SEPA
United States
Environmental Protection
Agency
Office of Air Quality
Planning and Standards
Research Triangle Park NC 27711
EPA-450/3-78-111
November 1978
Air
Screening Study
on Feasibility of Standards
of Performance for Two
Wood Pulping Processes
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EPA-450/3-78-111
Screening Study on Feasibility
of Standards of Performance
for Two Wood Pulping Processes
by
C.M. Thompson, W.C. Micheletti, and J.C. Terry
Radian Corporation
Austin, Texas 78766
Contract No. 68-02-2608
EPA Project Officer: George B. Crane
Emission Standards and Engineering Division
Prepared for
U.S. ENVIRONMENTAL PROTECTION AGENCY
Office of Air, Noise, and Radiation
Office of Air Quality Planning and Standards
Research Triangle Park, North Carolina 27711
November 1978
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This report has been reviewed by the Emission Standards and Engineering Division of the Office of Air
Quality Planning and Standards, EPA, and approvedfor publication. Approval does not signify that the
contents necessarily reflect the views and policies of the Environmental Protection Agency, nor does
mention of trade names or commercial products constitute endorsement or recommendation for use.
Copies of this report are available through the Library Services Office (MD-35), U.S. Environmental
Protection Agency, Research Triangle Park, N.C. 27711; or,for a fee, from the National Technical
Information Services, 5285 Port Royal Road, Springfield, Va. 22161.
Publication No. EPA-450/3-78-111
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ACKNOWLEDGEMENTS
Radian would like to express sincere appreciation to Mr. George Crane,
EPA Project Officer, for his helpful guidance and to all government and
industrial personnel contacted for their kind cooperation. A special note
of thanks is extended to those companies which arranged for mill visits:
Boise Cascade Corporation Salem, Oregon
Longview Fibre Company Longview, Washington
Menasha Corporation North Bend, Oregon
Publishers Paper Company Oregon City, Oregon
Weyerhaeuser Company Cosmopolis, Washington
Their genuine interest and continual cooperation was an invaluable aid in
preparing this screening study.
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ABSTRACT
This report is a screening study for the sulfite and neutral sulfite
semichemical (NSSC) wood pulping processes. The screening study was pre-
pared by Radian Corporation for the Emissions Standards and Engineering
Division of the U. S. Environmental Protection Agency. The purpose of
the screening study is to develop background information on both pulping
processes and to advise on the feasibility and need for standards of
performance for either or both of them.
This report provides a general industry description and discusses
in detail the operation of both wood pulping processes. Potential emission
sources are identified, as well as available methods of emission control.
In addition, existing applicable regulations are summarized, national
emissions are estimated, and specific analytical methods are discussed.
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TABLE OF CONTENTS
Section Page
ACKNOWLEDGEMENTS iii
ABSTRACT. iv
1.0 EXECUTIVE SUMMARY 1-1
1.1 Description of Processes Studied 1-1
1.2 Scope of Work 1-2
1.3 Results 1-5
2.0 CONCLUSIONS AND RECOMMENDATIONS 2-1
2.1 Conclusions 2-1
2.2 Recommendations 2-3
3. 0 DESCRIPTION OF THE WOOD PULPING INDUSTRY 3-1
3.1 Description of Sulfite and NSSC Pulping 3-3
3 .2 The Sulf ite Pulping Industry 3-5
3.3 The Semichemical Pulping Industry 3-17
4.0 PROCESS DESCRIPTION AND EMISSIONS SOURCES 4-1
4.1 Sulf ite Process 4-1
4.2 Neutral Sulf ite Semichemical (NSSC) Process 4-20
5.0 EMISSION CONTROL SYSTEMS 5-1
5-1 Control of Sulfur Dioxide Emissions 5-1
5-2 Control of Particulate Emissions 5-8
5-3 Candidate Best Control Systems 5-9
6.0 EXISTING EMISSIONS REGULATIONS 6-1
6.1 Emissions Regulations for Sulf ite Pulping 6-1
6.2 Emissions Regulations for NSSC Pulping 6-2
6.3 Additional Relevant Regulations 6-3
7.0 ESTIMATED EMISSIONS
7.1 Emission Test Data 7-1
7.2 Emission Factors 7-5
7.3 Estimation of Nationwide Emissions 7-23
7.4 Model IV Calculations 7-27
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TABLE OF CONTENTS (continued)
Section Z.age
8.0 SAMPLING AND ANALYSIS FOR AIR EMISSIONS FROM SULFITE AND
NSSC PULP MILLS 8~l
8.1 Measurement of Volumetric Gas Flow Rates 8-2
8.2 Sample Handling and Conditioning 8-3
8.3 Concentration Measurements 8-5
APPENDIX A - LIST OF MILLS PRODUCING WOOD PULP BY THE SULFITE
PROCESSES AND MILLS PRODUCING SEMICHEMICAL PULP A-l
APPENDIX B - SULFITE PULPING MODEL IV CALCULATION B-l
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LIST OF TABLES
Table Page
3-1 1978 CAPACITY FOR WOOD PULP ACCORDING TO GRADE 3-4
3-2 CHARACTERISTICS OF MILLS PRODUCING SULFITE PULP 3-9
3-3 CHARACTERISTICS OF MILLS PRODUCING SEMICHEMICAL PULP AND
ASSOCIATED WITH KRAFT MILLS 3-23
3-4 CHARACTERISTICS OF MILLS IN THE UNITED STATES PRODUCING
SEMICHEMICAL PULP AND NOT ASSOCIATED WITH KRAFT MILLS 3-28
5-1 SULFITE MILLS WITH CANDIDATE BEST CONTROL SYSTEMS 5-10
6-1 STATE IMPLEMENTATION PLANS (SIP) FOR SULFUR EMISSIONS 6-4
6-2 STATE IMPLEMENTATION PLANS (SIP) FOR PARTICULATE
EMISSIONS 6-10
6-3 CALIFORNIA SULFUR DIOXIDE EMISSION REGULATIONS 6-22
6-4 CALIFORNIA PARTICULATE EMISSION REGULATIONS 6-23
7-1 SUMMARY OF UNCONTROLLED AND CONTROLLED EMISSION FACTOR
DATA AND RECOVERY/CONTROL METHODS FOR SULFITE PULPING,
ACID PLANT EMISSIONS 7-6
7-2 SUMMARY OF UNCONTROLLED AND CONTROLLED EMISSION FACTOR
DATA AND RECOVERY/CONTROL METHODS FOR SULFITE PULPING,
DIGESTER DISCHARGE SYSTEM EMISSIONS 7-7
7-3 SUMMARY OF UNCONTROLLED AND CONTROLLED EMISSION FACTOR
DATA AND RECOVERY/CONTROL METHODS FOR SULFITE PULPING,
RECOVERY SYSTEM EMISSIONS 7-11
7-4 AVERAGE UNCONTROLLED AND CONTROLLED EMISSION FACTORS
FOR SULFITE PULPING 7-14
7-5 SUMMARY OF UNCONTROLLED AND CONTROLLED EMISSION FACTOR
DATA AND CONTROL METHODS FOR NSSC PULPING 7-15
7-6 ESTIMATED NATIONWIDE EMISSIONS 7-22
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LIST OF FIGURES
Figure Pa§e
3-1 The pH of solutions containing various combinations
of sulfite, bisulfite, and sulfurous acid 3-7
3-2 Regional distribution of operating sulfite pulp mills 3-14
3-3 Trends in capacities and production rates for sulfite
paper grade pulps and dissolving pulps 3-16
3-4 Regional distribution of semichemical pulp mills
associated with kraft pulp mills 3-26
3-5 Regional distribution of operating semichemical pulp
mills not associated with kraft pulp mills 3-31
3-6 Trends in capacity and production of semichemical pulp.... 3-33
4-1 Generalized sulfite process 4-3
4-2 Magnesium base recovery system 4-11
4-3 Ammonium base recovery system 4-14
4-4 Stora sodium base recovery system 4-16
4-5 Liquor preparation system 4-18
4-6 Generalized neutral sulfite semichemical (NSSC) process... 4-21
Vlll-
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1.0 EXECUTIVE SUMMARY
This report represents the results of a screening study which considered
the feasibility and need for developing new source performance standards for
two wood pulping processes. The wood pulping processes considered were the
sulfite process and the neutral sulfite semichemical (NSSC) process. The
sulfite process is actually a group of related processes. This chapter
provides a brief description of the screening study and lists the major
results of the study.
1.1 DESCRIPTION OF PROCESSES STUDIED
The sulfite processes account for about 5.5 percent of all wood pulp
produced in the United States. The sulfite processes are all descendants of
the process which is now referred to as the calcium acid sulfite process.
This process was originally referred to simply as the sulfite process. It
was the dominant commercial process used to produce wood pulp by chemical
means from about 1890 to the mid-1920's.
Other sulfite processes differ from the original process by the use of
different bases (magnesium, ammonia, or sodium) in the cooking liquor. Use
of these other, "soluble," bases makes it possible to produce wood pulp
using a less acidic cooking liquor than that required when calcium is the
base. Pulping processes using the less acidic cooking liquor are referred
to as "bisulfite" processes. Description of which sulfite process is
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being used at a particular mill requires specification of both base and pH
range (acid sulfite or bisulfite).
Many grades of paper and other wood products (rayon, cellulose acetate)
can be made from pulp produced by the sulfite processes. But, the share of
the wood pulp market belonging to pulp produced by the sulfite processes has
steadily declined since commercial introduction of the kraft process.
The NSSC process accounts for about 5.9 percent of all wood pulp
produced in the United States. The NSSC process is a much newer process
than the calcium acid sulfite process. The NSSC process was introduced in
the late 1920's and its commercial development has paralleled that of the
kraft process. The market share is limited by the demand for the
relatively coarse grade of pulp usually produced. Most semichemical pulp is
used to make corrugating medium. Hardwoods, not suitable for pulping by
other processes, sawdust, wood shavings and even bar.k and twigs are used
as raw materials for the NSSC process. There is a current trend for NSSC
pulping to be replaced by other semichemical pulping processes. The
driving force behind this change is the difficulty in disposing of the spent
NSSC liquor in an environmentally acceptable manner.
1.2 SCOPE OF WORK
The paragraphs below describe the objectives of this screening study,
the approach taken to reach the objectives and the limitations of the
study.
1.2.1 Objectives
The objective of this project was to develop information required
to advise on the feasibility and need for standards of performance for
two wood pulping processes. The processes considered-were the sulfite pro-
cess and the neutral sulfite semichemical (NSSC) process.
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1.2.2 Approach
Background information relating to the feasibility and need for
standards of performance for the two wood pulping processes was collected
and is organized in this report.
Information was collected from the following sources;
the open literature,
persons within the EPA,
persons in state agencies in Washington, Oregon and
Wisconsin,
The National Council of the Paper Industry for Air and
Stream Improvement (NCASI),
The American Paper Institute,
The Northwest Pulp and Paper Association, and
persons at individual mills.
Reports of all contacts and copies of all correspondence are included in
the docket for this report. Contacts included visits to five operating
pulp mills. Pertinent references not in the open literature and other
relevant information are included in the docket prepared with this report.
The sections which follow provide descriptions of the industry, the
processes and applicable control methods. Emission test data is described
and presented. Emission factors are calculated for a number of systems
in sulfite mills and NSSC mills. Nationwide emissions are calculated for
current conditions, for continued operation under current regulations, and
for operation under possible new source performance standards more strict
than current standards. In addition, sampling and analytical methods applr
cable to these processes are described.
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1.2.3 Limitations
This study is .limited, to atmospheric emissions of
pollutants from the sulfite processes and the neutral sulfite semichemical
process. Emissions from power boilers associated with these mills are
specifically excluded. Possible emissions from bleaching operations are
not included in the study. Bleach plant emissions are generally con-
sidered to be small.
The screening study concentrates o.n emissions of sulfur dioxide and
particulates. These are reported to be the major pollutants associated
with these processes. Emissions of nitrogen oxides from recovery furnaces
burning ammonia base spent sulfite liquor are discussed briefly.
Possible emissions of organic pollutants are not considered and no informa-
tion was found concerning these emissions.
The duration of this screening study was limited to four months. The
level of effort was limited to a nominal 1500 manhours. Within these time
constraints it was necessary to rely on secondary sources for much of the
information required. In many cases information from one source would
conflict with that from another source. In some cases the conflicting
information is reported with the statement that a conflict exists. In
other cases the information considered to be most reliable was reported
A number of errors were detected in the information obtained and although
efforts were made to correct as many as possible, inaccuracies undoubtedly
exist in the information included in this report.
Another limitation involves the statistical categories used by the
industry for reporting pulp mill capacities and production rates. The
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statistical categories do not match the processes under consideration.
Estimates had to be made as to what proportions of the pulp included in
the various statistical categories were produced by the processes under
consideration.
1.3 RESULTS
The results of the screening study are listed below.
* Although the sulfite and NSSC processes are in widespread
commercial use, each mill is unique in its specific
application of the processes.
Both the sulfite and NSSC processes are declining
industries with regard to capacity and production.
It is not possible to document the rate of decline of
pulp production by the sulfite process. Dissolving
pulp is produced using the sulfite process and using
the kraft process. Statistical sources which report
production and capacities do not report the type of
process used to manufacture dissolving pulp.
* No firm statement can be documented about the rate
of decline of NSSC pulping in the U. S. There
seems to be a trend to replace NSSC liquor by
alternate cooking liquors to produce semichemical
pulp. Statistics relating to production and
capacity for production of semichemical pulp give
only the total amount of semichemical pulp produced;
no information is provided on the process used to
produce the pulp.
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* Some sources of information fail to distinguish clearly
between sulfite mills using cooking liquors with pH below 7
and neutral sulfite semichemical mills.
* The major atmospheric pollutants emitted from the sulfite
process are sulfur dioxide and particulates. The
primary emission sources are the digesters, the cooking
liquor preparation system, and the recovery system.
Depending on the cooking liquor base, minor amounts of
ammonia, nitrogen oxides, and reduced sulfur species may
also be emitted.
The major atmospheric pollutant from the NSSC process, as
carried out at mills which are not associated with kraft
mills, is particulates. The primary emission source is
the recovery system. Some recovery systems may emit
significant amounts of sulfur dioxide. Other types of
recovery systems may emit reduced sulfur species.
The only separately identifiable emission sources
for NSSC mills which are integrated with kraft mills
are the liquor preparation system and the digester.
For mills which prepare cooking liquor from sulfur
and sodium carbonate (or sodium hydroxide), sulfur
dioxide emissions from these sources are very low.
No emission data were obtained for mills which use
green liquor to prepare NSSC liquor.
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Incremental emissions from kraft recovery boilers, which
are the result of adding spent NSSC liquor to kraft
black liquor before recovery, are covered by existing
kraft mill regulations.
Only a few states have implemented regulations specif-
ically designed to limit emissions from the sulfite or
NSSC process. Regulations for the NSSC process are
usually incorporated with regulations for the kraft
wood pulping process. Many states may attempt to
regulate the sulfite and NSSC processes as generalized
industrial sources. The degree of enforcement is unknown.
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2.0 CONCLUSIONS AND RECOMMENDATIONS
2.1 CONCLUSIONS
The conclusions reached as a result of this screening study are out-
lined in the following two subsections.
2.1.1 Sulfite Process
Based on background information for the sulfite wood pulping process,
the following conclusions have been developed.
The declining capacities and productions of the
sulfite processes will continue as other wood pulping
processes are improved or developed to produce comparable
grades of pulp from similar types of wood. Stringent en-
vironmental regulations, especially those associated
with water effluents, are accelerating this trend.
Based on Model IV calculations, estimated uncontrolled
SOz emissions from the digester and the cooking liquor
preparation system are 29.0 and 2.5 kg/Mg of pulp
(58.0 and 5.0 Ib/ton), respectively. For a mill
operating under NSPS, corresponding SOa emission
limits would be 0.26 kg/Mg of pulp (0.52 Ib/ton)
for both the digester and the cooking liquor
preparation system.
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The recovery system emits S02 and particulates. Based
on Model IV calculations, estimated uncontrolled
emissions from this unit in a typical sulfite mill
are 9.36 kg S02/Mg of pulp (18.7 Ib/ton) and 1.8 kg
particulates/Mg of pulp (3.6 Ib/ton). For a mill
operating under NSPS, the S02 emission limit would
be 1.22 kg/Mg (2.44 Ib/ton). (Note: These emission
figures represent composite data for four types of
cooking liquor and should not be used without
consulting the Model IV calculation in Appendix B.)
Those states which have regulations for the sulfite
process have achieved a reasonable level of emissions
control. For those states which do not have regu-
lations, not enough data exist to determine the
current level of emissions control.
2.1.2 NSSC Process
Based on background information for the NSSC wood pulping process,
the following conclusions have been developed.
The production of semichemical pulp is expected to
increase slightly over the next few years. Even
though the NSSC process is probably the "best" way
to produce semichemical pulp from a process
standpoint, environmental restrictions are creating
a trend toward alternate processes. The rate of de-
cline of NSSC pulping is very difficult to define
because semichemical pulp statistics do not differen-
tiate among the various semichemical processes.
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Additional work will be required to estimate atmos-
pheric emissions or to determine the effect of state
regulations. At present, emission data for the
NSSC process are too sparse.
2.2 RECOMMENDATIONS
Recommendations developed as a result of this screening study are
based on the criteria discussed below.
Industry Growth - Based on historical data and other
available statistics, will the capacity and production
increase or decrease through 1983? Will new technology
result in substantial expansions or modifications
through 1983? Will obsolete equipment be replaced?
Status as a Major Source - Will the construction of
a new mill or the expansion or modification of an
existing mill result in the atmospheric emission
of any criteria pollutant equal to or greater than
91 Mg per year (100 tons per year)?
Degree of State Regulation and Enforcement - What
portion of the total U. S. capacity is operating
under state regulations? Are the state regulations
enforced?
Relocation Potential - Will the industry relocate
in another state to avoid strict emission regulations
in a particular state?
Impact of NSPS - Based on Model IV calculations, what
will be the reduction in national emissions
(T_ - T,T) resulting from NSPS?
S N °
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Health and Welfare - Will implementation of NSPS
improve ambient air quality as reflected by at-
mospheric modeling?
2.2.1 Sulfite Process
Based on the data compiled during this study, the sulfite wood pulp-
ing process does not merit further consideration for the development of
new source performance standards. The reasons for this recommendation are
based on a review of the criteria as discussed below.
Growth - Overall production of wood pulp by the sulfite
process will decline over the next five years. During
that period only one new sulfite mill is being con-
sidered, but its construction appears uncertain.
No breakthroughs in sulfite pulping technology
are anticipated.
Major Source - If a new, 182 Mg/day (200 ton/day) sulfite
mill was constructed, it would be classified as a
major source. Uncontrolled atmospheric emissions would
be 6.77 Gg S02/yr (1200 ton/yr) and 298 Mg particu-
lates/yr (328 ton/yr). As previously discussed, the
likelihood of a new sulfite mill is doubtful.
Regulations - At present, a large portion of the U. S.
sulfite pulp capacity is operating under relatively
strict regulations. Almost 71% is operating under
state S02 emission regulations. The result is
a reduction of almost 73% over uncontrolled SOa
emissions. In addition, 64% is operating under
state particulate emission regulations. The result
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is a reduction of approximately 1% over uncontrolled
emissions. Most state regulations closely approxi-
mate the emission limits for best available control
technology and enforcement is strict.
Relocation - The sulfite industry is not given to
relocation. In Alaska, Oregon, and Washington, where
strict emission regulations have been implemented, a few
mills have closed, but most have made modifications in order
to be in compliance with the state regulations.
Impact - The impact of New Source Performance
Standards as estimated by a Model IV calculation
is much lower than originally predicted by
TRC in 1975. According to the revised Model IV
calculation, sulfite wood pulping places in the
lower one third of all industries when ranked
according to impact, (T - T ), for both S02
o IN
and particulate emissions reduction.
Only one state, Oregon, has done any ambient
air quality modeling for atmospheric emissions
from sulfite pulp mills. The Oregon emission
regulations are designed to achieve a specified
ambient air quality based on this modeling. The
extent and accuracy of this modeling is unknown.
2.2 NSSC PROCESS
Additional data is needed to determine whether the development of
new source performance standards for the NSSC wood pulping industry is
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justified. The necessary information for this decision is either unavailable
or incomplete. Therefore, additional effort is recommended in the following
areas.
Industry Capacity and Productions - Detailed NSSC data
is required as opposed to the general semichemical
statistics that are currently available. At pre-
sent, it is impossible to differentiate between
NSSC and semichemical data without direct contact
with each semichemical mill.
Emission Data - Well documented emission data for the
following process units and pollutants are needed:
1) Digesters: S02
2) Cooking liquor preparation systems: SOa
3) Recovery systems: SOa, reduced sulfur species
(HaS, etc.), and particulates.
State Regulations and Enforcement - Regulatory
information is needed to determine the extent of
regulations, particularly in regard to NSSC mills
associated with kraft mills, and the degree of
enforcement being exercised.
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3.0 DESCRIPTION OF THE WOOD PULPING INDUSTRY
The annual capacity of the wood pulping industry in the United States
in 1978 is reported by the American Paper Institute1 to be 50,676 Gg
(55,861,000 tons). Several grades of pulp are included in this total
capacity. Several processes are used to produce this pulp. Three organ-
izations (the United States Department of Commerce Bureau of the Census,
the United States International Trade Commission and the American Paper
Institute) publish statistical information related to wood pulp capacity
and production in the United States. In each case the statistical data
are presented by grades of wood pulp produced. The major grades of wood
pulp recognized by these organizations are:
dissolving and alpha,
sulfite paper grades,
sulfate and soda paper grades,
* semichemical, and
mechanical.
In some cases statistical data are reported for categories within the
major grades such as bleached and unbleached sulfite and bleached and un-
bleached sulfate pulp.
Processes which produce dissolving and special alpha pulp, sulfite
paper grade pulp, and sulfate paper grade pulp are called chemical pulping
processes. In these processes the lignin which holds the cellulose fibers
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together is dissolved by chemical means. The material is essentially
completely pulped and requires very little if any mechanical action to
complete the pulping process. Dissolving pulps require additional chemical
treatment. The yield of pulp for the chemical processes is usually about
30 to 50 percent of the wood fed to the digester. The yield of some
chemical pulping processes may be as high as 55 or 60 percent. The portion
of the wood not recovered as pulp appears largely as dissolved organic
materials in the spent cooking liquor.
In the production of semichemical pulp, the pulping process is only
partially carried out in the digester. The remainder of the pulping oper-
ation is carried out mechanically using presses and disc refiners. The
yield of semichemical pulps is usually in the range 68 to 85%.
Mechanical pulps are produced primarily by mechanical action. Ground-
wood pulp, used in newsprint is produced entirely by mechanical action.
The yield is usually about 95 percent of the wood fed to the grinders.
Several other processes produce pulp primarily by mechanical action,
although partial pulping may be accomplished by the action of heat or
chemicals. These processes typically have yields above 85 percent. Pulp
grades produced by these processes include thermomechanical, chemi-
mechanical, defibrated and exploded pulps.
The current program is concerned with estimation of air emissions
from the sulfite process and the NSSC process. These processes are used
to produce dissolving and special alpha pulp, sulfite paper grade pulp and
semichemical pulp. However, some dissolving pulp is produced using the
sulfate (kraft) process and some semichemical pulp is produced using
processes other than the NSSC process.
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Dissolving and special alpha pulps are generally used as chemical
feedstocks rather than as raw materials for the manufacture of paper
related products. Photographic film, cellulose acetate and rayon are made
from these pulps. Sulfite paper grade pulps are used to make a variety of
paper products including tissue, fine writing paper, and as part of the
furnish for newsprint. Most semichemical pulp is used to produce corruga-
ting medium. However, some semichemical pulp is used to produce specialty
products such as glassine paper and as part of the furnish for a variety
of paper grades.
3.1 DESCRIPTION OF SULFITE AND NSSC PULPING
The current program has considered that group of wood pulping processes
which has the common feature of having the bisulfite ion present in the
cooking liquor. These processes have been referred to as the sulfite
process and the neutral sulfite semichemical (NSSC) process.
The sulfite process is in fact a group of related processes. These
processes are usually used to produce chemical pulps. As indicated in the
previous section, paper grade sulfite pulps and some dissolving and special
alpha pulps are produced by these processes. In addition, one plant is
reported to use an acidic (pH 4) sulfite process occasionally to produce
. , . , , 1 > 2 i 3 > 1 0
semichemical pulp.
Historically, the neutral sulfite semichemical (NSSC) process was the
dominant process used to produce semichemical pulp. Most semichemical pulp
is still produced using this process. However, other processes produce a
significant fraction of the semichemical pulp now made.
Table 3-1 gives the capacity for the various grades of pulp produced
in the United States. The processes under consideration produce a relatively
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Table 3-1. 1978 CAPACITY FOR WOOD PULP ACCORDING TO GRADE'
Dissolving and special alpha
Sulfite paper grades
Sulfate and soda paper grades
Semichemical
Mechanical
Screenings
Total
Gg/yr
1,416
2,045
34,650
4,265
8,106
65
50,675
Capacity
Thousands'
of tons/yr
1,561
2,254
38,195
4,701
8,935
72
55,717
Percent
2.8
4.0
68.6
8.4
16.0
0.1
99.9
Consumption, 1976-1979 Capacity with Additional Data for 1980-1982.
New York. Revised data, March 13, 1978.
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small fraction of the total pulp produced in the United States. Even if
all dissolving pulp were produced by sulfite processes and all semichemical
pulp by the NSSC process, these processes would account for only slightly
more than 15% of the wood pulp produced in the United States.
3.2 THE SULFITE PULPING INDUSTRY
This section describes several features of the sulfite wood pulping
processes. Cooking liquors used by the industry are described. The geo-
graphical distribution of plants is presented. Production history and
projected production trends are presented within the limitations of
available data. More details regarding the processes, including descrip-
tions of processes, recovery systems, process emissions, and emission
control systems are given in later sections.
3.2.1 Cooking Liquors Used in the Sulfite Processes
In the nomenclature commonly employed in the wood pulping industry
the general term sulfite process refers to any one of several processes
which use cooking liquors that are acidic and contain bisulfite ion. From
1890 to 1950 the only commercially important process which fit this
description used a cooking liquor prepared from sulfurous acid and lime-
stone. A large excess of sulfurous acid was required to keep the calcium
ion in solution. The pH of the cooking liquor was below 2. It contained
as much as 8 percent sulfur dioxide by weight. This process was commonly
called the sulfite process.
During the 1950's several modifications of this process were intro-
duced on a commercial scale. The modifications included using other,
"soluble", bases instead of calcium. The other bases used were magnesium,
sodium and ammonia. The use of these other bases also made it possible
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to use a cooking liquor with a higher pH (usually in the range pH 3-4).
As the nomenclature has evolved the term acid sulfite process is now
applied to those processes using a cooking liquor with a pH less than 2 and
the term bisulfite process is now applied to those processes operating in the
pH range 2-6.3 To specify a sulfite process, both pH range and base need to
be stated.
There are seven possible sulfite processes: acid sulfite pulping using
calcium, magnesium, sodium or ammonia and bisulfite pulping using magnesium
sodium, or ammonia. Six of these possible processes are actually being used
by at least one plant in the United States in 1978. Within the limits of
the information collected for this screening survey, no plant has been
identified in the United States which practices bisulfite pulping using
sodium as the base.
Figure 3-1 illustrates the pH of solutions containing various
combinations of sulfite ion (SOs"), bisulfite ion (HSOa ), and sulfurous
acid (HaSOs) in the presence of sodium and magnesium ions. This figure
shows that acid sulfite solutions contain approximately equal amounts of
bisulfite ions and sulfurous acid and are highly buffered. The sulfur in
bisulfite cooking liquors is primarily in the form of bisulfite ion with
relatively low concentrations of sulfurous acid or sulfite ion present.
Since buffering requires the presence of two species (HaSOa, HSOs or
HSOa-, SOa ) in approximately equal concentrations, the true bisulfite
cooking liquors are not buffered.
Pulping processes using magnesium or sodium as the base recover the
chemical values of the base for economic reasons. The recovery systems
involve combustion of spent cooking liquor. Sulfur and heat values in
the liquor are recovered in addition to the base. Spent sulfite liquors
3-6
-------
10.0
9.0 __
8.0
7.0 _
6.0
"S 5.0
4.0
3.0
2.0 _
1.0 _
Sulfite
Bisulfite 50 60
H2S03 50 40
30 grams per liter total SOz concentration
3.0Z total SO2
60 70 80 90
40 30 20 10
Figure 3-1. The pH of solutions containing various combinations of
sulfite, bisulfite, and sulfurous acid.
Source: Tomlinson, G. H., II. pulp. In: Kirk-Othmer Encyclopedia
of Chemical Technology, Vol. 16, Standen, A. (ed.) New ?ork
John Wiley and Sons, Inc., 1968. p. 713.
Used with permission of John Wiley and Sons, Inc.
3-7
-------
which use ammonia as the base are usually incinerated. Heat is recovered for
economic reasons and sulfur is recovered for environmental reasons. Ammonia
is not recovered.
No practical means has been found for recovering either calcium or sulfur
from calcium base spent sulfite liquor. Spent sulfite liquor from mills using
acid sulfite cooks with either calcium or ammonia as the base can be evapor-
ated and used for road binding material. These spent sulfite liquors can
also be neutralized and used to grow Torula yeast or can be processed to
make a variety of products including surface active agents, fertilizers,
animal feeds, ethanol, and vanillin.
Air emissions from a sulfite mill depend on the process used, the
recovery system used, if any, how efficiently the recovery system operates,
the type of air emission control equipment and how efficiently the air
emission control equipment is operated.
3.2.2 Characteristics of Sulfite Mills in the United States
Table 3-2 lists the location, capacity and process used for sulfite
mills currently operating in the United States. Available information about
recovery furnaces is listed. In many cases the information about recovery
furnaces is meager: only the name of the manufacturer or the fact there is
a furnace may be reported. The addresses and telephone numbers of these
mills are given in Appendix A (Table A-l). Table A-l also lists three pulp
mills which are listed as idle and two pulp mills which were closed perman-
ently in the spring of 1978.
The Crown Zellerbach mill in Lebanon, Oregon is included in Tables 3-2
and A-l because at least part of its capacity is used to produce sulfite
pulp, The pH ranges used at this mill correspond with those normally
associated with sulfite pulping. This mill is reported to produce semi-
chemical pulp in addition to sulfite pulp.
