std. Methods Ingredients? Source of distilled water
Routine check for copper? Seed Procedure: Std. Methods? If no
describe:
D.O. Measurement: Winkler . Electrode .
Standardization method:
Incubation Temp. * . Temp checked how often?
No. days incubated . . Selection of reported results:
(a) ©2 Depletion, mg/1 min; max.
(b) Seed correction?
Procedure:
-------
Mill:
Location:
Page 3 of 10
How often does mill run standard glucose-glutamic acid test:
Has mill changed above procedures in last 12-months? If yes, explain in Sec. VI
Bench Sheets Available for Susp. Solids? . for BOD?
Turbidity: (a) Jackson candle (b) Turbidimeter
(c) Other
III. Available Mill Data: Indicate frequency of mill test.
A. . Location (Name and sampling point symbol per sketches)
Location
Flow
TSS
BOD
. PH
Color
Turb.
Temp.
Other
12-month daily waste records enclosed in duplicate for raw waste?_
charge? __; intermediate treatment? . If not, when
12-month daily tonnage records enclosed?
; final dis-
Duplicate
If not, when
During 12-month data period, did any process or treatment upset last over 30 days?_
Did this affect data? ; if yesi explain in Section VI.
-------
Mill:
Location:
Page A of 10
B. Also note any discharges for which routine mill data does not exist, with
estimates of Flow, BOD, and TSS, and show in sketch.
C. Recommended split sampling program. If possible, select routine mill
samples for raw waste, final discharge, and intermediate treatment.
Location
Final Effluent
Secondary Influent
Primary Influent
Decker Filtrate
First Stage Cl? Filtrate
~ ' ~ ~ ~ ^ T "£••
1st Stage Caustic Filtrate
Symbol
Composite
Frequency
Mill Samole
-------
APPENDIX III
PRODUCTION DATA SUMMARY FORM
-------
Mill I.D. No._
Subcategory
PRODUCTION DATA SUMMARY
DATE
TOTAL
PRODUCTION
TONS/DAY
BLEACH PLANT PROD.
HARDWOOD
TONS/DAY
SOFTWOOD
TONS/DAY
PAPER MACHINE PROD.
MARKET PULP PROD.
-------
APPENDIX IV
COLOR DATA SUMMARY FORM
-------
COLOR DATA SUMMARY
Mill I.D. No._
Subcategory
DATE
SAMPLE POINT
FLOW
(MGD)
4,
\
'
i
1
TOTAL
PRODUCTION
TONS/DAY
NCASI METHOD
COLOR
(PPM)
COLOR
»;DAY
COLOR
#/TON
EPA METHOD
DOMINANT
WAVELENGTH
(mu)
HUE
-
LUMINANCE
(X)
PURITY
«)
-------
APPENDIX V
SPLIT SAMPLES RESULTS FORM
-------
Mill I.D. No.
Subcategory
SPLIT SAMPLE RESULTS
§>ATE
SAMPLE POINT
RESULTS
MILL
E.G. JORDAN
NCASI
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APPENDIX VI
EPA COLOR SURVEY SUPPLEMENTAL DATA
QUESTIONNAIRE
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7501900
EPA COLOR SURVEY
^_
\ SUPPLEMENTAL DATA QUESTIONNAIRE
Mill Namr>.
Mill Numbe\r
Location
Mill Contact'*,
. .
Color Survey tw
The following information must be for the color survey dates shown above.
1. WOOD SPECIES) (Tons /Day)
A. Pulped B. Bleached
Hardwood Softwood Hardwood Softwood
Day 1
\
Day 2
Day 3
2. K OR KAPPA NUMBERS AFTER BROWNSTOCK WASHERS
3. SALTCAKE (Pounds/Ton) AFTER BROWNSTOCK WASHERS
4. SALTCAKE (Pounds/Ton) AFTER SCREEN ROOM DECKER
i
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