3-8
-------
Table 3-2. CHARACTERISTICS OF MILLS PRODUCING SULFITE PULP
State
Alaska
Alaska
Florida
Maine
New York
Oregon
Oregon
Oregon
Oregon
Pennsylvun La
City
Ketchikan
Sitka
Fernandlna
Beach
Mlllinocket
Glens Falls
Lebanon
Oregon City
Newberg
Salem
Mehoopany
Company
Ketchikan Pulp Co.
Alaska Lumber &
Pulp Co. Inc.
ITT Rayonier Inc.
Great Northern
Paper Co.
Finch Pruyn &
Co. Inc.
Crown Zellerbach
Publishers Paper Co.
Publishers Paper Co.
Boise Cascade Corp.
Procter & Gamble
Capacity Base
Mg/day
558 Mge>f
544 Mgf
408 NH3p
544b Mg8
272 NI13
91 NH3h
209 Mg1
227 Mg1
227b NI13J
218C NH3e
Acid Sulfite Recovery
Or Bisultite Furnaces
Acid Sulfltef 4 B&Wb
Acid Sulfitef 3 B&Wb
Bisulfite8
Bisulfite1 2 Loddbyb
,
Acid Sulfite . Liquor sold concen-
and Bisulfite trated or dried
Bisulfite1 B&W1
Bisulfite1 BiW1
Acid Sulfite Furnace
Paper Products Co.
Washington Bellingliam Georgia-Pacific Corp.
454
Ca
Arid Sulfite
Products such as
ethanol and vanillin
are produced - no
burning.
(Continued)
-------
Page Two
Table 3-2. (Continued)
State
Washington
Washington
Washington
Washington
Washington
Washington
to Wisconsin
M
O
Wisconsin
Wisconsin
Wisconsin
Wisconsin
Wisconsin
City
Camas
Cosmopolis
Everett
Hoquiam
Longview
Port Angeles
Appleton
Brokaw
Green Bay
Green Bay
Park Falls
Peshtigo
Company
Crown Zellerbach
Weyerhaeuser Co.
Scott Paper Co.
ITT Rayonier Inc.
Weyerhaeuser Co.
ITT Rayonier Inc.
Consolidated
Papers Inc.
Wausau Paper
Mills Co.
American Can Co.
Procter & Gamble
Paper Products Co.
Flambeau Paper Co.
Badger Paper Mills
Capacity Base
Mg/Day
400 Mge'h
408 Mg6'1
757m NH,6'1"
430 Nae>"
363 Mge
454 NH3C
112 Cad
169 Mgd'e
136 Cad'e
377d NH3d
100 Cad
100 Cad
Acid Sulflte
or Bisulfite
Bisulfiteh
Acid Sulflte1
Bisulfite
Acid Sulfite"
Bisulfite0
Acid Sulfite
Acid Sulfite
Acid Sulfite
Acid Sulfite
Recovery
Furnaces
Furnace '
Furnace
m
Furnace
Kraft Type"
Copeland
Liquor burned
Inc.
Wisconsin Port Edwards Nekoosa Papers Inc. 195
Mg
Copeland
(Continued)
-------
Page Three
Table 3-2. (Continued)
Scate
City
Company
Capacity
Mg/Day
Base
Acid Sulfite
or Bisulfite
Recovery
Furnace
Wisconsin
Wisconsin
Rhlnelander
Rothschild
St. Regis Paper Co.
Weyerhaeuser Co.,
Paper Division
TOTAL CAPACITY OF MILLS
PRODUCING SULFITE PULP
68
181
8002
Ca Acid Sulfite
d,e
Ca
Acid Sulfite
Unless otherwise noted, capacity figures are from personal communication from Isaiah Gellman,
Executive Vice President, National Council of the Paper Industry for Air and Stream Improvement Inc.,
New York. NY. Letter dated 20 June 1978.
.1 Post's 1978 Pulp and Paper Directory, Miller Freeman Publications Inc., San Francisco, CA (1977).
C Hendrickson, E. R., J. E. Roberson, and J. B. Koogler, Control of Atmospheric Emissions In the Wood Pulping
Industry, Environmental Engineering, Inc. Gainesville, Florida, CPA Contract No. CPA 22-69-18. March 1970.
Dldler, Paul, Wisconsin Department of Natural Resources, Bureau of Water Management, Personal communication
with C. M. Thompson, Radian Corp. July 18, 1978.
6 Cillespie William J., Special Projects Manager, National Council of the Paper Industry for Air and Stream
Improvement, Inc. New York, NY. Letter dated June 13, 1970.
Miller Stanley F., Personal.communication with W. C. Mlcheletti and C. M. Thompson, Radian Corp. during
visit to Publisher's Paper Company In Oregon City, Oregon.
8 Reef, TAPPI 54(4):564-567. 1971.
(continued)
-------
Page Four
Table 3-2. (Continued)
Personal communication from T. R. Aspitarte, Manager, Environmental Developmental Programs, Crown
Zellerbach, Camas, Washington. Letter dated 7 June 1978.
Personal communication with Rod Schmall, Manager of Environmental Services, Publisher's Paper
Company, Oregon City, Oregon. Telephone conversation, dated 31 May 1978.
Personal communication with Bill Gray, Technical Director, Boise Cascade Corporation, Salem, Oregon.
Telephone conversation dated 31 May 1978.
k
Personal communication with Fred Fenske, Engineer, Industrial Branch, Washington Department of
Ecology (DOE), Lacy, WA. Comment made during visit to Washington DOE, 19 June 1978.
1
Personal communication with K. R. Devones, Technical Director, Weyerhaeuser Co., Cosmopolis, Washington.
Telephone conversation dated 1 June 1978.
Personal communication with A. Murl Miller, Manager of Environmental Resources, Scott Paper Co.,
n" "^ 3°' 19?8- 3&3 "8 Pei" day °f Prodllct:ion capacity will be phased out by
1 June"1! 978° U°n "^ Jlm Maxfield' ITT Ray°nler. Hoquiam, Washington. Phone conversation
°f Envlroni"ental Quality, Sulfite Pulping - Emissions and Control, A Background Report
Undated. --- ------ * --- ---
r- , Document: Acid SulHte Pulping. Final Report. Environmental Science and Engineering,
Gainesville, Florida. EPA-450/3-77-005, PB 264 301, EPA Contract No. 68-02-1402. January 1977. p. 29a.
-------
Sulfite mills are concentrated in the Pacific Northwest in the states
of Washington, Oregon and Alaska and in the Midwest in the state of Wisconsin.
Other operating mills are in Florida, Maine, New York, and Pennsylvania.
Two mills in Maine and one in Minnesota are idle. Two mills were shut down
permanently in the spring of 1978; one was in Washington and one was in
Wisconsin. Figure 3-2 indicates the approximate location of the 26 opera-
ting sulfite mills remaining in the United States.
The total capacities of the mills operating in the Pacific Northwest
represent 64 percent of the national capacity. The total capacities of mills
operating in Wisconsin represent 18 percent of the national capacity and the
capacities of the eastern mills total 18 percent of the national capacity.
According to the base used, 14 percent of the sulfite capacity is in mills
using calcium as the base; 45 percent is in mills using magnesium as the
base; 35 percent is in mills using ammonia as the base and 5 percent is in
one mill using sodium as the base.
Six of the seven mills using calcium as the base are in Wisconsin.
Seven of the ten mills using magnesium as the base are in the Pacific
Northwest. The mills using ammonia as the base are widely distributed. The
single mill using sodium as the base is in Washington.
3.2.3 Trends in the Capacity and Production of Sulfite Pulp
As indicated in Section 3.0, the statistical data regarding production
trends and .capacity trends are reported according to grade of pulp produced
and not according to process. The sulfite process is used to produce
sulfite paper grade pulp and dissolving pulp. Some dissolving pulp is also
produced using the sulfate (kraft) process.
The American Paper Institute5 has reported that the capacity for paper
grades of sulfite pulp is 5970 Mg per day (6,582 short tons per day). (This
calculation was based on 354 operating days per year.)
3-13
-------
Brokaw
Mnelander
Port Ange^e
lloqulnm
Ijiingvlew
Camas
Nfwberg
Sa I cm
l^ehano
Mlllinocket
(liens Fnlls
opany
Fernandlna Beard
FlRure 3-2. Regional distribution of operating snlflte pnlP mills.
-------
The 1978 capacity for dissolving pulp is reported to be 4046 Mg per
day (4460 short tons per day). Thus, the total capacities for paper grade
sulfite pulp and dissolving pulp are 10,017 Mg per day. The total capa-
cities of the sulfite mills listed in Table 3-2 are 8002 Mg per day (8820
short tons per day). Direct subtraction indicates that about half of the
dissolving pulp capacity is associated with the sulfate process. It
must be realized that the above result is only an estimate. The individual
mill capacity numbers in Table 3-2 are from the National Council of the
Paper Industry for Air and Stream Improvement, Inc. (NCASI) and a few other
sources. These capacity figures do not always agree with individual mill
capacity figures obtained from other sources (Post's 1978 directory and
contacts with personnel at individual mills).
Another factor influencing the validity of the above estimate is the
fact that the capacity of a given mill is not fixed. The capacity of a
given mill will vary with the type of pulp produced. Mills which produce
dissolving pulp often also produce paper grade pulp and can change the
amount of each type of pulp produced to suit changing market conditions.
Russell 0. Blosser5 (NCASI) has pointed out that the capacity for
paper grade sulfite decreased from 7720 Mg per day (8510 tons per day)
in 1960 to 5770 Mg per day (6360 tons per day) in 1978. This represents
a 25 percent decrease in capacity over a period of 18 years. Mr. Blosser
did not address trends in capacity for dissolving pulp produced by the
sulfite process. Therefore, his statistics fail to include about one-
fourth of the sulfite pulp industry.
Figure 3-3 illustrates the trends in capacity for producing sulfite
paper grade pulps and dissolving pulps for the years 1967 through 1982.
Capacities for the years 1979 through 1982 represent projections. The
3-15
-------
I
I-1
c^
8.0
7.0
6.0
5.0
4.0
0 Capacity for sulfite or dissolving pulp
0 Projected capacity for siilflte or dissolving pulp
Production of sulfltc pulp
() Production of dissolving pulp
82
Figure 3-3. Trends in rapnr U UT, and production rates for sulflto paper grade pulps and
d fssolvIng pu1ps.
Sources: American Paper Institute. Paper, Paperboard, Wuodpulp, Fiber Consumption,
1976-1979 Capacity wttli Additional Data for 1980-1982. New York.
U. S. Department of Commerce, Bureau of the Census. Current Industrial
Reports, Pulp, Paper, and Board, Washington, n. C., Yearly Summaries for
I9h7-197h.
U. S. Department of Commerce, Bureau of the Census. Current Iudnstil.il
Reports, Pulp, Paper, and Board, Washington, D. C., Monthly Summaries
For Felmiary, 1977 - February 1978.
02-3342-1
-------
projections past 198Q were based on information presented concerning
capacity under consideration. The capacity for producing sulfite paper
grade pulp shows a steady decline totaling about 15% from the years 1967
to 1972. Capacity increased slightly from 1972 to 1976, then fell again.
The closing of two small mills in the spring of 1978 and the planned phasing
out of 363 Mg per day capacity by January 1979 continue the trend of
decreasing capacity. The American Paper Institute survey7 indicates that
a capacity addition of 205 Mg per day is under consideration for 1982. Even
if this capacity increase occurs, 1982 capacity will be below 1978 capacity.
Figure 3-3 also illustrates trends in production. Production of sulfite
paper grades of pulp has generally run slightly over 90 percent of capacity
for the past 10 years. There was a significant dip in production in 1975.
Production of dissolving and special alpha grades of pulp has generally run
about 95 percent of capacity. Significant drops in production occurred in
1975 and 1976. Drops in capacity followed closely the drops in production.
3.3 THE SEMICHEMICAL PULPING INDUSTRY
Semichemical pulp is produced partly by chemical action and partly by
mechanical action. Wood chips or sawdust are digested with a cooking liquor
to partially dissolve the lignin which holds the cellulose fibers together.
The digested chips are pressed to remove some of the cooking liquor and to
separate some of the fibers. More liquid is added and the partially pulped
chips are sent through refiners which complete the pulping process
mechanically.
Semichemical pulping has been defined by the American Pulp and Paper
Association Committee on Coordination of Research as follows:
3-17
-------
"A broad definition of semichemical pulping would be
pulp produced in a yield range between that obtained by
ordinary or full chemical pulping and that obtained by
groundwood pulping, using any type of pulping liquor.
The range of pulp yield most often thought of for
semichemical pulping is between 68 and 85 percent."
In the past the dominant cooking liquor for producing semichemical pulp
was a neutral sulfite solution. The sulfite solution was prepared using
sodium as the base and was buffered so the final pH of the cook leaving the
digester was between 7 and 9. This process is known as the neutral sulfite
semichemical (NSSC) process and is still widely used. However, a significant
fraction of semichemical pulp is now produced using other cooking liquors.
3.3.1 Cooking liquors Used in the Semichemical Processes
In current practice, semichemical pulp is produced using neutral sul-
fite liquor,9 a non-sulfur liquor containing sodium carbonate and sodium
hydroxide, ° kraft green liquor, 1>12 kraft green liquor containing some
sodium sulfite, 3 and ammonium bisulfite liquor (with an initial pH of
4).11*'15 As stated above, the NSSC process usually is carried out
using sodium as the base. However, one plant in Tennessee uses ammonia
as the base in the NSSC cooking liquor.16 The discussion below will deal
primarily with the neutral sulfite cooking liquor. The other liquors will
be discussed to the extent necessary to describe the place of neutral sul-
fite cooking in the production of semichemical pulp.
Sodium based neutral sulfite cooking liquors can be prepared in
several ways. The method chosen for liquor preparation will depend upon
the process used for recovery of the spent liquor and in some cases the
costs of alternate raw materials.
Many plants prepare neutral sulfite cookiag liquor directly. When
this method is used, the liquor is prepared by contacting an aqueous
3-18
-------
solution of a base with a gas stream containing sulfur dioxide. The base
maybe either sodium carbonate (soda ash) or sodium hydroxide (caustic soda).
Contact is usually carried out countercurrently in a packed tower. A
solution of sodium sulfite results. Additional base will be added to provide
buffering action. The amount of additional base required will depend on the
wood species and the age of the feed material. Some plants combine
commercial sodium sulfite with the base to prepare the cooking liquor.
Preparation of cooking liquor from fresh raw materials requires that the
spent liquor not be recycled to the NSSC cooking operation. Several fates
are possible for the spent liquor. In the past the spent liquor was often
dumped into a lagoon or the nearest stream. Effluent limiations have made
this practice no longer feasible.
If the NSSC mill is operated in conjunction with a kraft mill the spent
liquor can be used as makeup for the kraft operation. Using the spent
semichemical liquor as makeup to a kraft mill is possible only if the semi-
chemical operation is a fraction the size of the kraft operation. In
addition, the continuing "tightening up" of the sulfur balance (and in some
cases the sodium balance) make it more difficult for kraft mills to accept
the spent NSSC liquor.
Green liquor, either from a kraft mill or from a kraft type recovery
furnace, can be used to prepare neutral sulfite cooking liquor. Several
methods have been given in the literature. A brief review of five methods
is given in Environmental Pollution Control, Pulp and Paper Industry, Part I,
Air.17 Other methods are described in the Kirk-Othmer Encyclopedia.18
Most of the methods for prearing NSSC liquor from green liquor have
in common the treatment of green liquor with carbon dioxide. This treatment
3-19
-------
releases hydrogen sulfide and makes, a solution of sodium bicarbonate. The
hydrogen sulfide is burned to produce sulfur dioxide. The sulfur dioxide
and sodium bicarbonate are recombined to make NSSC cooking liquor. Variations
exist in the ways the above steps are carried out. In the process developed
by the Institute of Paper Chemistry, sulfur dioxide is contacted directly
with flue gas to drive off hydrogen sulfide and produce NSSC liquor.
Neutral sulfite semichemical mills which are not operated in conjunction
with a kraft mill usually operate one of two types of recovery furnaces. One
type of recovery furnace operates under reducing conditions and the other
operates under oxidizing conditions. Most of the furnaces which operate under
reducing conditions produce a smelt which makes green liquor when dissolved
in water. The green liquor produced is similar in chemical composition to
kraft green liquor. These furnaces are referred to as kraft-type recovery
furnaces. Preparation of NSSC liquor from green liquor is carried out as
outlined above. Another option available to these mills is direct use of
the green liquor as cooking liquor to produce semichemical pulp.
Furnaces made by SCA-Billerud also operate under reducing conditions.
The spent liquor is pyrolyzed. This pyrolysis produces hydrogen sulfide and
other reducing gases and solid sodium carbonate and soot. The reducing
gases are burned to produce a stream rich in sulfur dioxide. The sulfur
dioxide is recovered using sodium carbonate leached from the solids.
Fluidized bed combustion is used in the furnaces which operate under
oxidizing conditions. Concentrated spent liquor is sprayed into the
furnace from the top and hot air is forced into the bottom of the furnace.
The ash formed is composed primarily of sodium sulfate. It contains about
10% sodium carbonate with minor amounts of calcium and potassium salts.
3-20
-------
The ash forms into spherical pellets in the fluidized bed. The ash can be
used as make-up for the kraft process if a kraft mill can be found which is
willing to use it and if transportation can be arranged. Otherwise, disposal
of the soluble ash is often a problem.
3.2.2 Characteristics of Semichemical Mills in the United States
It is theoretically possible to produce semichemical pulp from any
liquor used to prepare chemical pulp. To do so cooking time must be
shortened or the temperature lowered in the digester. The partially
pulped wood can then be treated mechanically to complete the pulping
process.
As noted, there is a natural relationship between operation of a NSSC
mill and operation of a kraft mill. This relationship exists because the
kraft mill can accept the spent liquor from the NSSC operation. On the
other hand it is possible to prepare NSSC cooking liquor from kraft green
liquor. One obvious way to eliminate the processing steps required to
prepare NSSC liquor from kraft green liquor is to use kraft green liquor
as the cooking liquor. A number of plants follow this procedure.
A spot check of several semichemical plants associated with kraft
plants indicates that there is a trend toward replacing NSSC liquor with
kraft green liquor in the production of semichemical pulp.
Plants which have made this conversion or which plan to in the near
future are doing so largely in response to environmental pressures. As
the mills discharge fewer pollutants, the kraft mill can no longer accept
the output from a NSSC mill as makeup. Producing NSSC liquor from kraft
green liquor requires at least two process steps and can involve emission
of atmospheric pollutants such as hydrogen sulfide or sulfur dio:-:ide.
3-21
-------
On the other hand, some NSSC mills not associated with kraft mills
are converting to non-sulfur cooking liquors. Most of these conversions
have been made as the result of environmental pressures. Owens-Illinois,
the first U.S. company to operate commercially the Institute of Paper
Chemistry (IPC) method, has gone to a non-sulfur cooking liquor at both
its semichemical plants.19'20 Three other plants have been reported to
be operating non-sulfur processes.
Table 3-3 lists capacities and cooking liquors for semichemical plants
in the United States associated with kraft mills. The capacities of the
associated kraft mills are listed. Table A-2 (Appendix A) gives the
addresses and telephone numbers of these plants. Mills were listed as
having associated kraft capacity if the same company had kraft capacity
at the same location.
It is quite likely that some of the mills which are listed as using
NSSC liquor no longer do so. Much of the information regarding cooking
liquor comes from Hendrickson e~b at.21 This report was prepared in early
1970. A spot check of semichemical mills operated in association with
kraft mills indicates a trend toward substituting green liquor for NSSC
liquor in the semichemical cook. Of the six plants contacted, two use
kraft green liquor,22'23 one uses a mixture of green liquor and sulfite
liquor2' and three25'25'27 use NSSC liquor. One of the mills using green
liquor had used NSSC liquor until two or three years ago.28 One of the
mills29 using NSSC liquor plans to rebuild their digester and convert to
green liquor within 2 years.
Figure 3-4 illustrates the geographical distribution of semichemical
mills associated with kraft mills. They are concentrated in the north-
3-22
-------
Table 3-3. CHARACTERISTICS OF MILLS PRODUCING SEMICHEMICAL PULP AND ASSOCIATED WITH KRAFT MILLS
State
California
Florida
Georgia
Georgia
Louisiana
Louisiana
Louisiana
Louisiana
New Hampshire
North
Carolina
Oklahoma
Oregon
City
Antioch
Fernandina Beach
Cedar Springs
Savannah
Bastrop
Bogalusa
Hodge
West Monroe
Berlin
Plymouth
Valliant
Albany
Company
Fibreboard Corp.
Container Corp. of
America
Great Southern Paper
Co.
Union Camp Corp.
International Paper
Co.
Crown Zellerbach
Continental Forest
Industries
Olinkraft Inc.
Brown Co. , Paper
Group
Weyerhaeuser Co.
Weyerhaeuser Co.
Western Kraft Paper
Capacity
Mg/Day
218
317
308
272
408
136
227
227
190
227
725
181
Associated
Kraft
Capacity
Cooking Liquor Mg/Day
a
Kraft green liquor
NSSCb
NSSCb
a
Kraft green liquor
NSSC8
NSSCd
NSSC8
Mixture of kraft
green liquor and
sulfite6
NSSC3
NSSC8
Kraft green liquor
b
NSSC
400
1270
1615
2310
1090
1225
1270
1040
700
1130
1360
500
Oregon
Toledo
Group
Georgia-Pacific Corp. 227
(continued)
Kraft green liquor
1000
-------
Page Two
Table 3-3. (continued)
State City Company
South Georgetown International Paper
Carolina Co.
Virginia Covington Westvaco Corp.
Virginia Hopewell Continental Forest
Industries
Washington Longview Longview Fibre Co.
Washington Longview Weyerhaeuser Co.
U)
1 Washington Wallula Boise Cascade Corp.
-P-
Total Capacity of Mills Producing
Semichemical Pulp and Associated
With Kraft Mills
Total Capacity of Mills Reported
to be Using Kraft Green Liquor
Total Capacity of Mills Reported
to Use NSSC Process and Associ-
ated with Kraft Mills
Capacity
Mg/Day
2958
272
159
200
218
249
5056
1660
3396
Associated
Kraft
Capacity*
Cooking Liquor Mg/Day
NSSC8 14008
NSSC8 1000
NSSC8 800
NSSCh 1720
Kraft green liquor1 280
NSSC8 420
^Post's 1978 Pulp and Paper Directory, Miller Freeman Publications Inc., San Francisco, California (1977)
Personal communication with William J. Gillespie, Special Projects Manager, National Council of the Paper Industry
for Air and Stream Improvement, Inc., New York. Letter dated 13 June 1978.
CPersonaL communication with Dr. Glenn Kimble, Air and Water Conservation Director, Union Camp Corporation,
Savannah, Georgia. Telephone conversation dated 9 June 1978. This plant switched from NSSC about 1975.
-------
t-o
Ln
Page Three
Table 3-3. (continued)
Personal communication with R. M. Rogan, Technical Supervisor, Crown Zellerbach, Bogalusa, Louisiana.
Telephone conversation dated 8 June 1978 and letter dated 14 June 1978. This mill plans to change
to kraft green liquor within 2 years.
p
Personal communication with R. A. Somsen, Technical Services Director, Olinkraft Inc., West Monroe,
Louisiana. Telephone conversation dated 9 June 1978.
Personal communication with D. McLaughlin, Environmental Engineer, Georgia-Pacific, Toledo, Oregon.
Telephone conversation dated 1 June 1978
Tlendrickson, E. R., J. E. Roberson, and J. B. Koogler, Control of Atmospheric Emissions in the Wood
Pulping Industry Environmental Engineering, Inc. Gainesville, Florida, CPA Contract No. CPA 22-69-18. March 1970.
'Personal communication with N. H. Anderson, Mill Manager, Longview Fibre Co., Longview, Washington.
Telephone conversation dated 30 May 1978.
Battan, Howard R, George J. Ahlquist, and Edward J. Snyder. "Green Liquor Pulping of Southern Oak
for Corrogating Medium" TAPPI 59, (6), pp. 130-133. June 1976.
-------
Longvleu (2)
Toledo
Albany
BerlJn
Covington
lopewetl
Plymouth
Georgetown
Savannah
Cedar Springs
Fernandina Heach
Figure 3-4. Regional distribution of semlchemical pulp mills associated with kraft pulp
mills.
-------
western and southeastern portions of the United States.
Table 3-4 lists the capacities, cooking liquors, and recovery systems
for semichemical mills with no apparent associated kraft capacities. The
addresses and telephone numbers of these plants are given in Appendix A
(Table A-3). Some of the cooking liquor information may not be current.
The known shifts to non-sulfur cooking liquor have occurred since 1970. The
information available about recovery systems generally does not describe
these systems adequately. The information is not specific enough to
determine the type of recovery system in operation at each plant.
According to Tables 3-3 and 3-4 the total capacity of semichemical
mills in the United States is 12,950 Mg of pulp per day (14,275 tons per
day). Of this total capacity 5,060 Mg per day is in mills associated with
kraft mills and 7900 Mg per day is in stand alone semichemical mills. The
capacity of plants reported to use green liquor is 1,660 Mg per day and the
capacity of plants known to use a non-sulfur process is 2,115 Mg per day.
If all the remaining mills use the NSSC process the total capacity for
NSSC pulp is 9,180 Mg per day (10,120 tons per day). Using these figures,
approximately 70 percent of the semichemical capacity uses NSSC cooking
liquor. This figure may be larger than the actual NSSC capacity since
some mills which are indicated as using the NSSC process may have switched
to an alternate cooking liquor.
The American Paper Institute survey30 lists the 1978 capacity for semi-
chemical pulp as 12,150 Mg per day (13,400 tons per day). The difference
between this figure and the capacity totals from Tables 3-3 and 3-4 (about
6 percent) is not significant and reflects the differences in capacities
reported by different sources of information.
3-27
-------
Table 3-4. CHARACTERISTICS OF MILLS IN THE UNITED STATES PRODUCING
SEMICHEMICAL PULP AND NOT ASSOCIATED WITH KRAFT MILLS
State
Alabama
Alabama
Indiana
Iowa
Iowa
to Kentucky
oo
Michigan
Michigan
Michigan
Minnesota
Mississippi
New Hampshire
City
Mobile
Stevenson
Terre Haute
Dubuque
Fort Madison
Hawesville
Filer City
Ontonagon
Otsego
Saint Paul
Meridian
Groveton
Company
National Gypsum Co.
Mead Corp.
Weston Paper & Mfg.
Co.
Celotex Corp.
Consolidated
Packaging Corp.
Western Kraft Paper
Group
Packaging Corp. of
America
Hoerner Waldorf
Menasha Corp.
Hoerner Waldorf
Flintkote Co.
Groveton Papers Co.
Capacity
Mg/Day
1593
680b
245b
227a
127b
250b
544b
400b
204b
318a
45a
272b
Cooking Liquor
NSSCb
NSSCb
NSSCb
NSSCb'C
NSSCb'°
NSSC;b
Non-Sulfur0
NSSC;b>°
Non-Sulfur
NSSCE
NSSCb
Recovery
System3 Comments
None Listed International Paper Co.
and Scott Paper Co. each
have large kraft mills
in Mobile
1 SCA-Billeruda
None Listed
None Listed
1 Copeland3
1 Copeland
1 B and Wa
Zimpro Wet3
oxidation
system
Dorr-Oliver3
None Listed
None Listed
None Listed
(continued)
-------
Page Two
Table 3-4. (continued)
State
New York
New York
Ohio
Ohio
Oregon
Pennsyl van la
U)
1
J^ Pennsylvania
Puerto Rico
South Carolina
Tennessee
Tennessee
Virginia
Virginia
City
Lyons Falls
Plattaburgh
Clrclevllle
Coshocton
North Bend
Erie
Sunbury
Arecibo
llartavllle
llarriman
New Johnsonvllle
Big Island
Rivtrvllle
Capacity
Company Kg/Day
Georgia-Pacific Corp. 109B
Georgia-Pacific Corp. 9la
Container Corp. of 272
America
Stone Container Corp. 408
Menasha Corp. 181
Hammermlll Papers 350
Croup
Celotex Corp. 21 7a
Carlbe Inc., Productos 113a
Fore at ales
Sonoco Products Co. 408
Harrlman Paperboard 227b
Corp.
Inland Container Corp. 358
Owens-llllnols Inc. 522a
Virginia Fibre Corp. 463a
Recovery
Cooking Liquor System3 Comments
NSSC6 None Listed
NSSCe None Listed
NSSCb'c None Listed
NSSC3' >C> 2 Copeland3 Post's lists capacity of
590 Mg/daya
NSSC Dorr-Oliver Incinerator not listed In
Post's Directory
NSSC6 B and W3
None Listed3
None Listed3
NSSCb'c' Sulfite Recov-
ery Process3
NSSCb None Listed3
b a f
NSSC B and W Amraoni.i base
Non-SulfurC 2 Smelters3
Non-Sul fur 1 B and W3
(continued)
-------
Page Three
Table 3-4. (continued)
OJ
1
tjj
o
State City Company
Wisconsin Green Bay Green Bay Packaging Co.
Wisconsin Tomahavk, Owens-Illinois Co.
Total Capacity of Operating Semichemical
Mills Not Associated with Kraft Mills
Total Capacity of Mills Reported to be
Using Non-Sulfur Cooking Liquor
Capacity of Remaining Operating Semi-
chemical Mills Not Associated with
Kraft Mills
Capacity Recovery
Hg/Day Cooking Liquor Systema Comments
181b NSSCb>c Dorr-Oliver3
526a Non-Sulfurc 1 B and W3
(kraft type)8
7897
2115
5782
aPost's 1978 Pulp and Paper Directory, Miller Freeman Publications, Inc. San Francisco, California (1977).
Personal communication with Isaiah Gellman, Executive Vice President,
National Council of the Paper Industry
for Air and Stream Improvement, Inc., New York, NY. Letter dated 20 June 1978.
°Personal communication with William J. Gillespie, Special Projects Manager, National Council of the Paper
Industry for Air and Stream Improvement, Inc., New York, NY. Letter dated 13 June 1978.
Personal communication with Tom Williscroft, Plant Manager, Menasha Corp., North Bend, Oregon. Verbal
communication during plant visit, 23 June 1978.
eHendrickson, E. R., J. E. Roberson, and J. B. Koogler. Control of Atmospheric Emissions in the Wood Pulping
Industry Environmental Engineering, Inc. Gainesville, Florida. CPA Contract No. CPA 22-69-18. March 1970.
Bryan, William P.,"Inland's Tennessee Mill Was First Designed for Ammonia Base NSSC" Paper Trade Journal
156(40): pp. 36-40, September 25, 1972. '
^Galeano, Sergio F. and Byron M. Dillard, "Process Modifications for Air Pollution Control in Neutral
Sulfite Semichemical Mills" JAPCA 22(3) p. 195., March 1972.
-------
Plnttshurgh
U)
I
LO
Groveton
Lyons Fal Is
Coshocton
Clrcleville
Rlvervllle
Big Island
H.iwesvl 1 le
Green Bay
Terre
Haute
Filer City
sego
Harrlman
Hart HviI 1e
Aren iho
Figure 3-5. Regional dint rlbnt inn of operating Rcmichemlrn I pulp mills not associated wltli
kraft pulp mills.
-------
Figure 3-5 illustrates the geographical distribution of stand alone
semichemical plants. They are scattered throughout the eastern United States.
One is in Oregon and one is in Puerto Rico.
3.3.3 Trends in the Capacity and Production of Semichemical Pulp
Figure 3-6 shows the trends in the capacity for production of semi-
chemical pulp for the years 1967 through 1982. Capacities for the years
1979 through 1982 represent projections. The projections past 1982 were
based on information presented concerning capacity under consideration.31
Capacity for producing semichemical pulp rose sharply from 1971 to
1973 and again from 1975 to 1978. Projections indicate a slower rise over
the next few years. Production figures have been rather erratic. Production
has been over 85 percent of capacity in nine of the last eleven years.
Production dropped to 75 percent of capacity in 1975.
The American Paper Institute survey32 indicates that a capacity addi-
tion of 716 Mg per day is under consideration for 1981.
3-32
-------
OJ
I
OJ
3
"8
13.0-
12.0
11.0
10.0
9.0
8.0
67
w Capacity for producing semlchemlcal pulp
^ Projected capacity for producing semichemical pulp
v Production of semichemlcal pulp
T~
68
i
69
i
70
71
72
73
75
Year
r-
76
77
r-
78
79
80
81
Sources:
Figure 3-6. Trends in capacity and production of semichemical pulp.
American Paper Institute. Paper, Paperboard, Woodpulp, Fiber Consumption,
1976-1979 Capacity vith Additional Data for 1980-1982. Now York.
U. S. Department of Commerce, Bureau of the Census. Current Industrial
Reports, Pulp, Paper, and Board, Washington, D. C., Yearly Summaries for
1967-1976.
U. S. Department of Commerce, Bureau of the Census. Current Industrial
Reports, Pulp, Paper, and Board, Washington, D. C., Monthly Summaries for
Febru.iry, 1 97 7-February 1978.
82
02-3341-1
-------
REFERENCES
1. Gillespie, W. J., NCASI. Private communication with Wayne C. Micheletti,
Radian Corporation. June 13, 1978.
2. Aspitarte, T. R., Crown Zellerbach, Camas, Washington. Private
communication with Wayne C. Micheletti, Radian Corp. June 7, 1978.
3. Sulfur Dioxide in Sulfite Cooking Liquor. TAPPI. Atlanta, Georgia.
T604su-70. 1970.
4. Gillespie, W. J., NCASI. Private communication with Wayne C. Micheletti,
Radian Corporation. June 13, 1978.
5. American Paper Institute. Paper, Paperboard, Woodpulp, Fiber
Consumption, 1976-1979 Capacity with Additional Data for 1980-1982.
New York.
6. Blosser, R. 0., NCASI. Private communication with Wayne C. Micheletti,
Radian Corporation. June 1, 1978.
7. American Paper Institute. Paper, Paperboard, Woodpulp, Fiber Consump-
tion, 1976-1979 Capacity with Additional Data for 1980-1982. New York.
8. Durgin, A. G. and T. W. Small, Jr. Semichemical Pulping. In: Modern
Pulp and Papermaking, 3rd edition, Calkin, J. B. (ed.). New York,
Reinhold Publishing Corporation, 1957. p. 157.
9. Anderson, N. S., Longview Fibre Co., Longview, Washington. Private
communication with Wayne C. Micheletti, Radian Corporation. May 30, 1978.
10. Early, F., Environmental Protection Agency, National Enforcement Invest-
igation Center, Denver. Private communication with Wayne C. Micheletti,
Radian Corporation. May 17, 1978.
11. Early, F., Environmental Protection Agency, National Enforcement Invest-
igation Center, Denver. Private communication with Wayne C. Micheletti,
Radian Corporation. May 17, 1978.
12. McLaughlin, D., Georgia Pacific Corporation, Toledo, Ohio. Private
communication with C. M. Thompson, Radian Corporation. June 9, 1978.
3-34
-------
13. Somsen, R. A., Olinkraft, Inc., West Monroe, Louisiana. Private
communication with C. M. Thompson, Radian Corporation. June 9, 1978.
14. Gillespie, W. J. NCASI. Private communication with Wayne C. Micheletti,
Radian Corporation. June 13, 1978.
15. Aspitarte, T. R., Crown Zellerbach, Camas, Washington. Private
communication with Wayne C. Micheletti, Radian Corporation. June 7, 1973.
16. Bryan, William P. "Inland's Tennessee Mill was First Designed for
Ammonia Base NSSC." Paper Trade J. 156 (40): 36-40. September 1972.
APTIC Abstract 046832.
17. Environmental Pollution Control, Pulp and Paper Industry, Part 1, Air.
Environmental Protection Agency, Office of Technology Transfer.
EPA-625/7-76-001. October 1976.
18. Tomlinson, G. H., II. Pulp. In: Kirk-Othmer Encyclopedia of Chemical
Technology, Vol. 16, Standen, A. (ed.). New York, John Wiley & Sons,
Inc., 1968. p. 716.
19. Early, F., Environmental Protection Agency, National Enforcement
Investigation Center, Denver. Private communication with Wayne C.
Micheletti, Radian Corporation. May 17, 1978.
20. Didier, P. and D. Evans, Wisconsin Department of Natural Resources,
Bureau of Water Management and Bureau of Air & Solid Waste Management.
Private communication with Wayne C. Micheletti, Radian Corporation,
June 6, 1978.
21. Hendrickson, E. R., J. E. Roberson, and J. B. Koogler, Control of
Atmospheric Emissions in the Wood Pulping Industry, Vol. 1, Dept.
of Health, Education and Welfare, Consumer Protection and Air
Pollution Control Administration. Final Report, Contract No. CPA
22-69-18, March 15, 1970, (Appendix A).
22. Mclaughlin, D., Georgia Pacific Corporation, Toledo, Ohio. Private
communication with C. M. Thompson, Radian Corporation. June 1, 1978.
23. Kimble, G., Union Camp Corporation, Savannah, Georgia. Private
communication with C. M. Thompson, Radian Corporation. June 9, 1978.
24. Somsen, R. A., Olinkraft, Inc., West Monroe, Louisiana. Private
communication with C. M. Thompson, Radian Corporation. June 9, 1978.
25. Anderson, N. H., Longview Fibre Company, Longview, Washington. Private
communication with Wayne C. Micheletti, Radian Corporation. May 30,
1978.
26. Rogan, R. M. , Crown Zellerbach Corporation, Bogalusa, La. Private
communication with C. M. Thompson, Radian Corporation. June 9, 1978.
3-35
-------
27- Smith, D., Great Southern Paper Company, Cedar Springs, Ga. Private
communication with C. M. Thompson, Radian Corporation. June 27, 1978.
28. Kimble, G., Union Camp Corporation, Savannah, Ga. Private communication
with C. M. Thompson, Radian Corporation. June 9, 1978.
29. Rogan, R. M., Crown Zellerbach Corporation, Bogalusa, La. Private
communication with C. M. Thompson, Radian Corporation. June 14, 1978.
30. American Paper Institute. Paper, Paperboard, Woodpulp, Fiber Consump-
tion, 1976-1969 Capacity .with Additional Data for 1980-1982..^New York.
31. American Paper Institute. Paper, Paperboard, Woodpulp, Fiber Consump-
tion, 1976-1969 Capacity with Additional Data for 1980-1982. New York.
32. American Paper Institute. Paper, Paperboard, Woodpulp, Fiber Consump-
tion, 1976-1969 Capacity with Additional Data for 1980-1982. New York.
3-36
-------
4.0 PROCESS DESCRIPTION AND EMISSIONS SOURCES
The purpose of this chapter is to describe the sulfite and neutral
sulfite semichemical wood pulping processes and to identify the types and
sources of atmospheric emissions associated with each process. Both pulping
processes are well proven and in widespread commercial use, but neither
process is well defined. That is to say, both processes are subject to a
number of variations, depending on the type of wood used and paper product
produced. For this reason, flow sheets with rigorous mass and energy balances
are not included. Instead a generalized flow sheet of each process has been
prepared showing the major process units. These process units are described
in detail and the potential atmospheric emission sources are discussed.
4.1 SULFITE PROCESS
The pulping of wood by the sulfite process involves the dissolution of
lignin in the wood chips by chemical attack in order to free cellulosic
fibers. The chemical attack is accomplished by cooking the wood chips in
one of several acidic liquors for a specified period of time. In this
respect, the sulfite wood pulping process is a fairly standard industrial
procedure. However, the use of different cooking liquors results in the
generation of different spent liquors which require proper treatment.
Since water pollution restrictions prevent dumping of the spent liquor,
a number of process schemes have been devised to recover heat and/or chemi-
cals from the spent liquor. The variety of these recovery systems means
4-1
-------
that there is no "typical" sulfite process, but rather a number of processes
which establish a certain degree of uniqueness for each sulfite pulp mill.
The major units in the sulfite pulping process are the digester, the
blow pit or dump tank, the washers and screens, the evaporators, the re-
covery system, and the liquor preparation system. These process units are
shown in Figure 4-1. Each of these units is a potential emission source
for atmospheric pollutants.
4.1.1 Digesters
4.1.1.1 Process Description
Two types of digesters are used in wood pulping operations: batch
and continuous. The batch digester is the most common type used in the
sulfite process. It is a large cylindrical vessel capable of handling 18 Mg
(20 tons) of wood chips at a time.1 The chips are fed into the digester
through a large opening in the top until the vessel is full. The top
opening is sealed and freshly prepared sufite cooking liquor is added until
the wood chips are completely covered. Steam is added until the mixture
has reached the proper pressure and temperature.
The pressure and temperature of the digester contents are then main-
tained for a specified period of time while the chips "cook". Typical
operating pressures may vary from 500 to 860 kPa (80 to 125 psi). Typical
temperatures may range from 135 to 170°C (275 to 340°F). The cooking time
is usually between four and eight hours. The operating conditions chosen
by a particular mill depend on the type of wood being pulped, the desired
yield and product, and the type of cooking liquor.2
The cooking liquor is a solution of sulfurous acid (HzSOa) and a
bisulfite salt, such as sodium bisulfite (NaHSOs). During the cooking
4-2
-------
Wood Chips
Batch Digester
(SOz)
Unbleached
Pulp Storage
Spent Liquor Storage
Recovery System
(SOi, participates)
Evaporators
(SOt)
Liquor Preparation
System
(SOi)
Figure 4-1. Generalized sulfite process.
(Potential pollutants shown In parenthesis)
70-1260-1
4-3
-------
cycle, the cellulose-lignin complex is separated by the chemical action of
either dissolved sulfite ions (SOs ) or dissolved bisulfite ions (HSOa ).
The exact reaction sequence is unknown. Some believe that as the sulfite
ions from the sulfurous acid react with the lignin, more sulfite is supplied
by the dissociation of the bisulfite salt. In this way, the bisulfite
buffers the cooking liquor by maintaining a reasonably constant sulfite
concentration.3 Still others believe that the primary reaction is between
the lignin and the bisulfite ions, with a base, such as sodium, acting as a
buffering agent to prevent polycondensation of lignin.^
Digester pressure is also kept constant during the cooking cycle by
drawing off amounts of liquid and gas. These relief streams may be directed
to a number of other process units, but are usually sent to a liquor storage
tank or a high pressure accumulator.
When the cooking cycle is completed, the digester can be emptied in a
number of ways. In the past, the most common practice was blowing. In this
method of discharging the pulp the digester pressure is relieved to about
207 to 276 kPa (30 to 40 psig), a large valve near the base of the digester
is opened, and the contents of the unit are blown into_an open _pit,. In some
cases, the pulp is blown "uphill" from the bottom of a digester into a blow
pit located 1.5 to 3 meters (5 to 10 feet) higher. The minimum pressure
for a "clean blow" (one in which all the pulp is removed from the digester)
is reported to be 377 kPa (40 psig).5
Recently, pulp mills have been using a lower pressure blow or a dump.
In a low pressure blow the digester pressure is relieved to a level slightly
above atmospheric before the digester contents are dumped into an open tank
located directly beneath the unit. To ensure a clean blow, a cool rinse
liquor may be added to the digester. The rinse liquor is usually spent
4-4
-------
sulfite cooking liquor that has been recycled or waste wash water.
Another method of emptying the digester is the pulp pump-out system.
It is more expensive and time consuming than either high-pressure blowing
or near-atmospheric dumping. Consequently, the pulp pump-out system has
achieved only limited use. Unlike the other two methods, this system is
totally enclosed. Following a cook, the digester pressure is relieved to
atmospheric, the lower valve is opened, and the contents are mechanically
pumped from the digester to a closed dump tank. To ensure complete pulp
removal, the digester is usually rinsed with spent sulfite liquor or waste
wash water.
Continuous digesters are most commonly used in NSSC pulping operations.
However, at least one sulfite pulp mill uses a continous digester.5 In
this type of digester, an uninterrupted flow of wood chips passes through
the unit where steam and cooking liquor are added. The method of
conveyance may be mechanical or gravity flow. Since the process is
continuous, blow pits of dump tanks are used as hold vessels before the
pulp is sent to washers. In some cases a continous diffusion washing stage
is integrated with the digester.
4.1.1.2 Emission Sources
Batch digesters have two potential sources of atmospheric emissions:
relief gases removed from the unit during the cooking cycle or prior to
pulp discharge and blow gases expelled during the pulp discharge. Depending
on the pH of the cooking liquor, digester relief gases may contain high
concentrations of sulfur dioxide. Acid sulfite cooking liquors usually
have a pH less than 2.0 and are more likely to release large amounts of
gaseous S02 in the digester. For a bisulfite liquor (pH between 2 and 5),
the amount of gaseous SOi evolved during the cook is much less.
-------
During the cooking cycle, relief gases are continously removed in order
to maintain a constant digester pressure. In addition, a large amount of
relief gas may be vented from the system prior to the digester blow, depen-
ding on the type of pulp discharge being practiced. Both types of relief
gas contain significant amounts of SOz. Since the purpose of the pre-blow
digester relief is to reduce blow emissions, this relief is usually collected
for appropriate disposal.
Digester blow emissions can be very large. The emissions will depend
on the type of pulp discharge practiced. For a high pressure blow, the pulp/
liquor slurry is passing from a pressurized to atmospheric regime with the
initial liquor temperature above the boiling point. Consequently, the
liquor flashes and produces large amounts of steam. Similarly, the sulfur
dioxide, which was more soluble at high pressure, is desorbed and liberated
with the steam. Cooking liquors with high sulfite concentrations (low pH)
produce greater S02 emissions.
Emissions resulting from a digester blow are short and infrequent. .A
blow will last only a few minutes with the peak flows and concentrations
lasting for five to six minutes.8 Since the blow occurs only at the end
of a cooking cycle, the emissions for each digester should occur no more
than once every four to eight hours. Pulp mills, however, will have
several digesters operating on a staggered sequence so that one digester
or another will be blowing every hour or two.
Digester blow emissions are reduced considerably in a low pressure
blow. Much of the S02 is removed in the relief gases when the digester
pressure is lowered. The emissions are reduced even further if a cool
rinse liquor is added. The rinse liquor lowers the slurry temperature and
4-6
-------
therefore decreases the amount of liquor that flashes when the pulp is
discharged.
Since pulp pump-out systems are completely enclosed, digester blow
emissions are virtually eliminated. These systems are expensive and time
consuming, however, and have received only limited use.
The only source of emissions from continous digesters is pressure
relief gases. Since the discharge of pulp is uninterrupted, there is no
intermittent digester blow and, therefore, no emissions associated with this
step in the pulping operation. Continuous digesters are, for the most part,
completely closed systems and normally use a cooking liquor in the pH range
of 4 to 6. These features mean that continuous digesters usually have
9
negligible emissions.
4.1.2 Blow Pits/Dump Tanks
4.1.2.1 Process Description
Blow pits and dump tanks are used as temporary storage vessels for the
large amounts of pulp and liquor which are intermittently discharged from
batch digesters. Blow pits and dump tanks may receive pulp from one or
several digesters. Following discharge to these vessels, the pulp is
drained of spent sulfite liquor and then transferred to the washers. In
some cases, acid sulfite pulp may also be neutralized. The spent liquor
is either directed to a recovery system for recovery of heat and/or
chemicals or treated for disposal or sale.
At one time, some mills also used these vessels for pulp washing. Once
the spent sulfite liquor had drained, the vessel would be flooded with water
and allowed to drain again. This procedure would be repeated several times,
until the operator was satisfied, based on his experience, that the pulp was
well washed. The wastewater from this pulp washing procedure would be very
4-7
-------
dilute and would require extensive concentration before it could be fed to
the recovery system- Therefore, this type of pulp washing is now
considered inefficient and is rarely practiced at present.
4.1.2.2 Emission Sources
The emissions most commonly associated with blow pits and dump tanks
result from the discharge of pulp from batch digesters. For the purposes
of this study, these emissions are considered to be from the digester and
are discussed in Section 4.1.1.2.
In the event that a blow pit or dump tank is also used for pulp washing,
small amounts of sulfur dioxide may be emitted. When the cool wash water
contacts the hot pulp, steam is produced and some sulfur dioxide may
vaporize. These SOa emissions would be very low.
4.1.3 Washers and Screens
4.1.3.1 Process Description
From the blow pits and dump tanks the pulp is directed to a system of
washers and screens. The washers rinse the pulp with hot water to remove
remaining spent sulfite liquor. Several types of washers are currently in
use, but the most common is a series of rotary drum vacuum filters, arranged
for multistage countercurrent washing. Wash water may be either evaporator
condensate or fresh water. The effluent wash water is sent to spent liquor
storage.
The purpose of screens is to prepare a pulp of uniform consistency by
removing uncooked knots, fiber bundles, and other oversize material.
4.1.3.2 Emission Sources
Washers and screens are usually considered to be very minor sources of
sulfur dioxide emissions.10'11 Depending on the cooking liquor pH and the
type of washers and screens employed, the emissions may be low enough that
4-8
-------
S02 recovery through scrubbing is not practical.12 However, if other SOz
emissions sources are well controlled, then washers and screens may be
a significant fraction of the total mill emissions.
4.1.4 Evaporators
4.1.4.1 Process Description
The pulp and paper industry is the single largest user of evaporator
equipment. The purpose of the evaporators is to increase the total solids
content of the spent sulfite liquor from about 15 percent to as much as 55
to 65 percent. The liquor is then either sold as a by-product or combusted
in a furnace for recovery of heat and/or chemicals. Two mills (one in
Oregon and one in Wisconsin) sell the concentrated spent liquor to yeast
plants that remove much of the organic material. At the Oregon mill the
residue is returned and burned once the nutrient value of the spent liquor
has been used by the yeast growing process.* "*
Any one of several evaporator types can be used, including horizontal
spray film, long tube vertical, and vapor recompression. Each mill is
unique unto itself. Some mills have relatively simple systems involving
only one type of evaporator. Other mills have evaporator systems which use
a combination of several types of units.
4.1.4.2 Emission Sources
The evaporation of spent sulfite liquor releases sulfur dioxide. The
more acidic the cooking liquor, the more SOz is released during the evapor-
ation process. For a multiple-effect vacuum evaporation plant, similar to
those found in Kraft pulping operations, there are two potential emission
sources. The vacuum system vent is the main emission point for evporator
gases. And the hotwell is the main emission point for evaporator condensates.:5
*-9
-------
The hotwell is a shell and tube surface condenser used to reduce the amount
of evaporator offgas by indirect condensation. The hotwell condensate may
contain appreciable amounts of dissolved SOz This condensate is usually
combined with the evaporator system condensate. Both points are considered
minor, but do contribute to the total sulfur dioxide emissions from the mill.
4.1.5 Recovery Systems
4.1.5.1 Process Description
The type of recovery system and the type of liquor base are very closely
related. In fact, the two greatest factors in the choice of a base appear to
be the end use qualities of the pulp and the recovery system. 6 The amount
of chemicals which can be recovered also depend on the base. For example,
if a mill uses a magnesium base cooking liquor, the magnesium and sulfur can
be recovered as magnesium oxide (MgO) and sulfur dioxide, respectively. On
the other hand, for an ammonia base only the sulfur can be recovered, while
the nitrogen is lost as molecular nitrogen (N2). A small fraction of the
ammonia is converted to nitrogen oxides (NO ).
X
Not only are there different recovery systems for different bases, but
there can also be different recovery system designs for a single base.
Usually these designs vary as to the amount and type of heat recovery or the
method of SOj removal. Heat can be recovered by producing steam, heating
process water or evaporating spent liquor. Sulfur dioxide is usually removed
by scrubbing the furnace flue gas in venturi scrubbers, packed bed absorbers
or tray towers.
4.1.5.1.1 .Magnesium Base Recovery Systems
A typical magnesium base recovery system is shown in Figure 4-2. Spent
sulfite liquor (SSL) is fed into a combination recovery boiler. Depending on
the solids content of the SSL, supplemental fuel'(oil or natural gas) may be
4-10
-------
Spent Sulfite
Liquor
Exhaust
(S02, particulates)
t
Direct Contact
Evaporator
Recovery Boiler
Steam
HgO Ash Tank
MgO Make-up
To Cooking Liquor
Preparation System
figure 4-2. Magnesium base recovery system.
(Potential pollutants shown In parenthesis)
70-1256-1
-------
necessary to support combustion. The magnesium and sulfur are oxidized
to magnesium oxide and sulfur dioxide, respectively. Organic material is
oxidized to carbon dioxide and water. Heat is recovered by the production
of steam.
Recovery boiler flue gas is passed through a system of multiclones to
collect the magnesium oxide. The collection efficiency is typically 98%. 7
The MgO is washed to remove soluble impurities such as Na , K , and S0i+
without significant loss of MgO. The magnesium oxide is then slaked in a
mixing tank to produce magnesium hydroxide, Mg(OH)2. The magnesium hydroxide
is used as a scrubbing liquor in the flue gas venturi scrubbers which are
located downstream of the direct contact evaporator. This evaporator is
another means of heat recovery. Hot flue gas from the recovery boiler
evaporates water from the spent sulfite liquor and increases the solids
concentration prior to firing of the liquor.
Flue gas from the direct contact evaporator is then directed to a
series of four venturi scrubbers for countercurrent SOz scrubbing with
magnesium hydroxide. The magnesium hydroxide solution absorbs the sulfur
dioxide to produce magnesium bisulfite (Mg(HS03)2) which is used for cooking
liquor preparation. In place of venturi scrubbers, some recovery systems
use packed bed absorbers for SO^ removal. Both types of systems are reported
to have scaling problems with precipitated magnesium sulfite ("monosulfite").l 8
If the Mg(OH)z concentration is increased, the SOz removal efficiency will
also increase, but the scaling problem will become more severe. The build
up of scale is alleviated by temporarily lowering the Mg(OH)2 concentration
or periodically washing the scurbbers with a low pH aqueous solution such as
evaporator condensate. Built up scale is removed periodically by mechanical
means.
4-12
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4.1.5.1.2 Ammonium Base Recovery Systems
For an ammonium base mill, the only chemical recovered is sulfur
dioxide. Most of the nitrogen in the spent sulfite liquor is present in
the form of ammonium salts. Depending upon combustion conditions, the
recovery furnace flue gas will contain nitrogen in a variety of forms.
The gaseous forms include molecular nitrogen (N2), nitrogen oxides (NO ),
and ammonia (NH3). In addition, ammonium sulfite [(NHlt)2S03] and ammonium
sulfate [(NHO2SOtJ may be present as particulates.19
A sample ammonium base recovery system is shown in Figure 4-3. The
spent sulfite liquor is burned with supplemental fuel (natural gas or oil)
when necessary. Heat is recovered through steam production. The flue gas
is directed to some type of sulfur dioxide recovery system. The system
may consist of a series of venturi scrubbers, packed bed absorbers, tray
towers or any combination thereof. In the example illustrated in Figure 4-3,
the S02 is absorbed by a recirculating solution of ammonium hydroxide
(NHitOH), which is distributed as a spray in a two stage absorber. A
continuous bleed stream of ammonium bisulfite (NHitHSOa) is drawn from the
bottom of the absorber and sent to the cooking liquor preparation system.
4.1.5.1.3 Calcium Base Recovery Systems
Calcium base sulfite pulping presents a special problem in relation to
the recovery of cooking chemicals. When the spent calcium sulfite cooking
liquor is combusted, the principal inorganic products are calcium carbonate
(CaCOs) and calcium sulfate (CaSOO- These compounds do not lend themselves
to the economic reprocessing of fresh cooking liquor. In addition, calcium
salts, particularly calcium sulfate are known to cause equipment scaling
problems, such as on evaporator surfaces. Therefore, the evaporation and
burning of calcium base spent liquor has not been widely practiced in the
4-13
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Exhaust
(302, partic.ulates)
Two Stage
Absorber
Spent Sulfite
Liquor *
|W\
NIK OH
Recovery Boiler
To Cooking Liquor
Preparation System
Steam
Figure 4-3. Ammonium base recovery system.
(Potential pollutants shown in parenthesis)
70-1257-1
4-14
-------
United States. Instead, those calcium base mills still in operation have
developed markets for essentially all of their spent liquor, either as a
concentrated liquor or spray-dried solid.20
4.1.5.1.4 Sodium Base Recovery Systems
Sodium base recovery systems differ from the other types of recovery
systems previously described in that the sodium is recovered in a smelt
containing sodium sulfide (Na2S) and sodium carbonate (Na2C03). Several
modern recovery systems are available, including the STORA process, the
SCA-Billerud process, the Tampilia process, the Sivola-Lurgi process, and
the Institute of Paper Chemistry method.21
The STORA process is very flexible and can be applied to various cooking
methods. It offers a representative example of a sodium base recovery
system. An outline of the STORA process is shown in Figure 4-4. Smelt from
the recovery furnace is dissolved in water to produce a green liquor that is
treated with COz to remove hydrogen sulfide (HzS). The bottoms from the
carbonation tower contains sodium carbonate (NazCOa) and sodium bicarbonate
(NaHCOs). This solution is treated with sodium bisulfite (NaHSOa) to form
sodium sulfite (NazSOs) for cooking liquor preparation and C02 for recycle
to the carbonation tower.
The bottoms of the sulfiting tower may be further fortified by scrubbing
SOz from the recovery furnace flue gas. Some of the sodium sulfite is sent
to a bisulfite tower for the production of sodium bisulfite either for cooking
liquor preparation or for recycle to the sulfiting tower.
The hydrogen sulfide off-gas from the carbonation tower is sent to a
Glaus reactor for the production of liquid sulfur. This sulfur is burned to
form S02 which is then purified for recycle to the Glaus reactor. Some of
the SOz is directed to the bisulfite tower for the production of sodium bisulfite,
4-15
-------
Spent
Sulfite-
Li ijuor
Recovery Furnace
Carbonation
Tower
NaaS + Na
Fxhaust
(S02)
1
Na2C03
NaHC03
ne C<
rubbf
V
JS
"r
Si
f
If]
Tot
s
NazSCh
_^_ To Cooking Liquor
Preparation
Bisulfite
Tower
S02
NaHSOa
Steam
1I20
To Cooking Liquor Preparation
Figure tt-it. Stora sodium base recovery system.
(Potential pollutants shown in parenthesis)
70-1259-1
-------
Depending on the pulping process requirements, a suitable cooking
liquor can be prepared by mixing the proper proportions of sodium sulfite
and sodium bisulfite. If a higher pH is needed as for semichemical pulping,
some sodium bicarbonate can be bypassed directly to the sodium sulfite
solution. These options for cooking liquor preparation characterize the
STORA process as one of the more versatile sodium base recovery systems.
4.1.5.2. Emission Sources
Recovery systems are designed to incinerate spent sulfite liquor and to
produce in a recoverable form the chemicals necessary to produce fresh
cooking liquor. Except for sodium base recovery systems that generate a
useable sodium smelt, all the chemicals are recovered from the recovery
boiler/furnace flue gas. These chemicals may be either in a gaseous state,
such as sulfur dioxide, or in a particulate form, such as magnesium oxide.
Depending on the efficiency of a recovery system, trace amounts of these
chemicals may pass through the system and be discharged to the atmosphere
from the flue gas exhaust stack. In addition, the recovery systems are not
specifically designed for the removal of other chemical species such as
sulfates, which would also be discharged from the flue gas exhaust stack.
4.1.6 Liquor Preparation Systems
4.1.6.1 Process Description
The purpose of the liquor preparation system (also referred to as acid
preparation) is to provide fresh cooking liquor for the digesters. For
magnesium, ammonia, or sodium base systems, liquor preparation is very
closely associated with the recovery system. The weak acid produced by SOa
removal in the recovery system is used for the cooking liquor preparation.
In many cases the recovery system and the liquor preparation system are so
closely integrated that it is difficult to consider them as two distinct
4-17
-------
Relief Gas
from Digester
High Pressure
Accumulator
Low Pressure
Accumulator
r
Cooking Liquor to Digester
or Storage
S02
-?. Liquor From the Recovery System
Acid Fortification Tower
S02
Liquid Sulfur
f
Sulfur Burner
Figure 4-5. Liquor preparation system.
I-18
-------
systems. The STORA sodium base recovery system described in Section 4.1.5.1.4
is a good example.
Cooking liquor preparation consists of fortifying weak acid liquor from
the recovery system with additional sulfur dioxide, as shown in Figure 4-5.
Liquid sulfur is burned to produce SOa which is then absorbed by the weak
acid liquor in an acid fortification tower. Then, depending on the desired
strength (pH) of the cooking liquor, it can be further fortified in a low
pressure and/or high pressure accumulator. Accumulators are sprayed chambers
where steam is condensed and S02 from process unit relief gases is absorbed
for subsequent reuse in the cooking liquor.22
When preparing calcium base cooking liquors, water is substituted for
the weak acid liquor usually supplied from the recovery system. The water is
run countercurrent to S02 through a series of two or three Jenssen towers
(absorbers) which are packed with limestone. The resulting calcium
bisulfite liquor may then be fortified in one or more accumulators.
The final composition of a cooking liquor is determined by the amount
of combined SOa and total SOz By definition, the amount of combined SOz is
that amount of SOa theoretically equivalent to monosulfite, for example CaSOa.
Total SOa is the amount of combined S02 plus the amount of S02 as sulfurous
acid (HaSOa). A typical cooking liquor for an acid calcium sulfite process
will have a composition of approximately 1% combined SOa and 6% total SOa.
4.1.6.2 Emission Sources
The major emission source in the liquor preparation system is the acid
fortification tower or Jenssen towers. The weak acid from the recovery
system does not absorb all the sulfur dioxide passing through the tower.
In some cases the excess S02 is sent to the recovery system for removal. In
many instances, however, the acid fortification tower is vented directly to
4-19
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the atmosphere.
The accumulators may also discharge vent gases containing S02 directly
to the atmosphere. Many pulp mills have arranged a system of cascading S02
vent gases, i.e., digester to high pressure accumulator to low pressure
accumulator to acid fortification tower. Still, several other mills have no
such system and the accumulators vent directly to the atmosphere.
4.2 NEUTRAL SULFITE SEMICHEMICAL (NSSC) PROCESS
The pulping of wood by the neutral sulfite semichemical (NSSC) process
actually involves two processes, a chemical action to partially free
cellulosic fibers by lignin sulfonation and a mechanical action to completely
free the fibers by friction and compression. Although NSSC pulping has been
practiced for over forty years, the operations and equipment are not yet
standardized to the extent of modern kraft pulping. In fact, many mills
are tailor-made to meet particular circumstances.
A generalized flow diagram for the NSSC process is shown in Figure 4-6.
Wood chips are fed to a continuous digester for chemical attack on the
cellulose-lignin complex. The partially pulped chips pass through a blow
tank for liquor drainage and through presses for additional liquor removal.
The chips are then fed to refiners for mechanical defibering and through
washers and screens for rinsing and removal of unpulped material. The spent
liquor is either recovered in systems similar to those used in the sulfite
process or combined with the liquor used in the kraft process as a source
of make-up chemicals.
4.2.1 Digesters
4.2.1.1 Process Description
Unlike the sulfite process, the most common type of digester in the
4-20
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Steam
Wood
Chips
Continuous Digester
(S02)
Recovery System
(SO2, p.irtlcu-
Intes)
To Kraft System for
Cross Recovery
Kvaporators
(S02)
Liquor Prepnrnt l<
System
(S02)
Figure 4-6. Cenor/iHzcd nciitr.il sulflti1 Romli-liomlc.il (NSSC) procoss.
(Pntciil Inl pollutnntn shown In pnrenthcsl.s)
/0-1250-1
-------
NSSC process is the continuous digester. There are several types of con-
tinuous digester designs based on a variety of inlet and outlet devices
used to convey wood chips through the system. Operating conditions for
these digesters are slightly more intense than the batch digesters
described in Section 4.1.1.1. Temperatures and pressures may range from
160 to 185°C (320 to 365°F) and from 690 to 1100 kPa (100 to 160 psi),
respectively.25 Digestion time is considerably less for the NSSC process,
usually on the order of thirty minutes to three hours. Pulping may be
conducted in either the liquid or vapor phase. Although sodium is the most
common cooking liquor base, magnesium and ammonia base liquors can also
be used.26
Depending on the operating pressure, the partially pulped chips are
discharged in a number of ways. Pressurized digesters will blow the chips
through some type of pressure control valve into a blow tank. A digester
operating at atmospheric pressure will normally have the chips scraped into
a conveyor serving an orifice for discharge to a blow pit.
4.2.1.2 Emission Sources
The continuous diges;ters have two potential sources of atmospheric
emissions: relief gases and blow gases. Both types of emissions might
contain sulfur dioxide, but only in trace amounts. The relatively high pH
of the cooking liquor (usually between 7 and 8) indicates that high SOz
concentrations in these gases are very unlikely. Indeed, source test data
for blow emissions at one NSSC mill estimated SOz emissions at 0.045g SC-2/kg
of pulp production (0.09 lb/ton).27
For plants associated with kraft mills, digester relief and blow gases
may also contain hydrogen sulfide, if green liquor is used in the cooking
process. No sampling data is available to confirm the possibility.28
4-22
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4.2.2 Blow Tanks
4.2.2.1 Process Description
For continuous digesters, blow tanks act as a hold tank where spent
liquor can drain from the freshly discharged pulp slurry. The blow tanks
are equipped with a leach caster with revolving arms and plows that work
downward to sweep the cooked chips to an outlet. Pressurized digesters will
generally blow into a cyclone where steam is separated. The cooked chips
drop from the cyclone into tanks with live bottoms or into some other type
of conveyance device for transport to the presses.
4.2.2.2 Emission Sources
Blow tank emissions result from the gases evolved during the discharge
of partially pulped chips from the digesters. These emissions are expected
to be very low and are discussed in Section 4.2.1.2.
4.2.3 Presses
4.2.3.1 Process Description
The partially pulped chips from the blow tank are normally deliquored,
rinsed with white water from the paper machines, deliquored again, and then
fed to the refiners. In addition, the presses are used to impart a
beneficial prefiberizing action to the fibrous material. The total elapsed
time for this operation is kept at a minimum in order to permit hot refining
and to prevent possible pulp discoloration.
4.2.3.2 Emission Sources
At this point in the pulping process most of the spent liquor has been
removed and the presses are not considered a potential source of atmospheric
emissions.
4-23
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4.2.4 Refiners
4.2.4.1 Process Description
The purpose of the refiners is to provide the mechanical action by
which the cellulosic fibers in the partially pulped chips are finally
freed. Although several models of refiners are currently in commercial use,
the most common are based on variations of the single rotating disc
type. Cast alloy plates are bolted to a refiner disc and they form the
refining surface. The discs are powered to speeds of 600 to 1800 rpm by
synchronous or induction motors of up to 11 kW (1500 hp).29 The result is
a combination of frictional and centrifugal actions that weakens the fiber
bonds causing the partially pulped chips to disintegrate first into fiber
bundles and eventually into individual fibers. The pulp is then ready for
final washing and screening.
4.2.4.2 Emission Sources
The refiners are not considered a potential source of atmospheric
emissions.
4.2.5 Washers and Screens
4.2.5.1 Process Descriptions
The Washers and screens are used to rinse the pulp and remove any
remaining chips which are only partially cooked. The accepted pulp is
sent on for further processing, usually into corrugating medium, and the
rejected pulp is returned to the refiners or digesters. Wash wastewater is
combined with the spent cooking liquor for treatment or disposal.
4.2.5.2 Emission Sources
The washers and screens are not considered a potential source of at-
mospheric emissions.
4-24
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4.2.6 Disposal of Spent Cooking Liquor
4.2.6.1 Process Description
In the NSSC process, spent cooking liquor may be disposed of in one of
two ways: transfer to an associated kraft pulping process or evaporation
and incineration for recovery of chemicals in systems very similar to those
used in the sulfite process. Those mills that are operated in association
with a kraft process will mix the spent sulfite liquor with the kraft
cooking liquor as a means of sodium and sulfur chemical makeup. In this
case, the NSSC process is considered to be free of emissions normally
associated with the disposal of spent cooking liquor as the chemicals are
now part of another process.
For those mills that recover heat and chemicals from the spent cooking
liquor, the systems are almost identical to those designed for the sulfite
process. The liquor is evaporated and incinerated, and the cooking liquor
chemicals are recovered, when possible, to regenerate a fresh cooking liquor
For sodium base systems, an alternate route to the typical smelt-producing
incinerator is combustion in a fluidized bed. In this technique the
liquor is evaporated to about 35% solids and sprayed into the furnace for
combustion at about 660°C (1220°F). The inorganic products are mostly
sodium sulfate with a little sodium carbonate. These inorganic products
form pellets that compose the fluidized bed. A portion of the bed is
continuously withdrawn from the bottom of the bed to balance the incoming
feed. The pellets cannot be reused for preparing fresh cooking liquor
and are usually sold to a sulfate mill.
4.2.6.2 Emission Source^
For an integrated NSSC-kraft pulping operation, there will be no
atmospheric emission sources attributed to the NSSC process. If chemical
-------
recovery is practiced, then potential emission sources will include the
evaporator gases and the recovery system exhaust. Of these two sources,
the recovery system exhaust is the most significant. In many cases the
evaporator gases are vented to the recovery system, so there is only a
single source. The exhaust stack may be the source of SOz and particulate
emissions.
4.2.7 Liquor Preparation System
4.2.7.1 Process Description
The methods of preparing NSSC cooking liquor are comparable to those
used in sulfite pulping. The major exception is the difference in liquor
pH levels. Since the NSSC cooking liquor is designed for neutral pH levels
(7 to 8), acid fortification equipment is unnecessary. Cooking liquor can
be freshly prepared by contacting a sodium hydroxide solution with SOz from
a sulfur burner. The contacting equipment can be a packed bed absorber or
tray tower. If cross recovery is practiced, then fresh cooking liquor must
be continuously prepared.
However, if a recovery system is employed for spent liquor disposal
then cooking chemicals can be recycled. A good example is the STORA process
described in Section 4.1.5.1.4. If the cooking base is ammonia, fresh
ammonium hydroxide make-up is required because of the combustion of ammonia
in the recovery system.
4.2.7.2 Emission Sources
The major emission source in cooking liquor preparation is the packed
bed or tray tower used for absorbing S02. These absorbers can be operated
at low S02 loadings and high efficiencies to produce a neutral sulfite
cooking liquor. One mill reports operating a packed bed absorber at 99.9%
efficiency and measuring typical S02 concentrations of 5 to 15 ppm in the
31 4-26
-------
REFERENCES
1. Linero, A. Background Document: Acid Sulfite Pulping, Final Report.
Environmental Science and Engineering, Inc. Gainesville, Florida.
EPA-450/3-77-005, PB 264 301, EPA Contract No. 68-02-1402. January
1977. p. 4.
2. Compilation of phone surveys. Radian Corporation. Austin, Texas.
3. Sulfite Pulping, Emissions and Control. A Background Report for
Sulfite Pulp Mill Regulations. Oregon Department of Environmental
Quality, Air Quality Control Division, p. 2.
4. Britt, K. W., ed. Handbook of Pulp and Paper Technology, revised
second edition. New York, Van Nostrand Reinhold, 1970. p. 160.
5. Linero, A. Background Document: Acid Sulfite Pulping, Final Report.
Environmental Science and Engineering, Inc. Gainesville, Florida.
EPA-450/3-77-005, PB 264 301, EPA Contract No. 68-02-1402. January
1977. p. 5.
6. Sulfite Pulping, Emissions and Control. A Background Report for
Sulfite Pulp Mill Regulations. Oregon Department of Environmental
Quality, Air Quality Control Division, p. 10.
7. Environmental Pollution Control, Pulp and Paper Industry, Part 1, Air.
Environmental Protection Agency, Office of Technology Transfer. EPA
625/7-76-001. October 1976. p. 14-17.
8. Sulfite Pulping, Emissions and Control. A Background Report for
Sulfite Pulp Mill Regulations. Oregon Department of Environmental
Quality, Air Quality Control Division, p. 5.
9. Environmental Pollution Control, Pulp and Paper Industry, Part 1, Air.
Environmental Protection Agency, Office of Technology Transfer. EPA
625/7-76-001. October 1976. p. 14-17.
10. Sulfite Pulping, Emissions and Control. A Background Report for
Sulfite Pulp Mill Regulations. Oregon Department of Environmental
Quality, Air Quality Control Division. p. 16.
4-27
-------
11. Linero, A. Background Document: Acid Sulfite Pulping, Final Report.
Environmental Science and Engineering, Inc. Gainesville, Florida.
EPA-450/3-77-005, PB 264 301, EPA Contract No. 68-02-1402. January
1977- p. 7.
12. Environmental Pollution Control, Pulp and Paper Industry, Part 1, Air.
Environmental Protection Agency, Office of Technology Transfer. EPA
625/7-76-001. October 1976. p. 14-17.
13. Considine, D. M., ed. Chemical and Process Technology Encyclopedia.
New York, McGraw-Hill, 1974. p. 451.
14. Micheletti, W. C. and C. M. Thompson. Trip report, Boise Cascade,
Salem, Oregon. Radian Corporation. Austin, Texas. June 22, 1978.
15. Environmental Pollution Control, Pulp and Paper Industry, Part 1, Air.
Environmental Protection Agency, Office of Technology Transfer. EPA
625/7-76-001. October 1976. p. 14-17.
16. Britt, K. W., ed. Handbook of Pulp and Paper Technology, revised
second edition. New York, Van Nostrand Reinhold, 1970. p. 169.
17. Micheletti, W. C. and C. M. Thompson. Trip report, Publishers Paper
Co., Oregon City, Oregon. Radian Corporation. Austin, Texas. June
22, 1978.
18. Sulfite Pulping, Emissions and Control. A Background Report for
Sulfite Pulp Mill Regulations. Oregon Department of Environmental
Quality, Air Quality Control Division, p. 12.
19. Environmental Pollution Control, Pulp and Paper Industry, Part 1, Air.
Environmental Protection Agency, Office of Technology Transfer. EPA
625/7-76-001. October 1976. p.. 14-27.
20. Britt, K. W., ed. Handbook of Pulp and Paper Technology, revised
second edition. New York, Van Nostrand Reinhold, 1970. p. 168.
21. Environmental Pollution Control, Pulp and Paper Industry, Part 1, Air.
Environmental Protection Agency, Office of Technology Transfer. EPA
625/7-76-001. October 1976. p. 14-22.
22. Sulfite Pulping, Emissions and Control. A Background Report for
Sulfite Pulp Mill Regulations. Oregon Department of Environmental
Quality, Air Quality Control Division, p. 5.
23. Standen, Anthony, ed. Kirk-Othmer Encyclopedia of Chemical Technology,
volume 16, revised second edition. New York, Wiley, 1968. pp. 714.
24. Britt, K. W., ed. Handbook of Pulp and Paper Technology, revised
second edition. New York, Van Nostrand Reinhold, 1970. p. 200-201.
4-28
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25. Britt, K. W., ed. Handbook of Pulp and Paper Technology, revised
second edition. New York, Van Nostrand Reinhold, 1970. p. 204.
26. Standen, Anthony, ed. Kirk-Othmer Encyclopedia of Chemical Technology,
volume 16, revised second edition. New York, Wiley, 1968. p. 702.
27. Micheletti, W. C. and C. M. Thompson. Trip report, Longview Fibre
Company, Longview, Washington. Radian Corporation. Austin, Texas.
June 21, 1978.
28. Compilation of Air Pollutant Emission Factors, second edition, supple-
ment seven. Environmental Protection Agency. Research Triangle Park,
North Carolina. AP-42. April 1977- p. 10.1-9.
29. Britt, K. W., ed. Handbook of Pulp and Paper Technology, revised
second edition. New York, Van Nostrand Reinhold, 1970. p. 160.
30. Standen, Anthony, ed. Kirk-Othmer Encyclopedia of Chemical Technology,
volume 16, revised second edition. New York, Wiley, 1968. p. 701.
A_7Q
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5.0 EMISSION CONTROL SYSTEMS
The sulfite wood pulping process typically results in two types of
atmospheric emissions: sulfur dioxide and particulates. Unlike the kraft
pulping process, there are no foul odors emitted because volatile reduced
sulfur compounds are not products of the lignin-bisulfite reaction. How-
ever, when an ammonium base cooking liquor is used, the possibility of
ammonia and nitrogen 6xide (NO )" emissions from the recovery system does
X
exist. Onl;y a limited amount of information is available on these
1 2
emissions, but they are not considered to be major pollutants.
i
5.1 CONTROL OF SULFUR DIOXIDE EMISSIONS
Atmospheric emissions of sulfur dioxide are from four major sources:
digester relief vent, blow pit vent, recovery system exhaust, and liquor
preparation system. The first two sources are a direct result of the
actual pulping process. The last two sources are associated with the
production of fresh cooking liquor. In addition, there are other minor
SO? emission sources, most notably the washers and screens, and' the
evaporators.
5.1.1 Digester Relief Vent
During the pulp cooking cycle small amounts of gas and liquor are
intermittently removed from the digester. This relief of gas and liquor
maintains constant cooking conditions in the digester and ensures the
production of a uniform quality pulp. The digester relief gas contains
5-1
-------
high concentrations of SOa and is a major source of SOa emissions when
vented directly to the atmosphere.
Usually one of two process changes is made to effectively control
emissions from the digester relief vent. The relief gases may be directed
to a high or low pressure accumulator so that the SOa may be recycled to
fresh cooking liquor. After passing through the accumulators, the relief
gases may be sent to the recovery system so that the S02 is absorbed in the
weak acid liquor which is eventually used for the production of fresh cooking
liquor.
Another means of controlling SOa emissions from the digester relief
vent is to direct the relief gases to a scrubber specially designed
for that purpose. This approach may not be practical for some mills
since it can be difficult to design a scrubber that will efficiently
remove appreciable amounts of SOa from intermittent quantities of gas.
On the other hand, for a large mill which may be operating several
digesters simultaneously, the feed gas to the scrubber is much more
uniform in composition and flow rate.
5,1.2 Digester Blow
Perhaps the largest single source of sulfur dioxide emissions is the
digester blow. When the cooking cycle is complete, the hot pulp is
forced under pressure from the digester into a blow pit. The hot,
pressurized spent cooking liquor flashes during the blow, releasing
large quantities of steam and sulfur dioxide. These emissions can be
reduced either by collecting and scrubbing the blow -gases or by
modifying the pulp discharge operation to prevent liquor flashing.
Controlling SOa emissions with a scrubber offers a definite advantage
5-2
-------
in that it requires little or no alteration to the existing digesters
and blow tanks. The entire area would need to be completely enclosed for
the collection of blow gases. However, this should not be a problem unless
the plant layout imposes unusually strict space limitations. The major
problem with this control method is proper scrubber design. A blow will
last only a few minutes with the peak flows and concentrations lasting
only five to six minutes. Therefore, a scrubber must be designed for
a maximum gas and vapor flow which is many times the average gas flow,
and likewise for peak concentrations of SOz.
An additional problem is the slurry used for an absorbing medium.
The obvious choice for any given mill is an alkaline solution of the
cooking liquor base used at that mill. For example, a magnesium base mill
would use a magnesium hydroxide slurry for scrubbing SOz. To do other-
wise would only create another pollution problem, disposal of the
scrubber effluent. Of the four chemical bases, sodium appears to be the
best suited for scrubbing. Both magnesium and calcium require cumbersome
4
slurry systems. And the use of ammonium hydroxide may result in the
emission of ammonia or of an ammonium sulfite particulate. Yet even
with these problems, SOa recovery efficiencies are reported to be as
high as 97% for this type of control.
Recently, many pulp mills have been modifying the pulp discharge
operation in an effort to reduce sulfur dioxide emissions. The basic
principle is to prevent liquor flashing by reducing the temperature and
pressure of the pulp/liquor slurry prior to discharge, Two of the most
common modifications are the low pressure blow or dump system and the
pump-out system.
5-3
-------
The low pressure blow or dump system involves lowering the digester
pressure to nearly the atmospheric level and then discharging the pulp
into a dump tank located directly beneath the digester. In some instances
all or part of the hot spent cooking liquor may be drained from the
digester and replaced by cooler water from the pulp washers. This
lowers the pulp temperature and reduces the steam flashing on discharge.
Emissions from dump tanks have been reported to be under 0.005 g/kg of
pulp (0.01 Ib/ton) at one mill.
There are several significant problems associated with the low
pressure blow or dump system. First, there is the problem of relief
gases. In order to lower the digester pressure to near atmospheric,
digester gases containing large amounts of SOa must be withdrawn and
sent to appropriate treatment units. If the gases are vented to the
recovery system or the liquor preparation system, such large inter-
mittent doses may upset the efficiency of that particular system.
Secondly, there is the problem of sunken dump tanks. Most of the
sulfite mills currently operating were originally built with blow pits
that are not located directly beneath the digester. Therefore, using
a low pressure dump would require major equipment modifications, assuming
there was allowable space. Finally, there is the problem of reduced
capacity. This type of pulp discharge is more time consuming than a
high pressure blow and consequently increases the time requirement for
use of a digester.
In the pump-out system, the digester pressure is relieved to nearly
the atmospheric level and then the pulp/liquor slurry is pumped from the
5-4
-------
digester into a closed storage vessel. Since the system is completely
enclosed, all relief and vent gases can be collected and S02 emissions from
the discharge of pulp are kept at a minimum. In some instances aJ 1 or part _of
the spent cooking liquor may be withdrawn and replaced with water from the
pulp washers to cool the pulp.
The pump-out system has problems very similar to those associated with
the dump system. Although all relief and vent gases are collected, there
may still be the problem of proper treatment^ Equipment modification is not
nearly as drastic for the pump-out system. The pulp storage tanks, which
serve the same purpose as a dump tank, do not need to be located directly
beneath the digesters. The pumps can be sized to transfer the pulp/liquor
slurry to storage tanks located at any level in the plant, As before, there
will also be a loss of pulping capacity due to the increased time required
for pulp discharge. A mill in Oregon which has gone to the pump-out
system, has had to increase their number of digesters from six to eight in
Q
order to maintain their original capacity.
Determining which type of SOa control method is economically best is
very difficult. Cost information is extremely limited and subject to a
number of factors that vary from mill to mill, such as plant layout, age
of equipment, and cooking liquor base, A report published by the Oregon
State Department of Environmental Quality states that, on the surface,
scrubbers, dump systems, and pump-out systems appear to have comparable
costs.
5.1.3 Recovery System Exhaust
The recovery system is inherently a pollution control system. It is
5-5
-------
designed to reduce water pollution by providing an alternate means of
disposal for spent sulfite liquor. The recovery system is made economically
attractive by its ability to recover expensive chemicals necessary for the
preparation of fresh cooking liquor. With the exception of sodium base
liquors, all recovery systems are designed to recover sulfur as sulfur
dioxide from the recovery furnace flue gas. Depending on the efficiency of
SOa removal, large quantities of sulfur dioxide can be emitted from the
recovery system exhaust stack.
The current method of recovering SOa is to pass the flue gas through a
multistage system of absorbers or Venturis and scrub the gas with an
alkaline solution. Theoretically, if the scrubbers were made large enough
and enough alkaline solution were used, SOa exhaust emissions could be
reduced to zero. Practically, however, this would result in a scrubber
slurry effluent of too great a quantity and too dilute a concentration to
be of any use in cooking liquor preparation.
Hence, the best means of controlling SOa emissions from the recovery
system exhaust is the proper operation of a well designed scrubber system.
This does not preclude the addition of another scrubber to an already
existing recovery system. Depending on SOa control measures implemented
at other emission sources in the mill, the recovery system scrubbers may
become overtaxed. For'example, if digester relief and blow gases are vented
to the recovery system, an additional scrubber may be necessary to avoid a
system upset from the sudden surge in SOa laden gases.
The scrubber system design will depend primarily on the type of alkaline
scrubbing medium. Calcium hydroxide and magnesium hydroxide are considered
5-6
-------
rather cumbersome slurries because of their tendency to scale. Therefore,
when using these bases, venturi scrubbers are preferred for their induced
slurry turbulence. Even so, some mills have reported continued scaling
problems with Venturis. On the other hand, ammonium hydroxide and sodium
hydroxide are somewhat easier to handle and may be effectively used in
towers packed with an inert matrix or fitted with a number of perforated
plates. Because of high costs, SOa recovery has been limited to 50 to 80
percent depending on the base and recovery system.11 However, SOz recovery
as high as 95 percent has been reported for mills operating under strict
environmental regulations. 2
5.1.4 Liquor Preparation System
Sulfur dioxide emissions from the liquor preparation system can be
appreciable since the purpose of this system is to produce fresh cooking
liquor by fortifying weak acid liquor with SOa- The major emission source
is the acid fortification tower which may vent large amounts of S02 directly
to the atmosphere. These emissions can be reduced by proper equipment design
and operation to ensure almost complete absorption of SOi by the weak acid
liquor. Any tower offgas containing significant amounts of S02 can then
be directed to the recovery system for removal or to an additional scrubber.
In addition to the acid fortification tower, the accumulators also
have offgas vents that are sometimes released directly to the atmosphere.
These emissions are best controlled by cascading the vent gases from one
process unit to another. For instance, relief gases from the digester are
directed to the high pressure accumulator in which portions of S02 are
redissolved in fresh cooking liquor. The high pressure accumulator will,
in turn, vent to the low pressure accumulator, which will subsequently vent
5-7
-------
to the acid fortification tower. At each step along the cascade of units,
some SO is redissolved in the freshly prepared cooking liquor. Offgas from
the acid fortification tower is ultimately sent to the recovery system for
removal of remaining SOa
5.1.5 Minor Emission Sources
The washers and -screens, and the evaporators are jasually
considered minor SOa emission sources. However, if other major sources are
well controlled, these sources can contribute an appreciable fraction"of the
overall emissions. In many cases these sources are uncontrolled.
Two major control options are available for reducing the emissions
from stock washers and screens. In both opt ions , vapors from the washers
and screens are collected in hoods and removed from the work areas by fans.
If the hoods are close fitting, then the total gas flow rate will be low and
the vapors will contain considerable amounts of SOa In such cases, it is
usually practical to send the vapors to the S02 scrubbers in the recovery
system. On the other hand, if the total gas flow rate is high, then the
S02 vapors will be relatively dilute. Under these circumstances, the
best control is to pass the gas through a water wash column (often referred
to as a nuisance tower) for SOa removal before venting to the atmosphere.
5.2 CONTROL OF PARTICULATE EMISSIONS
The only source of particulate emissions is the recovery system exhaust
stack. Depending on the chemical base of the cooking liquor, the nature of
these emissions can vary. For each base, however, the major particulates
are sulfates and any contaminants that were introduced into the system by
the wood chips.
5-8
-------
The most common means of controlling these emissions is to pass the
recovery system flue gas through a demister prior to exhaust. Although
demisters have proven to be very efficient, they can also pose a considerable
maintenance problem. Demisters will plug quite often, particularly when
burning supplemental fuel oil in the recovery incinerator.13 In addition, the
pressure drop across the demisters can be considerable, so that fans with
high energy motors are required.
Another potential means of controlling particulates is the use of
electrostatic precipitators. Some kraft mills successfully use electrostatic
precipitators for the removal of fly ash from recovery furnace exhaust.
Removal efficiencies are typically very high (99+%). but the capital and
operating costs for these units are also high. As of yet, there is no
indication that electrostatic precipitators will be implemented in the
sulfite or NSSC pulping sector.
5.3 CANDIDATE BEST CONTROL SYSTEMS
Since each mill is unique in its application of the sulfite or neutral
sulfite semichemical pulping process, no single best control system can be
defined for the control of atmospheric emissions. Instead, the process
design and control requirements for each mill must be reviewed on a case by
case basis. The exact emission control strategy for a particular mill will
depend on the age and type of equipment currently in use, the type of cooking
liquor, the availability of space to retrofit or add equipment, and the
associated capital and operating costs. A few mills in the Pacific Northwest
have installed the best control systems for their specific operation.
Information concerning these control systems is presented in Table 5-1. In
addition, some generalizations concerning candidate best control systems are
discussed below.
5-9
-------
Table 5-1. SULPITE MILLS WITH CANDIDATE BEST CONTROL SYSTEMS
PERSONNEL TO CONTACT FOR FURTHER INFORMATION
CANDIDATE BEST CONTROL SYSTEM
1
M
O
Holse Cascade Corporation
SaJ em, Oregon
Georgia-Pad fie Cor|>.
Bell Jnghdm, Washington
Publ J alujcs Paper
Newberg, Oregon
Oregon Cjty, Oregon
Weyerhauuser Company
Cotiiiiopo L Is, Washing! on
Mr. Bill Gray
Technical Director
315 Commercial St. S.
Salem, Oregon 97301
(503) 362-2421
Mr. J. H. Dunkak
V.P. and General Manager
P. O. Box 1236
Belllngltam, Washington 98225
(206) 733-4410
Mr. P. J. Delekto
Technical Director
P. 0. Box 70
Ncwberg, Oregon 97132
(503) 538-2151
Mr. Rodney Schniall
Manager of Environmental Services
419 Main Street
Oregon City, Oregon 97045
(503) 656-5211
Mr. K. R. Devones
Technical Director
P. 0. Box 280
Cosmopolis, Washington 98537
(206) 532-7110
Mist eliminator to reduce particulate
emissions,, (This mill operates under air
emissions limitations more stringent than
those for any other mill in the United
States.) Pulp pump-out system to reduce
digester discharge emissions.
Scrubber system to treat digester blow
and relief emissions and acid plant
emissions.
Scrubber system to treat digester blow
and relief emissions.
Pulp pump-out system and scrubber to reduce
digester discharge emissions
Overall process control to reduce emissions
-------
5.3.1 Digester Relief Vent
From an economic standpoint, probably the best means of controlling
emissions from the digester relief vent is to direct these gases to the
recovery system or liquor preparation system. This method of control requires
minimal process alteration and capital investment. However, care must be
taken not to overload the design capacities for either the recovery system
or the liquor preparation system. If these systems are unable to handle the
digester relief gases, the next best control method is the installation of
a scrubber. Reported emissions for the two control methods are comparable.
5.3.2 Digester Blow
Digester blow emissions can be controlled either by collecting blow
gases for scrubbing or by reducing blow gases by discharge modifications.
Scrubbing usually requires complete enclosure of the digester blow area and
installation of a new scrubber. Pulp discharge modifications require
considerable equipment alterations for pressure relief, cooling liquid
addition, and possible pulp pump-out. In addition, pulp discharge modifi-
cations increase digester turnaround time and consequently decrease mill
production. While neither control system is economically attractive, both
systems achieve similar emissions reductions.
5.3.3 Recovery System Exhaust
The best means of controlling SOa emissions from the recovery system
exhaust is the proper operation of a well designed scrubber system. For
recovery systems which accept digester relief and blow gases, an additional
scrubber may be necessary to avoid a system upset from the sudden surge in
SOa laden gases.
5-11
-------
The best means of controlling particulate emissions from the recovery
system stack is to install a demister prior to flue gas exhaust. Demisters
may also aid in increased SOz removal.
5.3.4 Liquor Preparation System
The best means of controlling emissions from the liquor preparation
system is proper design and operation. Such a system would consist of an
acid fortification tower capable of almost complete absorption of SOz by
the weak acid liquor. This result may be achieved by placing two towers
in series. The system would also be designed for cascading of process
unit vent gases to prevent any atmospheric release of SOz
The SOa emissions from the liquor preparation system in a calcium
base mill are usually higher than other sulfite mills. These mills are
continuously preparing fresh cooking liquor without the benefit of a weak
acid recycle stream from the recovery system. Therefore, it may be necessary
to install a caustic scrubber for treating offgas from the acid preparation
tower in calcium base mills.
5-12
-------
REFERENCES
1. Environmental Pollution Control, Pulp and Paper Industry, Part 1, Air.
Environmental Protection Agency, Office of Technology Transfer. EPA
625/7-76-001. October 1976. p. 14-28.
2. Compilation of Air Pollutant Emission Factors, second edition, supple-
ment seven. Environmental Protection Agency. Research Triangle Park,
North Carolina. AP-42. April 1977.
3. Sulfite Pulping, Emissions and Control. A Background Report for
Sulfite Pulp Mill Regulations. Oregon Department of Environmental
Quality, Air Quality Control Division, p. 2.
4. Environmental Pollution Control, Pulp and Paper Industry, Part 1, Air.
Environmental Protection Agency, Office of Technology Transfer. EPA
625/7-76-001. October 1976. p. 14-15.
5. Sulfite Pulping, Emissions and Control. A Background Report for
Sulfite Pulp Mill Regulations. Oregon Department of Environmental
Quality, Air Quality Control Division. p. 2.
6. Environmental Pollution Control, Pulp and Paper Industry, Part 1, Air
Environmental Protection Agency, Office of Technology Transfer. EPA
625/7-76-001. October 1976. p. 14-15.
7. Sulfite Pulping, Emissions and Control. A Background Report for
Sulfite Pulp Mill Regulations. Oregon Department of Environmental
Quality, Air Quality Control Division, p. 8.
8. Micheletti, W. C. and C. M. Thompson. Trip report, Boise Cascade,
Salem, Oregon. Radian Corporation. Austin, Texas. June 22, 1978.
9. Sulfite Pulping, Emissions and Control. A Background Report for Sulfite
Pulp Mill Regulations. Oregon Department of Environmental Quality, Air
Quality Control Division, p. 8.
10. Micheletti, W. C. and C. M. Thompson. Trip report, Publishers Paper
Co., Oregon City, Oregon. Radian Corporation. Austin, Texas.
June 22, 1978.
5-13
-------
11. Environmental Pollution Control, Pulp and Paper Industry, Part 1, Air.
Environmental Protection Agency, Office of Technology Transfer. EPA
625/7-76-001. October 1976. p. 14-20.
12. Linero, A. Background Document: Acid Sulfite Pulping, Final Report.
Environmental Science and Engineering, Inc. Gainesville, Florida.
EPA-450/3-77-005, PB 264 301, EPA Contract No. 68-02-1402. January
1977. p. 22.
13. Micheletti, W. C. and C. M. Thompson. Trip report, Boise Cascade,
Salem, Oregon. Radian Corporation. Austin, Texas. June 22, 1978.
5-14
-------
6.0 EXISTING EMISSIONS REGULATIONS
Only a few states have existing regulations designed specifically to
limit the atmospheric emissions resulting from the pulping of wood by the
sulfite or neutral sulfite semichemical processes. The purpose of this
chapter is to provide an overview of those existing emissions regulations
which will probably affect the sulfite and NSSC pulping industries. A
complete listing of the current relevant state implementation plans for
sulfur and particulate emissions is given in Tables 6-1 through 6-4.
These tables present the state regulations as given in The Environment
Reporter State Air Laws.1 Consequently, the emissions limitations are in
English units (Ib/ton and Ib/hr). To convert to metric units (g/kg and
kg/hr), divide the corresponding English unit by 2.0 and 2.2, respectively.
6.1 EMISSIONS REGULATIONS FOR SULFITE PULPING
At present, ten states regulate sulfur emissions and six states
regulate particulate emissions from the sulfite wood pulping process. Only
four states (Alaska, New Hampshire, Oregon, and Washington) regulate both
sulfur and particulate emissions. Five of the states which have sulfite
mill regulations do not have any sulfite mills. Some of these states do
have neutral sulfite semichemical mills and the sulfite mill regulations
are probably applied to the NSSC mills.
For the most part, these regulations are designed to limit S02 emissions
6-1
-------
from the digesters (or blows), recovery systems, and the mill in general
(i.e., washer vents, storage tanks, etc.). S02 limitations are normally
expressed as g SOz/kg of air dried pulp (Ib/ton) or ppm SOz . The most
restrictive regulations limit total S02 emissions from the mill to 4.5 g/kg
of pulp (9.0 Ib/ton). To meet these regulations, the mill would have to
reduce uncontrolled emissions approximately 89%.
Particulate regulations apply only to recovery system exhaust stacks.
The particulate limitations are typically expressed as g particulate/kg of
air dried pulp (Ib/ton). The most restrictive regulations limit particulate
emissions from the recovery system exhaust stack to 1.0 g/kg of pulp
(2.0 Ib/ton). To meet these regulations, the mill would have to reduce
uncontrolled emissions approximately 44%.
6.2 EMISSIONS REGULATIONS FOR NSSC PULPING
Currently three states regulate SOa emissions and four states regulate
particulate emissions from the NSSC wood pulping process. Only two states
(Alabama and Louisiana) regulate both sulfur and particulate emissions.
Unlike the sulfite regulations, which are specifically designed for that
process, the NSSC emissions limitations are closely associated with those
limitations designated for the kraft process. These regulations probably
represent an effort by the states to regulate two integrated processes as
one. No states have implemented regulations specifically designed for
NSSC pulping. However, the state of Washington is currently gathering
data to determine the need and possible form for specific NSSC emissions
regulations.2
6-2
-------
6.3 ADDITIONAL RELEVANT REGULATIONS
In states which have not established specific regulations for the
sulfite and NSSC pulping operations, these processes will probably be
required to meet the emissions limitations designed for process units.
These regulations normally determine the allowable emissions from an
equation based on the process weight rate. The process weight rate is
usually defined as the total weight of all materials introduced into the
process, divided by that period of time (in hours) during which such
materials are introduced into the process. Liquid and gaseous fuels,
uncombined water and combustion air are excluded from the weight of
materials introduced into the process. The process weight rate is usually
calculated in kg/hr (ton/hr) and the allowable emissions are typically
determined in g/hr (Ib/hr). The extent to which these regulations are
enforced with regard to sulfite and NSSC pulping operations is unknown.
Some states also have opacity regulations, usually based on the
Ringleman number. With the exception of ammonia base systems, opacity
requirements should not be a problem. However, for an ammonia base
liquor, the recovery system exhaust stack may emit particulates of
ammonium sulfate and ammonium sulfite that produce a blue haze. The extent
to which opacity regulations are enforced with respect to sulfite and NSSC
pulping operations is unknown.
6-3
-------
Table 6-1 . STATE IMPLEMENTATION PLANS (SIP) FOR SULFUR EMISSIONS
SttiLo
Alabama
Alaska
Arizona
Arkansas
Ca 1 j fornia
Colorado
Connecticut
Type of Pulping Process Unit Type
Kraft and neutral sulfite Recovery furnaces, lime kilns,
mllJs digesters, multiple effect
evaporators
Sulfite mills Blow pits, washer vents, storage
tanks, digester relief and
recovery systems
Recovery furnace stack
Digesters and multiple
effect evaporators (for
non-condensibles)
Sulfite mills Blow pJts, washer vents,
storage tanks, and
digester relief and
recovery systems
All industrial process units
See Table 6-3 California Sulfur Dioxide Regulations
Any process opening
Any process unit
Sulfite mills Blow pits, washer vents, storage
tanks, digester relief, recovery
Emissions Limitations
Existing Sources
TRS < 1.2 Ib (expressed as H2S dry)/
ton of air-dryed pulp
E < 20 Ib sulfur oxides (expressed
as S02)/ton of pulp
TRS < 5 ppm (expressed as IhS on a
dry basis)
TRS < level obtained by the reduction
achieved by thermal oxidation In a
lime kiln
E < 9 Ib sulfur oxides (expressed as
SOa)/ air-dried ton of pulp
produced
E < 0.2 ppm S02 (30 rain. avg. outside
premises)
E < 500 ppm S02
E < 5 tons S02/day
E < 9.0 Ib/ton of air-dried pulp
produced
New Sources
BPACT
Same as
existing
Same as
existing
Same as
existing
Same as
exist Ing
Same as
existing
E < 2 tons
S02/day or
BPACT
Same as
existing
system, etc.
(Continued)
-------
Pnge Two
Tnble 6-1. (continued)
ON
in
Sliitc Type of Pulping Process
Ui'lnwnre
Fl..r Id.i
Cnirgl.i
ll.iw.il 1
Idaho
111 InolH
lut) l.'in.'i
Emissions Limitations
Unit Type Existing Sources
Sulfur recovery operations E < 2000 ppm by volume or
E< 2.5(P) + 300
Where: E - emission (Ib/lir)
P - production rate
(ton/day)
None
Stacks<90 feet E - 1.2(F)(hs)
Stacks - 90 feet E -40002
Noncombustlon process sources E £ 19.5 (P)
New Sources
Same
None
Same
Same
Same
None
None
Same
Same
as exist Ing
as existing
ns exist ing
as existing
as existing
ns oxl at 1 ng
I., w.i
Process units capable of
emitting SO
Where: E cm»oa»u>i» \»t* «»**«!»»/
P total process capacity
(ton/hr)
E < 500 ppm SO-(bnsed on volune)
None
Same as existing
None
(Continued)
-------
Page Three
Table 6-1. (continued)
State Type of Pulping Process
Kentucky Sulflte mills
Louisiana Kraft and neutral
sulflte mills
Maine Sulflte mills
Maryland
Massachusetts
Michigan
1 Minnesota
°* Mississippi
Missouri
Emissions Limitations
Unit Type , Existing Sources
Blow pits, washer vents, storage E <_ 9.0 Ib/ton of air dried pulp
tanks, digester relief, recovery produced
systems, etc.
E < 2000 ppm St>2 by volume at
standard conditions
E < 401bSOifelr drledtonof sulfite
pulp produced
All Industrial process units E <_ 2000 ppm S02
All industrial process units E < 500 ppm SO
and BACT
None
None
All Industrial process units E < 2000 ppm SO- by volume
E < 2000 ppm S02 by volume
E < 70 mg/m3 of H SO^ and/or
S03
E < 1000 Ib SO./hr
E < 0.03 ppm ICS (30 rain avg)
^ 2
E £ 0.05 ppm H2S (5 rain avg)
New Sources
Same as existing
Same as existing
Same as existing
E < 500 ppm S02
Same as existing
None
None
E 5 500 ppmv S(>2
E < 500 ppnv S02
E < 35 mg/m3' ot ll.,S04
and/or 803
E < 1000 lbSO?/hr
E < 0.03 ppmlLs
T30 min av,g)
E 0.05 ppm
(5 min avg)
Montana
Nebraska
All industrial process units
None
Cannot exceed 1972 emissions
None
(Continued)
-------
Page Four
TII hie 6-1. (continued)
State Type of Pulping Process
Nevada
New Hampshire Sulflte mills
New Jersey
Ni-w Mexico
New York
North Carol lua
North Dakota
Ohio Sulflte mills
Emissions Limitations
Unit Type Existing Sources
All industrial process units E < 0.292(P) '
Where:
E D emissions (Ib/hr)
P - total feed sulfur Ub/hr)
When E < 10, then E <_ 1000 ppm
E < 20 Ib/air dried ton of
sulflte pulp produced
All industrial process units E < 2000 ppm SO^
None
None
None
All Industrial process units Maintain Ambient Air Quality Standards
Total SO < 9 Ib/ton of air dried pulp
New Sources
Same
Same
Same
None
None
None
Same
Same
as existing
as existing
.is existing
as exlRting
as existing
Oklnhomn
AlI pulp mills
Sulflte mills
Blow system
Recovery system
Total Dally
produced
Total SO <^ 18 Ib/ton of air dried pulp
produced (two liour avg)
SO £ 0.2 ll'/niln/ton of unbleached pulp
charged to digester (15 nin avg)
SO- < BOO ppm (hourly avg)
SO < 20 Ib/ton of air dried unbleached
pulp produced
Same as existing
Same an exlnllng
(C o n t I a u e
-------
Page Five
Table 6-1. (continued)
I
co
Emissions
State Type of Pulping Process
Pennsyl vanla
Rhode 1 stand
South Carolina
South Dakota
Tennessee Class I County
Unit Type
All industrial process units
All industrial process units
All industrial process units
Limitations
Existing Sources
E < 500 ppm S02
None
None
Maintain Ambient
E < 500 ppm S02
by volume (dry)
Air
(dry
Quality
; one hr
Standards
avg)
New
Same
None
None
Same
Same
Sources
as existing
as existing
as existing
Texas
I It-ill
Vermont
Virginia
Washington
Class II, lit Counties
Class IV, V, VI Counties
Sulflte mills
All Industrial process units
All industrial process units
All industrial process units
All industrial process units
All industrial process units
All industrial process units
Mill practicing SSL Incineration
Hill not practicing SSL incineration
Blow system
Recovery system and acid plant
Recovery system and acid plant
in areas of special need
'"Z \*JLJ » «Jiic lit avgs
E <_ 1000 ppm SO (dry; one hr avg)
E <_ 2000 ppm S02(dry; one hr avg)
SO- < 0.4 ppm (net ground level
concentration; 30 mln avg)
H2S £ 0.08 ppra (net ground level
concentration; 30 rain avg)
Maintain primary and secondary
Ambient Air Quality Standards
None
E < 2000 ppm SO by volume
Total Dally SO <_ 20 ]b/ton ADU pulp
Total Daily SO^ < 4 Ib/ton ADU pulp
S02 £ 0.2 Ib/mln/ton of unbleached pulp
charged to digester (15 mln avg)
SO <_ 800 ppm (dry; hourly avg)
SO <_ 300 ppm (dry;hourly avg)
Same as existing
Same as existing
Same as existing
None
Same as existing
Same as existing
Same as existing
Same as existing
SO < 200 piim(dry;hr
(Cunt Inued)
-------
Page Six
Tablr 6-1. (continued)
SlaLe
Type of Pulping Process
Unit Type
Emissions Limitations
Existing Sources
New Sources
vO
Wont Virginia
Wl BCOIlBln
Wyoming
All Industrial process units
SO <_ 2000 ppm by volume
None
None
Same, as existing
None
None
111'ACT: Best Practical Available Control Technology
II AC I: Item Avnllnhle Control Technology
-------
Table 6-2 .STATE IMPLEMENTATION PLANS (SIP) FOR PARTICULATE EMISSIONS
o
State
Alabama
Alaska
Arizona
Arkansas
Emissions Limitations
Type of Pulping Process Unit Type Existing Sources
Kraft and neutral Recovery furnaces E £ 4.0 Ib/ton of pulp
sulfite mills
Smelt dlssolver vents E £ 0.5 Ib/ton
I.ime kilns E £ 1.0 Ib/ton of pulp
Kraft and sulfite Blow pits, washer vents, storage E £ 2.0 Ib/ton of pulp
pulp mills tanks, digester relief and
All industrial process units For units < 30 ton/hr
E = 3.59 (F)"-bZ
For units > 30 ton/hr
E = 17.31 (P)0-16
Where:
E - emissions (Ib/hr)
P = process weight (ton/hr)
All industrial process units For units < 30 ton/hr
E = 3.59 (p)0.62
For units > 30 ton/hr
E = 17.31 (p)0.16
Where:
E - emissions (Ib/hr)
P = process weight (ton/hr)
Note: E cannot exceed
1000 Ib/day or 100 Ib/hr
New Sources
BPACT
BPACT
BPACT
Same as
Existing
Same as
Existing
Same as
Existing
Cat JCornia
See Table 6-4
California Particulate Emission Regulations
(Continued)
-------
Page Two
Table 6-2 (continued)
Stale
Type of Pulping Process
Unit Type
Emissions Limitations
Existing Sources
New Sources
Colorado
Conned Ictit
in* l.iwnrc
Klor I da
All Industrial process units
All Industrial process units
All Industrial process units
All industrial process units
All industrial process units
For units < 30 ton/lir
E - 3.59 (P) °-62
For units > 30 ton/hr
K - 17.31 (P)»-16
Where:
E * emissions (Ih/hr)
P - process weight (ton/lir)
For units <. 30 ton/hr
E - 3.59(P) °-62
For units > 30 ton/hr
E = 17.31 (P)°.l6
Where:
E = emissions (Ib/hr)
P - process weight (ton/hr)
E < 0.2 grains/standard cubic foot
For units <^ 30 ton/hr
E = 3.51 (P)'-"
For units > 30 ton/hr
E - 17.31 (P)e-It
Where:
E = emissions (Ib/hr)
P = process weight (ton/hr)
E - 4.1 (P)*-"
Where:
E - emissions (Ib/hr)
P process weight (tons/hr)
Same as existing
Same as existing
Samu as exist ing
latest Reasonably
Available Control
Technology
For l'< ID
E - /i.J(P)'-"
For r > 30
E-|55(l')°'" !-'(>
(Cont Inued)
-------
Page Three
Table 6-2. (continued)
Type of Pulping Process
Unit Type
Emissions Limitations
Existing Sources
New Sources
I
M
N>
Hawaii
Idaho
11 lino Is
Indiana
Ail industrial process units
All industrial process units
A31 industrial process units
All Industrial process units
For units < 30 ton/hr
F, = 4.1 (Pi0-67
For units > 30 ton/hr
F. = 40.0
Where:
E - emissions (Ib/hr)
P = process weight (ton/hr)
For units £ 30 ton/hr
E = 4.10 (P)"'67
For units > 30 ton/hr
E = [55 30 ton/hr
E = f55(P)D-n]-40
Where:
E = emissions (Ib/hr)
P = process weight (ton/hr)
For units <_ 30 ton/hr
E = 4.10 (F)"-67
For units > 30 ton/hr
E = |55(P)"-11]-40
Where:
E = emissions (Ib/hr)
P = process weight (ton/hr)
Same as
existing
Same as
existing
For P < 450
E = 2.54(P)°'S3'1
For P > 450
E = 24.8(P)0-16
Same as
exist Ing
(Continued)
-------
Page Four
Table 6-2. (continued)
Slate
Type of Pulping Process
Unit Type
Emissions Limitations
Existing Sources
New Sources
Kentucky
Krnft and neutral
milflie mills
All Industrial process units
All Industrial process units
All Industrial process units
Recovery furnaces
Smell dlssolvor vents
Line Kilns
For units S_ 30 ton/hr
E I.IO(P)1-67
For units > 30 ton/lir
E - 155(P)"-11)-40
Where:
E - emissions (Ib/hr)
P - process weight (ton/lir)
or
K 5 0.1 graln/SCF of exhaust gas
For units < 30 ton/hr
E = 4.lO(Py-"
For units > 30 tou/hr
E = (55(P)'-ll]-'iO
Where:
K - emissions (Ih/hr)
P = process weight (ton/hr)
For units < 30 ton/hr
E = i-lOlP)1"'"
For units > 30 ton/hr
F. - l55(P)°-nMO
Where:
E > emissions (Ib/hr)
P - process weight (ton/hr)
E < 4 Ih/equlvalent pulp ton
E < 0.5 lb/equivalent pulp ton
E <_ 1 .0 Irt/equlvnlont pulp ton
Same as
existing
Same as
existing
Same as
exinlLng
BI'Af
(C o n t I n ii e d)
-------
Page Five
Table 6-2. (continued)
I
M
-P-
State
Ma Ine
Type of Pulping Process Unit Type
All industrial process units
Emissions Limitations
Existing Sources
For units < 30 ton/hr
E = 3.59(Py-S2
New Sources
Same as
existing
Maryland
Massachusetts
Michigan
All Industrial process units
All industrial process units
All industrial process units
For units > 30 ton/hr
E = 17.31 (P)'-16
Where:
E = emissions (Ib/hr)
P - process weight (ton/hr)
None
E = |55(P)°-11]-''0
Where:
E = emissions (Ib/hr)
P = process weight (ton/hr)
For units < 30 ton/hr
E < 4.10(PT>'87
For units > 30 ton/hr
E <^ [55(P)°'1M-40
Whe re:
E » emissions (Ib/hr)
P = process weight (ton/hr)
For units < 30 ton/hr
E = 3.59 30 ton/hr
E = 17.31(P)°'Ie
Where:
E = emissions (Ib/hr)
P = process weight (ton/hr)
E = %([55(P)0-11J-AO)
E = emissions (Ib/hr)
P = process weight i
(ton/hr)
Same as
existing
Same as
existing
(Continued)
-------
Page Six
Table 6-2. (continued)
Type of Pulping Process
Emissions Limitations
Unit Type
Existing Sources
New Sources
Mississippi
Missouri
CT>
I
Nrhraskn
All Industrial process units
All Industrial process units
All industrial process units
All Industrial process units
E = 4.10(P)"-67
Where:
E - emissions (Ib/hr)
P = process weight(ton/lir)
For units < 10 ton/hr
E = 4.10(P7«-'7
For units > 30 ton/hr
E = (55.0 30 ton/hr
E = |55.0(P)"-" |-40
Where:
E Demissions (Ib/hr)
P = process weight (ton/hr)
For units < 30 ton/hr
E = i4.10{fT-tJ
For units > 30 ton/hr
E - |55.OCP)*-11!-**)
Where:
f. - emissions (Ih/hr)
P B process weight (ton/hr)
Same as
existing
Same as
existing
Same ns
exist ing
Same HS
exist 1ng
(Cont inued)
-------
Page Seven
Table 6-2. (continued)
I
M
O
Type of Pulping Process
Unit Type
Emissions Limitations
Existing Sources
Nevmla
All Industrial process units
New Hampshire Sulfite mills
New Jersey
All industrial process units
For units <_ 30.000 kg/hr
E <_ 0.193(P)°-6'
For units > 30,000 kg/hr
E = U1.78(P)'-U]-18.14
Where:
E = emissions (kg/hr)
P = process weight (kg/hr)
For units < 30 ton/hr
E <_ 5.05(P)°-67
For units > 30 ton/hr
New Mexico
Where :
E = emissions (Ib/hr
P = process weight (ton/hr)
For R £ 50
E = 0.5
For 50 < R < 3000
E = R/100
For R >_ 3000
E = 30
Where:
E = allowable emissions (Ib/hr)
R = uncontrolled emissions (Ib/hr)
None
New Sources
Same ns
existing
For units <^ 30 ton/hr
For units> ton/hr
E< |55(PJI>11]-40
Where:
E = emissions (Ib/hr)
P = process weight
(ton/hr)
Same as
existing
None
(Continued)
-------
I'age F.I glit
Table 6-2. (continued)
SLatf
Type of Pulping Process
Unit
Emissions Limitations
Existing Sources
New Sources
New York
North Carolina All pulp mills
a*
(-
-J Nurtli IMkutn
All Industrial process units
Recovery furnace stack
Dissolving tank vent
Line Kiln stack
All Industrial process units
All Industrial process units
For units < 30 ton/lir
E £ 0.024(P)'-SS5
For units > 50 ton/lir
E < (3q(P)°-«tJl-50
Where:
E = emissions (Ib/hr)
P = process weight (Ib/hr)
E <^ 3.0 Hi/equivalent ton of air
dried pulp
E < 0.6 Ib/equlvalent ton of air
dried pulp
E <_ 0.5 Ib/equlvalent ton of air
dried pulp
Fur units < 30 ton/lir
E <_ 4.10(PT*'"
For units > 30 ton/hr
E £I55(P)0-I1)-40
Where:
E = emissions (Ib/hr)
P => process weight (t»n/hr)
For units < 30 ton/lir
E <^ 4.10(py-'7
For units > 30 ton/hr
E <^ |55(P)1-Ml-*»
Where:
E = emissions (Ib/hr)
P process weight (ton/hr)
Same as
existing
Same as
exist Ing
Same as
exist Ing
Sane as
exist In
(Cont Inued)
-------
Page Nine
1'jihle 6-2. (continued)
Type of Pulping Process
Unit Type
Emissions Limitations
Existing Sources
New Sources
Ok 1 a homa
All Industrial process units
M
CO
Oregon
Pennsylvania
Sulflte mills
KImde Islnnd
Recovery furnace stack
All Industrial process units
All Industrial process units
For units < 30 ton/hr Same as
E <_ 4.10(py-67 existing
For units > 30 ton/hr
E = [55(P)"-1I]-''0
Where:
E = emissions (Ib/hr)
P = process weight (ton/hr)
E £ 4 Ib/ton of air dried Same as
unbleached pulp produced existing
For V <_ 150,000 Same as
E <_ 0.04 existing
For 150,000< V< 300,000
E <_ 6000/(V-1)
For V >_ 300,000
E £ 0.02
Where:
E - emissions (grains/dry SCF)
V = effluent gas volume (dry SCF)
For units < 30 ton/hr Same as
E <_ 4.10(PT°-67 existing
For units > 30 ton/hr
E <_ (55(P)°'l']-40
Where:
E = emissions (]b/hr)
P = process weight (tnn/hr)
(Cont Inued)
-------
Page Ten
Table 6-2. (continued)
Type of Pulping Process
Unit Type
Emissions Limitations
Existing Sources
Hew Sources
Soul h Oirnlinn All pulp manufacturing
plants
Siiulh Dakota
TrXllH
Recovery furnace stack
Dissolving tank vents
Line kiln stack
All Industrial process units
All industrial process units
All industrial process units
E £ 2.75 Ib/ton ADU pulp produced
E <_ 1.0 Ib/ton ADU pulp produced
E <_ 1.0 Ib/ton ADU pulp produced
For units <_ 30 ton/hr
E £ 4.10(P)*'"
For units > 30 ton/hr
E <_ (55 30 ton/lir
E <_ |55(P)0-"|-40
Where:
E = emissions (Ib/hr)
P 3 process weight (ton/hr)
For units £ 20 ton/hr
E <_ 3.12(P)°-"5
For units > 20 ton/hr
E <_ 25.4(P)°-lt7
Where:
E = emissions
P « process weight (ton/tir)
Same as
existing
Same as
existing
For units <_ 30 ton/hr
E < 3.59(P)0'82
Fur units >30 ton/hr
E £ 17.31 (I')"'15
Where:
E = emissions
P = process weight
Same as
existing
(Continued)
-------
Page Eleven
Table 6-2. (continued)
N3
O
Emissions Limitations
SLiltl!
Utah
Vermont
Virginia
Type of Pulping Process Unit Type
All industrial process units
with uncontrolled emissions
greater than 100 ton/yr
All industrial process units
All industrial process units
Existing Sources
85% collection efficiency required
E £ 0.1 lb/1000 Ib of undiluted
exhaust gas at actual conditions
See Table I in state regulations
For units < 30 ton/hr
E < 4.10(P7°-167
New Sources
Same as
existing
Same as
existing
Same as
existing
Washington
West Virginia
Sulfite mills
Recovery system
Recovery system in areas of
special need
All industrial process units
For units > 30 ton/hr
E < [55(P)''"1-40
Where:
E = emissions (Ib/hr)
P - process weight (ton/hr)
E <_ 4 Ib/ton ADD pulp (dally avg)
E £ 2.5 Ib/ton ADD pulp (daily avg)
For units < 100,000 Ib/hr
E <_ 0.22(P)-0.4
For units >_ 100,000 Ib/hr
E <_ 21.2
Where:
E = emissions (Ib/hr)
P - process weight (10s Ib/hr)
£ 2 Ib/ton of
AMI pulp (daily avg)
Same as
existing
(Continued)
-------
Pau»> Twelve
T.ibJe 6-2. (continued)
Sl.lUl
Type of Pulping Process
Unit Type
Enlsslons Limitations
Existing Sources
New Sources
Wls
All Industrial process units
Wy..m1nK
All industrial process units
For units < 30 ton/lir
E £ 3.59(P)~0-t!
For units > 30 ton/hr
E < 17.3HP)*-"
Where:
E = emissions (Ib/hr)
P = process weight (ton/hr)
For units £ 30 ton/hr
E < 4.10(P)°-67
For units > 30 ton/hr
E < |55(P)*-"1-«0
Where:
E = emissions (Ih/hr)
P = process weight (ton/hr)
Same as
existing
For units < 30 ton/hr
K £ 3.5'J(P)lliliJ
For units >30 ton/hr
Where:
E - cmlBslon (Ih/hr)
P = procesK weight
(ton/lir)
HI'ACT: Bent Praitlcnl Avallnhle Control Technology.
-------
Table 6-3. CALIFORNIA SULFUR DIOXIDE EMISSION REGULATIONS
County, or City
Emission Regulation
Alpine, Butte, Calaveras, Colusa,
El Dorado, Fresno, Glenn, Imperial,
Inyo, Kern, Kings, Los Angeles, Madera,
Merced, Modoc, Mono, Nevada, Placer,
Plumas, Sacramento, San Joaquin, San
Lui3 Obispo, Stanislaus, Sutter, Tou-
lumne, Tulare, Yolo-Solano
E <_ 2,000 ppm 502
Del Norte, Humboldt, Menodicino,
Northern Sonoma, Shasta, Trinity
E <_ 1,000 ppm^ SOz
Ventura
For process units E <_ 500 ppm SOz
For combustion units E <_ 300 ppm SOz
Alameda, Contra Costa, Marin, San
Francisco, San Mateo, Santa Clara
San Diego
E <_ 300 ppmv SOz
E <_ 50 ppmv SOz
Lake
None
E = allowable emissions
This table represents a compilation of regulations as published by the coun-
ties and air pollution control districts. The accuracy and completeness
of this listing is subject to the availability of current regulatory informa-
tion.
6-22
-------
Table 6-4. CALIFORNIA PARTICIPATE EMISSION REGULATIONSa
County or City
Emission Regulation
Alameda, Contra Costa, Marin, Sacramento,
San Diego, San Francisco, San Luis
Obispo, San Mateo, Santa Barbara, Santa
Clara
E <_ 4.10(P)
and
E } 40
0.67
Butte, Colusa, Del Norte, Glenn
Humboldt, Mendocino, Modoc, Shasta,
Northern Sonoma, Sutter, Trinity
For P £ 30, E <_4.10(P)°'67
For P > 30, E <55(P)°-11-40
Calaveras, El Dorado, Fresno, Imperial,
Kern, King, Madera, Merced, Nevada,
Placer, Plumas, San Joaquin, Stanislaus,
Toulunme, Tulare
For P <_30, E <3.59(P)
For P >30, E <17.31(P)
0.62
0.16
Alpine, Inyo, Mono
See Regulation IV, Table II
Lake
Loa Angeles
See Section 4.12, Table TV
N0.67
For P <5, E <_4.14(P)
For 5 500, E <30
0.235
Ventura
See Rule 53
Yolo-Solano
See Rule 2.19
E - allowable emissions (Ib/hr)
? - process weight rate (ton/hr)
a This table represents a compilation of regulations as published by the
counties and air pollution control districts. The accuracy and complete-
ness of this listing is subject to the availability of current regulatory
information.
6-23
-------
REFERENCES
1. Compilation of Regulations from the Environment Reporter State Air
Laws. Washington, D. C., Bureau of National Affairs.
2. Trip Report, Washington Department of Ecology, Lacey, Washington.
Austin, Texas. Radian Corporation, June 19, 1978. Micheletti, W. C.
and C. M. Thompson.
6-24
-------
7.0 ESTIMATED EMISSIONS
This section discusses the data available for estimation of nation-
wide emissions. The types of emission test data available are described.
Methods for sampling and chemical analysis of pollutants from the sulfite
and NSSC processes are described. Current emission regulations are listed.
Emission factors based on emission test data are presented and average
emission factors are calculated. Nationwide emissions are estimated for
some unit processes.
7.1 EMISSION TEST DATA
The only files containing significant amounts of moderately well
documented emission test data found during this screening study are in the
states of Washington and Oregon. Within the limitations of the screening
study a diligent search was carried out to locate as much emission test
data as possible.
Within the EPA the following people were contacted:
Jim Eddinger RTF, (OAQPS, Emission Standards and
Engineering Division)
Tom Lahre RTP, (OAQPS, Monitoring and Data Analy-
sis Division)
George Cushnie Washington, D. C., (Effluent Guide-
lines Division)
7-1
-------
George Hert Chicago (EPA Region V)
Curt Willard Cincinnati (IERL)
Frank Early Denver (National Enforcement Investi-
gation Center)
In addition to communeiations with people within the EPA, representa-
tives of the pulp industry were contacted early in the study. Paper in-
dustry representatives contacted were: Russell 0. Blosser, Technical
Director of the National Council of the Paper Industry for Air and Stream
Improvement Inc. (NCASI) and Larry Burke of the Northwest Pulp and Paper
Assocation.
The people within the EPA and the trade associations listed above
suggested that emission test data were most likely to be found in state
agencies responsible for control and improvement of air quality.
Appropriate state agencies in Oregon and Washington were contacted
first because they are the only two states which require source sampling.
They also require continuous monitoring of major sources producing sulfur
dioxide emissions and frequent monitoring of major sources producing parti-
culate emissions. Wisconsin requires annual reports of emissions. But,
these reports may be based on emission factors or material balances in-
stead of source monitoring.
7.1.1 Emission Test Data Available from the State of Oregon
The files of the Oregon Department of Environmental Quality (DEQ) con-
tain emission reports from the sulfite and NSSC pulp mills in Oregon. The
files contain reports of emissions of sulfur dioxide and particulates
(where appropriate) from major emission sources in each plant. The time
period covered by the files varies slightly from plant to plant. Generally,
7-2
-------
data is available from some time during 1972 to the present. Annual summary
sheets are available.
The monitoring points are the outlets of the emission control system
for the recovery systems and for the digesters. Relatively sparse data
are available for uncontrolled emissions. Some early reports include
emission data for acid fortification towers.
Additional information in the Oregon DEQ files include Air Contami-
nant Discharge Permits and Permit Review Reports for each mill. Air
Contaminant Discharge Permits include:
performance standards and emission limitations,
compliance demonstration schedule,
monitoring and reporting requirements, and
general conditions and background.
In addition to the specific permitting provisions these documents in-
clude brief descriptions of the mills. The Oregon DEQ files also contain a
report prepared in the early seventies listing several characteristics of
the sulfite and NSSC plants in Oregon. Some estimates of uncontrolled emis-
sions are in this report. The DEQ files contain correspondence with the in-
dividual mills concerning compliance procedures. Some of this correspondence
contains descriptions of emission control equipment. These descriptions
are often incomplete.
7.1.2 Emission Test Data Available from the State of Washington
In the state of Washington the agency charged with regulating air
quality is called the Department of Ecology (DOE). This agency has five
types of files relating to air emissions. They are:
Engineering Files,
Special Studies Files,
7-3
-------
Regulatory Orders,
Source Testing by DOE, and
Emission Files.
A brief description of the type of information available in each follows.
7.1.2.1 Engineering Files
These files contain process diagrams for the processes as they existed
in the early seventies. The information in these files tends to relate
more to equipment than to process flows. Some general descriptions of
emission control measures are included. In general, there is no mass or
energy balance information and no emission flow data. These files are not
up to date, although they do contain some scattered information designed
to update them.
7.1.2.2 Special Studies Files
These files document studies made for each plant to identify major
emission points. These files are in the state archives and are not
readily avaialable. One example of these files was available for inspec-
tion. The special studies files may contain useful data concerning un-
controlled emissions and emissions from miscellaneous sources.
7.1.2.3 Regulatory Orders
These orders describe the emissions limits prescribed for a given
plant with a timetable for compliance. The format required for reporting
emissions to the state and the methods for making calculations are given.
In addition, these orders describe briefly the history of the air emission
control program at each plant.
7.1.2.4 Source Tests
These files contain the results of source tests made by personnel
from the Department of Ecology. These tests have been made more often for
7-4
-------
some plants than others. Approximately 3 to 6 source tests for sulfur
dioxide and particulates have been made for each plant for the years
1972 to 1978. These reports contain a brief description of the pulp mill
and process source, test procedures, data, calculations, and results.
7.1.2.5 Emission Files
These files contain emission data reported by individual plants on a
monthly basis. The files cover the time period from about 1972 to the
present. The early data is more scant than recent data. Data before 1974
has been placed in the state archives and is not readily available.
Sulfur dioxide concentrations are presented as daily averages. Particu-
lates are measured 3 or 4 times per month. No annual summaries are avail-
able.
7.1.3 Emission Data Available from the State of Wisconsin
The Wisconsin Department of Natural Resources (DNR) Bureau of Air
Management has prepared a computerized emissions inventory of all point
sources reported in the state. The inventory is arranged according to
air regions. A loan copy of the printout for the Lake Michigan I air
region was obtained. This region contains three sulfite mills and one
NSSC mill. Emission factors were given for several sources in these
mills including digesters and acid fortification towers. No basis for
these emission factors was reported. No emission test data were listed
for sources other than power boilers. Flow rates are given for some ef-
fluent streams.
7.2 Emission Factors
The emission factor data obtained as described in Section 7.1 is
compiled in Tables 7-1 through 7-3 and Table 7-5. Average emission factors
7-5
-------
Table 7-1. SUMMARY OK UNCONTROLLED AND CONTROLLED EMISSION FACTOR DATA AND RECOVERY/CONTROL METHODS FOR SULF1TE PULPING, ACID PLANT EMISSIONS
Company
Ammonia Base Mills
Scott Paper Co.
Scott Paper Co.
Scott Taper Co.
ITT Rayonier
Calcium Base Mills
Georgia Pacific
Georgia Pacific
Georgia Pacific
American Can Co.
American Can Co.
Consolidated Papers
Sodium Base Hill
ITT Rayimler
ITT Rayonier
Emission Factors Data used in Average
Location (g S02/kg pulp) Control Method and Comments Emission Factor Calculation
Everett, WA 0.18a
Everett. WA 0.002£
Anacortes, WA O.ll"
Port Angeles, WA 0.20a
Belllngham, WA 0. 30a
Bellingham, WA 0.04
Bellingham, WA <0.01°
Greenbay, WI 3.8a
Greenbay, WI 3.8d
Appleton, WI 1.2d
lloquiara, WA 0.08a
Hoquiam, WA 0.138
Anjnonia absorption followed by water & YES
caustic scrubbing
Ajpmonla absorption followed by water & NO
caustic scrubbing
Ammonia absorption, water scrubbing, control YES
of process variables
Packed tower and Jenssen tower with limerock YES
Not described."1 NO
Emissions from digester vent system are combined with YES - new system
emissions from acid plant and treated in a caustic installed
scrubber.8 June 1977
Jenssen Tower scrubber YES
Not described NO
Not described YES
Not described"1 NO
Not dcscribede YES
'Unero, A. Background Document: Acid Sulflte Pulping, Final Report. Environmental Science and Engineering
Inc. Gainesville, Florida. EPA-450/3-77-005, PB 264 301, EPA Contract No. 68-02-1402. January 1977.
'Washington, DOE, Monthly Emission Reports, January 1978 through May 1978.
'Washington, DOE, Source test, September 22, 1977.
'uisii'iisln Department of Natural Resources, llureati of Air Management, 1977 Air Emission Inventory, Lake Michigan I, May 26, 1978
'Washington, DOE, Monthly Emission Reports, April 1977 through May 1978.
Washington, DOE, Source Test Report. Test performed January 17, 19, 1978. Report dated February 6, 1978.
^Washington, TOE, Regulatory Order Docket, No. DE 78-108, Appendix B, Fact Sheet, February 27, 1978.
-------
T.ilil.- 7-2. SUMMARY OF UNCONTROLLED AND CONTROLLED EMISSION FACTOR DATA AND RECOVERY/CONTROL METHODS FOR SULFITE PULPING, DIGESTER DISCHARGE SYSTEM
EMISSIONS
COM I1 ANY
MILL LOCATION
EMISSION FACTORS
(g S02/kg polp)
CONTROL METHOD AND COMMENTS
DATA USED IN AVERAGE EMISSION
FACTOR CALCULATIONS
Ma gnealum Kaae Sulflte Mills
Great Northern Millinocket, ME
Pub] Inborn Paper Newberg, OR
Publishers Paper Newberg, OR
Publishers Paper Newberg, OR
1'iihl isher.s I'aper Oregon City, OR
Ptibl inhere Paper Oregon City, OR
Publishers Paper Oregon City, OR
Publishers Paper Oregon City, OR
Crown ZclJerbach Camaa, WA
Crown 7-cl lerbacli Cantas, WA
Weyerhaeufier Longview, WA
Ammonia Base Sulftte Mllla
Rulne Cascade Salem, OR
3.2"
0.6a
22b
0.9C
O.la
26.q
1.2e
0.5C
1.0"
1.0f
o.oie
25
Cool water added at end of cycle
Two stage turbulent contact absorber
system installed In September 1971;
SO2 emissions reduced by 982.
None
Two stage turbulent contact absorber
Horizontal packed-bed scrubber and digester pump-out
system. System Installed In November 1974; SO?
emissions reduced by 992?
None
Low pressure, relief stack, sprays
Pump-out system and caustic scrubber
Magnetite process began In 1972; lower free SOj
In cook liquor.
Quench pimped Into blow line during blow8
Digester Is dumped; the dump tank is vented to
recove ry furnace absorber
None. Installed digester pump-out system J.mujry 1974.
Since installation of pump-out, system, d Igt-stor umlssioi
have be«n passed through recovery system absorber and
not reported separately.
1
>ns
YES
NO
YES
YES
NO
YES
NO
YES
YES
NO
NO
(C o n t 1 n u e d)
-------
Page 2
Table 1-2. (Continued)
I
00
COMPANY
Ammonia
Boise
Finch
Base Sulfite
Cascade
Pruyn
MILL LOCATION
Mills
Salem, OR
Glens Falls, NY
EMISSION FACTORS
(g S02/kg pulp)
406
None
CONTROL METHOD AND COMMENTS
Low pressure, relief stack, sprays
Continuous digester. This is a bisulfite
mill. The continuous digester eliminates
the discharge to the blowpit.e
DATA USED IN AVERAGE EMISSION
FACTOR CALCULATIONS
YES
NO
Scott Paper Co. Anacortes, WA 12
Scott Paper Co. Everett, WA 0.2a
Scott Paper Co. Everett, WA 0.2
ITT Rayonler Port Angeles, WA 0.2
Procter & Gamble Creen Bay, WI 4.7
None, other than pressure relief system. This
mill closed permanently in March 1978.
Pressure relief system vented to acid plant.
Condensation system and scrubber. About 54%
of plant serviced by recovery system, 46% by
acid plant.
The stack sampled serves 12 digesters. Six are
blown at 172 kPa (25 psi) and six are dumped
at atmospheric pressure. The effluent gases
are cooled and passed through spray towers with
water as the absorbing liquid.
Packed tower followed by Jensscn lime rock scrubber.
Not described; Basis for emission factors not given.
YES
YES
NO
YES
NO
Calcium Base Acid Sulfite Mills
Georgia Pacific Belllngharo, WA
Georgia Pacific Belllngham, WA
Georgia Pacific Bellingham, WA
Georgia Pacific Beilingham, WA
American Can Co. Greenbay, WI
American Can Co. Greenbay, WI
0.01
0.041
10/e
a.k
Caustic scrubbing facility.
Emission rate Includes contribution from acid plant.
Caustic scrubber offgas.
Stack scrubber; before caustic was used.
Unknown.
Partial relief of pressure before digester discharge.
Basis for emission factor not given.
NO
YES
NO
NO
YES
YES
(C o n t 1 n 11 e d)
-------
Page 3
Table 7-2. (Continued)
I
vo
COMPANY HILL LOCATION
Sodium Base Acid Sulftte Mill
ITT Rayonler Hoqulam, WA
ITT Rayonler Hoqulam, WA
EMISSION FACTORS
(g SOa/kg pulp)
1.0a'k
0.8"
CONTROL METHOD AND COMMENTS
Chemical scrubber.
Unknown .
DATA USED IN AVKRAGE EMISSION
FACTOR CALCU1.ATIONS
NO
YES
Llncrn, A. Background Document: Acid Sulfice Pulping, Final Report. Environmental Science and Engineering
Inc. Gainesville, Florida. EPA-450/3-77-005, PB 264 301, EPA Contract No. 68-02-1402. January 1977.
Oregon DEQ, Annual Summaries of Monthly Monitoring Reports, February through August 1972.
COregon DEQ, Annual Summaries of Monthly Monitoring Reports, January through December 1977.
Oregon DEQ, Annual Summaries of Monthly Monitoring Reports, January through December 1977.
^Oregon Department of Environmental Quality, Air Quality Control Division, Sulfite Pulplng-Emlsslons and Control, a Background Report for
Sulftte Pulp Mill Reflations, undated.
Oregon DEQ, Monthly Monitoring Report, April 1978.
BAnpitarle, T. R. Crown Zellerbach Environmental Services, Camas, WA. Personil communication with Wayne Mlcheletti, Radian Corporation, June 7, 1978.
'Viuhington, DOE, Source Test Report. Tests performed January 17 and 19, V978. Report dated February 6, 1978.
^Oregon DEQ Annual Summary of Monthly Monitoring Report, July 1972 through December 1973.
'Wisconsin Department of Natural Resources, Bureau of Air Management, 1977 Air Emission Inventory. Lake Michigan I, May 26, 1978.
u
Literature source notes that data are unreliable.
Washington, DOE. Monthly Emission Reports, January 1978 through May 1978.
"VlaBhinRton, DOE Source Test 77-34, September 22, 1977.
(Continued)
-------
O
Page >t
Table 7-2. (Continued)
Footnotes continued...
"Washington DOE, Monthly Emission Reports, April 1977 through May 1978. Based on 15.6 kg (34.5 Ib) sulfur dioxide lost from
blow pit vent stacks/
Schmall, Rodney, Publishers Paper Co., Oregon City, OR, Personal communication with Carol May Thompson, Radian Corporation, May 31, 1978.
Hoover, Richard, Scott Paper Company, Anacortes, HA, Personal communication with Wayne C.
^Oregon DEQ, Annual Summaries of Monthly Monitoring Reports, January through October 1974.
Hoover, Richard, Scott Paper Company, Anacortes, HA, Personal communication with Wayne C. Micheletti, Radian Corporation, June 1, 1978.
-------
Table 7-3. SUMMARY OF UNCONTROLLED AND CONTROLLED EMISSION FACTOR DATA AND RECOVERY/CONTROL METHODS
FOR SULFITE PULPING, RECUVERY SYSTEM EMISSIONS *
COMPANY
Emission Factors
MILL LOCATION for Sulfur Dioxide
(R SOz/ke pulp)
Magnesium Base Sulfice Mills
Great Northern
Publishers Paper
Publishers Paper
Publishers Paper
Publishers Paper
Publishers Paper
Publishers Paper
Crown Zellerbach
Crown Zellerbach
Weyerhaeuser
Wcyerliae»»er
**-""«-«
Mllllnocket, ME 4.6a
Newberg, OR 6.4a
Newberg, OR B.0b
Newberg, OR 5.7°
Oregon City, OR 5a
Oregon City, OR 13. 9b
Oregon City, OR 4.8C
Comas, WA 2.9a
Camas, WA 3.98
Coaraopolls, WA 4.9a
Coaroopolls, HA 10
Cosmopolla , WA 11. 5f
n IJ_ I.IA f\ a*
Emission Factors
for Parcitulates RECOVERY/CONTROL SYSTEM DATA USED IN AVERAGE
(8 Partlculates/kg pulp) EMISSION FACTUR CALCULATIONS
1.4"
0.9a
i.ob
1.4C
1.0a
1.4b
1.2C
1.4a
1.78
1.5a
2.4-5.Sd
4.6£
, .1
Multlclones and
Multiclones and
Multlclones and
Multiclones and
Multlclones and
Multlclones and
Multlclones and
Multiclones and
Unknown.
4 Venturl Scrubbers
4 Vpnturi Scrubbers
4 Venturi Scrubbers
4 Venturl Scrubbers
4 Venturl Scrubbers
3 Venturl Scrubbers
4 Venturl Scrubbers
4 Venturl Scrubbers
Absorption System and Recovery not
described.
Packed towers
Recovery furnace
methods being
No. 1 (Sampling
tested)
M_ 1 ft* 1 *__
YES
NO-
YES
YES
NO
YES
YES
YES
NO
NO
NO
NO
Mr»
Wcyerha
methods being tested)
(Continued)
-------
Page 2
Table 7-3.
(Continued)
SUMMARY OF UNCONTROLLED AND CONTROLLED EMISSION FACTOR DATA AND RECOVERY/CONTROL METHODS
FOR SULFITE PULPING, RECOVERY SYSTEM EMISSIONS
COMPANY
MILL LOCATION
Emission Factors Emission Factors
for Sulfur Dioxide for Particulates
(g SO^/kg) (g Partlculates/kg)
RECOVERY/CONTROL SYSTEM
DATA USIiD IN AVERAGE
EMISSION FACTOR CALCULATIONS
- Weyechaeuser
Weyerhaeuser
Weyerhaeuser
Coamopolia, WA
Cosraopolia, WA
Coaraopolla » WA
4.4e
3.5e
3.8e
1.8e
2.0e
1.6e
Recovery furnace No. 1, Packed towers
Recovery furnace No. 2, Packed towers
Recovery furnace No. 3, 3 Venturi
YES
YES
YES
Weyerhaeuser Longvlew, WA
Ammonia Base Sulfite Mills
Boise Cascade Salem, OR
Boise Cascade Salem, OR
Boise Cascade
Salem, OR
Scott Paper Co. Everett, WA
Scott Paper Co. Everett, WA
ITT Rayonier Port Angeles, WA
Sodium Base Sultlte Mill
ITT Rayonler Hoquiam, WA
ITT Rayonier Iloquiam, WA
ITT Rayonler Iloquiam, WA
4.1a
2.3"
2.2
4.2a
O.la
27 k
0.1*
"
2.4"
0.2a
2.31
o.3J
0.4a
0.2h
0.4a
1.9a
5k
1.4 l
scrubbers plus a packed tower.m
«Absorptlon System and Recovery not
described.
YES
S02 scrubber (95%) followed by Brinks NO
eliminator.3
Scrubbing with ammonia In perforated YES
plate tower" before Installation of
Brinks mist eliminator in June 1975.
Scrubbing with ammonia after installation YES
of Brinks mist eliminator.
Ammonia scrubbing, followed by mist
eliminator.3
Ammonia scrubbing followed by Brinks
eliminator.
YES
NO
YES
Unknown NO
Before controls added Y^S
Controls not described in reference YES
-------
l'age 3
Table 7-3.
Linero, A. Background Document: Acid Sulflle Pulping, Final Report. Environmental Science and Engineering
Inc. Gainesville, Florida. EPA-450/3-77-005, PB 26* 301, EPA Contract No. 68-02-1402. January 1977.
Oregon OEQ, Annual Summary of Monthly Monitoring Report, April 1972 through December 1972.
c
Oregon DEQ, Annual Summary of Monthly Monitoring Reports, January 1977 througli December 1977.
Oregon Department of Environmental Quality, Air Quality Division, Sulflte Pulping - Emissions and Control, a Background Report for Sulflte
Pulp Mill Regulations, undated.
Washington, DOE, Monthly Emission Reports, December 1977 through April 1978.
fWaahlngton DOE, Source Teat, April 19, 1972.
^Washington DOE, Mill Emission Report, April 1978.
"Washington, DOE Source Test Report. No. 78-3. Test date:January 17 and 19,1978; Report date: February 6, 1978.
Oregon DEQ, Annual Summary of Monthly Monitoring Reports, January 1976 through December 1974.
Oregon DEQ, Annual Summary of Monthly Monitoring Reports, January 1977 through December 1977.
Washington, DOE, Regulatory Order No. 38-4, December 18, 1972, Amended July 17, 1973.
Washington DOE, Sulflte Hill Emission Report, April 1978.
"Vllrhelftt 1, Wayne and Carol May Thompson, Trip Report of Visit to Ueyerliaueser Mill in Cosmopolls, UA , June 20, 1978.
"M It I ic It'til, Wayne and Carol May Thompson Trip Report of Visit to Boise Cascade Mill In Salem, OR, June 22, 1978.
-------
Table 7-4. AVERAGE UNCONTROLLED AND CONTROLLED EMISSION FACTORS FOR SULFITE PULPING.
SOURCE
Acid Plant
(ammonia base)
Acid Plant
(calcJura base)
Acid Plant
(sodium base)
Digester Discharge
Recovery Furnace
(magnesium base )
Recovery Furnace
(ammonia base)
Recovery Furnace
(.sodium base)
rnuTDm an nv MII i c unnrMinc Average Emission Factors Average Emission Factors
CONTROL NO. OF MILLS NO. OF MILLS f(|r |ulfu, Dioxide for I'urticulates
(No. of data points) (w/at least 5 mos. (gSOi/kg pulp) (g particulates/kg pulp)
monitoring) Range Average Range Average
Ammonia scrubbing followed by 3
caustic scrubbing, water scrubbing
or scrubbing in presence of llmeror.k
Caustic scrubber (Includes emissions 1
from digester vent)
Controls not described in reference 2
Controlled but controls not described 1
In reference
None 5
Partial relief of pressure 2
Pressure relief, quench liquid added 2
Scrubbers 6
Scrubbing with magnesium bisulfite for 2
economic reasons
Scrubbing with magnesium bisulfite to 8
meet environmental regulations
Ammonia scrubbing without mist eliminator 1
Ammonia scrubbing with mist eliminator 3
Not controlled or only partially controlled 1
Controlled, but description of controls not 1
obtained
3 0.1-0.2 0.2
1 0.04
1.2-3.8 2.5
1 0.1
3 22-40 29
1 12-16 14
1.0-3.2 2.1
4 0.04-0.9 0.4
2 8.0-13.9 11.0 1.0-1.4
7 2.9-5.9 4.2 1.2-2.4
1 8.4
3 2.1-4.2 2.9 0.2-0.4
27.
0.1
._
1.2
1.6
2.3
0.3
b.
1.4
' This process may be controlled only by control of process variables.
As explained In the text, this degree of control represents "uncontrolled emissions" for magnesium base recovery systems.
'Six mills are represented but one mill lias 3 recovery systems so 8 recovery systems are represented
-------
Table 7-5. SUMMARY OF UNCONTROLLED AND CONTROLLED EMISSION FACTOR DATA AND CONTROL METHODS FOR NSSC PULPING.
SOURCE
Acid Plant or
Cooking Liquor
Preparation
Digester System
^j Recovery System
1
M
Oregon DEQ Annual Sunn
b()regon UKQ, Air Contai
L Washington DOE Report.
lo Washington DOE,
COMPANY
Menasha Corp.
Menasha Corp.
Longvlew Fibre Co.
Menasha Corp.
Longvlew Fibre Co.
Menaaha Corp.
Green Bay Packaging Inc.
Green Bay Packaging Inc.
LOCATION ,SS
(g SOi/kg pulp)
North Bend, OR 0.0038
North Bend, OR <0.03b
Longvlew, WA 0.40C
@120 Mg/day
(60! capacity)
North Bend, OR Zerod
Longvlew, WA 0.36e
North Bend, OR No data
Green Bay, WA 0.01g
Green Bay, WA 0.01B
narleaof Monthly Monitoring Reports. April through December 1973
ninant Discharge Permit Review Report (File 06-0015, December 16,
. Air Emissions; Exhibit II
June 19, 1978.
- Air. December 22, 1972. As reported
FACTORS
(g partlculates\
kg pulp )
None
None
None
None
None
1.7£
79/B
1.1*
and January through
1974.)
by W. C. Mlcheletti
CONTROL
None
None
None
None
None
Furnace operation and direct
contact evaporator
None
Venturi Scrubber
July 1976.
and C. M. Thompson In Trip Report
Oregon DM} ntr contaminant Discharge Permit Review Report (File 06-0015, December 16, 1974.)
1 Letter from .1. W. Klein (Longvlew Fibre) to Richard Burkhalter(Washington DOE). Dated: July 1, 1971. AS reported by W. C. Mlrhelcttl nnd C. M.
ThunniR.in In Trip Report to Washington DOE. June 19. 1978.
'Oregon DKQ Annual Summaries of Monthly Monitoring Reports, February 1977 through November 1977.
"Wisconsin UNR, Bureau aC Air Management, 1977 Air Emission Inventory, May 26, 1978. Emission factors In this reference are given in terms
of amount of liquor burned. This emission factor was calculated by multiplying the given emission factor by the given amount of liquor burned
PIT yt.ir to obtain the total amount of emissions per year. The total annual emissions were then divided by the annual capacity of the plant
obtained by multiplying the dally capacity given in Table 3-2 by the nurnter of days the mill operated in 1977 (306 days).
-------
for sulfite processes are listed in Table 7-4. The emission factors are
given in grams of pollutant per air dry unbleached kilogram of pulp.
These emission factors can be converted to pounds pollutant per air dried
unbleached ton of pulp by multiplying by two. Emission data which were
not presented in terms of amount of pulp produced were converted using
appropriate calculations. In some cases, mill capacities as listed in
Table 3-2 were required for these calculations.
Potential major sources of emissions for sulfite processes are acid
absorption towers, digester discharge systems and recovery systems. The
only pollutant of significance from acid absorption towers and digester
discharge systems is sulfur dioxide. Recovery systems emit sulfur dioxide
and particulates.
Some concern has been expressed1 regarding NO emissions from ammonia
X
base spent sulfite liquor recovery systems. A recent EPA document2 cites
the results of a private study. This study found flue gas nitrogen oxide
concentrations of 200 to 500 ppm by volume as NOa - Peak values up to 1000
ppm were observed. Emission factors for nitrogen oxides were reported to
average 8.3 g NOa per kg pulp produced. Emission factors were reported
to range from 4.7 to 11.8 g N02 per kg pulp. All nitrogen oxides were
reported as nitrogen dioxide. The concentrations of nitrogen oxides re-
ported are substantially higher than the 25 to 75 ppm NO reported for
X.
magnesium base sulfite recovery furnaces and kraft recovery furnaces.
Some of the emissions listed in Tables 7-1 through 7-3 and 7-5
represent the average of continuous monitoring efforts for an extended
period of time (typically five months to one year) . Other emissions are
the results of monitoring for shorter lengths of time or of single sets of
7-16
-------
tests. In some cases the number or type of measurements made to obtain
the factors listed are not given in the references cited.
Potential emission sources for the NSSC process are: acid absorp-
tion towers, digesters, and recovery systems. Emissions from these sources
are discussed within the limits of the data obtained.
7.2.1 Emission Factors for Acid Plants at Sulfite Mills
Data concerning acid plant emissions were obtained for seven mills.
The mills are listed in Table 7-1. Three of the mills are ammonia base
mills, three are calcium base mills and one is a sodium base mill. All
magnesium base mills from which data were obtained vented acid plant
emissions through the recovery system or the digester gas control system
so no separate acid plant emissions were identifiable.
Factors influencing emissions from acid absorption towers include the
type and concentration of absorbing solution, the gas to liquid ratio and
the control systems added to the absorption tower. Another factor
influencing the amount of sulfur dioxide emitted is the amount of make-up
sulfur added to the system. Magnesium, ammonia and sodium base mills
usually recover sulfur values from the spent cooking liquor. Calcium
base mills do not. Therefore, a much larger amount of make-up sulfur is
required for calcium base mills than for other sulfite mills. This higher
make-up requirement makes acid plant emissions higher on the basis of a
per unit weight of pulp produced for calcium base mills than for other
sulfite mills.
Control measures applied to sulfur dioxide absorption towers include
control of process variables, or addition of scrubbers.
7-17
-------
7.2.2 Emission Factors for Digester Discharge at Sulfite Mills
Emissions from discharging the contents of the digesters appear to
depend more upon the method used to empty the digester than on any other
factor. Theoretically, the pH of the cooking liquor should have a signi-
ficant influence on emissions since much more free sulfur dioxide is
available in an acid sulfite liquor than in a bisulfite liquor. However,
the data in Table 7-2 do not show a large effect of pH. The Publisher's
Paper Co. mills at Newberg and Oregon City are bisulfite mills and the
Boise Cascade mill in Salem is an acid sulfite mill. Uncontrolled emis-
sion factors averaged over periods of at least seven months for the three
plants are: 22, 26, and 25 g SOz per kg pulp, respectively.
' Control measures used to reduce emissions from digester discharge
include pressure relief in the digester before it is emptied, addition of
quench liquor and use of scrubbers. Neutralization of the pulp-liquor
slurry leaving the digesters is practiced by some mills.
7.2.3 Emission Factors for Recovery Systems at Sulfite Mills
The base used in the cooking liquor will determine the design of
the recovery system. Mills using cooking liquor with calcium as the base
do not practice chemical recovery for return to the process. Calcium
(and ammonia) spent sulfite liquor is used as road binding materials or is
processed for use in drilling muds, fertilizers, or animal feed. Products
such as vanillin and ethanol are made from the spent sulfite liquor by
some calcium base mills. Two mills (one calcium base and one ammonia base)
use the spent liquor as a nutrient to grow special varieties of yeast.
Some calcium base spent sulfite liquor is incinerated to avoid water
pollution problems. This means of disposal is used only when the supply
7-18
-------
of spent sulfite liquor exceeds the demand for the purposes listed above.
Incineration of calcium base spent sulfite liquor creates a particulate
emission problem.3 However, no data were located as to the amount of
emissions this incineration produces.
Consolidated Papers' Mill in Appleton, Wisconsin burned calcium base
liquor for 29 days in 1977. However, the burning was carried out in a
boiler which used natural gas as fuel for 295 days and Number 2 fuel oil
as fuel 50 days."* Presumably, the spent sulfite liquor was fired with
one or another of the other fuels. No data were presented which could be
related to emissions resulting from the burning of the calcium base spent
sulfite liquor.
Mills which use magnesium as the base in the cooking liquor have
always been designed with recovery systems. Recovery of magnesium is
required for the mills to be economically competitive. Recovery of sulfur
also has been standard practice in these mills.
For magnesium base mills the distinction between uncontrolled and
controlled emissions is only a matter of degree. "Uncontrolled emis-
sions" can be defined to be the level of emissions using the degree of
control exercised before environmental regulations were instituted. "Con-
trolled emissions" would be the level of emissions resulting after addi-
tional controls were added to meet environmental regulations.
Data for three magnesium base mills (Publisher's Paper, Newberg,
Oregon; Publisher's Paper, Oregon City, Oregon, and Weyerhaeuser, Cos-
mopolis, Washington) for the time period 1971-1972 (see Table 7-3)
show average sulfur dioxide emissions from recovery systems of 8.0, 13.9
and 10.0 g sulfur dioxide per kg unbleached pulp produced. The Washington
7-19
-------
and Oregon state regulations permit 10 g sulfur dioxide per kg pulp for
all mill emissions. These same three mills had average emissions of 5.7,
4.8 and 3.9 g sulfur dioxide per kg pulp in 1977-78. The average emissions
for the three mills before 1973 was 10.6 g SOz per kg pulp. The average
for the same three mills in 1977-78 was 4.8 g SOa per kg pulp. These
reductions in sulfur dioxide emissions were achieved by more careful
operation of the recovery train in some cases. In other cases, additional
absorbing units had to be added to the recovery train.
Particulate emissions from the recovery systems for the three mills
discussed above were 1.0, 1.4 and 2.4-5.6 g particulates per kg pulp before
1973. In 1977 and early 1978 the particulate emissions of the same three
mills was 1.4, 1.2 and 1.8 g particulates per kg pulp. Particulate emis-
sions increased slightly for one mill and remained about the same for another,
Particulate emissions for the third mill decreased significantly. The
control methods used for particulates at these mills are the same as
control methods used for sulfur dixoide. Mist eliminators have been added
at times to reduce particulate emissions. Plugging of the mist eliminators
has been a problem and none of these three mills had a mist eliminator in
operation in mid-1978.
7.2.4 Average Emission Factors for Sulfite Mills
The average emission factors for sources in sulfite mills listed in
Table 7-4 were calculated from the emission factors listed in Tables
7-1 through 7-3. Average factors are listed for sources within sulfite
mills and for varying degrees of control (including no control) on each
of the sources. When data were available from more than one similar source
the emissions were averaged. The paragraphs below give the procedure which
7-20
-------
was used to select which emission factors were included in the averages
presented in Table 7-4.
To obtain an average emission factor all sources having similar
characteristics were grouped together. If more than one set of data was
available for an emission factor from a source in a given mill, the "best"
factor was chosen. Generally, the "best" factor was that one which re-
presented the most recent monitoring over an extended period of time.
Factors based on extended monitoring were chosen over those based on single
tests. If the same source in the same mill fit different categories of
control at different times, the emission factors usually were included
in each category.
The average emission factors were calculated by averaging the "best"
emission factors for each source in each category of control. Columns
in Tables 7-1 through 7-3 indicate which data were chosen for averaging.
Table 7-4 indicates the number of data points included in the average.
Table 7-4 also lists the number of data points included in the average
which represent averages of long-term monitoring data. Ranges and average
emission factors for sulfur dioxide and particulate emissions are given.
7.2.5 Emission Factors for NSSC Mills
Potential emission sources at NSSC mills include the acid absorption
tower, the digester and the recovery furnace or incinerator. Data listed
in Table 7-5 indicate that emissions from the acid absorption tower and
the digester are very low. The recovery furnace emissions factors listed
in Table 7-5 are from only one type of incinerator. Several types of re-
covery furnaces and incinerators are used by mills using the NSSC process.
7-21
-------
Table 7-6. ESTIMATED NATIONWIDE EMISSIONS
K>
ho
SOURCE
Acid Plant
(ammonia base)
Acid Plant
(calcium base)
Acid Plant
(sodium base)
Digester Discharge
Recovery furnace
(ningneslnm base)
Recovery Furnace
(ammonia base)
Recovery furnace
(sodium base)
CONTROL (
Scrubber
Scrubber
Control of
process variables
Controls not
described
None
Partial pressure
relief
Partial pressure
relief-quench
liquid added
Scrubbers
Scrubbing for
economic recovery
Scrubbing to meet en-
vironmental regula-
tions
Scrubbing w/o mist
eliminator
Scrubbing w/mlst
eliminator
Controlled
AVERAGE EMISSION FACTORS
S02/kg PULP) (g PARTICULATES/kg
0.2
0.04
2.5
0.1
29.
14.
2.1
0.4
6.0 1.2
4.2 1.6
8.4 2.3
2.9 0.3
0.1 1.4
ESTIMATED CAPACITY
PULP) (Mg PULP/DAY)
2804
454
697
430
505
2194
5031
908
2709
1366
1438
430
ESTIMATED NATIONWIDE EMISSIONS'1
(kg S02/DAY) (kg PARTICULATES/DAY)
561.
18.
1742.
43
7070
4607
2012
5448 J090.
11378 4334
11474 3142
4170 431
43 602
48,566 9,599
estimated nationwide emissions are based on capacity figures because capacities of individual plants are available whereas production
rates of Individual plants are r\ot a,va.tlable. The. nrod,iiQtion ra t e in the sulfite wood pulping industry averaged 90 percent for sulflte paper
grades of pulp and 95 percent for dissolving and special alpha grades of pulp. A weighted average utilization factor of 91 percent is appropriate.
-------
7.3 ESTIMATION QF NATIONWIDE EMISSIONS
Table 7-6 presents estimates of nationwide emissions. These estimated
emissions are obtained by multiplying the estimated capacity associated
with each source and each control method by the appropriate average emis-
sion factors.
The assumptions made in estimating capacity associated with each
source are presented below. All capacities are taken from Table 3-2. For
these calculations it has been assumed that the ITT Rayonier Mill in
Washington is the only operating sodium base acid sulfite mill in the
United States.
7.3.1 Estimation of Nationwide Emissions from Acid Plants at Sulfite Mills
Emission factors from acid plants depend on the base used to pre-
pare cooking liquor and whether acid tower emissions are scrubbed. All
magnesium base mills for which information was obtained passed acid plant
emissions through the recovery systems. Consequently, no emission factors
are listed for acid plants associated with mills using magnesium as the base.
The total capacity of sulfite mills using ammonia as the base is
2804 Mg of air dried unbleached pulp per day. Three ammonia base mills
for which data were available used some type of scrubber after the acid
absorption tower. The assumption was made that all acid plants associated
with ammonia base mills use some form of scrubbing after the acid absorp-
tion tower.
The total capacities of sulfite mills using calcium as a base is
1151 Mg per day. It is known that the mill in Bellingham, Washington
passes the off-gas from the acid absorption towers through a scrubber.
The capacity of this mill is 454 Mg per day. All other calcium base
mills are in Wisconsin. The assumption was made that the emissions from
7-23
-------
the acid plants of all the calcium base mills in Wisconsin could be de-
scribed by the average emission factor determined from two Wisconsin
mills.
There is only one sodium base mill in the United States and the
emission factor from the acid plant associated with it is known.
7.3.2 Estimation of Nationwide Emissions from Digester Discharge Sys-
tems at Sulfite Mills
Emission factors from digester discharge systems depend primarily
upon the methods used to control these emissions. There are 26 operating
sulfite mills in the United States. The total capacity of all sulfite
mills is 8002 Mg/day. One sulfite mill is known to use a continuous
digester and the digester discharge emissions are reported to be zero.5
The capacity of this mill is 272 Mg per day. The remaining 25 mills
are presumed to use batch digesters.
Three mills (in Cosmopolis and Longview, Washington and Salem,
Oregon) are known to pass digester discharge emissions through the recovery
system. These three mills were assumed to have emissions similar to
those which have separate scrubbers. The total capacity of these mills
is 998 Mg per day. Mills in Everett, Port Angeles, Camas, Bellingham, and
Hoquiam, Washington and Oregon City and Newberg, Oregon are known to have
scrubbers on digester discharge systems. The total capacity of these
plants is 2477 Mg per day. The assumption was made that the two Alaskan
mills also have scrubbers or their equivalent to control digester dis-
charge emissions. This assumption seems reasonable since the Alaskan
air emission regulations are very similar to those in Washington and Ore-
gon. These two mills have a combined capacity of 1102 Mg per day.
7-24
-------
The mill in Maine relieves the pressure and quenches the pulp
before the digester is emptied. The capacity of this mill is 544 Mg
per day. The calcium base mill in Green Bay, Wisconsin partially relieves
the pressure and blows the digesters. The capacity of this mill is 136
Mg per day.
No information was obtained concerning the methods for controlling
blow pits emissions from the remaining 2017 Mg/day capacity. Since all
mills, except the one in Lebanon, Oregon, were in states which do not have
strict sulfur dioxide emission regulations for sulfite pulp mills, the
remaining capacity was split between quenching and partial pressure re-
lief. Approximately four times as much capacity was assumed to use
quench liquid as to use pressure relief alone.
7.3.3 Estimation of Nationwide Emissions from Recovery Systems at Sulfite
Mills
Emission factors from recovery systems depend on the base used
in the cooking liquor and the degree of control used on the recovery system.
As discussed in a previous section of this report, all magnesium base
sulfite mills have recovery systems. Seven of the 10 magnesium base
sulfite mills are in Washington, Oregon and Alaska. These mills have a
combined capacity of 2709 Mg per day. Emission factors appropriate to
operation under strict environmental controls were applied to these mills.
The remaining mills are in Maine and Wisconsin. The total capacity of these
mills is 908 Mg per day. These mills were assumed to be operating with
emissions appropriate to economic recovery of mangesium oxide.
The total capacity of mills using ammonia as a base is 2804 Mg
per day. Three of these mills are reported to be operating with mist
7-25
-------
eliminators. Their combined capacity is 1438 Mg per day. It was assumed
that the remaining mills are operating without mist eliminators.
The emission factors for the sodium base mill are known. Calcium
base mills do not have recovery systems.
7.3.4 Estimation of Nationwide NO Emissions from Ammonia Base Sulfite Mills
~~ . . . J£
The total capacity of sulfite mills using ammonia as the base is
2804 Mg per day. The average emission factor reported for NO emissions
from ammonia base mills is 4.7 kg NO per Mg pulp (as NOa). These figures
X
yield an estimated nationwide emission rate of 13 Mg NO per day.
X
7.3.5 Estimated Nationwide Emissions from NSSC Pulp Mills
Potential emission sources in NSSC mills include the acid absorp-
tion tower, the digester and the recovery system. Maximum nationwide
emissions can be estimated for the acid plants and the digesters. But,
not enough information is available to estimate nationwide emissions from
recovery systems associated with NSSC mills.
In Section 3.2.2 the maximum NSSC pulping capacity in the U. S.
was estimated to be 9180 Mg per day. The highest emission factor listed
in Table 7-5 for the acid plant associated with a NSSC mill is 0.40 g
SOz per kg pulp. If this emission factor is used, the maximum nationwide
emissions from NSSC acid plants are 3.7 Mg sulfur dioxide per day. A
similar calculation using the highest emission factor for the digester
system yields a maximum emission of 3.3 Mg sulfur dioxide per day.
Emission factor data were obtained from the recovery systems of
two stand alone NSSC mills. Both these mills use Dorr-Oliver incinerators.
The information on recovery systems listed in Table 3-4 indicates that
these systems are not typical of the industry as a whole. Extrapolation
7-26
-------
of the emission factors for these recovery systems to the industry as a
whole could lead to misleading results. Therefore, no estimates of nation-
wide emissions from NSSC recovery systems were made.
7.4 MODEL IV CALCULATIONS
Model IV is a means of quantitatively estimating the anticipated
impact of standards of performance in preventing atmospheric emissions.
The potential emission reduction resulting from the application of stan-
dards of performance is expressed as :
(Tg - TN) (7-1)
where:
T = Emission under baseline year control regulations
T = Emissions under new or revised standards of performance.
In 1975, The Research Corporation of New England prepared Model IV estimates
for a number of industries, including sulfite and NSSC wood pulping.6
The information obtained for the NSSC process during the current screening
study is too sparse to allow for a revised Model IV calculation for this
industry. However, the updated information obtained for the sulfite process
allows for an almost completely revised Model IV calculation. The steps
in calculating the revised Model IV estimate are outlined in Appendix B.
According to these calculations, implementation of new source per-
formance standards would reduce SOa emissions by 4.23 Gg/year (4,670
tons/year) in 1983. Particulate emissions would be decreased by 237 Mg/yr
(263 tons/yr) in 1983. The Research Corporation of New England had pre-
dicted SOa and particulate emission reductions of 49 Gg/yr (54,000 ton/yr)
and 0.0 Gg/yr (0.0 ton/yr), respectively.7
7-27
-------
REFERENCES
1. Early, Frank, EPA National Enforcement Investigation Center Denver,
Co. Personal communication with Wayne C. Micheletti, Radian Corpora-
tion, May 17, 1978.
2. Environmental Pollution Control, Pulp and Paper Industry, Part 1,
Air. Environmental Protection Agency, Office of Technolgy Transfer.
EPA 625/7-76-001. October 1976. p. 14-27.
3. Didier, Paul, Wisconsin Department of Natural Resources, Bureau of
Water Management. Personal communication with Carol May Thompson,
Radian Corporation, July 18, 1978.
4. Wisconsin Department of Natural Resources, Bureau of Air Management,
1977 Air Emission Inventory, Lake Michigan I, May 26, 1978.
5. Oregon Department of Environmental Quality, Air Quality Control
Division, Sulfite Pulping - Emissions and Control; A Background Report
for Sulfite Pulp Mill Regulations, undated.
6. Hooper, T. G. and W. A. Marrone. Impact of New Source Performance
Standards on 1985 National Emissions from Stationary Sources. Volume
1, Final Report, Main Text, and Appendices I through III. The Research
Corporation of New England. Wethersfeld, Connecticut. EPA Contract
No. 68-02-1382, Task 3. October 1975. p. 15.
7. Hooper, T. G. and W. A. Marrone. Impact of New Source Performance
Standards on 1985 National Emissions from Stationary Sources. Volume
1, Final Report, Main Text, and Appendices I through III. The Research
Corporation of New England. Wethersfeld, Connecticut. EPA Contract
No. 68-02-1382, Task 3. October 1975. p. 59, 63.
7-28
-------
8.0 SAMPLING AND ANALYSIS FOR AIR EMISSIONS FROM SULFITE
AND NSSC PULP MILLS
This chapter describes methods for sampling and chemical analysis
which are applicable to the determination of air emissions from sulfite
and NSSC pulp mills. The methods described are applicable to major emission
points such as acid fortification towers, digester discharge systems and
recovery furnace stacks. Manual methods and methods for continuous
monitoring are also described.
The major pollutant emissions from sulfite and NSSC mills are sulfur
dioxide, particulates, and in some cases total reduced sulfur species (TRS).
Emissions from unit operations such as digester discharge systems and acid
fortification towers, contain sulfur dioxide, but negligible concentrations
of particulate matter. Emissions from recovery furnaces, spray dryers, and
smelt tanks contain particulate matter and sulfur dioxide. Emissions of
reduced sulfur compounds are possible from kraft type recovery furnaces,
and their associated smelt tanks. Emissions of reduced sulfur species also
are possible from sulfiting towers used to prepare NSSC liquor from green
liquor.
Measurements of sulfur dioxide and total reduced sulfur concentrations
can be made manually using EPA source sampling methods or continuously using
instrumental techniques. Accurate measurements of particulate concentrations
must be made manually. Approximate particulate concentration can be
8-1
-------
monitored continuously. The paragraphs below outline the procedures which
are currently used to measure air pollutant emissions from pulp mills.
8.1 MEASUREMENT OF VOLUMETRIC GAS FLOW RATES
To determine the pollutant flow rate in a gas leaving a system, the
volumetric flow rate of the gas and the pollutant concentration in the gas
must be known. Volumetric flow rates are determined by measuring linear
flow rates and multiplying by the cross sectional area of the stack or vent.
EPA Methods 1 through 4 offer a means for obtaining all the information
required for determination of volumetric flow rates. These methods are
applicable in stacks or ducts with diameters 0.30 meter or greater. The
flow in the stack at the sampling point must meet certain stability criteria,
EPA Methods 1 through 4 are used with EPA Methods 5 and 6 for manual deter-
mination of emission rates for particulates and sulfur dioxide.
EPA Method 1 gives a procedure for locating traverse points in the
stack or duct. EPA Method 2 gives the procedure for determining average
gas velocity in the stack. EPA Method 3 gives the procedure for calcu-
lating the dry molecular weight of a combustion gas by analyzing the gas
for carbon dioxide and oxygen. (Method 3 may have to be modified for some
pulp mill streams.) Method 4 gives the procedure for determining the
moisture content of the gas. Method 5 gives the procedure for determining
particulate emissions by collecting particulates on a heated filter.
Method 6 gives the procedure for measuring sulfur dioxide concentration in
a flue gas.
Once the characteristics of a gas stream are determined, continuous
monitoring of gas velocity can be carried out by placing a pitot tube at
a point of average gas velocity. The flow rate from small vents can be
measured by inserting a pitot tube into an appropriate position in the
8-2
-------
vent. Accurate velocity measurements cannot be made using a pitot tube.
if the linear flow rate is below 3 or 4 meters per second.
In some cases alternate methods for estimating volumetric flow rates
must be used. One alternate method is to use the capacity of the fan used
to move the gas as a measure of the flow rate. Other methods of estimating
flow rates will depend upon the physical characteristics of the individual
emission point. Time (level of effort) limitations imposed on the current
screening study precluded retrieval and documentation of information
related to accuracy and precision of analytical methods.
8.2 SAMPLE HANDLING AND CONDITIONING
Manual methods for obtaining samples include techniques to withdraw
a known amount of sample from the stream, to separate gases and particu-
lates, and to prevent uncontrolled condensation of water vapor. Instru-
ments which have detectors which operate outside the stack also require
sample handling and conditioning systems. Careful design and proper
operation of such systems is vital to the successful operation of
continuous monitors.
The purpose of sample handling and conditioning systems is to
transfer the sample from the sampling point to the detector. Usually
neither the concentration nor the character of the constituents to be
measured should be changed. In some cases interfering species are
removed in the sample conditioning step. In other cases controlled
chemical changes are effected (e.g., oxidation of reduced sulfur species
to sulfur dioxide for determination of TRS).
The sample handling and conditioning system may contain several
elements to achieve the goals outlined above. The elements of a sample
handling and conditioning system may include: the sample probe, the
8-3
-------
conditioning device (or devices), the gas moving system, and sampling
lines.
The sample probe may be a stainless steel tube with a 90 degree bend
on the end for gas streams containing negligible quantities of particu-
lates. Streams from the digester, acid fortification tower, evaporators,
and stock washers contain negligible concentrations of particulate
matter.
Sample probes for gas streams containing high concentrations of
particulate matter usually include a filtering device. The filtering
device may be a porous ceramic probe, a plug of glass wool or a. heated
filter. Gaseous emissions from recovery furnaces or incinerators, from
smelt tanks and from spray dryers contain significant concentrations of
particulate matter.
In nost systems the major purpose of the conditioning device is to
prevent uncontrolled condensation of water vapor in the gas stream.
Unwanted condensation can be prevented by keeping the temperature of all
parts of the system above the dew point of the gas, by withdrawing
moisture through a semipermeable membrane, or by diluting the sample with
a dry gas. To dry a gas sample using a membrane, a membrane is used which
will selectively allow water vapor to pass through. A dry gas is passed
across one side of the membrane and the sample across the other side.
Water vapor passes through the membrane from the wet sample gas to the
dry receiving gas.
Some gas conditioning systems include components designed to remove
interfering species from the sample before the sample reaches the detector
As indicated above, some systems change the chemical composition of the
8-4
-------
sample in a controlled manner to facilitate detection.
The gas moving system usually includes a pump or aspirator to pull gas
through the system. For detectors which must be operated under positive
pressure, a positive displacement leakproof vacuum pump must be located
upstream of the detector. In many cases the pump or aspirator is located
downstream of the detector. Flow controlling and measuring devices are
included in the gas moving system.
Sample transfer lines must be large enough to provide a low pressure
drop and short enough to provide a low retention time. The material must be
inert to avoid loss of the material being measured by physical absorption
or chemical reaction. Polyethylene or Teflon are the usual materials.
Electrically heated Teflon tubing is commercially available.
8.3 CONCENTRATION MEASUREMENTS
Concentrations of pollutants present in the gas phase can be monitored
continuously or manually. Continuous monitoring of major emission streams
is a useful tool to determine whether a given mill is meeting emission
regulations. Particulate emissions are usually measured manually.
8.3.1 Manual Methods for Measuring Sulfur Dioxide Concentrations
The two leading methods for measuring sulfur dioxide concentrations
manually are EPA Method 6 and the Reich test. In EPA Method 6 the filtered
gas is first drawn through 80 percent isopropanol to remove sulfur trioxide.
After sulfur trioxide is removed, sulfur dioxide is collected and oxidized
in impingers containing 3 percent hydrogen peroxide. Sulfur dioxide is
determined as sulfate using the barium perchlorate-thorin titration.
In the Reich test the gas stream containing sulfur dioxide is passed
through a solution containing a known amount of iodine with some starch
indicator. The gas stream is passed through until the color of the iodine
8-5
-------
and the starch indicator is almost completely discharged. The volume of
gas is measured using a wet test meter.
8.3.2 Methods for Continuous Measurement of Sulfur Dioxide Concentrations
Four instrumental methods are available for monitoring sulfur dioxide
emissions from pulp mills.
8.3.2.1 Coulometric Titration
One of the most popular instruments for monitoring sulfur dioxide
concentrations in pulp mill effluents uses coulometric titration. An
elemental halogen (bromine or iodine) is used to oxidize sulfur dioxide
to sulfate. The elemental halogen is generated from the corresponding
halide ion (Br or I ) electrolytically.
The instrument is set to maintain a fixed level of elemental halogen.
As the concentration of sulfur dioxide increases, the amount of current
required to maintain the preset concentration of elemental halogen
increases. The current through the cell is converted to an equivalent
voltage and the voltage used to operate a continuous recorder. The
recorder can be calibrated to give the sulfur dioxide concentration
directly. The sensitivity of the instrument can be varied by changing the
preset concentration of elemental halogen.
Any species which can be oxidized by the halogen used under the
conditions in the cell will interfere with the measurement of sulfur
dioxide. Serious interferences are not present in most gas streams from
mills using sulfite processes. However, in mills using kraft type
reduction furnaces (sodium base sulfite mills) hydrogen sulfide could
present serious interferences. Other species which may interfere are
organic sulfur gases, olefinic and aromatic hydrocarbons, terpenes,
acrolein and
8-6
-------
8-3.2.2 Electrochemical Membrane Cells
In electrochemical membrane cells the conditioned gas sample passes
through a detection cell. One wall of the detection cell is a semipermeable
plastic membrane. The sulfur dioxide in the gas selectively diffuses
through the membrane and into an electrolyte solution. The sulfur dioxide
produces a change in the electrochemical potential across the cell that is
directly proportional to the concentration in the sample gas.
Electrochemical membrane cells are more selectively responsive to
sulfur dioxide than coulometric titration cells. The cells are reported
to respond linearly over a concentration range from 0.01 to 5000 ppm by
volume. The gas handling system for the electrochemical membrane cell
must include a leakproof vacuum pump upstream of the detector because
the membrane cells must be operated under positive pressure.
Particulate matter must be removed from the sample before it enters
the detection cell. Water vapor must be removed or reduced before
entering the detection cell. Sulfuric acid vapor causes severe corrosion
problems.
8.3.2.3 Conductivity Cells
Total sulfur oxides in gas streams from digesters and acid making
towers or acid fortification towers may be monitored using conductivity
cells. These relatively simple inexpensive nonspecific detectors can be
used for these streams because only negligible quantities of interfering
conductivity-producing gases or particulates are present. The gas is
withdrawn from the duct or flue and passed through a water scrubber. The
soluble gases dissolve in the water which is then passed through a
conductivity cell.
8-7
-------
8.3.2.4 Ultraviolet Spectrophotometry
Sulfur dioxide absorbs ultraviolet radiation; the absorbance
maximum is at 280 rim. Assuming that no interferences are present, the
amount of ultraviolet radiation (with wavelength approximately 280 nm)
absorbed by a gas is proportional to the concentration of sulfur dioxide
in the gas. Nitrogen dioxide is an interfering species.
Ultraviolet Spectrophotometry can be applied to the gas in the stack
or the gas can be withdrawn from the stack for analysis. One instrument
provides corrections for nitrogen dioxide interference.
8.3.3 Methods for Manual Measurements of Concentrations of Particulate
Matter
EPA Method 5 provides a standard means for measuring concentrations
of particulate matter. This method measures only particulate matter
collected on a filter maintained at 120 ± 14°C throughout the sampling
period. EPA Methods 1-4 are applied simultaneously to locate points for
sampling and to determine gas characteristics.
Washington Department of Ecology (DOE) Method 5 uses a sampling
train which is essentially identical to that specified by EPA Method 5.
The DOE method specifies an acetone wash of all sample exposed surfaces of
the sample probe before the filter. In addition, the contents of the
impingers downstream from the filter, and the water and acetone rinses of
sample exposed surfaces downstream of the filter are collected. All
liquid samples are evaporated and the weights of the solid materials
obtained are added to the weight of material collected on the filter to
determine total particulate concentrations.
An alternate procedure for measurement of particulate concentrations
8-8
-------
is to pass the gas sample through an impinger train. The material left over
after evaporation of the liquid in the impingers is taken as a measure of
the particulate matter in the gas stream. This method generally gives
significantly lower particulate concentrations than do methods which employ
filters. Two mills in Oregon (belonging to Publisher's Paper Company) are
using this method.
8.3.4 Continuous Monitoring of Particulate Emissions
Continuous monitors using bolometers or transmissometers have been used
to monitor particulate emissions. These devices are more suitable for
detecting upset conditions than for actual measurement of particulate
emissions.
8.3.5 Manual Measurement of Hydrogen Sulfide Emissions
EPA Method 11 provides a manual means of measuring hydrogen sulfide
emissions. This method is applicable to emissions from kraft type recovery
furnaces and associated smelt tanks. It is not applicable to emissions from
digesters in mills which produce semichemical pulp using a cooking liquor
which contains green liquor. The gases from these digesters contain organic
sulfur species such as methyl mercaptan in addition to hydrogen sulfide.
Hydrogen sulfide is the main reduced sulfur species present in kraft type
recovery furnace flue gases and the emissions from the associated smelt
tanks. Significant emission concentrations of other reduced sulfur species
can occur in systems when green liquor is used as the cooking liquor.
In this method hydrogen sulfide is collected in a series of midget
impingers containing alkaline cadmium hydroxide. After the collection is
complete, hydrogen sulfide is released from the precipitated cadmium
sulfide. A known amount of acidic iodine solution is used to effect this
release. The hydrogen sulfide is oxidized by the iodine and the excess
8-9
-------
iodine is back titrated with standard sodium thiosulfate.
8.3.6 Semicontinuous Monitoring of Total Reduced Sulfur (TRS) Compounds
When the concentrations of the different reduced sulfur species making
up the TRS emissions is desired, gas chromatography is employed. The
application of this method is described in EPA Method 16. Two gas chroma-
tographic columns are used: one for low molecular weight gases and the
other for higher molecular weight gases. Flame photometric detection is
used.
8.3.7 Continuous Monitoring of TRS
Total reduced sulfur species may be monitored continuously using
either coulometric techniques or electrochemical membrane cells. If
coulometric detection is used sulfur dioxide must be removed from the
sample before it reaches the coulometric titration cell. And, the cell
must be calibrated for the particular mixture of reduced sulfur species
present in the gas. An alternate procedure is to remove sulfur dioxide
from the sample, oxidize the reduced sulfur species to sulfur dioxide and
measure the resulting sulfur dioxide concentration. Gas handling and
conditioning systems have been designed so that both sulfur dioxide and
TRS can be measured coulometrically in the same stream.
To determine TRS using an electrochemical membrane any sulfur dioxide
originally present in the sample must be removed. The reduced sulfur
species are oxidized to sulfur dioxide and the resulting sulfur dioxide
concentration is measured in an electrochemical membrane cell.
8-10
-------
REFERENCES
1. Environmental Pollution Control, Pulp and Paper Industry, Part 1, Air.
Environmental Protection Agency, Office of Technology Transfer. EPA
625/7-76-001. October 1976. p. 17-7
2. Environmental Pollution Control, Pulp and Paper Industry, Part 1, Air.
Environmental Protection Agency, Office of Technology Transfer. EPA
625/7-76-001. October 1976. p. 17-8.
8-11
-------
APPENDIX A
LIST OF MILLS PRODUCING WOOD PULP BY THE SULFITE PROCESSES AND MILLS PRODU-
DUCING SEMICHEMICAL PULP
A-l
-------
Table A-l. MILLS IN THE UNITED STATES PRODUCING SULFITE PULP
>
N>
State
Alaska
Alaska
Florida
Malno
Maine
Halite
Minnesota
City and County
Ketchlkan
Southeastern
County
Sitka
Southeastern
County
Fernandlna Beach,
Nassau County
Brewer
Penobscot
County
mlllnocket
Penobscot
County
Wins low
Kennebec
County
Cloquet
Carlton
County
Company
Ketchlkan Pulp Co., Div.
Louisiana-Pacific Corp.
(Exec, office In Portland,
OR)
Alaska Lumber and Pulp Co.
Inc.
ITT Rayonler Inc., Fernan-
dlna Dlv.
(Exec. Office In New York.
NY)
Eastern Fine Paper Inc.,
Affl. of Eddy Paper Co.
Ltd.
(Exec, office In Hull,
Que.)
Great Northern Paper Co. ,
A Great Northern Nekooea
Co.
(Exec, and sub. offices In
Stamford, CT)
Scott Paper Co., Northeast
Oper.
(Exec, office In Phila-
delphia, PA)
Potlatch Corp., Northwest
Paper Dlv.
(Exec, office In San
Capacity
Address and Telephone (Me/day) (tons/day) Comments
Box 1619 558 615
Ketchlkan, AK (99901)
Box 1050 544 600
Sltka, AK (99835)
Phone: 907-747-2265
Fernandlna Beach, FL (32034) 408 450
Phone: 904-261-3612
Box 129 (172)b (190) Mill idle1
Brewer, ME (04412)
Phone: 207-989-7070
Mllllnocket, ME (04462) 544b 600
Phone: 207-723-5131
Ulnslow, ME (04901) (440) (485) Mill Idle8
Phone: 207-872-2751
Cloquet, MN (55720) (109) (120) Mill Idle8
Phone: 218-879-2300
Francisco, CA)
(Continued)
-------
Page Two
Table A-l. (continued)
State
New York
Oregon
Oregon
Oregon
Oregon
Pcnnsy 1-
vml la
Wnshlng-
ton
City and County
Ciena Falls
Warren County
Lebanon
Linn County
Oregon City
Clackatnas County
Newberg
Yamhlll County
Salem
Marlon County
Mehoopnny
Wyoming County
Anacortes
Skagit County
Company
Finch, Fruyn & Co. Inc.
Crown 7-ellerbach
(Exec, office In San
Francisco, CA)
Publishers Paper Co.,
Sub. of the Times Mirror
Co.
Publishers Paper Co.,
Newberg Div., Sub. of
the Times Mirror Co.
(Exec, office in Oregon
City. OR)
Boise Cascade Corp., Paper
Group Div.
(Exec, office in Boise
ID)
(Div. office in Portland,
OR)
Procter & Gamble Paper Pro-
ducts Co., Sub of the
Procter & Gamble Co.,
(Exec, office In Cincin-
nati, OH)
Scott Paper Co., West Coast
Div.
Capacity
_.. Address and Telephone (Mg/day) (tons/day) Comments
1 Glen St. 212 300
Ciena Falls, NY (12801)
Phone: 518-793-2541
Box 486 91 100
Lebanon, OR (97355)
Phone: 503-258-3121
419 Main St. 209 230
Oregon City, OR (97045)
Phone: 503-656-5211
Box 70 227 250
Newberg, OR (97132)
Phone: 503-538-2151
315 Commercial St. S. 227b 250
Salem, OR (97301)
Phone: 503-362-2421
Box 32 218C 2'nc
Mehoopany, PA (18629) '
Phone not given
B°* 19° .,.» (12?) <"0) Mill ah,,t Huwn'po.
^"^A "1 9 P "t'y *prt,1R .978
(Exec, office in Phila-
delphia, PA)
Phone: 206-293-2144
(continued)
-------
Page Three
Table A-l (continued)
State
Washing-
ton
Washing-
ton
Washing-
ton
Washing-
ton
Washing-
ton
Washing-
ton
Washing-
ton
City and County
Bellingham
What com County
Camas
Clark. County
Cosmo polls
Graya Harbor
County
Everett
Snohomish
County
Hoquiam
Grays Harbor
County
Long view
Cowlitz County
Tort Angeles
C la 11 am County
Company
Georgia-Pacific Corp.,
Tissue Products Div.
(Exec, office in Portland,
OR)
Crown Zellerbach
(Exec, office in San Fran-
cisco, CA)
Weyerhaeuser Co., Pulp Div.
(Exec, office In Tacoma,
WA)
Scott Paper Co., Northwest
Operations
(Exec, office in Phila-
delphia, PA)
ITT Rayonler Inc., Grays
Harbor Div.
(Exec, office In New York,
NY)
Paperboard Div.
(Exec, office in Tacoma,
WA)
ITT Rayonier Inc., Port
Angeles Div.
Capacity
Address and Telephone (Mg/day) (tons/day) Comments
300 W. Laurel St. 454 500
Bellingham, WA Box 1236 (98225)
Phone: 206-733-4410
Camas, WA (98607) 400 440
Phone: 206-834-3021
Box 280 408 450
Cosmopolia, WA (98537)
Phone: 206-532-7110
Everett, WA (98201) 757 835
Phone: 206-259-7333
Box 299 430 475
Hoquiara, WA (98550)
Phone: 206-532-1410
Longview, WA (98632) 363 400
Plione: 206-425-2150
Box 191 454 500
Port Angeles, WA (98362)
(Exec, office In New York, Phone: 206-457-3391
NY)
(continued)
-------
Page Four
Table A-l (continued)
State
Wisconsin
Wisconsin
Wisconsin
Wisconsin
W 1 scons In
Wlaconsln
Wisconsin
Wisconsin
City and County
Appleton
Outagamle
County
Brokaw
Marathon County
Green Bay
Brown County
Green Day
Brown County
Oconto Falls
Oconto County
Park Falls
Price County
Peshtigo
Harlnctte County
Port Edwards
Wood County
Company
Consolidated Papers Inc
(Exec, office in Wis-
consin Rapids, WI)
Wausau Paper Mills Co.
American Can Co .
(Exec, office in Green-
wich, CT)
Procter & Gamble Paper
Products Co.
(Exec, office in Cincin-
nati, OH)
Scott Paper Co.
(Exec, office in Phila-
delphia, PA)
Flambeau Paper Co.
Badger Paper Mills Inc.
Nekoosa Papers Inc., Sub
of Great Northern Nekoosa
Capacity
Address and Telephone (Mg/day) (tons/day) Comments
1130 E. John 112 123
Appleton, WI (54911)
Phone: 414-733-4461
Brokaw, WI (54417) 169 186
Phone: 715-675-3361
Day St. 136 150
Green Bay, WI (54305)
Phone: 414-432-7721
Box 1510 377d 416d
Green Bay, WI (54305)
Phone: 414-468-2200)
Central Ave. (106) (117) Mill shut down , Spring
Oconto Falls, WI (54154) 1978
Phone: 414-846-3411
200 N. 1st Ave. 100 110
Park Falls, WI (54552)
Phone: 715-762-3231
W. Front St., Box 149 100 110
Peshtigo, WI (54157)
Phone: 715-582-4551
100 Wisconsin River Dr. 195 215
Port Edwards, WI (54469)
Corp.
(Exec, office In Stamford,
CT)
Phone: 715-887-5111
(continued)
-------
Page Five
Table A-l (continued)
Capacity
State City and County Company Address and Telephone (Ha/day) (tons/day) Comments
Wisconsin Rhlnelauder St. Regis Paper Co., Print- 515 W. Davenport St. 68 75
Onelda County Ing & Packaging Papers Rhtnelander, WI (51501)
Ulv. Phone: 715-369-4305
(Exec, office in New York.
NY)
Wisconsin Rothschild Weyerhaeuser Co., Paper Div. Box 200 181 200
Marathon County (Exec, office in Tacoma, Rothschild, WI (54474)
WA) Phone: 715-359-3101
TOTAL CAPACITY OF OPERATING SULFITE MILLS IN THE UNITED STATES 8002 8820
Unless otherwise noted, capacity figures are from a personal communication from Isaiah Gellman, Executive Vice President, National
Council of the Paper Industry for Air and Stream Improvement, Incorporated, New York, NY. Letter dated 20 June 1978.
1 Post's 1978 Pulp and Paper Directory, Miller Freeman Publications, Inc., San Francisco (1977).
c llendrickson, E. R., J. E. Roberson, and J. B. Koogler, Control of Atmospheric Emissions in the Hood Pulping Industry, Volume 1, Final
Report: Contract No. CPA 22-69-18. March 15, 1970.
Personal communication with Paul Dldier, Wisconsin Bureau of Water Management; telephone report dated 18 July 1978.
6 Personal communication with Richard Hoover, General Superintendent, Scott Paper Company, Anacortes, Washington, Telephone conversation
dated 1 June 1978.
-------
Table A-2. MILLS IN THE UNITED STATES PRODUCING SEHICIIEMICAL PULP AND ASSOCIATED WITH KRAFT HILLS
State
Cat 1 ferula
Florida
Georgia
Georgia
Louisiana
l.nn Is 1 ana
l.mi Is i nna
City and County
Antloch
Contra Costa
County
Fernandlna Beach
Nassau County
Cedar Springs
Early County
Savannah
Chatham County
Bastrop
Morehouse Parish
Bogalusa
Washing! on
Parish
Hodge
Jackson Parish
Company
Flbrehoard Corp., San
Joaquin Dlv.
(Exec. Office In
San Francisco, CA)
Container Corp. of America
Sub. ol" Marcor Inc.
(Exec. Office in
Chicago, IL)
Great Southern Paper Co.,
A Great Northern
Nekooaa Ci>. (Exec.
Office in Stamford, CT)
Union Camp Corp.
(Exec. Office In
Wayne, NJ)
International Paper Co.,
Industrial Packaging
Div. (Exec. Office in
New York, NY)
Crown Zellerbach, Mill
Dlv. (Kxec. Office in
San Francisco, CA)
Con t Inenlal Forest Indus-
tries, Continental
Capacity a
Address and Telephone (Mg/day) (Tons/dny) Comments
Wilbur Ave. 218 240
Antiocli, CA (94509)
N 8th St. 317 350
Femandina Beach, FL
(32034)
901-261-5551
Box 44 308 340
Cedar Springs , GA
(31732)
912-372-4541
Box 570 273 300
Savannah , CA
(31402)
912-236-5771
f. Jefferson., Box 312 408 450
Bastrop, LA (71220)
318-281-1211
Box 1060 136 15U
Bogalusa, LA
(70427)
504-732-2511
llodge , LA (71247) 227 250
318-259-4421
Croup, Inc. (Exec. Office
In New York, NY)
(c o l
t 1 n u e d)
-------
Page Two
Table A-2 (continued)
I
00
State
Louisiana
New Hamp-
shire
North
Carolina
Oklahoma
Oregon
Oregon
South
Carolina
City and County
West Monroe
Ouachita Parish
Berlin
Coos County
Plymouth
Martin County
Valllant
McCurtaln County
Albany
Linn County
Toledo
Lincoln County
Oeorgetown
Georgetown
County
Company
Olinkraft Inc. (Exec.
Office at this
location)
Brown Co., Paper Group
(Exec. Office in
Pasadena, CA)
(Dlv. Office In
Kalamazoo, Ml)
Weyerhaeuser Co., North
Carolina Oper., Fiber
Dlv. (Exec. Office in
Tacoma, WA)
Weyerhaeuser Co. (Exec.
Office in Tacoma, WA)
Western Kraft Paper Group,
Div. of Willamette In-
dustries (Exec. Office
In Portland, OR)
Georgia-Pacific Corp.
(F.xec. Office In
Portland, OR)
International Paper Co.,
Industrial Packing Div.
(Kxec. Office In New
Capacity
Address and Telephone (Mg/day) (Tons/day) Comments
Box 488 227 250
West Monroe, LA (71291)
318-362-2000
650 Main St. 190 210
Berlin, Nil (03570)
603-752-4600
Box 746 227 250
Plymouth, NC (27962)
919-793-8111
Drawer C 725 800
Valliant, OK (74764)
405-933-7211
Box 339 181 200
Albany, OR (97321)
503-926-2281
Box 580 227 250
Toledo, OR (97391)
503-336-2211
Box 528 1400 1550
Georgetown, SC (29440)
803-546-6111
York, NY)
(continued)
-------
Page Three
Table A-2 (continued)
Stale City and County
Virginia
Virginia
Wash Ington
Wash 1 ngton
Washington
Coving ton
Alleghany
County
Mopewell
Prince George
County
Longview
Cowlltz County
Longview
Cowlitz County
Wallula
Walla Walla
County
'Unless otherwise noted, Infortnatioi
San Francisco, California (1977)
llt'nd r I ckson ,
E. R. , J. E. Roberaon
Company
Westvaco Corp., Bleached
Board Dlv. (Exec. Office
In New York, NY)
Continental Forest Indus-
tries, Continental Group
Inc. (Exec. Office in
New York, NY)
Longview Fibre Co.
Weyerhaeuser Co., Pulp
& Paperboard Div.
(Exec. Office in
Tacoma, WA)
Bolae Cascade Corp.,
Paper Group Dlv.
(Exec. Office In
Bnlse, ID) (Dlv.
Office In Portland,
OR)
A Is from Post's 1978 Pulp and
, and J. B. Koogler, Control of
Capacity
Address and Telephone (Mg/doy) (Tons/day) Comments
Covlngton, VA (24426) 273 300
703-962-2111
Box 201 159 175
llopewell, VA (23860)
804-458-9831
Box 639 200 220
Longview, WA (98632)
206-425-1550
Longview, WA (98632) 2)8 240
206-425-2150
Box 500 249 275
Wallula, WA (99363)
509-547-2411
Paj>er Directory. Miller Freeman Publications, Inc.
Atmospheric Emissions in the Wood Pulping Industry, Volume 1, Flnnl
Deport: Contract No. CPA 22-69-18. March 15, 1970.
-------
Table A-3. MILLS IN THE UNITED STATES PRODUCING SEMICHEMICAL PULP WITH NO ASSOCIATED KRAFT MILLS
I
!-
O
State City and County
Alabama Mobile
Mobile County
Alabama Stevenson
Jackson County
Indiana Terre Haute
Vlgo County
Iowa Dubuque
Dubuque County
Iowa Fort Madison
Lee County
Kentucky Hawesvllle
Hancock County
Michigan Filer City
Company
National Gypsum Co.
(Exec, office in Dallas,
TX)
Mead Corp., The Paperboard
Dlv. Mead Paper Group
(Exec, office In Dayton, OH)
Ueston Paper & MFG. Co., The,
Terre Haute Mill
Celotex Corp., The, Sub. of
of Jim Walter Corp.
(Ki-p.c. office in Tampa, FL)
Consolidated Packaging
Corp.
(Exec, office In Chicago,
IL)
Western Kraft Paper Group,
Wtlliamette Industries Inc.
Wescor Dlv.
Packaging Corp. of America,
Capacity
Address and Telephone (Mg/day) (Tons/day) Comments
Box 1188 159a 175
Mobile, AL (36601)
Phone: 205-433-3971
Box H 680b 750
Stevenson, AL (35772)
Phone: 205-437-2161
Pralrieton Rd . S Voorhees 245b 270
St.
Terre Haute, IN (47808)
Phone: 812-234-6688
Box 569 227a 250
Dubuque, IA (52001)
Phone: 319-588-1481
Box 250, Foot of 18th St. 127b 140
Fort Madison, IA (52627)
Phone: 319-372-3152
Box 159 2501' 275
Hawesvllle, KV (42348)
Phone: 502-927-2641
Filer City, MI (49634) 544b 600
Manistee County
Div. of Tenneco, Inc.
(Exec, office In Evaneton,
IL)
Phone: 616-723-9951
(continued)
-------
Page Two
Table A-3 (continued)
State
Michigan
Michigan
Minnesota
Miss Issippi
New Hamp-
shire
N.'w York
City and County
Ontonagon
Ontonagon County
Otsego
Allegan County
Saint Paul
Ramsey County
Meridian
Lauderdale County
Groveton
Coos County
Lyons Fulls
Lewis County
Company
lloerner Waldorf, Div. of
Champion International
Corp.
(Exec, office In St. Paul,
UN)
Menasha Corp., Paperboacd Dlv.
(Exec, office In Neenah,
WI)
lloerner Waldorf, Dlv. of
Champion International
Corp., St. Paul Mill
(Exec, office In Stamford,
CT)
Fllntkote Co. , The
(Exec, office in Stamford,
CT)
Crovc'ton Papers Co., Sub.
of Diamond International
Corp.
(Exec, office in New York,
NY)
Georgia-Pacific Corp., Lyons
Falls Dlv.
Capacity
Address and Telephone (Mg/day) (Tons/day) Comments
11% Lake shore Rd . 400b 440
Ontonagon, MI (49953)
Phone: 906-884-4121
320 N. Farmer St., Box 155 204b 225
Olsego, Ml (49078)
Phone: 616- 692-6141
2250 Wabash Ave. 3l8a 350
Saint Paul, MN Box 3260
(55165)
Phone: 612-641-498
Box 1551 45a 50
Meridian, MS (39301)
Phone: 601-482-0151
Croveton, Nil (03582) 272b 300
Phone: 603-636-1154
Lyons Falls, NY (13368) 109a 120
Phone: 315-348-8411
(Exec, office in Portland,
OR)
(cont Inued)
-------
Page Three
Table A-3 (continued)
Capacity
State
New York
North
Carolina
Ohio
Ohio
Oregon
City and County
Plattsburgh
Clinton County
Sylva
Clrclevllle
Plckaway County
Coshocton
Coahocton
County
North Bend
Company
Georgia-Pacific Corp.,
Tissue Products Dlv.
(Exec. Office In
Portland, OR)
Sylva Paperboard
Container Corp. of Amer-
ica, Sub. of Marcor,
Inc. (Exec. Office In
Chicago, IL)
Stone Container Corp.
(Exec. Office In
.Chicago, IL)
Menasha Corp,, Paperboard
Address and Telephone-
Box 789
Plattsburgh, NY (12901)
518-561-3500
Not Listed In Post's
Directory
401 W. Mill St.
Clrclevllle, OH (43113)
614-474-2146
500 N. Fourth St.
Coshocton, OH (43812)
614-622-6543
Box 329
(Hg/day)
91a
(245)b
272b
408b
181b
(Tons/day) Comments
100
(270) Mill ldlea
300
450
200
Coos County
Pennayl- Erie
vanla Erie County
Pennsyl- Sunbury
vanla Northumberland
County
Puerto Areclbo
ArecIbo
District
Dlv. (Exec. Office In
Neenah, WI)
llaininerniill Papers Group
Uiv. of.'Hammermlll Paper Co.
Erie Plant
Celotcx Corp., Sub. of
Jim Walter Corp
(Exec. Office In Tampa, FL)
Carlbe Inc., Productos
Forestales, Areclbo
Mill
North Bend, OR (97459)
503-756-5171
East Lake Road, Box 1440 35QC 385
Erie, PA (16533)
503-756-5171
Front & Susquehanna St. 217a 240
Sunbury, PA (17801)
717-286-5831
Box 695 113a 125
Areclbo, PR (00612)
809-878-7100
B&H recovery listed
(continued)
-------
Page Four
Table A-3 (continued)
I
M
OJ
State
South
Carolina
Tennessee
Tennessee
Virginia
Virginia
Virginia
City and County
llartsvllle
Darlington
County
llarrlman
Roane Cointy
New Johnsonvllle
Humph rays
County
Big Island
Bedford
Comity
Lynchburg
Campbell
County
Rlvervllle
Aralierst
Coiilty
Company
Sonoco Products Co.
(Exec. Office at
this location)
Harrlman Paperboard
Corp. , Dtv. of
Lawrence Paporboard
Corp.
Inland Container Corp.
(Exec. Office In
Indianapolis, IN)
Owens-Illinois Inc.,
Foreat Products Dlv.
(Exec. Office In
Toledo, OH)
Mead Corp., Mead Paper-
Board Products, Mead
Paperboard Group
(Exec Office In
Uaycon, Oil)
Virginia Fibre Corp.
Rlvervllle Mill
Capacity
Address and Telephone (Mg/day) (Tons/day) Comments
N. Second St. 408b 450
Hartsvllle, SC (29550)
803-383-7000
Emory St. 227b 250
llarrlman, TN (37748)
615-882-1812
Box 299 358b 395
New Jolinsonvllle, TN
(37134)
615-535-2161
Big Island, VA (24526) 522a 575
804-299-5911
Box 980 (172>b (190) Mill Idle
Lynchburg, VA (24505)
804-847-5521
Rlvervllle, VA 663° 510
Box 339, Amlierst, VA
(24521)
804-933-8643
(continued)
-------
Page Five
Table A-3 (contlnuued)
I
M
*-
State
Wisconsin
City and County
Green Bay
Brown County
Company
Green Bay Packaging Inc.,
Paper Mill Div.
(Exec. Office in
Green Bay, WI)
Capacity
Address and Telephone (Mg/day) (Tons/day)
Box 1107 181b 200
Green Bay, WI (54305)
414-465-5000
Comments
Wisconsin Tomahawk
Lincoln
County
Owens-Illinois Inc.
(Exec. Office In
Toledo, OH)
Tomahawk, WI (54487)
715-453-2131
526a
Total Capacity of Operating Semichemlcal 7897
Mills Not Associated with Kraft Mills
580
8705
aPost'3 1978 Pulp and Paper Directory, Miller Freeman Publications, Inc., San Francisco, California (1977).
Personal communication with Isaiah Gillman, Executive Vice President, National Council of the Paper
Industry for Air and Stream Improvement, Inc., New York, NY. Letter dated 20 June 1978.
^Hendrlckson, E. R. , J. E. Roberson, and J. B. Koogler, Control of Atmospheric Emissions in the Wood Pulping Industry, Volume 1,
Final Report: Contract No. CPA 22-69-18. March 15, 1970.
-------
APPENDIX B
SULFITE PULPING MODEL IV CALCULATION
B-l
-------
SULFITE PULPING MODEL IV CALCULATION
The symbols used in the Model IV calculation are defined in Table G-l.
1. Assume1 a straight line construction and modification rate to replace
obsolete capacity: P, = 0.031
2. Assume a compound construction and modification rate to increase (de-
crease) industry capacity
P
Sulfite Pulp Capacity Fractional Increase
Year (Gg/day) (Decrease)
1967
1968
1969
1970
1971
1972
1973
1974
1975
1976
1977
AVERAGE
9.050
8.825
8.675
8.530
8.450
8.325
8.350
8.500
8.365
8.235
8.002
-0.0122
-0.0108
-0.0100
-0.0091
-0.0090
-0.0079
-0.0106
-0.0199
-0.0219
-0.0283
-0.0140
Sulfite pulp capacity is determined by adding 50% of the dissolving
pulp grade capacity to the sulfite paper grade capacity in Figure 3-3.
The baseline year is 1977. P is calculated from the following equa-
tion.
J.977-XCapacity(1977) f n
Pc ~ \ Capacity (X) l (B"1}
3. A equals the sum of the sulfite pulping capacity by all four chemical
bases. Therefore,
B-2
-------
Table B-l. SYMBOLS USED IN MODEL IV CALCULATION
TQ = total emissions in the i year under baseline year regulations (tons/
S yr)
T = total emissions in i year under new or revised NSPS which have been
promulgated in the jc^ year (tons/yr)
K = normal fractional utilization rate of existing capacity, assumed con-
stant during time interval
A = baseline year production capacity (production units/yr)
B = production capacity from construction and modification to replace ob-
solete facilities (production units/yr)
C = production capacity from construction and modification to increase out-
put above baseline year capacity (production units/yr)
p = construction and modification rate to replace obsolete capacity
(decimal fraction of baseline capacity/yr)
P = construction and modification rate to increase indsutry capacity (deci-
c mal fraction of baseline capacity/yr)
Es = allowable emissions under existing regulations (mass/unit capacity)
En = allowable emissions under standards of performance (mass/unit capacity)
Eu = emissions with no control (mass/unit capacity)
B-3
-------
A = Ca + Mg + Na + NH3
= 1.151 + 3.617 + 0.430 + 2.804
= 8.002 Gg/day
4. K = 0.91 (from Section 3.2.3)
5. Uncontrolled emissions (Eu) are calculated as follows:
SOa
(Mg/Gg pulp)
Particulate
(Mg/Gg pulp)
Digester discharge
Acid plant
Recovery system
Ca
29.0
2.5
Na
= 4'97
1-45
3617\
80021
(1.6) = 0.72
(5'0) - °'27
.9.36
40.86
1.8
1.8
6. Allowable emissions (En) under standards of performance are calculated
as follows:
S02
(Mg/Gg pulp)
Particulate
(Mg/Gg pulp)
Digester discharge
Acid plant
Recovery system
.;.Ca
0.2
0.2
2.67
Na
- o.oi
1.47
- °-72
= 0.08
4.15
4.55
En = (1.3)(4.55) = 5.92
0.94
0.94
En = (1.3)(0.94) = 1.22
B-4
-------
A new standard cannot be set at average best controlled emission level
for all sulfite systems. This would imply that a mill would have to achieve
lower emissions than the best controlled emission level in order to be in
compliance with the new standard. Therefore, an adjustment factor (1.3)
is included to increase the emission limit for the new standard.
7- Allowable emissions (Es) under existing regulations are calculated
as follows:
N
Es = Z Es^ (B_2)
where Es. = Emission limitation in i state
A. = Decimal fraction of total capacity located in i
state
i = Individual state
N = Total number of states over which capacity is distri-
buted.
If a state had sulfite pulping capacity, but no specific sulfite regu-
lations, then Es. = Eu.
SULFUR DIOXIDE
State Es A.
Alaska (10 Mg/Gg Pulp)(f^jf) =1-38
Florida (40.86 Mg/Gg pulp) = 2.08
544 \
Maine (20 Mg/Gg pulp) =1-36
New York (40.86 Mg/Gg pulp)(g§g) = 1.39
Oregon (10 Mg/Gg pulp)(g^) = 0.94
Pennyslvania (40.86 Mg/Gg pulp)(g§|) = 1.11
Washington (10 Mg/Gg pulp)(|§§|) = 4 . 08
Wisconsin (40-86 Mg/Gg pulp)(|§|
19.63 Mg/Gg
3-5 PulP
-------
PARTICULATES
State Es.A.
Alaska
Florida
Maine
New York
Oregon
P ennsy Ivania
Washington
Wisconsin
(1.0
(1.8
(1.8
(1.8
(2.0
(1.8
(2.0
(1.8
Mg/Gg
Mg/Gg
Mg/Gg
Mg/Gg
Mg/Gg
Mg/Gg
Mg/Gg
Mg/Gg
,/1102\
pulp)(8002j
i \/ 408\
pulp)l8002J
W 544^l
pulp; ( 8002/
)( 212\
pu p V8002/
_..i_\ / 754\
\ O U(J^ /
( 218 \
Pulp^ \8002/
,/3266\
pUlp) ^gQQ2j
,/1438\
P P-'\8002/
= 0.14
= 0.09
- 0.12
= 0.06
= 0.19
= 0.05
= 0.82
- 0.32
1.79 Mg/Gg
pulp
8. B * AiPb = (8.002 Gg pulp)(1983-1977)(0 .031)
= 1.488 Gg pulp/day
9. C = A[(l + Pc)i - 1] = (8.002 Gg pulp)[(l - 0.0140)(1983"1977) - 1]
= -0.649 Gg pulp/day
10. SULFUR DIOXIDE
Tc = EsK(A + C) = (19.68 Mg SOa/Gg pulp)(.91)(8.002-0.649 Gg,pulp)
o cisy
= 131.7 Mg S02/day
TN = EsK(A - B) + EnK(B + C)
= (19.68 Mg S02/Gg pulp)(.91)(8.002 - 1.488 Gg pulp/day) +
(4.55 Mg SOa/Gg pulp)(.91)(1.488 - 0.649 Gg pulp/day)
= 120.1 Mg S02/day
TS - TN= (131.7 - 120.1) Mg SO /day = 11.6 Mg S02/day
= (12.8 ton S02/day)
11. PARTICULATES
T - EsK(A + C) = (1.79 Mg part./Gg pulp)(.91)(8.002 - 0.649 Gg pulp/
day)
= 11.98 Mg part/day
B-6
-------
= EsK(A - B) + EnK (B + C)
= (1.79 Mg part/Gg pulp) (. 91) (8. 002 - 1.488 Gg pulp/day) +
(0.94 Mg part/Gg pulp) (. 91) (1. 488 - 0.649 Gg pulp/day)
= 11.33 Mg part/day
TS ~ TN= C11-98 - 11.33)Mg part/day = 0.65 Mg part/day
(0.72 ton part/day)
B-7
-------
REFERENCES
1. Hooper, T. G. and W. A. Marrone. Impact of New Source Performance
Standards on 1985 National Emissions from Stationary Sources. Volume
I, Final Report, Main Text, and Appendices I through III. The Re-
search Corporation of New England. Wethersfeld, Connecticut. EPA
Contract No. 68-02-1382, Task 3. October 1975. p. 63.
B-8
-------
TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing!
1. REPORT NO.
EPA-45Q/3/78-111
3. RECIPIENT'S ACCESSION NO.
4. TITLE AND SUBTITLE
Screening Study on Feasibility of Standards of Perfor-
mance for Two Wood Pulping Processes
5. REPORT DATE
Issued November 1978
6. PERFORMING ORGANIZATION CODE
. AUTHOR(S)
C. M. Thompson, W. C. Micheletti, J. C. Terry
8. PERFORMING ORGANIZATION REPORT NO.
9. PERFORMING ORGANIZATION NAME AND ADDRESS
Radian Corporation
8500 Shoal Creek Blvd.
Austin, Texas 78758
10 PROGRAM ELEMENT NO.
11. CONTRACT/GRANT NO
EPA 68-02-2608
12. SPONSORING AGENCY NAME AND ADDRESS
Environmental Protection Agency
Office of Air Quality Planning and Standards
Emission Standards and Engineering Division
Research Triangle Park, N. C. 27711
13. TYPE OF REPORT AND PERIOD COVERED
Final
14. SPONSORING AGENCY CODE
EPA/200/04
15. SUPPLEMENTARY NOTES
16. ABSTRACT
This report is a screening study for the sulfite and neutral sulfite semichemical (NSSC)
wood pulping processes. The purpose of the screening study is to develop background
information on both pulping processes and to advise on the feasibility and need for
standards of performance for either or both of them. This report provides a general
industry description and discusses in detail the operation of both wood pulpingprocesse;
Potential emission sources are identified, as well as available methods of emission
control. In addition, existing applicable regulations are summarized, national emis-
sions are estimated, and specific analytical methods are discussed.
17.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.IDENTIFIERS/OPEN ENDEDTERMS
c. COSATI Held/Group
Air Pollution Control Equipment
Pulp Manufacture
Sulfite Pulping
Performance Standards
Air Pollution Control
Stationary Sources
Wood Pulping
18. DISTRIBUTION STATEMENT
Unlimited
19. SECURITY CLASS /This Report,
Unclassified
21. NO OF PAGE;
190
20 SECURITY CLASS 'Th
Unclassified
22 PRICE
EPA Fo,m 222C-1 (Rev. 4-77}
5 C SSC _E TE
B-9
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